1Bottles Group Production of Bisphenol-A
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Transcript of 1Bottles Group Production of Bisphenol-A
1
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 220˚C and a melting
point of 150-170˚C. 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
2
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 by-
products 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.
3
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 5
Environmental & safety hazards 4
Economics & availability of process 3
Efficiency 2
Process Control & Suitability 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.
4
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(-)
Batch
(-17)
Versatile (+2)
used when products are produced
with the same processing
equipment (+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)
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)
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.
5
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 (-)
Acid catalyzed
(-14)
higher recycle rate (+2)
readily and widely used
technology (+3)
corrosive (-4)
requires management of acid
waste disposal (-4)
leads to lower conversion rate(-5)
higher utility consumption (-3)
higher maintenance cost (-3)
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)
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.
6
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(+) Disadvantages(-)
CSTR
Continuous
stirred tank
reactor
(+1)
Can run in both batch and
continuous mode of operation
(+2)
Low operating cost (+3)
Easier to maintain (+3)
Lower conversion per unit volume
(-5)
More inclined to homogenous types
of reactions (-2)
PFR
Plug flow reactor
(+12)
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)
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.
7
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(+) Disadvantages(-)
Fixed bed
(+13)
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)
Difficult in catalyst replacement
(-2)
Poor temperature control (-1)
Undesired heat gradients (-1)
Fluidized Bed
(-8)
Easier catalyst regeneration and
replacement (+2)
Rapid mixing (+2)
Efficient heat transfer (+2)
High maintenance cost (-3)
Particle entrainment (-4)
Erosion (-4)
New technology (-3)
Fluidized bed offers advantages that can’t 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.
8
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 Advantages(+) Disadvantages(-)
Steam
distillation
(+3)
Good temperature control (+1)
Cost effective method (+3)
Efficient (+2)
Readily available technology (+3)
High equipment cost (-3)
High operating costs (-3)
Vacuum
distillation
(+0-)
Lower level of residue build up
(+4)
Reduced temperature at low
pressures (+2)
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.
9
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.
Table 2.6 Types of Crystallizer [10]
Type of Crystallizer Advantages (+) Disadvantages (-)
Forced Circulation
Crystallizer
(-4)
Minimize energy
consumption (+3)
Less maintenance
cost (+3)
Detrimental product
quality (-5)
Reduces product
purity (-5)
Fractional Melt Crystallizer
(+1)
Lower energy
demand for freezing
process (+3)
high selectivity of
crystallization (+5)
high demands on the
equipment
construction (-3)
equipment is complex
and expensive (-3)
poor temperature
control in washing (-
1)
Vacuum Cooling Crystallizer
(-2)
suitable
crystallization method
for continuous
operation (+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 100°C - 120°C instead of
160°C - 170°C.
10
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 (+) Disadvantages (-)
Shell & Tube
(+7)
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)
Initial cost is high (-
3)
Finding leakage is
difficult (-4)
Careful dismantling
and assembling to be
done (-4)
Spiral Plate and Tube
(+1)
High overall heat-transfer
coefficients (+2)
Reduces fouling (+4)
High cost (-3)
Capacities are limited
(-1)
Not for large scale
applications (-1)
Plate fin heat exchanger
(-4)
High heat transfer
efficiency (+2)
Larger heat transfer
area (+2)
Able to withstand
high pressure (+4)
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)
11
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, 4‘-
Isopropylidendiphenol, 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 75˚C 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.
12
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.
13
B. Block Scheme
Bleed
Phenol Recycle
2,143.64 t/a (0.018)
101,091.01 t/a (0.84) 10,389.47 t/a
Phenol
98,947.37 t/a
(0.82)
120,000 t/a BPA
Acetone 132,533.12 t/a (1.0) 120,000 t/a
30,526.32 t/a (0.25) (1.10) (1.0)
31,442.11 t/a (0.26) 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
Reaction
Section
4.4 bar
75°C
Splitting
Section
0.75 bar
116°C
Acetone
Recovery
1.013 bar
88°C
BPA
Crystallization
3 bar
80-95°C
Phenol
Recovery
0.75 bar
152°C
14
C. List of Pure Component Properties
PURE COMPONENT PROPERTIES
Component Name Technological Data Medical Data
Design Systematic
Formula Mol.
Weight
g/mol
Boiling
Point
(1)
°C
Melting
Point
(1)
°C
Density
(2)
kg/m3
MAC LD
Value
mg/m3
g
Notes
Acetone Propanone
C3H6O
58.08
56.11
-95.55
789.9
- 1.159
1,2,4
Phenol Phenol
C6H6O 94.11 181.7 40.5 1.071 - 1 1,2,3
BPA 4'-dihydroxy-
2,2-diphenylpropane
C15H16O2 228.29 360.5 155 1.2 170 >2 5,6
Water Hydrogen
Oxide
H20
18 100 0 998.2 - - -
Notes:
(1) At 101.3 kPa
(2) Density at 20°C
(3) Skin Contact
(4) Oral in g for Humans per kg weight
(5) MAC in air
(6) LD50 studied in rats
15
3.3 Basic Assumptions
A. Plant Capacity:
The plant is designed to produce 120,000 tons of grade A 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. By-
products 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.
16
C. Battery Limit
Inside Battery Limit Outside Battery Limit
Process Equipments
Two Fixed Bed Catalytic Reactors
Three Fractional Melt Crystallizers
Three Distillation Columns
Wastewater Treatment Facility
Power / Electrical Generators
Transformers
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
Incoming Stream Components
Amount
(tons/yr)
Outgoing stream Components
Amount
(tons/yr)
Phenol
(Php 40,849.67 per metric ton)
98,947.37
Bisphenol A
(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
857.46 tpa
AMBERLYST 33
-gel w/ HSO3 functional group -uniformity coefficient- <= 1.60
-Capacity: 4.8 eq/kg; 1.35 eq/L -harmonic mean size- 0.550-0.7 mm
-Max operating temp : 130 degrees Celsius -fines content: <0.425 0.8% max
-Coarse Beads: >1.180 2%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.
