PETROLEUM REFINING

CONTENTS
 Indian refining scenario
 Refining
 History of refining
 Refinery process overview
 Primary separation
 Atmospheric and vacuum distillation
 Important specifications of main refinery products
 Conversion process
 Gasoline up gradation
 Octane boosters
 Conversion of heavies to light oil
CONTENTS (contd.)
 Treatment processes
 Lube oil manufacture
 Lube oil processing steps
 Lube processing schematic
 Indian lube industry
 Utility and offsite facilities
 Optimization of refinery operations
 Inputs to linear programming model
 Refinery configuration
 Future of refining scenario
 Conclusion
 References
INDIAN REFINING SCENARIO
 India’s current crude refining capacity is
148 MMTPA.
 18 refineries ,4 planned( IOCL Paradip, BPCL Bina,
HPCL Bhatinda, RPL’s Jamnagar.)
 IOCL-10 refineries, BPCL-4 refineries, HPCL-2
refineries, RIL-1Jamnagar refinery,Essar-1Vadinar
refinery.
 India’s petroleum product consumption is 99.682
MMTPA in 2006-2007.
S.No Name of the Company Location of the Refinery Capacity
1 Indian Oil Corporation Limited (IOCL) Guwahati 1.00

2 Indian Oil Corporation Limited (IOCL) Barauni 6.00

3 Indian Oil Corporation Limited (IOCL) Koyali 13.70

4 Indian Oil Corporation Limited (IOCL) Haldia 6.00

5 Indian Oil Corporation Limited (IOCL) Mathura 8.00

6 Indian Oil Corporation Limited (IOCL) Digboi 0.65

7 Indian Oil Corporation Limited (IOCL) Panipat 6.00

8 Hindustan Petroleum Corporation Limited (HPCL) Mumbai 5.50

9 Hindustan Petroleum Corporation Limited (HPCL) Visakhapatnam 7.50

10 Bharat Petroleum Corporation Limited (BPCL) Mumbai 6.9

11 Chennai Petroleum Corporation Limited (CPCL) Chennai 9.5

12 Chennai Petroleum Corporation Limited (CPCL) Nagappatinam 1.0

13 Kochi Refineries Ltd. (KRL) Cochin 7.5

14 Bongaigaon Refinery & Petrochemicals Bongoingaon 2.35

15 Numaligarh Refinery Ltd.(NRL) Numaligarh 3.00

16 Mangalore Refinery & Petrochemicals Ltd. (MRPL) Mangalore 9.69

17 Tatipaka refinery (ONGC) Andhra Pradesh 0.078

18 Reliance Petroleum Ltd. (RPL).Pvt. Sector Jamnagar 33.00

 Map of Refineries in India

Source : www.mapsofindia.com
REFINING
 The basic process unit in a refinery ,a crude oil distillation unit-
splits crude into fractions by distillation at atmospheric pressure.
Basic refineries normally have crude distillations units, catalytic
reforming, hydro treating units.
 An oil refinery is an industrial process plant where crude oil is
processed and refined into useful petroleum products, such as
gasoline and diesel fuel
 Demand for lighter products such as gasoline and diesel fuel
has increased the need for most sophisticated processing and
complex refineries have vaccum distillation, catalytic cracking,
hydro cracking units. Cracking units processes heavy vaccum oil
into gasoline, gas oil and heavy fuel oil.
HISTORY OF REFINING
YEARS PROCESS DRIVING FORCES PRODUCTS
1860 Atmospheric To separate fuel, light Naptha, Tar, Fuel oil
distillation oils and tar
1870 Vaccum distillation Lubricants were Npatha, Tar, Fuel Oil,
distilled out under Lubricating Oil,
vaccum to meet the Feedstock for thermal
lubricating oil cracking
requirements
1900 Thermal cracking Initially developed to Increased production
crack heavy residual of gasoline
fuel to reduce its
viscosity
1930-40 Desulphurisation, The boom in Higher O.N gasoline,
Improved quality of automobile industry ATF, Kerosene,
lube oil and improved, more Diesel, Lubricating
powerfull engines oils, Bitumen.
resulted in increased
demand of gasoline
and higher octane no.
requirement.
 History of Refining
Years Process Driving Forces Products

