Hidratação Direta Propeno

Ethanol and Isopropanol, Synthetic, Supp. A.
Part 1, January 1974
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
Ethanol and Isopropanol, Synthetic, Supp. A. Part 1, January 1974
a
CONTENTS
a
l
INTRODUCTION
SUMMARY ...........................
ISOPROPANOL BY DIRECT HYDRATION OF PROPYLENE:

REVIEW'OF PROCESSES .....................
Tokuyama Technology .....................

Deutsche Texaco Technology
.................
7
13
ISOPROPANOL BY TOKUYAMA TECHNOLOGY
19
........................
.............
Process Description .....................

Process Discussion
.....................
Cost Estimates
.......................
19
27
28
ISOPROPANOL BY A PROCESS USING CATION EXCHANGE

RESIN CATALYST
/ ......................
35
Process Description .....................

Process Discussion
.....................
Cost Estimates
.......................
35
45
46
UPDATED PROCESSES FOR VAPOR PHASE DIRECT HYDRATION

OFOLEFINS
.........................
53
APPENDIX A
DESIGN AND COST BASIS
APPENDIX B
SUMMARY OF WASTE STREAMS ..............
CITEDREFERENCES
...............
........................
PATENT REFERENCES BY COMPANY
..................
55
59
63
67
ILLUSTRATIONS
3.1
Equilibrium Conversion of Propylene to Isopropanol
. . . .
17
3.2
Isopropanol Production Rate with

Deutsche Texaco Catalyst
. . . . . . . . . . . . . . . . .
18
4.1
Isopropanol by Tokuyama Technology
. . . . . . . . . . . .
23
4.2

Effect of Capacity and Operating Level on
Production Cost . . . . . . . . . . . . . . . . . . . . . .
33
Isopropanol by a Process Using Cation Exchange

Resin Catalyst
. . . . . . . . . . . . . . . . . . . . . .
41

Resin Catalyst
Effect of Capacity and Operating Level on
Production Cost . . . . . . . . . . . . . . . . . . . . . .
51
5.1
5.2
Vii
TABLES
2.1
2.2
3.1
Process for Producing Isopropanol by Liquid Aqueous

Phase Direct Hydration of Propylene
Comparison of Economics . . . . . . . . . . . . . . . . . .
Process for Producing Isopropanol by Liquid Aqueous

Phase Direct Hydration of Propylene
Comparison of Technologies
. . . . . . . . . . . . . . . .
Isopropanol by Direct Hydration of Propylene

Patent Summary
. . . . . . . . . . . . . . . . . . . . . .
3.2
Tokuyama Experimental Data
. . . . . . . . . . . . . . . .
14
4.1

Bases for Reactor Design
. . . . . . . . . . . . . . . . .
19

Major Process Equipment and Utilities Summary . . . . . . .
22

Stream Flows
. . . . . . . . . . . . . . . . . . . . . .
25

Total Capital Investment
. . . . . . . . . . . . . . . . .
29

Production Costs
. . . . . . . . . . . . . . . . . . . . .
31

Resin Catalyst
Bases for Reactor Design
. . . . . . . . . . . . . . . . .
35

Resin Catalyst
Major Process Equipment and Utilities Summary . . . . . . .
39

Resin Catalyst
Stream Flows
. . . . . . . . . . . . . . . . . . . . . . .
43

Resin Catalyst
Total Capital Investment
. . . . . . . . . . . . . . . . .
47

Resin Catalyst
Production Costs
. . . . . . . . . . . . . . . . . . . . .
49
Ethanol or Isopropanol by Vapor Phase Direct

Hydration of Olefins
. . . . . . . . . . . . . . . . . . .
54
Summary of Waste Streams in SRI Design Cases
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
This report emphasizes the economics and technology for isopropanol

produced by the direct hydration of propylene.
Design cases based in
part on Tokuyama Soda and Deutsche Texaco technologies are included.
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.
Tokuyama Soda and Deutsche Texaco have commercial isopropanol
plants that presumably use technologies somewhat similar to those described

in this report.
Appendix A contains a definition of terms, design conditions, and
the cost basis used. 'Appendix B presents waste disposal data.
Special acknowledgment is given the Loprest Company (fabricators of
ion exchange equipment) of Rodeo, California, and Dow Chemical Company
(manufacturers of ion exchange resins similar to those used in the report)
for their help in the design work.
SUMMARY
This report emphasizes the manufacture of isopropanol (IPA) by the

direct hydration of propylene.
SRI also updated designs for ethanol and
isopropanol manufacture (see Section 6) by direct hydration that were

included in PEP Report 53.
The earlier report emphasized processes wherein hydration is carried
out by water and olefinic reactants in the vapor phase.
The current re-
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.
When feasible, SRI used information authored by Deutsche Texaco
personnel for the latter process.
Even though the two processes have
significantly different reaction systems, the overall economics appear

to be quite similar.
Both of these processes apparently offer superior
economics to the vapor phase direct hydration process (Hibernia-Scholven*

technology) that was updated in Section 6.
However, the SRI design for
the updated process contains appreciable uncertainties
that could well
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.
Both processes have been
commercialized in the last several years and appear to offer advantages
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
Battery limits, excluding catalyst
7.0
6.6
Utilities and tankage
3.3
3.3
11.8
11.4
Labor (operators, maintenance,

control laboratory)
0.12
0.12
Propylene at 2.8$/lb
2.17
2.31
Miscellaneous materials
0.07
0.07
Utilities
0.88
0.92
Overhead, taxes, and insurance
0.16
0.16
G&A, sales, and research
0.75
0.75
Interest on working capital
0.07
0.07
Depreciation of fixed capital
0.33
0.32
to.071
(0.12)
4.48
4.60
Capital investment (million $1
Total fixed capital, not including

waste disposal
Production cost ($/lb)
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
tons/yr) at 0.9 Stream Factor
Process Using
Tokuyama Soda
Technology
Process Using
Cation Exchange
Resin Catalyst
Plant yield on propylene (%)
95.7
89.4
Conversion of propylene per

pass (%I
65.0
75.3
Selectivity on propylene (%)
98.5
96.0
Average reaction temperature (OF)
490
282
Reaction pressure (psia)
3000
1200
Molar ratio of water .to olefin

at reactor inlet
27.7
13.8
4
Type of reaction system
2
*
Reactor space-time-yield
[g IPA/(hr x liter)]
260
108
Steam (lb)
4.4
6.1
Cooling water (gallons)
22.9
22.4
Power (kwh)
0.041
0.026
Natural gas (Btu)
1,780
Number of reactors
Utilities,* per lb of alcohol
Operators (men/shift)
Packed columns, countercurrent flow with catalyst soluble in aqueous

phase.
t
Trickle cocurrent flow over resin catalyst.
*
Battery limits.
over other recently patented direct hydration processes.
A brief descrip-
tion of the two processes follows:
IPA by Tokuyama Technology

