苯和环己烯分步制联环己烷过程催化剂设计及性能提升研究

刘瑞林; 王森; 孟繁春; 李卓; 杨慧敏; 赵世超; 覃勇; 张斌

doi:10.1016/S1872-5813(24)60457-3

苯和环己烯分步制联环己烷过程催化剂设计及性能提升研究

doi: 10.1016/S1872-5813(24)60457-3

刘瑞林^{1, 2,},
王森^{1, 2,},
孟繁春^{1, 2,},
李卓^{1, 2,},
杨慧敏^{1, 2,},
赵世超^{1, 2,},
覃勇^{1, 2,},
张斌^{1, 2, ,}

1.
中国科学院山西煤炭化学研究所煤炭高效低碳利用全国重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 10049

基金项目: 国家自然科学基金 (22072172，22202227)，国家杰出青年科学基金（21825204），中国科学院青年创新促进会（Y2021056），榆林学院与大连清洁能源国家实验室合作基金（YLU-DNL Fund 2022007）和山西省科技创新团队专项资金（202304051001007）资助

详细信息

通讯作者:
Tel: 0351-4040420 , E-mail: zhangbin2009@sxicc.ac.cn

中图分类号: O643
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出版历程
- 收稿日期: 2024-03-14
- 修回日期: 2024-04-04
- 录用日期: 2024-04-07
- 网络出版日期: 2024-05-21

The study of design and performance improvement of catalysts for the stepwise production of bicyclohexane from benzene and cyclohexene

LIU Ruilin^{1, 2
,},
WANG Sen^{1, 2
,},
MENG Fanchun^{1, 2
,},
LI Zhuo^{1, 2
,},
YANG Huimin^{1, 2
,},
ZHAO Shichao^{1, 2
,},
QIN Yong^{1, 2
,},
ZHANG Bin^{1, 2
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds: The project was supported by National Natural Science Foundation of China (22072172、22202227), National Science Fund for Distinguished Young Scholars (21825204), the Youth Innovation Promotion Association CAS (Y2021056), Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (YLU-DNL Fund 2022007), the special fund for Science and Technology Innovation Teams of Shanxi Province (202304051001007).

摘要

摘要: 联环己烷是一种高储氢密度、低沸点储氢试剂。与联苯加氢相比，苯和环己烯烷基化制环己基苯再加氢是一种有望实现大规模制备联环己烷的途径。在成熟的烷基化技术基础上，需进一步开展高效环己基苯加氢催化剂的研发。本研究首先使用酸化的USY分子筛催化苯和环己烯烷基化至环己基苯，获得100%转化率和产物选择性。进一步通过原子层沉积（ALD）在γ-Al₂O₃表面预先沉积不同厚度的TiO₂膜后再负载铂颗粒制得Pt/TiO₂/γ-Al₂O₃催化剂，研究TiO₂膜提升催化剂环己基苯加氢性能机制。TEM、CO脉冲吸附、CO-DRIFTs、准原位XPS、H-D交换和H₂-TPR表征显示，与Pt/γ-Al₂O₃相比，Pt/TiO₂/γ-Al₂O₃催化剂不改变Pt颗粒的分散度，但能够形成新的Pt-TiO₂相互作用，提高铂表面电子密度、平面活性位点比例和降低氢溢流能垒，提升环己烷基苯加氢性能。研究为进一步发展联环己烷有机液态储氢试剂提供理论支持。相关金属-载体相互作用调控策略可应用于其他芳香性分子高效加氢催化剂的研制。
- 有机液态储氢 /
- 联环己烷 /
- 加氢 /
- 金属载体相互作用 /
- 原子层沉积
Abstract: Bicyclohexane is a hydrogen storage reagent with high hydrogen density and low boiling point. Compared with the hydrogenation of biphenyl, the alkylation of benzene and cyclohexene to cyclohexylbenzene and hydrogenation is a promising way to prepare cyclohexane on a large scale. The research and development of high-efficiency cyclohexyl benzene hydrogenation catalyst should be further developed based on mature alkylation technology. This paper used an acidified USY molecular sieve to catalyze the alkylation of benzene and cyclohexene to cyclohexylbenzene, which achieved 100% conversion and selectivity. Furthermore, Pt/TiO₂/γ-Al₂O₃ catalyst is prepared by pre-deposition TiO₂ film of different thicknesses on γ-Al₂O₃ surface and then supported with platinum particles by Atomic layer deposition (ALD). The role of TiO₂ film in improving the cyclohexylbenzene hydrogenation performance of the catalyst is studied. TEM、CO pulse chemisorption, CO-DRIFTs, quasi-in situ XPS, H-D exchange, and H₂-TPR characterization show that compared with Pt/γ-Al₂O₃, TiO₂ thin films on Pt/TiO₂/γ-Al₂O₃ do not change the dispersion of Pt particles, but can form new Pt-TiO₂ interactions. The hydrogenation performance of cyclohexylbenzene was improved by increasing the electron density and the proportion of planar active sites on the surface of platinum and reducing the energy barrier of hydrogen spillover. The research provides theoretical support for further bicyclohexane organic liquid hydrogen storage reagent development. The relevant metal-support interaction regulation strategy can be applied to the development of efficient catalysts for other aromatic molecules hydrogenation.
- organic liquid hydrogen storage /
- bicyclohexane /
- hydrogenation /
- metal-support interaction /
- atomic layer deposition

