CHAPTER I

INTRODUCTION
Bisphenol A or BPA is produced in the reaction of two moles of phenol and 1 mole of
acetone in stoichiometry. It is an organic compound with the chemical formula C15H16O2
having a molecular weight of 228.29 g/mol. It has a boiling point of 220C and a melting
point of 150-170C. The boiling point of BPA is high due to the size of its molecules and its
polarity.
The main application of BPA is in the production of polycarbonate plastics and epoxy
resins. For example, polycarbonate is used in eyeglass lenses, medical equipment, water
bottles, digital media (e.g., CDs and DVDs), cell phones, consumer electronics, computers
and other business equipment, electrical equipment, household appliances, safety shields,
construction glazing, sports safety equipment, and automobiles. Among the many uses for
epoxy resins are industrial floorings, adhesives, industrial protective coatings, powder
coatings, automotive primers, can coatings and printed circuit boards. It has been used in a
wide variety of consumer products for several decades and continues to be manufactured in
large quantities around the world. Because of this, almost everyone is exposed to it to some
degree. BPA exposure may occur through the consumption of food and water that had
sustained contact with packaging materials made from BPA. Exposure may also occur from
the environment; commonly detected at low concentrations in both indoor and outdoor air,
surface water, and house dust. It may leach from polycarbonates and epoxy resins used in
food cans and bottles to result in possible widespread exposure of the general public to low
daily doses. A study of almost 1,500 people assessed exposure to BPA by looking at levels of
the chemical in urine. It was found that higher BPA levels were significantly associated with
heart disease, diabetes, and abnormally high levels of certain liver enzymes.
Europe and United States dominate the world BPA market as stated by the
new market research report. BPA production is more widespread across developed regions
though PF (phenol-formaldehyde) resins and BPA are manufactured in every region.
However, due to recent rise in demand, especially in Asian markets, investments in facilities
for manufacturing BPA would commence in developing areas as well. Asian countries,
especially China are expected to witness strong growth in BPA consumption. According to
Global Industry Analysts, the world market for BPA is projected to exceed 6.3 million metric
tons by the year 2015. This is primarily driven by a strong demand from polycarbonate

resins, and robust growth in the Asian regions, primarily in China. The major feed stocks for
BPA production, which are phenol and acetone, are commercially available and also in
demand chemicals for various applications like solvents. About 40% of the world demand of
phenol is in the production of BPA which has the highest percent of consumption while 25%
of the world acetone demand is used for BPA. China manufacturers sell their BPA ranging
from $100-$10,000 per metric ton which designing a plant for BPA will have a large profit
due to the high demand of polycarbonate and epoxy resins today and for the next progressing
years. [1]
Today, there are different processes employed for the production of BPA. The new
improved process is the ion exchange resin catalyzed reaction which our design preferred the
most. The design is condensation reaction of acetone in excess phenol with the presence of an
acidic ion exchange resin, polystyrene divinyl-benzene. The reaction will take place in a
fixed bed reactor. Recovery of reactants and separation of the desired products from the byproducts is done through distillation. Purification process is held at different temperature in
different crystallizers. The design is to yield high purity BPA, approximately 99.5-99.9%
pure.

Chapter II
PROCESS OPTIONS AND SELECTION
2.1 Criteria in process option and selection
Considering the processes available is an important step in designing. Factors and
criteria should be considered by the designers. Table 2.1 shows the criteria in which an option
will be rated upon on.
Table 2.1 Criteria and corresponding rating.
Criteria for Selection

Rating

Product quality and yield

Environmental & safety hazards
Economics & availability of process
Efficiency
Process Control & Suitability

5
4
3
2
1

Note: 5- Highest; 1-lowest

This particular design is for the production of high quality BPA in high yield, thus
process selection should primarily account the effect of the particular option has on the
product quality and yield. Environmental and safety hazards should also be considered, even
above the over-all economics, efficiency and suitability. The criteria for selection are based
on the designers intuition.

2.2 Over-all mode of operation

The mode of operation should be one of the first to be considered in process option
and selection since it dictates the flow of operation. Batch and continuous mode of operation
are compared in table 2.2
Table 2.2 Advantages and disadvantages of continuous and batch process [2]
Process

Advantages(+)

Disadvantages(-)

Versatile (+2)
used when products are produced
with the same processing
equipment (+3)

Batch
(-17)

Continuous
(+4)

enhances operational efficiency

(+2)
leads to higher yield and lower
impurities (+5)
less non-productive time
ideal for products with short
reaction times (+2)
ideal for plants having large
capacities (+3)

lower installation efficiency (-2)

causes disparities in product
quality (-5)
lack of possibility of reaction heat
removal (-2)
more unproductive time (-2)
preferable with products of short
lifetime (-5)
requires shut down for fouling
materials (-3)
applicable only to seasonal raw
materials (-3)
implies higher capital cost before
any production can occur (-3)
higher investment cost in control
and automation equipment (-3)
not versatile (-2)

Considering the capacity of 120,000 tons/year alone, the mode of operation to choose
is continuous rather than batch. The former also provides higher yield and efficiency that may
answer the problem of the disadvantage that concerns about capital costs.

2.3 Catalyst
Catalysts are used to aid in the reaction; it may hasten or slow down a reaction. The
production of BPA may proceed with a homogeneous catalyst or a heterogeneous catalyst to
accelerate the reaction of acetone and phenol. In relation to the production of BPA, the
former may also be called acid catalyst while the latter as ion exchange resin catalyst. Table
2.3 shows the disadvantages and advantages of the two.
Table 2.3 Comparison of acid catalyzed and ion exchange resin catalyzed [3]
Process

Advantages (+)

Disadvantages (-)

higher recycle rate (+2)

readily and widely
technology (+3)

used

Acid catalyzed
(-14)

Ion exchange
resin catalyzed
(IER)
(+25)

non-corrosive (+4)
ideal for high purity products
(+3)
good
in
acid
handling
requirement (+4)
reduces the disposal of catalyst
waste (+4)
low by product formation (+5)
lower utility consumption (+3)
lower maintenance cost (+3)
higher conversion and better
selectivity (+5)

corrosive (-4)
requires management of acid
waste disposal (-4)
leads to lower conversion rate(-5)
higher utility consumption (-3)
higher maintenance cost (-3)

higher costs (-3)

new technology (-3)

Designers chose IER over acid catalyzed based on the presented comparison. IER is
also the latest technology in BPA production. Amberlyst 33 is specifically chosen for the
process since it is manufactured specifically for production of BPA of high purity.

2.4 Reactor
The production of BPA mainly starts in the reactor. Selection for the type of reactor
should be in consideration to the type of feed, mode of operation and products desired. Table
2.4 shows the pros and cons of the CSTR and PFR types of reactor.
Table 2.4 CSTR vs PFR [4]
Type of reactor

Advantages(+)

CSTR
Continuous
stirred tank
reactor
(+1)

PFR
Plug flow reactor
(+12)

Disadvantages(-)

Can run in both batch and

continuous mode of operation
(+2)
Low operating cost (+3)
Easier to maintain (+3)

High
volumetric
unit
conversion (+5)
Suitable
for
continuous
operation (+1)
Lower operating costs (labor
costs) (+3)
Ideal for large scale production
(+2)
Can be used by both
heterogeneous
and
homogenous reactions (+2)
Most suitable when dealing
with heterogeneous catalysts
(+1)

Lower conversion per unit volume

(-5)
More inclined to homogenous types
of reactions (-2)

poor temperature control (-1)

Higher maintenance cost (-1)

The PFR is favorable for the production of BPA since it suits the mode of operation,
type of catalyst and the reaction of phenol and acetone itself.

2.4.1 Type of PFR or Catalytic Reactor

There are two possible PFRs that can be used specially when dealing with
heterogeneous catalysis. The comparison of the two is shown in table 2.4.1
Table 2.4.1 Fixed bed and Fluidized bed [5]
Type of PFR

Advantages(+)

Fixed bed
(+13)

Fluidized Bed
(-8)

Disadvantages(-)

High conversion efficiency (+2)

Low cost (+3)
Minimal maintenance (+3)
Higher ratio of catalyst to
reactants (+2)
Longer residence time giving a
more complete reaction (+2)
Minimal wear on catalyst and
equipment (+2)
Widely used type of PFR reactor
(+3)
Easier catalyst regeneration and
replacement (+2)
Rapid mixing (+2)
Efficient heat transfer (+2)

Difficult in catalyst replacement

(-2)
Poor temperature control (-1)
Undesired heat gradients (-1)

High maintenance cost (-3)

Particle entrainment (-4)
Erosion (-4)
New technology (-3)

Fluidized bed offers advantages that cant be provided by the fixed bed reactor, but
the technology is still raw and needs more research for optimum usage. Fixed bed reactor will
be used in the production of BPA since it provides advantages that result to higher yield and
conversion. Though providing some disadvantages, the fixed bed reactor offers the best
choice for reactor selection.

2.5 Distillation
The reaction of 1mol of acetone and 2mol of phenol theoretically produces 1mol of
BPA and 1mol of water where BPA is the desired product. Water together with some by
products in the reactions such as dimer and chroman compounds are to be separated through
distillation. Un-reacted acetone is also separated. Since the reaction is done in excess phenol,
it is also separated to be recycled in the process. Table 2.5 shows the options for distillation
in the production of BPA.
Table 2.5 Types of Distillation [9]
Type of
distillation
Steam
distillation
(+3)
Vacuum
distillation
(+0-)

Advantages(+)

Disadvantages(-)

Good temperature control (+1)

Cost effective method (+3)
Efficient (+2)
Readily available technology (+3)
Lower level of residue build up
(+4)
Reduced temperature at low
pressures (+2)

High equipment cost (-3)

High operating costs (-3)

High operating costs (-3)

New technology (-3)

Steam distillation is more preferred by the designers for it is efficient. It is also a

technology that is readily available.

2.6 Crystallization
After the separation of the desired product from the impurities, excess phenol,
unreacted phenol and water, BPA is then purified through crystallization. Table 2.6 shows the
possible types of crystallizer that can be used in the purification process.

Type of Crystallizer

Table 2.6 Types of Crystallizer [10]

Advantages (+)

Forced Circulation
Crystallizer
(-4)

Fractional Melt Crystallizer

(+1)

Minimize energy
consumption (+3)
Less maintenance
cost (+3)
Lower
energy
demand for freezing
process (+3)
high selectivity of
crystallization (+5)

Disadvantages (-)

Vacuum Cooling Crystallizer

(-2)

suitable
crystallization method
for continuous
operation (+1)

Detrimental product
quality (-5)
Reduces product
purity (-5)
high demands on the
equipment
construction (-3)
equipment is complex
and expensive (-3)
poor temperature
control in washing (1)
Requires accessory
vacuum hardware that
may increase capital
costs (-3)

Forced circulation crystallizer is an obvious better choice rather than fractional melt
crystallizer but since one of its disadvantages is the reduction of product purity and the
detrimental of product quality, the designers selects fractional melt crystallization for the
production of BPA. It can also work at lower energy requirement since the crystallization of
BPA can be carried out at a relatively low melt temperature of 100C - 120C instead of
160C - 170C.

2.7 Heat Exchanger

BPA is a heat sensitive material therefore it is important for the designers to design
heat transfer equipments, either cooling or heating purposes to avoid the formation of
unwanted isomers. Table 2.7 presents the possible choices of heat exchanger for the
production of BPA.
Table 2.7 Types of Heat Exchanger [10]
Type of Heat Exchanger
Advantages (+)
Shell & Tube
(+7)

Spiral Plate and Tube

(+1)

Heat transfer efficiency

is more (+2)
Can be easily cleaned
(+4)
Compact design (+3)
Capability
of
withstanding
high
pressure (+4)
Maintenance is simple
(+3)
Turbulent flow help to
reduce deposits which
would interfere with heat
transfer (+2)
High overall heat-transfer
coefficients (+2)
Reduces fouling (+4)

Plate fin heat exchanger

(-4)

High heat transfer

efficiency (+2)
Larger heat transfer
area (+2)
Able to withstand
high pressure (+4)

10

Disadvantages (-)

Initial cost is high (3)

Finding leakage is
difficult (-4)
Careful dismantling
and assembling to be
done (-4)

High cost (-3)

Capacities are limited
(-1)
Not for large scale
applications (-1)
Might cause clogging
as the pathways are
very narrow (-4)
Difficult to clean the
pathways (-4)
Aluminum alloys are
susceptible to
Mercury Liquid
Embrittlement
Failure (-4)

CHAPTER III
BASIS OF DESIGN
3.1 Description of the Design
BPA, also called diphenylolpropan (DPP) or 2, 2-Bis-(4-hydroxyphenyl) propane or 4, 4Isopropylidendiphenol, is produced from phenol and acetone. The name indicates that the formation
of a molecular BPA, two (bis) molecules of phenol and acetone molecule are needed. The BPA
making takes place according to reaction:

Amberlyst 33

BPA has a high demand in the world market especially in China and the use of BPA
as a precursor in polycarbonate and epoxy resins production has increased rapidly. The
objective of this design is to produce 120,000 tons/year of pure BPA (99.5%-99.9%) and the
process will be done continuously. The plant will be situated in City of Naga, Cebu
Philippines.

