A review on kinetics and reactor concept design of propylene epoxidation using H2 and O2

doi:10.11949/0438-1157.20201247

Abstract

Abstract:

Propylene oxide (PO) ranks among the 35 chemicals with the highest production capacity in the world, and is the second largest propylene derivative after polypropylene. It is mainly used to produce polyether polyols, polyurethanes, etc. Compared with traditional PO production technology such as the chlorohydrin, co-oxidation and HPPO method, using H₂ and O₂ to oxidize propylene for PO production (HOPO) has the advantages of environmental friendliness, simple process and good economic efficiency. It is the ideal technology for PO production. In this review, the reaction kinetics of the propylene epoxidation using H₂ and O₂ reaction are highlighted, including the main and side reaction kinetics and deactivation models. The reactor concept design based on safe operation is summarized. The existing problems of HOPO reaction are analyzed and possible research focus is remarked from the aspects of side reaction pathways, deactivation kinetics and kinetics on catalyst pellet.

Key words: catalysis, propylene oxide, kinetics, propylene epoxidation, reactor

摘要：

环氧丙烷（PO）在全球产能最高的35种化学品中，是仅次于聚丙烯的第二大丙烯衍生物，主要用于生产聚醚多元醇、聚氨酯等。相比传统的氯醇法、共氧化法和双氧水直接氧化法（HPPO）等PO生产工艺，丙烯在氢氧混合气中一步环氧化制PO（HOPO）具有工艺简单、选择性高、产物易分离、能耗低等突出优势，是生产PO的理想工艺。重点介绍了丙烯氢氧环氧化反应动力学研究进展，包括主、副反应动力学模型以及催化剂失活模型。总结了基于该过程安全操作的反应器概念设计进展。分析了丙烯氢氧环氧化反应存在的挑战，从副产物生成途径、失活动力学及颗粒催化剂上的动力学等方面展望了可能的研究方向。

关键词: 催化, 环氧丙烷, 动力学, 丙烯环氧化, 反应器

CLC Number:

TQ 203.2

DU Wei, ZHANG Zhihua, DUAN Xuezhi, ZHOU Xinggui. A review on kinetics and reactor concept design of propylene epoxidation using H₂ and O₂[J]. CIESC Journal, 2021, 72(1): 116-131.

杜威, 张志华, 段学志, 周兴贵. 丙烯氢氧环氧化动力学与反应器概念设计研究进展[J]. 化工学报, 2021, 72(1): 116-131.

