Fundamentals of Refining PDF

Refining
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OLEUM &
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UNIV ER SIT
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MB-107
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COLLEGE OF MANAGEMENT AND ECONOMICS STUDIES (CMES)
Course Code: MB-107

Course Name: Refining
UNIVERSITY OF PETROLEUM & ENERGY STUDIES
Contents
Unit 1
Growth & Development of Refining Industry in India ................................... 1
Unit 2
Crude Oil and its Characteristics ...................................................................... 7
Unit 3
Specifications of Petroleum Products & Related Tests ................................ 23
Unit 4
Integrated Refinery & Petrochemical Plants ................................................. 53
Unit 5
Future Refining Scenario .................................................................................. 85
Unit 6
Advances in Petroleum Refining ..................................................................... 89
Unit 7
Hydrocarbon Loss Minimization ...................................................................... 93
Unit 8
Energy Conservation ......................................................................................... 95
Unit 9
Gross Refining Margin ...................................................................................... 99
Unit 10
Oil Accounting .................................................................................................. 103
Unit 11
Excise & Custom Petroleum Products ....................................................... 107
Objective
The objective of this course is to give an insight into various facets of petroleum refining for
producing finished products of the desired specifications. Various refining processes used
in the refineries have been dealt in this module. Characteristics of crude and specifications
of various petroleum products have been explained in detail. Dealing with growth and
development of petroleum refining industry in India, latest advancements in various
technologies for improving profitability of the refineries in the face of increasingly stringent
product specifications for meeting environmental stipulations have also been described.
An Overview
Refining of petroleum for producing fuel and related products for automobiles, domestic
consumption and meeting the needs of the power sector, petrochemicals, fertilizers etc.
and other industries, is very vital for the economic progress of the country. The refining
industry in India has made tremendous progress since independence with its march in
time with the country's economic growth and overall progress. Starting with the
establishment of the first public sector refinery at Guwahati (Assam) in 1962, it has come a
long way with the setting up of most modern, state of the art and highly energy efficient
refineries of the present day. India has 17 operating refineries processing both indigenous
and imported crudes. The crude processing capacity of the country has increased from 6
MMTPA in 1962 to 113 MMTPA as of today. Oil companies in India have met the challenges
of the petroleum market product demands with the desired stringent specifications from
time to time, by making changes/ improvements in their processes while at the same time
sustaining their profitability.
The refineries are highly capital-intensive industries with a medium gestation period and
produce crucial products for meeting the country's needs including that of defence. For
setting up a 6 MMTPA capacity refinery complex with marketing facilities, investments to
the tune of Rs 5000 crores are required. These refineries need to be run efficiently so as to
make profits, and hence need to be modernised and updated from time to time.
The module on refining covers various facets of petroleum refining. Various refining
processes used in the refineries have been dealt with in this module. Characteristics of
crude oil and specifications of various petroleum products have been explained in detail.
Dealing with growth and development of petroleum refining industry in India, latest
advancements in various technologies for improving profitability of the refineries in the
face of increasingly stringent product specifications for meeting environmental stipulations
have also been described.
Unit 1
Notes
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Growth and Development of

Refining Industry in India
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Objectives
After studying the unit, the learner will be able to:
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Get an overview of the growth of the Indian Refining Industry after

independence.
Know about special features of Indian Refining Industry.
Get a good idea of various challenges facing the industry in the

present time/in future and strategies for meeting the same.
With the growth of industry and improvement in the living

standard of people, demand for petroleum products is
increasing rapidly. Consequently, there is a thrust on
increasing their supply by enhancing refining capacity.
First refinery in India started soon after oil production
started in Digboi, Assam. Thereafter addition of refineries
and capacity augmentation continued unabated. Now we are
having seventeen operating refineries with a total capacity
of 113 MMTPA.
The Important Milestones

1866
Oil discovery at Nahorpung, Assam.
1889
Oil Production started at Digboi, Assam.
1893
First Refinery started at Margharita, Assam.
1899
Assam Oil Company was formed.
1901
Digboi
Refinery
was
commissioned
supplanting the earlier refinery at Margarita.
1947- 1957
Setting up of three coastal refineries by Multi

National Oil Companies (MNCs)
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The MNCs were already marketing petroleum

products in India by then.
1954
Indian Oil exploration with the help of Russian

Geologists.
1956
Formation of Oil and Natural Gas Commission

for exploration and production of crude oil and
gas.
1958
Discovery of Cambay oil field.
1958
Indian Refineries Ltd (IRL) was formed in the

public sector to install refineries and pipelines
in India.
Oil India Ltd (OIL) was formed as a joint

venture company between Government of
India and Burmah Oil Co.
1959
Indian Oil Company formed for marketing of

petroleum products.
1962
The first refinery in the public sector

commissioned at Guwahati (0.75 MMTPA)
under IRL.
1963
Indian Oil Blending Ltd A JV between Indian

Oil Co. and Mobil Petroleum Co. Inc. was
formed for manufacture of lube oils and
greases.
1964
IRL was dissolved and merged with Indian Oil

Co. Ltd, to form Indian Oil Corporation Ltd
(IOCL).
1974
IOBL became part of IOCL.
1981
Assets of erstwhile Assam Oil Co. were taken

over and vested in IOC as Assam Oil Division
(AOD).
1998
Panipat Refinery of IOC commissioned.
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2 at Mumbai (Esso & Burmah Shell)
fo
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ST U DI ES
Reader may like to draw a

Geneological Chart of the current
refineries operative in India.
Please classify by company,
technology
and
year
of
establishment and expanded
capacity wherever applicable by
the end of 10th 5 year plan i.e.
2006 07.
OLEUM &
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Activity 1 A
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Refining
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UNIT 1
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1999
2000
Growth and Development of Refining Industry in India
Reliance Petroleum Refinery at Jamnagar,

commissioned.
Numaligarh refinery commissioned.
3
Activity 1 B
What are various options for
increasing the Refining Capacity
in the country?
In the five decades since independence, 16 refineries have

been added in the public/private/ joint sectors (including
three in the private sector by MNCs, which subsequently
became PSUs).
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Future Outlook* (as per 2025 vision document)
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Total Refining Capacity

MMTPA
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2002 03
135
Barauni Expansion
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Haldia Expansion
HPCL, Mumbai Expansion
CPCL, Nagapatinam
RPL Expansion
Essar Oil
2003 04
170
Koyali Expansion
Panipat Expansion
BPCL Expansion
CPCL Expansion
BRPL Expansion
Paradip
Essar Oil Expansion
Nagarjuna Oil
2004 05
176
Kochi Refinery Expansion
2005 06
214
Essar Oil Expansion
RPL Expansion
Bhatinda
2006 07
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221
BRPL Expansion
Bina
* The anticipated growth in petroleum products may not take place
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Refining Capacity in India as in the year 2002
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No.
Refineries
MMTPA
Year of
Commissioning
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1.
Indian Oil Corporation Limited, Digboi
0.65
1901
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2.
Indian Oil Corporation Limited, Guwahati
1.00
1962
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3.
Indian Oil Corporation Limited, Barauni
3.30 (6.0)
1964
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4.
Indian Oil Corporation Limited, Koyali
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5.
Indian Oil Corporation Limited, Haldia
3.75 (7.5)
1974
6.
Indian Oil Corporation Limited, Mathura
7.50
1982
7.
Hindustan Petroleum Corporation Limited, Vizag
7.50
1975
8.
Hindustan Petroleum Corporation Limited, Mumbai
5.50
1954
9.
Bharat Petroleum Corporation Limited, Mumbai
8.90
1955
10.
Cochin Refineries Limited, Cochin
7.50 (10.5)
1966
11.
Chennai Petroleum Corporation Limited, Chennia
6.50 (9.5)
1969
12.
Bongaigaon Refineries Limited, Bongaigaon
2.35
1972
13.
Madras Refineries Limited (CBR), Nagapatinam
0.50
1994
14.
Mangalore Refineries & Petrochemicals Ltd., Mangalore
6.00 (9.0)
1995
15.
Indian Oil Corporation Limited Panipat
6.00
1998
16.
Reliance Petroleum Limited, Jamnagar
27.00
1999
17.
Numaligarh Refineries Ltd., Numaligarh
3.00
2000
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13.5 (18)
Total Capacity
1965
112.45
Indian Refining Industry Emerging Scenario

u
Shifting product demand
Stringent product specifications
Stringent environmental regulations
Feedstock quality deterioration
Globalisation
Deregulation of oil and gas sector
Indian Refining Industry Special Features

u
Larger requirement of middle distillates (diesel,

kerosene)
Prevalence of old as well as modern technologies
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UNIT 1
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Growth and Development of Refining Industry in India
A few refineries with size far lower than world

standards.
Strategies for Indian Refineries
5
Activity 1 C
i.
Describe special features of

Downstream Industry.
ii. Challenges
faced
and
strategies to meet the same.
Residue upgradation technologies for heavy crudes
Technologies for producing lighter fuels
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Process technologies to improve quality with respect to:
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performance parameters
eco-friendly products
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Value addition to refinery streams
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Increased emphasis on Process Control/ Automation
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Evolutionary/innovative technological changes expected

rather than revolutionary ones
Refineries to be integrated ,compact and flexible with

respect to crude/ product mix.
Future Technological Challenges

u
Meeting higher demand of petroleum products (viz.

distillates)
Meeting higher standards of product qualities
More emphasis on environment
Value addition to refineries
Technologies to improve margins
Zero emission refinery
Capacity Increase (To Meet Demand of

Petroleum Products )
u
Low cost revamps/ addition of units
Run length improvement of units
Infrastructure development for crude receipt/storage/

distribution
Installation of matching secondary processing plants.
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Value Addition
u
Production of value added products from refinery

streams
Propylene, butene 1, butene 2, N Paraffin, Lab,

Benzene, Toluene, Hexane, P Xylene etc.
Generation of power from heavy ends
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Distillation Range Improvement

u
New residue conversion technologies like FCC,

Hydrocracker, RDS-RFCC
Advanced controls and optimisation
Advanced catalysts
Continuous simulation of plants/ product mix through

computer models
Prudent selection of technologies and proper

integration of secondary units/ plants.
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Review Questions
1.
Please identify technological challenges that refineries

will face in future.
Unit 2
Crude Oil and Its
Characteristics
Activity 2 A
How is the crude oil formed?
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Objectives
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Understand the chemistry of petroleum, different types of crudes

and their characteristics.
Develop an insight into the significance of various characteristics

of crudes and method of determination of the same.
Get an idea of various crudes used in Indian Refineries.
Appreciate the difference between Indian crudes and typical middle

east crudes.
Crude Oil Characteristics and its Significance

(General Information)
Crude oils are formed by the action of geological processes
on the remains of ancient marine life.
It is a complex mixture of hydrocarbons and over 16,000
compounds have been identified in one sample.
Composition varies widely:
By geographical location
Mix of individual wells
Variance of wells with time
Chemistry of Petroleum
Crude oil contains almost all known hydrocarbons and nonhydrocarbons. As it is drawn from the earth, it also contains
impurities like water, mud and salts which get associated
during its production and transportation.
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Crude oil, the basic raw material of refining industry, is a

mixture of eight different hydrocarbon families:
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i.
Paraffins
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ii.
Cyclopentanes
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What are the type of hydrocarbons

present in the crude?
OLEUM &
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Activity 2 B
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iii. Cyclohexanes
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iv.
Cycloheptanes
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v.
Di-cyclo-paraffins
vi.
Benzenes
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vii. Aromatic cycloparaffins
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viii. Dinuclear and polynuclear

Aromatics are present in smaller amounts in compounds
containing metallic constituents such as Vanadium, Nickel,
Iron, Copper, Magnesium, Calcium, Zinc, Titanium etc.
Besides impurities such as Sulphur, Nitrogen and Oxygen
compounds mostly present in high boiling point fractions are
also present in crude oil. Based on boiling point, the fractions
are separated and given secondary treatment to utilise it as
finished products. Based on proportion of types of
hydrocarbon, it can be divided into Paraffin, Napthenic and
Aromatic categories. The purely hydrocarbon content may
be as high as 97% and as low as 50% for heavy crude oils. The
non-hydrocarbon portion retains hydrocarbon characteristics
as the molecules contain one or two atoms of elements other
than carbon and hydrogen. The carbon content is between 83
to 87% and hydrogen content between 11 to 14%. The ratio
of carbon to hydrogen increases from the low to high
molecular weight fraction due to increase in polynuclear
aromatic and multi ring cycloparaffins in these higher boiling
fractions. Atmospheric distillation is adopted for separating
the compounds present into various fractions upto 366C:i.
Overhead gases containing mainly methane, ethane,

propane and butane.
ii.
C590 C light naptha
iii. 90C140C heavy naptha

iv.
140C204C Mineral Turpentine Oil (MTO)
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UNIT 2
Crude Oil and its Characteristics
v.
140C240C Aviatin Turbine Fuel (ATF)
vi.
140C270 Kerosene
9
Activity 2 C
i.
vii. 270C340C Gas oil

viii. 340C366C Jute Batching Oil (JBO)
How do you classify crudes

based on proportion of type of
hydrocarbon present in them?
ii. What is Crude Assay? How are

these Assays utilized?
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366C plus fraction i.e. Reduced Crude Oil (RCO) is subjected

to vacuum distillation for obtaining vacuum gas oils, raw
Lube Distillate and short residue. Various fractions obtained
from atmospheric and vacuum distillation are given further
treatment to meet required specifications for use.
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Crude Assay
__________________
Crude Assay is the determination of properties of various

fractions of crude oil. This is done to assess the utility
of the crude for processing for production of various
products and their yields. Crude Assay Data are utilised for
the following:
u
Crude oil selection
Crude oil grading
Crude valorization
Crude swapping
Crude imports
Creation of new infrastructure at the existing refineries
Grassroot refineries
Production planning management
Inventory problems
Demand/supply gaps
Types of Evaluations
Preliminary Assay
u
Crude characteristics Consistency of crude supply.
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Short Evaluation
u
Crude characteristics
Absorption of new
crude in fuel refinery
TBP assay
To study the change in

quality of crude over a
period of time
Yield data and key

u
characteristics of straight
run cuts in fuel range and
long residue
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Detailed characterisation of crude oil

including all micro
constituents.
Detailed Evaluation
u
Design data for grass

root refinery
TBP assay in
atmospheric and
vacuum range
Product optimisation
Selection and design of

secondary conversion
units.
Yield and characteristics of sets of distillates

in atmospheric and
vacuum range with
variation in IBP, FBP
characterisation of
several long and short
residues.
Information Required
u
Base and general properties of crude oil
Presence of impurities
Operating and design data
Fractionating or TBP distillation curves
Equilibrium of flash vaporization curves
API or specific gravity curves of each fraction

distilled.
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Property curves of fractions vs% distilled
11
Notes
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Mid% curves
Yield% curves
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ISO% curves
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u
Properties and yield of straight run fractions and

residues
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Detailed composition of light distillates
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Hydrocarbon Type Distribution of Middle and Heavy

Distillates
Characteristics of Crude Oil

Basic Properties
Impurities
Density & API
Water Content
Reid Vapour Pressure (RVP)
Salt Content
Light End Analysis
BS & W
Pour Point
Sulphur Content
Viscosity
Nitrogen Content
Wax Content
Inorganic and
Asphaltenes
Total Acid
Carbon Residue
Trace Metals
Ash Content
Distillation Characteristic (D86 or D285)
Base of Crude Oil
Crude Oil Characteristics and their Significance

Density
Density is used for:
u
Weight to volume or vice versa calculations
Checking the consistency of crude supply
Control of refinery operations
Used in various correlations
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MASS (M)
Density =
VOLUME (V)
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Also gives a rough indication of type of crude oil
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M/V
Specific GRAVITY=
M/V (WATER)
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141.5
API GRAVITY=
131.5
SP.GR AT 60/60F
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Examples:
Water
= 10 API
Kerosene
= 45 API
Motor Gasoline
= 58 API
Natural Gasoline = 75 API

Crude oils are categorised based on gravity
Light grades
: Above 33 degree API
Medium grades
: 23-33 degree API
Heavy grades
: upto 22 degree API
CRUDE
Narimanam
Ankleshwar
Jotana
Bombay High
Heera
Kalol
Rumaila
Ratna
Rostam
Jhalora
Basrah
Sobashan
N. Gujarat
Geliki
Nahorkatiya
Kuwait IF IR.
Oman
Elmorgan
Jorajan
Kharsang
Lakwa
Jhalora
Density
0.7920
0.7930
0.8161
0.8278
0.8412
0.8414
0.8448
0.8484
0.8495
0.8496
0.8527
0.8549
0.8553
0.8675
0.8688
0.8698
API
47.08
46.85
41.80
39.35
36.62
36.55
35.90
35.20
35.00
35.16
34.40
33.99
33.85
31.50
31.30
31.10
TYPE
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P
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I
P
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I
I
P
I
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I
TOTAL DISTILLATE UPTO 370C

79.6
78.2
52.0
65.4
60.6
47.0
55.7
51.0
59.7
42.1
52.5
43.0
44.0
54.5
60.9
47.0
0.8727
0.8821
0.8910
0.8952
0.8986
30.55
28.84
27.22
26.50
25.87
I
N
N
N
I
48.1
60.7
61.7
53.7
31.8
Kothana
Rudrasagar
Sanand
N- Kadi Mix
Badarpur
Santhol
0.9000
0.9210
0.9242
0.9340
0.9430
0.9507
25.64
22.10
21.45
19.91
18.39
17.29
I
N
I
I
N
I
28.2
60.3
24.4
27.6
60.6
22.9
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Sulphur
Notes
Crude oils are also categorised based on sulphur.

u
13
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Sulfur is a measure of sourness and sweetness of

crude
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Sweet grades<0.5% of Sulphur
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Sour grades >0.5% of Sulphur
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Sulphur is passed on to products as much as regulations or

market accepts. It is removed in hydrotreater by reacting
with H2 and recovered as elemental sulfur in SRU.
Reid Vapour Pressure (RVP) and Light End Analysis

