BISPHENOL-A

Researched and Compiled by: CHALMER M. BELARO

1. Chemical and Physical Description

1.1. Physical Properties
Bisphenol A, also known as
2,2-Bis(4-hydroxyphenyl) propane and
4,4-Isopropylidenediphenol, shown in
Fig. 1, is a white crystalline solid,
appearing like small white to light
brown flakes or powder, with mild
phenolic odor but is not volatile, which
sinks in water. Its specific gravity is
given as 1.195 at 25/25. There is no

Figure 1. Bisphenol A (PC Grade)

data regarding its vapor density. For

the boiling point, records show discordant temperature ranges and imprecise pressures;
181 to 195 at 4 mm Hg, 195 to 200 at 6 mm Hg, 230 at 7.6 mm Hg. Other sources
suggest 100-200 range of boiling point. BPA is volatilized only in traces by steam at 1
atm. Pure BPA has a melting point of 157. Other physical properties of BPA are
presented in Table 1.
Table 1. Other physical properties of BPA

Bulk density

0.492 g/cm3

Heat of vaporization at 1 atm

404 J/g

Flash point

227

Solubility at water at 83

0.344 wt %

1.2. Chemical Properties

The chemical properties of Bisphenols are
determined by Phenolic OH groups, the aromatic
rings and the alkyl bridge. They therefore undergo
the

same

reactions

as

the

corresponding

substituted monophenols. They are also suitable

as building block for higher molecular mass linear
polyesters and polyethers because of their
bifunctionality. Bisphenols which are alkyled ortho
to the OH group readily trap radicals and are
therefore

suitable

as

stabilizers.

Under

hydrogenation condition, BPA is cleaved to give

4isopropylphenol, alkali catalyzed cleavage
gives 4-isopropylphenol in good yields. Both
compounds are good to obtain by other methods.
The

alkali

catalyzed

cleavage

of

various

Bisphenols has been investigated. The cleavage

Figure 2. a. 2D structure of BPA (Upper)

b. 3D conformer of BPA (lower)

can also be catalyzed by acid to form indans and spirobisindans. The purely thermal
cleavage is generally less forward. Chemical structure of the substance is shown in Fig.2.

2. Production

Bisphenol A is a
component

of

polycarbonate plastics
and epoxy resins and is
one

of

volume

the

highestchemicals

produced globally.

Process technologies available for the manufacture of BPA on commercial level

are:

Condensation of phenol with acetone using acid as catalyst;

Condensation of phenol with acetone using ion exchange resin catalyst.

Acid catalyzed condensation of phenol and acetone is one of the commercial

route commonly used for BPA production being the oldest process for its production. In
this process phenol and acetone in 3:1 molar ratio are reacted in four glass lined stirred
reactor at 50 and 1 atm pressure using anhydrous hydrochloride catalyst and methyl
mercaptan as promoter. The residence time is around 3hr in this process in all four
reactors. The reaction is exothermic, cooling water is passing through the reactor jacket
for cooling. Around 99% of the acetone is converted into BPA. Phenol is used in the excess
to ensure predominance of the forward reaction. The most important controlling parameter
is temperature. Higher temperature causes the isomerism of BPA. With further increase
in temperature, viscosity of reaction mixture keeps on increasing. Hydrochloric acid is
stripped off from the crude product of the reactor which is recovered and recycled. The
product is further purified in the next distillation column where water is separated. During
distillation, some stabilizers are added to prevent isomerism of bisphenol to o- and pisomers. The reaction product is then distilled under a reduced pressure in phenolbisphenol a column. Further the purification of BPA for removal of o- and p- isomers takes
place. The product is further purified by crystallization.
Table 2 presents the raw material requirement per 1000 kg of BPA required in its
manufacturing.
Table 2. Raw Material Requirement for Acid-catalyzed
Condensation of Phenol and Acetone

Process selectivity

95%

Phenol

860 kg

Acetone

275 kg

Steam (Energy) requirement

12.5 GJ/ton

The typical BPA product obtained is 99.9% pure while the typical feasible plant
capacity is 7000 MTPA (metric tons per area) to 30000MTPA.

