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PETROLEUM

PRODUCTS
LPG

Composition of LPG
Liquid petroleum gases are usually mixtures of saturated and unsaturated
hydrocarbons in the C3 and C4 range. LPG consists one or more of the following
hydrocarbons:
■ Propane
■ N-butane
■ Butylene (C4H8)
■ Propylene (C3H6)
■ Iso- Butane
Properties of LPG
■ Characterized by their high calorific values and high degree purity.
■ Vapours pressure is one of the important characteristics of LPG.
■ The main difference b/w commercial propane and butane is in the vapour pressure.
■ LPG has very low Sulphur content.
■ The density of LPG in its liquid form is about half that of water. Its heavier than air.
■ In case of LPG vapor leak, it will collect at ground level.
■ Flammability of LPG are much narrower than most other gaseous.
■ LPG is odorless and non- corrosive to steel and generally to copper and copper
alloys.
■ Its has no lubricating properties.
■ LPG in vapour phase is slightly anaesthetic (inhaled in high conc)
Production of LPG:

■ There are two main sources of LPG. These are;


(a) Extraction of LPG from natural gas at well head.
(b) Refining of Crude oil.
Extracted of LPG from Natural Gas:
The are several processes by which LPG can processed from natural gas. These are:
I. Compression and cooling
II. Adsorption
III. Absorption
IV. Cryogenic Processes
Refining of Crude Oils:
Bulk of lPG supplies come from refineries. LPG is manufactured at the refineries by
separation of the above mentioned gases from the main refinery gases produced from
distillation, thermal / catalytic cracking, reforming and hydrocracking processes.

Process Feed Main Product Yield of


cracked
LPG, wt %
Catalytic Cracking Naphtha Aromatics, gasoline blendstock 5 – 10 %
Catalytic Cracking Vacuum gas oil Cycle oil for blending in diesel oil 12 %
Coking Residuum Coke 5-10 %
Hydrocracking Vacuum gas Component of middle distillates 3 – 15 %

Yield of Cracked LPG from conversion Processes


■ Treatment
■ LPG produced from gulf crudes require only caustic wash as the mercaptans level is
below 50 ppm.
■ Cracked LPG from FCC unit processing feedstock from gulf crudes requires amine
wash for H2S removal followed by merox treatment.
■ Ethyl mercaptans (about 50 ppm) is added for odourisation.
Uses of LPG:
■ LPG use as a domestic fuel for internal combustion engine and feedstock for the
various chemicals and olefins (by pyrolysis).
■ LPG supplied for domestic purposes is usually mixture of propane and butane.
(butane is pre dominating in warmer countries and propane being in greater
proportion in colder countries.
■ LPG has many industrial applications. It is used for portable blow lamp, soldering,
brazing , wielding , annealing and hardening steel cuttings etc.
■ As a fuel for internal combustion engines, it is extremely good.
Naphtha

Naphtha is a generic name given to light hydrocarbon boiling in the gasoline range. It is
light distillate obtained from refining of crude oil.
The boiling ranges of various types of naphtha from 60 – 170 C.
Naphtha are usually classified as light, intermediate, and heavy naphtha.
If Naphtha fractions boil below 100 C, classified as light Naphtha.
Heavy Naphtha boil above 150 C.
Intermediate naphtha boiling range lies b/w 100 and 150 C.
Methods of Manufacture of Naphtha:
■ Naptha is produce by atmospheric distillation of crude oil. This is called straight run
naphtha.
■ Several conversion process such as visbreaking, fluid catalytic cracking,
hydrocracking, coking also produced naphthas. These are called cracked Naphthas.