RVP indicates relative Percentage of gaseous and lighter
hydrocarbons in crude oil.
Component
RVP, Kg/cm2
Propane
14.1 Kg/cm2
Butane
6.6 Kg/cm2
Crude Oil
0.01-0.05
Light end analysis carried out by GLC actually gives the

percentage of hydrocarbons upto C5 and is the basis of
assessing the LPG potential of crude.
TYPICAL HYDROCARBON ANALYSIS
Components
% WT on Crude
C1
ND
C2
TRACES
C3
0.1
ISO-C4
0.1
N-C4
0.3
ISO-CS
0.3
N-C5
0.5
TOTAL
1.3
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Flow Characteristics of Crude Oils
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Characteristics
BH Crude
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WAX, % WT
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Pour Point,C
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Viscosity Kinematic cst
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AT 37.8 C, 50C
Geological Characteristics
Yield Value Dynes/ cm2 AT
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32C
45.0
2.0
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24C
85.0
5.0
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18C
222.0
10.0
16C
330.0
12.5
32C
7.9
9.6
24C
30.7
14.7
18C
43.7
16.0
16C
45.0
17.3
10.9
Basrah Crude
3.5
+30
-24
4.30, 3.32
6.18, 4.84
Plastic Viscosity, C.P. AT
Pour Point
u
Indicates relative amount of wax present in crude oil
Is the temperature below which pumping and

transportation problems may be encountered
Along with viscosity, is used in pumping and design

calculations:
Wax Content
Normal paraffins above C16 are solid at somewhat ambient
temperatures. These hydrocarbons
u
Affect the flow behaviour of crude
Affect the product quality of gas oil, VGO and asphalt
Lube manufacture is also dependent on wax content of

the crude.
Salt Content
It is measure of contamination in crude that will cause
overhead corrosion or foul up exchangers by settling and
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UNIT 2
15
sealing. It is removed in desalter by washing and settling

mainly chlorides and sulphates of Na, K, Ca, Mg.
Resins
Particulates
Waxy Agglomerates
Brine Droplet
Asphaltenes
Na+
COO-
Na+
COO-
Alkyl Benzene
Activity 2 D
i.
How do you separate various

fractions present in crudes?
ii. What are various impurities in

crudes, their bad effects and
how are these impurities
removed?
iii. Method of determination of
salt content, BS&W & Viscosity.
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Naphthenates
Carboxylates
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FIGURE 2.1 POSTULATED STRUCTURE OF STABLISED EMULSION
Problems Encountered Due to Salts
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Irregular behaviour in distillation
Equipment corrosion in the atmospheric distillation

caused by HCL liberated due to hydrolysis of chlorides
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Increased Consumption of Amonia

u
Salt is a major cause of blocking and fouling of heat

exchangers
Residual product contamination

Total Chloride evolved as
Ashci
HCL%%
100
75
50
25
0
0
100
200
300
400
PTB AS
as NACL
Salt Content of Crude PTO
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Salts may vary widely in ratio of metal ions, though

common averages are Na: 70-75%, Mg: 15-20%, Ca: 10%.
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k~ e
k ; k k f D r o
Mg is most prolific producer of HCL with Ca and Na in

descending order
Small quantities of HCL may substantially enhance

corrosion of sulphur compounds
__________________
__________________
OLEUM &
GY
Notes
E TR
ER
Refining
16
FP
__________________
__________________
__________________
Methods for Determination of Salt Content

1.
IP 77/72
Extraction with water KCNS/Ag No 3

titration
2.
ASTM D3230
Conductivity measurement based on

calibration with Na, Ca, Mg chlorides
standard solutions in mixed alcohol.
__________________
__________________
__________________
__________________
Sediment and Water
Sediment has no relationship with salt but both might

increase with connate water
Sediment
Fine particles of sand clay,

volcanic ash, drilling mud, rust,
iron sulphide, metals and scale
Damaging Effects
Plugging Abrasion and residual

product contamination
Water causes irregular behaviour in distillation.
Sediment in crude oil is measured by the following methods:

BS & W
ASTM D 96
Sediment by extraction
ASTM D 4007
Water content
DEAN & STARK

ASTM D 4006
Sediment in crude is determined for custody transfer

purposes
Lower the sediments and water, higher the reliability

of the unit. It is also a major pointer for corrosive
materials in crude.
YO
OLEUM &
n ~;
ST U DI ES
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GY
UNIV ER SIT
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FP
UNIT 2
k~ e
k ; k kf D r o
Asphaltenes, Carbon Residue and Ash Content

Asphaltenes
u
Are polynuclear condensed aromatic hydrocarbons

having high molecular weight
These are insoluble in heptane and soluble in Benzene/
Toluene
17
Activity 2 E
Significance of TAN & KUOP.
__________________
__________________
__________________
__________________
__________________
__________________
Asphaltenes and carbon residue indicate the extent to

which heavy hydrocarbons are present in crude oil.
Ash Content
u
Metallic constituents concentrate in the ash of the crude

oil
Carbon Residue
Its a carbonacous residue formed after evaporation
and pyrolysis of the sample. The residue is coke and
determined by
Conradson residue method ASTM D 189
Ramsbottom carbon residue ASTM D 624
Micro-carbon residue method ASTM D 4630
Viscosity
It is a measure of resistance to flow and is an important
parameter for effective desalting. It is also highly dependant
on temperature.
High viscosity crudes need high temperatures for effective
desalting. There is a limit for temperature in desalters
operation.
KUOP
It is a measure of parafinity vis--vis aromaticity of crude.
High KUOP is desired for high conversion in FCC, aromatic
molecules cannot be cracked in FCC. They will simply take
a ride through the plant.
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YO
UNIV ER SIT
__________________
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__________________
__________________
fo
n ~;
EN
ST U DI ES
What are various crudes

processed in Indian Refineries?
Where are Indigenous crude
found? What is the sulphur content
of Indian crudes?
OLEUM &
GY
Activity 2 F
E TR
ER
Refining
18
FP
k~ e
k ; k k f D r o
TAN
TAN is actually Total Acid Number.
It is a measure of Naphthenic Acid (NA) contents in crude.
This leads to corrosion in various sections of the unit. Over
1,500 known NA species are present in crude.
All napthenic 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 and monitoring mechanisms
must be put in place.
Selection of Crude Oil

Technology trends in petroleum refining are driven by the
external forces of product demand, product specifications
(including environmental consideration), feed stock quality
and availability. Crude oil will gradually become heavier and
higher in sulphur content. Refineries, of late, have been
sincerely attempting to produce fuels to comply with stricter
environmental regulations particularly gasoline and diesel
and are in the process of reducing the sulphur levels in
distillates and fuel oil. Attention is now also being paid to
reduce lead and benzene levels in gasoline. Various gasoline
and diesel specifications applicable worldwide are given in
the later part of this chapter.
Crude processed in India are:
1.
Indigenous crude oil sources

a.
Bombay high and satellite fields
b.
North Gujarat and Ankaleshwar crude
c.
Assam crudes
d.
KG Basin-Rava crude
e.
Cauvery Basin crude
All the above crudes are low sulphur =<0.5% wt, low
metal content, poor potential to yield LOBS and
bitumen, and some are waxy in character.
YO
OLEUM &
n ~;
2.
ST U DI ES
fo
EN
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FP
UNIT 2
k~ e
k ; k kf D r o
19
Activity 2 G
Imported crudes are sourced mostly from:

a.
Gulf Region
b.
Nigeria
c.
Malaysia
d.
Australia
What straight run fractions are

obtained
in
Atmospheric
Distillation? And in Vacuum
Distillation?
__________________
__________________
__________________
The above crudes are specially selected for production of

Bitumen/LOBS/ATF, beside fuel products.
__________________
These crudes are having varying range of sulphur from low

of high.
__________________
Comparison of Crudes
__________________
__________________
__________________
__________________
Comparison of Indian crudes and typical Middle-east crude

mix for yield and key properties of straight run cuts:1.
Gases upto 20C
4.
GAS OIL 250370C
2.
Naphtha I.B.P.- 140c
5.
Vacuum GAS OIL 370530C,
3.
KEROSENE 140-250C
6.
Short Residue 530, C+.
1
2
AROM. 16% Vol

NAPH. 52% VOL
COTANE NO.
73.7
SMOKE POINT
14mm
Arom. 36%
VOL.
E.P.T.<60C
DIESEL INDEX
33
POUR POINT
9C
KUOP II-61
KIN. VISC. AT
96.9C
7 0St
API 3.8
ASSAM CRUDE
MIX API 29.85
SULPHUR 0.24%
Wr. POUR POINT
+30C WAX
CONTENT 10.8%
Wt.
KUOP 11.30
1-2
15.0
17.6
27.1
27.2
AROW 5.8% VOL.

NAPH 40.6%
V.O.N.O.
SMOKE PT. 23
mm AROM. 1:1 %
VOL F.P.T.-54C
DIESEL INDEX 57
POUR POINT +3
KUOP 12.10
KIN VISC. AT
100 C
8.120 SI
API 13.58
POUR POINT
+48
KIN. VISC. AT
100C 150(27 0SI
CCR 14.77% Wt.
N.9
NORTH GUJARAT
CRUDE MIX
API 26.83
SULPHUR 0.17%Wt.
POUR POINT+21
WAX CONTENT
6.8% Wt
KUOP 12.0
0.4
4.4
10-1
19.2
31.2
34.7
3.8
AROM: 6.6%
VOL
OCTANE No.
67.5
SMOKE POINT
27mm
AROM. 15% VOL.
F.P.T.48C
DIESEL INDEX
67
POUR +POINT
+6C
KUOP 12-70
KIN. VISC. AT
100C
405 0St
API 16.5
CCR 9.92% WI.
POUR POINT +
68C
24.9
22.3
23.9
18.8
6.3
GANDHAR+ANKLESWAR (60. 40 VOLT

CRUDE MIX
API 46.9
SULPHUR 0.041 % Wt.
POUR POINT+27C
WAX CONTENT 8.9%
Wt.
__________________
YO
UNIV ER SIT
__________________
__________________
__________________
__________________
__________________
__________________
ARON 21.3%
VOL. NAPH. 25%
VOL OCTANE
NO. 69-6
SMOKE POINT
17mm
AROM. 26.9%
VOL. F. PT. -49C
DIESEL INDEX
56
POUR POINT
+3C
18.6
20.9
KUOP 12.37 KIN

VISC. AT 98.9C
5.36 0St
24.7
DIESEL INDEX
58
POUR POINT
12C
28.4
KUOP 12.31 KIN

VISC. AT 100C
4.83 0St
15.7
6.2
API 16.35, CCR

10.4 % Wt POUR
POINT+ 60C
4.7
__________________
API 9.51
CCR 19.2% Wt.
POUR POINT
+72C
SMOKE POINT
27mm Arom. 16%
Vol,. F. PT57C
30.4
24.0
__________________
__________________
2.7
ARON 4% VOL.
OCTANE
NO.61.9
BOMBAY HIGH API

39.35 SULPHER
0.17% Wt. POUR
POINT+ 30C WAX
CONTENT 10.6%
Wt. KUOP 11.70
NARIMANAM
CRUDE
API 47.08
SULPHUR 0.085%
Wt. POUR POINT 0
WAX CONTENT
2.8% Wt. KUOP
11.98
21.8
fo
n ~;
EN
ST U DI ES
__________________
1.9
OLEUM &
GY
Notes
E TR
ER
Refining
20
FP
k~ e
k ; k k f D r o
2.1
AROM 7.3% VOL

OCTANE No. 53.8
SMOKE POINT
26mm
AROM. 18.6%
VOL. F.P.T.56C
DIESEL INDEX
58
POUR +POINT
9C
KUOP 11-94
KIN. VISC. AT
100C
5.98 0St
API 7.43
CCR 19.85% Wt.
POUR POINT +
54C
KIN. VISC. AT
100C
903.650St
10.7
16.1
18.1
22.5
30.5
Kuwait+Lt. IRANIAN
FOMAN (56: 36: 6 VOL. )
API 31.1
SULPHUR 2.28% Wt.
POUR POIN T(30C
WAX CONTENT 1.1%
Wt. KUOP II.98
Selection of Crude(s) for a Refinery

Based on product demand, type of products, processing
schemes of refineries, metallurgy of existing plant and
equipment, crudes are selected after evaluating detailed
crude Assay Data. Mostly, a mixture of crudes is selected
for a refinery to optimise the cost and meeting products
quality specifications.
Review Questions
1.
Describe different characteristics of crudes dealt with

in this unit, their significance and typical values/ units
of measurement.
2.
Draw a comparison of indigenous crudes with Typical

Middle East Crude(s) vis--vis important specifications
of Petroleum Products.
YO
OLEUM &
n ~;
3.
ST U DI ES
fo
EN
GY
UNIV ER SIT
E TR
ER
FP
UNIT 2
k~ e
k ; k kf D r o
From which Indian crudes, can you produce
21
Notes
__________________
a.
ATF
b.
Bitumen
__________________
c.
Lubes
__________________
d.
Micro-crystalline wax
__________________
e.
Good Quality Calcined Petroleum Coke
__________________
__________________
__________________
__________________
__________________
__________________
23
Unit 3
Notes
__________________
Specifications of Petroleum
Products and Related Tests
__________________
__________________
__________________
__________________
__________________
__________________
__________________
Objectives
__________________
__________________
y
Understand the specifications of various petroleum products, their

significance and their determination/tests.
Appreciate crucial specification of HSD & MS from Environmental

Pollution Standpoint & Strategies for meeting stringent norms for
future Euro III/IV, Bharat III/IV.
Specifications
What are Specifications?
Any material which is intended for use in a particular
application should have certain characteristics so that it is
suitable for use in that application. These characteristics are
quantified to make them absolute and also to remove any
ambiguity in the interpretation. These quantified
characteristics are called specifications.
Some important tests conducted on petroleum products

and included in specifications:
Flash Point
RON
Color
Pour Point
MON
BMCI
Distillation
AKI
Bromine Number
Copper Corrosion
Cetane Number
Benzene Content
Silver Corrosion
Cetane Index
Density
Sulphur
Smoke Point
Sediment
Viscosity
Aniline Point
Water
Potential Gum
Carbon Residue
Weathering Test
Existent Gum
Vapour Pressure
YO
fo
n ~;
EN
ST U DI ES
UNIV ER SIT
OLEUM &
GY
Notes
E TR
ER
Refining
24
FP
k~ e
k ; k k f D r o
Significance of Tests
__________________
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__________________
__________________
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__________________
__________________
__________________
Flash Point
It is the minimum temperature at which the sample gives
sufficient vapour which forms an explosive mixture with air
giving a flash when a flame is applied to it under conditions
of the test method.
Flash point is associated with safety during storage and
application in some respects. When a product like kerosene
is stored either at home or at a commercial location, it forms
vapour above it depending upon the ambient temperature.
If the vapour so formed is sufficient to form an explosive
mixture with air, there would be explosions when a small
naked flame is exposed to it. Each country has it own
legislation with respect to flash point depending upon the
climatic conditions of the country.
Pour Point
When heavy petroleum oils containing wax are allowed
to settle (like in storage tanks), wax separates out from
them making the oil immobile. If the oil does not move,
it cannot be pumped. The temperature at which the
oil becomes immobile (does not move) is termed as
pour point when tested under the conditions of the test
methods.
Distillation
The volatility of an oil is indicated by its distillation
characteristics. Unlike pure compounds, petroleum oils are
mixtures of several hydrocarbons and so will have a boiling
range instead of boiling point. The oil should have suitable
boiling range (volatility) so that it can be used in a particular
application. For example, Motor Gasoline which is used in
spark ignition internal combustion engines, has the following
specifications for distillation:
Recovery upto 70o C
10 to 45% Min
Recovery upto 100o C
40 to 70% Min
Recovery upto 180o C
90% v Min
YO
OLEUM &
n ~;
ST U DI ES
fo
EN
GY
UNIV ER SIT
E TR
ER
FP
k~ e
k ; k kf D r o
UNIT 3
Specifications of Petroleum Products & Related Tests
Since the application is in a spark ignition engine, the

fuel should easily vaporise to a sufficient degree so that
when a spark is applied it can ignite. The specification for
recovery at 70 o C is laid to meet this requirement. The
maximum limit of 45% is laid to prevent some other
undesirable effects such as vapour lock. This quality is called
easy start.
The specification for recovery at 100oC is set to give power
to engine and take load.
The specification for recovery at 180oC and final boiling point
are set to prevent crank case oil dilution and unburnt
hydrocarbon in tail gases (air pollution).
Copper Corrosion
The fuel product comes on contact with metal parts such as
transfer pipe from storage tank, storage tank itself, the
burner in a kerosene stove, stove body itself, storage and
transportation equipment like pumps, storage vessels etc.
If the product is corrosive, it will corrode these parts and
reduces their life. Copper corrosion test indicates whether
the product is corrosive to copper containing alloys or not.
This test is applicable to all fuels.
Silver Corrosion
This test is done for Aviation Turbine Fuel (ATF)Jet A1 Type
Some aircrafts of civil aviation and defence use a silver lining
in the fuel transfer lines. In order to protect this lining, the
fuel should not be corrosive to silver. Hence this test is done
for ATF. This is a requirement for Indian region only. Western
countries and USA do not use this test any more.
Sulphur
Sulphur, besides being corrosive to the fuel systems, is a
pollutant to the air and affects life. Global efforts are being
made to minimise the sulphur content in motor gasoline, high
speed diesel and fuel oils.
25
Notes
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YO
UNIV ER SIT
__________________
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fo
n ~;
EN
ST U DI ES
__________________
OLEUM &
GY
Notes
E TR
ER
Refining
26
FP
k~ e
k ; k k f D r o
Viscosity
Viscosity is the resistance to flow. The unit of absolute or
dynamic viscosity is Poise and that of kinematic viscosity is
Stoke. Viscosity is an important property for lube oils
because it gives the lubricating property to the oil. This is
required to prevent wear and tear in the moving parts of a
machine on account of metal to metal contact. For fuel oils,
it gives flow properties which are needed for pump selection
for transporting.
Viscosity is measured in several ways. The most common
are Kinematic Viscosity measured in centi-stokes and Saybolt
Universal Viscosity measured in seconds.
Potential Gum
This test is applicable to motor gasoline which may contain
unsaturated hydrocarbons (olefins). Olefins are oxidised by
atmospheric oxygen to a gummy material which sticks to
the carburetor jet of the vehicle or inlet valve leading to valve
sticking which in turn results in the malfunction of the
engine. This type of gum is characterised by Potential Gum
test. It does not show the exact amount of gum that would
form on storage but gives a directional indication. The unit
of measurement is mg per liter.
Existent Gum
This test is applicable to motor gasoline.
If motor gasoline contains any soluble solid residue, the
residue gets deposited in the carburetor and other parts
after the gasoline is vaporised. Such deposit may clog the
jet and prevent fuel flow due to which the engine stops. That
is why this test is done on MS. The specification is 40 mg per
litre max.
One point should be noted. Some solid material is added to
MS deliberately for some purposes. Example: Dye to identify
the MS from others. These type of residues are excluded
from the specification.
YO
OLEUM &
n ~;
ST U DI ES
fo
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FP
k~ e
k ; k kf D r o
UNIT 3
Octane Number
27
Notes
It is defined as the per cent volume of iso octane in a mixture

