2012 PTQ q1

special features
OutlOOK
autOmatiOn and cOntrOl
envirOnmental
refining
gas prOcessing
petrOchemicals
PETROLEUM TECHNOLOGY QUARTERLY
ptq
Q1 2012
cover and spine copy 10.indd 1 8/12/11 09:34:10
www.ptqenquiry.com
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2012. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic,
mechanical, photocopying, recording or otherwise without the prior permission of the copyright owner.
The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care
has been taken in the preparation of all material included in Petroleum Technology Quarterly the publisher cannot be held responsible for any
statements, opinions or views or for any inaccuracies.
3 All at sea
ChrisCunningham
5 Outlook

15 ptq&a

21 Catalysts for maximising middle distillates
RubenMiravallesandTamaraGalindoRepsol
27 Using cold boiler feed water for energy recovery
AliSanDoG
anTurkish Petroleum Refneries Corporation

33 Cost estimating for turnarounds
GordonLawrence Asset Performance Networks
45 Abatement of hydrogen sulphide in asphalt
JenniferDraperandJosephStarkBaker Hughes
51 Oxygen enrichment in desulphurisation
ShivanAhamparamandStephenHarrisonLinde
55 Green retarder technology for the styrene industry
LishengXu,JavierFlorencio,VincentLewisandChristopherMorrison Nalco
AnaGuzman,CarmenMonfortandAnaOlivares Repsol Qumica Tarragona
65 Energy recovery with compact heat exchangers
MarcosMatsufugiAlfa Laval
71 Low rare earth catalysts for FCC operations
YenYungandKenBruno Albemarle Corporation
81 Catalyst additives reduce rare earth costs
RayFletcher Intercat
85 Consolidation of refnery control rooms
EricJanKwekkeboomYokogawa Europe & Africa
93 Integrated monitoring for optimising crude distillation
GregoryShahnovsky,TalCohenandRonnyMcMurrayModcon-Systems Ltd
102 Crude oil vapour pressure testing
HannesPichlerandKlausHense Grabner Instruments, a subsidiary of Ametek
105 Optimised hydrogen production by steam reforming: part I
SankeRajyalakshmi,KedarPatwardhanandPVBalaramakrishna
Larsen and Toubro
111 Improved catalytic reforming
AnthonyPoparad,BeatrixEllis,BryanGloverandStephenMetro
UOP LLC, A Honeywell Company
119 New crude oil basket for hydrogen savings
RajeevKumar,PrashantPariharandRaviKVoolapalli
Corporate R&D Centre, Bharat Petroleum Corporation Ltd
125 Industry News
126 Technology in Action
Covercaption:JettoweratSuncorsSarniarefnery,Ontario,Canada Photo:Suncor

Q1 (Jan, Feb, Mar) 2012
www.eptq.com
p
t
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Y L R E T R A U Q Y G O L O N H C E T M U E L O R T E P
contents/ed com copy 13.indt 1 12/12/11 13:47:42

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T
he European Union has arguably
been the global leader in biodiesel
production and use, with overall
biodiesel production increasing from 1.9
million tonnes in 2004 to nearly 10.3 million
tonnes in 2007. Biodiesel production in the
US has also increased dramatically in the
past few years from 2 million gallons in
2000 to approximately 450 million gallons
in 2007. According to the National Biodiesel
Board, 171 companies own biodiesel
manufacturing plants and are actively
marketing biodiesel.1. The global biodiesel
market is estimated to reach 37 billion
gallons by 2016, with an average annual
growth rate of 42%. Europe will continue to
be the major biodiesel market for the next
decade, followed closely by the US market.
Although high energy prices,
increasing global demand, drought
and other factors are the primary
drivers for higher food prices, food
competitive feedstocks have long
been and will continue to be a major
concern for the development of biofu-
els. To compete, the industry has
responded by developing methods to
increase process effciency, utilise or
upgrade by-products and operate
with lower quality lipids as
feedstocks.
Feedstocks
Biodiesel refers to a diesel-equivalent
fuel consisting of short-chain alkyl
(methyl or ethyl) esters, made by the
transesterifcation of triglycerides,
commonly known as vegetable oils or
animal fats. The most common form
uses methanol, the cheapest alcohol
available, to produce methyl esters.
The molecules in biodiesel are pri-
marily fatty acid methyl esters
(FAME), usually created by trans-
esterifcation between fats and metha-
nol. Currently, biodiesel is produced
from various vegetable and plant oils.
First-generation food-based feedstocks
are straight vegetable oils such as
soybean oil and animal fats such as
tallow, lard, yellow grease, chicken fat
and the by-products of the production
of Omega-3 fatty acids from fsh oil.
Soybean oil and rapeseeds oil are the
common source for biodiesel produc-
tion in the US and Europe in quanti-
ties that can produce enough biodie-
sel to be used in a commercial market
with currently applicable
PTQ Q1 2012 3
Editor
Chris Cunningham
[email protected]
Production Editor
Rachel Storry
[email protected]
Graphics Editor
Rob Fris
[email protected]
Editorial
tel +44 844 5888 773
fax +44 844 5888 667
Business Development Director
Paul Mason
[email protected]

Advertising Sales
Bob Aldridge
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Advertising Sales Offce
tel +44 844 5888 771
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Publisher
Nic Allen
[email protected]
Circulation
Jacki Watts
[email protected]
Crambeth Allen Publishing Ltd
Hopesay, Craven Arms SY7 8HD, UK
tel +44 844 5888 776
fax +44 844 5888 667
ISSN 1362-363X

Petroleum Technology Quarterly (USPS 0014-781)
is published quarterly plus annual Catalysis edition
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Vol 1 No 1
Q1 (Jan, Feb, Mar) 2012
All at sea
I
t being that time of the year, this issue of PTQ features our annual Outlook
section, which leads off with a concise appraisal of the state of the global
refning industry from the IEAs Executive Director, Maria van der Hoeven
(see p5). The story, not unexpectedly, can be distilled to: lots more capacity on
the way, with pressure building on more established centres of over-capacity.
A key image of the industry in years gone by was of crude carriers waiting
offshore the worlds refning hubs for the best pricing opportunities to
unload. In recent years, refners have become major exporters and the picture
is of shiploads of petroleum products chasing each other around the worlds
oceans competing for markets.
In the frst nine months of 2012, according to the Energy Information
Administration, the US exported 655 million barrels of fnished petroleum
products, including 121 million barrels of gasoline. At the same time, the
country imported 264 million barrels of fnished petroleum products, includ-
ing 32 million barrels of gasoline. Whether or not it is a long-term trend,
Americans are driving less. No refner wants to deal with the economics of
running a plant under capacity, so export markets are the means to shore up
production levels. This in turn means that quantities of crude oil imports,
and therefore prices, have held up.
How long refners in North America and Europe can hold onto those mar-
kets is a matter for some conjecture. A couple of examples from fast-growing
centres of refning may help to illustrate. According to Indias oil minister, in
a statement in December, the nations annual oil refning capacity will rise by
over 60% to 310 million tonnes by 201617 after new refneries in the states of
Orissa and Punjab are commissioned. At present, the refning capacity of
Indian refneries is around 190 million tonnes. India currently has enough
refning capacity for its local markets, with fuel demand at 140 million tonnes
in 201011. Domestic demand is projected to rise by 45% per annum up to
2017, which is some way short of accounting for a 60% increase in capacity.
In the far smaller but energy-rich United Arab Emirates, developments are,
proportionately, just as signifcant. Forty years ago, there were no refneries
in the UAE and the country depended on imports of petroleum products to
meet demand. The frst, 15 000 b/d refnery opened in 1976, but the recent
completion of the Ruwais expansion takes the Emirates refning capacity to
774 000 b/d. Signifcantly, current refning capacity is not geared simply to
local markets. Fuel oil production is being kept to a minimum and product
specifcations are geared to international markets. Sulphur levels in gasoline
and diesel produced at Ruwais will be as low as those in Europe and other
developed countries. Total refning capacity will grow by another 200 000
b/d when the $3 billion Fujairah refnery is completed in 2016. The outcome
of the UAEs fast-paced developments will be a combined total of 500 000
b/d of petroleum products, of which close to 200 000 b/d is slated for addi-
tion to the global export market.
The IEAs contribution to Outlook points out the inevitable consequences
of capacity additions across Asia and the Middle East: over-capacity in
Europe and North America is likely to bend under the strain imposed by
more, and more modern, refneries pouring products into the global export
pool. The least competitive refneries will succumb.
CHRIS CUNNINGHAM
p
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contents/ed com copy 13.indt 2 12/12/11 14:42:52
low rare earth loves
high performance
BASFs Rare Earth ALternative (REAL) solutions target the needs
of todays Fluid Catalytic Cracking (FCC) catalyst market.
Through a world-class combination of technology, technical
service, procurement expertise, and investments in manufacturing
and R&D, BASF delivers performance and value to customers
looking for options to reduce rare earth costs.
At BASF, we create chemistry.
www.catalysts.basf.com/refning
www.ptqenquiry.com
basf.indd 1 8/12/11 15:05:34
Maria van der Hoeven
Executive Director
IEA
T
he story of refning is one
of two divergent trends.
Huge and modern capacity
increases are being built in key
emerging markets, and particularly
in Asia. But in developed OECD
markets, refners are seeing their
already low operating rates and
proftability squeezed further by
the newer additions. What will be the end game? The
simple answer is that we expect signifcant excess
refning capacity for at least another several years,
pushing many European and other OECD refneries to
close up shop.
Following the economic recession of 2008-2009, and
maturing OECD oil demand relative to the rapid growth
seen in the non-OECD, the OECD oil refning sector has
come under intense economic and operational pressure.
The new refning capacity in emerging countries is often
developed with high complexity, and is sometimes built
more for strategic than purely economic reasons. This
new capacity will place further pressure on OECD
refners not only because it is more effcient and of a
larger scale, but also because the differentiation between
environmental standards places OECD operators at a
further cost disadvantage.
As highlighted in the IEAs Medium Term Oil and Gas
Markets 2011, the world will add an additional 9.7
million b/d of crude distillation capacity post-2010, to
reach a total of 103 million b/d in 2016. This compares
to forecast demand growth of some 7 million b/d in the
period, of which an increasing share will be met by non-
refned supplies, such as biofuels, gas and coal to
liquids, NGLs and condensates, which bypass the
refning system.
Some 95% of additions are planned in the non-OECD,
and most notably in Asia. China alone is expected to
account for a third of global capacity growth, or 3.3
million b/d. That is largely in line with demand growth
estimates. While project uncertainty here is ever present,
the governments strategy seems to balance concerns
over surplus capacity and increased product import
requirements. Projects scheduled for the tail end of the
forecast are therefore likely to be managed in line with
evolving demand prospects. The rest of Asia will see a
further 1.3 million b/d added in the period, or 13% of
P
global growth, while signifcant investments are also
taking place in the Middle East and Latin America.
In contrast with Chinas caution, India is expanding
its refning industry strategically, to establish itself as a
key product exporter in the Asia Pacifc region. India is
already exporting high-quality products to the US, Latin
America and Europe since the opening of Reliances
huge new Jamnagar export plant in 2009. The country is
likely to further increase product surpluses as refnery
capacity is expanded by more than 1 million b/d by
2016. In the Middle East, Saudi Aramco has revived its
ambitious refnery expansion plan, which was
temporarily put on hold during the recession. It seems
that three of the four proposed mega-projects will now
come to fruition, with two 400 000 b/d projects likely
before 2016. Elsewhere in the region, the UAEs 400 000
b/d Ruwais project is expected in 2014. Latin American
expansions are dominated by Brazil, which is likely to
add 1 million b/d of capacity by 2016 through several
greenfelds projects.
Emerging market plans seem to be driven by various
objectives. Some major consumers wish for greater
product self-suffciency, while others are positioning
themselves as regional hubs. At the same time, some
erstwhile crude exporters are trying to shift to the export
of higher value-added products. Most are driven by a
mix of these goals.
OECD refning offers a stark contrast to this booming
picture. Since the economic downturn, a total of 1.8
million b/d of crude distillation capacity has been shut
(or is frmly committed to shut) in the coming years.
That is the result of two things: structurally declining
demand and increased competition from the non-OECD.
The picture looks particularly bleak in Europe, where
seven refneries have already closed. Furthermore,
several plants have lately been sold to cash-rich
upstream non-OECD interests (Rosneft, CNPC and
Essar, among others). The US sector is interesting, as the
country is transforming into a signifcant product
exporter - a major turnaround from its position as a net
importer of more than 2 million b/d only a few years
ago. Diverging markets also exist within the country,
with those enjoying access to now very cheap crude
from the US Midwest at a great advantage, especially
compared to those in the diffcult East Coast refnery
market. With lower US gasoline import needs, European
refners face further pressure, as they are structurally
inclined towards gasoline production (and less towards
distillates). In the OECD Pacifc, industry rationalisation
also continues apace, with Japan accounting for the
www.eptq.com PTQ Q1 2012 5
Outlook for 2012
What are the important trends affecting the downstream processing industry this year?
Executives and experts forecast challenges and prospects that could affect proftability
outlook copy.indd 1 13/12/11 10:58:35
brunt. By 2014, Japanese refners face tough choices of
closing capacity or investing heavily in upgrading units.
As in the rest of the OECD, further capacity
rationalisation, over and above that already announced,
is likely before the market fnds a new equilibrium.
The global refning market is seeing a contrast
between developed and emerging economies, which is
familiar in so many areas of global economic activity.
The story is one of booming growth versus stagnation
or contraction compounded by technologically superior
and larger-scale competition. Given the short- to
medium-term economic picture and resulting demand
uncertainties, refners would be wise to maximise the
fexibility of their capacity plans, and to see what 2012
will bring. Some will not have that luxury.
Umberto della Sala
President & Chief Operating Offcer
Foster Wheeler
W
e are certainly seeing
robust activity in all of
the hydrocarbon-related
business sectors in which Foster
Wheelers Global Engineering
and Construction Group operates:
onshore and offshore upstream oil
and gas, midstream/LNG, refning,
chemicals, pharmaceuticals, metals
and mining and power.
Certainly, we have a good prospects pipeline, although
it is true that clients are in some cases taking longer to
reach fnal investment decision or are releasing projects
in phases. We have a number of projects that are going
through the fnal investment decision-making process
and for which we believe we are well positioned. And
we are seeing new opportunities continuing to emerge,
particularly in Asia, the Middle East and South America.
Looking forward into 2012, we see three key themes,
which are in many ways the same three that we saw at
the start of 2011, but these are now coming into even
sharper focus. First is local service delivery. This has
always been important to us and is becoming an even
stronger area of focus for us and for our clients. We have
made further strides forward this year, for example in
Saudi Arabia and in Azerbaijan, by developing our own
resources and by building relationships with local or
regional client and/or contractors to enable us to deliver
the Foster Wheeler product locally and competitively to
our clients, for the long-term, in line with local content
requirements and our clients preferences.
Second, the emphasis is on upstream. We are seeing
clients splitting their organisations into separate
upstream and downstream companies, and many of
international oil companies are focusing more of their
planned capital spend on the upstream sector (many
include LNG in this category). The offshore and onshore
upstream sector remains a strategically important market
for us and one in which we are further developing our
skills, service portfolio and geographic presence.
The third theme relates to the size and complexity of
projects. Large projects are getting even larger and more
complex; for example, the scope and scale of some of
the planned investments in the Middle East, South
America and Asia. In a number of these regions, new
approaches are required, including bringing sources of
external fnancing, leveraging local partnerships and
developing innovative execution strategies, such as
smart cloning for fast-track delivery, or employing a
modular design and build approach in areas where
resources are constrained. Size and complexity play to
our strength, and we are now leveraging our skills and
experience in delivering these complex hydrocarbons
projects into the metals and mining sector.
As we have said before, competition remains strong
everywhere. We are focusing on those opportunities
where we believe we have differentiators, such as our
technologies, our know-how, our client relationships,
our global presence and our ability to work with clients
from the earliest phases of projects to help them shape
their investment, and our proven track record of safely
delivering technically complex and very large projects.
Leon de Bruyn
Managing Director
Chevron Lummus Global
F
ear of change is a natural
human emotion and especially
felt in todays tough economic
market. As daily crises are
announced, the energy industry
is reeling from the challenges
that could cause our industry to
fall farther and farther behind in
meeting the worlds increasing
energy demands.
Actually, the energy industry is currently in a period
of technical innovation that is quietly, yet surely,
improving the future of energy for generations to come.
We now expect to produce a more diverse supply of
cleaner energy products available globally with extended
lifecycles. Here are a few examples that were considered
major world crisis problems only a few years ago, while
now they are viewed as challenges that lead us to
innovations that help make positive changes:
The anxiety over the inevitable onslaught of peak oil
that had been discussed and argued for years
The competition for scarce energy causing future
wars, famine, destruction of wildlife habitat and global
warming as carbon heavy fuels were consumed more
and more rapidly
The future of energy expected to be particularly tough
for the developing world that needs it to decrease
poverty and develop their countries potential in a
brutal market
The environmental goals that were always viewed to
be in confict with world economic growth.
And in the US, the Energy Policy will force consumers
to pay higher and higher prices for transportation fuels
6 PTQ Q1 2012 www.eptq.com
www.ptqenquiry.com
www.ptqenquiry.com
cbi.indd 1 8/12/11 22:05:08
as carbon gets taxed, coal mines are shut, petroleum
supplies shrink and where bio-derived fuels, wind and
solar power are mandated and subsidised. In each and
every one of these areas, investments in R&D are
steadily changing in direction from negative to positive
in coal, shale, petroleum, biofuels, wind and solar. It is
with such advanced, innovative technologies that we are
able to discover new unconventional resources to
produce products for our future.
The continuous search for energy effciency at all
levels in our industry, whether driven by emissions and
carbon footprint reduction, energy utilisation or
economic optimisation, continues to propel research and
development breakthroughs. We continue to see new
materials in catalysis and higher performance catalysts,
manufacturing improvements, process innovations and
equipment design advancements, and we are even
rethinking our basic assumptions and conventional
wisdoms, among others. This relentless search at
Chevron Lummus Global has resulted in new-generation
Isocracking applications, such as integrating
hydrocracking for fuels and lubes, integrating
hydrocracking and hydrotreating functions, and
optimised partial conversion. The frst of these new-
generation Isocracking units that we designed were
started successfully in the last couple of years.
Heavy oil development continues to be economic and
highly attractive in North and South America.
Horizontal drilling and multistage fracking will
eventually unlock trillions of dollars of new oil and gas
shale reserves in the Americas, Europe and Asia. These
technologies will continue to improve the useful life of
these reserves, which are estimated to last multiple
decades.
Our latest heavy oil catalyst technologies allow the
production of light clean transport fuels while still
reducing the overall carbon intensity of the combined
process. Catalyst innovation continues as a platform for
greater R&D investment for Chevron Lummus Global.
We have a great history and continue to develop and
commercialise lower cost, higher performance
hydrotreating and hydrocracking catalysts that are ft
for purpose to convert heavy oil fractions to high-value,
salable products.
Heavy oil recovery and upgrading will move well
above 2 Million b/d as improved thermal technologies
make their application economic at crude oil prices as
low as $50/bbl. We also anticipate a technology push
into the subsurface areas of heavy oil production, where
in-situ upgrading may prove feasible and economic in
the next few years. Subsurface upgrading technology is
an area that could prove as revolutionary as the recent
shale technologies have been in unlocking previously
unrecoverable oil assets.
Recovered heavy oils such as bitumen are being
converted in LC-Fining complexes in Canada and
elsewhere to synthetic crude or fnished products. We
have furthered the LC-Fining technology and integrated
it in upgrading schemes with other proven processes
such as solvent deasphalting and delayed coking. As a
result, recovery of heavy oil and conversion to transport
fuels has become more economically attractive,
unlocking resources.
Bio-derived fuels are not doomed to causing infation
by driving up food prices. Non-food crops will prove to
be cost-effective sources of biofuel feedstocks in the near
future as our latest R&D investments come on line.
Chevron Lummus Global is now working in partnership
with ARA to bring our frst dedicated demonstration
biorefnery on line by 2014.
Maybe we will always continue to fear change in our
energy industry, but here we must recognise that a new
generation of engineers, scientists and investors are
coming behind us to meet the energy and environmental
goals of a growing population.
Charles Drevna
President
National Petrochemical & Refners Association
(American Fuel & Petrochemical Manufacturers as of 25
January 2012)
P
olitical and regulatory
uncertainty abounds for
petroleum refners and
petrochemical manufacturers in the
US in 2012, making it impossible
to predict with certainty what
changes lie ahead. 2012 also brings
one change I can predict for the
110-year-old trade association
I represent: NPRA, the National Petrochemical &
Refners Association. On 25 January, we will change
our name to AFPM, the American Fuel & Petrochemical
Manufacturers. We are adopting this new name because
it better describes who we are and what we do.
Regarding the outlook for our industries in 2012,
much depends on actions by Congress, President
Obama, the US Environmental Protection Agency and
the courts. President Obama, his EPA and the Senate
majority remain focused on increasing over-regulation
and increasing taxes on companies that produce oil and
natural gas and that manufacture fuels and
petrochemicals. The policies they advocate are part of
an anti-fossil fuels agenda that would raise the cost of
petroleum fuels and petrochemicals in an effort to make
so-called alternatives that receive billions of dollars in
taxpayer subsidies more competitive.
The majority in the House of Representatives is
seeking to rein in over-regulation by EPA. The
environmental agency wants to require fuel and
petrochemical manufacturers to spend billions of dollars
to reduce emissions, even though these reductions
would bring little or no environmental beneft and
would increase energy costs, trigger job losses, and
harm US economic and national security.
At the same time, the outcome of lawsuits will
determine how far EPA can go in some of its regulation
of fuel and petrochemical manufacturers. One major
case before the US Court of Appeals for the District of
Columbia Circuit challenges EPAs endangerment
www.ptqenquiry.com
pcs 1.indd 1 9/12/11 16:46:31
fnding. This fnding concluded that greenhouse gas
emissions threaten the environment and public health,
and is the foundation of EPAs greenhouse gas
regulations. My trade association has joined with other
groups to argue that since the Clean Air Act never
authorised greenhouse gas regulation, the only way to
impose such a regulation would be for Congress to pass
a new law.
AFPM will continue to support sensible and benefcial
environmental regulation. But we believe that Americas
national interest would best be served by comprehensive
and objective cost-beneft analyses of regulations to
determine which make sense and which do more harm
than good.
We will continue to make our case in 2012 that EPA
should not have unchecked power to take any action it
wants without specifc authorisation by Congress in
the single-minded pursuit of unrealistic and harmful
overregulation. It is time for higher consumer costs, lost
jobs, and damage to Americas economic and national
security to be considered as relevant factors in weighing
whether ever-more stringent regulations are benefcial.
Eric Benazzi
Marketing Director
Axens
T
he main trends that will
dominate the market for
refnery products over the
next 20 years are now well known.
World demand for oil products or
their equivalents is likely to increase
at an average rate of a little less
than 1% per year up to 2030 when
it will represent about 104 million
b/d of oil equivalent. However, this growth will not
be distributed evenly around the world. Growth in
road diesel, currently at 1.8% per year, will continue at
a higher rate than that of gasoline (0.8% per year) for
which new demand will be mainly located in emerging
countries. Whereas, in the OECD developed countries
demand will drop by an average of 0.8% per year,
generating refning overcapacity.
Demand for refnery products will also be infuenced
by legislation that will impose the incorporation of
increasing quantities of biofuels, notably those derived
from recycling lignocellulosic biomass. The situation is
different in emerging countries. These countries whose
GDP is growing at a fast rate have populations who
aspire to greater mobility. Therefore, demand for oil
products in these regions is due to rise at the rate of 1.6%
per year over the coming years and will represent 65%
of world demand by 2030.
Demand for natural gas will also continue to increase
in all the regions of the world, driven by the production
of electricity and the needs of industry. In Europe, its use
represents one of the best compromises for combining
economic competitiveness with the reduction of
greenhouse gases. In North America, the exploitation of
unconventional gas sources is a game changer that
will have lasting repercussions in the energy, refning
and petrochemical sectors.
While these contrasting trends offer opportunities for
development, there are also negative aspects. Worries
and risks are present, linked to the fnancial crisis that is
shaking Europe and which could, if the European
governments do not restore confdence quickly, plunge
the rest of the world into a deep fnancial crisis.
The fact is that emerging countries continue to rely on
the spending of richer countries to fuel their growth
needs; this is especially true for China. In 2010, Chinese
consumer spending represented only 34% of GDP
compared to 60% within OECD countries.
Nevertheless, due to the growing infuence of
emerging countries in the world, they will need to shift
their economies to concentrate more on domestic
consumption. This will mean that the organisation of
entire industries will have to change. Higher wages will
be required for this kind of rebalancing and the
population will claim a higher level of social security
and welfare. As a result, the catching up of developing
markets will provide opportunities for developed
countries.
In 2012, the magic words will be:
Flexibility and revamping of existing units to reduce
the gasoline/diesel imbalance
Integration between refning and petrochemicals will
be part of the solution to recover valuable products such
as propylene from low-value heavy feeds
Squeezing the most from the bottom of the barrel will
be required to take advantage of lower priced heavy
crudes and to maximise motor fuel yields
Tightening of fuel quality specifcations will persist
worldwide, requiring catalysts that perform even better.
Innovation in both technology and catalysts will
continue to be the best tools to respond to market
changes and to maximise proftability.
Colin Chapman
President
Euro Petroleum Consultants
I
n the refning and petrochemical
Industry, it is true to say that
the only constant in the
industry is change. Over the past
decades, refners and petrochemical
companies have had to meet
challenges posed by legislation:
Refners: to continuously improve
product qualities for transportation
fuels
Petrochemical producers: to produce higher valued
products to differentiate from competitors.
In the gas sector, the introduction of shale gas on the
global horizon is having a major impact on the future
global gas markets and, in particular, in the Middle East
and Russia. To meet these challenges, technology
improvements have played a key role. We have seen
www.ptqenquiry.com
3400 Bissonnet
Suite 130
Houston, Texas 77005
USA
Ph: [1] (713) 665-7046
Fx: [1] (713) 665-7246
[email protected]
www.revamps.com
PROCESS
CONSULTING
SERVICES,INC.
upsets from water slugs and
other unpredictable situations
that have damaged internals,
resulting in diluent losses and
high vacuum unit overhead con-
densable oil. Diluent is neither
cheap nor plentiful, and high
vacuum column operating pres-
sure will reduce overall liquid
volume yields. And if the design
of the delayed coker fractionator
is based on todays experience
with conventional heavy feed-
stocks you will be lucky to run
six months.
What all this means is that
special process and equipment
designs are needed to satisfy
the special demands of pro-
cessing oil sands crudes. Such
processes are not generated by
computer based designers who
have little or no experience and
never leave the office. They are
developed only by engineers
with know-how who have real
experience wearing Nomex
suits
and measuring true unit per-
formance in Northern Alberta.
Shouldnt this be kept in mind
by those considering long term
supply agreements?
Oil Sands Crude
Profits and
Problems?
Canadian bitumen production
currently runs about 1 MMbpd,
with some being sold as Synbit
and Dilbit. Over the next 10-12
years output is expected to
increase to 3.5 MMbpd and more
refiners will begin investing to
process it and come to depend
on the Synbit and Dilbit for a
significant part of their supply.
Few today, however, have ever
processed these feeds at high
blend ratios, and are unaware
that conventional process and
equipment designs are not up
to the job. Canadian oil sands
feedstocks are extremely hard
to desalt, difficult to vaporize,
thermally unstable, corrosive, and
produce high di-olefin product
from the coker. If you intend to
lock into a long-term supply,
therefore, it is imperative that you
consider reliability and run length
from a particular design.
Too low tube velocity in the
vacuum heater tubes will lead to
precipitation of asphaltenes. Too
fast a flow rate will erode the
tube bends. If coil layout, burner
configuration and steam rate are
not correct, run length will be
measured in months, not years.
Diluent recovery unit designs
must take into account possible
For a discussion of factors
involved in designing refinery units
to process difficult oil sands feed-
stocks, ask for Technical Papers
#234 and 238.
10 PTQ 01:10 01 PC PTQ 0107 ADF 10/19/07 4:42 PM Page 1
ad copy 2.indt 1 8/12/11 21:19:00
signifcant improvements in catalysts, plant designs and
equipment.
This overview will focus on the Middle East gas and
petrochemicals markets and their impact on the global
markets. As the Middle East region looks to produce
and export more refned products, predominantly ultra-
low-sulphur diesel (ULSD), that meet the latest
environmental specifcations, radical changes are taking
place in the established refning infrastructure and also
produce more higher valued speciality products in the
petrochemical sector, instead of commodity products.
Investment for new refneries and petrochemical
facilities and new process technologies are being
reconsidered as the economic climate has changed
drastically in the last few years. Middle East producers
are taking a fresh look at their existing assets and the
options open to them to meet the increased production
and product quality demands for the future. Projects are
being scaled back to meet the new global situation.
However, we have recently seen an announcement on
a project for the largest integrated refnery petrochemical
complex in the world. The Sadara complex will beneft
from low-cost ethane and propane feedstock from the
adjacent Satcorp Complex and also from economy of
scale. The complex will produce a variety of propylene-
based products and aromatics. The project is estimated
to cost $20 billion. About 45% of the products are
destined for the Asian markets and 25% for other
countries in the Middle East.
Sadara is the reincarnation of the $28 billion Dow/
Aramco Ras Tanura Integrated Project (RTIP). The
project was abandoned in 2010 due to escalating costs
and a lack of agreement between the parties. Nearer
term, Petro Rabighs $10 billion expansion on the Red
Sea is being reconfgured from its original plan to
produce 17 products in a $6.7 billion investment. Major
quantities of speciality liquid chemicals will still feature.
And in the immediate future, there is the $10 billion
Saudi Kayan complex. Kayan has been producing major
quantities of liquids and polymers for some time and
will eventually manufacture 18 products.
These projects are based on low-cost feedstock and
beneft from economies of scale. Middle East prices are
usually fxed at favourable rates. The Saudi price for
natural gas, the dominant feedstock for the
petrochemical industry in the Middle East, is $0.75/
million Btu. This compares with much higher prices in
other regions, which can vary from $310/million Btu.
The objective of the low Saudi price level was to
guarantee very attractive internal rates of return for the
potential international partners whose technology was
required to develop the petrochemical sector. The price
level has been fxed for decades. However, the price is
due to be revised at the end of 2011 and is the subject of
much debate in the region and beyond.
Saudi Arabia is in the leader of the move towards
differentiated, higher valued speciality liquid chemicals.
Other countries in the region are also moving into
speciality liquid chemicals. The move to downstream
speciality liquids is a strategy to stimulate economic
diversifcation in the country, leading to greater
employment prospects by creating locally available
chemical and polymer building blocks for local
conversion industries. This enables added value to be
captured in the region. Why ship acetone from the
Middle East to China, where it is converted into acrylic
glass, and then ship it all the way back to the Middle
East for use in signs and windows?
So more changes are on the horizon in the refning
petrochemicals and gas sectors in the Middle East. Many
of these topics will be presented and debated at our
upcoming ME-TECH 2012 in Dubai, 1314 February.
This overview was prepared with assistance from Leslie McCune,
Managing Director of Chemical Management Resources.
Rajeev Gautam
President & CEO
T
his past year was an exciting
one for UOP and across
the refning, petrochemical,
natural gas and biofuels industries
where we work. We have high
expectations for 2012 and continue
to dedicate ourselves to developing
and delivering unique solutions
www.ptqenquiry.com
that will address key trends in distillate production
growth, novel refning technologies that will allow
refners to get more valuable product from every barrel
of oil and the growing use of non-fossil feedstock
sources.
There will be a continued emphasis on hydrocracking
technology, catalysts and equipment for on-spec
distillate production, especially in emerging regions
like the Middle East, Asia and India, where capacity
growth will be the strongest. This shift in product mix
is a long-term trend, and we have committed
signifcant resources to driving technology
enhancements, new products and improvements in
hydrogen management and energy effciency to
improve yields and proftability. Additionally, heavy
crude is becoming a larger feedstock resource, and a
refners ability to process these heavier sources can
offer a boost in margins. Our recently commercialised
Unifex process delivers 90% conversion to transport
fuels while minimising by-products.
Another emerging trend that offers a great deal of
opportunity for our customers is the continued growth
in petrochemicals demand worldwide and the
increased return on investment that producers can
achieve by integrating their refneries and
petrochemical complexes. UOP offers a number of
novel approaches that can maximise production
effciency and leverage low-cost feedstocks.
Our latest innovation in FCC technology, the UOP
RxPro process, can achieve more than 20 wt%
propylene yield from an FCC utilising advanced
reactor technology and confgurations found in our
conventional FCC designs. In aromatics, technology
and catalyst innovations are driving a signifcant
increase in throughput at existing facilities along with
step-change enhancements in energy effciency.
Additionally, we expect that the demand for solutions
that produce propylene at high effciency from cost-
advantaged feeds, such as our own Olefex technology,
will remain an attractive option, especially as the shale
gas boom drives LPG economics and availability.
We have seen the renewable fuels industry make
some important steps forward over the last year,
including the ASTM International approval of natural
oil-based biofuels for commercial passenger fight and
an impressive number of certifcation tests on military
platforms. More and more global customers and
governments are realising the importance of alternative
options and that there are viable technologies available
today. Renewable feedstocks have an enormous
potential to contribute to our hydrocarbon supply and
we expect to see the momentum for these technologies
grow. The frst UOP Ecofning unit for green diesel
production will come online by the end of 2012.
Looking into 2012, we understand that our customers
must focus on getting the highest return on their
investments, maximising the yield on every single
barrel of oil that they process.
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call for papers 2011.indd 1 13/12/11 16:03:31
www.mprservices.com
MPR Services, Inc. Introduces
New and Improved, Compact Technology
with Limiting Use of Resources and Energy
www.ptqenquiry.com
mpr.indd 1 8/3/11 14:07:58
Q
There are so many catalyst/process options for
maximising the LCO yield. What delivers the maximum yield
at a competitive cost?
A
Yen Yung, Global Technical Specialist, Albemarle,
[email protected]
Ken Bruno, Global Applications Technology Manager, FCC,
Albemarle, [email protected]
The amount of light cycle oil (LCO) for blending to
diesel from the fuid catalytic cracking (FCC) unit can
be increased by adopting the following operation
strategy:
Sharper fractionation of the FCC feed to minimise
the amount of material boiling below 370C, the so-
called diesel-range fraction of the FCC feed
Minimise the initial boiling point of the LCO as
much as possible while respecting the specifcations for
diesel, such as the fash point. The LCO yield will then
increase at the expense of gasoline. This recommenda-
tion applies to all columns in which diesel-range
fractions are separated from gasoline. Some units have
been able to minimise the LCO initial boiling point to
about 165C
Maximise the end point of LCO at the expense of the
initial boiling point of heavy cycle oil while taking care
that the specifcations for diesel for example, density
and viscosity are not exceeded.
The above refect the frst points the refnery operator
should take care of before taking any other measures.
In addition, an optimal FCC catalyst has to be selected
based on the following considerations.
Most FCC units have been designed for operation in
the LCO overcracking mode for the sake of high gaso-
line yields. Nonetheless, a substantial increase in LCO
in the 3040 wt% range can be obtained. An obstacle to
overcome is the potential loss in bottoms conversion.
The actual yield of gasoline and LCO will depend on
operating severity, feed type and quality, and catalyst.
The challenge is to selectively crack the large slurry
molecules to LCO, while keeping down the coke yield
and avoiding overcracking of LCO molecules into
lighter products. This means increasing the reaction
rates of the LCO-producing reactions while decreasing
the rates of the LCO-consuming reactions to gasoline
and to coke. It is generally accepted that mesopore and
macropore activity, the so-called alumina matrix activ-
ity, favours bottoms cracking, while zeolite provides
for higher LPG and gasoline selectivity. Therefore,
middle distillate production is generally favoured by
higher matrix cracking (as evidenced by a higher meso
surface area) and reduced zeolite cracking. In other
words, middle distillate production increases as the
zeolite-to-matrix ratio (Z/M) decreases.
For greatest bottoms conversion, the feed molecules
need to reach the active sites quickly. Conversion of the
desirable products in the diesel boiling range and other
secondary reactions, such as hydrogen transfer, aroma-
tisation and condensation, must be avoided. This is
achieved by increasing the accessibility of the catalyst.
Accessibility, related to mass transfer, is the property
that allows the feed molecules to rapidly reach the
active sites and primary products to escape promptly,
prior to any deleterious secondary reactions.
Outstanding performance of highly accessible catalysts,
as measured by our internally developed Albemarle
Accessibility Index (AAI) method, has been confrmed
in several applications.
Albemarle has a full line of MD catalysts. Amber MD
and especially Upgrader MD feature the highest matrix
cracking and AAI in industry. Amber MD is recom-
mended for gasoil feed applications, and the Upgrader
catalyst family is recommended for cracking residual
feedstocks. For applications requiring fexibility, our
bottoms conversion additive BCMT-500 is recom-
mended for all types of feedstock. In addition,
Albemarles technical specialists have special tools for
selecting the proper FCC catalysts grades, including
low rare earth (LRT) technology alternatives, and opti-
mising unit operations.
The two examples below show that a very high LCO
yield can be achieved. The frst example concerns an
FCC unit processing vacuum gasoil with a typical API
of 23 and a sulphur content of about 1 wt%. The cata-
lyst used is Amber MD, the unit riser outlet
temperature was 518C, the combined feed tempera-
ture 226C and the cat-to-oil ratio 7.0 kg/kg. The
special unit feature is that the gasoline endpoint is
minimised to an ASTM D-86 endpoint of 149C, while
the LCO endpoint is very high at an ASTM D-86
endpoint of 379C. Thanks to these cutpoints and the
ptq&a
Additional Q&A can be found at www.eptq.com/QandA
Mesopore and macropore activity
favours bottoms cracking, while
zeolite provides for higher LPG
and gasoline selectivity
Q&A copy 9.indd 1 9/12/11 09:55:39
use of Amber MD, a yield of 44 wt% LCO is obtained,
having a typical cetane index of 34. This unit applies
no bottoms recycle.
The second example is an Amber MD application
processing vacuum gasoil. The severity is very low:
low reaction temperature (499C), high combined feed
temperature (368C) and low catalyst-to-oil ratio (4.0
kg/kg). Bottoms recycle (the recycle rate/fresh feed
ratio varied between 0.51.0 vol/vol) is applied to
enhance the production of LCO. Note that the volume
of recycle can be as high as the fresh feed intake. In
this example, gasoline endpoint is also minimised.
LCO yield and cetane index are very high: 42.4 wt%
and 34, respectively.
A

Ray Fletcher, Senior Technologist, Intercat, RFletcher@
intercatinc.com
There are several options for maximising LCO produc-
tion on the FCC unit. Since increasing LCO yield is
achieved by reducing conversion, there will be a corre-
sponding increase in slurry yield. The proftability
achieved in a maximum LCO operation is directly
related to the ability to prevent or limit this increase in
slurry yield. Another important consideration that is
typically overlooked is the anticipated duration of
favourable diesel market economics.
Achieving desired yield selectivities is rarely the
result of a single variable optimisation. It is very
unlikely to be able to maximise LCO yield entirely
through catalyst reformulation. Intercat strongly
recommends that the FCC operator works closely with
their chosen catalyst supplier to optimise the catalyst
formulation. However, it must not be overlooked that
the catalyst supplier will rarely be able to meet tran-
sient LCO market opportunities adroitly.
This is due to the fact that there are often large
volumes of catalyst within the manufacturers strategic
stocks held in reserve for the refner, catalyst shipments
in transit plus fresh catalyst within the catalyst hopper.
In addition, the unit must be 3540% changed out
before the refner can begin to see selectivity differ-
ences. The typical time frame for the refner from the
point of decision until the unit begins to see selectivity
changes will often be at least two to three months.
This long lag time has been suffcient to prevent
most refners from attempting to proft from market
shifts. Intercat offers an alternative solution that will
enable the refner to proft from both short- and long-
term market diesel demand.
The frst step to maximising the LCO yield
1
on the
FCC unit is to ensure that the unit independent vari-
ables have been optimised (see Figures 1 to 8). Note
that the absolute value and slope for each independent
variable will vary unit by unit. These standard shifts
for maximum LCO are provided below.
Reduce riser outlet temperature (+0.75 wt% for -10F)
Increase preheat temperature (+0.15 wt% for +10F)
Reduce gasoline and point (+1.7 wt% for -10F)
Recycle slurry (LCO ~3040% of conversion)
Increase CRC for partial-burn units (~12 wt%)
Reduce catalyst activity (0.25 wt% for -1 wt%).
The most typical variable shifts for maximum LCO
include reduced riser outlet, reduced gasoline end
point, reduced catalyst activity via lower catalyst addi-
tions, recycling slurry up to the unit constraints
(typically main air blower or wet gas compressor) plus
optimisation of catalyst circulation rate via preheat
temperature.
The catalytic variables for LCO maximisation include:
Decrease zeolite concentration
Decrease rare earth on zeolite
Increase matrix composition (acid sites residing in
pores greater than 8 )
Optimised catalyst architecture. This may be defned
as pore volume or accessibility, depending on your
catalyst supplier.
The standard catalyst formulation for maximum
diesel includes a reduction in zeolite content plus rare
earth on zeolite, and an increase in active alumina with
www.ptqenquiry.com
The frst step to maximising the
LCO yield on the FCC unit is to
ensure the unit independent
variables have been optimised
2 kemesuL u, lnslde-OuL ueslgn Approuch, Ar]kh\Zk[hg Ikh\^llbg`,
2006.
3 kemesuL u, lmprovlng perIormunce Lhrough low-cosL modlIcuLlon oI
Lower lnLernuls, IMJ, Q2 2010.
4 NleuwoudL l, ^m Ze, kevump & reLune, Ar]kh\Zk[hg >g`bg^^kbg`, ]uly
2009, 14, 7, S660.
Darius kemesat ls u lrocess ConsulLunL wlLh Koch-GllLsch Cunudu,
Iocuslng on provldlng soluLlons Lo lncreuse cupuclLy, producLlvlLy und
rellublllLy oI reInlng und peLrochemlcul sepuruLlon sysLems. He holds un
MSc und lhu Irom Lhe UnlverslLy oI Culgury, Cunudu, MA Irom HerloL-
WuLL UnlverslLy, UK, und Lng Irom McMusLer UnlverslLy, Cunudu.
au| wenger ls u Senlor llunL Lnglneerlng lroIesslonul worklng Ior
numerous mldsLreum operuLors. He hus been lnvolved ln numerous
opLlmlsuLlon pro|ecLs Lo lmprove overull usseL uLlllsuLlon und holds un
englneerlng degree Irom Lhe UnlverslLy oI Culgury und MSc Irom Lhe
UnlverslLy oI vlcLorlu.
ppp'îmj'\hf K>O:FIL+)***0
data points below the average expected ethane recov-
ery after the revamp was a lower than average inlet
pressure. As pressure is lowered, there is a decreased
level of energy available to transform into refrigera-
tion, so the beneft of the increased tray effciency is
not fully realised. Another option for revamp is to
provide booster compression to maintain a minimum
inlet pressure at all times. This would capture the dual
beneft of the trays, providing the expected incremen-
tal recovery and the gain in recovery from a higher
pressure. For the cases where the average ethane
recovery was greater than 5%, the inlet feed pressure
was elevated, which allowed the separator tempera-
ture to be reduced for increased refux to improve
ethane recovery. The impact of this situation was an
additional 22.5% ethane recovery. As a result, the
overall ethane recovery translates to around a 3.54%
increase from the revamped trays.
No incremental operating costs are needed for this
type of revamp. The value gain (incremental revenue
minus incremental cost) from the incremental ethane
recovered quickly covers the cost of the revamp
(equipment and installation) to create a payback of
approximately three months.
There is room on the Superfrac trays to increase fow
by 15%. Other equipment around the tower limits an
increased fow and provides the next debottlenecking
opportunity.
Conc|usion
The incremental ethane production from this type of
revamp project is consistently higher than anticipated,
and the project has been considered a success at the
four units with a payback of less than half a year. Three
more revamps on Alberta-based demethanisers are
planned to be executed by Koch-Glitsch for Q4 2011.
The Inside-Out Design Approach used by Koch-Glitsch
aimed to provide the project team with confdence in
the gain in value proposed in recommendations for the
tower internals revamp.
Other revamp options to further increase the ethane
recovery of these entire facilities are also being
considered.
uemlsLer, Mux-lruc, Mlnlvulve und SuperIruc ure murks oI Koch-GllLsch
Ll.
keferences
1 Huung, ^m Ze, lrocesses Ior hlgh C
2
recovery Irom LNG purL ll.
schemes bused on expunder Lechnology, AlChL Sprlng NuLlonul MeeLlng,
Orlundo, lL, 2006.
Average, % Maximum, % Minimum, %
2.0 7.9 0.2
Overa|| incrementa| ethane recovery ca|cu|ated post-revamp
1ab|e 2
% of data points Average in range
>S% C
2
recovery 8 6.0%
2S% C
2
recovery 64 2.2%
<2% C
2
recovery 28 1.8%
8reakout of incrementa| ethane recovery
ca|cu|ated post-revamp
1ab|e 3
Kidextractor
Quarter page
After you have used
it the first time, the
Kid Extractor will
become your trusty
hydraulic-tube-
bundle-extractor
KIDExtractor Ltd.
P.O. Box 11, Zebbug
MALTA
Tel. 00356-21-462891
Fax. 00356-21-462755
MOBILE: 00356-94-20596
E-mail: [email protected]
Website: www.kidextractor.com
www.imjenquiry.com
koch.indd 4 5/9/11 13:22:50
Q&A copy 9.indd 2 9/12/11 09:55:52
Figure 1 LCO Yield vs riser temperature
19.0
21.0
20.5
20.0
19.5
18.5
18.0
17.5
17.0
16.5
960 980 1020 1000
L
C
O
,

v
o
l
%
Riser outlet, F
16.0
Figure 2 Slurry yield vs riser outlet temp
7.5
8.5
8.0
7.0
6.5
6.0
5.5
5.0
960 980 1020 1000
S
l
u
r
r
y
,

v
o
l
%
Riser outlet, F
4.5
Figure 3 LCO Yield vs preheat temperature
20.5
20.0
19.5
19.0
18.5
18.0
350 450 550
L
C
O
,

v
o
l
%
Preheat temperature, F
17.5
Figure 4 Slurry yield vs preheat temperature
8.0
7.5
7.0
6.5
6.0
350 450 550
S
l
u
r
r
y
,

v
o
l
%
Preheat temperature, F
5.5
Figure 5 LCO yield vs gasoline end point
30
32
28
26
24
22
20
320 360 440 400
L
C
O
,

v
o
l
%
Distillation temperature, F
18
Figure 6 LCO yield vs CFR
20.5
20.6
20.4
20.3
20.2
20.1
20.0
1.00 1.01 1.02 1.03
L
C
O

y
i
e
l
d
,

v
o
l
%
CFR
19.9
1.4
1.3
1.2
1.1
1.0
0.9
0.0 0.2 0.4 0.6 0.8
L
C
O
/
S
l
u
r
r
y
CRC, wt%
0.8
Figure 7 LCO yield vs CRC
3.0
2.5
2.0
1.5
1.0
0.5
68 70 72 74 76
L
C
O
Activity, wt%
0.0
Figure 8 Delta LCO yield vs activity
Q&A copy 9.indd 3 9/12/11 09:56:04
optimisation of catalyst particle diffusional characteris-
tics. The most successful catalyst reformulations feature
a reduction in the zeolite-to-matrix (Z-to-M) ratio.
These formulation changes are worth consideration if
optimal diesel market conditions are expected to last
more than four to six months.
An alternative approach to LCO maximisation for
those refners operating in dynamic diesel markets is to
apply an additive approach (see Figures 9 and 10).
Intercat has successfully applied its bottoms cracking
additive (BCA) in over 41 FCC units globally. The aver-
age LCO yield increase in these applications has
exceeded 2.0 wt% (see Tables 1 and 2). This approach
employs a reduction in the circulating inventory Z-to-
M. Empirical observation has shown that the main air
blower and wet gas compressor loadings have been
unaffected in every application. This enables refners to
base load BCA into their FCC units without negatively
impacting throughput. Intercat further enables refners
a swift return to typical Z-to-M levels in the circulating
inventory via injection of Hi-Y, which is an additive
containing very high levels of zeolite.
This approach has been commercially proven in
multiple FCC units to swiftly increase LCO yields. Its
primary advantage is to enable refners to optimise the
Z-to-M level of the circulating inventory in response to
actual market demand. Intercat supplies state-of-the-art
loading systems without charge to those refners inter-
ested in using this approach.
1 Fletcher R P, Opportunities for On-Demand LCO Maximization, AM-09-69,
2009 NPRA Annual Meeting.
Figure 9 BCA-105 performance
24
28
26
22
20
62 64 66 68 70 72
L
C
O
,

w
t
%
Conversion, wt%
18
Base
BCA-105
10
14
12
8
6
62 64 66 68 70 72
S
l
u
r
r
y
,

w
t
%
Conversion, wt%
4
Base
BCA-105
Figure 10 BCA-105 performance
Design criteria Charge Base btms Additions Yield selectivities
Region Design Supplier API CCR Yield API Cat, tpd BCA, % Dry gas LPG Gaso LCO Slurry Coke
Europe UOPSBS Albemarle 23.1 0.82 6.0 0.5 6.5 -0.60 0.0 1.0 5.0 -1.5
NAmerica KelloggUltra Grace 22.5 2.28 17.8 10.0 10.0 10.0 0.00 0.00 3.3 -3.3 -3.3 0.0
Asia Kellogg CCIC 26.6 3.7 9.6 8.1 7.3 8.0 -0.05 -1.2 -1.2 3.3 -0.5 -0.9
NAmerica KelloggF IMP 24.1 8.8 -0.5 4.5 -0.05 0.0 -0.8 2.9 -1.0 -0.4
NAmerica Sinclair Albemarle 23.3 2.3 4.5 10.6 9.0 0.8 2.7 -2.0
Europe UOPSBS Albemarle 20.0 4.7 10.5 3.0 5.0 12.0 -0.10 0.0 2.0 2.0 -3.9 0.0
NAmerica UOPStack Grace 24.4 0.2 14.3 2.0 6.5 0.00 0.4 2.0 -3.5 0.0
NAmerica KelloggF Grace 26.3 8.8 3.0 2.9 -0.90 0.9 -1.0 1.8 0.0 -0.2
Asia UOPSBS 20.7 0.3 13.0 13.2 1.5 3.0 -0.05 0.0 -0.2 1.7 -1.7 0.0
NAmerica KelloggUltra IMP 24.7 5.8 4.6 1.4 -0.24 1.5 2.0 1.5 -1.4 -0.8
Asia R2R 21.7 2.39 12.0 -1.7 5.0 6.9 1.3 -1.3
Asia R2R Grace 20.0 4.9 16.0 -1.5 6.5 1.0 -1.0
NAmerica UOPSBS Grace 22.7 0.29 9.8 -2.0 3.0 10.0 0.00 0.0 0.0 1.0 -1.0 0.0
Overview of BCA performance in LCO mode
Table 1
Minimum Average Maximum

