Professional Documents
Culture Documents
Report
No.
53Al
Interim
SYNTHETIC ETHANOL
AND ISOPROPANOL
by PARK
L. MORSE
January
A private
report
PROCESS
*
STANFORD
1974
by the
ECONOMICS
RESEARCH
PROGRAM
MENLO
INSTITUTE
I
PARK,
CALIFORNIA
a
CONTENTS
a
l
INTRODUCTION
SUMMARY ...........................
7
13
19
........................
.............
19
27
28
35
35
45
46
53
APPENDIX A
APPENDIX B
CITEDREFERENCES
...............
........................
..................
55
59
63
67
ILLUSTRATIONS
3.1
. . . .
17
3.2
18
4.1
. . . . . . . . . . . .
23
4.2
33
41
51
5.1
5.2
Vii
TABLES
2.1
2.2
3.1
3.2
. . . . . . . . . . . . . . . .
14
4.1
19
22
25
29
31
35
39
43
47
49
54
61
4.2
4.3
4.4
4.5
5.1
5.2
5.3
5.4
5.5
6.1
B.l
ix
. . . . . . .
INTRODUCTION
In
addition, design cases for ethanol and isopropanol manufacture that were
presented in Process Economics Program Report No. 53 (issued in 1969) are
updated.
Technical information for the study was taken from nonconfidential
sources.
SUMMARY
port evaluates the more recently developed reaction systems that operate
with liquid water and a high density propylene phase.
Table 2.1 summarizes the results of SRI's economic evaluation of the
Tokuyama Soda process, and a process using a cationic exchange resin catalyst.
exceed in significance those encountered by SRI in evaluating the processes shown in Table 2.1.
The stoichiometric equation for the hydration of propylene to IPA is
C3%
+ %O -
(CH3)sCHOH
A technical comparison of the two SRI design cases for liquid aqueous
phase direct hydration is shown in Table 2.2.
Now Veba-Chemie.
Table 2.1
PROCESSES FOR PRODUCING ISOPROPANOL BY LIQUID AQUEOUS PHASE
DIRECT HYDRATION OF PROPYLENE
COMPARISON OF ECONOMICS
Capacity = 360 Million lb/yr (163,000 metric
tons/yr)
at 0.9 Stream Factor
CE Cost Index = 142
Process Using
Tokuyama Soda
Technology
Process Using
Cation Exchange
Resin Catalyst
7.0
6.6
3.3
3.3
11.8
11.4
0.12
0.12
Propylene at 2.8$/lb
2.17
2.31
Miscellaneous materials
0.07
0.07
Utilities
0.88
0.92
0.16
0.16
0.75
0.75
0.07
0.07
0.33
0.32
to.071
(0.12)
4.48
4.60
Fuel credit
Net production cost, excluding
waste disposal and royalty
Confidence rating
Table 2.2
PROCESSES FOR PRODUCING ISOPROPANOL BY LIQUID AQUEOUS PHASE
DIRECT HYDRATION OF PROPYLENE
COMPARISON OF TECHNOLOGIES
Capacity = 360 Million lb/yr (163,000 metric
tons/yr) at 0.9 Stream Factor
Process Using
Tokuyama Soda
Technology
Process Using
Cation Exchange
Resin Catalyst
95.7
89.4
65.0
75.3
98.5
96.0
490
282
3000
1200
27.7
13.8
4
2
*
Reactor space-time-yield
[g IPA/(hr x liter)]
260
108
Steam (lb)
4.4
6.1
22.9
22.4
Power (kwh)
0.041
0.026
1,780
Number of reactors
Operators (men/shift)
A brief descrip-
rated from the crude alcohol by lowering the pressure, the unreacted propylene being recycled to the reactor.
tains most of the IPA.
the predominately
By means
The anhydrous
IPA is passed over activated carbon and marketed as premium grade isopropanel.*
Liquid propylene is
heated to 265'F by admixing with hot water before entering the reactor.
A dilute aqueous alcohol solution and a gas phase are discharged at the
base of the reactor.
a-
taining dilute IPA, is then sent to the purification section for concentration and purification.
Tokuyama Technology
Tokuyama Soda has developed and commercialized a high-pressure,
high-temperature process for converting propylene and water to IPA by
use of a liquid phase reaction.
a-
potassium, lithium, copper, beryllium, magnesium, calcium, barium, strontium, zinc, cadmium, aluminum, chromium, manganese, iron, cobalt, or nickel.
If the valence of X is equal to a, the sum of am + n is equal to 4 (m and
n are both positive integers).
aa
-
the pH rises and presumably must be adjusted before the catalyst solution
7
Table
3.1
ISOPROPANOL BY DIRECT
OF PROPYLENE
PATENT
Reference No./
Patent No.
Patent
Priority
Application
Assignee
OC
Atm
Catalyst
HYDRATION
SUMMARY
Examnle
Products
Raw Materials
Notes
67521
J 45-29163
J 43-14621
Mar. 8, 1968
Asahi Chem.
Ind.
100
14
Gelatinized
silica sol
Propylene
67543
Brit 1,238,556
US 749,308
Aug. 1, 1968
Celanese
150
103
Sulfonated copolymer of
styrene and divinylbenzene
Propylene,
and l&PO4
67549
US 3,644,497
US 772,817
Celanese
160
Propylene
Nov.
67524
J 47-23524
J 44-31449
Apr. 25, 1969
Mitsui
Toatsu
300
Diatomaceous
earth + Rap04
67523
J 47-23523
J 47-23523
June 17, 1969
Mitsui
Toatsu
180
Oxides
Zn
46209
US 3,497,436
us 606,759
Jan. 3, 1967
Monsanto
Electric
charge
67477
us 3,450,777
J 39-54792
Sept. 29, 1964
Tokuyama
200
10
w-n-0
Propylene
and water
IPA
Yield = 8.0%
sv
= 380
= 1.
67525
J 47-45323
J 43-77010
Oct. 24, 1968
Toray
200
10
Dealkalinated
zeolite
Propylene
and water
IPA
Yield = 5.1% on
water
= 2.4.
67532
Fr 2,098,801
USSR 3
USSR
180
16
H3p04 on borosilicate
Propylene
and water
IPA
Yield = 5.5%
The propylene vapor leaving the reactor is condensed and recycled to the reactor.
