FeMn、FeMnNa和FeMnK催化剂上合成气制低碳烯烃的比较

doi:10.3866/PKU.WHXB201408051

物理化学学报 >> 2014, Vol. 30 >> Issue (10): 1932-1940.doi: 10.3866/PKU.WHXB201408051

FeMn、FeMnNa和FeMnK催化剂上合成气制低碳烯烃的比较

李江兵^1,2, 马宏方¹, 张海涛¹, 孙启文³, 应卫勇¹, 房鼎业¹

1. 华东理工大学大型工业反应器工程教育部工程中心化学工程联合国家重点实验室, 上海 200237;
2. 石河子大学化学化工学院, 新疆兵团化工绿色过程重点实验室, 新疆石河子 832003;
3. 煤液化及煤化工国家重点实验室, 上海 201203

收稿日期:2014-06-20 修回日期:2014-08-04 发布日期:2014-09-30
通讯作者: 应卫勇 E-mail:wying@ecust.edu.cn
基金资助:
国家重点基础研究发展计划（973）（2010CB736203）和国家高技术研究发展计划（863）（2011AA05A204）资助

Comparison of FeMn, FeMnNa and FeMnK Catalysts for the Preparation of Light Olefins from Syngas

LI Jiang-Bing^1,2, MA Hong-Fang¹, ZHANG Hai-Tao¹, SUN Qi-Wen³, YING Wei-Yong¹, FANG Ding-Ye¹

1. State Key Laboratory of Chemical Engineering, Engineering Research Center of Large Scale Reactor Engineering and Technology of the Ministry of Education, East China University of Science and Technology, Shanghai 200237, P. R. China;
2. Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, The Xinjiang Uygur Autonomous Region, P. R. China;
3. State Key Laboratory of Coal Liquefaction and Coal Chemical Technology, Shanghai 201203, P. R. China

Received:2014-06-20 Revised:2014-08-04 Published:2014-09-30
Contact: YING Wei-Yong E-mail:wying@ecust.edu.cn
Supported by:
The project was supported by the Major State Basic Research Program of China (2010CB736203) and National High-Tech R&D Program of China (2011AA05A204).

摘要/Abstract

摘要：

研究了钠、钾助剂对FeMn 合成低碳烯烃催化剂结构及性能的影响. 低温N₂吸附、X射线光电子能谱（XPS）、X射线衍射（XRD）、H₂程序升温还原（H₂-TPR）、CO/CO₂程序升温脱附（CO/CO₂-TPD）、Mössbauer 谱和CO+H₂反应的研究结果表明，增加Mn助剂含量促进了活性相的分散和低碳烯烃的生成，而过多锰助剂在催化剂表面的富集则降低了费托合成反应的CO转化率；钾助剂和钠助剂的加入均抑制了催化剂的还原并且促进了CO₂和CO的吸附. 比较还原后（H₂/CO摩尔比为20）和反应后（H₂/CO摩尔比为3.5）催化剂的体相结构可以发现，在FeMn、FeMnNa和FeMnK催化剂中，由于钾助剂的碱性和CO吸附能力较强，因此体相中FeC_x的含量相对较高；而活性测试结果表明，FeMnNa催化剂拥有最好的CO转化率（96.2%）和低碳烯烃选择性（30.5%，摩尔分数）.

关键词: 低碳烯烃, 费托合成, 铁锰催化剂, 钠助剂, 钾助剂

Abstract:

The influence of sodium and potassium promoters on the structure and reaction behavior of an FeMn catalyst toward light olefin synthesis from syngas was investigated by N₂ adsorption, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), H₂ temperature-programmed reduction (H₂-TPR), CO/CO₂ temperature-programmed desorption (CO/CO₂-TPD), Mössbauer spectroscopy (MES) and CO+H₂ reaction. We found that an increase in manganese improves the dispersion of the active Fe component and light olefin selectivity; however, excessive enrichment with the Mn promoter on the catalyst surface suppresses CO conversion. Potassium and sodium inhibit the reduction of the catalyst in H₂ and improve the adsorption of CO₂ and CO because of the enhanced surface basicity of the catalysts. After reduction with syngas (n_H₂/n_CO=20) and reaction with syngas (n_H₂/n_CO=3.5), the analysis of the bulk structure was compared with those of the FeMn, FeMnNa, and FeMnK catalysts. The results show that FeC_x is found in relatively high levels in the FeMnK catalysts because of the stronger alkalinity and adsorbability of CO. However, Fischer-Tropsch synthesis (FTS) results indicate that sodium and potassium improved the selectivity toward light olefins. The best catalytic performance was achieved by the FeMnNa catalyst. Its CO conversion and light olefins selectivity were 96.2% and 30.5% (molar fraction), respectively.

Key words: Light olefin, Fischer-Tropsch synthesis, FeMn catalyst, Sodium promoter, Potassium promoter

李江兵, 马宏方, 张海涛, 孙启文, 应卫勇, 房鼎业. FeMn、FeMnNa和FeMnK催化剂上合成气制低碳烯烃的比较[J]. 物理化学学报, 2014, 30(10), 1932-1940. doi: 10.3866/PKU.WHXB201408051

LI Jiang-Bing, MA Hong-Fang, ZHANG Hai-Tao, SUN Qi-Wen, YING Wei-Yong, FANG Ding-Ye. Comparison of FeMn, FeMnNa and FeMnK Catalysts for the Preparation of Light Olefins from Syngas[J]. Acta Phys. -Chim. Sin. 2014, 30(10), 1932-1940. doi: 10.3866/PKU.WHXB201408051