Feed quality
Gravity 20.0 23.1 26.6
Sulphur 0.20 1.20 2.30
CCR 0.20 2.19 4.90
Nitrogen 200 729 1390
Operations
Reactor temp 919 966 993
Regenerator temp 1216 1303 1360
Catalyst adds, tpd 1.4 4.3 10.0
BCA conc, % 3.0 7.8 12.0
Equilibrium catalyst
MAT 61 67 71
Ni 355 2287 5700
V 693 2396 7500
Yield selectivities
Dry gas -0.9 -0.2 0.0
LPG -1.2 0.2 1.5
Gasoline -1.2 0.3 2.0
LCO 1.0 2.3 5.0
Slurry -3.9 -1.7 0.0
Typical yields of BCA in LCO mode
Table 2
Q&A copy 9.indd 4 9/12/11 16:52:25
Q
Are low rare earth catalyst additives for SO
x
reduction
available?
A
Alan Kramer, Global FCC Additives Specialist, Albemarle,
[email protected]
Yes, Albemarles SO
x
Master is a zero rare earth SO
x
reduction additive that has been in use since 2005.
Albemarle originally developed SO
x
Master in response
to the known negative effects of cerium in partial-
combustion FCC units. As rare earth prices escalated,
refners operating in full combustion have turned to
SO
x
Master to control both SO
x
emissions and rare earth
costs. It has been used by over 20 refneries around the
world.
Switching SO
x
Master requires special attention due
to the differences in performance characteristics
between SO
x
Master and cerium-containing SO
x
reduc-
tion additives. Albemarle has collected the
best practices and lessons learned from the multitude
of additive trials our technical service teams have
performed globally. We have condensed this
information into an effcient trial execution template,
designed to keep the refnery in compliance with its
SO
x
emissions regulations, while becoming acquainted
with the new additive. This template consists of four
main components: prerequisite data gathering and
analysis, baseline establishment, SO
x
Master transition,
and the ongoing demonstration of performance.
In conclusion, refners should not have to settle for
new low rare earth SO
x
additives when non-rare earth
alternatives are already available.
A
Ray Fletcher, Senior Technologist, Intercat, RFletcher@
intercatinc.com
Cerium plays a signifcant role in additives for SO
x
reduction. Reducing the additive cost by simply drop-
ping the cerium oxide concentration will work up to a
certain point. However, exceeding this point will result
in loss of SO
x
-reducing activity, leading to substantially
increased additive injection rates.
Intercat has developed a low-cerium SO
x
-reducing
additive, Super SO
x
Getter-II, in which the cerium oxide
content has been reduced by 50%. The activity of this
additive has been observed to be at least equal to the
benchmark SO
x
-reducing additive, SO
x
Getter, which
contains twofold more cerium oxide. Over 38 FCC
units are now continuously injecting SO
x
Getter-II with-
out any loss in SO
x
absorption effciency. This
technology enables refners faced with stringent SO
x
emissions standards to reduce their operating budget
without compromising effectiveness. Additional R&D
work is currently under way to further reduce this
cerium level; it is expected that SO
x
Getter-III will
shortly become available with much lower cerium
content.
Intercat has developed a rare earth-free SO
x
-reducing
additive, Cat-Aid. This additive is effective where
ultra-low levels of SO
x
reduction are not required.
This additive is lower in cost but requires higher
concentrations in the circulating inventory. It has
the side beneft of passivating vanadium and
absorbing feed nitrogen, leading to enhanced conver-
sion together with a reduction in fresh catalyst
additions. This additive provides add-on features for
refners who do not yet require reductions in SO
x
to
ultra-low levels.
Q
Is it possible to predict desalter performance accurately
when switching between crude blends?
A
Sam Lordo, Marketing Manager-Process NA, Nalco
Energy Services, [email protected]
Not without a lot of testing and knowledge of the indi-
vidual crudes that comprise the blend. Even after that
the models used are not accurate enough to fully
predict impacts on desalination, dehydration and oil
undercarry.
cheap crudes and supplemental feedstocks drive plan-
ning decisions. The task at hand is to decide how to
prepare and protect your hydrocracker or hydrotreater
from silica and other contaminants that will force you
into an early shutdown. No-one wants to turn an oper-
ating unit around prior to a planned event, as the cost
and disruption to the entire facility are enormous.
Todays refners have competing forces at play: inex-
pensive, opportunity feeds containing high levels of
contaminants combined with the need to keep the unit
operating until the next scheduled turnaround or
longer.
Innovative technology solutions can help address this
issue. CLG has catalyst systems available to handle
silica and other contaminants. Our catalysts are capable
of handling high levels of silica and can be designed to
handle specifc contaminants as well as optimised for
particular operating conditions and expectations. We
offer a complete line of guard systems and catalysts to
protect your investment, as well as to allow you to opti-
mise your refnery and operate it at its full potential.
:
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NHIAr]khikh\^llbgÌkhc^\mM^\agheh`r@khni
Silicon is a contaminant that is present in all delayed
coker-derived feedstocks and also observed in straight-
run gas oils derived from certain crudes. Catalyst
loading strategies are available to manage silicon in the
feed while maintaining the desired catalyst cycle life.
The frst bed in a hydroprocessing unit reactor includes
a graded bed consisting of several layers of different
materials, with the objective of protecting the down-
stream catalyst from plugging due to particulates and/or
deactivation due to metals, sodium, silicon or other
contaminants.
If the unit feedstock contains silicon, one of the
materials utilised in the graded bed would be a cata-
lyst optimised for silicon uptake. A high surface area
catalyst is recommended to provide high silicon
removal capacity without signifcantly impacting cata-
lyst activity. UOP specifes catalysts manufactured by
our alliance partner Albemarle, which are well suited
to silicon removal. The specifc materials are selected
based on the nature of the unit feedstock (naphtha or
distillate vs heavy gas oils) and the processing
objectives.
It is not required that all silicon in the feed be
trapped in the graded bed, since the main hydrotreat-
ing catalyst typically retains a reasonable activity even
when loaded with some silicon. The graded bed
volume may be limited by the need to maintain a
certain volume of active treating catalyst. In this case,
there will be some breakthrough of silicon from the
graded bed into the main catalyst as the cycle
progresses. However, by optimising the proportion of
silicon trap versus active catalyst, suffcient activity
may be retained to reach the desired cycle length. It
should be noted that sulphur breakthrough into the
main catalyst will prevent the catalyst from being
regenerated and reused, since silicon is not removed
during a catalyst regeneration.
:
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The good news is that silicon is a relatively mild
poison for hydrotreating catalyst. It can come into the
hydrotreater as a solid (eg, sand particulates) or as a
dissolved organic material. If silica (SiO
2
) comes into
the unit as a particulate, it will tend to build up the
pressure drop in the unit by flling in void space in the
1IMJJ-+)** ppp'îmj'\hf
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0rabner nstruments Messtechnik 0mbH / A-1220 Vienna/Austria / Dr. 0tto-Neurath-0asse 1
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4.-0.0#1130#
.0-!#11,*78#0
- VP oI gasoline, crude oil and LP0
- A5TM D511, 5188, 377, 378,
87, EN 1301-1+2, P3, 0, 81
- Highest accuracy Ior best
possible blending to oIIicial limits
- Up to 2 sample streams
- Automatic calibration
- Fast and easy maintenance
- Automatic lubrication
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Q&A copy 8.indd 3 13/9/11 12:03:34
www.ptqenquiry.com
Reducing the additive cost by
simply dropping the cerium oxide
concentration will work up to a
certain point
Q&A copy 9.indd 5 9/12/11 09:56:27
Grace Davison leads the industry with the first commercially
successful zero and low rare earth FCC catalysts:
the REpLaCeR
TM
family.
REp R
TM
Worried about the
high cost of rare earth?
www.grace.com
www.e-catalysts.com
www.ptqenquiry.com
grace.indd 1 8/12/11 21:10:12
Catalysts for maximising middle distillates
I
ncreasing middle distillates
consumption in Europe is a trend
that began in the 1990s and is
expected to continue in the future,
while at the same time gasoline
demand is decreasing. This has
resulted in an imbalance between
demand and supply for middle
distillates and gasoline in Europe,
meaning that refners face an
important challenge of increasing
the gasoil-to-gasoline ratio in the
refnery. There are many options by
which refners can raise the produc-
tion of middle distillates at the
expense of gasoline. For example,
refneries can operate their FCC
units in maximum distillates mode.
The Repsol Puertollano refnery is
an inland refnery located in the
centre of Spain. The refnery proc-
esses heavy crudes with a deep
conversion scheme, which includes
a delayed coker and FCC and mild
hydrocracker (MHC) units. The
complex also includes an ethyl tert-
butyl ether (ETBE) and a
hydrofuoric acid alkylation unit,
which process the C
4
fraction from
the FCC unit. The FCC unit is a
40 500 b/d Exxon Flexicracker,
which was started up in 1983. In
2004, an Axens MHC was installed
for FCC feedstock pretreatment, in
order to adapt product quality to
the more stringent regulations of
maximum sulphur in fuels. Since
then, 9095% of the feedstock proc-
essed by the FCC unit is mild
hydrocracker residue (RMHC), with
the other 510% being a heavy feed-
stock, such as atmospheric residue,
which is necessary to close the unit
heat balance.
The main objective at the
Puertollano FCC unit is the maxim-
Collaboration in catalyst development and application, from laboratory scale to
commercial operation, enabled a refner to achieve production objectives
Ruben MIRavalles and TaMaRa GalIndo
Repsol
isation of middle distillates
production. Other unit objectives
include a reduction in light naphtha
yield, maximum olefn content and
a minimum motor octane number
(MON) value required. To achieve
these objectives, the unit operates at
very low severity (low riser temper-
ature, cat-to-oil ratio and e-cat
activity), with maximum slurry
recycle. Producing maximum
middle distillates in the Puertollano
FCC unit case is a diffcult chal-
lenge. The severely hydrotreated
RMHC feedstock is highly crackable
with a very poor selectivity to
middle distillates. In addition, the
coke-making tendency of the
RMHC feed is very low. Therefore,
processing this feedstock at low
severity requires maximum slurry
recycle and the simultaneous
processing of a certain amount of
heavy feedstock, such as atmos-
pheric residue, in order to close the
heat balance.
Processing of atmospheric residue
in this unit has several disadvan-
tages. For example, low-sulphur
atmospheric residues must be proc-
essed in the FCC unit in order not
to penalise the sulphur balance.
Therefore, light crudes, which are
not the optimum feedstock in the
refnery scheme, must be distilled
to feed the FCC unit. Processing of
atmospheric residue in the FCC
unit also results in high metals
contamination on the e-cat, with a
subsequent increase in catalyst
consumption.
Collaboration project
Grace Davison has been the FCC
catalyst supplier for the Puertollano
FCC unit for several years. Grace
has continually made innovations
in catalyst technology, which has
allowed the Puertollano FCC unit
to better adapt to the changing
production scenarios. Before the
start-up of the MHC unit, the Goal
catalyst from Grace Davison was
used. After the start-up of the FCC
pretreatment and in order to adapt
to the signifcant feed quality
change and operating conditions in
the FCC unit, the Goal catalyst was
replaced by the Nomus-100 catalyst
based on frst-generation EnhanceR
technology.
Later, Grace Davison developed
the Nomus-Dmax catalyst, which is
a second-generation EnhanceR cata-
lyst for increased middle distillates
yields, and this catalyst was also
successfully applied to the
Puertollano FCC unit operation. In
order to fully optimise the challeng-
ing Puertollano operation, Grace
Davison and Repsol decided to start
a joint collaboration project to
develop a new generation of cata-
lysts for middle distillates
maximisation in hydrotreated feed-
stock scenarios.
Increasing
middle distillates
consumption in
europe is expected to
continue, while at the
same time gasoline
demand is decreasing
repsol.indd 1 9/12/11 10:03:42
formulations and tested them on a
laboratory scale in an ACE
(advanced catalyst evaluation) unit.
A total of 19 catalysts were evalu-
ated in the frst round to select the
best zeolite, matrix and post-
treatments, and six of the highest
performing catalysts were fne-
tuned and tested again in a second
round of trials. Upon completion,
the top four catalysts were selected
for the following phase of the
project, which consisted of an eval-
uation in the Repsol DCR-II pilot
plant unit. Process modelling with
FCCSim was used to translate pilot
plant results to the commercial unit,
to check unit constraints and to
optimise operating conditions for
the new catalysts. The catalyst that
showed the best performance in
both a high and low metals
scenario, the DieseliseR-Sol 16 cata-
lyst, was manufactured by Grace
Davison on an industrial scale and
the results from its commercial use
in Puertollanos refnery will now
be discussed.
Commercial application of DieseliseR
The DieseliseR-SOL 16 catalyst trial
began in September 2009. During
the catalyst turnover, the feed rate
in the commercial unit was variable,
with alternating operations at a
minimum feed rate during the end
of 2009 and early 2010 with periods
of high throughput. Independently
of the total feed rate, the improve-
ment in heat balance closure
achieved with the new DieseliseR-
SOL 16 catalyst has allowed a
desired progressive reduction in the
low-sulphur atmospheric residue
(AR) processing (see Figure 1).
Due to the reduction in the
amount of atmospheric residue
needed to close the heat balance,
contaminant metals on e-cat have
been signifcantly reduced, in
particular by deactivating metals
such as vanadium and sodium. The
periods of low feed rate have also
contributed to lower contaminant
metals levels on e-cat. Consequently,
the catalyst addition rate has been
progressively decreased until it
reached the minimum technically
needed to maintain levels in the
regenerator and stripper (see
Figure 2).
Two different scenarios were
defned for the development of the
new catalyst: a high metals scenario,
corresponding to atmospheric resi-
due processing and high metals on
e-cat; and a low metals scenario,
with no atmospheric residue proc-
essed and low metals on e-cat. In
the frst phase of the project, Grace
Davison developed several catalyst
200
180
160
140
120
100
8
0
/
6
0
/
1
0
8
0
/
7
0
/
1
3
8
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1
r
h
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t

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e
t
a
r

d
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e
F

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e
l
c
y
c
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r

y
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u
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s

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t
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h
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30
25
20
15
10
5
0
Feed rate S|urry recyc|e AR rate
Nomus-Dmax 121 Diese|iseR-SOL16
Figure 1 Feed rate, atmospheric residue rate and slurry recycle
3.0
2.5
2.0
1.5
1.0
0.5
0
1
/
0
6
/
0
8
3
1
/
0
7
/
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t

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,

t
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r
V
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a

e
-
c
a
t
,

p
p
m
0.0
10000
9000
8000
7000
6000
5000
4000
3000
Catalyst addition
V+Na
Figure 2 Catalyst addition vs vanadium and sodium levels on e-cat
200
180
160
140
120
100
8
0
/
6
0
/
1
0
8
0
/
7
0
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d
i
M
80
49
47
45
43
55
53
51
41
39
37
30
Feed rate Midd|e disti||ates
Figure 3 Middle distillates (140380C) production
repsol.indd 2 9/12/11 16:56:32
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dupont.indd 1 1/9/11 20:47:42
During the catalyst turnover, a
continuous increase in middle distil-
lates (140380C) was recorded in
the unit (see Figure 3), thus achiev-
ing a signifcant improvement in the
main production objective.
Reduction in light naphtha
production using the DieseliseR-
SOL 16 catalyst is also clear (see
Figure 4), although in this case the
comparison is not so straightfor-
ward because the level of olefns
promoter in the inventory has not
been constant. Due to lower propyl-
ene demand, olefns promoter
usage was stopped during the
DieseliseR-SOL 16 catalyst period,
as can be seen in the graphic of
P
2
O
5
on e-cat (see Figure 5). This
factor must be taken into account
because it is necessary to discount
the olefns promoter effect for the
comparison of the two catalysts.
Shifts in commercial yields with
the new catalyst are detailed in
Table 1. The deltas have been
obtained as the difference between
average values from several test
runs performed in the commercial
units with the Nomus-Dmax 121
catalyst, before catalyst substitution,
and the DieseliseR-SOL 16 catalyst
at around 60% turnover. Regarding
operating conditions, it can be seen
that riser temperature and MAT
activity have been held constant on
average between the two periods.
Feed rate was slightly lower during
the DieseliseR-SOL 16 catalyst
period, whereas slurry recycle was
slightly higher.
The main change in operating
conditions was the reduction in
olefns promoter addition rate due
to lower propylene demand.
Nevertheless, the effect of olefns
promoter on the yields in Table 1
has been corrected. Results show an
impressive increase of more than
3 wt% in middle distillates, similar
bottoms production and a signif-
cant reduction in light naphtha,
thus achieving the desired FCC
product yields to better suit market
demand. The decrease in propylene
production is not an issue in the
current situation as a result of low
product demand, and in any case
LPG production loss could be easily
recovered with the addition of
ZSM-5 additive.
E-cat comparison
Direct comparison of the previous
and current catalyst in the industrial
unit is diffcult. First, feedstock qual-
ity has been variable, with
atmospheric residue being progres-
sively reduced during the catalyst
turnover. Second, some of the oper-
ating conditions that greatly impact
yields and selectivity, such as feed
rate (which affects residence time)
and olefns promoter addition rate,
have been varied during the
DieseliseR-SOL 16 catalyst turnover.
For this reason, in order to check
the good results observed during
the industrial trial, several Nomus-
Dmax 121 and DieseliseR-SOL 16
e-cat samples collected from the
commercial FCC unit were tested in
the DCR pilot plant at Repsols
research and development facilities.
200
180
160
140
120
100
8
0
/
6
0
/
1
0
8
0
/
7
0
/
1
3
8
0
/
9
0
/
9
2
8
0
/
1
1
/
8
2
9
0
/
1
0
/
7
2
9
0
/
3
0
/
8
2
9
0
/
5
0
/
7
2
9
0
/
7
0
/
6
2
9
0
/
9
0
/
4
2
9
0
/
1
1
/
3
2
0
1
/
1
0
/
2
2
0
1
/
3
0
/
3
2
0
1
/
5
0
/
2
2
0
1
/
7
0
/
1
2
0
1
/
9
0
/
9
1
0
1
/
1
1
/
8
1
1
1
/
1
0
/
7
1
1
1
/
3
0
/
8
1
1
1
/
5
0
/
7
1
1
1
/
7
0
/
6
1
1
1
/
9
0
/
4
1
r
h
/
t

,
e
t
a
r

d
e
e
F

%
t
w

,
a
h
t
h
p
a
n

t
h
g
i
L
80
Feed rate Light naphtha
24
22
20
18
16
14
12
10
Figure 4 Light naphtha (C
5
90C) production
30
25
20
15
10
5
8
0
/
6
0
/
1
0
8
0
/
7
0
/
1
3
8
0
/
9
0
/
9
2
8
0
/
1
1
/
8
2
9
0
/
1
0
/
7
2
9
0
/
3
0
/
8
2
9
0
/
5
0
/
7
2
9
0
/
7
0
/
6
2
9
0
/
9
0
/
4
2
9
0
/
1
1
/
3
2
0
1
/
1
0
/
2
2
0
1
/
3
0
/
3
2
0
1
/
5
0
/
2
2
0
1
/
7
0
/
1
2
0
1
/
9
0
/
9
1
0
1
/
1
1
/
8
1
1
1
/
1
0
/
7
1
1
1
/
3
0
/
8
1
1
1
/
5
0
/
7
1
1
1
/
7
0
/
6
1
1
1
/
9
0
/
4
1
%
t
w

,
t
a
c
-
e

5
0
2
P
0
50
45
40
35
Figure 5 Olefns promoter on e-cat (wt% P
2
O
5
)
yield (DR16 - base)
Yields:
Conversion @ 161C -3.8
Fuel gas 0.2
C
3
total -1.18
C
4
total -1.15
LPG -2.3
LCN-L -2.9
LCN-M 1.1
Gasoline -1.7
Middle distillates 3.5
DO 0.3
Coke 0.0
Operating conditions:
Feed rate, t/h -24.9
RA rate, t/h -6.4
Slurry recycle, m
3
/h 5.8
Feed density -0.0042
Riser temperature, C 0
Preheat temperature, C 11
MAT activity, wt% 0
Olefns promoter, % e-cat -2.5
Yields and operating data comparison of
DieseliseR-SOL 16 vs Nomus-Dmax 121
Table 1
repsol.indd 3 9/12/11 10:04:02
provided a successful outcome in
an area of joint interest. It has been
an exemplary project, covering all
the stages from research in new
catalytic technology to development
and testing, frst at laboratory scale,
followed by pilot plant validation
and successful application to
commercial production and
operation.
EnhanceR, DieseliseR-SOL, NOMUS-DMAX,
NOMUS-100 and GOAL are marks of Grace
Davison.
Rubn Miravalles works in the Refning
Department of Repsols R&D Division where
he is in charge of the FCC research project
and has acquired broad experience in catalyst
characterisation and selection, modelling and
process studies. He holds a bachelors degree in
chemistry from the University of Burgos, Spain,
and a masters in refning, gas and marketing
from the Instituto Superior de la Energia.
Tamara Galindo is a Process Engineer at
Repsols Puertollano refnery, Spain, where she
is in charge of several processes. She holds
a bachelors degree in chemical engineering
from Rey Juan Carlos University, Madrid, and
a masters in refning, gas and marketing from
the Instituto Superior de la Energia.
For the pilot plant comparison, the
e-cat samples were tested at constant
operating conditions, which simu-
lates operation in the industrial unit,
using a representative feed sample
collected from the Puertollano unit.
The results of pilot plant comparison
of both catalysts at constant coke,
which are shown in Table 2,
confrmed the excellent results
observed in the commercial unit.
Conclusions
The development of a new genera-
tion of EnhanceR FCC catalysts for
maximising middle distillates has
resulted in a signifcant beneft for
the Puertollano refnery. The
DieseliseR-SOL 16 catalyst has
achieved an improvement in the
two main production objectives
namely, a signifcant increase in
middle distillates production in a
very challenging hydrotreated
scenario and a decrease in gasoline
production thus allowing the
FCC unit product yields to better
match the refnerys demand. The
optimised catalyst also allows the
FCC units heat balance to be closed
without having to process atmos-
pheric residue, which provides a
reduction in e-cat metals and cata-
lyst consumption, and a decrease in
the sulphur content of FCC
products.
Last, but not least, this project
involved close collaboration
between Repsol and Grace, which
Table 3
yield (DR16 - base)
Yields:
Conversion @ 161C -4.4
Sulfhydric 0.0
Fuel gas 0.1
C
3
total -0.47
C
4
total -0.50
LPG -1.0
LCN-L -2.5
LCN-M 1.0
Gasoline -3.4
Middle distillates 3.0
DO 1.2
Coke 0.0
Total 0.0
DCR pilot plant comparison of e-cats
at constant coke
Table 2
Determination of Sulfur and other elements
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Using cold boiler feed water for
energy recovery
S
team at different pressure
levels is used for many
purposes in refneries, includ-
ing power production (steam
turbines), heating, steam tracing,
stripping, atomising and deaeration.
Steam is produced from fred utility
boilers, cogeneration units (gas
turbine HRSGs), furnace waste heat
boilers, product rundowns, column
refuxes and so on by adding heat to
supplied boiler feed water. Boiler
feed water is conventionally
supplied by deaerators, where steam
is used to heat water to saturation
conditions at a certain pressure to
strip dissolved oxygen, with the aim
of preventing corrosion in steam
production units. In this article, the
benefts of providing cold boiler feed
water from membrane deaerators to
steam-producing or water-heating
waste heat streams will be explained,
with some typical examples for an
oil refnery.
Membrane deaerators
Membrane deaerator technology is
used for degassing liquids around
the world. They are widely used for
removing oxygen from water, as
well as for carbon dioxide removal.
They have displaced the vacuum
tower, forced draft deaerator and
oxygen scavengers for over 20
years. Membrane contactors are
used extensively for the deaeration
of liquids in the microelectronics,
pharmaceutical, power (boiler feed
water), food and beverage, indus-
trial, photographic, ink and
analytical markets. A trial study of
the scope of a heat recovery project
has been carried out within a refn-
ery, where the aim of the project
was to decide whether this technol-
Feeding membrane deaerated cold boiler feed water to appropriate units will
enable waste heat to replace substantial steam duty in a refnery
AliSAn DoG
An
Turkish Petroleum Refneries Corporation
ogy should be used extensively for
the deaeration of boiler feed water,
together with existing conventional
steam deaerators.
Membrane deaerator systems
consist of membrane contactors
combined in series, parallel or both,
designed according to the water
fow, pressure drop limitations and
oxygen concentration needed at the
outlet of the system. The contactors
work on the basic principle of
letting only gas (oxygen) molecules
pass to the other side of membranes,
where a vacuum is applied via a
vacuum pump and sweep gas
(high-purity nitrogen) is supplied.
Oxygen molecules in the water side
have a high partial pressure
compared to the vacuum side, so
they tend to pass through the
hydrophobic membranes. Here,
high-purity sweep gas is introduced
to the vacuum side to prevent
oxygen from concentrating in the
vacuum side, which sustains the
mass transfer effciency (partial
pressure difference).
The maximum oxygen concentra-
tion requirement for boiler feed
water in this scenario is 7 ppb.
However, 1 ppb was targeted when
selecting the confguration for this
project (to be on the safe side). The
purity of the sweep gas nitrogen has
critical importance when selecting
the best confguration because it
obviously has to contain a minimum
amount of oxygen. In this case, the
refnery has a high-purity nitrogen
ring (99.99 vol%) which is mainly
consumed by reformers and other
processes that need high-purity
nitrogen. Nitrogen consumption by
the membranes is very low
(~10 Nm
3
/h, of course depending
on water fow and oxygen concen-
tration targeted) when compared to
process needs (in the range of
several thousand Nm
3
/h) and there-
fore does not have a negative effect
on the refnery nitrogen balance.
Nitrogen is purchased by the
refnery and delivered by trucks,
which periodically supply high-
purity nitrogen to the main tanks in
the refnery nitrogen system (ring).
In a refnery without an available
nitrogen ring, a nitrogen tank, sized
according to the capacity of the
system, will be needed. This can be
periodically flled with the nitrogen
provided by trucks. The other needs
for the system are a small amount
of electricity and cooling water for
the vacuum pump system, which
are easily accessible in the refnery
confguration.
Water temperature at the
membranes is another point of
importance in the systems confgu-
ration. The level of oxygen
dissolved in water depends on the
temperature of the water. The solu-
bility of gases decreases with
increasing temperature. Usually, at
atmospheric temperatures, ~6 ppm
(6000 ppb) of oxygen is dissolved in
water. Depending on the water
temperature, solubility can be
between 5 and 8 ppm. Therefore,
depending on the water tempera-
ture, the membrane system load
changes. In this projects scenario,
demineralised water is heated by
condensate drum fash vapour and
the temperature to the membrane
deaerator system will change
between 30 and 50C, depending
on the ambient temperature. A high
temperature is good for effcient
oxygen removal; however, another
tupras.indd 1 9/12/11 10:15:23
important point is that tempera-
tures above 60C are not desirable
for the membranes, as they may be
damaged at such temperatures,
depending on the operating pres-
sure. The demineralised water
system pressure in this case is 68
kg/cm
2
g, which can easily be
decreased to 5 kg/cm
2
g or less with
the appropriate valves.
The advantages of the membrane
deaerator system, including low
investment and operating costs and
relatively small size, make it an
appropriate selection for the cold
boiler feed water heat recovery
project. Membrane deaerator
systems can be purchased from
various OEM frms.

Case 1
Energy recovery from a hydrocracker
hydrogen production unit
Waste heat from the hydrocracker
hydrogen steam reformer furnace is
one of the main steam producers
from a furnace waste heat boiler.
Approximately 90120 t/h of
38 kg/cm
2
g steam is produced from
furnace waste heat, depending on
the units working capacity. Boiler
feed water is supplied at 55 kg/
cm
2
g and 125C, and this is pumped
from the deaerator at the utility
production unit. Boiler feed water
is frst heated by the shift converter
outlet raw hydrogen stream, which
has impurities such as water vapour
(over 40 wt%), CO, CO
2
, CH
4
and
N
2
. After heating boiler feed water,
this hydrogen stream is than cooled
down further by air and cooling
water to get rid of water and
dissolved gases. Condensate is
taken from hot and cold condensate
drums, then the steam is stripped
of its dissolved gases and sent back
to the utility production unit. The
boiler feed water heating scheme
prior to the hydrogen reformer
furnace steam generator inlet is
shown in Figure 1.
For the most part, the latent heat
of condensation of water vapour in
the raw hydrogen stream is given
to the boiler feed water to boost
steam production. A portion of
condensate recovered from this
used heat is taken from the hot
condensate drum, while the rest of
the heat is wasted to air and cool-
Raw gas
to H/E
67587 kg/hr
260.0C
24.6 kg/cm
2
BFW to H/E
118000 kg/hr
125.0C
55.0 kg/cm
2
BFW to steam
generator
118000 kg/hr
185.8C
54.3 kg/cm
2
Raw gas
to 1. drum
67587 kg/hr
157.9C
24.4 kg/cm
2
Condensate
to stripper
6345 kg/hr
157.9C
24.4 kg/cm
2
Raw gas
to 1. cooler
61242 kg/hr
157.9C
24.4 kg/cm
2
Raw gas
to 2. cooler
61242 kg/hr
55.0C
24.2 kg/cm
2
Raw gas
to 2. drum
61242 kg/hr
28.0C
24.1 kg/cm
2
Hydrogen
from 2. drum
39245 kg/hr
28.0C
24.1 kg/cm
2
Condensate
to stripper
21996 kg/hr
28.0C
24.1 kg/cm
2
E-203
E-205
E-206
C-207
C-208
Figure 1 Hydrogen unit boiler feed water heating (before cold BFW)
Raw gas
to H/E
67587 kg/hr
260.0C
24.6 kg/cm
2
BFW to H/E
118000 kg/hr
50.0C
55.0 kg/cm
2
BFW to steam
generator
118000 kg/hr
172.9C
54.3 kg/cm
2
Raw gas
to 1. drum
67587 kg/hr
134.4C
24.4 kg/cm
2
Condensate
to stripper
18362 kg/hr
134.4C
24.4 kg/cm
2
Raw gas
to 1. cooler
49225 kg/hr
134.4C
24.4 kg/cm
2
Raw gas
to 2. cooler
49225 kg/hr
55.0C
24.2 kg/cm
2
Raw gas
to 2. drum
49225 kg/hr
28.0C
24.1 kg/cm
2
Hydrogen
from 2. drum
39284 kg/hr
28.0C
24.1 kg/cm
2
Condensate
to stripper
9941 kg/hr
28.0C
24.1 kg/cm
2
E-203
E-205
E-206
C-207
C-208
Figure 2 Hydrogen unit cold boiler feed water heating
tupras.indd 2 9/12/11 10:15:39
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merichem 2.indd 1 13/12/11 09:50:21
ing water. In this layout, 7.4 Gcal/h
is recovered by heating boiler feed
water, while 17.4 Gcal/h is wasted.
In the current project, cold boiler
feed water (3050C) will be
supplied from the membrane deaer-
ators to this unit through existing
feed water pumps. The driving force
for heat transfer will be increased in
exchanger E-203 (see Figure 1) and
more latent heat of condensation
will be recovered. In this way, steam
used in the deaerators is saved and
water is heated by waste heat.
The initial projected layout for
50C feed water temperature is
shown in Figure 2. The energy
recovered in E203 increases to 14.6
Gcal/h. Some 7.2 Gcal/h of net
energy is saved by providing cold
feed water to this exchanger and
recovering more heat of condensa-
tion in the raw gas stream. In other
words, 118 t/h of boiler feed water
at 50C does not need to be heated
to 125C with steam in the deaera-
tor. This is equal to ~8.8 Gcal/h
steam duty saving in the deaerator
according to the simple formula:
Q=m*cp*dt.
However, because the heat
exchanger exit temperature (waste
heat steam generator economiser
inlet) is a little lower, a portion of
this saving is lost and a net
7.2 Gcal/h is saved.
This heat recovery may be
increased further by adding some
area to the heat exchanger, making
up for the lost portion of heat recov-
ery. For example, 33% additional
surface area in E-203 increases the
recovered energy by 1.1 Gcal/h.
Other side benefts of this project
are electricity savings from air
cooler fans and cooling water
savings, as with any other process
heat recovery project. The other
important saving is the stripping
steam from the condensate CO
2

stripper. The overall temperature of
the total condensate from two
drums increases, thus decreasing
the CO
2
solubility, which reduces
the need for stripping steam.
Case 2
Energy recovery from a gas turbine
heat recovery steam generator
Boiler feed water to a gas turbine
HRSG is provided from the same
header to the oil-fred utility boilers.
The water temperature is kept above
140C to prevent sulphuric acid
corrosion in the boiler economisers.
However, only natural gas is fred in
the gas turbine and there is no risk
of sulphuric acid corrosion in the
HRSG, so cold water can be fed to
the economiser. The only concern is
to keep the temperature above water
dew point. In this way, the driving
force for heat transfer will be
increased in the economiser and
more heat will be recovered during
feed water preheating. Steam used
in the deaerator to heat the water
will be replaced by waste heat.
Initial conditions are 69.8 t/h of
68 kg/cm
2
g steam production and
the stack temperature is 233C.
According to trial and error calcula-
tions, if water is supplied at 50C,
net heat recovered from the exhaust
gas increases by 6 Gcal/h. In fact,
the steam saving for boiler feed
water heating is approximately
7.5 Gcal/h. However, since the
economiser outlet temperature to
the steam drum is lower (the
approach temperature is higher),
there is a steam production loss of
~1.5 Gcal/h from the HRSG, which
decreases the net saving to 6 Gcal/
h, as stated. By adding some addi-
tional economiser area, this loss can
be compensated and more heat will
be recovered from the exhaust gas,
increasing it to 7.5 Gcal/h and
more.
It is important that the water
temperature entering the econo-
miser should be kept above the
water dew point of the exhaust gas.
This is done by taking some water
from the existing hot boiler feed
water line and setting the tempera-
ture to the HRSG above 50C.
Other cases
Other potential users of cold boiler
feed water are product rundown or
column refux steam producers (or
boiler feed water heaters), which
are placed before air coolers, reac-
tor effuent streams before air
coolers, and so on. For example,
steam production from vacuum
residue or other product rundowns,
and steam production/boiler feed
water heating in column refux
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payback time, the possibility of
implementing the project without
process unit shutdowns and the use
of newer technology, the project is
a very important contribution to the
refnerys energy roadmap studies.
Alis an Dogan is a Process and Equipment
Development Supervisor in Head Offce
Technical Services Management with Turkish
Petroleum Refneries Corporation (Tpras ). He
holds a BS in chemical engineering from Middle
East Technical University, Ankara, Turkey.
Email: [email protected]
streams are common in refneries.
One other potential area of applica-
tion is fuel gas (or natural gas)
burning furnaces ftted with waste
heat boilers. As in the cogeneration
examples, water can be fed cold to
these units provided its tempera-
ture is above the water dew point
of the fue gas. Low-temperature
waste heat streams can also be used
for boiler feed water heating
purposes, to boost steam produc-
tion in process plants.
The confguration of refnery
steam and electricity production is
important when calculating the
corresponding cash benefts of this
project. After calculating the duty
and amount of steam savings from
the waste heat sources, we shall
look at the overall steam and elec-
tricity balance to calculate the real
cash income of the project. It is
obvious that large amounts of low-
pressure deaerator steam will be
saved. In the refnery where the
project is being applied, low-
pressure steam is extracted from
electricity-generating turbo alterna-
tors and process rotary equipment
turbines. Higher-pressure turbine
steam is produced via fuel-burning
boilers. In addition, there are the
gas turbine cogeneration unit and
condensing turbines already
mentioned.
In this scenario, low-pressure
steam produced for the deaerators
is reduced; the net reduction is
approximately 1525% (depending
on the season) of the total low-
pressure steam extraction from the
turbo alternators. The project
decreases the turbo alternator loads,
together with the fuelled boiler
steam loads. The electricity lost
from the turbo alternators is
compensated by the gas turbine
cogeneration unit, which is much
more effcient. Therefore, the over-
all effciency of the electricity
generation system is also increased,
accounting for some additional fuel
savings. For the sake of simplicity,
this additional duty saving is not
taken into account in this article.
An alternative scenario would be
the replacement of lost electricity
by condensing turbines, which
would decrease the net energy
saving delivered by the project.
Conclusion
Within the ongoing project, by feed-
ing membrane deaerated cold boiler
feed water to appropriate units, it is
expected that a net saving of 16
Gcal/h of steam duty will be made.
This duty will be replaced directly
by waste heat. The payback period
for the investment is less than fve
months. By adding additional area
to the related exchangers, savings
can be increased to over 22 GCal/h.
Considering the benefts, the short
Table 3
The frst investment level consists
of operational adjustments that can
be made in refning processes.
These solutions are largely focused
on the optimisation of operating
conditions and considered to be
low-cost options. Table 2 shows
some selected operational adjust-
ments. The impact of these,
however, may be somewhat limited
due to constraints on processing
equipment and auxiliary units.
The second investment level
includes hardware and catalyst
changes available to refners when
processing opportunity crudes. In
general, these strategies and solu-
tions are better served to meeting
specifc goals than operational
adjustments; the solutions, however,
are more costly than simply imple-
menting operational changes.
The third investment level repre-
sents the most capital-intensive
alternatives for improving a refners
ability to process opportunity
crudes. The installation of modifed
processes, revamps of older process
units and the installation of new
process equipment can be completed
to meet one or more of the objectives
while processing additional volumes
of opportunity crudes. For a grass-
roots refnery, the solutions in this
category can be used as a guide for
selecting a refnery confguration
that will enable the processing of
low-cost opportunity crudes.
<hg\enlbhg
In order for refners to decide to
process opportunity crudes or not,
they must look at various factors,
with particular consideration given
to evolving market conditions and
climate change legislation. Since each
refnery has its unique set of internal
and external challenges and pros-
pects, SWOT (strength, weakness,
opportunity and threat) analyses are
to be undertaken so that the plant
can maximise proftability by procur-
ing lower-cost opportunity crudes,
making the products in demand both
now and in the future, and driving
down operating costs. The goal is not
only to sustain the business, but also
to prosper in the long haul.
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The highlights of the trial include
Reactor temperatures increased
Residue conversion increased by
Vacuum tower bottoms sediment
was well below target during the
trial, including a 10 wt% increase in
Fouling rates were substantially
-
Vacuum residue feed rate
All LC-Fining reactors were stable
No fouling was observed in the
Asphaltene conversion increased
Neste Oil and HTI completed a 40-
day commercial trial at the Porvoo
refnery. The trial successfully
-
ment in the LC-Fining units
performance. The test was successful
in that the residue conversion
increased by about 10 wt%, with
substantially reduced fouling
-
ment, including the vacuum tower
The technology was used in the
LC-Fining unit following a spring
2010 turnaround and has been used
continuously since the summer of
-
ing, the advantages observed
during the 40-day test were
confrmed. The vacuum tower
bottoms sediment was reduced well
below the maximum operating
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Cost estimating for turnarounds
T
urnarounds are major events
for refneries and other petro-
chemical facilities. They
typically cost signifcant sums of
operational expense (opex) and capi-
tal expense (capex) money to
execute. They cause lost opportunity
cost through lost production while
the facility is shut down. If poorly
managed, turnarounds offer signif-
cant risk of accidents. If poorly
executed, they can also be the cause
of signifcant production disruption
after startup, due to leaks and other
production trips. Hence, there is a
potential to save signifcant sums of
money, by ensuring turnarounds are
run correctly.
However, despite the large poten-
tial for saving money, there has,
until recently, been very little focus
in the turnaround world on making
sure turnarounds are run cost eff-
ciently or on fnding ways to
improve cost estimating and execu-
tion skills. In the past seven to eight
years, this attitude has begun to
change and turnaround teams are
beginning to look at how they can
improve. One potentially rich source
of ideas on how to improve is for
the turnaround teams to examine
how their capital project brethren
estimate and execute projects. In the
capital project world, the potential
for leaving money on the table
due to poor project estimating and
execution has meant that decades of
time and effort have been spent, and
continue to be spent, on developing
techniques to ensure that estimation
and execution is carried out
effciently.
This article focuses on cost estima-
tion. It does not presume to provide
all the answers on how to improve
Cost estimates for refnery turnarounds can lack accuracy, but lessons learned
from capital project estimating could improve matters
Gordon LawrenCe
Asset Performance Networks
turnaround cost estimates. Rather, it
attempts to lay the groundwork for
a discussion on how to improve cost
estimating in process facility turna-
rounds. It highlights the point that
cost estimating in the turnaround
world is currently not very accurate.
It then goes on to look at ideas on
how to improve cost estimate accu-
racy, by looking at ideas that might
be adapted from the capital project
world. In particular, it looks at the
stage gate approval system, the
development of scope and estimate
bases for different levels of estimate
accuracy, and at the development of
allowances for known unknowns
and contingency for unknown
unknowns. Finally, it makes some
suggestions for the next steps in
developing better turnaround cost
estimates.
what is a process industry
turnaround?
A turnaround (in the context of the
process industries) is defned by the
American Petroleum Institute as a
planned, periodic shutdown (total or
partial) of a... process unit or plant
to perform maintenance, overhaul
and repair operations and to inspect,
test and replace process materials
and equipment.
1
Refneries and
other petrochemical facilities that
run on a continuous rather than a
batch production cycle must, every
few years, shut down operations to
provide access to the production
units in order that essential mainte-
nance, modifcation and inspection
work can be carried out that could
not be done while the units are in
operation.
Turnarounds are events that are
planned well in advance and
typically take place on a four-to-six
year cycle. The length of a typical
turnaround execution phase (ie, the
period when the facility is shut
down and hydrocarbon free) is
usually around three-to-fve weeks.
The scope of a turnaround typi-
cally includes:
Inspection of equipment to
company regulations or governmen-
tal rules
Inspection of pipework for corro-
sion and erosion damage, both
internal (process weak points) and
external (corrosion under insulation,
or CUI)
Cleaning, repair and maintenance
of equipment, pipework and instru-
mentation (pulling and cleaning heat
exchanger tube bundles, repairing
leaks in pipework or checking of
pressure relief valves)
Minor upgrades and modifcations
to the facilities (items controlled
under the management of change
[MoC] procedures)
Tie-ins for capital projects.
Historically poor estimation and
execution effciency
Historically, there was a tendency
among operating companies to view
turnarounds as an inevitable and
necessary evil, and to accept that
they would cost what they cost
and take as long as they take.
However, in recent years, there has
been a growing recognition that this
attitude leaves money on the table
in the form of the opportunity cost
of lost production while the facility
is shut down for longer than neces-
sary; and unnecessarily excessive
expenditure of money during the
turnaround, through running the
turnaround ineffciently.
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results in a 50% accuracy estimate,
the following conceptual design
stage results in a 30% estimate, and
the fnal basic design stage results in
a 10% estimate. Hence, the focus of
the stage is in developing a scope
basis to meet the estimate basis
requirements for the level of accu-
racy intended
The project cannot proceed to the
next stage without frst going
through a stage gate review to check
whether it has achieved the required
scope and estimate basis
Full funding of the project is
usually only received at the end of
the third, basic design phase.
The focus, therefore, in the capital
project world is on calculating How
much money do we need in order to
carry out this scope?.
Turnarounds
In the turnaround world, there has
been a movement in recent years
towards a form of stage gated
approach, in an attempt to improve
front-end defnition. However, the
system is not yet as clearly defned
as in the capital project world.
There are some key differences in
the way the approach is applied.
The length of each stage is (more or
less) fxed, based on the amount of
time remaining until the turnaround
In order to improve turnaround
effciency, there is a need to examine
the estimation of costs for turna-
rounds, the estimation of schedule
time, and the effciency of planning
and execution of the turnaround.
This article focuses on the frst of
those three areas, the estimation of
costs.
Accuracy of turnaround cost
estimates
A cost estimate needs to be accurate
in order to provide management
with the information needed to
decide how to proceed, to allow
cash fow planning and to aid in
frm control of expenditure.
In a survey of conference partici-
pants at the Turnaround Industry
Networking Conference (TINC)
Europe, held in March 2011 in
Amsterdam, The Netherlands,
2
83%
of respondents said that their turna-
round control budget was intended
to be a 10% estimate (see Figure 1).
3