100688
Brit 1,166,121
Ital 22,094
Oct. 4, 1965
Edison
International
250
45
H3p04-MOO3
Propylene
and water
Acetone,
acids
Reaction
67494
US 3,548,013
US 561,836
June 30, 1966
Standard
of Ind.
Oil
257
458
Silica-alumina
Propylene
and water
IPA
Yield = 27%
67499
Brit 1,281,120
J 34798
May 8, 1969
Tokuyama
Soda
280
240
N+HSi(W3C&O)q
Propylene
and water
IPA
Yield/pass
Selectivity
STY
67529
Fr 2,059,246
US 853,489
Aug. 27, 1969
UOP
150
80
MeS&H
and
dioxane
Propylene
and water
IPA
Yield = 32%
1,
1968
Soda
of Ti and
dis-
paste
and water
Performance
IPA
Yield = 36%
Yield = 30.8%
and water
Yield = 33.1%
Conv. = 65%
Propylene
and water
IPA
Yield = 2.1%
Propylene
and water
IPA
Yield = 2.2%
Propane
water,
and Co,
IPA, and
100,000 volts/cm
= 70%
= 99%
= 182
time = 30 minutes
in autoclave.
ratio water/olefin
= 2.4.
Table
3.1
(Concluded)
ISOPROPANOL
BY DIRECT
HYDRATION
OF PROPYLENE
PATENT
Reference No./
Patent No.
Priority
Application
323154
Brit 1,269,553
Ger P1,768,207
Apr. 13, 1968
/
Assignee
OC
Atm
Veba-Chemie
Catalyst
HsPGa on carrier
Patent Example
Raw Materials
Propylene
and water
Products
Performance
Low molecular weight polymers are normally entrained with recycle olefin and carried back to
the reactor where they deactivate the catalyst.
Polymer formation is greatly reduced by keeping
recycle olefin concentration at 95% or higher.
Also see 67531.
67569
67571
Ger 2,147,740
Deutsche
Texaco
135-155
100
Amberlite@
etc.
252,
Propylene
and water
Notes
IPA
Ger 2,147,737
67570
Ger 2,147,739
SUMMARY
STY = 108-126
67572
Ger 2,147,738
67578
J 48-26711
J 46-59942
Aug. 10, 1971
Mitsui
Toatsu
200
67579
J 48-32809
J 46-64744
Aug. 26, 1971
Mitsui
Toatsu
250
67580
J 48-32810
J 46-64745
Aug. 26, 1971
Mitsui
Toatsu
200
67568
us 3,705,912
US 127,030
Mar. 22, 1971
UOP
140
18
45-84
Re207
Propylene
and water
IPA
Yield = 34.2%
Conv. = 37.5%
Pyromellitic
anhydride
Propylene
and water
IPA, Me,CO
(trace), and
isopropyl ether
Yield = 36%
Conv. = 37.5%
Sulfonic
CFaSOaH
Propylene
and water
Yield = 65.0%
Conv. = 66.5%
Propylene
and water
IPA
Mo(V1)
acids:
oxalate
Molar
ratio water/
11
is used again.
Lower con-
feeding the aqueous phase at the top and olefin at the bottom would be
ideal.
reactor to obtain the single pass performance data shown in Table 3.2.
The material of construction used in commercial reactors has not
been disclosed.
tion >lOppm
In addition, an Fe concentra-
Tokuyama Soda
Selectivity is high,
13
Table 3.2
TOKUYAMA EXPERIMENTAL DATA
Run 1
Run 2
Run 3
Run 4
Propylene
Propylene
Propylene
Ethylene
Butene*
Cq,sHSW
AlHSW
Na,HSW
Na,HSW
0.001
3.0
0.001
3.1
0.001
3.0
0.001
3.0
0.001
3.0
0.26
3.0
0.26
3.0
0.26
3.0
0.24
3.0
0.56
3.0
Reaction conditions
Temperature ('C)
Pressure (kg/en?)
280
250
280
250
280
250
300
300
220
200
Product
IPA,
IPA
IPA
Ethanol
Butanols
Conversion (96)
71
73
69
44
61
Selectivity (%)
99
99
99
95
95
Yield (%I
70
72
68
42
58
STY [g alc./(liter of
reactor vol x hr)]
260
267
252
166
429
Olefin feed
Aqueous solution+
Catalyst component
Molar concentration
of SW (mol/liter)
PH
.Na,HSW
Run 5
*
The starting butene was a mixture of 40% isobutylene and 4m butene-1, the
balance being substantially butane, and the main product was a mixture of
secondary and tertiary butanol at a mixing ratio of about 1:l.
'SW is abbreviation for [Si(W,CJo),].
14
Figure 3.2
Texaco) may be the basis for some of the technology practiced commercially.
The patent data indicate that the catalyst declines about 6% in activity
over the first 1,000 hours.
conducted with sulfuric acid.
ture from 125 to 155'C to compensate for the tendency of the catalyst to
lose activity.
allowing the liquid phase to trickle downward over the catalyst, the gas
phase moving concurrently with the liquid.
Commercial propylene usually contains some propane, and hence simple
recycle of unreacted feed to extinction is not feasible.
options would appear open to the IPA manufacturer:
15
However, two
The Deutsche Texaco technology has been used in part by SRI for a
design case in Section 5.
16
Figure 3.1
EQUILIBRIUM
CONVERSION
OF PROPYLENE
Temperature,
125
I50
175
200
TO ISOPROPANOL
OC
225
275
250
300
325
loo
90
80
70
212 atm
( \
60
50
40
30
20
IO
250
300
350
400
450
Temperature,
Source: 67576
17
500
OF
550
600
650
Figure 3.2
ISOPROPANOL
PRODUCTION
RATE WITH
DEUTSCHE
TEXACO
CATALYST
74
78
82
86
PROPYLENE
Source:
IN FEED, mol%
67576.
18
90
94
Process Description
The flow diagram for SRI's design case is shown in Figure 4.1.
The
200 section:
Table 4.1
The Tokuyama
Table 4.1
ISOPROPANOL BY TOKUYAMA TECHNOLOGY
BASES FOR REACTOR DESIGN
465-518
3000
27.7
Na3HCSi(%qd41
0.001
3
65.0
98.5
64.0
260
gal/yr to feed an acetone plant)* and anhydrous IPA (27.7 million gal/yr
for marketing).*
Fresh liquid propylene (95 mol%) and recycle propylene are pumped
through heater E-102 and into the base of reactor R-101.
