丙烷脱氢制丙烯催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2020-1990

摘要/Abstract

摘要：

丙烷脱氢产业的迅猛发展亟需研发新一代高性能催化剂。本综述阐述了近年来新型负载型Pt纳米簇、金属氧化物和碳材料在丙烷脱氢反应中的研究进展。文章指出：Pt纳米簇的分散性和稳定性是决定其脱氢性能的关键因素；通过发展新合成技术和调节载体性质能改进其催化活性。金属氧化物中不饱和金属阳离子是脱氢反应的活性位点；调节载体的性质、优化制备方法以及结构掺杂都可显著提高其催化活性。碳材料中的含氧官能团被认为是丙烷脱氢反应的活性中心；对碳材料的比表面积、孔道性质及含氧官能团的数量等参数进行合理调控，能改善其催化性能。最后，文章提出未来的研究将重点解决Pt纳米簇的抗烧结性能弱、氧化物的本征活性低、碳材料高温稳定性差的问题，实现该领域的重大突破。

关键词: 烷烃, 催化剂, 脱氢, 构-效关系, 稳定性

Abstract:

With the rapid development of propane dehydrogenation for the production of propylene, it is urgent to develop a new generation of high-performance catalysts. In this review, recent progresses of supported Pt nanoclusters, metal oxides, and carbon materials in propane dehydrogenation are discussed. The dispersion and stability of Pt nanoclusters are the key factors affecting the dehydrogenation performance. The catalytic activity of Pt nanoclusters can be improved by developing new synthesis techniques and adjusting the properties of supports. The unsaturated metal cations in metal oxides are the active sites for dehydrogenation reaction. The catalytic activity can be significantly improved by adjusting the properties of supports, optimizing the preparation methods, and structural doping. The oxygen-containing functional groups in carbon materials are considered to be active sites for propane dehydrogenation reaction. The catalytic performance of carbon materials can be enhanced by tuning the surface area, pore property, and the number of oxygen-containing functional groups. Future studies should be focused on improving the anti-resistant ability of Pt nanoclusters, enhancing the intrinsic activity of oxides, and increasing the thermal-stability of carbon materials, which leads to breakthroughs in the development of propane dehydrogenation catalyst.

Key words: alkane, catalyst, dehydrogenation, structure-activity relationship, stability

中图分类号:

O643.3

徐志康, 黄佳露, 王廷海, 岳源源, 白正帅, 鲍晓军, 朱海波. 丙烷脱氢制丙烯催化剂的研究进展[J]. 化工进展, 2021, 40(4): 1893-1916.

XU Zhikang, HUANG Jialu, WANG Tinghai, YUE Yuanyuan, BAI Zhengshuai, BAO Xiaojun, ZHU Haibo. Advances in catalysts for propane dehydrogenation to propylene[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 1893-1916.

