INTRODUCTION

Petroleum and derivatives such as asphalt have been known and used for almost 6000 years and
there is evidence of use of asphalt in building more than 600 years ago. Modern petroleum
refining began in 1859 with discovery of petroleum in Pennsylvania and subsequent
commercialization. The exploration of petroleum originated in the latter part of the nineteenth
century [Speight, 1999].

CRUDE OIL AND NATURAL GAS ORIGIN, OCCURRENCE,

EXPLORATION AND DRILLING
Oil and natural gas were formed hundred years ago from the prehistoric plant and animals. it is
believed that hydrocarbon formed by the thermal maturation of organic matter buried deep in
earth. over the millions of years under extreme pressure and high temperature these organic
matter converted to hydrocarbons consisting of oil and gas. Hydrocarbons are present in the
variety of forms: koregen, asphalt, crude oil, natural gas, condensates, and coal in solid form.

Oil and gas production includes exploration, drilling, extraction, stabilization. The underground
traps of oil and gas are called reservoir. Various types of traps are structural traps, stratigraphic
traps and combination traps Most reservoir contain water also along with oil and gas. Reserves
are classified as proven, probable and possible reserves. Earlier finding of oil and gas was matter
of luck and hit and miss process. Tools used for oil and gas exploration are based and dependent
on gravity change, magnetic field change, time, change and electrical resistance. However it has
become now more challenging and complex. With advent of three dimensional seismic
technology which is based on the sound waves, identify the subsurface formation by reflection of
sound, there has been much improvement in identification of oil and gas traps and reservoirs.
Seismic technology significantly improves the method of estimating the oil and gas deposits.
Next step after exploration is the drilling of exploratory well. Drilling may be vertical drilling or
horizontal drilling. Drilling may be performed on-shore or off-shore. Horizontal drilling and
hydro-fracturing has resulted in economical and more productive drilling of shale gas which was
not economical with conventional vertical drilling.

COMPOSITION OF PETROLEUM (CRUDE OIL)

Petroleum (Crude oil) consists of mainly carbon (83-87%) and hydrogen (12-14%) having
complex hydrocarbon mixture like paraffins, naphthenes, aromatic hydrocarbons, gaseous
hydrocarbons (from CH4 to C4H10) [Mukhulyonov et al., 1964]. Table M-VI 1.1 gives more
details about composition of petroleum. Besides crude oil also contains small amount of non
hydrocarbons (sulphur compounds, nitrogen compounds, oxygen compounds) and minerals
heavier crudes contains higher sulphur. Depending on predominance of hydrocarbons, petroleum
is classified as paraffin base, intermediate base or naphthenic base.

Table M-VI 1.1: Composition of Petroleum

Hydrocarbons
Hydrogen Distinguishing Major
Remarks
Family characteristics hydrocarbons
Paraffins Straight carbon Methane, ethane, General formula CnH2n+2
(Alkanes) chain propane, butane, Boiling point increases as the
pentane, hexane number of carbon atom increases.
With number of carbon 25-40,
paraffin becomes waxy.
Isoparaffins Branched Isobutane, The number of possible isomers
(Iso alkanes) carbon chain Isopentane, increases as in geometric
Neopentane, progression as the number of carbon
Isooctane atoms increases.
Olefins One pair of Ethylene, General formula CnH2n
(Alkenes) carbon atoms Propylene Olefins are not present in crude oil,
but are formed during process.
Undesirable in the finished product
because of their high reactivity. Low
molecular weight olefins have good
antiknock properties.
Naphthenes 5 or 6 carbon Cyclopentane, General formula CnH2n+2-2Rn
atoms in ring Methyl RN is number of naphthenic ring
cyclopentane, The average crude oil contains about
Dimethyl
50% by weight naphthenes.
cyclopentane,
Naphthenes are modestly good
 cyclohexane, components of gasoline.
1,2 dimethyl
cyclohexane.
Aromatics 6 carbon atom Benzene, Aromatics are not desirable in
in ring with Toluene, Xylene, kerosene and lubricating oil.
three around Ethyl Benzene, Benzene is carcinogenic and hence
linkage. Cumene, undesirable part of gasoline.
Naphthaline

Non Hydrocarbons
Non-hydrocarbons Compounds Remarks
Sulphur compounds Hydrogen sulphide, Undesirable due to foul odour
Mercaptans 0.5% to 7%
Nitrogen compounds Quinotine, Pyradine, The presence of nitrogen
pyrrole, indole, carbazole compounds in gasoline and
kerosene degrades the colour of
product on exposure to sunlight.
They may cause gum formation
normally less than 0.2.
Oxygen compounds Naphthenic acids, phenols Content traces to 2%. These
acids cause corrosion problem at
various stages of processing and
pollution problem.

Source: Mall,2007
PROCESSING OF PETROLEUM (CRUDE OIL)
Processing of Petroleum from drilling: when petroleum is drilled and brought to the surface, the
pressure drops resulting in separation of gases from the crude oil. Further processing of crude
involves separation of water and oil and salt. Associated natural gas is further processed for
separation of natural gas, condensate, acid gases. Crude oil varies in appearance from brownish
green mobile liquid to black viscous and sometimes semisolid. . Figure M-VI 1.1 illustrates the
process of oil and gas processing [Ravindranath and Habibula, 1992]
.
CRUDE OIL PROCESSED IN INDIA
Both indigenous and imported crude oil are processed in India. Various imported sources of
crude oil is given in Table M-VI 1.2.There has been continuous changes in the crude oil quality.
Now imp
ported crudee oils are beeing heavierr with higheer sulphur coontent. Channging worlddwide
crude oiil scenario is given in
n Table M-VI 1.3. Inddigenous crrude oil is also varyinng in
characterristics. Rajassthan crude oil contain
ns high sulphhur and maay pose seriious challenge to
Indian petroleum refining indusstry Typicall characterisstics of variious indigennous crude oil is
given in Table M-VI 1.4.

Figure M-VI
M 1.1: Oil and G
Gas Processsing
Sou
urce: Ravindraanath and Haabibula, 1992
Table M-VI 1.2: Imported Crude Sources
Middle East Kuwait, Dubai, S. Arabia( Arab Mix, Arab medium), Iraq,
Abu Dhabi, UAE(upper Zakum,Murban,UM Shaif)
Iran, Kuwait : Ratawai, Egypt( Suez Mix, Zeit mix),
Mediterranean Libya - Es Sider
West Africa Nigeria-Bonny Light, Eseravos, Forcados, Penington,
Quaiboe)
Angola, -Cabinda, Palanca, Girassol
Eq. Guinea -Ceiba, Zaffiro
Congo -Nikossa, Kitina
Far East Malaysia -Labuan, Miri Light
Australia -Barrow Island, Cooper Basin,Chalis
Brunei -Seria Light

Table M-VI 1.3: Worldwide Crude quality

Properties 1985 1990 1995 1999 2010

Sulphur,Wt % 1.14 1.12 1.31 1.41 1.51

API gravity 32.7 32.6 32.4 32.2 31.8

Residue in crude 19 19.4 19.8 20.2 21.3

,vol %

‘S’ in residue ,Wt 3.07 3.26 3.61 3.91 4.0

%
Metals in residue, 275 286 297 309 320
ppm

Source: Samanti,R.K. “Refining challenges and Trends” 6th summer School on “Petroleum
refining and petrochemicals” June 6, 2012, Organised by New Delhi

Table M-VI 1.4: Characteristics of Various Crude Oil

Sources of indigenous Salient features
crude
Assam Crude Nahorkatia/ 31 oAPI, Sulphur 0.3%, Pour point +30 oC, High
Moran aromatics, Total distillate yield 65%.
ONGC, Lawkwa, 27 o API, Sulphur 0.3%, High aromatics, Distillate yield
Rudrasagar 57%.
Ankleshwar Crude 48 oAPI, Sulphur 0.1%, Pour point +18 oC, Distillate
 yield 80-82% (Light distillates 24%, Middle distillate
47%), Wax content 9.9%, total sulphur 0.02%.
North Gujarat Crude 28 oAPI, Sulphur content 0.1%, Pour point +27 0C,
Distillate yield low 33-35%, High organic acidity.
Bombay High Crude 38 oAPI, Sulphur 0.2%, Pour point +30 oC, Distillate
yield 65-70% (Light distillate 24%, Middle distillates
46%), High aromatics.
Narimanam Crude 46 oAPI, Sulphur 0.1%, Pour point 3 oC, Distillate yield
80%.
KG Basin Ravva Crude 36 oAPI, Sulphur 0.1%, Pour point +30 oC, Distillate
yield 61%.
Source: Mishra & Unnikrishnan, 1996, p.22

REFINERY PROCESSES
Refining of crude oils or petroleum essentially consists of primary separation processes and
secondary conversion processes. The petroleum refining process is the separation of the different
hydrocarbons present in the crude oil into useful fractions and the conversion of some of the
hydrocarbons into products having higher quality performance. Atmospheric and vacuum
distillation of crude oils is the main primary separation processes producing various straight run
products, e.g., gasoline to lube oils/vacuum gas oils (VGO). These products, particularly the light
and middle distillates, i.e., gasoline, kerosene and diesel are more in demand than their direct
availability from crude oils, all over the world. The typical refinery operation involves separation
processes, conversion processes, finishing processes, environmental protection processes.
Typical refinery process diagram is shown in Figure M-VI 1.2.

SEPARATION PROCESSES
Ÿ Distillation
Ÿ Absorption
Ÿ Extraction
Ÿ Crystallisation
Ÿ Adsorption

PRIMARY DISTILATION (Atmospheric Distillation)

Ÿ Refinery gases
Ÿ Liquefied petroleum gases
 Ÿ Gasolines or naphtha (light/heavy)
Ÿ Kerosene, lamp oil jet fuel
Ÿ Diesel oil and domestic heating oils
Ÿ Heavy Industrial fuels

SECONDARY DISLLATION (Vacuum Distillation)

Ÿ Light Distillate
Ÿ Middle distillate
Ÿ Heavy distillate
Ÿ Asphalt/bitumen

CONVERSION PROCESSES
Process for Improvement of Properties
Ÿ Catalytic reforming
Ÿ Isomerisation
Ÿ Alkylation
 Figure M-VI 1.2: Typical Refinery Processes and Products

Thermal processes:
 Ÿ Visbreaking
Ÿ Coking

Catalytic Processes
Ÿ Catalytic cracking(FCC)
Ÿ Hydrocracking
Ÿ Steam reforming
Ÿ Hydroconversion

FINISHING PROCESSES
Ÿ Hydrotreatment/hydrogenation
Ÿ Sweetening

ENVIRONMENTAL PROTECTION PROCESSES

Ÿ Acid gas processing
Ÿ Stack gas processing
Ÿ Waste water treatment process

TYPES OF PETROLEUM REFINING PROCESSES

PRIMARY PROCESSES: Separating crude into its various fractions e.g. CDU/VDU

SECONDARY PROCESSES: Processing residues from primary processes and upgrading them
to distillates e.g. FCCU, HCU

RESIDUE UPGRADATION PROCESSES: Bottom of the barrel upgradation eg. RFCCU,

DCU, DCC

FINISHING/ PRODUCT QUALITY IMPROVEMENT PROCESSES: Processes to improve

product quality and meet stringent product quality specifications eg. DHDS, DHDT, CRU

REFINING CAPACITY
Global oil consumption and refining capacity, World Refining Capacity Country wise 2009 are
given in Table M-VI 1.5 and Figure M-VI 1.3. Present refining capacity in India is million tones
per annum. The present import of crude in India is around 180 million tones per annum. It is
expected that the import of crude oil has to exceed 240 million tones per annum in the next five
years, if GDP growth of around 6 to 7percent were to be sustained [Venkat, 2012].
Table M-VI 1.5: Global Oil Consumption and Refining Capacity 2009
million barrel/d
Region Oil consumption Refining Remarks
capacity
Asia Pacific 25.99 26.81 Just matching
North america 22.83 21.13 Deficit
Europe and 19.37 24.92 Surplus
Eurasia
S & cent 5.65 6.69 Surplus
.America
Middle east 7.15 7.86 Surplus
Africa 3.08 3.26 Surplus
Total 84.04 90.66 Surplus
Source: Samanti,R.K. “Refining challenges and Trends.6th Summer School on “ Petroleum refining and
petrochemicals” June 6,2011, Organised by New Delhi

RUSSIAN
FED., 6% JAPAN, 5%
CHINA, 10% S. KOREA,
3%

INDIA, 4%

ITALY, 3%
USA, 19%
S. ARABIA,
2%

OTHERS , GERMANY,
45% 3%

Figure M-VI 1.3: World Refining Capacity Country wise 2009

Total: 90.7 mbpd (4533 MMTPA)
Sources: Mr. R.K. Samtani, DGM (Exploration & Production) IOC ltd. 6th June 2011
Changing Scenario in Gasoline and Diesel Specifications
Major Parameters of Gasoline Specifications [Table M-VI 1.6]
• Lead phase out
• Lower RVP
• Lower benzene & aromatics
• Lower olefin content
• Limited Oxygen content
• Lower Sulfur content
Major Parameters of Diesel Specifications [Table M-VI 1.7]
• Low sulfur
• Low aromatics
• High cetane number
• Lower density
• Lower distillation end point

Table M-VI 1.6: Key Specification of Gasoline

Specification BIS BS-II Euro-III Eqv. Euro-IV Eqv .
2000 Regular Premium Regular Premium
Sulphur,ppmw 1000 500 150 150 50 50
(max)
RON,Min 88 88 91 95 91 95
MON,Min No No 81 85 81 85
spec. spec.
AKI,Min 84 84 81 85
Benzene 5 3 1 1 1 1
vol%(max)
Aromatics No No 42 42 42 35
vol%(max) spec. spec.
Olefins No No 21 18 21 81
vol%(max) spec. spec.
Source: Rajgopal, S. “Refining challenges and Trends.6th summer School on “Petroleum refining
and petrochemicals” June 6,2012, Organised by New Delhi

Table M-VI 1.7: Key Specification of High Speed Diesel (HSD)

Specification BIS2000 BS-II Euro-III Euro III
Equ. Equiv.
Density@15oC 820-860 820-860 820-845 820-845
Kg/m3
Sulphur content 2500 500 350 50
ppmw(max)
Cetane 48 48 51 51
number(min)
Distillation 370 370 360 360
99% Vol (oC
max)
Polycyclic No spec. No spec 11 11
aromatics
hydrocarbons
(PAH),%
massmax
Source: Rajgopal, S. “Refining challenges and Trends.6th summer School on “Petroleum refining
and petrochemicals” June 6,2012, Organised by New Delhi

MAXIMIZING VALUE ADDITION TO REFINERY STREAMS

For a refinery to be successful today, it has to be integrated with petrochemical to benefit from
better realization from value added products and to mitigate the effect of volatile oil process and
highly competitive refining business [Singh and Vaidya, 2012]. Some of the streams which can
maximize value addition to the refinery is given in Table M-VI 1.8.

