In bed and downstream hot gas desulphurization during solid fuel gasification: A review

Syngas produced by gasification process of biomass fuels is an environmental friendly alternative to conventional petrochemical fuels for the production of electricity, hydrogen, synthetic transportation biofuels and other chemicals. However, the advanced utilization of syngas is significantly limited due to the contaminants which can seriously deactivate the catalysts used for downstream reaction such as steam reforming methane, Fischer–Tropsch synthesis and corrosion of downstream equipments such as a gas turbine. Among the contaminants, sulphur compounds produced in the gasification process, which are mainly H2S with small amounts of COS, CS2 and thiophenes depending on process conditions, must be removed. For biomass feedstock advances are required in the cleanup technologies and processes to upgrade the raw product gas with minimal impact on the overall process efficiency. Hot gas desulphurization (HGD) can improve the overall thermal efficiency due to the elimination of fuel gas cooling and associated heat exchangers. With this aim, the present review paper highlights currently developed methods used for desulphurization of hot gas produced from gasification process of solid fuels. The methods presented here are for both in situ and downstream sulphur capture. Also, the attention is paid to the regeneration of the used materials. In situ sulphur capture is mainly done by using calcium-based sorbents such as limestone and dolomite, whereas downstream sulphur capture is mainly focused on the use of regenerable single, mixed, and supported metal oxides. A comparison is indicated at the end to show the sulphur loading of various materials.

[1]  Yang Wang,et al.  Sol-gel auto-combustion synthesis of zinc ferrite for moderate temperature desulfurization , 2007 .

[2]  J. Vohs,et al.  Determining the Ce2O2S–CeOx phase boundary for conditions relevant to adsorption and catalysis , 2003 .

[3]  Z. Wang,et al.  Regenerative Adsorption and Removal of H2S from Hot Fuel Gas Streams by Rare Earth Oxides , 2006, Science.

[4]  F. R. Groves,et al.  High temperature gas desulfurization with elemental sulfur production , 1999 .

[5]  Rachid B. Slimane,et al.  A Regenerable Copper-Based Sorbent for H2S Removal from Coal Gases , 1998 .

[6]  Jenny M. Jones,et al.  Removal of H2S by spray-calcined calcium acetate , 1999 .

[7]  S. Yaşyerli,et al.  Activities of Copper Oxide and Cu−V and Cu−Mo Mixed Oxides for H2S Removal in the Presence and Absence of Hydrogen and Predictions of a Deactivation Model , 2001 .

[8]  M. T. Hepworth,et al.  KINETICS OF Mn-BASED SORBENTS FOR HOT COAL GAS DESULFURIZATION , 1997 .

[9]  Andreas Hornung,et al.  HTHP syngas cleaning concept of two stage biomass gasification for FT synthesis , 2008 .

[10]  M. Hasatani,et al.  Kinetic studies on the reactions involved in the hot gas desulfurization using a regenerable iron oxide sorbent—I , 1981 .

[11]  H. Atakül,et al.  Removal of H2S from fuel gases at high temperatures using MnO/γ-Al2O3 , 1995 .

[12]  M. T. Hepworth,et al.  Desulfurization of Hot Coal-Derived Fuel Gases with Manganese-Based Regenerable Sorbents. 2. Regeneration and Multicycle Tests , 1994 .

[13]  J. Jia,et al.  Mesoporous SBA-15 Supported Iron Oxide: A Potent Catalyst for Hydrogen Sulfide Removal , 2008 .

[14]  Makoto Nunokawa,et al.  Moderate temperature gas purification system: Application to high calorific coal-derived fuel , 2008 .

[15]  T. Kyotani,et al.  Removal of H2S from hot gas in the presence of Cu-containing sorbents , 1989 .

[16]  J. Swisher,et al.  Review of metals and binary oxides as sorbents for removing sulfur from coal-derived gases , 1992, Journal of Materials Engineering and Performance.

[17]  Javad Abbasian,et al.  Copper-Based Sorbents for Coal Gas Desulfurization at Moderate Temperatures , 2000 .

[18]  Mohammad Nurunnabi,et al.  Fischer–Tropsch Synthesis over Ru Catalysts by Using Syngas Derived from Woody Biomass , 2009 .

[19]  C. Wen,et al.  Kinetic studies on the reactions involved in the hot gas desulfurization using a regenerable iron oxide sorbent—II: Reactions of iron sulfide with oxygen and sulfur dioxide , 1981 .

[20]  N. Woudstra,et al.  Impact of Biomass-Derived Contaminants on SOFCs with Ni/Gadolinia-Doped Ceria Anodes , 2008 .

[21]  Mikko Hupa,et al.  Hydrogen Sulfide Capture by Limestone and Dolomite at Elevated Pressure. 1. Sorbent Performance , 1996 .