1930 to Sulfur removal Development in this period was Higher

1940 processes, mostly automobile industry O.N.
processes for driven. The boom in automobile gasoline
improved quality industry and improved, more aviation
of lube oil powerful engines resulted in gasoline,
(Dewaxing, increased demand of gasoline kerosene,
Solvent and higher octane number diesel
Extraction), requirement. Demand for lubricating
Gasoline quality aviation gasoline with very high oils,
and demand octane number (over 100 O.N.) bitumen.
driven processes and need for better quality of
(Catalytic lubricating oils for the engines
Cracking, also created drive for new
Alkylation, processed.
Polymerization)
 History of Refining
Years Process Driving Forces Products
1940 to Hydro- Growth and investment Less of fuel oil,
1960 desulphurization, still automobile industry more of white
improved cracking driven. Further Products,
processes, growth development of sulfur petrochemical
of Petrochemical removal processes. feedstock.
Industry Petrochemical feedstock
generation.
1960 to Hydro cracking Better quality Increased
1970 specifications for white amount of light
products with wider products
range of feedstock.
 History of Refining
Years Process Driving Forces Products
1970 Deep Hydro- Stricter specifications Higher quality
onwards desulphurization, on sulfur content for all and
other sulfur removal products, concern for environment
processes environment and friendly fuels
replacement of TEL regulations on for automobile.
by MTBE as octane environment resulted in Increased
booster, use of a lot of investment on sulfur
alkylation and such processes. This production and
isomerization to get made refinery hydrogen
high octane operations non- demand in a
gasoline. profitable. Restriction of refinery.
aromatics in gasoline
lead to greater use of
other octane boosting
processes.
 History of Refining
Years Process Driving Forces Products
1990 Deeper sulfur The investments to meet Increased
onwards removal quality and environment production on
integration of specifications made the petrochemical
refinery with operation of a stand- feedstock and
petrochemical alone refinery integration with
and other uneconomic. petrochemical
industries. units.
 Refinery Configuration of the Sixties
FUEL GAS
LPG
Crude NAPHTHA
Oil Tetraethyl
Lead GASOLINE
REFORMING
KEROSENE

HSD DIESEL

FUEL OIL

ATMOSPHERIC
DISTILLATION FCC

LUBES
LUBE PLANT

VACUUM
DISTILLATION RESID/FUEL
VISBREAKING
 Modern Refinery Configuration
FUEL GAS
Butanes
LPG
Isomerization Octane Booster

NAPHTHA
Crude
Oil REFORMING GASOLINE
HDS KEROSENE

HDS HDS DIESEL

FUEL OIL
ATMOSPHERIC
DISTILLATION Aromatics
FCC
Extraction
BTX
LUBE PLANT LUBES

VACUUM
Hydrocracking HDT
DISTILLATION
VISBREAKING RESID/FUEL
COKE
REFINERY PROCESS OVERVIEW

 Primary separation
 Conversion processes: -
1. Product Up gradation
2. Conversion of heavy residues to
lighter products
 Treatment processes
 Processing for lube oils
PRIMARY SEPERATION
 Atmospheric Distillation: -
1. First step in the refinery processing to separate out the raw
products (cuts) by distillation under pressures above atmospheric
pressures
2. To separate the light cuts by heating the crude oil to 350-370 C
at pressures close to atmospheric pressures
3. Light and white products like MS, SKO, ATF, HSD etc. are
distilled out as raw products for further processing.
4. Residue which is left behind at the bottom of the distillation
column after atmospheric distillation is called long residue
PRIMARY SEPERATION (contd.)

 Vaccum distillation: -
1. The second step in the refinery process
2. The limitation of distilling at higher temperature (above 350-370 C),
crude oil starts cracking i.e. the heavier molecules start braking into
smaller molecules. Uncontrolled cracking results in coke formation and
production of unstable olefinic hydrocarbon products
3. In vaccum distillation, the long residue from atmospheric distillation
is heated to around 350-370 C and distilled under vaccum conditions
4. This units yields vaccum gas oil as distillates which are used as
feedstock for cracking to lighter products (Feed for cracking or lube oil
manufacture)
5. The residue which is left after vaccum distillation is called “Short
Residue”
 ATMOSPHERIC AND VACCUM
DISTILLATION CUTS
<35c Butane and Lighter -------LPG recovery

Atmos 35-80 C Light Gasoline -----Motor Gasoline Blending

pheric
distilla 80-140 C Naptha -----Cat. Reforming
tion
Crude oil 140-250 C Kerosene ------Hydro Treating

