Petrochemical Engineering – II

Unit - II

Aromatics-BTX derivatives
• Ethyl Benzene and Styrene
• Phthalic Anhydride
• Linear Alkyl Benzene
• Phenol [C6H5OH]
• Maleic Anhydride [HC=CHC(O)OC(O)]
• Nitrobenzene [C6H5NO2]
• Aniline [C6H5NH2]
• Bisphenol-A
• Alpha Methyl Styrene [C6H5C(CH3)=CH2]
• Dodecyl Phenol [C12H25C6H4OH]
• Fumaric Acid [HOOCCH=CHCOOH]
• Isophthalic Acid [C6H4(COOH)2]
• Benzoic Acid [C6H5COOH]
• Benzyl Chloride [C6H5CH2Cl], Benzal Chloride [C6H5CH2Cl], Benzotrichloride [C6H5CCl3]
• Benzaldehyde [C6H5CHO]
• Nitrotoluenes [mono nitrotoluenes(MNT)], Dinitrotoluenes(DNT), Trinitrotoulenes (TNT)
• Cyamene [CH3C6H4CH(CH3)2]
• Cresols [CH3 C6H4OH]
• Nonylphenol [C9H19C6H4OH]
• Diisopropyl Benzene (DIPB)
• Hydroquinone [C6H4(OH)2]
• Anthraquinone [C6H4(CO)2 C6H4]
• p-Diethyl benzene (PDEB)
 Aromatics-BTX derivatives
• Aromatic hydrocarbons- Benzene, Toluene, Xylene (BTX) and ethyl benzene
are major feed stocks for intermediates which are used in production of
Synthetic fiber, resins,
synthetic rubber, explosives, pesticides,
detergents, dyes, etc.
Product profile of Aromatics
 Phthalic Anhydride
• Phthalic anhydride is the organic compound with the formula C6H4(CO)2O.
• It is the anhydride of phthalic acid.
• This colourless solid is an important industrial chemical, especially for the large-
scale production of plasticizers for plastics.
• In 2000, the world wide production volume of phthalic anhydride is estimated to
be about 32,32,000 tones per year.

Uses
• Phthalic anhydride is widely used in industry for the
production of certain dyes.
• A well-known application of this reactivity is the preparation of
the anthroquinone dye quinizarin(Green Dye)
by reaction with para-chlorophenol followed by hydrolysis of the chloride.

Process Technology
• Phthalic anhydride was first reported in 1836 by Auguste Laurent.
• It is presently obtained by catalytic oxidation of ortho-xylene and naphthalene
("Gibbs phthalic anhydride process"):
C6H4(CH3)2 + 3 O2 → C6H4(CO)2O + 3 H2O C10H8 + 4.5 O2 → C6H4(CO)2O + 2 H2O + 2 CO2
• Global demand of phthalic anhydride is projected to rise from
1,47,000 tonnes in 2001-02 to 2,07,000 tonnes in the year 2006-07.
• The total demand for o-Xylene is projected to go up 2,09,000 tonnes by
2006-07.
• With the production of p-Xylene in the RIL Jamnagar plant
availability of o-Xylene has improved.
catalyst: V2O5 supported
on silica or silicon carbide
promoted with titanium
oxide metal

