ZrO2晶相对ZnO/ZrO2+SAPO-34双功能催化剂上合成气制烯烃反应的影响

doi:10.1016/S1872-2067(21)63908-6

催化学报 ›› 2022, Vol. 43 ›› Issue (3): 877-884.DOI: 10.1016/S1872-2067(21)63908-6

ZrO₂晶相对ZnO/ZrO₂+SAPO-34双功能催化剂上合成气制烯烃反应的影响

刘朝鹏^a^,^b^,^c, 倪友明^a^,^b, 胡忠攀^a^,^b, 傅怡^a^,^b^,^c, 房旭东^a^,^b^,^c, 蒋齐可^a^,^b, 陈之旸^a^,^b, 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(筹), 辽宁大连 116023
^c中国科学院大学, 北京 100049

收稿日期:2021-06-18 修回日期:2021-06-18 出版日期:2022-03-18 发布日期:2022-02-18
通讯作者: 朱文良,刘中民
基金资助:
国家自然科学基金(21978285);国家自然科学基金(21991093);国家自然科学基金(21991090);中国科学院A类战略性先导科技专项课题(XDA21030100);大连高层次人才创新支持计划(2017RD07);国家高层次人才特殊支持计划(SQ2019RA2TST0016)

Insights into effects of ZrO₂ crystal phase on syngas-to-olefin conversion over ZnO/ZrO₂ and SAPO-34 composite catalysts

Zhaopeng Liu^a^,^b^,^c, Youming Ni^a^,^b, Zhongpan Hu^a^,^b, Yi Fu^a^,^b^,^c, Xudong Fang^a^,^b^,^c, Qike Jiang^a^,^b, Zhiyang Chen^a^,^b, 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:2021-06-18 Revised:2021-06-18 Online:2022-03-18 Published:2022-02-18
Contact: Wenliang Zhu, Zhongmin Liu
Supported by:
National Natural Science Foundation of China(21978285);National Natural Science Foundation of China(21991093);National Natural Science Foundation of China(21991090);Transformational Technologies for Clean Energy and Demonstration, Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21030100);Dalian High Level Talent Innovation Support Program(2017RD07);National Special Support Program for High Level Talents(SQ2019RA2TST0016)

摘要/Abstract

摘要：

烯烃是重要的化工原料, 目前主要通过石油催化裂化得到. 随着石油资源的消耗以及人们对烯烃需求的日益增长, 开发非石油路线制取烯烃势在必行. 合成气可以从煤、天然气和生物质等获得, 由合成气作为重要的C1平台分子一步制取烯烃(STO)的过程受到了广泛关注. 将合成气制甲醇/二甲醚的金属催化剂与甲醇制烯烃的分子筛催化剂耦合得到的混合双功能催化剂, 可以使合成气高选择性地转化为烯烃. 其中, ZnO/ZrO₂金属氧化物催化剂被广泛应于合成气的活化, 然而, 该金属氧化物结构对混合双功能催化剂上合成气制烯烃反应的影响尚不明确. 本文合成了单斜相ZrO₂ (m-ZrO₂)和四方相ZrO₂ (t-ZrO₂), 并负载ZnO制成催化剂, 再将其与SAPO-34分子筛物理混合得到混合双功能催化剂, 用于合成气制烯烃反应中. 在较优化的条件下, ZnO/m-ZrO₂与SAPO-34分子筛组成的双功能催化剂CO转化率为27.9%, 低碳烯烃选择性高达80.5%, 性能明显优于ZnO/t-ZrO₂+SAPO-34双功能催化剂.
为研究ZrO₂晶相对催化合成气制烯烃反应性能的影响, 对ZnO/ZrO₂进行红外光谱表征. 结果表明, ZnO/m-ZrO₂较ZnO/t-ZrO₂具有更多的表面羟基和更多的路易斯酸性位点. 金属氧化物表面的路易酸主要与催化剂表面不饱和的金属离子有关, 而且Zr基催化剂表面羟基有助于缺陷氧的形成, 因此, ZnO/m-ZrO₂催化剂表面应该具有更高浓度的氧缺陷位. 光电子能谱进一步证明了ZnO/m-ZrO₂表面有更高浓度的氧缺陷位. 另外, Zr基催化剂上表面羟基还有利于CO与其形成羧酸盐物种, 在623-673 K条件下的CO原位吸附的红外光谱表明, ZnO/m-ZrO₂催化剂上CO吸附的浓度及其表面羧酸盐浓度均明显高于ZnO/t-ZrO₂催化剂, 这与ZnO/m-ZrO₂表现出更好的催化合成气转化性能一致.
为了探究该催化剂体系上合成气制烯烃的反应路径, 分别对两种晶相的ZnO/ZrO₂和相应的双功能催化剂进行了原位红外监测. 与CO红外漫反射相比, 合成气氛围下金属氧化表面除了存在吸附态的CO和甲酸盐物种, 还存在表面甲氧基物种, 后者是合成气制甲醇/二甲醚过程重要的中间物种. 对合成气制烯烃过程中分子筛上的停留物种进行分析, 结果发现, 停留物种中含有多甲基苯、多甲基萘等甲醇制烯烃过程中的烃池物种. 另外, 合成气氛围下双功能催化剂甲氧基信号峰明显弱于金属氧化物表面甲氧基的信号强度, 表明STO过程应该是合成气制甲醇/二甲醚与甲醇制烯烃的串联过程.
综上所述, 在STO反应中, 相较于ZnO/t-ZrO₂催化剂, ZnO/m-ZrO₂催化剂具有更高浓度的表面羟基物种、路易斯酸密度和表面氧缺陷位, 从而有利于羧酸盐及甲氧基中间物种的形成, 进而提高了混合双功能催化剂催化STO反应性能.