Table M-VI 1.8: Maximizing Value Addition to Refinery Streams

Streams Utilization
Fuel Gas H2
FCC
Ethylene Ethyl Benzene to Styrene
Propylene Cumene, Iso-Propanol
Butylene Methyl Ethyl Keton, MTBE,
Xylenes
C3 Propylene + H2
C4 Discussed Separately
LPG BTX
C5 TAME
Light naphtha LPG, BTX
Heavy Naphtha Aromatics
Kerosene n-paraffins to LAB
LCO (FCC unit) Mixed Naphthalenes
Coker Kerosene α-Olefins
Sources: M. O. Garg Director Indian Institute of Petroleum, Dehradun 23 rd National Convention of
Chemical Engineers IIT Roorkee, 5 – 7 October 2007
REFERENCE

1. Garg, M. O., Invited talk 23 rd National Convention of Chemical Engineers IIT Roorkee, 5 –
7 October 2007
2. Mishra, A.K, Unnikrishnan, A., “Overview of the quality of crude oils processed in India”
1996, p.22 Challenges in crude oil evaluation: edt. Nagpal, J.M., New Delhi, Tata McGraw-
Hill Publishing Company Ltd, 1996, p. 1.
3. Mukhulyonov, I.U., Kuznetsov, D., Averbukh, A., Tumarkina, E., Furmer “Chemical
Technology” Mir Publishers Moscow,1974
4. Rajgopal, S., “Petroleum refining and petrochemicals” Refining challenges and Trends 6th
summer School on June 6,2012, Organised by New Delhi
5. Ravindranath,K., Habubula,M. “Hydro carbon condensate Fractionation in oil and gas
processing complex”, Chemical Engineering world, Vol 27, No.10, 1992, p.43
6. Samanti,R.K., “Refining challenges and Trends” 6th summer School on “ Petroleum refining
and petrochemicals” June 6,2012, Organised by New Delhi
7. Samtani R.K., DGM (Exploration & Production) IOC ltd. 6th June 2011
8. Singh, S., Vaidya,S.M., “The benefits from refinery and petrochemical Integration”
Chemical Industry digest August 2012,p67
9. Speight J.G. “The chemistry and technology of Petroleum”, Marccel Decker, Inc, New York,
1999.
10. Venkatraman, N.S., “Algae biofuel could be India’s savior” chemical News July, 2012, p.40
 EVALUATION OF CRUDE OIL, PETROLEUM
PRODUCTS AND PETROCHEMICALS
Indigenous and imported crude oils are being process in India for production of gasoline, diesel,
kerosene and lube oil, wax and feed stock for petrochemical industry like naphtha, kerosene etc.
Various sources of indigenous crude are:
· Assam crude
· Bombay high and satellite fields, North Gujarat & Ankhleshwar
· KG basin-Rava crude
· Cauvery basin crude
· Rajasthan crude
Various sources of imported crude are
· Arab mix,
· Lavan blend
· Upper Zakum
· Iran mix
· Dubai
· Kuwait crude
· Suez mix
· Zeit bay
· Quaiboe
· Miri light
· Bonny light

TYPES OF EVALUATION
Depending on the objective of evaluation, following are the types of evaluation generally carried
out.
§ Preliminary Assay: Which is generally comprised of
· Key basic properties of crude oil
 · Distillation data generated through a semi fractionating or fractionating
distillation
§ Short Evaluation:
· Physico-chemical properties of crude oil fractionating TBP distillation data
· Yield and some key characteristics of major straight run products (Naphtha,
Kerosene, Gas oil cuts and Atmospheric residue)
§ Detailed Evaluation:
· Physico-chemical properties of crude oil TBP distillation Assay (Atmospheric and
vacuum range)
· Detailed studies on studies on several straight run cut in fuel oil, lube oil and
secondary processing feedstocks and bitumen.

CRUDE OIL EVALUATION [ Joshi & Vijh,1996]

Quality of crude being processed affect
· Plant capacity
· Feed stock availability and quality for downstream units
· Product pattern
· Overall economics
Significant effect on processing scheme and product pattern
Effect of change in crude quality
· Change of product pattern
· Change of processing scheme
· Throughput
· Economics
· Effluent quality
Various parameters for prediction of crude oil storage and handling behavior are viscosity, pour
point, H2S, base of the crude (characterization factors, BMCI index, viscosity index),
mercaptans, acidity, salt and BS & W, distillation, RVP, characteristics of crude, light end
analysis, rheology, corrosiveness, impurities, volatility, LPG potential, sulphur wax, CR, Trace
metals, naphthenic acid, asphaltenes etc. Details description of parameters are given in Table M-
VI 2.1.

Table M-VI 2.1: Various Parameters used for Storage & Handling of Crude
Oil
Parameters Significance Description
Density and Weight to volume and vice versa Density = Mass/volume
API gravity. calculation, checking consistency of API gravity =
crude oil, control of refinery operation 141.5 - 131.5
and give a rough estimation of crude sp.gr.at15.6 /15.6o C
oil. API gravity of lighter crude oil
may be of the order of 45 whereas in
heavier asphaltenes API is 10-12.
Reid vapor Indicates the relative percentage of 145
Degree Be =145-
pressure and gaseous and lighter hydrocarbons. sp.gr.
light end
analysis
Cloud point For estimating the relative amount of
and Pour wax present in the crude oil. Cloud
Point point gives a rough idea above which
the oil can be safely handled.
Viscosity Viscosity indicates the relative Kinematic viscosity = absolute
mobility of various crude oils. viscosity/ density
Temperature has a marked effect on Redwood Viscometer, Saybolt
viscosity. Viscometer are used
Aniline point Aniline point indicates the lowest
temperature at which the oil is
completely mixed with an equal
volume of aniline. High aniline point
indicates that the fuel is Paraffinic and
hence has a high diesel index and very
good ignition quality.
Asphaltenes, Carbon residue and asphaltenes It is determined by Conradson
carbon indicate the presence of heavier carbon residue and Ramsbottom
residue and hydrocarbons in the crude. Carbon carbon residue method.
asphalt residue is the measure of thermal coke
content forming property.
Flash and Flash point is the lowest temperature at Penskys Martens open/closed cup
fire point which application of the test flame is used.
causes the vapour and air mixture
above the sample to ignite.
Fire point is the lowest temperature at
which the oil ignites and continues to
burn.
Smoke point It is an indication of the smoking Smoke volatility Index( SKI)
tendency of fuel. It is used for = Smoke point + 0.42 x recovery
evaluating the ability of kerosene to at 204 oC
burn without producing smoke. It is the
maximum flame height in mm at which
the fuel will burn without smoking.
Acidity It is an indication of the corrosive
properties of products.
Copper This test serves as a measure of
corrosion possible difficulties with copper, brass,
test bronze part of the fuel system.
Water, salt These causes irregular behavior in the Water content is determined by
and distillation and cause blocking and Dean & Starck. Sediment and
sediments fouling of heat exchanger and result in water is determined by
corrosion centrifuging a mixture of crude
oil and toluene. Salt content is
determined by titrating the water
extract with KCNS/AgNO3.
Parameters Significance Description
Base of the For characterisation of the crude oil Characterization factor
crude oil base- paraffinic / intermediate K= 3 TB / Sp. Gr at 15.6/15.6.
/Naphthenic and for measurement of TB =Mean av. Boiling point in
the aromaticity. Various parameters Rankin
used are characterisation factor, BMCI, paraffinic base k= >12.1;
VGC Intermediate base k= 11.5-12.1;
naphthenic k = 11.5; aromatics k
= 9.8-12.0
BMCI (Bureau of Mines
Correlation Index)
BMCI= 48640/ oK + 473.7 g-
456.8
K= avg. boiling point in oK, g
specific gravity 15.6/15.6 oC
BMCI value:
 Paraffinic = <15;
Intermediate =15-50; Naphthenic
= >50
Viscosity Gravity correlation
(VGC)
VGC= 10 G - 1 . 0752 log( V - 38 )
10 - log( V - 38 )

G is sp gravity and V is Saybolt

universal viscosity
Paraffinic base: 0.80-0.83;
Intermediate base: 0.83-0.88,
Naphthenic base: 0.88-0.95
TBP Assay It is done for generating distillation
data and for study of variations of
some key properties throughout the
distillation range.
Gum It is indication of gum at the time of
test and amount of deposition during
service time.
Colour Indication of the thoroughness of the
refining process.
Antiknock Octane number is the percentage of Research octane number (RON)
quality iso-octane in the reference fuel which and Motor octane number (MON)
(octane match the knocking tendency of the are two methods used.
number) fuel under test Anti knock index (AKI)=
(RON + MON)/2
Cetane Cetane number is the percentage of
number cetane which must be mixed with hepta
methylnonane to give the same ignition
performance as the fuel in question.
Stability test It is used for the evaluation of storage
stability and resistance to oxidation.
Carbon CH ratio=(74+15d)/(26-15d),
Hydrogen where d is sp. Gr. at 15 oC/15oC
ratio
Diesel index It is an indication of ignition quality of Diesel index =
a diesel. (Aniline point in oF x API)
/100
Diesel Index = cetane number-
10/0.72
Weathering This test shows the volatility of the
 test for LPG LPG
Frass This is the temperature below which
breaking the bitumen tends to break rather than
point flow.
Source: Mall, 2007

PRODUCT EVALUATION:
Major parameters for gasoline and diesel specification are given below
Major Parameters of Gasoline Specifications
Major parameters for gasoline included in Bharat or Euro norms are
• Lead phase out
• Lower RVP
• Lower benzene & aromatics
• Lower olefin content
• Limited Oxygen content
• Lower Sulfur content
Other parameters of importance are RON, MON, Lead, gum, oxidation stability, density, VLI
index, FBP. In case of reformulated gasoline aromatics, olefins oxygen, Antiknock index, vapor
lock index
Major Parameters of Diesel Specifications
Major parameters for diesel included in Bharat or Euro norms are
• Low sulfur
• Low aromatics
• High cetane number
• Lower density
• Lower distillation end point
Other parameters for diesel are density, viscosity, cetane number distillation range, sulphur,
carbon residues, oxidation stability, Flash point, acid value, ash and water contents
EVALUATION OF FEED STOCKS FOR PETROCHEMICALS
(OLEFIN, AROMATICS, AND LINEAR ALKYL BENZEN (LAB)
PLANTS)

Olefin , aromatic and LAB production are three major Petrochemical building blocks. Various
feed stocks olefins, aromatics and surfactants are given in Table M-VI 2.2.
Input cost of feed constituents is a major portion of the variable cost of production in
petrochemical plants. Major feed input olefin, aromatics and surfactants are Ethane propane
from natural gas, naphtha, kerosene from the refinery and LPG from refinery, pyrolysis gasoline
from steam crackers, Benzene from aromatic plant. Feed quality monitoring and improvement
efforts are therefore very important aspects having significant impact on the economics of the
operation cost. The precursors and undesirable constituents in feed including catalyst and
adsorbents poisons should be known, analyzed and monitored continuously.

Table M-VI 2.2: Feed stocks for Olefin, Aromatics ans LAB
Plant Feed stock
OLEFINS
Ethane, Propane, Naphtha, Gas oil

Naphtha, Pyrolysis gasoline, LPG

AROMATICS

LAB Kerosene for paraffins, benzene

OLEFIN PLANTS
Olefins playing important role in petrochemical industry by providing raw materials for chemical
intermediates like ethylene oxide ethylene glycol, acetaldehyde, vinyl chloride etc and poly
olefins. Olefin production requires more paraffinic naphtha.
Desired components in feed for olefins productions [Dave and Khurana, 1996]:
 · Naphthenes: Naphthene yield olefins of higher carbon number. Butane yield increases
appreciable with naphthenic feed. Naphthenes also enhance production of aromatics.
· Aromatics: The aromatics is feed are highly refractory and they pass through the furnace
unreacted.
· Sulphur: The sulphur in feed suppress stream reforming reaction catalyzed by nickel
present in radiant coil. Optimum level of sulphur is 1 ppm.
· Physical Properties: Density, distillation range are useful and give a rough assessment of
feed quality.
· Ethylene: The following components in feed give ethylene in decreasing order:
· Ethane, Butane to Decane, 3 and 2 Methyl hexane, 2 methyl Pentane/ 2,2 Dimethyl
Butane, Isopentane
· Propylene: The following components in feed give propylene in decreasing order:
· Isobutane, n-nutane, n-propane, 3 methyl pentane, 2,3 dimethyl butane, 2 methyl
hexane, n-pentane, 3 methyl hexane, iso pentane.
· Butadiene: The following components of feed give butadiene is decreasing order:
· Cyclo hexane, methyl cyclo pentane.

