木炭水蒸气催化气化制取合成气
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摘要
以木炭为原料,选用KOH、K_2CO_3、KHCO_3、KNO_3为催化剂,在上吸式固定床气化炉中,进行水蒸气催化气化制取合成气实验。考察了不同催化剂、催化剂用量、水蒸气流量、气化温度对木炭水蒸气气化的炭转化率、产氢率、气体组成体积分数和H_2/CO值的影响。实验通过炭吸收催化剂溶液来负载催化剂,实验结果表明:4种催化剂都可提高木炭气化效率,在浸渍相同质量分数的催化剂溶液下,催化活性顺序为KOH>K_2CO_3>KHCO_3>KNO_3。碳转化率及产氢率都随着催化剂溶液浓度的增加而增大,但浓度过高增加趋势逐渐变缓,催化剂溶液质量分数在4%～6%较为合适。增加水蒸气流量,气体产物中H_2体积分数增大,H_2/CO值增大。升高温度可促进炭气化反应,950℃时碳转化率和产氢率分别达到98.7%和145.23g/kg。实验可得到H_2/CO比1.53～4.09范围间的合成气,可用于合成甲醇、甲烷、二甲醚等燃料。
Charcoal catalytic steam gasification for syngas was investigated using a lab-scale fixed bed gasifier to study the effects of different catalysts, temperature, and steam flow rate. Four alkali salts of KOH, K_2 CO_3, KHCO_3 and KNO_3 were selected to pretreat charcoal. This paper discusses production of syngas from steam catalytic gasification of charcoal in a lab-scale ?xed bed reactor, using KOH, K_2 CO_3,KHCO_3 and KNO_3 as catalysts. The effects of different catalysts, steam flow rate and gasification temperatures on carbon conversion rate, hydrogen production rate, volume fraction of gas composition and H_2/CO value of charcoal vaporization were investigated. The method of char absorbing catalyst was used to load catalyst in this work. The experiment used the absorption of potassium salt solution by carbon to load catalysts. The experimental results show that the four kinds of potassium salts can all improve the gasification efficiency of charcoal. With the same mass fraction of potassium salt solution, the catalytic activity of the four catalysts is in the order: KOH > K_2 CO_3> KHCO_3> KNO_3. In addition, the rate of carbon conversion and hydrogen yield production increased with increasing concentration of the catalyst concentration, but the increasing trend slows down gradually. With further increase the trend of high concentration increased gradually, so the mass fraction of catalyst solution was more appropriate in the 4%—6% range. The H_2 composition and the H_2/CO ratio enhances with the increases of steam flow rate. The rise of temperature can promote carbon gasification reaction and the carbon conversion and hydrogen yield can reach 98.7% and 145.23 g/kg at 950℃. The syngas of H_2/CO ratio in the range of 1.53—4.09 was obtained. A promising application for biomass is liquid fuel synthesis, such as methanol or dimethyl ether(DME).
Charcoal catalytic steam gasification for syngas was investigated using a lab-scale fixed bed gasifier to study the effects of different catalysts, temperature, and steam flow rate. Four alkali salts of KOH, K_2 CO_3, KHCO_3 and KNO_3 were selected to pretreat charcoal. This paper discusses production of syngas from steam catalytic gasification of charcoal in a lab-scale ?xed bed reactor, using KOH, K_2 CO_3,KHCO_3 and KNO_3 as catalysts. The effects of different catalysts, steam flow rate and gasification temperatures on carbon conversion rate, hydrogen production rate, volume fraction of gas composition and H_2/CO value of charcoal vaporization were investigated. The method of char absorbing catalyst was used to load catalyst in this work. The experiment used the absorption of potassium salt solution by carbon to load catalysts. The experimental results show that the four kinds of potassium salts can all improve the gasification efficiency of charcoal. With the same mass fraction of potassium salt solution, the catalytic activity of the four catalysts is in the order: KOH > K_2 CO_3> KHCO_3> KNO_3. In addition, the rate of carbon conversion and hydrogen yield production increased with increasing concentration of the catalyst concentration, but the increasing trend slows down gradually. With further increase the trend of high concentration increased gradually, so the mass fraction of catalyst solution was more appropriate in the 4%—6% range. The H_2 composition and the H_2/CO ratio enhances with the increases of steam flow rate. The rise of temperature can promote carbon gasification reaction and the carbon conversion and hydrogen yield can reach 98.7% and 145.23 g/kg at 950℃. The syngas of H_2/CO ratio in the range of 1.53—4.09 was obtained. A promising application for biomass is liquid fuel synthesis, such as methanol or dimethyl ether(DME).
引文
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[10]NZIHOU A,STANMORE B,SHARROCK P.A review of catalysts for the gasification of biomass char,with some reference to coal[J].Energy,2013,58(3):305-317.
[11]PERONDI D,POLETTO P,RESTELATTO D,et al.Steam gasification of poultry litter biochar for bio-syngas production[J].Process Safety&Environmental Protection,2017,109:478-488.
