PETRO CHEMICALS

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Crude oils differs in their properties because of the variable ratios of the
crude oil components.
For a refiner it is necessary to group crudes with similar characteristics.
The following describes three types of crudes:
Paraffinic, Naphthenic and Asphaltic
CnH2n+2

1. Paraffinic—the ratio of paraffinic hydrocarbons is high compared

to aromatics and naphthenes.
2. Naphthenic—the ratios of naphthenic and aromatic hydrocarbons
are relatively higher than in paraffinic crudes.
3. Asphaltic—contain relatively a large amount of polynuclear aromatics,
a high asphaltene content, and relatively less paraffins than
paraffinic crudes.
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PARAFFINIC HYDROCARBONS

Paraffinic hydrocarbons: source of petrochemicals ranging

from methane, to heavier hydrocarbon (gases and liquid)

These compounds are the precursors for olefins through cracking

processes. The C6–C9 paraffins and cycloparaffins are especially
important for the production of aromatics through reforming.
METHANE (CH4)
Methane is the main component of many natural gas. It is a colorless,
odorless gas that is lighter than air. Methane is pretty inert.
Reacts with O2 and Cl2 under certain condition.
Oxidized with a limited amount of O2 to CO-H2 (synthesis gas) at high temp.
It is an important building block for many chemicals. (It is also an important
source for carbon black.
Methane may be liquefied under very high pressures and low temperatures.
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carbon black

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Carbon black is a fundamental component in the electrodes in a LIB
(Lithium Ion battery), because it increases the electrical conductivity of the
system, enabling a better battery performance. The total market demand
for carbon black for Lithium Ion batteries is 20kt.

Carbon black has efficacy to improve the fast-charging ability of anodes.

The introduction of carbon black reduces the resistance of
Li + intercalation. Pouch cells with high energy density and fast-charging
ability are achieved. The optimized battery retains 87% of the initial
capacity after 500 cycles.

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ETHANE (CH3-CH3)

Ethane is an important intermediate for the production of ethylene.

Ethane, like methane, is inert, colorless gas that is insoluble in water.
It does not react with acids and bases. It can also be partially oxidized to
a CO and H2 (synthesis gas) or chlorinated to useful solvents.

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 PROPANE (CH3CH2CH3)
Propane is a more reactive than CH4 and C2H6 due to the presence of
two secondary hydrogens.

LPG is a mixture of propane and butane and is mainly used as a

fuel. Feedstock for the production of propylene.

Liquid propane is a selective solvent used to separate paraffinic

constituents in lube oil base stocks from harmful asphaltic materials.

Used as refrigerant for liquefying natural gas and for

the recovery of condensable hydrocarbons from natural gas.
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8
BUTANES (C4H10)
The C4 acyclic compound consists of two isomers: n-butane
and iso-butane (2-methylpropane).

Uses:
Used as a fuel gas in LPG mixture.
Feedstock for steam cracking units for olefin production.
Dehydrogenation of n-butane to butenes and to butadiene is an important route
for the production of synthetic rubber.

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If you are interested ??:

Isomerization reaction:

Maleic anhydride production:

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 Alternative methods of getting butadiene

Cycloalkanes

Usually cycloalkane will give lower yields of ethylene than the corresponding straight
chain alkanes. They tend to give dienes along with other products.

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Starting materials for acetic acid and maleic anhydride production.

Isobutane is an alkylating agent for the production of alkylates (mixture of

branched hydrocarbons in the gasoline having high octane ratings

Trimethyl
pentanes

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Dehydrogenation of isobutane produces isobutene, which is a reactant
for the synthesis of methyl tertiary butyl ether (MTBE).

This compound is currently in high demand for preparing unleaded

gasoline due to its high octane rating and clean burning properties.

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OLEFINIC HYDROCARBONS

The important olefins are ethylene, propylene, butylenes, and isoprene.

Olefins have higher reactivity's and reacts with water, oxygen, hydrochloric
acid, and chlorine to form valuable chemicals. (similar to rancidity of oils)
Plymerized to important polymers such as polyethylene and polypropylene.

