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Department of Chemical & Biomolecular
Senior Design Reports (CBE)
Engineering
4-9-2002
Aurindam Ghatak
University of Pennsylvania
Claire Pinto
University of Pennsylvania
daRosa, Calvin; Ghatak, Aurindam; and Pinto, Claire, "Production of Acetaldehyde from Acetic Acid" (2002). Senior Design Reports
(CBE). 45.
http://repository.upenn.edu/cbe_sdr/45
The economics of the process is strongly dependent on the price of acetic acid, and we examined scenarios
under which acetic acid was available at either $0.16/lb or $0.12/lb. The total capital investment in either
situation is approximately $47,000,000. If acetic acid is available at $0. 16/1b, we estimate an IRR of 11.3 %,
but if acetic acid can be purchased for $0.12/Ib the IRR is 18.5% after 20 years. It is our recommendation to
pursue more research into projecting both the cost of acetic acid and the market for acetaldehyde. If acetic
acid will be available at the lower price, the company should pursue production of acetaldehyde.
Authors:
Calvin daRosa
Aurindam Ghatak
Claire Pinto
Faculty Advisor
April 9, 2002
University of Pennsylvania
/,.,
0rJ~11 6( /1 L ,::;'1./ 6:.r/ J} - ~
Cl
I
09 April 2002
Enclosed in this report is the completed economic analysis of our proposed process. The
process is designed to produce and recover acetaldehyde at high purity from acetic acid.
This process design recovers 12,818 lblhr of acetaldehyde by extractive distillation at
99.6 % weight purity. A second commodity chemical, ethyl acetate, is produced as a
byproduct in this process and is purified by a series of distillation columns. Ethyl acetate
is produced at a rate of 1,139 lblhr and purity of 99.6 weight percent.
Capital cost estimations and profitability analysis have been completed for our process.
Financial modeling of our process assuming the price of acetic acid to be 0.16/lb yielded
an Investors Rate of Return (IRR) of 11.4 % and a Total Capital Investment (TCI) of
$47,242,990. This scenario is not economically feasible. However, when the price of
acetic acid is taken to be $0.12/lb, the IRR and TCI are 18.5 % and $47,224,990
respectively. In the light of that fact that the possible legislation ofMTBE out of gasoline
might make this process more economically attractive, the group recommends further
research into the feasibility of such a plant and the possible future construction of the
facility given the realization of the second scenario.
Sincerely,
~0?d4---
Calvin P. daRosa
~ Aurindam K. Ghatak
{)jJaU~~
CO'
Claire L. Pinto
TABLE OF CONTENTS
Condensers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Tanks . . .. . .................................................. 67
Equipment Cost Summary......... . ..... . ..... ...... . .. . .. . ...... . .... . ... . ........ 135
Fixed-Capital Investment Summary.................... ...... . ..... ... ... .... . .... 137
Important Considerations ...... , .... . ... . .. . .... .. ... '" .... .. ..... . ..... . .. ........ .141
Operating Cost and Economic Analysis ................. ...... . ..... .......... .. . 145
Bibliography.... ........ , .. .. ..... . ....... . .......... . , ...... . .... .. ... ....... . ....... 162
Appendix A: Unit Cost Calculations . . ........ ... ..... .. .... . ..... . ..... ...... . .. .163
Appendix B: Utility Cost Calculations ... .. .................... . ... .... .......... .201
Appendix C: Aspen Plus Results ... . ... . .... . . .. ........ .. ... . ... . ........ . ..... ...207
Appendix D: Problem Statement. ... . .......... . ........... .. ........... ....... .... 269
Appendix E: Patent. .... . ....................... .. ... . ..... . , ..... ............. , ..... .273
Abstract
acetaldehyde by hydrogenation ofacetic acid over a 20% wt. palladium on iron oxide
catalyst. The reaction conditions used are the optimum according to a patent filed by
Eastman Chemical (Tustin, et.al., U.S . Patent No. 6,121,498): temperature is range is
from 557-599 of at a pressure of254 psi. The conversion of acetic acid in the reactor is
carbon dioxide, and the light hydrocarbons methane, ethane, and ethylene. Acetaldehyde
is purified in a series of steps: it is first absorbed with an acetic-acid rich solvent, then
then used to recover additional acetaldehyde from the vapor distillate of the main
separation. Acetic acid is purified and recycled to the reactor to limit the amount of
The economics of the process is strongly dependent on the price of acetic acid,
and we examined scenarios under which acetic acid was available at either $0.16/Ib or
If acetic acid is available at $0. 16/1b, we estimate an IRR of 11.3 %, but if acetic acid can
be purchased for $0.12/Ib the IRR is 18.5% after 20 years. It is our recommendation to
pursue more research into projecting both the cost of acetic acid and the market for
acetaldehyde. If acetic acid will be available at the lower price, the company should
6
Introduction
was chosen as the primary product because of its wide use in industry and the
acetate is produced as a side product. Table 1 below shows basic chemical information
Table 1: P -f f duct
Acetaldehyde Ethyl Acetate
(grimary product) {side product)
Synonym Ethanal Acetic acid ethyl ester
Molecular Formula C 2H 4O CH 3COOC 2H s
Molecular Weight 44.05 88.0
CAS No. 75-07-0 141-78-6
Melting point -190.3 OF -117 OF
Boiling point 69.6 OF 171F
Density 0.6149 g/cm J 1.108 g/cm J
I. Uses
the production of pyridine and pyridine bases, peracetic acid, pentaerithritol, butylene
glycol and chloral. It is used in the production of esters, particularly ethyl acetate and
isobutyl acetate (lARC V.36 1985; Chern. Prod. Synopsis, 1985). It is also used in the
esters, paraldehyde halogenated derivatives (lARC V.36, 1985). Acetaldehyde has been
used in the manufacture of aniline dyes and synthetic rubber, to silver mirrors and to
harden gelatin fibers (Merck, 1989). It has been used in the production of polyvinyl acetal
L
resins, in fuel compositions and to inhibit mold growth on leather (lARC V.36, 1985).
explosives, lacquers and varnishes, photographic chemicals, phenolic and urea resins,
compound for the intended use as a flavoring agent (Furia and Bellanca, 1975; HSDB,
goods, fruit juices, candy, desserts, and soft drinks. In 1976, approximately 19,000 Ib of
acetaldehyde were used as food additives, primarily as fruit and fish preservatives and as
Ethyl acetate, the side product of this process, is widely used in printing inks, paints
II. Production
Acetaldehyde was first produced commercially in the United States in 1916. U.S.
(lARC V.36, 1985). There has been an overall decline in the demand for acetaldehyde
due to the use of more economical starting materials for principal derivatives and a lower
demand for some acetal derivatives (Chern. Prod., 1985). However, in recent times due to
estimated U.S. exports of acetaldehyde were 1.2 billion lb (Chemical Products Synopsis,
1985).
Acetaldehyde can be made commercially via the Wacker process, the partial
oxidation of ethylene. The major disadvantage of that process is that it is very corrosive
the reaction is prone to over-oxidation of the ingredient, the products of which are
thermodynamically more stable than acetaldehyde which is the partial oxidation product.
This over oxidation of the ingredient reduces the yield of acetaldehyde produced and
air and ethanol vapor is fed into a multi-tubular reactor. Temperature is maintained
between 750-932 of (400-500 C), and the pressure at 29.4 psi. The catalyst used is
chromium activated copper. Vapor coming out of the reactor is passed through a scrubber
and unreacted ethanol is separated and recycled. However, this process gives a relatively
The process investigated in this report converts acetic acid into acetaldehyde.
generated from inexpensive methanol. Due to the possible legislation ofMTBE out of
gasoline, there may be a worldwide glut of methanol, so any chemicals that use methanol
may become much more economically attractive. That is why acetic acid is our starting
material of choice.
9
The catalyst used in this process is 20% palladium on an iron oxide support. This
catalyst gives a selectivity of 86% to the desired reaction at 46% acetic acid conversion.
Though this process can also be effectively catalyzed by mercury compounds, the toxic
The reaction is carried out in a packed bed reactor at a temperature range between
557 and 599 of. The following reactions occur in the reactor:
Under reaction conditions, the selectivity to reaction (1) is 86%. This facilitates a good
yield of acetaldehyde and further justifies the cost of the reactor conditions. The product
is then passed through an absorber and then separated as the distillate using a fractional
distillation column. The following reaction occurs in the distillation column to produce
ethyl acetate:
azeotrope in the acetic acid separation column, which makes it easier to separate the
acetic acid. This acetic acid is then recycled back to the reactor. After being separated
from the water, first in a decanter and then by distillation, the ethyl acetate is purified to
10
The Gulf Coast is the location of choice for this plant. This is primarily due the region
being an industrial belt. As a consequence, storage facilities as well as raw materials are
readily available and cheap. As mentioned in the problem statement, due to this choice of
location, it is assumed that hydrogen can be purchased over the plant fence for $0.50Ilb at
200 psig. Additionally, the prices of utilities are relatively inexpensive. Natural gas is
psi at $2.46IMLbs.
EP A regulates acetaldehyde under several Acts such as the Clean Air Act (CAA) and
the Clean Water Act (CWA). EPA has established water quality criteria, effluent
guidelines, rules for regulating hazardous spills, general threshold amounts and
requirements for the handling and disposal of acetaldehyde wastes. Process enclosures,
local exhaust ventilation and other engineering controls must be used to maintain
Acetaldehyde is an extremely flammable liquid and vapor. Its vapor may cause flash
ensure that the temperature of the product does not rise above 15C.
Acetaldehyde is also a potential cancer hazard. High vapor concentration may cause
drowsiness or irritation of the eye and respiratory tract. For eye protection, safety glasses
with side shields and a face shield need to be worn by people with risk of exposure.
Additionally, chemical resistant gloves, boots and protective clothing appropriate for the
11
risk of exposure need to be worn. Decontamination facilities such as eye bath, washing
Ethyl acetate, on the other hand, is not subject to EPA emergency planning
requirements under the Superfund Amendments and Reauthorization Act (SARA) (Title
III) in 42 USC 11022. However, ethyl acetate is an irritant of the eyes and upper
respiratory tract at concentrations above 400 ppm [NLM 1992]. Ethyl acetate
eczema of the skin [Hathaway et al. 1991]. As a consequence, ethyl acetate is stored in a
cool, dry, well-ventilated area in tightly sealed containers. Splash-proof chemical safety
goggles or face shields and coveralls should be worn during any operation involving
12
PURGE2
TO TO
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o o
LEGENDS
9 Temperature
;, FEED TODC-SOO)
Y Pressure F-230
LEGENDS OFFGAS
9 Temperature
COOLANT
y Pressure
iY2
l
"
GJ SPLIT FROM DE-720
HAC PRODUCT2
DC-10
HAC PRODUCT1
...l-
SOLVENT FOR Z
AB-320
ACETALDEHYDE FROM ACETIC ACID PROCESS (PART 3 OF 3)
40
TO P-620
28
DE 720
STEAM __ ._~ .
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u.
LEGENDS
y Temperature
STEAM
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~WASTEWATER
MATERIAL BALANCE
Item Number: S-101 S-102 S-103 S-103b S-104 S-201 S-202 S-203 S-204 S-205
Temperature (oF) 77 263.2 369.9 369.9 238 241 .9 280.10 464.7 477.6 599
Pressure (psia) 14.7 20.1 98 .6 98 .6 14.7 263 .0 245 .9 255.0 254.8 252.0
Total Mass Flow (Ib/hr) 21,447.80 438.03 20,743.76 20,686 .08 42,571.91 42,571 .91 20,783.29 42,571.91 20,402.42 62,974.33
Components (Ib/hr):
HYDROGEN trace trace trace trace 2,339 .05 trace 7,781.47 7,781.47
CO2 trace trace trace trace 1,790.54 trace 5,137.53 5,137 .53
METHANE 516.52 1,495.12 1,495.12
ETHYLENE 302.49 855.34 855.34
ETHANE 303 .96 855.42 855.42
ACETALD trace trace trace trace trace 4,445.69 trace 621.46 621.46
ACETONE trace 0.006 0.006 0.006 0.006 219.70 0.006 285.40 285.40
ETHYLACE 1.47 0.016 0.016 1.49 1.49 299.41 1.49 906.51 908 .00
ETHANOL < 0.001 < 0.001 < 0.001 0.001 0.001 254 .71 0.001 17.25 17.25
<f
WATER 21,447.80 0.001 366.13 365.11 365.11 365.11 2,376.36 365 .11 933.97 1,299.08
HOAC 436.55 20,377 .61 20,320.95 42,205.31 42,205.31 7,934.87 42,205 .31 1,512.96 43,718 .26
Temperature (oF) 556.8 556.8 556.8 202.6 268 280.1 113 113 159.2 126.4
Pressure (psia) 250.9 250.9 250 .9 262 .8 245.92 245.7 244.7 244.7 235.0 234 .9
Total Mass Flow (Ib/hr) 62,977.88 42,195.18 20,782 .70 20,402.42 42,195.18 62,979.67 62,979 .67 23,469.70 62,277.91 65,870.50
Components (Ib/hr):
HYDROGEN 7,088 .04 4,748.99 2,339.05 7,781.47 4,748.99 7,088.04 7,088.04 7,088.02 trace 0.02
CO2 5,425.89 3,635.35 1,790.54 5,137.53 3,635.35 5,425.88 5,425.88 5,328.15 trace 122.96
METHANE 1,565.20 1,048.68 516.52 1,495.12 1,048.68 1,565.20 1,565.20 1,543.27 trace 28.45
ETHYLENE 916.61 614.13 302.48 855 .34 614.13 916.63 916.63 893.76 trace 27.13
ETHANE 921.10 617.13 303 .96 855.42 617.13 921.10 921.10 898.61 trace 31 .92
ACETALD 13,468.60 9,023.96 4,444.64 621.46 9,023.96 13,471 .78 13,471.78 6,792.88 6.47 6,167.54
ACETONE 665.97 446.20 219.77 285.40 446 .20 665.76 665.76 119.04 785.89 615.79
ETHYLACE 908.03 608.38 299.65 906.51 608 .38 907.31 907.31 126.56 2,775.68 1,983.88
ETHANOL 771 .86 517 .15 254.71 17.25 517.15 771 .84 771.84 33.52 110.70 126.75
..J WATER 7,201.54 4,825.03 2,376.51 933.97 4,825.03 7,201 .08 7,201.08 266.36 13,552.93 12,873.06
HOAC 24,045.05 16,110.18 7,934 .86 1,512.96 16,110.18 24,045.05 24,045.05 379.53 45,046.25 43,892.99
Temperature (oF) 113 159.4 159.4 77 152.3 120.9 121 .8 101.8 98.3 101.81
Pressure (psia) 244 .7 233.5 233.0 214.7 212.7 229.9 43 .5 32.0 30.1 32 .0,
Total Mass Flow (Ib/hr) 39,509.77 19,877.11 19,618.71 785.61 20,404.31 105,380.47 105,379.58 10,354.66 2,463.56 2,885.40
Components (Ib/hr):
HYDROGEN 0.02 7,088.00 6,995.85 785.61 7,781.46 0.04 0.04 trace trace 0.04
CO2 97.73 5,205.19 5,137 .53 5,137.53 220.69 220.69 5.53 1.30 215.16
METHANE 21.93 1,514.82 1,495.13 1,495.13 50.38 50.38 2.39 0.54 47 .99
ETHYLENE 22.87 866 .63 855 .36 855.36 50 .01 50.00 8.07 1.88 41 .93
ETHANE 22.49 866.69 855.42 855.42 54.41 54.41 4.78 1.09 49 .63
ACETALD 6,677.43 631.81 . 623.59 623 .59 12,846.44 12,843.29 10,306.52 2,455.29 2,527.19
ACETONE 546.90 289.14 285.38 285.38 1,162.51 1,162.71 trace trace trace
ETHYLACE 781 .38 918 .35 906.41 906.41 2,764.63 2,765.36 trace trace
ETHANOL 738.33 17.47 17.24 17.24 865.07 865.08 trace trace
.g WATER 6,935.17 946.23 933 .93 933.93 19,807.78 19,808.00 27.372 3.456 3.46
HOAC 23,665.52 1,532.78 1,512 .85 1,512.85 67,558 .51 67,559.63 trace trace
Temperature (oF) 10 262 .7 262 .6 158 262 .7 263.2 117.5 118.1 275.2 182.5
Pressure (psia) 28.0 37.8 37 .8 31.8 37 .8 100.0 35.0 98 .0 95.0 40 .0
Total Mass Flow (Ib/hr) 421 .84 92,139.53 62,277 .57 62,277 .91 29,861 .62 29,861.62 22,326 .31 22,326.31 31,444 .17 5,111 .13
Components (Ib/hr):
HYDROGEN 0.041 trace trace trace trace trace < 0.001 < 0.001 < 0.001 < 0.001
CO2 213.86 trace trace trace trace trace trace . trace trace trace
METHANE 47.45 trace trace trace trace trace
ETHYLENE 40.05 trace trace trace trace trace
ETHANE 48.54 trace trace trace trace trace
ACETALD 71.90 9.57 4.87 6.47 3.10 3.10 17.83 17.83 20.93 4.82
ACETONE trace 1,162.71 785.95 785.89 376.83 376.83 1,598.79 1,598.79 1,975.61 487.45
ETHYLACE 4,106.58 2,775.97 2,775.68 1,330.91 1,330.91 17,200.99 17,200.99 18,531 .88 4,044 .88
ETHANOL 163.78 110.71 110.70 53 .08 53.08 110.58 110.58 163.66 31.88
::0
WATER < 0.001 20,051.42 13,553.36 13,552 .93 6,498.49 6,498.49 1,746.22 1,746.22 7,878.58 540 .20
HOAC 66,645.46 45,046.71 45,046.25 21,599 .21 21,599.21 1,651.91 1,651.91 2,873 .51 1.90
Temperature (oF) 214 .1 113 182.3 181.9 184.3 117.5 259.4 234.1 182.1 167.6
Pressure (psia) 39 .0 36 .0 24 .7 25.0 24 .9 35.5 35 .0 27.4 25.0 22 .0
Total Mass Flow (Ib/hr) 36,555.16 36,555.16 5,111.13 4,356.10 755 .20 8,295.16 2,161 .83 9,262 .68 1,194.31 439 .28
Components (Ib/hr):
HYDROGEN < 0.001 < 0.001 < 0.001 < 0.001 trace trace trace trace
CO2 trace trace trace trace I
METHANE I
ETHYLENE
ETHANE
ACETALD 25.83 25.83 4.82 4.66 0.17 3.63 0.32 3.31 3.16
ACETONE 2,463 .10 2,463.10 487.45 424 .01 63 .50 439 .38 145.94 293.44 229 .99
ETHYLACE 22,576.48 22,576.48 4,044.88 3,434.98 610 .00 803 .75 19.51 784 .24 174.35
ETHANOL 195.55 195.55 31.88 29 .15 2.74 55 .58 50.45 5.13 2.39
WATER 8,418 .79 8,418.79 540.20 462.28 77.92 6,208 .52 2,161.83 8,263 .04 107.31 29.39
~
HOAC 2,875.41 2,875.41 1.90 1.02 0.88 784 .29 783.42 0.88 trace
Process Description
1. Reaction Section
The feedstocks for the reaction of interest are acetic acid and hydrogen.
Hydrogen gas is available at 200 psig, and the acetic is available as a liquid. We assumed
both starting materials to be at 77 OF. These starting materials are each mixed with
recycle streams composed primarily of the respective reactant before proceeding to the
reactor. The pure acetic acid feed stream S-101 is combined with recycle streams S-102
and S-1 03, which originated at the ethyl acetate distillation column DC-91 0 and the
acetic acid distillation column DC-61 0, respectively. In preparation for the high
pressures required for reaction, the acetic acid feed is pumped to 263 psi by the acetic
acid feed pump, P-110 (see Unit Description on p. 54). The pure hydrogen feed, S-402,
is mixed with the mostly-hydrogen recycle stream S-40 1, and this combined stream is
compressed from 213 psi to 263 psi in the compressor CP-410 (see Unit Description on p.
40). This is a very expensive part of the process because of the price of both the
The combined acetic acid stream S-201 is passed through heat exchanger HX-200
(see Unit Description on p. 50), where hot reactor effluent in stream S-206b, heats the
acetic acid from a liquid at 242 OF to a partial vapor at 465 OF. In the process, the reactor
effluent is cooled to its dew point of280 OF. A different portion of the reactor effluent,
stream S-206a, is used to heat the hydrogen feed S-207 from 203 OF to 478 OF in the heat
exchanger HX-21 0 (see Unit Description on p. 51). The cooled reactor effluent S-208
exiting HX-21O is also at its dew point of280 OF and 246 psi, this was done for ease of
mixing when two reactor effluent streams are reunited. The hot acetic acid and hydrogen
23
streams, S-203 and S-204 respectively, are both fed to the fired heater F-230 (see Unit
conditions occur at approximately 570 of, but the reaction is endothermic, so heat would
heat the reactants to a higher temperature rather than attempt to insulate the reactor. The
feed temperature of 599 of is well within the range of suggested temperatures for this
reaction (Testin, et al.). F-230 is designed to operate on natural gas, but waste material
streams OFFGAS and ACETONE WASTE are rich in hydrogen and hydrocarbons and
are also burned in F-230. These streams are used to furnish 8,547,300 Btu/hr of the
15,291,600 Btu/hr required to operate the furnace . More energy could be taken from
these streams as well as the purge streams, but limiting the amount of energy derived
from waste streams to approximately 55% makes controlling the heating rate of the
furnace more reliable. Any portion ofthese streams that is not used in the furnace is sent
containing a packed bed of20% wt. Pd- Fe203 catalyst pellets. In order to ensure the
proper oxidation state for the desired conversion, the hydrogen and acetic acid are fed in
a 5/1 molar ratio. Conversion of acetic acid is only 46 %; this is in order to improve the
formed in the reactor include ethanol, acetone, carbon dioxide, and light hydrocarbons.
24
2. Acetaldehyde Purification
The reactor effluent S-206 is then split into two streams and used to preheat the
acetic acid and hydrogen feeds. It is split instead of passing sequentially into the heat
exchangers so that both the hydrogen and acetic acid feeds can be heated to higher
temperatures. After passing through the heat exchangers, the temperature of the
combined stream is 280 of, its dew point. This is hot enough to supply energy
sequentially to the reboilers of the azeotropic distillation column (DC-900) and the
acetone waste column (DC-81 0), but the amount of steam and cooling water utilities
saved would not counteract the need to move the hot fluid over long distances and the
After passing through the acetic acid heat exchanger HX-200 and the hydrogen
heat exchanger HX -210, the separate reactor effluent streams are mixed together, forming
stream S-301. This stream must be cooled further in order to achieve high recovery in the
absorber column; cooling water is used to cool the stream to 113 of in HX-300 (see Unit
Description on p. 51). This partially condenses the stream, and the cool effluent, S-302 is
fed to the flash vessel FV -310 (see Unit Description on p. 50) to separate the liquid and
vapor phases. Only the vapor stream S-303 exiting the flash vessel is sent to the absorber
AB-320 (see Unit Description on p. 39), which it enters on the bottom stage. The solvent
fed to the top stage of the absorber is the acetic acid-rich bottoms product from
acetaldehyde distillation column DC-500 (see Unit Description on p. 44). Under the
conditions of high pressure (the top stage operates at 233.5 psi), this solvent
preferentially absorbs the acetaldehyde, allowing hydrogen, carbon dioxide, and other
25
light materials to escape: 85 % of the acetaldehyde is recovered, but only 3.5% of the
economics of the process. As the recycle amount increases, the recovery of acetaldehyde
increases, but at the expense of larger diameters for both the absorber and the distillation
column, as well as a more difficult separation of the acetaldehyde from the water and
acetic acid. The selected solvent recycle allows recovery of 95% of the acetaldehyde,
while also leaving a feasible separation and relatively low column costs. The pressure of
the absorber is also as high as possible in order to improve acetaldehyde recover and limit
the amount of work the compressor CP-410 must do. The mainly-hydrogen vapor exiting
AB-320 is recycled to the reactor, with a 1.3% purge taken to prevent excessive buildup
of light components. This purge stream PURGE2 is burned in the flare stack. The
bottoms product from the absorber, S-305, is combined with S-306, the liquid exiting the
flash vessel FV-310. S-305 and S-306 contain 10% and 17% acetaldehyde by mass,
respectively. At the time of mixing, the pressure is still high, 230 psi. The combined
stream S-50 1 is passed through a valve to reduce the pressure to 43 psi before being fed
is preferred to keep the pressure elevated to reduce the need for refrigerants to condense
the vapor. However, acetaldehyde fonns an azeotrope with water at pressures higher
than 30 psi, and this becomes more water-rich with increasing pressure. In addition, the
presence oflight components such as carbon dioxide and methane require adjustments to
26
be made in the distillation. First, they lower the boiling point ofthe mixture further,
making it more difficult to use cooling water to condense the distillate. Second, their
concentration is high enough that even if the acetaldehyde is completely separated from
the heavier components, its purity will still be only 97.2% wt., which is not high enough
to be sold. Thus, this column requires a partial condenser with both liquid and vapor
distillate: the liquid is taken as the acetaldehyde product, while the vapor distillate is fed
to another column where additional acetaldehyde can be removed from the lighter
condenser at 32 psi. Since the liquid-liquid separation of acetaldehyde and water actually
increases with temperature, one alternative examined carrying the high pressure from the
absorber into the distillation column, then allowing the two liquid phases to separate in a
decanter. This method did not produce acetaldehyde at the required purity, was difficult
to control, and required very high reboiler temperatures. A second alternative involved
using the main column as selected, but also adding an absorbing column, in which the
acetic acid-rich bottoms product would be used to absorb acetaldehyde. This did not
produce sufficient separation, and the added flow into the distillation column increased
distillation column at 32 psi. The distillate vapor fraction was varied to keep the
temperature of the distillate at 102 OF, which can be cooled using cooling water. The
liquid product, HAC PRODUCT, contains 10,355 Iblhr (82,012,000 Ib/yr) of99.5% wt
acetaldehyde. The vapor distillate S-504 is 22 % by mole of the total distillate and
contains 2,527 Iblhr of acetaldehyde. Since this is a significant portion of the product, it
27
was necessary to recover as much of this stream as possible. The vapor distillate is then
sent to the bottom stage of a small secondary column, DC-51 0 (see Unit Description on
p. 46), which has a refrigerated condenser at 10 of. A second product stream, HAC
PRODUCT, exits the bottom stage ofDC-510 and contains 24641blhr (19,515,000 lb/yr)
of99.7 wt% acetaldehyde. Sixty tons of refrigeration is required at the condenser, and
ammonia absorption system RF-520 (see Unit Description on p. 64). Decreasing the
temperature further would increase the yield of acetaldehyde, but at the expense of more
expensive equipment and a larger heat duty. In this design, 71.9 Iblhr (569,000 lb/yr) of
acetaldehyde is lost to the stream OFFGAS . This stream, with its high levels of methane,
ethane, and ethylene is burned in the fired heater, F-230, to reduce natural gas costs.
reaction between ethanol and acetic acid, which forms ethyl acetate and water.
Equilibrium for this reaction is achieved wherever acetic acid and ethanol are present
together, but for the purposes of this design, it was assumed this reaction occurs only in
the bottom stage ofDC-500, where the high temperatures and the presence of acetic acid
and ethanol in the liquid phase especially favor this reaction. When equilibrium is
reached, over 80% of the ethanol has been reacted. The presence of ethyl acetate is very
important in the acetic acid separations section of the process, where ethyl-acetate forms
an azeotrope with water, easing the separation of water from acetic acid. The bottoms
product S-506 from the acetaldehyde distillation column is split, with part proceeding to
the acetic acid separation sequence, and the remainder being cooled by cooling water in
the heat exchanger HX-530 (see Unit Description on p. 52) and then recycled to the top
28
stage of the absorber AB-320, where it acts as the solvent to preferentially absorb
acetaldehyde.
The main goal of the acetic acid separation column DC-610 (see Unit Description on
p. 46) is to obtain a pure stream of acetic acid, which can be recycled to the reactor feed.
The reasons for this are twofold. The primary reason is that the high cost of acetic acid
makes it economically feasible for us to reuse the unreacted acetic acid rather than
dispose of it. This is particularly relevant because of the low conversion in the reactor,
which results in a significant amount of unreacted acetic acid in the system. The second
reason is that acetic acid is an impurity in water and its substantial presence in the
There are two streams entering the acetic acid distillation column. The feed stream, S
602, is the bottoms from the acetaldehyde separation columns and enters DC-61 0 at the
h
1i of 30 actual trays. It primarily consists of the unreacted acetic acid and the products
of side reactions such as water, ethyl acetate, acetone, and ethanol. The recycle stream S
603 fed to the second stage is rich in ethyl acetate and is used to facilitate the low boiling
water - ethyl acetate azeotrope, which makes the separation of acetic acid in the bottoms
easier. The feeds S-602 and S-603 are pumped to 100 psi and 98 psi, respectively, before
entering the column. The condenser is operated at 95 psi because as pressure increases,
the water-ethyl acetate azeotrope becomes more water-rich, easing the separation from
acetic acid. This significantly increases the purity of acetic acid that is collected at the
bottoms. lfthe same process were operated at 37.8 psi (the pressure of the feed stream),
then the mass fraction is only .92-.93 as opposed to .982 at this pressure. Though the
29
higher pressure increases the cost, it is a cost that is well incurred since the acetic acid
increase in the bottoms is critical as it lowers the acetic acid that is lost in the wastewater
stream. Further increases in pressure beyond 95 psi cause very marginal increases in the
acetic acid mole fraction and do not justify the additional costs.
The nwnber of equilibrium stages calculated is 18. The increased separation with
additional stages is minimal after 18 stages and does not justify the increasing cost. The
calculated tray efficiency is 61 %, meaning 30 actual trays are required. We use a kettle
reboiler in this process and a total condenser. A total condenser is used because the
distillate must be fed to the decanter DE-720 (see Unit Description on p. 44) as a liquid.
Before the distillate enters the decanter, it goes into a mixer, M-700. The mixer
incorporates the distillate stream of the acetic acid separation colwnn with the distillate
stream of the DC-900 col umn, whiCh primarily consists of ethyl acetate and water, and
the bottoms of the acetone separation column, DC-81 0, which contains ethyl acetate that
was contained in the water-rich stream coming out of the decanter and water and acetone
impurities. The pressure across the mixer drops to 39 psi. This is done because operating
the remaining distillation columns in the separation sequence at higher pressure does not
produce results that are significantly favorable enough to account for incurring the higher
cost when the separating columns were operated at a higher pressure. In addition, this
places less of a load on the pump P-730 (see Unit Description on p. 56), which must
increase the pressure of recycle stream S-705 to only 40 psi before sending it to the
mIxer.
The exit stream from the mixer has a temperature of214 of and is cooled to 113 of
by passing it through the heat exchanger HX-71 0 (see Unit Description on p. 52). The
30
exit stream from this heat exchanger is fed to the decanter DE-720, which is used to
separate the water from the ethyl acetate in the feed stream. The water rich stream S-801
contains 74.8% by mass of water and S-901 contains 77.0% ethyl acetate.
The ethyl acetate-rich organic layer exiting the decanter in stream S-90 1 is sent to the
ethyl acetate splitter, which recycles 78.9% of the stream to the acetic acid distillation
column where it enhances the separation of water from acetic acid. The rest of the stream
is fed into the distillation column DC-900 (see Unit Description on p. 48).
Column DC-900 is used to separate water from the acetic acid and ethyl acetate in
S-90 1. The low-boiling azeotrope of water and ethyl acetate is taken in the distillate
along with acetone and acetaldehyde, leaving a bottoms product that is primarily ethyl
acetate and acetic acid. The acetic acid is purified and recycled to the reactor, and the
ethyl acetate is sold as a product. The distillate stream of this distillation, S-706, is
recycled to the decanter DE-720. This is to separate the water from the ethyl acetate,
which is then either recycled to the acetic acid distillation column, or purified for sale.
The separation in DC-900 was achieved by using a condenser pressure of 30 psi and 12
equilibrium stages (20 actual trays). A total condenser and kettle reboiler are used in this
process.
The bottoms product of DC-900, S-902, is 72% ethyl acetate by mass, with acetic
acid composing most of the balance. This stream enters the ethyl acetate distillation
column, DC-91 0 (see Unit Description on p. 48), at stage 13 of23 (tray 25 of 43). The
main purpose of this column is to separate the ethyl acetate from the acetic acid at a level
31
of purity whereby the ethyl acetate can be sold. This column is operated at a condenser
pressure of 16 psi and the distillate contains 99.6% mass of ethyl acetate. The bottoms
product contains 99.7% by mass of acetic acid and is recycled back to the reactor via the
stream S-1 02. Ethyl acetate is stored in a cool, dry, well-ventilated area with a holding
capacity of 7300 ft3 (enough capacity to hold 14 days worth of ethyl acetate production)
The water-rich stream S-SO 1 exiting the decanter is then sent to the stripper ST -SOO
(see Unit Description on p. 66). The condenser is operated at a pressure of25 psi. The
bottoms stream of this column is sent to a waste treatment plant for purification before it
is disposed off. The distillate, S-S04, primarily contains acetone and ethyl acetate and is
fed to the acetone separation column, DC-Sl 0 (see Unit Description on p. 47), at stage S
of 11 (13 th of IS actual trays). A partial condenser is used for the stripper because utility
costs are decreased by not condensing the vapor and feeding a dew point vapor to the
The acetone distillation column, DC-S1 0, aims to remove all of the acetone from the
feed stream as the distillate and remove it from the system. The acetone in the distillate
cannot be made pure enough to be sold as a side product, unlike ethyl acetate. This
column has IS actual trays and operates at a condenser pressure of 22 psi. The bottoms
product S-707 mainly contains ethyl acetate and is mixed with S-706, the distillate stream
of the DC-900 column, via the mixer M-740. The combined stream, S-705, is at 24 psi
32
and is pumped to 40 psi before being fed to the mixer M-700 where it is mixed with the
33
34
Because of the high temperatures required for the reactor and the many dis61lation
columns, supplying energy for heating and cooling process streams is of paramount
concern for the economics of the process. The largest heating and cooling requirements
are found in the acetic acid distillation column, which requires 39,534,800 Btu/hr for the
reboiler at 370 of and 36,586,600 Btulhr for the condenser. These requirements are
satisfied with 300 psia stearn (dropped from its source at 600 psig) and cooling water,
respectively. The reboilers and condensers for each of the other columns are handled
similarly (using steam at the appropriate pressure), except for the low-temperature
absorption to cool a 40% ethylene glycol in water solution that circulates in the
condenser. The glycol removes 612,900 Btulhr of heat by partially condensing the
distillate ofDC-5IO at 10 OF. Because of heat leak to the surroundings and inefficiencies
in heat transfer, we assumed that the ammonia absorption system must supply 900,000
Btu/hr of refrigeration. Assuming the ammonia system operates at -10 OF, 507
Btu/min/ton are required for steam in the generator and 5.4 gpm/ton of water are required
for the conditioner (McKetta). The refrigeration load is 75 tons, requiring 2,497,500
Btulhr of steam at 300 OF (68 psi) and 24,000 gpm of cooling water.