Some of the key properties for evaluation of naphtha for olefin production are density, ASTM
distillation, TBP, FBP, Saybolt colour, sulphur, RVP and paraffin, naphthanes and aromatics
content

AROMATIC PLANT
Aromatics especially benzene toluene, xylenes (p- and o-xylenes) are important petrochemical
feed stocks for manufacture of synthetic fibre, pesticides, explosive, surfactants, synthetic
rubber. Aromatics are either processed in Refinery in Catalytic reforming are processed
separately separately in petrochemical complex for manufacture of p-xylene required for
DMT/PTA plant. Quality of naphtha and impurities present in naphtha are very crucial in quality
of aromatics as well as long life of catalyst..
Naphtha cut C6 to C9
Paraffin, Napthenes, Aromatics 110 to 140 oC
Dehydrogenation of C8Napthene yield C8 aromatics. Most desirable component
90% of C8napthalene in feed get converted to C8 aromatics
· C8 Paraffin's: Dehydro cyclisation of C8 paraffin's yield aromatics difficult to 20%
C8paraffins gets converted to C8 aromatics.
· C8 Aromatics: Pass as refractory and directly contribute to C8 aromatic production.
· C8 Aromatic Precursors: It is useful to monitor aromatic precursors= 0.2* C8 P + 0.9 *
C8 N + 1.0 C8 A
Some of thre key properties of naphtha aromatic pro duction are density, ASTM distillation,
IBP,FBP sulphur, nitrogen, chloride, metallic poisons, component analysis for paraffins,
naphtthanes and aromatics (PNA) [Dave and Khurana, 1996]:

SURFACTANTS:
Linear alkyl benzene is one of important feed stock for production of surfactant whose demands
is increasing with increasing population all over the world. LAB requires paraffins for
production of olefins of carbon range C10-12 to have more biodegradable detergent. Benzene is
required for alkylation of olefin to produce LAB. Feed stock for praffins are Kerosene feed 150-
265 oC cut from refinery containing mainly nC7 to NC18 components which is fractionated to
remove lighter and heavier fractions. The fractionated cut is hydrotreated for removal of sulphur
and nitrogen catalyst which are poisonous to molex adsorbent molecular sieve.
Desirable:
LAB requires olefin and benzene. At present trend is for manufacture of biodegradable low
molecular weight LAB, Paraffins containing nC10 to nC13 carbon atoms are required in LAB
manufacture which is obtained by fractionation of kerosene. Nc12 improve the flammability of
LAB product [Dave & Khurana 1996].
Some of the undesirable components in the feed which are sensitive to molex molecular sieves
are contaminants like water, sulphur, nitrogen, oxygen, chlorides, metallic poisons.Kkey
properties of LAB feed stocks are density, ASTM distillation, IBP,FBP, sulphur, bromine index
,aromatics, saybolt colour, smoke point, flash point, nitrogen component analysis for n-C10 to
nC13, total normal paraffins.

REFRENCES:

1. Bhatnagar, A. K., “Analytical Development in crude oil and product characterization”, in

Challenges in crude oil evaluation: ed. Nagpal, J.M., New Delhi, Tata McGraw- Hill
Publishing Company Ltd, 1996, p. 1.
2. Dave, R. R., Khurana, M. L. “Evaluation of feed stocks for aromatics olefins and surfactants
Plants”, in Challenges in crude oil evaluation: ed. Nagpal, J. M., New Delhi, Tata McGraw-
Hill Publishing Company Ltd, 1996, p. 139.
3. Hobson, G.D., Pohl, W., “Modern Petroleum Technology”, Vol. I & II, 5th edition, John
Wiley & Sons, New York, 1986.
4. Joshi,M.K., Vijh,L.K., “Effect of crude quality on processing scheme and product slate” in
Challenges in crude oil evaluation: ed. Nagpal, J.M., New Delhi, Tata McGraw- Hill
Publishing Company Ltd, 1996, p. 39.
5. Mall,I. D., “ Petrochemical Process Technology”, First edition, Macmillan India 2007
 CRUDE OIL DISTILLATION

INTRODUCTION
Refining of crude oils or petroleum essentially consists of primary separation processes and
secondary conversion processes. The petroleum refining process is the separation of the different
hydrocarbons present in the crude oil into useful fractions and the conversion of some of the
hydrocarbons into products having higher quality performance. Atmospheric and vacuum
distillation of crude oils is the main primary separation processes producing various straight run
products, e.g., gasoline to lube oils/vacuum gas oils (VGO). These products, particularly the light
and middle distillates, i.e., gasoline, kerosene and diesel are more in demand than their direct
availability from crude oils, all over the world.

PRETREATMENT OF CRUDE OILS

Crude oil comes from the ground, which contains variety of substances like gases, water, dirt
(minerals) etc. Pretreatment of the crude oil is important if the crude oil is to be transported
effectively and to be processed without causing fouling and corrosion in the subsequent
operation starting from distillation, catalytic reforming and secondary conversion processes.

IMPURITIES
Impurities in the crude oil are either oleophobic or oleophilic.

OLEOPHOBIC IMPURITIES: Oleophobic impurities include salt, mainly chloride &

impurities of Na, K, Ca& Mg, sediments such as salt, sand, mud, iron oxide, iron sulphide etc.
and waterpresent as soluble emulsified and /or finely dispersed water.

OLEOPHILIC IMPURITIES: Oleophilic impurities are soluble and are sulphur compounds,
organometallic compounds, Ni, V, Fe and As etc, naphthenic acids and nitrogen compounds.

Pretreatment of the crude oil removes the oleophobic impurities.

PRETREATMENT TAKES PLACE IN TWO WAYS:

Ÿ Field separation
Ÿ Crude desalting
Field separation is the first step to remove the gases, water and dirt that accompany crude oil
coming from the ground and is located in the field near the site of the oil wells.

The field separator is often no more than a large vessel, which gives a quieting zone to permit
gravity separation of three phases: gases, crude oil and water (with entrained dirt).

CRUDE DESALTING
It is a water washing operation performed at the refinery site to get additional crude oil clean up.
Ÿ Crude Oil Desalting consists of

Ÿ Purifying process

Ÿ Remove salts, inorganic particles and residual water from crude oil

Ÿ Reduces corrosion and fouling

Desalting process is used for removal of the salts, like chlorides of calcium, magnesium and
sodium and other impurities as these are corrosive in nature. The crude oil coming from field
separator will continue to have some water/brine and dirt entrained with it. Water washing
removes much of the water-soluble minerals and entrained solids (impurities). There are two
types of desalting: single & multistage desalting. Commercial crudes, salt contents 10-200 ppb,
earlier 10-20 ppb were considered satisfactorily low. However, many refiners now aim at 5 ppb
or less (1-2 ppb) which is not possible through single stage desalting, hence two stage desalting
is required.

Desalting process consists of three main stage: heating, mixing and settling.

Crude oil is heated upto 135-141oC in the train of heat exchanger operating in two parallel
section. The temperature in desalting is maintained by operating bypass valve of heat exchanger.
Single stage desalting with water recycle is usually justified if salt content in crude is less than
40 ppb. Two stage desalting involves dehydration followed by desalting. Double stage desalting
is better for residuum hydrotreating. Fuel oil quality is better.
Desalting process is two stage process: forming emulsion of crude and water and demulsification
in which emulsion is broken by means of electric field and demulsifying chemicals.Desalting is
carried out by emulsifying the crude oil and then separating the salt dissolved in water. Two
phases water/oil is separated either by using chemicals to break down the emulsion or by passing
high potential electric current. By injecting water the salts dissolved in the water and solution are
separated from the crude by means of electrostatic separating in a large vessel.

Operating Variables in Desalter: Some of the variables in the desalter operation are crude
charge rate, temperature, pressure, mixing valve pressure drop and wash water rate, temperature,
and quality, desalting voltage. Crude oil temperature charged to the desalter is very important for
the efficient operation of desalter. Lower temperature reduce desalting efficiency because of
increased viscosity of oil while higher temperature reduce desalting efficiency due to greater
electrical conductivity of the crude. Pressure in the vessel must be maintained at a high value to
avoid vaporization of crude oil pressure which result in hazardous ondition, erratic operation and
a loss of desalting efficiency. Flow diagram for crude oil desalting is given Figutre MIV

Unrefined Desalted
Crude Oil Crude Oil
Preheat heat Two stage Desalter
Demulsifier exchanger
Effluent
Water
Process Mixing
Water Unit

Figure M-VI 2.1 Crude oil Desalting

CRUDE OIL DISTILLATION

Desalted crude flows to atmospheric and vacuum distillation through crude pre flashing section.
Atmospheric distillation column (ADU) and Vacuum distillation column (VDU) are the main
primary separation processes producing various straight run products, e.g., gasoline to lube
oils/vacuum gas oils (VGO). These products, particularly the light and middle distillates, i.e.,
gasoline, kerosene and diesel are more in demand than their direct availability from crude oils,
all over the world.
Crude oil distillation consists of atmospheric and vacuum distillation. The heavier fraction of
crude oil obtained from atmospheric column requires high temperature. In order to avoid
cracking at higher temperature the heavier fraction are fractionated under vacuum. Typical flow
diagram of crude oil distillation is given in Figure M-VI 2.2. Various Streams From
Atmospheric And Vacuum Distillation Column is given in Table M-VI 2.2

Figure M-VI 2.2: Atmospheric and Vacuum Crude oil distillation

Table M-VI 2.2: Various Streams From Atmospheric And Vacuum
Distillation Column

Column Fraction Temperature Carbon Uses

range
Atmospheric Fuel Gases >40 C1-C2 Fuel
column LPG C3-C4 Domestic fuel
Straight run 20-90 C6-C10 Gasoline pool
gasoline/
Naphtha 130-180 C6-C10 Catalytic reforming
(Medium and and aromatic plant
heavy) feed stock
Steam cracker,
synthesis gas
manufacture
Kerosene 150-270 C11-12 Aviation turbine fuel,
Domestic fuel, LAB
feed stock (paraffin
source)
Light gas oil 230-320 C13-C17 High speed diesel
component
Heavy gas oil 320-380 C18-C25 High speed diesel
component
Vacuum Light vacuum 370-425 C18-C25 Feed to FCC /HCU
column gas oil
Heavy vacuum 425-550 C26-C38 Feed to FCC /HCU
gas oil
Vacuum slop 550-560 RFCCU feed
Vacuum Residue >560 >C38 Bitumen/ Visbreaker
feed

ATMOSPHERIC COLUMN: Various steps in atmospheric crude oil distillation are

Ÿ Preheating of Desalted crude
Ÿ Preflash
Ÿ Distillation
Ÿ Stabilization of Naphtha

The desalted crude oil from the second stage desalting process is heated in two parallel heat
exchanger. The preheated crude having temperature of about 180oC is goes to pre flash drum where
about 3-4percent of light ends are removed. The preheated crude from the preheater section is further
heated and partially vaporized in the furnace containing tubular heater. The furnace has two zones:
radiant section and convection section. The radiant zone forms the combustion zone and contains the
burners. In convection zone the crude is further heated (inside the tube) by the hot flue gases from the
radiant section.

Heated and partially vaporized crude from the fired heaters enters the flash zone of the column and
fractionated in the atmospheric column. The distillation section consist of overhead section, heavy
naphtha section, kerosene section, light gas oil section, heavy gas oil section and reduced crude section
each section contains circulating reflux system.

Naphtha stabilizer, caustic wash and naphtha splitting section: The unstablished naphtha from the
atmospheric distillation column is pumped to the naphtha stabilizer section for separation of stabilized
overhead vapours which is condensed to recover LPG which is treated in caustic and amine treating
unit. The stabilized naphtha is further separated into light, medium and heavy naphtha.

PRODUCTS of ADU: Major product from atmospheric column are light gases and LPG, light
naphtha,medium naphtha,heavy naphtha,kerosene,gas Oil(diesel),atmospheric residue.

Ÿ Unstabilized Naphtha consists of LPG, naphtha and light gases (C-5 115 oC)
Ÿ Intermediate Naphtha (Bombay High) (135oC) Solvent Naphtha
Ÿ Heavy Naphtha (130-150 oC) routed to diesel or naphtha.
Ÿ Kero/ATF (140-270/250oC)
Ÿ Light Gas Oil (250/270-320oC)
Ÿ Heavy Gas Oil (320-380oC)
Ÿ Reduced Crude Oil

Major products separated in atmospheric column:

Operating Variables in ADU unit are

Ÿ Furnace coil outlet temperature

Ÿ Crude distillation Column top pressure and top temperature
Ÿ Stripping Steam flow
Ÿ Product withdrawal Temperatures

VACUUM DISTILLATION COLUMN (VDU)

The bottom product also called reduced crude oil, from the atmospheric column is fractionated in the
vacuum column. Reduced crude oil is very heavy compared to crude oil distilling under pressure
requires high temperature. Distillation under vacuum permits fractionation at lower temperature which
avoid cracking of the reduced crude oil and coking of the furnace tube. Vacuum is maintained using
three stage steam ejector. The reduced crude oil from atmospheric column at about 360oC is heated
and partially vaporized in the furnace. The temperature in the flash zone of the tower is controlled by
the furnace coil outlet temperature. The preheated and partially vapourised reduced crude enters the
flash zone of vacuum column where it is fractionated into various streams.

