Mo掺杂改性NiC/Al-MCM-41的芘催化加氢性能

doi:10.16085/j.issn.1000-6613.2024-0102

化工进展 ›› 2024, Vol. 43 ›› Issue (5): 2386-2395.DOI: 10.16085/j.issn.1000-6613.2024-0102

• 化石能源的清洁高效转化利用 • 上一篇

Mo掺杂改性NiC/Al-MCM-41的芘催化加氢性能

桂鑫¹(), 陈汇勇¹, 白柏杨², 贾永梁¹, 马晓迅¹()

^1.西北大学化工学院，碳氢资源清洁利用国际科技合作基地，陕北能源先进化工利用技术教育部工程研究中心，陕西省洁净煤转化工程技术研究中心，陕北能源化工产业发展协同创新中心，陕西西安 710127
^2.陕西煤基特种燃料研究院有限公司，陕西西安 710069

收稿日期:2024-01-14 修回日期:2024-03-17 出版日期:2024-05-15 发布日期:2024-06-15
通讯作者: 马晓迅
作者简介:桂鑫（1998—），女，硕士研究生，研究方向为煤焦油催化加氢。E-mail：18834162858@163.com。
基金资助:
国家自然科学基金(22078266)

Catalytic hydrogenation of pyrene over Mo-doped NiC/Al-MCM-41

GUI Xin¹(), CHEN Huiyong¹, BAI Boyang², JIA Yongliang¹, MA Xiaoxun¹()

^1.International Science & Technology Cooperation Base of MOST for Clean Utilization of Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of Education for Advanced Use Technology of Shanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Collaborative Innovation Center for Development of Energy and Chemical Industry in Northern Shaanxi, School of Chemical Engineering, Northwest University, Xi’an 710127, Shaanxi, China
^2.Shannxi Coal Based Special Fuel Research Institute, Xi’an 710069, Shaanxi, China

Received:2024-01-14 Revised:2024-03-17 Online:2024-05-15 Published:2024-06-15
Contact: MA Xiaoxun

摘要/Abstract

摘要：

通过水热合成法分别制备了负载型NiC/Al-MCM-41和NiMoC/Al-MCM-41催化剂，并将其应用于芘加氢反应。采用X射线衍射（XRD）、X射线光电子能谱（XPS）、傅里叶变换红外光谱（FTIR）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、N₂物理吸附、NH₃程序升温脱附（NH₃-TPD）和热重（TG）对催化剂进行表征，并通过间歇高压反应釜对催化剂的芘加氢活性进行评价。探究Mo掺杂改性对NiC/Al-MCM-41催化剂物理-化学结构及加氢反应活性的影响，揭示催化剂物理和化学性质与加氢活性之间的构效关系。结果表明，在反应温度为340℃、H₂压力为6MPa、连续反应2h时，NiMoC/Al-MCM-41催化剂表现出最佳的加氢活性，且具有一定的再生性能。相较于NiC/Al-MCM-41催化剂，Mo掺杂改性使得芘加氢转化率和深度加氢选择性分别从65.2%和58.9%提升至90.8%和76.2%，有效地提高了催化剂的加氢反应性能。但由于积炭堵塞催化剂孔道，阻碍了芘分子在催化剂孔道内的扩散转递，导致NiMoC/Al-MCM-41催化剂的稳定性较差，后续应进一步提高催化剂的抗积炭性能。

关键词: 多环芳烃, 芘, 加氢, 催化剂, Mo掺杂

Abstract:

Supported NiC/Al-MCM-41 and NiMoC/Al-MCM-41 catalysts were prepared by hydrothermal synthesis and utilized in pyrene hydrogenation. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ physical adsorption, NH₃ temperature-programmed desorption (NH₃-TPD), and thermogravimetric analysis (TG). The hydrogenation activity of the catalysts was evaluated in a batch high-pressure reactor. The effects of Mo doping on the physical-chemical structure and hydrogenation activity of NiC/Al-MCM-41 catalyst were investigated, and the structure-activity relationship between the physical and chemical properties of the catalyst and hydrogenation activity was explored. The results showed that the NiMoC/Al-MCM-41 catalyst exhibited the best hydrogenation activity and could be partially regenerated at a reaction temperature of 340℃, H₂ pressure of 6MPa, and continuous reaction for 2h. Compared with NiC/Al-MCM-41 catalyst, Mo doping increased the conversion of pyrene from 65.2% to 90.8% and deep hydrogenation selectivity from 58.9% to 76.2%, which effectively improved the hydrogenation performance of the catalyst. However, the stability of NiMoC/Al-MCM-41 catalyst was poor due to the carbon deposition caused by pore channel blocking of the catalyst, which hindered the diffusion and transfer of pyrene molecules in the pore channels. Therefore, the catalyst resistance to carbon deposition should be further improved in the future.

