gas

2011

PTQ supplement

gas cov copy 3.indd 1 9/3/11 13:04:31

 Creating excellence from raw materials
you need a specialist
W W W. T O P S O E . C O M

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with Topse Technologies
Haldor Topse offers you the technology, catalyst and experience for profitable use of your natural gas feed
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Through research-driven technologies, Haldor Topse offers impartial counselling on the selection of the best technology
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haldor.indd 1 8/3/11 13:27:06

 ptqPETROLEUM TECHNOLOGY QUARTERLY

2011
gas
www.eptq.com

5 Amines in bad odour

Chris Cunningham

7 Enhanced sulphur recovery from lean acid gases

Angela Slavens and Justin Lamar Black & Veatch
Djordje L Nikolic and Theo Brok Shell Global Solutions International

19 Cryogenic monitoring
Jerry Worsley Sensornet

25 Glycol dehydration of high-acid gas streams

John Carroll Gas Liquids Engineering
Nathan Hatcher and Ralph Weiland Optimized Gas Treating

35 Controlling corrosion in amine treatment units

Jaya Rawat, Peddy V C Rao and N V Choudary
Bharat Petroleum Corporation Ltd

41 A promoter for selective H2S removal: part I

Gerald Vorberg, Ralf Notz and Torsten Katz BASF SE
Wieland Wache and Claus Schunk Bayernoil Raffineriegesellschaft

48 Estimating gas hydrate inhibitor loss: a case study
Alireza Bahadori Curtin University

The Pearl gas-to-liquids project, Ras Laffan, Qatar. Photo: Shell

2011. 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.

contents/ed com copy 8.indt 1 9/3/11 14:40:37

 MER-0308 LO-CAT Chemist PTQ Spread.pdf 1 1/7/11 3:55 PM

MERICHEM COMPANY

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axens.indd 1 10/12/09 12:59:39

 T tq
p 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
PETROLin
tonnes M TECHBiodiesel
EU2007. NOLOGY QU ARTERLY
production in the
US has also increased dramatically in the
Amines in bad
odour
past few years from 2 million gallons in 2000
to approximately 450 million gallons in 2007.
According to the National Biodiesel Board,

A
171 companies own biodiesel manufacturing
Editor mine capture of acid gases and amine plants themselves are not
plants and are actively marketing biodiesel.1.
Chris Cunningham unexpected topics for discussion by industry experts in this issue of PTQ
[email protected]
The global biodiesel market is estimated Gas. However, recent news has focused not so much on amine technology
to reach 37 billion gallons by 2016, with an for dealing with acid gas components of natural gas as on its application to the
Production Editor
average annual growth rate of 42%. Europe downstream capture of gas combustion products, meaning, of course, CO2. With
Rachel Zamorski
will continue to be the major biodiesel
[email protected] carbon issues looming over the hydrocarbons industry in all of its forms, the story
market for the next decade, followed closely of the Mongstad gas power plant in Norway, which includes a flagship project to
by the USEditor
Graphics market. demonstrate large-scale capture and storage (CCS) of CO2, is causing no end of
Although
Rob Fris high energy prices, confusion for climate change policy makers in Europe.
[email protected]
increasing global demand, drought DONG Energy and Statoil have been working at Mongstad to build a ther-
and other factors are the primary driv- mal power plant, with the aim of integrating it into Statoils neighbouring oil
Editorial
ers for higher food prices, food refinery, while DONG operates and owns the plant. It has been built to supply
tel +44 844 5888 773
competitive feedstocks
fax +44 844 5888 667 have long been Mongstad and a production platform in the North Sea with electricity and
and will continue to be a major heat, and to supply a gas treatment plant with electricity. So far so good.
concern forSales
Advertising theManager
development of biofu- One of the chief ideas behind Mongstad is to strengthen the refinerys posi-
els. To compete, the industry has
Paul Mason tion as an efficient supplier of refined products. At maximum utilisation, the
[email protected]
responded by developing methods to power plant can deliver 280 MW of electricity and about 350 MW of heat. Now
increase process efficiency, utilise or it is up and running, it is no doubt meeting all of those targets. All of the CO2
Advertising Sales
upgrade by-products and operate with it currently produces is released to the atmosphere, which is fine at present
Bob Aldridge
lower quality lipids as feedstocks.
[email protected] because full-scale CCS was not planned to begin until 2014.
But this is where the controversy begins. The CCS arm of the venture was
Feedstocks
Advertising Sales Office first delayed to 2018 and most recently, on Statoils advice, the Norwegian
Biodiesel
tel +44 844refers to a diesel-equivalent
5888 771 government has delayed it further. According to Norways Petroleum and
fax +44 844 5888 662
fuel consisting of short-chain alkyl Energy Ministry, that advice centres not on the technical issues of making a
(methyl or ethyl) esters, made by the CCS project work but on whether amine technology can be used at all, on
Publisher
transesterification of triglycerides, grounds of health and safety. There is a need for greater knowledge of the
Nic Allen
commonly known as vegetable oils or
[email protected] effects of using amine technology on health and the environment, says the
animal fats. The most common form ministry. Now the government wants to look at alternative options for imple-
uses methanol, the cheapest alcohol
Circulation menting CCS.
available,
Jacki Watts to produce methyl esters. While this has, not unexpectedly, put Statoil in bad odour with local environ-
[email protected]
The molecules in biodiesel are primar- mentalists, who were just about prepared to put up with another major
ily fatty acid methyl esters (FAME), gas-fired power plant provided the CO2 it produces could be effectively
Crambeth Allen Publishing Ltd
usually created by transesterification contained, the ramifications travel much further. The EU is preparing to imple-
Hopesay, Craven Arms SY7 8HD, UK
between
tel +44 844 fats
5888 and776methanol. Currently, ment a large-scale programme to demonstrate CCS. Following the European
biodiesel
fax +44 844is5888 produced
667 from various tradition for these matters, individual countries will demonstrate their own
vegetable and plant oils. First-genera- flagship projects. The most successful are likely to become standards for future
tion
ISSN food-based
1362-363X feedstocks are straight implementation among the 27 states of the EU.
vegetable oils such as soybean oil and That programme is scheduled to begin in 2015, which puts Mongstad out the
animal fats such as tallow, lard, yellow
Petroleum Technology Quarterly (USPS 0014-781)
running. To make matters worse for the Norwegian government, it was being
grease,
is publishedchicken fatannual
quarterly plus andCatalysis
the by-products
edition relied on to supply a key demonstration of CCS in a major gas power plant,
by Crambeth Allen Publishing Ltd and is distributed
of the
in the USA byproduction
SPP, 75 Aberdeenof Omega-3
Rd, Emigsville, PA fatty which leaves a significant gap in the programme once it begins. A project
acids from fish
17318. Periodicals postageoil. Soybean
paid at Emigsville PA.oil and touted by the national government as a Moon landing when it was first
Postmaster: send address changes to Petroleum
rapeseeds oil are
Technology Quarterly c/o POthe common source announced looks to be firmly Earth-bound.
for biodiesel
Box 437, Emigsville,production
PA 17318-0437 in the US and Why has there been further delay to the Mongstad project? Statoil is increas-
Back numbers available from the Publisher
Europe in inc
at $30 per copy quantities
postage. that can produce ingly worried, apparently, about the production of nitrosamines as a
enough biodiesel to be used in a component of the process of amine capture of CO2 and the effects of these
commercial market with currently substances on human health, which many view with more than a pinch of
applicable technologies. scepticism.
First-generation feedstocks for
chris cunningham

GAS 2011 5

contents/ed com copy 8.indt 2 9/3/11 13:07:16

 PROCESS INSIGHT
Selecting the Best Solvent for Gas Treating

Selecting the best amine/solvent for gas treating is not a trivial task. Tertiary Amines
There are a number of amines available to remove contaminants such A tertiary amine such as MDEA is often used to selectively remove
as CO2, H2S and organic sulfur compounds from sour gas streams. H2S, especially for cases with a high CO2 to H2S ratio in the sour gas.
The most commonly used amines are methanolamine (MEA), One benet of selective absorption of H2S is a Claus feed rich in H2S.
diethanolamine (DEA), and methyldiethanolamine (MDEA). Other MDEA can remove H2S to 4 ppm while maintaining 2% or less CO2 in
amines include diglycolamine (DGA), diisopropanolamine (DIPA), the treated gas using relatively less energy for regeneration than that
and triethanolamine (TEA). Mixtures of amines can also be used to for DEA. Higher weight percent amine and less CO2 absorbed results
customize or optimize the acid gas recovery. Temperature, pressure, in lower circulation rates as well. Typical solution strengths are 40-50
sour gas composition, and purity requirements for the treated gas weight % with a maximum rich loading of 0.55 mole/mole. Because
must all be considered when choosing the most appropriate amine for MDEA is not prone to degradation, corrosion is low and a reclaimer
a given application. is unnecessary. Operating pressure can range from atmospheric,
typical of tail gas treating units, to over 1,000 psia.
Mixed Solvents
In certain situations, the solvent can be customized to optimize the
sweetening process. For example, adding a primary or secondary
amine to MDEA can increase the rate of CO2 absorption without
compromising the advantages of MDEA. Another less obvious
application is adding MDEA to an existing DEA unit to increase the
effective weight % amine to absorb more acid gas without increasing
circulation rate or reboiler duty. Many plants utilize a mixture of amine
with physical solvents. SULFINOL is a licensed product from Shell Oil
Products that combines an amine with a physical solvent. Advantages
of this solvent are increased mercaptan pickup, lower regeneration
energy, and selectivity to H2S.

Primary Amines Choosing the Best Alternative

The primary amine MEA removes both CO2 and H2S from sour gas Given the wide variety of gas treating
and is effective at low pressure. Depending on the conditions, MEA options, a process simulator that can
can remove H2S to less than 4 ppmv while removing CO2 to less than accurately predict sweetening results is a
100 ppmv. MEA systems generally require a reclaimer to remove necessity when attempting to determine
degraded products from circulation. Typical solution strength ranges the best option. ProMax has been proven
to accurately predict results for numerous
from 10 to 20 weight % with a maximum rich loading of 0.35 mole
process schemes. Additionally, ProMax
acid gas/mole MEA. DGA is another primary amine that removes
can utilize a scenario tool to perform
CO2, H2S, COS, and mercaptans. Typical solution strengths are 50-
feasibility studies. The scenario tool may
60 weight %, which result in lower circulation rates and less energy
be used to systematically vary selected
required for stripping as compared with MEA. DGA also requires
parameters in an effort to determine the
reclaiming to remove the degradation products. optimum operating conditions and the appropriate solvent. These
Secondary Amines studies can determine rich loading, reboiler duty, acid gas content of
The secondary amine DEA removes both CO2 and H2S but generally the sweet gas, amine losses, required circulation rate, type of amine
requires higher pressure than MEA to meet overhead specications. or physical solvent, weight percent of amine, and other parameters.
Because DEA is a weaker amine than MEA, it requires less energy for ProMax can model virtually any ow process or conguration
stripping. Typical solution strength ranges from 25 to 35 weight % with including multiple columns, liquid hydrocarbon treating, and split ow
a maximum rich loading of 0.35 mole/mole. DIPA is a secondary amine processes. In addition, ProMax can accurately model caustic treating
that exhibits some selectivity for H2S although it is not as pronounced applications as well as physical solvent sweetening with solvents such
as for tertiary amines. DIPA also removes COS. Solutions are low as Coastal AGR, methanol, and NMP. For more information about
in corrosion and require relatively low energy for regeneration. The ProMax and its ability to determine the appropriate solvent for a given
most common applications for DIPA are in the ADIP and SULFINOL set of conditions, contact Bryan Research & Engineering.
processes.

Bryan Research & Engineering, Inc.

P.O. Box 4747 Bryan, Texas USA 77805
979-776-5220 www.bre.com [email protected]
www.ptqenquiry.com
for further information

bre.indd 1 8/3/11 13:36:38

 Enhanced sulphur recovery from
lean acid gases
A preferred acid gas enrichment scheme is combined with two gas-treating
schemes to examine the lifecycle cost of a sour natural gas treatment facility

Angela Slavens and Justin Lamar Black & Veatch

Djordje L Nikolic and Theo Brok Shell Global Solutions International

T
he exploitation of increasingly content and affirmed that, at such a The purpose of the previous
difficult natural gas reserves low H2S concentration, reliable study was to compare alternative
has risen in recent years, Claus unit operation can be acid gas enrichment processing
requiring the removal of a number difficult. schemes for a given lean acid gas
of harder to remove sulphur The 2010 study considered the stream composition and flow rate,
species, as well as H2S, CO2 and use of the acid gas enrichment but not to consider the impact that
H2O. In addition, maximum limits (AGE) process to increase acid gas the upstream acid gas removal unit
for sulphur content in pipeline gas H2S concentration, as a means to (AGRU) solvent selection can have
continue to tighten. As a result, the alleviate the problems associated on the acid gas quality. However,
treating requirements for gas field with the lean acid gas feed to the in most situations, it is important to
development projects have signifi- Claus SRU/TGTU. It also addressed consider the overall sour gas treat-
cantly increased in complexity, the fact that the conventional AGE ment flow scheme rather than
often requiring a combination of processing scheme cannot achieve simply evaluating the acid gas
process steps and units. As the high sulphur recovery when COS processing in isolation, as synergies
development of difficult sour gas often exist between the various
fields is expected to further increase processing units (AGRU/AGE/
in the future, strategic integration It is important to SRU/TGTU) that provide opportu-
of various gas-treating process units nities for optimisation of the overall
is necessary to achieve an overall consider the overall flowsheet.
optimised flow sheet with lowest This article compares three differ-
lifecycle cost. The ability to combine sour gas treatment ent Sulfinol AGRU options for
technologies and process units in development of the overall flow
the optimum configuration results flow scheme scheme for treatment of a sour
in a competitive advantage for natural gas stream containing
addressing challenges and opportu-
rather than simply significant quantities of organic
nities posed by undeveloped sour evaluating the acid gas sulphur (methyl and ethyl
gas fields. mercaptan). Although COS was
In 2010, a study by Black & processing in isolation an additional organic sulphur
Veatch compared several alterna- compound considered in the 2010
tive Claus sulphur recovery unit study, it would typically not be
(SRU)/tail gas-treating unit (TGTU) and mercaptans are present, due to present in acid gas from the over-
configurations for achieving high the fact that selective treating head of a chemical amine solvent or
sulphur recovery and reliable oper- solvents commonly utilised for acid hybrid chemical/physical solvent
ation from lean acid gas containing gas enrichment do not absorb these regenerator. This is primarily due
high concentrations of carbonyl organic sulphur species and allow to the fact that absorbed COS is
sulphide (COS) and mercaptans. them to slip to the incinerator. hydrolysed to H2S and CO2 in the
The lean acid gas stream that was Several acid gas enrichment solvent regeneration step of the
used as the basis for comparison of processing schemes were compared, AGRU. All Sulfinol solvents remove
the process configuration test cases and it was concluded that when COS to a large extent in the main
had an H2S concentration of 25 acid gas COS/mercaptan levels are absorber of the AGRU. With
mole% and an organic sulphur high enough to reduce sulphur Sulfinol-X, deep removal of COS
concentration of 1 mole%. The recovery with conventional acid gas can be achieved due to the presence
study noted that a lean acid gas enrichment below an acceptable of piperazine, which enhances COS
stream such as this could be level, an alternative enrichment hydrolysis. With Sulfinol-M, most
produced from sweetening natural design configuration should be of the COS would be absorbed due
gas with a high COS/mercaptan considered. to the larger number of trays

www.eptq.com GAS 2011 7

b&v.indd 1 9/3/11 13:01:07

 utilising some of the acid gas treat-
Sour natural gas feed stream used for comparison of test cases
ment schemes presented in the 2010
article. The optimum configura-
Component Sour natural gas, lbmoles/hr Sour natural gas, mole fraction tions, in terms of relative Capex
H2O 10.63 0.126
CO2 784.69 9.300 and Opex, are presented.
H2S 270.00 3.200
N2 421.88 5.000 Test cases
C1 6618.37 78.440 The sour natural gas stream used
C2 210.94 2.500
C3 101.26 1.200 for comparison of the various proc-
iC4 4.21 0.050 ess configuration test cases is shown
C4 4.21 0.050 in Table 1. Sulphur content is 96.1
iC5 1.26 0.015 t/d. About 2% of the acid gas
nC5 1.26 0.015
C6 3.37 0.040 sulphur is present as mercaptans;
CH4S 4.06 0.048 therefore, recovery of mercaptan
C2H6S 1.34 0.016 sulphur is important if high sulphur
Total 8437.47 100.000 recovery is to be achieved.
Temperature, F 95
Pressure, psia 870 The treated gas specifications
used for the comparison test cases
are shown in Table 2. The specifica-
Table 1 tions considered are typical for
pipeline-quality natural gas. Table 3
and Table 4 describe the three
Treated gas specifications
process configuration test cases
compared in this article, each of
Gas stream Specification Value which is illustrated in Figures 13.
Sales gas H2S, ppmv <5
Total sulphur, ppmv <20
The Case 1 process configuration
CO2, mole% <1.0 is shown in Figure 1. Sour natural
Fuel gas H2S, ppmv <100 gas is processed in a Sulfinol-X
Tail gas ex-TGTU absorber H2S, ppmv <250 AGRU, producing a lean acid gas
stream containing H2S and
Table 2 mercaptans. Sulfinol-X technology
employs piperazine accelerator in
Test cases for comparison addition to MDEA, sulpholane and
water. This solvent formulation
meets both low H2S and CO2 speci-
Test case Description fications, as well as low
1 Sulfinol-X main gas treating, conventional SRU/SCOT1 using MDEA
2 Sulfinol-X main gas treating, SRU/SCOT using Sulfinol-M acid gas enrichment specifications of trace sulphur
and tail gas treating, routing of enrichment absorber overhead to SCOT species (such as mercaptans, COS
3 Sulfinol-M main gas treating with integrated enrichment step and tail gas and organic sulphides). The
absorber, conventional SRU/SCOT using Sulfinol-M, routing of enrichment Sulfinol-X unit has a standard
absorber overhead to SCOT
configuration consisting of a main
absorber, hydrocarbon flash vessel
Table 3 with associated absorber and a
regeneration section. The hydrocar-
Test case process configurations
bon flash minimises co-absorbed
hydrocarbons in the acid gas. The
lean acid gas stream from the
Test case AGRU solvent AGE solvent TGTU solvent AGE overhead routing AGRU regenerator is processed in a
1 Sulfinol-X MDEA
2 Sulfinol-X Sulfinol-M Sulfinol-M To TGTU, per Case 4 from 2010 article
conventional two-bed Claus SRU.
3 Sulfinol-M Sulfinol-M Sulfinol-M To TGTU, per Case 4 from 2010 article SRU tail gas flows to an MDEA-
based Shell Claus Offgas Treatment
(SCOT)1 TGTU, where residual
Table 4 sulphur species in the SRU tail gas
are converted to H2S, which is
employed. Since Sulfinol is a hybrid treated flash gas would not be a subsequently removed in the down-
chemical/physical solvent, for the differentiator between the three stream TGTU absorber. The TGTU
reasons described above, COS cases studied in this article; hence, regenerator regenerates the rich
captured in the absorber will not be COS has been omitted from the MDEA solvent, and the overhead
present in the acid gas. Therefore, it analysis. from this tower is routed to the
is anticipated that the small varia- The resulting acid gas from each front of the SRU for the recovery of
tions of COS in the sales gas and AGRU configuration is processed sulphur in this stream.

