蒸气浸渍法制备完全无氯CuY催化剂及其氧化羰基化性能

doi:10.16085/j.issn.1000-6613.2020-0510

化工进展 ›› 2021, Vol. 40 ›› Issue (1): 242-246.DOI: 10.16085/j.issn.1000-6613.2020-0510

蒸气浸渍法制备完全无氯CuY催化剂及其氧化羰基化性能

王玉春¹(), 刘赵荣¹, 谭超², 孙鸿¹, 李忠³

^1.运城学院应用化学系，山西运城 044000
^2.宜宾学院过程分析与控制四川省高校重点实验室，四川宜宾 644000
^3.太原理工大学煤科学与技术教育部和山西省重点实验室，山西太原 030024

收稿日期:2020-04-03 出版日期:2021-01-05 发布日期:2021-01-12
通讯作者: 王玉春
作者简介:王玉春（1980—），女，副教授，从事碳一化学及多相催化研究。E-mail：wyc0104@126.com。
基金资助:
过程分析与控制四川省高校重点实验室项目(2019004);运城学院应用基础研究项目(CY-2019032);运城学院博士科研启动项目(YQ-2019024);运城学院学科研究项目(XK-2019018)

Preparation of chlorine-free CuY catalysts by vapour impregnation and their application for oxidative carbonylation

Yuchun WANG¹(), Zhaorong LIU¹, Chao TAN², Hong SUN¹, Zhong LI³

^1.Department of Applied Chemistry, Yuncheng University, Yuncheng 044000, Shanxi, China
^2.Key Lab of Process Analysis and Control of Sichuan Universities, Yibin University, Yibin 644000, Sichuan, China
^3.Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2020-04-03 Online:2021-01-05 Published:2021-01-12
Contact: Yuchun WANG

摘要/Abstract

摘要：

以具有升华性质且易分解的乙酰丙酮铜为铜源，NH₄Y分子筛为载体，采用蒸气浸渍法制备了CuY催化剂，考察了其对甲醇氧化羰基化合成碳酸二甲酯的催化性能，并采用XRD、H₂-TPR和NH₃-TPD等表征手段研究了催化剂上铜物种的分散状态、催化活性中心的含量及催化剂的酸强度和浓度，发现铜物种在Y分子筛载体上高度分散，且Y分子筛载体的晶体结构保持完好。在N₂∶H₂=12∶1的气氛中，250℃还原得到的催化剂CuY/250催化活性中心含量最高，催化活性也达到了最佳，其甲醇转化率为11.1%，碳酸二甲酯的时空收率和选择性分别为200.5mg/(g·h)和60.3%。

关键词: 蒸气浸渍, CuY催化剂, 制备, 甲醇氧化羰基化, 碳酸二甲酯

Abstract:

CuY catalysts were prepared by vapour impregnation with copper acetylacetonate as the copper source and NH₄Y zeolite as the support. The performance of the catalysts was evaluated by using direct vapor-phase oxidative carbonylation of methanol to dimethyl carbonate (DMC) as a model reaction. The surface dispersion, active component content, acid strength and concentration of the as-prepared catalysts were characterized by X-ray diffraction (XRD), H₂-temperature programmed reduction (H₂-TPR) and NH₃-temperature programmed desorption (NH₃-TPD), respectively. It was found that copper species were highly dispersed on the Y zeolite and the crystal structure of the Y zeolite remained intact. For the CuY/250 catalyst activated at 250℃ and in the atmosphere of N₂∶H₂=12∶1, the active component content was the highest and the catalytic activity was excellent. The obtained methanol conversion, space time yield and selectivity of dimethyl carbonate were 11.1%, 200.5mg/(g·h) and 60.3% respectively.

Key words: vapour impregnation, CuY catalyst, preparation, oxidative carbonylation of methanol, dimethyl carbonate

中图分类号:

O643.36

王玉春, 刘赵荣, 谭超, 孙鸿, 李忠. 蒸气浸渍法制备完全无氯CuY催化剂及其氧化羰基化性能[J]. 化工进展, 2021, 40(1): 242-246.

Yuchun WANG, Zhaorong LIU, Chao TAN, Hong SUN, Zhong LI. Preparation of chlorine-free CuY catalysts by vapour impregnation and their application for oxidative carbonylation[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 242-246.

图/表 5

图1 NH4Y载体和催化剂的XRD谱图

图2 催化剂的H2-TPR谱图及其高斯拟合图

图3 催化剂的NH3-TPD谱图

表1 催化剂NH3-TPD的定量分析

催化剂	NH₃脱附量/μmol·g^-1
催化剂	50～200℃	200～290℃	290～450℃
CuY/200	4.562	0.9788	1.571
CuY/250	4.944	1.094	1.446
CuY/300	3.750	0.7400	0.9974

图4 甲醇氧化羰基化反应中催化剂的催化活性

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蒸气浸渍法制备完全无氯CuY催化剂及其氧化羰基化性能

Preparation of chlorine-free CuY catalysts by vapour impregnation and their application for oxidative carbonylation

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