Page 96 - 《精细化工》2021年第8期

第 38 卷第 8 期 精 细 化 工 Vol.38, No.8
202 1 年 8 月 FINE CHEMICALS Ang. 2021

催化与分离提纯技术
固体碱 KF/MgAl-LDO 催化苯酚与

碳酸二甲酯合成苯甲醚

1*
1
王玉斌 1,2 ，陈 彤 ，王公应
（1. 中国科学院成都有机化学研究所，四川 成都 610041；2. 中国科学院大学，北京 100049）

摘要：以 Mg(NO 3 ) 2 •6H 2 O 和 Al(NO 3 ) 3 •9H 2 O 为原料，共沉淀法制备了镁铝水滑石（MgAl-LDHs），以 MgAl-LDHs
为前驱体，高温焙烧得到类水滑石 MgAl-LDO 和不同碱金属卤化物（MX）掺杂的固体碱催化剂 MX/MgAl-LDO。
对其进行 XRD 表征和 Hammett 法碱性滴定，并考察了其催化苯酚与碳酸二甲酯（DMC）合成苯甲醚的活性。
结果显示，前驱体 MgAl-LDHs 的 Mg/Al 物质的量比、沉淀 pH 及焙烧温度均影响 KF/MgAl-LDO 的结构和碱性；
KF 的掺杂大幅增加了催化剂的碱量，且碱强度（H 0 ）在 11.0~15.0 区间强碱的碱量提升更为显著，KF/MgAl-LDO
增加的强碱性位主要是由 KMgF 3 和 K 2 CO 3 提供。当 KF 掺杂量为 KF/MgAl-LDO 质量的 33%时，KF/MgAl-LDO
具有最好的催化性能。在 DMC/苯酚物质的量比为 2∶1，KF/MgAl-LDO 用量为苯酚质量 1%，200 ℃下反应 4 h，
苯甲醚收率为 95.2%。对催化剂催化活性与碱性关系分析发现，催化剂的活性与总碱量正相关，而碱强度在
11.0~15.0 区间的强碱性位具有最高的催化效率。
关键词：固体碱；镁铝水滑石；氟化钾；碳酸二甲酯；苯甲醚；催化技术
中图分类号：TQ426；TQ241 文献标识码：A 文章编号：1003-5214 (2021) 08-1590-08

Synthesis of anisole from phenol and dimethyl carbonate
catalyzed by solid base KF/MgAl-LDO

1,2
1*
1
WANG Yubin , CHEN Tong , WANG Gongying
（1. Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, Sichuan, China; 2. University
of Chinese Academy of Sciences, Beijing 100049, China）
Abstract: Magnalium hydrotalcites (MgAl-LDHs) were prepared using Mg(NO 3 ) 2 •6H 2 O and Al(NO 3 ) 3 •9H 2 O
as raw materials by co-precipitation method. Then, hydrotalcite like MgAl-LDO and solid base catalyst
MX/MgAl-LDO doped by different alkali metal halides (MX) were prepared by calcination at high
temperature using MgAl-LDHs as precursor. The samples were characterized by XRD and Hammett indicator,
and the catalytic activity for the synthesis of anisole from phenol and dimethyl carbonate (DMC) was
investigated. The results showed that the Mg/Al molar ratio, precipitation pH and calcination temperature of
the precursor MgAl-LDHs all affected the structure and alkalinity of KF/MgAl-LDO. The doping of KF
greatly increased the base amount in the catalyst, and the strong base amount increased more significantly
when the base strength (H 0 ) was in the range of 11.0~15.0, which was mainly provided by KMgF 3 and K 2 CO 3 .
When the doping dosage of KF was 33% of the mass of KF/MgAl-LDO, the prepared KF/MgAl-LDO
catalyst exhibited the best catalytic properties. Under the conditions of the molar ratio of DMC to phenol of
2∶1, catalyst dosage being only 1% of the mass of phenol, reaction temperature of 200 ℃ and reaction
time of 4 h, the yield of anisole was 95.2%. The analysis of the relationship between catalytic activity and
alkalinity of the catalyst indicated that the activity of the catalyst was positively correlated with the total base

收稿日期：2021-02-06; 定用日期：2021-04-19; DOI: 10.13550/j.jxhg.20210143
基金项目：四川省重点研发项目（2021YFG0109）
作者简介：王玉斌（1996—），男，硕士生，E-mail：bywangyb@.foxmail.com。联系人：陈 彤（1967—），女，博士，研究员，E-mail：
chentongw@sina.com。