RESEARCH PROGRESS IN OXIDATIVE DEHYDROGENATION OF PROPANE TO PROPYLENE

Abstract

Abstract: Propane dehydrogenation is a key industrial process for propane utilization and propylene production, including direct dehydrogenation of propane (DHP) and oxidative dehydrogenation of propane (ODHP). Although DHP has been industrialized, it still faces issues such as thermodynamic equilibrium limitations, high energy consumption, and coke deposition on catalyst. ODHP, by contrast, can break through thermodynamic limitations and enable higher single-pass propane conversion, demonstrating good application prospects. Herein, the recent progress in two types of ODHP catalysts was comprehensively reviewed: metal catalysts (vanadium based, Mo/Ni based, cobalt based) and non-metal catalysts (boron based and carbon based).The reaction mechanisms on metal and non-metal catalysts, and the latest achievements in reaction engineering and process optimization were explored, which can made up for the shortcomings of traditional ODHP, such as excessive oxidation leading to low selectivity and yield of propylene. In future, we should focus on three key directions: the development of efficient catalysts, clarification of reaction mechanisms, and optimization of oxidant systems, to promote the industrialization of ODHP technology.

Key words: propane, oxidative dehydrogenation, propylene, catalyst, mechanism

References

[1] Sattler J J, Ruiz-Martinez J, Santillan-Jimenez E, et al. Catalytic dehydrogenation of light alkanes on metals and metal oxides[J]. Chem Rev, 2014, 114 (20): 10613-10653. [2] Chernyak S A, Corda M, Dath J-P, et al. Light olefin synthesis from a diversity of renewable and fossil feedstocks: state-of the-art and outlook[J]. Chemical Society Reviews, 2022, 51 (18): 7994-8044. [3] Monai M, Gambino M, Wannakao S, et al. Propane to olefins tandem catalysis: a selective route towards light olefins production[J]. Chem Soc Rev, 2021, 50 (20): 11503-11529. [4] Zheng Y, Zhang X, Li J, et al. CO2-assisted oxidation dehydrogenation of light alkanes over metal-based heterogeneous catalysts[J]. Chinese Journal of Catalysis, 2024, 65: 40-69. [5] Dai Y, Gao X, Wang Q, et al. Recent progress in heterogeneous metal and metal oxide catalysts for direct dehydrogenation of ethane and propane[J]. Chemical Society Reviews, 2021, 50 (9): 5590-5630. [6] Song S, Sun Y, Yang K, et al. Recent progress in metal-molecular sieve catalysts for propane dehydrogenation[J]. ACS Catalysis, 2023, 13 (9): 6044-6067. [7] Chen S, Chang X, Sun G, et al. Propane dehydrogenation: catalyst development, new chemistry, and emerging technologies[J]. Chemical Society Reviews, 2021, 50 (5): 3315-3354. [8] Gao X, Cai C, Tian S, et al. Performance descriptor of subsurface metal-promoted boron catalysts for low-temperature propane oxidative dehydrogenation to propylene[J]. Journal of the American Chemistry Society, 2024, 146 (51): 35165-35174. [9] Li P, Zhang X, Wang J, et al. Engineering O-O species in boron nitrous nanotubes increases olefins for propane oxidative dehydrogenation[J]. Journal of the American Chemistry Society, 2022, 144 (13): 5930-5936. [10] Chu C, Chen B, He Y, et al. CO2-assisted dehydrogenation of propane by atomically dispersed Pt on MXenes[J]. ACS Catalysis, 2024, 14 (13): 9662-9677. [11] Wang J, Zhu M-L, Song Y-H, et al. Molecular-level investigation on supported CrOx catalyst for oxidative dehydrogenation of propane with carbon dioxide[J]. Journal of Catalysis, 2022, 409: 87-97. [12] Wang J, Song Y-H, Liu Z-T, et al. Active and selective nature of supported CrOx for the oxidative dehydrogenation of propane with carbon dioxide[J]. Applied Catalysis B: Environmental, 2021, 297, 120400. [13] Kondratenko E, Cherian M, Baerns M, et al. Oxidative dehydrogenation of propane over V/MCM-41 catalysts: comparison of O2 and N2O as oxidants[J]. Journal of Catalysis, 2005, 234 (1): 131-142. [14] 苏聪龙, 侯朝鹏, 李红伟. 丙烷脱氢制丙烯催化剂研究进展[J]. 低碳化学与化工, 2025. [15] 孔维杰, 杨春亮, 卜婷婷, et al. 碳基硼基催化体系丙烷氧化脱氢催化剂的研究进展[J]. 