一氧化碳完全氧化整体催化剂的研究
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摘要
整体催化剂用于一氧化碳完全氧化具有很大的优越性。本文制备了两种类型的整体催化剂，即单一过渡金属氧化物整体催化剂和复合氧化物整体催化剂。首先采用Taguchi试验方法对单一过渡金属氧化物整体催化剂制备过程进行设计实验。通过在整体催化剂制备过程中采用不同涂层、活性组分及其负载方法以求获得最优的催化剂。同时对所制备的最优催化剂加入贵金属助剂进行改性。
采用溶胶/母体混合法以及溶胶、凝胶法制备了钴基复合氧化物整体催化剂。本文对采用的催化剂制备方法进行了详细叙述，使用SEM、TEM、XRD、TPR等手段对催化剂进行了物化性质表征。
以CO完全氧化为目标反应，在整体催化剂反应器中评价了浸渍法和沉积沉淀法制备的CuOx、MnOx及CoOx系列过渡金属整体氧化物催化剂，和溶胶/母体混合法以及溶胶、凝胶法制备的钴基复合氧化物整体催化剂。结果表明，单一过渡金属氧化物中以沉积沉淀法制备的CoOx/SiO2（酸性）整体催化剂具有较高的燃烧反应活性，贵金属的加入对其催化活性影响不显著。
复合氧化物催化剂中，以FC化合物为母体的整体催化剂表现出了最高的CO燃烧反应活性，与单一过渡金属氧化物相比活性得到了显著的提高。
本文将不同方法所制备的催化剂与活性评价结果进行关联，考察了活性与催化剂结构的关系。并对整体催化剂的涂层机理进行了详细的阐述。
同时，本文也考察了整体催化剂与颗粒催化剂催化性能的差异，表明整体催化剂用于催化氧化反应具有很大优越性。
Monolithic catalyst is advantageous for total oxidation of carbon monoxide. In this work, two kinds of monolithic catalyst were prepared. They are single transition metal oxide and composite oxide monolithic catalysts. First, Taguchi method is used to investigate the effects of different washcoatings, active components and their loading methods in the preparation process of the single transition metal oxide monolithic catalysts in order to achieve the optimal combination of the preparation conditions. Then, the best catalyst is doped with noble metals to improve its catalytic activity.
Cobalt-Alumina composite oxides deposited on monoliths were prepared by sol/precursors coating and sol-gel coating methods. Different preparation methods are discussed thoroughly in this thesis. The physical-chemical properties of the catalysts were characterized with SEM, XRD, TPR and TEM techniques.
Using CO total oxidation as probe reaction, the transition metal oxides CuOx, MnOx, CoOx monolithic catalysts prepared by impregnation and deposit-precipitation were tested in monolithic reactor. Cobalt-Alumina composite oxides deposited on the monoliths prepared by sol/precursors coating and sol-gel coating methods were also investigated for CO total oxidation. The catalyst screening results showed that CoOx/SiO2(acid) was the most promising system in the single transition metal oxides monolithic catalysts. Doping noble metals has no significant effect on the activity of the CoOx/SiO2(acid).
As the composite oxides were concerned, the monolithic catalyst that was prepared from Feitknecht compound precursors showed the highest activity in the total oxidation of CO. The catalytic activity was obviously promoted compared to single transition metal oxides.
In this work, different preparation methods and the activities of the catalysts are related in order to investigate the correlations of the catalyst’ s structure with its activity. Meantime, the coating mechanisms are also discussed in this thesis.
Finally, the monolithic catalyst is compared with the particle catalyst by testing for the CO total oxidation. The results indicate that monolithic catalyst used for catalytic oxidation is much more advantageous than particle catalyst.
