Chapter one

COAL AND PETROLEUM PROCESSING

1.1. Origin of Coal and Its Ranking
Coal is a combustible black or brownish-black sedimentary rock usually occurring in rock strata
in layers or veins called coal beds or coal seams. The harder forms, such as anthracite coal, can
be regarded as metamorphic rock because of later exposure to elevated temperature and pressure.
Coal is composed primarily of carbon along with variable quantities of other elements, chiefly
hydrogen, sulfur, oxygen, and nitrogen. Throughout history, coal has been a useful resource for
human consumption. It is primarily burned as a fossil fuel for the production of electricity and/or
heat, and is also used for industrial purposes such as refining metals. Coal forms when dead plant
matter is converted into peat, which in turn is converted into lignite, then anthracite. This
involves biological and geological processes that take place over a long period of time.
As geological processes apply pressure to dead biotic material over time, under suitable
conditions it is transformed successively into:
 Peat, considered to be a precursor of coal, has industrial importance as a fuel in some
regions.
 Lignite or brown coal is the lowest rank of coal and used almost exclusively as fuel for
electric power generation.
 Sub-bituminous coal, whose properties range from those of lignite to those of bituminous
coal, is used primarily as fuel for steam-electric power generation and is an important
source of light aromatic hydrocarbons for the chemical synthesis industry.
 Bituminous coal is dense sedimentary rock, black but sometimes dark brown often with
well defined

Carbonisation of coal
 There are a number of carbonization processes. The carbonization conversion occurs
through pyrolysis or destructive distillation, and it produces condensable coal tar, oil and
water vapor, non-condensable synthetic gas, and a solid residue-char. The condensed
coal tar and oil are then further processed by hydrogenation to remove sulfur and
nitrogen species, after which they are processed into fuels. The typical example of
carbonization is the Karrick process. The process was invented by Lewis Cass Karrick in
the 1920s. The Karrick process is a low-temperature carbonization process, where coal is
heated at 680 °F (360 °C) to 1,380 °F (750 °C) in the absence of air. These temperatures
optimize the production of coal tars richer in lighter hydrocarbons than normal coal tar.
However, the produced liquids are mostly a by-product and the main product is semi-
coke, a solid and smokeless fuel.

Gasification of Coal
Coal gasification can be used to produce syngas, a mixture of carbon monoxide (CO) and
hydrogen (H) gas. This syngas can then be converted into transportation fuels like gasoline and
diesel through the Fischer-Tropsch process. This technology is currently used by the Sasol
chemical company of South Africa to make gasoline from coal and natural gas. Alternatively, the
hydrogen obtained from gasification can be used for various purposes such as powering a
hydrogen economy, making ammonia, or upgrading fossil fuels.

1
During gasification, the coal is mixed with oxygen and steam (water vapor) while also being
heated and pressurized. During the reaction, oxygen and water molecules oxidize the coal into
carbon monoxide (CO) while also releasing hydrogen (H) gas. This process has been conducted
in both underground coal mines and in coal refineries.

(Coal) + O2 + H2O → H2+ CO2

If the refiner wants to produce gasoline, the syngas is collected at this state and routed into a
FischerTropsch reaction. If hydrogen is the desired end-product, however, the syngas is fed into
the water gas shift reaction where more hydrogen is liberated.
CO + H2O → CO2 + H2

Hydrogenation of Coal
One f the main methods of direct conversion of coal to liquids by hydrogenation process is the
Bergius process. The Bergius process was developed by Friedrich Bergius in 1913. In this
process, dry coal is mixed with heavy oil recycled from the process. Catalyst is typically added
to the mixture. The reaction occurs at between 400 °C (752 °F) to 500 °C (932 °F) and 20 to 70
MPa hydrogen pressure. The reaction can be summarized as follows:
n C + (n + 1) H2 → CnH2 n + 2

