BISPHENOL-A FROM PHENOL AND ACETONE WITH AN ION

Transcription

Process Economics Reviews, PEP'82-1, September 1982
PROCESS
ECONOMICS
PROGRAM
SRI INTERNATIONAL
Menlo Park, California
94025
PEP Review No. 82-l-l
BISPHENOL-A FROM PHENOL AND ACETONE WITH AN
ION EXCHANGE RESIN CATALYST--UNION CARBIDE TECHNOLOGY
l
Yoshio Kosaka and Kenneth B. Sinclair
(September 1982)
ABSTRACT
Bisphenol-A is produced commercially by the acid catalyzed condensation of phenol and acetone under mild conditions of temperature and
pressure. This review evaluates the use of a cation exchange resin condensation catalyst according to Union Carbide technology. The process
avoids the handling of highly corrosive streams usual in traditional
HCl catalyeed processes and appears to be capable of producing very
high purity polycarbonate grade bisphenol-A simply.
Compared with the HCl catalyzed process, the resin catalyzed process has a 2-3c/lb lower net production cost for polycarbonate grade
product. Production costs for epoxy gr-adeproduct are the same for
both processes. The resin catalyzed process shows a higher return on
investment for both polycarbonate and epoxy grade products.
Introduction
The production of bisphenol-A from phenol and acetone was evaluated in detail in PEP Report 81, November 1972. The process evaluated
used an anhydrous hydrogen chloride catalyst and required extensive
facilities for recovery of the catalyst and for purification of the
bisphenol-A product. The presence of both HCl and water necessitated
extensive use of exotic materials in contact with process streams. The
bisphenol-A was purified by recrystallization from benzene. Product
purity as
99.5%.
An alternative catalyst system now widely employed is based on the
use of a cation exchange resin as the condensation catalyst. Such processes are believed to have been developed by Bayer, Dow, Rhone-Progil,
Shell, and Union Carbide. These processes have the distinct advantage
that the catalyst is noncorrosive.
In this review, Union Carbide's resin catalyzed process technology
is evaluated both to elucidate the characteristics of this catalyst
system and to update bisphenol-A production economics on the basis of
modern technology. Some information on reaction chemistry is included
in this review; Report 81 contains a more detailed discussion.
Industry Status
As shown in Table 1.1, world production capacity for bisphenol-A
in 1981 was about 800,000 metric tons per year, with virtually all of
it being in North America, Western Europe, and Japan.
Major end-uses of bisphenol-A are epoxy resins and polycarbonate
resins which, in the United States, account for 94% of total demand.
Until 1976, epoxy resins were the largest consumer. From 1977 to 1980,
consumptions for epoxies and polycarbonates were about equal, but the
higher growth rate projected for polycarbonates is expected to make
this the major end-use in future. Other uses of bisphenol-A include
polyarylates and specialty polyester resins, polysulfone engineering
resins, and certain types of flame retardants.
Table 1.1
BISPHENOL-A PRODUCTION CAPACITY
Number of
Producers
United States
Canada
Mexico
Western Europe
Japan*
Total
424
10
2
5
1
1'
7
North America
France
Federal Republic of Germany
The Netherlands
United Kingdom
Nameplate Capacity, l/1/81
(thousand metric tons/yr)
436
45
105
90
22
1
2
2
1
6
262
-2
15
85
783
*Capacity will expand to 130,000 tons per year by 1983.
Source: Chemical Economics Handbook, SRI International.
Physical Properties
Bisphenol-A is a white solid in which the molecules consist of two
phenol groups joined through the center carbon atom of a propane molecule.
Its physical properties are listed in Table 1.2.
Because a variety of synonyms are used for bisphenol-A in the
chemical and patent literature, its identity is not always apparent to
the casual reader. Some of these synonyms are:
l
p,p'-Isopropylidenediphenol
l
4,4'-Isopropylidenediphenol
l
2,2-(4,4'-Mhydroxydiphenyl)propane
3
Table 1.2
PHYSICAL PROPERTIES OF BISPHENOL-A
Appearance
White crystals, flake or prills
Odor
Mildly phenolic
Specific gravity at 25/25oC
1.195
Bulk density, flakes (lb/ft3)
36-42
Molecular weight
228.28
Freeting point (OC)
157.0
Boiling point at 4 mm Rg (OC)
220
Flash point, Cleveland open cup (OC)
207
Vapor pressure,(mn Hg)
179oc
0.2
193oc
1.0
21ooc
2.25
240.8OC
10.0
273OC
40.0
339oc
400.0
360.5OC
760.0
Heat of fusion (Btu/lb)
55.2
Solubility, approximate (gm/lOO gm
solvent at 250C)
Acetone
120
Benzene
0.2
Carbon tetrachloride
co.1
Ethyl ether
>llO
Heptane
co.1
Methanol
>120
Toluene
0.2
Water (250C; 83OC)
<O.l; 0.34
Toxicity: Low in acute oral toxicity and only mildly irritating to the
skin and eyes. Solutions greater than 1X, in some solvents,
are capable of marked irritation and injury both to the skin
and eyes. Dusts may produce irritation of the upper respiratory passages, with sneezing and a burning sensation in the
nose.
Sources:
354251 and trade literature.
4
l
2,2-Bis-(4-hydroxyphenyl)propane
l
2,2-Bis-(p-hydroxyphenyl)propane
l
2,2-Di-(4-hydroxyphenyl)propane
l
g,g-Bis-(4-hydroxyphenyl)propane
l
p,p'-Dihydroxydiphenyldimethylmethane
l
Diphenylolpropane (common in Europe)
Bisphenol-A is usually sold under two general specifications: an
epoxy grade containing as much as 5% impurities but normally being
about 99% purity, and a polymer grade with an assay greater than 99.5X,
normally about 99.8% purity or above. Typical specifications are shown
in Table 1.3. The impurities present are phenol, the 2,4*-bisphenol
isomer, trisphenol, and chromans (Dianin's compound) which are described below. The main reason for the very high purity requirement
for the polymer grade is the tendency for these impurites to form color
bodies under the alkaline reaction conditions used in polycarbonate
production. The APHA colors of the melt and of caustic solutions are
thus commonly used to specify polymer grade product. The quantities of
impurities are determined by gas chromatography (354047).