[22]  W. V. Swaaij,et al.  THE SULPHIDATION OF CALCINED LIMESTONE WITH HYDROGEN SULPHIDE AND CARBONYL SULPHIDE , 1995 .

[23]  T. Wheelock,et al.  Development of an advanced calcium-based sorbent for desulfurizing hot coal gas , 2001 .

[24]  H. Matsuda,et al.  Dry, high-temperature De-SO2 and De-H2S via treated calcium-based materials , 1997 .

[25]  Joseph M. Norbeck,et al.  Removal of Hydrogen Sulfide from a Steam-Hydrogasifier Product Gas by Zinc Oxide Sorbent , 2007 .

[26]  S. Yaşyerli,et al.  Removal of hydrogen sulfide by clinoptilolite in a fixed bed adsorber , 2002 .

[27]  Douglas P. Harrison,et al.  Evaluation of candidate solids for high-temperature desulfurization of low-Btu gases , 1976 .

[28]  M. Flytzani-Stephanopoulos,et al.  Reduction and Sulfidation Kinetics of Cerium Oxide and Cu-Modified Cerium Oxide , 2002 .

[29]  S. Lynn,et al.  Study of Calcium-Based Sorbents for High-Temperature H2S Removal. 3. Comparison of Calcium-Based Sorbents for Coal Gas Desulfurization , 1995 .

[30]  J. Poston A reduction in the spalling of zinc titanate desulfurization sorbents through the addition of lanthanum oxide , 1996 .

[31]  S. Yaşyerli,et al.  Mn−Cu and Mn−Cu−V Mixed-Oxide Regenerable Sorbents for Hot Gas Desulfurization , 2005 .

[32]  H. Kamiya,et al.  Dry gas cleaning in coal gasification systems for fuel cells using composite sorbents , 2008 .

[33]  T. Wheelock,et al.  A Regenerable Calcium-Based Core-in-Shell Sorbent for Desulfurizing Hot Coal Gas , 2002 .

[34]  J. Abbasian,et al.  Desulfurization of fuels with calcium-based sorbents , 1990 .

[35]  Hengyong Xu,et al.  A sulfur-tolerant Pd/CeO 2 catalyst for methanol synthesis from syngas , 2008 .

[36]  Y. Sakata,et al.  Modification of ZnO−TiO2 High-Temperature Desulfurization Sorbent by ZrO2 Addition , 1999 .

[37]  H. Chu,et al.  Hydrogen sulfide removal from coal gas by the metal-ferrite sorbents made from the heavy metal wastewater sludge. , 2008, Journal of hazardous materials.

[38]  H. Atakül,et al.  Investigation of CuO/mesoporous SBA-15 sorbents for hot gas desulfurization , 2008 .

[39]  R. Ma,et al.  A study on regeneration of Mn–Fe–Zn–O supported upon γ-Al2O3 sorbents for hot gas desulfurization , 2003 .

[40]  R. Moliner,et al.  Performance of Mn and Cu mixed oxides as regenerable sorbents for hot coal gas desulfurization , 2000 .

[41]  A. Atimtay,et al.  Zeolite-Supported Metal Oxide Sorbents for Hot-Gas Desulfurization , 1998 .

[42]  R. Moliner,et al.  Characterization of Mn and Cu oxides as regenerable sorbents for hot coal gas desulfurization , 2000 .

[43]  A. M. Squires,et al.  Desulfurization of fuels with calcined dolomite. 1. Introduction and first kinetic results , 1971 .

[44]  E. Podlaha,et al.  Ceria−Zirconia High-Temperature Desulfurization Sorbents , 2005 .

[45]  J. Swisher,et al.  Thermodynamic analysis of sorption reactions for the removal of sulfur from hot gases , 1992 .

[46]  D. Carpenter,et al.  Review of Mid- to High-Temperature Sulfur Sorbents for Desulfurization of Biomass- and Coal-derived Syngas , 2009 .

[47]  Jae-Chang Kim,et al.  Two-stage desulfurization process for hot gas ultra cleanup in IGCC , 2006 .

[48]  Freek Kapteijn,et al.  A high capacity manganese-based sorbent for regenerative high temperature desulfurization with direct sulfur production: Conceptual process application to coal gas cleaning , 2003 .

[49]  Toshimitsu Suzuki,et al.  Preparation of zinc ferrite in the presence of carbon material and its application to hot-gas cleaning , 2004 .

[50]  M. T. Hepworth,et al.  Desulfurization of Hot Coal-Derived Fuel Gases with Manganese-Based Regenerable Sorbents. 1. Loading (Sulfidation) Tests , 1994 .

[51]  H. Jun,et al.  A Study of Zn−Ti-Based H2S Removal Sorbents Promoted with Cobalt Oxides , 2001 .

