CH216

INDUSTRIAL CHEMISTRY II
Definition of industrial Organic Chemistry
• It is that discipline of chemistry, that is mainly concerned with large scale production of organic
chemicals and chemical products for the economic benefit.

• The chemical industry comprises the companies that produce industrial chemicals. Central to the
modern world economy, it converts raw materials into more than 70,000 different products.

• Industrial chemists work with chemical engineers to turn breakthroughs in chemical science

into mass-produced goods. The duties include improving existing chemical production technology,
methods, materials, and processes

• The chemical industry focusing on organic chemicals can be divided into a number of sub-
sectors and the most common are:
 Petroleum sector
 Plastics and plastic products
 Pharmaceuticals
 Herbicides and pesticides manufacturers
 Detergents and healthcare products
Production of Industrial Chemical and Processing of Raw Materials
• Industrial chemicals and raw materials are produced in dedicated chemical
plants.
• Process flow diagrams have been developed to understand various processes
taking at each unit and these are product specific.
• This is communicated through various process symbols.
• A process flow diagram is very important as it enables one to understand what is
happening at each production stage.
• In the next slides are some of the most common process symbols common is any
process flow diagram especially for the production of industrial organic chemicals
COMMON PROCESS FLOW SYMBOLS
Vertical fixed bed
Empty (reactor) Packing, e.g. reactor with one
vessel, vertical catalyst bed reactor and multiple
beds

Continuous
Multitubular Phase separator
Stirred Tank
reactor (based on density)
Reactor (CSTR)

Knock-out
drum Tray column Packed Column
 Heat exchanger (basic
symbol) Cooling (usually Heating (also
Process fluids with air or without circle)
Arrow shows direction of water)
heat flow

Heating by steam
condensation. Usually Furnace (heater) Compressor
as column reboiler & expander

pump
Filter Cyclone
Organic Chemical Raw Materials
• Raw materials for organic chemicals and chemical products can be classified into
non-renewable and renewable raw materials.

Fossil based Raw materials

• Crude oil based
• Natural gas
• Coal based raw material

Natural based organic chemical raw materials

• Plant/Agro-based raw materials
• Sugarcane (ethanol), biogas
• Vegetable oils (glycerine, bio-diesels,)
• Animal based raw materials
• Dairy products (lactic acid, cheese), Insulin, proteins, gelatine, biogas
Crude Oil
• The larger part of crude oil consists of alkanes, cycloalkanes, and aromatics.
• The heavier the crude the more polycyclic aromatic compounds it will contain.
heavier crudes yield a lower proportion of useful products.
• A further disadvantage of the heavier crudes is that they contain more
polynuclear aromatics (PNAs), which tend to lead to carbonaceous deposits
(“coke”) during processing.
• Crudes do also minor amounts of
so-called hetero-atoms are also
present, the major ones being sulfur,
nitrogen, and oxygen.
• Of these, sulfur is highly undesirable
because it leads to corrosion,
poisons catalysts, and is
environmentally harmful.
• Therefore, it must be removed
POLYNUCLEAR AROMATICS FOUND IN CRUDE OIL
Sulphur Containing Compounds in Crude Oil
Nitrogen containing compounds in crude oil
• Crude oils reserves are estimated at
1,650,585,140,000 barrel.

• Daily consumption are estimated at

35,442,913,090 barrel per day (47
yrs)

• According to the British oil company's

2019 Statistical Review of World
Energy report, Venezuela is the
leading country in terms of oil
reserves, coming in at 300.3 billion
barrels.
• Energy Outlook 2019 (IEO2019), the global supply of crude oil, other liquid
hydrocarbons, and biofuels is expected to be adequate to meet the world's demand
for liquid fuels through 2050ccording to the U.S. Energy Information
Administration's (EIA) International.
After it has been mined, crude oil must undergo the following processing

steps

• separate (by distillation or absorption)

• crack (breaking large chains of molecules into smaller ones)

• Re-shape (rearranging of molecular structure)

• combine (combining smaller molecules to make larger ones)

• treat (chemical removal of contaminants)

Coal Resources
• Estimated World coal reserves in 2018 stood at 1055 billion
tonnes and are heavily concentrated in just a few countries: US
(24%), Russia (15%), Australia (14%) and China (13%).

• Most of the reserves are anthracite and bituminous (70%).

• Coal is a mixture of high-molecular-weight polycyclic aromatic

compounds, such as benzene C6H6, toluene C6H5CH3, xylene
C6H4(CH3)2, naphthalene C10H8, anthracene C14H10, pyrene
C16H10 and their derivatives with high mass fraction of carbon, as
well as of water and volatile substances.

• Estimated depletion is 133 years

• Estimated Zim’s 2016 reserves 553,359,620 tonnes

Biomass as an alternative raw material
• There is an increasing global urgency to reduce the dependence on oil and other
fossil fuels.

• Biomass holds the promise of allowing a really sustainable development for the
production of energy, fuels, and chemicals.

• The present worldwide energy consumption corresponds to about 10% of the

biomass produced and in the year 2050 this number is expected to increase to 40%.

• Present agriculture cannot provide the amounts of biomass needed without affecting
the food and feed industries.

• Surplus land, which is not used for forestry production, nature reserves, or animal
grazing, has to be involved in biomass production; the good news is that this land is
available in the world.
Biomass and Biomass Processing
There are many sources of biomass for processing into value added
products (wood, garbage, agriculture, landfill gas and alcohol fuels)
• Conversion methods are:
 (1) biological, (2) physical, (3) chemical, (4) physic-chemical

Types of biomass Bio-mass processing

Natural Gas
• Natural gas is a mixture of hydrocarbons with methane as the main constituent.

• It can be found in porous reservoirs, either associated with crude oil or in

reservoirs in which no oil is present.

• Natural gas can be a source of energy as well as a raw material for the
petrochemical industry.

• Besides hydrocarbons, natural gas usually contains small amounts of non-

hydrocarbon gases such as carbon dioxide, nitrogen, and hydrogen sulphide.

• Estimated world reserves as of 2017 6,922,922,000 cubic ft

• Depletion at current production levels 52 years excluding future discoveries

Natural gas reserves of major producing countries
Production of Synthesis Gas
• Synthesis gas (syngas) is a general term used to designate mixtures of
hydrogen and carbon monoxide in various proportions.
• Can be produces from a variety of sources, mostly natural gas and coal.
• The following are the common processes
Reactions from Natural Gas
CH4 + H2O → CO + 3H2 (Steam Reforming) H= +206 kJ/mol

CO + H2O → CO2 + H2 (Water Gas Shift) H= -41 kJ/mol

CH4 + CO2 → 2CO + 2H2 H= +247 KJ/mol

CH4 → C + 2H2 H= +75 kJ/mol

2CO → C + CO2 H= -173 kJ/mol

2CH4 + O2 → 2CO + 8H2 (Partial oxidation) H= -36 kJ/mol

CH4 + O2 → CO2 + 2H2O H= -803 kJ/mol

2CO + O2 → 2CO2 H= -284 kJ/mol

2H2 + O2 → 2H2O H= 242 kJ/mol

 Removal of CO, CO2 and
Removal H2S adsorption on CH4 by adsorption
activated carbon
CO + H2O → CO2 + H2
CO + H2O → CO2 + H2

Simplified scheme for steam reforming process

Process description
• Natural gas is fed through a desulphurizer where
hydrogen sulphide is removed by adsorption.
• A desulphurizer is an adsorber filled with activated
carbon.
• Desulpurized natural gas is mixed with steam and fed
into a reformer heated at 500 oC.
• The natural gas-steam mixture passes through tubes
filled with catalyst. The gas mixture leaving the tubes is
Syngas plus other components (CO2 and methane).
• The impure gas mixture is fed into a pressure swing
adsorber where CO, CO2 and CH4 are removed.
• The gas exiting the adsorbers is pure hydrogen
• Process can be adjusted to produce purified syngas.
Autothermal Reforming Process
• In autothermal reforming, heat is generated in the
reactor by combustion of part of the feed with
oxygen;
• The product distribution changes to lower H2/CO
ratios.
• Autothermal reforming is the combination of steam
reforming and partial oxidation in a single reactor in
the presence of a catalyst.
• The reactor is a refractory-lined pressure vessel.
Therefore, higher pressures and temperatures can
be applied than in steam reforming.
• Part of the feed is oxidized in the combustion zone
(2200 K) lower part the remaining feed is
catalytically reformed with the produced carbon
dioxide and H2O (1200-1400 K, 20-100 Bar)
Coal Gasification
• Gasification of coal to produce syngas dates back to the end of the eighteenth
century.
• Use of this technology continued until the discovery of oil after the 2nd World
War.
• After the 1973 oil crisis, there is a renewed interest in coal gasification
technologies.
• In 2007, 49% of syngas produced by coal gasification was used to produce Fischer–
Tropsch liquids 32% as a raw material for the chemical industry, 11% for power
generation, and 8% for gaseous fuels.
• The application of coal gasification for power generation in a so-called integrated
gasification combined cycle (IGCC) is a relatively recent development.
Coal Gasification Technologies
Moving Bed Lurgi Gasifier
• The Lurgi (nowSasol–Lurgi) moving bed gasifier is operated
countercurrently;
• The coal enters the gasifier at the top and is slowly heated
and dried (partial pyrolysis) on its way down while cooling
the product gas as it exits the reactor.
• The coal is further heated and devolatilized as it descends.
• In the gasification zone, part of the coal is gasified into
steam and carbon dioxide, which is formed in the
combustion zone upon burning of the remaining part of the
coal.
• The highest temperatures (circa 1300 K) are reached in the
combustion zone near the bottom of the reactor.
Fluidized bed gasifier (Winkler, high temperature).
• The Winkler fluidized bed gasifier is a back-mixed reactor in
which coal particles in the feed are well mixed with coal particles
already undergoing gasification.
• The intensive mixing results in excellent mass and heat transfer.
• This gasifier operates at atmospheric pressure and moderate
uniform temperature.
• Char particles that leave the reactor with the product gas are, to a
large extent, recovered in cyclones and
• recycled to the reactor.
• Dry ash leaves the reactor at the bottom.
The Koppers–Totzek entrained flow gasifier
• The Koppers–Totzek entrained flow gasifier is a
plug-flow system in which the coal particles react
concurrently with steam and oxygen at
atmospheric pressure.
• The residence time in the reactor is a few
seconds.
• The temperature is high in order to maximize coal
conversion.
• At this high temperature, mainly carbon
monoxide and hydrogen are formed and hardly
any by-products.
• Ash is removed as molten slag.
• The entrained flow gasifier is the only gasifier that
can handle all types of coal.
Syngas Composition from Different Gasifiers Using Oxygen as Oxidant
Recent Development
Gasifier Technologies
• Shell Gasifier
• General Electric (GE),
• ConocoPhillips (COP)
gasifier
• Mitsubishi Heavy
Industries (MHI) Gasifier
Characteristics of some Important Entrained Flow Processes
Gasification Capacities
Application of Coal Gasification
Production of Low Calorific Gas (lean gas)
• This is usually used for heating or power generation.
coal→ CO/H2 → CH4
• Developments are however currently on hold due the discovery and exploitation
of very cheap shale gas.