Figures/Tables 6

References 44

45	Harris J W, Arvay J, Delgass W N, et al. Propylene oxide inhibits propylene epoxidation over Au/TS-1[J]. J. Catal., 2018, 365: 105-114.
46	Kanungo S, Ferrandez D M P, D'angelo F N, et al. Kinetic study of propene oxide and water formation in hydro-epoxidation of propene on Au/Ti-SiO₂ catalyst[J]. J. Catal., 2016, 338: 284-294.
47	Schildberg H. The course of the explosions of combustible/O₂/N₂ mixtures in vessel-like geometry[J]. Forschung Im Ingenieurwesen-eng. Res., 2009, 73: 33-65.
48	Kumar R. Flammability limits of hydrogen-oxygen-diluent mixtures[J]. J. Fire Sci., 1985, 3: 245-262.
49	Schröder V, Emonts B, Janßen H, et al. Explosion limits of hydrogen/oxygen mixtures at initial pressures up to 200 bar[J]. Chem. Eng. & Tech., 2004, 27(8): 847-851.
50	Lee W S, Akatay M C, Stach E A, et al. Gas-phase epoxidation of propylene in the presence of H₂ and O₂ over small gold ensembles in uncalcined TS-1[J]. J. Catal., 2014, 313(5): 104-112.
51	Lu M, Tang Y, Chen W, et al. Explosion limits estimation and process optimization of direct propylene epoxidation with H₂ and O₂[J]. Chinese. J. Chem. Eng., 2019, 27(12): 2968-2978.
52	Liu Q, Wang T, Qiu J, et al. A novel carbon/ZSM-5 nanocomposite membrane with high performance for oxygen/nitrogen separation[J]. Chem. Comm., 2006, 11: 1230-1232.
53	Rebrov E, Croon M H J M, Schouten J C. Design of a microstructured reactor with integrated heat-exchanger for optimum performance of a highly exothermic reaction[J]. Catal. Today, 2001, 69: 183-192.
54	Fukuda M, Korematsu K, Sakamoto M. On quenching distance of mixtures of methane and hydrogen with air[J]. Bulletin of JSME, 1981, 24: 1192-1197.
55	Yuan Y H, Zhou X G, Wu W, et al. Propylene epoxidation in a microreactor with electric heating[J]. Catal. Today, 2005, 105(3): 544-550.
56	Jensen K. Flow chemistry —microreaction technology comes of age[J]. AIChE J., 2017, 63: e15642.
1	张健, 谢妤, 牛志蒙. 环氧丙烷生产技术及市场综述[J]. 化工科技, 2010, 18(3): 75-79.
	Zhang J, Xie Y, Niu Z M. Production technology of epoxypropane and its market analysis[J]. Sci. Tech. Chem. Ind., 2010, 18(3): 75-79.
57	Oyama S T, Zhang X, Lu J, et al. Epoxidation of propylene with H₂ and O₂ in the explosive regime in a packed-bed catalytic membrane reactor[J]. J. Catal., 2008, 257(1): 1-4.
58	Shu-Ichi N S. A one-step conversion of benzene to phenol with a palladium membrane[J]. Science, 2002, 295(5552): 105-107.
59	Sasidharan M, Patra A K, Kiyozumi Y, et al. Fabrication, characterization and catalytic oxidation of propylene over TS-1/Au membranes[J]. Chem. Eng. Sci., 2012, 75: 250-255.
60	Kertalli E, Perez Ferrandez D M, Schouten J C, et al. Direct synthesis of propene oxide from propene, hydrogen and oxygen in a catalytic membrane reactor[J]. Ind. Eng. Chem. Res., 2014, 53(42): 16275-16284.
61	Adhikari S, Fernando S. Hydrogen membrane separation techniques[J]. Ind. Eng. Chem. Res., 2006, 45(3): 875-881.
62	Zhang Y, Wu Z, Hong Z, et al. Hydrogen-selective zeolite membrane reactor for low temperature water gas shift reaction[J]. Chem. Eng. J., 2012, 197: 314-321.
63	Lu G Q, Diniz Da Costa J C, Duke M, et al. Inorganic membranes for hydrogen production and purification: a critical review and perspective[J]. J. Colloid Interface Sci., 2007, 314(2): 589-603.