采用溶胶/母体混合法以及溶胶、凝胶法制备了钴基复合氧化物整体催化剂。本文对采用的催化剂制备方法进行了详细叙述，使用SEM、TEM、XRD、TPR等手段对催化剂进行了物化性质表征。
以CO完全氧化为目标反应，在整体催化剂反应器中评价了浸渍法和沉积沉淀法制备的CuOx、MnOx及CoOx系列过渡金属整体氧化物催化剂，和溶胶/母体混合法以及溶胶、凝胶法制备的钴基复合氧化物整体催化剂。结果表明，单一过渡金属氧化物中以沉积沉淀法制备的CoOx/SiO2（酸性）整体催化剂具有较高的燃烧反应活性，贵金属的加入对其催化活性影响不显著。
复合氧化物催化剂中，以FC化合物为母体的整体催化剂表现出了最高的CO燃烧反应活性，与单一过渡金属氧化物相比活性得到了显著的提高。
本文将不同方法所制备的催化剂与活性评价结果进行关联，考察了活性与催化剂结构的关系。并对整体催化剂的涂层机理进行了详细的阐述。
同时，本文也考察了整体催化剂与颗粒催化剂催化性能的差异，表明整体催化剂用于催化氧化反应具有很大优越性。
Monolithic catalyst is advantageous for total oxidation of carbon monoxide. In this work, two kinds of monolithic catalyst were prepared. They are single transition metal oxide and composite oxide monolithic catalysts. First, Taguchi method is used to investigate the effects of different washcoatings, active components and their loading methods in the preparation process of the single transition metal oxide monolithic catalysts in order to achieve the optimal combination of the preparation conditions. Then, the best catalyst is doped with noble metals to improve its catalytic activity.
Cobalt-Alumina composite oxides deposited on monoliths were prepared by sol/precursors coating and sol-gel coating methods. Different preparation methods are discussed thoroughly in this thesis. The physical-chemical properties of the catalysts were characterized with SEM, XRD, TPR and TEM techniques.
Using CO total oxidation as probe reaction, the transition metal oxides CuOx, MnOx, CoOx monolithic catalysts prepared by impregnation and deposit-precipitation were tested in monolithic reactor. Cobalt-Alumina composite oxides deposited on the monoliths prepared by sol/precursors coating and sol-gel coating methods were also investigated for CO total oxidation. The catalyst screening results showed that CoOx/SiO2(acid) was the most promising system in the single transition metal oxides monolithic catalysts. Doping noble metals has no significant effect on the activity of the CoOx/SiO2(acid).
As the composite oxides were concerned, the monolithic catalyst that was prepared from Feitknecht compound precursors showed the highest activity in the total oxidation of CO. The catalytic activity was obviously promoted compared to single transition metal oxides.
In this work, different preparation methods and the activities of the catalysts are related in order to investigate the correlations of the catalyst’ s structure with its activity. Meantime, the coating mechanisms are also discussed in this thesis.
Finally, the monolithic catalyst is compared with the particle catalyst by testing for the CO total oxidation. The results indicate that monolithic catalyst used for catalytic oxidation is much more advantageous than particle catalyst.
引文
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2. 许业伟，袁文辉. 广东化工，2001，3: 2.
3. 牛学坤，陈标华等. 环境污染治理技术与设备，2000，1(2).
4. R.B.Jagow, R.A.Lamparter, T.katan et al. Am.Soc.Mech.Eng.Pap. 77-ENAs-28 (1977).
5. C.Xu, J.Tamaki, N.Miura et al. Chem.lett., 1990, 441.
6. P.G.Hamison & M.J.Willett. Nature, 1988, 332-337.
7. D.S.Stark & M.R.Harris. J.Phys.E:Sci.Instrum., 1983, 16:492.
8. D.S.Stark, A.Crocker& G.J.Steward. J.Phys.E:Sci.Instrum., 1983, 16:158.
9. D.S.Stark and M.R.Harris. J.Phys.E:Sci.Instrum., 1988, 21:715.
10. T.Engel, G.Ertl. Adv. Catal., 1979, 28:1
11. M .Che, C.O.Bennett. Adv. Catal., 1989, 36:55.
12. J.A.Rodriguez, D.W.Goodman. Surf.Sci.Rep., 1991, 14:1.
13. Friedrich M Hoffmann, Daniel J Dwyer. Surface Science of Catalysis, 1991:10.
14. T.Engel, G.Ertl. J Chem Phys., 1978, 69:1267.
15.C.T.Campbell, G.Ertl, H.Kuipers et al. J Chem. Phys., 1980, 73:5862.