17
PLANT LAYOUT
Legend, Inside Battery Limit:
- Pre-heater for phenol
- Fixed bed Reactor
- Distillation Column 1
- Distillation Column 2
- Distillation Column 3
- Control Room
- Dryer
- Crystallizers
- Acetone Storage
- Phenol Storage
- Bisphenol A Storage
18
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 Annual Value (Php)
(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 154,512.60
Total Production Costs 5,289,112,437.60
Total Production Costs + Utility Costs = 5,818,023,681 Php
Table 2. Total Product Revenue
Product Production Unit Price Annual Value (PhP)
(tpa) (Php/ton) (Php/year)
BPA 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.
19
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)
Enthalpy of
formation
(kJ/kg)
Antoine Constants
A B C
Acetone -94.8 56.2 -0.24 3.017 x 10^4 47 235 -2,602.87 -3,710.78 7.02447 1161.0 224
Phenol 40.9 181.8 1.47 60.3509 60.5 419 -346.5 -1,023.44 7.133 1516.79 174.95
Water 0 100 - 3.173 x 10^3 217.5 373.95 -12,678.19 -13,411.62 7.96681 1668.21 228.0
p’-p’ Bisphenol-A 150-157 360.5 3.4 5.3 x 10^-6 28.92 575.89 -41.23 -1,074.94 13.2599
– 7821.36
176.40
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
20
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 + dT
3 in J/gmol-K
A 102b 10
4c 10
8d
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†
21
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.
22
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
23
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(µ) = A * ( 1/T – 1/B), T(Kelvin) and µ(cP)
Component A B
Acetone 367.25 209.68
Phenol 1405.5 370.07
Water 658.25 283.16
† taken from SuperPro Designer v8.5 Database
24
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 75˚C 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 116.32˚C 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 99.96˚C.
Phenol Recovery
In the third distillation column, the operating temperature and pressure is 151.2˚C and
0.73 bar which separates the vapor at 164˚C which is phenol recycled to the feed stream. The
bottom is at 138.57˚C 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 75˚C. 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 50˚C then partial melting at
80˚C 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.
25
PROCESS YIELDS
Process Streams
Name: Ref.
Stream
kg/s t/h t/t product
IN OUT IN OUT IN OUT
Feed (Phenol) < 1> 3.82 - 13.74 - 0.82 -
Acetone < 2> 1.18 - 4.24 - 0.25 -
BPA <28> - 4.63 - 16.67 - 1.00
Water <11> - 0.37 - 1.31 - 0.07
Wastes - - - - - - -
Total 5 5 17.98 17.98 1.07 1.07
Steam Cooling Water
Phenol BPA
Acetone Water
13.74t/h
(0.82t/t)
4.24 t/h
(0.25 t/t)
BPA Condensation Reaction
16.67t/h
(1.00t/t)
1.31t/h
(0.07 t/t)
311.95t/h
(18.71t/t)
74.55t/h
(4.47t/t)
26
SUMMARY OF UTILITIES
EQUIPMENT
NR.
UTILITIES
Heating Cooling Power
Load
(kW)
Steam
(t/yr)
Load
(kW)
Cooling
Water (t/yr)
Load
(kW)
Electr.
(kWh/h)
R01 44,064
R02 44,064
E01 129,600
E02 1,134.30 1,406,237.7
E03 190.7 2,345.76
E04 80.2 986.4
E05 129,600
E06 1,222.0 15,030
E07 95.64 118,241.28
E08 30.7 38,086.56
S01 272.495 336,129.12 1.498
S02 0.627 259,200 1.473
S03 0.627 259,200 1.501
D01 0.122 24.192
P01 0.4452
P02 0.1872
P03 2.099
P04 0.5452
P05 0.0477
P06 0.0477
P07 0.0005
P08 0.0005
P09 0.0041
P10 0.0065
P11 0.0065
TOTAL 1,494.276 536,786.35 1,533.14 2,246,022.66 4.474 3.3901
27
CHAPTER VI
MASS AND HEAT BALANCES
Table 6.1 Overall Mass and Heat Balance
IN EQUIPM.
IDENTIF.
OUT
Plant EQUIPMENT EQUIPMENT Plant
Mass
kg/s
Heat
kW
Mass
kg/s
Heat
kW
Stream
Nr.
Stream
Nr.
Mass
kg/s
Heat
kW
Mass
kg/s
Heat
kW
3.93
1.18
5.11
3.93
1.18
5.11
-626.01
-626.01
<1>
<2> R01
Total
<4> 5.11
5.11
-626.01
-626.01
5.11
5.11
-345.13
-345.13
<4> E01
Total
<5>
5.11
5.11
-345.13
-345.13
5.11
5.11
13.626
2169.984
2050.829
4234.439
<5>
<6>
<7>
C01
E06
E02
Total
<9>
<8>
0.40
4.71
5.11
2291.578
1942.861
4234.439
0.40
0.40
2291.578
77.912
74.049
2443.539
<10>
<14>
<13>
C02
E07
E03
Total
<15>
<12>
0.36
0.04
0.40
1601.167
842.372
2443.539
0.36
4.71
1942.861
189.291
130.921
<18>
<21>
<19>
C03
E08
E04
<22>
<20>
0.05
4.66
543.055
1720.018
28
4.71 2263.073 Total 4.71 2263.073
4.66
4.66
850.574
850.574
<19> E05
Total
<25> 4.66
4.66
850.574
850.574
4.66
4.66
-272.614
-272.614
<25> S01 <26> 4.66
4.66
-272.614
-272.614
4.66
4.66
327.15
327.15
<26> S02
Total
<27> 4.66
4.66
327.15
327.15
4.66
4.66
163.59
163.59
<27> S03
Total
<28> 4.66
4.66
163.59
163.59
4.63
4.63
54.531
54.531
<28> D01
Total
<29> 4.63
4.63
54.531
54.531
4.63
5.11 5.11
OUT-IN: 9093.142 OUT-IN: 9093.142
29
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 Raoult’s 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 Fenske’s Equation and Gilliland’s
Equation respectively. The minimum reflux ratio and the actual reflux ratio were calculated
using Underwood’s Equation. The actual numbers of stages were computed by getting the
overall column efficiency, which was computed using O’Connell’s 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 Kirkbride’s 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
30
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.
