Effect of phosphorus loadings on the performance of Co-Mo/γ-Al2O3 in hydrodesulfurization of coal tar

HU Nai-fang; CUI Hai-tao; QIU Ze-gang; ZHAO Liang-fu; MENG Xin-xin; ZHAO Zheng-quan; AO Guang-yu

Volume 44 Issue 6

Jun. 2016

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2016 > 44(6): 745-753

HU Nai-fang, CUI Hai-tao, QIU Ze-gang, ZHAO Liang-fu, MENG Xin-xin, ZHAO Zheng-quan, AO Guang-yu. Effect of phosphorus loadings on the performance of Co-Mo/γ-Al2O3 in hydrodesulfurization of coal tar[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 745-753.

Citation:

HU Nai-fang, CUI Hai-tao, QIU Ze-gang, ZHAO Liang-fu, MENG Xin-xin, ZHAO Zheng-quan, AO Guang-yu. Effect of phosphorus loadings on the performance of Co-Mo/γ-Al₂O₃ in hydrodesulfurization of coal tar[J]. Journal of Fuel Chemistry and Technology, 2016, 44(6): 745-753.

Citation:

PDF( 7467 KB)

Effect of phosphorus loadings on the performance of Co-Mo/γ-Al₂O₃ in hydrodesulfurization of coal tar

1.
Laboratory of Applied Catalysis and Green Chemical Engineering, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
College of Chemistry and Chemical Engineering, Xi'an University of Petroleum, Xi'an 710065, China
4.
College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
5.
CHI FENG BO YUAN KE JI YOU XIAN ZE REN GONG SI, Chifeng 025350, China

More Information

Corresponding author: Tel: 0351-4041526, E-mail: lfzhao@sxicc.ac.cn
Received Date: 2015-12-16
Rev Recd Date: 2016-01-22

Available Online: 2021-01-23

Publish Date: 2016-06-10

Abstract

Abstract

With the fixed loadings of molybdenum oxide of 13.50% and cobalt oxide of 2.11%, respectively, the Co-Mo/γ-Al₂O₃ catalysts were modified by adding different mass concentration of phosphoric acid via separate-step impregnation method. The effect of different phosphorus loadings of catalysts on the hydrodesulfurization performance was studied using middle temperature coal tar from Chifeng, Inner Mongolia. The structural properties of catalysts were characterized by the temperature programmed desorption of NH₃ (NH₃-TPD), XRD, XPS and other methods. The results show that a proper loading of phosphorus can weaken the interaction between the support and the active components, improve the dispersion of active compents on the surface of support, and promote the reduction and sulfuration of the active components and the distribution of acid, which can improve the hydrodesulfurization performance of the catalysts. The catalyst prepared with the phosphoric acid of 4% concentration exhibits the highest hydrodesulfurization activity with the sulfur removal of 96.98%. The effect of mass concentration of phosphoric acid on the hydrodesulfurization activety of the prepared catalysts is in the order of 4% >2% >6% >1% >0 >8%.
- phosphorus modification,
- Co-Mo catalysts,
- coal tar,
- HDS

FullText(HTML)

References(31)