The acetic acid and hydrogen streams, S-20I and S-207 respectively, which are
the reaction starting materials must be heated from 242 OF and 203 OF to 599 OF before
entering the reactor. This is above the optimal reaction temperature of 572 OF, but still
within the range of recommended temperatures (Tustin, et.a!.). It was heated to this
temperature because the primary reaction is endothermic, and by heating above the
35
optimal temperature we allow the temperature in the reactor to decrease as the reaction
progresses. This method was used because it was suggested that this would be more
efficient than attempting to insulate the reactor at the high temperature required. The
reaction consumes 2,677,000 Btu/hr, and the effluent is a total vapor at 557 OF. The hot
reactor effluent is split and sent to separate heat exchangers to heat the hydrogen and
acetic acid feed streams. The rate of energy transferred to the acetic acid in HX-200 is
4,305,300 Btu/hr, and 8,741,000 Btulhr is transferred to the hydrogen stream in HX-21 O.
Following this, the hydrogen and acetic acid feed streams still require 12,692,000 Btu/hr
to reach 599 OF; this is accomplished in the fired heater, F-230. Waste streams OFFGAS
and ACETONE WASTE are burned to produce 8,547,300 Btulhr, and natural gas is
required for the rest of the duty, which because of inefficient heat transfer is 15,291,600
Btulhr total. After being cooled to its dew point by the reactor feeds, the reaction product
HX-300.
The option of using heat from the reactor effluent stream S-401 at 280 OF to heat
the reboilers ofDC-900 and DC-810 was examined, but ultimately rejected. There is
sufficient energy in S-401 to maintain a 45 OF driving force with the bottoms, but
substituting this method for steam heating did not justify the need to pump the hot fluid
over long distances and the more complicated control aspects. Heat integration among
the condensers and reboilers in the separation section was not attempted because the
operating pressures needed to optimize product composition and column costs does not
36
The utility requirements are summarized in the table below.
37
The costs listed are what would be paid if these utilities were purchased from an
outside source. This was not done for steam and cooling water, because it was
determined that building allocated facilities would be more profitable (see Appendix, p.).
38
Unit Descriptions
Absorber
The absorber unit AB-320 is a trayed tower used to separate the acetaldehyde
from light hydrocarbons, carbon dioxide, and the unreacted hydrogen that results from
feeding that material in large excess. The primary objective of this unit is to recover as
much acetaldehyde as possible because 1.3 % of the material leaving through the top of
the column leaves the system as PURGE. 23,470 Iblhr of the vapor stream S-303 is fed
to the bottom stage of the column, and 62,278 lb/hr of S-304, the solvent recycled from
the bottoms of the acetaldehyde distillation column, is introduced on the top stage. This
solvent level was chosen to balance the amount of acetaldehyde recovered in the absorber
with the ease of separation of the acetaldehyde from the remaining liquid, which contains
a lower fraction of acetaldehyde as solvent flow increases. The recovery stream S-305
exits as a liquid from the bottom stage, and has a total flow of 65,871 lb/hr with an
acetaldehyde mass fraction of 0.094. S-401 exits the top of the column and contains
mostly unreacted hydrogen and light gas side products; 98.7% of this stream is recycled
to the reactor, the remainder is purged and burned in the flare stack.
The top stage pressure in the absorber is 233.5 psi, with the intention of keeping
the pressure as high as possible without resorting to compressing the reactor effluent.
The absorber was designed to recover over 85 % of acetaldehyde fed to it, so that the
resulting loss to purge would be only approximately 0.15 % of acetaldehyde. This design
led to a column containing 15 theoretical trays; the O'Connell correlation was used to
calculate the stage efficiency (Seader). This was found to be 51 %, requiring 30 actual
39
trays. Using equations and tables found in Seider, the calculated dimensions were 2.5 ft
diameter and a height of 74 ft; the associated bare module cost of the tower and trays is
$120,000. The material used for both the column and the trays is stainless steel because
Compressor
to compress 20,404 felhr of the mixed hydrogen stream S-207 from 212.7 psi to 262.8
psi. The temperature of the stream also increases, from 152.3 OF to 202.6 oF. The load
required was limited as much as possible by maintaining high pressures throughout the
reactor section of the process, while still ensuring that the feed to the compressor was
above its dew point. The power is 330.9 kW, and the efficiency is estimated by Aspen to
be 72%. This leads to an electricity requirement of 459.6 kW. The material used was
stainless steel, and the bare module cost was calculated to be $2,628,000.
Condensers
distillation column, DC-500. A partial condenser with both liquid and vapor distillate is
employed for two reasons. First, the significant concentration of light compounds such
as carbon dioxide would cause the acetaldehyde purity in the product to be too low if a
40
single disti llate stream was taken. Second, condensing those light gases and all of the
acetaldehyde would require very low temperatures and a large amount of refrigeration.
Instead, the fraction of vapor distillate was set in order to have a distillate temperature of
102 of, which can be achieved with cooling water. To accomplish this, 22% of the
distillate remains vapor; this stream (S-504) contains approximately 20% of the
acetaldehyde produced, and this is recovered in the DC-51 0 column. The condenser is
made of stainless steel, and has a heat duty of 10,559,800 Btulhr. Using a heat transfer
coefficient of97.6 BtU/(hr-ft2-0F), B-JAC estimates a surface area of 13,109 ft2; because
of this large size and the temperature crossover of the hot and cold stream temperatures,
B-JAC split this exchanger into two in series. A 1-8 shell-and-tube heat exchanger was
designed, with a length of 8 ft., and shell size of 70 in. The estimated installed cost from
B-JAC is $209,960.
C-520, a partial condenser with all vapor distillate, is used for DC-51 0, the
temperature requirement would be unreasonably low, and there is little processing benefit
from having a liquid distillate. The heat duty of the condenser is only 612,900 Btu/hr at
10F, making refrigerant cooling a practical solution for this process. A 40%-ethylene
glycol in water solution is circulated in the condenser to cool the distillate. The heat
surface area is 403.2 ft2. In order to limit the amount of glycol solution needed to cool
the condenser, the solution is heated from -5 OF to 30 OF; because of the temperature
41
crossover, two condensers, both 1-2, are required in series. The length ofthe tube is 14
ft., and the shel1 width is 10.75 in. The material used was stainless steel. The estimated
The condenser used for the acetic acid distillation column is a total condenser,
because in the next step in the process the liquid distillate is fed to the decanter DE-720.
Cooling water is used, and the exiting distillate has a temperature of275 of. The heat
duty is 36,586,600 Btu/hr, and using an estimated heat transfer coefficient of 129 BtU/(hr
ft 2 _OF), the required surface area is 2,494 ft2. A single 1-4 shell-and-tube heat exchanger
is used for this process. The tube length is 10ft., and the shell diameter is 38 in. Using
stainless steel as the material, B-JAC estimated the installed cost of this item to be
$64,710.
For the stripper, a partial condenser was used because sending S-804 to the
acetone distillation column DC-81 0 as a vapor reduced the overall utility requirements
without significantly altering the separation. The condenser C-800 is a 1-4 shell-and-tube
heat exchanger, made of stainless steel. The required heat duty is 994,200 Btu/hr, and
using a heat transfer coefficient of 112 Btu/(hr-ft2 -OF), the required surface area is 112.2
ft2. The shell diameter is 8.6 inches and the tube length is 16 ft. The installed cost is
$7,570.
42
C-810 (see spec. sheet p. 78)
The condenser for the acetone distillation column DC-81 0 is a 1-4 shell-and-tube
heat exchanger made of stainless steel. The heat duty is 428,700 Btu/hr, with a distillate
temperature of 168 of. A partial condenser with all vapor distillate was used because the
unnecessary to condense the stream. The heat transfer coefficient is 95 Btu/(hr-ft2 _OF),
and the resulting area is 78 ft2. The tube length is 10ft., and the shell diameter is 8.6 in.
A total condenser is used for the near azeotrope distillation column DC-900. The
heat exchanger is a 1-2 shell-and-tube heat exchanger made of stainless steel. This
condenser subcools the product to 2 of below the saturation temperature so that when the
disti llate is mixed and fed to the pump P-730, the feed stream is a total liquid. The
distillate temperature is 18l.9 of, and the heat duty is 2,911,400 Btu/hr. Using a heat
transfer coefficient of 105 Btu/(hr-ft2 _OF), B-JAC estimated the required surface area to
be 275 ft2. The tube length is 14 ft., and the shell thickness of 12.75 in. The installed
cost is $9,250.
A total condenser is used for the ethyl acetate distillation column so that the liquid
ethyl acetate can be recovered and stored. C-910 is a 1-8 shell-and-tube heat exchanger
made of stainless steel. The distillate temperature is 175 of, and the heat duty is 509,600
43
Btulhr. The effective surface area based on an estimated heat transfer coefficient of72.6
Btul(hr-ft 2_OF) is 473 ft2. The tube length is 6 ft., and the shell diameter is 24 in. The
Decanter
The purpose of the decanter is to separate water from the ethyl acetate in the inlet
stream S ~ 704. It achieves this to an extent of getting a water-rich stream, S-80 1 with
74.8% by mass of water and an ethyl acetate rich stream, S-901 with 77 .0% by mass of
ethyl acetate. The outlet temperature of the decanter is 117 .5F and its outlet pressure is
35.5 psi . The capacity of the decanter is based on a 10 minute residence time at half full
and equals 214 ft3. The decanter is a horizontal, stainless steel vessel, with a diameter of
4.5 ft. and length of 13.5 ft; using cost charts, we determined its bare module cost to be
$63,000.
Distillation Columns
DC-500 is the major unit for separating acetaldehyde from the heavier
components in the reactor effluent: acetic acid, water, acetone, ethyl acetate, and ethanol.
Even though acetone's boiling point is closest to acetaldehyde's, the key heavy
low as 30 psi, water forms an azeotrope with acetaldehyde, which becomes richer in
water as pressure increases. As a result of this, the pressure of the condenser was set at
32 psi to limit the recovery ofthis azeotrope. Acetaldehyde's relatively low boiling point
44
(10F) makes this low pressure undesirable because of difficulties in condensing the
material, but attempted higher pressure methods such as liquid-liquid separation from
calculations provided the minimum number of stages as 20 and the minimum reflux ratio
as 1.61. At 1.3 times the minimum reflux (LID = 2.09), the Gilliland correlation yields
the estimated number of stages as 40. This actual conditions used in the simulation were
a reflux ratio of 2.40, and 40 equilibrium stages. The tray efficiency is 56%, necessitating
71 actual trays. Stream S-501 enters above the 50 th stage to provide a larger rectifying
section, allowing better purification of the acetaldehyde distillate. Using cost charts
available in Seider, the distillation column dimensions are 4.5 ft in diameter, and 157 ft.
taB; the estimated cost of the column and trays was $1,013,500. IPE estimated the
column dimensions as a 4 ft. diameter and 171 ft. height. The material and labor cost
using lPE was estimated as $1,087,000. The height was determined by taking a 2-f1. tray
spacing, a 4-ft. disengagement height for the condenser, and a 10-ft. bottoms sump.
DC-500 also has the esterification reaction in which acetic acid and ethanol react
to form water and ethyl acetate (Reaction 5, p. 10). This reaction is very important to the
process, and the patent describes adding sulfuric acid to catalyze this reaction if it does
not occur in sufficient yield. Under the conditions of this column, that step was not
necessary. This reaction is important because ethyl acetate is needed in the acetic acid
separation section to form a low-boiling azeotrope with water in order to facilitate the
separation of water from acetic acid. The ethyl acetate-water product is favored
thermodynamically, and under the reaction conditions over 80% of the ethanol reacts.
45
The ethyl acetate can then be purified, and we are able to purify and sell 1,139 Ib/hr of
ethyl acetate.
flow of 10,355 Ib/hr. The bottoms product, S-506, contains 92,140 Iblhr of 72.4 %wt
acetic acid, with water being the other major component. Only 9.6 Ib/hr of acetaldehyde
is in this stream. S-506 is split, with part returning to the absorber AB-320 as the solvent,
and the remainder proceeding to the acetic acid separations section, where pure acetic
acid is recycled to the reactor and ethyl acetate is purified for sale.
condense acetaldehyde from the vapor distillate of the main acetaldehyde distillation
column. S-504 enters the column on the bottom stage, from which the second
acetaldehyde product HAC PRODUCT is also taken. The temperature of the condenser
good yield is only three, but low tray efficiency (26 %) caused by the large relative
volatility of ethane to acetaldehyde leads to the need to for eight actual trays. The height
of the column is 30 ft, and its diameter is 1.5 ft. Stainless steel is used for the tower and
trays. The bare module cost of the column, using cost charts, is $62,500.
The acetic acid separation column was designed for 18 equilibrium stages. The
efficiency is 61 %, and the actual number of trays is 30. Assuming a 2-ft. tray spacing, as
46
well as the sump and disengagement heights, the height ofthe column is 74 ft., and the
diameter is 10.5 ft. The acetic acid-rich stream recovered as the bottoms of the
acetaldehyde distillation column enters DC-610 at tray 17. The ethyl acetate-rich recycle
stream S-603 enters the colurrm on the second tray and is used to form the ethyl acetate
water azeotrope, which makes the separation of acetic acid from water simpler. The
bottoms rate is 20,744 lblhr, the molar reflux ratio is 2.5 and the condenser pressure is 95
psi. On the recommendation of the industrial consultants, stainless steel was the material
chosen for the tower and the trays. This is because acetic acid has a corrosive effect on
carbon steel and stainless steel is sufficiently corrosion resistant. The bare module cost of
This acetone distillation colurrm is designed to remove the acetone from the system in the
distillate to be used as fuel in the fumace. The distillate stream, ACETONE WASTE,
primarily contains acetone, ethyl acetate and water with very small quantities of
acetaldehyde and ethanol. The bottoms stream, S-707, contains 80.8 % ethyl acetate and
10.3 % water. Eleven equilibrium stages were designed for the column; the tray
efficiency of 60.8 % implies the need for 19 actual trays. Using 2-ft. tray spacing, and 14
ft. total for the sump and disengagement heights, the column is 52 ft. tall, with a 1.5 ft.
diameter. Based on the flow rates a smaller diameter is necessary to avoid flooding, but
the 1.5-ft. diameter produces an aspect ratio of 35, which is much more reasonable. The
stripper distillate stream S-804 enters the column at tray 13. The distillate rate is 439
lblhr, the molar reflux ratio is 4 and the condenser pressure is 22 psi. Stainless steel was
also the material of choice for this column. Its bare module cost is $103,600.
47
....
Th.is column is designed to remove the acetone, ethanol and the ethyl acetate-water
azeotrope as the distillate and isolate the acetic acid and the remaining ethyl acetate in the
bottoms. The ethyl-acetate rich stream S-901 from the decanter is fed at the 10th tray.
Twelve equilibrium stages are needed for the separation, and the efficiency is 60%,
requiring 20 actual trays. To that end, this separation column is 54 ft in height and has a
diameter of 2 ft. The distillate rate is 4356 lblhr, the reflux ratio is 1.8 and the condenser
pressure is 30 psi. Stainless steel was also the materiaJ of choice for this column. Its bare
This ethyl acetate distillation column is designed to purify ethyl acetate as the distillate to
a level at which it can be sold. The bottoms product is acetic acid, which is recycled to
the reactor. Twenty-three equilibrium stages are needed for this separation; the tray
efficiency is 41.5 %, and the actual number of trays is 45. This separation column is 104
ft in height and has a diameter of 3 ft. Stream S-S-804 enters the column at tray 25. The
distillate rate is 1139 lblhr, the reflux ratio is 1.8 and the condenser pressure is 16 psi.
Stainless steel was also the material of choice for this column. Its bare module cost is
$433,400.
48
Fired Heater
In order to completely heat the hydrogen and acetic acid feed streams, S-204 and
S-203, to the desired reaction temperature, energy must be supplied by burning fuel in the
fired heater F-230. F-230 is a vertical cylindrical fired heater. 20,402Ib/hr of the
gaseous hydrogen feed S-204 at 478 of and 42,571 lblhr of the partial vapor S-203 at 465
OF are fed to F-230 separately because they are different phases. The heat duty required
to raise the temperature of the streams to 599 OF to prepare for the reactor is 12,692,000
Btulhr. Assuming a stack temperature of 650 of, according to McKetta the efficiency is
83% and thus the required total heat duty is 15,291,600 Btulhr. This is furnished by
burning natural gas, along with waste streams from the process: OFFGAS and ACTONE
WASTE. The cost for this unit was estimated based on a design heat duty of 20,000,000
Btu/hr. This leads to an installed cost of $609,400 (Walas). The material used is
stainless steel because it is able to handle the high temperatures and also will not corrode
in the presence of acetic acid. Of the 15,291,600 Btulhr required to heat the process
streams, 8,547,300 Btulhr (56 %) is supplied from burning the process streams. This
amount was chosen in order to balance the cost of natural gas that must be bought with
the control and safety concerns that would be associated with using waste streams for
49
Flash Vessel
The flash vessel FY -310 is used to separate the liquid and vapor portions of the
reactor effluent leaving the heat exchanger HX-300. The volumetric flow rate into the
minute holdup time at half full, is 16,860 ft3. This is a large process vessel, and the
diameter was set at 17 ft., so that it would not have to be fabricated on the site. The
length height is 76.5 ft. This is made of stainless steel because of the corrosion caused by
acetaldehyde and acetic acid. The bare module cost for the flash vessel is $1,832,000.
Heat Exchangers
HX-200 is used to increase the temperature of the acetic acid feed stream S-20 1
from 242 OF to 465 OF, where it is a partial vapor. To do this, 20,783 lb/hr of reactor
effluent S-206b is cooled from 557F to 280F, its dew point. The amount of heat
transferred is 4,305,300 Btulhr, and the estimated heat transfer coefficient between the
vapor and liquid was 10.8 BtU/(hr_ft2 _OF). This is relatively low for what is primarily
steel. The surface area is 8,343 fe, the tube length is 20 ft., and the shell diameter is 48
so
In HX-210, 20,840 lb/hr of the hydrogen feed stream S-201 at 202.6 of 1S heated
to 477.6 of by cooling 42,1961b/hr of the reactor effluent S-206a from 557 of to 280F.
This temperature is chosen because it is the dew point of S-206a at the operating
pressure, and having only vapor will ease mixing with S-206b, which is also cooled to its
dew point. This is a 1-1 shell-and-tube heat exchanger, which requires three exchangers
in series because of the large surface area required . The amount of heat transferred is
8,741,000, and using B-JAC the heat transfer coefficient was estimated to be 16.7
Btu/(hr-ft2_OF). The total required surface area is 8920 ft2, and the dimensions are a 10ft.
tube length and 60 in . shell diameter. HX-210 is composed of stainless steel to prevent
corrosion. The installed cost estimated by B-JAC was $630,750 for the three in series.
HX-300 is used to decrease the temperature of 62,979 Iblhr of the cooled reactor
effluent S-301 from 280F to 113F in order to increase the recovery of acetaldehyde in
the absorber AB-320 . S-301 enters as a dew point vapor, and is partially condensed in
the heat exchanger. Cooling water is used to transfer 20,300,000 Btulhr from S-301. The
heat exchanger is a 1-8 shell-and-tube heat exchanger made of stainless steel. The
estimated heat transfer coefficient used was 70.9 Btul(hr-fe-OF), requiring a size of6687
ft2. The tube length is 12 ft ., and shell diameter is 58 in. The estimated installed cost for
HX-300 is $163,820.
51
Stream S-506a, the solvent for the absorber, flows at a rate of 62,278 Ib/hr and a
temperature of 263 of into the heat exchanger HX-530. Cooling water is used to lower
the temperature to 157 of because more acetaldehyde is absorbed when the feeds to the
absorber are at lower temperatures. The required heat transfer rate is 2,736,000 Btulhr.
The estimated heat transfer coefficient in B-JAC is 105 Btu/(hr-fe_OF), which appears to
be reasonable for liquid-liquid heat transfer. The required area is 320 ft2, and the
estimated price is $10,750. The material used for the heat exchanger is stainless steel,
and it is a 1-2 shell-and-tube exchanger. The tube length is 20 ft., and the shell diameter
is 10.8 in.
HX-710 employs cooling water to reduce the temperature ofthe S-703 from 260.3 OF
to 113.0F before it is fed to the decanter DE-720. The exchanger has a heat duty of
3,689,100 Btu/hr. A heat transfer area of 921 ft2 is calculated for HC-71 0 in B-JAC based
heat exchanger with the following dimensions: tube length is 20 ft., shell diameter is 18
in. Stainless steel is the material of construction, and the installed cost is $15,940.
52
Mixers
M-220, M-310
Both M -220 and M-31 0 are used to mix reactor effluent, and a small pressure
drop is assumed across each. M-220 mixes 20,783 lb/lrr ofS-202 and 42,196 lb/hr ofS
208, both at 280 OF and 246 psi, the dew point of the vapors. These streams had been
used to heat the acetic acid and hydrogen feeds . These streams are mixed to allow a
single heat exchanger, HX-300, to cool the streams before feeding the resulting vapor
stream to the absorber AB-320. M-310 mixes 65,871 lblhr of the recovered absorber
bottoms S-305 and 39,510 lblhr of the liquid stream S-306 exiting the flash vessel. There
is a pressure drop of 5 psi across the mixer; this pressure drop can be almost arbitrarily
large, because the mixed stream is then passed into the valve V-50 1 to decrease its
M-400
Mixer M-400 combines the pure hydrogen gas feed at 215 psi a and 77 OF with the
hydrogen-rich stream S-402a at 159 OF and 233 psi. The pressure of the combined
stream is decreased to 213 psia. This pressure is low enough to ensure that the vapor is
above its dew point and no liquid will be fed to the compressor. The outlet temperature is
152 OF.
M-700
M-700 combines the 31,444 Iblhr liquid distillate from the ace6c acid distillation
column at 275.2F and 95 psi with the recycle stream S-702 which is at 182.5 F and 40
53
psi and has a flow rate of 5, 111 Ib/hr. It integrates the two streams to liquid stream S-703
and lowers the pressure to 39 psi, with the corresponding temperature of214.1 of.
M-740
M-740 combines the 43561blhr liquid stream S-706 (distillate from the near
azeotrope distillation column) at 181.9 of and 25 psi with liquid stream S-707 (the
bottoms from the acetone distillation column) which is at 184.3F and 24.9 psi and has a
flow rate of755 lb/hr. The combined stream is a liquid with a flow rate of 5,111 Ib/hr at
Pumps
Pump P-ll 0 is used to increase the pressure of the combined acetic acid feed
stream S-1 04 to 263 psi, so that it will be at the proper pressure for reaction. The
entering stream is at ambient pressure because it includes the pure acetic acid feedstock
S-101, assumed to be at 14.7 psi. The net required power is 9.7 kW, but since the
efficiency is only 0.52 the total power supplied is 18.6 kW. This result from the
simulation agrees well with the hand-calculation for required power included in the
appendix. This is a centrifugal pump made of stainless steel. The purchase cost,
determined from cost charts, is $11,570 and the bare module cost is $57,860.
54
Pump P-540 is used to increase the pressure of the absorber solvent stream S-507
from 31.8 psi to 235 psi so that it can be fed to the top stage of the absorber AB-320,
which is at high pressure to maximize acetaldehyde recovery. The volumetric flow rate
is 1149 ft3/hr. The power requirement is 9.7 kW, but the efficiency is 0.52, so the total
power is 18.6 kW. This is a stainless steel centrifugal pump, and the bare module cost is
$57,860.
Pump P-600 is used to increase the pressure of the acetic acid distillation column
feed from 37.8 psi to 100 psi. The power requirement is 1.86 kW, but because of the
P-620 pumps the S-901 recycle stream from the stream splitter to the second stage
of the acetic acid distillation column DC-61 O. It increases the pressure ofthe stream from
85 psi to 98 psi . The temperature of the stream is virtual1y unaffected by this change in
pressure. An efficiency of 0.44 is used for the centrifugal pump. The electricity
3
requirement is 3.1 kW. The volumetric flow rate is 400 ft 1hr. The estimated bare
55
P-730 pumps the recycle stream S-705 from the mixer M-740 to the mixer M-700. It
increases the pressure of the stream from 24.7 psi to 40 psi. The temperature of the
0.27 is used for the centrifugal pump. The electricity requirement is 0.27 kW. This is a
stainless steel centrifugal pump, and the flow rate is 98 ft 3l1rr. The estimated bare module
cost is $12,860.
centrifugal pump made of stainless steel, and used to pump the bottoms of DC-500. The
capacity is 289 gpm, and its power requirement is 7.46 kW. The estimated bare module
The reboiler pump for the acetic acid distillation column is constructed from
SS304. It has a design pressure of 93.65 psig, a design temperature of 408.30F and a
driver power of 11.2 kW. It is a centrifugal pump. The bare module cost is estimated to
be $45,000.
56
The reboiler pump for the acetone distillation column DC-Sl 0 is constructed from
SS304. It has a design pressure of 15.00 psig, a design temperature of215.97F and a
driver power of 0.1 kW. Based on cost charts for centrifugal pumps, the bare module
cost is $10,930.
The reboiler pump for the near azeotrope column DC-900 is constructed from SS304.
It has a design pressure of 15.00 psig, a design temperature of 231.94F and a driver
power of 0.37 kW. It is a centrifugal pump, and the bare module cost for this pump is
$14,410.
The reboiler pump for the ethyl acetate distillation column DC-91 0 is constructed
from SS304. It has a design pressure of 15.00 psig, a design temperature of 312.94F and
a driver power of 0.3 kW. The bare module cost for this centrifugal pump is $13,540.
The reflux pump for the acetaldehyde distillation column DC-500 is a stainless
steel centrifugal pump with a capacity of67.6 gpm. The work output is 1.49 kW, and the
57
PR-510, the reflux pump for the refrigerated acetaldehyde recovery column, is a
centrifugal pump made of stainless steel. Its capacity is 3.5 gpm at a driver power of 0.25
PR-610 is the reflux pump for the acetic acid distillation column. The required
power is 5.6 kW. It is a stainless steel centrifugal pump. The bare module cost is
$35,360.
The reflux pump for the stripper S-800 is made of stainless steel. It is a
centrifugal pump with required power of 0.25 kW. The bare module cost is $12,860.
The reflux pump for the acetone distillation column is a centrifugal pump and
made of stainless steel. The power required is 0.1 kW, and the bare module cost is
$10,290.
The power for the reflux pump for DC-900 is 1.1 kW. It is a centrifugal pump,
and the material is stainless steel. The bare module cost is $19,930.
58
PR-910 (see spec. sheet p. 111)
The reflux pump for the ethyl acetate distillation column is made of stainless
steel. It is a centrifugal pump with driver power of 0.1 kW. The bare module cost is
$10,290.
Since the purchase cost for each of the pumps listed above is relatively small compared to
the total capital investment of this process, a spare for each pump was purchased to avoid
Reactor
pellets. The design ofthe reactor was limited somewhat by the reaction information
available in the Eastman Chemicals patent regarding this process (Tustin et aL, U.S Pat.
No.6, 121,498). The desired reaction (1) is the reduction of acetic acid to form
acetaldehyde.
ethanol (2).
In process simulations, reaction (2) was not modeled as a sequential reaction, but instead
59
(2a)
A major factor in the design of the catalyst for this process was to promote (1), while
suppressing (2). This can also be accomplished by lowering the acetic acid conversion:
Other side reactions that were considered in designing the reactor were the production of
acetone from acetic acid (3), as well as the formation of light hydrocarbons (4).
Reaction (4) is used merely as a material balance to account for side products listed in the
patent. Selectivity to methane and C2 hydrocarbons (ethylene and ethane) was presented
as 2% total, so we assumed 1 % to methane and 0.5% for each ethylene and ethane.
The reaction conditions allow 46% conversion of acetic with reaction selectivities listed
in Table 7.
The gas hourly space velocity (GHSV) for volumes of gas per volume of catalyst was
reported as 2600 hr- 1 under the reaction conditions. The catalyst consists of 20%
palladium on iron oxide pellets. Based on a feed gas flow rate into the reactor of
224,307 ft 3/hr, this implies a catalyst bed volume 0[86.3 ft 3 (see Appendix for
Calculations). The reactor diameter is 4 ft., and the height of the catalyst bed is 6.9 ft. In
60
addition, the reactor has a 6 ft. footer, O.S ft. distributor, O.S ft. catalyst support, and a 3 ft.
header. The total height of the reactor is 17 ft. The bare module cost ofthe reactor, a
vertical vessel, is $267,400. A catalyst density of 42 lb/ ft3 was assumed, producing 3623
lb of catalyst in the reactor. At a price of $1 ,6S0/lb (Dr. Rob Becker), the cost for a
The operating conditions for the reactor are based on the optimal conditions
described in the patent: the feed enters at S99 of and 2S2 psia, with a hydrogen to acetic
acid ratio of SI1 by mole. Under the conditions of the patent, the catalyst does not show
significant degradation in perfonnance with time on stream, and because coking is not
complete replacement once every five years. The material of construction for the reactor
is stainless steel. One benefit of the catalyst described in the patent for the process is the
methods employed earlier. It was suggested that carbon steel may be satisfactory for the
material, since gaseous acetic acid is not expected to be corrosive. However, on the
suggestion of Bruce Vrana to limit possible sources of corrosion throughout the process,
we decided to use stainless steel for this vessel. Stainless steel is also stable at the
Reboilers
The reboiler for the acetaldehyde distillation column DC-SOO is a kettle reboiler
constructed from stainless steel. The heat duty is 16,892,000 BtU/hr at a bottoms
61
temperature of262.7 of. Steam purchased at 75 psig is used to provide the energy. Two
reboilers in parallel are used, and the effective heat transfer area is 8,108 ft2. The
estimated heat transfer coefficient is 105 Btu/(hr-ft 2_OF). The installed cost calculated by
B-JAC is $153,460.
The reboiler for the acetic acid distillation column, constructed of stainless steel,
employs 600 psig steam for the 39,534,800 BTUlhr heat duty. The process fluid is at a
pressure of 98 .6 psi. The heat transfer area required is calculated to be 7,200 ft2 assuming
The reboiler for the acetone distillation column, constructed of stainless steel,
employs 35 psig steam for the 252,310 Btu/hr heat duty. It is a kettle reboiler. The
process fluid is at a pressure of 22 psi. The heat transfer area required is calculated to be
120.2 ft2 assuming a heat transfer coefficient ofl 02 BtU/(hr_ft2 _OF) . Its installed cost is
$10,620.
The reboiler for the distillation column DC-900, constructed of stainless steel,
employs 35 psig steam for the 3,150,280 Btulhr heat duty. The process fluid is at a
pressure of 30 psi. The heat transfer area required is calculated to be 626 ft? assuming a
62
heat transfer coefficient ofl 0 l.5 Btu/(hr-ft2 _OF). The installed cost for this kettle reboiler
is $15,520.
The reboiler for the ethyl acetate distillation column, constructed of stainless
steel, employs 75 psig steam for the 486,920 Btu/hY heat duty. The process fluid is at a
pressure of 20.1 psi . The heat transfer area required is calculated to be 109 ft2, based on
an estimated heat transfer coefficient of 100 Btul(hr-ft2_OF). Its installed cost is $8,740.
Reflux Accumulators
Liquid reflux from the top stage of the acetaldehyde distillation column DC-500 is
returned to the reflux accumulator D-500. The vessel is stainless steel to prevent
corrosion from acetic acid or acetaldehyde. It is a horizontal vessel with diameter equal
to 3.5 ft. and a height of 10ft. The capacity of the accumulator is 852 gallons, and the
510 is made of stainless steel and has a capacity of 53 gal. Its diameter is 1.5 ft, and it's
length is 5.5 ft. The material is stainless steel and the estimated bare module cost is
$16,624.
63
This reflux accumulator for the acetic acid distillation column is constructed of SS304
and has a capacity of 3000 gallons. The dimensions of the vessel are 5.0 ft in diameter
This reflux accumulator for the stripper, constructed of SS304, has a capacity of
66 gallons. The dimensions of the vessel are 1.5 ft in diameter and 6.0 ft in length. Its
The reflux accumulator for the acetone distillation column has a capacity of 50
gal. It is a horizontal vessel with 1.5 ft diameter and 5.5 ft length. The material is
This reflux accumulator for this distillation column is constructed of SS304 and has a
capacity of 187 gallons. The dimensions of the vessel are 2 ft in diameter and 8 ft in
This reflux accumulator for the ethyl acetate distillation column, constructed of
SS304, has a capacity of 48 gallons. The dimensions of the vessel are 1.5 ft in diameter
64
Refrigeration System
The refrigeration unit was not rigorously designed, but the estimated costs of
purchasing and operating a packaged unit were analyzed. This refrigeration unit cools an
ethylene glycol solution, which in turn is used to provide a heat duty of 612,900 Btu/hr to
the condenser C-520 at 10F. Assuming "heat leak" of 30% of refrigeration produced,
the refrigeration unit was designed to operate at 900,000 Btu/hr (75 tons). Since heat
would be transferred indirectly through a glycol solution, the refrigeration unit itself was
considerably more expensive and more heat loss is expected. According to costing
estimates, a refrigeration unit this size costs $356,800 installed (Walas). Because of
uncertainties regarding how complete this quoted system is, and factoring in costs for the
glycol solution and holding tanks, we set the installed cost at $500,000 for this unit.