Key words: polycyclic aromatic hydrocarbons, pyrene, hydrogenation, catalyst, Mo doping

中图分类号:

TQ536

桂鑫, 陈汇勇, 白柏杨, 贾永梁, 马晓迅. Mo掺杂改性NiC/Al-MCM-41的芘催化加氢性能[J]. 化工进展, 2024, 43(5): 2386-2395.

GUI Xin, CHEN Huiyong, BAI Boyang, JIA Yongliang, MA Xiaoxun. Catalytic hydrogenation of pyrene over Mo-doped NiC/Al-MCM-41[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2386-2395.

图/表 14

图1 芘加氢反应路径[20]

图2 载体和催化剂的XRD谱图

图3 催化剂的XPS谱图

图4 载体和催化剂的FTIR谱图

图5 载体和催化剂的SEM图和EDX元素映射图

图6 NiMoC/Al-MCM-41催化剂的TEM图

图7 载体和催化剂的N2吸附-解吸等温线和孔径分布

表1 载体和催化剂的物理特性

样品

比表面积（BET）

/m²·g^-1

孔容

/cm³·g^-1

平均孔径

/nm

图8 载体和催化剂的NH3-TPD

图9 失活的NiMoC/Al-MCM-41催化剂的相关表征

表2 失活的NiMoC/Al-MCM-41催化剂的物理特性

样品

比表面积（BET）

/m²·g^-1

孔容

/cm³·g^-1

平均孔径

/nm

图10 不同活性相催化剂的芘加氢性能

图11 NiMoC/Al-MCM-41催化剂在不同反应条件下的芘加氢性能

图12 NiMoC/Al-MCM-41催化剂的稳定再生性能

参考文献 38

1	古丽娜尔·图尔逊, 李国峰. 煤焦油中芳烃化合物催化加氢机理研究进展[J]. 合成材料老化与应用, 2021, 50(3): 141-143.
	GULNAR Tursen, LI Guofeng. Research progress in catalytic hydrogenation of aromatic compounds in coal tar[J]. Synthetic Materials Aging and Application, 2021, 50(3): 141-143.
2	FU Wenqian, ZHANG Lei, WU Dongfang, et al. Mesoporous zeolite-supported metal sulfide catalysts with high activities in the deep hydrogenation of phenanthrene[J]. Journal of Catalysis, 2015, 330: 423-433.
3	马雪飞, 李宗鸿, 肖植煌, 等. 有机液体储运氢技术经济分析与比较[J]. 现代化工, 2022, 42(6): 202-205, 210.
	MA Xuefei, LI Zonghong, XIAO Zhihuang, et al. Techno-economic analysis and comparison of liquid organic hydrogen carrier system[J]. Modern Chemical Industry, 2022, 42(6): 202-205, 210.
4	LIU Daocheng, CHEN Yu, JING Jieying, et al. Synthesis of Ni/NiAlO _x catalysts for hydrogenation saturation of phenanthrene[J]. Frontiers in Chemistry, 2021, 9: 757908.
5	ZHANG Minghui, SONG Qingyun, HE Zexing, et al. Tuning the mesopore-acid-metal balance in Pd/HY for efficient deep hydrogenation saturation of naphthalene[J]. International Journal of Hydrogen Energy, 2022, 47(48): 20881-20893.
6	WANG Enhua, HU Di, XIAO Chengkun, et al. Highly dispersed Pt on core-shell micro-mesoporous composites assembled by mordenite nanocrystals for selective hydrogenation of polycyclic aromatics[J]. Fuel, 2023, 331: 125852.
7	JACQUIN Mélanie, JONES Deborah J, Jacques ROZIÈRE, et al. Novel supported Rh, Pt, Ir and Ru mesoporous aluminosilicates as catalysts for the hydrogenation of naphthalene[J]. Applied Catalysis A: General, 2003, 251(1): 131-141.
8	HAO Jing, ZHANG Guofeng, ZHENG Yiteng, et al. Controlled synthesis of Ni₃C/nitrogen-doped carbon nanoflakes for efficient oxygen evolution[J]. Electrochimica Acta, 2019, 320: 134631.
9	WANG Hao, CAO Yingjie, ZOU Guifu, et al. High-performance hydrogen evolution electrocatalyst derived from Ni₃C nanoparticles embedded in a porous carbon network[J]. ACS Applied Materials & Interfaces, 2017, 9(1): 60-64.
10	ANDRÉ Rémi F, MEYNIEL Léna, CARENCO Sophie. Nickel carbide (Ni₃C) nanoparticles for catalytic hydrogenation of model compounds in solvent[J]. Catalysis Science & Technology, 2022, 12(14): 4572-4583.
