A Report on

Production of Phenol from 99.9%

pure Cumene from Naptha cracker

Production of 99.99% pure Bisphenol

A from 99.99% pure Phenol

Major Project Report submitted by

Virender Pratap Singh
Department of Chemical Engineering,
IIT Roorkee
On
November 24, 2014

Table of content
Phenol
1. Uses & present status of the product

Page 2

2. Market Prospects

Page 5

3. Available process for the production of product

Page 7

4. Techno-Economic appraisal of alternative processes

Page 10

5. Selection of Technology/Scheme
5.1 Basis of Selection

Page 11

5.2 Details of selected process - Sunoco/UOP Process

Page 11

5.3 Process flow and recent technology advances

Page 12

6. Raw Material
6.1. Sources of raw material

Page 25

6.2 Availability of Cumene

Page 27

6.3 Import Data

Page 27

6.4 Export Data

Page 30

6.5 Prevailing Prices

Page 31

6.6 Government Policies & Import duty

Page 31

BisPhenol A
1.
2.
3.
4.
5.

Uses & present status of the product

Market Prospects
Available process for the production of product
Techno-Economic appraisal of alternative processes
Selection of Technology/Scheme

References

1|Page

Page 32
Page 34
Page 35
Page 36
Page 37

Page 46

Phenol
1. Uses & present status of the product
The main use of phenol is as a feedstock for phenolic resins, bisphenol A and
caprolactam (an intermediate in the production of nylon-6). It is used in the
manufacture of many products including insulation materials, adhesives, lacquers,
paint, rubber, ink, dyes, illuminating gases, perfumes, soaps and toys. Also used in
embalming and research laboratories. It is a product of the decomposition of organic
materials, liquid manure, and the atmospheric degradation of benzene.
It is found in some commercial disinfectants, antiseptics, lotions and ointments. Phenol
is active against a wide range of microorganisms, and there are some medical and
pharmaceutical applications including topical anaesthetic and ear drops, sclerosing
agent.
It is also used in the treatment of ingrown nails in the "nail matrix phenolization
method".
Another medical application of phenol is its use as a neurolytic agent, applied in order
to relieve spasms and chronic pain. It is used in dermatology for chemical face peeling.
Phenol is a toxic and corrosive compound often used in DNA extractions -- not exactly
the kind of thing you want to eat. A variety of organic compounds, however, contain the
same chemical group and structural features that distinguish phenol, and many of
these other compounds are beneficial for your health. Compounds in this class are
collectively called phenols.
Cancer Prevention
Some phenolic compounds are believed to be cancer chemopreventives, compounds
that may decrease your risk of developing cancer. Epigallocatechin-3 gallate, for
example, is a phenolic compound found in green tea and believed to be a cancer
chemopreventive. A broad group of phenolic compounds called flavonoids are common
in plants; according to a review in the "British Journal of Nutrition," there is evidence to
suggest many flavonoids like anthocyanins may have anticancer effects.
Antioxidants
Many phenolic compounds found in plants may have antioxidant effects, meaning they
react with and capture dangerously reactive compounds called free radicals before the
2|Page

radicals can react with other biomolecules and cause serious damage. Flavnoids and
tocopherols are two broad classes of phenolic compounds with antioxidant properties.
Resveratrol, a phenolic compound found in grape skins and red wine, also has
antioxidant effects.
Other use are housing construction, fiber, detergents, gazing, coating, sheets and films
etc.
Apart from various uses phenol is toxic material should be handled carefully. In
presence of light or higher temperature decomposition of phenol takes place so should
be kept in dark container and away from sunlight.
The most important chemical made from phenol is bisphenol A, which is used to make
the polycarbonates. Phenol is also catalytically reduced to cyclohexanol, which is used in
the manufacture of polyamides 6 and 6,6.
Phenol is also used to make a range of thermosetting polymers (resins). It reacts with
methanal in the presence of a catalyst to form phenol-methanal resins.
Among the other uses of phenol is the production of phenylamine (aniline) needed, for
example, for the manufacture of dyes. Antiseptics such as 2,4-and 2,6-dichlorophenols
are also made from phenol.
Phenolic resins are found in myriad industrial products. Phenolic laminates are made by
impregnating one or more layers of a base material such as paper, fiberglass or cotton
with phenolic resin and laminating the resin-saturated base material under heat and
pressure. The resin fully polymerizes (cures) during this process. The base material
choice depends on the intended application of the finished product. Paper phenolics
are used in manufacturing electrical components such as punch-through boards and
household laminates. Glass phenolics are particularly well suited for use in the high
speed bearing market. Phenolic micro-balloons are used for density control. Snooker
balls as well as balls from many table-based ball games are also made from phenol
formaldehyde resin. The binding agent in normal (organic) brake pads, brake shoes and
clutch disks are phenolic resin. Synthetic resin bonded paper, made from phenolic resin
and paper, is used to make countertops.
Phenolic resins are also used for making exterior plywood commonly known as WBP
(Weather & boil proof) Plywood because Phenolic resins have no melting point but only
a decomposing point in the temperature zone of 220 degree Celsius & above. Phenolic
resin is used as a binder in loudspeaker driver suspension components which are made
of cloth.

3|Page

4|Page

2. Market Prospects 1.

Phenol Consumption 7166000 tonnes consumption in 2002

2.

Consumption Growth (%)

1997-2002

2002-2007

2007-2012

2009-2014

2014-19

5.2

4.4

1.7

5.1

2.5

3.

Capacity in 2002 - 7,843000 tonnes

4.

Production in 2010 8 million tonnes

5.

Capacity in 2010 10.4 million tonnes

Demand: The outlook for the phenol market in 2014 is uncertain, particularly for major
derivative Bisphenol A (BPA) which drives global demand. The global demand for phenol
has been steadily increasing over the last 10 years. In 2000, global phenol demand
stood at 6,072,774 tons, before increasing to 7,934,218 tons in 2010. A significant
portion of the increase in demand for phenol was from the Asia-Pacific region, and this
is expected to continue in the forecast period. The Asia-Pacific region is expected to
account for 51.2% of global phenol demand in 2020. The global demand for phenol will
increase to reach 11,576,620 tons by 2020.
According to SRI consulting report 2010 global production and consumption of phenol
were both around 8.0 million tonnes with global capacity utilization of 77%. Phenol
consumption is expected to average growth of 5.1percent per year from 2009 to 2014
and around 2.5% from 2014-19. Phenol is consumed mainly for production of bisphenol
A and phenolic resins which accounted for 42% and 28% respectively of total phenol
consumption in 2009.

