板翅式甲醇水蒸汽重整制氢反应器的研究
|
摘要
本论文目的是研发大能量密度的氢源系统,特别是小规模的分散制氢氢源系统和燃料电池车载氢源系统。
论文提出了温度均匀分布的甲醇水蒸汽重整反应器的设计思路,并根据此思路,借鉴板翅式换热器的优点,创新研制了全新结构的集成板翅式甲醇重整制氢反应器(简称重整器),集催化燃烧反应、甲醇和水蒸发以及重整反应为一体,使得整个系统的能量效率较高,可实现完全自供热。考察了不同条件对甲醇重整制氢过程和床层温度分布的影响,验证了反应器具有良好的稳定性。
为了反应器的优化和放大提供理论依据,论文建立了板翅式重整器内多反应耦合过程的三维数学模型,对重整器内部的温度分布和浓度分布进行了数值计算。计算结果表明:该板翅式重整器各腔的温度分布均匀,无热点分布;模型能较准确地预测重整腔内的CO 和H_2的浓度分布。同时,还利用数学模型对反应器的结构参数进行了专门的研究,得到了结构参数影响板翅式重整器性能的初步规律。
在实验和理论的基础上,论文研究了板翅式重整器在放大过程中涉及的问题和解决技巧,成功设计了5kW 重整器。并以此重整器为核心,联合CO 选择氧化的净化反应器,通过多段换热器对整个系统的能流、物流进行宏观管理与微观调控,成功研制了5kW 的氢源系统样机。
This paper is to develop the fuel processing system with high energy density. Thefocus is on small on-site hydrogen generation system and on-board hydrogengeneration system for the proton exchange membrane fuel cell (PEMFC).
The methanol steam reforming system, which is adopted in the reformer, has beenthermodynamically analyzed and calculated. A compact plate-fin reactor (PFR)consisting of closely spaced plate-fins, in which endothermic and exothermicreactions take place in alternate chambers, has been studied. In the PFR, which wasbased on a plate-fin heat exchanger, catalytic combustion of the reforming gas, as asimulation of the fuel cell anode off gas (AOG), supplied the necessary heat for thereforming reaction. One reforming chamber, which was for hydrogen production,was integrated with two vaporization chambers and two combustion chambers toconstitute a single unit of PFR. The PFR is very compact, easy to be placed on boardand to scale up. The effect of the ratio of water/methanol on the performance of thePFR has been investigated, and temperature distributions in different chambers werestudied. Besides, the stationary behavior of the plate-fin reactor was also investigated.Heat transfer of the reactor was enhanced by internal plate-fins as well as by externalcatalytic combustion, which offer both high methanol conversion ratio and low COconcentration.
A model describing the reaction process in the PFR was derived using athree-dimensional numerical model for crossflow arrangement. Temperaturedistributions in different chambers and composition distributions in reformingchamber have been caculated, and the effect of the ratio of water/methanol on theperformance of the PFR has also been calculated. Theoretical predictions of thetemperature distributions in the PFR were in good agreement with experimentalvalues. In addition, the numerical model was able to accurately predict the methanol
conversion and the reformate composition in reforming chamber. The numericalmodel was also used to describe the effect of configuration parameter on methanolreforming in PFR. The computational results indicate that the combined flowarrangement, which include crossflow, coflow and counterflow, should be adopted inpractical reactor design. The material with higher thermal conductivity should beselected preferentially. In order to minimize the heat transport resistance, small finspace and height should be applied in the reactor design. Based on the PFR, a scale-up reactor was designed and operated continuously for1000 hours, with high methanol conversion ratio and low CO concentration. Acompact integrated fuel processing system consisting of a 5kW PFR and multi-stagepreferential oxidation reactor is designed in this paper. Both internal plate-fins andexternal catalytic combustion were used to enhance heat transfer of the reformer,which offer both high methanol conversion ratio and low CO concentration. So thatthe water–gas shift reactor, which provides primary CO cleanup, is not necessary inthis fuel processing system. It will result in simplification of the fuel processingsystem design and capital cost reduction. The performance of the main componentsin the fuel processing system has been investigated. The axial temperatures of thedifferent chamber in 5kW PFR were uniform, and the temperatures at the inlet andoutlet of the PROX reactors were controlled strictly by plate-fin exchangers so that itcan minimize parasitic hydrogen oxidation. In addition, the results indicated that thisfuel processing system can provide a high concentration of hydrogen and the systemefficiency is always kept above 75%. It is further demonstrated that the fuelprocessing system could be operated autothermally and exhibited good test stability.
论文提出了温度均匀分布的甲醇水蒸汽重整反应器的设计思路,并根据此思路,借鉴板翅式换热器的优点,创新研制了全新结构的集成板翅式甲醇重整制氢反应器(简称重整器),集催化燃烧反应、甲醇和水蒸发以及重整反应为一体,使得整个系统的能量效率较高,可实现完全自供热。考察了不同条件对甲醇重整制氢过程和床层温度分布的影响,验证了反应器具有良好的稳定性。
为了反应器的优化和放大提供理论依据,论文建立了板翅式重整器内多反应耦合过程的三维数学模型,对重整器内部的温度分布和浓度分布进行了数值计算。计算结果表明:该板翅式重整器各腔的温度分布均匀,无热点分布;模型能较准确地预测重整腔内的CO 和H_2的浓度分布。同时,还利用数学模型对反应器的结构参数进行了专门的研究,得到了结构参数影响板翅式重整器性能的初步规律。
在实验和理论的基础上,论文研究了板翅式重整器在放大过程中涉及的问题和解决技巧,成功设计了5kW 重整器。并以此重整器为核心,联合CO 选择氧化的净化反应器,通过多段换热器对整个系统的能流、物流进行宏观管理与微观调控,成功研制了5kW 的氢源系统样机。
This paper is to develop the fuel processing system with high energy density. Thefocus is on small on-site hydrogen generation system and on-board hydrogengeneration system for the proton exchange membrane fuel cell (PEMFC).