References

[1]	WARD J W. Hydrocracking processes and catalysts[J]. Fuel Process Technol, 1993, 35(1):55-85. https://www.researchgate.net/publication/223148828_Hydrocracking_processes_and_catalysts
[2]	WARD J W. Design and preparation of hydrocracking catalysts[J]. Stud Surf Sci Catal, 1983, (16):587-618.
[3]	张世万, 徐东升, 周霞萍, 尹思聪, 张丕祥.煤焦油加氢裂化反应及其催化剂的研究[J].现代化工, 2011, 31(11):73-77. http://www.cnki.com.cn/Article/CJFDTOTAL-XDHG201111021.htm ZHANG Shi-wan, XU Dong-sheng, ZHOU Xia-ping, YIN Si-cong, ZHANG Pei-xiang. Study on reaction of coal tar hydrocracking and its catalysts[J]. Mod Chem Ind, 2011, 31(11):73-77. http://www.cnki.com.cn/Article/CJFDTOTAL-XDHG201111021.htm
[4]	孙晓艳.煤焦油净化及加氢反应研究.青岛:青岛科技大学, 2012. SUN Xiao-yan. Research on the coal tar decontamination and reactions of coal tar hydrogenation. Qingdao:Qingdao University of Science & Technology, 2012.
[5]	雷振, 胡冬妮, 潘海涛, 陆江银.煤焦油加氢催化剂的研究进展[J].现代化工, 2014, 34(1):30-35. http://www.cnki.com.cn/Article/CJFDTOTAL-WGTX201602104.htm LEI Zhen, HU Dong-ni, PAN Hai-tao, LU Jiang-yin. Research progress of coal tar catalytic hydrogenation[J]. Mod Chem Ind, 2014, 34(1):30-35. http://www.cnki.com.cn/Article/CJFDTOTAL-WGTX201602104.htm
[6]	田梦, 周厚峰, 张谦温.煤焦油加氢脱硫脱氮催化剂研究进展[J].工业催化, 2014, 22(4):253-258. http://www.cnki.com.cn/Article/CJFDTOTAL-GYCH201404003.htm TIAN Meng, ZHOU Hou-feng, ZHANG Qian-he. Research progress in desulfurization and denitrification catalysts for coal tar hydrogenation[J]. Ind Catal, 2014, 22(4):253-258. http://www.cnki.com.cn/Article/CJFDTOTAL-GYCH201404003.htm
[7]	张登前, 段爱军, 赵震, 姜桂元, 万国赋, 黄卫强.加氢脱氮催化剂及反应机理研究进展[J].现在化工, 2007, 27(1):54-59. http://www.cnki.com.cn/Article/CJFDTOTAL-XDHG2007S1012.htm ZHANG Deng-qian, DUAN Ai-jun, ZHAO Zhen, JIANG Gui-yuan, WAN Guo-fu, HUANG Wei-qiang. Research advance in catalysts and reaction mechanism for hydrodenitrogenation[J]. Mod Chem Ind, 2007, 27(1):54-59. http://www.cnki.com.cn/Article/CJFDTOTAL-XDHG2007S1012.htm
[8]	WALENDZIEWSKI J. Properties and hydrodesulfurization activity of cobalt molybdenum phosphorus alumina catalysts[J]. React Kinet Chem Lett, 1991, 43:107-113. doi: 10.1007/BF02075420
[9]	IWAMOTO R, GRIMBLOT J. Genesis structural and catalytic properties of Ni-Mo-P/alumina based hydrotreating catalysts prepared by a solgel method[J]. Stud Surf Sci Catal, 1999, 127:169-176. doi: 10.1016/S0167-2991(99)80406-6
[10]	曹光伟, 罗锡辉, 刘振华, 何金梅.加氢处理催化剂的制备和表征I:MoNiP/Al₂O₃催化剂的制备及助剂的作用[J].催化学报, 2001, 22(2):143-147. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200102010.htm CAO Guang-wei, LUO Xi-hui, LIU Zhen-hua, HE Jin-mei. Preparation and characterization of hydrotreating catalysts I:Preparation of MoNiP/Al₂O₃ and effect of promoters[J]. Chin J Catal, 2001, 22(2):143-147. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200102010.htm
[11]	SAJKOWSKI D J, MILLER J T, ZAJAC G W. Phosphorus promotion of Mo/Al₂O₃ hydrotreating catalysts[J]. Appl Catal, 1990, 6:205-220. https://www.researchgate.net/publication/250691720_Phosphorus_promotion_of_MoAl2O3_hydrotreating_catalysts