化工进展, 2021, 40 (S1): 223-230. [16] Liu Y, Feng W, Li T, et al. Structure and catalytic properties of vanadium oxide supported on mesocellulous silica foams (MCF) for the oxidative dehydrogenation of propane to propylene[J]. Journal of Catalysis, 2006, 239 (1): 125-136. [17] Mazzocchia C, Aboumrad C, Diagne C, et al. On the NiMoO4 oxidative dehydrogenation of propane to propene: some physical correlations with the catalytic activity[J]. Catalysis Letters, 1991, 10: 181-191. [18] Huang M-X, Wu X, Yi X-D, et al. Highly dispersed CoOx in layered double oxides for oxidative dehydrogenation of propane: guest–host interactions[J]. RSC Advances, 2017, 7 (24): 14846-14856. [19] Frank B, Zhang J, Blume R, et al. Heteroatoms increase the selectivity in oxidative dehydrogenation reactions on nanocarbons[J]. Angewandte Chemie International Edition, 2009, 48 (37): 6913-6917. [20] Sun X, Ding Y, Zhang B, et al. New insights into the oxidative dehydrogenation of propane on borate-modified nanodiamond[J]. Chemical Communications, 2015, 51 (44): 9145-9148. [21] Zhu Y, Chen R, Yang Y, et al. Low temperature catalytic activity of molybdenum promoted two-dimensional boron nitride in propane oxidative dehydrogenation reaction[J]. Chemical Engineering Journal, 2024, 490, 151364. [22] Gao X, Zhu L, Yang F, et al. Subsurface nickel boosts the low-temperature performance of a boron oxide overlayer in propane oxidative dehydrogenation[J]. Nature Communications, 2023, 14 (1): 1478. [23] Grant J T, Carrero C A, Goeltl F, et al. Selective oxidative dehydrogenation of propane to propene using boron nitride catalysts[J]. Science, 2016, 354 (6319): 1570-1573. [24] Liu Q, Li J, Zhao Z, et al. Design, synthesis and catalytic performance of vanadium-incorporated mesoporous silica KIT-6 catalysts for the oxidative dehydrogenation of propane to propylene[J]. Catalysis Science & Technology, 2016, 6 (15): 5927-5941. [25] Guo X-P, Wang X-X, Lu H-Q, et al. Mesoporous sol–gel silica supported vanadium oxide as effective catalysts in oxidative dehydrogenation of propane to propylene[J]. RSC Advances, 2023, 13 (33): 22815-22823. [26] Mitran G, Ahmed R, Iro E, et al. Propane oxidative dehydrogenation over VOx/SBA-15 catalysts[J]. Catalysis Today, 2018, 306: 260-267. [27] Balogun M L, Adamu S, Ba-Shammakh M S, et al. Promotional effects of CO2 on the oxidative dehydrogenation of propane over mesoporous VOx/γAl2O3 catalysts[J]. Journal of Industrial and Engineering Chemistry, 2021, 96: 82-97. [28] Gambo Y, Adamu S, Lucky R A, et al. Decoupling reaction network and designing robust VOx/Al2O3 catalyst with suitable site diversity for promoting CO2-mediated oxidative dehydrogenation of propane[J]. Chemical Engineering Journal, 2024, 479: 147458. [29] Yan X, Xu X, Sun Y, et al. Mo–V–Al–K–O catalyst for low-temperature oxidative dehydrogenation of propane[J]. Molecular Catalysis, 2024, 569: 114640. [30] Zhang S, Liu H. Insights into the structural requirements for oxidative dehydrogenation of propane on crystalline Mg-V-O catalysts[J]. Applied Catalysis A: General, 2018, 568: 1-10. [31] Watson R B, Ozkan U S. K/Mo catalysts supported over sol–gel silica–titania mixed oxides in the oxidative dehydrogenation of propane[J]. Journal of Catalysis, 2000, 191 (1): 12-29. [32] Putra M D, Al-Zahrani S M, Abasaeed A E. Oxidative dehydrogenation of propane to propylene over Al2O3-supported Sr–V–Mo catalysts[J]. Catalysis Communications, 2011, 14 (1): 107-110. [33] Stern D L, Grasselli R K. Propane oxydehydrogenation over molybdate-based catalysts[J]. Journal of Catalysis, 1997, 167 (2): 550-559. [34] Farin B, Devillers M, Gaigneaux E M. Nanostructured hybrid materials as precursors of mesoporous NiMo-based catalysts for the propane oxidative dehydrogenation[J]. Microporous and Mesoporous Materials, 2017, 242: 200-207. [35] Li J-H, Wang C-C, Huang C-J, et al. Mesoporous nickel oxides as effective catalysts for oxidative dehydrogenation of propane to propene[J]. Applied Catalysis A: General, 2010, 382 (1): 99-105. [36] Zhang Q, Cao C, Xu T, et al. NiO–polyoxometalate nanocomposites as efficient catalysts for the oxidative dehydrogenation of propane and isobutane[J]. Chemical Communications, 2009, 2376-2378. [37] Baoyi S, Aiju X, Jiang W. The impact of preparation methods on the structure and catalytic performance of NiMoO4 for oxidative dehydrogenation of propane[J]. Integrated Ferroelectrics, 2016, 171 (1): 16-22. [38] 宋卫余, 杨坤, 赖自强, 等. Mo基、W基催化剂的制备及其丙烷脱氢性能研究[J]. 