5Liquid Fuels

LI INTRODUCTION
The importance of liquid fuels is best
exermplificdby the fact almost all internal combustion
angines run on them. Lite wouldcome to a standstill if we that are denied this commodity, either
irom nature or frOm synthetic sources. The use of
liquid fuels in heat generation in ovens
and furnaces is expanding rapidly. The
development of highly
varving burning rates has made this possible. Furthermore, weefficient oil burners of widely
on petroleum as a source of carbon and hydrogen for the are increasingly dependent
productionof chemicals, fertilisers.
dyestuffs. plastics, detergents and fibres.
Petroleum accounts for the bulk of the liquid fuels. The other liquid fuels in use are
crude benzol, synthetic liquid fuels made from coal, shale oil, alcohol and oil coal tar.
from tar sands.
5.2 PETROLEUM

The term petroleun means oil obtained from the earth. Mineral oil, crude petroleum, crude oil.
crude or simply oil are other names for petroleum. Petroleum varies widely in
may be a straw-coloured liquid or even a black, viscous material. Most
appearance. It
petroleums, however.
are dark-coloured, highly mobile liquids in which gas is dissolved and solids are both dissolved
anddispersed. Sometimes, the gas separates naturally and gives rise to reserves of natural gas.
Once the liquid and gas are removed, the solids are separated on exposure to the surtace of the
carth and a natural asphalt deposit results. Harder types of natural asphalt are readily mistaken
1or asapropelic coal.
Petroleum Occurs in areservoir rock which has fluid holding capacity, porosity and tluid
trans1mit ing capacity and permeability. Most reservoir rocks are sedimentary rocks consisting
Coarse-grained minerals, such as, sand, sandstone, grit, limestone and dolomite. The upward
Migration of the fluid from the reservoir rock is prevented by an upper stratum called cap rvck
arealing formation. Acap rock has very tine pores and low permeability. Typical cap rocks
clays and shales. The migration of the fluid in other directions is prevented by suitable
geological formations of the reservoir rock and cap rock. These are known as oil trapS.
principle, the boundary between the cap rock and the reservoir rock should be conver
upward. The exact form varies widely. The simplest forms are tlat-lying convex lens and the
anticline and dome. The trapping of oil and gas is facilitaed by the presence of water or brine
seals (Fig. 5.1).
 7ITTTI777

Oilwith dissolved gas

Water

oiland gas
1.Cap rock impermeable to
oil andgas
2. Bottom rock impermeablec to
permeable
3. Reservoir rock porous and
and gas
Figure 5.I Vertical cross section of an anticlinal accumulation of oil

Table 5.I Reserves of crude oil in India (million tonnes)

2005 2006 2007
Area 1990 2000 2002 2003 2004
357 376 387 357
Onshore 307 317 332 339
382 410 369 369
Offshore 432 386 409 422
761 739 786 756 726
Total 739 703 741

Source: Ministry of Petroleum and Natural Gas, Govt. of India, Petroleum Statistics,
http:/petroleum.nic. in/petstat.pdf

Exploration for oil reservoirs is conducted by geological and geophysical techniques. Once
promising rock structures are confirmed, the actual presence of oil is established by drilling.
Usually, several deep bores are drilled to prove the existence or absence of a commercial
reservoir. Petroleum deposits occur in most parts of the world but commercial quantities
are produced mainly in a wide belt stretching from Indonesia through Myanmar (Burma),
India, the Middle East and Central Europe to North and South America. The most widespread
distribution is in the continent of North America, throughout the United States, Canada and
Mexico. The major oil fields are located in the Middle East (mainly Saudi Arabia, Iran, Kuwait.
Iraqand AbuDhabi) accounting for about 56.3%o of the world proved reserves of petroleum of
about 1.317 billion barrels (Table 1.2 and Fig. 1.2). The other major oil-bearing countries are
Russia 8.6%, Mexico 7%, USA 5%, Venezuela 3.6%, Libya 3% and Nigeria 2.3%.
Petroleumproduction in India
About 1.4 Mkm² or about 42% of total land area in India consists of oil
rocks. The offshore sedimentary basin exists up to a water depth of yielding sedimentary
0.4 Mkm². India's first oil well, 3Im deep, was drilled with a 200 m with an area of
steam-powered drill near an ol
seepage at Nahar Pong in Assam in l866. It failed to strike oil. On 26 March 1867, oil was
struck at 35.5 m at Makum in the Digboi area. A few more
wells
production was successful byl889-only 30years after the drillingwere dug and commercial
of the Drake well in the
 Table 5.2 Production of crude oil in India (thousand tonnes)
Item 2000-01 2001-02 2002--03 2003-04 2004-0S 2005-06 2006-07*
(April-Dec)
(a) Onshore
Gujarat 5815 6002 6042 6131 6187 6251 4697
Assam S199 5095 4660 4703 4474 3329
4592
Arunachal 78 69 74 83 J04
77
Pradesh
Tamil Nadu 436 440 395 375 391 385 267
Andhra Pradesh 263 283 300 281 226 216 185
Total (a) 11791 11889 11471 11456 11590 11430 8559
Of which
OIL 3286 3182 2951 3002 3196 3234 2351
ONGC 8428 8636 8445 8380 8320 8095 6087
JVCPrivate 77 71 75 74 74 101 121

(b) Offshore
ONGC(Mumbai 16629 16074 17560 17677 18165 16309 13409

High)
JVCPrivate 4006 4069 4013 4240 4226 4451 3516
Total (b) 20635 20143 21573 21917 22391 20760 16925
Grand total (a+b) 32426 32032 33044 33373 33981 32190 25484

*Provisional
Source: AnnualReport 2006-2007, Ministry of Petroleum and Natural Gas, Govt. of India

USA. Initially the crude was refined in a small refinery at Margherita. The first full-fiedged
refinery was commissioned at Digboi in 1899, with acapacity of about 90 kl per day. Through
oil fields have
the exploration work of governmentand semi-government agencies, several more Gujarat,
been discovered-Ankleswar, Kalol, Sanand, Nawagam, North Kadi, and others in
Moran-Nahorkatiya, Hugrijan, Rudrasagar, Lakwa and Galeki in Assam, Bombay High and
Godavarioffshore in the east.
Cambay in the western offshore, Palk Strait in the south and the
in the country.
Exploration isgoing on to ascertain theproved and recoverable oil deposits
The story of Bombay High (ONGC(Mumbai High)] is fascinating. The tirst step in offshore
(ONGC)in 1962 in the Gulf
exploration was taken bythe Oiland Natural Gas Commission
Cambay. The Bombay High was delineated by seismic surveys during 1964-67. Then
of
pace quickened and detailed seismic surveys were carried out. In view of the difficult
the The jack up
bydrometeorological and sea-bed conditions, foreign experts were consulted.
drilling rig, Sagar Samrat, arrived in Bombay in 1973.
production was started in May 1976 at the rate of 4300 barrels of oil per
Commercial
0.2 million tpy. The contribution of Bombay High led to a sharp rise in the
day (BOPD) or
figure. Table 5. l gives the crude oil reserves up to 2007. The total reserves in 2007
Production
49% was in the onshore area and the remaining
Sland up to 726 million tonnes, out of which
S1% was in the offshore area.
 of refineries as on TJuly 2005 (million
Table 5.3 Company-wise locations andcapacity
metric tonnes per annum)
Locationof Capacity
SI. No. Name of thecompany
the refinery (mmtpa)
Guwahati L.00
Indian Oil Corporation Lid. (IOCL)
2 Barauni 6.00
IOCL
3. IOCL Koyali 13.70

