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<< If you like this Book, than support the author and BuY it >>
PETROLEUM REFINING
TECHNOLOGY

Dr.RAM PRASAD
B.E.(HO~S.),M.Tech., Ph.D.
ASSISTANT PROFESSOR
DEPARTMENT OF CHEMICAL
ENGINEERING HARCOURT BUTLER TECHNOLOGICALINSTITUTE,

KHANNA PUBLISHERS
Operational Office: 4575115, Onkar House, Room No. 3-4, Ground Floor,
Darya Ganj, New pelhi-110002
Phone: 23243042 Fax: 23243043
Despatch Office:
11, Community Centre, Ashok Vihar, Phase 2
Delhi-110052. Phone : 27224179
Regd. Office:
2-B, Nath Market, Nai Sarak, Delhi-110006.
Ph. 23912380
Published by :
Romesh Chander Khanna
for KHANNA PUBLISHERS
2-B, Nath Market, Nai Sarak
Delhi- 110 006 (India)

-,*

It givesme a great pleasure in presenting the book on "Petroleum


RefiningTechnology'
.The relvant topics for working Chemical/Petroleurn Engineers in Petroleum-
Refineries have.",,
been covered.
The first chapter gives an account of theories of oil and gas formahon, methods f o
p ,
exploration and drilling for oil and gas. It highlights the development of
petroleum refininB
industry in India.
,.
<

Q All Riehfq,Regerv,ed

This book orpart thereof cannot be tmnslated or reprodued i n any form (exceptfor
review or
criticism) without the written permission of the Author and the Publishers.

The knowledgeof chemisty and compositionof crude oil isessentialin the selectionof
the
refining processes. The characteristics, constituents and classification of crude
coils have been.
discussed.in chapter 2.
Indian crudes such as Bombay l-hgh,Assam are waxy in nature. These require sped;
method for transportation. The problems related to the handling of waxy crude oils
and their
-feasible solutions have heen discussed in chapter 3.
Quality control of petroleum-productsisa necessity if the products are to give
satisfactory
wrformance to the customers. Bureau of ,lndian~Standard;
New Delhi sfandaLdizes ~rocedure
ind issues specifcationsfor eachpetroleumproducts.~efktion,methodandsignifi-eof
the
various laboratory tests have been given in chapter 4.

First Edition
Fifth Reprint :2008

Price :Rs. 185.00

Computer Typeset and Figures designed by :


Steps Computers, D-2/77, Dayd Pur, Delhi 110 094
Ph. 218-1367

Printed at.. Print India. Delhi-95


Chapter 5discusses manufacture,properties and uses of petroleum products.
Thischapter
covers LPG, naphtha, gasoline, kerosine, ATF, diesel fuel, fuel oil, hydrocarbon
solvenk " '
lubricating oils, petroleum waxes, bitumen and petroleum coke.
Petroleum refining processes have been discussed in six chapter (611). Crude ou
distillation is the first unit in the refinery and carried out in two stages-
atmosphericand vacuum,
Before discucssing these processes the removal of impurities by electrical
desalting process ha,
been discussed.The influenceof the process variables on the opera tion of a
fractionatingcolumn
?.*
and the scope for improvement have been discussed in Chapter 6.
Crude oil distilltion produces reside which is to be upgraded. Thennal
conversio~~..
processes for this purpose include visbreaking and coking. These processes have
been discussea
in chapter 7.
lh
Catalytic conversion processes use catalyst and either change carbon number or
carbon/
hydrogen ratio. The most important processes include fluid catalyticcracking,
catalytic reforming,hydrocracking,catalyticalkylation, isomerizsltion and
polymeriza tion Catalytic isom& tion
neither changes carbon number nor carbon/hydrogen ratio. These processes have been
dis-,.
cussed in chapter 8.

Finishing processes are necessary to make the petroleum products suitable for use
with
respect to performance,corrosivity, suitabilityon storage,odour etc. Various
finishing processes
such as hydrogen sulphideremoval processes, sulphur recovery processes,
sweeteningprocess-,,.
es, solvent extraction processes and hydrotreating processes have been discussed in
chapter 9.
(iv)
L@~&&@p@b*ould possess and maintain proper viscosity, flow as liquid at thehandling
and
operatingtemperature and have good thermal and oxidation stability. Lubricating
oils of various
grades are manufactured by mixing of the selected lubricating oils base stock and
additives. A
modem lube oil complex consists of vacuum distillationunit, solvent deasphalting
unit, solvent
extraction unit, solvent dewaxing unit and hydrofinishing unit. These processes
have been
discussed in chapter 10. The details on the manufacture of petroleum waxes have
also been
presented ir\ this chapter.

Chapter 11discusses the manufatture of bitumen from crude oil.

Generationof process engineershave accepted corrosion as a fact of life, an


incurablevirus
whose progress may be slowedbut never stopped. Corrosioh can reduce the lifeof
refinery units.
Chpater 12 disucsses typk and forms of corrosion and their control in crude oil
distillation,
thermal cr?cking, fluid catalyticcracking,amine gas processing,and steamand
condensatelines.
Air, water and soil are vital of life on this planet. These resources are to be
protected and
used wisely. Chapter 13 discusses air pollutions, water pollution and sludge
treatment and
disposal.

2'

1.1 INTRODUCTION
1.2 FORMATION OF OIL AND GAS
1.3 OIL AND GAS EXPLORATION
1.4 DRILLING FOR OIL AND GAS
1.5 PRODUCTION OF CRUDE OIL AND NATURAL GAS
1.6 PETROLEUM REFINING, OPERATION AND OPTIMIZATION
1.6.1 Selection of Processes for Optimization
1.6.2 Optimization in a Running Refinery
1.6.3- Refining Capacity in India

Chapter 14, highlights, designs and operation of pebbleurn processing equipments.


It is hoped that this book in its present form will be useful for the students of
chemical
engineering.

1 PETROLEUMEXPLORATION,PRODUCTION AND REF~NING

2 CRUDE OILS CHEMISTRY AND COMPOSITION


i

I will be highly grateful, if short comings of this edition inform of contents,


errors are
highlighted to me.
-Ram Prasad
K ~ ~ P W

2.1 INTRODUCTION
2.2 CHARACTERISTICSOF CRUDE OILS
2.3 CONSTlTUENTSOF CRUDE OILS
2.3.1 Hydmarbons
2.3.2 Non-Hydrocarbons
2.4 CLASSIFICATION OF CRUDE OILS
2.4.1 Characterization Factor
2.4.2 Correlation Index
2.4.3 Method of Structural Group Analysis

3 TRANSPORTATION OF WAXY CRUDE OILS


3.1 INTRODUCTION
3.2 PIPELINE TRANSPORTATION
3.3 WAXY CRUDE OILS
3.3.1 Definitions of Rheological Parameters
3.3.2 RheologicalClassification of Fluids
3.4 FLOW PROPERTIES OF WAXY CRUDE OILS
3.5 PUMPABILITY CHARACTERIS~CSOF WAXY CRUDE OILS
3.5.1 Temperature
3.5.2 Yield Stress-Model Pipeline Test
3.5.3 Flow at Restart
3.5.4 Effective Pipelie Viscosity
3.6 METHODS FOR PIPELINE TRANSPORTATION OF WAXY CRUDE OILS
3.6.1 Use of Pow-Point Depressants/Flow Improvers
3.6.2 Mechanism of Flow Improvement
3.6.3 Point of Additive kijection
3.6.4 Pour point Reduction by Additives
3.6.5 Effect of Flow Improvers on Yield Stress and Viscosity
3.6.6 lncorporation of Low Pour Point Crudes in Waxy Crudes
3.6.7 Crude Oil Conditioning
-

1-14
1
2
2
3
5
8
9

10
11

15-28
15
15
16
17
22

25
26
28
28

29-44
(vii)

4 --Q~~&JTY~ONTR
OF
OPETROLEUM
L
PRODUCTS

45-64

4.1 INTRODUCTION
4.2 CLASSIFICATION OF LABORATORY TESTS
4.3 DISTILLATION
4.4 VAPOUR PRESSURE
4.5 FLASH POINT AND FIRE POINT
4.6 OCTANE NUMBER
4.7 PERFORMANCENUMBER
4.8 CETANE NUMBER
4.9 ANILINE POINT
4.10 DIESEL INDEX
4.11 CALCULATED CETANE INDEX
4.12 CALORIFIC VALUE
4.13 SMOKE POINT
4.14 CHAR VALUE
4.15 VISCOSITY
4.16 VISCOSITY INDEX
4.17 PENETRATION TESTS
4.18 FREEZING POINT
4.19 CLOUD POINT AND PQUR POINT
4.20 DROP POINT OF GREASE
4.21 MELTING AND SEITING POINTOF WAX
4.22 SOFENING POINT OF BITUMEN
4.23 INDUCTION PERIOD OF GASOLINE
4.24 THERMAL STABILITY OF JET FUELS
4.25 GUM CONTENT
4.26 TOTAL SULPHUR
4.27 ACIDITY AND ALKALINITY
4.28 COPPER-STRIPCORROSION TEST
4.29 SILVER-STRIPCORROSION TEST FOR AVIATION TURBINE FUELS
4.30 ASH
4.31 CARBON RESIDUE
4.31.1 Conradson Method
4.31.2 Ramsbottom Method
4.32 COLOUR
4.33 DENSITY AND SPECIFIC GRAVITY
--.
4.34 GAS CHROMATOGRAPHY OF PETROLEUM GASES AND LIQUIDS
4.35 REFRACTIVE INDEX OF HYDROCARBON LIOUIDS
--4.36 LEAD IN GASOLINE
4.37 WATER SEPAROMETER INDEX (MODIFIED) (WSIM)
4.38 DUCTILITY
-

S PETROLEUM PRODUCTS
5.1 LIQUEFIED PEIROLUEM GASES
5.1.1 Composition of LPG
5.1.2 Properties of LPG
5.1.3 Production of L K
5.1.4 Uses of LPG
NAPHTHAS
5.2.1 Methods of Manufacture of Naphthas
5.2.2 Composition of Naphthas

5.2.3 Usesof Naphthas


5.3 MOTOR SPIRIT
5.3.1 Spark-Ignition Engine
5.3.2 Composition of Gasolines
5.3.3 Properties of Gasolines
5.3.4 Types of Additives Used in Gasolines
5.3.5 New Gasoline Blending Components
5.3.6 Alternative Gasoline Fuels
5.4 KEROSINE
5.4.1 Manufacture of Kerosines
5.4.2 Composition of Kerosines
5.4.3 Properties of Kerosines
5.4.4 Uses of Kerosines
5.5 AVIATION TURBINE FUELS
5.5.1 Composition of ATFs
5.5.2 Properties of ATFs
5.5.3 ATF Additives
5.5.4 Storage and Handling Problems

Y'

5.6.1 Compression-Ignition
FUELS
(Diesel) Engine
5.6.2 Composition of Diesel Fuels
5.6.3 Properties.of Diesel Fuels
5.6.4 Additives for Diesel Fuels
5.6.5 Alternative Diesel Fuels
T,~NELOILS
5.7.1 Nature and Composition of Fuel Oils
5.7.2 Properties of Fuel Oils
5.7.3 Combustion of Fuel Oils
5.7.4 BumersCharacteristics and Applications
5.7.5 Storage, Handling and Preparationof Fuel Oils
5.8 PETROLBUM HYDROCARBON SOLVENTS
5.8.1 C~ppositionof Hydrocarbon Solvents
5.6.2 Classificationof Hydrocarbon Solvents
5.8.3 Manufacture of Hydrocarbon Solvents
5.8.4 Properties of Hydrocarbon Solvents
5.8.5 Uses of Hydrocarbon Solvents
LUBRICATING OILS
,, 5.9.1 Mineral Oil-Based Lubricants
vt!'d
5.9.2 Synthetic Lubricants
5.9.3 Basic Functions of Lubricants
5.9.4 Automotive Engine Oils
5.9.5 Indushial Lubricating Oils
5.9.6 Electrical Insulating Oils
5.9.7 Jute Batching Oils
5.9.8 White Oils
5.9.9 Steam Turbine Oils
5.9.10 Metal Working Oils
5.9.11 Miscellaneous Oils
5.10 PETROLEUM WAXES
5.10.1 Types of Petroleum Waxes
5.10.2 Properties of Petroleum Waxes
5.10.3 Manufacture of Petroleum Waxes
5.10.4 Uses of Petroleum Waxes
5.10.5 Quality Requ~rements-Industry-wise/End-use
wlsr

d3w

65-176
LC
A 1 BITUMENS
5.11.1 Asphalts
5.11.2 Petroleum Bitumens
5.113 &lty Specificstiow of Bitumens
5.1 1.4 Physical and Chemical Characteristicsof Bitumens
5.11.5 Uses of Bitumens
5.12 PETROLEUM COKE
5.12.1 Types of Petroleum Cokes
5.12.2 Properties of Petroleum Cokes
5.12.3 Storage and Transportation of Petroleum Cokes
5.12.4 Uses of Petroleum Cokes

6 CRUDE OIL DISTILLATION


6.1 INTRODUCTION
6.2 IMPURITIES IN CRUDE OILS
6 3 NEED FOR DESALTING OF CRUDE OILS
6.4 ELECTRICAL DESALTING OF CRUDE OILS
6.4.1 Process Description
6.4.2 P r o m Variables
6.4.3 Typical Operating Conditions
6 5 CRUDE OIL DrsTnLATION
6 6 ATMOSPHERIC DISTILLATION OF CRUDE OIL
6.6.1 Process Description
6.6.2 Prefractionation
6.63 Typical Yield Pattern
6.7 VACUUM DISTILLATION OF REDUCED CRUDE OIL
6.7.1 Process Description
6.8 OPERATION OF FRACTIONATING COLUMNS
6.8.1 Temperature
6.8.2 Column Pressure
6.8.3 Flow Rates
6.8.4 Reflux
6.8.5 Reboiler/Stripping Ste? .
6.8.6 Stability of Column Ope; hon
6.9 IMPROVEMENTS IN FlZACTIONATINGCOLUMNS

'4. THERMAL CONVERSION PROCESSES


7.1 INTRODUCTION
7.2 THERMAL CRACKING REACTIONS
7.3 THERMAL CRACKING
7.3.1 Process Description
7.3.2 Typical Operating Conditions
7.3.3 Typicak Yield Pattern
7.4 VISBREAKING
7.5 CONVENTIONAL VISBREAKING
7.5.1 Process Description
7.5.2 Process Variables
7.5.3 Typical Operating Conditions
7.5.4 Typical Yield Pattern
7.5.5 Decoking of Furnace Tubes

177-191
177
177
178
178
178
180
181
181
182
182
184

7.5.6 Maximization of Diesel Oil Production


7.6 SOAKER VISBREAKING
7.6.1 Conventional Soaker Visbreaking
7.6.2 High Conversion Soaker Visbreaking
7.7 COKINC
7.8 DELAYED COKING
7.8.1 Process Description
7 8.2 Process Variables
7.8.3 Typical Operating Condi tions
7.8.4 Typical Yield Pattern
7.8.5 Needle Coke Processing
7.9 FLUIDCOKINC
7.9.1 Rocess Description
7.9.2 Typical Operating Conditions
7.9.3 Typical Yield Pattern
7.10 REXICOKING
7.10.1 Process Description
7.10.2 Dual Gasification Flexicoking Process
7.10.3 Comparison of Conventional and Dual Gasification Proresses
7.11 OTHER COKING PROCESSES
7.12 CALCINATION OF GREEN COKE
7.12.1 Process Description
7.12.2 Typical Calcination Data

8 CATALYTIC CONVERSION PROCESSES


8.1

INTRODUCrlnN
-

192-221
192

193
194
195
195
1%
196
196
197
138
199
200
200

8.2.1 Development of Fluid Catalytic ~ r a c h g


8.2.2 Technological Aspects of Fluid Catalytic Cracking
8.2.3 Principles of Operhtion
8.2.4 Process Description
8.2.5 Process Variables-Reactor Section
8.2.6 Process Variables-Regeneration Section
8.2.7 Feedstock Characteristics
8.2.8 Typical Operating Conditiow
8.2.9 Typical Yield Pattern
8.3 CATAI.YTIC REFORMING
8.3.1 Reforming Reactions
8.3.2 ReformingCatalysts
8.3.3 Process Description
8.3.4 Process Variables
8.3.5 Typical Operating Conditions
5.3.6 Typical Yields and Product Quality
8.3.7 Pretreatment of Catalytic Refomer Feedstock
8.3.8 Catalytic Reforming For Aromtics Production
8.4 HYDROCRACKNG
8.4.1 Applications of Hydrocracking
8.4.2 Types of I-lydrocracking
8.4.3 Hydrocracking Reactions
8.4.4 Hydrocracking Catalysts
8.4.5 Process Description
8.4.6 Typical Operating Conditions

222-266
(xi)

(4

10.3 VACUUM DISTILLATION


10.3.1 Process Description
10.3.2 Typical Operating Conditions
10.3.3 Typical Yield Pattern and Product Quality
10.4 SOLVENT DEASPHALTING PROCESS
10.4.1 Process Description
10.4.2 Process Variables
10.4.3 Typical Operating Conditions
10.4.4 Typical Yield Pattern and Feed/Product Quality
10.5 SOLVENT EXTRACTION OF LUBE OIL FRACTIONS
10.5.1 Comparison of Furfural, NMP and Phenol
10.5.2 Process Description
10.5.3 Typical Operating Conditions
10.5.4 Typical Yield Pattern and Feed/Product Quality
10.6 SOLVENT DEWAXWG PROCESS
10.6.1 Process Description
10.6.2 Typical Operating Conditions
10.6.5 Typical Yield Pattern and Feed/Product Quality
10.7 HYDROFINISHING PROCESS
10.7.1 Process Descrition
10.7.2 Typical Operating Conditions
10.7.3 Feed and Prod:lct Quality
10.8 MANUFACTURE OF PETROLEUM WAXES
10.9 WAX SWEATING-PRINCIPLESAND APPLICATIONS
10.10SOLVENT DEOILING
10.10.1Fundamentals of Solvent Deoilig
10.10.2Process Description
10.10.3Process Variables
10.10.4Typical Operating Conditions
10.10.5F i s h i n g of Waxes

8.4.7 Typical Yield Pattern


8.5CATALYTIC ALKYLATION
8.5.1 Alkylation Reactions
8.5.2 H,SO, Alkylation Processes
8.5.3 HF Alkylation Processes
8.5.4 Process Variables
8.5.5 Typical Operating Conditions
8.5.6 Comparison of %SO, and HF Alklation Processes
18.6 CATALYTIC ISOMERIZATION
8.6.1 Chemistry and Catalysts of the Process
8.6.2 UOP Butamer Isomerization Process
8.6.3 UOP Penex Process
8.7 CATALYTIC POLYMERIZATION
8.7.1 Chemistry and Catalysts of the Process
8.7.2 UOP Catalytic Polymerization Process
8.7.3 IFP Dimersol Process

9.1 INTRODUCTION
9.2 HYDROGEN SULPHIDE REMOVAL PROCESSES
9.2.1 Absorption by Regenerative Solvents
9.22 Adsorption on Solid Beds
9.3 SULPHUR CONVERSION PROCESSES
9.3.1 Claus Process
9.3.2 Selective Oxidation Processes
9.3.3 Wet Oxidation Based on Aqueous Solutions
9.3.4 Thermal Cracking of Y S
19.4 SWEETENING PROCESSES
9.4.1 Caustic Treatment
9.4.2 Solutizer Process
9.4.3 Doctor Treating Process
9.4.4 Copper Chloride Sweetening
9.4.5 Hypochlorite Sweetening
9.4.6 Air and Inhibitor Treating Process
9.4.7 Merok Processes
9.4.8 Sulphuric Acid Treatment
9.4.9 Clay Treatment
9.5 SOLVENT EXTRACTION PROCESSES
4.5.1 Edeleanu Process
9.5.2 Udex Process
9.53 Sulfolane Process
9.6 HYDROTREATING PROCESSES
9.6.1 Applications of Hydrotreating
9.6.2 Hydrotreating Reactions
9.63 Hydrotreating Process for Distillate Desulphurization
9.6.4 Hydrotreating Process for Smoke Point Improvement

10 LUBE OIL MANUFACTURING PROCESSES


10 1 INTRODUCTION
10.2 EVALUATION OF CRUDE OILS FOR LUBE OIL BASE STOCKS MANUFACTURE

11 MANUFACTURE OF BITUMENS

320-327

11.1 INTRODUCTION
11.2 SELECTION OF CRUDE OIL
11.3 METHODS OF MANUFACTUREOF BITUMENS
11.3.1 Distillation
11.3.2 Solvent Precipitation
11.3.3 Air Blowing
11.4 AIR BLOWING PROCESS
11.4.1 Process Description
11.4.2 Process Variables
11.4.3 Typical Operating Conditions
11.5 TYP!CAL REFINERY PRODUCTION
11.5.1 Cutback Bihunens
11.5.2 Bihunen Emulsions
11.6 HANDLING AND DISTRIBUTION

296-319
296
296

12 CORROSION CONTROL IN REFINING PROCESSES


12.1 TYPES OF CORROSION
12.2 FORMS OF CORROSION

328-338
2

PETROLEUMRERNlMp TECHNp4OQY

1.2 FORMATION OF OIL AND GAS

There are two theories of the genesis of petroleum: the organic theory and non-
orgMc
theory. The former holds that petroleum is of an organic origin and is the
currently
favoured proposal. It predicts limited reserves worldwide; moreover Indian reserves
are
predicted as minimal. The latter maintains that it is of non-organic genesis,
supposedly of
primordial origin. On the basis of this theory, oil reserves would be much larger
than those
predicted by the organic theory. India, oil-poor in the organictheory, is predicted
to be oil-rich
in the non-organic one.
The non-organic theory that was much prevalent earlier suggests that oil is formed
by the action 'of waikr on metallic caibides or by atmospheric radioactivity or by
cosmic
radiation. ?he rme occurrence of oil in,meteorite~,igneous dykes and in petrozoic
rocks
weighs in favour of the non-organic theory.
The organic theory which is the most prevalent today, suggests that the petroleum
was formed from remains of plants and animals that died millions of years ago and
accumulated on ocean floors. Tiny, minute marine animals and plants comprising
mainly algae,
fungi, diatoms and foraminifera used to float on the surface of the sea and were
abundant
during the Mesozoic (about 225 million years back) and Cainozoic (about 65 million
years
back) period. On the other hand, rock surface and land are continuously getting
eroded.
Broken pieces of material like sand, clay, lime are carried away by rain and
subsequentJy
depamted on beds of oceans. In millions of years the sediments pile up to a great
height
(several thousands of metres) and subsequently, pressure and temperature continue
tq rise
in *ose rocks. Shells and skeletons of dead planktong, sponges and jelly fish
sublime.on sea
bed and subsequently get buried under the piling sediments. Aerobic bacteria
present infie
ocean flgor and sediments act as scavengers and attack the organic patter. Some
complex
chemical bansformation takes place that is facilitated by the enormous
overburdeq,:pressure, rising temperature and the absence of oxidizing agent. The
process continues
through various complicated stages and chemical reactionsforming fats, amino acids,
lipids
and finally into oil and gas. Oil is produced within the temperature range of
100-200DC. Source rock when subjected to greater overburden pressure and
temperature
beyond 160C for a long period does not generate liquid oil but gas.
Amongst the different sedimentary rocks like sandstones, shales, clays and
limestones,
the clays are more suitable for formation of oil and serve as 'source rocks'. With
the piling
up of sediments, lower sediments get progressively compressed and the fluids in
them are
squeezed out. Oil formed in the clay rises up or sideways and if the rock above
is,like a
sandatme with pore spaceo, fissures and fractures, the oil tends to get accumulated
in such
a reservoir, provided this upward and sideways migration is prevented by the
intervention
of an impervious layer of rock known as cap rock from moving further. This layer
traps the
oil. In a normal oil pool gas remains at the top, oil below i t and water further
below. These
pools remain intad till disturbed by earth.
1.3 OIL AND GAS EXPLORATION

Oil exploration is a complex process. It begins with prognostication and involves


au
entire gamut of activities. m e hunt for the hydrocarbons is focused at the
favourable
or promising areas based on geological considerations. Geological survey aims at
selection
'and mapping of such areas which satisfy the criteria of being sedimentary rocks
preferably
of marine origin with the presence of anticline structures of Mesozoic (50 percent
of oil
produced belongs to this era), Cainozic (40 percent of oil produced belongs to this
era) and
Paleozic (10 percent of oil produced belongs to this era) periods.

kfikwkr;~

x ~ t ~ ~ A ~ ~ o h ; ~ AND
R b REFINING
~ a r c n o ~

Owing to the presence of fault planes and fissures, a seepage of oil to ihe surface
may take
place. The analysis of surface samples of soil, water and oil or gGy'in such
cake$'; for
detection of oil and gas is known as geochemical prospecting.
Magnetic surveys are then done. Magnetometer survey is carried out either on the
ground or from the air by air-borne magnetometer. It is based on the principle that
the
magnetic attraction on the surface depends on the magnetic intensities of the rocks
and their
distance from the surface. It helps to delineate the nature and possible dip angle
of the
subsurface rocks. Dip is the angle that a geological stratum makes with a
horizontal plane
(the horizon): the inclination downward or upward of a stratum or bed. The same
principle
can be applied to the measurement of the gravitational attraction at the surface by
a
gravimeter. These two methods together help in demarcating areas having thicker
pile of
sediments with better chances of oil.
The seismic method of oil and gas exploration involves generation of a series of
shock
waves in the subsurface and picking up the reflected waves by sensitive geophones
which
are laid along a line on the surface. The time taken for the return signifies the
velocities
through the subsurface rocks and these can be interpreted to assess the nature of
rocks and
their angle of dip.
The field studies are supported by an e q u d y elaborate testing of samples in the
laboratory. Sophisticated modern equipment like Electron Microscope, Mass
Spectrograph, X-rays Chromatograph, Nuclear Magnetic Resonance (NMR),Spectroscopy,
Infia-red, Ultra-violet and Differential Thermal Analysis (DTA) are indispensable
aids. On
the basis of all these studies, the most suitable places where oil is likely ta be
found is
selected for drilling.
1 1~ Q L ~ NFOR
G OIL AND GAS

The drilling equipment (shown in Fig. 1.1)consists of a tall huge tower called
'derrick'
anchored to the ground, engines, Qd pumps, water tanks, draw-works and many other
modules. The travelling block is suspended from the crown block (a large pulley at
the top of
the derrick). The swivel, attached by a large hook to the travelling block, can
rotate freely,
and the kelly is fitted onto this. Rotary table at the centre of the derrick floor
holds the kelly
(which has a square or hexagonal cross-section) and can be rotated at a desired
speed by
the engine. To begin drilling, the kelly is hauled up the derrick, its bottom is
fitted with a
drill bit and lowered through the rotary table until that bit is resting on the
earth. With the
starting of the engine, the rotary table rotates the kelly and the drill bit which
is pressed
hard against the earth by the weight of the drill string above, cuts and penetrates
the rock
at the bottom.
Much of the success of drilling depends on the quality of mud which is a specially
prepared
slurry of water, various chemicals and adhesives like barytes, bentonites,
xanthanite. It is
pumped through the drill column to carry out several important functions such as
removing
cuttings to the surface, cooling the bit (heat generated is due to friction),
lubricating the
bit, providing buoyancy to the drill string to reduce the hook load, retaining the
side wall of
the well from caving in, allowing to examine the hole by lowering' a variety of
instruments
and balancing the formation pressure that prevents the formation fluids from
running into
the well. With the increase in depth of the open hole, the side walls of the well
tend to collapse.
To avoid this, a casing pipe is introduced into the hole. The annular portion
between the hole
and the casing pipe is cemented. M h e r drilling is carried out with smaller
diameter bit, and
at a certain depth a smaller diameter casing is introduced and cemented in the same
manner.
v

LC.

