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FINAL REQUIREMENT
PETROCHEMICALS
Title
INDUSTRIAL CHEMISTRY
Subject
GROUP 12
CAUILAN, KEICEE
MAMBA, RHEA
ODRUNIA, CHRISTINE JOY
UBIÑA, KATE HYACINTH
Professor
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I. Introduction
PETROCHEMICAL INDUSTRIES apply the knowledge of PETROCHEMISTRY to
transform petroleum into petrochemicals and petrochemicals into petrochemical products.
PETROCHEMISTRY
PETROCHEMICAL
PETROLEUM PETROCHEMICAL PRODUCTS
S PETROCHEMICAL
INDUSTRY
A. Petrochemistry
Petrochemistry is a branch of chemistry that deals with petroleum, natural gas and their
derivatives. It studies the transformation of crude oil (petroleum) and natural gas into useful
products or raw materialswhich are used to make many other products in the petrochemical
industry.
B. Petrochemical Industry
Petrochemical industries are specialized in the production of petrochemicals that have
various industrial applications.It is a fairly young industry since it only started to grow in the
1940s, more than 80 years after the drilling of the first commercial oil well in 1859. By the late
1950s, petrochemicals became one of the largest industries.
The growth and development of petrochemical industries depends on the marketability and
applicability of these petrochemicals for the manufacture of petrochemical products through
petrochemical processes which are made possible by knowledge and application of
petrochemistry.
II. Petrochemical
PETROCHEMICALS – are chemicals produced directly and indirectly from hydrocarbons of
petroleum.
Petroleum
It is a complex mixture of hydrocarbons formed by the decomposition of fossil remains.
It exists as a liquid (crude oil), gas (natural gas) or as solids (oil shales)
The term petroleum comes from the Latin stems petra, “rock,” and oleum, “oil.”
The world consumes 30 billion barrels (4.8 km3) of oil per year.
The Middle East contains 45-60% of world’s petroleum reserves.
Ghawar – world’s largest oil field.
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PRIMARY RAW MATERIALS, natural gas and crude oil, are the main sources for
hydrocarbon intermediates also known as the SECONDARY RAW MATERIALS or
FEEDSTOCKS – the starting raw materials used for the production of petrochemicals.
COMPOSITION
The principal component of most natural gases is methane.
A typical sample of natural gas when it is collected at its source contains about:
80% methane (CH4)
7% ethane (C2H6)
6% propane (C3H8)
4% butane and isobutane (C4H10)
3% pentanes (C5H12).
Crude Oil
DEFINITION
Crude oil (petroleum) is a naturally occurring brown to black flammable liquid. It is a
complex liquid mixture made up of a vast number of hydrocarbon compounds that
consist mainly of carbon and hydrogen in different proportions.
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Crude oils are generally classified based on the predominant proportion of similar
hydrocarbon molecules.
Paraffinic—the ratio of paraffinic hydrocarbons is high compared to aromatics and
naphthenes.
Naphthenic—the ratios of naphthenic and aromatic hydrocarbons are relatively higher
than in paraffinic crudes.
Asphaltic—contain relatively a large amount of polynuclear aromatic, a high
asphaltene content, and relatively less paraffins than paraffinic crudes.
COMPOSITION
A typical sample of crude oil contains about:
85%-90% carbon
10%-14% hydrogen
0.2%-3% sulfur
<0.1%-2% nitrogen
1%-1.5% oxygen
Crude petroleum contains hydrocarbon and non-hydrocarbon compounds.
FRACTIONAL
DISTILLATION (Columns)
FRACTIONAL DISTILLATION Demethaniser
Deethaniser
Depropaniser
Debutaniser
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A. Natural Gas
Hydrocarbons heavier than methane present in natural gases are recovered and separated by
LEAN OIL EXTRACTION.
Ethane
Natural Gas
Natural Liquids (NGL)
LEAN OIL EXTRACTION LPG
Gas
B. Crude Oil
Because the substances in the crude oil have different boiling points, they can be separated
using FRACTIONAL DISTILLATION.
Fractional Distillation
It is a physical process that refines the crude oil without altering its molecular structure
into useful products.
Fractional distillation is the separation of a mixture into its component parts, or fractions,
separating chemical compounds by their boiling point by heating them to a temperature at
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which one or more fractions of the compound will vaporize. It uses distillation to
fractionate.