64	Iulianelli A, Liguori S, Wilcox J, et al. Advances on methane steam reforming to produce hydrogen through membrane reactors technology: a review[J]. Catal. Rev., 2016, 58(1): 1-35.
65	Gao J, Lun Y, Hu Y, et al. The effect of A-site element on CO₂ resistance of O₂-selective La-based perovskite hollow fibers[J]. J. Ind. Eng. Chem., 2017, 53: 276-284.
66	Zhang P, Tong J, Huang K. Self-formed, mixed-conducting, triple-phase membrane for efficient CO₂/O₂ capture from flue gas and in situ dry-oxy methane reforming[J]. ACS Sustain. Chem. & Eng., 2018, 6(11): 14162-14169.
67	Dixon A G, Moser W R, Ma Y H. Waste reduction and recovery using O₂-permeable membrane reactors[J]. Ind. Eng. Chem. Res., 1994, 33(12): 3015-3024.
68	Tan X, Li K. Design of mixed conducting ceramic membranes/reactors for the partial oxidation of methane to syngas[J]. AIChE J., 2009, 55(10): 2675-2685.
69	Tan X, Li K. Fluidized bed membrane reactors[M]// Inorganic Membrane Reactors: Fundamentals and Applications. New York: John Wiley & Sons Inc., 2015: 215-226.
70	Lu M, Wang G, Zhang Z, et al. Microporous inert membrane packed-bed reactor for propylene epoxidation with hydrogen and oxygen: modelling and simulation[J]. Chem. Eng. Process., 2017, 122: 425-433.
2	薛金召, 牛小娟, 汪希领,等. 国内环氧丙烷市场分析及技术进展[J]. 化工进展, 2015, 34(9): 3500-3506.
	Xue J Z, Niu X J, Wang X L, et al. Market analysis and technology progress of domestic propylene oxide[J]. Chem. Ind. Eng. Progress, 2015, 34(9): 3500-3506.
3	2019中国环氧丙烷产业链年度报告[R]. 上海: 亚化咨询, 2019.
	Annual report of China propylene oxide industrial chain in 2019[R]. Shanghai: ASIACHEM, 2019.
4	Nijhuis T A, Makkee M, Moulijn J A, et al. The production of propene oxide: catalytic processes and recent developments[J]. Ind. Eng. Chem. Res., 2006, 45(10): 3447-3459.
5	Russo V, Tesser R, Santacesaria E, et al. Chemical and technical aspects of propene oxide production via hydrogen peroxide (HPPO Process)[J]. Ind. Eng. Chem. Res., 2012, 52(3): 1168-1178.
6	Min B K, Friend C M. Heterogeneous gold-based catalysis for green chemistry: low-temperature CO oxidation and propene oxidation[J]. Chem. Rev., 2007, 107(6): 2709-2724.
7	宋钊宁, 冯翔, 刘熠斌,等. 丙烯直接气相临氢环氧化催化剂结构调控和催化剂构-效关系研究进展[J]. 化学进展, 2016, 28(12): 1762-1773.
	Song Z N, Feng X, Liu Y B, et al. Advances in manipulation of catalysts structure and relationship of structure-performance for direct propene epoxidation with H₂ and O₂[J]. Progress in Chem., 2016, 28(12): 1752-1773.
8	Schmidt F, Bernhard M, Morell H, et al. HPPO process technology a novel route to propylene oxide without coproducts[J]. Chem. Today, 2014, 32: 31-35.
9	Sinha A K, Seelan S, Tsubota S, et al. A three-dimensional mesoporous titanosilicate support for gold nanoparticles: vapor-phase epoxidation of propene with high conversion[J]. Angew. Chem. Int. Ed., 2004, 43(12): 1546-1548.
10	Chowdhury B, Bravo-Suárez J J, Daté M, et al. Trimethylamine as a gas-phase promoter: highly efficient epoxidation of propylene over supported gold catalysts[J]. Angew. Chem. Int. Ed., 2006, 45(3): 412-415.
11	Huang J, Akita T, Faye J, et al. Propene epoxidation with dioxygen catalyzed by gold clusters[J]. Angew. Chem. Int. Ed., 2009, 48(42): 7862-7866.
