ISSN NO. 2230-7850.

Research Paper - Chemistry

Vol.I, Issue VI / Jul 11 pp227....

Ethyl acetate synthesis by esterification of acetic acid with ethanol over a heteropolyacid on montmorillonite K10
Bhimashankar R. Pirgonde 1 , Hanumant Gurav2, Vijay V. Bokade* 3, 1) Dept. of chemistry , Sangameshwar College , Solapur,
*Corresponding author

Email : pirgonde@yahoo.com

2,3) Catalysis Division, National Chemical Laboratory, Pune-411008 India Email: vv.bokade@ncl.res.in Tel: 91-20-2590-2458 , Fax: 91-20-2590-2634 Abstract
Ethyl acetate is an industrially important product in the manufacture of paint, varnish, confectionary, perfumes, fruits, wine and asphyxiant. In present work, liquid phase esterification of acetic acid with ethanol over dodecatungestophosphoric acid supported on K10 montmorillonite was systematically studied and optimization of process parameters was carried out. The 20% m/m DTPA/K10 was found to be the optimum catalyst with 90% acetic acid conversion and 100% ethyl acetate selectivity. The results are novel. Keywords: Acetic acid, Ethanol, Heteropolyacid, Montmorillonite K10, Ethyl acetate.

1. Introduction Esterification of carboxylic acids with alcohols in the presence of acid catalysts has been the subject of investigation by many research workers. Both homogeneous and heterogeneous catalysts have been used for this purpose. A number of techniques, including microwave applications, have been developed for the esterification process 12-14. Most of the reported procedures for the synthesis of esters require the use of mineral acids, which are environmentally hazardous and unacceptable. Considering the impact of these chemicals on the environment there is an urgent need to develop a more ecofriendly method for the production of esters. The use of zeolites as solid catalysts in organic transformations in place of conventional catalysts is on the increase 8-11. Protonated forms of zeolites have been found to be efficient catalysts in esterification reactions 7. Esters obtained from small chain acid and alcohols are very important industrially. The esterification reactions to obtain these esters are Indian Streams Research Journal

usually catalyzed by sulphuric or p-toluenesulphonic acid. Although these acids are very active, major problems are related to environmental concerns, besides the corrosive nature and difficulties to separate them from reaction mixture 1-5. The use of solid acids has gained attention. Examples of solid acids catalysts for esterification reactions include: ion exchange resins (eg. amberlyst 15, smopex-101), zeolites (eg. Y, USY, BEA, MOR, ZSM-5), sulphated oxides (eg. SO4/ZrO2), niobic acid and supported heteropolyacids (eg. H4SiW12O40/ ZrO2) (Bhatt, 2005; Jermy, 2005). Even though the esterification reaction looks simple, it is an equilibrium process (with low equilibrium constant), and in order to get improved yields much engineering should be done 9-10. The esterification of carboxylic acids by alcohols is catalyzed by strong acids. Their role is to protonate the carbonyl group, which makes it far more electrophilic and reactive towards the alcohol As a result, the esterification of carboxylic acids became a convenient model reaction for evaluating the activity of solid acids 6. (Reaction Scheme). 227

Ethyl acetate synthesis by esterification.....

O HC 3 O H
+ H

Vol.I, Issue VI / Jul 11 pp227.... The crystallinity and the phase purity of ynthesized samples were determined by powder X-ray diffraction (XRD) (Rigaku Miniflex, Japan, Cu-Ka)
+ O

O H 3C O 2H C 5

+ C2H5OH
E thanol

-HO 2
+ -H

A cetic A cid
+ H

E A thyl cetate

O H
+ O -H H O HC 3 O H

Fig.

H 3C

+ O

H 3C -H 2O

O H H

The aim of this work was to develop the new catalyst and process parameters for the synthesis of ethyl acetate by esterification of acetic acid with ethanol. The heteropolyacid supported on clay as a potential catalyst for the selective formation of ethyl acetate is presented. The different effect of process parameters is also studied and discussed in this work. The study was further extended to see the feasibility of heteropolyacid supported on clay as a catalyst for other alcohols like methanol, isopropanol and n-butanol. 2. Experimental 2.1 Chemicals Dodecatungstophosphoric acid

I N T E N S I T y (a . u .)
0 2 0 4 0 6 0

S H/ 1 T K/ 0

DP / 1 TA 0 K

D A/1 M A /0 K

K1 0

8 0

2 (d g e e re )

2.3.2 Nitrogen adsorption The specific surface area was obtained from nitrogen adsorption - desorption isotherms at 77K measured in an SA 3100, USA analyzer. The surface area was calculated by the BET method Table 1.
Table 1: - Nitrogen A dsorption by BET method. No. 1 2 3 4 Catalyst K10 20% m/m DTPA/K10 20% m/m DMAA/K10 20% m/m STH/K10 BET Surface 2 Area (m /g) 223 135 141 104