5|Page

Year

Installed Capacity
(in x10^3 MT)

Production
(in x10^3 MT)

Consumption
(in x10^3 MT)

2006-07

-------------------

71.27

137.43

2007-08

-------------------

74.94

175.73

2008-09

-------------------

75.75

165.47

2009-10

-------------------

71.59

171.94

2010-11

-----------------

79.81

202.01

2011-12

77.13

65.93

211.54

2012-13

77.13

59.92

232.24

2013-14

77.13

46.39

258.35

Fig. 2 Yearwise Installed Capacity, Production & Consumption of India

Year

Exports
(quantity in MT)

Exports
(Value in lakhs)

Imports
(quantity in MT)

Imports
(Value in lakhs)

2006-07

68754

40552

66158

37795

2007-08

102871

66153

100793

63950

2008-09

92918

46763

89723

43010

2009-10

103071

51907

100351

48638

2010-11

123490

93671

122197

91350

2011-12

146762

111194

145616

109047

2012-13

172758

139980

172323

138952

2013-14

214098

172427

211956

169197

6|Page

Fig. 3

Producers

Location

Phenol Capacity (kT/year)

Hindustan Organic
Chemicals

Kochi

42

SI Group India Ltd

Navi Mumbai

37

3. Available process for the production of product Significant improvements in the technology for the production of phenol have been
made over the past decade. New catalysts and processes have been commercialized for
the production of cumene via alkylation of benzene with propylene. Recent process
design innovations have been commercialized for the cumene hydroperoxide route that
remains the process of choice for the production of phenol. All of this effort has been
directed at improving yield, process economics/costs, and process safety for the
preparation of phenol as a key intermediate for the growing bis-phenol A and phenolic
resins markets. A review of technology offerings by major licensors of these new
7|Page

processes is provided as well as a discussion of key process differences and recent

advances.
Current state-of-the-art processes for the production of cumene as a feedstock for
phenol involve technology offerings from UOP, Badger Licensing (formerly ExxonMobil
and the Washington Group) and CDTech based on zeolitic catalysis. For cumene
hydroperoxide processing to phenol technology, offerings by UOP/Sunoco (formerly
Allied-UOP technology), GE/Lummus, and KBR (Kellogg-Brown & Root formerly BPHercules technology) represent the state-of the-art based on the autocatalytic cumene
oxidation and dilute acid cleavage (cumene hydroperoxide decomposition) processing
routes.
Much of the improvement in these technologies falls along the lines of improved yield
and stability for the zeolitic cumene technologies and improved yield, safety, and
economy for the phenol technologies. A brief discussion regarding alternative methods
of phenol production such as the toluene oxidation route and direct oxidation of
benzene to phenol is also presented as shifting economic considerations in the future
may

make

these

processes

more

attractive.

A. Sunoco/UOP Phenol process

The Sunoco/UOP Phenol process produces high-purity phenol and acetone by the
cumene peroxidation route, using oxygen from air. This process features low-pressure
oxidation for improved yield and safety, advanced CHP cleavage for high product
selectivity, an innovative direct product neutralization process that minimizes product
waste, and an improved, low cost product recovery scheme. The result is a very low
cumene feed consumption ratio of 1.31 wt. cumene/wt. phenol that is achieved without
acetone recycle and without tar cracking. The process also produces an ultra-high
product quality at relatively low capital and operating costs. Extensive commercial
experience has helped to validate these claims.
B. KBR 4th Generation Phenol process
KBR 4th Generation Phenol process also claims improvements for the cumene
peroxidation route for a process based on high-pressure oxidation technology. These
include improved oxidation yield, an advanced cleavage system, elimination of tar
cracking, and an efficient energy and waste management system.
C. GE/Lummus Process
It claims various improvements to the cumene peroxidation process. It is similar to KBR
in that it is also based on high-pressure oxidation technology. Improvements include
enhanced oxidation reaction rates, an advanced cleavage section using a co-catalyst,
elimination of tar cracking, and an improved product recovery scheme.
8|Page

Overall process description/chemistry

The main reactions for phenol and acetone production via cumene peroxidation are
shown in Fig. 4. Both reactions are highly exothermic. Oxidation of cumene to cumene
hydroperoxide (CHP) proceeds via a free-radical mechanism that is essentially autocatalyzed by CHP. The decomposition reaction is catalyzed by strong mineral acid and is
highly selective to phenol and acetone. In practice, the many side reactions which take
place simultaneously with the above reactions are minimized by optimization of process
conditions. Dimethylphenylcarbinol is the main oxidation by-product, and the
DMPC/AMS reactions play a significant role in the plant.

9|Page

4. Techno-Economic appraisal of alternative processes

GE/Lummus claims an improved flow scheme to clean up acids and other activity
depressing components present in the recycle cumene stream. This results in enhanced
cumene oxidation rates for their high-pressure oxidation technology. However, the
process is more likely to have higher yields of these components as a result of the
higher operating pressure. This requires greater measures to ensure adequate clean up
compared to a more modern low-pressure system that provides higher oxidation yields.
Also, the high pressure system is more complex and costly and requires higher air
compression costs. With either low-pressure or high-pressure oxidation, the oxidation
air strips light acids out of the oxidation products.
With Sunoco/UOP low pressure oxidation, the air stripping combined with partitioning
of the acids to the condensate in the spent air cumene recovery system and the weakcaustic scrubbing of the recycle cumene is so effective that no other method of acid
removal is required. This does not appear to be the case for GE/Lummus high-pressure
oxidation.
KBR employs a similar high-pressure oxidation technology for the manufacture of
phenol. KBR claim to have eliminated the sodium carbonate scrubbing system
completely thereby reducing capital and operating costs. The aqueous effluent rate for
the oxidation section is also said to be reduced by as much as 75% resulting in off-site
treating savings. However, similar to GE/Lummus, higher reactor/compressor section
10 | P a g e

costs and lower yields are likely to more than offset these gains compared to lowpressure technology.
GE/Lummus claims improvements in the CHP decomposition technology. The
technology employs a cocatalyst CHP cleavage process using a very precise mix of NH3
and H2SO4 to control acidity at the optimal level for maximum yield. However, use of
such a pre-neutralized acid mix may greatly reduce reaction rate; resulting in much
higher decomposer residence times.

5. Selection of Technology/Scheme
5.1 Basis of Selection
Sunoco/UOP Process was chosen based on the benefits mentioned in the technoeconomic appraisal above.
5.2 Details of selected process - Sunoco/UOP Process
The major processing steps include:
(1) Liquid-phase oxidation of cumene to cumene hydroperoxide [CHP]
(2) Concentration of CHP
(3) Acid-catalyzed decomposition of concentrated CHP to phenol and acetone
(4) Neutralization of acidic decomposition product
(5) Fractionation of the neutralized decomposition product for recovery of acetone,
phenol, AMS, and residue
(6) Recovery of phenol and the effluent wastewater via an extraction process to prepare
it for further downstream treatment required to meet effluent quality specifications
(7) Hydrogenation of AMS back to cumene for recycling to synthesis; or, optionally,
refining of AMS for sale as a product

11 | P a g e

The details of each of these main processing steps are discussed as follows highlighting
recent technological advances made by various licensors of phenol technology.