图/表 22

参考文献 153

1	SU D S, PERATHONER S, CENTI G. ChemInform abstract: nanocarbons for the development of advanced catalysts[J]. Chemical Reviews, 2013, 113(8): 5782-5816.
2	RAZAVIAN M, FATEMI S. Synthesis and application of ZSM-5/SAPO-34 and SAPO-34/ZSM-5 composite systems for propylene yield enhancement in propane dehydrogenation process[J]. Microporous & Mesoporous Materials, 2015, 201: 176-189.
3	QI Wei, YAN Pengqiang, SU Dangsheng. Oxidative dehydrogenation on nanocarbon: insights into the reaction mechanism and kinetics viain situ experimental methods[J]. Accounts of Chemical Research, 2018, 51(3): 640-648.
4	FAN Zeyun, ZHANG Zhixiang, FANG Wenjian, et al. Low-temperature catalytic oxidation of formaldehyde over Co₃O₄ catalysts prepared using various precipitants[J]. Chinese Journal of Catalysis, 2016, 37(6): 947-954.
5	中国产业信息网.中国丙烯市场供需现状分析及预测[EB/OL]. .
	Web of China Industry Information. The analysis and forecast of China’s propylene market supply and demand status[EB/OL]. .
6	SERRANO-RUIZ J C, SEPÚLVEDA-ESCRIBANO A, RODRÍGUEZ-REINOSO F. Bimetallic PtSn/C catalysts promoted by ceria: application in the nonoxidative dehydrogenation of isobutane[J]. Journal of Catalysis, 2007, 246(1): 158-165.
7	ZHANG J, LIU X, BLUME R, et al. Surface-modified carbon nanotubes catalyze oxidative dehydrogenation of n-Butane[J]. Science, 2008, 322(5898): 73-77.
8	ZHAO Huahua, SONG Huanling, XU Leilei, et al. Isobutane dehydrogenation over the mesoporous Cr₂O₃/Al₂O₃ catalysts synthesized from a metal-organic framework MIL-101[J]. Applied Catalysis A: General, 2013, 456: 188-196.
9	YARULINA I, DE WISPELAERE K, BAILLEUL S, et al. Structure-performance descriptors and the role of Lewis acidity in the methanol-to-propylene process[J]. Nature Chemistry, 2018, 10(8): 804-812.
10	TASBIHI M, FEYZI F, AMLASHI M A, et al. Effect of the addition of potassium and lithium in Pt-Sn/Al₂O₃ catalysts for the dehydrogenation of isobutane[J]. Fuel Processing Technology, 2007, 88(9): 883-889.
11	ATANGA M A, REZAEI F, JAWAD A, et al. Oxidative dehydrogenation of propane to propylene with carbon dioxide[J]. Applied Catalysis B: Environmental, 2018, 220: 429-445.
12	CAVANI F, BALLARINI N, CERICOLA A. Oxidative dehydrogenation of ethane and propane: how far from commercial implementation?[J]. Catalysis Today, 2007, 127(1/2/3/4): 113-131.
13	盖希坤, 田原宇, 夏道宏. 丙烷催化脱氢制丙烯工艺分析[J]. 炼油技术与工程, 2012, 40(12): 27-32.
	GAI Xikun, TIAN Yuanyu, XIA Daohong. Study on technology of propane dehydrogenation for propylene production[J]. Petroleum Refinery Engineering, 2012, 40(12): 27-32.
14	STEPHANIE S, SABBE M K, GALVITA V V. Positive effect of Ga-promoting on the catalytic dehydrogenation of propane over a Pt catalyst[C]//18th Netherlands’ Catalysis and Chemistry Conference (NCCC), 2017.
15	JIANG Guiyuan, ZHANG Li, ZHAO Zhen, et al. Highly effective P-modified HZSM-5 catalyst for the cracking of C₄ alkanes to produce light olefins[J]. Applied Catalysis A: General, 2008, 340(2): 176-182.
16	CHEN De, HOLMEN A, Zhijun SUI, et al. Carbon mediated catalysis: a review on oxidative dehydrogenation[J]. Chinese Journal of Catalysis, 2014, 35(6): 824-841.
17	KAINTHLA I, BHANUSHALI J T, KERI R, et al. Activity studies of vanadium, iron, carbon and mixed oxides based catalysts for the oxidative dehydrogenation of ethylbenzene to styrene: a review[J]. Catalysis Science & Technology, 2015, 5(12): 5062-5076.
18	FENG Jing, ZHANG Mingsen, KE Li, et al. Research progress in propane dehydrogenation catalysts[J]. Industrial Catalysis, 2011, 19(3): 8-14.
19	ZHANG Lingfeng, LIU Yalu, HU Zhongpan, et al. Advance in catalysts for propane dehydrogenation to propylene[J]. Acta Petrol Sinica, 2015, 31(2): 400-417.
20	GRUNERT W. Principles and practice of heterogeneous catalysis[J]. Focus on Catalysts, 2015, 7: 7.
21	ZHOU Shijian, ZHOU Yuming, ZHANG Yiwei, et al. The synthesis of new coke-resistant support and its application in propane dehydrogenation to propene[J]. Journal of Chemical Technology & Biotechnology, 2016, 91(4): 1072-1081.
22	YU Changlin, XU Hengyong, GE Qingjie, et al. Properties of the metallic phase of zinc-doped platinum catalysts for propane dehydrogenation[J]. Journal of Molecular Catalysis A: Chemical, 2007, 266(1/2): 80-87.
23	SATTLER J J, GONZALEZ-JIMENEZ I D, MENS A M, et al. Operando UV-vis spectroscopy of a catalytic solid in a pilot-scale reactor: deactivation of a CrO_x/Al₂O₃ propane dehydrogenation catalyst[J]. Chemical Communications, 2013, 49(15): 1518-1520.
24	SEARLES K, CHAN Kawing, BURAK J A M, et al. Highly productive propane dehydrogenation catalyst using silica-supported Ga-Pt nanoparticles generated from single-sites[J]. Journal of the American Chemical Society, 2018, 140(37): 11674-11679.
25	LI Jiacheng, LI Jianmei, ZHAO Zhen, et al. Size effect of TS-1 supports on the catalytic performance of PtSn/TS-1 catalysts for propane dehydrogenation[J]. Journal of Catalysis, 2017, 352: 361-370.
26	SOKOLOV S, STOYANOVA M, RODEMERCK U, et al. Comparative study of propane dehydrogenation over V-, Cr-, and Pt-based catalysts: time on-stream behavior and origins of deactivation[J]. Journal of Catalysis, 2012, 293: 67-75.
27	XIONG Haifeng, LIN Sen, GOETZE J, et al. Thermally stable and regenerable platinum-tin clusters for propane dehydrogenation prepared by atom trapping on ceria[J]. Angewandte Chemie International Edition, 2017, 56(31): 8986-8991.
28	ZHOU Shijian, ZHOU Yuming, ZHANG Yiwei, et al. The synthesis of new coke-resistant support and its application in propane dehydrogenation to propene[J]. Journal of Chemical Technology & Biotechnology, 2016, 91(4): 1072-1081.
29	ZHANG Yiwei, ZHOU Yuming, QIU Anding, et al. Propane dehydrogenation on PtSn/ZSM-5 catalyst: effect of tin as a promoter[J]. Catalysis Communications, 2006, 7(11): 860-866.
30	SATTLWER J J H B, MENS A M, WECKHUYSEN B M. Real-time quantitative operando raman spectroscopy of a CrO_x/Al₂O₃ propane dehydrogenation catalyst in a pilot-scale reactor[J]. ChemCatChem, 2014, 6(11): 3139-3145.
31	MCGREGOR J, HUANG Zhenyu, PARROTT E P J, et al. Active coke: carbonaceous materials as catalysts for alkane dehydrogenation[J]. Journal of Catalysis, 2010, 269(2): 329-339.
32	LIAN Zan, ALI S, LIU Tianfu, et al. Revealing Janus character of the coke precursor in the propane direct dehydrogenation on Pt catalysts from a kMC simulation[J]. ACS Catalysis, 2018, 8(5): 4694-4704.
33	AIRAKSINEN S M K, KRAUSE A O I. In situ characterisation of carbon-containing species formed on chromia/alumina during propane dehydrogenation[J]. Journal of Catalysis, 2005, 230(2): 507-513.
34	CASPARY K J, GEHRKE H, HEINRITZ-ADRIAN M. Handbook of heterogeneous catalysis[M]. Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
35	LI Qing, Zhijun SUI, ZHOU Xinggui, et al. Coke formation on Pt-Sn/Al₂O₃ catalyst in propane dehydrogenation: coke characterization and kinetic study[J]. Topics in Catalysis, 2011, 54(13/14/15): 888-896.
36	SHAN Yuling, WANG Ting, Zhijun SUI, et al. Hierarchical MgAl₂O₄ supported Pt-Sn as a highly thermostable catalyst for propane dehydrogenation[J]. Catalysis Communications, 2016, 84(5): 85-88.
37	SHAN Yuling, ZHU Yian, SUN Zhijun, et al. Insights into the effects of steam on propane dehydrogenation over a Pt/Al₂O₃ catalyst[J]. Catalysis Science & Technology, 2015, 5(8): 3991-4000.
38	HAUSRE A W, HORN P R, HEAD-GORDON M, et al. A systematic study on Pt based, subnanometer-sized alloy cluster catalysts for alkane dehydrogenation: effects of intermetallic interaction[J]. Physical Chemistry Chemical Physics, 2016, 18(16): 10906-109017.
39	YANG Minglei, ZHU Yian, FAN Chen, et al. DFT study of propane dehydrogenation on Pt catalyst: effects of step sites[J]. Physical Chemistry Chemical Physics, 2011, 13(8): 3257-3267.
40	ZHU Jun, YANG Minglei, ZHU Yian. Size-dependent reaction mechanism and kinetics for propane dehydrogenation over Pt catalysts[J]. ACS Catalysis, 2015, 5(11): 6310-6319.
41	SUN Guodong, ZHAO Zhi Jian, MU Rentao, et al. Breaking the scaling relationship via thermally stable Pt/Cu single atom alloys for catalytic dehydrogenation[J]. Nature Communications, 2018, 9(1): 4454-4462.
42	NAKAYA Y, HIRAYAMA J, YAMAZOE S, et al. Single-atom Pt in intermetallics as an ultrastable and selective catalyst for propane dehydrogenation[J]. Nature Communications, 2020, 11(1):2838-2845.
43	VU B K, SONG M B, AHN I Y, et al. Propane dehydrogenation over Pt-Sn/rare-earth-doped Al₂O₃: influence of La, Ce, or Y on the formation and stability of Pt-Sn alloys[J]. Catalysis Today, 2011, 164(1): 214-220.
44	SRISAKWATTANA T, SURIYE K, PRASERTHDAM P, et al. Preparation of aluminum magnesium oxide by different methods for use as PtSn catalyst supports in propane dehydrogenation[J]. Catalysis Today, 2020, 358: 90-99.
45	XIA Ke, LANG Wanzhong, LI Peipei, et al. The influences of Mg/Al molar ratio on the properties of PtIn/Mg(Al)O-x catalysts for propane dehydrogenation reaction[J]. Chemical Engineering Journal, 2016, 284(15): 1068-1079.
46	XU Zhikang, XU Rui, YUE Yuanyuan, et al. Bimetallic Pt-Sn nanocluster from the hydrogenolysis of a well-defined surface compound consisting of [(Al≡O)Pt(COD)Me] and [(Al≡O)SnPh₃] fragments for propane dehydrogenation[J]. Journal of Catalysis, 2019, 374: 391-400.
47	ROCHLITZ L, SEARLES K, ALFKE J, et al. Silica-supported, narrowly distributed, subnanometric Pt-Zn particles from single sites with high propane dehydrogenation performance[J]. Chemical Science, 2020, 11(6): 1549-1555.
48	NANDA K, SAHU S, BEHERA S. Liquid-drop model for the size-dependent melting of low-dimensional systems[J]. Physical Review A, 66(1): 013208.
49	MORGAN K, GOGUET A, HARDACRE C. Metal redispersion strategies for recycling of supported metal catalysts: a perspective[J]. ACS Catalysis, 2015, 5(6): 3430-3445.
50	BARTHOLOMEW C H. Mechanisms of catalyst deactivation[J]. Applied Catalysis A: General, 2001, 212(1): 17-60.
51	HATANAKA M, TAKAHASHI N, TAKAHASHI N, et al. Reversible changes in the Pt oxidation state and nanostructure on a ceria-based supported Pt[J]. Journal of Catalysis, 2009, 266(2): 182-190.
