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Production of butyl acetate by Reactive distillation.

Manufacture and synthesis of n-butyl acetate is commonly done by esterification of n-butanol with
acetic acid via reactive distillation method and in presence of an acid catalyst. Concentrated
sulfuric acid in some cases is used as a homogenous catalyst. However, the use of sulfuric acid as
a catalyst presents challenges such as corrosion and difficulty in separation and recycling the
catalyst. Hence application of heterogonous catalysts such as strong acid ion-exchange resins in
the esterification reaction of n-butanol with acetic acid is seen as a better alternative. Examples of
heterogeneous catalysts that have employed in the synthesis of n-butyl acetate include:
commercial resins like Amberlyst-15 and Dowex 50; zeolites and supported metal oxides like
VO2O5, WO3 and MoO3. Also there cases where biocatalysts have been applied in the preparation
of n-butyl actetate, for instance Adrea et. al. [5] reported reaction conversion as high as 90% while
using Candida antarctica lipase B (Novozym 435) as a catalyst.

The development of a heterogeneously catalyzed reactive distillation process for the production of nbutyl acetate by the esterification of n-butanol with acetic acid is presented. Thermodynamic aspects of
the considered system are discussed, and UNIQUAC interaction parameters are given. The reaction
was catalyzed heterogeneously by a strongly acidic ion-exchange resin (Amberlyst-15). The reaction
kinetics was investigated, and the kinetic constants for a pseudohomogeneous kinetic model are
presented. Reactive distillation experiments were performed using the structured catalytic packing
Katapak-S. Several operation conditions were varied (reboiler duty, reactant ratio, total feed rate), and
two different setups were realized experimentally. The experimental results are presented in comparison
with simulation results. An equilibrium stage model is capable of describing the experiments
quantitatively. n-Butanol conversions of 98.5% accompanied with n-butyl acetate purities of 96.9% were
achieved using an equimolar total column feed. The simulation was used subsequently to determine the
influence of important design factors such as feed location, use of a prereactor, and numbers of reactive
and nonreactive stages, resulting in an optimized process. [1]

This paper studies reactive distillation for the synthesis of n-butyl acetate from n-butanol esterification with
acetic acid over Amberlyst -15. This study is carried out to influence the unwanted side product dibutylether
formation, produced by butanol dehydration. First of all, activity based intrinsic reaction kinetics for the main
reaction (esterification) and the side reaction (etherification) have been developed. Effect of various parameters
such as temperature, mole ratio, catalyst loading and catalyst particle size was studied. The intrinsic kinetic
parameters related to Pseudohomogeneous (PH), Eley-Rideal (RE), Langmuir Hinshelwood Hougen Watson
(LHHW), and modified LHHW (ML) models were developed. Good agreement between the model predictions and
experimental data were obtained. For the main reaction RE model or modified LHHW model and for the side
reaction LHHW model are appropriate representations of intrinsic kinetics. The developed rate expression were
then used for the simulation based design of reactive distillation column for the production of butyl acetate with
the goal of eliminating the side product formation and achieving high purity of desired product butyl acetate. A
simple equilibrium stage, steadystate reactive distillation column model was developed and validated using

expeimental data from the literature. The following column configurations are invesigated: (a) column with non . [2] In this paper. The effects of operating variables on the n-butanol conversion and n-butyl acetate purity were further investigated. and (c) conventional distillation column with pump around reactor. non . For each configuration. n-butanol conversion and n-butyl acetate purity all reached greater than 96% [3] . a reactive distillation (RD) column was applied for synthesis n-butyl acetate from nbutanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model for separation were employed to study the RD process. effect of design parameters such as.reactive rectifying section and reactive stripping section (b) column with non . catalyst loading. 8 reaction stages and 13 stripping stages by the simulation study. reboiler heat duty.reactive rectifying section. catalyst section length and location. According to the simulation results. and feed stage location were investigated with the objective to achieve desired goal.reactive stripping section and reactive middle section. The optimal column configuration for the production of n-butyl acetate was designed with 5 rectifying stages. The results obtained from the equilibrium stage model agreed well with the experiments.

