表面活性剂对水热法合成MoS<sub>2</sub>加氢脱硫催化剂的影响

钦柏豪; 杨运泉; 刘文英; 王威燕; 杨余; 何兵

表面活性剂对水热法合成MoS₂加氢脱硫催化剂的影响

湘潭大学化工学院, 湖南湘潭 411105

基金项目: 教育部化工过程模拟与优化工程研究中心开放基金(2008HGZX02); 湖南省教育厅开放基金(10K062)。

详细信息

通讯作者:
杨运泉(1963-),男,教授。Tel:13055142055,E-mail:yangyunquan@xtu.edu.cn

中图分类号: O643.36
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- 被引次数: 0
出版历程
- 收稿日期: 2012-03-06
- 修回日期: 2012-06-08
- 刊出日期: 2012-11-30

Effect of surfactants on preparation of MoS₂ catalyst by a hydrothermal method

School of Chemical Engineering, Xiangtan University, Xiangtan 411105, China

摘要

摘要: 采用水热法合成了MoS₂加氢脱硫催化剂,用物理吸附、XRD、SEM、TEM等手段对催化剂进行表征,并以噻吩为模型化合物研究不同类型表面活性剂对合成MoS₂催化剂活性的影响。结果表明,加入表面活性剂制备的催化剂颗粒疏松均匀,比表面积、孔容、孔径都较大,并且MoS₂层状堆叠数目增加;所制催化剂在噻吩加氢脱硫反应中均显示出较好的催化活性,在573 K、4.0 MPa条件下,噻吩加氢脱硫的转化率均大于97.0%,加入阳离子表面活性剂的Mo-S-C催化活性最高,噻吩转化率可达到99.9%。MoS₂催化剂的活性顺序为Mo-S-C>Mo-S-S>Mo-S-P>Mo-S-N。
- MoS₂ /
- 水热合成 /
- 噻吩 /
- 加氢脱硫
Abstract: MoS₂ hydrodesulfurization catalyst was prepared by hydrothermal method. The resulting materials were characterized by BET, XRD, SEM and TEM. The influences of different surfactants on activity of catalyst were studied by measuring the hydrodesulfurization (HDS) of thiophene. The results showed that the catalyst particles with the addition of surfactants were loose, while the catalyst without the addition of surfactant exhibited serious agglomeration phenomenon. The surface area, pore volume, diameter and the number of the stacked layer of the catalysts with the addition of surfactants were much greater than those of catalysts without surfactants. The catalysts with surfactants showed high activity in the HDS of thiophene, the conversion of thiophene could reach to 97.0% at 573 K and 4.0 MPa pressure. Furthermore, the catalyst with the addition of cation surfactants showed the highest activity among these catalysts, and the conversion of thiophene was 99.9%. By comparing the conversion, the reactivity order of the catalysts was: Mo-S-C>Mo-S-S>Mo-S-P>Mo-S-N.
- MoS₂ /
- hydrothermal synthesis /
- thiophene /
- hydrodesulfurization

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参考文献(31)

SONG C. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel[J]. Catal Today, 2003, 86(1/4): 211-263.

BRUNET S, MEY D, PEROT G. On the hydrodesulfurization of FCC gasoline: A review[J]. Appl Catal A, 2005, 287(2): 143-172.

STANISLAUS A, MARAFI A, RANA M S. Recent advances in the science and technology of ultra low sulfur diesel(ULSD) production[J]. Catal Today, 2010, 153(1/2): 1-68.

CHIANELLI R R, BERHAULT G, TORRES B. Unsupported transition metal sulfide catalysts: 100 years of science and application[J]. Catal Today, 2009, 147(3/4): 275-286.

EIJSBOUTS S, MAYO S W, FUJITA K. Unsupported transition metal sulfide catalysts: From fundamentals to industrial application[J]. Appl Catal A, 2007, 322(16): 58-66.