52	TAUSTER S J, FUNG S C. Strong metal-support interactions: occurrence among the binary oxides of groups ⅡA—VB[J]. Journal of Catalysis, 1978, 55(1): 29-35.
53	TAUSTER S J, FUNG S C, GARTEN R L. Strong metal-support interactions. group 8 noble metals supported on TiO₂[J]. Chemischer Informationsdienst, 1978, 9(16): 170-175.
54	LEE J, JANG E J, OH D G, et al. Morphology and size of Pt on Al₂O₃: the role of specific metal-support interactions between Pt and Al₂O₃[J]. Journal of Catalysis, 2020, 385: 204-212.
55	KWAK J H, HU Jianzhi, MEI Donghai, et al. Coordinatively unsaturated Al³⁺ centers as binding sites for active catalyst phases of platinum on gamma-Al₂O₃[J]. Science, 2009, 325(5948): 1670-1673.
56	SHI Lei, DENG Gaoming, LI Wencui, et al. Al₂O₃ nanosheets rich in pentacoordinate Al³⁺ ions stabilize Pt-Sn clusters for propane dehydrogenation[J]. Angewandte Chemie: International Edition, 2016, 54(47): 13994-13998.
57	ZHANG Yiwei, ZHOU Yuming, SHI Junjun, et al. Comparative study of bimetallic Pt-Sn catalysts supported on different supports for propane dehydrogenation[J]. Journal of Molecular Catalysis A: Chemical, 2014, 381: 138-147.
58	DENG Lidan, MIURA H, TETSUYA S, et al. Strong metal-support interaction between Pt and SiO₂ following high-temperature reduction: a catalytic interface for propane dehydrogenation[J]. Chemical Communications, 2017, 53(51): 6937-6940.
59	TOLEK W, SURIYE K, PRASERTHDAM P, et al. Effect of preparation method on the Pt-In modified Mg(Al)O catalysts over dehydrogenation of propane[J]. Catalysis Today, 2020, 358: 100-108.
60	LIU Jie, YUE Yuanyuan, LIU Hongyang, et al. Origin of the robust catalytic performance of nanodiamond-graphene-supported Pt nanoparticles used in the propane dehydrogenation reaction[J]. ACS Catalysis, 2017, 7(5): 3349-3355.
61	LIU Jie, LI Jiaquan, RONG Junfeng, et al. Defect-driven unique stability of Pt/carbon nanotubes for propane dehydrogenation[J]. Applied Surface Science, 2019, 464(15): 146-152.
62	ZHU Yanru, AN Zhe, SONG Hongyan, et al. Lattice-confined Sn (Ⅳ/Ⅱ) stabilizing raft-like Pt clusters: high selectivity and durability in propane dehydrogenation[J]. ACS Catalysis, 2017, 7(10): 6973-6978.
63	XU Zhikang, YUE Yuanyuan, BAO Xiaojun, et al. Propane dehydrogenation over Pt clusters localized at the Sn single-site in zeolite framework[J]. ACS Catalysis, 2020, 10: 818-828.
64	SUN Qiming, WANG Ning, FAN Qiyuan, et al. Subnanometer bimetallic platinum-zinc clusters in zeolites for propane dehydrogenation[J]. Angewandte Chemie: International Edition, 2020, 59(44): 19450-19459.
65	WANG Yansu, HU ZhongPan, YUAN Zhongyong. Ultrasmall PtZn bimetallic nanoclusters encapsulated in silicalite-1 zeolite with superior performance for propane dehydrogenation[J]. Journal of Catalysis, 2020, 385: 61-69.
66	LIU Lichen, LOPEZ-HARO M, LOPES C W, et al. Atomic-level understanding on the evolution behavior of subnanometric Pt and Sn species during high-temperature treatments for generation of dense PtSn clusters in zeolites[J]. Journal of Catalysis, 2020, 391: 11-24.
67	LIU Lichen, LOPEZ-HARO M, LOPES C W, et al. Structural modulation and direct measurement of subnanometric bimetallic PtSn clusters confined in zeolites[J]. Nature Catalysis, 2020, 3: 628-638.
68	ZHU Jie, RYOTA O, RYO I. Ultrafast encapsulation of metal nanoclusters into MFI zeolite in the course of its crystallization: catalytic application for propane dehydrogenation[J]. Angewandte Chemie International Edition, 2020, 59(44): 19669-19674.
69	WANG Haizhi, SUN Lili, Zhijun SUI, et al. Coke formation on Pt-Sn/Al₂O₃ catalyst for propane dehydrogenation[J]. Industrial & Engineering Chemistry Research, 2018, 57(26): 8647-8654.
70	ZIMMER H, DOBROVOLSZKY M, TETENY P, et al. Hydrogen control of platinum-catalyzed skeletal reactions of alkanes: selectivity and surface species[J]. The Journal of Physical Chemistry, 1986, 90(20): 4758-4764.
71	LARSSON M, MAGNUS H, BLEKKAN E A, et al. The effect of reaction conditions and time on stream on the coke formed during propane dehydrogenation[J]. Journal of Catalysis, 1996, 164(1): 44-53.
72	YANG Minglei, ZHU Yian, FAN Chen, et al. Density functional study of the chemisorption of C₁, C₂ and C₃ intermediates in propane dissociation on Pt(111)[J]. Journal of Molecular Catalysis A: Chemical, 2010, 321(1/2): 42-49.
73	SABBE M K, CANDUELA-RODRIGUEZ G, REYNIERS M F, et al. DFT-based modeling of benzene hydrogenation on Pt at industrially relevant coverage[J]. Journal of Catalysis, 2015, 330: 406-422.
74	LI Qing, Zhijun SUI, ZHOU Xinggui. Kinetics of propane dehydrogenation over Pt-Sn/Al₂O₃ catalyst[J]. Applied Catalysis A: General, 2011, 398(1/2): 18-26.
75	SAERENS S, SABBE M, GALVITA V, et al. Positive effect of Ga-promoting on the catalytic dehydrogenation of propane over a Pt catalyst[J]. ACS Cataysis, 2017, 7: 7495-7508.
76	ZAERA F, CHRYSOSTOMOU D. Propylene on Pt(111) Ⅱ. Hydrogenation, dehydrogenation, and H-D exchange[J]. Surface Science, 2000, 457(1/2): 71-88.
77	SIDDIQI G, SUN Pingping, GALVITA V, et al. Catalyst performance of novel Pt/Mg(Ga)(Al)O catalysts for alkane dehydrogenation[J]. Journal of Catalysis, 2010, 274(2): 200-206.
78	ZANGENEH F T, MEHRAZMA S, SAHEBDELFAR S. The influence of solvent on the performance of Pt-Sn/θ-Al₂O₃ propane dehydrogenation catalyst prepared by co-impregnation method[J]. Fuel Processing Technology, 2013, 109: 118-123.
79	JANG E J, LEE J J, JEONG H Y, et al. Controlling the acid-base properties of alumina for stable PtSn-based propane dehydrogenation catalysts[J]. Applied Catalysis A: General, 2019, 572: 1-8.
80	WANG Tuo, JIANG Feng, LIU Gang. Effects of Ga doping on Pt/CeO₂‐Al₂O₃ catalysts for propane dehydrogenation[J]. AIChE Journal, 2016, 62(12): 4365-4376.
81	LONG Liuliu, XIA Ke, LANG Wanzhong, et al. The comparison and optimization of zirconia, alumina, and zirconia-alumina supported PtSnIn trimetallic catalysts for propane dehydrogenation reaction[J]. Journal of Industrial and Engineering Chemistry, 2017, 51(25): 271-280.
82	JIANG Feng, ZENG Liang, LI Shuirong, et al. Propane dehydrogenation over Pt/TiO₂-Al₂O₃ catalysts[J]. ACS Catalysis, 2015, 5(1): 438-447.
83	ZHOU Hualan, GONG Jingjing, XU Bolian, et al. PtSnNa/SUZ-4: an efficient catalyst for propane dehydrogenation[J]. Chinese Journal of Catalysis, 2017, 38(3): 529-536.
84	LEE M H, NAGARAJA B M, NATARAJAN P, et al. Effect of potassium addition on bimetallic PtSn/θ-Al₂O₃ catalyst for dehydrogenation of propane to propylene[J]. Research on Chemical Intermediates, 2016, 42(1): 123-140.
85	DAUN Yongzheng, ZHOU Yuming, ZHANG Yiwei, et al. Effect of sodium addition to PtSn/AlSBA-15 on the catalytic properties in propane dehydrogenation[J]. Catalysis Letters, 2011, 141(1): 120-127.
86	LOBERA M P, HERGUIDO J, SCHUUMAN Y, et al. TAP studies of Pt-Sn-K/γ-Al₂O₃ catalyst for propane dehydrogenation[J]. Chemical Engineering Journal, 2011, 171(3): 1317-1323.
87	LI Bing, XU Zhenxin, JING Fangli, et al. Facile one-pot synthesized ordered mesoporous Mg-SBA-15 supported PtSn catalysts for propane dehydrogenation[J]. Applied Catalysis A: General, 2017, 533: 17-27.
88	BAI Linyang, ZHOU Yuming, ZHANG Yiwei, et al. Effect of magnesium addition to PtSnNa/ZSM-5 on the catalytic properties in the dehydrogenation of propane[J]. Industrial & Engineering Chemistry Research, 2009, 48(22): 9885-9891.
89	BAI Linyang, ZHOU Yuming, ZHANG Yiwei, et al. Influence of calcium addition on catalytic properties of PtSn/ZSM-5 catalyst for propane dehydrogenation[J]. Catalysis Letters, 2009, 129(3/4): 449-456.
90	ALY M, FORNERO E L, GALVITA V V, et al. Effect of boron promotion on coke formation during propane dehydrogenation over Pt/γ-Al₂O₃ catalysts[J]. ACS Catalysis, 2020, 10(9): 5208-5216.
91	ZHU Haibo, ANJUM D H, WANG Qingxiao, et al. Sn surface-enriched Pt-Sn bimetallic nanoparticles as a selective and stable catalyst for propane dehydrogenation[J]. Journal of Catalysis, 2014, 320: 52-62.
92	ZHANG Yiwei, ZHOU Yuming, HUANG Li, et al. Structure and catalytic properties of the Zn-modified ZSM-5 supported platinum catalyst for propane dehydrogenation[J]. Chemical Engineering Journal, 2015, 270: 352-361.
93	CAMACHO-BUNQUIN J, FERRANDON M S., SOHN H, et al. Atomically precise strategy to a PtZn alloy nano-cluster catalyst for the deep dehydrogenation of n-butane to 1,3-butadiene[J]. ACS Catalysis, 2018, 8(11): 10058-10063.
94	CYBULSKIS V J, BUKOWSKI B C, TSENG H T, et al. Zinc promotion of platinum for catalytic light alkane dehydrogenation: insights into geometric and electronic effects[J]. ACS Catalysis, 2017, 7(6): 4173-4181.
95	SUN Pingping, GEORGES S, WILLIAM C V. Novel Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation[J]. Journal of Catalysis, 2011, 282(1): 165-174.
96	LIU Xue, LANG Wanzhong, LONG Liuliu, et al. Improved catalytic performance in propane dehydrogenation of PtSn/γ-Al₂O₃ catalysts by doping indium[J]. Chemical Engineering Journal, 2014, 247: 183-192.
97	ZHANG Yiwei, ZHOU Yuming, SHI Junjun, et al. Propane dehydrogenation over PtSnNa/La-doped Al₂O₃ catalyst: effect of La content[J]. Fuel Processing Technology, 2013, 111(3): 94-104.
98	HAN Zhiping, LI Shuirong, JIANG Feng, et al. Propane dehydrogenation over Pt-Cu bimetallic catalysts: the nature of coke deposition and the role of copper[J]. Nanoscale, 2014, 6(17): 10000-10008.
99	FREY F E, HUPPKE W F. Equilibrium dehydrogenation of ethane, propane, and the butanes[J]. Industrial & Engineering Chemistry, 1933, 25(1): 54-59.
100	WECKHUYSEN B M, SCHOONHEYD T R A. Alkane dehydrogenation over supported chromium oxide catalysts[J]. Catalysis Today, 1967, 51(2): 223-232.
101	ADAMS C R. Catalytic oxidations with sulfur dioxide : Ⅰ. Exploratory studies[J]. Journal of Catalysis, 1968, 11(2): 96-112.
102	HARDCASTLE F D, WACHS I E. Raman spectroscopy of chromium oxide supported on Al₂O₃, TiO₂ and SiO₂: a comparative study[J]. Journal of Molecular Catalysis, 1988, 46(1/2/3): 173-186.
103	VUURMAN M A, WACHS I E. In situ Raman spectroscopy of alumina-supported metal oxide catalysts[J]. Journal of Physical Chemistry, 1992, 96(12): 5008-5016.