Composition Of Naphtha:
Naphtha is a complex mixture of hydrocarbons. Its composition depends on the crude
oil processed and the conversion process employed. The composition of naphtha, two
types of analyses are usually carried out. These are;
■ Hydrocarbon type analysis
■ Individual component wise analysis
The hydrocarbon type analysis determines the % of paraffins, olefins, naphthenes and
aromatics.
The hydrocarbon type composition of naphthas from crudes for boiling ranges of 60 –
85 C, 110 – 120 C, 120 – 130 C and 130 – 140 C.
Use of Naphtha:
■ The use of naphtha in fertilizer and petrochemical industries and as gasoline.
■ Naphtha extensive use as fertilizer feedstock where it is steam reformed to give
synthesis gas, the starting material for fertilizers
■ In petrochemical industry, naphtha (C5 – 140 C) is used as feedstock for steam
crackers, producing hydrogen, methane, ethylene, propylene, the butenes,
butadiene and to lesser extent benzene and isoprene. These are large raw material
for large number of petrochemicals.
Types of naphtha End uses
Light Naphtha (a) Gas making gasoline

(b) Special gasoline

(a) Aviation gasoline

(b) Motor gasoline


(c) Marine gasoline

Intermediate naphtha (d) Commercial solvent – rubber , lacquer and pesticides diluents
(e) Benzene – high octane gasoline component , solvent , petrochemical manufacture
(f) Toluene - solvent, high – octane gasoline component, chemical intermediate, explosive
(g) Xylenes – High octane gasoline component, lacquer and enamels, chemical intermediate.

(h) Olefins and diolefins (i) Ammonia production


(a) Varnish manufactures and paints

Heavy Napthas (b) Thinner for paints, varnishes, lacquers


(c) Special solvent for dry cleaning trade
(d) Minerals spirits – Thinnes for paints and varnishes and turpentine susbtitute
Motor Spirit

■ Motor spirit, commonly known as petrol or gasoline, is one of the most widely used
petroleum products.
■ The primary quality factors for gasoline to give optimal performance concern
combustion, volatility and cleanliness (for both engine and emissions).
■ Composition of gasoline
I. Gasoline are prepared by mixing various components produced by refining
processes such as atmospheric distillation, polymerization, isomerization,
alkylation, catalytic reforming , catalytic cracking, hydrocracking and visbreaking.
II. Gasoline is light distillate and consists of the boiling range of 30 to 180 C.
III. Hydrocarbon ranging from C5 to about C10.
IV. The main types are ;
(a) normal and straight chain paraffin
(b) iso or branched chain paraffin
(c) cycle paraffin
(d) aromatics
(e) olefins
v. Octane numbers of normal paraffins beyond C5 is very poor. Iso-paraffin have high
octane numbers followed by cycle paraffins.
VI. Aromatics and olefins too have high octane numbers. High proportions of olefins are
not tolerated in gasoline for reason of storage stability and gum forming tendency.
Kerosene

■ Distillate fraction of crude oil in the boiling range of 150 – 250 C.


■ Kerosene can’t burnt in liquid state.( it has been in the form of vapor and mixed with
the oxygen in the air in the correct ratio to form combustible mixture)
■ Gasoline evaporates rapidly at ambient temperatures, but kerosene evaporates
more slowly.
Manufacture Of kerosene

■ Straight run kerosene cut crude are unsuitable for marketing purposes because of
its aromatic content.
■ The main disadvantages of high aromatics content is that kerosene burnt with
smoky flame.
■ In order to produce superior quality of Kerosene, which will burn with stipulated
flame height without smoke, the straight run kerosene is treated with sulphur
dioxide to reduce the aromatic content.
■ Another method to treat Kerosene from either sweet or sour crudes is Hydrofining or
hydrotreatment.
■ By hydrotreatment of kerosene fraction, aromatics converted in naphthenes thereby
producing an improvement in burning characteristics.
Composition of kerosene

■ Various types of hydrocarbon present in kerosene are (a) paraffins (b) naphthenes ©
aromatics and non hydrocarbon compounds. Sulphur, nitrogen, oxygen and metals.
■ Carbon number of hydrocarbons present varies from 10 to 14.
■ Paraffin have the least tendency towards smoky formation and aromatics the greatest.
Properties Of kerosene

■ The smoke point of kerosene is an important burning characteristics.