4. IOCL Haldia 6.00

5 IOCL Mathura 8.00
6 IOCL Digboi 0.65
7 IOCL Panipat 6.00
8 Hindustan Petroleum Corporation Ltd. (HPCL) Mumbai 5.50
HPCL Visakhapatnam 7.50
10. Bharat Petroleum Corporation Lid. (BPCL) Mumbai 6.90
11. Chennai Petroleum Corporation Ltd. (CPCL) Manali 9.50
12. CPCL 1.00
Nagapattnam
13. Kochi Refineries Ltd. (KRL) Kochi 7.50
14.
Bongaigaon Refinery &Petrochemicals Ltd. (BRPL) Bongaigaon 2.35
15.
Numaligarh Refinery Ltd.(NRL) Numaligarh 3.00
16. Mangalore Refinery &Petrochemicals Ltd. (MRPL) Mangalore 9.69
17. Tatipaka refinery (0NGC) Andhra Pradesh 0.078
18. Reliance Petroleum Ltd. (RPL) (Pvt. Sector) Jamnagar 33.00
Total
127.37
Source: Ministry of Petroleum and Natural Gas, Govt. of India,
http://petroleum.nic. in/refi.htm
The state-wise crude oil production is shown in Table 5.2.
was 32.190 Mt,out of which Bombay High alone The total production in 2005-06
the onshore companies, Oil India Limited accounted for 16.309 Mt (or 50.7%). Among
for about 8.1 Mt. accounted for about 3.2 Mt in 2005-06 and ONGC
It is of interest to note from Table 5.2,
in the country is very low in compared to Table 5.1, that the crude oil production
comparison to total reserves. There is thus a high scope for
expansion in the production figures by expanding the existing
refineries. According to the report of the Ministry
were 18 refineries in the country with a of Petroleum and refineries/establishing
new
Natural Gas, 2005, there
being as high as 127.1 Mt so that the per total capacity of 127.4 Mt per vear, the throughput
Table 5.3 gives the break-up of the cent utilisation the capacity was very high (99.5).
of
refineries in
Reliance Industries Limited at Jamnagar (33.0 MtIndia. Gujarat has the two largest refineries.
Koyali (13.7 Mt per year). Mention may also be per year) and the India Oil Corporation a
(9.7 Mt per year) and the Manali made of the
in West Bengal is also refinery in Tamil Nadu (9.5 Mt Mangalore
refinery in Karnataka
per year). The Haldia refinery
mentionable (6.0 Mt per year).
5.2.I ORIGIN OF PETROLEUM

The origin of petroleum is not satisfactorily Droved. A large number of theories have been
suggested from time to tinme. According to some, petroleum is of inorganic origin, being
formed by the action of water on metallic carbides or by the interaction of water and carbon
monoxide on alkali or alkaline carth metals. According tÍ others, petroleum was formed from
organie sources, animal or vegetable, by aprocess of destructive distillation. All these theories
have been rejected because they require some improbable materials or
prOcesses.
The vast poolof intormation gathered by petroleum geologists, chemists and geophysicIStS
has led tothe emergence of some rational views on the genesis of petroleum. For the sake of
convenience four phases of petroleum genesis are recognised:
embeddment of organic matter in source beds,
conversion of source material into a fluid,
migration of oil into the reservoir rock,
secondary transformation of oil inthe reservoir rock.
It is generally accepted that crude has been derived from the organic matter originally present
in marine sediments. The probable sources are plankton, marine algae, sea grass and larger
marine animals. Some terrestrial and freshwater plants may also have taken part in petroleum
formation. The absence of a reasonable amount of phosphorus in petroleum is an argument
against the involvement of fish in the processes. The dead organic matter settles down to the
bottom of shallow seas and lagoons. The settling process is facilitated by the presence of
mineral particles transported by flowing water to places where the current is less strong. The
settled debris is attacked by anaerobic bacteria. Most of the organic compounds are destroyed
and lost. Unsaturated fatty oils and fatty acids which survive the bacterial attack undergo
polymerisation into insoluable solids. These are buried under the steadily increasing cover of
sediments, while anaerobic bacteria continue to act on them. In the process of compaction, the
water content diminishes from 70%-80% to 10% or less. As a result of continued bacterial
decomposition under anaerobic conditions (reducing atmosphere), the decarboxylation and
becomes more
other reductionprocesses takeplace and the composition of the organic matter
and more petroleum-like. bed needs a
The formation of oil from the consolidated organic material of the source
considerable degree of degradatioin. The presence of thermo-labile and optically active
Substances like porphyrines and some nitrogen and sulphur containing complexes in crudes rule
the genesis of petroleum.
Qut the involvement of high temperatures, such as, above 200°C, in
material takes place are
Ihe probable processes by which the degradation of the source
anaerobic bacterial action,
low temperature cracking in presence of clay and mineral catalysts,
ITadiation by radioactive materialsassociated with sedimentary rocks.

temperature catalytic cracking is believed to be the major process by which oil was
LOW
produced from consolidated source material.
Table 5.4 Continued
Refinery/Location Installed capacity
as on Refinery crude throughput
T:4.226 1.4.2007 1990-91 2000-01 2(02-03
2003-04 2004-05 2005-06 20000
MRPL, 9690 9690 () 6438
Mangalore. 7253 10069 |1809 12014 12536
Kamataka
(b) PRIVATE 33000 43500 0 26033 30544 38379
SECTOR 32345 34309 33163
RPL, Janmna 33000 33000 26033 30544 32345 34309 33163 36616
gar, Gujarat
ESSAR Oil 10500
Ltd, Vadinar 1763
Total (a+b) 132468 148968 51772 103444 112559 121840 127416 130109 146551
* Provisional
Source: Ministry of Petroleum and Natural Gas, Govt. of India,
petstat.pdf Petroleum Statistics, http:llpetroleum.nic.in/

With the increase in the overburden, the source rockS are subjected to
cause the liquids to migrate to the reservoir rocks. During migration the compression and
composition of oil may
change by filtration, solution or adsorption. Both vertical and lateral migrations are
0il reserves were built up by migration of oil from a number of source beds. After possible.
reaching
the reservoir rocks, oil may or may not have undergone significant changes in its
composition.
depending upon its early history and the nature of the reservoir rock. The agencies for secondary
transformations are radioactivity, bacterial action and catalytic influence of rocks. An additional
factor in the case of shallow layers that are imperfectly sealed at the top is evaporation.
The reservoir rocks have been found to belong to widely varying geological eras, namely
Palacozoic, mesozoic, teritiary and quanemary, (see age of coaldeposits, Table 3.16). The bulk
of the oil fields are from the mesozoic (120-200 million years) and tertiary (oilgocenemiocene
periods, 20 40 million years) eras. Although it has not been possible to establish the precise
Tanks or degree of maturity of crudes of different geological ages, it appears from general
observation that crudes from older reservoir rocks are lighter and more simple in structure and
yield larger amounts of distillates compared to younger crudes. There are, however, exceptions
tO this. It has also been generally found that oils become lighter in going basinward in any
horizon (Hilt's rule).
5.2.2 PETROLEUM PRODUCTION