PRODUCTS FROM VDU: Various products from VDU areLight gasoil, Heavy gas oil, light
lube distillate, medium lube distillate, heavy lube distillate and vacuum column residue

OPERATING PRESSURE OF VACUUM COLUMN:

Ÿ About 90-95 mm Hg at the top and

Ÿ About 135-140 mm Hg at the bottom

CHEMICAL INJECTION SYSTEM:

Chemical injection system consist of caustic injection and ammonia injection and use of
corrosion inhibitor, use of demulsifier, addition of trisodium phosphate in boiler feed water..
Corrosion in the atmospheric tower overhead system is a common phenomenon and the problem
is increasing with increasing use of the heavier crude oil. Corrosion is primarily due to hydrogen
chloride, which is produced by hydrolysis of the chloride salts remaining after desalting. Other
sours of corrosion are naphthenic acid and hydrogen sulphide. High caustic injection is to
avoided as high caustic injection system may lead to fouling in vacuum and visbreaker furnaces.
ammonia injection is done to maintain the pH. Corrosion inhibitor in kerosene and naphtha is
required to combat the corrosion. De-emulsifier is used to demulsify the water and crude
emulsion. Trisodium phosphate is used to maintain pH and prevent corrosion in the boiler drums

EFFECT OF CRUDE CHARACTERISTICS:

Crude oil characteristics plays important role in the product distribution, processing scheme and
quality of product. Effect of Crude Characteristics on Performance of crude distillation. Effect of
Crude Characteristics on Performance of crude distillation is given in Table M-VI 2.3
Table M-VI 2.3. Effect of Crude Characteristics on Performance of crude
distillation
Characteristics Effect
API API A Measure of “heaviness” or “lightness”
API = (141.5 / density) - 131.5
API > 30 Light Crude
API < 28 Heavy Crude
Viscosity: A measure of resistance to flow and is important parameter for
effective desalting and highly dependant on temperature. High
viscosity crudes need high temperatures for effective desalting.
There is a limit for temperature in desalters.
UOP It is measure of parafinity vis-à-vis aromaticity of Crude
K(Characterisation High UOP K is desired for high conversion in FCC
factor) High UOP K is desired for high conversion in FCC
Aromatic molecules can not be cracked in FCC. They will simply
take ride through the plant.
Total acid Total Acid Number: A measure of Naphthenic Acid contents in
number(TAN) Crude leads to corrosion in various sections of the unit Over 1,500
known NA species are present in crude.
All Nap. Acids are not corrosive. Latest research indicates that
TAN is not a complete Corrosion Index
TAN with 2.5 may corrode at higher rate than TAN with say 6 !
Detailed metallurgical reviews & monitoring mechanism must be
put in place.
BS&W BS&W Bottom Sediments & Water is a measure of water, water
Bottom dissolved ,substances, mud, sand & sludge. Lower the BS&W - the
Sediments & higher the reliability of the Unit. BS&W is one of the major pointer
Water for corrosive materials in crude.

Sulfur Sulfur is a measure of “sourness” & “sweetness” of crude

passed onto products as much as regulations or market accepts
. It is removed in hydrotreaters by reacting with H2 and recovered
as elemental Sulfur in sulphur recovery unit
S > 2.5 Sour Crude, S < 2 Sweet Crude
Total salts Total salts A Measure of contaminant in Crude that will cause
overhead corrosion or foul-up exchangers by settling &
scaling. It is removed in desalters by washing & settling
VGO metals VGO metals is a measure of metals content in VGO
fraction Ni & V are known poisons of VGO hydrotreter catalyst.
Metals in VGO are controlled by controlling wash rate in Slop
Wax section of vacuum column
References
1. Mall, I.D., “Petrochemical process technology” First edi., New Delhi, Macmillan India 2007
2. Mandal, K.K. “Improve desalter control”, Hydrocarbon processing, April, 2005,p.77
3. Watkins, R.N. “Petroleum refinery distillation”, Second edition,1979, Gulf Publishing
Company, Houston
 THERMAL CRACKING, VISBREAKING AND
DELAYED COKING
With the continuous depletion in world oil reserves and increasing demand of petroleum
products, the refiners are forced to process more and heavier crude [Tondon et al., 2007. The cost
advantage of heavy crudes over light crudes has incentivized many Indian Refineries to process
heavier crude, therefore increasing the heavy residue produced at a time when fuel oil demand is
declining [Haizmann et al., 2012]. In order to dovetail both the requirement for processing crude
oil of deteriorating quality and enhancing distillates of improved quality, technological
upgradation have been carried out at refineries which takes care of processing heavy crudes as
well as maximizing value added products and stringent product quality requirements [Sarkar,S.,
Basak,T.K. “ Heavy oil processing in IOCL Refineries]’ Compedenum 16th Technology meet,
Feb 17-19, 2011]. Some of the Residue Upgradation Technologies in Indian Refineries is given
in Table M-VI 4.1.
Table M-VI 4.1: Residue Upgradation Technologies in Refineries
Delayed Coking and Visbreaking Technology for the bottom of the barrel
upgradation; means of disposing of low value
resids by converting part of the resids to more
valuable liquid and gas products.
Uniflex Technology: Technology for processing low quality residue by
thermal cracking to produce high quality distillate
products.
Fluidized Catalytic Cracking (FCC) and A technology introduced to contain generation of
Residual Fluidized Catalytic Cracking black oil from refinery and to increase the
(RFCC) production of high value products like LPG, MS
and Diesel.
Hydrocracking Processes for Residue up gradation FCC process,
delayed coking process &visbreaking
Deep Catalytic Cracking (DCC) and For selectively cracking feed stocks to light
IOCL’s INDMAX olefins.

CRACKING
Cracking of heavy residue is most commonly used method for upgradation of residues. This
involves of decomposition of heavy residues by exposure to extreme temperatures in the
presence or absence of catalysts.
THERMAL CRACKING: Cracking at elevated temperatures in the absence of catalyst eg:
Visbreaking, delayed coking, Fluid coking etc.

CATALYTIC CRACKING: Cracking in presence of catalyst eg: FCC , Hydrocracking, DCC

CRACKING MECHANISM
Cracking takes place by Free Radical mechanism.
INITIATION
C6H14à C2H5 O + C4H9 O
PROPAGATION
C2H5 O + C6H14à C2H6 + C6H13 O
C4H9 O + C6H14à C4H10 + C6H13 O
C4H9 Oà C3H6 + CH3 O
C6H13 Oà C4H8 + C2H5 O (MANY OTHER PRODUCTS)
TERMINATION
C2H5 O + CH3 Oà C3H8
During the cracking operation, some coke is usually formed. Coke is the end product of
polymerisation reaction in which two large olefin molecules combine to form an even larger
olefinic molecule
C10H21-CH=CH2 + CH2=CH-C10H21® C10H21-CH=CH-CH2-CH2-C10H21

THERMAL CRACKING
Thermal cracking process for upgradation of heavy residue has been used since long and still it is
playing an important role in the modern refinery through upgradation of heavy residue and
improving the economics of the refinery through the production of lighter distillate and other
valuable product like low value fuel gas and petroleum coke. Although petroleum coke was first
made by North Western Pennsylvanian the 1860’s using cracking, however, a real breakthrough
in the thermal cracking process was with development of the first cracker by William Burton and
first used in 1913.Heavy residues are a mixture molecules consisting of an oil phase and an
asphaltene phase in physical equilibrium with each other in colloidal form.
Asphaltenes are high molecular weight, relatively high atomicity molecules containing high
levels of metals. During thermal cracking, the long molecules thus depleting the oil phase in the
residue.
Asphaltene cracking is the most difficult component to process and asphaltenes in the feed
remain unaffected, additional asphaltenes may be formed by secondary polymerisation reactions.
At a certain condition asphaltenes is disturbed and asphaltenes precipitate. At this stage of
conversion the product residue becomes unstable.
Under condition of thermal cracking, hydrocarbons, when heated, decompose into smaller
hydrocarbon molecules. The UOP thermal cracking process is based on two coil design for
selective cracking of topped or reduced crudes into valuable products >3500C. Table M-VI 4.2
shows the various thermal cracking process and process conditions.

Higher Boiling Petroleum Stock Lower Boiling Products

Free radical chain reaction:
Free radical + Hydrocarbon Stable End Product
Thermal Treatment; Medium, High,Ultra High (Cracking with higher Temperature and with very
short residence time)
Reactions
- Cracking of side chains free aromatic group
- Dehydrogenation of naphthenes to form aromatics.
- Condensation of aliphatic to form aromatics.
- Condensation of aromatic to form higheraromatics.
- Dimerisation or oligomerisation
Development of Cracking Processes:
Year Process
1861 Thermal cracking
1910 Batch Thermal Cracking
1912 Burton Cracking
1914-22 Continuous Cracking Process
PROCESS VARIABLES: Feed stock properties, Cracking Temperature, Residence time,
PressureThermal Cracking: Medium, High, Ultra High (Cracking with higher Temperature and
with very short residence time)

Table M-VI 4.2: Various Thermal Cracking Process and Process Conditions
Process Process conditions
Mild thermal cracking (low severity)
Mild (470-500oC) heating at 50-200 psig
Improve the viscosity of fuel oil
Visbreaking
Low conversion (10%) to 4300F
Residence time1-3 min
Heated coil or drum
Operates in semi batch mode
Delayed
Moderate (900-960oF) heating at 90 psig
coking
Soak drums (845-900oF) coke walls
 Coked until drum solid
Coke (removed hydraulically ) 20-40% on feed, Yield 4300F, 30%
Server (510-520oC) heating at 10 psig
Oil contact refractory coke
Fluid Coking
Bed fluidized with steam-even heating, Higher yield of light ends
(<Cs),Less coke yield
A continuous fluidised bed technology which converts heavy
Flexicoking residue to lighter more valuable product. The process essentially
eliminates the coke production. Temperature 525oC

VISBREAKING
Visbreaking is essentially a mild thermal cracking operation at mild conditions where in long
chain molecules in heavy feed stocks are broken into short molecules thereby leading to a
viscosity reduction of feedstock. Now all the new visbreaker units are of the soaker type. Soaker
drum utilizes a soaker drum in conjunction with a fired heater to achieve conversion [Sieli, 1998]
Visbreaking is a non-catalytic thermal process. It reduces the viscosity and pour point of heavy
petroleum fractions so that product can be sold as fuel oil. It gives 80 - 85% yield of fuel oil and
balance recovered as light and middle distillates. The unit produces gas, naphtha, heavy naphtha,
visbreaker gas oil, visbreaker fuel oil (a mixture of visbreaker gas oil and vsibreaker tar). A
given conversion in visbreaker can be achieved by two ways:
· High temp., low residence time cracking: Coil Visbreaking.
· Low temp., high residence time cracking: Soaker visbreaking.

Reaction in visbreaking
CH3-CH2-CH2-CH2-CH2-CH2-CH3 CH3-CH2-CH=CH2 + CH3-CH2-CH3

Soaker Visbreaking Process

The furnace operators at a lower outlet temperature and a soaker drum is provided at the outlet
of the furnace to give adequate residence time to obtain the desired conversion while producing a
stable residue product, thereby increasing the heater run and reducing the frequency of unit shut
down for heater decoking [Sieli,1998]. The products from soaker drum are quenched and
distilled in the downstream fractionator. Process diagram for visbreaking with soaker is shown in
Figure M-VI 4.1.
Objective: To lower the viscosity of heavy residues under relatively milder cracking condition
than the conventional cracking processes.
Feed Atmospheric residues àTo get gasoline and diesel oil
Vacuum residues àTo reduce viscosity
Reaction:
- Splitting of C-C bond.
- Oligomerization and cyclisation to naphthenes of olefinic compounds.
- Condensation of the cyclic molecules to polyaromatics.
Side reactions: Foramation of H2S, thiophenes, mercaptans, phenol
Products:
The cracked product contains gas, naphtha, gas oil and furnace oil, the composition of which will
depend upon the type of feedstock processed. A typical yield pattern may be gas 1-2%, naphtha
2-3%, gas oil 5-7%, furnace oil 90-92%.
Visbreaking Conditions:
Inlet Temperature: 305-3250C (15-40 bar)
Exit: 480-5000C (2-10 bar)
With soaking 440-4600C (5-15 bar)
Feed: 900C pretreated with VB tar to 3350C
Visbreaking Furnace:
Convection zone àtop àto thermal efficiency.
Radiation zone àbottom tubes.
Avg. heat flow à 22-30 kw/m2

Variables:
Variables in visbreaker are feed rate, furnace transfer temperature, visbreaker tar quench to
transfer line, fractionation pressure, fractionation top temperature, circulation, reflux flow,
visbreaker tar quench to fractionator bottom, visbreaker tar quench to visbreaker tar stripper
bottom, stabilizer temperature and pressure.
The purpose of visbreaking is to produce lower viscosity fuel oil.
Soaking Drum
Soaking drum is used to lengthen the feed residence time so that the furnace can operate at lower
temperature. Soaker results in saving of energy because of the lower temperature with less coke
tendency, larger gas oil yield
Advantages:
- 15% reduction in fuel oil
- Larger running time between two decoking operations. coke deposit rate 3-4 times slower
than in conventional units.
- Better selectivity towards gas and gasoline productivity.
 Figure M-IV 4.1: Visbreaking with Soaker

Coil Visbreaker: In coil visbreaking process the desired cracking is achieved in the furnace
at high temperature and the products of cracking are quenched and distilled in a downstream
fractionator. Advances in visbreaker coil heater design now allows for the isolation of one or
more heater passes for decoking, eliminating the need of shut the entire visbreaker down for
furnace decoking. Integration of the coil visbreaking process with vacuum units is also being
considered in many areas of the world [Sieli,1998]

COKING
Coking is very severe form of thermal cracking and converts the heaviest low value residue to
valuable distillates and petroleum coke. Relatively severe cracking operations to convert residual
oil products and represents the complete conversion of petroleum residues to coke and lighter
product. Recycle is used to further convert heavy distillate fractions to lighter products
Mechanism of coke formation: The colloidal suspension of the asphaltenes and resin compounds
is distorted, resulting in precipitation of highly cross linked structure of amorphous coke. The
compounds are also subjected to cleavage of the aliphatic groups. Polymerisation and
condensation of the free aromatic radicals, grouping a large number of these compounds to such
a degree that dense high grade coke is eventually formed
The process involves thermal conversion of vacuum residue or other hydrocarbon residue
resulting in fuel gas, LPG, naphtha, gas oil and coke and essentially a complete rejection of
metals. Various types of coking processes are delayed coking, fluid coking and flexi coking.