of iso octane and normal heptane that gives the same
knocking as that of the fuel when tested under defined
conditions.
Iso octane is assigned a value of 100 and normal heptane 0
octane number.
Normal paraffins have the lowest octane number. Next comes
napthenes followed by iso paraffins, olefins and aromatics
for the same carbon number. However, this is only a general
rule and may differ in the case of iso paraffins. Some of them
have lower octane numbers than corresponding napthenes
and some other higher octane number depending upon the
branching of the iso paraffin. Similarly Octane numbers of
olefins may also differ slightly as given below:
l
n-Hexane
24.8
Cyclohexane
83
2,2 Dimethy 1 Butane
91.8
2-Methyl Pentane
73.4
Hexene-2
90
Benzene
>100
N-Heptane
Methyl Cyclohexane
75
2,3 Dimethyl Pentane
88
2 Methyl Hexene-1
92
Toluene
107
Octane numbers are not truly additive. When used singly,

the hydrocarbons behave in some way and when used in a
mixture, they behave in another way. For example, Toluene
has a RON 107 when it is a single component system. But
when it is mixed with other hydrocarbons, it behaves as if
its octane number is > 120.
Some schools of thought say that in multi-component
systems, like naptha, octane number is additive on weight
percent basis. Some others believe that it is additive on mol.
__________________
__________________
__________________
__________________
__________________
__________________
__________________
__________________
__________________
__________________
YO
UNIV ER SIT
__________________
fo
n ~;
EN
ST U DI ES
__________________
OLEUM &
GY
Notes
E TR
ER
Refining
28
FP
k~ e
k ; k k f D r o
per cent basis. In effect, there are always some exceptions

and some deviations.
__________________
Research Octane Number and Motor Octane Number.
__________________
These are determined under different conditions of the test.
__________________
Test Condition
RON
MON
Engine speed
600 RPM
900 RPM
__________________
Spark advance
13 o
Variable
__________________
Mixture Temp
--
300 o F
In Take Air Temp
125o F
100 o F
__________________
__________________
__________________
AKI (Anti Knock Index)

It is defined as the average of RON and MON.
AKI = (RON + MON)/2
Anti Knock Index is regarded as more critical for engine
performance than RON alone.
Cetane Number
This test is applicable to diesel fuels which use ignition by
compression.
Cetane number is defined as the per cent volume of n-cetane
in a mixture of n-Cetane and alpha methyl naphthalene that
would give the same knocking as that of the fuel under test.
n-Cetane is assigned a value of 100 and alpha methyl
naphthalene a value of 0.
Alpha methyl naphthalene has some storage stability
problem. It turns red when exposed to air. So, although it is
a primary fuel, a secondary fuel for routine use is also stated
in the test method. This is hepta Methyl Nonane (HMN).
Another consideration for using HMN is its easier
availability.
This test has reverse characteristics of octane number.
Here, normal paraffins have highest cetane number followed
by naphthenes, iso paraffins, olefins and aromatics in general
YO
OLEUM &
n ~;
k~ e
k ; k kf D r o
ST U DI ES
fo
EN
GY
UNIV ER SIT
E TR
ER
FP
UNIT 3
but the order may vary depending upon the chain length of
iso paraffins.
29
Notes
__________________
Cetane Index
__________________
It is an alternative to cetane number. It is nearly equal to

cetane number but not an actually determined value required
cetane engine. Cetane index is not applicable to fuels
containing cetane improves.
__________________
__________________
__________________
__________________
__________________
Smoke Point
Smoke point is defined as the maximum length of the flame
which does not give smoke when tested under prescribed
conditions using the prescribed apparatus.
Smoke point shows the hydrocarbon nature of the fuel.
Paraffins have high smoke points followed by naphthenes
and then by aromatics.
The test is applicable primarily to kerosene. The main
purpose of kerosene is for use in lantern. If the kerosene
gives smoke when it burns, it gives less light. As the flame
size increases the light given out would also be more. But if
the kerosene starts giving smoke, the height of the flame
has no meaning. So the higher the flame without smoke, the
better.
Smoke point is related to hydrogen content of the fuel. The
higher the hydrogen content, the higher will be the smoke
point. Paraffins contain highest hydrogen content for the
same carbon number. So the smoke point of paraffins is
highest.
The specification of smoke point for kerosene in our country
is 18 mm minimum.
Aniline Point
Aniline point is the minimum temperature at which equal
volumes of sample and aniline are miscible.
Aniline point gives the hydrocarbon nature of the oil.
Aromatic hydrocarbons have lower aniline points and
paraffinic hydrocarbons have higher aniline points.
Naphthenic hydrocarbons have intermediate aniline points.
__________________
__________________
__________________
YO
UNIV ER SIT
__________________
__________________
__________________
__________________
__________________
__________________
__________________
__________________
__________________
fo
n ~;
EN
ST U DI ES
__________________
OLEUM &
GY
Notes
E TR
ER
Refining
30
FP
k~ e
k ; k k f D r o
Aniline point in combination with density /specific gravity/

API gravity gives a quick idea of some important properties
like Diesel Index, Aniline-Gravity Product which are
important properties for diesel and ATF. Aniline gravity
product is an alternative to calorific value.
Carbon Residue
Every oil, when it burns, forms a carbon deposit which is
very difficult to burn. This carbon deposits on burner tips
chocking the orifices due to which the flow of oil stops and
burner tip needs to be cleaned. If this carbon deposit is more,
the burner tips have to be cleaned more frequently.
Carbon residue test gives an indication of the amount
of carbon that would form when the oil is pyrolysed and
burned.
There are two methods to determine carbon residue:
1.
Ramsbottom Carbon Residue (RCR)
2.
Conradson Carbon Residue (CCR)
Vapor Pressure
This is an indirect method of estimating most extreme low
temperatures under which initial vaporisation can be
expected to take place. It can be considered as a semi
quantitative measure of the amount of most volatile material
present in the product. It can also be used as a means of
predicting the maximum pressures which may be
experienced at fuel tank temperatures.
Colour
Two types of tests are applicable to petroleum products
1) Saybolt colour and 2) ASTM Color. The former is
applicable to white oils like kerosene, naphtha, MTO etc and
the other is applicable to diesel, vacuum distillates etc. The
colour gives an indication of the degree of refining or
contamination with foreign bodies.
YO
OLEUM &
n ~;
ST U DI ES
fo
EN
GY
UNIV ER SIT
E TR
ER
FP
k~ e
k ; k kf D r o
UNIT 3
BMCI (Bureau of Mines Correlation Index)

BMCI is an indication of predominant nature of
Hydrocarbons in a product.
31
Notes
__________________
__________________
__________________
All normal paraffins have BMCI zero or less than zero.
__________________
A high BMCI indicates predominantly Aromatic nature.
__________________
A low BMCI indicates predominantly paraffinic nature.
__________________
__________________
Intermediate BMCI indicates mixtures of both and also

naphthenic nature.
__________________
BMCI more than 100 indicates presence of condensed rings.
__________________
BMCI of some hydrocarbons

Hydrocarbon
BMCI
N Paraffins
0 or < 0
Iso Paraffins
< 15
Cyclohexane
50
Benzene
99
BMCI is a calculated value form density and 50% boiling

point. It is defined as,
BMCI (48640 / K) + (473.7 * G) 456.8
Where,
K = 50% Boiling Point in
G = Specific Gravity @ 20
K
/ 4o C
There are graphical correlations between BMCI and

Viscosity and Density also which are nearly equal to the
calculated value.
Bromine Number
Bromine number is defined as the grams of bromine that
react with 100 grams of the sample.
Bromine number gives the olefinity of the sample.
__________________
YO
UNIV ER SIT
__________________
fo
n ~;
EN
ST U DI ES
__________________
OLEUM &
GY
Notes
E TR
ER
Refining
32
FP
k~ e
k ; k k f D r o
Olefins react with bromine giving additional products. Each

double bond absorbs two atoms of bromine.
Example:
__________________
__________________
CH3CH2CH2CH2CH = CH2+Br2
__________________
Benzene Content
__________________
__________________
__________________
__________________
__________________
CH3CH2CH2CH2CHBRCH2Br
This test is applicable to motor gasoline.

Benzene is carcinogenic (causes cancer). Its limit in MS is
recognised by all countries. The specification for benzene in
India is 5%v for general supplies and 1% v max for supplies
to NCR.
Density
Petroleum products are liquids. They are sold on a
volume basis but the custody transfers are effected on
weight basis. Density is required for mass balance calculation
and is also useful for several correlations which indicate the
hydrocarbon nature and other properties.
Some of such correlations are, BMCI, Kuop, VGC.
Weathering Test
This test is applicable to LPG. It indicates the amount of
non vaporisable matter in LPG.
Specifications of Petroleum Products

LPG (IS 4796)
Test
Unit
Density
kg / M3
o
Volatility (95% Ev Temp) C

o
Vapor Pressure @ 38 C
Specification
Report
+2 Max
kg / cm2
Copper Corrosion @ 38 C
7 Max
1 Max
Sulphur
%w
0.05 Max
Odor
--
Identifiable
YO
OLEUM &
n ~;
ST U DI ES
fo
EN
GY
UNIV ER SIT
E TR
ER
FP
UNIT 3
k~ e
k ; k kf D r o
33
Motor Gasoline (IS 2796 - 2000)

Test
Unit
Color
-o
Density @ 15 C
kg / M3
Activity 3 A
Method
Requirement
Visual
Orange
P:16
710 770
P : 18
10 45
Distillation
What are different Petroleum

Products?
__________________
__________________
Recover @ 70 C % v
o
Recovery @ 100 C % v
__________________
40 70
Recovery @ 180 C % v
__________________
90 min
Final Boiling Point C
215 max
__________________
__________________
Research Octane Number
P:27
88 min
Anti Knock Index
P:26 & P:27
84 min
P:29
40 max
Existent Gum
gm/M3
__________________
__________________
(Solvent washed)
Potential Gum
gm/M3
p:147
50 max
Sulphur
%w
P:34
0.1 max
Lead as Pb
gm/1
ASTM D 5059
0.013
Reid Vapor Pressure
KPa
P:39
35-60
VLI Summer Winter
---
750 max
Benzene %v
ASTMD 3606
5 max
__________________
__________________
950 max
1max for NCR
Cu Corrosion
P:15
@ 50 C for 3 Hrs
Water Tolerance
Summer
10
Winter
Oxygenates % v
ASTM D 4815-89
15 max
NB: 1) MFA containing Phosphorus compounds should not be used

2) Potential Gum before doping MFA
PC Naphtha
Test
Unit
Method
Requirement
Appearance
Visual
Clear and Bright
Color
Visual
Colourless
Density @ 15 C
kg/M3
P:16
To Report
Distillation IBP
P:18
28 min
FBP
160
Total Paraffins
%w
ASTM D 5443
74 min
Normal Paraffins
%w
ASTMD 5443
36 min
Iso/Nor Paraffin Ratio
1.05 max
n C6
%w
To Report
nC7
%w
To Report
Contd...
YO
UNIV ER SIT
%w
Olefins
%w
P:23
1 max
Total Sulphur
ppm w
P:34 B
100 250
Mercaptan Sulphur
ppm w
P:109
150 max
__________________
Reid Vapor Pressure
Kpa
P:39
To Report
__________________
@ 38C
__________________
Chlorides
ppm w
ASTMD 4929
5 max
__________________
Lead
ppb w
P:82
100 max
__________________
Arsenic and Mercury
ICP
To Report
What are the key specifications of

Motor Spirit, LPG, HSD,
Petrochemical Naphtha, ATF?
How do these affect performance?
__________________
__________________
__________________
__________________
EN
fo
n ~;
ST U DI ES
Aromatics
OLEUM &
GY
Activity 3 B
E TR
ER
Refining
34
FP
k~ e
k ; k k f D r o
10 max
Superior Kerosene (IS 1459 - 1974)

Test
Unit
Method
Requirement
Acidity (Inorganic)
mgKOH/gm
P:2
Nil
mg/kg Oil
P:5
20 max
Burning Quality
__________________
Char value
Bloom on chimney
not darker than grey
Color (Saybolt) Undyed
Units
P:14
Dyed
+10
Blue
Copper Corrosion
@ 50 o C for 3 Hrs
Density @ 15 o C
P:15
Not worse than 1
kg/M3
P:16
To Report
%v
P:18
20 min
Distillation
Recovery @ 200
Final Boiling Point
Flash Point Abel
P:20
35 min
Smoke Point
mm
P:31
18 min
Total Sulphur
%w
P:34
0.25 max
300 max
Aviation Turbine Fuel (IS 1571 - 1992)

Test
Unit
Method
Requirement
Appearance
--
Visual
Bright, Free from solid

matter and visually
undissolved water.
Acidity Total
mg KOH/gm
P:113
0.015 max
Aromatics
%v
P:23
25 max
Olefins
%v
P:23
5.0 max
Total sulphur
%w
P:34B
0.30 max
Mercaptan sulphur
%w
P:109
0.003
Contd...
YO
OLEUM &
n ~;
ST U DI ES
fo
EN
GY
UNIV ER SIT
E TR
ER
FP
k~ e
k ; k kf D r o
UNIT 3
35
Notes
Distillation
10 % v Recovered at
degree C
P:18
205 max
__________________
50 % v Recorded at
degree C
P:18
Report
__________________
90 % Recovered at
degree C
P:18
Report
__________________
Final Boiling Point
degree C
P:18
300 max
__________________
Flash Point
degree C
P:20B
38 min
__________________
Density @ 15 C
kg/M3
P:16
0.775 to 0.840
__________________
Freezing Point
degree C
P:11
Minus 47 max
@ Minus 20 C
cST
P:25
8.0 max
Aniline Gravity Product
---
P:3
4800
Smoke point
mm
ISO 3014
25 min
Naphthalenes
%v
ISO 3014
3.0 max
---
P:15
1 max
---
IP 227
1 max
mm
P:97
25 max
Visual
3 max No Peacock
Or abnormal color
deposits
__________________
Kinematic Viscosity
__________________
__________________
__________________
Copper Corrosion
% 100 degree C for 2 Hrs
Silver Corrosion @ 50
degree C for 4 Hours
Thermal Stability
Pressure Differential
Tube Rating Visual
Existent Gum
mg/100 ml
P:29
7 max
MSEP
---
P:142
85 min
Electrical Conductivity
ps/M
IP 274
50 to 450
Lubricity mm
ASTMD 5001 Report
High Speed Diesel (IS 1460 2000)

Test
Unit
Method
Requirement
Acidity Inorganic
mg KOH/Gm
P:2
Nil
Acidity Total
mg KOH / Gm
P:2
0.2 max
Aah
%w
P:4
0.01
RCR
%w
P:8
0.3 (on 10 % residue)
Cetane Number OR
---
P:9
48 min
Cetane Index
---
ASTMD 4737 46 min
Pour Point
---
P:10
3 Winter
@ 100 degree C for 3 Hrs - - -
P;15
1 max
Density @ 15 degree C
P:16
820-860
Copper Corrosion
kg/M3
Contd...
YO
UNIV ER SIT
P:18
85 min
__________________
Recovery at 370 degree C % v
P:18
95 min
__________________
Flash Point
P:20
35 min
__________________
Kin Viscosity @ 40 deg C
cST
P:25
2.0 to 5.0
__________________
Sediments
%w
P:30
0.05
__________________
Total Sulphur
%w
P:33
0.25
Water Content
%v
P:40
0.05 max
CFPP
deg C
P:110
6 Winter
degree C
n ~;
k~ e
k ; k k f D r o
18 Summer
__________________
Total Sediments
__________________
fo
ST U DI ES
Recovery at 350 degree C % v
__________________
EN
Distillation
__________________
__________________
OLEUM &
GY
Notes
E TR
ER
Refining
36
FP
mg/100 ml
UOP 413
60o C,
400 Proposed
1.5 max
Lubricity HFRR Scardia

Micron at
Light Diesel Oil (IS 1460 - 2000)

Test
Unit
Method
Requirement
PSS
Acidity Inorganic
mg KOH/Gm
P:2
Nil
---
Ash
%w
P:4
0.02 max
0.005 max
RCR on whole sample
%w
P:8
1.5 max
0.3 max
Pour Point
deg C
P:10
12 Summer
0 max
21 Winter
0 max
Copper Corrosion
@ 100 deg C for 3 Hrs
---
P:15
2 max
1b
Flash Point (PMCC)
deg C
P:21
66 min
66 min
Kin Vis @ 40 deg C
cST
P:25
2.5 to 15.7
2.5 to 5.0
Sediments
%w
P:30
0.1 Max
0.05 max
Density @ 15 deg C
kg / M3
P:16
Report
910 max
Total Sulphur
%w
P:33
1.8 max
0.35 max
Water content
%v
P:40
0.25 max
0.05 max
Petroleum Coke (IS 8402 - 1994)