[H3PO4.12WO3.xH2O] (DTPA), dodeca- molybdo phosphoric acid ammonium salt hydrate [H12Mo12N3O40P+aq] (DMAA), sodium tungstate hydrated purified [Na12WO4. 2H2O] (STH), Clay (Montmorillonite, K-10), Acetic acid (99%) and alcohols (99%) were obtained from M/s S.D. Fine Chemicals, Mumbai. All reagents are of analytical grade and used without further purification. 2.2 Catalyst Preparation DTPA/montmorillonite was prepared by impregnation. An amount of 2 g DTPA was dissolved in methanol and was added slowly to 20 g K10 with stirring. The paste was dried on a water bath, then at 90oC to remove methanol completely. Prior to use, the sample was dried at 100oC to remove moisture. The composition of the catalysts was 1030% m/m DTPA/K10. 2.3 Catalyst characterization 2.3.1 Powder X-ray diffraction Indian Streams Research Journal

2.4 Reaction Procedure The esterification reaction of acetic acid with each alcohol was carried out in a stirred batch reflux system. A 50ml glass round bottom flask was charged with acetic acid and the respective alcohol, both weighted sequentially, followed by the addition of the preactivated catalyst (10% m/m of acetic acid). The reagent amounts were calculated according to

228

Ethyl acetate synthesis by esterification.....

Vol.I, Issue VI / Jul 11 pp227....

the desired molar ratio for each reaction (2:1 acid: Table 2 Catalyst Selection alcohol). Then, the system was heated up to the reaction temperature, the reaction was carried out for 8h and finally the product was collected after removing the catalyst. The product was analyzed by gas chromatography. 2.5 Analysis The liquid reaction products were analyzed by using Gas Chromatography (GC -1000) (packed column, liquid phase 5% SE-30, solid support CHW-HP, 1/8 diameter x 8 length) with nitrogen as a carrier gas and programmable temperature range of 40 to 200oC. The reaction products were also studied by GC-MS (Shimadzu-QP5000).
Catalyst Thermal K 10 20 % m/m DMAA/K10 82.8 100 20% m/m STH/K10 76.8 100 20% m/m DTPA/K10 89.8 100

% Conv. Acetic acid % Sel. Ethyl acetate

40 100

63.9 100

Reaction Conditions: - Catalyst loading: 10 %m/m of acetic acid, Reaction temperature: 1000C, Mole Ratio (acetic acid: ethanol): 2:1, Conv.: Conversion, Sel.: Selectivity Reaction time: 8h

3.2 Effect of reaction temperature Increasing the reaction temperature from 80 to 100oC increases the acetic acid conversion from 62.12% to 89.8% with 100% ethyl acetate selectivity (Table 3). Above 100oC, identical acetic acid conversion was observed.

3. Result and Discussion 3.1 Catalyst selection The montmorillonite K10 Table 3: Effect of reaction temperature and different heteropolyacid (HPA) on K10 were screened for the acetic acid ethylation at identical process parameters: 100oC, Mole ratio (acetic acid: ethanol) 2:1 and catalyst loading of 10% m/m with respect to acetic acid. Each reaction was conducted for the reaction period of 8h and data is included in the Table 2. Usually, the yield of the ester can be
Reaction temperature(0C)

80

90

100

110 89.5 100

% Conv.Acetic 62.1 Acid

% Sel.Ethyl acetate

76.0 89.8 100

100 100

increased by additional use of either alcohol or acid. of acetic acid, Catalyst: 20% m/m DTPA/K10, Mole As the acetic acid is less expensive reagent, it was Ratio (acetic acid: ethanol):2:1,Conv.: Conversion,

Reaction Conditions: - Catalyst loading: 10 %m/m

used in excess in this study. The Table 3 reveals that Sel.: Selectivity. Reaction time: 8h. all the HPA loaded samples has shown better activity compared to montmorillonite K10. Amongst studied 3.3 Effect of molar ratio of acetic acid: ethanol samples, 20% m/m DTPA/K10 was observed to The experimental results tempted to further explore be the best sample with 89.8% acetic acid conversion and 100% selectivity of ethyl acetate. the efficacy of the 20%m/m DTPA/K10 catalyst for The montmorillonite K10 has shown 63.9% acetic this reaction by increasing the acetic acid concentration acid conversion as against thermal reaction (40%). in the feed. The acetic acid mole was increased as The increased in acetic acid conversion with HPA loaded K10 samples may be due to increase in 0.0333, 0.0666 and 0.1000. The results are depicted acidity and surface area of HPA loaded K10 samples. 20% m/m DTPA/K10, the optimum catalyst sample was used for the further investigation. as Table 4. The acetic acid conversion was found to be identical at 89%. The ethyl acetate selectivity was

Indian Streams Research Journal

229

Ethyl acetate synthesis by esterification..... observed to be 100% for all experiments. The 1:2 molar ratio of ethanol: acetic acid was observed to be optimum. Table 4 Catalyst Selection
Acetic acid: Ethanol % Conv. Acetic acid %Sel.Ethyl acetate