DELAYED COKING
Delayed coking process is used to crack heavy oils into more valuable light liquid products with
less valuable gas and solid coke as byproducts. Although first delayed coking plant was built
in1930, however delayed coking process has been evolving for 78 years, the past few years have
seen changes in feed stock that has major impact on the design and operation of delayed coking
[Catala, 2009].
Delayed coking consists of thermal cracking of heavy residue in empty drum where deposition of
coke takes place. The product yield and quality depends on the typed feedstock processed.
Typical delayed coking consists of a furnace to preheat the feed, coking drum where the
fractionation of the product takes place.
The feed is first preheated in furnace where the desired cooking temperature is achieved and fed
to the coking drums normally installed in pairs where the cracking reaction takes place and the
coke is deposited in the bottom of the reactor. The coke drums overhead vapour flows to the
fractionating column where they are separated into overhead streams containing wet gas LPG
and naphtha and two side gas oil streams.
Recycled stream from the fractionating column combines with the fresh feed in the bottom of the
column and is further preheated in coke heaters and flows to the coke drums. When a coke drum
is filled, the heated streams from the coke heated are sent to the other drum. Process flow
diagram for delay coking is shown in Figure M-VI 4.2.
The reaction involved in delayed coking is partial vaporization and partial cracking, cracking of
two vapour phase in the coke drum and successive cracking used polymerization of liquid
phaseresulting in formation of coke in the drum.
Feed: Vacuum residue, FCC residual, or cracked residue. Studies show that feedstock quality
and severity on conversion impact the stability of visbreaker residue [Stratiev et al., 2008]
Product: Gases, Naphtha, Fuel oil, Gas oil and Coke.
 Figure M-IV 4.2: Process Flow Chart of Delayed Coking

Operating Variables
Feed stocks variables: Chracterisation factor, degree of reduction, conardson carbon, sulphur
content, Metallic constituents.Low feed stock characterisation factor and high carbon residue
increase coke yield and quality of gas oil end point.

Engineering Variables: Batch, Semi continuous or continuous, Capacity and size factors, Coke
removal equipment, Coke handling, Storage and Transportation

Operating Variables: Various operating variables in delayed coking are temperature, pressure,
recycle ratio, transfer temperature, and coke chamber pressure.

Higher temperature: Results in more vaporization of the inlet material causing low coke yield.
A furnace outlet temperature of 485-505 0C is maintained. High temperature results in hard coke
while coke is soften when too low temperature is maintained.

Higher pressure: Results in an increase in coke and gas yields which is undesirable as basic
objective is to improve the yield of distillation with less coke.

Higher recycle ratio: Results in higher coke and gas yields. Lower recycle ratio is always
desirable for higher yield of liquid product.
Coke yield =1.6 CCR(conardson carbon residue)
Gas yield= 7.8+.144xCCR
Naphtha yield=11.29+0.343CCR
Gas yields =110-coke-gas yield-naphtha yield
Low feed stock characterization factor and high carbon residue increase coke yield and quality of
gas oil end point.

Fluid Coking:Fluid coking is non- catalytic fluid bed process whereresidue is coked by
spraying into a fluidized bed of hot, fine coke particles. Higher temperature with shorter contact
time than delayed coking results in increased light and medium hydrocarbons with less cake
generation. Shorter residence time can yield higher quantities of liquid less coke, but the product
have lower value [Rana et al., 2007].

Flexi Coking:It is continuous process involves thermal cracking in a bed fluidized coke and
gasification of the coke produced at 870 oC. This process contains an additional step of
gasification(Temp: The gases leaving the gasifier is low calorific value fuel gas at 800-1500
kcal/m3 (4200 to 5000 kJ/std m3 and is burned in the furnace or power plants.It can be applied to
wide variety of feed stocks.

UOP UniflexTM Process [ Haizimann et al.,2010]: It is high conversion, commercially

proven technology, that processes low quality residue streams, like vacuum residue, to make
very high quality distillate products. The process utilizes thermal cracking to reduce molecular
weight of the residue in the presence of hydrogen and a proven proprietary, nano sized catalyst to
stabilize the cracked products and inhibit the formation of coke precursors. The main products
from uniflex are naphtha and diesel with a yield of greater than 80 vol%.

REFRENCES
1. Catala, K.A., Karrs, M.S., Sieli, G., “Advances in delayed coking heat transfer equipment”
Hydrocarbon Processing February 2009, p.45
2. Haizmann, R.S., Hunt, P., Srinivas, A., Banerjee, S., “Maximize return from every barrel:
Proven residue upgrading technology” J. of Petrofed, Jan-March 2012, Vol.11, p.38
3. http://www.exonmobil.com/refiningtechnologies
4. http://www.fwc.com/publications/tech_papers/oil-gas/visbreaking.cfm
5. Rana, M.S., Samano, V., Ancheyta, J., Diaz, J.A.I. “A review of recent advances on process
technologies for upgrading of heavy oils and residua”, Fuel, vol. 86, (9), June 2007, 1216-
1231
6. Sarkar, S., Basak, T.K. “Heavy oil processing in IOCL Refineries”, Compendium 16th
Technology meet, Feb 17-19, 2011.
7. Sieli, G.M., “Visbreaking the next generation” Foster wheeler publication, 1998.
8. Stratiev, D., Kirilov, K., Belchev, Z., Petkov, P., “How feed stocks affect visbreaker
operations”, Hydrocarbon processing, June 2008,p.105
9. Tondon, D., Dang, G.S, Garg M.O., “Visbreaking: a flexible process to reduce the pour point
of heavy crude oils” J. of Petrotech society, June, 2007, p.44.
 CATALYTIC CRACKING
Catalytic cracking process was developed in1920 by Eugene Houdry for upgradation of residue
was commercialized latter in 1930. Houdry process was based on cyclic fixed bed configuration.
There has been continuous upgradation in catalytic in catalytic cracking process from its incept
of fixed bed technology to latter fluidized bed catalytic cracking (FCC).The feed stock for
catalytic cracking is normally light gas oil from vacuum distillation column. Catalytic cracking
cracks low value high molecular weight hydrocarbons to more value added products (low
molecular weight) like gasoline, LPG Diesel along with very important petrochemical feedstock
like propylene, C4 gases like isobutylene, Isobutane, butane and butane. Main Catalytic Cracking
Reaction is given in Table M-VI 5.1.

Main reactions involved in catalytic cracking are

Ÿ Cracking
Ÿ Isomerisation
Ÿ Dehydrogenenation
Ÿ Hydrogen transfer
Ÿ Cyclization
Ÿ Condensation
Ÿ Alkylation and dealkylation
Major primary reactions taking place in catalytic cracking is given in Table
Paraffins Smaller paraffins + olefins
Alkyl naphthene naphthene + olefin
Alkyl aromatic aromatic + olefin
Multiring naphthene alkylated naphthene with fewer rings

Table M-VI 5.1 Main Catalytic Cracking Reaction

Paraffins Cracking Paraffins + Olefins
Olefins
 Cyclization Coke

Naphthenes

Aromatics

Trans alkylation Different alkyl aromatics

FLUID CATALYTIC CRACKING

Fluid catalytic cracking is now major secondary conversion process in Petroleum refinery since
1942. there are more than 400 FCC units in world. The process provides around 50 percent of all
transportation fuel and 35percent of total gasoline pool. Major land marks in the history of FCC
has been:[Ghosh,2002]

· Introduction of zeolite catalyst during 1960 which has resulted in lower residence time
· Introduction of ultra stable Y-zeolite in mid 60’s
· Switch over from bed cracking to riser cracking
· Introduction of large number of additives for boosting of gasoline octane/yield of light
naphtha
· SOx control
· Nickel and vanadium passivation
FCC is a multi-comp
ponent cataly
yst system with
w circulatiing fluid bedd reactor sysstem with reeactor
Regeneraator system configuratio
on. Figure M-VI
M 5.1 shhows detail s of FCC pprocess and FCC
reactor.
Flue Gas
G Re
eactor vapors
Over head gases
s
Process Air

Treated gas

Power
P
Re
ecovery
Steam

Boiler Feed
Water
LPG

Unsaturatted Gas
Concenntrator

Sppent
Cattalysis Main
Fractionating
Catalyst Fluid Cattalytic Column Heavy
Reg
generator Cracking n
naphtha Gasoline
Reacttor
Process Air Regenerrated
Cataly
yst

Light
Cycle Oil

Steam Raw oil

·
Fuel Oil

Fig
gure M-VII 5.1: Fluiid Catalytiic Crackin
ng Processs and FCC
C Reactor
FEED STOCK
Vacuum gas oil (VGO), Hydro-treated VGO, Hydro-cracker bottom, Coker gas oil (CGO), De-
asphalted oil (DAO), Reduced crude oil (RCO), Vacuum residue (VR)
· Typical feedstock consists of Vacuum and Atmosphere gas oil but may include other
heavy stream.
· Major contaminant in the feed includes carbon residue and metals.
· While FCC process feed containing up to 4% Conradson carbon MSCC can process all
kinds of feed.
Process Steps
Three basic functions in the catalytic cracking process are:
Reaction - Feedstock reacts with catalyst and cracks into different hydrocarbons;
Regeneration - Catalyst is reactivated by burning off coke; and recerculated to reactor
Fractionation - Cracked hydrocarbon stream is separated into various products like LPG and
gasoline, like light cycle oil and heavy cycle oil are withdrawn as side stream

Reactor and Regenerator Section: Catalyst section consists mainly of the reactor and
regenerator
· The feed to unit along with recycle streams is preheated to temperature of 365oC-370Oc
and enters the riser where it comes in contact with hot regenerated catalyst ( at a
temperature of about 640-660oC. Finely divided catalyst is maintained in an aerated or
fluidized state by the oil vapors.
· The catalyst section contains the reactor and regenerator & catalyst re circulates between
the two.
· Spent catalyst is regenerated to get rid of coke that collects on the catalyst during the
process. Spent catalyst flows through the catalyst stripper to the regenerator, where most
of the coke deposits burn off at the bottom where preheated air and spent catalyst are
mixed. Fresh catalyst is added and worn-out catalyst removed to optimize the cracking
process
Fractionation - Cracked hydrocarbon stream is separated into various products. LPG and gasile
are removed overhead as vpour. Unconverted product like light cycle oil and heavy cycle oil are
withdrawn as side stream. Overhead product is sent to stabilsation section where stablised
gasoline is separated from light products from which LPG is recovered.

Typical operating parameter of FCC

Raw oil feed at heater inlet : 114 cubic meter /h
Furnace outlet temperature : 291oC
Reactor feed temperature : 371oC
Reactor Vapour temperature : 549oC

Product Obtained
· Light gas -H2, C1, and C2s
· LPG C3s and C4s – includes light olefins
· Gasoline C5+ high octane component for gasoline pool or light fuel
· Light cycle oil (LCO) blend component for diesel pool or light fuel
· Heavy cycle oil (HCO) Optional heavy cycle oil product for fuel oil or cutter stock
· Clarified oil (CLO) or decant oil: slurry for fuel oil
· Coke by-product consumed in the regenerator to provide the reactor heat demand

FCC Catalysts
Major breakthrough in the catalytic racking process was development zeolite catalysts which
demonstrated vastly superior activity, gasoline selectivity, and stability characteristics compared
to original amorphous silica alumina catalyst [Hemler & Smith, 2004].

Year 1950 1970 1990

Zeolite content, wt% 0 10 Upto 40
Particle density, g/cc 0.9 1 1.4
Relative Attrition Index 20 5 1

Today’s FCC catalysts Porous spray dried micro-spherical powder

· Particle size distribution of 20 -120 micron & particle density ~ 1400 kg/m3
 · Comprising Y zeolite in many derivatives of varying properties
· Supplied under various grades of particle sizes & attrition resistance
· Continuing improvement metal tolerance, coke selectivity
New bread of catalyst are high metal tolerance with high matrix catalyst having better
accessibility, regenerability and strippability [Ghosh, 2006]

Options for Clean Fuel:

For upgrading FCC products into acceptable blending components following three steps are
being used [Letzsch, 2005];
· Severe hydro processing of feed to FCC
· Treating each of the products in hydrotreater
· Combination of both upstream and downstream processing

MODIFIED CATALYTIC CRACKING PROCESSES

Resid FCC (RFCC) Process:
The RFCC process uses similar reactor technology as the FCC process and is targeted for
residual feeds greater than 4 wt-% Conradson carbon. A two stage regenerator with catalyst
cooling is typically used to control the higher coke production and resulting heat.

