还原温度对Fe-Mo催化剂性质及F-T合成性能的影响

秦绍东; 张成华; 许健; 吴宝山; 相宏伟; 李永旺

还原温度对Fe-Mo催化剂性质及F-T合成性能的影响

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001;
2.
中国科学院研究生院, 北京 100049

基金项目: 国家杰出青年科学基金(20625620); 国家自然科学青年基金(20703054)。

详细信息

通讯作者:
张成华, Tel: (0351) 7560668; E-mail: zhangchh@sxicc.ac.cn。

中图分类号: TQ529.2
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出版历程
- 收稿日期: 2011-03-07
- 修回日期: 2011-06-21
- 刊出日期: 2012-02-29

Effect of reduction temperature on the properties and Fischer-Tropsch synthesis performance of Fe-Mo catalysts

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;
2.
Graduate University of Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 研究了还原温度对Fe-Mo催化剂性质及费托(F-T)合成性能的影响。采用N₂物理吸附、X射线衍射、穆斯堡尔谱和H₂程序升温脱附技术对催化剂进行了表征。结果表明,随还原温度升高,金属铁晶粒粒径增大,金属铁上的H₂吸附量先升后降;催化剂还原度提高,反应态催化剂碳化铁含量递增。催化剂F-T合成性能在280 ℃、1.5 MPa、2 000 h^-1、合成气H₂/CO比为2.0条件下在固定床反应器中测试。反应结果表明,随还原温度提高,催化剂接近稳态时的活性和重质烃选择性(C₅⁺)先升后降,而甲烷选择性则先降后升。350 ℃还原催化剂具有最佳F-T合成反应性能。
- 费托合成 /
- 铁基催化剂 /
- 钼助剂 /
- 氢气吸附 /
- 还原温度
Abstract: Effects of reduction temperature on the properties and Fischer-Tropsch synthesis (FTS) performance of Fe-Mo catalyst were studied. Catalysts were characterized by N₂ adsorption, X-ray diffraction (XRD), Mssbauer effect spectroscopy (MES) and H₂ temperature-programmed desorption (TPD). The characterization results indicate that the crystallite size of metallic iron, the reduction degree and the carbide content (in catalysts after reaction) monotonously increase with increasing reduction temperature, while the amount of H₂ chemisorption on metallic iron sites show a maximum at reduction temperature at 350 ℃. FTS performance was tested in a fixed-bed reactor at 280 ℃, 1.5 MPa, 2 000 h^-1 and syngas H₂/CO= 2.0. It is found that the steady-state FTS activity and the heavy hydrocarbons (C₅⁺) selectivity of the catalyst increase up to 350 ℃, and then decrease with further increasing reduction temperature. The catalyst redu at 350 ℃shows the optical FTS performance.
- Fischer-Tropsch synthesis /
- iron-based catalyst /
- Mo promotion /
- hydrogen adsorption /
- reduction temperature

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参考文献(23)

DRY M E. The Fischer-Tropsch process: 1950-2000[J]. Catal Today, 2001, 71(3/4): 227-241.

陈建刚, 相宏伟, 李永旺, 孙予罕. 费托法合成液体燃料关键技术研究进展[J]. 化工学报, 2003, 54(4): 516-523. (CHEN Jian-gang, XIANG Hong-wei, LI Yong-wang, SUN Yu-han. Advance in key techniques of Fischer-Tropsch synthesis for liquid fuel production[J]. Journal of Chemical Industry and Engineering (China), 2003, 54(4): 516-523.)

王建华, 杨勇, 常杰, 相宏伟, 李永旺, 易凡, 徐斌富. 还原参数对F-T合成Fe-Mn催化剂物相结构的影响[J]. 天然气化工, 2006, 31(4): 32-37. (WANG Jian-hua, YANG Yong, CHANG Jie, XIANG Hong-wei, LI Yong-wang, YI Fan, XU Bin. Effect of reduction parameters on the structure of Fe-Mn catalyst for Fischer-Tropsch synthesis[J]. Natural Gas Chemical Industry, 2006, 31(4): 32-37.)

SHROF M D, KALAKKAD D S, COULTER K E, KHLER S D, HARRINGTON M S, JACKSON N B, SAULT A G, DATYE A K. Activation of precipitated iron Fischer-Tropsch synthesis catalysts[J]. J Catal, 1995, 156(2): 185-207.

BUKUR D B, LANG X, DING Y. Pretreatment effect studies with a precipitated iron Fischer-Tropsch catalyst in a slurry reactor[J]. Appl Catal A, 1999, 186(1/2): 255-275.

HAO Q-L, LIU F-X, WANG H, CHANG J, ZHANG C-H, BAI L, XIANG H-W, LI Y-W, YI F, XU B-F. Effect of reduction temperature on a spray-dried iron-based catalyst forslurry Fischer-Tropsch synthesis[J]. J Mol Catal A, 2007, 261(1): 104-111

DING M, YANG Y, WU B, XU J, ZHANG C, XIANG H, LI Y. Study of phase transformation and catalytic performance on precipitated iron-based catalyst for Fischer-Tropsch synthesis[J]. J Mol Catal A, 2009, 303(1/2): 65-71.

