乙烷与苯经接力催化路线制备乙苯

doi:10.11949/0438-1157.20210050

摘要/Abstract

摘要：

设计乙烷经氯氧化制备乙烯再与苯烷基化一步法制备乙苯的接力催化路线。研制铈基氧化物作为活化乙烷生成中间产物乙烯的催化剂，并耦合H-ZSM-5沸石分子筛与苯进一步烷基化生成乙苯。在Mn/CeO₂氧化物与H-ZSM-5沸石分子筛以研磨混合形成的双功能催化剂上，实现了乙烷与苯催化制备乙苯的可控接力催化。考察了氧化物的组成、氧化物与沸石分子筛的耦合方式与最适质量配比、沸石分子筛的硅铝比对接力催化反应的影响，并进行了催化剂稳定性研究。结合X射线衍射（XRD）、NH₃程序升温脱附（NH₃-TPD）、透射电子显微镜（TEM）、X射线荧光光谱分析（XRF）等表征手段分析了催化剂结构及其与催化性能的构效关系。提出后续催化剂研究的关键在于分子筛烷基化能力以及抗流失能力的提高。

关键词: 乙苯, 乙烷, 苯, 接力催化, 分子筛, 氧化铈

Abstract:

This work designs a tandem route for the production of ethylbenzene (EB) directly from ethane and benzene via the ethylene intermediate. The tandem reaction consists of chlorine oxidation of ethane to form ethylene and the alkylation reaction between ethylene and benzene. In this paper, cerium-based oxide was selected as the catalyst for activating ethane to produce ethylene, and the H-ZSM-5 zeolite was used to be further alkylated with benzene to produce ethylbenzene. We investigate the optimization of the selected oxides, and the effects of the ratio of oxides and zeolites, acidity of zeolite on catalytic performances of tandem reaction over Mn/CeO₂-H-ZSM-5 bifunctional catalyst. The stability of catalyst is also investigated. Combining X-ray diffraction (XRD), NH₃ temperature programmed desorption (NH₃-TPD), transmission electron microscopy (TEM), and X-ray fluorescence spectroscopy (XRF) techniques, the structure of catalyst and the relationship of structure and performances are further studied. The research suggests that the key to subsequent catalyst research lies in the improvement of zeolite alkylation ability and anti-loss ability.

Key words: ethylbenzene, ethane, benzene, tandem catalysis, zeolite, cerium oxide

中图分类号:

TQ 028.8

程挥戈, 牛韦, 汤兴蕾, 岳亮旭, 康金灿, 张庆红, 王野. 乙烷与苯经接力催化路线制备乙苯[J]. 化工学报, 2021, 72(7): 3658-3667.

CHENG Huige, NIU Wei, TANG Xinglei, YUE Liangxu, KANG Jincan, ZHANG Qinghong, WANG Ye. Synthesis of ethylbenzene from ethane and benzene by tandem catalysis[J]. CIESC Journal, 2021, 72(7): 3658-3667.

图/表 12

图1 乙烷氯氧化、乙烯与苯烷基化的催化反应性能

Fig.1 Catalytic performances of chlorine oxidation of ethane and alkylation reaction of ethylene and benzene

图2 Mn/CeO2氧化物与H-ZSM-5(25)分子筛的耦合方式对反应性能的影响（反应条件：W(Mn/CeO2) = 0.5 g, T = 450℃, P = 0.1 MPa, F(total) = 40 ml/min, time on stream 2.5 h, C2H6/benzene/HCl/O2/N2/He = 1/3.2/3/1/1.5/3.5, Mn/CeO2∶H-ZSM-5= 1∶2）

Fig.2 Effect of contact manner of Mn/CeO2 oxide and H-ZSM-5(25) zeolite on catalytic performances others—C2H4Cl2 and hydrocarbons

图3 Mn/CeO2氧化物与H-ZSM-5分子筛的质量比对催化性能的影响（反应条件：W = 1.5 g, T = 450℃, P = 0.1 MPa, F(total) = 40 ml/min, time on stream 2.5 h, C2H6/benzene/HCl/O2/N2/He = 1/3.2/3/1/1.5/3.5）

