Course: Chemical Technology (Organic) Module VI

Lecture 1
Introduction: Status of
Petroleum Refinery, Crude Oil
And Natural Gas Origin,
Occurrence, Exploration,
Drilling And Processing, Fuel
Norms

 LECTURE 1
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

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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

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 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
Sulphur compounds Hydrogen sulphide,
Mercaptans
Nitrogen compounds Quinotine, Pyradine,
pyrrole, indole, carbazole
Oxygen compounds Naphthenic acids, phenols
Remarks
Undesirable due to foul odour
0.5% to 7%
The presence of nitrogen
compounds in gasoline and
kerosene degrades the colour of
product on exposure to sunlight.
They may cause gum formation
normally less than 0.2.
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.

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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

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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

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 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
Distillation
Absorption
Extraction
Crystallisation
Adsorption

PRIMARY DISTILATION (Atmospheric Distillation)

Refinery gases
Liquefied petroleum gases

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 Gasolines or naphtha (light/heavy)

Kerosene, lamp oil jet fuel
Diesel oil and domestic heating oils
Heavy Industrial fuels

SECONDARY DISLLATION (Vacuum Distillation)

Light Distillate
Middle distillate
Heavy distillate
Asphalt/bitumen

CONVERSION PROCESSES
Process for Improvement of Properties
Catalytic reforming
Isomerisation
Alkylation

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 Figure M-VI 1.2: Typical Refinery Processes and Products

Thermal processes:

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 Visbreaking
Coking

Catalytic Processes
Catalytic cracking(FCC)
Hydrocracking
Steam reforming
Hydroconversion

FINISHING PROCESSES
Hydrotreatment/hydrogenation
Sweetening

ENVIRONMENTAL PROTECTION PROCESSES

Acid gas processing
Stack gas processing
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].

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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

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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

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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 -Olefins
Sources: M. O. Garg Director Indian Institute of Petroleum, Dehradun 23 rd National Convention of
Chemical Engineers IIT Roorkee, 5 7 October 2007

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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 Indias savior chemical News July, 2012, p.40

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