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J

Z m

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ape 9 m m 0 E g
m

E k " "

;ilc

a m ! $

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gap

u:gg

! $ a m
m q s
e lat sr 1r n
% C a w B r ,+

E'm

$ 3
1 -". a $8' 2. goR m3 kg,pg
< q U w
0
9 C w m
g g $$
@'"
2 B $6.;

- 0

1 8 - g $ g * C P gg
m g s p
P :&g
3
5: - i g s e . * , . g g 3
c a c 8 - s l$go"*g
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clmem
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20"s

" W X
ptliwUk,

''

pores. Second limitation is,$hat,the advapcing. water f q n t


:bypaqsessjgpif~qt.~rt$n?~~of
the reservoir due to difficult :wellplacements and wexpe+g:.,geologi+ c d g u r a t
i ~ n s .
This lack of a perfect!sweep efficiency is responsible for leavingbehind crude
oil'$ -!as not
reached by water.flood.
,.
Anumber of methodsltechniques are employed to recqver the rem&ing oil. The
diffkrent
techniques may be ,broadly classified into three categories:
( a )Miscible/immiscible displacement process
o

Miscible hydrocarbon displacement (LPG enriched gas & lean gas)


Carbon dioxide injection
Inert gas injection (Nitrogen, air, etc.)

( b )Thermal recovery processes


Steam stimulatibn
Steam flooding (including hot water)
In-situ combustion
(c) Chemical flooding processes

Suifactant$olyrnei injection
Polymer injection
Alkaline flooding
Selection of a suitable EOR method requires a careful analysis of reservoir
configuration and the oil properties. Trapping and release of fluids from porous
media is
a complex phenomena. For a spe.cific system, trapping behaviour is controlled by
Ci), the pore
geometry of rock matrix, (ii) fluid-rock properties, in particular, wettability and
(iii)
fluid-fluid i n t e r a ~ o n sincluding viscosity, rock density difference,
interfacial tension
and, partition coefficient. The general properties of pore system, its shape, size
and
distribution in the rock plays an important role in trapping of oil. It is
established that (1)
Trapping of fluids occurs in unique and reproducible patterns which are controlled
by
capillary forces, (2) Nearly complete networks of interconnected equal size pores
exist
throughout the pore size distribution, (3).individual pores have good accessibility
with
adjacent pores, thereby allowing alternate paths of flow around igolated immobile
phases, (4)
Fluids can be trapped at pore constrictions for all degrees of wetting. Non-wetting
pqases are trapped in discontinuous masses whose lengths are largely determined by
interfacial tension and potential gradient. For selection of suitable EOR methods
laboratory investigation under simulated conditions of reservoir are necessary.
Mathematical models (3 phase, 3 dimension) are used to analyze the reservoir
geometry. The past
performance of the reservoir is matched to predict the performance of reservoir
under
different operating conditions. Based on these modelling studies, the most suitable
EOR
methoais selected for maximum~productionof the oil in place.
In India, the increase in crude oil production is not significant during the last 4
5
years. No new oil fields with substantial reserve is discovered. The percentage of
primary recovery in the total oilgroduction is gradually decreasing. Rate of
production from
Bombay High is reported to have already shown the declining trend. Some of the old
oil
fields of Assam and Gujarat under prevailing price structure have already reached
their
economic limit. On economic terms, both ONGC and OIL may prefer to plug the well,
pull

.:: .;,

; ~ t o ~ A n o ~ ; ~ ~ bAND
~ uRERNING
cno~
&:'A

the pipe and abandon t h e lfield. It is beWr ts use EOR meth6da after primary
recovery.
It is imperative that proper assessment of EOR potential in the country is required
for making
recovery plans. The successful application of any EOR process depends on its
viability. The
price of oil is the most important factor for how much will be produced and when.
Gas
injection may not find wideapplication in India. It is true that natural gas or
associated gas,
propane, enriched gas and lean gas are available in India. But the pressure
required to liquefy
the gas is high and it may not suit the shallow Indian reservoirs. So is the case
with air and
nitrogen gas injection. But in some reservoirs carbon dioxide could be injected.
Again it
depends on the availability of low cost carbon dioxide in plenty. It is estimated
that about
4-6 million cubic feet of CO2 is required to recover a barrel of crude oil,
Although thermal
methods predominate as most successful EOR processes, they may not be applicable on
a
large scale in India. Depq of the Indian reservoir and API values of 28 - 45
restrict the
injection of steam or hot water for additional recovery because of apparently
unattractive
cost benefit ratio. Of course in Western sector it may be successful in some
reservoirs. In-situ
combustion is the most difficult method to predict properly. Moreover, it is
economical
and successful in heavy oil recovery only. It appears that the chemical flooding
viz.
polymer flooding or surfactant-polymer flooding may prove successful in India. For
alkaline flooding, acid number of the crude must be high which is not so with
Indian crudes.
Polymer flooding method may become more popular in India not only for its easy
handling but
also for the economic returns. Surfactant/polymer flooding is required to be
assessed
properly, particularly the non-compatible nature of surfadant to various monovalent
and
bivalent metal ions and in Indian reservoimkhese metals are plenty.
The production of crude oil in India is given in Table 1.1.From a meagre 0.5
million
tonnes of oil produced from one of the oldest oilfields in the world-Digboi in
Assam, the
indigenous crude production is expected to go up to 44.45 MMTPA (million metric
tonnes
*r d u r n ) by the turn of the century. Till 1947, India used to produce around
0.5 to 1.0
MMTPA of crude oil from Digboi and Naharkatia fields of Assam. After independence
in
1947, two public sector companie~wete formed by Government of India, namely Oil &
Natural Gas Commission (ONGC)and Oil India Limited (OIL)to explore and produco oil
and
liatural gas in India from both onshore and offshore fields. Up to 1960, India was
practically depending on imported crude oil.
ONGC first struck oil in Cambay in 1958-59 and in Ankaleahwar fields (Gujarat)in
1960,
followed by oil finds in other pmta of Gujarat such as Nawagam, Ahmedabad, Mehsana,
Gandhar, Kalol, Tapti basin, 'etc. Biggest oil field struck by ONGC was Bombay High
r
offihore fielda in Arabian sea in 1974. In 1976, ONGC found a large sour gas r e s
e ~ o i at
South Bassein, south of Bombay High offshore fields. Also, gadoil was found in
smaller
quantities a t Heera, Panna, Ratna and Neelam offshore fielda in Arabian sea.
Crude production in the country has been going through fluctuating fortunes. From a
high of 34.09 million tomeu in 1989-90, it dipped to 26.95 million tomes in 1992-93
and
stayed a t that level in the following year also. But in the past couple of years
there has been
a recovery and the crude production was 33.865 million tomes in 1997-98. The
offshore
reserves account for about 63 percent of total oil produced in the country. This
reveals how
poor the country is in on shore oil reserves and how much it is dependent on Bombay
High.
The production of natural gas in the country is currently about 74 million standard
cubic
metres per day and the total gas availability for sale is about 61 million standard
cubic metres
per day.
~FTR[31;ELlM,~ERPTORATION~~ODUCTION
AND REFINING

Table 1.1 Production of Crude Oil4n &dia

r9

is used as feedstock-fonUdex unitito prPduce benzene an& toluene. Kerosine


fkacti~nsfrom
certain crudes such as Assam crude do'not meet specification on amoke point due to
higb aromatic content. To improve smoke point of these fractions, Edeleanu process
is usually
employed.

1.6 PETROLEUM REFINING, OPERATION AND OPTIMIZATION

Crude oil in its raw form has got very limited use. By adopting various refining
processes
in the refineries, crude oils are separated into a number of fractions which are
suitable for
various uses. Crude oils received from oil fields are stored in refinery storage
tanks. .From
these takes crude oil is fed to the atmospheric distillation unit. All the crude
oils are basically
mixture of hydrocarbons which can be physically separated in groups of different
boiling range
by the conventional process of distillation. The fractionation of crude oil yields
the following
streams in the order of rising boiling ranges :
Methane, Ethane and Propane mixture
Liquefied Petroleum Gas (LPG)
NaphthasfGasoline fractions
KerosindAviation Turbine Fuel (ATF)
High Speed Diesel Oil (HSD) and Light Diesel Oil (LDO)
Reduced crude oil (RCO)
Depending upon the crude oils properties and impurities present in them, the above
products are further treated to meet the required specification. Reduced Crude Oil
is further
distilled under vacuum to recover some more lighter fractions. This process
produces light
vacuum gas oil (LVGO),heavy vacuum gas oil (HVGO) and vacuum residue (VR).In order
to
meet the viscosity specification of fuel oil, heavy residues such as HVGO, RCO and
VR are
processed in visbreaking unit to reduce their viscosity. To produce bitumen, the
vaccum
residue is air-blown in Bitumen Blowing Unit. To maximize the production of middle
distillates, heavy residues such as HVGO are processed in fluid catalytic cracking
(FCC) unit,
hydrocracking unit and coking unit. Straight-run naphtha of low Octane Number is
processed
in catalytic reforming unit to enhance its Octane Number. Reformate rich in
benzenhluene

1.6.1 Selection of Processes for Optimization


Optimization is the process of determining the best poseible way of selecting the
proces.
scheme and fixing the unit capacities etc. The selection of procesdprocessing
scheme is to be
optimized considering all the objective functions. The following factors would
influence + .
decision making in the selection of processes and process scheme for a given
refinery :
Type of crude
Product slate
Product specification
~nve*tme;t and operating costs
Merits/demerits of alternative processes.
Type of crude. The tyRe of c v d e to be processed in a refinery yill have a
bearipg on t;
process scheme? For example, crudes containing high sulphur require the
iqstallation of
desulphq+ation processps/sweeteningprocesses for streams. Kerosine from Aghajari c
n
has a peculiar problem of colour dekrioragon on ptorage which cannot be corrected
by treating
in an Merox upit apd hence desulphurieatiop w i t would be req%ed. Some crudes are
I
suitable for m&ing lubricabg oils, a n d , q p ~are
e not suitable for making bitumen. In some
cases the prodpcts do not require any tieatment like some of the in9genous crudes
e+Therefore, each and every stream from the crude distillap?,n unit has to be
evaluated tol
making a suitable scheme of treatmentdsecondq processing facilities.
e o d u c t slate. The capacity of the refiney, the type (lube or non-lube) and
size oft.,
secondary groceseiffgwjb is largely governed by the product slate which jn turn is
decided
by the dem,pd of petroleum,~roducts,The process scheme is selected so as to match
with tproduct slate. b Indiq, generally the yaximization of middle distillates
is,the main criteria.
In U.S.A., the production ,of light djetillateq particularly, motor spirit is
maximized in F r '
unit by keeping high severity operations, If the objective is to maximize HSD in a
refinery
processing high sulphur crudes, it would be advantageous to provide an FCC unit
with 9
desulphurisation unit either for straight-run gap oil or cycle oils so as
to,upgrade the heavl-.
ends to the maximum poaeible extent as limited by sulphur specifications. For
extreme
maximization of middle distillates, a hydrociacker can also be considered which
upgrades t
heavy ends to the middle distillates (ATFkerosineiHSD)better than any other
knownprocess.
Yield of kerosin$HSD from a hydracracker is of the order of 80 to 85 percent as
compared
about 50 percent from FCC unit.
Product specifications. Geaerally the treatment processes are governed by tF
specifications of the products. Depending on the type of crude processed and the
quality or
streams, a judicious selection of treating processes has to be made from a simple
chustic wash
Merox sweetening units to a hydro=deeulphurisation unit. The flash point of the
midc.distillates are often relaxed, with a view to m-ize
these products. Therefore, to take
advantage of such relaxed specifications, it would be desirable to provide a
naphtha splitt
column inthe process scheme, sa that heavy naphtha can be injected into
kerosinddiesel cuts.
Investment and operating aosts, This is a very important point to be kept in view
whilfixing the refrnery capacity, selecting the processes and sizing the unit
capacities. However,
the selection of process technology at times may entirely be'governed by the
products demand
rather than by investment cost limitations. Investment costs are function of
refinery size ar.-
rw

P E 7 R r % g E U M f E X W a ~ ~ ~ E I M : T lAND
O N REFINING

i t & a s n p ~ ~ ~ ~ y t ~ f ~ h ltihe
e tm'1~1wmp1~xityi~ze6ults
:fox~
as!the capa@f increases.
~ n v 8 8 k r n ~ n ~ p e m ~ r w e s s i n g , c a p progressively
acity
go,down.h some cas$s,,apartidar
planh~siree~~~eomeieW~miud~md
k s o m e othea w e e it maypot be.ecoaomie;JI. For
example; some oil companies do not consider it economical to provide FCC Unit of
less than
0.6 MMTPA capacity. Similarly, the latest trends are to provide single crude
distillation unit
of 8 to 10 MMTPA capacity.
,
i
.-$Qxp~f$he,plants*tveconsuming high amount of fue1,ahd utilities. This aspect has
to be
kept i P ~ X i e w ~ ~ w ~ ~ s e 3 eacprocess-For
ting.
example, inxase ofhyQrgcracker, thetotal energy
c ~ n s ~ p t ' i bo spr ~ b ~ $
u.6
t times than that of Fluid catalytic cracker. Fufiher, a substantial
quantity,q&p~pSlthai~
copsumed to meet the hydrogen, requirelpent of h y & g c ~ ~ & n gThe
.
total energy consumption in a fuel refinery would.be of the order of 10 to
11percent.
One has to be cautious in the selection of new process technology keeping in viey
the
situation, location and availability of local expertise. Some of the
technol~giesfor upgradation
of the heavy residues may not be straight way made applicable @ Indian conditions.
Develop
ments like continuous catalyst regeneration may not be verJ;atractive to refineries
which
upqaSI&qaphthaf?r #e production of motor spirit ?f bqder*te o c h k q u m ~ t . ' ~
e s u l P h ~ s a tio~iof Gel oil which i s $ow being practiced elsewhere with7 the
okijedive df rMucing$ollution
in concd+qa$ed @au$+al flrei-i? rimy-not &e appli,cable+@s?in_e other situations, y
h e p
p:ol$t$m - h @ s a$$ow. HydroqackinP ddugb a "e$j yitd pmck$s fo; h&hiking'niiddle
distillates h p a soEh@dcatkdmi!llurgy
and ikgu+ea szecid operatibnd &d rnewnqnce
c a i e : ~ o c e s , o , w a@ted,forJFct hydiocrack@g"ofreeidu'es abuld call yo; s
f i & q t high
i'?vestm~tsand Gg'hop,perqkirig costs becaube df the hjrdrdgen
rkquirementh,,pa&~ularlykor
high &l@.u&des'.'R.eddced d v d e oil; fiod indigent& crucY$d because oftheir low ?
ulpRur
and metal conbl;t$ &ohla dre better suitedto thiktype of te&ology.
Me$ta/demqets
alterqdivq pyoces&ir: There may be more than qne prvess to do
the '&me m e OF operatidin. Fbr exhljk, th'e'r~are various'types of
swebtenihgl$hce~sfor
naphtha@and ultihat&ly chohh has to be & b e on the meritk &&demerits of
aeihdiyidual
processes, opkrating cpqp t+d quality of t&e pfoduct etc. Fo* extractipn of
aromatics:fiom
kerosine, apart from conventional Edelead~prdcess one coqd possibly choose
shlfolane
process or &d,hydr"dgenation in orddr to irp~rovethec'amoke'poiht. For the
extraction of
arqmatics f r ~ m t h lube
e oil distillates either furfural or phenol extraction could be adopted.
i

..

,I-

OF

1.6.2 ~ ~ t & i ? h t iin


~ an R ~ n n i n Refinery
g
dPtimization ofthe operition bf a runxi&;! refineiy is sutij&d to the influence of
various
factors. There are, some factors which are beyond refinery's control. These include
:
I
(a) c h h e mixture
(b) Type of processing units
(c) Demaqd pattern
(d) Movement constraints
(el Product specifications
E a r n a l streams
(g) Industrial relations.
Those factors which are within refinery's control are given below.
(a) To investigate the possibilities of improving over processing capacities not
only for
crude oil but also for secondary processing units.
(b) To adopt various effective measures of controllingthe erosion/corrosionin
processing
units to improve their service factors.

(c) To.plan(shut downs of vari6us unitsratoptimum time tu avoid the&@?&ed htiiitieb

consqmptions.
,,I,,
(d) Various streams obtained f ~ diffvrent
m
pftcesslirg units a i 6<ikgntilized to
produce the finishedprodncts. Several streams can be utilized in the production of
more than one product. The blenditigphttern of some products likembtor spirit and
HSD &o significantly influence the consumption of high priced intpbtted chemicals
like antiknock compounds, cetane improvers etc. This aspect should also be kept in
view while routing the different streams for production of these products.
(e) The profitability of a refinery can,be increased considerably by slight
reduction in
the bperating costs of its units. In order to achieve this, the operatjng
conditions of
the unit should be optimized by optimizing the reflw ratios of columns, excess air
in the heaters and maintaining a proper control on utilities and chemical
compositions in these units.
1

1.6.3 RefJning Capacity in India


in I?$+ as' on,\.Qi1997 stands at 61.55 MMTPA of which 58.55
MSd'I'PA is a c c b u n ~ dfor by the puljlic sector refineries @able 1.2). ~ ' ~ R
P
accduhts
L
for the
btlbce. ~jt$'the ~ngoi~~gcomh$,~ioning
of IOC'a Pqnipat re@ery,,+e,~@re~in$capacity
wh ri?ach k~67.55 ~lk'&~.'~e"el'alexpansion projectk ahd grassfoot ikfineries hive
been
planned to enhance the,rehipg capaqity in the c o m S . About 31 myion tonnes of
adqtional
&.dIAi%k 'capacityi s li~e1Ptb bki cr'@~d'ibB e ?omtry 1b9 Ftii'th: commi&i6:n$k of
a
li&ge ~riv@f$sector refine'rj. a$d completion'of the eXli+dion, p~dq-es
Public
s&&r/jdint sector r'efineries. Thi'major con9biition is e,xpected to c6rne4fi6h
riiinery
being set up at Jamnagar'by Reliance: The compii(y has heeled up thd capacity #
%refine*
to 27 MILITPA from the-earlier plan of 15,MMTPAreFnery. Among the public secp~!
efineries,
IdC's Gujarat refinery has undertaken a h.749 crore programme to exband its
~apacityby
3 MMTPA. HPCL's Visakhapatnam refinery has undertaken a Rs. 998 crore programme to
expand its capacity by 3 MMTPA. MRPL, the joint venture between HPCL and the Aditya
Birla group is expanding itsccapaditYbjr 8 MMTPAat'&e'stirhatedlcost of Rs.3490
crore. IOC
Barauni refinery has an installed capaciwof3.3 MMTPA. The capacity is primarily
limited
due to crude supply constraints from Assam oilfields. Now, the Haldia-Barauni crude
pipeline
Iins been laid and is under commissioning to supply imported crude to Barauni.
Apart from
these capacity additions in 1999, Essar's refinery atrJamnagaris likely to be
commissioned in
Xinrch 2G02. The refinery was planned with a 9 MMTPA capacity, but Essar has since
scaled
u p the capacity to 12,MMTPA.

l'hd total xefm$g.i{payjty

&p
+!

Table 1.2 Refining Capacity i n India


Company

Refinev

CapacityMMTPA
(as on 1.4. 1997),
IOC

Guwahati
Barauni
Gujarat
Haldia
Mathura

1.0

Digboi*

3.3
9.5
3.75
7.5
0.65
P p , Q L E U W E v b P R w Q M ; PblQpUGTION AND REFININ0

*AOC,Digboi was taken over by the government in October 1981 and merged with IOC
The refinery production and consumptionof petdeqm+productsi s giyen$Tables 1.3-1.4.
In In$a the consumption of light.and heavy distillateshave beensfagnatkdgver
t$epe.eod of
last Siie years. How+,
the demand foi midd1,e ,&atjljates'ia'~'&ei$big's@ong'50
.ip
h$
r e c k t times. In order to meet :the' increasing d.em?d for, middle disFla%s:!60-
65%),'the
second& and tertiary processink f@$ilities'
. &e
. becoming$& bf1;1.bd.y~
yelink$
. . cpmplqxts.
. .

'

.::....,

.. ..

'

H 4 t o pmqesscrud? bib,?=
gpttihgg+temati&awti6n:L d$&l?*%~+&<~j$?s ki+
couM 'increase i h e r e f i n e ~
efficienqies.'@e n,eedto co'nv* bottomcif:?+eb,arrelil:iii$ocleiitofuel
as~~mes,si~ific.mtim~;twce,
ipIn,$a p@icul,+lyj@ 09pool 4aficit,c?nt$etddb$lwh a&d
India costiflues to dep,pnd feafly on impoited crude 'oil. '&e.,e$sting refineries
skbuld
therefore upgrade,t&eirtechnologies, o p ~ i z e s n e r g y : c @ s ~ p*dt i
~fmpro+e&fficiencyof
furnaces and process equipmeritsto kclude the f1exib;iQt.yt;d p+c&g the broad
spect,mm
.
. .c ~ d e
oil.
Tablg 1.3 Refinery Production in India
(In Thousand Tonnee)

ATF

3.
.-

HSD
LDO
Heavy ends
Furnace oil
LSHSHSHWRFO

I
[

1001
7371
1108
7907
4041
2079

1519
14624
1177
10016
3791
4164

. ... .

1801
$j85
1609
18196
4879
4550

'

1,

1636
18289
1453
13389
6358
4044

Table 1.4 Consumption of Petroleum Products in India


(In Thousand Tonnes)
PETRQLCUM1REFINING TECHNOLOGY

..

1.S. Abbas, p e noxi-orgapic theory of the genesis of petroleum, Current Science,


Vol. 71,
NO,9, ppF877-684 (1996X,
"
2. P. Dutia, The oil refining industry in India, Chemical Industry Digest, pp. 103-
110
(hhrch 1997).
3. A. Borthakur, K.V. Rao and B. Subrahmanyam, Recent trends in enhanced oil
recovery
by chemical methods, Chemical Engineering World, Vol. XXXII,No. 4, pp. 83-86
(1997).
4. A.X'~r0r.a:Status. &projectionsin the oil refining sector, Chem. Engg. Progress,
Vol.
XXXE.N,o. 4, pp. 87-88 (1997).
5. Aqonymous. India still lagging potential as major player on worid energy
markets, Oil &
Gas J., pp. 19-22 (Feb. 12,1996).

CRUDE OlLS CHEMISTRY AND COMPOSITION

2.1 INTRODUCTION
Petroleum, etymologically, means rock oil. It is natural organic material composed
principally of hydrocarbons which occur in the gaseous or liquid state in
geological traps. The
liquid ,part obtained after the removal of dissolved gas is commonly referred fto
as crude
petroleum or crude oil or simply crude.
Crude oil o c m in many different parts of the world, and its structure and
composition
variestaccording to its source to such an extent that each producing area, and
field, and
reseryoir bears its own profile just as individually as finger prints identify man.

2.2 CHARACTERISTICSOF CRUDE OlLS


Crude oil has been defined as a naturally occurring mixture, consisting
predominantly of
hydracarbons andor of sulphur, nitrogen andor oxygen derivatives of hydrocarbons,
which is
removed &om the earth in a liquid state or is capable of being removed. Crude oil
is commonly
accompanied by varying quantities of extraneous substances such as water, inorganic
matter
and gas. The removal of such extraneous substances alone does not change the status
of the
mixture as crude oil. If such removal appreciably affeds the composition of the oil
mixture,
then the resulting product is no longer crude oil.
Crude oils range widely in their physical and chemical properties. Typical
properties of
several crudes are given in Table 2.1. Crude oils are brownish (light oils having
large amounts
of distillates) to brownish black (heavy oils) in colour. Heavy oils have an
unpleasant odour
(garlic like) due to the sulphur compounds, while the light crudes have pleasant
aromatic like
smell. Though general, this is-not $ways true. Data for a considerable number of
crude oils
indicate the specific gravities between 0.73 id'
1.02; most crudes gaving specific gravities
lying -&tween 0.80 and 0.95. These values are for surface conditions of temperature
and
pressure. The kinematic viscosities vary from 0.7 to 1300 cSt a t 37.8"C; the bulk
of the values
being in the range of 2.3-23 cSt.
In terms of elements, crude oils are composed principally of carbon and hydrogen.
Of the
other elements present, sulphur, nitrogen and oxygen appear as heteroatoms in
hydrocarbon
derivatives, some of which occur as petroporphyrins, i.e. complexes involving
traces of metals
(mainly vanadium and nickel). Carbonthydrogen ratio is usually between 6 and 8. A
wide range
of metallic elements have been found, generelly as traces, in the small amount of
ash obtained
by burning many crude oils. The elemental composition of crude oils is given in
Table 2.2.
PETROLEUM REFININGTECHNOLQGY

16

2.3 CONSTITUENTS OF CRUDE OILS

The main constituents of crude oils are hydrocarbons. The proportions of the
different
types of hydrocarbona vary from one crude oil to another. Many members of each type
are
presegt. Naphthenic acids, complex nitrogen compounds, and mercaptans account for
some of
the-yxygen, nitrogen and sulphur present in crude oils. In additioq, the resinous
and asphaltic
substances present in some crudes contain oxygen and sulphur. Inorganic sulphur can
be
present as hydrogen sulphide (HzS) dissolved in the oil. Crude oil also contains
trace elements
suth as metals, mostly in -small quantities-some contained in water impuritieg and
some
existing as complexes in the hydrocarbon phase.
Table 2.1 Typical Properties of Crude Oils