The methanol steam reforming system, which is adopted in the reformer, has beenthermodynamically analyzed and calculated. A compact plate-fin reactor (PFR)consisting of closely spaced plate-fins, in which endothermic and exothermicreactions take place in alternate chambers, has been studied. In the PFR, which wasbased on a plate-fin heat exchanger, catalytic combustion of the reforming gas, as asimulation of the fuel cell anode off gas (AOG), supplied the necessary heat for thereforming reaction. One reforming chamber, which was for hydrogen production,was integrated with two vaporization chambers and two combustion chambers toconstitute a single unit of PFR. The PFR is very compact, easy to be placed on boardand to scale up. The effect of the ratio of water/methanol on the performance of thePFR has been investigated, and temperature distributions in different chambers werestudied. Besides, the stationary behavior of the plate-fin reactor was also investigated.Heat transfer of the reactor was enhanced by internal plate-fins as well as by externalcatalytic combustion, which offer both high methanol conversion ratio and low COconcentration.
A model describing the reaction process in the PFR was derived using athree-dimensional numerical model for crossflow arrangement. Temperaturedistributions in different chambers and composition distributions in reformingchamber have been caculated, and the effect of the ratio of water/methanol on theperformance of the PFR has also been calculated. Theoretical predictions of thetemperature distributions in the PFR were in good agreement with experimentalvalues. In addition, the numerical model was able to accurately predict the methanol
conversion and the reformate composition in reforming chamber. The numericalmodel was also used to describe the effect of configuration parameter on methanolreforming in PFR. The computational results indicate that the combined flowarrangement, which include crossflow, coflow and counterflow, should be adopted inpractical reactor design. The material with higher thermal conductivity should beselected preferentially. In order to minimize the heat transport resistance, small finspace and height should be applied in the reactor design. Based on the PFR, a scale-up reactor was designed and operated continuously for1000 hours, with high methanol conversion ratio and low CO concentration. Acompact integrated fuel processing system consisting of a 5kW PFR and multi-stagepreferential oxidation reactor is designed in this paper. Both internal plate-fins andexternal catalytic combustion were used to enhance heat transfer of the reformer,which offer both high methanol conversion ratio and low CO concentration. So thatthe water–gas shift reactor, which provides primary CO cleanup, is not necessary inthis fuel processing system. It will result in simplification of the fuel processingsystem design and capital cost reduction. The performance of the main componentsin the fuel processing system has been investigated. The axial temperatures of thedifferent chamber in 5kW PFR were uniform, and the temperatures at the inlet andoutlet of the PROX reactors were controlled strictly by plate-fin exchangers so that itcan minimize parasitic hydrogen oxidation. In addition, the results indicated that thisfuel processing system can provide a high concentration of hydrogen and the systemefficiency is always kept above 75%. It is further demonstrated that the fuelprocessing system could be operated autothermally and exhibited good test stability.
引文
[1] Srinivasant S, Velve O A and Manko D J. High energy efficiency and high power density PEMFC-electrode kinetics and mass transport. Journal of power Sources, 1991, 36(3): 299-320.
[2] Emonts B, B?gild Hansen J, L?gsgaard J?rgensen S, H?hlein B and Peters R. Compact methanol reformer test for fuel-cell powered light-duty vehicles. Journal of power Sources, 1998, 71(1-2): 288-293.
[3] Detlef zur Megede. Fuel processors for fuel cell vehicles. Journal of power Sources, 2002, 106(1-2): 35-41.
[4] Edwards N, Ellis S R, Frost J C, Golunski S E, van Keulen A, Lindewald N G, and Reinkingh J G. On-board hydrogen generation for transport applications: The HotSpotTM methanol processor. Journal of Power Sources, 1998, 71(1-2):123-128.
[5] Robert S, Wegeng, Larry R. Pederson, Ward E, TeGrotenhuis and Greg A. Whyatt. Compact fuel processors for fuel cell powered automobiles based on microchannel technology. Fuel Cells Bulletin, 2001, 3(28):8-13.
[6] Kumberger et al. Catalyst for steam-reforming methanol. US Patent 6,051,163. 2000.
[7] Nojima, Shigeru, Yasutake and Toshinobu. Methanol reforming catalyst, method of manufacturing methanol reforming catalyst and method of reforming methanol. US Patent 6,576,217.2003.
[8] Hirabayashi. Hydrocarbon fuel reformer. US Patent 6,692,707. 2004.
[9] Kuwaba. Reformer for fuel cell system. US Patent 6,632,409. 2003.
[10] 亓爱笃, 王树东, 付桂芝, 吴迪镛. 甲醇水蒸气、氧气重整制氢研究进展—质子交换膜 燃料电池氢源的开发. 石油与天然气化工, 1999, 28(2):82-85.
[11] 亓爱笃,洪学伦,王树东,付桂芝,吴迪镛. 甲醇氧化重整制氢反应动力学的研究. 天 然气化工, 2000, 25(4):18-21.
[12] 王胜年,洪学伦,王树东,吴迪镛. Cr-Zn 催化剂上甲醇水蒸汽重整反应动力学I. 本 征动力学. 石油化工, 2001, 30(4): 259-262.
[13] 王胜年,王树东,吴迪镛,付桂芝. Cr-Zn Cr-Zn 催化剂上甲醇水蒸汽重整反应动力学Ⅱ. 宏观动力学. 石油化工, 2001, 30(8): 593-596.
[14] Wang YH, Wu DY. The experimental research for production of hydrogen from n-octane through partially oxidizing and steam reforming method International. International Journal of Hydrogen Energy, 2001, 26(8):795-800.