郝庆兰, 白亮, 郝栩, 相宏伟, 李永旺, 易凡, 徐斌富. 还原温度与时间对铁基催化剂浆态床F-T合成性能的影响[J]. 燃料化学学报, 2005, 33(5): 590-596. (HAO Qing-lan, BAI Liang, HAO Xu, XIANG Hong-wei, LI Yong-wang, YI Fan, XU Bing-fu. Effect of reduction temperature and duration on iron-based catalyst for slurry phase Fischer-Tropsch synthesis[J]. Journal of Fuel Chemistry and Technology 2005, 33(5): 590-596.)

DUN O W, GULARI E, NG K Y S. Fischer-Tropsch synthesis on charcoal-supported molybdenum: The effect of preparation conditions and potassium promotion on activity and selectivity[J]. Appl Catal, 1985, 15(2): 247-263.

Van STEEN E, VILJOEN E L, van de LOOSDRECHT J, CLAEYS M. Evaluation of molybdenum-modified alumina support materials for Co-based Fischer-Tropsch catalysts[J]. Appl Catal A, 2008, 335(1): 56-65.

MA W, KUGLER E L, WRIGHT J, DADYBURJOR D B. Mo-Fe catalysts supported on activated carbon for synthesis of liquid fuels by the Fischer-Tropsch process: Effect of Mo addition on reducibility, activity, and hydrocarbon selectivity[J]. Energy Fuels, 2006, 20(6): 2299-2307.

QIN S, ZHANG C, XU J, WU B, XIANG H, LI Y. Effect of Mo addition on precipitated Fe catalysts for Fischer-Tropsch synthesis[J]. J Mol Catal A, 2009, 304(1/2): 128-134.

秦绍东, 张成华, 许健, 吴宝山, 相宏伟, 李永旺. Mo、Cu助剂对FeK/SiO2催化剂费托合成性能的影响[J]. 催化学报, 2010, 31(9): 1132-1138. (QIN Shao-dong, ZHANG Cheng-hua, XU Jian, WU Bao-shan, XIANG Hong-wei, LI Yong-wang. Mo and Cu Modified FeK/SiO2 Catalysts for Fischer-Tropschsynthesis[J]. Chinese Journal of Catalysis, 2010, 31(9): 1132-1138.)

YANG Y, XIANG H-W, TIAN L, WANG H, ZHANG C-H, TAO Z-C, XU Y-Y, ZHONG B, LI Y-W. Structure and Fischer-Tropsch performance of iron-manganese catalyst incorporated with SiO2[J]. Appl Catal A, 2005, 284(1/2): 105-122.

LEE M-D, LEE J-F, CHANG C-S. Effect of addition of chrominum, manganese, or molybdemum to iron catalysts for carbon sioxide hydrogenation[J]. Appl Catal, 1991, 72(2): 267-281.

ZHANG H, SHEN J, GE X. The reduction behavior of Fe-O-Mo catalysts studied by temperature-programmed reduction combined with in-situ Mssbauer spectroscopy and X-ray diffraction[J]. J Solid State Chem, 1995, 117(1): 127-135.

沈俭一, 章素, 林励吾. 非担载铁-钼催化剂在氢还原过程中的物相研究[J]. 分子催化, 1993, 7(1): 9-15. (SHEN Jian-y, ZHANG Su, Lin Li-wu. A study on the phase of unsupported iron-molybdenum catalyst during reduction in hydrogen[J]. Journal of Molecular Catalysis(China), 1993, 7(1): 9-15.)

YAMADA M, YASUMARU J, HERCULES D M. Distribution of molybdenum oxidation states in reduced molybdenum/alumina catalysts: correlation with benzene hydrogenation activity[J]. J Phys Chem, 1991, 95(18): 7037-7042.

MERRILL P B, MADIX R J. Hydrogen bonding on iron: correlation of adsorption and desorption states on Fe(100) and perturbation of the Fe-H bond with coadsorbed CO[J]. Surf Sci, 1996, 347(3): 249-264.

LOHITHARN N, GOODWIN J G Jr, LOTERO E. Fe-based Fischer-Tropsch synthesis catalysts containing carbide-forming transition metal promoters[J]. J Catal, 2008, 255(1): 104-113.

SUDSAKORN K, GOODWIN J G Jr, ADEYIGA A A. Effect of activation method on Fe FTS catalysts: Investigation at the site level using SSITKA[J]. J Catal, 2003, 213(2): 204-210.

MURCHISON C M, MURDICK D A. Use syngas for olefin feedstock[J]. Hydrocarbon Process, 1981, 60(1): 159-164.

DUN J W, GULARI E, NG K Y S. Fischer-Tropsch synthesis on charcoal-supported molybdenum: The effect of preparation conditions and potassium promotion on activity and selectivity[J]. Appl Catal, 1985, 15(2): 247-263.

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