~ h l b r b i ,pi,iphyrin&,a+e
~~~.
tj.eeII'1y$,d8 &.sinam,;af d @ + ~ . ~ # & ~~.. ~ &
-. l...
& l A,%.
~ P %C.$ $ e
compoun$s indicate a contributio? from,plant 6Ou,Kei3, a
~
o
~
~
~
pr $!uk ~ ~ ~
Hi$tp~ji,dnd
hob$ljly B ~'ed$cin&eriiri~iiibnf:
@&l$pi
iio@hynnshm%%dn
i.a *&&: bd+it.i$b0$ b o w n h b t c61p"hli
$~vh~s':inkP+$~<&{~&~#&,
&egikihblebomilaht tjbdrees: 1 s o j x i d hy&r:,brbo$s 8'iG been
r.e~<&~ed:th'e'~:bFdd$&%ai
have structurkri tjrpital of substaixes'formea biologically: Other
hydrocarboiii'st~u~tu~es~~ith
. biol'dg;icali*ni&,
li'a"sbeen.detecb'd. .', . ,- <;:: :, . ; : . , ;: . <.;; <:.;
:;:<.Th&
w&&p, &#b&ted .with ?oil:ma.gas & c c u m y l ~ t ~$8:
o :usually
n~
- jn&&$aljris~lifiB)i
and
appears Mmany fnstmces to' be modified$eaWater,tkepnncipa1:diKere'nc~s~bei~
a'deficiency
in sulphates, relatively less magnesium and commonly.,greaterconcentration than
normal sea
water. Traces of hydrocarbons andorgrtllic acids are pksent.
:

2.3.1 Hydrocarbons
Hydrocarbons are compounds composed solely of hydrogen (H) and carbon (C). The main
types of hydrocarbons present in crude oils are alkanes, cycloalkanes, arenes and
hybrids
involving combination of these types. They range widely in boiling point, and many
cannot be
distilled under atmospheric pressure without breakdown.
Alkanes.These are open-chain saturated hydrocarbons. They are also known
asparaffins.
They can be divided into two types:
Straight chain alkanes - x~ormal
Branched chain alkanes - iso or neo
When carbon atoms are connected in a straight chain, they are known as straight
chain
alkanes. When carbon atoms are connected in a branched fashion,they are known as
branched
'
chain alkanes.
'
Alkanes have a general formula Cn H2n + 2, where n is the number of carbon atoms.
The
names ofthe alkanes end in -me. The first four alkanes have specialnames (methane,
ethane,
propane, butane) related to their histories
H
H H
H H H
H H H H
I I I I
I 1 I
I
I I
H-C-C-C-H
H-C-C-C-C-H
H-C-H
H-C-C-H

H
methane
15. ( ~ econtent,
h
wt. %

16.

12.0

(KUOP
1

11.8

0.0047

0.006

11.7

0.004

Table 2.2 Elemental composition of crude oils


-

------

Element

Amount, w f 8

83.9-86.8

11.0-14.0

0.06-8.00

0.02-1.70

0
Metals

0.08-1.82
0.0-0.14

-
I

H H
ethane

I I I I
H H H H
butane

I l l
H H H
propane
,tif

From pentane (C5 Hlz) onwards, Latin or Greek numerals are used to reveal the
number
of carbon atoms per molecule. A few examples are given below:
CH3 - CHz - CHZ- CHZ- CH3
n-pentane

CH3 - CHz - CHz - CHz - CH2 - CHz - CHz - CH3


n-octane ,

From butane (C4Hio) onwards, alkanes may exist in two or more forms
(isomers)differing
in structure. For example, butane may exist in two forms as follows:

n-butane

I
cH3
isobutane

I,
Ill
, , ~ m & ~ , . p e ! m n ~ ~ i n ~ b t ' ; s....~ ~- ...~ ~ ; d i i ~ b ~ ~ b ~ ~5
~,: 3F.j ~ ~ I w

amY1um for
ine f B h ~ i i ~ ~ ~ O ~ ~ ' b ~ f i v ~ ~ t i ' 6 ~ .
nsmr
~di.;~!
pentylenes may supersede this. For the higher members of the series the IUPAC
system is
used. For example,
'H
,;

H %
HI
-C-H
Blphenyl

Naphthalene

Anthracene

Phenanthrene

The moat common mononuclear ammatics found in crude oils,are toluene and m-xylene.
The possible constituents of crude oils. include polynuclear species containing up
to a t least
eight condensed rings. Many polycyclic aromatic hydrocarbons present in petroleum
are
carcinogens.
Alkenes. ,These are openchain unsaturated hydrocarbons,c o n w g a carbon-cirbon
d&&rh:!b.
ona; T
~tgn&~ the
~ : , chbbn-h,+ddi6h
~
pr!op,c~~hk.xrPi.it:~'d
'driabsgj,cli,c
m4;'th
*t{a%ahe;.
CiH,,
e i e l y i:A,
fe :
eak.e)i :, ,an.d,,:& ?-1;'d;a:vi8r
I .......f......
*e., we
.' '.. iS( ; .GoS
*em rs o C ~ Wl ~ l
pF&, .Ad$&.& 6 4 ?',le;&:,6f
.$&.&;::hd&
$
,p&
*ivLfds&dtutai,is&h&&:&po8diti1;,d'e ped&g,,od ,&ei'&Pti:bh'
s;i hl,&Ij:6$d
within the basic
hainmu.&
,
for =hpr8',
. ~ 6 : i t i ~ g h c ~ w & ' b ~ & n nljre~ ~ 6 . a ~
expected, as follows:

..

'

p,@adlene . . . . .

H H H H
I l l 1
C=C-C-C-H

H H H H
I I I I
H-C-C=C-C-H
I
I
H
H
but-2-ene

The number indicates the number of the first of the doubly bonded carbon atoms,
numbered from the end nearer the double bond. In addition, the typical side-chain
isoniei is
. . . ... . . . . . > I ! ; , ; , . ,,.
.,:, ,
expected, that.is
,
, I '
,.: :
H3C H

' I
C=C
' I
H3C H

;j,

..

.-8

, :
VC,,.

.;

,.

isobutene (2methylpropene)
The two possible geometrical isomers of but-2-me are the foliowing:
H-C-CH3
CHR-C-H

.:;

:I
,:&penWeriw
t ':.
.. ; , ,<, ;,!

: . l;'3-butadl@ne:

,.

-..:. .I3,
;b'he~ttiine

!
: .: :'
'
.
A l ~ e e ~ ~ e e . a r e o p e n - c h a i n ~ h y d r o e a rcboo~ntsa h i n
onecarbon-ctybon
g
triple bond.
The fin&.member:o$thi~~s~eesi~acetylene,
Cfia,:wbich,appe~~8;injexten44
f o h ' l a as:the
linear molecule: H-CGH. Additional members of the alkyne seriea:.comphe,-open-chain
molecules somewhat similar to the higher alkenes but with each double bond replaced
by a
t r i ~ l ebond. The.IWAC system of nomenclature.ri~pliesthroughout t h e series as
with the
alcenes, but t h e des&tem
treats tho!~~htah&abers.
as d&vativee,:of acetylene. Thus, .I:
,
for example,. H.arnWfijjcbuld
.
be d e s d & d !& .&itherbut-l--ge' b i s&ylacetylene. The
and relative densities of the alkynes are slightly higher than those of the
boiling
,
corresponding alkanes.
Cycloalkanoarenes. These, also called naphthenoaromatics, are mixed polycyclic
hydrocarbons and possess structures involvingfusion of aromatic with alicyclic
rings, and may
...
carry aliphatic side chains. These h y $ ~ ~ & ~ ~ ; ~ Q
appearing
u$
in the kerosine fraction,
increasing in concentration in the higher-boiling dbtillaticn fractions and
residues. Bicyclic
~?!p~t$enp~~m~$c..
$nee.tu.prn~ti-~
r h g . &dfpop alicxy&c).ingee.?:p.$+in
and..theic,alkyl
4$vativ$
3;"
r'la!jiy$~.+&dadt' .9,keroeifte..apd:h&
. . ......<...
gas ,oi4,
..... ,Ew
, . -pl
of+
, C:Q ~ P O ~ W &
present
.
are.
. . giyen.belpw :
...
. .
I. . . .
. .
. . .
. . >

,!.

;,

.'; ; ; . <

!.:.

v.

.'

'

.,
-

L.

...

. . . .

These isomers are classified by the Latin preiixes cis (on this side) and trans
(across)
indicating the relative locations of the two end methyl groups. Coneequeptly, there
are four
isomeric butenesin all.

i.,.

.,

I n ~ a n O ' ( ~ ~ " ,'::o"~

.
.

.k(~ln.~Cio,H,2).. .. ...,,. . ..

(1,2, 3, Ctetrahydmnaphaalene)

..

.
d '

2.3.2 Non-Hydrocarbons

Crude oils contain appreciable amounts of organic compounds with structures


incorporating one or more (the same or different) atoms of sulphur, nitrogen, or
oxygen in addition to
carbon and hydrogen and some of these are associated with metals such an vanadium
and
nickel, i.e. they are organometallic in nature.
Sulphur compounds. Sulphikr'is th8 mast.abundant atomic constituent of &de oils,
otherthan carbon and hydrogen. One of the origins of sulphur compo.ydsin the c v d
e oils is
~~&~~tcird:kulphiw~h-*~i;it
.dtigs;siie$.bf&e.filarit
and'mirriLl $&&;ns'd;po&ted,&
.;<,

:<,..

.,<

'.

CH3 SH
methapethld
(methyl mercaptan)

QHGHzSH
, e@anethiiol

(ethyl,merw~tan)

>.,v.-

'(CHsh Ck SH
~sopropanethlol
(~sopmp$imercaptan)

m ~ h e x a n a m w p h l d e )

.,,!

geological beds. The other origin is the biogenic reduction ~f'"dil$h'&.~'&de oil*
"&-y
considerably i n their sulphur content ranging from a few hundredths by weight to
as ;puch
#rceht OT sdbhdi. ~ u l b h u ycokedf of 13.95% foddd $ d a d p o i n t (inetah
State in
Ui$.;Aj?.is #e,&ghkst
. I :.. record&
.
sulphur cdptent of any cqde:oil.
. . .,.. I'.
. . , *
.
The * u l p h ~com~~unds~'~re'se'nt
in c k d e oils can' be dividedlinto thiolq, &on& and
.
. .
Wlphides and thiophenes. (':
i@.Thiolsi.alsocalled mercaptans,-are&hesulphur ana1ogues:ofthe alcohols
(i.d.thiodcohols)
and characterized by the presence of the sulp-hydryl group, -SHd which takes the
place of a
hydrogen.atom in,an alkane-p~:cycloalk.ane
molscule.;Thiols:are.t&amain;sul$hur.compo~ds
of lower~boiling.(.petroleum~~fraotioh~
(blow 200C). Etamples uf.this'dltrss ohaul~hurCOWpounds are givep belaw:
"

(CHI CHdz S
3-thiap'entane
(dlethyl sulphlde)

CH3 CHSCHCH3
I
I
CH3 CH3
2,4-dlmethyl-3thiipentane
(dhwrwyl sulphide)

As in the case of thiols, the sulphides are generally very malodouroue.


Afew low molecular weight disulphides (dithiaabnw) have also beenshownto be present
in crude&.The accurrence of disulphides in;prudeoile may be owing to the secondary
reaction
of thiols with tln olriaant such as air or free sulphur. Organic disulphides are
isologs of the
organic peroxides, ROOR, but are much morestable. Examplea are given below:

23-dlthlabutane
(methyl dlsulphlde)

CHs
2-memyC3!&lthiehuxane
~ a ~ ~ . d l s u l p h I d e )

Some examples of thiophenes found in crudes are given below:

thlophene

2-emytthlophene

benzo(b)thlophene

'The #resence of thiols:'in the.~~etr~~c!u~il"hattions


ca;i+ies -cofp5sioR,I!rcibkems, c'talyit
p&sdin& an.d ~ple'&*t'i~60rata~,&d pf& oaouis. mbjg:a'te n& bMc:h&lj; poi*oi;d&
'.

.?C,..

~.
..

..

in low concentration, however, and they are often used as odourants iii LPQThe
ibwer thibls
are the inost malodourous..One part in 50 million of ethanethiol can be detected in
air by the
human nose. The odour is strong at 0.6 ppm arid distinct at 0.03-0.07 ppm. In high
concentrations, the odour ohanges to something like that of chloroform.
Thiols are stronger acids than alcohols, and use is made of this to remove low
molecular
weight thiols from light gasolines with caustic soda solution.
Hydroprocessingtechniques are
employed to desulphurise other oil fractions and here combined sulphur is
eliminated as
hydrogen sulphide from all type of-compoundcontaining this heteroatom.

Thiophene and its alk$ dNvativee are n o ~ y , r ~ l a t i v ~ I y . sconstituents


c~ce
of crude
oils, but condensed system-benzothiophenes, dibenzothiophenes, and higher
polycyclics (e.g.
benibnaphth~thio~henes)
are impartant component8ofall high aulphur crudes. Thiophene
derivatives are p d c u l a r l y abundant in erude oils containing high
proportions ofmmatics,
resins and asphaltenes.
syao~spaaj
jo d0n)Fse nam se .-a 'leaq ag!aads 'queqsuoa blpad-bq!soasr~ 'ququo3 uaSorp6q
s-e qans savadord i a q o pue d0nx u a a w q pado~a~ap
suo!+81auoa Lxequaura~duroaaqq
u! saq lo33ej a w j o etlaqnJasn u y u r a q , 'uo!qaeq a w u! suoqieaolplCqjoadLq
~ep!+%d re jo
aaueu!uropa~da w q e 3 ! p ~03 pasn aq trea suogaeq wna~oqadjo donxjo sanIea aq? '
m u
sa!lamoxv
0'11 - 0'6
sauayqqd8~
0'zT - 0.11
sugsisd
O'ET - 9'ZT

910aplu3 JO uo!pa&ssa13 j o - p o q l a ~ go
d npamg
~
Sn p.g e l q ~ ~
:shio~~oj
SB am su0q~eoo"pbqjosassel:, p a r a m 103dbnx j o f ~ ~ r i p A
.s!sap.jq+am E uo angppe SF l g a e j uoge5pajSs.req3 s m spuqq LO s a q q x rod
.pa,ws!p
s3tim1onguaarad (jdp w ( ~ '09
i "0s '01 qF! samqe&&&q' ~*'I@BX$AB
Kq ahma u o r p m s i ~ ~
N J , u10~~~paqe$4ds~~1oga~rg
~
rtrna~oiqada 9 3 0 qqod ~Utfi0~'&833~%?
aqL . 3 ; g 9 a 9 ~ / 3 0 ~ b ' g
3~ ~ ~ ~ ~ ~ ? qij
& p~s :7
~ p'P :yo 'F& xZ;!~:dq a s e ~ a ~a w
e r! u a:?qm

(TIZ)--1

3 = aonx
,
(9J)

:uqskdi& B p o n d J ap7 q ' 8 r @ p ~ o m'k+efi~gaads


'
q q y $$dd Z q o q &qqa.uoa IWBJ
'(*03~s?sn~q'E@ti,61arimn)
sodidq p&~aAap%! 'donx 'i$$b& u o ~ e ~ ~a bu q' j
I
i
o
~
~
~ 1 . ~v ~ ~
,

,
I

~ P a q d ~ g ~?F
q EI!O;aP!v
.
30 uoRe~J!$m %
?I.! W+:(PUO!TW.
Xaq, s y ~ ~ ? ~ , ? ~ , ; ~ ~ ) , j o ~ ~ & y e @
~ Wp a s ~ w .ys a u ! m ~ n e a m psn<eyqs39*np3033a ~I!Q,a p r u ~ j o , ~ w p ~
m ~ ~ ~ 1 r 3 ~ a ~

? K J ! ? ~R
~ SY
2.4.2 Correla$inqJn~@xi
. . - ~c~oe~ F index
p ((311,

..

.,;:,

developed by US Bureav of ~ i n e s is, Biven by the following

,u

empiiiical eqfiation:;
,.

11

: ..,

., ..,.

: ,:I.,: ;

..

, i',.

TRANSPORTATION OF WAXY CRUDE OILS


where fi ie'the average boiling point, OR ,'determined by the standard-
BureaU8'dfMbes
distillation method and G is the specific gravity at 15.56C/15.560C.
CI values of a petroleum fraction between 0 and 15 indicate that the components of
the
fraction are'predominantly paraffinic in nature. CI values between 15 and 50
indicate a
predominance either of naphthencs or of mixtures of paraffins, naphthenes a d
qomatics in
the p&roleum fraction. CI values above 50 indicate a predominance of aromatics in
the
,
I
,
fraction.
.

3.1 INTRODUCTION

2.4.3 Method of structural Group Analysis


The methodi?f.siyctyd group analysk.,deseribq?the .ch$ajier; qf.the fraction in
terms
of elements constituting a h theticalaverage
molecule2Pavingthe chemical and pbxeiqal
..! . . . I . . . '
properties of the eumof ' e .indiiridual comporien&..,p;f;@2:Bacti,on,.
awprdb..to .thek
concentration.This methodclarjsifiesthe crude.oilsinto:.sev& Classes (Table 2.7).

p..,
,

Table 2.15Denomination and Classification of Crude Oil Classes


-

Class
I
I1

Denomination of crude oils

Parec
Parfinic-naphthenic

Class delimitation by structuml in& values


%C, 2 72
%CP 2 50; %CP + %CN 2 90

1. G.D. Hobson (ed.), Modem Petroleum Technology, Part 1(Chapter 91, 5th edition,
John Wiley & Sons, New York, (1984).
2. L.F. Hatch and S. Matar, From Hydrocarbons to Petrochemicals, ~ u lPubyishing
f
Company, (1981).
3. L.F. Hatch, A chemical view of refining, Hydrocarbon Processing, Vol. 48, No. 2,
77-78 (1967).
4. B.B. Agrawal and I.B.Gulati, Trace metals in petrolem and petroleum products;
Part I - Occurrence, nature & significance, Petroleum and Hydrocarbons, Vol. 6,
NO.4, 193-197 (1972).
5. B.B. Agrawal and I.B. Gulati, Trace metals in petroleum and petroleum produds ;
Part 11 - Individual constituents and their significance. Petroleum and
Hydrocarbons, Vol. 6, No. 4, 198-202 (1972).
6. P. Jones, The presence of trace elements in crude oils and allied substances,
The
Institute of Petroleum, 73-76 (AprilJ u n e 1988).

I
I

1
I
1

Crude oils contain a mixture of light and heavy hydrocarbons. Typically, a


stabilized oil
may contaitl paraffinic, naphthenic and aromatic components as heavy as Cso. In
addition,
poli& ahd asphaltenes M& also be'present. The lighter componentsin the crude oil
kdep the
he&d& toxhpohents in solution. This solubility depends very strongly on the
temperature. If
the temperature of the oil is decreased, the soldbility of the h e a w
hjkirocarbons atiy be
sufficientlyreduced to cause precipitation of these components in the form of solid
wax crystals.
The polars and asphaltenes may also co-precipitate with wax crystals. The
phenomenon of
wax separation from petroleum fluids at low temperatures has been a problem to
users of
petroleum products for a long period. It can occur in lubricating oils, residual
fuels and crude
oils. '
The presence of wax crystals changes the flow behaviour of the crude oil from
Newtonian
to non-Newtonian. The wax crystals usually lead to higher viscosity with increased
energy
consumption for'pumping and a decreased capacity. In addition, if the oil is cooled
during
transportation, the wax crystals tend to deposit on the colder pipe wall. Wax
deposits can lead
to increased pipeline roughness, reduced effective diameter, more frequent pigging
requirement and potential blockage. If these deposits get too thick, they can
reduce the capacity of
the pipeline and cause problems during pigging. Wax deposition in process equipment
may
lead to more frequent shutdowns and operational problems. In extreme cases, wax
crystals
may also cause oil to gel and lead to problems of restarting the pipeline.
Great potential savings can be derived from accurate prediction of wax formation.
The
knowledge of the magnitude of wax deposition can lead to reduction of insulation
requirements
for production and transportation systems. Conversely, problems with wax can be
addressed
in an early stage of a project so that sufficient thermal insulation is planned for
instead of
expensive chemical injection and loss in capacjty or loss of availability. Process
heat loads can
be reduced by increasing efficiency of heat transfer. Capacity reduction in heat
exchangers
can be overcome.This reduction results from blockage or vibration problems. The
size of export
pump8 and flow lines c+ be reduced by an accurate knowledge of the effect
of,waxformation
on crude viscosity. The minimum pigging frequency can be estimated. In addition,
problems
related to start up and shutdown can be solved cost effectively.
The crystallization of wax in crude oils causes severe difficultiesin pipelining
and storage.
The crystallization of waxes at low temperature causes reduced liquidity of waxy
crude oils
which considerably w p e r s the transportation of crude oils through long distance
pipelines.
Several methods exist for handling waxy crudes for ease of transportation. For
example,
pigging the pipeline is useful for removing thin layers of wax only. A highly waxy
crude may
TRASPORTATIQNQR WAXY,CRUDE OILS

PETROLEUM'REFININGTECHNOLOGY

to be the:waxy. Such a,classificatioo~wasbased-on the wax content.oEthe,cmdeaad


itspour
point; The,characteristics of some of these crudes are given in-Table3:l. In-
contrast,mos$of
the MiddleEast crude oils have a pour pointbelow 0 OC and wax contentless than
7wt.kand
therefore pose no problems in pipeline transportation even at low temperatures.
Waxy crude oils exhibit non-Newtonian behaviour a t temperatures below about 10C
above the pour point. The wax can crystallize as the crude is cooled to form gel or
a partial gel.
Under static conditions a rigid gel is formed, but if the crude is cooled while in
motion, the
apparent viscosity will increase but the material remains fluid: Therefore, the
rheological
properties are functions of temperature, shear rate, shear stress and past history.
Problems
in pumping these crudes will occur if the temperature drops and the fluid becomes
non-Newtonian and if gel formation occurs after a shutdown. The pipeline facility
must be designed to
recover from these problems or prevent them. A realistic approach should be
developed based
upon an extensive evaluation of the rheological behaviour of the crude oil under
representative
temperature and shear conditions. The two rheological parameters of which knowledge
is
indispensable for transporting waxy crude oil through pipeline are viscosity and
yield stress.
Before we go further into rhealogical behaviour of the crude oils, a few relevant
terms that will
be frequently used are defined below.

require fiequent.piggingtokeep the wax accumulation manageable. Apigging operation


often
rattires significant amounts of costly offshore man-hours. Taking into
consideration all the
&o-economic
aspects additive treatment is reported to be the most suitable method for the
t k w o r t a t i o n of waxy crude oil, which can depress the pour point and
improve the flow
characteristics at low temperatures.
,\,

~.$+~P~~~U~~'~R~NSPORTATION
For the transportation of large quantities of crude oils, pipelines are the most
economic
means. Under safety aspects, transportation by pipeline guarantees the best
protection for the
environment. Further, there is no handling of other traffic and no disturbance by
noise or air
pollution. A continuous supply to the refineries is normally assured and this is
not endangered
by weather conditions such as fog, icy roads, or traffic conditionsalong inland
waterways, such
as high or low water level, ice, etc.
However, each pipeline system requires very high investment which should be used
most
economically. The most economical and efficient operation of a pipeline could be
reached by
maintaining a continuous constant flow rate without any interruption. Also, ip
respect of a
reliable and continuous supply to the refineries, a steady-state throughput, with
some seasonal
fluctuations due to market requirements, should be envisaged. Otherwise, additional
storage
volume has to be provided for large quantities of crude oil and this would be very
expensive.
Interruptions by shutdown of a pipeline are by no means desirable. However, a
shutdown
may occur due to the following operational reasons:
(a)There ia an inadequate stock of oil in the terrnind. This could be caused by
distribution
in tanker schedules, for instance, due to weather conditions.
(b) There are no delivery requirements by the refineries fed by pipeline. This
could be
caused by disruption in operations sf one or more of the processing units of the
refineries, for
instance, due to equipment breakdown.
(c) A pressure test for leakage control of the pipeline has to be performed.
( d ) Repair, maintenance work on the pipeline system including pumps is required.
(e) The pipeline might be shutdown automatically by exceeding the operational
safety
limits.
These shutdowns are not expected to last longer than 3-4 day. Under extreme
conditions
one could think of extraordinary long shutdowns. The reasons might be government
action,
earthquake, strike, war, etc. However, under normal conditions, they are'not
expected.
I n e n transporting waxy crude oils, these operational points of view'are of
considerable
importance.

able 3.1 Characteristics of Waxy Crude Oils

3.3 WAXY CRUDE OlLS


The crude oils pumped in pipelines up to the early sixties generally showed normal
characteristics in respect of pumping conditions such as viscosity'and low pour
point. nowever,
the opening up of remote oil fields in North Africa and India in the 1960's to
exploit the low
sulphur (but waxy) crudes in these locations, and the need to pump tKese oils
through the
much colder pipelines has led'oil producers to study the pumpability of waxy crudes
at
temperatures below the pour point limit. The advantages of these crude'oils in
respect of high
reserves, low sulphur content, good distillate product yield and its low dscous
flow under fair
temperature conditions are, however, partly compensated by the disadvantage of high
wax
content, which results in a high pour point and under certain conditions of low
temperatures
could create operational difficulties after a long-term shutdown of the pipeline.
Worldwide,
one can distinguish about 1500 varieties of crude oil of which 10 to 20 percent are
considered

31

3.3.1 Definitions of Rheological Parameters


SHear stress. Consider the steady flow of a fluid in a horizontal pipe of circular
cross-section. The fluid flows with an average velocity of U in apipe of inside
diameter D. The pressure
difference between two points 1 and 2, separated by a distance of L is (Pi - P2).
q e decrease in pressure in the fluid reflects the applied force causing the fluid
to flow
and if the flow is steady (i.e. no change in the flow and hence velocity), this
force must be
counter-balanced by a shear force of equal magnitude at the wall of the pipe. If r,
is the shear
stress at the pipe wall, then force acting on the fluid at the wall must be - 71 DL
rw.The
negative sign indicates that this force acts in a direction opposite to the
direction of flow. The
(Pi - P2). In steady state (no
force acting upon the fluid due to pressure difference is
acceleration), the sum of these two forces is zero. Therefo;e, w6 can write
I
The above eQUatibh rneteliy shews thaCthe,sheaps&ss at-thepipe w l i@jUsti&pther
~ e a n of
s e*@&ioh bP"dti%n~losd.-~rbin
E1$,3j1, itfdlfowru that.avddab1e~hear'strgSs~or
a
particular pipeline depends,on the leligtbd the line between twa,pump stations! and
the
pressure difference. The availdble sheatj $tress can<be1 increased by increasing
the initial
pressure, PI, and/or, reducing the section length of pipe, L. An example of
calcu\ati~nof
available shear 'stress is given,below.

TRA&&RYAT~ON

OF WAXY CRUbE OILS

,For laminar flow in pipes, friction loss ie given by


&.
32 p U
-(PI
= -P2)
which can be rearranged in the form

[(PI P2)DI4LI -- TW
(8UD)
-(8UD)
.

Therefore, for laminar flow,

.
J3.3)

Rate of shear = 8U/D


and for turbulent flow,

*..(3.4)
Rate of shear = (SU/D) Cr
where Cri3 correction factor which depends upon Reynolds number.
Yield stress. It measures the ability of fluid to restart its flow aRer shutdown of
the
transportation system. The yield stress of an oil, at a given temperature is
defined as the shear
stress required to initiate flow. It can thus be directly compared with theshear
stress available
or allowable in a pipeline. The yield stress of waxy crudes ie influenced by-ite
temperature
history, shear history, aging and composition.

Density of crude at pumping temperature

:.

2
-

'=
STATION : VIRAMGAN TO ABU ROAD
SVatic head at Viramgan
Static head dt";sb'u Road
Pump puction
Differentialheaq of each of the pumpa at rated flow
Two pumps willtbe operated in series.
Ressure drop ah Abu Road
Resdure dtop in the liile

o2

Pressure drop

3.3.2 Rheological Classification of Fluids


There exists a rate of shear and shear stress at each point in a flowingfluid. In
determining
the rheology of fluids, any one of the following b a i c behaviour patterns (fluid
types) may be
found upon agitation of the fluid a t constant temperature.
Newtonian fluids.A Newtonian fluid is one whose visco~itya t a given temperature ie
independent of the rate of shear. There is a linear rdationship between the shear
streas and
the rate of shear for a Newtonian fluid. The viscosity of a Newtonian fluid a t a
given
temperature is constant regardless of the velocity, previous agitation or shearing
of the fluid.

Inside diameter of line


Line length
Shear strees

= 0.000339 psi

P
Fluids

= 23.4 dynes/m2

If the available shear stress is equal to or more than the.


forcp peeded to
overcome the shear streas at the.innersqfape of the pjpe, $hen tbe,flow
l$e initiated.
Shear rate. consider two p&allq;lplanes of area A, separated by &:d~erqntiai&jtance
dr. The space between the two planes is filled with a fluid. The lower plane is
fixed. A small
force F applied to the upper plane wiv give it a velocity dU in the direction of
the force. If there
is no slip between the wall and the flGd, the fluid adjacent to the upper plane or
wall &q also
have a velocity dU in the direction of the applied force and the fluid next to the
lower plane or
whll will have a zero velocity. Thus, a unifoy velocity gradient of magnitude
dU/&ris set up
in the fluid since the shear force F is uniform across the distance dr;The velbcity
gradient,
dU/cir, is commonly referred to as the rate of shear. The shear force per unit
area, F/A, is called
the shear stress.
Viscosity. It measures the ability of fluid to flow during steady state condition.
It is the
property of a fluid that resisp a shear force. It can be thought of as the friction
resulting when
one layer of fluid moves relative to another. Viscosity, p, can be defined as the
ratio of the shear
stress to the rate of shear.

Purely viscour flddr

P
Time dependent

Flg. 3.1 RheologlcalclasslficaUon of lulds.


I
I

35

WRASPORTATIONOF WAXY CRUM,OILS

Non-Newtonian fluids. A non-Newtonian fluid is one whose viscosity at a given


temperature is dependent on the rate of shear. A fluid having a viscosity greater
than 20 Pa.s is likely
to be non-Newtonian. The viscosityof non-Newtonianfluids may increase or decrease
with the
rate of shear, depending on the type of fluid. The classification of non-Newtonian
fluids is
depicted in Fig. 3.1.
Time-independent non-Newtonian fluids. A non-Newtonian fluid is said to be
timeindependent if the shear stress at any rate of shear is constant with time. The
properties of
such fluids dependonly on the magnitude of theimposed shear stresses and not on
theduration
of the stresses.
If the viscosity decreases with increase in the rate of shear, the fluid is known
as a
pseudoplastic fluid. This behaviour,is generally restricted to a certain range of
shear rates. At
a very low or high shear rate, fluid,maybe Newtonian.
If the viscosity inkeases with increase in rate of shear,the fluid is known as
dilatpnt fluid.
Bingham-plastic fluids exhibit a definite yield stress below whith no flow occuis
(the
behaviour is that of a solid). A finite force must be applied to produce movenlent.
The line*
relationship between the rate of shear and shear stress for Bingham-plastic fluids
does not
pass thmugh the origin.
Time-dependent non-Newtonian-fluids, A non-Newtonian fluid is said to be time-
dependent if the shear stress changes with the duration of shear. In other words,
the viscosity
of such fluids at any time depends on the amount of previous agitatidn or shearihg
of the fluid.
A fluid whose viscosity decreases with time at a given shear rate is called
thixotropic.'If the