Phthalic anhydride from Naphthalene

Catalyst: V2O5 and Titanium Oxide
Temperature: 3800C ;
EXOTHERM
IC

Phthalic anhydride from o-Xylene

• Linear Alkyl Benzene(LAB)
• Linear alkylbenzene is a family of organic compounds with the
formula C6H5CnH2n+1.
• Typically, n lies between 10 and 16, although generally supplied as a
tighter cut, such as C12-C15, C12-C13 and C10-C13, for detergent use.
• The CnH2n+1 chain is unbranched.They are sometimes called LABs.
• They are mainly produced as intermediate in the production of
surfactants, for use in detergent.
• Since the 1960s, LABs have emerged as the dominant precursor of
biodegradable detergents.
LAB production in INDIA
• Indian Petrochemicals Co. Ltd,Vadodara – 50,000 tonnes
• Reliance Industries - 1,00,000 tonnes
• Tamil nadu Petro products Ltd, - 1,20,000 tonnes
Manali - 75, 000 tonnes
• Nirma , mehsana - 1,20,000 tonnes
• Indian Oil Co. Ltd, Vadodara
Composition of LAB and its influence in the performance of
detergents:
• Light duty liquids for the use in light household applications
such as dish washing are produced from LAB with carbon
numbers between C11-C12.
• Heavy duty laundry applications require LAB with C12-C14.
• Higher carbon numbers in the range of C16-C24 are used as
lubricants, detergents additives in the form of alkyl benzene
sulphonates.
• The alkyl benzene sulphonate derivatives of C16 and high
have low solubility in water and are well suited for use as
lubricants and cutting fluids.
Process
Technology:
• The process of LAB manufacture involves:
i. Separation of n-paraffins from kerosene by
adsorption using Molecular sieve
ii. Dehydrogenation of n-paraffins to n-olefins and
coupling of these olefins with benzene in the
presence of catalyst.
• About 85% of the world LAB is based on HF
alkylation technology.
• After the first commercial scale production of LAB in
1995, all new LAB production plants are based on solid
bed/fixed bed alkylation technology.
• Some of the advantages of the solid bed alkylation
technology process are:
i. Better product quality.
ii. less process equipment due to elimination of HF which
requires additional steps like HF handling,
regeneration ,purification and waste treatment.
iii. less maintenance cost.
iv. less cost of equipment and material of construction.
• Hydrotreated kerosene is a typical feedstock for high purity
• Feedstock for LAB – Kerosene and Benzene
LAB Manufacture from fixed Bed Technology
 PHENOL
• Phenol is one of the most important petrochemicals.
Ranging from solvents to polymers, phenol is required
for several petrochemical processes as an important raw
material.
• Phenol can be produced from many sources such as
 Cumene
 Toluene
 Benzene
• Depending upon these raw materials, various chemical
transformations.
• The major use of phenol in the manufacture of Adipic
acid, aniline, Bisphenol-A, Caprolactam, Salicylic acid
and Xylenols etc.,
 Name of the units Installed Capacity
Hindustan Organics Chemicals Ltd, 50000 TPA
Ambalamugal, Cochin
Herdillia Chemicals Ltd, Thane, 30000 TPA
Maharashtra
Neyveli Lignite Corpoation Tamil 10000 TPA
Naidu

An early commercial route, developed by Bayer and Monsanto in the early

1900s, begins with the reaction of a strong base with benzene sulfonate:
C6H5SO3H + 2 NaOH → C6H5OH + Na2SO3 + H2O
Other methods under consideration involve:
•Hydrolysis of Chloro-benzene using base or steam (Raschig-Hooker process):
C6H5Cl + H2O → C6H5OH + HCl
•Direct oxidation of Benzene with Nitrous Oxide a potentially "green"
process:
C6H6 + N2O → C6H5OH + N2
• oxidation of Toluene as developed by Dow Chemical:
C6H5CH3 + 2 O2 → C6H5OH + CO2 + H2O
High-purity phenol and acetone from cumene(the Kellogg Brown
& Root (KBR) phenol process )
• Cumene is oxidized (1) with air at high efficiency (+95%) to produce cumene
hydro peroxide (CHP), which is concentrated (2) and cleaved (3) under high-
yield conditions (+99%) to phenol and acetone in the presence of an acid
catalyst.
• The catalyst is removed and the cleavage mixture is fractionated to produce high-
purity products (4 – 8), suitable for all applications. AMS(alpha methyl styrene)
is hydrogenated to cumene and recycled to oxidation or optionally recovered as
a pure byproduct.
• Phenol and acetone are purified. A small aqueous effluent is pretreated to allow
efficient biotreatment of plant wastewater.
• With AMS hydrogenation, 1.31 tons of cumene will produce 1 ton of phenol and
0.615 tons of acetone. This high-yield process produces very high quality phenol
and acetone products with very little heavy and light end byproducts. With over
40 years of continuous technological development, the Kellogg Brown & Root
(KBR) phenol process features low cumene and energy consumptions, coupled
with unsurpassed safety and environmental systems.
High-purity phenol and acetone from cumene
Phenol production from Cumene
(cumene peroxidation route)
Reactions :
Peroxidation:
Cumene + Air ⟶ Cumene Hydroperoxide
Hydrolysis:
𝐻2 𝑆𝑂4
Cumene Hydroperoxide Phenol + Acetone
• For Peroxidation :
Operating conditions: Normal T & P
Emulsification agent: NaOH (Alkali)
• For Hydrolysis :
10 – 25 % H2SO4 (Aqueous) is used
Operating conditions: 800C and atmospheric pressure
conditions
Phenol production from Cumene