oil may be obtained from surface outcrops, from hand dug shallow pits or from
Occasionally
Seepage into mine galleries. However, the usual production is only from wells. The method
that is mostly used for digging a well is the rotary drilling system which utilises the principle
 and
of torsional grinding or cutting. The cquipment assembly is called a drilling rig it
of four main parts: consists
and
Derrick, a tall steel structure cquipped with hoisting gear for raising
drilling cquipment: lowering the
Drill colunn Or stem consisting of a main section of steel pipes (drill pipe) with at
its
lower end some extra heavy pipe (drillcollars). to which the bit is attached:
Rotating mechanism at the upper end of the drill column, that is at the surface, which is
a hollowv bar of Square or hexagonal cross section (the kelly or grief stem), and this
through a Square or hexagonal hole in the machinc (rotary table) which provides the slides
rotary movement:
" Mud circulation sstem at the top of the kelly is the so-called swivel through which a
thin
mud (drilling fluid) passes from a flexible hose:; the bottom half of the Swivel revolves
with the kelly while the top does not, and the flexible hose is attached to it. The top
of the swivel is also attached tothe hoisting mechanism. part
The hoisting system is controlled from a working platform built within the derrick above
ground level. A central power unit drives the various moving parts usually by mechanjcal
power transmission. The heart of the fluid circulation system is the mud pump plant. The mud
Ispumped down the drillpipe through the holes of the bit and returned to the pump section via
the annular space between the drill pipe and the walls of the bore hole. The mud brings the bi
cuttings with it. It is thereafter passed through a vibrating screen and/or settling pits before it
returns to the pump section tank.
An efficient mud circulation is perhaps the most important single factor required to drill
an oil well rapidly without accidents and difficulties. The drilling fluid serves four principal
functions, namely (i) cools the bit, (ii)flushes cut the cuttings, (iii) supports the bore wall by
hydraulic pressure, (iv) penetrates porous rock to form aseal of mud cake and (v) prevents
theescape of oilor gas through pores and cracks. Drilling muds are essentially colloidal clay
suspensions with additives to control viscosity.
The main boring is of 20-30 cm in diamneter and the depth ofa well may
Wells of more than 7.5 km have also been drilled while quite shallow vary from 1.5-4.5 km.
wells also
entire well is provided with a casing of steelpipes right upto the productive work exist. The
prevents the collapse of the bore walls and ensures that other extraneous flujds do layer. This
not enter the
well. Asteel tubing is suspended from the well-head up to the
with control valves and outlet pipe at the well-head. oil-bearing rock. It is provided
Oil is normally under pressure in the
reservoir. The
of compressed gas above the oil or a mass of water source of the pressure may be a boay
the oil to flow towards the foot of the well and underlying the oil. These pressures caust
drive it
flow). When oil pressure is low or it falls as the oil well upis the tubing to the surface (natural
by sendinggas at high pressure through the depleted. the lifting may be done
annulus between the casing and the tubing, or D)
providing a suitable pumping device at the lower end of the
method of secondary recovery of oil; water is tubing. Water flooding is another
wellson the periphery of the oil field. injectedinto the reservoir rock through Separate
 Cte total production irom cach well is
productionfrom a number of wells in piped to a gathering station meant for collecting
the the area. The gas is separated by directing the fluid
against baffles in cyl1ndrIcal pressure
settingout in tanks or by
vesscls. The water and solids are separated either by
recOvery of LPG and natural
centrifuging. The gas is called wet natural gas. It is processedlfor the
gasoline and put to other uses. The crude is sent to the refinery.
Rarely is crude oil directly used.

5.2.3 COMPOSITION OF
PETROLEUM
lalike coal. the ultimate analysis of crude
RC87%. hydrogen 11%%-14%, sulphur 0.5%-3%, petroleum varies wíthin a narrow range; carbon
gen 2%-3%. Theash of crudes is only nitrogen 0.1% (rarely up to 1%) and
0.1% or less. Practically all metals have been
in the petroleum ash; themost widely found
occurring elements are silicon, iron, aluminium,calcium,
magnesium, nickel and sodium. A few crude oils contain appreciable
Crude petroleum is essentially amixture of quantities of vanadium.
and aromatics are present in all crudes inhydrocarbons.
widely
Paraffins, naphthenes (cycloparaffins)
varying proportions. Only olefins and
acetvlenes are absent. Olefins are formed in the processing of petroleum. Only the lower
boiling fractions of crudes contain different types of
weight hydrocarbons include complex structures hydrocarbon as such. The higher molecular
containing aromatic and naphthenic rings
with paraffinic side chains. Sulphur, nitrogen and oxygen are
of bydrocarbons, for example, aliphatic mercaptans and present in the form of derivatives
polyalkylated quinolines, isoquinolines and pyridines, fatty disulphides, aromatic sulphides.
acids, naphthenic acids, phenols
and complex asphaltenes and resins.

5.2.4 CLASSIFICATION OF PETROLEUM

Ihe great variations in the nature and concentration of petroleum
components render it very
OiThcult to evolve a simple but satisfactory classification system. However, a three group
Classification is sometimes used by petroleum refiners for commercial practices. According to
this system, the following three
types of crudes are recognised:
Paraffn-base crude which produces aresidue containing both wax and asphalt.
Asphalt-base crude which yields a black and lustrons residue of asphalt.
O Mixed-base crude which produces a residue containing both wax and asphalt.
A
misnomner 'naphthene-base' is sometimes used inlieu of asphalt-base in the mistaken belief
easphalt-base crudes consist largely of naphthemic hydrocarbns. About 90% of the
crudes produced at present fall in the category of mixed-base.
The above classification is based on the principle that the nature of the residue determines
he nature of the whole crude. This is only of limited validity. Moreover, the grouping of the
buk of the Crudes under mixed-base also give an incomplete picture. These considerations
have led tothe development of anumber of improved systems. Out of them, the classification
of Lane and Garton is most widely used (Table 5.5). This is briefly discussed overleaf.
 Garton
to Lane and
petroleum according
Table 5.5 Classification of crude Key fraction 2
Key fraction 1 Sp.gr. 6O/60°F
SLNo. Sp.gr.60°/60°F 15.5°/15.5°C "API
15.5°/15.5°C "API
08762or less (30 or more)
(40 or more)
0.825 | or less 0.934-0.8762 (30 to 20)
or morc)
Parafffin 0.825|or less (40 0.934 or more (20 or less)
Paraffin-intermediate or more)
0.8251 or less (40 0.934-0.8762 (30to20)
Paraffin-naphthene 0.82510.8601 (40to 33) 0.8762 or less (30 or more)
4 Intermediate 0.8251-0.8602 (40 to 33) 0.934 or more (20 or less)
Intermediate-paraffin 0.8251-0.8602(40 to 33)
Intermediate-naphthene 0.934 or more (20or less)
or less)
0.8602 or more (33 0.8762 or less (30 or more)
Naphthene or less)
0.8602 or more (33
7

Naphthene-paraffin 0.934-0.8762(30 to 20)

or less)
Naphthene-internmediate 0.8602 or more (33
5.2.7.
give density as degree API, vide section
Note: Figures in brackets

recovered from the crudes on the basis of boiling range:

Two arbitrary fractions are and (i) 275-300C at a pressure of 40 mm of mercury
pressure,
(i) 250-275 °Cat l atmosphere and the latter, key fraction 2. Each fraction is classifed
1
The former is termed key fraction according to specific gravity, and the crude is classifed
as paraffin,intermediate or naphthene (Table 5.5). Following this system, acrude oil is called
on the nature of the key fractions
according to whether the cloud point of the key fraction 2 is below or
wax-free or wax-bearing have found that 85% of the crudes examined
respectively. Lane and Garton
above 5°F(-15°C),
into the three simple namely paraffin, intermediate or naphthene. Paraffin-naphthene or
fell
intermediate-naphthene crudes were not found to exist.
over the three-group classification n
The system of Lane and Garton is an improvement
might predominate in one fraction and
as much as it recognised that one type of hydrocarbon characterises the nature of only
another might predominate in another fraction. However, it
data. Mor
two fractions and that too by the approximate method of using specific gravity
detailed studies are necessary for the complete characterisation of crudes.
Not each crude can yield all the products of right quality and in commercially recoverabie
quantities. Typical paraffin-base and asphalt-base crudesdiffer widely in this respect (Table .0
Mixed-base crudes have properties intermediate between these two. Modern refinery processe
crudes
however. can overcome the deficiencies of crude to alarge extent. In general paraffin-base veld
crudes
yield good quality kerosene, diesel fuel, lubricants and waxes, while asphalt-base
good quality gasolines and asphalts. The refinery processes are largely influenced by they
crude to be treated.
the old
Crude oil from Pennsylvania (USA) and certain fields in Rumania, Poland and
areasim
USSR may be classified as paraffin-base, Crudes from California (USA) and Some East
Mexico, Venezuela and the old USSR serve as examples of The Middle
crudes form a large group o1 the mixed-base type.
asphalt-base oils.
up to
Some crudes need special mention. Borneo crudes yield gasoline containing u
fractions directly
40% simple aromatic hydrocarbons. Another be used
Indonesian crude(Tarakan) may
 Table 5.6 Comparisonof paraffin-base and asphalt-basecrudes
Propertis Paraffin-hase Asphalt-hase
Speciftic gravity low
high
Yieldof straight-run gasoline high low
Octane mumber of gasoline low high
Odour of gasoline Sweet or sour aromatic or sour
Sulphur content of fractions low high
Smoke point of kerosene high low
Cetane number of diesel high low
Pour point of dicsel high low
Yield of lubricants high low
Viscosity index of lubricants high low

fuell or light furnace oil. Light Kettleman Hills (California) crude practically consists
xdiesel
ofgasolineonly.
crudes
Nature of Indian
the characteristic
The ail fields of India yield highly waxy and mixed-base crudes. Some of
varies from 22.3-38.5.
ronerties of three Indian crudes are given in Table 5.7. The APIgravity
content is
he ightest being Bombay High and the heaviest the Cambay crude. The sulphur
eny low in all Indian crudes. The crude from Bombay High is almost
sulphur-free. The wax
content is hightest for Cambay and lowest for Bombay High. and Nahorkatiya
The yieldof straight-run gasoline is more than 20% from Bombay High
the lowest from Cambay.
and less than 10% from Cambay. The recoveryof total distillates is
gasoline contains more
The Bombay High crude is very highly aromatic. Its straight-run
and Cambay are 20-25 and
than 60%aromatics. The corresponding figures for Nahorkatiya Southeast Asian
common feature of
5%, respectively. The high aromatic content is a
CTUdes.

5.2.5 PETROLEUM PROCESSING

dirt. water andmuch of the associated natural gas, the crude is separated into
ier Temoval of simple purification
further subject to
"alons by distillation and the resultant fractions are the nmanufacture of diverse petroleum
Teatment
or complex conversion processes for
more in a
refining and are carried out
as petroleum
products. . All these processes are referred to
Tehinery. grouped under three main heads, namely
Refinery processes may be conveniently
example, distillation and solvent extraction,
for
2. Physical Separation processes,
example, cracking, visbreaking and coking, polymerisation.
3. BrRebuieakdown
lding
processes, for
processes,for example reforming, alkylation, isonerisation and
 Table 5.7 Characteristic properties of Indian crudes
Nahorkatiya, Bombay
Cambay. High offshore
Assam
Gujarat
0.8324
0.8574
Specific gravity, 15.5°/15.5C API 0.8638
38.5
223 33.5
2.60 0.06
Water content. per cent v/v
0.014 nil
Salt content. per cent w/w 0.05
0.13 0.17
SulphurCOntent. per cent w/w 4.91 5.1
Kinematic viscosity at 37.8C. CS 35.6
Calorific value, kcal/kg 10800
30-32 27.0
Pour point. C 35.0
Distillation characteristics
41.0 38.0
IBP. C 62.5
23.0 22.0
Upto 1SOC. per cent v/v 9.2
32.5 33.0
150-300C. per cent v/v 26.5
300-465 C. per cent v/v 35.25 32.2
Total up to 465 °C, per cent v/v 70.95 87.7
Fraction up to 150°
Sp.gr.(15.5°/15.5°C) 0.7195 0.7471
Refractive index, 20*C 1.4041 1.4222
Aromatic content 3-5 20-25
Fraction 150-300 °C
Sp.gr. (15.5 °/15.5°C) 0.7920 0.8516
Refractive index, 20°C 1.4404 1.4777
Fraction 300-450C
Sp.gr. (15.5°/15.5°C) 0.8698 0.9273
Sulphur. per cent w/w 0.05 0.24
Wax content. per cent w/w 32.2 24.4
Short residue (>465°C)
Sp.gr. (15.5 /15.5C) 0.9554 1.0050
Penetration number 50 16
Softening point (R and B),°C 55 67
Wax (300-465°C), on the basis 16 12
of crude, per cent w/w

Various product streams are further refined before marketable products are obtained. According
tothe processes used, refineries may be classified as simple, more complex, or fully integrated.
Simple refineries produce only a limited range of products, mainly gasolines, kerosenes and
avíation turbine fuels, gas and diesel oils, and fuel oil. Besides a crude oil atmospheric distillatiou
unit, the onlyother unitsare those for reforming and for purification treatnment. The
in more complex refineries are usually a vacuunm additionaluntts
with the units for the processing of cracked gases by distillation
unit and a cracking plant togethe
Premium motor and aviation gasolines and bitumenpolymerisation, alkylation and other meths.
are the notable additional products.
The whole range of petroleum products is
additional units include ahigh vacuunn fractionatingobtained in the fully integrated retineries.
oils, a de-asphalting unit, a solvent extraction unit, a unit for the preparation of lubrie
dewaxing unit, and a coking unit. S
 1950, integrated
preferred. There refinerics
are export
which are cheaper to build and operate in the long run have been
oriented refineries located nearrefineries located at. or ncar the crude oil sources and market-
the markets for the petroleun
tankers. the products. The advent of huge oil
the increasingdevelopments of in the piping of oils and the
oil strategy of
installation
A retinery may draw its market-oriented refineries. government nave led
crude oil supplyfrom a single or many oil
not very different they may be fields. If the crudes are
fuels may be kept separate from those blended before processing. Those yielding superior distiiiate
superior lubricantsor asphalts may be producting inferior stocks. Similarly. the oils that yield
segregated. It is not
fraction for gasoline production.necessary extend such segregation
to the cracking of heavier to