Raw Material for the chemical Industry

• Syngas from coal gasication can be used for the production of liquid
transportation fuels, for instance in Fischer–Tropsch type reactions

coal → CO/H2 → hydrocarbons + alcohols

Production of hydrogen
• Syngas from coal gasification can be a source of hydrogen
coal → CO/H2 → water-gas shift → H2
Integrated Gasification Combined Cycle (IGCC)
• This is a relatively recent development in power generation.
• It consists of a coal gasifier and a combination of a gas turbine and a steam
turbine for power generation.
• The world’s first IGCC power plant of semi commercial size (253 MW), presently
owned by Nuon, has been successfully operated at Buggenum, The Netherlands, since
1994 and more plants have be built since then
IGCC Technologies
Basically there are three technologies and these are based on the gasifier
configuration:
• Entrained flow gasifiers, in which pulverized coal particles and gases flow
concurrently at high speed. They are the most common option for coal
gasification.

• Fluidized bed gasifiers, in which coal particles are suspended in the gas flow,
and therefore coal feed particles, are mixed with the particles undergoing
gasification.

• Moving bed gasifiers, in which gases flow relatively slowly upward through the
bed of coal feed.
General IGCC Process Description
• Coal particle and Oxygen from the air separation unit are ignited in a Gasier
• The gas from the gasifier flows into a gas cooler, after which particulates are
removed in a cyclone and candle filter.
• The gas is then sent to a gas cleaning unit, where, among other things, sulfur
compounds are converted into sulfur and removed which features a COS
hydrolysis and H2S absorption unit, a Claus plant a gas saturator, and a water
cleaning system.
• The purified gas is sent to the gas turbine, where it is burned with compressed
air to provide a stream of hot, high-pressure gas.
• The gas expands and conducts work on the turbine blades to turn the shaft that
drives both the compressor and an electricity generator.
• The exhaust gases from the gas turbine are sent to a waste heat boiler, where
high pressure steam is generated by heat exchange with boiler feed water.
• This steam is used in the steam turbine for the generation of additional electricity
Bulk Chemicals From Synthesis Gas
Methanol Production and Uses
• It is used as a solvent or as an
intermediate.

• It is also increasingly used in the

energy sector.

• The diagram on the left shows some

uses of methanol and also shows
that the chemical is in high demand.

• Worldwide, over 90 methanol plants

have a combined production capacity
of about 110 million metric
tons (almost 36.6 billion gallons or
138 billion liters).
Synthesis Gas for Methanol Production
• most syngas for methanol production is produced by steam reforming of natural
gas.
• The ideal syngas for methanol production has a H2/CO ratio of about 2 mol/mol.
• A small amount of carbon dioxide (about 5%) increases the catalyst activity.
• A H2/CO ratio lower than 2 mol/mol leads to increased by-product formation
(higher alcohols, etc.),
• a higher ratio results in a less efficient plant due to the excess hydrogen present
in the syngas, which has to be purged.
• The composition of syngas depends on the feedstock used.
Reactions in methanol Synthesis:
CO + 2 H2 → CH3OH rH298 = −90.8 kJ/mol

CO2 + 3 H2 → CH3OH + H2O rH298 = −49.6 kJ/mol

The two methanol forming reactions are coupled by the water–gas shift reaction:

CO + H2O → CO2 + H2 rH298 = −41 kJ/mol

Methanol Syntheses
• Initially, industrial synthesis were based on catalysts that
were fairly resistant to impurities but very active or selective.
• The heart of the process is a reactor with a circulation loop.
• Crude ethanol is distilled to separate from water and Multitubular Reactor

impurities (higher alcohols)

• The conversion per pass is low with facilitates good
temperature control
• Special reactors have been designed and the most common
are Quench and multitubular reactors
Quench Reactor
Simplified Process flow diagram for the production of Methanol
Technologies for Methanol Synthesis
The BASF Methanol Process
Process Conditions
(i) 320-380 oC
(ii) 340 bar
(iii) ZnO/Cr2O3 (ca 70:30)

• Cold gas is injected at may places in the catalyst bed to avoid temperatures that
would shift equilibrium away from methanol.
• Catalyst has a service life of several years and is resistant to poisoning at low
concentrations
• By-products, dimethyl ether, dimethyl formate and higher alcohols are separated
by distillation with low- and high boiling column.
• Residence time: 1-2 seconds (meant to suppress side reactions)
• Conversions per pass: 12-15%
ICI Low Pressure Methanol Production process
• Was first operated at pilot scale in 1966

• Today, about 65% of the world’s methanol production is based on the ICI
process.

Operating Conditions
i) Temperature 240-260 oC
ii) Pressure: 50-100 bar
iii) Catalyst: Cu-Zn-Al oxide

• An adiabatic reactor is used with a single catalyst bed.

• The reaction is quenched by adding cold reactant gas at different heights in the
catalyst bed.
ICI Process Description
• Fresh syngas is compressed and mixed with recycle gas.
• The mixture is heated with reactor effluent.
• Subsequently, about 40% of the stream is sent to the reactor after undergoing
supplementary preheating also by the reactor effluent.
• The rest is used as quench gas.
• The reactor effluent is cooled by heat exchange with the feed and with water
required for high-pressure steam generation, and then by passage through an
air-cooled exchanger in which the methanol and water are condensed.
• Gas/liquid separation is carried out in a vessel under pressure.
• The gas is recycled after purging a small part to keep the level of inerts (mainly
argon) in the loop within limits.
• The crude methanol is purified in two columns.
• The first column removes gases and other light impurities, the second
separates methanol from heavy alcohols (side stream) and water
ICI Low Pressure Methanol Process flow diagram
Production of Formaldehyde
• Accounts for about 35% of methanol consumption and is based on one of the
following reactions:

CH3OH → CH2O + H2 rH298 = 85 kJ/mol

2CH3OH + O2 → 2CH2O + 2H2O rH298 = −158 kJ/mol

• formaldehyde can be produced by dehydrogenation or by partial oxidation

Methods for Formaldehyde Production

• Silver Catalyst Process
• Metal Oxide Process
Silver Based Catalyst Formaldehyde Production
• Dehydrogenation and partial oxidation are often carried out over a silver-
based catalyst.
• A single reactor is used in which the heat produced by the exothermic partial
oxidation reaction supplies the heat for the endothermic dehydrogenation
reaction.
ACETIC ACID PRODUCTION
1. Fermentation of sugars
• Age-old process for the production of acetic and still the route for production
of vinegar.
• Sugars are fermented to ethanol followed by subsequent oxidation to acetic
acid.

2. Liquid phase oxidation of acetaldehyde

• Process first commercialized in 1916 and proceeds through a radical
mechanism as follows:
3. Direct Liquid Phase Oxidation of Naphtha or n-butane

2CH3CH2CH2CH3 + 5O2 → 4CH3COOH + 2H2O

• Was once the route for the production of acetic acid because of the low
cost of hydrocarbons.

• Major drawbacks are:

(i) 50% of the feed is converted to by-products such as formic acid,
higher acids and aldehydes which are of limited market value.
(ii) (ii) The process requires a very complex purification train, adding to
investment and operation costs

• Very small portion of acetic acid is manufactured by this route.

4. Hydroformylation of methanol

CH3OH + CO → CH3COOH

• First commercial plant was in 1963 when new cobalt/iodide catalyst

system was developed by BASF.
• In 1968 Monsanto introduced a carbonylation process using a novel highly
active and selective Rhodium based catalyst.
• Carbonylation accounts for 75% of the global acetic acid production.
• Further research and development work led to the development of the
Cativa Process by BP in 2000.
• The process uses iridium based catalysts which is much cheaper than
rhrodium
• The process operates under less severe conditions and yield are very
high.
Methanol Carbonylation
Monsanto Process for Acetic Acid Production
• Carbon monoxide and methanol are fed to a sparged CSTR containing the
catalyst (see next slide).
• Reaction takes place in the liquid phase under relatively mild conditions.
• Non-condensable by-products, mainly carbon dioxide and hydrogen, which are
formed by the water–gas shift reaction, are vented from the reactor.
• This vent gas is combined with off-gas from the light ends column and sent to a
scrubber to recover the volatile and toxic methyl iodide.
• Liquid is removed from the reactor through a pressure reduction valve and enters
a flash vessel, resulting in a gas and a liquid phase.
• The liquid phase, which contains the dissolved catalyst complex, is recycled to the
reactor. The gas phase, containing most of the acetic acid product, water, methyl
acetate, and methyl iodide, is sent to a distillation train for purification.
• In the light ends column, methyl acetate, methyl iodide and part of the water are
removed and recycled to the reactor.
• Wet acetic acid is taken as a side stream from this column and fed to the drying
column, where dry acetic acid is removed as bottoms product.
• The overheads of the drying column, containing a mixture of acetic acid (≈35%)
and water, are recycled to the reactor.