 Fresh cumene is mixed with hydrogenated unreacted cumene, cumene +

alpha methyl styrene (recycle streams).
 The pre-purification step involves converting unsaturates such as alpha
methyl styrene and others to saturates. This is done by using nickel
catalyst at 100 oC and feeding hydrogen to the pre-purification reactor.
The product from this unit then mixes with the fresh cumene.
 The fresh cumene and processed cumene and alpha methyl styrene are
fed to the oxidation reactor. The oxidation reactor refers to a gas liquid
reaction between air (Oxygen) and the cumene.
Cont…

 An emulsion of cumene is prepared in the oxidation reactor by

adding alkali to it.
 pH is maintained in the range of 8.5 – 10.5 to suit good
emulsification conditions.
 After reaction, vent gases are condensed and recycled back and the
product is sent to a cleavage unit.
 The cleavage unit consists of a stirrer and is fed with fresh and
recycled H2SO4 aqueous solution to enable the hydrolysis of
cumenehydroperoxide.
 Cont…
 The product streams from the cleavage unit enter a settler (phase
separator) which upon gravity settling yields two streams namely the
acid rich aqueous stream and the phenol rich organic stream.
 The aqueous stream consists of the sulphuric acid and is sent back to the
cleavage unit as a recycle stream.
 The organic stream consists of cumene (unreacted), phenol (product),
acetone (side product), alpha methyl styrene (side product) and
acetophenone (side product)An emulsion of cumene is prepared in the
oxidation reactor by adding alkali to it.
 The organic stream from the gravity settler unit then enters a scrubber
fed with water. In this operation, water extracts the remaining acids in
the organic stream and produces crude phenol stream. Water leaving the
unit consists of acidified wash water.
Cont…

 The crude phenol then enters a distillation unit that separates acetone
from the other components.
 The bottom product from this distillation column enters a vacuum
distillation column that produces cumene as a top product.
 The bottom product from the distillation column enters another
vacuum distillation unit to produce alpha methyl styrene.
 The bottom product of this distillation column enters the final
vacuum distillation unit to produce phenol as top product and
acetophenone as the bottom product.
Phenol from Cumene process
The Sunoco/UOP phenol process produces high-quality
phenol and acetone by liquid- phase per-oxidation of
cumene.

Key process steps:

1.oxidation and concentration
2. decomposition and neutralization
3. phenol and acetone purification
4.AMS (alpha methyl styrene) hydrogenation or AMS refining
Oxidation and concentration:
• Cumene is oxidized to cumene hydroperoxide (CHP). A small amount of
dimethylphenylcarbinol (DMPC) is also formed, but low-pressure and
low-temperature oxidation results in very high selectivity of CHP.
• CHP is then concentrated and unreacted cumene is recycled back to the
oxidation section.
Decomposition and neutralization:
• CHP is decomposed to phenol and acetone, accompanied by dehydration
of DMPC to alphamethylstyrene (AMS), catalyzed by mineral acid. This
unique design achieves a very high selectivity to phenol, acetone and AMS
without using recycle acetone.
• The high total yields from oxidation and decomposition combine to
achieve 1.31 wt cumene/wt phenol. Decomposed catalyst is neutralized.
Phenol and acetone purification:
• Phenol and acetone are separated and purified. A small amount of
byproduct is rejected as heavy residue.