16. R.P.H.Gasser. An Introduction to Chemisorporption and Catalysis by Metals, Clarendon Press, Oxford, 1985, Chapter 9.
17. P.D.Petrolekas, I.S.Metcalfe. Trans.IchemE, 73A, 1995:122.
18. G.G.Jernigan, G.A.Somorjai. J.Catal., 1994, 147:567.
19. Guido Saracco, Vito Specchia. Chemical Engineering Science, 2000, 55 897-908.
20. Gabriele Centi. Journal of Molecular Catalysis A: Chemical, 2001, 173: 287–312.
21. Q.H.Xia, K.Hidajat, S.Kawi. Catal. Today, 2001, 68:255.
22. M.A.Centeno, M.Paulis, M.Montes et al. Appl. Catalysis A:General, 2002, 234:65.
23. S.Salvatore, M.Simona, C.Carmelo et al. Appl. Catalysis B: Environmental, 2003,40: 43.
24. Daniela Terribile, Alessandro Trovarelli. Catal. today, 1999, 47: 133-140.
25. G.Busca, M.Daturi. Catal. Today, 1997, 33: 239-249.
26. G.Busca, M.Baldi, C.Pistarino et al. Catal. Today, 1999, 53: 525.
27. C.Hettige, K.R.R.Mahanama, D.P.Dissanayake. Chemosphere, 2001, 43: 1079.
28. A.P.Antunes, M.F.Ribeiro, J.M.Silva et al. Appl. Catalysis B: Environmental,
2001, 33: 149.
29. L.Kiwi-Minsker, I.Yuranov, E.Slavinskaia et al. Catal. Today, 2000, 59: 61.
30. M.P.Anna, S.Krystyna. Catal. Today, 2000, 59: 269.
31. Ch.Subrahmanyam, B.Louis, F.Rainone et al. Appl. Catalysis A: General, 2003, 241: 205.
32. L.Kiwi-Minsker, I.Yuranov, B.Siebenhaar et al. Catal.Today, 1999, 54:39.
33. B.N.Racine, M.J.Sally, B.wade et al. J.Catal., 1991, 127:307.
34. G.S.Zafiris, R.J.Gorte. J.Catal., 1993, 140:418.
35. K.I.Choi, M.A.Vannice. J.Catal., 1991, 131:361.
36. R.K.Herz, A.Badlani, D.R.Schryer et al. J. Catal., 1993, 141:219.
37. 王乐夫，徐可岱. 天然气化工，1989，14(1): 10.
38. 史泰尔斯A B催化剂载体与负载催化剂. 北京：中国石化出版社，1992：251.
39. D.R.Schryer, B.T.Upchurch, J.D.V.Norman et al. J.Catal., 1990, 122:193.
40. G.B. Hoflund, S.D.Gardner, D.R.Schryer et al. Appl. Catal., 1995, 6:117.
41. Steven D.Gardner, Gar B. Hoflund, Billy T.Upchurch, J.Catal., 1991, 6:17.
42. S.D.Gardner, G.B.Hoflund, D.R.Schryer, Langmuir, 1991, 7:2135.
43. Youzhu Yuan, Kiyotaka, Huilin Wan et al. Catal.Lett., 1996, 42:15.
44. Youzhu Yuan, Kiyotaka, Huilin Wan et al. J.Catal., 1997, 170:191.
45. 王金安，许勇，汪仁. 催化学报，1994, 15(3):212.
46. S.Imamura, H.Sawada, K.Uemura et al. J.Catal, 1988, 109:198.
47. 罗梦飞，袁贤鑫.催化学报，1995，16(4): 328.
48. O.Mitsutaka, M.Noriaki, K.Eiko et al. J. Catal., 2002, 208:485
49. H.A.Jones, H.S.Taylor. J.Phys.Chem., 1923, 27:623.
50. J.W.Bijsterbosch, J.C.Muijsers, A.D.Vanlangeveld et al. Fundamental Aspects of Heterogenous Catalysis Studies by Particle Beams. Edited by H.H.Brongersma, 52. R.A.Vansanten. Plenum Press. New York: 1991, 221.