[12]FENG Y,ZHANG L,HU Z,et al.Hydrogen-rich gas production by steam gasification of char derived from cyanobacterial blooms(CDCB)in a fixed-bed reactor:influence of particle size and residence time on gas yield and syngas composition[J].International Journal of Hydrogen Energy,2010,35(19):10212-10217.
[13]YAN F,LUO S Y,HU Z Q,et al.Hydrogen-rich gas production by steam gasification of char from biomass fast pyrolysis in a fixed-bed reactor:influence of temperature and steam on hydrogen yield and syngas composition[J].Bioresource Technology,2010,101(14):5633-5637.
[14]YAN L,CAO Y,He B.On the kinetic modeling of biomass/coal char co-gasification with steam[J].Chemical Engineering Journal,2018,331:435-442.
[15]HUHN F,KLEIN J,JUNTGEN H.Investigations on the alkalicatalysed steam gasification of coal:kinetics and interactions of alkali catalyst with carbon[J].Fuel,1983,62(2):196-199.
[16]CHEN Z,DUN Q,SHI Y,et al.High quality syngas production from catalytic coal gasification using disposable Ca(OH)2,catalyst[J].Chemical Engineering Journal,2017,316:842-849.
[17]孙立.生物质热解气化原理与技术[M].北京:化学工业出版社,2013.SUN Li.Theory and technology of biomass pyrolysis and gasification[M].Beijing:Chemical Industry Press,2013.
[18]WAHEED Q M K,WU C,WILLIAMS P T.Hydrogen production from high temperature steam catalytic gasification of bio-char[J].Journal of the Energy Institute,2015,89(2):222-230.
[19]NANOU P,MURILLO H E G,SWAAIJ W P M V,et al.Intrinsic reactivity of biomass-derived char under steam gasification conditions-potential of wood ash as catalyst[J].Chemical Engineering Journal,2013,217(2):289-299.
[20]张报安,黄河,金玳.用动力学参数对炭气化催化剂性能的表征[J].大连理工大学学报,1985(2):9-15.ZHANG Bao’an,HUANG He,JIN Dai.Characterization of carbon gasification catalysts by kinetic parameters[J].Journal of Dalian University of Technology,1985(2):9-15.
[21]SHANG J Y,WOLF E E.FTIR studies of potassium catalyst-treated gasified coal chars and carbons[J].Fuel,1983,62(2):252-255.
[22]HUTTINGER K J,MINGES R.Water vapour gasification of carbon:Improved catalytic activity of potassium chloride using anion exchange[J].Fuel,1985,64(4):486-490.
[23]王永刚,谢克昌,凌开成,等.碱金属催化剂在煤气化过程中的作用机理[J].太原理工大学学报,1988(3):55-65.WANG Yonggang,XIE Kechang,LING Kaicheng,et al.Action mechanism of alkali metal catalysis in the gasification of coal/char[J].Journal of Taiyuan University of Technology,1988(3):55-65.
[24]SAMS D A,TALVERDIAN T,SHADMAN F.Kinetics of catalyst loss during potassium-catalyzed CO2gasification of carbon[J].Fuel,1985,64(9):1208-1214.
[25]GUERRA L,ROSSI S,RODEIGUES J,et al.Methane production by a combined Sabatier reaction/water electrolysis process[J].Journal of Environmental Chemical Engineering,2017,6(1):671.
[26]INAYAT A,AHMAD M M,MUTALIB M I A,et al.Effect of process parameters on hydrogen production and efficiency in biomass gasification using modelling approach[J].Journal of Applied Sciences,2010,10(24):3183-3190.
[2]MCKENDRY P.Energy production from biomass(Part 3):gasification technologies[J].Bioresource Technology,2002,83(1):55.
[3]阴秀丽,常杰,汪俊锋,等.生物质合成气合成甲醇[J].太阳能学报,2005,26(4):518-522.YIN Xiuli,CHANG Jie,WANG Junfeng,et al.Biomass syngas the methanol synthesis from biomass-derived syngas[J].Acta Energiae Solaris Sinica,2005,26(4):518-522.
[4]蓝平,蓝丽红,谢涛,等.生物质合成气制备及合成液体燃料研究进展[J].化学世界,2011,52(7):437-441.LAN Ping,LAN Lihong,XIE Tao,et al.Progress of biomass-syngas production and synthetic liquid fuels from biomass-syngas[J].Chemical World,2011,52(7):437-441
[5]MUNASINGHE P C,KHANAL S K.Chapter 4:Biomass-derived syngas fermentation into biofuels[M]//Biofuels.Amsterdam:Elsevier,2011:79-98.
[6]SCHUSTER G,LOFFER G,WEIGL K,et al.Biomass steam gasification--an extensive parametric modeling study[J].Bioresource Technology,2001,77(1):71-79.