12	Haruta M, Uphade B S, Tsubota S, et al. Selective oxidation of propylene over gold deposited on titanium-based oxides[J]. Res. Chem. Interm., 1998, 24(3): 329-336.
13	Chowdhury B, Bravo-Suárez J J, Mimura N, et al. In situ UV-vis and EPR study on the formation of hydroperoxide species during direct gas phase propylene epoxidation over Au/Ti-SiO₂ Catalyst[J]. J. Phys. Chem. B, 2006, 110(46): 22995-22999.
14	Suárez J J B, Bando K K, Lu J, et al. Transient technique for identification of true reaction intermediates: hydroperoxide species in propylene epoxidation on gold/titanosilicate catalysts by X-ray absorption fine structure spectroscopy[J]. J. Phys. Chem. C, 2008, 112(4): 1115-1123.
15	Chen J, Halin S J, Pidko E A, et al. Enhancement of catalyst performance in the direct propene epoxidation: a study into gold–titanium synergy[J]. Chem. Cat. Chem., 2013, 5(2): 467-478.
16	Ishida T, Koga H, Okumura M, et al. Advances in gold catalysis and understanding the catalytic mechanism[J]. Chem. Rec., 2016, 16(5): 2278-2293.
17	Kalvachev Y A, Hayashi T, Tsubota S, et al. Vapor-phase selective oxidation of aliphatic hydrocarbons over gold deposited on mesoporous titanium silicates in the Co-presence of oxygen and hydrogen[J]. J. Catal., 1999, 186(1): 228-233.
18	Uphade B S, Akita T, Nakamura T, et al. Vapor-phase epoxidation of propene using H₂ and O₂over Au/Ti-MCM-48[J]. J. Catal., 2002, 209(2): 331-340.
19	Qi C, Akita T, Okumura M, et al. Effect of surface chemical properties and texture of mesoporous titanosilicates on direct vapor-phase epoxidation of propylene over Au catalysts at high reaction temperature[J]. Appl. Catal., A, 2003, 253(1): 75-89.
20	Sinha A K, Seelan S, Akita T, et al. Vapor phase propylene epoxidation over Au/Ti-MCM-41 catalysts prepared by different Ti incorporation modes[J]. Appl. Catal., A, 2003, 240(1): 243-252.
21	Mul G, Zwijnenburg A, van der Linden B, et al. Stability and selectivity of Au/TiO₂ and Au/TiO₂/SiO₂catalysts in propene epoxidation: an in situ FT-IR Study[J]. J. Catal., 2001, 201(1): 128-137.
22	Lee W S, Akatay M C, Delgass W N, et al. Reproducible preparation of Au/TS-1 with high reaction rate for gas phase epoxidation of propylene[J]. J. Catal., 2012, 287: 178-189.
23	Lee W S, Akatay M C, Stach E A, et al. Enhanced reaction rate for gas-phase epoxidation of propylene using H₂ and O₂ by Cs promotion of Au/TS-1[J]. J. Catal., 2013, 308(4): 98-113.
24	Huang J, Takei T, Akita T, et al. Gold clusters supported on alkaline treated TS-1 for highly efficient propene epoxidation with O₂ and H₂[J]. Appl. Catal., B, 2010, 95(3): 430-438.
25	Feng X, Duan X, Zhou X G, et al. Au nanoparticles deposited on the external surfaces of TS-1: enhanced stability and activity for direct propylene epoxidation with H₂ and O₂[J]. Appl. Catal., B, 2014, 150/151(9): 396-401.
26	Zhan G, Du M, Sun D, et al. Vapor-phase propylene epoxidation with H₂/O₂ over bioreduction Au/TS-1 catalysts: synthesis, characterization, and optimization[J]. Ind. Eng. Chem. Res., 2011, 50(15): 9019-9026.
27	Zhang Z, Zhao X, Zhou X G, et al. Uncalcined TS-2 immobilized Au nanoparticles as a bifunctional catalyst to boost direct propylene epoxidation with H₂ and O₂[J]. AIChE J., 2020, 66(2): e16815.