Petroleum distillation
The refiningof petroleum begins with the
separation of the crude by distillation into a number
of fractions. The distillation is carried out first
under atmospheric pressure and the residue from
this primary distillation (reduced crude or long residue) is then
primary distillation is also known as the topping of the crude oil.distilled under vacuurn. The
The maximum temperature
upto which a crude can be heated without cracking is about 400°C. This
sets the limit of the
maximum amount of distillate that can be collected byatmospheric distillation. Steamis used
to facilitate the vaporisation of the high boiling
constitutents. The recovery of still heavier
fractions, upto 600°C boiling range, is possible in the vacuum units further assisted by the
admission of steam.
Fractions into which crudes are commonly separated are named in Table 5.8 with their
approximate boiling ranges and uses. Primary distillation usually recovers fractions upto gas
o1ls, while vacuum distillation recovers vacuum gas oil, raw lubricating oil distillates and
asphalt or bitumen. The actual practice in a plant considerably varies from plant to plant.
depending upon the type of crude input and the demand of products. On the one hand the crudes
themselvesyield fractions of different quality and quantity, and on the other. the boiling ranges
of petroleum products considerably overlap each other. The nomenclature of the tractions also
changes accordingly.
While vacuum distillation is a one-stage operation, primary distillation may be run in one or
twostages. Figure 5.2 shows a flow-sheet of a complete three-stage crude distillation unit. The
boiling upto
irst stage operates at 3 to 4 kgt/cm² pressure and produces gases and light distillatesecond
9OC. The bottoms from the first stage are heated to about 4O0°C and sent to the stage
distillation column which operates at atmospheric pressure. Naphtha is recovered as top stream
reheated to about
erude is
Wnile kerosene andgas oil are withdrawn as side streams. The reduced
the top stream
00°C and pumped to the vacuum column (50 to 100 mm Hg pressure). Here
asphalt or biumen and heavy turnace
S araw lubricating oil. The bottoms are used in making microcrystalline waxis recovered
OI. Parafffin wax is manufactured fromvacuum gas oilwhile
or residues from parattinic crudes.
Om certain typesof heavy lubricating oil distillates
components as mpurlies. These are purified by
1he side streams contain some lightercarries off the lighter compOneNts bick to the main
passingthrough steam-strippers. Steam obtained at the bottomof the stripper.
Oumn while the purified fraction is
 ruels and CombuStion

Gas

To vac

Naphtha Heavy gas oil

Fecd Kerosene
Light Lube oil
distillate Gas oil
furnace
Furnace

Residual fuel oil Bitumen

Topped crude stream
Figure 5.2 Three-stage distillation of crude oil

Table 5.8 Common fractions from crude petroleum

Fraction Approximate boiling range, "C Uses

Fuel gas - 162 to -42 containing methane, ethane and

some propane; used as refinery
fuel.
Propane -42 liquefied petroleum gas (LPG)
Butane -12 to -0.5 LPG component of gasolines in
cold climate
Light naphtha -1to 150 straight run gasoline, solvents,
depentanised added toheavy
naphtha feed for reforming
Heavy naphtha 150 to 205
catalytic reformer feed, component
of jet fuels and solvents
Kerosene 205 to 260
illuminant, fuel
Stove oil 205 to 290 fuel
Light gas oil 205 to 315
fuel oil, diesel fuel, absorbent
Heavy gas oil 315 to 430
Vacuum gas oil
catalytic cracking feed
430to 540
catalytic cracking teed, suitable
Residue (short residue) 595 and above
crudes yield lubricating oils
heavy fuel oil and asphalt or
bitumen, petroleunm coke making

Fractionating columnsvary greatly in sIZe.The usual dimensions are 3 m

height. Plates of variousdesigns are used by diameter and 30to 35 Ml
spacing are usually suficient between two different retfineries.Three to five plates, at 0.56
columns. Thisnumber is two to three for vacuumneighbouring product streams in atmospherl
owing to the increased difference of columns where fractionation is more efficie
vapour pressure of components and also
larger spacing of plates. because of ue
 Flue gases

Oil
Oil

ooo00o%
Oil
Oil
Burner fuel + air
Burner fuel + air

Figure 5.3 Box-type pipestill

In the distillation units,crudes are

heated in
with a relatively long but small diameter pipe.pipestills. Apipestill is a special type of furnace
The pipe consists of a large number of tubes
connected through bends. The tubes are housed inside the furnace chamber in single and
multiple rows. The furnace is built in two sections, namely, radiant and convection. The tubes
in the radiant section receive heat directly from the
flame and those in the convection section
recover heat from the hot gases travelling to the stack. There are
depending upon the arrangement of tubes and direction of liquid different designs for pipestills
the oldest and quite widely used (Fig. 5.3). The furnace is flow. Box-type stills are
divided into two chambers by a
bridge wall. Separate burners are put on the side walls. The convection section is separated
from the radiant section by a row of tubes. The crude is pumped into
the pipe inlet at the
convection section. The final heating to about 400°C takes place when the preheated crude
passes through the radiant section tubes. High rates of heat transfer are obtained by radiation
and convection and by high liquid flow rates in the pipe. The high flow rate of the crude also
ensures high productivity and prevents local overheating which might otherwise cause cracking
and coke deposition.The box-type stills have inputcapacities of 5-20 million kcal/h. The heat
flux is 15,000-40,000 kcal/m² of circumferential tube area per hour and the heat release is
20,000-45,000 kcal/m² furnace volume per hour. A high proportion of the total heat transter
between 55% and 60% is by radiation.
Stabilisation: Natural gasoline,cracked gasoline and similar stockscontain dissolved hydro
carbons (gaseous and very highly volatile liquids) which tend to escape during storage.
Stabilisation is the process of removing these lighter components and making such stocks
stable and suitable for storage and handling. A typical cracked gasoline may contain more
than 10% of butane and lighter hydrocarbons. Stabilisers are essentially high pressure.
8to 15 kgflcm', fractionating columns using 40to 50 plates and high retlux rations. The escap
Ing vapours on condensation separate into gaseous and liquid streams. The liquid is refluxed
and also recovered as a speciality product. The stabilised gasoline is withdrawn from the bot
tom through aheat exchanger whichpreheats the feed. Extra heat issupplied at the bottom of
the tower by means of a reboiler.
 from petroleum or shale(IS:1593--|982)
Table 5.12 Specitications torfucl ois derived Grades
Characteristic Medium Medium High
Low
VisCosity viscosity viscosity
viscosity 2

66 66
66
66
(closed),C, min 180 370
Flash point(Penskv Martens) max 80
125
Kinematic viscosity,centistokes at 5OC, L.0
L.0 L.0 L0

Water c0ntent. per cent by volume, max 0.1 0.1 0.1 0.1
4,0 4.5
Ash. per cent by mass, maN 3.5 4.0
Sulphur. total percent by mass, max 0.25 0.25 0.25 0.25
Sediment. per cent by mass, max nil nil nil
nil
Acidity, inorganic

Lubricants
wide range of products. Base oils are obtained as distillates or residual
Lubricants include a requirementsof individual operations.
products inthe refinery and are blended to meet specific
conventional additives include fatty oils, lard and fatty acids. Some of the additives
The
contain constituents like sulphur, lead, graphite, molybdenum disulphide or metal soaps, Anti
metal surfaces from
Oxidants and anti-corrosion agents are also sometimes added to protect the
corrosion.