Operating costs were estimated based on the amount of steam and cooling water required
Splitters
PRODSPL is used to split the reactor product S-206 into two separate streams to
heat the acetic acid and hydrogen feeds. This is done rather than introduce S-206 to the
heat exchangers sequentially because it allows the temperature of both S-201 and S-207
65
iIii
to be raised to nearly the same value. Because of the difference in the calculated heat
duties in HX-210 and HX-200, one third of the S-206 is sent to HX-200, with the
SPLIT splits the hydrogen rich gas stream exiting the absorber AB-320 into a
recycle to the reactor, and PURGE, which is flared. The flow rate into SPLIT is 19,877
Ib/hr, and 98.7 % is recycled to the reactor. This split fraction is as high as could be
process. SPLIT2 splits 92,140 lblhr of S-506 into the solvent for the absorber AB-320 at
62,277 lb/hr and the balance to the acetic acid distillation column. SPLIT2's role is to
recycle acetic-acid rich solvent back to AB-320 where it absorbs acetaldehyde. The split
fraction was set by the interest of maximizing recover of acetaldehyde without causing
ETACSPLIT splits the 28181.37Ib/hr liquid stream S-901 at 117.5F and 35.5 psi
into two separate streams. 79.17% by mass gets diverted to the liquid stream that is
Stripper
This stripping is designed to remove the water from the system in the bottoms to be sent
dispose of it. The bottoms stream, WASTE WATER, contains 89.2% by mass of water.
66
The main impurities in this stream are acetic acid (8.5%) and acetone (1.6%). The
distillate stream, S-804, primarily contains ethyl acetate and acetone. The stripper was
designed using 4 equilibrium stages; the tray efficiency is 34.8%, so the actual number of
trays is 12. Since there is no reboiler in this column, there is not a bottoms sump, but
there is a 4-ft. disengagement height for the condenser. To that end, this separation
column is 28 ft. in height and has a diameter of 1 ft.; both the trays and the column itself
are constructed out of stainless steel. The water-rich decanter product stream S-80 1
enters the column at tray 2. Steam is introduced into the stripper at 2161 lb/hr at the
bottom tray. The distillate rate is 1194 lb/hr and the operating pressure is 22 psi. The
Tanks
Storage tank T -1 is used to hold a one-day supply of acetic acid feed. It holds
only this much because our facility is on the site of a major chemical company, so there is
no need for us to maintain a large inventory. At steady state, the volumetric flow rate of
pure acetic acid feed is 320 ft 31hr, which would imply the need for a 7,680 ft3 holding
tank for the reactant. The tank is made from stainless steel to resist corrosion. The bare
Tank T -2 holds a 12-hour supply of the bottoms product from the acetic acid
distillation column, stream S-103. The volumettic flow rate is 402 ft31hr, and the
67
necessary volume for the holding tank is 4824 ft3. The material of construction is
Tank T -3 holds a 12-hour supply of the acetic acid bottoms product from the ethyl
acetate distillation column. The volumetric flow rate of this stream is 7.5 ft 31hr, so the
required tank volume is 90 ft3. This vessel is made of stainless steel and has a bare
module cost of $6,940. Both T -3 and T -2 can be used to store additional acetic acid that
will be necessary at start-up, when there are no recycle streams to augment the fresh feed.
Tank T -4 is used to hold a fourteen day supply of ethyl acetate product. The
volumetric flowrate of the product stream is 21.8 ft3 1hr, so a tank with a volume of7,309
ft3 (207 m 3) is required. This is a stainless steel vessel, and the bare module cost is
$115,700.
Holding tank T-5 holds the combined acetaldehyde product from the HAC
combined volumetric flow rate is 275 felhr, and the required volume is 92,400 [e. The
material of construction is stainless steel because high levels of acetaldehyde can corrode
carbon steel. Because of acetaldehyde's low boiling point, there must be cooling
facilities to keep the temperature below 60 OF, this is considered when calculating the
68
bare module cost, as the purchase cost was multiphed by a factor of two (in addition to
the bare module factor) to account for refrigeration. The purchase cost is $66,860, and
Storage tank T-6 is used to hold the intermediate S-501, before entering the
the reactor effluent S-206, but its high temperature and large volumetric flow rate
because of the large presence of hydrogen and carbon dioxide gas make this impractical.
In case of plant stoppages that stream must be flared. The volumetric flow rate of the
distillation column feed is 1810 fe!hr, so a tank that can hold a 12-hour supply of this
material must have a volume of 21,720 ft3 (615 m 3). This tank must be made out of
stainless steel because of the corrosion risk from acetic acid. The bare module cost is
$127,300.
Tank T -7 holds the bottoms product S-506 from the acetaldehyde distillation
column DC-500; this location is chosen because if there is a shutdown in the acetic acid
separations section, the acetaldehyde reaction/purification section can still operate. The
volumetric flow rate ofS-506 is 1700 ft3/hr, so a 12-hour hold of it will occupy 20,400
fe . This must be made of stainless steel because of the high acetic acid level, and its cost
is $115,700.
69
Valve
The valve V-SOl is used to decrease the pressure of the feed to the acetaldehyde
distillation column from 230 psi to 43.5 psi. The flow rate of the stream is l05,380 lblhr.
The pressure of this liquid stream is decreased because the acetaldehyde distillation
70
lL
Sl.33HS NOll.VJlilIJ3dS l.INn
ABSORBER
Operation: Continuous
Comments & Drawings: See process flowsheet pg. 13 and Appendix A p. 177.
72
Compressor
Principal Function: To increase the pressure of the hydrogen feed into the furnace
Operation: Continuous
Materials
handled: Inlet Stream Outlet Stream
S-403 S-207 -
Quantity (lblhr): 20,404.31 20,402.42
Composition (lblhr):
Hydrogen 7,781.46 7,781.47
Carbon Dioxide 5,137.53 5,137 .53
Methane 1,495.13 1,495.12
Ethylene 855.36 855.34
Ethane 855.42 855.42
Acetaldehyde 623 .59 621.46
Acetone 285 .38 285.40
Ethyl Acetate 906.41 906.51
Ethanol 17.24 17.25
Water 933.93 933 .97
Acetic Acid 1,512.85 1,512.96
73
749473
14 Noncondensable Ib/h 584
15 ..
16 Temperature (In/Out) F 115 101.8 90 105
17 Dew / Bubble point . __._- F 110.55 --.- .- -
18 Density Ib/ft3 0.235 46.676 -_ .. 61.587 61 . 07~_ _
~ _._
Latent
........_...heat
_-.... BTUllb 187.8 192.7
JElI~. ~. pre~sLJ.rE:!.(abs~l,!,~)
~ ~i 32 80
26 Velocity ftls 9.8 2.96
27 Pressure dro p, allow./calc. . .. Q.~i 2 1.412 20 [ ' 4.987
28 Fouling resist. (min) ft2*h*F/BTU 0.003 0.003
29 Heat exchanged 10530000 .. J3TU/h MTD corrected 9.3 F
30 Transfer rate, Service 86.34 Dirty 97.6 Clean 276.49 BTu/(h*ft2*F)
31 CONSTRUCTION OF ONE SHELL Sketch
32 .._-_. Shell Side Tube Side
40 Tube No. 4378 00 0.75 Tks-avg 0.065 in Leng!b.. .. ... ft Pitch 0.9375 in
41 Tube type Material CS ---.. I Tube !2attem 3..0
42 Shell
---
CS 10 0070 in Shell cover -- _._-
43 Channel or bonnet C$ .. Channel cover ..........._-
44 Tubesheet-stationa~ CS _ _ ..I!:!~~?_~.eet-floating
45 Floating head cover .. _ J.m!2ingen:l~l p.~<?tection Plate on bundle .... _.".
46 Baffle-crossing CS Type single seg Cut(%~1_4? vert S!2acing: dc p.?? ".".__ .. ._- in
47 Baffle-long Seal'!y..Q~. --
1 Inlet 23
.-.................
in
- - .- - -
48 Supports-tube
49 Bypass seal
.. _ U-bend
-ILJ.be-tubesheet joint
T~Re
9!oove/ex!2and
-
..-..
- -~,.- -
303 0.8165
0.108 0.258
.....l06.6
8
261 Velocity ftls 9.98
27 Pressure drop, allow./calc. psi I 2
- -0.89
- 20 1.156
281 Fouling resist. (min) ft2*h*F/BTU 0.003 0.003
291 Heat exchanged 612890 BTu/h MTD corrected 48.37 F
- - - -
301 Transfer rate, Service 31.43 Dirty 32.18 Clean 40 .9 BTu/(h*ft2*F)
,,=
, je; CW
... ----------+-----~--'-'=-'---------+-------=-.:..::....--- .- . -
f-'1-=6+-T;:.;emc..:1J::.p~e;:.;r-=a.:.:tu:.:r.e::....>.:
(I'-"n/-=O:...::u"'t)'___ _ _._ ______ - ----=-+---=-=-=-=---1--=-'-~.-~--=-"---_+_--
308.23 270 88 :....:
17 Dew / Bubble ~oint 308.23 235.31
18 Density 0.421 51.55 ..... _... 62.241 , -~
~
LocatiOn :
3 _~ervice of Unit: Our Reference:
4 Item No.: C-800 Your Reference:
5 1Date: Rev No.: Job No. :
61 Size 8--192 in TY2.e BEM hor Connected in 1 garallel 1 series
71 Surf/unit(elf.) 112.2 ft2 Shell s/unit 1 Surflshell (elf.) 112.2 ft2
8 PERFORMANCE OF ONE UNIT
~I' Fluid allocation Shell Side Tube Side
10 Fluid name S- ~a.t C. W
11 1Fluid quantity, Total Ib/h 10586 32660
f-=--I----,-",,,-=->.:.n/Out) .. . _ .. !~'-I! 4160 . j I
_. Ib/h 6427 10586 32660 32660
14 Noncondensable Ib/h
1
15
- - - - ---. ' .1 I
16 Tem . erature (In/Out) F 184.8 181.7 90 120
~~J3_ubble point
1QA Q
17 FI 183.65
50~~~8 __ J.__~~;:24
18 Densi ______ ..____ __._ _ _ Ib/ft3 1__ --
0.238
- -""-_._ 61 .864
19 Viscosity cp 0.01 -- 0.561
~. _~olecular wt, Vap 62.27 60.93
211'0<?Lecular wt, NC
22 Specific heat BTU/(lb*F~ I 0.36.----.-- 0.6136
-
23 Therma.Lconductivity BTU/(ft*h*F 0.01 0.076
24 Latent heat BTUllb 391.5 397.7
25 Inlet pressure (absolute) psi I 27
26. Velocity ftls_1 38 42
27 Pressure drop. ,?lIow.lcalc. psi 3 I 2.855
28 Fouling resist. (min) ft2*h*F/BTU ~
0 .(
29 I Heat exchanged 97 9980 BTU/h MTD cc: .rrecled
30 I Transfer rate , Service 111.78 Dirty 112.22 Clean 438.22
31 CONSTRUCTION OF ONE SHELL Sketch
32 Shell Side Tube Side
'''J J U'~
,,,on pressur~
331 OesignlTest si 7?i ___ LQ{)de 75/ / Code
34 Design temperature
35 Number passes per shell
F 250 180
4 ~~
? t
36 Corrosion allowance .. in _ __.9,Q..?;,.:".5 --1
1 '1
a
Heat Exchanger Specification Sheet
1 Company: --_. __.._._ ---_ .... _ - - - --
2 Location:
r - - - - -----
---3.. Service
............. __ .. __ .of Unit: C-810 Our Reference:
-
4 Item No.: ----
Your Reference:
5 Date: Rev No.: Job No.:
6 Size 8 --120 in Type BEM hor Connected in 1 ~arallel 1series
7 Surf/unit(eff.) 77.6 ft2 Shells/unit 1 Surf/shell (eff.) 77.6 ft2
8 PERFORMANCE OF ONE UNIT
9 Fluid allocation Shell Side Tube Side
10 Fluid name S-!/ll'; r-- CW
11 Fluid quantiY. Total Ib/h 1714
- - - --- 14289
J1. 1-- VapQlj.ln/Outl. Ib/h 1714
13 Liquid Ib/h 1714 14289 14289
14 Noncondensable Ib/h
-- - -
15
16 Temperature (In/Out) F 174 .5 167.6 90 120
17 Dew / Bubble Q.oint F 170.2
18 Density Ib/ft3 0.185 49.348 62.224 61.864
19 Viscosity cp 0.042 . - _ .". 0.261 ._..... 0.762 0.561
20 MQIEi..~!ar wt, Va ~
~J Molecular wt, NC
22 Specific heat ._ - - - --_.._._ .. _.. BTU/(lb"F) 0.3426 0.567 1 1.0006 0.9998
~Q~~~~ I ~~~:==
23 Thermal conductivity BTU/(ft*h"F) 0.01 0.099
BTU/lb 246.2
~ ~~ ntheat 247.9
25 Inlet pressure (absolute) ...._--_.. _--_ ... _
psi 22 . -- --_._-- _......._--_80
26 ~~L~ --_. ftls 9.66 2.76
27 Pressure drop, allow./calc. psi 2 0.363 15 1.206 _.
1 - - -
28 Fouling resist. (min) ft2*h*F/BTU 0.003 0.003
29 Heat exchang~_d 428730 BTu/h MTD corrected
._-_._-_ .. _... _.... 62.71 F
30 Transfer rate, Service 88.15 95.04 Dirty Clean 245.66 BTu/(h*ft2*F)
31 CONSTRUCTION OF ONE SHELL Sketch
32 SheIlSid~ __ '--__ I'=!Q~..lcli!__ _
57 ._-
58
Heat Exchanger Specification Sheet
1 Company: "'''" . _,.
- Item No.:
c--- C-900 Your Reference: _._-_.-
- "- _ ....
5 Date: Rev No.: Job No.:
Size ....--
-~ ----_ 12--168 in Type BEM hor Connected in 1 parallel -. 1series
.. _.,------ __
7 Surf/unit(eff.) 275.2 ft2 Shells/unit 1 Surf/shell (eff.) 275.2 ft2
8 PERFORMANCE OF ONE UNIT
9 Fluid allocation Shell Side Tube Side
- .. _ .-._-----
10 Fluid name :) - 7<,.\ cw I
11 Fluidquantitv, Total Ib/h 24205 97030 _... _-
11501
~ _Vapor (In/Out) Ib/h
13 Liquid Ib/h 12704 24205 97030 97030
14 Noncondensable Ib/h
15
16 Temperature (In~Out) F 215 183.9 90 120
17 Dew / Bubble point F 215 210.56
-
,.:L~ ~J2Q~!Y. Iblft3 0.225 51.137 62.224 61.862
..1~ '{iscosity cQ 0.071 0.266 0.762 0.561
20 Molecular wi, Va~ ______ 56.19 ... 60.08 "'
80
0.364 ..
1'1
10 Fluid name C. W
11 Fluid quanti!!', To!?1 Ib/h 8763 16983
-
12 Vapor (In/OutL-.._.. Ib/h 8763 5634
-
-_.
13 Liquid Ib/h 3129 16983 16983
14 Noncondensable Ib/h
15 - - -
16 Temperature (In~Q.l!!) F 181.6 175 90 120
17 Dew / Bubble J!9J.rlL F 175.4
18
._--.-
Density . . - - . Ib/ft3 0.203 51.497 62.224 61.864
19 Viscosity -- ... cp 0.091 0.255 0.762 0.561
20 Molecular wt, Vap ..
21 Molecular wt, NC
22 Specific heat BTU/(lb*F) 0.3126 .. 0.505 1.0006 0.9998
23 Thermal conductivity BTUJ(ft*h*F) 0.009 0.074 .__ .. 0.352 0.364
24 Latent heat BTUlib 156 157.1 .. -----_.... _-_.
25 Inlet pressure (absolute) psi 16 .. _._-_ ... _ 80
26 Velocity ftls 9.9 0.71
27 Pressure drop, allow.lcalc. . psi 5 0.315 15 ..___J 0.22
28 Fouling resist. (min) ft2*h*F/BTU 0.003 0.003
29 Heat exchanged 509570 BTu/h MTD corrected 69.13 _....E...
30 Transfer rate, Service 15.59 Dirty 72.57 Clean 139.86 BTUJ(h*ft2*F)
31 CONSTRUCTION OF ONE SHELL Sketch
32 Shell Side Tube Side
33 DesiqnlTestEessure psi 751 ICode 751 ICode e ? !
~
34 Design temp_erature F 250 180 .. ' ,
35 Number passes per shell 1 8
i !
36 Corrosion allowance in 0.0625
37 Connections In 6/150 ANSI 2/150 ANSI
38 Size/rating Out
--- ._-_._
6/150 ANSI 2/150ANSI
~~ .... _.. _. __ . in/ Intermediate 1/150 ANSI /150 ANSI
Tube No. 410
40 -.------_._- OD 0.75 Tks-avg 0.065 in Length 6 ft Pitch 0.9375 in
41 Tube type Material CS I Tube pattern 30
42 Shell SS304 ID
----
OD 24 in Shell cover .. - --- -
Channel
43 - -_.. _--or bonnet CS Channel cover
1--
44 Tubesheet-.~tational.. SS304 __.
1-._. Tub~~heet-floating
45 Floating head cover _ Impinqem~PE()t~ction Plate on bundle
46 Baffle-crossing SS304 Type _single seg Cut(%d} 43 -~ - .
vert Spacing: dc 30 .__. _ -in
47 Baffle-long Seal type I Inlet 20.25
-- in
48 Supports-tube U-bend lYJ:>e__.
49 Bypass seal Tube-tubesheet joint _.gr()ove/~_x"pand
50 Expansion joint .~
. -- - .
Type ----.. _-,...... _.
51 RhoV2-lnlet nozzle 757 Bundle entrance 99 Bundle exit 36 Ib/(ft*s21
52 Gaskets - Shell side Tube Side .. - .. _--_ ...... ... _-_.
53 Floating head .".-,--- _ ..
54 Code requirements ASME Code Sec VIII Div 1 TEMA class B -~,, - ..-
55 Weight/Shell 2571.3 Filled with water 4020.3 Bundle 1640.9 Ib
56 Remarks . _---- .. -- .. __ .. _
.
57 -. ---"
58
DECANTER
Principal Function: Separating out all of the water from the ethyl acetate
Operation: Continuous
Materials
handled: Inlet Stream Outlet Streams I
81
Distillation Column
Operation: Continuous
82
CONDENSER COLUMN
Identification Item Condenser column Date: 4/9/02
Item # DC-510 By: cp
No. Required 1
Principal Function: Separates the Acetaldehyde from the offgas outlet stream from
the main acetaldehyde column
Operation: Continuous
83
Distillation Column
Operation: Continuous
84
DISTILLA TION COLUMN
Operation: Continuous
- --"
85
DISTILLATION COLUMN
Operation: Continuous
86
DISTILLATION COLUMN
Operation: Continuous
I
I
I
Acetone 0.89 0.89 trace I
- - - - - - - - -
87
.......
FIRED HEATER
Operation: Continuous
Design Data: Heat Duty (MMBTU/hr) 15.29 Average Pressure (psia): 253
Material of Construction: Stainless Steel
Comments and Drawings: See process flowsheet pg. 13 and Appendix A p. 180.
88
FLASH VESSEL
Principal Function: Separates the S-302 stream into a vapor and liquid
Operation: Continuous
- - ~ - ----.-
89
=-_ _ __
11 Fluid quantity. Total _______._--=I.=.b/'-'..h+-_ _ _--=:c2Q; g L_____l -_ _ _ -=27:..r6:..::5:.::2e-_ _
-.-
12 Vapo~_ln/Qut)
-"-_ __ _ _ __ __ _-"I b/h 20322 20322
3733
---
~+-~~~--------------~I~b/~h
13 Liquid
_ _ _ __ -,~----+-~~~-~-~~~
27652 23919
l--"-'-i_--'-'-'''-====~
14 Noncondensable _ __ _ ___ __ ---'-''lb''''/h'_'+_-.--- - -_ t _ - - --_t_
.- -
15
--
~+__'_'=:J"--e.:.;=c:::..l"-"-'::.=L---------------'-F+_-~55"-'6"".9~---
16 Temperature (In/Out) I- -~~-+--..::..:....:..:=
241.9
- 464.7
17 Dew / Bubble point F 463.45
~ Density_ __ _ __ __ _ _ _ _ _~lb~/~tt=_3~-~~-_+-~~
0.294 0.406=--__+ 58_042 1.925
19 Viscosity cp 0.017 0.013 0.375 0.015
~2c:c0-t-'-'-Mc:cO-,-,le",c.=.
ul:.::
a.;....
r "'-'-".
wt.-'-'-
V a-'-
p_ ___.. .___ _ _ __ _ _ _ _--t_ _ _ _ ___t_- - ---
........
~2c.:.
1-t-'-'-Mc:co-'-'le'-=c.=.
ul:.::
a.;...."'-'-".
r wt . _--=~N C __ _._..__
. _ __ ____ _ _ +-_ _____t_.I -.- ... ~-.
......;..:;;..;;;..::.-.::..:.=__ _ _ _ __ ._ _ __ _ _ _ __ _ .._ _
I
1" - - - - -. -+1- - - - +------+-----+-----
16 TemR~@_~re (In/Out) F 556.8 280.1 202.6 475.51
17 _Dew I By'p_ble point F
18 Densi _ ____ .___ __._.___... _.___.__._._ _ _!2!~-0.293 0.405
!Q. Viscosi _ _ .._ _ _ ____ .c;p.. 0.017 0.013
20 Molecular w1, Vap
211 Molecular w1. NC
22 S ecific heat BTU/(lbF~ I 0.7766
--._-=
E- 0.7339
f}_ Thermal co.Q.ductivity BTU/(ft*h*F 0.09 0.073
24 Latent heat BTUllb I
- -
f2ll!,-et pressure (absolute) 25
I
26 Veloci 8.
27 Pressure drop. allow.lcalc. psi 5 3.16 I 8 0.386
281 Fouling resist. (min) ft2*h*F/BTU 0.003 0.003
29 Heat exchanged 8740987 BTu/h MTD- cc-Irrected
-
30 Transfer rate , Service 5.72 Dirty 16.7 Clean 18.72
31 1 CONSTRUCTION OF ONE SHELL Sketch
32 Shell Side Tube Side
331 DesignlTest pressure psi 260/ ! Code 280/ / Code
34 Design temperature
35 Number passes per shell
36 1Corrosion allowance
F
I I
w-~
37 Connections In 10 / 300 ANSI 81300 ANSI .I
~_~_J3ize/rating Out 10 / 300 A_~SI 10 / 300 ANSI I
39 inl Intermediate / 300 ANSI ___ 1 300 ANSI I
40 Tube No. 3427 _ 00 0.75 Tks-avg 0.049 in LenRth 10 _ ______ ft Pitch 0.9375 in
41 Tube type __._...________ Material SS304 [ Tube pattern 30
42 Shell
.-.:::.
SS304
-' 10 00 60 in . ._ Shell cover
~ 'yJl_<l.r1IlE!L.Qr bonnet SS304 .. ~hannel cover
~l.l!~E!he.E!!:~tationary SS304 ___ _Iu_be.sheet-f1oating
45 Floating head cover Impingeme..f!!J~ rotec!Q_
n _ . _~one
46 Baffle-crossing SS304 Type single seg Cut(%d) ~_'2.<?I. Spacing: clc 24.75 in
47 Baftle-Iong Seal type . 1 Inlet 20.125 in
48 Supports-tube _.__ _ _ _ .. _ U-bend __.._.--.!YP.e _ _ __
49 B ass seal .... ._ _._....
Tube-tubesheet joint groove/expand_
50 Expansion jOint Type __ _._.___._.____...__
51 RhoV2-lnlet nozzle 1506 Bundle entrance
- 1732 ..-- . ...... _
._-_._-..........
Bundle exit __ . 1256 .._ _I_
b/tf!':~~
1---'1-t-=:.::::.:.:=:c.:.L'
Company: - - -- - -- - - - - - - -- - -- -- - -. -- - - - - - - -.."...- - - - - - - -
2 Loca tion:
f--=+-===;;.;.:,..- - - - - - -- - - - - - - -- - . - - -- --"--.-- - - - - - - -".- - - - - - - -
Our Reference:
3 Service of Unit: - - - - - _::::..::.:....:....:.::..:..::.:..=.:-=-=.:'--------_._- - - - -- - - - _.. _ - -- --
--~ Item No.:
.: HX-300
='__--'-..c..:....::.::.=--_ __ _ _ Your Reference: _ __ _ __ _ _ __ _ ._ _ _ _ _ _ _ _ ___________
....:....::=-:c..:.::.;c::.:...::=.::..:....
5 Date: Rev No.: Job No.:
6 Size 57 --144 in Type 8EM hor Connected in 1 parallel 1 series
7 Surf/unit(eff.) 6687.1 ft2 Shells/unit 1 Surf/shell (eff.) 6687.1 ft2
8 PERFORMANCE OF ONE UNIT
f~+-'-=::"'O:::==~
9 Fluid allocation _____ ________I ----'--S7h..:.:e:::,":_:S::.::ide
"'=---- -_j-------'Tc.::u:.:::bc::-
e_S,,,,,id,,,,,eoC-.__ .____
.
10 Fluid name S -301 C Wo.
~~~~~~~~---------~
11 Fluid quantity. Total lb~/h~----~6-=3r03~1'-----+_----~71~7r3~7~7____._.
~_j__~='-'-'-'.::.==-<----------.---'I.::cb/"-'h+_---'5::.:.7..:::6""05"--_+--1.:.::8:.:::0~78
12 Vapor (in/Out) "---I_---- ____j__---
~_ _'=i.9.':l.lL. ____ _ ____._ _ _ _ _ _ _ _-'-'lb<,/"'h 1_ _ _ _ _ _ _!_'--3:::.:9::.::5:.::2~7-_t_-7
'-1-'-'-"
7 3"-7
7'---_!_--'-7-'-1.:..:73:::.:7-'-7--
~j_____ _
"'!Qn_~!!__
de n?a
__bl ~. Ibtl! __ . 5427 - .--t. -- - -
1~ - - - - -- - -- , - . - -- -- - - - +- -- - ---1--- - - - - 1 - -- - - ,,
16 Temperature (In/Out) r---_-'-"-"___ +-_---=90=--_-+_ _ 1..?Q.__._
17 Dew / Bubble point . -...- - - - - - - - ' - t--=-'-'- "'-"-- - 1 -- - -- + _ - - -- -1-- - - - -
~ Q~..!l~_ _ _ _ __ _ _ _ _ _ _ _.__'~,. 61.587 60.566
19 Vis~~l'_ __ _ __ _ _ _ _ __ _ _...::=.I-----":.:.=...=-- +_-...::.:.::.='---t- _ ::.:
0 ."-.::::
78 3 =----1_---"..:.:
.5::.:.7...:.1_ _
1
!-"2:.-:0_f-'-'
Mo:.:,::.:
.:.:: lec:..::"" ula:.;,.r..:.;"". IP'___ _ _ _ _ _ __ _ __ -t-_....:.::..:.:::.:._ __._f-- .:.=.:.:...::...--t----- - -t----.- -
wt ' -V:...:a:;<
I-c2:. :1--1-'-'
M.:.::o:.:,:le:..:c:..::u.:..:
la:.;,.r..:.;
wt c;J.""N
.;:..C
=--_ _ __ _ _ _____ _-+_--..:4c.:4..:.:.0::.:1_.._ _".._..:.44..:.;.'-=-0..:...1_-+_ ____ --1_ _ _ __ _ 1
1-"'2=2+-=,-pe
S",::.;c""ifi.:.:;
lc:..oh.:.::ec=t
a.:..._ _ _ _ _ _ _ _ _-=B::.:T:..::U:..;./(>.::lb::-_*r:l_-=-0.'-'..7..:..::.. 184-=----1-_-=- 0.c=.91
5.::..-=-----1f-_=_0:.::
.9..::.30=-:2=----1-_ __ 0.9567
~2~3+"- T::.:.~~~~-=~n
he rma l co c:.:d::.::u:..::c:::.-'-'
tiv i~tty_ _ _ _ _ _____'B::<.T.:..:U~""'(1ft"--'-h'-*F'__":)4-_...:0
:::.:.-=7
0'__ _+-.......::0:.:.:
.0::.::9::.::9'--_+-_.0.0.:._30.5.::..6=--_ 1--_0..::..::..8
::.:36 =--_1
~2:.::'4+=-~te-,-,
La ~ n.:..:th c:.:e::.::::,_
at __ __ _ _ _ _ _ _.......::B""'Tc.::U<'-/"' lb'-l____ _---+_ _ _ _ _+_- -""".----"'-- -____ I
34 Desiqn temperature
35 Number passes per shell
F .._....::.34-'-'0= --_ _ _ +___...:1:.::8:.::0_ _ --1
1 S
~
.
;
.
4.~8~S.:::
u ~~"'
pP(O rts:..:
-t:.::
u.:::::::_..
be _ _ _ __ __ ____'U
::<.-_"b_=
e::.:.:::_.._
nd ... _ __ _ _ ______T.Y~_._ ____. ___"._._..._ ._ _
_
,~~)'P.ass seal __ Iu.Q.~..::!.':l.besheet joint_.. .. . __grQ.ove/expand
5~0_+=-~~~~
Ex p a n s::.::
io::.:
n..J;joi
:::;::.:.
nt:..-_ _ _ ._ _ _ _ _ _ __ _ __T:.ry,pEe_ '-= _ _ _ __ _ _ __ _ _ _ ____ .......".......__
51 RhoV2-I nlet nozzle 1257 Bu nd Ie en tran ce =-=--_ _ _ __ _~-=
"-354 B u'_'_=~
nd l e..::e..:..;
x'_'_it......:..11,-1_
.
_ _ Ig/m:'l@
5~2~G
:::;a~s::.:
k_=ts_'
e =_ -.:.::::.:.
S h::.::e::.:.
II .:::.id_=
s:.:: e_ __ _ _ _______ _......:. T_=be
u.::."---"""___
Side'--_ __ __ ,, __ ._. "_____ . __ _ _ _ ._ _
. ~5::!..3j---......:.F..:.:=o
lo a'-"ti.:..:
n-"g--'-'h-=ad
e=:::.....-.-------- . - - - . - _._...........__.__ _ __ ___. . _-- -- - - -
54 Code reg uiremen~.._ ._ _-'A..:cS=M~E....:C""'od=e....:S""'e::.::c:...V:..:I.:.:".:::.D~iv:....:...1_ ___ ._ _ . TEMA class .=B_ _ _ _ _ _ __
55 WeighVSheil 33610.4 Filled with water 52103.5 Bundle 24991 .7 Ib
56 Remarks
~5~7+------------ ..- - - - - -- - - --- -- - - -- -,,---- - -- -- .-.._""..""___.......... _.
58
Heat Exchanger Specification Sheet
1 Company:
2 Location: ._---_._ ---_._--_.._ - -...__.._ -_._ - - --
3 Service of Unit: Our Reference: -_._-----------_._ ._ ._-_ .. -- -
4 Item No.: HX-530_._--_._-----_._..__Your
... _--_.. "
Reference:
... .._---.-.----- _ - --- - _
.. ..
~ .
34 Design temRerature F 330 180 ,
35 Number Rasses per shell 1 2
~ I
36 Corrosion allowance in 0.0625
37 Connections In 3/ 150 ANSI 6/ 150 ANSI
Out 3/ 150 ANSI
~ _Si?e/rating 6/ 150 ANSI
;39 in / Intermediate / 150 ANSI / 150 ANSI
40 Tube No. 82 00 0.75 Tks-avg 0.065 in Length 20 tt Pitch 0.9375 in
41 Tube type . Material CS I Tube Rattern 30
42 Shell SS304 ID OD 10.75 in Shell cover
43 Channel or bonnet CS Channel cover ._.
44 Tubesheet-statio~'~Q~ Tubesheet-floating
.5~ Floating head cover Impinqement protection None
46 Baffle-crossing_ SS304 T~e single seg Cut(%d) 27 hor SRacing: dc 4.625 in
47 Baffle-Ionq Seal type 1 Inlet 10.5625 in
48 Supports-tube U-bend Type
49 Bypass seal Tube-tubesheet joint qroove/expand
50 Expansion joint Type
51 RhoV2lnlet nozzle 1130 Bundle entrance 129 Bundle exit 120 Ib/(ft*s2)
52 Gaskets - Shell side Tube Side
53 Floating h~l.g_ .._
-'- . -_...._--- - _. __ ._.. _...._... _- - -----_._-- ---_.
B ... _--_.-.-_.. _..._
54 Code reQl!irements___. ... _._._~SME_~.Q1?_9~.c;.Y"1 Div 1 ----------_._..TEMAciass
"--- _.... __...__ ._-_..... _-_ - ._ .._-_.
55 WeiqhUShell 1538.1 Filled with water 2250.1 Bundle 935 Ib
~ rB~f!1arks
2- f--.
58
-
. C'1.
Heat Exchanger Specification Sheet
1 Comf2 an t . .. .
2 Location: -_._.-- .
3 Service of Unit: .....HX-710
_ Our Reference:
4 Item No.: Your Reference:
--, .. _---_.__._-_..
5 Date: Rev No.: Job No.:
6 Size 17 --240 in Typ-e BEM hor Connected in 1 f2arallel 1 series
7 Surf/unit(eft.) 921 ft2 Shells/unit 1 Surf/shell (eft.) 921 ft2
8 PERFORMANCE OF ONE UNIT
9 Fluid allocation Shell Side Tube Side
10 Fluid name Cw S-70;
11 Fluid Quanl!.!Y, Total Ib/h 122949 40674
E _._Yi3.por (In/Out) Ib/h
13 Liquid Ib/h 122949 122949 40674 40674
14 Noncondensable Ib/h
15
16 Temperature (In/Out) F 90 .. 120 257 113
17 Dew / ~ubble point F ._-
18 Density Iblft3 62.224 61 .862 49.737 55.839
19 Viscosity cp 0.762 0.561 0.212 0.49
20 Molecular wt, Vap
21 Molecular wt, NC
22 Specific heat BTu/llb*F) 1.0006 0.9998 0.6598 0.6038
0.141
~ Thermal conduclivi!):' BTUI(ft*h*Fl. 0.352 0.364 0.146
24. Latent heat
.- --- BTUllb
E r1-~let f2ressure (abs.olute) psi 80 '_.