The process design includes condensation reaction of 1 mol of acetone to an excess

mole of phenol in a fixed bed catalytic reactor at 75C by a sulfonated polystyrene
divinylbenzene ion exchange resin catalyst (Amberlyst 33). Excess phenol will help in the
complete conversion of acetone; avoid the formation of different by-products and to ensure
the predominance of forward reaction. The by-products formed are water, o-p BPA, dimers,
spirobiindane, chroman and trisphenols but in minimal amounts. Crystallization, phenol
removal and recovery and the purification of BPA which yields 99.5%-99.9% succeeds the
reaction.

11

3.2 Process Definition

A. Process Concept Chosen
The process chosen is IER catalyzed system because it is a more favorable technique
for BPA production providing important advantages such as its non-corrosiveness in contrast
to HCl. It eliminates the acid handling requirement and reduces the management of waste
disposal regarding catalysts. It has a low utility consumption and maintenance cost therefore
lowering operating and capital costs as well. In terms of purity, M.M. Sharma studied that it
is more advantageous to use IER catalysts when producing high purity BPA. It was also
studied that the technology stated above has high activity and selectivity resulting to a
complete conversion of acetone and maximum conversion of phenol with low by product
formation.
A continuous operation will be preferred in the BPA production. It will be done by
continuously reacting phenol using IER and continuously or essentially continuously
removing water from the system. The continuous removal of water allows for increased
catalytic activity of the resin and therefore improved productivity. Process efficiency is
further enhanced by conducting the process in a device configured to have a combination of
series, parallel or reverse flows which are optionally arranged so the process results in higher
yield and lower impurities. The batch has still some disadvantages which are typical for not
continuous kind of process like lower installation efficiency resulting from technological
stoppages to charge and discharge the reactors, disparities in product quality caused, among
other things, by overheating the catalyst bed packed with a stationary reaction mixture during
the production breaks, due to lack of possibility of reaction heat removal. Thus, our process
design will be done in continuous operation.
Among many IER catalysts used, the sulfonated polystyrene-co-divinylbenzene resin
is the most preferred due to its many advantages including its high conversion when used in
the process, ease of handling, structural uniformity and high abundance in acid sites. Sulfonic
acid type IERs are of gel-type or microporous type but gel-type is advisable because the
activity thereof remains unchanged during use and the industry standard Amberlyst is chosen
by the designers because of its high performance, excellent BPA quality, its lack of
corrosivity and its safety and ease of handling.

12

B. Block Scheme
Bleed

Phenol Recycle
2,143.64 t/a (0.018)

101,091.01 t/a (0.84)

Phenol
98,947.37 t/a
(0.82)

10,389.47 t/a

Reaction
Section

Acetone
30,526.32 t/a (0.25)

4.4 bar
75C

132,533.12 t/a
(1.10)

Splitting
Section

Acetone
Recovery

Phenol
Recovery

0.75 bar
116C

1.013 bar
88C

0.75 bar
152C

31,442.11 t/a (0.26)

BPA
Crystallization
120,000 t/a
(1.0)

3 bar
80-95C (1.0)

BPA
120,000 t/a

122,143.65 t/a (1.02)

Water
9,473.69 t/a (0.079)
Acetone Recycle
915.79 t/a (0.008)
Bleed

N.B.: Figures between brackets () are t/t values.

Total In: 129,473.69 tpa

Total Out: 129,473.69 tpa

13

C. List of Pure Component Properties

PURE COMPONENT PROPERTIES

Component Name

Design

Systematic

Acetone

Propanone

Phenol

Phenol

BPA 4'-dihydroxy2,2-diphenylpropane

Water

Hydrogen
Oxide

Notes:
(1)
(2)
(3)
(4)
(5)
(6)

Technological Data

g/mol

Boiling
Point
(1)
C

Melting
Point
(1)
C

Density
(2)
kg/m3

58.08

56.11

-95.55

789.9

94.11

181.7

40.5

C15H16O2

228.29

360.5

H20

18

100

Formula

C3H6O

C6H6O

Mol.
Weight

Medical Data

At 101.3 kPa
Density at 20C
Skin Contact
Oral in g for Humans per kg weight
MAC in air
LD50 studied in rats

14

MAC
Value

LD
Notes

mg/m3

1,2,4

1.159

1.071

1,2,3

155

1.2

170

>2

5,6

998.2

3.3 Basic Assumptions

A. Plant Capacity:
The

plant

is

designed to

produce

120,000 tons

of

grade

p,p'

isopropylidenebisphenol (BPA) per year by condensation of acetone and phenol with the
presence of an IER catalyst specifically sulfonated polystyrene divinyl benzene. The
production of BPA is to answer the demand of both polycarbonate and epoxy resin
industry of the Philippines and neighboring countries like Taiwan and China. The process
designed shall react 1 mol of acetone to an excess mole of phenol to favor the forward
reaction of acetone and phenol and to achieve a high conversion of acetone to BPA. Byproducts formed in the reaction are treated accordingly before disposal or utilization
thereof.
B. Location
Naga, Cebu Philippines is the proposed location for the BPA production plant. It is

selected based on the given set of criteria: (i) availability of space (ii) availability
of utilities: water, fuel, power (iii) accessibility or transport facility (iv) climate (v)
availability of labor and (vi) proximity to the market. The plant shall have an
estimated land area of 350 hectares. The site is strategically chosen since it provides
accessibility to both land and sea. Accessibility to sea is greatly considered since the raw
materials, acetone and phenol are imported from China. The designers also considered
exporting the product to China and other Asian countries depending on the demand of the
polycarbonate and epoxy resin industries in the Republic of the Philippines.

15

C. Battery Limit
Inside Battery Limit

Outside Battery Limit

Process Equipments

Wastewater Treatment Facility

Two Fixed Bed Catalytic Reactors

Power / Electrical Generators

Three Fractional Melt Crystallizers

Transformers

Three Distillation Columns

Quality assurance Laboratory

Maintenance
Administration building
Pipes
Port Area
Boiler
Condenser / Cooler

Storage tanks / Warehouse for:

Raw materials (acetone and phenol)

Product (Bisphenol A)

D. In and Out going streams

Amount
Incoming Stream Components

Amount

(tons/yr)

Outgoing stream Components

Phenol
(Php 40,849.67 per metric ton)

(tons/yr)

Bisphenol A
98,947.37

(Php 173,696.26 per metric ton)

120,000

Acetone
(Php 40,849.67 per metric ton )

30,526.32

Water

9,473.69

AMBERLYST 33
(Php5,150,421 per metric ton)

1.8

By-products

AMBERLYST 33
-gel w/ HSO3 functional group
-Capacity: 4.8 eq/kg; 1.35 eq/L
-Max operating temp : 130 degrees Celsius
-Coarse Beads: >1.180 2%max

857.46 tpa

-uniformity coefficient- <= 1.60

-harmonic mean size- 0.550-0.7 mm
-fines content: <0.425 0.8% max
-physical form: amber spherical beads

Note: basis of conversion of US dollar to Philippine peso was based on the daily exchange rate of January 6, 2013.

16

PLANT LAYOUT

Legend, Inside Battery Limit:

- Pre-heater for phenol
- Fixed bed Reactor

- Dryer

- Distillation Column 1

- Crystallizers

- Distillation Column 2

- Acetone Storage

- Distillation Column 3

- Phenol Storage

- Control Room

- Bisphenol A Storage

17

3.4 Economic Margin

A design is profitable if the economic margin from the total revenues of one year production
is 70% or higher. The table below shows a tabulation of the cost of raw materials and the total product
revenue.
Table 1. Cost of Raw Materials and Total Product Revenue
Raw Materials

Consumption

Unit Price

(t/a)

(Php/ton)

(Php/year)

Phenol

98,947.37

40,849.67

4,041,967,728

Acetone

30,526.32

40,849.67

1,246,990,196

AMBERLYST 33Wet

8.073944 kg

5,150.42/kg

Total Production Costs

Annual Value (Php)

154,512.60
5,289,112,437.60

Total Production Costs + Utility Costs = 5,818,023,681 Php

Table 2. Total Product Revenue
Product

BPA

Production

Unit Price

Annual Value (PhP)

(tpa)

(Php/ton)

(Php/year)

120,000

171,568.63

20,588,235,290.0

Total

20,588,235,290.0
Economic Margin = (Revenue Cost of Materials) / Revenue
=

x 100

= 71.74%

Since the economic margin is above 70%, the production of BPA from acetone and phenol is
profitable. These calculations are made with the assumptions that the prices are constant within the
project time period.

18

CHAPTER IV
THERMODYNAMIC PROPERTIES
In order to be able to calculate the mass and energy balances, thermodynamic poperties should be specified. Table 4.1 below presents the
different thermodynamic properties of the compounds involved in BPA Production.
Table 4.1 Thermodynamic Properties of Pure Components

Compounds

Melting
Point
(OC)

Boiling
Point
(OC)

Partition
Coefficient

@25 OC
(log Kow)

Vapor Pressure

@25 OC
(Pa)

Critical
Pressure
(atm)

Critical
Temp
(OC)

Gibbs Free
Energy of
Formation
(kJ/kg)

Antoine Constants

Enthalpy of
formation
(kJ/kg)
A

Acetone

-94.8

56.2

-0.24

3.017 x 10^4

47

235

-2,602.87

-3,710.78

Phenol

40.9

181.8

1.47

60.3509

60.5

419

-346.5

-1,023.44

Water

100

3.173 x 10^3

217.5

373.95

-12,678.19

-13,411.62

p-p Bisphenol-A

150-157

360.5

3.4

5.3 x 10^-6

28.92

575.89

-41.23

-1,074.94

Dimers

151.2

398.8

5.5

3.21 x 10^-6

Trisphenol

215.3

505.7

5.8

4.81 x 10^-10

Sprirobiindane

178

425.9

6.3

2.7 x 10^-7

Chroman

131.8

363.5

3.6

5.08 x 10^-5

o-p Bisphenol-A

141.5

377.3

5.0

5.98 x 10^-5

taken from SuperPro Designer v8.5 Database

19

7.02447

1161.0

224

7.133

1516.79

174.95

7.96681

1668.21

228.0

7821.36

176.40

13.2599
-

4.1 Heat Capacity data

The heat capacities of the different components used in the design are given in the
table below. The heat capacity data are presented as a function of temperature
Table 4.2 Heat capacity data

Component

Solid/Liquid
Cp, J/gmol-K

Gaseous Cp, a + bT + cT2 + dT3 in J/gmol-K

A

102b

104c

108d

Water

75.2400

32.2400

0.1924

0.1053

-0.3596

Phenol

196.4000

-13.6952

48.4328

-3.0936

7.2371

Acetone

126.4000

6.3010

26.0600

-1.2530

2.0380

Bisphenol A

533.6600

-72.9483

148.1326

-11.6775

35.9722

taken from SuperPro Designer v8.5 Database

4.2 Vapor-Liquid Equilibrium and Phase diagram
The VLE of the different binary systems and the phase diagrams used in the design
are given below.