Ion exchange resin catalyzed condensation of phenol with acetone is the new
improved process for the production of Bisphenol-A. Ion exchange resin is todays
preferred catalyst system for BPA manufacturer. It replaces older acid based technologies
by doing away with acid based environment. All of the problems associated with handling
acids, including corrosion and disposal of acid waste are eliminated. Its a fully continuous
process that incorporates catalytic stripping, a novel reactor technology for the
condensation of phenol and acetone. This advanced technology maximizes yield and
conversion using an environmentally preferred ion exchange resin catalyst. The new
reaction system promotes the BPA condensation reaction under highly favorable reaction
condition while simultaneously removing the water of reaction. The catalytic stripping
reactor provides a very high effective phenol to acetone ratio that, together with an
improved high activity and high selectivity catalyst, results in complete conversion of
acetone and max phenol conversion, with low by product formation. Much higher
conversion and better selectivity are achieved than with other ion exchange catalyst
system. This reduces recycles and utility consumption thereby reducing operating and
capital costs. High phenol conversion permits a simple 1 stage crystallization system.
Raw material consumption per 1000 kg of BPA obtained in this process is
presented in Table 3.
Table 3. Raw Material Consumption for Ion Exchange Resin Catalyzed
Condensation of Phenol and Acetone

Process selectivity

98.5%

Phenol

835 kg

Acetone

265 kg

Steam (Energy) requirement

6 GJ/ton

The typical BPA product obtained is 99.93%-99.98% pure while the typical
feasible plant capacity is 25000 MTPA to 100000MTPA.
More detailed comparison of the two processes in manufacturing BPA is presented
in Table 4.

Table 4. Comparison of Different Processes Available for Production of Bisphenol A

Acid Catalyzed
Ion Exchange Resin
Parameter of Differentiation
Catalyzed Process
Process
99.90
Not normalized

99.93-99.98

Phenol consumption (kg/t) max

860

835

Acetone consumption (kg/t) max

275

265

Steam (Energy) Requirement

(GJ/t)
Catalyst life time (years)

12.5

10

Up to 15

Present at greater
extent

Not such problems

seen yet

Acid Handling

Required

Not required

Disposal of waste

A problem

No such problems

Conversion rate

Low

High

Recycle Rate

High

Low

Capital Investment

High

Low

Utility Consumption

High

Low

Maintenance Cost

High

Low

Multi stage portfolio

Single stage portfolio

HCl

High activity ion

exchange resin catalyst

BPA purity (%)

2-4 isomers ppm (max)
Color (APHA) max

Corrosion problem

Stage
Catalyst

150

Due to the above-mentioned points of advantages of condensation of phenol and

acetone with ion exchange resin catalyst, it is apparently more economical, less polluting,
and most advanced technique for the production of BPA, thus, will be more explored in
this paper.

2.1. Chemical reactions involved

The basic reaction of the acid-catalyzed condensation of acetone with 2 moles of
phenol is:

The heat of reaction, for reactants and products in their natural physical state at
25, is calculated from heats of formation as +18.4 kcal/mol. Severe conditions are not
required; a 1:2 molar ratio mixture of acetone and phenol, in the presence of concentration
hydrochloric acid or sulfuric acid at 70% at room temperature deposits a mass of crude
BPA crystals. The reaction conditions predominantly favor the formation of the product,
however, an excess of 1 mol of phenol is maintained in the production of BPA to ensure
this condition.
The reaction proceeds with an electrophilic attack of the proton from the acidic
catalyst on the molecule of acetone. This first step of the mechanism is very similar to the

