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CLC number: TQ032.4

On-line Access: 2021-02-05

Received: 2020-03-31

Revision Accepted: 2020-07-12

Crosschecked: 2021-01-14

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Citations:  Bibtex RefMan EndNote GB/T7714


Bin-bo Jiang


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Journal of Zhejiang University SCIENCE A 2021 Vol.22 No.2 P.106-115


Modification of acidity in HZSM-5 zeolite for methane-methanol co-reaction

Author(s):  Bing-jie Zhou, Zhi-xiang Xi, Yue Yu, Bin-bo Jiang, Jing-dai Wang, Zu-wei Liao, Zheng-liang Huang, Yong-rong Yang

Affiliation(s):  Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China; more

Corresponding email(s):   jiangbb@zju.edu.cn

Key Words:  Methane conversion, Methanol, Co-reaction, Acidity, HZSM-5

Bing-jie Zhou, Zhi-xiang Xi, Yue Yu, Bin-bo Jiang, Jing-dai Wang, Zu-wei Liao, Zheng-liang Huang, Yong-rong Yang. Modification of acidity in HZSM-5 zeolite for methane-methanol co-reaction[J]. Journal of Zhejiang University Science A, 2021, 22(2): 106-115.

@article{title="Modification of acidity in HZSM-5 zeolite for methane-methanol co-reaction",
author="Bing-jie Zhou, Zhi-xiang Xi, Yue Yu, Bin-bo Jiang, Jing-dai Wang, Zu-wei Liao, Zheng-liang Huang, Yong-rong Yang",
journal="Journal of Zhejiang University Science A",
publisher="Zhejiang University Press & Springer",

%0 Journal Article
%T Modification of acidity in HZSM-5 zeolite for methane-methanol co-reaction
%A Bing-jie Zhou
%A Zhi-xiang Xi
%A Yue Yu
%A Bin-bo Jiang
%A Jing-dai Wang
%A Zu-wei Liao
%A Zheng-liang Huang
%A Yong-rong Yang
%J Journal of Zhejiang University SCIENCE A
%V 22
%N 2
%P 106-115
%@ 1673-565X
%D 2021
%I Zhejiang University Press & Springer
%DOI 10.1631/jzus.A2000126

T1 - Modification of acidity in HZSM-5 zeolite for methane-methanol co-reaction
A1 - Bing-jie Zhou
A1 - Zhi-xiang Xi
A1 - Yue Yu
A1 - Bin-bo Jiang
A1 - Jing-dai Wang
A1 - Zu-wei Liao
A1 - Zheng-liang Huang
A1 - Yong-rong Yang
J0 - Journal of Zhejiang University Science A
VL - 22
IS - 2
SP - 106
EP - 115
%@ 1673-565X
Y1 - 2021
PB - Zhejiang University Press & Springer
ER -
DOI - 10.1631/jzus.A2000126

A co-reaction of methane with methanol over zeolite catalysts has emerged as a new approach to the long-standing challenge of methane transformation. However, the effect of catalyst acid properties on the co-reaction has been rarely studied. In this study, a series of HZSM-5 zeolites with comparable diffusion abilities and various acidities were synthesized directly through steaming with 100% water vapor at 693 K. The co-reaction of methane and methanol was subsequently evaluated. Brønsted acidity at 0.262 mmol/g was detected to reach the maximum methane conversion of 5.42% at 673 K, which was also the odd point in the relationship between acid concentration and C4 hydrogen transfer index. Moreover, the influence of methanol feed was investigated over parent and steamed ZSM-5 catalyst, with results showing that excessive acid sites or methanol molecules reduce methane conversion. It is proposed that acid sites adsorbed with methanol molecules construct the methane activation sites. Hence, a proper design of zeolite acidity should be achieved to obtain higher methane conversion in the co-reaction process.


创新点:1. 实现了低温下的甲烷活化;2. 通过水蒸气处理单因素调控HZSM-5催化剂的酸性;3. 提出了HZSM-5上甲烷与甲醇的共活化机制.
方法:1. 通过水蒸气处理,得到孔结构和扩散能力差异小而酸性差异显著的系列HZSM-5催化剂(图1-6);2. 通过催化剂性能考评,对比研究不同酸性HZSM-5上的甲醇反应以及甲烷甲醇耦合反应过程(图7);3. 在酸性不同的催化剂上研究甲醇空速对甲烷转化的影响(图9).
结论:1. 在HZSM-5催化剂上,存在最适酸浓度,可使甲烷转化率最高;2. 酸浓度更高的催化剂,其达到最大甲烷转化率所对应的甲醇空速更大;3. 吸附有甲醇分子的酸位点构成了耦合反应中甲烷的活化中心.


