Cu-Zn-Al基催化剂制备及催化等离子体转化甲烷制甲醇
|
摘要
为了探讨催化剂对低温等离子体转化甲烷制甲醇的影响,将Cu-Zn-Al基催化剂引入介质阻挡放电系统,进行了甲烷等离子体-催化制甲醇的研究,考察了催化剂填装方式、催化剂载体、催化剂助剂对甲醇生成的影响。结果表明,将催化剂负载在堇青石蜂窝陶瓷上(Cu-Zn-Al/HC)的填装方式可获得较好的催化效果;堇青石表面结构对甲醇的生成具有显著影响,将催化剂负载在经酸蚀处理的堇青石蜂窝陶瓷上(Cu-Zn-Al/HC-AE),可使单位能耗甲醇产量提高28%;在催化剂中添加助剂Ce利于甲醇的生成,应用Cu-Zn-Al-Ce/HC-AE催化剂时,单位能耗甲醇最大产量较单纯等离子体体系提高了183.7%。基于等离子体-催化甲烷反应结果和发射光谱原位诊断,推断等离子体与催化剂协同转化甲烷制甲醇反应中甲醇通过自由基反应和费托合成两条途径生成。
In order to investigate catalyst effects on methane conversion to methanol by low-temperature plasma, dielectric barrier discharge plasma combined with Cu-Zn-Al-based catalysts was applied. Effects of catalyst filling mode, catalyst carrier and catalyst auxiliaries on methanol formation were investigated. The results show that the catalyst loaded on cordierite honeycomb ceramics(Cu-Zn-Al/HC) exhibits excellent catalytic activity. The surface structure of cordierite has a significant effect on methanol formation. A Cu-Zn-Al/HC-AE catalyst was prepared by loading the Cu-Zn-Al catalyst on cordierite honeycomb ceramics after acid etching, and methanol productivity was increased by 28% per unit energy consumption. Addition of Ce into catalysts can facilitate methanol formation, and the maximum methanol productivity is increased by 183.7% compared with pure plasma system. The results of plasma-catalyst reaction and emission spectrum in situ diagnosis indicate that methanol is formed through approaches of free radical reaction and Fischer-Tropsch synthesis.
In order to investigate catalyst effects on methane conversion to methanol by low-temperature plasma, dielectric barrier discharge plasma combined with Cu-Zn-Al-based catalysts was applied. Effects of catalyst filling mode, catalyst carrier and catalyst auxiliaries on methanol formation were investigated. The results show that the catalyst loaded on cordierite honeycomb ceramics(Cu-Zn-Al/HC) exhibits excellent catalytic activity. The surface structure of cordierite has a significant effect on methanol formation. A Cu-Zn-Al/HC-AE catalyst was prepared by loading the Cu-Zn-Al catalyst on cordierite honeycomb ceramics after acid etching, and methanol productivity was increased by 28% per unit energy consumption. Addition of Ce into catalysts can facilitate methanol formation, and the maximum methanol productivity is increased by 183.7% compared with pure plasma system. The results of plasma-catalyst reaction and emission spectrum in situ diagnosis indicate that methanol is formed through approaches of free radical reaction and Fischer-Tropsch synthesis.
引文
[1]DONG Xiao-su(董晓素),LI Feng(李枫),ZHAO Ning(赵宁),et al.CO2 hydrogenation to methanol over Cu/Zn/Al/Zr catalysts prepared by liquid reduction(液相还原法制备Cu/Zn/Al/Zr催化剂用于CO2加氢合成甲醇)[J].Chinese Journal of Catalysis(催化学报),2017,38(4):717-725.
[2]Olah G A,Goeppert A,Prakash G K S.Chemical recycling of carbon dioxide to methanol and dimethyl ether:from greenhouse gas to renewable,environmentally carbon neutral fuels and synthetic hydrocarbons[J].Journal of Organic Chemistry,2009,74(2):487-498.