39
26 Velocity _. ftls 2.57 2.6
27 Pressure drop, allow.lcalc. ... 20 psi 19.818 3 2.503
28 Foulinq resist. (min) ft2*h*F/BTU 0.003 0.003
29 Heat ex~hanged 3689136 BTU/h MTD corrected 46.41 _----.L
30 Transfer rate, Service 86.31 95.47 Dirty Clean 260.06 BTu/(h*ft2*F)
31 CONSTRUCTION OF ONE SHELL Sketch
32 -_. Shell Side Tube Side
33 g~~gnfTest ~ressure psi 751 ICode 751 I Code 3 t
~
~ r-!2-~_~lgn temf2erature F 180 320 , ,
,
- . - ~ -.-----
Ot l
PUMP
Principal Function: Increase the pressure of the S-104 Stream from M-100
Operation: Continuous
Composition (lb/hr):
Hydrogen trace trace
Carbon Dioxide trace trace
Methane
Ethylene
Ethane
Acetaldehyde trace trace
Acetone 0.006 0.006
Ethyl Acetate 1.49 1.49
Ethanol 0.001 0.001
Water 365.11 365.11
Acetic Acid 42,205.31 42,205.31
Design Data:
Type: Centrifugal Efficiency: 0.52
Pressure Change (psia): 248.3 Electricity Required (KW) 18.6
Volumetric Flow Rate (ft31hr): 720.2 Material of Construction: Stainless Steel
Net Work (hp): 24.9
Comments and Drawings: See process flow sheet pg.13 and pricing info on Appendix A pg.184
95
PUMP
Principal Function: To increase the pressure of the S-507 stream from HX-530
Operation: Continuous
Composition (lb/hr):
Hydrogen trace trace
Carbon Dioxide trace trace
Methane trace trace
Ethylene trace .trace
Ethane trace trace
Acetaldehyde 6.47 6.47
Acetone 785.89 785.89
Ethyl Acetate 2,775.68 2,775.68
Ethanol 110.70 110.70
Water 13,552.93 13,552.93
Acetic Acid 45,046.25 45,046.25
Design Data:
Type: Centrifugal Efficiency: 0.56
Pressure Change (psia): 203.2 Electricity Required (KW~ 18.6
Volumetric Flow Rate (ft3Ihr): 95307 Material of Construction: Stainless Steel
Net Work (hp): 25 .3
Comments and Drawings: See process flowsheet pg.14 and pricing info on Appendix A pg.185
96
PUMP
Operation: Continuous
Composition (lb/hr):
Hydrogen trace trace
Carbon Dioxide trace trace
Methane trace trace
Ethylene trace trace
Ethane trace trace
Acetaldehyde 3.10 3.10
Acetone 376.83 376.83
Ethyl Acetate 1,330.91 1,330.91
Ethanol 53.08 53.08
Water 6,498.49 6,498.49
Acetic Acid 21,599.21 21,599.21
Design Data:
Type: Centrifugal Efficiency: 0.49
Pressure Change (psia): 62.2 Electricity Required (KW~ 3.83
Volumetric Flow Rate (ft31hr): 551.7 Material of Construction: Stainless Steel
Net Work (hp): 5.14
Comments and Drawings: See process flowsheet pg.14 and pricing info on Appendix A pg.186
97
PUMP
Principal Function: Increase the pressure of the S-604 stream from DE-720
Operation: Continuous
Composition (lblhr):
Hydrogen < 0.001 < 0.001
Carbon Dioxide trace trace
Methane
Ethylene
I Ethane
I
I Acetaldehyde 17.83 17.83
Acetone 1,598.79 1,598.79
Ethyl Acetate 17,200.99 17,200.99
Ethanol 110.58 110.58
I
Water 1,746.22 1,746.22
Acetic Acid 1,651.91 1,651.91
Pressure (psia): 35 98
Design Data:
Type: Centrifugal Efficiency: 0.44
Pressure Change (psia): 9 Electricity Required (KW~ 0.44
Volumetric Flow Rate (ft3 /hr): 399.2 Material of Construction: Stainless Steel
Net Work (hp): 0.6
Comments and Drawings: See process flowsheet pg.14 and pricing info on Appendix A pg.187
98
PUMP
Operation: Continuous
Composition (lblhr):
Hydrogen < 0.001 < 0.001
Carbon Dioxide trace trace
Methane
Ethylene
Ethane
Acetaldehyde 4.82 4.82
Acetone 487.45 487.45
Ethyl Acetate 4,044.88 4,044.88
Ethanol 31.88 31.88
Water 540.20 540.20
Acetic Acid 1.90 1.90
Design Data:
Type: Centrifugal Efficiency: 0.3
Pressure Change (psia): 703 Electricity Required (KW; 1.25
Volumetric Flow Rate (ft3/hr): 97 Material of Construction : Stainless Steel
Net Work (hp): 1.68
Comments and Drawings: See process flowsheet pg.15 and pricing info on Appendix A pg.187
- - - - -
99
PUMP
Operation: Continuous
Composition (lb/hr):
Hydrogen trace trace
Carbon Dioxide trace trace
Methane trace trace
Ethylene trace trace
Ethane trace trace
Acetaldehyde 7.21 7.21
Acetone 1,162.69 1,162.69
Ethyl Acetate 4,106.62 4,106.62
Ethanol 163.78 163.78
Water 20,050.10 20,050.10
Acetic Acid 66,639.65 66,639.65
Design Data:
Type: Centrifugal Efficiency: 0.56
Pressure Change (psia) 2 Electricity Required (K" 7.46
Volumetric Flow Rate 289.23
I Material of Construction Stainless Steel
Net Work (hp): 4.18
100
PUMP
Operation: Continuous
Composition (lb/hr):
Hydrogen trace trace
Carbon Dioxide trace trace
Methane O.OOE+OO O.OOE+OO
Ethylene O.OOE+OO O.OOE+OO
Ethane O.OOE+OO O.OOE+OO
Acetaldehyde 0.00 0.00
Acetone 0.01 0.01
Ethyl Acetate 0.02 0.02
Ethanol 0.00 0.00
Water 366.31 366 .31
Acetic Acid 20,371.87 20,371 .87
Design Data:
Type: Centrifugal Efficiency: 0.56
Pressure Change (psia) 0.1 Electricity Required (KVI 11.2
Volumetric Flow Rate I 493.46 Material of Construction Stainless Steel
Net Work (hp): 4.68
101
PUMP
Operation: Continuous
Composition (lb/hr):
Hydrogen 220E-27 2.20E-27
Carbon Dioxide 0,00 0.00
Methane 0.00 0.00
Ethylene 0.00 0,00
Ethane 0,00 0.00
Acetaldehyde 0.17 0,17
Acetone 63.50 63.50
Ethyl Acetate 610.00 610.00
Ethanol 2.74 2.74
Water 77.92 77.92
Acetic Acid 0.88 0,88
Design Data:
Type: Centrifugal Efficiency: 0.56
Pressure Change (psia) 0.1 Electricity Required (KVI 0.097
Flow Rate (gpm): 4.24 Material of Construction Stainless Steel
Net Work (hp): 0.04
102
PUMP
I
Iden tifica tion Item Pump Date: 4/ 1/02 1
Item # PB-900 By: akg
No. Required 1
Operation: Continuous
Composition (lblhr):
Hydrogen trace trace
Carbon Dioxide trace trace
Methane 0.00 0.00
Ethylene 0.00 0.00
Ethane 0.00 0.00
Acetaldehyde 0.00 0.00
Acetone 0.89 0.89
Ethyl Acetate 1,137.03 1,137.03
Ethanol 0.24 0.24
Water 1.78 1.78
Acetic Acid 438.03 438 .03
Design Data:
Type: Centrifugal Efficiency: 0.6
Pressure Change (psia) 0.1 Electricity Required (K\\ 0.37
Flow Rate (gpm): 44.5 9 Material of Construction Stainless Steel
Net Work (hp): 0.17
103
PUMP
Operation: Continuous
Composition (1blhr):
Hydrogen 0.00 0.00
Carbon Dioxide 0.00 0.00
Methane 0.00 0.00
Ethylene 0.00 0.00
Ethane 0.00 0.00
Acetaldehyde 0.00 0.00
Acetone 0.00 0.00
Ethyl Acetate 1.48 1.48
Ethanol 0.00 0.00
Water 0.00 0.00
Acetic Acid 436 .56 436.56
Design Data:
Type: Centrifugal Efficiency: 0.56
Pressure Change (psia) 0.1 Electricity Required (K~ 0.3
Flow Rate (gpm): 2200.93 Material of Construction Stainless Steel
Net Work (hp): 0.125
104
PUMP
Operation: Continuous
Composition (lb/hr):
Hydrogen 0.041 0.041
Carbon Dioxide 220.678 220.678
Methane 50.39 50.39
Ethylene 49.998 49.998
Ethane 54.4 54.4
Acetaldehyde 12,833.82 12,833.82
Acetone trace trace
Ethyl Acetate trace trace
Ethanol trace trace
Water 30.79 30.79
Acetic Acid trace trace
Design Data:
Type: Centrifugal Efficiency: 0.6
Pressure Change (psia) 2 Electricity Required (K'VI 1.49
Flow rate (gpm) 67.57 Material of Construction Stainless Steel
Net Work (hp): 0.62
-
105
PUMP
Principal Function:
Operation: Continuous
Composition (lb/hr):
Hydrogen
Carbon Dioxide 37.26 37.26
Methane 2.836 2.836
Ethylene 13.04 13.04
Ethane 9.23 9.23
Acetaldehyde 2,007.65 2,007 .65
Acetone trace trace
Ethyl Acetate trace trace
Ethanol trace trace
Water trace trace
Acetic Acid trace trace
Temperature (oF): 94 10
Pressure (psia): 30 28
Design Data:
Type: Centrifugal Efficiency: 0.6
Pressure Change (psia) 2 Electricity Required (K'" 0.25
Flow Rate (gpm) 3.5 Material of Construction Stainless Steel
Net Work (hp): 0.2
106
PUMP
I
Principal Function: Return reflux to acetic acid distillation column.
Operation: Continuous
Composition (lb/hr):
Hydrogen 8.00E-05 8.00E-05
Carbon Dioxide 1.71 E-08 1.71 E-08
Methane 0.00 0.00
Ethylene 0.00 0.00
Ethane 0.00 0.00
Acetaldehyde 22 .03 22.03
Acetone 1,974.66 1,974.66
Ethyl Acetate 18,527.79 18,527.79
Ethanol 163.64 163.64
Water 7,876 .99 7,876.99
Acetic Acid 2,872.85 2,872.85
Design Data:
Type: Centrifugal Efficiency: 0.6
Pressure Change (psia) 2 Electricity Required (K~ 5.6
Flow Rate (gpm): 241.8 Material of Construction Stainless Steel
Net Work (hp): 2.34
107
PUMP
Operation: Continuous
Composition (lblhr):
Hydrogen trace trace
Carbon Dioxide 0.00 0.00
Methane 0.00 0.00
Ethylene 0.00 0.00
Ethane 0.00 0.00
Acetaldehyde 3.52 3.52
Acetone 293.40 293.40
Ethyl Acetate 784 .07 784.07
Ethanol 5.13 5.13
Water 107.27 107.27
Acetic Acid 0.88 0.88
Design Data:
Type: Centrifugal Efficiency: 0.6
Pressure Change (psia) 2 Electricity Required (K'-' 0.25
Flow Rate (gpm): 9.46 Material of Construction Stainless Steel
Net Work (hp): 0.11
108
PUMP
Operation: Continuous
Composition (lb/hr):
Hydrogen 2.00E-08 2.00E-08
Carbon Dioxide 0.00 0.00
Methane 0.00 0.00
Ethylene 0.00 0.00
Ethane 0.00 0.00
Acetaldehyde 3.35 3.35
Acetone 229.90 229.90
Ethyl Acetate 174.07 174.07
Ethanol 2.39 2.39
Water 29.35 29.35
Acetic Acid 0.00 0.00
Design Data:
Type: Centrifugal Efficiency: 0.6
Pressure Change (psia) 2 Electricity Required (K'" 0.097
Flow Rate (gpm): 4.09 Material of Construction Stainless Steel
Net Work (hp): 0.043
109
PUMP
Operation: Continuous
Composition (lb/hr):
Hydrogen 2.13E-05 2.13E-05
Carbon Dioxide 4.48E-09 4.48E-09
Methane O.OOE+OO O.OOE+OO
I
Ethylene O.OOE+OO O.OOE+OO
Ethane O.OOE+OO O.OOE+OO
Acetaldehyde 4.95 4.95
Acetone 423 .97 423.97
Ethyl Acetate 3,435.12 3,435.12
Ethanol 29.16 29 .16
Water 462.42 462.42
Acetic Acid 1.02 1.02
Design Data:
Type : Centrifugal Efficiency: 0.6
Pressure Change (psia) 2 Electricity Required (K" 1.12
Flow Rate (gpm): 10.425 Material of Construction Stainless Steel
Net Work (hp) : 0.5
110
PUMP
Operation: Continuous
Composition (lb/hr):
Hydrogen 0.00 0.00
Carbon Dioxide 0.00 0.00
Methane 0.00 0.00
Ethylene 0.00 0.00
Ethane 0.00 0.00
Acetaldehyde 0.00 0.00
Acetone 0.89 0.89
Ethyl Acetate 1,135.56 1,135.56
Ethanol 0.24 0.24
Water 1.78 1.78
Acetic Acid 1.48 1.48
Design Data:
Type: Centrifugal Efficiency: 0.6
Pressure Change (psia) 2 Electricity Required (KVI 0.097
Flow Rate (gpm): 4.43 Material of Construction Stainless Steel
Net Work (hp): 0.043
111
REACTOR
Operation: Continuous
112
Heat Exchanger Specification Sheet
1 Company: -'
2 Location: ......~
1..:'2 --- r- - - -
16 Tem~rature (In/Out) F 255.5 262.66 280.95 280.95
17 Dew / Bubble ~oint F 255.5 280.95 280.95
18 Density - ..--.--... -----. Ib/ft3 53.886 0.18 0.115 57 .874
19 Viscosity_ cp 0.268 0_013 0_014 0.212
-~ .-- . -
~
33 DesignfTest Pt~ssure P~! 751 ICode 751 ICode
34 Design teml2er~_ture F 330 350
35 Number passes_per shell 1 2 - I I
;; "t
Heat Exchanger Specification Sheet
1 Company: -
2 Location:
3 Service of Unit: Our Reference: . ---
4 Item No.: R-610 Your Reference:
5 Date: Rev No.: Job No.:
6 Size 49/63 --240 in TY12e BKU hor Connected in 1 [!arallel 1 series
7 Surf/unit(eff.) 7200 ft2 Shells/unit 1 Surf/shell (eff.) 7200 ft2
8 PERFORMANCE OF ONE UNIT
9 Fluid allocation Shell Side Tube Side
c-!Q. - Fluid
- ' . . __ ..name
S -iO) STEAfI?
Ib/h 210358 48604
r1-! !!!.lQ_guantity, Total
12 Vapor (In/Out) Ib/h 191005 48604
13 Liquid Ib/h 210358 19353 48604
14 Noncondensable Ib/h
15
16 Tem~erature (In/Out) F 358.3 369.9 415.6 415.6
17 Dew / Bubble point F 358.35 415.6 415.6
t-- -
18 Densi!Y Iblft3 53.128 0.647 0.606 53.281
19 Viscosity cp 0.174 0.014 0.017 0.137
20 Molecular wt, Vap 54 - r-___54
---.-
21 Molecular wt, NC
22 Specific heat ~_TUl(lb*F) 0.6376 0.3969 0.7365 1.0511
23 Thermal conductivity BTU/(ft*h*F) 0.09 0.015 0.022 0.375
24 Latent heat BTUlib 193.3 813.4 _ _ 1i13.4_
25 Inlet pressure (absolute) psi 98.6 293
26 Velocity - ftls 12.18
27 Pressure drop, allow.lcalc. psi 2 0.262
28 Fouling resist. ' (min) ft2*h*F/BTU 0.003 0.003
29 Jieat exchanged 39535070 BTu/h MTD corrected 50.33 F
30 Transfer rate, Service 109.1 Dirty 112.49 Clean 442.42 BTu/(h*ft2*F)
31 CONSTRUCTION OF ONE SHELL Sketch
~ ~c:!.ereguirements
ASME Code Sec VIII Div 1 TEMA class B
55 WeighVShell 31395.9 Filled with water 64245.4 Bundle 21981 .2 Ib
56 J~emarks
57
58
Heat Exchanger Specification Sheet
2 Location:
'~. "'~" ----
----_._--_._-- _ .
1---3. .~e-",ice of Unit: Our Reference:
4 Item No.: R-810 Your Reference:
51 Date: Rev No.: Job No.:
6 Size 15 I 20 -48 in Type BKU hor Connected in 1 parallel 1series
7 Surf/unit(eff.) 120.2 ft2 Shells/unit 1 Surflshell (eff.) 120.2 ft2
81 PERFORMANCE OF ONE UNIT
9 Fluid allocation Shell Side Tube Side
10., -11:;;
~I ____~F,I---~~~--+---~~--_+
16 Temperature (In/Ol''' 1 AA ~.1 235 235
171 Dew I Bubble pn;n.
uuvv, .... e,",,11 n F+I--------t---'-=-=~-__j---.-::='----'I_--'='----
183.37 235 235
18 Oensi
19 Viscosi
Ib/ft3
cp
51.07
0.266
0.211
_.....__ ...__ .... ..
0.063
0.056
--..
59.228
- --- r-~
0.013 0.256
20 Molecular wt, Vap__
,.~.!. Molecular wt, NC
22 S ecific heat u, "'I'U , ' I _____ _ _
23 l}:1~Lf!lal .co
-:=n:.::d:.::u:.::
c.::.'_'i_"''--
tiv ty _
__ _ _ _ ___=~
24 Latent hea:..;:t_ _ __
25 !il!~tprt3.~sure (absolute 1
26 Velocity
~
l.3.p~~JgnlTest pressure psi 75/ / Code 75/ / Code ~ I "
~
8 ~P2orts-tuQe .. U-bend Typ~
49 ~~?EO.aL Tub.~::!lJ!>~ sheetjoil1t. ___g~.<2.ove~!.p'!:l.d
50 rE-X2~!l.~!On jOint Tipe
51 RhoV2-lnletn()zzle 158 Bundle entrance .._ Bundle....._exit
..... _.. _--_.- Iblm=!i.~)
~? _Q?~~t~: Shell side . Tube. ~id_e___._ _ _.
53 _... Floating head
54 ..Code reql,lirernel!~ _ _... ASME_<;:ode ~ec VIII Oiv 1 TEMA class B
55 Weight/Shell 847 Filled with water 2000.5 Bundle 318.9 Ib
56 1 Remarks._ __ _ .
57
1 1
58
, 'C
Heat Exchanger Specification Sheet
1 Company: , -
2 Location :
3 Service of Unit: Our Reference :
--.
4 Item No.: R-900 Your Reference:
5 Date: Rev No.: Job No.:
6 Size -... 17/ 22 --192 in Type BKU hor Connected in 1 parallel 1 series
7 Surf/unit(eff.) 626.3 ft2 Shells/unit 1 Surf/shell (eff.) 626.3 ft2
8 PERFORMANCE OF ONE UNIT
9 Fluid allocation Sheil Side Tube Side
-
r!-0_ Fluid name <;-~1 .<.rC'A m
rlj f luid quantity, Tolal Ib/h 211522 3393
12 Vapor (In/Oul) Ib/h 14872 3393
13 Liquid Ib/h 211522 196650
--- -- - - .3393
- -
14 Noncondensable Ib/h ... _._
15
".
16 Temperature (In/Out) F 212.6 221 269 .99 269.99
17 Dew / Bubble point --, .. __.. F 220.61 269.99 269.99
18 Density Iblft3 50.663 0.331 0.097 58.206
19 Viscosity CD 0.242 I 0.093 0.013 0.221
20 Molecular wt, Vap __ __ __ 86.57 86.48
21 Molecular wt, NC ._-_... _--.- - ..
22 Specific heat BTu/{lb*F) 0.5242 0.3262 0.5362 1.0082
23 Thermal conductivi!,y BTU/(Wh*Fl 0.069 0.01 0.016 0.398
24 Latent heat BTUllb 149.2 928.4 928.4
25 Inlet pressure -<absolute) psi 28 42
26 Velocity tUs 47.99
27 Pressure d_rop, allow.lcalc. psi 2 I 0.28
28 Fouling resisl (min) ft2*h*F/BTU 0.003 0.003
29 Heatexchanqed 3150000 BTU/h MTD corrected 50.38 F
30 Transfer rate . Service 99.82 Dirty 101 .53 Clean 310 .51 BTu/(h*ft2*Fl
31 CONSTRUCTION OF ONE SHELL Sketch
32 Shell Side Tube Side
I I I
33 DesiqnfTest pressure psi 751 I Code 751 I Code
34 Desiqn temperature
35 Number passes per shell
F 290
1
330
2 oX1n~::n
I I I I
36 Corrosion allowance in 0.0625
37 Connections In 4 / 150ANSI 4/150 ANSI
38 Size/rating Out 4 / 150 ANSI 1/ 150-------_
ANSI ..
~ - - -- bonnet
Channel or CS Channel cover
44 Tubesh~et-stationa!:y SS304 _~~~b.eet-floating
45 Floating head cover Impingement protection None
SS304 Ty~Single Spacing: dc 23 .625
.46
Baffle-crossing seg Cut(%d) 44 vert in
in
330
1 . __
..._
-_.. __ ._--- ---
...
380
_ - 2---- - - ~ I t
lQ. r--
E. Connections In 1/150ANSI 2 / 150 ANSI
38 Size/ratinq Out 4 / 150ANSI 1/ 150 ANSI
39 in / Intermediate 1/ 150 ANSI / 150 ANSI
40 Tube No. 44Us 00 0 .75 Tks-avg 0.065 in Length 6 ft Pitch 1 in
41 Tube type Material CS I Tube pattem 90
42 Shell SS304 10 00 12.75 in ._hell cover SS304
-
43 Channel or bonnet SS304 Channel cover
44 Tubesheet-stationary SS304 Tubesheet-floati~ -_ .. _--
45 Floating..head cover Im(2ingement (2rotection None
46 Baffle-crossing SS304 T:te e Single seg Cut(%d) 45 vert S(2acing: dc 23 in
47 Baffle~.lg.f1g Seal t}I(2e I Inlet 23 in
..
48 .!3.l!P(2orts-tube ._._ _ U-bend T:tee
-- -~ - .--
-
49 B:t(2ass seal Ty~e-tubesheet joint groove/exeand
50 Expa,:,sion joint _
.-.. -.. . _
TYQe
51 _RhoV2-lnlet nozzl~._..... ~22. __ ... _. Bundle entrance Bundle exit Ibl(ft*s2)
52 Gaskets - Shell .side Tube Side -
- "-"
I II
REFLUX ACCUMULATOR
Operation: Continuous
118
REFLUX ACCUMULATOR
Operation: Continuous
119
REFLUX ACCUMULATOR
Operation : Continuous
120
REFLUX ACCUMULATOR
Operation: Continuous
121
REFLUX ACCUMULATOR
Operation: Continuous
122
REFLUX ACCUMULATOR
Operation: Continuous
123
REFLUX ACCUMULATOR
Operation: Continuous
124
Refrigeration Unit
Operation: Continuous
Materials handled:
I
I
Utilities: I
I
125
STRIPPER
Principal Function: Separate out the wastewater from the aqueous outlet stream of the decanter
Operation: Continuous
I
I
I
126
STORAGE TANKS
Operation: Continuous
Ethyl Acetate
Ethanol I
Water
Acetic Acid
Temperature (oF): 77
Pressure (psia): 14.7
127
4
STORAGE TANKS
Principal Function: Holding tank: for Acetic Acid recycle stream (S-l 03)
Operation: Continuous
Hydrogen trace
Acetaldehyde trace
Acetone 0.006
Water 366.13
Acetic Acid 20,377.61
128
STORAGE TANKS
Principal Function: Holding tank for Acetic Acid recycle stream (S-1 02)
Operation: Continuous
129
STORAGE TANKS
Operation: Continuous
130
STORAGE TANKS
Operation: Continuous
I
131
STORAGE TANKS
Principal Function: Holding tank for feed to the Acetaldehyde distillation column (DC-500)
Operation: Continuous
132
STORAGE TANKS
Principal Function: Holding tank for bottoms stream of distillation column (DC-500)
Operation: Continuous
133
..
r
Pressure valve
Principal Function: To decrease the pressure of the feed stream to the acetaldehyde separation
column
Operation: Continuous
Utilities:
134
EQUIPMENT COST SUMMARY
EguiQment Purchase
name DescriQtion Cost Source
135
EguiQment Purchase
name Description Cost Source
136
The bare module cost of equipment was determined using cost charts that can be found in
Ulrich. The purchased cost of each piece of equipment was determined by the charts. Then,
each piece of equipment was multiplied by the appropriate bare module factor based on
operating pressure and materials of construction to find the bare module cost for each piece of
equipment individually. The total bare module cost was determined by summing the individual
bare module costs. Nearly all of the equipment was available in charts from which the purchase
cost could be read, and then mUltiplied by the appropriate factor to find the bare module cost.
The exceptions to this were the heat exchangers, the fired heater, and the refrigeration unit. We
used B-lAC to design the heat exchangers, including the condensers and reboi1ers . B-lAC
rigorously designed the heat exchangers and also returned an estimated cost of material and
labor. For heat exchangers, Ulrich estimates that this cost is 2.34C p , and the bare module cost is
3.18 Cpo Assuming similar escalation in prices for our equipment, the ratio of bare module cost
to installed cost equals 3.1812.34 = 1.36. The cost of the heat exchangers designed using B-lAC
The costs for the refrigeration unit and fired heater were estimated using equations found
in Walas. These equations calculated the installed costs for these pieces of equipment.
Assuming similar ratios for the installed costs of these pieces of equipment as Ulrich provides
for heat exchangers, the ratio of bare module cost to installed cost for this equipment is also 1.36.
Estimates for pump costs were determined from cost charts provided by Ulrich. The
pump power was taken from the Aspen Plus output for stand-alone pumps, and from IPE
equipment sizing for reflux and reboiler pumps. The output this program provides for individual
equipment is its installed cost. The large storage tanks were also cos ted llsing cost charts
137
available in Ulrich. Using the factors provided, the bare module cost could be determined
directly.
By using this method to determine the equipment bare module costs, and adding
$5,979,000 for the catalyst (see Appendix for calculations), the total bare module cost, CTBM ,
determining the total permanent investment. It was estimated that 5% of the total bare module
cost should be set aside for each site preparation and service facilities. Allocated utility faci lities
for cooling water and steam were build, at a total cost of$4,387,000 (see Appendix B, p. 203).
These additional costs are added to the bare module cost to produce the direct permanent
investment, which equals $26,439,037. An estimate of 15% of the direct permanent investment
is set aside for contingencies. Adding this to the direct permanent investment yields the total
depreciable capital, $30,404,892. Two percent of the total depreciable capital is then set aside
for land costs, and 12 % for startup costs. This allotment for startup is slightly higher than
normally suggested, but we believe it is warranted because of the complexities of our process
and the many recycle streams that must be accounted for. Adding the startup and land costs to
the total depreciable capital produces the total permanent investment, $34,661,557.
138
139
Ii
140
Important Considerations
Acetaldehyde is an extremely flammable liquid and vapor. Its vapor may cause flash
Acetaldehyde is therefore stored in stainless steel tanks with a refrigerating system to ensure that
the temperature of the product does not rise above 60 OF. This is why is important to have a
Acetaldehyde is also a potential cancer hazard. High vapor concentration may cause
drowsiness or irritation of the eye and respiratory tract. For eye protection, safety glasses with
side shields and a face shield need to be worn by the workers at this plant with risk of exposure.
Additionally, chemical resistant gloves, boots and protective clothing appropriate for the risk of
exposure need to be worn. Decontamination facilities such as eye bath, washing facilities and
Acetic acid is strongly corrosive and causes serious bums. At temperatures above 102 OF
explosive acetic acid vapor/air mixtures may be fonned. In order to prevent such hazards, there
should be no open flames, no sparks and no smoking in the premises. Also, above 102F, a
closed system needs to be used as does ventilation, and explosion-proof electrical equipment.
effects, acetic acid is a lachrymator. Prolonged exposure to acetic acid causes sore throat, cough,
headache, dizziness, shortness of breath and labored breathing. Workers with potential exposure
to acetic acid need to be provided with protective gloves, protective clothing and breathing
protection. Leaking acetic acid liquid must be collected in sealable containers and cautiously
neutralized with sodium carbonate. Acetic acid is hannful to aquatic organisms and therefore it
must not be disposed into water bodies without adequate treatment and/or dilution.
141
Hydrogen is even more flammable then acetic acid and it undergoes many reactions with
air, oxygen, chlorine, fluorine, strong oxidants that cause fire or explosions. Exposure to
hydrogen also causes dizziness, asphyxia, labored breathing and unconsciousness. Therefore, in
addition to the safety precautions that need to be taken for acetic acid, hydrogen gas cylinders
must not be handled with oily hands and must be stored in a cool place. In case of spillage, the
danger area must be evacuated and the vapor must be removed with fine water spray. Because of
the dangers associated with storing hydrogen, we receive our supply via a pipeline.
Another aspect taken into consideration was that the furnace operates at temperatures
around 600F. Therefore, steps must be taken to ensure that faults in the process do not make it
necessary for the entire process to shut down since it will be very economically unfeasible and
wasteful to have to shutdown and restart the furnace, especially since it will take an extended
period of time to reach the desired temperature again. Thus, there is a storage tank for the
reactor effl uent before it is fed to the acetaldehyde distillation column. If other parts of the
system fail, the furnace can still operate and feed its product to that tank. It would be more
beneficial to have a storage tank immediately following the reactor, but the high temperature and
high hydrogen composition makes that unfeasible. There will also not be difficulty with a supply
of feed to the furnace if other systems break down, since the acetic acid and hydrogen feedstocks
can be fed virtually directly to the furnace if it is necessary to keep the reaction proceeding.
Also, there is a storage tank for the bottoms of the acetaldehyde distillation column. This allows
the acetaldehyde recovery section and the acetic acid separation section to operate if the other
Startup is a special concern for this facility because ofthe importance of recycle streams
to the operation of the absorber AB-320 and the acetic acid distillation column DC-610. A tank
142
holding acetic acid should be positioned near the absorber to provide solvent to the top stage
during startup. This stream is usually furnished from the bottoms product of the acetaldehyde
distillation column, but that will not be operating at the beginning of the process. Ethyl acetate
must also be purchased and stored so that it can be used to form the azeotrope in the acetic acid
distillation column. Aspen simulation results imply that without an initial charge of ethyl acetate
to this column, there is no phase separation in the decanter DE-720, and no ethyl acetate product
is recovered. More energy in the form of natural gas must also be supplied at startup. This is
partially because of the need to heat a cold furnace, but also because there are no waste streams
that can be burned for fuel, and there is no hot reactor effluent to preheat the reactor feeds.
Because waste streams are used for fuel in the furnace, careful control is necessary to ensure that
small irregularities in process conditions do not lead to either excessive or insufficient heating in
Plant-wide control is also a major issue in this complicated design. Controls should also
be placed before the compressor CP-41 0 in order to ensure that the entering stream will be only
vapor. If the feed stream is cooled below its dew point, a valve may open to reduce pressure and
vaporize the entire stream. This would increase the duty on the compressor, but is necessary for
its long-tenn operation. There is similar attention paid to ensuring that the feed to the recycle
pump P-730 is entirely liquid. The distillate of the near azeotrope distillation column DC-900 is
subcooled to limit the chances that the pressure drop associated with the mixer would partially
vaporize the feed to the pump. The composition of the stream should be monitored, and ifthere
is any vapor a small cooling jacket can be used to decrease the temperature and produce a total
liquid.
143
The amount of acetic acid and hydrogen feeds, as well as their ratio must also be
controlled, for two reasons. First, the plant design is optimized for the flow rates that were used;
if the amount of either feed changed substantially, then unexpected difficulties may result when
the effects of recycle streams are considered. Second, in order to keep the proper oxidation state
for the catalyst, it was determined that a hydrogen/acetic acid mole ratio of 511 is optimal. If this
is not maintained, then the performance of the catalyst may degrade quickly.
144
The Economics Spreadsheet developed by Holger Nickish was used to evaluate the
process. Two different scenarios were considered in evaluating the economic viability of this
design process. In the first, the acetic acid feed was available at $0.161Ib. In the second case,
legislation to eliminate MTBE from gasoline created a glut of methanol, which can be used to
produce acetic acid. In this situation, the cost of acetic acid is $0.12/Ib. Besides these costs (and
the associated change in the working capital), all costs are the same under both scenarios. The
The annual costs associated with operating the plant under these conditions are
summarized in the Fixed Costs and the Variable Costs tables on pages 146 and 147. Heuristics
for calculating the annual costs are based on the cost sheet outline provided in Table 10.1 of
Seider, Seader, and Lewin. We do not need to purchase the steam and water utilities because we
built the dedicated facilities and assigned the price to allocated costs, part of the Direct
Permanent Investment. Costs for natural gas, electricity, and wastewater disposable were
We assumed three operators per shift, each earning an annual salary of $40,000. The
major fixed costs we encountered stemmed from the wages and services for maintenance. The
total maintenance costs amount to $2,447,000/year. The cost for replacement catalyst is also
considered here. $543,500 per year is set aside for the catalyst, which we assume we must
The variable costs are based primarily on the cost of the hydrogen and acetic acid
feedstocks. Acetic acid is especially expensive, costing $0.27 per pound of acetaldehyde
produced. Because of the allocated facilities for stean1 and cooling water, the utility costs are
145
Fixed Costs
Acetaldehyde Production. Acetic Acid $0, 16/1b
April 9, 2002
TOTAL
Operation
Maintenance
\vageSandBene~~_ _ __ __ _ _ __ __ _ __ _ _ ~$~
1,~0_64~,~00_0~1'
Salaries and Benefits $266,000 .
Materials and Services $ 1,064,000
Maintenance Overhead $53,000
Operating Overhead
146
Variable Costs
147
only $0.005/lb of acetaldehyde. For the production level used in this plant, the annual amount of
The working capital was determined by assuming a 14-day supply of the products
acetaldehyde and ethyl acetate, and a one-day supply of acetic acid. This supply can be so low
because our site is shared with a major chemical company. Hydrogen is piped directly to the
facility, so it is not stored. We also hold 30 days of accounts receivable to account for payment
occurring monthly. Additionally, a spare charge of catalyst is held because it is a special catalyst
that could not be ordered quickly if its performance declined. The total working capital for this
process is $12,580,684. This is added to the total permanent investment (TPI) to find the total
capital investment (TCI). The TCI is $47,242,990. A summary of the steps taken to determine
Finally, the profitability of this design was examined. The return on investment (ROI) in
the third year is 11.4%. Investor's rate of return (IRR) and the net present value (NPV) were
calculated based on a cost of capital of 15 %. Using a five-year depreciation cycle and a 20-year
plant life, the IRR is 11.1 % and the NPV is -$5 ,830,000. The annual cash flows are presented in
the table labeled Cash Flows on p. 150. Clearly, construction should not proceed under these
conditions.
