Acetaldehyde Production by Ethanol Dehydrogenation

Background

Acetaldehyde is a colorless liquid with a pungent, fruity odor. It is primarily used

as a chemical intermediate, principally for the production of acetic acid, pyridine and

pyridine bases, peracetic acid, pentaeythritol, butylene glycol, and chloral. Acetaldehyde

is a volatile and flammable liquid that is miscible in water, alcohol, ether, benzene,

gasoline, and other common organic solvents. The goal of this project is to design a

grass-roots facility that is capable of producing 95,000 tons of acetaldehyde per year by

ethanol dehydrogenation.

Process Description

A preliminary base case BFD for the overall process is shown in Figure 1.

Unit 100

A PFD of Unit 100 is shown in Figure 2. Ethanol, an 85-wt.% solution in water,

Stream 1, is combined with 85-wt.% ethanol recycle stream, Stream 23, from Unit 200.

The resultant stream, Stream 2, is then pumped to 100 psia and heated to 626°F in E-101

and E-102 before being fed to R-101, an isothermal, catalytic, packed-bed reactor, where

the ethanol is dehydrogenated to form acetaldehyde. The reactor effluent is then cooled

in E-103 and E-104. The resultant two-phase stream, Stream 8, is then separated in V-

101. The vapor, Stream 9, is sent to T-101 where it is contacted with water, which

absorbs the acetaldehyde and ethanol from the vapor stream. The resulting vapor

effluent, Stream 11, is then sent for further processing and recovery of valuable
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hydrogen. Alternatively, this stream could be used as fuel. Stream 12, the liquid, is

combined with Stream 14, the liquid effluent from V-101, and sent to Unit 200.

Unit 200

A PFD for Unit 200 is shown in Figure 3. Stream 15 enters T-201 where the

crude acetaldehyde, Stream 16, exits as the distillate. This crude acetaldehyde is then

sent to T-203 where the acetaldehyde is purified to 99.9-wt.%, Stream 17. The bottoms,

Stream 18, is sent to waste treatment. The bottoms from T-201, Stream 19, is sent to T-

202 to begin the purification process of ethanol. In T-202, ethyl acetate and some water

is removed from Stream 19 and exits as the distillate, Stream 20, which is then sent to

waste treatment. The bottoms, Stream 21, is sent to T-204 where ethanol is separated

from butanol, ethyl acetate, and most of the water. These impurities exit in Stream 22

and are sent to waste treatment. The distillate consists of an 85-wt.% solution of ethanol,

which is then recycled back to Unit 100 to be used in the feed. Waste streams, Streams

18, 20, and 22, all contain small quantities of valuable chemicals. Methods for their

separation and purification should be investigated.

Necessary Information and Simulation Hints

The following reactions occur during the dehydrogenation of ethanol:

CH 3CH 2OH → CH 3CHO + H 2 (1)

2CH 3CH 2OH → CH 3COOC2 H 5 + 2 H 2 (2)

2CH 3CH 2OH → CH 3 (CH 2 )3 OH + H 2O (3)

CH 3CH 2OH + H 2O → CH 3COOH + 2H 2 (4)

The conversion of ethanol is assumed to be 60.8%. The yields for each reaction are as

follows:
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(1) acetaldehyde 91.7%

(2) ethyl acetate 3.8%

(3) butanol 2.4%

(4) acetic acid 2.1%

References are not available for these values. Since reaction kinetics were not

available, the above conversions were assumed in the design of the process.

NRTL thermodynamics was used for K-values, as suggested by the Chemcad

expert system.