ETHYLENE (CH2=CH2)

Colorless gas with a sweet odour, slightly soluble in water and alcohol.
Highly active compound that reacts easily by addition to many chemicals
and produces some useful chemicals such as:
ethyl alcohol, 1,2-dichloroethane, vinyl chloride.
(how would you synthesized them?)

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Ethylene is an active alkylating agent for the production of ethyl
benzene, which is dehydrogenated to styrene. Styrene is a monomer used
in the manufacture of many commercial polymers and copolymers.

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ETHYLENE (CH2=CH2)

Ethylene can be polymerized to different grades of polyethylenes or

copolymerized with other olefins.
Catalytic oxidation of ethylene produces ethylene oxide, which is
hydrolyzed to ethylene glycol.
Ethylene glycol is a monomer for the production
of synthetic fibers.

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PROPYLENE (CH3CH=CH2) optional slide

Mainly obtained from refinery gas streams, by cracking processes (of

propane). The main source of propylene, however, is “steam cracking” of
hydrocarbons, where it is coproduced with ethylene.

But most “hemolysis” reaction do not start their reaction by undergoing

homolysis, but rather by suffering hydrogen atom abstraction from the
–CH2- position. In this process a secondary hydrogen radical will be generated

The C-C b-session of this radical will give an alkene other than ethylene
and a small primary radical

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Propylene can be polymerized alone or
copolymerized with other
monomers such as ethylene.
Chemicals derived are: isopropanol, allyl
alcohol, glycerol, and acrylonitrile.

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BUTYLENES (C4H8)
Butylenes (butenes) are by-products of cracking processes and steam
cracking units for ethylene production. Dehydrogenation of butanes is a
second source of butenes. However, this source is becoming more
important because isobutylene is currently highly demanded for the
production of oxygenates as gasoline additives (MTBE, see slide 10).
.

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The four butene isomers:

Many industrial reactions involving cis- and

trans-2-butene produce the same products.
For this reason, it is economically feasible to
isomerize 1-butene to 2-butene (cis and trans)
and then separate the mixture.

Four butene problem??

why, isomerize xxx

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An alternative method for separating: By treating with cold sulfuric acid, which
polymerizes to di- and tri-isobutylene. The dimer and trimer of isobutene have
high octane ratings and are added to the gasoline pool.

??

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THE DIENES
Dienes are aliphatic compounds having two double bonds either
conjugated or nonconjugated (little industrial importance).

An important difference between conjugated and nonconjugated

dienes is that the former compounds can react with reagents such
as chlorine, yielding 1,2- and 1,4-addition products.

??

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BUTADIENE (CH2=CH-CH=CH2)

Butadiene is the most important monomer for synthetic rubber. It can be

polymerized to poly-butadiene or copolymerized with styrene to styrene-
butadiene rubber (SBR).

Butadiene is an important intermediate for the synthesis

hexamethylenediamine (HMDA) and adipic acid (precursors for nylon-66).

??

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Mechanism part optional

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Chloroprene is another butadiene derivative for the synthesis of
neoprene rubber (below is DuPont's method).

Rubber

??

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Butadiene is highly reactivity and low cost,
obtained mainly as a coproduct with other light olefins from steam cracking
units for ethylene production.
Other sources of butadiene are the catalytic dehydrogenation of
butanes (C-4) and n-butenes, and dehydration of 1,4-butanediol.

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Isoprene is another conjugated diene for synthetic rubber production. The
main source for isoprene is the dehydrogenation of C5 olefins. It can also be
produced through several synthetic routes using reactive chemicals such as
isobutene, formaldehyde, and propene.

AROMATIC HYDROCARBONS

Benzene, toluene, xylenes (BTX), and ethylbenzene are the aromatic

hydrocarbons with a widespread use as petrochemicals. sulfolane
Precursors for many commercial chemicals and polymers such as phenol,
trinitrotoluene (TNT), nylons, and plastics. ???

