RAW MATERIAL FOR ORGANIC CHEMICAL

INDUSTRIES
INTRODUCTION
Chemical process industry play an important role in the development of a country by providing a
wide variety of products, which are being used in providing basic needs of rising population which
is 6.4 billion globally and 1.2 billion in India in 2012. Chemical process industries uses raw
material derived from petroleum and natural gas, salt, oil and fats, biomass and energy from coal,
natural gas and a small percentage from renewable energy resources.
Although initially manufacture of organic chemicals initially started with coal and alcohol from
fermentation industry, however later due to availability of petroleum and natural gas dominated
the scene and now more than 90% of organic chemicals are produced from petroleum and natural
gas routes. However, rising cost of petroleum and natural gas and continuous decrease in the
reserves has spurred the chemical industry for alternative feedstock like coal, biomass, coal bed
methane, shale gas, sand oil as an alternate source of fuel and chemical feedstock.

ENERGY RESOURCES
Energy play vital role an important role for the development of any country and to meet the
challenges due to increasing population it has become one of the very important to optimize its use
and look for alternative energy resources. Coal remains the dominant source of energy meeting
52.4% of India’s prime energy needs while oil and natural gas met 41.6% of energy requirement
in 2008-09. Power sector accounted for 77% of the non-coking coal off-take. As per planning
commission projections till 2032, coal will continue to have a dominant share meeting over 50%
of primary commercial requirement [Dutta, 2011].
World and India Energy consumption scenario is given in Figure M-I 2.1 [Hindu Industrial
directory, 2007]. The world energy consumption had projected to increase by 58% over a 24 year
period from 2001 to 2025. The total energy use projected to grow from 404 in 2001 to 640

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quadrillion BTU in 2025 [Energy outlook, 2003]. India’s requirement for fossil fuels by 2030 is
estimated by various agencies is in the range of 337 to 462 million tones of oil, 99 to 184 million
tones oil equivalent of gas and 602 to 954 million tones of coal Indian energy’s [Hindu industrial
directory, 2007].

Nuclear Nuclear
6% Hydro 1%
Hydro 5%
6% Gas
8%
Oil Oil
37% 33%

Gas
24%

Coal
Coal 53%
27%

World 74.5 Bnbbl OE India 2.7 Bnbbl OE

Figure M-I 2.1: Indian Energy Scenario

RAW MATERIALS FOR ORGANIC CHEMICAL INDUSTRIES

Although initially manufacture of organic chemicals initially started with coal and alcohol from
fermentation industry, however later due to availability of petroleum and natural gas dominated
the scene and now more than 90% of organic chemicals are produce from petroleum and natural
gas routes. However, rising cost of petroleum and natural gas and continuous decrease in the
reserves as spurred the chemical industry for alternative feedstock like coal, biomass, coal bed
methane, shale gas, sand oil as alternate source of fuel and chemical feedstock. Table M-I 2.1 gives
the details of raw materials for chemical process industries. Raw materials for chemical industries
are classified as primary raw materials and basic intermediates. Although major organic chemicals
are produced from petroleum feed stock, however alternative raw materials are available which
are getting attention. Detail of feedstock for organic chemical industries is

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shown in Figure M-I 2.2. Table M-I 2.2 shows the details of natural gas and petroleum fractions
as petrochemicals feedstock. Alternative Routes to Principal Organic Chemicals is given Table
M-I 2.3
Table M-I 2.1: Raw Material for Chemical Process Industries
Primary Raw Materials:
Gaseous Natural gas, condensate, refinery gases, coal Bed
methane, gas hydrate
Liquids Naphtha, kerosene, gas oil, middle distillates
Solids Coal, coke, wax, residues
Oils and fats Tallow and coconut oil, palm oil and other oil
Biomass Alcohol, paper, energy,
Salt Chlorine, caustic soda, soda ash
Sulphur Sulphuric acid, fertilizer,
Lime stone Cement, lime

Basic Intermediates:
Paraffins Methane , propane, butane and higher hydrocarbons
Ethylene, propylene, butadiene , alcohol, vinyl chloride

Olefins and Ethylene, propylene,, butadiene , alcohol, vinyl chloride

derivatives
Aromatics Benzene Toluene Ethyl benzene, Xylenes, Naphthalene

Secondary Intermediates:
Monomer: Caprolactam, adipic acid, hexamethylene diamine, terephthalic acid and acrylonitrile
for synthetic fibres, intermediates for dye stuff industry and pesticides.