Test
Unit
Method
Requirement
PSS
Moisture as Received
%w
P: 132
10 max
8 max
Initial drying
%w
P: 132
2.0 max
---
Ash on Dry basis
%w
P: 126
0.45 max
1.0 Max
Volatile Matter
%w
P: 134
11 max
8 max
Moisture after
Contd...
YO
OLEUM &
n ~;
ST U DI ES
fo
EN
GY
UNIV ER SIT
E TR
ER
FP
UNIT 3
k~ e
k ; k kf D r o
Density (Dry)

kg/ M3
P: 133
Report
560 min
Total Sulphur
Notes
__________________
Fixed Carbon
(On Dry Basis)
37
%w
Calculation 85 min
88 min
__________________
%w
P: 33
7.0 max
__________________
2.5 max
__________________
Trace metals
UOP 389 Report
150 max
__________________
Silicon as Si
ppm w
Iron as Fe
ppm w
150 max
__________________
Vanadium as V
ppm w
1600 max
__________________
Nickel as Ni
ppm w
400 max
__________________
Hardgrove Grindability
__________________
Index
GCV
ASTMD 4097 50 MIN

Kcal/ Kg
---
8000 min.
Properties of Petroleum Products and their

Significance
Gasoline
Effect of Chemical Composition on Gasoline Quality
Octane number is the most important property of motor
gasoline. Composition of motor gasoline profoundly affects
its performance in the engine and equally controls its
behaviour under storage and handling.These are described
below:
Paraffins (Cn H2n+2)
Thermally and chemically most stable compounds.
Have poor octane number
Increasing the chain length reduces the octane number
Knock resistance increases with branching
Adding methyl groups (CH3) to the side chain in the

central position increases the knock resistance
Olefins (Cn H2n)
Oxidation and thermal stability is poor in general
More knock resistance than their corresponding

saturated compounds.
__________________
YO
UNIV ER SIT
EN
fo
n ~;
ST U DI ES
__________________
OLEUM &
GY
Notes
E TR
ER
Refining
38
FP
k~ e
k ; k k f D r o
Cycloparaffins (CnH2n)
Poorer knock resistance than corresponding aromatics
__________________
Lengthening of side chain decreases knock resistance
__________________
Branching of side chain is beneficial.
__________________
__________________
__________________
Aromatics (CnH2n-6CnH2n-12 etc)
__________________
Aromatics have excellent knock resistance qualities.
__________________
__________________
__________________
Properties of Gasoline and Oxygenated Compounds

Property
Methanol
Chem.
CH30H
Ethanol
C2H5OH
Isopropyl
Alcohol
Tertiary
Butyl Alcohol
C3H70H
C4H90H
MTBE
Gasline
C4H9OCH3
C8H15 (Av.)
Formulae
Mol. Wt.
32
46
60
74
88
111
Oxygen
50
35
27
22
18
Cont. % mass
B.P.C
65
78.3
82.2
82.8
55
30-20
Stoichio-
6.4
9.0
10.3
11.1
11.7
14.6
Lat. Heat of
Vap. Btu/Gal
(J/lit)
3300
2600
2100
1700
900
800
(11.8)
(9.3)
(7.5)
(6.1)
(3.2)
(2.9)
Net
Heat
comb. MJ/Kg
21
28
32
35
35
43
SolubiSolubility in
water, g/100g
water
4.8
Trace
RON
107
108
112
113
116
87-93
101
82-87
Meteric A/F
MON
Gasoline Properties Needed for Acceptable Performance

Fuel Performance Required
Handling and Storage
Property Controlled for Automotive Gasoline

Volatility
Vapour
(Water/Sediments/Gum)
Pressure
Contamination
Copper Corrosion
Combustion
Engine Cleanliness
Octane Number Volatility/Distillation Range Gravity

Hydrocarbon Compostion
Sulphur
Existent Gum
Oxidation Stability
Combustion and Knock

Before combustion, air and fuel is heated up in combustion
chamber, there is an induction period before normal hot
YO
OLEUM &
n ~;
k~ e
k ; k kf D r o
ST U DI ES
fo
EN
GY
UNIV ER SIT
E TR
ER
FP
UNIT 3
flame occurs. During this induction period, oxidation of fuel

takes place with the formation of intermediate products such
as peroxides, aldehydes and peracids. Formation of
peroxides, aldehydes and peracids prevents knock due to
their ability to dissociate and promote such type of
intermediate reactions.
Knocking Tendency
High Anti-knock Value: Aromatics, Isoparaffins (highly
branched)
Intermediate Anti-knock Value: Mixed parffins e.g.
isoparaffins with little branching, Naphthenes.
Low Anti-knock Value: Paraffins
Combustion Chamber Deposits

Deposits are formed by
Incomplete Combustion
Partial Oxidation
Cracking
Condensation and Polymerisation of fuel and

lubricants
May contain nonvolatile reaction products of

additives
Deposits can lead to:
Pre-ignition
Peak pressure and temperature will increase due to
apparent increase in compression ratio and poor heat
transfer due to heat insulation effect.
Loss of power due to reduction in volumetric efficiency
Exhaust valve corrosion
Spark plug fouling
39
Notes
__________________
__________________
__________________
__________________
__________________
__________________
__________________
__________________
__________________
__________________
YO
fo
n ~;
EN
ST U DI ES
UNIV ER SIT
OLEUM &
GY
Notes
E TR
ER
Refining
40
FP
k~ e
k ; k k f D r o
Volatility
__________________
__________________
__________________
Volatility of gasoline is its tendency to pass from liquid to

vapour phase. Volatility influences:
Ease of starting
Rate of warm up and acceleration
__________________
Tendency to vapour lock
__________________
Carburettor icing
Crankase dilation
Fuel economy
__________________
__________________
__________________
__________________
__________________
Ease of Starting
For a cold engine start, enough gasoline in the intake air
must be evaporated. Ease of starting depends on:
y
Fuel volatility
Engine design
Cranking speed
Engine oil viscosity
Warm Up and Acceleration

It depends on:
1.
Fuel volatility and ambient temperature
2.
Provision for thermostatical controlled hot spots. Warm

up is mainly a cold weather problem.
Vapour Lock and Percolation

Vapour lock is a function of :
1.
Volatility characteristics of fuel
2.
Fuel requirement of engine at the moment
3.
Ability of fuel pump to handle the vapour
YO
OLEUM &
n ~;
ST U DI ES
fo
EN
GY
UNIV ER SIT
E TR
ER
FP
UNIT 3
k~ e
k ; k kf D r o
4.
The temperature and pressure in the fuel system
5.
The temperature of ambient air,

temperature and barometric pressure.
underbonet
41
Notes
__________________
__________________
__________________
Measurement of Volatility
1.
__________________
__________________
ASTM D-86 Distillation
__________________
2.
Significant temperatures are
__________________
Initial boiling point
__________________
Temperature corresponding to 10% Vol.
FBP
Non-volatile residue left in the flask.
__________________
__________________
Reid vapour pressure (RVP)

Controls the volatility due to lighter ends.
TYPICAL VALUES OF VAPOUR PRESSURES
(RVP)
K g /c m
P ro p a n e
PSI
KPa
1 4 .1
200
1 3 8 2 .8
B u ta n e
5 .6
80
5 4 9 .2
M o to r G a s o lin e
0 .7
10
6 8 .6
3.
Vapour lock index (VLI)

10 RVP+ E 70
Gives better indication of vapor locking.
Carburetor Icing
It occurs due to following:
Stoppage of the fuel flow due to clogging of the jetice
Formation of ice on the walls of carburetor ventenary

which causes the engine to stall due to over-rich fuel/
air mixture
YO
UNIV ER SIT
High volatility of fuel
How is gum formed in motor spirit,

what is its impact and how is it
overcome?
Cold and humid climate are favorable for icing.
fo
n ~;
EN
ST U DI ES
OLEUM &
GY
Activity 3 C
E TR
ER
Refining
42
FP
k~ e
k ; k k f D r o
__________________
Remedial Measures
__________________
Control of fuel volatility
Providing heating of carburetor body or the intake air,

particularly during warm up period
__________________
Providing greater throttle opening during starting
__________________
By incorporation of anti-icing agents
__________________
__________________
__________________
__________________
__________________
Anti-freeze type
__________________
Surface active agents
Oxidation Stability
Gum formation takes place in storage due to oxidation/
polymerisation reaction undergone by the unsaturated
hydrocarbons and it accelerates at higher temperatures.
Gum is a rubber like resinous material and is insoluble in
later stage of formation. Sulphur and nitrogen compounds
also take part in these reactions
Gum formation is influenced by storage conditions,
temperature, access of air and light, and catalysts
particularly traces of copper.
Impact of Gum Formation

y
May cause intake valve sticking due to deposition of

Gum, and may lead to valve burning
May cause malfunctioning of carburetor float or impair

the functioning of throttle
Deposits formed in the intake may restrict engine

breathing and reduce the efficiency of hot spots resulting
in increased warm up period
It can lead to increased sludge and varnish deposits in

the engine.
YO
OLEUM &
EN
n ~;
ST U DI ES
fo
GY
UNIV ER SIT
E TR
ER
FP
UNIT 3
k~ e
k ; k kf D r o
Sulphur Compounds and Corrosiveness:
43
Notes
Most of the sulphur compounds are removed in the

manufacturing processes. If these H2S and COS are mainly
corrosive and RSH is distinctively unpleasant.
__________________
__________________
__________________
__________________
Sulphur, on oxidation, forms oxides of sulphur which react

with water to form sulphuric acid.
A direct result of leakage of unburnt fuel can be corrosion of
engine parts.
Stringent specifications are required to be followed due to
environmental considerations.
Automotive industry requirement for meeting Euro III/
IV emission standards for Motor Gasoline.
RON
MON
89
79 to continue for old cars
91
81 to be widely available
93
83 to continue for high CR cars
Benzene content
1% Max
Aromatics
40% Max
Olefins
25% Max
Lead Content
0.005% Max
Sulphur Content
0.05% Max
Oxygen Content
2.70 Max
Diesel Fuels
BIS Grades of Diesel Fuels
There are three grades of diesel:
High Speed Diesel (HSD)
Light Diesel Oil (LDO)
Marine Diesel (MD)
__________________
__________________
__________________
__________________
__________________
__________________
YO
UNIV ER SIT
CETANE NUMBER
Heavy SR Naphtha
148-204
28-42
Kerosine
204-260
45-50
__________________
LT. SR Gas Oil
250-315
45-50
__________________
Heavy Gas Oil
315-350
50-55
__________________
LT. Cycle Oil
204-343
15-20
Hydro Cracker Go
204-343
50-60
Coker Kerosene
204-340
15-20
__________________
__________________
n ~;
ST U DI ES
B0ILING RANGE C
__________________
__________________
fo
EN
k~ e
k ; k k f D r o
HSD Blending Components (Typical)
__________________
__________________
OLEUM &
GY
Notes
E TR
ER
Refining
44
FP
FUEL Performance Requirements
__________________
Performance
Handling & Storage
Property
Control characteristics
- Volatility
- Flash Points
- Flow
- Viscosity
- Corrosive constituents
- Water & sediments
- Contaminants
- Copper corrosion
- Cloud/Pour pt.
- CFPP
Combustion
- Ignition Delay
- Cetane Number
- Volatility
- Distillation Range
- Heat content
- Gravity
- Cloud & Pour Point
Cleanliness
Use
During
- Heavier constituents
- Metals
Carbon Residue on 10%, Bottom Ash

Content, Sulphur Content, Stability
Exhaust Emission Standards
- Corrosive constituents
Effect of Diesel Fuel Hydrocarbon Type Composition on its

Quality
Paraffins
Have the best combustion characteristics and highest

cetane numbers
With molecular weight of n-parrafins, cetane number

increases
Isoparaffins have lower cetane numbers than the

paraffins of same carbon numbers. With branching
cetane number is lowered.
Olefins
Olefins have lower cetane numbers than paraffins of

corresponding structures and follow similar rules of
branching
ST U DI ES
n ~;
YO
EN
GY
UNIV ER SIT
OLEUM &
fo
E TR
ER
FP
UNIT 3
k~ e
k ; k kf D r o
Presence of olefins gives rise to poor oxidation

stability.
Naphthenes follow olefins in cetane quality but are a

good deal higher than aromatics.
__________________
__________________
__________________
__________________
Impart lowest cetane number and most important factor

controlling the cetane number of cracked gas oil
Aromatics ring condensation and the side chain
branching on rings that cause molecular configuration
of lowest cetane numbers.
Ignition Quality
This is the most important property that controls combustion
process. It is measured as a cetane number which is a
measure of ignition delay and is controlled by
Fuel composition and characteristics
Engine design
Fuel and air inlet temperature
Degree of atomisation.
As a result of abnormal ignition delay, large quantities of oil

are gathered in the combustion chamber. Spontaneous
burning and detonation of this surplus fuel in combustion
chamber causes rough ignition which is termed as diesel
knock or cetane knocking.
Cetane Improver Additives

Base Diesel Cetane No. 44
Additive dozes 1.5%
__________________
__________________
Aromatics
Notes
__________________
Naphthenes
45
Increase in CN
Isoproyle Nitrate
17
n Amyl Nitrate
23
__________________
__________________
__________________
YO
UNIV ER SIT
__________________
__________________
__________________
22
Octyl Nitrate
19
fo
n ~;
EN
ST U DI ES
__________________
Cyclohexyl Nitrate
OLEUM &
GY
Notes
E TR
ER
Refining
46
FP
k~ e
k ; k k f D r o
Flow Properties
__________________
Viscosity
__________________
Viscosity of diesel fuel has an effect on handling of the

fuel by pump and injector system.
High viscosities can cause
__________________
__________________
__________________
__________________
Poor atomisation
Large droplets
High spray jet penetration
Low viscosity results in a spray which is too soft and

thus does not penetrate sufficiently. As a result
combustion is impaired and power economy is
decreased.
Lubricating oil properties of such fuels are usually poor
HSD viscosity range is generally 2.0 to 5.0 cst.
Heavy distillates, when used as diesel fuel, are generally

preheated.
Cloud Point
u
Congealing wax settles out and blocks fuel system line

and filters.
The temperature at which precipitation occurs depends

on the composition and boiling range of the fuel.
Cloud point indicates the temperature at which waxes

start precipitating.
Cold Filter Plugging Point (CFPP)

u
Cloud point being a static test does not truly represent

actual running conditions.
CFPP is defined as highest temperature expressed as

a multiple of 1 o C at which the fuel when cooled
YO
OLEUM &
n ~;
ST U DI ES
fo
EN
GY
UNIV ER SIT
E TR
ER
FP
UNIT 3
k~ e
k ; k kf D r o
under prescribed conditions will not flow through a

filter or requires more than 60 sec for 20 ml to pass
through.
47
Notes
__________________
__________________
Pour Point
__________________
__________________
Pour point gives a useful guide to the lowest

temperature at which the fuel can be cooled with setting.
Cleanliness in Use
Carbon Residue
u
Gives some indication of coke forming / deposit forming

tendencies in the engine.
Deposits are mainly carbonaceous matter, ash,

resins etc.
Type of deposits is also an important factor. Hard

abrasive deposits can do more harm than soft fluffy
deposits.
The test can also be used to detect contamination by

heavy residues.
Maintenance life and period of over-haul mainly

depends on deposit control.
Ash Content
u
Indicates the presence of small quantities of metallic

soap or volatile porphyrines.
Unburned metallic constituents have abrasive action

and cause wear by adversely affecting the nature of
deposits.
Water and Sediments

u
These may come into the fuel through contamination

during storage and handling.
They can cause clogging of filters.
Sediments cause wear and create deposits both in the

injection system and engine itself.
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__________________
__________________
__________________
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Sediment and Gum Forming Reactions (Diesel Fuel

Stability)
1.
Oxidative Gum Reactions
__________________
__________________
Alkenee + Oxygen
..
Gum
__________________
Reaction time
..
Weeks to months
__________________
__________________
2.
Acid Base Reactions
__________________
Organic acid + Basic Nitrogen Sediments
__________________
Reaction Time
Hours to weeks
__________________
3.
Esterification reactions
Aromatic Hydrocarbons + Hetrocylic Nitrogen +
Benzothiols
Multi-step Process
Sediments
Reaction Time
..
Weeks to months
These are more predominant in diesel fuel instability.
Corrosive Constituents
Sulphur Content
u
Strict emission regulations require stringent sulphur

specifications
Due to high sulphur, combustion products corrode and

also contribute to deposit formation.
Low speed diesel engines can tolerate more sulphur,

because
They are large in size and are stationary
They are high power output type
They run under relatively constant speed and load

conditions
Their operating temperatures, cooling water and

combustion zone temperatures tend to remain at
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an equilibrium rather than to fluctuate between

high and low.
Tests carried out

u
Estimation of sulphur content
Copper strip corrosion test.
Acid value
u
Total and Inorganic
Potentiometeric Acid/Base titration
49
Notes
__________________
__________________
__________________
__________________
__________________
__________________
__________________
__________________
__________________
Residual Fuels Oils

Changes in quality of fuel oils in Indian refineries are
due to:
u
Frequent changes in crude quality and blend ratios
Intake of more of heavy crudes
Introduction of various secondary conversion processes

for maximisation of middle distillates.
Components of Residual Fuel Oils

u
Long residue
Short residue
Heavy cycle oil, clarified oil from FCC
Hydrocracker bottoms
Visbroken products
TAR from thermal conversion process
Slop
Uses
u
Steam boilers
Industrial applications requiring heat
Gas turbines
Diesel engines
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Activity 3 D
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Summary of Fireside Problems Related to Fuel Quality
Effect of metals in furnace oil?

