植物固体纤维丝在NiMo柴油加氢脱硫催化剂中的应用
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摘要
通过在氧化铝载体加入微米级植物固体纤维丝扩孔,制备出NiMo柴油加氢脱硫催化剂。采用BET、XRD、SEM、Raman与TEM对制备的载体及催化剂进行表征研究。结果表明,植物固体纤维丝能够在催化剂中构建出部分直筒大孔,NiM o活性组分在催化剂载体上实现了高度分散,活性相M oS2堆叠层数集中在3-5层,平均MoS2条长度为4.49 nm。研究了催化剂载体中植物固体纤维丝含量对催化剂活性的影响,并与常规氧化铝载体催化剂进行了对比,高压微反评价结果表明,开发的含有3%(质量分数)植物固体纤维丝NiMo柴油加氢脱硫催化剂比常规NiMo催化剂活性更高,其加氢脱硫活性提高了5%-15%。
The micron-sized plant fiber filaments were used as templates to obtain cylindrical macropores during the gamma alumina support preparation. The support was then used to prepare the NiMo/alunima diesel hydrodesulfurization catalyst. The prepared catalyst and alumina support were characterized by BET,XRD,SEM,Ruman and TEM. The characterization results showed that the plant fiber filaments in the catalyst constructed some straight holes,the NiMo active components on the catalyst support were highly dispersed and the active phase MoS2 stacked layers were mainly concentrated in 3-5 layers and the average length of MoS2 bars was 4.49 nm. The influence of plant fiber filament content on the performance of diesel hydrodesulfurization catalyst was studied and compared with conventional catalysts. The high-pressure micro-reverse evaluation results showthat the developed NiMo diesel hydrotreating catalyst containing 3%( mass ratio) plant fiber filament has5%-15% higher activity than the conventional NiMo catalyst.
The micron-sized plant fiber filaments were used as templates to obtain cylindrical macropores during the gamma alumina support preparation. The support was then used to prepare the NiMo/alunima diesel hydrodesulfurization catalyst. The prepared catalyst and alumina support were characterized by BET,XRD,SEM,Ruman and TEM. The characterization results showed that the plant fiber filaments in the catalyst constructed some straight holes,the NiMo active components on the catalyst support were highly dispersed and the active phase MoS2 stacked layers were mainly concentrated in 3-5 layers and the average length of MoS2 bars was 4.49 nm. The influence of plant fiber filament content on the performance of diesel hydrodesulfurization catalyst was studied and compared with conventional catalysts. The high-pressure micro-reverse evaluation results showthat the developed NiMo diesel hydrotreating catalyst containing 3%( mass ratio) plant fiber filament has5%-15% higher activity than the conventional NiMo catalyst.
引文
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[7]杨卫亚,凌凤香,张会成,王少军,沈智奇.具有三维贯通多级孔道结构大孔氧化铝的制备与表征[J].燃料化学学报,2018,46(5):558-563.(YANG Wei-ya,LING Feng-xiang,ZHANG Hui-cheng,WANG Shao-jun,SHEN Zhi-qi. Synthe sis and characte rization of hie rarchically porous alumina w ith thre e-dime nsional inte rconne cte d pore structure[J]. J Fuel Chem Technol,2018,46(5):558-563.)
[8]李红,陈胜利,董鹏,周倩.新型大孔结构重油加氢催化剂的制备、表征与评价[J].燃料化学学报,2009,37(4):444-447.(LI Hong,CHEN Sheng-li,DONG Peng,ZHOU Qian. Preparation,characterization and catalytic performance of novel macroporous catalysts for heavy oil hydrogenation[J]. J Fuel Chem Technol,2009,37(4):444-447.)
[9]汪怀远,朱友庄,赵景岩,程小双,张志华. TiO2载体特性对二苯并噻吩加氢脱硫性能的影响[J].化工学报,2013,64(7):2462-2467.(WANG Huai-yuan,ZHU You-zhuang,ZHAO Jing-yan,CHENG Xiao-shuang,ZHANG Zhi-hua. Effect of charateristics of TiO2 carrier on performance of dibenzothiopene hydrodesulfurization[J]. J Chem Ind Eng,2013,64(7):2462-2467.)