Table 1.3
TYPICAL BISPHENOL-A SPECIFICATIONS
Epoxy Grade
Polymer Grade
Melting point (OC)
155.0 min
156.5 min
APHA color, 5Og/70 ml MeOH
100 max
25 max
Phenol content (wt%)
0.2 max
0.1 max
Moisture (wt% as shipped)
0.15 max
0.15 max
Iron content (ppm)
1.5 max
1.0 max
Ash (wt%)
0.02 max
0.02 max
Source: 354251.
Chemistry
The bisphenol-A production process evaluated in this review uses a
sulfonated styrene-divinylbenzenecation exchange resin catalyst (e.g.,
Dowex@ 50-X-4) for the liquid phase condensation of phenol with acetone:
OH
2 x 94
phenol
+
CH,
-
ii
C -
CH,
228
Bisphenol-A
58
acetone
18
water
The resin catalyst is active only in its anhydrous (phenol swollen) form and the degree of conversion to bisphenol-A (BPA) is thus
limited by the water by-product. A large excess of phenol is used to
increase BPA yield per pass.
The reaction product is an equilibrium mixture of the 4,4'- and
2,4'-bisphenol isomers, and small quantities of impurities such as
trisphenols and isomers of Manin's compound as follows (354037).
(11
2-(2-Hydroxyphenyl)-2-(Chydroxy~enyl)propa~
or 2,4’-bisphenol-k
OH
Freazing point = 11 l°C
(2)
2,4-Bir(qcrdimethyll-hydroxybenzyl)phanol
or bisphenol-X:
C"3 - 7 - CH,
Fraeting point = 181OC
6H
Co’-klydroxyphenyl)-2,2,4-trimrthylchroman
(3)
or codimar or Dianin’s compound:
Freezing point = 158OC
OH
(4)
2-(4’.HydroxyphanylI-2,4,4,trimathylchroman
or isomeric codimar, an isomar of Dianin’s compound:
0
\I
OH
0
Fraazing point - 133OC
0
2
\
I
C"3
CH3
CH3
The first two compounds result from a substitution reaction taking
place with hydrogen in the ortho position rather than in the
para
position on the phenol molecule. The Dianin's compound isomers are
formed by reaction of phenol with trace amounts of mesityl oxide,
(CH&C=CH-
(C=O)-CH3,
present in the reaction mixture.
7
In addition to these by-products, higher-condensation products,
tarry resins, and very small proportions of highly colored compounds
characterized by intense absorption of ultraviolet light, are also
present in the
reactor product (354134, 354218).
Since the 4,4'- and 2,4'-bisphenol-A isomers are in equilibrium in
&he reaction product, the 2,4'-isomer can be recycled continuously to
the reactor feed to ensure 100% yield of the 4,4'-isomer. The 2,4'isomer is thus not in itself an objectionable component in process
streams. Similarly, some
of the polyphenols which are not high colored
can be tolerated in process streams and in epoxy grade BPA product.
The highly colored chromophoric impurities, however, must be removed
from the process irrespective of whether epoxy grade or polymer grade
BPA is being produced. This is achieved by absorbing these impurities
in a bed of sulfonated styrene-divinylbenzenecation exchange resin.
Once loaded, the absorption bed is regenerated by washing with wet
phenol (20% water) (354218, 354221).
In the production of high purity polymer grade BPA, higher polyphenols and tars must be removed to prevent buildup in recycle streams.
This is achieved by cleavage of the polyphenols at elevated temperature
and in the presence of an alkali catalyst to form phenol and paraisopropenyl phenol (PIPH). The PIPH readily dimerize8 at room temperature so that the cleavage product contains both PIPH monomer and dimer
(354251). The phenol, PIPH, and dimer are separated from heavy noncleavable tars and the alkali catalyst by distilling these products
overhead simultaneously with the cleavage reaction:
c, EH
PIPH
2
CH,
-
k
-
CH,
CH3
PIPH dimer
Under acidic conditions the dimer
form and,
in addition,
quantitative
yields
readily
the monomer reacts with
of
reverts
to
phenol
the monomeric
to give
nearly
BPA:
6 + 6 - o”~rQo”
3
C -
CH,
!H 2
phenol
BPA
PIPH
In the process evaluated here, this rearrangement occurs simul-
-
taneously with the removal of color bodies, the cation exchange resin
in the color absorption bed acting as the acid catalyst. This
rearrangement is an essential step after cleavage since PIPH Is itself
a major source of color bodies in BPA products. In the presence of
air, PIPH is readily oxidized to a peroxide which in turn further
reacts to form colored polymeric compounds (354222).
Another advantage of this rearrangement step is that it reduces
the equilibrium concentrations of 2,4’-isomer and polyphenols in the
main condensation rea’ctorproduct (354041). Under anhydrous condf-
-
tions, the cation exchange resin acts to rearrange the 2,4’-bisphenol-.4
to the desired 4,4’-isomer. Since both water and acetone are essentially absent in recycle streams, conditions favor this isomerization
reaction and the concentration of the 2,4’-isomer in the condensation
a-
reactor feed is substantially lower. Surprisingly, this also reduces
the equilibrium concentration of 2,4‘-isomer in the condensation reaction product stream by about half. Normally the steady state concentration of by-products obtained in the reactor product stream when
0
recycling all by-products without rearrangement is about 40 wt% on a
9
phenol-free basis. When a rearrangement step is included in the recycle circuit, this equilibrium by-product concentration falls to about
20 wt%.
The net
result is a marked reduction in by-product concentra-
tion throughout the system, improving the efficiency of bisphenol-A
separation and thus yielding a higher purity product.
The recovery of high purity BPA from the reaction mixture is
achieved by crystallization. BPA is relatively unstable at elevated
temperatures and should preferably be processed at less than 15OoC.
Low temperature crystallixation can be achieved by recovering a high
purity 1:l molar phenol/BPA crystal adduct which can subsequently be
split into its two components. Bisphenol-A and phenol form a peritectic and eutectic system, as shown in Figure 1.1. The equimolar
adduct contains about 30 wt% phenol and has an incongruent freezing
point (354251). Crystallieation from mixtures containing S-58% BPA
yields the equimolar adduct, while crystallization from more concentrated mixtures yields BPA crystals. Because the reaction impurities
are all soluble in phenol at temperatures between 37 and 9S°C, high
purity adduct crystals can be obtained, given adequate crystal washing.