104	DINES T J, INGLIS S. Raman spectroscopic study of supported chromium() oxide catalysts[J]. Physical Chemistry Chemical Physics, 2003, 5(6): 1320-1328.
105	WECKHUYSEN B M, VERBERCKMOES A A, DEBAERE J, et al. In-situ UV-vis diffuse reflectance spectroscopy-on line activity measurements of supported chromium oxide catalysts: relating isobutane dehydrogenation activity with Cr-speciation via experimental design[J]. Journal of Molecular Catalysis A: Chemical, 2000, 151(1/2): 115-131.
106	PUURUNEN R L, WECKHUYSEN B M. Spectroscopic study on the irreversible deactivation of chromia/alumina dehydrogenation catalysts[J]. Journal of Catalysis, 2002, 210(2): 418-430.
107	AIRAKSINEN S M K, OUTI A, KRAUSE I, et al. Reduction of chromia/alumina catalyst monitored by DRIFTS-mass spectrometry and TPR-Raman spectroscopy[J]. Physical Chemistry Chemical Physics, 2003, 5(20): 4371-4377.
108	CONLEY M P, DELLEY M F, COMAS-VIVES A, et al. Heterolytic activation of C—H bonds on Cr^Ⅲ—O surface sites is a key step in catalytic polymerization of ethylene and dehydrogenation of propane[J]. Inorganic Chemistry, 2015, 54(11): 5065-5078.
109	XIE Yufei, LUO Ran, SUN Guodong, et al. Facilitating the reduction of V—O bonds on VO_x/ZrO₂ catalysts for non-oxidative propane dehydrogenation[J]. Chemical Science, 2020, 11: 3845-3851.
110	LIU Gang, ZHAO Zhijian, WU Tengfang, et al. On the nature of active sites of VO_x/Al₂O₃ catalysts for propane dehydrogenation[J]. ACS Catalysis, 2016, 6(8): 5207-5214.
111	GONG Jinlong, ZHAO Zhijian, WU Tengfang, et al. Hydroxyl-mediated non-oxidative propane dehydrogenation over VO_x/γ-Al₂O₃ catalysts with improved stability[J]. Angewandte Chemie: International Edition, 2018, 57(23): 6791-6795.
112	KITAGAWA Hiroyoshi, SENDODA Yoko, Yoshio ONO. Transformation of propane into aromatic hydrocarbons over ZSM-5 zeolites[J]. Journal of Catalysis, 1986, 101(1): 12-18.
113	CYBULSKIS V J, PRADHAN S U, JUAN J L Q, et al. The nature of the isolated gallium active center for propane dehydrogenation on Ga/SiO₂[J]. Catalysis Letters, 2017, 147(5): 1252-1262.
114	CHEN Miao, XU Jie, SU Fangzheng, et al. Dehydrogenation of propane over spinel-type gallia-alumina solid solution catalysts[J]. Journal of Catalysis, 2008, 256(2): 293-300.
115	WNAG Pengzhao, XU Zhikang, ZHU Haibo. Unmodified bulk alumina as an efficient catalyst for propane dehydrogenation[J]. Catalysis Science & Technology, 2020, 10: 3537-3541.
116	YUN Jangho, LOBO R F. Catalytic dehydrogenation of propane over iron-silicate zeolites[J]. Journal of Catalysis, 2014, 312(15): 263-270.
117	CHEN Chong, ZHANG Shoumin, WANG Zheng, et al. Ultrasmall Co confined in the silanols of dealuminated beta zeolite: a highly active and selective catalyst for direct dehydrogenation of propane to propylene[J]. Journal of Catalysis, 2020, 383: 77-87.
118	OTROSHCHENKO T, KONDRATENKO V A, RODEMERCK U, et al. ZrO₂-based unconventional catalysts for non-oxidative propane dehydrogenation: factors determining catalytic activity[J]. Journal of Catalysis, 2017, 348: 282-290.
119	WANG Guowei, ZHANG Huanling, ZHU Qingqing, et al. Sn-containing hexagonal mesoporous silica (HMS) for catalytic dehydrogenation of propane: an efficient strategy to enhance stability[J]. Journal of Catalysis, 2017, 351: 90-94.
120	WANG Haoren, HUANG Huiwen, BASHIR K, et al. Isolated Sn on mesoporous silica as a highly stable and selective catalyst for the Propane dehydrogenation[J]. Applied Catalysis A: General, 2020, 590: 117291-117299.
121	YUE Yuanyuan FU Jing, WANG Chuanming, et al. Propane dehydrogenation catalyzed by single Lewis acid site in Sn-Beta zeolite[J]. Journal of Catalysis, 2021, 395: 155-167.
122	HU Bo, SCHWEITZER N M, ZHANG Guanghui, et al. Isolated FeⅡ on silica as a selective propane dehydrogenation catalyst[J]. ACS Catalysis, 2015, 5(6): 3494-3503.
123	SCHWEITZER N M, HU Bo, DAS U. Propylene hydrogenation and propane dehydrogenation by a single-site Zn²⁺ on silica catalyst[J]. ACS Catalysis, 2014, 4(4): 1091-1098.
124	HU Bo, GETSOIAN A B, SCHWEITZER N M, et al. Selective propane dehydrogenation with single-site Co^Ⅱ on SiO₂ by a non-redox mechanism[J]. Journal of Catalysis, 2015, 322: 24-37.
125	DAI Yihu. γ-Al₂O₃ sheet-stabilized isolate Co²⁺ for catalytic propane dehydrogenation[J]. Journal of Catalysis, 2019, 381: 482-492.
126	SHAO Chuntao, LANG Wanzhong, YAN Xi, et al. Catalytic performance of gallium oxide based-catalysts for the propane dehydrogenation reaction: effects of support and loading amount[J]. RSC Advances, 2017, 7(8): 4710-4723.
127	BAI Peng, MA Zhipeng, LI Tingting, et al. Relationship between surface chemistry and catalytic performance of mesoporous γ-Al₂O₃ supported VO_x catalyst in catalytic dehydrogenation of propane[J]. ACS Applied Materials & Interfaces, 2016, 8(39): 25979-25990.
128	LANG Wanzhong, HU Changlong, CHU Lianfeng, et al. Hydrothermally prepared chromia-alumina (xCr/Al₂O₃) catalysts with hierarchical structure for propane dehydrogenation[J]. RSC Advances, 2014, 4(70): 37107-37113.
129	HU Ping, LANG Wanzhong, YAN Xi, et al. Influence of gelation and calcination temperature on the structure-performance of porous VO_x-SiO₂ solids in non-oxidative propane dehydrogenation[J]. Journal of Catalysis, 2018, 358: 108-117.
130	SEARLES K, GEORGES S, SAFONOVA O, et al. Silica-supported isolated gallium sites as highly active, selective and stable propane dehydrogenation catalysts[J]. Chemical Science, 2017, 8(4): 2661-2666.
131	HU Bo, KIM W G, SULMONETTI T P, et al. Mesoporous CoAl₂O₄ spinel catalyst for non-oxidative propane dehydrogenation[J]. Chemcatchem, 2017, 9(17): 3330-3337.
132	WU Tengfang, LIU Gang, ZENG Liang, et al. Structure and catalytic consequence of Mg-modified VOx/Al₂O₃ catalysts for propane dehydrogenation[J]. AIChE Journal, 2017, 63(11): 4911-4919.
133	KIM T H, GIM M Y, SONG J H, et al. Deactivation behavior of CrO_y/Al₂O₃-ZrO₂ catalysts in the dehydrogenation of propane to propylene by lattice oxygen[J]. Catalysis Communications, 2017, 97(5): 37-41.
134	WANG Guowei, SHAN Honghong, GAO Yanan, et al. Effect of sulfate addition on the performance of Co/Al₂O₃ catalysts in catalytic dehydrogenation of propane[J]. Catalysis Communications, 2015, 60: 42-45.
135	SOKOLOV S, STOYANOVA M, RODEMERCK U, et al. Effect of support on selectivity and on-stream stability of surface VO_x species in non-oxidative propane dehydrogenation[J]. Catalysis Science & Technology, 2014, 4(5): 1323-1332.
136	KUMAR M S, HAMMER N, CHEN D. The nature of active chromium species in Cr-catalysts for dehydrogenation of propane: new insights by a comprehensive spectroscopic study[J]. Journal of Catalysis, 2009, 261(1): 116-128.
137	PIOVANO A, GROPPO E, BRAGLIA L, et al. Insights into Cr/SiO₂ catalysts during dehydrogenation of propane: an operando XAS investigation[J]. Catalysis Science & Technology, 2017, 7(8): 1690-1700.
138	REN Yingjie, WANG Jie, HUA Weiming, et al. Ga₂O₃/HZSM-48 for dehydrogenation of propane: effect of acidity and pore geometry of support[J]. Journal of Industrial & Engineering Chemistry, 2012, 18(2): 731-736.
139	GONG Ting, QIN Lijun, LU Jian, et al. ZnO modified ZSM-5 and Y zeolites fabricated by atomic layer deposition for propane conversion[J]. Physical Chemistry Chemical Physics, 2016, 18(1): 601-614.
140	CHEN Chong, HU Zhongpan, REN Jintao, et al. ZnO nanoclusters supported on dealuminated zeolite β as a novel catalyst for direct dehydrogenation of propane to propylene[J]. ChemCatChem, 2019, 11(2): 868-877.
141	AUROUX A, MONACI R, ROMBI E, et al. Acid sites investigation of simple and mixed oxides by TPD and microcalorimetric techniques[J]. Thermochimica Acta, 2001, 379(1/2): 227-231.
142	ADAM W, ANNA R, BARBARA M, et al. High-performance Cr-Zr-O and Cr-Zr-K-O catalysts prepared by nanocasting for dehydrogenation of propane to propene[J]. Catalysis Science & Technology, 2017, 7(24): 6059-6068.
143	ROMBI E, GAZZOLI D, CUTRUFELLO M G, et al. Modifications induced by potassium addition on chromia/alumina catalysts and their influence on the catalytic activity for the oxidative dehydrogenation of propane[J]. Applied Surface Science, 2010, 256(17): 5576-5580.
144	CABRERA F, ARDISSONE D, GORRIZ O F. Dehydrogenation of propane on chromia/alumina catalysts promoted by tin[J]. Catalysis Today, 2008, 133: 800-804.
145	LIU Lei, DENG Qingfang, YUAN Zhongyong. Ordered mesoporous carbon catalyst for dehydrogenation of propane to propylene[J]. Catalysis Communications, 2011, 47(29): 8334-8336.
146	LIU Lei, DENG Qingfeng, YUAN Zhongyong. HNO₃-activated mesoporous carbon catalyst for direct dehydrogenation of propane to propylene[J]. Catalysis Communications, 2011, 16(1): 81-85.
147	LI Lina, ZHU Wenliang, LIU Yong, et al. Phosphorous-modified ordered mesoporous carbon for catalytic dehydrogenation of propane to propylene[J]. RSC Advances, 2015, 5(69): 56304-56310.
148	WANG Rui, SUN Xiaoyan, ZHANG Bingsen, et al. Hybrid nanocarbon as a catalyst for direct dehydrogenation of propane: formation of an active and selective core-shell sp²/sp³ nanocomposite structure[J]. Chemistry-A European Journal, 2014, 20(21): 6324-6331.
149	LIU Lei, DENG Qingfang, REN Tiezhen, et al. Synthesis of ordered mesoporous carbon materials and their catalytic performance in dehydrogenation of propane to propylene[J]. Catalysis Today, 2012, 186(1): 35-41.
150	HU Zhongpan, REN Jintao, YANG Dandan, et al. Mesoporous carbons as metal-free catalysts for propane dehydrogenation: effect of the pore structure and surface property[J]. Chinese Journal of Catalysis, 2019, 40(9): 1385-1394.
151	HU Zhongpan, CHEN Chong, REN Jintao, et al. Direct dehydrogenation of propane to propylene on surface-oxidized multiwall carbon nanotubes[J]. Applied Catalysis A: General, 2018, 559: 85-93.
152	HU Zhongpan, ZHANG Lingfeng, WANG Zheng, et al. Bean dregs‐derived hierarchical porous carbons as metal‐free catalysts for efficient dehydrogenation of propane to propylene[J]. Journal of Chemical Technology & Biotechnology, 2018, 93(12): 3410-3417.
153	PAN Shangfa, YIN Jianglong, ZHU Xuelian, et al. P-modified microporous carbon nanospheres for direct propane dehydrogenation reactions[J]. Carbon, 2019, 152: 855-864.