148
TOTAL
Working Capital
Inventory
IAcetaldehyde 3,891,000 Ibs $ 1.868,000
Ace,tic Acid 465 ,070 Ibs $74,000 1
H yd~'ogcn Ibs SO
Total Inventory: $1 ,942,000 I
Accounts Receivable: 30 days S4,430,000
149
or,:..,.'
V'l';"'';:J'''-~
Cash- Flows :1:fJ;ll.'
~
~. ~.,1
~,
l/$
.l; '!,.CJ
o
0\0
~
T ~ ~
~
I'.-'t:i
-J /'~. .
v
~
.~
~
0"
(j v
~
.$
.~
$
~O::,,'ri
$
",0
vO
tf
~
Ib
.<i
vo.~
"
tf
q,(>
<J
!;
.,
~
~
,,'&
,c::-
0
.
(>0
~
/
0
'"/I
~
~
,,'ri
q,
~q,
<q'ri
...
~
II @
~c::-
.
of
......
~'ri
c::-
v'ri
.
.
d
~
~
~
.:.q,
~
4.
~
/'
($11,554,000)
=
($11,554,000) ($11.554,000)
($11,554,000) ($11,554,000) ($21,601,000)
($24.135.000) ($24,13~~ ($39,851,000)
($3.699.000) $3,233,000 ($37,725,000)
i~3,8!_1..:?9_~)
$2.868,000
__ _
.- -".-,,-- ..... . _ J~~~ ~~~~!OOO)
.. $7,221.000
$9,523.000
~
($28.861,000)
-_._ ._----_.__ ..._---. -----_... _....._...... _-_.
1'1--'--'- -'---' 11 $4,545,0~~~ _ _ $~,538.000 ($25,170,000)
~~~~~~~~~FJ~~-----iH~~:~~~ II ~:~i~~~:~6~1
_~.!.~OOO
I_ -:;::--:-'-:-::..::..:.::..:.:::..._~'~_~
.,~.. ~61.000
$7.061.000
$ 7.061.000"
- ($17,403,000)
----_.
($15,658.000)
"'-' ,
;~.i"'~
1 ~~.
..,,; 1:Jl:'"
1.
acetic acid being available at $0.12/Ib. The input summary for this case is presented on pages
152 and 153. The annual costs associated with operating the plant were calculated in the same
manner as they were in the first scenario. The results are summarized on the pages 154 and 155
in the Fixed Costs and Variable Costs sheets. Under both circumstances the total fixed cost sums
to the same amount: $4,740,500. The variable cost does change dramatically, however, as acetic
acid costs only $0.20/1b of acetaldehyde formed, rather than $0.27/Ib as in the first case. This
result leads to a savings in raw material costs of nearly $7,000,000/year, the costs decrease from
$30,290,000 to $23,495,000. Other variable costs were not affected by the acetic acid price.
The working capital is affected somewhat by the lower price of acetic acid because the
one-day supply of acetic acid is not worth as much when acetic acid is less expensive. Thus, the
amount of working capital required for the supply of acetic acid decreases from $74,000 to
$56,000. The working capi tal under these circumstances is $12,562,684, and the TCI is
$47,224,990. These results are summarized in the Venture Guidance Appraisal on p. 156.
The economics of this process was analyzed using the same metrics used to examine the
first scenario. As a result of the substantial decrease in variable costs, the ROI in the third year
improved to 19.5 %. Using the same five-year depreciation schedule and 20-year plant life as
before, the IRR is 18.5 % and the NPV is $12,162,000. The annual cash flows are summarized
in the table Cash Flows on p. 157. The economics of this process is strongly dependent on the
cost of acetic acid. If acetic acid is available at $0.12/Ib, then it is profitable to follow this
design. The rate ofretum is not significantly higher than the cost of capital (15 %), so the
potential reward for building this plant would be relatively small. Thus, more research should be
done to ensure acetic acid can be purchased at the lower price before production proceeds.
151
Input Summary
April 9.1001
General Information
- - - -- -- - - - -- - - -- - - -_.... __ - - -
..
PackHging
Labor: 0.00 per Ib Acetaldehyde
M aterials: 0.00 per lb Acetaldehyde
Byproducts
lb Ethyl Acetat~per lb Acetaldehyde: 0.0888820 Price per lb Ethyl Acetate: $0.6000
Fixed Costs
Operations
Number of Operators per Sh 3 (assuming 5 Shifts)
Annual Wages per Operator: $40,000 Including Benefits
Employee Benefits: % of wages
Direct Salaries and Benefits: 15 % of wages
'a ting Supplies and Selvices: 6 % of wages
TechIlical Assistance to Mar $52,000 per labor year
Control Laboratory: $57,000 per labor year
Maintenance
Wages: 3.50 % of Total Depreciable Capital, Including Benefits
Employee Benefits: % of wages
Salalies and Benefits : 25.00 % of Maintenance Wages and Benefits
Materials and Services: 100.00 % of Maintenance Wages and Benefits
Maintenance Overhead: 5.00 % ofI'vlaintenance Wages and Benefits
Operating Overhead
General Plant Overhead: 7.10 % of Mainlenance and Operations Salaries, Wages and Benefits
Mechan.ical Department Sep 2.40 % of Maintenance and Operations Salaries, Wages and Benefits
loyee Relations Department: S.90 % of Maintenanee and Operations Salaries, Wages and Benefits
Business Services: 7.40 % of Maintenance and Operations Salaries, Wages and Benefits
Property Taxes and Insurance
roperty Taxes and Insurance 1.50 % of Total Depreciable Capital
Depreciation
Direct Plant 8.00 % of Total Depreciable Capital
Allocated Plant 6.00 % of Allocated Costs
Catalyst Replacement
~.a.~~yst Rep!aCC1n~~.~_._ S_4_3-',S
-_0_0_.0_0_ $c...I-"'y_e_aT_ _ __ _ __ _
Financial Information
Cost of Capital: 15.00 %
GeneTallnflation Rate : %
Product Price Inflation Rate: %
variable Cost Inflation Rate: %
Fixed Cost Inflation Rate: %
Income Tax Rate: 37.00 %
153
I
Fixed Costs
Acetaldehvde Production. Acetic Acid $0. l21lb
April 9, 2002
TOTAL
Operation
Maintenance
I
Operating Overhead
iGeneralPiant Overhead
I
head: $3741,000
$4,740,500 I
154
Variable Costs
Acetaldehyde Production. Acetic Acid $0,12/1b
Aprij 9. 2002
TOTAL
IAcetic Acid ------------~~,
20 ,08 per Ib Acetaldehyde
--~---------
IHydrogcn 3,O/ per Ib Acetaldehyde
Total Raw Materials: 23.J 4 pel' Ib Acetaldehyde $23,496,000 $23,496,O(fO
Utilities
, N3tur~ _SJas __ O. 12 pcr Ib_~~etal<:lehyde _
~
-lectriCiiY O,lS per Ib Acetaldehyde
155
Venture Guidance Appraisal
Acetaldehyde Production. Acetic Acid $O.12/1b
April 9, 2002
Working Capital
$5,979,000
$229,684
$6,208,684
$12,562,684
156
:Cash Flows
14. ." " it', gj ' "- .~ . 'i:j~i:i-l- .:1.1 .-1' ~":""i-",-;w.I'r n
f-pl'll ~1; 2002 , ., .~ ., Acetaldehvde Acid $0 1211h . ~I'"~'-'. ."~~-;;. . ' +~!t;
l:.;... .
".
1< I II
.
1 H. I
_. f 7 7
~ fI
~ 1- }~
~ ~\.
"
I ...
q,'tJ
,,~v
~'(:s:
,'"
(b~ ~
c.P
'tJ
t?
0'tJ
'"
~
f
q,
~
0
0
t?
0'"
(j
.!!
q,
,~
(j
,<f
"
0'"
,i
q,
A.'tJ
r-q,
~
+
/I;;
/1
/,
,~l::
L ~
Of
0'tJ r"~
....
@
,
..),; ~CJ r-.'ri .~ .~ ~
q,~ , .q, 0 <t.;
'tJ 'tJ
.::i .~
q,
<
,L ~~:_ _~_
~o ~ , ~ ~~ '-# ~ ~_._
-oJ q,Q. 'b'
J
2003
2005 450
aa
it T~o~ ~ _o.!!.... __~STRUCTION
CONS TRUCTION
$21,928,000
df
U ($11.554.000)
($11,554,000) --(i12.563POOi
($10,896,000) ($4,741,000) ($6,932,000)
($11,554,000 )
($24,117,000 )
($641,000 )
($11,554,000 )[1
($24,117,000)"
($641,000)
($11,554.000)
($24,117,000)
$6,291,000
($21,601,000)
($39,837,000)
($35,701,000)
ji,
.~~~: 900 ~~~!~~7.~.9~ ~::..~ ~-=- =-~-=-= ~?2:!93,000) ($4,741,000) ($6,655,000) ~_10,668,OOO ($3 ,947,000) $6'72. 1'.0 00 .. d $13,376,000 .. ($22,451,000) , .. ~.:e L' I
2008 90,0 $43,857,000 ($21,793,000) ($4,741 ,000) ($3,993,000) : $13,330,000 ($4 ,932,000) $8,398,000 II $12,391,000 ($17,094,000) ".i
)i~O~ !!!!O )4_~'~~~'~iO_ ~------ -- - - -- - -- -- ($22,793~()OO-) - ---($4,741.000) - - ($3,993,000) ' ~.:~.!330,~~ __ J!~~~~9~) ___ _~~~~~~0_0. 1.--$~~1.2~~ ($12,436,000) _." -.:;':
i ~~~Q I"~ ,i__$~3~~_~:~0~ .__ _ _ _ _ _ _ _ . ($21.793,000) ($4,741,000) ($1,997,000) ' $1"5,326,00~.. _~$5,67 1,OO~ _ _ ~9!!~_~~000 ! . $11 ,652,000 ($8,627,000)
II
. --==-
I
. 2011 900 $43,857,000 ; ($21,793,000) ($4.741,000) $17,323.000 ($6,410,000) $10,913,000 h $10,913,000 ($5 ,525,000) 'f-J~ '-I. ~
2()12. 900' ~3.- 857 000 ~r ="(S~~!.93:.000) _.. ($4,741,000) $1 7,3.23,0'00- ---($6.4. 10
,000) - - S10,91ioOo-U $10,913,000 _...Jg~??.:~.C!.<:.2 '"
2013 90.0 I $43,857 ,000 1_ _ _ ___. . _ _ _ _ . _J~21.79~,~"~?) ($4,741 ,000) __ ~17:.0~~:~0.... L$.~,4:.0:~.~91. 1-_~~_0.:?~3,000 II_S10,g13:~ ($48 1,000)
1 2014_. 90.0 '1_ $4 ~8~,000 i _.__ ($21, ~ ($4,741 ,000) $ 17,323,000 (56,4 10,000) $10,913,000 ' $ 10,9 13,000 _ _ $_1~5~
.2015, ~ _ ,~3:~! ...... _ _ _ _ _ __ --'~OOO) ($4.741.000 ) _ $17.323 ,000 1-_~S.6,410 , OOO) $10,913 ,C!.00 S10,913,OOO ~~~?~ ,"
2_01_6 190~ . _ I, . ___ $10 , 913,0~~ _ $10,91?~ _ _~4.:.875 ,~
~
$43,857,000 (521,793,000) . ($4.741 ,000) $17 ,323.000 ($6 ,410,000)
2017 900 ,1
=-=.
$43,857 ,000 (S21 ,793,000) ($4,741 ,000) $17,323,000 (56,410,000) $10,913,000 $10,913,000 $6,216.000 . '. "',
2018 ~90 0 -$43,857"0~O ~~ ($21.793,000)_ ($4 ,741 ,000) . ~_ ~17,323:OOO (56,410,000) 1- ~-!~~?1 ~,OO~ ~~1 3.0?~ _ _~i;~~'2:00~ ~~::~~~~2'i]tl
2019 900 -.!43 ,857 ,000 I I~ __ ($21,793,000) ($4.741,000) $17 ,323:000 ($6,410,000) $10 ,913,000 $10.913.000 $~:39~:.?C!.? ' .,
2020 900
'. 2021
-
900
---. $43,857 ,000
$43,857,000
'j
. ($21 ,793.000)
($21,793,000)
($4,741,000 )
($4,741 ,000)
-
!
$ 17,323,000
$17,32.3,000
--_.
(56,4 10,000)
($6,410,000)
$10 ,9 13,000
$10,913,000
- $ 10,913,000
_.-
$10,913 ,000 $9,278,000
S10,045,OOO ' ,
~ -2022 90.0 I $43,857,000
t"- - -
(521.793,000) ---($4,741,000) 1 $17.323:000 ---($6,410.000) $10,913,000 $10,9 13000 --S-;O,712,O'OO- ,'- J ..~t-"""i,1: :.~~.:
I
1. ",'
202~ _ 90.0 J $43,857 ,000 _. _($21 ,7~~,OOO) ($4 ,741.000) $17,323.000 ($6,410,000) $ 10,913,000 $10,913,000 ~~?_~?9~_ ~.;.J>.-",,;,~q
~
(
900-',
-
$43,857,000 $12,563:9~?" _ ($21.793,000)
. -- ($4.741,000) IL
.
$29,886,000
----
($11 ,058,000)
$18.828.000 ~,~38,gOO _' ___S 12,~62,OOO
_
... .. r--;I;'lH;
158
patent filed by Eastman Chemical. The acetaldehyde is recovered by first absorbing it with an
acetic acid-rich solvent, then separating the acetaldehyde from water and acetic acid in a
distillation column. In order to attain high recovery of the low boiling (b.p. = 70 OF)
acetaldehyde at the purity required for sale, the vapor distillate from the primary acetaldehyde
distillation column is fed to a smaller column with a condenser operating at 10 F that condenses
the acetaldehyde while allowing lighter gases such as carbon dioxide, methane, and ethylene to
escape. Large amounts of both hydrogen and acetic acid can be recycled to the reactor in order
to minimize the amount of fresh feedstock that must be purchased. Ethyl acetate, which forms as
a by-product in the acetaldehyde distillation column can be purified and sold, generating
The profitability of this facility is very sensitive to the price of acetic acid. If the price of
acetic acid remains at its current level of $0.16/Ib , then this design would not be profitable and
should not be pursued. If the price of acetic acid decreases to $0.12 /Ib, there is an opportuni ty to
profit from manufacturing acetaldehyde by the process we have described. Further studies are
needed to project the market for acetaldehyde and whether we will be able to sell the
$100,000,000 pounds per year we produce. In addition, there should be a study to determine the
probable price of acetic acid in the near future. If acetic acid can be purchased as cheaply as
$0.12 /Ib and the market will support the introduction of 100,000,000 Ib/yr of acetaldehyde, then
159
160
Acknowledgements
We would like to express our appreciation to Prof. Leonard Fabiano, our advisor, Dr.
John Vohs, our faculty advisor, and Dr. Bruce Vrana, who gave us this problem, for helping us
and guiding us with this design project. We would also like to thank the following people who
Fellow Students
161
Bibliography
Agreda, Victor and J.R. Zoeller Ed., Acetic Acid and its Derivatives, Marcel Dekker, New York
(1993).
Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed. Wiley, New York (1991).
Levenspiel, Octave. Chemical Reaction Engineering, 3rd ed., Wiley, New York, (1999).
McKetta, John J. Ed. Encyclopedia of Chemical Processing and Design. Marcel Dekker, New
York (1997).
Perry, R.H. and D.W. Green, Ed., PeID's Chemical Engineers' Handbook, 7th ed. McGraw-Hill,
Peters, M.S. and K.D. Timmerhaus, Plant Design and Economics for Chemical Engineers, 4th
Seader, J.D. and EJ. Henley, Separation Process Principles, Wiley, New York (1998)
Seider, Warren D., J.D. Seader, and Daniel R. Lewin. Process DesignPrinciples,Wiley, New
York (1999).
Tustin, G.c., et a1. "Method for Producing Acetaldehyde from Acetic Acid." U.S. Patent No.
6,121,498.
Ulrich, G.D., A Guide to Chemical Engineering Process Design and Economics, Wiley, New
York (1984)
162
91
:y XIUN:tIddV
164
Current CE =405
C~002:= 405
CE I982 := 315
COMPRESSOR CP-410
Powernet := 443.8hp
Powernet = 330.942 kW
11 := 0.72
Power
Power:= net
0.72
Power = 459.641 kW
5
C p = 3.6 x 10
Cp = $360,000
F BM := 7.3
C BM := FBMC p
C BM = 2.628 x 10
C_BM = $2,628,000
165
d1 =moles of light key (acetaldehyde) in distillate
d
j
=
moles of heavy key (water) in distillate
b
j
=moles of heavy key (water) in bottoms
d j := 291.3229
b'=
J . 1113
b i := 0.21 7
a := 2
j
IOg(di . b ;
dJ bI
Nmjn := -J"O"og....::,(a-)~
Nmin = 19.737
(
i
_ d - afeed-
_ Xj.feed
dj
l).feed
J
Lmin - ....0.-_ _ _ _ _- - " - _ - "
afeed - I
166
To find relative volatility of the feed, use the geometric mean of the relative volatilities on
equilbrium stages 27 and 28.
CX feed := (3 13) 2
CX feed = 6.245
d,I
- - - cxfeed'-
dJ J
(
xi.feed l).feed
Lmin :=
cxfeed - 1
Lmin = 491.106
D = moles of distillate
D:= 304 .8
Lmin = 1.611
o
Rmin := 1.61 I
R = 2.094
At 1.3 times the minimum reflux ratio, the actual number of required stages can be
determined by the Gilliland Correlation.
R - Rmin
X:=
R+I
X=0.156
N - Nmin
y=
N+ I
167
Y = 0.499
Y + Nmin
N := - - -
1-Y
N = 40.422
The actual conditions used in the simulation was a reflux ratio of 2.40, with 40 equilibrium stages.
These calculations were done using Excel spreadsheets. The following explanation outlines
the equations and assumptions used in performing the calculations.
As a first step to finding the dimensions of the column tower, the flow parameter (FP) was
calculated from the values of the liquid and vapor flow rates in the top stage of the column and
the liquid and vapor densities which we got from the Aspen simulation of our process.
Additionally, the surface tension of the liquid gives us the flooding velocity. We assumed a tray
spacing of 24 inches (61 Omm) Using the known variables for the vapor flow rate, flooding velocity
and the density of the vapor phase, the diameter of the column was determined from the
following equation :
Where:
D = Tower diameter
p = Density
Ib
V:= 151800
hr
1b
P v := 0.464
ft3
m
U:= 1.16
s
D = 10.3ft
Since towers are fabricated in increments of 0.5 ft., the calculated diameter of 10.3 ft.
is rounded up to 10.5 ft.
168
The tower height was computed by multiplying the number of trays with the tray
spacing and allowing a 10-ft high bottoms sump below the bottoms tray and a 4-ft
disengagement height above the top tray. All other distillation columns are computed
similarly. The absorber does not have either of the additional heights because there
is no condenser or reboiler. The stripper does not have a reboiler, and thus there is
no need for a 10-ft. bottoms sump.
The bare module cost of the tower is estimated from the following equation:
Where,
This equation holds for operating pressure> 7 barg. For lower pressure, the pressure
factor is approximately 1.
The bare module cost of the trays are estimated from the following equation :
Where,
=
D Tower diameter in meters
The actual number of trays is computed by dividing the number of equilibrium stages
used in the simulation by the tray efficiency. The O'Connell Correllation is used to find the
tray efficiency for distillation columns (Seader and Henley):
Eo =0.503.(aopf 00226
For the absorber and stripper, the tray efficiency is calculated as follows:
L L
Log(Eo) = 1.597 - 00199010g KMLO
PL /lLJ - 0.0896 ((KM
log PL'/l JJ2
(
Where
169
K =K-value of species being absorbed or stripped
PL =density of the liquid
ML =molecular weight of the liquid
For the reflux accumulator, the total liquid (reflux + distillate) flow rate leaving the
accumulator = the vapor flow rate from the top tray. The accumulator volume is calculated
using the following equation :
The length can then be found from the Length/Diameter ratio, and figure 9.3 (a) of
Seider, Seader, and Lewin can be used to estimate the cost.
The following pages summarize the calculations of the cost for the various columns.
The reboilers and condensers were priced separately using B-JAC because it is more
rigorous and precise.
170
Reflux Accumulator
top stage vol (ft"3/hr) 685
Vol. flow rate (ft"3/min) 11 .41666667
Accumulator Volume (ft"3) 114.1666667
Diameter (L to D = 4) 3.312298574
Length 13.2491943
Rounded diameter (ft) 3.5 meters 1.06707317
Rounded length (ft) 10 meters 3.04878049
Fm 4
Fp 1.1
Fbm 8.004210526 Current Price
Cp 4000 $5,192
Cbm 32016.84211 $41,560
171
ACETIC ACID DISTILLATION COLUMN DC-610
Input I
Liquid Vapor
Flow rate (Ib/hr) 210500 151800
Density (lb/ft"3) 80.63198482 0.464469959
Molecular weight
Surface tension (dyne/cm) 34 n/a
Reflux Accumulator
top stage vol (ft"3/hr) 2243
Vol. flow rate (ft"3/min) 37.38333333
Accumulator Volume (ft"3) 373.8333333
Diameter (L to D =4) 4.918609886
Length 19.67443954
Rounded diameter (ft) 5 meters 1.52439024
Rounded length (ft) 20 meters 6.09756098
Fm 4
Fp 1.1
Fbm 8.004210526 Current Price
Cp 9000 $11 ,683
Cbm 72037.89474 $93,511
172
ACETONE DISTILLATION COLUMN DC-810
Input
Liquid Vapor
Reflux Accumulator
top stage vol (ft"3/hr) 40
Vol. flow rate (ft"3/min) 0.666666667
Accumulator Volume (ft"3) 6.666666667
Diameter (L to D = 4) 1.285047805
Length 5.140191221
Rounded diameter (ft) 1.5 meters 0.457317
Cbm 13607.15789
$17,663
Purchased Cost -
$7,738.74
$10,045
173
NEAR AZEOTROPE DISTILLATION COLUMN DC-900
Input
Liquid Vapor
Density (lb/ft"3)
79.33146894 0.464469959
Molecular weight
Surface tension (dyne/cm) 16 n/a
Reflux Accumulator
Length
7.985884624
Fbm
8.004210526 Current
Cp 2100 $2,726
Cbm 16808.84211 $21,819
Purchased Cost
11074.07308 $14,375
Flow parameter
0.081592715
Flooding capacity factor/Cf (m/s) 0.096763678
C
0.092540186
U (85% of Uf)
1.024986476
Diameter (m)
0.475956465
Diameter (ft)
1.561137206
Current Cost
Purchased Cost
229.3287683 $298
Purchased Cost
$11,303.40 $14,673
174
ETHYL ACETATE DISTILLATION COLUMN DC-910
Input
Liquid Vapor L V
Flow rate (Ib/hr) 3222 2789 36814 73444
Density (lb/ft"3) 86 .39141231 0.46446996 930 5
Molecular weight
Surface tens ion (dyne/cm) 17 n/a
Reflux Accumulator
175
STRIPPER ST -800
,
Input
Liquid Vapor
Flow rate (Ib/hr) 14550 7637
Density (lblft"3) 83 .60459256 0.33441837
Molecular weight
Surface tension (dyne/cm) 60 n/a
Reflux Accumulator
top stage vol (ft"3/hr) 53
Vol. flow rate (ft"3/min) 0.883333333
Accumulator Volume (ft"3) 8.833333333
Diameter (L to D = 4) 1.41142534
Length 5.645701361
Rounded diameter (ft) 1.5 meters 0.457317073
Rounded length (ft) 6 meters 1 .829268293
Fm 4
Fp 1
Fbm 7.424736842 Current Price
Cp 1800 2,337
Cbm 13364.52632 17,348
I,:
Calculations
Bare module cost of tower 219579.8593 285,032
Purchased Cost 2666.115202 3,461
176
ABSORBER AB-320
Input Iii1:J/;j
Liquid Vapor
Flow rate (Ib/hr) 105300 23160
Density (lb/ft"3) 86.984076 0.33441837
Molecular weight
Surface tension (dyne/cm) 31.839 n/a
Calculations I
Current Price
Bare module cost of tower 82886.3851 $107,593
Purchased Cost 20349.1044 $26,415
Current Price
$9'73~1
Bare Module Cost of trays 7495.776
Purchased Cost 249.8592 $324
177
REFRIGERATED ACETALDEHYDE RECOVERY DC-510
Input
Liquid Vapor
Reflux Accumulator
top stage vol (ft"3/hr) 40
Diameter (L to D = 4)
1.285047805
Length
5.140191221
Fbm
8.004210526 Current Price
Cp 1600 $2 ,077
Cbm 12806.73684 $16,624
Calculations
. Current Price
Flow parameter
0.059904267
Flooding capacity factor/Cf (m/s) 0.1 00340717
C
0.099316617
Flooding velocity/Uf (m/s) 1.410515226
U (85% of Uf)
1 .198937942
Diameter (m)
0.076954233
Diameter (ft)
0.252409884
Rounded Tower Diameter (ft) 1.5
Purchased Cost
216 .0493598 $193
178
DECANTER DE-720
ft3
Flow := 643
hr
V:= Flow(lOmin)2
Assume UD =3
2
n D L
V=-
4
3
nD 3
V=-
4
D:= (4.V) 3
3 n
D = 4.497ft
D:= 4.5ft
L:= 3D
L = 13.5ft
L=4.115m
D=1.372m
179
From cost chart, Cp in 1982 is $7,000
C~002
Cp := 7000- -
CE I982
3
Cp = 9 x 10
Cp = $9,000
Pressure Factor:
Fp:= I
Material Factor:
FM := 4.0
4
C BM = 6.3x 10
CE l985 := 325
In Aspen:
Estimate a stack temperature of 670 F. Using a table found in McKetta. find the efficiency.
efficiency:= 0 .83
Ocalc
Q:=--
efficiency
Q= 15.292
180
Use Q =20 MMBtu/hr for design
Q:= 20
k is material factor
k:= 42
Design Factor
fd := 0
Pressure factor
f p .=
. 0
CE J985
5
Clnstalled = 6.1 05 x 10
C_lnstalled = $610,500
Estimate bare module cost and purchase costs using table based on estimates for
bare module costs as a function of purchased cost found in Seider (343)
ClnstaJled
C p :=
2.34
5
C p = 2.609 x 10
Cp = $260,900
CBM := 3.18C p
C
BM = 8.296 x 105
C_BM = $829,600
181
FLASH VESSEL (FV-310)
V := flowrate(5 min) 2
4 3
V = 1.686 x 10ft
Because required volume will be large, in order to limit the size of the radius, so that it can be
transported directly, instead of fabricating it on site, an aspect ratio of 4.5 is selected.
I 2
-nD L
4
=V
1 2 .
-n D (4.5-D) =V
4
4.Y ) 3
D '= -
( 4.5-n
D = 16.833 ft
D:=17 ft
L:= 4.5D
L = 76.5 ft
In order to use the cost charts, length and diameter must be in meters.
D=5.182m
L = 23.317m
The length of 5.182 m is beyond the cost chart's range, but we will extrapolate based on the
lines that are present
C~002
C p := 150000 - -
CE 1982
5
C p = 1.929 x 10
Cp = $192,900
182
Pressure Factor
Fp:== 1
Material Factor
FM :== 4 .0
C BM :== FBMC p
C BM == 1.832 x 10
C_BM =$1,832,000
Compare cost estimated using B-JAC with estimates from cost chart. Surface area
calculated using B-JAC is used because it is more accurate than the area from the
Aspen results.
2
SA :== 8343.ft
SA == 775 .09m
CE2002
C p :== 40000 CE
I982
4
C p == 5.143 x 10
Cp = $51,430
Fp:== 1.05
FM := 3.0
FpFM == 3.15
FSM := 6
183
C BM := 651430
5
C BM = 3.086 x 10
C_BM = $308,600
Using B-JAC, the estimated purchase cost was $83,255.
Bare-Module cost estimate was $265,000
The prices are comparable, but the bare module cost estimated from B-JAC (and used for
calculating the total cost) is 14% lower than the bare module cost using cost charts.
by Aspen .
Powernet := 13hp
Powernet = 9.694 kW
YJ := 0.52
Powernet
Power:= - -
YJ
Power = 18.642 kW
Power = 25hp
C~002
C p := 9000 - -
CE 1982
4
C p =1.157 x l0
Cp = $11,570
Material Factor
FM := 1.9
Pressure Factor
Fp:= 1.1
184
C BM := FBMCp
C BM = 5.786 x 10
C_BM = 57,860
Power requirement for this pump can also be calculated by hand, without using the
Aspen results.
This can be done using the following equation , found on p. 804 in Seider, Seader, and Lewin.
(gpm)(psidifference)
hpower = ...:='---'....:..:....----'
(1714)( efficiency)
ft3
gpm:= 719.6
hr
min
efficiency:= 0.52
(89 .7)(248.3)
hpower:= (1714)(0.52)
hpower = 24.989
The power requirement of 25 hp used for the calculations agrees well with this result.
Powernet := 15.6hp
Powernet = 11.633 kW
11 := 0.57
Powernet
Power:= - - -
11
Power = 20.409 kW
CE 2002
C p := 9000--
CE I982
185
4
C p = U57 x 10
Cp=$11,570
Fp:= 1.1
4
CBM = 5.786 x 10
C_BM = $57,860
Powernet := 2.49 bp
Powernet = 1.857 kW
0.485
1'] :=
Powernet
Power := - -
1']
Power = 3.828kW
C~002
C p := 4800--
CE I982
3
C p = 6.171 x 10
Cp = $6,171
4
CBM = 3.086 x 10
186
ETHYL ACETATE PUMP P-620
Powernet := 1.83hp
Powernet = 1.365 kW
T]:= 0.44
Power
Power := net
T]
Power=3 .10IkW
CE2002
C p := 4500- -
CE I982
3
C p = 5.786 x 10
Cp = $5,786
C mV1 := FBMC p
C BM = 2.893 x 10
C_BM = $28,930
Powernet := 0.11 hp
0.30
T] :=
Powernet
Power :=
11
Power = 0.273 kW
CE2002
C p := 2000- -
CE I982
3
C p = 2.571 x 10
Cp = $2,571
C BM := Cp-FBM
4
C BrvI = 1.286 x 10
187
THE REFLUX AND REBOILER PUMPS WERE NOT SIZED USING ASPEN. THE
POWER REPORTED IS TAKEN TO BE THE TOTAL INPUT REQUIREMENT (CONSIDERS
EFFICIENCY)
Power:= 7.46kW
C~002
C p := 2800- -
. CE
I982
3
C p =3 .6 x 10
Cp =$3,600
4
C BM = 1.8 x 10
Power:= Il .2kW
C~002
C p := 7000--
CE I982
3
C p = 9 x 10
Cp = $9,000
4
C BM = 4.5 x 10
Power := 0.097kW
188
C p := 1700. CI1002
CE I982
Cp = 2.186 x 10
Cp = $2,186
C BM := FBMC p
C BM = 1.093 x 10
C_BM = $10,930
NEAR AZEOTROPE DISTILLATION COLUMN REBOILER PUMP PB-900
Power:= O.37 kW
C := 2200. CI1002
p
CE I982
Cp = 2.829 x 10
Cp = $2,829
C BM := FBMC p
~M = 1.414 x
4
10
C_BM = $14,140
Power:= 0.30kW
C := 2J 00 . CI1002
p
CE I982
C p = 2.7 x 10
Cp = $2,700
C BM := FBMC p
C BM = 1.35 x 10
189
ACETALDEHYDE REFLUX PUMP PR-500
Power:= 1.49kW
C~002
C p := 3300- -
CE 1982
3
C p = 4.243 x 10
Cp = $4,243
4
C BM = 2.121 x 10
Power := 0.25kW
C~002
C p := 2000 - -
CE 1982
3
C p = 2.571 x 10
Cp = $2,571
4
C BM = 1.286 x 10
Power:= 5.6kW
190
C := 5500. CE:2002
p
CE I982
C p = 7.071 x 10
Cp = $7,071
C BM := FBMCp
CBM = 3.536 x 10
C_BM = $35,360
Power:= 0.25kW
C := 2000.
p C~002
CE I982
Cp = 2.571 x 10
Cp = $2,571
C BM := FBMC p
CBM = 1.286 x 10
C_BM = $12,860
Power:= 0.097kW
CE 2002
C p := 1600--
CE 1982
3
C p = 2.057 x 10
Cp = $2,057
CBM := FBMC p
191
Cp = $2,057
4
C BM = 1.029 x 10
Power:= 1.l2kW
C~002
C p := 3100--
CE l982
3
Cp = 3.986 x J 0
Cp = $3,986
4
C BM = 1.993 x 10
Power := 0.097kW
C~002
C p := 1600--
CE 1982
3
C p = 2.057 x ]0
Cp = $2,057
4
C BM = 1.029 x 10
192
REFRIGERATION SYSTEM RF-520
The cost calculations are based on table 20.2 in Walas.
The amount of cooling required for the condenser C-520 is 613,000 Btu/hr. Assuming 33% of
cooling is lost to "heat leak" 900,000 Btu/hr of cooling is required of the refrigeration system .
Q := 0.9 MM Btu/hr
Temperature factor for refrigeration at -20 C
F:= 2.10
CE 1985
Cinstalled = 3.568 x J 0
Since it is unclear what is included in the purchase cost of the refrigeration system, in finding
the total cost of equipment, we assume an installed price of $500,000 to ensure that all pumps,
tanks, and the glycol solution are accounted for.
REACTOR RX-240
Amount of catalyst required is determined by the space velocity.
GHSV = vreactants
Vcatalyst
GHSV:= 2600.hr- J
v ft3
reactants:= 224307
hr
Vreactants
Vcatalyst:= GHSV
Take the diameter of the reactor to be 4 ft., and find the required height of the catalyst bed .
Footer: 6 ft.
Total length:
L:= h + lOft
L = 16.865 ft
Round this up :
L :=17ft
L
- = 4.25
This is a reasonable aspect ratio; the diameter does not need to be re-evaluated.
