乙炔选择性加氢：催化剂结构敏感性分析及调控

doi:10.16085/j.issn.1000-6613.2020-1228

摘要/Abstract

摘要：

Pd催化乙炔选择性加氢是石脑油蒸汽裂解和煤基电石乙炔路径制备聚合级乙烯的关键。传统的Pd基催化剂使用成本较高且选择性和稳定性较差。本文综述了近年来乙炔选择性加氢催化剂结构敏感性及其调控方面的相关研究进展，重点介绍了包括活性金属粒径、纳米颗粒形貌和电子结构等对乙炔选择性加氢反应性能的重要作用，进而阐明了催化剂结构调控的目标与方向。进一步归纳总结了针对该反应特性的催化剂结构定向调控的研究进展，主要包括合金和金属间化合物催化剂、单原子及其合金催化剂的设计。通过合理地调控催化剂结构，优化关键物种的吸脱附和反应动力学行为，能够显著提高乙炔加氢催化剂的选择性及稳定性。在未来的研究中，如何针对该反应特性，构筑高效、稳定和低成本的催化剂将会是该体系催化剂研究的重点与难点。

关键词: 乙炔, 催化, 加氢, 结构敏感性, 反应动力学

Abstract:

Selective hydrogenation of acetylene catalyzed by Pd-based catalysts is crucial in the production of polymer-grade ethylene from both steam cracking process of naphtha and the coal-based acetylene feedstock. The traditional Pd-based catalysts are expensive, and exhibit poor selectivity and stability. This review summarizes recent research advances in the structure-sensitivity of catalyst and the corresponding regulation of catalysts' structures. The effects of particle sizes, morphologies and electronic structures of active metal nanoparticles on the catalytic performance are demonstrated, which provides the target of structure regulation toward enhanced performance. Furthermore, the research progress related to the precise structure regulations for the catalysts are summarized based on the characteristics of hydrogenation of acetylene, including the introduction of a second metal to prepare alloy or intermetallic compounds catalysts and the design of single atom and single atom alloy catalysts (SAC and SAA). By rationally regulating the structure of catalysts, we could optimize the adsorption/desorption behavior of key species involved in the reaction and the reaction kinetics, and then the selectivity and stability of catalysts can be significantly improved. In the future research, the rational design of highly efficient, stable and low-cost catalysts for the reaction would be the key issue.

Key words: acetylene, catalysis, hydrogenation, structure-sensitivity, reaction kinetics

中图分类号:

O643

李雨柔, 葛小虎, 曹约强, 段学志, 周兴贵, 袁渭康. 乙炔选择性加氢：催化剂结构敏感性分析及调控[J]. 化工进展, 2020, 39(12): 4845-4855.

Yurou LI, Xiaohu GE, Yueqiang CAO, Xuezhi DUAN, Xinggui ZHOU, Weikang YUAN. Selective hydrogenation of acetylene: structure sensitivity of catalysts and precise regulation[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 4845-4855.