AMS hydrogenation or AMS refining:

• AMS is hydrogenated back to cumene and recycled to oxidation, or
AMS is refined for sale.
• Cumene peroxidation is the preferred route to phenol, accounting for
more than 90% of world production.
• The Sunoco/UOP Phenol process features low feedstock
consumption (1.31 wt cumene/wt phenol) without tar cracking,
avoiding the expense and impurities associated with tar cracking.
• High phenol and acetone product qualities are achieved through a
combination of minimizing impurity formation and efficient
purification techniques.
• Optimized design results in low investment cost along with low utility
and chemicals consumption for low variable cost of production.
Sunoco/UOP phenol process
 Phenol from Chlorobenzene route

Reactions There are three reactions to convert benzene to phenol using

chlorination route
Chlorination
Benzene + Cl2 monochloro benzene
Catalyst: Fe or FeCl3 , Operating temperature: 85 C
Causticization
Benzyl chloride + NaOH sodium benzoate
NaOH is in aqueous media
Operating conditions: 425 oC and 350 atms, Exothermic reaction
Hydrolysis
Sodium benzoate + HCl (aq) Phenol + NaCl (aq)
Operating conditions: Nothing specific
 Phenol from Chlorobenzene route

Process details:
 Benzene is first dried. Dry benzene and FeCl3 catalyst enters
the chlorination reactor.
 After the solid-gas-liquid reaction, the products are further
heated up to enter a fractionator
 The fractionator separates benzene as a top product and
monochloro benzene as the bottom product. The top product
also consists of HCl off gas that is obtained as the vapour
stream from the partial condenser.
 The benzene is further cooled and sent back to the reactor
and also as a reflux to the fractionator
 Phenol from Chlorobenzene route

 The bottom product monochloro benzene is mixed with 10

% NaOH solution and diphenyl oxide to enter a high
pressure pump followed with heat integrated heat exchanger
that pre-heats the feed to higher temperature.
 The feed then enters the causticization reactor which has
cooling water tubes to control the temperature.
 The product stream is cooled using heat integrated
exchanger and then enters a neutralizer that is fed with the
HCl obtained from the fractionator partial condenser.
 After neutralization, the product phenol is separated from
the aqueous phase using gravity settling principle
Phenol from Chlorobenzene route
 Phenol by Benzene Sulphonation Process
Benzene can be converted to phenol with the help of inorganic acids and salts and this process
is oldest of all the processe.
This process involves four major chemical reactions which are:
1. Sulfonation: Benzene is reacted with sulphuric acid to form benzene sulphonic acid at
150 to 170 deg centigrade
2. Neutralization: Benzene sulphonic acid is reacted with sodium sulfite to form sodium
benzene sulphonate
3. Fusion: Sodium benzene sulphonate is fused with sodium hydroxide to form sodium
phenoxide
4. Acidification: sulphuric acid and sodium phenoxide are reacted to produce crude
phenol and sodium sulphite.
The above reaction step explains the requirement of the unit operation equipments in the
process as
• Filtration: Pressure filter and centrifuge used in separation of sodium sulphate and
sodium sulphite
• Distillation: Separation of phenol from crude phenol
• Crystallization: Separation and recovery of sodium sulphite
Phenol by Benzene Sulphonation Process
 Phenol using Oxychlorination route
• Reactions
• First reaction
Benzene + HCl + Oxygen Benzyl chloride + Water
Catalyst: FeCl3+ CuCl2, Operating conditions: 240oC and atmospheric pressure
• Second reaction
Benzyl chloride + water Phenol + HCl
Catalyst: SiO2, Operating conditions: 3500C and atmospheric pressure
Here, HCl is regenerated and will be recycled.
Phenol from Oxy chlorination route
• In this process, Benzene is used to extract phenol from phenol +
water mixture.
• This unit is termed as an extraction unit (liquid - liquid extraction
principle).
• Therefore, this unit takes up fresh benzene and phenol + water
mixture and produces two streams namely water stream (bottom
product) and benzene + phenol stream (top product). The water
stream is fed to a scrubber unit .
• Then onwards, the organic mixture is fed to a distillation column
that produces purer benzene as the top product. The bottom
product is phenol with other impurities.
• The bottom phenol rich product is sent to the phenol fractionator
to obtain waste product as top product and pure phenol as bottom
product.
• The purer benzene then enters the Hydrochlorination reactor in which a
mixture of HCl and O2 is fed at 220o C. Under these conditions, Benzene
will be also in vapour state.
• Therefore, the reactor is a gas solid reactor.
• The conversions are pretty low and not more than 20 % of the benzene is
converted to benzyl chloride.
• Eventually, the products are sent to two fractionators that separate
unreacted benzene, crude benzyl chloride and poly benzyl chlorides as
various products.
• The unreacted benzene is sent back to the hydrochlorination reactor as a
recycle stream.
• The crude benzyl chloride then enters an absorber unit A where phenol is used to
purify the benzyl chloride from other organic compounds (such as benzene and
polybenzyl chlorides).
• The purified benzyl chloride stream then enters the hydrolysis reactor in which
water is passed along with benzyl chloride over the silica catalyst. The reactor
itself is a furnace with catalyst loaded in the tubes and hot fuel gases are circulated
in the shell to obtain the desired higher temperature.
• Under these conditions, both reactants are in vapour state (with the benzyl
chloride boiling point of 179 o C) and therefore, the reaction is also a gas solid
reaction.
• After hydrolysis reaction, the product vapors are sent to a partial condenser that
separates the HCl from the organic phase. The HCl is recycled to the hydro-
chlorination reactor.
• The phenol rich product stream is sent as a solvent for the scrubber (unit A) that
purifies crude benzyl chloride to purer benzyl chloride. The bottom product from
the scrubber (i.e., unit A) enters another scrubber (unit B) that receives water
from the extractor. The unit B enables washing of the phenol to remove any water
soluble impurities. The water from the unit B enters the hydrolysis reactor.
 Maleic Anhydride [HC=CHC(O)OC(O)]