The hydration of propylene to IPA in this technology is conducted
at about 490'F and 3000 psia in the presence of a soluble catalyst of
Na9H[SiW~,~~)41m
Liquid propylene is heated to 465'F before being intro-
duced in the bottom of a packed reactor.
The olefin then moves counter-
current to liquid water containing the catalyst, a dilute crude alcohol

being discharged at the base of the column.
The unreacted olefin is sepa-
rated from the crude alcohol by lowering the pressure, the unreacted propylene being recycled to the reactor.
tains most of the IPA.
the predominately
The resultant aqueous stream con-
The IPA is then concentrated by distillation,
aqueous fraction being returned to the reactor, the IPA
concentrate being sent to the purification section of the plant.
By means
of distillation a 91 ~01% IPA product and an anhydrous IPA product are

produced.
The 91 voi% IPA is used for acetone manufacture.
The anhydrous
IPA is passed over activated carbon and marketed as premium grade isopropanel.*
IPA by a Process Using Cation Exchange Resin Catalyst

The hydration of propylene to IPA in this technology is conducted
at about 280'F and 1200 psia by passing propylene and an aqueous phase
downward over an acidic cation exchange resin.
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.
The unreacted gaseous olefin is recycled to the
reactor after being separated from a liquid phase.
The liquid phase, con-
a-
taining dilute IPA, is then sent to the purification section for concentration and purification.
The latter operations are similar to the pro-
cedures described under the Tokuyama Soda technology; however, a much

larger quantity of water is separated (as a liquid phase) from the
alcohol and returned to the reactor as recycle.
*
Tokuyama customers have not required this step.
6
ISOPROPANOL BY DIRECT HYDRATION OF

REVIEW OF PROCESSES
PROPYLENE:
This section of the report contains a patent review and a discussion

of the more pertinent technological advances since the 1969 PEP report on
ethanol and isopropanol.
the 1969 report,
Table 3.1 summarizes the patents issued since
Major technological advancements have been made by

Their technologies are summarized
Tokuyama Soda and Deutsche Texaco.

below.
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-
A small concentration of the catalyst
in an aqueous phase selectively converts at a high rate liquid propylene

to IPA.
The catalyst formula can be written as XmHn[Si(Wa010)4] where X is
hydrogen, ammonium, methyl ammonium, ethyl ammonium, ethanol ammonium,
propyl ammonium, or a water-soluble,
salt-forming metal such as sodium,
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
-
Tokuyama Soda has used the abbreviation SW for silicotungstate

l3~w3qo)41.
A few of the catalysts tested are H4SW, NaaHSW, LiaHSW,
and Cui., HSW.
The pH of the aqueous catalyst solution must be controlled
to around 2.0 to 4.5.
At lower pH's polymerization of the olefin occurs.
Typically, the pH of the catalyst solution is adjusted to around 3 by

the addition of acids or bases, the choice depending on the degree of
acidity of the catalyst in question.
During the conversion of the olefin
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
Acetic acid and

molybdophosphoric
acid
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
Molar ratio CsRs/BaO
= 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
Molar ratio CsRs/RsO
= 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
Acetone yield = 29%

IPA yield
= 8
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%
Reactor effluent is cooled at 458 atm and

organic phase is separated from an aqueous
liquid phase that is recycled to the reactor.
The organic phase is flashed, the olefin being
separated from IPA and recycled.
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%
Molar ratio CeBs/RaO = 20.
IPA and diisopropyl ether
Yield = 30.8%
Deactivation of catalyst is combated by addition

of 0.1 wtX RaPGa. Formerly the use of stainless
steel would deactivate system. IPA/DIPE = 8 wt
ratio.
and water
IPA and isopropyl

acetate
Yield = 33.1%
Conv. = 65%
Probably olefin first forms ester with the acid.

Then ester is hydrolyzed to alcohol.
Propylene
and water
IPA
Yield = 2.1%
Propylene
and water
IPA
Yield = 2.2%
Propane
water,
and Co,
IPA and n-propanol
IPA, and
100,000 volts/cm
= 70%
= 99%
= 182
and 200 set used for reaction.
time = 30 minutes
in autoclave.
Molar ratio water/olefin = 27. Alcohol, water,

and a completely soluble catalyst leave the
reactor.
After separation, an aqueous phase containing the catalyst is returned to the reactor.
Also see Tokuyama Soda patents identified by
reference numbers 67562, 67563, 67564, and 67565.
Molar
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
Sept. 24, 1971

c
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
IPA and diisopropyl ether
SUMMARY
STY = 108-126
67572
Ger 2,147,738
r Trickle flow of aqueous phase over catalyst and

downflow of gas with molar ratio of water/olefin
2 13 give high selectivity and yield/pass.
Heated water enters top of reactor, cooler water
is added along reactor length to serve as a
quench.
Catalyst has high activity for at least
8,000 hours.
L
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%
45 minute batch reaction.

olefin = 6.4.
Pyromellitic
anhydride
Propylene
and water
IPA, Me,CO
(trace), and
isopropyl ether
Yield = 36%
Conv. = 37.5%
1 hour batch reaction.

olefin = 6.4.
Sulfonic
CFaSOaH
Propylene
and water
IPA, acetone, and

isopropyl ether
Yield = 65.0%
Conv. = 66.5%
90 minute batch reaction.

olefin = 15.
Propylene
and water
IPA
Mo(V1)
acids:
oxalate
16 hour batch reaction.

olefin = 2.
Molar
ratio water/
Molar ratio water/
Molar ratio water/
Molar ratio water/
11
is used again.
Other than the drop in pH, the catalyst is stable and
requires little replacement.