MONSANTO ACETIC ACID PRODUCTION PROCESS FLOW DIAGRAM

CATIVA PROCESS
• The reactor is not mechanically stirred; a
jet loop reactor is used, in which the
reactor contents are mixed by the jet
mixing effect of the cooling loop.
• A (finishing) plug-flow reactor is installed
after the first reactor for increased carbon
monoxide conversion.
• Because the iridium catalyst system is
stable at low carbon monoxide pressures,
a much lower water concentration (<8 wt
%) can be used.
• As a result, one less distillation column is
required and the light ends column and
drying column can be combined into a
single column.
Comparison on processes for acetic acid production
HYDROFORMYLATION
• Discovered by Otto Roelen in German and is also referred to as Oxo-Synthesis.
• In hydroformylation, a formyl group (CHO) and hydrogen atom are added to a
double bond as indicated in the reaction scheme below:

• Products of hydroformylation are intermediates for the production of several

types of alcohols.
Catalysts
• Hydroformylation catalysts are based on rhodium and cobalt.
• The first catalyst was developed in 1940 and was cobalt hydridocarbonyl
(HCo(CO)4 and was operated at high pressures of 200-450 bars
• In 1960 more more stable tributylphosphine-substitutes carbonyl catalyst
(HCo(CO)3P(n-C4H9)3 were developed.
• Further research led to the development of catalyst systems that could effect
hydroformylation reaction under mild condition yielding high aldehydes.
• In 1970 rhodium complexes modified with triphenylphosphine (TPP) ligand were
developed, i.e. HRh(CO)(PPh3)3
• Since 1980 rhodium cataysts with soluble ligands, triphenylphosphine-m-
trisulphonic trisodium salt (TPPTS) were developed.
Process for hydroformylation of propene
Low-Pressure Oxoprocess
• Reactions are catalysed by rhodium catalysts and by adding the right ligand, the
selectivity towards linear product is high.
• Reaction takes place in a continuous stirred tank reactor and much lower
pressure than the processes without modified cobalt catalyst.
General Procedure
• Gaseous reactants are fed to the reactor through a sparger.
• The reactor contains the catalyst dissolved in the product butryaldehyde and by-
products (trimers and tetramers). Rhodium catalyst remain in the reactor and
small amounts of it recycled.
• Gaseous effluent passes through demister in which fine droplets of catalyst that
are contained in the product gases are removed and fed back to the reactor.
• Reaction products and unconverted propene are condensed and fed to the
gas/liquid separator
• Propene apart from a small purge stream is recycled
• Liquid reaction prods are fed into a stabilizer column before subsequent
separation by distillation

Rhodium catalysed hydroformylation of propene (low-Pressure Oxo

Process)
Process with a bi-phasic Catalyst System
• The process is based on water-soluble rhodium catalyst developed by
Rhurchemie/Rhoné-Poulenc now Calenese.
• Catalyst contains polar ligands (sulphonated triphenylphosphines) which are
highly water soluble.
• Catalyst is however insoluble in the organic phases resulting in a bi-phasic
reaction medium.
• Before entering the reactor, syngas is passed through a stripping column to
recover unreacted propene.
• Liquid reactor effluent is fed to a separator where dissolved gaases are
removed and butryaldehyde are separated from the catalyst solution.
• The catalyst solution is returned to the reactor via a heat exchanger in which
steam is generated.
PROCESS FOR THE HYDROFORMYLATION OF HIGHER ALKENES
Conventional Cobalt based Processes
• First process was based on unmodified cobalt catalyst: Hco(CO)4
• The catalyst requires high pressures and temperature to ensure stability.
• Hydroformylation of higher is used to produce plasticizer and detergent range
alcohols and is still in use to this day.
• To minimize catalyst consumption and to avoid problems of downstream
processing, it is important that cobalt is recovered.
• This led to the development of the Kuhlmann (now Exxon-Mobil) process which
is based on the cobalt catalyst cycle:
2HCo(CO)4 + Na2CO3 → 2NaCo(CO)4 + H2O + CO2
• The sodium salt is water soluble. This enables the recovery of the cobalt
catalyst by scrubbing with water. The aqueous solution of cobalt as sodium salt
is transformed to active catalyst by reaction with sulphuric acid.
2NaCo(CO)4 + H2SO4 →2HCo(CO)4 + NaSO4
The complex is soluble in alkenes and can therefore be returned to the reactor
Low Pressure Cobalt based Process for Direct Product of Alcohols
PRODUCTION OF OLIFINS
Production of lighter olifins
• The main feedstock is derived from crude oil, through various thermal cracking
processes of which steam cracking is one of them.
• The main products of such processes are ethane, propene and butane.
• Treatment of light alkanes (ethane, propane and butane) by steam cracking
results in the formation of corresponding alkenes
• Generally the yield in alkanes increases with increase in temperature.
• From the diagram below, smaller molecules would require higher temperatures
than larger molecules.
• The conversion is favoured by lower partial pressures.
Mechanism of cracking of reactions
• The reaction takes place in three steps, namely initiation, propagation and
termination
Initiation
Involves homolytic cleavage of C-C bonding resulting in formation of methyl
radicals

Propagration
• Proceeds by reaction of methyl radical with
ethane, thereby forming methane and ethyl
radical.The ethyl radical decomposes forming
ethane. The hydrogen radical reacts with ethane
forming hydrogen and ethyl radical and so on.

Termination
Involves combination of radicals
Cracking of heavier alkanes/crude
• Similar, but more complex reactions accompany cracking of heavier.
• In this case, primary cracking products may undergo secondary reactions such
as further cracking, dehydrogenation and condensation.
• These secondary reactions mat lead to coke formation, the amount of which
depends on reaction conditions.
Industrial Process for steam cracking
• A mixture of hydrocarbons and steam is
passed through the tubes placed inside the
furnace heated by combustion of natural
gas, LPG, or fuel oil
• The furnace consist of the convection
section in which the hydrocarbons feed
and the steam are preheated and a
radiation section in which the reaction
takes place.
• The hydrocarbon undergoes rapid
cracking, subsequently, the products are
quenched to prevent further reaction
• The residence time is very short (<1 s).
Product distribution
• As for ethane as feedstock, it depends on process parameters such as
temperature, pressure, steam-to-ethane ratio.
• As for naphtha, no general product distribution can be given since they are
composed of a wide range of hydrocarbons ranging from C3-C15.
• However, naphtha composition expressed as percentage of alkanes,
naphthenes and aromatics present has a profound effect on the cracking yield.
Generally, alkanes are easy to crack compared to naphthenes and aromatic
hydrocarbons.
Steam cracker designs and configurations
Product Processing
• Processing of cracked gas depend on the feedstock
• Cracking gaseous feedstock is less complicated than from liquid feedstock
(naphtha and fuel)
• Product from gaseous feedstock is firstly cooled in the transfer line exchanger
and is subjected to multi-stage compression.
• Before the last stage compressor, acid gas components such as H2S and CO2
are removed.
• After the last compressor, water is removed by chilling and drying over zeolite
• The last stage involves fractionation by by cryogenic distillation at less than 273
K and pressures ranging 15-35 bar.
• Cryogenic separation is energy intensive as it requires refrigeration.
• The separation by distillation of ethane/ethane and propene/propane mixture is
very difficult require 80-150 trays for the former and 160 trays for the latter.
Ethene Oligomerization
• Initially lineae 1-alkenes where produced through thermal cracking process
of waxes (i.e. high molecular weight alkanes) or dehydration of 1-alcohols.
• Since mid-1970s C4-C18 have been produced by oligomerization of ethane
• Most of ethene oligomerization processes are based on Ziegler-Natta
catalyst.
• Yields by the SHOP process are very high compared to other process (see table)
Application of alkenes produced by oligomerization of ethane

Reactions of the SHOP PROCESS

• Oligomization is a catalytic chain growth reaction similar to polymerization but
the chains formed are much shorter.
• Key to oligomerization is the catalyst with a unusual ligand that allows
oligomerization but because of size inhibits chain growth to the polymer
• Oligomerization produces 1-alkenes ranging from C4 to C40 with even number
of carbons.
• However <C20 are favoured
• C10-C18 contain valuable intermediates
• C4-C8 fractions have limited commercial value
• The smaller chain alkenes (C4-C8) can be converted to higher chain fractions
(C10-C18) through double bond isomerization followed by a metathesis reaction
(see next slide).
Process Description of the SHOP PROCES
Catalysts
• Oligomerization reaction is carried out in a series of reactor (only one shown
below) in a polar solvent with rates of reaction being controlled by the rate of
catalyst control.

• Heat of reaction is removed by water cooled heat exchangers between reactors.

• Un converted ethane is separated from the taw liquid phases in a high pressure
separator and recycled.

• The catalyst solution is separated from 1-alkene products and fed back into the
oligomerization reactor

• 1-alkene are separated into desired product fractions in two distillation columns
• Firstly, the C4-C10 1-alkenes are stripped off

• Then C20+ fractions are removed from the C12-C18 1-alkenes which can be
separated into desired fractions or individual 1-alkenes.
• Part of C4-C12 fraction is combined with C20+ fraction to be isomerized and
subjected to metathesis.

• About 90% of the alkenes converted to internal alkenes by isomerization.

• Subsequent metathesis contains only about 11-15% per pass of the desired C11-
C14 linear internal alkenes.

• These are separated by distillations and can then be converted to detergent

alcohols by hydroformylation.

• The lighter alkenes are recycled to the metathesis reactor, while the higher
alkenes are subjected to isomerization and are recycled to extinction.
Products from ethylene
• Ethylene oxide and acetaldehyde are the most significant products of partial
oxidation of ethylene
• Ethylene oxide because of the strained ring is a very reactive chemical and
hence an important raw material for the production of a wide range
intermediates and consumer products.
• Ethylene oxide can be produced through:
 Indirect oxidation with intermediate ethylene chlorohydrin. The process is
expensive and has thus been largely abandoned.
 Direct oxidation of ethylene. This is now the most dominant process for the
production of million tons worldwide.
• The production of ethylene oxide worldwide is expected toexpand by 10 million
metric tons in five years, from 26 million metric tons in 2018, reaching
approximately 36 million metric tons in 2023.
Chlorohydrin Process
• The first process to be developed for the production of ethylene oxide.
• In this process, ethylene reacts with hypochloroous acid (a chlorine source)
to produce ethylene chlorohydrin in the first step.
• The ethylene chlorohydrin is converted with hydrated lime or coasting soda
to form the final product ethylene oxide.

• The process has been abandoned due to:

 High chlorine consumption
 High salt load
 Resulting unwanted chlorinated by-products
Direct Ethylene Oxidation
• The main reaction involve is the partial oxidation of ethylene in the presence of
silver catalysts.

• The reaction is normally accompanied by two side reactions, i.e oxidation of

ethylene and ethylene oxide product.