[3]Olah G A,Prakash G K S,Goeppert A.Anthropogenic chemical carbon cycle for a sustainable future[J].Journal of the American Chemical Society,2011,133(33):12881-12898.
[4]Aasberg-Petersen K,Bak Hansen J H,Christensen T S,et al.Technologies for large-scale gas conversion[J].Applied Catalysis A:General,2001,221(1-2):379-387.
[5]XU Feng(徐锋),LI Chuang(李创),ZHU Li-hua(朱丽华).Study on activation and conversion of methane using non-thermal plasma(低温等离子体促进煤层甲烷活化转化)[J].Journal of Heilongjiang University of Science&Technology(黑龙江科技大学学报),2015,25(6):597-601.
[6]SHAO Tao(邵涛),ZHANG Cheng(章程),WANG Rui-xue(王瑞雪),et al.Atmospheric-pressure pulsed gas discharge and pulsed plasma application(大气压脉冲气体放电与等离子体应用)[J].High Voltage Engineering(高电压技术),2016,42(3):685-705.
[7]LI Ming-shu(李铭书),LI Sheng-li(李胜利),LI Dong(李东),et al.Experimental study of the synergistic effect of catalyst and pulsed discharge plasma on removal of dimethyl sulfide(催化剂协同脉冲放电等离子体处理甲硫醚气体的实验研究)[J].High Voltage Engineering(高电压技术),2016,42(2):462-467.
[8]WU Zu-liang(吴祖良),ZHU Zhou-bin(朱周彬),ZHANG Xu-ming(章旭明),et al.Study on n-decane removal by plasma assisted noble metal catalysis(等离子体强化贵金属催化净化正葵烷的研究)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2017,31(6):1452-1458.
[9]Mahammadunnisa S K,Krushnamurty K,Subrahmanyam C H.Catalytic nonthermal plasma assisted co-processing of methane and nitrous oxide for methanol production[J].Catalysis Today,2015,256(part1):102-107.
[10]Indarto A.Partial oxidation of methane to methanol with nitrogen dioxide in dielectric barrier discharge plasma:experimental and molecular modeling[J].Plasma Sources Science and Technology,2016,25(2):25002.
[11]Chen L,Zhang X W,Huang L,et al.Partial oxidation of methane with air for methanol production in a post-plasma catalytic system[J].Chemical Engineering and Processing.2009,48(8):1333-1340.
[12]Chen L,Zhang X W,Huang L,et al.Post-plasma catalysis for methane partial oxidation to methanol:role of copper promoted iron oxide catalyst[J].Chemical Engineering&Technology,2010,33(12):2073-2081.
[13]Chen L,Zhang X W,Huang L,et al.Application of in-plasma catalysis and post-plasma catalysis for methane partial oxidation to methanol over a Fe2O3-Cu O/γ-Al2O3 catalyst[J].Journal of Natural Gas Chemistry,2010,19(6):628-637.
[14]Huang L,Zhang X W,Chen L,et al.Direct oxidation of methane to methanol over Cu-based catalyst in an AC dielectric barrier discharge[J].Plasma Chem Plasma Process,2011,31(1):67-77.
[15]Indarto A,Song H K.Partial oxidation of methane with Cu-Zn-Al catalyst in a dielectric barrier discharge[J].Chemical Engineering and Processing,2008,47(5):780-786.
[16]Lau S P,Chen L,Lin J,et al.Synergism between Cu and Zn sites in Cu/Zn catalysts for methanol synthesis[J].Applied Surface Science,1999,152(3-4):193-199.
[17]Indarto A.Methanol synthesis from methane and oxygen with[Ga Cr]/Cu-Zn-Al catalyst in a dielectric barrier discharge[J].Ionics,2014,20(3):445-449.
