纳米钙基吸附剂脱碳强化生物乙醇蒸汽重整制氢工艺
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摘要
将纳米钙基二氧化碳吸附剂用于反应脱除二氧化碳,强化生物乙醇蒸汽重整制氢反应过程。研究反应温度、水醇摩尔比和反应空速等工艺条件对乙醇制氢反应转化率和产物氢气浓度的强化作用效果。研究表明,在常压下,反应温度为560℃,水醇摩尔比为7:1,乙醇体积空速为800 h-1时,乙醇转化率为90.5%,气相色谱检测反应产物气体中氢气浓度为98.2%,CO浓度仅为0.05%,无CO2存在。研究结果对采用生物乙醇制氢提供燃料电池原料氢气具有参考意义。
A nano Ca-based CO2 adsorbent was used to facilitate sorption enhanced steam reforming of bio-ethanol. Effects of reaction temperature, steam to ethanol molar ratio and ethanol space velocity on bio-ethanol conversion and hydrogen content were studied. The results show that ethanol conversion is 90.5% under reaction conditions of steam to ethanol molar ratio = 7:1, ethanol volume space velocity = 800 h-1, reaction temperature = 560℃ and atmospheric pressure. Hydrogen concentration at outlets is 98.2% and carbon monoxide concentration is 0.05% without carbon dioxide detected. This study is helpful for hydrogen production from bio-ethanol for fuel cell application.
A nano Ca-based CO2 adsorbent was used to facilitate sorption enhanced steam reforming of bio-ethanol. Effects of reaction temperature, steam to ethanol molar ratio and ethanol space velocity on bio-ethanol conversion and hydrogen content were studied. The results show that ethanol conversion is 90.5% under reaction conditions of steam to ethanol molar ratio = 7:1, ethanol volume space velocity = 800 h-1, reaction temperature = 560℃ and atmospheric pressure. Hydrogen concentration at outlets is 98.2% and carbon monoxide concentration is 0.05% without carbon dioxide detected. This study is helpful for hydrogen production from bio-ethanol for fuel cell application.
引文
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[11]TANG Qi(唐琪),WU Su-fang(吴素芳).The effect of Ca O content on sorption performance of nano-Ca O based CO2 adsorbent(Ca O含量对纳米Ca O/Al2O3吸附剂性能的影响)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2012,26(1):31-36.
[12]SHI Yu-yao(史余耀),LAN Pei-qiang(兰培强),WANG Yan(王燕).Modified kinetics model of nano-Ca O reactions with CO2 in a Ca O-based adsorbent(钙基吸附剂中纳米Ca O与CO2反应动力学模型的改进)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2015,29(1):96-101.
[13]SHI Qi(师琦),WU Su-fang(吴素芳),JIANG Ming-zhe(蒋明哲),et al.Reactive sorption-decomposition kinetics of nano Ca-based CO2 sorbents(纳米钙基CO2吸附剂反应吸附与分解动力学)[J].CIESC Journal(化工学报),2009,60(3):641-648.
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[15]HE Jun(贺隽),WU Su-fang(吴素芳).The characteristics of sorption enhanced steam methane reforming for hydrogen production on a complex catalyst(吸附强化的甲烷水蒸汽重整制氢反应特性)[J].Chemical Reaction Engineering and Technology(化学反应工程与工艺),2007,23(5):470-473.
[16]LI Lian-bao(李联豹).Study on the reactive characteristics and kinetics of the reactive sorption catalyst in the RSER process for hydrogen production(RSER制氢过程复合催化剂反应特性及动力学研究)[D].Hangzhou(杭州):Zhejiang University(浙江大学),2008.
[17]LU Shang-qing(卢尚青),WU Su-fang(吴素芳).Advances in calcium carbonate thermal decomposition(碳酸钙热分解进展)[J].CIESC Journal(化工学报),2015,66(8):2895-2902.
[18]CHEN Jian-feng(陈建峰),JIA Zhi-qian(贾志谦),WANG Yu-hong(王玉红),et al.Synthesis and characterization of cube-shaped Ca CO3 nanometer particles in high gravity field(超重力场中合成立方形纳米Ca CO3颗粒与表征)[J].Chinese Journal of Chemical Physics(化学物理学报),1997,10(5):457-460.
[19]Wu S F,Li Q H,Kim J N,et al.Properties of a nano Ca O/Al2O3 CO2 sorbent[J].Industrial&Engineering Chemistry Research,2008,47(1):180-184.
[20]Liu R J,Chen J F,Guo F,et al.Kinetics and mechanism of decomposition of nano-sized calcium carbonate under non-isothermal condition[J].Chinese Journal of Chemical Engineering,2003,11(3):302-306.
[21]YUE Lin-hai(岳林海),SHUI Miao(水淼),XU Zhu-de(徐铸德),et al.The crystal structure of ultra-fine Ca CO3 and its thermal decomposition(超细碳酸钙微晶结构与热分解特性)[J].Chemical Research In Chinese Universities(高等学校化学学报),2000,21(10):1555-1559.
[22]YUE Lin-hai(岳林海),SHUI Miao(水淼).Decomposition kinetics of nano-particle calcite(纳米级粒径超细碳酸钙热分解动力学)[J].Chinese Journal of Inorganic Chemistry(无机化学学报),1999,15(2):225-229.
[23]WANG Wen-jun(王文举).Reforming of ethanol for hydrogen production catalyzed by nickel catalysts(Ni催化剂催化乙醇重整制氢的研究)[D].Tianjin(天津):Tianjin University(天津大学),2009.
[2]MAO Zong-qiang(毛宗强).Nations quicken pace of developing hydrogen energy market:a brief introduction to WHEC2010(世界各国加快氢能源市场化步伐——记第18届世界氢能大会(WHEC 2010))[J].Sino-Global Energy(中外能源),2010,15(7):29-34.