5.3 Process flow and recent technology advances

5.3.1 Oxidation section process flowUsing the Sunoco/UOP process as an example, Fig. 7 shows a typical series flow twooxidation reactor configuration for the low-pressure technology. As many as 56
reactors or more reactors can be used in multiple reaction trains depending on the
capacity of the unit, location, processing objectives, and to stage the investment over
time as capacity increases are needed.
The fresh cumene feed is pumped from the oxidation day tank to the combined feed
surge drum. Recycle cumene streams from other sections of the plant are combined
and flow through the feed pre-wash column, where organic acids are removed by
scrubbing with weak caustic and water. The recycle cumene then joins with the fresh
cumene feed in the combined feed surge drum. The combined feed is then pumped to
oxidizer No. 1.

12 | P a g e

Cumene is also used for various utility-like purposes through the plant. Cumene is sent
from the day tank to the phenol recovery section on a batch basis as make-up solvent. It
is also used as pump seal flush in the various sections of the plant. The two oxidizers
are in series with respect to liquid flow but in parallel with respect to air flow. The
oxygen requirement for the oxidizers is supplied from atmospheric air. The air is first
filtered and then compressed before going into the oxidizers through a sparger. The
heat of reaction in the first oxidizer is balanced by adjusting the temperature of the cool
cumene feed, so that no other cooling is required.
For large phenol units, it is economical to recover the heat of reaction from the second
oxidizer by heat integration with the concentration section. The hot oxidizer circulating
liquid stream is used to supply heating to the pre-flash column upper vaporizer. The net
oxidate from oxidizer No. 2 (effluent from oxidation section) flows directly to the
concentration section. As shown in the flow diagram (Fig. 8) again for the Sunoco/ UOP
process, the spent air streams from both oxidizers are combined and routed through a
water-cooled condenser, a chilled condenser and an entrainment separator for the
maximum removal of hydrocarbon and cumene. From the entrainment separator, the
air flows to the charcoal absorbers.
Two of the adsorbers are always on line in series flow, while the third one is being
regenerated with steam. The cleaned air from the charcoal absorbers is vented to safe
atmospheric disposal. A catalytic incinerator is usually not needed to meet emission
limits, but one can be provided if regulations stipulate incineration as the emission
13 | P a g e

control method. The cumene collected by the charcoal adsorbers is recovered by

desorption with low-pressure steam followed by condensing the steam and decanting
the cumene and water phases. The cumene is then recycled to the
feed pre-wash column.

Recent advances in oxidation section technology

For the Sunoco/UOP technology, recent improvements to the oxidation section include:
(1) The use of high-efficiency charcoal adsorption to recover trace products from spent
air
(2) Use of an emergency water spray installation and elimination of oxidizer rupture
disks
(3) A reduction in oxygen content of vent gas thus reducing air compressor capacity
(4) The elimination of the requirement for caustic scrubbing of fresh feed from zeolitic
cumene

unit

(5) Use of a dilute caustic wash tower that replaces the feed wash mixer/settler system
(6) The integration of the decanter with the concentration section vacuum system and
elimination

of

the

vent

gas

scrubber

(7) The integration of the feed coalescer into the combined feed surge drum and
(8) The use of common spares for oxidizer pumps and emergency coolers.
All of these improvements serve to reduce capital and operating costs of the process
making it one of the most effective phenol processes available

14 | P a g e

5.3.2 Concentration section process flow

An example of the typical flow for the concentration section of the process where CHP
in the oxidizer reactor effluent is concentrated to a level of 7585 wt.% prior to
decomposition to phenol and acetone is shown for the Sunoco/UOP process in Fig. 9.

The oxidate from the last oxidizer flows to the concentration section to recover
unreacted cumene. For large phenol units, it is economical to use a two-column
concentration system, in which the heat of reaction from oxidizer No. 2 and very lowpressure steam are used to vaporize cumene in the first (pre-flash) column, reducing
the size of the main flash column. The pre-flash drum and flash column operate under
vacuum to minimize the temperature necessary to concentrate the CHP. The vacuum is
typically generated by an ejector system. Under vacuum in the pre-flash drum, cumene
vaporizes in the upper vaporizer using heat from the second oxidizer cooler. Additional
cumene vaporizes in the lower vaporizer with heat supplied by very low-pressure
steam. Final CHP concentration is achieved in the flash column vaporizer and flash
column, both of which operate under deeper vacuum than the pre-flash drum. The preflash drum bottoms stream flows through the flash column vaporizer, where additional
cumene vaporizes using heat from low-pressure steam.
The CHP content of the flash column overheads is minimized by rectification in the flash
column, using either screen trays or packing, whichever is more economical. The flash
column overheads, consisting of primarily cumene, is recycled to the oxidation section
via the feed pre-wash column. The concentrated CHP collects in the integral
receiver/cooler at the bottom of the flash column, where it is cooled to a safe
15 | P a g e

temperature. The CHP concentrate from the flash column bottoms reservoir is then
pumped to the decomposition section.
A cumene quench tank is also provided in this section for automatic emergency
quenching of various strategic sections of the concentration section if necessary to
maintain safe operating temperatures in the event of an incipient CHP decomposition
excursion.
Recent advances in Concentration section technology
For the Sunoco/UOP process, recent improvements include:
(1) Heat integration with oxidation section
(2) A two-stage concentration section consisting of pre-flash and flash column
(3) Elimination of overhead receivers
(4) Use of a Packinox style exchanger in the flash column condenser
(5) Use of power traps instead of level-controlled pumped condensate pots.
All of these improvements are claimed to reduce capital costs for the process.
5.3.3 Decomposition section flow
The decomposition or cleavage section of the process involves the catalytic
decomposition of concentrated CHP in the presence of ppm levels of acid to crude
phenol and acetone. The most effective technology for this section is a unique two-step
process described in U.S. Patent 4,358,618 by Sifniades/Allied Corporation patented in
1982. The process involves the use of a back mixed reactor section at low
temperature/higher contact time for the main CHP decomposition step followed by a
plug flow dehydration section at higher temperature/short contact time for conversion
of dicumylperoxide (DCP) to AMS. The process represents a breakthrough in AMS yield
improvement and with the expiration of the patent in 1999, is currently being used by
all licensors as the process of choice for modern high yield phenol technology. An
example of the most advanced decomposer technology is the process offered by
Sunoco/UOP shown in Fig. 10. It consists of a very simple but elegant drum and loop
reactor design where concentrated CHP from the concentration section flows into the
decomposer drum, along with a metered amount of water to maintain optimal reaction
conditions in the decomposer recycle loop. Sulfuric acid is injected via injection pumps
into the loop to provide the catalyst required for the decomposition of CHP to phenol
and acetone. A circulation pump is provided to circulate the content of the decomposer.
Sulfuric acid is injected into the circulating stream to such an extent that the
decomposition of CHP and dehydration of dimethylphenylcarbinol (DMPC), a key byproduct of oxidation reaction, are precisely controlled. The level of unreacted CHP is
monitored via calorimeters, to which part of the acid catalyst flow is routed.
16 | P a g e

The effluent from the decomposer is pumped to the dehydrator in which the effluent is
heated to a temperature where remaining DMPC is dehydrated and DCP converted to
AMS at very high yield. This is a unique advantage of the Sunoco/UOP decomposition
technology. The Sunoco/UOP process produces approximately 90% AMS yield from
DMPC. This also results in higher phenol yield, thus lower cumene consumption and
less residue (e.g., tar) formation.