The catalyst concentration is about 0.001 mol per liter.
Lower con-
centrations cause a falloff in activity; however, higher concentrations

cause no substantial benefit.
Either agitated batch-type or continuous column-type reactors are
It would appear that a packed column
suitable for the olefin conversion.
feeding the aqueous phase at the top and olefin at the bottom would be
ideal.
The product, together with catalyst solution and unconverted ole-
fin would then be removed as bottoms.
Inert gases or liquids present would
be expected to accumulate at the top of the columns where they could be

easily removed.
It is believed that Tokuyama Soda used a similar type
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.
The low pH and high temperature would indicate that
carbon steel would corrode quite rapidly.
tion >lOppm
lowers catalyst activity.
In addition, an Fe concentra-
Accordingly, the use of ion ex-
changers, nonferrous materials, or chelating agents has been discussed

in a Tokuyama patent (67562).
Apparently diisopropyl ether and possibly trace amounts of polymer
and acetone are the only significant by-products formed.
Tokuyama Soda
has stated that acids and aldehydes are not by-products.

The Tokuyama Soda technology has been used by SRI for a design case
in Section 4.
The reader is referred to the design case for Tokuyama
recovery and purification technology.
Deutsche Texaco Technology

Deutsche Texaco has developed and commercialized a process for converting propylene and water to IPA under a moderate pressure and temperature.
The conversion is conducted with mixed phases of liquid and gas
in contact with an acid-type ion exchange resin.
Selectivity is high,
only a small amount of polymer and diisopropyl ether being formed.
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
Feeding rates [kg/

(liter of reactor
vol x hr)]
Olefin
Aqueous solution
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
Except as noted, the technology in this subsection is based largely

on articles published by Deutsche Texaco personnel (67575, 67576).
Commercially,
100 atm.
the reaction is carried out at 130 to 150C and 60 to
The moderate temperatures and pressures are feasible because of
the favorable thermodynamic equilibrium that is established and because

of the high activity of the catalyst.
Figure 3.1 is a Deutsche Texaco
equilibrium diagram that clearly shows that at temperatures as low as 250

to 300F, and pressures around 71 atm, 90% of a pure propylene feed theoEven when 20% inerts are present it
retically can be converted to IPA.
is possible to obtain equilibrium conversions around 80%.
Figure 3.2
shows the reaction rate as a function of propylene concentration in the

organic feed.
A patent (67472) assigned to Rheinpreussen
(integrated with Deutsche
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.
It is conjectured that regeneration could be
A more recent patent (67570) shows a 15%
falloff in activity for an Amberlite@ 252 catalyst over an 8,000 hour

period.
These excellent results were achieved by increasing the tempera-
ture from 125 to 155'C to compensate for the tendency of the catalyst to
lose activity.
Presumably the decrease in activity continues until re-
generation is an economic necessity.

The optimum water-to-propylene
15:l.
molar ratio in the reactor is 12.5 to
If lower ratios are used, or if water distribution in the reactor
is poor, polymer formation is favored.
Good distribution is provided by
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
Route unconverted Cs's to propylene plant

Recycle part of unconverted Cs's to reactor, using the remainder for propylene plant, or as fuel.
The Deutsche Texaco technology has been used in part by SRI for a
design case in Section 5.
The reader is referred to that section for
information on recovery and purification technology.
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
This section presents a design case based on Tokuyama technology.

Section 3 contains a review of patents and the technologies of Tokuyama
Soda and Deutsche Texaco.
Process Description
The flow diagram for SRI's design case is shown in Figure 4.1.
The
plant is composed of the following two sections:

100 section:
Propylene and water are converted to

crude IPA
200 section:
Crude IPA is concentrated and refined to

form -91 vol%IPA and anhydrous IPA.
The design is based on technical material forwarded to SRI by

Tokuyama Soda (67573) and a Tokuyama Soda patent (67499).
shows the bases used by SRI for design of the reactor.
Table 4.1
The Tokuyama
material did not include distillation facilities for producing 91 ~01%

IPA or for treating anhydrous IPA with activated carbon followed by distillation.
SRI added each of these process steps.
Table 4.1
BASES FOR REACTOR DESIGN
Reaction temperature (OF)

Molar ratio of water/olefin in feed to reactor
Catalyst
Catalyst concentration in water (mol/liter)
pH of catalyst solution
Conversion of propylene per pass (%I
Selectivity of IPA on propylene (96)
Yield of IPA on propylene per pass (%I
STY [g IPA/(hr)(liters of reactor volume)]
19
465-518
3000
27.7
Na3HCSi(%qd41
0.001
3
65.0
98.5
64.0
260
Major equipment and utility requirements are given in Table 4.2.

Stream rates for producing about 360 million lb/yr of 100% IPA are given
in Table 4.3.
The production is split between -91
~01% IPA (30.4 million
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-
ward movement through the packing, contact is made with a downward-flowing

aqueous phase (stream 5) that contains the soluble silicotungstate catalyst.
Inert gas (propane, etc.) and some propylene are discharged at the
top of the reactor.
IPA and unconverted reactants are discharged at the
bottom at about 3000 psia, and then flow to separator V-101 where the
pressure is let down to 65 psia.
The flashed vapor phase, together with
propylene from C-101 is recycled to the reactors.

The liquid phase from V-101, containing the catalyst as well as most
of the water and IPA discharged from the reactor, is fed to the azeotropic
column C-101.
The catalyst and a great share of the water is taken off
A small stream (stream 50) is bled off to prevent the buildup

of high boiling polymers in the catalyst system, t The remainder of the
as bottoms.
bottoms flow to one of three catalyst storage tanks (T-lOlA-0.
Each of
the tanks operates automatically on the following three hour cycle:

b
Receiving, 1 hr
Discharging, 1 hr
Makeup of chemicals and mixing, 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
The overhead from C-101 is partially condensed.
The vapor phase
(stream 9), which is mostly propylene, is recycled to the reactor after

a small stream (stream 10) is bled off to prevent a buildup of nonreactive
*
The liquid phase (stream 11) is crude IPA that contains water,
components.
ether, and polymer as impurities.
The crude IPA is first mixed with a small amount of caustic solution
to neutralize any acidic components and then is fed to light ends column
c-201.
Ether, water, and a small amount of IPA and polymer are distilled
overhead and condensed to form two liquid layers.

