生物质催化制备甲烷的反应路径和催化剂研究进展
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摘要
甲烷是氢碳比最高的烃,也是一种具有较高燃烧热值的清洁能源。在生物质制备甲烷的方法中,生物质发酵法和生物质合成气发酵法因活性菌的温度敏感性而受到限制。因此,本文介绍了近年来生物质合成气催化制备甲烷的反应机理及相应的催化剂体系研究进展,重点讨论了合成气中CO甲烷化和CO_2甲烷化反应机理,以及催化剂中活性成分、载体、助剂对甲烷化的影响。同时,介绍了反应条件温和的生物质催化水热法,简述了反应路线及近年来的研究现状。最后,从技术的角度对该甲烷化的反应机理和高效、稳定的催化剂研究进行了展望。
Methane is the hydrocarbon with highest hydrogen-carbon ratio, and is a kind of clean energy with high combustion calorific value as well. During the preparation of methane from biomass, biomass fermentation and biomass syngas fermentation are limited by the temperature sensitivity of active bacteria. This paper introduces the research progress of reaction mechanism and corresponding catalyst system of biomass synthesis gas to methane by chemical catalysts. The reaction mechanism of CO methanation and CO_2 methanation in syngas, as well as the effects of active ingredients, supports and promoters in catalysts on methanation are mainly discussed. At the same time, the catalytic hydrothermal method of biomass with mild reaction conditions is also introduced. The reaction route and research progress in recent years are briefly described. Finally, methanation reaction mechanism and efficient, stable catalysts are perspective remarked from the technical point of view.
Methane is the hydrocarbon with highest hydrogen-carbon ratio, and is a kind of clean energy with high combustion calorific value as well. During the preparation of methane from biomass, biomass fermentation and biomass syngas fermentation are limited by the temperature sensitivity of active bacteria. This paper introduces the research progress of reaction mechanism and corresponding catalyst system of biomass synthesis gas to methane by chemical catalysts. The reaction mechanism of CO methanation and CO_2 methanation in syngas, as well as the effects of active ingredients, supports and promoters in catalysts on methanation are mainly discussed. At the same time, the catalytic hydrothermal method of biomass with mild reaction conditions is also introduced. The reaction route and research progress in recent years are briefly described. Finally, methanation reaction mechanism and efficient, stable catalysts are perspective remarked from the technical point of view.
引文
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[2] 王建楠,胡志超,彭宝良,等.我国生物质气化技术概况与发展[J].农机化研究,2010,32(1):198-201.WANG J N,HU Z C,PENG B L,et al.General situation and development of biomass gasification technology in China[J].Journal of Agricultural Mechanization Research,2010,32(1):198-201.
[3] PANAGIOTOPOULOU P,KONDARIDES D I,VERYKIOS X E.Mechanistic study of the selective methanation of CO over Ru/TiO2 catalyst:Identification of active surface species and reaction pathways[J].The Journal of Physical Chemistry C,2011,115(4):1220-1230.
[4] TISON Y,NIELSIN K,MOWBRAY D J,et al.Scanning tunneling microscopy evidence for the dissociation of carbon monoxide on ruthenium steps[J].The Journal of Physical Chemistry C,2012,116(27):14350-14359.
[5] ENGBAEK J,LYTKEN O,NIELSEN J H,et al.CO dissociation on Ni:The effect of steps and of nickel carbonyl[J].Surface Science,2008,602(3):733-743.
[6] ECKLE S,ANFANG H G,BEHM R J.Reaction intermediates and side products in the methanation of CO and CO2 over supported Ru catalysts in H2-rich reformate gases[J].The Journal of Physical Chemistry C,2011,115(4):1361-1367.
[7] ANDERSSON M P,ABILD-PEDERSEN F,REMEDIAKIS I N,et al.Structure sensitivity of the methanation reaction:H2-induced CO dissociation on nickel surfaces[J].Journal of Catalysis,2008,255(1):6-19.
[8] MIAO B,MA S S K,WANG X,et al.Catalysis mechanisms of CO2 and CO methanation[J].Catalysis Science & Technology,2016,6(12):4048-4058.
