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



- 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.


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


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




General Details

Service


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


Heating

: reboiler

Process Condition


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


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




General Details

Service


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


Heating

: reboiler

Process Condition


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


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



EQUIPMENT NR. :

NAME :

S02

BPA Crystallizer


Diameter m 2.12

Height m 4.24


Process Conditions




Residence Time h 1





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



EQUIPMENT NR. :

NAME :

S03

BPA Crystallizer


Diameter m 2.12

Height m 4.24


Process Conditions




Residence Time h 1





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



General Data


- Cooler - Reboiler

- Condenser





- Vertical

Capacity [kW] : 345.13



˚C] : 500

Log Mean Temperature Diff. (LMTD) [˚C] : 8..93



Correction Factor LMTD : 1


Process Conditions

Medium

Mass Stream [kg/s]

Mass Stream

- Evaporize [kg/s]

- Condense [kg/s]



Temp. IN [˚C]

Temp. OUT [˚C]

Pressure [bar]

Material


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



Tube OD – 1.25 in


45



General Data


- Cooler - Reboiler

- Condenser





- Vertical

Capacity [kW] : 850.5737701



˚C] : 500

Log Mean Temperature Diff. (LMTD) [˚C] : 51.04



Correction Factor LMTD : 0.966


Process Conditions

Medium

Mass Stream [kg/s]

Mass Stream

- Evaporize [kg/s]

- Condense [kg/s]



Temp. IN [˚C]

Temp. OUT [˚C]

Pressure [bar]

Material


Cooling water

5

~

~

4.18

~

25

40.697

CS

BPA, phenol. Water

4.66

~

~

2.869867

~

138.5728

75

CS

Remarks:



Tube OD – 1.25 in


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:


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:


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:


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:


Q= nCpdT

= 19.04mol/s(1.2J/mol-K)(308-348)K

Q= -912.48 W

For Water:


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:




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:




Pressure = 3 bar


Output:


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



Pressure = 3 bar


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:


(%)

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:




Pressure = 3 bar


Output:


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



Pressure = 3 bar



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):


(%) 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




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



distillate:



88

Where

By iteration;




Tave(column temp) =

Calculating for the Vapour Pressure and Relative Volatility Using Antoine Equation


Vapour pressure Acetone:


Data:

Antoine Coefficient

Component A B C

Water 7.96681 1668.21 228

Acetone 7.11714 1210.595 229.664

89



Calculating for Rm:

Underwood Equation:

Solving for

By iteration:

Solving for R,



90


of R.K. Sinnott]



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


91




area:



92






93

P=560

mmHg

T=151OC

3rd

Distillation Column: Equipment Design



distillate:



94

Where

By iteration;




Tave(column temp) =

Calculating for the Vapour Pressure and Relative Volatility:

Using Antoine Equation


Vapour pressure Phenol:


Data:

Antoine Coefficient

Component A B C

Water 7.96681 1668.21 228

Phenol 7.13301 1516.79 174.954

95



Calculating for Rm:

Using Underwood Equation:

Solving for

By iteration:

Solving for R:

96




of R.K. Sinnott]



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


97




area:



98






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:






100

Outlet


(%)

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:




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


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:






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:




Pressure = 3 bar


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:






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:




Pressure = 3 bar


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



Enthalpy = 1,035.460 KW∙hr/hr

Water: Mass Flowrate = 8.39173 Kg/hr


Concentration = 994.70433


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




Drying Gas Requirement: 5 wt. gas/wt. evaporated

Evaporation Rate: 20 (Kg/hr)/m3

BPA:


Mass Component = 100%

Concentration = 1,111.0369909 g/L


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


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


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


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


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


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


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


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


EU Classification: Toxic, Corrosive, Combustible

Flash Point: 227 °C

Auto-Ignition Temperature: 510-570 °C

Octanol/water partition

coefficient as log Pow:

3.32

1bottles group production of bisphenol-a

Documents

bpa production

production of bpa

bpa exposure

bpa consumption

manufacturing bpa

world bpa market

boiling point of bpa

higher bpa levels