Hydrogen production from biomass coupled with carbon dioxide capture: The implications of thermodynamic equilibrium

Abstract In this work we report on the consequences of thermodynamic equilibrium for hydrogen ( H 2 ) generation via steam gasification of biomass, coupled with in situ carbon dioxide ( CO 2 ) capture. Calcium oxide (CaO) is identified as a suitable sorbent for CO2 capture, capable of absorbing CO2 to very low concentrations, at temperatures and pressures conducive to the gasification of biomass. The proposed process exploits the reversible nature of the CO2 capture reaction and leads to the production of a concentrated stream of CO2, upon regeneration of the sorbent. We develop a thermodynamic equilibrium model to investigate fundamental reaction parameters influencing the output of H2-rich gas. These are: (i) reaction temperature, (ii) reaction pressure, (iii) steam-to-biomass ratio, and (iv) sorbent-to-biomass ratio. Based on the model, we predict a maximum H2 concentration of 83%-mol, with a steam-to-biomass ratio of 1.5 and a Ca-to-C ratio of 0.9. Contrary to previous experimental studies, this maximum H2 output is reported at atmospheric pressure. Model predictions are compared with an experimental investigation of the pyrolysis of pure cellulose and the reactivity of CaO through multiple CO2 capture and release cycles using a thermogravimetric analyser, coupled with a mass spectrometer (TGA–MS). On this basis, we demonstrate the applicability of thermodynamic equilibrium theory for the identification of optimal operating conditions for maximising H2 output and CO2 capture.

[1]  J. Grace,et al.  Equilibrium modeling of gasification: a free energy minimization approach and its application to a circulating fluidized bed coal gasifier , 2001 .

[2]  Debabrata Das,et al.  Hydrogen from biomass , 2003 .

[3]  Bo Feng,et al.  Screening of CO2 adsorbing materials for zero emission power generation systems , 2007 .

[4]  M. Antal,et al.  Simultaneous thermogravimetric-mass spectrometric studies of the thermal decomposition of biopolymers. 1. Avicel cellulose in the presence and absence of catalysts , 1988 .

[5]  Robin W. Hughes,et al.  Design, Process Simulation, and Construction of an Atmospheric Dual Fluidized Bed Combustion System for In Situ CO2 Capture Using High-temperature Sorbents , 2005 .

[6]  Himanshu Gupta,et al.  Multicyclic Study on the Simultaneous Carbonation and Sulfation of High-Reactivity CaO , 2004 .

[7]  Norma Amadeo,et al.  Thermodynamic analysis of hydrogen production from ethanol using CaO as a CO2 sorbent , 2004 .

[8]  Yoshizo Suzuki,et al.  Developing an innovative method, HyPr-RING, to produce hydrogen from hydrocarbons , 2002 .

[9]  K. Kuramoto,et al.  Coal gasification with a subcritical steam in the presence of a CO2 sorbent: products and conversion under transient heating , 2003 .

[10]  Hiroyuki Hatano,et al.  Continuous experiment regarding hydrogen production by Coal/CaO reaction with steam (II) solid formation , 2006 .

[11]  Hiroyuki Hatano,et al.  Continuous experiment regarding hydrogen production by coal/CaO reaction with steam (I) gas products , 2004 .

[12]  E. J. Anthony,et al.  Capture of CO2 from combustion gases in a fluidized bed of CaO , 2004 .

[13]  Hiroyuki Hatano,et al.  Hydrogen production from heavy oil in the presence of calcium hydroxide , 2003 .

[14]  William R. Smith,et al.  Chemical Reaction Equilibrium Analysis: Theory and Algorithms , 1982 .

[15]  J. R. Kim,et al.  Biomass gasification in a circulating fluidized bed , 2004 .

[16]  Dennis Witmer,et al.  Thermodynamic analysis of hydrogen production by steam reforming , 2003 .

[17]  S. Kersten.  Biomass gasification in circulating fluidized beds , 2002 .

[18]  Himanshu Gupta,et al.  Kinetics and Structural Characterization of Calcium-Based Sorbents Calcined under Subatmospheric Conditions for the High-Temperature CO2 Capture Process , 2007 .