[10]张美云,苏治平,陆赵情,张美娟.原纤化处理植物纤维对其多孔材料结构和性能的影响[J].陕西科技大学学报(自然科学版),2017,35(1):1-5.(ZHANG Mei-yun,SU Zhi-ping,LU Zhao-qing,ZHANG Mei-juan. Effect of the fibrillation of plant fibers on the structure and properties of its porous composite material[J]. J Shanxi Univ Sci Technol,2017,35(1):1-5.)
[11]朱崇业,牛国兴,陈海鹰,李全芝,陆秋韵,王家寰,方维平.钼镍系列加氢处理催化剂的表面活性结构[J].复旦学报(自然科学版),1995,34(5):490-500.(ZHU Chong-ye,NIU Guo-xing,CHEN Hai-ying,LI Quan-zhi,LU Qiu-yun,WANG Jia-huan,FANG Wei-ping. Surface species structure of nickel-molybdenum hydrotreating catalyst[J]. J Fudan Univ(Sci Technol),1995,34(5):490-500.)
[12]张成,王永林,杨春雁,隋宝宽,杨刚,王刚,赵国利. NiMo/TiO2-Al2O3催化剂活性相表征及加氢脱硫反应性能研究[J].工业催化,2012,20(5):31-35.(ZHANG Cheng,WANG Yong-lin,YANG Chun-yan,SUI Bao-kuan,YANG Gang,ZHAO Guo-li. Characterization of active phase of Ni Mo/TiO2-Al2O3catalyst and its performance in hydrodesulphurization reaction[J]. Ind Catal,2012,20(5):31-35.)
[13]袁蕙,徐广通,齐和日玛,李会峰,卢立军,杨行远,塔娜.激光拉曼光谱在加氢脱硫催化剂Co-Mo/Al2O3中的应用研究[J].光谱学与光谱分析,2014,34(2):435-438.(YUAN Hui,XU Guang-tong,QI He-rima,LI Hui-feng,LU Li-jun,YANG Xing-yuan,TA Na. Laser Raman spectra study on Co-Mo/Al2O3hydrodesulphurization catalysts[J]. Spectrosc Spectral Anal,2014,34(2):435-438.)
[2]王健,张阳,储宇,卢学斌.柴油产品质量升级方案探讨[J].当代化工,2018,47(3):635-638.(WANG Jian,ZHANG Yang,CHU Yu,LU Xue-bin. Discussion on the quality upgrading scheme of diesel products[J]. Contemp Chem Ind,2018,47(3):635-638.)
[3]张乐,李明丰,聂红,李会峰,王哲,胡志海,刘学芬,丁石.高性能柴油超深度加氢脱硫催化剂RS-2100和RS-2200的开发及工业应用[J].石油炼制与化工,2017,48(6):1-6.(ZHANG Le,LI Ming-feng,NIE Hong,LI Hui-feng,WANG Zhe,HU Zhi-hai,LIU Xue-fen,DING Shi. Development and application of higly avtive ultra deep diesel HDS catalyst RS-2100 and RS-2200[J]. Pet Process Petrochem,2017,48(6):1-6.)
[4]李士才,张斌,蒋学章. FH-UDS催化剂生产国Ⅴ柴油工业运行结果[J].当代化工,2017,46(11):2313-2315.(LI Shi-cai,,ZHANG Bin,JIANG Xue-zhang. Commercial application results of diesel(Ⅴ)production unit using FH-UDS catalyst[J].Modern Chem Ind,2017,46(11):2313-2315.)
[5]王丹,宋金鹤,韩志波,温广明,张文成.柴油加氢精制催化剂的开发及工业应用[J].石油化工,2017,46(2):241-247.(WANG Dan,SONG Jin-he,HAN Zhi-bo,WEN Guang-ming,ZHANG Wen-cheng. Development and commercial application of diesel hydrotreating catalyst[J]. Petro Chem Ind,2017,46(2):241-247.)
