Pervaporation-assisted esterification of lactic and succinic acids with downstream ester recovery

Abstract Reactors coupled with membrane separation, such as pervaporation, can help enhance the conversion of reactants for thermodynamically or kinetically limited reactions via selective removal of one or more product species from the reaction mixture. Esterification of lactic acid (C 3 H 6 O 3 ) and succinic acid (C 4 H 6 O 4 ) with ethanol (C 2 H 5 OH) to generate ethyl lactate (C 5 H 10 O 3 ) and diethyl succinate (C 8 H 14 O 4 ), respectively, is studied in well-mixed reactors with solid catalysts (Amberlyst XN-1010 and Nafion NR50) and two pervaporation membranes (GFT-1005 and T1-b) in this article. The results of catalyst compatibility and membrane stability studies are discussed. Experiments with a closed-loop system of a “batch” catalytic reactor and a pervaporation unit employing GFT-1005 reveal that for esterification of both lactic and succinic acids, fractional conversions of the two reactants exceeding the corresponding maximum values in a reaction-only operation and close to unity are obtained by stripping water, a reaction product. The kinetics of pervaporation is studied to obtain a working correlation for the flux of water in terms of temperature and water concentration on the feed side of the pervaporator. The efficacy of pervaporation-aided esterification is illustrated by attainment of near total utilization of the stoichiometrically limiting reactant within a reasonable time. Protocols for recovery of ethyl lactate and diethyl succinate from pervaporation retentate are discussed and simultaneous esterification of lactic and succinic acids, which is an attractive and novel concept, is proposed.

[1]  J. Rhee,et al.  Removal of water produced from lipase-catalyzed esterification in organic solvent by pervaporation. , 1995, Biotechnology and bioengineering.

[2]  H. Kita,et al.  PERVAPORATION-AIDED ESTERIFICATION OF OLEIC ACID , 1993 .

[3]  Heikki Haario,et al.  Development of a kinetic model for the esterification of acetic acid with methanol in the presence of a homogeneous acid catalyst , 1997 .

[4]  Philip Herkimer Groggins,et al.  Unit Processes in Organic Synthesis , 1935, Nature.

[5]  J. Falconer,et al.  Separating organics from water by pervaporation with isomorphously-substituted MFI zeolite membranes , 2002 .

[6]  Ana M. Eliceche,et al.  Optimisation of azeotropic distillation columns combined with pervaporation membranes , 2002 .

[7]  Richard D. Noble,et al.  Membrane separations technology : principles and applications , 1995 .

[8]  V. Dubey,et al.  Pervaporative separation of ethanol/water azeotrope using a novel chitosan-impregnated bacterial cellulose membrane and chitosan–poly(vinyl alcohol) blends , 2005 .

[9]  R. Huang,et al.  Pervaporation membrane separation processes , 1991 .

[10]  Liu Xuehui,et al.  Kinetic model for an esterification process coupled by pervaporation , 2001 .

[11]  H. Schwarz,et al.  Polyelectrolyte membranes for aromatic–aliphatic hydrocarbon separation by pervaporation , 2005 .

[12]  Q. Liu,et al.  Modeling of esterification of acetic acid with n-butanol in the presence of Zr(SO4)2·4H2O coupled pervaporation , 2002 .

[13]  M. David,et al.  Pervaporation-esterification coupling. I, Basic kinetic model , 1991 .

[14]  Jan Degrève,et al.  Pervaporation of water¿alcohol mixtures and acetic acid¿water mixtures , 2005 .

[15]  Robert Y. M. Huang,et al.  Studies of a membrane reactor: Esterification facilitated by pervaporation , 1996 .

[16]  Xu Zhenliang,et al.  Modified aromatic polyimide membrane preparation and pervaporation results for esterification system , 1995 .

[17]  Soo-Bok Lee,et al.  Pervaporation of fluoroethanol/water and methacrylic acid/water mixtures through PVA composite membranes , 2005 .

[18]  I. Ortiz,et al.  Pervaporative recovery of acetic acid from an acetylation industrial effluent using commercial membranes , 2005 .

[19]  M. Kariduraganavar,et al.  Preparation and characterization of novel pervaporation membranes for the separation of water–isopropanol mixtures using chitosan and NaY zeolite , 2005 .

[20]  J. Keurentjes,et al.  The esterification of tartaric acid with ethanol: Kinetics and shifting the equilibrium by means of pervaporation , 1994 .

[21]  H. Kita,et al.  Synthesis of crown ether-containing copolyimides and their pervaporation properties to benzene/cyclohexane mixtures , 2005 .

[22]  H. Kita,et al.  Esterification of Carboxylic Acid with Ethanol Accompanied by Pervaporation , 1988 .

[23]  Shih-Perng Tsai,et al.  Esterification of Lactic Acid and Ethanol with/without Pervaporation , 2003 .

[24]  T. Mohammadi,et al.  Pervaporation of dilute alcoholic mixtures using PDMS membrane , 2005 .

[25]  M. Bruening,et al.  Ultrathin, cross-linked polyimide pervaporation membranes prepared from polyelectrolyte multilayers , 2005 .

[26]  L. Domingues,et al.  Studies of a pervaporation reactor : kinetics and equilibrium shift in benzyl alcohol acetylation , 1999 .