Following up-
bottom at about 3000 psia, and then flow to separator V-101 where the
pressure is let down to 65 psia.
Each of
Receiving, 1 hr
Discharging, 1 hr
Catalyst (stream 20), and an acid (stream 19) to adjust for pH's higher
than 3, are added to the makeup tank to allow for losses in the system.
The solution being discharged from catalyst storage is returned to the
reactor after first being mixed with fresh water.
*
About 180 million lb/yr of 100% alcohol is produced for each of the
two products.
t Tokuyama Soda has informed SRI that high boiling oligomers do not.form.
Accordingly, stream 50 is probably not required.
20
Ether, water, and a small amount of IPA and polymer are distilled
are split, one half being used for manufacture of 91 ~01% IPA and the
remainder being used for producing pure IPA.
The 91 ~01% IPA is produced as a distillate in C-202.
In the pro-
duction of pure IPA the bottoms from C-201 are first dehydrated.
Benzene
In the design
the bottoms are recycled to C-101; however, SRI has learned that it is
acceptable to return them directly to the reactor.
off as bottoms from C-204 and then removed as a distillate from C-205.
The anhydrous distillate is then passed over activated carbon and filtered.
The use of activated carbon is discussed further in the following subsection.
A summary of waste disposal streams is included in Appendix B.
SRI uses two bleed streams (6 and 10) to prevent a buildup of a range
of molecular species in the system. Tokuyama Soda has indicated that
its existing commercial design requires but one bleed stream.
21
Table 4.2
ISOPROPANOL BY TOKUYAMA TECHNOLOGY
MAJOR PROCESS EQUIPMENT AND UTILITIES SUMMARY
Capacity = 360 Million lb/yr (163,000 metric
tons/yr) at 0.9 Stream Factor
Yajor Process Equipment
Equipment
Number
N8lne
Height
(it)
Diameter
(ft)
Remarks
Material of Construction
Reactors
Reactors (2 units)
R-101
316
6.0
35
30 ft of packing each
ss-clad shell;
porcelain packing
Material of Construction
Shell
Trays
Coluallls
c-101
c-201
c-202
c-203
C-204
C-205
C-206
Aaeotropic column
Light enda
Heavy ends column
Benzene recovery column
Drying column
Finishing column
Activated carbon treaters
(2 units)
30
92
42
62
75
32
15
12.4
6.3
4.0
4.2
11.0
4.9
3.0
316 8s
Carbon
Carbon
Carbon
Carbon
Carbon
Gize, ea
(sq ft)
Heat Load, ea
(million
Btu/hr)
Carbon
clad
steel
steel
steel
steel
steel
steel
316 88
Carbon
Carbon
Carbon
Carbon
Carbon
steel
steel
steel
steel
steel
Material of Construction
Shell
TUbeS
Exchangers
E-101
E-102
R-103
E-104
E-105
R-106
E-107
R-106
E-109
E-110
E-201
g-202
E-203
Condenser
Heater
Exchanger
Beater
Cooler
Condenser
Reboiler
Condensers
(2 units)
Exchangers (2 units)
Cooler
Reboiler
Condenser
Reboiler
Condenser (air cooled)
Reboiler
Condenser
Reboiler
Reboiler
Condenser (air cooled)
E-204
E-205
E-206
E-207
E-206
E-209
60
4.20
400
22.60
5,000
630
110
620
2,200
6,000
4,OW
660
2,400
3,920
460
1,400
600
6,700
5,100
1,090
1,700
Carbon steel
Carbon steel
316 8s
Carbon
steel
Carbon steel
Carbon
steel
Carbon steel
Carbon steel
316 8s
Carbon steel
Carbon steel
Carbon
steel
Carbon
steel
Carbon steel
Carbon steel
Carbon steel
Carbon steel
Carbon steel
Carbon steel
135.00
30.00
1.00
16.50
43.00
50.50
21.60
11.60
34.10
33.00
9.30
10.90
12.00
73.30
61.30
13.10
13.10
Baterial of Construction
Vol, ea (gal)
Vessels and Tanks
v-101
v-102
v-201
v-202
v-203
v-205
T-101
T-161
T-201
)4
Beparator
Reflux drum
Reflux drum
Reflux drum
Reflux drums
Surge vessel
(3 units)
Propylene storage tank
Carbon steel
Carbon
steel
316 as
316 8s
Carbon steel
Carbon steel
316 ss
Carbon steel
316 ss
316 88
Carbon
ateel
Carbon steel
Carbon steel
Carbon steel
Carbon steel
Carbon steel
Carbon steel
Carbon
steel
Carbon steel
2,600
316 ss
Carbon steel
Carbon steel
Carbon steel
Carbon steel
Carbon steel
Fiberglass
Carbon
steel
Carbon steel
10,000
3,000
600
6,000
3,000
60,000
65,000
200
22
12
44
20
40
36
15
valve
valve
valve
valve
valve
valve
trays,
trays,
trays,
trays,
trays,
trays,
24
24
24
24
24
24
in.
in.
in.
in.
in.
in.
spacing
spacing
spacing
spacing
spacing
spacing
Equipment
Number
Remarks
Material of Construction
Vol, ea (gal)
Name
Vessels and Tanks
(Continued)
T-202
T-203
T-252
T-253
(2 units)
(2 units)
Alcohol storage tanks
(2 units)
Alcohol storage tanks
(2 units)
33 )000
37,000
1,200,000
Carbon steel
Carbon steel
Carbon steel
1,400,000
Carbon steel
Size (bhpl
Compressors
K-101
K-102
Carbon steel
Carbon steel
710
300
Compressor
Compressor
Pumps
100 section:
200 section:
Battery Limits
Total
100
Section
17,500
3,500
56
56
1,969
1,767
102
50,000
152,000
Electricity (kw)
Steam
202,000
Utility
62
82
20,000
17,000
Additional Requirements
To Operate Utilities
Electricity (kw)
Makeup Water (gpml
Steam
226
20
Cooling water
-261
-350
487
370
Total
200
Section
14,000
3,000
Figure 4.1
ISOPROPANOL BY
TOKUYAMA TECHNOLOGY
150Fb
Cw/vE-IM
utr,
.- .--.
Acid
Liqdd
Propylene
hilr
Cad.nsat.
R-101
RMCbl
(2 hih)
v-101
s9$umt~
c-101
Azwlroplc Column
l-lOlA,,a6C
cddyst 5torape
!
