CO_2催化加氢制甲醇进展
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摘要
CO_2的大量排放给人类生存环境带来威胁的同时也造成资源的严重浪费,实现资源→CO_2→资源的可持续循环是解决该问题的理想途径,因此,CO_2加氢制甲醇倍受关注。国外完成中试试验,国内仍处于小试阶段。受CO_2富集及H_2制取成本的限制,CO_2加氢制甲醇技术须利用先进技术与可再生资源获得廉价的原料气。Cu-Zn系催化剂为有工业化前景的CO_2加氢制甲醇催化剂,但存在活性与选择性差的问题,未来活性组分高度分散和具有高比表面积的纳米催化材料的研制是比较可行的研究思路。
A great deal of CO_2 emission has caused a threat to human survival environments and a waste of resources. The implementation of resources→CO_2→resources continuous circulation is an ideal way to solve the problem. Therefore,methanol synthesis from CO_2 hydrogenation has attracted much attention. Its pilot scale test was completed abroad,however the experimental stage was still going on at home. Because of being restricted by the cost of CO_2 enrichment and H_2 preparation,the technology of methanol synthesis from CO_2 hydrogenation should made use of advanced technology and renewable resources to acquire cheap raw material gases. Although their activity and selectivity were not good enough,Cu-Zn catalysts had the best industrialization prospects for methanol synthesis from CO_2 hydrogenation. It is a relatively feasible research idea that nanometer catalytic materials with a high specific surface area and highly dispersed active component are prepared.
A great deal of CO_2 emission has caused a threat to human survival environments and a waste of resources. The implementation of resources→CO_2→resources continuous circulation is an ideal way to solve the problem. Therefore,methanol synthesis from CO_2 hydrogenation has attracted much attention. Its pilot scale test was completed abroad,however the experimental stage was still going on at home. Because of being restricted by the cost of CO_2 enrichment and H_2 preparation,the technology of methanol synthesis from CO_2 hydrogenation should made use of advanced technology and renewable resources to acquire cheap raw material gases. Although their activity and selectivity were not good enough,Cu-Zn catalysts had the best industrialization prospects for methanol synthesis from CO_2 hydrogenation. It is a relatively feasible research idea that nanometer catalytic materials with a high specific surface area and highly dispersed active component are prepared.
引文
[1]2014年二氧化碳减排与利用行业分析[EB/OL].[2014-08-26].http://www.doc88.com/p-5364167323774.html.
[2]连普琛,郭岩,拾静漪.CO2催化加氢研究进展[J].内蒙古石油化工,2015,(1):27-28.
[3]张丽平.甲醇生产技术新进展[J].天然气化工(C1化学与化工),2013,38(1):89-94.Zhang Liping.Recent progress in methanol production technology[J].Natural Gas Chemical Industry,2013,38(1):89-94.
[4]Olah G A,Goeppert A,Prakash G K S.跨越油气时代:甲醇经济[M].胡金波,译.北京:化学工业出版社,2007.
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[6]王献红,王佛松.二氧化碳的固定和利用[M].北京:化学工业出版社,2011:67-72.
[7]黄诚.甲醇生产技术研究最新进展[J].乙醛醋酸化工,2015,(1):25-27.
[8]苗方,高红.二氧化碳加氢制甲醇研究进展[J].化工设计通讯,2014,40(2):53-56.Miao Fang,Gao Hong.The research developments of CO2hydrogenation to prepare methanol[J].Chemical Engineering Design Communications,2014,40(2):53-56.
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[10]黄诚.二氧化碳加氢制甲醇研发进展[J].乙醛醋酸化工,2015,(2):31-33.
[11]那和保志.温室气体再生化学资源——为了持续不断发展三井化学的挑战[R].天津:亚洲石化科技大会,2011.
[12]许文娟,马丽萍,黄彬,等.CO2催化加氢研究进展[J].化工进展,2009,28(z1):284-289.
[13]凌华招,张晓阳,胡志彪,等.C312型中低压甲醇合成催化剂[J].天然气化工(C1化学与化工),2009,34(6):54-58.Ling Huazhao,Zhang Xiaoyang,Hu Zibiao,et al.C312 catalyst for methanol synthesis at low or medium pressure[J].Natural Gas Chemical Industry,2009,34(6):54-58.