■ The tendency of kerosene to smoke is mainly dependent on the types of
hydrocarbon present.
■ The tendency of kerosene to smoke decreases in the order:
Aromatics > naphthenes > isoparaffins > Paraffins
Uses of Kerosene

■ Kerosene is used as domestic fuel. It is used for cooking and lighting. Whether it is
used for lighting in lamps or in cooking stoves, it has to be first turned into vapour.
This is done by using wicks or by pressure.
■ Kerosene is also used manufacture insecticides, herbicides and fungicides. These
are used to control pests, wed and fungi.
■ The extracted aromatics are suitable raw materials for the manufacture of aromatic
solvents and aromatic process oils.
Aviation Turbine Fuels

■ A potential fuel for the gas turbine engines used in aircraft requires high
thermal stability, high heat content, low vapour pressure , good combustion
characteristics, good viscosity – temperature relationship, high density, high
specific heat, uniformity and good handling characteristics.
■ The combustion properties of aviation fuels (ATF) using several of the
following tests: Smoke point , luminometer number, aromatic content aniline
point and gravity.
■ There are two basic types of ATF (i) Kerosene type (ii) Gasoline type.
■ The kerosene type ATF used gas turbine engines while gasoline cut ATF
required for limited military us as in supersonic aircraft.
Composition of ATFs

■ ATF are distillate fractions of crude oil in the boiling range 150 – 270 C.
■ consist predominantly of hydrocarbons with minor constituents of sulphur , nitrogen and
oxygen compounds. And traces of particulate matter and water as contaminants.
■ Paraffin and naphthenes are the major compounds in ATF. ( ratio varies with crude
sources)
■ Aromatics are present in ATF principally as monocyclic hydrocarbons with small
quantities of two-three ring compounds. These have a more luminous flame than
paraffin and cause smokiness and carbon deposition.
■ The hydrotreating of ATF tends to reduce aromatics.
■ The total sulphure is limited to 0.2 wt %. Mercaptans is controlled for its corrosiveness to
copper and cadmium and for its disagreeable odour. (0.001%)
Diesel Fuels

■ Categorized in High speed diesel (HSD) and low diesel oil (LDO).
■ HSD used in automotive purposes as in buses, lorries, diesel locomotives.
■ LDO used in stationary and marine diesel engines as installed in ship used for
electricity generation.
■ Diesel fuels for automotive use good ignition quality to ensure easy starting and
smooth running.
■ Sulphur content must be critically controlled to minimize environmental pollution ,
corrosion , wear and tear.

composition

■ Less volatile middle distillate fractions of crude oil boiling range is 150 – 400 C
suitable for diesel
■ Hydrocarbon present in the diesel fuels includes paraffin, naphthenes, olefins and
aromatics.
■ Carbon number fuel range from C 12 to 18.
■ Diesel fuel contain both saturated and straight or unbranched chain unsaturated
hydrocarbons.
FUEL OILS