Recent advances in Decomposition section technology

In addition to very high yields across the decomposer section, the Sunoco/UOP
technology offers the following recent improvements:
(1) The implementation of advanced process control (APC)
(2) A reduction in required recycle rate from 100:1 to 25:1
(3) The elimination of water injection tank and pumps
(4) Use of acid totes to eliminate the acid tank dependent on unit size and client
preference
(5) Design of the unit for safe containment in most probable relief situations and
elimination of the catch tank.
The major advantage of these improvements is reduced capital costs and improved
process yields and economics. AMS yields as high as 8590% across the decomposer
section have been demonstrated making the Sunoco/UOP technology one of the most
selective offerings in the industry today.
17 | P a g e

5.3.4 Neutralization section process flow

The acid catalyst that is added in the decomposition section must be neutralized to
prevent yield loss due to side reactions and protect against corrosion in the
fractionation section. The Sunoco/UOP Phenol process uses a novel approach for
neutralization: the acid catalyst is neutralized by injecting a stoichiometric amount of a
diamine which does not need to be removed from the process, as shown in Fig. 11.
The main advantages of direct diamine neutralization over conventional systems are:
(1) A new/simplified design that is easy to operate and reduces capital cost
(2) Process uses soluble salts that reduces reboiler fouling and lowers maintenance
costs
(3) Does not require water addition for neutralization which in turn lowers wastewater
production and reduces distillation utilities.

Recent advances in Neutralization section technology

By replacing older ion exchange resin technology with the new direct neutralization
process, Sunoco/UOP claim that phenolic wastewater production can be reduced by
45% or more at lower capital cost.

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5.3.5 Acetone refining section process flow

Acetone is a major by-product of the CHP oxidation process for the production of
phenol. The overall economics of the process are highly dependent on production of
high quality acetone (e.g., 99.799.9% purity) for sales in the solvents market and bisphenol A markets.
Fig. 12 shows the typical flow scheme for the Sunoco/UOP process. Fractionation feed
goes from the fractionation feed tank to the crude acetone column. Water is injected as
necessary to the bottom of the crude acetone column to increase the volatility of the
acetone and maintain the bottom temperature. The overhead of the column, consisting
of acetone, water and some cumene flows to the finished acetone column (FAC).
The key impurities removed in the FAC are aldehydes, which have been historically
analyzed with the permanganate fading test, and water. More recently, as the product
quality demands for acetone have increase, most phenol producers use gas
chromatography (GC) as the definitive method for determining aldehyde content. The
Permanganate Fading test is simply not effective for aldehydes unless the level is in the
range of several hundred ppm or more. Caustic is injected into the FAC column to
catalyze the condensation of trace aldehydes. The heavier condensation products are
less volatile and leave with the FAC bottoms.
High-purity acetone flows by gravity from the FAC side cut near the top of the column to
the acetone product day tank. The net bottoms stream of the FAC flows to the FAC
bottoms drum where cumene and water are separated. The water goes to the sewer
while the cumene is recycled to the oxidation section.

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Recent advances in Acetone refining section technology

Recent improvements for the Sunoco/ UOP process include the use of stabbed-in
condensers and elimination of overhead receivers, where appropriate, to save capital
cost.
5.3.6 Phenol fractionation and purification process flow
Once the crude phenol has been produced, it must be further fractionated to prepare a
finished product that is of sufficient purity to meet downstream user specs. An example
of the phenol purification is shown in Fig. 13. It is based on Sunoco/UOP technology
using AMS hydrogenation as a means of recycling the by-product AMS to maximize
phenol production.
The bottoms material from the crude acetone column flows to the cumene/AMS column
where cumene and AMS are recovered overhead and sent to the cumene caustic wash
in the phenol recovery section. A chemical agent is injected into the bottom half of the
column for the removal of carbonyl impurities such as acetol (a-hydroxyacetone) and
mesityl oxide from the phenol. The bottoms from the column are routed through a
chemical treatment reactor which provides residence time for the chemical treatment
reactions.

20 | P a g e

The effluent from the chemical treatment reactor flows to the crude phenol column
where the heavy components distill to the bottoms and then flow into the residue
stripper column for removal as the net residue by-product. This separate residue
stripper column section allows the final stripping of phenol from the residue to be
conducted at higher vacuum, which allows both the crude phenol column and residue
stripper column to be reboiled with medium-pressure steam. Thus, no high-pressure
steam is required for the phenol plant! The residue product has flow and combustion
properties similar to No. 6 fuel oil, and is typically charged to a dedicated burner a
boiler furnace.
The crude phenol column has a top pasteurizing section to remove the small amount of
light by-products generated during distillation. The main product from the column is
taken off as a side cut and flows to IX resin treaters, in which the ion exchange resin
catalyzes conversion of methylbenzofurans (MBF) and residual AMS to high-boiling
components. MBF and AMS are otherwise difficult to remove by distillation. The effluent
from the IX resin treaters goes to the phenol rectifier, where the heavy components
along with some phenol are distilled to the bottoms and recycled back to the crude
phenol column. The phenol rectifier also has a top pasteurizing section for removal of
small amounts of light by-products generated during distillation. Phenol product flows
by gravity from the rectifier side cut to storage.

Recent advances in Phenol purification section technology

For the Sunoco/UOP process, improvements in the phenol fractionation and purification
section included:

21 | P a g e

(1) Replacement of the azeotropic phenol stripper with chemical/resin treating

(2) Elimination of the acid neutralizer system
(3) Use of stabbed-in condensers and elimination of overhead receivers where
appropriate.
The main benefit of these changes has been reduced capital/utilities cost while
maintaining the already very high overall phenol product quality. Further, equipment
sizes and wastewater have been significantly reduced by implementation of the
advance Sunoco/UOP Phenol recovery technology shown in Fig. 14.

5.3.7 AMS hydrogenation section flow

The Sunoco/UOP Phenol process utilizes AMS hydrogenation technology developed by
Huels. The Huels MSHPTM process is a mild hydrogenation process based on a Pd
containing catalyst system that operates at moderate pressure. The process achieves
nearly complete conversion of AMS with very high selectivity to cumene resulting in a
very low overall process cumene/phenol consumption ratio of 1.31 w/w. The simple
process shown in Fig. 15 has been demonstrated to operate without significant catalyst
deactivation over multiple years of operation.
In this section the AMS in the cumene/AMS stream from the phenol recovery section is
selectively hydrogenated to cumene by the Huels MSHP process. The fresh
cumene/AMS feed is mixed with reactor effluent recycle and hydrogen. The combined
feed passes through Hydrogenation Reactor No. 1, where the bulk of the AMS is
hydrogenated to cumene. The reaction is highly exothermic.
22 | P a g e

The reactor effluent recycle is cooled before joining with the fresh feed. The net flow
goes to Hydrogenation Reactor No. 2 as a finishing reactor to complete conversion of
AMS to cumene. Product from the second reactor goes through the product cooler and
then to the product separator. Hydrogen flow is once through, with only a slight excess
over stoichiometric. The flow rate of feed hydrogen is regulated based on the flow of
excess hydrogen and light gases from the product separator. Dissolved gases which
come out of solution when the liquid flashes to low pressure are disengaged in the flash
drum. The cumene liquid product is then recycled to oxidation.