Crud* Ale&d
1 -
Fresh Activated
30% NoOH
T-202A&B
Pnhydmm IPA
V-205
c-201
Ligh? End,
Collmm
c-202
Hwvy Ends
CdWl
C-203
Benzene Recovery
CdWtl
c-20(
DrybaR Column
C-205
Finishing Cdumn
Line Filter
i
:
C-206A&B
Activated Cmko
Treater
23
1_.,_.._._
._..,_.___..
. ....- -
-..- ----------.--.
_ --._,.,-.
-.----,.
I..
-.-
. .
. .
,.
:...
.
..:
;.
. .
-,
:,
.
:_
..,
,i
-.,.
..
..
..;.
.-
..-
-.
Table 4.3
(1)
---
Activated carbon
Benzene
Diisopropyl ether
Acid
Isopropanol
Ne.aHbi(Ws4c)cl
Pkymert
Propane
Propylene
Sodium hydroxide
water
42.12
600.35
--
---1,566.11
63.35
0.08
74.66
1,215.40
1.063.59
0.06
32.54
415.11
-1.063.36
11.45
30.00
-tr
-32.639.06
(29)
(30)
--
(2.6)
(27)
--
--
---
-401.70
765.14
tr
-1.24
363.40
--tr
66.39
(25)
-----
12.05
- (6)
(5)
5.66
63.35
--
(4)
--
--
Activated carbon
Ben?Zne
Diisopropyl ether
Acid
Isopropanol
Na0H[Wh4c).
1
Polymert
Propane
Propylene
Sodium hydroxide
water
(3)
(2)
-380.57
6.02
(28)
--
--
--
362.67
364.57
--
tr
-
tr
--
--
-0.62
191.70
1.24
9.02
-183.78
tr
---
0.62
191.70
(7)
---
- (9)
(8)
--
10.74
tr
927.59
4.72
tr
664.24
-41.94
6.00
---
11.45
31.29
32.72
417.39
32.919.94
11.45
31.22
17.63
227.43
31,656.58
(31)
(32)
-------
--
--
--
-(10)
--
--
(14)
---
(15)
(16)
--
--
4.72
777.61
tr
66.42
tr
86.42
-1.22
---776.96
11.45
30.00
-30.970.91
11.45
-30.970.91
----
--I
-
17.65
225.16
---
0.18
2.27
(33)
(34)
(35)
2.106.70
-805.14
2,108.70
805.14
-50.49
-205.99
50.49
205.99
2.159.19
1,011.13
384.57
----920.16
--728.46
---634.08
-442.36
-1,362.54
tr
-0.62
--
---
--362.57
-
--2.00
tr
--0.62
-
---
(39)------(40)
-383.34
-
--1.07
--
(41)
---11.90
(17)
(18)
---tr
86.42
11.45
30.00
--31,077.61
(42)
--
(43)
----
(44)
---
0.15
0.15
2.30
---
---1.10
tr
-0.62
1.10
(20
(19)
---
*
----
5.65 lb
-106.7
4.72
777.61
-1.22
-1.24
765.42
---(22)
-
(23)
1,005.36
-146.24
--
----191.70
(48)
(49)
3.5 lb/hr
--
3.5 lb/hr
--
-4.72
-0.63
--
--
---
----0.62
10.61
--1,000.64
-133.56
257.73
--469.86
(47)
(24)
--
(46)
(45)
--382.27
-1.21
-0.32
256.52
67.84
(50)
---
-tr
-
--
tr
-1.24
6.45
tr
---298.39
25
Process Discussion
It was necessary to make several assumptions in closing the material
balance.
the phase split in V-101 are not known, hence the material balance at
this point in the process is uncertain.
A small amount of acid probably must be added to maintain the catalyst
system at a pH of 3.
acetic acid would permit adequate catalyst activity and not pose the
corrosion problem that hydrochloric or sulfuric acid would.
The liquid from the reactor is considered to be corrosive because
of the presence of the acidic catalyst solution.
If corrosive com-
Tokuyama Soda has informed SRI that its IPA customers do not require
an activated carbon treatment of the product.
27
Sweetening on cycle.
bed.
Adsorption
During adsorption there may be a tendency of carbon fines or impurities to plug the flow.
Cost Estimates
The battery limits and utilities investment, together with other
capital requirements, are given in Table 4.4.
in Table 4.5.
Tokuyama
Soda
(67573)
SRI
$2.6*
$2.3
0.72-t
3.5
0.09
0.73t
4.4
0.04
Table 4.4
ISOPROPANOL BY TOKUYAMA TECHNOLOGY
TOTAL CAPITAL INVESTMENT
Capacity = 360 Million lb/yr (163,000 metric
tons/yr) at 0.9 Stream Factor
CE Cost Index = 142
Reaction-Recovery
cost
Purification Section
Capacity
Exponent
DOWll
cost
ulr
--
Section
Capacity
Exponent
cost
Down
l!L-
Total
capacity
Exponent
Down
J!L-
431,200
0.95
0.95
n.95
0.62
161,61Kl
0.64
0.47
185,300
431,200
69,900
93 )900
0.60
0.59
91,400
0.61
671,500
732,100
0.95
0.94
139,400
O.XG
0.40
0.82
163,200
0.41
0.40
276,700
0.H9
0.62
23,200
0.26
0.22
415,600
0.66
0.54
Il.61
0.44
470,900
0.95
0.79
792,500
0.91
0.95
0.95
n.t49
0.52
0.95
231,500
183
) 200
299,900
2,202,600
0.62
0.72
$1,767,000
0.65
0.76
7,006,000
0.77
0.67
$5,569,000
0.81
0.74
sl.439.oor)
0.95
0.79
0.76
0.79
0.91
0.95
0.52
566,600
Cooling water
Process water
steam
Inert gas
Tankage
Dowtherm@
4,000
4,000
1.053,200
260,700
61,500
72,300
0 39
904,600
133.100
0.73
0.73
244,200
244,200
0.50
0.50
10,900
771,500
2,866,900
0.89
0.63
921.200
0.76
0.70
$2,045,700
0.93
0.89
Utilities 0 tankage
investment
3,265,OOO
0.86
0.80
935,000
0.75
0.66
$2,330,000
0.91
n.xs
$10,273,000
0.80
0.71
$6,504,000
b.80
0.72
$3.769,000
0.80
0.68
Total
1.541.000
$11,814,000
Interest on construction
loan at 9.5%/yr*
746,000
start-up cost
933
Working capital
) 000
2,609,OOO
Table 4.5
Ethanol and Isopropanol, Synthetic, Supp. A. Part 1, January 1974
Units/lb
c/kg
Purification
Section