The remaining 17% said that their
estimate was supposed to include
suffcient contingency/reserve that
it was a not to exceed number.
None said that their budget was
intended to be a 30% estimate.
We then took a sample of 93 recent
turnarounds and in each case
compared the total actual cost for
the turnaround (including both capi-
tal and maintenance work) with the
control budget. Figure 2 plots the
over- or under-run of the actual
costs, expressed as a percentage of
the control budget. It shows the
mean (the horizontal bar) and 80%
confdence range (the vertical bar) of
the results in our sample set and
compares it to the results we would
have expected if the cost estimates
truly were 10%, or if they were
30%.
Based on the results shown in
Figure 2, we can say that turnaround
cost budgets tend, on average, to
under-estimate the actual cost by
around 16% (the distance of the
mean bar from the 100% point)
and the budgets themselves show a
variability of closer to 30% accu-
racy than their purported 10%
accuracy (the vertical line shows the
80% confdence range around the
mean).
Clearly, there is an opportunity to
improve cost estimating accuracy in
turnarounds.
Comparing capital projects with
turnarounds
Cost estimating of capital projects in
the process industries has gone
through a number of improvements
over the years. It may well be that
some of the lessons and devices
used in capital projects can provide
a basis from which to develop a
system for better turnaround
estimates.
Stage gates
Capital projects
In the capital project world, it is now
generally accepted that front-end
defnition is the key to a successful
project. In order to achieve good
front-end defnition, capital project
teams have largely moved toward a
stage gated approach, whereby the
design proceeds through three
distinct stages of ever-improving
scope defnition.
4
Key points are:
The length of each stage is a func-
tion of the work required to be
completed in that stage
The culmination of each stage is a
cost estimate, with the estimates
getting more accurate with each
succeeding stage. Generally speak-
ing, the feasibility stage of a project
120
160
170
150
140
130
110
100
90
80
70
Theoretical range
10% estimate
Theoretical range
30% estimate
Turnaround
actual costs
P90
P10
Mean
N=93
A
c
t
u
a
l

t
u
r
n
a
r
o
u
n
d

c
o
s
t
s

a
s

a

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r
o
p
o
r
t
i
o
n

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f

t
h
e

b
u
d
g
e
t
,

%
60
Figure 2 Accuracy of turnaround control estimates: expectation and reality
Figure 1 Expectation of accuracy in turnaround control estimates: vox populi
z4302.indd 1 12/13/2011 7:56:19 AM
www.ptqenquiry.com
linde.indd 1 13/12/11 09:44:23
starts. Generally, by about 1412
months before the turnaround, the
frst review of status will be held. A
second review may be held around
nine-to-six months before and the
last review about three-to-two
months before.
The stages are not focused on
scope defnition for cost estimates
of a given accuracy. Instead of the
issuance of an estimate marking the
end of a stage, the ends of these
stages are delineated by their prox-
imity to the start date of the
turnaround. There are guidelines
on what level of scope defnition
should be expected at each of these
turnaround stage gates, but these
guidelines are not as universally
adopted as their counterparts are
on capital projects.
By the nature of a turnaround,
refusing to let a turnaround team
proceed to the next stage because it
is insuffciently prepared at the time
of the stage gate review is not
usually a feasible option. The budget
tends to be fxed back at the 30%
or even 50% estimate stage.
Consequently, with turnarounds, the
focus tends to be on How much
scope can we carry out for this
amount of money? rather than the
capital project paradigm of How
much money do we need in order to
carry out this scope?.
Scope basis and estimate basis
In this section, we make a distinc-
tion between the scope basis (the
level of defnition of the design
deliverables and documents) and
the estimate basis (the methodology
used to calculate costs, based on
those deliverables).
Capital projects
In the world of process industry
capital projects, the scope basis
and the estimate basis are both
relatively well defned for various
levels of estimate accuracy, from
50% down to 10% or better. One
well-known example of where this
is documented is AACE International
Recommended Practice No. 18R-97.
5

Lawrence also lists typical require-
ments.
4
(Table 1 and Table 2 are
adapted from Lawrence, 2008.) In
addition, it is accepted practice to
document the cost estimate in a
written basis of estimate
document.
Early estimate: 50% rough order of
magnitude
In capital projects, the frst cost
estimates are usually highly deter-
ministic, using high-level factoring
methods rather than the stochastic
approach of calculating from the
bottom up. The cost of a facility is
typically factored off such details as,
for example, the production capacity
of the new facility, with adjustments
made for infation and location. Such
estimates generally have little in
terms of scope basis, often merely
an outline of the facility capacity
Table 1
50% ROM
estimate
General project data
Engineering deliverables
Project scope
description
Facility capacity
Facility location
Ground surveys
Project
execution plan
Contract strategy
Project schedule
Cost estimating plan
Plot plans
Process flow diagrams
Utility flow diagrams
Project execution plan
P&IDs
Heat and material
balances
Process
equipment list
Utility
equipment list
Electrical single line
diagram
Process engineers
equipment datasheets
Mechanical engineers
equipment datasheets
Equipment general
arrangement
Block flow diagrams
30% ROM
estimate
10%
control
estimate
General
General
None
None
None
Outline
None
None
None
None None
None
None
None
None
None
None
None
None
Assumed
Assumed
Level I
milestones
Defined
Defined
Defined
Defined
Defined Defined
Defined
Level III
detailed
resource
loaded
schedule
Defined
Defined
Defined
Defined
Specific
Complete
Complete
Complete
Complete
Complete
Complete
Complete
Complete
Complete
Complete
Complete
Complete
Complete
Complete
Complete
Specific
Preliminary
Preliminary
Preliminary
Preliminary
Preliminary
Preliminary
Preliminary
Preliminary
Preliminary
Preliminary
Preliminary
Preliminary
Level II
preliminary
the previous turnaround scope, and
the estimate basis uses that historical
total cost.
Conceptual estimate: 30%
On turnarounds, teams appear to
aim to have the overall scope frozen
and challenged by this point.
However, this has not always been
achieved. In terms of deliverable
documents for the scope basis, the
mechanical workpacks are usually
developed. The estimate basis is a
mix of deterministic and stochastic,
as the mechanical work packs are
costed (in-house) in some detail, but
the other work (electrical, instru-
mentation scaffolding, insulation,
and so on) is usually factored off the
mechanical costs, using historical
factors.
Authorisation/control estimate: 10%
Some turnaround teams do now
have all discipline scopes developed
and externally costed. However, in
our experience, the number of teams
that take their estimates to this level
of detail are relatively few, despite
the fact that most teams claim their
control estimates are 10% or better.
Work breakdown structure
Capital projects
All companies have their own varia-
tions on how they prefer to break
down costs within the estimate.
Indeed, the work breakdown struc-
ture (WBS) may differ slightly, from
project to project, depending on the
scope. Nevertheless, at a high level,
there is a measure of agreement
across the industry on how to break
down capital project costs. The
breakdown tends to be as shown in
Table 3.
Turnarounds
At present, there is no clear, common
agreement across the process indus-
tries on a high-level WBS for
turnaround costs. Most turnaround
teams split costs into direct costs
costs that can be specifcally assigned
to a cost object, such as an item of
existing plant and indirect costs
costs that cannot easily be directly
attributed to a cost object. However,
the defnition of what should be
considered direct or indirect cost
varies from site to site (presumably
required. The estimate basis relies
on historical data of the total cost of
the entire facilities rather than
detailed cost data.
Conceptual estimate: 30%
In capital projects, a considerable
amount of work would be completed
on the scope basis, coming close to
freezing the overall scope and devel-
oping many of the design drawings
by the time this estimate was
prepared.
The estimate basis would have
moved from a high-level, determin-
istic estimate to a mix of the
stochastic and deterministic, and the
team moves towards Lang factors or
other, similar methods to calculate
the project cost (factoring off one
element of the project scope, most
typically the equipment cost).
Authorisation/control estimate: 10%
By this stage, the scope basis on a
capital project is generally very
detailed, with completed P&IDs,
order specifcations for major equip-
ment and so forth. The estimate
basis is now stochastic, built bottom
up from the material take-offs and
using market cost data rather than
historical database information.
Turnarounds
There appears to be no document
equivalent to AACE International
Recommended Practice No. 18R-97
for process industry turnarounds. In
the absence of such a document, we
have informally surveyed a number
of turnarounds to look at the vari-
ous scope and estimate bases used
by the turnaround teams to develop
estimates of nominal accuracies of
50%, 30% and 10%.
The frst problem we have encoun-
tered is that there is some variation
in the methods used. Second, the
concept of writing down a detailed
basis of estimate document is
something that still has to take root
in the turnaround world; hence,
understanding how each estimate
was developed is diffcult. (We were
occasionally given documents
described by the team as the basis
of estimate, but these were gener-
ally extremely simple, high-level
notes on the estimate spreadsheet
itself rather than a formal and
detailed document.) Nevertheless,
we have attempted to provide a
general overview of the methods
being used by turnaround teams for
the various estimates.
Early estimate: 50% rough order of
magnitude
The early estimate is frequently
merely the cost of the last turna-
round, adjusted for infation, with
perhaps an educated guess as to
how the scope may have grown or
shrunk since the last turnaround.
The scope basis is therefore merely
Table 2
"ASIC
DESIGN
%NGINEERING
Pactored, based on
previous, similar
facilities (based on
production capacity,
facility surface area
similar metric)
%QUIPMENT
"ULK
MATERIAL
#ONSTRUCTION
LABOUR
50% ROM
estimate
30% estimate
10% control
estimate
8udget estimate,
or factored off
equipment
8udget quotes for
ma|or items,
database costs
for remainder
Complete
Pirm quote
8udget quotes
based on detailed
material take-offs
8udget quotes
based on detailed
material take-offs
Pirm quotes for
ma|or items,
budget quotes
for remainder
Pactored off
equipment
Pactored off
equipment
Detailed estimate
www.ptqenquiry.com
we are the people
of Baker Hughes.
and we are prepared
to respond.
www.bakerhughes.com
Maximize proft and reduce fnancial risk with Baker Hughes
PREPARED TO RESPOND
(P2R
) services. Our fast fuel additive

delivery teams keep your fuel and crude oil cargos on spec.
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barges, P2R services increase its value and marketability while
minimizing risk and assuring HSE compliance.
Around the world, 24 hours a day, 365 days a year, experienced
Baker Hughes P2R service teams, with additives and equipment, can
deploy at a moments notice to test your cargo and treat it with the
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oil cargos meet specifcations, contact
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to learn how P2R services help you
capture your cargos full value.
2011 Baker Hughes Incorporated. All Rights Reserved. 32693
baker hughes.indd 1 12/12/11 16:11:46
because of different internal account-
ing practices).
The costs of owner supervision are
generally agreed to be indirect, since
at any hour of the day a team could
be supervising work on a range of
existing plant areas. Contracted
labour on tasks that can be assigned
to specifc existing plant items is
generally categorised as direct cost.
Furthermore, tracking this cost by
plant unit/area and by equipment
class/type and by equipment
number is relatively common.
However, costs such as rented
equipment (cranes, heat exchanger
bundle pullers, and so on) are less
consistently assigned to either direct
or indirect categories, presumably
because such items can only some-
times be attributed to a specifc plant
item (for instance, if a crane is only
needed to work on a specifc item).
Theoretically, it should be possible
to assign bulk material (pipe, valves,
for instance) to specifc plant items
and hence categorise the material as
direct. However, this is not always
done. One would logically expect
consumable materials such as weld-
ing rods to be indirect costs because
of the diffculty of assigning them to
specifc plant items. However, the
situation can be clouded by the fact
Table3
Table 3
Home Office
Field
Capital
Expense
Allowances for
unknown unknowns
Allowances for
known unknowns
Direct
Design
Engineering
Equipment
Contingency
Commissioning
Operations staff
Bulk materials
Construction labour
Construction
management/supervision
Temporary facilities,
craneage, scaffold, etc
Design
allowances
on each
line item
Escalation
allowances
on each
line item
Project
management/supervision
Indirect
that consumables and bulk materials
occasionally are not separated.
Allowances for uncertainty
Any cost estimate, by nature of it
being an estimate, requires funds for
the uncertain elements of the scope.
These uncertain elements can be
divided into known unknowns
and unknown unknowns. The
known unknowns are allowances
for items or quantities that the esti-
mator knows, from historical
evidence, will be needed in a specifc
line item of the estimate. The
unknown unknowns are the items
or quantities that were under-esti-
mated or completely overlooked in
the estimate. The estimator does not
know exactly in which line item the
funds will be needed, but history
tells the estimator that some funds
will be needed to bring the estimate
to the P50 point. These unknown
unknowns are contingency funds.
The need for contingency is a hotly
debated subject, but has been
discussed elsewhere
6
and we do not
propose to explore this topic here.
Capital projects
Known unknowns
The known unknowns in capital
projects take the form of design
allowances allocated to each line
item for the known unknown of
that line item (for instance, wastage
in the piping material take-off,
design development in equipment).
The amount of design allowance
to include is usually determined
through expert judgment based on
historical data.
Unknown unknowns
Contingency is for the unknown
unknowns in the estimate (for
instance, it is discovered during
construction that the need for an
electrical transformer was over-
looked in the design).
As discussed by Burroughs &
Juntima,
7
the amount of contingency
to include is typically calculated in
one of four ways:
As a predetermined percentage
(of the base estimate)
Through expert judgment (gut
feeling/experience) based on histori-
cal data
Through a Monte Carlo-type
review of the cost effect of expected
risks
Through use of a regression
model, based on historical data.
Turnarounds
In the case of funds for uncertainty,
there is a little more general agree-
ment than perhaps in other areas of
estimating for turnarounds, in as
much as it is generally accepted that
funds are needed for unknown
items.
Known unknowns
In turnarounds, the known
unknowns are (a) emerging work
(work to repair items that have
broken/failed between the comple-
tion of the estimate and the start of
the turnaround); and (b) discovery
work (repair work that is discov-
ered during the turnaround once
equipment or pipework is opened
up for detailed inspection).
In common with the design allow-
ances on capital projects, estimates
of likely emerging work and discov-
ery work should (in theory) be
calculable and assigned to specifc
estimate line items. (For instance, we
can expect other X valves to fail
between now and the shutdown, or
based on past experience we should
expect that the trays in column Z
will be discovered to be damaged
when we open it up.)
However, what we have observed
is that very often such items are not
reported in the estimate to this level
of detail. Instead, they tend to be
listed as single line items on their
own. In addition, anecdotally, we
observe that very often the discov-
ery work in particular appears to be
underestimated an optimism
about what is likely to be found
seeming to prevail.
The amount of emerging work
allowance and discovery work
allowance appears to be calculated
on the basis of experience from
previous turnarounds or from inti-
mate knowledge of the state of the
facility. But when it is based on
experience of previous turnarounds,
this experience is rarely backed up
by hard numbers, showing what
was spent in previous turnarounds
as a percentage of the base scope
cost.
Unknown unknowns
In turnarounds, just as in capital
projects, a contingency for the items
that were overlooked or completely
unforeseen at the time of the esti-
mate issue is required. (For instance,
money was included in the discov-
ery work allowance to spend three
days repairing trays in column X,
because the column was old and
was operating at low throughput.
However, it took two days longer
than expected to repair the trays in
column X. That extra two days cost
comes out of contingency.)
Whereas in capital projects contin-
gency is calculated on the basis of
one of four methods, each of which
has at least some logical foundation
to it, in turnarounds we observe that
contingency often appears to be
calculated simply as the difference
between the current base estimate
plus discovery and emerging work
allowances and the original, rough
estimate quoted to management
(assuming the rough estimate to be
a higher number!).
Quantifcation of turnaround
allowances
We then looked further into how
much allowance for uncertainty was
included by turnaround estimators
and how much was actually used.
How much is included?
The frst problem that we encoun-
tered in this study was that while
most turnaround teams recognise
the three main areas of unconfrmed
scope that need funding as being (1)
emerging work, (2) discovery work
and (3) contingency for the unfore-
seen, few teams clearly differentiate
between them in their estimates.
Indeed, in a survey that we carried
out, out of 216 turnarounds, only 34
(or 16%) could give a clear differen-
tiation in their cost estimate between
these three areas and the main
estimate.
Nevertheless, from the data gath-
ered we are able to show (see Figure
3) that teams typically include a total
of just under 13% of the base esti-
mate (where base estimate = the
total cost estimate before the three
uncertainty allowances are included)
as a total of all three allowance
amounts.
That funding breaks down in turn
into an average of 16% for emerging
work, 38% for discovery and 46%
for contingency (see Figure 4).
How much is spent?
We then attempted to look at how
much in each category is typically
consumed. From this information, we
hoped to begin developing guidelines
on calculating how much should be
included in an estimate. However,
we found that although some teams
have begun to track the consumption
of the three elements in their actual
costs this practice is still immature
within the turnaround community.
Without historical data on actual
expenditure in these three catego-
ries, it is impossible to close the
loop and begin developing guide-
lines on how much should be
included in each category in an
estimate.
Conclusions
The problem
Currently, turnaround cost estimates
are inaccurate in that, on average,
turnaround costs overrun their esti-
mates. They are also highly
unpredictable in the level of their
inaccuracy (that is, the overrun
does not remain within the claimed
10% accuracy of most estimates).
16
22
20
18
14
12
10
8
6
T
o
t
a
l

a
l
l
o
w
a
n
c
e
s

a
s

p
r
o
p
o
r
t
i
o
n

o
f

t
h
e

b
a
s
e

e
s
t
i
m
a
t
e
,

%
Emerging work + discovery work
+ contingency
4
+1SD
1SD
Mean
N=38
Figure 3 Uncertainty allowance included in estimate
Contingency
38%
Emerging
work
16%
Discovery
work
38%
N=34
Figure 4 Breakdown of uncertainty
allowance into emerging, discovery and
contingency
Furthermore, there is no clear
agreement on the defnition of
what information a cost estimate
should be based upon in order to
allow it to be defned as a 10%
estimate.
There are no guidelines on how to
calculate uncertainty allowances for
emerging work, discovery work and
contingency. Nor are many teams
gathering the actual cost expendi-
ture data that would allow such
guidelines to be developed in the
future.
Learning from capital projects
The capital project world historically
had similar problems with cost esti-
mating. Over the years, it has
improved through:
Tying estimates to stage gates
Clearly defning the scope basis
and estimate basis required for a
certain level of estimate accuracy
Using similar work breakdown
structures, allowing comparison
benchmarking of data
Gathering data on allowances for
uncertainty and developing logical
methodologies for estimating those
allowances.
The turnaround world has already
begun to learn from capital projects
by copying the stage gate approach.
There seems to be little reason to
suppose that turnaround teams
cannot continue to learn from capital
projects in order to develop turna-
round-specifc standards for scope
basis, estimate basis and calculation
of allowances.
Recommendations for immediate
action
If the estimation of turnarounds is
to become more accurate and
predictable, we recommend that, as
a frst step, a series of actions should
be adopted within the turnaround
community.
Defne the scope and estimate basis
There should be wide agreement on
what the scope and estimate basis
is for calling an estimate 50%, 30%
or 10% accurate. The capital projects
community has such agreement in
documents referred to earlier.
Suggested outline versions for turn-
arounds are given in Tables 4
and 5, respectively. Table 4
50% ROM
estimate
General turnaround scope data
Engineering deliverables
30% ROM
estimate
10%
control
estimate
Equipment count
Turnaround premises
Risk Based Inspection
(RBI) data
Maintenance turnaround
backlog
Listing little
definition
Baseline
no markup
None
None
None
None None
None
Original
baseline
None
Listing high
level, based
on asset
management
strategy
95%
complete
99%
complete
60-70%
complete
99%
complete
Hazard and Operability
study (HAZOP)
Listing high
level
60-70%
complete
100%
complete
Plant engineering design
changes (expense)
Listing not
all inclusive
60-80%
complete
100%
complete
Leak Detection And
Repair (LDAR)
Listing
preliminary
Listing
preliminary
Partial
markup
Partial
turnaround
markups
Partial for
new capital
Complete
listing
Previous turnaround
scope
Plot plans
logistics markups
Plant engineering
design packages
Major capital project
engineering design
Flare minimisation plan
Heat transfer data
Utility plan
Oils plan
P&ID markups
Process engineering
design basis for plant
engineering capital
Turnaround boundaries
Listing 90% Listing 90% Listing 90%
Process Hazard Analysis
(PHA)
Listing high
level
60-70%
complete
100%
complete
Management Of Change
(MOC) design changes
40-60%
complete
100%
complete
Complete
Complete
Complete
Complete
Complete
Complete
Complete
Complete
Preliminary
100%
complete
100%
complete
80-90%
complete
100%
complete
Preliminary
80-90%
complete
100%
complete
Capital projects
80-90%
complete
100%
complete
Listing
Listing
Listing
various
stages
Partial
Partial
Partial
None Complete Partial
None Complete Partial
Preliminary
Partial
None
Startup procedures
maintenance
(new equipment)
Complete Partial
Baseline
none for new
capital
Original Equipment
Manufacturer (OEM)
specifications & drawings
Complete
Preliminary
Plant projects
Standardise the WBS
Move towards a common standard
layout for cost estimates. The capital
projects community has such a
standard (see Table 3). A suggested
outline version for turnarounds is
shown in Table 6.

Track the uncertainty allowances
If the turnaround community is
ever to develop even rudimentary
rules of thumb for estimating
emerging work, discovery work
and contingency for the unforeseen,
it must begin to track expenditure
in these areas. This will require two
responses from the community: a
willingness to differentiate clearly
the three categories in cost esti-
mates; and a willingness to
accurately track actual expenditure
from these three categories during
a turnaround.
Tie the estimates to the stage gates
In the world of capital projects, the
stage gate culminates in a cost esti-
mate. Currently, the typical review
stages for preparation and planning
of a turnaround are not tied to a cost
estimate. Tying the estimate and
stage gate together could improve
review of planning and preparation
progress.
Recommendations for longer-term
next steps
This article covers only the frst steps
in improving the accuracy and
predictability of turnaround cost
estimates. Further steps need to be
taken. Once there is common agree-
ment on the minimum standard of
scope basis and estimate basis for
turnaround estimates, and once
turnaround teams begin gathering
actual uncertainty allowance data,
the community will then be in a
position to begin developing logical
methodologies for calculating more
accurately the required level of
allowance for uncertainty in emerg-
ing work, discovery work and
contingency for each turnaround.
Acknowledgements
The author would like to acknowledge the
encouragement offered during the preparation
of this article by Bobby Vichich, Vice President,
Turnarounds, at Asset Performance Networks,
as well as the invaluable advice (particularly,
but not only, relating to Table 4) of John Casper,
Senior Consultant and Subject Matter Expert
for Turnarounds and Capital Projects, at Asset
Performance Networks.
References
1 http://www.api.org/aboutoilgas/sectors/
refning/refnery-turnaround.cfm.
2 http://ap-networks.com/latest-news/tinc-
europe-2011-summary.html.
3 We are very aware of the fact that in recent
years the preference within project cost
estimating circles is not to talk of a typical
10% or 30% estimate, but rather to talk
of classes of estimates. This is because of
the need to recognise that for the same level
of scope defnition, two projects could have
different levels of estimate accuracy because
of the inherent risks in their characteristics. For
example, a new technology project probably
carries more risk than a similar-sized project
expanding an existing plant. However, the
turnaround world has not yet reached that
level of sophistication. Hence, for the survey,
we used terms that are readily recognised, such
as 10% estimate.
Table 6
4 Lawrence G R, Stage gated approval processes
a practical way to develop and flter capital
investment ideas, Pharmaceutical Engineering,
vol 20, No 2, March/April 2008.
5 AACE International Recommended Practice
No. 18R-97; cost estimate classifcation system,
as applied in engineering, procurement, and
construction for the process industries.
6 Lawrence G R, The use and misuse of
contingency or why cutting contingency
makes projects more expensive, not less.
Pharmaceutical Engineering, vol 27, No 5, Sept/
Oct 2007.
7 Burroughs S E, Juntima G, Exploring Techniques
for Contingency Setting, AACE International
Transactions, Washington DC, 2004.
Gordon Lawrence is a Senior Consultant with
Asset Performance Networks, Amsterdam.
He holds a bachelors degree in chemical
engineering from Heriot-Watt University,
Edinburgh, a masters in biochemical
engineering from Birmingham University, and
an MBA from Strathclyde University Business
School, Glasgow.
Mechanical
work
Other
disciplines
Cost of the last
TA, adjusted for
inflation
Quantities for
mechanical work
from workpacks,
but then priced
in-house
Other disciplines
factored from
mechanical,
based on history
Quantities for all
disciplines
calculated and
priced by
contractors,
based on
workpacks
50% ROM
estimate
30% ROM
estimate
10% control
estimate
Home Office
Field
(during
shutdown
period)
Allowances for
unknown unknowns
Allowances for
known unknowns
Direct
(broken down by
unit/area, equipment
type and equipment
number
Field (before the
shutdown period)
Emerging
work
allowances
on each line
item
Discovery
work
allowances
on each line
item
Indirect
Contingency
Consumables
Equipment
Bulk materials
Turnaround planning
and preparation
Turnaround field
labour
Pre-turnaround field
work
Equipment rental
cranes, scaffold, etc
Logistics, temporary
facilities, etc.
Turnaround
management/
supervision
Direct
Indirect
Maintenance
Capital projects
Table 5
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JM_2168_Intercat_Ad.indd 1 02/12/2010 10:24
www.ptqenquiry.com
intercat.indd 1 8/12/11 21:13:09
Abatement of hydrogen sulphide
in asphalt
H
ydrogen sulphide (H
2
S) is a
naturally occurring gas
contained in many of the
worlds crude oils. It is also formed
by the degradation of sulphur
compounds in the oil when it is
exposed to high temperatures or
catalysts in the refning process.
Since the sulphur content of crude
oils is gradually increasing (see
Figure 1), H
2
S issues are expected
to remain a challenge for all aspects
of the refning industry, especially
when handling heavy oils.
Vacuum tower bottoms (VTBs),
the primary blending component
for asphalt production, have partic-
ularly high concentrations of H
2
S
because they do not undergo addi-
tional processing to remove H
2
S
through distillation, stripping and
sweetening processes as is done
with more refned fuels such as
gasoline, diesel fuel and home heat-
ing oils. VTBs are among the
heaviest of the products coming out
of the refnery and typically the
product in which sulphur
compounds concentrate. Due to the
viscosity of asphalt, it is stored at
high temperatures (300400F; 149
204C). These temperatures are high
enough to promote further thermal
cracking of sulphur-containing
compounds and the formation of
additional H
2
S. The amount of
cracking and H
2
S generation is
dependent on the structure of the
sulphur compounds present in the
oil and on the temperatures encoun-
tered during processing. Figure 2
shows a typical relationship
between storage temperature and
H
2
S formation.
Since H
2
S is a gas at typical stor-
age temperatures, it has a tendency
Risks of exposure at asphalt loading platforms require reliable monitoring of H
2
S
levels and a programme of abatement using effective chemical scavengers
JennifeR DRapeR and JoSepH StaRk
Baker Hughes
to migrate from the liquid phase
into the vapour phase above the oil.
Certain tank conditions, such as
increased liquid volume, agitation
and high temperatures, can exacer-
bate this already hazardous
situation by changing the partition
coeffcient (the ratio of H
2
S in the
liquid and vapour phases of the
crude oil) of the H
2
S in favour of
the vapour space. Asphalt is espe-
cially problematic because more
H
2
S partitions into the vapour
phase relative to other petroleum
products (see Table 1). Typically,
1 ppm of H
2
S in the liquid phase of
asphalt correlates to 400 ppm in the
vapour phase. Therefore, asphalt
1.2
1.6
1.4
1.0
0.8
0.6
0.4
0.2
1985 1990 1995 2000 2005 2010
S
u
l
p
h
u
r

c
o
n
t
e
n
t

b
y

w
e
i
g
h
t
,

%
0.0
figure 1 Trend in average sulphur content of US refnery crude oil inputs
Source: Energy Information Administration
6000
10000
9000
8000
7000
5000
4000
3000
2000
1000
0 100 200 300 400 500 600 700
H
2
S

g
e
n
e
r
a
t
e
d
,

p
p
m
Temperature, F
0
figure 2 Generation of H
2
S as a function of storage temperature. Samples held at
cracking temperature for one hour before analysis
also be a problem if the refnery or
storage facility is located close to
residential neighbourhoods. Wind
speed, direction and the topogra-
phy of the neighbouring areas can
either exacerbate or mitigate the
magnitude of the problem. H
2
S is
heavier than air and will tend to
settle in any low spots around the
storage facility, making these prime
areas for odour complaints, particu-
larly if the wind direction moves
the H
2
S towards the low spot.
Methods of analysis
Reliably determining the concentra-
tion of H
2
S in asphalt is diffcult. In
addition to the inherent danger of
working with a product that
contains high levels of H
2
S, there
are added complications relative to
the temperature of the material, its
viscosity and its tendency to quickly
lose H
2
S during testing. Testing is
most appropriately done on-site
with fresh asphalt sampled directly
from the unit into the sampling
container. Figure 3 shows the rapid
loss of H
2
S from sealed sampling
containers as a function of time and
loss of temperature. In this exam-
ple, three untreated asphalt samples
were taken consecutively from the
unit, sealed and tested at fve-
minute intervals. After 10 minutes,
a greater than 50% loss of H
2
S was
observed.
Baker Hughes feld can test method
Since the methodology for measur-
ing the performance of scavengers
is inherently variable, feld trials are
the most reliable way to determine
performance. Laboratory results can
be useful in predicting trends and
relative performance, but dosage
optimisation may only be achieved
through a feld trial. Baker Hughes
has developed a method to measure
the H
2
S content of asphalt safely
and to allow for a more reproduci-
ble means of establishing the
vapour phase in the sample
container. This method employs
quart-sized metal cans that are half-
flled with asphalt, sealed and
shaken using a specially designed
container that allows adequate
agitation of the sample while
protecting the operator from acci-
dental leakage of hot asphalt (see
can contain extremely high levels of
H
2
S in the vapour phase, even
exceeding 3% (30 000 ppm), which
can cause a variety of problems and
risks.
Concerns with asphalt H
2
S
Exposure risks
The foremost consideration when
dealing with hydrocarbons contain-
ing large amounts of H
2
S is safety
of personnel involved in its storage,
handling and transportation, and of
the community. Exposure to very
low levels of H
2
S can result in
signifcant health ramifcations. H
2
S
is especially insidious because it
deadens the sense of smell at
concentrations as low as 30 ppm,
and death can occur within a few
breaths at concentrations of 700
ppm.
Due to the toxicity of H
2
S, there
are regulatory limits at federal, state
and local levels, as well as limita-
tions placed by refneries and
terminals:
The American Conference of
Governmental Industrial Hygienists
(ACGIH) recently lowered the
recommended threshold limit value
(TLV) for H
2
S from 10 to 1 ppm,
and the short-term exposure limit
(STEL) from 15 to 5 ppm
The Occupational Safety and
Health Administration (OSHA)
limits H
2
S exposure to 20 ppm (ceil-
ing) and 50 ppm (peak, not to
exceed 10 minutes)
The National Institute for
Occupational Safety and Health
recommended exposure limit is 10
ppm maximum
Typical best practices limit the
levels of H
2
S to 100 ppm at barges
and 1015 ppm at truck loading
racks.
Air quality
Other regulatory limits are focused
on ambient air quality. The air
quality of communities located
around facilities that may emit H
2
S,
and the chronic health effects of
these emissions on nearby residents,
is a concern. Health effects from
chronic exposure to low levels of
H
2
S include headaches, insomnia,
nausea, shortness of breath and
eye irritation. Many states and
municipalities regulate the amount
of H
2
S permissible in the ambient
air, most of these as low as a few
parts per billion (ppb) of H
2
S. This
can limit asphalt production and
the flling of asphalt tanks due to
emissions during flling operations.
In addition to the inherent
dangers of chronic exposure to low
levels of H
2
S, nuisance odours can
600
900
800
700
500
400
300
200
100
0 5 10
300
500
H
2
S
,

p
p
m
Time elapsed after sampling, minutes
0
775
Figure 3 Infuence of time on H
2
S content of test samples
Petroleum product Partitioning rule of
thumb (ppm vapour
phase: ppm liquid phase H
2
S)
Asphalt 400:1
Gas oils 100:1
Diesel fuel 50:1
Gasoline 20:1
Partitioning coeffcient for common
petroleum products
Table 1
Figure 4). Untreated samples are
tested immediately using gas detec-
tion tubes. For the purposes of
screening additive performance, the
scavenger should be added to the
sample container prior to introduc-
ing the asphalt, then transported to
an oven in an insulated container,
where it is stored at temperatures
and time periods consistent with
those experienced in the feld.

Solutions to asphalt H
2
S problems
The issues presented by the high
H
2
S content of asphalt clearly
require serious consideration.
Operational solutions, such as air
blowing or sending off gases to a
purifcation system using flter
canisters, are often employed to
reduce these hazards. However, in
some cases, these are not suffcient
to reduce the H
2
S to acceptable
levels. The use of chemical H
2
S
scavengers, in conjunction with
appropriate engineering controls,
can reduce the H
2
S content of
asphalt blendstocks and keep the
H
2
S level low during extended stor-
age at elevated temperatures.
Scavengers reduce tank emissions
and the associated nuisance odours,
as well as decrease the safety risks
to those individuals involved in the
transfer, transportation and use of
these products.
Chemical additive solutions
There are many chemicals that will
react with H
2
S, including caustic,
peroxides, formaldehyde, nitrites
and many types of amines. All of
these function by converting the
H
2
S into other sulphur compounds.
The preferred method for scaveng-
ing H
2
S from hydrocarbon streams
is to use a chemical conversion
reagent. This type of additive
reacts with H
2
S irreversibly to form
thermally stable reaction products
and does not revert back to H
2
S if
exposed to higher temperatures
further downstream. Scavenger
programmes are selected depend-
ing on the nature of the H
2
S
problem being addressed and
the petroleum product being
treated.
The viscous nature of asphalt, its
necessarily high storage tempera-
tures and the propensity to continue
to produce H
2
S are challenges to
the effcient scavenging of H
2
S
from asphalt blending components.
Reducing the H
2
S content of asphalt
requires a chemical scavenger that
can function under severe condi-
tions. An asphalt H
2
S scavenger
must demonstrate the following
additional qualities:
Large H
2
S uptake capacity: the
scavenger must be very reactive
towards H
2
S to minimise the
required additive volume and cost
Rapid reaction with H
2
S: often
very little residence time is availa-
ble, so the scavenger must be able
to reduce H
2
S quickly
Non-reversible, thermally stable
reaction products: the reaction
product between the scavenger and
H
2
S must be thermally stable even
under the high-temperature condi-
tions of asphalt production, storage
and transportation
No detrimental effect on the
asphalt: asphalt has specifc quality
requirements; therefore the additive
cannot change its physical
attributes
Selective for H
2
S: application
economics are improved when the
scavenger targets H
2
S only and is
not consumed by other species.
Baker Hughes supplies several
oil-soluble and metal-based H
2
S
scavengers. Water-soluble additives
are generally not appropriate
because the product will fash off
water at temperatures above 200F
(93C), leading to potential safety
issues.
Conventional scavengers
Oil-soluble H
2
S scavengers are used
in high-temperature applications
where water tolerance is an issue.
These products perform and react
with H
2
S irreversibly to form a
thermally stable, oil-soluble alkyl
sulphide. They can be applied at a
wide range of temperatures, from
ambient up to 350F (177C), and
may be the product of choice for
viscous heavy oils and resids.
6000
10000
9000
8000
7000
5000
4000
3000
2000
1000
0 250 500 750 1000 1250 1500 1750 2000
H
2
S
,

p
p
m
Dosage of H
2
S scavenger, ppm
0
Novel scavenger No. 2
Novel scavenger No. 1
Conventional scavenger
Figure 4 Baker Hughes equipment safely measures H
2
S in hot asphalt
Figure 5 Reduction in H
2
S by conventional and metal-based H
2
S scavengers
manner. Field testing is always crit-
ical to ensure that the selected
additive is able to achieve the
appropriate level of H
2
S removal in
a commercial application without
negatively affecting the asphalt
quality.
Chemical additive selection
and application
Selecting the most appropriate
additive and its dosage requires
specifc knowledge of the applica-
tion in which it will be used as well
as awareness of the target levels
needed to meet specifc state, local
or facility regulations. The tempera-
ture of the fuel to be treated,
available injection locations, resi-
dence time and the test method by
which performance will be evalu-
ated are a few variables that should
be considered. For example, tradi-
tional organic-based additives can
be very effective in reducing H
2
S to
acceptable levels if the initial H
2
S
concentration is moderate (a few
thousand ppm or less) and the resi-
dence time is relatively long.
However, if the requirement is to
scavenge a large concentration of
H
2
S in a short amount of time, for
example, before the asphalt reaches
the frst storage tank, a metal-based
scavenger may be a more appropri-
ate choice.
Case study
The following case history illus-
trates some of the results achievable
using H
2
S scavengers in asphalt.
A refner with an existing H
2
S
abatement programme reported a
high number of H
2
S monitor alarms
from workers at the asphalt loading
rack and wanted to reduce those
incidences to zero. The existing
programme achieved some H
2
S
reduction, but was not able to get
the concentration of H
2
S low
enough to prevent exposure of
workers at their loading rack. A
plateau effect was observed where
additional additive usage did not
produce a corresponding reduction
in H
2
S content. A trial was
conducted using a metal-based H
2
S
scavenger. The results from the
feld trial are shown in Figure 6.
Signifcantly greater H
2
S reduction
(99.5% compared with 75%) was
Metal-based scavengers
Metal-based H
2
S scavengers are used
primarily to address the specifc
needs of very high-temperature
and high-H
2
S applications. These
additives can be used at temperatures
well in excess of 350F (177C) to
form thermally stable products.
These scavengers are able to achieve
H
2
S reduction levels that organic-
based additives simply cannot
support. These additives will react
much faster and scavenge more H
2
S
than traditional scavengers. While
these products are typically used to
treat asphalt, other applications can
be envisioned that are not sensitive
to metal content.
Figure 5 shows the performance
of metal-based scavengers in the
Baker Hughes Sulfx additive prod-
uct line relative to that of a more
conventional amine-based product.
The conventional scavenger achieves
a good reduction in H
2
S, but eventu-
ally plateaus in performance. The
metal-based scavengers are able to
achieve a 99% reduction in H
2
S at a
signifcantly lower dosage. The
increased reactivity with H
2
S gives
these products a favourable cost-
performance ratio relative to other
high-temperature H
2
S scavengers.
Dispersions of nano-particle metal
compounds in hydrocarbon medi-
ums are commonly used in the
industry and have largely become
an industry standard for the rapid
removal of large quantities of H
2
S
in high-temperature applications.
These products offer the advantage
of a large surface area available for
reaction with H
2
S and have proven
performance without any negative
impact on asphalt quality. A critical
consideration when choosing an
H
2
S scavenger is that not all
additives perform in an equivalent
6000
7000
8000
5000
4000
3000
2000
1000
Existing programme
4 dosage
Metal-based scavenger
1 dosage
H
2
m
p
p