催化剂	反应温度 /℃	反应原料比	总流速 /mL·min^-1	质量空速WHSV	丙烷始-末转化率/%	丙烯始-末选择性/%	反应时间 TOS/h	失活速率K_d/h^-1	制备方法	参考文献
Pt⁰Ga^δ⁺/SiO₂	550	C₃H₈/Ar=1∶4	50	98.3	31.9~18.2	约99	20	0.04	表面化学法	[24]
PtSn/TS-1	590	C₃H₈∶H₂∶N₂=1∶1∶4	—	3	53~47.5	92.5~93	7	0.03	水热+浸渍法	[25]
Pt/Al₂O₃	520	C₃H₈/H₂/N₂=4∶4∶17	50	4.0	5.8~2.6	70~68	12	0.070	浸渍法	[41]
PtCu/Al₂O₃	520	C₃H₈/H₂/N₂=4∶4∶17	50	4.0	13.1~12.4	87~89	120	0.0005	浸渍法	[41]
PtGa-Pb/SiO₂	600	C₃H₈/H₂/He=5∶3.9∶40	—	30.6	27~31	>99.6	50	0.0038	共沉淀法	[42]
PtSn/Mg(Al)O-sv	550	C₃H₈=20	—	1.13	27.7~27.8	>96.6	5	0.001	浸渍法	[44]
PtIn/Mg(Al)O-4	620	C₃H₈/H₂/Ar=8∶7∶35	—	3.3	45~61.3	95.3~96.2	12	—	浸渍法	[45]
PtSn₃/Al₂O₃	550	C₃H₈/H₂/N₂=1∶1∶8	80	11.8	40~38	>99.5	72	0.0012	表面化学法	[46]
Pt⁰Zn^δ⁺/SiO₂	550	C₃H₈/Ar=1∶4	50	32	35.3~26.6	97.6~96.3	30	0.014	表面化学法	[47]
Pt⁰Zn^δ⁺/SiO₂	550	C₃H₈/Ar=1∶4	50	75	30.2~16.2	98.1~95	30	0.027	表面化学法	[47]
PtSn/Al₂O₃片	590	C₃H₈/H₂/N₂=1∶1.25∶8	—	9.4	48.7~44.6	约99.1	24	0.007	浸渍法	[56]
Pt-Sn/SiO₂(1073K H₂)	500	C₃H₈/N₂=4∶1	100	47	27~12	90.9~99.5	3	0.33	浸渍法	[58]
Pt/Mg(In)(Al)O	550	C₃H₈=20	—	1.57	24.2~17.5	>98.2	5	0.081	共沉淀法	[59]
Pt/Mg(Sn)(Al)O	550	C₃H₈/H₂/N₂=1∶0.5∶2	—	14	29.4~27.8	93.7~99.2	240	0.0067	浸渍法	[62]
Pt/Mg(Sn)(Al)O	600	C₃H₈/H₂/N₂=1∶0.5∶2	—	14	48.3~43.0	86.4~98.1	48	0.11	浸渍法	[62]
Pt/Sn₂-Beta	580	C₃H₈/H₂/N₂=1∶1∶8	60	141	50~44	95~98	48	0.006	表面化学法	[63]
PtZn_x@S-1-H	550	C₃H₈/N₂=10∶30	40	3.6	47.4~40.4	93.2~99.2	217	0.001	原位合成法	[64]
PtZn@S-1	550	C₃H₈/N₂=11∶19	30	6.5	45.3~41.5	>99	60	0.002	原位合成法	[65]
K-PtSn@MFI	650	C₃H₈/N₂=5∶16	21	29.5	54~37	>99	70	0.099	原位合成法	[66]
K-PtSn@MFI-(600H₂-22h)	600	C₃H₈/N₂=5∶16.5	21.5	29.5	38.7~31.9	>97	25	0.012	原位合成法	[67]