[18]LI Zhi-xiong(李志雄),NA Wei(纳薇),WANG Hua(王华),et al.Direct syntheses of Cu-Zn-Zr/SBA-15 mesoporous catalysts for CO2 hydrogenation to methanol(Cu-Zn-Zr/SBA-15介孔催化剂的制备及CO2加氢合成甲醇的催化性能)[J].Chemical Journal of Chinese Universities(高等学校化学学报),2014,35(12):2616-2623.
[19]ZHAO Jiu-sheng(赵九生),CHEN Bao-shu(陈宝树),MA Fu-shan(马福善),et al.The effects of the composition of a Cu-based catalyst for methanol systhesis on its structure and property(合成甲醇Cu-Zn-Al催化剂中组成对其结构及催化性能的影响)[J].Journal of Chemical Industry and Engineering(China)(化工学报),1988,39(5):562-569.
[20]NI Wen(倪文),CHEN Na-na(陈娜娜).Advance in the study of cordierite mineralogy—I.Structure and composition of cordierite(堇青石矿物学研究进展—I堇青石的结构与化学成分)[J].Journal of Mineralogy and Petrolog(矿物岩石),1996,16(4):12.
[21]LU Gui-zeng(路贵增),LEI Ze(雷泽),ZHAO Hao-ying(赵昊鹰),et al.Preparation and catalytic activities of lanthanum strontium manganite based catalysts supported on honeycomb ceramics(蜂窝陶瓷负载锰酸锶镧基催化剂制备及性能)[J].Clean Coal Technology(洁净煤技术),2014,20(6):104-108.
[22]Mazzocchia C,Gronchi P,Kaddouri A,et al.Hydrogenation of CO over Rh/Si O2-Ce O2 catalysts:kinetic evidences[J].Journal of Molecular Catalysis A:Chemical,2001,165(1-2):219-230.
[23]SHI Li-min(士丽敏),CHU Wei(储伟),XU Hui-yuan(徐慧远),et al.Effect of Ce addition on the structure and properties of Cu Co oxide catalyst(稀土Ce对Cu Co氧化物催化剂结构与性能的影响)[J].Rare Metal Materials and Engineering(稀有金属材料与工程),2009,38(8):1382-1385.
[24]MAO Dong-sen(毛东森),GUO Sheng-qiang(郭胜强),YU Jun(俞俊),et al.Effect of cerium addition on the catalytic performance of Cu-Fe/Si O2 for the synthesis of lower alcohols from syngas(Ce添加对Cu-Fe/Si O2催化合成气制低碳醇性能的影响)[J].Acta Physico-Chimica Sinica(物理化学学报),2011,27(11):2639-2645.
[25]Okumoto M,Kim H H,Takashima K,et al.Reactivity of methane in nonthermal plasma in the presence of oxygen and inert gases at atmospheric pressure[J].IEEE Trangactions on Industry Applications,2001,37(6):1618-1624.
[26]Yao S L,Takemoto T,Ouyang F,et al.Selective oxidation of methane using a non-thermal pulsed plasma[J].Energy Fuels,2000,14(2):459-463.
[27]QIN Kun-yuan(丘坤元).Progress of free radical polymerization in recent years(自由基聚合近20年的发展)[J].Polymer Bulletin(高分子通报),2008,21(7):15-28.
[28]LI Jin-ping(李金平),DAI Bin(代斌),FAN Ting(范婷).Study on optical emission spectroscopy of pulse corona methane plasma(甲烷电离特性的等离子体发射光谱法研究)[J].Spectroscopy and Spectral Analysis(光谱学与光谱分析),2009,29(7):1979
[29]WU Li-feng(吴利峰).Emission spectroscopy diagnosis of hydrogen microwave plasma(微波氢等离子体发射光谱诊断)[D].Wuhan(武汉):Wuhan Institute of Technology(武汉工程大学),2010.