现代化工, 2022, 42 (7): 120-129. [39] Davies T E, García T, Solsona B, et al. Nanocrystalline cobalt oxide: a catalyst for selective alkane oxidation under ambient conditions[J]. Chemical Communications, 2006, 3417-3419. [40] Li Z, Peters A W, Bernales V, et al. Metal–organic framework supported cobalt catalysts for the oxidative dehydrogenation of propane at low temperature[J]. ACS Central Science, 2016, 3 (1): 31-38. [41] Michorczyk P, Ku?trowski P, Niebrzydowska P, et al. Catalytic performance of sucrose-derived CMK-3 in oxidative dehydrogenation of propane to propene[J]. Applied Catalysis A: General, 2012, 445-446: 321-328. [42] Goyal R, Sarkar B, Bag A, et al. Single-step synthesis of hierarchical BxCN: a metal-free catalyst for low-temperature oxidative dehydrogenation of propane[J]. Journal of Materials Chemistry A, 2016, 4 (47): 18559-18569. [43] 杜凯敏, 范杰. 丙烷氧化脱氢制丙烯研究进展[J]. 化工进展, 2019, 38 (6): 2697-2706. [44] Schumacher L, Hofmann K, Hess C. Elucidating the reaction mechanism and deactivation of CO2-assisted propane oxidative dehydrogenation over VOx/TiO2 catalysts: A multiple operando spectroscopic study[J]. ACS Catalysis, 2024, 15 (2): 939-955. [45] Blasco T, Galli A, Nieto J M L, et al. Oxidative dehydrogenation of ethane and n-butane on VOx/Al2O3 catalysts[J]. Journal of Catalysis, 1997, 169 (1): 203-211. [46] Dinse A, Frank B, Hess C, et al. Oxidative dehydrogenation of propane over low-loaded vanadia catalysts: Impact of the support material on kinetics and selectivity[J]. Journal of Molecular Catalysis A: Chemical, 2008, 289 (1-2): 28-37. [47] Xingtao G, P. R, Qin X, et al. Effect of coexistence of magnesium vanadate phases in the selective oxidation of propane to propene[J]. Journal of Catalysis, 1994, 148 (1): 56-67. [48] Liu G, Zhao Z-J, Wu T, et al. Nature of the active sites of VOx/Al2O3 catalysts for propane dehydrogenation[J]. ACS Catalysis, 2016, 6 (8): 5207-5214. [49] Madeira L M, Portela M F, Mazzocchia C. Nickel molybdate catalysts and their use in the selective oxidation of hydrocarbons[J]. Catalysis Reviews, 2004, 46 (1): 53-110. [50] Dias C R, Zavoianu R, Portela M F. Isobutane oxydehydrogenation on SiO2-supported nickel molybdate catalysts: Effect of the active phase loading[J]. Catalysis Communications, 2002, 3 (2): 85-90. [51] Z?voianu R, Dias C R, Portela M F. Stabilisation of β-NiMoO4 in TiO2-supported catalysts[J]. Catalysis Communications, 2001, 2 (1): 37-42. [52] Frank B, Morassutto M, Schom?cker R, et al. Oxidative dehydrogenation of ethane over multiwalled carbon nanotubes[J]. ChemCatChem, 2010, 2 (6): 644-648. [53] 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. [54] Zhang X, Ren B, Yang Z, et al. Transforming boron carbon nitride: A carbon-to-oxygen switch to boost propane oxidative dehydrogenation[J]. ACS Catalysis, 2025, 15: 9290-9300. [55] Tian J, Hu K, Fang L, et al. Optimizing boron oxide-support interactions for enhanced catalytic stability in propane oxidative dehydrogenation[J]. Chemical Engineering Journal, 2025, 513. [56] 陈淑. 过渡金属氧化物纳米介孔材料在丙烷选择性氧化脱氢制丙烯反应中的研究[D]. 杭州：浙江大学, 2015. [57] Xing F, Ma J, Shimizu K I, et al. High-entropy intermetallics on ceria as efficient catalysts for the oxidative dehydrogenation of propane using CO2[J]. Nature Communications, 2022, 13 (1): 5065. [58] Chen S, Pei C, Fu D, et al. Chemical looping for upgrading light alkanes: oxygen carriers, reaction kinetics, and reactor design[J]. Science China Chemistry, 2024, 68: 2343-2371. [59] 孙嘉辰, 裴春雷, 陈赛, et al. 化学链低碳烷烃氧化脱氢技术进展[J]. 化工学报, 2023, 74 (1): 205-223. [60] Wang X, Pei C, Zhao Z-J, et al. Coupling acid catalysis and selective oxidation over MoO3-Fe2O3 for chemical looping oxidative dehydrogenation of propane[J]. Nature Communications, 2023, 14 (1): 1-12. [61] Kotanjac ? S, van Sint Annaland M, Kuipers J A M. Demonstration of a packed bed membrane reactor for the oxidative dehydrogenation of propane[J]. Chemical Engineering Science, 2010, 65 (22): 6029-6035. [62] Jin Y, Meng X, Bo M, et al. Parametric modeling study of oxidative dehydrogenation of propane in La0.6Sr0.4Co0.2Fe0.8O3-δ hollow fiber membrane reactor[J]. Catalysis Today, 2019, 330: 135-141.