Vol.I, Issue VI / Jul 11 pp227.... 4. Conclusion The liquid phase esterification of acetic acid with ethanol to the synthesis of ethyl acetate over heteropolyacid supported on K10 was systematically studied. The 20% m/m DTPA/K10

2:01 89.8 100

4:01 89.4 100

6:01 90.5 100

was found to be the optimum catalyst with 89.8 % acetic acid conversion and 100% ethyl acetate selectivity. The study was further extended to explore the feasibility of 20%m/m DTPA/K10 as a catalyst

Reaction Conditions: - Catalyst loading: 10 %m/m of acetic acid, Catalyst: 20% m/m DTPA/K10, Reaction temperature: 100oC, Conv.: Conversion, Sel.: Selectivity. Reaction time: 8h.

for the esterification of acetic acid with other alcohols like methanol, iso-propanol and n-butanol. The 20%m/m DTPA/K10 has shown increased in activity

3.4 Effect of reaction time The experimental study was further extended to optimize the reaction time with 20% m/m DTPA/K10 catalyst. The results are presented as Table 5. The acetic acid conversion was observed to be increased from 73.3% (4h) to 89.8 % with increase in reaction time up to 8h. After reaction time of 8h, marginal increment in acetic acid conversion of 90.0% (10h) was observed. The reaction time of 8h was found to be optimum.

with increased in carbon number, at the optimized process parameters. The results are novel 5. References 1. Altiokka, M.R., Citak, A., 2003. Kinetic study of esterification of acetic acid withisobutanol in the presence of amberlite catalyst. Applied Catalysis A: General 239, 141-148. 2. Bhatt, N., Patel, A., 2005. Esterification of 1o and 2o alcohol using an ecofriendly solid

Table 5 Catalyst Selection

acid catalyst comprising 12-tungestosilicic

Reaction time (h) % Conv. Acetic acid %Sel.Ethyl acetate

4 73.3 100

6 82.8 100

8 89.8 100

10 90
3.

acid and hydrous zirconia. Journal of Molecular Catalysis A: Chemical 238, 223-228. Chen, X., Xu, Z., Okuhara, T., 1999. Liquid phase esterification of acrylic acid with 1butanol catalyzed by solid acid catalysts. Applied Catalysis A: General 180, 261-269. 4. Freese, U., Heinrich, F., Roessner, R., 1999. 230

100

Reaction Conditions: - Catalyst loading: 10 %m/m of acetic acid, Catalyst: 20% m/m DTPA/K10, Reaction temperature: 100oC, Molar ratio (acetic acid: ethanol): 2:1, Conv.: Conversion, Sel.: Selectivity.

Indian Streams Research Journal

Ethyl acetate synthesis by esterification..... Acylation of aromatic compounds on H-beta zeolites. Catalysis Today 49, 237-244. 5. Jermy, B.R., Pandurangan, A., 2005. Catalytic application of Al-MCM-41 in the esterification of acetic acid with various alcohols. Applied Catalysis A: General 288, 25-33. 6. Kovalchuk, T.V., Kochkin, J.N., Sfihi, H., Zaitsev, V.N., Fraissard, J., 2009. Oniumsilica-immobilized Keggin acids: Acidity and catalytic activity for ethyl tert-butyl ether synthesis and acetic acid esterification with ethanol. Journal of Catalysis (In Press). 7. Lasperas, M., Graffin, P., Geneste, P., 1993. One pot selective synthesis of ethyl esters from aromatic nitriles using acid faujasites as catalysts. Journal of Catalysis 139, 362-370. 8. Liu, W.T., Tan, C.S., 2001. Liquid phase esterification of propionic acid with n-butanol. Industrial Engineering Chemistry Research. 40, 3281-3286. 9. Ma, Y., Wang, Q.L., Yan, H., Ji, X., Qiu, Q., 1996. Zeolite catalyzed esterification I. Synthesis of acetates, benzoates and phthalates. Applied Catalysis A: General 139, 51-57. 10. Otera, J., 2004. Toward ideal (Trans) esterification by use of fluorous distannoxane catalysts. Account of Chemical Research 37, Indian Streams Research Journal 13.

Vol.I, Issue VI / Jul 11 pp227.... 288-296. 11. Pandey, A.K., Singh, A.P., 1997. A novel catalytic method for the acylation of aromatics to the corresponding ketones over zeolite catalysts. Catalysis Letter 44, 129133. 12. Peters, T. A., Benes, N.E., Holmen, A., Keurentjes, J.T.F., 2006. Comparison of commercial solid acid catalysts for the esterification of acetic acid with butanol. Applied Catalysis A: General 297, 182-188. Pipus, G., Plazi, I., Koloimi, T., 2000. Esterification of benzoic acid in microwave tubular flow reactor. Chemical Engineering Journal 76, 239-245. 14. Ramalinga, K., Vijayalakshmi, P., Kaimal, T.N.B., 2002. A mild and efficient method for esterification and transesterification catalyzed by iodine. Tetrahedran Letter 43, 879-882.

231