Vaccu 250-350 C Gas oil -------Diesel Oil Stock

m
Distill
ation 350-400 C Light Vaccum Gasoil ---------Lube Base stock

400-500 C Heavy Vaccum Gas oil -----Lube Base stock or

Cracking

500 C+ Straight Run residue--------for bitumen procesing

Crude Distillation
Introduction
Atmospheric Distillation of the crude is the first step in
the processing of crude oil in a refinery. It is physical
separation of oil components at slightly higher than
atmospheric pressure by heating to around 3500C + and
subsequently distilling into fractions (raw products cuts).
As crude oil starts cracking at temperatures higher than 370-
3800C, the residue from Atmospheric Distillation is
subsequently distilled under vacuum at similar temperatures.
This is called Vacuum Distillation. Distillation produces some
gases (LPG, Fuel Gas) and raw cuts of light products like
gasoline, naphtha, kerosene and diesel.
The residue from the bottom of the Atmospheric Distillation
Column is vacuum distilled to produce heavy gas oil,
which form the base stock to produce lubricants. The gas oil is
also sent to Cracking Unit to produce further light products.
Description
The fractionating column where multi-component distillation
takes place is the heart of the process.
The crude needs to be heated up before entering the
fractionation column. This is done at first in a series of feat
exchangers where heat is taken from outgoing products from
the column, which need to be cooled before being sent to
storage. Heat is also exchanged against condensing streams
from the top of the column. Optimum design of this heat
recovery train or pre-heat train is extremely important for
energy efficient operation of the column. Typically, the crude
will be heated up in this way upto a temperature of 200-2800C
by heat recovery alone, before entering a furnace.
As the raw crude oil received from oilfields contains water and
salt, it is normally sent for salt removing first, in a piece of
equipment called a desalter. This has been discussed in the
preceding section. The desalter is put midway in the pre-heat
train at temperature of around 1300C.
Downstream the desalter, crude is further heated up with heat
exchangers, and starts vaporizing at about 200-280 0C. Then
the crude enters the furnace where it is heated up further to
about 330-3700C. The furnace outlet stream is sent directly to
the fractionation column. Here, it is separated into a
number of fractions, each having a particular boiling
range.

At 3500C, and about 1 bar g, crude oil is partly vaporized and

the vapors rise up along the column through trays. The
vapors come into contact with liquid coming down from the
top of the column. The different fractions are gradually
separated from each other on the trays of the fractionation
column. The heaviest fractions condense on the lower trays
and the lighter fractions condense on the trays higher up in
the column. At different elevations in the column, with special
trays called draw-off trays, fractions are drawn out by gravity
through pipes, for further processing in the refinery.
At the top of the column, vapors are routed to an
overhead condenser, typically cooled by water or air
coolers. At the outlet of overhead condenser, vapors are
condensed into liquid (naphtha) and gases are separated
in an Accumulator at around 400C. Gases are routed to a
compressor for further recovery of LPG (C3/C4), while
the liquids (gasoline or naphtha) are pumped to a
stabilizer column. Part of the cold, condensed liquid is
put back at the top if the column as reflux.
The second and third (optional) side draw-offs from the main
fractionating column are diesel or gas oil fractions, boiling
in the range 200-4000C, which are ultimately used for
blending in the final diesel product. Similar as with the
kerosene product, the gas oil fractions (light and heavy gas
oil) are first sent to a side stripper before being routed to
further treating units.

At the bottom of the fractionation column a heavy,

brown/black colored residue is drawn off.

All the top and side draw-offs go for further treatment to

meet products specifications. The residue is vacuum
distilled (see section on Vacuum Distillation).
 Vacuum Distillation Unit
To Vacuum System

Vacuum Light Vacuum

Tower Gas Oil

Heavy Vacuum
Heater Gas Oil
Residue from
Atmospheric (cracker feed)
Distillation

Steam

Asphalt
IMPORTANT SPECIFICATIONS OF
MAIN REFINERY PRODUCTS
No. Refinery Specification
product
1 LPG Vapour pressure at 65c, propane content

2 Gasoline Octane No., Boiling range, Sulfur, Aromatics

3 Naptha Boiling range

4 Kerosene Smoke point, Flash point, Sulfur

5 Jet fuel Freezing point, Flash point, Boiling range

6 Diesel oil Cetane no., carbon residue, Pour point, Flash

point
7 Lubricating Oil Viscosity index, Carbon residue
CONVERSION PROCESS
 Conversion process means change of the molecules
of the raw products obtained from distillation by
reaction process under heat, pressure, along with or
without a catalyst, from one type of molecule to
another.
 Two types of conversion processes
1. Conversion for up gradation of product quality
2. Conversion to change heavy residual products
into light and high value products like gasoline and
diesel. These are called cracking processes
 GASOLINE UP GRADATION

Catalytic Reforming-
Catalytic reforming is a high temperature catalytic process
to convert low-octane naphthas into high-octane gasoline
blending components called reformats. Most straight run
naphthas from primary distillation of crude comprises of a lot
of low octane components like normal paraffins and five and
six carbon naphthenes. Reforming involves.
• Isomerization of paraffins
• Dehydrogenation of naphthenes like cyciohexanes to
aromatic hydrocarbons
• Dehydrocyclization of paraffins i.e. making them to cyclic
hydrocarbons and dehydrogenating them to aromatics.
This gives high octane gasoline blending stock. Also
hydrogen is generated as by-product.

Reforming process is also a source for feedstock for

petrochemical plants. Reformats can be produced with very
high concentrations of toluene, benzene, xylene, and other
aromatics useful both for gasoline blending and
petrochemical processing. Hydrogen, produced from
dehydrogenation and dehydrocyclization reactions is
separated from the reformats for recycling and use in other
refinery processes like hydrodesulphurization.