31
Major Equipments
Fig 7.1 Fixed Bed Catalytic Reactor
32
FIXED BED CATALYTIC REACTOR SPECIFICATION SHEET
EQUIPMENT NR. :
NAME :
R01 and R02
Fixed Bed Catalytic Reactor
Pressure [bara] : 4.4
Temperature [˚C] : 75
Volume [m3] : 4.09
Diameter [m] : 0.8
L or H [m] : 8.05
Thickness [mm] : 1.66
Residence time [mins] : 13.34
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
4
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
Number
-Series
-Parallel
1
-
Materials of Construction (1)
:
Trays:
Column: SS SA-240 GR-304
Other
Remarks:
(1) Stainless Steel Grade 304
33
DISTILLATION COLUMN & SPECIFICATION SHEET
EQUIPMENT NUMBER: C02
NAME : Distillation Column 1
General Details
Service
: - distillation / extraction / absorption / ----------
Column type
: -
Tray Number
: -
- Theoretical : 10
- Actual : 29
- Feed(actual) : 23
Tray Distance (HETP) [m] : 0.5
Column Diameter [m] : 1.5
Tray Material : SS314
Column Height [m] : 15.6
Column Material : CS
Heating
: reboiler
Process Condition
Stream Details Feed Top Bottom Reflux/ Extractant
Absorbent
side
stream
Temp. [degC] 93 99 134 49
Pressure [bara] 0.74 0.74 0.74 0.135
Density [kg/m3] 979.64 967.82 1078.94 1137.35
Mass Flow [kg/s] 5.11 0.40 4.72 5.73
Composition
mol% wt% mol% wt% mol% wt% mol% wt%
Acetone 1.44 0.69 2.94 8.87 0 0 2.94 8.87
Bisphenol A 48.23 7.15 0 0 94.98 98.19 0 0
Phenol 2.1 1.62 .04 0.21 4.07 1.73 .04 0.21
Water 48.23 90.55 97.02 90.93 0.95 .08 97.02 90.93
-------
-------
Column Intervals
Trays Packing
Not Applicable
Number of
Type
:
caps / sieve holes / -----------
----
: 70872 Material :
Active Tray Area [m3]
: 1.21 Volume :
Weir Length [m]
: 1.14 Length
:
Diameter of [mm]
Width
:
chute pipe / hole / ----------
---- : 8 Height :
Remarks:
34
Fig. 7.2 Distillation Column 1
35
DISTILLATION COLUMN & SPECIFICATION SHEET
EQUIPMENT NUMBER: C03
NAME : Distillation Column 2
General Details
Service
: - distillation / extraction / absorption / ----------
Column type
: -
Tray Number
: -
- Theoretical : 11
- Actual : 25
- Feed(actual) : 4
Tray Distance
(HETP)
[m] : 0.5
Column
Diameter
[m] : 1.24
Tray
Material
: SS314
Column
Height
[m] : 13.9
Column Material : CS
Heating
: reboiler
Process Condition
Stream Details Feed Top Bottom Reflux/ Extractant
Absorbent
side
stream
Temp. [degC] 98 77 100 100
Pressure [bara] .4 1.5 1 1.5
Density [kg/m3] 968.48 975.85 967.47 975.85
Mass Flow [kg/s] 0.40 .04 0.40 .04
Composition
mol% wt% mol% wt% mol% wt% mol% wt%
Acetone 2.94 8.89 74.8 90.53 99.89 0.20 74.8 90.53
Phenol 0.06 0.21 0 0 0.04 0.23 0 0
Water 97 90.9 25.2 9.47 0.06 99.57 25.2 9.47
-------
-------
-------
Column Intervals
Trays Packing
Not
Applicable
Number of
Type
:
caps / sieve holes /
---------------
: 49122 Material :
Active Tray
Area [m2]
: 0.84 Volume :
Weir Length [m]
: .95 Length
:
Diameter of
Width
:
chute pipe / hole /
-------------- : 8mm Height :
Remarks:
36
Fig 7.3 Distillation Column 2
37
DISTILLATION COLUMN & SPECIFICATION SHEET
EQUIPMENT NUMBER: C04
NAME : Distillation Column 2
General Details
Service
: - distillation / extraction / absorption / ----------
Column type
: -
Tray Number
: -
- Theoretical : 2
- Actual : 3
- Feed(actual) : 2
Tray Distance
(HETP)
[m] : 0.5
Column Diameter [m] : 0.727
Tray Material
: SS314
Column Height [m] : 2.515
Column Material : CS
Heating
: reboiler
Process Condition
Stream Details Feed Top Bottom Reflux/ Extractant
Absorbent
side
stream
Temp. [degC] 133 164 139 164
Pressure [bara] 0.74 0.74 0.74 1.9
Density [kg/m3] 1079.62 953.64 1076.67 953.64
Mass Flow [kg/s] 4.71 .05 4.66 4.94
Composition
mol% wt% mol% wt% mol% wt% mol% wt%
Acetone 0 0 0 0 0 0 0 0
Bisphenol A 94.97 98.19 0 0 98.05 99.3 0 0
Phenol 4.07 1.74 78.77 93.4 1.66 0.69 78.77 93.4
Water .95 .08 21.23 6.60 0.29 .01 21.23 6.60
-------
-------
Column Intervals
Trays Packing Not Applicable
Number of
Type
:
caps / sieve holes / -----------
----
: 16560 Material :
Active Tray Area [m2]
: 0.29 Volume :
Weir Length [m]
: 0.6 Length
:
Diameter of [mm]
Width
:
chute pipe / hole / ----------
---- : 8 Height :
Remarks:
38
Fig. 7.3 Distillation Column 3
39
Fig. 7.5 Fractional Melt Crystallizer
COOLING/
HEATING
MEDIUM IN
P-9
MELT
FEED
P-14
P-16 P-17
D=2.12 m
P-18
P-19
P-20
P-22
H=4.14 m
PRODUCT
COOLING/
HEATING
MEDIUM OUT
40
CRYSTALLIZER SPECIFICATION SHEET
*Values obtained from Superpro V8.5
EQUIPMENT NR. :
NAME :
S01
BPA Crystallizer
Effective Volume cu.m 15
Diameter m 2.12
Height m 4.24
Materials of Construction CS
Process Conditions
Feed Temperature ˚C 75
Operating Temperature ˚C 50
Operating Pressure bar 3
Residence Time h 1
Crystal Quantity cu.m 15
Slurry Quality cu.m 180
Power for Agitation kW 1.4977
Working/Vessel Volume Limits
Min Allowable %
Max Allowable %
15
90
Component Mass Flow
Rate
(kg/h)
Molar Flow Rate
(kmol/s)
Mass
Percentage
(%)
Conc.