L = 5.182m
D= l.219m
C~002
C p := 13000- -
CE 1982
4
C p = 1.671 x 10
Cp = $16,710
F M := 4.0
Pressure is 16 barg
Fp := 2.0
F BM := 16
194
C BM := FBMC p
C BM = 2.674 x J0
C_BM = $267,400
CATALYST COSTS
p := 42.~
ft3
Weightcatalyst := p .Vcatalyst
1650
Costcatalyst := - -
Ib
COS~otal =
6
5.979 x 10
Cost = $5,979,000
Estimate that catalyst must be replaced every 5 years, budget 20% replacement per year
900
Salvage:= -
Ib
5
Replacecosts = 5.435 x 10
Replacement = $543,500Iyr
195
ACETIC ACID HOLDING TANK T-1
Use 1-day supply of acetic acid, since facility is located on the site of major chemical manufacturer
ft3
vACOH := 320
hr
time := 24 hr
V := v ACOH" time
V = 217.473m
Use cubic meters, because those are the units required for cost chart.
C~002
C p := 20000
CE l982
4
Cp = 2.571 x 10
Cp =$25,710
FBM := 4 .5
5
C BM = l.l5 7 x 10
C_BM = $115,700
ft3
v:= 401.4-
hr
t := 12hr
V: = vt
V = 136.397m
C~002
C p := 9000
CE I982
4
C P = 1.157 x 10
Cp =$11,570
196
C BM := FBMC p
CBM = 5.207 x 10
C_BM = $52,070
ACETIC ACID HOLDING TANK (T-3)
v:= 7.542
hr
V:= v 1
v= 2.56 3m
CEz002
C p := 1200- -
CE 1982
3
C p = 1.543 x 10
Cp = $1,543
CBM := FBMCp
3
CBM = 6.943 x 10
C_BM = $6,943
1 := 1424h
1= 336 h
ft3
v:= 21.753
h
V:= v1
3
V = 206.968 m
C := 20000. CEz002
p
CE 1982
4
C p = 2.571 x 10
Cp = $25,710
197
5
CBM = 1.157 x 10
C_BM = $115,700
t := 1424hr
V:= vt
3 3
V =2 .61I x 10 m
CE:2002
C p := 52000 - -
CE 1982
4
C p = 6.686 x 10
Cp = $66,860
This tank must be refrigerated in order to keep the temperature of acetaldehyde below 60 F.
Assume that this doubles the bare module cost.
5
CBM = 6.0 17 x 10
t := 12 hr
ft 3
hr
198
V:= v!
V=615.1 85 m
C := 22000. CE:z002
p
CE 1982
C p = 2.829 x 10
Cp = $28,290
C BM := FBMC p
C BM = 1.273 x 10
C_BM = $127,300
This tank must hold a 12-hour supply of the acetaldehyde distillation column's bottoms, stream
S-506.
ft3
v:= 1699.945
hr
V := v!
3
V = 577.645 m
C := 20000. C"E:z002
p
CE I982
Cp = 2.571 x 10
Cp = $25,710
C BM := FBM C p
C BM = 1.157 x 10
C_BM = $115,700
199
200
lOZ
SNOILV'lil:)'lV:) ISO:) XII'lIIil
:gXION3ddV
202
COOLING WATER
Required cooling water is 385,000 gal/hr. Annual cost is determined considering a cost of
$0.33/1000gal, and operation at 7920 hr/yr.
gal
cw:= 385000
hr
cw yr gal
6 - I
total cw = 1.006 x 10 yr
According to Table 9.4 in Seider, Seader, and Lewin, the cost is $58/gpm
This book also lists the cooling water cost as $0.05/1 OOOgal, which is considerably
less expensive than our estimate. Thus, assume the allocated cost is $300/gpm.
3 gaJ
cw = 6.417 x 10
mm
Cost:= 6417300
Cost = 1.925 x 10
203
STEAM COSTS
35 psig steam :
Ib
F35 := 2898
hr
.00246
c '=-
35' lb
-I
C 35 = 7.129hr
75 psig steam:
lb
F75 := 16703
hr
-I
c75 := .002551b
-I
C 75 = 42 .593 hr
.0028
c600:= -
lb
-I
C 600 = 82 .981 hr
-I
C tot = 132 .703 hr
6
Cannual = l.051 x 10
204
C_annual =$1,051 ,00/yr
Cost for steam is allocated facility is $50 per pound per hour
Ib
SteaTTtot := 49238
hr
50
c:= -
Jb
hr
C alloc := SteaTTto(c
6
CalJoc = 2.462 x 10
C_alloc = $2,462,000
If generating the initial capital is not a concern, it appears to be more profitable to build an
allocated steam plant.
205
206
LOZ
:3 XIGN3:ddV
208
VESSELS
ITEM: AB-320
BLOCK: ABSORBER MODEL: RADFRAC
**********************
**** INPUT DATA ****
**********************
NUMBER OF STAGES 15
ALGORITHM OPTION STANDARD
ABSORBER OPTION YES
INITIALIZATION OPTION STANDARD
HYDRAULIC PARAMETER CALCULATIONS NO
INSIDE LOOP CONVERGENCE METHOD BROYDEN
DESIGN SPECIFICATION METHOD NESTED
MAXIMUM NO . OF OUTSIDE LOOP ITERATIONS 25
MAXIMUM NO. OF INSIDE LOOP ITERATIONS 10
MAXIMUM NUMBER OF FLASH ITERATIONS 50
FLASH TOLERANCE 0.00010000
OUTSIDE LOOP CONVERGENCE TOLERANCE 0.00010000
*******************
**** RESULTS ****
*******************
OUTLET STREAMS
RECYCLE RECOVERY
COMPONENT:
HYDROGEN 1.0000 .33439E-05
C02 .97692 .23077E-01
METHANE .98156 .18437E-01
ETHYLENE .96964 .30358E-01
209
VESSELS
ITEM: AB-320 (CONTINUED)
*** COMPONENT SPLIT FRACTIONS ***
OUTLET STREAMS
--------------
RECYCLE RECOVERY
COMPONENT:
ETHANE .96448 .35519E-01
ACETALD .92922E-01 .90708
ACETONE .31952 .68048
ETHYLACE .31643 .68357
ETHANOL .12114 .87886
WATER .68472E-01 .93153
HOAC .33743E-01 .96626
**NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS
FROM THE STAGE EXCLUDING ANY SIDE PRODUCT. FOR THE FIRST STAGE,
THE REPORTED VAPOR FLOW IS THE VAPOR DISTILLATE FLOW . FOR THE
LAST STAGE, THE REPORTED LIQUID FLOW IS THE LIQUID BOTTOMS FLOW.
ENTHALPY
STAGE TEMPERATURE PRESSURE BTU/LBMOL HEAT DUTY
F PSI LIQUID VAPOR BTU / HR
210
VESSELS
ITEM: AB-320 (CONTINUED)
**** MASS FLOW PROFILES ****
1 0.48004
2 0.47829
14 0.45827
15 0.44897
1 0.65502E-02
2 0.62734E-02
14 0.32669E-02
15 0 . 26719E-02
211
VESSELS
ITEM: AB-320 (CONTINUED)
**** K-VALUES ****
STAGE ACETALD ACETONE ETHYLACE ETHANOL WATER
1 0.56738 0.15000 0.13494 0.63870E-Ol 0.28036E-Ol
2 0.55500 0.14532 0.12980 0.60261E-Ol 0.27035E-Ol
14 0.38841 0.89122E-Ol 0.73773E-Ol 0.26616E-Ol 0.15269E-Ol
15 0.34653 0.76719E-Ol 0.61800E-Ol 0.20602E-Ol o .13012E-Ol
212
VESSELS
UNIT: DC-SO~
BLOCK: HACDIST MODEL: RADFRAC
---------- - - - - - - - - - - - - - - - - - - - - -
INLETS - DFEED STAGE 28
OUTLETS - UP STAGE 1
HAC PROD STAGE 1
BOTTOMS STAGE 40
PROPERTY OPTION SET: NRTL-RK RENON (NRTL) / REDLICH-KWONG
HENRY-COMPS ID: HC-l
**********************
**** INPUT DATA ****
**********************
NUMBER OF STAGES 40
ALGORITHM OPTION STANDARD
INITIALIZATION OPTION STANDARD
HYDRAULIC PARAMETER CALCULATIONS NO
INSIDE LOOP CONVERGENCE METHOD NEWTON
DESIGN SPECIFICATION METHOD NESTED
MAXIMUM NO. OF OUTSIDE LOOP ITERATIONS 60
MAXIMUM NO. OF INSIDE LOOP ITERATIONS 10
MAXIMUM NUMBER OF FLASH ITERATIONS 50
FLASH TOLERANCE 0.00010000
OUTSIDE LOOP CONVERGENCE TOLERANCE 0.00010000
** STOICHIOMETRIC COEFFICIENTS **
213
VESSELS
**** PROFILES
****
P-SPEC STAGE 1 PRES, PSI 32 . 0000
*******************
**** RESULTS ****
*******************
OUTLET STREAMS
--------------
UP HAC PROD BOTTOMS
COMPONENT:
OUTLET STREAMS
--------------
UP HAC PROD BOTTOMS
COMPONENT :
**NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS
FROM THE STAGE EXCLUDING ANY SIDE PRODUCT. FOR THE FIRST STAGE,
THE REPORTED VAPOR FLOW IS THE VAPOR DISTILLATE FLOW. FOR THE
LAST STAGE, THE REPORTED LIQUID FLOW IS THE LIQUID BOTTOMS FLOW.
214
VESSELS
ENTHALPY
STAGE TEMPERATURE PRESSURE BTU/LBMOL HEAT DUTY
F PSI LIQUID VAPOR BTU/HR
215
VESSELS
****MOLE-X-PROFILE ****
STAGE ACETALD ACETONE ETHYLACE ETHANOL WATER
1 0.99051 0.22339E-I0 0.19187E-21 0.10000E-29 0.64326E-02
2 0.99193 0.61500E-I0 0.23368E-20 0.10000E-29 0.77785E-02
26 0.94338 0.35829E-02 0.11977E-02 0.10380E-03 0.49697E-Ol
27 0.85026 0.80995E-02 0.69879E-02 o .13095E-02 0.10025
28 0.30917 0.79118E-02 0.10710E-Ol 0.56740E-02 0.33781
29 0.30551 0.89707E-02 o .11227E-Ol 0 . 57204E-02 0.33951
30 0.28841 0.12462E-Ol 0.13469E-Ol 0.59498E-02 0 . 34719
31 0.24067 0.21380E-Ol 0.21172E-Ol 0.68345E-02 0.36855
39 0.36284E-03 0.16277E-Ol 0.36185E-Ol 0.25265E-02 0 . 52784
40 0 . 94749E-04 0.87298E-02 0.20325E-Ol 0.15503E-02 0.48536
216
VESSELS
UNIT: DC-SOO (CONTINUED)
29 0.22931E-01
30 0 . 24868E-01
31 0.31729E-01
39 0.21834
40 0.28346
217
VESSELS
UNIT: DC-SOO (CONTINUED)
**** RATES OF GENERATION ****
LBMOL/HR
STAGE ACETONE ETHYLACE ETHANOL WATER HOAC
1 O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO
2 O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO
26 O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO
27 O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO
28 O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO
29 O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO
30 O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO
31 O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO
39 O.OOOOE+OO 15.22 -15.22 15.22 -15.22
40 O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO O.OOOOE+OO
218
VESSELS
UNIT: DC-SO~ (CONTINUED)
27 0.93878E-06 0.51417E-02 0.11761E-02 0.12057E - 02 0.12826E-02
28 O.52804E-07 0.55658E-02 0.12669E-02 0.12975E-02 0.13819E-02
29 0.18698E-12 o .13541E-03 0.22956E-04 0.85246E-04 0.61658E-04
30 0.66398E-18 0.32675E-05 0.41007E-06 0.55560E-05 0.27402E-05
31 0.24027E-23 0 . 77844E-07 0.71035E-08 0.34942E-06 0 . 12032E-06
39 0.43340E-2S 0.24668E-21 0.22727E-24 0.83377E-18 0.18409E-18
40 0.56299E-25 0.50694E-27 0.23109E-27 0.96721E-28 0.91632E-28
UNIT: DC-SID
BLOCK: COND MODEL: RADFRAC
INLETS - UP STAGE 3
OUTLETS - OFFGAS STAGE 1
HACPROD2 STAGE 3
PROPERTY OPTION SET: NRTL-RK RENON (NRTL) / REDLICH-KWONG
HENRY-COMPS ID: HC-1
**********************
**** INPUT DATA ****
**********************
219
VESSELS
UNIT: DC-510 (CONTINUED)
HYDRAULIC PARAMETER CALCULATIONS NO
INSIDE LOOP CONVERGENCE METHOD BROYDEN
DESIGN SPECIFICATION METHOD NESTED
MAXIMUM NO. OF OUTSIDE LOOP ITERATIONS 25
MAXIMUM NO. OF INSIDE LOOP ITERATIONS 10
MAXIMUM NUMBER OF FLASH ITERATIONS 50
FLASH TOLERANCE 0.00010000
OUTSIDE LOOP CONVERGENCE TOLERANCE 0.00010000
*******************
**** RESULTS ****
*******************
OUTLET STREAMS
- - - - - - - - - -
OFFGAS HACPROD2
COMPONENT:
HYDROGEN 1.0000 .15998E-07
CO2 .99396 .60437E-02
METHANE .98875 .11253E-01
ETHYLENE .95529 .44715E-01
ETHANE .97804 .21961E-01
ACETALD .28451E-01 .97155
ACETONE .56151E-03 .99944
WATER .54628E-04 .99995
220
VESSELS
UNIT: DC-SI0 (CONTINUED)
**** PROFILES ****
**NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS
FROM THE STAGE EXCLUDING ANY SIDE PRODUCT. FOR THE FIRST STAGE,
THE REPORTED VAPOR FLOW IS THE VAPOR DISTILLATE FLOW. FOR THE
LAST STAGE, THE REPORTED LIQUID FLOW IS THE LIQUID BOTTOMS FLOW.
ENTHALPY
STAGE TEMPERATURE PRESSURE BTU/LBMOL HEAT DUTY
F PSI LIQUID VAPOR BTU/HR
221
VESSELS
UNIT: DC-SI0 (CONTINUED)
**** K-VALUES ****
STAGE ACETALD ACETONE WATER
1 0.13562 0.23279E-01 0.12491E-02
2 0.79271 0.25559 0 . 32458
3 0.84216 0.27593 0.39036
BTU!HR PSI F
!============!============!============!============!
0.0 28.0000 94 . 0763 1.0000
- 2480.7655 28 . 0000 90.8666 DEW>1.0000
-5.5717+04 28.0000 89.5678 0.9189
- 1.1143+05 28.0000 87.9270 0.8345
-1.6715+05 28.0000 85.9013 0 . 7510
!------------+------------+--- - --------+ - -----------!
-2 . 2287+05 28.0000 83.3465 0.6687
-2.7859+05 28.0000 80.0428 0.5879
-3.3430+05 28.0000 75.6490 0.5095
-3 . 9002+05 28.0000 69.6249 0.4346
-4.4574+05 28.0000 61.1175 0.3649
!-------- -- --+------------+---- - -------+------------!
-5.0145+05 28.0000 48 . 8093 0.3025
! -5.5717+05 ! 28.0000 ! 32.1052 ! 0.2517 !
! -6 . 1289+05 ! 28.0000 ! 10.0064 ! 0.2088 !
222
VESSELS
ITEM: DC-610
BLOCK : ACOHDIST MODEL: RADFRAC
**********************
**** INPUT DATA ****
**********************
NUMBER OF STAGES 18
ALGORITHM OPTION 3-PHASE
ABSORBER OPTION NO
INITIALIZATION OPTION STANDARD
HYDRAULIC PARAMETER CALCULATIONS NO
INSIDE LOOP CONVERGENCE METHOD BROYDEN
DESIGN SPECIFICATION METHOD NESTED
MAXIMUM NO. OF OUTSIDE LOOP ITERATIONS 25
MAXIMUM NO. OF INSIDE LOOP ITERATIONS 10
MAXIMUM NUMBER OF FLASH ITERATIONS 50
FLASH TOLERANCE 0.00010000
OUTSIDE LOOP CONVERGENCE TOLERANCE 0.00010000
223
VESSELS
ITEM: DC-610 (CONTINUED)
*** COMPONENT SPLIT FRACTIONS ***
OUTLET STREAMS
--------------
DIST ACOHREC
COMPONENT:
**NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS
FROM THE STAGE INCLUDING ANY SIDE PRODUCT .
ENTHALPY
224
VESSELS
ITEM: DC-610 (CONTINUED)
3 2154. 2502.
9 2252. 2601.
10 3063. 2635. 743.2091
11 3070 . 2703.
16 3609. 2998.
17 3890. 3250.
LBMOL/HR BTU/LBMO
11 0.9662E+05 0 .7 516E+05
16 0.1724E+06 0.1158E+06
17 0.2103E+06 0.1516E+06
LB/HR
LIQUIDI LIQUID2
1 0.9481E+05 0.1524E+05
2 O.OOOOE+OO 0.5738E+05
3 O.OOOOE+OO 0.5333E+05
9 O.OOOOE+OO 0.6469E+05
10 O.OOOOE+OO 0.9590E+05
11 O.OOOOE+OO 0.9662E+05
16 0.1724E+06 O. OOOOE+OO
17 0.2103E+06 O.OOOOE+OO
18 0.2074E+05 O.OOOOE+OO
225
VESSELS
226
VESSELS
227
VESSELS
228
VESSELS
229
VESSELS
ITEM: DC-610 (CONTINUED)
**** MASS-Y-PROFILE ****
STAGE ETHANOL WATER HOAC
1 0.65513E-02 0.16053 0.17700E-01
2 0.52048E-02 0.25056 0.91385E-Ol
3 0.28900E-02 0.55676 0.28733
9 0.91664E-03 0.53909 0.43213
10 0.87919E-03 0.49301 0.47911
11 0.24770E-03 0.49777 0.49504
16 0 . 53428E-06 0.23756 0.76242
BTU/HR PSI F
!============!============!============!============!
0.0 98.6000 358.2887 0.0
!------ -- ----+------------+------------+------------!
BTU/HR PSI F
I============!============!============!============!
230
VESSELS
ITEM: DC-BIO
BLOCK: ACETONE MODEL: RADFRAC
INLETS - 45 STAGE 8
OUTLETS - WAS ACTON STAGE 1
RECY STAGE 11
PROPERTY OPTION SET: NRTL-RK RENON (NRTL) / REDLICH-KWONG
HENRY-COMPS ID: HC - l
**********************
**** INPUT DATA ****
**********************
NUMBER OF STAGES 11
ALGORITHM OPTION STANDARD
ABSORBER OPTION NO
INITIALIZATION OPTION STANDARD
HYDRAULIC PARAMETER CALCULATIONS NO
INSIDE LOOP CONVERGENCE METHOD BROYDEN
DESIGN SPECIFICATION METHOD NESTED
MAXIMUM NO. OF OUTSIDE LOOP ITERATIONS 25
MAXIMUM NO . OF INSIDE LOOP ITERATIONS 10
MAXIMUM NUMBER OF FLASH ITERATIONS 50
FLASH TOLERANCE 0.00010000
OUTSIDE LOOP CONVERGENCE TOLERANCE 0.00010000
231
VESSELS
*******************
**** RESULTS ****
*******************
*** COMPONENT SPLIT FRACTIONS ***
OUTLET STREAMS
--------------
WASACTON RECY
COMPONENT:
HYDROGEN 1.0000 .11031E-18
ACETALD .95262 .47380E-01
ACETONE .78379 .21621
ETHYLACE .22231 .77769
ETHANOL .46665 .53335
WATER .27389 .72611
HOAC .10587E-05 1.0000
ENTHALPY
STAGE TEMPERATURE PRESSURE BTU/LBMOL HEAT DUTY
F PSI LIQUID VAPOR BTU/HR
232
VESSELS
ITEM: DC-SIO (CONTINUED)
STAGE FLOW RATE FEED RATE PRODUCT RATE
LBMOL/HR LBMOL/HR LBMOL/HR
LIQUID VAPOR LIQUID VAPOR MIXED LIQUID VAPOR
1 30.78 7.694 7.6938
2 30.77 38.47
3 30.52 38.46
6 30.29 37.99
7 30.36 37.98 20.1111
8 30.31 17.94
10 30.21 17.83
11 12.42 17.79 12.4173
233
VESSELS
1 0.21205 0.20077E-08
2 0.25294 0.12424E-07
3 0.28091 O. 72702E- 07
6 0.31927 0.13779E-04
7 0.31985 0.77378E-04
8 0.32867 0.77710E-04
10 0.35226 0.88395E-04
11 0.36257 0.18483E-03
**** K-VALUES
****
STAGE WATER HOAC
1 0.80561 0.13357
2 0.84818 0 . 13742
3 0.87066 0.13810
6 0.91942 0.14199
7 0.94993 0.14694
8 0.95775 0.14718
10 0.98752 0.14936
11 1.0410 0.15731
1 0.82912E-01 0.15782E-07
2 0.93669E-01 0.94657E-07
3 0.10117 0.55028E-06
6 0.10770 0.10032E-03
7 0.10267 0.53526E-03
8 0.10463 0.53664E-03
10 0.10819 0.59838E-03
11 0.10320 O. 11605E- 02
234
VESSELS
BTU/HR PSI F
!============!============!============!============!
0.0 24.9000 183.1507 0.0
245.4757 24.9000 183 . 3695 BOO>O . O
2.2937+04 24.9000 183.4705 5.3156-02
4.5875+04 24.9000 183.5689 0 . 1068
6.8812+04 24.9000 183.6639 0.1604
!------------+------------+------------+------------!
9.1750+04 24.9000 183.7557 0.2141
1.l469+05 24.9000 183.8446 0.2676
1.3762+05 24.9000 183.9310 0.3212
1.6056+05 24.9000 184.0151 0.3747
1.8350+05 24.9000 184.0974 0.4283
- -----------+------------+------------+-----------
2.0644+05 24.9000 184.1782 0 . 4818
2 . 2937+05 24.9000 184 . 2581 0.5353
2.5231+05 24.9000 184.3375 0.5889
235
VESSELS
ITEM: DC-B10 (CONTINUED)
BTU/HR PSI F
!============!============!============!============!
0.0 22.0000 174.4885 1.0000
-3317.0574 22.0000 170.2403 DEW>1.0000
-3 .8 975+04 22.0000 170.0385 0.9339
-7.7950+04 22.0000 169.8144 0.8614
-1.1693+05 22.0000 169.5862 0.7887
!--------- -- -+----------- - +------------+------- - ----!
-1.5590+05 22.0000 169.3540 0.7158
-1.9488+05 22.0000 169.1176 0.6427
-2.3385+05 22.0000 168.8772 0.5695
-2 . 7283+05 22.0000 168 . 6329 0.4960
-3.1180+05 22.0000 168.3847 0.4223
!------------+------------+------------+------------!
-3 . 5078+05 22.0000 168.1326 0.3484
ITEM: DC-900
BLOCK: NEAZDIST MODEL: RADFRAC
ETACACOH STAGE 12
**********************
**** INPUT DATA ****
**********************
NUMBER OF STAGES 12
ALGORITHM OPTION STANDARD
ABSORBER OPTION NO
INITIALIZATION OPTION STANDARD
HYDRAULIC PARAMETER CALCULATIONS NO
INSIDE LOOP CONVERGENCE METHOD BROYDEN
DESIGN SPECIFICATION METHOD NESTED
MAXIMUM NO. OF OUTSIDE LOOP ITERATIONS 25
MAXIMUM NO. OF INSIDE LOOP ITERATIONS 10
MAXIMUM NUMBER OF FLASH ITERATIONS 50
FLASH TOLERANCE 0.00010000
OUTSIDE LOOP CONVERGENCE TOLERANCE 0.00010000
236
VESSELS
ITEM: DC-900 (CONTINUED)
**** COL-SPECS ****
*******************
**** RESULTS ****
*******************
OUTLET STREAMS
NEAZRECY ETACACOH
COMPONENT:
HYDROGEN 1.0000 .21252E-41
C02 1 . 0000 . 22584E-11
ACETALD .99999 .12760E-04
OUTLET STREAMS
NEAZRECY ETACACOH
COMPONENT:
ACETONE .99790 .20984E-02
ETHYLACE .75141 .24859
ETHANOL .99188 .81152E-02
WATER .99615 .38485E-02
HOAC .23235E-02 .99768
237
VESSELS
ENTHALPY
STAGE TEMPERATURE PRESSURE BTU/LBMOL HEAT DUTY
F PSI LIQUID VAPOR BTU/HR
238
VESSELS
239
...
VESSELS
ITEM: DC-900 (CONTINUED)
5 0.75130E-13 o .12734E-14 o .13609E-03 0.27583E-Ol 0.91743
6 o .54 879E-13 0.12934E-14 0.12321E-03 0.25539E-Ol 0.90293
7 O.OOOOOE+OO O.OOOOOE+OO 0.36259E-04 o .14205E-Ol 0.92785
10 O.OOOOOE+OO O.OOOOOE+OO 0.65900E-06 0.21505E-02 0.93053
11 O.OOOOOE+OO O.OOOOOE+OO 0.16568E-06 o .11273E-02 0.88163
12 O.OOOOOE+OO O.OOOOOE+OO 0.37708E-07 0.56526E-03 0.72045
BTU/HR PSI F
!============!============!============!============!
0.0 28.0000 212.6416 0.0
2510.6086 28.0000 212.8657 BUB>O.O
2.8639+05 28.0000 213.1768 8.2608-02
240
VESSELS
BTU/HR PSI F
!============!============!============!============!
0.0 25.0000 189.5595 1.0000
!------------+------------+------------+------------!
-1.0587+06 25.0000 184.9356 0.6368
-1.3234+06 25.0000 184.8049 0.5450
-1.5881+06 25 . 0000 184.6750 0.4533
-1.8527+06 25.0000 184.5426 0.3616
-2.1174+06 25.0000 184.4055 0.2699
------------+------------+------------+-----------
-2.3821+06 25.0000 184.2614 0 . 1782
UNIT: DC-910
BLOCK: ETACDIST MODEL: RADFRAC
241
VESSELS
UNIT: DC-9I0 (CONTINUED)
*** MASS AND ENERGY BALANCE ***
IN OUT RELATIVE DIFF .
TOTAL BALANCE
**********************
**** INPUT DATA ****
**********************
NUMBER OF STAGES
23
ALGORITHM OPTION
STANDARD
ABSORBER OPTION
NO
INITIALIZATION OPTION
STANDARD
FLASH TOLERANCE
0.00010000
OUTSIDE LOOP CONVERGENCE TOLERANCE
0.00010000
*******************
**** RESULTS ****
*******************
OUTLET STREAMS
ETOAC ACOHPROD
COMPONENT:
OUTLET STREAMS
ETOAC ACOHPROD
COMPONENT:
242
VESSELS
UNIT: DC-910 (CONTINUED)
*** SUMMARY OF KEY RESULTS ***
**NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS
FROM THE STAGE EXCLUDING ANY SIDE PRODUCT. FOR THE FIRST STAGE,
THE REPORTED VAPOR FLOW IS THE VAPOR DISTILLATE FLOW. FOR THE
LAST STAGE, THE REPORTED LIQUID FLOW IS THE LIQUID BOTTOMS FLOW .
ENTHALPY
STAGE TEMPERATURE PRESSURE BTU/LBMOL HEAT DUTY
F PSI LIQUID VAPOR BTU/HR
243
VESSELS
UNIT: DC-9ID (CONTINUED)
**** MASS FLOW PROFILES ****
244
VESSELS
21 0.91478
22 0 . 97228
23 0.99155
245
VESSELS
UNIT: DC-910 (CONTINUED)
14 0.39796E-08 0.20086E-03 0 . 93458 0.10010E-03 0.55380E-03
21 0.30286E-13 0.89279E-06 0.12007 0.99708E-05 0.33256E-04
22 0.28008E-14 0.23404E-06 0.40072E-01 0.33640E-05 0 . 13417E-04
23 O.OOOOOE+OO 0.57157E-07 0.12328E-01 0.10358E-05 0.49521E-05
BTU/HR PSI F
!============!============!============!============!
0.0 20.1000 261.7049 0.0
294.9185 20.1000 262.0238 BUB>O.O
4.4265+04 20 . 1000 262.2445 7.7763-02
8.8531+04 20.1000 262.4033 0.1562
1.3280+05 20.1000 262.5220 0.2349
!------------+------------+------------+------------!
1.7706+05 20.1000 262.6139 0.3136
2.2133+05 20.1000 262.6872 0.3924
2.6559+05 20.1000 262.7469 0.4712
3.0986+05 20 . 1000 262.7964 0.5501
3.5412+05 20.1000 262.8382 0.6290
!-------- - ---+------------+------------+------------!
3.9839+05 20.1000 262.8739 0 . 7080
4.4265+05 ! 20.1000 ! 262.9048 ! 0.7869 !
4.8692+05 ! 20.1000 ! 262.9318 ! 0.8659 !
246
VESSELS
BTU/HR PSI F
!============!============!============!============!
0.0 16.0000 181.6249 1 . 0000
-6816.3628 16 . 0000 175 . 4321 DEW>1.0000
-4.6325+04 16.0000 175 . 4104 0.9213
-9.2650+04 16.0000 175.3842 0.8290
-1.3897+05 16.0000 175.3565 0.7368
------------+------------+- - ----- - ----+-----------
-1.8530+05 16.0000 175.3266 0.6446
-2.3162+05 16.0000 175.2938 0.5524
-2.7795+05 16 . 0000 175.2572 0 . 4603
-3.2427+05 16 . 0000 175.2155 0.3681
-3.7060+05 16.0000 175.1674 0.2760
!------------+-------- - ---+-- - - - -------+-----------
-4.1692+05 16.0000 175.1107 0.1839
-4.6325+05 16.0000 175.0425 9.1967-02
- 5.0957+05 16.0000 174.9589 0.0
ITEM: DE-720
BLOCK: DECANTER MODEL: DECANTER
INLET STREAM: 14
FIRST LIQUID OUTLET : DECETAC
SECOND LIQUID OUTLET: DECWATER
PROPERTY OPTION SET: NRTL-RK RENON (NRTL) / REDLICH-KWONG
HENRY - COMPS ID: HC-l
247
VESSELS
ITEM: DE-720 (CONTINUED)
ACETALD 0 . 00071625 0.0011375 0.00021945 0.19293
ACETONE 0 . 051802 0.078651 0.020138 0.25604
ETHYLACE 0 . 31299 0.55781 0.024284 0.043534
ETHANOL 0.0051848 0.0068579 0.0032117 0.46833
WATER 0.57082 0.27694 0.91738 3.31255
HOAC 0.058487 0.078601 0.034766 0.44230
ITEM: ST-800
BLOCK: STRIPPER MODEL: RADFRAC
- - - - - - - - - - - - - - - - - - - - - - - - - ------
INLETS - DECWATER STAGE 2
STEAM STAGE 6
OUTLETS - 45 STAGE 1
WAS WATER STAGE 6
PROPERTY OPTION SET: NRTL-RK RENON (NRTL) / REDLICH-KWONG
HENRY-COMPS ID : HC-l
**********************
**** INPUT DATA ****
**********************
NUMBER OF STAGES 6
ALGORITHM OPTION STANDARD
ABSORBER OPTION NO
INITIALIZATION OPTION STANDARD
HYDRAULIC PARAMETER CALCULATIONS NO
INSIDE LOOP CONVERGENCE METHOD BROYDEN
DESIGN SPECIFICATION METHOD NESTED
MAXIMUM NO . OF OUTSIDE LOOP ITERATIONS 25
MAXIMUM NO . OF INSIDE LOOP ITERATIONS 10
MAXIMUM NUMBER OF FLASH ITERATIONS 50
FLASH TOLERANCE 0.00010000
OUTSIDE LOOP CONVERGENCE TOLERANCE 0.00010000
*******************
**** RESULTS ****
*******************
248
VESSELS
ITEM: ST-800 (CONTINUED)
OUTLET STREAMS
-------------
45 WASWATER
COMPONENT:
HYDROGEN 1.0000 . 86878E-27
ACETALD .91236 .87637E-Ol
ACETONE .66785 .33215
ETHYLACE .97572 .24277E-Ol
ETHANOL .92295E-Ol .90771
WATER .12820E-Ol .98718
HOAC .11172E- 02 .99888
**NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS
FROM THE STAGE EXCLUDING ANY SIDE PRODUCT. FOR THE FIRST STAGE,
THE REPORTED VAPOR FLOW IS THE VAPOR DISTILLATE FLOW. FOR THE
LAST STAGE, THE REPORTED LIQUID FLOW IS THE LIQUID BOTTOMS FLOW.
ENTHALPY
STAGE TEMPERATURE PRESSURE BTU/LBMOL HEAT DUTY
F PSI LIQUID VAPOR BTU/HR
249
VESSELS
ITEM: ST-800 (CONTINUED)
**** MASS FLOW PROFILES ****
1 0.28135 0.43113E-02
2 0.77683 0.28063E-01
3 0.77430 0.28444E-01
4 0.81800 0.31350E-01
5 0.91485 0.34845E-01
6 0.96450 0.27432E-01
1 0.29619 0.72549E-03
2 0.28462 0.35212E-02
3 0.28058 0.36938E-02
4 0.27099 0.51540E-02
5 0.40172 0.14821E-01
6 0.79228 0.28836E-01
250
VESSELS
****MASS-X-PROFILE ****
STAGE HYDROGEN ACETALD ACETONE ETHYLACE ETHANOL
1 0.12058E-14 0.11851E-02 0.16089 0.74947 0.35765E-02
2 O.OOOOOE+OO 0.79370E-03 0.12933 0.35181 0.61068E-02
3 O.OOOOOE+OO 0.70891E-03 0 . 16141 0.31223 0.82661E-02
4 O.OOOOOE+OO 0.49918E-03 0.17566 0.19631 o .13797E-01
5 O.OOOOOE+OO 0.18779E-03 0.90622E-01 0.38175E-01 0 . 14785E-01
6 O.OOOOOE+OO 0.34361E-04 0.15755E - 01 0.21066E-02 0.54470E-02
251
ITEM: HX-200
BLOCK: HOACHEAT MODEL: HEATX
HOT SIDE:
---------
INLET STREAM: RXHOAC
COLD SIDE:
----------
INLET STREAM: 2
252
PRESSURE SPECIFICATION:
HOT SIDE PRESSURE DROP PSI 5 . 0000
COLD SIDE PRESSURE DROP PSI 8.0000
1 1
RXHOAC ----->1 HOT 1-----> RX2
T= 5.5681D+02 1 1 T= 2.8014D+02
P= 2.5092D+02 1
1 P= 2.4592D+02
V= 1.0000D+00 I 1 V= 1 . 0000D+00
1 1
HOACHOT <-----1 COLD 1<----- 2
T= 4.6467D+02 I 1 T= 2.4194D+02
P= 2.5500D+02 1
1 p= 2.6300D+02
V= 1.3360D-01 1
1 V= O.OOOOD+OO
253
PRESSURE DROP:
HOT
1 I
RXHOAC VAP 1 VAP 1 RX2
------ >
1 1------ >
556.8 498.21 1 280 . 1
1 I
HOACHOT BOIL 1
LIQ 1 2
<- - --- 1 1<-----
464.7 464.21 1 241. 9
1 I
COLD
BTU/HR PSI F
!============!============!============!============!