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Figure M-I 2.2: Feed Stock for Organic Chemical Industries

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Table M-I 2.2: Natural Gas and Petroleum Fractions as Petrochemicals Feedstock
Petroleum
Intermediate Intermediate
Fractions and Source Composition
Processes Feedstock
Natural Gases
Refinery Distillation, Methane, ethane, Liquefaction, LPG, ethylene,
Gases catalytic propane, butane, cracking propylene,
cracking, BP upto 25 oC butane,
catalytic butadiene.
reforming
Naphtha Distillation and C4-C12 Cracking, Ethylene,
thermal & hydrocarbon, reforming, propylene,
catalytic BP 70 - 200 o C alkylation, butane,
cracking, disproportiona- butadiene,
visbreaking tion, benzene, toluene,
isomerisation xylene
Kerosene Distillation and C9-C10 Fractionation to Linear n C10 - n
secondary hydrocarbon, BP obtain C10-C14 C14 alkanes
conversion 175-275 o C range
processes hydrocarbon
Gas Oil Distillation of C10-C25 Cracking Ethylene,
crude oil and hydrocarbons BP propylene,
cracking 200-400 o C butadiene,
butylenes
Wax Dewaxing of C8-C56 Cracking C6-C20 alkanes
lubricating oil hydrocarbon
Pyrolysis Ethylene Aromatic, alkenes, Hydrogenation Aromatics
Gasoline cracker dienes, alkanes, distillation,
cycloalkane extraction,
crystallisation,
adsorption
Natural Gases Gas fields and Hydrogen, Cracking, Ethylene,
& Natural Gas crude oil methane, ethane, reforming, propylene, LPG,
Condensate stabilisation propane, pentane, separation aromatics, etc.
aromatics
Petroleum Crude oil Carbon Residue Carbon
Coke upgradation electrode,
processes,gasifi- acetylene, fuel
cation

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 Table M-I 2.3: Alternative Routes to Principal Organic Chemicals
Chemicals Petroleum Source Alternate Source
Methane Natural gas, Coal, as by-product of separation of coke
Refinery light gases oven gases (1920-30) or of coal
(de-methaniser overheads) hydrogenation (1930-40)
Ammonia Methane From coal via water gas (1910-20)
Light liquid hydrocarbons
Methyl Methane From coal via water-gas (1920-30); from
alcohol Light liquid hydrocarbons methane (from coal) by methane-stream and
methane oxygen processes (1930-40)
Ethylene Pyrolysis of gaseous liquid Dehydration of ethyl alcohol (original route).
hydrocarbons By-product in fractional distillation of coke
oven gas (1925-35). Hydrogenation of
acetylene (1940-45)
Acetylene Ethane Calcium carbide (original process). methane
from coal by partial combustion and by arc
process (1935-45)
Ethylene Ethylene From ethylene made as above (1925). In
glycol America, from coal via carbon-monoxide and
formaldehyde (1935-40)
Ethyl alcohol Synthetic ethyl alcohol , Fermentation of molasses (original route)
Acetaldehyde Co-product of paraffin gas Fermentation of ethyl alcohol, or acetylene
oxidation. Direct oxidation of from carbide (1900-10)
ethylene
Acetone Propylene Wood distillation (original process). Pyrolysis
of acetic acid (1920-30) or by acetylene-
stream reaction (1930-40)
Glycerol Propylene By-product of soap manufacture (original
process)
Butadiene 2-Butenes Ethyl alcohol (1915); acetaldehyde via 1:3-
Butane butanediol (1920-30); acetylene and
Synthetic ethyl alcohol formaldehyde from coal via 1:4-butanediol
By-product of ethylene by (1940-45); from 2:3-Butanediol by
pyrolysis of liquid hydrocarbons fermentation (1940-45)
Aromatic Aromatic-rich and naphthenic- By-products of coal-tar distillation
hydrocarbons rich fractions by catalytic
reforming and direct extraction
or by hydro-alkylation