This is a continuous process (not a batch process).
FRACTIONAL DISTILLATION OF CRUDE OIL
FRACTIONAL DISTILLATION
FRACTIONAL
DISTILLATION (Columns)
Demethaniser
Deethaniser
Depropaniser
Debutaniser
A. Methane (CH4)
The main component of natural gas.
It can berecoveredfrom dry natural gas and associated gas.
Methane is a clean fuel gas. Important source for carbon black. Liquefied under very
high pressures and low temperatures for transportation to long distances through
cryogenic tankers.
B. Ethane (C2H6)
Ethane's relation with petrochemicals is mainly through its cracking to ethylene.
Recovered from natural gas liquids and can also be separated from petroleum gas, a
mixture of gaseous hydrocarbons produced as a byproduct of petroleum refining.
Burned with methane as a fuel gas.
C. Propane (C3H8)
Obtained from natural gas liquids or from refinery gas streams.
Liquefied petroleum gas (LPG) = propane + butane and is mainly used as a fuel.
LPG is currently an important feedstock for the production of olefins for petrochemical
use.
D. Butane
Obtained from natural gas liquids and from refinery gas streams.
Butane is primarily used as a fuel gas within the LPG mixture.
Dehydrogenation of n-butane to butenes and to butadiene is an important route for the
production of synthetic rubber.
N-Butane is also a starting material for acetic acid and maleic anhydride production.
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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E. Naphtha
The overhead liquid distillate from the crude oil distillation unit is called virgin or
straight-run naphtha and that distillate is the largest source of naphtha in most petroleum
refineries. The naphtha is a mixture of many different hydrocarbon compounds.
In refining operations, however, it is customary to blend one type of naphtha with another
to obtain a required product or feedstock.
PETROCHEMICAL PROCESSES:
Conversion of Methane Methanol
The processes used to convert methane to methanol are CATALYTIC OXIDATION and
METHANOL SYNTHESIS.
A. Catalytic Oxidation
Methane is converted into methanol (methyl alcohol, CH3OH) by catalytic oxidation.
Catalytic oxidation is a process that oxidizes compounds using catalysts. The addition of
a catalyst accelerates the rate of oxidation by adsorbing the oxygen.
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B. Methanol Synthesis
Before methane is converted into methanol, methane will undergo steam reforming and
will produce syngas. The syngas produced will be converted into methanol by methanol
synthesis.
Methanol Synthesis Process Flow Diagram:
The reaction is exothermic in nature and so based on the equilibrium constant the
temperature of the reactor is maintained around 300 to 375 oC and pressure around 200 to
350 atm is required. As per the flow sheet synthesis gas is compressed and preheated to the
required temperatures of the reactor and fed to the reactor bottom, excess heat is recovered
by the steam generators. Outlet gas is let downed to the 14 atm toward the depressurizing
drum. The reactor used for this reaction is constructed with copper lined steel containing a
catalyst which is blended with zinc, manganese oxide and chromium. The depressurized
methanol will be in liquid state and it is treated with permanganate to remove impurities
obtained during the side reaction on the catalyst surface. Mostly lower molecular weight
dimethyl ether is obtained from the stripper top outlet and bottom high molecular weight
methanol is obtained for storage and transport. A final purification step is carried out at
methanol tower to remove water from methanol (CH3OH) because it is high solubility in
water.
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A. Propane Dehydrogenation
PDH is vital to the petrochemical industry because propylene is the second most
important starting product in the petrochemical industry after ethylene.
Dehydrogenation is a chemical reaction that involves the removal of hydrogen from a
molecule. It is the reverse of hydrogenation. This process is highly endothermic and
requires temperatures of 500 °C and above. Enzymes that catalyze dehydrogenation are
called dehydrogenases.
Propane Crygonic
Dryer
Feeds Sepator
The process consists of a reactor section, product recovery section and catalyst
regeneration section. Hydrocarbon feed is mixed with hydrogen-rich recycle gas and is fed
into a heater to be heated to over 540°C (1000°F) and then enters the reactors to be converted
at high mono-olefin selectivity. Several interstage heaters are used to maintain the reaction
through supplying heat continuously, since the reaction is endothermic. Catalyst activity is
maintained by the continuous catalyst regenerator (CCR) or by shutting down reactors one by
one and regenerating the reactor by using regeneration air. In the continuous catalyst
regenerator, catalyst is continuously withdrawn from the reactor, regenerated, and then fed
back into the reactor bed.
