PETROLEUM REFINING

PETROLEUM
• or crude oil, naturally occurring oily, bituminous
liquid composed of various organic chemicals.
• heavy liquid, inflammable, mineral oil stored
under the surface of the earth, and probably of
ancient marine animal origin
• consists chiefly of carbon and hydrogen in the
form of hydrocarbons and other constituents
(83-87% C; 11-15% H; 3% S,N,O)
Crude Oil
Classification of Crude Petroleum:
1. Paraffin Base
- crudes consist primarily of open-chain
compounds and furnish low-octane number
straight run gasoline and excellent but waxy
lubricating oil stocks
- paraffin types are composed of molecules in
which the number of hydrogen atoms is
always two more than twice the number of
carbon atoms
2. Intermediate Base
- contain large quantities of both paraffinic and
napthenic compounds and furnish medium grade
straight run gasoline and lubricating oils
- both wax and asphalt are found in these oils
3. Naphthene Base
- contain a high percentage of cyclic (naphthenic)
compounds and furnish relatively high octane
number straight run gasoline
- asphalt is present
- The characteristic molecules in the asphaltic types
are naphthenes, composed of twice as many
hydrogen atoms as carbon atoms
CONSTITUENTS OF PETROLEUM :
A. Aliphatics or open chain hydrocarbons
1. n-paraffin series (CnH2n + 2)
- predominate in most straight-run gasoline
ex. n-hexane, n-heptane
2. iso-paraffin series (CnH2n + 2)
- branched chain compounds are very desirable and
are frequently manufactured by catalytic
reforming, alkylation and isomerization
ex. 2 & 3 methylpentanes; 2 methylhexane
3. olefin series (CnH2n )
- series is either not present in crude oil or exists in
very small quantities
- possess better antiknock properties than normal
paraffins but have poorer properties than highly
branched paraffins and aromatics
- disadvantage is they polymerize and/or oxidize on
storage
ex. ethylene, propylene, butylene
B. Ring Compounds
1. naphthene series (CnH2n )
- same chemical formula as the olefin series but
its members are completely saturated
- second most abundantly occuring series of
compounds in most crudes
- predominate in most gas oils and lubricating
oils from all types of crudes
ex. methyl cyclopentane, cyclohexane
2. aromatic or benzene series (CnH2n – 6)
- exists only in small amounts
- produced by chemical processing and have
antiknock qualities
ex. benzene, toulene, ethylbenzene
Natural Gas
• occurs as accumulations in underground, porous
reservoirs with or without petroleum oil
• composed chiefly of hydrocarbons of the paraffin
series from methane up to pentane, carbon
dioxide, nitrogen, and sometimes helium, but few if
any unsaturated hydrocarbons
• products obtained are fuel, natural gasoline, LPG,
carbon black, helium, hydrogen and petrochemicals
Natural Gas Liquids
• different from the straight run or refinery
gasoline (distilled from crude oil)
• occurs when crude oil is forced from a well by
the pressure of the natural gas, some of its
lighter components are vaporized into the gas
Cracked or Refinery Gases
• natural gas is devoid of unsaturated
hydrocarbons and hydrogen but these
compounds are present in the cracked gases of
refining
• olefins from these gases are used in the
polymerization of gasoline, antifreezes,
petrochemicals, explosives, solvents, fumigants,
etc.
LPG or Liquified Petroleum Gas
• light hydrocarbons such as propane and butane
which are produced as by-products from
natural gasoline, that are “bottled” or
“liquified”
 Products of Refining :
1. Precursors of Petrochemicals
- intermediates leading to the finished and salable products
a. acetylene (C2H2)
- manufacture through pyrolysis or cracking of natural gas or liquid
hydrocarbon feeds
2 CH4 C2H2 + 3 H2 (1600K)
- employed with oxygen to give
a high welding temperature and
in the manufacture of industrial
chemicals such as vinyl chloride,
acrylonitrile and acetic acid
b. ethylene (C2H4)
- can be made from feed stocks varying from ethane to
heavy gas oil or even crude oil
- manufactured by cracking of material diluted with an
inert gas (steam) at a high temperature (9250C) and
with a short residence time (30-100 milliseconds)
yields a mixed product which must be separated to
obtain useful compounds
c. propylene (C3H6)
- gases under ordinary conditions that are