催化剂	反应温度 /℃	反应原料比	总流速 /mL·min^-1	质量空速WHSV	丙烷始-末转化率/%	丙烯始-末选择性/%	反应时间 TOS/h	失活速率K_d/h^-1	制备方法	参考文献
Pt⁰Ga^δ⁺/SiO₂	550	C₃H₈/Ar=1∶4	50	98.3	31.9~18.2	约99	20	0.04	表面化学法	[24]
PtSn/TS-1	590	C₃H₈∶H₂∶N₂=1∶1∶4	—	3	53~47.5	92.5~93	7	0.03	水热+浸渍法	[25]
Pt/Al₂O₃	520	C₃H₈/H₂/N₂=4∶4∶17	50	4.0	5.8~2.6	70~68	12	0.070	浸渍法	[41]
PtCu/Al₂O₃	520	C₃H₈/H₂/N₂=4∶4∶17	50	4.0	13.1~12.4	87~89	120	0.0005	浸渍法	[41]
PtGa-Pb/SiO₂	600	C₃H₈/H₂/He=5∶3.9∶40	—	30.6	27~31	>99.6	50	0.0038	共沉淀法	[42]
PtSn/Mg(Al)O-sv	550	C₃H₈=20	—	1.13	27.7~27.8	>96.6	5	0.001	浸渍法	[44]
PtIn/Mg(Al)O-4	620	C₃H₈/H₂/Ar=8∶7∶35	—	3.3	45~61.3	95.3~96.2	12	—	浸渍法	[45]
PtSn₃/Al₂O₃	550	C₃H₈/H₂/N₂=1∶1∶8	80	11.8	40~38	>99.5	72	0.0012	表面化学法	[46]
Pt⁰Zn^δ⁺/SiO₂	550	C₃H₈/Ar=1∶4	50	32	35.3~26.6	97.6~96.3	30	0.014	表面化学法	[47]
Pt⁰Zn^δ⁺/SiO₂	550	C₃H₈/Ar=1∶4	50	75	30.2~16.2	98.1~95	30	0.027	表面化学法	[47]
PtSn/Al₂O₃片	590	C₃H₈/H₂/N₂=1∶1.25∶8	—	9.4	48.7~44.6	约99.1	24	0.007	浸渍法	[56]
Pt-Sn/SiO₂(1073K H₂)	500	C₃H₈/N₂=4∶1	100	47	27~12	90.9~99.5	3	0.33	浸渍法	[58]
Pt/Mg(In)(Al)O	550	C₃H₈=20	—	1.57	24.2~17.5	>98.2	5	0.081	共沉淀法	[59]
Pt/Mg(Sn)(Al)O	550	C₃H₈/H₂/N₂=1∶0.5∶2	—	14	29.4~27.8	93.7~99.2	240	0.0067	浸渍法	[62]
Pt/Mg(Sn)(Al)O	600	C₃H₈/H₂/N₂=1∶0.5∶2	—	14	48.3~43.0	86.4~98.1	48	0.11	浸渍法	[62]
Pt/Sn₂-Beta	580	C₃H₈/H₂/N₂=1∶1∶8	60	141	50~44	95~98	48	0.006	表面化学法	[63]
PtZn_x@S-1-H	550	C₃H₈/N₂=10∶30	40	3.6	47.4~40.4	93.2~99.2	217	0.001	原位合成法	[64]
PtZn@S-1	550	C₃H₈/N₂=11∶19	30	6.5	45.3~41.5	>99	60	0.002	原位合成法	[65]
K-PtSn@MFI	650	C₃H₈/N₂=5∶16	21	29.5	54~37	>99	70	0.099	原位合成法	[66]
K-PtSn@MFI-(600H₂-22h)	600	C₃H₈/N₂=5∶16.5	21.5	29.5	38.7~31.9	>97	25	0.012	原位合成法	[67]