(g/l)
BPA
Phenol
Water
16667.65
114.13
1.68
0.0203
3.4255x10^-4
2.593x10^-5
99.31
0.68
0.01
1112.89
7.62
0.11
41
CRYSTALLIZER SPECIFICATION SHEET
*Values obtained from Superpro V8.5
EQUIPMENT NR. :
NAME :
S02
BPA Crystallizer
Effective Volume cu.m 15
Diameter m 2.12
Height m 4.24
Materials of Construction CS
Process Conditions
Feed Temperature ˚C 50
Operating Temperature ˚C 80
Operating Pressure bar 3
Residence Time h 1
Crystal Quantity cu.m 15
Slurry Quality cu.m 180
Power for Agitation kW 1.4977
Working/Vessel Volume Limits
Min Allowable %
Max Allowable %
15
90
Component Mass Flow
Rate
(kg/h)
Molar Flow Rate
(kmol/s)
Mass
Percentage
(%)
Conc.
(g/l)
BPA
Phenol
Water
16781.76
0.0167
1.68
0.0204
4.934x10^-8
2.593x10^-5
99.989
0.001
0.01
11138.32
0.00114
0.114
42
CRYSTALLIZER SPECIFICATION SHEET
*Values obtained from Superpro V8.5
EQUIPMENT NR. :
NAME :
S03
BPA Crystallizer
Effective Volume cu.m 15
Diameter m 2.12
Height m 4.24
Materials of Construction CS
Process Conditions
Feed Temperature ˚C 80
Operating Temperature ˚C 95
Operating Pressure bar 3
Residence Time h 1
Crystal Quantity cu.m 15
Slurry Quality cu.m 180
Power for Agitation kW 1.4977
Working/Vessel Volume Limits
Min Allowable %
Max Allowable %
15
90
Component Mass Flow
Rate
(kg/h)
Molar Flow Rate
(kmol/s)
Mass
Percentage
(%)
Conc.
(g/l)
BPA
Phenol
Water
16781.78
0.01678
1.662
0.0204
4.9586x10^-8
2.5648x10^-5
99.989
0.001
0.01
11138.32
0.00114
0.114
43
Fig. 7.5 Heat Exchanger Drawing
44
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
Heat Exchange Area [m2] : 25.8
Overall Heat Transfer Coefficient [W/m2
˚C] : 500
Log Mean Temperature Diff. (LMTD) [˚C] : 8..93
Passes Tube Side : 1
Passes Shell Side : 1
Correction Factor LMTD : 1
Corrected LMTD [˚C] : 8.93
Process Conditions
Medium
Mass Stream [kg/s]
Mass Stream
- Evaporize [kg/s]
- Condense [kg/s]
Average Specific Heat [kJ/kg˚C]
Heat of Evap/Condensation [kJ/kg]
Temp. IN [˚C]
Temp. OUT [˚C]
Pressure [bar]
Material
Shell Side Tube Side
Cooling water
5
~
~
4.18
~
25
46.50
CS
BPA, phenol, acetone, Water
5.1131
~
~
2.70
~
75
50
SS304
Remarks:
CS – carbon steel
SS304 – Stainless steel
Shell diameter – 12in
# of tubes in shell – 55
Tube OD – 1.25 in
Tube length – 16ft
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
Heat Exchange Area [m2] : 25.8
Overall Heat Transfer Coefficient [W/m2
˚C] : 500
Log Mean Temperature Diff. (LMTD) [˚C] : 8..93
Passes Tube Side : 1
Passes Shell Side : 1
Correction Factor LMTD : 1
Corrected LMTD [˚C] : 8.93
Process Conditions
Medium
Mass Stream [kg/s]
Mass Stream
- Evaporize [kg/s]
- Condense [kg/s]
Average Specific Heat [kJ/kg˚C]
Heat of Evap/Condensation [kJ/kg]
Temp. IN [˚C]
Temp. OUT [˚C]
Pressure [bar]
Material
Shell Side Tube Side
Cooling water
5
~
~
4.18
~
25
46.50
CS
BPA, phenol, acetone, Water
5.1131
~
~
2.70
~
75
50
SS304
Remarks:
CS – carbon steel
SS304 – Stainless steel
Shell diameter – 12in
# of tubes in shell – 55
Tube OD – 1.25 in
Tube length – 16ft
45
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
Overall Heat Transfer Coefficient [W/m2
˚C] : 500
Log Mean Temperature Diff. (LMTD) [˚C] : 51.04
Passes Tube Side : 8
Passes Shell Side : 5
Correction Factor LMTD : 0.966
Corrected LMTD [˚C] : 51.04
Process Conditions
Medium
Mass Stream [kg/s]
Mass Stream
- Evaporize [kg/s]
- Condense [kg/s]
Average Specific Heat [kJ/kg˚C]
Heat of Evap/Condensation [kJ/kg]
Temp. IN [˚C]
Temp. OUT [˚C]
Pressure [bar]
Material
Shell Side Tube Side
Cooling water
5
~
~
4.18
~
25
40.697
CS
BPA, phenol. Water
4.66
~
~
2.869867
~
138.5728
75
CS
Remarks:
Shell diameter – 12in
# of tubes in shell – 55
Tube OD – 1.25 in
Tube length – 16ft
46
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.
47
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.
48
Fig.8.3 Controls for 1st Distillation Column
49
Fig.8.4. Controls for 2nd Distillation Control
50
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.