8 GAS 2011 www.eptq.com

b&v.indd 2 9/3/11 14:41:41

 Treated
natural
gas

Regenerator
Main
absorber
To fuel
Sour
natural
gas

Flash
drum

Claus converters

Incinerator

Thermal
Air reactor
Fuel

Air
Sulphur Sulphur Sulphur

Hydrogenation
reactor
Quench TGTU Regenerator
Fuel column absorber
Inline
Air
burner/mixer

WHB

Figure 1 Case 1 process configuration: Sulfinol-X gas treating with conventional SRU/SCOT

Case 1 represents a conventional increase acid gas strength for minimising CO2 absorption.
base case to compare with Cases 2 improved Claus operation. Reduced CO2 solubility is desirable
and 3. The Case 1 AGRU produces The Case 2 process configuration in the AGE and TGTU absorbers to
a lean acid gas containing nomi- is shown in Figure 2. Sour natural prevent excessive CO2 flow through
nally 25 mole% H2S and 0.5 mole% gas is processed in a Sulfinol-X acid the SRU and TGTU, which increases
mercaptans, an acid gas stream gas removal unit similar to that in their size. AGE absorber overhead
similar to that used for comparison Case 1. Acid gas from the Sulfinol- gas, containing most of the CO2 in
of the test cases explored in the X unit is subsequently processed in the acid gas as well as other compo-
2010 article, with the absence of an enrichment absorber, which nents not absorbed by the
COS. As explained in the 2010 arti- absorbs H2S from the acid gas using Sulfinol-M solvent, flows to the
cle, acid gas at or below this Sulfinol-M solvent. Sulfinol-M tech- TGTU hydrogenation reactor rather
concentration makes sustainable nology employs MDEA, sulpholane than to the incinerator, similar to
Claus performance difficult due to and water, without piperazine, as is Cases 4A, 4B and 4C presented in
a low thermal reactor temperature the case with Sulfinol-X. This results the 2010 article. Routing the AGE
and acid gas flame instability. Cases in AGE and TGTU absorbers, which overhead to the hydrogenation
2 and 3 utilise enrichment to remove H2S and mercaptans while reactor allows conversion of the

www.eptq.com GAS 2011 9

b&v.indd 3 9/3/11 16:22:19

 Treated
natural
gas

Regenerator
Main
absorber
To fuel
Sour
natural
gas

Flash
drum

Claus converters

Incinerator

Thermal
Air reactor
Fuel

Air
Sulphur Sulphur Sulphur

Hydrogenation
reactor

Fuel
Quench TGTU AGE
Inline
column absorber absorber
Air burner/mixer

Hydrogenation
reactor

Regenerator
Fuel
Inline
Air burner/mixer

WHB

Figure 2 Case 2 process configuration: Sulfinol-X gas treating with SRU using enrichment, enrichment absorber overhead routed to SCOT

mercaptans in this stream to H2S, 1982. This feature is crucial to absorber overhead to the TGTU
for absorption in the downstream achieving high sulphur recovery allows conversion of these other
TGTU absorber, which also employs efficiency when acid gas for enrich- sulphur species to H2S, which can
Sulfinol-M solvent. Concentrated ment contains sulphur species other be recovered in the TGTU absorber.
acid gas flows from the Sulfinol-M than H2S. With conventional acid In order to avoid premature ageing
regenerator to the SRU/TGTU for gas enrichment, these other sulphur of the hydrogenation catalyst due
sulphur recovery. species are not absorbed using to the presence of heavier hydrocar-
Routing of an enrichment selective treating solvents and bons, two parallel hydrogenation
absorber overhead stream to a therefore flow unrecovered to the catalyst beds are employed, one for
TGTU was patented by Shell in incinerator. Routing the enrichment the main Claus tail gas and one for

10 GAS 2011 www.eptq.com

b&v.indd 4 9/3/11 16:22:29

 Treated
natural
gas

Main Enrichment
Regenerator
absorber absorber
To fuel
Sour
natural
gas

Flash
drum
Hot flash drum

Claus converters

Incinerator

Thermal
Air reactor
Fuel

Air
Sulphur Sulphur Sulphur

Hydrogenation
reactor

Fuel
Inline
Air burner/mixer

Hydrogenation
reactor
Quench TGTU
Fuel column absorber
Inline
Air burner/mixer

WHB

Figure 3 Case 3 PFD: Sulfinol-M gas treating with integrated enrichment step and tail gas treating, enrichment absorber overhead
routed to SRU/SCOT

the AGE overhead gas. This is a risk of contamination/premature It should be noted that the
deliberate deviation from the 2010 ageing to the AGE overhead reac- Sulfinol-M solvent circulation
study, which considered only a tor, which is the smaller of the two. system is integrated between the
single hydrogenation reactor for all If the need for premature change- AGE and TGTU absorbers similar
cases, which routed AGE overhead out of the catalyst in this reactor to the Case 4C configuration in the
gas through the TGTU. The reason arose, it would not result in signifi- 2010 study; 100% of the semi-rich
for the inclusion of parallel hydro- cant losses in overall sulphur solvent from the TGTU absorber is
genation reactors is to restrict the recovery efficiency. cascaded to the AGE absorber. Case

www.eptq.com GAS 2011 11

b&v.indd 5 9/3/11 16:22:38

 )1
BTI

HBT

AGRU
4PVS
(Sulfinol-X) 5SFBUFE

OBUVSBM OBUVSBM
HBT HBT 3FDZDMF
BDJE
HBT
 3JDI -FBO   4UBDL
  HBT
436 5(56 
"DJE
HBT UBJM
HBT UBJM
HBT
AGRU   
436 TGTU Incinerator
regenerator
(MDEA)
(Sulfinol-X)

4VMQIVS 4VMQIVS
QSPEVDU QJU
WFOU
 

Figure 4 Sulphur balance for Case 1: Sulfinol-X gas treating with conventional SRU/SCOT (sulphur flows in lbmoles/hr)

)1
BTI

HBT

"(36
4PVS
4VMOPM9
5SFBUFE

OBUVSBM OBUVSBM
HBT HBT
 3JDI -FBO 
 

"(36
SFHFOFSBUPS
"(&
BCTPSCFS
PWFSIFBE
4VMOPM9


"DJE
HBT 4UBDL
 HBT
436 5(56 
UBJM
HBT UBJM
HBT
 
"(& 436 5(56 *ODJOFSBUPS
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(sulphur flows in lbmoles/hr)

12 GAS 2011 www.eptq.com

b&v.indd 6 9/3/11 13:01:55

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SCOT (sulphur flows in lbmoles/hr)

4C was the optimal case from the Sulfinol-M solvent from all three removal specification that can be
2010 article, hence this configura- absorbers. Concentrated acid gas achieved with Sulfinol-X, the speci-
tion was selected without further flows from the Sulfinol-M regenera- fication of <1 mole% CO2 selected
analysis of Case 4A or 4B configu- tor to the SRU/TGTU for sulphur for this article can be easily
rations in this evaluation. recovery. achieved.
The Case 3 process configuration, Compared with Case 2, Case 3
which integrates acid gas enrich- has one solvent system instead of Comparison of sulphur recovery
ment within the AGRU, is shown in two, which eliminates one regenera- efficiency
Figure 3. Sour natural gas is proc- tor and reduces the equipment The overall sulphur recovery for
essed in a Sulfinol-M AGRU and count in the solvent storage and each of the test cases is given in
the resulting acid gas is processed drain systems, as well as reducing Table 5. The H2S removal and
in a conventional two-bed Claus operational complexity. The formu- sulphur recovery steps in each case
SRU. The Sulfinol-M AGRU lation of Sulfinol-M allows this have been modelled on a consistent
contains an enrichment step, which solvent to be used both for the basis. As a result, differences
consists of an additional hot flash selective and non-selective removal between cases reflect their particu-
vessel and an enrichment absorber. of H2S in the presence of CO2, lar process characteristics, without
In this enrichment section, rich depending on the process condi- influence from the inconsistencies
solvent is heated and flashed at tions. While Sulfinol-M cannot associated with variations in param-
reduced pressure. The CO2-rich reach the LNG-like deep CO2 eters such as H2S removal efficiency,
flash vapour flows to an enrichment
absorber, where lean Sulfinol-M
solvent absorbs H2S and some Comparison of sulphur recovery efficiency for test cases
mercaptans. The enrichment
absorber overhead flows to a sepa- Case 1 2 3
rate hydrogenation section of the HP flash gas to incinerator, lbmol/hr 0.083 0.080 0.031
TGTU, for conversion of mercaptans TGTU H2S to incinerator, lbmol/hr 0.425 0.410 0.391
to H2S, similar to the Case 2 flow- TGTU COS to incinerator, lbmol/hr 0.163 0.152 0.143
Pit sweep sulphur to incinerator, lbmol/hr 0.045 0.045 0.045
sheet. Also similar to Case 2, the Total sulphur to incinerator, lbmol/hr 0.716 0.687 0.610
Sulfinol-M solvent circulation Incinerator stack SO2, ppmv dry and air-free 266 269 249
system is integrated between the Total sulphur in treated natural gas, lbmol/hr 0.043 0.043 0.044
AGE and TGTU absorbers, as per Overall sulphur recovery, % 99.72% 99.73% 99.76%
Sulphur recovery of the sulphur complex, % 99.77% 99.78% 99.78%
the Case 4C configuration in the
2010 study. Case 3 employs a single
regenerator for regeneration of the Table 5

www.eptq.com GAS 2011 13

b&v.indd 7 9/3/11 13:02:04

 Comparison of solvent systems
Solvent system comparison for test cases
Solvent circulation rates and other
solvent system design data for each
Case 1 2 3 of the test cases are shown in
Main absorber
Lean solvent, gpm 1236 1236 1265 Table 6.
TGTU absorber Solvent flow rate to the main
Lean solvent, gpm 325 1015 1012 absorber is about the same in all
Inlet H2S, mole% 1.35 1.31 1.35 cases, with only a slightly higher
Inlet CO2, mole% 48.43 50.74 49.31
Overhead H2S, ppmv 248 249 248 requirement for the Sulfinol-M case
CO2 slip, % 93.6 88.9 88.2 (Case 3). In Cases 2 and 3, lean
AGE absorber Sulfinol-M solvent flows to the
Lean solvent, gpm - - - TGTU absorber with subsequent
Inlet H2S, mole% - 24.10 19.55
Inlet CO2, mole% - 69.62 74.90 cascading of the semi-rich TGTU
Overhead H2S, ppmv - 6526 6562 absorber bottoms to the AGE
CO2 slip, % - 88.1 88.7 absorber. Cases 2 and 3 have the
Main treating regenerator same lean solvent flows to the
Acid gas H2S, mole% 24.20 24.10 53.15
Total lean solvent, gpm 1284 1284 2338 TGTU absorbers and the same
Regeneration steam, lb/hr 55 888 55 888 129 387 semi-rich solvent flows to the AGE
AGE/TGTU regenerator absorbers. Thus, Case 2 has essen-
Acid gas H2S, mole% 28.46 57.22 - tially the same total solvent flow as
Total lean solvent, gpm 325 1015 -
Regeneration steam, lb/hr 19 221 53 949 - Case 3, with the only difference
Total solvent circulation, gpm 1609 2299 2338 being a minor incremental increase
Total regeneration steam, lb/hr 75 109 109 837 129 387 in flow for the Sulfinol-M main
absorber in Case 3. Sulfinol-M
requires more steam for regenera-
Table 6 tion than Sulfinol-X; therefore, Case
3 has a higher solvent regeneration
reboiler duty or circulation rate. performance. This is because the steam consumption rate than Case
Overall sulphur recovery reported 2010 study considered a lower 2. Case 1, because it does not
in Table 5 considers the sulphur TGTU absorber overhead H2S speci- perform acid gas enrichment, has
balance envelope around the entire fication than that in the Sulfinol the lowest total solvent circulation
gas treatment facility (AGRU/ schemes of this study (approxi- and steam consumption rates.
AGE/SRU/TGTU) and includes
sulphur lost in the treated natural Comparison of SRU/TGTU train size
gas stream, while sulphur recovery Most SRU and TGTU Most SRU and TGTU equipment
of the sulphur complex figures sizes are primarily determined by
reported in Table 5 considers only equipment sizes are the process gas volumetric flow
the sulphur balance around the rate. SRU, TGTU and incinerator
sulphur production facilities (AGE/ primarily determined volumetric gas rates for each test
SRU/TGTU). It is important to note case are given in Table 7.
that the 2010 study reported by the process gas Case 1 requires the largest SRU/
sulphur recovery efficiency figures TGTU train size due to the fact that
for the sulphur recovery complex
volumetric flow rate it processes SRU feed gas with the
only (ie, the second set of figures in lowest H2S concentration; flow rates
the table) and not for the overall are similar to those for Case 1 from
gas treatment facility. Furthermore, mately 180 ppmv versus 250 ppmv, the 2010 study. Cases 2 and 3
the sulphur complex recovery effi- respectively). significantly reduce the SRU size
ciency figures reported in the last All three cases are similar in because these alternatives minimise
row of Table 5 should not be used sulphur recovery efficiency (see CO2 flow through the SRU by slip-
in direct comparison with the Table 5). The sulphur balance ping CO2 from the enrichment step
recovery efficiency figures reported for each case is illustrated in with the use of Sulfinol-M solvent.
in 2010 for assessment of solvent Figures 46. Since the enrichment absorber over-
head is routed to the TGTU in
SRU/SCOT train size comparison for test cases Cases 2 and 3, the TGTU and incin-
erator sizes are not substantially
smaller than the Case 1 size.
Case 1 2 3
SRU tail gas, lbmol/hr 1870 1063 1108
TGTU feed gas, lbmol/hr 1870 1798 1727 Capital and operating
Incinerator process gas feed, lbmol/hr 1713 1648 1576 cost comparison
Table 8 shows estimated capital and
Table 7 operating costs for each case. Rough

14 GAS 2011 www.eptq.com

b&v.indd 8 9/3/11 14:42:33

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15_lurgi.indd 1 8/3/11 13:42:28

 instead of MDEA. In the 2010 study,
Cost comparison for test cases
the AGE/SRU/TGTU configuration
of Case 4C resulted in slightly
Case 1 2 3
Fuel lower capital cost than the conven-
Consumption, MMBtu/hr 32.3 26.8 30.6 tional SRU/TGTU configuration of
Yearly cost 1.7 1.4 1.6 Case 1, which did not include
Power enrichment. Here, Case 2 is slightly
Consumption, kW 1314 1348 1490
Yearly cost 0.7 0.7 0.8 higher in capital cost than Case 1.
600 psig saturated steam The difference between the results
Export, lb/hr 19 940 17 481 17 301 of the 2010 study and the results
Yearly credit 1.4 1.2 1.2 reported here is explained primarily
50 psig saturated steam
Import, lb/hr 58 964 99 383 118 769 by the fact that the hydrogenation
Yearly cost 3.5 5.9 7.0 step was split into two reactors
Maintenance and non-utility operating costs instead of combined into a single
Yearly cost (10% TIC) 8.7 9.2 9.4 reactor, as in the 2010 Case 4
Cost summary
Total yearly operation and maintenance cost 13.2 16.0 17.6 configurations.
Total installed cost 86.6 92.2 93.9 The important comparison is
Net present cost 171.9 195.6 207.6 between Cases 2 and 3, both of
Notes: Costs are reported in millions of US dollars.
which produce acid gas with a H2S
1. Costs were prepared using the following information: concentration high enough to ensure
* $6.00/MMBtu LHV fuel stable Claus SRU performance. In
* $0.064/kWh power
* $6.96/1000 lb 50 psig sat. steam both of these cases, the SRU, TGTU
* $8.31/1000 lb 600 psig sat. steam and incinerator portions are similar
* 355 operating days per year
* 15% annual rate of return in size and cost; therefore, the
* 25-year plant life difference in capital cost is in
the AGRU/AGE/TGTU treating
sections. Although Case 3, with its
Table 8 single Sulfinol-M solvent system,
requires fewer equipment items in
order of magnitude capital costs are makes the acid gas enrichment these sections, some of them are
provided on a US Gulf Coast basis achieved in the other cases desira- larger and therefore slightly more
and include engineering, procure- ble, in spite of their larger amine expensive than the equivalent equip-
ment and installation of all process units with higher energy ment items in Case 2. Sulfinol-M
and utility equipment; storage, consumption. requires more regeneration energy
metering and loading facilities; than Sulfinol-X, making the regener-
plus, construction indirects, spares, ation system larger. Additionally,
engineering and commissioning. Alternative acid gas Sulfinol-M requires a larger absorber
Items such as owners costs, land in the AGRU.
costs, escalation and contingency enrichment schemes Despite the fact that this analysis
are excluded. Operating costs are shows a slight preference for Case 2
discounted for each year of plant must be considered to over Case 3, the capital cost differ-
life and are added to capital cost to ential is small and quite possibly
form each cases net present cost.
achieve high sulphur within the margin of error of the
The conventional SRU/TGTU
arrangement paired with Sulfinol-X
recovery efficiency estimates. When operating costs are
considered, there is a greater depar-
treating for Case 1 serves as a when organic sulphur ture between the net present cost of
benchmark for comparison between the two options, with Case 2 still
the other cases, similar to the way compounds are emerging as the preferred configu-
in which the Case 1 conventional ration. However, the small
SRU/TGTU arrangement of 2010 present difference in net present cost
served as a benchmark for the suggests that a detailed analysis
enrichment cases studied at that The Case 2 Sulfinol-X design is between these two options should
time. The Sulfinol-X design of Case essentially the same as Case 1; be carried out when selecting the
1 represents an optimum approach however, in Case 2, the lean acid preferred scheme for a specific sour
if considering only the AGRU and gas from the AGRU is enriched to natural gas-treating application.
not the impact that the resulting improve Claus SRU operating
lean acid gas has on the down- performance, while also giving the Summary and conclusions
stream SRU. However, as benefit of reduced SRU size. The A 2010 analysis by Black & Veatch
ascertained in the 2010 study, Claus AGE/SRU/TGTU for Case 2 is acknowledged that acid gas enrich-
SRU operational difficulty caused similar to Case 4C from the 2010 ment should be considered when
by low acid gas H2S concentration study, but with Sulfinol-M solvent upstream AGRU configurations