The reactor effluent is compressed, dried and sent to a cryogenic separator where
hydrogen is recovered. The olefin product is sent to a selective hydrogenation process (SHP)
where dienes and acetylenes are saturated to mono-olefins. The propylene stream goes to a
deethanizer where light-ends are removed prior to the propane-propylene (P-P) splitter.
Unconverted feedstock is recycled back to the depropanizer where it combines with fresh
feed before being sent back to the reactor section
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Conversion of Ethane Ethylene, LPG Ethylene + Propylene + C4 Stream and
Naphtha C4 Stream
Ethane, Naphtha and LPG are thermally cracked by STEAM CRACKING to produce lighter
hydrocarbons.
A. Steam Cracking
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). Steam cracker units are facilities in which a feedstock such
as naphtha, liquefied petroleum gas (LPG), ethane, propane or butane is thermally
cracked through the use of steam in a bank of pyrolysis furnaces to produce lighter
hydrocarbons.
Separation Steam
Natural gas Separation Products
Unit Crackers
Natural gas first enters the gas separation unit to obtain different types of
hydrocarbons. Next, feedstock gases are thermally crack (up to 1100 C) in the process of
steam using pyrolysis furnaces to produce lighter hydrocarbons. At this stage, two
chemical reaction occur, splitting of C-H and C-C single bonds. The products obtained in
this step depend on the feedstock feed composition, hydrocarbon-to-steam ratio, and
cracking temperature. After reaching the cracking temperature, the hot gas mixture is
quickly quenched in the transfer line exchangers (TLE) to 550-650 C. TLE will be
subsequently cooled down to 300 C to avoid degradation by secondary reactions and
generate high pressure steam for driving compressors.
The products obtained depend on the composition of the feed, the hydrocarbon-to-steam
ratio, and on the cracking temperature and furnace residence time. Light hydrocarbon
feeds such as ethane, LPGs or light naphtha give product streams rich in the lighter
alkenes, including ethylene, propylene, and butadiene.
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A. Catalytic Reforming
Reforming takes straight chain hydrocarbons in the C6 to C8 range from the naphtha
and rearranges them into compounds containing benzene rings.
Catalytic reforming typically produces a reformate product containing C6 to C8
aromatics (benzene, toluene, xylenes) as well as paraffins and heavier aromatics
containing 9 to 11 or 12 carbon atoms.
Main process for upgrading low octane naphthas to high octane gasoline blending
components or chemicals intermediates (benzene/toluene/xylenes).
Number of Important Byproducts
H2 for Hydrotreating
C1 ‐ C2 for Fuel Gas
C3 ‐ C4 FOR LPG
C4'S to Mogas or Alkylation
Aromatics for Petrochemicals
PROCESS:
Basic Steps in Catalytic Reforming
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VIII. Primary and Secondary Petrochemicals
The petrochemicals obtained from the feedstocks are called PRIMARY
PETROCHEMICALS. While the petrochemicals obtained from primary petrochemicals by
chemical reaction are called SECONDARY PETROCHEMICALS.
A. Ethylene
It is the simplest form of olefinic hydrocarbon series and one of the most important raw
materials of the organic chemical industry. It occurs both petroleum and natural gas, but
the bulk of the industrial material is produced by heating of higher hydrocarbons.
Ethylene is a colorless gas with a sweet odor and taste. It is lighter than air. It is easily
ignited and a flame can easily flash back to the source of the leak.
Intermediates:
1. Polyethylene
Formed through polymerization of ethylene. Ethyl benzene – is formed by
combination of ethylene and benzene.
2. Ethyl benzene
Formed by combination of benzene and ethylene.
Derivative: Styrene
3. Ethylene dichloride
Formed by chlorination of ethylene.
Derivative: Vinyl chloride monomer
4. Ethylene oxide
Obtained through oxidation of ethylene.
Derivatives: Ethanolamines, Monoethylene glycol, Ethylene glycol ethers and
Diethylene glycol
5. Ethyl alcohol
Also called ethanol, produced by hydration of ethylene.