51. K.L.Choi, M.A.Vannice. J.Catal., 1991, 131:22.
52. Y.Jackie, Andreas Tschope, Doron Lecin. Nanostructured Materials, 1995, 6:237.
53. J.Mooi, P.W.Selwood. J.Amer.Chem.Soc., 1952, 74:1750.
54. A.Cimino, V.Indovina. J.Catal., 1974, 33:493.
55. S.B.Kaungo, J.Catal., 1979, 58:419.
56. F.L.Du, Z.L.Cui, Z.K.Zhang et al. Journal of Natural Gas Chemistry, 1997, 6(2):135.
57. 孙永安，张文韬，胡瑞生. 中国稀土学报，1997，15(2): 123.
58. 刘源，秦永宁，韩森. 催化学报，1998，19(2): 173.
59. Y.Zhang-Steenwinkel, J.Beckers, A.Bliek. Appl. Catalysis A: General, 2002, 235: 79.
60. A.Trovarelli, C.De Leitenburg, M.Boaro, R.Dolcetti. Catal. Today, 1999, 50:353.
61. C.E.Hori, H.Permana, K.Y.S.Ng, et al. Appl.Catal.B, 1998, 16:105.
62. D.Terribile, A.Trovarelli, J.Liorca et al. Catal. Today, 1998, 43:79.
63. E.S.Putna, T.Bunluesin, X.L.Fan et al. Catal. Today, 1999, 50:343.
64. M.Thammachart, V.Meeyoo, T. Risksomboon et al. Catal. Today, 2001, 68:53.
65. 王爱琴. 中国科学院大连化学物理研究所博士学位论文, 大连, 2001.
66. R.M.Heck, R.J.Farrauto, Catalytic Air Pollution Control: Commercial Technology, Wiley, New York, 1995.
67. R.J. Farrauto, K. Voss, Appl. Catal. B, 1996, 10: 29.
68. J. Lampert, S. Kazi, R.J. Farrauto. Appl. Catal. B, 1997, 14 : 211.
69. R.M. Heck, R.J Farrauto. CATTECH, 1997, 12: 117.
70. Industrial Catalytic News, 98, No. 11 1998.
71. T. A. Nijhuis, A.E.W. Beers, T. Vergunst et al. Catal. Rev.-Sci. Eng., 2001, 43: 345-380.
72.P.A.Beauseigneur, I.M.Lachman, M.D.Patil. US Patent 5, 334, 570,1994.
73.A.E.Duisterwinkel. Ph.D. Thesis, Delft University of Technology, Delft, 1991.
74. W.P.Addiego, I.M.Lachman, M.D.Patil, US Patent 5, 212, 130, 1993.
75. A.A.Klinghoffer, R.L.Cerro, M.A.Abraham. Catal. Today, 1998, 40:59.
76. J.S.Hepburn, H.G.Strenger, C.E.Lyman. Appl. Catal., 1989, 55:271.
77. L.M.Knijff, R.H.Bolt, R.van Yperen. Studies Surface Sci.Catal., 1991, 63:165.
78. 吴东方. 天津大学博士毕业论文, 天津, 2002.
79. Taguchi G. System of experimental design, 1988, New York: Kraus International Publications.
80. E. A. Dawson, P. A. Barnes. Appl. Catal. A: Gen., 1992, 90: 217.
81. 陈久岭. 天津大学博士毕业论文, 天津, 1999.
82. Avani F, Trifiro F, Vaccari A. Catal.Today, 1991, 11:173.
83. 朴玲钰. 天津大学博士毕业论文, 天津, 2002.
84. A.Christos, T.Athena. J. the European Ceramic Society, 2002, 22: 423.
85. I.Yuranov, N.Dunand, L.Kiwi-Minsker et al. Appl. Catalysis B: Environmental, 2002, 36: 183.
2. 许业伟，袁文辉. 广东化工，2001，3: 2.
3. 牛学坤，陈标华等. 环境污染治理技术与设备，2000，1(2).