Equipment Summary

E-101 Reactor Preheater

E-102 Reactor Preheater

E-103 Heat Exchanger

E-104 Heat Exchanger

E-105 Heat Exchanger

E-201 Condenser

E-202 Reboiler

E-203 Condenser

E-204 Reboiler

E-205 Condenser

E-206 Reboiler

E-207 Condenser

E-208 Reboiler

H-101 Fired Heater

P-101A/B Feed Pump

P-102A/B Dowtherm A Pump

P-201A/B Reflux Pump

P-202A/B Reflux Pump

P-203A/B Reflux Pump

P-204A/B Reflux Pump

T-101 Absorber

T-201 Distillation Column

T-202 Distillation Column

T-203 Distillation Column

T-204 Distillation Column

V-101 Flash Vessel

V-201 Reflux Vessel

V-202 Reflux Vessel

V-203 Reflux Vessel

V-204 Reflux Vessel

Stream Tables

Stream 1 2 3 4 5 6
Temp. (°F) 107.6 166.0 166.6 382.8 626.0 626.0
Press. (psia) 14.7 14.7 100 96.2 96.2 96.2
Vapor Fraction 0.0 0.0 0.0 1.0 1.0 1.0
Total Flow (lbmol/h) 1037.9 1498.7 1498.7 1498.7 1498.7 2076.0
Component Flows (lbmol/h)
Acetaldehyde -- 2.4 2.4 2.4 2.4 546.6
Acetic Acid -- -- -- -- -- 11.8
Butanol -- 2.3 2.3 2.3 2.3 15.8
Water 336.8 464.6 464.6 464.6 464.6 466.3
Ethanol 701.1 1028.9 1028.9 1028.9 1028.9 403.3
Ethyl Acetate -- 0.4 0.4 0.4 0.4 21.7
Hydrogen -- -- -- -- -- 610.4

Stream 7 8 9 10 11 12
Temp. (°F) 387.9 157.0 107.3 152.3 152.6 152.2
Press. (psia) 96.1 95.1 94.3 94.3 94.3 94.3
Vapor Fraction 1.0 0.4 1.0 0.0 1.0 0.0
Total Flow (lbmol/h) 2076.0 2076.0 683.6 3600.1 638.1 3645.7
Component Flows (lbmol/h)
Acetaldehyde 546.6 546.6 63.4 -- 0.9 62.5
Acetic Acid 11.8 11.8 -- -- -- --
Butanol 15.8 15.8 -- -- -- --
Water 466.3 466.3 5.7 3600.1 26.9 3578.9
Ethanol 403.3 403.3 3.2 -- -- 3.2
Ethyl Acetate 21.7 21.7 0.9 -- 0.2 0.7
Hydrogen 610.4 610.4 610.4 -- 610.4 0.2
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Stream 13 14 15 16 17 18
Temp. (°F) 107.3 209.0 173.8 190.1 184.5 259.9
Press. (psia) 94.3 94.3 94.3 94.3 94.3 94.3
Vapor Fraction 0.0 0.0 0.0 0.0 0.0 0.0
Total Flow (lbmol/h) 1392.4 1392.4 5037.7 603.5 539.0 64.6
Component Flows (lbmol/h)
Acetaldehyde 483.2 483.2 545.7 543.2 537.7 5.4
Acetic Acid 11.7 11.7 11.8 -- -- --
Butanol 15.8 15.8 15.8 0.1 -- 0.1
Water 460.6 460.6 4039.5 55.6 1.2 54.4
Ethanol 400.1 400.1 403.3 2.5 -- 2.4
Ethyl Acetate 20.8 20.8 21.5 2.2 -- 2.1
Hydrogen -- -- -- -- -- --

Stream 19 20 21 22 23
Temp. (°F) 293.4 267.2 297.4 315.1 274.9
Press. (psia) 94.3 94.3 94.3 94.3 94.3
Vapor Fraction 0.0 0.0 0.0 0.0 0.0
Total Flow (lbmol/h) 4435.1 54.3 4380.7 3920.0 460.7
Component Flows (lbmol/h)
Acetaldehyde 2.4 -- 2.4 -- 2.4
Acetic Acid 11.7 -- 11.7 11.7 --
Butanol 15.8 -- 15.8 13.4 2.4
Water 3985.0 11.3 3973.7 3845.8 127.9
Ethanol 400.9 24.1 376.8 49.0 327.8
Ethyl Acetate 19.4 19.0 0.4 -- 0.4
Hydrogen -- -- -- -- --