Units/l,000 kg
c/lb
0.1609 man-hr
0.05
0.06
0.01
0.11
0.13
0.02
164
210
33
55
167
11
109
43
22
0.12
0.26
407
233
174
2.17
0.01
4.78
0.02
7,803
43
11
16
210
17
7,803
43
167
6
11
16
43
11
8,019
81
33
532
9
188
582
20
132
1,618
Labor
Operating
Maintenance
Control laboratory
3 men/shift, $6.25/man-hr
3%/yr of battery limits cost
20% of operating labor
0.0001 man-hr
Total labor
Materials
Propylene
Catalyst
Activated carbon
Caustic
Maintenance
Operating
2.8c/lb (6.17c/kg)
$l.OO/lb ($2.2O/kg)
0.4$/lb (0.882$&g)
4$/lb (8.82c/kg)
3%/yr of battery limits cost
10% of operating labor
0.7741 lb
0.00012 lb
0.00759 lb
0.00108 lb
0.7741 tons
0.00012 tons
0.00759 tons
0.00108 tons
Total materials
0.06
0.13
2.24
4.93
8,100
0.05
0.60
0.11
1.32
0.06
0.16
0.01
0.13
0.35
0.02
165
'2,150
9
199
582
24
0.88
1.93
3,129
1,364
1,765
3.24
7.12
11,636
9,616
2,020
Utilities
Cooling water
Steam
Process water
Electricity
Natural gas
Inert gas (low pressure)
Total utilities
TOTAL DIRECT OPERATING
COST
22.99 gal
4.424 lb
0.0746 gal
0.0409 kwh
0.0018 million Btu
0.438 scf
191.9 cu m
4.424 tons
0.6228 cu m
90.24 kwh
997.7 ton cal
27.34 cu m
Plant overhead
0.09
0.20
326
0.07
0.15
236
Plant cost
3.40
7.47
12,198
0.75
1.65
2,700
Cash expenditures
4.15
9.12
14,898
0.33
0.73
1,181
9.5%/yr
0.07
0.15
248
4.55
10.00
16,327
Depreciation
Interest on working
TOTAL PRODUCTION
capital
COST
60c/million
Btu
(0.07)
(0.15)
4.48
9.85
11
4
(240)
16,087
31
Figure 4.2
ISOPROPANOL BY TOKUYAMA TECHNOLOGY
EFFECT OF CAPACITY AND OPERATING LEVEL ON PRODUCTION
COST
6.5
l-
I -
4.0
3.5
3.0
.5
,fi
.7
OPERATING
LEVEL,
33
.75
.a .05 .9 .951.0
fraction of design capacity
Process Description
The flow diagram for SRI's design case is shown in Figure 5.1.
The
200 section:
Table 5.1
ISOPROPANOL BY A PROCESS USING CATION
EXCHANGE RESIN CATALYST
BASES FOR REACTOR DESIGN
265-300
1200
13.75
75
96
72
108
purification section.
gal/yr* that is to feed an acetone plant) and pure anhydrous IPA (27.7 million gal/yr* for marketing).
Recycled hot water (stream 2) and fresh liquid propylene (95 mol%)
are mixed to form a two-phase (vapor-liquid) system.
The olefin-water
mixture is admixed with recycle stream 3 and the combination then enters
the top of reactor R-101 at 265'F and 1200 psia.?
trickles downward through a series of four beds packed with a cation exchange resin (such as Rohm and Haas' Amberlite 8 252),the gas phase moving
concurrently with the liquid; as IPA is formed, the heat of reaction is
compensated for by the addition of quench water (stream 4) into each of
the packed beds.
The reaction mix leaves the reactor at the base and flows to high
pressure separator V-101 where gas and liquid phases are split.
Pressure
is controlled in the reactor by regulating the flow of gas from the separator, the off-gas then being recycled to the reactor.
flows to low pressure separator V-102, where most of the remaining soluble
gas is flashed, and then compressed and recycled to the reactor.
However,
part of the recycle gas is bled from the system (s.tream 10) and returned
to the propylene plant for removal of propane.
About 180 million lb/yr of 100% alcohol is produced for each of two
products.
t
Deutsche Texaco does not recycle this stream to the reactor, but returns
it, along with stream 10, to the propylene plant.
36
Crude alcohol flows from the low pressure separator to light ends
column C-201 where ether, water, some IPA and a small amount of polymer
are distilled overhead, condensed into two liquid layers, and drawn off.
The upper, ether layer is used as fuel and also refluxed to the column
while the lower, water layer is discarded or incinerated.
The bottoms from C-201 are fed to C-202, where 91 ~01% IPA is distilled overhead.
In SRI's design
PAC-101 operates with two columns (A&C) on stream while duplicate columns
undergo some stage of regeneration.*
Stream
28,
from various other sources in the process, is fed (in stream 19) to
column c, which contains a weak acid cation exchanger such as Dowe x@ CCR-2
to remove Na+ and possibly other cations.
ward through a second column containing a weak base anion exchanger, such
as Dowe #
The cycle for each of two fully automated cation exchange columns
is as follows:
8 hours on stream
10 minutes backwash
40 minutes rinse.
the anion exchange columns was arbitrarily made the same as that of the
cation exchange column.
column A.
Anhydrous IPA is taken off as bottoms from C-204 and then removed
as a distillate from C-205.
