728 Section 5 The Professional Engineer, the Environment, and Communications
B.3 PRODUCTION OF ACETONE VIA THE DEHYDROGENATION
OF ISOPROPYL ALCOHOL (IPA) [1,2,3,4]
B.3.1 Process Notes
The prevalent process for the production of acetone is as a by-product of the :
manufacture of phenol. Benzene is alkylated to cumene which is further oxidized
to cumene hydroperoxide and finally cleaved to yield phenol and acetone. How-
ever, the process shown in Figure B.3 and discussed here uses isopropyl alcohol
(IPA) as the raw material. This is a viable commercial alternative and a few plants
continue to operate using this process. The primary advantage of this process is
that the acetone produced is free from trace aromatic compounds, particularly
benzene. For this reason acetone produced from IPA may be favored by the phar-
maceutical industry due to the very fight restrictions placed on solvents by the
Food and Drug Administration (FDA). The reaction to produce acetone from IPA
is given below:
vor PMOIAB E401 R01 E402 E403 P402NB HOT Veo. T-401
IPAFeeé IPAFeed IPAFeed IPA Reactor Trim Reactor Reactor Phase Acetone
Drum Pumps Vaporizer Reactor Effluent Cooler Cooler Heater Pumps Fumace Separator Stripper
Process Water ’ 5
poe
'soPropy! Alcoho!
Figure B.3 Preliminary Process Flow Diagram for the Production of Acetone
from Isopropyl Alcohol (Unit 400)
Arabyeis, Spillegs aut Paje Chuical Paste
Richard Tavtou 2+ al.Appendix B Information for the Preliminary Design of Four chemical Processes 729
(CH;);CHOH = (CH,),CO + H,
Isopropyl Alcohol Acetone
The reaction conditions are typically 2 bar and 350°C, giving single-pass conver-
sions of 85-92 %.
B.3.2 Process Description
Referring to Figure B.3, an azeotropic mixture of isopropyl alcohol and water (88
‘wt% IPA) is fed into a surge vessel (V-401) where it is mixed with the recycled
unreacted IPA/water mixture, Stream 14. This material is then pumped and va-
porized prior to entering the reactor. Heat is provided for the endothermic reac-
tion using a circulating stream of molten salt, Stream 4. The reactor effluent, con-
taining acetone, hydrogen, water, and unreacted IPA, is cooled in two exchangers
prior to entering the phase separator (V-402). The vapor leaving the separator is
(Text continues on p. 735)
T402 E404 V409. «E405. PHOSAIB P-4OAN'B T-409 E405 E407 V-404 P-4OSA/B E408
Acetone Acetone Acetone Acetone Acetone IPA IPA PA IPA IPA IPA Waste
Column Overhead Reflux Reboiler Reflux Column Column Overhead Reboiler Retlux Reflux Water
Condenser Drum Pumps Pumps Condenser Drum Pumps Cooler
Acetone
v-a08
403 AB
0s A
ow Je
408 AB £403 Waste Water
FA presi tar [TRS Deg = Acetone Pres]
Sener oo
Acetone from Isopropyl Alcohol (Unit 400) —— ed
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ale B.6 (Continued) oa
Stream No. 9 10 11 12 13 14 15 16 ce
Temperature (°C) m2 6 61 9 8 83 10933
Pressure (bar) 16 0¢«415 «15h 1200120«1A 2
Vapor Fraction 00 00 00 00 00 00 00 10
Mass Flow (tonne/h) 279 «422,«188 (092823 0.27 0.65 «O24
Mole Flow (kmol/h) 74.02 7251 32.29 41.73 1718 588 3585 38.60
Component Mole Flow
(kmol/h)
Hydrogen 00 —- -—- -~ ~~ =~ = 32 i
Acetone 3243 7246 3227 016 «482016 =~ 2.51
Isopropyl Alcohol 381 0.05 002 382 11510 382 — 0.02 -
Water 3775 87.75 5726 1.90 35.85
Utility hps cw ow cw ips, cw ips cw
Equipment E401 E402. E403 E40 E405 E406 E407 E408
Temperature 254 30 5 30 «16030160 30
In °C)
Temperature 254 40,15 40 160 «40160 40
Out °C)
Flow 209 7790 1350 74.00 168 «176003550 4.16
(tonne/h)Appendix B Information for the Preliminary Design of Four chemical Processes 735
scrubbed with water to recover additional acetone, and then this liquid is com-
bined with the liquid from the separator and sent to the separations section. Two
towers are used to separate the acetone product (99.9 mole %) and to remove the
excess water from the unused IPA, which is then recycled back to the front end of,
the process as an azeotropic mixture. Preliminary equipment summaries and
stream information are given in Tables B.5 and B.6, respectively.
B.3.3 Reaction Kinetics
The reaction to form acetone from isopropyl alcohol (isopropanol) is endothermic
with a standard heat of reaction of 62.9 kJ/mol. The reaction is kinetically con-
trolled and occurs in the vapor phase over a catalyst. The reaction kinetics for this
reaction are first order with respect to the concentration of alcohol and can be es-
timated from the following equation [3,4]:
E,
Tra = erp] Rt |°
gas _ kmol
ita = gas
with E, = 72.38MJ/kmol, ky = 351 x 10° =,
s TP reactor §
In practice, several side reactions can occur to a small extent. Thus, trace quanti-
tics of propylene, diisopropyl ether, acetaldehyde and other hydrocarbons and
oxides of carbon can be formed [1]. The non-condensables are removed with the
hydrogen while the aldehydes and ethers may be removed with acid washing or
adsorption. These side reactions are not accounted for in this preliminary design.
For the design presented in Figure B.3, the reactor was simulated with cata-
lyst in 2 inch (50.4 mm) diameter tubes each 20 feet (6.096 m) long and with a
cocurrent flow of a heat transfer medium on the shell side of the shell and tube
reactor. The resulting arrangement gives a 90% conversion of IPA per pass.
8.3.4 Vapor-Liquid Equilibrium
Isopropyl alcohol and water form a minimum boiling point azeotrope at 88 wt%
isopropyl alcohol and 12 wt% water. Vapor-liquid equilibrium (VLE) data are
available from several sources and can be used to back-calculate binary interac-
tion parameters or liquid-phase activity coefficients. The process presented in
Figure B.3 and Table B.6 was simulated using the UNIFAC thermodynamics
package in the CHEMCAD™ simulator. This package correctly predicts the for-
mation of the azeotrope at 88 wt% alcohol.