28	Qian G, Yuan Y H, Zhou X G, et al. Vapor phase propylene epoxidation kinetics[M]//Rhee H K, Nam I S, Park J M. Studies in Surface Science and Catalysis. Amsterdam: Elsevier, 2006: 333-336.
29	Chan K H, Tse R. Determination of the Arrhenius activation energy using a temperature-programmed flow reactor[J]. J. Chem. Edu., 1984, 61(6): 547.
30	Nijhuis T A, Gardner T Q, Weckhuysen B M. Modeling of kinetics and deactivation in the direct epoxidation of propene over gold–titania catalysts[J]. J. Catal., 2005, 236(1): 153-163.
31	Nijhuis T A, Weckhuysen B M. The direct epoxidation of propene over gold-titania catalysts-a study into the kinetic mechanism and deactivation[J]. Catal. Today, 2006, 117(1): 84-89.
32	Nijhuis T A, Visser T, Weckhuysen B M. The role of gold in gold-titania epoxidation catalysts[J]. Angew. Chem. Int. Ed., 2005, 44(7): 1115-1118.
33	Nijhuis T A, Visser T, Weckhuysen B M. Mechanistic study into the direct epoxidation of propene over gold/titania catalysts[J]. J. Phys. Chem. B, 2005, 109(41): 19309-19319.
34	Nijhuis T A, Sacaliuc E, Beale A M, et al. Spectroscopic evidence for the adsorption of propene on gold nanoparticles during the hydro-epoxidation of propene[J]. J. Catal., 2008, 258(1): 256-264.
35	Nijhuis T A, Sacaliuc-Parvulescu E, Govender N S, et al. The role of support oxygen in the epoxidation of propene over gold–titania catalysts investigated by isotopic transient kinetics[J]. J. Catal., 2009, 265(2): 161-169.
36	Nijhuis T A, Chen J, Kriescher S M A, et al. The direct epoxidation of propene in the explosive regime in a microreactor—a study into the reaction kinetics[J]. Ind. Eng. Chem. Res., 2010, 49(21): 10479-10485.
37	Chen J, Halin S J, Nijhuis T A, et al. Kinetic study of propylene epoxidation with H₂ and O₂ over Au/Ti-SiO₂ in the explosive regime[J]. J. Stat. Phys., 2011, 152(2/3/4): 1041-1104.
38	Taylor B, Lauterbach J, Delgass W N, et al. Reaction kinetic analysis of the gas-phase epoxidation of propylene over Au/TS-1[J]. J. Catal., 2006, 242(1): 142-152.
39	Joshi A M, Delgass W N, Thomson K T. Mechanistic implications of aun/ti-lattice proximity for propylene epoxidation[J]. J. Phys. Chem. C, 2007, 111(22): 7841-7844.
40	Wells D H, Delgass W N, Thomson K T. Evidence of defect-promoted reactivity for epoxidation of propylene in titanosilicate (TS-1) catalysts: a DFT study[J]. J. Am. Chem. Soc., 2004, 126(9): 2956-2962.
41	Joshi A M, Delgass W N, Thomson K T. Partial oxidation of propylene to propylene oxide over a neutral gold trimer in the gas phase: a density functional theory study[J]. J. Phys. Chem. B, 2006, 110(6): 2572-2581.
42	Bravo-Suárez J J, Lu J, Oyama S T, et al. Kinetic study of propylene epoxidation with H₂ and O₂ over a gold/mesoporous titanosilicate catalyst[J]. J. Phys. Chem. C, 2007, 111(46): 17427-17436.
43	Lu J, Zhang X, Bravo-Suárez J J, et al. Kinetics of propylene epoxidation using H₂ and O₂ over a gold/mesoporous titanosilicate catalyst[J]. Catal. Today, 2007, 123(1/2/3/4): 189-197.
44	Wang G, Cao Y, Zhang Z, et al. Surface engineering and kinetics behaviors of Au/uncalcined TS-1 catalysts for propylene epoxidation with H₂ and O₂[J]. Ind. Eng. Chem. Res., 2019, 58(37): 17300-17307.