[6]刘丽,郭蓉,孙进,丁莉,杨成敏,段为宇,姚运海.柴油加氢脱硫催化剂的研究进展[J].化工进展,2016,35(11):3503-3510.(LIU Li,GUO Rong,SUN Jin,DING Li,YANG Cheng-min,DUAN Wwei-yu,YAO Yun-hai. The research development of diesel hydrodesulfurization catalysts[J]. Chem Ind Eng Prog,2016,35(11):3503-3510.)
[7]杨卫亚,凌凤香,张会成,王少军,沈智奇.具有三维贯通多级孔道结构大孔氧化铝的制备与表征[J].燃料化学学报,2018,46(5):558-563.(YANG Wei-ya,LING Feng-xiang,ZHANG Hui-cheng,WANG Shao-jun,SHEN Zhi-qi. Synthe sis and characte rization of hie rarchically porous alumina w ith thre e-dime nsional inte rconne cte d pore structure[J]. J Fuel Chem Technol,2018,46(5):558-563.)
[8]李红,陈胜利,董鹏,周倩.新型大孔结构重油加氢催化剂的制备、表征与评价[J].燃料化学学报,2009,37(4):444-447.(LI Hong,CHEN Sheng-li,DONG Peng,ZHOU Qian. Preparation,characterization and catalytic performance of novel macroporous catalysts for heavy oil hydrogenation[J]. J Fuel Chem Technol,2009,37(4):444-447.)
[9]汪怀远,朱友庄,赵景岩,程小双,张志华. TiO2载体特性对二苯并噻吩加氢脱硫性能的影响[J].化工学报,2013,64(7):2462-2467.(WANG Huai-yuan,ZHU You-zhuang,ZHAO Jing-yan,CHENG Xiao-shuang,ZHANG Zhi-hua. Effect of charateristics of TiO2 carrier on performance of dibenzothiopene hydrodesulfurization[J]. J Chem Ind Eng,2013,64(7):2462-2467.)
[10]张美云,苏治平,陆赵情,张美娟.原纤化处理植物纤维对其多孔材料结构和性能的影响[J].陕西科技大学学报(自然科学版),2017,35(1):1-5.(ZHANG Mei-yun,SU Zhi-ping,LU Zhao-qing,ZHANG Mei-juan. Effect of the fibrillation of plant fibers on the structure and properties of its porous composite material[J]. J Shanxi Univ Sci Technol,2017,35(1):1-5.)
[11]朱崇业,牛国兴,陈海鹰,李全芝,陆秋韵,王家寰,方维平.钼镍系列加氢处理催化剂的表面活性结构[J].复旦学报(自然科学版),1995,34(5):490-500.(ZHU Chong-ye,NIU Guo-xing,CHEN Hai-ying,LI Quan-zhi,LU Qiu-yun,WANG Jia-huan,FANG Wei-ping. Surface species structure of nickel-molybdenum hydrotreating catalyst[J]. J Fudan Univ(Sci Technol),1995,34(5):490-500.)
[12]张成,王永林,杨春雁,隋宝宽,杨刚,王刚,赵国利. NiMo/TiO2-Al2O3催化剂活性相表征及加氢脱硫反应性能研究[J].工业催化,2012,20(5):31-35.(ZHANG Cheng,WANG Yong-lin,YANG Chun-yan,SUI Bao-kuan,YANG Gang,ZHAO Guo-li. Characterization of active phase of Ni Mo/TiO2-Al2O3catalyst and its performance in hydrodesulphurization reaction[J]. Ind Catal,2012,20(5):31-35.)
[13]袁蕙,徐广通,齐和日玛,李会峰,卢立军,杨行远,塔娜.激光拉曼光谱在加氢脱硫催化剂Co-Mo/Al2O3中的应用研究[J].光谱学与光谱分析,2014,34(2):435-438.(YUAN Hui,XU Guang-tong,QI He-rima,LI Hui-feng,LU Li-jun,YANG Xing-yuan,TA Na. Laser Raman spectra study on Co-Mo/Al2O3hydrodesulphurization catalysts[J]. Spectrosc Spectral Anal,2014,34(2):435-438.)