参考文献

1	TORRES GALVIS H M, DE JONG K P. Catalysts for production of lower olefins from synthesis gas: a review[J]. ACS catalysis, 2013, 3(9): 2130-2149.
2	BRIDIER B, PEREZ-RAMIREZ J. Cooperative effects in ternary Cu-Ni-Fe catalysts lead to enhanced alkene selectivity in alkyne hydrogenation[J]. Journal of the American Chemical Society, 2010, 132(12): 4321-4327.
3	MCCUE A J, ANDERSON J A. Recent advances in selective acetylene hydrogenation using palladium containing catalysts[J]. Frontiers of Chemical Science and Engineering, 2015, 9(2): 142-153.
4	尚国隆.电石法乙炔气清净工艺研究[D]. 青岛: 青岛科技大学, 2018．
4	SHANG G L. Study on the purification process of acetylene by calcium carbide[D]. Qingdao: Qingdao University of Science and Technology, 2018.
5	赵令玉.乙炔选择加氢制乙烯催化剂及反应工艺的研究[D]. 石河子: 石河子大学，2010．
5	ZHAO L Y. Catalysts to synthesis ethylene of selective hydrogenation of acetylene and its reaction technology[D]. Shihezi: Shihezi University, 2010.
6	BENAVIDEZ A D, BURTON P D, NOGALES J L, et al. Improved selectivity of carbon-supported palladium catalysts for the hydrogenation of acetylene in excess ethylene[J]. Applied Catalysis A: General, 2014, 482: 108-115.
7	CAO Y Q, FU W Z, SUI Z J, et al. Kinetics insights and active sites discrimination of Pd-Catalyzed selective hydrogenation of acetylene[J]. Industrial & Engineering Chemistry Research, 2019, 58(5): 1888-1895.
8	RUTA M, SEMAGINA N, KIWI-MINSKER L. Monodispersed Pd nanoparticles for acetylene selective hydrogenation: particle size and support effects[J]. The Journal of Physical Chemistry C, 2008, 112(35): 13635-13641.
9	SHI X X, LIN Y, HUANG L, et al. Copper catalysts in semihydrogenation of acetylene: from single atoms to nanoparticles[J]. ACS Catalysis, 2020, 10(5): 3495-3504.
10	KUO C T, LU Y, KOVARIK L, et al. Structure sensitivity of acetylene semi-hydrogenation on Pt single atoms and subnanometer clusters[J]. ACS Catalysis, 2019, 9(12): 11030-11041.
11	CRESPO-QUESADA M, YARULIN A, JIN M, et al. Structure sensitivity of alkynol hydrogenation on shape-and size-controlled palladium nanocrystals: which sites are most active and selective?[J]. Journal of the American Chemical Society, 2011, 133(32): 12787-12794.
12	á MOLNáR, SáRKáNY A, VARGA M. Hydrogenation of carbon-carbon multiple bonds: chemo-, regio-and stereo-selectivity[J]. Journal of Molecular Catalysis A: Chemical, 2001, 173(1/2): 185-221.
13	KIM S K, KIM C, LEE J H, et al. Performance of shape-controlled Pd nanoparticles in the selective hydrogenation of acetylene[J]. Journal of Catalysis, 2013, 306: 146-154.
14	YARULIN A E, CRESPO-QUESADA R M, EGOROVA E V, et al. Structure sensitivity of selective acetylene hydrogenation over the catalysts with shape-controlled palladium nanoparticles[J]. Kinetics and Catalysis, 2012, 53(2): 253-261.
15	YANG B, BURCH R, HARDACRE C, et al. Influence of surface structures, subsurface carbon and hydrogen, and surface alloying on the activity and selectivity of acetylene hydrogenation on Pd surfaces: a density functional theory study[J]. Journal of Catalysis, 2013, 305: 264-276.
16	NIU Y, ZHANG B, LUO J, et al. Correlation between microstructure evolution of a well-defined cubic palladium catalyst and selectivity during acetylene hydrogenation[J]. ChemCatChem, 2017, 9(18): 3435-3439.
17	TESCHNER D, BORSODI J, WOOTSCH A, et al. The roles of subsurface carbon and hydrogen in palladium-catalyzed alkyne hydrogenation[J]. Science, 2008, 320(5872): 86-89.
18	CRESPO-QUESADA M, YOON S, JIN M, et al. Shape-dependence of Pd nanocrystal carburization during acetylene hydrogenation[J]. The Journal of Physical Chemistry C, 2015, 119(2): 1101-1107.
19	WANG Y, YANG J, GU R, et al. Crystal-facet effect of γ-Al₂O₃ on supporting CrO_x for catalytic semihydrogenation of acetylene[J]. ACS Catalysis, 2018, 8(7): 6419-6425.
20	HE Y, FAN J, FENG J, et al. Pd nanoparticles on hydrotalcite as an efficient catalyst for partial hydrogenation of acetylene: effect of support acidic and basic properties[J]. Journal of Catalysis, 2015, 331: 118-127.