YOOSUK B, KIM J H, SONG C, NGAMCHARUSSRIVIVHAI C, PRASASSARAKICH P. Highly active MoS₂, CoMoS₂ and NiMoS₂ unsupported catalysts prepared by hydrothermal synthesis for hydrodesulfurization of 4, 6-dimethyldibenzothiophene[J]. Catal Today, 2008, 130(1): 14-23.

WANG L, ZHANG Y N, ZHANG Y L, JIANG Z X, LI C. Ultra-deep hydrodesulfurization of diesel fuels on trimetallic NiMoW sulfide catalysts[J]. Chem-Eur J, 2009, 15(46): 12571-12575.

NAVA H, ORNELAS C, AGUILAR A, BERHAULT G, FUENTES S, ALONSO G. Cobalt-molybdenum sulfide catalysts prepared by in situ activation of bimetallic (Co-Mo) alkylthiomolybdates[J]. Catal Lett, 2003, 86(4): 257-265.

NAVA H, PEDRAZA F, ALONSO G. Nickel-molybdenum-tungsten sulphide catalysts prepared by in situ activation of tri-metallic(Ni-Mo-W) alkylthiomolybdotungstates[J]. Catal Lett, 2005, 99(1/2): 65-71.

ALONSO G, BERHAULT G, AGUILAR A, COLLINS V, ORNELAS C, FUENTES S, CHIANELLI R R. Characterization and HDS activity of mesoporous MoS₂ catalysts prepared by in situ activation of tetraalkylammonium thiomolybdates[J]. J Catal, 2002, 208(2): 359-369.

FARAG H, SAKANISHI K, KOUZU M, MATSUMURA A, SUGIMOTO Y, SAITO I. Dibenzothiphene hydrodesulfurization over synthesized MoS₂ catalysts[J]. J Mol Catal A, 2003, 206(1/2): 399-408.

HUIRACHE ACUNA R, ALBITER M A, ORNELAS C, PARAGUAY DELGADO F, MARTINEZ SANCHEZ R, ALONSO G. Ni(Co)-Mo-W sulphide unsupported HDS catalysts by ex situ decomposition of alkylthiomolybdotungstates[J]. Appl Catal A, 2006, 308: 134-142.

HUIRACHE ACUNA R, ALBITER M A, ESPINO J, ORNELAS C, ALONSO G, PARAGUAY DELGADO F, RICO J L, MARTINEZ SANCHEZ R. Synthesis of Ni-Mo-W sulphide catalysts by ex situ decomposition of trimetallic precusors[J]. Appl Catal A, 2006, 304: 124-130.

GENUIT D, AFANASIEV P, VRINAT M. Solution syntheses of unsupported Co(Ni)-Mo-S hydrotreating catalysts[J]. J Catal, 2005, 235(2): 302-317.

ZHANG L, AFANASIEV P, LI D, SHI Y, VRINAT M. Synthesis of unsupported Ni-W-S hydrotreating catalysts from the oxothiosalt (NH₄)₂WO₂S₂[J]. C R Chim, 2008, 11(1): 130-136.

ZHANG L, AFANASIEV P, LI D, LONG X, VRINAT M. Solution synthesis of the unsupported Ni—W sulfide hydrotreating catalysts[J]. Catal Today, 2008, 130(1): 24-31.

毕云飞, 曾双亲, 聂红, 李大东, 杨清河, 李洪宝. 一种非负载型加氢催化剂的制备方法: 中国, 101468309. 2009-07-01. (BI Yun-fei, ZENG Shuang-qin, NIE Hong, LI Da-dong, YANG Qing-he, LI Hong-bao. The preparation method of a unsupported hydrotreating catalyst: CN, 101468309. 2009-07-01.)

徐学军, 王继锋, 刘东香, 王海涛, 冯小萍. 一种加氢催化剂的制备方法:中国, 101172261. 2008-05-07. (XU Xue-jun, WANG Ji-feng, LIU Dong-xiang, WANG Hai-tao, FENG Xiao-ping. The preparation method of a hydrotrating catalyst: CN, 101172261. 2008-05-07.)

