CHM 313
CHM 313
CHM 313
PETROLEUM FORMATION
KEROGEN: Kerogen is a mixture of organic chemical compounds that make up a portion of the organic matter in
sedimentary rocks
1. Diagenesis of kerogen is marked by decrease of oxygen and a corresponding increase of carbon content with
increasing depth. This stage of evolution results in a slight decrease in the ratio of hydrogen / carbon and a
marked decrease of oxygen / carbon
2
2. Catagenesis, the second stage of kerogen degradation, is marked by an important decrease of the hydrogen
content and of the hydrogen to carbon ratio, due to generation and release of hydrocarbons
3. Metagenesis is the last stage of the evolution of petroleum sediment. It is reached only at great depth, where
temperature and pressure are high. At this stage, organic matter is composed only of methane and a carbon residue.
The constituents of residual kerogen are converted to graphite carbon. 2
COMPOSITION OF PETROLEUM
Hydrocarbon Compounds
The principal constituents of most crude oils are hydrocarbon compounds. All hydrocarbon classes are present in the crude
mixture, except alkenes and alkynes. This may indicate that crude oils originated under a reducing atmosphere. The
hydrocarbons in crude oil are mostly alkanes (paraffins), cycloalkanes (naphthenes) and various aromatic hydrocarbons
the alkanes from pentane (C5H12) to octane (C8H18) are refined into petrol, the ones from nonane (C9H20) to hexadecane (C16H34)
into diesel fuel, kerosene and jet fuel.
- alkanes with more than 16 carbon atoms can be refined into fuel oil and lubricating oil
- The simplest mononuclear aromatic compound is benzene (C6H6). Toluene (C7H8) and xylene (C8H10) are also mononuclear
aromatic compounds found in variable amounts in crude oils 3
CH3
Examples CH3
CH3
CH3CH2CH2CHCH3
CH3(CH2)4CH3
n-hexane 2-methylpentane
CH3
Benzene Toluene Naphthalene
Xylene
Sulphur Compounds
Sulphur in crude oils is mainly present in the form of organosulphur compounds
CH3SH
methylmercaptan phenylmercaptan cyclohexythiol
CH3SCH3 CH3SSCH3
Dimethylsulpide Dimethyldisulphide S S
Thiolcyclohexane Thiophene
4
Nitrogen Compounds
Organic nitrogen compounds occur in crude oils either in a simple heterocyclic form as in pyridine (C5H5N) and
pyrrole (C4H5N), or in a complex structure as in porphyrin
Basic Nitrogen compounds Non-basic Nitrogen compounds
N N
N N N
Pyridine Quinoline H H H
Pyrrole Indole
Carbazole
Oxygen Compounds
COOH OH
O O
Furan Benzofuran
5
Metallic Compounds
Some of the more abundant are sodium (Na), calcium (Ca), magnesium (Mg), aluminium (Al), iron (Fe), vanadium
(V), and nickel (Ni).
Calcium and magnesium can form salts or soaps with carboxylic acids. These compounds act as emulsifiers, and
their presence is undesirable
2. Naphthenic – Naphthenic base stock, low pour, less wax and less asphaltic. The ratios of naphthenic and aromatic
hydrocarbons are relatively higher than in paraffinic crudes.
3. Asphaltic - contain relatively a large amount of polynuclear aromatics, high asphaltene content, and relatively less
paraffins than paraffinic crudes. It contains high sulphur, nitrogen and it is good for base oil.
6
THIRD WEEK
PROPERTIES OF CRUDE OILS
Kinetic methods of analysis are based on the rate at which a chemical or physical process involving the analyte
occurs.
Density
Density is defined as the mass of unit volume of a material at a specific temperature.
The density of a crude oil indicates how light or heavy it is, as a whole. Lighter crudes contain higher proportions of
small molecules
Specific Gravity
Specific gravity is used to calculate the mass of crude oils and its products
API Gravity
The API (American Petroleum Institute) gravity is another way to express the relative masses of crude oils. The API
gravity could be calculated mathematically using the following equation:
141.5
°𝐴𝑃𝐼 = − 131.5
𝑆𝑝. 𝑔𝑟. 60/60 7
A low API gravity indicates a heavier crude oil or a petroleum product, while a higher API gravity means a lighter crude or product
Sulphur Content
Of all the hetero-elements in crude oil, sulphur has the most important effects on refining.
