Methanol Synthesis: Optimal Solution for a Better Efficiency of the Process

In this research, an ANOVA analysis and a response surface methodology are applied to analyze the equilibrium of methanol reaction from pure carbon dioxide and hydrogen. In the ANOVA analysis, carbon monoxide composition in the feed, reaction temperature, recycle and water removal through a zeolite membrane are the analyzed factors. Carbon conversion, methanol yield, methanol productivity and methanol selectivity are the analyzed responses. Results show that main factors have the same effect on responses and a common significant interaction is not present. Carbon monoxide composition and water removal have a positive effect, while temperature and recycle have a negative effect on the system. From central composite design, an optimal solution is found in order to overcome thermodynamic limit: the reactor works with a membrane at lower temperature with carbon monoxide composition in the feed equal to 10 mol % and without recycle. In these conditions, carbon conversion, methanol yield, methanol selectivity, and methanol production are, respectively, higher than 60%, higher than 60%, between 90% and 95% and higher than 0.15 mol/h when considering a feed flow rate of 1 mol/h. A comparison with a traditional reactor is also developed: the membrane reactor ensures to have a carbon conversion higher of the 29% and a methanol yield higher of the 34%. Future researches should evaluate an economic analysis about the optimal solution.

[1]  George A. Olah,et al.  After Oil and Gas: Methanol Economy , 2004 .

[2]  J. Hansen,et al.  13.13 Methanol Synthesis , 2008 .

[3]  G. Olah,et al.  Anthropogenic chemical carbon cycle for a sustainable future. , 2011, Journal of the American Chemical Society.

[4]  Margaret J. Robertson,et al.  Design and Analysis of Experiments , 2006, Handbook of statistics.

[5]  Mario Ditaranto,et al.  Application of a Central Composite Design for the Study of NOx Emission Performance of a Low NOx Burner , 2015 .

[6]  Samuel Stucki,et al.  A membrane reactor for methanol synthesis , 1996 .

[7]  E. Heracleous,et al.  Overcoming the equilibrium barriers of CO2 hydrogenation to methanol via water sorption: A thermodynamic analysis , 2017 .

[8]  M. Saito,et al.  Development of copper/zinc oxide-based multicomponent catalysts for methanol synthesis from carbon dioxide and hydrogen , 1996 .

[9]  B. Haut,et al.  Development and analysis of a multifunctional reactor for equilibrium reactions: benzene hydrogenation and methanol synthesis , 2004 .

[10]  Jinfu Wang,et al.  Methanol Synthesis from CO2 Hydrogenation with a Cu/Zn/Al/Zr Fibrous Catalyst , 2009 .

[11]  Joseph G. Pigeon,et al.  Statistics for Experimenters: Design, Innovation and Discovery , 2006, Technometrics.

[12]  Marco Restelli,et al.  Considerations on the steady-state modeling of methanol synthesis fixed-bed reactor , 2011 .

[13]  Jyeshtharaj B. Joshi,et al.  Catalytic carbon dioxide hydrogenation to methanol: A review of recent studies , 2014 .

[14]  James G. Speight,et al.  Handbook of Alternative Fuel Technologies , 2007 .

[15]  Harold H. Kung,et al.  Methanol production and use , 1994 .

[16]  Gilbert F. Froment,et al.  A Steady-State Kinetic Model for Methanol Synthesis and the Water Gas Shift Reaction on a Commercial Cu/ZnO/Al2O3 Catalyst , 1996 .

[17]  A. Basile,et al.  A theoretical analysis of methanol synthesis from CO2 and H2 in a ceramic membrane reactor , 2007 .

[18]  S. Stucki,et al.  Verification of the membrane reactor concept for the methanol synthesis , 2001 .

[19]  George A. Olah,et al.  Chemical Recycling of Carbon Dioxide to Methanol and Dimethyl Ether: From Greenhouse Gas to Renewable, Environmentally Carbon Neutral Fuels and Synthetic Hydrocarbons. , 2009 .

[20]  G. Groppi,et al.  Enabling small-scale methanol synthesis reactors through the adoption of highly conductive structured catalysts , 2013 .

[21]  Waldemar Liebner,et al.  CO2-based methanol and DME – Efficient technologies for industrial scale production , 2011 .

[22]  I. Metcalfe,et al.  Methanol Synthesis from CO/CO2/H2over Cu/ZnO/Al2O3at Differential and Finite Conversions , 1998 .

[23]  H. Arakawa.  Research and development on new synthetic routes for basic chemicals by catalytic hydrogenation of CO2 , 1998 .

[24]  E. Drioli,et al.  Simulation of CO2 hydrogenation with CH3OH removal in a zeolite membrane reactor , 2002 .

[25]  A. Basile,et al.  An experimental study of CO2 hydrogenation into methanol involving a zeolite membrane reactor , 2004 .

[26]  Young Gul Kim,et al.  A Comparative Study of Methanol Synthesis from CO2/H2 and CO/H2 over a Cu/ZnO/Al2O3 Catalyst , 1993 .

[27]  Atsushi Urakawa,et al.  Towards full one-pass conversion of carbon dioxide to methanol and methanol-derived products , 2014 .

[28]  R. W. Rousseau,et al.  Methanol synthesis reactions: calculations of equilibrium conversions using equations of state , 1986 .

[29]  J. G. V. Bennekom,et al.  Methanol synthesis beyond chemical equilibrium , 2013 .

[30]  Jerzy Skrzypek,et al.  Thermodynamics and kinetics of low pressure methanol synthesis , 1995 .