Application of ternary spinel and twined ZSM-5 zeolite in methylation of benzene with carbon dioxide

doi:10.16085/j.issn.1000-6613.2024-0133

Abstract

Abstract:

Ternary spinel-type ZnGaAl metal oxide and twinned ZSM-5 zeolite were integrated to prepare bifunctional catalyst which were then applied in the methylation of benzene with carbon dioxide. Experimental results revealed that the ternary spinel effectively promoted the activity and the twinned ZSM-5 increased the para-xylene content in the products, compared with the bifunctional catalyst made from the binary ZnAl or ZnGa spinel and conventional ZSM-5 counterparts. This phenomenon can be attributed to the higher concentration of oxygen vacancies provided by the ternary ZnGaAl spinel which enhanced the adsorption towards carbon dioxide and therefore generated more intermediates to react with benzene. Besides, the weak surface acidities as well as the low exposure degree of (010) surface of twinned ZSM-5 efficiently suppressed the isomerization of xylene on zeolite surface and magnified the diffusion advantages of para-xylene. The optimal bifunctional catalyst at 425℃ and 3.0MPa exhibited a benzene conversion of 39.2% and a CO₂ conversion of 37.1%, with a total toluene and xylene selectivity of 91.2% and 55.6% of all the xylene isomers being para-xylene, which is significantly better than the bifunctional catalyst composed of binary spinel and conventional ZSM-5 zeolite.

Key words: carbon dioxide, hydrogen, benzene, molecular sieve, composites, catalysis

摘要：

将三元尖晶石型锌镓铝金属氧化物和孪晶ZSM-5分子筛制备成双功能催化剂用于苯与二氧化碳甲基化反应。结果表明，相对于二元锌铝或锌镓金属氧化物和常规形貌ZSM-5分子筛组成的双功能催化剂，三元锌镓铝尖晶石可提高催化剂的活性，孪晶分子筛可有效增加产物中对二甲苯的含量。结合各种表征发现，三元锌镓铝尖晶石所具有的更多氧空位强化了二氧化碳的吸附，能够产生更多的甲基化中间体；同时，孪晶分子筛较少的表面酸性位点和较低的(010)晶面暴露程度有效抑制了分子筛表面二甲苯的异构化反应并凸显了对二甲苯的扩散优势，使产物中对二甲苯含量超过了热力学平衡组成。优化后的催化剂在425℃、3MPa的反应条件下表现出高达39.2%的苯转化率和37.1%的二氧化碳转化率，产物中甲苯、二甲苯总选择性为91.2%，且对二甲苯在二甲苯中的比例高达55.6%，催化性能相比二元尖晶石和常规ZSM-5组成的双功能催化剂有显著提升。

关键词: 二氧化碳, 氢, 苯, 分子筛, 复合材料, 催化

CLC Number:

O643.36

YANG Fan, ZHAO Yitao, ZHU Xuedong, WANG Darui. Application of ternary spinel and twined ZSM-5 zeolite in methylation of benzene with carbon dioxide[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 856-866.

杨帆, 赵溢涛, 朱学栋, 王达锐. 三元尖晶石与孪晶ZSM-5分子筛在苯与二氧化碳甲基化中的应用[J]. 化工进展, 2025, 44(2): 856-866.

Figures/Tables 16

催化剂	苯转化率/%	产物选择性/%					芳环收率/%
催化剂	苯转化率/%	甲苯	二甲苯	乙苯	C₉₊重芳烃	对二甲苯/二甲苯	芳环收率/%
ZG/CZ5	37.1	75.5	18.4	2.5	3.6	25.1	97.1
ZA/CZ5	35.3	75.7	18.3	2.3	3.7	24.5	95.2
ZY/CZ5	22.5	89.4	8.4	1.3	0.9	26.2	95.8
ZC/CZ5	9.5	75.6	9.1	3.7	11.6	25.4	97.2
ZI/CZ5	1.2	51.7	37.2	0.8	10.3	27.2	98.6
ZF/CZ5	13.2	19.1	0.5	68.1	12.3	28.8	93.4
MG/CZ5	10.2	70.1	22.6	2.3	5.0	24.5	96.4
MA/CZ5	14.6	60.4	31.3	3.0	5.3	26.8	97.0