one in the production of phenolphthalein and DDT and in the alkylation of phenol with
olefins shown in the following reactions.
2.2. Unit operations / Unit processes involved
The main unit operations involved in production of BPA includes ion-exchange,
distillation, heat exchange, crystallization, stripping, and flaking.
A process catalyzed by a sulfonated cation exchange resin modified with 2mercaptoethanol is presented in Fig. 3 in Section 2.3. A mixture consisting of 83.4 %
phenol, 5.1% acetone, 0.1% water, 3.4% recycled BPA, and 8% recycled by-products are
preheated and fed to the reactor. The reactor is operated at 75 and pressure is kept
around 4.4. The residence time is set in one hour. The process runs to a 50% conversion
of acetone. The concentrator is operated at 200 mm Hg. The overhead at the concentrator
is a mixture of acetone, water and phenol at 18-20%. The bottom stream consists of
phenol, BPA, and by-products. The overhead passes through a series of distillation
columns with the first operating at 1700 and pressure of 560 torr will help in removing
water and unreacted acetone from the reactor effluent. Acetone and lights are sent to
second distillation column operating at 950 and then acetone is sent to the lights
absorber to produce a recycle acetone stream while water is sent for the waste water
treatment via recovery column. The bottoms of the crude column having the temperature
of 700 is sent to the crystallization feed pre-concentrator after it is passed from a heat
exchanger where inside temperature is 51 and it is cooled to 54, which distills phenol
and concentrates BPA to a level suitable for crystallization. BPA is separated from
byproducts in a proprietary solvent crystallization and recovery system where it is cooled
from 54 to 41 to produce the adduct of p-p BPA and phenol. Mother liquor from the
purification system is distilled in the solvent recovery column to recover dissolved solvent
which comes in this system through pump. After crystallization, the mixture is separated
in a centrifuge, washed with phenol, and freed of phenol by melting at 130, then
stripping in a column at 200 and 1 mm Hg. The solvent free mother liquor stream is
recycled to the recovery system. A purge from the mother liquor is sent to the purge
recovery system along with the recovered process water to recover phenol. The recovered
purified adduct is processed and fed at a temperature of 410 and pressure is kept
around 25 torr in a BPA finishing system to remove phenol from product, and the resulting

molten BPA of temperature 1750 is solidified in the flaker followed by a pump to produce
product prills which comes out at a temperature of 900 and is suitable for the BPA
market.

2.3. Process Flow Diagram

Figure 3. Ion Exchange Resin Catalyzed Process Flow Diagram for the Production of Bisphenol-A

The following table presents the amounts of phenol, acetone, BPA, and water in
the streams of the whole process.
Table 5. Streamwise Product Distribution

Stream No.

PHENOL
(kg/hr)

ACETONE
(kg/hr)

BPA
(kg/hr)

WATER
(kg/hr)

1
2

693.13

168.78

5.22

146.05

5.22

663.48

52.38

5.22

52.38

146.05

663.48

5.33

3.723

52.38

138.75

7.30

663.48

10

33.174

11

2.482

12

1.095

663.48

13

3.723

33.174

14

1.095

15

663.48

16

662.81

0.67

17

52.38

18

3.723

19

52.38

20

693.13

5.22

21

547.08

2.4. Equiment
Operating conditions of the equipment in the process were explained along with
the operations in Section 2.2.
One main equipment used in the process is the reactor. The kind of reactor varies
depending on the design preference of the manufacturer. Fig 4 is the schematic design
of the fluidized bed by Instytut Ciezkiej Syntezy Organicznej "Blachownia".

Figure 4. Fluidized Bed Reactor for Production of Bisphenol-A

Other equipment include distillation columns, crystallizer feed system, solvent

crystallization and recovery system, BPA finishing system, flaker, light absorber, and
recovery column.

3. Applications and Use

Application Overview:

Production of Polycarbonate:

4. References

Agrawal, R., & Suman, A. (2012). Production of Bisphenol A. District Guna: Department of Chemical
Engineering, Jaypee University of Engineering and Technology.
Association of Plastics Manufacturers. (2007). Applications of Bisphenol A. PlasticsEurope:
Polycarbonate/BPA Group.
Neagu, L. (1998). Synthesis of Bisphenol A with Heterogeneous Catalysts. Kingston, Ontario: Department
of Chemical Engineering, Queen's University.
O'Young, D., Hsieh, S., & Kelkar, V. (2007). United States of America Patent No. US 7,163,582 B2.
Sigma-Aldrich Co. LLC. (2012). Safety Data Sheet: Bisphenol A.
The Dow Chemical Company. (2012). Product Safety Assessment: Bisphenol A.