[7]李琳娜,应浩,涂军令,等.木屑高温水蒸气气化制备富氢燃气的特性研究[J].林产化学与工业,2011,31(5):18-24.LI Linna,YING Hao,TU Junling,et al.High-temperature steam gasification of sawdust for production of hydrogen-rich gas[J].Chemistry and Industry of Forest Products,2011,31(5):18-24.
[8]涂军令,应浩,吴欢,等.生物质炭水蒸气气化制取合成气[J].太阳能学报,2013,34(9):1514-1519.TU Junling,YING Hao,WU Huan,et al.Production of synthesis gas by steam gasification of biomass-derived char[J].Acta Energiae Solaris Sinica,2013,34(9):1514-1519.
[9]贾爽,应浩,孙云娟,等.生物质水蒸气气化制取富氢合成气及其应用的研究进展[J].化工进展,2018,37(2):497-504.JIA Shuang,YING Hao,SUN Yunjuan,et al.Research advance in biomass steam gasification for hydrogen-rich syngas and its application[J].Chemical Industry and Engineering Progress,2018,37(2):497-504.
[10]NZIHOU A,STANMORE B,SHARROCK P.A review of catalysts for the gasification of biomass char,with some reference to coal[J].Energy,2013,58(3):305-317.
[11]PERONDI D,POLETTO P,RESTELATTO D,et al.Steam gasification of poultry litter biochar for bio-syngas production[J].Process Safety&Environmental Protection,2017,109:478-488.
[12]FENG Y,ZHANG L,HU Z,et al.Hydrogen-rich gas production by steam gasification of char derived from cyanobacterial blooms(CDCB)in a fixed-bed reactor:influence of particle size and residence time on gas yield and syngas composition[J].International Journal of Hydrogen Energy,2010,35(19):10212-10217.
[13]YAN F,LUO S Y,HU Z Q,et al.Hydrogen-rich gas production by steam gasification of char from biomass fast pyrolysis in a fixed-bed reactor:influence of temperature and steam on hydrogen yield and syngas composition[J].Bioresource Technology,2010,101(14):5633-5637.
[14]YAN L,CAO Y,He B.On the kinetic modeling of biomass/coal char co-gasification with steam[J].Chemical Engineering Journal,2018,331:435-442.
[15]HUHN F,KLEIN J,JUNTGEN H.Investigations on the alkalicatalysed steam gasification of coal:kinetics and interactions of alkali catalyst with carbon[J].Fuel,1983,62(2):196-199.
[16]CHEN Z,DUN Q,SHI Y,et al.High quality syngas production from catalytic coal gasification using disposable Ca(OH)2,catalyst[J].Chemical Engineering Journal,2017,316:842-849.
[17]孙立.生物质热解气化原理与技术[M].北京:化学工业出版社,2013.SUN Li.Theory and technology of biomass pyrolysis and gasification[M].Beijing:Chemical Industry Press,2013.
[18]WAHEED Q M K,WU C,WILLIAMS P T.Hydrogen production from high temperature steam catalytic gasification of bio-char[J].Journal of the Energy Institute,2015,89(2):222-230.
[19]NANOU P,MURILLO H E G,SWAAIJ W P M V,et al.Intrinsic reactivity of biomass-derived char under steam gasification conditions-potential of wood ash as catalyst[J].Chemical Engineering Journal,2013,217(2):289-299.
[20]张报安,黄河,金玳.用动力学参数对炭气化催化剂性能的表征[J].大连理工大学学报,1985(2):9-15.ZHANG Bao’an,HUANG He,JIN Dai.Characterization of carbon gasification catalysts by kinetic parameters[J].Journal of Dalian University of Technology,1985(2):9-15.
[21]SHANG J Y,WOLF E E.FTIR studies of potassium catalyst-treated gasified coal chars and carbons[J].Fuel,1983,62(2):252-255.
[22]HUTTINGER K J,MINGES R.Water vapour gasification of carbon:Improved catalytic activity of potassium chloride using anion exchange[J].Fuel,1985,64(4):486-490.
[23]王永刚,谢克昌,凌开成,等.碱金属催化剂在煤气化过程中的作用机理[J].太原理工大学学报,1988(3):55-65.WANG Yonggang,XIE Kechang,LING Kaicheng,et al.Action mechanism of alkali metal catalysis in the gasification of coal/char[J].Journal of Taiyuan University of Technology,1988(3):55-65.
[24]SAMS D A,TALVERDIAN T,SHADMAN F.Kinetics of catalyst loss during potassium-catalyzed CO2gasification of carbon[J].Fuel,1985,64(9):1208-1214.
[25]GUERRA L,ROSSI S,RODEIGUES J,et al.Methane production by a combined Sabatier reaction/water electrolysis process[J].Journal of Environmental Chemical Engineering,2017,6(1):671.
[26]INAYAT A,AHMAD M M,MUTALIB M I A,et al.Effect of process parameters on hydrogen production and efficiency in biomass gasification using modelling approach[J].Journal of Applied Sciences,2010,10(24):3183-3190.