It is an oxygenated hydrocarbon used in a wide variety of high performance
solvent applications (toiletries and cosmetics, paints, lacquer thinners, printing
inks, dyes, detergents, disinfectants and pharmaceuticals), as a chemical raw
material for the production of a range of monomers and solvents, and is
essential in pharmaceutical purification. In transportation, ethanol is used as a
vehicle fuel by itself, blended with gasoline, or as a gasoline octane enhancer
and oxygenate.
Derivatives: Ethyl acrylate, Ethyl acetate and Ethyl amines
6. Acetaldehyde
Formed by catalytic oxidation of ethylene.
An aldehyde used as a starting material in the synthesis of acetic acid, n-butyl
alcohol, ethyl acetate, and other chemical compounds.
Derivative: Acetic acid
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B. Propylene
A colourless, flammable, gaseous hydrocarbon obtained from petroleum.
It is the second most important starting product in the petrochemical industry after
ethylene.
Intermediates:
1. Polypropylene
Formed by polymerization of propylene
polyolefin plastic type
2. Acrylic acid
Formed by catalytic partial oxidation of propylene
Important monomers used for the manufacture of polymer dispersions,
adhesives, flocculants, detergents, varnishes, fibres and plastics as well as
chemical intermediates.
Derivative: Polyacrylate
3. Acrylonitrile
Formed by catalytic ammoxidation of propylene
It is a chemical compound with a formula of C3H3N. This colourless liquid
often appears yellow due to impurities.
Derivatives: ABS plastics, NBR synthetic rubber, SAN plastics and Acrylic
fibres
4. Cumene
An aromatic derived from alkylation of benzene by propylene.
Derivatives: Phenol and Acetone
5. Propylene oxide
Formed by oxidation of propylene
It is a petrochemical used as a monomer in polymer production and as an
intermediate in the synthesis of other substances.
Derivatives: Monopropylene glycol, Propylene glycols, Propylene glycol
ethers and Polyols
6. Butyraldehyde
Formed by hydroformylation of propylene
It is a clear, colourless, flammable liquid, used chiefly as an intermediate in
the manufacture of resins.
Derivatives: Ethyl hexanol, N-butanol, Isobutanol and Acrylic acid
7. Isopropanol
Formed by hydration of propylene
It is a major component of rubbing alcohols.
It is a secondary alcohol.
One of the cheapest alcohols and has replaced ethanol for many uses because
of its similar solvent properties.
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It was formerly obtained largely by catalytic reduction of acetone; oxidation
of isopropanol is now the major source of acetone.
Derivatives: Acetone and Isopropyl acetate
C. C4 stream
Colourless gas with a pungent, gasoline-like odour, usually stored as a liquid under
pressure.
C4 derivatives are among the main olefin products coming from the steam cracker, along
with ethylene and propylene.
Butadiene is the most valuable product from the C4 fraction.
Intermediates:
1. Isobutylene
Formed dehydroisomerization of butane.
It is used in organic synthesis and in the production of high octane aviation
gasoline.
It is special because it is the only rubber that is gas impermeable.
It can hold air for long periods of time.
Derivatives: Polyisobutylene and MTBE
2. N-Butene
Formed by oxidative dehydrogenation of butane
Are formed during the cracking of petroleum to produce gasoline; they can
also be prepared commercially by the catalytic dehydrogenation of butanes.
Derivatives: Higher olefins
3. Butadiene
Formed by oxidative dehydrogenation of butane
It is a flammable gaseous olefin used in making synthetic rubbers.
Butadiene rubber has now completely displaced natural rubber in the
manufacture of automobile tires.
Derivatives: NBR nitrite synthetic rubber and SBR styrene butadiene rubber
D. Methanol
A colourless, flammable alcohol.
A chemical used in the production of formaldehyde, acetic acid and methyl methacrylate
(MMA), and is used as a solvent in many applications.
Intermediates:
1. Methyl methacrylate
Hydroesterification of ethylene and Condensation of MeP with formaldehyde
Methyl Methacrylate is a methyl ester of methacrylic acid.
Methyl methacrylate is a reactive resin, and the polymerized form is used as
cement in dentistry, orthopaedic surgery and ophthalmology.
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The monomer form of this agent has relaxation effect on smooth muscle
systemically, which might be a result of nitric oxide-mediated response.