[3]LANG Lin(郎林),LI Jian-ming(李键铭),YANG Wen-shen(杨文申),et al.Bio-ethanol catalytic steam reforming over Ni/KZSM-5catalysts(Ni/KZSM-5催化剂的生物乙醇水蒸气重整制氢催化性能)[J].Renewable Energy Resources(可再生能源),2017,35(2):185-191.
[4]Lapola D M,Turner B L.Indirect land-use changes can overcome carbon savings from biofuels in Brazil[J].Proceedings of the Natconal Academy of Sciences of the United States of America,2010,107(8):3388-3393.
[5]ZHANG Chao(张超),LANG Lin(郎林),YIN Xiu-li(阴秀丽).Reactors for hydrogen production by bio-ethanol reforming(生物乙醇重整制氢反应器)[J].Progress in Chemistry(化学进展),2011,23(4):810-818.
[6]Deluga G A,Salge J R,Schmidt L D,et al.Renewable hydrogen from ethanol by autothermal reforming[J].Science,2004,303(5660):993.
[7]Meng N,Dennis Y C,Michael K H.A review on reforming bio-ethanol for hydrogen production[J].International Journal of Hydrogen Energy,2007,32(15):3238-3247.
[8]Gunduz S,Dogu T.Sorption-enhanced reforming of ethanol over Ni-and Co-incorporated MCM-41 type catalysts[J].Industrial&Engineering Chemistry Research,2011,51(26):8796-8805.
[9]Lysikov A,Derevschikov V,Okunev A.Sorption-enhanced reforming of bioethanol in dual fixed bed reactor for continuous hydrogen production[J].International Journal of Hydrogen Energy,2015,40(42):14436-14444.
[10]He L,Berntsen H,Chen D.Approaching sustainable H2 production:sorption enhanced steam reforming of ethanol[J].Journal of Physical Chemistry A,2010,114(11):3834-44.
[11]TANG Qi(唐琪),WU Su-fang(吴素芳).The effect of Ca O content on sorption performance of nano-Ca O based CO2 adsorbent(Ca O含量对纳米Ca O/Al2O3吸附剂性能的影响)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2012,26(1):31-36.
[12]SHI Yu-yao(史余耀),LAN Pei-qiang(兰培强),WANG Yan(王燕).Modified kinetics model of nano-Ca O reactions with CO2 in a Ca O-based adsorbent(钙基吸附剂中纳米Ca O与CO2反应动力学模型的改进)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2015,29(1):96-101.
[13]SHI Qi(师琦),WU Su-fang(吴素芳),JIANG Ming-zhe(蒋明哲),et al.Reactive sorption-decomposition kinetics of nano Ca-based CO2 sorbents(纳米钙基CO2吸附剂反应吸附与分解动力学)[J].CIESC Journal(化工学报),2009,60(3):641-648.
[14]Wu S F,Beum T H,Yang J I,et al.The characteristics of a sorption-enhanced steam-methane reaction for the production of hydrogen using CO2 sorbent[J].Chinese Journal of Chemical Engineering,2005,13(1):43-47.
[15]HE Jun(贺隽),WU Su-fang(吴素芳).The characteristics of sorption enhanced steam methane reforming for hydrogen production on a complex catalyst(吸附强化的甲烷水蒸汽重整制氢反应特性)[J].Chemical Reaction Engineering and Technology(化学反应工程与工艺),2007,23(5):470-473.
[16]LI Lian-bao(李联豹).Study on the reactive characteristics and kinetics of the reactive sorption catalyst in the RSER process for hydrogen production(RSER制氢过程复合催化剂反应特性及动力学研究)[D].Hangzhou(杭州):Zhejiang University(浙江大学),2008.
[17]LU Shang-qing(卢尚青),WU Su-fang(吴素芳).Advances in calcium carbonate thermal decomposition(碳酸钙热分解进展)[J].CIESC Journal(化工学报),2015,66(8):2895-2902.
[18]CHEN Jian-feng(陈建峰),JIA Zhi-qian(贾志谦),WANG Yu-hong(王玉红),et al.Synthesis and characterization of cube-shaped Ca CO3 nanometer particles in high gravity field(超重力场中合成立方形纳米Ca CO3颗粒与表征)[J].Chinese Journal of Chemical Physics(化学物理学报),1997,10(5):457-460.
[19]Wu S F,Li Q H,Kim J N,et al.Properties of a nano Ca O/Al2O3 CO2 sorbent[J].Industrial&Engineering Chemistry Research,2008,47(1):180-184.
[20]Liu R J,Chen J F,Guo F,et al.Kinetics and mechanism of decomposition of nano-sized calcium carbonate under non-isothermal condition[J].Chinese Journal of Chemical Engineering,2003,11(3):302-306.
[21]YUE Lin-hai(岳林海),SHUI Miao(水淼),XU Zhu-de(徐铸德),et al.The crystal structure of ultra-fine Ca CO3 and its thermal decomposition(超细碳酸钙微晶结构与热分解特性)[J].Chemical Research In Chinese Universities(高等学校化学学报),2000,21(10):1555-1559.
[22]YUE Lin-hai(岳林海),SHUI Miao(水淼).Decomposition kinetics of nano-particle calcite(纳米级粒径超细碳酸钙热分解动力学)[J].Chinese Journal of Inorganic Chemistry(无机化学学报),1999,15(2):225-229.
[23]WANG Wen-jun(王文举).Reforming of ethanol for hydrogen production catalyzed by nickel catalysts(Ni催化剂催化乙醇重整制氢的研究)[D].Tianjin(天津):Tianjin University(天津大学),2009.