催化剂	反应温度 /℃	反应原料比	总流速 /mL·min^-1	质量空速WHSV	丙烷始-末转化率/%	丙烯始-末选择性/%	反应时间TOS/h	失活速率K_d /h^-1	制备方法	参考文献
VO_x/ZrO₂	550	C₃H₈/H₂/N₂=7∶36∶7	50	2.1	25~10	85~88	2	0.549	浸渍法	[109]
VO_x/Al₂O₃	600	C₃H₈/H₂/N₂=7∶7∶11	25	3	32~15	约94	4	0.245	浸渍法	[110]
VO_x/Al₂O₃	600	C₃H₈/N₂=7∶18	25	8	25~15	70~75	约1.5	0.423	浸渍法	[111]
Ga₈Al₂O₁₅	500	C₃H₈/N₂=1∶39	—	—	49.7~33.1	91.7~98	8	0.086	共沉淀法	[114]
[Fe]ZSM-5(MFI)	530	—	—	—	约7.2	约78	3	—	原位合成法	[116]
Co/Si-Beta	600	C₃H₈/N₂=5∶95	20	0.4	85~40	1~97	6	0.344	浸渍法	[117]
Sn-HMS	600	C₃H₈=5	—	0.4	约40	约90	170	—	水热法	[119]
SnO₂/SiO₂(ws)	600	C₃H₈=5	—	0.65	约30	约85	5	—	浸渍法	[120]
Fe_Ⅱ/SiO₂	650	C₃H₈/Ar=3∶97	55	0.38	4.9~6.3	>99	18	—	表面化学法	[122]
Co-Al₂O₃-HT	590	C₃H₈/H₂/N₂=1∶0.8∶3.2	—	2.9	23~22	约97	5	0.011	水热法	[125]
VO_x/meso-Al₂O₃	510	C₃H₈/N₂=4∶1	30	2.8	70~30	约85	10	0.169	浸渍法	[127]
GaO_x/SiO₂	580	C₃H₈/N₂=1∶10	16.5	0.59	65~45	约90	6	0.136	原位合成法	[130]
ZnO/Beta	600	C₃H₈/N₂=5∶95	20	0.4	52~38	约93	6	0.095	离子交换法	[140]