0.0 255.0000 241.9905 0.0
3.9139+05 255.0000 274.3506 0.0
7.8277+05 255.0000 305.1550 0.0
1.1742+06 255.0000 334.2501 0.0
254
HEATERS AND HEAT EXCHANGERS
ITEM: HX-200 (CONTINUED)
1 . 5655+06 255 . 0000 361.5443 0.0
------------+------------+-------- - ---+-----------
1.9569+06 255.0000 387 . 0089 0.0
------------+------------+------------+-----------
3 . 5225+06 255.0000 463 . 7365 2.3952-02
3 . 913 9+06 255 . 0000 464.2370 7 . 8545-02
4 . 3053+06 255.0000 464.6727 0.1336
BTU/HR PSI F
!============!============!============!============!
0.0 245.9153 556 . 7709 1.0000
------------+------------+------------+-----------
-1.9569+06 245.9153 433.7258 1.0000
------------+------------+------------+---------- -
-3.9139+06 245.9153 306.2390 1.0000
ITEM: HX-210
BLOCK: H2HEAT MODEL: HEATX
HOT SIDE:
COLD SIDE:
INLET STREAM: 7
OUTLET STREAM: H2HOT
PROPERTY OPTION SET: NRTL-RK RENON (NRTL) / REDLICH-KWONG
HENRY-COMPS 10: HC-l
255
PRESSURE SPECIFICATION:
HOT SIDE PRESSURE DROP PSI 5.0000
COLD SIDE PRESSURE DROP PSI 8.0000
STREAMS :
256
HEATERS AND HEAT EXCHANGERS
ITEM: HX-210 (CONTINUED)
HEAT TRANSFER COEFFICIENT:
AVERAGE COEFFICIENT (DIRTY) BTU/HR-SQFT-R 149.6937
PRESSURE DROP:
HOTSIDE, TOTAL PSI 5.0000
COLDSIDE, TOTAL PSI 8.0000
HOT
1
RXH2 VAP 1 RX3
------> 1------>
556.8 1 280.1
1
H2HOT VAP 1 7
<----- 1< - ----
477.6 1 202.6
1
COLD
BTU/HR PSI F
!============!============!============!============!
0.0 254.8160 202.6189 1.0000
257
HEATERS AND HEAT EXCHANGERS
ITEM: HX-2~O (CONTINUED)
6.3571+06 ! 254.8160 403.4280 ! l . 0000 !
7.1517+06 ! 254.8160 428.2150 ! l . 0000 !
!------------+--- - --------+------------+------------!
BTU/HR PSI F
!============!============!============!============!
0.0 245.9153 556.7709 1.0000
!------------+------------+------------+------------!
ITEM: HX-530
BLOCK: SOLVHEAT MODEL: HEATX
HOT SIDE:
HENRY-COMPS ID: HC - 1
COLD SIDE:
258
SPECIFIED VALUE F
158.0000
LMTD CORRECTION FACTOR
1.00000
PRESSURE SPECIFICATION:
STREAMS:
1 1
SOLV ----->1 HOT
1--- -- > SOLVCOOL
T= 2.6266D +02 1
I T= 1.5800D+02
P= 3.78000+01 1
1 P= 3.1800D+01
V= 0.00000+00 1
1 V= O.OOOOD+OO
1 1
CW20 <-----1 COLD 1<----- CW2
T= 1.19940+02 I I T= 9.0000D+01
P= 2.20000+01 I 1 P= 3.0000D+01
V= 0.00000+00 1
1 V= O.OOOOD+OO
LMTD (CORRECTED) F
100.78 80
259
HEATERS AND HEAT EXCHANGERS
ITEM: HX-530 (CONTINUED)
PRESSURE DROP:
HOTSIDE, TOTAL PSI 6.0000
COLDSIDE, TOTAL PSI 8.0000
HOT
SOLV LIQ
SOLVCOOL
----- > 1------ >
262.7 1 158.0
1
CW20 LIQ 1 CW2
<----- 1<-----
119.9 1 90.0
1
COLD
BTU!HR PSI F
!============!============!============!============!
0.0 31. 8000 252.2654 1.4239-02
!------------+---------- - -+------------+------------!
!------------+------------+------------+------------!
260
REATERS AND HEAT EXCHANGERS
ITEM: HX-710
BLOCK: COOLDIS MODEL: HEATX
HOT SIDE:
INLET STREAM: 13
OUTLET STREAM: 14
COLD SIDE:
HENRY-COMPS ID : HC-1
PRESSURE SPECIFICATION:
HOT SIDE PRESSURE DROP PSI 3.0000
COLD SIDE PRESSURE DROP PSI 5.0000
261
HEATERS AND HEAT EXCHANGERS
ITEM: HX-710 (CONTINUED)
STREAMS:
13 ----- >
HOT ----- > 14
T= 2.1413D+02
T= 1.1300D+02
P= 3.9000D+01
P= 3.6000D+01
V= 1.0459D-01
V= O.OOOOD+OO
PRESSURE DROP:
HOTSIDE, TOTAL PSI 3.0000
COLDSIDE, TOTAL PSI 5.0000
HOT
1
13 COND 1 14
------> 1------>
214.1 1 113.0
1
262
INLET STREAM: 3
OUTLET STREAM: DFEED
PROPERTY OPTION SET: NRTL-RK RENON (NRTL) / REDLICH-KWONG
HENRY-COMPS ID: HC-l
FLASH SPECIFICATIONS:
NPHASE 2
MAX NUMBER OF ITERATIONS 30
CONVERGENCE TOLERANCE 0.00010000
ITEM: CP-4l0
BLOCK: COMP MODEL : COMPR
INLET STREAM: 8
OUTLET STREAM: 7
263
ITEM: P-110
BLOCK: HOACPUMP MODEL: PUMP
FLASH SPECIFICATIONS:
LIQUID PHASE CALCULATION
NO FLASH PERFORMED
MAXIMUM NUMBER OF ITERATIONS 30
TOLERANCE 0 . 00010000
*** RESULTS ***
VOLUMETRIC FLOW RATE CUFT/HR 719.600
PRESSURE CHANGE PSI 248.300
NPSH AVAILABLE FT-LBF/LB 1.90509
FLUID POWER HP 12.9947
BRAKE POWER HP 24.9302
ELECTRICITY KW 18.5904
PUMP EFFICIENCY USED 0.52124
NET WORK REQUIRED HP 24.9302
ITEM: P-540
BLOCK: SOLVPUMP MODEL: PUMP
264
*** RESULTS * **
VOLUMETRIC FLOW RATE CUFT/HR 1,055.61
PRESSURE CHANGE PSI 203.200
NPSH AVAILABLE FT-LBF/LB 64.8476
FLUID POWER HP 15.6000
BRAKE POWER HP 27 . 3599
ELECTRICITY KW 20 . 4023
PUMP EFFICIENCY USED 0.57018
NET WORK REQUIRED HP 27.3599
ITEM: P-600
BLOCK: ACOHPUMP MODEL : PUMP
FLASH SPECIFICATIONS:
LIQUID PHASE CALCULATION
NO FLASH PERFORMED
MAXIMUM NUMBER OF ITERATIONS 30
TOLERANCE 0.00010000
ITEM: P-620
BLOCK: ETACPUMP MODEL: PUMP
265
YALYE, COMPRESSOR AND PUMPS
ITEM: P-620 (CONTINUED)
PROPERTY OPTION SET: NRTL-RK RENON (NRTL) / REDLICH-KWONG
HENRY-COMPS ID: HC-1
FLASH SPECIFICATIONS:
LIQUID PHASE CALCULATION
NO FLASH PERFORMED
MAXIMUM NUMBER OF ITERATIONS 30
TOLERANCE 0.00010000
ITEM: P-730
BLOCK: RECYPUMP MODEL: PUMP
INLET STREAM: 21
OUTLET STREAM: 20
PROPERTY OPTION SET: NRTL-RK RENON (NRTL) / REDLICH-KWONG
HENRY-COMPS ID: HC-1
266
VAL VE, COMPRESSOR AND PUMPS
ITEM: P-730 (CONTINUED)
ELECTRICITY KW 0 .2 7532
PUMP EFFICIENCY USED 0.29566
NET WORK REQUIRED HP 0.36921
267
268
69Z
:U XIUN3:ddV
270
Wacker process, the partial oxidation of ethylene. That process is very corrOSlve, requmng
expensive materials of construction. And like all oxidations, over-oxidation of the ingredient and
the product reduce the yield, and convert expensive ethylene into carbon oxides.
selective route to acetaldehyde could be found. Because of the possible legislation of MTBE out
of gasoline, there may be a worldwide glut of methanol, so any chemicals that use methanol may
become much more economically attractive. But the reduction of acetic acid to acetaldehyde is
However, Eastman Chemical has developed a selective palladium catalyst that glves
ethanol, acetone and ethyl acetate, all of which can be sold after puri fication .
ethanol and ethyl acetate, water and ethanol, and water and ethyl acetate. And the acetic acid
water and acetone-water mixtures are famous for their tangent pinches. Rigorous distillation
simulations with thennodynamics that accurately predict each of these azeotropes and pinches
271
Your company has asked your group to detennine whether this new technology should be
used in your Gulf Coast plant. Your job is to design a process and plant to produce 100 MM lb/yr
of acetaldehyde from acetic acid, which is available on the site. Based on past experience, you
know that you will have to defend any decisions you have made throughout the design, and the
Assume a U.S. Gulf Coast location on the same site as a large chemical plant.
Acetaldehyde can be sold for $0.18/Ib. However, ifMTVE is legislated out of gasoline, that
price might drop to $0.12/Ib. Test your economics with both prices, and make appropriate
recommendations. Hydrogen can be purchased over the plant fence for %0.50/Ib at 200 psig.
Ethanol, if99.95% pure, can be sold (on an excise tax-free basis) for $2.50/gal; however, the
ethanol-water azeotrope can also be sold into the fuel market for $1.60/gal. You may sell either
or both grades of ethanol, depending on which is most economical to produce. Ethyl acetate can
be sold for $0.60/Ib. Acetone can be sold for $0.20/Ib. You will need storage tanks, truck or
railcar loading stations, etc., for each byproduct that you sell, or you may burn them in the boiler
for fuel value. Byproducts sold much also meet nonnal purity specs for that chemical. All prices
The plant design should be as environmentally friendly as possible. Recover and recycle
process materials to the maximum economic extent. Also, energy consumption should be
minimized, to the extent economically justified. The plant design must also be controllable and
safe to operate. Remember that you will be there for the start-up and will have to live with
272
tLZ
86.,'IZI'9 -LN3-LVd S3-LV-LS G3-LINfl
:3XIGN3ddV
274
502/300, 325, 339 acid in the presence of an iron oxide catalyst containing
between 2.5 and 90 wt % Pd, more preferably 10 and 80 wi
[56] References Cited % Pd and most preferably 20 and 60 wt % Pd. The catalyst
has a specific surface area of less than 150 m 2 /g. Hydrogen
U.S. PATENT DOCUMENTS and acetic acid are fed to a reactor in a hydrogen to acetic
acid ratio of 2:1 to 25:1, more preferably in a hydrogen to
4,237,073 12/1980 Steppich el al. ........................ 568/401
acetic acid ratio of 3:1 to 15:1 and most preferably in a
4,268,362 5/1981 Ogawa et al. ............................ 203/28
zoic Acid to Benzaldehyde on Zro z Catalysts", Bull. Chem. the other products using azeotropic distillation. Water is
Soc., Jpn, pp. 3085-3090, (1993). contained in the other products, and the azeotrope is an
R. Pestrnan et al., "Selective hydrogenation of acetic acid, azeotrope of ethyl acetate and water. The unreacted acetic
towards acetaldehyde", Reel. Trav. Chim. Pays-Bas, 113, acid is separated in a column, and the column is controlled
pp. 426-430, (1994). to contain an ethyl acetate rich azeotrope of ethyl acetate and
10 9 18
FEED
-., )
275
6,121,498
Page 2
Pestrnan, et aI., "Identification of the Active Sites in .tbe 59, No.1, 1996, pp. 103-110.
Pestman, et ai., "Reactions of Carboxylic Acids on Oxides", Chemical Abstracts, vol. 113, No.8, Aug. 20, 1990, p . 136,
Journal of Catalysis, vol. 168, 1997, pp. 255-264. Abstract No. 61684.
276
LLl
11
m
m
o
-n
-
Gl
-
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co
It;:)
-u
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OI
0
co
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86r'rZy'9 OOOZ'6I' da S
'-.'.,/!'
d
FIG. 2 00
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43 ~
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ro
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35
L_ rn I ~ EtOAc
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REACTION AC
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6,121,498
1 2
METHOD FOR PRODUCING reaction (1) (300-400 C.). The above discussed reactions
" ACETALDEHYDE FROM ACETIC ACro related to hydrogen and acetic acid in the vapor phase are
summarized below:
BACKGROUND OF THE INVENTION
1. Field of the Invention 5
The present invention relates in general to producing (I) CR,C0 2 H + H 2 .... CH,CHO + H 20 lIG 3 OO" 'c. ~ +0, 8
acetaldehyde. More specifically, the present invention kcal/mole
relates to producing acet3.Jdehyde by hydrogenating acetic lIG4OO" c. ~ -0 ,04
kca l/mole
acid. (II) CHJCHO + H, .... CR,CR,OH lIG3 OO" c. ~ -0.4
10
2. Description of the Related Art kcal/mole
Acetaldehyde is an important industrial chemical. It has AG 4 OO" c, +2.5
kcal/mole
been used as a starting material for the commercial manu (ill) 2 CH3 C02 H -. CH,COCH, + CO2 + Hp.
facture of acetic acid, acetic anhydride, cellulose acetate,
other acetate esters, vinyl acetate resins, synthetic pyridine 15
derivatives, terephthalic acid, peracetic acid and pentaeryth The hydrogenation of acetic acid to acetaldehyde and
ritol. Historically, acetaldehyde has been used to produce water (reaction (I) is a mildly endothermic reaction. So, the
acetic acid, but improvements in technology have resulted in thermodynamics of this reaction improve as the temperature
is increased. The subsequent reaction (II), the hydrogenation
more economical acetic acid production from synthesis gas
of acetaldehyde to ethanol, is exothermic, and this reaction
(a mixture of carbon monoxide and hydrogen). This devel 20
becomes less favorable as the temperature increases. Since
opment implies that it may be more economically attractive the equilibrium of the acetic acid hydrogenation is poor, the
to produce acetaldehyde from acetic acid ratber than to reaction must be run with an excess of hydrogen to achieve
produce acetic acid from acetaldehyde if a technically viable appreciable acetic acid conversion. Thus, on a thermody
route existed. namic basis, ethanol formation will be favored at tempera
Acetaldehyde has been produced commercially by the 25 tures of 300-400 C. Reaction (III), the formation of
reaction of ethanol with air at 480 C. in the presence of a acetone, is essentially irreversible at all temperatures above
silver catalyst This process has been replaced by the current 0 C. and becomes very favorable thermodynamically as the
process, the Wacker oxidation of ethylene. Both of these temperature is increased. Increasing the temperature signifi
processes start with ethylene, and the Wacker route is more cantly above 400 C. will not likely improve the selectivity
direct and efficient than the ethanol oxidation route. Acetal-' 30 to tbe desired acetaldehyde product because of increasing
dehyde bas also been produced by the hydration of acety acetone production. Other reactions, sucb as the formation
lene. This process uses mercury salts as a catalyst, and of methane, carbon oxides and C2 hydrocarbons also are
mercury handling can cause environmental and safety prob relevant in acetic acid hydrogenation chemistry, but are of
lems. The use of acetylene causes safety concerns, and the less importance than the three reactions described above
high cost of acetylene relative to ethylene has rendered this 35 unless excessively high temperatures are used. In some
process obsolete, Acetaldehyde can also be produced by circumstances, the formation of ethyl acetate presumably
reacting synthesis gas over a rhodium on silica catalyst at through ethanol as an intermediate can also lower the
elevated temperature and pressure, but the selectivity to selectivity to the desired acetaldehyde.
acetaldehyde is poor, and the process has never been prac Thus, it appears that a IDajor challenge in producing
ticed commercially. Acetaldehyde has also been produced 40 acetaldehyde via acetic acid hydrogenation is catalyst
from tbe reaction of methanol witb synthesis gas at elevated desigIh The ideal catalyst should facilitate the initial hydro
temperature and pressure using a cobalt iodide catalyst with genation of acetic acid to acetaldehyde but have essentiaUy
a group 15 promoter, but this process also has never been, no activity for the subsequent hydrogenation to ethanol nor
practiced commercially. Although the Wacker process is the for the dimerization reaction producing acetone. If a catalyst
preferred commercial process at this time, it also has many 45 has even a small activity for conversion of acetaldehyde to
undesirable aspects. These include the special safety and ethanol or for the conversion of acetic acid into acetone, tben
handling problems associated witb reacting ethylene with extreme losses in acetaldehyde selectivity may occur if the
oxygen and the very corrosive nature of the aqueous acidic reaction is operated beyond the equilibrium conversion level
cbloride-containing reaction mixtures which necessitates allowed for converting acetic acid and hydrogen into acetal
very expensive materials of construction. Thus a need exists 50 dehyde and water. A need exists for a caialyst that selectively
for an acetaldehyde synthesis that is an improvement over hydrogenates acetic acid to acetaldehyde.
the existing known processes. Catalyst selectivity is only one requirement for a viable
A potentially attractive means to synthesize acetaldehyde acetaldehyde synthesis. The synthesis must also be operated
is by the hydrogenation of acetic acid. See reaction (1) in a manner that will allow for the facile recovery of the very
below. However the carboxylic acid group is generally 55 volatile acetaldehyde product, the recovery of byproducts
considered to be among the most difficult functional groups and the recycle of unconverted reactants. GeneraUy pro
to reduce by catalytic hydrogenation. Aldehyde groups, cesses that hydrogenate carboxylic acids to aldehydes do so
conversely, are easily reduced by catalytic hydrogenation to under conditions of about 1 bar pressure (all pressures given
alcohols. See reaction (II) below. Thus, under the conditions berein are in terms of absolute pressures) and hydrogen to
required to reduce a carboxylic acid, the aldehyde is often 60 carboxylic acid ratios approaching 50/1. Although these
not isolated in good yield because the aldehyde is further conditions may be sufficient for nonvolatile aldehydes, they
reduced to an alcohol. Furthermore, when the cart)Qxylic are impractical for acetaldehyde which boils at 19-20 C.
acid contains an a-hydrogen, conversion to a ketone, water Thus, a need also exists for a process that converts acetic
and carbon dioxide can occur. See reaction (III) below. This acid into acetaldehyde in a manner that is selective and
reaction becomes more prevalent as the number of 65 provides for the economical recovery of the acetaldehyde.
a-hydrogens increases. Thus, aCetone can be readily formed In spite of the thermodynamic limitations surrOllDding the
from acetic acid at the temperatures typically used for hydrogenation of carboxylic acids to aldehydes, several
27~
6,121,498
3 4
examples of this reaction appear in the prior art. Generally that there is an optimum Pt level, and tbat increasing the Pt
these reactions are performed at about 1 bar pressure in the level above 1.25 atomic % actually decreases the selectivity.
. :"
vapor phase in a large excess of hydrogen at temperatures Although the acetic acid hydrogenation process studied
ranging between 200 and 500 0 c., and the reaction is most by Ponec and coworkers is very selective to acetaldehyde, it
successful with aromatic carboxylic acids or aliphatic acids 5 is impractical as a commerciaiway to produce acetaldehyde.
containing few a-hydrogens. Van Geem et aI., in U.S. Pal. The impracticality stems from the need to isolate and collect
No. ~,336,81O, describe a Mn/Zn/Al oxide catalyst that acetaldehyde (normal boiling point-19-20 C.) from a
converts benzoic acid to benzaldehyde in the vapor phase at vapor stream where it is present in maximum concentrations
3300 C. in a large excess of hydrogen in 88.3% selectivity of 2-3% (or less, depending on tbe conversion) at about 1
at 98.9% conversion . Joentgen et aI., in U.s. Pat. No. 10 bar pressure. Water and byproducts must be removed from
5,059,716, describe catalyst system based on titanium or the mixture, and bydrogen and unconverted acetic acid must
vanadium oxides in conjunction with one or more metals be recycled to the reactor. These operations require that the
selected from Cr, Mo, Co, Ni, Zn, Cd and Cu for the temperature be lowered considerably from the 300--4000 C.
hydrogenation of aromatic and aliphatic carboxylic acids reaction temperature. A practical process requires much
contai.ning not more than one a-hydrogen at 325-425 0 C. at 15 lower hydrogen/acetic acid ratios and much higher reaction
1 bar in the presence of a large excess of hydrogen. pressures than used by Po nee.
Yokoyama et aI., in Stud. In Surf. Sci. and Cat. 1994, 90,
47-58 and in Bull Chern. Soc. Jpn. 1993, 66, 3085-3090, SUMMARY OF mE INVENTION
describe the use of zirconium oxide and modified zirconium Accordingly, it is an object of the present invention to
oxide catalysts for the hydrogenation of aromatic carboxylic 20
provide a method of producing acetaldehyde that avoids
acids to aldehydes under similar reaction conditions. dangers associated with mercury and acetylene.
Yokoyama et al., in U.S. Pat. No. 5,306,845, also describe
It is a further object of the present invention to provide a
the use of a purified chromium oxide catalyst for the
method of producing acetaldehyde tbat avoids handling
hydrogenation of both aromatic and aliphatic carboxylic
problems associated with reacting ethylene and oxygen.
acids under similar reaction conditions. This patent gives 25
several examples of the hydrogenation of high molecular It is a still further object of tbe present invention to
weight acids, such as stearic acid . Acetic acid is also stated provide a method of producing acetaldehyde that avoids
to be as a suitable acid, but no examples are given. corrosive aqueous acidic acid chloride-containing reaction
Yokoyama et al. stress that the reason for the high purity' mixtures.
requirement in the chromium oxide is to prevent the ketone 30 It is another object of the present invention to provide a
formation reaction. Welguny et aI., in European Patent method for hydrogenating acetic acid with good selectivity
Application EP 0 700 890 (1996), describe the use of for producing acetaldehyde .
oxide-supported tin catalysts for hydrogenation of a wide It is still another object of the present invention to provide
variety of carboxylic acids to aldehydes under the typical a method for hydrogenating acetic acid that allows for easy
high-temperature, high-hydrogen, low-pressure conditions 35 recovery of volatile acetaldehyde.
described previously. Although acetic acid is included in the These and other objects are accomplished by a method of
c1ainIs of tbis patent application, the only examples are for producing acetaldehyde that hydrogenates acetic acid in the
aromatic carboxylic acids and for pivalic acid. Ferrero et aI., presence of an iron oxide catalyst containing between 2.5
in Europe.an Patent Application No. EP 539,274 (1993), and 90 WI % Pd, more preferably 10 and 80 wt % Pd and
descnbe Ru-Sn-B on alumina catalysts for hydrogena 40 most preferably 20 and 60 wt % Pd. The catalyst has a
tion of a wide variety of carboxylic acids to aldehydes under specifrc surface area of less than 150 m 2 /g. Hydrogen and
the typical high-temperature high-hydrogen low-pressure acetic acid are fed to a reactor in a hydrogen to acetic acid
conditions described previously. Although the Ferrero patent, ratio of 2:1 to 25 :1, more preferably in a hydrogen to acetic
application gives no examples for acetic acid hydrogenation, acid ratio of 3:1 to 15:1 and most preferably in a hydrogen
it is mentioned in the claims. Most of the Ferrero reference 45 to acetic acid ratio of 4:1 to 12:1. The hydrogenation is
concerns the reduction of senecioic acid to prenal or the performed at a temperature of about 2500 C. to 400 C.,
reduction of aromat ic carboxylic acids to the corresponding more preferably about 270 0 C. to 3500 C. and most prefer
aldehydes. ably about 2800 C. to 325 0 C. The hydrogenation of acetic
The most definitive work on the acetic acid hydrogenation acid produces a partially gaseous prod1.1ct, and acetaldehyde
to acetaldehyde is described by Ponec and coworkers in 50 is absorbed from the partially gaseous product with a solvent
Reel. Trav. Chim. Pays-Bas 1994, 426--430, in J. Cata!' containing acetic acid. The gas remaining after tbe absorp
1994,148,261-269, inJ. Molecular Catalysis A: Chemical tion step contains hydrogen, and ,this gas is recycled for the
1995, 103, 175-180, in Applied Surface Science 1996, 103, hydrogenation of acetic acid . The absorbed acetaldehyde is
171-182, and in J. Cala/. 1997, 168, 255-264. These distilled to isolate same. After acetaldehyde is isolated from
workers have proposed a working mechanism for the reac 55 uoreacted acetic acid and the other products via distillation,
tion and have reported several examples of the conversion of the uoreacted acetic acid is separated from the other prod
acetic acid to acetaldehyde in good selectivity. The base ucts using azeotropic distillation. Water is contained in the
catalysts for these reductions are partially reduced metal other products, and the azeotrope is an azeotrope of ethyl
oxides having an intermediate metal-oxygen bond strength. acetate and water. The uoreacted acetic acid is separated in
Partially reduced iron oxide is the most selective metal 60 a column, and the column is controlled to contain an ethyl
oxide, and acetaldehyde selectivities almost as high as 80% acetate rich azeotrope of ethyl acetate and water.
could be obtained at 1.2 bar pressure and using a hydrogen/
acetic acid ratio=50/1 at 321 0 C. Addition of 5 wt. % Pt to BRIEF DESCRIPTION OF THE DRAWINGS
this catalyst furtber increases the selectivity to acetaldehyde The invention will be readily understood by reference to
to over 80%. With tin oxide, the addition of the Pt about 65 the following description of the specific embodiments
doubles the selectivity, increasing it from about 40% to described by way of example only, with reference to the
about 80%. Ponec mentions inJ. Cala/. 1997,168,255-264 accompanying drawings, wherein:
280
6,121,498
5 6
FIG. 1 is a schematic representation of components used A~, acetic acid is recovered from stream 33. This acetic acid
, ''''. to produce acetaldehyde; and . . may be mixed with hydrogen and fed to reactor RX via
FIG. 2 is an schematic representation of components used stream 3.
to recover acetic acid. The overhead from acetic acid column AC contains ethyl
acetate, water and other products. Because water is difficult
DETAILED DESCRIPTION OF TIlE to separate from acetic acid as mentioned above, it is
PREFERRED EMBODIMENTS important that excess water not be supplied via stream 35.
For this purpose, stream 32 is condensed in decanter cooler
The present invention will now be described with pre DC and then decanted in decanter DE. The aqueous phase
ferred embodiments and examples which are given by way 10 leaves decanter DE in stream 38, and the organic phase
of example only, not limitation. leaves in stream 37. A portion of stream 37 is supplied back
A specific embodiment of the process of the invention to the acetic acid column Ae. Another portion of stream 37
consists of two main sections: a reaction section and a is fed to azeotrope column Z via stream 39 to distill a "near"
recovery section shown schematically in FIGS. 1 and 2, ethyl acetate-water azeotrope. The mixture is a "near"
respectively. Acetic acid is converted to acetaldehyde and 15 azeotrope because it does not contain the exact azeotropic
water with excess hydrogen in the reaction section over a ratio of ethyl acetate to water. As mentioned above, the
catalyst containing iron and palladium in a fiXed-bed reactor azeotrope has a low boiling point and therefore can be
RX. The acetaldehyde product is recovered via distillation D removed as an overhead from azeotrope column Z. After
after absorption A using the acetic acid-rich distillation azeo column condenser ZC, the azeotrope is indirectly
bottoms as a solvent after cooling S. 20 recycled back to acetic acid column AC via stream 43.
Referring to FIG. 1, stream 3 is a feed to the reactor RX From the bottom of azeotrope column Z, stream 42 is
containing acetic and hydrogen. Although a 1-to-1 molar supplied to ethyl acetate column E after azco column
ratio is stoichiometrically sufficient for producing reboiler ZR. As mentioned above, excess hydrogenation of
acetaldehyde, an excess of hydrogen is supplied in feed 3. acetic acid produces ethanol. The ethanol can react with the
The reactor RX contains an iron oxide/palladium catalysl. 25 acetic acid and produce ethyl acetate in an esterification
Before the feed is supplied to the reactor, it is heated with process. This reaction occurs throughout the apparatus,
furnace F and reactor preheater PH. The product of reactor whenever ethanol and acetic acid are present together. The
RX is fed to an absorber A This product is hot and is cooled reaction may be especially prominent when both reactants
in feed effluent exchanger FE. Feed effluent exchanger FE are in the liquid phase. Ethyl acetate column E separates
also serves to preheat the feed 3 to the reactor. The product 30 ethyl acetate as an overhead. After ethyl acetate column
of reactor RX is substantially gaseous. Absorber A is used to condenser EC, stream 54 contains ethyl acetate which can be
liquify the acetaldehyde and other prodUCts. Cooled product sold as a finished product. From the bottom of ethyl acetate
4 supplied to the absorber A and acetic acid feed 7 is also column E, a somewhat small stream 55 of acetic acid is
supplied. Acetic acid from feed 7 captures the products and produced after ethyl acetate column reboiler ER.
allows hydrogen to pass via stream 6. A portion of the 35 As mentioned above, decanter DE separates aqueous
hydrogen is recycled via stream 10, recycle compressor RC products from organic products. The aqueous stream 38 is
and stream 13. Another portion of the hydrogen is purged via supplied to steam stripper SS. Steam stripper SS is a
stream 9, and tbis maintains the purity of hydrogen. Recycle distillation column heated by steam 46. Lighter organics
compressor RC compresses the hydrogen. Reactor RX and come off the top of steam stripper SS in stream 45 and waste
absorber A operate under pressure. The pressure in absorber 40 water comes off the bottom as stream 47. The organics in
A is from pressurized product in stream 4 and from pump streanr45 are supplied to waste acetone column W. Acetone
PU. has a very low boiling point, even lower than the azeotrope.
The liquid coming off of absorber A as stream 8 is sent to, Thus, a waste acetone stream 51 is produced after acetone
distillation column D to recover acetaldehyde. The overhead column condenser We. From the. bottom of the waste
from distillation column D is cooled via condenser C to 45 acetone column W, a near ethyl acetate-water azeotrope
condense same. A portion of the condensed liquid is sent stream 50 is recycled after acetone column reboiler WR.
back to the distillation column D as a reflux. Offgas 18 is not The two azeotrope recycle streams 50 and 43 are not
condensed and leaves the system shown in FIGS. 1 and 2. supplied directly back to the acetic acid columnAC. Instead,
Acetaldehyde product comes from stream 19, and tbis also they are fed to decanter cooler DC . ~nd decanter DE to
leaves apparatus shown in FIGS. 1 and 2. From the bottom 50 remove water.
of the distillation column, are-boiler RB is provided to The processes depicted in FIGS. 1 and 2 are designed for
supply the more volatile compounds back to the distillation optimum operation at the following conditions: 1) as/I
column D. Stream 23 is acetic acid rich and is partially molar ratio of hydrogen to acetic acid in the reactor RX feed
recycled to the absorber A. As mentioned previously, the 3, 2) byproduct ethanol is converted to ethyl acetate as
absorption in absorber A works best at lower temperatures, 55 dictated by chemical equilibrium at of conditions present in
and solvent cooler S is provided for this purpose. the bottom of the acetaldehyde recovery column D, and 3)
Stream 30 may contain ethyl acetate, water, acetic acid the reactor operates at 300 0 e., 17.2 bar, and 45% acetic acid
and acetone. To separate these compounds, the recovery conversion with a selectivity of 89% to acetaldehyde, 5% to
apparatus shown schematically in FIG. 2 is employed. First, ethanol, 4% to acetone (and COJ, and 2% to methane and
acetic acid column AC is used to separate out acetic acid. 60 C2 hydrocarbons (ethylene plus ethane). If the degree of
The boiling point of acetic acid is very close to that of water, ethyl acetate formation from ethanol and unconverted acetic
and it would normally be difficult to separate these two acid in the reactor RX is low, the reaction may be simply
components via distillation. To address tbis problem, ethyl catalyzed by adding sulfuric acid to the HOAc-rich solvent
,)
acetate is fed to acetic acid column AC via stream 35. Ethyl before recovery. The recovery scheme shown in FIG. 2 is
acetate forms an azeotrope with water. The azeotrope has a 65 bigbly dependent on this conversion of byproduct ethanol to
boiling point significantly lower than either water or ethyl ethyl acetate and is a significant part of the present inven
acetate. This enables separation. After acetic acid reboiler tion.
281
Ii.