51
Fig.8.6. Controls for Crystallizer
52
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
standard
Bisphenol A final
product
Catalyst
(Amberlyst
33)
Slipping hazard,
may cause an
explosive dust-air
mixture
May cause eye &
skin irritation
Pre-heated to
liquid and fed
back to reactor
May be disposed
of by
combustion in a
coal-fired boiler
Liquid Excess
phenol
Corrosive
Fed back to
reactor or used
in crystallizer for
washing
53
BPA isomers
& trinuclear
impurities
Tarry
substances or
pitch
Waste/ by-
product water
Cooling
water
Unreacted
acetone
Toxic if ingested
Toxic. Can cause
disorder in the
environment
Acidic since it is a
formed through an
acidic IER catalyst
Maybe
contaminated in
steel corrosion
Causes skin
irritation
Sent to a solvent
recovery system
and recycled
back to the
process
Marketed since
it is used in the
production of
carbon
electrodes
Treated in
wastewater
facility before
disposal
Recycled and
treated in water
treatment facility
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.
54
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 Deviation Possible Causes Consequences Actions required
No No flow
No Acetone (or Phenol) is
available at storage
Low Temperature in Phenol
Pre-Treatment Column
Pump fails (impeller
corroded, loss of drive,
motor fault (etc.)
Line blockage
Line Fracture
Loss of necessary feed
to reaction section and
reduction of output.
Flow slows down in
transfer line to Fixed
Bed Reactor
Pump overheats
Flow slows down
Leaks from pipelines
(a) Ensure that necessary feed is
available at storage tanks
(b) raise the temperature in Phenol
Pre-Treatment Column
(c) Regular inspection of pumps
(d) Install kickback on pumps and
spare pumps
(e) Regular patrolling, inspection
and maintenance of pipelines.
(f) covered in (e)
55
Table 10.1: HAZOP Study (continued)
More of
More flow
Control Valves fail open
Fixed Bed Reactor
overfills
Disturbances leading to
problems on reaction
section
(g) Regular inspection of
control valves
(h) Ensure the flow rate
necessary for the process and
the level for each vessel to
avoid overfilling
More
temperature
Temperature controller fail
Thermal expansion due to
fire or strong sunlight
Disturbance in the
reaction section
Some of the
compounds may
evaporate thus reduce
product output
Pipeline fracture
Vessels are subjected
to high pressure
(i) regular inspection of
temperature controllers
(j) Check whether there are
adequate alarms for any
undesired temperature increase.
More
pressure
Flow rate is higher than
desired
Control valves are closed in
error while pump is running
High pressure in
pipelines, reactor and
other vessels
Transfer line subjected
to full pump delivery or
surge pressure
(k) Install alarm for pressure
monitoring inside the reactor
(l) inspection of control valves
and pumps
56
Table 10.1: HAZOP Study (continued)
Guide
word Deviation Possible Causes Consequences Actions required
Less of Less flow Leaking valves and
pipelines
Valves are closed in error
Material loss adjacent
to public highway
Lesser Product output
(m) Regular inspection of
pumps, controllers, valves and
pipelines. Provide spare pumps
if necessary.
Less
temperature
Insufficient steam fed to the
distillation process
Disturbance in the
distillation process
(n)Ensure the steam available
for the distillation process.
As well
as
Excess
amount of
Acetone and
Phenol in
Recycle
section
Other
than
Maintenance Equipment Failure, flange
leak, etc.
Line cannot be
completely drained or
purged
(o) Install low-point drain and N
purge point downstream
57
FIRE AND EXPLOSION INDEX (F&EI)
Table 10.3 F&EI method for safety evaluation
Area/ Country: Philippines Division: Location: Naga, Cebu City Date:
Prepared by: CPDO4 Approved by: Building:
Reviewed by: CPD04 Reviewed by: Reviewed by: CPDO4
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 1
A. Exothermic Chemical Reactions 0.30- 1.25 0.3
B. Endothermic Process 0.20 - 0.40 0
C. Material Handling and Transfer 0.25- 1.05 0.4
D. Enclosed or Indoor Process Units 0.25- 0.90 0
E. Access 0.20- 0.35 0
F. Drainage and spill Control 0.25- 0.50 0.3
GENERAL PROCESS HAZARDS FACTOR (FI) 2
2. Special Process Hazards
Base Factor 1.00 1
A. Toxic Material(s) 0.20- 0.80 0.6
B. Sub- Atmospheric Pressure (< 500 mm Hg) 0.50 0
C. Operation In or Near Flammable Liquids
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 0
E. Pressure (operating pressure : 20 psig) 0-0.85
0.8
F. Low temperature 0.20- 0.30 0
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 0
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 0
L. Rotating Equipment 0.50 0
SPECIAL PROCESS HAZARDS FACTORS (F2 6.2
PROCESS UNIT HAZARDS FACTOR (F1 x F2)= F3 2x6.2 = 12.4
FIRE AND EXPLOSION INDEX (F&EI = F3 x MF)
58
CHAPTER XI
ECONOMICS
Table 11.1 Total Investment Costs
Fraction of Total
Investment Amount (Php)
Fixed Capital Costs 0.75 1,076,825,080.45
Equipment and installation
Piping, Instrumentation and Control 0.6 861,460,064.36
Indirect Costs, share of (*)
Buildings and Structures
Auxiliary facilities - utilities, land 0.15 215,365,016.09
Indirect Costs, share of (*)
Working Capital 0.15 161,523,762.07
Fixed Capital (typically 15%)
Recoverable at End of Plant Life
Investment (additional) for start-up until income starts
Start-up costs 0.1 10,768,250.80
- initial catalyst charge
5,300,813,548.62
- raw materials and intermediates
- finished product inventories
* Design, engineering, construction, cost estimation, supervision,
contingencies 6,549,930,641.94
59
Table 9.2 Summary of Annual Production Cost
TYPICAL VALUE (% of Item) Amount (PhP)
1 Raw Material -
5,300,813,548.62
2
Miscellaneous
Materials 10% Raw Material 530,081,354.86
3 Utilities -
2,001,121.68
4
Shipping and
Packaging 15% rawmaterial 795122032.3
5 Maintenance 10% Fixed Capital 107,682,508.05
7 Laboratory cost 10% Operating Labor 10368000
8 Supervision 10% Operating Labor 1036800
9 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
15
Research and
development 5% Operating Labor 518,400.00
TOTAL ANNUAL
PRODUCTION COSTS 7,487,485,885.65
60
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 % Net Cash Flow Cumulative Cash Flow
0 0 0 0
1 0 -1,076,825,080.45 -1,076,825,080.45
2 0 -161,523,762.07 -1,238,348,842.52
3 0 -5,311,581,799.00 -6,549,930,641.52
4 100 13,104,173,182.51 6,554,242,540.99
5 100 13,104,173,182.51 19,658,415,723.50
6 100 13,104,173,182.51 32,762,588,906.01
7 100 13,104,173,182.51 45,866,762,088.52
8 100 13,104,173,182.51 58,970,935,271.03
9 100 13,104,173,182.51 72,075,108,453.54
10 100 13,104,173,182.51 85,179,281,636.05
11 100 13,104,173,182.51 98,283,454,818.56
12 100 13,104,173,182.51 111,387,628,001.07
13 100 13,104,173,182.51 124,491,801,183.58
14 100 13,104,173,182.51 137,595,974,366.09
15 100 13,104,173,182.51 150,700,147,548.60
Note: year 0 – 3 is the proposed time frame for plant construction
61
Cash Flow Diagram
Rate of Return
ROR = 0.488
ROR = 48.8%
-20,000,000,000.00
0.00
20,000,000,000.00
40,000,000,000.00
60,000,000,000.00
80,000,000,000.00
100,000,000,000.00
120,000,000,000.00
140,000,000,000.00
160,000,000,000.00
0 2 4 6 8 10 12 14 16
Cu
mm
ula
tive
cas
h F
low
(P
hP
)
t(years)
Cash Flow Diagram
cash flow
62
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.