5.2.6 PROPERTIES AND TESTING OF PETROLEUM AND PETROLEUM PRODUCTS

It has been seen in the previous section that the petroleum products include a wide range of
substances. The properties that make them suitable for specificuses differ from case tocase. NO
single set of Lest procedures is therefore available for evaluating them. Some of the common and
special properties of petroleum products and the principle of the corresponding test procedures
are discussed below. Indian specifications for some products are given in Tables 5,9 to 5.12
Specific gravity
Specificgravity is used in calculations involving weights and volumes. Because of the
of the inherent chemical nature of the main closeness
components of petroleun products, it has been
possible to correlate their specific gravity with other important
gravity means higher concentraion ofcarbon in relation to parameters. Higher specite
lower calorific value (gross)on a weight basis. hydrogen. Hence, heavier oils have
The reverse is true if the calorific
equation is useful in the calculation of value
is expressed on a volume
basis.
gross caloritic values of petroleum oils: The following
C. = 12400 - 2100d2
(5.)
where, Cis the gross CV,
kcal/kg, and dis the specitic gravityat 15.5/15.5°C.
 Liquid Fuels

to many empirical correlations,

specific gravity is used as Degree API defined in the
following way by the Americal Petroleum
Institute:
141.5
°API= 131.5
Sp.gr. (15.5°/15.5°C) (5.2)
mhis is aslight variation of the Baume scale. Among
specific gravitythan the paraffins. Therefore a
hydrocarbons, the aromatics have higher
predictthe quality of a given product. knowledge of specific gravity can appreciably
Viscosity
Viscocity iS a very important property of fiuids and a measure of their resistance to flow. In
netroleum technology, this property is widely used in design calculations for transportation,
ombustion in burners and internal combustion engines and lubrication. It is an important
specification parameter for many petroleum products.
Viscosity may be determined in a U-tube viscometer and other convenient apparatus. The
conventional method for oils is to measure kinematic viscosity and express this in centistokes
or some arbitrary units. Standard equipment and standard procedure are used to measure the
time required for a fixed volume of oil to flow through an orifice of fixed dimension at a
certain temperature. Different standards vary in the design of the equipment and the procedural
details. The different standard viscometers used for oils are: Engler, Redwood No. I, Redwood
No I,Saybolt Universal and Saybolt Furol. The result is usually expressed as the number of
seconds required for the flow. In the Engler viscometer, the viscosity is expressed as a ratio of
the time of flow of equal volumes of oil and water and is called degree Engler. It is possible to
Convert the data of one standard into those of another and also into stokes (Table 5.13).
Viscosity is one of the most important criteria of fuel oils. It significantly influences the
case of handling and transport and the nature of storage. The viscostiy of the oil supplied to
atomising oil burners has adirect effect on aburner's performance, and hence on its combustion
eficiency. Residual oils have high viscosityat ordinary temperatures and need preheating
before atomisation. The viscosity of fuel oils falls as the temperature rises but becomes nearly
OIstant above 120°C. For atomisation, there is little gain in heating the oil beyond 120°C. The
mum viscosity for easy atomisation in conventional burners is 25 centistokes or 100 sec
Redwood No, I. For easy pumping in usual pipes, the maximum is 1,200 centistockes or
986 sec Redwood No. II.
There the capacity of the burner. While
are two oppoSing effects of oil preheatingtheonservice line aand atomisation in the
decreased viscosity facilitates flow of oil through
burner, decreased density resultsin the delivery of lesser weight off oil to the burner. There is
thereforean optimum temperature beyond which additional preheat actually
lowers the burner
capactiy.
The performance of diesel fuels also greatly depends upon their viscosity. Toolow a viscosity
Causes excessive leakage at the injection pistons while too high a viscosity produces coarse
oil droplets which result in the formation of engine deposits owing to incomplete combustion
 The action of lubricating oils in a
Owing to Oxidation and other particular system depends upon their particular viscosity.
reasons,
periodical replacement of the lubricant. viscosity changes appreciably which necessitates the
The cffect of
known. It a system is subjected to a
variation of temperature on viscosity of oils is well
varies beyond the tolerable limit, the
purpose temperature,
of lubrication
and if the viscosity of the lubricant
is defeated, It has been found that
the extent of variation in
11 lubricating oils. Paraffinicviscosity for a given temperature fluctuation is not the same for
stockS tend to resist alteration in viscosíty with temperature
thange while naphthenic stocks show large
dependence of viscosity on temperature. This
visCosity-emperature relationship of lubricating oils is
and is expressed as a number on an arbitrary scale. A denoted as the viscosity index (VI)
VIof 100 and anaphthenic Gulf Coast oil has a VI of 0.highly paraffinic Pennsylvania o1l has a
If L. HandU are the viscosities in CS
of the ) VI, 100 Vland the givenoil,
respectively, at 100°F.
L-U
VI= X100
L-H

Vfhe viscosity of the twO standard oils and the unknown sample must be the same at 210F.
The kinematic viscosity, U, of the sample is first determined at 210°F and the values of
L and H are then read from the standard ASTM chart corresponding to that viscosity of the
sample.
Oils with a high VI are preferred where a wide variation in temperature is encountered
as in the outdoor use of crank case oils and hydraulic oils. Certain additives, for example,
polybutenes improve the VI of oils. For high VI oils (VI>100), another parameter called
ViSCOSity index extension (VI) is used.

=
(antilog N) 1 +100
0.0075

log H- log U
where, N=
KVT;10
H= kinematic viscosity at 100°F of an oil having a VIof 100 using the standard
at 21l0°F
method and having the same viscosity as the unknownoil
U= kinemative viscosity at 100°F of the
unknown oil.
1I0°F
KVI,i, kinematic viscosity of thesample at 2
H>U

At very high pressures the viscosity of oils increases consideratbly. At apressure of 70 kgtlem',
solidify at 3,500 kgt/cm'.
e ncrease is by 15%. Most oils begin to Therefore the viscosity of oil blends has to be
VISCosity is not an additive property.
charts.
Aperimentally determined or calculated with the help of empirical blending
 Distillation range
between thetemperature at the
pointdifference tennperature initial
in test. It pertainsto distillate products such aas gasoline
point and at range
Distillation the endis the of a distillation
and kerosene. Residual fuel oils are not nornally subjected to a distillationtest. The singlemo boil ng
crudes is their distillationcharacteristics.
distillationfortest for petroleum products, a measured volume of the oil is distilled
Inthe criterion
important
which is suitably increased as the distillation proceeds. The initial
the specified rate
point (IBP) is the temperature when the first drop
at the end of distillation.
boiboilliinngg
falls fromthe condenser and the final
ispoint
maximum temperature recorded
.Mid-boiling potnt
(FBP) is the at which 50% of the oil distills off. Distillation is stopped at 360°C because
the temperature
necessary the distillation may be
further heating causes cracking of the residue. If petroleum products contined
under vacuum. The distillation range is of value in the evaluation of
Distillation parameters like mid-boiling point often find application in correlations for ot
important parameters.
Distillation data are conveniently used to construct very useful curves, for example te
boilingpoint (TBP) curves,and equilibrium or flash vaporisation curves. The TBP
curves gve
the variation of boiling point with the yieldsof distillates. Each point in the flash vaporisatiom
curve gives the total amount of vapourinequilibrium with the liquidat the particular temeprature
These curves are used in the design of continuous distillation equipment in refineries.