(BTX), and ethylbenzene are obtained from the catalytic reforming of heavy
naphtha. The product reformate is rich in C6, C7, and C8 aromatics, which
could be extracted by a suitable solvent such as sulfolane or ethylene glycol.
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Before natural gas is used it must be processed or treated to
remove the impurities and to recover the heavier hydrocarbons
(heavier than methane). 28
NATURAL GAS TREATMENT PROCESSES

Raw natural gases contain variable amounts of CO2, H2S and H2O.
Domestic consumption of crude gas:
(i) H2S is poisonous, cause of acid rain and corrodes metallic
equipments.
(ii) CO2 reduces the heating value and solidifies under the
high pressure and low temperatures
(iii) Higher hydrocarbons and water are undesirable

Q. Why only cow dungs are used as

feed in Biogas pant and not human
waste?

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Waste to Wealth

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Acid Gas Treatment:
Acid gases can be reduced or removed by
1. Physical absorption using a selective absorption solvent. ???
2. Physical adsorption using a solid adsorbent.
3. Chemical absorption where a solvent (a chemical) capable of reacting
reversibly with the acid gases is used.

1. Physical absorption using solvents:

Commercially used process are: Selexol, Sulfinol and Rectisol
The solvent used: Dimethyl ether and polyethylene glycol
No chemical reaction takes place
Absorb at low temperature and high pressure
Hydrocarbons escapes and the solvent is regenerated by reducing
the pressure.

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2. Physical adsorption using solid adsorbent:
Molecular sieves (zeolites) are widely used which absorb large amount of gases
Multiple absorption bed is used for continuous operation
Useful for low concentration of acid gases
Molecular sieves also absorb moisture.

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 ???
3. Chemical absorption (Chemisorption):
(i). Solution of a relatively weak base, such
as monoethanolamine and diethanol
amines are used. The acid gas (sulphides,
carbonates and bicarbonates) forms a
weak bond with the base which can be
regenerated easily. 33
(ii). Strong basic solutions: Effective, however, these solutions are not used for
treating large volumes because the acid gases form stable salts, which are not
easily regenerated

Water Removal
Necessary to reduce corrosion problem and prevent hydrate formation

???

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To prevent hydrate formation, natural gas is treated with glycols, which
dissolve water efficiently. Ethylene glycol (EG), diethylene glycol (DEG), and
triethylene glycol (TEG) are typical solvents for water removal.

???

Another way to dehydrate nature gas is

by injecting methanol in to the gas line

Molecular sieves are other adsorbent

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Condensable Hydrocarbon Recovery
or Natural Gas Liquids (NGL)
Hydrocarbons heavier than methane are valuable raw materials as well
as important fuels.
a) The first step is cool the treated gas by exchange with liquid propane.
b) The cooled gas is then washed with a cold hydrocarbon liquid, which
dissolves most of the condensable hydrocarbons.
c) The uncondensed gas (dry gas) is composed mainly
of methane with small amounts of ethane and heavier hydrocarbons.
d) The condensed hydrocarbons or natural gas liquids (NGL) are
stripped from the solvent and the solvent is recycled.
e) Both dry gas and NGL are used either as fuel or chemical feedstock

Other means of separation is by Cryogenic

Cooling(-150- 180 oF)
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NATURAL GAS LIQUIDS (NGL)

Natural gas liquids (condensable hydrocarbons) are those hydrocarbons

heavier than methane that are recovered from natural gas.
Natural gas liquids are normally fractionated to separate them into
three streams:
a) An ethane-rich stream, which is used for producing ethylene.
b) Liquefied petroleum gas (LPG), which is a propane-butane mixture.
It is mainly used as a fuel or a chemical feedstock.
c) Natural gasoline (NG) is mainly constituted of C5+ hydrocarbons
and is added to gasoline to raise its vapour pressure.
d) NLG contains significant amounts of cyclohexane, a
precursor for nylon 6

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CRUDE OILS
Crude oil (petroleum) is a naturally occurring
brown to black flammable liquid of variable
composition.