Problems
__________________
__________________
Causes
Solutions
Plugging of fuel lines

strainer and burner tips
Oxidation of the fuel to

produce acid and sludge
Addition of inhibitors and

sludge dispersants
Fuel system corrosion
Acidic, sulphur
compounds, water, sludge
Application of corrosion
inhibitors
High temperature fouling &

corrosion
Na, V in fuel form low

melting point sulphated
ash
- magnesium additives
__________________
__________________
__________________
__________________
- combination of both
__________________
__________________
__________________
__________________
- reduce excess air
Effect of Sulphur
u
Raises dew point of fuel gases
Increases formation of sulphur deposits in boiler

passages, economiser, airpreheater and chimney
Reduces efficiency by reducing permissible temperature
Accelerates formation of gum and sediments during

storage
Corrosion of process and plant equipment
Sulphur pick by product.
Effect of Metals
u
Vanadium is a major metallic impurity in residual fuel

oil. Causes corrosion in high temperature zone.
Sodium is recognised as a potential corrosion problem.
In combustion,
Na converts to
Na2O + Na2SO4
V converts to
V2O5 + V2O4
Na2 V2O5, Na2 V2O4 5V2O5
(Low melting ash deposits)
Other ash deposits are SiO2, AI2O3, Fe2O3
NaAIO2 has high melting point (3272 oF). It causes metal

spalling or breaking off of pieces of refractory due to its high
thermal expansion.
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Review Questions
51
Notes
__________________
1.
What is the significance of following tests and to what

petroleum product these are related:
__________________
Flash point
__________________
Distillation
__________________
Smoke point
__________________
Octane number
Cetane number
__________________
Viscosity
__________________
Silver corrosion
BMCI
Weathering test
Copper corrosion
Vapour pressure
2.
What specifications for Motor Spirit and HSD are

related to environmental pollution? What are the limits
for these specifications for Euro III / IV standards?
3.
What strategies are being adopted to improve these

specifications to desired ones from the present values?
What would be the impact on cost of production? (Refer
Bibliography)
4.
What streams of Process Plants in a Refinery are

utilised to produce HSD, MS, LPG and PC Naphtha?
(Refer Unit 4 & Bibliography).
__________________
__________________
__________________
53
Unit 4
Integrated Refinery and
Petrochemical Plants
Notes
__________________
__________________
__________________
__________________
__________________
__________________
__________________
Objectives
__________________
__________________
Understand the functioning of various process plants in a refinery

and their integration with one another.
Give insight into the feeds composition of various process plants

for production of finished products.
Give an overview of various off-site facilities in a Refinery.
Now a days, to minimise processing cost and optimise product

distribution, emphasis is laid on the following:
1.
Economies of scale Minimum 9-12 MMTPA refining

capacity.
2.
Refining and petrochemical plants are integrated.
3.
Feedstock flexibility To utilise low cost crudes.
4.
Supply chain optimisation from crude to products,

provides faster delivery and at lower cost.
A typical integrated refinery and petrochemical plant set

up is shown in attached block flow diagram. (Fig. 4.1)
Crude is normally received by tankers or pipelines into crude
tanks and allowed to settle for separation of water and
sludge. Then it is taken to Crude Distillation Unit (CDU)
which operates at atmospheric pressure for fractionation
into Gas, LPG, Naphtha, ATF, Kerosene, MTO, Diesel, Jute
Batching Oil (JBO) and Reduced Crude Oil (RCO). RCO is
fractionated in Vacuum Distillation Unit (VDU) to get VGO
and raw lube cuts. The raw streams from CDU are treated
in Merox, Hydrotreatment, Reforming, Isomerisation and
Fluid Catalytic Cracking plants to obtain components of
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Notes
__________________
Naphtha
__________________
Kerosen
Kerosene
__________________
Gasolene
Petro
__________________
Diesel
__________________
__________________
LPG
CRUDE
CRUDE
TANKS
CDU/
VDU
FCC
__________________
__________________
__________________
Propylene
Coker
Sulfur
Aro
Paraxylene
PP
Polypropelene
MPP
Power
__________________
FIGURE 4.1 INTEGRATED REFINERY AND PETROCHEMICAL BLOCK
DIAGRAM
finished saleable products. VGO is treated in FCCU to get

LPG, Propylene, Petrochemical feedstocks and components
for motor spirit and diesel. Raw lube cuts are treated for
removal of aromatics and wax and are hydrotreated to get
lube oil base stock. The short residue obtained from VDU
fractionator bottom is partly treated in coker unit to get
lighter value added products alongwith raw petroleum coke.
Vacuum residue can also be treated to extract out
Deasphalted Oil (DAO) and the residue left is asphalt. DAO
is treated in aromatic extraction unit, dewaxing unit and
hydrofinishing unit to obtain bright stock which is used for
Lube oils and grease manufacture. Asphalt and vacuum
residue can also be utilised for production of bitumen or as
fuel for furnaces and boilers. From FCCU, olefins, propylene,
various aromatics and naphthas are obtained which are used
as raw materials for polypropylene and aromatic
petrochemical plant. The Raw Petroleum Coke (RPC) is used
for generation of power and calcined petroleum coke. Sulphur
present in crude and various streams is converted to H 2S
during processing. In Sulphur plant, it is converted to
elemental sulphur which is sold as by-product. This also helps
in environmental protection. Hydrogen plant is installed to
produce hydrogen for meeting the requirement of various
Hydrotreatment processes.
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Integrated Refinery and Petrochemical Plants
55
Crude Distillation
Notes
Brief process descriptions have been provided (please refer

block flow diagram of CDU, VDU and SGU). This part has
three main sections.
__________________
__________________
__________________
__________________
1.
Desalting
2.
Distillation-Atmospheric & Vacuum
3.
Saturated Gas Concentration Unit (SGU)
__________________
S
G
C
Preheat 1
Desalter
Flash
Drum
Water in
Brine Out
Preheat 2
Preheat 3
__________________
__________________
Lean Gas
Other streams
from other limits
Crude in
__________________
F
u
r
n
a
c
e
__________________
LPG to Marox
__________________
Naptha to
Hydrotreater
LK/ATF
Atm
osp
heri
c
Col.
HK
Diesel
JBO
Fumace
LVGO
V
a
c.
C
o
l.
HVGO
TO FCC
Lube
distillates
Vacuum
Residue to
Belayed Coker/
Bitumen.
FIGURE 4.2 BLOCK FLOW DIAGRAM OF CDU/VDU/SGU
FIGURE 4.3 CRUDE AND VACCUM DISTILLATION UNIT IN A REFINERY
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Desalting
The crude oil is contaminated with various impurities
mainly salts of Ca, Mg, Na, CI, SO4, etc. These salts, however,
in small proportions in crude, can cause severe corrosion in
crude units, particularly in the overhead section. Several
refineries worldwide have faced emergency shutdowns or
have had to release hydrocarbons due to corrosion and
material failures. Hence, it is important to remove the salts
from crude prior to distillation. The desalters are designed
for 99% salt removal and reach less than 1 ptb (part per
thousand barrels) in desalted crude.
__________________
Crude oil received from tank farm is heated from 30 to 140150C in cold preheat trains. This is done by recovering heat
from outgoing products streams from the unit. This prepares
crude for efficient desalting. Then it is passed through a
desalter after being mixed with de-emulsifier and water
thru a mixer valve. In the desalter, crude passes through
high electric field. The salt dissolved in water settles at the
bottom as brine and desalted crude with less than one parts
per thousand barrel comes out from the top of the vessel.
Separation of water containing salt is enhanced by deemulsifier. Desalters remove salts, sludge and mud from
crude to avoid corrosion and fouling in exchangers columns
and downstream equipment.
Distillation Atmospheric & Vacuum

The desalted crude is then heated from 140 to 190 C at 25
Kg/a2 pressure by heating with a heavier hot stream. Then
it is taken to the flash drum. From the top we get lighter
components which directly go to the crude column. The
flashed crude is passed through hot preheat exchangers and
further heated from 190C to 250260C. The purpose of hot
preheat train is to recover heat from pump arounds to reduce
furnace duty. Furnace provides required heat for
fractionation in atmospheric column and crude is heated upto
385C.
The heated crude is fractionated in atmospheric distillation
column of CDU. The fractions below 165C are withdrawn
as column overheads and sent to SGU. Here mainly gases,
LPG and FRN are separated. Heavies boiling at more than
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UNIT 4
386 C are reheated under vacuum condition (to avoid

cracking) and fractionated in vacuum column of VDU.
Besides the straight run products such as LPG, Naphtha,
LK, HK and Diesel, the other distillation products are
intermediates viz. (1) Gas Oil (HAGO+LVGO+HVGO) which
become feedstock for FCC after treatment in VGOHT and
(2) VR which becomes feedstock for delayed coker. The LPG
is sent to LPG Merox unit for treatment before sending to
RTF. The FRN is directly sent to the HNUU in the aromatics
complex. The Light Kero (LK) fraction is routed as SKO to
RTF directly or via Kero Merox unit as ATF. The Heavy Kero
(HK) fraction is blended with diesel fraction. The diesel
fractions can be routed to DHT or RTF as required.
Saturated Gas Concentration (SGU)

The overhead liquid and gases from CDU, reformer and
hydrotreaters of petro-chemical complex are passed through
this plant to separate into following fractions:
1.
Gases (C 1+C 2 ) for burning into furnaces or as

petrochemical feedstock after H2S is removed in Amine
Treating Unit.
2.
LPG (C 3+C 4) for domestic and industrial use after

removal of Mercaptanes in Merox Unit.
3.
Naptha (C 5 to 165C) for sending to fertilizer or

petrochemicals plants as feedstock.
The typical streams obtained from crude oil by Atmospheric

and Vacuum distillation are given in the following table:
Fuel Gas
LPG
FRN
LK / ATF
HK
Diesel
HAGO
RCO (Atm. Residue)
LVGO
HVGO
VR
% of crude input
0.01 to 0.03%
1.0 to 1.5%
11 to 14%
10 to 11%
6 to 7%
16 to 17%
2.5 to 3.0%
2.5 to 3.5%
21 to 22%
23 to 26%
Cut range deg C

< C2s
C3C4s
C5s to 16s
165 227
227 270
270 370
370 392
<392
57
Notes
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__________________
__________________
__________________
__________________
__________________
__________________
__________________
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Product specifications and significance of the same is

given in Unit 3
Operating issues which need attention are:
__________________
__________________
__________________
1.
Crude mix and product yield pattern
2.
Corrosion impact on various equipment should be

known.
3.
Health of equipment and run length of unit is vital.
4.
Operating parameters such as pressure, temperature,

flows.
5.
Quality control of crude and products.
6.
Health, safety and environment (HSE) aspects.
7.
Energy conservation
8.
knowledge and skills of operating crews.
__________________
__________________
__________________
__________________
__________________
Diesel Hydro-Treatment
The purpose of diesel hydrotreating unit is to:
u
Remove sulphur and nitrogen
Convert olefins/aromatics to saturated compounds.
Remove contaminants like

organomettalic compounds.
oxygenates
and
The catalysts used in this plant are oxides of Ni and Mo/Co

& Mo impregnated on alumina base.
Salient Features
u
98% desulphurisation and 70% denitrification (VGO

hydrotreater).
Produce low sulphur, colour stable diesel.
Reduce aromatics and nitrogen in diesel.
Improve Diesel cetane no.
The feed to the unit consists of a mixture of SR diesel

and heavy kerosene from the Crude Unit, light coker
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59
gas oil, HCO from the Delayed Coking Unit and LCO from
FCCU
Notes
__________________
Diesel Hydrotreater
__________________
__________________
Make up H2
Ovhd.
condensor
Offgas to
SGCU
__________________
__________________
__________________
Recycle gas
Diesel
__________________
__________________
Diesel
VGO
VGO
Product
separator
LN
LN
Stripper
Hydrotreater
To waste
water system
FIGURE 4.4 HYDROTREATER BLOCK-FLOW DIAGRAM
Brief Description of the diesel hydro-treater follows.

The feed is pumped through cold and hot feed-reactor
effluent exchangers and then with recycled gas streams
through the combined feed heater. The combined feed heater
heats the feed up to the reactor inlet temperature. The
reactor consists of one vessel with two beds of catalysts,
consisting of one inert and three different types of catalysts.
Recycled gas is added as a quench between the beds to quench
the top bed heat of reaction. The reactor effluent is cooled
through a series of heat exchangers where it, in turn, heats
up the fresh feed, the stripper feed, the recycled gas and
then provides heat for generation of HP, MP and LP steam.
A wash water stream is then injected into the reactor effluent
before final cooling in the air-product condenser. From the
product condenser, the reactor effluent enters the separator.
The separator is a horizontal vessel with a water boot that
separates the recycled gas from the stripper feed and the
wash water from the stripper feed. The recycle gas goes
through a recycled gas water cooler and knockout drum to
remove heavier hydrocarbon components before entering the
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recycled gas scrubber. This scrubber is used to remove H2S

from the recycled gas by bringing it in contact with a liquid
stream of lean amine. The top of the vessel contains a water
wash section to pick up any entrained amine. The recycled
gas exits from the top of the recycle gas scrubber, and is
then mixed with makeup gas hydrogen before entering the
recycle gas compressor. The stripper feed is heated in a
series of exchangers where it in turn cools the stripper
bottoms, reactor effluent, before entering the stripper
column.
The stripper is used to remove H2S from the diesel product,
and also to separate unstabilised naphtha from the diesel
product. Both the net off gas and the unstabilised naphtha
liquid that are produced are routed to the Saturated Gas
Concentration Unit. The stripper bottom is cooled through
a series of exchangers, then further cooled by air and water
before entering the diesel product coalescer and the salt
drier which removes water prior to routing to the diesel
product blending system.
VGO Hydro-treatment
This is similar to diesel hydro-treater and is used for
preparing feed for FCC.
FIGURE 4.5 HYDRO-TREATER/ HYDRO-CRACKER IN A REFINERY
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61
Hydrogen Production and Management
Notes
__________________
Hydrogen Production Plant
__________________
Hydrogen is produced commercially using following

technologies:
(i)
__________________
__________________
__________________
Partial oxidisation
__________________
(ii) Coal gasification
__________________
(iii) Electrolysis of water
__________________
__________________
(iv) Steam hydrocarbon reforming
__________________
(v) Platforming as a by-product.

Refer hydrogen plant block flow diagram
Recycle H2
Refinery
fuel gas
Feed gas
compr.
HP BFW
Feed
purification
Steam
Generator
Steam
reformer
HP steam export
Shift & gas

cooling
Product
H2
Gas
purification
Natural gas
LPG
Main pumping section
Naphtha
(future)
Refinery general
fuel gas
Waste gas
FIGURE 4.6 HYDROGEN PLANT BLOCK FLOW DIAGRAM
Hydrogen Feed
Feed for hydrogen production plant (i) Refinery fuel gas,
(ii) saturated LPG, (iii) Natural gas, (iv) Light Naphtha.
Process Description
Feed (Refinery Fuel Gas, or Natural Gas or LPG or Hydrotreated Light Naphtha) is first mixed with recycle hydrogen
and passed through pre-treatment section. The function of
pre-treatment section is to remove sulphur in feed by
hydrogenation, in the form of H2S, and removal of chloride
by sodium aluminate, the catalyst used is CoMo or NaMo.
H2S is absorbed in Zno bed.
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If sulphur is <200 ppm, then single stage pre-treatment is

adopted. For sulphur >200 ppm, double stage pre-treatment
is used.
The De-sulphurised feed is pre-heated with steam and
passed through Nickle Catalyst packed in Vertical narrow
tubes mounted in the reformer furnance. This process is
endothermic and heat is supplied by fuel firing. Following
reactions take place:
__________________
__________________
__________________
Steam Reforming
CH4 + H2O l 3H2 + CO
CO + H2O l H2 + CO2
Water Gas Shift

CO + H2O l H2 + CO2
Steam is added in excess to promote above reactions.
Hydrogen gas produced is purified by pressure swing
adsorption (PSA) method.
PSA Cycle
One PSA cycle is built up of 2 basic phases:
Adsorption and Regeneration
Regeneration of PSA Bed

The regeneration phase is a chain of sub-phases consisting
of:
l
High to low pressure transition: Expansion
Provide purge and dump
Purging at low pressure
Low to high pressure transition back to adsorption

pressure: Repressurization.
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Hydrogen Management
Hydrogen gas in the refinery comes from
(i)
Hydrogen production plant as described above
(ii) Catalytic reformers
63
Notes
__________________
__________________
__________________
__________________
__________________
in the refinery
in the integrated petro-chemical plant
The hydrogen from both the sources is supplied to various

consumers like hydro-treatment plants etc. through high
pressure compressors and the excess gas is led to refinery
fuel gas system.
Need of hydrogen is increasing day after day for treating
the products like motor spirit, HSD, fuel oils and feeds for
FCC and other plants for bringing down sulphur.
Merox (Mercaptan Oxidation) Treatment

Process Description
Merox is the abbreviation of Mercaptan Oxidation. In this
process mercaptan is separated from hydrocarbon by
washing with caustic solution. The separated merceptan is
oxidised into disulfide form which can be disposed of in slop
stream. Organic sulphur from LPG, ATF/Kerosene and
Gasoline are removed by this process.
Hydrogen Sulfide (H2S) from LPG is removed by extraction
with regenerated lean Amine in Amine Treating Unit (A TU).
Treated LPG is passed through reactor and mixed with
caustic solution containing merox catalyst. Then it passes
through extractor to remove mercaptan. Then, it is washed
with water to remove caustic. Treated sweet LPG free of
H2S and Mercaptan is sent to storage.
In case of ATF/Kerosene and Gasoline treatment, first it is
mixed with caustic, air and catalyst and then passed to
reactor to convert mercaptanes to Disulfides, which is
separated from caustic and product in caustic sulphur.
Caustic in recycled. Sweetened product is stored in
intermediate tanks before blending into finished product.
__________________
__________________
__________________
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__________________
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Caustic Regeneration
RSH +
(oil phase)
__________________
NaOH
Aqueous
phase
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2RSSR + 2H2O
__________________
__________________
n ~;
Mercaptan gets converted into disulfides

4RSH + O2
__________________
fo
Following reactions take place
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64
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NaSR+ H2O
(Sodium Mercaptide soluble in
Aqueous phase)
Catalyst
4NaSR+02+2H2O
(Aqueous Phase)
45C
2RSSR+4NaOH
(oil Phase)
The purpose of caustic in Merox process is:

u
To transfer the mercaptane, or the thiol portion of the

mercaptane, to the aqueous phase.
To supply the alkaline environment needed for the

reaction to proceed in the desired direction.
FIGURE 4.7
MEROX TREATMENT PROCESS BLOCK FLOW DIAGRAM
This process is used for treating LPG, Gasoline and ATF.
Sulphur Recovery Plant

The objective of sulphur recovery plant is to convert H2S to
elemental sulphur.
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65
Notes
Sulphur recovery is required because of:

l
Increasing demand for environmental friendly fuels.
Increased used of high sulphur and heavier crudes in

future.
__________________
__________________
Tightening of emission standards by government/

Regulatory bodies.
__________________
__________________
__________________
__________________
__________________
Salient features of sulphur plant are:
__________________
l
Minimum sulphur recovery level of 98.7%
Ammonia destruction capability
Turndown capability 25%
__________________
__________________
Process Description
Refer sulphur plant block flow diagram (Figure 4..8)
Acid gasses from Amin Recovery Unit (ARU) and sour gasses
from sour water stripper are heated in pre-treater and burnt
in presence of regulated quantity of air from CLAUS Air
Blower in CLAUS Reaction Funance. The product from claus
reaction funance is passed thru 1st and 2nd pass condensers.
. Acid gases
from ARU
Thermal reactor
Claus reactor
CBA reactor
Condenser 2
Condenser 3
Air
Condenser 1
Sour gases
from WWSU
Liquid sulfur
degassing pit
To tail gas
incinerato
To sulphur
granulation unit
Air
FIGURE 4.8 SULPHUR PLANT BLOCK FLOW DIAGRAM
The sulphur condensed is routed to Liquid Sulphur

Degassing Pit. The unreacted vapour is passed thru claus
reactor. The vapour from the claus reactor outlet is passed
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thru 1st and 2nd pass condensers. The condensed sulphur is

taken to Liquid Sulphur Degassing Pit. The uncondensed
vapour is passed through Cold Bed Adsorption (CBA)
Reactors 1st and 2nd passes. The outlet vapour is passed
thru 1st and 2nd pass of CBA condenser. The condensed
sulphur is routed to liquid sulphur degassing pit and the
remaining gases are taken to tail gas incinerator for burning
and releasing thru high stack. Sulphur after Degassing is
taken to granulation unit from where it goes for despatch to
market. The off-gases from sulphur degassing pit is recycled
to CBA section for recovery of sulphur.
What is Claus Reaction?