Fig. 4.1 VLE for Water-Phenol system at 170oC

20

Fig. 4.2 VLE for Acetone-Water system at 90oC

Fig. 4.3 Boiling Point - Composition for Water-Phenol system at 560mmHg

The red curve represents the dew point and the blue curve represents the bubble point.
21

Fig. 4.4 Boiling Point - Composition for Acetone-Water system at 760mmHg

The red curve represents the dew point and the blue curve represents the
bubble point.
taken from SuperPro Designer v8.5 Database

22

4.5 Liquid Viscosity Data

The liquid viscosities of the different components used in the design are given in the
table below. The liquid viscosity data are presented as a function of temperature.
Liquid Viscosity, log() = A * ( 1/T 1/B), T(Kelvin) and (cP)
A

Acetone

367.25

209.68

Phenol

1405.5

370.07

Water

658.25

283.16

Component

taken from SuperPro Designer v8.5 Database

23

Chapter V
Process Structure and Description
Reaction Section
Phenol and acetone are used as raw materials. Acetone is liquid while phenol is solid
at room temperature. The type of reactor is a fix bed catalytic reactor operating at 75C and
4.4 bars. An ion exchange resin catalyst in the form of polystyrene divinyl benzene
(Amberlyst 33, commercial name) is packed randomly on the reactor.
Splitting Section
The products of reaction from the reactor section are introduced to the first distillation
unit which splits water and acetone in the distillate and phenol and BPA at the bottom. The
operating temperature and pressure is 116.32C and 0.75 bars.
Acetone Recovery
Acetone is recovered in the distillate while water is removed from the bottoms and
treated before proper disposal. Acetone is recovered back to the feed stream. The second
distillation column operates at 760 mmHg and the bottom temperature is at 99.96C.
Phenol Recovery
In the third distillation column, the operating temperature and pressure is 151.2C and
0.73 bar which separates the vapor at 164C which is phenol recycled to the feed stream. The
bottom is at 138.57C which is composed mainly of BPA and purified in the crystallization
section.
Crystallization Section
From the phenol recovery column, the products are introduced to a heat exchanger for
cooling to 75C. The type of crystallizer used is fractional melt crystallizer which introduces
a medium which is cooling water for crystallization and steam for partial and total melting. It
is arranged in series where crystallization is done and cooled to 50C then partial melting at
80C and the last stage which is the total melting at 95 C. In a multiple stage fractional melt
crystallization, the desired component purity of the crystalline medium is upgraded in each
successive stage through the phases of crystallization, partial melting and total melting. The
crystallizer is operated at 3 bars as the operating pressure to maximize the liquid fraction in
the crystallizer. The residence time in each BPA crystallizer is 1 hour. High purity BPA
crystals are produced and dried in a rotary drier.

24

PROCESS YIELDS

Name:
Feed (Phenol)
Acetone
BPA
Water
Wastes
Total

Ref.
Stream
< 1>
< 2>
<28>
<11>
-

Process Streams
kg/s
IN
OUT
IN
3.82
1.18
5

4.63
0.37
5

Steam

13.74
4.24
17.98

t/h

t/t product
IN
OUT

OUT
16.67
1.31
17.98

0.82
0.25
1.07

1.00
0.07
1.07

Cooling Water

74.55t/h
(4.47t/t)

311.95t/h
(18.71t/t)

Phenol

BPA

13.74t/h
(0.82t/t)

16.67t/h
(1.00t/t)

BPA Condensation Reaction

Acetone

Water

4.24 t/h
(0.25 t/t)

1.31t/h
(0.07 t/t)

25

EQUIPMENT
NR.
R01
R02
E01
E02
E03
E04
E05
E06
E07
E08
S01
S02
S03
D01
P01
P02
P03
P04
P05
P06
P07
P08
P09
P10
P11
TOTAL

SUMMARY OF UTILITIES
UTILITIES
Heating
Cooling
Load
Steam
Load
Cooling
(kW)
(t/yr)
(kW)
Water (t/yr)

1,134.30
190.7
80.2

Power
Load
Electr.
(kW) (kWh/h)

44,064
44,064
129,600
1,406,237.7

2,345.76
986.4
129,600

1,222.0

15,030
95.64
30.7
272.495

0.627
0.627
0.122

1,494.276

118,241.28
38,086.56
336,129.12

259,200
259,200
24.192

536,786.35

26

1,533.14

2,246,022.66

1.498
1.473
1.501

4.474

0.4452
0.1872
2.099
0.5452
0.0477
0.0477
0.0005
0.0005
0.0041
0.0065
0.0065
3.3901

CHAPTER VI
MASS AND HEAT BALANCES
Table 6.1 Overall Mass and Heat Balance
IN
Plant
Mass
kg/s
3.93
1.18
5.11

Heat
kW

Mass
kg/s
3.93
1.18

EQUIPMENT
Heat
Stream
kW
Nr.
-626.01
<1>
<2>

R01

Stream
Nr.
<4>

Total
E01

<5>

5.11
5.11

-626.01
-345.13

5.11

-345.13

5.11

13.626
2169.984
2050.829

<5>
<6>
<7>

C01
E06
E02

4234.439
2291.578
77.912
74.049

<10>
<14>
<13>

Total
C02
E07
E03

5.11
0.40

0.40
4.71

2443.539
1942.861
189.291
130.921

OUT

EQUIPM.
IDENTIF.

<4>

Total

<9>
<8>

C03
E08
E04

27

5.11
5.11

-626.01
-345.13

5.11

-345.13

0.40
4.71

2291.578
1942.861

5.11

4234.439

Plant
Mass
kg/s

0.36
<15>
<12>

Total
<18>
<21>
<19>

EQUIPMENT
Mass
Heat
kg/s
kW
5.11
-626.01

<22>
<20>

0.36
0.04

1601.167
842.372

0.40

2443.539

0.05
4.66

543.055
1720.018

Heat
kW

5.11
OUT-IN:

4.71

2263.073

4.66

850.574

4.66
4.66

4.71

2263.073

<25>

4.66

850.574
850.574
-272.614

Total
<19>

E05

850.574
-272.614

<25>

Total
S01

<26>

4.66
4.66

4.66
4.66

-272.614
327.15

<26>

S02

<27>

4.66
4.66

-272.614
327.15

4.66
4.66

327.15
163.59

<27>

Total
S03

<28>

4.66
4.66

327.15
163.59

4.66
4.63

163.59
54.531

<28>

Total
D01

<29>

4.66
4.63

163.59
54.531

4.63

54.531

4.63

54.531

Total

4.63

5.11
9093.142

OUT-IN:

28

9093.142

CHAPTER VII
EQUIPMENT DESIGN
Equipment design is an important part in designing a plant. The materials of
construction are chosen based on the compatibility of the components and the standard
operating conditions are met. All equipments inside the battery limit are dealt in this chapter
and auxiliary equipments are also specified.
Major Equipments
Fixed Bed Catalytic Reactor
The reactor is packed with polystyrene divinyl benzene which is an acidic ion
exchange resin. The material used in construction is stainless steel to avoid discoloration on
phenol that may later affect the purity of the product. An auxiliary reactor is available for
regeneration purposes of the catalyst.
Distillation Column
In the design of the distillation columns, constant molal overflow is assumed. The
mixtures are assumed to behave as ideal and the vapor and liquid equilibrium of the systems
are assumed to follow Raoults Law. All of the non-heavy keys are assumed to end up in the
bottoms stream and all of the non-light keys are assumed to end up at the distillate stream.
Bubble points and dew points of the feed, bottoms, and distillate are computed with the
assumption that the pressure is constant throughout the column. The minimum number of
stages and theoretical stages were calculated using Fenskes Equation and Gillilands
Equation respectively. The minimum reflux ratio and the actual reflux ratio were calculated
using Underwoods Equation. The actual numbers of stages were computed by getting the
overall column efficiency, which was computed using OConnells equation relating the
overall column efficiency to the average molar viscosity and to the density of the vapor of the
distillate. As the rule of thumb states, a 10% allowance to the actual number of stages was
added to the calculated actual number of stages from the overall column efficiency. The
actual feed stage was computed using Kirkbrides equation. The vapor velocity was then
calculated based on the equation given in the book Peters and Timmerhaus. The vapor
velocity at 80% flooding is obtained from the latter solved vapor velocity (without flooding).
The net area for separation, area of the column, and the column diameter is then solved using
the obtained vapor velocity. A downcomer area, assumed to be 15% of the column area, is
29

obtained. A weir length, assumed to be 77% column diameter, is then obtained. A weir height
of 12mm for vacuum distillation and 40mm for atmospheric distillation columns, hole
diameter of 8mm, tray spacing of 0.5m and a plate thickness of 5mm is then assumed(as
recommended by R.K. Sinnott). The height of the distillation column is then solved using the
assumed plate thickness, tray spacing, and number of actual trays is then computed. The
number of holes is then computed using the weir length and the column diameter.
Fractional Melt Crystallizer
In fractional melt crystallizer design, the values are obtained from Superpro based on
the mass flow rate and temperature of the components entering the equipment. The residence
time is based on the literature study and material of construction is a Carbon Steel type of
material. Cooling water is introduced to the first crystallizer to obtain a lower temperature
suitable for crystallization. Steam is introduced also to the second and third crystallizer for
partial melting and total melting of BPA.

30

Major Equipments

Fig 7.1 Fixed Bed Catalytic Reactor

31

FIXED BED CATALYTIC REACTOR SPECIFICATION SHEET

EQUIPMENT NR.
NAME
Pressure
[bara]
Temperature
[C]
Volume
[m3]
Diameter
[m]
L or H
[m]
Thickness
[mm]
Residence time
[mins]
Internals
-Tray Type
-Tray Number
-Fixed Packing
Type
Shape
-Catalyst
Type
Shape
Uniformity coefficient
Capacity
Harmonic mean size [mm]
Max operating temp [C]
Fines content
Coarse Beads
Number
-Series
-Parallel
Materials of Construction (1)
:

:
:
:
:
:
:
:
:
:

R01 and R02

Fixed Bed Catalytic Reactor
4.4
75
4.09
0.8
8.05
1.66
13.34

:
IER (AMBERLYST 33) gel-type
amber spherical beads
<= 1.60
4.8 eq/kg; 1.35 eq/L
0.550-0.7
130
<0.425 0.8% max
>1.180 2%max

1
Trays:
Column: SS SA-240 GR-304

Other
Remarks:
(1) Stainless Steel Grade 304

32

DISTILLATION COLUMN & SPECIFICATION SHEET

EQUIPMENT NUMBER:
NAME
:
Service
Column type
Tray Number
Tray Distance
Column Diameter
Column Height
Heating

Theoretical
Actual
Feed(actual)
(HETP) [m]
[m]
[m]

C02
Distillation Column 1
General Details
distillation / extraction / absorption / ----------

:
:
:
: 10
: 29
: 23
: 0.5
: 1.5
: 15.6
: reboiler

:
:

Tray Material
Column Material

SS314
CS

Process Condition
Stream Details

Temp.
Pressure
Density
Mass Flow
Composition
Acetone
Bisphenol A
Phenol
Water
-------------

Feed

[degC]
[bara]
[kg/m3]
[kg/s]

93
0.74
979.64
5.11
mol%
wt%
1.44
0.69
48.23
7.15
2.1
1.62
48.23
90.55

Top

Bottom

Reflux/

99
0.74
967.82
0.40
mol% wt%
2.94
8.87
0
0
.04
0.21
97.02
90.93

134
0.74
1078.94
4.72
mol% wt%
0
0
94.98 98.19
4.07
1.73
0.95
.08

Absorbent
49
0.135
1137.35
5.73
mol% wt%
2.94
8.87
0
0
.04
0.21
97.02 90.93

Extractant
side
stream

Column Intervals

Trays
Number of
caps
/
---Active Tray Area [m3]
[m]
Weir Length
[mm]
Diameter of
chute pipe
---Remarks:

Packing
Type
sieve holes

hole

Not Applicable
:

----------: 70872
: 1.21
: 1.14

Material
Volume
Length
Width

:
:
:
:

:8

Height

/ ----------

33

Fig. 7.2 Distillation Column 1

34

DISTILLATION COLUMN & SPECIFICATION SHEET

EQUIPMENT NUMBER:
NAME
:
Service
Column type
Tray Number
Tray Distance
Column
Diameter
Column
Height
Heating

:
:
:
:
:
:

11
25
4

0.5

[m]

1.24

[m]

:
:

13.9
reboiler

Theoretical
Actual
Feed(actual)
(HETP)
[m]

C03
Distillation Column 2
General Details
distillation / extraction / absorption / ----------