邵长丽, 殷长龙, 张俊萍, 陈世安, 刘晨光. 尿素反应法制备介孔Ni-Mo复合氧化物[J]. 无机化学学报, 2008, 24(11): 1782-1788. (SHAO Chang-li, YIN Chang-long, ZHANG Jun-ping, CHEN Shi-an, LIU Chen-guang. Synthesis of mesoporous Ni-Mo mixed oxides with urea method[J]. Chinese Journal of Inorganic Chemistry, 2008, 24(11): 1782-1788.)

赵悦, 殷长龙, 陈世安, 崔德强. 柴油超深度加氢脱硫非负载型Ni-Mo-W催化剂的研究[J]. 石油炼制与化工, 2009, 40(12): 26-29. (ZHAO Yue, YIN Chang-long, CHEN Shi-an, CUI De-qiang. Study on the unsupported Ni-Mo-W catalyst for ultra——deep hydrodesulfurization of diesel fuel[J]. Petroleum Processing and Petrochemicals, 2009, 40(12): 26-29.)

安高军, 柴永明, 陈照军, 刘晨光. 低温固相法制备非负载型介孔Ni-Mo-W硫化物催化剂[J]. 中国石油大学学报, 2007, 31(6): 156-160. (AN Gao-jun, CHAI Yong-ming, CHEN Zhao-jun, LIU Chen-guang. Preparation of unsupported and mesoporous Ni-Mo-W sulfide catalysts by low temperature solid-state reaction[J]. Journal of China University of Petroleum, 2007, 31(6): 156-160.)

SING K S W, EVERETT D H, HAUL R A W, MOSCOU L. PIEROTTI R A, ROUQUEROL J, SIEMIENIEWSKA T. Reporting physisorption data forgas/solid systems with special reference to the determination of surface area and porosity[J]. Pure Appl Chem, 1985, 57(4): 603-609.

KRUK M, JARONIEC M. Gas adsorption characterization of ordered organic-inorganic nanocomposite materials[J]. Chem Mater, 2001, 13(10): 3169—3183.

YOOSUK B, SONG C S, KIM J H, NGAMCHARUSSRIVIVHAI C, PRASASSARAKICH P. Effects of preparation conditions in hydrothermal synthesis of highly active unsupported NiMo sulfide catalysts for simultaneous hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene[J]. Catal Today, 2010, 149(1/2): 52-61.

UZCANGA I, BEZVERKHYY I, AFANASIEV P, SCOTT C, VRINET M. Sonochemical preparation of MoS₂ in aqueous solution: Replication of the cavitation bubbles in an inorganic material morphology[J]. Chem.Mater, 2005, 17(14): 3575-3777.

MAJHI A, PUGAZHENTHI G, SHUKLA A. Comparative study of ultrasound stimulation and conventional heating methods on the preparation of nanosized γ-Al₂O₃[J]. Ind Eng Chem Res, 2010, 49(10): 4710-4719.

VRADMAN L, LANDAU M V. Structure-function relations in supported Ni-W sulfide hydrogenation catalysts[J]. Catal Lett, 2001, 77(1/3): 47-54.

ZHANG L, LONG X, LI D, GAO X. Study on high-performance unsupported Ni-Mo-W hydrotreating catalyst[J]. Catal Commun, 2011, 12(11): 927-931.

AFANASIEV P. The influence of reducing and sulfiding conditions on the properties of unsupported MoS₂-based catalysts[J]. J Catal, 2010, 269(2): 269-280.

CRUZ-REYES J, AVALOS-BORJA M, FARIAS M H, FUENTES S. Hydrodesulfurization catalyst prepared by two methods analyzed by transmission elecron microscopy[J]. J Catal, 1992, 137(1): 232-242.

VATZQUEZ A, YANEZ M J, FUENTES S, AVALOS-BORJA M. High resolution electron microscopy characterization of sulfided palladium particles on amorphous SiO₂[J]. Catal Lett, 1994, 28(2/4): 351-360.

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