Zn-Zr-Al氧化物催化乙醇合成碳酸二乙酯

doi:10.1016/S1872-2067(19)63318-8

催化学报 ›› 2019, Vol. 40 ›› Issue (4): 515-522.DOI: 10.1016/S1872-2067(19)63318-8

Zn-Zr-Al氧化物催化乙醇合成碳酸二乙酯

张健, 阎婷婷, 杨宇森, 孙嘉略, 林彦军, 卫敏

北京化工大学, 化工资源有效利用国家重点实验室, 北京软物质科学与工程高精尖创新中心, 北京 100029

收稿日期:2018-10-29 修回日期:2019-01-05 出版日期:2019-04-18 发布日期:2019-03-14
通讯作者: 林彦军, 卫敏
基金资助:
国家重大研发计划（2017YFA0206804）；国家自然科学基金（21871021，21521005）；中央高校基础研究基金（buctylkxj01，XK1802-6）.

Zn-Zr-Al oxides derived from hydrotalcite precursors for ethanol conversion to diethyl carbonate

Jian Zhang, Tingting Yan, Yusen Yang, Jialue Sun, Yanjun Lin, Min Wei

State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2018-10-29 Revised:2019-01-05 Online:2019-04-18 Published:2019-03-14
Supported by:
This work was supported by the National Key R&D Program (2017YFA0206804), the National Natural Science Foundation of China (21871021, 21521005), and the Fundamental Research Funds for the Central Universities (buctylkxj01, XK1802-6)

摘要/Abstract

摘要：

乙醇作为一种重要的可再生平台化学品，其高值转化已引起研究者的广泛关注.碳酸二乙酯（DEC）是乙醇转化的重要衍生物，作为合成中间体、绿色溶剂和燃油添加剂，具有低毒、无污染的优点.目前，以乙醇为底物合成DEC主要有以下方法：光气法、氧化羰基化法、酯交换法和尿素醇解法.其中，尿素醇解法因成本低、操作简便、产物易分离等优点而备受关注，包括两个连续过程：乙醇和尿素反应生成中间体氨基甲酸乙酯（EC），EC与乙醇进一步反应生成DEC.本文采用水滑石（Zn₂Zr_xAl-LDH）为前体，经结构拓扑转变制备了一系列酸碱双功能金属氧化物催化剂（Zn₂Zr_xAl-MMO），用于催化乙醇合成DEC.通过改变LDHs前体元素比例调控氧化物的酸碱性质和催化性能，最优催化剂Zn₂Zr_0.1Al-MMO对产物DEC产率达到42.1%，为目前报道的金属氧化物催化剂的最高产率.
CO₂-TPD和NH₃-TPD结果表明，随着Zr含量的增加，催化剂的总碱性位点（B_TOTAL）和总酸性位点（A_TOTAL）浓度呈现先增加后减少的趋势，其中以Zn₂Zr_0.1Al-MMO样品最大，表明Zr对调节Zn₂Zr_xAl-MMO催化剂酸碱性质起到了关键作用.研究发现，Zn₂Zr_0.1Al-MMO催化剂样品具有最大浓度的中强碱位点（B_M）和弱酸位点（A_W）.为了揭示构效关系，进一步研究了DEC产率与催化剂酸碱位点浓度的函数关系.结果表明，DEC产率与中强碱位点（BM）或弱酸位点（AW）的浓度呈现正相关性；而且中强碱位点和弱酸位点之间的协同作用对提升催化性能有重要贡献.与目标催化剂相比，对照样品Zn₂Al-MMO表现出较高的EC产率（54.7%）和较低的DEC产率（28.3%），表明目标催化剂中的ZrO₂组分能够有效活化中间产物EC，促使其进一步转化为DEC.此外，ZrO₂和Al₂O₃均显示出较高的EC产率（68.0%和81.2%），但DEC产率（8.7%和5.3%）较低，说明目标催化剂中的ZnO组分能有效活化乙醇分子，消耗生成的中间体EC.原位红外结果证实，ZrO₂提供的弱酸性位点促进了尿素和中间产物EC的活化吸附，在2207cm^-1处观察到n_N=C=O特征吸附峰；而乙醇在中强碱性位点（Zn²⁺-O^2-）活化，在2973，2925，2900，1078和1052cm^-1处观察到乙醇的特征吸收峰.此外，Zn₂Zr_0.1Al-MMO催化剂表现出良好的稳定性和可重复使用性，循环使用5次后，DEC产率损失低于5%.

关键词: 水滑石, 金属氧化物, 酸碱催化反应, 乙醇转化

Abstract:

Ethanol conversion to high-value-added products has attracted considerable attention in both academic research and industrial fields. In this study, we synthesized a series of tunable acid-base bifunctional Zn-Zr-Al metal oxides (represented as Zn₂Zr_xAl-MMO) in light of the structural topotactic transformation of Zn₂Zr_xAl-hydrotalcite precursors (Zn₂Zr_xAl-LDH). The resulting Zn₂Zr_xAl-MMO catalysts were employed in the conversion of ethanol to diethyl carbonate. The Zr⁴⁺ ion content of the LDH precursor plays a key role in modulating the acid-base properties and determining catalytic performance:the Zn₂Zr_0.1Al-MMO sample exhibits the optimal catalytic behavior with a diethyl carbonate (DEC) yield of 42.1%, which is the highest reported for metal oxide catalysts. Structure-property correlation investigations revealed that the synergic catalysis between medium-strong basic sites and weak acid sites plays a predominant role in the catalytic behavior. Furthermore, in situ Fourier transform infrared measurements showed that the weak acidic site promotes activation adsorption of the reactant (urea) and the intermediate product (ethyl carbamate), while the medium-strong basic site accelerates ethanol activation. Moreover, the Zn₂Zr_0.1Al-MMO catalyst has the advantages of cost effectiveness, good stability, and reusability. Therefore, the acid-base bifunctional catalysts developed in this work can be employed as promising candidates in acid-base catalytic reactions such as ethanol conversion.

Key words: Hydrotalcite, Metal oxides, Acid-base catalytic reactions, Ethanol conversion

张健, 阎婷婷, 杨宇森, 孙嘉略, 林彦军, 卫敏. Zn-Zr-Al氧化物催化乙醇合成碳酸二乙酯[J]. 催化学报, 2019, 40(4): 515-522.

Jian Zhang, Tingting Yan, Yusen Yang, Jialue Sun, Yanjun Lin, Min Wei. Zn-Zr-Al oxides derived from hydrotalcite precursors for ethanol conversion to diethyl carbonate[J]. Chinese Journal of Catalysis, 2019, 40(4): 515-522.

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Zn-Zr-Al氧化物催化乙醇合成碳酸二乙酯

Zn-Zr-Al oxides derived from hydrotalcite precursors for ethanol conversion to diethyl carbonate

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