,
S
0
Storage tank
Rundown to storage
Unit out|et
Figure 6 Results from feld trial using metal-based H
2
S scavenger
15
25
20
10
5
A
l
a
r
m
s

p
e
r

d
a
y
Time
0
Figure 7 Reduction in alarms as a result of H
2
S scavenger programme
achieved using the metal-based additive at one-fourth
the dosage of the incumbent product. Through the use
of the scavenger programme, this refner was able to
achieve a dramatic reduction in the number of H
2
S
alarms reported (see Figure 7). This programme has
been in commercial use for more than fve years. It has
also resulted in fewer environmental incidents and
greater peace of mind for the refner, workers and
transportation companies.
Conclusions
The reduction of H
2
S in asphalt is an important consid-
eration because there is a signifcant risk of exposure to
people, equipment and the environment. Asphalt is
generally transferred at loading racks, where personnel
manning the loading rack may be exposed to toxic
vapours. Transport to terminals and application of the
fnal product are also situations where exposure to
potentially dangerous vapours containing H
2
S may
occur. The viscous nature of asphalt and the high
temperatures needed to work with this material make
for a dangerous combination when even low levels of
H
2
S are present in the liquid. However, removing H
2
S
from asphalt can be accomplished through the proper
application of a chemical scavenger. An additive
programme that uses best-in-class application technol-
ogy and test methods can optimise additive dosage,
improve scavenger response and allow refners to meet
their H
2
S specifcations economically.
A thorough understanding of the asphalt blending
confguration, tank residence times, available mixing
equipment and injection points is critical to designing a
programme that produces the desired results while
ensuring an optimised chemical programme. Diffculties
measuring H
2
S content in asphalt safely and reproduci-
bly can also be an issue. With the proper additive,
equipment and monitoring, H
2
S scavengers allow refn-
eries to increase employee safety, comply with
environmental regulations and minimise capital
expenditures.
SULFIX is a mark of Baker Hughes.
Jennifer Draper is Manager of the Technology Support Group for Fuel
Additives with Baker Hughes and has 13 years of fuel additives industry
experience, with particular areas of concentration including H
2
S
scavengers, distillate cold fow improvers and mercaptan scavengers. She
has a PhD in inorganic chemistry from Texas A&M University.
Joseph Stark is Director of the Petroleum Additives Group with Baker
Hughes; his previous roles with the company include Senior Synthetic
Chemist for the Refnery Process Group, Manager for Antifoulants and
Corrosion Groups, and Manager of R&D for the Oilfeld Chemicals Group.
He has a PhD in inorganic chemistry from Kansas State University and
holds nine patents. Email: [email protected]
Table 3
H
2
S scavengers allow refneries
to increase employee safety and
minimise capital expenditures
content fuel. The only exception may be if scrubbers
prove to be the preferred control technology. Ships can
use scrubbers to meet the SO
x
limits of ships emissions;
however, there has not been a substantial application
of scrubbers in marine vessels yet. By 2020 or 2025, the
spread between distillate and 3.5% sulphur residual
fuel is expected to be around $30/bbl and $35/bbl
respectively on our current price projections.
K^g^kl
Regardless of economies of scale, a refner producing any
amount of straight-run residue, VGO or fuel oil will have
to rethink their strategy with these new regulations.
Refners who process high-sulphur crude and blend
the residuum back to fuel oil will increasingly discover
that simple topping and hydro-skimming margins are
barely proftable.
The impact on refneries in the frst stages of the
new regulations is likely to be limited. However, when
the sulphur cap goes to 0.1% sulphur for ECAs and
then 0.5% sulphur globally, the effects could be quite
substantial. The impact of a global regulation is much
bigger than the effects of regulations followed by indi-
vidual countries (see Figure 3).
Already global growth in demand for distillate is
quite strong. Despite additions in refning capacity
over the past three years, we can foresee regional
diesel shortages in many markets as a result of
increased onshore demand (see Figure 4). Despite
more conversion capacity starting up over the next
couple of years, the question remains whether the
additional demand, created by moving from residual
fuel to marine diesels, can be met by existing conver-
sion capacity.
;e^g]^kl
The composition of the blending recipe for bunkers
has changed, as blenders have to blend lower-sulphur
residue and progressively more distillate into marine
bunkers. The sulphur constraint imposed at the begin-
ning of July 2010 meant that blenders had to further
blend down the sulphur content of 1.5% sulphur fuel
to 1% sulphur for the ECAs.
Looking at January 2012 onwards, blenders globally
will have to blend down the marine sulphur content
from 4.50% to 3.50%. As noted previously, we do not
see this as a major obstacle, as the average global qual-
ity (per IMO 2007) is already well below 3.5% sulphur.
The transition on a global level to 3.5% sulphur should
thus happen rather smoothly. Still, we do foresee some
increases in shipper fuel costs merely because the
specifcation changes, even if the fuels already meet
the new limit.
In the long run, the importance of blending opera-
tions will increase drastically, as the ECA marine fuel
product will have to meet 0.1% sulphur content, even
more so if the number of ECAs increases by 2015. By
2015, blenders will start increasing the amount of
distillate going into fuel oil. We anticipate that given
todays rule of thumb that intermediate fuel oil (IFO)
is 75% fuel oil and 25% distillate after 2015 and for
ppp'îmj'\hf IMJJ-+)***+0
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2
S Removal / Recovery
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Oxygen enrichment in desulphurisation
A
s a primary source of
sulphur emissions, the
refning segment of the
petrochemical industry has found
itself juggling fears around energy
insecurity with concerns about
climate change. Sulphur dioxide
(SO
2
) is one of the major air pollut-
ants that impact our climate and is
a key focus for the United Nations
and environmental activists. It can
be harmful to health, as it is a
potent asthma trigger and can cause
other potentially damaging respira-
tory health effects. When sulphur
combines with oxygen to create
SO
2
, it is defned as a critical air
pollutant by the US Environmental
Protection Agency (EPA) and can
form dangerous sulphates, which
can be breathed deep into the lungs.
Once oxidised by air, it also forms
sulphuric acid, the major compo-
nent of acid rain. Acid rain harms
fsh, damages forests and plants,
and can erode buildings.
SO
2
is formed when sulphur-
containing fuels, such as coal and
oil, are burned. The primary sources
of SO
2
emissions are power plants,
refneries and smelting facilities.
SO
2
is also found in the exhaust of
diesel fuel and gasoline. Despite
technological advances, controlling
sulphur remains a technical chal-
lenge for the petrochemical
industry, as the sulphur content of
the worlds dwindling crude oil
resources is increasing.
Almost every oil feld produces
crude with a unique mixture of
characteristics, which presents
distinct challenges to oil companies
involved in separating crude into
different products. In addition to
sulphur content, refneries are being
Oxygen enrichment technology is a viable and a cost-effective solution for
signifcantly increasing sulphur treatment capacity
ShivAn AhAmpArAm and Stephen hArriSOn
Linde
challenged to manage increased
levels of acid gas or sour water
stripper gas and the occasional lean
acid gas feed.
For refners, throughput can be
limited by the speed at which plants
can desulphurise crude. However,
the more stringent the desulphurisa-
tion process becomes, increasing
Claus plant loadings with hydrogen
sulphide (H
2
S) and ammonia, the
more frequently bottlenecks in the
production process also become.
Claus plants operating in refneries
process concentrated H
2
S fractions,
converting them into elemental
sulphur. The technology is also able
to destroy pollutants, particularly
ammonia.
increased capacity
Although not new, oxygen enrich-
ment technology has now come to
the fore as a viable and cost-
effective solution for signifcantly
increasing a plants sulphur
handling capacity, as well as
addressing problems associated
with contaminants such as ammo-
nia and hydrocarbons.
Oxygen enrichment of the
combustion air signifcantly
increases sulphur handling capac-
ity. Associated benefts include
increased productivity achieved
without changing the pressure
drop, more effective treatment of
ammonia-containing feeds and less
effort required for tail gas purifca-
tion (reduced nitrogen fow).
Oxygen enrichment is also a highly
customisable approach to improv-
ing Claus plant yield, with options
varying from low-level oxygen
enrichment to employing advanced
proprietary technology to bring
about capacity increases of up to
around 150%.
In practical terms, this means that
refneries can delay new Claus
investment decisions as they can
extend their existing Claus plant
capacity. This is a particular advan-
tage to those refneries whose plant
footprints cannot accommodate the
introduction of additional Claus
plants.
Low-level enrichment is achieved
by injecting oxygen via a diffuser
into the process air to the sulphur
recovery unit. The maximum oxygen
enrichment level that can be accom-
modated via this method is 28% and
provides a capacity increase of
approximately 30% when processing
acid gas rich in H
2
S, as is the case in
most oil refneries.
Generally, the sulphur plant will
require no equipment modifcation
other than the provision of a tie-in
point for oxygen injection into the
combustion airline.
1
However,
when even greater capacity is
needed and increased levels of
oxygen beyond 28% are required, it
is necessary to introduce the oxygen
into the reaction furnace separately
from the air supply, as the combus-
tion air piping in conventional
sulphur plants and air-only burners
is unsuitable for use with highly
oxygenated air.
Self-cooled burner
Addressing this challenge, a new
type of burner, Sure, developed by
Linde Gas, has been specifcally
designed for this purpose a self-
cooled tip-mix burner with separate
ports for acid gas, oxygen and air
supply. The burner can be used in
both end- and tangential-fred
linde.indd 1 9/12/11 12:02:57
guided by documented standards of
measurement and recommended
analytical methods such as various
ASTM methods. Similar procedures
are used to determine total sulphur
content in incoming natural gas
feedstocks. The analytical technique
most commonly used for this
purpose in modern refneries and
LNG processing terminals involves
chemiluminescence. These instru-
ments use a two-stage method,
where the sample is frst pyrolised
in a fame of purifed or synthetic air
and high-purity hydrogen under
vacuum to generate sulphur monox-
ide. This is then transported by a
carrier gas, typically argon or nitro-
gen at a purity of 99.999%, to a
chamber, where it reacts with ozone
to generate SO
2
and UV light. The
light generated is measured by a
photomultiplier tube to determine
the total quantity of sulphur in the
sample.
Another technique is atomic emis-
sions spectroscopy (AES), a method
of chemical analysis that uses the
intensity of light emitted from a
fame or plasma to determine the
quantity of sulphur in the sample.
The wavelength of the atomic spec-
tral line identifes the element,
while the intensity of the emitted
light is proportional to the quantity
of atoms present. AES is a sensitive
technology, capable of measuring
down to levels of parts per million
(ppm) and also of identifying actual
molecules, therefore providing both
qualitative and quantitative infor-
mation at these low levels. It is
suitable for measuring sulphur
levels as part of process control,
fnal product quality control and
for environmental emissions moni-
toring applications.
AES can also be combined with
inductively coupled plasma (ICP)
a technique that is highly sensi-
tive and can quantify concentrations
in the range of parts per million, or
even billion which would require
high-purity argon. Alternatively,
AES can be combined with gas
chromatography, where the tech-
nique would be referred to as
GC-AED. The chromatography
would consume a carrier gas, such
as high-purity helium, to drive the
sample through the column and
furnace designs. The burner
achieves effective mixing of H
2
S
and oxygen-enriched air over a
wide load range.
The intensive mixing characteristics
of these burners have been developed
through test work at Lindes own
pilot plant, a commercial-scale
sulphur recovery unit, harnessing
computational fuid dynamics (CFD)
modelling to achieve effective
contaminant destruction and signif-
cantly increased tonnage output.
For operation with high levels of
oxygen enrichment, greater than
45%, methods must be employed to
mitigate a high fame temperature
in the reaction furnace. The Sure
double combustion process
provides full capability at up to
100% oxygen in an uncomplicated
process that is easy to install, oper-
ate and maintain.
Double combustion
Double combustion, as the name
implies, splits the heat release into
two separate reaction furnaces with
cooling between. In the frst reaction
furnace, all amine gas, sour water
stripper gas and, if required, air are
fed to the Sure burner together with
the supplied oxygen, the level of
which depends on plant throughput.
The tip-mix burner allows for thor-
ough mixing, giving effective
contaminant destruction effciencies.
There is no sulphur condenser
between the frst waste heat boiler
(WHB) and the second reaction
furnace. Also, there is no burner in
the second reaction furnace. By
design, the gases exiting the frst
WHB and entering the second reac-
tion furnace are substantially above
the auto-ignition temperature of
H
2
S and sulphur vapour, under all
normal and turn-down operation
conditions. This system allows for a
low pressure drop, which is easy to
control and easy to install.
Temperature profle
The result of this type of control is
a temperature profle suited to the
Claus process. Operating tempera-
tures in the frst reaction furnace
are high enough to destroy ammo-
nia and hydrocarbons, but remain
well below refractory limitations.
KOA Oil in Japan has successfully
harnessed Lindes double combus-
tion process since 1990.
A novel approach has used the
benefts of a multi-pass WHB for
plants with a restricted footprint.
The zone between the frst and
second passes of the boiler is
utilised as the second reaction
furnace of the double combustion
process. In this situation, lances are
installed in the channel head
connecting the frst and second pass
of the WHB tube sheets (where the
remaining oxygen can be added).
For the optimum design and loca-
tion of the burner and oxygen
lances, Linde uses a validated CFD
model. This particular approach has
been operational at API Falconara,
Italy, since 1996 and at Shell Puget
Sound refnery and General
Chemicals Anacortes site.
The change-out of the WHB can
improve energy effciency at a plant
through the generation of valuable
high-pressure steam. Other energy
effciency benefts arise from the
much-reduced process gas fow
through the plant. This reduces the
converter reheat and incinerator
fuel gas requirements to a mini-
mum and reduced energy
requirements mean signifcantly
reduced carbon dioxide emissions.
Measuring sulphur levels
Inseparable from the crude oil refn-
ing process is the measurement of
sulphur levels present in raw mate-
rials during the process, in fnished
products and being emitted to the
atmosphere.
In refning process control, or for
determination of incoming crude oil
composition, sulphur is often meas-
ured quantitatively in percentages,
For operation with
high levels of oxygen
enrichment, methods
must be employed to
mitigate a high fame
temperature in the
reaction furnace
linde.indd 2 9/12/11 12:03:14
separate the various components, to
allow species identication in the
atomic emission detector. The
system would also require periodic
calibration with appropriate calibra-
tion gas mixtures.
Sulphur-containing molecules
The benet of these techniques is
that they can identify some of the
sulphur-containing molecules, such
as carbonyl sulphide, methyl
mercaptan or ethyl mercaptan, in
order to understand where the vari-
ous sulphur compounds originate
from. This is useful for crude oil
rening and equally relevant to
natural gas processing.
In addition to sulphuric acid as
the key component of acid rain,
other environmentally hazardous
sulphur components produced as a
result of crude oil processing
include H
2
S and carbonyl sulphide,
both highly corrosive and toxic
chemical compounds.
Environmental authorities such as
the EPA have applied stringent
regulations governing hazardous
emissions from industries such as
oil reneries and this, in turn, has
placed a heavy emphasis on accu-
rately measuring the sulphur
content of emissions.
To this end, among other meas-
urement techniques, reneries have
installed continuous emission moni-
toring systems (CEMS) in plant
stacks to measure emissions from
exhaust streams on a continuous
basis.
To be able to trust the values of
these analysers, very accurate cali-
bration gas mixtures are required.
In this realm, Linde supplies tracea-
ble calibration mixtures for
measuring sulphur compounds in
petrochemical renery stacks.
Verication programme
In 2010, the EPA, in cooperation
with the National Institute of
Standards and Technology (NIST),
conducted a blind audit of EPA
Protocol gases used to calibrate
CEMS and the instruments used in
EPA reference methods. These
gases and the associated quality
assurance/quality control checks
help to ensure the quality of the
emission data the EPA uses to
assess achievement of emission
reductions required under the
Clean Air Act.
This verication programme eval-
uated Linde in regard to how
accurately its products measured
SO
2
, nitrogen oxide and carbon
dioxide. Lindes US production site,
at Alpha New Jersey, passed the
audit with zero failures and, in
2011, the company was granted
continued approval to produce EPA
protocol gas standards both at this
site in the US and at an additional
site near Toronto, Canada.
As in other parts of the world, the
European Union is introducing
stricter limits on pollutant emis-
sions from light road vehicles,
particularly for emissions of nitro-
gen particulates and oxides. Since
2009, it has been mandatory to have
ultra-low-sulphur petrol and diesel;
that is, fuels containing less than 10
ppm of sulphur.
Analysis of sulphur compounds in
fuels has therefore not only become
a critical requirement, but so has the
need to measure for lower and lower
levels of sulphur compounds. It is
now vital to be able to detect
extremely low levels of sulphur,
down to parts per billion, and a
range of instrumentation techniques
and detectors are required to meet
these requirements. One of the typi-
cal methods used for the
determination of sulphur species in
fuel samples is GC separation
followed by sulphur chemilumines-
cence detection (SCD).
References
1 Heisel M, Schreiner B, De Lourdes Coude M,
Oxygen enrichment is an option to reduce
loadings for Claus plants, Hydrocarbon
Processing, Feb 2007.
Shivan Ahamparam leads Lindes global
marketing programme in chemistry and
energy from Murray Hill, New Jersey. She has
over 15 years experience in petrochemicals,
speciality chemicals and industrial gases, and
has a masters in mechanical engineering from
Auckland University, New Zealand, and a degree
in engineering from Canterbury University,
Christchurch, New Zealand .
Stephen Harrison leads Lindes global Specialty
Gases & Specialty Equipment business from
Munich, Germany. He has 20 years experience
in industrial gases and holds a masters in
chemical engineering from Imperial College,
London, UK.
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Green retarder technology for the
styrene industry
S
tyrene is an important petro-
chemical product that is used
as a starting material for a vari-
ety of polymer products, polystyrene
in particular. There are two main
industrial routes for the production
of styrene; namely, the EB/SM route
and the PO/SM (sometimes referred
to as the SM/PO) route. The EB/SM
route produces styrene through the
dehydrogenation of ethylbenzene.
The PO/SM route furnishes styrene
through the oxidation of ethylben-
zene and subsequent addition of
propylene to co-produce propylene
oxide and styrene, after dehydration
of the intermediate alcohol.
Ethylbenzene, used in both cases, is
produced through an alkylation
reaction between benzene and ethyl-
ene. As of 2009, total global styrene
capacity was about 30 million t/y,
of which about 80% was produced
through the EB/SM process and
20% through the PO/SM process.
Regardless of specifc licensed
technologies for styrene production,
crude styrene produced in the reac-
tion section needs to be purifed to
yield polymer-grade styrene mono-
mer. This is typically accomplished
through a series of distillation
towers designed to separate styrene
from unreacted ethylbenzene as
well as other reaction byproducts.
Polymer control in a styrene unit
Styrene is a very reactive monomer.
If not properly inhibited, it will
polymerise rapidly via a free radical
mechanism at elevated temperatures
typically encountered in the styrene
purifcation process. The polymeri-
sation reaction is self-initiating; no
initiators such as peroxides are
required to initiate the reaction proc-
Increased environmental and safety awareness in the styrene industry has led to
the development of more acceptable alternatives to toxic nitrophenolic retarders
LISheng Xu, JavIer FLorencIo, vIncent LewIS and chrIStoPher MorrISon Nalco
ana guzMan, carMen MonFort and ana oLIvareS Repsol Qumica Tarragona
ess. The amount of polymer formed
in a specifc production unit is a
function not only of the process
temperature, but also of the resi-
dence time and styrene monomer
concentration in the distillation
towers. Higher process temperatures
result in increased rates of polymeri-
sation. Furthermore, increased
residence times result in a greater
amount of polymer forming.
Proper polymer control in the
purifcation section of a styrene
plant is important for two main
reasons. First, styrene monomer
that is polymerised is an economic
loss for the producer, as it can no
longer be sold as styrene monomer.
Second, if polymerisation goes
unchecked, high polymer levels in
styrene monomer will result in an
increase in stream viscosity. While
polystyrene is soluble in styrene
monomer, very high levels of poly-
styrene can make the stream overly
viscous, causing diffculties in
pumping the material through the
process. Occasionally, high levels of
divinylbenzene (DVB) can also
result in the formation of insoluble
crosslinked polymer that will
deposit inside the tower.
technologies to control polymer
There are two categories of
compounds that are commonly
used for polymer control. The frst
category is a slow-reacting
compound, typically known as a
retarder. Today, the most commonly
used retarders in the industry are
nitrophenolic-based products, and
in particular DNBP (2,4-dinitro-6-
sec-butylphenol). The second
category is much faster reacting
and is sometimes referred to as a
true inhibitor. The true inhibitors
available on the market are mostly
proprietary formulations that offer
a faster polymer inhibition rate than
DNBP. Figure 1 shows the differ-
ence between a retarder and an
inhibitor. In the graph, uninhibited
styrene has an inherent polymerisa-
tion rate, as represented by the line
marked as untreated. A retarder
R
a
t
e

o
f

p
o
l
y
m
e
r

f
o
r
m
a
t
i
o
n
Time
Inhibited
Retarded
Untreated
Figure 1 Polymer inhibition behaviour: retarder vs inhibitor
nalco.indd 1 9/12/11 12:15:51
DNBP poses severe health risks. It
is also soluble in water at levels
that can be highly toxic and there-
fore a potential hazard in the
environment. Initially sold as a
herbicide, its use in agriculture has
long been banned in the US and
many other countries. While the
risk of exposure to DNBP in an
industrial setting is certainly lower
than in an agricultural setting,
handling DNBP is by no means
safe, since it has a very low LD50.
Industrial accidents do occur, and
operators and the environment in
the immediate vicinity of the plant
are always at risk as long as DNBP
is utilised. In recent years, the
potential risks of using DNBP in a
styrene plant have been highlighted
in many countries.
DNBP is also a major generator of
NO
x
when incinerated. In a typical
styrene plant, DNBP exits the unit
along with heavy tars, and the tar
stream is typically used as fuel.
While recovering fuel value, burn-
ing of tar containing DNBP
produces a signifcant amount of
NO
x
. Up to one-quarter of the
DNBP (by weight) is converted to
NO
x
when burned. NO
x
is a known
environmental pollutant, and many
countries have NO
x
emission limits
in place.
Future sustainable development
of the chemical industry is largely
dependent upon how successful the
industry is in improving the health,
environment and safety standards
of its operations. This requires fnd-
ing innovative ways by which
highly toxic materials can be
replaced by more environmentally
friendly alternatives. The develop-
ment of the Prism Green Retarder
technology is an effort aimed at
offering the industry a green alter-
native to DNBP.
To develop a green retarder, there
are two main criteria. First, it must
be less toxic than DNBP and gener-
ate less NO
x
when burned. Second,
it should have similar polymer
control properties (reaction rate) as
DNBP. It must be a true retarder.
Since a retarder is utilised to offer
longer polymer control times
during an emergency shutdown, a
higher reaction rate than DNBP is
not necessarily a desirable feature.
would slow the polymerisation rate
and is represented by the red line
with reduced slope. A true inhibitor
is faster reacting than a retarder;
therefore, the polymerisation rate
when an inhibitor is used would be
less than a retarder, as represented
by the orange line. However, due
to its rapid rate of reaction, inhibi-
tor is consumed much faster than a
typical retarder. Once consumed,
polymerisation resumes at the rate
of an uninhibited system, as repre-
sented by the second half of the
orange line.
Optimal approach to polymer
inhibition
The optimal approach to polymer
control in a styrene unit is to use a
combination of inhibitor and
retarder. This ensures polymer
control during both normal opera-
tions and emergency shutdowns.
During normal plant operations, a
faster reacting true inhibitor
provides superior polymer control
versus a retarder such as DNBP. In
fact, the faster the reaction rate of
an inhibitor, the more effective it is
in reducing polymer formation.
Nalco offers Prism inhibitors that
are several orders of magnitude
faster than DNBP for polymer
control in a styrene unit. Some
styrene producers only use DNBP
for polymer control, but with less
satisfactory results. However, when
emergency shutdowns occur, a
retarder is essential in protecting
the unit from excessive polymer
build-up. When a plant loses power,
it loses, in most cases, its ability to
pump the hot process stream out of
the distillation towers. It also loses
in most cases its ability to inject
polymer inhibitor and/or retarder.
Due to tower insulation, the hot
process fuid will remain at elevated
temperatures for an extended
period of time. This long residence
time can cause excessive polymer
build-up if not properly controlled.
In severe cases, high polymer levels
eventually lead to solidifcation and
can turn the distillation tower
contents into a solid block of poly-
mer a devastating outcome for
any facility. A fast-reacting inhibi-
tor, while excellent for controlling
polymer during normal operations,
can be quickly consumed during an
emergency shutdown, thus losing
its ability to protect the tower. On
the other hand, a retarder owing
to its slower reaction rate will
remain effective for longer and offer
prolonged protection for the tower.
The ratio between inhibitor and
retarder should be considered care-
fully to result in optimal cost
performance while ensuring safety
during an emergency shutdown.
A summary of the relative polym-
erisation rates of various inhibitors
and retarders is shown in Table 1.
Green retarder
As an effective retarder, DNBP has
been the product of choice for the
styrene industry. It is a reliable and
economic means of protecting the
tower during emergency shut-
downs. But DNBP is also highly
toxic. It causes reproductive and
developmental system damages in
mammals. It is classifed by
European Regulations as a CMR
(carcinogenic, mutagenic and repro-
ductive toxin substances) because it
is a reproductive toxin category 2
and 3, a chemical that will be
subject to further reviews for its
future use. Potential exposure to
2R
.
RR 10
9
M
-1
s
-1
(rate limit)
R
.
+ PRISM Inhibitor 10
7
-10
8
M
-1
s
-1
R
.
+ Hydroxylamines 10
5
M
-1
s
-1
R
.
+ AOH (retarders) 10
3
-10
4
M
-1
s
-1
R
.
+ 10
2
M
-1
s
-1
Table 1 Relative reaction rates
nalco.indd 2 9/12/11 12:16:04
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Cost is also an important factor
in the adaptation of green
retarder technology. Although
the green retarder concept has
been around for some time, the
costs of such products have
been prohibitively high until
recently, which has prevented
their widespread application.
The Prism Green Retarder
technology was developed as
part of Nalcos Prism product
line with these requirements in
mind. Specifcally, it has
considerably lower toxicity
and lower water solubility
than DNBP. Lower water solu-
bility reduces the risk of
contaminating the water
system, in the case of an acci-
dental release. In Figure 2, the
colour of water in the presence
of either Prism Green Retarder or
DNBP can be visually compared.
In the case of green retarder, the
water colour is unchanged, while
in the case of DNBP the water
turned to a pale yellow colour due
to the high water solubility of
DNBP. The green retarder also has
negligible NO
x
generation poten-
tial. Table 2 shows a comparison
between DNBP and the green
retarder.
From a performance standpoint,
the green retarder is comparable to
DNBP in its ability to control poly-
mer. Figure 3 shows the polymer
inhibition performance of both
DNBP and the green retarder under
various conditions in laboratory
tests.
Programme implementation
The accepted best practice for
polymer inhibition in a styrene
unit is to combine the use of a
retarder and an inhibitor,
providing strong polymer inhi-
bition during normal plant
operations and adequate
protection in the event of an
emergency shutdown. During
the implementation of a Prism
programme using an inhibitor
and green retarder, injection
points and dosages are adjusted
to optimise plant performance
and economics. A key perform-
ance indicator for most styrene
producers is the soluble poly-
mer level in the bottom of the
purifcation section distillation
tower. To accurately measure
soluble polymer levels, Nalco
developed a proprietary test
method that is more accurate than
the often-used ASTM method
D2121.
Before the implementation of a
replacement programme, a compre-
hensive MOC analysis (mechanical,
operational and chemical) approach
should be carried out to ensure
maximum return on investment
from the chemical treatment. This
approach involves a detailed plant
survey from both a mechanical and
operational standpoint. Critical
parameters to take into considera-
tion include tower bottom
temperatures, tower internal design,
stream compositions, tower resi-
dence times, tar recycle ratios, as
well as others. Soluble polymer
data are evaluated against chemical
injection dosages. Under the same
operating conditions, the soluble
polymer level is inversely propor-
tional to the inhibitor reaction rate
and dosage. A faster reacting inhib-
itor will result in a lower soluble
polymer make, as will a higher
inhibitor dosage of a slower react-
ing inhibitor. It is therefore
advantageous to employ the fastest
reacting polymer inhibitor
available.
Baseline data are collected and
benchmarked against a database
that contains information from over
30 styrene plants. This database
enables opportunities for improve-
ment to be identifed when
0.6
0.8
0.4
0.2
85C / 1 hr
150 ppm
85C / 4 hr
150 ppm
110C / 1 hr
120 ppm
110C / 2 hr
240 ppm
120C / 1 hr
500 ppm

t
a

t
n
e
t
n
o
c

r
e
m
y
l
o
P
%

,
e
t
a
t
s

y
d
a
e
t
s
0.0
DNBP
Prism Green Retarder
Figure 2 Colour comparison of the water phase in
contact with DNBP and green retarder
Figure 3 Polymer control performance: DNBP vs green retarder
Acute toxicity Water solubility, NO
x
potential,
Oral LD
50
rats, mg/kg mg/L kg_NO/T
DNBP 27 52 250
Green retarder >5000 0.02 Negligible
* Comparison based on active component. Toxicity characteristics of ethylbenzene solvent are not refected
in the comparison.
Comparison of DNBP and green retarder
Table 2
nalco.indd 3 9/12/11 12:16:18
designing treatment details. The
programme design also takes into
consideration the styrene markets
conditions to ensure maximum
return on investment.
To ensure a smooth transition, it
is advised that inhibitor application
should be commenced while leav-
ing DNBP injection unchanged. To
facilitate a safe withdrawal of DNBP
and the introduction of green
retarder, the inhibitor injection
should be increased prior to the
withdrawal of DNBP. At elevated
inhibitor levels, DNBP dosage is
gradually reduced until it is
completely removed from the
system. Green retarder is immedi-
ately introduced once DNBP is
removed from the system. Dosage
of both Prism Green Retarder and
Inhibitor should be optimised grad-
ually until the design dosage is
reached. Close monitoring of the
transition process is critical. Soluble
polymer levels should be monitored
at least once a day, optimally once a
shift.
Emergency shutdown risk
assessment
During an emergency shutdown,
polymer continues to form in hot
distillation towers. If not acted
upon expeditiously, all existing
inhibitor and ultimately retarder
will be consumed, causing cata-
strophic tower failure as a result of
polymer solidifcation. While a
retarder does provide prolonged
Retarder
injection
Inhibitor
injection
Inhibitor
injection
Lights
SM product
Heavies
Lights
tower
Styrene
tower
Figure 4 Viscosity profle of styrene with differing polymer content
Figure 5 Styrene purifcation for a PO/SM unit
95
105
85
75
65
55
45
0 100 200 300 400
T
e
m
p
e
r
a
t
u
r
e
,

C
Viscosity, cP
35
20% polymer
15% polymer
10% polymer
5% polymer
T
y
p
i
c
a
l

p
u
m
p
i
n
g

l
i
m
i
t
go to eptq.com
click on events
and find
information on
conferences
seminars
workshops
and
exhibitions
throughout
the year
eptq.com
nalco.indd 4 13/12/11 13:12:09
protection due to its lower
reactivity, its protection is fnite,
and it too will be consumed should
the situation not be rectifed swiftly.
Most plants have emergency shut-
down response procedures in place
to mitigate potential problems.
Some common measures include
gravity-fed or pumping of cold
ethylbenzene to dilute and cool the
tower contents, and emergency
generator-powered pumps to
remove the tower contents or to
add extra retarder or inhibitor.
Based on the emergency proce-
dure of the plant, one can estimate
the time required to carry out the
procedure to the point where the
tower is considered safe from poly-
mer build-up. This time can vary
widely from plant to plant due to
different emergency response
mechanisms, specifc column design
and operating conditions.
Ideally, the protection time a poly-
mer control programme (retarder
Table3
and inhibitor) offers should be
greater than the amount of time
required to implement the afore-
mentioned emergency procedure(s).
Thus the critical question is: does
the polymer control programme
offer suffcient tower protection time
in the event of an emergency
shutdown?
To answer this question, Nalco
developed a methodology to help
determine the available protection
time of a polymer control
programme in the event of an emer-
gency shutdown. This tool examines
operating conditions in the distilla-
tion train of a particular styrene
plant, the inhibitor and retarder
dosages, and experimentally deter-
mines the rate of polymer
accumulation in the system.
The available protection time is
defned as the time elapsed after
the emergency shutdown until the
polymer level reaches a critical level
whereby the process stream is too
viscous to pump. To determine at
what polymer level the viscosity
becomes excessively high, a series
of viscosity measurements were
taken using styrene monomer
containing various levels of poly-
mer (see Figure 4). From the graph,
one can see that at above 20% poly-
mer content, a signifcant increase
in viscosity threatens the pump
handling ability of the fuid.
Case study: Repsol Tarragona
Introduction
Repsols PO/SM styrene produc-
tion unit in Tarragona, Spain,
recently completed a feld trial
using Prism Green Retarder and
Inhibitor. Figure 5 shows a simple
unit schematic of the styrene purif-
cation section for the PO/SM unit.
Raw styrene from the reaction
section enters the lights tower of
the purifcation section frst. This
tower is designed to remove ethyl-
benzene as well as water on the
overhead, leaving styrene and other
heavy components in the bottom.
The lights tower feeds the product
tower where styrene is distilled
overhead, leaving heavier
compounds to exit from the tower
bottom.
Prior to the green retarder trial,
the polymer control programme
involved the use of Prism Inhibitor
and DNBP retarder. Both products
were injected into the refux line of
the lights tower. Additionally, an
inhibitor injection was applied to
the refux line of the styrene prod-
uct tower to provide extra polymer
control to that tower.
Goals
The goals of the trial were to replace
toxic DNBP with green retarder,
while maintaining adequate polymer
control both during normal opera-
tion and in the event of an
unexpected emergency shutdown.
Programme design
The dosages of inhibitor and green
retarder were carefully selected to
ensure polymer control while
remaining cost competitive relative
to the existing DNBP-based
programme. A styrene polymerisa-
tion risk assessment (SPRA) study
was carried out to ensure suffcient
6000
10000
11000
12000
9000
8000
7000
5000
4000
3000
2000
1000
0.0 0.5 1.0 1.5 2.0 2.5 3.0
m
p
p

,
r
e
m
y
l
o
p

e
l
b
u
l
o
S
Time, hours
0
Prism GR + inhibitor
Prism GR + inhibitor (repeat}
Current DNBP + inhibitor
Current DNBP + inhibitor
B|ank (repeat}
B|ank
Figure 6 Emergencyshutdownriskassessmentforlightscolumn
Lights column SM column
Normal Shutdown Normal Shutdown
SMconcentrationrelativetoSMconcentrationin
lightscolumnbottomduringnormaloperation 1.00 1.02 0.04 0.37
Temperaturerelativetotemperatureinlights
towercolumnduringnormaloperation 1.00 0.98 1.29 1.10
Note:Conditionscalculatedasrelativetolightstowerbottomnormaloperatingconditionstoprotect
confdentialplantdata
Compared shutdown conditions vs normal operation resulting from
column detailed modelisation
Table 3
nalco.indd 5 9/12/11 12:16:48
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polymerisation protection in the
event of an emergency shutdown.
The risk assessment study took
into account the tower internal
design, actual operating conditions
and chemical dosages. The target
was to model conditions of the
resulting liquid hold-up mixture in
the tower when the emergency
shutdown starts, and rate the
polymerisation severity for each
tower in case of an emergency
shutdown.
Additionally, bottom pumps
design was reviewed to confrm
that they could pump a solution
containing up to 20% polystyrene.
A quick evaluation would suggest
the product tower to be the most
critical unit in case of a shutdown
because it typically operates with
high temperatures in the bottom
and high-purity styrene. But after
applying the SPRA methodology, it
was discovered that the lights tower
was the most critical due to the
combination of styrene concentra-
tion and temperature, resulting in
the liquid mixture accumulated in
the bottom after the shutdown. This
demonstrates the value of applying
a thorough analysis of the system
prior to lab simulations and the
value of the SPRA methodology.
Table 3 shows a comparison
between the normal operating
conditions in the bottom of each
tower compared with a shutdown
estimation by the model. It can be
seen from the data that the lights
tower maintains roughly the same
conditions, while the product tower
bottom, despite increasing styrene
concentration during shutdown,
remains less severe due to the very
low styrene concentration in the
bottom during normal operation.
This lower severity in the product
tower was confrmed later through
laboratory simulation.
The model of the system revealed
the lights tower to be the most
severely affected unit, but the
polymerisation conditions during
the shutdown for that column could
be classifed as mild when
compared to other systems
surveyed. This allowed for a
substantial reduction in the retarder
dosage. The reduced dosage
showed in the industrial test proved
to be enough to ensure stable poly-
mer during process fuctuations
during plant operation.
Repsols operational procedures in
case of emergency shutdown were
studied in detail to understand how
polymerisation could be controlled
by means other than the existing
chemical residuals. Repsols design
and procedures allow a rapid
decrease in polymerisation severity.
A requested polymer control time of
three hours was established as the
requirement for the chemical treat-
ment programme in the simulation.
Figure 6 shows the polymer level
over time for both uninhibited and
inhibited (with proposed dosages
of inhibitor and retarder) situations
for the lights tower. The polymer
level was found to be below 1%
after three hours when inhibited
either with DNBP or green retarder
programmes. This provided conf-
dence that the designed and
industrially tested dosage combina-
tion of inhibitor and retarder offers
adequate protection in the event of
an emergency shutdown based on
their emergency procedures.
The results of the SPRA study can
be summarised as:
Lights tower is the most severe
column, but still this has low sever-
ity when compared to other plants
Green retarder programme
dosages were reduced to a mini-
mum to ensure the required three
hours of polymer control time while
having stable polymer during
normal operation.
Results
When implementing the switch from
DNBP to Prism Green Retarder,
soluble polymer levels were closely
monitored. Polymer levels from the
feed to the lights tower and bottoms
0.6
1.00
0.8
0.4
0.2
1 11 21 31 41 51 61 71 81
d
e
s
i
l
a
m
r
o
n

e
k
a
m

r
e
m
y
l
o
P
Days
0.0
Feed
Styrene tower
Lights tower
DNBP
programme
Prism
Green Retarder
programme
Figure 7 Polymer make levels before and after green retarder implementation
1.00
0.75
0.50
0.25
Retarder only Prism retarder
+ DNBP
Prism inhibitor
+ GR
t
s
o
c

c
i
f
i
c
e
p
s

e
v
i
t
a
l
e
R
0
Over the years Na|co Prism
programme has reduced
po|ymerisation costs by 40 whi|e
phasing out very toxic retarders
Figure 8 Evolution of costs of polymerisation with the Prism programme
nalco.indd 6 9/12/11 12:17:03
of both the lights tower and the
product tower were plotted (see
Figure 7). It is clear that polymer
levels were under control both
before and after the switch. Polymer
generation remained at the same
average level and with the same
variability with process fuctuations.
It is interesting to note that when
the plant was using the old retarder-
only programme polymer generation
was nine times higher than the aver-
age shown in Figure 7.
Figure 8 shows the evolution of
the costs of polymerisation in the
plant over the years with the imple-
mentation of Prism Inhibitor and
Green Retarder. Costs of polymeri-
sation are those costs identifed by
the plant as being related to polymer
control: antipolymerants costs and
the value of lost styrene production
in the form of polystyrene. It can be
seen that DNBP replacement by
green retarder has been achieved at
almost neutral cost, while the
replacement programme has
reduced the cost of polymerisation
by 40% compared with the old
retarder-only programme.
Conclusion
DNBP is a commonly used polymer
retarder in the styrene industry.
However, the high toxicity associ-
ated with DNBP has prompted the
development of a green retarder as
a safer and more environmentally
friendly replacement for DNBP.
Government regulations restricting
the use of DNBP in some countries
have also created demand for a
green retarder, a trend that is
expected to develop worldwide.
Green retarder technology
provides the benefts of low toxicity,
negligible NO
x
and polymer control
performance comparable to DNBP.
Programme effcacy has been vali-
dated through industrial testing.
Lisheng Xu is a Global Industry Development
Manager with Nalco Company in Sugar Land,
Texas, and is responsible for downstream
petrochemicals market development. He has
over 20 years experience in the chemicals and
petrochemicals industry.
Javier Florencio is an Industry Technical
Consultant with Nalco Europe and is
responsible for technical support and new
projects development in the downstream
petrochemicals European market. He has over
10 years experience in the chemicals and
Christopher Morrison is the Research and
Development Manager for Downstream
Petrochemicals with Nalco Company and has
over 10 years experience in the chemicals and
Vincent Lewis is Research Scientist in the
Downstream Petrochemicals Group with Nalco
Company and has 23 years experience in the
chemicals and petrochemicals industry.
Ana Guzmn is a Chemical Engineer with
Repsol Qumica Tarragona and has eight years
combined experience in the chemical and
petrochemical industries.
Carmen Monfort is the Plant Manager for the
PO/SM Plant with Repsol Qumica Tarragona
and has over seven years experience in the
Ana Olivares is the Product Engineer for
Intermediate Products with Repsol Qumica in
Tarragona. She has 14 years experience in the
Adding value to the oil,
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industries?
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ABB Engineering Services
(part of ABB Consulting)
Tel: +44 (0)1925 741111
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rentech.indd 1 8/12/11 22:03:40
Energy recovery with compact
heat exchangers
T
he refnery business is under
constant pressure to increase
effciency. A highly competi-
tive market combined with rising
energy and feedstock costs require
refneries to ramp up production
while cutting operating costs.
Switching from shell-and-tube to
welded plate heat exchangers (also
known as compact heat exchangers)
is a proven and straightforward
way of solving the problem. The
use of compact heat exchangers
offers benefts in four areas:
Energy savings
Less maintenance
Increased production
Lower installation costs.
Energy savings
Up to 50% of a refnerys operating
budget is tied up in energy costs,
making energy effciency a top
priority. Energetics Incorporated
estimates that the petroleum refn-
ing industry in the US could cut
energy use by as much as 54% by
incorporating best practices and
new technology.
3
Recovering and reusing energy is
a proftable and easy way to cut
energy costs. All refneries do this
to some extent, but most still use
outdated shell-and-tube heat
exchangers with low thermal eff-
ciency. Investing in more effcient
heat exchangers is proftable for
energy-intensive plants such as
refneries. Payback periods are often
less than six months.
Cut fuel costs
Heat recovery effciency can be
increased by up to 50% by simply
switching from shell-and-tube to
welded plate heat exchangers. More
Compact heat exchangers are used for heat recovery applications where high
effciency is vital, space or weight constraints apply, or exotic materials are required
MarCos MaTsufugi
Alfa Laval
energy is then put back to use,
energy that would otherwise have
gone to waste. Atmospheric and
vacuum distillation units are typical
units with a high energy consump-
tion and they represent an enormous
potential for better heat integration.
Preheating of crude oil is the
process that requires the largest
amount of energy and where most
gains can be made by using
compact heat exchangers for heat
recovery. There are plenty of other
units in a refnery, such as hydrot-
reating, reforming and FCC, where
switching to compact heat exchang-
ers can be very proftable.
Reduced fuel consumption also
leads to lower emissions of CO
2
,
NO
x
and SO
x
. If the plant operates
under a cap-and-trade system this
will cut operating costs even further.
Effciency up to fve times higher
The heat exchanger is a key compo-
nent in heat recovery. The choice of
heat exchanger is important and
has a direct impact on a companys
bottom line. Figure 1 shows the
heat recovery level as a function of
initial cost in a compact heat
exchanger and a shell-and-tube. The
yield from the compact heat
exchanger is up to 25% higher than
for the shell-and-tube at a compara-
ble cost. Shell-and-tube solutions
with the same level of heat recovery
are often several times more expen-
sive than a compact heat
exchanger.
Turbulence and counter-current fow
The superior thermal effciency of a
compact heat exchanger is a result
of its highly turbulent fow (see
Figure 2). The corrugated heat
exchanger plates cause much higher
turbulence in the fuid than in a
shell-and-tube at the same fow
velocity.
The formula below describes the
overall heat transfer coeffcient.
95
100
90
85
80
75
70
0 1
+25%
2 3 4 5 6
H
e
a
t

r
e
c
o
v
e
r
y
,

%
Cost units
65
Compact heat exchanger
Shell-and-tube heat exchanger
figure 1 Comparison between a shell-and-tube system with stainless steel tubes and
fusion-bonded compact heat exchangers
alfa laval.indd 1 9/12/11 12:30:00
fuid to a temperature that is higher
than the outlet temperature of the
hot fuid). This is especially impor-
tant in heat recovery, since the
maximum amount of energy is
recovered when the cold fuid is
heated to a temperature very close
to that of the hot fuid.
The high effciency means
compact heat exchangers can
exploit temperature differences as
low as 3C. This makes it possible
to recover heat from sources that
have previously been deemed
worthless.
Case study: feed/effuent exchanger
A refnery in the US replaced two
shell-and-tubes with a single
compact heat exchanger as a feed/
effuent exchanger in an isomerisa-
tion plant. The result was a 43%
increase in heat recovery, from 5.8
MW to 8.3 MW. As an added bonus,
the new solution also allowed the
refnery to eliminate a downstream
air cooler (see Table 1).
Case study: overhead condensers
A refnery in Italy replaced old air
coolers on the atmospheric distilla-
tion column with two compact heat
exchangers. The heat that was
previously cooled off into the air is
now recovered and used for
preheating crude oil. The result is
additional heat recovery of 11.5
MW (39.3 MMBtu/h) and an annual
saving in fuel of 2.5 million (see
Table 2).
Proftable energy recovery
Energy-saving investments often
have short payback periods, even at
much lower energy price levels
than todays. In the future, energy
effciency will most likely be a
prerequisite for staying in business.
In its World Energy Outlook 2008
report, the International Energy
Agency (IEA) predicts world energy
demand to increase by 45% over
the next 20 years.
2
It also predicts
that the supply of fossil fuels will
not be able to meet this demand,
even when taking new, undiscov-
ered felds into account.
More and more governments
around the world will probably
start charging industries for emit-
ting CO
2
, with emission credits
High turbulence increases the flm
heat transfer coeffcients (
1
and
2
).
Thin plates (small ) also have a
positive effect on heat transfer. The
result is an overall heat transfer
coeffcient (k) that is three to fve
times higher than for a shell-and-
tube heat exchanger:
1
-
1
+
1
+

k
1

2

k = Overall heat transfer coeffcient,
W/m
2
C
= Film heat transfer coeffcient,
W/m
2
C
= Wall thickness, m
= Wall conductivity, W/mC
Another important feature of
compact heat exchangers is the
capability to operate with a counter-
current fow; hot fuid enters the
heat exchanger at the end where
the cold fuid exits. This makes it
possible to handle crossing-temper-
ature programmes in a single heat
exchanger (that is, to heat the cold
Figure 2 The highly turbulent fow in a
plate heat exchanger results in superior
heat transfer
In
Out
Close
temperature
approach
T2
T1
In
Out
Temperature
cross
Figure 3 The capability to operate with a counter-current fow (hot fuid entering the
heat exchanger at the end where the cold fuid exits) makes it possible to handle
crossing-temperature programmes in a single heat exchanger
Table 1
Original design based Optimised design based
on shell-and-tubes on compact heat exchangers
Number of units 2 1
Heat load 5.8 MW (19.8 MMBtu/h) 8.3 MW (28.3 MMBtu/h)
Additional energy saved 0 2.5 MW (8.5 MMBtu/h)
Additional savings @ $24/MW
and 85% heater effciency 0 580 000 USD/year
Feed/effuent exchanger performance
Additional heat recovery 11.5 MW (39.3 MMBtu/h)
Crude inlet temperature (CIT) increase 12C (53.6F)
CO
2
reductions 29 ktons/year
Savings on fuel consumption 2500 /year
Overhead condenser exchanger performance
Table 2
alfa laval.indd 2 9/12/11 12:30:09
becoming more and more expen-
sive. The result of all this will
undoubtedly be increasing energy
prices; just how much is hard to
predict. In 2007, the IEA predicted
oil prices to stay at $5055 per
barrel until 2030. A year later, in
June 2008, they peaked at $147
dollars.
There are many ways to fght the
energy challenge. Consulting frm
McKinsey made a thorough investi-
gation of future energy needs and
supply, comparing the benefts of
different alternatives. It came to the
following conclusion:
McKinsey has looked long and
hard to obtain an affordable, secure
energy supply while controlling
climate change. Energy effciency
stands out as the single most attrac-
tive and affordable component of
the necessary shift in energy
consumption.
1
Obviously, the frst step towards
lower energy costs is to start using
less energy. Increasing effciency is
the least costly and most easily
implemented solution to the energy
challenge for most refneries.
Less maintenance
One of the key features of a
compact heat exchanger is the
highly turbulent fow. Apart from
improving heat transfer, it also
makes heat exchangers less suscep-
tible to fouling problems.
The high turbulence means foul-
ing deposits are not deposited on
the heat transfer areas. This results
in longer service intervals, more
operating time and more recovered
heat than with a shell-and-tube
design. Less fouling also leads to
lower cleaning costs.
This self-cleaning effect is espe-
cially large in spiral heat exchangers
(SHE). These are compact heat
exchangers with a single channel
design. This design causes fouling
deposits to be fushed away wher-
ever they start to build up. Spiral
heat exchangers are the correct
choice for heavy-fouling duties and
can handle solids, slurries and
fbres. Typical duties for spiral heat
exchangers in refneries are cooling
fuid catalytic cracking (FCC)
bottom products or visbroken
residues.
The smaller heat transfer area
compared to a shell-and-tube heat
exchanger means cleaning will be
both quicker and require fewer
cleaning chemicals. The small heat
transfer area also leads to a smaller
hold-up volume, which means
compact heat exchangers respond
faster to process changes. The
equipment can therefore be shut
down and restarted more quickly
when serviced.
Energy savings
Fouling leads to higher energy
consumption. Heat transfer eff-
ciency drops as fouling builds up,
meaning the boiler or burner has to
provide more heat. Pumping the
fuid through a fouled heat
exchanger also requires more power
to compensate for the increasing
pressure drop. Reduced fouling will
also have a positive effect on energy
bills.
Case study: feed/effuent
exchangers I
One of the largest refneries in the
US had severe fouling problems in
a desalter unit where two shell-and-
tubes were used for cooling the
desalter effuent. The problem was
solved by substituting the two
shell-and-tube exchangers for one
spiral heat exchanger. The higher
thermal effciency meant a heat
transfer area in the new heat
exchanger could be half the size of
the shell-and-tubes.
One of the main problems with
shell-and-tube exchangers was the
fast-increasing pressure drop
caused by fouling. After the spiral
heat exchanger was installed, the
pressure drop was stable and ther-
mal performance was much better
over time.
The old shell-and-tubes had to be
cleaned every month. The new
spiral heat exchanger was cleaned
Figure 4 The self-cleaning design of spiral heat exchangers is appropriate for fouling duties
120
100
80
60
40
20
0 2 4 6 8 10 12
H
e
a
t

t
r
a
n
s
f
e
r

c
o
e
f
f
i
c
i
e
n
t

c
o
m
p
a
r
e
d

t
o

d
e
s
i
g
n

v
a
l
u
e
,

%
Months in operation
0
Shell-and-tube cleaned 12 times a year
Spiral heat exchanger
Shell-and-tube cleaned twice a year
Figure 5 Comparison of heat transfer effciency for a spiral heat exchanger (blue) and a
shell-and-tube heat exchanger in an oil refnery visbreaker cooler
alfa laval.indd 3 12/12/11 13:37:04
heat exchangers than for shell-and-
tube exchangers. This is because
the costs for the heat exchanger and
installation are often lower, and
because the utility systems can be
used more effciently.
Lower costs for the heat exchanger
Since the required heat transfer area
is three-to-fve times smaller for a
compact heat exchanger than for a
corresponding shell-and-tube
design, much less material is
needed to build the unit. This has a
positive effect on price, especially
when tough conditions call for
exotic materials such as high-alloy
steel or titanium.
Case study: atmospheric distillation
unit I
Petrobras compared the costs for
shell-and-tubes and compact heat
exchangers. Heat exchangers were
to be used in an atmospheric distil-
lation unit, to preheat crude using
heat recovered from kerosene and
HVGO streams. The comparison
showed that the costs for shell-and-
tube exchangers were 3.8 and 5.6
times higher for the respective
positions.
Lower installation costs
Installation costs can be cut consid-
erably by using welded plate heat
exchangers instead of shell-and-
tube exchangers when expanding
plant capacity. The foundations can
be made smaller and the heat
exchangers are easier to ft into
existing structures thanks to their
compact nature and lighter weight.
When estimating the total
installed cost, a factor of 3.03.5
times the cost of the heat exchang-
ers is often used for shell-and-tubes,
compared to less than two for
compact heat exchangers.
Case study: atmospheric distillation
unit II
A refnery in Asia analysed differ-
ent options for heat recovery on the
atmospheric distillation column.
Special alloys had to be used in the
heat exchangers due to the aggres-
sive media. Since the shell-and-tube
solution would require a larger heat
transfer area, the cost became 2.3
times higher than for a compact
for the frst time after 14 months.
No heavy fouling was observed,
only a thin layer of grease on the
effuent side and minor scaling on
the feed-water side (see Table 3).
The compact nature of the spiral
heat exchanger means it is easier to
perform maintenance.
Increased production
Many refneries have bottlenecks
related to heating or cooling. It is
often impossible or very costly to
increase heating or cooling capac-
ity, meaning they are left
unresolved.
Investing in more effcient heat
exchangers is often the best way to
overcome these limitations. The
higher the effciency of the heat
exchanger, the more heat can fow
through it. This means the process
fuid is heated or cooled with the
extra degrees needed to resolve the
bottleneck, simply by raising heat
exchanger effciency. The result is
higher production capacity at a low
investment cost.
Compact heat exchangers resolve
bottlenecks without adding any
additional investment or operating
costs for more heating.
More performance per square metre
Thanks to the smaller heat transfer
area required, compact heat
exchangers offer signifcantly higher
capacity per square metre of foor
space than shell-and-tube exchang-
ers offer. As restrictions in space
and building structures often apply,
switching to compact heat exchang-
ers is a straightforward way to
boost production without having to
rebuild the plant. Using the same
support structures, you get the
required capacity boost simply by
substituting the old equipment with
new.
More uptime
Compact heat exchangers require
less downtime for maintenance
than do shell-and-tube exchangers,
since service intervals are longer
and the cleaning process is faster.
Increased uptime also leads to
higher production output over time.
In the desalter example above,
shell-and-tubes had to be cleaned
12 times per year and the compact
heat exchanger less than once a
year. The increase in uptime is
substantial and leads to higher
production output.
Case study: feed/effuent
exchangers II
To improve overall performance in
its semi-regenerative catalytic
reforming process, a refnery in
France replaced 12 shell-and-tube
feed/effuent heat exchangers with
a single, large-scale compact heat
exchanger. This resulted in a 33%
increase in capacity and reduced
pressure drop from 4 to 1.5 bar.
Improved heat recovery also led to
lower energy consumption by 5.6
MW (19.1 MMBtu/h) and lower
emissions for the fred heater. The
payback time was 12 months.
Lower investment costs
Total investment costs are usually
signifcantly lower for compact
Unit Cleaning frequency Cost per cleaning, Total cleaning costs
(per year) USD per year, USD
Shell-and-tubes(2) 12 6000 72000
Spiralheatexchanger(1) <1 3250 <3250
Feed/effuent exchanger performance
Table 3
Number of units Heat transfer area, m
2
Material Installed cost
Shell-and-tubes 8 5800 12Cr/CS 2.3X
Compactheatexchangers 2 1350 316L X
ADU exchanger performance
Table 4
alfa laval.indd 4 9/12/11 12:30:28
heat exchanger setup (see Table 4).
A shell-and-tube installation
(including space for extracting the
tubes) would also occupy a 20 times
larger volume on-site, 840 m
3
(12 x
14 x 5 m) compared to 37.8 m
3
(1.8
x 6 x 3.5 m).
Lower costs for utility systems
Before investing in new utility
systems such as cooling towers and
boilers, it is wise to see if the same
result can be achieved by increasing
heat recovery. Recovering more
energy in the process often leads to
reduced heating and cooling needs.
Switching to compact heat exchang-
ers often means production can be
increased while still using the same
utility systems.
Reliability
Compact heat exchangers offer the
best of two worlds and combine the
benets of traditional plate heat
exchangers with those of shell-and-
tube exchangers. The all-welded
design ensures trouble-free perform-
ance that does not change over time.
Many of the compact heat exchang-
reboilers) and where exotic materi-
als are required due to corrosion
(desalter water, naphtha toppings,
sour water, amines and alkylation).
The self-cleaning effect in spiral
heat exchangers also makes them
very suitable for heavy fouling
applications (cooling FCC bottoms
or visbroken residues).
References
1 Creyts J, et al, US energy savings:
Opportunities and challenges, McKinsey
Quarterly, Jan 2010.
2 International Energy Agency, World Energy
Outlook 2008, www.worldenergyoutlook.org/
2008.asp.
3 EDF Environmental Defense Fund, Think
US industries cant be more competitive? Think
again, 2010, http://apps.edf.org/documents/
11209_LCMI-Reneries.pdf.
Marcos Matsufugi is a Market Manager at Alfa
Laval, responsible for business and application
development for reneries. He has over 14
years experience in the rening market,
including eight years with Alfa Laval, and holds
a bachelors degree in chemistry from the
University of So Paulo, Brazil.
Table 3
ers that are in use in reneries have
been operating for decades and are
still delivering top results.
Apart from reliable sturdiness,
compact heat exchangers bring you
high efciency, compact size, mini-
mum maintenance, low pressure
drop and the ability to operate at
high pressures and temperatures.
They can be used in many positions
in a renery. The installations are
often for heat recovery applications,
where high efciency is essential
(crude preheating, feed/efuent
heat recovery and boiler feed water
preheating). Compact heat exchang-
ers are often being used where
space or weight constraints
apply (overhead condensers and
Compact heat
exchangers bring
high efciency
and minimum
maintenance
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nalco.indd 1 13/9/11 09:58:29
Low rare earth catalysts for FCC
operations
F
or decades, rare earth elements
have performed vital roles in
refnery catalysis and their
availability, at reasonable prices,
has been taken for granted.
However, when the global supply
became restricted, refners faced
spiralling costs and were forced to
re-examine how they used rare
earth elements.
Uses of rare earth elements
The rare earth elements are lantha-
num, cerium, praseodymium,
neodymium, promethium, samar-
ium, europium, gadolinium,
terbium, dysprosium, holmium,
erbium, thulium, ytterbium and
lutetium. Yttrium and sometimes
scandium are often grouped as rare
earth elements because of their
similar chemical properties.
1