16 GAS 2011 www.eptq.com

b&v.indd 9 9/3/11 13:02:27

 produce lean acid gas with H2S 2 Slavens A, Lamar J, ODell S, Francoviglia Justin Lamar is Sulphur Section Lead with
concentrations lower than that L, Enhanced sulfur recovery from lean acid Black & Veatch. Email: [email protected]
required to achieve reliable Claus gases containing COS and mercaptans, 2010
SRU operation (<25 mol%), and Laurance Reid Gas Conditioning Conference. Djordje Nikolic is Licensing Manager for
3 Nikolic D L, Wijntje R, Hanamant Rao P P, Upstream Gas Processing Gas & Liquids
concluded that alternative acid gas
Do you have hard to handle gases? Consider Treating with Shell Global Solutions
enrichment schemes must be
using this second-generation hybrid solvent International, Amsterdam, The Netherlands.
considered to achieve high sulphur for treating, Hydrocarbon Processing, Jul 2009, Email: [email protected]
recovery efficiency when organic 6771.
sulphur compounds are present. Theo Brok is a Senior Process Design
The preferred enrichment scheme Angela Slavens is Vice President and Sulphur Engineer and Subject Matter Expert, Gas &
from the 2010 study incorporates Technology Manager with Black & Veatch, Liquids Treating, with Shell Global Solutions
recycle of the unabsorbed enrich- Overland Park, Kansas, USA. International.
ment absorber overhead organic Email: [email protected] Email: [email protected]
sulphur to the TGTU for
high recovery efficiency, and
employs maximum solvent integra-

What Goes Around...

tion between the AGE and TGTU
absorbers for minimum capital and
operating cost. The preferred
enrichment scheme from the Remove Solids and Hydrocarbons from
2010 study has been selected in
combination with two different
your solvent with MPRs High Capacity,
Sulfinol gas-treating schemes to Easily Regenerated Media.
examine the lifecycle cost of the
entire sour natural gas treatment
Available Worldwide
facility.
The MPR SSX and HCX processes use our unique and proprietary media, which
In the current analysis, Case 2,
Sulfinol-X main gas treating with can easily be regenerated after exhaustion. They complement each other in way that
Sulfinol-M acid gas enrichment and allows them to surpass the capacity of standard cartridges and activated carbon
tail gas treating, results in a slightly filters, while bringing outstanding longevity.
lower lifecycle cost than Case 3, SSX and HCX Solve The Following Common Problems:
which is a fully integrated Sulfinol-
Plugging of heat exchangers, piping, towers
M approach for main gas treating,
and instruments
acid gas enrichment and tail gas
treating. Although the Case 2 life- Poor hydrocarbon separation from
cycle cost is lower, minimal cost amine solutions
difference between the two schemes High Amine losses
suggests that a detailed analysis Unstable Unit operations
should be carried out to determine Accelerated corrosion rates due
the preferred option for a specific to erosion
sour natural gas treating applica- Deactivation of Claus Catalyst in the SRU
tion. Additionally, it is important
not to overlook the somewhat SSX and HCX processes work by removing solids to
intangible operational and mainte- submicron size particles, while also removing hydrocarbons
nance benefits associated with (including diesel, gas oils, paraffins, BTEX and various petroleum
operating a single solvent system in intermediates) from amine solutions.
Case 3, versus two separate systems
Eliminating cartridge filters and activated carbon means eliminating filter replacement,
in Case 2, when selecting the best
configuration to meet a sour gas disposal and labor
processors needs. SSX and HCX processes are available exclusively from MPR Services, Inc..

Sulfinol and SCOT are trademarks of Shell. For more information, call 281-377-7424
or visit our website at www.mprservices.com

MPR Services, Inc., A Tessenderlo Kerley, Inc. Company.

Further reading 1201 FM 646, Dickinson, TX 77539-3014 U.S.A.
5FMFQIPOF

t
'"9

1 McNamara H J, Schilk J A, US Patent No. E-mail: JOGPNQSTFSWJDFT!ULJOFUDPN
t
NQSFVSPQF!ULJOFUDPN
t
NQSNJEEMFFBTU!ULJOFUDPN
4 356 161, Washington, DC, US Patent and 2011 Tessenderlo Kerley, Inc.
Trademark Office, 1982.

www.ptqenquiry.com
www.eptq.com for further information GAS 2011 17

b&v.indd 10 9/3/11 13:02:38

 Sweet
Sour

Gas processing expertise in a variety of avors.

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www.ptqenquiry.com
for further information

11_GOC_PTQ's Gas Supplement_AD.indd 1 2/21/11 2:41 PM

b&v.indd 1 8/3/11 14:17:05
 Cryogenic monitoring

Fibre optic distributed temperature sensing has several advantages over

conventional real-time data sensors in cryogenic leak detection at LNG terminals

Jerry Worsley
Sensornet

E
nvironmental and safety issues any cool-down or leak event. By Such a system can lead to
are becoming ever more contrast, using fibre optic DTS, the improved plant operation, allowing
important in the liquefied location of such an incident can be the monitoring system maintenance
natural gas (LNG) process industry. identified almost instantly and schedule to be aligned to other
As plants, pipelines and storage remedial action taken. In fibre optic safety integrity systems in the plant
facilities become larger in scale and DTS, the fibre is the sensor and the The sensing element is an intrin-
more complex, maximising safety measurement is totally non- sically safe passive sensing cable
and minimising risk requires an intrusive. No welds are required to with a design life of more than 30
absolute understanding. the pipe or vessel and the fibre can years, resulting in high reliability
It is estimated that more than 400 be easily strapped to the outside of and low maintenance
liquefaction, receiving and storage the pipe with no interruption to the The system is fully automated
facilities are either operating, under operational process. The fibre and so lowers operating costs with
construction or planned today. This provides its own communications less risk of human error. It can
effectively equates to more than 500 path and no additional tie cables interface with existing supervisory
storage tanks and well in excess of are required. Most importantly, control and data acquisition
1000 km of pipeline that requires DTS using optical fibres enables the (SCADA) and ESD or fire and gas
monitoring. capture of data every metre at near control systems using standard
Recent years have seen significant real-time speeds. It can detect and protocols.
developments in the technologies report cryogenic leaks to the emer- The benefits to an asset manager
available to effectively monitor an gency shutdown (ESD) system of such a system are clear. It can
ever-increasing number of facilities within 15 seconds. This enables the improve the safety of both the
and associated infrastructures. With ESD system to register and close infrastructure and of personnel,
conventional technology, there tradi- valves within 45 seconds. which can reduce insurance and
tionally has been a gap between A DTS system from Sensornet litigation costs, fulfil legal and plan-
what is thought to be occurring provides a cryogenic monitoring ning requirements, and enhance a
throughout an installation and what solution that can instantly locate a companys safety reputation. It can
is actually happening. However, temperature event anywhere in a also enhance plant reliability
technologies are now available that cryogenic process plant such as a through reduced downtime and
can overcome the limitations of LNG terminal. The DTS system can inspection time, while fewer
traditional measurement methods to be used in digital leak detection nuisance and false alarms can result
close that monitoring gap. and thermal profiling applications, in increased security and improved
Fibre optic distributed tempera- including LNG, liquefied petroleum productivity.
ture sensing (DTS) is one such gas (LPG), ethylene and CO2 load-
technology that has come to the ing and unloading pipelines, Principle of leak detection
fore as a realistic alternative moni- storage tanks, spill channels and using DTS
toring solution. This method of impounding basins, as well as the DTS is based on temperature meas-
monitoring has several key opera- cool-down monitoring of pipes and urements using fibre optic cables
tional advantages over conventional storage tanks. and can be used to detect both
real-time data (RTD) sensors. One From an operational perspective, liquid and gaseous leaks. The DTS
example of the benefits of DTS over the benefits of a digital cryogenic system illuminates the glass core of
traditional monitoring methods is temperature-monitoring system can the optical fibre with a 10-
that conventional thermal point be summarised as follows: nanosecond laser pulse, which
sensors are not able to provide full Leaks can be detected rapidly and corresponds to a 1m pulse. As the
coverage of a pipe or tank and mitigating action taken immediately, optical pulse propagates down the
therefore do not have the capability thus minimising the risk to opera- fibre, it undergoes scattering even
to pinpoint the precise location of tions personnel and equipment in the absence of impurities and

www.eptq.com GAS 2011 19

sensornet.indd 1 9/3/11 14:43:08

 structural defects. Part of this scat- situated within the control room specialist coatings are required.
tered radiation is known as Raman environment. However, a robustly Cables have been designed that are
scattering. As this vibration energy designed data acquisition device capable of consistently measuring
is a well-defined function of such as Sensornets Oryx system, temperatures down to -175C.
temperature, the ratio of the signals, which is made for deployment in
in conjunction with the time of harsh environments, can be posi- Pipeline monitoring
flight of an optical pulse, is used to tioned in the field, allowing the Monitoring the delivery, receiving
determine the temperature of the monitoring of hard-to-reach places. or recirculation lines from the vessel
fibre at a given point. The fibre optic cable is almost as to the tank or process facility is crit-
DTS can be used on long-distance important as the DTS itself, because ical, as this is one of the largest
pipelines, with repeater stations situ- it is the fibre that provides the sections of an infrastructure (which
ated every 80 km if required. This information. It is important to use can be up to several kilometres in
can be utilised for send-out lines or the right cable for the proposed length, often with limited access)
carbon capture and storage. More scope of work. For leak detection that can be exposed to the greatest
importantly for LNG applications, alone, it is possible to install a rela- amount of stress. Stories of pipe-
DTS can be equipped with multi- tively standard fibre optic cable. lines being lifted from their
plexing devices (also known as a However, the user should be supports due to performing the
mux) that can monitor several lines prepared for a one-time use only. cool-down process too quickly are
from a single unit. These could Tests have shown that standard not uncommon. The inclusion of
include delivery, recirculation and cable and fibre types detect the leak fibre optic monitoring can help
burn-off gas lines, as well as multi- at its initial stage, but when complete the cool-down process in
ple tanks, spillways and impounding subjected to temperatures of less a speedy but safe manner. Sections
pits. This can make DTS technology than -40C for even the shortest of fibre are strategically placed
a versatile and cost-effective option. periods of time the fibre and jacket directly onto the surface of the
construction deteriorate and become carrier pipe below the insulation
Fibre is the sensor unusable in the future. It may be layer. These are positioned on the
DTS systems consist of a limited acceptable in certain applications crown and the base of the pipe. By
number of components, which are for these cables to be sacrificial. For comparing the temperature of these
the DTS hardware and the sensing long-term use and cool-down moni- during cool-down, the product can
cable. The hardware is normally toring, cables and fibres with be delivered quickly and safely.

www.ptqenquiry.com
20 GAS 2011 for further information www.eptq.com

sensornet.indd 2 9/3/11 11:36:46

 PTQ_86x270:Layout 1 18-03-2010 17:58 Pagina 1

The same fibre can be routed along the length of pipe

outside the insulation layer and be used for leak detec-
tion. This fibre monitors the outside temperature of the
pipe. During leak conditions, the product returns to its
natural gaseous phase and cools the skin of the insula-
Italian design
tion to near cryogenic temperatures. The system can be
installed on different pipe configurations, including
A masterpiece
bare pipes, foam-insulated pipes and vacuum-insulated
piping, and has been independently verified by both
the TUV Nord and US Federal Energy Regulatory
Commission (FERC) for use on vacuum-insulated pipe
systems. The same monitoring lines can be extended to
cover the spillways and impounding pits two prime
locations for leak detection and monitoring.

Storage tank monitoring

For storage tanks, the sensing cable can be installed on
both the circumference (either within the annulus or in
the outer spillway) and the foundations of the tank.
This enables the system to check for leaks and monitor
the heating element to prevent frost heave. An addi-
tional fibre loop installed vertically up the wall of the
tank will also allow cool-down monitoring.
This solution can prove a very cost-effective alterna-
tive to resistance temperature detector sensors and
provides complete coverage and thus confidence for
the tank operator.
In older tank designs, DTS can be used to provide a
more reliable upgrade to the leak detection system by
installing the cable in the guttering in the perimeter of Creativity is the art we ap-
tanks, under valve spill trays and in tank overflow ply to achieve superior de-
sign and developments in
channels. The spill channels and impounding collection
technology.
channels are prime locations for products to collect in
For over 70 years we have designed and supplied
the event of a leakage. Installing sensing cables at low cost-effective technology, process plants and equip-
points in these locations provides an excellent early ment for the oil & gas and refining industry around
warning system. the world. With our expertise we provide tailor-
made solutions from studies and revamps to skid-
DTS in the real world mounted units and complete turnkey plants.
In compliance with Health and Safety Executive
requirements, the UKs National Grid Isle of Grain
LNG facilities asked Sensornet to provide a leak detec-
Oil & gas treatment
tion system. The monitoring system would be separation, dehydration and HC dew point control,
non-intrusive, permitting the continued operation of LPG and NGL recovery, sweetening,
the importation and recirculation pipelines during its mercaptan removal
installation and commissioning. Acid gas treatment & sulphur recovery
Traditional use of flow meters based on differential acid gas enrichment, Claus, ammonia Claus,
oxygen-enriched Claus, tail gas treatment,
flow measurement was considered inadequate to sulphur degassing
provide the required leak detection monitoring for
emergency shutdown purposes due to their relatively Advanced process controls
long response time. Other monitoring methods were Special process equipment
unable to provide distributed measurements over the
entire length of the pipeline. Therefore, a robust, non-
intrusive leak detection method was needed to provide
the required safety integrity level.
The system was designed with two cable loops and
two instrumentation units, capable of 1 out of 2 voting.
Each DTS system provides bidirectional monitoring
from either side of the loop, and the 24-way relay
SIIRTEC NIGI Engineering Contractors
modules provide hard wire contact relays to the client Via Algardi, 2 20148, Milan (Italy)
SCADA system in instances such as system error, Tel: +39-0239223.1 Fax: +39-0239223.010 Web: www.sini.it
Contact: [email protected]
where the rate of a temperature change exceeds a set

www.ptqenquiry.com
for further information
www.eptq.com GAS 2011 21

sensornet.indd 3 9/3/11 11:36:57

 temperature, where the minimum sensing cable affected by the historical analysis, they are
temperature exceeded a fibre break, temperature change, and the rate of available at any time from the hard
or where there is overheating in the leakage can be calculated by analys- drive located on the DTS system.
instrument cabinet. ing the distance the leak travels
The system provides non- over time. Environmental risk reduction
intrusive protection and was Temperature deviation of a single The financial cost of a leak can be
retrofitted by installation engineers point allows comparisons of a enormous; however, the greatest
in an operational plant without number of temperature values cost is to the environment.
having to shut down or stop opera- within any given zone, which can Environmental concerns are key not
tion. The independent fibre optic be set from 1m to 30km. Each only to the local authorities and
sensing cable loops covering both temperature point within a zone green groups, but also to the pipe-
pipelines provide added resilience normally has similar ambient prop- line operators, whose responsibility
to the installation. Additional multi- erties, so any significant variation is to ensure that risk is kept to a
plexer channels ensure future of a single temperature point minimum and, should a leak
expansion and flexibility, while self- compared with the average temper- occur, to react immediately and
contained test points were ature of the zone can indicate that effectively.
introduced at regular intervals on an event has occurred. Political sensitivities, pressure
the cable loops. These test points The DTS leak detection system from environmental groups and
are also used after the site accept- can also be configured to provide a costly litigation procedures have
ance tests (SAT) for periodic number of useful temperature acted as a warning to operators to
testing. comparisons. Absolute temperature ensure safety and environmental
To a tight deadline, sensing cables can vary, so it is not always a useful responsibilities are fulfilled and that
were installed in the pipeline corri- figure when used directly for leak approval is gained to construct
dor within culverts and on the pipelines through sensitive or
750m jetty section at Isle of Grain populated areas in the future.
using specialist access equipment. A robustly designed A system that monitors mission-
Sensornet deployed its Sentinel critical infrastructure, and obtains
DTS-XR20 system, which is opti- data acquisition meaningful and valuable informa-
mised to provide a temperature tion quickly and accurately, to allow
resolution of 0.1C in 10 seconds
device can be an asset to be as effective, safe and
along the entire length of the pipe-
line at 1.5m intervals. The high
positioned in the risk free as possible, is the desired
outcome.
specification of the XR20 allows the field, allowing the
plant to monitor the pipeline with Next-generation monitoring
accuracy and integrity. monitoring of Many methods for leak detection
The most valuable alarm criteria already exist. These include compu-
when detecting leaks are tempera- hard-to-reach places tational methods that are heavily
ture rate of change and temperature reliant upon statistical analysis;
deviation of a single point. In the mass balance techniques that
event a cryogenic leak occurs within detection. Obvious exclusions to the compare input and output values
the process plant, there will be a rule include cryogenic products and visual inspection by walking or
significant temperature drop (typi- such as LNG, which can reduce flying the line. Pigging is common
cally greater than 100C). surrounding the temperature to and may also be used to analyse
When the cryogenic fluid comes between -120C and -165C in the other aspects of the line. However,
into contact with the sensing cable, event of a leak. pigging can be disruptive to the
this will be detected instantly Each DTS unit is an autonomous operation and can carry its own
(down to 10 seconds) and device and an unlimited number risks. DTS is the only leak detection
pinpointed to within 1m. Since the can be connected to the SCADA or technique that can monitor an LNG
location of the leak can be detected distributed control system (DCS) facility in real-time and provide
instantly, rapid action can be taken network via standard communica- precise temperature and leak infor-
to mitigate any risk and control the tions protocols such as Modbus, mation to the nearest metre.
situation. Ethernet or Relay Contacts. This
Temperature rate of change at a allows the system to be used on
specific location can indicate that a pipelines varying from a few
Jerry Worsley is the Industrial Monitoring
significant temperature event has hundred metres up to thousands of
Manager for Sensornet. He has over 15
occurred in a relatively short space kilometres. Once networked, each years experience in the specification and
of time. This excludes any day/ device will only transmit alarm and deployment of fibre optic systems in oil
night or seasonal variations and regular health check data, ensuring and gas, construction and environmental
concentrates on shorter periods. the network is not overloaded with monitoring, and focuses on the
The volume of the leak can be esti- baseline fully distributed data. implementation of distributed sensing
mated from the physical length of Should these data be required for systems in the downstream process sector.