Tray
Material

SS314

Column Material

CS

Process Condition
Stream Details

Temp.
Pressure
Density
Mass Flow
Composition
Acetone
Phenol
Water
-------------------

Feed

[degC]
[bara]
[kg/m3]
[kg/s]

Top

98
.4
968.48
0.40
mol%
wt%
2.94
8.89
0.06
0.21
97
90.9

Bottom

77
100
1.5
1
975.85
967.47
.04
0.40
mol% wt% mol% wt%
74.8
90.53 99.89 0.20
0
0
0.04
0.23
25.2
9.47
0.06
99.57

Reflux/
Absorbent
100
1.5
975.85
.04
mol% wt%
74.8
90.53
0
0
25.2
9.47

Extractant
side
stream

Column Intervals
Packing
Type

Not
Applicable
:

: 49122

Material

: 0.84
: .95

Volume
Length
Width

:
:
:

: 8mm

Height

Trays
Number of
caps
--------------Active Tray
Area
Weir Length
Diameter of

sieve holes

[m2]
[m]
chute pipe

hole

-------------Remarks:

35

Fig 7.3 Distillation Column 2

36

DISTILLATION COLUMN & SPECIFICATION SHEET

EQUIPMENT NUMBER:
NAME
:
Service
Column type
Tray Number
Tray Distance
Column Diameter
Column Height
Heating

Theoretical
Actual
Feed(actual)
(HETP)
[m]
[m]
[m]

:
:
:
:
:
:

C04
Distillation Column 2
General Details
distillation / extraction / absorption / ----------

2
3
2

: 0.5
: 0.727
: 2.515
: reboiler

:
:

Tray Material
Column Material

SS314
CS

Process Condition
Stream Details

Temp.
Pressure
Density
Mass Flow
Composition
Acetone
Bisphenol A
Phenol
Water
-------------

Feed

[degC]
[bara]
[kg/m3]
[kg/s]

Top

133
0.74
1079.62
4.71
mol%
wt%
0
0
94.97
98.19
4.07
1.74
.95
.08

164
0.74
953.64
.05
mol%
wt%
0
0
0
0
78.77
93.4
21.23
6.60

Bottom

139
0.74
1076.67
4.66
mol% wt%
0
0
98.05 99.3
1.66
0.69
0.29
.01

Reflux/
Absorbent
164
1.9
953.64
4.94
mol% wt%
0
0
0
0
78.77 93.4
21.23 6.60

Extractant
side
stream

Column Intervals
Trays
Number of
caps
/
---Active Tray Area [m2]
[m]
Weir Length
[mm]
Diameter of
chute pipe
---Remarks:

Packing
Type
sieve holes

hole

Not Applicable
:

----------: 16560
: 0.29
: 0.6

Material
Volume
Length
Width

:
:
:
:

:8

Height

/ ----------

37

Fig. 7.3 Distillation Column 3

38

D=2.12 m
P-16

P-17
P-14

FEED
P-18
P-20

COOLING/
HEATING
MEDIUM IN

H=4.14 m

COOLING/
HEATING
MEDIUM OUT

P-9

MELT
P-19
P-22

PRODUCT

Fig. 7.5 Fractional Melt Crystallizer

39

CRYSTALLIZER SPECIFICATION SHEET

EQUIPMENT NR.
NAME

:
:

Effective Volume
Diameter
Height
Materials of Construction

S01
BPA Crystallizer
cu.m
m
m

15
2.12
4.24
CS

Process Conditions
C
C
bar
h
cu.m
cu.m
kW

Feed Temperature
Operating Temperature
Operating Pressure
Residence Time
Crystal Quantity
Slurry Quality
Power for Agitation
Working/Vessel Volume Limits
Min Allowable
%
Max Allowable
%
Component
Mass Flow
Molar Flow Rate
Rate
(kmol/s)
(kg/h)
BPA
Phenol
Water

16667.65
114.13
1.68

0.0203
3.4255x10^-4
2.593x10^-5

*Values obtained from Superpro V8.5

40

75
50
3
1
15
180
1.4977
15
90
Mass
Percentage
(%)
99.31
0.68
0.01

Conc.
(g/l)

1112.89
7.62
0.11

CRYSTALLIZER SPECIFICATION SHEET

EQUIPMENT NR.
NAME

:
:

Effective Volume
Diameter
Height
Materials of Construction

S02
BPA Crystallizer
cu.m
m
m

15
2.12
4.24
CS

Process Conditions
C
C
bar
h
cu.m
cu.m
kW

Feed Temperature
Operating Temperature
Operating Pressure
Residence Time
Crystal Quantity
Slurry Quality
Power for Agitation
Working/Vessel Volume Limits
Min Allowable
%
Max Allowable
%
Component
Mass Flow
Molar Flow Rate
Rate
(kmol/s)
(kg/h)
BPA
Phenol
Water

16781.76
0.0167
1.68

0.0204
4.934x10^-8
2.593x10^-5

*Values obtained from Superpro V8.5

41

50
80
3
1
15
180
1.4977
15
90
Mass
Percentage
(%)
99.989
0.001
0.01

Conc.
(g/l)

11138.32
0.00114
0.114

CRYSTALLIZER SPECIFICATION SHEET

EQUIPMENT NR.
NAME

:
:

Effective Volume
Diameter
Height
Materials of Construction

S03
BPA Crystallizer
cu.m
m
m

15
2.12
4.24
CS

Process Conditions
C
C
bar
h
cu.m
cu.m
kW

Feed Temperature
Operating Temperature
Operating Pressure
Residence Time
Crystal Quantity
Slurry Quality
Power for Agitation
Working/Vessel Volume Limits
Min Allowable
%
Max Allowable
%
Component
Mass Flow
Molar Flow Rate
Rate
(kmol/s)
(kg/h)
BPA
Phenol
Water

16781.78
0.01678
1.662

0.0204
4.9586x10^-8
2.5648x10^-5

*Values obtained from Superpro V8.5

42

80
95
3
1
15
180
1.4977
15
90
Mass
Percentage
(%)
99.989
0.001
0.01

Conc.
(g/l)

11138.32
0.00114
0.114

Fig. 7.5 Heat Exchanger Drawing

43

HEAT EXCHANGER SPECIFICATION SHEET

EQUIPMENT NUMBER : E01

In Series :
NAME
: Heat exchanger 1
In Parallel :
General Data
Service
:
- Heat Exchanger
- Vaporizer
- Cooler
- Reboiler
- Condenser
Type
:
- Fixed Tube Sheets
- Plate
- Floating Head
- Finned Tubes
- Shell & Tube
- Double Tube
Position
:
- Horizontal
- Vertical
Capacity
[kW]
:
345.13
2
Heat Exchange Area
[m ]
:
25.8
Overall Heat Transfer Coefficient
[W/m2 C] :
500
Log Mean Temperature Diff. (LMTD) [C]
:
8..93
Passes Tube Side
Passes Shell Side
Correction Factor LMTD
Corrected LMTD
Corrected
LMTD

Medium

:
:

1
1

:
1
[C]
:
8.93
Process Conditions
Shell Side
Cooling water

Tube Side
BPA, phenol, acetone, Water

[kg/s]

5.1131

[kg/s]
[kg/s]

~
~

~
~

[kJ/kgC]
[kJ/kg]

4.18
~

2.70
~

Temp. IN
Temp. OUT

[C]
[C]

25
46.50

75
50

Pressure
Material
Remarks:
CS carbon steel
SS304 Stainless steel
Shell diameter 12in
# of tubes in shell 55
Tube OD 1.25 in
Tube length 16ft

[bar]
CS

SS304

Mass Stream
Mass Stream
- Evaporize
- Condense
Average Specific
Average
Specific Heat
Heat
Heat of Evap/Condensation

44

EQUIPMENT NUMBER : E05

In Series :
NAME
: Heat exchanger 2
In Parallel :
General Data
Service
:
- Heat Exchanger
- Vaporizer
- Cooler
- Reboiler
- Condenser
Type
:
- Fixed Tube Sheets
- Plate
- Floating Head
- Finned Tubes
- Shell & Tube
- Double Tube
Position
:
- Horizontal
- Vertical
Capacity
[kW]
:
850.5737701
Heat Exchange Area
[m2]
:
24.7
2
Overall Heat Transfer Coefficient
[W/m C] :
500
Log Mean Temperature Diff. (LMTD) [C]
:
51.04
Passes Tube Side
Passes Shell Side
Correction Factor LMTD
Corrected LMTD

Medium
Mass Stream
Mass Stream
- Evaporize
- Condense

:
:

8
5

:
0.966
[C]
:
51.04
Process Conditions
Shell Side
Cooling water

Tube Side
BPA, phenol. Water

[kg/s]

4.66

[kg/s]
[kg/s]

~
~

~
~

[kJ/kgC]
[kJ/kg]

4.18
~

2.869867
~

Temp. IN
Temp. OUT

[C]
[C]

25
40.697

138.5728
75

Pressure
Material
Remarks:
Shell diameter 12in
# of tubes in shell 55
Tube OD 1.25 in
Tube length 16ft

[bar]
CS

CS

Average Specific Heat

Heat of Evap/Condensation

45

CHAPTER VIII
PROCESS CONTROL
Important conditions such as temperature, pressure, level and flow of the system are
to be maintained in the production of BPA by ion-exchange resin catalyzed process. To meet
these operating conditions, pressure gauges, temperature and level controllers are
appropriately positioned on each of the equipment.

Controlling Systems Used

Temperature Controller

Pressure Controller

Flow Controller

Level Controller

Fig.8.1 Controls for Feed Stream

The flow in the feed stream is maintained by means of the flow controller. If the measured
flow differs from the desired flow, the controller senses the error and changes the flow of the
stream.

46

Fig.8.2 Controls for Reactor

It is desired to maintain the temperature and pressure in the reactor by means of the
controller. If the measured temperature differs from the desired temperature, the controller
changes the flow of cooling water. If the pressure in the reactor is increased, the controller
senses the difference or error and the reactor stream is purge out to blow down vessel.

47

Fig.8.3 Controls for 1st Distillation Column

48

Fig.8.4. Controls for 2nd Distillation Control

49

Fig 8.5 3rd Distillation Control

It is desired to maintain the temperature in the distillation column by means of the controller.
If the desired temperature is decreased, the controller changes the flow of steam in the
reboiler that will provide the necessary heat requirement in the column.

50

Fig.8.6. Controls for Crystallizer

51

Chapter IX
Wastes
By-products of the reaction, unused reactants, start up and shut down products, spills,
products under company and market standards are considered wastes. The generation of
waste in an industrial plant is inevitable such that it is the responsibility of the designers on
how to handle and manage the wastes of the process to avoid environmental, health and
safety hazards.

Wastes can be classified as solid, liquid or gas. Recovery and treatment of useable
reactants, recycling of unwanted products, proper equipment design and marketing of useful
by-products are some of the solution to decrease waste generation in a plant. Table 9.1 shows
the waste produced in the production of Bisphenol A. It also shows the effects or the hazards
they propose and as well as how they are treated, recycled and disposed.

Table 9.1 Classification, Effects, Treatment and Disposal of Waste (Sinnott, 2005;
Sciencelab.com, Inc.2005)
Classification

Waste

Effects

Treatment &
Disposal

Solid

Below

Slipping

hazard,

standard

may

Bisphenol A final

explosive dust-air

product

mixture

Catalyst

(Amberlyst

cause

an

Pre-heated

to

liquid and fed

back to reactor

May cause eye &

May be disposed

skin irritation

of

33)

by

combustion in a
coal-fired boiler

Liquid

Excess

phenol

Corrosive

Fed

back

to

reactor or used
in crystallizer for
washing

52

BPA isomers

Toxic if ingested

Sent to a solvent

& trinuclear

recovery system

impurities

and

recycled

back

to

Tarry

process

Toxic. Can cause

substances or

disorder

pitch

environment

the

in

the

Marketed

since

it is used in the
production

of

carbon

Waste/

by-

product water

Acidic since it is a

electrodes

formed through an

Treated

acidic IER catalyst

wastewater
facility

Cooling

water

in

before

disposal

Maybe
contaminated in

steel corrosion

Recycled

and

treated in water
treatment facility

Unreacted

acetone

Causes

skin

irritation

Fed back to the

reactors

Gas

Exhaust

Steam

May cause skin

burns

No necessary
treatment

Phenol, BPA isomers, pitch are the wastes from the 2nd distillation of the proposed
process of the designers. Water formed in the reaction is recovered in the 1st distillation
column together with unreacted acetone. Cooling water is recovered from heat transfer
equipment.

