Glycerol ethers synthesis from glycerol etherification with tert-butyl alcohol in reactive distillation

Abstract This paper presents a study of glycerol etherification with tert-butyl alcohol catalyzed by Amberlyst 15 in reactive distillation (RD). A thermodynamic analysis is firstly investigated by applying three group contribution methods, to determine the equilibrium composition by minimization of the Gibbs free energy and to compare the predicted values against measured data. Next, the kinetic model parameters are regressed by matching measured data from an autoclave reactor. The activity based Langmuir–Hinshelwood model is found to give the best representation of the reaction rate data. The regressed kinetic rate expressions are also compared against independently measured data in fixed bed reactors reported in the literature and found to give a good match. Finally, using the developed models, it is shown by simulation as well as verification by experiments, that the suitable RD configuration for the production of glycerol ethers in RD is the one consisting of 6 rectifying stages and 6 reaction stages without stripping stage.

[1]  G. Vicente,et al.  Acid-catalyzed etherification of bio-glycerol and isobutylene over sulfonic mesostructured silicas , 2008 .

[2]  G. Lu,et al.  Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals. , 2008, Chemical Society reviews.

[3]  Rafiqul Gani,et al.  Multiple steady states detection in a packed-bed reactive distillation column using bifurcation analysis , 2010, Comput. Chem. Eng..

[4]  Martin Bajus,et al.  Etherification of glycerol and ethylene glycol by isobutylene , 2007 .

[5]  Robert C. Reid,et al.  Estimation of critical properties with group contribution methods , 1984 .

[6]  Martin Bajus,et al.  tert-Butylation of glycerol catalysed by ion-exchange resins , 2005 .

[7]  Preparation of tertiary amyl alcohol in a reactive distillation column. 1. Reaction kinetics, chemical equilibrium, and mass-transfer issues , 1997 .

[8]  Jorge A. Marrero,et al.  Group-contribution based estimation of pure component properties , 2001 .

[9]  S. Goto,et al.  Kinetics of liquid‐phase synthesis of ethyl tert‐butyl ether from tert‐butyl alcohol and ethanol catalyzed by ion exchange resin and heteropoly acid , 1995 .

[10]  Dennis J. Miller,et al.  Propylene glycol and ethylene glycol recovery from aqueous solution via reactive distillation , 2004 .

[11]  Efstratios N. Pistikopoulos,et al.  The interactions of design, control and operability in reactive distillation systems , 2001 .

[12]  W. Kiatkittipong,et al.  Self-Etherification Process for Cleaner Fuel Production , 2009 .

[13]  W. Kiatkittipong,et al.  Simultaneous enhancement of ethanol supplement in gasoline and its quality improvement , 2008 .

[14]  S. Goto,et al.  Kinetic Study on 2-Methyl-1-Butanol Dehydration Catalysed by Ion Exchange Resin , 2002 .

[15]  Rafiqul Gani,et al.  Estimation of mixture properties from first- and second-order group contributions with the UNIFAC model , 2002 .

[16]  S. Goto,et al.  Kinetic study on the dehydration of tert-butyl alcohol catalyzed by ion exchange resins , 1999 .

[17]  A. Krause,et al.  Thermodynamics and Kinetics of the Dehydration of tert-Butyl Alcohol , 2004 .

[18]  W. Kiatkittipong,et al.  Cleaner gasoline production by using glycerol as fuel extender , 2010 .

[19]  K. Joback,et al.  ESTIMATION OF PURE-COMPONENT PROPERTIES FROM GROUP-CONTRIBUTIONS , 1987 .

[20]  Alírio E. Rodrigues,et al.  Thermodynamic Equilibrium and Reaction Kinetics for the Esterification of Lactic Acid with Ethanol Catalyzed by Acid Ion-Exchange Resin , 2008 .

[21]  S. Goto,et al.  Sorption effect on kinetics of etherification of tert-amyl alcohol and ethanol , 2003 .

[22]  Günter Wozny,et al.  A new operation mode for reactive batch distillation in middle-vessel columns: Start-up and operation , 2008, Comput. Chem. Eng..

[23]  A. L. Ahmad,et al.  Production of isopropyl palmitate in a catalytic distillation column: Comparison between experimental and simulation studies , 2007, Comput. Chem. Eng..

[24]  M. Morbidelli,et al.  Chromatographic Reactors: Esterification of Glycerol with Acetic Acid Using Acidic Polymeric Resins , 2003 .

[25]  Eduardo S. Pérez-Cisneros,et al.  A reactive distillation process for deep hydrodesulfurization of diesel: Multiplicity and operation aspects , 2010, Comput. Chem. Eng..

[26]  Efstratios N. Pistikopoulos,et al.  The interactions of design control and operability in reactive distillation systems , 2002 .

[27]  W. Kiatkittipong,et al.  Kinetics of liquid phase synthesis of ethyl tert‐butyl ether from tert‐butyl alcohol and ethanol catalyzed by β‐zeolite supported on monolith , 2002 .

[28]  W. Kiatkittipong,et al.  Effect of mode of operation on hydrogen production from glycerol at thermal neutral conditions: Thermodynamic analysis , 2010 .

[29]  Duane T. Johnson,et al.  The glycerin glut: Options for the value‐added conversion of crude glycerol resulting from biodiesel production , 2007 .

[30]  S. Benson,et al.  Additivity Rules for the Estimation of Molecular Properties. Thermodynamic Properties , 1958 .

[31]  R. Gani,et al.  New group contribution method for estimating properties of pure compounds , 1994 .

[32]  Reetta Karinen,et al.  New biocomponents from glycerol , 2006 .

[33]  J. D. Seader,et al.  A generalized framework for computing bifurcation diagrams using process simulation programs , 2001 .

[34]  R. Reid,et al.  The Properties of Gases and Liquids , 1977 .

[35]  Jürgen Gmehling,et al.  Esterification of a Fatty Acid by Reactive Distillation , 2003 .

[36]  W. Kiatkittipong,et al.  A pervaporation membrane reactor for liquid phase synthesis of ethyl tert-butyl ether from tert-butyl alcohol and ethanol , 2002 .

[37]  A. Krause,et al.  Etherification of FCC light gasoline with methanol , 1996 .

[38]  Martin Bajus,et al.  Etherification of glycerol with tert-butyl alcohol catalysed by ion-exchange resins , 2006 .

[39]  Pertti Koukkari,et al.  Calculation of constrained equilibria by Gibbs energy minimization , 2006 .

[40]  N. Ozbay,et al.  Conversion of Biodiesel By-Product Glycerol to Fuel Ethers over Different Solid Acid Catalysts , 2010 .

[41]  S. Goto,et al.  Reactive Distillation for Synthesizing Ethyl tert-Butyl Ether from Bioethanol , 1999 .

[42]  Rafiqul Gani,et al.  A generalized reactive separation unit model. Modelling and simulation aspects , 1998 .

[43]  Jürgen Gmehling,et al.  Reaction Kinetics and Chemical Equilibrium of Homogeneously and Heterogeneously Catalyzed Acetic Acid Esterification with Methanol and Methyl Acetate Hydrolysis , 2000 .