Recent advances in AMS Hydrogenation section technology

Advances in the Sunoco/UOP/Huels AMS hydrogenation technology include:
(1) Elimination of the recycle hydrogen compressor
(2) Elimination of the hydrogen flash drum and pumps. Both of these improvements
save capital cost and utilities.
5.3.8 Tar Cracking
Both Sunoco/UOP and KBR claim that tar cracking of heavy ends produced in the
phenol process is no longer required due to the improvement in process yield achieved
over the last 10 years. KBR claims that phenolic tars have been reduced by as much as
40%. By eliminating tar cracking, phenol product purity has improved so that total
organic impurities (including cresols) have been reduced to 50 ppm, according to KBR.
Sunoco/UOP, with additional refinements in cumene and phenol fractionation
technology, have further reduced this level to about 30 ppm.
5.3.9 Phenol process safety
23 | P a g e

Safety considerations in the production of phenol and acetone from cumene include
design and operating criteria for processing the intermediate CHP. CHP decomposes
rapidly to phenol and acetone when exposed to strong acids, even at low temperatures.
This reaction is highly exothermic and is the second reaction step in the process.
At high temperatures, the rate of CHP decomposition catalyzed by weak acids would
also

become

significant.

In

addition,

CHP

reacts

with

cumene

to

form

dimethylphenylcarbinol. This reaction occurs to some extent under normal conditions

in the oxidation, concentration and decomposition sections, but the rate becomes
significant at higher temperatures. At still higher temperatures, CHP also decomposes
thermally to form acetophenone and methane. CHP decomposition catalyzed by weak
acids and the thermal CHP reactions would only become significant from a safety
standpoint in the event that heat cannot be removed. In such a case the increasing
temperature from the heat of reaction would result in a higher reaction rate, creating
the potential for an uncontrolled reaction.
Thus, the availability of heat exchangers, cooling medium, and pumps for cooling CHP
mixtures is critical from a safety standpoint. A significant advantage of the Sunoco/UOP
low-pressure oxidation technology in addition to high yields is the very mild operating
temperature (e.g., typically 8290 Degree Celcius) required for the process. The lower
oxidizer operating temperature translates into a much longer allowable operator
response time in the event intervention is required due to an upset to prevent oxidizer
temperatures that are high enough to promote CHP thermal decomposition. The
intervention response time may be as long as 24 h or more to avoid elevated
temperatures and high rates of CHP decomposition in the oxidizers. For high-pressure
processes such as KBR and GE/Lummus, the response time is much shorter, on the
order of only a few hours, to prevent accelerated CHP thermal decomposition due to
the higher initial process temperature (e.g., typically 95100 8C or more).
The Sunoco-UOP Phenol process design and operating criteria are based on an industry
accepted 10,000-year probability guideline. Safety provisions include emergency coolers
and pumps, reliable power supplies, reliable cooling water supply, and further backup
provisions including ability to use firewater as once through cooling water, and the
capability to use cool cumene to reduce (quench) temperature. For all cooling services
designated as critical, if cooling becomes unavailable, it must be possible to reestablish
cooling within 20 h with 99.99% certainty.
Analysis has shown that meeting this availability criterion typically requires a cooling
water supply system with a minimum of three pumps, with two normally operating and
the third in standby; and multiple independent power sources for the pumps and
cooling tower fan. For all pumping services designated as critical, if pumping becomes
24 | P a g e

unavailable, it must be possible to re-establish pumping within 20 h with 99.99%

certainty. Meeting this criterion typically requires multiple sources of power. Options for
multiple independent power sources can include, but are not necessarily limited to, an
emergency electric power generator, steam-driven turbine, a direct drive engine, or
multiple independent external electric power supplies. While the first three options are
less reliable than normal electrical power, the combination of multiple power sources
provides a more robust system than a typical single external electrical power supply.
For example, if a diesel powered emergency electric power generator is utilized, a
probability of 97% is typical. Emergency generators are less reliable than normal
electrical power because of the probabilities associated with failure to start, failure to
run, and unavailability due to testing and maintenance. Quantitative risk assessment is
typically performed to verify the reliability of such systems.

6. Raw Material
6.1. SOURCES OF RAW MATERIAL
Cumene peroxidation process is a process involves the liquid phase air oxidation of
cumene to cumene peroxide, which in turn is decomposed to phenol and acetone by
the action of acid. During the cumene peroxidation process, there are two main raw
materials used in this process which are cumene and oxygen. Oxygen is a gas form
fluid. Oxygen is colourless gas that can be found in the air. In the air there is 21% of
oxygen contains while another 79% is nitrogen gas. Oxygen acts as an oxidizer. Table
shown the physical and chemical properties of oxygen as well as cumene.
Most important cumene specifications:
Purity 99.90 wt-%, min.
Benzene 10 wt-ppm, max.
Toluene 5 wt-ppm, max.
Ethylbenzene 50 wt-ppm, max.
n-Propylbenzene 300 wt-ppm, max.
Butylbenzenes 100 wt-ppm, max.
(for 99.5 wt-% AMS purity)

25 | P a g e

PHYSICAL AND CHEMICAL PROPERTIES of CUMENE (TYPICAL)

PROPERTY

DATA & INFORMATION

Synonyms

Isopropyl benzene

Chemical Formula

C6H5CH(CH3)2

Physical State at room

temperature

Liquid

Odor

Aromatic

Appearance

Colorless liquid

Boiling Point Critical

Temperature

152C -

Melting Point

-------------------------

Specific Gravity

0.86 (Water = 1)

Molar mass

120.00 g/mol

Solubility in water

Negligible solubility in cold water

Vicosity
(cSt @ 40C)

0.7

Vapor Pressure

1.1 kPa (8 mm Hg) (at 20C)

Volatility

862 g/l VOC (w/v)

Flash point

Closed cup: 36C (96F). (Pensky-Martens.)

Additional
Properties

Paraffin, Isoparaffin and Cycloparaffin Hydrocarbons

Content = <1 Wt.% (ASTM D-1319);
Aromatic Hydrocarbon Content = >99 Wt. % (ASTM D1319);
Average Density at 60F = 7.19 lbs./gal. (Calculated via
ASTM D-287);
Aniline Cloud Point Temperature = 52F (11C) (ASTM D611);
Kauri-Butanol (KB) Value = 96 (ASTM D-1133);
Dry Point Temperature = 307F (153C) (ASTM D-86, D-850
or D-1078);
Evaporation Rate = 0.5 (n-Butyl acetate = 1.0);
Heat Value = 18,670 Btu. per pound

26 | P a g e

STABILITY AND REACTIVITY

Chemical
Stability

Stable.

Hazardous
Polymerization

Not expected to occur.