Sufficiently high sulphur levels in refinery streams can (1) deactivate (“poison”) the catalysts that promote desired chemical
reactions in certain refining processes, (2) cause corrosion in refinery equipment, and (3) lead to air emissions of sulfur
compounds, which are undesirable and may be subject to stringent regulatory controls.
In the refining industry, crude oil is called sweet (low sulphur) if its sulphur level is less than a threshold value (e.g., 0.5 wt%
(5,000 ppmw) and sour (high sulphur) if its sulphur level is above a higher threshold.
Pour Point
The pour point of a crude oil or product is the lowest temperature at which oil is observed to flow under the conditions of the
test. Pour point data indicate the amount of long-chain paraffins (petroleum wax) found in a crude oil.
Ash Content
This test indicates the amount of metallic constituents in a crude oil.
The ash left after completely burning an oil sample usually consists of stable metallic salts, metal oxides, and silicon oxide. The
ash could be further analyzed for individual elements using spectroscopic techniques
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FOURTH, FIFTH AND SIXTH WEEKS
PETROLEUM INDUSTRY
The petroleum industry is involved in the global processes of exploration, extraction, refining, transporting (with oil
tankers and pipelines), and marketing petroleum and petroleum products.
MODERN PETROLEUM PROCESSING
Seven basic processes in petroleum processing
Separation Combination
-Distillation -catalytic polymerization
-Solvent refining -alkylation
Conversion Treating, Finishing and Blending
-carbon removal -gasoline, kerosene, diesel
-Hydrogen addition -lubes and waxes
Reforming -asphalt
-catalytic reforming Protecting the Environment
-steam/hydrocarbon reforming -waste water tretament
Rearrangement -solid waste disposal
-isomerization -sulphur removal 10
Typical layout for an oil refinery
11
PHYSICAL AND CHEMICAL PROCESSES IN PETROLUEM REFINING
Physical Chemical
Thermal Catalytic
Distillation Visbreaking Hydrotreating
Solvent extraction Delayed cooking Catalytic reforming
Propane deasphlating flexicooking Catalytic cracking
Solvent dewaxing Hydrocracking
Blending Catalytic dewaxing
Desalting Alkylation
Polymerization
Isomerization
1. Desalting
Crude oil contains contaminants such as water, salts, and suspended solids and these must be removed so as to
reduce corrosion, plugging, and fouling of equipment and to prevent poisoning catalysts in processing units by
refining process.
In chemical desalting, water and chemical surfactant (demulsifiers) are added to the crude, which is heated so that
salts and other impurities dissolve or attach to the water, then held in a tank to settle out 12
Electrical desalting is the application of high-voltage electrostatic charges to concentrate suspended water globules in the
bottom of the settling tank. Surfactants are added only when the crude has a large amount of suspended solids
2. DISTILLATION
Distillation is a process which uses energy to separate products on the basis of boiling points.
Crude distillation separates raw crude oil feed (usually a mixture of crude oils) into a number of intermediate refinery
streams (known as “crude fractions” or “cuts”), characterized by their boiling ranges (a measure of their volatility, or
propensity to evaporate).
Each fraction leaving the crude distillation unit (1) is defined by a unique boiling point range (e.g., 180–250o F, 250–350o
F, etc.) and (2) is made up of hundreds or thousands of distinct hydrocarbon compounds, all of which have boiling points
within the cut range. These fractions include (in order of increasing boiling range) light gases, naphthas, distillates, gas
oils and residual oil. Each goes to a different refinery process for further processing
Fractional distillation is more useful than distillation for separating a mixture of substances with narrow differences in
boiling points, and is the most important step in the refining process.
The degree of fractionation, or sharpness of separation between hydrocarbons, depends on the number of trays and
their efficiency in achieving equilibrium between vapour and liquid 13
Fractional distillation products of petroleum
14
Atmospheric distillation
In the refining process is the separation of crude oil into various fractions by distillation in atmospheric and vacuum
towers. (the purpose of atmospheric is primary separation of various “cuts” of hydrocarbons. The heavy
hydrocarbon residue left at the bottom of the atmospheric distillation is sent to vacuum distillation column for
further separation. It separates lighter hydrocarbons from heavier hydrocarbons based on their boiling points.
Vacuum distillation
The principles of vacuum distillation resemble those of fractional distillation except that larger diameter columns
are used to maintain comparable vapor velocities at the reduced pressures.