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201408051

https://www.whxb.pku.edu.cn/CN/Y2014/V30/I10/1932

参考文献

(1) Janardanarao, M. Ind. Eng. Chem. Res. 1990, 29, 1735. doi: 10.1021/ie00105a001
(2) Ma,W. P.; Ding, Y. J.; Luo, H. Y.; Lin, P. Z.; Lin, L.W. Chinese Journal of Catalysis 2001, 22, 279. [马文平, 丁云杰, 罗洪原, 林培滋, 林励吾. 催化学报, 2001, 22, 279.] (3) Mirzaei, A. A.; Habibpour, R.; Kashi, E. Appl. Catal. A-Gen. 2005, 296, 222. doi: 10.1016/j.apcata.2005.08.033
(4) Dry, M. E.; Shingles, T.; Botha, C. S. V. H. J. Catal. 1970, 17, 341. doi: 10.1016/0021-9517(70)90109-0
(5) Lohitharn, N.; Goodwin, J. G., Jr. J. Catal. 2008, 260, 7. doi: 10.1016/j.jcat.2008.08.011
(6) Botes, F. G.; Govender, N. S. Energ. Fuel. 2007, 21, 3095. doi: 10.1021/ef7003464
(7) Ngantsoue-Hoc,W.; Zhang, Y. Q.; O’Brien, R. J.; Luo, M.; Davis, B. H. Appl. Catal. A-Gen. 2002, 236, 77. doi: 10.1016/S0926-860X(02)00278-8
(8) Wang, C.; Zhao, H. B.;Wang, H.; Liu, L. T.; Xiao, C. X.; Ma, D. Catal. Today 2012, 183, 143. doi: 10.1016/j.cattod.2011.10.020
(9) Dry, M. E.; Oosthuizen, G. J. J. Catal. 1968, 11, 18. doi: 10.1016/0021-9517(68)90004-3
(10) Yang, Y.; Xiang, H.W.; Xu, Y. Y.; Li, Y.W. Appl. Catal. A-Gen. 2004, 266, 181. doi: 10.1016/j.apcata.2004.02.018
(11) An, X.;Wu, B. S.; Hou,W. J.;Wan, H. J.; Tao, Z. C.; Li, T. Z.; Zhang, Z. X.; Xiang, H.W.; Li, Y.W.; Xu, B.; Yi, F. J. Mol. Catal. A: Chem. 2007, 263, 266. doi: 10.1016/j.molcata.2006.09.003
(12) Abbot, J.; Clark, N. J.; Baker, B. G. Appl. Catal. A-Gen. 1986, 26, 141. doi: 10.1016/S0166-9834(00)82547-6
(13) Galvis, H. M. T.; Bitter, J. H.; Khare, C. B.; Ruitenbeek, M.; Dugulan, A. I.; Jong, K. P. D. Science 2012, 335, 835. doi: 10.1126/science.1215614
(14) Zhang, J. L.; Ma, L. H.; Fan, S. B.; Zhao, T. S.; Sun, Y. H. Fuel2013, 109, 116. doi: 10.1016/j.fuel.2012.12.081
(15) Qian,W. X.; Zhang, H. T.; Ying,W. Y.; Fang, D. Y. J. Nat. Gas Chem. 2011, 20, 389. doi: 10.1016/S1003-9953(10)60203-4
(16) Herranz, T.; Rojas, S.; Pérez-Alonso, F. J.; Ojeda, M.; Terreros, P.; Fierro, J. L. G. Appl. Catal. A-Gen. 2006, 311, 66. doi: 10.1016/j.apcata.2006.06.007
(17) Tao, Z. C.; Yang, Y.;Wan, H. J.; Li, T. Z.; An, X.; Xiang, H.W.; Li, Y.W. Catal. Lett. 2007, 114, 161. doi: 10.1007/s10562-007-9060-6
(18) Cao, C. J.; Liu, X. G.; Ju, X. R.; Chen, X. R. Acta Phys. -Chim. Sin. 2013, 29, 2475. [曹崇江, 刘晓庚, 鞠兴荣, 陈晓荣. 物理化学学报, 2013, 29, 2475.] doi: 10.3866/PKU.WHXB201310101
(19) Leith, I. R.; Howden, M. G. Appl. Catal. 1988, 37, 75. doi: 10.1016/S0166-9834(00)80752-6
(20) An, X.;Wu, B. S.;Wan, H. J.; Li, T. Z.; Tao, Z. C.; Xiang, H. W.; Li, Y.W. Catal. Commun. 2007, 8, 1957. doi: 10.1016/j.catcom.2007.03.016
(21) Wang, H. L.; Yang, Y.; Xu, J.;Wang, H.; Ding, M. Y.; Li, Y.W. J. Mol. Catal. A: Chem. 2010, 326, 29. doi: 10.1016/j.molcata.2010.04.009
(22) Motjope, T. R.; Dlamini, H. T.; Hearne, G. R.; Coville, N. J. Catal. Today 2002, 71, 335. doi: 10.1016/S0920-5861(01)00460-6
(23) Yang, Y.; Xiang, H.W.; Tian, L.;Wang, H.; Zhang, C. H.; Tao, Z. C.; Xu, Y. Y.; Zhong, B.; Li, Y.W. Appl. Catal. A-Gen. 2005, 284, 105. doi: 10.1016/j.apcata.2005.01.025
(24) Jung, H.; Thomson,W. J. J. Catal. 1992, 134, 654. doi: 10.1016/0021-9517(92)90350-Q
(25) Tao, Z. C.; Yang, Y.; Zhang, C. H.; Li, T. Z.;Wang, J. H.;Wan, H. J.; Xiang, H.W.; Li, Y.W. Catal. Commun. 2006, 7, 1061. (26) Dry, R. E.; Shingles, T.; Bboshoff, L. J.; Oosthuizen, G. J. J. Catal. 1969, 15, 190. doi: 10.1016/0021-9517(69)90023-2
(27) Miller, D. G.; Moskovits, M. The Journal of Physical Chemistry 1988, 92, 6081. doi: 10.1021/j100332a047
(28) Zhang, X. J.; Liu, Y.; Liu, G. Q.; Tao, K.; Jin, Q.; Meng, F. Z.; Wang, D.; Tsubaki, N. Fuel 2012, 92, 122. doi: 10.1016/j.fuel.2011.07.041

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FeMn、FeMnNa和FeMnK催化剂上合成气制低碳烯烃的比较

Comparison of FeMn, FeMnNa and FeMnK Catalysts for the Preparation of Light Olefins from Syngas

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