Conditions to
Avoid

Keep away from heat, sparks and flame. Forms explosive

peroxides with prolonged storage

Materials
Incompatibility

Strong acids, alkalies, and oxidizers

Hazardous
Decomposition
Products

No additional hazardous decomposition products were identified

other than the combustion
products identified in Section 5 of this MSDS.

6.2 Availability of Cumene

Ashland Chemical, Inc. and Chevron Chemical Co. offer cumene in tank car, tank truck,
and barge quantities.
Cumene is available from various Naptha crackers across India which includes - IOCL
Panipat, Hazira of Reliance, IPCL Vadodara, Haldia of Haldia petrochemicals
6.3 Import Data
Major importers of cumene in India are Macoma Hardwares
Tuff Stone Marketing Pvt Ltd.
Chemilab Corporation
Schenectady Herdillia Limited
Bayer Abs Limited
7th Floor, Abs Towers Old Padra Road
BARODA , Gujrat
Btp India Private Limited
Kences Towers, (Ii Floor) , No.1, Ramakrishna Street,t.nagar,
CHENNAI, TAMIL NADU
27 | P a g e

28 | P a g e

29 | P a g e

6.4 Export Data

Major Exporters in India are Alok Industries Ltd.
43-b;mittal Tower Nariman Point,
MUMBAI. MAHARASHTRA
M-tex Exports
505,gagangiri Avenue, Samta Nagar,opp.raymonds,
THANE , MAHARASHTRA
Chemilab Corporation
55, B. R. B. Basu Road, B- Block, 3rd Floor, Room No. 55,
CALCUTTA , WEST BENGAL

30 | P a g e

6.5 Prevailing prices

6.6 Govt Policies and Import Duty

Import Duty on Cumene
Description

Duty (in
INR)

Basic Duty

5.00

Education Cess

2.00

Secondary Hiigher Education Cess

1.00

Contravailing Duty (CVD)

12.00

Additional Contravailing Duty

4.00

Additional Cess

0.00

National Calamity Contigent Duty (NCCD)

0.00

Abatement

0.00

Total Duty

22.85

31 | P a g e

Bisphenol
1. Uses & Importance Bisphenol is an important building block and its measure use is in the manufacture of
polycarbonate plastic and epoxy resins. Other uses include in flame retardants,
unsaturated polyester resin and polyacrylate, polyetherimide and polysulphone resin.
Some

common

uses

are

mentioned

below

Store Sales Receipts

Some thermal paper receipts can contain BPA as a component of the heat sensitive
coating that allows for inkless printing. This paper technology provides speedy, reliable
and cost-effective printing.
Packaging & Storage
BPA is used to make polycarbonate plastic and polymeric coatings called epoxy resins
for food packaging and storage that are essential to enhance the safety of our food
supply and contribute to healthy, modern life styles.
Medical
Polycarbonate plastic is used to make critical components of many medical devices and
their housings. Its optical clarity allows direct observation of blood or other fluids to
monitor proper flow. Health care providers depend on medical devices and equipment
made with BPA for a transparent view within the human body so they can check for the
presence of air bubbles or other obstructions during medical procedures.
Safety Equipment
BPA is regularly used to strengthen products for human health and safety. Products like
bike helmets, police shields, reading glasses and bullet-proof glass are all shatter
resistant because of BPA.
Electronics & Auto
BPA is used to make parts of cars, circuit boards, flat screen televisions and smart
phonesimproving safety and quality of many of the products.
Industrial & Business
From LED lights to adhesives, find out how BPA is used for industrial and architectural
purposes.

32 | P a g e

Optical Media

Compact Discs

CD-ROMs

Digital Versatile Discs

HD-DVDs

Blu-RayDiscs

Holography Discs

Innovative Data Storage Technology (e.g. Near Field Recording Discs)

Forgery-proof holographic shadow pictures in ID cards

Construction: Buildings

Sheets for roofing, conservatory glazing

Architectural glazing (e.g. sports arenas)

Greenhouse glazing

Rooflights

Cover for solar panels

Noise reduction walls for roads and train tracks

Car port covers

Glazing for bus stop shelters

Roadsigns

Internal safety shields for stadiums

Transparent cabins for ski lifts

Housings and fittings for halogen lighting systems

Roadsigns

Front panels for advertising posters, signboards(e.g. fuel stations)

Large advertising displays

Dust & water-proof luminaires for streetlights and lamp globes

Diffusing reflectors for traffic lights

Others: Safety

Safetygoggles

Protective visors for welding or handling of hazardous substances

Protective visors for motor bikes, snowmobiles

Motorbike and cycle helmets

Fencing helmets

33 | P a g e

Safety shields for policemen

Guards to protect workers from moving machine parts

2. Market Prospects

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

Polycarbonate resin are the largest and fast growing BPA market, consuming
60percent of the global production.

Epoxy production

34 | P a g e

3. Production Methods Various process technologies available for manufacture of bisphenol are:
A) Synthesis of Bisphenol-A from phenol and acetone using Organic-Inorganic
modified heteropoly acid catalyst
BPA is conventionally produced through acid catalyzed condensation reaction between
phenol and acetone by using ion-exchange resins promoted by mercapto compounds.
Excellent performance is shown by ion-exchange resins in experiments. It has been
tested that modified ion-exchange resins like Amberlyst show very good activity for BPA
synthesis. Because of thermal instability of resin catalysts, they cannot be used at
higher temperatures. The other problem being fouling of resin catalysts in the reactor.
Use of inorganic acid catalysts have been tried and found effective.Bisphenol-A is
synthesized using an effective design of heteropoly acid catalyst by organic-inorganic
dual modification. Dual modification was made by partial Cs ion exchange for lowering
acid strength and by immobilization of 2-diethylamino-ethanethiol (DEAT) adjacent to
protonic acid sites. Yields near to 94% is achieved on designed catalyst which is
equivalent to conventional ion-exchange catalyst (yield 96%). The aim of this study is to
develop an effective strategy of catalyst design for BPA synthesis. Ion exchange resins
are the preferred catalysts, but these have temperature limitations.
B) Synthesis of bisphenols using ion-exchange catalysts
Modification of an insoluble strong-acid cation-exchange resin in acid form by partial
neutralization with a mercaptoamine yields an improved catalyst for the preparation of
bisphenols by condensation of a phenol and a ketone.This invention relates to an
improved resin catalyst for the preparation of bisphenols and particularly bisphenol A.
More specifically, the improved catalyst is an insoluble strong-acid cation-exchange
resin in acid form modified by partial neutralization with a mercapto amine. Sulfur
compounds have long been recognized as effective promoters for the acid catalyzed
condensation of phenols and ketones to form bisphenols. For example, in US. Patent
2,359,242 Perkins and Bryner describe the use of H 5 in the condensation of phenol
with acetone, methyl ethyl ketone, cyclohexanone, and other similar ketones. In US.
Patent 2,917,550 Dietzler recommends as a promoter a soluble ionizable sulfur
compound such as H S, methyl mercaptan, ethyl mercaptan, or n-octyl mercaptan.Such
soluble promoters however introduce subsequent problems in the purification of the
bisphenol. Particularly when the bisphenol is used in the synthesis of epoxy and
polycarbonate resins, its purity is a critical factor. Extensive processing is often required.
Thus the search for improved catalysts, greater process efliciency and enhanced
product color, odor and purity continues.Recently Apel, Conte and Bender disclosed in
35 | P a g e

US. Patents 3,049,568 and 3,153,001 a resin catalyst prepared by partial esterification of
a substantially anhydrous strong-acid cation-exchange resin with a lower alkyl
mercaptoalcohol. By chemically bonding the mercaptan promoter to the insoluble resin
by esterification, contamination of the product with the mercaptan is reducedIt has now
been discovered that partial neutralization of a strong-acid cation-exchange resin with a
C -C alkyl mercaptoamine provides another new and improved resin catalyst for the
preparation of bisphenols. As illustrated by the following equation for partial
neutralization of a sulfonated aromatic resin with 2-mercaptoethylamine.