viscosity of a fluid increases with time at a given shear rate, We fluid is called
rheopectic.
1)
Viscoelastic fluids. These exhibit many characteristics of solids. Their resistance
to
deformation is proportional to the usual viscous effect, plus an elhticeffect that
is a a c t i o n
of time. When the rate of strain of such a fluid is suddenIyincreased, there is a
relaxation time
during which the stress changes from its origidal to a new steady-state value.
Equations
developed for pseudoplastic fluids can be applied to the steady-state flow of
viscoelastic fluids.

/ 2

Figure 3.2show8 thevariation of viscosity with shear rate for different types of
fluid. Curve
number 1 is typical of the response of a Newtonian fluid. A Bingham-plastic fluid
is characterized by a flow curve 2 which is a straight line having an intercept b
on the shear stress
axis. The stress is called the yield stress which must be exceeded for flow to
commence. The
flow behaviour is described by an equation
.,-.-,

With pseudoplastic behaviour, the fluid displays increasing viscosity with


decreasing
shear rate. This means that there is a non-hear relationship between shear stress
and shear
rate. Curve number 3 represents pseudoplastic behaviour. Dilatent beheviour is
depicted by
curve number 4.
Most waxy crude oil gels exhibit thixotropic or occasionally rheopectic behaviour.
When a
waxy crude oil is allowed to cool below its pour point under static condition in a
pipeline, the
paraffins will crystallize causing the entire mass of crude to gel. To initiate
flow again, a finite
pressure is required. For waxy crudes, yield stress is an inverse function of
temperature and
increases with decreasing temperature. With the crude oil that is below its pour
point, the wax
crystal structures in the oil start to breakdown as flow begins. This breakdown
depends both
on the time and rate of shear.
Start up pressure depends to a large extent on whether the oil is cooled under
static or
dynamic condition. For instance, the additional restart pressure will be
substantially higher

Shear rate

fig. 3.2 Typical non-~ewtionionfluids.

for a statically cooled pipeline (the fluid was above the pour point while flowing
and allowed
to cool during shutdown of the pipeline) than for one that has been dynamically
cooled (the
fluid was already below pour point when pipeline was sl~utdown),i.e. the cooling
occurred due
to the flow of the crude in the pipeline.
--

3.4. FLOW PROPERTIES OF WAXY CRUDE OILS

The viscosity of crude oil is perhaps it. most important physical property. For
most crudes,
at sufficientlyhigh temperature, the viscosityat a given temperahue is constant and
the crude,
is reduced,
although chemicallyverymmpl?~,is a simple N
e
v
however, the flow properties of a crude oil can readily change
very complex flow b e h a w due to the crystallization of
of asphaltenes. The waxes basically consist of
.
crystals Can
form an interlocking structure of plates, needle or malformed ~ s t a l sThese
entrap the oil into a gel-like struehue that is capable of forming thick deposits
in pipes and
TRASPORTATION OFWAXY CRUDE OILS

The .second step is to plot curves of viscosity versus rate of shear for different
pipeline
throughput as follows:
For a given flow rate, an equivalent shear rate is determined by Eq. 3.3. Assumin$
the
value for viscosity, the Reynolds number is calculated. If the flow is in turbulent
region, the
correction factor for rate of shear is read from the plot of the correction factor
for shear rate
versus Reynolds number. Using this factor the effective rate of shear is obtained.
By repeating
this for different values of viscosity, a curve of viscosity versus effective rate
of shear for a flow
rate can be superimposed on the plot of viscosity versus rate of shear for various
temperature.
The intersection of the constant throughput curves with the constant
temperaturecurves$ves
the appropriate viscosities to be used for these conditions. An effective viscosity
versus
temperature curve can be plotted for the various Chroughputs.As mentioned earlier,
using
these values of effectiveviscosity, pressure drops in the various sections of the
pipeline can be
calculated.

Correlation of the model pipeline test results for actual pipeline d e s i p ie


tlormally based
on the previous experience. Some of these correlations are developed by the
designers by pilot
plant tests simulating the field conditions in a test loop.
A general equation for calculating restart
r e q ~ r e m e for
h a cooled line is
p=-YLC
A
...(3.6)
where P is the pressure required, Y is the yield stress of gelled crude (thitr
value must be
determined in laboratory tests and is different for static and dynamic cooling), L
is the line
length, C is the circumference of inside pipe wall and A is the cross sectional
area of pipe.
3.5.3 Flow a t Restart
kc
At the time of restart of the pipeline because of very high viscosity,the flow rate
is ejrpected
to be low. This, however, depends on available shear stress as compared to
thejrield stress. In
any case, the minimum flow conditioris of the pumps have to be investigated. If a
pump is
operated at a very low flow rate, additional wear due to unbalanced flow is
expected. Further,
due to the poor efficiency,the oil will be heated and, after a short while, the
allowable maximum
temperature will be exceeded. This limits the allowable time for the operation of
the pumps
with low flow.
If the restart flow rates do not meet the pump requirements, gpecial pumps with
appropriate characteristics h i g h head, low flow) have to be used for restart of
the pipeline.
3.5.4.Effective Pipeline Viscosity
For determining pressure gradients in the pipeline, effective pumping viscosities
have to
be determined. Using these viscosities, the conventional formulae can be used for
calculation
of pressure dmp.
The effective pipeline viscosity for calculating frictional pressure drop at
various flow rates
and temperatures can be predicted by rotational viscometer tests. Due to wax
crystallization
at low temperature, the conventional capillary tube viscometers cannot be used.
Moreover, for
non-Newtonian fluids viscosity is dependent on shear rate. For this service as also
for other
sluny services, rotational viscometers are used. The sample is taken in a double w
d e d cup
(a refrigerant flowid in between the two walls). The outer cylinder is rotated by a
variable
speed motor. The &er cylinder is suspended from a torsion wire consisting of a
stainless steel
tube, the deflection being measured by a balanced pointer. The rpm of the outer
cylinder
multiplied by the instrument constant gives the shear rate. The deflection reading
of the
pointer multiplied by another instrument constant gives shear stress. The ratio of
shear stress
to shear rate gives the viscosity of the fluid.
When the oil is at such a temperature that flow is non-Newtonian, the Reynolds
number
is a function of viscosity which itself is a function of the effective rate,of
shear. Therefore, an
intermediate calculation is required to arrive at the appropriate pipeline
viscosity for calculating pressure drops.
Viscosity of the oil to be pipelined is determined at various temperature and rate
of shear
by rotational viscometers. These are used to plot-viscosity versus temperature
curves for
various rate of shear. This plot can be used to determine the temperature below
which the oil
will behave as non-Newtonian fluid. It is required to find the effective
viscrosities of the oil for
pumping at'different flow rates a t various temperatures.
The f i s t step is to use the plot of viscosity versus temperature-and plot curves
of viscosity
versus rate of shear for different temperatures.

3.6 METHODS FOR PIPELINE TRANSPORTATION OF WAXY CRUDE OILS

One of the following methods for pipelining waxy crude oils may be considered:
(a) Select pumps to allow a paralleYseries arrangement, whichcouldtransport at
slower
rateg and higher pressures when required. The piping could be manifold so that
parallel arrangement would be accommodated by repositioning of valves to handle
higher flow rates.
(b) Use of separate low flow, high head pumps for restarting.
Side traps at frequent interval? to allow short s6&ons to be started separately.
Reverse pumping to create back and forth pumping sequence which prohibits static
cool down.
Use of pour point depressants/flow improvers.
Adding hydrocarbon diluent such as a less waxy crude or light distillate.
Iqjection of water to form a layer between pipe wall and crude.
Mixing water with crude to form an emulsion.
Displacement with water or light hydrocarbonliquid in case of shutdown of pipeline.
Separation at higher than normal pressure to allow as much gas and light
hydrocarbons as possible to remain in the crude.
Conditioning the crude before pipelining to change the wax crystal structure and
reduce pour point and viscosity.
Further sub-division of pipeline into smaller segment or reducing batch length of
waxy m d e to increase maximum shear stress available.
Combination of the above methods.

Pipelining the crude as an oil in water (Om) emulsion reduces the flow properties
to nearly
the viscosity of the continuous water phase. An O N emulsion pipeline handling
40000 barrels
of oil per day (265 m3 h-l) of 70 vol.% crude oil has been operating in Kalimantan
(Borneo) in
Indonesia since 1962. Blending with a less waxy crude oil or distillate improves
the flow
properties by altering the wax solubility relationships. Both of these methods have
the
disadvantage of reducing the crude oil carrying capacity of the pipeline. Note that
separation
at the well head to include more condensate in the crudepjl (if available) has the
same effect
as dilution. There is one interesting case of a shear and t e ~ p e r a t u r
treatment
e
being used to
favourably alter the flow properties of waxy crude oils in (Assam (India). More
recently, pour
40

PETROLEUMREFININGTECHNOLOGY

point depressantdflow improvers have been developed that, in small concentration,


affect the
crystal growth, and as a result improve the flow properties.
Of the various methods developed, the use of pour point depressantdtlow improvers
is
found to be more attractive. The main attraction of this method is its relative
cheapnees and
variability of dosage with respect to the temperature and desired viscosity
requirements.

All of the above considerations point to additive injection into the crude stream
at well
head.
3.6.4 P o u r Point Reduction b y Additives
Pour point measurements on crude oils have been used to detect low temperature
handling
problems. However, as mentioned already, they do not necessarily predict the field
performance. Pour point can at best be used for preliminary screening of various
additives for their
potency with a particular crude oil.
These studies were carried out in the Salaya-Koyali-Mathura crude pipeline by Oil &
Natural Gas Commission, India. The line was originally designed for transportation
of low
pour point Middle East crude oils (Light Arabian and North Rumaila). With the
discavery of
the Bombay High crude oil, it was decided to process this crude too at these
refineries. Efforts
were made to find a suitable solution to the problem of pipeline transportation of
this high
pour point (30C) Bombay High crude oil to these refmeries during winter. It was
reported by
model pipeline tests that the line will not be able to take a restart after cooling
statically to
low winter temperature of around 16OC.
A number of flow improver additives were tested for their effectiveness on Bombay
High
crude. born preliminary tests, Shell-swim-5Tand Esso Paradyne-80 were reported to
be the
most effective additives in lowering pour point. Further tests by rotational
viscometers
indicated that, for similar level of dosage, both effective viscosity and yield
stress were reported
to be lower in case of Shell-swim-ST as compared to Esso Paradyne-80. It was
therefore
concluded that shell-swim-5T is superior to Esso Paradyne-80. Subsequently, Shell-
swim-5T
was used for transportation of the Bombay High crude to Uran terminal through the
submarine pipeline from the production platform. Extensive studies were
subsequently done
at IIP, Dehradun and Gujarat Refinery to determine the optimum doping conditions
for
Shell-swim-5T in Bombay High crude. k o m these.studies the optimum doping levels
were
reported to be 250-300ppm of the Shell-swim-5T.The effect of doping temperature on
the pour
point was reported to be negligible.

3.6.1 Use of P o u r Point DepressantslFlow Improvers


The injection of pour point depressantfflowimprover additives appears to hold the
greatest
promise of achieving the desired overall objectives of operational safety and
operating
economy. Now improvers should have the capacity to
reduce the pour point, viscosity and yield stress under dynamic conditions; and
restart the pumping after a shutdown with the available shew stress.
Chemically pour point depressantshlow improvers are ashless polymeric additives
which
when added into the crude oil a t 300-600 ppm level reduce the pour point and
viswsity of the
crude oil. Polymeric materials.widely used as pour point depressantdflow improvers
are (a)
alkyl acrylate polymers and cdpolymers, (b) o l e h alkyl maleate copolymers, (c)
vinyl ester
polymers and copolymers, and (dl alkylated polystyrene. Normally, the average
molecular
weight of the commercial available pour point depressants for crude oils is between
2000 to
20000.
Various flowimprovers developed a t RRL, Jorhat (India) are SWAT-104, SWAT-106,
FIR1
and FIRI-B. These are polymerdcopolymers,easily soluble in crude oil around 4M5OC
and
non-corrosive. They are used in pipelining crudes of Bombay High and Asssm (India).
3.6.2 Mechanism of Flow Improvement
When a waxy crude oil is cooled below its cloud point, the wax crystals form and
begin to
agglomerate and with further temperature reduction crystal agglomerationreaches a
point a t
which a gel structure is formed below the pour point due to interlocking of the
growidg crystals
and dependent on constituents like resins, asphaltenes, asphalts, paraffin and
microcrystalline waxes, etc., their molecular weight, structure and quantity and
also on the rate of cooling
and degree of agitation during cooling. When the additives or flow improvers are
added, they
alter the wax crystal size and shape in some manner and prevent the tendency to
interlock.
l'he'flow improvers or pour point depressants act by retarding the growth of the
wax crystals
in the XY crystallographic plane, thereby producing smaller crystals of higher
volume/surface
ratio. It appears that the flow improvers cocrystallizewith the growing wax
crystal, leading
to the formation of a fault in the otherwise compact regular wax crystal and
resulting in
diminished gel strength, so that by coating on to a growing wax crystal the flow
improvers
reduce the tendency of wax crystals to interlock.
3.6.3 Point of Additive Injection
As a general rule, the additives should be injected into the crude above or around
its cloud
point and also a t a temperature of some 20C above the pour point of the additive.
The additive
pour point could be depressed considerably by cutting (diluting) the basic
component with
kerosine, or aromatic solvents. The preferred location of iqjection should be a t a
point where
No heating of the oil is required (utilize the heat of formation)
Subsequent external application of heat can be avoided or minimised.
The maximum benefit can be derived in the system downstream.

41

TRASPORTATION'OFWAXY CRUDE OILS

3.6.5 Effect of Flow Improvers on Yield Stress a n d Viscosity


Significant reduction in yield stress and effective viscosities can be achieved by
doping
waxy crude oils with flow improvers. The following results were reported for the
effect of
Shell-swim-5T (flow improver) on Bombay High crude oil.

Yield stress @ 160 C

PPm
Nil

dyneslcm2

CP

330.0
62.5
62.5
45.8

'45.0
45.0
42.4
41.0

250
300

400
I

Viscosity @ 160C

Doping level

These results show significant reduction in yield stress with 250 ppm doping.
Further
improvement with higher doping levels is, however, marginal. In fact in some cases
the trend
was reported to be reversed with higher doping levels, as shown below by the
following model
pipeline tests conducted by ONGC.
42

PETROLEUMRWNINQ TECHNOLOGY
.
pintDePres-

TRASPORTATIONOF WAXY CRUDE OILS

Yield stress at 1kc,d y t w s ~ c m ~ Viscosity at 16C at flow deueIop.


ment, cP

sant in Bombay High

CNde

Nil

3.6.7 Crude Oil Conditioning

Test was
as oil could not be transferred to model pipeline
- abandoned
due to congealingat 18OC.

400

21.2

750

on n
1u.I.

1000

27.5

435 at 45 dynes/cm2
589 at 45 dynedcm2
966 at 45 dynes/cm2

Hence, optimum doping levels by extensive laboratory studies must be determined


before
starting additive injection.
1

3.6.6 Incorporation of Low Pour Point Crudes i n Waxy Crudes

Aa mentioned earlier, this can be one of the probable solutions to pipeline


transportation
problems of wary crudes provided the lowpour p i n t cmde is easily available for
blending and
no problems are expected to be encountered in processing the cmde blend as far aa
product
specificationsare concerned. Once again B e example of Salaya-Koyali-
Mathurapipeline can
be cited here. The Gujarat spd Mathura refineries fed by thispipeline
(Gujaratpartly) are to
p m n n partly Bombay High crude and partly low pour point Middle East crude. A
small
percentage of tbP Middle East cmde mixed with Bombay High cmde will not result io
any
serious processing problems. The reported results of laboratoq studies on blends of
Middle
E u t crude with Bombay High m d e indicate that the incorporation of Basrah cmde
in doped
Bombay High cmde shows no further reduction in pour point. I b i q could be due to
reduction
in percentage of n-parfins when Basrah cmde is mixed, the effect of pour point
depre~sant
being more predominant on n-paraffins as compared to iao-parafiins. However, a
significant
reduction in the yield stress of the blend is reported, as shown below.

100%Bomhnv Hioh
-I-.

330.0

100% Bombay High with 250 ppm of pour point depressant


90% Bombay High + 10% Basrah with 250 ppm pour point

62.5

5.0

de~resaant.

The doping temperature is quite important as far as yield stresses are concerned.
The
blends of Basrah with Bombay High crude doped at 50C is reported to give better
results as
compared to temperature of 30C. This is s h o w by the following experimental
results
reported.

Crude blend

Yield stress at 16"C, dynes/cm2

.
. - 250 ppm pour
Basrah with
90% Bombay High + 10% Basra1

point depressant
90% Bombay High + 10% Basrah with 300 ppm pour
point depressant
90% Bombay High + 10% Basrat
point depressant
E

50CDoping
50C Doping

5.0

5.0
5.0

This process is developed by Oil India Limited. The crude oil conditioning is a
unique
process in which the cmde oil is first heated to melt and dissolve the wax in it.
Thereafter, on
dynamic cooling and wbrkbg t b u g h the p m p the crude oil is subjected to static
cooling at
a predetermhed rate. The result is the conditioned crude oil which has much
improved
physical properties than the virgin crude oil. The conditioned crude oil remains
fluid at much
lower temperature and possesses satisfactmy physical properties so far as
transportation of
crude oil through the pipeline to refineries during the winter monUs is concerned.
This has
been employed for transporting wary crude oils from Assam (India).
I,the actual process the crude oil is heated to a temperature of lCOC in tube
heater.
Before entering into the tube heater, the crude oil passes through heat exchanger
and
exchanges heat with the outgoing oil from the heater, bringing down its temperature
to
65OC by dynamic cooling.The crude oil at 65OC is stared in a tank from where it
passes thmugh
a pump to static cooling vessels, commonly called conditioning vessels, These
vessels are
essentially sheU andtube heat exchangerd'in which crude oil is taken in the shell
side and
cooling water is passed through tubes. The con&oning vessels follow a batch time
cycle of
208 minutes to achieve coaling of crude oil &om 65OC to l8.S0C (this includes h ~ &
time
g
of
cmde oil and its emptying outtime also). The coolirigof the crude oil in the
conditiohg vessels
is effected by circulating watets, namely intemediate and relrigerated waters.
Intermediate
water is maintained in a closed circuit through a pump and heat exchanger in which
cooling
medium ia tbs cooling water. The refrigerated w a t u is also maintained in a
closed circuit
though a pump and absorption refrigeration machine. The c i r ~water
t
while f l o i n g paat
evaporator chamber of absorption refigeration machioe though tube bundles gets
chilled.
h the temperature of crude oilis brought down to the desired level of 18 - 2gC,
the cmde
oil from conditioningvessels is emptied out automatically into conditioned oil
storage tanks.
T h e conditioned
oil from these tanks flows pipeline pumps through a booster pump and this
.------completes the process of conditioning.

30C)Doping
3O0C)Doping
25.0

1
1

1 K. W. won, Thehodynamics for solid solution liquid - vapor equilibria :Wax phase
formation from heavy hydrocarbon mixtures, Fluid Phase Equilibria, Vol. 30, pp.

265-279 (1986).
2.

25.0

A ther-

modvnamic
--- -"
model for predicting wax formation in crude oils, AIChE J, Vol. 34,
3.
4
5-.

25.0
25.0

J.H.Hansen, A. Fredenslund, K.S.Pedersen and H.P. Ronningsen,

6.

NO.

12, pp. 1937-1942(1.988).


S. ~angul~,Ftheological~arameteraand
s o l u t i o ~ e m
of waxy cmde oil, URJh vol. 26, No. 2, pp. 33-34 (1989).
P. Datta, H. Dubey and K.L.Pate1, Pipeline transportation of waxy crude oil from
the oil fields, Chemical Engineering World, Vol. XW, pp. 43-45 (1990).,
-.
R. Prasad. Waxy crude oils, In PIPING DESIGN HANDBOOK J.J. Mcketta, Ed..
Marcel ~ikker,il992).
S. Naik, C.K Pathak, and V.P. Sharma, Effecte of our p i n t dep"essant8 on WaXY
Indian crude oil, IE(1) J., Vol. 69, Part CH2, p p 60-63, (1989).

s
4

PETROLEUM REflNlNG TECHNOLOGY

7. M. N. Sunil Kumar, Reviews on polymeric and copolymeric pour point depressants


for waxy crude oil, The Institute Of Petroleum, 0ct.-Dec., pp. 47-71 (1989).
8. B. Smith, Steps for finding crude properties, The Oil and Gas J., Vol. 77, No.
23, pp.
150-152 (1979).
9. L. T. Wardhaugh and D.V. Boger, Measurement of the unique flow properties of
waxy crude oils, Chem. Engg. Res. Des., Vol. 65, pp. 74-83 (1987).
10. B. Smith, Heat transfer explored in pipelining high-pour-point crude oil, The
Oil and
Gas J., Vol. 77, NO.25, pp.110-lll(1979).
11. B. Smith, Restart of heavy crude lines probed, The Oil and Gas J., Vo1.77, No.
27,
pp. 105-106 (1979).
12. B. Smith, Design of heavy crude facilities explored, The Oil and Gas J., Vol.
77, No.
29, pp. 69-70 (1979).
13. B.M.A. Rao, S.P. Mahajan and K.C.Khilar, A model on the breakdown of crude oil
gel, The Can. J. Of Chem. Engg., Vol. 63, No. 1, pp. 170-172 (1985).
14. T.Viswanathan and KC. Khilar, Hydrodynamically induced gel breakdown in pipes,
The Can. J. Of Chem. Engg., Vol. 67, No. 3, pp. 353-360 (1989).
15. 3. Sestak, M.E. Charles, M.G. Cawkwell and M. Houska, Start-up of gelled crude
oil
pipelines, Journal Of Pipelines, Vol. 6, No.1, pp. 15-24 (1987).
16. M.G. Cawkwell and M.E.Charles, An improved model for start-up of pipelines
containing gelled crude oil, Journal of Pipelines, Vol. 7, NO. 1, pp. 41-52,
(1987).
17. A. Majeed, B.Bringeda1 and S. Overa, Model calculates wax deposition for N. Sea
oils, The Oil Gas J , Vol. 88, No. 25, pp. 63-69 (June 18,1990).
18. R.A. Vora and D.P. Bharambe, Polymeric flow improvers, Indian J. Techol., Vol.
31, No. 9, pp. 633-635 (1993).
19. L.T. Wardhaugh and D.V. Boger, Flow characteristics of waxy crude oils
:Application to pipeline design, AIChE J., Vol. 37, No. 6, p. 871 (1991).
20. J.A. Svendsun, Mathematical modelling of wax deposition in oil pipeline
systems,
AIChE J., Vol. 39, NO.8, pp. 1377-1388 (1993).
21. T.F. Al-Fariss, Effect of wax on oil behaviour, Indian Chemical Engineer,
Vol. .=I,
NO.2, pp. 8-12 (1990).
22. G.P.van Engelen, C.L. Kaul, B. Vos and H.P. Aranha, Study of flow improvers for
transportation of Bombay High crude oil through submarine pipelines, Journal of
Pet. Tech., Vol. 33, No. 12, pp. 2539-2544 (1981).
23. T.R. Sifferman, Flow properties of difficult-to-handle waxycrude oils, Journal
of Pet.
Tech., Vol. 31, No. 8, pp. 1042-1050(1979).
24. C.A. Irani and J. Zajac, Handling of high pour point west African crude oils,
Journal
of Pet. Tech., Vol. 34, No. 2, pp. 289-298 (1982).
25. R.N. Tuttle, High-pour-point and asphaltic crude oils and condensates, Journal
of
Pet. Tech., Vol. 35, No. 7, pp. 1192-1196(1983).
26. E.D. Burger, T.K. Perkins and J.H. Striegler, Studies on wax deposition in t h
e h a n s
Alaska Pipeline, Journal of Pet. Tech., Vol. 33, No. 6, pp. 1075-1086(1981).
27. C. Chang, D.V. Boger and Q.D. Nguyen, TLEyielding of waxy crude oils, Ind. Eng*
Chem. Res., Vol. 37, No. 4, pp. 1551-1559 (1992).
QUALITY CONTROL OF
PETROLEUM PRODUCTS

~ O D U C T I O N

Qunlity control of petrolcum products 1s ;I n(bc(bssilq.il't hc protlucls ilrt! to


give sillisii~ctory
pedormance to the customcra. Keeping in view 11~.ascli~in(~ss
of mlch prlxluct. fi)r sp(*(:ilic
purpose, standnrd urganisations have t n f L r l md\v)(lsol'trsl.~and
s~cciticdinnc.Bur\.;iu I*
Indim Standard @IS), New Delhi is onc sc~chor~;rnis;~lion
in lndia which stantlnrdihcs
procedures and issues specilations. 111stiluteof Pctroleun~(ll').1J.K and Anlvrican
S(aic1y
for Testing & Materials (ASl"l'), U.S.A. ;IIX thc other two i ~ ~ ~ ~ )
organisiltions
o r l i ~ ~ ~ t wllosc'
methods and specifications are widely followed. Apart from BIS sl)ccifications, I!
cntral Board
Of Revenue, New I)elhi has certain othcr specifications tbr the purpoxc ol'cxcisc
Ic!vy. Some of
the important limits set by them are for carbon residue, flame height,fli~sh[mint.
a ~ visajsity.
~ d
4.2 CLASSIFICATION OF LABORATORY TESTS

!
I

Most of the laboratory tests can be broadly classified into seven groups 11;lst:tl
011 t11('
followingcharacteristics:
Volatility
Combustion
e Viscosity and consistency
e Melting point
e Oxidation
Corrosion and protection
e Miscellaneous tests
Volatility is the major dcterminant ofthc tendency of a hydrocarbon to produce
polontially
ex~losivevapours. I t is also critically important to an cmgine's start and warm-
up. Volatility
is gssessed by the following tests:
(a) Distillation
(b) Vapour pressure
(c) Flash point and fire point
The combustion properties of petroleum products are evaluated by the following
tests:
(a) Antiknock quality-Octane number, Performance number
(b) Ignition quality-Cetane number, Aniline point, Diesel index, Calculated cetanc
index
(c) Calorific value
( d )Burning quality-Smoke point, Char value
46

PETROLEUM REFlMlNGTECHNQLQGY
QUALITY CONTROL OF PETROLEUM PRODUCTS

The determination of viscosity and consistency of petroleum products is done by the


following tests:
(Q) Kinematic viscosity (Redwood, Saybolt, Engler)
(b)Viscosity index
(c) Penetration tests
The tests designed to ascertain the tendency of certain petroleum products to melt
or
liquefy,,tosolidify or to precipitate wax-like materials are:
(a)'k8ezing Point
(b) Cloud point and pour point
(c) Drop point of grease
(d) Melting and setting point of wax
(el Softening point of bitumen
Methods have been devised for the evaluation of storage stability and resistance to
oxidation for gasoline and aviation turbine fuel. These include:
(a) Induction period of gasoline
( b )Thermal stability of Jet fuels
(c) Gum content
Most crude oils are corrosive to greater or lesser extent, frequently due to the
presence of
sulphur compounds, organic acids (mainly naphthenic acids) and traces of brine.
Therefore,
test methods have been designed to evaluate the corrosive poteqtialities of the
petroleum
products which are obtained by processing of crude oils. The following methods are
available:
(a) Total sulphur
(b) Acidity and alkalinity
(c)Copper-strip corrosion test
(dl Silver-strip corrosion test for Aviation Turbine Fuels
The misceJlaneous tests include:
(a) Ash
(b) Carbon residue
(c) Colour
(d) Density.and%pecific gravity
(el Gas ckpmatography of petroleum gases and liquids
(f) Refractive index of hydrocarbon liquids