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图 1 （a）不同催化剂上环己基苯加氢制联环己烷性能；（b） Pt/30TiO₂/γ-Al₂O₃催化剂稳定性测试（反应条件：1.5 mL环己基苯，5 mL正庚烷，20 mg催化剂，反应温度50 ℃，3 MPa H₂，反应时间1 h）

Figure 1 (a) Catalytic performance of different catalysts for cyclohexylbenzene hydrogenation, (b) Stability test of Pt/30TiO₂/γ-Al₂O₃

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图 2 （a） Pt/γ-Al₂O₃、（b） Pt/10TiO₂/γ-Al₂O₃、（c）、（d） Pt/30TiO₂/γ-Al₂O₃的TEM图像

Figure 2 TEM image of Pt/γ-Al₂O₃ (a), Pt/10TiO₂/γ-Al₂O₃ (b), Pt/30TiO₂/γ-Al₂O₃ (c), (d)

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图 3 Pt/γ-Al₂O₃和Pt/nTiO₂/γ-Al₂O₃催化剂的Pt 4d XPS谱图（a）；还原后催化剂的Pt 4d XPS图谱（b）；还原后Pt/nTiO₂/γ-Al₂O₃催化剂的Ti 2p XPS谱图（c）

Figure 3 Pt 4d XPS spectra of Pt/γ-Al₂O₃ and Pt/nTiO₂/γ-Al₂O₃ (a), Pt 4d XPS spectra of reduced catalysts (b), Ti 2p XPS spectra of reduced Pt/nTiO₂/γ-Al₂O₃ catalysts (c)

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图 4 （a） Pt/γ-Al₂O₃和Pt/nTiO₂/γ-Al₂O₃催化剂的CO-DRIFTS谱图；（b）拟合结果归一化后不同峰所占的比例

Figure 4 CO-DRIFTS of Pt/γ-Al₂O₃ and Pt/nTiO₂/γ-Al₂O₃ catalysts, (b) The proportion of different peaks after the normalization of fitting results

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图 5 （a） Pt/γ-Al₂O₃的H-D交换红外光谱谱图；（b） Pt/30TiO₂/γ-Al₂O₃的H-D交换红外光谱谱图；（c） Pt/γ-Al₂O₃和Pt/nTiO₂/γ-Al₂O₃催化剂的H-D交换速率对比

Figure 5 (a) FT-IR spectra of the Pt/γ-Al₂O₃ during H-D exchange, (b) IR spectra of the Pt/30TiO₂/γ-Al₂O₃ during H-D exchange, (c) H-D exchange rates of Pt/γ-Al₂O₃ and Pt/nTiO₂/γ-Al₂O₃ catalysts

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图 6 （a） Pt/γ-Al₂O₃和Pt/nTiO₂/γ-Al₂O₃催化剂H₂-TPR谱图；（b）不同温度H₂消耗量对比

Figure 6 (a) H₂-TPR and (b) H₂ consumption at different temperatures for Pt/γ-Al₂O₃ and Pt/nTiO₂/γ-Al₂O₃ catalysts

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表 1 不同催化剂的苯和环己烯烷基化反应性能

Table 1 Catalytic performance of different catalysts for alkylation of benzene and cyclohexene

Samples	Si/Al ratio	Conversion/%	Selectivity/%
Samples	Si/Al ratio	Conversion/%	cycloxylbenzene	1-methyclopentylbenzene
Hβ	5.4	0	—	—
HY	5	0	—	—
Dry CT-275 ion-exchange resins	—	100	84	16
USY	13−17	0	—	—
Dry USY	13−17	55.4	100	—
Acidified USY	13−17	100	100	—
Reaction conditions: 4.6 mmol cyclohexene, 4mL benzene, 150 mg catalyst, 150 ℃ reaction temperature, 3MPa N₂, 4 h reaction time.

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表 2 不同催化剂Pt和Ti元素负载量、分散度、Pt颗粒尺寸

Table 2 Pt and Ti loading, dispersion and Pt particle diameter of different catalysts

Sample	Loading/%^a		Dispersion/%^b	d_TEM/nm^c
Sample	Pt	Ti	Dispersion/%^b	d_TEM/nm^c
Pt/γ-Al₂O₃	9.2	−	19.4	1.6±0.3
Pt/10TiO₂/γ-Al₂O₃	15.4	2.1	19.1	2.0±0.3
Pt/20TiO₂/γ-Al₂O₃	16.0	4.2	15.9	1.9±0.3
Pt/30TiO₂/γ-Al₂O₃	17.8	6.5	16.2	2.3±0.4
Pt/40TiO₂/γ-Al₂O₃	18.3	7.8	15.1	2.0±0.3
Note: ^a: ICP-OES results; ^b: CO pulse adsorption; ^c: TEM particle size distribution statistics.

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