C) ZnCl2-modified ion exchange resin as an efficient catalyst for bisphenol-A

production
A ZnCl2-modified ion exchange resin as the catalyst for bisphenol-A synthesis was
prepared by the ion exchange method. Scanning electron microscope (SEM),
thermogravimetric analyzer (TGA) and pyridine adsorbed IR were employed to
characterize the catalyst. As a result, the modified catalyst showed high acidity and good
thermal stability. Zn2+ coordinated with a sulfonic acid group to form a stable active site,
which effectively decreased the deactivation caused by the degradation of sulfonic acid.
Thus the prepared catalyst exhibited excellent catalytic activity, selectivity and stability
compared to the unmodified counterpart.To overcome the shortcomings of ion
exchange resins, numerous efforts have been made, including loading thiol groups
and/or amine groups by means of reduction, esterification, neutralization or ion
exchange method. Takahim and Toshitaka successfully synthesized a modified catalyst
with mercapto alkyl amine, which showed a great improvement in the condensation of
phenol and acetone. Carvill et al. discovered that 4-(2-mercaptoethyl)-pyridine was a
good modified reagent.Ion exchange resins have been used in other reactions, such as
esterification, transesterification, oligomerization. Low acid strength is also one of their
main drawbacks affecting the reaction efficiency. Some researchers attempted to solve
this issue by introducing Lewis acids into the resins. Magnotta and Gates reported that
the acidic property of the complex formed by AlCl3sulfonic acid can be similar to that of
the superacid solution of SbF5 + FSO3H. Shi showed that the efficiency of acid-catalyzed
transesterification and esterification reactions depend on the subtle balance between
Lewis and Brnsted acidities.

4. Techno-Economic appraisal of alternative processes

The use of a novel catalyst based on heteropolyacid supported on clay, particularly
dodecatungstophosphoric acid (DTP) supported on K-10 clay and its comparison with
commercially available resins such as Amberlyst-15, Amberlyst-31 and Amberlyst-XE36 | P a g e

717p shows DTP/K-10 is an efficient and re-usable catalyst which could be employed at
higher temperatures. The kinetics of the reaction with DTP/K-10 have shown interesting
features among which the formation of intermediate isopropenyl phenol was found to
be the rate determining step with the Eley-Rideal type of mechanism.of phenol to
acetone are required for a facile progress of the reaction as well as to suppress the side
reactions of acetone. Conventionally bisphenol-A is manufactured by the acid catalysed
condensation of phenol and acetone. Ion exchange resins are the preferred catalysts,
but these have temperature limitations. High molar proportions of phenol to acetone
are required for a facile progress of the reaction as well as to suppress the side
reactions of acetone. A large number of side-products are generated depending upon
reaction conditions and the type of catalyst. An ideal catalyst for this reaction should be
moderately acidic and shape selective, whereby lesser quantities of the by-products
would be formed. Ion exchange resins have been used in other reactions, such as
esterification, transesterification, oligomerization. Low acid strength is also one of their
main drawbacks affecting the reaction efficiency. Some researchers attempted to solve
this issue by introducing Lewis acids into the resins. It has been proved that the
coordination of a Lewis acid with a Brnsted acid can increase its original
acidity.Therefore, the design of dual acid catalysts based on resins can be advantageous
in the BPA production. In this study, ZnCl2 acting as a Lewis acid was added into cationic
ion exchange resins to fabricate a more efficient catalyst. To the best of our knowledge,
this is the first resin catalyst for producing BPA that contains both a Brnsted acid and a
Lewis acid.

5. Details of selected process

REACTION CHEMISTRY
The acid catalysed condensation of phenol and acetone in homogeneous medium leads
to several products; in particular with strong sulphuric and hydrochloric acids almost 28
products have been identified. Strong acids such as 70% sulphuric acid, hydrochloric
acid or sulphonated polystyrene divinylbenzene cation exchange

37 | P a g e

resins are industrially preferred. Fig. 1 shows the reaction scheme. In a strong
acid medium, acetone is protonated to a stable carbenium ion as shown by
reaction a in Fig. 1. Following steps occur:Reaction b-The carbenium ion adds to the limiting quinonoid structure of
phenol to yield a protonated carbinol.
Reaction c-The carbinol rearranges to release water and yields protonated
isopropenyl phenol.
Reaction d- The isopropenylphenol adds to a second phenol molecule to yield
bisphenol-A.
Several by-products are formed during this reaction and are shown in next fig.

38 | P a g e

39 | P a g e

The major one being the o,p 1 isomer formed by the reaction of p-isopropenyl-phenol
with the phenol in the ortho position (reaction f). Other side products are the chroman
derivatives formed by the reaction of phenol with mesityl oxide, which itself is a product
of self-condensation of acetone followed by dehydration (reaction e, Fig. 2). Out of the
28 products mentioned, those which are formed in relatively larger quantities are 2,2,4trimethyl chromen, 1,1,3-trimethyl-5-indanol, 9,9- dimethylxanthane and dimethyl
hydroxy biphenyl. The remaining by products constitute to less than 0.2% of the
reaction mixture. It is obvious from Fig. 2 that the formation of byproducts can be
suppressed if the self- condensation of acetone followed by dehydration leading to
mesityl oxide is avoided. One of the ways would be to employ excess of phenol over
acetone in batch experiments or semibatch mode of operation with continuous
addition of acetone making the phenol to acetone ratio very high.

40 | P a g e

Chemicals and catalysts

The preparation of alumina, zirconia, chromia exchanged clays and heteropoly
acid supported on clays has been detailed elsewhere [3,11]. Amberlyst-15,
Amberlyst-31 and Amberlyst XE-717p were procured from Rohm and Haas
(USA). K-10 and Filtrol-24 were purchased from Fluka (Switzerland) and
Engelhardt (Germany), respectively.