Fig.3 Catalytic performances of Mn/CeO2-H-ZSM-5-grind with different mass ratios of Mn/CeO2 oxide to H-ZSM-5 zeolite

图4 H-ZSM-5分子筛硅铝比对双功能催化剂反应性能的影响（反应条件：W = 1.5 g, T = 450℃, P = 0.1 MPa, F(total) = 40 ml/min, Mn/CeO2∶H-ZSM-5 = 1∶2, time on stream 2.5 h, C2H6/benzene/HCl/O2/N2/He = 1/3.2/3/1/1.5/3.5）

Fig.4 Effect of Si/Al ratio of H-ZSM-5 on catalytic performances over Mn/CeO2-H-ZSM-5 bifunctional catalyst

图5 Mn/CeO2-H-ZSM-5(38)- grind催化剂上反应性能随时间变化(反应条件：W = 1.5 g, T = 450℃, P = 0.1 MPa, F(total) = 40 ml/min, C2H6/benzene/HCl/O2/N2/He = 1/3.2/3/1/1.5/3.5)

Fig.5 Catalytic performances with time on stream over Mn/CeO2-H-ZSM-5-grindcatalyst

图6 Mn负载前后CeO2的XRD谱图

Fig.6 XRD patterns of CeO2 and Mn/CeO2

图7 Mn/CeO2、H-ZSM-5及其复合物的XRD谱图

Fig.7 XRD patterns of Mn/CeO2, H-ZSM-5 and Mn/CeO2-H-ZSM-5

图8 Mn/CeO2纳米棒的TEM图

Fig.8 TEM images of Mn/CeO2 nanorods

图9 Mn/CeO2与H-ZSM-5分子筛研磨复合后的TEM图

Fig.9 TEM images of Mn/CeO2-H-ZSM-5 catalysts

表1 催化剂反应前后的XRF分析结果

Table 1 XRF analysis of Mn/CeO2-H-ZSM-5 before and after catalytic reaction

Reaction time/h	Element content/% (mass)
Reaction time/h	Ce	Mn	Al	Si
0	15.86	2.16	0.84	34.3
2.5	15.91	2.07	0.81	34.0
35	16.43	1.62	0.75	39.7

图10 不同硅铝比的H-ZSM-5分子筛的NH3-TPD图

Fig.10 NH3-TPD profiles of H-ZSM-5 with different Si/Al ratio

图11 Mn/CeO2-H-ZSM-5-grind催化剂反应前后NH3-TPD图

Fig.11 NH3-TPD patterns of Mn/CeO2-H-ZSM-5-grind catalyst before and after reaction

