无溶剂法合成ZSM-5/SiC整体式催化剂制备生物燃料

doi:10.1016/S1872-2067(20)63550-1

催化学报 ›› 2020, Vol. 41 ›› Issue (7): 1118-1124.DOI: 10.1016/S1872-2067(20)63550-1

无溶剂法合成ZSM-5/SiC整体式催化剂制备生物燃料

朱秋艳^a, 王叶青^a, 王凌翔^a, 杨志远^a, 王亮^b, 孟祥举^a, 肖丰收^a,b

a 浙江大学化学系, 浙江省应用化学重点实验室, 浙江杭州 310028;
b 浙江大学化工与生物工程学院, 教育部生物质化工工程重点实验室, 浙江杭州 310028

收稿日期:2019-09-29 出版日期:2020-07-18 发布日期:2020-04-18
通讯作者: 王叶青, 肖丰收
基金资助:
国家重点研发计划（2018YFD1000806-01）；国家自然科学基金（21822203，91645105，91634201）；浙江省自然科学基金（LR18B030002）；中央高校资助.

Solvent-free crystallization of ZSM-5 zeolite on SiC foam as a monolith catalyst for biofuel upgrading

Qiuyan Zhu^a, Yeqing Wang^a, Lingxiang Wang^a, Zhiyuan Yang^a, Liang Wang^b, Xiangju Meng^a, Feng-Shou Xiao^a,b

a Key Laboratory of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China;
b Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310028, Zhejiang, China

Received:2019-09-29 Online:2020-07-18 Published:2020-04-18
Supported by:
This work was supported by the National Key Research and Development Program of China (2018YFD1000806-01), National Natural Science Foundation of China (21822203, 91645105, 91634201), Natural Science Foundation of Zhejiang Province (LR18B030002), and the funding of central universities.

摘要/Abstract

摘要： 传统合成整块载体负载分子筛催化剂的方法是水热法,这样往往伴随水资源浪费和釜内空间利用率低的问题.本文报道了应用无溶剂法在蜂窝结构的碳化硅(SiC)表面原位生长ZSM-5分子筛.进一步采用该法将Pd纳米粒子限域在ZSM-5分子筛内,合成Pd@ZSM-5/SiC双功能催化剂,并在油酸甲酯加氢反应中表现出较高的活性和高碳烷烃选择性.结果发现,Pd@ZSM-5/SiC表现出高选择性和耐久性,这归因于SiC优异的传质和导热特性.
X射线衍射、扫描电子显微镜和氮气吸附等结果表明,通过无溶剂法合成的分子筛具有很高的结晶度和纯度；高分辨透射电镜结果表明,在Pd@ZSM-5和Pd@ZSM-5/SiC催化剂中,Pd纳米粒子均被良好封装,并且粒径无明显差别,因此排除金属活性中心粒径的干扰.
油酸甲酯的直接加氢脱氧/脱羧可以制备具有高附加值的长链碳氢化合物,而碳氢化合物的裂解通常会伴随着低碳化合物等副产物的生成.我们比较了两种催化剂在350–500℃的转化率和高碳烷烃的选择性差异.在相同反应条件下,Pd@ZSM-5/SiC催化剂上油酸甲酯转化率始终高于Pd@ZSM-5.例如在450℃,Pd@ZSM-5和Pd@ZSM-5/SiC的转化率分别为97.6%和78.2%,当温度提升至500℃,Pd@ZSM-5/SiC将油酸甲酯完全转化,而Pd@ZSM-5的转化率仅为88%.在350℃时,Pd@ZSM-5/SiC以脱羧反应为主,其中C₁₇和C₁₈的选择性分别为67.3%和20.1%,C_6-12和C_13-16选择性分别为2.4%和5.0%.相比之下,Pd@ZSM-5催化剂C₁₇的选择性为39.4%,C₁₈的选择性为13.2%,C_6-12和C_13-16选择性分别为20.2%和20.6%.由此可见,Pd@ZSM-5对于高附加值的长链碳氢化合物的选择性远低于Pd@ZSM-5/SiC;这可能与在Pd@ZSM-5催化剂上更容易发生烷烃裂解副反应有关.值得注意的是,虽然升高温度会促进碳氢化合物的裂解,但是在Pd@ZSM-5/SiC催化剂上高碳化合物依然较多.例如,在500℃时,裂解是Pd@ZSM-5催化剂上的主要反应,C_1-5的选择性高达50.1%,C_6-12的选择性高达37.0%;而在Pd@ZSM-5/SiC的产物中,C_13-16的选择性为40.0%,C₁₇-18的选择性更是高达16.7%.此外,在450℃的油酸甲酯加氢连续实验中,Pd@ZSM-5/SiC比Pd@ZSM-5表现出更好的耐久性,且催化剂失活后可以通过焙烧手段再生.
上述结果表明,Pd@ZSM-5/SiC催化剂有利于加氢脱氧/脱羧反应制备有价值的高碳烃产品,更能抑制裂解副反应的进行.相比之下,传统的粉末催化剂对裂解产物仍具有较高的选择性,尤其是在较高的反应温度下.SiC载体的引入有利于高碳产物的传质,从而抑制了裂解反应.此外,碳化硅良好的导热性可以有效地防止催化剂在反应中的过热,同样有利于抑制碳氢化合物的裂解.

关键词: 分子筛, Pd@ZSM-5/SiC, 整体式催化剂, SiC, 无溶剂法

Abstract: Conventional synthesis of monolith-supported zeolite catalysts is based on a hydrothermal strategy. Here, we report a solvent-free crystallization process to coat ZSM-5 zeolite crystals on a monolithic SiC foam with a honeycomb structure (ZSM-5/SiC). Characterizations of the ZSM-5/SiC by scanning electron microscopy, N₂ sorption, and X-ray diffraction indicate that the zeolite sheath has been ideally coated on the surface of the SiC foam with high purity and crystallinity. Fixing Pd nanoparticles within the ZSM-5 zeolite crystals delivers a bifunctional Pd@ZSM-5/SiC catalyst, which exhibits high activity and selectivity toward diesel range paraffins in the hydrodeoxygenation of methyl oleate, a model molecule for biofuel. In comparison to the powder Pd@ZSM-5, the Pd@ZSM-5/SiC monolith catalyst shows more efficiency, which is attributed to the fast mass transfer and high heat conductivity on the honeycomb SiC structure. The durability test indicates that the Pd@ZSM-5/SiC catalyst is stable under the reaction and high-temperature regeneration conditions.

Key words: Zeolite, Pd@ZSM-5/SiC, Monolith catalyst, SiC, Solvent-free

朱秋艳, 王叶青, 王凌翔, 杨志远, 王亮, 孟祥举, 肖丰收. 无溶剂法合成ZSM-5/SiC整体式催化剂制备生物燃料[J]. 催化学报, 2020, 41(7): 1118-1124.

Qiuyan Zhu, Yeqing Wang, Lingxiang Wang, Zhiyuan Yang, Liang Wang, Xiangju Meng, Feng-Shou Xiao. Solvent-free crystallization of ZSM-5 zeolite on SiC foam as a monolith catalyst for biofuel upgrading[J]. Chinese Journal of Catalysis, 2020, 41(7): 1118-1124.

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无溶剂法合成ZSM-5/SiC整体式催化剂制备生物燃料

Solvent-free crystallization of ZSM-5 zeolite on SiC foam as a monolith catalyst for biofuel upgrading

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