催化剂	CO₂转化率/%	产物选择性/%			$E_{C O_{2}}$ /%	C平衡
催化剂	CO₂转化率/%	CO	C₁~C₄低碳烃	乙苯和C₉₊重芳烃	$E_{C O_{2}}$ /%	C平衡
ZG/CZ5	34.2	51.5	11.3	10.2	28.4	96.8
ZA/CZ5	32.5	59.7	1.4	10.6	27.2	98.9
ZY/CZ5	30.0	69.1	8.1	2.3	19.1	97.3
ZC/CZ5	40.0	81.6	3.3	6.6	5.3	99.7
ZI/CZ5	21.1	87.2	9.1	1.3	1.6	92.3
ZF/CZ5	37.7	43.4	34.0	22.3	1.3	95.8
MG/CZ5	13.4	66.8	1.3	9.6	20.4	100.5
MA/CZ5	17.0	61.5	1.2	11.7	24.2	99.2

催化剂	CO₂转化率/%	产物选择性/%			$E_{C O_{2}}$ /%	C平衡
催化剂	CO₂转化率/%	CO	C₁~C₄低碳烃	乙苯和C₉₊重芳烃	$E_{C O_{2}}$ /%	C平衡
ZG/CZ5	34.2	51.5	11.3	10.2	28.4	96.8
ZA/CZ5	32.5	59.7	1.4	10.6	27.2	98.9
ZY/CZ5	30.0	69.1	8.1	2.3	19.1	97.3
ZC/CZ5	40.0	81.6	3.3	6.6	5.3	99.7
ZI/CZ5	21.1	87.2	9.1	1.3	1.6	92.3
ZF/CZ5	37.7	43.4	34.0	22.3	1.3	95.8
MG/CZ5	13.4	66.8	1.3	9.6	20.4	100.5
MA/CZ5	17.0	61.5	1.2	11.7	24.2	99.2

样品	比表面积/cm²·g^-1	平均孔径/nm	总孔体积/cm³·g^-1	体相组成（摩尔比）	表面组成（摩尔比）
ZA	184	8.72	0.40	Zn∶Al=1∶2.09	Zn∶Al=1∶1.88
ZGA	165	16.83	0.64	Zn∶Ga∶Al=1∶0.94∶0.96	Zn∶Ga∶Al=1∶0.91∶0.92
ZG	157	15.77	0.62	Zn∶Ga=1∶1.92	Zn∶Ga=1∶1.78

样品	比表面积/m²·g^-1	微孔面积/m²·g^-1	总孔体积/cm³·g^-1	微孔体积/cm³·g^-1	Si/Al
CZ5	357	148	0.28	0.11	151.2
TZ5	336	157	0.21	0.13	153.6

催化剂	苯转化率/%	产物选择性/%					芳环收率/%
催化剂	苯转化率/%	甲苯	二甲苯	乙苯	C₉₊重芳烃	对二甲苯/二甲苯	芳环收率/%
ZA/CZ5	35.3	75.7	18.3	2.3	3.7	24.5	95.2
ZGA/CZ5	42.4	72.0	22.4	1.5	4.1	25.6	95.6
ZG/CZ5	37.1	75.5	18.4	2.5	3.6	25.1	97.1
ZGA/TZ5	39.2	67.8	23.4	5.9	2.9	55.6	96.3

催化剂	CO₂转化率/%	产物选择性/%			$E_{C O_{2}}$ /%	C平衡
催化剂	CO₂转化率/%	CO	C₁~C₄低碳烃	乙苯和C₉₊重芳烃	$E_{C O_{2}}$ /%	C平衡
ZA/CZ5	32.5	59.7	1.4	10.6	27.2	98.9
ZGA/CZ5	35.1	54.2	2.1	11.2	32.6	100.7
ZG/CZ5	34.2	51.5	11.3	10.2	28.4	96.8
ZGA/TZ5	37.1	49.3	13.1	11.1	26.6	96.6