(g) Lead in gasoline
(h)Water separometer index (modified)(WSIM)
( i ) Ductility
The definition, method and significance of tests mentioned above are given below.
4.3 DISTILLATION

The laboratory distillation test comprises a simple process in which 100 ml sample
is
vaporised in a suitably designed flask fitted with a thermometer, and condensed in
an
ice-cooled tube and collected in a measuring cylinder. Whereas an individual
hydrocarbon
would exhibit a single boiling point, commercial fuel blends boil over a range of
temperatures.
Corresponding readings of vapour temperature and condensate recovered are made at
prescribed intervals and the results are plotted in the form of distillation c w
e . The initial
boiling point (IBP) is taken as the temperature observed at the fall of the first
drop of
condensate, and the final boiling point (FBP) as the maximum temperature reached
during

the test. Due to small losses of vapour a t the connections and openings in the
apparatus and
the residue remaining in the flask on compfetion of the test, the total recovery
does not
generally exceed about 97 percent. A maximum distillation temperature limit of 370%
has to
be set, otherwise the heavier hydrocarbon molecules are liable to suffer from
cracking into
lighter molecules causing the distillation characteristics to change duringtheir
measurement.
Thus fiels heavier than gas oils cannot be tested completely for distillation
behaviour.
The distillation characteristics give a broad indication of fuel type. Being a
measure d
volatility, they determine the system of fuel metering required (wick feed,
carburation or
atomization), and are indicative of the vaporisation behaviour of fuels instorage
(vapour loss
and vapour lock), and in piston-engine manifolds (uniformity of distribution to
cylinders). The
extent of the distillation range for any given fuel is representative of the
availability of that
fuel from the parent crude oil. For a fuel with a high demand, the aim of the
supplier will be
to extend the distillation range as far as practicable. However, due to the
interrelationship
between properties and the associated problems, minimum and maximum limits,
respectively,
may need to be set for the initial and final boiling points.
The significance of this test varies from product to product. In case of crude oil,
the ASTM
distillation data give some idea of the frwtions that could be collected below
300C. If it is a
true boilkg point (T.B.P.) distillation, the TBP curve reveals a lot of
characteristics that are
useful for the design of the refinery. The 10vol.% of distillation for motor spirit
is an indication
of the ease with which the engine can be started. Too high a FBP will cause
crankcase oil
dilution.
4.4 VAPOUR PRESSURE

Vapour pressure of a liquid fuel may be defined as the pressure exerted by the
vapour
above the free surface of the liquid at the given temperature. For volatile,
nonviscous
petroleum products, it is determined by Reid method. This is the pressure exerted
by vapollr
when it is in equilibrium with the liquid under the conditions of test. For
liquefied petroleum
gas, the procedure is different and the determination should be done at 65%. The
conditions
under which vapour pressures are determined give results which are not true because
of the '
air which is invariably present in apparatus. n e true vapour pressure is higher
than the Reid
vapour pressure by about 5 to 9 percent but this relationship varies widely.
The standard Reid apparatus consists of a fuel chamber comectea to an air chamber
of
four times volume, and fitted with a pressure gauge.
This test is important with
,no-x
vzan.oort,pzur&&jg-the gdsoline
*types
of storage tanks employed and the starting characteristics of motor hels. High
t storage and transportation. In case of motor
vapour pressure entails loss of the ~ r o d u cin
spirit, it may cause vapour lock in the gasoline engines.
4.5 FLASH POINT AND FIRE POINT
Flash point and fire point can be taken as indirect measureof the product.
The flash point is the lowest temperature at which application of test flame causes
the vapour
above the oil to ignite. The fire point is the lowest temperatwe a t which the oil
ignites and
continues to burn for 5 second.
The determination of flash point of petroleum products consists of heating a given
volume
of liquid at a standard rate of temperature rise until vapour is produced to such a
degree as
to give a flammable mixture with air in an enclosed space (i.e. closed flash point
temperatye)
or with air in an open cup (i.e. the higher open flash point temperature), ignition
resulting
-

48

PETROLEUMREFINING T E ~ H N O ) ~ ~ & ~

tiom the applicalion of'a small flame. At firc point, not only will the vapour-air
mixture'fir)8h
but the liquid will continue to burn.
Abcl apparatus is used for determiningthc closed cup flash point of' petroleum
products
h ; t v i n ~tlash points between 19C and 49C. Pcnsky-Martens a p ~ a r a t u a
iused
s
for deteymining the flash point of fuel oils and lubricating o h , bitumcn other
than cutback bitumen having
;I ilaxh point :~br>vc
49OC. Clcvcland appariltus is used for determining the flash and fire points
of pctroleun~products cxccpt l'uucl oils and those products having an open cup
flash point below
79C.

Ylirsh p u n t measurcs thc tcntlcncy of the fuel to form a flammable mixture with
air under
conlrollcd laboratory conditions. This is tho only propcrty that must be considered
in assessing
the ovcrull tlammability l~azartlof a mntcrial. I t is used in shipping and safety
regulations
thnldcfinc flttmmable and combustible n~uterials.Petroleum products having low
flash points
irrlb~~otential
to fire hazards. Flash point can indicate the possible presence of highly volatile
ant1 tlan~n~ablo
materials in rclativoly nonvolatile or nonflammnble makrial.
4.6 OCTANE NUMBER

This is a n important test for measuring the antiknock quality of the gasoline
(petrol or
motor spirit). The knocking of the motor fuelsis compared using blends of reference
fuels. The
standard reference fuel8 used foroctanenumbers below 100areiso-octiineand normal
heptwe
which arc assigned valuerr of100 and 0, respectively, on the octane number scale.
The octane
number of thc fucl is defined atl the volume percentage ofiso-octane t2,2,4-
trimethyl pentane)
in a blcnd with n-heplanc which is equal to the test fuel in knockintensity under
standardised
and closely controllcd conditions of test in a single-cylinder, variable
cbmpression ratio
enbines, known as CFli cnginerr. Thus, a fuel of 87 octane number has a CFR engihe
performance matching that obtainable with a blend of 87 volume percent iso-octane
and 13
volume percent n-heptane. Thc rating can be done by either Research mcthod or Motor
method.
The differences in the two methods are as follows:
Octane numbcr rcquirc~ncntsof gasoline engines depend on their compression ratio.
If the
fuel meets the minimum requirements in respect of octane number it ensures trouble
Bee
ol~cration.Apart fiom being a nuisance, the knocking in an engine may result in
loss of energy
: ~ n da t times may cause severe damage to the engine.
4.7 PERFORMANCE NUMBER

This is used to estimate knoekihg characteristics of aviation gasolines of octane


number
highcr than 100. The standard reference fuels for knock ratings above 100 octane
number are
iso-octane and its blends with tetraethyl lead (TEL). The ratings of aviation
gasoline above
100 octane number are normally expressed as performance number.
The performance number scale is based on engine power output. The performance
number
of an aviation fuel represents approximately the maximum knock-free power output.
The

QUALITY CONTROL OF PETROLEUMPRODUCTS

49

onrformance number shows the percentage increase in aipcrafi engine power for
addition of
TEL to iso-octane and is given by
Performance number - 100)
Octane number = 100 + (
3
-

r-------

On the performance number scale, 100 octane number equals 100 performance number.
The ratings of aviation gasoline above 100 octane number can be done by
(a)Aviation method (lean mixture rating);
( b )Supercharge method (rich mixture rating); and
(c) xie ended motor method.
I n aviation method, the rating is done a t 1200 rpm by comparing the combustion
chamber
temperature for the fuel with those of the blends of known performance number. This
lean
mixture rating gives us an idea of the availability of knock limited power in spark
ignition
type aircraft engines when the aircraft is under cruising conditions.
In supercharge method, the rating is done a t 1800 rpm by comparing the h o c k
limited
power of the fuel with those for blends of iso-octane and isooctane plus TEL. This
is done a t
constant compression ratio by measuring indicated mean effective pressure a t
enough points
to define the mixture response curves for the sample and the reference fuels. When
the knock
limited power for the sample is bracketed between those for two adjacent reference
fuels, the
rating is cakulated by interpolation. The rich mixture rating indicates the a v d a
b z t y o f b o c k
limited power when the plane is under take-off conditions.
In extended motor method, the rating is done in a CFR engine normally used for
rating of
motor gasolines by motor method (rpm=9OO). The knocking intensity of the fuel is
bracketed
between reference fuel prepared from iso-octane and TEL and the performance number
is
calculated by interpolation.
4.8 CETANE NUMBER

Cetane number is related to the ignition delay of a fuel in a diesel engine, i.e.
how rapidly

to lower cetane numbers.


Cetane number of diesel fuels is determined in a single cylinder CFR engine by
comparing
the ignition delay characteristics of the diesel fuels with that of reference
blends of known
cetane number. Cetane number of a diesel fuel is defined as the whole number
nearest to the
value determined by calculation from the percentage by volume of normal cetane in a
blend
with h e p t a m e t w nonane which matches thdignition quality of the test fuel
when compared
bv this method..The matching blend percentages to the fiist decimal are inserted in
the
following equation to obtain the cetane number:
... (4.2)
Cetane number = % n-cetane + 0.15 (% heptamethyl nonane)
The shorter the ignition delay period, higher is the cetme number of the fuel.
Cetane number is the index of ignition quality of a fuel. High cetane number fuels
will
facilitate easy starting of compression ignition engines, particularly in cold
weathers, and
faster warm up. These also result in increased engine efficiency and power output,
reduced

,,
Q U A M Y CONTROL OF PETROLEUMPRODUCTS

exhaust smoke and odour and combustionnoise. In the absenceoftesten&e,the diegel


index
or the calculated cetane index will give an approximate idea ofthe ignitiofi quai*
ofthefdcl.
Cetane number can also be roughly assessed by the formula:
Cetane Number = 0.72 x Diesel Index + 10
... (4.3)
4.9 ANILINE POINT
Aniline is a poor solvent for aliphatic hydrocarbons and excellent one for
aromatics. This
propertg is used in the aniline point test. Aniline point of an oil is the e t u r
e &
l & f & J - a W - .
..
Equal volumes of the sample and aniline (5 ml each) are heated or cooled with
stirring in
a jacketed test tube and temperature at which complete miscibility occurs is noted.
High aniline point indicates that the fuel is highly paraffmic and nence has a high
diesel
mdex and very good ignition quality. In case pf ar~maGc&he-milanilhe
point is low u
e
._+,-.-" ~.rrc.-.n-.ro-i

4.10 DIESEL INDEX

Diesel index is an indication of the ignition quality of a diesel fuel. This is


dctemined by
calculation from the specific gravity and the aniline point of the sample. Although
it is ofthe
same order as the cetane number, it may differ widely from the cetme number. Higher
the
diesel index, better is the ignition quality of the diesel i e l . It is normally
used aa a guide to
ignition quality of the diesel fuel in the absence of test engine for the direct
measurement of
cetane number.
The diesel index is calculated as follows:
(a)

(b)
(c)

Diesel index = Aniline point, OF x OAPI


100
Diesel index = Aniline gravity constant
100
Diesel index = Cetane number 10
0.72

...(4.4)
...(4.5)
J4.6)
4.1 1 CALCULATED CETANE INDEX
Calculated Cetane Index (CCI) is based on specific gravity and the 10 percent, 50
percent
and 90 percent distillation temperatures of the fuels and it gives numbers that
correlate with
the engine-testing method. The relationship is given Ly the following four-variable
equation:
CCI = 45.2 + 0.0892 TION+ (0.131+0.901B)T ~ O+N(0.0523 - 0.428)Tgo~
+

where

0.00049 [(T~oN)~
- (T~oN)~]
+ 107B+ 6 0 ~ ~
TION= Ti0 - 215 ,OC
Tlo = 10 percent distillation temperature, OC
T ~ O=NTm - 260, OC
Tso = 50 percent distillation temperature, OC
T ~ O=N2'90 - 310 OC
T90 = 90 precent distillation temperature, "C
B = - 3.5(G-O.85) - 1

G = specific gravity at 15OC

J4.6)

38

Thirr CCI ia useful for estimating cetane numbers when a test engine is not
available for
direct measurement, and it may be convenientlyemployed for estimating cetane number
when
the quantity of sample available is too small for an engine rating.

CALORIFIC VALUE

This is the quantity of heat released per unit quantity of fuel, when it is burned
completely
with oxygen and the products of combustion returned to ambient temperature. This
quantity
of heat will include the heat of condensation (latent heat) of the water vapour
formed by the
'
combustion of the hydrogen in the fuel, as it cools to ambient conditions. It is
called the @
calorific value" or "hi~hercalorific yalue".
Most h z t i n g applications cannot recover the heat of the water vapour; it
simply escapes
with the vapoui out of the chimney. The potential heat content is therefore more
nearly
indicated by subtracting this latent heat from the gross calorific value, and the
resultant value
is called the net calorific value, or lower calorific value.
A weighed quantity of the sample is burned in a bomb calorimeter under controlled
conditions. The calorific value is calculated from the weight of the sample and the
rise in
temperature. I t can also be calculated from the formulae
J4.7)
Calorific value = 12400- 2100 p2

in which calorific value is in caYgm and p is density at 15OC in gm/crn3.


Calorific value is a measure of the energy available in a fuel. Thus a knowledge of
the
calorific value of the fuel, and the efficiency of the heating equipment, is
essential to compare
the merits and running costs of different fuels and energy costs. It is a critical
property of fuel
intended for use in weight-limited vehicles.
4.13 SMOKE POlNT

Smoke point is the maximum flame height in mm at which the fuel will b u m without
smoking *hen determined in a smoke point apparatus under specified conditions.
Smoke point apparatus comprises four main parts-lamp body, candle socket, candle
and
stand. The lamp body with chimney is fitted on the inside with a polished black
engraved scale
which is marked in white. A gallery is secured in the lower part of the body. The
candle socket
assembly is designed to give a smooth rise and fall over the total distance of
travel. To ensure
interchangeability the candle is finished to close tolerances. The assembly is
mounted on a
stand. The sample is burned in a standard lamp with a specified wick for five
minutes. The
height of the flame is read when it leaves no smoky tail.
This is an important test for evaluation of illuminating oils (kerosines) for their
ability to
bum without producing smoke and the assessment of the burning quality of aviation
fuels.
Higher the smoke point better is its domestic use. I t also serves as a guide to
assess the
aromatic content of kerosines.
4.14 CHAR VALUE

The amount and nature of the deposits (char) produced on a wick during combustion
depend on the hydrocarbon composition of the fuel and also on the design of the
appliances in
'which it is used. Char occurs as a result of the breakdown and decomposition of
the kerosine
under the local conditions existing at the wick surface, and these conditions will
also determine
what proportion of the decomposed products remains on the wick.
52

PETROLEUM REFININGTECHNOLOGY

OUAUTY CONTROL OF PETROLEUMPRODUCTS

4.15 VISCOSITY

'1

,
I

Kinematic viscosity is defined ris the mearidre of the r e d s t h i &to gravity


flow of a fluid,
the pressure head being proportional to the density. The time of flow of a fixed
volume of fluid
is directly proportional to its kinematic viscosity. The unit of kinematic viscosi$
is, cm2/s or
Stoke. The unit most usually used in measurement of the kinematic viscosity of
~etioleum
fuels is the centistoke (cSt) which is
Stoke.
Dynamic viscosity, also known as absolute viscosity, is the ratio of applied shear
stress to
rate of shear and thus a measure of the resistance of a fluid to flow. The unit of
dynamic
viscosity is gm1cm.s or Poise. Dynamic viscosity may be obtained from kinematic
viscosity by
multiplying it by the density of the fluid at the temperature at which measurement
was made.
Kinematic viscosity may be measured as an absolute property of the fuel, or
alternately
as a conventional property that is'dependent on the instrument and the method used.
Both
approaches depend on the efflux time of a given volume of sample flowing under its
own head
through a restriction. This follows because the force acting the laminar (low
speed) flow of a
fluid through a restriction is approximately proportional to the dynamic viscosity,
whereas
the force promoting the flow is that due to gravity, and is proportional to the
density of the
fluid. Hence the time taken for the gravity flow of a given volume of sample
through a
restriction is approximately proportional to the kinematic viscosity.
The conventional methods, which are generally simpler but less accurate, are
represented
by the Redwood instrument in the UK, Saybolt in the USA and Engler in continental
Europe.
They each comprise a sample cup fitted with a standard-sized oriiice in the base
and
surrounded by a waterjacket containing a heating device. When the temperature
reaches the
test level, the orifice is unsealed and the time of flow is determined for the
given volume of
sample. The result is reported as Redwood or Saybolt universal second or as Engler
degree,
given by the efflux time ratio for the sample and for water. When the efflux time
exceeds a
specified maximum-for example 2000 s-due to high viscosity, use is made of a
Redwood No. 2,
or a Saybolt Furol (fuel and road oils) instrument, incorporating a larger diameter
orifice.
The absolute determination of kinematic viscosity'generally employs a glass U-tube
viscometer with a capillary tube built into one leg. The length-diameter ratio is
such that end
effects are negligible and the precision is therefore higher. The instrument is
suspended
vertically in a thermostatically controlled water bath, and the time is measured
for a given
volume of sample to flow d o u g h the capillary. This measured time period is
inserted into an
\
equation to give a direct measure
of the kinematic viscosity in centistokes.
v=At-B/t
...(4.8)
where
A = instrument calibration constant;
B = instrument type constant, depending on the capillary diameter;
and
t = efflux time, s (Engler degree for Engler viscometer)
Table 4.1 gives the values of A and B for Redwood, Saybolt and Engler viscometers.
Viscosity is an important characteristic of a fuel and it is used for the pump
design. Pump
clearance are aGusted according to the viscssity and if i t is out of the range, it
will result in
pump seizer. Pump operation of an engjne depends on the proper visesity of the
liquid fuel.
The viscosity of liquid fuel is important to its flow through pipelines, injector
nozzles, and
orifices, and for atomization of fuel in the cylinder.

Table 4.1 Instrument Constant Values

4.1 6 VISCOSITY INDEX

Viscosity index (VI)is the most widely used way of characterizing the effect of
change of
temperature on the viscosity of any oil. Proposed by Dean and Davis, viscosity
index is an
empirical concept based on the behaviour of mineral oils. In this concept, an oil
whose viscosity
changes rapidly with change in temperature has a low VI. An oil with a minimum
change in
viscositywith change in temperature has a highVI. In this system, Pennsylvanian
(paraffinic)
oils of a selected type which show a desirable, relatively small change of
viscosity with change
in temperature, were assigned a VI of 100, while selected Texas Coastal oils
showing less
desirable viscosity-temperature characteristics were assigned a VI of O.VI is
governed by the
type of hydrocarbons in the oil.
Dean and Davis prepared tables giving the kinematic viscosities a t 40C and 100C
of the
Texas Coastal oils (L) and the Pennsylvanian oils (HI. The values of kinematic
viscosities of
L and H are given in Table 4.2. The VI of an oil can be calculated from the
equation

.,

v1=L-Ux100

L-H

where

U = kinematic viscosity at 40C of the oil whose VI is to calculated


L = kinematic viscosity at 40C of an oil of 0 VI
H = kinematic viscosity at 40C of an oil of 100 VI

.17 PENETRATIONTESTS

Several standard grades of bitumen are comlqercially available, which are normally
ssified into different grades by p e n e t r a t i o n p e sample of bitumen is
plzced in a
suitable container and brought to a temperature of 25OC in a water bath. The
weighted needle
is brought to the surface.and at the end of 5 seconds interval, the penetration the
needle
into the bitumen, in units of UlO mm is t e ~ v o nofthe
' b
$
The penetration at 25OC and the softening point, or penetrations a t two di erent
temperatures (for example, 25OC and 10C) can be used to define the extent to which
the consistency
of a bitumen changes with temperature. This an important characteristics for
bitupens, and
determines the type of bitumen used for a particular application. Various factors
have beexi

.,
QUAUTYCONTROLOF PETROLEUMPRODUCTS

used to define temperature 'dependence. The most commonl~used factor,.however, is


the
Penetration Index (PI),which is defined as follows :

Table 4.2 Values of H. L and D for Kinematic Viscosity at 100 O


C
(H = Kinematic viscosity at 40C of an oil of 100 VI, cSt,
,

L = Kinematic viscosity at 40 OC of an oil of 0 VI, cSt)

55
56

PETROLEUMREFININGTEFHNOLQGY

QUALITY CONTROL OF PETROLEUMPRODUCTS

57
grease' of an hknown formulation. It cannot be used to measure the upper operating
temperature limit for a grease.

log (800) - log (PEN25C) - 20 - PI 1


TRB 25
- [i?Gx][SO]

where TRBis the ring and ball softening point of the bitumen in "C.
etration of a
bitumenat the softening point temperature is about 800. Bitumens less n fected by
temperature change have positive values of PI and those ?ore affected by
temperature change negativ'e
values.

-?

4.18 FREEZING POlNT

Freezing point is the temperature at which crystals of hydrocarbons formed on


cooling
disappear when temperature of fuel is allowed to rise.
This method covers a procedure for the detection of separated solids in aviation
reciprocating engine and turbine engine fuels at any temperature likely to be
encountered during flight
or on the ground.
4.19 CLOUD POlNT AND POUR POlNT

--

Cloud point of petroleum products is the temperature at which a cloud or haze of


wax
crystals appears at the bottom of the test jar when the oil is cooled under
prescribed conditions.
It is generally determined for products that are transparent in a 43-mm thick layer
and have
cloud points below 49C.
The cold filter plugging point test is used to determine the extent to which diesel
fuel or
gas oil will flow, even though the temperature is below that at which wax crystals
normally
appear, i.e. cloud point.
Cloud point gives a rough idea of the temperature above which the oil can be safely
handled
without any fear of congealing or filter clogging.
Pour point is the lowest temperature expressed in multiple of 3C at which the oil
is
observed to flow when cooled and examined under prescribed conditions.
Pour point is a well-established test to estimate the temperature at which a sample
of oil
becomes sufficiently solid to prevent its movement by pumping. The pour point
temperature
depends to a large extent on the thermal history of the sample. Also, the pour
point indicates
the waxy nature of the oils.
4.20 DROP POlNT OF GREASE
The standard drop point tests indikte that the temperature at which the thickener
is so
soluble in the base oil that the grease becomes substantially fluid. Clay and dye
thickened
greases have no measurable drop points.
The drop point can be used to assess whether a grease of known formulation has been
properly made or to obtain an indication of the type of thickener which has been
used in a

'

4@
'
I

421 MELTING AND SElllNG POlNT OF WAX


The cooling curve method is used to determine the setting point of waxes. Molten
wax is
allowed to cool in a specified apparatus and the temperature is recorded at
frequent intervals
The point at which the temperature remains within a range of O.lC for one minute
is taken
as the setting point. This method is not suitable for microcrystalline or
intermediate waxes,
or blends of paraffin waxes with these or any additives.
The congealing point of a petroleum wax or petrolatum is determined by applying a
drop
of molten wax to a thermometer bulb, and noting the temperature at which it
congeals when
the thermometer is rotated under standardised cooling conditions.This method is
suitable for
all waxes.
The drop melting point of wax or petrolatum is determined by recording the
temperature
at which a drop of the sample falls from the bulb of a thermometer when heated
under standard
conditions.
These are considered to be suitable for checking the constant quality of wax output
in
refineries.
4.22 SOFTENING POlNT OF BITUMEN

Bituminous materials do not change from the solid state to the liquid state at any
definite
temperature, but gradually become softer and less viscous as the temperature rises.
For this
reason, the determination of the sofbning point must be made by a fixed arbitrary,
and closely
point is defmed as the temperature at which a substance attains a particular
under specified conditions of tes A steel ball of specified weight is placed
upon a disc of sample contained within a metal ng of specified dimensions. The
assembly is
heated at a constant rate anct the temperature at which the sample becomes soft
enough to
allow the ball, enveloped in a bitumen, to falld distance is taken as the softening
d

2 The ring and ball test for softening point measures the temperature in OC at
which a

standard disc of bitumen confined in a metal ring softens to such an extent, when
heated at a
rkteif 5"~/minute,that it deforms under the loading imposed by a small steel ball
which falls
a distance of 2.54 cm.
The determination of the softening point of bitumen is regarded by some as an
indication
of viscosity, although from the point of view of the application of bitumen its use
is limited to
that of its title. The softening point is used in the designation of hard bitumens
and oxidized
bitumens.
4.23 INDUCTION PERIOD OF GASOLINE
Induction period of gasoline is the time elapsed between the placing of the bomb in
the
bath and break point at 100C. Break point is the point in the pressure-time CUNe
that is
preceded by a pressure drop of exactly 2 psi within 15 minute and succeeded by a
drop of not
less than 2 psi in the next 15 minute.
Fifty millilitre of the sample is enclosed in a bomb with oxygen a t 100 psi and
heated in a
water bath at 100C. The pressure is then recorded either on a chart or read every
15 minutes
60

PETROLEUMREFINING~TECHNOLOGY

4.26 TOTAL SULPHUR

The test is continued until the break point is reached. The test result is reported
as induction
period in minute.
This test is conducted to assess the stability of gasoline in storage. This test
indicates the
presence,of unsaturated hydrocarbons in the fuel and hence its gum forming
tendency. Higher
the induction period, better is the storage stability of the fuel. An induction
period of 360
minute under laboratory conditions ensures storage stability of at least six month.
However,
this correlation may vary with different gasolines under different conditions.
4.24 THERMAL STABILITY OF JET FUELS

