氨合成钌基催化剂的研究进展
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摘要
近年来,钌基氨合成催化剂因其高活性、高稳定性和反应条件温和成为研究热点。综述国内外氨合成钌基催化剂的研究进展,重点介绍钌基催化剂载体、助剂和前驱体对氨合成反应性能的影响。石墨化程度高、导电性能良好的碳载体或氧化物与碳的复合载体是氨合成反应的良好载体;碱金属和碱土金属类助剂通过改变活性金属表面静电场,起到电子助剂的作用,并且碱土金属对反应的促进作用优于碱金属,稀土金属Sm能够抑制碳载体的甲烷化反应;与Ru Cl3相比,Ru3(CO)12是氨合成反应的理想前驱体。简介以电子化合物为载体的钌基氨合成体系,负载钌的高比表面积电子化合物C12A7:e-是强大的电子供体,能够提高氮气在钌上的解离程度,并能可逆地储存氢,有效抑制氢吸附对钌表面的毒害,从而大大提高氨合成反应活性。进一步开发温和条件下非贵金属高效氨合成催化剂将具有重要的理论和现实意义。
Recently,ruthenium based catalysts for ammonia synthesis have been attracting interest increasingly due to their higher activity,higher stability and mild reaction conditions. The advance in development of Ru based catalysts for ammonia synthesis at home and abroad,especially the influence of the catalyst supports,promoters and precursors on the performance of ammonia synthetic catalysts were introduced in this paper. The carbon supports,carbon covered oxide and their complex with high graphitic degree and good electrical conductivity were good choice for ammonia synthesis supports. Alkali metals and alkaline-earth metals were good promoters for ammonia synthesis,and the promoting effects of alkaline-earth metals were better than those of alkali metals. Rear earth metals Sm could inhibit carbon methanation. Compared with Ru Cl3,Ru3( CO)12was the ideal precursor for ammonia synthesis. A electride C12A7: e-with high surface area,which worked as an excellent electron donor and reversible hydrogen-storage material,was used as support for Ru based catalyst for ammonia synthesis,and the catalytic activity for ammonia synthesis was greatly enhanced. The development of non-noble metal ammonia synthesis catalysts under mild conditions in the future is also proposed.
Recently,ruthenium based catalysts for ammonia synthesis have been attracting interest increasingly due to their higher activity,higher stability and mild reaction conditions. The advance in development of Ru based catalysts for ammonia synthesis at home and abroad,especially the influence of the catalyst supports,promoters and precursors on the performance of ammonia synthetic catalysts were introduced in this paper. The carbon supports,carbon covered oxide and their complex with high graphitic degree and good electrical conductivity were good choice for ammonia synthesis supports. Alkali metals and alkaline-earth metals were good promoters for ammonia synthesis,and the promoting effects of alkaline-earth metals were better than those of alkali metals. Rear earth metals Sm could inhibit carbon methanation. Compared with Ru Cl3,Ru3( CO)12was the ideal precursor for ammonia synthesis. A electride C12A7: e-with high surface area,which worked as an excellent electron donor and reversible hydrogen-storage material,was used as support for Ru based catalyst for ammonia synthesis,and the catalytic activity for ammonia synthesis was greatly enhanced. The development of non-noble metal ammonia synthesis catalysts under mild conditions in the future is also proposed.
引文
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[2]刘化章.合成氨工业:过去、现在和未来[J].化工进展,2013,32(9):1995-2005.Liu Huazhang.Ammonia synthesis industry:past,present and future[J].Chemical Industry and Engineering Progress,2013,32(9):1995-2005.
[3]魏可镁.氨合成催化剂研究进展[J].工业催化,1992,1(1):8-14.Wei Kemei.Progress in catalysts for ammonia synthesis[J].Industry Catalysis,1992,1(1):8-14.