[15] 潘立卫,王树东. 板式反应器中甲醇自热重整制氢的研究. 燃料化学学报, 2004, 32(3): 362-366.
[16] Schmidt V M, Brockerhoff P, Hohlein B and Stimming U. Utilization of methanol for polymer electrolyte fuel cells in mobile systems. Journal of Power Source, 1994, 49(1-3): 299-313.
[17] Shoesmith J P, Collins R D, Oakley M J and Stevenson D K. Status of solid polymer fuel cell system development. Journal of Power Source, 1994, 49(1-3):129-142.
[18] 王胜年. Cr-Zn 催化剂上甲醇水蒸汽重整制氢反应动力学研究. 硕士论文, 中国科学院 大连化学物理研究所, 2000.
[19] Pour V, Barton J and Benda A. Kinetics of Catalyzed Reaction of Methanol with Water Vapour.Coll Czechoslov Chem. Commun, 1975, 40:2923～2934.
[20] Amphlett J C, Evans M J, Jones R A, Mann R F and Weir R D. Hydrogen production by the catalytic steam reforming of methanol 1. The thermodynamics. Canadian Journal of Chemical Engineering, 1981, 59(6):720-727.
[21] Amphlett J C, Evans M J, Jones R A, Mann R F and Weir R D. Hydrogen production by the catalytic steam reforming of methanol Part 2: Kinetics of methanol decomposition using girdler G66B catalyst. Canadian Journal of Chemical Engineering, 1985, 63(4):605-611.
[22] Amphlett J C, Mann R F and Weir R D. Hydrogen Production by the Catalytic Steam Reforming of Methanol. Part3: Kinetics of Methanol Decomposition Using C18HC Catalyst.Can J Chem Eng, 1988, 66(6):950-956.
[23] Idem R O, Bakhshi N N.Production of hydrogen from methanol 1.Catalyst characterization. Industrial & Engineering Chemistry Research, 1994, 33(9): 2056-2065.
[24] Idem R O, Bakhshi N N.Production of hydrogen from methanol 2.Experimental studies. Industrial & Engineering Chemistry Research, 1994, 33(9): 2047-2055.
[25] Idem R O, Bakhshi N N. Production of Hydrogen from Methanol over Promoted Coprecipitated Cu-AlCatalysts: The Effect of Various Promoters and Catalyst Activation Methods. Industrial & Engineering Chemistry Research, 1995, 34(5):1548-1557.
[26] Idem R O, Bakhshi N N. Characterization studies of calcined, promoted and non-promoted methanol-steam reforming catalysts. Canadian Journal of Chemical Engineering, 1996, 74(2):288-300.
[27] Philpott J E. On-site production of hydrogen. Platinum Metals Review, 1976, 20(4):110-113.
[28] Jiang C J, Trimm D L, Wainwright M S and Cant N W. Kinetic mechanism for the reaction between methanol and water over a Cu-ZnO-Al_2O_3 catalyst. Applied Catalysis A: General, 1993, 97(2):145-158.
[29] Ma L, Jiang C, Adesina A A, Trimm D L and Wainwright M S. Simulation studies of autothermal reactor system for H2 production methanol steam reforming. The Chemical Engineering Journal, 1996, 62:103-l 11.
[30] Choi Y, Stenger H G. Fuel cell grade hydrogen from methanol on a commercial Cu/ZnO/Al_2O_3 catalyst. Applied Catalysis B: Environmental, 2002, 38(4):259-269.
[31] Samms S R, Savinell R F. Kinetics of methanol-steam reformation in an internal reforming fuel cell. Journal of Power Sources, 2002, 112(1):13-29.
[32] Nagano S, Miyagawa H, Azegami O and Ohsawa K. Heat transfer enhancement in methanol steam reforming for a fuel cell. Energy Conversion and Management, 2001, 42(15-17):1817-1829.
[33] Velu S, Suzuki K, Kapoor M P, Ohashi F and Osaki T. Selective production of hydrogen for fuel cells via oxidative steam reforming of methanol over CuZnAl(Zr)-oxide catalysts. Applied Catalysis A: General, 2001, 213(1):47-63.
[34] Tsai A P, Yoshimura M. Highly active quasicrystalline Al-Cu-Fe catalyst for steam reforming of methanol. Applied Catalysis A: General, 2001, 214(2):237-241.
[35] Wies W, Emonts B and Peters R. Methanol steam reforming in a fuel cell drive system. Journal of Power Sources, 1999, 84(2): 187-193.
[36] Schuessler M, Portscher M and Limbeck U. Monolithic integrated fuel processor for the conversion of liquid methanol. Catalysis Today, 2003, 79-80:511-520.
[37] Agrell J, Birgersson H and Boutonnet M. Steam reforming of methanol over Cu-ZnO-Al2O3 catalyst: a kinetic analysis and strategies for suppression of CO formation. Journal of Power Sources, 2002, 106 (1-2):249-257.
[38] 江一蛟,陶鹏万.甲醇转化制氢和保护气技术.工厂动力,1998, 75:30-37.
[39] Su Tien-Bau, Rei Min-Hon. Steam Reforming of Methanol over Nickle and Copper Catalysts. J. Chin. Chem. Soci., 1991, 38:535-541.
[40] Mizuno K, Yoshikawa K, Wakejima N, Takeuchi Y and Watanabe A. Production of Synthesis Gas with Various Compositions of H2, CO, and CO_2 from Methanol and Water on a Ni-K/Al_2O_3 Catalyst. Chemistry Letters, 1986, 179(11):1969-1972.
[41] Iwasa N, Kudo S and Takahashi H. Highly Selective Supported Pd Catalysts for Steam Reforming of methanol.Catal Lett, 1993, 19:211～216.