4. R.B.Jagow, R.A.Lamparter, T.katan et al. Am.Soc.Mech.Eng.Pap. 77-ENAs-28 (1977).
5. C.Xu, J.Tamaki, N.Miura et al. Chem.lett., 1990, 441.
6. P.G.Hamison & M.J.Willett. Nature, 1988, 332-337.
7. D.S.Stark & M.R.Harris. J.Phys.E:Sci.Instrum., 1983, 16:492.
8. D.S.Stark, A.Crocker& G.J.Steward. J.Phys.E:Sci.Instrum., 1983, 16:158.
9. D.S.Stark and M.R.Harris. J.Phys.E:Sci.Instrum., 1988, 21:715.
10. T.Engel, G.Ertl. Adv. Catal., 1979, 28:1
11. M .Che, C.O.Bennett. Adv. Catal., 1989, 36:55.
12. J.A.Rodriguez, D.W.Goodman. Surf.Sci.Rep., 1991, 14:1.
13. Friedrich M Hoffmann, Daniel J Dwyer. Surface Science of Catalysis, 1991:10.
14. T.Engel, G.Ertl. J Chem Phys., 1978, 69:1267.
15.C.T.Campbell, G.Ertl, H.Kuipers et al. J Chem. Phys., 1980, 73:5862.
16. R.P.H.Gasser. An Introduction to Chemisorporption and Catalysis by Metals, Clarendon Press, Oxford, 1985, Chapter 9.
17. P.D.Petrolekas, I.S.Metcalfe. Trans.IchemE, 73A, 1995:122.
18. G.G.Jernigan, G.A.Somorjai. J.Catal., 1994, 147:567.
19. Guido Saracco, Vito Specchia. Chemical Engineering Science, 2000, 55 897-908.
20. Gabriele Centi. Journal of Molecular Catalysis A: Chemical, 2001, 173: 287–312.
21. Q.H.Xia, K.Hidajat, S.Kawi. Catal. Today, 2001, 68:255.
22. M.A.Centeno, M.Paulis, M.Montes et al. Appl. Catalysis A:General, 2002, 234:65.
23. S.Salvatore, M.Simona, C.Carmelo et al. Appl. Catalysis B: Environmental, 2003,40: 43.
24. Daniela Terribile, Alessandro Trovarelli. Catal. today, 1999, 47: 133-140.
25. G.Busca, M.Daturi. Catal. Today, 1997, 33: 239-249.
26. G.Busca, M.Baldi, C.Pistarino et al. Catal. Today, 1999, 53: 525.
27. C.Hettige, K.R.R.Mahanama, D.P.Dissanayake. Chemosphere, 2001, 43: 1079.
28. A.P.Antunes, M.F.Ribeiro, J.M.Silva et al. Appl. Catalysis B: Environmental,
2001, 33: 149.
29. L.Kiwi-Minsker, I.Yuranov, E.Slavinskaia et al. Catal. Today, 2000, 59: 61.
30. M.P.Anna, S.Krystyna. Catal. Today, 2000, 59: 269.
31. Ch.Subrahmanyam, B.Louis, F.Rainone et al. Appl. Catalysis A: General, 2003, 241: 205.
32. L.Kiwi-Minsker, I.Yuranov, B.Siebenhaar et al. Catal.Today, 1999, 54:39.
33. B.N.Racine, M.J.Sally, B.wade et al. J.Catal., 1991, 127:307.
34. G.S.Zafiris, R.J.Gorte. J.Catal., 1993, 140:418.
35. K.I.Choi, M.A.Vannice. J.Catal., 1991, 131:361.
36. R.K.Herz, A.Badlani, D.R.Schryer et al. J. Catal., 1993, 141:219.
37. 王乐夫，徐可岱. 天然气化工，1989，14(1): 10.
38. 史泰尔斯A B催化剂载体与负载催化剂. 北京：中国石化出版社，1992：251.
39. D.R.Schryer, B.T.Upchurch, J.D.V.Norman et al. J.Catal., 1990, 122:193.
40. G.B. Hoflund, S.D.Gardner, D.R.Schryer et al. Appl. Catal., 1995, 6:117.
41. Steven D.Gardner, Gar B. Hoflund, Billy T.Upchurch, J.Catal., 1991, 6:17.
42. S.D.Gardner, G.B.Hoflund, D.R.Schryer, Langmuir, 1991, 7:2135.
43. Youzhu Yuan, Kiyotaka, Huilin Wan et al. Catal.Lett., 1996, 42:15.
44. Youzhu Yuan, Kiyotaka, Huilin Wan et al. J.Catal., 1997, 170:191.
45. 王金安，许勇，汪仁. 催化学报，1994, 15(3):212.