• Industrial processes attain a selectivity of 65-75% ethylene oxide

• Industrial catalysts generally contain up to 15% Ag on a support. Other catalyst
characteristics are proprietary and accounts for the large number of industrial
processes in existence today.
• Inhibitors such as 1,2-dichloroethylene are used prevent total oxidation and hence
improve on selectivity.
Process description
• The process can be oxygen or air based.
• The process is highly exothermic and requires careful removal of heat of reaction
to avoid local hot spots which cause loss of activity due to sintering
• A boiling liquid e.g. water circulates between the tubes of multi-tubular reactor and
function as heat transfer agent.
• The heat of reaction is used to generate medium pressure steam.
• When pure oxygen is used, typical conditions are 20-30 bar and 250-300 oC.
• Oxygen is kept at 6-8 vol-% to avoid combusting ethylene oxide
• Selectivity to ethylene oxide is 70-80% at an ethylene oxide conversion of 8-10 %.
• The work of reaction gases begins in an absorption column, where EO is washed
out with water
• EO is then driven out of aqueous solution with steam in a stripping column
(desorber) and fractionated in distillation columns
• EO/water mixtures are in part directly converted into glycol.
Products from ethylene oxide
• More 65% of ethylene oxide is converted to ethylene glycol.
• Ethylene glycol is expected to have a global production capacity amounting
to more than 65 million metric tons in 2024. That is a fairly significant
increase from the world's production capacity of ethylene glycol in 2019, which
was nearly 42 million metric tons.
• Ethylene glycol is used an anti-freeze for engines, for production of
polyethylene (PET)
• Diethylene glycol is applied in the production of polyurethane, polyesters,
softeners and plasticizers.
• The second largest use of ethylene oxide is the production of surface active
agents (e.g. non-ionic alkylphenol ethoxylate and detergent alcohol ethoxylate).
These surface active agents are used in household laundry and dishwashing
formulations.
• Further products from ethylene oxide are ethanol amines
Acetaldehyde from ethylene
• The process was developed between 1957 and 1959 by Wacker and
Hoest and hence the process is known as the Wacker-Hoest process
• The process involves an exothermic catalytic direct oxidation of ethylene
in the presence of noble metal catalysts.

• The catalyst is a two-component system consisting of PdCl2 and CuCl2.

• In 2020, market volume of acetaldehyde worldwide amounted to nearly
1.2 million metric tons. It is forecast that the market volume of this
organic compound will grow to around 1.6 million metric tons worldwide in
the year 2026.
• 85% of world production is achieved through the Wacker-Hoest process
Process Description
• Large scale manufacture of acetaldehyde takes place in a two phase
system (gas/liquid).
• The gaseous reaction components (ethylene and air/O2 react with the
acidic (HCl) aqueous catalyst solution in titanium or lined bible column
reactor.
• Two versions of the process were developed at the same time:
1. Single Step process: reaction and regeneration are conducted
simultaneously in the same reactor. Oxygen is used as a oxidizing
agent.
2. Two Step Process: In which reaction and regeneration take place
separately in two reactors. In this case, air can be used for the
oxidation
Single Step Process
• Ethyene and O2 are fed into the catalyst solution at 3 bar and 120-130 oC, where
35-45% of the ethylene is converted.
• Resulting heat of reaction is utilized to distil off acetaldehyde and water from the
catalyst solution, which must be recycled to the reactor
• In this way, 2.5-3.0 m3 H2O per ton acetaldehyde are recycled
• Pure O2 and Ethylene, to minimize losses which would result when discharging
accumulated inert gas.
Two-Step Process
• Ethylene is almost converter with the catalyst solution at 105-110 oC and 10 bar.
• After reducing pressure and distilling off acetaldehyde/water mixture, the catalyst
solution is regenerated with air at 100 oC and 10 bar in the oxidation reactor.
• Acetaldehyde is concentrated and by-products are removed by a two step
distillation.
• Selectivities of almost 94% are achieved
Vinyl Chloride
• Vinyl chloride is a monomer for PVC, and was produced by addition of HCl to
acetylene.

HCΞCH + HCl → H2C=CHCl

• The acetylene route fell out of favour for safety and economic reasons and was
superseded by ethylene based processes.
• Initially ethylene based processes involved chlorination of ethane, followed by
dehydrochlorination to vinyl chloride:
Disadvantage of the process:
 HCl is corrosive
 HCl value is small and must be used at the site of manufacture.
 Disposal presented economic and environmental problems.
 Half the chlorine was wasted
• Step 1: Producing ethylene dichloride (C2H4Cl2)
Chlorine is extracted from sea salt via electrolysis, and ethylene is derived from hydrocarbon raw
materials. These are reacted to produce ethylene dichloride (1,2-dichloroethane).

C2H4 + Cl2 = C2H4Cl2

• Step 2 - Producing Vinyl Chloride Monomer (VCM)

The ethylene dichloride is then decomposed by heating in a high temperature furnace or reactor.

C2H4Cl2 = C2H3Cl + HCl

• The hydrogen chloride is reacted with more ethylene in the presence of oxygen (a reaction known
as oxychlorination). The resultant ethylene dichloride is decomposed according to the above
equation, and the hydrogen chloride is again returned for oxychlorination.

2HCl + C2H4 + ½ O2 = C2H4Cl2 + H2O

= C2H3Cl + HCl2 + H2O
• The overall reaction can be shown by adding together the above equations:
2C2H4 + Cl2 + ½ O2 = 2C2H3Cl +H2O
Production of Propylene Oxide
• Like ethylene oxide, propylene oxide is a raw material of a number of
intermediates.
• Propylene oxide is less toxic than ethylene oxide.
• Two major processes for the manufacture propylene oxide are:
 Chlorohydrin Process and accounts for 39% for the world capacity
 Indirect oxidation of propylene oxide and accounts for 51% combined world
capacity.
• A recent developments involve the manufacture of propylene oxide via catalytic
epoxidation using H2O2, and hydroperoxidation of cumene and propylene.
• Direct oxidation of propylene is less efficient and results mainly in the formation of
acrolein and total oxidation.
• In 11 years, the global production capacity of propylene is expected to expand
from 130 million metric tons in 2019 to approximately 192 million metric tons by
2030, mostly due to propylene production plants expected to open in Asia and the
Middle East during that timeframe
Chlorohydrin Process
• The process is achieved in two reaction steps:(i) Chlorohdrination, (ii)
Dehydrochlorination.

• In chlorohydrination step, the 1. Chlorihydrination

H3C H
reactants, are converted into two + 2HOCl
propylene chlorohydrin isomers (90% H H

1-chloro-2-propanol and 10% 2-

chloro-1-propanol) OH Cl
H3C C C H
• In the 2nd step, the aqueous H H 2. Dehydrochlorination
propylene chlorohydrin is treated with Cl
+
H O
slaked lime and caustic soda leading H3C C C OH
+ Ca(O H) 2 H
+CaCl 2 + 2H2O
to formation of propylene oxide and H H
H3C
H
H

corresponding inorganic salts. + 2 NaO H

O H
+ 2NaCl + 2H 2O
• Yields of 96% can be achieved. H3C
H
H
Process description
• In the chlorohydrin reactor, gaseous propylene and chlorine are mixed with
excess water and propylene chlorohydrin is formed at 30-50 oC and 2-3 bar.
• Reaction products remain in aqueous solution, and water, acting as a diluent
minimizes formation of by-products.
• Water also act as a reactant and cooling medium.
• In the separator, the vent gas is removed from the propylene chlorohydrin
solution and sent to a scrubber unit.
• The aqueous reaction solution is sent to the saponifier where lime or NaOH are
added. In the saponifier, dehydrochlorination takes place leading to optimal
formation of propylene oxide
• To avoid hydration, propylene oxide is removed from the reaction mixture by
stripping with steam and sent to the distillation column
• Crude propylene oxide is distilled and propylene oxide is collected as a light end
product.
Summary of Methods of Producing Propylene Oxide
Uses of Propylene Oxide
• PO is an important basic chemical intermediate. Virtually all the PO produced
is converted to derivatives often for applications similar to those of EO.

• PO is used primarily to produce polyethers, polyols, propylene glycols,

polypropylene glycol ethers and many other usefuful products.
Benzene and Production of Benzene Derivatives
Benzene and Production of Benzene Derivatives
• Benzene is the most important precursor for many various intermediates and for
the cycloaliphatic compounds.
• 75-90% of benzene is converted to ethylbenzene, isopropyl benzene and
cyclohexane.
• Alkylation is a preliminary step to production of styrene (vinyl-benzene) and
phenol.
• Hydrogenation is preliminary step to production of cyclohexanone and
cyclohexyl alcohol.