[42] Iwasa N, Masuda S, Ogawa N and Takezawa N.Steam reforming of methanol over Pd/ZnO: Effect of the formation of PdZn alloys upon the reaction. Applied Catalysis A: General, 1995, 125(1):145-157.
[43] Iwasa N, Masuda S and Takezawa N. Steam reforming of methanol over Ni, Co, Pd and Pt supported on ZnO. Reaction Kinetics and Catalysis Letters, 1995, 55(2):349-353.
[44] Kobayashi H, Takazawa N, Minochi C. Methanol Reforming Reaction over Copper-containing Mixed Oxides. Chemistry Letters, 1976, 60(2):1347-1350.
[45] Minochi C, Kobayashi H, Takazawa N. The Catalytic activities of Methanol Reforming Catalysts and Their Preparations. Chemistry Letters, 1979, 89(5):507-510.
[46] Breen J P, Ross J R H. Methanol reforming for fuel-cell applications: development of zirconia-containing Cu-Zn-Al catalysts. Catalysis Today, 1999, 51(3-4):521-533.
[47] 房鼎业等,甲醇生产技术及进展, 第一版, 华东化工学院出版社, 1990.
[48] 宋维端, 肖任坚, 房鼎业.甲醇工学.化学工业出版社,1996.
[49] Amphlett J C.An Experimental Design for Determining the Optium Method of Ctalyst Preparation. Stud Surf Sci Catal,1992,73:345～352.
[50] Pourv B J. Kinetics of Catalyzed Reaction of Methanol with Water Vapour.Coll Czechoslov Commun, 1980, 45:3402～3407.
[51] Santacesaria E, Carra S. Kinetics of Catalytic Steam Reforming of Methanol in a CSTR Reactor. Applied Catalysis, 1983, 5(3):345～358.
[52] Agaras H, Cerrella G and Laborde M A. Copper Catalysts for the Steam Reforming of Methanol: Analysis of the preparation variables. Applied Catalysis, 1988, 45(1):53～60.
[53] Takahashi K, Takezawa N and Kobashi H. Mechanism of steam reforming of methanol a copper-silica catalyst. Applied catalysis, 1982, 2(6):363-366.
[54] Jiang C J, Trimm D L, Wanwright M S and Cant NW. Kinetic study of steam reforming of methanol over copper-based catalyst. Applied Catalysis A: General, 1993, 93(2):245-255.
[55] Jenkins J W, Shutt E. Hot spot reactor: Hydrogen generation using a novel concept. Platinum Metals Rev., 1989, 33:118-127.
[56] Amphlett J C, Mann R F and Peppley B A. On board hydrogen purification for steam reformation/PEM fuel cell vehicle power plants. International Journal of Hydrogen Energy, 1996, 21(8):673-678.
[57] Huang Ta-Jen, Wang Sun-Way. Hydrogen production via partial oxidation of methanol over a copper-zinc catalyst. Applied Catalysis, 1986, 24(1-2):287-297.
[58] Huang Ta-Jen, Chren Shiou-Lih. Kinetics of partial oxidation of methanol over a copper-zinc catalyst. Applied Catalysis, 1988, 40(1-2):43-52.
[59] Nagano S, Miyagawa H, Azegami O, Ohsawa K. Heat transfer enhancement in methanol steam reforming for a fuel cell. Energy Conversion & Management, 2001, 42 :1817-1829.
[60] Rampe T, Heinzel A and Vogel B. Hydrogen generation from biogenic and fossil fuels by autothermal reforming. Journal of power Sources, 2000, 86(1-2): 536-541.
[61] Halvorson T, and Farris P. Onsite hydrogen generator for vehicle refueling application, Proceedings of the 97 World Car Conference, Riverside, CA, 1997, 331-338.
[62] Hunter J B, McGuire G. Method and apparatus for catalytic heat exchange. US Patent 4,214,867. 1980.
[63] De Groote A M, Froment G F, Kobylinski Th. Synthesis gas production from natural gas in a fixed bed reactor with reversed flow. Canadian Journal of Chemical Engineering, 1996, 74:735-742.
[64] Ma L, Trimm D L. Alternative catalyst bed configurations for the autothermic conversion of methane to hydrogen. Applied Catalysis A: General, 1996, 138: 265-273.
[65] Wolf D, H?henberger M and Baerns M. Exernal mass and heat transfer limitations of the partial oxidation of methane over a Pt/MgO catalyst -consequences for adiabatic reactor operation. Industrial & Engineering Chemistry Research, 1997, 36: 3345-3353.
[66] Avic A K, Trimm D L and ?lsen ?nsan Z. Heterogeneous reactor modeling for simulation of catalytic oxidation and steam reforming of methane. Chemical Engineering Science, 2001, 56(2):641-649.
[67] Zanfir M, Gavriilidis A. Catalytic combustion assisted methane steam reforming in a catalytic plate reactor. Chemical Engineering Science, 2003, 58(17): 3947-3960.
[68] Polman E A, Der Kinderen J M, Thuis F M A. Novel compact steam reformer for fuel cells with heat generation by catalytic combustion augmented by induction heating. Catalysis Today, 1999, 47(1-4): 347-351.
[69] Frauhammer J, Eigenberger G, Hippel L v and Arntz D. A new reactor concept for endothermic high-temperature reactions. Chemical Engineering Science, 1999, 54(15-16): 3661-3670.
[70] Sundaresan M, Ramaswamy S, Moore R M and Hoffman M A. Catalytic burner for an indirect methanol fuel cell vehiclefuel processor, Journal of Power Sources, 2003, 113(1):19~36.
[71] Oertel M, Schmitz J, Weirich W, Jendryssek-Neumann D and Schulten R. Steam reforming of natural gas with integrated hydrogen sepatation for hydrogen production. Chem Eng Technol, 1987, 10(4):248-255.
[72] Gryaznov V M.Hydrogen permeable palladium membrane catalysts. Platinum Metals Review, 1986, 30(2):68-72.