1.2 Petroleum – Origin, Classification and Mining

Petroleum is derived from Greek: petra (rock) + Latin: oleum (oil) or crude oil is a naturally
occurring, flammable liquid consisting of a complex mixture of hydrocarbons of various
molecular weights and other liquid organic compounds, that are found in geologic formations
beneath the Earth's surface.Petroleum is a fossil fuel derived from ancient fossilized organic
materials, such as zooplankton and algae. Vast quantities of these remains settled to sea or lake
bottoms, mixing with sediments and being buried under anoxic conditions. As further layers
settled to the sea or lake bed, intense heat and pressure built up in the lower regions. This process
caused the organic matter to change, first into a waxy material known as kerogen, which is found
in various oil shales around the world, and then with more heat into liquid and gaseous
hydrocarbons via a process known as catagenesis. Formation of petroleum occurs from
hydrocarbon pyrolysis in a variety of mainly endothermic reactions at high temperature and/or
pressure. Petroleum is a mixture of a very large number of different hydrocarbons; the most
commonly found molecules are alkanes (linear or branched), cycloalkanes, aromatic
hydrocarbons, or more complicated chemicals like asphaltenes. Each petroleum variety has a
unique mix of molecules, which define its physical and chemical properties, like color and
viscosity. The alkanes, also known as paraffins, are saturated hydrocarbons with straight or
branched chains which contain only carbon and hydrogen and have the general formula
CnH2n+2.They generally have from 5 to 40 carbon atoms per molecule, although trace amounts of
shorter or longer molecules may be present in the mixture. The petroleum industry generally
classifies crude oil by the geographic location it is produced in (e.g. West Texas Intermediate,
Brent, or Oman), its API gravity (an oil industry measure of density), and its sulfur content.
Crude oil may be considered light if it has low density or heavy if it has high density; and
it may be referred to as sweet if it contains relatively little sulfur or sour if it contains substantial
amounts of sulfur.

2
Distillation of Petroleum
Distillation is a method of separating mixtures based on differences in volatilities of components
in a boiling liquid mixture. The first and the most fundamental step in the refining process (after
the crude oil has been cleaned and any remnants of brine removed) is distillation
Fractional distillation of crude oil: Generally crude oil contains compounds having boiling
points upto 400OC. In this process, crude oil is heated to above 400 OC in a pipe. Its vapors are
allowed to enter into a fractionating tower having different compartment to collect different
volatilities. These are now condensed to liquid and are separated.
Distillation involves the separation of the different hydrocarbon compounds that occur naturally
in a crude oil into a number of different fractions (a fraction is often referred to as a cut).In the
atmospheric distillation process (Fig. 1.1), heated crude oil is separated in a distillation column
(distillation tower, fractionating tower, atmospheric pipe still) into streams that are then purified,
transformed, adapted, and treated in a number of subsequent refining processes, into products for the
refinery's market. The lighter, more volatile, products separate out higher up the column, whereas the
heavier, less volatile, products settle out toward the bottom of the distillation column. The fractions
produced in this manner are known as straight run fractions ranging from (atmospheric tower) gas,
gasoline, and naphtha, to kerosene, gas oils, and light diesel, and to (vacuum tower) lubricating oil and
residuum. The atmospheric residuum is then fed to the vacuum distillation unit at the pressure of 10
mmHg where light vacuum gas oil, heavy vacuum gas oil, and vacuum residue are the products.

Figure 1 .1 An atmospheric distillation unit

3
1.7 Cracking, Alkylation, Hydrotreating and Reforming
1.7.1 Cracking
Cracking processes break down heavier hydrocarbon molecules (high boiling point oils) into lighter
products such as petrol and diesel. These processes include catalytic cracking, thermal cracking and
hydrocracking.
e.g. A typical reaction:

Catalytic cracking is used to convert heavy hydrocarbon fractions obtained by vacuum

distillation into a mixture of more useful products such as petrol and light fuel oil. In this
process, the feedstock undergoes a chemical breakdown, under controlled heat (450 – 500 C) and
pressure, in the presence of a catalyst - asubstance which promotes the reaction without itself
being chemically changed. Small pellets of silica -alumina or silica - magnesia have proved to be
the most effective catalysts.
The cracking reaction yields petrol, LPG, unsaturated olefin compounds, cracked gas oils, a
liquid residue called cycle oil, light gases and a solid coke residue. Cycle oil is recycled to cause
further breakdown and the coke, which forms a layer on the catalyst, is removed by burning. The
other products are passed through a fractionator to be separated and separately processed.