[14]张晓阳,胡志彪,凌华招,等.二氧化碳加氢合成甲醇催化剂及工艺研究开发[J].天然气化工(C1化学与化工),2011,36(6):45-49.Zhang Xiaoyang,Hu Zibiao,Lin Huazhao,et al.Research and development of the catalyst and process for hydrogenation of carbon dioxide to methanol[J].Natural Gas Chemical Industry,2011,36(6):45-49.
[15]An X,Ren F,Li J L,et al.A Highly active Cu/Zn O/Al2O3nanofiber catalyst for methanol synthesis through CO2and CO hydrogenation[J].Chinese Journal of Catalysis,2005,26(9):729-730.
[16]王丹君,陶芙蓉,赵华华,等.Cu/Zn O/Al2O3催化剂的共沉淀-蒸氨法制备及其对二氧化碳加氢制甲醇的研究[J].分子催化,2011,25(2):124-129.Wang Danjun,Tao Furong,Zhao Huahua,et al.Preparation of Cu/Zn O/Al2O3catalyst via coprecipition-amonia evaporation for methanol synthesis from CO2and H2[J].Journal of Molecular Catalysis,2011,25(2):124-129.
[17]吴瑛,吴彬福,王海涛,等.Mn助剂对CO2加氢合成甲醇催化剂Cu/Zn/Al2O3的改性作用[J].浙江师范大学学报(自然科学版),2008,31(1):55-59.Wu Ying,Wu Binfu,Wang Haitao,et al.Effect of Mn on the Cu/Zn/Al2O3catalyst of methanol synthesis[J].Journal of Zhejiang Normal University(Natural Sciences),2008,31(1):55-59.
[18]马晓然,王康军,吴静.Cu-Zn O-Al2O3-Zr O2催化二氧化碳加氢合成甲醇的研究[J].沈阳化工大学学报,2012,26(4):314-317.Ma Xiaoran,Wang Kangjun,Wu Jing.Synthesis of methanol from CO2hydrogenation over Cu-Zn O-Al2O3-Zr O2catalyst[J].Journal of Shenyang University of Chemical Technology,2012,26(4):314-317.
[19]Arena F,Barbera K,Italiano G,et al.Synthesis,characterization and activity pattern of Cu-Zn O/Zr O2catalysts in the hydrogenation of carbon dioxide to methanol[J].Journal of Catalysis,2007,249(2):185-194.
[20]Raudaskoski R,Niemela M V,Keisi R L.The effect of ageing time on co-precipitated Cu/Zn O/Zr O2catalysts used in methanol synthesis from CO2and H2[J].Topics in Catalysis,2007,45(1/4):57-60.
[21]Guo X M,Mao D S,Wang S,et al.Combustion synthesis of CuO-Zn O-Zr O2catalysts for the hydrogenation of carbon dioxide to methanol[J].Catalysis Communications,2009,10(13):1661-1664.
[22]常琴琴,赵博,杨萌,等.Cu/Zn比对CuO/Zn O/Zr O2催化CO2加氢合成甲醇性能的影响[J].化学工程,2015,43(5):58-63.Chang Qinqin,Zhao Bo,Yang Meng,et al.Effect of Cu/Zn on performance of catalysts for methanol synthesis from CO2hydrogenation[J].Chemical Engineering(China),2015,43(5):58-63.
[23]郭晓明,毛东森,卢冠忠,等.Zn O对CO2加氢制甲醇用CuO-Zr O2催化剂性能的影响[J].上海应用技术学院学报(自然科学版),2013,13(4):259-263.Guo Xiaoming,Mao Dongsen,Lu Guanzhong,et al.The influence of Zn O on the performance of CuO-Zr O2for methanol synthesis via CO2hydrogenation[J].Journal of Shanghai Institute of Technology(Natural Science),2013,13(4):259-263.
[24]赵云鹏,贾丽华,孙德智,等.CO2加氢合成甲醇CuOZn O-Ti O2催化剂的制备与表征[J].天然气化工,2011,36(5):17-20.Zhao Yunpeng,Jia Lihua,Sun Dezhi,et al.Preparation and characterization of CuO-Zn O-Ti O2catalyst for methanol synthesis from carbon dioxide hydrogenation[J].Natural Gas Chemical Industry,2011,36(5):17-20.