Jet fuel thermal oxidation tester (JFTOT) is used to measure the high temperature
stability of gas turbine fuels. This subjects the test fuel to conditions which can
be related to
those occumng in gas turbine engine fuel systems. The fuel is pumped at a fixed
volumetric
flow rate through a heater after whichit enters thestainless steel filter whert!
fuel degradation
products may become trapped. The apparatus requires 600 ml of test fuel for a 2.5
hour test.
The essential data derived are the amount of deposits on an aluminium heater tube,
and the
rate of plugging of filter located just downstream of the heater tube.
In the JFTOT a charge is placed in a reservoir and the whole system is pressurized
to 3.45
MPa with nitrogen. This ensures a single-phasereaction in the heated section. The
fuel passes
from the reservoir through a 0.45 micron filter, to remove trace particulate
matter, and into
the reactor section, where it passes upwards in an annular space over iyaluminium
tube and
out via a 17 micron stainless steel filter through a heat exchanger, to cool it,
and back to the
top of the reservoir. The used and unused fuel in the reservoir are separated by a
floating
piston. The fuel is rated by a visual tube rating or by placing the tube in a Tube
Deposit Rater.
In this the tube is rotated at a constant speed and its surface scanned by two
light sources
reflecting off the tube on to a photocell. The photocell gives a signal to a meter.
Also, the
differential pressure across the 17 micron filter is measured.
The test results are indicative of fuel performance during gas turbine operation
and can
be used to assess the level of deposits that can form when liquid fuel contacts a
heated surface.
4.25 GUM CONTENT
The gum compounds which can be present or produced in the fuel are classified into
two
types for test evaluation. Existent gum may be already formed in the fuel and can
be deposited
from solution as the fuel evaporates. Potential gum may be formed under extended
storage
conditions during which unstable hydrocarbonsare thereby polymerized and oxidized
to form
gums.
Existent gum is the amount of nonvolatileheptane insoluble residue left when the
sample
is evaporated in a jet of hot air at 160C. For jet fuels, the evaporation is camed
out in a jet
of superheated steam at 232OC.
Potential gum is the amount of gum formed afier the sample is aged in an oxidation
stability bath and evaporated under specified conditions.
Gum is always troublesome in any fuel and it may cause piston ring sticking and
deposits
on engines. The amount of gum points to the presence of olefins which have very
poor storage
stability. The existent gum test is claimed to measure the amount of gum or gum-
forming
compounds existing in the fuel, while the potential gum test attempts to predict
the tendency
to form gum on storage and use. These gum tests are usually used as refinery
control methods.

QUALITY CONTROLOF PETROLEUM PRODUCTS

"
I

1
I

g1

.: .

This is determined by lamp method or wickbold procedure for volatile petroleum


Products
and by bomb method for heavier products. Sulphur in the sample is oxidized by
combustion ,
and is estimated volumetrically after absorption in Hz02 or by gravimetric methods
after
converting into barium sulphate.
Sulphur compounds pose a dual problem: they not only cause environmental pollution
from their combustion products, but these products are also naturally corrosive and
cause
severe physical problems to engine parts. A knowledge of the sulphur content of
petroleum
products is therefore of importance to both refiner and user.
d c l D I T Y AND ALKALiNln

New and used petroleum products may contain acidic constituents present as
additives or
as degradation products, such as oxidation products, formed during service. Total
acidity is a
measure of the combined organic and inorganic acidity.
The acids in the sample are extracted in neutral alcohol andthen titrated against
standard
alcoholic potassium hydroxide under hot conditions.
Total acidity is an indication of the corrosive properties of the product.
Inorganic acidity
is a measureof the mineral acid present. Organic acidity is obtained by deducting
the inorganic
acidity from the total acidity.
ER-STRIP CORROSION TEST

products contain sulphur compounds, most of which are removed during


refining; Of the sulphbr compounds remaining in the petroleum product, however,
some can
have a corroding effect on various metals. This corrosivity is not necessarily
directly related
to the total sulphur content. The effect can vary according to other chemicals and
types of
sulphur compounds present.
which is then
A cleaned and smoothly ~oli$hedcopper strip is irnmerse&&hsm@&
mamtained at the specified temperature for the specified length of time. This strip
is removed
L a m p l e , washed with aromatic and sulphur free petfoleum spirit and examined
for
evidence of etching, pitting or discolouration. It is then compared with F T M
copper-strip
corrosion standkd colour code. Th_eclass%cation cbde indkates that the numbers 1 ,
2 , 3 and
4 designate slight tarnish,'moderate tarnish, dark tarnish m d
corrosion,kespectively. Sub-scripts-a-e describe a standard colour reproduction'in
the standard chart. For example, the
classification code l a indicates slight tarnish with a light orange colour.
C ~ h itest
s serves as a measure of possible difficulties with copper, brass, or bronze parts
of
the fuel systems.

4.29 SILVER-STRIP CORROSION TEST FOR AVIATION TURBINE FUELS

A Polished silver strip is completely immersed in Aviation Turbine Fuel at 45 f 1C


for a
period of 16hour. At the enctof this period, the silver strip is removed from the
sample, washed
and evaluated for corrosion against the set of standard.
Since some parts of the fuel pumps in aircraft are made of silver, the corrosive
tendency
of the he1 for silver assumes special significance.The cumulative effect of
corrosion on such
a vital component in the aircraft is hazardous.
_?

4.30 ASH

-h~ji{:!:*;:~
: p > 5 ~ z :.b,,:;.7!t$;
~ y ~j !;,;~
: ;.,:,.t;.3:
... c ,~:.., ~ ~ ~. ~.. ~
<..

.,&h.@n!~esultfr0.p oi1,water-solpble metallic cqpounds, or extraneous solids, such


as

<,

di&qj&+s$,~.:~~:~.
. ,
.
..
'A kqom'p~,ogn$:.qf
3aible is ignited and the c a r b o n a ~ i oresidue
~s
I&ib
. heated
..
to
800C in a muffle hrnace, cooled and weighed as ash.

I.

Table 4.3 ColourMeasurementmethods,


-. :.-;- , .!l:.,,.:. ...
, ,:
. - . .
..
.
i

Main equcpment

Saybolt chromometer

Chromometer

ASTM Colour

Calorimeter

Colour of dyed aviation


gasoline
Colour by the Lovibond
tintometer

'

'

,,.

. .

. ,

Colour scale
I
+30to - 16
Oto8

Colour comparator

.,

Applt'catlon
White
products
petroleum

Heavy petroleum
products, lubricating oils
Dyed aviation gasoline

Permanent colour glass


disc
Lovibond tintometer Colour standards of dif- A11 petroleum products
ferent rating for red, yel- except black oils and
low, blue and neutral tint bitumens
-J

Specific gravity is the ratio ofthedensity ofafluidtothatofwaterat the same


temperature.
The temperature usually specified is 15.56OC. In the USA, specific gravity of an
oil is often
- e , ~ ~ e s s as
e ddegrees kP1.API gravity is an arbitrary figure related to the specific gravity
of
jytroleum products in accordance with the formula:
141.5
. ,
Degrees API =
- 131.5
Specific Gravity at 15.56C115.560C
. .(4.11)

onradson Method
quantity of sample is placed in a crucible and subjected to destructive
distill$tion. The residue undergoes cracking and coking reactions during' fixed
period of severe
heating. At the end of the specified heating period, the crucible containing the
carbonaceous
residue is, cooled in a desiccator and weighed. The residue remaining is calculated
as the
'percentage of the original sample and reported as conradson carborl residu

?,

The specific.gravity is an indication of thetype of hydrocarbon present, being


highest for
aromatics and lowest for paraffins. The API gravity reverses this relationship. The
most accurate method of determining the specificgravity of an oil is to weigh a
known
volume in a specific-gravity bottle at 15.56OC. A correction may be applied by
measuring the
'specific gravity at some conventional temperature near 15OC and adding or
subtracting
0.00063 per O C above or below 15OC.
' Another method for determining the specific gravity of the oil is by means of a
set of
hydrbmeters. A hydrometer is placed in the 6il sample at 15.56OC and allowed to
come to rest.
The specific gravity is shown on the scale at the point coincident with the surface
of the oil.
Accurate determinations of the density, specific gravity and API graliity-of
petroleum
products are necessary for the conversion of measured volumes to volumes a t
standard
temperature of lb.56OC. When the volume of oil is known, its mass can be
calculated. These
factors govern the quality of cmde petroleum. These properties, however, are
uncertain
indications of fuel quality, unless correlated with other
A correlation of fuel density
with particulate emissions indicates increasing particulate emissions with
increasihgdensity.

Method
e sample S t e r being weighed into a special glass bulb having a capillary opening
is
'plackd. in"&metdfurnace maintaihed a t 550C for 20 i I'minute. Thesampleie thus
quickly
'1heatedytothe point, atwhich all volatile Matter i~evaporatedout of the bulb with
or without
decompositionwhile the heavier residue remaining in the bulb undergoes cracking and
cqking
reactions. Aftek a specified 20 minate heatingperiod, the bulb is removed from the
bath, cooled
in a desiccator and again weighed. The residue remaining is calculated as the
percentage of
the original e m p i e and reported as ramsbottom carbon residu
of a fuel oil when
C?+on ;&due gives a measure of
h$ated in a buI6 under prescribed conditions. While not directly correlating with
engine
deposits, *s property is considered as an approximation. For example, carbon
residue value
of die& h e 1 corielates with the amount of carbonaceous depmits the fuel will
form.& the
combustion chamber of the engine. The expected carbon deposits in the combustion
chamber
is greater for higher value of the carbon residue. Carbon residue is also used in
design
calculation of vessels.

4.34 GAS CHROMATOGRAPHY OF PETROLEUM GASES AND LIQUIDS

4.32 COLOUR

Colouris an indication of the degree of refining of the products. Various test


methods used
for the measurement of colour of petroleum products along with their main items
equipment
and product application range are given in Table 4.3.

Density of a fluid is its mass per unit volume. It is measured over a range of
temperatures.
usually for convenience a t the temperature at which the fuel is to be stored.

w r b o n residue can be defined as the amount of carbon residue left after


evaporation and
pyrolysis of an oil and is intended to provide some indication of relative coke
forming tendency.
Either Coriradson method or Ramsbottom method can be used to determine the carbon
residue of petroleum products.

4.33 DENSITY AND SPEClFlC GRAVITY

..;.,,:<,<
% * , ( ...(,....
.rll..-..
. ~ . ..

Name

A b ~ w l e d g eof, the amount of a product's ash forming material can provide


information
on whethemthe-product is suitable for use in a given application.

I
,;,,il5

fi measured volume of the gas sample is introduced into a chromatographic column


and
transported through the column, the sample is split into various components, either
by
adsorption or partition, depending on the column packing. The composition of the
sample is
determined from the chromatograms by measuring the area under the peaks. An
identification
of the components is done by noting the elution time.
- .
4.35 REFRACTIVE INDEX OF HYDROCARBON LIQUIDS

Refractive index is defined as the ratio of the velocity of light (of specified
wavelent$) in
air to its velocity in the substance under examination. It may also be defined as
the sine of the
64

PETROLEUMREFINING TECHNOLOGY

angle of incidence divided by sine of the angle of refradion, as light passes from
air into the
substance. The refractive index of liquids varies inversely with both wavelength
and temperature. Refractive intercept is calculated by

'

Refractive intercept = n - 2

...(4.12)
where ri is the refractive index at 20C and p is the density at 20C,gm/cm3.
' ~ i ~ h t h e content
ne
in naphthas can be easily calculated by knowing the refractive index
and density of the saturates fractions as determined by the refractive intercept
method. There
is a relation between the molecular weight, aromatics and refractive index of
hydrocarbons
and hence the determination of refractive index gives an indication of the content
of aromatics
in the hydrocarbon fractions.
4.36 LEAD IN GASOLINE

The lead alkyl is converted to lead chloride and extracted from the gasoline by
refluxing
with concentrated hydrochloric acid. The acid extract is evaporated to dryness. Any
organic
material present is removed by oxidation with nitric acid and the lead is
determined
gravimetrically as lead chromate. The method covers the gravimetric determination
of the
total lead content of gasoline and other volatile distillates blended with lead
alkyls (tetraethyl
lead or tetramethyl lead, etc.).
!
Tetraethyl lead is added in gasoline to improve the octane number but it is highly
poisonous. Hence, its concentration in gasoline is restricted and its handling is
done with
utmost precaution.

4.37 WATER SEPAROMETER INDEX (MODIFIED) (WSIM)


This is carried out with a water separometer. It~measuresthe water separation
characteristics of fuels expressed in terms of WSIM.
An emulsion of water and fuel is prepared and passed through a cell containing a
standardized 'fibreglass' coalescer.~Theeffluent from the cell is examined for
entrained water
by light transmission. A numerical scale (0-100) rates the case with which the fuel
releases
gxpu!sified water.
:,,WSIMis a measure of fuel cleanliness relative to its freedom from surfactant
materials.
A higher WSIM rating indicates that the fuel is cleaner relative to surfactant
materials.
4.38 DUCTlLlPl
Bituminous surfaces exposed to varying temperature conditions undergo a great deal
of
elrpansion and contraction. Therefore an important characteristic of the Kinder is
its ductility
and the degree of ductility has an effect on the cracking of bituminous surfaces
caused by traffic
stress. The ductility of bitumen is expressed as the distance in centimeter to
wfich a standard
briquette can be elongated before the thread formed breaks under the specified
conditions.
A molten bitumen sample is poured into a standard mould, allowed to coal to room
temperature and then placed in a water bath so that the briquette can be brought to
test
temperature before mounting in the testing machine. Ductility testing machine
consists of a
moving carriage moving over a lead screw.An electricmotor driven reduction gear
unit ensures
smooth constant speed and continuous operation. The temperature is controlled
thermostatically.
-7

Bitumen having high ductility may be more temperature susceptible.

:&,tfYiiiiiiFYB,'C!'C!E
Td'(jr:&,M6i;.4*c$i

.'"

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<,.:

'.,

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.,:,,,;!!,:,:l:.ji:.:

,! :..1<.<7<.

g&$rakf

%+;*::i g ~ j k : 'Y$<.T,
: ~ ~t:F* 1% ,
.
.

, ~ r i t & ~ ~ ~
hefi+.
. + .;
;
.ji
.!,_
-'
li&t, $Kp$$&Pi.
i?
: .,$>,..
t6mp&f&@
:;.:.I
d & T ons
~ denved
$ ~ h from.
~ but
~ fieirol'eum
<
condensed
, ~ ~whl~h
to the m
Iiquidtitst.eatnmbievt
by aP$ffclAbhfsprri:da@&O
$!! B ' & B & ~ ~ & K x h ~ ~ ~ ~ @ & ~ ~ ~ ~ < $ & & t ~ &
are
&4&eY
Ir4:. ! ,
:,$tored
: ~ tfanap6~d
d
&liiji$duids.bnder praswe. p hey are sold .apmpane or butane
or
undr
..
bj2~?y8>.:sj...tis:

tgffl,.

3:&&&!.....
L!

.,.

, .

j+xp,..d,) & . , J A ~ ~ ~u::.


.

......
p7$~c5$~+5~~9~@~~$l~~.tPo
z.,
,(,

:i~~f;'e'~~ideTame~sU~~~~S.~n~~ne,
\....
.., ,. ' ' ?"
. . . . . . .

*,:a,

it..

~ b ~ ~ t : ~ ~ ~ , . H p. .. . . ~, ~ ~ i ~ J ~ d i ~ .

-:,<,.-;.

;.

....;....

6;:$.i'embairt2bn%
itI;~pG
:..

;...

:.>,:
,?..! i!.

. .-

. . .., ,..
.

.,.I>'!>
,

,, ~
,
~
~
,
~
,
, mu i i h k
s s of ~saturated
a
and
l unsaturated
l
~
hydrocar.!bdtSgl$
be:cyand ~r~~&-f,p~-~h'sis~ af.o*?r rn0fe of fie foll&ghydrocarbons:
' * Propylene (C3H6)
h o p b e.........
(C3Hsj
. . . . ., . . . . . . . . .
0' . n-butane &!jH$)
'.
.
. . .
..,.
1~0-6uta"
.
Butylene (C4Hs)
~races'tosmnli auantiti&sof one or more of the follow&g hydrocarbons may. also be
presen..
I
Ethylene (CzH4)
Ethane (CzH6)
-Penbane (c5H12)
Pentene (CsHlo) )ii
. \)
,i)~ P separated
G
from heavier hydrocarbons by r straight distillation process contains only
the saturated hydrocarbons wliereas ZPGaobtained from conversion processes such as
tht
macatalytic cracking,
,:< ., ;' reforming
, c :.and hydmcracking contains unsaturated hydrocmtio~
. . as

- ..

,,

gq10j

...L.,

@li+.

: Bulleau of Tndian811Standarde-4BIS)have categoised

LPG as under:
Commercid b u t m e k a-hydmcarbon-product
- .
composed re dominantly of butane
ibutyleneb or their mixtures.
(I%)' Comme~ciakbutaneapropane mixture - a hydrocarbon ~ r o d u c tcomposr '
predominantly of a mixture of butanes andlor butylenes with propane andJ~1
propylene.
' (C) Commercial propane- a hydqocarbon product composed
predorninandflfprophpropylene or their mixture.
The requirements of LPG are e v e n in Table 5.1. LPG produced at Indian refinen
conforms to grade B.
I

.(A)

>

,
i
h
1d'fldi~~Mtkl~ie~h8'c~fig1(~~~)
uiifir the Yeed~&sfi&\ffb$W"hi'&xddp
&-fed
SU-+& j f l r- ;
v
v
C Q ~ ~ ~ ~ to
U the
O Ureactor
B \ ~ tower, fmm which, a t thetsamet&e,kk8alyhtia k&5&jw1@h&nf
combus$on
.< ed&es, it is e&emely
to a regenerator where coke deposited on the catalys6is burnt & ~ ~ h ' & n t k a d
f f l ~ $ o h ~ t h e
h g and hardening, steel;utting e t c h f u e for i
n .
I
reactor is fractionated in main fractionating column into so called light
endq;mf~dkb&t~late
good, but it has yet ta l e c o m e p o p u1 l ~ .
and heavy fraction#. Uncondensed overhead gases and catalytically c r a o k & i q g
~ e l ~are
e
, ik
routed for LPG recovery. The uncondensed gases are compressed,
moledaq~pha&$&uqces5,2 NAPHTHAS
sively to two absorbers which employ cracked gasoline and light cycle oil
respectively as
name give? td light hydrocarbons bgilin&$he:ge.gasoline range. I t is
, Naphtha is a
absorbents to increase hgbt ~ ? ~ r ~ ~ ~ v e w ~ , ~ ~ fmm
h g aabsmber
s o l i p is45tfi8p&,d,
e
off its
refipwg of crude:~il.y e bo~lingfiiagesof various types of
-,
kfedto a debpta?iger ~ ~ l ~ ~ , ~ ~ b , & ~ i a c k e datlight distillate
obtaine4,frop
lighter ends in a stripperjl'he stripped g~sol$ne
naphthas
produced
include:
C5
85OC. Cs 118C, C5 140d, CS;
~ ~ O O C C5
,
1 7 5 0 and
~
LPG is taken as overhead producp. L P q q 4:yerhead product from debptahipfr ,
$oJu+n is
.
t
treated further to conform to required specikations.
C5
200C.
In
these
iiitial
boilink
point
(IBP)
is
c
o
n
s
t
s
n
t
.
~
~
t
~
~
b
o
ranges
i
l
i
n
~
can
be
-.
Coker gases are compressed in two stage compressor and routed to the bloi~&$
$&k~~orber
60 - 85Oc, 85 - llo0C, p + l l p - 140",~.w a s are u s u a l l ~classified a s
light.hterme&ate
~ $ @ d f ? ~ ~ ;is $used,
? ~as~absorbing
~
medium. Gases from ap$tha a sorber to are
and heavy naphthas. I t t h h a p h t h a fraction ~ lbe1ovk1000($,
s
it ii,"c1bsified as l g h t naphtha.
~k'&
interniediate naphtha ~ k b @ % $ & ~ ~ g < ? ibetween
es
;&aer a sqrbe, ,,,y coker'kerpsi$, ~L%"kerosifibkord kerdsine a!sor~& % d ~ ~ ~ R
the
'v
H~~~
naphgaboils
above
150C.
For
Imw$$a$tidnating,k71mnnb,!the ,ckkii;~*li8?%ighte'rrehds
(C1 and-cijkre s,thr&qdffG o d
*
4
'
3
Ti)OPC.
'
rich nabhka in a $ l p $ y r ?ndtc$&et'riom' ?,' / stri$eP$re
??<kd
back. to naiht& &$?$erfto
3:
_I__
'
I
ki
recover back QqC4s. St$&r
&dfd&~"&n~&$'
,,) n j g "~' V"t
3 9 ~ 1 ~ a @ l . $ ~ ~ h $ ~ P, $$92 v t h ~ ~ a i n
5
.
2
.
1
Method.
of
~
*
a
c
t
m
&
o
~
~
a
*
h
t
h
g
~
'' !
debutanise; wliCrbiWG is iuihii?iwn %om bpan&'t"hb"lfi&d c6ke'r liaphthd
6&d&.
Naphtha is prod&ed by atm~sfihericdistillation of cmds bil?&s./s &e+straight-run
bPG
tmatment.
Most of le*elik
s t r a i gbelow-5q
h t a n LPG
produced
reguires
only
naphtha. Several c~nversionprocesses such ad visdre&jng$?uid c tal*
crnf~ng,
w8s)rasthb
mercaptaii
ppm.
Causticfrom
washGulf
alb&cmdes
doeanat
bring down
caustic
hydmcracling, cokingalso ?roduce llqphthj. TEssb @ bd2d crgcked 'pa!hth&.
the percaptan content-of LPG in respect of,Aghajari ?rude and-he-e Merox treatment
The important chatacterjsticsof t%aphthi?ractions6~ d a e r e n t l @ b ~ a r eg v
e n h Table
(extractive type) is nwessary. Straight-run LPG produced fro~&$&...d& is BenGraily
~ petrochemic$ and
fe&lher inapm can be
5.3. The proper qualitypf naphtha f o the
sweet but requires mildpcausticwash.
,
achieved by dearomatising the naphtha with or without reforming openh;ams ~ g otor
extracLikewise cracEed LJ'G produced from pro&ssing of Indian cFdeL
lres
-- caustic
tion Ofaromatics. Higharomptic naphtha is not gly.s;auisapce @ k s p mndsbies, but
also
Cracked LPG from F ~ Cunit
' processing feedstock from ~ u l nuddk'irei$Ares
f
amine wash
for,
wash.
consumes &a enerfl
in thd cracking operafions$ithout P i n g m y useful ~ r d u c t s .SO, it
H2S removal follwed by Merox treatment. The Memx process is one of oxidation of the
produces more coke and increases the downtime in both the patmehemica1 p d
fertilizer
medaptans with ail. in ~kaIjne'r+$$m in tffe pre$& of~~el~t6d1i~&n'&&$d~fi&
i$t&&.
industries. On the other haid, the eyiracted aromatic fraction can:be used in
thqaoufacture
The mercaptans are converted to di~~lphkdes
whidi i r e &&ively odod~1dd~ddn~ko~&'ive
r , n '
of synthetic fibres.
compounds. A small amount may remain in the treated LPG but the bulk is transferred
with
the caustic to a'regeneratorwhere sodium m$rcaptanine ik'conveited B diluphide oil
and
,&&2 Composition of Naphthas
NaOH is regenerated. The insoluble disulphide oil is removed thereby reducing the
total
.
is a complex mixture of hydrocarbons. Its mmpositiopdep&ds o&+e crude oil
s~@tiur.
proce sed and the conversion.proce~gemployed. For the composition o q b a p h v ,
two types
Qdourisation. Since LPG is used as domestic fuel the chances of fire in confined
locations
of analyses a i e usually carried out. These are:
b e c o i ,?rgein the case 0Ia:cidental leakage. Beingagas this sh?uld betmost
easily detectable
by smell alone. Since constituents of LPG do not have any characteristic o&ur,'it;s
cimb;on
~vdrocarbontype analysis
practice to deliberately mix highly odoriferous additives in LPG to ilnpart a
distinct odour.
.
Individual component wise analysis
Most commonly used substances are low molervlar weight organif thfols
(mtb$ahlf&':d;
he hydrocarbontype~alysisdeterm~n~~thepercenta~~of
~ ~ @ m olefi&naphthenes
s ,
have an pbnoxous odour in concentrated form and serve as-effective4 0 u r markersin
dilutqt
and aromatics. Gfferent tj$es of c o ~ p o ~ n found
d a inpaphtba fracti~nsfmv
v uses are
'
form (ppm levels). Some compounds of this type are ethyl and $tbb$l mercaptans. ~ ~
~ $ 8 $ t s t
given in Table 5.bThe approximat&cdrbon dumber range of the p r d d u is
~ slap 8 v e n in the
made-Doctor negative and then ethyl mercaptan (about 50 ppm) is usually added.
same table. In Table 5.5, a summan, of quality+of the naphtha-fiqctions porn
various ,
'
indigenous and certain imp~rtedand worldWidqyailable cmde);&h respecQ9 the para!' ,
fidnaphthendar~maticc~ntentso f q e i r na$hth@fracGons $re given. The vque
indicated 1s
-5J.4 Uses of LPG
for the full ranggnaphthd (C5 - 140C). -~ h ~ h y d r o c a r b type
o n composition of naphthas fionl
.&pGisbwedaofq avarious
domestic
fuel, 8 fuel
internal
copbustionLPG
engine
anQa feydstopk
for
themanufacture
chemicals
andfor
olefins
(by pyrolysis.).
supplied
for,dbmestic
Indian crudes is @en in Table 5.6 for boiling ranges of 60 85OC, 110 l2O0C, 120
130"~'
P U Y Y ~ S
is~ysually,
~
a mixture of propane and butane, butanes predominating in warmer
and 130 - 14o0C:
countries and propane being in greater proportion in colder countries. LPG' has
many
industrial applications. It is used for portable blow-lamps, soldering, brazing,
welding, anneal2 3 Uses of Naphthas
The major end-uses of naphthas are listed in Table 5.7. The use of naphthas in
fefland petrochemical industries and as gasoline is discussed below.
IA

)
-

f,"

i , t < \ 2

1
1
I

a,

"
.\

.L

.;

.,.,,,,!

idj;'

'

$pbl""

Ii

i
I

'

J.

-
I.
a::

:
.

(a)Gas making;gasoline
(6)Special ias&:ne
?

...

~ e i v n&ht;kab.
y

,,

. . . . . .

End'uses

>.

:
.

,..

. . .

'

.
(a)

1~

-'

..

:.

L
,

?z

20

E
Zc

v
-.-. . m

*,.
.-:

..

i:

..-

. . . .
. .
.,..

f d ) ~omm&ia@olv~nts-~ubber,
lacquer &id pesticide diluents
lie) ~ e n z e n -e ~i%h-o&ne'gasolieecbmjmnhnt; solver$, petrochemical
manufacture;
.
. .
Toluene - Solvent, high-octaneasol~necomponent, chemical i n t e r m c d i a t e ,
e ,
Xylenees - ~ r - o l i n e
component, lacquer and enameis, chemical inteimediate
.,
.
. , ..
(h)Olefins -and'$iole&s
.. '
. .,
. . *.. .. .. ... . . .. . .. . . .
( i j ~ m m ( i n i aprobuc&n
....
.. . -. . . . . ..,
.
, t.
.
. . . . .. , .:,. -.
.~.-..> - . . . . . . .
:
V h f & ~ ( ~ a r n i&;nuf&ture:and
sh
pi$&inaphtha
~:r:
.
. . -. . --. .. .. :.: . . . . r . . . .
.
:.
,
..
,.. ,
..,,.. . ~.
.
.
r paint& va&ishes,jacquPs ... ' i,
:. . . .. .. . .> . ' ... . . .. .. . .. .. . .
- ( 6~ h i n n efor
. ,.
. . >
.' (=) s t o d d a d ~ulvefit?&ecib &l&&&foi\:dijc& m$ng'*idk::.
'
. . ..
.. . -. . ,
.- . .<- . .*
. .,
&
c d ? ~ ~ j ~ ~s&.itu@
~ ~ 'I..
~ ..t :: i . -< . . e .
;. (d) Mineral ~ p i r i t s - ~ G n nfoF~8ifitg-

~ n t e h e d i a t e n a p h t h & - '(6)&ation g&lineji.


i b ) hiotor &asoliie :6

Type of naphtha
Light riaphthas

a b l e 5.7 Mqjor End-Use*of Naphthas


Table 5.6 Hydrocarbon Type Composition of ~ a ~ h t hfrom
a s Some Indian Crudes
.,-

~:~@00mbu6tion~qlixalb&~s$i~:~~
@ ~ ~ a i ~ y ~ h ~ : s p & i g n i t i &m&
~ ~ @ gmj nw~ ,
On en&nddes&ad ~ ~ ~ 4 ~ ~ l i h r ~ ~ , ~ ~ i d B a 1 i C b n i l i t M n . 8 ~ ~
e ~ ' ~ i n ~ d f R d r a . ~ x C f ; ; g ~ ~ ~
p ~ ~ g ~ p ~ ~ ~ d k l p a ~ o & h ~ "nfi~a1~khe:gasP1i~a&ii&bs8;.~~&;r~e
~ ~ b i i . & i ~ ~ ~ ~ ,
. Y e r e f j s & i ~ t e ~ po aa ~u rg~e & b ~ ~ h 6 ~ r d ~ g ~ f t h B f l ~ ~ ,
& & U 1 ~ s' & , a $ ~ ~ ~ ~ ~ & i h
grmssurc
in the end gas zone, which is thatpart:of the p s o l i n s a i r
mixturewher~theflame h@
mtyet
reached. T h @ l s c m o s e h ~ P L p e ~ ~ ~ ~ p ~ ~ $ u ~ a ~ ~ t b ~ ~ ~ & ~ ~
~ . ~ n ~ ~ ~ ~ ~ ~ ~ t h 6 ~ ~ & s b l i ~ e ~ t 0
undergoprc+me reactions: Amongst-themyn preflamepriducts are the:highly temperature
(Heavyends contamination
~ ,\',,:.:,.xTl.
e ~ .,;:~,i: ~ t ~ v e ~ ~ ~ " ,rtain
d ~ ~c.itical
~ ~ t ~d& 'b ~~~ : fe ~~f i ~ ~ ~h t r~athe
t&
i oend:gas
n~, ~ $ ~ & ~ 1 ~ $
...
Preformed gum i~purities ' . I ....
win';pontaneo";,$
;ini&
>.": ,.,:";.:'.
.
.
e arrival pf the flame f r ~ n t e m a n a t i n ~ f r o.the
m sparking
Improper volathiti coir&b%r . , r:
Pobr cold starting
plug: this causes detonation or' knocking. If, on the other hand, the flame fmnt
,
end
Water
contamination
sasEone before the @$d UPof th$@$&fi, t&reshold:per6~ideconcentrati~n,~~
co@JJ&ion
;;. .:!, ,
of the gasoline-air m ~,x. ,t u r \?fiI.k-be.w~t&jut
e
kbock.
Hot
fuel
problems
.Improper-volotilityeontro1.-. . .t.
.:;.,, ,
!. <
:,, ,
,
. .. ..
........
~
e
~
~:
~
~
. .
. . . . .. . .. . ..
.
.
.
~ i g b r 5.1
e i~h'dia~~~ii:6f~~.dt~~ir!a~1~dj~~il1,ati~n
CUrye ffp ga890na 6nd.itagwjR~anCe
Carburetor1
High
Pcrformqi:,&g
~ ! $ . $ ~ ~ impurities
f c o ! $ $,; ~:,,~i. &.: .,.: :
system fouling
"ark-Wition engine perfor&&i. T h y fiont-end (0 to20 perbent e ~ a ~ o r a f a d j
~ ~ ~ ~ ~ e ' ~ inauction
~~~1d
- .~
s t b i n g and& bl)trQ~l.$as9&-p~,~k,qr~~~r~sti~s
o f n f"ll-bbili,ngg9$~~~$,.$&$f~&b the k i d
.
,
.
Soluble
metal
:
cpetaminants
range (2O'toso'p&ic$nte v a p ~ a t e a ) i $ ~ i c & orddve&,ifity
~~ve
a$&
:+,$;&
f; h;.
&wr.m
ntdminatiUI'i . ". . . . . . . . .
'::
:, :-.
.-:
:. ..;. .:;:: :,4 !
. . . ,
Filter plugging
;
.:
.
...._..... 2,. .., ,
. @ifi,:(~!$Pm)iC,o~ta&nation ,.,,..,,
~ , f g h , ~ ~ o ~content
i$ic
Spark plug fouling
X V ; ~. ~ i
:

:.y2i;;k..t:ii

;
i:.

.: l "

'

i . . - ~ . ~ ~ : . ~ ; i : ~ ~ . f ~:

::,~s:5,,:<L3

,'<::!%:-,..I;

" :

'

,,

......

::

-d

..

,.:,

-I

. .

. .
,
,

/volatility characteristice The volatility of gasoline affectstha Q ~ & af


~ the
~
$
~
. .
ecengine i s a number of ways, which ~reaey$~,o~-,~gr~ng,
r$p:;!f
warm;yf3 vapour lock,
carburetor icing and crankcase d i l ~ t i o n r ( ~ , & , ~ ~of,
~the,.~~p~.e.~Iub~.~.a~~~~g.~.oil
$i~n
with the
higher boiling constituents of the gasoline): The fuel must be sufficiently
volatilc to give easy
t i opnr o q r ,d.E$.ribution bctyeen*the
starting, rapid warm-up, and a ~ e q ~ g t e ~ g a p o r i ~for
cylinders; Conversely, it must n ~b:b'&'"ol&ti~&tli~t
t
',kipour losses fibm the'fud @hk are !, ' '.
.exccssivear that-vapourisforme&i-t@ ffibf%ficcausing vapouf'#&k'rnich dj%&&d the
flow of fuel to the carburetor. To som&&kf'6fil%hcsec o n f l i c t i ~ @ i i ~ l ~
~ &can;6?ibet
cnts
by
,
usinga nibre volatile gasoline in wintcr than in summer, but some dcgrce of
.compfomise
is
. . .
: . . . .<'i. . . . .
.
. .' ...
/ :.. :.. ..l ..: .. .
obvi~usl~~~ecessar~.
'

J o x i d a t i o n Stabilit~
or gasolines. ~hi~d~pg~d~stori\ge!g~s:o!irlps
undf.pg~~&a)y.but
progressive oxidatibn dcterioration. Thc rcsult of' this is formation of n ~ n - v
d a t ~ ! ~ ~ ~ , m m y
residues. If present in the gasolincs, thc gummy residucs can causc multiplc
Gouble, such as
deposit formation in thc carburctor parts,p&pPr&~,~ifA1d~o.f$~~t~jpluIji$~p&~p-+i~
the

%,~Y~~RoT@@~
Fig. 5.1 Typical distillationcurve for gasoline.

s . m A ~ ~ p i w y h $~r .y. ~ ~ ~ ~ l ~ ~ ~ c c i f i L ~ ~ l ~ ~ ~ ~ , r p ~ c
tian&&p :q~qq~"r~.;o&g~?.ppcscnt.
jn.;;tk f4&lj(erjst~nt
gum);. ~8fi$a~EFia!bFF:y~~r:$~~~~$
proccdur* arc used to dctermlnc thc tendency of w m f ~ r , @ a t i ~ ~ ~ ~ ~ ~ ~ ~
~ ~ ~ ~ ~ ; f p p & ~
..il3g;(+m&qna~ion :is! due:tp;.o~iPativ.c.
#g&g@ti~g~$$lyfqc\ j ~ f i ~ $ ~ # ~ ~ ~ $ k ~ . f i f &
? @ ; i r r , d ~+~g k o s 4 d a t i p a0nc.c initiate?. $Pp-941~?~~?~~9f!
~4f0~73~~3~%k~~fir0$cs
chain reaction. The primary products of auto-oxidation are hydibpcroxidcgl:T
,,~.~$ecompose

+& ~ ~ ~ ~ r $ , ~ f ~ a ~ ~free~ .radic:?1,~,1~~~i~g,


f o ~ m i ~ ~P
m ~ r e

F~,$~.'F!J:~C$?

The phenomenon of preignition is encountered in gasoline engines. The deposits in


the
combustion chamber are supposed to be resppnsible far hot spots which are
responsible for
preignition. Some of these deposits arise from tail ends of fuel and lube oil
aaumulating,in
the combustion chamber. These form carbonaceous deposits which may trap lead salts
also.
The build up of such deposits affects the octane requirement of the engine. When
lead halides
or sulphates get deposited on the spark plug they cause low shunt resistance (short
circuiting).

tpPP~!?$~$~I~&~9

am$n&$Fgo$?by+&!

fa-$&~<~&lz&;:!6
~ ~ r i ~ m ~ r e ~ h yguh
~ r.rmati1onn,
o,a~.FB~P[s4~~@&y~~~ti'Jr.I;:2$~
p ~ r ~ ~rpc
i I:d,?.j...,.....G.
ee .s ~~ S~...O ~ ~ ~ < aiC!?$i$)it
S
:$%".,
to p d f o r m a t i o n duridg++&i~&.uiatea
also ui;aerpo & ~ ~ : ; x l ~ t ~ o r i ~ ~ ~ g % + $ $' $ ! . . ~
Most petrole"? products a& $u$ceptible to deterioration~n~ f ~ ~ f t , d!,\ri $ :
$*pi?
~
composition a n & ~ h 2 ~ ~ & $ 2.~. c & . o famaunts
~ m 2 1 1 of nitrogen, sulphbr, organla
S:;, - %:d: % ~ g ~ ~ .
. . h l ;d
, :.
I

''

.
c

'.
..
~ ~ 0 6uvqq&antqvlualls
~ s a!mouoaa
~ ~pus ~~va!qae~d
~ aiom B sluasa~d'~anamoq' s a ~ g ! p p v
.aq3 4 s u p ! 30 i o ~ q u o.mar,
~ 4 BUE ~ q a ~ n q 103
~ e Laua~uaq
a
a w uo v a g a pqmw
JO
,:j:

s . . s p 4 ~ p ~ 1 au!pssD
~~
. d n - u ~ ~ saugua
fi
S u ~ ~ Ln [p~ s [ n a ! w dS U ! ~ [ Buana
~ S pus S y u u ~
au@pa~qsnolq,o)lnsar s!q& .~oqunqrBaag) u!q$+ a Z a q U V J 1!8 q a ~ aqq
y m q emqs\ow

1 u n 3 ~ i d m a qlua!qms do1 L l a ~ ! l ~ l pus


a l 4!p!m"'( @!qJ9 sUo!q!pUoa ' p u n '~0!$dLLms00~
lay
assanu! PUB O ~ U lay/l!B
J
qasdn usa s i q a m q ~ e aU! Uo!$BzIuoJ m s p r m o Q m o ~ S u p p g ~
, .apap!1La!pqp~o san!qsnuap a u ! u q p a u a ~ d o ~pus
d au!arslp ava~&qqa
aqq a m aqaqq 30 UOQI~UOSv o w a u . U O ~ J B s!q3 quanad q pasn a m s ~ o q q ! q
uao;)u&z~p
~
1sqar.u p m ' s U O ! ) ~ Buo!~vp!xo
~
aqq* a
usa addoa s s ym.s p l a m y s p a g .aylos& aql
JO &!1enb aBv1qs a w uo rmga snouaqalap paaunouold v aney q pun03 uaaq ansq a q l o
d a g
gtq Lnm qay? pug b e m qeqq q q a w jo q u n o m s aavq aqq JO amos .saoqs~~3sep
pla~?
.au!10svS s h e w u! qusppo-!qus anymga 3603 alow u a g e 6\ d q i m ! ~
aual6ueqd aaud iayS!q sq! q!dwap pus quauodmoa Bu!pua~qquyalo Byup3quca saq1os&
u! quappa L[m1n3!3led S! s!~J,-1ouaqd 1L.118 aqq wv,q qmpyo-!?us an!Vaga slow s!
au!nra!p
aualLuaqd .~sa!peiap!xoiad q$!mSu!qasai 4u o ! q a ~ u!sqa
a ~ s!qq $!q!qy 'sau!m!p a u a ~ u a q ~ a o
slouaqd 1Lyle se qans ' s 3 u s p ~ o - ! q .SIB3!pBl
q
ap!xorad s a A [ o n ~ ~ ' Q a ! ~ d ov! ~q Ba ap ~ p n ~
aai) 8
paaaCd oq paAa!laq s! a u ! ~ o s s l ~uo!qepedlap
o
anlyappo a u -suo!qsagpads aqodnS
worn u! quasa~dale squamar!nbai .Q!l!qqs uo!q~p!xop w a r n B ' q u q s ~ g.sqmp!
xo-gq ,

;
s~anoldux!uo!qsnqux03 (n
q u a 2 ~ a q a a(a)
spunoduxoa %u!a!-!qw ( p )
6 " T ~ W B a p la^ (3)
9 w p u r 0 - 9 v (Q)
"p"lod~oa J i ~ u y - 9 W ( a )
:Molaq w qu!od m a p I e u o w u y m o y pag!sse[a aq us3 sau!loss2 u! pasn aah!q!
ppnjo
sadLq a q ~ e l q p
a suog!sodmoa p w ' s u o ! p u y 1 ! a v ' s a u ! ~ b h&
i ~paen B ~ A ~ I J P B
jo 6%
mom^ .Lam Fa!uo,uoaa us u! s u o v u y a s a q v o q ?no Xuea sSi9!pps a u ! p s s
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aualdyqa pue apForq!p
aualdla se ,qanw s~a~uaheas
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Detergents.
. . , , , . + . . . The
,,. . control of deposit build-up in carburetor; fuel, injection equipment and
., ) ,
inlet system.canbffer significant performance benefits. These include:
,,
exhaust:eniissions,
:,:: . .. :..,
,..!.,.- ,xi;
. .
(bl!mp=$$id fuel e ~ o n c & ~ ,
(c) Improved-vehicle driv'eabi~it~,
and
(d)Reduced maintenance costs.
The use of.;low levels of carburetor detergents typically amides; fatty amines and
imidazolines can,give good control of carburetor deposits.
Combustion improver*. A range of additives for combustion improvement have been
used. These intluae:
(a)h a d appreciytoyisuch as tertiary but$ acetate which were effective a t
extonding the
anti-knock effectiveness of leqd alkyls a t high additive concentraticins.
(b),;Qepgs~,mbdifiprs
sych a s the phosphorus and,bp~n,compbundsextensively used to
. .
increase the g1oW:pointof engine deposits.
. ,:
,
(c) ' m e catalytic approach where the ?atalyst is added to the fuel which ,appeaia
, , . 4.,, t o
. be
.
. .
increasingly considered.

ta?$Zd&ced

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5 k ; ~ e Gaso1ine!Blendinggc~mpopent8
w
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.

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In recent times, pollution, from automobileexhausts: has increased


toalarming~li.Velsi
Starting from April 1, 1995, new c ~ r s ~ ~ in
o lfour
d metropolitan cities of India, i.e. Dclhi,
Mumbai, Calcutta, Chennai are fitted with a catalytic converter on their exhaust
pipes.
Catalytic
,. .~.! , . . converter is an anti-~llutiori'devicetittcdto
the exhaustsygtcm o f ~ e h ~ d & ~ I t ~ ~ c l p s
prevent em~ssio~of'noxious
gasds i n t the
~ atmosphere. ~ t . i s - t u ~ u l : & i n . s h&id.
a ~ ec0nipAse.a
hoiit?'jico~lj.hetallicor ccrariii'cd'i'Sc coated With 'noble metals like p l ~ t i
n ~ ' ~ & h d i p a l l a d i u m .
~o!k&Febl~jAiy B e ' i 6 l l ~ o f ~ a t a t a in
l ~ ~ii:lractibn
1
which wridbis exhaust;eonponents ltke.
carbbfit"monoxideand hydro'carbons Bafrn~ess~by
converting. thcminto carbon. dioxide 'and,
wat'e%:Thcse inetals are spread over a Inrgb surfaccto proddeihbimatc.wntact
between
exhaust gases and catalysts.Catalytje corivdrtcrs n i e rcquirgd.::to simultnne&sly
:remove
tdfg~0Eeil'pal~utants,~rc6ist.'Cahlyst:poisoning
bycontam'irrants;md:~~tJlo~g~~~~Ofa.a.~two
t ~ e ~ ~ o f . ~ a ~ ~ ~ y t i t ~ c oTwo-way
n v e r t c systems
rs.
using.plabinum and:palladi~,:.yhich.remove
o~'1~'c~~b~n~m~nbxideand~hydrdcnrbons~
leavingnitrogen oxidcs unchwgd.:~he~latt'cr.,is
o%idf~ed-th,rm&h..air,:
pump; Threc-way catalytinysbms. Oqplpy plati~mGipall~diY$;!~ayd
rhodium to remove all thrcepollu~ananbsimultnne~uoly.,had-
i.n-,thegawli~~:issj~ju~ious
tha..honeycomb disc of the:conu~rterand poisons the noble m e t a l . ~ , i n , ~ h
~a",r+uc~s
d~@~~
its potency; . . .,. , ' . . ... .,.
.
..
-Bheiaquirement olprod~cingunleaded gasoline will result in octane s$ortages qt
many
manufacturing sites.!The use of oxygenates in gasolines is made for raising thc
gasolinq pool
volume and its octane level, especially in the critical front-end ran* The
excellent byming
properties of oxygenated compounds result in increased operating cficicncy of. the
engines,
thus compensating for the loww calorific vrlucs of the oxygcnatw. Simultaneously,
11.wer
~ i % ~ : ~ ~ & ~ ~ & ~ ~ 9 ;p~@@I~i$$t1gey~a$R~$pg$iF~~$5f33~e?~
9f+~$j-i~i~i
$&$faee
acti.y.e;~~Q&j$jgj
gge;&.&& , - .~p!5
' a # @ $ t i ~ c ? $ ~ #
~
&
'
b
.
&
~
~
~
~
~ @ ~ ~ . a ( ~ i ~ ~ ~ e ~ ~ i ~ ~ i f ~ ~ . . ~ hdk@k?b;~ijt:!?
~ 5 p . i ,"y?~#?&+
! ! g i ~ p j n t a i ~ ~ ~ ~ q ~ ~ : s u c h ~ ~ ~ ~ ~ ~ ~ ~ $ ~ ~ ~ ~ ~ ~ ~ ~ ; ~
~ ~ ~ $
~ ~ R k f l f i ; & @ i ~ ' @ & ~ ~ & ~ ~ let& ~ w ~ ~ ~ h ~ ~ p l ~ ~ ~ ~
,a. ....~...f. "(,...;
B%,
P
i'
, O : m ~ t ~ y l ~ e t ~ e i i l ~ ~ ~ ~ '
,

cffective~Thesui(aekactive c ~ ~ ~ o h ~ ~bysfo~ming&fi~MB~~~i~~&j&over,~bk~Fatal
~ f ~ n ~ t i , ~ ~
surfaces& the carburetor and prcventihjj Mherine to them. ~~h~ c h ~ ~ ~ ~ ~ j c ~
~ ~ $ o u n ~ ; ' ; ~ n
be
as surface a ~ t ~ ~ " Q ~ ! f j n ~ b $+@,thqp..c$ten
~ ~ ~ ~ u @ , dinclude
~
the compounds
~ s e a?.carburetor
d
detergents orenginec~eanlinessadditives which are discussed below.
Dete?$$~t). "P control of deposit build-UPin carburetor, fkekinjectioneguipmentand
inle,bSyst.eb$?hXFb:fferS@ificant.performan~6kn&fits.These include:
:
:. :.
.>
&$'~ed~dd~e~ha"~t:
, . (:,.
&h5kiions,
...,.
,,.
..,. !
.
.
it
::; ($1!:mpr{+df~el
econo&y,
(c) Improved vehicle driveability, and
(dl Reduced maintenance costs.
The use of,-bw levels of carburetor detergents typically amides, fatty amines and
imidazolines can give good control of carburetor deposits.
Combustion improvers. A range of additives for combustion improvement have been
used. These include:
(a)cad ~ @ ~ ~ & i ~ ~ ~ s . ~ ~ c ~ : abbtil-&tiitit@
s t e r t i ~ which
r y were eBertive a t extending the.
anti-knock e&?~+venessoflead alkyls a t high additive coqoenhativnsi
( ~ @ ~ . ~ ? $ , m ? ~ i f s.$+
i , y s aq.the p h o s p h o ~and
~ boion,compaunds extensively used to
.:..
.
,: ,. .. . . .,
..
increase the glow:point of engine depoiib.
- . , .:
.
d ? ~ ~ i ~ . ~ p p r ?where.
, a c h thecatalyst
in
addid
b,
the
fuel
which
a
p
p
e
a
r
~
t
o
be
,. .
. . , '",.:".
*. . . . ..
increasingly constdefid.
: . \ l.,,

5 h ~ e Gasoline
w
BlendingComnonenta
- . . . ..
In recen't:times,:pul.lutian:from autpmobile.lexhausts! .has incr
Starting from April 1, 1995, new c&++"ild-?~
fo0.f metrepditan ci$cs of :Iodia, i.e. Dclhi,
Mumbai, Calcutta, Chennai are fitted with a catalytic convcrter on their exhaust
pipes.
Cat&l@ideonwrter is an s"ti:p6llutibi d&ice fiftdiJ.td the eih.aust s y ~ ~ c ~ o f
& e ~ . ~ ~ . ~ ~ ~ t . ! ~ c ] P S
$&&df , , . & ~ i ~ & n ~ o f n o ~ i o u s ' ~ a k ~ s & ' d p h e r & ,
ig,ahla$in ,shapL*.and
',
:'~m.p&ae:a.
h d f i ~ ~ b ~ b . h ~
ce~amic
l i ~ od%+&
r coatcdwittnoble met& hke pl&tjfil&.~ndi~&l]&jum:
hlibbekal$'$&f Bi&?&;d$cataly+tib a:rea&i&n.which rendcf;i!exh~~bcomponM~9'1ijke
hydr~arij&s n.h&mta*r jay wnvhDinLzithrm:..intoJc'~rbon::.di~xide,-.and
$&~@~r",r&ehe5fiet;a1~.
a*C s
. read iver;-a large sgifac@;-to.provide
&timqtctcon.tact b e t w e n
e*ust
gases and catl~stsiCatalyticconverb~s
a r e ruquir~d':~t!simuhnebUsly :remoue
t.pght'~awh~ nts,~cxsf~t,Ida~l~st~poisoning~~by.eon~ami~.~
.
ati+la~tJo~~~$el..a.~two
t ~ 6 ~ , 6 ~ h ~ ~ i k ~ c ~ n ~ b r t '~jrbtemsusingpldinum
dr~.~~o+wap nn~alladiynj~~~c,h.~mov~
~''~$s$&>~.
.
uf~cturqd
by,fepentqt@n,9f,i!@fg:,
tvra12~mduc,@.
. :: ., ,. >,.:
@ r ~ ~ ~ o x i d o ~ a . d ; ~ h y d r d ~ al cra W
v i nnb~n i b m n oiidca h,nchq$.::T.he !l$t$.;ib
::;*5gjhflpltJ$&;mm.\,
.,,.,?, ,., , i L '<. r. ,' .:: . , I :
,iofiw@ng
5 +.reen;
ethanol by volume are sold in Sdhth kihxica 9.W~!>,
%;RF~:
., & J : ~ " .
.th
- .
BY?d?i!~d"'$h~iiQgh-oir.
pump;:Thr&woy .catil@c systems, crnpluy , @ & i n . m J p d l a d i , pand
~
p p r t i q such.as better w a M
.:. ~ . i ~ $ ~ ~ ? O .
rhodium to remove ill,thre6pollutdnts
~irnnltaneuusly;laad:inth~.g@ig~ia.ir\ju~iou~t'o,
' t i~e*~,&
$J&
$$f$
; 14biahi=gidsponent
. .
'pithout
.
..
.
kh0nev-b
discof the: conxocter, gndpoirma ,&henoble m a t n l s,. i f i 3 ~ h y ~ d ~ v j ~
~
apdre$uces
.
its pobnpy,;..:.-!.!;.:
:..,
i o v m m & subsidies its price is currently u n a t t r a c ~ v e/nm*~,~$*tnes-:,
;; .
;. !,: , r::
. . .. .,
..:. p#3B.,Lpia pro,du!e$,b~ ,a simp! ,
~
~
~
~
y
~
,,, ~
~
a
i"he&quiremnttor p.rod~cing:un'loaded~asolioe
will re"$, i n &tqo s&~.a@ceqt many
"e~faetiatin~;sites:~The
use of.ixygcnntcsin gasolincs is made for rai$.i.ng.ihc gaio~ind..
joo]
repre? nts a way,to use metbanpl
rn Feltber
t q r : gfrom
F o l mFCC
? (fluid eiit&lpialytiscrackyg) o&-gples ar
is available
3
volumeandits octane ,level, cspecialb in. tho critical front-end range. The r.&ell&
bUrohg
steamcrackers. ~~t the amount of isobutylene available fmm these sources Is very
'lrnlted'
. . Propertie? of oxygcnatcd compounds result in increased operating,cfficicney of
thc 'on$nes,
The isobut.lene content in the c4fractions from steam cracker varies from 4' to
45.Prcent
.
thus compensating for the lower ealoritir valucs of tho oxypcnates. ~ i ~ u i t ~ n
e o ulbwcr
sl~,
;
,

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PETROLEUMR , - M ~ ~

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~ ~ ~ ~ f $ i bc%he
f h ~ blehthig
~ & h tompbbnt~71tg
~
!nohitmid ~ s n d : n ~ n ~ ~ & l I dz$ifills
t&k~j
e x ~ e l ~ ~ t f ( t ~ $ d ~ ~ ~ bWtaiVdh
a a t ~ &th
e r i no
d ~odpatibilit~fpmb]emx
It ean;bc blehded
a t ' t E P f ~ d W e ~ ~ a a liiixhire
dhe
can\be handledy &$pod
dist)ibukd via e$jtabli&e&
edgines i ~ c t u d f ~ .
*, ,.. ,-.
c h ~ ~ e l ~ ~ ~ U $ t h ~ ~ d h b t i o n ~wni et hc1s&r~st ha~~1 n o l
~is~eipeaialiy,atfractiue
~?,~~l
for
,(4 cNqii lightyeigl$ gas with a hi$h @ition t
e ,r.pidly*m
p
dispew~@?~ntO
b
~ shortage
~
and
~ insufficient
~
e
reforming r a p a ~ i t ~ ; ~ ~ e ( l oflMfJBE(in
iof~o~i~~
.
;
..
ii&&pe&pb
~t
~um&kerbp~f~tu~e;~&~r:waui:a,fi~GVG;
LJ.'d't"
'
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k
l
l
l
l
.
*
?
+
,
,
,
,
cases appears favomble when compared with other octane enhancers. MTBE blending
.l , , , .
i , , - ~ ;~
o%%'i
"dJ..7 4fl.fiI ' i d k , . , * r l r - ~bi,,:
.
L:J~.
additive&jot
n o r m ~ ~ ~ r f ~ ~ ~~ b ~~ ~ e~r . s~~ c e~ ~ u ~~ t pgasoline
e$ ~ &
~ Q ~N r ~ ,,b,~,,~,atm~s&p~g
u i ~ o ~ b ~i..
~
e r &8NG +idiahqi.@~BD.
rz;Ie"nc@iCSGineeds no. ,. dl<*''
.
can be pmduced by catnh.hc reforming, with relatively less yield loss. MTBE to the
extent of
& ~ , , , ~ t i ; ~ ~ C ~ ~ ~ g e n ~ ; . fl<UdW
s u Qh.'+,SxX.
~ ~ ~1 11.4
~ ~i b; tf ~ ~ , t l $ ~ ~ ~ ; ~
11 vol.% is-beingble~de$inAmerican and Eumpean gmo]inea.
~..,:,y.r(@
M~~~mjPb1lu~an~&missi$h~~ctl~r~t~re'i9.fi~6ip;lifii:~t
redubtion:
and
, )of@o'
rl'
'
~S%%$&~PS &b?dk WLGTBE:
pr&c&
by additsel ye&&\
Of tertiary
:gh kl+; 3 u g ~ ~ m ~ ~ d & & & ~ o n R 1 ~ ~ f ~ f i r i O'1~$7>dc!1
~ ~ ~ 'iz .x(%o':? .Ll'll "
amylede%4~&~k%&6E,
prg$kiice of acidic~r~i4ctio
$9 9" t " ~ ~ ""8w~.:)ii
74
[vb;
.':cd "11flf4' '
~ E~ , I,a s-(it a~slightly
fighera*g
$ i h h ~ s o m e i v h a t l ~ w eoctane
r
val& ~ M T B E~ . AT M
f u & ~ ~ ~ ~ ~IF,~y;@p
$ j &&ib(i&a&,qd'mdrgfggtlltzp:>~:~~
~ \ ~
With ~ ! i o f " h x z l r ~ ~ e p d s .
Abi&;'&x~e~@Q$b
~ e ~ @ & o f & ~ ~ ~ ~ @ a d ~ r f $ t j ~ ~ l @ @ ~ & t r b I 'g,~ s ' d b ~ s n
o t r ~ i W h w e
iitasi&$@anc.
as a t iab
- hao mems
t k eLbrqmndntbas2h
~ ? @ ; ~ ~ t ~ ~ i @ + & b ~ g ~ & .~i&j$%&kii<e@i4
.~dySgg
ij61~1&$@ I 8@6&t+&4)5j
6 1 2 2iY+%al *
h p ~ l i h i ~- ~ ~
48 ;
m @ul #gcbrrgd
somed refmeries
b cbemi&al
$k,
*lti,
va
Sngineshave allongMe. ~ ~ ~ d $
a%!6e" aii Tn A SaT Qt ~ sift
c
~
o
&
~ trr y ~k ' i~ u ~ @ ~
a d d b,>-$ ,11h b u ~ p t~o&&b~:-lifit
l
s h i n ef r a a .
~ ~ I no yi91 t r *
1.. I
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-- l,x)fsv,,, *ne:t L 1,. !zLv
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T h e m o 3 t + t e n t i @ a ~ t i v e gdaoline fuels for spark ignition engines,


b o t h ~ f i o ~ l ~ d i ~
slnte*and world enerWscenari0, areliquefied petkleum gas (LPG), c o m ~ r e s q e $
p p ~ $ ~ ~ ~
(CNG),p@ue18 and glyh$ls.
LPG. m e Me of LPG ad hlel for spark-@ition inbines has already &ehvsk&&k$h~'
,fd'm:
advantages of fiPG over liquid fuels include the following:
I
,
(a) LPG mixes.more readily *i$X air.
(b)' It
be used a t somewhat leaner~air/fuelratios.
'
(c) fi @veslower emisSi0ns ofpollutants ?carbon monoxide and unburnt hy&wapbo&).
(d) I t reduces cqybustion chamber dehsits.
k ) I t had excellent ;in'ti-hoi~+iforriizince, providid unsaturates are
excessive proportians.
,..
(f) It is resistant to preignition.
I
,
&?) It gives excellent cold-start and w a h - u p p&-fJn;iance.

m&hs6 br , d ~ ~ ~ i ~ f ~ $ $ ~ b ~ ~ ~ ~ i ~i jt #~ ~~ ha 1~ ~i ?+ $~ %~ tE:Y3 d'


~h 2&~ J & s t ~
:gad
:id?b&u#1$~&$~1,j
"&&&~i,i1\; f@&S@~&~.ei~~
l~'@k%i&'b$~ f i i ? F ' i '
9

';l ~(l~.il.f;30"P!B&le'B1~iig6YY~!
*i';"i[j"'
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station costa of CNG are very high.