[4]郑晓玲,魏可镁.第二代氨合成催化体系——钌系氨合成催化剂及其工业应用[J].化学进展,2001,13(6):472-480.Zheng Xiaoling,Wei Kemei.The second generation catalysis system for ammonia synthesis——ruthenium based ammonia synthesis catalyst and its industrial application[J].Progress in Chemistry,2001,13(6):472-480.
[5]Boudart M.Kinetics and mechanism of ammonia synthesis[J].Catalysis Reviews-Science and Engineering,1981,2(1):1-15.
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[7]Hinrichsen O.Kinetic simulation of ammonia synthesis catalyzed by ruthenium[J].Catalysis Today,1999,53(2):177-188.
[8]Bielawa H,Hinrichsen O,Birkner A,et al.The ammoniasynthesis catalyst of the next generation:barium-promoted oxide-supported ruthenium[J].Angewandte Chemie-International Edition,2001,40(6):1061-1063.
[9]Murata S,Aika K I.Preparation and characterization of chlorine-free ruthenium catalysts and the promoter effect in ammonia synthesisⅠ.An alumina-supported ruthenium cata-lyst[J].Journal of Catalysis,1992,136(1):110-117.
[10]Boujana S,Demri D,Cressely J,et al.FT-IR and TPD studies on supported-metal and promoter-metal interaction Pt and Pd catalysts[J].Catalysis Letters,1990,7(5/6):359-366.
[11]Tanaka S,Ichikawa M,Naito S,et al.Behavior of hydrogen chemisorbed over electron donor-acceptor complexes of aromatic hydrocarbons with sodium in hydrogen exchange and hydrogenation reactions[J].Bulletin of the Chemical Society of Japan,1968,41(5):1278-1278.
[12]Murata S,Aika K I.Preparation and characterization of chlorine-free ruthenium catalysts and the promoter effect in ammonia synthesisⅡ.A lanthanide oxide-promoted Ru/Al2O3catalyst[J].Journal of Catalysis,1992,136(1):118-125.
[13]Aika K I,Takano T,Murata S.Preparation and characterization of chlorine free ruthenium catalysts and the promoter effect in ammonia synthesisⅢ.A magnesia supported ruthenium catalyst[J].Journal of Catalysis,1992,136(1):126-140.
[14]Urabe K I,Ozaki A,Aika K I,et al.Activation of nitrogen by alkali metal supported transition metalⅣ.Effect of potassium on kinetics of isotopic equilibration of nitrogen on ruthnium catalysts[J].Journal of Catalysis,1975,38(1/3):430-434.
[15]Urabe K I,Aika K I,Ozaki A.Activation of nitrogen by alkali metal-supported transition-metalⅥ.Hydrogen effect on isotopic equilibration of nitrogen and rate-determining step of ammonia synthesis[J].Journal of Catalysis,1976,42(2):197-204.
[16]傅武俊,郑晓玲,刘广臻,等.活性炭载体对钌催化剂制备及其活性的影响[J].工业催化,2003,11(7):45-48.Fu Wujun,Zheng Xiaoling,Liu Guangzhen,et al.Influence of activated carbon on activity of ammonia synthesis catalysts[J].Industrial Catalysis,2003,11(7):45-48.
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[18]张留明,林建新,倪军,等.钌基氨合成催化剂的制备方法[J].化工进展,2011,23(11):2225-2232.Zhang Liuming,Lin Jianxin,Ni Jun,et al.Preparation methods of ruthenium catalysts for ammonia synthesis[J].Progress in Chemistry,2011,23(11):2225-2232.
[19]Mc Carroll J J,Tennison S R,Wilkkinson N P.Catalysts and their use in ammonia Production:US,4600571[P].1984-03-07.
[20]Kowalczyk Z,Sentek J,Jodzis S,et al.Thermally modified active carbon as a support for catalysts for NH3synthesis[J].Carbon,1996,34(3):403-409.
