oxygenated solvent) with the formula CH3COOC2H5 and having a molecular weight of 88.10. This colorless liquid has a characteristic, pungent smell like certain glues or nail polish removers, in which it is used. Ethyl acetate is the ester from ethanol and acetic acid; it is manufactured on a large scale for use as a solvent. Ethyl acetate is a moderately polar solvent that has the advantages of being volatile, relatively non-toxic, and non-hygroscopic. It is a weak hydrogen bond acceptor, and not a donor due to the lack of an acidic proton. Ethyl acetate can dissolve up to 3% water and has a solubility of 8% in water at room temperature. It is unstable in the presence of strong aqueous bases and acids. It is soluble in most organic solvents, such as alcohol, acetone, ether and chloroform. It has been also used as solvent in many chemical processes for replacing aromatic compounds which generated serious damage to the environment and human beings (1). References:
1. F. M. Kerton, Alternative Solvents in Organic
Chemistry, Cambridge: The Royal Society of Chemistry, 2009. 1.3 Chemical Properties/Reactions: There are two chemical reactions of ethyl acetate (4, 5):
1.3.1 Hydrolysis Ethyl acetate and other esters can be hydrolyzed to the corresponding carboxylic acid and ethanol. In the case of ethyl acetate, the reaction is prepared using acids or bases as catalysts and the products: acetic acid and ethanol are produced after a twostep mechanism.
𝐶𝐻3𝐶𝑂𝑂𝐶2𝐻5 + 𝐻2𝑂 ⇄ 𝐶2𝐻5𝑂𝐻 + 𝐶𝐻3𝐶𝑂𝑂𝐻 (1.1)
1.3.2 Transesterification Another important ethyl acetate reaction is the transesterification, where the methoxy group from the ester can be substituted by R- group from an alcohol.
(1.2) References: 4. https://www.softschools.com/formulas/chemistry/e thyl_acetate_formula/416/ 5. https://www.solventis.net/products/esters/ethyl- acetate/ 1.5 Production of Ethyl Acetate: The production of ethyl acetate in industries is mainly classified into three categories. First, the classical Fischer esterification process (see eqn. 1.3) of ethanol with acetic acid. This process includes the usage of acid (6) catalysts such as sulfuric acid and p-toluene sulfonic acid (7, 8).
𝐶2𝐻5𝑂𝐻 + 𝐶𝐻3𝐶𝑂𝑂𝐻⇄𝐶𝐻3𝐶𝑂𝑂𝐶2𝐻5+𝐻2𝑂 (1.3)
This reaction converts ethyl acetate in about 65%
(9) yield at room temperature . In the United States, this method is used commercially to produce more than 100 million pounds of ethyl acetate annually, mainly for use as a solvent in the paint industry, but also as a solvent for nail polish and various glues (10).
Second, by Tishchenko reaction of acetaldehyde
(see eqn. 1.4). This makes use of aluminum tetroxide as a catalyst.
2𝐶𝐻3𝐶𝐻𝑂→𝐶𝐻3𝐶𝑂𝑂𝐶2𝐻5 (1.4)
The exothermic conversion of acetaldehyde
takes place at 0 – 5 ⁰C (with cooling) in this solution. This reaction gives the selectivity roughly 96% at conversion 95% (based on acetaldehyde) (6) .
Third process is the one which has just been
recently commercialized, is addition of acetic acid to ethylene using clay and heteropoly acid as the catalyst of the reaction (see eqn. 1.5).
𝐶𝐻2=𝐶𝐻2+𝐶𝐻3𝐶𝑂𝑂𝐻→𝐶𝐻3𝐶𝑂𝑂𝐶2𝐻5 (1.5)
This new reaction has considerable benefits over
conventional technologies since it eliminates the intermediate step for the production of ethanol and also avoids environmental hazards related with other processes by using supported heteropoly acid on silica (11) .