The typical operating conditions are 500-5300C and 20-25

kg/Sq. cm pressure.
GASOLINE UP GRADATION (contd.)

 New processes other than catalytic reforming were

developed
1. Isomerisation- To convert straight chains paraffin's
to branched chains isomers
2. Alkylation- To combine paraffin components with
butane to form isomers
3. Polymerization- To transform some lighter
hydrocarbons into high octane gasoline
4. Fluid Catalytic Cracking units- One of the main
sources of high octane gasoline
 OCTANE BOOSTERS
MTBE had been developed as an oxygenate to improve
combustion performance and reduce vehicles’ environmental
emissions. Following problems with MTBE seeping out from
old, poorly maintained service station gasoline tanks and
mixing with groundwater, MTBE has now been banned in
California and, more recently, in a number of other US states
as well.
Although it was known that iso-octane could replace MTBE,
no one knew how to produce it on an industrial scale. Possible
processes, such as alkylation, were hampered by the fact that
their use of hydrofluoric acid and sulfuric acid made them un-
attractive from an environmental standpoint.
 “Producing iso-octane using NExOCTANE
technology is a perfect route for replacing MTBE production,
and enables producers to benefit from all the investments
they’ve made in their MTBE units.
OCTANE BOOSTER CONT………
 All MTBE producers will eventually be faced with the
same challenge, and all of them need to find something
to fill the gap that will be left when MTBE is phased out
from the US market.

 “ Although every conversion project is unique, we’ve

seen that NExOCTANE is very flexible in meeting
customers’ needs and really does let them leverage the
existing equipment at their MTBE plants.”
CONVERSION OF HEAVIES TO
LIGHT OIL
 Thermal Cracking- Done with heat alone at high
temp.
1. Vis - breaking
2. Coking
 Hydro cracking- Cracking under heat, pressure and
presence of hydrogen
 FCC (Fluid Catalytic Cracking)- is carried out with a
fluidized bed of catalyst. FCC yields gasoline of
higher O.N along with gases, Kerosene and diesel
fractions. Some heavy oil is also produced from
FCC called cycle oil.
Hydrocracking

As the name implies, hydrocracking is cracking in

presence of hydrogen. It is a catalytic process at high
temperatures and high pressure. The initial development of the
process had the limitation of operation at very high pressures
(above 200 bar). The development of improved catalyst made
it possible to operate the process at considerably lower
pressure, about 70-150 bar at temperatures of 350 to 4300C.
The main advantages of hydrocracking process are :
 Its flexibility with respect to production of gasoline and
middle distillates.
 Quality of its products
 Ability to handle a wider range of feedstock like cycle oils
from other cracking units.
 Does not yield any coke as by-product.
 Better conversion of the gas oil and residues into useful
products.
TREATMENT PROCESSES
 Sulfur removal-
1. Hydro desulphurization- Sulfur is removed by
reaction of hydrogen with sulfur bearing components
of oil. This produces hydrogen sulfide. Hydrogen
sulfide is converted to sulfur in the refinery by a
process known as Claus process.
2. Hydro treating, Hydro finishing and Merox
sweating of LPG and Gasoline is done to remove
traces of contaminants by treating with hydrogen or
other reagents
 Process Units in a Refinery
S.No. Process Unit S.No. Process Unit
Types of Process Types of Process
Primary Separation Conversion of Heavies
1 Atmospheric Distillation 11 Visbreaking
2 Vacuum Distillation 12 Coking
3 Naphtha Stabilization 13 Fluid Catalytic Cracking
14 Hydrocracking
15 Thermal Cracking
Gasoline Upgradation Sulfur Removal
4 Catalytic Reforming 16 Hydrodesulphurization
5 Alkyation 17 Gas Sweetening
6 Isomerization 18 Sulfur Recovery (Claus)
7 Polymerization 19 Tail Gas Treatment
20 Hydrogen Plant
Petrochemicals Feedstock
Generation
8 Aromatics Extraction
9 Xylene Separation
10 Naphtha Feedstock
Preparation
REFINERY CONFIGURATION
 Refinery integration

Petrochemical

Petro-
chemical
Crude Refinery Petro-chemical
products
products

Power Power
steam Power plant

H2
CONCLUSION
 The future refinery configurations will need
1. To reduce Black oil generation (residue up gradation),
2. Stringent product quality specifications particularly for auto fuels,
3. Generate more value added products,
4. Have flexibility to process wide range of crude
5. Improved operational performance, thus leading to improved profit
margins.

 In summary the future refinery configuration will represent an integration

of refinery projects with petro chemicals/petro chemical products,
gasification route to power generation for internal use an export and
conversion of NG wherever available, to Methanol and fertilizers.