Alkylation and hydrogenation Products of Benzene

Ethylbenzene
• Most is manufactured by alkylation with ethylene
• Small amounts can be obtained from super fractionation of C8 aromatic cuts.
Processes for the production of ethyl benzene
Liquid-phase ethylation in the presence of Lewis acids
• This performed in the presence of Friedel-Crafts catalysts such as:
• AlCl3, BF3, FeCl3, ZrCl4, SnCl4, H3PO4 or alkaline earth phosphates.
• Alkylation of benzene with ethylene is carried at 85-95 oC and a slight pressure (1-7 bar).
• 0.6:1 mixture of ethylene and benzene is continuously fed into the bottom of the
alkylation column, while catalyst (AlC3) is introduced periodically at the head of the
column.
• Simultaneously, little ethyl chloride is added as promomoter and the by-product HCl acts
as a co-catalyst for AlCl3.
• 1kg AlCl3 catalyst is required per 100 kg ethyl benzene.
• Multi-ethylated benzene can be dealkylated in special reaction with AlCl 3 at 200 oC
before being recycled to the reaction and hence increase ethybenzene selectivity to 94-
96%.
• Reaction mixture consisting of 45% benzene, 37% ethyl benzene, 15% diethyl benzene
and 1% tarry residues is separated into its components in a 4 column distillation unit.
Process flow diagram for the production of ethyl benzene
Gas Phase Alkylation of Benzene
• The ethylation of benzene is carried ou tat 300 oC and 65 bar over acidic catalysts
such as Al2O3∙SiO2 (Koppers Process), H3PO4/SiO2 (UOP).
• To avoid further alkylation at high temperatures f the gas phase process, the mole
ratio of ethylation to benzene must be adjusted to 0.02:1, i.e benzene must be in
excess
The Mobil-Badger Process
• The reaction is performed in the presence of aluminium silicate (zeolite ZSM5), at
435-450 oC and 14-28 bar.
• The catalyst is re-generated after 2-4 weeks and hence the reactor section in the
plant must be duplicated.
• Achievable conversion is 85% with ethyl benzene selectivity of 98%.
• Produced ethyl benzene is exclusively used for the production of styrene
• In the five year period from 2018 to 2023, the global production capacity of ethylbenzene
is forecasted to experience a considerable growth, from around 39 million metric tons in
2018 to approximately 48 million metric tons in 2023.
Production of Styrene
• The main manufacturing process for styrene is the direct hydrogenation of
ethylbenzene.
• Initially, catalyst systems were based on three component system of ZnO, Al2O3
and CaO.
• Today, they are based on iron oxide, Cr2O3 with KOH or K2CO3 acting as
promoters.
• The reaction is performed in multitubular reactor packed with the catalyst
• Conversion ranges 60-70% and selectivity 85-90%
• The catalyst life is 2-4 years.
• For the industrial production, both isothermal and adiabatic dehydrogenation
processes are used.
BASF Dehydrogenation Process
• The BASF is an isothermal ethylbenzene dehydrogenation process (see
process flow diagram in next slide.
• Ethylbenzene and low pressure steam are fed into a vaporizer, heated in heat
exchangers to over 590 oC and then passed into a reactor.
• A multi-tubular reactor is used and heated by flue gases at 720-750 oC.
• Reactor product, leaving the reactor at 580 oC is cooled in heat exchangers
and the ethylbenzene vaporizer to 160 oC and condensed in a air cooler.
• The crude styrene contains 60-65% styrene, ethylbenzene and higher boiling
aromatics
• Other smaller fractions are benzene and toluene.
• The reaction gas consists approximately 90-95% hydrogen
• Crude styrene is purified in a series of distillation trains.
Adiabatic process
• The dehydrogenation of ethylbenzene is carried out in two stages.
• Ethylbenzene and steam (ca 15%) are heated to 550 oC.
• Additional superheated steam at 720oC is fed so that the mixture enters the
first reactor at 630-640 oC and some 35% ethylbenzene is converted.
• In the second stage, further dehydrogenation occurs, following additional
superheating to 640 oC.
• The styrene content in the reaction product is 60-65 oC
• Purification is carried out at the lowest possible temperature under vacuum to
avoid polymerization.
• 4-tert-butylcatechol are added to prevent polymerization.
• Process flow diagram for the distillation of crude styrene is shown in the next
slide.
Production of Cumene

• After ethylbenzene, cumene (isopropylbenzene) is the most important

derivative of benzene.
• It is produced by benzene alkylation
• Recovery from coal or petrochemical streams is uneconomical.
• The compound gained technical importance following the discovery of
phenol synthesis via oxidation.
• Cumene can also be produced by reaction of benzene and isopropyl
chloride in the presence of aluminium filings and dry hydrogen chloride and
a yield of 66% is achievable.
Alkylation of benzene with propylene
• Process is carried out in a similar way as the benzene/ethylene alkylation
• Generally excess benzene is used to minimize formation of highly alkylated
products
• The reaction is performed either in the gas phase or in the liquid phase.
• Alkylation in the liquid phase can be achieved in the presence of H2SO4 or
AlCl3 at 30-40 oC
• It can also be achieved in the presence of HF at 50-70 oC at propylene
pressures of upto 7 bar
• Gas phase alkylation benzene/propylene (5:1) takes place in the presence of
H3PO4/SiO2 catalyst at 250-350 oC and pressures of 30-45 bar.
• The reaction is carried out in the presence of steam to achieve better control
of exothermic conversion.
• World production is approximately 15 million metric tons and most of is used
for the production of phenol and acetone.
Production of Phenol
• Coal tar is still an important source of phenol
• Requirements for phenol rose sharply with the use of picric acid as an explosive
during the Boer War (1899-1902) and World War I.
Phenol form Cumene
• Consumption of phenol also rose noticeably with increase in its importance as a
raw material for phenolic resins, for the manufacture of -caprolactam and
production of bis-phenol.
• Oxidative conversion of cumene into phenol and acetone is today the dominant
process and has proven to be environmentally friendly.
Process description
• Cumene is first oxidized at 90-100 oC and at a pressure of 6 bar by air, with
addition of soda solution (pH 7-8) to yield the hydroperoxide.
• Oxidation is carried out to a cumene hydroperoxide content of about 30%.
• Unconverted cumene is separated from the hydroperoxide by distillation
• The hydroperoxide is concentrated to 65-90 %.
• Catalytic cleavage of cumene hydroperoxide occurs with the addition of 0.1-2%
sulphuric acid (40%) at boiling temperature, whereby the reaction is cooled by
evaporation of acetone
• To minimize formation of by-products, the residence time restricted to 45-60 sec.
• Reaction products are neutralized with dilute caustic solution or phenolate lye.
• After separation of catalyst, the constituents are separated by distillation.
• High molecular tar residues are thermally cracked into phenol, -methylstyrene
and cumene. The remaining tar oil is used as the reaction medium.
• Methylstyrene, a by-product of the process is hydrogenated to cumene
Other Processes for phenol production
1. Benzene sulphonation and alkali fusion
2. Synthesis of phenol via benzene chlorination
3. Production of phenol by toluene oxidation
4. Recovery of phenol from products of coal pyrolysis
5. Recovery of phenol from carbolic oil.
Phenol derivatives
• Phenol displays a high reactivity than benzene due to the –OH group and
hence is used to produce a variety phenol derivatives.
• It is also used to produce phenol/formaldehyde resins

Bisphenol A
• This is produced by acid catalysed condensation of phenol and acetone.

• This phenol derivative is highly reactive and is used in the production of resins
• Other bisphenol derivatives are bisphenol F and S.
Process description for the production of bisphenol A
• The acid catalysed reaction is generally carried out at 50-90 oC with hydrogen
chloride or on sulphonated cross-linked polystyrene as a fixed bed, 15-fold
excess of phenol.
• When hydrogen chloride has been separated by distillation or neutralization,
bisphenol A crystallizes as an adduct with phenol.
• The adduct is thermally split by distillation.
• Subsequent refining is carried out by recrystallization from aromatic or
heptane/aromatic mixture.
• Yields of 80-95% can be obtained
• Other methods for producing Bisphenol A are:
 Reaction of phenol with methylacetylene on ion exchange resins.
 Reaction of isopropenylphenol with phenol in the presence of Friedel-Crafts
catalysts
Application of bisphenol
Production of epoxy resins

Production of polycarbonates

Production of high temperature resistant polysulfone plastic

 Cyclohexanol and cyclohexanone
• These compounds are produced from phenol as intermediates for synthetic
fibres (Nylon 6,6 and Nylon 6) via adipic acid and caprolactm respectively.
Production of Cyclohexanol
• Phenol is vaporized with recycled
and make-up hydrogen.

• It is hydrogenated in excess
hydrogen at 129-200 oC and 20 bar
on silica or aluminium oxide catalyst
which are modified with nickel.

• Cyclohexanol is separated by
condensation and the yield are
quantitative.
Cyclohexanone
• Cyclohexanone is produced by catalytic hydrogenation of phenol in the gas
phase at 140-170 oC on a catalyst bed at atmospheric pressure.
• Catalyst, generally contains palladium at concentrations of 0.2-0.5 wt% on
zeolites
• The yield is over 95%
Alkylated phenols
• Most important commercial alkylphenols are methylated derivatives (cresols and
xylenols), butylated phenols and alkyl chains.
Cresols
• These methylated derivatives of cresols can be produced from coal tar (40-59%).
• Sources of cresols are refinery streams arisng during processing of heavy
naphtha from cracker which contain 60% cresol.
• Third source is the coal gasification with tar by-products (SASOL)
• Cresol can be manufactured by alkaline hydrolysis of chlorotoluene prepared
according to the reaction scheme below

• The isomer mixture is hydrolysed in long tubular reactor under 280-300 bar at
390 oC yielding o-, m- and p-cresol in the ratio 1:2:1 respectively.
• Cresols (m- and p-) can also be synthesised by oxidation of cymene.
• Friedel-Crafts propylation of toluene at 60-80 oC in the presence of AlCl3 yield a
mixture of cymene

• Oxidation of cymene mixture is carried out via the hydroperoxide rould followed
by acid cleavage.
• The resultant mixture which predominantly 99.5% has a m-/p- ratio of 1.5:1.
Production of o-cresol and 2,6-xylenol
• The reacyion is carried out in the gas
phases at 300-400 oC wilth Al2O3
catalysts in a multi-tubular reactor.
• After removing water, subsequent
distillation separates the dried mixture
into products anisole/phenol, 99%-
pure cresol and 2,6-xylenol
• Phenol and anisole are recycled.
• Higher alkylated phenols can be
recovered from the distillation residue
Uses of o-cresol
• Used in the production of 4-chloro-o-cresol.
• Reacting 4-chloro-o-cresol with choroacetic acid or 2-chloropropionic acid lead
to formation of hormone –type herbicide such as 4-chloro-2-
methylphenoxyacetic acid (MCPA) and2-(4-chloro-2-methylphenoxy)-propionic
acid.
• Alkylation of o-cresol with propene yields carvacrol (2-methyl-5-
isoproplphenol) which I is used as an antiseptic.
• M-cresol is mainly used for the production of thymol, which is obtained by
isopropylation at 360 oC and 50 bar
• Hydrogenation of thymol leads to menthol, a component of fragrances with a
peppermint odor.
Production of Fenitrothion

• Fenitrothion is a synthetic organophosphate acetylcholinesterase inhibitor and

endocrine disrupter that is used as a pesticide.
• It is characterized as a volatile yellow brown oily liquid, and exposure occurs by
inhalation, ingestion, or contact.
• The manufacturing process involves nitrsation of m-cresol with nitrous acid
esters, and subsequent oxidation of the nitroso compounds with nitric acid to
yield 4-nitro-m-cresol.
• When t4-nitro-m-cresol is acted upon by O,O-dimethyl thiophosphoric acid
chloride, fenitrothion is formed.
 Other cresol derivatives

Fenvalerate Deltamethrin

BHT Phosphate esters

Chlorinated phenols
• Commonly used as intermediates for the manufacture of agricultural chemicals
• o-chlorophenol is obtained as the main product of chlorination with NaOCl/HCl.
• It is used for the manufacture of pentachlorophenol and the insecticide profenofos

• p-chlorophenol can be produced by reaction of phenol with sulfuryl chloride in the

presence of FeCl3 or AlCl3
• An important product of p-chlorophenol is the fungicide triadimefone, which is
obtained from -bromopinacolone and sodium p-chlorophenoxide with
subsequent bromination and final treatment with 1,2,4-triazone (see next slide)
Commercially most important polychlorinated phenols are:
Production of Toluene Derivatives
Introduction
• Toluene is a major product from catalytic reforming with a global production
exceeding 32 million mt.
• Only 1 million mt is consumed for chemicals while the balance is subjected to
hyrododealkylation and disproportionation to augment benzene and xylene output
(see reaction schemes below).

