螯合剂对Co-Mo/Al<sub>2</sub>O<sub>3</sub>成型加氢脱硫催化剂性能的影响

柳来栓; 裴甜婕; 安文平; 李裕; 李楠

螯合剂对Co-Mo/Al₂O₃成型加氢脱硫催化剂性能的影响

中北大学化工与环境学院, 山西太原 030051

基金项目: 山西省科技重大专项（20111101013）；山西省自然科学基金（2009011011-4）。

详细信息

通讯作者:
柳来栓，Tel：13834565576，E-mail：liulaishuan@nuc.edu.cn。

中图分类号: O643.36
计量
- 文章访问数: 849
- HTML全文浏览量: 37
- PDF下载量: 650
- 被引次数: 0
出版历程
- 收稿日期: 2013-12-05
- 修回日期: 2014-03-19
- 刊出日期: 2014-06-30

Effect of the chelating agent on the hydrodesulfurization activity of extruded Co-Mo/Al₂O₃ catalysts

School of Chemical Engineering and Environment, North University of China, Taiyuan 030051, China

摘要

摘要: 以拟薄水铝石为原料，添加有机溶剂，经挤条成型、干煅、焙烧制备了比表面积大、孔分布宽的柱状γ-Al₂O₃载体；采用共浸渍法制备了系列Co-Mo/Al₂O₃催化剂（CoO和MoO₃质量分数分别为2%和8%）。利用低温氮吸附、XRD和H₂-TPR技术对催化剂进行了表征，考察了螯合剂柠檬酸（CA）、草酸（OA）和乙二胺四乙酸（EDTA）对成型催化剂粗苯加氢脱硫活性的影响。结果表明，添加螯合剂后，催化剂的前驱体主要沉积在载体的3~10 nm中孔内，活性组分以无定形态高度分散在载体上。添加CA可提高催化剂的还原性，显著降低Mo⁶⁺的还原温度。在300 ℃、3.0 MPa、液体空速（LHSV）为2 h^-1和氢油体积比为600的条件下，噻吩硫的脱除率可达到99.9%以上。
- 螯合剂 /
- Co-Mo/Al₂O₃ /
- 成型催化剂 /
- 加氢脱硫 /
- 拟薄水铝石 /
- 柠檬酸
Abstract: γ-Al₂O₃ monolith support with high surface area and wide pore size distribution was obtained by extruding the mixture of pseudo boehmite and organic additives, as well as subsequent drying and calculation; a series of Co-Mo catalysts with ca. 8% molybdenum and 2% cobalt were prepared through co-impregnation of the support with solutions of ammonium heptamolybdate, cobalt nitrate and the chelating agent of citric acid (CA), oxalic acid (OA) and ethylenediamine tetraacetic acid (EDTA). The Co-Mo/Al₂O₃ catalysts were characterized by nitrogen sorption, XRD and H₂-TPR; the effect of chelating agents on their textural properties and activity in hydrodesulphurisation (HDS) of a commercial crude benzol was investigated. The results indicated that the catalyst precursors were mostly deposited over the surface of the mesopores with a diameter between 3 and 10 nm; the addition of chelating agent results in a high dispersion of Co-Mo species on the alumina support. The H₂-TPR results revealed that the addition of CA is able to improve the catalyst reducibility and shift the reduction temperature of Mo⁶⁺ to lower temperature. For the HDS reaction of the real-feedstock in a down-flow tubular reactor under 300 ℃, 3.0 MPa, a liquid hourly space velocity (LHSV) of 2 h^-1, and a hydrogen/oil volume ratio of 600, the removal of thiophene sulfur reaches 99.9% over the CA-promoted Co-Mo/Al₂O₃ catalyst.
- chelating agent /
- Co-Mo/Al₂O₃ /
- preformed catalyst /
- hydrodesulfurization /
- pseudo boehmite /
- citric acid

HTML全文

参考文献(16)

齐和日玛, 李会峰, 袁蕙, 张韫宏, 徐广通. Al₂O₃性质对加氢脱硫催化剂Co-Mo/Al₂O₃活性相形成的影响[J]. 催化学报, 2011, 32(2): 240-249. (Qiherima, LI Hui-feng, YUAN Hui, ZHANG Yun-hong, XU Guang-tong. Effect of alumina supports on the formation of active phase of selective hydrodesulfurization catalysts Co-Mo/Al₂O₃[J]. Chinese Journal of Catalysis, 2011, 32(2): 240-249.)

李广慈, 赵会吉, 赵瑞玉, 刘晨光. 不同扩孔方法对催化剂载体氧化铝孔结构的影响[J]. 石油炼制及化工, 2010, 41(1): 49-53. (LI Guang-ci, ZHAO Hui-ji, ZHAO Rui-yu, LIU Chen-guang. Effects of various pore-enlarging methods on the pore structure of alumina catalyst support[J]. Petroleum Processing and Petrochemicals, 2010, 41(1): 49-53.)