■ Fuel oils are essentially made up of residues remaining from atmospheric and
vacuum distillation and conversion processes after removal of lighter hydrocarbons.
■ The viscosity of residues can also be reduced in Visbreaking process. The finished
blend of fuel oil may contain a number of components obtained from different
sources.
■ The chemical nature of fuel oils is most complex. The fuels oils are predominantly
composed of higher molecular weight compounds known as asphaltic bitumen.
■ Fuel oil used in industrial furnace.
Properties of Fuel Oils
■ Important physical and chemical properties of fuel oils are as follows;
■ Viscosity: the viscosity of the fuel oils and its variation with temperature determine the
flow of the fuel oil to the burner and the type of atomizer to be used. Viscosity is reduced
by heating using electricity or steam coils.
■ Pour Point: determine the temperature at which the fuel oil storage tanks are to be
maintained to ensure flow into the feedlines.
■ Water and Sediment : they are not present to any significant extent in the fuel when
manufactured, but picked up in traces in the distribution system and during storage.
Water can accumulate from tank breathing in moist air. Its is soluble in fuel oil at low
ppm level. Sediment is defined as material insoluble in toluene. Its comprises of smaller
particles of pipe, tank scale and a few fibers. Sludge and sediment formation determine
the possible life of the oil during storage. Unsatisfactory blending or the presence of
unstable, oxidizable component of an oil can cause the separation of sludge, emulsion
and sediments can cause clogging of filters or nozzles and corrode storage tanks and
pipeline.
■ Sulphur Content: depend on type of crude processed in the refinery. The max amount of
Sulphur of the crude is concentrated in residual oil. The Sulphur content should not be
more than 4.0 wt %. High Sulphur content in a fuel oil (a) raise the dew point of the flue
gas (b) increase the formation of sulphate deposit in boiler, economizer and air
preheater. © increase corrosion and pollution effect (d) reduce combustion effect (e)
contaminate products in direct contact with the furnace gases such as glass and steel
(f) accelerates the gum and sediment formation during storage.
■ The ash content of fuel oils is small usually less than 0.05 %. It is mainly of
vanadium and sodium with lesser amount of nickel and minute traces of metals.
■ V and Ni are present in oil as organic compounds. Despite desalting processes up to
50ppm of salt can remain in the residual fuels as marketed.
Petroleum Hydrocarbon Solvents

■ Hydrocarbon solvents are volatile fractions derived from the fractionation of


petroleum stream
■ Most of the important grades of hydrocarbon solvents are clear, water-white liquids.
■ These solvents are immiscible with water but are completely miscible with other
commonly used organic solvents.
■ The hydrocarbon solvents are used in wide range of products and industrial
chemicals , in the manufacturing of paint, printing inks, polishes, adhesives etc.
■ The hydrocarbon solvents comprises part of the finished product.
■ The use of hydrocarbon solvent may be found in many extraction processes such as
extraction of vegetable oils from oil seeds, minerals, pharmaceuticals .
Composition Of Hydrocarbon Solvent

■ Hydrocarbon solvent are mixture of chemically different hydrocarbon molecules. The


composition of particular solvent is usually quoted in term of type of hydrocarbon
present i.e. paraffin, naphthenes, aromatics and olefins.
■ The proportions of these groups of hydrocarbon types effect on physical properties
such as solvent power, viscosity, density and colour.
■ Small amounts of non-hydrocarbon compounds such as oxygen and oxygenated
compound can be present. However these compounds are usually removed to very
low level during manufacturing process.
Classification of Hydrocarbon Solvents

■ SBPs (Special Boiling Point spirits) these represent a range of products other
characterized by a number e.g SBP1 , SBP2 etc. these solvent are essentially aliphatic
solvent within the temp range 45 – 160 C.
■ Isoparaffinic Solvents: these solvents consist mainly isoparaffins with negligible amounts
of other types of hydrocarbons. These are manufactured from lower molecular weight
hydrocarbons by alkylation.
■ Aromatics Solvents: these solvent are available in full range. The fast evaporating types
are essentially toluene and xylenes.
■ White Spirits: these solvents boil within the range 150-220 C. the other names used for
white spirit includes minerals turpentines, minerals spirits and Stoddard solvent . White
spirit are not de-aromatized.
■ De-aromatized Solvents: these solvent have much odour than conventional regular
grades.
Manufacture of Hydrocarbon Solvents

■ There are three main step involved in the manufacturing hydrocarbon solvent: these
are;
■ Distillation: Volatility of the hydrocarbon solvents is controlled by distillation . Most
hydrocarbon solvents are manufactured in solvent distillation column from
hydrotreated and hydrodesulphurised feedstocks.
■ Chemical Conversion & Separation: hydrocarbon solvent with very low benzene
contents are required in oil seed extraction, printing inks , adhesive and polyolefins
manufacture. The removal aromatics from solvent fractions improves the solvent
power. De – aromatized solvents are manufactured by catalytic hydrogenation and
solvent extraction process. Catalytic hydrogenation convert aromatics into
naphthenes.

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