Bgnfuel~.Synthetic fuels (synfuels) can be produced from coal, cil shale and tar
sands. A
co'pmy, sasol, in south &a is producing synfuels froid ctgltWgfnatr@is th%
+kQrAp1ete
~ b h & o & ~ ~ ~ ~ ~ B ~ a m - a nm
db
drO@urifikhtlbn-d;th'e
xy@~.
gas: s p t h e s Y d & d t s

s..,

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t i

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f i e use O T ~ P as
G a fuel for ?Etr$-ignition e n 6 s Khg 2 h+ber of d$hanM&i:heSe
include tde follbwing:
' I , ,
(a) LPG ,muat be stored and trans&rted in tanka cap.ble &fyithstat;@d,
hjgh,
pressure.
(6) LPG tank is quite bulky.
(c) The performance O ~ L P G
in tenns ~f emisyions,
myis
on
its composition. The WC.4 ratio and the level of Lnsatwates
strbngly
Y$jlence
(7d ecoriimY
I

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,,b,

c
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b

depe*degt

~ e O B ~ ~ ~ ~ f i ~ f a 'md:$&me:methm&l~einextr
~ ~ Y ~ ~ & ~ d%i?=$e~l
~ ~ ~ ~ ~ n
~ l ~ f i g ~ # i j f h ~ d t & & f ~kEe
~h
f f~ i~ iong ei h . a ~ i d ~ a t i , b 1 r n o n d r i d & u a r a m i m 8 ~ ~ ~ ~
1t1givesil l@d r@gd of&~yd~oc,atb'bn~
of dif%mtid&
I~d@&~Qh~gi~~~&&
s(aa&b'#~
b G ( & ~tif ffox&eh&ert SLID?&'BS i a l ~ ~ f ~dfi:k~f6DL~8881*
i~l~'
&Q~&a&$w&@&~&&&ei&
P --_.._
~ ~frbnt;th&htct6~
----~ t s tail gab & e h p & & e n &
@qujh&b@Wed ~ ~ ~ o a u e p ~ h p' t~~ e~s see fssuch
u ~a3e iaamerkatibn~
~ ~
~~la.tiAnl
p ~ ~ $ t ~ m ~ ~ ~ ~ I [ ~ . l I ~ ~ ~ ~ B, x u~ i ; k. . i ~ s s e r i e s
i~ii~~&ri'~~~~~b~~~h~r~&hno~and~thand11h2t~
f u e ~ ~ f d r s ~ ~ k ~ iengines.
~ n i t i o nethanol and ethanol differ m y k r a & ~ ~ m g h ~ b ~ b ~
~ b a d t i ~ t i c s i t h a J ; , wimporkant
e
to t h e i f i d i s t r i b ~ t i ~ ~uselas
r n d a &el-fon w=k+i&on
&$-&Pf.,Ql2
&~$a~<ie&fiiijfih~ %most~ ~ f i ~ ~ t ~ c h a r q c t e r i s t i q ..'"mb~ :.
t l s . i ~ ~ b : ! . ~ ; . ~ ~ '

7 @&wed to typkalpsolioe, metha1ial~~uiretr44%


as m u ~ l a - a i r ~ f o 1 1 ( 1 0 m b - ~ ~ & ~
&@~asnhacii
-BF&
and .equirbs3!7 timesas much heat f o r v ~ ~ o r i z ~ t i ~ n ~ ~ ~ h e i w ~ e s
~ n ~ )
comparisons fop ethanol are: 6lY'aamuch air, 66% as much energy, and-2.6timea
thbh~etld.
vaporization. The ratios of heat of vaporization to heat of combwtion show that
fn.a Weh
.sa!qs!~aqaemqa B y n q u! quawaaodw! ue Bu!anpo~dLqa.raq3 'saueqqgd~u,oq~
pa)nnuor~sq m a =!qewole ?m!per) au!soaay s p q u a w s a q ~ ~ p L q L
.(.~sqj
a ipw Q.mnqse) W!+*nb su!mq PW qPIO3-0'
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d u ~ a RIQWBA~
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qe
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4,
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e "spupodmb~
n ~ e q a qu a % q p p a s t4pm0@03
~ b p l s e P ~ ~ ~ l o ~ w a ~ s p e ~ uwu~a mq ~
q q~ ~~~n~us
np y~ ~ ~aqq
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d apporp
I

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' ~ W W W i ~ ~ ~ % ~ m ~ ~ W 3 ~mqd1n8
P ~ w~b f4l w~w pp a?q ,x~ o
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ayrwq
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If
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1sa(qeu8osp
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raLe1 ~ o p qXs ~ A m LIa3 sad4
Jaw .Ia&'ii@ i58~iffffn#nPltf&dtlatto55 ~ 5 ~ & d h ~ P d &4'dkdd
~ t $ b'~6t.d
%q$sa'$$t~~dh u n q
a&tq%a!~~~,
aqi+$&S
asd6~%iq&@ri~kri1~~q
~ u a u t + % 3 &3!5 quapg)ns Bqaq a q s o ~ a q30 41J9810~ qua~aqtf! a q uo b1a~s
r a u o d ~ ~
$ 1 ~,n'.~uC"!~e~~fi
rrprri;p!c
i.a z a i s : .r i;o..-..*:-ti.~i .-;*;.i
. g i ~ z l ~ ~ $ ~ & w ~ & A
Jag!. 6 r d f i & k ~ 1 ) $ ~ % ~ ~ ~ ' ~ ~ & ~ f s%~U~bk$a@;a~kt$~!tadmq
5pa~qjd
q!B@sea~aq
PUB
fiif@ffi@%@36%& 'Q'd8$ks'wf~q&~q
.!&i@~fb#'h o , ~ p z ~ f i & ' + \ ~ ~ + q ~ e
JO s&U6~~fi~@f~C&5'4k1r%b!$~'~ode~a aqq a s e a o q q h s s a a a u s! qf'nrwmq
agsamop
u! p * d a ~ ~ $ g 0 ~ ~ 4 ~ t l 4 a t d % ! ~ ;anappe
t ~ u ~ o&
~ p.L1arols
s
u o o l sqsrodena a q s o ~ ~a n~ q
' s a l ~ ~ ~ a ~ s p ~ ~ ~ ~ q ~ ~ ~ w ~ ~ ~ ~ ~ ~ d 1 ~ !w pd~8oa W
5 j~! a~wam lq ~ ~ 4 d m a
L p a ~ m m ~ b g e x ~ ~ # ~ w U a t r ~ q doqs paaodxa
w~pqq
uaqm quapa autos oq a z o d s a aupofay
s + h a o l ~ r n m a 1 0 ~ 1i
~w
d!
' a m u r . a r q a v q u r q u w o p q o!ar qaa.um ew q z pa q q
u a a oaq~x7pQaqw
p m a n o d w o ~ 0aqq3u!aq 4 s s q 31 -aqswp!nbg aqq q quanq aq qortusa
au!so~ax? p g 0 9 b rR~ aBa~~-%v!l!oqt~w~~~!o
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~

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*, :.'i~lf!q,
-

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3fils~j~~e
uther extra t'
Qce qes for the sep atipn of aromatics a d o n - o atics use solvents
with much highBr'?fk'B$$biiie$ ~H&"~%B~~$'~I~~W&~BQ&S#~~'~~G"&Q~~~
very
in that rafthates with very low,
as
well
as
extracts
with
very
high
arpmatics
contentr
can be
-- ..--.
made, Of the processes ayaJpRIe? the Shell%.ulfi&e
extra<$i<< p G e & i. wide$ u b d ,
especial1y.for the
aromatics from hydrocarbon mirtlires h u o r e piqduction of low-aromatic!solvents.
. -+irrq;:ltnz.~-t,
. -%

extractionbf..~

5.5 AVIATION TURBINE FUELSA

L,,

A potentialfuel for'the gas turbine engines usedin


alcr~Fe~tlir~s8highl~~mdstabi1itY,
high heat content, low vapour pressure, good combustion charakt+ris$di zodd kis-
tytemperature relationship, hi&, density, high specific heat, a u # J o ~ t ~ 7 # y
~ g ~ + ~ q d l i n g
charac$ngtics. The combustion properties of aviation turbine fiiet ( A g J i l f i
~ y t i ~ e l a f i
controlled using several of the following five tests: smoke point, l u m i d ~ m e
t a ~ u ~ b e r .
7
aromatics content, aniline point.and mavitv.
,.
lr
,
The heat of combustion ishormally ,calculated f~~~-,-@j9aP~t~ad@g~tYYY
&)ely
hvb basic types ofATFs, the k ~ m s i n etype and U e wide-cut$; ,
$jnek&,a$hgmira\18ed
worldwide+ The kerosine t y p "of
~ ATF is a much modikC&f@R@+;&l&iTR~gpr
kernsin; oeginally used in gas fYrbine engines, whilst the mde-cdFap my ~JJ AT is a
wider bGiling range fuel incl~dibdsomegasoline fraction. h $8&&:idird$e+
r eeia'Ij?ed
fuel grades are required for limited military use, as irl su~db!oriidaFr$r'affv '
tk ?'-;'
The properties that control ATF quality are listed in Table 5.14. ~ohb&fi$g'*&alit~
relates those properties which directly affect the ability of a fuel to ignite
properly. With g ~ s
turbine engines, the volatility factor assures delivery of
fuel~ta~b~e+tb~bi~e~~hb;bpIe~~ith
satisfacto~ignitionand flame propagation characteristics. Ioturbin&engines,the
Liishduld
mt allow deposit. to form in fuel nozzles, fuel control systems, turbine blades,
cpatings and
wale, all of which will degrade performance.

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tbsq a ,n $ ~~f i :~& &j~-~ ~~5~


~ ~~~ ~ ~ g ; ~A $ ( q : a~3 u 8 m d~.E ' a. ( 1.~; w r i ' a ~

1.18.

1 a y i d[as~a@8~.ua3~55ga
aqpelh " ~ l j ~ ~ ~ ~ ; r ~ ! ~ ~ . p ~ ~
d a8u-n~p ~
i ~~a :d ~* ~a p o u f . ~ ~

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d : ' a ~ P ~ . ~. ~ ~ I i r 4
~ q ~ ~ 4 3 ! u w q ~ ~ 1 6 : s ~ p u'angdps
s : u a ~ &'~uaS~~s~Q.uogrea~o
o
saxqdtuma~uii3~0.
ap~on~uou
'qq2fiwi;tel~oqow+~&g
:!qje~i ,.'
.am,
~ daq&'.;rnqIltis yqiqqnuug~,,:
, + ~ ~ q ~ . ~ .imOi.
: u p .~ ~
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.

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3 I O ~~ W ~ ~W
s.Wfl:uf
; ~ paw'qap
p & i ~S~ p & ~ p~r ~ g e ~ $ ~ o ! p ~ a a ~ e a i f 5 ~
U? Lru!elu WJJO~ u n o d w uasOq!~
o~
'pmporqu! uaeq wq qsa?uo)souo~d g s - r a n ~ as 'sdmnd
p n j alubsu! juasaid '<$pedi a ~ uo
~ uo*os
$+k,ji$$
l~clese
cYbja)cld
:b.- :qgsi
uO!sOuOa
d%s-~addoJa nq ~aliu!l
s p u n o d ~ r o ~ . g ~ ~ q ~ o ~iaq$o)oro@w
~ x a ~ d w ~ ad e a j a ~
',% T W O asl sIa1 4 m ~ d s ~ l a w
~ ~no o amq % j ; ~ s u o ! ) ~ ~ g ! a aad su .inopo alqeaases!p
Sq! 103 p w run!olpe3 pus iadd0J OT s s a u a ~ ~ s sii
o atifij.
~ ~dflsagyads pa1lol)ooa s! m q d ~ r r ~ ~ .
,>*:Oq Pa?!uY s! ~
~ J ~ Yq ~ I1Pu~ 0 "Alll02i.?lb
%~ .:~.@?q2r3~@a~oxd
a q p w .UOR!SO~WO~
aqzft0.s p pi^ p b q $ ! ipalIoJ1uoa
~ ~ ,,. ... . . s! q u ? e d ua83i$ih p&;inqdlns 3o imoursiu
.uasbo
u~3oaq!u'~nqd[nrilqm~?uoa~
~ ~ ~ . j ~ ~~~ ~ : u ~ ~ ~u a & ~ ~ ~ du ~ q ~ ~ a ~aa~
r p X .Y ~- ~o o u
~
. u o g s n q u o ~ ~ oS@J&~JSB
,I~~
p,& iuyls*d
o a a ~ a aq ? a ~ a o u a ~ ~ s a ~ w n bs~mn&-p:~.9?~?ie~iEa~;~,.;&sr;@;~$~~,
.
qjIV&
:,
asp* pa b + ~ JcJ?m?'lJ
v a ' ~ ! I F ~ wl ~ T! a ~ u d~p b .~[ o ~o~~q p ~~~ ~ u9 a a ~m s a~y..a r~~
.
- .
- ,
. .
.
,2rrtsci -rut .Ti-:: . i11;7,c::
YaIy .4.!auqn[-.~opu@unr
.WP$W~ .
~
~
w
- ., ~ , . ' ~ . s!~ . ~ ~ ~o l d d~~ , ~ q~ ~ p oJm a a ~
arlr.
P@uo al(l
n? la@ aQ.3,p@@roliqnlm uoIS0- p a ~ ~ ~ d d ~
"B P (Wdd er o r ) d l g w n b p u r s y ;apg q!s . ~ q $ $ i i @ ? ' p ~ awrnd
~ ~ d ' d~;;n',a-~&;og~b;
sPua7 s m 'pa?e3uqn[ p n ~
.(~al!qua s! q a x h d ~ - & ~ ~ ~ 6i'Xii&d$i
~ ~ 4.G3i;L.
~ ~ ~, ~ + ,
I?Tr;r9fl~BtXOVOd
P J P p YSOWa% -sa!qeyoas ciqnp,?~,w+pu%
sdAvlo BvqL&,$zPLtt.,am .

*.c:?.:e'o
ilw

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The volatilityaf ATPa is contfdled to minimize the]oS8 off&f&$ &$$&uri;ided.&,.raR


tanks due to boiling-off at high i1ditude8. Fop this
the
"&&i&$ '#k;$Ji$he .tn,
ATF is desirable. Distillatioq apeiifirntjon reguire~at l e s t 20 vol,c
r&dJ$e'&~$.~~,&jt+~The
20 p r c e n t point control8 hvnt-e~d.w]ati]ity,
and ensures ~ ~ k & : f ~ & ~ g j j j ~ + ~ a ~ i ~ y : $ ~ w &
001d atadbg and limit evaparaWon losses s t high altitudes,,
.,'
i
. ..
*uh-igniti?n of ATF can happen with a alght leak of fu&'from the engine .h&&: ifter
~h~f!b~!A!::"~.f?pa he1 line fracture during aperation. T ~ : ~ ~ & ~ r BU$
e , f.&i%n
W
~ ~ cw ~~a i n ec r e a s in
e ~vapour
~ proe?Un,
~
&.the atmOspherii ~~eBB,uiB;i-a~'d<~e.2fb-~yam\1i
~rew",""duel
increaa,ldao tho ~ut~-,gnjtion
tempe&"&j in;&&&,
'.
, .
6

.)

"",

Thermal properties. Jet engines require the use of fuels which ha*Lowfreezin~poinh
,
and maintain their flow properties. A high degree of thermal stability of fuels is
nqbirea t.a
PETROLEUM l i l & P N M N B k O Q W '

94

A ~ t y p i c a l a ~ i ~ i ~ n 0 * b ~ ~ ~ l i ~ Wknown
0 ~ ~ ~ ~ i ; P . 4 ~ , ,
tank~.bemeagure4directlyby
portable ( . m & t e ~ ~ :~ ~ r + ~ f i i by..
f u rMaibak
e d ~ ' or Emcee ~ l e c t ~ r . ~ , ~ ~ ~ . ; : ~ ? ~ ~ . ~ ~ $ ~ { ~ ~ ~ ,
demink'r d i ~ e ~ w a ~ ~ i ~ ~ ~ & & k ~CU;
i NT~USATE.
E y s f 'ha9:$~~w:10:~.~&td&bhvi$;,~he
.~~~:
e o d ~ ~ t l ~ t h t 4 . & e ~ : ~ f f e t t t t hkhi&rthe!~habgedi~nv,aree:ratt
re~avedifibm~tli'e;fue1,'
as conductivity unit @U). %he.c.onduetivity of a fuel in a

that..isthe-charge.relaxation. The time taken f~?lttl&.~cH&if&?ik~he


.itel.$0. Qll from.,agiven
valud~&lh&h2I&fl&iue~~(6he:.dud1'sS
half-walue.&im'e.=,tI/y
=12/con~ctivity'~(CU);.sec)i@ves
an
indi~~tio~E.wBether.static
charges.are.likely to..be'l$i~iddy~$i??fibt;
Chargeq.:c,a.n.ac~umulat.e
. . . . . .
t o l a ~ a p p , ~ c i ~ b l , ~ : e e x t ~ rif.thct.
i t : . ~re1,mation:
nly
tim~and.:~he~h.alf~~aIue
time. aIe. .higlxi,.
. . . . . . .r.;;r:
. . . l.;
.,, mg.
~gefi~ation~~o~~static:electrical:~rges,in~handling,oE~~Fs
.
has.Iong:beenirecopnized
as#~~dti'all&t;ph~zd~n
d ~. ~m~bAe r o ~ m ~ ~ ~ v e r i g g ~ p u r n p j nline
g ~ .velocities,
ates,
bottom
adoptedby.the majqr. oil
loading-(no.splash filling) and settling tifiidi'-~tiv8:b&fi$g2!~'e'1?:ii~1y.
cofhyl&~le~
.iii:stahdaid;ptactid&dor safe:handlin&.:df~thesq.pxod~ts.
:4s awadditipna1;safety
prg@,ution a static dissipator g ; r l d i t ~ v e . ~ a ' ~ ~ b e t i ' d d ~ d
~ . ~ ~per_mit~A,f9r,.u.~~.
~~~~~~~~.ad$itiv~.
in ..:@@lD1.2494.specification :is. -~alledi;@~&~~an~~-~,@~~~addi~on?rate
to -tharjfiiel~B:Zippm
(rnaxilnuml..:The!amou?t ofadditi~e~ r r e e ~ u i ~ ~ , d e ~ e ~ ~ g ~ R ~ ~
f<&p..ybi?h
~ t k ~ 1 6 ,..the
&d~,~~{r
fuel was produced, since the additive ie$Giise'is' affeit5dXytFC vahatfoii hi t h 6
th6mical
~ ~ , ~ p . , i o ~ ~ ~ f It
, ti%lts;yfd
R~~M
t4.q.djilpte
1 ~ 8,stati~
$ j q ~ i ~ a y'.$h,,@$l.be,fol;q
t $
,mq+ing
pltfi4dMw& tqp!4+,fud..Thie,,k done.(o
ens~~e.,g@gw$e.~~j~~~[~fl~fi~~~$q~~i~eeit,,3~eIfrleJi
.
.::::S&qtjc dis?iea,Wr, d4iti~iti~~ln+the-~~~~~~t~~tio~;~~qf#)~~~~~
'p$p;:pJfi~$Ay&hf
b$ereaL
U~bili$91 ~*$.akivefitabili%~,of~t)sfupl.or
it@~ w b y g t ~ ~ ~ q &&
yt ~ ~ t z ~ ~ ~
in t h e additive may re4pc.e .tlle,kater seeqromkkr : i r ! ~ - ( ~ p $ l i
~ .........
~ q ~1:bx;&6<4t:;5
~ ,.(. -W...
. . . . ,:
. . .
P.?~!I~.s.,.
.,.
.,.,
,
>,,;'?
,: .,:.i.<. .
. .. . ..
i;

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!DIESELFUELS
. .. . . . .. . . .
.:
:::~l,~,:'a.+::,;.,, . ;:~i.
?, . . . . . .
.,,:
. - . . ,?,.
,
k i g h speed die~el
toil (HSJWand,ligh~diesel;oil(ZW)~tiretpro~ur~:~~~~.Ogr
.cowtw.~
H ~ D
is:Wldely usedindiesel:engine f ~ r a . u t o ~ o t j r r ; e ; . ~ . ~ ~ o ~ e S .
, , a ~ ~ p ~ ~ ~ e s ; ~ o ~ ~ ~ ~ ~ ~ j ~ ~ ~ ~ ~ ~ ~ ~ p t j v e s .
Statjlonary.anti marine! diese1:engisas:as:. hsfa!J.ed;iqn?;hips,or
.ugg$.f~r:;dec@yi$yge,neratiqn
ompared ...b
:theIr~et,qfrwor~d,.
! ~ d i a ' s , ~ e q ~ d [ . ~ ~ ; d i*, ~A",..
~rowhly
~ ~ f ~ ~sijr
ls,is.
gasqline. .~irlces&rakhkru~~#e:sel
fj-$ctlpfiifo5;p,@~&:5~.%!dq,?il;~.ifiWSd,
'varying amduots..@fselected: cracke,dddij;sti!l.akp: from iconvqcsipn;. p$c@pee .
' s ~ c ~ , , g ~ , f l q i d d
rata!@k crackipgV.h~dr~cr,8cking,
cykiqg areiwd,t.o:incpqp$t+e.y@u.me ay.qjlabl.e:'formeeting
the growing demand of diesel fuels.
.
.
.:.: i T k ,P ~ W
! ~X
+ i ~ , f ? ~ t %?$ern!
$ ~ ~ p f~f;..~?vp~;e.9,sio?~i,~tip,n~e&$~~~f
f
aqy;qpl.ustion,
volatility .and.~ieanli,~~~fi.~$:b?~hi~
r ~ ; @ n ~ ~ ! ~ d . , t ~ : i r ~ ~ ~qq~,e:def
i d ~ i ~ ~$'$y2,yl
~~
th~(Bt
p ~ t r Pd F ~ ~ c~, U&@ Y a~c.li?@d:i~;~91)~~.~t{8,,$?~&~p9E~l$e.pd;,p.19
relates those properties which directly affect the abilitjr'dhi.~fudto
$;properly. ieiil f&ls
must be suitable for handling by the injection equipment. The handlingialid storage
characteristic is a function of volatility, fluidity, contami?a,ti,qn ddfin:
yfinement and product
s h i ~ 9?r!qovement.
~t
The characteristic,of cl&"filihebsdu~n~liki~sk633f&.t~d~&&i~tikition.
. . .
ti[ace:contamlnation,dfid kh&&gre$ :of +~$i:$n~~~tab;ili~j;of
t h I;di-ti~ar;I'~:fi~l:.
.
!::.: . . :
! ~ i e ~ ~ l ~ u ; ~ ' f o ~(I&& begded
gbo;d igniti;niiuali+, o ensufe
'.... $ d&y staitirig aha
~ u l ~ l i conteit
ur
m u s t bk c;iti&liy c6~&bll&'~6.iiii;ii&h&.eiivit~~~~fit~l
Poll,ution,Combsion,wear and
.

automot+

<!

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Fig. 5.2. Typical oscilloscopetraces forcompression ignition

. .
PETROLEUMRfflNlNa TECHNOLOQY
....

and

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r.: ;.: ,? r,:fhtr'$


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3,

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. ., . . .,
..

. . .. . .. . .. . .. . . . .

(d)Nkdedin
the
es/tikation of &ane index :
.
.
,
S~@cgravity (o)
for t6e w.nvira& ~ f ~ e & ~ ~ o l . db;v-~. l i -, & &
. . ! I,
.&
.

,&a;
.

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temperature of 15'C

%i
!

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(b) Greater carbon depaits expected for higher values of m'bn reeidue
11. Particulate

matter
I

(a) Indicates the potential of emission of particulate matter

(b) Co~taineprimarily carbon particla


(c) h u h n a o y w t @ h t e 9 finned
l u p h a s e &qg&) 'pprtidm:
' a b f ~ ~mr b d c 9 p~ g e m c m a t e d iq? en%nme$t u e L d o m 4cawe an ill e
f f a on human health Exeasslve soot W d e a m w t clog the exhaust valves
(
::-. 'r
,

7 2 . Aeh

(a') Resulte from oil. water-s01"ble P e ~ r c o m ~ -w


~ o r

loG&,

such w dirt and mat.


(6) Can be uaed to decide product's suitability fdr a given application
13. Sulphur
(a)Controlled to . ' ' cornion, wear and tear
(b) Caueee environmental pollution from their combustion p d u e t e
I
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~(c,ccirrosive in nature and causes p h p i d problem to en&e parta
Particulate matter con*
primarily carbonpartic1es. Carbonaceous prticuIa?s that
f o m h m gas-phase proceaaea a r e generally referred to a.smt, and those t h a t
develop fmm
p~mlysiaof liquid hydrocarbon fuels a r e generally referred to aa coke. Because
mot particu-

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