催化剂	CO₂转化率/%	产物选择性/%			$E_{C O_{2}}$ /%	C平衡
催化剂	CO₂转化率/%	CO	C₁~C₄低碳烃	乙苯和C₉₊重芳烃	$E_{C O_{2}}$ /%	C平衡
ZA/CZ5	32.5	59.7	1.4	10.6	27.2	98.9
ZGA/CZ5	35.1	54.2	2.1	11.2	32.6	100.7
ZG/CZ5	34.2	51.5	11.3	10.2	28.4	96.8
ZGA/TZ5	37.1	49.3	13.1	11.1	26.6	96.6

References 29

1	韩腾飞, 徐红, 葛晖, 等. 苯与合成气烷基化催化剂的研究进展[J]. 化工进展, 2020, 39(8): 3057-3065.
	HAN Tengfei, XU Hong, GE Hui, et al. Progress of alkylation catalysts for benzene with syngas[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3057-3065.
2	ZUO Jiachang, LIU Chong, HAN Xiaoqin, et al. Steering CO₂ hydrogenation coupled with benzene alkylation toward ethylbenzene and propylbenzene using a dual-bed catalyst system[J]. Chem Catalysis, 2022, 2(5): 1223-1240.
3	ZUO Jiachang, CHEN Weikun, LIU Jia, et al. Selective methylation of toluene using CO₂ and H₂ to para-xylene[J]. Science Advances, 2020, 6(34): eaba5433.
4	TING Kah Wei, KAMAKURA Haruka, POLY Sharmin S, et al. Catalytic methylation of aromatic hydrocarbons using CO₂/H₂ over Re/TiO₂ and H-MOR catalysts[J]. ChemCatChem, 2020, 12(8): 2215-2220.
5	SHANG Xin, LIU Guodong, SU Xiong, et al. Preferential synthesis of toluene and xylene from CO₂ hydrogenation in the presence of benzene through an enhanced coupling reaction[J]. ACS Catalysis, 2022, 12(21): 13741-13754.
6	LIU Xiangyu, PAN Yanling, ZHANG Peng, et al. Alkylation of benzene with carbon dioxide to low-carbon aromatic hydrocarbons over bifunctional Zn-Ti/HZSM-5 catalyst[J]. Frontiers of Chemical Science and Engineering, 2022, 16(3): 384-396.
7	CHENG Junjun, ZHAO Yitao, XU Guohao, et al. Zn _x Zr/HZSM-5 as efficient catalysts for alkylation of benzene with carbon dioxide[J]. Frontiers of Chemical Science and Engineering, 2023, 17(4): 404-414.
8	ZHAO Yitao, CHENG Junjun, ZHANG Peng, et al. Examination of key factors determining the catalytic performance of Zn-Ga/HZSM-5 bifunctional catalysts and establishment of reaction network in alkylation of benzene with carbon dioxide[J]. Applied Catalysis A: General, 2022, 643: 118785.
9	TING Kah Wei, KAMAKURA Haruka, POLY Sharmin S, et al. Catalytic methylation of m-xylene, toluene, and benzene using CO₂ and H₂ over TiO₂-supported Re and zeolite catalysts: Machine-learning-assisted catalyst optimization[J]. ACS Catalysis, 2021, 11(9): 5829-5838.
10	Vlasta MOHAČEK-GROŠEV, Martina VRANKIĆ, Aleksandar MAKSIMOVIĆ, et al. Influence of titanium doping on the Raman spectra of nanocrystalline ZnAl₂O₄ [J]. Journal of Alloys and Compounds, 2017, 697: 90-95.
11	JAIN Megha, Manju, KUMAR Ravi, et al. Defect states and kinetic parameter analysis of ZnAl₂O₄ nanocrystals by X-ray photoelectron spectroscopy and thermoluminescence[J]. Scientific Reports, 2020, 10(1): 385.
12	CHIKOIDZE Ekaterine, SARTEL Corinne, MADACI Ismail, et al. P-type ultrawide-band-gap spinel ZnGa₂O₄: New perspectives for energy electronics[J]. Crystal Growth & Design, 2020, 20(4): 2535-2546.
13	SHAN Guiye, WANG Shuang, FEI Xiaofang, et al. Heterostructured ZnO/Au nanoparticles-based resonant Raman scattering for protein detection[J]. The Journal of Physical Chemistry B, 2009, 113(5): 1468-1472.