参考文献 40

1	Cavani F, Trifirò F. Alternative processes for the production of styrene[J]. Applied Catalysis A: General, 1995, 133(2): 219-239.
2	Vrieland G E, Menon P G. Nature of the catalytically active carbonaceous sites for the oxydehydrogenation of ethylbenzene to styrene: a brief review[J]. Applied Catalysis, 1991, 77(1): 1-8.
3	Kainthla I, Bhanushali J T, Keri R S, 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.
4	Bokade V V, Yadav G D. Heteropolyacid supported on acidic clay: a novel efficient catalyst for alkylation of ethylbenzene with dilute ethanol to diethylbenzene in presence of C₈ aromatics[J]. Journal of Molecular Catalysis A: Chemical, 2008, 285(1/2): 155-161.
5	Yang W M, Wang Z D, Sun H M, et al. Advances in development and industrial applications of ethylbenzene processes[J]. Chinese Journal of Catalysis, 2016, 37(1): 16-26.
6	Liu S L, Chen F C, Xie S J, et al. Highly selective ethylbenzene production through alkylation of dilute ethylene with gas phase-liquid phase benzene and transalkylation feed[J]. Journal of Natural Gas Chemistry, 2009, 18(1): 21-24.
7	Zhong L, Yu F, An Y, et al. Cobalt carbide nanoprisms for direct production of lower olefins from syngas[J]. Nature, 2016, 538(7623): 84-87.
8	Li Y J, Zhang T T. Integration and optimized utilization of naphtha resources[J]. China Petroleum Processing and Petrochemical Technology, 2010, 12(2): 51-56.
9	Haribal V P, Chen Y, Neal L, et al. Intensification of ethylene production from naphtha via a redox oxy-cracking scheme: process simulations and analysis[J]. Engineering, 2018, 4(5): 714-721.
10	曹杰, 迟东训. 中国乙烯工业发展现状与趋势[J]. 国际石油经济, 2019, 27(12): 53-59.
	Cao J, Chi D X. Development status and trend of ethylene industry in China[J]. International Petroleum Economics, 2019, 27(12): 53-59.
11	Zhao Z T, Chong K T, Jiang J Y, et al. Low-carbon roadmap of chemical production: a case study of ethylene in China[J]. Renewable and Sustainable Energy Reviews, 2018, 97: 580-591.
12	黄格省, 师晓玉, 张彦, 等. 国内外乙烷裂解制乙烯发展现状及思考[J]. 现代化工, 2018, 38(10): 1-5.
	Huang G S, Shi X Y, Zhang Y, et al. Situation of ethylene production via ethane cracking and considerations[J]. Modern Chemical Industry, 2018, 38(10): 1-5.
13	徐海丰. 2018年世界乙烯行业发展状况与趋势[J]. 国际石油经济, 2019, 27(1): 82-88.
	Xu H F. Global ethylene industry in 2018 and its development trend[J]. International Petroleum Economics, 2019, 27(1): 82-88.
14	Dasani D, Wang Y, Tsotsis T T, et al. Laboratory-scale investigation of sorption kinetics of methane/ethane mixtures in shale[J]. Industrial & Engineering Chemistry Research, 2017, 56(36): 9953-9963.
15	Scott A R. Composition of coalbed gases [J]. In Situ, 1994, 18(2): 185-208.
16	Nakano S, Yamamoto K, Ohgaki K. Natural gas exploitation by carbon dioxide from gas hydrate fields—high-pressure phase equilibrium for an ethane hydrate system[J]. Proceedings of the Institution of Mechanical Engineers, Part A: Journal of Power and Energy, 1998, 212(3): 159-163.
17	Choudhary V R, Uphade B S, Mulla S A R. Coupling of endothermic thermal cracking with exothermic oxidative dehydrogenation of ethane to ethylene using a diluted SrO/La₂O₃ catalyst[J]. Angewandte Chemie International Edition in English, 1995, 34(6): 665-666.
18	Yang J I, Kim J N, Cho S H, et al. Catalytic composites based on yttria stabilized zirconia for oxidative dehydrogenation of ethane[J]. Korean Journal of Chemical Engineering, 2004, 21(2): 381-384.
19	温翯, 郭晓莉, 苟尕莲, 等. 乙烷裂解制乙烯的工艺研究进展[J]. 现代化工, 2020, 40(5): 47-51.
	Wen H, Guo X L, Gou G L, et al. Process research advances in ethane cracking to ethylene[J]. Modern Chemical Industry, 2020, 40(5): 47-51.
20	Olah G A, Schilling P, Staral J S, et al. Electrophilic reactions at single bonds(ⅪⅤ): Anhydrous fluoroantimonic acid catalyzed alkylation of benzene with alkanes and alkane-alkene and alkane-alkylbenzene mixtures[J]. Journal of the American Chemical Society, 1975, 97(23): 6807-6810.