53

CHAPTER X
PROCESS SAFETY

Every operating industrial plant faces a certain amount of risk, whether it is ensuring
the health and well-being of their employees or protecting their premises. So, necessary
precautions got to be needed to prevent present and future risks that may happen during the
operation. This chapter is intended to introduce you to the need for process safety, the safety
handling of the materials involved, together with its physical and chemical properties, and the
effects of these materials to the environment and humans.

Hazard and Operability Study (HAZOP)

Table 10.1: HAZOP Study of Storage Tank and Fixed Bed Reactor Section in PFS

Guide
word
No

Deviation

Possible Causes

Consequences

No flow

No Acetone (or Phenol) is

Loss of necessary feed

(a) Ensure that necessary feed is

available at storage

to reaction section and

reduction of output.

available at storage tanks

Low Temperature in Phenol Flow slows down in

Pre-Treatment Column
transfer line to Fixed

Actions required

(b) raise the temperature in Phenol

Pre-Treatment Column

Bed Reactor
Pump fails (impeller

Pump overheats

corroded, loss of drive,

motor fault (etc.)
Line blockage
Line Fracture

(c) Regular inspection of pumps

(d) Install kickback on pumps and
spare pumps

Flow slows down

(e) Regular patrolling, inspection

Leaks from pipelines

and maintenance of pipelines.

(f) covered in (e)

54

Table 10.1: HAZOP Study (continued)

More flow

Control Valves fail open

Fixed Bed Reactor

overfills

(g) Regular inspection of

control valves

Disturbances leading to (h) Ensure the flow rate

More

problems on reaction

necessary for the process and

section

the level for each vessel to

avoid overfilling

Temperature controller fail

temperature

Thermal expansion due to

fire or strong sunlight

More of

Disturbance in the

(i) regular inspection of

reaction section

temperature controllers

Some of the
compounds may

(j) Check whether there are

adequate alarms for any

evaporate thus reduce

product output

undesired temperature increase.

Pipeline fracture
Vessels are subjected
to high pressure
More

Flow rate is higher than

High pressure in

(k) Install alarm for pressure

pressure

desired

pipelines, reactor and

other vessels

monitoring inside the reactor

Control valves are closed in Transfer line subjected

(l) inspection of control valves

error while pump is running to full pump delivery or and pumps

surge pressure

55

Table 10.1: HAZOP Study (continued)

Guide
word

Deviation

Possible Causes

Less of

Less flow

Leaking valves and

pipelines

Material loss adjacent

to public highway

Valves are closed in error

Lesser Product output

Consequences

Actions required
(m) Regular inspection of
pumps, controllers, valves and
pipelines. Provide spare pumps

Less
temperature

As well

Excess

as

amount of
Acetone and

if necessary.

Insufficient steam fed to the Disturbance in the

distillation process
distillation process

(n)Ensure the steam available

for the distillation process.

Equipment Failure, flange

Line cannot be

(o) Install low-point drain and N

leak, etc.

completely drained or
purged

purge point downstream

Phenol in
Recycle
section
Other
than

Maintenance

56

FIRE AND EXPLOSION INDEX (F&EI)

Table 10.3 F&EI method for safety evaluation
Area/ Country: Philippines

Division:

Location: Naga, Cebu City

Prepared by: CPDO4

Approved by:

Building:

Reviewed by: CPD04

Reviewed by:

Reviewed by: CPDO4

Date:

Materials in process units: Acetone, Amberlyst 33, Bisphenol A (BPA), Phenol, Water
State of Operation:
Design
Startup

Basic Material(s) for material Factor: Bisphenol A (BPA)

Material Factor (MF) :

1. General Process Hazards

Penalty Factor Range

Penalty Factor
Used

Base Factor

1.00

A. Exothermic Chemical Reactions

0.30- 1.25

0.3

B. Endothermic Process

0.20 - 0.40

C. Material Handling and Transfer

0.25- 1.05

0.4

D. Enclosed or Indoor Process Units

0.25- 0.90

E. Access

0.20- 0.35

F. Drainage and spill Control

0.25- 0.50

0.3

GENERAL PROCESS HAZARDS FACTOR (FI)

2. Special Process Hazards

Base Factor

1.00

A. Toxic Material(s)

0.20- 0.80

0.6

B. Sub- Atmospheric Pressure (< 500 mm Hg)

0.50

1. Tank Farms Storage Flammable Liquids

0.50

0.5

2. Process Upset of Purge Failure

0.30

0.3

3. Always in Flammable Range

0.80

0.5

D. Dust Explosion

0.25- 2.00

C. Operation In or Near Flammable Liquids

0-0.85

E. Pressure (operating pressure : 20 psig)

0.8

F. Low temperature

0.20- 0.30

G. Quality of Flammable/ unstable Material:

0.20- 0.30

0.3

1. Liquids or Gases in Process

0.1-3.0

0.3

2. Liquids or Gases in Storage

0.1-1.65

0.3

3. Combustion Solids in Storage, Dust in Process

0.1-1.65

H. Corrosion and Erosion

0.10- 0.75

0.5

I. Leakage- Joints and Packing

0.10- 1.50

0.5

J. Use of Fired Equipment

0.1-1.0

0.6

K. Hot oil Heat Exchange System

0.15- 1.15

L. Rotating Equipment

0.50

SPECIAL PROCESS HAZARDS FACTORS (F2

6.2

PROCESS UNIT HAZARDS FACTOR (F1 x F2)= F3

2x6.2 =

FIRE AND EXPLOSION INDEX (F&EI = F3 x MF)

57

12.4

CHAPTER XI
ECONOMICS
Table 11.1 Total Investment Costs
Fraction of Total

Fixed Capital Costs

Investment

Amount (Php)

0.75

1,076,825,080.45

0.6

861,460,064.36

0.15

215,365,016.09

0.15

161,523,762.07

Equipment and installation

Piping, Instrumentation and Control
Indirect Costs, share of (*)
Buildings and Structures
Auxiliary facilities - utilities, land
Indirect Costs, share of (*)

Working Capital
Fixed Capital (typically 15%)
Recoverable at End of Plant Life

Investment (additional) for start-up until income starts

Start-up costs

0.1

- initial catalyst charge

10,768,250.80
5,300,813,548.62

- raw materials and intermediates

- finished product inventories
* Design, engineering, construction, cost estimation, supervision,
contingencies

6,549,930,641.94

58

Table 9.2 Summary of Annual Production Cost

TYPICAL VALUE (% of Item)

Raw Material

Amount (PhP)

5,300,813,548.62

Miscellaneous
2

Materials

10%

Utilities

Raw Material

530,081,354.86
2,001,121.68

Shipping and
4

Packaging

15%

rawmaterial

Maintenance

10%

Fixed Capital

107,682,508.05

Laboratory cost

10%

Operating Labor

10368000

Supervision

10%

Operating Labor

1036800

Plant overhead

50%

Operating Labor

5184000

10

Capital Charges

15%

Fixed Capital

161,523,762.07

11

Insurance

1%

Fixed Capital

10,768,250.80

12

Local Taxes

2%

Fixed Capital

21,536,501.61

13

Royalties

1%

Fixed Capital

10,768,250.80

14

Sales Expenses

10%

Raw Material

530,081,354.86

5%

Operating Labor

518,400.00

Research and
15

development

795122032.3

TOTAL ANNUAL
PRODUCTION COSTS

7,487,485,885.65

59

Annual Income

The estimated annual income is 20,588,235,290.0 based on a 120,000 ton plant

capacity. The unit price of the product is 171,568.63 per ton.
Net Income
The annual cash flow can be calculated through this eqn:
Annual income Annual production costs = net income
20,588,235,290.0 - 7,487,485,885.65= 13,104,173,182.51
Cash Flow
t(years)

sales %
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

Net Cash Flow

0
0
0
0
100
100
100
100
100
100
100
100
100
100
100
100

Cumulative Cash Flow

0
-1,076,825,080.45
-161,523,762.07
-5,311,581,799.00
13,104,173,182.51
13,104,173,182.51
13,104,173,182.51
13,104,173,182.51
13,104,173,182.51
13,104,173,182.51
13,104,173,182.51
13,104,173,182.51
13,104,173,182.51
13,104,173,182.51
13,104,173,182.51
13,104,173,182.51

Note: year 0 3 is the proposed time frame for plant construction

60

0
-1,076,825,080.45
-1,238,348,842.52
-6,549,930,641.52
6,554,242,540.99
19,658,415,723.50
32,762,588,906.01
45,866,762,088.52
58,970,935,271.03
72,075,108,453.54
85,179,281,636.05
98,283,454,818.56
111,387,628,001.07
124,491,801,183.58
137,595,974,366.09
150,700,147,548.60

Cash Flow Diagram

Cash Flow Diagram

160,000,000,000.00
140,000,000,000.00

Cummulative cash Flow (PhP)

120,000,000,000.00
100,000,000,000.00
80,000,000,000.00
cash flow

60,000,000,000.00
40,000,000,000.00
20,000,000,000.00

0.00
0
-20,000,000,000.00

8
t(years)

Rate of Return

ROR = 0.488
ROR = 48.8%

61

10

12

14

16

CHAPTER XII
CONCLUSIONS AND RECOMMENDATIONS
Bisphenol A is a colorless, odorless substance and is usually solid at room
temperature. BPA is a monomer used to make polycarbonate and epoxy resins. China has the
largest demand of BPA such that its total capacity for production of BPA does not meet its
demands, thus some of the product are imported from the United States of America and other
BPA producing countries outside Asia. A production plant in the Philippines of the product is
feasible since the product may be of lower cost than the products from non-Asian countries. It
also lowers the possible risks that transportation offers of raw materials and finished product.

The plant is designed to have a 120,000 ton/yr capacity. The target market of the
design is mainly the polycarbonate industry which requires 99% pure BPA. The design
process is condensation of acetone in excess phenol with the presence of an ion-exchange
resin, Amberlyst33, to produce a high purity bisphenol A. This specific process is chosen
since it is a new technology such that the product of this particular design can compete
against the products produced in other countries. It is also more suitable when manufacturing
high purity BPA. With it being a new technology, safety and environmental hazards were
also reduced to a minimum compared to older technology such as the acid catalyzed process
which uses a strong acid as a catalyst for the reaction.

The estimated annual net income is 13,104,173,182.51 with an estimated investment

of only 6,549,930,641.94 which is clearly profitable. This suggests that this design will be a
profitable venture to invest.

The approval and construction of this design may lead to the start of polycarbonate
and epoxy industries in the Philippines especially in Cebu since the proposed plant location is
in the municipality of Naga, Cebu.

62

REFERENCES
[1] Navid Naderpur ,(2008), Petrochemical production processes.
[2] A. Chakrabarti, M.M. Sharma, React. Polym. 20 (1993)
[3] B.C. Gates, Catalytic Chemistry, Wiley, New York, 1992.]
[4] De Jong, "The alkylation of phenol with isobutene", Remelt, 83, 469--476, 1964.
De Jong J .I. And Dethmers F .H.D ., "The formation of 2,2- bis(4-hydroxyphenyl)-propane
(bisphenol A) from phenol and acetone", Rec. Tray. Chin],, 84, 4, 460-464, 1965.
[5]

Agrawal, et.al. Production of BPA . Jeypee University of Engineerin and Technology

[6] Mendirata. Ion exchange catalyzed bisphenol process. US 4391997. Filed Oct. 23, 1981.
Published July 5, 1983.
[7] Cipullo et al. Use of partial acetone conversion for capacity increase and quality/ yield
improvement in the bisphenol A reaction. US 00531243A. Filed Mar. 22, 1993.
Published May 24, 1994
[8] Catalyst for Production of Bisphenol compound and method for producing bisphenol
compound. EP 2497574A. Filed Nov. 8, 2010. Published Sept 12, 2012.
[9] Oyevaar et al. Process for Manufacture for Bisphenols. US 6635788B1. Filed Dec. 20,
2002. Published Oct 21, 2003.
[10] Blaschke et al. Process for the preparation of high purity Bisphenol A. US 7427694B2.
Filed Jan. 9, 2008. Published Aug 1, 2008.
[11]
[12]

Navid Naderpur ,(2008), Petrochemical production processes

A.
Chakrabarti,
M.M.
Sharma,
React.
Polym.
B.C. Gates, Catalytic Chemistry, Wiley, New York, 1992.]

20

[13] worklaw, A Process to Obtain Bisphenol A Preliminary Technical Information

[14] National Recommended Water Quality Criteria 1.Correction, EPA 22-Z-99-001,
April 1999. Standard Methods for the Examination of Water and
[15] Wastewater, APHA, AWWA and WEF, Washington, D.C.(20th Ed., l998).