[2]Olah G A,Goeppert A,Prakash G K S.Chemical recycling of carbon dioxide to methanol and dimethyl ether:from greenhouse gas to renewable,environmentally carbon neutral fuels and synthetic hydrocarbons[J].Journal of Organic Chemistry,2009,74(2):487-498.
[3]Olah G A,Prakash G K S,Goeppert A.Anthropogenic chemical carbon cycle for a sustainable future[J].Journal of the American Chemical Society,2011,133(33):12881-12898.
[4]Aasberg-Petersen K,Bak Hansen J H,Christensen T S,et al.Technologies for large-scale gas conversion[J].Applied Catalysis A:General,2001,221(1-2):379-387.
[5]XU Feng(徐锋),LI Chuang(李创),ZHU Li-hua(朱丽华).Study on activation and conversion of methane using non-thermal plasma(低温等离子体促进煤层甲烷活化转化)[J].Journal of Heilongjiang University of Science&Technology(黑龙江科技大学学报),2015,25(6):597-601.
[6]SHAO Tao(邵涛),ZHANG Cheng(章程),WANG Rui-xue(王瑞雪),et al.Atmospheric-pressure pulsed gas discharge and pulsed plasma application(大气压脉冲气体放电与等离子体应用)[J].High Voltage Engineering(高电压技术),2016,42(3):685-705.
[7]LI Ming-shu(李铭书),LI Sheng-li(李胜利),LI Dong(李东),et al.Experimental study of the synergistic effect of catalyst and pulsed discharge plasma on removal of dimethyl sulfide(催化剂协同脉冲放电等离子体处理甲硫醚气体的实验研究)[J].High Voltage Engineering(高电压技术),2016,42(2):462-467.
[8]WU Zu-liang(吴祖良),ZHU Zhou-bin(朱周彬),ZHANG Xu-ming(章旭明),et al.Study on n-decane removal by plasma assisted noble metal catalysis(等离子体强化贵金属催化净化正葵烷的研究)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2017,31(6):1452-1458.
[9]Mahammadunnisa S K,Krushnamurty K,Subrahmanyam C H.Catalytic nonthermal plasma assisted co-processing of methane and nitrous oxide for methanol production[J].Catalysis Today,2015,256(part1):102-107.
[10]Indarto A.Partial oxidation of methane to methanol with nitrogen dioxide in dielectric barrier discharge plasma:experimental and molecular modeling[J].Plasma Sources Science and Technology,2016,25(2):25002.
[11]Chen L,Zhang X W,Huang L,et al.Partial oxidation of methane with air for methanol production in a post-plasma catalytic system[J].Chemical Engineering and Processing.2009,48(8):1333-1340.
[12]Chen L,Zhang X W,Huang L,et al.Post-plasma catalysis for methane partial oxidation to methanol:role of copper promoted iron oxide catalyst[J].Chemical Engineering&Technology,2010,33(12):2073-2081.
[13]Chen L,Zhang X W,Huang L,et al.Application of in-plasma catalysis and post-plasma catalysis for methane partial oxidation to methanol over a Fe2O3-Cu O/γ-Al2O3 catalyst[J].Journal of Natural Gas Chemistry,2010,19(6):628-637.
[14]Huang L,Zhang X W,Chen L,et al.Direct oxidation of methane to methanol over Cu-based catalyst in an AC dielectric barrier discharge[J].Plasma Chem Plasma Process,2011,31(1):67-77.
[15]Indarto A,Song H K.Partial oxidation of methane with Cu-Zn-Al catalyst in a dielectric barrier discharge[J].Chemical Engineering and Processing,2008,47(5):780-786.
[16]Lau S P,Chen L,Lin J,et al.Synergism between Cu and Zn sites in Cu/Zn catalysts for methanol synthesis[J].Applied Surface Science,1999,152(3-4):193-199.
[17]Indarto A.Methanol synthesis from methane and oxygen with[Ga Cr]/Cu-Zn-Al catalyst in a dielectric barrier discharge[J].Ionics,2014,20(3):445-449.
