Preparation of Zn(OAc)2/SiO2 catalyst with better stability prepared by solvothermal impregnation method and its application in methyl N-phenyl carbamate

doi:10.16085/j.issn.1000-6613.2018-0408

Abstract

Abstract:

Zn(OAc)₂ exhibits excellent catalytic performance in the methyl N-phenyl carbamate (MPC) synthesis using aniline and dimethyl carbonate (DMC), but it cannot be reused. Zn(OAc)₂/SiO₂ catalyst was prepared by solvothermal impregnation with DMC as the solvent in this paper. Zn(OAc)₂/SiO₂ was characterized by XRD、FTIR and TG-DTA. The results suggested that Zn(OAc)₂ and ZnO were well dispersed on SiO₂ surface. At reaction temperature of 190℃, reaction time of 5h, n _DMC∶n _aniline of 20∶1 and m _aniline:m $Z n (O A c) 2 / S i O 2$ of 0.2, Zn(OAc)₂/SiO₂ showed the best catalytic performance, giving an aniline conversion of 97.2% and a MPC selectivity of 89.4%. The obtained Zn(OAc)₂/SiO₂ showed better stability than that prepared by incipient impregnation. After the Zn(OAc)₂/SiO₂ was used for the seventh time, aniline conversion and MPC selectivity were found to be 79.1% and 79.2%, respectively and the catalytic activity decrease is attributed to the formation of ZnO. The deactivated Zn(OAc)₂/SiO₂ can be regenerated with the catalytic activity almost the same as that of the fresh catalyst.

Key words: dimethyl carbonate, methyl N-phenyl carbamate, aniline, zinc acetate/silica, solvothermal impregnation, catalyst, stability, regeneration

摘要：

Zn(OAc)₂对由碳酸二甲酯（DMC）和苯胺合成苯氨基甲酸甲酯（MPC）的反应具有优异的催化性能，但存在易失活、不能重复使用的缺点。为此，以DMC为溶剂，利用溶剂热浸渍法制备Zn(OAc)₂/SiO₂催化剂，并对其催化性能进行了研究。利用XRD、FTIR和TG-DTA等方法对其进行了表征，结果表明，Zn(OAc)₂/SiO₂催化剂表面存在Zn(OAc)₂和ZnO，且其在SiO₂表面分散较好；优化了Zn(OAc)₂/SiO₂催化剂的反应条件，当反应温度为190℃、反应时间为5h、苯胺与DMC的摩尔比为1∶20、催化剂与苯胺质量比为0.2时，苯胺的转化率为97.2%，MPC的选择性为89.4%。和等体积浸渍法制备的催化剂相比，溶剂热浸渍法制备的Zn(OAc)₂/SiO₂催化剂具有较好的稳定性，重复使用7次，苯胺的转化率下降至79.1%，MPC的选择性下降至79.2%。Zn(OAc)₂/SiO₂活性下降的原因是由于ZnO的生成，并对其进行了再生，再生后的催化剂活性与新鲜催化剂接近。

关键词: 碳酸二甲酯, 苯氨基甲酸甲酯, 苯胺, Zn(OAc)₂/SiO₂, 溶剂热浸渍, 催化剂, 稳定性, 再生

CLC Number:

TQ426

Xiangcong PENG,Zhimiao WANG,Hongqin LI,Wei XUE,Fang LI,Yanji WANG. Preparation of Zn(OAc)₂/SiO₂ catalyst with better stability prepared by solvothermal impregnation method and its application in methyl N-phenyl carbamate[J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1396-1402.

彭向聪,王志苗,李红芹,薛伟,李芳,王延吉. 溶剂热浸渍法制备高稳定性Zn(OAc)₂/SiO₂催化剂及其催化合成苯氨基甲酸甲酯[J]. 化工进展, 2019, 38(03): 1396-1402.

Figures/Tables 11

References 25

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反应温度 /℃	苯胺转化率 /%	MPC选择性 /%	产物分布（摩尔分数）/%
反应温度 /℃	苯胺转化率 /%	MPC选择性 /%	MPC	NMA	DPU	DMA
160	43.8	89.7	85.0	11.4	0.9	1.9
170	76.5	89.5	88.1	7.6	1.4	1.6
180	88.3	90.2	88.1	7.8	0.9	2.3
190	97.2	89.4	89.5	6.2	0.3	3.7

反应温度 /℃	苯胺转化率 /%	MPC选择性 /%	产物分布（摩尔分数）/%
反应温度 /℃	苯胺转化率 /%	MPC选择性 /%	MPC	NMA	DPU	DMA
160	43.8	89.7	85.0	11.4	0.9	1.9
170	76.5	89.5	88.1	7.6	1.4	1.6
180	88.3	90.2	88.1	7.8	0.9	2.3
190	97.2	89.4	89.5	6.2	0.3	3.7

反应时间/h	苯胺转化率/%	MPC 选择性/%	产物分布（摩尔分数）/%
反应时间/h	苯胺转化率/%	MPC 选择性/%	MPC	NMA	DPU	DMA
1	31.8	86.5	82.3	14.7	1.5	0
3	83.6	85.9	85.6	9.1	1.3	2.7
5	97.2	89.4	89.5	6.2	0.3	3.7
7	98.4	85.1	88.5	5.8	0.2	5.3

反应时间/h	苯胺转化率/%	MPC 选择性/%	产物分布（摩尔分数）/%
反应时间/h	苯胺转化率/%	MPC 选择性/%	MPC	NMA	DPU	DMA
1	31.8	86.5	82.3	14.7	1.5	0
3	83.6	85.9	85.6	9.1	1.3	2.7
5	97.2	89.4	89.5	6.2	0.3	3.7
7	98.4	85.1	88.5	5.8	0.2	5.3

催化剂用量/g	苯胺转化率/%	MPC 选择性/%	产物分布（摩尔分数）/%
催化剂用量/g	苯胺转化率/%	MPC 选择性/%	MPC	NMA	DPU	DMA
0.07	86.9	81.6	82.8	10.3	1.2	4.6
0.15	94.9	85.8	87.1	7.9	0.5	4
0.20	97.2	89.4	89.5	6.2	0.3	3.7
0.28	96.6	88.5	88.5	6.6	0.3	4.3

Preparation of Zn(OAc)₂/SiO₂ catalyst with better stability prepared by solvothermal impregnation method and its application in methyl N-phenyl carbamate

溶剂热浸渍法制备高稳定性Zn(OAc)₂/SiO₂催化剂及其催化合成苯氨基甲酸甲酯

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n _DMC/n _AN	苯胺转化率/%	MPC 选择性/%	产物分布（摩尔分数）/%
n _DMC/n _AN	苯胺转化率/%	MPC 选择性/%	MPC	NMA	DPU	DMA
10	97.4	85.5	86.8	6.8	0.4	5.7
15	97.1	86.7	87.0	7.5	0.3	4.9
20	97.2	89.4	89.5	6.2	0.3	3.7
25	92.6	92.1	86.7	8.1	0.4	4.3

催化剂	苯胺转化率/%	MPC 选择性/%
新鲜Zn(OAc)₂/SiO₂	97.2	89.4
再生Zn(OAc)₂/SiO₂	98.0	84.5

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