46. S.Imamura, H.Sawada, K.Uemura et al. J.Catal, 1988, 109:198.
47. 罗梦飞，袁贤鑫.催化学报，1995，16(4): 328.
48. O.Mitsutaka, M.Noriaki, K.Eiko et al. J. Catal., 2002, 208:485
49. H.A.Jones, H.S.Taylor. J.Phys.Chem., 1923, 27:623.
50. J.W.Bijsterbosch, J.C.Muijsers, A.D.Vanlangeveld et al. Fundamental Aspects of Heterogenous Catalysis Studies by Particle Beams. Edited by H.H.Brongersma, 52. R.A.Vansanten. Plenum Press. New York: 1991, 221.
51. K.L.Choi, M.A.Vannice. J.Catal., 1991, 131:22.
52. Y.Jackie, Andreas Tschope, Doron Lecin. Nanostructured Materials, 1995, 6:237.
53. J.Mooi, P.W.Selwood. J.Amer.Chem.Soc., 1952, 74:1750.
54. A.Cimino, V.Indovina. J.Catal., 1974, 33:493.
55. S.B.Kaungo, J.Catal., 1979, 58:419.
56. F.L.Du, Z.L.Cui, Z.K.Zhang et al. Journal of Natural Gas Chemistry, 1997, 6(2):135.
57. 孙永安，张文韬，胡瑞生. 中国稀土学报，1997，15(2): 123.
58. 刘源，秦永宁，韩森. 催化学报，1998，19(2): 173.
59. Y.Zhang-Steenwinkel, J.Beckers, A.Bliek. Appl. Catalysis A: General, 2002, 235: 79.
60. A.Trovarelli, C.De Leitenburg, M.Boaro, R.Dolcetti. Catal. Today, 1999, 50:353.
61. C.E.Hori, H.Permana, K.Y.S.Ng, et al. Appl.Catal.B, 1998, 16:105.
62. D.Terribile, A.Trovarelli, J.Liorca et al. Catal. Today, 1998, 43:79.
63. E.S.Putna, T.Bunluesin, X.L.Fan et al. Catal. Today, 1999, 50:343.
64. M.Thammachart, V.Meeyoo, T. Risksomboon et al. Catal. Today, 2001, 68:53.
65. 王爱琴. 中国科学院大连化学物理研究所博士学位论文, 大连, 2001.
66. R.M.Heck, R.J.Farrauto, Catalytic Air Pollution Control: Commercial Technology, Wiley, New York, 1995.
67. R.J. Farrauto, K. Voss, Appl. Catal. B, 1996, 10: 29.
68. J. Lampert, S. Kazi, R.J. Farrauto. Appl. Catal. B, 1997, 14 : 211.
69. R.M. Heck, R.J Farrauto. CATTECH, 1997, 12: 117.
70. Industrial Catalytic News, 98, No. 11 1998.
71. T. A. Nijhuis, A.E.W. Beers, T. Vergunst et al. Catal. Rev.-Sci. Eng., 2001, 43: 345-380.
72.P.A.Beauseigneur, I.M.Lachman, M.D.Patil. US Patent 5, 334, 570,1994.
73.A.E.Duisterwinkel. Ph.D. Thesis, Delft University of Technology, Delft, 1991.
74. W.P.Addiego, I.M.Lachman, M.D.Patil, US Patent 5, 212, 130, 1993.
75. A.A.Klinghoffer, R.L.Cerro, M.A.Abraham. Catal. Today, 1998, 40:59.
76. J.S.Hepburn, H.G.Strenger, C.E.Lyman. Appl. Catal., 1989, 55:271.
77. L.M.Knijff, R.H.Bolt, R.van Yperen. Studies Surface Sci.Catal., 1991, 63:165.
78. 吴东方. 天津大学博士毕业论文, 天津, 2002.
79. Taguchi G. System of experimental design, 1988, New York: Kraus International Publications.
80. E. A. Dawson, P. A. Barnes. Appl. Catal. A: Gen., 1992, 90: 217.
81. 陈久岭. 天津大学博士毕业论文, 天津, 1999.
82. Avani F, Trifiro F, Vaccari A. Catal.Today, 1991, 11:173.
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