Fluid catalytic cracking uses a catalyst in the form of a very fine powder which flows like a
liquid when agitated by steam, air or vapour. Feedstock entering the process immediately meets a
stream of very hot catalyst and vaporises. The resulting vapours keep the catalyst fluidised as it
passes into the reactor, where the cracking takes place and where it is fluidised by the
hydrocarbon vapour. The catalyst next passes to a steam stripping section where most of the
volatile hydrocarbons are removed. It then passes to a regenerator vessel where it is fluidised by
a mixture of air and the products of combustion which are produced as the coke on the catalyst is
burnt off. The catalyst then flows back to the reactor. The catalyst thus undergoes a continuous
circulation between the reactor, stripper and regenerator sections.

4
The catalyst is usually a mixture of aluminium oxide and silica. Most recently, the introduction
of synthetic zeolite catalysts has allowed much shorter reaction times and improved yields and
octane numbers of the cracked gasolines.

Thermal cracking uses heat to break down the residue from vacuum distillation. The lighter
elements produced from this process can be made into distillate fuels and petrol. Cracked gases
are converted to petrol blending components by alkylation or polymerisation. Naphtha is
upgraded to high quality petrol by reforming. Gas oil can be used as diesel fuel or can be
converted to petrol by hydrocracking. The heavy residue is converted into residual oil or coke
which is used in the manufacture of electrodes, graphite and carbides.

Hydrocracking can increase the yield of petrol components, as well as being used to produce
light distillates. It produces no residues, only light oils. Hydrocracking is catalytic cracking in the
presence of hydrogen. The extra hydrogen saturates, or hydrogenates the chemical bonds of the
cracked hydrocarbons and creates isomers with the desired characteristics. Hydrocracking is also
a treating process, because the hydrogen combines with contaminants such as sulphur and
nitrogen, allowing them to be removed. Gas oil feed is mixed with hydrogen, heated, and sent to
a reactor vessel with a fixed bed catalyst, where cracking and hydrogenation take place. Products
are sent to a fractionators to be separated. The hydrogen is recycled. Residue from this reaction is
mixed again with hydrogen, reheated, and sent to a second reactor for further cracking under
higher temperatures and pressures. In addition to cracked naphtha for making petrol,
hydrocracking yields light gases useful for refinery fuel, or alkylation as well as components for
high quality fuel oils, lube oils and petrochemical feedstocks. Following the cracking processes
it is necessary to build or rearrange some of the lighter hydrocarbon molecules into high quality
petrol or jet fuel blending components or into petrochemicals. The former can be achieved by
several chemical processes such as alkylation and isomerisation.

5
 UNIT TWO
MAIN PETROCHEMICALS
Petrochemical is any chemical (as distinct from fuels and petroleum products) manufactured
from petroleum (and natural gas) and used for a variety of commercial purposes. The definition,
however, has been broadened to include the whole range of aliphatic, aromatic, and naphthenic
organic chemicals, as well as carbon black and inorganic materials such as sulfur and ammonia.
Petroleum and natural gas are made up of hydrocarbon molecules, which comprise one or more
carbon atoms, to which hydrogen atoms are attached. Currently, oil and gas are the main sources
of the raw materials because they are the least expensive, most readily available, and can be
processed most easily into the primary petrochemicals . Primary petrochemicals include: olefins
(ethylene, propene, and butadiene), aromatics (benzene, toluene, and the isomers of xylene), and
methanol. Thus, petrochemical feedstocks can be classified into three general groups: olefins,
aromatics, and methanol; a fourth group includes inorganic compounds and synthesis gas
(mixtures of carbon monoxide and hydrogen) In many instances, a specific chemicals included
among the petrochemicals may also be obtained from other sources, such as coal, coke, or
vegetable products. For example, materials such as benzene and naphthalene can be made from
either petroleum or coal, whereas ethyl alcohol may be of petrochemical
or vegetable origin.As stated above, some of the chemicals and compounds produced in a
refinery are destined for further processing and as raw material feedstocks for the fast growing
petrochemical industry. Such nonfuel uses of crude oil products are sometimes referred to as its
nonenergy uses. Petroleum products and natural gas provide two of the basic starting points for
this industry; methane from natural gas, and naphtha and refinery gases. Petrochemical
intermediates are generally produced by chemical conversion of primary petrochemicals to form
more complicated derivative products. Petrochemical derivative products can be made in a
variety of ways: directly from primary petrochemicals; through intermediate products that
still
contain only carbon and hydrogen; and through intermediates that incorporate chlorine,