[21]Jiang W,Li Y,Han W F,et al.Effect of the graphitic degree of carbon supports on the catalytic performance of ammonia synthesis over Ba-Ru-K/HSGC catalyst[J].Journal of Energy Chemistry,2014,23(4):443-452.
[22]Zhong Z H,Aika K I.The effect of hydrogen treatment of active carbon on Ru catalysts for ammonia synthesis[J].Journal of Catalysis,1998,173(2):535-539.
[23]Wei G,Wang L H,Lin Y J,et al.Novel ruthenium catalyst(K-Ru/C60/70)for ammonia synthesis[J].Chinese Chemical Letters,1999,10(5):433-434.
[24]Chen H B,Lin J D,Cai Y,et al.Novel multi-walled nanotubes-supported and alkali-promoted Ru catalysts for ammonia synthesis under atmospheric pressure[J].Applied Surface Science,2001,180(3/4):328-335.
[25]Xu Q C,Lin J D,Li J,et al.Combination and interaction of ammonia synthesis ruthenium catalysts[J].Journal of Molecular Catalysis A:Chemical,2006,259(1/2):218-222.
[26]Li Z L,Liang C H,Feng Z C,et al.Ammonia synthesis on graphitic-nanofilament supported Ru catalysts[J].Journal of Molecular Catalysis A:Chemical,2004,211(1/2):103-109.
[27]Liang C H,Li Z L,Qiu J S,et al.Graphitic nanofilaments as novel support of Ru-Ba catalysts for ammonia synthesis[J].Journal of Catalysis,2002,211(1):278-282.
[28]Baker R T K.Factors controlling the mode by which a catalyst operates in the graphite-oxygen reaction[J].Carbon,1986,24(6):715-717.
[29]Zhu Y F,Li X N,Ji D C,et al.Study on the carbon-methanation and catalytic activity of Ru/AC for ammonia synthesis[J].Chinese Journal of Chemical Engineering,2004,12(3):384-387.
[30]Rao K S R,Rao P K,Masthan S K,et al.New type of carbon coated alumina supports for the preparation of highly ctive ruthenium catalysts for ammonia synthesis[J].Applied Catalysis,1990,60(1):L19-L22.
[31]Rao K S R,Masthan S K,Prasad P S S,et al.Effect of barium addition on the ammonia synthesis activity of a caesium promoted ruthenium catalyst supported on carbon-covered alumina(CCA)[J].Applied Catalysis,1991,73(1):1-5.
[32]Guraya M,Sprenger S,Rarog-Pilecka W,et al.The effect ofpromoters on the electronic structure of ruthenium catalysts supported on carbon[J].Applied Surface Science,2004,238(1):77-81.
[33]Rossetti I,Mangiarini F,Forni L.Promoters state and catalyst activation during ammonia synthesis over Ru/C[J].Applied Catalysis A:General,2007,323:219-225.
[34]Rossetti I,Pernicone N,Forni L.Promoters effect in Ru/C ammonia synthesis catalyst[J].Applied Catalysis A:General,2001,208(1/2):271-278.
[35]Muhler M,Rosowski F,Hinrichsen O,et al.Ruthenium as catalyst for ammonia synthesis[J].Studies in Surface Science and Catalysis,1996,101:317-326.
[36]Larichev Y V,Moroz B L,Zaikovskii V I,et al.XPS and TEM studies on the role of the support and alkali Promoter in Ru/Mg O and Ru-Cs+/Mg O catalysts for ammonia synthesis[J].The Journal of Physical Chemistry C,2007,111(26):9427-9436.
[37]Kowalczyk Z,Jodzis S,Rarog W,et al.Carbon supported ruthenium catalyst for the synthesis of ammonia:the effect of the carbon support and barium promoter on the performance[J].Applied Catalysis A:General,1999,184(1):95-102.
[38]Elofson R M,Gadallah F F.Transition metal catalyst:US,4142993[P].1977-12-07.
[39]Kadowaki Y,Aika K.Promoter effect of Sm2O3on Ru/Al2O3in ammonia synthesis[J].Journal of Catalysis,1996,161(1):178-185.