The vacuum is produced by steam ejectors in vacuum distillation. Components that are less volatile can be distilled
without raising the temperature to the range at which cracking occurs
3. Solvent extraction process is used primarily for the removal of constituents that would have an adverse effect on
the performance of the product in use. The quality of kerosene is improved by the extraction of aromatic
compounds that burn with a smoky flame. Another important operation is the removal of heavy aromatic
compounds from lubricating oils. Removal improves viscosity-temperature relationship of the oil, extending the
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temperature range over which satisfactory lubrication is obtained.
4. Adsorption Certain highly porous, solid materials have the ability to select and adsorb specific types of molecules,
thus separating them from other types. Silica gel is used in this way to separate aromatics from other hydrocarbons,
and activated charcoal is used to remove liquid components from gases.
5. Propane deasphalting
Coke-forming tendencies of heavier distillation products are reduced by removal of asphaltenic materials by solvent
extraction. Liquid propane is a good solvent. Deasphalting is based on solubility of hydrocarbons in propane.
6. Solvent dewaxing
Solvent dewaxing is used to remove wax from either distillate or residual basestock at any stage in the refining
process. It involves three steps
– mixing the feedstock with a solvent (toluene or methyl ethyl ketone)
– precipitating the wax from the mixture by chilling
– recovering the solvent from the wax and dewaxed oil for recycling by distillation and steam stripping.
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7. Blending
Blending is the physical mixture of a number of different liquid hydrocarbons to produce a finished product with
certain desired characteristics. Additives including octane enhancers, anti-oxidants, antiknock agents, gum and rust
inhibitors, detergents, etc. are added during and/or after blending to provide specific properties not inherent in
hydrocarbons.
Cracking
Cracking is the name given to breaking up large hydrocarbon molecules into smaller and more useful bits. This is
achieved by using high pressures and temperatures without a catalyst, or lower temperatures and pressures in the
presence of a catalyst
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Thermal Cracking
In thermal cracking, high temperatures (typically in the range of 450-750°C) and pressures (up to about 70
atmospheres) are used to break the large hydrocarbons into smaller ones. Thermal cracking gives mixtures of
products containing high proportions of hydrocarbons with double bonds – alkenes
Visbreaking, another thermal cracking process, reduces viscosity of heavy crude oil residues to make them more
suitable for inclusion in fuel oils.
Steam cracking is a petrochemical process in which saturated hydrocarbons are broken down into smaller, often
unsaturated, hydrocarbons. It is the principal industrial method for producing the lighter alkenes (or commonly
olefins), including ethene (or ethylene) and propene (or propylene).
Catalytic Cracking
Dissociation of larger and stable molecules sometimes requires catalysis. Refinery products such as gasoil and fuel
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oil may be passed through catalytic cracker to obtain gasoline and diesel as major products and byproduct
Hydrocracking
Hydrocracking is a catalytic cracking process assisted by the presence of an elevated partial pressure of hydrogen
gas. The function of hydrogen is the purification of the hydrocarbon stream from sulphur and nitrogen hetero-
atoms.
Hydrocracking is normally facilitated by a bifunctional catalyst that is capable of rearranging and breaking
hydrocarbon chains as well as adding hydrogen to aromatics and olefins to produce naphthenes and alkanes.
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Reforming Process
•Dehydrogenation is a process in which hydrogen atoms are being taken away from saturated hydrocarbons
structure leaving product of unsaturated hydrocarbons such as the dehydrogenation of cyclohexane to aromatics.
•Dehydrocyclization is a process in which hydrogen atoms are being taken away from aliphatic hydrocarbons
yielding aromatics such as dehydrocyclization of paraffin.
-3H2
•Alkylation
Alkylation combines light olefins (primarily C4s, and some C3) with iso-butane to produce a high-octane (≈ 90–94
RON) gasoline blendstock (alkylate). Virtually all alkylation units use a strong liquid acid catalyst – either hydrofluoric
acid (HF) or sulphuric acid (H2SO4), depending on the process.