recoverable, mainly from cracking, to furnish
gasoline blending stock
d. toulene (C7H8)
- made from petroleum raw materials, actually
occurring in recoverable quantities from certain
stocks
- made by dehydrogenation of naphtha feedstocks
2. light distillates
a. gasoline
– most important fuel product
- colorless, liquid hydrocarbon obtained in the
fractional distillation of petroleum
- ordinary gasoline consists of the hydrocarbons
between C6H14 and C10H22
which distill off between 69 – 1740C
Octane number
• a measure of the suitability of a fuel for high-
compression engines
• percentage of iso-octane (2,2,4
trimethylpentane) which, when added to n-
heptane, knocks in a special test engine to the
same degree as the fuel being tested
• standard of measure of detonation in the
engine
b. aviation gasoline
- an octane number of 100 or
even higher, is composed of
about 1/3 alkylate derived from
isobutane and gaseous olefins, blended with catalytically
cracked gasoline and suitable crude distillate, to which several
cubic centimeters of TEL (tetraethyllead) per gallon is added
to reduce the knocking tendency
- sulfur quantity should be between 0.1 – 0.2% although it
does not cause serious corrosion if it is as high as 0.2%
c. naphtha
- volatile petroleum fractions
that are used as commercial
solvents in paints, for dry
cleaning and as ethylene
feedstocks
- graded according to the range of temperature over which
they distill
- light, colorless to straw colored liquid which distills off from
petroleum between 70 – 900C
- ranges from C16H14 to C7H18
d. kerosene
- used in jet airplanes than
aviation gasoline in all other
airplanes
- used as a fuel and for illuminating purposes
- a light, oily liquid obtained in the fractional
distillation of petroleum
- it distills off after the gasoline, and between the
limits of temperature of 174 – 2880C
- a hydrocarbon of composition of C10H22 to C16H34
3. intermediate distillates
• include gas oil, heavy
furnace oil (domestic),
cracking stock, diesel
fuel oil, absorber oil, and distillates cracked and
reformed to produce gasoline of adequate
quality
• often distillates are blended with heavy tar to
reduce the viscosity of the tar so that it can be
marketed as fuel oil
4. heavy distillates
• include lubricating oils (also from residues),
heavy oils for various purposes and waxes
• are hydrocracked to lighter distillate fuels and
to gasoline
a. residues
– include asphalt, residual fuel oil, coke and
petrolatum
- petroleum coke is used commercially for
electrodes in the manufacture of calcium
carbide, in paints and in the ceramics industry
b. asphalt
- used as a paving
or roofing materials
for waterproofing
structures
- properties may be altered by heating it to a high
temperature and partly oxidizing it by blowing air
through it
c. petrolatum
- jellylike substance obtained in the fractional
distillation of petroleum
- sometimes called petroleum jelly
- composition is between C17H36 to C21H44
- distills off above 3030C
- used for lubricating purposes and for compounding
rubber and as an ointment for pharmacy trade
d. greases
- constitute a large group of different materials that
fall into 3 classes :
1. mixtures of mineral oil and solid lubricants
2. blend of waxes, fats, resin oils and pitches (tar)
3. soap-thickened mineral oils
e. petroleum chemical or petrochemicals
ex. ammonia, carbon black and other
organic and inorganic chemicals
Processing or Refining :
1. cracking or pyrolysis
- breaking down of large hydrocarbon molecules
into smaller molecules by heat or catalytic
action
- zeolite catalysts are used
C17H15.C15H30.C7H15 C7H16 + C6H12:CH2 + C14H28:CH2
heavy gas oil gasoline gasoline recycle
(antiknock) stock
2. polymerization
• linking of similar molecules
• joining together of light olefins
C C heat C C
pressure
C-C=C + C-C=C C-C-C-C=C + C-C-C=C-C
catalyst
C C C C
unsaturated short longer chains
chains
 3. alkylation
• the union of an olefin with an aromatic or
paraffinic hydrocarbon
catalyst
unsaturated + isosaturated saturated branched chain
C
C=C + C-C-C C-C-C-C
C C
ethylene isobutane 2,2-dimethylbutane,
or neohexane
4. hydrogenation
• the addition of hydrogen to an olefin
C H2 C
C-C-C =C-C C-C-C-C-C
C C catalyst C C
diisobutylene isooctane
C2H4 + H2 C2H6
ethene ethane
5. hydrocracking
• addition of hydrogen at a high temperature