[40]Aika K,Niwa Y.Basic concepts and properties of new generation ammonia synthesis catalysts for industrial use[J].Studies in Surface Science and Catalysis,1998,121,327-332.
[41]祝一锋,李小年,季德春,等.活性炭负载钌基氨合成催化剂炭甲烷化反应的抑制[J].化学通报,2002,65(12):845-858.Zhu Yifeng,Li Xiaonian,Ji Dechun,et al.Resistance of carbon methanation on active carbon supported Ru based ammonia synthesis catalyst[J].Chemistry,2002,65(12):845-858.
[42]Murata S,Aika K I.Removal of chlorine ions from Ru/Mg O catalysts for ammonia synthesis[J].Applied Catalysis A:General,1992,82(1):1-12.
[43]Moggi P,Albanesi G,Predieri G,et al.Ruthenium cluster derived catalysts for ammonia synthesis[J].Applied Catalysis A:General,1995,123(1):145-159.
[44]Kitano M,Inoue Y,Yamazaki Y,et al.Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store[J].Nature Chemistry,2012,4(11):934-940.
[45]Inoue Y,Kitano M,Kim S W,et al.Highly dispersed Ru on electride[Ca24Al28O64]4+(e-)4as a catalyst for ammonia synthesis[J].ACS Catalysis,2014,4(2):674-680.
[2]刘化章.合成氨工业:过去、现在和未来[J].化工进展,2013,32(9):1995-2005.Liu Huazhang.Ammonia synthesis industry:past,present and future[J].Chemical Industry and Engineering Progress,2013,32(9):1995-2005.
[3]魏可镁.氨合成催化剂研究进展[J].工业催化,1992,1(1):8-14.Wei Kemei.Progress in catalysts for ammonia synthesis[J].Industry Catalysis,1992,1(1):8-14.
[4]郑晓玲,魏可镁.第二代氨合成催化体系——钌系氨合成催化剂及其工业应用[J].化学进展,2001,13(6):472-480.Zheng Xiaoling,Wei Kemei.The second generation catalysis system for ammonia synthesis——ruthenium based ammonia synthesis catalyst and its industrial application[J].Progress in Chemistry,2001,13(6):472-480.
[5]Boudart M.Kinetics and mechanism of ammonia synthesis[J].Catalysis Reviews-Science and Engineering,1981,2(1):1-15.
[6]王丽华,何守正,廖代伟,等.氨合成钌催化剂及其催化反应机理研究进展[J].化学进展,1999,11(4):376-384.Wang Lihua,He Shouzheng,Liao Daiwei,et al.Advances in the catalysts and mechanism for ammonia synthesis[J].Progress in Chemistry,1999,11(4):376-384.
[7]Hinrichsen O.Kinetic simulation of ammonia synthesis catalyzed by ruthenium[J].Catalysis Today,1999,53(2):177-188.
[8]Bielawa H,Hinrichsen O,Birkner A,et al.The ammoniasynthesis catalyst of the next generation:barium-promoted oxide-supported ruthenium[J].Angewandte Chemie-International Edition,2001,40(6):1061-1063.
[9]Murata S,Aika K I.Preparation and characterization of chlorine-free ruthenium catalysts and the promoter effect in ammonia synthesisⅠ.An alumina-supported ruthenium cata-lyst[J].Journal of Catalysis,1992,136(1):110-117.
[10]Boujana S,Demri D,Cressely J,et al.FT-IR and TPD studies on supported-metal and promoter-metal interaction Pt and Pd catalysts[J].Catalysis Letters,1990,7(5/6):359-366.
[11]Tanaka S,Ichikawa M,Naito S,et al.Behavior of hydrogen chemisorbed over electron donor-acceptor complexes of aromatic hydrocarbons with sodium in hydrogen exchange and hydrogenation reactions[J].Bulletin of the Chemical Society of Japan,1968,41(5):1278-1278.