H CH3 CH3
H3C
CH3
2 +
•Isomerization
Isomerization rearranges the low-octane C5 and C6 normal-paraffin molecules in light SR naphtha to produce the corresponding,
higher-octane C5 and C6 iso-paraffins, thereby significantly increasing the octane of the resulting naphtha stream (isomerate) and
making it a valuable gasoline blendstock. It involves the molecular restructuring of material while retaining the same number of
atoms i.e., isomerization of o‐xylene and m‐xylene to p‐xylene. As an additional process benefit, isomerization produces a
product containing essentially no sulfur and no benzene. Hence, some refineries recently have added isomerization capacity as a
CH3 CH3
means of meeting stringent new benzene standards on their gasoline output.
CH3
CH3 22
Catalytic Reforming
In catalytic reforming, a naphtha-type material serves as the feedstock, but the reactions are carried out in the
presence of hydrogen, which inhibits the formation of unstable unsaturated compounds that polymerise into
higher-boiling materials.
In most catalytic reforming processes, platinum is the active catalyst distributed on the surface of an aluminum
oxide carrier.
Polymerization
Polymerization combines two or three light olefin molecules (C3 or C4) to produce a high- octane, olefinic gasoline
blendstock (poly gasoline) component.
Etherification
Etherification combines C4 and/or C5 olefins produced by FCC plants with a purchased alcohol (methanol or ethanol)
to produce an ether (a class of oxygen-containing organic compounds). Ethers are premium gasoline blendstocks,
with very high octane and other desirable blending properties.
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Hydrotreating Processes
Treating processes are chemical reactions that remove heteroatoms (e.g., sulfur, nitrogen, heavy metals) and/or
certain specific compounds from crude oil fractions and refinery streams, for various purposes. The most important
purposes are (1) meeting refined product specifications (e.g.; sulfur in gasoline and diesel fuel, benzene in gasoline,
etc.) and (2) protecting the catalysts in many refining processes from deactivation (“poisoning”) resulting from
prolonged contact with hetero-atoms. By far the most widely-used of the various treating technologies is catalytic
hydrogenation, or hydrotreating.
Hydrotreaters remove heteroatoms by reacting the refinery streams containing the hetero-atom(s) with hydrogen in
the presence of a catalyst. The hydrogen combines with the hetero-atom(s) to form non-hydrocarbon molecules
that are easily separated from refinery streams.
Hydrotreating focused on sulfur removal is often referred to as hydro-desulfurization; hydrotreating focused on
nitrogen removal is called hydro-denitrification.
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Hydro-denitrification
Hydro-desulfurization
25
TENTH AND ELEVENTH WEEKS
PETROCHEMICALS
Petrochemicals refer to organic hydrocarbon chemicals produced using petroleum products such as crude oil,
natural gas and natural gas condensate as raw materials.
In general, the petrochemical industry uses raw materials from the petroleum industry to manufacture products
such as plastic resins, synthetic fibers, synthetic rubbers, surface coating materials and various types of adhesives.
These products are considered primary raw materials for human beings’ basic consumption items, occupational
tools and equipment, and various amenities for mankind.
Intermediate petrochemical industry uses upstream petrochemical products as feedstock and supplies to
downstream petrochemical industry. Its products are grouped on the basis of their upstream petrochemicals, as
follows:
1. Alkane Intermediates, namely, products from upstream methane, such as methanol, formaldehyde, ammonia,
phosgene, etc.
2. Olefin Intermediates, namely, ethylene products such as ethylene dichloride, (EDC), vinyl chloride monomer
(VCM), ethylene oxide (EO), and ethylene glycol (EG), propylene products such as oxo alcohol and acrylonitrile
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3. Aromatic Intermediates, namely, benzene products such as ethyl benzene (EB), styrene monomer(SM), cyclohexane and
paraxylene products, etc.
Downstream petrochemical Industry uses upstream or intermediate petrochemical products as feedstock to manufacture
downstream products or end products prior to conversion in other industries. They are categorized by end product, as follows:
1. Plastic resins
2. Synthetic Fibers
3. Synthetic rubbers
4. Synthetic coating and Adhesive materials
2. Unsaturated hydrocarbons
Methane is cracked (by pyrolysis) with the help of suitable catalysts to get ethylene, propylene and acetylene. These are used to
29
produce other products
Carbon black
Methane is converted into carbon black (a form of carbon) by pyrolysis (cracking) and hydrogen is obtained as a byproduct.
Carbon black is used as a black pigment in the production of black printing ink and in rubber tyre industry
CH4 C + 2H2
Hydrogen
Hydrogen obtained by pyrolysis of methane is used for the manufacture of ammonia gas. Ammonia is used as a raw material for
manufacture of urea (a fertilizer), ammonium nitrate and several other products.
