Methanol synthesis from syngas obtained by supercritical water reforming of glycerol

Abstract A process for producing methanol from the synthesis gas obtained by reforming of glycerol using supercritical water is studied. The process also produces power from the huge pressure energy of product gas just at the outlet of the reformer by a turbine. The expanded product gas is conditioned in a PSA system, which has three sections so as to produce a H 2 -rich gas stream, a CO-rich gas stream and CO 2 for sequestration. Thus, it can be achieved the feed required for the methanol synthesis. The surplus hydrogen is sent to a fuel cell to generate power, and the PSA off-gas, purge from the methanol loop and gases separated from the crude methanol are burnt in a furnace to achieve an energy self-sufficient process. By changing the reforming temperature, the water-to-glycerol mass ratio and the purge from the methanol loop, the conditions for optimizing the overall process relative to methanol and power productions were achieved. Thus, by reforming at 1000 °C and 240 atm, and performing the methanol synthesis at 250 °C and 85 atm, the optimal conditions were a water-to-glycerol mass ratio of 1.68 with a purge ratio of 0.2. Under these conditions 0.270 kg MeOH/kg glycerol and overall energy efficiency of 38.0% were obtained. The separated CO 2 for sequestration is 0.38 kg/kg of glycerol.

[1]  Michael Stöcker,et al.  Methanol-to-hydrocarbons: catalytic materials and their behavior 1 Dedicated to my wife Wencke Ophau , 1999 .

[2]  Timothy Christopher Golden,et al.  Purification of Hydrogen by Pressure Swing Adsorption , 2000 .

[3]  Yang Guo,et al.  Review of catalytic supercritical water gasification for hydrogen production from biomass , 2010 .

[4]  Wei Feng,et al.  Analysis of Methanol Production from Biomass Gasification , 2011 .

[5]  Paul A Webley,et al.  Cycle development and design for CO2 capture from flue gas by vacuum swing adsorption. , 2008, Environmental science & technology.

[6]  Phillip E. Savage,et al.  Organic Chemical Reactions in Supercritical Water. , 1999, Chemical reviews.

[7]  Hao Wang,et al.  Thermodynamic analysis of hydrogen production from glycerol autothermal reforming , 2009 .

[8]  L. E. Borges,et al.  Production of renewable hydrogen from aqueous-phase reforming of glycerol over Pt catalysts supported on different oxides , 2011 .

[9]  S. A. Tabak,et al.  Conversion of methanol over ZSM-5 to fuels and chemicals , 1990 .

[10]  K. Pant,et al.  Hydrogen production from glycerol by reforming in supercritical water over Ru/Al2O3 catalyst , 2008 .

[11]  Amornchai Arpornwichanop,et al.  Thermodynamic study of hydrogen production from crude glycerol autothermal reforming for fuel cell applications , 2010 .

[12]  C. Pevida,et al.  Evaluation of Activated Carbon Adsorbents for CO2 Capture in Gasification , 2009 .

[13]  Pedro Ollero,et al.  Thermodynamic study of the supercritical water reforming of glycerol , 2011 .

[14]  G. Cerrato,et al.  Glycerol steam reforming for hydrogen production: Design of Ni supported catalysts , 2012 .

[15]  P. Spath,et al.  Preliminary screening: Technical and economic assessment of synthesis gas to fuels and chemicals with emphasis on the potential for biomass-derived syngas , 2003 .

[16]  Eize Stamhuis,et al.  ON CHEMICAL-EQUILIBRIA IN METHANOL SYNTHESIS , 1990 .

[17]  Harvey G. Stenger,et al.  Kinetics, simulation and insights for CO selective oxidation in fuel cell applications , 2004 .

[18]  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 .

[19]  D. Agar,et al.  Thermally integrated bio-syngas-production for biorefineries , 2009 .

[20]  B. Metz.  IPCC special report on carbon dioxide capture and storage , 2005 .

[21]  D. Azevedo,et al.  Adsorption of CO2 on nitrogen-enriched activated carbon and zeolite 13X , 2011 .

[22]  Richard G. Herman,et al.  Catalytic synthesis of methanol from COH2: IV. The effects of carbon dioxide , 1982 .

[23]  Tomoaki Minowa,et al.  Biomass gasification in near- and super-critical water: Status and prospects , 2005 .

[24]  Sidharth Abrol,et al.  Modeling, simulation and advanced control of methanol production from variable synthesis gas feed , 2012, Comput. Chem. Eng..

[25]  Kevin Kendall,et al.  Steam reforming of biodiesel by-product to make renewable hydrogen. , 2008, Bioresource technology.

[26]  André Faaij,et al.  Future prospects for production of methanol and hydrogen from biomass , 2002 .

[27]  Vince White,et al.  Advanced hydrogen and CO2 capture technology for sour syngas , 2011 .

[28]  A. Rodrigues,et al.  Syngas Stoichiometric Adjustment for Methanol Production and Co-Capture of Carbon Dioxide by Pressure Swing Adsorption , 2012 .

[29]  M. Fan,et al.  Methanol and Derivatives , 2010 .

[30]  Liejin Guo,et al.  Hydrogen production by biomass gasification in supercritical water: A systematic experimental and analytical study , 2007 .

[31]  A.A.C.M. Beenackers,et al.  Comparison of two-phase and three-phase methanol synthesis processes , 1996 .

[32]  Abdolhossein Jahanmiri,et al.  Optimization of methanol synthesis reactor using genetic algorithms , 2005 .

[33]  James A. Dumesic,et al.  A review of catalytic issues and process conditions for renewable hydrogen and alkanes by aqueous-phase reforming of oxygenated hydrocarbons over supported metal catalysts , 2005 .

[34]  Yongping Hou,et al.  The analysis for the efficiency properties of the fuel cell engine , 2007 .