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ROUTES TO PRODUCE CHEMICALS
• Steam Reforming and Partial Oxidation (Synthesis gas (CO+H2 and H2& N) to produce
synthesis gas
• Cracking and Pyrolysis to olefins (C2H4,C3H6, C4H8 and olefins)
• By-products (Pyrolysis gasoline and Higher liquids, Gas condensate) for aromatics
• Catalytic Reforming to produce mainly BTX from naphtha.
• Dehydrogenation of Paraffin(Paraffin: ethane, paraffin) to produce olefin
• Petrocoke and Biomass gasification
• GTL(Gas to liquid), MTO (Methanol to Olefin),
• Coal to liquid fueland coal to chemicals
• Dehydrogenation (olefin) and alkylation (alkylate) from kerosene for LAB
• Saponification of oil and fats and recovery of chemical from glycerin

NATURAL GAS AS CHEMICAL FEED STOCK

 Chemicals from methane
 Chemicals from C2 – C4
 C5 + (natural gasoline)
 Methane/total natural gas

ROUTES FOR NATURAL GASES AS CHEMICAL FEED STOCK

 Cracking of natural gas to olefins, C4 and C5 chemicals
 Steam reforming and Partial oxidation for synthesis gas
 Conventional steam reforming
 Partial oxidation (POX)
 Catalytic partial oxidation (CPO)
 Combined reforming
 Combined reforming with performer
 Gas-heating reforming (GHR)
 Auto-thermal reforming
 Combined auto-thermal reforming (CAR)
 Kellogg heat reforming exchanger system (KRES)

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  Cyclar process: For production of aromatics fro natural gas (Propane and butane)
 Oxidative coupling of methane (natu al gas) to olefins

NAPHTHA AS CHEMICAL FEED STOCK

Naphtha is the most versatile chemical feedstock and its use depends on composition, boiling
range, end use market requirements. Naphtha remains prominent feedstock (52%) for olefin

production from steam cracker. Feedstock of olefins is shown in Figure M-I 2.3. Catalytic

reforming of naphtha produces aromatics which is important chemical feed stock for organic
chemical industries for producing synthetic fibre, pesticides explosive, dyes intermediate,

plasticizer, solvent etc. Some of the routes for conversion of naphtha to petrochemicals are
Steam reforming/ Partial oxidation of naphtha: For production of synthesis gas and
derivatives
Cracking of naphtha: For production of olefins, C4 and C5 hydrocarbons, pyrolysis
gasoline for aromatic production
Catalytic reforming of naphtha: For production of aromatics- benzene, toluene, xylenes,

Propan
p
Ethane, e, 8%
30% Butane,
4%

Others,
2%

Gas Oil,
4% Naphth
a, 52%
Production by Feedstock

Figure M-I 2.3: Olefin Feed Stock

KEROSENE AS FEED STOCK FOR LAB

n-Paraffins from SR Kerosene : n-Paraffins are extracted using adsorptive separation by
molecular sieves. These paraffins are excellent feedstock for LAB. Various steps involved are:
Kerosene Pre-fractionation: To tailor the kerosene to desired carbon range
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Hydrotreatment: To remove sulfur, nitrogen and olefins and oxygenates which might poison
the Molex adsorbent.

ALTERNATE FEED STOCK FOR CHEMICAL INDUSTRY

In view of dwindling fossil fuel sources and increasing cost of crude and volatile market oil, there
is tremendous activity all over world to utilize alternative feedstock’s alternative feedstock
includes biomass and algae, coal, petrocoke, waste plastic for production of synthesis gas, olefin,
methanol, ethanol and derivatives, naphtha.