When two molecules of Hydrogen Sulphide (H2S) react with
one molecule of Sulphur Dioxide (SO 2) to give elemental
sulphur in the presence of Alumina Catalyst, the reaction is
called Claus Reaction
2H2S + SO2
3/nSn + 2H2O
n=No. of atoms in Sulphur molecule.

u
1/3rd of total H2S in feed gas is burned to SO2, this SO2

reacts with remaining H2S to give elemental Sulphur
in Claus Reactor
H2S+3/20 2SO2+H2O
2H2S + SO23/n Sn+2H2O
Overall Reaction 3H2S + 3/2 O23/nSn + 3H2O
Process Variables
Air to Acid Gas Ratio
H2S/SO2 Ratio = 2:1
344C
Claus Reactor Outlet Temp

Incinerator Temperature
650+ 50C
Amine Treating Unit (ATU)

The purpose of this process unit is to remove H2S from fuel
gases to meet environmental requirements.
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Process Description
67
Notes
__________________
Refer figure 4.9 simplified block flow diagram
__________________
The fuel gas containing H2S is introduced in Middle section

of Amine Absorber Column where Lean Methyl Diethanol is
introduced near top section. By counter current flow H2S is
absorbed in Amine and sweet fuel gas (FG) free of H2S comes
out from column top. The rich Amine from bottom of the
absorber column is taken to Flash Drum where any fuel gas
carried over is separated out. The rich Amine is then pumped
through heater where it is heated by the hot lean amine
stream coming from bottom of Amine stripper. In the
stripper, Amine Acid Gas from top of the column is routed
to sulphur recovery plant along with sour gases from other
process units. The lean Amine from bottom of the stripper
exchanges heat with Rich Amine and then pumped to storage
tank through cooler for recycling to Amine Absorber.
Sweet FG
Absorption
Section
Lean Amine
FG
Regeneration
Section
Stpr
Abs
Lean Amine Header

Rich Amine Header
FIGURE 4.9
Amine Storage Section
SIMPLIFIED BLOCK DIAGRAM ATU
Process Chemistry
The circulating amine is 35% MDEA solution,
Hydrogen sulfide H2S OR HSH is a weak acid and ionizes in
water to form hydrogen ions and sulfide ions.
HSH
H+ + SH
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Ethanol amines or weak bases ionize in water to form amine

as hydroxyl ions
(CH 2OHCH 2)2NCH 3+H 20
CH2OHCH2)2NHCH3+OH
When H2S dissolves into the solution containing the amine

ions, it will react to form a weakly bonded salt of the acid
and the base.
(CH2OHCH 2)2 NCH 3+SH
(CH2OHCH2)2NSCH3
The sulfide ion is absorbed by the amine solution. Overall
__________________
__________________
(CH 2OHCH 2) 2NCH 3+H 2S
(CH2OHCH2)2NSCH3
Delayed Coking
Coker Unit
The purpose of coking unit is to produce valuable distillates
and Petroleum coke (by-product) by upgrading heavy residual
stocks from vacuum distillation and other process units
generating heavy stock. This unit is also known as delayed
coker. Slops from various other process units which do not
find proper home can also be processed in coker to get
valuable products. The feed to this unit is subjected to severe
thermal cracking thereby producing refinery fuel gas, coker
gasoline, coker kerosene, coker gas oil, coker furnace oil,
residual furnace oil and coke.
Process Description
Refer block flow diagram of coker
Feed is preheated by exchanging heat with hot streams.
Thereafter, it is heated to 250C in convection section of the
furnace before it enters the bottom section of fractionator
column. The hot cracked hydrocarbon vapours from coke
chambers top via a separator enters the zone of abovementioned fractionator column. The heavy hydrocarbon
fractions in these vapours condense in lower section of the
column and are withdrawn from bottom along with primary
feed by secondary feed pump.
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LLP Flare
Notes
Heavy cycle gas oil
Light cycle gas oil
HP flare
Vacuum
Residue
tank
Unsat gas
conc. unit
Coker
FG
distribution
system
amine
__________________
To HNUU
To LNUU
Unsat
LPG
Merox unit
To LPG
spheres
Lean amine
__________________
__________________
__________________
__________________
To flare
Coker consumption
To light slop oil tank
Rich
FO
tank
69
To heavy slop oil tank
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__________________
__________________
Amine treating
Coke
handling
system
FIGURE 4.10
__________________
To ETP
COKER BLOCK FLOW DIAGRAM
The secondary feed is heated in the remaining part of

the convection section and full radiation section of the
furnace to around 500C and enters the coke chambers
where final cracking takes place. The vapours from top of
the coke chambers is quenched with cold vacuum distillates
before it enters the separator. The liquid product
accumulated at separator bottom is pumped out as Residual
Fuel Oil (RFO).
The vapour is routed to bottom of fractionator as mentioned
earlier. From the fractionator, products withdrawn are Light
Kerosene (LK), Heavy Kerosene (HK), gas oil and coking
fuel oil (CFO). Fractionator vapour top is condensed in over
head condenser to produce gas and coker gasoline and coker
naphtha (light coker naphtha and heavy coker naphtha). The
petroleum coke is accumulated in coke-chamber, is cooled
by steam and water and thereafter removed by hydraulic
de-coking method which cuts the hard coke with high
pressure water jets. The coke is removed by grab crane. After
crushing and sizing, it is transported to store yard or sent to
coke calcination plant.
Facilities are also provided in the plant to produce LPG and
release fuel gases to fuel gas system.
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Advantages of Delayed Coker

u
Minimum investment for given value addition
Zero fuel oil generation
__________________
Coke can be used as fuel for power plant.
__________________
No catalyst cost.
Capability to process refinery slops and sludge.
__________________
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Mechanism of Coking
Cracking is a phenomenon by which large oil molecules are
thermally decomposed into smaller lower-boiling molecules:
at the same time some of these molecules, which are reactive,
combine with one another to give even larger molecules than
those in the original stock. The more stable molecules leave
the system as cracked Naphta, Kero, Diesel (LCGO), Gas oil
(HCGO) etc. and the reactive once polymerise, forming
cracked fuel oil and coke.
Fluidised Catalytic Cracking (FCC)

Fluid Catalytic Cracking has developed into a major
upgrading process in the oil refining industry for conversion
of heavy fuel oil into more valuable products ranging from
light olefins to LPG, naphtha and middle distillates. The
attractiveness of FCC process is to its flexibility to process
wide range of feedstocks from a variety of crudes and its
favourable economics of operation. The objective is to
maximise Olefins, LPG, C7 C9 aromatics, high throughput
and minimise LCO and bottoms.
Hot regenerated catalyst is mixed at the bottom of reactor
with raw feed and steam. After pre-acceleration, it is brought
in to contact with the staged feeds supplied as finely
atomised droplets. Feed instantaneously vaporises and
travels up the riser with the catalyst where conversion
reaction takes place. At the top of reactor, the vapour is
disengaged from catalyst. The vapour is sent to main
fractionating column. In this column, mainly LPG, Gasoline,
middle distillates and decanted oil are obtained. The spent
catalyst is steam stripped to remove hydrocarbon vapour and
then sent to two stage regenerators for burning coke before
it is recycled to reactor alongwith makeup catalyst to reactor.
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Air is injected in catalyst regenerator for burning coke. Water

generated in the system leaves with flue gas from Power
Recovery Train. Flue gases are sent to CO boiler and
thereafter to a clean up system to remove particulates, SOx
and NOx. ZSM additive is added to catalyst to increase LPG
yield.
Residues are also used as feedstock in RFCC.
71
Notes
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FCC
__________________
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FIGURE 4.11
FCC UNIT BLOCK FLOW DIAGRAM
Petrochemical Process Plants

Aromatics Plant
The aromatics complex is a fully integrated facility for
the production of paraxylene and orthoxylene, comprising
of platformer primarily to produce feed for main
plants.
Aromatics complex processes special cut naptha to produce
paraxylene and orthoxylene as the major products and some
other by-products which include Benzene, Light Reformate,
LPG, H2, Fuel Gas and heavies.
The Paraxylene plant consists of the following units. (Refer
figure 4.12 Aromatics Complex Block Diagram Flow).
Heavy Naphtha Unionfining Unit (HNUU)

The function of this hydrotreating unit is to treat the feed
naphtha and remove impurities like heavy metals, sulfur,
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nitrogen and olefins, which are poison for Platformer

catalyst.
Platformer Unit
The platformer unit processes hydrotreated naphtha from
the Heavy Naptha Unifining unit, stripper column bottoms,
for the production of aromatics for downstream unit
processing and separation. Major reactions taking place in
platforming unit are as follows:
1.
Dehydrogenation of naphthenes
2.
Hydrocracking of paraffins
3.
Isomerisation
4.
Dehydrocyclisation of paraffins
The spent catalyst is regenerated continuously in situ, which

takes place in Cyclemax CCR.
Xylene Fractionation Unit

Xylene fractionation unit includes a xylene column and
associated equipments to fractionate Isomar Deheptaniser
bottoms and Tatoray Toluene column bottoms into an
overhead product that is suitable as feedstock to the Parex
process unit. The column is designed to both recover
Orthoxylene into the bottom product or to minimise the loss
of Orthoxylene into the bottom products Xylene rich
overhead vapor are used as heating medium in Raffinate &
Extract . Column Reboilers & also to generate MP Steam.
Orthoxylene Fractionation Unit

This unit includes an orthoxylene column and associated
equipments for the production of a high purity orthoxylene
product and a heavy aromatic column and associated
equipments for the production of a C9-C1O aromatic
overhead stream to be used as feed to the Tatoray unit, a
sidecut stream with a 215C endpoint for use as a gasoline
blending component and a heavy aromatic bottom stream to
be used as fuel oil.
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Parex Process Unit

The process is selective adsorption of Paraxylene (PX)
on molecular sieve and subsequent desorption of PX by
a suitable desorbent. The molecular sieve is basically
Y type zeolite (alumina silica) which preferentially
adsorbs PX.
Toulene column bottoms and C8 isomerates from Isomar
section are fed to the xylene fractionation column. The
overhead product of the xylene columns are feed to the parex
unit.
73
Notes
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Feed and desorbent goes to the Parex adsorbent chambers

via rotary valve. PX gets adsorbed on the molecular
sieve and subsequently desorbed. Two streams come out
of the chambers known as raffinate stream and extract
stream.
Raffinate stream is fed to the raffinate column. Its side cut
product which is mixed xylenes lean in paraxylene, is fed to
isomer unit while the bottom product desorbent is recycled
back to Parex adsorbent chambers.
The extract stream consist of PX, Toluene and Desorbent.
PX and Toluene are separated as overhead products
in extract column (feed to finishing column) while the
bottom product Desorbent is recycled to Parex absorbent
chambers.
PX and Toluene are separated in a finishing column.
Paraxylene is withdrawn from bottom and overhead product
Toluene is recycled back to Tatoray unit.
Isomer is a catalytic isomerisation process to efficiently
convert a mixture of C8 aromatics to a near equilibrium mix
that favours PX and OX production from metaxylene and
ethyl benzene.
The Tatoray unit includes reformer splitter column, two
parallel reactor trans, stripper, benzene are toluene column.
Objective of the units is to maximise xylene production by
transalkylation of C7 and C9 aromatics.
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Notes
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FIGURE 4.12 AROMATCS COMPLEX BLOCK FLOW DIAGRAM
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Polypropylene
It is designed to produce homo, random and impact
copolymer. The main raw materials are propylene and
hydrogen. (Refer Figure 4.13 Propylene Block Flow Diagram)
The plant consists of:
1.
Purification Section: For propylene to remove

impurities like Sulphur, CO, CO 2 , O 2 ' purification
section for hydrogen and nitrogen gas before supplying
them to reaction area. Impurities like CO, CO2 from H2
and O2 from N2 are removed.
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75
Notes
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FIGURE 4.13
POLYPROPYLENE BLOCK FLOW DIAGRAM
2.
Reaction Section: Here polymerisation reaction of

purified propylene takes place in fluidised bed reactor
in the presence of slurry catalyst (TiC14, supported on
MgCl2 in slurry form in mineral oil); co-catalyst Triethyl
Aluminium, purified hydrogen and selectivity control
agent Peraethoxy Ethyl Benzoate or N-Proypl
Trimethoxy Silane in the reactor.
3.
Pelleting Section: Polypropylene (PP) resin is

transferred from reactor to product receiver using
dense phase conveying system. The conveying gas which
is a mix of hydrocarbon and nitrogen is separated from
the resin in disengaging section of product receiver. The
unreacted monomers are purged with light recycles and
sent for recovery to vent recovery system. PP requires
the incorporation of a variety of additives to aid its
processing and achieve the end use properties. The
polymer is fed into the melt pump to develop necessary
pressure for extrusion through the die plate. The
Polymer strands are palletised in underwater pelletiser
and the pellets are carried by pellet water system to
agglomerate remover where chunks and clusters are
removed. The pellets are then dried, classified
and conveyed to the blending silos from where they are
bagged.
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Vent Recovery Section: This system is designed to

recover monomer, polymer and nitrogen. All waste
flammable gases are vented to the HP or LP flare header,
which are passed through knockout pot and burnt at
flare stack burning tip.
Typical Refinery and Petrochemicals complex Product

Pattern
Propylene
2.0%
__________________
LPG
7.0%
__________________
Gasoline
8.0%
__________________
Naphtha
8.5%
Reformate (Petrochemicals feed)
9.5%
HSD/SK/ATF
48.0%
Coke
8.0%
Sulphur
1.5%
Fuel and Loss
7.5%
Typical Refinery Product Pattern

Input
Crude Oil
% of Crude
100.0
Products
LPG
2.1
Net Naphtha
5.0
MS
Others
Light Distillates
11.2
-18.3
ATF
2.6
SKO
9.0
HSD
35.1
LDO
16.0
Others
Middle Distillates
1.1
63.7
LSHS for sale
3.3
Others
7.9
Heavy Ends
11.6
Total Prods
93.6
Gross F&L
6.8
Total
100.0
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Typical Yield Pattern of FCC
77
Notes
__________________
Feed:
100%
__________________
Low S VGO
53.7
__________________
CGO
20.3
__________________
DWO
9.0
__________________
17.0
__________________
VR
Output
__________________
Gas
3.9
__________________
H2S
0.5
__________________
LPG
12.7
__________________
Gasoline
12.5
TCO
53.4
CLO
8.6
Coke
7.9
Loss
0.5
Total
100.0
Typical Yield Pattern of Delayed Coking Unit

Input = RCO
100%
Output:
LPG
2.5
Cok. Gasoline
4.5
Cok. Kero-I (LK)

Cok. Kero-II (HK)
22.5
--
Cok. Gas Oil (CGO)
24.5
CFO
14.5
RFO
6.5
RPC
16.3
GAS
6.3
Loss
2.4
Total
100.0
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Typical Yield Pattern of Hydro-treater
__________________
Input:
__________________
VGO
__________________
100.0
H2
__________________
2.0
Total
__________________
102.0
Output
__________________
__________________
__________________
__________________
__________________
H2S
1.2
GAS
1.3
LPG
3.0
LT. Naphtha
11.5
Hy. Naphtha
4.0
SKO/ATF
27.0
HSD
43.8
Bottoms
10.0
Loss
0.2
Total
102.0
Offsite Facilities and its Management

In a Refinery, 80% to 90% area is covered by offsite facilities.
Traditionally, more attention used to be given to process
units. However, with Refinery margin shrinking, stringent
safety, Health and Environmental stipulations, and
increased customer expectations, now more and more
emphasis is given for improved profitability through:
l
Improved operations
Advanced process control system
Good inventory management
Optimisation of storage facilities & other offsites.
Major offsite functions in a Refinery are:
1. Crude oil receipt

Normally crude oil is received in land locked refineries
through crude pipelines from the production source. Before
bringing the crude from oil fields, gas, water and sludge are
removed by settling and processing through desalters. In
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coastal refineries, crude oil is received through tankers.