C17H15.C15H30.C7H15 + H2 C7H16 + C7H16 + C15H32

heavy gas oil straight branched recycle
chain chain stock
gasoline
6. isomerization
• alteration of the arrangement of the atoms in a
molecule without changing the number of
atoms
3000C C
C-C-C-C C-C-C
straight AlCl3 branched
chain chain
7. reforming or aromatization
• conversion of naphthas to obtain products of
higher octane number
• similar to cracking but more volatile charge
stocks are used
• catalysts usually contain rhenium, platinum or
chromium
CH3CH2CH2CH2CH2CH2CH3 CH3 + 4H2
n-heptane Cr2O3 on Al2O3 toulene
8.esterification and hydration
• making of esters by addition of acid into a
paraffin
C2H4 + H2SO4 C2H5O.HO.SO2 + (C2H5O)2SO2

C2H5O.HO.SO2 + (C2H5 )2O.SO2 + H2O H2SO4 +

C2H5OH + C2H5OC2H5
Vibroseis Truck
• In order to determine the structure of underground
rock layers at a site in California, this substantial
vibroseis truck thumps the ground with a large
baseplate mounted between its wheels. The thumps
send out seismic vibrations, or shear-waves, at a
known frequency. A network of seismometers called
geophones records the arrival time of the shear-
waves.
Oil Drill Rig and Reservoir
• The rotary drilling rig uses a series of rotating pipes, called the
drill string, to tap into an oil reservoir. The drill string is
supported by a derrick, and turned by the rotary table on its
floor. Mud-like fluid circulated by a pump removes cuttings as
the teeth of the drill bit dig into the rock around the reservoir.
Petroleum reservoirs occur in many places. They form as a
result of intense pressure on top of layers of dead marine and
land organisms mixed with sand or silt. The reservoir shown
abuts a salt dome, which has trapped a layer of oil and natural
gas between itself and nonporous rock. Because they have no
space into which to expand, the gas and crude oil are under
high pressure and will tend to rush explosively out of the
channel opened by the drill rig.
Oil Refining and Fractional Distillation
• The first stage in the refining of crude oil is to
separate it into parts called fractions, according to
molecular weight. The crude oil is heated in a
furnace and passed into the fractionating column, in
which the temperature decreases with increasing
height. The fractions with heaviest molecular weight,
which will become lubricating oils, waxes, and so on,
can exist in vapour form only in the lower part of the
column, and are drawn off there. The lighter
fractions, which will become jet fuel, petrol, and so
on, are driven higher up the column, where they are
drawn off. All the fractions receive numerous and
complex further treatments to turn them into the
desired end-products.
Chemical Treatment
• to remove or alter the impurities in petroleum
products in order to produce marketable material
Purposes:
1. to improve the color
2. to improve the odor
3. to remove sulfur compounds
4. to remove gums, resins and asphaltic materials
5. to improve its stability to light and air
Removal of sulfur by:
• hydrogenation – also removes metals and
nitrogen
• treatment with caustic soda
• treatment with caustic soda plus catalyst
(merox)
• treatment with ethanolamines
Doctor Treatment
• method of “doctoring” the oil to reduce the
odor and alteration of objectionable sulfur
• process consists in agitating the oil with an
alkaline solution of sodium plumbite and a
small amount of sulfur
• sulfur compounds usually found in oils are
mercaptans (gives the material a disagreeable
odor and cause corrosion)
2 RSH + Na2PbO2 (RS)2Pb + 2 NaOH