22 GAS 2011 www.eptq.com

sensornet.indd 4 9/3/11 11:37:10

 www.ptqenquiry.com
for further information

burkhardt.indd 1 20/9/10 10:10:44

 www.ptqenquiry.com
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cansolv.indd 1 8/3/11 13:53:57

 Glycol dehydration of high-acid
gas streams
A model based on mass and heat transfer closely predicts plant performance data
for glycol dehydration of high-acid gas streams

John Carroll Gas Liquids Engineering

Nathan Hatcher and Ralph Weiland Optimized Gas Treating

G
lycol dehydration is a proc- There are other facets of glycol two topics are inter-related because
ess that presents some dehydration that are interesting just both require the accurate assess-
unique challenges from both from an applied science viewpoint. ment of the interactions between
technical and computational stand- One of them is the heat transfer situ- components in the vapour phase;
points. In the first place, modern ation that ensues in a regenerator however, the solubility calculation
designs almost invariably use tower using both stripping gas and a is more demanding.
internals consisting of structured reboiler (Stahl column). When the Normally, to model the solubility
packing rather than the more tradi- hot gas hits the bottom of the pack- of a gas in a liquid, one uses the
tional bubble cap trays. Structured ing in the wash section atop the Henrys Law approach. A thermo-
packing offers a lower pressure column, it finds itself suddenly dynamically complete version of
drop and considerably higher going from an environment in which Henrys Law2,3 is:
capacity than trays, and it is well it is saturated with water in equilib-
suited to handling the very low L/ rium with a predominantly TEG >vi (P Pjo)H (1)
a~ixiHij exp = P v
G ratios common in dehydration. stream into an environment where it RT i i
However, until now, the height of is grossly under-saturated with
the packing was estimated using respect to the pure water stream in where
rules of thumb, not good engineer- the wash section. This causes i: Activity coefficient
ing science. Mass transfer rate-based extremely rapid humidification, and xi: Mole fraction of component i in
modelling, on the other hand, uses the humidification process extracts the solvent (its solubility)
science and therefore offers greater the necessary heat of vapourisation Hij: Henrys constant for solute i in
reliability of design. The other chal- as sensible heat from the liquid solvent j, kPa/mol frac
-
lenge of dehydration using any water phase. Sudden humidification vi Partial molar volume of i in
glycol is thermodynamic: water is can drop the wash water tempera- solvent j at infinite dilution,
the component of interest but it is ture by 3040F or even more. m3/kmol
probably natures most perversely This article addresses the efficacy Pjo: Vapour pressure of the solvent,
non-ideal chemical, which makes it of a new mass and heat transfer kPa
challenging to devise a truly accu- rate-based model in terms of how P: Total pressure, kPa
rate model for the vapour-liquid well it reflects known phase behav- R: Universal gas constant,
equilibrium, especially in systems iour and how closely it predicts 8.314 kJ/kmolK
with a high-acid gas content. known plant performance data T: Absolute temperature, K
Traditionally, sweetened gases using both bubble cap trays and yi: Mole fraction of component i in
have been the main candidates for packed columns without recourse the vapour
dehydration, mostly using triethyl- to height equivalent to a theoretical iv Fugacity coefficient for
ene glycol (TEG) prior to entering plate (HETP) or height of transfer component i in the vapour,
the transmission pipelines. More units (HTU) estimates and other unitless
recently, there has been much inter- rules of thumb.
est in sour gas injection as a means Most people believe that Henrys
of disposing of gas streams of too Phase equilibrium Law is only applicable to dilute
low quality for sulphur recovery. In Our phase equilibrium concerns are solutions, but the form in Equation
the context of carbon capture, the twofold: accurate calculation of the 1 can be applied without restriction.
recovered CO2 is compressed, lique- equilibrium water content of high- It would be unusual to do so, but
fied and injected into underground and low-pressure gases containing this equation can even be applied
formations. Handling these sour very high levels of CO2 and/or H2S; to mixtures that are not typically
and high CO2 streams requires and calculation of the solubility of considered to refer to the solubility
dehydration prior to compression all gases, including water, in the of a gas in a liquid at all; for exam-
and/or liquefaction. dehydration solvent itself. These ple, methanol and water.

www.eptq.com GAS 2011 25

ogtrt.indd 1 8/3/11 14:50:14

 can be greater than unity; however,
Saturated water content of gases
it is rarely greater than two.
Therefore, it is very important to
GPSA ref. Mole % (dry basis) Temp, F Pres, psia H2O lb/MMscf include this contribution in the
CH4 CO2 H2S Measd ProTreat
Ex 20-1 100 0 0 150 1000 220 216 solubility model.
Ex 20-2 80 20 0 160 2000 172 188 The fugacity coefficient in the
Fig 20-9 0 100 0 100 500 132 125.3 vapour phase can be calculated
750 110 102.5 using an equation of state such as
1000 125 100.7
2000 215 215.1 the Soave-Redlich-Kwong (SRK) or
3000 238 247.8 Peng-Robinson (PR) equations.
5.31 94.69 0 100 850 88 96.9 These cubic equations of state have
1125 81 99.2 been used for many years for
1500 128 148.6
2000 139 184.2 modelling the fluid properties and
Fig 20-16 89 11 0 100 2000 40.6 41.1 phase equilibrium in petroleum
89 11 0 160 1000 286 283.9 systems containing light hydrocar-
80 20 0 100 2000 40.6 45.1 bons and a few associated
80 20 0 160 1000 282 292.5
80 20 0 160 2000 172 188.5 non-hydrocarbons such as carbon
92 0 8 130 1500 111 103.5 dioxide, hydrogen sulphide and
72.5 0 27.5 160 1367 247 252.6 nitrogen. However, they are less
83 0 17 160 1000 292 293.4 successful with water and other
30 60 10 100 1100 81 81.2
9 10 81 100 1900 442 264.4 polar substances such as alcohols
5.31 94.69 0 77 1500 109.2 95 and glycols. Typically, the equa-
5.31 94.69 0 122 2000 164.6 234.5 tions of state must be modified to
predict accurately the pure compo-
Table 1 nent properties, and the mixing
rules must account for the complex
The numerical value of the 1.1. Neglecting the Poynting effect interactions.
Henrys constant is a function of altogether at these conditions means At low pressure, both the
both the solute and the solvent. the solubility is under predicted by Poynting correction and the fugac-
Thus, the Henrys Law constant, Hij, approximately 10%. ity coefficients are approximately
is different for methane in water A common definition used in unity. Furthermore, if the solubility
than it is for methane in methanol, describing the solubility of a gas in is low, Equation 1 reduces to the
and Hij is different still for ethane a liquid is partial pressure. The more familiar form of Henrys Law:
in water. Furthermore, for every partial pressure, Pi, of a component
solute-solvent pair, the Hij is a func- in a gas mixture is defined as: xiHij = yiP (4)
tion of the temperature. When
comparing different solutes in the Pi = yiP (2) or equivalently:
same solvent, the larger the Henrys
constant the lower the solubility of The non-idealities in the vapour xiHij = Pi
(5)
the solute. phase are embodied in the fugacity
The activity coefficient accounts coefficient. As an approximation, Physically, this equation says that
for the effect of concentration on the fugacity is to the partial pres- the solubility of a gas increases
the activity of the component in the sure as the compressibility factor is directly as the partial pressure of
liquid phase. The infinite dilution to the molar volume. Included in the component in the gas increases.
definition of the activity coefficient this quantity is the effect of pres- However, this idealised version is
is used here; its significance is that sure, temperature and composition limited to about 200300 kPa and
at infinite dilution, the activity coef- on the gas phase non-ideality. For gases with solubilities less than
ficient defined this way is unity. an ideal gas mixture, the fugacity about 0.1 mol%.
The exponential term is the coefficient of all components, i, in The ProTreat simulation tools
Poynting correction. It accounts for the mixture is unity: dehydration model uses the Peng-
the effect of pressure on the refer- Robinson equation of state (EOS)
ence fugacity, and it is important iv = 1 (3) for the vapour phase and currently
(significantly different from unity) offers a four-suffix Margules equa-
only at high pressure. For a small However, for a non-ideal mixture, tion activity coefficient model based
molecule such as methane, hydro- this quantity can be less than, on the data of Bestani & Shing1 for
gen sulphide or carbon dioxide in greater than or equal to unity. At the liquid phase, as reported by
water, the partial molar volume at relatively low pressure, it is gener- Clinton et al.4 A similar model
infinite dilution is approximately ally less than unity and it can be as based on the less conservative data
0.032 m3/kmol. Thus, at 7000 kPa small as 0.1 (and even smaller for of Parrish et al6 is planned for a
and 20C (293K), the Poynting liquids). At high pressure and high future release.
correction for these systems is about temperature, the fugacity coefficient There are two important aspects

26 GAS 2011 www.eptq.com

ogtrt.indd 2 8/3/11 14:50:24

 to thermodynamic modelling of Figure 1, but the stripper can also
Water content vs tray count
phase equilibrium in glycol dehy- be simulated without this column if
dration systems: the water content desired. Two condenser outlet
of the treated gas; and the hydro- Number Water streams permit the withdrawal of
of trays lb/MMscf
carbon, acid gas and especially the 5 8.5 wet stripping gas and/or water
benzene, toluene, ethylvenzene and 6 6.7 vapour from the system (Stream 19)
xylene (BTEX) content of the water- 7 5.7 and the removal of a specifiable
laden glycol. Table 1 compares 8 5.1 portion of condensed water (Stream
ProTreat model results with Gas 20), with the remainder returned
Processors Suppliers Association Table 2 as reflux.
(GPSA) Data Book entries for satu- Table 2 shows the effect of the
rated water content. Generally, stream may be absorbed in the TEG actual tray count on the water
ProTreat reproduces measured solution. ProTreat results conform content of the dehydrated gas.
values of water content to within closely to the conclusions of RR- ProTreat simulation indicates six
the accuracy of the data. The Peng- 131, as they should, because trays are adequate to reduce the
Robinson EOS that performs these ProTreats solubility model has water content from 88.7 lb/MMscf
saturated water content calculations been regressed to the actual meas- to the target level of <7 lb/MMscf
applies a large number of interac- ured BTEX solubilities. (32F dew point). Tower diameter
tion parameters (kijs) for the for 70% flood is 3ft. These values
interactions between water and the Process simulation are in line with GPSA Data Book
various gases, as well as between The GPSA Data Book contains a nice results. In summary, the available
the gases themselves. example of dehydration with TEG data indicate that the model is accu-
Other components whose solubil- (Example 2011). The gas is water rately reflecting literature data on
ity in TEG is pertinent are the acid saturated at 600 psia, with other the vapour-liquid equilibrium
gases and hydrocarbons, especially particulars noted in Figure 1. Two (VLE) and general TEG dehydra-
the BTEX components. Vapour- cases are detailed, both requiring tion experience, as reported by
liquid equilibrium constants two theoretical stages. One uses GPSA.
(K-values) for BTEX are available in bubble cap trays, which, at a tray
GPA RR-131, and the data there efficiency of 2530%, translates into Dehydration column performance
have been used to fit the ProTreat 68 actual trays. The other case uses Until now, only an equilibrium-stage
solubility model for these species. 10ft of an unspecified structured model has been available for calcu-
The data indicate that at typical packing. ProTreat has provision for lations involving the performance of
contactor conditions, approximately a separate Stahl column, shown structured packing. However, the
1030% of the aromatics in the gas immediately below the stripper in HETP of the particular packing is

<7 lb H20/MMscf
(<0.01474 mole% H20) Dehydrated gas
Outlet
12
22 24
99%wt TEG
3 gal TEG/lb H20 removed (5.1 gpm)
5
Contactor
9 8 CB 7 23 6
Outlet
Recycle Controller Cooler Stripper
19
Two ideal stages
Diameter = 3.4 ft
11 27 21
25-30% efficiency
30 MMSCFD gas 6.8 bubble cap trays, or
100F 10 ft of structured packing
600 psia 350 MBTU/hr
Water saturated 20
1 reboiler duty
Lean/rich 3 2

Stahl column

Stripping
26 gas
10 4

Figure 1 GPSA Data Book example 20-11

www.eptq.com GAS 2011 27

ogtrt.indd 3 8/3/11 14:50:33

 that there can be a significant
0 temperature bulge in dehydration
M125.X columns caused by the phase
5 M170.X
Distance from top of bed, ft change (condensation) of the water
M2.X
being absorbed. Water absorption
10 M250.X
generates sensible heating equiva-
M350.X
lent to its latent heat of
15
condensation. Also, when small-
crimp packings are used, the
20
temperature bulge is closer to the
25 bottom of the column because the
larger surface area allows water to
30 absorb so much faster. Figure 3
shows the water content of the gas
35 at various positions along the
height of the column. It is evident
40 that, after traversing the bottom
1000 110 120 130 140 20ft of M350.X packing, the gas is
Temperature, F about as dry as 99.95 wt% TEG at
100F can get it. With M125.X pack-
Figure 2 Temperature profiles and the effect of packing size in the Mellapak X Series ing, on the other hand, water is still
being removed even after the gas
surely related to packing size. For degree crimp angle) packings affects has passed through 40ft of packing.
structured packing, size can be dehydration performance. For So the required bed height is very
expressed in terms of specific surface Sulzer Mellapak structured pack- much a function of the packing size.
area and crimp size, characteristics ings, the packing designation (eg, It is not that rules of thumb cannot
that are geometrically related. Under M250.X) is a close indicator of the be made to work; rather, it is that
otherwise identical process condi- specific area, in this case 250 m2/m3. the right rules of thumb, at least for
tions, one should expect that large Simulations were all run with 40ft packing, depend on too many
crimp packing will require a deeper of packing and the absorber was parameters (not just packing type
bed to give the same performance as sized for 70% flood (911ft diameter and size but also on the gas and
a relatively short bed of small crimp depending on crimp size). The solvent fluxes through the column)
packing simply if for no other reason absorber was set up to dehydrate 49 and this makes them rough at best
than because the surface area of the 000 lbmol/h of wet sweet methane and unreliable at worst. Until now,
small crimp material is so much (trace CO2 and H2S) using 250 gpm the answer to this dilemma has
larger. of 99.95 wt% TEG. been to over-build the columns;
Figures 2 and 3 are simulations of The gas-phase temperature however, in a competitive environ-
how packing size within the profiles for the various packing ment, surely being able to avoid
Mellapak X Series (roughly 60- sizes shown in Figure 2 indicate over-design gives the knowledgea-
ble contractor and the astute
internals vendor a commercial
0 advantage. Mass and heat transfer
M125.X rate-based simulation is the preci-
5 M170.X sion tool that allows this to be
Distance from top of bed, ft

M2.X done.
10 M250.X Figure 4 shows that the blanket
M350.X rule of thumb of 68 trays for
15 dehydration can be a gross over-
simplification. The number of trays
20
depends at least on the dryness to
be achieved; that is, the dryness of
25
the solvent. If the target dew point
is not too stringent (say, 10 or 20lb
30
H2O/MMscf), 6 or 8 trays seem
35 adequate. But in very low dew
point applications, such as LNG
40 plants, two or three times that
0 1 10 100 1000 number of trays may be required to
Water in gas, Lb/MMscf get to the desired dryness. With
99.97% TEG, for example, it is
Figure 3 How water removal depends on packing size and packed bed depth possible to get to below 1 lb/MMscf

28 GAS 2011 www.eptq.com

ogtrt.indd 4 8/3/11 14:50:43

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burckhardt2.indd 1 9/3/10 14:25:09
 water content in the treated gas by
100
more than a factor of two. Stripping
gas permits more water removal
from the solvent and increases the
Dry gas water content,

dry TEG from 98.8 wt% to 99.8

10 wt%. This particular treated gas is
lb/MMscf

dry enough by transmission line

standards, but it is a long way from
dry enough for an LNG plant, for
1 99.97% example. However, this demon-
99.95% strates the principle that a Stahl
99.90% column can serve a useful purpose
99.50% it should be used when treated
0.1 gas needs to be drier than usual.
0 8 12 16
Number of trays
Observations from a mass transfer
rate model
Figure 4 Water removal to low dew points requires deeper beds and more trays The mass and heat transfer rate
model uses real trays, both in
water content, but even after 16 solvent from the reboiler and number and mechanical detail, and
trays, water is still being removed. contacting it with a flow of dry real packing in terms of actual bed
For the particular conditions inert gas. Stahl columns are essen- depths of a specific packing with
simulated in this study, it should be tial when the dried gas must have a defined geometry, including crimp
mentioned that high TEG viscosity very low dew point. Figure 5 shows angle, crimp size, surface treatment,
is a consideration and will nega- the effect of stripping gas rate (SCF specific surface area and vendor.
tively affect internals performance per gallon of TEG solvent) on the The simulation of a packed column
compared with light hydrocarbons, TEG purity and on the water begins by finely segmenting the
for example. At the solvent mois- content of the treated gas for packed height into a large number
ture levels encountered in these Example 20-11 from the GPSA Data of thin cross-sectional slices to
simulations, viscosity is not signifi- Book scaled up by a factor of five approximate the continuous nature
cantly affected by water content, and using six bubble cap trays in of contacting in packing. As a
and at the lowest temperature (feed the absorber and a 10ft bed of result, one gets to observe mass and
solvent at 100F) the viscosity is FlexiPac 1.6Y in the regenerator heat transfer effects on a fairly
about 19 cP (for reference, corn (includes a 2ft reflux wash section). detailed scale.
syrup is 50100 cP). This does not In terms of scale, the absorber is Figure 6 shows the vapour and
necessarily rule out using trays, nearly 7ft in diameter and is drying liquid temperature profiles through
although it does tend to make gas that is water saturated at 600 a 10ft-deep bed of 2in metal Nutter
structured packing more attractive. psia and 100F. The regenerator is Rings in a regenerator operating at
only 15in in diameter. 1 psig. The dehydrator is treating
Stahl columns and stripping gas The simulation results in Figure 5 440 MMscfd of wet, sweet gas with
A Stahl column gives an extra stage show that using even a modest flow a TEG flow of 1000 gpm, and the
of regeneration by taking the of stripping gas can reduce the bone-dry nitrogen stripping gas
flow to the Stahl column is 1.9 scf/
gal. The bed starts with a 2ft-deep
  wash section for TEG recovery
followed by an 8ft-deep stripping
  section for water removal. The

D r y
ga s,
lb/ M M sc G

Glyc ol
pur iU y w t %

 
stripper was simulated by dividing
it into 40 segments, each having a
  3in depth. Finer segmentation is,
of course, possible, but it
  adds nothing to the detail and
  very little more to the accuracy of
the simulation. We will traverse
 5&(
XU  the regeneration column, starting
MC..TD' with the condensate (essentially
 
      
pure water), which enters the
Stripping gas rate, SCF/gallon column from the condenser at
180F and is heated by the gas
stream (stripping gas and water),
Figure 5 Effect of stripping gas flow on solvent dryness and water content of gas which is at 198F.