BIOMASS
Biomass resources like crop residues, forage, grass, crops, wood residues, forest residues, short
rotation energy crops and cellulosic components of municipal solid waste can be use as alternative
feedstock for production of synthesis gas, ethanol, and naphtha through FT process. Alternative
energy resources will play a growing role and biofuels mainly ethanol are expected to grow
rapidly, reaching about 2% of total liquid supplies by 2030 [Singh et al., 2008]. Some of the routes
for conversion of biomass to heat & power, transport fuels, bioethanol is given in Figure M-I 2.4
[Banerjee et al., 2011].
The constantly depleting resources of conventional energy and the steeply escalating price of fossil
fuels have led to the need of alternate energy sources. Second generation production of bioethanol
production is gaining increasing impetus due to abundant availability, high cellulose d
hemicelluloses content of lingo-cellulose materials [Tuil et al., 2008]. Biotechnological route for
bioethanol production utilizing lingo cellulose material involves delignification, sacchrification
and fermentation. The most common process of bioethanol production from sacchrified lingo
cellulosics involves hydrolysis of cellulose and fermentation in the same reactor [Lo, 2009].
Options for Conversion of Biomass to Fuel and Power and Chemical feed stock is given in Figure
M-I 2.5.

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 Figure M-I 2.4: Biomass Conversion Technologies for Chemical Production

Figure M-I 2.5: Options for Conversion of Biomass to Fuel and Power and
Chemical feed stock
ETHANOL
There are three types of feedstocks for ethanol production [Tuli et al. 2008]
Sugars: Molasses, cane sugar, beat sweet sorghum and fruits
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Starches: Corn, wheat, rice, potatoes, cassava, sweet potatoes etc
Lignocellosic: Straw, bagasse, other agricultural residues, wood, energy crops
Algae: Ethanol production
Biomass can be also used a feedstock for methanol production and hydrogen through synthesis
gas produced from biomass gasifiers.

Ethanol from Algae

Direct to Ethanol technology, a novel technology developed by Algenol is in Pilot plant testing at
Dow Chemical’s Freeport, Texas to produce ethanol by photosynthesis from CO2, H2O and
sunlight instead of producing carbohydrates [Dutta, 2011]

COAL
Coal is another promising feed stock as huge amount of coal reserves is available in India and
other part of the world. Based on the production of coal gasification unit it will be possible to to
produce large number of chemicals. Possibility Coal as a source of petrochemicals, which again
explored all over the world [Handa and Ganesh, 2010]
Coal was the original feed stock for production of large number of chemicals through coke oven
plants, synthesis gas from gasification, acetylene fro calcium carbide route. However, due to
availability of petroleum based raw material presently more than 90% of chemicals are produce
from petroleum and natural gas. Due to volatile market of crude oil and dwindling petroleum
resources, coal is emerging as alternative feedstock for chemical industry as huge coal reserves are
available all over the world. Various routes for utilization of coal as chemical feedstock and fuel
are [Duchesne, 2011, Patil, 2009, Furimsky, 1999]:
 Gasification
 Coal to fuel through FT process
 Coal to methanol technology, Liquid phase Methanol process from coal (LPMEOHTM)
 Methane to MTO plus Olefin cracking process (OCP)

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  Coal to Olefin technology
 Coal to Plastic technology

PETROCOKE
Due to the use of heavy crude oil, huge amount of petrocoke is being produce from the
thermal cracking process in the refinery. Although petrocoke is being used as fuel in
cement industry however it can be a promising raw material for production of synthesis
gas, hydrogen, methanol through petrocoke gasification. Through FT synthesis the
synthesis gas can be converted to fuel also. Utilization of petrocoke offers an alternative
to handle high sulfur and metal containing residues in a refinery with value addition.
Reliance is already in process of implementing petrocoke gasification to utilize its
petrocoke.

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