10
Figure 1.1
MELTING
POINT
DIAGRAM
PHENOL-BISPHENOL-A
FOR THE
SYSTEM
160
150
140
130
120
ou
110
Adduct +
bisphenol -A
cfystals
0
10
20
30
WEIGHT
40
50
60
70
I
I
80
90
loo
PERCENT BISPHENOL-A
Source: 354251.
11
PEP Review
No.
82-l-l
Process Description
This evaluation is based on a unit designed to produce 120 million
lb/yr of bisphenol-A at an on-stream factor of 0.9 (7,884 hr/yr). The
product is a high purity BPA grade suitable for polymer production and
containing 99.7 wt% BPA. The unit would also be suitable for producing
a lower purity epoxy grade BPA with some savings in operating costs.
Key process conditions and design assumptions used as a basis for
design are summarized in Table 1.4. The process flow scheme is shown
in Figure 1.2 (foldout at end of this paper). Material flows of the
numbered streams In this flow diagram are given in Table 1.5 and major
process equipment is listed in Table 1.6.
Referring to Figure 1.2, phenol and acetone in a molar ratio of
1O:l are heated to the reaction temperature in preheater E-101 and sent
continuously to BPA condensation reactors R-lOlA,B, which are jacketed
vessels packed with ion exchange resin and which operate in parallel.
Phenol and acetone are reacted at 167Op (7SOc) and marginally superatmospheric pressure to produce BPA.
The residence time is 1 hour and
the conversion to BPA, based on acetone, is about 50%.
The reaction
temperature is maintained by circulating tempered cooling water through
the jacket.
The effluent stream from the reactor is pumped to concentrator
E-103, in which unreacted acetone, water, and some phenol are removed
at 284O~ (14OOC) and 200 mm Hg.
The distillate from the concentrator
is sent to dehydration column C-101.
The concentrator bottoms, now consisting of BPA, phenol and reaction by-products, are pumped to crystallizer V-102, where they are
cooled to llS°F (46OC) to produce a slurry of 1:l molar phenol/BPA
adduct crystals in mother liquor.
The slurry is sent to the first batch centrifuges, M-lOlA,B, and
the mother liquor is separated from the crystals. The separated mother
liquor is collected in buffer tank T-104. The crystals are washed with
12
Table 1.4
BISPHENOL-A FROM PHENOL AND ACETONE
WITH AN ION EXCHANGE RESIN CATALYST
DESIGN BASES AND ASSUMPTIONS
BPA synthesis reaction
Reactor type
Jacketed column packed with ion
exchange resin
Reaction temperature
75oc (1670F)
Reaction pressure
Atmospheric
Residence time
1 hr
Phenol/acetone feed mol ratio
lO.O:l
Conversions per pass
Phenol
10.1%
50.5%
Ace tone
Selectivity to 4,4*-bisphenol-A
80.5%
Cleavage reaction*
Reactor type
Distillation column with 5
valve trays
160°c (320OF)
Reaction pressure
200-250 mm Hg
Residence timet
100 minutes
NaOH/BPAs feed weight ratio
0.0038:1
Tar/product weight ratio
0.065:1
Tar/cleaved BPA's weight ratio
0.15:1
Weight ratio of BPA cleaved/isomer
cleaved
1:l
Conversion per pass on total BPA's
80%
Selectivity on total BPA's
To phenol
To PIPH
To tar
100%
74.4%
25.6%
13
PEP
Review No. 82-l-l
Table 1.4 (Concluded)
WITH AN ION EXCHANGE RESIN CATALYST
DESIGN BASES AND ASSUMPTIONS
Rearrangement and decolorization
Reactor type
Jacketed column packed with ion
exchange resin
70°C (158OF)
Reaction pressure
Atmospheric
Residence time
20 minutes
Phenol/PIPH feed mol ratio
56:l
Conversion per pass
Phenol
PIPH
1.8%
100%
Selectivity to 4,4'-BPA
100%
Regeneration of rearrangement reactor
Temperature
70°C (158OF)
Pressure
Atmospheric
Solvent for desorption
Phenol (80 wt%)/water (20 wt%)
mixture
Elution rate
1 reactor volume/hr
Operating rates
Rearrangement and decolorization
Desorption
24 hr/day
12 hr/day
*Including BPA and BPA isomer.
*Bottoms flow basis.
14
phenol filtrate from the second centrifuge, M-102. The wash liquor is
combined with the separated mother liquor.
The crystals are discharged to V-103, where they are reslurried in
recycle phenol from phenol stripper E-106 and fresh phenol feed from
storage. The slurry of crystals in phenol is pumped to the second
centrifuge, M-102. The crystals are centrifuged, washed with pure
phenol from the phenol stripper and sent to melter V-104. The separated phenol is collected in buffer tank T-103 to be used as wash
liquor for the first centrifuge.
The phenol/BPA adduce crystals are melted in V-104 at 2660~
(13O'C) to give a solution of BPA in pure phenol. This is pumped to
phenol stripper E-106, in which phenol is evaporated from the product
at 392'F (2OOOC) and 5 mm Hg.
The evaporated phenol is recycled to
adduct reslurry vessel V-103 and the second centrifuge, M-102.
The
molten product from the phenol stripper is cooled and flaked for packing.
The distillate separated from the condensation reactor effluent in
concentrator E-103 is dehydrated in dehydration column C-101 by introducing a dry acetone vapor stream from acetone column C-102. An essentially anhydrous mixture of phenol and acetone is obtained at the
bottom of column C-101. This mixture is cooled and returned to the
reactor feed tank.
The distillate from the dehydration column, consisting of acetone
and water with only traces of phenol, enters the acetone column, in
which acetone and water are separated-water leaving the column as bottoms and dry acetone leaving the column as distillate. The water is
sent to waste treatment for removal of trace quantities of phenol.
A portion of the dry acetone is recycled to the reactor feed tank.
The remainder is vaporieed and returned to the bottom of the dehydration column as a drying agent.
A portion of the recycle mixture of mother liquor and wash liquor
from the crystal separation step is sent to cleavage column C-103, in
15
PEP Review
No.