14	XUE Zhenggang, CHENG Zhixuan, XU Jin, et al. Controllable evolution of dual defect Zn_i and V_O associate-rich ZnO nanodishes with (0001) exposed facet and its multiple sensitization effect for ethanol detection[J]. ACS Applied Materials & Interfaces, 2017, 9(47): 41559-41567.
15	LIU Fengjun, WANG Xinzhen, CHEN Xiaoyan, et al. Porous ZnO ultrathin nanosheets with high specific surface areas and abundant oxygen vacancies for acetylacetone gas sensing[J]. ACS Applied Materials & Interfaces, 2019, 11(27): 24757-24763.
16	WANG Chen, ZHANG Jianli, GAO Xinhua, et al. CO₂ hydrogenation to linear α-olefins on FeC _x /ZnO catalysts: Effects of surface oxygen vacancies[J]. Applied Surface Science, 2023, 641: 158543.
17	WANG Chuanfu, ZHANG Lei, HUANG Xin, et al. Maximizing sinusoidal channels of HZSM-5 for high shape-selectivity to p-xylene[J]. Nature Communications, 2019, 10(1): 4348.
18	KLINE Charles H, Jr, TURKEVICH John. The vibrational spectrum of pyridine and the thermodynamic properties of pyridine vapors[J]. The Journal of Chemical Physics, 1944, 12(7): 300-309.
19	CONNELL Glen, DUMESIC J A. Acidic properties of binary oxide catalysts: Ⅱ. Mössbauer spectroscopy and pyridine adsorption for iron supported on magnesia, alumina, and titania[J]. Journal of Catalysis, 1986, 102(1): 216-233.
20	EMEIS C A. Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J]. Journal of Catalysis, 1993, 141(2): 347-354.
21	YANG Yu, ZHANG Ping. Dissociation of H₂ molecule on the β-Ga₂O₃ (100)B surface: The critical role of oxygen vacancy[J]. Physics Letters A, 2010, 374(40): 4169-4173.
22	PAN Yunxiang, MEI Donghai, LIU Changjun, et al. Hydrogen adsorption on Ga₂O₃ surface: A combined experimental and computational study[J]. The Journal of Physical Chemistry C, 2011, 115(20): 10140-10146.
23	NYBERG Mats, NYGREN Martin A, PETTERSSON Lars G M, et al. Hydrogen dissociation on reconstructed ZnO surfaces[J]. The Journal of Physical Chemistry, 1996, 100(21): 9054-9063.
24	LING Yunjian, LUO Jie, RAN Yihua, et al. Atomic-scale visualization of heterolytic H₂ dissociation and CO _x hydrogenation on ZnO under ambient conditions[J]. Journal of the American Chemical Society, 2023, 145(41): 22697-22707.
25	BLEKEN Francesca Lønstad, CHAVAN Sachin, OLSBYE Unni, et al. Conversion of methanol into light olefins over ZSM-5 zeolite: Strategy to enhance propene selectivity[J]. Applied Catalysis A: General, 2012, 447/448: 178-185.
26	WESTGÅRD ERICHSEN Marius, SVELLE Stian, OLSBYE Unni. H-SAPO-5 as methanol-to-olefins (MTO) model catalyst: Towards elucidating the effects of acid strength[J]. Journal of Catalysis, 2013, 298: 94-101.
27	GOBIN O C, REITMEIER S J, JENTYS A, et al. Diffusion pathways of benzene, toluene and p-xylene in MFI[J]. Microporous and Mesoporous Materials, 2009, 125(1/2): 3-10.
28	YANG Fan, FANG Yuehua, LIU Xiangyu, et al. One-step alkylation of benzene with syngas over non-noble catalysts mixed with modified HZSM-5[J]. Industrial & Engineering Chemistry Research, 2019, 58(31): 13879-13888.
29	BREEN John, BURCH Robbie, KULKARNI Manisha, et al. Enhanced para-xylene selectivity in the toluene alkylation reaction at ultralow contact time[J]. Journal of the American Chemical Society, 2005, 127(14): 5020-5021.

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