38
Table 5.2
ISOPROPANOL BY A PROCESS USING CATION
EXCHANGE RESIN CATALYST
MAJOR PROCESS EQUIPMENT AND UTILITIES SUMMARY
Capacity =,360 Million lb/yr (163,000 metric
tons/yr) at 0.9 Stream Factor
Major Process Equipment
Bquipment
Number
R-101
Name
Reactors (4 units)
Height
(ft)
Diameter
(ft)
Material of Construction
40
8.0
Remarks
Material of Construction
Shell
Trays
Columns
c-201
c-202
C-203
C-204
C-205
C-206
Ether column
Aseotropic column
Benzene recovery column
Drying column
Finish column
Activated carbon treaters
(2 units)
92
30
62
75
32
15
12.8
10.4
4.2
11.0
4.9
3.0
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Size, ea
(sq ft)
Heat Load, ea
(million
Btu/hr)
steel
steel
steel
steel
steel
steel
Carbon
Carbon
Carbon
Carbon
Carbon
steel
steel
steel
steel
steel
Material of Construction
Shell
Tubes
Exchangers
E-101
E-102
E-103
E-104
E-105
E-106
E-201
E-202
E-203
E-204
E-205
E-206
E-207
E-208
E-209
E-210
Heater
Exchanger
Cooler
Condenser
Condenser
Cooler
'
Reboiler
Condenser
Reboiler
Condensers (2 units)
Reboiler
Condenser
Reboiler
Reboiler
Condenser
2xchanger
3.40
36.40
0.60
0.60
0.20
46.60
80.60
71.30
67.60
37.20
12.00
73.30
61.30
13.10
13.10
1.70
100
1,900
40
30
10
2,200
4,100
7,700
3,380
6,000
600
6,700
5,100
1,090
1,700
80
~01,
ea
Carbon
316 6s
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
steel
steel
steel
steel
steel
steel
steel
steel
steel
steel
steel
steel
steel
steel
steel
316 ss
316 ss
316 ss
Carbon
316 ss
316 ss
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
Carbon
v-202
V-203,4
V-205,6
T-101,2
T-151
T-201
T-202
T-203
T-204
T-252
T-253
steel
steel
steel
steel
steel
steel
steel
steel
steel
steel
Material of Construction
(gal)
Vessels R Tanks
6eparators
Reflux drum
Reflux drum
Reflux drums
6urge vessels
steel
1,200
9,000
5,000
6,000
20,009
13,000
65,000
200
33,000 s
37,000
2,000
1,200,000
316 ss clad
steel
Carbon steel
Carbon steel
Carbon steel
Fiberglass
Carbon steel
Carbon steel
Carbon steel
Carbon steel
Carbon steel
Carbon steel
1.400,000
Carbon steel
Carbon
39
44
12
40
36
15
valve
valve
valve
valve
valve
trays,
trays,
trays,
trays,
trays,
24
24
24
24
24
in.
in.
in.
in.
in.
spacing
spacing
spacing
spacing
spacing
..--.--
., ,,. L
-i_
I... _
@
Equipment
Number
Remarks
Material of Construction
Size
Name
Compressors
K-101
K-102
Compressor
Carbon steel
Carbon steel
13 bhp
100 bhp
Compressor
Package Units
PA0101
500 gpm
Ion exchanger
Pumps
100 section:
200 section:
Battery limits
Total
100
Section
--
17,200
2,700
83
63
200
Section
a,
Cooling water
(gpm)
14,500
1,lSS
794
394
279,000
4,000
275,000
23,000
lS,OOO
5,000
Utility
Steam
312
2s
Cooling water
-257
-344
569
372
Total
Additional Requirements
To Operate Utilities
Makeup Water
Electricity (kw)
(gpm)
Figure 5.1
,........................................................................................................................RE~,o~EcoMRy
E-104 I
Liquid Qs to
Pmpyheu Pkmt
Liquid
PwI*ll*
_-.
SECTION
. . .. .. . . .. . . . .. . .. . . . . . .. . . . . . .. . . .. . .. . . . . .. . . . . .. . . . . . .. .. .. . . .. . . . .. . . . . .. . . .. . . . . . . . . . . .. . . .. . . . .... .. . . . .. .. .. . . . . ..
Rim0
limo
Aqu-
sI
looOF
1200 pi0
-1
Rockwash
-I
1x1
b-1
1x1
I
Fmm C-2026262
Reostion Quench
v-101
HI& Fmwm
Se$amtaI
R-101
RM.Zlor
(4 Units)
Cd.
IPA
wear tkPAC-101
rkgeonnotim
(Column A)
v-102
Low Ptmwa
Separo~
la
PAC-I01
Exsho~~
Jwb NoOH
15OF
15 pi0
I T-201
212F
To C-202
c-201
Ether Column
c-202
Azeatropic
Column
c-203
hnnrma Recovery
COIUM
C-2Q4
Drying Column
C-205
Finishing Column
C-206ARB
Ac&otad Cohn
TrtStCf
. ...-
. ..y
,.
.r;::
-..
..;
.I,
_.
ei
_.
Table 5.3
Ethanol and Isopropanol, Synthetic, Supp. A. Part 1, January 1974
(3)
(2)
Sulfuric acid
Polymer
Propane
Propylene
Sodium hydroxide
Water
--
--
Activated carbon
Benzene
Diisopropyl ether
Acid
Isopropanol
---
-L
45.15
222.15
0.01
---
224.85
--
270.00
1,080.OO
((11
(9)
--
--
--
780.84
780.84
-
1.18
(10)
--
15.07
-
15.07
-
--
1.18
tr
270.00
21.26
21.26
248.75
266.76
-
21.00
--
21.00
245.76
-
14.054.18
12.685.04
2,165.Ol
17.45
12.667.59
.-I
--
--
(71
.-_
f6l
---
--
0.04
-
857.85
--
15)
(4)
14,034.23
1.01
19.94
--
15.07
-
1.18
--
45.15
--
44.61
--
--
3.50
932.31
(19)
--
---
0.09
14,033.22
(16)
(15)
----
---
780.84
0.82
--
--
--
--
--
1.48
14,832.60
592.00
----(22)
(21)
---
0.04
--
340.00
( 20)
2,310.36
---
--15.01
-
780.84
---
1.18
-
--
184.56
--
---
3,194.84
-
440.20
426.12
12.07
--
--
--
--
251.34
--
250.16
-
--
0.05
-
--
--
--
--
--
1.57
621.94
218.36
402.55
1.57
14.041.59
(26)
(25)
3.209.91
--
(24)
(23)
766.76
13.638.01
(27)
Activated carbon
Benzene
Diisopropyl ether
Acid
Isopropanol
Sulfuric acid
Polymer
Propane
Propylene
Sodium hydroxide
Water
----
---
766.76
--
-0.05
-384.49
0.05
--
--
1.57
13,638.01
(29)
----------
(28)
1.57
13.270.00
-184.56
(30)
(32)
(31)
--
384.49
-2.108.70
--
805.14
---
----
184.56
913.02
(33)
-2,108.70
--
805.14
---728.46
(34)
50.49
205.99
---634.08
(36)
(35)
-50.49
205.99
-449.52
2,159.19
-1.011.13
---384.49
---1,362.54
-----
(37)
(38)
---
382.57
1.92
--
----
----
(39)
(40)
-383.34
-1.07
--
--
--
--
---
(42)
o----
--
--0.15
_-
----
11.85
(43)
--0.15
---1.10
(44)
(45)
(46)
--
--
2.22
382.27
3.5 lb/hr
--
(47)
3.5 lb/hr
---
--
--
--
---
- (48)
15.07
2.01
---
---
--
1.18
-
--
--
--
1.10
--
10.75
--
1.03
-(49)
----1.57
8.00
43
Process Discussion
It was necessary to make several assumptions in closing the material
bal
ante.