Darkslateblue:Affiliate; Royal Blue:Author; Turquoise:Article


[1]Bjørgen M, Joensen F, Spangsberg Holm M, et al., 2008. Methanol to gasoline over zeolite H-ZSM-5: improved catalyst performance by treatment with NaOH. Applied Catalysis A: General, 345(1):43-50.

[2]Brandenberger S, Kröcher O, Casapu M, et al., 2011. Hydrothermal deactivation of Fe-ZSM-5 catalysts for the selective catalytic reduction of NO with NH3. Applied Catalysis B: Environmental, 101(3-4):649-659.

[3]Cao ZW, Jiang HQ, Luo HX, et al., 2013. Natural gas to fuels and chemicals: improved methane aromatization in an oxygen-permeable membrane reactor. Angewandte Chemie International Edition, 52(51):13794-13797.

[4]Chang FX, Wei YX, Liu XB, et al., 2007. A mechanistic investigation of the coupled reaction of n-hexane and methanol over HZSM-5. Applied Catalysis A: General, 328(2):163-173.

[5]Choudhary VR, Mondal KC, Mulla SA, 2005. Simultaneous conversion of methane and methanol into gasoline over bifunctional Ga-, Zn-, In-, and/or Mo-modified ZSM-5 zeolites. Angewandte Chemie International Edition, 44(28):4381-4385.

[6]Fernandez C, Stan I, Gilson JP, et al., 2010. Hierarchical ZSM-5 zeolites in shape-selective xylene isomerization: role of mesoporosity and acid site speciation. Chemistry– A European Journal, 16(21):6224-6233.

[7]Gao Y, Zheng BH, Wu G, et al., 2016. Effect of the Si/Al ratio on the performance of hierarchical ZSM-5 zeolites for methanol aromatization. RSC Advances, 6(87):83581-83588.

[8]Groen JC, Moulijn JA, Pérez-Ramírez J, 2005. Decoupling mesoporosity formation and acidity modification in ZSM-5 zeolites by sequential desilication-dealumination. Microporous and Mesoporous Materials, 87(2):153-161.

[9]Haw JF, 2002. Zeolite acid strength and reaction mechanisms in catalysis. Physical Chemistry Chemical Physics, 4(22):5431-5441.

[10]He P, Jarvis JS, Meng SJ, et al., 2019a. Co-aromatization of methane with propane over Zn/HZSM-5: the methane reaction pathway and the effect of Zn distribution. Applied Catalysis B: Environmental, 250:99-111.

[11]He P, Wang AG, Meng SJ, et al., 2019b. Impact of Al sites on the methane co-aromatization with alkanes over Zn/ HZSM-5. Catalysis Today, 323:94-104.

[12]Ilias S, Bhan A, 2013. Mechanism of the catalytic conversion of methanol to hydrocarbons. ACS Catalysis, 3(1):18-31.

[13]Janssen AH, Koster AJ, de Jong KP, 2001. Three-dimensional transmission electron microscopic observations of mesopores in dealuminated zeolite Y. Angewandte Chemie International Edition, 40(6):1102-1104.

[14]Jarvis J, Wong A, He P, et al., 2018. Catalytic aromatization of naphtha under methane environment: effect of surface acidity and metal modification of HZSM-5. Fuel, 223: 211-221.

[15]Karakaya C, Morejudo SH, Zhu HY, et al., 2016. Catalytic chemistry for methane dehydroaromatization (MDA) on a bifunctional Mo/HZSM-5 catalyst in a packed bed. Industrial & Engineering Chemistry Research, 55(37):9895-9906.

[16]Li L, Stroobants C, Lin KF, et al., 2011. Selective conversion of trioses to lactates over Lewis acid heterogeneous catalysts. Green Chemistry, 13(5):1175-1181.

[17]Li QY, He P, Jarvis J, et al., 2018. Catalytic co-aromatization of methane and heptane as an alkane model compound over Zn-Ga/ZSM-5: a mechanistic study. Applied Catalysis B: Environmental, 236:13-24.