[73] 孙立新. 钯膜反应器操作参数优化及甲醇制氢反应的研究. 硕士论文, 中国科学院大 连化学物理研究所, 1995.
[74] Belousov I G, Legasov V A and Rusanov V D. Plasmochemical concept for thermochemical hydrogen production. International Journal of Hydrogen Energy, 1980, 5(1):1-6.
[75] O'Brien C J, Hochgreb S, Rabinovich A, Bromberg L and Cohn D R. Hydrogen production via plasma reformers. Proceedings of the Intersociety Energy Conversion Engineering Conference, 1996, 3:1747-1752.
[76] Bromberg L, Cohn D R, Rabinovich A and Alexeev N. Plasma catalytic reforming of methane. International Journal of Hydrogen Energy, 1999, 24(12):1131-1137.
[77] Bromberg L, Cohn D R, Rabinovich A, Alexeev N, Samokhin A, Ramprasad R and Tamhankar S. System optimization and cost analysis of plasma catalytic reforming of natural gas. International Journal of Hydrogen Energy, 2000, 25(12):1157-1161.
[78] Tonkovich A Y, Jimenez D M, Zilka J L, LaMont M, Wang Y and Wegeng R S. Microchannel chemical reactors for fuel processing. Proceedings of the Second AIChE International Conference on Microreaction Technology, 1998, 186-195.
[79] Martin P M, Bennett W D, Hammerstrom D J, Johnston J W and Matson D W. Laser micromachined and laminated microchannel components for chemical sensors and heat transfer applications. SPIE Conference Proceedings, 1997, 3224:258-265.
[80] Matson D W, Martin P M, Tonkovich A Y and Roberts G L. Fabrication of a stainless steel microchannel microcombustor using a lamination process. SPIE Conference Proceedings, 1998, 3514:386-392.
[81] Tonkovich A Y, Zilka J L, LaMont M J, Wang Y and Wegeng R S. Microchannel reactors for fuel processing applications. I. Water gas shift reactor. Chemical Engineering Science, 1999, 54(13-14):2947-2951.
[82] H?hlein B, Boe M, Bogild-Hansen J, Br?ckerhoff P, Colsman G, Emonts B, Menzer R and Riedel E. Hydrogen from methanol for fuel cells in mobile systems: development of a compact reformer. Journal of Power Sources, 1996, 61(1-2): 143-147.
[83] Pena M A, Gomez J P and Fierro J L G. New catalytic routes for syngas and hydrogen production. Applied Catalysis A: General, 1996, 144(1-2):7-57.
[84] Docter A and Lamm A. Gasoline fuel cell systems. Journal of Power Sources, 1999, 84(2): 194-200.
[85] Brown L F. A comparative study of fuels for on-board hydrogen production for fuel-cell-powered vehicles. International Journal of Hydrogen Energy, 2001, 26(4):381-397.
[86] Trimm D L and Onsan Z I. Onboard fuel conversion for hydrogen-fuel-cell-driven vehicles. Catalysis Reviews, 2001, 43:31-84.
[87] Zalca J M, L?ffler D G. Fuel processing for PEM fuel cells: transport and kinetic issues of system design. Journal of Power Sources, 2002, 111(1): 58-64.
[88] L?ffler D G, Taylor K, Mason D. A light hydrocarbon fuel processor producing high-purity hydrogen. Journal of Power Sources, 2003, 117(1-2):84-91.
[89] Privette R M. Fuel Processor for Fuel Cell Mobile Electric Power. Proceedings from the DOD Mobile Electric Power Fuel Cell Symposium, April 24, 1997.
[90] Edlund D. AUV/UUV fuel cell propulsion options. Proceedings of the IEEE Symposium on Autonomous Underwater Vehicle Technology, 2002:71-73.
[91] Lee S H D, Pereira C, Ahmed S and Krumpelt M. Fuel flexible fuel processor for reforming hydrocarbon-based fuels.2000 AIChE Annal Meeting, November 12-17, 2000, Los Angeles, CA.
[92] Ahmed S, Kumar R and Krumpelt M. Fuel processing for fuel cell power systems. Fuel Cells Bulletin, 1999, 2(12):4-7.
[93] Heinzel A, Vogel B and Hübner. Reforming of natural gas-hydrogen generation for small scale stationary fuel cell systems. Journal of Power Sources, 2002, 105(2):202-207.
[94] Vogel B, Heinzel A. Reformer development at Fraunhofer ISE. Fuel Cells Bulletin, 1998, 1(3):9-11.
[2] Emonts B, B?gild Hansen J, L?gsgaard J?rgensen S, H?hlein B and Peters R. Compact methanol reformer test for fuel-cell powered light-duty vehicles. Journal of power Sources, 1998, 71(1-2): 288-293.
[3] Detlef zur Megede. Fuel processors for fuel cell vehicles. Journal of power Sources, 2002, 106(1-2): 35-41.
[4] Edwards N, Ellis S R, Frost J C, Golunski S E, van Keulen A, Lindewald N G, and Reinkingh J G. On-board hydrogen generation for transport applications: The HotSpotTM methanol processor. Journal of Power Sources, 1998, 71(1-2):123-128.
[5] Robert S, Wegeng, Larry R. Pederson, Ward E, TeGrotenhuis and Greg A. Whyatt. Compact fuel processors for fuel cell powered automobiles based on microchannel technology. Fuel Cells Bulletin, 2001, 3(28):8-13.
[6] Kumberger et al. Catalyst for steam-reforming methanol. US Patent 6,051,163. 2000.
[7] Nojima, Shigeru, Yasutake and Toshinobu. Methanol reforming catalyst, method of manufacturing methanol reforming catalyst and method of reforming methanol. US Patent 6,576,217.2003.