11	XIONG Kun, LI Li, ZHANG Li, et al. Ni-doped Mo₂C nanowires supported on Ni foam as a binder-free electrode for enhancing the hydrogen evolution performance[J]. Journal of Materials Chemistry A, 2015, 3(5): 1863-1867.
12	OUYANG Ting, YE Yaqian, WU Chunyan, et al. Heterostructures composed of N-doped carbon nanotubes encapsulating cobalt and β-Mo₂C nanoparticles as bifunctional electrodes for water splitting[J]. Angewandte Chemie International Edition, 2019, 58(15): 4923-4928.
13	SHEN Zhibing, FU Rao, ZHANG Shangli, et al. Selective hydrogenation of polycyclic aromatics to monocyclic aromatics over NiMoC/Hβ catalysts in a methane and hydrogen environment[J]. China Petroleum Processing and Petrochemical Technology, 2023, 25(2): 92-100.
14	JIANG Chenguang, WANG Yonggang, ZHANG Haiyong, et al. Effect of PDADMAC with different molecular weight regulating Hβ Properties on hydrogenation performance of NiMoC/Hβ catalysts[J]. Fuel Processing Technology, 2021, 213: 106704.
15	CHEN Wenbin, Francoise MAUGÉ, VAN GESTEL Jacob, et al. Effect of modification of the alumina acidity on the properties of supported Mo and CoMo sulfide catalysts[J]. Journal of Catalysis, 2013, 304: 47-62.
16	ITO Koki, KOGASAKA Yoshifumi, KUROKAWA Hideki, et al. Preliminary study on mechanism of naphthalene hydrogenation to form decalins via tetralin over Pt/TiO₂ [J]. Fuel Processing Technology, 2002, 79(1): 77-80.
17	JIANG Chenguang, WANG Yonggang, ZHANG Haiyong, et al. Effect of initial Si/Al ratios on the performance of low crystallinity Hβ-x zeolite supported NiMo carbide catalysts for aromatics hydrogenation[J]. Catalysis Science & Technology, 2019, 9(18): 5031-5044.
18	USMAN Muhammad, LI Dan, RAZZAQ Rauf, et al. Novel MoP/HY catalyst for the selective conversion of naphthalene to tetralin[J]. Journal of Industrial and Engineering Chemistry, 2015, 23: 21-26.
19	TAGHVAEI Hamed, MOADDELI Ali, Ali KHALAFF-NEZHAD, et al. Catalytic hydrodeoxygenation of lignin pyrolytic-oil over Ni catalysts supported on spherical Al-MCM-41 nanoparticles: Effect of Si/Al ratio and Ni loading[J]. Fuel, 2021, 293: 120493.
20	KORRE Styliani C, KLEIN Michael T, QUANN Richard J. Polynuclear aromatic hydrocarbons hydrogenation. 1. Experimental reaction pathways and kinetics[J]. Industrial & Engineering Chemistry Research, 1995, 34(1): 101-117.
21	MENG Fanyu, ZHANG Shule, ZHANG Mingjia, et al. The mechanism of Ce-MCM-41 catalyzed peroxone reaction into ·OH and ·O 2 - radicals for enhanced NO oxidation[J]. Molecular Catalysis, 2022, 518: 112110.
22	QIN Jing, LI Baoshan, ZHANG Wen, et al. Synthesis, characterization and catalytic performance of well-ordered mesoporous Ni-MCM-41 with high nickel content[J]. Microporous and Mesoporous Materials, 2015, 208: 181-187.
23	HAN Guihong, ZHAO Jing, YANG Ze, et al. Facile hydrothermal synthesis and enhanced electrochemical properties of a layered NiSiO/RGO nanocomposite with an interesting dandelion-like structure[J]. Dalton Transactions, 2021, 50(39): 13756-13767.
24	HUANG Ting, SHEN Tao, GONG Mingxing, et al. Ultrafine Ni-B nanoparticles for efficient hydrogen evolution reaction[J]. Chinese Journal of Catalysis, 2019, 40(12): 1867-1873.