[12]Murata S,Aika K I.Preparation and characterization of chlorine-free ruthenium catalysts and the promoter effect in ammonia synthesisⅡ.A lanthanide oxide-promoted Ru/Al2O3catalyst[J].Journal of Catalysis,1992,136(1):118-125.
[13]Aika K I,Takano T,Murata S.Preparation and characterization of chlorine free ruthenium catalysts and the promoter effect in ammonia synthesisⅢ.A magnesia supported ruthenium catalyst[J].Journal of Catalysis,1992,136(1):126-140.
[14]Urabe K I,Ozaki A,Aika K I,et al.Activation of nitrogen by alkali metal supported transition metalⅣ.Effect of potassium on kinetics of isotopic equilibration of nitrogen on ruthnium catalysts[J].Journal of Catalysis,1975,38(1/3):430-434.
[15]Urabe K I,Aika K I,Ozaki A.Activation of nitrogen by alkali metal-supported transition-metalⅥ.Hydrogen effect on isotopic equilibration of nitrogen and rate-determining step of ammonia synthesis[J].Journal of Catalysis,1976,42(2):197-204.
[16]傅武俊,郑晓玲,刘广臻,等.活性炭载体对钌催化剂制备及其活性的影响[J].工业催化,2003,11(7):45-48.Fu Wujun,Zheng Xiaoling,Liu Guangzhen,et al.Influence of activated carbon on activity of ammonia synthesis catalysts[J].Industrial Catalysis,2003,11(7):45-48.
[17]Schlogl R.Catalytic synthesis of ammonia a“never-ending story”?[J].Angewandte Chemie-International Edition,2003,42(18):2004-2008.
[18]张留明,林建新,倪军,等.钌基氨合成催化剂的制备方法[J].化工进展,2011,23(11):2225-2232.Zhang Liuming,Lin Jianxin,Ni Jun,et al.Preparation methods of ruthenium catalysts for ammonia synthesis[J].Progress in Chemistry,2011,23(11):2225-2232.
[19]Mc Carroll J J,Tennison S R,Wilkkinson N P.Catalysts and their use in ammonia Production:US,4600571[P].1984-03-07.
[20]Kowalczyk Z,Sentek J,Jodzis S,et al.Thermally modified active carbon as a support for catalysts for NH3synthesis[J].Carbon,1996,34(3):403-409.
[21]Jiang W,Li Y,Han W F,et al.Effect of the graphitic degree of carbon supports on the catalytic performance of ammonia synthesis over Ba-Ru-K/HSGC catalyst[J].Journal of Energy Chemistry,2014,23(4):443-452.
[22]Zhong Z H,Aika K I.The effect of hydrogen treatment of active carbon on Ru catalysts for ammonia synthesis[J].Journal of Catalysis,1998,173(2):535-539.
[23]Wei G,Wang L H,Lin Y J,et al.Novel ruthenium catalyst(K-Ru/C60/70)for ammonia synthesis[J].Chinese Chemical Letters,1999,10(5):433-434.
[24]Chen H B,Lin J D,Cai Y,et al.Novel multi-walled nanotubes-supported and alkali-promoted Ru catalysts for ammonia synthesis under atmospheric pressure[J].Applied Surface Science,2001,180(3/4):328-335.
[25]Xu Q C,Lin J D,Li J,et al.Combination and interaction of ammonia synthesis ruthenium catalysts[J].Journal of Molecular Catalysis A:Chemical,2006,259(1/2):218-222.
[26]Li Z L,Liang C H,Feng Z C,et al.Ammonia synthesis on graphitic-nanofilament supported Ru catalysts[J].Journal of Molecular Catalysis A:Chemical,2004,211(1/2):103-109.
[27]Liang C H,Li Z L,Qiu J S,et al.Graphitic nanofilaments as novel support of Ru-Ba catalysts for ammonia synthesis[J].Journal of Catalysis,2002,211(1):278-282.