21	Isaev S A, Vasina T V, Bragin O V. Alkylation of benzene by propane over zeolite-containing pentasil-alumina compositions and dealuminated pentasils[J]. Bulletin of the Russian Academy of Sciences, Division of Chemical Science, 1992, 41(12): 2143-2146.
22	Kato S, Nakagawa K, Ikenaga N O, et al. Alkylation of benzene with ethane over platinum-loaded zeolite catalyst[J]. Catalysis Letters, 2001, 73(2/3/4): 175-180.
23	Lukyanov D, Vazhnova T. A kinetic study of benzene alkylation with ethane into ethylbenzene over bifunctional PtH-MFI catalyst[J]. Journal of Catalysis, 2008, 257(2): 382-389.
24	Zhou W, Kang J, Cheng K, et al. Direct conversion of syngas into methyl acetate, ethanol, and ethylene by relay catalysis via the intermediate dimethyl ether[J]. Angew. Chem. Int. Ed., 2018, 57(37): 12012-12016.
25	Zhou W, Cheng K, Kang J C, et al. New horizon in C1 chemistry: breaking the selectivity limitation in transformation of syngas and hydrogenation of CO₂ into hydrocarbon chemicals and fuels[J]. Chemical Society Reviews, 2019, 48(12): 3193-3228.
26	Kang J, He S, Zhou W, et al. Single-pass transformation of syngas into ethanol with high selectivity by triple tandem catalysis[J]. Nature Communications, 2020, 11(1): 827.
27	Yu F C, Wu X J, Zhang Q H, et al. Oxidative dehydrogenation of ethane to ethylene in the presence of HCl over CeO₂-based catalysts[J]. Chinese Journal of Catalysis, 2014, 35(8): 1260-1266.
28	Shavaleev D A, Pavlov M L, Basimova R A, et al. Synthesis of a zeolite-containing catalyst for gas-phase alkylation of benzene with ethylene[J]. Petroleum Chemistry, 2020, 60(10): 1164-1169.
29	Zhang Z Q, Ding J, Chai R J, et al. Oxidative dehydrogenation of ethane to ethylene: a promising CeO₂-ZrO₂-modified NiO-Al₂O₃/Ni-foam catalyst[J]. Applied Catalysis A: General, 2018, 550: 151-159.
30	Cheng K, Zhou W, Kang J C, et al. Bifunctional catalysts for one-step conversion of syngas into aromatics with excellent selectivity and stability[J]. Chem, 2017, 3(2): 334-347.
31	Cuo Z X, Wang D D, Gong Y, et al. A novel porous ceramic membrane supported monolithic Cu-doped Mn–Ce catalysts for benzene combustion[J]. Catalysts, 2019, 9(8): 652.
32	Gärtner C A, Van Veen A C, Lercher J A. Oxidative dehydrogenation of ethane: common principles and mechanistic aspects[J]. ChemCatChem, 2013, 5(11): 3196-3217.
33	Li C W, Sun Y, Hess F, et al. Catalytic HCl oxidation reaction: stabilizing effect of Zr-doping on CeO₂ nano-rods[J]. Applied Catalysis B: Environmental, 2018, 239: 628-635.
34	Katada N, Igi H, Kim J H. Determination of the acidic properties of zeolite by theoretical analysis of temperature-programmed desorption of ammonia based on adsorption equilibrium[J]. The Journal of Physical Chemistry B, 1997, 101(31): 5969-5977.
35	徐如人, 庞文琴, 霍启升, 等. 分子筛与多孔材料化学[M]. 2版. 北京: 科学出版社, 2015.
	Xu R R, Pang W Q, Huo Q S. Molecular Sieves and Porous Materials Chemistry [M]. 2nd ed. Beijing: Science Press, 2015.
36	Shirazi L, Jamshidi E, Ghasemi M R. The effect of Si/Al ratio of ZSM-5 zeolite on its morphology, acidity and crystal size[J]. Crystal Research and Technology, 2008, 43(12): 1300-1306.
37	Zhu H B, Liu Z C, Kong D J, et al. Synthesis and catalytic performances of mesoporous zeolites templated by polyvinyl butyral gel as the mesopore directing agent[J]. The Journal of Physical Chemistry C, 2008, 112(44): 17257-17264.
38	Janssens T V W. A new approach to the modeling of deactivation in the conversion of methanol on zeolite catalysts[J]. Journal of Catalysis, 2009, 264(2): 130-137.
39	刘巧玲. 含氯化氢废气的处理与回收利用[J]. 化工管理, 2017,(23): 226-228.
	Liu Q L. Treatment and recovery of waste gas containing hydrogen chloride [J]. Chemical Enterprise Management, 2017,(23): 226-228.
40	黄冬兰. 膜法分离丙烯和氯化氢混合气[D]. 大连: 大连理工大学, 2004.
	Huang D L. Study on separation of propylene/hydrogen chloride mixture gas by membrane technology[D]. Dalian: Dalian University of Technology, 2004.

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