Depending on the capacity of the refinery, crude tankage
available, draft available at receiving oil jetty, size of crude
oil tanker varies from small to very large. Quantity of crude
received in the refinery is monitored by measuring dip of
receiving tank and flow metre readings installed on crude
pipeline. India imports almost 70% of its crude oil
requirement. Due to strategic reasons, crude oil storage is
being increased from 15 days to 45 days of the refinery
capacity.
2. Crude preparation for feeding to distillation units

Though in the oil field, major quantity of sludge, water and
associated salts are removed before bringing crude to
refineries, yet some quantities of sludge and water still are
received in the refinery tanks. This is removed by allowing
the crude to settle in the tanks and draining from bottom to
the effluent treatment system. The final removal of water
associated with salts and sludge takes place in desalter in
the crude distillation unit. Unless crude preparation is done
properly, the unit performance will be affected adversely
due to fouling of pipes, exchangers, furnace tube corrosion,
corrosion of various equipments and upsets in plant
operation. This will also lead to increased fuel consumption
and loss in the units.
3. Receiving rundown streams from various units

From crude distillation unit and other secondary units, we
get various products streams, most of which are to be treated
in secondary processing units and blended in required
proportion to produce finished products which are then
dispatched to the market. Except LPG and Naptha, all other
products are blends of various streams from different units.
Depending on the capacity of refinery, number of products
marketed, types of crude oil processed, complexity of the
refinery, the tankages provided for receipt of rundown
streams varies. Facilities for water draining and
reprocessing of offspec. streams are provided. Flexibility is
also provided for alternative routing of streams incase there
is change in demand in product pattern. Light and heavy
79
Notes
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slop tanks are also provided to receive offspec. Streams

during start up, shutdown, emergencies and upsets in the
plants. The same are reprocessed in the units in a regulated
manner during normal run. By on-line blending and utilising
advanced process control, the tankage for receiving rundown
streams can be minimised. Pump stations are provided for
transfer of products.
4. Blending the rundown streams

Various straight run streams and secondary processing units
streams are mixed in suitable proportion for the production
of finished marketable petroleum products. The mixture is
circulated in the tank to make it of uniform quality. After
settling in tank for draining any water and testing the sample
in the laboratory to ensure that it meets quality
specifications, it is dispatched to market. Storage facility at
various locations particularly for MS, SKO and HSD is being
augmented. It is proposed to provide 35 days storage
capacity based on 75% utilisation factor.
5. Co-ordination with laboratory

After blending of various streams and circulation in tank,
samples of products are sent to the laboratory for testing.
Once the product meets the quality specification as per BIS
or customers requirement, then the certificate of quality is
issued by the laboratory. Thereafter, product is despatched
to market.
6. Despatch of finished products:

The certified products are stored in finished product tanks
before dispatch.
Petroleum products are evacuated from the refinery by
following modes:
1.
Pipelines
2.
Rail
3.
Road
4.
Coastal
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1.
Pipelines: Out of the above dispatch modes of

petroleum products, maximum dispatch takes place
through pipelines (60 - 70%). Pipeline systems have
following in-built advantages over other means of
transportation available for petroleum products:
1.
2.
It is the second cheapest mode of transport next to

large capacity tankers.
With advanced control system and proper
operation, it is possible that the products reach
their destination in a "refinery-good" condition.
This is so even in respect of sensitive quality control
products such as ATF, Naptha etc.
3.
Minimum transit loss
4.
Planned product movement
5.
Flexibility in operation independent of other

transportation systems. During floods and natural
calamities, it is not affected.
2.
Rail: Tank wagons are the second bulk carrier specially

constructed for this purpose and can take products to
far off places. The wagons for transporting heavy
products such as FO, LSHS etc, are provided with steam
coils for heating the product before unloading at the
destination.
3.
Road: The third mode of transportation is tank lorries

or tank trucks, which are used to supply product to
nearby locations by road. Steam coils are provided to
heat the product before unloading in case of tank trucks
for Bitumen, LSHS, FO, etc.
4.
Coastal: Tankers of various capacities are used for

dispatch of product from coastal refineries. For short
distance and small quantity of coastal product
movement, barges are used. The large capacity tankers
are the cheapest mode of transport.
The products movement of the refinery gets adversely
affected due to failure/breakdown of transport system.
81
Notes
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Flexibility to a small extent exists to switch over from

one mode to other mode. However, refinery builds up
stock in its tanks during such emergencies, to an extent
beyond which through-put of process units is cut thus
affecting the production.
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Notes
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Refining
82
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7. Flare management
__________________
__________________
__________________
__________________
__________________
To take care of emergency release of gaseous hydrocarbon,

flare headers are provided for collecting off gases from
process units and offsite areas. After seperating the
entrained liquid, the gas is burnt at high point to avoid
hazard and pollution. Three categories of flare systems are
provided:
a.
High pressure flare
b.
Low pressure flare
c.
H2S flare
8. Refinery water supply

The following important water supply systems exist in the
refinery.
1.
Fresh water supply system: This provides utility

water supply, make up to the circulating water system,
make-up to fire water supply system and make up to
drinking water treatment system.
2.
Fire water supply system: Throughout the process

units and offsites areas, the fire water supply pipeline
network is laid in the form of ring. Firewater tanks are
provided in offsites area to have an immediate supply
source for fighting any major fire. In critical areas, long
distance throw nozzles are provided.
3.
Recirculating hot and cold water system: For cooling

of hot products, this system is provided. It is having
chemical treatment system to avoid scaling and
corrosion in related pipelines and equipment. Cooling
Towers are also provided in the system where water is
cooled by evaporation before recirculation. Blow-down
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UNIT 4
in the form of leakage and manual draining is provided

to avoid build up of salt concentration. Make up water
is taken from fresh water system. In some of the coastal
refineries, once through cooling water system is used
and sea water is utilised for the cooling of products.
4.
Captive power plant: To provide uninterrupted power

and steam supply for running the pumps, compressors
and other equipment, captive power plant is provided
in the refinery. For meeting any emergency, alternative
source of power supply from outside is also lined up.
Superheated and saturated steam at various pressures
are also supplied for process units and offsites area from
this system. Steam is used for heating, stripping in
columns, atomisation of fuel oil before burning in
furnace, fire-fighting, driving steam turbines and power
generation. Fresh water is used in DM plant before
utilising in boilers for steam generation. To ensure
supply of steam and power to critical plants/equipment
in emergencies, load shedding scheme exists.
5.
Fuel oil and fuel gas system: For providing fuel supply
to process units furnaces, and boilers in captive power
plant, this system is provided. In fuel gas, mostly
methane, ethane and purged gases from hydrogen units
are used. The supply system is maintained at constant
pressure. For fuel oil, varying range of fuels from LDO
to Asphalts are used. Storage tanks, blending facilities
and pumping system are provided for supply of fuel oil
to furnaces and boilers.
6.
Hydrogen, Nitrogen and air supply systems:

Hydrogen is generated in Hydrogen plant or catalytic
reformer unit. It is utilised in hydro-treatment units. It
is a very hazardous gas to handle as the flame can not
be seen.
Nitrogen is used for catalyst regeneration, blanketing
tanks from atmospheric oxygen in the case of lubes and
other products which form explosive mixture when
coming in contact with air, and maintaining inert
atmosphere in the process unit equipment. Nitrogen is
83
Notes
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produced in generators installed in the refinery or is

purchased from outside. Air is used for utility purposes,
catalyst regeneration, decoking of furnace tubes and
instrumentation etc. It is taken from atmosphere and
compressed before using.
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OLEUM &
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Refining
84
E TR
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Review Questions for Offsites
__________________
1.
What are the important offsite facilities in a refinery?
__________________
2.
How do these facilities affect the proper functioning of

the refinery? Explain each facility wise, specially their
impact whenever there is a failure.
__________________
__________________
Review Questions for all Process Plants

1.
Explain briefly in your own works.

i.
The function of each process plant (11 plants)
ii.
Feed composition
iii. Yield pattern.

iv.
2.
Critical parameters for optimal operation
Which components of various process streams in

different process plants (% wise) are utilized for the
prouction of LPG, MS, HSD, ATF, Furnace Oil, PC
Naphtha and Fertilizer Naphtha.
85
Unit 5
Future Refining Scenario
Activity 5 A
Describe the scenario of
availability of sweet & sour crudes
in the next two decades.
__________________
__________________
__________________
__________________
__________________
Objectives
__________________
__________________
Understand Future Refining Scenario in terms of availability of

crudes, stringent specifications of various petroleum products,
dwindling refinery margins etc.
Strategies for overcoming various challenges.
Keeping in view environmental considerations, cost

optimisation, energy conservation and product quality
requirement, it is envisaged that future refineries will have
to face many challenges they will be highly complex,
integrated, diversified and fully automated.
Worldwide availability of sweet and light crude is
decreasing, therefore, future refineries will have to be ready
to process heavy and sour crudes. This will call for superior
metallurgy in the plants and pre and post treatment of oil
products leading to higher capital and operating costs. To
improve profitability and meet statutory requirements,
following actions need to be taken:
u
Distillates yield improvement
Production of high value products
Energy optimisation
Hydrocarbon loss minimisation
Effective environmental management
Product quality upgradation
Product inventory reduction
__________________
__________________
__________________
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What do you understand from

Integration of Refinery with petrochemicals/ fertilizers, power
plants? How does it improve the
Bottom Lines?
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Activity 5 B
OLEUM &
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Refining
86
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Besides conventional process units, future refineries will also

have:
u
Quality related units:
Facilities for benzene management
DHDS (Diesel Hydro-desulphurisation)
__________________
Fuel oil HDS (Hydro-desulphurisation)
__________________
Hydrotreatment.
__________________
__________________
__________________
__________________
__________________
__________________
Environment management related units:
Tail gas treatment
High efficiency SRUs (Sulphur Recovery Units)
Bottom of the barrel upgradation related unit
Computerised integrated refinery
Energy efficient processes
Diversified and integrated refinery with power

plant, petrochemicals and fertilizers
__________________
__________________
Synergy in power with fertilizer co-production
Efficient utilisation of low value refinery residue

for production of power. Power plant supplies
power and steam required in refinery.
Co-production of value added fertilizer.
No additional raw material handling and common

fire fighting facilities.
Overall economics considerably enhanced
Already under way in the USA, the Netherlands

and Italy.
Refinery of 21st century
Operate with fewer & highly educated people
Few operators grouped in a central blast proof

control room like the cockpit of modern aeroplanes.
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Future Refining Scenario
Possible employment of robots
Computerised system supervising operations

automatically
87
Notes
__________________
__________________
__________________
On-line analysers and blending
__________________
Computerised performance monitoring
__________________
Automated dispatch and offsites operations
Flexible work hours
__________________
In the new refineries, following technology gaps and to be

covered:
u
Reduction of S (sulphur) from MS, HSD and FO.
Reduction of FO production and increase in distillate

production to 85%+.
Plant/ equipment should require less space.
Review Questions
1.
2.
What modifications would be needed in refinery process

plants for
-
Changing over from sweet crude to sour crude
Technological improvements/additions for meeting

future more stringent specifications of HSD and
MS. So as to conform to Emission norms.
To increase/improve profitability.
What do you understand from flexibility of Refinery

operations in the competitive environment?
__________________
__________________
__________________
__________________
89
Unit 6
Advances in Petroleum
Refining
Note
__________________
__________________
__________________
__________________
__________________
__________________
__________________
Objectives
__________________
__________________
__________________
Understand in a generic fashion advances in refining process

technologies
-
For making eco-friendly products
For value addition to improve the bottomline
For best practices in refining operations
For energy optimization
Various issues faced by the refining industry have led to

many major developments in this area. The challenges are:
1.
Crude oil is becoming heavier and higher in sulphur and

metal content.
2.
Reduced growth in fuel oil demand.
3.
Rapid growth in light/middle distillates.
4.
Stringent environmental regulation for cleaner

products/processes and demand for quality products.
5.
Declining refining margins
6.
Improved engine design/automobiles need better quality

fuel and lubricating oils.
Advances in refining technology can be broadly divided into

the following categories.
1.
Improved and integrated refining

u
Production of better quality products
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Residuation in residues/heavier ends
What
are
known/proven
improvements as on date, in
Refining Process Technologies?
Management of power and utilities.
__________________
2.
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Activity 6 A
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Refining
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Value addition
u
Petrochemicals production
Better quality and increased lube oil production
__________________
Power generation from heavier petroleum products
__________________
Speciality chemicals production.
__________________
__________________
__________________
__________________
__________________
__________________
__________________
Improvements are taking place in many areas. Some of them

are listed below:
u
Distillation
Fluid Catalytic Cracking (FCC), Resid Fluid Catalytic

cracking (RFCC).
Delayed coking Needle coke manufacturing,

VisbreakerSoaker Technology.
Hydro processing
Hydro treatment of various streams including

residues.
Hydro cracking
Super Oil Cracking (SOC) of heavy distillates to get 90%

conversion to distillates.
Mobil distillate Dewaxing (MDDW) to upgrade

heavy fuel oil to high quality distillate and gas yield of
93- 95%.
Isomerisation
Catalytic Reforming
Alkylation
Etherification
Power generation by petroleum residue and coke by

using Gasification Combined Cycle (GCC) technology.
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UNIT 6
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Advances in Petroleum Refining
91
In this process alongwith power, steam and H2 can be

produced which are required in the refinery.
Notes
__________________
__________________
More and more use of information technology.
Modelling simulation are being used for:
__________________
__________________
__________________
Information Gathering, Decision Making and

Business Profitability.
Accurate process models for different processes
(e.g., FCC, Hydrocracking, Cat Reforming, etc) are
being developed and increasingly used for
optimization, trouble shooting, design and optimal
control and technology development.
Typical application of information technology in a
refinery
Guide logistic
planning
Refinery
planning
Primary
logistic
management
Refinery
scheduling
Primary
logistic
management
Secondary
logistic
management
Significance of process modelling

Trouble
shooting
Pilot plant
scale up
Reactor
design
Catalyst
health
monitoring
Modelling
and
simulation
Operator
training
Catalyst
selection &
optimisation
Process
optimisation
Feedstock
selection
Refinery integration and value addition strategies
Small and medium refineries
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Activity 6 B
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Refining
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Integration with speciality chemicals for value

addition
__________________
Anode grade coke, needle coke production
__________________
Microcrystalline wax production
Alpha-olefins production
What are various routes for value

addition in Petroleum Refining?
__________________
__________________
__________________
__________________
__________________
__________________
Larger refineries
Petrochemical integration and speciality products
Integration of refining and power generation

IGCC Technology
Lubes and fuel integration
__________________
__________________
u
Other major strategies of integration
Integration with IT
Process simulation and optimisation
Advanced control and hierarchical control systems
Review Questions
1.
Explain the following processes and relate the same to

the relevant products:
-
Isomerization
Alkylation
Etherification
DHDS
Catalytic reforming
Catalytic cracking
Thermal cracking (Refer Bibliography)
2.
Explain the known/proven processes of Hydrogen

Generation from heavy residues/petroleum coke/ coal
bed methane?
3.
How is IT utilised for improved/on-line performance

monitoring of refineries?
93
Unit 7
Hydrocarbon Loss
Minimisation
Activity 7 A
i.
What should be ideal losses

in any Process Control?
__________________
__________________
__________________
__________________
__________________
__________________
Objectives
__________________
__________________
Understand the significance of losses in a refinery and their impact

on profitability
Understand sources/areas of losses and measures adopted by
the refineries for their reduction.
During the processing of crude petroleum products, handling

and dispatches from refinery, hydrocarbon losses take place
on various accounts. Efforts are to be made to bring the loss
to a level of less than 0.3% of crude processed. Auditing of
the systems and operations will lead to continuous
improvement.
Following areas need to be monitored/looked into:
A.
B.
__________________
Apparent losses
i.
Measuring devices in storage tanks and custody

transfers for proper accounting
ii.
Automating road/rail dispatch facilities.
Real losses
i.
Vapour recovery from flare and product loading

facilities
ii.
Handling of light hydrocarbon slop in process unit

and offsite area in closed blow down system
iii. Conversion of fixed roof tanks to floating roof tanks

for low flash products including diesel and use of
proper type of roof seals.
__________________
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What are international

standards for Refinery
Losses? What methods have
been adopted in Indian
refineries to bring down the
losses to International
standard?
ii. What is BS&W? How is it

related with losses in Refining
operations?
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Activity 7 B
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Refining
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iv.
Automatic tank gauging
v.
Use of proper mixers in crude tanks for minimising

sludge formation and modern method of removal
and recovery of only sludge/oil to reduce loss
vi.
Minimising slop generation to reduce evaporation

loss in slop handling system
__________________
vii. Close monitoring of BSW in crude processed to

avoid plant upsets and increased losses.
__________________
viii. Routing of all sour gases to sulphur recovery unit
__________________
ix.
__________________
Routing of off gases from vacuum column to

furnaces.
__________________
__________________
__________________
__________________
__________________
__________________
Review Questions
1.
What will be the order of magnitude of savings in a six

million tones per year capacity refinery, if the losses
are reduced by 0.2%, cost of crude being $ 25/barrel?
95
Unit 8
Energy Conservation
Activity 8 A
i.
What strategies have been

adopted to optimize energy
consumption.
-
For old refineries
For grass-root refineries
__________________
__________________
__________________
Objectives
__________________
__________________
__________________
Appreciate the role of/ urgency for energy conservation and

optimisation of energy consumption in refining industry.
Get a generic idea of various strategies adopted for energy

optimisation.
__________________
__________________
__________________
__________________
Conservation of oil and gas has assumed greater importance

in view of the emphasis on demand side management of
energy. Average fuel loss in the refineries in India during
200001 was 7-35% which is higher compared to global levels
(of similar configuration).
Energy optimisation for a refinery begins early in the
development and design stage with the establishment of a
set of energy saving guidelines applicable to the project. Some
of the areas given below need to be looked into:
1.
Integration of heat exchange system of the units to

utilize the heat from hot stream of another unit crude
distillation unit and vacuum distillation units are heat
integrated.
2.
Optimisation of heat exchangers train use of pinch

technology.
3.
Direct hot feed from one unit to another unit without

passing through intermediate tanks.
4.
Energy efficient processes/equipment such as furnaces,

pumps, exchangers etc. Provision of air preheter in
furnace.
5.
Proper insulation of hot products and steam lines.
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How do DDCS and advanced

process controls help conserve
energy?
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Activity 8 B
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Optimisation of
i.
Reflux ratio in distillation process
ii.
Solvent feed ratio in extraction process
7.
Use of soaker technology for visbreaking.
8.
Use of microprocessor based control system alongwith