[28]Baker R T K.Factors controlling the mode by which a catalyst operates in the graphite-oxygen reaction[J].Carbon,1986,24(6):715-717.
[29]Zhu Y F,Li X N,Ji D C,et al.Study on the carbon-methanation and catalytic activity of Ru/AC for ammonia synthesis[J].Chinese Journal of Chemical Engineering,2004,12(3):384-387.
[30]Rao K S R,Rao P K,Masthan S K,et al.New type of carbon coated alumina supports for the preparation of highly ctive ruthenium catalysts for ammonia synthesis[J].Applied Catalysis,1990,60(1):L19-L22.
[31]Rao K S R,Masthan S K,Prasad P S S,et al.Effect of barium addition on the ammonia synthesis activity of a caesium promoted ruthenium catalyst supported on carbon-covered alumina(CCA)[J].Applied Catalysis,1991,73(1):1-5.
[32]Guraya M,Sprenger S,Rarog-Pilecka W,et al.The effect ofpromoters on the electronic structure of ruthenium catalysts supported on carbon[J].Applied Surface Science,2004,238(1):77-81.
[33]Rossetti I,Mangiarini F,Forni L.Promoters state and catalyst activation during ammonia synthesis over Ru/C[J].Applied Catalysis A:General,2007,323:219-225.
[34]Rossetti I,Pernicone N,Forni L.Promoters effect in Ru/C ammonia synthesis catalyst[J].Applied Catalysis A:General,2001,208(1/2):271-278.
[35]Muhler M,Rosowski F,Hinrichsen O,et al.Ruthenium as catalyst for ammonia synthesis[J].Studies in Surface Science and Catalysis,1996,101:317-326.
[36]Larichev Y V,Moroz B L,Zaikovskii V I,et al.XPS and TEM studies on the role of the support and alkali Promoter in Ru/Mg O and Ru-Cs+/Mg O catalysts for ammonia synthesis[J].The Journal of Physical Chemistry C,2007,111(26):9427-9436.
[37]Kowalczyk Z,Jodzis S,Rarog W,et al.Carbon supported ruthenium catalyst for the synthesis of ammonia:the effect of the carbon support and barium promoter on the performance[J].Applied Catalysis A:General,1999,184(1):95-102.
[38]Elofson R M,Gadallah F F.Transition metal catalyst:US,4142993[P].1977-12-07.
[39]Kadowaki Y,Aika K.Promoter effect of Sm2O3on Ru/Al2O3in ammonia synthesis[J].Journal of Catalysis,1996,161(1):178-185.
[40]Aika K,Niwa Y.Basic concepts and properties of new generation ammonia synthesis catalysts for industrial use[J].Studies in Surface Science and Catalysis,1998,121,327-332.
[41]祝一锋,李小年,季德春,等.活性炭负载钌基氨合成催化剂炭甲烷化反应的抑制[J].化学通报,2002,65(12):845-858.Zhu Yifeng,Li Xiaonian,Ji Dechun,et al.Resistance of carbon methanation on active carbon supported Ru based ammonia synthesis catalyst[J].Chemistry,2002,65(12):845-858.
[42]Murata S,Aika K I.Removal of chlorine ions from Ru/Mg O catalysts for ammonia synthesis[J].Applied Catalysis A:General,1992,82(1):1-12.
[43]Moggi P,Albanesi G,Predieri G,et al.Ruthenium cluster derived catalysts for ammonia synthesis[J].Applied Catalysis A:General,1995,123(1):145-159.
[44]Kitano M,Inoue Y,Yamazaki Y,et al.Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store[J].Nature Chemistry,2012,4(11):934-940.
[45]Inoue Y,Kitano M,Kim S W,et al.Highly dispersed Ru on electride[Ca24Al28O64]4+(e-)4as a catalyst for ammonia synthesis[J].ACS Catalysis,2014,4(2):674-680.