25	JIANG Jing, LIU Qiuxia, ZENG Chunmei, et al. Cobalt/molybdenum carbide@N-doped carbon as a bifunctional electrocatalyst for hydrogen and oxygen evolution reactions[J]. Journal of Materials Chemistry A, 2017, 5(32): 16929-16935.
26	HUANG Xiaoyu, ZHANG Wei, PENG Yaowei, et al. A multifunctional layered nickel silicate nanogenerator of synchronous oxygen self-supply and superoxide radical generation for hypoxic tumor therapy[J]. ACS Nano, 2022, 16(1): 974-983.
27	WANG Pengyan, QIN Rui, JI Pengxia, et al. Synergistic coupling of Ni nanoparticles with Ni₃C nanosheets for highly efficient overall water splitting[J]. Small, 2020, 16(37): 2001642.
28	DOUKKALI M EI, PAUL S, DUMEIGNIL F. New insights in single-step hydrodeoxygenation of glycerol to propylene by coupling rational catalyst design with systematic analysis[J]. Applied Catalysis B: Environmental, 2023, 324: 122280.
29	SU Xiaoping, AN Pu, GAO Junwen, et al. Selective catalytic hydrogenation of naphthalene to tetralin over a Ni-Mo/Al₂O₃ catalyst[J]. Chinese Journal of Chemical Engineering, 2020, 28(10): 2566-2576.
30	HUANG Guan, SUN Zhichao, YU Zhiquan, et al. Supported Ni₂P catalysts derived from nickel phyllosilicate with enhanced hydrodesulfurization performance[J]. Journal of Catalysis, 2023, 419: 37-48.
31	El‑AHWANY Omnia M, AWADALLAH Ahmed E, ABDEL-AZIM Samira M, et al. Chemical vapor deposition synthesis of high-quality Ni₃C/GNPs composite material: Effect of growth time on the yield, morphology and adsorption behavior of metal ions[J]. Chemical Papers, 2022, 76(3): 1579-1592.
32	王悦燚, 王婧, 贾永梁, 等. 硫化钼催化剂用于催化多环芳烃芘的加氢反应[J]. 煤炭转化, 2023, 46(6): 1-11.
	WANG Yueyi, WANG Jing, JIA Yongliang, et al. Molybdenum sulfide catalyst for hydrogenation of PAHs pyrene[J]. Coal Conversion, 2023, 46(6): 1-11.
33	LI Kang, ZHU Jianfeng, XU Zhanwei, et al. Tremella-like Mo and N codoped graphitic nanosheets by in situ carbonization of phthalocyanine for potassium-ion battery[J]. ACS Applied Materials & Interfaces, 2021, 13(26): 30583-30593.
34	LU Xinyu, GUO Haoquan, CHEN Jiajia, et al. Selective catalytic transfer hydrogenation of lignin to alkyl guaiacols over NiMo/Al-MCM-41[J]. ChemSusChem, 2022, 15(7): e202200099.
35	陈秀莹, 谢慧琳, 胡文斌, 等. MCM-41负载Pt-Al催化剂的制备及其表征[J]. 化工学报, 2018, 69(S1): 72-79.
	CHEN Xiuying, XIE Huilin, HU Wenbin, et al. Preparation and characterization of MCM-41 supported Pt-Al catalysts[J]. CIESC Journal, 2018, 69(S1): 72-79.
36	GUO Haoquan, ZHAO Jiwu, CHEN Yu, et al. Mechanistic insights into hydrodeoxygenation of lignin derivatives over Ni single atoms supported on Mo₂C[J]. ACS Catalysis, 2024, 14(2): 703-717.
37	CHEN Changzhou, LIU Peng, XIA Haihong, et al. Catalytic conversion of lignin to liquid fuels with an improved H/C_eff value over bimetallic NiMo-MOF-derived catalysts[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(41): 13937-13952.
38	CHEN Tingsheng, YANG Wenyi, DU Zhenyi, et al. Effects of mesopore introduction on the stability of zeolites for 4-iso-propylphenol dealkylation[J]. Catalysis Today, 2021, 371: 40-49.

