基于金属有机骨架和稻谷壳前体构筑ZnZrO x &bio-SAPO-34双功能催化剂及CO2加氢制低碳烯烃

doi:10.16085/j.issn.1000-6613.2021-2028

摘要/Abstract

摘要：

CO₂过量排放导致全球气候异常，通过CO₂催化加氢将CO₂转化为具有高附加值的基础化学品或燃料是实现碳循环的有效方式，同时也有助于实现我国的“碳中和”目标。本文报道了基于稻谷壳前体制备具有多层次、相互贯通的介孔及大孔结构的bio-SAPO-34分子筛，该结构有利于反应过程中反应中间体的传质。本文系统地研究了分子筛前体液浓度、微孔导向剂种类及浓度、生物模板加入量等因素对bio-SAPO-34合成过程中维持生物模板分级结构的影响规律。将bio-SAPO-34与ZnZrO _x 固溶体氧化物组装构筑ZnZrO _x &bio-SAPO-34双功能催化剂用于催化CO₂加氢制备低碳烯烃反应。在380℃、3MPa的反应条件下，双功能催化剂的CO₂转化率为11.8%，低碳烯烃的选择性为66.4%（占烃类产物），且经过连续反应60h后未发现催化剂明显失活。

关键词: 二氧化碳, 生物模板, 分子筛, 催化, 还原

Abstract:

The excessive emission of greenhouse gas CO₂ has caused global climate change. Catalytic conversion of CO₂via hydrogenation is a promising route for the achievement of carbon circular economy and carbon neutralization target. In this study, the bio-SAPO-34 with multiple meso- and macro- structures was synthesized by using rice husk as the bio-template. The hierarchical structure of bio-SAPO-34 facilitated the diffusion of reaction intermediates and improved the catalytic activity. The effect of synthesis parameters such as precursor concentration, structure-directing agent and the amount of rice husks on the replication the architecture of rice husks biotemplate have been systematically studied. Moreover, the ZnZrO _x was composited with bio-SAPO-34 to form ZnZrO _x &bio-SAPO-34 bifunctional catalyst for CO₂ hydrogenation to light olefins. Under reaction conditions of 380℃ and 3MPa, the selectivity of low olefins was 66.4% (in hydrocarbon products) with a CO₂ conversion of 11.8%. Furthermore, the obtained ZnZrO _x &bio-SAPO-34 bifunctional catalysts showed excellent stability in a 60h long-term test.

Key words: carbon dioxide, biotemplating, molecular sieves, catalysis, reduction

中图分类号:

TQ013

李雯, 詹国武, 黄加乐, 李清彪. 基于金属有机骨架和稻谷壳前体构筑ZnZrO _x &bio-SAPO-34双功能催化剂及CO₂加氢制低碳烯烃[J]. 化工进展, 2022, 41(3): 1298-1308.

LI Wen, ZHAN Guowu, HUANG Jiale, LI Qingbiao. Synthesis of ZnZrO _x &bio-SAPO-34 bifunctional catalysts derived from metal organic frameworks and rice husk template for CO₂ hydrogenation to light olefins[J]. Chemical Industry and Engineering Progress, 2022, 41(3): 1298-1308.

图/表 9

图1 基于稻谷壳制备bio-SAPO-34的流程图

图2 com-SAPO-34样品的照片和SEM图以及bio-SAPO-34样品的照片、SEM图和EDX元素面扫图

图3 不同合成条件所制备样品的XRD图与SEM图（非最优合成条件）

图4 不同合成反应条件下所制备的bio-SAPO-34样品的XRD谱图

图5 不同RH/Al所合成样品的SEM图

图6 com-SAPO-34及bio-SAPO-34的孔结构表征[图(c)、(d)中黑线代表累计入汞量；红线为大孔孔径分布曲线]

图7 com-SAPO-34及bio-SAPO-34的酸性表征

图8 反应温度对ZnZrO x &bio-SAPO-34催化活性的影响与ZnZrO x &bio-SAPO-34稳定性评价结果（60h）

图9 双功能催化剂中金属氧化物和分子筛的亲密度研究a—单独ZnZrO x 床层；b—ZnZrO x 与bio-SAPO-34上下双床层叠放；c—ZnZrO x 与bio-SAPO-34及石英砂三者研磨混合；d—ZnZrO x 与bio-SAPO-34粉末通过研钵研磨混合；e—ZnZrO x 与bio-SAPO-34研磨压片混合

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基于金属有机骨架和稻谷壳前体构筑ZnZrO _x &bio-SAPO-34双功能催化剂及CO₂加氢制低碳烯烃

Synthesis of ZnZrO _x &bio-SAPO-34 bifunctional catalysts derived from metal organic frameworks and rice husk template for CO₂ hydrogenation to light olefins

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