82-l-l
which both BPA and its 2,4'-isomer contained in the mixture are cleaved
to p-isopropenyl phenol (PIPH) and phenol at 320O~ (16OOC) and 200-250
mm Hg, in the presence of an alkali catalyst. Most of the phenol and
PIPH formed are simultaneously distilled from the reaction mixture.
The remaining phenol and PIPH, and unreacted BPA and its isomer are
separated from the residual tars in BPA evaporator E-118, at 4500F
(2320C) and 15 mm Hg.
The distillates from the cleavage column and the
evaporator are combined with
the
remainder of the recycle mixture and
sent to rearrangement reactors R-102A,B,C. These are jacketed vessels
packed with cation exchange resin and operating slightly above atmospheric pressure. TWO reactors are on-line while the third is being
regenerated.
The rearrangement between the cleavage products to form the
desired BPA takes place at 158OF (7OOC). The effluent stream from the
reactor is recycled directly to condensation reactor feed tank T-101.
A small amount of highly colored compounds, which are by-products
of bisphenol-A reaction and are present in the mother liquor recycle
stream, are adsorbed by the ion exchange resin in the rearrangement
reactors. These color bodies are desorbed from ion exchange resin by a
periodic wash with phenol/water mixture containing 20 wt% water.
phenol/water mixture is then separated
The
from the color bodies by evapora-
tion, and is reused.
16
Table 1.5
BISPHENOL-A
PROM PHENOLAND ACETONEWITH AN ION EXCHANGERESIN CATALYST
Plant Capacity: 120 Millionlb/yr
at
(7.884 hr/yr)
0.9 Stream
Factor
Mol
Stream
Plowe (lb/hr)
weoxLooooooo
94.1 13,368
- 139,633 123,388 97,814 27,773 4,710,483 91,496 2,848
Phenol
--4,202
38.1
- 4,381
8,383 4,247
Acetone
-Trace
Trace
1,341 Trace 1,341
18.0
-198
Water
--8,431
228.3
10,046 23,738 23,738
BPA
30
12,370
228.3
--9,041 12.370 12,370
BPA isomer
-- 21,643 21.643
-I
BPA/phenoladduct 322.4
---Tar
--pIsopropenylpheno1134.2
40.0
Sodiumhydroxide
-
-
I
-
---
13,368 4,381 167.303 167,304
1,632
142
73
1,726
Totallb/hr
lb mol/he
Mol
Wt
133,942
Stream
(10)
(11)
(12)
(13)
1,198
33,316 4,710,483 133,942 24,323
30,038 1,131
98
433
Plowa (lb/hr)
(14)
(13)
(16)
(17)
(18)
(19)
15 4.903
94.1 110,720 12,921 20.013 2,848 22,072 9,166
13 9,131
Phenol
--------38.1
Acetone
Trace
---------18.0
Water
-- 13,327 13,327
13,173
228.3
8,431
-BPA
30
-30
-30
30
-BPA Isomer
228.3 12,339
-30
-- 21,643 21,643
----BPAiphenoladduct 322.4
--------Tar
--_
---134.2
p-I~opropenylphenol
40.0 ---------Sodim hydroxide
131,490 12,921 42,690 24,323 22,072 24,323 13,372 9,131 13,220 4,903
Total lb/hr
67
97
67
52
137
98
233
163
lb mol/hr
1,268
280
%l
Wt
(20)
(21)
(22)
StreamFlows (lb/hr)
(23) (24) (23)
(26)
(27)
(28)
-- 43,939 66.781
Phenol
94.1 4,246
- 27,773
--- 2,104 40,863
Acetone
38.1
- 42,967 2,099 42,967
11
1.390
137
216 1,373
203 Trace Trace
Water
18.0
-we
--BPA
228.3
3,346 5,083
---4,900 7,440
BPA isomer
228.3
---BPA/phenoladduct 322.4
-------Tar
----134.2
p-18opropenylphenol
-Sodiumhydroxide
40.0 ---- 31
-- Totallb/hr
lb mol/hr
4,246 44,337 30,029 43.183 1,373 2,113 41.068 32,185 79.306
828
732
76
37
303
43
340
713
765
(30)
(31)
StreamFlowa (lb/hr)
(32) (33)
(34)
(33)
(29)
-31
---
---31
62
2
(36)*
94.1 44.792 1.866 1,866
- 113.438
Phenol
--38.1
Acetone
18.0
31
31
Water
47
5,132
228.3
47
SPA
9,041
228.3
1.6OL 1,601
BPA isomer
---BPAjpheooladduct 322.4
-989
989
Tar
-2,887
p-Isopropenylphenol
134.2 2,618
269
269
40.0
31
Sodiomhydroxide
-- 31
3,783 1,020 130.329 130,532 21,000
Totallb/hr
1,291
29
lb wl/hr
1,269
412
111,414 16.800
-31 4.200
10.046
-9.041
----me
*Operation12 hr/day.