These elements have a wide range
of industrial applications. They
have taken an important role in oil
refning catalysts, additives and
processes for many years, and also
make vital contributions to other
applications. Selected end uses for
rare earths are shown in Table 1.
Global demand for rare earth
elements is currently about 134 000
t/y, but worldwide annual produc-
tion amounts to 124 000 tonnes, the
Features including high zeolite and matrix stability and high accessibility
architecture characterise a family of low rare earth FCC catalysts
Yen YUng and Ken BrUno
Albemarle Corporation
difference being drawn from previ-
ously mined stocks.
However, the availability of rare
earths can no longer be taken for
granted. In 2009, China, the largest
producer of rare earth elements,
output 97% of the worlds rare
earths measured in terms of oxide
content. However, the country cut
its export of rare earths from about
50 000 tonnes in 2009 to 30 000
tonnes in 2010. The country also
plans to reduce output further by
eliminating prohibited rare earth
mining operations. This is likely to
restrict the availability of rare earth
elements even more. Greater empha-
sis by the Chinese authorities on the
safety and environmental aspects of
mining operations are likely to
increase operating costs. The much-
reduced availability of rare earths
means that their price has soared.
The price for lanthanum, for
example, surged from some $6000/t
in May 2010 to about $140 000/t in
May 2011.
There are limited sources of rare
earth elements outside China, but
the quantities currently produced
are too low to have any signifcant
impact on short-term supply.
Initiatives are being taken in, for
example, Australia, Brazil, Canada,
South Africa, Greenland and the
US, to fnd and develop new
sources of rare earths or to reopen
mines previously considered uneco-
nomic. But, as demand is projected
to increase from 134 000 t/y to
180 000 t/y in 2012, it is unlikely
that any new rare earth production
will close the widening gap in the
short term, as greenfeld mining
projects could take 10 years to reach
production.
2

rare earth elements in FCC
catalysts
Rare earths have found applications
in oil refning for FCC catalysts and
additives, which use lanthanum
and cerium. Lanthanum and cerium
are used in FCC catalysts because
they substantially increase the
activity and stability of the zeolite,
which is the most active component
in the catalysts. Lanthanum is most
Light rare earth element Major end use Heavy rare earth element Major end use
Lanthanum Hybridengines,metalalloys,refningcatalysts Terbium Phosphors,permanentmagnets
Cerium Automotivecatalysts,refningcatalysts,metalalloys Dysprosium Permanentmagnets,hybridengines
Praseodymium Magnets Erbium Phosphors
Neodymium Automotivecatalysts,harddrivesinlaptops,headphones,hybridengines Holmium Glasscolouring,lasers
Samarium Magnets Thulium MedicalX-rayunits
Europium Redcolourationfortelevisionandcomputerscreens Ytterbium Lasers,steelalloys
Gadolinium Magnets
Selected uses of rare earth elements
Table 1 Adapted from: DOI, US Geological Survey, Circular 930-N
The much-reduced
availability of rare
earths means that
their price has soared
albemarle.indd 1 13/12/11 13:13:42
butylenes. Vacuum gas oils and
residue are the main oil streams fed
to the FCC unit. These are charac-
terised by heavy molecules with
large average diameters. Residue
feedstocks have the largest diameter
molecules and are rich in contami-
nants such as nitrogen, sulphur, V,
Ni, sodium, calcium and iron,
which attack the active sites of the
catalyst or restrict the diffusion of
feed molecules into or valuable
products out of the structure of the
catalyst particles. Bottoms conver-
sion and product selectivity then
become poor and negatively affect
refnery margins.
4
For this reason, Albemarle has
championed the development and
application of stable, advanced
catalyst technologies and architec-
tures to maximise the diffusion of
feed molecules into these active
sites and of the desired products
out of the active sites to maximise
product upgrading.
5

The technologies can be divided
into: matrix components, which are
essential for pre-cracking of the
large feed molecules; zeolites,
which provide the high cracking
activity needed for further cracking
of the intermediate molecules to
valuable gas oil, gasoline and LPG;
and binders to ensure high struc-
tural integrity for the catalyst
particles. If necessary, speciality
components are used for function-
alities such as enhanced resistance
to poisons like metals. All these
components are integrated into a
structure featuring high accessibil-
ity to ensure optimal diffusion of
the large feed and intermediate
molecules to the active sites and of
the valuable products out of these
active sites to achieve maximum
upgrading and minimise down-
grading to less valuable products
such as gas and coke (see Figure 1).
In addition, high levels of zeolite
and active matrices can be incorpo-
rated into the catalyst.
High-stability zeolites
The company has developed a
range of high-stability zeolites,
defned as Albemarle Developed
Zeolites (ADZ), to cover applica-
tions required by the oil refning
industry. The companys full range
commonly used to increase the
activity and stability of zeolites.
3

The effects of lanthanum on the
performance of a zeolite-containing
FCC catalyst are shown in Table 2.
This data was obtained from labo-
ratory work in which two catalysts
were compared in the short-contact-
time riser test (SCT-RT) after a two-
step cyclic metal deactivation with
5000 ppm of nickel (Ni), 5000 ppm
of vanadium (V) and a residue
feedstock. The catalysts have the
same composition, but the frst one
has not been exchanged with rare
earth and the second one contains
1 wt% RE
2
O
3
. (These zeolites have
not undergone ADZT-200 stabilisa-
tion technology, which is discussed
later in this article.)
This comparison at a constant
catalyst-to-oil ratio (C/O) shows
the typical changes through apply-
ing rare earth exchange to zeolites:
The activity is substantially
increased, which results in much
higher liquefed petroleum gas
(LPG) and, particularly, gasoline
yield, mainly at the cost of bottoms
The olefnicity of the LPG fraction
is decreased
Owing to the lower olefnicity,
gasoline olefnicity and octanes will
also decrease
Coke and delta coke are
increased.
No other elements have yet been
found to increase zeolite activity
and stability as effciently and cost-
effectively as lanthanum and
cerium.
Albemarles FCC catalysts
Main features
FCC provides value to the oil
refner by its ability to convert a
wide range of marginal feedstocks
into transportation fuels and LPG,
especially gasoline, propylene and
Catalyst No rare earth Rare earth exchanged
RE
2
O
3
, wt% 0.0 1.0
Conversion at C/O = 4 wt/wt, wt% Base +6.9
Yield structure, wt%
Dry gas Base +0.90
Propane Base +0.19
Propylene Base +0.44
n-butane Base +0.15
i-butane Base +0.66
Butylenes Base +0.28
Gasoline Base +4.8
Light cycle oil Base -1.1
Bottoms Base -5.8
Coke Base +0.9
Selectivities, wt/wt
C
3
-olefnicity Base -0.02
C
4
-olefnicity Base -0.08
Gasoline/conversion Base +0.01
Coke/second order conversion Base -0.40
Laboratory comparison of two catalysts with the same formulation but with and
without rare earth exchange
Table 2
Speciality
components
Matrices
Zeolites
Binders
Highest accessibility
Tailored physical properties
Ultimate performance
Figure 1 Tailored FCC components and
high accessibility technologies are applied
to obtain catalysts with premium
performance
albemarle.indd 2 9/12/11 12:39:39
of zeolites covers low hydrogen
transfer applications, which are
required for maximisation of gaso-
line octanes, and/or producing
high quantities of light olefns,
particularly propylene and buty-
lenes (see Figure 2). ADZs are also
available for the high hydrogen
transfer activity that is required to
maximise catalyst activity and/or
to maximise gasoline volume at low
gasoline olefnicity.
Zeolites were introduced in the
early 1960s and resulted in a step
change in FCC, as catalysts contain-
ing zeolites are far more active and
more selective for producing gaso-
line and LPG, and feature superior
thermal and hydrothermal stability
compared with amorphous cata-
lysts. It is well known that cracking
selectivity is catalysed by Brnsted
acid sites, which can donate a
hydrogen cation, or by Lewis acid
sites, which can accept a lone pair
of electrons.
6
Zeolite Y is the main
zeolite widely applied for the crack-
ing of large hydrocarbon molecules,
as its high silica-to-alumina ratio
(SAR) results in increased activity
and (hydro)thermal stability.
Brnsted acid sites are introduced
into these zeolites by exchanging
sodium with a combination of
metals and ammonia. Traditionally,
the metals most commonly used are
rare earth metals, as they substan-
tially increase catalyst activity and
gasoline selectivity,
3
and because
they used to be very cost-effective.
The introduction of high-activity
and (rare earth) metal-exchanged
zeolites enabled the introduction of
short-contact-time plug-fow riser
FCC and residue FCC unit designs.
4

Low rare earth technology (LRT),
which Albemarle used in early
applications of zeolites for FCC, is
addressed later. This discussion
elaborates on the other important
features of premium catalysts,
which excel in activity and stability
demanded in times of soaring
rare earth prices.
ADZs are characterised by the
following common features:
7
High SAR: a zeolites SAR is a
measure of its acid strength and
density. The higher the SAR, the
lower the site density and the
higher the zeolites strength. The
higher SAR zeolites are hydrother-
mally more stable and produce
high-octane gasoline
Control of the amount of zeolite
non-framework alumina to provide
tailored cracking activity while
minimising the formation of gas
and coke associated with excessive
non-framework alumina on the
zeolite surface.
The high SAR of an ADZ provides
the additional beneft of higher cata-
lyst stability compared with zeolites
featuring lower SAR (see Figure 3).
Thanks to this higher stability, a
higher activity can be obtained with
the same amount of zeolite; alterna-
tively, less rare earth is required for
the same activity at constant zeolite
intake when compared with a lower-
SAR zeolite.
The pore size of the zeolite Y cage
structure, where most cracking
reactions occur, is about 0.74 nm
and, therefore, the zeolite will not
admit hydrocarbon molecules with
boiling points above 480C, as these
molecules have kinetic diameters
well above 1 nm. Consequently,
intermediate molecules have to be
generated in a larger pore system
and on the zeolites surface.
Speciality alumina for bottoms
cracking and Ni and V passivation
Staged cracking is required to
maximise bottoms conversion (see
Figure 4). Albemarle has developed
and applies several special matrices
to selectively crack the large hydro-
carbon molecules. These special
matrices are called Albemarle
Developed Matrices (ADM) and
form a perfect combination with
ADZs. The best known is ADM-60
because of its ability to passivate
the deleterious effect of Ni by
strongly reducing its dehydrogena-
tion ability, which reduces coke and
gas make. The most powerful
bottoms conversion comes from
applying the high-activity ADM-20.
ADMs can be combined to obtain
synergistic effects that maximise
bottoms conversion at minimum
gas and coke make.
8

In addition, separate metal traps
can be incorporated to further
enhance V tolerance for maximum
processing of residue feedstocks, as
is applied in Coral SMR.
9
These
metal traps are not based on rare
earth elements and therefore the
costs of these catalysts are unaf-
fected by increases in rare earth
prices. The development of new
ADMs continues. Recently,
Low
Low High
O
c
t
a
n
e
O
l
e
f
i
n
s
Hydrogen transfer
High
T
r
a
d
i
t
i
o
n
a
l

r
a
n
g
e

o
f

z
e
o
l
i
t
e
s
A
l
b
e
r
m
a
r
l
e

r
a
n
g
e

o
f

z
e
o
l
i
t
e
s
Figure 2 A wide range of ADZs for all applications
1.1
1.2
1.0
0.9
Low SAR High SAR
S
u
r
f
a
c
e

a
r
e
a

r
e
t
e
n
t
i
o
n
,

s
t
a
b
i
l
i
t
y
0.8
Figure 3 Albemarles ADZ with a higher
SAR features a larger surface area
retention for higher stability and activity
albemarle.indd 3 9/12/11 12:39:54
barrier formation and consequently
diminish the mass transfer charac-
ter of the catalyst.
13
The catalyst
accessibility (the mass transfer char-
acter) may then drop below a
minimum acceptable value. A fast
and reliable method that positively
identies an emerging contamina-
tion problem with an equilibrium
catalyst (E-cat) is the Albemarle
Accessibility Index (AAI) test.
14
Data from the commercial opera-
tion of a residue FCC unit conrm
that potential losses in conversion,
gasoline yield and bottoms conver-
sion can be predicted by monitoring
the AAI of the unit E-cat inventory
(see Figure 6). In addition, a
detailed analysis of Albemarles E-
cat database conrms that the drop
in conversion, gasoline yield and
bottoms conversion (higher slurry
yield) can be correlated with a too-
low AAI.
15
The yield structure will
deteriorate rapidly once the AAI
drops below a critical value. This is
indicated by the dotted lines in
Figure 6, in which the dotted verti-
cal line denotes the critical AAI.
This critical AAI depends on the
units design and type of feedstock.
The delta values shown on the y-
axis in Figure 6 are the difference
between the observed value and the
value calculated by an FCC unit
model (for instance, Catop) that
corrects for all conditions (process,
feed and catalyst) except AAI.
When the AAI is above the critical
value, the yield difference will
nominally stay at about zero or
improve slightly. The signicant
negative deviation at values below
the critical AAI is caused by the
diffusional constraints limiting the
conversion of heavy molecules to
lighter products.
Albemarle has developed FCC
catalysts with high accessibility, as
accessibility makes better utilisation
of the active ingredients, especially
the (small-pore) zeolites, possible.
Figure 7 shows that high-accessibil-
ity catalysts offer more hydrocarbon
molecules for cracking to the zeolites
at all contact times. Hence, high
accessibility permits higher cracking
activity, especially in modern short-
contact-time cracking. The estimates
shown in Figure 7 have been made
using a model that relates the
ADM-25 was introduced for ne-
tuning the catalyst active sites by
creating a new type of silico-alumi-
nate interaction. ADM-25, along
with the new manufacturing tech-
nology Onyx, is being used in the
GO-Ultra FCC catalyst line.
10

Albemarle expects to expand its
ADM portfolio soon with a new
matrix component technology.
The companys compounding
technology enables the use of a
large quantity of active ADM for
high activity. Consequently, less
rare earth is required on the cata-
lyst for the same activity (see Figure
5).
Maximum diffusion to acid sites and
resistance to contaminant poisoning
Accessibility in FCC catalysts
became an issue when the amount
of residue feedstock being proc-
essed increased signicantly. The
molecules in this type of feedstock
have a boiling range above 570C
and a molecule size of 12.5 nm.
11
These molecules cannot easily enter
the zeolite structure, which has a
pore size of only 0.74 nm.
Conversion is maximised by offer-
ing a high accessibility to enable the
feed molecules to reach the active
sites quickly. These molecules are
cracked by the ADM to smaller
molecules for subsequent cracking
by the zeolite.
Catalyst accessibility also became
an issue when FCC units were
modied to have shorter contact
times, as this requires a higher
activity catalyst. Since higher acces-
sibility enables the feed molecules
to get to the catalyst active sites
quicker, (bottoms) conversion is
much better when using a high-
accessibility catalyst.
12
The signicance of high accessi-
bility was proved when, through
advances in unit design, operating
strategies and catalyst technologies,
a signicant increase in the amount
of refractory residue feedstocks
going to the FCC unit was realised.
Consequently, the incidence of iron,
and often calcium and nitrogen,
poisoning in residue FCC units
became more frequent. Contaminant
iron causes densication of the
surface of the catalyst and, along
with calcium, forms a barrier that
restricts the diffusion of large
hydrocarbon molecules to the active
sites of the catalyst, thereby reduc-
ing the rate of conversion in the
riser. This increase in refractory
residue feedstocks also brought
even higher levels of Ni, V and
sodium, which also contribute to
80
RE203 =
2.0 wt
RE203 =
0.5 wt
70
60
High zeo|ite
(other supp|iers}
High matrix
(A|bermar|e}
%
t
w

,
y
t
i
v
i
t
c
A
Catalyst type
50
Figure 5 Albemarle uses high matrix
levels catalyst, resulting in high activity
at low rare earth levels
Figure 4 The staged cracking model
Binder
Zeolite
Heavy oil
Gasoline
Pre-cracking of heavy molecules
by matrix
High accessibility structure
High pore volume and high
cracking activity

!LLOWSLARGEHEAVYFEEDMOLECULES
ACCESSTOTHEACTIVESITES
!LLOWSPRODUCTSTOLEAVEWITHOUT
UNDERGOINGSECONDARYREACTIONS
Matrix
FCC catalyst model
albemarle.indd 4 9/12/11 12:40:12
The proftability formula
When oil refneries need to prioritize increased production and lower operating
costs, the easy way to higher effciency is to switch from shell-and-tubes to
compact heat exchangers. This often results in major cuts in operating and
capital costs, and higher production capacity.
Compact heat exchangers offer benefts for refneries in four areas. When adding
these up, the secret to staying ahead of the competition becomes obvious.
We call this the proftability formula.
For more information, visit www.alfalaval.com/refnery
P
P
I
0
0
4
5
8
E
N

1
1
0
8
www.alfalaval.com/refnery
www.ptqenquiry.com
alfa laval.indd 1 13/9/11 11:00:20
average size of the feed molecules to
the calculated E-cat AAI.
The toxic effect of nitrogen
poisoning, which neutralises the
catalysts acidic sites, appears when
processing opportunity feedstocks
such as coker gas oil, shale oil, tar
sands and direct coal liquids.
16
Higher accessibility also offers
improved resistance to this type of
poisoning. Another important
aspect is that a higher AAI enables
higher activity to be obtained when
using, for example, less zeolite or
less rare earth for zeolite stabilisa-
tion. AAI is therefore an important
tool in producing low rare earth
technology catalysts.
Low rare earth catalysts
Soaring rare earth prices are forcing
refners operating FCC units to look
for alternative catalysts to reduce
their costs. Particularly in applica-
tions requiring maximum octanes,
Albemarle has applied low rare
earth ADZs. Previous-generation
low rare earth catalysts, such as
Octaboost and Octavision, were
developed for refners aiming to
raise octane and the production of
isobutylene as a feedstock for
alkylation.
17
With the introduction
of ZSM-5 additives for cracking
olefns precursors to propylene and
butylenes and increasing gasoline
octane, there was less need to use
lower levels of rare earth zeolites,
as a combination of ZSM-5 addi-
tives and higher rare earth zeolites
appeared to be an economical solu-
tion for many applications.
Therefore, the industry trend was
to raise the level of rare earth in
FCC catalysts and complement it
with ZSM-5 if needed.
Although the benefcial effects of
rare earths, especially lanthanum,
on FCC catalyst activity, stability
and tolerance to V poisoning are
recognised, the company has
continued to reduce the amount of
rare earth in FCC catalysts and
additives. The use of the rare earth-
free SO
x
-reducing additive
SO
x
Master;
18
the application of rare
earth-free metal traps in, for exam-
ple, Coral SMR and Upgrader; and
the application of AFX,
19
which can
have very low rare earth zeolites,
refect efforts in the feld of the
cost-effective use of rare earth
elements in FCC catalysts and
additives.
ADZT-200 for higher activity
The benefcial effect of rare earth on
catalyst activity is shown in Figure
8. The data in this fgure is for a
vacuum gas oil feed with FCC cata-
lysts having the same composition
but varying rare earth content on
zeolite that have been deactivated
after a metal pore volume impreg-
nation (1000 ppm Ni, 1000 ppm V)
and steaming for 20 hours at 788C.
It can be seen that the highest
gain in activity is obtained with the
frst 0.7 wt% of rare earth oxide
content and that the effect dimin-
ishes at an elevated level. Compared
with a rare earth-free FCC catalyst,
the 3.0 wt% rare earth oxide FCC
catalyst has signifcantly higher
activity at approximately 10 wt%.
0
2
-2
-4
-6
-8
1 3 5 7
%
|
o
v

,
n
o
i
s
r
e
v
n
o
c

a
t
l
e
D
AAI
-10
0
2
-2
-4
-6
-8
1 3 5 7
%
|
o
v

,
e
n
i
l
o
s
a
g

a
t
l
e
D
AAI
-10
0
-2
2
4
6
8
1 3 5 7
%
l
o
v

,
y
r
r
u
l
s

a
t
l
e
D
AAI
10
Figure 6 Signifcant losses in conversion, gasoline yield and bottoms conversion once
AAI decreases below a critical value (denoted by the solid vertical lines) are shown for a
commercial unit
albemarle.indd 5 9/12/11 12:40:23
The company has developed
several zeolite stabilisation methods
for use in lieu of or complementary
to zeolite rare earth exchange. The
company has found that ADZT-200
(Albemarle Developed Zeolite
Technology) stabilisation technol-
ogy is most effective. During
application of ADZT-200, the zeolite
undergoes a treatment that is used
to complement rare earth exchange
and that is most effective when a
low to modest rare earth exchange
is applied (see Figure 9).
The benefts of ADZT-200 are
confrmed in commercial operation
(see Table 3). In this comparison,
ADZT-200 was applied to an
Albemarle catalyst. For the same
catalyst addition rate, ADZT-200
can provide substantially higher
conversion, gasoline octane and
gasoline volume under the same
main operating conditions. The
Albemarle catalyst features lower
rare earth content than the competi-
tors catalyst.
Using the catalyst technology
described, the company has intro-
duced its LRT FCC catalyst line:
ADZT-200 A zeolite enhancement
treatment to maximise the zeolite
activity and reduce the need for
rare earth
High zeolite intake The catalyst
technologies permit the use of high
zeolite content for increased
activity
High SAR Y-zeolites Result in high
zeolite stability and require less
rare earth
Highest amount of selective
alumina Enables the inclusion of a
high amount of selective matrix.
High catalyst activity and perform-
ance are obtained with less rare
earth
Highest AAI High accessibility
60
100
90
80
70
50
40
30
20
10
Zero Short Medium Long

,

e

s
e
e
i
n
g

r
e
a
c
t
a
n
t
s
t
i
l
o
e
z

f
o

n
o
i
t
r
o
p
o
r
P
Zeolite-hydrocarbon relative-contact time

0
Low accessibi|ity
High accessibi|ity
Figure 7 Higher accessibility offers more molecules the opportunity to undergo selective
zeolite cracking and, hence, effectively increases activity
12
10
8
6
4
2
0 1 2 3 4 5
D
e
l
t
a

a
c
t
i
v
i
t
y
,

w
t
%
RE203 on catalyst, wt%
0
First 0.5-0.7% rare
earth oxide is optimal
Figure 8 The effect of rare earth on catalyst activity
12
10
8
6
4
2
0 1 2 3 4 5
D
e
l
t
a

a
c
t
i
v
i
t
y
,

w
t
%
RE203 on catalyst, wt%
0
2% activity increase
with ADZT-200
ADZT-200 zeolite
Standard zeolite
Figure 9 ADZT-200 enhances the catalytic activity of zeolites with low to modest rare
earth exchange

Competitor Albemarle
Catalyst data
Activity, wt% Base Base+3
RE
2
O
3
, wt% 2.6 1.3
Catalyst addition
rate, t/D Base Base
E-cat Ni+V, ppm Base Base
FCC unit data
Conversion, lv% 80.1 83.5
C
2
-, wt% 4.0 3.2
LPG, wt% 18.0 20.0
Gasoline, wt% 47.9 50.7
Light cycle oil, wt% 12.3 11.9
Slurry, wt% 9.5 6.2
Coke, wt% 8.3 8.0
Gasoline MON 81.2 81.5
Commercial comparison of an
Albemarle FCC catalyst featuring
ADZT-200 technology against a
competitor catalyst
Table 3
albemarle.indd 6 9/12/11 12:40:37
optimally utilises the zeolite and
matrix in the catalyst to provide
maximum activity for a given rare
earth
Optional metal trapping function-
ality Employing metal-tolerant and
trapping technologies enhances a
catalysts performance and activity,
in particular, for rare earth-free
metal-resistant technologies
Optimised proprietary manufactur-
ing technologies Enable maximum
effectiveness and fexibility.
The LRT line complements the
current range (see Table 4).
Commercial experience with
LRT catalysts
Commercial experience in FCC units
confrms the benefts of the LRT line
of catalysts in residue and vacuum
gas oil feedstock applications.
The frst application (see Table 5)
is processing 15% vacuum tower
bottoms. The unit performance was
suboptimal owing to poor bottoms
conversion and far too low an AAI.
The decision was taken to switch to
an Upgrader LRT residue catalyst
featuring a much higher AAI, a
higher matrix surface area and a
lower rare earth content (0.85 wt%
compared with 2.3 wt%). Dry gas
production and bottoms yield were
lower and gasoline production was
higher. In addition, the much
higher AAI, which was well above
the critical AAI, provided the fexi-
bility to process even more residue
feedstock. The economic benefts,
based on only the improved yields,
were calculated to be more than $20
million/y.
In a different application, the
catalysts rare earth content was
maintained at 2.2 wt% but the AAI
and the matrix activity signifcantly
increased. The E-cat AAI increased
by three points, while the matrix
surface area increased by 30 m
2
/g.
For the same feed and main operat-
ing conditions, the catalyst addition
rate was reduced from 5.4 t/d to 4.7
t/d, the gasoline yield increased by
1.5 vol%, and the slurry yield
decreased by 0.8 vol% (see Table 6).
Despite the lower catalyst addition
rate, the activity of the circulating
catalyst inventory increased by
3 wt%, which confrms higher
activity by using high accessibility
combined with high matrix activity.
Two more applications, one with
residue feedstock, the other with
gas oil feedstock, are shown in
Table 7. In both these applications,
LRT catalysts have been used for
more than fve years to deliver
premium performance shown by
the low yield of slurry oil. In the
gas oil application, maximisation of
gasoline yield is required, whereas
high light cycle oil yield is targeted
in the residue application. The cata-
lysts rare earth level is less than 0.6
wt% in both cases.
Conclusions
Rare earth elements have been of
great importance to oil refners for
processing marginal feedstocks in
the FCC unit, which is still the
preferred unit for converting
marginal feedstocks into LPG and
transportation fuels. However, soar-
ing rare earth prices have created
turmoil for the refning industry.
Albemarles LRT FCC catalyst line
is based on proprietary ADZT-200
zeolite treatment and higher SAR for
high activity and enhanced zeolite
stability. In addition, technological
advances, including high zeolite and
matrix intake and high accessibility
architecture, are applied in LRT
products. Moreover, the opportunity
to further increase FCC unit profta-
bility by processing more low-cost
residue feedstock is available when
employing LRT catalysts. Overall
rare earth use is lower and better
performance is obtained.
GO LRT and Amber LRT for gas
oil operations, and Coral LRT
and Upgrader LRT for residue
Segment Gasoline/conversion Olefns/octane LCO
Lowest coke Maximum bottoms Maximum C
4
=/octane
cracking C
3
=
VGO Go-Ultra Amber AFX Action AmberMD
GoLRT AmberLRT
Residue Coral Upgrader AFX Action UpgraderMD
CoralSMR UpgraderR+
CoralLRT UpgraderLRT
Novel and proven Albemarle LRT FCC catalysts
Table 4
Competitors catalyst Upgrader LRT
Operating conditions
Feedrate,B/D Base Base+3000
FeedAPI 27.4 25.8
FeedConradsoncarbonresidue,wt% 1.0 1.0
Vacuumtowerbottoms,% 14 17
Preheattemperature,C 245 238
Riseroutlettemperature,C 529 529
Regeneratorbedtemperature,C 723 717
E-cat properties
Activity,wt% 65 65
RE
2
O
3
,wt% 2.3 0.85
Catalystadditionrate Base Base
Matrixsurfacearea,m
2
/g 37 83
AAI 2 7
FCC unit yields
C
2
minus,scf/B 406 330
LPG,vol% 20.8 19.6
C
3
=/totalC
3
0.75 0.76
C
4
=/totalC
4
0.56 0.64
Gasoline,vol% 52.9 62.5
Slurry,vol% 19.4 20.9
SlurryAPI 12.9 4.2
Conversion,vol% 64.2 70.9
Proftability Base Base+>$20million/y
Upgrader LRT gave improved performance in a residue feedstock application at
substantially lower rare earth content than the previous catalyst
Table 5
albemarle.indd 7 9/12/11 12:40:51
feedstocks, are FCC catalysts for
maximising FCC unit proftability
under current rare earth market
conditions. LRT products have
demonstrated improved activity
and increased bottoms conversion
to transportation fuels at lower rare
earth levels.
ACTION, AFX, AMBER, CORAL, GO-ULTRA,
ONYX and UPGRADER are all trademarks of
Albemarle Corporation.
References
1 Morteani G, The rare earths: their minerals,
production and technical use, Eur. J. Mineral,
1991, 3, 641650.
2 DeSoto T, Raring to go, Hydrocarbon
Engineering, Sept 2011, 6064.
3 Lemos F, Rama Ribeiro F, Infuence of
lanthanum content of LaHY catalysts on their
physicochemical and catalytic properties,
Applied Catalysis, 39, 1988, 227338.
4 de Kroes B, Groeneboom C J, OConnor P,
New zeolites in FCC, paper F1-Ketjen, Catalysts
Symposium, 1986 Amsterdam.
5 OConnor P, Verlaan J P J, Yanik S J, Challenges,
catalysts technology and catalytic solutions in
resid FCC, Catalysis Today, 43, 1998, 305313.
6 Scherzer J, The preparation and
characterization of aluminum-defcient
zeolites, catalytic materials, J. Am. Chem. Soc.,
1984, 157-200.
7 Desai P H, Haseltine R H, Advanced FCC
catalysts formulations can be used to boost
motor octane number of gasoline, Oil & Gas
Journal, 23 Oct 1989, 6876.
8 Humphries A, Yanik S J, Desai P H, Gerritsen
L A, OConnor P, Zeolite developments in fuid
catalytic cracking address the new refnery
challenges, Akzo Catalysts Symposium, 1997.
9 Pouwels A C, Vreugdenhil W, Ingenuity and
developments in resid cracking catalysts, Akzo
Nobel SCOPE symposium, paper F-2, Florence,
Italy, 2004.
10 Adkins B, Bruno K, Yung K Y, Maximising
fuels from the FCC unit, PTQ, Q2 2010.
11 Hodgson M, Looi C K, Yanik S, Avoid
excessive RFCCU catalyst deactivation
Improve accessibility, Akzo Nobel Catalysts
Symposium, 1998.
12 van de Gender P, Yung K Y, Commercial
operation confrms performance benefts of
highly accessible Akzo Nobel catalysts, Akzo
Nobel Catalysts Symposium, 1994.
13 Foskett S A, Rautiainen E, Control iron
contamination in resid FCC, Hydrocarbon
Processing, Nov 2001, 7177.
14 Yung K Y, Jonker R J, Meijerink B, A novel
and fast method to quantify FCC catalyst
accessibility, ACS National Meeting, Aug 2002,
Boston.
15 Hakuli A K, Imhof P, Kuehler C W,
Understanding FCC catalyst architecture and
accessibility, EcoMagic, Akzo Nobel Catalysts
Symposium, Jun 2001.
16 Fu C-M, Schaffer A M, Effect of nitrogen
compounds on cracking catalysts, ACS, 1985.
17 Plantenga F L, Miles T, Catalytic options
for future European FCC operations, European
Refning Technology Conference, London, 1996.
18 Kramer A, Avoiding the low sulfur diet
new catalytic ways to cost-effectively reduce
product sulfur and SO
x
emissions, paper AM-
11-04, NPRA AM, San Antonio, 2011.
19 Propylene maximization in FCC and residue
FCC Albemarle AFX catalysts: the preferred
option, Albemarle Catalyst Courier, 79, Spring
2011.
Yen Yung is Global Technical Specialist for
Albemarle, Amsterdam, The Netherlands. He
has over 20 years experience in FCC catalysts,
technical service and troubleshooting.
Ken Bruno is Global Applications Technology
Manager, FCC, for Albemarle, Houston,
Texas. He was a specialist in FCC catalyst
technology at the Amoco Research Center,
then at Amocos (BP) Whiting refnery before
joining Albemarle. He has a PhD in chemical
engineering from the University of Notre
Dame, Indiana.

Competitors catalyst Albemarle catalyst with LRT options
Feed properties
Feed rate, B/D Base Base
Gravity, API 23.1 23.1
Sulphur, wt% 0.3 0.3
Conradson carbon residue, wt% 1.0 1.0
Riser outlet temperature, C 535 535
Regenerator bed temperature, C 696 697
C/O, wt/wt 6.5 6.5
Catalyst data
Catalyst addition rate, t/D 5.4 4.7
E-cat activity, wt% 68 71
E-cat matrix surface area, m
2
/g Base Base +30
E-cat AAI Base Base +3
RE
2
O
3
, wt% 2.2 2.2
Yields (TBP)
LPG, lv% 29.6 28.6
Gasoline, lv% 48.9 50.4
LCO, lv% 18.2 18.1
Slurry, lv% 10.7 9.9
Coke, wt% 6.0 6.0
Conversion, lv% 71.1 71.1
At equal fresh catalyst RE
2
O
3
, better performance is obtained at a lower catalyst
addition rate. Albemarles catalyst features a higher AAI and matrix surface area
Table 6
Amber LRT, vacuum gas oil application Upgrader LRT, residue application
Feed quality
API 26.1 25.9
Conradson carbon residue, wt% 0.1 2.9
E-cat properties
Activity, wt% 73 66
RE
2
O
3
, wt% 0.5 0.55
Ni, ppm 50 2145
V, ppm 125 4180
Riser temperature, C 527 529
Regenerator temperature, C 688 727
FCC unit yields
C
2
minus, wt% 2.4 5.0
LPG, vol% 31.9 22.6
Gasoline, vol% 60.9 51.7
LCO, vol% 16.9 26.1
Slurry, vol% 3.1 5.5
Conversion, vol% 80.0 68.4
Low rare earth Amber LRT and Upgrader LRT perform well in gas oil
residue feedstock applications respectively
Table 7
albemarle.indd 8 9/12/11 12:41:08
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Catalyst additives reduce rare earth costs
R
are earth is an integral compo-
nent of todays FCC catalyst.
Rare earth stabilises the
zeolite, adding substantial activity, is
sometimes used as a vanadium trap
and is also present as an oxidising
agent within SO
x
additives. Rare
earth is therefore an essential
element in todays FCC catalyst tech-
nologies, supplying increased
activity, improved gasoline yields
and oxidation function in SO
x
addi-
tives. Rare earth has also passed
through a price surge, increasing
over 1500% in the last 18 months.
In an attempt to reduce catalyst
costs, most FCC catalyst suppliers
have begun offering very low or
zero rare earth formulations.
Reducing rare earth drops a cata-
lysts intrinsic activity, potentially
leading to large increases in catalyst
addition rates and potentially offset-
ting these savings in rare earth costs.
An alternative solution for many
refners is to use a rare earth-free
metal trap. One such technology
is Cat-Aid, which has been shown
to trap vanadium and absorb feed-
stock nitrogen. The net result
produces an increase in conversion,
along with reduced catalyst addition
rates and/or rare earth concentra-
tions. Additionally, Intercat has
successfully commercialised new
SO
x
-reducing additive technology
containing 50% less cerium. This
additive has exceeded expectations
in every commercial trial.
This article provides guidelines for
the FCC operator, enabling the most
effective application of these two
technologies. Best available technol-
ogy related to the injection of these
additives into the circulating inven-
tory will be discussed.
Catalyst additive technologies help to control rare earth costs in fresh FCC
catalyst additions and in SO
x
capture
Ray FletCheR
Intercat
Reducing FCC catalyst costs
Rare earth levels on fresh catalyst
prior to the recent price escalation
had risen to an average value of
approximately 2.5 wt%. This increase
in concentration was due to the
strong positive impact of rare earth
on both catalyst stability and activ-
ity. The result of this increased
concentration has been an overall
reduction in fresh catalyst addition
rates, observed industry wide.
The rare earth effect is strongest
within units processing heavy feed-
stocks. These feedstocks typically
produce higher delta coke, resulting
in more severe hydrothermal condi-
tions within the regenerator. Rare
earth-stabilised zeolites better with-
stand the high-severity conditions
observed within the regenerator.
These feedstocks also typically
contain higher concentrations of
vanadium and nitrogen, which have
the effect of reducing catalyst activ-
ity. Rare earth provides additional
activity to counteract the loss in
activity imparted by these poisons.
With the recent rare earth price
escalations, refners have been
driven to reduce rare earth levels on
their fresh catalyst in order to
contain operating costs. The net
result of this change is a reduction
in catalyst stability and intrinsic
activity. These two effects require
refners to increase their fresh cata-
lyst addition rate. These increased
additions offset the reduction in
fresh catalyst pricing.
Intercat has commercialised a rare
earth-free metal trap, Cat-Aid, capa-
ble of passivating vanadium and
absorbing nitrogen. Vanadium passi-
vation limits the formation of
vanadic acid and its subsequent
attack on the zeolite within the cata-
lyst particle. Vanadic acid attack
results in dealumination of the
zeolite crystal, leading to activity
loss. Cat-Aid effectively limits the
negative impact of vanadium in the
circulating catalyst inventory.
Cat-Aid has the additional beneft
of absorbing nitrogen present in the
feedstock (see Figures 1 and 2).
0.89
0.84
0.79
0.14 0.24 0.34 0.44 0.54
n
o
i
s
r
e
v
n
o
C
Catalyst additions, lb/bbl
0.74
Cat-Aid 8.3
Cat-Aid 6.6
Cat-Aid 4.9
No Cat-Aid
Figure 1 Cat-Aid reduces catalyst additions
intercat.indd 1 12/12/11 13:12:22
application. The net result of nitro-
gen absorption by the metal trap
particle is to retain base catalyst
activity, which leads to increased
conversion and reduced catalyst
additions.
One refner using Cat-Aid recently
took the opportunity to reduce the
rare earth level on their fresh cata-
lyst (see Figures 3 and 4). The rare
earth level was reduced by 1.2 wt%,
which led to a 2.0 wt% loss in MAT
activity. However, conversion on the
unit was constant. Additionally, the
refner was able to reduce their fresh
catalyst addition rate by 17%. The
additive cost was fully compensated
by the combined effect of the
reduced rare earth level plus the
reduced catalyst addition rate. As an
added beneft, the refner was able
to lower the SO
x
-reducing additive
injection rate due to the inherent
capability of Cat-Aid to absorb SO
x

in the regenerator.
Cat-Aid is most effective in FCC
units processing heavy feedstocks.
Two simple guidelines enable the
refner to determine whether it will
be effective in their specifc opera-
tion. It performs best in units
sensitive to nitrogen poisoning. It is
recommended that the process engi-
neer plot conversion versus nitrogen.
The unit will respond well to Cat-
Aid injection if the slope of this
curve is greater than or equal to 1.0
wt% conversion loss per 200 ppm
basic nitrogen. Second, the vana-
dium passivation functionality of
this catalyst will be most effective
when the concentration of vanadium
on equilibrium catalyst is greater
than 2000 ppm.
Controlling SO
x
-reducing
additives costs
High-activity SO
x
-reducing additives
are tri-functional catalysts. These
functionalities include an oxidation
step to convert SO
2
to SO
3
, a chemi-
sorption step of SO
3
onto surface
oxide sites, followed by a reduction
in the chemisorbed SO
3
to H
2
S in the
riser and reactor stripper. Cerium
oxide is the catalyst that oxidises
SO
2
to SO
3
.
It is important to understand how
cerium oxide functions as both an
oxidant and oxygen carrier in SO
x
-
reducing additives.
1
The mixture of
Nitrogen is a temporary poison that
neutralises FCC catalyst acid sites,
thereby suppressing activity. These
adsorbed nitrogen-bearing molecules
are then oxidised in the regenerator,
thereby uncovering the previously
inactive acid site. These acid sites
are then subjected to further nitro-
gen poisoning during subsequent
feed contact in the riser mixing zone.
Cat-Aid has been observed to absorb
nitrogen in every commercial
73
75
74
72
71
70
69
68
1000 1200 1400 1600 1800 2000 2200
%
|
o
v

,
n
o
i
s
r
e
v
n
o
C
Total nitrogen, ppm
67
Cat-Aid
Base
70
74
72
68
66
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8
%
l
o
v

,
y
t
i
v
i
t
c
A
Equilibrium rare earth
64
Base
Cat-Aid
73
75
71
69
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8
%
|
o
v

,
n
o
i
s
r
e
v
n
o
C
Equilibrium rare earth
67
Base
Cat-Aid
Figure 2 Cat-Aid absorbs nitrogen
Figure 3 Activity effect
Figure 4 Cat-Aid maintains conversion
intercat.indd 2 12/12/11 13:12:32
two oxidation states, Ce(III) and
Ce(IV), creates defect sites in the
crystal structure where oxygen ions
are missing (oxygen vacancies).
These vacancies are lled up in the
regenerator, allowing cerium oxide
to act as a monatomic oxygen
sponge. Monatomic oxygen is more
reactive than molecular oxygen.
Cerium oxide is therefore a very
effective catalyst for oxidation
reactions.
Reducing the additive cost by
simply dropping the cerium oxide
concentration works up to a certain
point. However, exceeding this point
results in loss of SO
x
-reducing activ-
ity, leading to substantially increased
additive injection rates. As an exam-
ple, current-generation zero rare
earth SO
x
additives have shown
themselves to be unsuitable for use
where high levels of SO
x
reduction
are required.
Capitalising on the depth of its
R&D knowledge, Intercat has devel-
oped and commercialised a low
cerium SO
x
-reducing additive, Super
SO
x
Getter-II, in which the cerium
oxide content has been reduced by
50%. The activity of this additive has
been observed to be at least equal to
the benchmark SO
x
-reducing addi-
tive, Super SO
x
Getter, containing
twofold more cerium oxide. Over 38
FCC units are now continuously
injecting Super SO
x
Getter-II without
any loss in SO
x
absorption efciency.
This technology enables reners
faced with stringent SO
x
emissions
standards to reduce their operating
budget without compromising effec-
tiveness. Additional R&D work is
currently under way to further
reduce this cerium level, using the
expertise of the Johnson Matthey
research group, which has extensive
expertise in cerium catalysis. It is
expected that Super SO
x
Getter-III
will shortly become available, with a
much lower cerium content.
As has previously been
mentioned, Cat-Aid is also able to
absorb SO
x
, but it does have a
limited capacity. This additive will
be effective at controlling SO
x
emis-
sions where ultra-low emissions are
not required. It has been effectively
utilised for SO
x
control in such
operations and it is a rare earth-free
technology.
Additive injection technology
Intercat loaders are present in over
285 reneries around the world (see
Table 1). Separate additive injection
is extremely important to get the
full benet of additives such as Cat-
Aid and Super SO
x
Getter-II.
Premixing into the base catalyst
restricts the renery to just one
concentration. This imparts a huge
cost on a renery needing to control
SO
x
emissions. Decreasing SO
x
addi-
tive additions is not possible
without a loss in catalyst activity,
and increasing SO
x
additive addi-
tions requires increased catalyst
addition rates. The added costs of
such an impractical solution are too
high to be worth consideration.
Intercat provides state-of-the-art
loader technology without charge
to reners injecting Cat-Aid or
Super SO
x
Getter-II.
Conclusions
Catalyst additive technologies exist
to help the rener control rare earth
costs in both their fresh catalyst
additions and in SO
x
capture tech-
nology. These technologies have the
added advantage of being able to be
used only when required.
Furthermore, the injection rate may
be adjusted according to need.
Finally, Intercat provides loader
technology to a rener wishing to
inject these additives into their circu-
lating inventory.
Reference
1 2011 NPRA Q&A Panel response to Question
#96 by Ray Fletcher.
Ray Fletcher is a Senior Technologist with
Intercat Inc, Sea Girt, New Jersey. He has worked
as a process engineer on FCC, hydrotreating,
catalytic reforming, alkylation and catalytic
polymerisation. He has a chemical engineering
degree from University of Washington.
Region Number
North America 158
Asia 73
Europe 30
South America 18
Africa/Middle East 7
Total 286
Intercat loaders
Table 1
1 DURANIT
inert ceramic balls