primarily water and is discarded or incinerated.
The bottom layer is

Part of the top layer,
consisting of mostly diisopropyl ether, is drawn off and used as fuel,

while the remainder is refluxed to the column.
The bottoms from C-201
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
(stream 32).is used as reflux in C-204 and acts as an azeotroping agent

for water.
The water distilled off is condensed, separated from a benzene
layer, and eventually is removed as bottoms from C-203.
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.
Anhydrous IPA is taken
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
MAJOR PROCESS EQUIPMENT AND UTILITIES SUMMARY
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
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
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
Table 4.2 (Concluded)

Major Process Equipment
.
I
Equipment
Number
Remarks
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)
(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:
14 operating, no spares; 688 operating bhp

21 operating, no spare*; 56 operating bhp
Utilities Summary (Average Conaumptions)
Battery Limits
Total
100
Section
Cooling water (gpm)
17,500
3,500
Process water (gpm)
56
56
1,969
1,767
102
50,000
152,000
Electricity (kw)
Steam
202,000
at 150 psig (lb/hr)
Natural gas (million Btu/hr)

Inert gas, low pressure (scfh)
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_.,_.._._
._..,_.___..
. ....- -
-.-_ - -.--.--- __.-_.__..__.._

_.-.-._.._--l--.-------.------.--
-..- ----------.--.
_ --._,.,-.
-.----,.
I..
-.-
. .
. .
,.
:...
.
..:
;.
. .
-,
:,
.
:_
..,
,i
-.,.
..
..
..;.
.-
..-
-.
Table 4.3

STREAM FLOWS
Capacity = 360 Million lb/yr
(163,000 metric tondyr)
(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)
Stream Flows (lb-mol/hr)

(12)
(11)
(13)
--
--
(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)
Stream Flows (lb-mol/hr)

(36)
(37)
(36)
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
Add acid to achieve pH = 3.

tMixture
.
of high and low molecular wt polymers.
25
Process Discussion
It was necessary to make several assumptions in closing the material
balance.
It was assumed that polymers of varying chain length and di-
isopropyl ether are the only by-products formed in significant quantity.

Some of the polymers were assumed to have higher boiling points than
water and accordingly to circulate between the catalyst storage (T-101)
and the reactor.
stream 50.
A buildup of the polymer is prevented by use of bleed
Most of the low boiling polymers are assumed to distill over-
head in column C-201, the remaining polymers being removed as bottoms

from C-202.
The vapor-liquid equilibrium constants required for estimating
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.
The preferred acid has not been revealed; however,
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.
It is not known whether
the distillate from C-101 contains components corrosive to carbon steel.

Nonetheless, because of the low cost entailed, SRI treated the distillate
with caustic before beginning purification of the IPA.
If corrosive com-
ponents are present in the distillate, it will be necessary to change the

choice of materials for E-108 and V-102 from carbon steel to stainless.
SRI is not informed on the commercial technology used for treatment
of IPA with activated carbon.
practice is not known.
speculative one.
In addition, the purpose and extent of this
As a result, SRI's design for the treatment is a
It would seem probable that the use of activated carbon
is justified commercially on the basis of improving odor.*
Tokuyama Soda has informed SRI that its IPA customers do not require
an activated carbon treatment of the product.
27
The following sequence is used in each of two columns:

.
Impurities adsorbed from anhydrous IPA by use of a flow

of 2,800,OOO gal of IPA per charge of carbon (1 lb
carbon/l,000 gal).
Na blow to remove IPA from bed, the IPA being returned

to c-208.
Sweetening off cycle. Process water is used to remove

residual IPA from bed, the effluent liquid being returned
to c-202.
Column recharged with fresh carbon.
Sweetening on cycle.
bed.
Adsorption
Pure IPA is pumped briefly through
(repeat of first item).
During adsorption there may be a tendency of carbon fines or impurities to plug the flow.
A once-a-day backwash with pure IPA should
alleviate the problem.
Cost Estimates
The battery limits and utilities investment, together with other
capital requirements, are given in Table 4.4.
in Table 4.5.
Production costs are given
Figure 4.2 shows production cost as a function of plant
capacity and operating level.

Tokuyama Soda has made public cost and performance data for their
process (67573).
This information is compared with SRI's as shown below:
Tokuyama
Soda
(67573)
SRI
Battery limits investment for 30,000 metric

tons/yr (million $1
$2.6*
$2.3
Raw materials and utilities

Propylene (lb/lb)
Steam (lb/lb)
Electricity (kwh/lb)
0.72-t
3.5
0.09
0.73t
4.4
0.04
Based on 266 yen = US$l.

t
As pure propylene.
28
Table 4.4
TOTAL CAPITAL INVESTMENT
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-
Battery limits equipment,

f.o.b.
Reactors
Columns
Vessels & tanks
Exchangers
Compressors
Pumps
Total
Battery limits investment
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
Utilities & tankage

117,700
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
BATTERY LIMITS &

Ul'ILITIESCOST
$10,273,000
0.80
0.71
$6,504,000
b.80
0.72
$3.769,000
0.80
0.68
Total
General service facilities et 15% of above

TOTAL FIXED CAPITAL
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
TOTAL CAPITAL INVBS'I?dBNT,

$16,104,000
not including land
Interest calculsted over half of construction Period of 16 months,
Table 4.5

PRODUCTION COSTS
Capacity = 360 Billion lb/yr
(163,000 metric tons/yr)
CE Cost Index = 142
Basis or Unit Cost
Units/lb
c/kg
Costs by Section (thousand $/yr)

Reaction-Recovery
Thousand
Section
Wyr
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)
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)
Zc/l,OOO gal (0.528c/cu m)

$1.35/1,000 lb ($2.98/tori))
35$/1,000 gal (9.25c/cu m)
1.35$/kwh (1.35'$/kwh)
9Ochillion
Btu (0.357c/ton cal)
15$/1,000 scf (0.53c/cu m)
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
8oo/oof total labor
0.09
0.20
326
Taxes and insurance
2%/yr of fixed capital
0.07
0.15
236
Plant cost
3.40
7.47
12,198
G&A, sales, research
0.75
1.65
2,700
Cash expenditures
4.15
9.12
14,898
10o/o/yrof fixed capital
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
By-product fuel credit,

streams 6 and 10
NET PRODUCTION COST
60c/million
Btu
(0.07)
(0.15)
4.48
9.85
11
4
(240)
16,087
31
Figure 4.2
EFFECT OF CAPACITY AND OPERATING LEVEL ON PRODUCTION
COST
6.5
l-
I -
4.0
3.5
3.0
.5
.52 .54 .56 .5B .6
,fi
.7
OPERATING
LEVEL,
33
.75
.a .05 .9 .951.0
fraction of design capacity
ISOPROPANOL BY A PROCESS USING CATION