• Maleic anhydride is an organic

compound with the formula
C2H2(CO)2O.
• It is the acid anhydride of Maleic acid
and in its pure state it is a colourless or
white solid.
• Demand of Maleic anhydride is
projected to go up to 39000 tonnes by
2006-07.
• Global capacity and consumption of
MA are around 1.578 &1.230 million
tonnes.
Process Technology:

• Maleic anhydride is manufacture from benzene by butane oxidation

Reactions:
- Benzene + O2 (Air) ⟶ Maleic anhydride + H2O + CO2
- Reaction is exothermic
- Operating temperature is 400 – 500 oC
- Catalyst is V2O5
- For fumaric acid, the reaction is Maleic acid ⟶ Fumaric acid.
- Fumaric acid is an isomer of Maleic acid.
- HCl is used as a catalyst for the isomerisation reactor at normal
pressure and temperature.
Process Technology:

• Benzene or butane is first vaporized in excess air.

• Then the mixture enters the catalytic tubular reactor (with shell
arrangement). The catalytic reactor is circulated with salt solution so
as to absorb the heat generated using the reaction.
• The reactor products enter a waste steam recovery boiler where the
boiler water is converted to steam.
• The product vapors eventually enter an integrated heat exchanger to
exchange heat with the pre-heated feed stream.
• Eventually, the vapors are condensed followed with gravity settling
to remove tar as a product in the gravity settling. The vapors then
enter a water scrubber to obtain 40 % maleic acid solution. The
leaving gases consist mainly of CO2.
Process Technology:

• The maleic acid from the absorber is partially sent to a dehydrator that
removes water using azeotropic distillation principle. The purified
maleic anhydride product is further sent to vacuum distillation to
obtain the maleic anhydride product.
• The dilute maleic acid solution is partially sent to an isomerisation unit
where HCl is used as the isomerisation catalyst.
• After reaction, the product is sent to a centrifuge that separates water
from the fumaric acid.
• Eventually, fumaric acid is sent to a drier to obtain dry fumaric acid.
Manufacture of Maleic anhydride
Uses:
 Maleic anhydride can be used as a highly
reactive and versatile raw material.
 It can be used in the manufacture of alkyd resins,
which in turn are used for making paints and
coatings.
 It can also be used in making agricultural
chemicals like herbicides, pesticides and plant
growth regulators.
Nitrobenzene [C6H5NO2]