30 GAS 2011 www.eptq.com

ogtrt.indd 5 8/3/11 14:50:53

 As the condensate trickles down
through the bed, it continues to be 0
heated by the wet stripping gas, but 1

Distance from top of bed, ft

within the first 18in its temperature 1
reaches a peak (194.5F) and then
3
suddenly plummets to about 160F.
The gas becomes hotter as we 4
descend through the column, and 5
eventually it experiences a rapid 6
climb to 294F. The question is: why 7
do the phase temperatures trend
8
this way? The answer for the gas
9 Vapour
phase is relatively simple: feed, Liquid
preheated to 300F, enters the 10
column at the 2ft level and flashes 150 175 200 225 250 275 300 325 350
into its vapour and liquid parts. Temperature, F
The fact that the vapour tempera-
ture changes radically at the feed Figure 6 Temperature profiles in regenerator with stripping gas via Stahl column
point is simply the result of the hot
feed meeting a cold reflux water As we traverse lower into the the vapour back into the liquid in
stream. But why does the reflux column and approach the bottom of the bottom couple of segments of
water cool so much? the stripping section, liquid starts the stripping section.
When the vapour leaves the top of to meet much hotter vapour coming Figures 7a and b are intended to
the stripping section, its water from the reboiler. (The bubble point show how the use of stripping gas
content is very nearly in equilibrium of TEG-water mixtures is quite affects these temperature profiles.
with the liquid in the stripping sensitive to water content when the The plots are for the same 10ft bed
section. The liquid there is better water content is low.) This cools the of Flexipac 1.6Y structured packing
than 95 wt% TEG with only 5 wt% vapour and heats the liquid, and referenced in Figure 5. Even when
(1718 mol%) water. So, although again some of the heat transfer is stripping gas is not used, the
saturated with water, it is saturated the result of water transferring from condensed water leaving the reflux
with only an 18 mol% water phase.
When it hits the first reflux segment,
this vapour is suddenly exposed to 
a pure, hot water stream (flowing

D ist a nc e
f rom
t op
of


from the wash section), so it is seri-

ously under saturated against pure

water. The consequence then is for
be d,
f t

water to evaporate as fast as possi- 

ble so as to resaturate the hot gas, 
now against pure hot water. This is 
a typical humidification operation 7BQPVS

and has some interesting character- -JRVJE

istics. The evaporation process is not          
mass transfer rate limited. Rather, it Temperature, F
is limited by the rate at which the
latent heat of vapourisation

demanded by the humidification
process can be drawn from the bulk 

D ist a nc e
f rom
t op

liquid to the gas-liquid interface. 

This process is one of heat transfer
of
be d,
f t


and, indeed, the rate of humidifica- 
tion right above the feed point is

controlled by essentially conductive

heat transfer across the liquid film 7BQPVS
running over the packing. The proc- 
-JRVJE
ess is heat transfer rate limited. The 
mass transfer driving force for           
humidification is so high that Temperature, F
enough heat is drawn from the
reflux water to cool it, in this case by Figure 7 Stripping gas is not necessary for anomalous temperature profiles
approximately 33F. (a) No stripping gas (b) Stripping gas at 3 scf/gal

www.eptq.com GAS 2011 31

ogtrt.indd 6 9/3/11 14:45:02

 assuming six bubble cap trays for
100 contacting. This is not much of an
Sweet
improvement for nearly a 50%
Water in treated gas, CO2
120 increase in reboiler energy. Are
H2S
there enough absorber trays to take
lb/MMscf

advantage of the greatly improved

80
TEG dryness? The number of trays
was increased from 6 to 8 in the
60 glycol contactor, while maintaining
the lean glycol purity of 99.96 wt%.
40
This dropped the water content by
5 10 15 20 an order of magnitude, from 2.0 to
Number of trays 0.2 lb/MMscf. Twelve trays gave
no improvement. So much for rules
Figure 8 Effect of tray count on water content of methane, CO2 and H2S dehydrated of thumb!
with 99.5 wt% TEG at 15 psig and 100F using bubble trays Finally, at 12 trays of dehydrator
contacting, some of the reboiler
section meets a much hotter gas, bulge in the reflux section is a duty was traded for stripping gas.
and a good part of the temperature consequence of the dilution by Lowering the reboiler duty from 2.5
equilibration takes place by water nitrogen. We note in passing that, to 2.0 MMBtu/hr and doubling the
evaporation from the reflux stream. to maintain water balance, the no stripping gas rate (from 3 to 6 SCF/
This is, again, a humidification stripping gas case required a 212F gallon) resulted in a predicted
process and the reflux water cools condenser temperature versus 180F water content of 0.13 lb/MMscf (a
as a result of the demand for latent for the case with stripping gas. dew point well below the hydrate
heat for vapourisation. In Figure 7b, formation temperature). Simulated
the presence of stripping vapour Factors that affect dehydration of glycol purity was 99.975 wt%. So it
dilutes the gas leaving the stripping sweet gases appears that stripping gas is a more
section, which results in slightly To learn more about the practical effective way to improve dehydra-
more driving force for humidifica- limits of glycol dehydration, a tion system performance.
tion together with the small sensitivity analysis was conducted, There is much that can be learned
additional capacity of the gas for starting with the 3 SCF/gallon by playing with a mass transfer rate
water. (How much the stripping stripping gas rate at 1.72 MMBtu/ model, even for such a seemingly
gas adds to the driving force and hr reboiler duty referenced in the mundane process as glycol dehy-
capacity depends on the relative preceding section. First, the reboiler dration. The mass and heat transfer
flows of stripping gas versus duty was increased to 2.5 MMBtu/ rate model allows one to probe the
reboiler vapour.) Again, the reflux hr, which amounted to an increase limits of what is in practice
water temperature peaks and then from 1124 to 1634 Btu/gallon. This possible; for example, trading
drops from 197F to about 141F, change allowed the glycol purity to expensive reboiler duty for possibly
for a total cooling of 56F, the same increase from 99.79 to 99.96 wt% cheaper stripping gas, or optimising
as for the case without stripping TEG. The water content of the dehydration unit performance in a
gas. However, with stripping gas dehydrated gas was predicted to demanding LNG setting. Since this
(dry nitrogen), the temperature drop from 2.7 to 2.0 lb/MMscf, kind of tool is so reflective of the
real engineering physics, the real
chemistry and the real processing
130 happening in an amine, dimethyl
Sweet ether of polyethyleneglycol
120
CO2 (DMPEG) or glycol plant, using the
Water in treated gas,

110 H2S tool as a virtual laboratory, pilot

100 plant and full-scale virtual plant is
lb/MMscf

90 very attractive.
80
70
Dehydration of nearly pure acid
gases: H2S
60
Down-well disposal of acid gases
50 (so-called acid gas injection)
40 requires the gas to be compressed
12 16 20 24 28
to a very high pressure. If the gas is
Packing depth, ft
wet, compressing it will cause
liquid water to drop out and this
Figure 9 Effect of tray count on water content of methane, CO2 and H2S dehydrated with liquid will be saturated with acid
99.5 wt% TEG at 15 psig and 100F using Mellapak M170.X structured packing gas at high pressure. Unless one is

32 GAS 2011 www.eptq.com

ogtrt.indd 7 8/3/11 14:51:14

 prepared to build compressors and cannot be vented to atmosphere artificial residence times, HETPs,
other equipment from unobtainium, with the water vapour stripped HTUs and other rules of thumb.
it is paramount that the water be from the solvent. The mass transfer rate-based tower
removed from the gas before Its high solubility in TEG is really model does not use rules of thumb
compression. Therefore, it is of the main difficulty with dehydrat- it uses science and good engi-
interest to compare dehydration of ing very high concentration H2S; neering to predict performance.
otherwise pure but water-saturated otherwise, in terms of just water These results were all obtained
H2S with the equivalent sweet gas absorption, the acid gases are no without any correction factors
volume. As Figure 8 shows, it is more challenging than any other whatsoever. They are true predic-
difficult to lower the water content gas from a purely process stand- tions in every sense of the word.
to the same level as high-pressure point. The difficulty is accurately
pipeline gas, for example, simply representing the gas-phase non- ProTreat is a mark of Optimized Gas Treating
because of the treating pressure. idealities that arise from the highly Inc.
The lines in this plot are simulation polar nature of water and H2S.
results for bubble cap trays in a References
1 Bestani B, Shing K S, Infinite dilution activity
10ft-diameter column treating 30 Conclusions
coefficients of water in TEG, PEG, glycerol and
MMscfd of either pure methane, Rules of thumb are fraught with
their mixtures in the temperature range 50 to
CO2 or H2S saturated with water at danger because often the rules 140C, Fluid Phase Equilibria, 50, 1989.
120F. Lean solvent is 200 gpm of simply do not apply. A blanket tray 2 Carroll J J, What is Henrys Law?, Chem. Eng.
99.5 wt% TEG at 100F. Figure 9 efficiency of 25% is close to the Prog., 87, 9, 1991, 4852.
shows similar results for Mellapak truth most of the time. But in deep 3 Carroll J J, Use Henrys Law for
M 170.X structured packing. water removal, 25% is optimistic multicomponent mixtures, Chem. Eng. Prog.,
Under otherwise identical condi- 88, 8, 1992, 5358.
tions, the water content of H2S in 4 Clinton P, Hubbard R A, Shah H, A review
equilibrium with the lean TEG is The mass transfer of TEG-water equilibrium data and its effect
on the design of glycol dehydration units,
somewhat higher than it is for
either CO2 or even methane. This rate-based tower Laurence Reid Gas Conditioning Conference,
Norman, OK, 2008.
has to do with the very polar nature
of H2S, which binds water more model uses science 5 Engineering Data Book, Gas Processors
Suppliers Association, 12th Ed, vol II, 20, 2004.
tightly to itself than CO2 does. But
this is information that can be and good engineering 6 Parrish W R, Won K W, Baltatu M E, Phase
behavior of the triethylene glycol-water system
gleaned more easily directly from
VLE calculations. The mass transfer
to predict and dehydration/regeneration design for
extremely low dew point requirements, 65th
rate-based dehydration model,
however, shows that in this instance
performance Annual Convention of the GPA, San Antonio,
TX, 1986.
H2S is pretty much completely
dehydrated after about 12 trays and, unless one adds several addi- John J Carroll is the Director, Geostorage
(about 20ft of packing), whereas tional safety trays, failure will Process Engineering for Gas Liquids
CO2 and methane require 15 trays threaten. The situation with pack- Engineering, Ltd in Calgary, Canada. He
(2426ft of packing) to reach their ing, be it random or structured, is was recently appointed Honored Visiting
ultimate dryness. much worse. Quoting or recom- Professor at Southwest Petroleum University
In an overall sense, the acid gases mending a single HETP or HTU is in Chengdu, China. He holds bachelor and
doctoral degrees in chemical engineering
appear to be no harder than hydro- foolhardy. The right value depends
from the University of Alberta, Edmonton.
carbons to dehydrate, although H2S on the packing as well as on the
Nathan Hatcher is Vice-President, Technology,
is very polar, which leaves it a little operating conditions and the gas Optimized Gas Treating, Buda, Texas. He has
wetter than most other gases. dryness sought. Rules of thumb had spent most of his career in amine treating and
However, there is nothing particu- their place when the best one could sulphur recovery, and has extensive experience
larly challenging about dehydrating do was an equilibrium-stage calcu- in the practical application of process
the acid gases, except for their high lation, and reliance had to be placed simulation to operations, troubleshooting and
solubility in the TEG solvent. For on experience as expressed (and training. He holds a BS in chemical engineering
the conditions corresponding to mis-expressed) in such rules of from the University of Kansas.
Figures 8 and 9 (15 psig and 120F), thumb. Today, we have available Email: [email protected]
the methane, CO2 and H2S content powerful heat and mass transfer Ralph Weiland founded Optimized Gas
Treating in 1992 and has been active in Canada,
of the rich solvent is simulated to rate-based simulation tools, and
Australia and the US in research in gas treating
be 8.4 ppm, 0.66 mol% and 3.32 reliance on rules of thumb and
since 1965.He developed the first mass
mol%, respectively. Thus, the water- other approximations and guesti- transfer rate-based model for amine columns
laden solvent contains quite a bit of mates is no longer warranted. for Dow Chemical and the Windows-based
H2S and this must be removed The beauty of the heat and mass ProTreat process simulation package. He holds
before the solvent is regenerated to transfer rate-based approach to BA.Sc, MA.Sc, and PhD degrees in chemical
a suitable state of dryness, because simulation is that one never has to engineering from the University of Toronto.
it is a certainty that this much H2S worry about tray efficiencies, Email: [email protected]

www.eptq.com GAS 2011 33

ogtrt.indd 8 11/3/11 11:21:17

 Serving you along
the entire LNG Value Chain.
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Linde AG for further information
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E-Mail: [email protected], www.linde.com

z4151.indd 1 07.09.2010 09:54:10

linde.indd 1 8/3/11 13:57:52
 Controlling corrosion in amine
treatment units
A range of measures can be taken to minimise corrosion in amine units

Jaya Rawat, Peddy V C Rao and N V Choudary

Bharat Petroleum Corporation Ltd

T
he amine unit plays a vital
role in the petroleum refining, Treated gas
gas processing, coal gasifica-
tion and ammonia manufacturing
Acid gas
industries. With advances in hydro-
Absorber
processing technologies to reduce Feed
sulphur levels in gasoline and gas Condenser
diesel fuels, the requirement for an Flash Reflux
efficient, well-established and relia- drum drum
ble separation system for the Stripper
removal of gases such as H2S and Water
Rich
CO2 has become an important amine Sour condensate
requirement for refiners. Amine
NaOH Product
treatment has proved to be the
Lean/rich Waste
principal commercially established
method for gas/liquid purifications exchanger
Lean
by removal of H2S and CO2. Lean amine
cooler
In many cases, the removal of
only H2S is required; CO2 remains
in the system, where it can be Figure 1 Process flow diagram for amine treatment unit
managed by optimising the reaction
rates of amines and treating gases. stable salts (HSS) are formed and amine then goes to the regenerator
The treatment involves the removal they gradually build up beyond column. In the regenerator column,
of H2S and CO2 gases from flue tolerable limits in the amine circula- the rich amine solution is stripped
gases and LPG, with the help of tion loop. Amine plant operational of its absorbed sour gases, with
amines such as monoethanolamine problems, such as excessive foam- steam as the heating medium, so
(MEA), diethanolamine, (DEA) ing, corrosion and capacity that the regenerated amine can be
methyldiethanolamine (MDEA) and reduction, are often attributed to reused in the absorber.
diisopropanolamine (DIPA), which the accumulation of amine HSS. The steam strips out the absorbed
have a tendency to absorb both the Significant amine loss has been H2S and CO2 present in the amine
gases. In an absorber column, sour observed in the operation of these solutions according to the following
flue gas or LPG comes into contact units because of its high foaming reactions:
with lean amine. The treated gas/ characteristics.
LPG goes for end use and the H2S- R2NH3S R2NH + H2S (1)
rich amine then goes to the Amine treatment process
regenerator column. The treatment involves the removal (R2NH3) CO3 R2NH + CO2 + H2O (2)
During this process, major prob- of H2S and CO2 from fuel gas and
lems of corrosion and instability of LPG with the help of amine solu- where R is a CH2CH2OH group.
operation raise a significant threat tions, which tend to absorb both The liberated acid gases and
to an amine gas-treating plant, gases. A process flow diagram of steam from the top are cooled in
resulting in unscheduled break- the unit is shown in Figure 1. In the the overhead condensers. The
downs and outages. Major corrosion absorber column, the sour fuel gas uncondensed gas goes to the
failures in these units have been or LPG comes into contact with sulphur recovery unit via a pres-
attributed to free acid gas and high lean amine, which absorbs H2S and sure control valve and condensed
temperatures. Within this process, CO2. The treated gas/LPG goes for liquid is pumped back to the
contaminant byproducts called heat end use and the H2S- and CO2-rich column as a total reflux. From the

www.eptq.com GAS 2011 35

bpcl.indd 1 8/3/11 14:53:49

 regenerator bottom, lean amine systems is caused by an accumula-
exchanges heat with feed-rich Sweet gas tion of high concentrations of H2S,
amine before entering the nitrogen compounds and CO2 along
absorbers. with a variety of acids. Rich amine
Lean solvent
causes pitting of the exchangers
Absorption process Liquid
and piping, as well as the reboiler
The absorption process is used to Natural section, where free acid gases and
gas
remove a component (solute) from Gas higher temperatures are the main
the gas stream by contacting the driving forces of corrosion
gas with a liquid solution (see
Figure 2 and Equation 3): Rich solvent Formation of heat stable amine salts
Heat stable amine salts (HSAS) are
Cooling
Figure 2 Schematic presentation of formed by the reaction of inorganic
Lean amine + H2S + CO2 amine rich in H2S + CO2
Heating (3)
absorption process contamination of the amine solution
with strong and weak acids. Acids
ucts. H2S formed during some increase the corrosion, fouling and
The amine solvent is the water reactions also causes corrosion in emulsification potential and reduce
solution of an alkanolamine used to iron-based metallurgies by forming the gas-treating capacity. HSAS are
remove the H2S, mercaptans and iron sulphide (FeS). CO2 corrosion heat stable because these acids are
CO2. The most common amines is caused by the reduction of undis- not removed in the regenerator.
used include MEA, DEA, DIPA, sociated carbonic acid in turbulent Acids with a pKa of less than 5 will
MDEA and diglycolamine (DGA). areas, where a passive ferrous form HSAS, mainly formic, cyanic
These amines are very water solu- carbonate scale is unable to form. and sulphuric acids. Formic acid is
ble because they contain hydroxyl Carbonic acid can undergo the very corrosive to carbon steel and
groups. The nitrogen or ammonia following reactions: stainless steel in the absence of
group (NH3) reacts with the acid oxygen, while MDEA formate is
gas to form a water-soluble salt. H2CO3 + e- HCO3- +H (4) more corrosive than formic acid
Typical properties of the amines alone. Although low concentrations
and their structures are given in H2CO3 CO2 + H2O (CO2 gas evolution) (5) of HSAS are not corrosive, corro-
Table 1. sion, fouling and foaming increase
Some of the important criteria for The organic acids and many as the acids concentration increases.
the selection of amines are: amine degraded products, high The reaction of amines with weak
High solubility velocities and turbulence break acid gases gives thermally reversi-
Low volatility and viscosity down an FeS protective layer and ble salts as follows:
Easy recovery remove iron from the metal. The
Least corrosive and least cost. corrosion product is water stable MDEA + H2S MDEAH + HS- (6)
until it contacts the high H2S
Corrosion problems in amine units concentrations in the absorber. FeS The reaction of amines with acids
Corrosion in the amine system is is formed and precipitates to create stronger than acid gases produces
mainly caused by acid gases, strong deposits, while acid is returned to HSAS:
acids, contamination such as amine resume the corrosion cycle.
HSS and amine degradation prod- Corrosion in the overhead MDEA + H MDEAH+ + X- (7)

where HX is a strong acid and X-

Amine solvents denotes an acid anion such as
formate, acetate, propionate, glyco-
H2N
S.No. Amine Chemical structure
OH Molecular Base strength, late, oxalate, sulphate, thiosulphate,
solvent H2N H
N
weight pKa thiocyanate, phosphate, nitrate and
OH
Monoethanolamine (MEA)
HO OH 61.8 9.52 chloride. Alkalies such as NaOH
H
N
Diethanolamine (DEA) HO O OH
105.14 8.88 and KOH also react with strong
HO acids and contribute to the forma-
O
Diglycolamine (DGA) or 105.14 9.50 tion of HSAS.
aminoethoxyethanol HO H2N
Salts formed by either of these