[18]LI Zhi-xiong(李志雄),NA Wei(纳薇),WANG Hua(王华),et al.Direct syntheses of Cu-Zn-Zr/SBA-15 mesoporous catalysts for CO2 hydrogenation to methanol(Cu-Zn-Zr/SBA-15介孔催化剂的制备及CO2加氢合成甲醇的催化性能)[J].Chemical Journal of Chinese Universities(高等学校化学学报),2014,35(12):2616-2623.
[19]ZHAO Jiu-sheng(赵九生),CHEN Bao-shu(陈宝树),MA Fu-shan(马福善),et al.The effects of the composition of a Cu-based catalyst for methanol systhesis on its structure and property(合成甲醇Cu-Zn-Al催化剂中组成对其结构及催化性能的影响)[J].Journal of Chemical Industry and Engineering(China)(化工学报),1988,39(5):562-569.
[20]NI Wen(倪文),CHEN Na-na(陈娜娜).Advance in the study of cordierite mineralogy—I.Structure and composition of cordierite(堇青石矿物学研究进展—I堇青石的结构与化学成分)[J].Journal of Mineralogy and Petrolog(矿物岩石),1996,16(4):12.
[21]LU Gui-zeng(路贵增),LEI Ze(雷泽),ZHAO Hao-ying(赵昊鹰),et al.Preparation and catalytic activities of lanthanum strontium manganite based catalysts supported on honeycomb ceramics(蜂窝陶瓷负载锰酸锶镧基催化剂制备及性能)[J].Clean Coal Technology(洁净煤技术),2014,20(6):104-108.
[22]Mazzocchia C,Gronchi P,Kaddouri A,et al.Hydrogenation of CO over Rh/Si O2-Ce O2 catalysts:kinetic evidences[J].Journal of Molecular Catalysis A:Chemical,2001,165(1-2):219-230.
[23]SHI Li-min(士丽敏),CHU Wei(储伟),XU Hui-yuan(徐慧远),et al.Effect of Ce addition on the structure and properties of Cu Co oxide catalyst(稀土Ce对Cu Co氧化物催化剂结构与性能的影响)[J].Rare Metal Materials and Engineering(稀有金属材料与工程),2009,38(8):1382-1385.
[24]MAO Dong-sen(毛东森),GUO Sheng-qiang(郭胜强),YU Jun(俞俊),et al.Effect of cerium addition on the catalytic performance of Cu-Fe/Si O2 for the synthesis of lower alcohols from syngas(Ce添加对Cu-Fe/Si O2催化合成气制低碳醇性能的影响)[J].Acta Physico-Chimica Sinica(物理化学学报),2011,27(11):2639-2645.
[25]Okumoto M,Kim H H,Takashima K,et al.Reactivity of methane in nonthermal plasma in the presence of oxygen and inert gases at atmospheric pressure[J].IEEE Trangactions on Industry Applications,2001,37(6):1618-1624.
[26]Yao S L,Takemoto T,Ouyang F,et al.Selective oxidation of methane using a non-thermal pulsed plasma[J].Energy Fuels,2000,14(2):459-463.
[27]QIN Kun-yuan(丘坤元).Progress of free radical polymerization in recent years(自由基聚合近20年的发展)[J].Polymer Bulletin(高分子通报),2008,21(7):15-28.
[28]LI Jin-ping(李金平),DAI Bin(代斌),FAN Ting(范婷).Study on optical emission spectroscopy of pulse corona methane plasma(甲烷电离特性的等离子体发射光谱法研究)[J].Spectroscopy and Spectral Analysis(光谱学与光谱分析),2009,29(7):1979
[29]WU Li-feng(吴利峰).Emission spectroscopy diagnosis of hydrogen microwave plasma(微波氢等离子体发射光谱诊断)[D].Wuhan(武汉):Wuhan Institute of Technology(武汉工程大学),2010.