Most of the
45
.Sweetening on cycle.
through bed.
Adsorption
the problem.
Cost Estimates
The battery limits and utilities investments, together with other
capital requirements, are given in Table 5.4.
in Table 5.5.
follows.
Texaco used a higher At for cooling water and made more extensive use of
air coolers.
Deutsche
Texaco
Battery limits investment for
100,000 metric tons/yr (million $1
Raw materials and utilities
Propylene (lb/lb)
Steam (lb/lb)
Cooling water (gal/lb)
Process water (gal/lb)
Electricity (kwh/lb)
SRI
!$4.9*
$4.6
0.74-t
0.78-t
6.3
4.2
0.08
0.06
6.1
22.4
0.11
0.03
Table 5.4
ISOPROPANOL BY A PROCESS USING CATION
EXCHANGE RESIN CATALYST
TOTAL CAPITAL INVESTMENT
Capacity = 360 Million lb/yr (163,000 metric
tons/yr) at 0.90 Stream Factor
CE Cost Index = 142
-L!Lcost
Reaction-Recovery
section
Total
Capacity
Exponent
E!!!!!
purification Section
Capacity
Exponcnl
capacity
Exponent
cost
DlJWll
208,000
132,300
254,200
0.80
0.58
0.62
0 55
25,400
0.36
0.29
5 619,900
0.72
0.59
0.84
$2,111,000
0.71
0.54
0.95
0.77
0.95
0.95
0.73
0.79
0.77
0.89
0.51
0.73
48X,600
0.95
0.79
1.344,lOO
16,600
771,500
0.95
0.95
0.95
o.n9
0.51
0.95
cost
A!JL
DOWll
-.
441,600
0.95
0.95
53,200
71,900
47,900
479,300
0.70
0.79
0.76
0.92
0.68
0.72
0.76
0.90
$1,093,900
0.90
0.88
42,600
0.40
0.40
$4,447,000
0.85
91,000
5,300
19,500
60,500
133,100
441,600
206,000
185,500
326,100
47,900
504,700
$1,713,800
0.84
0.76
42,600
$ 6,558,OOO
0.81
0.74
0.43
0.7H
Inert gas
Tankage
579,800
5,300
1,363,600
77.300
904;600
$ 2,930,600
0.94
0.86
309,400
0.66
0.71
S2,621,200
0.95
o.nx
$ 3,336,OOO
0.91
0.83
352,000
0.83
0.68
$2,984,000
0.92
o.ns
BATTERY LIMITS IE
UTILITIES COST
$ 9,894,OOO
0.64
0.77
$4,799,000
0.85
0.83
s5,095,000
fl.S4
0.71
Total
1,484.OOO
$11,378,000
676,000
Start-up cost
1,072,OOO
Catalyst cost
140,000
Working capital
TOTALCAPITAL IRVRSTMRRT,
not including land
2,671,OOO
$15,937,000
47
Table 5.5
Ethanol and Isopropanol, Synthetic, Supp. A. Part 1, January 1974
Total Costs
Thousand
Basis or Unit Cost
Units/lb
4 men/shift, $6.25/man-hr
3%/yr of battery limits cost
20% of operating labor
0.0001 man-hr
$/yr
Units/l,000 kg
c/lb
C/kg
0.2146 man-hr
0.06
0.05
0.01
0.13
0.11
0.02
219
196
44
99
133
20
120
63
24
0.12
0.26
459
252
207
2.31
0.01
5.09
0.02
8,333
133
10
11
63
12
Labor
Operating
Maintenance
Control laboratory
Total labor
Materials
Propylene
Caustic
Sulfuric acid
Activated carbon
Maintenance
Operating
2.8'$/lb (6.17c/kg)
3.8C/lb (8.38$&J
0.9$/lb (1.98$/kg)
0.4$/lb (0.88X-&)
30/o/yrof battery limits cost
10% of operating labor
0.8267 lb
0.00133 lb
0.00175 lb
0.00759 lb
0.8267 tons
0.00133 tons
0.00175 tons
0.00759 tons
Total materials
0.05
0.01
0.11
0.02
8,333
18
6
11
196
22
2.38
5.24
8,586
8,482
104
0.05
0.82
0.11
1.81
0.09
0.02
26
43
14
84
21
137
2,927
0.04
0.01
163
2,970
14
126
27
0.92
2.03
3,300
188
3,112
3.42
7.53
12,345
8,922
3,423
18
6
Utilities
Cooling water
Steam
Process water
Electricity
Inert gas (low pressure)
Total utilities
TOTAL DIRECT OPERATING
COST
22.6 gal
6.11 lb
0.1096 gal
0.026 kwh
0.5037 scf
188.6 cu m
6.11 tons
0.9144 cu m
57.33 kwh
31.44 cu m
Plant overhead
0.10
0.22
367
0.06
0.13
228
Plant cost
3.58
7.88
12,940
0.75
1.65
2,700
Cash expenditures
4.33
9.53
15,640
Depreciation
0.32
0.71
1,138
9.5Wyr
0.07
0.15
254
4.72
10.39
17,032
42
6
By-product credit
Fuel credit, Stream 10
Fuel credit, Stream 48
NET PRODUCTION COST
60c/million
6O$/million
Btu
Btu
(0.10)
(0.02)
4.60
(0.22)
(0.04)
10.13
(351)
(90)
16,591
49
Figure 5.2
7.0
I I I
I I I
.65
.7
.75
I-
6.5
3.5
3.0
I
.5
LEVEL,
.a .a5 .9 .951.0
51
Processes evaluated earlier in the report use direct hydration reaction systems that operate with liquid water and a high density propylene
phase, the product mainly being contained in a liquid effluent.