[8] Hirabayashi. Hydrocarbon fuel reformer. US Patent 6,692,707. 2004.
[9] Kuwaba. Reformer for fuel cell system. US Patent 6,632,409. 2003.
[10] 亓爱笃, 王树东, 付桂芝, 吴迪镛. 甲醇水蒸气、氧气重整制氢研究进展—质子交换膜 燃料电池氢源的开发. 石油与天然气化工, 1999, 28(2):82-85.
[11] 亓爱笃,洪学伦,王树东,付桂芝,吴迪镛. 甲醇氧化重整制氢反应动力学的研究. 天 然气化工, 2000, 25(4):18-21.
[12] 王胜年,洪学伦,王树东,吴迪镛. Cr-Zn 催化剂上甲醇水蒸汽重整反应动力学I. 本 征动力学. 石油化工, 2001, 30(4): 259-262.
[13] 王胜年,王树东,吴迪镛,付桂芝. Cr-Zn Cr-Zn 催化剂上甲醇水蒸汽重整反应动力学Ⅱ. 宏观动力学. 石油化工, 2001, 30(8): 593-596.
[14] Wang YH, Wu DY. The experimental research for production of hydrogen from n-octane through partially oxidizing and steam reforming method International. International Journal of Hydrogen Energy, 2001, 26(8):795-800.
[15] 潘立卫,王树东. 板式反应器中甲醇自热重整制氢的研究. 燃料化学学报, 2004, 32(3): 362-366.
[16] Schmidt V M, Brockerhoff P, Hohlein B and Stimming U. Utilization of methanol for polymer electrolyte fuel cells in mobile systems. Journal of Power Source, 1994, 49(1-3): 299-313.
[17] Shoesmith J P, Collins R D, Oakley M J and Stevenson D K. Status of solid polymer fuel cell system development. Journal of Power Source, 1994, 49(1-3):129-142.
[18] 王胜年. Cr-Zn 催化剂上甲醇水蒸汽重整制氢反应动力学研究. 硕士论文, 中国科学院 大连化学物理研究所, 2000.
[19] Pour V, Barton J and Benda A. Kinetics of Catalyzed Reaction of Methanol with Water Vapour.Coll Czechoslov Chem. Commun, 1975, 40:2923～2934.
[20] Amphlett J C, Evans M J, Jones R A, Mann R F and Weir R D. Hydrogen production by the catalytic steam reforming of methanol 1. The thermodynamics. Canadian Journal of Chemical Engineering, 1981, 59(6):720-727.
[21] Amphlett J C, Evans M J, Jones R A, Mann R F and Weir R D. Hydrogen production by the catalytic steam reforming of methanol Part 2: Kinetics of methanol decomposition using girdler G66B catalyst. Canadian Journal of Chemical Engineering, 1985, 63(4):605-611.
[22] Amphlett J C, Mann R F and Weir R D. Hydrogen Production by the Catalytic Steam Reforming of Methanol. Part3: Kinetics of Methanol Decomposition Using C18HC Catalyst.Can J Chem Eng, 1988, 66(6):950-956.
[23] Idem R O, Bakhshi N N.Production of hydrogen from methanol 1.Catalyst characterization. Industrial & Engineering Chemistry Research, 1994, 33(9): 2056-2065.
[24] Idem R O, Bakhshi N N.Production of hydrogen from methanol 2.Experimental studies. Industrial & Engineering Chemistry Research, 1994, 33(9): 2047-2055.
[25] Idem R O, Bakhshi N N. Production of Hydrogen from Methanol over Promoted Coprecipitated Cu-AlCatalysts: The Effect of Various Promoters and Catalyst Activation Methods. Industrial & Engineering Chemistry Research, 1995, 34(5):1548-1557.
[26] Idem R O, Bakhshi N N. Characterization studies of calcined, promoted and non-promoted methanol-steam reforming catalysts. Canadian Journal of Chemical Engineering, 1996, 74(2):288-300.
[27] Philpott J E. On-site production of hydrogen. Platinum Metals Review, 1976, 20(4):110-113.
[28] Jiang C J, Trimm D L, Wainwright M S and Cant N W. Kinetic mechanism for the reaction between methanol and water over a Cu-ZnO-Al_2O_3 catalyst. Applied Catalysis A: General, 1993, 97(2):145-158.
[29] Ma L, Jiang C, Adesina A A, Trimm D L and Wainwright M S. Simulation studies of autothermal reactor system for H2 production methanol steam reforming. The Chemical Engineering Journal, 1996, 62:103-l 11.
[30] Choi Y, Stenger H G. Fuel cell grade hydrogen from methanol on a commercial Cu/ZnO/Al_2O_3 catalyst. Applied Catalysis B: Environmental, 2002, 38(4):259-269.
[31] Samms S R, Savinell R F. Kinetics of methanol-steam reformation in an internal reforming fuel cell. Journal of Power Sources, 2002, 112(1):13-29.
[32] Nagano S, Miyagawa H, Azegami O and Ohsawa K. Heat transfer enhancement in methanol steam reforming for a fuel cell. Energy Conversion and Management, 2001, 42(15-17):1817-1829.
[33] Velu S, Suzuki K, Kapoor M P, Ohashi F and Osaki T. Selective production of hydrogen for fuel cells via oxidative steam reforming of methanol over CuZnAl(Zr)-oxide catalysts. Applied Catalysis A: General, 2001, 213(1):47-63.
[34] Tsai A P, Yoshimura M. Highly active quasicrystalline Al-Cu-Fe catalyst for steam reforming of methanol. Applied Catalysis A: General, 2001, 214(2):237-241.
[35] Wies W, Emonts B and Peters R. Methanol steam reforming in a fuel cell drive system. Journal of Power Sources, 1999, 84(2): 187-193.