63
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] Navid Naderpur ,(2008), Petrochemical production processes
[12] A. Chakrabarti, M.M. Sharma, React. Polym. 20 (1993)
B.C. Gates, Catalytic Chemistry, Wiley, New York, 1992.]
[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).
64
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
O’Young 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
65
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:
66
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
67
IN = OUT
5.107371778 = 0.3979543811 + 4.715134056
5.11 = 5.11
Second Distillation (Acetone Recovery Column)
________________________
_______________________
________________________
IN = OUT
0.3979543811 = 0.03819611667 + 0.3597582678
0.3979 = 0.3979
C02
68
Third Distillation Column (Partial Phenol Recovery Column)
________________________
0.05306306313885 kg/s
________________________
________________________
4.662070917 kg/s
IN=OUT
4.715134056 = 0.05306306313885 + 4.662070917
4.715134056 = 4.715134056
C03
69
Crystallizers
IN=OUT
4.662070917 kg/s = 4.662070917 kg/s
4.6154 x 10^-4 kg/s water
4.662 kg/s BPA
4.6154 x 10^-4 kg/s water
IN=OUT
4.6297 = 4.6297
Crystallizer 1
Crystallizer 2
Crystallizer 3
Drier
70
APPENDIX II
HEAT AND ENERGY BALANCE
Heat Balance- Reactor
Reaction Temperature: 348 K
Pressure: 4.4 bars
Heat Capacity Constants:
Component A B c
Phenol 207.48 -103.75 274
Acetone 71.96 20.1 -12.78
BPA Cp = 1.2
Inlet
Inlet Temperature: 298 K
Ingredient Name Flowrate (kg/s) Mass Component (%)
Phenol 3.6564 76.27
Acetone 1.137 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(3482-298
2) + (274x10-6)/3(348
3-298
3)]
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(3482-298
2) + (-12.78x10-5)/3(348
3-298
3)]
Q= 120781.8 W
Qin= 514862.12 W
71
Outlet
Component Flowrate (kg/s) Mass Component (%)
Bisphenol-A 4.340 90.54
Phenol 0.0775 1.62
Acetone 0.033 0.69
Water 0.3427 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(3082-348
2) + (274x10-6)/3(308
3-348
3)]
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(3082-348
2) + (-12.78x10-5)/3(308
3-348
3)]
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
72
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 = mcp∆T
=
Q =
Solving for T2 of the cooling water:
Qhot = -Qcold
345.13 =
°C
T2 = 46.51°C ≈319.67 K
CpH2 O =
Cpphenol =
Cpacetone =
73
CpBPA = =
Heat Balance of 2nd
Heat Exchanger:
Q = mcp∆T where: Cp =
=
Cp = 2.869867
Q =
Solving for T2 of H2O:
=
K
T2 = 313.8473096 K ≈ 40.697 °C
Heat Balance- Distillation Columns
Operating Conditions
Equipment Bottoms(Kelvin) Tops(Kelvin)
C01 372.39 406.87
C02 349.74 372.96
C03 436.86 411.57
Heat of Vaporization constants
Tc(K) A b
Acetone 508 44497.1062 0.3818
Phenol 694 70126.2112 0.396
H2O 647 60334.5172 0.4132
Bisphenol 852 121393.1481 0.4077
Hvap(J/mol)=A(1-Tr)^b
C01 C02 C03
Top(sat vap) Bottom(sat liq) Top(sat vap)
Bottom(sat
liq)
Top(sat
vap)
Bottom(sat
liq)
Acetone 26874.47 24026.41438 28507.05 26831.74 21007.79 23594.04
Phenol 51713.46 49442.28108 53126.21 51677.53 47329.53 49120.37
H2O 42342.52 40058.74696 43752.19 42306.57 37910.94 39733.08
Bisphenol - 93162.31956 - 95993.79 - 92760.24
74
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 # Reflux Ratio D(kmol/hr) V(kmol/hr)
C01 1.5 74.59 186.48
C02 2 2.87 8.61
C03 3.5 2.41 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 # QB(kW)
C01 2050.83
C02 74.05
C03 130.92
75
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)
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 # QB (kW)
C01 1942.86
C02 842.37
C03 1900.48
Solving for the energy in the distillate stream,
QD = Qfeed - QB + QC + QR
Equipment # QD (kW)
C01 2291.58
C02 1601.17
C03 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.