EXCHANGE RESIN CATALYST
This section presents a design case based on a cation exchange resin

catalyst.
Although SRI drew heavily on literature published by Deutsche
Texaco, the design is not intended to represent the commercial practice

followed by Deutsche Texaco.
Section 3 contains a review of patents and
the technologies of Tokuyama Soda and Deutsche Texaco.
Process Description
The flow diagram for SRI's design case is shown in Figure 5.1.
The
plant is composed of the following two sections:

100 section:
Propylene and water are converted to crude IPA
200 section:
Crude IPA is concentrated and refined to form

~91~01%
IPA and anhydrous IPA.
The design is based largely on Deutsche Texaco articles and patents

(67569, 67570, 67571, 67572, 67575).
A patent (67472) assigned to
Rheinpreussen, which is integrated with Deutsche Texaco, is believed to

also have application.
Table 5.1 shows pertinent details of the reaction system.
Table 5.1
BASES FOR REACTOR DESIGN
Reaction temperature (OF)

Molar ratio of water/olefin in feed
Conversion of propylene per pass (%)
Selectivity of IPA on propylene (%I
Yield of IPA on propylene per pass (%I
STY [g IPA/(hr x liters of catalyst)]
35
265-300
1200
13.75
75
96
72
108
The exact processing steps used by Deutsche Texaco for purifying

two grades of alcohol, if indeed this was the intent, were not clear from
the literature.
As a result SRI made assumptions in the design of the
purification section.
It is understood that Deutsche Texaco uses a
significantly different purification train and only produces anhydrous

premium grade alcohol.
Major equipment and utility requirements are tabulated in Table 5.2.
Stream rates for producing N360million
Table 5.3.
lb/yr of 100% IPA are given in
The production is split between -91~01%
IPA (30.4 million
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.?
The liquid phase
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.
The liquid phase
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.
Half of the product is sent to the acetone plant, the
remainder is pumped to C-204 for dehydration.

Benzene (stream 32) as used as reflux in C-204 and acts as an
azeotroping agent for removing water from IPA.
The water that is distilled
is condensed, separated from a benzene layer, and eventually removed as

bottoms from PAC-101.
The aqueous bottoms (stream 28) from C-202 contains sodium ions and
possibly some iron ions that must be removed
used in R-101.
before the water can be re-
This is accomplished by routing stream 28, as well as
stream 22, through ion exchange resins in PAC-101.
In SRI's design
PAC-101 operates with two columns (A&C) on stream while duplicate columns
undergo some stage of regeneration.*
Stream
28,
in combination with water
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.
The effluent is passed down-
ward through a second column containing a weak base anion exchanger, such
as Dowe #
WGR, to remove S04-- ions.
Regeneration of the cation exchanger
is accomplished by washing with 0.075 wt% HaSO, (stream 16) followed by

a thorough water rinse (stream 15).
The cycle for each of two fully automated cation exchange columns
is as follows:
8 hours on stream
10 minutes backwash
It is understood that Deutsche Texaco uses a significantly different

design than SRI for PAC-101.
37
40 minutes acid wash
40 minutes rinse.
Because of the lack of information on SO,"
content, the size of
the anion exchange columns was arbitrarily made the same as that of the
cation exchange column.
No effort was made to fix the sodium hydroxide
(stream 14) and rinse requirements
(stream 13) for the regeneration of
column A.
Anhydrous IPA is taken 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.
38
Table 5.2
Capacity =,360 Million lb/yr (163,000 metric
Bquipment
Number
R-101
Name
Reactors (4 units)
Height
(ft)
Diameter
(ft)
40
8.0
316 ss-clad shell
Remarks
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
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
Propylene storage tank

(2 units)
(2 units)
(2 units)
(2 units)
steel
steel
steel
steel
steel
steel
steel
steel
steel
steel
(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... _
Table 5.2 (Concluded)

tons/yr)
@
Equipment
Number
Remarks
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:

Utilities Summary (Average Consumptions)
Battery limits
Total
100
Section
--
17,200
2,700
83
63
200
Section
a,
Cooling water
(gpm)
14,500
Process water (gpm)

Electricity (kw)
1,lSS
794
394
Steam used at 150 psig (lb/hr)
279,000
4,000
275,000
Inert gas, low pressure (scfh)
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
ISOPROPANOL BY A PROCESS USING

CATION EXCHANGE RESIN CATALYST
,........................................................................................................................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
water Far PAC-101
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

STREAM FLOWS
(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)
stream Flows (lb-mols/hr)

(11)
--- (12)
--
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
Stream Flows (lb-mols/hr)*
(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
Streams 13, 14, 17, and 18 were not estimated.
43
Process Discussion
It was necessary to make several assumptions in closing the material
bal
ante.
It was assumed that polymers of varying chain length and di-
isopropyl ether are the only by-products formed in significant quantity.

Some of the polymers were assumed to have higher boiling points than
water and accordingly to circulate between T-102 and the reactor.
buildup of the polymer is prevented by use of stream 12, which is used

along with acid for regeneration of the cation exchanger.
Most of the
low boiling polymers are assumed to distill overhead in column C-201.

The vapor-liquid equilibrium constants required for estimating the phase
split in V-101 are not known, hence the material balance at this point
in the process is uncertain.
SRI designed for a slight rise in temperature through the reactor.
A recent Deutsche Texaco patent (67570) describes operation with a fairly
uniform temperature through the reactor.
Over a period of time temperature
is allowed to increase to compensate for a decrease in catalyst activity.