21	CAO Y Q, FU W Z, REN Z, et al. Tailoring electronic properties and kinetics behaviors of Pd/N-CNTs catalysts for selective hydrogenation of acetylene[J]. AIChE Journal, 2020, 66(4): e16857.
22	VILé G, ALBANI D, ALMORA-BARRIOS N, et al. Advances in the design of nanostructured catalysts for selective hydrogenation[J]. ChemCatChem, 2016, 8(1): 21-33.
23	NIKOLAEV S A, ZANAVESKIN L N, SMIRNOV V V, et al. Catalytic hydrogenation of alkyne and alkadiene impurities from alkenes. Practical and theoretical aspects[J]. Russian Chemical Reviews, 2009, 78(3): 231.
24	CAO Y Q, SUI Z J, ZHU Y A, et al. Selective hydrogenation of acetylene over Pd-In/Al₂O₃ catalyst: promotional effect of indium and composition-dependent performance[J]. ACS Catalysis, 2017, 7(11): 7835-7846.
25	MARKOV P V, BUKHTIYAROV A V, MASHKOVSKY I S, et al. PdIn/Al₂O₃ intermetallic catalyst: structure and catalytic characteristics in selective hydrogenation of acetylene[J]. Kinetics and Catalysis, 2019, 60(6): 842-850.
26	FENG Q C, ZHAO S, WANG Y, et al. Isolated single-atom Pd sites in intermetallic nanostructures: high catalytic selectivity for semihydrogenation of alkynes[J]. Journal of the American Chemical Society, 2017, 139(21): 7294-7301.
27	ZHOU H R, YANG X F, LI L, et al. PdZn intermetallic nanostructure with Pd-Zn-Pd ensembles for highly active and chemoselective semi-hydrogenation of acetylene[J]. ACS Catalysis, 2016, 6(2): 1054-1061.
28	SHAO L D, ZHANG W, ARMBRüSTER M, et al. Nanosizing intermetallic compounds onto carbon nanotubes: active and selective hydrogenation catalysts[J]. Angewandte Chemie: International Edition, 2011, 50(43): 10231-10235.
29	GLYZDOVA D V, VEDYAGIN A A, TSAPINA A M, et al. A study on structural features of bimetallic Pd-M/C (M: Zn, Ga, Ag) catalysts for liquid-phase selective hydrogenation of acetylene[J]. Applied Catalysis A: General, 2018, 563: 18-27.
30	RIYAPAN S, ZHANG Y, WONGKAEW A, et al. Preparation of improved Ag-Pd/TiO₂ catalysts using the combined strong electrostatic adsorption and electroless deposition methods for the selective hydrogenation of acetylene[J]. Catalysis Science & Technology, 2016, 6(14): 5608-5617.
31	ZHANG R, ZHANG J, ZHAO B, et al. Insight into the effects of Cu component and the promoter on the selectivity and activity for efficient removal of acetylene from ethylene on Cu-based catalyst[J]. The Journal of Physical Chemistry C, 2017, 121(50): 27936-27949.
32	YANG B, BURCH R, HARDACRE C, et al. Origin of the increase of activity and selectivity of nickel doped by Au, Ag, and Cu for acetylene hydrogenation[J]. ACS Catalysis, 2012, 2(6): 1027-1032.
33	STUDT F, ABILD-PEDERSEN F, BLIGAARD T, et al. Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene[J]. Science, 2008, 320(5881): 1320-1322.
34	SPANJERS C S, HELD J T, JONES M J, et al. Zinc inclusion to heterogeneous nickel catalysts reduces oligomerization during the semi-hydrogenation of acetylene[J]. Journal of Catalysis, 2014, 316: 164-173.
35	CAO Y Q, ZHANG H, JI S F, et al. Adsorption site regulation to guide atomic design of Ni-Ga catalysts for acetylene semi-hydrogenation[J]. Angewandte Chemie, 2020, 132(28):11744-11749.
36	LIU Y, LIU X, FENG Q, et al. Intermetallic Ni_xM_y (M= Ga and Sn) nanocrystals: a non-precious metal catalyst for semi-hydrogenation of alkynes[J]. Advanced Materials, 2016, 28(23): 4747-4754.
37	LI Q, WANG Y, SKOPTSOV G, et al. Selective hydrogenation of acetylene to ethylene over bimetallic catalysts[J]. Industrial & Engineering Chemistry Research, 2019, 58(45): 20620-20629.
38	LIN J, WANG A Q, QIAO B T, et al. Remarkable performance of Ir₁/FeO_xsingle-atom catalyst in water gas shift reaction[J]. Journal of the American Chemical Society, 2013, 135(41): 15314-15317.
39	CAO L, LIU W, LUO Q Q, et al. Atomically dispersed iron hydroxide anchored on Pt for preferential oxidation of CO in H₂[J]. Nature, 2019, 565(7741): 631-635.