HO H2N
N
OH reactions lower the pH of the solu-
Methyldiethanolamine (MDEA)
HO OH 119.16 8.56 tion and increase conductivity,
N
thereby making the system more
acidic and prone to corrosion.
Diisopropanolamine (DIPA) H 133.19 8.82
N This article deals with the differ-
HO OH
H ent types of corrosion mechanisms
N
HO OH in an amine treatment unit and the
Table 1 control strategies to deal with them,

36 GAS 2011 www.eptq.com

bpcl.indd 2 8/3/11 14:53:56

 including selection criteria for
Corrosion rates of various alloys with amine solvents
amine solvents and metallurgical
guidelines for the construction of
amine plants. Metals Corrosion rates, MPY
DEA solvent MEA solvent MDEA solvent
Carbon steel 15.7 10.6 8.4
Results and discussion 304 SS 10.5 5.8 3.4
Corrosion studies were carried out 316 SS 9.5 3.8 1.2
with rich and lean solutions of DEA Monel 5.6 4.5 0.9
under varying operating conditions
with various metallurgies, such as Table 2
carbon steel, stainless steel and
Monel. The solvents used for the
experiments were DEA, MEA and 
7FMPDJUZ

NTFD
MDEA. Weight loss studies were  7FMPDJUZ

NTFD

C or r os i on
r a t e ,
M P Y
carried out on the process samples 7FMPDJUZ

NTFD
using carbon steel coupons accord-  7FMPDJUZ

NTFD
ing to ASTM G1-90 and ASTM G 
3172. The experimental setup
consisted of a reactor, condensers 
and a constant temperature bath.

Various corrosion coupons of carbon
steel were placed with the help of 
specially designed coupon holders

in the reactor and condenser section -FBO
BNJOF 3JDI
BNJOF
in such a way as to observe corro- Amine types
sion in the liquid as well as vapour
phase. The liquid temperature was Figure 3 Corrosion rates of rich and lean amine at various fluid velocities
maintained at 120 +/- 1C. A filming
amine-based corrosion inhibitor was loaded with acid gases, their various loadings of H2S. It was
used and its dosages with various tendency to cause erosion and observed that the corrosion rate
samples were optimised. The corrosion increases, so that, in the rises with an increasing H2S concen-
weights of the coupons were meas- event of higher fluid velocities tration. Furthermore, corrosion
ured before and after the test, and along with turbulence, the passive rates are greater at higher tempera-
corrosion rates were then calculated. layer of FeS becomes damaged, tures. At 120C, a corrosion rate of
which results in higher corrosion 40 mil/y was obtained with a H2S
Effect of corrosion rate with rates. The recommendation is to loading of 5%. Hence, at higher
various metallurgies operate at lower velocities with rich temperatures, with greater percent-
The results of the corrosion studies amine solutions rather than lean ages of H2S, the use of a corrosion
were obtained from various amine amine solutions inhibitor is recommended.
solutions, including DEA, MEA and
MDEA, along with various metall- Effect on corrosion rate of varying Effect of corrosion inhibitor
urgies (see Table 2). Amine temperatures Corrosion inhibitors of the filming
solutions at 15% along with 5000 The corrosion rates of carbon steel amine type were found to be the
ppm of dissolved H2S were used were studied at temperatures vary- most suitable for reducing corrosion.
for the studies. ing between 60C and 120C, with Concentrations of corrosion inhibitor
It was observed that corrosion
rates are lower with Monel and 
stainless steel metallurgies, )4



compared to carbon steel. Further )4


Cor rosi on
r at e ,
MPY


corrosion rates were observed to be )4


lower with MDEA and MEA, 

compared to DEA. 

Effect of fluid velocities on 
corrosion rates 
Corrosion rates vary with fluid 
velocities and amine types. A fluid

velocity higher than 1.5 m/sec is, in   
the case of a rich amine solution, Temperature, C
more corrosive than a lean amine
solution. When amine solutions are Figure 4 Corrosion rates at various H2S conc and temperature

www.eptq.com GAS 2011 37

bpcl.indd 3 8/3/11 14:54:08

 Pump and water wash to control
25
Corrosion inhibitor (0 ppm) overhead corrosion usually caused
Corrosion inhibitor (5 ppm) by ammonia salts deposition
20 Corrosion inhibitor (10 ppm) Corrosion monitoring by ER and
Corrosion rate, MPY LP probes. LP probes should use a
15
data logger to average multiple
readings
Routine amine tests should be
10
performed for amine concentration,
acid gas loading and foaming
5 tendency
Rigorous analysis for acids and
0 metals should be conducted every
60 90 120 46 weeks.
Temperature, C
Summary
Figure 5 Corrosion rates with different dosages of corrosion inhibitor Corrosion in amine treatment units is
critical as it involves a check on vari-
varying from 5 to 20 ppm were used amine loading and increasing the ous operating and mechanical
for the studies, along with DEA and circulation rate parameters, such as the selection of
a 5% H2S loading. A reduction in the Circulation rate increases the corro- solvent, operating conditions and
corrosion rate was observed at all sive action of HSAS, flashing acid gas metallurgies. It can be minimised by:
temperatures in the range 60120C. amine degradation products, high A suitable selection of solvent
The corrosion rate was very high temperature, acid gas loading and Monitoring HSAS and metals and
without a corrosion inhibitor (22 high amine concentration. minimisation of HSAS formation
mil/y at 120C), whereas a signifi- The selection of proper corrosion
cant reduction in the corrosion rate Use of corrosion inhibitors inhibitor with optimised dosage
was observed after dosing the corro- Injection of filming amine-type and its injection at proper locations
sion inhibitor at 10 ppm. inhibitor should be carried out in in the unit
the regenerator overhead, directly Water washing the overhead
Corrosion control strategies in upstream of the problem area, with reflux
amine treatment units usually via the reboiler feed line Continuous corrosion monitoring.
Minimising HSAS formation Inhibitor injection rates and
HSAS build-up tolerance is dosages should be based on contin- Acknowledgement
specific to the amine solution used uous corrosion monitoring. The authors express their sincere thanks
With increased HSAS concentra-
to BPCL management for their constant
encouragement and support.
tion (above 4%), fouling, foaming Important properties of corrosion
and corrosion problems increase. inhibitors References
With MEA and DEA (10% of amine Low to no foaming tendency 1 Dupart M S, Bacon T R, Edwards D J,
concentration), 23% HSAS does Good solids dispersion Hydrocarbon Processing, 1993, 311.
not create severity, but, in the case Good solubility in water 2 Verma N, Verma A, Fuel Processing
of MDEA, 2% HSAS creates severe Should provide good adherence Technology, 90, 2009, 483489.
corrosion. to FeS protective layer on the metal 3 Fontana M G, Corrosion Engineering, McGraw
surface Hill Publication, 1987.
4 Rooney P R, Dupart M S, Bacon T R,
Optimising fluid velocities Effective against organic acid,
Hydrocarbon Processing, 1997, 6571.
High velocities and turbulence CO2, H2S and amine degradation
damage the protective FeS layer. product corrosion Jaya Rawat is a Deputy Manager, R&D, in the
The process of forming scale results Compatibility with all the alloys Corporate R&D Centre of Bharat Petroleum
in higher corrosion rates, as erosion in the system. Corporation Ltd, Surajpur, India. She holds a
forces removal of the scale doctorate in chemistry and has published 50
To reduce erosion, amine veloci- Inhibitor injection points and research papers and five patents.
ties should be no greater than corrosion monitoring Email: [email protected]
1 m/sec (3 ft/s) in exchangers and Commonly added to the regenera-
Peddy V C Rao is Senior Manager, R&D, with
Bharat Petroleum Corporation Ltd. He holds a
2.1 m/s (7 ft/s) in piping. tor overhead, the inhibitor returns to
doctorate in chemistry from Indian Institute of
the tower with the reflux and then is
Technology, Bombay. India.
Acid loadings distributed throughout the unit Email: [email protected]
Acid gas loading, circulation rate Water wash the overhead N V Choudary is a Chief Manager, R&D, with
and amine concentration should also condenser with a reflux slipstream, Bharat Petroleum Corporation Ltd. He holds a
be adjusted to minimise corrosion routinely purge the ammonia in the doctorate in chemistry, has published over 70
Amine concentration should be reflux accumulator and inject the research papers and filed over 50 patents.
increased accordingly before rich inhibitor in the reboiler feed line Email: [email protected]

38 GAS 2011 www.eptq.com

bpcl.indd 4 8/3/11 14:54:15

 A promoter for selective H2S
removal: part I
A new MDEA promoter achieves very low H2S lean loadings and the option for
flexible design of acid gas enrichment units by varying absorber heights

Gerald Vorberg, Ralf Notz and Torsten Katz BASF SE

Wieland Wache and Claus Schunk Bayernoil Raffineriegesellschaft

T
he selective removal of H2S achievable lean loadings are an where simultaneous removal of H2S
has become an important option to adjust selectivity by vary- and CO2 is intended. This means
topic over past decades. This ing the absorber height without that suitable solvents have different
is driven by several factors, one losing control over a tight H2S spec- characteristics.
being the production of an H2S- ification with a sufficient safety
enriched, and thus high-quality, margin. H2S selectivity
Claus gas in MDEA-based acid gas This article gives an overview of Definitions
enrichment (AGE) units. the principles, while part II (see In industry, various expressions for
Other fields where selective gas PTQ, Q2 2011) shows the ability of H2S selectivity are used to judge the
treatment would also be beneficial this promoter system to drop H2S selectivity of an absorption process
are natural gas and refinery appli- lean loadings in a refinery amine with regard to H2S compared to
cations. For sour gas fields, this system. CO2. In the following, the most
application is becoming increas- Acid gas removal with amine- important examples are given (cH2S
ingly attractive due to limited sweet based solvents is a mature and and cCO2 stand for molar concen-
gas resources. For refineries, debot- widespread application in the oil tration in gas streams):
tlenecking issues and an increased and gas industry. Besides specific
flexibility for processing different design variations, acid gas removal H2S selectivity (rigorous definition)
crudes are the most important units (AGRU) always follow the H2S selectivity is calculated as:
drivers. principle of an absorber-regenerator
From an operational perspective, configuration. First, acid gases are H S_selectivity = (CH2S feed gas - CH2Streated gas)/CH2Sfeed gas
savings in energy and circulation removed from the fluid stream in
2
(CCO2 feed gas - CCO2treated gas)/CCO2feed gas
rate, as well as a reduction in equip- the absorber by the liquid solvent
ment sizing, are the obvious typically at 2050C and elevated CO2 co-absorption (or CO2
benefits of enhanced selective pressures up to 80 bar, depending pick-up)
treatment. In addition, tight envi- on the feed gas conditions. In a CO2 co-absorption in the absorber
ronmental regulations and sulphur second step, the dissolved acid is specified as:
specifications are attributed to this gases are desorbed in a regenerator
subject. at inverse conditions. Desorbed C treated gas
CO2_co-absorption = 1- CO2
The principles for the selective acid gases can be further processed CCO2 feed gas
removal of H2S with amine-based in Claus sulphur recovery units
solvents follow three major routes: (SRU), reinjected for enhanced oil CO2/H2S ratio comparison (often
Hindered amines, controlling the recovery (EOR) or simply flared. used for acid gas enrichment)
selectivity primarily in the absorber When focusing on the two main The decrease in CO2/H2S ratio indi-
Various design options and acid gas components, CO2 and H2S, cates the efficiency of an acid gas
absorber internals, affecting the process designers differentiate enrichment unit:
difference in CO2 and H2S mass between total acid gas removal and
transfer kinetics selective sulphur removal or simply Ratio C feed gas
= CO2
C acid offgas
vs Ratioacid offgas CO2
feed gas
Promoted tertiary amines, focus- selective removal. As the name CH2S
feed gas CH2S acid offgas
ing more on enhanced regeneration implies, selective sulphur removal
and thus leading to lower H2S selectively removes H2S, while A proper comparison of these
loadings. other acid gases, for instance CO2, expressions for different solvents or
With respect to the final point, are slipped into the treated gas. applications must be evaluated with
the advanced promoter system Consequently, selective removal great care, since the absolute level
presented in this article can be a has a different focus compared with of H2S in the treated gas is less
considerable leap forward for more total acid gas removal processes, considered. In other words, H2S
flexible selective designs. Very low, such as BASFs aMDEA process, selectivity is well defined, but not

www.eptq.com GAS 2011 39

basf.indd 1 9/3/11 12:35:20

 particularly suitable for judging H2S specifications in
treated gas.

BORSIG
The following example, calculated according to the
rigorous definition, might show the difference:

Feed gas: H2S 1 v% CO2 5 v%

Treated gas case 1: CO2 1.5 v% H2S 1 vppm H2S selectivity = 1.428
Treated gas case 2: CO2 1.5 v% H2S 50 vppm H2S selectivity = 1.421

Dependency on operating conditions

Selective treatment with amine-based solvents gener-
ally takes advantage of the rapid reaction of H2S
compared to the kinetically hindered reaction of CO2;
CO2 first has to react with water to form carbonic acid.
In particular, tertiary amines are often used for selec-
tive applications, as they are unable to form
carbamates, the only fast reaction involving CO2.
These are the reactions of tertiary amines in aqueous
solutions:

Reaction of water and amine (fast)

_
R1R2R3N + H2O R1R2R3NH+ + OH
_
2 H2O H3O + OH
+

H2S reaction (fast)

_
H2S + H2O HS + H3O+

CO2 reactions (overall reaction slow):

_
CO2 + 2H2O HCO3 + H3O+ (slow)
_ _
HCO3 + OH H2O + CO32- (fast)

In this reaction system, CO2 co-absorption, and thus

Leading Technology for H2S selectivity, is heavily influenced by reaction condi-
tions such as the temperature and concentration of CO2
Innovative Solutions and H2S in the liquid phase. This means higher pressure
and temperature, as well as a higher CO2/H2S ratio in
the feed gas, favour CO2 co-absorption and lower H2S
Process Gas Waste Heat selectivity.
Recovery Systems
for ammonia, methanol, hydrogen, gas-to-liquid plants, coal Applications
gasification plants, direct reduction plants in iron metallurgy, Selective H2S removal is predominantly required and
waste heat boilers in nitric acid, caprolactam and formalde- applied in the following segments:
hyde plants, waste heat boilers downstream of the partial
Natural gas (NG)
oxidation of oil and natural gas
Refinery off-gas (ROG)

Quench Coolers Claus tail gas (TG)

for ethylene cracking furnaces: AGE.

