链状ZSM-5分子筛耦合Cu-Fe3O4用于CO2加氢制轻质芳烃

徐祥龙; 文承彦; 金科; 林溢琦; 马隆龙; 王晨光

doi:10.1016/S1872-5813(22)60017-3

链状ZSM-5分子筛耦合Cu-Fe₃O₄用于CO₂加氢制轻质芳烃

doi: 10.1016/S1872-5813(22)60017-3

徐祥龙^{1, #,},
文承彦^{1, #},
金科^{2, 3, 4},
林溢琦⁵,
马隆龙^1, ,,
王晨光^{2, 3, 4, ,}

1.
东南大学能源与环境学院，江苏南京 210009
2.
中国科学院广州能源研究所，广东广州 510640
3.
中国科学院可再生能源重点实验室，广东广州 510640
4.
广东省新能源和可再生能源研究开发与应用重点实验室，广东广州 510640
5.
郑州大学化工学院，河南郑州 450001

基金项目: 广东省重点领域研发计划（2020B1111570001），江苏省研究生科研与实践创新计划（KYCX20_0095）和中央高校基本科研业务费专项资金（3203002104D）资助

详细信息

通讯作者:
Tel：13829724756，13825023727，E-mail：mall@seu.edu.cn

wangcg@ms.giec.ac.cn

共同第一作者
中图分类号: TK6
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出版历程
- 收稿日期: 2022-01-26
- 修回日期: 2022-03-19
- 录用日期: 2022-04-12
- 网络出版日期: 2022-05-11
- 刊出日期: 2022-10-21

Chain-like ZSM-5 zeolite coupled with Cu-Fe₃O₄ for CO₂ hydrogenation to light aromatics

XU Xiang-long^{1, #
,},
WEN Cheng-yan^{1, #},
JIN Ke^{2, 3, 4},
LIN Yi-qi⁵,
MA Long-long^{1
, ,},
WANG Chen-guang^{2, 3, 4
, ,}

1.
Southeast University, School of Energy and Environment, Nanjing 210009, China
2.
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
3.
Key Laboratory of Renewable Energy, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
4.
Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China
5.
Zhengzhou University, Chemical Engineering College, Zhengzhou 450001, China

Funds: The project was supported by R&D Plan of Key Fields in Guangdong Province (2020B1111570001), Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX20_0095) and the Fundamental Research Funds for the Central Universities （3203002104D）

摘要

摘要: 近年来，二氧化碳（CO₂）的捕获与利用受到广泛关注，尤其CO₂加氢直接制轻质芳烃（如苯、甲苯和二甲苯等）已被当作一条具有潜力的化学品生产路线，但有效调控芳烃产物分布及提高目标芳烃选择性仍是一个巨大的挑战。在此，本研究提供了一种由铜改性铁基催化剂耦合链状ZSM-5分子筛组成的双功能催化剂用于CO₂加氢一步高效制备轻质芳烃。采用了XRD、SEM、TEM、ICP-AES、Py-FTIR和N₂吸附-脱附等表征手段对双功能催化剂组分进行了分析，研究了分子筛酸密度和长径比（即b轴/a轴）对芳烃选择性及分布的影响。结果表明，具有高酸密度及适当长径比的链状ZSM-5分子筛能促进产物的C−C偶联并抑制CH₄的生成，从而有效提高芳烃的选择性及甲苯的时空收率（STY）。
- 二氧化碳加氢 /
- 芳烃 /
- ZSM-5 分子筛 /
- Cu-Fe₃O₄ /
- 双功能催化剂
Abstract: The capture and utilization of carbon dioxide (CO₂) have attracted much attention in recent years; in particular, the direct hydrogenation of CO₂ to light aromatics has been considered as a potential route to produce high value-added chemicals. However, it is still a big challenge to adjust the aromatic distribution and achieve a high selectivity to the targeted products. In this work, a bifunctional catalyst that combines the Cu-modified Fe₃O₄ and the chain-like ZSM-5 zeolite is used for the hydrogenation of CO₂ to light aromatics. The catalyst components were characterized by XRD, SEM, TEM, ICP-AES, Py-IR and N₂ adsorption-desorption; the effect of acid density and length-to-diameter ratio (b-axis/ a-axis) of zeolite moiety on the selectivity and distribution of aromatic products was then investigated. The results indicate that the chain-like ZSM-5 zeolite moiety with high acid density and appropriate length-to-diameter ratio can promote the C–C coupling for CO₂ hydrogenation and inhibit the formation of CH₄, which can improve the selectivity to aromatics and the space time yield (STY) of toluene.
- carbon dioxide hydrogenation /
- aromatics /
- ZSM-5 zeolite /
- Cu-Fe₃O₄ /
- bifunctional catalyst
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1) 共同第一作者

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FIG. 1882. FIG. 1882.

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图 1 不同长径比的CZ5和Cu-Fe₃O₄的XRD谱图

Figure 1 XRD patterns of the Cu-Fe₃O₄ catalyst and various ZSM-5 zeolites

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图 2 Cu-Fe₃O₄的(a) SEM、((b)、(c)) TEM和(d-f) EDS-mapping照片

Figure 2 SEM image (a), TEM images ((b), (c)) and EDS-mapping ((d)–(f)) of the Cu-Fe₃O₄ catalyst

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图 3 不同链长的CZ5的SEM和TEM照片以及b轴长度分布

Figure 3 SEM and TEM images and b-axis length distributions of zeolite samples: ((a1), (a2)) CZ5-3.7; ((b1), (b2)) CZ5-2.9; ((c1), (c2)) CZ5-1.7 and ((d1), (d2)) CZ5-0.6

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图 4 CZ5样品在77 K下N₂吸附-脱附等温曲线

Figure 4 N₂ adsorption-desorption isotherms of various CZ5 zeolites

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图 5 CZ5样品于350 ℃时的吡啶红外吸附谱图

Figure 5 FT-IR spectra of various CZ5 samples collected at 350 ℃

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图 6 催化剂的CO₂加氢反应性能

Figure 6 Performance of various bifunctional catalysts in CO₂ hydrogenation

(a): hydrocarbon distribution, CO₂ conversion, and CO selectivity; (b): the relative content in products and STY of BTX

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图 7 不同氛围下甲苯在BTX中相对占比随长径比的变化

Figure 7 Content of toluene in BTX for the aromatization over CZ-5 zeolites with different length-to-diameter ratio under different atmospheres (a): propene; (b): 1-octene; (c): CO₂/H₂

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表 1 CZ5样品物理化学性质

Table 1 Physicochemical properties of various CZ5 zeolite samples

Catalyst	Si/Al*	Lewis acidity/（μmol·g⁻¹）	Brønsted acidity/（μmol·g⁻¹）	Total acidity/ （μmol·g⁻¹）	S_BET /(m²·g⁻¹)
CZ5-0.6-41.8	165	9.1	32.7	41.8	−
CZ5-0.6-44.7	83	5.2	39.5	44.7	398.8
CZ5-0.6-61.0	61	8.8	52.2	61.0	−
CZ5-1.7-52.4	88	4.3	48.1	52.4	377.6
CZ5-2.9-59.5	85	3.1	56.4	59.5	376.3
CZ5-3.7-28.7	90	2.3	26.5	28.7	369.7
*Calculated from ICP-AES

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