催化剂	反应温度 /℃	反应原料比	总流速 /mL·min^-1	质量空速WHSV	丙烷始-末转化率/%	丙烯始-末选择性/%	反应时间TOS/h	失活速率K_d /h^-1	制备方法	参考文献
VO_x/ZrO₂	550	C₃H₈/H₂/N₂=7∶36∶7	50	2.1	25~10	85~88	2	0.549	浸渍法	[109]
VO_x/Al₂O₃	600	C₃H₈/H₂/N₂=7∶7∶11	25	3	32~15	约94	4	0.245	浸渍法	[110]
VO_x/Al₂O₃	600	C₃H₈/N₂=7∶18	25	8	25~15	70~75	约1.5	0.423	浸渍法	[111]
Ga₈Al₂O₁₅	500	C₃H₈/N₂=1∶39	—	—	49.7~33.1	91.7~98	8	0.086	共沉淀法	[114]
[Fe]ZSM-5(MFI)	530	—	—	—	约7.2	约78	3	—	原位合成法	[116]
Co/Si-Beta	600	C₃H₈/N₂=5∶95	20	0.4	85~40	1~97	6	0.344	浸渍法	[117]
Sn-HMS	600	C₃H₈=5	—	0.4	约40	约90	170	—	水热法	[119]
SnO₂/SiO₂(ws)	600	C₃H₈=5	—	0.65	约30	约85	5	—	浸渍法	[120]
Fe_Ⅱ/SiO₂	650	C₃H₈/Ar=3∶97	55	0.38	4.9~6.3	>99	18	—	表面化学法	[122]
Co-Al₂O₃-HT	590	C₃H₈/H₂/N₂=1∶0.8∶3.2	—	2.9	23~22	约97	5	0.011	水热法	[125]
VO_x/meso-Al₂O₃	510	C₃H₈/N₂=4∶1	30	2.8	70~30	约85	10	0.169	浸渍法	[127]
GaO_x/SiO₂	580	C₃H₈/N₂=1∶10	16.5	0.59	65~45	约90	6	0.136	原位合成法	[130]
ZnO/Beta	600	C₃H₈/N₂=5∶95	20	0.4	52~38	约93	6	0.095	离子交换法	[140]

催化剂	反应温度 /℃	反应原料比	总流速 /mL·min^-1	质量空速WHSV	丙烷始-末转化率 /%	丙烯始-末选择性 /%	反应时间TOS/h	失活速率K_d /h^-1	制备方法	参考文献
OMC-1	600	C₃H₈/N₂=1∶19	40	0.59	69.3～44.5	62.2～85.1	100	0.01	有机自组装法	[145]
OMC-2	600	C₃H₈/N₂=1∶19	40	0.59	65.7～39.3	70.6～88.6	100	0.01	有机自组装法	[145]
CMK-3	550	C₃H₈/N₂=1∶19	40	0.59	54.3～49.8	27.6～68.0	100	0.018	硬膜版法	[145]
MCO	600	C₃H₈/N₂=1∶19	40	0.59	32.9～21.2	66.3～86.6	50	0.012	酸洗法	[146]
P/CMK-3	600	C₃H₈/N₂=1∶19	20	0.59	约28	约88	24	—	杂原子掺杂法	[147]
ND-1000	550	C₃H₈/He=1∶49	15	—	约10.6	约90	8	—	高温退火法	[148]
HOMC	600	C₃H₈/N₂=1∶19	40	0.59	20.1～10.3	66.1～78.5	50	0.016	水热法	[149]
COMC	600	C₃H₈/N₂=1∶19	40	0.59	22.6～12.1	89～95.1	50	0.015	酸洗法	[149]
MC-2-600	600	C₃H₈/N₂=1∶19	20	0.59	37～31	85～89	10	0.027	水热法	[150]
so-MWCNTs	600	C₃H₈/N₂=1∶19	20	0.59	11.2～5.8	92.1～87.9	4	0.179	酸洗+热处理法	[151]
BDAC-700	600	C₃H₈/N₂=1∶19	20	0.59	41.3～24.7	88.6～93.5	50	0.015	碱洗法	[152]
BDAC-800	600	C₃H₈/N₂=1∶19	20	0.59	42.5～29	89.2～91.3	50	0.012	碱洗法	[152]
PT-MCNs	600	C₃H₈/N₂=1∶19	20	0.59	32.3～18	约90	10	0.077	水热法	[153]
PMCNs	600	C₃H₈/N₂=1∶19	20	0.59	26～16	约88	10	0.061	水热法	[153]