•Nitrobenzene is an organic compound with the

chemical formula C6H5NO2.
•It is a water-insoluble pale yellow oil with an
almond-like odor.
•It freezes to give greenish-yellow crystals.
•It is produced on a large scale from benzene as a
precursor to aniline.
•In the laboratory, it is occasionally used as a solvent,
especially for electrophilic reagents.
• Nitrobenzene is the important feedstock for aniline and a
major portion of nitrobenzene is used directly or indirectly as
aniline in dye manufacture.
• Aniline is used as raw material for the manufacture of a large
number of chemicals like Methylene Diphenyl
diisocyanate(MDI), Rubber processing chemicals like
antioxidants, stabilizers, agricultural chemicals include aniline
based fungicide, insecticides, animal repellants , dyes and
pigments.
Process Technology of Nitrobenzene:
• Nitrobenzene is manufactured by the nitration of benzene in
a mixed acid solution(HNO3/H2SO4).
• The mixed acid provides nitronium ion which is the
electrophilic agent in nitration.
• Nitration is carried out in a series of agitated reactors made
of cast iron or steel.
• Temperature is maintained at around 1800C.
• The reaction mixture from the nitrator is fed to a separator
where nitrobenzene is separated .
• Crude nitrobenzene is washed with water and dilute sodium
carbonate.
• Benzene and water are separated from Nitrobenzene in a
distillation column and recycled.
• However, where high purity nitrobenzene is required, it may
be purified by further distillation
Nitrobenzene from Benzene
 Aniline [C6H5NH2]

–Aniline, phenylamine or aminobenzene is an organic compound

with the formula C6H5NH2.
–Consisting of a phenyl group attached to an amino group, aniline is the
prototypical aromatic amine.
–Being a precursor to many industrial chemicals, its main use is in the
manufacture of precursors to polyurethane.
–Like most volatile amines, it possesses the somewhat unpleasant odor of
rotten fish.
–It ignites readily, burning with a smoky flame characteristic of aromatic
compounds.
–Aniline is colorless, but it slowly oxidizes and resinifies in air, giving a
red-brown tint to aged samples.
Product profile of Aniline
Process technology of Aniline:
• Aniline can be produced either by the Ammonolysis of
Chlorobenzene or by the reduction of nitrobenzene in liquid or
vapor phase in the presence of hydrogen.
• Catalyst in the liquid phase processes includes nickel, copper, or
cobalt supported on a suitable inert carrier, palladium or
platinum or their mixture supported on carbon.
• The vapor phase reduction processes catalysts include copper,
copper oxide, nickel and molybdenum.
• It can be also made by Ammonolysis of phenol.
• Vapor Phase Hydrogenation of Nitrobenzene
– In this process preheated nitrobenzene is vaporized;
– Nitrobenzene and Hydrogen in molar ratio of 9:1 is fed to the
fluidized bed catalytic reactor consisting of copper-on-silica.
– Cooling device removes heat generated during reaction.
– The reactor exit gases are filtered in a metallic filter provided at
the top of the reactor and are condensed and sent to a separator
from which the gases containing hydrogen are recycled.
– The liquid layer in the separator is distilled to remove the heavy
ends
– The crude aniline purified by vacuum distillation.
– Temperature maintained here is 2800-2900C.
Aniline from Nitrobenzene
• Ammonolysis of Chlorobenzene: aniline is produced
by Ammonolysis of Chlorobenzene at 200-2200C and 55-73
kg/cm2 pressure in presence of copper catalyst.

• Ammonolysis of Phenol: the process involves Ammonolysis of

phenol in the vapor phase at around 400- 4200C at about 1.6 KPa
with excess of ammonia in the presence of silica/alumina
catalyst.
Uses of Aniline:

–The largest application of aniline is for the preparation of

methylene diphenyl diisocyanate (MDI). The majority of aniline
serves this market.
–Other uses include rubber processing chemicals (9%), herbicides
(2%), and dyes and pigments (2%).
–Drugs prepared from aniline is paracetamol (acetaminophen,
Tylenol). The principal use of aniline in the dye industry is as a
precursor to indigo, the blue of blue jeans.
Bisphenol-A(BPA)
–Bisphenol A (BPA) is an organic compound with the chemical
formula (CH3)2C(C6H4OH)2.
–It is part of the bisphenols group of chemical compounds with two
hydroxyphenyl functionalities.
–It is a colorless solid that is soluble in organic solvents, but poorly
soluble in water. Having two phenol functional groups, it is used to
make polycarbonate polymers and epoxy resins, along with other
materials used to make plastics.
–Bisphenol A has a vapor pressure of 5*10−6 Pa.
–BPA exhibits hormone-like properties that raise concern about its
suitability in consumer products and food containers.
–Since 2008, several governments have questioned its safety, which
prompted some retailers to withdraw polycarbonate products.
–A 2010 report from the United States Food and Drug
Administration (FDA) warned of possible hazards to fetuses, infants,
and young children.
–In September 2010, Canada became the first country to declare BPA
a toxic substance.
–The European Union, Canada, and recently the United States have
banned BPA use in baby bottles.
Process technologies for the manufacture of Bisphenol:
• Condensation of phenol with carbonyl compounds
• Condensation of phenol with alkenyl phenol
• Condensation of phenol with ethylene and acetylenes
• Condensation of phenol with alkyl benzene
• Amongst the above process technologies, acid condensation of
phenol and acetone is only one commercial route commonly
used by Bisphenol manufactures.
India and Global demand of Bisphenol [Chemical
business, 2012]
• Demand of Bisphenol in India during 2010-11 was 30,000
tonnes per annum
• Global installed capacity: around 5.2 million tones
• Global demand around 4.2 million tones
• Global growth rate in demand 5 to 6percent
Process Technology:
• Bisphenol from Phenol and Acetone (Acidic condensation of
Phenol and Acetone)
– Phenol and Acetone in 3:1 molar ratio are reacted in four glass lined
stirred reactors at 500C and 1 atm pressure using anhydrous
hydrochloride catalyst and methyl mercaptan as promoter.
– The residence time is 3hr in each of these four reactors
– The reaction is exothermic, cooled by cooling water
– Around 99% of Acetone is converted to Bisphenol.
– Phenol is used in excess to ensure the predominance of the forward
reaction.
– Most important controlling parameter is Temperature
– Higher temperature causes the isomerization of Bisphenol
– The product is further purified in next distillation column where
water is separated
Bisphenol From Phenol and Acetone
 Benzoic Acid(C6H5COOH)

 Benzoic acid is used in the manufacture of caprolactum, phenol and

terephthalic acid and used as mordant.
Process technology:
 Liquid phase catalytic oxidation of toluene in the presence of cobalt
acetate at 1650C & 11.2 atm pressure.
The major processing steps in the manufacture of benzoic acid:
 Catalytic liquid phase air oxidation of toluene
 Stripping of unreacted toluene and light end precursors from the
benzoic acid for recycle
 Distillation of recover benzoic acid as a pure overhead product.
Benzoic Acid from Toluene
 Benzoic acid is also produced by oxidation of toluene in acetic
acid solution in presence of bromide ions
Uses:
 It is used as a Mordant, seasoning of tobacco, in dentifrices
(Dentifrices are agents used along with a toothbrush to clean
and polish natural teeth. ) and medicines.
 The growth of Diet soft drinks market has increased the demand
of benzoic acid as sodium and potassium benzoate.
 Sodium salt of benzoic acid is used in food and fruit beverages.
 It is also used for Manufacture of Diethylene glycol benzoate and
butyl benzoate which are used as plasticizers and perfume
ingredient.
 Terephthalic acid (TPA) and Dimethyl
Terephthalate (DMT)
 Terephthalic acid (TPA) and Dimethyl Terephthalate (DMT)
are major building blocks for manufacture of polyethylene
terephthalate (Polyester) fibers and resins.
 The increase in the PET demand in the major market fibers,
film and rigid packaging has been the primary drivers for the
DMT/TPA market.
 Uses of purified terephthalic acid: PSF (Polyester Staple
Fibre), PFY (Polyester FilamentYarn) Polyester resins, PET
 Production of DMT
Hercules/ Dynamit Nobel Process:
• This is the most widely used route for the production of DMT where p-
xylene and methanol comprise the feedstock.
• It involves four steps, which alternate between liquid-phase oxidation and
liquid-phase esterification.Two reactors are used.
• First, p-xylene is oxidized with air to p-toluic acid in the oxidation reactor,
and the contents are then sent to the second reactor for esterification with
methanol to methyl p-toluate (p-toluic ester).
• The toluate is isolated by distillation and returned to the first reactor where it
is further oxidized to monomethyl terephthalate, which is then esterified in
the second reactor to dimethyl terephthalate.
 p-Xylene, air, and catalyst are fed continuously to the oxidation reactor where
they are joined with recycle methyl p-toluate(p-toluic esters(PTE)).
 Typically, the catalyst is a cobalt salt, but cobalt and manganese are also used
in combination.
 The oxidation reactor is maintained at 140–180◦C and 500–800 kPa (5–8
atm).
 The heat of reaction is removed by vaporization of water and excess p-xylene;
these are condensed, water is separated, and p-xylene is returned
continuously. Cooling coils can also be used.
 The oxidation reactor effluent and methanol are sent to the esterification
reactor, which operates at up to 250◦C and a pressure sufficient to maintain
the liquid phase.This latter is about 2500 kPa (25 atm).
 The oxidation products are converted to methyl p-toluate and dimethyl
terephthalate without a catalyst. Excess methanol is supplied, and steam and
vaporized methanol are removed and enter a methanol recovery column.
 The esterification products flow to a crude ester column, which
separates the toluate from the terephthalate. The overhead stream of
methyl p-toluate is returned to the oxidation reactor, and the bottom
stream of dimethyl terephthalate goes to a primary distillation.
 The distillate is dissolved in methanol, crystallized, and solid dimethyl
terephthalate is recovered.
 The dimethyl terephthalate can then be either recrystallized or distilled
to yield the highly pure material needed for the polyesterification
reaction.
 The overall yield of the process is at least 87 mol %.
Manufacture of DMT
Manufacture of DMT by Nobel process
Manufacture of DMT by Witten Process
TPA (Amco Proess)
Process consists of two steps:
 Oxidation of p-Xylene to crude terephthalic
acid
 Purification of crude terephthalic acid by
crystallization.
 Oxidation of p-Xylene