关键词: 合成气制烯烃, 晶相, ZnO/ZrO₂, SAPO-34, 双功能催化剂

Abstract:

The utilization of metal oxide-zeolite catalysts in the syngas-to-olefin reaction is a promising strategy for producing C₂-C₄ olefins from non-petroleum resources. However, the effect of the crystal phase of metal oxides on the catalytic activity of these oxides is still ambiguous. Herein, typical metal oxides (ZnO/ZrO₂) with different crystal phases (monoclinic (m-ZrO₂) and tetragonal (t-ZrO₂)) were employed for syngas conversion. The (ZnO/m-ZrO₂+SAPO-34) composite catalyst exhibited 80.5% selectivity for C₂-C₄ olefins at a CO conversion of 27.9%, where the results are superior to those (CO conversion of 16.4% and C₂-C₄ olefin selectivity of 76.1%) obtained over (ZnO/t-ZrO₂+SAPO-34). The distinct differences are ascribed to the larger number of hydroxyl groups, Lewis acid sites, and oxygen defects in ZnO/m-ZrO₂compared to ZnO/t-ZrO₂. These features result in the formation of more formate and methoxy intermediate species on the ZnO/m-ZrO₂ oxides during syngas conversion, followed by the formation of more light olefins over SAPO-34. The present findings provide useful information for the design of highly efficient ZrO₂-based catalysts for syngas conversion.

Key words: Syngas-to-olefins, Crystal phase, ZnO/ZrO₂, SAPO-34, Composite catalyst

刘朝鹏, 倪友明, 胡忠攀, 傅怡, 房旭东, 蒋齐可, 陈之旸, 朱文良, 刘中民. ZrO₂晶相对ZnO/ZrO₂+SAPO-34双功能催化剂上合成气制烯烃反应的影响[J]. 催化学报, 2022, 43(3): 877-884.

Zhaopeng Liu, Youming Ni, Zhongpan Hu, Yi Fu, Xudong Fang, Qike Jiang, Zhiyang Chen, Wenliang Zhu, Zhongmin Liu. Insights into effects of ZrO₂ crystal phase on syngas-to-olefin conversion over ZnO/ZrO₂ and SAPO-34 composite catalysts[J]. Chinese Journal of Catalysis, 2022, 43(3): 877-884.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63908-6

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图/表 5

Table 1 Catalytic STO conversion over various composite catalysts.

Composite catalyst	CO conversion (%)	CO₂ selectivity (%)	Hydrocarbon distribution (%)
Composite catalyst	CO conversion (%)	CO₂ selectivity (%)	CH₄	C₂-C₄⁼	C₂-C₄^o	C₅₊
t-ZrO₂+SAPO-34	0.5	undetected	9.1	76.6	12.2	2.1
m-ZrO₂+SAPO-34	3.6	42.2	2.3	82.3	12.6	2.7
ZnO/t-ZrO₂+SAPO-34	14.6	44.2	2.4	79.4	16.4	1.8
ZnO/m-ZrO₂+SAPO-34	22.4	44.8	1.7	84.5	11.5	2.2

Fig. 1. Catalytic STO conversion over (ZnO/ZrO2+SAPO-34) composite catalysts. (a) Effect of reaction pressure (648 K, 2500 mL g-1 h-1, H2/CO molar ratio = 2/1); (b) effect of reaction temperature (1.5 MPa, 2500 mL g-1 h-1), H2/CO molar ratio = 2/1); stability of STO reactions over (ZnO/m-ZrO2+SAPO-34) (c) and (ZnO/t-ZrO2+SAPO-34) (d), (648 K, 1.5 MPa, 2500 mL g-1 h-1, H2/CO molar ratio = 2/1).

Fig. 2. Structural characterization. (a) XRD patterns; (b,c) HRTEM images of ZnO/m-ZrO2 and ZnO/t-ZrO2 catalysts; (d,e) elemental mapping of ZnO/m-ZrO2 and ZnO/t-ZrO2 catalysts.

Fig. 3. FT-IR and XPS data. (a) FTIR spectra of ZnO/ZrO2 catalysts; (b) O 1s XPS profiles of ZnO/ZrO2 catalysts; (c) FTIR spectra of ZnO/ZrO2 catalysts after pyridine adsorption and evacuation at 423 K; (d) DRIFTS profiles after CO adsorption at 643 K.

Fig. 4. In situ DRIFT spectra for syngas conversion over various catalysts. Reaction conditions: 648 K, 0.1 MPa, syngas refers to the mixed gas of CO/H2/Ar = 31.7/63.3/5.

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ZrO₂晶相对ZnO/ZrO₂+SAPO-34双功能催化剂上合成气制烯烃反应的影响

Insights into effects of ZrO₂ crystal phase on syngas-to-olefin conversion over ZnO/ZrO₂ and SAPO-34 composite catalysts

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