Main constituents of crude oil

1. Hydrocarbon compounds.
2. Non-hydrocarbon compounds.
3. Organometallic compounds and inorganic salts.
Hydrocarbons
The main constituents of crude oils are hydrocarbons. Numerous hydrocarbons are
present in the crude mixture, except alkenes and alkynes. This may indicate that
crude oils originated under a reducing atmosphere (in the absence of oxygen).
• Alkanes (paraffin)
• Cycloparaffins (naphthenes)
• Aromatics
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 Alkanes (paraffins):

Cycloparaffins (Naphthenes): Saturated cyclic hydrocarbons,

normally known as naphthenes, are also part of the hydrocarbon
constituents of crude oils.

They are important precursors for aromatic hydrocarbons

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Aromatic Compounds
Benzene, toluene, and xylenes (BTX) are important petrochemical
intermediates as well as valuable gasoline components.
Separating BTX from crude oil distillates is not feasible because they are
present in low concentrations.
Enriching a naphtha fraction with these aromatics is possible through a
catalytic reforming process.

Only a few aromatic-cycloparaffin

compounds have been isolated
and identified. Tetralin is an
example of this class.

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2. Non-hydrocarbon compounds.
Various non-hydrocarbon compounds namely sulfur, nitrogen, oxygen and
metallic (traces) are found in all crudes.

The presence of these impurities

is harmful and may cause
problems to certain catalytic
processes (catalytic poisoning).
Fuels having high sulfur and
nitrogen levels cause pollution
problems (acid rain) in addition to
the corrosive nature of their
oxidized products.

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Sulfur Compounds
Sulfur compounds are mainly present in the form of organosulfur
compounds. H2S is the only important inorganic sulfur compound found in
crude oil. Its presence, is harmful because of its corrosive nature.

Classification ???

Most sulfur compounds can be removed

from petroleum streams through
“hydrotreatment” or “hydrodesulfurization”
processes, where hydrogen sulfide is
produced and the corresponding
hydrocarbon released. Hydrogen sulfide is
then absorbed in a suitable absorbent and
recovered as sulfur. (Circular economy)
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Nitrogen Compounds
Organic nitrogen compounds occur either as heterocyclic
(pyridine and pyrrole, or in a complex structure as in porphyrin.

Nitrogen compounds are more thermally stable than sulfur compounds and
accordingly are concentrated/magnified in heavier petroleum fractions.
Light petroleum streams may contain trace amounts of nitrogen
compounds, which should be removed because they poison many
processing catalysts.
During hydrotreatment of petroleum fractions, nitrogen compounds are
“hydrodenitrogenated” to ammonia and the corresponding hydrocarbon.

porphyrin
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Classificatio
n

Both class are aromatics

Some time V and Ni are found

Separation of nitrogen compounds is

difficult, they are susceptible to alteration
and loss during handling. However, the
basic low molecular weight compounds
may be extracted with dilute mineral acids.
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Oxygen Compounds
Oxygen compounds are more complex than the sulfur compounds.
Their presence is not poisonous to processing catalysts.
Many compounds found in crude oils are weakly acidic (carboxylic acids,
cresylic acid, phenol, and naphthenic acid).
Naphthenic acids are mainly cyclopentane and cyclohexane
derivatives having a carboxyalkyl side chain. They have commercial
value and are extracted using a dilute caustic soda solution.

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 Less abundant and little
commercial value.

Metallic Compounds
Abundant metals found are Na, Ca, Mg, Al, Fe, V, and Ni.
Present either as salts, (NaCl and MgCl) or in the form of organometallic
compounds (as in porphyrins).
Ca and Mg can form salts with carboxylic acids (soap) which act as emulsifiers,
which is undesirable.
NaCl and MgCl produce HCl, which is very corrosive.
Desalting crude oils is a necessary.
Vanadium and nickel are poisons to many catalysts
Solvent extraction are used to reduce the concentration of heavy
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