[12]	胡大为, 杨清河, 孙淑玲, 牛传峰.磷对MoCoNi/Al₂O₃催化剂性能及活性结构的影响[J].石油炼制与化工, 2011, 42(5):63-73. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201105004.htm HU Da-wei, YANG Qing-he, SUN Shu-ling, NIU Chuan-feng. Effect of phosphorrus on the performance and active component structure of MoCoNi/Al₂O₃ catalyst[J]. Pet Process Petrochem, 2011, 42(5):63-73. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201105004.htm
[13]	USMAN, YAMAMOTO T, KUBOTA T, OKAMATO Y. Effect of phosphorus addition on the active sites of a Co-Mo/Al₂O₃ catalyst for the hydrodesulfurization of thiophene[J]. Appl Catal A:Gen, 2007, 326(2):219-225. doi: 10.1016/j.apcata.2007.04.014
[14]	周慧波, 张舜华, 侯凯湖. P和NTA对Co-Mo选择性加氢脱硫催化剂性能的影响[J].石油炼制与化工, 2010, 41(1):40-43. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201001014.htm ZHOU Hui-bo, ZHANG Shun-hua, HOU Kai-hu. Effect of P and NTA on the catalytic performance of Co-Mo selective hydrodesulfurization catalyst[J]. Pet Process Petrochem, 2010, 41(1):40-43. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201001014.htm
[15]	唐莉, 孙雪芹, 刘丛华, 丁伟, 黄晓亮, 高雄厚.磷改性对Al₂O₃酸性和催化活性的影响[J].应用化工, 2012, 41(10):1785-1787. http://www.cnki.com.cn/Article/CJFDTOTAL-SXHG201210033.htm TANG Li, SUN Xue-qin, LIU Cong-hua, DING Wei, HUANG Xiao-liang, GAO Xiong-hou. Effects of phosphorus modification on acid and catalytic activity of Al₂O₃[J]. Appl Chem Ind, 2012, 41(10):1785-1787. http://www.cnki.com.cn/Article/CJFDTOTAL-SXHG201210033.htm
[16]	石垒, 张增辉, 邱泽刚, 郭芳, 张伟, 赵亮富. P改性对Mo-Ni/Al₂O₃煤焦油加氢脱氮性能的影响[J].燃料化学学报, 2015, 43(1):75-80. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18558.shtml SHI Lei, ZHANG Zeng-hui, QIU Ze-gang, GUO Fang, ZHANG Wei, ZHAO Liang-fu. Effect of phosphorus modification on the catalytic properties of Mo-Ni/Al₂O₃ in the hydrodenitrogenation of coal tar[J]. J Fuel Chem and Technol, 2015, 43(1):75-80. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18558.shtml
[17]	郭蓉, 沈本贤, 方向晨, 凌昊.载体孔结构对加氢脱硫催化剂催化性能的影响[J].石油学报, 2012, 28(5):725-729. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG201205005.htm GUO Rong, SHEN Ben-xian, FANG Xiang-chen, LING Hao. Effect of support pore structure on hydrodesulfurization performance of catalyst[J]. Acta Pet Sin, 2012, 28(5):725-729. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG201205005.htm
[18]	LEWANDOWSKI M, SARBAK Z. The effect of boron addition on hydrodesulfurization and hydrodenitrogenation activity of NiMo/Al₂O₃ catalysts[J]. Fuel, 2000, 79(5):487-495. doi: 10.1016/S0016-2361(99)00151-9
[19]	杨锡尧.固体催化剂的研究方法[J].石油化工, 2002, 31(1):63-73. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG200201020.htm YANG Xi-yao. The study methods of solid catalysts[J]. Petrochem Technol, 2002, 31(1):63-73. http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG200201020.htm