2 special reformed packings
6 liquid distrubutors / collectors
7 random packings made of plastic
8 random packings made of metal
9 random packings made of ceramic
10 software and consulting
4 support plates / grids
5 feed devices: gas / liquids
3 droplet separators / demisters
P. O. Box 552, D - 56225 Ransbach-Baumbach
Phone +49 26 23 / 895 - 0, [email protected]
Tower packings,
catalyst support
material and
column equipment.
For further information
please visit:
www.vff.com
1
1
2
2
3
6
6
4
4
4
4
5
7
7
8
10
10
8
9
9
Please visit us
Hall: 4.0
Stand: D66
www.ptqenquiry.com
intercat.indd 3 9/12/11 12:51:45
www.ptqenquiry.com
M 8 8 L l
^K'Z/
uS
Selecting the best amine/solvent for gas treating is not a trivial task. There are a number of amines available to remove con-
taminants such as CO
2
, H
2
S and organic sulfur compounds from sour gas streams. The most commonly used amines are
monoethanolamine (MEA), diethanolamine (DEA), and methyldiethanolamine (MDEA). Other amines include diglycolamine
(DGA), diisopropanolamine (DIPA), and triethanolamine (TEA). Mixtures of amines can also be used to customize or optimize
the acid gas recovery. Temperature, pressure, sour gas composition, and purity requirements for the treated gas must all be
considered when choosing the most appropriate amine for a given application.
Primary Amines
1 MLA CC
S
u
MLA P
S CC

MLA
1

MLA uCA
CC
S CCS 1

MLA uCA
Secondary Amines
1 uLA CC
S
MLA
8 uLA MLA
1

ulA
P
S
ulA CCS S
1
ulA Aul SuLllnCL
Tertiary Amines
A MuLA
P
S CC
S
C P
S C
P
S MuLA P
S
CC

uLA P
CC

1
8 MuLA

C

Mixed Solvents
l
S l
MuLA CC
MuLA M
MuLA
CC

M
SuLllnCL
S C
A
P
S
Choosing the Best Alternative
C

M

A M
1

1

M

l M

C AC8
nM l M

8 8 L
Process
Selecting the Best Solvent
for Gas Treating
Insight:
bre.indd 1 8/12/11 15:07:38
Consolidation of refnery control rooms
T
he consolidation of control
rooms was conducted in
several refneries in the 1990s
and early 2000s as a means of reduc-
ing the number of operators and
improving effciency for enhanced
competitiveness. The characteristics
of consolidated control rooms vary,
refecting the history of a refnery.
However, the adverse business envi-
ronment in recent times has meant
that the oil industry has had to
consider approaches other than
consolidation. In many plants,
migration of the distributed control
system (DCS) gives an opportunity
to investigate the control room
confguration and operational
management system for achieving
safer, more stable and more effcient
operation.
This article describes refnery
modernisation activities that led
towards an ideal refnery that
enables safe, stable and effcient
operation. In the example described,
Yokogawa was asked to contribute
to a major part of the modernisa-
tion relating to DCS migration and
control room consolidation.
Yokogawa offered the Refnery
Operation Modernisation Service,
one of its VigilantPlant Services,
which features four solutions:
consolidated refnery production
control including consolidated
control room design; operator train-
ing system (OTS); capture and
amalgamation of best practices
(SOPs); and safety instrumented
system (SIS).
Major issues for modernisation
Over the years, the refner had
upgraded its units one by one,
with the aim of creating a high-
Migration of a refnerys DCS provided an opportunity to reconfgure and
consolidate the control rooms and operational management system
EriC Jan KwEKKEbooM
Yokogawa Europe & Africa
conversion refnery, and the
operations department had also
been expanded to as many as six
operating sections responsible for
each unit. In all, the refnery had
four distributed control rooms and
DCSs acting independently. The
control systems were supplied by
two vendors and were of several
generations, because they had been
introduced as process installations.
This presented several challenges:
The detailed design of the DCS
varied among the different opera-
tions sections
Each operations section had its
own operational procedures
There was a lack of communica-
tion between operations sections
since they mainly relied on informa-
tion carried through instrumentation
signal cables or via the supervisory
information system
The CPU utilisation rate and the
number of instruments to be
handled by each DCS were
approaching allowable limits due to
the repeated expansion and modif-
cation of process units
The segmented organisation
resulted in differing requirements
for the education and training of
operators, different spare parts for
the DCSs, and different procedures
for the maintenance engineers.
To solve these problems and to
more actively achieve safer and
more effcient operation of the refn-
ery, and to transfer the knowledge
of veteran operators, the refnery
decided to combine the processes of
consolidating the production organi-
sation and control rooms with the
migration of the production control
system to the latest one.
activities towards an ideal refnery
The refnery authorised a phased
plan towards an ideal refnery to
meet the demographic challenges
presented by knowledgeable veter-
ans retiring and their places being
taken by less experienced person-
nel, with a target date of 2013 (see
Figure 1). In Phase 1, the consolida-
tion of control rooms and the
migration of the production control
system were scheduled to be
completed in June 2009. After the
physical migration, organisational
re-engineering was planned, as
Phase 2, to establish the consoli-
dated operation centre by 2011.
This project was triggered by a
report by a business improvement
working group to the refnerys top
management in 2004. Until the
formal launch of the project in 2007,
the control room consolidation
working group in the refnery iden-
tifed the issues involved for safe,
stable and effcient operation, as
well as the training of younger
operators for knowledge transfer.
During this preparation phase,
The segmented
organisation
resulted in differing
requirements for
the education and
training of operators,
and different spare
parts for the DCSs
yokogawa.indd 1 9/12/11 13:00:51
ing basic design policies for the
system to achieve these purposes
defned by the refner:
The consolidated refnery produc-
tion control system: this includes
not only the consolidation of control
rooms and the migration of the
control system planned in Phase 1,
but also further system enhance-
ment for improving plant operation
and for operator training scheduled
in Phase 2, implemented in 2011
Highly effcient operation
Safety management
Refnery-wide operation: in the
near future, refnery operation will
be integrated into one unit, from
crude processing to product
shipping
Operator training for sharing and
improving operational expertise:
the same DCS information is avail-
able everywhere in the refnery, in
meeting rooms, in the feld and in
the offce. Operational assistance
systems are standardised
High availability of the systems:
the intention is to improve the
Yokogawa proposed a visual
concept of an ideal refnery and the
human-centred confguration of the
consolidated control room, includ-
ing its migration plan, in
collaboration with the refners
working group. In Phase 1 of the
project, named the control room
consolidation project, Yokogawa
undertook the migration work
including control room design.
Control room consolidation project
The refnery was operated by six
sections: the on-site plant sections
1-4, the power and utilities section,
and the offsite section, distributed
in four control rooms. The initial
study concluded that the control
rooms should be consolidated into
one by constructing a new control
room, and that the control systems
should be migrated, taking the
opportunity of a large turnaround
scheduled for June 2009. The
planned DCS migration was not a
simple replacement of each existing
DCS system, but introduced a
supervisory DCS that could control
and monitor the whole plant. It also
included implementation of the
consolidated safety instrumented
system (SIS) to enhance the safety
of the entire plant.
The main purposes of the control
room consolidation and the system
migration are as follows:
Enhance agility and co-operative-
ness in the refnery, and enhance
the integrity of information systems
throughout the supply chain, from
plant operation to shipping
Improve safety and establish a
more effcient operation by system-
atic operator training to retain
operational expertise, capturing
operational procedures and amal-
gamating the derived best practices
as improved standard operational
procedures
Prepare the environment for the
above two major aims by construct-
ing a new consolidated control
room and a new system, thus estab-
lishing operational integrity.
Yokogawa proposed the follow-
Improvement WG
Consolidating entire operation
groups
Creating a production centre
2004 2005 2009 SDM SDM 2011 2012 2013
Oil Company
activities
Yokogawa
activities
Proposing control
room consolidation
Control room
consolidation project
Improvement
Ideal refinery
Image of consolidated
control room
t
t
Standardised system operation
Implementation
t
t
Lifecycle service t
New consolidated control room 2009
Consolidation of control rooms
Consolidated control room 2011
Production centre
Business-
improvement WG
Work flow analysis
Reporting for an
ideal refinery
Refinery-wide
consolidation WG
Scoping
Tendering
Deciding the
EPC contractor
Production
department DCS WG
Deciding the vendor
Basic and detailed
design
Attending the system
test
Switchover
construction
2006 2007 2008
Distributed control rooms
Phase 1
Consolidation of control rooms and
migration of the production system
Phase 2
Integrated production centre
Consolidation of operation sections
Ideal refinery
Figure 1 Activities toward an ideal refnery
yokogawa.indd 2 9/12/11 13:01:03
availability of each device, network
and piece of software by designing
the systems with full consideration
of systems operation and
maintenance.
Project implementation
Yokogawa proposed the Refnery
Operation Modernisation Service to
solve the various issues in the refn-
ery. It consists of four solutions: the
consolidated refnery production
control system; consolidated control
room design; OTS; and SIS for the
refnery.
The proposed consolidated refn-
ery production control system
utilises the full functions of Centum
VP, Yokogawas latest integrated
production control system. The
system can realise effcient refnery
operation in a consolidated control
room by covering a broad range of
plant areas and by incorporating
many applications such as advanced
process control, operation assist-
ance, alarm analysis and SISs (see
Figures 2 and 3).
The human-machine interface
(HMI) for the consolidated control
system was confgured by utilising
the HMI technology of the Centum
VP. The new HMI can contribute to
safe, stable and effcient operation
in the following ways:
Improved operability by adopting
a multi-window function
Integrated operation of multiple
systems including DCS, SIS,
advanced process control system,
operation assistance system,
alarm analysis system, and supervi-
sory emergency shutdown system
using integrated terminal
functions
Custom-designed furniture for
comfortable operation and dual
monitoring displays for suffcient
information
Reduced noise because of the fan-
less housing design
Dedicated operational HMI
console for temporary use
A space-saving layout by adopting
portable HMI consoles that are on-
line detachable from the DCS bus.
Refnery-wide DCS bus and
supervisory DCS
The supervisory DCS is installed on
top of each unit DCS that collects
refnery-wide data, such as utility
data through the refnery-wide DCS
bus, and monitors the performance
of the refnery. The supervisory
DCS also has a refnery-wide
control function such as utility
balance, and plant manipulations
can be carried out through local
DCS HMI.
In the future, this supervisory
DCS will play an important role for
total production management of the
refnery, from crude processing to
product shipping.
Large channel capacity and
high-speed DCS bus
The consolidation of multiple large
systems such as the total refnery
system without losing information
was achieved by a high-speed
network. Yokogawa provides the
Vnet/IP large channel-capacity DCS
bus, which eases the restrictions on
Operation support system
Unit DCS
Alarm management system
Safety instrumented system
DCS bus
Unit DCS
DCS bus
Unit DCS
DCS bus
Consolidated emergency
shutdown system
Ubiquitous LAN
Common database of
utility data
Advanced process control
system
ERP
+ Plant-wide network
Manufacturing
execution system
Supervisory DCS
Utility
Landing
Crude oil
tank
Blender
Product
tank
Shipping
CDU
Secondary
processing
units
Intermediate
tank
Operator
training system
FCC
CDU
t
t
Vnet/IP
Figure 2 Overview of the consolidated refnery production control system
yokogawa.indd 3 9/12/11 13:01:15
Operator training system
In 2008, the refnery introduced a
new type of fuid catalytic cracker
as its second unit. The new unit
was very different from the existing
one in operation, and so the refn-
ery decided to introduce an OTS to
ensure a quick start-up. The OTS
was confgured by combining
Yokogawas OmegaLand dynamic
simulator alongside the DCS.
Moreover, since the existing DCS
was migrated to the latest version
of Centum VP accompanied by the
consolidation of control rooms, the
OTS was also used for operator
training of the new operation
screens for the consolidated refnery
production control system. This
reduced the risk involved changing
a DCS vendor and enabled quick
start-up of the new DCS.
The OTS was set up in the newly
constructed training room, and a
new system for the crude distilla-
tion unit (CDU) was also developed
to transfer the expertise of veteran
operators.
Taking the opportunity of DCS
migration, the consolidated SIS was
installed to enhance the safety of
the entire refnery. The existing
emergency shutdown (ESD) system
using a conventional relay system
was replaced with the SIL3-certifed
ProSafe-RS safety instrumented
system, which meets all require-
ments covered by IEC 61508/JIS C
0508.
The SIS is part of the core infra-
structure of the consolidated
refnery production control system
for safe and effcient operation (see
Figure 4). The system can also be
integrated with the DCS and ESD
triggers, and events can be seen on
the same HMI of the DCS.
Emergency responses can be
carried out on the HMI display of
the DCS along with the new ESD
console.
The reliability of the ESD system
has been improved by the follow-
ing features of ProSafe-RS:
Diagnosis of the entire path from
a system I/O card to emergency
shutdown valves without obstacles
such as hard relays
Diagnosis of wiring from ESD
data communication between
devices and systems.
DCS everywhere using a
ubiquitous LAN
The terminal service function of the
Centum VP provides an environ-
ment for remote viewing of DCS
screens. All the information in the
DCS is visible in real time from
anywhere in the refnery, whether
in meeting rooms or at individual
desks in offces, through the ubiq-
uitous LAN. This helps to transfer
operational expertise and develop
human resources.
Standardising and improving
operation methods
In the course of the system consoli-
dation, existing different system
specifcations must be consolidated
into one standard set of specifca-
tions. These include specifcations
for applications and HMI. In stand-
ardising the system interface,
operation procedures were also
reviewed and improved by apply-
ing enhanced standard operating
procedures (SOP) for eventual
standardisation and as such ready
for further evolution, thus provid-
ing an environment for transferring
expertise and continuous improve-
ment of operator skills.
Ease of maintenance
Large-scale complex systems
require vigilant design to improve
integrity and availability. High-
reliability design policies including
redundancy, duplication and quick
system recovery are adopted. In
addition, remote maintenance
enables problems to be detected
and solved at an early stage, lead-
ing to stable operation.
Human-centred design for
consolidated control room
For the new consolidated control
room, Yokogawa designed the
layout, lighting and acoustic
systems, taking into account ergo-
nomic factors such as operability,
workability, visibility and comfort.
The control room layout also takes
such factors as communication
between sections and future expand-
ability into consideration. As a
result, the new control room is
human-centred in terms of both
comfort and vigilance (see Figure 3).
Figure 3 Illustration of consolidated control room concept
The SIS is part of the
core infrastructure
of the consolidated
refnery production
control system for
safe and effcient
operation
yokogawa.indd 4 9/12/11 13:01:26
www.ptqenquiry.com
mogas.indd 1 8/6/11 11:55:48
Table 3
contact signals including pressure
switches
Partial stroke test of emergency
shutdown valves.
ProSafe-RS is not a simple
replacement of a relay-based SIS
distributed throughout the renery,
but a renery-wide SIS that will
also provide simultaneous emer-
gency shutdown of the entire
renery along with automation of
the prioritised emergency pressure
reduction sequence in the event of
a large-scale earthquake.
Migration process
The migration of the DCSs through-
out the renery and the migration
of the existing ESD circuit to
ProSafe-RS had to be completed
during the short period of the
scheduled turnaround in 2009.
Table 1 shows the outline of the
migration. Although it was a big
project, it was completed in just 14
days.
System migration in such a short
time and without any trouble was
achieved thanks to meticulous
preparation, detailed scheduling
including resource allocation, a start-
up team supported by a backup
team, specialists and subsystem
engineers capable of quick trouble-
shooting, and a hot line to the
quality assurance department.
Effects of control room
consolidation
Among the many positive effects of
the consolidation of the control
rooms, the greatest is a sense of unity
and face-to-face communication
between people, allowing them to
broaden their outlook by working
together.
The renovated control room makes
people feel relaxed and secure, and
Consolidated refinery
production control system
HMI of unit DCS
Vnet/IP
Vnet/IP
Vnet/IP
Expanded I/O bus
Optical cable
Supervisory DCS bus Supervisory DCS bus
Satellite control
rooms
Satellite control
room
Satellite control
rooms
ESD console
Consolidated control room
Optical cable
SIS for
common units
Unit SIS Unit ESD
Consolidated
SIS
Expanded I/O
Self-diagnosis
Wiring diagnosis
Redundant
High-speed event logger
DCS compatible
Figure 4 Safety instrumentation for the renery based on ProSafe-RS
Item Description
Control room Consolidating four control rooms into one
Yokogawas start-up team Up to 60
Total loop and interlock tests Switched signal: approx 15 000 points, completed in 14 days
System migration Simultaneous migration of 144 eld devices.
Breakdown:
HMI: 44; server: 16; control station: 68; safety controller: 14
Outline of the consolidation during the 2009 scheduled turnaround
Table 1
yokogawa.indd 5 13/12/11 13:15:19
as a result they can concentrate on plant operation.
Improvements in data integrity and data availabil-
ity accelerate communication between units to
optimise the operation among units. Standardisation
of operational procedures, a secondary effect of the
system consolidation, has promoted the transfer of
operational expertise. Introduction of the SIS has
enhanced safety. Another intangible but valuable
effect of the renovation is the motivation of young
operators. They are stimulated by the new control
room, the new systems and the new way of plant
operation, as are all the people in the refnery.
Continuous improvement activities towards
establishing the production centre are expected to
create a variety of effects in the future.
Future plan
The consolidation of control rooms and the migra-
tion of the production system prepared the
infrastructure for further improvements at the
refnery. The next steps towards organisational
and operation procedural renovations have
started.
Increased productivity of operators as a result of
consolidation will be used for further improve-
ment of plant operation as well as human resource
development. Yokogawa continues the develop-
ment of industry solutions such as Production
Instructor and Exapilot, contributing to the tasks
of capturing, amalgamating and optimising opera-
tional procedures as a contribution to operator
effectiveness.
The consolidated control room is now the centre
of operation and it will be an enabler of two-way
optimisation of refnery operation, both refnery-
wide and organisation-wide. The refnery can be
operated refnery-wide as one unit, while organisa-
tional integration can realise fexible production to
accommodate a changing environment.
Eric Jan Kwekkeboom is Business Development Manager, Oil & Gas
Downstream Industry Solutions, with Yokogawa Europe and Africa
in Amersfoort, The Netherlands, managing market development
in oil and gas downstream business, refnery and petrochemical
industry segments in particular. He holds bachelors degrees in
process engineering and chemical engineering and graduated in
business-to-business marketing.
The renovated control room
makes people feel relaxed and
secure, and as a result they can
concentrate on plant operation
SAMSON AG MESS- UND REGELTECHNIK
Weismllerstrae 3
60314 Frankfurt am Main Germany
Phone: +49 69 4009-0 Fax: +49 69 4009-1507
Internet: www.samson.de www.samsongroup.de
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itw.indd 1 10/12/09 12:46:08
Integrated monitoring for optimising
crude distillation
R
efneries are among the most
complex of processing sites.
They include many, entirely
different, physical and chemical
processes. These include atmos-
pheric and vacuum distillation, and
chemical reactions such as cracking,
isomerisation, hydrogenation, desul-
phurisation, aromatisation and
blending. Many processes are inter-
linked. The product of one unit
serves as the feed for other, consecu-
tive processes. Any failure,
shutdown or lack of control of one
of these processes will immediately
affect another process in the produc-
tion chain and will have an impact
on the entire economy of the refn-
ery, its revenue, proft or loss.
The majority of chemical indus-
tries process raw materials with
defned specifcations. Refneries
must cope with a dependency on
non-specifc, fuctuating crude oil
compositions. Trends and differ-
ences in crude oil prices, the size of
tankers that can make harbour to
supply a refnery, political instabili-
ties in oil exporting countries,
changing product specifcations and
the equipment available in the
refnery dictate that crude switch-
ing and/or crude blending are
inevitable. Crude blending is also
one of the practices applied by
refneries to increase the margin
between the cost of the crude feed
and the revenue from selling the
fnal products.
Differences in crude oil composi-
tions from various locations impact
the production capacity of the refn-
ery to deliver the volume of
required distillates that the refnery
is committed to bring to market.
The economics of refning are even
On-line process analysers in crude distillation units prevent lost throughput caused
by non-conforming process conditions and crude oil switching
GReGORy ShahnOvSky, Tal COhen and ROnny McMuRRay
Modcon-Systems Ltd
more complicated because each
refnery is unique. Many refneries
are designed differently to fulfll
their initial target to produce a
certain range of petroleum products
from a defned quality of crude oil.
At present, refneries must be fexi-
ble enough to respond immediately
to crude oil changes and deviations
in product demands as a result of
the changing global economy.
The required fexibility in the
management of a refnery and the
complexity of the different proc-
esses, crude oils and distillates can
only be achieved by stringent moni-
toring of the quality of the incoming
material and the outgoing product
streams in each refnery unit. None
of the product streams are stan-
dalone. The root of each stream is
found in the crude oil that has been
delivered to the distillation towers.
Challenge of crude distillation
unit optimisation
The effciency of a refnery to
produce petroleum distillates is
directly linked to:
The crude oil that is delivered to
the refnery
The equipment of the refnery
The maximum throughput of
crude oil and petroleum products
The ability to produce the distil-
lates with the highest value at
maximum yield.
Optimising the process conditions
of the crude distillation unit is a
main challenge for each refnery. It
increases proft by producing the
required range of distillates at
maximum yield and at minimum
cost. To achieve this goal, full and
real-time monitoring and control of
each incoming stream of crude oil
and outgoing distillate stream is an
inevitable requirement to ensure:
Minimum infuence on produc-
tion capacity for each required
distillate due to crude oil changes
Minimum infuence on distillate
quality upon crude oil switching
Maximum production of high-
value distillates. Overlapping
characteristic boiling ranges exist
between two neighbouring refnery
fractions. Maximum distillation
proft is achieved by shifting the cut
points towards the highest value
products
Maximum stability of the quality
of each distillate throughout the
entire distillation process
Minimised production of off-spec
or borderline materials and, as a
result, the need for re-reprocessing
or blending.
The quality and the cost of crude
oil depends on its origin. Blending
various types of crude oil is
required to reduce the cost of the
crude oil feed to be distilled and to
adapt the crude oil feed so that it
can be processed properly by the
equipment available in the refnery.
Crude oil differences result in a
Strict and adequate
monitoring of all
streams is crucial
to ensure maximum
effciency of
the crude distillation
unit
modcon.indd 1 9/12/11 13:51:28
Crude oil arrives at the refnery
contaminated with water, brine,
salts that are partially crystallised
and dispersed in the oil, sulphides,
sediments and traces of heavy
metals. Some of the brine is emulsi-
fed with the oil fraction, so
demulsifcation and separation of
the water fraction from the organic
material must be conducted. The
crude oil is treated by chemicals
and water-washed to remove solu-
ble inorganic salts. Electrostatic
separation is applied to break the
emulsion, to improve the separation
between the water and oil phase.
Removal of the salts, halogen ion
and sulphides is of high importance
to prevent corrosion and excessive
fouling of the pipes and other refn-
ery equipment. Installation of a
dedicated crude oil analyser enables
continuous quantifcation of critical
properties of the crude oil stream.
This system of salt measurement is
based on the behaviour of saltwa-
ter/crude oil emulsions infuenced
by electromagnetic felds. A main
advantage of a crude analyser is
that the need for any added
solvents is omitted. On-line quanti-
fcation of any variation of the API
number, the salt content, the H
2
S
content and the water content of
the crude oil enables adjustment of
the operating conditions of the
desalter in real time. Process chemi-
cals and water can be delivered in
suffcient but not excessive
quantities to the desalting process
to remove undesired salts and H
2
S.
On-line and real-time analysis of
crude oil properties processed by the
desalter increases its effectiveness to
provide crude oil ready for distilla-
tion. By continuously monitoring the
quality of the crude oil feed to the
crude distillation unit, immediate
corrections to the desalters process
conditions can be executed, to main-
tain a constant quality of desalted
crude oil and direct adjustments
upon crude switching.
The implementation of a crude
analyser will have a cost-reducing
effect, as it has an impact on the
energy consumption of the de-emul-
sifer, the consumption of wash
water, a reduction in the corrosion
of the pipelines and equipment, and
it predicts the API of the feed
variation in the distillate distribution
produced by the crude distillation
unit under the same process
conditions. To achieve maximum
production effciency and product
yield, continuous re-adjustment and
fne-tuning of process conditions is
inevitable.
Ongoing laboratory analyses are
expensive and time consuming. The
time lapse from sampling to analyti-
cal reporting increases the likelihood
of a refnery to produce off-spec or
borderline material. Delayed aware-
ness of the defcient qualities of
distillates will delay the implemen-
tation of process adjustments. The
crude distillation unit could operate
in an inadequate and non-proftable
mode for a long period of time. In
addition, any other failure or
malfunction of the crude distillation
unit could result in reduced produc-
tion capacity or even a total
shutdown of the plant if not handled
immediately.
To optimise process parameters
to produce the required range of
distillates at the highest yields,
while taking into account the char-
acteristics of the crude oil to be
processed, strict and adequate
monitoring of all streams is crucial
to ensure maximum effciency of
the crude distillation unit.
Full control of product quality
can only be achieved by an inte-
grated system of on-line crude and
distillate analysers. The analyser
must provide continuous, instanta-
neous information on the quality
and physical properties of the
incoming crude oil and the outgo-
ing streams of distillate streams of
naphtha, kerosene, LGO and HGO,
as well as the vacuum distilled
products LVGO and HVGO.
Real-time corrective actions need to
be taken to guarantee optimised
operation of the crude distillation
unit.
To achieve this, an integrated
system has been developed, to
enable full management of the
crude distillation units perform-
ance. It starts with the incoming
crude entering the desalter and
continues until the fnal distillates,
which are produced by the atmos-
pheric and vacuum towers.
The integrated system is
composed of:
A crude oil analyser (desalter
control)
Near infrared (NIR)-based
analysers
Magnetic resonance spectrometry
(MRS)-based analysers
Analyser management software
Automatic validation software for
on-line process analysers.
Desalter control
The amount of water, salts and
sediment in the crude oil received
by refneries varies widely accord-
ing to the source of crude oil,
pre-processing at the site of its
source and the means of transport
of crude from source to refnery.
Desalter
control room
Analyser Analyser
Desalter 1 Desalter 2
Analyser
To
CDU
Crude
oil
Fresh water /
solution
Figure 1 Flow chart of the crude analyser setup in a desalter system
modcon.indd 2 9/12/11 13:51:46
entering the crude distillation unit.
Optimal performance of the entire
process is achieved by mounting the
analysers before, between and after
the desalters (see Figure 1).
Crude distillation unit
Crude oil pretreated by the desalter
is transferred to the crude distilla-
tion unit for fractionation into the
different distillates according to
their boiling ranges:
Gases with low boiling points
(32C)
Light straight-run naphtha
(3288C)
Heavy straight-run naphtha
(88193C)
Kerosene (193271C)
Light gas oil (271321C)
Heavy gas oil (321 427C)
Vacuum gas oil (427566C).
Exact cut points between the distil-
lates are determined with respect to
the initial and fnal boiling point, as
specifed by local and international
standards, or by the required physi-
cal properties needed for further
processing. The boiling ranges of
neighbouring distillates partially
overlap. It is up to each refnery to
shift the exact cut point so that the
maximum production capacity for
each product towards the most valu-
able distillates is achieved.
Prediction of the yield of distilla-
tion can be made by using
algorithmic techniques such as
linear programming (LP). However,
any unexpected discrepancy
between the crudes actual proper-
ties and the LP model will directly
impact distillation effciency.
Process control of modern refner-
ies is computerised to a large extent.
However, human intervention
cannot be eliminated from the over-
sight and control of the entire
process. Both automatic and human
control of the refnery units needs
to receive a continuous stream of
real-time data for the process. Any
delay will infuence the decision to
perform a required action to main-
tain constant production according
to the predetermined programme.
To achieve proper control of proc-
ess units in refneries, classical
analytical methodologies are not
adequate. Laboratory analyses are
expensive and time consuming and
include many steps such as
sampling, sample handling, sample
preparation, measurements, data
handling and reporting. The delay
between sampling and production
of analytical results prevents process
conditions being corrected at the
earliest stages in the event of any
discrepancy. Effcient processing in
the crude distillation unit has the
following minimum requirements:
Actual information about critical
properties, which are representative
of the crude oil or crude blend to
be processed
Effcient operation of the atmos-
pheric and vacuum towers to
provide high-value distillates at the
highest feasible yield
A real-time, accurate and reliable
overview of product quality at any
stage of the crude distillation
process
The ability to correlate between
the quality of incoming crude oil
feed and outgoing streams of
distillates.
On-line spectrometric
process analysers
Total analysis of the physical prop-
erties of a distillate or fnal blend is
a time-consuming operation. Each
analysis is conducted separately
according to the appropriate ASTM-
defned method.
On-line, dedicated ASTM process
analysers are expensive. Each indi-
vidual physical property to be
measured requires a dedicated
analyser. Full monitoring requires
purchasing a large number of
analysers and bearing the cost of
maintenance and calibration.
The physical properties of crude
oil, distillates or blends are an over-
all outcome of the infuence of the
physical properties of each individ-
ual substance in the matter.
Identifcation of these compounds
enables a quantitative prediction of
the physical properties of the entire
mixture. As physical properties
correlate with their chemical
compositions, spectrometric meth-
ods are applicable to quantitatively
predict physical properties of a
composition of chemical substances
as in the refnery stream. They
make it possible to quickly provide
full information about compliance
with specifed product qualities.
Two spectrometric methods are
widely used to control the process
conditions of units in the refnery:
Near Infrared Spectrometry (NIR)
Magnetic Resonance Spectrometry
(MRS).
NIR spectrometry
Near infrared (NIR) technology is
0.4
1.2
1.0
0.8
0.6
0.2
0.0
-0.2
-0.4
-0.6
800 840 880 920 960 1000
e
s
n
o
p
s
e
r

r
e
s
y
l
a
n
A
Wavelength, nm
-0.8
3km bre
6m of bre
Figure 2 Infuence of optical fbre length on the NIR spectrum
Spectrometric
methods are
applicable to
quantitatively predict
physical properties
of refnery process
streams
modcon.indd 3 9/12/11 13:51:58
thenes, paraffns, olefns and the
C-number.
Since it is an optical method, the
implementation of NIR technology
is restricted to transparent solutions
only. A second drawback of NIR
technology is its lack of linear
response. Particularly in certain
regions of the infrared, the absorp-
tion of light does not correlate
linearly with the concentrations of
chemical compounds according to
the Beer-Lambert law. Moreover, its
linear response is also affected by
overlapping of spectral peaks and
inferior resolution between peaks
assigned to various molecular
bonds. This is caused predomi-
nately by different excitation
energies assigned to each chemical
bond.
(MRS) is a non-optical method that
enables molecules to be distin-
guished according to their chemical
structures. It is based on differences
in the alignment of hydrogen atoms
under the infuence of a magnetic
feld. When a group of nuclei with
spins is placed in a static magnetic
feld of 60 MHz, each nucleus aligns
with the magnetic feld. With the
formation of small magnetic felds
based on the absorption spectrum
of the near infrared spectrum
within the range 7501050 nm. This
covers the spectrum of petroleum
products. Each petroleum product
has its specifc fngerprints in the
NIR spectrum, which represent the
products composition. Statistical
correlation between NIR data and
the results of laboratory analysis
enable physical properties to be
predicted to a high accuracy.
NIR technology includes a NIR
analyser connected to its feld units
by standard optical fbre cables.
The feld unit is mounted on a
bypass pipe of the stream to be
monitored. It can be installed at
any location in the refnery, up to
3km from the NIR analyser. The
optical signal is not infuenced by
the length of the optical fbre (see
Figure 2).
An advantage of NIR technology
is that the distillate to be measured
fows continuously through the
feld probe. This enables measure-
ments to be performed in
continuous mode. As an optical
method free of mechanical sampling
systems, the optical multiplexer
enables instantaneous multiple
analyses of various streams. Field
units are simple and maintenance
free. They do not contain any
mechanical parts (see Figure 3).
A light source is transmitted by
an optical fbre analyser to the feld
unit. The beam passes through the
distillate that is fowing continu-
ously through the feld probe. The
transmitted light is returned via the
optical fbre back to the detector of
the analyser. Spectral data are proc-
essed by chemometric models and
converted to quantitative values of
a predetermined variety of physical
properties.
In combination with the proper
chemometric, NIR technology quan-
tifes the required physical
properties in naphtha, kerosene and
gasoil by one single measurement.
These properties include density,
IBP, FBP, T10%, T90%, freeze point,
pour point, fash point, cloud point,
cetane number, benzene, naph-
Figure 3 Fixed measuring probes of a NIR
on-line process analyser
Parameter NIR analyser MRS analyser
Method Near infrared Nuclear magnetic resonance
Optical method Magnetic method
Analysed species O-H, C-H, N-H bond stretch in H-Nuclei
Quantitative analyses Non-specifc towards molecules. Based on Based on exact quantifcation of hydrogen nuclei assigned
fngerprints of the mixture to specifc molecules
Chemometric models No-linear response; linear extrapolations of Linear response. Enables linear extrapolations of the model
the model omitted
Required sample properties Transparent and free of water Transparent or opaque or dense, and wet samples
Calibration modelling Requires deconvolution of NIR combinations, Correlates - distinguishes peaks and linear responses
overtones and chemometrics
Sampling system Continuous fow through. Fixed probe Valve system connected to pipes (stop/fow operation).
mounted on pipes (bypass) Fast loop bypass pipes (changes from one stream to another)
Analyser to sampling probe connection Optical fbre Pipe system
Analyser location from probe Remote from probe, up to 3km Probe integrated in analyser
Multistream sample switching Optical multiplexer Mechanical switching between streams. Consecutive
measuring mode between streams
Lag time between results and actual sample None Depends on pipe length
Linear response of measurement Low. Defcient linear spectral response in High. Linear response of hydrogen content with spectral
mid and near IR response
Reliability upon crude change Sensitive. Accuracy infuenced by compounds, No sensitivity to crude switching. Accurately quantifes
containing elements other than carbon or specifc hydrogen atoms. Specifc to chemical structures of
hydrogen atoms. Non-specifc to chemical molecules
structures of the molecule
Stream temperature changes Lightly sensitive Insensitive
Comparison between NIR and MRS process analysers
Table 1
modcon.indd 4 12/12/11 13:37:42
that oppose the externally applied
feld, the effective magnetic feld at
the nucleus is reduced. Types of
nuclei and chemical bonds in the
molecule infuence this phenome-
non in different ways and enable
the determination of the chemical
structure of different species in
molecules.
MRS is an electronic method and
has the beneft of being applicable
to measuring transparent, opaque
and dense solutions alike. It can be
used to quantify the physical prop-
erties of crude oils, the entire range
of distillates, or any other refnery
product.
The concept of MRS process
analysers is based on the assign-
ment and quantifcation of the
different types of hydrogen atoms
of organic molecules or water
present in distillates or crude oils.
The linear spectral response corre-
lates accurately with the hydrogen
atoms assigned to different molecu-
lar species of the substances that
make up the refnery stream.
The spectrum is infuenced by the
nature of neighbouring chemical
carbon-carbon bonds and neighbour-
ing non-carbons in the molecular
structure. Assignments can be made
to identify whether these molecules
are linear or branched paraffns,
olefns, mono-aromatics, polyaromat-
ics, heterocyclic, naphthenic, acids,
oxygenates or water (see Figure 4).
In combination with the proper
chemometrics, MRS technology is an
effective tool to quantify physical
properties of the following refnery
streams: crude oil, naphtha, kerosene,
gasoil, LGO, HGO, bottom residues
and vacuum distillates by one single
measurements. The physical proper-
ties include: density, API, IBP, FBP,
T10%, T90%, RVP, fash point, pour
point, cloud point, freeze pint, cetane
number, PONA, benzene, naph-
thenes, paraffns, olefnes, aromatic
content and water.
The majority of currently available
on-line process analysers are charac-
terised by their high sensitivity to
minor fuctuations in temperature.
A newly developed MRS on-line
magnetic resonance- based process
analyser includes innovative hard-
ware and software to eliminate this
temperature sensitivity.
Comparison of NIR and MRS
The characteristics of NIR and MRS
technologies are summarised in
Table 1.
Spectrometric methods in crude oil
distillation units
Effective operation of crude distilla-
tion depends on maintaining the
correct temperature profle within
the atmospheric and the vacuum
towers. It is a direct outcome of the
composition of the crude oil and
the range and quantity of distillates
to be produced.
The composition of each individ-
ual distillate and its resulting
physical properties is linked to the
0 8 7 6 5 4 3 2 1
H-types observed in a gasoline
1
H NMR spectrum, ppm
H
H R
R
H H
R R
R H
R H
CH
3
CH
3
CH
3
CH
2
CH
Oxygenate
Crude
oil
Gas
(butane and lighter)
Light naphtha
Heavy naphtha
Kerosene
Light gas oil
Heavy gas oil
LVGO
HVGO
Residue
NIR* = Applicability is transparency dependent
MRS
Bottom
residue
Desalter
Atmospheric
distillation
tower
Vacuum
distillation
tower
MRS
MRS or NIR
MRS or NIR
MRS or NIR
MRS or NIR*
MRS
MRS
MRS
Figure 4 MRS spectrum of gasoline
composition of the crude oil. To
achieve maximum distillation
yield, on-line monitoring of the
crude oil composition is a basic
requirement. By on-line monitor-
ing of the physical properties and
assay of the incoming crude oil
feed, immediate corrections to the
temperature profle can be estab-
lished to maintain a constant
stream of distillates. When crude
switching occurs, only on-line
monitoring of the crude oil assay
minimises the impact of the
switch on production capacity.
Adjustments to process conditions
can be implemented without delay
and will reduce the impact of
Figure 5 Implementation of NIR and MRS in the crude distillation unit
modcon.indd 5 12/12/11 13:37:51
crude switching on product yield
and quality.
The limitations of NIR spectrome-
try as an optical method disqualifes
its application to crude oils and
heavy distillates. For this reason,
only MRS analysers can be applied
to crude monitoring.
Combined multiple measurement
of the assay and other physical
properties of crude oil, such as API
number, water content, pour point
and fash point, by a single analyser
can provide full assessment and
control of an incoming crude oil
stream.
Monitoring of the distillates from
the atmospheric tower can be
partially established either by NIR
process analysis or by a MRS-based
analyser (see Figure 5). The method
of choice depends on the transpar-
ency of the distillate stream to be
measured. In principle, naphtha,
kerosene and diesel oil are measura-
ble by NIR and MRS alike. However,
traces of heteroatomic molecules,
which are present at different levels
in crude oils, will distill alongside
the required distillates. These mole-
cules absorb light in the NIR region.
If they are not included in the chem-
ometric model, interference affects
the accuracy of analytical results.
This does not apply to MRS spec-
trometry. Heavier distillates such as
heavy gasoil, atmospheric bottoms
residue and the vacuum distillation
products, LVGO, HVGO and
bottoms residue are preferably
analysed by MRS only.
A combination of NIR and MRS
technology provides an effcient
tool to manage all streams of the
crude distillation tower for continu-
ous fne-tuning of operating
conditions to maximise the yields
of distillates.
On-line monitoring of each distil-
late enables accurate determination
of its upper distillation points
(T90% - FBP) and its lower distilla-
tion points (T10% - IBP). It enables
accurate cutting between two neigh-
bouring distillates towards the
fraction of higher value (kerosene
in diesel, diesel in AGO) from the
heavier cut (see Figure 6).
This is achieved by adjusting the
distillation towers temperature
profle, while being in control of its
response towards the qualities of
the distillates. Uncontrolled adjust-
ment of process conditions may
lead to the production of off-spec
distillates. On-line monitoring of
the quality of distilled naphtha,
kerosene and diesel is highly
important. It indicates the stability
of the process and prevents the risk
of uncontrolled overshooting when
changing the process conditions.
Beyond that, any discrepancy in the
process or the product quality can
immediately be handled. The risk
of producing unnecessarily off-spec
or borderline materials is drastically
reduced, so preventing the need for
reblending or reprocessing. Smooth
fne-tuning of process conditions
can be completed without any risk
of overshooting, and any discrep-
600
800
750
700
650
550
500
450
400
350
Kero
(CDU1)
Kero
(CDU2)
Diesel
(CDU2)
AGO
(CDU2)
Kero product
(hydrotreater)
T
e
m
p
e
r
a
t
u
r
e
,