[52]  K. R. G. Hein,et al.  Coal/biomass co-gasification in a pressurised fluidised bed reactor , 1999 .

[53]  Harold H. Kung,et al.  Deactivation of methanol synthesis catalysts - a review , 1992 .

[54]  Francisco García-Labiano,et al.  Utilization of Calcium Acetate and Calcium Magnesium Acetate for H2S Removal in Coal Gas Cleaning at High Temperatures , 1999 .

[55]  Wanwang Peng,et al.  Research improvement in Zn-based sorbent for hot gas desulfurization , 2008 .

[56]  E. Sasaoka,et al.  Stability of Zinc Oxide High-Temperature Desulfurization Sorbents for Reduction , 1994 .

[57]  Chunshan Song,et al.  Hydrogen and Syngas Production and Purification Technologies , 2010 .

[58]  M. T. Hepworth,et al.  Desulfurization of Hot Coal-Derived Fuel Gases with Manganese-Based Regenerable Sorbents. 3. Fixed-Bed Testing , 1995 .

[59]  S. Garimella,et al.  Kinetic study on the reactions involved in hot gas desulfurization using a regenerable iron oxide sorbent—III. Reactions of the sulfided sorbent with steam and steam-air mixtures , 1985 .

[60]  A. M. Squires,et al.  Desulfurization of fuels with half-calcined dolomite: first kinetic data. [Use for removal of H sulfide] , 1972 .

[61]  Maria Flytzani-Stephanopoulos,et al.  Cu−Cr−O and Cu−Ce−O Regenerable Oxide Sorbents for Hot Gas Desulfurization , 1997 .

[62]  Huiqin Fan,et al.  Testing of Iron Oxide Sorbent for High-Temperature Coal Gas Desulfurization , 2005 .

[63]  S. Yaşyerli,et al.  Dynamic analysis of removal and selective oxidation of H2S to elemental sulfur over Cu–V and Cu–V–Mo mixed oxides in a fixed bed reactor , 2004 .

[64]  Jianglong Yu,et al.  Removal of sulfur at high temperatures using iron-based sorbents supported on fine coal ash , 2010 .

[65]  S. Gangwal,et al.  Development of zinc ferrite sorbents for desulfurization of hot coal gas in a fluid-bed reactor , 1992 .

[66]  Chang-Keun Yi,et al.  A Study of Zn−Ti-Based H2S Removal Sorbents Promoted with Cobalt and Nickel Oxides , 2004 .

[67]  R. H. Borgwardt,et al.  Reaction of hydrogen sulfide and sulfur with limestone particles , 1984 .

[68]  J. Fierro,et al.  Characterization of zinc oxide and zinc ferrite doped with Ti or Cu as sorbents for hot gas desulphurization , 1997 .

[69]  Chih-hung Chang,et al.  The preparation of a high surface area metal oxide prepared by a matrix-assisted method for hot gas desulphurization , 2005 .

[70]  Z. Wang,et al.  Cerium Oxide-Based Sorbents for Regenerative Hot Reformate Gas Desulfurization , 2005 .

[71]  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 .

[72]  William Nimmo,et al.  The effect of sintering on sulphur capture by limestone and dolomite , 2005 .

[73]  Chih-hung Chang,et al.  The preparation and desulfurization of nano-size ZnO by a matrix-assisted method for the removal of low concentration of sulfur compounds , 2008 .

[74]  S. Yaşyerli Cerium–manganese mixed oxides for high temperature H2S removal and activity comparisons with V–Mn, Zn–Mn, Fe–Mn sorbents , 2008 .

[75]  H. Verelst,et al.  Transition metal oxides for hot gas desulphurisation , 1999 .

[76]  J. Goodwin,et al.  Hot Gas Removal of Tars, Ammonia, and Hydrogen Sulfide from Biomass Gasification Gas , 2007 .

[77]  S. Rapagnà Steam-gasification of biomass in a fluidised-bed of olivine particles. , 2000 .

[78]  R. T. Yang,et al.  Calcium silicates: A new class of highly regenerative sorbents for hot gas desulfurization , 1979 .

[79]  S. Yaşyerli,et al.  Synthesis and Activity Comparison of Copper-Incorporated MCM-41-Type Sorbents Prepared by One-Pot and Impregnation Procedures for H2S Removal , 2008 .

[80]  K. Xie,et al.  Bench-Scale Testing of Zinc Ferrite Sorbent for Hot Gas Clean-up , 2007 .

[81]  K. Cen,et al.  The fractal dimension of calcined limestone and its sulfur-removal reactivity , 1997 .

[82]  Adel F. Sarofim,et al.  Sulfidation of zinc titanate and zinc oxide solids , 1992 .

[83]  J. Otero,et al.  A study on sulphidation and regeneration of Z-Sorb III sorbent for H2S removal from simulated ELCOGAS IGCC syngas , 2005 .