Deep Catalytic Cracking (DCC):

Milli Second Catalytic cracking (MSCC) Process:
Improvements in riser termination devices have led to significant decreases in post-riser
residence time and post-riser cracking. The benefits of shorter catalyst-and oil contact time have
been lower dry gas yields, lower delta coke on catalyst and more selective cracking to gasoline
and light olefins.
• Due to improvement in reactor design there is lower regenerator temperature and higher
catalyst recovery.
Petro FCC Process
The Petro FCC process targets the production of petrochemical feedstock rather than fuel
products. This new process, which utilizes a uniquely designed FCC unit, can produce very high
yields of light olefins and aromatics when coupled with aromatics complex. The catalyst section
of the Petro FCC process uses a high-conversion, short-contact time reaction zone that operates
at elevated reactor riser outlet temperatures

Indmax Technology- Residue to Olefin was developed by IOC R&D center and has
been successfully commissioned in IOC Guwahati Unit [Bhatacharya, 2001]
Some of the special features of the technology are:
Operational features of Indmax technology
· Very high cat/oil ratio(15-25)
· Higher riser temperature (>5500 C)
· Higher riser steam rate
· Relatively lower regeneration temperature.
Benefits
· LPG 35-65 wt%
· Propylene 17-25 wt% feed
· High octane gasoline (95+)
Multifunctional proprietary catalyst
· Higher propylene selectivity
· Superior metal tolerance
· Lower coke mate

Maximizing Propylene Output in FCC

New FCC processes are being operated to maximize the yield of propylene due to growing
demand of propylene. Significant scope exists in the refinery in Asia region to enhance the
production of propylene in Asia region [Ghosh, 2006]. Maximizing propylene yield from FCC is
typically accomplished by combining a low rare earth catalyst system with severe reaction
condition [Amano,T.,Wilcox,J. and Pouwels,C. “ Process and catalysis factors to maximize
propylene output” Petroleum Technology Quarterly 3, 2012,p.17]. some of the olefin
maximizing technology are deep catalytic cracking (DCC) based on riser bed catalytic cracking,
Propylene –Max technology by ABBS Lummus global, Maxofin Process by Mobil-M.W. Kellog

HYDROCRACKING
The development of upgrading technology for heavier stocks having high sulfur, nitrogen and
heavy metal (Ni, V) are becoming important. Hydrocracking is one of the most versatile
processes for the conversion of low quality feed stocks into high quality products like gasoline,
naphtha, kerosene, diesel, and hydrowax which can be used as petrochemical feed stock. Its
importance is growing more as a refiners search for low investment option for producing clean
fuel. New environmental legislations require increasing and expensive efforts to meet stringent
product quality demands.
Hydrocracking processes uses a wide variety of feed stocks like naphtha, atmospheric gas oil,
vacuum gas oils, coke oils, catalytically cracked light and heavy cycle oil, cracked residue,
deasphalted oils and produces high quality product with excellent product quality with low sulfur
contents. Comparison of catalytic cracking and hydrocracking is given in Table M-VI 5.1.
The history of the hydrocracking process goes back to late 1920 when hydrocracking technology
for coal conversion was developed in Germany. During World War II, two stage hydrocracking
were applied in Germany, USA and Britain. However, real breakthrough in hydrocracking
process was with the development of improved catalyst due to which processing at lower
pressure. Hydrocracking can process wide variety of feedstocks producing wide range of
products.
Feed: Straight run gas oil, Vacuum gas oils, Cycle oils, Coker Gas oils, thermally cracked
stocks, Solvent deasphalted residual oils, straight run naphtha, cracked naphtha.
Product: Liquefied petroleum gas (LPG), Motor gasoline, Reformer feeds, Aviation turbine
fuel, Diesel fuels, heating oils, Solvent and thinners, Lube oil, FCC feed
Table M-VI 5.1: Comparison of Catalytic Cracking and Hydrocracking
Catalytic Cracking Hydro-cracking
Carbon rejection Hydrogen addition
Riser-regenerator-configuration Downflow packed bed
LPG/gasoline Kerosene/diesel
Product rich in unsaturated components Few aromatics, low S- and N-content in
product

Recent Development Hydrocracking:

There has been continuous development in the hydrocracking technology both in process and
catalyst. Some of the important development in hydrocracking has been mild hydrocracking and
resid hydrocracking. Mild hydrcracking (MHC) is characterized by relatively low conversion
(20-40%) as compared to convention hydrocracking which give 70-100% conversion of heavy
distillate at high pressure. MHC route produces low sulphur (10 ppm sulphur as desired by future
diesel specification) diesel. New mild hydrocracking route produces 10 ppm sulphur diesel
which is produced by hydro-cracking under mild pressure. MHC allows increasing diesel
production through VGO hydro-conversion.
The yield of middle distillates obtained from hydro cracker is much more than that obtained from
other processes also, hydro cracker does not yield coke or pitches as by product. The increased
demand for environmentally acceptable products forced the refiners to accept stringent
specifications for gasoline & diesel necessitating the use of hydrocracking technology to limit
sulphur & aromatic in petroleum products. No post treatment is required for the hydro cracker
products.

Hydro-treatment & Hydrocracking Catalyst

Hydrocracking processes involved two types of catalyst:
· Hydro pretreatment catalyst
· Hydrocracking catalyst
Hydrotreating (Pretreat) Catalyst
The main objective of pretreat catalyst is to remove organic nitrogen from the hydro cracker feed
allowing
(i) Better performance of second stage hydrocracking catalyst, and
(ii) The initiation of the sequence of hydrocracking reactions by saturation of aromatic
compounds
Pretreat catalyst must have adequate activity to achieve above objectives within the operating
limits of the hydrogen partial pressure, temperature and LHSV.

Hydrocracking Catalyst
Hydrocracking catalyst is a bi-functional catalyst and has a cracking function and hydrogenation-
dehydrogenation function. The former is provided by an acidic support whereas the latter is
imparted by metals. Acid sites (Crystalline zeolite, amorphous silica alumina, mixture of
crystalline zeolite and amorphous oxides) provide cracking activity. Metals [Noble metal (Pd, Pt)
or non noble metal sulphides (Mo, Wo or Co, Ni)] provide hydrogenation dehydrogenation
activity. These metals catalyze the hydrogenation of feedstocks making them more reactive for
cracking and hetero-atom removal as well reducing the coke rate
Zeolite based hydrocracking catalysts have following advantages of greater acidity resulting in
greater cracking activity; better thermal/hydrothermal stability; better naphtha selectivity; better
resistance to nitrogen and sulphur compounds; low coke forming tendency, and easy
regenerability.

Once though Hydrocracking Process

The unit consists of the following sections:
· Furnace
· First stage Reactor section
· Second stage Reactor section
· High pressure separator
· Fractionation Section
· Light Ends Recovery section
In single stage process both treating and cracking steps are combined in a single reactor. Single
stage hydrocracking flow diagram is show in Figure M-VI 5.3[ Mall,2007].
In this process the feed along with recycle unconverted residue from the fractionator is first
hydro-treated in a reactor and then the combined stream gases are fed to second reactor where
cracking takes place in the presence of hydro-cracking catalyst.
In the single stage process the catalysts work under high H2S and NH3 partial pressure.

Gas to
Make up
amine LPG
Hydrogen Recycle treatment
Gasoline
I II

D istilla tion
Kerosene

S trip pe r
1st R e actor

2 nd R ea cto r

S ep arator

Furnace Diesel

Preheater

Residue

Hydrogen
Feed

Figure M-VI 5.3: Once Through Hydrocracking

Two Stage Hydrocracking Process

The unit consists of the following sections:
· Furnace
· First stage Reactor section.
· Second stage Reactor section
· Third stage reactor
· Fractionation Section
 · Light Ends Recovery section
Preheated feed is first hydro treated in a reactor for desulphurization and denitrogenation in
presence of pretreat catalyst followed by hydrocracking in second reactor in presence of strongly
acidic catalyst with a relatively low hydrogenation activity. In the first stage reactor the sulphur
and nitrogen compounds are converted to hydrogen sulphide and ammonia with limited
hydrocarcking. The two stages process employs interstage product separation that removes H2S
and NH3. In case of two stage process, hydrocracking catalyst works under low H2S and NH3.
Process flow diagram for two stage hydrocracking process is shown in Figure M-VI 5.4 [ mall
2007].
Gas to amine
treatment
Reactor1 LPG

Reactor2
Reactor3 Gasoline
Heater

Distillation
Stripper
Kerosene

Diesel

Heater

Feed
Residue
Separator

Hydrogen

Figure M-VI 5.4: Two Stage Hydrocracking Process

HYDROCRACKING CHEMISTRY
Hydrocracking process is a catalytic cracking process which takes place in the presence of an
elevated partial pressure of hydrogen and is facilitated by bio-functional catalyst having acidic
sites and metallic sites. During hydrocracking process hydrotreating reactions and hydrocracking
reactions are two major reactions which take place.
A typical hydrocracking reaction is as follows.
· C22 H46 + H2¾¾¾® C16H34 + C6H14
Various hydrotreating reactions are hydrodesulphurization, denitrogenation, hydro
deoxygenation, hydro metallization, olefin hydrogenation partial aromatics saturation.
Various hydrocracking reactions are splitting of C-C bond and or C-C rearrangement reaction
(hydrisomerisation process) Hydrogenation and dehydrogenation catalyst.

Effect of Operating Parameters

Various operating parameters affecting hydrocracking are
· Reaction temperature
· Hydrogen partial pressure
· Hourly feed velocity of the feed
· Hydrogen recycle ratio
Temperature increase in temperature accelerates cracking reaction on acid sites and displaces the
equilibrium of hydrogenation reactions towards dehydrogenation. Too high temperature limits
the hydrocracking of aromatic structure [Raseev, 2003].
The pressure influences significantly the equilibrium of dehydrogenation-hydrogenation
reactions that takes place on the metallic sites. The increase in pressure for a given molar ratio
H2/feed corresponds to increase in the partial pressure of hydrogen, will produce an increase the
conversion of the aromatic structures to saturated products which will improve the quality of jet
fuel, diesel fuel and oil with very high viscosity index.

Effect of Feedstock: a higher content of aromatic hydrocarbons requires higher pressure and
higher hydrogen/feed ratio, the lowest possible temperature and a higher hydrogen consumption
of hydrogen and the severity of the process
Effects of Feed Impurities: Hydrogen sulphide, nitrogen compounds and aromatic molecules
present in the feed affect the hydrocracking reactions. Increase in nitrogen result in lower
conversion.
Ammonia inhibits the hydrocracking catalyst activity, requiring higher operating temperatures.
Polymeric compounds have substantial inhibiting and poisoning effects. Polynuclear aromatics
present in small amount in the residue deactivate the catalyst.
Effect of various parameters on catalyst life:
Variable Change Effect on catalyst life
Feed rate Increase-Decrease
Conversion Increase-Decrease
Hydrogen partial pressure Increase-Increase
Reactor pressure Increase-Increase
Recycle gas rate Increase -Increase
Recycle gas purity Increase -Increase

HYDRO-CRACKING TECHNOLOGY PROVIDER

· Chevron: Isocracking
· UOP: Uni-cracking
· IFP: Hydrocarcking
· B.P. U.K: Hydrocracking
· Shell: Hydrocracking
· Standard Oil: Ultracracking
· Linde: Hydrocarking
· Union Oil Co.: Uni-cracking

CATALYST DEACTIVATION
Catalyst activation may occur due to coke deposition and metal accumulation.
Coke Depositions may be due to condensation of poly-nuclear and olefinic compounds into high
molecular weight which cover active sites. Metal Accumulation occurs at the pore entrances or
near the outer surface of the catalyst

CATALYST REGENERATION
Catalyst regeneration is done by burning off the carbon, and sulphur and circulation of circulate
nitrogen with the recycle compressor, injecting a small quantity of air and maintaining catalyst
temperature above the coke ignition temperature.

REFERENCES
1. Amano, T., Wilcox, J., Pouwels, C., “Process and catalysis factors to maximize propylene
output”, Petroleum Technology Quarterly, 3, 2012, p.17
2. Debasis Bhattacharyya, “Fluid Catalytic Cracking: Process Fundamentals”, 6th Summer
School on Petroleum Refining & Petrochemicals 6th–10th June, 2011
3. Ghosh, S “Fluid catalytic cracking: An overview & future scenario”, Indian Chemical
Engineer special Issue, Vol 1,2002, p.27
4. Ghosh, S. “Recent advances in fluid catalytic cracking”, Petrotech society’s summer school
program on advances in Petroleum Refining industry, 3-8 July 2006 held at IIPM, Gurgaon
5. Hemler, C.L. and Smith, L.F., “UOP fluid catalytic cracking Process” in Hand book of
Petroleum refining Processes edited by Meyers, R.A. Third edition The McGraw-Hill
Publication data 2004.
6. Letzsch, W., “Improve catalytic cracking to produce clean fuels”, Hydrocarbon processing
Feb, 2005,p.77
7. Mall,I.D. “Petrochemical processes technology” First Edi., New Delhi, Macmillan India,
2007
8. Raseev, S. “Hydrocracking in Thermal and Catalytic Processes in Petroleum refining”
Marcel Dekker, Inc2003, p.681.
9. Verma, RP. “Hydroprocessing:Indian scenario” Indian Chemical Engineer Special issue,
Vol 1, 2002.
 CATALYTIC REFORMING
Catalytic reforming is a major conversion process in petroleum refinery and petrochemical
industries. The reforming process is a catalytic process which converts low octane naphthas into
higher octane reformate products for gasoline blending and aromatic rich reformate for aromatic
production. Basically, the process re-arranges or re-structures the hydrocarbon molecules in the
naphtha feedstocks as well as breaking some of the molecules into smaller molecules. Naphtha
feeds to catalytic reforming include heavy straight run naphtha. It transforms low octane naphtha
into high-octane motor gasoline blending stock and aromatics rich in benzene, toluene, and
xylene with hydrogen and liquefied petroleum gas as a byproduct. With the fast growing demand
in aromatics and demand of high - octane numbers, catalytic reforming is likely to remain one of
the most important unit processes in the petroleum and petrochemical industry. Various
commercial catalytic reforming processes is given in Table M-VI 6.1.

Table M-VI 6.1: Various Catalytic Reforming Processes

Process Licensor
Rheniforming Chevron oil
Power forming ESSO Oil/EXXON
Magna forming Altalntic Richfield oil
Ultra forming British petroleum
Houdriforming Houdry process
CCR Plateforming UOP
Octanising Axen

OCTANE NUMBER OF HYDROCARBONS

Octane number is a measurement of antiknock characteristics of fuels
· Among the same carbon number compounds, the order of RONC is (Research Octane
Number )
Paraffins < Naphthenes < Aromatics
· Branched paraffins also have high octane. It increases with degree of branching.
Therefore, octane number of naphtha can be improved by reforming the hydrocarbon molecule
(Molecular rearrangement). Octane number of various hyrdrocarbons is mention in Table M-VI
6.2. Such rearrangement takes place in reforming reactors in presence of catalyst by way of
numerous complex reactions.

