在固定床反应器上考察了原粒度(1～3 mm)CeO2助Co/SiO2催化剂的费托反应性能,提出了催化剂失活的机理,并采用程序升温还原、X射线衍射和X射线光电子能谱对催化剂进行了表征.结果表明,在1.5 Mpa,488 K和400 h-1条件下进行的300 h稳定性实验中,原粒度CeO2助Co/SiO2催化剂上的CO平均转化率达到41%,液态烃选择性达到85%,液态烃中C10+烃的质量含量占88%以上.反应器出口的催化剂中有少量的CoO和Co2SiO4生成催化剂的失活过程受动力学控制而非热力学控制,催化剂的失活机理为:高分散的纳米Co离子在反应器出口高水蒸气压力的作用下,以CoO为中间物种,与水合SiO2作用生成Co2SiO4,即Co+H2O→CoO+H2,SiO2+H2O→Osi(OH)2,2CoO+Osi(OH)2→Co2SiO4+H2O.
参考文献
| [1] | Nikolopoulos A A;Gangwal S K;Spivey J J .[J].Studies in Surface Science and Catalysis,2001,136(0Ⅵ):351. |
| [2] | Hilmen A M;Schanke D;Holmen A .[J].Catalysis Letters,1996,38(3-4):143. |
| [3] | Kogelbauer A.;Oukaci R.;Goodwin JG. .RUTHENIUM PROMOTION OF CO/AL2O3 FISCHER-TROPSCH CATALYSTS[J].Journal of Catalysis,1996(1):125-133. |
| [4] | Schanke D.;Blekkan EA.;Hilmen AM.;Hoff A.;Holmen A.;Vada S. .STUDY OF PT-PROMOTED COBALT CO HYDROGENATION CATALYSTS[J].Journal of Catalysis,1995(1):85-95. |
| [5] | Tsubaki N;Sun S;Fujimoto K .[J].Journal of Catalysis,2001,199(02):236. |
| [6] | Iglesia E .[J].Studies in Surface Science and Catalysis,1997,107(0Ⅳ):153. |
| [7] | Das T K;Jacobs G;Patterson P M;Conner W A Li J L Davis B H .[J].FUEL,2003,82(07):805. |
| [8] | Haddad GJ.;Goodwin JG.;Chen B. .EFFECT OF LA3+ PROMOTION OF CO/SIO2 ON CO HYDROGENATION[J].Journal of Catalysis,1996(1):274-281. |
| [9] | 熊建民,丁云杰,王涛,吕元,朱何俊,罗洪原,林励吾.La2O3助剂对Co/AC催化剂上费-托合成反应性能的影响[J].催化学报,2005(10):874-878. |
| [10] | Moradi G R;Basir M M;Taeb A;Kiennemann A .[J].Catalysis Communications,2003,4(01):27. |
| [11] | 陈建刚,相宏伟,王秀芝,孙予罕,刘涛,胡天斗,谢亚宁.锆助剂含量对钴基费-托合成催化剂的影响[J].催化学报,2000(04):359-362. |
| [12] | Guerrero-RuizA;Sepúlveda-EscribanoA;Rodriguez-Ramos I .[J].Applied Catalysis A:General,1994,120(01):71. |
| [13] | Barrault J;Guilleminot A;Achard J C;Paul-Boncour V Percheron-Guegan A .[J].Applied Catalysis,1986,21(02):307. |
| [14] | Ernst B;Hilaire L;Kiennemann A .[J].Catalysis Today,1999,50(02):413. |
| [15] | 李强 .[D].北京:中国石油大学(北京),2001. |
| [16] | Kogelbauer A;Weber J C;Goodwin J G .[J].Catalysis Letters,1995,34(3-4):259. |
| [17] | Schanke D;Hilmen A M;Bergene E;Kinnari K Rytter E Adnanes E Holmen A .[J].Catalysis Letters,1995,34(3-4):269. |
| [18] | Hilmen A M;Schanke D;Hanssen K F;Holmen A .[J].Applied Catalysis A:General,1999,186(1-2):169. |
| [19] | Li J L;Davis B H .[J].Studies in Surface Science and Catalysis,2004,147:307. |
| [20] | Chen J G;Wang X Z;Xiang H W;Sun Y H .[J].Studies in Surface Science and Catalysis,2001,136:525. |
| [21] | Van Berge P J;Van de Loosdrecht J;Barradas S;Van der Kraan A M .[J].Catalysis Today,2000,58(04):321. |
| [22] | Kiss G.;Kliewer CE.;DeMartin GJ.;Culross CC.;Baumgartner JE. .Hydrothermial deactivation of silica-supported cobalt catalysts in Fischer-Tropsch synthesis[J].Journal of Catalysis,2003(1):127-140. |
| [23] | Saib AM;Borgna A;de Loosdrecht JV;van Berge PJ;Niemantsverdriet JW .XANES study of the susceptibility of nano-sized cobalt crystallites to oxidation during realistic Fischer-Tropsch synthesis[J].Applied Catalysis, A. General: An International Journal Devoted to Catalytic Science and Its Applications,2006(0):12-19. |
