Cu-BTC衍生的CuOx/C催化甲醇氧化羰基化合成碳酸二甲酯性能
Performance of Cu-BTC-derived CuOx/C for methanol oxidative carbonylation to dimethyl carbonate
李文杰 1高山林 2赖春波 2肖婉婧 1李心灵 1林慧博 1王馨雨 1徐成华 1邓志勇1
作者信息
- 1. 成都信息工程大学 资源环境学院,中-塞环境与能源"一带一路"联合实验室,大气环境模拟与污染控制四川省高校重点实验室,成都 610225
- 2. 上海华谊控股集团有限公司 上海煤基多联产工程技术研究中心,上海 200040
- 折叠
摘要
碳基材料负载Cu是一类高效的甲醇氧化羰基化合成碳酸二甲酯催化剂,但存在Cu纳米颗粒易团聚和氧化等问题.采用溶剂热法制备了Cu-BTC,并以其为前驱体,在N2 气氛下热解,制备了碳负载Cu及其氧化物(CuOx/C)催化剂.考察了热解温度对Cu纳米颗粒粒径、Cu的价态以及甲醇氧化羰基化合成碳酸二甲酯性能的影响.表征结果显示,升高热解温度有利于Cu2+还原为(Cu0+Cu+),但会导致Cu纳米颗粒团聚.催化剂活性随着热解温度升高而降低,当热解温度为 300℃时,制备的CuOx/C-300具有最优的催化活性,碳酸二甲酯的时空收率为 1 209 mg·g-1·h-1,归因于Cu纳米颗粒的粒径最小(7.5 nm).经过 6次循环实验后,碳酸二甲酯的时空收率降至 468 mg·g-1·h-1,催化剂失活的主要原因是(Cu0+Cu+)的氧化和Cu纳米颗粒团聚.
Abstract
Carbon-based material supported Cu is an efficient catalyst for methanol oxidative carbonylation to dimethyl carbonate,but Cu nanoparticles are prone to agglomeration and oxidation.Cu-BTC were prepared by hydrothermal method.And then CuOx/C catalysts was prepared by pyrolysis Cu-BTC under N2 atmosphere.The effect of pyrolysis temperature on Cu nanoparticle size,Cu valence state and performance for methanol oxidative carbonylation to dimethyl carbonate were investigated.The characterization results show that increasing the pyrolysis temperature is beneficial to the reduction of Cu2+to(Cu0+Cu+),but would lead to the agglomeration of Cu nanoparticles.Catalytic activity decreases with the increasing of pyrolysis temperature.CuOx/C-300,prepared by pyrolysis of Cu-BTC at 300℃,shows the optimized catalytic activity and the space-time yield of dimethyl carbonate is 1 209 mg·g-1·h-1.This is attributed to the smallest particle size of Cu nanoparticles(7.5 nm).In addition,the space-time yield of dimethyl carbonate decreased to 468 mg·g-1·h-1 after 6 cycle experiments.The main reasons for catalyst inactivation are the oxidation of(Cu0+Cu+)and the agglomeration of Cu nanoparticles.
关键词
催化剂/碳基材料/Cu纳米颗粒/碳酸二甲酯/MOFs/热解/氧化羰基化Key words
catalyst/carbon-based materials/Cu nanoparticles/dimethyl carbonate/MOFs/pyrolysis/oxidative carbonylation引用本文复制引用
基金项目
四川省科技计划(2022ZYD0049)
四川省科技计划(2021YFG0225)
上海煤基多联产工程技术研究中心开放课题(GZKF-MJDLC-03)
成都信息工程大学科研基金(KYTZ202118)
出版年
2024
NETL
NSTL
万方数据