Table M-VI 6.2: Octane Number of Various Hydrocarbons

Hydrocarbon Octane number
n-Butane 94.0
i-Butane 102.0
n-Pentane 61.8
i-Pentane 93.0
n-Heptane
octane 100.0
toluene 119.7

Feed consists of Heavy straight run gasoline (HSR), Naphtha, Heavy hydro cracker naphtha and
Naphtha containing (C6-C11) chain paraffins, olefins, naphthenes & aromatics.

PROCESS STEPS IN CATALYTIC REFORMING

Basic steps in catalytic reforming involve
· Feed preparation: Naphtha Hydrotreatment
· Preheating: Temperature Control,
· Catalytic Reforming and Catalyst Circulation and Regeneration in case of continuous
reforming process
· Product separation: Removal of gases and Reformate by fractional Distillation
· Separation of aromatics in case of Aromatic production

NAPHTHA HYDRO TREATMENT

Naphtha hydrotreatment is important steps in the catalytic reforming process for removal of the
various catalyst poisons. It eliminates the impurities such as sulfur, nitrogen, halogens, oxygen,
water, olefins, di olefins, arsenic and other metals presents in the naphtha feed stock to have
longer life catalyst. Figure M-VI 6.1 illustrate hydrotreatment of naphtha.
· Sulphur: Mercaptans, disulphide, thiophenes and poison the platinum catalyst. The
sulphur content may be 500 ppm.
· Maximum allowable sulphur content 0.5 ppm or less and water content <4 ppm.
· Fixed bed reactor containing a nickel molybdenum where both hydro de sulphurisation
reactions and hydro de nitrification reactions take place.
· The catalyst is continuously regenerated. Liquid product from the reactor is then stripped
to remove water and light hydrocarbons.
Various sections in the naphtha hydro treatment unit are:
Charge Heater: Preheating reactor feedstock to reaction temperature of 340 oC. Charge heater
has four passes four gas burners. Heater tubes are made up of SS-321
Reaction Section: The reactor consists of two catalyst beds.
Stripping Section: Stripping section uses air for stripping the light ends mainly hydrogen
sulfide from reactor product, stripper temperature 14 kg/ cm2 and temp. 172 0C
Stripper Reboiler: Stripper reboiler supply heat required for striper

Operating Variables Naphtha Hydrotreatmernt

· Reactor temperature
· Space velocity
· Hydrogen partial pressure
· H2/HC ratio, feed quality
· Stripper bottom temperature

Flue gas
Make up Recycle Hydrogen
Hydrogen

Low
Temp
Feed Heater Flash

Hydro desulfurisation
Treater Stripper

High
Temp.
flash

Desulfurised feed

Figure M-VI 6.1: Hydrotreatment of Naphtha

CLASSIFICATION OF PROCESSES
· Semi Regenerative catalytic reforming
· Cyclic catalytic reforming
· Continuous catalytic reforming(CCR)
Various Types of Catalytic Reformers
Semi-Regenerative Fixed Bed reactors: In this type of reformers the catalyst generally
has a life of one or more years between regeneration. The time between two regeneration is
called a cycle. The catalyst retains its usefulness over multiple regeneration.
Cyclic Fixed Bed Reformers: Cyclic reformers run under more severe operating conditions
for improved octane number and yields. Individual reactors are taken offline by a special valving
and manifold system and regenerated while the other reformer unit continues to operate.
Continuous Reformers: In these reformers the catalyst is in moving bed and regenerated
frequently. This allows operation at much lower pressure with a resulting higher product octane,
C5+, and hydrogen yield. These types of reformers are radial flow and are either separated as in
regenerative unit or stacked one above the other.

Semi- regenerative Catalytic Reforming Process

A semi-regenerative process uses low platinum and regeneration is required only once a year.
The process consists of typically three reactor beds & furnace preheaters. The dehydrogenation is
highly endothermic and large temperature drop as the reaction proceeds. Multiple reactors with
intermediate reheat is required. Dehydrogenation of naphthene takes place in first reactor and
requires less catalyst. Preheat of feed is required. Last reactor for isomerization of paraffins.
Typical catalyst distribution in three reactors are 20, 30 and 50percent. Figure M-VI 6.2 shows
typical catalytic reforming process[ Mall,2007].

Catalyst Regeneration
Performance of the catalyst decreases with respect to time due to deactivation. Reasons for
deactivation
· Coke formation
· Contamination on active sites
· Agglomeration
· Catalyst poisoning
Activity could be restored if deactivation occurred because of coke formation or temporary
poisons.

Objective of Regeneration
· Surface area should be high
· Metal Pt should be highly dispersed
 · Acidity must be at a proper level
· Regeneration changes by the severity of the operating conditions
· Coke formation can be offset for a time by increasing reaction temperatures.

Naphtha

Hydro

Reformer No. 2

Reformer No. 3
desulphurisation

Reformer No. 1
Sulphur< 5 ppm

Chloride Preheat
furnace
Heater

Light
C 3 /C 4
end
Reformate
Light end

Stabiliser
column

Cooler

Reform ate
Flash
Drum

Figure M-VI 6.2: Catalytic Reforming Process

REACTIONS IN CATALYTIC REFORMING

Following are the most prevalent main reactions in catalytic reforming
Desirable
· Dehydrogenation of naphthenes to aromatics
· Isomerisation of paraffins and naphthenes
· Dehydrocyclisation of paraffins to aromatics
Non-Desirable
· Hydrocracking of paraffins to lower molecular weight compounds

Dehydrogenation & Dehydrocyclization: Highly endothermic, cause decrease in

temperatures, highest reaction rates, aromatics formed have high B.P so end point of gasoline
rises
Dehydrogenation reactions are very fast, about one order of magnitude faster than the other
reactions. The reaction is promoted by the metallic function of catalyst
Methyl cyclohexane à Toluene + H2
MCP à Benzene + H2

Dehydrocyclisation: It involves a dehydrogenation with a release of one hydrogen mole

followed by a molecular rearrangement to form a naphthene and the subsequent dehydrogenation
of the naphthene.
i-paraffins to aromaticsof paraffins
n-heptane à toluene + H2
Favourable Conditions: High temperature, Low pressure, Low space velocity, Low H2/HC
ratio

Isomerisation: Branched isomers increase octane rating, Small heat effect, Fairly rapid
reactions.

Favourable Conditions: High temperature, Low pressure, Low space velocity, H2/HC ratio
no significant effect
n-Hexane à Neohexane

Naphthenes dehydro-Isomerisation: A ring re-arrangement reaction, Formed alkyl-cyclo-

hexane dehydrogenate to aromatics.• Octane increase is significant, Reaction is slightly
exothermic

Coking: Coking is very complex group of chemical reactions. Linked to heavy unsaturated
products such as poly-nuclear aromatics. Traces of heavy olefines and di-olefines promote
coking. High feed FBP favors coking. Poor feed distribution in the reactor promotes coking
favored by high temperature

Hydrocracking: Exothermic reactions, slow reactions, consume hydrogen, produce light

gases, Lead to coking, Causes are high paraffin conc feed

Favourable conditions: High temperature, High pressure

PROCESS VARIABLES
Following variables affect the reformate yield and quality of the product [Little, 1985; Raseev,
2003; Mohan, 2011]. Favorable conditions for different reforming reactions is mention in Table
M-VI 1.3.

· Reaction temperature
· Space velocity
· Reaction pressure
· H2/HC ratio
· Feedstock Characteristics

Table M-VI 6.3: Favorable Conditions for Different Reforming

Reactions
Reaction Pressure Temperature
Dehydrogenation of Low pressure High temperature
naphthenes to aromatics
Isomerisation of naphthenes Indeterminate Indeterminate
Dehydrocylistion of Low pressure High temperature
paraffins to aromatics
Hydrocracking High pressure High temperature

FEED QUALITY
· Naphthenes dehydrogenate very fast and give rise to aromatics. Therefore, N + 2A is taken as
index of reforming. Higher the N + 2A, better is quality to produce high aromatics.
N = Naphthenes % A = Aromatics %
· Lighter fraction have a poor naphthene and aromatic content are, therefore, poor feed for
reforming. Low IBP feed results in lower aromatics and H2 yield.
· Heavy fractions have high naphthene and aromatic hydrocarbon content. Therefore, good
reforming feed but tendency of coke formation is high.

REACTION TEMPERATURE
Temperature is the most important operating parameter
· By simply raising or lowering reactor inlet temperature, operators can raise or lower the
octane number of the product.
· Since all the reactor inlet temperatures are not necessarily identical, it is commonly
accepted to consider the Weighted Average Inlet Temperature (WAIT)

SPACE VELOCITY
· Liquid hourly space velocity (LHSV)
· Weight hourly space velocity (WHSV)

Vol/Hour of Reactor Charge (60F & 14.7 Psia)

LHSV =
Vol. of Catalyst
Weight/Hour of Reactor Charge
WHSV =
Weight of Catalyst

Reforming LHSV range = 1.0 to 3.0 l/hr

Below 1.0 LHSV, undesired side reactions namely hydrocracking occurs which reduce reformate
yield .i.e., for every rise in LHSV of 0.1 between 1 to 2, about the 2oC rise in temperature is
required. The lower the space velocity (i.e., higher contact time), the higher the severity
assuming all other conditions unchanged. Lowering the space velocity has the same effects as
increasing temperature, i.e. Increase the octane, decrease the product yield, decrease H2 purity,
Increase coke deposit

REACTION PRESSURE
Reforming reaction pressure ranges (5 – 35 kg/sq. cm.). Decreasing pressure increases
dehydrogenation of naphthenes and dehydrocyclisation of paraffins which favours an increase in
production of aromatics and hydrogen (increase catalyst coking and shorter cycle life). Higher
pressure causes higher rates of hydrocracking reducing reformate yield but decreases coking of
catalyst resulting in longer cycle life.

HYDROGEN TO HYDROCARBON RATIO

 Moles of H 2 in Re cycle Gas
Hydrogen : Hydrocarbon Ratio = Moles of Hydrocarbons
Main purpose of hydrogen recycle is to increase hydrogen partial pressure in the reaction.H2
reacts with coke precursors removing them from the catalyst reforming polycyclic aromatics.
Higher the H2/HC ratio, higher the cyclic length. Two main reasons for reducing H2:HC ratio
· Reduction in energy costs for compressing and circulating H2.
· Favours naphthene dehydrogenations and dehydrocyclisation reaction
Lowering of H2/HC Ratio, From 8 to 4 carbon increase in 1.75 times and from 4 to 2 carbon
increase 3.6 times

CATALYST IN CATALYTIC REFORMING

Monometallic: (Pt),
Bimetallic: (Pt, Rhenium)
Acid Activity: Halogens/silica incorporated in alumina base.
Metallic Function: It promote dehydrogenation and hydrogenation. It also contribute to
dehydrocyclisation and isomerisation.
Acid Function: It promotes isomerisation, the initial step in hydrocracking, participate in
paraffin dehydrocyclisation.

Stages in historical development of reforming catalyst in Indian scene

· Development of lows Pt monometallic catalyst IRC-1002 by IPCL for BT Production.
· Commercialization of IRC-1001 catalyst in the first reactor of IPCL’s three reactor system
for Xylenes Production-1987.
· Scale up and manufacture of bimetallic catalyst IPR-2001 at IPCL’s catalyst division
· Commercialization of bimetallic catalyst at MRL for gasoline production 1990
· Commercialization of bimetallic catalyst IRC-1002 by IPCL for BT Production
· Commercialization of monometallic catalyst at IRC-1002 in BPCL Reformer for BT
production -1990
· Development of improved versions of reforming catalysts:
· High Rhenium Catalyst – Recipe ready for scale up.
 · Multimetallic Catalyst – Recipe ready for commercial trial.
· Spheroidal Catalyst - CCR operations recipe in advanced stage
· Catalyst used now a days is platinum on alumina base.
· For lower pressure stability is increased by combining rhenium with platinum.
· Pt serve as a catalytic site for hydrogenation and dehydrogenation reactions
· Chlorinated alumina provides acid site for isomerization, cyclization & hydrocracking
reactions.
· Catalyst activity reduced by coke deposition and chlorine loss
· As catalyst age’s activity of the catalyst decreases so temperature is increased as to
maintain the desired severity.

Advantages Of Bimetallic And Multimetallic Catalyst Over

Monometallic Catalyst

Enhanced Resistance to Coking

· Lower Fouling
· Higher coke tolerance
· Longer cycle length for S-R units
· Low pressure and low H2/HC ratio
Operation
· High Octane
· High aromatics
· High yields of desirable products
Better yield stability
Lower temperature requirement
Better tolerance to high temperature
Better regenerability
High ultimate life

CATALYST POISONS
Temporary Poisons: Temporary poisons are those impurities which can be removed during
various pretreatment process like sulphur, nitrogen
Permanent Poisons: Permanent Poisons are those impurities present in the feed which is
irreversible damage to the catalyst
Source and maximum level of catalyst poisons are given in Table M-VI 1.4.