6,121,498
7 8
Mass-separating agents other than ethyl acetate are pos 90 wt % Pd with the balance of the weigbt calculated as
sible. Such agents may be selected from those 'organic Fe Z0 3 (the actual chemical nature of the iron mayor may not
compounds that from a minimum-boiling azeotrope with be Fe2 0 3 depending on the specific method of catalyst
water and separate into water-rich and organic-rich liquid synthesis used). More preferred catalysts contain between
phases upon condensation. Those skilled in the art ofsepa 5 10 and 80 wt % Pd based on Fe Z0 3 The most preferred
rations may select such an alternate to ethyl acetate and catalysts contain between 20 and 60 wt % Pd based on
modify the process depicted in FIG. 2 appropriately. Fe2 0 3 . Catalysts containing low amounts of palladium per
However, as ethyl acetate is a coproduct of the process its form well under low-pressure high-hydrogen conditions, but
use as an azeotroping agent avoids introducing another 10 may not perform well under the high-pressure low-hydrogen
compound to the process and as such is used in the preferred conditions preferred in the invention. Catalysts containing
embodiment. low amounts of palladium may rapidly lose their activity and
In the preferred embodiment the azeotroping agent both selectivity under the high-pressure low-hydrogen conditions
forms a minimum boiling azeotrope with water and forms preferred in the invention. Excessively high amounts of
two liquid phases upon condensation. Potential azeotroping 15 palladium are uneconomical and may produce excessive
agents include, but are not limited to, acrylonitrile, allyl amounts of hydrocarbons. The active components of the
acetate, allyl acetone, allyl cyanide, benzene, I-butanol, catalyst of the invention can be supported, but the support
l-butenylethyl ether, l-butoxy-2-propanol, butyl acetate, should be unreactive for the conversion of acetic acid to
butyl acetoacetate, butyl acrylate, n-butyl aniline, butyl 20 acetone. The catalyst should have a surface area below 150
benzoate, butyl butyrate, butyl chloride, butyl ether, butyl mZ/g. Catalysts with excessively high surface areas can
isopropenyl ether, 2-butyl octanol, butyraldehyde, exhibit reduced selectivity to the desired acetaldehyde. The
butyronitrile, carbon disulfide, carbon tetrachloride, catalysts of the invention may be reduced in hydrogen prior
2-chloroethyl ether, chloroform, chloroisopropyl ether, to their use in the reaction of hydrogen and acetic acid by
crotonaldehyde, cyclohexane, cyc!ohexanone, 25 contacting the catalysts with hydrogen at about between 50
cyclopentanone, diallyl acetal, diallyl amine, dibutyl acetal, and 500 C. and at about 1-50 bar pressure. More preferred
dibutyl amine, dibutyl ethanolamine, 2,3-dichloropropanol, pre reduction conditions are between 200 and 400 0 C. and
dicyclopentadiene, diethyl acetal, diethyl butyral, 1-20 bar pressure, and the most preferred pre reduction
0
diisobutylene, diisobutyl ketone, dimethyl butyral, 2,5 30 conditions are between 250 and 350 C. and 1-5 bar
dimethyl furan, 2,6-dimethyl-4-heptanol, pressure.
dimethylisobutyral, dipropyl acetal, dipropyl ketone, It is rather important that the catalyst be in a correct
epichlorohydrin, ethyl acetate, ethyl acrylate, n-ethyl oxidation state, and the correct oxidation state should be
aniline, ethylbenzene, 2-ethylbutanol, 2-ethylbutyl acetate, readily regenerated under the reaction conditions. If tbe
2-ethylbutyl butyrate, ethylbutyl ether, ethylbutyl ketone, 35 catalyst is in an over oxidized state, then acetone becomes
2-ethylbutyraldehyde, ethylcrotonate, ethylene dichloride, the predominant product. The selective catalysts contain a
ethyl formate, 2-ethylhexanol, 2-ethylhexyl acetate, mixture of zero valent metal and metal oxide phases. If tbe
2-ethythexyl amine, 2-ethylhexyl chloride, 2-ethylhexyl catalyst is in an over reduced state, methane becomes the
crotonate;2-ethylhexyl ether, ethylidene acetone, predominant product. Addition of Pd to the catalyst facili
40
4-ethyloctanol, ethyl propionate, heptane, 2-heptyl acetate, tates tQe formation and maintenance of the desired oxida tion
3-heptyl acetate, hexaldehyde, hexane, hexanol, 2-hexenal, state.
hexyl acetate, hexyl chloride, isobutyl alcohol, isophorone, The catalysts of the invention are reactive and selective
isopropyl acetate, isopropylbenzene, isopropyl chloride, iso-' under a wide variety of conditions. Temperatures can range
propyl ether, mesityl oxide, methacrylaldehyde, l-methoxy 45 from about 250 to 400 C. More preferred temperatures
l,3-butadiene, 3-methoxybutyl acetaie, methylamyl ketone, range from 270 to 3500 c., and the most preferred tempera
methylene chloride, 2-methyl-5-ethyl pyridine, 5-methyl-2 ture range is from 280 to 325 0 C. At low temperatures the
hexanone, methylisobutyl ketone, methylisopropenyl rate may be low and, if the mixture is low in hydrogen, the
ketone, n-methylmorpholine, 2-methyl pentanal, 2-methyl reaction can also be limited by the equilibrium restrictions
pentanol, 4-methyl-2-pentanol, 4-methyl-2-pentene, 50 dictated by the thermodynamics of the reaction. Excessively
4-methyl-2-pentyl acetate, 2-methylpropyl acetate, methyl high temperature can lead to lower acetaldehyde selectivity
propyl ketone, nonane, paraldebyde, pentane, 2,4 due to the formation of acetone and hydrocarbons. Pressures
pentanedione, 3-pentanol, propionitrile, propyl chloride, can range from less than 1 bar to greater than 50 bars, and
propylene dichloride, styrene, tetrachloroethylene, 1,4 55 the catalysts will still have excellent rates and acetaldehyde
thioxane, toluene, triallyl amine, l,l,2-trichloroethane, 1,1, selectivities provided the right temperatures and hydrogen to
2-trichloroethylene, valeraldehyde, valeric acid, vinyl acetic acid ratios are used. At pressures of about 1 bar at
acetate, vinylallyl ether, vinylbutyl ether, vinyl butyrate, 300 0 C. and at hydrogen to acetic acid ratio of about 40,
vinyl crotonate, vinylethyl ether, vinyl-2-ethylhexyl ether, excellent rates and conversion are seen even with Fe 2 0 3
vinylisobutyl ether, vinyl isobutyrate, vinyl isopropyl ether, 60 containing no Pd. The rate and selectivity under these
vinyl-2-methyl pentanoate, vinyl propionate, vinylpropyl conditions are even higher if Pd is added to the Fe Z0 3 in the
ether, and m-xylene. Among these, ethyl acetate is preferred levels preferred in the present invention. However the recov
since, as mentioned above, it is a coproduct and its use does ery and recycle portions of the process of the invention
'. not introduce anotber component to the separation. 65 become impractical at these low-pressure high-hydrogen
The catalyst (in reactor RX) of the invention contains iron conditions. Lowering the hydrogen to acetic acid ratio at low
and palladium. Catalysts can contain between about 2.5 and pressure lowers the rate and conversion to impractical levels
282
6,121,498
9
10
and places the catalyst in an unfavorable oxidati?o state than acetaldehyde (boiling po~nt 19-20~ C.) using a so~vent
causing increased selectivity to acetone. Generally an rich in acetic acid . The conditions used III absorber A will be
increase in hydrogen plus acetic acid pressure increases the largely dictated by the temperature, press~re, and composJ
rate and degree of acetic acid conversion if other conditions tion of the reactor effluent and tbe desIred aceta~dehyde
remain unchanged. Selectivity can also change as the pres 5 recovery. Acetaldehyde recoveries over 50% are desIred and
sure is increased. Ethyl acetate, which normally is not a may be obtained by proper choice of conditions. Generally,
signillcant product at low. pressure, becomes a significant recovery improves with decreasing temperature, increasing
product as the pressure increases. Acetone, which can be a pressure, and increasing solvent feed rate. This is why the
significant product under low-pressure low-hydrogen 10 temperature of the reactor effluent is decreased via a reactor
conditions, is not a significant product at high-pressure feed-effiuent heat exchanger FE as depicted in FIG. 1.
low-hydrogen conditions provided the catalyst contains Preferably, the temperature of the effiuent will be reduced
about 20 wt % Pd based on Fe2 0 3 If the catalyst contains below 250 0 C. prior to absorption. More preferred are
significantly less than about 20 wt % Pd based on Fez0 3 , temperatures below 2000 C. with temperatures below 1500
then the activity and acetaldehyde selectivity of the catalyst 15 C. most preferred.
rapidly deteriorate with time on stream, and acetone and The pressure in absorber A is important to acetaldehyde
ethyl acetate selectivity increase under ~igh-~ressure low- recovery and should be as high as practically possible. This
hydrogen conditions. Pressures from. acellc aCId and. h!dro pressure should be close to that used in the reactor after
gen greater than SO bars can cause Increased selectiVity to taking into account pressure drops and placement of the
ethanol and ethyl acetate. However the use of di~uen~s ~o 20 gaseous recycle compressor RC. As noted previously, cata
increase the pressure significantly above SO. bars IS Wlt~n lyst selectivity to acetaldehyde suffers when the combined
the spirit of tbe invention. and can be done WIthout ha:mmg . partial pressure of hydrogen and acetic acid exceeds 50 bars
the selectivity. In view of the above-mentIOned which effectively limits the absorber pressure to below 60
considerations, the preferred pressure of acetic acid plus 25 bar after accounting for diluents. So, a broad range of
hydrogen for the process of the invention is between abOut absorber pressure is S to 60 bar with pressures of 6 to 25 bars
5 and 50 bars. A more preferred pressure of hydrogep plus preferred.
acetic acid is betw~en about 5 and 30 bars, and the most The composition of the absorber solvent in stream 7 will
preferred pressure IS be~een ~bout 6 an~ 20 bars. . 30 depend on catalyst selectivity and .acetic acid conversion in
The catalysts of the lllvention are acllve under a WIde the reactor. It should contain mostly unconverted acetic acid,
range of hydrogen to acetic acid ratios. The rate of the however with at least 50 wt % acetic acid ranging up to 9S
reaction increases as the amount of hydrogen increases. The wt % at' low conversion levels. Preferably the acetic acid
rate of reaction first increases as the amount of acetic acid content of stream 7 will be between 60 and 85 wt %. Solvent
increases then decreases as the amount of acetic acid 35 rates will be dictated by the desired acetaldehyde recovery
increases further. As mentioned above excessive amounts of in absorber A but should range between a solvent to absorber
acetic acid at low pressure can place the. catalyst in the feed (stream 4) ratio of 0.1 to 20 wt/WI and preferably
wrong oxidation state giving low rates and lllcreased selec between 1 and 10 wt/wt. .
tivity to acetone. Acetal~ehyde can be produced at hyd~ogen 40 The gaseous product of stream 6 from the absorber will
to acetic acid ratios rangmg from about 2:1 to SO:l.or higher. contain mostly unconverted bydrogen and light gases
However, in view of the recovery and rec~cle ~0I11~ns of the formed as reaction byproducts. This stream will be largely
invention, the preferred hydrogen to acellc aCid raho rangc:s, recycled to the reactor with a purge rate set to maintain a
from about 2:1 to 2S:1. More preferred hydrogen to acetic desired hydrogen purity. While none of these light gases
acid ratio ranges from about 3:1 to lS:l, and the most 45 have been shown to have a deleterious effect on catalyst
preferred ratio ranges from 4:1 to 12:1. performance, it is expected that the hydrogen content oftbe
The gas hourly space velocity (GHSY, vo.lumes o~ ~eac- gaseous recycle 13 should exceed SO mol % with purities
tants contacting the catalyst per hour at reactIOn condilions) between 60 and 9S mol % preferred.
depends on the other p~r~eters descnbed p~eviously. ~en- 50 The second major separation step is recovery of the
erally ~e space veloc.lt~ IS chosen to proVlde the deSired acetaldehyde via distillation in distillation column D. Col
converSIon. The selecuvlty to acetal~ehyde decreases as the umn pressure is important for producing liquid stream 19
acetic acid cODversion increases. This effect can be. ~re~ter from this relatively low-boiling acetaldehyde component
at very .low hydr.ogen levels because once ~he equilibnum (19-200 C.) and should be as high as possible to minimize
conversIOn level IS reached any further reachon converts the 55 refrigeration requirements in the overhead condenser. Mini
acetaldehyde into ethanol and ethyl acetate. Under th~ mo~t mum column pressure is 1 bar with preferred pressures from
preferred conditions of temperature, hydrogen to acetic aCid 5 20 b
ratio and hydrogen plus acehc " aCId pressure It..IS pre erre d t0 to ar.
283
6,121,498
11 12
chromatography. Metered gas flows were provided .by six In some cases a higher temperature was used for the reduc
Tylan Model FC-260 mass flow controllers. Electric tem tion. When the reactor was idle between acetic acid hydro
perature control and monitoring were provided by a Dow genation experiments with the same catalyst charge, hydro
Camile control system interfaced with a Gateway Model gen flow (22.4 SCCM) was maintained at 3000 C.
2000 486DXJ33 computer. All gas delivery lines were teed 5 High pressure acetic acid hydrogenation reactioIlS were
into pressure relief columns containing water to prevent performed in a reactor constructed from a 12 inch length of
. accidental over pressurization. Acetic acid was fed by meter Hastelloy C tubing having an outer diameter of . inch. All
ing hydrogen or nitrogen through a temperature-controlled gas flow, pressure and temperature control devices were
vaporizer containing the acetic acid. The temperature of the 10 controlled by a Camile Model 3300 process monitoring
vaporizer was maintained by a circulating water/ethylene and control system interfaced with an IBM Model 750-P90
glycol bath. Product analysis was performed by on-line gas computer. Hydrogen flow was provided by a Brooks mass
chromatography utilizing a Hewlett-Packard Model 3790A flow controller, and acetic acid was fed using dual ISCO
gas chromatograph fitted with a 6 fLxlfs inch stainless steel high pressure syringe pumps. The device was fitted with a
column containing 80/120 Carbopack B/6.6% CarbowaX 15 relief valve set for 35 bar. Pressure was controlled by a
20M. Products were analyzed by this on-line gas chromato modified Research Control Valve with a pressure transducer
graph with the column programmed for 80 C. for 0 minutes, located between the flow controller and the reactor. A
4 C./minute to 150 0 C. and 1500 C. for 0 minute using a 2-micron filter was placed between the reactor and the
flame ionization detector. A4-port Valco Industries sampling 20 Research Control Valve. The product exiting the Research
valve was used to send the feed mixture to the reactor or to Control Valve was fed to a Valco Industries 6-port gas
the gas chromatograph for analysis. Two six-port Valco chromatographic sampling valve containing a 1 mL sample
Industries gas chromatographic sampling valves containing loop. The gas chromatographic sampling valve was inter
1 mL volume sample loops were used to sample the reactant faced to a Hewlett-Packard Model 3790A gas chroma to-
stream or the product stream. All tubing lines connecting the 25 graph fitted with a 6 ft.XI/S inch stainless steel column
exit of the acetic acid vaporizer, bypass valve, reactor, containing 80/120 Carbopack B/6.6% Carbowax 20M.
six-port sampling valves and the gas chromatograph.. were Products were analyzed by this on-line gas chromatograph
constructed of Ifs-inch stainless steel and were heated with with the column programmed for 80 0 C. for 0 minutes, 4
temperature-controlled heating tapes to 1500 C. The three ' 30 C./minute to 1500 C. and 1500 C. for 0 minute using a flame
sampling valves were heated to 1500 using valve ovens. The ionization detector. The transfer lines, filter and Research
reactor was constructed of main section of 8-inch longx8 Control Valve connecting the reactor to the gas chroma to-
mm 0.0. borosilicate glass fused to a lower section con graphic sampling valve were heated to 200 0 C. by a
sisting of 6-inch longx7.5 mm 0.0.-3 mm 1.0. capillary temperature-controlled heating tape. The gas Chromato
tubing. The reactor had a I-inch longx8 mm 0.0. borosili 35 graphic sampling valve and the transfer line connecting it to
0
cate side arm situated at 90 and 1 inch down from the top the gas chromatograph were maintained at 150 C. The
of the 8 mm 0.0. glass portion of the main reactor section. reactor tube was loaded to position the accurately weighed
The three openings to the reactor were fitted with 2-inch catalyst charge (typically 0.2 g) in the middle of the reactor.
long .-incb 0.0. kovar metal tubing sealed to the end of the 40 Quartz fines (1 inch layer), 12x20 mesh quartz chips (35
glass. Accurately weighed catalyst charges (typically 0.2 g) inches-layer) and quartz or glass wool plugs were placed on
were loaded into the reactor by first inserting a glass or both sides of the catalyst charge. The entire length of the
quartz wool plug from the top of the reactor into the top part, reactor was heated with a temperature-controlled heating
of the capillary section and then placing the catalyst charge tape. The acetic acid was delivered to the reactor via a line
on top of the glass or quartz wool plug. A thermocouple was 45 passing concentrically through the reactor head and about an
inserted through the top of the reactor into the catalyst bed inch into the upper portion of the heated portion of the
and sealed to the kovar tube with Swagelok fittings. The reactor. The hydrogen delivery line and the relief valve were
reactant mixture was fed through the side arm, and the also fitted to the reactor head. Thus the upper portion of the
product exited at the base of the reactor. The kovar portions heated reactor acted as an acetic acid vaporization and vapor
50
of the reactor inlet and outlet were connected to the stainless mixing zone. Catalysts were reduced in hydrogen (25
steel transfer lines using Swagelok fittings. The reactor SCCM) at 1.7 bar at 300 C. in the reactor over night or
was heated with a vertically-mounied single element electric longer before feeding hydrogen and acetic acid. Reactions
furnace containing a 12-inch long heat zone. The apparatus were started by setting the bydrogen and acetic acid feeds to
allowed for additional hydrogen or inert gas to be metered 55 the desired rates at the 1.7 bar setting and then selling the
into the vapor stream exiting the temperature-controlled pressure to tbe desired amount. When the reactor was idle
vaporizer. The acetic acid partial pressure could be con between acetic acid hydrogenation experiments with the
trolled by altering the temperature of the vaporizer or by same catalyst charge, hydrogen flow (22.4 secM) at 1.7 bar
adding hydrogen or inert gas to the vapor stream exiting the was maintained at 300 C.
temperature-controlled vaporizer. The apparatus could also 60 The following definitions apply to the specific examples:
easily be configured to allow inert gas to be metered to the Space velocity (SV or GHSV)=volumes of gas per vol
temperature-controlled vaporizer. This flexibility in setting ume of catalyst per hour under reaction conditions,
the feed composition facilitated the study of the reaction Space time yield (STY)agrams of product produced per
kinetics. Normally catalysts were reduced in hydrogen (22.4 65 liter of catalyst per hour,
standard cubic centimeters per minute, SCeM) overnight at % acetic acid conversion=100(mmoles acetic acid
3000 C. before feeding the acetic acid and hydrogen mixture. reacted)/(mmoles acetic acid fed),
284
6,121,498
13 14
% acetic acid accountability=100(mmoles aceti>; acid Catalyst No.8: Pd sponge. Pd sponge (20 mesh, Alfa lot
recovered+mmoles acetate equivalents in products)/ #00777) was used as received.
(=oles aceticacid fed); Example 1
% normalized selectivity=100(mmoles product)/(total
This example illustrates the effect of changing the weight
mmoles all products).
percentage of Pd on Fe 20 3 by large amollDts under a
Catalysts
The catalysts used in the examples were obtained by the stand ard set of feed conditions at one bar pressure. The
methods that follow. . example illustrates that acetic acid conversion is low when
the catalyst contains 0 or 100% Pd and that the selectivity to
Catalyst No . 1: Fe 2 0 3 . Fe 2 03 (Aldrich, lot
#DQ15808DQ, 99.98% purity) was used as received. 10 methane is high . The example also illustrates that, of tbose
catalysts converting over 90% of the acetic acid, the catalyst
Catalyst No. 2: 2.5% Pd on Fe20 3. A solution was
containing 10 wt % Pd produces acetaldebyde at the higbest
prepared from Pd(N03)2xHz0 (442 mg, Alfa lot
rate and selectivity with the lowest methane selectivity. The
#120982,39.9% Pd) and water (10 mL). This solution
example further shows that althougb the catalyst containing
was added to 20x40 mesh Catalyst No.1 (7_1607 g) 15 no Pd had the highest acetaldehyde selectivity, it also had the
contained in an evaporating dish. The mixture was lowest acetic acid conversion. The relationship between
dried on the steam bath and calcined in a muffle furnace acetaldehyde selectivity and conversion will become more
for 4 hours at 400 C. apparent in subsequent examples. Tbe data for Example 1
Catalyst No.3: 5% Pd on Fe 20 3. A solution was prepared were collected at a point in time when the catalyst activity
from Pd(N0:J2xHz0 (127 mg, Alia lot #120982, 20 was high and are presented in Table 1.
39.9% Pd) and water (2 mL). This solution was added
Example 2
to Catalyst No.1 (1.0294 g) contained in an evaporat .
ing dish. The mixture was dried on the steam bath and This. example compares the performance of catalysts
25 containlD~ 2.5. and 5 wt.% Pd under conditions ?~ compa
Ca ta Iyst N0.: 4 lO ot
-;0
Pd
calcined in a muffie furnace for 5 hours at 400 C.
F A I .
on ez 3' so ution was pre
.' rable acelic aCid conversIOn. The same feed condllions used
. ' ,
pared from Pd(N0 )2 xH 20 (251 mg,Alfa lot #120982, ill Example 2 were used as lD Ex:rn:ple 1, and the data were
3
39.9% Pd), Fe(N03)3. 9Hz O (5.06 g, MallincJ.aOdt lot colle~ted after the catalyst a~t!Vlty had moder~ted thus
Vll'T'J) d
#5032 n.n~. an wa er t (10 L) 'T' h' I t' allowmg for the lower conversIOns. The example illustrates
m. JO t 15 so u IOn was th b a l " 5 m Pd' I ' th
. d fr .. 'd 30 at t e cat yst contammg wt -/0 15 more se ectJve an
added a separate soI utlOn prepare om cltnc aCI ..
' I C I 'al) that contalmng 2.5 wt % Pd when run at the same level of
(2 .59 g, E astman Ch emlca ompany pant maten "d . Th I fu b ill h
. d th acelic aCI conversIOn. e examp e rt er ustrates t at
and water (5 m). L The mIxture was evaporate on e . . . . .
d ' fIl much higher acetaldehyde selectIVIty at much hlgber acetic
steam bath to a sea Iy mass and th en calClDe ill a mu e . . .. . .
c 5 h 4000 C aCid conversIOn can be achieved With catalysts contalDillg
fu mace lor ours a t . 35
. Pd than the Fe 20 3 catalyst of Example 1. The data for
Catalyst No.5: 20% Pd on Fez 0 3' A solutIOn was pre E xamp Ie 2 are presente d'ill T able 2 .
pared from Pd(N03hxH 20 (501 mg, Alfa lot #120982,
39.9% Pd), Fe(N03)3.9Hz0 (5,06 g, Mallinckrodt lot Example 3
#5032"KHTJ) and water (10 mL). To this solution was This example compares the performance of catalysts
added a separate solution prepared from citric acid 40 conta:iJ)ing 5 and 10 wt % Pd IlDder conditions of comparable
(2.23 g, Eastman Cbemical Company plant material) acetic acid conversion. The same feed conditions used in
and water (5 mL). The mixture was evaporated on the Example 3 were used as in Example 1, and the data were
steam bath to a scaly mass and then calcined in a muffle' collected while the catalyst activity was higbest thus allow
furnace for 5 hours at 400 C. 45 ing for the higher conversions. The example illustrates that
Catalyst No.6: 40% Pd on Fe20~. A solution was pre the catalyst containing 10 wt % Pd is more selective than
pared from Pd(N03)2xH20 (Alpha lot #120982, 39.9% that containing 5 wt % Pd when run at the same level of
Pd), Fe(N03hx9H20 (Mallinckrodt lot #5032 KJITJ) acetic acid conversion. The example further illustrates tbat,
and water (10 mL). To this solution was added a at one bar pressure, the optimum performance is achieved
separate solution prepared from cilric acid (Eastman 50 when the Pd level of 10 wt %. The data for Example 3 are
Cbemical Company plant material) and water (5 mL). presented in Table 3.
The mixture was evaporated on the steam bath to a Example 4
scaly mass and then calcined in a muffle furnace for 5
This example illustrates the effects of changing the mole
hours at 400 C. The amount of Pd(N03hxH20 used in 55
fraction of acetic acid in hydrogen (XHOAJ at various space
Catalyst No.5 was approximately doubled to achieve
velocities on tbe performance of the 5 wt % Pd on FeZ0 3 at
40% Pd.
one bar pressure. The example illustrates that high acetal
Catalyst No. 7: 80% Pd on Fe20 3. A solution was pre
dehyde selectivity can be achieved at higb acetic acid mole
pared from Pd(N03)2xH20 (2.005 g, Alfa 101#120982,
60 fraction, but that it is difficult to obtain higber conversions
39.9% Pd), Fe(N03)3.9H20 (1.01 g, Mallinckrodt lot by lowering the space velocity when tbe acetic acid mole
#5032 KHTJ) and water (lOmL). To this solution was
fraction is high at one bar pressure. The data for Example 4
added a separate solution prepared from citric acid
are presented in Table 4.
(1.93 g, Eastman Chemical Company plant material)
and water (5 mL). The mixture was evaporated on the 65 Example 5
steam bath to a scaly mass and then calcined in a muffle This example illustrates tbe performance of tbe 10 wI. %
furnace for 5 hours at 400 C. Pd on Fe 20 3 at 250 psig pressure and at a 5/1 bydrogenJ
285
6,121,498
15 16
acetic acid ratio as a function of time on stream. The "
example illustrates that good rate and acetaldehyde selec TABLE 1
tivity can be achieved, but that the rate, conversion and
acetaldehyde selectivity decrease after a certain time on Effect of a to 100 wt %Pd 00 tlle Performance of Fop, Olt21ysIS
stream. The example also illustrates that the selectivity to Wt%Pd 0 10 20 40 80 1()0
low-hydrogen conditions. The performance data for 10 G/(l-hr) HAc 280 499 157 79 45
% HAc sel.' 80 56 38 35 15 4
Example 5 are presented in Table 5.
%acetone sel. 0.6 3.1 2.7 1.1 0.2 0.3
%EtOH sel. 7 38 50 55 22 0.4
Example 6 %CH., set. 10.5 2.7 8.5 8.6 62.9 95.4
% C, H. C. sel.' 3.1 0.1 0.7 0.3 0 0.1
This example illustrates the performance of the 40 wt % 15 % HOAc acct. 100 100 108 107 105 100
Pd on Fe2 0 3 at 17.2 bar gauge pressure at 7/1 and 5/1
hydrogen/acetic acid ratios with time on stream. 1bis Conditions: 90 SCCM H2 containing 2 mol % HOAc, 0.2 g catalyst, 300
example also iliustrates that the performance of this catalyst e.
'Selectivities are normalized.
does not deteriorate in the manner exhibited by the 10 wt % 20 "c, HydrocarlJOllS - ethylene + ethane.
Pd catalyst of Example 5. The performance data for "'Acetic acid accountability.
Example 6 are presented in Table 6.
TABLE 2
Wt%Pd 25
%HOAc Conv. 54 50 52 50 45 59 51 48 45
G/(l-lu:) HAc 597 621 656 698 527 748 694 674 662
% HAc sel. 78 79 77 80 73 82 84 84 84
%acetone sel. 0.8 0.8 0.9 0.8 1.6 0.7 0.7 0.6 0.6
% EtOH seL 15 15 17 14 18 12 10 9 9
%CH., sel. 4 .6 4.1 4.4 3.8 6.1 5.2 5.7 5.9 5.9
% C2 H. e. sel." 1.0 0.9 0.9 0.8 1.6 0.7 0.7 0.6 0.6
%HOAc accl'" 91 107 103 103 101 97 101 102 105
Example 7
TABLE 3
This example illustrales the integx.ated process of the 45
TABLE 5 TABLE 6
25
Effect of Tune on Stream on the Perfomance of 10 WI % Pd/F~03 Effects of Hydrogen/Acetic Acid Ratio and Tinte on Stream on the
at 250 psig aDd 5/1 Hydrogen/Acetic Acid Ratio. Performance of 40 WI % Pd/Fe203 at 250 psig.
% ca.
sel. 0.7 0.7 % EtOAc sel. 2.1 5.6 6.3
TABLE 7
HOAc Hydrogenation Reaction Section Balance
Stream 11 13 18 19 23 30 31 33 36
Temperature C 67.3 77.6 37.8 37.8 167.8 167.8 167.8 37.8 66.7
Pressure BAR 19.0 19.0 6.9 6.9 6.6 6.6 6.6 2.8 19.0
Vapor Frnction 0.848 1.000 1.000 0.000 0.010 0.010 0.010 0.000 0.847
Mole Flow KGMOUHR 4982 3845 22 318 4466 737 3729 3729 4982
Mass Flow KGIHR 63088 18807 510 13455 183638 30312 153325 153325 63086
\blume Flow M3/HR 6348 5914 84 18 465 77 389 155 6333
Enthalpy MJIHR -3888JO -57092 -2J48 -61647 -1624722 -268188 -1356535 -1397118 -388610
Mole Flow KGMOUHR
HOAC 742.54 15.63 0.00 0.00 2265.66 373.98 1891.67 1891.67 748.43
H2 3742.14 3332.30 5.28 0.05 0 .00 0.00 0.00 0.00 3742.14
HAC 33.21 33.21 5.94 293.39 0.30 0.05 0.25 0.25 33.21
. J
METHANE 358.78 356.76 8.40 2.95 0.00 0.00 0.00 0.00 358.76
ACETONE 2.59 2.59 0.00 0.06 26.65 4.40 22.25 22.25 2.59
ETHANOL 0.23 0.23 0.00 0.00 6.11 1.01 5.10 5.10 6.12
287
6,121,498
19 20
,-.--
"
Stream 11 13 18 19 23 30 31 . 33 36
ETIIEI'! 28.43 28.43 1.28 2.18 0.00 0.00 0.00 0.00 28.43
H2O 28.98 28.98 0.11 16.85 2071.76 341.98 1729.78 1729.78 23.09
CO2 39.37 39.37 1.49 2.61 0.00 0.00 0.00 0.00 39.37
ITOAC 5.89 5.89 0.00 0.00 95.49 15.76 79.73 79.73 0.00
Mass Fraction
HOAC 0.7070 0.0500 0.0000 0.0000 0.7410 0.7410 0.7410 0.7410 0.7120
H2 0.1200 0.3610 0.0210 0.0000 0.0000 0.0000 0.0000 0.0000 0.1200
HAC 0.0230 0.0790 0.5130 0.9610 0.0001 0.0001 0.0001 0.0001 0.0230
METHANE 0.0910 0.3090 0.2840 0.0040 0.0000 0.0000 0.0000 0 .0000 0.0910
ACErONE 0.0020 0.0080 0.0000 0.0003 0.0080 0.0080 0.0080 0.0080 0.0020
ETHANOL 0.0002 0.0008 0.0000 0.0000 0.0020 0.0020 0.0020 0.0020 0.0040
ETIIENE 0.0130 0.0430 0.0700 0.0050 0.0000 0.0000 0.0000 0.0000 0.0130
H2O 0.0080 0.0280 0.0040 0.0230 0.2030 0.2030 0.2030 0.2030 0.0070
CO2 0.0270 0.0930 0.1280 0.0090 0.0000 0.0000 0.0000 0.0000 0.0270
ETOAC 0.0080 0.0280 0.0000 0.0000 0.0460 0.0460 0.0460 0.0460 0.0000
TABLE 8
HOAc Hydro~nation Recovery Section Balance
Saeam 1 2 3 5 7 8 9 12
288
6,121,498
21 22
13. The method according to claim 1, wherein tbe step of from tbe mixture of ethyl acetate, water, acetic acid and
.\ absorbing acetaldehyde is run at a iemperature below 2000 acetone using decantation, steam stripping and distillation .
C. 25. Tile method according to claim 16, wherein step (c)
14. The method according to claim 1, wherein the step of produces acetaldehyde product and a mixture containing
absorbing acetaldehyde is run at a temperature below 1500 acetic acid, a portion of the nllxture containing acetic acid
C. being used in step (b) as the solvent for absorbing acetal
15.- The method according to claim 1, wherein step (b) dehyde.
produces a gaseous remainder containing hydrogen, the 26. A process for the preparation and recovery of acetal
gaseous remainder being recycled to step (a) for the hydro dehyde comprising the steps of:
genation of acetic acid.
16. The method according to claim 1, further comprising 10 (a) contacting within a reactor zone hydrogen and acetic
the step of (c) distilling the absorbed acetaldehyde from the acid with a hydrogen to acetic acid molar ratio of less
solvent containing acetic acid. than 25 in the presence of an iron oxide catalyst
17. The method according to claim 16, wherein step (c) is containing between 20 and 90 wt. % palladium at
performed at a pressure of 1 bar or greater. temperatures between 250 and 400 0 C. and pressures
15
18. The method according to claim 16, wherein step (c) is between 5 and 50 bar;
performed at a pressure from 5 to 20 bar. (b) absorbing the reaction product in acetic acid-rich
19. The method according to claim 16, wherein step (c) solvent and returning a major portion of the uncon
produces acetaldehyde product and a mixture of ethyl densed gases to the reactor zone;
acetate, water, acetic acid and acetone, the method further 20 (c) distilling the acetaldehyde from the acetic acid-rich
comprising the step of (d) recovering the acetic acid from the solvent;
mixture of ethyl acetate, water, acetic acid and acetone using (d) recovering unconverted acetic acid by azeotropic
an azeotropic distillation. distillation;
20. The method according to claim 19, wherein a hetero (e) returning the recovered acetic acid to the reactor zone;
geneous water azeotrope is used for the azeotropic distilla 25
and
tion.
21. The method according to claim 19, wherein an azeo (f) recovering the coproducts water, acetone and ethyl
trope of ethyl acetate and water is used for the azeotropic acetate by decantation, steam stripping and distillation.
distillation. 27. A method of producing .acetaldehyde, comprising the
22. The method according to claim 21, wherein the 30
steps of:
unreacted acetic acid is separated in a column, and the (a) supplying hydrogen and acetic acid to a reactor in a
column is controlled to contain an ethyl acetate rich azeo hydrogen to acetic acid ratio of 2:1 to 25:1; and
.(
trope of ethyl acetate and water. (b) hydrogenating acetic acid in the reactor at a pressure
23. The method according to claim 19, wherein step (a) is between about 5 and 50 bars and a temperature of about
conducted in a reactor zone, the method further comprising 35 250 0 C. to 400 c., the hydrogenation being conducted
the step of returning acetic acid recovered in step (d) to the in the presence of an iron oxide catalyst containing
reactor zone. between 20 and 60 WI. % palladium.
24. The method according to claim 19, further comprising
the step of (e) recovering ethyl acetate, water and acetone * * * * *
289