Uncatalysed is operated at 800 oC and

100 bar
Catalysed reaction is operated at 600 oC,
40-60 bar in the presence of oxides of Cr,
Pt, Mo or Co
• By-product methane is converted to synthesis gas and can be used to provide
hydrogen for hydrodealkylation.
• Below is another variant (see reaction scheme below) of hydrodealkylation which
involves disproportionation and transalkylation.
• The reaction is an important source for for mixed xylenes and is carried out in the gas
phase in the presence on nonnoble metal catalyst.

• A third possible approach, is a transalkylation which involves interaction of toluene

with mesitylene (a compound produced during cat. Reforming.
• In this reaction a methyl group migrates from mesitylene to touene giving two
molecules of xylenes
Nitration of Toluene
• Nitration leads to formation of a mixture of nitro-compounds depending on
reaction conditions.
• Industrially, nitration is carried out at less
than 60oC to limit both methyl group and
aromatic neucleus being oxidatively
attacked.

• Mono nitration is carried out between 30 and 45oC and three monomers are
formed (see reation scheme above). Production capacities exceed 200,000 tpa
• At higher temperatures by the following by products are formed.
Mononitrotoluenes are further nitrated to obtain six possible dinitrotoluene in the
following rations 2,4-isomer (74-76%), 2,6-isomer (19-21%) and negligible
amounts of other isomers.
CH3 CH3 CH3 CH3
CH3 CH3
NO 2 NO 2 NO 2 O N
2 NO 2

NO 2 O 2N
O 2N NO 2 NO 2
NO 2
NO 2

Dinitrotoluenes are dissolved in MeOH and hydrogenated continuously to diaminitoluens at 150-

180 oC and 65-130 bar. Other catalysts such as Pt and Pd can be used as substitute.

CH3
H 2 /N i CH3
NO 2 CH3 -
150 180°C NH2 CH3
O 2N NO 2
+ 65 - 130 bar
H2N NH2
+
NO 2
NH2
Production of diisocyanates
• Diaminotoluenes are converted to diisocyanates by reaction with phosgene and
intermediate isomeric carbamoyl chlorides are formed.
• Carbamoyl chloride is formed at 0-30 oC and diisocyanate formation occurs at
160-180 oC.
• Conversion is about 80%.
• Treatment of residue with alkali provides for unreacted diaminotoluenes to be
recycled

Diisocyanates are important isomers for the production of

polyurethane plastics
Production of metolachlor
• 2-Toluidine is ethylated with organometallic aluminium reagents.
• The resultant 2-ethyl-6-methyl-aniline in made to react with 2-chloro-1-
methoxypropane and
• the reaction product is condensed with chloroacetyl chloride.

CH3 NH2
NH2 H5C2 CH3
(C 2 H 5 ) 3 Al

C2H5 Cl C 2H 5 CH3
CH3
H3C
NH2 N CH3
H
CH3 CH3

C 2 H5 CH3 O
C2 H5 CH3
Cl
N CH3 Cl

H N CH3

CH3
CH3 O Cl

M eto lachlo r
Production of and Uses o Xylene Derivatives
O-Xylene and derivatives
Phthlic Acid Productio
Background
• Phthalic acid was discovered by the French chemist Auguste Laurent in 1836.
• Commercial production of PA was taken up BASF in 1872
• The process involved oxidation of naphthalene with manganese dioxide and
hydrochloric acid and was used as base material for the production of dyes.
• Major setback was that yield were very low even under drastic conditions
involving use of concentrated acid.
• Further R&D work by BASF led to the development operating at low
temperatures with yield of upto 87%.
• The process involved use of cylindrical catalyst containing vanadium pentoxide,
20-30% K2SO4 and 60-70% POROUS SILICA.
• Reaction was carried out in multi-tubulor reactor
• About 1945, production of PA from oxidation of o-xylene was developed in USA
• The catalyst was a low porosity which was coated with 7-8% molten V2O5.
Production of phthalic acid
• Today the production of phthalic acid is from both naphthalene and o-xylene.
• A distinction is made between low temperature process (BASF catalyst, von
Heden catalyst) and high temperature processes, which are operated at 450
o
C.

• Commercial oxidation of o-xylene in a fixed bed is exclusively carried out in

multitubular reactors.

• The most common catalyst is vanadium pentoxide, the reactivity of which is

modified by the addition of salts (e.g. K2SO4) and oxides e.g. TiO2 and by the
shape of the surface coated catalyst.

• In place of the earlier cylindrical catalysts pellets, spherical pellets with smooth
or porous surface made from MgSiO3, quartz or SiC are used to obtain high
space velocities.
REACTION SCHEME FOR OXIDATION OF o-XYLENE
Low Temperature Process (BSAF Process)
• o-Xylene is fed into the multi-tubular reactor with air which has been pre-heated to
150 oC.
• Heat of reaction is removed by means of a salt bath of KNO 3/NaNO2 (59/41%) with a
melting point of around 141 oC and is used to generate high pressure steam.
• The hot reaction gases leave the reactor at a temperature of 350-450 oC and are fed
to the gas separator.
• Cooling to separate the crude phthalic anhydride and heat for melting are provided
by a heat transfer oil.
• Before the final upgrading by distillation, the crude phthalic anhydride is thermally
pre-treated at temperatures of 230-300 oC in a pre-condenser.
• This causes by-products (maleic anhydride, 0-tolualdehyde etc) to be partly
decomposed, resinified of driven off.
• The heat pre-treated crude phthalic anhydride is fractionated in continuous
distillation columns
• Yield is approximately 80%
Production of Phthalic Esters
Phthalic esters are the most important industrial plasticizers and are prepared from
most commercially available aliphatic or cyclic alcohols.
Most common alcohols are: isooctyl-, isononyl-, straight chain C7-C9 alcohols.
Below are characteristic properties of phthalic esters
Reaction scheme below depicts a two stage esterification of phthalic anhydride
• The reactions are mostly acid catalyst

• Production of phthalic esters is acid catalyzed and is carried out in a stirred

reactor.
• Using isooctyle example, PA and the alcohol are fed in the molar ratio of
1:2.5.
• The resulting reaction water is distilled azeotropically with the alcohol acting
as an entrainer
• On completion of reaction, traces of uncoverted monoester are neutralized by
alkali.
• Further processing results in the isolation of pure purer product.
PROCESS FLOW DIAGRAM FOR THE PRODUCTION OF
PHTHALIC ESTERS
Other Phthalic Anhydride Product
Quinophthalone

Phthalonitrile

Copper phthalocyanine
Phthalimide O
O
NH 3
220 - 280 °C
O NH
Yield 98%

O O

Folget (Fungicide)

Anthranilic acid
Nitration o-Xylene
HNO 3 /H 2 S O 4 O 2N CH3 CH3
CH3 H2N
T= 30°C H2

CH3 CH3
CH3

• Nitration of o-xylene takes place at 30 oC

• The separation of isomers is by distillation and crystallization.
• Formed 3,4-dimethyl nitrobenzene can be reduced to 3,4-xylidine
• 3,4-xylidine is a raw material for the production of riboflavin (vitamin B2)
Oxidation of p-Xylene: Terephthalic Acid (TPA)and Dimethyl terephalate
DMT) Production.
• TPA and DMT are common monomers for the production of polyethylene
terephatalate (PET) by polycondensation with ethylene glycol (see reaction
schemes below)
Production of Terephthalic acid
• Old method involves oxidation with nitric acid as shown in the reaction
scheme:

• Reaction Conditions:
• T=165 oC
• P=10 bar
• Yield: 40%

• The terephthalic produced through this route had nitrogen compounds as

impurities and hence required further purification.
O OH
CH3

+ HNO 3

CH3
O OH
Current Production Methods
Amoco Process
• Liquid-phase oxidation of p-xylene with air.
• Xylene, acetic acid, air and catalyst (e.g. cobalt acetate, NaBr, CBr 4) are
continually fed in to the reactor.
• Oxidation occurs at temperatures ranging from 175 to 230 oC and pressures
of 15-35 bar.
• Heat of reaction is removed by vaporizing acetic acid and is fed back into
the process.
• Residence time ranges from 30 minutes to 3 hours depending on process
conditions and conversion is over 95%.
O OH
CH3

+ O2

CH3
O OH
Process flow Diagram of the Amoco Process for Terephthalic Acid Production

Refining of crude TPA

• Crude TPA contains a number of by-products, compounds with one
functional group such as benzoic acid and methylbenzoic acid
• Crude TPA is slurried with water and after being heated to 250 oC, the slurry
is pumped into hydrogenation reactor, which contains a noble metal catalyst
(e.g. Pd) on carbon carrier
• The liquid-phase hydrogenation removes impurities which have a tendency
to discolour.
Production of Dimethyl terephthalate
• The process is carried out because of the difficulty in producing terephthalic
acid for polymerization.
• The reaction scheme is illustrated below”

• The process involves oxidation of p-xylene to p-methylbenzoic acid followed

by esterification with methanol.
• In the next step, the second methyl group is oxidized resulting in the
formation of terephthalic acid monomethyl ester which is converted to the di-
ester, dimethyl terephthalate by further adding of methanol.
PROCESS FLOW DIAGRAM FOR THE PRODUCTION OF DIMETHYL
TEREPHTHALATE USING THE DYNAMIT NOBEL/WITTEN PROCESS
PROCESS DESCRIPTION OF THE WITTEN PROCESS
• P-Xylene, air and catalyst are fed continuously into the oxidation reactor, to
which recirculated p-methylbenzoic acid methyl ester is added.
• Oxidation is effected at temperatures of 140-170 oC and a pressure of 4-7 bar.
• Heat of reaction is removed by evaporization of water and excess p-xylene.
• Further reaction with methanol is carried out at 200-250 oC under slightly
raised pressure (20 bar) in the esterification reactor to keep the mixture in the
liquid phase.
• Esterification products flow to the crude column, where p-methylbenzoic acid
methyl ester is separated from crude DMT
• p-Methyl benzoic acid is recycled to the oxidation reactor where oxidation of
the 2nd methyl group occurs.
• The crude DMT is purified to fiber grade quality by distillation and
crystallization with MeOH, and subsequent re-distillation in a column with 30
trays.
• The yield is about 87%
The Henkel I Process
• The process was operated in the 1970.Phthalic snhydride is converted to the
dipotassium salt of phthalic acid.