[25]于杨,郝爱香,陈海波,等.Ti O2助剂对Cu-Zn O/Zr O2催化剂催化CO2加氢制甲醇反应性能的影响[J].天然气化工,2011,36(5):17-20.Yu Yang,Hao Aixiang,Chen Haibo,et al.Effect of Ti O2as promoter on catalytic performance of Cu-Zn O/Zr O2in hydrogenation of CO2to methanol[J].Natural Gas Chemical Industry,2011,36(5):17-20.
[26]Jia L S,Gao J,Fang W P,et al.Carbon dioxide hydrogenation to methanol over the pre-reduced La Cr0.5Cu0.5O3catalyst[J].Catalysis Communications,2009,10(15):2000-2003.
[27]李桂英,胡常伟.Fe助剂对CuO/Al2O3催化剂上CO2+H2合成甲醇影响的研究[J].天然气化工,2005,30(3):13-16.Li Guiying,Hu Changwei.The promotion effect of Fe on CuO/Al2O3catalyst for the synthesis of methanol from CO2+H2[J].Natural Gas Chemical Industry,2005,30(3):13-16.
[28]王冠男,陈礼敏,郭园园,等.铬助剂对Cu/Zr O2/CNTsNH2催化剂催化CO2加氢合成甲醇性能的影响[J].物理化学学报,2014,30(5):923-931.Wang Guannan,Chen Limin,Guo Yuanyuan,et al.Effect of chromium doping on the catalytic behavior of Cu/Zr O2/CNTs-NH2for the synthesis of methanol from carbon dioxide hydrogenation[J].Acta Physico-Chimica Sinica,2014,30(5):923-931.
[29]Soczynski J,Grabowski R,Olszewski P,et al.Effect of metal oxide additives on the activity and stability of Cu/Zn O/Zr O2catalysts in the synthesis of methanol from CO2and H2[J].Applied Catalysis A:General,2006,310:127-137.
[30]贾淼尧,高文桂,王华,等.助剂二氧化硅对CO2加氢制备甲醇CuO-Zn O-Al2O3-Zr O2催化剂性能的影响[J].化工进展,2015,34(2):407-412.Jia Miaoyao,Gao Wengui,Wang Hua,et al.Effect of promoter silica on performance of CuO-Zn O-Al2O3-Zr O2catalyst for methanol synthesis from CO2hydrogenation[J].Chemical Industry and Engineering Progress,2015,34(2):407-412.
[31]Lee D,Lee J Y,Lee J S.Effects of palladium particle size in hydrogenation of carbondioxide to methanol over Pd/Zn O catalysts[J].Studies in Surface Science and Catalysis,2004,153:169-172.
[32]Kim C H,Lee J S,Trimm D L.Catalytic hydrogenation of CO2to methanol over Pd/Zn O:metal-support interaction[J].Studies in Surface Science and Catalysis,2004,153:61-66.
[33]Collins S E,Baltanás M A,Bonivardi A L.An infrared study of the intermediates of methanol synthesis from carbon dioxide over Pd/β-Ga2O3[J].Journal of Catalysis,2004,226(2):410-421.
[2]连普琛,郭岩,拾静漪.CO2催化加氢研究进展[J].内蒙古石油化工,2015,(1):27-28.
[3]张丽平.甲醇生产技术新进展[J].天然气化工(C1化学与化工),2013,38(1):89-94.Zhang Liping.Recent progress in methanol production technology[J].Natural Gas Chemical Industry,2013,38(1):89-94.
[4]Olah G A,Goeppert A,Prakash G K S.跨越油气时代:甲醇经济[M].胡金波,译.北京:化学工业出版社,2007.
[5]仇冬,刘金辉,黄金钱.CO2加氢合成甲醇反应及其催化剂研究进展[J].化学工业与工程技术,2005,26(4):17-20.Qiu Dong,Liu Jinhui,Huang Jinqian.Research progress on the process and catalyst for synthesizing methanol from carbon dioxide and hydrogen[J].Journal of Chemical Industry&Engineering,2005,26(4):17-20.
[6]王献红,王佛松.二氧化碳的固定和利用[M].北京:化学工业出版社,2011:67-72.
[7]黄诚.甲醇生产技术研究最新进展[J].乙醛醋酸化工,2015,(1):25-27.
