[1]张磊,贺黎文,和法端,等.柠檬酸改性金属磷化物对4,6-二甲基二苯并噻吩加氢脱硫性能[J].常州大学学报(自然科学版),2021,33(01):20-28.[doi:10.3969/j.issn.2095-0411.2021.01.004]
　ZHANG Lei,HE Liwen,HE Faduan,et al.Study of Hydrodesulfurization of 4,6-Dimethyldibenzothiophene over Metal Phosphide Catalysts Modified by Citric Acid[J].Journal of Changzhou University(Natural Science Edition),2021,33(01):20-28.[doi:10.3969/j.issn.2095-0411.2021.01.004]
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柠檬酸改性金属磷化物对4,6-二甲基二苯并噻吩加氢脱硫性能()
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常州大学学报(自然科学版)[ISSN:2095-0411/CN:32-1822/N]

卷:
第33卷
期数:
2021年01期
页码:
20-28
栏目:
化学化工
出版日期:
2021-01-20

文章信息/Info

Title:
Study of Hydrodesulfurization of 4,6-Dimethyldibenzothiophene over Metal Phosphide Catalysts Modified by Citric Acid
文章编号:
2095-0411(2021)01-0020-09
作者:
张磊1; 2; 贺黎文1; 和法端1; 郑世富1; 何明阳1; 2; 唐天地1; 2
(1. 常州大学 石油化工学院, 江苏 常州 213164; 2. 江苏省绿色催化材料与技术重点实验室(常州大学), 江苏 常州 213164)
Author(s):
ZHANG Lei1; 2;  HE Liwen1;  HE Faduan1;  ZHENG Shifu1;  HE Mingyang1; 2;  TANG Tiandi1; 2
(1. School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China; 2. Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University, Changzhou 213164, China)
关键词:
加氢脱硫;  金属磷化物;  柠檬酸;  4; 6-二甲基二苯并噻吩
Keywords:
hydrodesulfurization;  metal phosphide;  citric acid;  4; 6-DMDBT
分类号:
TE 62
DOI:
10.3969/j.issn.2095-0411.2021.01.004
文献标志码:
A
摘要:
研究了柠檬酸(CA)对磷化物催化剂(Ni2P, MoP和WP)的加氢脱硫性能的影响, 并通过N2吸附、XRD、TEM和H2-TPR等表征手段分析CA对载体的质构性质、磷化物活性相形貌以及金属-载体之间的相互作用的影响。在4,6-二甲基二苯并噻吩(4,6-DMDBT)的催化反应中, 引入CA提高了Ni2P和MoP催化剂的本征活性。如Ni2P/SiO2-CA和MoP/SiO2-CA, 其催化转换频率分别为6.2×10-4 s-1和1.8×10-4 s-1, 优于Ni2P/SiO2(5.8×10-4 s-1)和MoP/SiO2(1.4×10-4 s-1), 而引入CA降低了WP催化剂的加氢脱硫活性。结果表明, 引入CA增强了金属Ni或Mo与SiO2载体之间的相互作用, 提高磷化物活性相的分散度, 暴露更多的活性位点, 导致催化活性增加, 而对于WP催化剂却未观察到此现象。 此外, Ni2P/SiO2-CA也具有较高的表观催化性能, 对4,6-DMDBT的转化率为87.2%, 高于Ni2P/SiO2催化剂(77.8%)。
Abstract:
The influence of the citric acid(CA)on the hydrodesulfurization(HDS)performance of the metal phosphide catalyst was studied. A series of characterization methods including N2 adsorption, XRD, TEM, and H2-TPR were used to analyze the effect of CA on the textural properties, the morphology of metal phosphide active phase, and metal-support interaction. An activity test for the HDS of the 4,6-dimethyldibenzothiophene(4,6-DMDBT)demonstrated that the catalytic activity of the Ni2P and MoP catalysts were improved by the addition of CA. The obtained turnover frequencies for Ni2P/SiO2-CA and MoP/SiO2-CA were 6.2×10-4 s-1and 1.8×10-4 s-1, respectively, higher than that Ni2P/SiO2(5.8×10-4 s-1)and MoP/SiO2(1.4×10-4 s-1)catalysts without CA. By contrast, no enhancement was obtained for the supported WP catalyst. The characterization results suggested that the addition of CA into the Ni or Mo species impregnation solution could strengthen the metal-support interaction, resulting in the metal phosphide active phase with good dispersion, which was not observed for the WP catalyst. Then, the more exposure of the active sites for metal phosphide catalyst could enhance the catalytic performance. Also, the apparent catalytic activity for Ni2P/SiO2-CA in the HDS of the 4,6-DMDBT was 87.2%, much higher than that of Ni2P/SiO2 catalyst(77.8%).

参考文献/References:

[1]段为宇, 郭蓉,卜岩, 等. 柴油超深度加氢脱硫催化剂研究进展[J]. 炼油技术与工程, 2019, 49(11): 32-36.
[2]ZHANG C, BRORSON M, LI P, et al. CoMo/Al2O3 catalysts prepared by tailoring the surface properties of alumina for highly selective hydrodesulfurization of FCC gasoline[J]. Applied Catalysis A: General, 2019, 570: 84-95.
[3]李天敏, 张君涛, 申志兵, 等. 负载型磷化镍催化剂的制备及其催化应用[J]. 工业催化, 2019, 27(9): 19-25.
[4]ZHANG L, FU W, YU Q, et al. Ni2P clusters on zeolite nanosheet assemblies with high activity and good stability in the hydrodesulfurization of 4,6-dimethyldibenzothiophene[J]. Journal of Catalysis, 2016, 338: 210-221.
[5]郑世富, 张磊, 何明阳. CoMo/MgO催化剂的制备及其对4,6-二甲基二苯并噻吩的加氢脱硫性能[J]. 石油学报(石油加工), 2019, 35(4): 676-684.
[6]PRINS R, BUSSELL M E. Metalphosphides: preparation, characterization and catalytic reactivity[J]. Catalysis Letters, 2012, 142(12): 1413-1436.
[7]BUI P, CECILIA J A, OYAMA S T, et al. Studies of the synthesis of transition metal phosphides and their activity in the hydrodeoxygenation of a biofuel model compound[J]. Journal of Catalysis, 2012, 294: 184-198.
[8]STINNER C, PRINS R, WEBER T. Formation,structure, and HDN activity of unsupported molybdenum phosphide[J]. Journal of Catalysis, 2000, 191(2): 438-444.
[9]PHILLIPS D C, SAWHILL S J, SELF R, et al. Synthesis,characterization, and hydrodesulfurization properties of silica-supported molybdenum phosphide catalysts[J]. Journal of Catalysis, 2002, 207(2): 266-273.
[10]STINNER C, TANG Z, HAOUAS M, et al. Preparation and 31P NMR characterization of nickel phosphides on silica[J]. Journal of Catalysis, 2002, 208(2): 456-466.
[11]ZUZANIUK V, PRINS R. Synthesis and characterization of silica-supported transition-metal phosphides as HDN catalysts[J]. Journal of Catalysis, 2003, 219(1): 85-96.
[12]OYAMA S T, WANG X, REQUEJO F G, et al. Hydrodesulfurization of petroleum feedstocks with a new type of nonsulfide hydrotreating catalyst[J]. Journal of Catalysis, 2002, 209(1): 1-5.
[13]WANG X, CLARK P, OYAMA S T. Synthesis,characterization, and hydrotreating activity of several iron group transition metal phosphides[J]. Journal of Catalysis, 2002, 208(2): 321-331.
[14]CLARK P A, OYAMA S T. Alumina-supported molybdenum phosphide hydroprocessing catalysts[J]. Journal of Catalysis, 2003, 218(1): 78-87.
[15]SHU Y, LEE Y K, OYAMA S T. Structure-sensitivity of hydrodesulfurization of 4,6-dimethyldibenzothiophene over silica-supported nickel phosphide catalysts[J]. Journal of Catalysis, 2005, 236(1): 112-121.
[16]OYAMA S T, LEE Y K. The active site of nickel phosphide catalysts for the hydrodesulfurization of 4,6-DMDBT[J]. Journal of Catalysis, 2008, 258(2): 393-400.
[17]YANG S, PRINS R. New synthesis method for nickel phosphide hydrotreating catalysts[J]. Chemical Communications, 2005(33): 4178-4180.
[18]WANG R, SMITH K J. Hydrodesulfurization of 4,6-dimethyldibenzothiophene over highsurface area metal phosphides[J]. Applied Catalysis A: General, 2009, 361(1/2): 18-25.
[19]VANDILLEN A, TERORDE R, LENSVELD D, et al. Synthesis of supported catalysts by impregnation and drying using aqueous chelated metal complexes[J]. Journal of Catalysis, 2003, 216(1/2): 257-264.
[20]PEÑA L, VALENCIA D, KLIMOVA T. CoMo/SBA-15 catalysts prepared with EDTA and citric acid and their performance in hydrodesulfurization of dibenzothiophene[J]. Applied Catalysis B: Environmental, 2014, 147: 879-887.
[21]WANG R, SMITH K J. The effect of preparation conditions on the properties of high-surface area Ni2P catalysts[J]. Applied Catalysis A: General, 2010, 380(1/2): 149-164.
[22]ZHANG L, DAI Q, FU W, et al. CoMo catalyst on zeolite TS-1 nanorod assemblies with high activity in the hydrodesulfurization of 4,6-dimethyldibenzothiophene[J]. Journal of Catalysis, 2018, 359: 130-142.
[23]NIKULSHIN P A, MINAEV P P, MOZHAEV A V, et al. Investigation of co-effect of 12-tungstophosphoric heteropolyacid, nickel citrate and carbon-coated alumina in preparation of NiW catalysts for HDS, HYD and HDN reactions[J]. Applied Catalysis B: Environmental, 2015, 176/177: 374-384.
[24]WANG X, CLARK P, OYAMA S T. Synthesis, characterization, and hydrotreating activity of several iron group transition metal phosphides[J]. Journal of Catalysis, 2002, 208(2): 321-331.
[25]CLARK P, LI W, OYAMA S T. Synthesis and activity of a new catalyst for hydroprocessing: tungsten phosphide[J]. Journal of Catalysis, 2001, 200(1): 140-147.
[26]王广建, 赵强, 陈国良, 等. 柠檬酸引入方式对CoMo/TiO2-Al2O3催化剂加氢脱硫性能的影响[J]. 工业催化, 2019, 27(7): 54-60.
[27]朱立, 周亚松, 魏强, 等. 柠檬酸-水热组合改性对NiW/Al2O3催化剂加氢性能的影响[J]. 石油学报(石油加工), 2013, 29(5): 773-777.
[28]KLIMOVA T E, VALENCIA D, MENDOZA-NIETO J A, et al. Behavior of NiMo/SBA-15 catalysts prepared with citric acid in simultaneous hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene[J]. Journal of Catalysis, 2013, 304: 29-46.

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备注/Memo

备注/Memo:
收稿日期:2020-10-25。
基金项目:江苏省高等学校自然科学研究面上资助项目(18KJB530002); 江苏省“六大人才高峰”高层次人才资助项目(2018-XCL-100)。
作者简介:张磊(1986—),男,河北深州人,博士,讲师。E-mail: lqzhang@cczu.edu.cn
更新日期/Last Update: 2021-01-20