[36] Schuessler M, Portscher M and Limbeck U. Monolithic integrated fuel processor for the conversion of liquid methanol. Catalysis Today, 2003, 79-80:511-520.
[37] Agrell J, Birgersson H and Boutonnet M. Steam reforming of methanol over Cu-ZnO-Al2O3 catalyst: a kinetic analysis and strategies for suppression of CO formation. Journal of Power Sources, 2002, 106 (1-2):249-257.
[38] 江一蛟,陶鹏万.甲醇转化制氢和保护气技术.工厂动力,1998, 75:30-37.
[39] Su Tien-Bau, Rei Min-Hon. Steam Reforming of Methanol over Nickle and Copper Catalysts. J. Chin. Chem. Soci., 1991, 38:535-541.
[40] Mizuno K, Yoshikawa K, Wakejima N, Takeuchi Y and Watanabe A. Production of Synthesis Gas with Various Compositions of H2, CO, and CO_2 from Methanol and Water on a Ni-K/Al_2O_3 Catalyst. Chemistry Letters, 1986, 179(11):1969-1972.
[41] Iwasa N, Kudo S and Takahashi H. Highly Selective Supported Pd Catalysts for Steam Reforming of methanol.Catal Lett, 1993, 19:211～216.
[42] Iwasa N, Masuda S, Ogawa N and Takezawa N.Steam reforming of methanol over Pd/ZnO: Effect of the formation of PdZn alloys upon the reaction. Applied Catalysis A: General, 1995, 125(1):145-157.
[43] Iwasa N, Masuda S and Takezawa N. Steam reforming of methanol over Ni, Co, Pd and Pt supported on ZnO. Reaction Kinetics and Catalysis Letters, 1995, 55(2):349-353.
[44] Kobayashi H, Takazawa N, Minochi C. Methanol Reforming Reaction over Copper-containing Mixed Oxides. Chemistry Letters, 1976, 60(2):1347-1350.
[45] Minochi C, Kobayashi H, Takazawa N. The Catalytic activities of Methanol Reforming Catalysts and Their Preparations. Chemistry Letters, 1979, 89(5):507-510.
[46] Breen J P, Ross J R H. Methanol reforming for fuel-cell applications: development of zirconia-containing Cu-Zn-Al catalysts. Catalysis Today, 1999, 51(3-4):521-533.
[47] 房鼎业等,甲醇生产技术及进展, 第一版, 华东化工学院出版社, 1990.
[48] 宋维端, 肖任坚, 房鼎业.甲醇工学.化学工业出版社,1996.
[49] Amphlett J C.An Experimental Design for Determining the Optium Method of Ctalyst Preparation. Stud Surf Sci Catal,1992,73:345～352.
[50] Pourv B J. Kinetics of Catalyzed Reaction of Methanol with Water Vapour.Coll Czechoslov Commun, 1980, 45:3402～3407.
[51] Santacesaria E, Carra S. Kinetics of Catalytic Steam Reforming of Methanol in a CSTR Reactor. Applied Catalysis, 1983, 5(3):345～358.
[52] Agaras H, Cerrella G and Laborde M A. Copper Catalysts for the Steam Reforming of Methanol: Analysis of the preparation variables. Applied Catalysis, 1988, 45(1):53～60.
[53] Takahashi K, Takezawa N and Kobashi H. Mechanism of steam reforming of methanol a copper-silica catalyst. Applied catalysis, 1982, 2(6):363-366.
[54] Jiang C J, Trimm D L, Wanwright M S and Cant NW. Kinetic study of steam reforming of methanol over copper-based catalyst. Applied Catalysis A: General, 1993, 93(2):245-255.
[55] Jenkins J W, Shutt E. Hot spot reactor: Hydrogen generation using a novel concept. Platinum Metals Rev., 1989, 33:118-127.
[56] Amphlett J C, Mann R F and Peppley B A. On board hydrogen purification for steam reformation/PEM fuel cell vehicle power plants. International Journal of Hydrogen Energy, 1996, 21(8):673-678.
[57] Huang Ta-Jen, Wang Sun-Way. Hydrogen production via partial oxidation of methanol over a copper-zinc catalyst. Applied Catalysis, 1986, 24(1-2):287-297.
[58] Huang Ta-Jen, Chren Shiou-Lih. Kinetics of partial oxidation of methanol over a copper-zinc catalyst. Applied Catalysis, 1988, 40(1-2):43-52.
[59] Nagano S, Miyagawa H, Azegami O, Ohsawa K. Heat transfer enhancement in methanol steam reforming for a fuel cell. Energy Conversion & Management, 2001, 42 :1817-1829.
[60] Rampe T, Heinzel A and Vogel B. Hydrogen generation from biogenic and fossil fuels by autothermal reforming. Journal of power Sources, 2000, 86(1-2): 536-541.
[61] Halvorson T, and Farris P. Onsite hydrogen generator for vehicle refueling application, Proceedings of the 97 World Car Conference, Riverside, CA, 1997, 331-338.
[62] Hunter J B, McGuire G. Method and apparatus for catalytic heat exchange. US Patent 4,214,867. 1980.
[63] De Groote A M, Froment G F, Kobylinski Th. Synthesis gas production from natural gas in a fixed bed reactor with reversed flow. Canadian Journal of Chemical Engineering, 1996, 74:735-742.
[64] Ma L, Trimm D L. Alternative catalyst bed configurations for the autothermic conversion of methane to hydrogen. Applied Catalysis A: General, 1996, 138: 265-273.
[65] Wolf D, H?henberger M and Baerns M. Exernal mass and heat transfer limitations of the partial oxidation of methane over a Pt/MgO catalyst -consequences for adiabatic reactor operation. Industrial & Engineering Chemistry Research, 1997, 36: 3345-3353.
[66] Avic A K, Trimm D L and ?lsen ?nsan Z. Heterogeneous reactor modeling for simulation of catalytic oxidation and steam reforming of methane. Chemical Engineering Science, 2001, 56(2):641-649.