[1]	吴达, 蒋淑娇, 魏强, 袁胜华, 杨刚, 张成. 能源转型中渣油高效利用技术的研究进展[J]. 化工进展, 2024, 43(5): 2343-2353.
[2]	王冰, 王磊, 黄欣茹, 袁红鹏, 赖小娟, 李朋. 一种耐酸耐碱高强树脂的合成及性能[J]. 化工进展, 2024, 43(4): 1992-2000.
[3]	刘若璐, 汤海波, 何翡翡, 罗凤盈, 王金鸽, 杨娜, 李洪伟, 张锐明. 液态有机储氢技术研究现状与展望[J]. 化工进展, 2024, 43(4): 1731-1741.
[4]	王红妍, 马子然, 李歌, 马静, 赵春林, 周佳丽, 王磊, 彭胜攀. 燃煤耦合可再生燃料烟气多污染物协同催化脱除研究进展[J]. 化工进展, 2024, 43(4): 1783-1795.
[5]	陈家一, 高帷韬, 阴亚楠, 王诚, 欧阳鸿武, 毛宗强. 电化学沉积法制备质子交换膜燃料电池催化剂[J]. 化工进展, 2024, 43(4): 1796-1809.
[6]	吴晨赫, 刘彧旻, 杨昕旻, 崔记伟, 姜韶堃, 叶金花, 刘乐全. 粉体光催化全水分解技术研究进展[J]. 化工进展, 2024, 43(4): 1810-1822.
[7]	刘雨蓉, 王兴宝, 李文英. 分子筛负载Pt催化剂酸性位点调控及对蒽深度加氢性能的影响[J]. 化工进展, 2024, 43(4): 1832-1839.
[8]	郭潇东, 毛玉娇, 刘相洋, 邱丽, 于峰, 闫晓亮. Ni/Sm₂O₃-CeO₂/Al₂O₃催化剂氧空位对二氧化碳低温甲烷化的影响[J]. 化工进展, 2024, 43(4): 1840-1850.
[9]	高飞, 刘志松, 潘珂珂, 刘敏敏, 代斌, 但建明, 于锋. 蛭石基FeCeO _x 催化剂及CO选择性催化还原NO[J]. 化工进展, 2024, 43(4): 1851-1862.
[10]	刘方旺, 韩艺, 张佳佳, 步红红, 王兴鹏, 于传峰, 刘猛帅. CO₂与环氧化物耦合制备环状碳酸酯的多相催化体系研究进展[J]. 化工进展, 2024, 43(3): 1252-1265.
[11]	张鹏飞, 严张艳, 任亮, 张奎, 梁家林, 赵广乐, 张璠玢, 胡志海. C $9 +$ 重芳烃催化加氢脱烷基技术研究进展[J]. 化工进展, 2024, 43(3): 1266-1274.
[12]	谷星朋, 马红钦, 刘嘉豪. 雷尼镍的磷量子点改性及其催化加氢脱硫性能[J]. 化工进展, 2024, 43(3): 1293-1301.
[13]	张书铭, 刘化章. 基于BP神经网络模型优化Fe_1-_x O基氨合成催化剂[J]. 化工进展, 2024, 43(3): 1302-1308.
[14]	陈风, 王宣德, 黄伟, 王晓东, 王琰. HZSM-22的粒径调控及Pt/HZSM-22的正十二烷加氢异构催化性能[J]. 化工进展, 2024, 43(3): 1309-1317.
[15]	萧垚鑫, 张军, 单锐, 袁浩然, 陈勇. Pt/CaO材料催化糠醇加氢制备戊二醇[J]. 化工进展, 2024, 43(3): 1318-1327.

Mo掺杂改性NiC/Al-MCM-41的芘催化加氢性能

Catalytic hydrogenation of pyrene over Mo-doped NiC/Al-MCM-41

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 14

参考文献 38

相关文章 15

编辑推荐

Metrics

本文评价