17
TABLE
1.6
BISPHENOL-A
ION
EXCHANGE
MAJOR
FROM PHENOL
AND
RESIN
CATALYST
ACETONE
WITH
EQUIPMENT
CAPACITY:
120
MILLION
LB (54,000
POLYMER
GRADE
BISPHENOL-A
AT 0.90
STREAM
FACTOR
METRIC
TONS)/YR
E;;;;::“’
--------_
NAME
--__--_-_____-_-_--_--
SIZE
REMARKS
-____--___--_-----_------------
MATERIAL
OF CONSTRUCTION
_--___--__---_-----_------
REACTORS
R-18lA.B
EPA
I-l#ZA-C
REARRAWCPWEWT
NEAT
REACTOR
REACTOR
EXCHANCERS
DlAr
HEIGHT:
9.0
39
FT
FT
EA
DIAI
NElCNT:
5;:
;;
EA
REACTOR
E-I#2
CONCENTRATOR
PREHEATER
E-113
CONCENTRATOR
E-I#4
E-103
E- 106
CRYSTALLIZER
E-116
PHENOL
STRIPPER
E-187
PHENOL
CONDENSER
E-106
C-ill
CONDENSER
COOLER
18.9
439
6.4
CARBON
STL
316
CARBON
STL
316
SS
316
ss
11.3
CARBON
STL
316
ss
13.6
CARBON
STL
316
ss
316
ss
3.6
241
3.3
CARBON
STL
316
ss
1.6
CARBON
STL
316
ss
E-109
C-181
CONDENSER
5.771
20.9
CARBON
STL
CARSON
E-Ill
C-ill
REBOILER
2.7611
13.2
CARBON
STL
316
E-Ill
ACETONE
CARBON
STL
CARBON
E-112
C-Ill
SOTTON
CAR6ON
STL
316
E-113
C-112
CONDENSER
9.661
36.5
CARBON
STL
CARllON
STL
E-114
C-II2
RESOILER
3.661
36.5
CARBON
STL
CARBON
STL
E-115
C-l#S
PREHEATER
361
5.1
CARBON
STL
316
E-116
t-1#3
CONDENSER
771
12.6
CARBON
ST1
316
so
E-117
C-II3
REBOILER
12.9
CARBON
STL
316
ss
E-115
SPA
EVAPORATOR
316
ss
E-119
E-116
1.3
CARBON
STL
316
ss
E-129
REARRANPEWENT
1.2
CARSON
STL
316
ss
CARBON
STL
316
SS
316
ss
SE
VAPORIZER
63#
COOLER
E-122
E-122
PNENOL/NZ#
E-123
E-122
E-I24A.I
TEMPERED
E-125
T-I#1
E-126
E-127
1.1
261
91
COOLER
PREHEATER
21#
171
VAPORIZER
CONDENSER
WATER
3
2.611
COIIDENSER
E-121
9.4
26P
2
431
7.52
9.6
1.2#8
COOLER
6.141
EA
5#
9.5
EA
EXCHANGE
RESIN
PACKING
17
FT
OF
ION
EXCNAN6E
RESIN
PACKING
STL
ss
ss
CARBON
STL
316
CARBON
STL
CARION
STL
CARBON
STL
CARlON
STL
T-112
BASE
HEATER
51
#.I4
CARION
STL
CARBON
STL
T-I#3
5ASE
NEATER
51
#.#4
CARBON
STL
CARlON
STL
STL
E-120
T-1#4
5ASE
NEATER
58
1.14
CARBON
STL
CAROON
E-129
T-185
9ASE
NEATER
51
1.14
CARBON
STL
CARSON
STL
E-138
T-I#6
6ASE
NEATER
!w
#.#I
CARBON
STL
CAR5ON
STL
E-131
T-I#7
5ASE
NEATER
61
1.84
CARBON
STL
CARBON
STL
E-132
T-151
BASE
NEATER
5#
l .14
CARBON
STL
CARBON
STL
E-133
T-153
BASE
HEATER
68
#.#I
CARION
STL
CARBON
STL
CAR5ON
STL
N-ill
1ON
STL
NEATER
lURltACES
OF
ss
BASE
1.14
FT
ss
1.26#
1.99n
27
TUBES
m----m----
9.1##
43#
PREHEATER
CLAD
RESINS
SNELL
__----__--
1
761
CLAD
316 ss
NEAT
LOAD
tNl4 BTU/HI)
-----------
95
PREHEATER
ss
RESINS
PACKlNfi:
AREA
(SO
FT)
-------
E-181
316
PACKING:
NEAT
LOAD
tWM ITUINR)
--------m-v
DOUTNERH
HEATER
16.5
18
PEP Review
No. 82-l-l
TABLE
1.6
(CONTINUED)
BISPHENOL-A
ION
EXCHANGE
MAJOR
FROM PHENOL
AND
RESIN
CATALYST
ACETONE
WITH
EPUIPNENT
CAPACITY:
120 MILLION
LB (54.110
POLYMER
GRADE
BISPHENOL-A
AT 1.91
STREAM
FACTOR
METRIC
TONSFIVR
EWl:W::NT
MATERIAL
OF
REMARKS
________--____--___------------
CONSTRUCTION
TANKS
T-101
REACTOR
T-102
SISPNENOL
T-IS3
NO.1
T-104
FEED
TANK
304
ss
EPUIPPED
WITH
HEATING
COIL
STORAGE
2.#U#
304
ss
EOUIPPED
WITH
NEATINC
COIL
BUFFER
TANK
2,511
304
ss
EPUIPPED
WITH
HEATING
COIL
NO.2
5UFFER
TANK
lO.NB8
314
ss
EQUIPPED
WITH
HEATIN
COIL
T-105
NO.3
SUFFER
TANK
lO.BN
314
ss
EOUIPPED
WITH
HEATING
COIL
T-106
NO.1
PHENOL/N20
TANK
3#.###
314
ss
EDUIPPED
WITH
HEATING
COIL
T-107
NO.2
PHENOL/N20
TANK
a#,
SP4
SE
EQUIPPED
UITN
HEATING
COIL
T-151
PHENOL
314
ss
EOUIPPED
WITH
HEATING
COIL
T-152
ACETONE
T-153
ALKALI
EPUIPPED
UITN‘NEATINC
T-154
TEMPERED
A
2#,###
STORAGE
0n0
16#.##~
STORAGE
TANK
WATER
TANK
VESSELS
O#.##B
CARBON
STL
3.631
RUBBER
LND
66 .##I
CARBON
STL
VOLUME
(CAL1
-------mm-mm
.
v-101
CONCENTRATOR
v-102
CRYSTALLIZER
v-103
ADDUCT
V-104
MELTER
v-105
PHENOL
V-106
C-101
REFLUX
DRUM
2.210
CARSON
STL
V-107
C-W2
REFLUX
DRUM
4.3##
CAROON
STL
V-108
C-113
REFLUX
DRUM
1.111
316
SS
CLAD
v-109
E-116
RECEIVER
211
316
SS
CLAD
V-l
PWENOLINLO
RECEIVER
IOU
316
SS
v-111
JACKET
FOR
V-113
v-112
JACKET
FOR
V-114
10
RECEIVER
TANK
RECEIVER
DEHYDRATION
c-102
ACETONE
c-103
CLEAVAGE
SS
CLAD
316
ss
CLAD
2.001
316
SS
CLAD
AGITATED
AND
JACKETED.
O.#N
316
SO
CLAD
AGITATED
AND
JACKETED.