The SRI design for the ion exchange treatment is highly speculative.
This was caused by lack of knowledge of the identity and quantity of all
of the ions present.
SRI is not informed on the commercial technology used for treatment
of IPA with activated carbon.
this practice is not known.
is a speculative one.
In addition, the purpose and extent of

As a result, SRI's design for the treatment
It would seem probable that the use of activated
carbon is justified commercially on the basis of improving odor in top

quality cosmetics.
The following sequence is used in each of two columns:
l
Impurities adsorbed from anhydrous IPA by use of a flow

of 2,800,OOO gal of IPA per charge of carbon (1 lb carbon/
1,000 gal).
Na blow to remove IPA from bed, the IPA being returned

to c-202.
Sweetening off cycle. Process water is used to remove

residual IPA from bed, the effluent liquid being returned
to c-202.
45
Column recharged with fresh carbon.
.Sweetening on cycle.
through bed.
Adsorption
Pure IPA is pumped briefly
(repeat of first item).
During adsorption there may be a tendency of carbon fines or impurities

to plug the flow.
A once-a-day backwash with pure IPA should alleviate
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.
Production costs are given
Figure 5.2 shows production cost as a function of plant
capacity and operating level.

Deutsche Texaco has supplied cost and performance data for its
process.
This information is compared with SRI's in the tabulation that
follows.
Cooling water is much higher for SRI's design; possibly, Deutsche
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 $1
Raw materials and utilities
Propylene (lb/lb)
Steam (lb/lb)
Cooling water (gal/lb)
Process water (gal/lb)
Electricity (kwh/lb)
Based on 3.22 DM = US$l.

t
As pure propylene.
46
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
TOTAL CAPITAL INVESTMENT
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
Battery limits equipment,

f.o.b.
Reactors
columns
Vessels & tanks
Exchangers
Compressors
Pumps
Total
Ion exchanger
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
Utilities and tankage

Cooling water
Process water
Steam
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
Utilities & tankage

investment
$ 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
General service facilities at 15% of above

TOTAL FIXED CAPITAL
Interest on construction
loan at 9.5$/yr*
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
Interest calculated over half of construction period of 15 months.
47
Table 5.5

PRODUCTION COSTS
CE Cost Index = 142
Total Costs
Thousand
Basis or Unit Cost
Units/lb
4 men/shift, $6.25/man-hr
0.0001 man-hr
$/yr
Costs by Section (thousand $/yr)

Purification
Reaction-Recovery
Section
Section
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
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)
2c/l,OOO gal (0.528c/cu m)

$1.35/1,000 lb ($2.98/tori))
35$/1,000 gal (9.25c/cu m)
1.35c/kwh (1.35$/kwh)
15c/1,000 scf (0.53$/cu Ill)
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
80% of total labor
0.10
0.22
367
Taxes and insurance
2%/yr of fixed capital
0.06
0.13
228
Plant cost
3.58
7.88
12,940
G&A, sales, research
0.75
1.65
2,700
Cash expenditures
4.33
9.53
15,640
Depreciation
lOX/yr of fixed capital
0.32
0.71
1,138
Interest on working capital
9.5Wyr
0.07
0.15
254
4.72
10.39
17,032
TOTAL PRODUCTION COST
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
ISOPROPANOL BY A PROCESS USING CATION EXCHANGE RESIN CATALYST

EFFECT OF CAPACITY AND OPERATING LEVEL ON PRODUCTION COST
7.0
I I I
I I I
.65
.7
.75
I-
6.5
3.5
3.0
I
.5
.S2 ..54 .56.58 .6

OPERATING
LEVEL,
.a .a5 .9 .951.0
fraction of design capacity
51
UPDATED PROCESSES FOR VAPOR PHASE

DIRECT HYDRATION OF OLEFINS
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.
Table 6.1 summarizes the results.
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.
For the process producing isopropanol, the
following adjustments were made to the 1969 case:

.
Plant capacity was increased to correspond to designs

in Sections 4 and 5 of this report.
Provision was made to produce 91 ~01% IPA (produced

in 1969 report) and anhydrous IPA. The revised design
produces products corresponding to those of the designs
in Sections 4 and 5 of this report.
Costs were updated.
In the earlier report, SRI also evaluated a process based on Pullman

technology.
No updating of that process was attempted in the current
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
Ethanol (95 ~01%)
Isopropanolt
Organic feed
Ethylene
Propylene
Plant capacity (million lb/yr of

alcohol)
187 (as 199%)
360
Average reaction temperature (OF)
530
407
1000
590
Molar ratio of water to olefin at

reactor inlet
0.50
0.95
(as
100%)
Number of reactors
Type of reaction system
Downflow of reactants
over catalyst
Downflow of reactants
over catalyst
Yield of olefin/pass (%I
4.4
5.6
Conversion of olefin/pass (%I
4.4
5.7
Reactor space-time-yield [g alcohol/

(hr x liter)]
91
101
Plant yield on olefin (%I
81
84
9.3
71.2
0.056
2,650
4.5
44.4
0.026
3,260

(million $1
7.7
8.5
Utilities and tankage investment

(million $1
2.69
3.6
TOTAL FIXED CAPITAL, not including

waste disposal (million $1
11.89
13.9
6.61
(0.17)
5.21
(0.13)
6.449
'5.08
Utilities,* per lb of alcohol

Steam (lb)
Cooling water (gal)
Power (kwh)
Natural gas (Btu)
Production cost** (C/lb)

Total production cost
Fuel credit for bleed
stream
NET PRODUCTION COST, excluding

waste disposal and royalty
Current confidence rating
*
Now Veba-Chemie.
t 50% of capacity to 91 ~01% IPA, 50% to anhydrous IPA.

0
Battery limits.
0Off-site tankage not included.
Depends on specific denaturing requirements.
**Ethylene at 3.5c/lb, propylene at 2.8Wlb.

Ethylene consumption for ethanol =
0.7707 lb/lb ethanol; propylene consumption for IPA = 0.8508 lb/lb IPA.
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.
This area was selected because it is
the petrochemical center of the United States.
The capital costs for
other locations have been correlated with Houston costs.
Cooling Water Conditions

Cooling water conditions assumed for the designs in this report
are:
Dry bulb air temperature
Wet bulb air temperature
Cooling water temperature
Cooling water range
100F
SOOF
85'F
20F
Definitions
The following definitions of terms are used in this report:
Conversion
- ratio of material reacted to material fed,

mol%
Selectivity
- ratio of product desired to material reacted, mol%
Space-time yield - product rate per unit reactor volume,

g/(hr x liters)
(SW
Space velocity
(Sv)
- (volume of feed per hour at STP)/volume

of catalyst, hr-'
STP
- standard temperature and pressure
Ton
- the short ton (2,006 lb avoirdupois) is

used in material balances
Yield
- ratio of product desired to material fed,

mol%
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-
eral services facilities not directly associated with process operations

were assumed to be 15% of battery limits and utilities investment.
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%.
It does not al,low for fringe benefits, which were assumed to be

The effective total rate was estimated at $6.25/hr, using a 10%
shift overlap.
Operating labor requirements were estimated subjectively
and reflect the complexity of the process.