[9] LEITENBURG C D,TROVARELLI A,KA?PAR J.A temperature-programmed and transient kinetic study of CO2 activation and methanation over CeO2 supported noble metals[J].Journal of Catalysis,1997,166(1):98-107.
[10] AKAMARU S,SHIMAZAKI T,KUBO M,et al.Density functional theory analysis of methanation reaction of CO2 on Ru nanoparticle supported on TiO2(101)[J].Applied Catalysis A:General,2014,470:405-411.
[11] ALADNA P A U,OCAMPO F,KOBL K,et al.Catalytic CO2 valorization into CH4 on Ni-based ceria-zirconia.Reaction mechanism by operando IR spectroscopy[J].Catalysis Today,2013,215:201-207.
[12] UPHAM D C,DERK A R,SHARMA S,et al.CO2 methanation by Ru-doped ceria:The role of the oxidation state of the surface[J].Catalysis Science & Technology,2015,5(3):1783-1791.
[13] HWANG S,LEE J,HONG U G,et al.Methane production from carbon monoxide and hydrogen over nickel-alumina xerogel catalyst:Effect of nickel content[J].Journal of Industrial and Engineering Chemistry,2011,17(1):154-157.
[14] ZHANG G Q,SUN T J,PENG J X,et al.A comparison of Ni/SiC and Ni/Al2O3 catalyzed total methanation for production of synthetic natural gas[J].Applied Catalysis A:General,2013,462/463:75-81.
[15] HU D C,GAO J J,PING Y,et al.Enhanced investigation of CO methanation over Ni/Al2O3 catalysts for synthetic natural gas production[J].Industrial & Engineering Chemistry Research,2012,51(13):4875- 4886.
[16] SHINDE V M,MADRAS G.CO methanation toward the production of synthetic natural gas over highly active Ni/TiO2 catalyst[J].AIChE Journal,2014,60(3):1027-1035.
[17] LI P P,ZHU M Y,DAN J M,et al.Two-dimensional porous SiO2 nanomesh supported high dispersed Ni nanoparticles for CO methanation[J].Chemical Engineering Journal,2017,326:774-780.
[18] CHEN X,JIN J H,SHA G Y,et al.Silicon-nickel intermetallic compounds supported on silica as a highly efficient catalyst for CO methanation[J].Catalysis Science & Technology,2014,4(1):53-61.
[19] ZHANG J Y,XIN Z,MENG X,et al.Effect of MoO3 on the heat resistant performances of nickel based MCM-41 methanation catalysts[J].Fuel,2014,116:25-33.
[20] HWANG S,LEE J,HING U G,et al.Hydrogenation of carbon monoxide to methane over mesoporous nickel-M-alumina(M= Fe,Ni,Co,Ce,and La) xerogel catalysts[J].Journal of Industrial and Engineering Chemistry,2012,18(1):243-248.
[21] 周龙,马丽萍,陈建涛,等.Ni/γ-Al2O3对二氧化碳加氢甲烷化的催化活性研究[J].化学世界,2015,56(1):16-21.ZHOU L,MA L P,CHEN J T,et al.Study on catalytic activety of Ni/γ-Al2O3 for CO2 methanation by hydrogenation[J].Chemical World,2015,56(1):16-21.
[22] AZIZ M A A,JALIL A A,TRIWAHYONO S,et al.Highly active Ni-promoted mesostructured silica nanoparticles for CO2 methanation[J].Applied Catalysis B:Environmental,2014,147:359-368.
[23] LIU J,LI C M,WANG F,et al.Enhanced low-temperature activity of CO2 methanation over highly-dispersed Ni/TiO2 catalyst[J].Catalysis Science & Technology,2013,3(10):2627-2633.
[24] ZHOU G L,LIU H R,CUI K K,et al.Methanation of carbon dioxide over Ni/CeO2 catalysts:Effects of support CeO2 structure[J].International Journal of Hydrogen Energy,2017,42(25):16108-16117.