316
SS
CLAD
TRAYS.
24
b.##H
11,000
DIAMETER
(FT)
_-------
C-101
316
2##
COLUMNS
MISCELLANEOUS
701
lO.I##
RESLURRV
COIL
COLUMN
COLUMN
COLUMN
NE IENT
(FT)
______
6.H
2#
6.5
1#5
6.0
21
CLAD
CAROON
STL
CARSON
STL
TRAYS/
PACKING
__-__-----
SNELL
------mm_______
316
SE
CARBON
316
CLAD
STL
SS
316
SS
CARBON
CLAD
316
SS
6
STL
VALVE
47
VALVE
5
VALVE
TRAYS.
IN
24
TRAVS.
24
IN
IN
SPACING
SPACING
SPACING
EOUIPMENT
M-I#lA,B
NO.1
CENTRIFUGE
H-112
NO.2
CENTRlFUfE
W-IBSA-C
FLAYER
n-104
E-183
VACUUM
PUMP
CARBON
STL
58
HP
M-186
E-l@6
VACUUM
PUMP
CAROON
STL
S#
HP
M-106
C-In3
VACUUM
PUMP
CARBON
STL
6#
HP
N-107
E-116
VACUUM
PUMP
CARBON
STL
21
HP
N-106
E-122
VACUUM
PUMP
CAROON
STL
On
HP
EA
EA
316
ES
40
IN
BASKET.
OBNP
316
15
32
IN
OASKET,
SUNP
3#4
OS
125
So
FT
SINGLE
DRUM
FLAKER
PUMPS
100
SECTION:
65.
INCLUDING
34
OPEMTINC.
31 SPARES:
766
OPERATING
BNP
19
PEP Review
No. 82-l-l
Process Discussion
The ion exchange resin catalyst used for both condensation and
rearrangement is a sulfonated styrene-divinylbenzenecation exchange
resin. Specific grades cited in patent references are:
Amberlite ICE-100
Rohm and Haas Co.
Dowex so-x-4
Dow Chemical Co.
Permutit QH
Permutit-Boby Co.
Chempro C-20
Chemical Process Co.
The resins used today are probably developments of these original
grades and they may therefore be sold under different grade designations. Although the resin is theoretically not consllmedin the reactions, some degradation or gradual loss of activity can be expected.
Such deactivation may be partially reversible by suitable acid treatment but it is likely that periodic replacement of the resin beds will
be required. The frequency of replacement is not known but the average
replacement rate is claimed to be less than 2 lb/metric ton of BPA product (354251). For this evaluation we have assumed a nominal replacement rate of 1.5 lblmetric ton at a resin value of $3/lb, or 0.2c/lb
BPA.
Although the process as designed is expected to yield polymer
grade product, much depends on the efficiency of crystal washing in the
adduct separation step and on the efficiency of separation of tars from
process eitreanus
h the cleavage system. The efficiency of the crystal
separation step could be improved vlth a more complex wash system or
with an additional reslurry/centrifuge step. The efficiency of tar
eeparation could be improved by operating with a lower tar content in
the evaporator bottoms.stream (stream 33.). The direct result of this
mu&d
be an increase In pheaol usage.
If the total flow rate of this
rtream were increased by about 50x,,specific phenol consumption would
r&m
ft- 0.878 lb/lb BPA to 0.91 lb/lb (see reference 354252).
20
For the production of less pure, epoxy grade BPA, the unit could
be operated with the cleavage system on bypass. This would result in
savings of about 5 gal/lb BPA of cooling water circulation and 1.4
lb/lb BPA of steam. The net savings in utilities costs would be lc/lb
BPA.
Raw materials efficiencies would be virtually unaffected since
the condensation reactor effluent is an equilibrium mixture. Byproducts removed with the BPA product would be replaced by increased
by-product production in the reactor. Phenol loss in the tars blowdown
stream would be unaltered.
Process Economics
Investment costs have been estimated at a PEP Cost Index of 425
(1958 - loo), corresponding approximately to 2nd quarter 1982 U.S. Gulf
Coast conditions. Table 1.7 shows the investment cost required for a
unit to produce 120 million lb/yr of high purity bisphenol-A.
Table 1.8 shows the production cost estimate for this plant based
on a 0.9 stream factor (7,884 hr/yr). The indicated raw material efficiencies are 93.9% of theoretical on phenol and 88.3% on acetone. Raw
materials are valued at approximate May 1982 list prices. Raw materials costs alone account for 61% of product value and fixed costs for
30%.
In this table, credit is taken for the by-product tar stream at a
nominal fuel value of 11,000 Btu/lb, on the assumption that it is incinerated in the utility boilers or Dowtherm@ heating system. The
indicated net production cost of 60&b
and product value of 70c/lb
compare with current list prices of 66c/lb for polymer grade
bisphenol-A and 62c/lb for epoxy grade.
The variation of BPA production cost with plant capacity and with
plant operating level is shown in Figure 1.3.
21
TABLE
1.7
BISPHENOL-A
ION EXCHANGE
TOTAL
FROM PHENOL AND
RESIN
CATALYST
CAPITAL
WITH
INVESTMENT
120 MILLION
LB (54,000
METRIC
POLYMER
GRADE BISPHENOL-A
AT 0.90
STREAM
FACTOR
CAPACITY:
PEP COST
ACETONE
INDEX:
TONS)/YR
425
COST
-----------BATTERY
LIMITS
EQUIPMENT,
REACTORS
COLUMNS
VESSELS
+ TANKS
EXCHANGERS
FURNACES
MISCELLANEOUS
EQUIPMENT
PUMPS
F.O.B.