Flash point and fire point

The flash point is defined as the minimum temperature at which the given oil evolves just
sufficient vapour to form an inflammable mixture with air, as shown by the formation of 1
momentary flame (flash) when an external source of fire is brought in contact with the vapour.
The fire point is the minimum temperature at which the oil
instead of just flashing. For the same product the fire point is vapours will continue to burm
higher than the flash point. I
I5 customary to determine and report both the
(fiash point) is itself a measure of the fire risk oftemperatures, although the lowe temperature
The permissible conditions of storage and useanareoil or any inflammable liquid in bulk.
below 23°C(gasoline), between 23°C and 66°C different for products with flash po
o1ls). The oils of the first category are (kerosene) and above 66C (fuel oils and ga
transport and storage, and are subject toregarded as dangerous and highly inflammeeie
points above 66°C are strict government regulations. Fuel oils with tlash
Besides regarded as safe.
limits of thedependingon such inherent properties of the oil asthe
vapour-air
test procedure and the mixture, the flash point also volatility and the intlamnability
apparatus,the
barometric depends
pressure. Two types of upon the design of the
1. The apparatus are commonly used:
Pensky-Mart
2. The Abel ensfor oils with with flash point above
apparatus apparatus for oils
Kerosene tested in the Abel, and
is flash points 50°C,
below this
apparatus. Both these fuel
apparatuses
oil,
are of the
temperature.
diesel fuels and gas -Martens
oils in the Pensky- cup
closed-cup type. The oil is heated in a closed
 LIquid Fueis

underspecified conditions and a pilot flame is introduced into the vapour space by opening a
shutter in the lid. The American Tag apparatus is
similar to Abel.
Flash points of lubricating oils, some crude ojls and residues are often determined by tne
onen-cup tests. Either the Pensky-Martens cup or the Clevelendopen-cup is used.The open
cuptestis liable to error and gives only approximate values. The open-cup flash point is higher
thanthe closed-cup value for the same sample.
The flash point and the fire point give indications of the range and nature of the boiling point
curve. The flash pointof lubricantshelps toindicate the relative amountof low-boiling mateial
present in it.
These temperatures must not be confused with the completely unrelated spontaneous
ignition temperature (SIT)(see Chapter 8).

Pour point and cloud point

These are used as criteria for fuel oils lubricating oils and diesel fuels used incold surroundings.
The pour point is defined as the temperature 5°F (2.8°C) higher than that at which the oil ceases
to flow when cooled and tested according to prescribed conditions. The cessation of flow
results from an increase in viscosity or from the crystallisation of wax from the oil. Heavy fuel
oils have quite a high pour point and heating facilities are usually necessary in order toensure
the satisfactory flow of the oil. Fuel oils of wax-bearing crudes have much higher pour point
than those derived from crudes of low wax content. A low pour point is the desired property of
an oil in respect of handling incold atmosphere.
The cloud point is defined as the temperature at which an oil becomes cloudy when it is
cooled in a specified manner. Thistemperature is higher than the pour point (usually by 5°C to
6°C). The cloud is due to wax crystals. If the oil is moist then also itmay become cloudy due
to the immisibility of oil and water at the low temperature. The cloud point is more significant
than the pour point for diesel fuels where the wax crystals can plug the filters in the fuel
injection system and stop the flow even when the oil is above its pour point.
point of an
Asphaltic substances act as pour point depressants, that is, they reduce the pour
01l by inhibiting the growth of wax crystals. Pour points may also be reduced by increasing
naphthenes and aromatics have a
Lne proportion of lighter hydrocarbons in an oil. Ingeneral, undesired components of fue!
lower pour point than paraffins. Unfortunately the former are the
oils and diesel fuels.

Smoke point and char value

to assess the burning quality of kerosene as an
These empirical criteria are determinedkerosene should be clean in respect of smoke in the
quality
illuminant or as a fuel. A good toadstool on the wick. Smoking is due primarily to aromatic
flame and the deposits, char or related to both aromatics and disulphides. The smoking
char deposits are
hydrocarbons; determined by the smoke point test, andithe deposit forming tendency
tendencey of kerosene
by the char value test.
is
 The smOke point is the maximum flame height in millimetres at which kerOsene will b
without smoking in a standard apparatus. Good quality kerosene shows a
20 to 25 mm. Careful acid treatment raises the smoke point to abOve 30 mm. smoke
point of
The char value is the amount of char in milligrams, for every kilogram of
keroseneTheburned.
which is formed on the wick of a standard lamp burning under prescribed conditions. ch
value of a high grade kerosene should not exceed 20 mg/kg.
The formation of smoke and char depends upon the type of burning appliance also. Sorme
appliances need kerosene of high smoke point and low char value. Yellow flame, wick-fod
appliances,for example, railway signal lamps which are required to burn for prolonged periods
without attention, fall into this category. Blue flame appliances, for example, space heaters
can tolerate kerosenes of lower smoke point and higher char value.
The burning quality of kerosene is also judged by its tendency to form awhite or grey
deposit or bloom on the glass chimney of lamps, which leads to a reduction in the illumination
power. Disulphides are believed to be responsible for the bloom.
Carbon residue
This property is important for oils used in gas production, in diesel engines, in burners and for
lubricating oils used in motors. When an oil is heated both evaporation and cracking set in.
The heavier, complex compounds form, on decompostion, some
as carbon residue. There are two methods for the carbonaceous depositsknown
determination of this residue. Conradson's
and Ramsbottom's. The Conradson test is used for fuel oils and
the Ramsbottom test for
lubricating oils. The distillate fuels have a low carbon residue and the test is applied on the
10% residue after distilling off 90% of the fuels. Kerosenes have
so low a residue that this test
is meaningless and the char value is determined in lieu of
carbon residue.
Fuels for high speed diesel engines shouldhave a
than 0.1% on a 10% distillation residue. Low and Conradson carbon residue of not more
medium
higher values of Conradson carbon. The nature of the carbon speed engines can tolerate mucn
important. If the deposit is fiuffy it is easily removed with the deposits in diesel engines is very
exhaust gases. On the other hand
compact deposits get firmly attached to the engine parts.
Atomising burners are practically insensitive to the
gas oils used in the vaporising burners should have carbon residue of the fuel. However tie
0.05% on the 10% distillation residue. Conradson carbon value not exceeals

Sulphur content
All crudes contain sulphur. Even
after
petroleum products contain sulphur. In passing through various purification processe
in the boiling range of the product. Somegeneral
typicalthe sulphur increase
values are: content
keroseneincreases
0.05%-0.2%,with the
gasoiland
diesel oil 0.3%-1.5% and fuel oil
2%-4%. The high value, 4% is for the furnace oilsof
high sulphur crudes. heavy
The sluphur content of oils is best
determined by using a bomb
values are obtained by the lamp method in which a known weight of the
Approximalte
oil is burnedinanaf
calorimeter.
current and the combustion products passed throuch an alkaline solution, the sulphur bei"g
finally estimated in the solution as
sulphuric acid.
The suiphur content should be as low as DOssible. Sulbhur is argely present in oils in the
form of corrosive organic compounds. On
combustion it givesoff foul gases.
Moisture

The solubility of water in oils is quite low -0.005% to 0.05% under ordinary
may however be present in the dispersed state in residual fuel oils up to 1%. conditions. 1
undesirable. Its separation from oils is facilitated by preheating. The Dean andWater
in oils 1s
is used for the determination of moisture in oils. Stark meth0d
The sample is heated with xylene wne
forms an azeotrope with water. The distilled vapours on
condensation and settling give water
as a separate layer which can be measured. The Karl Fischer test
can be used to
determine water content of 50 to 1000 ppm in oils. The method consists of accurately
titration with a special reagent. electrometric
Ash