 p-xylene is oxidized with air at 20 am pressure & 200-

2100C temperature in the presence of catalyst cobalt
acetate, manganese acetate and hydrobromic acid as a
promoter.
 The reaction is carried out in the presence of acetic
acid.
 Terephthalic acid is crystallized in series of crystallizers
under vacuum.
 The slurry from the third crystallizer is filtered in a
rotary filter, washed and the crude TPA is sent to a
dryer where the residual acetic acid is removed.
Purification of crude TPA

 The purification of crude TPA consists of catalytic hydrogenation

and re-crystallization of crude TPA.
 TPA slurry in water is hydrogenated in the presence of palladium
catalyst, where 4-carboxy benzaldehyde is reduced to p-toluic
acid and other coloring impurities are also reduced to removable
material.
 The solution from the reactor at 2500C & 80 bar pressure is
flashed through a series of crystallizers.
 The purifiedTPA is crystallized, centrifuged and dried.
Manufacture of TPA by Amco Process
 TPA (Mobil process)
 P-xylene is oxidized in the presence of cobalt based catalyst without using any
promoter.
 The reaction takes place in the acetic acid medium at around 1300C.
 Methyl ethyl ketone is used as the activator.
 After cooling, washing and centrifuging, crude TPA is passed on to the
purification section.
 Here the purification of crude TPA takes place in two steps:
 The crudeTPA is slurred with acetic acid and charged to the leaching stage.
 During leaching impurities, like p-carboxyl benzaldehyde and cobalt catalyst are
removed from the Crude TPA.
 Crude TPA (about 99.5%) is further purified by sublimation.
 Crude TPA from the leaching operation is dispersed in steam, hydrogen and
catalyst are added to the dispersed TPA, Which is then passed through a heat
furnace.
 The purifiedTPA vapours after separating impurities are condensed.
Some of the advantages ofTPA over DMT :
 Per unit of polyester produced is about 15 percent less than that of TPA
required.
 Bulk density of TPA is 1.0 tonne/m3 as compared to DMT (0.5
tonne/m3). Thus transportation costs and storage requirements for TPA
are significantly lower.
 TPA process required a lesser feed mole ratio of glycol to PTA of around
1.2 against 1.6 for DMT.
 Esterification reaction of TPA does not require any catalyst whereas the
trans esterification of DMT has to be catalyzed.
 With TPA process water is the byproduct whereas with DMT process
methanol is the byproduct. Therefore, more process hazards in handling
methanol.
 With the TPA process, it is easier to reclaim polymer.
 Product fromTPA is better with respect to thermal and hydrolytic stability.
 Product cost in case of TPA is lesser due to reduced raw material
requirement, reduced transport and handling cost.