Page 179 - 《精细化工）》2023年第10期

第 40 卷第 10 期 精 细 化 工 Vol.40, No.10
20 23 年 10 月 FINE CHEMICALS Oct. 2023

催化与分离提纯技术
异山梨醇焦油还原制备 Co-Mo C 催化合成
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2,5-二羟基对苯二甲酸二甲酯

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赵世丽 ，单玉华 1,2* ，胡林玲 ，蔡志祥 ，李焱叶 ，刘 平 1,2
（1. 常州大学 石油化工学院，江苏 常州 213164；2. 江苏省先进催化与绿色制造协同创新中心，江苏 常
州 213164）
摘要：异山梨醇焦油在无水 K 2 CO 3 催化下高温原位还原四水合钼酸铵和六水合硝酸钴制备了钴杂化碳化钼
（Co-Mo 2 C），采用 XRD、N 2 吸附-脱附、SEM、XPS 对所制备样品进行了表征。将制备的 Co-Mo 2 C 用于催化
O 2 氧化丁二酰丁二酸二甲酯（DMSS）合成 2,5-二羟基对苯二甲酸二甲酯（DMDHT）。考察了煅烧温度、
n(Co)︰n(Mo)、氧化反应条件对 DMDHT HPLC 纯度和收率的影响。结果表明，异山梨醇焦油在 850 ℃原位还
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原四水合钼酸铵和六水合硝酸钴 4 h 制得了比表面积为 134 m /g 的 Co-5Mo 2 C-4（其中，5 为 Mo 和 Co 物质的量
比值，4 为煅烧时间，h），其较好的催化性能归因于 Co 与 Mo 2 C 的协同作用。在 2.00 g Co-5Mo 2 C-4 催化作用
下，DMSS 在 110 ℃、1.00 MPa O 2 气氛中反应 4 h，可得到收率为 88.22%、HPLC 纯度为 99.98%的 DMDHT。
Co-5Mo 2 C-4 具有良好的循环性能，循环使用 6 次后，DMDHT 的收率仅下降 1.7%；循环使用 9 次后，DMDHT
的收率下降了 7.3%。
关键词：异山梨醇焦油；原位还原；钴杂化碳化钼；催化氧化；二羟基对苯二甲酸二甲酯
中图分类号：TQ 245.4 文献标识码：A 文章编号：1003-5214 (2023) 10-2257-07

Preparation of Co-Mo 2C with isosorbitol-tar reduction for catalytic synthesis

of dimethyl 2,5-dihydroxyterephthalate

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ZHAO Shili , SHAN Yuhua 1,2* , HU Linling , CAI Zhixiang , LI Yanye , LIU Ping
（1. School of Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, China; 2. Advanced
Catalysis and Green Manufacturing Collaborative Innovation Center, Changzhou 213164, Jiangsu, China）
Abstract: Cobalt-hybrid molybdenum carbide (Co-Mo 2C) was prepared by in situ reduction of ammonium
molybdate tetrahydrate and cobalt nitrate hexahydrate with isosorbitol-tar in the presence of anhydrous
K 2CO 3 at high temperature and characterized by XRD, N 2 adsorption-desorption, SEM and XPS. The
Co-Mo 2C obtained was then used to catalyze the oxidation of dimethyl succinate (DMSS) by O 2 to form
dimethyl 2,5-dihydroxyterephthalate (DMDHT). The effects of calcination temperature, molar ratio of Co to
Mo and oxidation conditions on HPLC purity and yield of DMDHT were investigated. The results showed
that Co-5Mo 2C-4 (Where, 5 is the molar ratio of Mo to Co, and 4 is the calcined time, h) with a specific
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surface area of 134 m /g could be successfully synthesized by in situ reduction of ammonium molybdate
tetrahydrate and cobalt nitrate hexahydrate at 850 ℃ for 4 h with isosorbitol-tar, and exhibited good
catalytic property due to the synergistic effect of Co and Mo 2C. Under the conditions of 2.00 g
Co-5Mo 2 C-4 as catalyst, 1.00 MPa O 2, reaction temperature of 110 ℃, and reaction time of 4 h,
DMDHT with a yield of 88.22% and HPLC purity of 99.98% was obtained. Meanwhile, Co-5Mo 2 C-4
showed good cycling performance. The yield of DMDHT decreased by only 1.7% after 6 recycles, and
7.3% after 9 recycles.
Key words: isosorbitol-tar; in situ reduction; cobalt doped molybdenum carbide; catalytic oxidation;

收稿日期：2022-11-02; 定用日期：2023-02-24; DOI: 10.13550/j.jxhg.20221000
作者简介：赵世丽（1996—），女，硕士生，E-mail：872511615@qq.com。联系人：单玉华（1965—），男，教授，E-mail：yvhvashan@126.com。