• In the next step, the dipotassium salt is isomerized to dipotassium terephthalate

under a pressure of carbon dioxide (10-50 bar) at a temperature of 350-400 oC.
The Henkel II Process
• Toluene is oxidized in air over a cobalt catalyst to yield benzoic acid which is
transformed to potassium benzoate by subsequent neutralization.
• In the presence of cadmium oxide or zinc oxide, at temperatures of 450 oC and
under carbon dixide pressure, disproportionation to dipotassium terephthalate
occurs.
• This is then converted into terephthalic acid
• Benzene is the by-product of disproprtionation.
m-Xylene and its derivatives
• M-Xylene application is limited to the production of isophthalic acid, nitrated
m-xylenes and m-xylene diamines

Production of isophthalic acid

• The oxidation process is based on the liquid phase oxidation for the
production of terephthalic acid (TPA).

• Air oxidation is conducted in acetic acid in the presence of cobalt and

manganese salts and bromine, at temperatures ranging from 170-230 oC and
pressures of 20-25 bar.

• Following the reaction, isophthalic acid is separated by crystallization and the

mother liquor is recycled.
Production of isophthaloyl chloride
• Isophthaloyl chloride is an important derivative of isophthalic acid
• It is produced by chlorination (SOCl2/Cl2) of m-xylene via the intermediate
1,3-bis-(trichloromethyl)-benzene and its reaction with isophthalic acid.
• Isophthaloyl chloride, along with m-phenylenediamine, serves as monomer
components for the production of the high-strength and heat-resistant fiber.
Production of m-xylenediamine
• M-xylene can be converted into isopththalodinitrile with NH3 and air
• Isophthalodinile is transformed into m-xylene-diamine by hydrogenation

• Uses
• Curing agent for epoxy resins
• Monomer component in the production of special polyamides
• Chlorination of isophthalodinitrile leads to formation of the fungicide
tetrachlorophthalodinitrile (chlorothalonil)
CN
CN
Cl Cl
C l2
-H Cl
Cl CN
CN
Cl
Edible oils, fats and waxes
• These are naturally occurring esters of long straight-chains of carboxylic
acids and belong to a saponifiable group of lipids.
• Saponifiable lipids contain an ester group and react with hot sodium
hydroxide solution undergoing hydrolysis (Saponification)
• Saponification is a chemical process in which an ester is heated with an
aqueous alkali to form an alcohol and sodium salt of the corresponding
ester. The sodium salt is called SOAP.

• Fats and oils are esters of glycerols in which each of the three hydroxyls
groups has been converted to an ester
• Triesters are known as triglycerides.
• The differences among triglycerides are because of the length of the
hydrocarbon chain and the number of position double bonds.
• Hydrocarbon chains may be completely saturated or may contain more double
bonds.
• Waxes are monoesters of long-chain fatty acids usually containing 24-28
carbon atoms with long-chain fatty primary alcohols.
• A fatty alcohol has a primary alcohol (-CH2OH) attached to 16-36 carbon
atoms long chains
• Waxes are normally saturated.
Sources of edible Oils and Main Fats
• Hundreds of plants and animals produce fats and oils in sufficient quantities to
warrant processing into edible oils (see table below)
General edible oil processing steps

Whole seed Grading & Cleaning Extraction

Purification Crude Oil Extraction

Refined Oil Seed meal

In general, fats and oil undergo four processing steps

Refining
Extraction/rendering (Neutralization or
Degumming)

Deodorization Bleaching
Extraction
• Fats and oils are extracted from either plants or animals
• For example, the adipose tissue of the pig is heated, melts the fat and it is
further processed
• Butter is made by reversing the oil in water emulsion of cream into a water in
oil emulsion.
• Plant procedures involve a variety of different extraction methods.

• Types of extraction include:

 Rendering
 mechanical pressing
 Solvent extraction
Rendering
• Meat scraps are heated in steam or water to cause the fat to melt
• The melted fat then rises, water and remaining tissue settle below.
• The melted fat is then separated by skimming or centrifugation.
• A similar method is used for extraction of palm oil from fresh palm fruits.
• The fat can be obtained from any of the following three methods:
a. Dry rendering
b. Wet rendering
c. Low-temperature wet rendering
Mechanical pressing
• Pressing is used for oilseeds or fruit rich oils
• The oil bearing tissues are rolled, crushed or ground into flakes and the heated
by steam at 70 oC
• Various types of mechanical expellers or presses are used to squeeze oil from
oil seed.
• Seeds are usually first cooked slightly to partially breakdown the cell structure
and to melt the fat for easier release of oil.
• The heat from cooking or grinding should not be excessive as it may darken
the colour of the oil.
• With some seeds (e.g. corn) only the germ portion of the seed is pressed to
obtain oil, whereas with seed residues by being pumped through multiple filter
cloths or by centrifugal clarification.
Samples of oil expellers
Solvent Extraction
Common approach in large scale operations to remove the oil from cracked seeds
at low temperatures with a nontoxic solvent such as hexane,
The solvent is percolated through the seeds, and after the oil is extracted, the
solvent is distilled from the oil and recovered for re-use.
Combined processes employ pressing to remove most of the oil followed by solvent
extraction to recover final traces.
Oil free residual seed meal is then ground for animal feed.
Refining of crude oil
• Crude oils as received from the extraction plant contain several non-triglycerides
components which must be removed.
• Refining consist of several processes which accomplish this aim.
• In refining, physical and chemical processes are combined to remove undesirable
natural as well as environmental-related components from the crude oil.
• These components comprise for example phosphatides, free fatty acids, pigments
(chlorophyll), odours and flavours (including aliphatic aldehydes and ketones),
waxes as well as heavy metals, pesticides etc.
• Depending on the requirements, the following basic processes are implemented:
 Degumming for the removal of phosphatides.
 Neutralization for the removal of fatty acids
 Bleaching for the removal of colour
 Deodorization to distil odours and flavors as well as free fatty acids and
 Winterization for separation of waxes
Degumming
• This is the first step in the refining process of many oils.
• Oils are mixed with water to hydrate phosphatides, which are removed by
centrifuging. Phosphoric acid or citric acid or silica gel are added to enhance the
process.
• Degumming removes valuable emulsifiers such as lecithin
• Cotton seed oils are not degummed, but degumming is necessary for such oils as
soybean and canola.
• The aim of degumming operation:
 The emulsifying action of phospholipids increases oil losses during alkali
refining.
 Gums lead to brown discoloration of oil after heating during deodorization
 Salts may be formed with copper, magnesium, calcium and iron, thereby
accelating oxidative degradation of oil.
• Different degumming processes are carried out to remove phosphatides. For
efficient and economic application of this procedure appropriate machines and
equipment are used: Degumming methods are (i) water degumming (ii) acid
degumming (iii) enzymatic degumming.

Water Degumming
• A large part of phosphatides (gums) can be hydrated quickly and easily. If the
pressed or extracted oil contains considerable quantity of gums the oil is subjected
to the water degumming process immediately following extraction.
• In this process, water is added to the oil. After a certain reaction period the hydrated
phosphatides can be separated either by decantation (settling) or continuously by
means of centrifuges.
• In this process step, a large part of hydratable and even small portion of the non-
hydratable are removed
• The extracted gums can be processed into lecithin for food, feed or technical
purposes.
Water degumming process steps
• Oil is heated to 60-70 oC
• This is followed by water addition and mixing
• The hydration mixing takes 30 minutes
• Separation of hydrated gums is carried out through centrifugation
• This is then followed by vacuum drying of degummed oil
• Gums dried for edible lecithin or recombined in mean
Acid degumming
Dry acid degumming: Dry acid degumming is particularly suitable for the
process of oils with low gum contents such as palm oil, coconut oil or animal
fats. Intensive mixing is implemented following addition of acid to the pr-heated
crude oil.
The benefits of the dry acid degumming are:
• Long service life (the components are acid proof)
• Low investment costs
• Environmentally-friendly as no wastewater or soap stock occur

Wet acid degumming: Initially oils with higher gum contents (e.g. corn oil) are
similarly processed as in dry acid degumming. However, to achieve gum
hydration water is added following acid apportioning. The gums are removed by
a separator prior to bleaching.
This process enable easy separation of gums in oil types with higher non-
hydratable gums contents (e.g. rape oil and soybean oil)
Enzymatic degumming
• Enzymatic degumming was first introduced the German Lurgi Company as
the Enzy Max process”.
• The EnzyMax process into for different steps:
i. Tthe adjustment of optimal conditions for the enzyme reaction, i.e.
optimal pH with a citrate buffer and the optimal temperature.
ii. The addition of the enzymatic solution
iii. The enzyme reaction
iv. The separation of lysophoshatiede from the oil at about 70 oC

For the enzymatic degumming, the following enzymes are used:

• Lecitase 10L (pancreatic phospholipase A2)
• Lecitase Novo (microbial lipase)
• Lecitase Ultra (microbial lipase)
Process Layout for enzymatic degumming
Generalized process for degumming
Neutralization
• The objective of neutralization is the removal of free fatty acids
• Neutralization of vegetable oils is essential:
 to ensure removal of gums, waxes, phosphatides and free fatty acids
(FFA) from the oil;
 To impart uniform colour by removal of colouring pigments and
 To get rid of unpleasant smell from the oil by removal of odiferous
matter.