63

(1993)

Du Pont de Nemours & Company, Solid Acid Catalysis Using ion-exchange resins. 2001
Hart et.al,. Sulfonated poly(styrene-co-divinylbenzene) ion exchange resins acidities and
catalytic activities in aqueous reactions. University of Huddersfield. 2001.
M.M. Sharma. Some novel aspects of cationic ion-exchange resins as catalysts. University of
Bombay. 1995
Mohaparta. Physico-chemical pre-treatment and biotransformation of wastewater and
wastewater sludge Fate of Bisphenol A. Universite de Quebec. 2010.
Walas. Reaction Kinetics. University of Kansas. 1999
Kissinger et al. Process for the manufacture of Bisphenol A. Filed Dec. 15, 1998, published
Feb. 6, 2001
OYoung et al. System and method of producing BPA using direct crystallization of BPA in a
single crystallizer stage. US 7,163,582B2. Filed Sep. 12,2003. Published Jan.
16,2007.
Mitsui Chemical Inc. Process for production of Bisphenol A. EP 1607380A. Filed March 25,
2004. Publlished Dec. 12, 2005.
Cipullo et al. Use of partial acetone conversion for capacity increase and quality/ yield
improvement in the bisphenol A reaction. US 00531243A. Filed Mar. 22, 1993.
Published May 24, 1994

64

APPENDIX 1
MASS BALANCES
Mass Balance of the Reactor:
Solving for molar flow rate (Kmol/s):
Phenol:

Acetone:

Solving for mass flow rate (Kg/s):

Phenol:

Acetone:

Reactor Outlet:
Solving for molar flow rate (Kmol/s):
Phenol:

Acetone:

65

BPA:

Water:

Solving for mass flow rate:

Phenol = 0.0496 Kg/s
Acetone = 0.0353 Kg/s
BPA = 4.6297 Kg/s
Water = 0.3655 Kg/s
Mass Balance of the Distillation:
First Distillation (Splitter)

________________________

C01

_______________________

________________________

66

IN = OUT
5.107371778 = 0.3979543811 + 4.715134056
5.11 = 5.11
Second Distillation (Acetone Recovery Column)

________________________

C02

_______________________

________________________

IN = OUT
0.3979543811 = 0.03819611667 + 0.3597582678
0.3979 = 0.3979

67

Third Distillation Column (Partial Phenol Recovery Column)

________________________
0.05306306313885 kg/s
C03

________________________

________________________
4.662070917 kg/s
IN=OUT
4.715134056 = 0.05306306313885 + 4.662070917
4.715134056 = 4.715134056

68

Crystallizers

Crystallizer 1

Crystallizer 2

IN=OUT
4.662070917 kg/s = 4.662070917 kg/s

4.6154 x 10^-4 kg/s water

4.662 kg/s BPA

Drier

4.6154 x 10^-4 kg/s water

IN=OUT
4.6297 = 4.6297

69

Crystallizer 3

APPENDIX II
HEAT AND ENERGY BALANCE
Heat Balance- Reactor
Reaction Temperature: 348 K
Pressure: 4.4 bars
Heat Capacity Constants:
Component
Phenol
Acetone
BPA

A
207.48
71.96
Cp = 1.2

B
-103.75
20.1

c
274
-12.78

Inlet
Inlet Temperature: 298 K
Ingredient Name
Phenol
Acetone

Flowrate (kg/s)
3.6564
1.137

Mass Component (%)

76.27
23.72

For phenol:
Molar flow rate: 38.9 mol/s
Cp = a+bT+cT2
Q= nCpdT
Q= 38.9mol/s(207.48 + (-103.75x10-3)T + (374x10-6)T2 ) dT
= 38.9[207.48(348-298) +(-103.75X10-3)/2(3482-2982) + (274x10-6)/3(3483-2983)]
Q= 394080.3 W
For Acetone:
Molar flow rate: 19.60 mol/s
Cp = a+bT+cT2
Q= nCpdT
Q= 19.60mol/s(71.96 + (20.1x10-2)T + (-12.78x10-5)T2 ) dT
= 19.6[71.96(348-298) +(20.1x10-2)/2(3482-2982) + (-12.78x10-5)/3(3483-2983)]
Q= 120781.8 W
Qin= 514862.12 W

70

Outlet
Component
Bisphenol-A
Phenol
Acetone
Water

Flowrate (kg/s)
4.340
0.0775
0.033
0.3427

Mass Component (%)

90.54
1.62
0.69
7.15

Outlet Temperature: 308 K

For phenol:
Molar flow rate: 0.824 mol/s
Cp = a+bT+cT2
Q= nCpdT
Q= 0.824mol/s(207.48 + (-103.75x10-3)T + (374x10-6)T2 ) dT
= 0.824[207.48(308-348) +(-103.75X10-3)/2(3082-3482) + (274x10-6)/3(3083-3483)]
Q= -6689.71 W
For Acetone:
Molar flow rate: 0.569 mol/s
Cp = a+bT+cT2
Q= nCpdT
Q= 0.569mol/s(71.96 + (20.1x10-2)T + (-12.78x10-5)T2 ) dT
= 0.569[71.96(308-348) +(20.1x10-2)/2(3082-3482) + (-12.78x10-5)/3(3083-3483)]
Q= -2825.01
For Bisphenol-A:
Molar flow rate: 19.04 mol/s
Q= nCpdT
= 19.04mol/s(1.2J/mol-K)(308-348)K
Q= -912.48 W
For Water:
Molar flow rate: 19.04 mol/s
Q= nCpdT
= 19.04mol/s(4.2J/mol-K)(308-348)K
Q= -3198.72 W
Qout = Qphenol+Qacetone+QBPA+Qwater = -13625.92 W

71

Heat of Reaction:
Heat of formation Phenol: -165.64 kJ/mol
Heat of formation BPA: -369 kJ/mol
Heat of formation Water: -285.8kJ/mol
Heat of formation Acetone: -226kJ/mol
2Phenol + Acetone= BPA + Water
Heat of Reaction = heat of formation products - heat of formation reactants
= (-369-285.8)-(2(-165.64)-226)
= -97520 W
Q= Product -Reactant + Heat of Reaction
=-13625.92-514862.12+-97520
Q= -626007.12 W
Volume of cooling water added to decrease the temperature from 348 K to 308K.
Q= mCpdT
-626007.12 J/s = m(4.2J/gK)(308-348)K
m= 3726.23 g/s= 3.726 kg/s of cooling water
Heat Balance of 1st Heat Exchanger:
Q = mcpT
=
Q=
Solving for T2 of the cooling water:
Qhot = -Qcold
345.13 =

T2 = 46.51C 319.67 K

CpH2 O =
Cpphenol =
Cpacetone =

72

CpBPA = =

Heat Balance of 2nd Heat Exchanger:

Q = mcpT

where: Cp =

Cp = 2.869867

Q=

Solving for T2 of H2O:

=

T2 = 313.8473096 K 40.697 C
Heat Balance- Distillation Columns
Operating Conditions
Bottoms(Kelvin)
372.39
349.74
436.86

Equipment
C01
C02
C03

Acetone
Phenol
H2O
Bisphenol

Acetone
Phenol
H2O
Bisphenol

Tc(K)
508
694
647
852

Tops(Kelvin)
406.87
372.96
411.57

Heat of Vaporization constants

A
44497.1062
70126.2112
60334.5172
121393.1481

Hvap(J/mol)=A(1-Tr)^b
C01
C02
Bottom(sat
Top(sat vap) Bottom(sat liq) Top(sat vap)
liq)
26874.47
24026.41438
28507.05
26831.74
51713.46
49442.28108
53126.21
51677.53
42342.52
40058.74696
43752.19
42306.57
93162.31956
95993.79
73

Top(sat
vap)
21007.79
47329.53
37910.94
-

b
0.3818
0.396
0.4132
0.4077

C03
Bottom(sat
liq)
23594.04
49120.37
39733.08
92760.24

Overall Heat Balance around a Distillation Column:

In = Out
Heat supplied in the Reboiler + Energy of Feed = Heat removed in the condenser +
Energy of bottoms + Energy of
Distillate
Qfeed +

QR

QB

QC

QD

Energy Balance around the Reboiler:

Qb = Hvap(V)
Qb = m(steam)(Enthalpy of steam)

Energy Balance around the condenser:

Qc = Hvap(V)
Qc = m(cooling water)dT
Energy of bottoms(saturated liquid) = B(Hvap)

Solving for amount of vapor to be vaporized,

V = D( R+1)
Equipment #
C01
C02
C03

Reflux Ratio
1.5
2
3.5

D(kmol/hr)
74.59
2.87
2.41

V(kmol/hr)
186.48
8.61
10

Solving for the amount of heat to be added to the reboiler to obtain the amount of vapor to be
vaporized,
QB = V(Hvaporization @ bubble pt conditions,bottoms)
Equipment #
C01
C02
C03

QB(kW)
2050.83
74.05
130.92
74

Solving for the amount of heat to be removed from the vapor to condense it to a saturated
liquid,
QC = V(Hvaporization @ dew point conditions,distillate)
Equipment #
C01
C02
C03

- QC(kW)
2169.98
77.91
189.29

Solving for the Energy in the bottoms stream, assuming the bottoms stream is a saturated
liquid at bubble point conditions;
QB = B(xb,iHvap,i)
C01
C02
C03
x,phen
0.040694 0.0004411 0.016569295
x,h2o
0.009498 0.9989482 0.002945083
x,acetone
0 0.0006107 0.980485622
x,bis
0.949807
0
0
Equipment #
C01
C02
C03

QB (kW)
1942.86
842.37
1900.48

Solving for the energy in the distillate stream,

QD

Qfeed

QB

QC

Equipment #
C01
C02
C03

QR

QD (kW)
2291.58
1601.17
543.05

Inlet stream to the 2nd distillation column = Distillate outlet from the 1st distillation column,
Inlet stream to the 3rd distillation column = Bottoms outlet stream from the 1st distillation
column.