S
1,717,200
346,600
1.191,800
3;641,400
225.200
896;i00
609,600
----------9
8,629.000
TOTAL
BATTERY
LIMITS
CONTINGENCY,
8ATTERY
EOUIPMENT
25.0
LIMITS
5,885,000
----------S 29,425,000
PERCENT
INVESTMENT
S
2,010,800
2,324,000
199,800
657,700
1.377.000
----------S
6.569.000
+ STORAGE
GENERAL
SERVICE
WASTE TREATMENT
OFF-SITES
TOTAL
25.0
0.75
0.65
0.68
0.58
0.96
0.82
0.50
0.68
0.90
0.77
0.62
0.55
0.59
0.90
0.86
0.79
6,022,000
1.5059000
s--m------8 14,096,000
PERCENT
39524,000
---s---w--S 17.620.000
0.79
0.70
8 47.0459000
0.72
0.62
INVESTMENT
FIXED
0.74
0.53
0.46
0.75
0.79
0.49
0.44
FACILITIES
TOTAL
CONTINGENCY,
0.79
0.68
0.57
0.84
0.79
0.63
0.59
8 23,540,000
INSTALLED
OFF-SITES,
INSTALLED
COOLING
TOWER
STEAM GENERATION
INERT
6AS
TANKAGE
WAREHOUSE
FACILITIES
UTILITIES
CAPACITY
EXPONENT
---m-----DOWN
UP
---s
-s--
CAPITAL
22
PEP Review
No.
82-l-l
TABLE
1.8
BISPHENOL-A
ION EXCHANGE
PRODUCTION
PEP
VARIABLE
COST
FROM PHENOL AND
RESIN
CATALYST
ACETONE
WITH
COSTS
INDEX:
425
COSTS
UNIT
-------------
CONSUMPTION/LB
--------------
COST
C/LB
------
RAW MATERIALS
PHENOL
ACETONE
CAUSTIC
CATALYST
GROSS
SODA (50
MAKEUP
X1
38
32
6.75
3.00
C/
C/
C/
S/
LB
LB
LB
LB
0.878
0.288
0.0041
0.00068
LB
LB
LB
LB
33.36
9.22
0.03
0.20
-----42.81
4.6
Cl
LB
-0.067
LB
-0.31
RAW MATERIALS
BY-PRODUCTS
TAR
AT
FUEL
VALUE
UNIT
---------s------
COST
CONSUMPTION/LB
--------------
CONSUMPTION/KG
--------------
UTILITIES
COOLING
WATER
STEAM
ELECTRICITY
NATURAL
GAS
INERT
GAS,
LO P
TOTAL
5.4
7.00
3.6
4.17
73
C/l,000
GAL
S/l,000
LB
C/KWH
S/MM BTU
C/1,000
SCF
53
6.76
0.075
1.549
0.657
GAL
LB
KWH
BTU
SCF
442
6.76
0.166
860
38.8
LITERS
KG
KWH
KCAL
LITERS
0.29
4.73
0.27
0.65
0.05
-e---m
5.99
UTILITIES
23
PEP Review
No.
82-l-l
1.8
TABLE
(CONTINUED)
BISPHENOL-A
ION EXCHANGE
PRODUCTION
PEP
FROM PHENOL
AND
RESIN
CATALYST
ACETONE
WITH
COSTS
COST
INDEX:
425
(1)
CAPACITY
(MILLION
INVESTMENT
BATTERY
OFF-SITES
(S
LB/YR)
------
TOTAL
FIXED
SCALING
19.7
10.9
----mm
30.6
CAPITAL
EXPONENTS
COSTS
COSTS
(3)
OPERATING
LABOR,
7/SHIFT,
S17.50/HR
MAINTENANCE
LABOR,
2 PCT/YR
OF BL INV
CONTROL
LAB LABOR,
20 PCT OF OP LABOR
LABOR
COSTS
MAINTENANCE
OPERATING
TOTAL
MATERIALS,
2 PCT/YR
OF BL INV
SUPPLIES,
10 PCT OF OP LABOR
DIRECT
COSTS
PLANT
OVERHEAD,
80 PCT OF LABOR COSTS
TAXES
AND INSURANCE,
2 PCT/YR
OF TFC
DEPRECIATION,
10 PCT/YR
OF TFC
PLANT
G+A,
NET
ROI
GATE
SALES,
COST
RESEARCH.
PRODUCTION
BEFORE
PRODUCT
240
------
29.4
17.6
-----47.0
47.3
30.4
-----77.7
0.62
0.72
(C/LB)
RAW MATERIALS
BY-PRODUCTS
UTILITIES
VARIABLE
120
------
MILLION)
LIMITS
PRODUCTION
(2)
60
TAXES,
42.81
-0.31
5.99
-----48.49
42.81
-0.31
5.99
-----48.49
1.79
0.66
0.36
-----2.81
0.89
0.49
0.18
-s---1.56
0.45
0.39
0.09
-----0.93
0.66
0.18
0.49
0.09
0.39
0.04
52.14
50.63
49.85
2.24
1.02
5.10
-----60.50
1.25
0.78
3.92
-mm--56.58
0.74
0.65
3.24
-----54s.48
(3)
5 PCT
OF
SALES
3.30
-----63.80
3.30
-s---59.88
3.30
-e-e-57.78
PCT/YR
OF
TFC
12.75
-----76.55
9.79
m----69.67
8.09
-----65.87
COST
25
42.81
-0.31
5.99
---w-48.49
VALUE
---------_---------------------------------------------------(1)
(2)
(3)
OF POLYMER
GRADE BISPHENOL-A
BASE CASE
FOR BASE CASE ONLY:
MAY BE
DIFFERENT
FOR
OTHER
CAPACITIES.
24
PEP Review
No.
82-l-l
Figure 1.3
BISPHENOL-A
FROM PHENOL AND ACETONE
WITH AN ION
Effect of Operating
EXCHANGE
RESIN CATALYST
Level and Plant Capacity
I
I
I
I
on Production Cost
PEP Cod Index: 425
l
0.5
I
I
I
I
0.6
0.7
0.8
0.9
OPERATING
1.0
LEVEL, fmction of design capacity
25
PEP Review
No.
82-l-l
Comparison with-the HC1 Catalyzed Process
Three significant differences are immediately apparent in comparing this evaluation with our 1972 evaluation of the HCl catalyzed process. Firstly, the 1972 evaluation is based on a phenol-to-acetone
reactor feed ratio of 4: 1 and an acetone conversion of 99% per pass,
compared with the 1O:l ratio a.nd50.5% conversion used in this evaluation. Thus the reactor feed flowrate in this evaluation is 4.4 times
greater per pound of BPA than in the earlier evaluation and utilities
consumptions (particularly that of steam) are correspondingly higher.