- Transfer Line Exchangers (TLE) AGE has probably been the most important driver for
- BORSIG Linear Quenchers (BLQ) the development of selective solvents in recent years. It
requires utmost H2S selectivity in order to get a H2S-rich
Scraped Surface Exchangers feed gas for the downstream Claus SRU or for down-
hole reinjection. For instance, a minimum H2S
Other BORSIGProducts: concentration of 25 vol% is a guiding value for SRUs.
Compressors, Compressor Valves and Blowers, Membrane Higher H2S concentrations are naturally more desirable.
Technology, Boiler and Power Plant Technology, Industrial
Upgrading and debottlenecking measures triggered
and Power Plant Services
the move to more selective treatment in refineries by
replacing unselective with selective generic solvents. In
fact, the majority of refinery expansions lead to a higher
total sulphur nameplate capacity by processing more
BORSIG GROUP sour crudes. Without significant mechanical changes,
Egellsstrasse 21
D-13507 Berlin/Germany
capacity increases of more than 25% have been achieved,
as mainly H2S, instead of CO2 and H2S, has been proc-
Phone: +49 (30) 4301-01 Fax: +49 (30) 4301-2236
E-mail: [email protected] www.borsig.de essed along the entire acid gas removal chain. Moreover,

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basf.indd 2 9/3/11 12:35:56

 tighter sulphur regulations in many
Characterisation of H2S selective applications
countries have been fulfilled in
combination with improved sulphur
recovery rates by implementing Natural gas Acid gas enrichment Refinery offgas Tail gas
Typical feed gas specification
Claus tail gas treatment (TGT), pH2S, mbar/psi Up to 10 000/145 Below 500/7.25 Up to 2000/29 Below 100/1.45
where H2S is selectively removed pCO2, mbar/psi Up to 10 000/145 Below 2000/29 Up to 1000/14.5 Below 500/7.25
and returned to the Claus inlet. Typical treated gas specification
From todays market perspective, cH2S, vppm 510 5100 5100 550
CO2 slip Flexible Very high Medium High
selective acid gas removal in natu- System hold-up Large Medium Medium Small
ral gas is an increasingly interesting
application. On the one hand, the p = partial pressure/c = concentration

utilisation of more sour gas fields is

increasing rapidly, while the access Table 1
to sweet natural gas resources
becomes more and more limited the inability to enter into the incorporate two useful properties
(sour in colloquial terms means H2S carbamate reaction with CO2. Its at low acid gas partial pressures;
>5 vol%). On the other hand, for ability to change its characteristics as a secondary amine, the reaction
sales gas specification, operators either for total acid gas removal or is fast and acid gas capture capac-
request not the highest level but a selective removal by adding an acti- ity is higher compared to tertiary
dedicated or even an adjustable vator or a promoter has increased amines. In contrast to generic
level of selectivity. This means that its range of application because of: secondary amines, steric hindrance
CO2 slip, and thus H2S selectivity, Availability and pricing due to the shape of the molecule
needs to be controlled to match, for Fewer corrosion issues than with reduces the CO2 equilibrium load
instance, a certain calorific value for primary and secondary amines and thus increases the selectivity.
the sales gas. CO2 treated gas speci- Good absorption performance However, both advantages are
fications between 1.5 and 2.5 vol% Suitability for generic designs progressively reduced at increas-
are most common. But what does Selectivity adjustment by blend- ing acid gas partial pressures, such
this mean for selective designs? ing with other amines as those in most natural gas appli-
In fact, the quality and quantity Low regeneration demand for cations (see Table 1). Thus, for
of production wells change over the absorbed CO2. highly selective applications at low
years, but the treated gas specifica- H2S partial pressures, such as acid
tion should remain within a narrow Promoted MDEA gas enrichment, hindered amines
window at all times. This task is a H2S is a stronger acid than CO2 and are better positioned and highly
challenge for both process design thus has a stronger binding energy efficient. Moreover, the relatively
and solvent activity. Proper selec- at the stripper temperature. high price level of hindered amines
tive designs should be able to Consequently, amine regeneration makes it more economical in small
handle: of H2S down to trace levels becomes plants (AGE) than in large (natural
Various turndown rates progressively more difficult. In gas) plants.
Changing environmental condi- particular, designs with very low
tions, in particular temperature H2S specifications in the low ppm Design specifics for selective
Various feed gas scenarios. range may use regeneration treatment
Table 1 shows an overview of the promoters in order to release H2S For the design, various aspects have
application fields and their major more easily from the solution. In to be taken into account:
differences in conditions and this regard, MDEA acidified with H2S specification in the treated
requirements. The listed criteria are phosphoric, sulphuric or other acids gas
crucial for the solvent as well as for becomes regenerated more easily. CO2 specification/slip in the
design selection. Even the unintentional acidification treated gas
by formation of heat stable salts Feed gas conditions (composition,
Solvents for H2S selective treatment (HSS) and their acids acetates, pressure and temperature), which
Three types of solvents are most formates, sulphates and so on may vary over the plants lifetime
suitable for selective treatment: leads to a very efficient H2S Required CO2/H2S ratio in the
generic methyldiethanolamine, regeneration boost. However, the acid off-gas
MDEA, (tertiary amine) and blends, level of acidification has a certain Ambient conditions
promoted MDEA and severely ster- limit, as there is an impact on the Flexibility/turndown rate
ically hindered amines. pH value of the amine solution and Footprint and size of the plant.
the equilibrium curve of the acid For MDEA-based or other
Generic MDEA (tertiary amine) gas solubility in the solvent. solvents, for which selectivity is
and blends controlled by kinetic effects, several
Among selective amines, MDEA is Severely sterically hindered amines factors are important for design:
the most common due to its many Sterically hindered amines, such as CO2 reaction kinetics and number
beneficial properties, in particular tertiarybutylaminoethoxyethanol, of theoretical stages, mass transfer

www.eptq.com GAS 2011 41

basf.indd 3 9/3/11 12:36:11

 and internals selection, and temper- tions, in the very low ppm range, force for the mass transfer at the
ature and selectivity. are required. This means that a absorber overhead.
design with a large safety margin is
CO2 reaction kinetics and number of highly advisable. As a consequence, Mass transfer and internals selection
theoretical stages process designers apply multiple The pathways of mass transfer for
With respect to kinetics, shorter amine feed points to the absorber CO2 and H2S are quite different.
absorber columns reduce the over- to adjust the mass transfer area. In While CO2 absorption is affected by
all mass transfer area and overall some cases, even flexible weir mass transfer limitations in the
retention time, so CO2 absorption is heights are designed as a sophisti- liquid phase, the instantaneous H2S
reduced to a certain extent. cated solution. An even higher reaction in the solvent moves the
However if the absorber height is degree of selectivity through reduc- major H2S mass transfer resistance
too short, H2S may not be absorbed tion of the tower height could be into the gas phase. As a conse-
sufficiently. In todays selective achieved by reducing the lean load- quence, an adequate design tool has
designs, very tight H2S specifica- ings and by increasing the driving to consider these mass transfer
resistances for different compo-
nents. Rate-based simulation tools,
which also need detailed input for
the column internals, are capable of
AdvAmine & AdvaSulf predicting operational conditions
with the required accuracy. They

your best tools

can even predict operating condi-
tions depending on the flow regime.
The results often depend on the

in sour gas treatment choice of internals: trays versus

packing.
Trays are very robust and, with
respect to multiple amine feed
Prosernat offers points, the design is easy to imple-
a global range ment. In addition, fouling or
of advanced technical solutions plugging is a minor issue. On the
for sour gas treatment other hand, a packing design usually
and sulphur recovery
enables smaller column diameters to
be selected and provides more safety
and flexibility for changing L/G
ratios. However, the installation of
multiple amine feed points is more
complex. Lower liquid hold-up and
lower back-mixing tendencies
increase the selectivity substantially
compared to trays operated in their
standard envelope.
AdvAmine Temperature and selectivity
HiLoadDEA
Feed gas and amine temperatures
MDEAmax
are crucial factors for CO2 co-absorp-
energizedMDEA
tion and resulting selectivity, but the
AdvaSulf influence from a designers perspec-
Claus tive is limited to the available
Tail Gas Treatment, Clauspol II, cooling capabilities. In regions where
Sulfreen, Sultimate seasonal ambient temperatures may
Sulphur degassing, Aquisulf differ by more than 40C (72F) and
peaks may reach 50C (122F) or
more this is a particular challenge.
By taking the most severe condi-
tions for instance, high amine
and feed gas temperatures as an
Tour FRANKLIN - 100/101 TERRASSE BOIELDIEU example, CO2 at a high partial pres-
F-92042 Paris La Dfense Cedex - France sure will be absorbed more easily
Phone: + 33 1 47 67 20 00 - Fax: + 33 1 47 67 20 07
e-mail: [email protected]
in the amine solution. In addition,
http://www.prosernat.com the heat of CO2 and H2S absorption
expedites the formation of an

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42 GAS 2011 www.eptq.com

basf.indd 4 9/3/11 12:36:25

 adverse temperature profile in the
absorber (see Figure 1). The contin- 50
uing acceleration of this
45

Absorber height, segments

phenomenon has a negative influ-
40
ence on overall gas capacity and
H2S selectivity. Besides the specific 35
heat of absorption and the amount 30
of absorbed CO2 and H2S, further 25
parameters, such as the specific 20
heat capacity of gas and liquid
15
phases, heat transfer as well as the
L/G ratio, play an important role. 10
It is obvious that at this point cross- 5
over effects between CO2 and H2S 0
start to increase the complexity of 40 45 50 55 60 65 70 75 80 85
the system. It is therefore important Temperature, C
to understand the temperature
profile and location of the tempera- Figure 1 Absorber, liquid-phase temperature profiles red: feasible T-profile at
ture bulge, in particular its distance appropriate L/G ratio; blue: T-bulge profile at too low L/G ratio
from the very sensitive absorber
top, to predict the absorption psi). At these conditions, MDEA- hindered amines are comparatively
performance of an operating plant. based solvents are closer to more sensitive regarding the
Taking these issues into account, hindered amines from a selectivity absorption performance. In some
design flexibility for selective natu- perspective. In addition, the rela- cases, additional side coolers may
ral gas plants is driven by: tively high total acid gas partial help to increase the performance of
Variation in absorber height pressures of natural gas plants these processes. Last but not least,
through multiple amine feed points reduce the acid gas capacity advan- the size of todays natural gas
Low lean amine loading to tage of hindered amines. Moreover, trains, with an amine hold-up of
achieve H2S specification with suffi- temperature profile and bulge several hundred tonnes, makes the
cient safety margin control at high ambient tempera- use of MDEA-based solvents much
Flexibility in circulation rate to tures often determine the circulation more economical.
manage the temperature profile in rates of many AGE units and result
the absorber and control CO2 mass in relatively low acid gas loadings Promoted MDEA solvent for
transfer in the amine solution in the refineries
Sufficient reboiler energy to keep absorber bottom. The required The AGRU setup of a refinery is
the lean loading low at various over-circulation may become even very complex and the different
circulation rates. worse for hindered amine designs, requirements of the absorbers prefer
since the advantage of higher acid an all-fits-one solution. Although
Promoted MDEA solvent for natural gas absorption capacity is partly acid gas partial pressures are differ-
gas plants compensated by the lower heat ent from those of natural gas plants,
Most natural gas plants have CO2 capacity of a smaller solvent flow MDEA-based solvents are well
partial pressures >1.5 bara (>21.8 rate. Temperature bulge effects in established and are represented

Absorber Desorber
6 Top 10
9
5 Acidified MDEA
8 MDEA
MDEA
7
4 Acidified MDEA
6
3 5
4
2
3
2
1 High acid gas Low acid gas
concentration 1 concentration
0 0
7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 Bottom 7.5 8.0 8.5 9.0 9.5
pH pH

Figure 2 Example of pH profiles in an absorber (left) and a desorber (right) with generic MDEA and acidified MDEA

www.eptq.com GAS 2011 43

basf.indd 5 9/3/11 12:36:36

 120C
H2S partial pressure

MDEA
MDEA + promoter
Promoted MDEA

50C
Stripper
sump
Absorber
head

H2S loading

Figure 3 Influence of the acidic promoter formulation on the isothermal equilibrium curves at 50C and 120C (H2S partial pressure
regime of 1 mbar)

_
today in more than 40% of all refin- loadings. In this respect, the HS anion, described in the follow-
ery amine systems. In addition, the promoter formulation provides an ing reaction:
relatively high refill demand comes option to design selective units with
H2S + MDEA HS- + MDEAH+
along with pricing and availability. a high degree of flexibility by vary-
With respect to regeneration energy, ing absorber heights, while low CO2 desorption can be described
the unintentional and sometimes acid gas lean loadings keep H2S by the following net equilibrium
quick formation of HSS to concen- outlet concentrations at a very low reaction:
trations of up to 3 wt% is supportive level.
-
to some extent. However, corrosion The following describes the mech- CO2 + MDEA + H2O HCO3 + MDEAH+
issues force refiners to neutralise anism of achieving low acid gas
those acids with caustic solution. lean loadings. The purpose of desorption is to
strip H2S and CO2 from the rich
New-generation promoter system Principles solution to obtain a regenerated
A new promoter has been devel- Desorption mechanism in solvent. As a consequence of CO2
oped and incorporated: BASFs the stripper and H2S mass transfer from the
selective sMDEA+ technology. This H2S desorption follows an equilib- liquid phase into the gas phase, the
promoter formulation is highly effi- rium reaction between amine, above two equilibrium reactions
cient in achieving very low H2S lean protonated amine and the dissolved move towards the left side and the
pH value of the solution increases
accordingly from the top to the
bottom of the stripper.
MDEA 0.5 0.0060
H2S lean loading, mol/mol

Since CO2 is a weaker acid

H2S lean loading, Nm3/to

Acidified MDEA
sMDEA+ 0.4 0.0048 at typical stripper temperatures
compared with H2S, CO2 is prefera-
25 0.3 0.0036 0.30 bly released in the upper part of the
stripper, whereas a significant
H2S lean loading, Nm3/to

H2S lean loading, Nm3/to

0.2 0.0024
20 0.24 amount of H2S as the stronger
0.1 0.0012 acid is released in the lower part
of the stripper. Releasing CO2 and
15 0.18
0.0 0.0000 obtaining low residual CO2 concen-
Regeneration energy trations becomes easier than
10 0.12 achieving low H2S residual loading,
which requires much more strip-
5 0.06 ping stream and reboiler energy.
Low acid gas concentrations in
the lean solvent are directly linked
0 0.00
Regeneration energy to the maximum achievable gas
purities in the absorber overhead:
unfortunately, most gases have very
Figure 4 H2S regeneration lab tests (reduced desorber height) tight H2S specifications for

44 GAS 2011 www.eptq.com

basf.indd 6 9/3/11 14:46:11

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Valve (numerous options) For top performing mass transfer and tower internal components let AMISTCO
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amistco.indd 1 8/3/11 14:02:35

 Figure 5 illustrates the corre-
 sponding H2S concentration profile
 in the gas phase for a 10m packed-

Absor be r
h e i gh t ,
m  bed absorber with a feed gas partial

pressure for CO2 of ~2 bar (29 psi)
and H2S ~1 bar (14.5 psi) at 40C

(104F). As a matter of equilibrium,
 the respective H2S specification for
 MDEA is in the low hundreds
 ppmv range, while for acidified
 .%&" MDEA the H2S specification would

"DJEJFE
.%&" be around a tenth of this. In the
T.%&" sMDEA+ case, the ultra-low lean

& & & & & & &
loading in the 1E-4 mol/mol range
H2 S concentration, mol% is able to achieve a treated gas
specification below 5 ppmv, with
sufficient safety margin and a negli-
Figure 5 Absorber H2S profile [0] gible impact on the H2S absorption
capacity at the absorber bottom.
instance, 510 vppm for natural gas; However, a decrease in the pH To reach a similar low lean load-
see Table 1 but much looser CO2 value in the stripper and an increase ing with a state-of-the-art acidified
specifications. However, this in the protonated amine concentra- MDEA, a doubling of the H3PO4
requirement is in opposition to the tion also affect the absorber pH concentration would be required.
chemistry of H2S desorption, value (see Figure 2) and thus the But, as a consequence of this meas-
described above. equilibrium loading. Consequently, ure, the absorber equilibrium curve
Another effect that hampers H2S acidification is limited to some and thus the entire acid gas capac-
desorption is related to the pH extent, so acidified MDEA solvents ity would suffer, requiring a
value increasing steadily towards may require an increase in liquid compensation of approximately
the stripper sump. As a conse- flow rate to cope with this negative 512% higher amine liquid load.
quence, the ratio between side effect. This is a crucial point,
protonated HS- and H2S increases especially at elevated amine and Conclusions
according to the well-known corre- feed gas temperatures above 40C Besides highly selective AGE appli-
lation between the pH value and (104F). cations, H2S selective acid gas
pKa values of an acid/base system: The respective isothermal equilib- removal has become an increasingly
rium curves demonstrate that an important field for world-scale
log f
[HS-]
p = pH - pKaH2S ideal promoter system needs to natural gas plant designs. Contrary
[H2S] have an acidic character in the to acid gas enrichment techniques,
stripper bottom, but a neutral selectivity and thus CO2 slip are
Considering these issues, it impact in the absorber overhead limited and require some adjusta-
becomes obvious how energy inten- (see Figure 3). In addition, no nega- bility and flexibility.
sive the purification of gases down tive side effects, such as foaming, From a solvent technology
to very low H2S ppm levels can be corrosion, thermal instability or perspective, advanced H2S selective
when amine-based solvents are even evaporation, should occur. acid gas removal can be carried out
used. In this respect, the addition of Such a tailor-made solvent which through sterically hindered amines
an acid to amine solvents has at least comes close to the ideal or tertiary amines, both in combina-
become a common solution to over- solvent has been developed and tion with other amines or a
come the effect of high pH value is described next. promoter system. Additionally,
and to detain acid/base reactions in sophisticated design measures are
the stripper sump. Regeneration test runs and applied to ensure a reliable
In other words, a further decrease achievable absorber specifications operation.
in H2S loading can be obtained by Figure 4 shows the graph of a Todays plants require a very high
shifting the equilibrium of the regeneration lab test run with degree of flexibility in turndown
reaction MDEA, acidified MDEA (H3PO4) rates, changing feed gas specifica-
and MDEA with the new promoter tions and conditions. In addition,
_
H2S + MDEA HS + MDEAH+ system (sMDEA+ technology), with very tightly treated gas sulphur
the residual H2S lean loading specifications in the low ppm range
towards the H2S side, by adding a (Nm3/t, mol/mol) against regenera- (<5 ppmv) are mandatory.
strong acid (AH) to the system: tion energy, Q. In the important The high acid gas partial pressures
regime of very low loadings (<0.5 in most natural gas applications, and
Nm3/t, <6E-3 mol/mol), a magni- the requirement for adjustable
_ -
HS + AH H2S + A fied graph illustrates the difference. selectivity, make MDEA-based

46 GAS 2011 www.eptq.com

basf.indd 7 11/3/11 11:37:45

 technologies attractive due to model of acid gas absorption/stripping using Ralf Notz is a Research Engineer at BASF SE in
competitive solvent prices and methyldiethanolamine with added acid, Gas Ludwigshafen. He holds a diploma in process
generic designs. For opex, capex and Separation & Purication, Jun 1991, vol 5. engineering from the University of Stuttgart
4 Kohl A L., Nielsen, Gas Purication, 5th ed, and a PhD in CO2 capture from power plant ue
specication purposes, acidic
Gulf Publishing Corp, 1997. gas by reactive absorption from the Institute
promoted systems are in use to
5 Weiland R H, Dingman J C, Effect of solvent of Thermodynamics and Thermal Process
overcome the relatively high H2S blend formulation on selectivity in gas treating, Engineering at the University of Stuttgart.
binding energy and to lower resid- 45th Annual Laurance Reid Gas Conditioning Email: [email protected]
ual H2S loading in the amine. Conference, Norman, Oklahoma, 1995. Torsten Katz is head of the Global Technology
However, current acidied state- 6 Huffmaster M A, Stripping requirements for Team at BASF SE and coordinates BASFs
of-the-art systems also have their selective treating with Sulphinol and amine new business development activities in gas
limits, as the improved regenera- systems, 47th Annual Laurance Reid Gas treatment. He studied mechanical engineering
tion will trigger an inverse effect on Conditioning Conference , Norman, Oklahoma, at the Technical University of Aachen, Germany
the entire capacity. Alternatively, 1997. (RWTH Aachen) and holds a PhD in evaporation
the new, proprietary promoter 7 Weiland R H, Sivasubramanian M S, Dingman technology.
J C, Effective amine technology: controlling Email: [email protected]
system described in this article
selectivity, increasing slip, and reducing sulphur, Wieland Wache is a Process Engineer at
shows different behaviour: a
53th Annual Laurance Reid Gas Conditioning Bayernoil Renery in Vohburg, Germany.
substantial increase in regeneration Conference, Norman, Oklahoma, 2003. He holds a diploma in chemistry from the
ability while hardly affecting 8 A Renery for Bavaria, ofcial Bayernoil Technical University (RWTH) Aachen and a PhD
absorption capacity. brochure, July 2009. in chemical engineering on Fischer-Tropsch
synthesis and dehydrogenation of middle
Further reading Gerald Vorberg is a Senior Technology Manager distillates from the University of Bayreuth.
1 Bullin J A, Polasek J, Selective absorption in BASFs Gas Treatment team in Ludwigshafen Email: [email protected]
using amines, 61st GPA Conference, Tulsa, and Project Leader for Selective Acid Gas Claus Schunk is Plant Manager at Bayernoil
Oklahoma, 1982. Removal. He joined BASFs Catalyst Group in Renery in Vohburg and was formerly Lead
2 Harbison J L, Handwerk G E, Selective removal 1997 as a Global Product Technology Manager Process Engineer for the development and
of H2S utilizing generic MDEA, 37th Annual and holds a diploma in chemical engineering implementation of the OATS units. He holds
Laurance Reid Gas Conditioning Conference, from the University of Applied Sciences (FHT), a diploma in process engineering from the
Norman, Oklahoma, 1987. Mannheim, Germany. Technical University Karlsruhe.
3 Carey T R, Hermes J E, Rochelle G T, A Email: [email protected] Email: [email protected]