75

In summary;
Equipment #
C01
C02
C03

Qb
2050.828942
74.04872979
130.9208438

IN
Qc
2169.983881
77.91243917
189.2906762

OUT
Qf
13.62592
2291.577646
1942.861097

BOTTOMS
1942.861097
842.3719186
1900.484314

DISTILLATE
2291.577646
1601.166896
543.0545012

Heat Balance- Crystallizers

Inlet
From Superpro:
Ingredient Name
Bisphenol-A
Phenol
Water

Flowrate (kg/s)
4.6297
0.03220
0.00016

Mass Component
(%)
99.3059
0.6907
0.0034

Concentration
(g/L)
1,112.84185
7.73992
0.03846

Mass Component
(%)
99.3750
0.6216
0.0034

Concentration
(g/L)
1,130.7428
7.073062
0.039051

Total Flowrates:
Mass Flowrate = 16,783.455 Kg/hr
Volumetric Flowrate = 14,976.937 L/hr
Temperature = 75 C
Pressure = 1.013 bar
Enthalpy = 0.227 kWhr/s

Outlet
Component
Bisphenol-A
Phenol
Water

Flowrate (kg/s)
4.63292
0.02898
0.00016

Total Flowrates:
Mass Flowrate = 16,783.455 Kg/hr
Volumetric Flowrate = 14,742.565 L/hr
Temperature = 50 C
Pressure = 3 bar
Enthalpy = 0.151 KWhr/s

76

Cp ave = (0.9931)(2.3406 kJ/kg.K) + (6.907x10^-3)(2.08936 KJ/kg.K) + (3.432x10^-5)(4.18

KJ/kg.K)
Cp ave = 2.3390 kJ/kg.K
Q = mCp ave(T2-T1)
Q = (4.66206 kg/s) (2.3390 KJ/kg.K) (50-75) K
Q = -272.614 kW

@ Crystallizer 2
Inlet:
Component
Bisphenol-A
Phenol
Water

Mass
Component(%)
99.3750
0.6216
0.0034

Flowrate (kg/s)
4.63292
0.02898
0.00016

Concentration
(g/L)
1,130.7428
7.073062
0.039051

Total Flowrates:
Mass Flowrate = 16,783.455 Kg/hr
Volumetric Flowrate = 14,742.565 L/hr
Temperature = 80 C
Pressure = 3 bar
Enthalpy = 0.151 kWhr/s

Output:
Component
Bisphenol-A
Phenol
Water

Mass
Component(%)
99.4387
0.5579
0.0034

Flowrate (kg/s)
4.63581
0.02601
0.00016

Concentration
(g/L)
1,111.048586
6.233727
0.038347

Total Flowrates:
Mass Flowrate = 16,783.455 kg/hr
Volumetric Flowrate = 15,013.719 L/hr
Temperature = 80 C
Pressure = 3 bar
Enthalpy = 0.242 kWhr/s

Cp ave = (0.99375)(2.3406 KJ/kg.K) + (6.216x10^-3)(2.08936 KJ/kg.K) + (3.4x10^-5)(4.18

KJ/kg.K)
Cp ave = 2.3391 KJ/kg.K
77

Q = mCp ave(T2-T1)
Q = (4.662 kg/s) (2.3391 KJ/kg.K) (80-50) K
Q = 327.15 kW

@ Crystallizer 3
Input:
Component
Bisphenol-A
Phenol
Water

Mass Component
(%)
99.4387
0.5579
0.0034

Flowrate (kg/s)
4.63581
0.02601
0.00016

Concentration
(g/L)
1,111.048586
6.233727
0.038347

Total Flowrates:
Mass Flowrate = 16,783.455 Kg/hr
Volumetric Flowrate = 15,013.719 L/hr
Temperature = 80 C
Pressure = 3 bar
Enthalpy = 0.242 kWhr/s

Output:
Component
Bisphenol-A
Phenol
Water

Mass
Component(%)
99.4944
0.5021
0.0034

Flowrate (kg/s)
4.63841
0.02341
0.00016

Concentration (g/L)
1,101.48417
5.558939
0.037995

Total Flowrates:
Mass Flowrate = 16,783.455 kg/hr
Volumetric Flowrate = 15,153.071 L/hr
Temperature = 95 C
Pressure = 3 bar
Enthalpy = 0.287 kWhr/s

Cp ave = (0.994944)(2.3406 KJ/kg.K) + (5.021x10^-3)(2.08936 KJ/kg.K) + (3.4x10^-5)(4.18

KJ/kg.K)
Cp ave = 2.3394 KJ/kg.K

78

Q = mCp ave(T2-T1)
Q = (4.662 kg/s) (2.3394 KJ/kg.K) (95-80) K
Q = 163.59 kW

Drier (Rotary):
Component
Bisphenol-A
Phenol
Water

Mass Component
(%)
99.4944
0.5021
0.0034

Flowrate (kg/s)
4.63841
0.02341
0.00016

Concentration (g/L)
1,101.48417
5.558939
0.037995

Temperature = 100 C
Pressure = 1.013 bar
Cp ave = (0.994944)(2.3406 KJ/kg.K) + (5.021x10^-3)(2.08936 KJ/kg.K) + (3.4x10^-5)(4.18
KJ/kg.K)
Cp ave = 2.3394 KJ/kg.K
Q = mCp ave(T2-T1)
Q = (4.662 kg/s) (2.3394 KJ/kg.K) (100-95) K
Q = 54.531 kW

79

APPENDIX III
EQUIPMENT DESIGN
Design of a Reactor:
Given: k = 0.2157 h-1
XA = 0.97
CAo = 73.14 mol
Required: VR
Solution:

Assume:
For cylinders:

Therefore,
m

80

Design of Distillation Columns 1,2,3

1st Distillation Column: Equipment Design
Assuming the feed is saturated liquid;

P=560
mmHg
T=116OC

Calculating for the bubble point of feed and bottoms and for the dew point of the
distillate:
For bubble point calculations:

For dew point calculations

Where

81

By iteration;
TF (bubble point) = 92OC
TD (distillate, dew point) = 99OC
TB(bottoms, bubble point) = 134OC
Tave(column temp) =
Calculating for the Vapour Pressure and Relative Volatility:
Using Antoine Equation
Data:
Antoine Coefficient

Vapour Pressure H2O:

Vapour pressure Phenol:

Relative Volatility:

82

Component

Water

7.96681 1668.21 228

Phenol

7.13301 1516.79 174.954

Calculating for Minimum Number of Stages:

Using Fenske Equation:

Calculating for Rm:

Using Underwood Equation:

Solving for

By iteration:

Solving for R:

Calculating for Number of theoretical stages:

Using Gilliland Equation:

83

Calculating for Actual Number of Stages: Using OConnells Correlation [Eq. 11.67
of R.K. Sinnott]

Actual Feed Location:

Using Kirkbride Equation:

, the feed plate is 23 stages above the stripping section

Calculation of the column height:

Calculation of column diameter:

84

Solving for the net column area used for the separation;

Solving for the area of the column, assuming that the column area is 85% of the net column
area:

Solving for the column diameter:

Solving for the downcomer area:

Calculating the active area:

For single pass plates,

85

Solving for the weir length:

For weir height and hole diameter,

Solving for the number of holes:

86

2nd Distillation Column: Equipment Design

Assuming the feed is saturated liquid;

P=760
mmHg
T=88OC

Calculating for the bubble point of feed and bottoms and for the dew point of the
distillate:
For bubble point calculations:

For dew point calculations

87

Where

By iteration;
TF (bubble point) = 98OC
TD (distillate, dew point) = 77OC
TB(bottoms, bubble point) = 100OC
Tave(column temp) =
Calculating for the Vapour Pressure and Relative Volatility Using Antoine Equation
Data:
Antoine Coefficient

Vapour Pressure H2O:

Vapour pressure Acetone:

Relative Volatility:

88

Component

Water

7.96681 1668.21

Acetone

7.11714 1210.595 229.664

228

Calculating for Minimum Number of Stages:

Using Fenske Equation:

Calculating for Rm:

Underwood Equation:

Solving for

By iteration:

Solving for R,

Calculating for Number of theoretical stages:

Using Gilliland Equation:

89

Calculating for Actual Number of Stages: Using OConnells Correlation [Eq. 11.67
of R.K. Sinnott]

Actual Feed Location:

Using Kirkbride Equation:

, the feed plate is 21 stages above the stripping section.

Calculation of the column height:

90

Calculation of column diameter:

Solving for the net column area used for the separation;

Solving for the area of the column, assuming that the column area is 85% of the net column
area:

Solving for the column diameter:

Solving for the downcomer area:

91

Calculating the active area:

For single pass plates,

Solving for the weir length:

For weir height and hole diameter,

Solving for the number of holes:

92

3rd Distillation Column: Equipment Design

Assuming the feed is saturated liquid;

P=560
mmHg
T=151OC

Calculating for the bubble point of feed and bottoms and for the dew point of the
distillate:
For bubble point calculations:

For dew point calculations

93

Where

By iteration;
TF (bubble point) = 133OC
TD (distillate, dew point) = 163OC
TB(bottoms, bubble point) = 138OC
Tave(column temp) =
Calculating for the Vapour Pressure and Relative Volatility:
Using Antoine Equation
Data:
Antoine Coefficient

Vapour Pressure H2O:

Vapour pressure Phenol:

Relative Volatility:

94

Component

Water

7.96681 1668.21 228

Phenol

7.13301 1516.79 174.954

Calculating for Minimum Number of Stages:

Using Fenske Equation:

Calculating for Rm:

Using Underwood Equation:

Solving for

By iteration:

Solving for R:

95

Calculating for Number of theoretical stages:

Using Gilliland Equation:

Calculating for Actual Number of Stages: Using OConnells Correlation [Eq. 11.67
of R.K. Sinnott]

Actual Feed Location:

Using Kirkbride Equation:

, the feed plate is 2 stages above the stripping section.

Calculation of the column height:

96

Calculation of column diameter:

Solving for the net column area used for the separation;

Solving for the area of the column, assuming that the column area is 85% of the net column
area:

Solving for the column diameter:

Solving for the downcomer area:

97

Calculating the active area:

For single pass plates,

Solving for the weir length:

For weir height and hole diameter,

Solving for the number of holes:

98

Design of a Crystallizer
1

3
Inlet
From Superpro:
Ingredient Name
Bisphenol-A
Phenol
Water

Mass Component
(%)
99.3059
0.6907
0.0034

Flowrate (kg/s)
4.6297
0.03220
0.00016

Total Flowrates:
Mass Flowrate = 16,783.455 Kg/hr
Volumetric Flowrate = 14,976.937 L/hr
Temperature = 75 C
Pressure = 1.013 bar
Enthalpy = 0.227 kWhr/s
99

Concentration
(g/L)
1,112.84185
7.73992
0.03846

Outlet
Component
Bisphenol-A
Phenol
Water

Mass Component
(%)
99.3750
0.6216
0.0034

Flowrate (kg/s)
4.63292
0.02898
0.00016

Concentration
(g/L)
1,130.7428
7.073062
0.039051

Total Flowrates:
Mass Flowrate = 16,783.455 Kg/hr
Volumetric Flowrate = 14,742.565 L/hr
Temperature = 50 C
Pressure = 3 bar
Enthalpy = 544.979 KWhr/hr

Crystallizer:
P = 3 bar
Power = 1.499 KW

Residence Time = 1 hr
Working/Vessel Volume = 90%
Working Volume = 14,976.94 L or 15m3

Working/Vessel Volume Limits

Min Allowable 15 %
Max Allowable 90%
Crystal Data:
T = 50 C
Cooling Duty = 234,460.37 Kcal/hr
272.4947036 KW
Chilled Water:
Inlet Temperature = 5 C
Outlet Temperature = 10 C
Rate = 46,680.60 Kg/hr
@ Crystallizer 2
Inlet:

Component

Flowrate
(Kg/hr)

Bisphenol-A
Phenol
Water

16,781.75987
0.0167
1.67835

Mass
Component
(%)
99.9899
0.0001
0.01
100

Concentration
(g/L)
1,138.32026
0.00114
0.11384

Total Flowrates:
Mass Flowrate = 16,783.455 Kg/hr
Volumetric Flowrate = 14,742.565 L/hr
Temperature = 50 C
Pressure = 1.013 bar
Enthalpy = 544.979 KWhr/hr

Crystallizer:
P = 3 bar
Power Consumption (for Agitation) = 1.473 KW
Volume = 14,742.56 L
Residence Time = 1 hr

Working/Vessel Volume Limits:

Min Allowable 15 %
Max Allowable 90%
Heating:
Evaporation Temperature = 100 C
Evaporation Heat = 539.489 Kcal/Kg 0.627 KW
Agent:
Steam @ Temperature = 152 C
Output:

Component

Flowrate
(Kg/hr)

Bisphenol-A
Phenol
Water

16,781.77665
0
1.67835

Mass
Component
(%)
99.99
0
0.01

Total Flowrates:
Mass Flowrate = 16,783.455 Kg/hr
Volumetric Flowrate = 15,013.719 L/hr
Temperature = 80 C
Pressure = 3 bar
Enthalpy = 871.967 KWhr/hr

101

Concentration
(g/L)
1,117.762774
0
0.111787

@ Crystallizer 3
Input:

Component

Flowrate
(Kg/hr)

Bisphenol-A
Phenol
Water

16,781.77665
0.01678
1.66156

Mass
Component
(%)
99.99
0.0001
0.0099

Concentration
(g/L)
1,117.76284
0.00112
0.11067

Total Flowrates:
Mass Flowrate = 16,783.455 Kg/hr
Volumetric Flowrate = 15,013.719 L/hr
Temperature = 80 C
Pressure = 1.013 bar
Enthalpy = 871.966 KWhr/hr
Crystallizer:
P = 3 bar
Power Consumption (for Agitation) = 1.5014 KW
Residence Time = 1 hr
Working/Vessel Volume = 90%
Working Volume = 15,013.72 L
Working/Vessel Volume Limits:
Min Allowable 15 %
Max Allowable 90%
Heating:
Evaporation Temperature = 100 C
Evaporation Heat = 539.489 Kcal/Kg 0.627 KW
Agent: Steam @ Inlet Temperature = Output Temperature = 152 C
Output:

Component

Flowrate
(Kg/hr)

Bisphenol-A
Phenol
Water
Total:

16,781.79343
0
1.66156
16,783.45499

Mass
Component
(%)
99.9901
0
0.0099

102

Concentration
(g/L)
1,107.484677
0
0.109652

Total Flowrates:
Mass Flowrate = 16,783.455 Kg/hr
Volumetric Flowrate = 15,153.071 L/hr
Temperature = 95 C
Pressure = 3 bar
Enthalpy = 1035.459 KWhr/hr
Drier (Rotary):

Component

Flowrate
(Kg/hr)

Bisphenol-A
Water
Total:

16,781.77665
1.67835
16,783.455

Mass
Component
(%)
99.99
0.01

Temperature = 95 C
Pressure = 1.013 bar
Enthalpy = 1,035.460 KWhr/hr
Water: Mass Flowrate = 8.39173 Kg/hr
Temperature = 25 C
Concentration = 994.70433
Pressure = 1.013 bar
Steam: Inlet Temperature = Output Temperature = 152 C
Specific Amount: 2 Kg/Kg evaporated
Rate: 3.36 Kg/hr
Outlet:
Water: Mass Flowrate = 10.070 Kg/hr
Volumetric Temperature = 10.371 L/hr
Temperature = 90 C
Pressure = 1.013 bar
Enthalpy = 1.051 KWhr/hr
Drying Gas Requirement: 5 wt. gas/wt. evaporated
Evaporation Rate: 20 (Kg/hr)/m3

BPA:
Mass Flowrate = 16,781.77665 Kg/hr
Mass Component = 100%
Concentration = 1,111.0369909 g/L
Enthalpy = 980.787 KWhr/hr
103

Concentration
(g/L)
1,107.48341
0.11076

APPENDIX IV
PROCESS STREAM SUMMARY
Table 4.1
Components

Stream 1=3
kg/s
kmol/s

Stream 2
kg/s
kmol/s

Stream 4=5
kg/s
kmol/s

Acetone

1.1777

0.0203

0.0353

6.07 x 10^-4

Phenol

3.8174

0.0406

0.0826

8.78x10^-4

BPA

4.6297

0.0203

Water

0.3655

0.0203

Table 4.2
Components

Stream 6=9
kg/s
kmol/s

Stream 7=8
kg/s
kmol/s

Acetone

0.0353

6.07x10^-4

Phenol

8.3x10^-4

8.78x10^-6

0.0818

BPA

4.6297

Water

0.3618

0.02

Stream 10=11
kg/s
kmol/s
0.0353

8.69x10^-4 8.3x10^-4
0.0203

3.66x10^-3 3.66x10^-3

6.07x10^-4
8.78x10^-6

0.3618

0.02

Table 4.3
Components

Stream 12=13
kg/s
kmol/s

Stream 14=15
kg/s
kmol/s

Stream 16-17
kg/s
kmol/s

Acetone

7.1x10^-4

1.215x10^-4

0.0346

5.95x10^-4

0.0346

5.95x10^-4

Phenol

8.3x10^-4

8.78x10^-6

BPA

Water

0.3582

0.0199

0.0036

2x10^-4

0.0036

2x10^-4

Table 4.4
Components

Stream 18
kg/s
kmol/s

Stream 19=20
kg/s
kmol/s

Stream 21=22
kg/s
kmol/s

Acetone

0.0496

5.3 x10^-4

Phenol

0.0818

8.69x10^-4

0.0322

3.42 x10^-4

BPA

4.6297

0.0203

4.6297

0.0203

Water

3.66x10^-3

3.66x10^-3

0.00016

8.89x10^-6

104

1.9x10^-4 1.1 x10^-5

Table 4.5
Components

Stream 23
kg/s
kmol/s

Stream 25
kg/s
kmol/s

Stream 26
kg/s
kmol/s

Acetone

Phenol

0.0827

8.79x10^-4

0.0322

3.42 x10^-4

0.02898

3.1 x10^-4

BPA

4.6297

0.0203

4.63292

0.0203

Water

0.00016

8.89x10^-6

0.00016

8.89x10^-6

Table 4.6
Components

Stream 27
kg/s
kmol/s

Stream28=29
kg/s
kmol/s

Acetone

Phenol

0.02601

2.76x10^-4

0.02341

2.49 x10^-4

BPA

4.63581

0.02031

4.63841

0.02032

Water

0.00016

8.89x10^-6

0.00016

8.89x10^-6

105

APPENDIX V

PROCESS FLOW SCHEME

106

APPENDIX VI
ECONOMIC EVALUATION

Table A.6.1 Major Equipments Purchase Cost

Purpose

# of
units

Cost/unit (PhP)

total Purchase cost (PhP)

Fixed Bed Reactor

Reaction

2480279.746

4960559.492

Distillation Column

Separation

2480279.746

2480279.746

SuperPro Designer v8.5

Plant Design & economics
for ChE

Crystallizer

Purification

82,459,136.46

82459136.46

SuperPro Designer v8.5

Dryer

Equipment

Source

Purification

975,847.77

975847.7688

SuperPro Designer v8.5

Conveyor

Transport

10653004.81

21306009.62

SuperPro Designer v8.5

Pumps

Transport
Heat
transfer

12

8,863,950.57

106367406.8

SuperPro Designer v8.5

1,057,168.42

4228673.665

SuperPro Designer v8.5

Steam

1,065,300.48

3195901.443

SuperPro Designer v8.5

Acetone tank

storage

2,520,940.07

2520940.069

SuperPro Designer v8.5

Phenol Silo

Storage

2805562.335

SuperPro Designer v8.5

Condenser

Transport

2,805,562.34
3252825.896

9758477.688

SuperPro Designer v8.5

Heat Exchangers
Reboiler

Purchase Equipment cost TOTAL:

251467838

107

Table A.6.2. Major Equipment Fixed Capital Cost

Heat
Exchangers

Conden
ser

Fixed bed
reactor

Distillation
Column

Crystallize
r

Dryer

pumps

Conveyor

Reboiler

Acetone
Storage tank

Phenol
Silo

4228673.665

9,758,4
77.69

4,960,559.4
9

2,480,279.7
5

82,459,13
6.46

975847.
7688

10636740
6.8

2130600
9.62

3195901.
443

2520940.069

2805562.
335

Equipment Erection, f1

0.4

0.4

0.45

0.4

0.45

0.5

0.5

0.4

0.4

0.5

Piping, f2

0.7

0.7

0.45

0.7

0.45

0.2

0.2

0.7

0.7

0.2

0.1

0.2

0.2

0.1

0.1

0.1

0.1

0.1

0.05

0.15

0.15

0.05

0.25

0.5

0.5

0.25

0.25

0.15

0.15

0.25

0.05

0.05

0.05

0.05

2.8
59,656,8
26.93

3.4
10,866,0
64.91

3.4
8,571,196.24

2.8
7,855,57
4.54

0.25

0.25

0.25

0.05

0.05

0.05

0.1

0.1

0.1

1.4

1.4

1.4

15,212,4
90.87

11,999,674.7
3

10,997,8
04.35

EQUIPMENT:
TOTAL PURCHASE COST (PCE)

Instrumentation, f3

0.2

0.2

0.15

0.2

0.15

0.1

Electrical, f4

0.1

0.1

0.1

0.1

0.1

0.1

Buildings, process, f5

0.15

0.15

0.1

0.15

0.1

0.05

Utilities, f6

0.5

0.5

0.45

0.5

0.45

0.25

Storages, f7

0.15

0.15

0.2

0.15

0.2

0.25

Site Development, f8

0.05

0.05

0.05

0.05

0.05

0.05

Total (A) = (1+ f(1-9))

TOTAL PHYSICAL PLANT COST
(PPC) PPC=PCE*A

3.4
14,377,490.

3.4
33,178,
824.14

3.15
15,625,762.
40

3.4
8,432,951.1
4

3.15
259,746,2
79.86

2.8
2,732,37
3.75

Design and Engineering, F10

0.25

0.25

0.25

0.25

0.25

0.25

Contractor's Fee, F11

0.05

0.05

0.05

0.05

0.05

0.05

Contingencies, F12

0.1

0.1

0.1

0.1

0.1

0.1

1.4
20,128,486.6
4

1.4
46,450,
353.79

1.4
21,876,067.
36

1.4
11,806,131.
59

1.4
363,644,7
91.80

1.4
3,825,32
3.25

Total (B)= 1+ f (10-12)

FIXED CAPITAL COST = PPC * B
TOTAL FIXED CAPITAL
INVESTMENT:

0.45
0.45
0.15
0.1
0.1
0.45
0.2
0.05
3.15
335,057,3
31.42
0.25
0.05
0.1
1.4
469,080,2
63.98

1,076,825,080.45

108

0.2
0.05
0.1
1.35
80,536,7
16.36

APPENDIX VII
Material Safety Data Sheet

Acetone
Composition
Substance Formal Name:

Propan-2-one

Substance Chemical
Formula:
Synonyms:

(CH3)2CO
Dimethyl ketone, 2-Propanone, Pyroacetic Acid,
Dimethyl
Formaldehyde
Physical and Chemical Properties

Appearance:

Clear, colorless and highly volatile liquid

Odor:

Mint-like, fragrant, ethereal

Initial boiling point:

56 C (132.8 F)

Freezing point:

-95.35 C (-139.63 F)

Vapor Pressure:

24 kPa @ 20 C

Specific Gravity:

0.790 @ 20 C

Solubility:

Completely miscible in water

Dynamic viscosity:

0.32 centipoise (cP) @ 20 C

Vapor density (air=1):

2.0

Molecular weight

58.08 g/mole
Hazards Identification

Emergency Overview:

Danger, Extremely Flammable liquid and vapor

Flash Point:

-20 C (-4 F)

Auto-Ignition Temperature:

465C (869F)

Upper flammable limit in

air:

12.8 % (v/v)

109

Lower flammable limit in

air:
Hazard Class:

2.1 % (v/v)
3 (Flammable Liquid)

Phenol
Composition
Substance Chemical
Formula:
Synonyms:

C6H6O
Carbolic acid, benzenol, phenylic acid,
hydroxybenzene, phenic acid
Physical and Chemical Properties

Appearance:

Transparent crystalline solid

Odor:

Sweet and tarry

Boiling point:

181.7 C, 455 K, 359 F

Melting point:

40.5 C, 314 K, 105 F

Vapor Pressure:

47 Pa @ 20 C

Specific Gravity:

0.790 @ 20 C

Solubility:

Moderate (8.3 g/100 mL@ 20 C

Vapor density (air=1):

3.2

Molecular weight:

94.11

Acidity (pKa):

9.95 (in water)

max:

270.75 nm

Dipole moment:

1.7 D
Hazards Identification

EU Classification:

Toxic, Corrosive, Combustible

110

Flash Point:

79 C (174 F)

Auto-Ignition Temperature:

715C

Explosive limits, vol% in

air:
Octanol/water partition
coefficient as log Pow:

1.36 10
1.46

Bisphenol A
Composition
Substance Chemical
Formula:
Synonyms:

C15H16O2 / (CH3)2C(C6H4OH)2
p,p'-isopropylidenebisphenol, 2,2-bis(4hydroxyphenyl)propane, 4,4'-(propane-2,2diyl)diphenol
Physical and Chemical Properties

Appearance:

White solid

Boiling point:

220 C, 493 K, 428 F (4 mmHg)

Melting point:

158-159 C, 431-432 K, 316-318 F

Vapor Pressure:

47 Pa @ 20 C

Solubility, g/100ml:

0.03 (very poor)

Density:

1.20 g/cm

Molecular weight:

228.3
Hazards Identification

EU Classification:

Toxic, Corrosive, Combustible

Flash Point:

227 C

Auto-Ignition Temperature:

510-570 C

Octanol/water partition
coefficient as log Pow:

3.32

111

112