PEP
Report 53, issued in 1969, evaluated processes wherein reactants and products within the reactor are principally in the vapor phase.
This section
of this report updates the earlier so-called vapor phase direct hydration
processes.
The current results for the ethanol process were obtained by using
updated costs, the plant capacity and design remaining essentially the
same as in the 1969 report.
report, because the confidence rating, which was poor in 1969, would not
be improved by information acquired since then.
53
Table 6.1
ETHANOL OR ISOPROPANOL BY VAPOR PHASE DIRECT HYDRATION OF OLEFINS
Hibernia-Scholven*
Technology
Shell Technology
Product
Isopropanolt
Organic feed
Ethylene
Propylene
360
530
407
1000
590
0.50
0.95
(as
100%)
Number of reactors
Downflow of reactants
over catalyst
Downflow of reactants
over catalyst
4.4
5.6
4.4
5.7
91
101
81
84
9.3
71.2
0.056
2,650
4.5
44.4
0.026
3,260
7.7
8.5
2.69
3.6
11.89
13.9
6.61
(0.17)
5.21
(0.13)
6.449
'5.08
stream
*
Now Veba-Chemie.
Battery limits.
0Off-site tankage not included.
54
Appendix A
DESIGN AND COST BASIS
Design and costs were based on an assumed plant location along the
U.S. Gulf Coast at Houston, Texas.
100F
SOOF
85'F
20F
Definitions
The following definitions of terms are used in this report:
Conversion
Selectivity
STP
Ton
Yield
55
Cost Basis
Capital Investment
Equipment costs were estimated primarily from correlations in the
literature, adjusted to a Chemical Engineering Cost Index of 142.
Battery limits capital investment costs were calculated by the
method of Hirsch, modified with respect to alloy piping (24249).
Gen-
Production Costs
Operating labor wage rates were based on those estimated for Houston.
The base rate of $4.75/hr was derived from U.S. national average rates in
industrial chemical plants corrected to the Houston area.
This figure
includes allowances for working foremen, average overtime, and shift premium.
21%.
shift overlap.
personnel located at the plant site and services directly associated with
operations and maintenance.
Confidence Ratings
SRI uses only nonconfidential
Economics Program.
Therefore,
rigorous calculation, but most often only simplified design methods are
warranted.
process scheme.
and from process to process in a given study, depending on the nature and
amount of information available.
The confidence ratings are therefore presented as a means of summarizing SRI's overall appraisal of the reliability of the cost estimate
or process scheme or both.
mediate situations.
Some production-cost elements are considered in arriving at confidence ratings.
Prices of mate-
rials are not usually considered in confidence ratings, because SRI may
not have access to prevailing contract prices.
Table B.l
Process
Isopropanol from propylene, Figure
4.1
(Tokuyama Technology)
SUMMARY OF
WASTE STREAMS
Stream
Number
Source
of Waste
Remarks
6 (g)
R-101
To fuel
10 629
c-101
and
To fuel
25 (1)
c-201
and
To waste pond or
incinerator
26 (11
c-202
To wastc pond or
incinerator
47 (1 + s)
C-206A&B
46 (1)
C-201
To fuel
50 (1)
c-101
To waste pond or
incinerator
10 (1)
v-101,2
To propylene
for recycle
17 and
16 (11
PAC-101
Est. at 17,000
to 34,000
lb/hr of water with
small quantity of acid,
caustic, and high boilers
25 (1)
c-201
To waste pond or
incinerator
47 (1 + s)
C-206A5B
48 (1)
c-201
To fuel
plus
and
plant
The waste streams shown are those anticipated during normal plant operation.
In addition to
the quantities shown, there will be liquid discharges resulting from normal leakage of pumps
Extraneous water
and other equipment and vapor discharges resulting from tankage breathing.
will periodically enter the waste system from washing down the operating area and from other
In addition, there can be large, abnormal discharges resulting from
maintenance operations.
operating errors, the functioning of safety valves, draining and purging of equipment during
turnarounds, and the like.
61
CITED REFERENCES
24249
Hirsch, J. I-I.,
et al., "EstimatingPlant InvestmentCostsIn
Chem. Eng. Progr., 56 (December 1960), 37-43
46209
67472
67477
67494
67499
67521
67523
67524
67525
67529
67531
67532
67543
63
67549
67562
67563
67564
67565
67568
67569
67570
67571
67572
67573
Tokuyama Soda Co., Ltd., "Tokuyama'sDirect Hydration IPA Process," Technical Brochure, 1973
67575
67576
67578
67579
64
67580
100888
323154
Books
B-l
B-2
65
PATENT
ACC.
CHAP.
NO.
NO.
67521
67543
67549
67532
67569
67570
67572
67571
67569
67570
67571
67572
lOORes
67523
67524
67570
b7579
67580
46209
67472
67472
67694
67562
67563
67564
67565
67477
67499
67525
67529
67568
323154
67531
3
:
3
3
i
4
4
4
4
3
3
3
REFERENCES
BY
ASAHI
CHEMICAL
CELANESE
CELANESE
DALIN,
DEUTSCHE
DEUTSCHE
DEUTSCHE
DEUTSCHE
DEUTSCHE
DEUTSCHE
DEUTSCHE
DEUTSCHE
M. A.,
TEXACO
TEXACO
TEXACO
TEXACO
TEXACO
TEXACO
TEXACO
TEXACO
INDUSTRY
ET
AL,
EDISON INTERNATIONAL
MITSUI TOATSU CHEMICALS
MITSUI TOATSU CHEMICALS
3
7
3
MONSANTU
RHEINPREUSSEN
A.G..
FUER
BERGRAU
RHEINPREUSSEN A.G..
FUER BERGRAU
STANDARD
OIL, INDIANA
TOKUYAMA SODA
TOKUYAMA
SODA
TOKUYAMA SODA
TOKUYAMA SODA
TOKUYAMA SODA
TOKUYAMA
SODA
TORAY
UNIVERSAL OIL PRODUCTS
UNIVERSAL
OIL PRODUCTS
VEBA-CHEMIE
VEBA-CHEMIE
4
3
3
7
3
7
3
i
3
3
z
COMPANY
COMPANY
MITSUI TOATSU
CHEMICALS
67
UND
CHEMIE
uun CHEMIE