com/article/10. Rafael C. Stein. Ghamghui H.net/Hugovic9/kinetic-study-of-esterification-of-acetic-acid-with-nbutanol-and-isobutanol-catalyzed-by-ion-exchange-resin http://www.slideshare.980-987 4. pp. J. Graebin.researchgate.K & Bager. Reaction Kinetics.sciencedirect.com/science/article/pii/S1381116914004580 http://www. S. pp. Mejdoub H. Eng. Marco A. (2003).ddbst.com/science/article/pii/S1631074812001373 http://www. pp. E. . Gangadwala. Journal .. Production of butyl acetate by catalytic distillation: reaction kinetics and process design studies.com/en/EED/VLE/VLE%201-Butanol%3BAcetic%20acid%20butyl %20ester%3BAcetic%20acid%3BWater. Rodrigues (2011) Rapid and high yields of synthesis of butyl acetate catalyzed by Novozym 435:Reaction optimization by response surface methodology.2060-2072 5.A. Gargouri Y. 2311-2316 http://www. Lorenzoni..php J Biosci Bioeng.29(10). & Tech.S. Pilot-Plant Experiments. In ISMR3 .sciencedirect. Ind.CCRE18: joint research symposium of the 3rd International Symposium on Multifunctional Reactors and the 18th Colloquia on Chemical Reaction Engineering (pp. Zhixian Huang. 2007 Apr. Andréa B. Production of butyl acetate ester by lipase from novel strain of Rhizopus oryzae. Res.1023%2FA%3A1013227131728 http://www. Eng. Yanxiang Wu (2011) Reactive Distillation for producing n-butyl Acetate: Experiment and simulation. Shakoor. Ayub. Martins. Hui Tian. Chinese Journal of Chemical Engineering. Process Biochemistry 46. André S. & Mahajani.1. Ting Qui. Sven Steinigeweg and jürgen Gmehling (2002) n-Butyl Acetate Synthesis via Reactive Distillation: Thermodynamic Aspects. Miled N. Chem.. Kienle. 3.G.. A. pp 5483–5490 2. Sukkar. MZ. and Simulation Studies.springer.41 (22). Roberto FernandezLafuente.103(4):368-72. 20(5).Z.M (2011) Reaction Kinetics of Acetic Acid and n-Butanol Esterification Catalyzed by Dowex 50 Catalyst. Natália G. Ben Salah R1.. 191-194).net/publication/244494778_Esterification_of_Acetic_Acid_with _n_Butanol_Using_Molybdenum_Oxides_Supported_on_-Alumina http://link. Xiaoda Wang.

In this paper is described the optimization of the esterification reaction of butyl acetate synthesis catalyzed . Vol. the synthesis activity was improved in the presence of heptane and hexane with conversion yields of 80% and 76%. However. This flavor compound can be used in food. vapor pressures and UNIQUAC interaction parameters were investigated. A maximum conversion yield of 60% in a solvent-free system was obtained under the following conditions: amount of immobilized lipase. acetic acid/butanol molar ratio. PUB.Jun2011. and in incubation temperature. 500 IU. In contrast. 25 Issue 2. a 2 m column with nonreactive and reactive zones filled with Amberlyst 15 and Raschig rings. For this purpose. The thermodynamic aspects of considered system are discussed. Reaction experiments were carried out in a stirred batch reactor at temperature range of 343 to 363 K. equilibrium constant. Atalay. Compared with a solvent-free system. oryzae lipase was also studied in the presence of organic solvents. 1:1. under various catalyst loads and various starting reactants feed ratios. DATE June 2011 SOURCE Chemical & Biochemical Engineering Quarterly.. E. respectively within the range of study. Only 3% of butyl acetate was obtained when free lipase was used in the synthesis containing only the substrates. amount of catalyst and reboiler temperature and three different column configurations were realized experimentally.Author information Abstract A new lipase preparation from Rhizopus oryzae was used to catalyze the esterification reaction between acetic acid and butanol to produce butyl acetate ester (pineapple flavor). Several operating conditions such as total feed flow rate. molar ratio of butanol to acetic acid. The production of butyl acetate esters by immobilized R. amount of initially added water. Reactive distillation experiments were carried out to provide high purity butyl acetate.5 % were obtained at the optimum operating conditions The reaction kinetics of the n-butanol esterification and acetic acid on acidic solid catalyst named Dowex 50 under atmospheric pressure was investagated in this work. S. respectively. 45%. p221 SOURCE TYPE Academic Journal DOC. F. The butyl acetate purity of 82 % and acetic acid conversion of 80. cosmetic and pharmaceutical industries. Immobilized lipase could be repeatedly used for three cycles without a decrease in synthesis activity. 25 g and 383 K. 1. 37 degrees C. solventfree systems tend to purify more easily the products without any toxicity and inflammability problems Esterification of Acetic Acid with Butanol: Operation in a Packed Bed Reactive Distillation Column AUTHOR(S) Sert. were used in the experiments. The experimental optimum values of these parameters obtained were 1. the conversion yield reached 25% when immobilized lipase was used under the same conditions. TYPE Article ABSTRACT The esterification reaction between acetic acid and butanol was investigated in a reactive distillation column. The synthesis of butyl acetate catalyzed by immobilized lipase in nonconventional media was optimized.6 mol h–1.

Direct enzyme reuse or washing with water produced a rapid decrease on enzyme activity. This fast and high yield of conversion represents a large improvement to previously reported results.5 h. or suspending the immobilized enzyme in water for 24 h. The best acid concentration for the reaction without enzyme inactivation was determined to be 0.25% of substrate wt. . were evaluated using central composite design and response surface methodology. over 90% of conversion was obtained in 2. substrate molar ratio of 3:1 butanol:acetic acid. Under these conditions.by Candida antarctica lipase B (Novozym 435). and added water. enzyme content. The reaction parameters temperature. enzyme content of 7. and their responses measured as conversion yields. Enzyme reuse was tested performing three different treatments before each batch: washing the enzyme system with either n-hexane or water.. added water 0. substrate molar ratio. while washing with n-hexane allowed enzyme to be reused for 6 reactions cycles keeping around 70% of its activity. The optimal conditions for butyl acetate synthesis were found to be temperature of 40 ◦C.5% of substrate wt.3 M.