2. Formaldehyde
Formed by oxidative dehydrogenation of methanol
Formaldehyde is a colorless, strong-smelling gas used in making building
materials and many household products.
It is used in pressed-wood products, such as particleboard, plywood, and
fiberboard; glues and adhesives; permanent-press fabrics; paper product
coatings; and certain insulation materials.
3. MTBE (Methyl Tertiary Butyl Ether)
Formed by catalytic etherification of isobutylene with methanol
MTBE (methyl tertiary-butyl ether) is a flammable, colorless liquid that
dissolves easily in water. It is part of a group of chemicals known as fuel
oxygenates.
MTBE and other oxygenates make gasoline burn better, which lowers harmful
carbon monoxide and other emissions from vehicles, reducing air pollution.
E. Benzene
Simplest aromatic compound with a ring of six carbon atoms and six hydrogen atoms.
Benzene is a clear, colorless, highly flammable and volatile, liquid aromatic hydrocarbon
with a gasoline-like odor.
Intermediates:
1. Ethylbenzene
Formed by combination of ethylene and benzene, and is then dehydrogenated
to styrene for use in the production of plastics and synthetic rubber.
Derivative: Styrene
2. Cumene
Formed by alkylation of benzene by propylene.
An aromatic derived from benzene and propylene and is used in turn to
produce polycarbonates, phenolic resins and essential pharmaceuticals such as
aspirin and penicillin.
Derivatives: Phenol and Acetone
3. Cyclohexane
Formed by hydrogenation of benzene
an aliphatic cyclic hydrocarbon derived from benzene used as an intermediate
to produce nylon
Derivative: Nylon
4. Alkylbenzene
Formed by alkylation of benzene
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One of the most important organic raw material for the production of synthetic
detergents.
Derivative: Surfactants
F. Toluene
A colourless aromatic hydrocarbon used extensively as starting for making benzene and
xylenes.
Toluene is a clear colorless liquid with a characteristic aromatic odor. Flash point 40°F.
Less dense than water (7.2 lb / gal) and insoluble in water. Hence floats on water. Vapors
heavier than air.
Intermediates:
1. TDI- toluene di-isocyanate
Nitration of toluene, hydration of dinitrotoluene and Reaction of phosgene and
toluene diamine
An organic compound that is prepared from toluene.
Derivative: Polyurethane
2. Solvents
Liquids that have the ability to dissolve, suspend or extract other materials,
without chemical change to the material or solvent.
Solvents make it possible to process, apply, clean or separate materials. Water
is an inorganic solvent. Organic solvents include hydrocarbon solvents,
oxygenated solvents and chlorinated solvents.
G. Xylenes
A colourless liquid aromatic hydrocarbon of which there are several forms.
Colorless, water-insoluble, flammable, toxic, isomeric liquids, C8H10, of the benzene
series, obtained mostly from coal tar: used chiefly in the manufacture of dyes.
It is used as solvents, as components of aviation fuel, and as raw materials for the
manufacture of dyes, fibres and films.
Paraxylene is commercially the most important.
Intermediates:
1. Paraxylenes
Used to make polyesters, which have applications in clothing, packaging
and plastic bottles.
Derivative: Polyester
2. Orthoxylenes
An isomer of mixed xylene. It is primarily used in plasticisers, medicines
and dyes.
Derivative: Plasticisers
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IX. Secondary Petrochemicals and Petrochemical Products
The SECONDARY PETROCHEMICALS are put to some use or may be further processed
by a chemical reaction or a series of reactions to get PETROCHEMICAL PRODUCTS for other
end uses.
Ethylene oxide
Ethanolamine
Glycol ethers
Ethyl alcohol Paints and
Polyether polyol varnishes
Mono Ethylene Glycol Plastics
Polyesters Fabrics
Ethylene Polyethylene
Solvents Automotive
Ethylamine Paper
Acetic acid Pharmaceuticals
Ethyl dichloride
Vinyl chloride monomer
Polyvinyl chloride
Acetaldehyde
MMA
Plastics
PMMA Automotive
Synthetic resins Construction
Methanol Phenolic Resins Pharmaceutical
Formaldehyde Polyurethane Photographic
Textile
MTBE
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Primary Secondary Petrochemical Major End Consumer
Petrochemicals Petrochemicals Products Industries
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