nitrogen , or oxygen in the finished derivative. In some cases, they are

finished products; in others, more steps are needed to arrive at the desired composition. Of all the
processes used, one of the most important is polymerization. It is used in the production of
plastics, fibers, and synthetic rubber, the main finished petrochemical derivatives. Some typical
petrochemical intermediates are vinyl acetate for paint, paper and textile coatings, vinyl chloride
for polyvinyl chloride (PVC), resin manufacture, ethylene glycol for polyester textile fibers, and
styrene that is important in rubber and plastic manufacturing. The end products number in the
thousands, some going on as inputs into the chemical industry for further processing. The more
common products made from
petrochemicals include adhesives, plastics, soaps, detergents, solvents, paints, drugs,
fertilizer, pesticides, insecticides, explosives, synthetic fibers, synthetic rubber, flooring,
and insulating materials.

2.2 Petrochemicals from methane, Ethylene, propylene, and butylenes

2.2.1 Chemicals from Methane
A large percentage of important chemicals derived from methane. Many inorganic compounds, not just
ammonia, are derived from synthesis gas, made from methane by steam reforming. carbonylation of
methanol to acetic acid, now the most important process for making this acid. Vinyl acetate is made from

6
acetic acid.

Synthesis of Methane derivatives

2.2.2 Derivatives of Ethylene
Numerous chemicals and polymers per year are made from ethylene, by far the most important organic
chemical.
The top derivatives of Ethylene

Ethylene dichloride
Vinyl chloride
Acetic acid
Vinyl acetate
Ethylbenzene

7
Styrene
Ethylene oxide
Ethylene glycol

Fig. Synthesis of the top ethylene derivative chemicals

Nearly all ethylene dichloride is made into vinyl chloride, which is polymerized to the important
plastic poly(vinyl chloride) (PVC).Perchloroethylene (perc) is used as a dry cleaning agent a
chemical intermediate , and a metal cleaning agent . Perc has a share of the dry cleaning
business. Methyl chloroform is one of a few chlorinated compounds that has low toxicity, but it
is being phased out because of its ozone depleting potential. Sometimes called "1,1,1," it is used
as a chemical intermediate , a metal cleaning agent , and as an ingredient in adhesives, coatings,

8
and inks . Vinylidene chloride is polymerized to a plastic. The ethylenediamines are used as
chelating agents, the most important being ethylenediaminetetracetic acid (EDTA).

2.2.3 Chemicals from Propylene

The official production of propylene is usually about half that of ethylene, only because a large
part of the propylene is used by petroleum refineries internally to alkylate gasolines. Of the
propylene used for chemical manufacture, nearly 40% is polymerized to polypropylene.The
other top chemicals derived from polypropylene are :

 Acrylonitrile
 Propylene Oxide
 Cumene
 Phenol
 Acetone
 Bisphenol A
 t-Butyraldehyde

9
 Fig. Synthesis of top propylene derivative chemicals.

2.4 Manufacture of Acetylene, Ethylene Oxide, Acrylonitile, Dimethyl

Therephthalate
2.4.1. Manufacturing Processes for Acetylene
A. Manufacture Based on Calcium Carbide
The worldwide production of calcium carbide from the strongly endothermic (AH = + 111 kcal
or 465 kJ/mol) electrothermal reaction between quicklime and coke at 2200-2300 o
C . Calcium carbide can be converted into acetylene and calcium hydroxide in an exothermic
reaction with H2O:
CaC2 + 2H2O → HC=CH + Ca(OH)2
B. Thermal Processes
Numerous processes for the manufacture o f C2 H are based on the uncatalyzed pyrolysis of
hydrocarbons in the C-range from methane to light petrol to crude oil. With newer process,
developments higher boiling fractions, residual oils, and even coal can also be used. In principle,
thermodynamics and kinetics have a deciding influence on the choice of reaction conditions
2.4.2 Manufacture of Ethylene oxide
Ethylene oxide (EO) and acetaldehyde are the most to significant partial Oxidation products
ethylene. They are isomeric. Largest volume application of ethylene (worldwide) is in the
manufacture of low- and high-density polyethylene
A. Ethylene Oxide by the Chlorohydrin Process
The two-step chlorohydrin process for the epoxidation of low olefins is rarely used with ethylene
today, though it is still used with propene . In this process, the non isolated ethylene chlorohydrin
intermediate was converted into ethylene oxide by heating with lime water:

10
B. Ethylene Oxide by Direct Oxidation
Partial oxidation of ethylene with silver catalysts is an exothermic reaction

11