[18]Lin LF, Qiu CF, Zhuo ZX, et al., 2014. Acid strength controlled reaction pathways for the catalytic cracking of 1-butene to propene over ZSM-5. Journal of Catalysis, 309:136-145.

[19]Lin LF, Zhao SF, Zhang DW, et al., 2015. Acid strength controlled reaction pathways for the catalytic cracking of 1-pentene to propene over ZSM-5. ACS Catalysis, 5(7):4048-4059.

[20]Liu Y, Li DF, Wang TY, et al., 2016. Efficient conversion of methane to aromatics by coupling methylation reaction. ACS Catalysis, 6(8):5366-5370.

[21]Luzgin MV, Toktarev AV, Parmon VN, et al., 2013. Coaromatization of methane with propane on Mo-containing zeolite H-BEA: a solid-state NMR and GC-MS study. The Journal of Physical Chemistry C, 117(44):22867-22873.

[22]Majhi S, Pant KK, 2014. Direct conversion of methane with methanol toward higher hydrocarbon over Ga modified Mo/H-ZSM-5 catalyst. Journal of Industrial and Engineering Chemistry, 20(4):2364-2369.

[23]Mentzel UV, Shunmugavel S, Hruby SL, et al., 2009. High yield of liquid range olefins obtained by converting i-propanol over zeolite H-ZSM-5. Journal of the American Chemical Society, 131(46):17009-17013.

[24]Mier D, Aguayo AT, Gayubo AG, et al., 2010. Synergies in the production of olefins by combined cracking of n-butane and methanol on a HZSM-5 zeolite catalyst. Chemical Engineering Journal, 160(2):760-769.

[25]Mohammadparast F, Halladj R, Askari S, 2015. The crystal size effect of nano-sized ZSM-5 in the catalytic performance of petrochemical processes: a review. Chemical Engineering Communications, 202(4):542-556.

[26]Morejudo SH, Zanón R, Escolástico S, et al., 2016. Direct conversion of methane to aromatics in a catalytic co-ionic membrane reactor. Science, 353(6299):563-566.

[27]Niu XJ, Gao J, Wang K, et al., 2017. Influence of crystal size on the catalytic performance of H-ZSM-5 and Zn/H-ZSM-5 in the conversion of methanol to aromatics. Fuel Processing Technology, 157:99-107.

[28]Niwa M, Sota S, Katada N, 2012. Strong Brønsted acid site in HZSM-5 created by mild steaming. Catalysis Today, 185(1):17-24.

[29]Schwach P, Pan XL, Bao XH, 2017. Direct conversion of methane to value-added chemicals over heterogeneous catalysts: challenges and prospects. Chemical Reviews, 117(13):8497-8520.

[30]Sharanda LF, Shimansky AP, Kulik TV, et al., 1995. Study of acid-base surface properties of pyrogenic γ-aluminium oxide. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 105(2-3):167-172.

[31]Sowerby B, Becker SJ, Belcher LJ, 1996. Modeling of 2-methylpentane cracking: the application of adsorption equilibrium constants estimated using proton affinities. Journal of Catalysis, 161(1):377-386.

[32]Spivey JJ, Hutchings G, 2014. Catalytic aromatization of methane. Chemical Society Reviews, 43(3):792-803.

[33]Taifan W, Baltrusaitis J, 2016. CH4 conversion to value added products: potential, limitations and extensions of a single step heterogeneous catalysis. Applied Catalysis B: Environmental, 198:525-547.

[34]Vollmer I, Li GN, Yarulina I, et al., 2018. Relevance of the Mo-precursor state in H-ZSM-5 for methane dehydroaromatization. Catalysis Science & Technology, 8(3):916-922.

[35]Wang AG, He P, Yung M, et al., 2016. Catalytic co-aromatization of ethanol and methane. Applied Catalysis B: Environmental, 198:480-492.

[36]Xu J, Zheng AM, Wang XM, et al., 2012. Room temperature activation of methane over Zn modified H-ZSM-5 zeolites: insight from solid-state NMR and theoretical calculations. Chemical Science, 3(10):2932-2940.

[37]Yu ZW, Li SH, Wang Q, et al., 2011. Brønsted/Lewis acid synergy in H-ZSM-5 and H-MOR zeolites studied by 1H and 27Al DQ-MAS solid-state NMR spectroscopy. The Journal of Physical Chemistry C, 115(45):22320-22327.

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