金属氧化物催化剂上合成气转化中羧酸盐物种促进芳烃的生成

doi:10.1016/S1872-2067(20)63691-9

催化学报 ›› 2021, Vol. 42 ›› Issue (5): 835-843.DOI: 10.1016/S1872-2067(20)63691-9

金属氧化物催化剂上合成气转化中羧酸盐物种促进芳烃的生成

陈之旸^a^,^b^,^c, 倪友明^a^,^b, 文富利^a^,^b^,^c, 周子乔^a^,^b^,^c, 朱文良^a^,^b^,^*(), 刘中民^a^,^b^,^c^,^#()

^a中国科学院大连化学物理研究所, 甲醇制烯烃国家工程实验室, 辽宁大连116023
^b中国科学院大连化学物理研究所, 洁净能源国家实验室, 辽宁大连116023
^c中国科学院大学, 北京100049

收稿日期:2020-06-02 接受日期:2020-06-02 出版日期:2021-05-18 发布日期:2021-01-29
通讯作者: 朱文良,刘中民
基金资助:
国家自然科学基金(21978285);中国科学院A类战略性先导科技专项课题(XDA21030100)

The carboxylates formed on oxides promoting the aromatization in syngas conversion over composite catalysts

Zhiyang Chen^a^,^b^,^c, Youming Ni^a^,^b, Fuli Wen^a^,^b^,^c, Ziqiao Zhou^a^,^b^,^c, Wenliang Zhu^a^,^b^,^*(), Zhongmin Liu^a^,^b^,^c^,^#()

^aNational Engineering Laboratory for Methanol to Olefins, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bDalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^cUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-06-02 Accepted:2020-06-02 Online:2021-05-18 Published:2021-01-29
Contact: Wenliang Zhu,Zhongmin Liu
About author:^# E-mail: liuzm@dicp.ac.cn
^* Tel/Fax: +86-411-84379418; E-mail: wlzhu@dicp.ac.cn;
Supported by:
National Natural Science Foundation of China(21978285);“Transformational Technologies for Clean Energy and Demonstration”, the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21030100)

摘要/Abstract

摘要：

芳烃是重要的化工原料, 目前主要通过石油催化裂化和催化重整制得. 随着石油资源的消耗以及芳烃的需求日益增长, 开发非石油路线制备芳烃势在必行. 因此, 从煤、天然气和生物质出发, 经合成气一步制芳烃(STA)广受关注. 将合成气制甲醇的金属催化剂和甲醇制芳烃的分子筛催化剂复合, 可以制备双功能催化剂, 用于合成气反应可高选择性得到芳烃. 然而, 关于此过程中芳烃的生成机理仍有争论. 目前人们认为, 生成芳烃的中间体主要分甲醇和其他含氧物种(乙烯酮, 醛类)两种. 本文以ZnCrAlO_x和H-ZSM-5为模型催化剂, 进行合成气制芳烃、甲醇制芳烃和丙烯制芳烃反应, 确定了传统的甲醇制芳烃路径不是合成气制芳烃中的主要途径, 并通过原位傅里叶变换红外光谱和气相色质谱解释了STA反应中两种活性组分距离越近, 芳烃选择性越高的原因, 从而提出了在合成气制芳烃过程中芳烃的生成机理.

通过比较双功能催化剂上合成气、甲醇以及丙烯的反应性能发现, 在甲醇和丙烯转化时, 其芳烃选择性远小于合成气转化时的, 由此可认为, 在合成气制芳烃的路径主要不经由传统的甲醇制芳烃, 而是通过烯烃聚合脱氢生成芳烃.

红外表征和共进料实验表明, 合成气可以在金属催化剂表面生成甲酸盐物种, 它可与烯烃反应生成羧酸盐物种, 再迁移到分子筛上反应生成芳烃, 且羧酸盐物种在分子筛上的芳构化能力要高于丙烯; 即使在氢气氛围下, 当丙烯的芳构化能力受到氢气极大抑制时, 羧酸盐物种仍能高选择性生成芳烃.

本文制备了一系列金属催化剂和分子筛物理接近距离不同的双功能催化剂, 研究了合成气在双功能催化剂上制芳烃时, 金属催化剂和分子筛二者组分的距离对芳烃选择性的影响. 随着二者接近距离的增加, 芳烃选择性急剧增加; 通过GC-MS分析合成气转化时的停留物种, 发现随着二者接近距离的增加,羧酸盐物种和甲基环戊烯酮的量明显增加, 因此, 羧酸盐物种和甲基环戊烯酮物种在生成芳烃中起到了重要的作用.

综上所述, 我们提出了STA中一条新的芳烃生成路径, 并证明了羧酸盐物种是其中重要的中间物种. 它经由金属表面的甲酸盐物种和烯烃反应生成, 随后迁移到分子筛上生成甲基环戊烯酮物种, 再脱水生成芳烃.