DDCS (Digital Distributed Control System) and
advanced process control.
9.
Heat recovery from process streams for heating colder

process streams/ boiler feed water.
__________________
__________________
__________________
__________________
__________________
__________________
__________________
10. Power generation in new refinery will be through

combined cycle operation integrated with gasification.
11. Steam system High pressure steam will be cascaded
down to lower level by back pressure turbines either
generating power or coupled with various key process
compressors and pumps. Pressure reduction of steam
through a control valve will be minimised.
12. Minimise leakage through glands/seals of pumps,
compressors and turbines.
13. Low level heat recovery.
14. Soot blowers for convection section of furnaces to
improve heat recovery in furnaces.
15. Steam generation from hot streams.
16. Benchmarking, gap analysis and setting targets.
17. Energy audit for continuous improvement of energy
performance.
Review Questions
1.
How does energy consumption at Indian refineries

compare with best run refineries over-seas? Express
this in energy consumption indices like
-
EII (Energy Intensity Index)
NRG Factor in MBTU's per NRGF for fuel + loss
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UNIT 8
Energy Conservation
Explain the role of house-keeping measures for bringing

down energy consumption resulting in energy
conservation. Enumerate some important measures of
this nature which the refineries/ chemical industries
take.
97
Notes
__________________
__________________
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99
Unit 9
Gross Refining Margin
Notes
__________________
__________________
__________________
__________________
__________________
__________________
__________________
Objectives
__________________
__________________
__________________
Provide an appreciation for various elements affecting GRM which

in essence is the profitability of a refinery.
Acquaint with the netback estimation method used for selection

of crude for any refinery.
Gross Refining Margin (GRM) is the differential between

the product realisation and the cost of crude processed to
obtain these products. GRM of a particular refinery will
depend upon various internal and external factors. Some of
these factors are discussed below:
Internal Factors
u
The crude mix (low sulphur and high sulphur) processed

by the refinery
The secondary processing facilities available with the

refinery which affect the product yield of the refinery
The fuel used and losses incurred in the production

processes.
External Factors
u
The international prices of various crudes and products
The demand and supply balance of various products

refined by the refinery
The duty structure prevailing in the country relating to

crude and products.
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The operating cost of the refinery includes various elements,

some of which are as under:
u
Power and fuel: Fuel is used either directly in the

refining process or to generate power and utilities to be
used in the refining process. Fuel may be purchased from
outside suppliers (like natural gas), power from
electricity board or internal refined products (like
LSHS, FO or HSD) may be used as fuel.
Chemicals and catalysts: During the refining process

of petroleum products, various chemicals and catalysts
are used. The purpose of chemicals is mainly to improve
the quality of products so as to meet the desired
specifications. Catalysts are used in various reformers
and other secondary processing facilities.
Establishment cost: This is related to the manpower

deployed and includes the salary and wages paid to staff,
overtime, bonus etc.
Repair and maintenance cost: It is incurred in various

mechanical, electrical and civil jobs carried out for the
maintenance of plant and machinery.
General administrative cost: This cost includes

expenses such as traveling. Printing, insurance and
other related overhead expenditure.
Depreciation: Operating cost includes depreciation on

plant and machinery, furniture, equipment and other
fixed assets used in the refining process towards general
wear and tear.
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What are various factors which

affect GRM?
OLEUM &
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Activity 9 A
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Refining
100
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Net Margin
The net margin is the difference between gross margin and
operating cost. This is virtually the net profit to the refinery.
Net Margin
Gross margin Operating cost.
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UNIT 9
Gross Refining Margin
101
For higher profitability, gross margin should be increased

and operating cost reduced by increased efficiency in refining
operations. Attachment 1 shows a sample calculation for
gross and net margin for a refinery.
ATTACHMENT 1: GROSS MARGIN
Explain how netback estimation

method is used for crude selection
for a refinery?
__________________
__________________
Rs/Crores
Realisation of transfer of products
Activity 9 B
4050
__________________
__________________
__________________
Cost of crude (inclusive of freight, wharfage, customs duty)

Gross margin
3720
330
__________________
__________________
__________________
Thput-MMT
3.98
GROSS margin Rs/MT
829
Margin Rs/BBL
112
Margin US $/BBL
US $ 2.30
Less: Operating cost Rs/MT
500
Net margin Rs/MT
329
Net back estimation

In the net back system, the estimated realisation is
calculated on the basis of expected yield from the particular
refinery for a specific crude. For the purpose of procurement
of crude for a particular refinery, net back estimation is used
to evaluate the suitable crude for the refinery. The crude
which is having higher net back to the refinery is normally
procured for it.
Attachment 2 gives a sample netback calculation to select
the best crude out any of seven crudes, considered. All these
7 crudes are sweet (low sulphur) crudes. F.Dos gives the
highest netback of Rs 1054/MT vs TAPIS with lowest netback
of Rs 41/MT.
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Notes
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ATTACHMENT 2: SAMPLE WORKING OF NETBACK CALCULATIONS
__________________
PROD
PRICE
__________________
CRUDE
PRICE
__________________
__________________
__________________
__________________
__________________
__________________
__________________
__________________
BRENT
BL
RS/MT
F.DOS
11987
BON. LT.
11361
11714
LABUAN
ESCRAVOS
11994
11987
TAPIS
MIRI
12859
11994
4
LPG
14599
NAP
12260
10
MS
14832
12
12
12
12
13
12
12
SKO
13617
11
11
11
11
11
11
11
HSD
14361
48
58
54
58
51
53
59
OF
10100
L.SHS
10100
RPC
5535
SULPHUR
256
SL. WAX
13851
F&L
10
12
11
10
TOTAL
100
100
100
100
100
100
100
DIST%
86.0
86.0
87.0
87.0
82.0
91.0
89.0
CRUDE
VALUE,RS/MT
11987
11361
11714
11994
11987
12859
11994
PROD
VALUE,
RS/MT
12408
12415
12454
12570
12593
12900
12780
LESS IPN
COST, RS/MT
NET BACK,
RS/MT
100
421
1054
740
476
100
606
41
686
Review Questions
1.
What are the most crucial factors and which are indeed
controllable, affecting GRM?
2.
What are various options for reducing Refining Costs

in competitive world?
103
Unit 10
Oil Accounting
Notes
__________________
__________________
__________________
__________________
__________________
__________________
__________________
Objectives
__________________
__________________
__________________
Provide a general idea of accounting methods for crude and

petroleum products and its significance.
While the physical handling of crude oil, intermediates and

finished petroleum products is done by operations personnel,
the Oil Accounting Section of the finance department of a
refinery/warehouse is responsible for correct depiction of
the quantitative and financial records pertaining to the crude
oil and petroleum products.
Quantitative accountal and correct payment of duties on
finished petroleum products is the focal area of the oil
accounting section. The following are its key functions.
1. Accounting of Crude Oil Receipts and Duty
Implications Thereon
Crude oil received under bond from port locations and rewarehoused in a refinery needs to be accounted on FIFO
basis and appropriate customs duty is required to be paid
and accounted for the quantity taken in the process of
refining. This is known as ex-bonding of crude.
2. Accounting of Manufactured Petroleum products and
Those Received for Blending, etc.
The duty liability on petroleum products arises when the
process of manufacture is completed, although the discharge
of duty obligation is allowed to be deferred to the time of
removal from the refinery/onward removal to warehouse.
Hence, tank accountal of receipts and removals is to be
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OLEUM &
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Notes
Refining
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maintained by taking dip measurements and quality testing

reports.
3. Despatch of Finished Petroleum Products
Assessment to central excise duties is invoice-based. Whether
the goods removed are duty-paid or under bond, the excise
duty liability is determined at the time of removal from the
refinery warehouse. With the invoice being the document in
support of cenvat credit claim that may accrue to a customer,
the invoice/application for duty-free removal is the
cornerstone for correct excise assessment of removals.
__________________
4. Compliance of Excise Procedure and Maintenance of

Records
The excise department tests compliance of law and procedure
primarily through the records maintained by the oil accounts
section of the assessee. For duty-paid goods, the liability
likely to arise during a working day is to be deposited in
advance through treasury challan at the bank and the deposit
credit is to be utilised in accordance with the invoices issued
for the clearances. This is done through the PLA (Personal
Ledger Account). The DSA (Daily Stock Account) is to be
maintained for opening balances, production, dispatch and
closing balances of all certified finished products of the
refinery warehouse. Intimations/declarations are to be
submitted to the range office for any act or action that may
be regarded as having an impact on revenue.
5. Material Balancing, Production Statistics and
Periodical returns and Statements
As the crude oil is processed through a combination of
distillation and blending, intermediary products arise during
the course of manufacture of certified finished petroleum
products. The control over inputs and outputs during this
refining process is achieved through the daily material
balancing done through the quantitative measurement of
tank and line-fill quantities of the crude, intermediaries and
finished products. The production statistics are correlated
to the standard product pattern and the actual distillate yield
for any particular period of time.
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fo
EN
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UNIT 10
Oil Accounting
Statutory returns as per excise procedure are filed

periodically by the oil accounts section with the range office.
Records, returns, documents, etc prepared by the oil
accounting section are open to inspection by the range office.
Letters, show cause notices, if any, are normally issued
through the oil accounts section.
Review Questions
105
Notes
__________________
__________________
__________________
__________________
__________________
__________________
__________________
1.
2.
Method and system of accounting crude and petroleum

products in a refinery?
How is the excise/customs procedure followed by oil
accounting section?
__________________
__________________
__________________
107
Unit 11
Excise and Custom Petroleum
Products
Activity 11 A
What is the present level of custom
and excise duties on crude and
various petroleum products? What
is the rationale for fixing the same?
__________________
__________________
__________________
__________________
Objectives
__________________
__________________

y
Give an overview of excise and customs procedures/formalities

as applicable.
Provide an appreciation for the manner in which custom and excise

duties affect profitability.
The removal of petroleum products manufactured in

refineries is either to direct customers or through marketing
network (warehouses/ depots/terminals, etc) for sale
therefrom. Products belonging to oil marketing companies
are also dealt through intercompany transactions.
These products are either removed on payment of excise
duty, or under bond without payment of excise duty. In the
latter case, the duty obligation on the manufactured goods
is discharged from the warehouse when it is finally cleared
for sale. In certain cases, the goods are removed under bond
to special industrial undertakings like SEBs, FCI, etc who
are licensed to deal with manufactured excisable goods
without payment of duty.
The products are removed through pipelines, tank wagon
(railways), tank lorries (oil tankers), or barges (through
waterways).
The primary raw material for finished petroleum products
is crude oil, indigenous and imported. Indigenous crude oil
attracts Nil rate of excise duty, whereas imported crude oil
attracts 10% customs duty. Indigenous crude oil is sourced
from Gujarat and Assam oilfields and from offshore oilfields
of India. Imported crude of different varieties as per
__________________
__________________
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__________________
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When is it desirable to export/

import any product based on
custom/excise duties prevailing?
OLEUM &
GY
Activity 11 B
E TR
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Refining
108
FP
k~ e
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processing requirement are brought through different ports

of the country.
While crude oil only attracts the basic customs duty, other
items of import attract additional duty of customs (equivalent
to the excise duty attracted for such items under the central
excise tariff) and special additional duty of customs on
selective basis as notified. The additional duty of customs
levied under the Customs Tariff Act and the excise duty
levied under the Central Excise Tariff Act are allowed to be
set-off as duty credit by the refineries (manufacturer) under
the Cenvat Credit Scheme of central excise. During discharge
of excise duty obligations arising on the removal of finished
petroleum products from the refineries on duty-paid basis,
the refineries use the accumulated cenvat credit in lieu of
cash payment.
Other than basic excise duty, there is a levy, on selective
basis by notification, of special excise duty, additional duty
of excise (Re. 1 per litre on Motor Spirit commonly known as
petrol and on high speed diesel oil commonly known as
diesel), and recently introduced special additional duty of
excise on MS.
Petroleum products are handled under the SelfAssessment Scheme of Self Removal Procedure (SRP) of
central excise. The excise assessee is required to take
necessary actions to be within the legal and procedural
requirement of excise and customs law, without physical
supervision of the department. At the refinery/warehouse,
the department is represented by the jurisdictional officerin-charge (superintendent) of the Excise Range Office who
has been given power of unified customs and central excise
control over imported crude oil and excisable finished
products of the refinery.
Review Questions
1.
In the event of excess refining capacity (with glut in the

market), what level(s) of production should be maintained
to meet domestic demand and export the product?
2.
What is the significance of bonded warehouse? How are

crude and products removed and accountal done?
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UNIT 11
Excise and Custom Petroleum Products
Bibliography
109
Notes
__________________
1.
2.
3.
4.
Advanced Petroleum Refining, Dr. G.N. Sarkar, Khanna

Publishers, Delhi
__________________
__________________
Reading Material of Programme on Petroleum Refining

and Petrochemical Technology, Indian Institute of
Petroleum, Dehradun.
__________________
Reading materials of programme on Refining &

Petrochemicals of various Petroleum Companies.
__________________
Petroleum Refining Engineering, W.L. Nelson, Mc.Graw

Hill.
5.
Handbook of Petroleum Refining Process, Robert A.

Meyers
6.
A layman's Introduction to Oil Refining - D.G. Crook
7.
"Managing Modern Offsite Operation" by Patrick B.

Truesdale and J. Dauglas AMOS
8.
Course contents on Refinery Loss Control by Dr. Eric

Robinson and Dr. John Miles at Singapore, 20-21st May,
1996.
References
1.
Advanced Petroleum Refining, Dr. G.N. Sarkar, Khanna Publishers,

Delhi
2.
Petroleum Refining Engineering, W.L. Nelson, McGraw Hill
3.
Modern Petroleum Refining Processes, Dr. B.K. Bhaskar Rao, IIT,

Kharagpur
4.
Advances in Petroleum Chemistry and Refining - Kennetha A. Kobe,

John J. Moketta
5.
The Chemistry and Technology of Petroleum (Mercel Dekkar), Speight

J.G.
6.
Petroleum Monthly Publication, Malaysia
7.
Hydrocarbon Processing
8.
New Challenges, Technologies Options for Refineries - IOC, R&D Report

No. 96018, March, 1996
9.
KBC Petrofine Users Manual
10.
A Layman's Introduction to Oil Refining - D.G. Crook
11.
Refinery Loss Controls - Course Manual Presented by Dr. Eric Robinson

and Dr. John Miles on 20-21 May 1996 at Singapore.
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Refining

COLLEGE OF MANAGEMENT AND ECONOMICS STUDIES (CMES)

Course Code: MB-107

Growth & Development of Refining Industry in India ................................... 1

Crude Oil and its Characteristics ...................................................................... 7

Specifications of Petroleum Products & Related Tests ................................ 23

Integrated Refinery & Petrochemical Plants ................................................. 53

Future Refining Scenario .................................................................................. 85

Advances in Petroleum Refining ..................................................................... 89

Hydrocarbon Loss Minimization ...................................................................... 93

Energy Conservation ......................................................................................... 95

Gross Refining Margin ...................................................................................... 99

Oil Accounting .................................................................................................. 103

Excise & Custom Petroleum Products ....................................................... 107

Growth and Development of

Get an overview of the growth of the Indian Refining Industry after

Know about special features of Indian Refining Industry.

Get a good idea of various challenges facing the industry in the

With the growth of industry and improvement in the living

The Important Milestones

Oil discovery at Nahorpung, Assam.

Oil Production started at Digboi, Assam.

First Refinery started at Margharita, Assam.

Assam Oil Company was formed.

Setting up of three coastal refineries by Multi

The MNCs were already marketing petroleum

Indian Oil exploration with the help of Russian

Formation of Oil and Natural Gas Commission

Discovery of Cambay oil field.

Indian Refineries Ltd (IRL) was formed in the

Oil India Ltd (OIL) was formed as a joint

Indian Oil Company formed for marketing of

The first refinery in the public sector

Indian Oil Blending Ltd A JV between Indian

IRL was dissolved and merged with Indian Oil

IOBL became part of IOCL.

Assets of erstwhile Assam Oil Co. were taken

Panipat Refinery of IOC commissioned.

2 at Mumbai (Esso & Burmah Shell)

Reader may like to draw a

Growth and Development of Refining Industry in India

Reliance Petroleum Refinery at Jamnagar,

In the five decades since independence, 16 refineries have

Future Outlook* (as per 2025 vision document)

Total Refining Capacity

* The anticipated growth in petroleum products may not take place

Refining Capacity in India as in the year 2002

Indian Oil Corporation Limited, Digboi

Indian Oil Corporation Limited, Guwahati

Indian Oil Corporation Limited, Barauni

Indian Oil Corporation Limited, Koyali

Indian Oil Corporation Limited, Haldia

Indian Oil Corporation Limited, Mathura

Hindustan Petroleum Corporation Limited, Vizag

Hindustan Petroleum Corporation Limited, Mumbai

Bharat Petroleum Corporation Limited, Mumbai

Cochin Refineries Limited, Cochin

Chennai Petroleum Corporation Limited, Chennia

Bongaigaon Refineries Limited, Bongaigaon

Madras Refineries Limited (CBR), Nagapatinam

Mangalore Refineries & Petrochemicals Ltd., Mangalore

Indian Oil Corporation Limited Panipat

Reliance Petroleum Limited, Jamnagar