• Two different neutralization principles are:

 Chemical Neutralization, which the removal by a chemical reaction with
alkali (caustic soda).
 Physical neutralization which is the removal by distillation at higher
temperature and low vacuum.
Bleaching
• During the bleaching process, trace metals, colour bodies such as chlorophyll,
soaps and oxidation products are removed using bleaching clays which adsorb
the impurities.
• Bleached oils are nearly colourless and have a peroxide value of almost zero.
• Depending on the desired finished product, oils are then subjected to one or
more of the following processes.
Deodorization
• Deodorization is a steam distillation process carried out under vacuum, in
which volatile compounds are removed from the oil.
• This may be a batch or continuous process.
• The end product is a bland oil with low level of free fatty acid and zero
peroxide value
• This step also removes any residual pesticides or metabolites that might be
present.
• Some manufacturers favour the use of cotton seed because it can be
deodorized lower temperatures, which results in more tocopherols (natural
antioxidants) being retained.
• Deodorization produces some of the purest food.
Batch Deodorization process flow diagram
Hydrogenation
• Process used to convert liquid fats to plastic fats, thereby making them
suitable for the manufacture of margarine.
• Hydrogenated oils and fats exhibit improved oxidative stability and colour.
• In hydrogenation process, hydrogen is added directly to double bonds of
fatty acids.

• Raney nickel type and copper containing catalysts are normally used.
• Trans fats are made through the chemical process called hydrogenation
of vegetable oils
• Hydrogenation solidifies liquid oils and increases shelf life and the flavour
stability of oils and foods that contain them
Winterization (fractionation)
• Oils such as salad oils, or oils that are to be stored in cool places undergo a
process called winterization so that they will not become cloudy when
chilled.
• The refined, deodorized oils are chilled with gentle agitation, which causes
higher melting fractions to precipitate.
• The fraction which settles out is called stearin.
• Soybean oil does not require winterization, but canola, corn, cottonseed,
sunflower, safflower and peanut oils do.
• Normally, a winterized oil should remain clear for 24 hrs at 0 oC. This
corresponds to a wax content below 50 ppm
Soaps and Detergents
Definition of a soap
• Soaps are water soluble sodium or potassium salts of fatty acids containing
8-22 carbon atoms.
• Fatty acids are generally a mixture of saturated and unsaturated moieties.

• Examples of soaps
Soap Making
• The basic chemical reaction in soap making is saponification.
• Saponification is a process of making soaps by hydrolysis fats or edible oils
with alkalis

Fat/edible oil + NaOH → Soap + Glycerine

• The other method soap making comprises fat splitting followed by the
neutralization process by sodium hydroxide
• Third approach is the methanolysis of triglycerides in the presence of enzymes
(lipase) to produce fatty methyl ester and glycerine, followed by saponification.
Detergents
Definitions
• Detergent is a substance that's used for cleaning. Detergent is similar to soap,
but it's stronger and dissolves more completely in water. Detergents are special,
powerful cleansers that can break up dirt, oils, and grease in clothing or on
dishes.

Surface active agent

A chemical compound, which when dissolved or dispersed in a liquid, is absorbed
at an interface giving rise to a number of chemical properties. The compound
include in its molecule one group that has an affinity for polar surfaces, ensuring
solubilisation in water and a group that has little affinity for water
Amphiphilic substance
• Amphiphilic" is used to describe the properties of a certain group of
chemicals. A chemical substance being amphiphilic possesses both
hydrophilic and lipophilic functional groups. As a result, amphiphilic compounds
show good affinity for both water and oil.
Formulation of detergents
• Detergents are complex formulations that contain 25 different ingredients that
can be categorized into the following main groups:
 Surfactants
 Builders
 Bleaching agents
 Additives

• Each group of detergents has it’s own specific function during the washing
process.
• They have a synergistic effect on one another
• The powdered detergent is about 35%, so the production of the powdered
detergent in the world is about 27.5 million tons and consumption is about
4.2 kg per person-year.
Surfactants
• These are represent the most important group of detergent componets and are
present in all types of detergents.
• In general, surfactants are water-soluble surface-active agents comprising a
hydrophobic group (a long alky chain) attached to hydrophilic group.

• There are four main groups of surfactants, namely

 Nonionic surfactants
 Anionic surfactants
 Cationic surfactants and
 Amphoteric surfactants
Nonionic surfactants:
• These contain non-ionic constituents and the majority of these are condensation
products of ethylene oxide with a hydrophobe.

RO-(CH2-CH2-O)nH
Alkyl poly(ethylene glycol)ethers

• This hydrophobe is invariably a high molecular weight material with an active

hydrogen atom and non-ionic material can be one of the one of the following
reaction products:
 Fatty alcohol and alkylphenol condensate
 Fatty acid condensate
 Condensate of ethylene oxide with an amine
 Condensate of ethylene oxide with an amide.
Nonionic surfactant based on fatty alcohol and alkyphenol
• Alcohol ethoxylate and alkylphenol ethoxylates are produced by reaction of
alcohol with excess ethylene oxide.

• Optimum detergency is found in the

range of 10-15 ethylene oxide
molecules per molecule of fatty alcohol
• Nonylphenol (or octyl) are widely used
with 8-12 ethylene oxide molecules per
molecule fatty alcohol.
Nonionic surfactants based on Fatty Acid Condensate
• Fatty acid condensates are prepared by the reaction of fatty acids with ethylene
oxide.
• This surfactants are prone to alkaline or acid hydrolysis

• The condensates can also be produced produces by esterification of fatty acids

with polyethylene glycol.
Condensates of ethylene oxide with an amine
• The condensation of alkylamines with ethylene oxide leads to secondary or
tertiary substitutes depending on the concentration of ethylene oxide.
• This class of non-ionic surfactants has not
bee largely used in cleaning detergents.

• However, it is noteworthy that these

material in acidic media can exhibit cationic
characteristics whereas in neutral or
alkaline solution they are nonionic
Nonionic surfactants based on ethylene oxides with amide
• Fatty acid alkanolamides are amides of alkylolamines and
fatty acids.
• Certain members of this group exhibit detergency and
others do not
• The non detergent materials are converted into detergents
by condensation with ethylene oxide.

• This non-ionic surfactants find only a little application in

laundry detergents
• They are used as foam boosting, i.e. adding desired stability
to the foam produced by detergents.
Cationic surfactants
• These invariably contain amino compounds and the
most widely used are quaternary ammonium salts,
such as cetyltrimethylammonium chloride, a well-
known germicide, and distearyldimethylammonium
chloride (DSDMAC) known as fabric softener for cotton
diapers and as a laundry rinse-cycle fabric softener.
Other Cationic surfactants are:

Imidazolium salts, such as 1-alkylamidoethyl- Alkyldimethylbenzylammonium

2-alkyl-3-methylimidazolium methylsulphate chloride

N-methyl-N,N-bis[2-(16-18-ccyloxy)ethyl]-N-(2-hydroethyl) ammonium metho sulphate

Anionic surfactant
• These represent the largest class of synthetic surfactants

SO3Na

Methods of Preparation
Suphonation with sulphuric acid
Sulphur trioxide sulphonation
Secondary alkane sulfonates
• These are still valued as anionic surfactants for consumers products.
• They are known to have:
 high solubility,
 fast wetting properties,
 chemical stability to alkali, acids and strong oxidants such as chlorine

• They are produced by photochemical sulfoxidation or sulfochlorination of

suitable C12-C18 paraffin cuts.
• SAS have similar properties as linear alkyl sulfonates (LAS)
Other sulfonated derivatives

Sulfonated olifins

-Sulfo fatty acid ester

Alkyl ether sulfates (AES)

Amphoteric surfactants
• These compounds have the characteristics of both anionic dtergents and
cationic fabric softeners.
• They tend to work best at neutral pH, and are found in shampoos, skin
cleaners and carpet shampoos
• The surfactants are rarely employed in laundry detergents because of their
high costs
PRODUCTION COSTS OF FUELS AND CHEMICALS MANUFACTURING
Price of Chemical Products
Depends on:
• Structural demand for the product.
• The price of oil and other raw materials.
• The actual availability of the product.

The relationship between price and demand is the result of competition

between products:
 If a product becomes cheaper, it accesses new markets and can be
used as raw material for new products.
 Product with a smaller demand are manufactured at a smaller scale and
therefore mostly at a lower efficiency, which results in higher production
costs.
Investment Costs
• Investment costs are determined by:
• Delivered equipment costs (reactors, heat exchangers, boilers etc.)
• Indirect costs for erection, piping, engineering etc.
• These are estimated by factors shown in the table below
For quick estimation of investment costs, the overall factor method developed by Lang
(1948) can be used:
• The cost of each equipment is estimated and summed, an finally multiplied with the
overall factor.
• According to Lang (1948), the overall factor for a plat for solid processing is 3.9 and
liquid processing 4.8
• According to Smith (2005) it’s 4.4 and 5.8 respectively.
• Generally, a 100-fold increase in investment is needed for a 1000-fold increase in
capacity and the following formula can be used

With 0.4<n<o.8, typically n=2/3

I= investment cost
Cannual production capacity
• Accurate determination of investment costs is complicated and labor
intensive.
• For an estimation of ±30% accuracy requires an accurate identification
and sizing of large pieces of equipment.
• Scientists and engineers need simple and crude methods to estimate
investment costs.
Variable costs
These are cost that depend mostly on the scale of production and these
are mainly:

Feedstock: variable costs arise from consumption and price of

feedstock.
• Consumption depends on the technology applied and rarely exceeds
110% of the stoichiometric consumption in modern plants.
• As for feedstock and product prices, data are available in the
literature and various websites.

Catalyst Costs
These vary in a wide range of USD0.01 to USD100- ton-1.
Energy Costs
• Required to run pumps and compressors or to heat process streams.
• Can amount to 25kt-1 and includes consumption of fuel, steam and electricity
• Energy requirements depend on
• heat of reaction, whether exothermic or endothermic.
• Technology – older technologies tend to consume more energy than new
technologies
Operating costs
• consist of variable and fixed costs
• Variable costs depend on actual consumption and on the price of various
streams needed for production.

• Fixed costs include maintenance, labour, overheads and above all the
provision to recover investment and capital expenditure.