| [24] | Saib A M;Borgna A;Van de Loosdrecht J;Van Berge P J Geus J W Niemantsverdriet J W .[J].Journal of Catalysis,2006,239(02):326. |
| [25] | Huffman GP.;Zhao JM.;Huggins FE.;Hoost TE.;Halvorsen S. Goodwin JG.;Shah N. .IN SITU XAFS INVESTIGATION OF K-PROMOTED CO CATALYSTS[J].Journal of Catalysis,1995(1):17-25. |
| [26] | Saib A M;Borgna A;Van de Loosdrecht J;Van Berge P J Niemantsverdriet J W .[J].Journal of Physical Chemistry B,2006,110(17):8657. |
| [27] | 代小平,余长春,沈师孔.助剂CeO2对Co/Al2O3催化剂上F-T合成反应性能的影响[J].催化学报,2001(02):104-108. |
| [28] | Jacobs G;Das T K;Zhang Y Q;Li J L Racoillet G Davis B H .[J].Applied Catalysis A:General,2002,233(1-2):263. |
| [29] | Barrault J;Alouche A;Paul-Boncour V;Hilaire L Percheron-Guegan A .[J].Applied Catalysis,1989,46(02):269. |
| [30] | Trovarelli A.;Dolcetti G.;Lorca JL.;Deleitenburg C. .CO2 METHANATION UNDER TRANSIENT AND STEADY-STATE CONDITIONS OVER RH/CEO2 AND CEO2-PROMOTED RH/SIO2 - THE ROLE OF SURFACE AND BULK CERIA[J].Journal of Catalysis,1995(1):111-124. |
| [31] | Ernst B;Libs S;Chaumette P;Kiennemann A .[J].Applied Catalysis A:General,1999,186(1-2):145. |
| [32] | Burroughs P;Hammett A;Orchard A F;Thornton G.[J].Journal of the Chemical Society Dalton Transactions,1976(17):1686. |
| [33] | Rodriguez-Ramos I;Guerrero-Ruiz A;Fierro J L G .[J].Applied Surface Science,1989,40(03):239. |
| [34] | Lee SC.;Jang JH.;Lee BY.;Kim JS.;Kang M.;Lee SB.;Choi MJ.;Choung SJ. .Promotion of hydrocarbon selectivity inCO(2) hydrogenation by Ru component[J].Journal of molecular catalysis, A. Chemical,2004(1/2):131-141. |
| [35] | Puskas I;Fleisch TH;Full PR;Kaduk JA;Marshall CL;Meyers BL .Novel aspects of the physical chemistry of CO/SiO2 Fischer-Tropsch catalyst preparations - The chemistry of cobalt silicate formation during catalyst preparation or hydrogenation[J].Applied Catalysis, A. General: An International Journal Devoted to Catalytic Science and Its Applications,2006(0):146-154. |
| [36] | Jablonski JM.;Krajczyk L.;Wolcyrz M. .On cobalt silicate formation during high-temperature calcination of impregnated cobalt/silica catalysts[J].Journal of Catalysis,1998(2):530-534. |
| [37] | Van Berge P J;Van De Loosdrecht J;Visagie J L .[P].US 6835690,2004. |
| [38] | Hilmen A M;Schanke D;Holmen A .[J].Studies in Surface Science and Catalysis,1997,107:237. |
| [39] | Rothaemel M;Hanssen K F;Blekkan E A;Schanke D Holmen A .[J].Catalysis Today,1997,38(01):79. |
| [40] | Trovarelli A .[J].Catalysis Review:Science and Engineering,1996,38(04):439. |
| [41] | Van Steen E;Claeys M;Dry M E;Van de Loosdrecht J Viljoen E Visagie J L .[J].Journal of Physical Chemistry B,2005,109(08):3575. |
| [42] | Iglesia E .[J].Applied Catalysis A:General,1997,161(1-2):59. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%