[20]	BENLEOU P, DELMON B. Modified aluminas:Relationship between activity in 1-butanol dehydration and acidity measured by NH₃-TPD[J]. Catal Today, 1989, 5:121-137. doi: 10.1016/0920-5861(89)80020-3
[21]	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. doi: 10.1016/S1872-5813(10)60020-5 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 struture of NiMo/Al₂O₃ catalyst[J]. J Fuel Chem Technol, 2010, 38(1):69-74. doi: 10.1016/S1872-5813(10)60020-5
[22]	RAMIREZ J, CONTRERAS R, CASTILLO P. Characterization and catalytic activity of Co-Mo HDS catalysts supported on alumina-MCM-41[J]. Appl Catal A:Gen, 2000, 197(1):69-78. doi: 10.1016/S0926-860X(99)00534-7
[23]	BRITO J L, LAINE J. Reducibility of Ni-Mo/Al₂O₃ catalysts:A TPR study[J]. J Catal, 1993, 139(2):540-550. doi: 10.1006/jcat.1993.1047
[24]	侯祥麟.中国炼油技术[M].北京:石化出版社, 2011. HOU Xiang-lin. The Technology of Chinses Oil Refining[M]. Beijing:Petrochemical Press, 2011.
[25]	李童, 董群, 冯熙桐.加氢催化剂预硫化技术研究进展[J].化学工程师, 2014, (1):42-44. http://www.cnki.com.cn/Article/CJFDTOTAL-HXGC201401013.htm LI Tong, DONG Qun, FENG Xi-tong. Research progress in the hydrogenation catalyst presulfurization[J]. Chem Eng, 2014, (1):42-44. http://www.cnki.com.cn/Article/CJFDTOTAL-HXGC201401013.htm
[26]	CHEN W, MAVGE F, VAN GESTEL J, NIE H, LI D, LONG X. Effect of modification of the alumina cidity on the properties of supported Mo and CoMo sulfide catalysts[J]. J Catal, 2013, 304:47-62. doi: 10.1016/j.jcat.2013.03.004
[27]	齐和日玛, 袁慧, 张韫宏, 李会峰, 徐广通.原位FTIR和XPS研究汽油选择性加氢脱硫催化剂的活性和选择性[J].光谱学与光谱分析, 2011, 31(7):1752-1757. http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN201107010.htm QIHE Ri-ma, YUAN Hui, ZHANG Yun-hong, LI Hui-feng, XIU Guang-tong. In situ FTIR and XPS study on selective hydrodesulfurization catalyst of FCC gasoline[J]. Spectrosc Spect Anal, 2011, 31(7):1752-1757. http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN201107010.htm
[28]	孙淑玲, 石亚华, 徐广通, 王锦业. Co-Mo加氢脱硫催化剂的TEM表征[J].石油炼制与化工, 2006, 37(11):2-6. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH200611001.htm SUN Shu-ling, SHI Ya-hua, XIU Guang-tong, WANG Jin-ye. Characterization of Co-Mo hydrodesulfurization catalyst by TEM[J]. Pet Process Petrochem, 2006, 37(11):2-6. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH200611001.htm
[29]	LI M, LI H, JIANG F, CHU Y, NIE H. The relation between morphology of (Co) MoS₂ phase and selective hydrodesulfurization for CoMo catalysts[J]. Catal Today, 2010, 149:35-39. doi: 10.1016/j.cattod.2009.03.017
[30]	屈明达, 鹗忠明.煤焦油的加氢处理[J].化工技术经济, 2005, 23(6):49-51. http://www.cnki.com.cn/Article/CJFDTOTAL-HGJJ200506010.htm QV Ming-da, E Zhong-ming. Coal tar oil hydrogenation[J]. Chem Techno-Econo, 2005, 23(6):49-51. http://www.cnki.com.cn/Article/CJFDTOTAL-HGJJ200506010.htm
[31]	张世万.煤焦油催化加氢轻质化.南昌:东华理工大学, 2011. ZHANG Shi-wan. Study on light-end products of coal tar with catalytic hydrogenation and catalyst. Nanchang:East China University of Technology, 2011.