5. Methanol
Methane is converted into methanol by catalytic oxidation
CH4 + O2 CH3OH
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Petrochemicals from Ethylene
Ethylene is obtained by pyrolysis of natural gas or from naphtha by cracking. Ethylene is an unsaturated hydrocarbon and has a
carbon-carbon double bond. Therefore, ethylene is very reactive and can be converted to a variety of petrochemicals and useful
end products.
The major petrochemicals produced from ethylene are:
1. Ethanol
2. Ethylene oxide
3. Ethylene glycol
4. Dichloroethane
5. Vinyl chloride
6. Polyethylene
7. Ethyl benzene
Ethanol
Ethanol is made by hydration of ethylene. It is used as a solvent and a raw material for the manufacture of acetic acid, ethyl
acetate and a large number of other useful products.
H2C = CH2 H O/H SO CH3CH2OH
2 2 4 31
Ethylene Oxide
Ethylene is oxidized to ethylene oxide with air or oxygen in the presence of a catalyst.
catalyst H2C CH2
H2C CH2
O2
O
ethylene dioxide
Ethylene Glycol
Ethylene glycol (1,2-dihydroxyethane) is manufactured by starting with ethylene. There are several methods by which ethylene is
converted to ethylene glycol.
H2C = CH2 HO – CH2 – CH2 – OH
(ethylene glycol)
Dichloroethane
Dichloroethane (1,2-dichloroethane) is made from ethylene by the reaction of chlorine. It is used as a starting material for
several other raw materials like ethylene glycol, vinyl chloride, etc.
Polyethylene
On polymerization ethylene gives polyethylene (polyethene), which is an important plastic material.
nH2C = CH2 CH2-CH2 [-CH2-CH2] -CH2-CH2
(ethylene) (polyethylene)
Ethyl Benzene
Ethylene reacts with benzene in the presence of a suitable catalyst to give ethyl benzene. Ethyl benzene is converted to
styrene. Styrene is a raw material for the manufacture of important plastic material polystyrene.
CH2CH3
ethylbenzene
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Petrochemicals from Propylene
Propylene is obtained by pyrolysis of natural gas or by cracking of naphtha. Propylene is an unsaturated hydrocarbon.
The main petrochemicals produced from propylene are:
1. Iso-propyl alcohol
2. Polypropylene
3. Cumene (isopropyl benzene)
4. Glycerol
Petrochemicals from Acetylene
Acetylene (ethyne) is obtained by pyrolysis of natural gas. It is an unsaturated hydrocarbon. It has a carbon-carbon triple bond. It
is highly reactive in nature.
The major petrochemicals produced from acetylene are:
1. Vinyl chloride, vinyl acetate and acrylonitrile
2. Acetaldehyde
Petrochemicals from Butadiene
1,3-Butadiene is obtained from naphtha by cracking. It is a diene, that is, it has two carbon-carbon double bonds.
It is a monomer for polybutadine which is used as a substitute for natural rubber. Butadiene and styrene on polymerization give a
34
copolymer called BUNA-S
Petrochemicals from Benzene
Benzene is obtained from reformed naphtha. Naphtha is subjected to catalytic reforming (also called aromatization). In the
process, aliphatic hydrocarbons present in naphtha are converted to aromatic hydrocarbons.
Important petrochemicals obtained from benzene are:
1. Ethyl benzene and cumene
2. Chlorobenzene
3. Nitrobenzene
4. Cyclohexane
5. Linear alkyl benzenes (LAB)
6. Branched alkyl benzenes (BAB)
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TWELVETH AND THIRTEENTH WEEKS
36
SUGGESTED TEXTS FOR FURTHER READING
➢ Matar, S,L.; HatchMatar, F.S. & Hatch, L.F. (1994). Chemistry of Petrochemical Processes. (2nd
ed.). Texas USA
➢ David, S.J.; Jones J. & Peter P., Pujado P. (2006). Handbook of Petroleum Processing (1st ed.).
Springer
➢ James, H.; Gary G.; Glenn E., & Handwerk H. (2001). Petroleum Refining: Technology and
Economics (4th ed.). CRC Press
➢ James, G. & Speight S. (2006). The Chemistry and Technology of Petroleum (4th ed.). CRC
Press
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