[8]苗方,高红.二氧化碳加氢制甲醇研究进展[J].化工设计通讯,2014,40(2):53-56.Miao Fang,Gao Hong.The research developments of CO2hydrogenation to prepare methanol[J].Chemical Engineering Design Communications,2014,40(2):53-56.
[9]王珊.西班牙科学家将二氧化碳转化甲醇或解决世界能源难题[EB/OL].2013-11-14[2013-12-12].http://gb.cri.cn/42071/2013/11/14/6071s4321608.htm.
[10]黄诚.二氧化碳加氢制甲醇研发进展[J].乙醛醋酸化工,2015,(2):31-33.
[11]那和保志.温室气体再生化学资源——为了持续不断发展三井化学的挑战[R].天津:亚洲石化科技大会,2011.
[12]许文娟,马丽萍,黄彬,等.CO2催化加氢研究进展[J].化工进展,2009,28(z1):284-289.
[13]凌华招,张晓阳,胡志彪,等.C312型中低压甲醇合成催化剂[J].天然气化工(C1化学与化工),2009,34(6):54-58.Ling Huazhao,Zhang Xiaoyang,Hu Zibiao,et al.C312 catalyst for methanol synthesis at low or medium pressure[J].Natural Gas Chemical Industry,2009,34(6):54-58.
[14]张晓阳,胡志彪,凌华招,等.二氧化碳加氢合成甲醇催化剂及工艺研究开发[J].天然气化工(C1化学与化工),2011,36(6):45-49.Zhang Xiaoyang,Hu Zibiao,Lin Huazhao,et al.Research and development of the catalyst and process for hydrogenation of carbon dioxide to methanol[J].Natural Gas Chemical Industry,2011,36(6):45-49.
[15]An X,Ren F,Li J L,et al.A Highly active Cu/Zn O/Al2O3nanofiber catalyst for methanol synthesis through CO2and CO hydrogenation[J].Chinese Journal of Catalysis,2005,26(9):729-730.
[16]王丹君,陶芙蓉,赵华华,等.Cu/Zn O/Al2O3催化剂的共沉淀-蒸氨法制备及其对二氧化碳加氢制甲醇的研究[J].分子催化,2011,25(2):124-129.Wang Danjun,Tao Furong,Zhao Huahua,et al.Preparation of Cu/Zn O/Al2O3catalyst via coprecipition-amonia evaporation for methanol synthesis from CO2and H2[J].Journal of Molecular Catalysis,2011,25(2):124-129.
[17]吴瑛,吴彬福,王海涛,等.Mn助剂对CO2加氢合成甲醇催化剂Cu/Zn/Al2O3的改性作用[J].浙江师范大学学报(自然科学版),2008,31(1):55-59.Wu Ying,Wu Binfu,Wang Haitao,et al.Effect of Mn on the Cu/Zn/Al2O3catalyst of methanol synthesis[J].Journal of Zhejiang Normal University(Natural Sciences),2008,31(1):55-59.
[18]马晓然,王康军,吴静.Cu-Zn O-Al2O3-Zr O2催化二氧化碳加氢合成甲醇的研究[J].沈阳化工大学学报,2012,26(4):314-317.Ma Xiaoran,Wang Kangjun,Wu Jing.Synthesis of methanol from CO2hydrogenation over Cu-Zn O-Al2O3-Zr O2catalyst[J].Journal of Shenyang University of Chemical Technology,2012,26(4):314-317.
[19]Arena F,Barbera K,Italiano G,et al.Synthesis,characterization and activity pattern of Cu-Zn O/Zr O2catalysts in the hydrogenation of carbon dioxide to methanol[J].Journal of Catalysis,2007,249(2):185-194.
[20]Raudaskoski R,Niemela M V,Keisi R L.The effect of ageing time on co-precipitated Cu/Zn O/Zr O2catalysts used in methanol synthesis from CO2and H2[J].Topics in Catalysis,2007,45(1/4):57-60.
[21]Guo X M,Mao D S,Wang S,et al.Combustion synthesis of CuO-Zn O-Zr O2catalysts for the hydrogenation of carbon dioxide to methanol[J].Catalysis Communications,2009,10(13):1661-1664.