These three processes of ethyl acetate synthesis are
explained via the following figure (12):
Figure 1.1: Ethyl Acetate Synthesis Processes
1.5.1 Fischer Esterification Process: It is a process of producing ethyl acetate and it is an equilibrium reaction occurring between acetic acid and ethanol. There are two methods of this process:
1- Conventional Method:
In using conventional method of Fischer esterification
process for producing ethyl acetate, one of the key issues that should be addressed is low reaction conversion. As a result of this low conversion, heavy capital investments and high energy costs are inevitable in this process, especially, based on the experience. The equilibrium reactor has two products streams both of which were distilled. The streams gave the following results. The output vapor steam had 95% Ethyl Acetate and Ethanol 3.8% with minute quantities of water and acetic acid. The residue containing ethanol, acetic (13) acid and water was recycled . This method is operated either batch or continuous. See the following figures (1.1 and 1.2) (14): Figure 1.1: Batch Conventional Method of Ethyl Acetate Production Process Figure 1.2: Continuous Conventional Method of Ethyl Acetate Production Process 2- Reactive Distillation (RD) Method: Reactive distillation, combination of chemical reaction and multicomponent distillation in a single unit, has proven to be advantageous over conventional process systems consisting of separate reactor and distillation unit. Commercial applications of Reactive Distillation include following (15): • The esterification of acetic acid with ethanol to produce Ethyl acetate and water. • The reaction of formaldehyde and methanol to produce methylal and water, using a solid acid catalyst. • The esterification of acetic acid with methanol to produce methyl acetate and water, using sulfuric acid as catalyst. • The reaction of isobutene with methanol to produce methyl-tert-butyl ether (MTBE), using a solid, strong–acid ion-exchange resin catalyst. There are many documented success stories involving the industrial implementation of reactive distillation. The applications of reactive distillation in the chemical and petroleum industries have increased rapidly in the past decade. One such example is the manufacturing of methyl acetate by the Eastman Chemical Company. In this case a single reactive distillation column replaced the traditional flow sheet consisting of eleven major unit operations along with an assortment of heat exchangers, pumps and controllers. The result was a five- fold reduction in capital investment and energy consumption over the conventional design for methyl acetate production. The advantages of Reactive Distillation can be summarized as below (16): • Increased speed and improved efficiency. • Lower costs – reduced equipment use, energy use and handling. • Less waste and fewer byproducts • Improved product quality–reducing opportunity for degradation because of less heat; • heat duty can be reduced by utilizing the heat of reaction (if present) in situ. • Recycle costs for excess reactant, which is necessary for a conventional reactor to prevent • side reactions and chemical equilibrium limitation, can be reduced. • Reaction conversions can be increased by overcoming chemical equilibrium limitation • through the removal of reaction products. • Limitation of azeotropic mixture can be overcome by reaction. In spite of above stated benefits of reactive distillation, cannot be used for every process that requires reaction and separation in a single unit. It has some constraints. In general, reactive distillation is not attractive for supercritical condition, for gas-phase reaction, and for reaction that must take place at high temperature and pressures, and/or that involves solid reactants or products (16). In the production of ethyl acetate using reactive distillation system (see figure 1.3), the main problems encountered in achieving high purity products are summarized subsequently (16):
•Unfavorable reactant conversion;
• Similar K-values of ethanol, water, and ethyl acetate; •Temperature profile in the column; • The system is strongly non-ideal Figure (1.3): Ethyl Acetate Reactive Distillation Process
Where: F0 represents the heavy reactant (Acetic Acid)
F1 represents the light reactant (Ethanol) 1.5 References:
Profile," Chemical Weekly, pp. 179-186, 10 August 2004.
8. R. K. G. V. K. Damandeep Singh, "Simulation of
a Plant Scale Reactive Distillation Column for Esterification of Acetic Acid," Computers and Chemical Engineering, no. 73, pp. 70-81, 2015.
9. H. C. M. Bijay N. Pattanik, "Ethyl Acetate:
Properties, Production Processes and Applications- A Review," International Journal of Current Research and Review Vol. 3, pp. 23-40, 2011.
10. C. M. H. L. E. C. H. H. David J. Hart, Organic
Chemistry: A Short Course, 13th Edition, Belmont: Brooks Cole, 2012.
11. J. R. Sowa, Catalysis of Organic Reactions,
Boca Raton: Taylor & Francis Group, 2005.
12. M. Ashley, Renewable Processing: The Green
Alternative, INGENIA ISSUE 29 DECEMBER 2006, pp. 46-50.
13. B. N. Pattanaik and H. C. Mandalia, ETHYL
ACETATE: PROPERTIES, PRODUCTION PROCESSES AND APPLICATIONS - A REVIEW, International Journal of Current Research and Review Vol. 03 issue 12 December 2011, pp. 23-40.
14. Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 9, pp. 374-400.
15. Seader J.D. and Henley E. J (2006). Separation
process principle, Wiley John Wiley & Sons, Inc.
16. Terril, D.L., L.F. Sylvestre, and M.F. Doherty,