F
0 12 24
Time, hrs
300
T50
T90
T10
Figure 6 Measurement of crude unit rundown streams
ancy or malfunction in the crude
distillation unit can be dealt with
immediately.
Total on-line analyser management
and control
Both MRS and NIR-based analysers
are correlative methods. To achieve
the highest available accuracy of
the analysers, a full-distributed
analyser management and control
system has been developed. It
provides an effcient tool for main-
tenance calibration and validation
of the analyser systems. It is confg-
ured to be connected to remote
systems. It monitors and records
the operating state of the installed
equipment and validates a wide
variety of analysers and instru-
ments. The software can monitor
and control a wide range of analys-
ers. A graphic display of data from
multiple analysers provides histori-
cal data on analyser performance.
Highest accuracy is achieved by
two different modes of validation
and calibration of the analysers:
By running samples with the
known quantities value of a
required physical property
By a continuous comparison of
analyser readouts with laboratory
results, referring to the same time
of sampling.
The software manages validation
procedures according to ASTM
D3764. It performs alarm manage-
ment and controls active streams to
be sent to the analyser.
All measurements obtained from
on-line analysers of the different
streams are localised on one single
display. An accurate overview of
the quality of all individual process
streams is provided to the operator,
which enables effcient correction of
process conditions to be made,
which are based on the response of
the operators actions with respect
to the changing physical properties
of the streaming distillates. To
maintain the highest accuracy,
continuous calibration of the
analyser is highly recommended.
Conclusion
Strict monitoring of all incoming
and outgoing streams in the
crude distillation unit is of the high-
est priority to ensure optimal
modcon.indd 6 9/12/11 13:52:36
performance of the distillation proc-
ess. Laboratory analyses are time
consuming and cause a lag between
discovering any discrepancy in
product quality and applying a
corrective response. Optimal
performance of the crude oil distil-
lation unit can only be achieved by
a continuous mode of on-line meas-
urement of the physical properties
and quality of each stream using
accurate, calibrated on-line process
analysers. This enables ongoing
correlation between the crude oil
and the various distillates, as well
as between the distillates them-
selves. Many dedicated ASTM-based
analysers are required to achieve
this goal. However, their cost of
installation and maintenance is
high.
Spectrometry-based correlative
analysers are able to perform
simultaneous multiple measure-
ments of a variety of physical
properties. Spectrometry-based
correlative on-line analysers
provide full coverage of all incom-
ing and outgoing streams, and
enable operators to carry out
immediate processing adjustments.
These tools enable smooth and eff-
cient operation of the crude
distillation unit to produce the
desired distillates at maximum
yield. They also make it possible to
minimise the impact of crude
switching and maximise the yield
and capacity of desired distillates
by appropriate shifting of the cut
points of the required distillation
ranges.
The commitment of each refnery
to increase its refnery margin is
directly linked to its readiness to
install an on-line multiple-stream
process analyser. Before a decision
is taken on which analyser system
is most effective for a refnery, the
differences in properties between
the NIR and MRS methods should
be taken into consideration.
However, the best performance can
only be achieved by an incorpora-
tion of both NIR and MRS
technologies.
Gregory Shahnovsky is the Chief Executive
Offcer of Modcon-Systems Ltd, Akko, Israel,
a developer of process analysers, optimisation
and control solutions. With over 25 years
experience in the chemical and petrochemical
industries, he holds a MSc in process
control engineering and a MBA in business
administration.
Tal Cohen is Vice President of R&D and
Business Development at Modcon-Systems Ltd
and previously held positions of CEO, CTO and
VP R&D in high tech companies.
Ronny McMurray is an Application Scientist
at Modcon-Systems Ltd, with experience
in applied R&D and as chief chemist in the
chemical and petroleum industries. He holds a
PhD in chemistry.
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Crude oil vapour pressure testing
I
t is very important for the true
vapour pressure (TVP) and Reid
vapour pressure (RVP) of crude
oil to be tested when dealing with
its production and storage. The
vapour pressure indicates how the
crude oil will perform during
handling, highlights conditions
under which bubbles are likely to
build and shows where pressure
build-ups of escaping light ends
could happen. As such, vapour pres-
sure measurement prevents costly
damage to pipelines or vessels trans-
porting crude oil. It also provides
guidance on how transportation
facilities need to be built to survive
a worst-case scenario.
Pipeline operators determine TVP
and bubble point before transport-
ing the crude to a distribution
point. With wellhead crude, gas has
to be removed to meet pipeline,
storage and tanker specifcations.
Excess gas can be separated or
fared to regulate the vapour pres-
sure and prevent any damage to
the transportation medium. If the
vapour pressure of the crude case
is too high, two main safety issues
can arise. The frst is pumping cavi-
tation during transfer operations
and the second is vapour pressure
in the pipeline, or in a vessel, which
could rise because of temperature
changes. Once the transportation
medium is exposed to direct
sunlight, the vapour pressure of the
crude oil rises and, in the worst
case scenario, causes damage.
Hence, it is advisable for operators
to be equipped with a vapour pres-
sure analyser, to prevent costly
damage and to provide evidence
that the released crude is delivered
according to specifcations.
Vapour pressure testing is an important safety check in the transport, storage and
blending of crude oil
Hannes PIcHler and Klaus Hense
Grabner Instruments, a subsidiary of Ametek
TVP measurement and bubble point
determination
The exact defnition of TVP and
bubble point is a topic of wide
discussion in the engineering
community. First, it is worth
mentioning that the bubble point
refers to a temperature, whereas the
bubble point vapour pressure refers
to a pressure. According to the
International Maritime Organisation,
the TVP and bubble point pressure
(BPP) are equal: The TVP or bubble
point vapour pressure is the equilib-
rium vapour pressure of a mixture
when the gas/liquid ratio is effec-
tively zero. It is the highest vapour
pressure which is possible at any
specifed temperature. As the
temperature of a petroleum mixture
increases, its TVP also increases. If
the TVP exceeds atmospheric pres-
sure, the liquid commences to boil.
(IMO, 2006, p140). In this defnition,
TVP is essentially the total vapour
pressure (P
tot
) of the crude oil minus
the vapour pressure of air and the
dissolved gases in the sample (P
gas
).
The resulting value is the absolute
vapour pressure (P
abs
or P
liquid
) of the
liquid, commonly referred to as
TVP, as measured by ASTM D2879
(US EPA, 2006). The ASTM D2879
method should be used only for
single-component substances. Crude
oil in general is a multi-component
liquid and thus requires a different
form of analysis.
The equation TVP = BPP at a
vapour-to-liquid ratio (V/L ratio) of
0/1 addresses the common practical
problems for crude oil transporta-
tion. In foating roof tanks, the roof
is placed directly on the liquid crude
oil, while in pipelines the liquid
crude oil is pressurised. In both
cases, the V/L ratio is effectively
zero and the TVP measurement
gives a precise indication of the
bubble point pressure at a specifed
temperature.
In some cases, the equation is not
suffcient. In multi-component
mixtures, bubbles tend to build
whenever the vapour pressure of
the liquid exceeds the environmental
pressure (IMO, 2006), independent
of whether the V/L ratio is 0/1 or
100/1. Three factors have an infu-
ence on the bubble point: pressure,
volume and temperature. A more
accurate defnition takes different
temperatures and V/L ratios into
account when determining the
bubble point: in a multi-component
mixture, the bubble point is the
temperature at which the frst
bubbles appear at a fxed V/L ratio.
Pumping cavitation
One of the major risks when trans-
porting crude oil is pumping
cavitation. Cavitation happens when
the TVP or bubble point vapour
pressure at a V/L ratio near 0/1 is
reached and usually has drastic
effects. In a pumping system, the
crude oil is accelerated, generating
areas of low pressure. When the
surrounding pressure is lower than
the vapour pressure of the crude oil,
bubbles build, grow, then collapse,
generating high pressure and high
temperatures at the bubble surface.
Near a fxed surface, for instance in
a pumping system, the collapse of
the cavitation bubble will generate a
shockwave directed to a nearby
surface, which can damage the
transportation system or the pump.
For correctly dimensioning new
pipelines and pumping systems, and
grabner.indd 1 9/12/11 14:20:45
unexpected pressure increase in the
pipeline or the tanker. Whereas
dead crude oil is mostly unprob-
lematic when transported, live
crude oil contains volatiles. Volatiles
such as natural gases increase the
vapour pressure of the crude case.
When the transportation medium
for live crude a pipeline or a
tanker is exposed to direct
sunlight and heats up, the vapour
pressure can increase considerably.
The vapour pressure of live crude
oil flled at 20C can more than
double if the temperature of the live
crude oil is increased to 50C.
The absolute pressure increase
from temperature fuctuations is
even higher if the live crude oil is
transported at a very low V/L ratio.
In Russia, it is necessary to test the
vapour pressure of crude oil at a V/
L of 0.02/1 to simulate the condi-
tions in a tanker or a pipeline.
Typically, 98% of a tankers volume
is flled with crude oil. The increase
in vapour pressure that results from
this can be seen in Figure 1.
The testing of vapour pressure at
different temperatures and V/L
ratios answers many questions that
arise from crude oil transportation:
How much will the vapour pres-
sure rise if the crude oil at a V/L of
0.02/1 (98% flled with liquid) is
transported at 50C rather than
37.8C because the tanker is exposed
to sunlight?
Do control personnel need to
reduce the vapour pressure prior to
shipment or storage?
Is it necessary for specifc crude
cases containing volatiles to fll a
tanker up to only 90% to prevent
damage to the tanker or air pollu-
tion by excessive outgassing?
Is the vapour pressure low enough
that it is possible to blend in some
natural gas prior to shipment with-
out risking damage?
Vapour pressure analyser
It is essential to continuously moni-
tor vapour pressure, TVP and BPP
at different V/L ratios to help opera-
tions regulate their transportation
system immediately. The Minivap
On-line vapour pressure process
analyser from Grabner Instruments
can measure TVP or BPP at different
temperatures in the range of 2060C
for writing standard operating
procedures, it is important to know
the vapour pressure of the crude oil.
To prevent bubble building and
pumping cavitation in an installed
transportation system, it is necessary
to ensure that the pressure in the
transportation system is higher than
the vapour pressure of the crude for
any expected condition.
If the vapour pressure is too high,
pressure, volume or temperature
have to be modifed. The pressure in
the transportation system can be
increased to exceed the vapour pres-
sure of the crude oil. Also, the
vapour pressure of the crude oil can
be reduced, for instance by the sepa-
ration or burning of excess gases,
which reduces the volume. As a
third option, the temperature for
transportation and thus the vapour
pressure of the crude oil can be
reduced. Lord & Ruddin suggest oil
degasifcation or oil cooling to
reduce the vapour pressure: The
degasifcation program removes gas
from oil in selected caverns, which
reduces its bubble point pressure
and gas-oil ratio, which in turn
signifcantly increases the predicted
margin of system performance
under the safety criteria.
2
Crude oil producers face a
complex problem here: when crude
oil is extracted, it is not homoge-
nous. The vapour pressure of the
crude can change during oil produc-
tion. Also, the presence of various
amounts of natural gas in the crude
changes the V/L ratio considerably
and increases the vapour pressure
dramatically. Plus, highly viscous
crude oil needs to be transported at
a high temperature to guarantee a
fow in the pumping system and in
the pipeline. Temperature changes
in turn affect the vapour pressure.
Depending on the amount of light
ends delivered with the crude oil,
the vapour pressure of the crude oil
will be signifcantly higher for 60C
compared to the vapour pressure at
37.8C. Most vapour pressure testers
measure crude oil only at 37.8C
(100F) and a V/L ratio of 4/1. But
crudes can sometimes be transported
at 85C and at a V/L ratio close to
0/1. Under these extreme condi-
tions, some volatiles might begin to
dissolve even in dead crude oil
and produce a gaseous mixture,
causing a non-linear pressure
increase. This risk cannot be fore-
seen if the vapour pressure is
measured at 37.8C and a V/L ratio
of 4/1 only.
For adequate risk management
regarding the bubble point, it is thus
important to measure the vapour
pressure at different temperatures
and at a V/L ratio of 0/1. Only a
vapour pressure analyser that can
monitor vapour pressure at different
temperatures and V/L ratios will
allow the operator to regulate their
transportation system immediately.
Vapour pressure increase in the
transportation medium
Another potential problem when
transporting crude oil is an
180
240
220
200
160
140
120
100
80
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
p
,

k
P
a
V/L ratio
60
Figure 1 Vapour pressure of crude oil at different vapour-liquid ratios at 37.8C (100F)
grabner.indd 2 9/12/11 14:20:57
and to simulate TVP for even higher
temperatures. It also enables meas-
urement of a V/L ratio down to
0.02/1 in a pressure range of 01000
kPa.
The analyser incorporates the
ASTM D 6377 method, which is the
latest standard for the vapour pres-
sure determination of crude oil
without sample preparation. This
method replaces the 80-year-old-
plus ASTM D323 and is used to
measure TVP or BPP in the analyser.
With the vapour pressure process
analysers sample conditioning
system, the pressurised crude oil is
transferred directly to the measuring
chamber and the vapour pressure is
measured against a vacuum by a
single expansion of a built-in piston.
A three-point expansion sequence is
performed at different V/L ratios,
then a curve ft is performed for
assessing the TVP at a V/L of 0/1
(see also Lord & Rudeen, 2010).
The Minivap On-line also incorpo-
rates the triple expansion method
for vapour pressure measurement
according to ASTM D6378, which
allows for direct measurement of the
total vapour pressure (P
tot
) of the
sample, and the vapour pressure of
both the liquid (Pabs or P
liquid
) and
the gases (P
gas
) in the sample (see
Figure 2). Based on the fact that the
vapour pressure of liquids remains
constant and that all components
such as dissolved air follow the ideal
gas equation, (p*V)/T = constant, an
expansion is performed in three
steps at a constant temperature.
Three total pressure values are
determined, and from these the
partial pressure of the air, the solu-
bility factor of the liquid and the
absolute vapour pressure of the
liquid are calculated. Results for the
TVP (P
tot
) of the sample, the pressure
of the liquid (P
abs
or P
liquid
) and the
pressure of the gas (P
gas
) are availa-
ble every fve to seven minutes. The
precision of this measurement is
ASTM Round Robin proven and
signifcantly better than that of clas-
sical vapour pressure test methods.
Crude blending
An analyser that can be used to
measure both TVP and RVPE will
repay its cost in a short time.
Usually, suppliers and refners agree
over the maximum vapour pressure
limits of crude oil delivered to a
plant or terminal. This is necessary
to ensure safety for transportation
and storage, and to guarantee that
the refner receives crude of a certain
quality. In this process, crude oil
blending is a means of increasing
the sales price or facilitating the
processing of crude oil. By blending
lower-grade crude oil with higher-
grade crude oil or natural gas to
reach, but not exceed, target specif-
cations, the price valuation of crudes
can be increased signifcantly. Profts
are earned if target specifcations are
reached by blending the minimum
amount of high-grade crude oil with
low-cost hydrocarbons.
The addition of these hydrocar-
bons is limited by the maximum
RVP. Depending on the RVP prior
to blending, typically ratios of 15%
hydrocarbons are blended into the
crude. The highest accuracy in
vapour pressure tests according to
standards is the ultimate goal of
every blending facility because it
increases the possible blending ratio.
The precision of the Minivap On-
line allows for close C
4
blending to
RVP limits and the highest proft
generation. With a measurement
method that fully complies with the
strictest ASTM, EN and IP standards,
as well as US EPA regulations for
vapour pressure testing of crude oil,
gasoline and LPG, no further testing
in the laboratory needs to be done to
certify the accuracy of the
measurement.
References
1 Specialized Training for Oil Tankers,
International Maritime Organisation, Model
Course1.02,Edition(TB102E),London,2006.
2 Lord D L, Rudeen D K, Strategic Petroleum
Reserve Crude Oil Equation of State Model
Development - Current Performance Against
Measured Data, Research Report, Sandia
National Laboratories, Albuquerque, NM &
Livermore,CA,2010.
3 OrganicLiquidStorageTanks,Compilation of
Air Pollutant Emission Factors, Emission Factor
DocumentationforAP-42,5thed,I,7.1,Offce
ofAirQualityPlanningandStandardsOffceof
AirandRadiation,USEPA,Durham,NC,2006.
Hannes Pichler isaProductMarketingManager
with Grabner Instruments, a subsidiary of
automatic petroleum testing equipment
developerAmetek. He holds a MSc degree in
naturalsciencesfromtheUniversityofVienna.
Klaus Hense is Head of R&D at Grabner
Instruments, where he focuses on the
development and improvement of measuring
methods for the chemical and petrochemical
industry. He holds a PhD in physics from the
TechnicalUniversityinVienna.
P
1
P
2
P
3
P
1
P
2
P
3
P
gas1
P
gas2
P
gas3
V
1
V
2
V
3
Figure 2 Vapourpressuremeasurementusingthetripleexpansionmethod
Idealgaslaw:(p*V)/T=constant
AtaspecifedtemperatureTthefollowingequationapplies:
P
gas1
*[V
1
+V
gas
]=P
gas2
*[V
2
+V
gas
]=P
gas3
*[V
3
+V
gas
]
P
1
=[P
liquid
+P
gas1
]
P
2
=[P
liquid
+P
gas2
]
P
3
=[P
liquid
+P
gas3
]
[P
liquid
]=[P
3
-P
gas3
]
grabner.indd 3 9/12/11 14:21:08
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fw.indd 1 12/12/11 13:36:06
Optimised hydrogen production by steam
reforming: part I
H
ydrogen is a particularly
important feedstock in refn-
eries because of stringent
environmental legislation for
producing low-sulphur gasoline
and diesel fuels. The refnery
hydrogen requirement is fulflled
through the route of steam methane
reforming (SMR) of natural gas.
SMR is a highly energy-intensive
technology and this energy require-
ment can be minimised by
combining various reforming tech-
niques. In this article, process
optimisation of the hydrogen plant
is carried out to minimise natural
gas consumption by considering
operating parameters such as the
steam-to-carbon ratio, various reac-
tor confgurations, methane slip,
choice of product purifcation step,
and natural gas composition in a
conventional SMR process.
In a second article to follow, new
process schemes incorporating an
Modelling optimisation of process and design parameters for minimising natural
gas consumption in hydrogen production by steam reforming
Sanke RajyalakSHMi, kedaR PatwaRdHan and P V BalaRaMakRiSHna
Larsen and Toubro
autothermal reformer (ATR) and a
heat exchange reformer (in series
and parallel combination with the
ATR) offered by licensors are evalu-
ated and compared with the
conventional process. It has been
observed that the new schemes,
from the point of view of natural
gas consumption, are more benef-
cial compared with the conventional
process but at a cost of lower steam
production from the hydrogen
plant. Hence, where the natural gas
price is substantial and dominates
the plant operating cost, the new
process scheme should be utilised.
Along with increased hydrogen
consumption for deeper hydrotreat-
ing, additional hydrogen is needed
for processing heavier and higher
sulphur crude slates. In many refn-
eries, hydroprocessing capacity and
the associated hydrogen network
limits refnery throughput and oper-
ating margins. Furthermore, higher
hydrogen purities within the refn-
ery network are becoming more
important to boost hydrotreater
capacity, achieve product value
improvements and lengthen catalyst
life cycles. Improved hydrogen utili-
sation and expanded or new sources
for refnery hydrogen and hydrogen
purity optimisation are now required
to meet the needs of the future
market for transportation fuels and
the drive towards higher refnery
proftability.
A variety of process technologies
can be used for hydrogen produc-
tion, including steam reforming,
cracking, gasifcation and electroly-
sis. The choice depends on the scale
of production required and the cost
of available feedstocks.
For large-scale production, the
steam reforming of natural gas has
become the preferred solution. In
some cases, partial oxidation has
also been used, particularly where
Feed
pretreatment
NG
(from BL)
Steam
export
BFW water
(from BL)
Natural gas (secondary fuel)
Heat
recovery-I
Heat
recovery-II
PSA off gases (primary fuel)
Steam
reformer
CO-shift
converter
H
2
(to BL)
H
2
purification
Waste heat
recovery
Process
condensate
stripper
Figure 1 Typical steam methane reformed hydrogen plant block diagram
l& t.indd 1 4/1/12 10:15:19
Choice of hydrogen purifcation
step.
The following assumptions were
made while carrying out the
analysis:
Impurities in feed are effciently
removed in the feed purifcation
stage. The total volume of reactors
in the purifcation stage does not
change within the variation of oper-
ating parameters under study
Hydrogen production is fxed at
90 000 Nm
3
/h for any variation in
the operating parameter
PSA effciency is 89%
The kinetics of the reaction are
taken from the open literature and
are not specifcally applicable to
any particular catalyst.
Methane slip
The steam methane reforming reac-
tion is strongly endothermic and is
therefore favoured by a higher
temperature. Typical reformer
outlet temperatures fall in the range
810900C. As the temperature is
increased, the hydrogen yield
increases, which is observed as a
reduction in the methane concentra-
tion in the reformer effuent, known
as methane slip. The higher the
yield, the less the amount of feed-
stock that will be consumed.
Due to the lower methane slip,
the calorifc value of the PSA off-
gas is reduced and, since this
stream is the base load fuel for the
reformer, the supplementary fuel
(natural gas) imported to the hydro-
gen unit increases (see Figure 2).
This effect is enhanced because the
higher reformer outlet temperature
increases its radiant duty. The
supplementary fuel has a relatively
small fow and is strongly infu-
enced by small changes to the
reformer heat balance so that, in
this case, there is a small increase in
the total feed/fuel consumption.
This effect is due to the increase in
radiant duty and reduction in the
steam requirement for the process
feed, giving the net increase in the
steam available for export. The
higher reformer outlet temperature
shifts the heat balance to produce
more steam from more feed/fuel.
Steam-to-carbon ratio
The feed gas to the reformer is a
heavy oil is available at low cost.
However, oxygen is then required
and the capital cost of producing
oxygen plant makes partial oxida-
tion expensive. On the other hand,
the steam reforming of natural gas
offers an effcient, economical and
widely used process for hydrogen
production, and provides near-
and mid-term energy security and
environmental benefts. The eff-
ciency of the steam reforming
process is about 65% to 75%,
among the highest of current
commercially available production
methods.
The SMR process is divided into
sections: feedstock purifcation for
the removal of sulphur and
other impurities; steam reforming
for synthesis gas generation;
shift conversion/carbon monoxide
removal; and hydrogen purifcation.
A general block diagram with natu-
ral gas as the feedstock is shown in
Figure 1.
Natural gas feed is preheated in
coils in the waste heat section of the
reformer, and sulphur is removed
over a zinc oxide catalyst. Process
steam is added, and the mixture of
natural gas and steam is further
preheated before entering the tubu-
lar reformer. Here, conversion to
equilibrium of hydrocarbons to
hydrogen, carbon monoxide and
carbon dioxide takes place over a
nickel-based reforming catalyst. The
gas exits the reformer and is cooled
by steam production before enter-
ing the shift converter. Over the
shift catalyst more hydrogen is
produced by converting carbon
monoxide and steam to carbon
dioxide and hydrogen. The shifted
gas is cooled further to an ambient
temperature before entering the
pressure swing adsorption (PSA)
unit. High-purity hydrogen product
is obtained, and the off-gas from
the PSA unit is used in the reformer
as fuel supplemented with natural
gas fuel. Combustion air for the
tubular reformer burners can be
preheated in coils in the reformer
waste heat section. Part of the steam
produced in the hydrogen plant is
used as process steam; the excess
steam is exported.
The objective of this study is to
analyse the process parameters of
the present confguration and to
identify optimum conditions to
enhance the process performance.
Different process layouts with high,
medium- and low-temperature shift
reactors and also with different
purifcation processes (PSA and
methanator) are studied and
compared.
Identifcation and optimisation of
process parameters
The study focuses on the optimisa-
tion of process/design parameters
for the minimisation of natural gas
consumption. The study is particu-
larly useful in countries such as
India, where natural gas prices
dominate operating cost. The most
important parameters to infuence
natural gas consumption are:
Methane slip
Steam-to-carbon ratio
Natural gas composition
Shift converter confguration
30000
50000
40000
20000
10000
0 1 2 3 4 5 6 7
N
a
t
u
r
a
l

g
a
s

c
o
n
s
u
m
p
t
i
o
n
,

N
m
3
/
h
r
Methane slip, %
0
NG fuel
Total NG
NG feed
Figure 2 Effect of methane slip on natural gas consumption
l& t.indd 2 4/1/12 10:15:38
mixture of steam and hydrocarbon
gas. The mixture is characterised by
the steam-to-carbon ratio, which is
the molar ratio of steam to the reac-
tive carbon contained in the
hydrocarbon gas. A higher steam-
to-carbon ratio drives the reaction
closer to the equilibrium and
increases the hydrogen yield.
Reforming catalysts require steam
to be present in excess, increasing
the volumetric throughput and cost
of the plant, so there is always inter-
est in reducing the steam-to-carbon
ratio. In doing so, there is an increase
in feedstock consumption, which is
almost balanced by a decrease in
demand for supplementary fuel (see
Figure 3). The mechanism of these
effects is opposite to that for a higher
reformer outlet temperature, in that
the methane slip increases and the
PSA off-gas contains more calorifc
value. The decrease in steam-to-
carbon ratio gives rise to an increase
in the reformer radiant duty, which
increases the steam generated in the
convection section. Less steam is
used in the process and the steam
exported from the plant is further
increased. In this case, the signifcant
beneft of a lower steam-to-carbon
ratio is clearly shown. A lower
steam-to-carbon ratio is limited by
the catalyst performance and
tendency of the feedstock to form
carbon at the reformer inlet.
Natural gas composition
Natural gas mainly contains meth-
ane in the range (7598% by
volume) along with higher hydro-
carbons (C
2
+ components) and inert
gases. The higher hydrocarbons
contribute to the calorifc value of
the natural gas as well the hydro-
gen production. The inerts in
natural gas add only to the natural
gas volumetric fow rate and thus
contribute only to capital cost (due
to an increase in the piping and
equipment sizes) and operating cost
(higher power consumption in
compressor). The cost of the natural
gas is calculated on the basis of the
calorifc value. Here it should be
noticed that higher HC content in
the natural gas contributes to higher
hydrogen production for the same
quantity of feed gas. Hence, the
natural gas consumption as feed
decreases with the calorifc value.
Higher HC in the feed also contrib-
utes to more CO
2
, resulting in
higher off-gases from the PSA.
Thus, for the same methane slip,
the contribution from the off-gas is
more in the case of higher HC natu-
ral gas, resulting in a reduction in
the supplementary NG fuel require-
ment. The following graph is
plotted as calorifc value against the
total NG consumption for the given
hydrogen production. The graph
also provides the operating cost for
the natural gas for the hydrogen
plant within the range of calorifc
values considered. The operating
cost is calculated by multiplying x-
axis and y-axis value by the NG
unit cost, which is considered as
29$/Gcal with reference to the
Indian scenario. Hence, for case 1,
the operating cost due to NG works
out to be:
=8565(X-axis value, Kcal/Nm
3
)*43878(Y-axis
value, Nm
3
/hr) *29($/Gcal)
= 10899$/hr.
From Figure 4, it can be seen that
even though NG consumption
reduces with the increase in calo-
rifc value, the operating cost
increases.
Shift reactor confguration
A typical steam-to-carbon ratio in a
confguration containing an HTS
reactor is 2.8. The steam-to-carbon
ratio will depend not only on the
pre-reformer/reformer catalyst but
also on the type of shift converter
catalyst. All HTS catalysts are based
on Fe-Cr oxides that over-reduce
when the steam-to-hydrogen ratio
drops below certain limits. The
30000
50000
60000
40000
20000
10000
1.5 2.0 2.5 3.0 4.0 3.5 4.5 5.0 5.5
N
a
t
u
r
a
l

g
a
s
,

N
m
3
/
h
r
S/C ratio
0
NG fuel
Total NG
NG feed
Figure 3 A wide range of ADZs for all applications
40000
46000
44000
42000
38000
36000
34000
32000
30000
8000 8500 9000 9500 10000 10500 11000 11500
T
o
t
a
l

N
G

c
o
n
s
u
m
p
t
i
o
n
,

N
m
3
/
h
r
O
p
e
r
a
t
i
n
g

c
o
s
t
,

$
/
h
r
NG calorific value, Kcal/Nm
3
Operating costs
NG consumption
11100
11150
11050
11000
10950
10900
10850
Figure 4 Effect of methane content in natural gas on specifc energy
l& t.indd 3 4/1/12 13:21:23
maintained at 860C. A
prereformer/reformer/HTS/LTS
scheme is optimum and provides
~3.5% savings in natural gas
consumption over a reformer/HTS
combination (see Figure 5a).
The prereformer helps in the
reduction of natural gas consump-
tion as feed as well as fuel. Above
that, the prereformer offers other
advantages such as fexibility in
handling natural gas feed composi-
tion, a reduction in reformer heat
duty, and reformer catalyst protec-
tion. Hence, it has become an
essential part of hydrogen plants.
Even though MTS saves on natural
gas consumption, the catalyst volume
requirement is very high compared
to other shift confgurations (see
Figure 5a). As a result, MTS is only
used for smaller capacity hydrogen
plants, while for larger plants it is
used in combination with LTS.

Hydrogen purifcation
In modern plants, PSA is used for the
fnal hydrogen purifcation instead of
CO
2
absorption followed by a meth-
anator. PSA gives a high-purity
hydrogen product of 9899%, while
an absorption/methanator combina-
tion provides purities in the range
9094% (see Figure 5b). Natural gas
consumption will be 12% less than
with a PSA purifcation step. Hence,
in refnery operations where hydro-
gen purity is not essential, a hydrogen
plant with the later combination may
be preferred.
Generation of base case with
optimised parameters and
comparison with operating data
Overall hydrogen production
depends upon the consumption of
utilities, which typically include
feed, fuel, boiler feed water, electri-
cal power, cooling water and steam
production/import. Of these utili-
ties, feed and fuel contribute more
than 90% of the total utilities cost.
The major utility besides natural gas
is steam, as it is produced as by-
product in the plant. The credit
given for export steam can have a
signifcant impact on utility costs,
especially when refnery utility costs
are favourable for steam production.
The steam produced in the plant
has internal consumers within
consequence of this over-reduction
is the formation of higher hydrocar-
bons and oxygenates by the
Fischer-Tropsch reaction.
The steam-to-dry gas ratio will be
0.460.52 for HTS catalysts and 0.39
for MTS catalyst at the converter
inlet. Different shift converter
confgurations were studied by
fxing the natural gas feed fow rate
and the steam-to-carbon ratio. The
reformer outlet temperature is
Figure 5a Effect of shift reactor confguration on natural gas consumption
100
99
98
97
96
95
HTS
98.26
100.00
96.45
98.15
96.94
98.64
HTS+LTS MTS

,
n
o
i
t
p
m
u
s
n
o
c

l

N
G
a
t
o
t

e
v
i
t
a
l
e
R
%
94
Without prereformer
With prereformer
3
5
4
2
1
0 HTS HTS
(HTS+LTS)
LTS
(HTS+LTS)
MTS
R
e
l
a
t
i
v
e

c
a
t
a
l
y
s
t

v
o
l
u
m
e
0
Without prereformer
With prereformer
Figure 5b Catalyst requirement for shift reactor confguration
105
100.00 100.00 100.00
85.64
88.38
100
95
90
85
80
0 NG feed NG fuel Total NG
R
e
l
a
t
i
v
e

N
G

c
o
n
s
u
m
p
t
i
o
n
,

%
75
Methanator
PSA
94.36
Figure 6 Comparison of purifcation methods
l& t.indd 4 4/1/12 10:16:10
boundary limits. Most important
among them are steam-driven
turbines for BFW pumps, ID and FD
fans, process steam for reforming,
process condensate stripper, while
other consumers include steam trac-
ing, lube oil heating, losses and so
on. Steam production within the
plant should be adequate for these
contributors, and surplus steam is
exported. A simulation carried out
for the entire hydrogen plant is
shown in Table 1, along with the set
of optimised parameters studied.
Conclusion
Natural gas offers greater advan-
tages over other feedstocks for
hydrogen production in terms of
simplicity of use, operating cost and
capital cost. For economic produc-
tion of hydrogen utilities such as
natural gas as feed, fuel and steam
are the important parameters.
However, steam export is important
only when there is a need from
other parts of the refnery. Hence,
the overall objective should be to
minimise natural gas consumption
for the hydrogen plant. Hydrogen
plant capacity, end use and export
steam requirement usually govern
the selection of an optimum set of
operating parameters for a new
hydrogen plant.
Sanke Rajyalakshmi is a Process Engineer
specialising in simulation with the Chemical
Engineering Group of Larsen and Toubro,
Powai, India. She holds a masters in chemical
engineering from the National Institute of
Technology, Warangal.
Kedar Patwardhan is a Senior Process Engineer
with the Chemical Engineering Group of
Larsen and Toubro, specialising in simulation,
modelling and process design. He holds a PhD
from the Institute of Chemical Technology,
Mumbai. Email: [email protected]
P V Balaramakrishna is Head of the Chemical
Engineering Group of Larsen and Toubro,
specialising in process design, advanced process
control and process plant optimisation. He
holds a masters in chem engineering from the
Indian Institute of Technology, Kanpur.

Operating parameters Calculated Reference I Reference II Reference III
Approx. capacity, Nm
3
/hr 50 000 100 000 40 000
Methane slip 3.92 6.74 2.69 6.74
Steam-to-carbon ratio 2.6 2 2.59 2.0
NCV, Kcal/Nm
3
11 211 9393 9765 9393
Shift reactor confguration MTS+LTS MTS MTS+LTS MTS
Purifcation step PSA PSA PSA PSA
Utilities, per Nm
3
of hydrogen Calculated Reference I Reference II Reference III
Natural gas feed, Nm
3
/Nm
3
0.257 0.352 0.278 0.352
Natural gas fuel, Nm
3
/Nm
3
0.064 0.025 0.086 0.023
Total feed + fuel, Nm
3
/Nm
3
0.321 0.377 0.363 0.375
HP export steam, kg/Nm
3
0.424 0.695 0.620 0.674
Electric power, kWH/Nm
3
0.0012 0.017 0.038 0.017
BFW requirement, kg/Nm
3
1.222 1.166 1.142 1.145
CW req., kg/Nm
3
2.34 1.9 11.3 1.9
Utilities consumption in a hydrogen plant
Table 1
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l& t.indd 5 4/1/12 10:16:26
Improving Operational Effciencyin the ME Downstream Industry Through Technology Innovations
ME-TECH
2
nd
MIDDlE EasT TEchnOlOgy FOruM
14 & 15 FEbruary, MaDInaT JuMEIrah, DubaI, uaE
gas PrOcEssIng, OIl rEFInIng, rEsIDuE-uPgraDIng & PETrOchEMIcals
Organised by: supported by
sponsored by:
register at www.europetro.com
email: [email protected] tel: +44 20 7357 8394
Key conference Topics
Gas Processing
global gas Market Developments
Impact of shale gas on regional Markets
latest advances for gTl, lng, gas to chemicals
Refning
Outlook for ME refning Industry
update on Projects in the region
latest Technology & catalyst Developments for clean Fuels
reducing cO2, Energy Effciency & carbon capture
Petrochemicals
Key challenges Facing ME Petrochemical Producers
adding Feedstock Flexibility to Ethane crackers
Technologies for Meeting Future Propylene Demand
Value Maximization of c4 stream from crackers
latest Technology Developments for aromatics
Residue Upgrading
Where next for resid upgrading in the ME
case studies on recent resid Projects
latest Delayed coking solutions
latest Technology Options for resid upgrading
epc.indd 1 8/12/11 21:15:42
Improved catalytic reforming
M
odern CCR Platforming
units operate with pres-
sures as low as 35 lb/in
2
g,
which allows for a high selectivity
to desired products (C
5
+ reformate
and hydrogen) and a minimal
production of undesired products
(methane, ethane and LPG). CCR
reforming catalysts contain plati-
num, which is required to catalyse
important reforming reactions. The
level of platinum required on the
catalyst has been considerably
reduced over time as feedstock
contaminant levels and regenera-
tion quality have improved.
Rhenium is not used, since CCR
reforming catalysts do not need to
be as stable as fxed-bed reforming
Catalyst solutions help to improve the proftability and reliability of
reforming units
Anthony PoPArAd, BeAtrix ellis, BryAn Glover and stePhen Metro
catalysts. However, CCR reforming
catalysts do use other metals, most
notably tin, to enhance catalyst
selectivity. While most CCR reform-
ing catalysts are bi-metallic
(containing platinum and tin), other
proprietary promoter metals are
also used in some catalysts, with
their objective being catalyst selec-
tivity enhancement. UOP offers a
wide range of CCR Platforming
catalysts for use in UOP-designed
CCR Platforming Process units or
CCR reforming units designed by
other licensors. The company also
offers many services that can assist
reforming unit operators improve
unit proftability and reliability.
More than 300 CCR reforming units
have been licensed throughout the
world, with more than 250 of those
being UOP CCR Platforming
Process units. A block fow diagram
of a typical UOP CCR Platforming
Process unit is shown in Figure 1.
Recent shifts in the demand for
reformate (used for both gasoline
blending and petrochemicals
production) and hydrogen have
caused many reforming unit opera-
tors to have to adjust their
operations considerably from their
initial designs. This has caused
many reforming units to be oper-
ated in a less effcient manner.
Many units that were designed
decades ago are also more prone to
reliability issues.
Separator
Net gas
compressor
CCR
regenerator
Stacked
reactor
Stabiliser
Combined
feed
exchanger
Heater
Fuel gas
Light
ends
Aromatics
rich reformate
Recovery
section
Spent
catalyst
Fired heaters
Naphtha feed
from treating
Net H
2
rich gas
Figure 1 UOP CCR Platforming Process unit
uop.indd 1 9/12/11 14:37:51
their catalyst before the surface area
drops this low. Some of UOPs
customers have established guide-
lines to automatically change a
reforming catalyst when the cata-
lyst surface area drops to a certain
level.
Alumina phase damage
As mentioned above, reforming
catalyst uses gamma-phase alumina
as its base. Gamma alumina has a
high surface area, which allows for
good chloride retention and metals
dispersion on the catalyst. During
catalyst regeneration, excessive heat
can be generated if coked catalyst is
allowed to come into contact with a
regeneration gas stream containing
high levels of oxygen. The heat
generated during the rapid combus-
tion of coke can thermally damage
the catalyst base, irreversibly
converting the gamma alumina to
undesirable phases such as theta or
alpha. High levels (greater than 5%
to 10%) of theta or alpha alumina
in the catalyst will rapidly reduce
the catalyst surface area, causing a
drop in catalyst performance. These
undesirable phases of alumina also
cause the catalyst to become weak-
ened and in turn can lead to
excessive amounts of fnes make in
the unit. High fnes make can lead
to screen plugging and mechanical
damage, which can result in further
poor performance. Some of UOPs
customers have guidelines estab-
lished for changing out catalyst
when the amount of phase damage
on the catalyst reaches certain
levels.
Metals poisoning
Certain metal contaminants present
in the feed to the reforming unit
may irreversibly accumulate on the
reforming catalyst and adversely
affect its performance over time.
Most metal contaminants should be
trapped by the catalyst in the
upstream naphtha hydrotreating
unit (NHT). NHT catalyst can
become saturated with metals,
however, which causes the contami-
nants to be sent to the downstream
reforming unit.
Most metal poisons, notably
arsenic, lead and silicon, affect the
metal functionality of the reforming
Options for improving
proftability
Due to shifting demands for refor-
mate and hydrogen products,
changes in feedstocks and product
specifcations, many reforming
units are currently being operated
with feed quantities, feed qualities
and unit severities that are signif-
cantly different from their original
design points. This can lead to inef-
fcient operation and decrease
proftability. This article will focus
on several solutions involving cata-
lysts that reforming unit operators
can utilise to improve their
proftability.
Evaluating current catalyst
performance to determine when a
changeout is warranted is a critical
component to maintaining profta-
ble operations in reforming units.
Once a changeout is justifed, deter-
mining which catalyst features are
able to provide the most proftable
operations becomes important.
Catalyst changeout criteria
The frst step in evaluating how
catalysts can improve the proftabil-
ity of a reforming unit is to
determine when a catalyst
changeout will be required. In UOP
CCR Platforming units, it is possi-
ble to change the catalyst on the
fy (without needing to shut down
the reactor section to unload cata-
lyst), so a changeout can be
performed at virtually any time. It
is sometimes desirable to change
the catalyst during a scheduled
turnaround, however, since this
will allow for a thorough inspection
and cleaning of the reactor inter-
nals. In fxed-bed reforming units,
catalyst changeouts are conducted
during catalyst regeneration,
although the regeneration can be
abbreviated if all of the catalyst is
being changed out.
Each reforming unit operator will
have a different economic situation
to evaluate when contemplating a
catalyst changeout. However, there
are several factors that all operators
should consider.
Higher performance catalyst
available
In some cases a changeout can be
justifed even if the existing catalyst
is still in good condition. If the
increased performance (increased
yields, ability to process more feed
or to run to a higher severity)
results in an acceptable economic
payout period, catalyst replacement
can be considered at any time. Most
operators typically wait until the
existing catalyst performance has
declined due to some factor, as
described below, before changing
the catalyst, however.
Low catalyst surface area
Chloride is injected into the reform-
ing unit at prescribed rates to reach
a target level of chloride on the
catalyst. Controlling the chloride
level on the catalyst is very impor-
tant, since chloride catalyses
important reforming reactions. Too
much chloride on the catalyst can
lead to excessive cracking, which
reduces the yields of desired prod-
ucts. Reforming catalysts use
gamma-phase alumina as their
base. The gamma alumina in fresh
reforming catalyst has a high
surface area (in some cases,
upwards of 200 m
2
/g), which
allows the catalyst to retain chloride
well. Each time the catalyst is
regenerated, a small amount of
surface area is lost. Since chloride
retention on the catalyst is propor-
tional to surface area, taking care to
regenerate the catalyst effciently
can help to minimise the surface
area loss and maintain good chlo-
ride retention of the catalyst. The
higher the catalyst surface area, the
easier it also is to disperse the
metals on the catalyst during the
regeneration procedure.
It is essential to have good metals
dispersion on the catalyst to allow
the metals to effectively catalyse
reforming reactions. As the surface
area on the catalyst slowly declines
over time, it becomes increasingly
diffcult to keep chloride on the
catalyst at the appropriate level and
to keep the metals on the catalyst
well dispersed. At some point in
time, catalyst performance may be
affected, and a catalyst changeout
may become warranted. Some
customers have been able to oper-
ate for extended periods with low
surface area levels (near 120 m
2
/g);
however, most customers do change
uop.indd 2 9/12/11 14:38:01
catalyst. Other contaminants such
as fuoride affect the acid function-
ality of the reforming catalyst.
Corrosion products from within the
reforming unit such as iron will
also accumulate on the catalyst,
which can affect the pore structure
of the alumina base and inhibit
reforming reactions from occurring
properly. Various metals levels can
build gradually over time on the
reforming catalyst, or very quickly
if the upstream NHT catalyst
allows metals breakthrough to the
reforming unit. Metals contamina-
tion can become so severe that
signifcant performance debits are
seen, sometimes requiring catalyst
changeouts.
A best practice is to have the cata-
lyst supplier periodically monitor
the reforming catalysts condition
to track metals contamination over
time. This can alert an operator to a
gradual or sudden increase of
certain metals so corrective action
can be taken, hopefully before cata-
lyst replacement becomes necessary.
The catalyst analytical service
program offered by UOP for users
of its Platforming catalysts (for both
CCR and Fixed-Bed Platforming
catalysts) does routinely test for
metals contamination.
Convenience
In some cases, catalyst is changed
out in conjunction with a planned
turnaround. If CCR reforming unit
reactors are unloaded for reactor
internals inspection, it can be risky
to reload the existing catalyst. This
is because a highly coked type of
catalyst known as heel catalyst is
unloaded along with normal cata-
lyst. Care must be taken to
segregate heel catalyst from normal
catalyst and not allow it to be
reloaded into the reactors after the
inspection is completed. This is
because it is very diffcult to
successfully burn the coke from
heel catalyst without damaging
catalyst or equipment in the regen-
eration section. So some CCR
reforming unit operators avoid this
risk by reloading new catalyst into
the reactors after a reactor inspec-
tion, especially if the existing
catalyst does show signs of
performance decline.
Improved catalyst selectivity
In reforming, catalyst selectivity is
a relative measure of the amount of
desired products (C
5
+ reformate
and hydrogen) made with a
constant feed quantity and quality
and a constant conversion level
(reformate octane or aromatics
content). A catalyst with high selec-
tivity will produce a greater yield
of desired products than a catalyst
with low selectivity. Maximising
catalyst selectivity is critical for
reforming operators, since high
selectivity will lead to high yields
of high-value desired products and
low yields of low-value undesired
products (methane, ethane and
LPG).
Catalyst selectivity can be
improved somewhat by reducing
the chloride content of the reform-
ing catalyst. This is because
acid-catalysed cracking reactions,
which cause reduced selectivity, are
minimised with low catalyst chlo-
ride levels. However, there are
limitations as to how far the cata-
lyst chloride level can be dropped.
Reforming unit operators who
desire maximum yields of desired
products should consider choosing
a high-selectivity catalyst for their
next changeout.
Operators who are running at
low severity and/or low through-
put should target maximising the
selectivity of their reforming cata-
lyst in order to maximise the
proftability of the reforming unit.
Even small changes in selectivity
can have a large impact on the prof-
itability of a reforming unit. It is
not uncommon for the economic
payout for switching to a new cata-
lyst to be less than one year.
Reforming unit operators should
track their catalyst selectivity over
time (generally by comparing the
actual yields to predicted yields for
a given feed and severity) in order
to ensure that catalyst selectivity
remains as high as possible.
In fxed-bed reforming, modern
catalysts may use a promoter metal
in addition to the standard plati-
num and rhenium in order to
maximise catalyst selectivity. UOPs
newest Fixed-Bed Platforming cata-
lysts, R-98 and R-500, employ
proprietary promoters to boost
selectivity and maximise proftabil-
ity. R-98 was introduced in 2005
and is currently loaded in more
than 30 fxed-bed reforming units
throughout the world. R-500 was
introduced in 2010 and is in
commercial operation in several
units. In certain instances, non-
promoted catalysts such as UOPs
R-86 can provide high selectivity as
well. To date, R-86 has been loaded
into more than 100 fxed-bed
reforming units throughout the
world since its introduction in 2001.
UOPs R-56 catalyst, which has
been loaded in more than 150 units
since its inception in 1992, is still
used today for customers who
desire a particularly robust catalyst
that can perform well despite a
relatively high concentration of feed
contaminants. UOP can perform
yield estimates to evaluate how
catalysts will perform under certain
conditions in order to help our
customers decide which catalyst
choice is right.
In CCR reforming, promoter
metals other than the traditional
platinum and tin may also be used
on the catalyst in order to boost
selectivity. In certain cases (generally
when the feed has a low paraffn
content or the desired severity is
low), the promoter(s) do not boost
the catalyst selectivity by a large
amount, so traditional non-promoted
catalysts can be used. UOP has done
extensive research on the usage of
promoters other than platinum and
tin in CCR reforming catalysis.
Table 1
Name Year Introduced Relative density Promoter? Comment?
R-56 1992 High No Robust, high contaminant tolerance
R-86 2001 Low No Extensive experience, low base fll cost
R-98 2005 Low Yes High selectivity, low metals fll cost
R-500 2010 High Yes High activity, stability, selectivity
UOP Fixed-Bed Platforming catalysts
Table 1
uop.indd 3 9/12/11 14:38:11
Platforming catalyst in 2010. R-500
has a very high catalyst activity,
with more than 10F better activity
than any of UOPs other Fixed-Bed
Platforming catalysts. Better catalyst
activity translates to lower start-of-
run (SOR) reactor temperatures for
each cycle of a fxed-bed reforming
unit. Reduced SOR temperature
requirements can help to reduce
fuel fring or to extend cycle lengths
for those customers whose cycle
lengths are dictated by reaching
maximum reactor temperatures or
fred heater limitations. A US
refner who loaded R-500 in late
2010 reports that the activity of R-
500 is ~15F better at SOR than the
previous competitors catalyst that
had been loaded in the unit for
approximately one year. The R-500
catalyst has successfully undergone
regeneration and returned to start-
ing activity levels.
Catalyst activity is also an impor-
tant factor to consider when
evaluating CCR reforming catalysts.
Units running at high throughput
and/or high severity can be near
mechanical design temperature
limitations or heater limitations
(fuel fring limitations, heater tube
wall or bridgewall limitations, etc).
In those situations, using a high-
activity catalyst is of paramount
importance so that throughput and
severity targets can be maintained.
When a high-activity catalyst is
desired, UOP normally recom-
mends its R-264 high-density or
R-234 low-density catalyst, since
these catalysts offer good selectivity
at the highest possible activity.

Options for improving reliability
While many reforming units,
especially CCR reforming units,
have been commissioned in the
past two decades, there are a very
large number of fxed-bed and CCR
reforming units operating today
that have been in service for several
decades. Reliability has become an
increasingly important issue for
reforming units as operators strive
to keep units on stream for longer
periods and gain a competitive edge.
Reforming unit operators should
begin thinking about reliability as
soon as a new unit is commissioned
to help ensure long equipment life
While some promoters can be bene-
fcial to maximise catalyst selectivity,
the use of such promoters must be
balanced against other factors such
as the ability to maintain acceptable
catalyst activity over the life of the
catalyst.
UOPs newest CCR Platforming
catalysts, R-254 and R-284, do
contain a proprietary promoter to
increase catalyst selectivity. These
new catalysts build upon the
successful performance of UOPs R-
274 catalyst, which uses the same
proven promoter as these new cata-
lysts. R-274 has been loaded in
more than 15 units worldwide to
provide superior selectivity. R-254,
which modifes the relative metals
levels of platinum, tin and the
proprietary promoter relative to R-
274, has been commercialised in
early 2011 in a UOP CCR
Platforming unit in the US.
Additional loads have either come
on-stream or are in the process of
starting up. The adjustment in
metals content for R-254 allows for
the superior selectivity seen in R-
274 with a signifcant improvement
in catalytic activity. This allows R-
254 to be considered for a wider
variety of applications than was
possible for R-274. High-density R-
284 is also available to deliver the
absolute highest selectivity of any
UOP CCR Platforming catalyst
while maintaining high catalyst
activity. UOPs non-promoted CCR
Platforming catalysts such as R-264
and R-234 can also deliver good
catalyst selectivity with even higher
levels of catalyst activity. Table 2
shows a comparison of the CCR
Platforming catalysts from UOP.