The phenol-to-acetone feed ratio affects the overall yield of BPA and
the formation of by-products, Including color forming compounds. Low
phenol-to-acetone ratios lead to low BPA yields and high by-product
formation. Industry reviewers of the 1972 evaluation indicated that a
feed ratio of 8:l might be necessary in order to achieve the required
EPA yields and low color body formation. We believe that an 8:l ratio
would be used in designing an HCl catalyzed process to meet 1982 raw
material costs and product color standards.
The second significant difference between the two evaluations
appears in the final BPA crystal recovery operation. The present evaluation uses
a two stage countercurrent centrifuggtion and washing
scheme for crystal recovery, whereas the 1972 evaluation uses a single
ccntrifugation st8ge. It is certain that the product color standard
achievable with the 1972 scheme is significantly poorer than that
achievable with the present scheme, particularly in combination with
the 10-r phenol to acetone reactor feed ratio. The product purity and
color standards achievable with the single centrifugation stage are
probably comparable with those achievable in the resin catalyzed process operating with the cleavage system on bypass, i.e., producing BPA
of higher purity than is uslrallyrequired for epoxy resin applications
but
not sufficiently high to meet current polycarbonate grade specifl-
C8tiOU8.
We believe th8t 8n HCl catalyxed process designed to produce
pdyccrrbonate grad8 BPA of a standard equivalent to that produced by
th8 resin catalyzed process would require significantly improved solvent purification facilities and a second crystal washing and centrifugation stage.
26
The third significant difference between the two evaluatfons
appears in the environmental aspects of the two processes. The resin
catalyeed process is essentially nonpolluting. The scheme used to
separate reaction water from the process gives an effluent with a low
phenol content; it is suitable for feeding directly to biological treatment. The HCl catalyzed process as evaluated in 1972 would not meet
today’s environmental standards without significantly higher investment
in effluent treatment to control phenol release in aqueous streams and
benzene vapors in operating areas.
To compare the two processes on a common basis, we have updated
the 1972 investment and operating cost estimates as shown in Table 1.9.
The comparison assumes production of a good epoxy grade product. The
resin catalyzed process operates with the cleavage system on bypass.
The HCl catalyzed process operates with an 8:l phenol-to-acetone feed
ratio and requires increased investment for environmental control.
The
table
shows that, although the HCl catalyzed process has a higher
investment cost, net production costs are essentially the same for
epoxy grade BPA.
For a given product value, the percentage return on
investment is higher for the resin catalyzed process.
For polycarbonate grade BPA, production costs for the resin catalyzed process are lc/lb higher than shown in Table 9.1 but we estimate
the increase for the HCl catalyzed process to be about 2-3c/lb in production cost and 4-5c/lb in product value.
27
Table 1.9
PROCESS COMPARISON
FOR EPOXY GRADE BPA
(120 Million lb/yr)
Resin
Catalyzed
HCl
Catalyzed
Battery limits investment, $ million
29.4
37.7
Offsites investment, $ million
17.6
17.3
47.0
55.0
42.8
4.7
43.5
2.4
48.5
45.9
1.1
2.4
49.6
48.3
9.3
10.2
58.9
58.5
9.8
11.5
68.7
70.0
Total fixed capital, $ million
Production costs, c/lb
Raw materials
Utilities
Variable costs
Fixed costs
TOTAL DIRECT COSTS
Overhead, depreciation, etc.
NRT PRODUCTION COST
R.O.I. at 25% of T.F.C.
PRODUCT VALUE
28
FIGURE 1.2 (sheet 1 of 2)
WITH ION EXCHANGE RESIN CATALYST
(UNION CARBIDE PROCESS)
T-151
Plmol
-
Stamp
.
Wohr
ConoMtmtor
Tb
v-w
:
E-104
ikhmlkl
LP stm
15 PI0
i
(
:Aota
i
:
:
E-102
To T-101
VlpXirCr
M
to WDlh
E-114
Rdoiler
ll5'F
I
1
R-101 AM
i
2
:
BPA kaaon
T(
3
i
:
T-152
i
Amtax Staqc
Tallk
:
M
E-102
M
cmuntmtm
v-101
GnantnJtol
bainr
i
ToV-102
Fmm V-IOJ
:
8 i
3 P
Crpr)allizer
z&l
M-102
Cryxtdlinr
r-,--
Bi+wt&A
PdcingordStomga
No.2
Centrifuge
:
i
i
MPStm
15Opig
cw
:
:
:
:
i
M-102
AthwC
LP stm
I5 pig
j
:
.
TOM-lOl*ap
TcmpredCmling
&7'F
Wdcr
.s
E-l&
PhenolStriper
PhenolReceiver
T-102
Rirphenol
A
Fldr*n
FIGURE 1.2 (shot 2 of 2)
WITH ION EXCHANGE RESIN CATALYST
(UNION CARBIDE PROCESS)
I
:
:
i
T-101
:
:
c-103
No. 2
BuffirTd
i
Cl*waBa
C&M
T-IQ
E-119
E-116
thdemmr
cad-r
E-12,
E-120
PdWbr
ND.3
RuffwTd
T-1W
ckndmmer
No. 2
PhB
-.Td
~l/n)O
V-MB
i
Rdluxbnm
Fmm M-101 MB
---1
t
:
:
:
F
3agF
MP%
150 mla
@I
MQnm
ci
lLPShn
; I5 pig
D&m10-A
300°F
x
T
T~toDinpd
Tarto Fuel
To T-101
;
i
:i
v-110
He
R
15B'F
~-------A
.
Tempd
Coding Water
E-115
Pmhmter
E-117
Rekoiler
E-118
BPAEvapomtw
;:i
ii3
i
8
1-b
T-153
:
:
:
i
I
ToVocwn
AlkaliTack
-
:
175'F
lSe"F
i
;
Ii
;
i
;
ll5'F
:
:
:
.
;
E-122
v-109
R-103 A rhw C
T-106
Rmminr
Reanolgcn*nt
Re~etm
No.1
F'hcml/l120Tank
E-17.2
P&d&O
Vqmrlzer
v-110
Phmo1&0
Receiver
i
l
LP5tm
.
I5 pig
i
:
.
:
:
.

BISPHENOL-A FROM PHENOL AND ACETONE WITH AN ION

Transcription

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