Total maintenance costs were assumed at 6% of battery limits investment with a fifty-fifty split between materials and labor.
Major raw material costs were based on estimated contract prices or
refinery transfer values.
Prices of other materials were based on sale
values reported by the U.S. Tariff Commission or listed market prices.

Utility costs were those given by Bauman (B-2) for the Gulf Coast area.
Factory overhead was also arbitrarily assumed.
It includes all staff
personnel located at the plant site and services directly associated with
operations and maintenance.
Confidence Ratings
SRI uses only nonconfidential
Economics Program.
information in studies for the Process
Data on pilot plant operations are seldom available,
and frequently even data on physical properties are incomplete or absent.

56
Therefore,
in some instances, there may be enough information to enable
rigorous calculation, but most often only simplified design methods are
warranted.
The factoring methods used in the estimation of capital costs
also have some limitations.
Errors in the design and cost of individual
equipment items, nevertheless, do tend to randomize, and it is believed

that the estimated capital costs for the overall process as described are
usually accurate within l 20%.
The greatest fundamental uncertainty lies in the conception of the
The degree of uncertainty varies widely among studies,
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.
An "A" rating is used when a relatively large
amount of basic design information is available, when the process scheme

is firmly established, and when there has been an opportunity to verify
SRI's evaluation through either the comments of reviewers or comparison
with other cost data.
A "D" rating, on the other hand, is used when
little information is available, and when there has been inadequate

verification.
"B" and "C" ratings are subjective appraisals of inter-
mediate situations.
Some production-cost elements are considered in arriving at confidence ratings.
These may include operating and maintenance labor re-
quirements, materials consumption, and utilities usage.
Prices of mate-
rials are not usually considered in confidence ratings, because SRI may
not have access to prevailing contract prices.
However, the prices used
in this report are SRI's best estimates of either contract prices or

transfer charges.
Other charges, such as G&A, are necessarily arbitrary
and are also omitted from the confidence ratings.

It should be emphasized that any rating is applicable only to the
process scheme presented in the report.
The process may be based on a
patent assigned to a particular company, but it should not be taken as

representing the process used by that company, or offered by a licensor,
unless it is so stated in the report.
57
Table B.l
Process
Isopropanol from propylene, Figure
4.1
(Tokuyama Technology)
Isopropanol from pr*

pylene, Figure 5.1
(process using
cation exchange
resin catalyst1
SUMMARY OF
WASTE STREAMS
Stream
Number
Source
of Waste
IN SRI DESIGN CASES*
Flow Rate of Component
Remarks
6 (g)
R-101
2,186 lb/hr of propane

and propylene
To fuel
10 629
c-101
104 lb/hr of propane

propylene
and
To fuel
25 (1)
c-201
7,960 lb/hr of water

some IPA
and
To waste pond or
incinerator
26 (11
c-202
211 lb/hr of aqueous NaOH

with traces of polymer
To wastc pond or
incinerator
47 (1 + s)
C-206A&B
194 lb/hr of water with

some carbon
To waste pond aftcsr

filtering
46 (1)
C-201
629 lb/hr of isopropyl

ether with some water,
alcohol, and polymer
To fuel
50 (1)
c-101

traces of polymer
To waste pond or
incinerator
10 (1)
v-101,2
3,931 lb/hr of propane

and propylene
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
To waste pond after

neutralization
25 (1)
c-201

some IPA
To waste pond or
incinerator
47 (1 + s)
C-206A5B
194 lb/hr of water with

some carbon
To waste pond after

filtering
48 (1)
c-201
1,780 lb/hr of isopropyl

ether with some water,
alcohol, and polymer
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
Burleson, J. C., et al. (to Monsanto), "Manufactureof Alcohols

from HydrocarbonsUsing a Silent Electric Discharge,"US
3,497,436 (Feb. 24, 1970)
67472
RheinpreussenA.G. Fuer Bergbau und Chemie, "Preparationof

Alcohols and Ethers," Belgian 716,619 (Dec. 16, 1968)
67477
Mizutani, Y., et al. (to Tokuyama Soda), "Alcohols from Hydration

of Olefins," US 3,450,777 (June 17, 1969)
67494
Rosscup, R. J., et al. (to Standard Oil, Indiana), "Process for

the Production of Alcohols,w US 3,548,013 (Dec. 15, 1970)
67499
Tokuyama Soda, "MonohydricAlcohols Preparation,"British

1,281,120 (July 12, 1972)
67521
Asahi Chemical Industry, "Preparationof Alcohols," Japanese

45-29163 (Sept. 24, 1970)
67523
Mitsui Toatsu Chemicals, "Olefin Hydration Catalyst, "#Japanese

47-23523 (June 30, 1972)
67524
Mitsui Toatsu Chemicals, "HydrationCatalyst for Olefins,"

Japanese 47-23524 (June 30, 1972)
67525
Toray, "Productionof Alcohols by Direct Hydration of Olefins,"

Japanese 47-45323 (Nov. 15, 1972)
67529
Schmerling, L. (to Universal Oil Products), "Alcohols by Catalytic

Reaction of Alkenes with Water," French 2,059,240 (May 28,
1971)
67531
Veba-Cheaie, "CatalyticHydration of Ethylene and Propylene,"

French 2,072,568 (Sept. 24, 1971)
67532
Dalin, M. A., et al., "IsopropanolProduction,"French 2,098,801

(March 10, 1972)
67543
Celanese, "Olefin Hydration with Water Using Ion Exchange Resin

Catalyst," British 1,238,556 (July 7, 1971)
63
67549
Mesich, F. G. (to Celanese), "Alcohol Production,"US 3,644,497