[1]	Cheng CHENG, Zhongdi DUAN, Haoran SUN, Haitao HU, Hongxiang XUE. Lattice Boltzmann simulation of surface microstructure effect on crystallization fouling [J]. CIESC Journal, 2023, 74(S1): 74-86.
[2]	Yepin CHENG, Daqing HU, Yisha XU, Huayan LIU, Hanfeng LU, Guokai CUI. Application of ionic liquid-based deep eutectic solvents for CO₂ conversion [J]. CIESC Journal, 2023, 74(9): 3640-3653.
[3]	Yuyuan ZHENG, Zhiwei GE, Xiangyu HAN, Liang WANG, Haisheng CHEN. Progress and prospect of medium and high temperature thermochemical energy storage of calcium-based materials [J]. CIESC Journal, 2023, 74(8): 3171-3192.
[4]	Linzheng WANG, Yubing LU, Ruizhi ZHANG, Yonghao LUO. Analysis on thermal oxidation characteristics of VOCs based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3242-3255.
[5]	Mengmeng ZHANG, Dong YAN, Yongfeng SHEN, Wencui LI. Effect of electrolyte types on the storage behaviors of anions and cations for dual-ion batteries [J]. CIESC Journal, 2023, 74(7): 3116-3126.
[6]	Yaxin CHEN, Hang YUAN, Guanzhang LIU, Lei MAO, Chun YANG, Ruifang ZHANG, Guangya ZHANG. Advances in enzyme self-immobilization mediated by protein nanocages [J]. CIESC Journal, 2023, 74(7): 2773-2782.
[7]	Xiaoling TANG, Jiarui WANG, Xuanye ZHU, Renchao ZHENG. Biosynthesis of chiral epichlorohydrin by halohydrin dehalogenase based on Pickering emulsion system [J]. CIESC Journal, 2023, 74(7): 2926-2934.
[8]	Tan ZHANG, Guang LIU, Jinping LI, Yuhan SUN. Performance regulation strategies of Ru-based nitrogen reduction electrocatalysts [J]. CIESC Journal, 2023, 74(6): 2264-2280.
[9]	Zhenghao YANG, Zhen HE, Yulong CHANG, Ziheng JIN, Xia JIANG. Research progress in downer fluidized bed reactor for biomass fast pyrolysis [J]. CIESC Journal, 2023, 74(6): 2249-2263.
[10]	Xiaowen ZHOU, Jie DU, Zhanguo ZHANG, Guangwen XU. Study on the methane-pulsing reduction characteristics of Fe₂O₃-Al₂O₃ oxygen carrier [J]. CIESC Journal, 2023, 74(6): 2611-2623.
[11]	Guangyu WANG, Kai ZHANG, Kaihua ZHANG, Dongke ZHANG. Heat and mass transfer and energy consumption for microwave drying of coal slime [J]. CIESC Journal, 2023, 74(6): 2382-2390.
[12]	Lei MAO, Guanzhang LIU, Hang YUAN, Guangya ZHANG. Efficient preparation of carbon anhydrase nanoparticles capable of capturing CO₂ and their characteristics [J]. CIESC Journal, 2023, 74(6): 2589-2598.
[13]	Jipeng ZHOU, Wenjun HE, Tao LI. Reaction engineering calculation of deactivation kinetics for ethylene catalytic oxidation over irregular-shaped catalysts [J]. CIESC Journal, 2023, 74(6): 2416-2426.
[14]	Zedong WANG, Zhiping SHI, Liyan LIU. Numerical simulation and optimization of acoustic streaming considering inhomogeneous bubble cloud dissipation in rectangular reactor [J]. CIESC Journal, 2023, 74(5): 1965-1973.
[15]	Quanbi ZHANG, Yijin YANG, Xujing GUO. Catalytic degradation of dissolved organic matter in rifampicin pharmaceutical wastewater by Fenton oxidation process [J]. CIESC Journal, 2023, 74(5): 2217-2227.

A review on kinetics and reactor concept design of propylene epoxidation using H₂ and O₂

丙烯氢氧环氧化动力学与反应器概念设计研究进展

RichHTML

PDF (PC)

Knowledge

Cited

Abstract

Cite this article

share this article

Figures/Tables 6

References 44

Related Articles 15

Recommended Articles

Metrics

Comments