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第 36 卷第 1 期 精 细 化 工 Vol.36, No.1
201 9 年 1 月 FINE CHEMICALS Jan. 2019

催化与分离提纯技术
MIL-100(Fe)催化正戊醛自缩合反应性能

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王 娣，李步卫，安华良 ，赵新强 ，王延吉
（河北工业大学 化工学院，绿色化工与高效节能河北省重点实验室，天津 300130）

摘要：以硝酸铁和 1,3,5-苯三甲酸为原料，采用水热法制备了金属有机骨架材料 MIL-100(Fe)催化剂，采用 XRD、
SEM、BET 对其结构进行了表征。评价了 MIL-100(Fe)催化正戊醛自缩合合成 2-丙基-2-庚烯醛的反应性能。根
据 GC-MS 分析结果，推测了该反应体系中的副产物以及可能发生的副反应。通过条件优化实验，得到适宜的反
应条件为：催化剂用量为 15%（以正戊醛的质量为基准，下同）、反应温度为 130 ℃、反应时间为 8 h。在该条
件下，正戊醛转化率为 73.5%，2-丙基-2-庚烯醛收率和选择性分别为 63.2%和 86.0%。MIL-100(Fe)催化剂重复
使用 4 次后，催化活性没有明显下降，通过 XRD、FTIR 分析证明其催化剂结构未发生坍塌。建立了 MIL-100( Fe)
催化正戊醛自缩合反应网络。
关键词：正戊醛；羟醛缩合；2-丙基-2-庚烯醛；MIL-100(Fe)；反应网络；催化技术
中图分类号：TQ 203.2 文献标识码：A 文章编号：1003-5214 (2019) 01-0094-07

MIL-100(Fe) Catalyzed Self-Condensation of n-Valeraldehyde

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WANG Di, LI Bu-wei, AN Hua-liang , ZHAO Xin-qiang , WANG Yan-ji
（Hebei Provincial Key Laboratory of Green Chemical Technology and Efficient Energy Saving, School of Chemical
Engineering and Technology, Hebei University of Technology, Tianjin 300130, China）

Abstract: Metal-organic framework MIL-100(Fe) catalyst was prepared by hydrothermal method using
ferric nitrate and benzene tricarboxylic acid as raw materials. Its structure was characterized by XRD, SEM
and BET. Its catalytic performance for n-valeraldehyde self-condensation to 2-propyl-2-heptenal was
evaluated. According to the results of GC-MS analysis, the by-products and possible side reactions in the
reaction system were speculated. The effect of reaction conditions on 2-propyl-2-heptenal synthesis was
investigated and the suitable reaction conditions were determined as follows: a weight percentage of
MIL-100(Fe)=15% (benchmarked against the quality of n-valeraldehyde, the following is the same), a
reaction temperature of 130 ℃, and a reaction time of 8 h. Under the above conditions, the conversion of
n-valeraldehyde was 73.5%, the yield and selectivity of 2-propyl-2-heptenal were 63.2% and 86.0%,
respectively. The MIL-100(Fe) catalyst could be reused for four times without a significant loss in its
catalytic performance. XRD and FTIR analysis showed that the catalyst structure did not collapse. Lastly, a
possible reaction network of MIL-100(Fe) catalyzed n-valeraldehyde self-condensation was established.
Key words: n-valeraldehyde; aldol condensation; 2-propyl-2-heptenal; MIL-100(Fe); reaction network;
catalysis technology
Foundation items: National Natural Science Foundation of China (21506046, 21476058); Natural Science
Foundation of Tianjin City (16JCQNJC06100)

2-丙基庚醇是一种重要的用于合成增塑剂的 （DOP）相比，DPHP 具有低毒、低挥发性及低雾
[1]
醇，主要用于合成邻苯二甲酸二（2-丙基庚）酯 化性等优点 。正戊醛自缩合合成 2-丙基-2-庚烯醛
（DPHP）。与传统增塑剂——邻苯二甲酸二辛酯 是工业生产 2-丙基庚醇工艺中实现碳链增长的关键

收稿日期：2018-03-20; 定用日期：2018-08-13; DOI: 10.13550/j.jxhg.20180188
基金项目：国家自然科学基金（21506046，21476058）；天津市自然科学基金青年项目（16JCQNJC06100）
作者简介：王 娣（1992—），女，硕士生。联系人：安华良（1981—），男，副研究员，电话：022-60202427，E-mail：anhl@hebut.edu.cn;
赵新强（1963—），男，教授，博士生导师，电话：022-60202427，E-mail：zhaoxq@ hebut.edu.cn。