(Feb. 22, 1972)
67562
Izumi, Y., et al. (to Tokuyama Soda), "CatalyticHydration of

Olefins," French 2,132,257 (Nov. 17, 1972)
67563
Izumi, Y., et al. (to Tokuyama Soda), "Hydrationof Olefins,"

Japanese Kokai 47-30608 (Nov. 9, 1972)
67564
Izumi, Y., et al. (to Tokuyama Soda), "Hydration of Propylene,

Ethylene, and Butene," Japanese Kokai 47-31909 (Nov. 14, 1972)
67565
Izumi, Y., et al. (to Tokuyama Soda), "Hydrationof Propylene,

Ethylene, and Butene," Japanese Kokai 47-31908 (Nov. 14, 1972)
67568
Massie, Sr N. (to Universal Oil Products), "Preparationof

Alcohols by Catalytic Hydration of Olefinic Compounds,tl
US
3,705,912 (Dec. 12, 1972)
67569
Brandes, G., et al. (to Deutsche Texaco), "IsopropylAlcohol by

Catalytic Hydration of Propene," German Offen. 2,147,737
(March 29, 1973)
67570
Brandes, G., et al. (to Deutsche Texaco), "ContinuousManufacture

of IsopropylAlcohol," German Offen. 2,147,739 (April 5, 1973)
67571
Brandes, G., et al. (to Deutsche Texaco), ?ontinuous Manufacture

of IsopropylAlcohol," German Offen. 2,147,740 (April 5, 1973)
67572
Brandes, G., et al. (to Deutsche Texaco), "Isopropanolby

Catalytic Hydration of Propene," German Offen. 2,147,738
(March 29, 1973)
67573
Tokuyama Soda Co., Ltd., "Tokuyama'sDirect Hydration IPA Process," Technical Brochure, 1973
67575
Neier, W., et al., 'Use Cation Catalyst for IPA," Hydrocarbon

Process. (November 1972), 113-16
67576
Neier, W., et al., "IsopropylAlcohol by Direct Hydration,"

Chem. Tech. (February 1973), 95-9
67578
Kanamaru, M., et al. (to Mitsui Toatsu Chemicals), "Olefin

Hydration to Alcohols," Japanese Kokai 48-26711 (April 9, 1973)
67579
Kanamaru, M., et al. (to Mitsui Toatsu Chemicals), "Alcohols

from Olefins by Catalytic Hydration," Japanese Kokai 48-32809
(May 2, 1973)
64
67580
Tsumura, R., et al. (to Mitsui Toatsu Chemicals), "Alcohols

from Olefins by Catalytic Hydration," Japanese Kokai 48-32810
(May 2, 1973)
100888
Edison International,"Liquid Phase Oxidation of Olefins,"

British 1,166,121 (Oct. 8, 1969)
323154
Veba-Chemie, 'ImprovementsIn and Relating to the Production

of Alcohols by Hydration of Olefins,' British 1,269,553
(April 6, 1972)
Books
B-l
Perry, T. H., et al., eds., "Chemical Engineers' Handbook," 4th

ed., McGraw-Hill,New York, 1963
B-2
Bauman, H. C., "Fundamentalsof Cost Engineering in the Chcmicnl

Industry,"Reinhold, New York, 1964
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
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

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Ethanol and Isopropanol, Synthetic, Supp. A.

Part 1, January 1974

Ethanol and Isopropanol, Synthetic, Supp. A. Part 1, January 1974

ISOPROPANOL BY DIRECT HYDRATION OF PROPYLENE:

Tokuyama Technology .....................

ISOPROPANOL BY TOKUYAMA TECHNOLOGY

Process Description .....................

ISOPROPANOL BY A PROCESS USING CATION EXCHANGE

Process Description .....................

UPDATED PROCESSES FOR VAPOR PHASE DIRECT HYDRATION

DESIGN AND COST BASIS

SUMMARY OF WASTE STREAMS ..............

PATENT REFERENCES BY COMPANY

Ethanol and Isopropanol, Synthetic, Supp. A. Part 1, January 1974

Equilibrium Conversion of Propylene to Isopropanol

Isopropanol Production Rate with

Isopropanol by Tokuyama Technology

Isopropanol by Tokuyama Technology

Isopropanol by a Process Using Cation Exchange

Isopropanol by a Process Using Cation Exchange

Ethanol and Isopropanol, Synthetic, Supp. A. Part 1, January 1974

Process for Producing Isopropanol by Liquid Aqueous

Process for Producing Isopropanol by Liquid Aqueous

Isopropanol by Direct Hydration of Propylene

Tokuyama Experimental Data

Isopropanol by Tokuyama Technology

Isopropanol by Tokuyama Technology

Isopropanol by Tokuyama Technology

Isopropanol by Tokuyama Technology

Isopropanol by Tokuyama Technology

Isopropanol by a Process Using Cation Exchange

Isopropanol by a Process Using Cation Exchange

Isopropanol by a Process Using Cation Exchange

Isopropanol by a Process Using Cation Exchange

Isopropanol by a Process Using Cation Exchange

Ethanol or Isopropanol by Vapor Phase Direct

Summary of Waste Streams in SRI Design Cases

Ethanol and Isopropanol, Synthetic, Supp. A. Part 1, January 1974

This report emphasizes the economics and technology for isopropanol

Design cases based in

part on Tokuyama Soda and Deutsche Texaco technologies are included.

Tokuyama Soda and Deutsche Texaco have commercial isopropanol

plants that presumably use technologies somewhat similar to those described

Ethanol and Isopropanol, Synthetic, Supp. A. Part 1, January 1974

This report emphasizes the manufacture of isopropanol (IPA) by the

SRI also updated designs for ethanol and

isopropanol manufacture (see Section 6) by direct hydration that were

The current re-

When feasible, SRI used information authored by Deutsche Texaco

personnel for the latter process.

Even though the two processes have

significantly different reaction systems, the overall economics appear

Both of these processes apparently offer superior

economics to the vapor phase direct hydration process (Hibernia-Scholven*

However, the SRI design for

the updated process contains appreciable uncertainties

that could well

Both processes have been

commercialized in the last several years and appear to offer advantages

Ethanol and Isopropanol, Synthetic, Supp. A. Part 1, January 1974

Battery limits, excluding catalyst

Utilities and tankage

Labor (operators, maintenance,