40	THOMAS J M, RAJA R, LEWIS D W. Single-site heterogeneous catalysts[J]. Angewandte Chemie: International Edition, 2005, 44(40): 6456-6482.
41	DAI X Y, CHEN Z, YAO T, et al. Single Ni sites distributed on N-doped carbon for selective hydrogenation of acetylene[J]. Chemical Communications, 2017, 53(84): 11568-11571.
42	KYRIAKOU G, BOUCHER M B, JEWELL A D, et al. Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations[J]. Science, 2012, 335(6073): 1209-1212.
43	ZHAO Y, ZHU M Y, KANG L H. The DFT study of single-atom Pd₁/gC₃N₄catalyst for selective acetylene hydrogenation reaction[J]. Catalysis Letters, 2018, 148(10): 2992-3002.
44	HUANG F, DENG Y C, CHEN Y L, et al. Atomically dispersed Pd on nanodiamond/graphene hybrid for selective hydrogenation of acetylene[J]. Journal of the American Chemical Society, 2018, 140(41): 13142-13146.
45	HUANG F, DENG Y C, CHEN Y L, et al. Anchoring Cu₁ species over nanodiamond-graphene for semi-hydrogenation of acetylene[J]. Nature Communications, 2019, 10(1): 1-7.
46	HUANG X H, XIA Y J, CAO Y J, et al. Enhancing both selectivity and coking-resistance of a single-atom Pd₁/C₃N₄ catalyst for acetylene hydrogenation[J]. Nano Research, 2017, 10(4): 1302-1312.
47	ZHOU S Q, SHANG L, ZHAO Y X, et al. Pd single-atom catalysts on nitrogen-doped graphene for the highly selective photothermal hydrogenation of acetylene to ethylene[J]. Advanced Materials, 2019, 31(18): 1900509.
48	ZHUO H Y, YU X, YU Q, et al. Selective hydrogenation of acetylene on graphene-supported non-noble metal single-atom catalysts[J]. Science China Materials, 2020, 63(9): 1741-1749.
49	PEI G X, LIU X Y, WANG A, et al. Ag alloyed Pd single-atom catalysts for efficient selective hydrogenation of acetylene to ethylene in excess ethylene[J]. ACS Catalysis, 2015, 5(6): 3717-3725.
50	PEI G X, LIU X Y, WANG A, et al. Promotional effect of Pd single atoms on Au nanoparticles supported on silica for the selective hydrogenation of acetylene in excess ethylene[J]. New Journal of Chemistry, 2014, 38(5): 2043-2051.
51	PEI G X, LIU X Y, YANG X, et al. Performance of Cu-alloyed Pd single-atom catalyst for semihydrogenation of acetylene under simulated front-end conditions[J]. ACS Catalysis, 2017, 7(2): 1491-1500.
52	LIU D. DFT study of selective hydrogenation of acetylene to ethylene on Pd doping Ag nanoclusters[J]. Applied Surface Science, 2016, 386: 125-137.
53	CAO X, MIRJALILI A, WHEELER J, et al. Investigation of the preparation methodologies of Pd-Cu single atom alloy catalysts for selective hydrogenation of acetylene[J]. Frontiers of Chemical Science and Engineering, 2015, 9(4): 442-449.
54	BATISTA J, PINTAR A, GOMIL?EK J P, et al. On the structural characteristics of γ-alumina-supported Pd-Cu bimetallic catalysts[J]. Applied Catalysis A: General, 2001, 217(1/2): 55-68.
55	J?RGENSEN M, GRO?NBECK H. Selective acetylene hydrogenation over single-atom alloy nanoparticles by kinetic Monte Carlo[J]. Journal of the American Chemical Society, 2019, 141(21): 8541-8549.
56	RILEY C, ZHOU S, KUNWAR D, et al. Design of effective catalysts for selective alkyne hydrogenation by doping of ceria with a single-atom promotor[J]. Journal of the American Chemical Society, 2018, 140(40): 12964-12973.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[6]	王正坤, 黎四芳. 双子表面活性剂癸炔二醇的绿色合成[J]. 化工进展, 2023, 42(S1): 400-410.
[7]	高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.
[8]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[9]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[10]	许友好, 王维, 鲁波娜, 徐惠, 何鸣元. 中国炼油创新技术MIP的开发策略及启示[J]. 化工进展, 2023, 42(9): 4465-4470.
[11]	耿源泽, 周俊虎, 张天佑, 朱晓宇, 杨卫娟. 部分填充床燃烧器中庚烷均相/异相耦合燃烧[J]. 化工进展, 2023, 42(9): 4514-4521.
[12]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[13]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.
[14]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[15]	高彦静. 单原子催化技术国际研究态势分析[J]. 化工进展, 2023, 42(9): 4667-4676.