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 Estimating gas hydrate inhibitor loss:
a case study
A predictive tool is used to understand and predict the loss of methanol during
natural gas hydrate inhibition

Alireza Bahadori
Curtin University

T
he amount of methanol to be Methanol is the most commonly intermittent application (mainly
injected as a hydrate inhibitor used hydrate inhibitor in subsea during start-up or shutdown).
must not only be sufficient to petroleum industries, gas treatment However, when it is injected contin-
prevent freezing of the inhibitor and processing, pipelines and wells, uously, as is often observed in gas
water phase, but also to provide for with worldwide usage worth systems, it is sometimes regener-
the equilibrium vapour-phase several million dollars per year.1 ated.1,2 The losses to the vapour
content of the inhibitor and the Due to its high volatility, methanol phase can be prohibitive, in which
amount that is soluble in the is lost in the vapour phase. Often, case operators select monoethylene
condensate liquid phase. In this when applying methanol as an glycol.
article, a case study is presented inhibitor, there is a significant Considering all of these issues,
showing how the information expense associated with the cost of there is a significant need for the
gained from a predictive tool can lost methanol. development of an accurate and
be used to understand and predict The amount of methanol injected simple-to-use predictive tool to
the loss of methanol during natural to treat the water phase, including represent methanol loss during gas
gas hydrate inhibition. According the amount of inhibitor lost to the hydrate inhibition. Predictive tools
to this study, more than $3700/day vapour phase and the amount that to minimise the complex and time-
is the cost of lost methanol for 3 x is soluble in the hydrocarbon liquid consuming calculation steps are also
106 m3/d of natural gas. phase, equals the total amount of an essential requirement. It
Gas hydrate formation in natural required methanol. is apparent that mathematically
gas and natural gas liquids (NGL) In addition, one of the primary compact, simple and reasonably
systems can block pipelines, equip- factors in the selection process is accurate equations, which contain
ment and instruments, restricting or related to the possibilities for recov- fewer tuned coefficients, would be
interrupting the flow, which leads ery, regeneration and reinjection of preferable for computationally inten-
to safety hazards and substantial the spent material. Usually, metha- sive simulations. The present study
economic risks.1,2 nol is not regenerated because of its discusses the formulation
of a novel and simple predictive tool
that could be of significant impor-
Tuned coefficients for the prediction of methanol vapourisation loss
tance to natural gas engineers.

Coefficient Values for pressure Values for pressure between Methanol vapourisation loss during
less than 6000 kPa 6000 and 20000 kPa
gas hydrate inhibition
A1 4.5112124 x 104 5.32442401 x 103
B1 -6.5625532 x 108 3.64817009 x 107 Equation 1 shows a definition of
C1 2.7486759 x 1012 -1.43519141 x 1012 methanol vapourisation loss:
D1 -3.26326963 x 1015 5.41358084 x 1015 methanol vapour composition to
A2 -3.6813711 x107 -4.71938915 x 106
methanol liquid composition.
B2 5.3777095 x 1011 -2.60914887 x 1010
C2 -2.25654440 x 1015 1.17661977 x 1015 Equation 2 is an Arrhenius-type
D2 2.68069426 x 1018 -4.48418384 x 1018 function to correlate methanol
A3 1.00121117 x 1010 1.39340046 x 109 vapourisation loss as a function of
B3 -1.46856806 x 1014 6.012666228 x 1012
temperature (K), wherein the
C3 6.17387798 x 1017 -3.21209807 x 1017
D3 -7.33914654 x 1020 1.237524600 x 1021 relevant coefficients (see Table 1)
A4 -9.07444577 x 1011 -1.369737341 x 1011 are correlated as a function of
B4 1.3364870 x 1016 -4.38900897 x 1014 pressure in kPa(abs) (Equations
C4 -5.6294519 x 1019 2.919844093 x 1019
36).
D4 6.696496249 x 1022 -1.137898262 x 1023
kg methanol (1)
LM = Million standard m3 gas
Table 1 Mass% methanol in water phase

48 GAS 2011 www.eptq.com

curtin.indd 1 9/3/11 12:49:34

 exponential function to develop the
Tuned coefficients for the prediction of
tool leads to well-behaved (that is,
methanol loss in the condensate phase
smooth and non-oscillatory) equa-
tions, enabling fast and more
Coefficient Value
A1 1.6812339429 x 103 accurate predictions.
B1 -1.0803155907 x 104
C1 2.2311693912 x 104 Methanol loss in condensate liquid Our new clean-fuels
D1 -1.4729301398 x 104
phase during gas hydrate inhibition plant is straining the
A2 -1.564777661 x 106
Equation 7 represents the proposed
B2 9.9874920671 x 106
governing equation in which four
auxiliary units!
C2 -2.0506540953 x 107
D2 1.3479263861 x 107 coefficients are used (Equations
A3 4.8553968051 x 108
811) to correlate methanol solubil-
B3 -3.0835714347 x 109
C3 6.2988799656 x 109 ities in the liquid hydrocarbon
D3 -4.1248186297 x 109 phase () in mole fraction as a
A4 -5.0424809928 x 1010 function of temperature (T) for a
B4 3.1810877336 x 1011
given methanol mass fraction in
C4 -6.4667402344 x 1011
D4 4.220547048 x 1011 the aqueous phase, where the rele-
vant coefficients are shown in How can we boost their capacity
Table 2 Table 2: without major construction?
b c d TO MEET CLEAN FUELS require-
ln(LM) = a + + 2+ 3 b c d
T T T (2) ln() = a1 + + 2 + 3 ments for gasoline, a medium-sized
T T T (7) 0LGZHVWHUQUHQHU\DGGHGDORZ
Where: Where: VXOIXUIXHOVWHFKQRORJ\SODQW*DVROLQH
B C D a = A1 + B1 + C12 + D13 (8) WKURXJKSXWZDVXQFKDQJHG+RZHYHU
a = A1 + 1 + 21 + 31 WKHVKDUSLQFUHDVHLQVXOIXUUHPRYDO
P P P (3) b = A2 + B2 + C22 + D23 (9)
c = A3 + B3 + C32 + D33 (10) UHTXLUHGPRUHK\GURJHQIURPWKH
B2 C2 D2 d = A4 + B4 + C42 + D43 (11) K\GURJHQXQLWDQGVHQWPRUHVXOIXU
b = A2 + + + gases to the amine treaters and
P P2 P3 (4)
GRZQVWUHDPVXOIXUXQLWV7KHVH
These optimum tuned coefficients DX[LOLDU\XQLWVEHFDPHERWWOHQHFNV
B3 C3 D3 RYHUGULYHQDWWKHFRVWRISURGXFW
c = A3 + + +
P P2 P3 (5) help to cover temperatures in the
SXULW\DQGDPLQHFRQVXPSWLRQ
range 240320K and methanol
B4 C4 D4 concentrations up to 0.70 mass
d = A4 + + +
P P2 P3 (6) fraction in the aqueous phase.
The optimum tuned coefficients
The novel tools proposed in the shown in Table 2 can be further
present work are simple formula- retuned quickly according to
tions. Furthermore, the selected the proposed approach1,2 if

Comparison with reported data3 of predicted results of methanol vapourisation loss

Temp, Pressure, Reported methanol Calculated methanol Percentage

K kPa vapourisation loss3 vapourisation loss absolute 2QVWXG\LQJWKHK\GURJHQDPLQH
kg methanol kg methanol deviation DQGVXOIXUXQLWV$PLVWFRIRXQGPDQ\
Million standard m3 gas LM = Million standard m3 gas RSSRUWXQLWLHVIRULPSURYLQJVHSDUDWLRQ
Mass% methanol in water phase Mass% methanol in water phase HIFLHQF\DQGFDSDFLW\7KHSUREOHPV
261.15 2000 11 10.916 0.76 ZHUHVROYHGZLWKRXWPDMRUFRQVWUXFWLRQ
277.15 2000 32.7 32.217 1.47 E\DSSO\LQJPRGHUQWHFKQRORJ\WRPLVW
269.15 3000 15.9 15.229 4.22 HOLPLQDWRUVOLTXLGOLTXLGVHSDUDWRUV
281.15 3000 31.2 31.605 1.29 DQGWRZHUWUD\VDQGSDFNLQJ5HVXOWV
271.15 4000 14.6 14.639 0.26 LQFOXGHGKD]HIUHHSURGXFWDQG
283.15 4000 29.85 30.232 1.27 UHGXFHGDPLQHFRQVXPSWLRQ1RZD
273.15 5000 14.6 14.402 1.35 GLHVHOFOHDQIXHOVSODQWLVEHLQJDGGHG
285.15 5000 29.3 28.592 2.41
275.15 6000 14.8 14.609 1.29
287.15 6000 29.2 29.218 0.06
Read more on this topic at
277.15 7000 27.8 27.605 0.70 www.amistco.com
279.15 8000 16.8 16.973 1.03
283.15 9000 20.9 20.755 0.69
285.15 10 000 22.2 22.236 0.16
279.15 20 000 13.7 13.699 0.007
289.15 20 000 23 22.95 0.21
3KRQH)D[
Average absolute deviation percent (AADP) 1.07% [email protected]
KU(PHUJHQF\6HUYLFH
Table 3

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curtin.indd 2 9/3/11 12:49:43

 more data become available in the
future.
0.025
hydrocarbon phase, mole fraction Methanol mass fraction = 0.60 It is expected that efforts during
Dissolved methanol in liquid

Methanol mass fraction = 0.02 this investigation will pave the way
0.020 to an accurate prediction of metha-
nol loss in the liquid hydrocarbon
0.015 phase () in mole fraction, as well
as methanol vapourisation loss in
various conditions, which can be
0.010
used by engineers and scientists for
monitoring the key parameters
0.005 periodically.

0.000 Results
220 240 250 260 270 280 290 300 310 320 Table 3 presents the summary of
Temperature, K accuracies with the proposed
predictive tools in terms of average
Figure 1 Performance of proposed tool for prediction of solubility of methanol in the absolute deviation percentage with
hydrocarbon condensate phase reliable data.3 It shows that the
proposed correlation has an
average absolute deviation percent-
age of less than 1.1%, which can be
considered to be a very small devia-
Solubility of methanol in condensate

102
tion from reliable data. Figures 1
hydrocarbon liquid, mole fraction

and 2 show the proposed methods

104 results and performance in the
prediction of methanol solubility in
106 the hydrocarbon liquid phase for a
wide range of conditions from two
108
different viewpoints. They show
that high temperatures and more
injected methanol in the aqueous
1010 Temperature = +50C
Temperature = 15C
phase lead to higher solubility of
methanol in the liquid phase. Table
1012 4 illustrates the accuracy of the
102 101 proposed correlation in predicting
Methanol mass fraction in water phase the solubility of methanol in
paraffinic hydrocarbons in compari-
Figure 2 Performance of proposed tool for prediction of solubility of methanol in son with some reported data.3 The
hydrocarbon condensate phase from another view point accuracy of correlation in terms of
average absolute deviations
is 2.12%.
Comparison with reported data3 of calculated solubility of methanol in hydrocarbons The following is a case study
showing how the information
Temp, Methanol mass Calculated solubility Reported solubility Absolute evolving out of a predictive tool
C fraction of methanol in of methanol in deviation, can be used to understand and
hydrocarbons, hydrocarbons, % predict the loss of methanol during
mole fraction mole fraction3 natural gas hydrate inhibition.
12 0.20 0.00099 0.001 1
30 0.20 0.00294 0.003 2 According to these calculations,
50 0.20 0.006 0.006 0 $3701/day is the cost of methanol
21 0.35 0.0044 0.004 1 loss, which is calculated by
47 0.35 0.01035 0.01 3.5 this simple predictive tool for
-10 0.60 0.00295 0.003 1.6
2 0.60 0.00514 0.005 2.8 3 x 106 m3/d of natural gas leaving
43 0.60 0.02034 0.02 1.7 an offshore platform.
-40 0.70 0.0021 0.002 5
0 0.70 0.0073 0.0071 2.8 Case study
50 0.70 0.0265 0.027 1.9
As indicated, 3 x 106 m3/d of natu-
Average absolute deviation, % 2.1 ral gas leaves an offshore platform
at 38C and 8300 kPa (abs), and the
water content is 850 mg/Sm3. The
Table 4 gas comes onshore at 4C and 6200

50 GAS 2011 www.eptq.com

curtin.indd 3 9/3/11 12:49:54

 kPa (abs), and water content is 152 Losses = 14.58 x 10-6 (kg/m3)/(wt%
f3 x 10 Sm p f56m p f778kgp f1kgmolep = 933
6 3 3

mg/Sm
slip
3.
(minimum The hydrate
removal) temperature
to meet methanol) day 10 Sm3 m3
6
140 kg kg
of theAmerican
North gas is treating
18C. Associated
specica- Daily vapourisationNew losses
Mexico = 14.58 x mol/day.

Spray Regime Correction Factor

condensate
tions. Due toproduction
the small amountis 56mof 3
/ 10-6 (3 x 106)(27.5) = 1203 kg/day.
(million
acid gas standard
removal, m the). absorbers
3
The conden- in 1203 kg/day ($3/kg) = $3609/day Kg mol methanol = 933(0.0011) =
sate has
these plantsa density of 778 kg/m
were operated and
at small is the cost of vapourised methanol 1.026 moles/day.
a molecular
liquid rates and massvery of low140. weir
The calculated by this predictive
Iowa tool. Kg methanol = (1.026) (32) = 32.84
required
loads. methanol inhibitor
Simulations fell far shortconcen-
of kg/day.
tration in the
agreeing withwater thephaseeldto data.
avoid Solution for methanol loss in The methanol in the condensate
hydrate
Eventually, formation
it was realised is that27.5%.
the condensate phase phase can be recovered by down-
Calculate were
absorbers the mass wellrate
intoofthe inhibitor
spray Win = 850 mg/Sm3 stream water washing.
regime
loss inand theProTreats
water phase mass transfer
and the Wout = 152 mg/Sm3 Alberta Cost per month = ($3/kg) (30.72
North Texas
coef
amountcientofcorrelations
methanol were loss in inap-
the W = 698 mg/Sm3 North Texas India
kg/day)(30 day/month)
Base
= $2956
plicable North Texas
hydrocarbon liquid phase, aswere
because they well Water condensed = (3 x 10 ) (698) = per
6
month.
North Texas
developed
as the amount fromofdata on trays
methanol oper-
vapouri- 2094 x 106 mg/day = 2094 kg/day The total cost of methanol loss per
ating
sation loss. Consider the priceTo
in the froth regime. of Calculate mass rate of inhibitor in Weir day
Load will become 92 + 3609 =
reproduce
methanol asthe performance
$3 per kg. data, the water phase: $3701/day.
the vapour-side mass transfer coef- ?b`nk^+Ahpma^\hkk^\mbhg_Z\mhk_hklikZrk^`bf^hi^kZmbhgoZkb^lpbmap^bkebjnb]ehZ]
Solution
cients had to be increased by
for methanol mi =
0.275(2094)
= 794 kg/day References
upwards
vapourisation factor
of a loss of 10 or more, from 1plants
0.275in Canada, the US and multiplying
1 Bahadori A,the gas-side
Vuthaluru H B,mass
Energytrans-
& Fuels,
and the liquid-side
X = 0.275 mass fraction coefofcients had
methanol India and span the full
Estimate losses to hydrocarbonspectrum of fer
24, coef
2010, cient
29993002. (the same factor
to be decreased
T = 277.15K correspondingly. weir loads
liquid phase from
fromabout 2.2 m3method
proposed /mhr divided theA,liquid
2 Bahadori coef
Vuthaluru H B,cient)
Journaluntil
of Loss
Since then, six more commercial (3atgpm/ft) to 45 m 3
/mhr (60 gpm/ Prevention in the
agreement Process
with theIndustries, 23, 3, 2010,
performance
For vapourisation loss of methanol, 4C and 27.5 wt% MeOH:
tower performance data sets with ft). 379384.
we use the tuned coefficients a =Each plant was xsimulated
9.136448034367 101 rst data was obtained.
3 GPSA Engineering Data Book, 12th ed, 2004,
absorbers
reported inatTable low 1:weir load have using ProTreats database
b = -8.869793699719 x 10 4 correla- Figure 2 shows how the results
Gas Processors Suppliers Assoc, Tulsa, USA.
come to light.
a = -1.6454503534842 The only non-propri-
x 10 3 tions for tray mass
c = 2.8126995933983 x 107 transfer compare with each other and how
etary set of measurements
b =1.3743444476865 x 10 6 is from a coef
d = -3.0722013379 x 109 using the
cients (froth regime), the correction alters with changing
Alireza Bahadori works in the Chemical
plant operated
c = -3.8051922967936 by
x 108 Signalta owsheet shown of in
The solubility Figurein the
methanol 1. weir load. Department
Engineering The plot shows
of CurtinaUniversity
truly
Resources
d = 3.4980770983675 x 1010 Alberta,
near Forestburg, Simulations were repeated for
hydrocarbon phase is estimated tovari- remarkable degree of correlation,
of Technology, Perth, Western Australia.
Canada.
LM = 14.58These eight data sets are
4
ous values 0.0011
be around of a orconstant factor,
0.11 mol%: especially in view of the fact that
Email:[email protected]

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