Improved catalyst activity
In reforming, catalyst activity is a
relative measure of the reactor
temperature required to reach a
certain conversion level (reformate
octane or aromatics content). With
constant feed quantity and quality,
a catalyst with higher activity can
reach the desired conversion level
at lower reactor temperatures than
a catalyst with lower activity at
constant operating conditions.
Catalyst activity becomes very
important in high-severity opera-
tions, since the reforming unit
heaters are limited in the amount of
heat they can produce and there are
metallurgical temperature limits in
the reactor circuit. If the desired
production rate is also being
pushed, high-activity catalyst
becomes very important too, since
an increased feed rate requires
more temperature to reach a
constant conversion level.
Catalyst activity can be improved
slightly for an existing catalyst by
increasing the amount of chloride
on the catalyst, since higher chlo-
ride levels on the catalyst raise the
catalyst activity. However, high
catalyst chloride levels also decrease
the selectivity to desired products.
So there is a limit as to how much
the chloride can be raised on a cata-
lyst to improve activity. Reforming
unit operators who are activity
limited and who desire to be able
to process more feed to a constant
conversion level or the same feed to
a higher conversion level should
consider a change to a higher activ-
ity catalyst. If there is an ability to
process more feed or increase the
severity of a reforming unit, opera-
tors should take advantage of this
since both scenarios would cause
an increase in the total number of
octane barrels of reformate
produced.
In fxed-bed reforming, UOP
introduced R-500 Fixed-Bed
Name Year Introduced Relative density Promoter? Comments
R-234 2000 Low No Extensive experience, low fll cost
R-254 2010 Low Yes High selectivity, good activity
R-262 2007 High No High contaminant tolerance
R-264 2004 High No Highest activity, high selectivity
R-274 2002 Low Yes High selectivity
R-284 2010 High Yes Highest selectivity
UOP CCR Platforming catalysts
Table 2
uop.indd 4 9/12/11 14:38:23
www.ptqenquiry.com
Dont miss your industrys most
important gathering of the year!
Manchester Grand Hyatt Hotel
San Diego, California
March 11 13, 2012
In 2012, were changing our
name from NPRA to AFPM,
American Fuel & Petrochemical
Manufacturers to better describe
who we are and what we do.
And you can still count on us
to bring you the most compre-
hensive conference program for
the refning and petrochemical
industries.
SERVING YOU
wItH PRIDE
tHE 2012 AFPM (NPRA)
ANNUAl MEEtING
This years program has
something for everyone
from process and operations
engineers to senior manage-
ment. Keynote sessions
feature top government
offcials and corporate CEOs.
Breakouts cover nearly every
facet of refning technology.
And networking opportunities
abound at our receptions
and affliate-hosted
events. Help us celebrate
our new beginning.
Register at www.afpm.org or
www.npra.org.
afpm.org
afpm.indd 1 13/12/11 13:17:15
and stable production of reformate
and hydrogen. This section will focus
on catalyst solutions that reforming
unit operators can utilise to improve
their reforming unit reliability.
Proper care of the existing cata-
lyst or a changeout to a new catalyst
can also help improve reforming
unit reliability, as discussed below.
Sound regeneration practices
One of the most important factors
in maintaining the overall reliability
of reforming catalyst for both CCR
and fxed-bed applications is to
practise sound regeneration tech-
niques. Catalyst damage can easily
occur during catalyst regeneration
due to the high temperatures that
can occur during the carbon burn
phase of the regeneration, and cata-
lyst life can by dramatically
shortened if the damage becomes
excessive. Other steps during the
regeneration process, such as oxy-
chlorination and reduction, also
play a vital role in determining the
overall performance of the catalyst
in the reforming unit. Optimising
each regeneration step can help to
ensure the reforming catalyst will
reliably perform for many regenera-
tion cycles. UOP Platforming unit
operators can consult their General
Operating Manuals or contact UOP
for more details on effective catalyst
regeneration procedures.
Improved catalyst stability
In reforming, catalyst stability is
defned as the tendency of a catalyst
to form coke under a certain set of
operating conditions. Catalysts with
high stability make less overall coke
at constant conditions than catalysts
with low stability. Catalyst coke
make is also proportional to catalyst
surface area, so catalysts with higher
surface areas will make more coke
than catalysts with lower surface
areas. This is an important factor to
remember when changing catalysts,
since the catalyst surface area is
signifcantly higher for fresh catalyst
after a catalyst reload.
In CCR reforming, high catalyst
stability is generally desired to mini-
mise the coke made on the catalyst
in the reactor section. While some
CCR reforming units today struggle
with making enough coke to
maintain constant regeneration
operations, it is still widely recog-
nised that CCR reforming catalysts
should have a high level of stability.
This is so units can easily catch up
from occasional downtime in the
regenerator section without sacrifc-
ing severity of operation in the
reactor section.
It is normally understood that
issues with making enough coke on
the catalyst in the reactor section
should be dealt with by modifying
process conditions in the reactor
section. Methods to increase the
catalyst coke make include decreas-
ing the unit pressure, reducing the
hydrogen-to-hydrocarbon ratio or
running feed to the unit with an
increased ASTM D86 end point. As
discussed above, modifcations can
be made to the regeneration section
to allow for more or less coke burn-
ing in the regeneration section as
required. All modern UOP CCR
Platforming catalysts have excellent
catalyst stability to enhance the fex-
ibility of operations in CCR
Platforming units.
In fxed-bed reforming, high cata-
lyst stability is generally desired in
order to maximise the achievable
cycle length (the period of time in
between catalyst regenerations) at a
constant set of operating conditions.
UOPs R-500 Fixed-Bed Platforming
catalyst offers ~25% better catalyst
stability than other commercially
available UOP Fixed-Bed Platforming
catalysts. This means that units can
run to cycle lengths that are at least
25% longer than existing cycles at
constant conditions. If the cycle
length is kept at historical levels,
higher severity operation (increased
feed rate, decreased feed quality,
increased product severity, reduced
reactor pressure, etc) can be achieved
while keeping the cycle length
constant. If the cycle length and all
operating conditions are kept
constant, the yield decline seen over
the course of the fxed cycle is
decreased, which increases the aver-
age yields seen over the course of
the cycle. This combination of poten-
tial advantages makes R-500 a very
fexible catalyst that can address
many needs for just about any fxed-
bed reforming unit operator. Other
UOP Fixed-Bed Platforming
catalysts such as R-56, R-86 and R-98
also offer high catalyst stability and
allow for fexible operations in fxed-
bed reforming units.
Reduced fnes make
In CCR reforming, catalyst circu-
lates in a closed loop from the
reactor section to the regeneration
section and back. As the catalyst
circulates, some fnite amount of
attrition occurs. Catalyst attrition is
undesirable for several reasons.
First, catalyst attrition produces
catalyst dust and other fnes that
may plug up reactor or regenerator
internals. This pluggage can lead to
high pressure drop in the reactors
or diffculties effectively burning
the coke off the catalyst in the
regeneration section. Catalyst attri-
tion also causes a loss in the
circulating inventory of catalyst, so
make-up requirements multiply
with increased attrition.
In a CCR reforming unit, increases
in catalyst attrition over time can be
caused by changes in the mechanical
equipment in the circulating cata-
lysts path or by changes to the
strength of the catalyst itself. The
strength of the catalyst can be
compromised if the catalyst is
subject to abnormally high tempera-
tures, where the alumina phase of
the catalyst base changes from its
normal gamma state to undesirable
states such as theta or alpha. Catalyst
attrition should be monitored over
time so changes to the attrition rate
can be quickly detected and correc-
tive action can be taken.
Higher platinum-containing catalysts
Reforming catalysts perform best
when feed contaminants, such as
sulphur, are kept below prescribed
values (normally 0.5 wppm of the
feed). Further, reforming catalysts
also perform best when the metals
on the catalyst are well dispersed
during catalyst regeneration. For
units that have issues with main-
taining low feed sulphur content or
for units that have a diffcult time
consistently dispersing metals on
the catalyst during regeneration,
UOP has developed catalysts
with higher-than-normal platinum
content. The extra platinum on
these catalysts allows for suffcient
uop.indd 5 9/12/11 14:38:37
platinum to be available to catalyse
reactions even if some of the plati-
num is unavailable due to poor
dispersion. These catalysts with
higher platinum contents also have
an optimised platinum-to-tin ratio
in order to ensure good catalyst
performance with minimal side
effects, such as high coke make.
For these situations, UOPs
primary CCR Platforming catalyst
of choice is R-262, which contains a
20% higher platinum loading than
in R-264. R-262 is recommended for
some older generation CCR
Platforming units and is typically
also recommended when UOP cata-
lyst is used in CCR reforming units
designed by others. R-262 is also
being used by several customers
with relatively high sulphur levels
in the feed to their reforming units.
For fxed-bed reforming, high-
density catalysts such as UOPs
R-56 and R-500 contain higher
amount of platinum per unit
volume than its lower density cata-
lysts. These catalysts are therefore
recommended to customers who
have diffculties successfully regen-
erating their catalyst or have issues
with maintaining feed contaminants
at prescribed levels.
Conclusion
While growth in gasoline demand
has been recently more moderate,
reformate remains an important
component for use as a high octane
blending component in gasoline and
as an aromatics-rich petrochemical
feedstock. In addition to the produc-
tion of liquids, reforming is very
important for hydrogen production
to feed other process units. Global
CCR reforming capacity additions
have been approximately 4.5%, with
higher growth rates in emerging
regions such as China and India,
and fat-to-declining growth in
developed regions such as the US
and Europe. Installed capacity for
fxed-bed reforming is on the decline
via unit retirement. Virtually every
reforming unit operator faces multi-
ple challenges in todays climate
related to technology, operations
and proftability.
There are many catalyst solutions
to manage the up-down world of
reforming today. Capabilities and
enablers a refner should consider
when selecting a technology
provider to partner with to identify
the optimal economic solution for
addressing future processing needs
include:
Full understanding of the
constraints within the reforming
unit, both process and catalyst
Comprehensive knowledge of
unit functionality, operating condi-
tions and the variables that affect
unit performance
Knowledge, experience and abil-
ity to apply a broad portfolio of
catalyst choices to attain the desired
processing and fnancial objectives.
This article is based on a paper given at the
NPRA Annual Meeting, 2022 March 2011, San
Antonio, Texas.
The frst half of this article was published in
Revamps 2011.
Steve Metro is Global Business Manager
inHoneywell UOPs Catalyst, Adsorbents &
Specialties business unit. He has been with
UOP for over 25 years, holding positions in
R&D, manufacturing, engineering, product
line management and marketing. He holds
a BS in chemistry from Northeastern Illinois
University.
Bryan Glover is Business Leader for Gasoline
Technologies in Honeywell UOPs Process
Technology and Equipment business unit.
He has been with UOP for 25 years, holding
positions in R&D and technical service. He
holds a degree in chemical engineering from
Michigan Technological University and an MBA
from the University of Chicago.
Anthony Poparad is Senior Manager, Naphtha
Catalyst Sales Support, in Honeywell UOPs
Catalyst, Adsorbents & Specialties business
unit. He has been with UOP for 21 years,
holding positions in R&D, engineering, technical
services, sales and sales support. He holds a BS
in chemical engineering from Rose-Hulman
Institute of Technology, Indiana.
Beatrix Ellis is Services Product Line Manager
for Honeywell UOP. She has been with UOP for
15 years, holding positions in R&D, engineering,
feld, technical and regional services, sales
support and product management. She holds
a degree in chemical and process engineering
from Newcastle University, UK.
viscosity, providing engineers with real-time informa-
tion on oil quality.
Each viscometer is mounted on a skid where the
refner mixes gas and lube oil for a screw compressor.
When the gas/oil mixture leaves the compressor, it is
recycled. Three separation flters on the compressor
skid remove 9798% of the gas from the oil. Over
time, the remaining 23% of the gas can cause the
lube oil to lose its lubricity or lubrication quantities
and, as this happens, the viscosity of the oil drops.
When the oil viscosity drops to a certain level, the oil
must be changed to protect the equipment and keep
the process operating time on target. The installation
comprises Cambridge Viscosity VISCOpro 1600
viscometers, which are ftted with the suppliers 392
process sensors and are Class 1 Div 1 Group B, C and
D certifed.
According to the installer, this precautionary
maintenance operation saves on machinery
failures, downtime and maintenance costs for the
refnery.
and meets all specifcations for fight, including a
freeze point at -47C maximum and a fash point at
3C minimum.
Honeywell has produced more than 700 000 gallons
of Honeywell Green Jet Fuel from sources such as
camelina, jatropha and algae for use in commercial
and military testing. In each of the biofuel fights
conducted to date, Green Jet Fuel has met all specif-
cations for military and commercial fights without
any modifcation to the aircraft or engines.
Flights powered by Green Jet Fuel have required
Honeywell to work with the US Department of
Defense, Boeing, Airbus, Honeywell Aerospace, Rolls-
Royce, GE and airlines including Continental, Air
New Zealand, KLM, Interjet, TAM and Japan Airlines.
The fuel has powered 19 fights to date. Flights by the
US Navy and US Air Force that were powered by the
biofuel include those by an F/A-18, which was the
frst aircraft to break the sound barrier while fying on
a 50:50 blend of biofuel. The Air Force has already
certifed the F-16 and the C-17 for use and plans to
have 100% of its feet certifed by 2013.
A US-based oil company with refnery installations in
North and South America is combating machinery
failures, downtime and maintenance labour costs by
installing viscometers. The aim is to monitor oil
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case studies copy 4.indd 2 14/9/11 13:47:19
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New crude oil basket for hydrogen savings
I
n the world of petroleum refning,
optimal use of hydrogen is the
key to maximising a refners
proftability. In fact, the presence of
hydrogen in petroleum oils and/or
fractions should decide the actual
value of hydrocarbons. The def-
ciency of hydrogen in crude oil is
normally compensated by the addi-
tion of hydrogen in hydroprocessing
units in order to meet stringent fuel
specifcations. In this scenario, refn-
ers need to understand the balance
of hydrogen and carbon for achiev-
ing the best margin. The hydrogen
content of crude oils and their
straight-run products for low-API
and high-sulphur, and for high-API
and low-sulphur, crude oils have
been studied (see Figure 1).
1
The
hydrogen content of distillates is
higher than crude oil and has a
higher monetary value than crude
oil. On the other hand, the hydrogen
content of residues is lower, as is
their value.
This directly implies that hydro-
gen addition to upgrade crude oil
to produce valuable distillates will
result in increased product value,
but at the cost of additional hydro-
gen. Therefore, it is essential to
characterise feedstock crude oils for
hydrogen content so that excessive
hydrogen addition is not added on
to the cost of crude processing.
Crude oils mainly contain carbon,
hydrogen and many undesirable
components. In petroleum refning,
maximum effort goes into dealing
with impurities, which results in
higher processing costs. The cost of
crude oil amounts to 8090% of the
total cost to a refner; hence, the
selection of an appropriate crude oil
basket is of the highest importance.
2

The processing requirements of opportunity crudes are considered for the
operations of the Indian refneries
Rajeev KumaR, PRashanT PaRIhaR and RavI K voolaPallI
Corporate R&D Centre, Bharat Petroleum Corporation Ltd, India
In the current refning climate,
processing opportunity crude oils
and meeting critical product speci-
fcations such as Euro III, IV and V
is the real challenge for improving
refnery margins. As the word
hydrocarbon suggests, only
hydrogen and carbon are the desir-
able components in their different
forms. All other components, in any
structural or free form, are undesir-
able impurities. These impurities
imbalance the hydrogen content of
petroleum and are colloquially
known as hydrogen guzzlers in
the course of hydroprocessing to
meet product specifcations.
3
Vacuum gas oils (VGO) derived
from high-sulphur and low-API
crude oils consume lots of hydro-
gen during hydroprocessing and,
thus, it results in exorbitant cost. In
order to minimise hydrogen
consumption in the hydrocracking
unit, a new crude basket has been
proposed. The characteristics of
VGO, such as aromatic and sulphur
content and other impurities that
consume maximum hydrogen for
saturation, are minimised in the
new crude basket. These properties
also affect catalyst activity and, in
turn, the run length, which restricts
the throughput capacity of the
hydrocracking unit, with hydrogen
unit capacity being constant. The
methodology for hydrogen
consumption is based on the
12
18
16
14
10
8
6
4
2
Crude oils LPG Naphtha Kero. Gas oil LR VR
H
y
d
r
o
g
e
n

c
o
n
t
e
n
t
,

w
t
%
0
Low API, high S
High API, low S
Figure 1 Hydrogen content of crude oils and products from (LA, HS) and (HA, LS)
vacuum gas oils
derived from
high-sulphur and
low-aPI crude oils
consume lots of
hydrogen during
hydroprocessing
bpcl.indd 1 13/12/11 13:16:13
units.
5
The main culprits among
poor characteristics of VGO are
aromatics, sulphur and other impu-
rities such as vanadium, nickel and
nitrogen, which either consume
hydrogen for saturation and/or are
a serious threat to catalyst life, run
length and unit capacity. Thus,
there is a need to select new crude
oils, which can minimise hydrogen
consumption.
To reduce hydrogen consump-
tion, a superior-quality VGO needs
to be sourced, perhaps from costlier
crude oils (high API, low sulphur).
It is a challenge to meet the
requirement of current trends and
the processing opportunity crude
oils to minimise hydrogen
consumption in hydroprocessing.
In order to save hydrogen in
hydroprocessing, a study has been
carried out at the Corporate R&D
centre, BPCL, for the selection of a
basket of crude oils. The character-
istics of VGO are the basis for
estimating hydrogen savings in the
hydrocracker. The present approach
to selecting a crude basket is based
on the cost of processing VGO in
the hydrocracker. For the present
study, operation of the hydroc-
racker at a refnery has been
considered for selection of a new
crude basket. The cost savings
derived are in comparison with the
processing of Arab Mix crude oil as
a base case. Since the cost of new
crude oils is not fxed, a detailed
techno-economic study would be
required before selecting them for
processing in the refnery.
Methodology for estimation of
hydrogen consumption
With regard to the fundamentals of
the hydrocracking process and the
reaction mechanism for saturation
reactions, the characteristics of VGO
are the key factors for hydrogen
consumption. The controlling varia-
bles are carbon-to-hydrogen ratio,
aromatics content, and sulphur,
nitrogen and metals levels.
Screening of the crude oil basket
was carried out by considering the
various constraints related to the
characteristics of VGO. The key
constraints are shown in Table 1.
To estimate hydrogen consump-
tion, the balance of carbon,
balance of carbon, hydrogen and
impurities to screen the new crude
oils in comparison with the high-
sulphur crude oils typically
processed as the base case for esti-
mating their benefts. As the costs
of crude oils and distillate yields
are the most important variables for
achieving overall beneft, a detailed
techno-economic study is essential.
Processing low-API and high-sulphur
crude oils
The world over, processing oppor-
tunity crude oils is the current
refning trend for targeting higher
refning margins. These crude oils
are available at a lower cost with a
compromise on factors such as API,
sulphur content, TAN, and others.
These crude oils produce inferior-
quality atmospheric, vacuum gas
oil and lots of residues that require
either additional refning processes
and/or evacuation at a lower cost.
Hydroprocessing such streams
consumes large quantities of hydro-
gen at a high cost.
4
Although it is known that the cost
of crude oils has a large infuence
on the economics of the refning
business, the cheaper crude oils add
lots of processing costs in order to
meet the critical product specifca-
tions of Euro III, IV and V product
grades. This results in a squeezing
of benefts and may lead to a
reversal in the trend of processing
opportunity crude oils.
Since opportunity crude oils not
only infuence processing costs
because of their defciency in
hydrogen but also produce lots of
residues, refners are forced to sell
fuel oils with additional distillate as
cutter. Other, secondary units such
as fuid catalytic cracking units
suffer feedstock availability and
frequently have to run at lower
capacity as a result of the high resi-
due yields obtained from cheaper
crude oils. And the distillates
produced from cheaper crude oils
consume large quantities of hydro-
gen during hydroprocessing, which
means further additional cost.
Therefore, the increasing criticality
of product specifcations requires
selection of a new crude oil basket
for minimising processing costs
through hydrogen savings. In the
present study, the selection of a
new crude oil basket has been
carried out to enlarge a refnerys
existing crude basket.
The VGO drawn from low-API,
high-sulphur crude oils is streamed
towards hydroprocessing, which
leads to high levels of hydrogen
consumption. The characteristics of
VGO as a feedstock are the key
factors infuencing hydrogen
consumption and so it is essential
to evaluate them. The characteris-
tics of VGO are mainly infuenced
by vacuum tower operations,
endpoints and types of crude oils
processed in crude distillation
VGO (360-565) Min/Max Arab Mix crude
Density, Gm/cm
3
0.8352-0.9050 0.931
Sulphur, wt% <2.0 2.85
Paraffns, vol% >55.0 47.78
Aromatics, vol% <25 25.30
Total N
2
, ppm <1000 1200
V, ppm <0.5 1.85*
Ni, ppm <0.5 1.85*
* total metals
VGO characteristics for hydrogen savings and base case data
Table 1
The world over,
processing
opportunity crude
oils is the current
refning trend for
targeting high
refning margins
bpcl.indd 2 9/12/11 15:01:16
hydrogen and impurities was
considered across the hydrocracker
unit when upgrading VGO to
superior-quality distillates.
The following assumptions are
made for the selection of a crude
basket for hydrogen savings:
Hydrogen savings are solely
based on varying VGO quality with
respect to the base case crude
The cut point for VGO has been
dened in the range 360565C
The model is based on the hydro-
processing units capacity
All components other than carbon
and hydrogen are considered as
impurities for the purpose of
calculation
The nal distillate properties meet
product specications
The cost of hydrogen is $4440/t.
Hydrocracker unit conguration
Typically, renery congurations
are reliant on the capacity of the
primary units and, more impor-
tantly, on the types of crude oils
processed. In recent advances in
secondary processing, hydrocracker
units are being set up to accommo-
date heavy/vacuum gasoils for
upgrading, so the capacity of these
units depends on the yield proles
of the crude oil. However, the qual-
ities of the feedstock are also found
to be key constraints to the capacity
of the units. In order to operate the
hydrocracker unit at full capacity,
the appropriate selection of crude
oil and crude oil blends is essential.
The present study has been carried
out for the selection of a new crude
basket for BPCLs reneries.
The hydrocracker at Mumbai
renery is a 1.75 million t/y unit
licensed by Chevron Lummus
Global. It was constructed as part
of a renery modernisation project
(see Figure 2). The hydrocracker is
a two-stage unit that has been
designed to produce middle distil-
late fuel of superior quality. The
present study provides scope for
accommodating streams such as
FCC cycle oils (high on olens and
aromatics) along with superior-
quality VGO sourced from the new
crude basket as hydrocracker feed.
Also, the crudes oils that minimise
hydrogen consumption in the
hydrocracking unit should produce
Feed
+ H
2
H
2
Quench Quench
Unconverted oil
Hydrogen
recovery
section
First stage
reactors
Second stage
reactor
Separator
Fractionator
LPG
Naphtha
Middle
distillates
UCO to
LOBS
Figure 2 Block diagram of conguration of hydrocracker unit
1.5
2.5
2.0
1.0
0.5
0.83 0.84 0.85 0.86 0.87 0.88 0.89 0.90 0.91
H
2

c
o
n
s
u
m
p
t
i
o
n
,

w
t
%
VGO density, gm/cm
3
0.0
Figure 3 Variation in hydrogen consumption with VGO density
1.5
2.5
2.0
1.0
0.5
6.4 6.5 6.6 6.7 6.8 6.9 7.0 7.1
H
2

c
o
n
s
u
m
p
t
i
o
n
,

w
t
%
C/H
0.0
Figure 4 Variation in hydrogen consumption with carbon-to-hydrogen ratio
bpcl.indd 3 9/12/11 15:01:30
Hydrogen consumption study
VGO derived from the vacuum
tower varies in quality due to the
types of crude oils processed at the
primary units. Quality also depends
on vacuum tower operation. The
current trend towards processing
opportunity crude oils that contain
many impurities results in an accu-
mulation of these impurities at high
percentages in the heavier petro-
leum fractions. This gives rise to a
lot of additional costs for hydro-
processing to meet fnal product
specifcations at the secondary
units. In addition, the cheaper crude
oils produce a lot of residues, some-
times more than 25 wt%, which
needs to be evacuated.
1
In this
scenario, it is essential to have a
thorough understanding of the
feedstock and any additional costs
in order not to reverse the trend
towards processing cheaper crude
oils. However, the entry of resid-
uum upgrading processes such as
delayed coking and solvent deas-
phalting mean that the negative
issues involved in processing
opportunity crudes may be compen-
sated through additional distillate
yields.
In the present study, the aim is to
achieve hydrogen savings with
respect to variations in VGO qual-
ity in the boiling range 360565C.
VGO quality has been studied in
terms of hydrogen defciency and
the presence of contaminants that
result in hydrogen consumption.
Variations in hydrogen consump-
tion with VGO density and
carbon-to-hydrogen ratio are shown
in Figures 3 and 4. It has been
observed that higher VGO density
results in more hydrogen consump-
tion. In a similar way, a higher
carbon-hydrogen ratio means a
lower hydrogen content in the
VGO, which will therefore consume
more hydrogen during processing.
The effect of the level of impurities
on hydrogen consumption is shown
in Figure 5. The types of crude oils
processed are a very important
factor in understanding hydrogen
consumption and processing diff-
culties. It is also known that sulphur
content and aromatics/aniline point
are critical properties of the feed-
stock in determining the hydrogen
high-quality atmospheric gasoil,
which can further minimise hydro-
gen consumption in the diesel
hydrodesulphurisation unit (with
scope for increasing throughput). It
will also improve the catalyst life
and reduce coke build-up during
the run.
1.5
2.5
2.0
1.0
0.5
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
H
2

c
o
n
s
u
m
p
t
i
o
n
,

w
t
%
Impurities, wt%
0.0
Figure 5 Variation in hydrogen consumption with impurities
1.5
2.5
2.0
1.0
0.5
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
H
2

c
o
n
s
u
m
p
t
i
o
n
,

w
t
%
Sulphur, wt%
0.0
Figure 6 Variation in hydrogen consumption with sulphur
1.5
2.5
2.0
1.0
0.5
85 90 95 100 105 110 115 120 125
H
2

c
o
n
s
u
m
p
t
i
o
n
,

w
t
%
Aniline point, C
0.0
Figure 7 Variation in hydrogen consumption with aniline point
bpcl.indd 4 9/12/11 15:01:44
Table3
consumption required for upgrad-
ing VGO to distillates. Variations in
hydrogen consumption with
sulphur and aniline point are
shown in Figures 6 and 7 respec-
tively. As the graphs show, a low
sulphur and high aniline content in
feedstock are found to be more suit-
able for hydrogen savings.
A new crude oil basket
A new crude oil basket is required
for hydrogen savings in hydro-
processing units. In order to
minimise hydrogen consumption,
the principal hydrogen guzzlers are
identifed. These properties are
density, sulphur, aromatics and
nitrogen. Considering Arab Mix
VGO as a base case for limiting
values of these critical properties,
screening of crude oils has been
accomplished for comparison with
base case VGO hydrocracking.
The approach for estimating
hydrogen consumption for a new
crude oil basket is based on the
hydrogen balance across the hydroc-
racking system. Carbon, hydrogen
and impurities levels have been
considered for the balance, with
specifed assumptions. Data for
crude oils, their origin, VGO
characteristics and potential for
hydrogen savings are shown in
Table 2.
It has been observed that crude
oils with low sulphur and a high
API number are more suitable for
hydrogen savings, which implies
that opportunity crude oils require
higher levels of hydrogen consump-
tion and, thus, an additional cost of
processing. In this scenario, process-
ing opportunity (low-API and
high-sulphur) crude oils for beneft
would be contradictory. However,
the overall distillate yield profle,
residue yields and differential cost
of high-sulphur and low-sulphur
crude oils would be important
decision-making factors for process-
ing these feedstocks. Although the
total processing cost of refning
involves up to only 10% of the
crude cost, the hydrogen cost, resi-
due yields, equipment failure and
downtime due to processing oppor-
tune crude oils may require serious
thought when looking into the
current processing trends. Thus, a
detailed crude evaluation would be
Crude basket Origin Density, SUL, Aromatics, N
2,
H
2
consumption, Savings,
Gm/cm
3
wt% vol% ppm wt% $ million/day
Sahil AbuDhabi 0.9046 1.590 19.62 657 2.23 0.08
Asab AbuDhabi 0.9020 1.630 23.61 548 2.20 0.09
BuHasa AbuDhabi 0.9050 1.450 22.38 673 2.20 0.09
Montrose NorthSea 0.8956 0.372 22.5 640 1.72 0.21
Mubarek Sharjah 0.8887 0.673 20.58 411 1.7 0.21
Duncan NorthSea 0.8964 0.230 20.46 652 1.69 0.22
Djeno Congo 0.8934 0.150 17.05 968 1.63 0.23
Gippsland/Bass Victoria 0.8870 0.167 23.15 366 1.52 0.26
Wyoming Wyoming 0.8786 0.294 6.42 357 1.43 0.28
LucinaMarine Gabon 0.8808 0.054 20.24 991 1.41 0.29
LakeArthur Louisiana 0.8807 0.133 21.4 43.8 1.40 0.29
Minas Indonesia 0.8789 0.106 19.69 675 1.39 0.29
Zueitina Libya 0.8741 0.108 10.56 656 1.31 0.31
Sarir Libya 0.8693 0.180 22.19 621 1.26 0.32
Lufeng Guangdong 0.8668 0.049 13.21 577 1.18 0.34
Sembilang Indonesia 0.8626 0.199 13.6 586 1.17 0.35
NanhaiLight Guangdong 0.8638 0.095 20.4 639 1.16 0.35
Widuri Sumatra 0.8612 0.082 8.01 569 1.11 0.36
Anoa Indonesia 0.8620 0.078 7.99 115 1.11 0.36
NileBlend Sudan 0.8600 0.035 14.23 251 1.07 0.37
CooperBasin Australia 0.8567 0.058 9.69 236 1.02 0.38
Lalang Indonesia 0.8564 0.074 15.66 306 1.03 0.38
Dulang Malaysia 0.8537 0.078 15.93 217 0.98 0.39
Kerapu Sumatra 0.8499 0.038 19.66 247 0.92 0.41
Jackson Australia 0.8437 0.052 15.73 172 0.82 0.43
BuAttifel Libya 0.8402 0.039 6.94 56 0.76 0.45
Altamont Utah 0.8366 0.027 8.03 181 0.71 0.46
ArabMix Saudia 0.9310 2.850 NA 1200 2.56 Base
VGO characteristics of a new crude oil basket for hydrogen savings
essential prior to selecting them for
processing. It will be necessary to
consider how the new crude basket
will ft into existing refnery confg-
urations, including primary and
secondary units, and also into the
current market demands for
products.

Future directions
It would be helpful to understand
the existing crude basket for addi-
tional refning process cost and
benefts. In order to predict the
status of the current crude oil
basket, a crude selection model can
be proposed, which is able to
accommodate all the processing
costs as per refnery confgurations,
such as diesel, VGO, residue evacu-
ations and delayed coker. In this
case, the sensitivity analyses would
also be important for validation of
the trends for uncertainty of hydro-
gen, fuel oils and crude costs.
Conclusions
A new crude oil basket based on
high-API and low-sulphur crude
oils is found to be more suitable for
hydrogen savings during hydro-
Table 2
bpcl.indd 5 9/12/11 15:02:26
processing. This will help to expand
the existing crude oil basket and to
prioritise crude oils for processing.
The new crude oil basket for hydro-
gen savings in the hydrocracking
unit offers scope for increasing
throughput so that hydrogen plant
capacity would not be the limiting
factor. The new crude oil basket
also opens up avenues for improv-
ing the overall performance of FCC
units.
In the current refning climate,
processing more opportunity crudes
and making hydrogen savings is a
contradictory concept. Processing
low-API, high-sulphur crude oils
may not always be benefcial unless
the differential costs of low-sulphur
and high-sulphur crude oils are
large enough.
Acknowledgement
The authors express their thanks to Mr K
V Seshadri, ED (MR/R&D) of BPCL for his
continuous mentoring on research activities,
encouragement and magnanimity. Thanks
to Mr Pranab Kumar Rakshit for being the
frst reader and his valuable inputs. Thanks to
CRDC colleagues for constant appreciation and
support.
References
1 Hand Book on Crude Oil Evaluations, vol 1
& 2, Corporate R&D Centre, Bharat Petroleum
Corporation Ltd., India 2007.
2 Kumar R, Thorat T S, Chithra V, Rathore
V, Peddy V C Rao, Choudary N V, Processing
opportunity crude oils catalytic process
for high-acid crudes, Hydrocarbon World, 4, 2,
6468, 2009.
3 Scherzer J, Gruia A J, Hydrocracking Science
and Technology, Marcel Dekker New York,
1996.
4 Ancheyta J, Snchez S, Rodrguez M A,
Kinetic modeling of hydrocracking of heavy oil
fractions: a review, Catalysis Today, 109, 14,
7692, 2005.
5 Kumar R, Chithra V, Shalini G, Sonal M,
Peddy V C Rao, Choudary N V, Maximization
of VGO through deep-cut distillation, PTQ, Q1,
8791, 2011.
6 US Bureau of standards, Miscellaneous
Publication No. 97 (9.11.1929).
Rajeev Kumar is Deputy Manager (R&D)
with Bharat Petroleum Corporation Ltd., India.
His areas of interest are crude oil processing,
refning processes, modelling, simulation
and optimisation, and process development
for biodiesel and biolubricants production. He
holds a masters in chemical engineering from
Indian Institute of Technology, Kanpur, India.
Prashant Parihar is Deputy Manager (R&D)
with Bharat Petroleum Corporation Ltd., India,
with more than fve years experience in
hydroprocessing and optimisation of refning
processes. He holds a masters in chemical
engineering from Institute of Chemical
Technology, Mumbai.
Ravi K Voolapalli is Chief Manager at Corporate
R&D Centre, Bharat Petroleum Corporation Ltd.,
India, with 21 years research experience and
areas of interest including refnery processes,
coal-to-liquid technologies, modelling,
scale-up and optimisation. He holds a BTech
degree in chemical engineering from Andhra
University, Visakhapatnam, a MTech degree
in chemical engineering from Indian Institute
of Technology, Kanpur and a PhD in chemical
engineering from Imperial College, London.
Email [email protected]
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call for papers 2011.indd 1 13/12/11 16:03:31
bpcl.indd 6 13/12/11 16:05:22
A better view of catalyst activity
Teams of catalyst researchers from
Albemarle Corporation and Utrecht
University, The Netherlands, have
devised a new method that will
increase the ability to visualise the
components of catalysts. Their
research shows that it is possible to
pinpoint the actual active sites in
fuid catalytic cracking (FCC) cata-
lysts without destroying the
catalysts in the process.
Research to develop more eff-
cient FCC catalysts has been limited
to activity measurements, model
studies and analyses of spent cata-
lysts. The tools and methods
developed in this collaboration
enable researchers to study both the
accessibility of active sites as well
as view 3D maps of the active sites
inside the actual catalysts.
To address limited understanding
of the distribution and activity of
individual zeolitic domains at
different life stages of catalysts, the
researchers developed a staining
method to visualise the structure of
zeolite particulates and other FCC
components and constructed
Brnsted acidity map at the single
particle level using fuorescence
microscopy. By applying a statisti-
cal methodology to a series of
catalysts deactivated via industrial
protocols, the teams established a
correlation between Brnsted acid-
ity and cracking activity. They say
that the method has clear
potential for catalyst diagnostics by
determining Brnsted acidity distri-
butions for FCC materials.
Gas treatment for grassroots
Brazil refnery
Petrobras has awarded Haldor
Topse a supply contract covering
two SNOX off-gas treatment
plants. The plants will be installed
at the new RNEST refnery in
Pernambuco, Brazil, and the
contract covers internals for 80 wet
sulphuric acid (WSA) condensers
for the condensation of sulphuric
acid, eight units for acid mist
P
control and a complete acid system.
The plants will clean the off-gases
from three boilers that supply elec-
tricity and steam for internal use in
the refnery. The boilers are fred
with heavy fuel oil and pet coke.
Based on catalytic processes, SNOX
technology converts sulphur diox-
ide to industrial-grade sulphuric
acid and nitrogen oxides to
nitrogen.
In addition to treating the boiler
fue gases, the plants will treat
Claus plant tail gases, amine gases
containing hydrogen sulphide and
gases containing ammonia. The
plants are designed for the possible
elimination of the Claus plants,
which would mean that all sulphur
compounds in the refnery would
be converted to sulphuric acid.
The plants will be installed in
parallel and will each treat up to
650 000 Nm
3
/h. In addition to the
production of sulphuric acid, up to
100 t/h of high-pressure steam will
be exported from the plants to the
refnery steam grid.
The supply of equipment will
continue through 2012 and start-up
is planned for 2013.
Cold climate LNG exceeds
ratings
The worlds northernmost natural
gas liquefaction plant, Hammerfest
LNG on the island of Melkya,
800km north of the Arctic Circle
near Hammerfest in Norway, has
exceeded expectations in perfor-
mance tests and has been rated
with a capacity of up to 109% of
original design capacity. The plant
was designed by Statoil and Linde.
The results of the assessment
show that all performance guaran-
tees related to product quality,
capacity and energy consumption
have been met. In particular, energy
consumption for the liquefaction
service was reduced signifcantly
below the guarantee values. Hence,
the Hammerfest LNG is, according
to the developers, the worlds most
energy-effcient LNG base load
Industry News
plant. It has a capacity of 4.3 million
t/y of LNG and is based on a lique-
faction process, Mixed Fluid
Cascade, jointly developed by
Statoil and Linde, that is optimised
for Arctic conditions. Due to limited
plot space and diffcult conditions
for construction, the plant was
designed to be compact and
modular.
At its heart is the central process
module with a weight of 35 000
tonnes. This huge LNG plant
module was prefabricated in a
Spanish yard as a foating module
and was transported by sea to
Melkya. Hammerfest LNG also
uses a direct seawater cooling
system, which is suitable for Arctic
weather conditions. Carbon dioxide
separated from the process gas is
reinjected into a reservoir under
the seabed and the site has
fareless plant operation. All
main compressors are electrically
driven.
Jazan awards for Axens
Saudi Aramco has awarded Axens
a contract to supply a range of tech-
nologies for its Jazan Refnery &
Terminal Project. The refnery is
scheduled to be commissioned in
December 2016 and will have a
capacity of 400 000 b/d. Axens will
supply units and equipment for
naphtha hydrotreating for feedstock
purifcation; Aromizing CCR
reforming for aromatics production;
a C
5
/C
6
isomerisation unit to
provide a high-octane component
for the gasoline pool; and a
ParamaX complex to produce high-
purity paraxylene and benzene.
These units are designed and
integrated to maximise gasoline
production and the aromatics
throughput for petrochemicals
production.
A Prime-D gas oil desulphurisa-
tion hydrotreater, one of the worlds
largest, will produce diesel with
less than 10 ppm sulphur. The refn-
ery will deliver gasoline and diesel
to meet Euro V specifcations.
ind news copy 10.indd 1 9/12/11 16:26:46
Hindustan Petroleum Corporation Limited (HPCL) is
using Honeywell Process Solutions Mobile Stations to
support its new fuid catalytic cracking unit project in
Mumbai. The Mobile Stations have been introduced to
increase productivity and reduce the operating costs of
standard communications infrastructure supporting the
Rs 900 crore ($200 million) unit by accelerating the
commissioning of different systems and subsystems.
HPCL operates two major refneries in India, which
produce petroleum fuels with a combined annual
output of 14.8 million tonnes. The company previously
experienced delays in commissioning activity associ-
ated with the use of handheld transceivers to
communicate with the control room for operations,
such as transmitter testing, control valve stroke check-
ing, loop checking, determining run indication status
and mapping third-party devices with DCS via the
Modbus messaging protocol. Following the introduc-
tion of mobile operator technology, HPCL was able to
push forwards the schedule, reportedly saving Rs 1.5
crore ($333 000) per day and improving productivity
by 20% during the commissioning phase of the FCC
project. The company has also adopted more feld-
related applications using the same wireless network.
The aim of this wireless technology is to extend the
application of process automation beyond the control
room. Mobile Station is designed to increase access to
critical process information, historical data, graphics
and other functions to feld operations, says Honeywell.
It comprises a group of solutions for relaying control
system information to users operating remotely from
the control room. Its applications include read-only
access over the intranet for multiple users, up to secure
system access for mobile operators. For instance,
Mobile Access for eServer Standard enables device-
independent access to process information, so that
plant data can be viewed directly on a wireless hand-
held device using a web browser. Mobile Access for
eServer Premium provides read-only access to process
information and displays system data from the
Experion system directly on a wireless handheld
Reduce gasoline cutpoint
Venturi steam traps solve condensate
pressure problem
device; this prevents unwanted access to control func-
tions while still viewing live process graphics. Mobile
Access for Station is a fully functioning Experion
process control station on a handheld device; opera-
tional changes are controlled by system permissions
assigned to the operator and handheld device.
You can transport crude oil to a refnery, but you cannot
necessarily make it move. A well-known phenomenon
at oil terminals in cold regions is that crude oil trans-
ported in railway cars can be too stiff to unload. To help
solve this problem of reduced fow characteristics, tech-
nology provider Neste Jacobs which began life as the
engineering department of Finnish refner Neste has
developed an unloading device called Ecoarm. It is a
ready-to-use system that can be used as is or confgured
by combining top-unloading, bottom-unloading or top-
warming technologies.
Traditionally, oil transported by train is unloaded
through valves underneath the tank. The tool used for
this is a base unloading arm with a built-in heating
system. But if bottom unloading is not possible, which
quite often is the case in the Baltic region where Neste
operates, the car must be unloaded from the manhole
on top of the tank. To enable this, it is a time-
consuming and ineffcient operation during the winter
to warm the tank from the outside with, for example,
hot steam.
The Ecoarm heats the oil via the top manhole and
from the inside out. Broadly, the system consists of a
pump nozzle equipped with a heating coil that has two
extendable hot oil spray nozzles on both sides. First,
the pump nozzle is heated and pressed into the stiff
oil. When it begins to thin out around the nozzle, the
oil is pumped to a heat exchanger on the outside, from
which hot oil is sent back into the spray nozzles.
As the oil thins, beginning from the midsection of the
tank, the nozzles begin to move sideways and upwards
and gradually rise to the top of the tank. This way, all
the oil is warmed up and can be unloaded.
According to Neste Jacobs, with the Ecoarm, unload-
ing can be carried out with high-volume fows in cold
weather. The equipment is hydraulically operated and
steered remotely, to make it safe to operate. The system
operates well below fashpoint, and possible volatile
organic compounds can easily be collected. It is
supplied along with traditional base unloading
systems. But if the bottom valve of a base unloading
system is broken, the newer alternative is available for
warming up the oil and making it possible to unload
in cold weather.
Technology in Action
Unloading crude oil in a cold climate

Wireless operators support new
FCC unit
Mobile Station is designed to
increase access to critical
process information, historical
data and graphics
location with low pressure, such as the fash tank or
amine storage tank.
After several minutes of operation, the system rinses
the amine from the resin and resin regeneration takes
place. Concentrated regenerant (sodium hydroxide) is
diluted to the required strength automatically in the
regenerant reservoir. After regeneration, a water wash
step rinses residual traces of regenerant from the resin.
Effuents generated during the regeneration and wash
are directed to waste.
The system generates an alkaline waste stream that
consists of the HSS removed from the resin, as well as
excess regenerant and some amine that is lost to waste.
This stream can be directed to waste treatment as is or
split into concentrated and dilute waste streams. In
some cases, the dilute waste may be suitable for other
process uses, so only the concentrated waste is sent for
treatment.

Development of the BP/Davy Fischer-Tropsch (FT)
process at BPs Conversion Technology Centre in Hull,
England, is being accelerated using high throughput
experimentation techniques. The FT process is used to
convert syngas from unconventional resources, such as
natural gas, coal or biomass, into synthetic fuels and
lubricants. The process developers are seeking their
frst licence. Meanwhile, BP and Davy Process
Technology are working on process enhancements
through studies of, for instance, reaction kinetics and
catalyst performance.
Heidelberg, Germany-based hte has provided in-house
testing capacities and a project team for the collabora-
tion with BP, and has been developing its own
technology for FT synthesis so that BP can perform large
numbers of data measurements rapidly in support of
catalyst and process scale-up. Used systematically, these
data generate information on reaction kinetics, the
fundamentals of start-up and activation, and the impact
of key process parameters. This supports the implemen-
tation of BP/Davy FT technology across a variety of
potential applications and feedstocks.
During 2011, BP and Davy chose three EPC contrac-
tors to promote the commercialisation of the BP/Davy
FT process. CB&I Lummus, Jacobs Engineering Group
and The Shaw Group signed agreements to work with
BP/Davy on opportunities to commercialise the BP/
Davy FT process.
The BP/Davy fxed-bed FT process is an option for
producing diesel, jet fuel (JP8) and naphtha from natu-
ral gas, biomass or coal-derived syngas. The technology
has been demonstrated in Nikiski, Alaska, with full-
scale fxed-bed reaction tubes, where the nominal 300
b/d complex met all of its performance targets. The
process is available for licence, while continuing devel-
opment work by BP and Davy is concerned with
retroft enhancements to the process.
In addition, an EU directive requires special valve
arrays on the bottom of train cars transporting oil, so
old cars with traditional valves cannot be used in EU
countries such as Finland. The problem is that the
traditional base unloading equipment with built-in
warmers does not ft if the tank has EU-adapted
bottom valves. To address this problem, Neste Jacobs
has recently developed a light version of the Ecoarm,
in which the top-warming arm does not have a pump.
In this case, unloading is carried out by gravity
through the valves at the bottom of the tank.
Russian production and investment company TAIF-NK
has installed a continuous amine purifcation system at
its refnery in the republic of Tatarstan, in preference to
a system with periodic operation, for dealing with
contaminants arising from acid gas removal. The
system is Eco-Tecs Amine Purifcation System
(AmiPur) to reduce contaminants, and TAIF is located
in Nizhnekamsk, where it neighbours refnery OJSC
Taneco, which also operates AmiPur.
In oil refning and gas processing, amine chemistry is
essential for removing hydrogen sulphide and/or
carbon dioxide in order to meet product specifcations,
emissions standards or other process requirements.
During operation various contaminants enter, or are
produced, within the amine circuit. Contaminants
include heat stable salts (HSS), solid particulates and
hydrocarbons, resulting in operational problems.
By incorporating AmiPur into the refning process,
TAIF can achieve the continuous removal of HSS from
its amine solution, allowing it to maintain a low, stable
concentration of HSS with predictable amine character-
istics. This also reduces corrosion by-products,
minimises fouling of the heat exchanger and contactor
surfaces, improves heat transfer, and curbs the costs
associated with cleaning of fouled equipment, accord-
ing to Eco-Tec.
There are basically two steps in the AmiPur operat-
ing cycle: HSS loading and caustic regeneration. This
cycle is automatically repeated every 20 minutes. The
system is installed on a slipstream of the lean amine
line downstream of the cooler and the fltration system.
After a polishing cartridge flter, the lean amine solu-
tion is directed through the resin column and HSS are
removed. The purifed amine solution is directed to a

Continuous amine purifcation in acid
gas treatment

High throughput supports FT process
development
Amine chemistry is essential
for removing hydrogen sulphide
and/or carbon dioxide in order
to meet product specifcations
ABB Automation Products 100
ABB Global Consulting 63
Achema 2012 118
Albemarle Catalysts Company IBC
Alfa Laval 75
Amistco Separation Products 26 & 30
Axens OBC
Baker Hughes 39
BASF Corporation, Catalysts Division 4
Bryan Research & Engineering 84
Burckhardt Compression 57
CB&I 7
China Intl Sulphur & Sulphuric Acid Conference 69
DuPont Sustainable Solutions 23
Enersul 32
Flexim 53
Foster Wheeler 104
Grabner Instruments 19
Grace Davison 29
Haldor Topse IFC
Hoerbiger Kompressortechnik Holding 109
Intercat 44
ITW 92 & 117
Johnson Screens 80
KBC Advanced Technologies 2
KIDExtractor 16
Linde 36
ME-TECH 2012 110
Merichem Company 29 & 50
Mogas Industries 89
MPR Services 14 & 31
Nalco Energy Services 70
2012 AFPM (NPRA) Annual Meeting 115
OHL Gutermuth Industrial Valves 99
Paharpur Cooling Towers 54
Process Consulting Services 9 & 11
Refning China 2012 13 & 124
Rentech Boiler Services 64
Sabin Metal Corporation 34
Samson 91
Simili Technologies 12
Spectro Analytical Instruments 25
Vereinigte Fllkrper-Fabriken 83
Yokogawa Europe 49
Zeeco 61
Alphabetical list of advertisers
For more information on these advertisers, go to www.ptqenquiry.com
ad index copy 12.indd 1 13/12/11 15:02:12
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albemarle.indd 1 8/12/11 15:03:03
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The winning catalyst combination
for your hydrocracker
Single source lSC 9001 lSC 14001 CHSAS 18001
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HRK, HDK, HK series: the expert trio to maximize
cycle length, activity and middle distillates selectivity
Hydro_cats_ad_fin.indd 1 26/7/11 12:35:06
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anTurkish Petroleum Refneries Corporation

contents/ed com copy 13.indt 1 12/12/11 13:47:42

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