聂红, 李明丰, 高晓东, 李大东. 石油炼制中的加氢催化剂和技术[J]. 石油学报(石油加工), 2010, 10(S): 77-81. (NIE Hong, LI Ming-feng, GAO Xiao-dong, LI Da-dong. Hydrogenation catalyst and technology in petroleum processing[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2010, 10(S): 77-81.)

李宇慧, 冯丽娟, 王景刚, 徐康文, 李春虎. MoO₃/A1₂O₃介孔催化剂在柴油氧化脱硫中的应用[J]. 石油学报(石油加工), 2011, 27(6): 878-883. (LI Yu-hui, FENG Li-juan, WANG Jing-gang, XU Kang-wen, LI Chun-hu. Oxidative desulfurization of diesel oil by mesoporous catalyst MoO₃/Al₂O₃[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2011, 27(6): 878-883.)

LIU F, XU S P, CHI Y W, XUE D F. A novel alumina-activated carbon composite supported NiMo catalyst for hydrodesulfurization of dibenzothiophene[J]. Catal Commun, 2011, 12(6): 521-524.

周同娜, 尹海亮, 柳云骐, 韩姝娜, 柴永明, 刘晨光. 磷含量对NiMo/γ-Al₂O₃催化剂活性相结构的影响[J]. 燃料化学学报, 2010, 38(1): 69-74. (ZHOU Tong-na, YIN Hai-liang, LIU Yun-qi, HAN Shu-na, CHAI Yong-ming, LIU Chen-guang. Effect of phosphorus content on the active phase structure of NiMo/Al₂O₃ catalyst[J]. Journal of Fuel Chemistry and Technology, 2010, 38(1): 69-74.)

INAMURA K, UCHIKAWA K, MATSUDA S, AKAI Y. Preparation of active HDS catalysts by controlling the dispersion of active species[J]. Appl Surf Sci, 1997, 121(1): 468-475.

倪月琴, 臧璟龄, 张吉仁. 加氢脱氮催化剂活性相的表征——Ⅰ. 硫化Mo/Al₂O₃的表面和化学结构[J]. 催化学报, 1991, 12(1): 14-19. (NI Yue-qin, ZANG Jing-ling, ZHANG Ji-ren. Characterization of active phase of hydrode-nitrogenation catalyst——Ⅰ. The surface and chemical structure of sulfided Mo/Al₂O₃[J]. Chinese Journal of Catalysis, 1991, 12(1): 14-19.)

赵振兴, 夏春谷, 薛群基, 李殿卿, 刘鹏程. 球形SiO₂-Al₂O₃的制备、结构和性能[J]. 物理化学学报, 2007, 23(4): 549-553. (ZHAO Zhen-xing, XIA Chun-gu, XUE Qun-ji, LI Dian-qing, LIU Peng-cheng. Preparation, structure and properties of spherical SiO₂-Al₂O₃ composites[J]. Acta Physico-Chimica Sinica, 2007, 23(4): 549-553.)

QU L L, ZHANG W P, KOOYMAN P J, PRINS R. MAS NMR, TPR and TEM studies of the interaction of Ni Mo with alumina and silicaalumina supports[J]. J Catal, 2003, 215(1): 7-13.

HENKER M, WENDLANDT K, VALYON J, BRONMANN P. Structure of MoO₃/A1₂O₃-SiO₂ catalysts[J]. Appl Catal, 1991, 69(1): 205-220.

MARZARI A J, RAJAGOPAL S, MIRANDA R. Bifunctional mechanism of pyridine hydrodenitrogenation[J]. J Catal, 1995, 156(2): 255-264.

VAKROS J, KORDULIS C, LYCOURGHIOTIS A. Cobalt oxide supported γ-alumina catalyst with very high active surface area prepared by equilibrium deposition filtration[J]. Langmuir, 2002, 18(2): 417-422.

RAJAGOPAL S, MARINI H J, MARZARI J A, MIRANDA R. Silica alumina supported acidic molybdenum catalysts TPR and XRD characterization[J]. J Catal, 1994, 147(2): 417-428.

ZHAO H B, ZHANG Z S, ZHANG J, RING Z. Aqueous interfacial chemistry in the catalyst preparation of NiMo/Al₂O₃ system by EDTA-containing impregnation[J]. Energy Fuels, 2006, 20(5): 1822-1827.

RINALDI N, YOSHIOKA M, KUBOTA T, OKAMOTO Y. Hydrodesulfurization activity of Co-Mo/Al₂O₃ catalysts prepared with citric acid: Post-treatment of calcined catalysts with high Mo loading[J]. J Jpn Petrol Inst, 2010, 53(5): 292-302.

施引文献

资源附件(0)

访问统计