[25] ZHEN W L,LI B,LU G X,et al.Enhancing catalytic activity and stability for CO2 methanation on Ni@MOF-5 via control of active species dispersion[J].Chemical Communications,2015,51(9):1728-1731.
[26] TADA S,OCHIENG O J,KIKUCHI R,et al.Promotion of CO2 methanation activity and CH4 selectivity at low temperatures over Ru/CeO2/Al2O3 catalysts[J].International Journal of Hydrogen Energy,2014,39(19):10090-10100.
[27] RAHMANI S,REZAEI M,MESHKANI F.Preparation of highly active nickel catalysts supported on mesoporous nanocrystalline γ-Al2O3 for CO2 methanation[J].Journal of Industrial and Engineering Chemistry,2014,20(4):1346-1352.
[28] 周龙,马华菊.暴玮.La-Ni/γ-Al2O3对二氧化碳加氢甲烷化的催化活性研究[J].化工技术与开发,2018,47(6):11-13.ZHOU L,MA H J,BAO W,et al.Study on La-Ni/γ-Al2O3 catalytic hydrogenation of carbon dioxide for methane[J].Technology & Development of Chemical Industry,2018,47(6):11-13.
[29] GUO M,LU G X.The regulating effects of cobalt addition on the catalytic properties of silica-supported Ni-Co bimetallic catalysts for CO2 methanation[J].Reaction Kinetics,Mechanisms and Catalysis,2014,113(1):101-113.
[30] SOLIS-GARCIA A,FIERRO-GONZALEZ J C.Mechanistic insights into the CO2 methanation catalyzed by supported metals:A review[J].Journal of Nanoscience and Nanotechnology,2019,19(6):3110-3123.
[31] RAHMANI S,REZAEI M,MESHKANI F.Preparation of promoted nickel catalysts supported on mesoporous nanocrystalline gamma alumina for carbon dioxide methanation reaction[J].Journal of Industrial and Engineering Chemistry,2014,20(6):4176-4182.
[32] HE L,LIN Q Q,LIU Y,et al.Unique catalysis of Ni-Al hydrotalcite derived catalyst in CO2 methanation:Cooperative effect between Ni nanoparticles and a basic support[J].Journal of Energy Chemistry,2014,23(5):587-592.
[33] GRA?A I,GONZáLEZ L V,BACARIZA M C,et al.CO2 hydrogenation into CH4 on NiHNaUSY zeolites[J].Applied Catalysis B:Environmental,2014,147:101-110.
[34] RIVERO-MENDOZA D E,STANLEY J N G,SCOTT J,et al.An alumina-supported Ni-La-based catalyst for producing synthetic natural gas[J].Catalysts,2016,6(11):170-173.
[35] YUAN C K,YAO N,WANG X D,et al.The SiO2 supported bimetallic Ni-Ru particles:A good sulfur-tolerant catalyst for methanation reaction[J].Chemical Engineering Journal,2015,260:1-10.
[36] LI T,WANG S,GAO D N,et al.Effect of support calcination temperature on the catalytic properties of Ru/Ce0.8Zr0.2O2 for methanation of carbon dioxide[J].Journal of Fuel Chemistry and Technology,2014,42(12):1440-1446.
[37] GARBARINO G,BELLOTTI D,RIANI P,et al.Methanation of carbon dioxide on Ru/Al2O3 and Ni/Al2O3 catalysts at atmospheric pressure:Catalysts activation,behaviour and stability[J].International Journal of Hydrogen Energy,2015,40(30):9171-9182.
[38] SHARMA S,HU Z P,ZHANG P,et al.CO2 methanation on Ru-doped ceria[J].Journal of Catalysis,2011,278(2):297-309.
[39] XU J H,LIN Q Q,SU X,et al.CO2 methanation over TiO2-Al2O3 binary oxides supported Ru catalysts[J].Chinese Journal of Chemical Engineering,2016,24(1):140-145.
[40] ZAMANI A H,ALI R,ABU BAKAR W A W.Optimization of CO2 methanation reaction over M*/Mn/Cu-Al2O3(M*:Pd,Rh and Ru) catalysts[J].Journal of Industrial and Engineering Chemistry,2015,29:238-248.
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