Equipment # - QC(kW)
C01 2169.98
C02 77.91
C03 189.29
76
In summary;
Equipment #
IN OUT
Qb Qc Qf BOTTOMS DISTILLATE
C01 2050.828942 2169.983881 13.62592 1942.861097 2291.577646
C02 74.04872979 77.91243917 2291.577646 842.3719186 1601.166896
C03 130.9208438 189.2906762 1942.861097 1900.484314 543.0545012
Heat Balance- Crystallizers
Inlet
From Superpro:
Ingredient Name Flowrate (kg/s) Mass Component
(%)
Concentration
(g/L)
Bisphenol-A 4.6297 99.3059 1,112.84185
Phenol 0.03220 0.6907 7.73992
Water 0.00016 0.0034 0.03846
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 kW∙hr/s
Outlet
Component Flowrate (kg/s) Mass Component
(%)
Concentration
(g/L)
Bisphenol-A 4.63292 99.3750 1,130.7428
Phenol 0.02898 0.6216 7.073062
Water 0.00016 0.0034 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 = 0.151 KW∙hr/s
77
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 Flowrate (kg/s) Mass
Component(%)
Concentration
(g/L)
Bisphenol-A 4.63292 99.3750 1,130.7428
Phenol 0.02898 0.6216 7.073062
Water 0.00016 0.0034 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 kW∙hr/s
Output:
Component Flowrate (kg/s) Mass
Component(%)
Concentration
(g/L)
Bisphenol-A 4.63581 99.4387 1,111.048586
Phenol 0.02601 0.5579 6.233727
Water 0.00016 0.0034 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 kW∙hr/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
78
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 Flowrate (kg/s) Mass Component
(%)
Concentration
(g/L)
Bisphenol-A 4.63581 99.4387 1,111.048586
Phenol 0.02601 0.5579 6.233727
Water 0.00016 0.0034 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 kW∙hr/s
Output:
Component Flowrate (kg/s) Mass
Component(%) Concentration (g/L)
Bisphenol-A 4.63841 99.4944 1,101.48417
Phenol 0.02341 0.5021 5.558939
Water 0.00016 0.0034 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 kW∙hr/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
79
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 Flowrate (kg/s) Mass Component
(%) Concentration (g/L)
Bisphenol-A 4.63841 99.4944 1,101.48417
Phenol 0.02341 0.5021 5.558939
Water 0.00016 0.0034 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
80
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
81
P=560
mmHg
T=116OC
Design of Distillation Columns 1,2,3
1st Distillation Column: Equipment Design
Assuming the feed is saturated liquid;
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
82
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
Vapour Pressure H2O:
Vapour pressure Phenol:
Relative Volatility:
Data:
Antoine Coefficient
Component A B C
Water 7.96681 1668.21 228
Phenol 7.13301 1516.79 174.954
83
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:
84
Calculating for Actual Number of Stages: Using O’Connell’s 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:
85
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,
86
Solving for the weir length:
For weir height and hole diameter,
Solving for the number of holes:
87
P=760
mmHg
T=88OC
2nd
Distillation Column: Equipment Design
Assuming the feed is saturated liquid;
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
88
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
Vapour Pressure H2O:
Vapour pressure Acetone:
Relative Volatility:
Data:
Antoine Coefficient
Component A B C
Water 7.96681 1668.21 228
Acetone 7.11714 1210.595 229.664
89
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:
90
Calculating for Actual Number of Stages: Using O’Connell’s 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:
91
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:
92
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:
93
P=560
mmHg
T=151OC
3rd
Distillation Column: Equipment Design
Assuming the feed is saturated liquid;
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
94
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
Vapour Pressure H2O:
Vapour pressure Phenol:
Relative Volatility:
Data:
Antoine Coefficient
Component A B C
Water 7.96681 1668.21 228
Phenol 7.13301 1516.79 174.954
95
Calculating for Minimum Number of Stages:
Using Fenske Equation:
Calculating for Rm:
Using Underwood Equation:
Solving for
By iteration:
Solving for R:
96
Calculating for Number of theoretical stages:
Using Gilliland Equation:
Calculating for Actual Number of Stages: Using O’Connell’s 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:
97
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:
98
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:
99
Design of a Crystallizer
1 2
3
Inlet
From Superpro:
Ingredient Name Flowrate (kg/s) Mass Component
(%)
Concentration
(g/L)
Bisphenol-A 4.6297 99.3059 1,112.84185
Phenol 0.03220 0.6907 7.73992
Water 0.00016 0.0034 0.03846
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 kW∙hr/s
100
Outlet
Component Flowrate (kg/s) Mass Component
(%)
Concentration
(g/L)
Bisphenol-A 4.63292 99.3750 1,130.7428
Phenol 0.02898 0.6216 7.073062
Water 0.00016 0.0034 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 KW∙hr/hr
Crystallizer:
P = 3 bar Residence Time = 1 hr
Power = 1.499 KW 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)
Mass
Component
(%)
Concentration
(g/L)
Bisphenol-A 16,781.75987 99.9899 1,138.32026
Phenol 0.0167 0.0001 0.00114
Water 1.67835 0.01 0.11384
101
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 KW∙hr/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)
Mass
Component
(%)
Concentration
(g/L)
Bisphenol-A 16,781.77665 99.99 1,117.762774
Phenol 0 0 0
Water 1.67835 0.01 0.111787