Preparation of dodecatungstophosphoric acid (dtp) supported

on clay (DTP/K-IO)
Approximately 10 g of K-10 clay was dried in an oven at 120C for 1 h of which 8 g were
weighed for subsequent experiment. 2 g of dry DTP was also weighed.The HPA was
dissolved in 8 ml of dry methanol. This volume of solvent was approximately equal to
the pore volume of the catalyst. The solution was added in aliquots of 1 ml each to the
clay under constant stirring with a glass rod or kneading it properly. The solution was
added at time intervals of 30 sec. Initially and up to the addition of 6 ml of the DTP
solution, the clay was in the powdery form but upon subsequent addition the clay
formed a paste. Further kneading of the paste for 10 min. yielded a dry free flowing
powder. The preformed catalyst was dried in an oven at 120 C for 1 h and then
calcined at 275C for 3 h.

Reaction procedure
All the experiments were carried out in a 100 ml Parr autoclave equipped with a
four bladed turbine impeller. The temperature was maintained within i0.5C of
the desired value. The vessel was also equipped with a speed regulator that could
maintain the desired speed at + 1% of the set value. Predetermined quantities of
reactants and the catalyst were charged into the autoclave and the temperature was
raised to the desired value. Once the temperature was attained the initial sample was
withdrawn at time=0 and the stirrer was started. Further samples were withdrawn at
definite time intervals. A typical experiment consisted of 5.28 g (0.091 gmol) of acetone,
42.77 g (0.451 gmol) of phenol, 1.25 g of catalyst (loading of catalyst, 0.0268 g/cm 3 of
the liquid phase). The reaction temperature was maintained at 100C and 135C for the
ion exchange resins and inorganic catalysts, respectively.

Analysis
The samples were analysed in a gas chromatograph (Perkin-Elmer Model 8500)
equipped with a flame ionisation detector. A 2 0.003 m column packed with 10% OV41 | P a g e

17 supported on chromosorb WHP was used. Calibration curves were prepared by

using standard samples and synthetic mixtures in order to quantify the data.
Results and discussion
1) Comparison of the activity of the catalysts
A maximum of six products were detected in the reaction mixture. The products were
identified as 1,1,3-trimethyl-5-indenol, 2,2,4-trimethyl chromen, 9,9- dimethyl xanthane,
dimethyl hydroxy biphenyl, o,p-l-bisphenol and bisphenol- A. In the case of Amberlyst31 and Ambedyst-XE-717p only o,p-l-bisphenol and bisphenol-A were formed, whereas
in the case of Amberlyst-15, all the by products were formed in large quantities
resulting in a lower selectivity to bisphenol-A.
Since it was desired to test the efficacy of dodecatungstophosphoric acid supported on
K-10, a few experiments were also conducted with the support clay K-10 as well as
Filtrol-24 as shown in Table 1. Both K-10 and Filtrol-24 were rather ineffective. As was
expected, Lewis acid type catalysts, such as alumina exchanged K-10, zirconia K-10,
chromia exchanged K-10 and sulphated zirconia calcined at 650C did not show any
conversion at 135C after 4 h of reaction The Bronsted acid type catalyst were more
effective.
Amberlyst-XE-717p is a promoted ion-exchanger where 17% of the acid sites are
promoted with an undisclosed molecule [21]. The activity of the catalyst and selectivity
for bisphenol-A were very high. The exchange with any sulphur compound reduces the
acidity of the catalyst, whereby the yield of bisphenol- A is increased. The main side
reactions were of acetone, particularly the formation of mesitylene and its subsequent
reactions. The mesitylene reactions are promoted by strong acidic sites. The sulphur
compounds selectively poison the strong acidic sites which are responsible for side
reactions. The activity and selectivity of Amberlyst-15 are much lower than over DTP/K10 and Amberlyst-31, both of which having similar activities; but the latter being more
selective. Amberlyst XE- 717p is more active and selective than both DTP/K-10 and
Amberlyst-31.However, Amberlyst-31 and Amberlyst-XE-717p, like any other ion
exchanger have very poor thermal stability. They can be used at a maximum
temperature of. By contrast, the clay modified catalysts can be used at temperatures as
high as 300C. The lower selectivity of bisphenol-A with DTP/K-10 could be due to its
high acidity giving rise to a variety of by-products. If the acidity of the catalyst is
controlled by reducing the activity of some of the sites; for instance, by doping with
sulphur compounds the formation of byproducts could be lowered. Further, some
reactions can occur on the external surface of the catalysts without any shape
selectivity.
42 | P a g e

2) Effect of speed of agitation

Fig. shows the conversion of acetone at different time intervals. The conversions were
found to remain practically the same at speeds beyond 1000 rpm thereby indicating
absence of solid-liquid mass transfer resistance. Further reactions were conducted at a
speed of 1000 rpm. Since acetone was taken as a limiting reactant it could be concluded
that any external resistance to its transfer from the bulk liquid phase to the external
surface of the catalyst was absent.

Effect of catalyst loading

Fig. shows the plot of initial rate of reaction of acetone (roi , gmol/cm3/s) against
catalyst loading (w, g/cm3). It indicates that the rate of reaction increases linearly up to a
loading of 2.6z 10 -2 g/cm 3 and thereafter remains constant even though the loading is
almost doubled. Since the number of acidic sites available in the reaction medium is
proportional to the available intra-particle surface, the initial rate of reaction of acetone
should be directly proportional to catalyst loading (mass/volume) if there are no intraparticle diffusion limitations.
This indicates the following:
An intra-particle diffusion limitation was set in for the transfer of acetone from the
exterior surface of catalyst beyond a solid loading of 2.6x l0 2 g/cm 3, acetone being the
limiting reactant (CAo << Cpo).
43 | P a g e

 The side reactions were also significant due to extra available active sites.
It clearly demonstrated that mass transfer limitations were set in and not all internal
surface area was utilised for the reaction. In fact, the acetone concentration would
become zero at a certain distance from the centre of the particle and the reaction would
become intra-particle mass transfer controlled. Further experiments were therefore
done at catalyst a loading of 2.6 x l0 -2 g/cm 3 in the absence of intra particle resistance.

Effect of temperature
Fig. shows plots of conversion of acetone with time at temperatures of 120, 135 and
150C. The rate of reaction increases as the temperature increases. The conversions at
120C are linear with respect to time showing zero-order dependence on acetone
concentration. The other two lines indicate non-zero order dependence which will be
discussed later in the kinetic interpretation.

44 | P a g e

Conclusion
The reaction of phenol and acetone was studied over different catalysts. DTP/K- 10,
Amberlyst-31 and Amberlyst XE-717p were found to be better catalysts. DTP/K-10 is
reusable and better as regards its use at higher temperatures. The kinetics was studied
with DTP/K-10 as catalyst where the rate determining step is the formation of pisopropenylphenol from chemisorbed acetone and phenol from the liquid phase within
pores according to Eley-Rideal mechanism. The catalyst was characterised fully. By
taking higher mole ratio of phenol to acetone, a number of byproducts are avoided. The
kinetic model was found to fit the data satisfactorily.

45 | P a g e

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https://www.zauba.com/customs-import-duty/CUMENE/india.html
https://www.zauba.com/importanalysis-CUMENE/hs-code-29096000-report.html
http://www.seair.co.in/product-import-data/cumene-import-data.aspx
www.sciencedirect.com
www.wikipedia.com

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