[22]常琴琴,赵博,杨萌,等.Cu/Zn比对CuO/Zn O/Zr O2催化CO2加氢合成甲醇性能的影响[J].化学工程,2015,43(5):58-63.Chang Qinqin,Zhao Bo,Yang Meng,et al.Effect of Cu/Zn on performance of catalysts for methanol synthesis from CO2hydrogenation[J].Chemical Engineering(China),2015,43(5):58-63.
[23]郭晓明,毛东森,卢冠忠,等.Zn O对CO2加氢制甲醇用CuO-Zr O2催化剂性能的影响[J].上海应用技术学院学报(自然科学版),2013,13(4):259-263.Guo Xiaoming,Mao Dongsen,Lu Guanzhong,et al.The influence of Zn O on the performance of CuO-Zr O2for methanol synthesis via CO2hydrogenation[J].Journal of Shanghai Institute of Technology(Natural Science),2013,13(4):259-263.
[24]赵云鹏,贾丽华,孙德智,等.CO2加氢合成甲醇CuOZn O-Ti O2催化剂的制备与表征[J].天然气化工,2011,36(5):17-20.Zhao Yunpeng,Jia Lihua,Sun Dezhi,et al.Preparation and characterization of CuO-Zn O-Ti O2catalyst for methanol synthesis from carbon dioxide hydrogenation[J].Natural Gas Chemical Industry,2011,36(5):17-20.
[25]于杨,郝爱香,陈海波,等.Ti O2助剂对Cu-Zn O/Zr O2催化剂催化CO2加氢制甲醇反应性能的影响[J].天然气化工,2011,36(5):17-20.Yu Yang,Hao Aixiang,Chen Haibo,et al.Effect of Ti O2as promoter on catalytic performance of Cu-Zn O/Zr O2in hydrogenation of CO2to methanol[J].Natural Gas Chemical Industry,2011,36(5):17-20.
[26]Jia L S,Gao J,Fang W P,et al.Carbon dioxide hydrogenation to methanol over the pre-reduced La Cr0.5Cu0.5O3catalyst[J].Catalysis Communications,2009,10(15):2000-2003.
[27]李桂英,胡常伟.Fe助剂对CuO/Al2O3催化剂上CO2+H2合成甲醇影响的研究[J].天然气化工,2005,30(3):13-16.Li Guiying,Hu Changwei.The promotion effect of Fe on CuO/Al2O3catalyst for the synthesis of methanol from CO2+H2[J].Natural Gas Chemical Industry,2005,30(3):13-16.
[28]王冠男,陈礼敏,郭园园,等.铬助剂对Cu/Zr O2/CNTsNH2催化剂催化CO2加氢合成甲醇性能的影响[J].物理化学学报,2014,30(5):923-931.Wang Guannan,Chen Limin,Guo Yuanyuan,et al.Effect of chromium doping on the catalytic behavior of Cu/Zr O2/CNTs-NH2for the synthesis of methanol from carbon dioxide hydrogenation[J].Acta Physico-Chimica Sinica,2014,30(5):923-931.
[29]Soczynski J,Grabowski R,Olszewski P,et al.Effect of metal oxide additives on the activity and stability of Cu/Zn O/Zr O2catalysts in the synthesis of methanol from CO2and H2[J].Applied Catalysis A:General,2006,310:127-137.
[30]贾淼尧,高文桂,王华,等.助剂二氧化硅对CO2加氢制备甲醇CuO-Zn O-Al2O3-Zr O2催化剂性能的影响[J].化工进展,2015,34(2):407-412.Jia Miaoyao,Gao Wengui,Wang Hua,et al.Effect of promoter silica on performance of CuO-Zn O-Al2O3-Zr O2catalyst for methanol synthesis from CO2hydrogenation[J].Chemical Industry and Engineering Progress,2015,34(2):407-412.
[31]Lee D,Lee J Y,Lee J S.Effects of palladium particle size in hydrogenation of carbondioxide to methanol over Pd/Zn O catalysts[J].Studies in Surface Science and Catalysis,2004,153:169-172.
[32]Kim C H,Lee J S,Trimm D L.Catalytic hydrogenation of CO2to methanol over Pd/Zn O:metal-support interaction[J].Studies in Surface Science and Catalysis,2004,153:61-66.
[33]Collins S E,Baltanás M A,Bonivardi A L.An infrared study of the intermediates of methanol synthesis from carbon dioxide over Pd/β-Ga2O3[J].Journal of Catalysis,2004,226(2):410-421.