关键词: 羧酸盐, 合成气制芳烃, 复合催化剂, ZnCrAlO_x, H-ZSM-5

Abstract:

Syngas to aromatics (STA) over bifunctional catalysts has attracted much attention in recent years, but the mechanism underlying the formation of aromatics remains controversial. The critical reaction intermediates, carboxylates, were first identified and then confirmed to essentially promote aromatization in the syngas conversion over a ZnCrAlO_x&H-ZSM-5 composite catalyst. This study provides evidence that the carboxylates can be formed during the reactions of formate species and olefins. In addition, it is shown that the carboxylates favor the formation of aromatics over H-ZSM-5 even in the presence of H₂. A novel mechanism for the formation of aromatics via the generation and transformation of carboxylate intermediates is proposed, and the transformation of carboxylates to aromatics via methyl-2-cyclopenten-1-one (MCPO) intermediates is indeed likely. A better understanding of the formation mechanism of aromatics would help optimize the composite catalyst.

Key words: Carboxylates, Syngas-to-aromatics, Composite catalysts, ZnCrAlO_x, H-ZSM-5

陈之旸, 倪友明, 文富利, 周子乔, 朱文良, 刘中民. 金属氧化物催化剂上合成气转化中羧酸盐物种促进芳烃的生成[J]. 催化学报, 2021, 42(5): 835-843.

Zhiyang Chen, Youming Ni, Fuli Wen, Ziqiao Zhou, Wenliang Zhu, Zhongmin Liu. The carboxylates formed on oxides promoting the aromatization in syngas conversion over composite catalysts[J]. Chinese Journal of Catalysis, 2021, 42(5): 835-843.

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图/表 12

Fig. 1. Comparison of catalytic results for syngas and methanol conversion. (a) Syngas conversion over various composite catalysts. Space velocity = 2000 (only for ZnCrAlOx) or 1500 (for other catalysts) mL g-1 h-1, 4.0 MPa, H2/CO/Ar = 47.5:47.5:5, 633 K , time on stream = 3 h. Note that C5+ excludes aromatics; ZnCrAlOx&H-ZSM-5 prepared by grinding; ZnCrAlOx+H-ZSM-5 prepared by mixing granules; ZnCrAlOx/H-ZSM-5 denoted as dual-bed catalysts. (b) Methanol conversion over H-ZSM-5 and ZnCrAlOx&H-ZSM-5 in various atmospheres. Space velocity = 6000 (for H-ZSM-5) and 1500 (for ZnCrAlOx&H-ZSM-5) mL g-1 h-1, liquid MeOH flow rate: 0.004 mL min-1, 633 K, 4.0 Mpa, time on stream = 3 h. N2+H2 denotes N2/H2/MeOH = 4:4:1, N2 denotes N2/MeOH = 8:1, CO+H2 denotes CO/H2/MeOH = 4:4:1, N2+CO denotes N2/CO/MeOH = 4:4:1.

Fig. 2. Relationship between lower olefins and aromatics during the reactions. (a) Effect of space velocity on the formation of lower olefins and aromatics in syngas conversion over ZnCrAlOx&H-ZSM-5. 4.0 MPa, H2/CO/Ar = 47.5:47.5:5, 633 K, time on stream = 4 h. (b) Conversion of propene over various catalysts in CO. Reaction conditions: 633 K, 4 MPa, CO:He:C3H6 = 20:19:1, space velocity = 6000 (for H-ZSM-5) and 1500 (for other catalysts) mL h-1 g-1, time on stream = 4 h.

Fig. 3. In situ DRIFT spectra for the conversion of CO and C3H6 over ZnCrAlOx (a) and ZnCrAlOx&H-ZSM-5 (b). Reaction conditions: 0.1 MPa, 573 K, CO = 5 mL min-1, C3H6 (5%C3H6+95% N2) = 5 mL min-1.

Fig. 4. Identification of carboxylates. (a) GC-MS profiles of products for the conversion of the mixture of CO, H2, ethanol and C3H6 over ZnCrAlOx. Catalyst mass = 0.3 g, space velocity = 2000 mL min-1, CO/H2/EtOH/C3H6 (molar ratio) = 42.5:42.5:13.0:7.0, 0.1 MPa, 573 K. (b) DRIFT spectra of zinc methacrylate as stand reference.

Fig. 5. Investigation of the role of carboxylates in the formation of aromatics via the STA reaction. (a) Effect of co-feeding methyl crotonate with C3H6 over H-ZSM-5 in N2 atmosphere. 633 K, 0.1 Mpa, space velocity = 1500 ml h-1 gcat-1, time on stream = 2 h. (b) Comparisons of propene and carboxylates conversions over H-ZSM-5 in N2 or H2. 1.0 MPa, 633 K, ratio of N2 or H2/C3H6 to methyl crotonate or methyl butyrate = 81 (on a carbon basis), time on stream = 2 h.

Fig. 6. The effect of the proximity of oxide and zeolite on the acidic property of H-ZSM-5 and the formation of retained organics. (a) FTIR subtraction relative to adsorption of DTBPy. (b) GC-MS chromatograms of retained organics in various catalysts after syngas conversion. Space velocity = 1500 mL g-1 h-1, 4.0 MPa, H2/CO/Ar = 47.5/47.5/5, 633 K, time on stream = 1 min. Peak numbers correspond to compounds listed in Table S1.

Scheme 1. Proposed mechanism of the STA reaction over a composite catalyst. M denotes ZnCrAlOx; R, R1, and R2 denote H and alkyl groups.

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金属氧化物催化剂上合成气转化中羧酸盐物种促进芳烃的生成

The carboxylates formed on oxides promoting the aromatization in syngas conversion over composite catalysts

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