Table M-VI 1.4: Source and Maximum Level of Catalyst Poisons

POISONS MAX. LEVEL WT% SOURCE
Arsenic 1 PPB SR or Cracked Naphtha
Lead 5 PPB Recycle
Copper 5 PPB Corrosion
Mercury 5 PPB Naphtha condensate
Iron 5 PPB Corrosion
Silicon 5 PPB Foaming additives
Nickel 5 PPB Corrosion
Chromium 5 PPB Corrosion

REFRENCES
1. Lapinski, M.L., Baird L., James, “Handbook Petroleum refining”, Ed. Meyers, R.A., The
McGraw Hill Companies , R. 4.32004.
2. Litle, D.M. “Catalytic Reforming”, Penn well, Tulsa, Okla, 1985, p.2.
3. Mall, I.D. “Petrochemical processes technology”, First Edi., New Delhi, Macmillan India,
2007
4. Mohan Lal “Catalytic Reforming” Process, Catalysts and Reactors 6th Summer School on
Petroleum Refining & Petrochemicals Indian Institute Of Petroleum Management Gurgaon
June 6-10 2011
5. Prasada T.S.R. “Catalytic Reforming and recent Indian achievements” oncology Vol6,
No.12, May1992, p.1.
6. Raseev, S. “Thermal and catalytic Processes in Petroleum Refining”, Marcel, Dekker, Inc
New York 2003.
7. Saxena A. K “Catalytic reforming” Advances in Petroleum Refining, Petrotech Summer
School, IIPM Gurgaon, 5th July 2006.
 LECTURE 7
ALKYLATION, ISOMERISATION AND
POLYMERISATION
ALKYLATION
Alkylation process commercialized in 1938, since then there has been tremendous growth in the
process. In US and Europe about alkylate is about 11-12 percent and 6 percent in the gasoline
pool respectively. Alkylate is a key component in reformulated gasoline. Alkylation processes
are becoming important due to growing demand for high octane gasoline and requirement of low
RVP, low sulphur, low toxics. Alkylate is an ideal blend stock to meet these requirement.
[D’Aquino & Mavridis, 2007]
The process of alkylation different iso-parraffins using olefins were developed during thirties
using aluminium chloride catalyst, however, later catalyst was replaced by HF and sulfuric acid.
Although butylenes alkylation is one of the most commonly used process, however, alkylation of
amylenes obtained from C5 fraction of FCC can be another route to increase the availability of
alkylate. Alkylation of C5 cut from FCC can significantly reduce RVP of finished gasoline pool.
C5 alkylate: Amylene alkylation has two fold advantage: It increase the volume of alkylate
available while decreasing Reid vapor pressure and olefinic content of gasoline blend stocks
The process of HF alkylation produces high octane blend stock for iso-parraffin (mainly iso
butane) and olefin (propylene, butylene and amylenes) in the process of HF catalyst to meet all
the criteria of reformulated gasoline. Replacing high risk toxic liquid acids, such as hydrofluoric
acid (HF) and sulphuric acid with solid acid catalysts is challenging goal iso-parraffin alkylation
technology.
Process
The reaction involved in aliphatic alkylation consists of conversion of iso-butane and butylenes
to iso-octanes using HF catalyst. Commonly alkylation process used are mention in Table M-VI
7.1.

The side reaction results in increased iso-butane consumption increased acid consumption
increased acid soluble formation, equipment handling and for the corrosion problem. Figure M-
VI 7.1 gives the details of iso-parraffin alkylation mechanism [Mukherjee & Nehlsen, 2006]
Some of the other side reaction is the formation of paraffin, which boils above and below the
desired product. Impurities in the feed acid and normal operating practices all can contribute to
additional side reactions. Comparison of Alkyclean Technology with Modern Sulphuric Acid
and Hydrofluoric Acid Technologies is shown in Table M-VI 7.2.
The key factors to be controlled in alkylation process are [Jezak, 1994]
· Maintaining proper composition of reaction mixture which include isobutene olefins and
the HF acid
· Maintaining the proper reaction environment which includes adequate contacting,
controlled temperature, and freedom from surges.
· Making a proper separation of the reactor effluent into its various components

Table M-VI 7.1: Common Alkylation Processes

Process Description
CONOCO Phillips Alkylation of propylene, butylenes, pentenes and isobutane to high
process (ReVA Process) quality motor fuel using HF catalyst
Stratco INC Alkylation of propylene, butylenes and amylenes with isobutane
using strong sulfuric acid to produce high octane branched chain
hydrocarbons using effluent refrigeration alkylation process
UOP HF Alkylation Alkylation of isobutane with light olefins (propylene, butylenes
Process and amylenes to produce branched chain parafinic fuel) using
hydrofluoric acid catalyst. More than 100 commercial process
TM
UOP Alkylene UOP Alkylene process is based on solid catalyst(HAL-100) for
alkylation of light olefins and isobutane to form a complex
mixture of isoalkanes which are highly branched
trimethylpentanes(TMP) that have high octane blend values of
approximately100
Exxon Alkylation Alkylation of propylene, butylenes and penrylene with isobutene
in the presence of sulphuric acid catalyst using autorefrigeration.
Products: a low sensitivity, highly iso, low RVP, high octane
gasoline blend stock paraffinic
AlkylClean solid Acid The alkylation process uses a robust zeolite solid acid catalyst
alkylation technology formulation coupled with a novel reactor processing scheme to
( ABBLumus global) yield a high quality alkylate product. The catalyst contains no
halogen
Source : ABB Lumus Global www.abb.com/lumus
Table M-VI 7.2: Comparison of Alkyclean Technology with Modern
Sulphuric Acid and Hydrofluoric Acid Technologies
Parameter Modern sulphuric Modern hydrofluoric Alkyclean
acid technology acid technology
Base condition C4 feedstock C4=feedstock C4=feedstock
Product RON 95 95 95
Product MON Base Base or better Base or better
Alkylate yield Base BASE 90% of base
Total installed cost Base 85% OF BASE 50% of base
Total installed cost, Base Less None
including
OSBL(regeneration,
facilities, and /or safety
installations)
ASO yield Base Less None
Equipment maintenance High High Much lower
Corrosion problems Yes Yes Higher
reliability and on stream Base Base Match fcc or
factor better/shorter
Safety Unit specific safety C safety precautions No special
precautions as well as required that extend precautions
transport precautions throughout refinery other than those
unit specific very specific for any refinery
precautions process unit
Catalyst H2SO4 HF Zeolite
Environmental Significant waste Significant waste No emissions to
streams generated streams generated air, water, or
ground
Source: Refining processe’98 Hydrocarbon processing November 1998, 53, Graves, 2003,
Rroseseler, 2003, Himes et al., 2003, Gravely, 2004.
 Figure M-VI 7.1: Iso-paraffin Alkylation Mechanism
Source: (Mukherjee & Nehlsen, 2006)

ISOMERISATION
Petroleum fractions contain significant amounts of n-alkanes and the isomerisation of alkanes
into corresponding branched isomers is one of the important process in refining [Mastuda,T.,
sakagami,H. and takahashi, N. Catalysis today 81, 2003 p.31]. The highly branched paraffins
with 7-10 carbon atoms would be the best to fulfill the recent requirements of the reformulated
gasoline [Rossini, S. Catalysis Today 2003,77, 467]. The production of paraffin bases high –
octane gasoline blend stock, such as isomers from isomerisation of light and mid cut naphtha
might be a key technology for gasoline supply to cope with future gasoline regulation
[Visanandham & Garg, 2010]
Light naphtha and paraffin isomerisation recognizes emerging technologies in order to boost
octane in light gasoline fractions. Recent pricing trends show isomerisation could be a significant
contributor to octane pool which will offset the loss from gasoline desulfurisation and aromatic
reduction. Isomerate as % of gasoline used is USA 8percent, Western Europe 16percent.
Isomerisation involves
· Isomerisation of Light paraffins
· Isomerisation of C5-C6paraffins
· Isomerisation of n-butane
Isomerisation of C5-C6 paraffins: Allow low octane number paraffins 5 and 6 carbon atoms into
higher octane number paraffins
n-pentanen-isopentane:
n-hexane to 2-methyl pentane, 3 methyl pentane (low octane 75)
2,2 dimethyl butane, 2,3 dimethyl butane
Isomerisation of n-Butane; to produce isobutene feed for alkylation or as source of isobutene
dehydrogenation to manufacture MTBE

Isomerisation Catalyst
Two types of isomerization catalyst, zeolite and chlorinated alumina, has been used. Zeolite
catalyst requires higher temperatures and provide lower octane boost while chlorinated alumina’s
results in highest octane, however, it has higher sensitivity to feed stock impurities requiring
strict feed pretreatment to eliminate oxygen, water, sulphur and nitrogen is containing
compounds [Domergue & Matthews, 2001].
· Zeolite
· Chlorinated alumina
Zeolite catalyst requires higher temperatures and provide lower octane boost
Chlorinated alumina’s results highest octane, however, it has higher sensitivity to feed stock
impurities requiring strict feed pretreatment to eliminate oxygen, water , sulphur and nitrogen
containing compounds

Isomerisation of Light Naphtha

C5/C6 feed either from straight run crude distillation or from catalytic reforming. Table M-VI
7.3 gives details of isomerization of light paraffins catalyst.
Reformate: separated in lighter mostly benzene and heavier containing C7
Catalyst: Zeolite or Pt on Chlorinated alumina
Operating Condition:
Pt on chlorinated Pt on zeolite
alumina
Temperature oC 120-180 250-270
Pressure 20-30 15-30
Space velocity h-1 1-2 1-2
H2 /HC ratio 0.1-2 2-4
Product RON 83-84 78-80
ONCE THROUGH PROCESS
Recycle Process: Unconverted n-paraffins and any single branched isomers from double
branched isomers
Recycling with Distillation: Deisohexaniser
Recycling with Adsorption: Adsorption on Molecular sieve: n-paraffins are adsorbed and
separated by desorption

Table M-VI 7.3: Isomerisation of Light Paraffins Catalyst

Isomerisation Catalyst
1st generation Friedel and Crafts AlCl3 catalysts, exhibit very high
activity at low temp980-100oC
2nd generation Metal/ support bifunctional catalyst essentially
Pt/alumina sensitivity to poisons are less acute,
however, require higher temperature (350-550oC.
3rd generation Metal/support bifunctional catalysts with increased
acidity by halogenation of the alumina support.
Sensitive to poisons and need pretreatment,
Corrosion problem. High activity at low
temperature9120oC-to 160oC
4th generation Bifunctional zeolite catalysts, very resistant to
catalyst poison and feed does not need pretreatment

Isomerisation of n-butane
To produce isobutene feed for alkylation or as source of isobutene dehydrogenation to
manufacture MTBE

UOP Butamar Process:

Catalyst: Pt/chlorintated Al2O3
Operating Condition: Temperature: 180-220 oC,
Pressure: 15-20 bar
Soacevel: 2h-1
H2/HC: 0.5 to 2

UOP isomerisation Technologies:

Some of the UOP Light paraffin isomerisation technology are [Rajaram Panchapakesan, 2005]
PenexTM: Higher octanes, higher product yields more than 120 licensed units
Par-IsomTM: UOP introduced par-ISOM TM in 1996 using zeolite chloride sulfate of
zirconium catalyst. It is chracterised by lower equipment cost, multiple catalyst approach. Some
advantage of Penex process Maximum octane bbls, high octane, best long-term profitability
higher investment cost. It can handle undesired feedstocks including feed and process high
TM
benzene content feeds. It has wide range of operation. Penex once through Penex plus for
extra high benzene levels DIH, DIP/DIH, MDEX TM
Penex:Para-ISOM process with PI-242 catalyst: Best LPG production , good octane, rapid
payback, low investment cost

POLYMERISATION
Polymerization processes have received considerable interest in petroleum refining because
of the higher requirement of reformulated gasoline and phasing of MTBE. The process may be
attractive in two main areas [Leprince, 1998].
· Upgrading of C2 and C Temperature: 150-200oC, Pressure: 30-50bar, space velocity 0.3-
0.5 m3/h per m3 cuts from catalytic cracking for oligmerization ethylene & propylene to
olefinic gasoline.
· Producing high quality middle quality

REFERENCES
1. D’Aquino & Mavridis, 2007
2. Domergue, B, Matthews, R. “Advanced recycle paraffin isomerisation technology”
Petroleum technology quarterly, Spring 2001, p.29.
3. Gravely, M.L. “CONOCO Phillips reduced volatility Alkylation Process” (ReVAP) in Hand
Book of Petroleum Refining Process 2nd edition, edited by Meyers, R.A. McGraw Hill
Companies, 2004, p.1.79.
4. Graves, D.C. “STRACTO Effluent refrigerated H2SO4 alkylation system” in Hand Book of
Petroleum Refining Process 2nd edition, edited by Meyers, R.A. McGraw Hill Companies,
2004, p.1.33.
5. Himes, J.F., Meister, J.M., Nowak, Franz-Marcus “UOP HF alkylation technology” in Hand
Book of Petroleum Refining Process 2nd edition, edited by Meyers, R.A. McGraw Hill
Companies, 2004, p.1.33.
6. Jezak, A., “C5 Alkylate: A Superior blending component”, Hydrocarbon processing/February
1994, p.47.
7. Leprince, P., “Oligmerisation” in IFP Petroleum refining Part 3 conversion processes” edited
by Leprince, P. Editions Technip, 1998, p.321.
8. Mastuda,T., Sakagami, H., Takahashi, N., Catalysis Today, 81, 2003 p.31
9. Mukherjee, M., Nehlsen, J., “Consider catalyst developments for alkylation production”
Hydrocarbon processing, Sep., 2006, p.85.
10. Rajaram Panchapakesan “Latest development UOP isomerisation catalysts”, National
workshops on catalysts in hydrocarbon processing, Nov 25-26, 2005, organised by memorial
trust New Delhi -110001.
11. “Refining processes”, Hydrocarbon processing November 1998, 53,
12. Roeseler, “UOP AlkyleneTM process for motor fuel alkylation” Hand Book of Petroleum
Refining Process 2ndedition, edited by Meyers, R.A. McGraw Hill Companies, 2004, p.125.
13. Rosini,S., Catalysis Today 2003,77, 467
14. Visanandham.N, Garg, M.O., “A novel catalyst for Improved C+ isomerisation of naphtha”
Chemical Industry Digest May 2010, 65.