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 KW∙hr/hr
102
@ Crystallizer 3
Input:
Component Flowrate
(Kg/hr)
Mass
Component
(%)
Concentration
(g/L)
Bisphenol-A 16,781.77665 99.99 1,117.76284
Phenol 0.01678 0.0001 0.00112
Water 1.66156 0.0099 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 KW∙hr/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)
Mass
Component
(%)
Concentration
(g/L)
Bisphenol-A 16,781.79343 99.9901 1,107.484677
Phenol 0 0 0
Water 1.66156 0.0099 0.109652
Total: 16,783.45499
103
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 KW∙hr/hr
Drier (Rotary):
Component Flowrate
(Kg/hr)
Mass
Component
(%)
Concentration
(g/L)
Bisphenol-A 16,781.77665 99.99 1,107.48341
Water 1.67835 0.01 0.11076
Total: 16,783.455
Temperature = 95 °C
Pressure = 1.013 bar
Enthalpy = 1,035.460 KW∙hr/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 KW∙hr/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 KW∙hr/hr
104
APPENDIX IV
PROCESS STREAM SUMMARY
Table 4.1
Components Stream 1=3 Stream 2 Stream 4=5
kg/s kmol/s kg/s kmol/s 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 Stream 7=8 Stream 10=11
kg/s kmol/s kg/s kmol/s kg/s kmol/s
Acetone 0.0353 6.07x10^-4 - - 0.0353 6.07x10^-4
Phenol 8.3x10^-4 8.78x10^-6 0.0818 8.69x10^-4 8.3x10^-4 8.78x10^-6
BPA - - 4.6297 0.0203 - -
Water 0.3618 0.02 3.66x10^-3 3.66x10^-3 0.3618 0.02
Table 4.3
Components Stream 12=13 Stream 14=15 Stream 16-17
kg/s kmol/s kg/s kmol/s 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 Stream 19=20 Stream 21=22
kg/s kmol/s kg/s kmol/s 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 1.9x10^-4 1.1 x10^-5
105
Table 4.5
Components Stream 23 Stream 25 Stream 26
kg/s kmol/s kg/s kmol/s 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 Stream28=29
kg/s kmol/s 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
106
APPENDIX V
PROCESS FLOW SCHEME
107
APPENDIX VI
ECONOMIC EVALUATION
Table A.6.1 Major Equipments Purchase Cost
Equipment Purpose # of
units Cost/unit (PhP) total Purchase cost (PhP) Source
Fixed Bed Reactor Reaction 2 2480279.746 4960559.492 SuperPro Designer v8.5
Distillation Column Separation 1 2480279.746 2480279.746 Plant Design & economics for ChE
Crystallizer Purification 1 82,459,136.46 82459136.46 SuperPro Designer v8.5
Dryer Purification 1 975,847.77 975847.7688 SuperPro Designer v8.5
Conveyor Transport 2 10653004.81 21306009.62 SuperPro Designer v8.5
Pumps Transport 12 8,863,950.57 106367406.8 SuperPro Designer v8.5
Heat Exchangers Heat
transfer 2 1,057,168.42 4228673.665 SuperPro Designer v8.5
Reboiler Steam 3 1,065,300.48 3195901.443 SuperPro Designer v8.5
Acetone tank storage 1 2,520,940.07 2520940.069 SuperPro Designer v8.5
Phenol Silo Storage 1 2,805,562.34 2805562.335 SuperPro Designer v8.5
Condenser Transport 3 3252825.896 9758477.688 SuperPro Designer v8.5
Purchase Equipment cost TOTAL: 251467838
108
Table A.6.2. Major Equipment Fixed Capital Cost
EQUIPMENT:
Heat Exchangers
Condenser
Fixed bed reactor
Distillation Column
Crystallizer
Dryer pumps Conveyor Reboiler Acetone
Storage tank Phenol
Silo
TOTAL PURCHASE COST (PCE) 4228673.665 9,758,4
77.69 4,960,559.4
9 2,480,279.7
5 82,459,13
6.46
975847.7688
106367406.8
21306009.62
3195901.443
2520940.069 2805562.
335
Equipment Erection, f1 0.4 0.4 0.45 0.4 0.45 0.5 0.45
0.5 0.4 0.4 0.5
Piping, f2 0.7 0.7 0.45 0.7 0.45 0.2 0.45
0.2 0.7 0.7 0.2
Instrumentation, f3 0.2 0.2 0.15 0.2 0.15 0.1 0.15
0.1 0.2 0.2 0.1
Electrical, f4 0.1 0.1 0.1 0.1 0.1 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 0.1
0.05 0.15 0.15 0.05
Utilities, f6 0.5 0.5 0.45 0.5 0.45 0.25 0.45
0.25 0.5 0.5 0.25
Storages, f7 0.15 0.15 0.2 0.15 0.2 0.25 0.2
0.25 0.15 0.15 0.25
Site Development, f8 0.05 0.05 0.05 0.05 0.05 0.05 0.05
0.05 0.05 0.05 0.05
Total (A) = (1+ Ʃf(1-9)) 3.4 3.4 3.15 3.4 3.15 2.8 3.15
2.8 3.4 3.4 2.8
TOTAL PHYSICAL PLANT COST (PPC) PPC=PCE*A 14,377,490.
33,178,824.14
15,625,762.40
8,432,951.14
259,746,279.86
2,732,373.75
335,057,331.42
59,656,826.93
10,866,064.91 8,571,196.24
7,855,574.54
Design and Engineering, F10 0.25 0.25 0.25 0.25 0.25 0.25 0.25
0.2 0.25 0.25 0.25
Contractor's Fee, F11 0.05 0.05 0.05 0.05 0.05 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 0.1
0.1 0.1 0.1 0.1
Total (B)= 1+ Ʃf (10-12) 1.4 1.4 1.4 1.4 1.4 1.4 1.4
1.35 1.4 1.4 1.4
FIXED CAPITAL COST = PPC * B 20,128,486.6
4 46,450,353.79
21,876,067.36
11,806,131.59
363,644,791.80
3,825,323.25
469,080,263.98
80,536,716.36
15,212,490.87
11,999,674.73
10,997,804.35
TOTAL FIXED CAPITAL INVESTMENT: 1,076,825,080.45
109
APPENDIX VII
Material Safety Data Sheet
Acetone
Composition
Substance Formal Name: Propan-2-one
Substance Chemical
Formula:
(CH3)2CO
Synonyms: 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: 465°C (869°F)
Upper flammable limit in
air:
12.8 % (v/v)
110
Lower flammable limit in
air:
2.1 % (v/v)
Hazard Class: 3 (Flammable Liquid)
Phenol
Composition
Substance Chemical
Formula:
C6H6O
Synonyms: 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)
λmax: 270.75 nm
Dipole moment: 1.7 D
Hazards Identification
EU Classification: Toxic, Corrosive, Combustible
111
Flash Point: 79 °C (174 °F)
Auto-Ignition Temperature: 715°C
Explosive limits, vol% in
air:
1.36 – 10
Octanol/water partition
coefficient as log Pow:
1.46
Bisphenol – A
Composition
Substance Chemical
Formula:
C15H16O2 / (CH3)2C(C6H4OH)2
Synonyms: p,p'-isopropylidenebisphenol, 2,2-bis(4-
hydroxyphenyl)propane, 4,4'-(propane-2,2-
diyl)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/cm³
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
112