[67] Zanfir M, Gavriilidis A. Catalytic combustion assisted methane steam reforming in a catalytic plate reactor. Chemical Engineering Science, 2003, 58(17): 3947-3960.
[68] Polman E A, Der Kinderen J M, Thuis F M A. Novel compact steam reformer for fuel cells with heat generation by catalytic combustion augmented by induction heating. Catalysis Today, 1999, 47(1-4): 347-351.
[69] Frauhammer J, Eigenberger G, Hippel L v and Arntz D. A new reactor concept for endothermic high-temperature reactions. Chemical Engineering Science, 1999, 54(15-16): 3661-3670.
[70] Sundaresan M, Ramaswamy S, Moore R M and Hoffman M A. Catalytic burner for an indirect methanol fuel cell vehiclefuel processor, Journal of Power Sources, 2003, 113(1):19~36.
[71] Oertel M, Schmitz J, Weirich W, Jendryssek-Neumann D and Schulten R. Steam reforming of natural gas with integrated hydrogen sepatation for hydrogen production. Chem Eng Technol, 1987, 10(4):248-255.
[72] Gryaznov V M.Hydrogen permeable palladium membrane catalysts. Platinum Metals Review, 1986, 30(2):68-72.
[73] 孙立新. 钯膜反应器操作参数优化及甲醇制氢反应的研究. 硕士论文, 中国科学院大 连化学物理研究所, 1995.
[74] Belousov I G, Legasov V A and Rusanov V D. Plasmochemical concept for thermochemical hydrogen production. International Journal of Hydrogen Energy, 1980, 5(1):1-6.
[75] O'Brien C J, Hochgreb S, Rabinovich A, Bromberg L and Cohn D R. Hydrogen production via plasma reformers. Proceedings of the Intersociety Energy Conversion Engineering Conference, 1996, 3:1747-1752.
[76] Bromberg L, Cohn D R, Rabinovich A and Alexeev N. Plasma catalytic reforming of methane. International Journal of Hydrogen Energy, 1999, 24(12):1131-1137.
[77] Bromberg L, Cohn D R, Rabinovich A, Alexeev N, Samokhin A, Ramprasad R and Tamhankar S. System optimization and cost analysis of plasma catalytic reforming of natural gas. International Journal of Hydrogen Energy, 2000, 25(12):1157-1161.
[78] Tonkovich A Y, Jimenez D M, Zilka J L, LaMont M, Wang Y and Wegeng R S. Microchannel chemical reactors for fuel processing. Proceedings of the Second AIChE International Conference on Microreaction Technology, 1998, 186-195.
[79] Martin P M, Bennett W D, Hammerstrom D J, Johnston J W and Matson D W. Laser micromachined and laminated microchannel components for chemical sensors and heat transfer applications. SPIE Conference Proceedings, 1997, 3224:258-265.
[80] Matson D W, Martin P M, Tonkovich A Y and Roberts G L. Fabrication of a stainless steel microchannel microcombustor using a lamination process. SPIE Conference Proceedings, 1998, 3514:386-392.
[81] Tonkovich A Y, Zilka J L, LaMont M J, Wang Y and Wegeng R S. Microchannel reactors for fuel processing applications. I. Water gas shift reactor. Chemical Engineering Science, 1999, 54(13-14):2947-2951.
[82] H?hlein B, Boe M, Bogild-Hansen J, Br?ckerhoff P, Colsman G, Emonts B, Menzer R and Riedel E. Hydrogen from methanol for fuel cells in mobile systems: development of a compact reformer. Journal of Power Sources, 1996, 61(1-2): 143-147.
[83] Pena M A, Gomez J P and Fierro J L G. New catalytic routes for syngas and hydrogen production. Applied Catalysis A: General, 1996, 144(1-2):7-57.
[84] Docter A and Lamm A. Gasoline fuel cell systems. Journal of Power Sources, 1999, 84(2): 194-200.
[85] Brown L F. A comparative study of fuels for on-board hydrogen production for fuel-cell-powered vehicles. International Journal of Hydrogen Energy, 2001, 26(4):381-397.
[86] Trimm D L and Onsan Z I. Onboard fuel conversion for hydrogen-fuel-cell-driven vehicles. Catalysis Reviews, 2001, 43:31-84.
[87] Zalca J M, L?ffler D G. Fuel processing for PEM fuel cells: transport and kinetic issues of system design. Journal of Power Sources, 2002, 111(1): 58-64.
[88] L?ffler D G, Taylor K, Mason D. A light hydrocarbon fuel processor producing high-purity hydrogen. Journal of Power Sources, 2003, 117(1-2):84-91.
[89] Privette R M. Fuel Processor for Fuel Cell Mobile Electric Power. Proceedings from the DOD Mobile Electric Power Fuel Cell Symposium, April 24, 1997.
[90] Edlund D. AUV/UUV fuel cell propulsion options. Proceedings of the IEEE Symposium on Autonomous Underwater Vehicle Technology, 2002:71-73.
[91] Lee S H D, Pereira C, Ahmed S and Krumpelt M. Fuel flexible fuel processor for reforming hydrocarbon-based fuels.2000 AIChE Annal Meeting, November 12-17, 2000, Los Angeles, CA.
[92] Ahmed S, Kumar R and Krumpelt M. Fuel processing for fuel cell power systems. Fuel Cells Bulletin, 1999, 2(12):4-7.
[93] Heinzel A, Vogel B and Hübner. Reforming of natural gas-hydrogen generation for small scale stationary fuel cell systems. Journal of Power Sources, 2002, 105(2):202-207.
[94] Vogel B, Heinzel A. Reformer development at Fraunhofer ISE. Fuel Cells Bulletin, 1998, 1(3):9-11.