The amount of ash in petroleum products is normally very low. The

zero ash but certain additives to gasolines or diesel fuels raise its distillates should have
value. Even a residual fuel
should not have ash exceeding 0.1%. Some constituents of petroleum ash have
effects. The presence of vanadium in fuel oil causes discolouration of the moltenvery harmful
while sodium causes bonding of ash constituents on boiler glass tanks,
refractories. superheaters and also attacks
Calorific value
The ultimate analysis of petroleum fuels does not vary widely.
Therefore their calorific value
also varies within a comparatively narrow range,
10,000-11,300 kcal/kg gross, the higher
figure being for gasolines and the lower for heavy furnace oils. Petroleum products are high in
hydrogen content, 11.8% to 14.5%,and hence their net calorific value is less than the gross by
as much as 620-760 kcal/kg. The calorific value of oils is
determined in a bomb
Empirical formulae are available for calculating the calorific value of petroleumcalorimeter.
fuels from
their specific gravity (Eq. 5.1).
Octane number
Maximum power is derived from gasoline when it burns silently and relatively slowly. Under
certain engine conditions the combustion may begin smoothly and then the whole of the unburnt
fuel may burn rapidlywith the formation of pressure waves (detonation). This leads to knocking
of the gasoline engine. Much of the generated power is wasted and the engine life is
shortened
When knocking occurs. A good gasoline should resist knocking. The anti-knock quality of ftuel
IS measured in a standard engine in terms of the relative performance of two standard fuels and
hen expressed as its octane number. By definition, the octane number of a gasoline is equal
lo the percentage by volume of iso-octane (2,2,4-trimethyl pentane) in a mixture of n-heptane
 and iso-octane having the same knocking tendency as thesample beingtested. n-Heptane is of
number. On the other hand.
poor anti-knock
excellent quality
anti-knock quality assigned
and isand zero octane iso-0ctane
has
is assigned an octane number 100. If agasoline matches with
80/20 blend of iso-0ctane and n-heptane, its octane number is 8O. Secondary reference fuet,
a
the octane number of gasoline.
are used inpracticc for experimentally determining depends upon the types of hydrocarbone
The anit-knock quality of agasoline primarily naphthenes, olefins and
present. Aromatics have the best anti-knock quality andiso-paratfins,
n-parafins follow in succession. Allhe refinery processes for the upgrading of gasolines aim
at the conversion of other hydrocarbons into aromatics and is0-paratins.
A certain minimum anti-knock quality is required for knock-free operation of a gasoline
engine. This requirement primarily depends on the engine compression ratio.In the USA
and Canada, the motor gasoline is marketed in two grades: regular with octane number 94
and premium with octane number 100. The motor gasolines in India have 83 and 93 as the
specified octane numbers. Aviation gasolines have octane numbers exceeding 100.
The octane rating of commercial gasolines is not entirely due to the hydrocarbons onlv.
Certainadditives are put into the gasoline toraise its octane number. The most effective and
common additive is tetraethyl lead (TEL)which is used in admixture with organic halides. The
halides are added to prevent the deposition of lead by forming volatile lead halides. Paraffins
and naphthenes have higher lead susceptiability than aromatics.
Other anti-knock agents are tetramethyl lead (TML) and tertiary butyl acetate. Methyl
cyclo-pentadienyl manganese tricarbinol may be used in conjuction with TEL for boosting the
octane number of motor gasoline.
Cetane number

There is a time lag (delay period) between the injection of diesel fuel into hot compressed air
and its ignition. If the delay period is unduly large there will be accumulation of too much fuel
in the cylinder, which will eventually burn with an undue rapidity. A rapid rise in the cylinder
pressure will follow and cause a diesel knock. The delay period is inherently connected with
the type of hydrocarbon. The preferred hydrocarbons in theorder of decreasing ignition quality
(increasing delay period) ae: n-paraffins, olefins, naphthenes, is0-paraffins and aromatics.
This grder is the reverse of the order for gasoline anti-knock quality, e
The ignitionquality of diesel fuel is measured in a standard engine by
of two reference fuels and expresssed interms of matching against blends
cetane number. A n-paraffin (n-hexadecane
cetane, C,H,) isgiven 100 cetane number andan aromatic
cetane numbr If thegiven fuel matcheswith a 40/60blend of (d-methyl naphthalene) is given zet
it is assigned a cetane number of 40 n cetane and Q-methvl naphthalene.
because theprimary references are costlypractice, secondary reference fuels are used in the te
and not easily available.
High speed engines, above I,500 rpm, need high
engine is not so demanding since there is more time cetane number (45-50) fuels. A low spee
number of 25 to 30 may suffice. available for the combustion. A cetai
Diesel fuels are composed largely of distillates.
and aromatics, and hence the
amount of cracked fractionsCracked fractions are rich inniso-paratins
in good diesel fuels should be low.
 1d Fuels

The cetane numbcr of diesel fucls rich in

hN (he addition ot alkyl nitrates (amyl and aromatics and iso-paraffins may be improvea
-nitrocarbamate), peroxides butyl nitrate), carbamates (isopropyl-n-metnyl
additives are less cffective
(ditertiary butyl peroxide) and metal-organic compounds. These
stocks.
towards catalytically cracked stocks than towards straight-run
Aniline point
This is detined as the temperature at which a liquid just
on equal volume of aniline. Aromatics are easily miscible becomes completely niscible with
with aniline and have a
oint. On the other hand, paraffins have high aniline point. This test is therefore anlow aniline
of the type of hydrocarbon present in a petroleum product. Hexyl benzene has an indication
of -12°C while cetane has avalue of 95.1°C. Ahigh aniline point is an aniline point
suitability as a diesel fuel. indication of high
The aniline point of adiesel fuel is usually converted into an empirical diesel index wih the
help of the following formula:
Diesel index Aniline point, "F X Degree API
100

Numerically the diesel index is usually three units higher than the cetane number. It is not a
very reliable parameter, however its ease of determination makes it popular in the evaluation
of the ignition quality of diesel fuels.

5.2.7 PETROLEUM REFININGIN INDIA

Petroleum refining in Indiastarted in 1893 with the setting up of asmallrefinery at Margherita

in Assam, which is now non-existent. Set up in 1899, the Digboi refinery represents the first
major refîinery in the country. With an initial refining capacity of 0.25 million tonnes of crude.
this was the only refinery up to 1954 and could meet 7% of the demand of petroleum products
Inthe country. The crude was available from the Digboi fields.
In the mid 1950s, three coastal refineries were set up by foreign-controlled oil distributing
cOmpanies, two on the west coast and one on the east coast. The crude rrequirements of
nese refineries were met by imports. Following the discovery of oil in new areas in Assam
and Gujarat, three government-controlled retineries were set up between 1962 and 196S at
Juwahati, Barauni and Koyali in succession. These were all based on indigenous crudes. In
petroleum
ne absence of substantial new oil finds, and with the growth in the demand of
Products in the country, three more coastal refineries were set up on the basis of imported
crudes, two in the south and one in the east. the import
ATter the discovery of the large oilreserves in the Bombay High oftshore areas,
of crude oil was sharply reduced and many refineries started operation with indigenous crude.
One more rehnery was set up at Bongaigaon in Assam in 1981 and, for the first time, alarge

refinery at Mathura in Uttar Pradesh in 1984 to process indigenous crude from

was built