Acetic Acid Separation Methods

Supervisore: Prof. H. S. Ghaziaskar

By: H. Rastegari
 Contents
Acetic Acid Uses

Acetic Acid Production

Acetic Acid Separation methods

Conclusion

References

1
Acetic Acid Uses
In vinyl acetate monomer production
In acetic anhydride production
As solvent in production of terphetalic acid
As recrystalization solvent
In Silage
In production of various acetates such as:

Sodium acetate
Copper acetate
Aluminum acetate
Palladium acetate

2
Acetic Acid Production

Chemical processes for acetic acid production:

Reaction of methanol with carbon monoxide

Reaction of acetylene with water followed by air oxidation
Fermentation of ethanol
Butane oxidation

3
Other chemical processes which produce acetic acid
as a by-product:

Manufacture of cellulose esters

Reactions involving acetic anhydride

Synthesis of glyoxal from acetaldehyde and nitric acid

Wood distillate

4
Problem

Separating acetic acid from water

5
Separation Methods
Separation Involving Phase Changes:

Simple Distillation
Azeotropic Distillation
Extractive Distillation
Reactive Distillation

Separation involving membranes:

Pervaporation
Evapomeation
Temperature Difference Evapomeation
Electrodialysis
Bipolar Membrane Electrodialysis
6
Simple Distillation
Physical separation process based on differences in volatilities

7
Disadvantage
Advantage
Large energy consumption
Simple and easy to operate

8
 Azeotropic Distillation

Distillation in the presence of entrainer

9
Desirable properties for an azeotropic entrainer :
Heterogeneous azeotrope

Commercially available and inexpensive

Nontoxic

Chemically Stable

Noncorrosive

Low heat of vaporization

The best entrainer is:

Alkyl Acetate

10
Effective parameters for alkyl acetate selection

Azeotropic temperature
Azeotropic composition
Aqueous phase composition and entrainer pricing

11
Advantage

Improving the economics of the separation

Disadvantage

Requiring large amount of entrainer

12
Extractive Distillation

Distillation in the presence of solvent

13
 Desirable properties for solvent:
 Nonvolatile

 High boiling point

 Make large difference in volatility between components

 Miscible with mixture and doesn´t form azeotropic

mixture
 Commercially available and inexpensive

 Noncorrosive

 Physically and chemically stable

14
 The best solvent is:

Trialkyl Amine

Advantage
Relatively little energy consumption

Disadvantage
Need additional heat requirement on the column
Some what larger plates

15
 Reactive Distillation
 Chemical separation method which combines simultaneous
chemical reaction and multicomponent distillation in the same
vessel

16
Mechanism of reaction:
First Step:

Second Step:

Third Step:

17
 Effect of various parameters on the acid conversion
Total feed flow rate
Optimum value:192 mL/h
Mole ratio

18
Feed
Reflux configuration
position

19
 Pervaporation (PV)
separation of liquid mixtures by partial vaporization through
membrane

20
Used membrane
Polydimethylsiloxane (PDMS)

Cross-linked polybutadiene

Silicalite-1 as adsorbent filler in PDMS membrane

Carbon molecular sieve in PDMS membrane

Silicalite-1(pure silica)

Ge-ZSM-5

Sn-ZSM-5

20
Effective parameters on separation performance
Si/Sn

Temperature

Acid concentration

Disadvantage

Shrinking and swelling of the membrane

21
Evapomeation(EV)

Vaporization of feed solution then permeation through

polymeric membrane

22
Effective parameters on separation performance
Temperature

Acid concentration

Disadvantage
membrane condensation in high acid concentration

23
Temperature Difference Evapomeation (TDEV)
Decreasing temperature in the membrane surrounding than
in the feed solution

24
Electrodialysis (ED)
Ion transportation from one solution through ion- exchange
membranes to another solution under the influence of an
electric potential difference

25
Application
Concentrating acetic acid from water containing %1(w/w)
acid to %10(w/w)

26
Importance
Make full use of our limited resources
Protect our environment

Disadvantage
Concentration efficiency up to %10
Low electric current efficiency (around %20)

27
Bipolar Membrane Electrodialysis (BME)

28
Application
Concentrating acetic acid from water containing %0.2(w/w)
acid to %14(w/w)

Disadvantage
Low electric current efficiency (around %40)

29
Conclusion
For high purity (%99.9) acetic acid Azeotropic Distillation
For reasonably pure acetic acid Extractive Distillation
For ester production Reactive Distillation
For separation from solution containing % (5-15) acid PV

30
 References
[1] Garwin, L., Hutchisoni, K., E., 1950. Industrial And Engineering
Chemistry 42(4), 727-730.
[2] Othmer, D., F., 1935. Industrial And Engineering Chemistry 27(3),
250-255.
[3] Lee, F., M., Wytcherley, R., W., Distillation, Academic Press, USA,
2000.
[4] Chien, I., L., Kuo, C., L., 2006. Chemical Engineering Science 61,
569-585.
[5] Wang, S., J., Lee, C., J., Jang, S., S., Shieh, S., S., 2008. Process
Control 18, 45-60.
[6] Garwin, L., Haddad, P., O., 1953. Industrial And Engineering Chemistry
45(7), 1558-1562.
[7] Lei, Z., Li, C., Li, Y., Chen, B., 2004. Separation And Purification
Technology 36, 131-138.
[8] Taylor, R., Krishna, R., 2000. Chemical Engineering Science 55, 5183-
5229.
[9] Saha, B., Chopade, S., P., Mahajani, S., M., 2000. Catalysis Today 60,
147-157.
[10] Yu, L., Guo, Q., Hao, J., Jiang, W., 2000. Desalination 129, 283-288.
[11] Sun, W., Wang, X., Yang, J., Lu, J., Han, H., Zhang, Y., Wang, J.,
2009. Membrane Science 335, 83-88.
[12] Li, G., Kikuchi, E., Matsukata, M., 2003. Separation Purification
Technology 32, 199-206.
[13] Toti, U., S., Kariduraganavar, M., Y., Soppimath, K., S., Aminabhavi,
T., M., 2002. Applied Polymer Science 83, 259-272.
[14] Asman, G., Anl, O., 2006. Separation Science And Technology 41(6)
1193-1209.
[15] Asman, G., Sanli, O., 2006. Applied Polymer Science 100, 1385-1394.

[16] Chien, I., L., Zeng, K., L., Chao, H., Y., Liu, J., H., 2004.Chemical

Engineering Science 59, 4547-4567.

[17] Kittur, A., A., Tambe, S., M., Kulkarni, S., S., Kariduraganavar, M.,

Y., 2004. Applied Polymer Science 94, 2101-2109.

Thanks for your attention
Acetic Acid Production

Glyoxal:
Simple Distillation
VHAC= (yHAC) / (xHAC)

VH2O= (yH2O) / (xH2O)

Dalton's Law:

PH2O= (yH2O) * pt

Raoult's law:

PH2O= (xH2O) * p0H2O

α = VH2O / VHAC

Fenske Equation:
(yH2O)/(1- yH2O) = αn+1 (xH2O)/(1- xH2O)
Azeotropic Distillation
Extractive Distillation
Solvent volume