[19]  M. W. Chase,et al.  NIST-JANAF Thermochemical Tables Fourth Edition , 1998 .

[20]  C. M. Kinoshita,et al.  An experimental investigation of hydrogen production from biomass gasification , 1998 .

[21]  John R. Grace,et al.  SO2 Removal and CO2 Capture by Limestone Resulting from Calcination/Sulfation/Carbonation Cycles , 2005 .

[22]  R. Barker,et al.  The reactivity of calcium oxide towards carbon dioxide and its use for energy storage , 1974 .

[23]  John P. Longwell,et al.  Product Layer Diffusion during the Reaction of Calcium Oxide with Carbon Dioxide , 1999 .

[24]  J. C. Abanades,et al.  Conversion Limits in the Reaction of CO2 with Lime , 2003 .

[25]  A. L. Ortíz,et al.  Hydrogen from methane in a single-step process , 1999 .

[26]  Douglas P. Harrison,et al.  Simultaneous shift reaction and carbon dioxide separation for the direct production of hydrogen , 1994 .

[27]  Hiroyuki Hatano,et al.  Process analysis for hydrogen production by reaction integrated novel gasification (HyPr-RING) , 2005 .

[28]  Toshiaki Hanaoka,et al.  Hydrogen production from woody biomass by steam gasification using a CO2 sorbent , 2005 .

[29]  N. Muradov,et al.  From hydrocarbon to hydrogen–carbon to hydrogen economy , 2005 .

[30]  R. Barker,et al.  The reversibility of the reaction CaCO3 ⇄ CaO+CO2 , 2007 .

[31]  Giampaolo Manfrida,et al.  An equilibrium model for biomass gasification processes , 1999 .

[32]  M. Antal.  Effects of residence time, temperature, and pressure on the steam gasification of biomass , 1979 .

[33]  L. T. Fan,et al.  Steam gasification of pure cellulose. 1. Uniform temperature profile , 1985 .

[34]  John R. Grace,et al.  Modeling of Sorption-Enhanced Steam Reforming in a Dual Fluidized Bubbling Bed Reactor , 2006 .

[35]  Robin W. Hughes,et al.  Improved Long-Term Conversion of Limestone-Derived Sorbents for In Situ Capture of CO2 in a Fluidized Bed Combustor , 2004 .

[36]  Syuan-Hong Lin,et al.  Hydrogen production from coal by separating carbon dioxide during gasification , 2002 .

[37]  Edward S Rubin,et al.  A technical, economic, and environmental assessment of amine-based CO2 capture technology for power plant greenhouse gas control. , 2002, Environmental science & technology.

[38]  Isabel Cabrita,et al.  The study of reactions influencing the biomass steam gasification process , 2003 .

[39]  Javier Herguido,et al.  Steam gasification of lignocellulosic residues in a fluidized bed at a small pilot scale. Effect of the type of feedstock , 1992 .

[40]  C. M. Kinoshita,et al.  Production of hydrogen from bio-oil using CaO as a CO2 sorbent , 2003 .

[41]  D. D. Perlmutter,et al.  Effect of the product layer on the kinetics of the CO2‐lime reaction , 1983 .

[42]  Zhihua Wang,et al.  Thermodynamic equilibrium analysis of hydrogen production by coal based on Coal/CaO/H2O gasification system , 2006 .

[43]  Andrew E. Lutz,et al.  Thermodynamic analysis of hydrogen production by partial oxidation reforming , 2004 .

[44]  José Corella,et al.  Steam gasification of cellulosic wastes in a fluidized bed with downstream vessels. , 1991 .

[45]  D. P. Harrison,et al.  HIGH TEMPERATURE CAPTURE OF CARBON DIOXIDE: CHARACTERISTICS OF THE REVERSIBLE REACTION BETWEEN CaO(s) and CO2(g) , 1995 .

[46]  K. Sumathy,et al.  AN OVERVIEW OF HYDROGEN PRODUCTION FROM BIOMASS , 2006 .

[47]  L. Fan,et al.  Carbonation−Calcination Cycle Using High Reactivity Calcium Oxide for Carbon Dioxide Separation from Flue Gas , 2002 .