首页|K/KCC-1催化碳酸二甲酯和乙醇酯交换合成碳酸甲乙酯

K/KCC-1催化碳酸二甲酯和乙醇酯交换合成碳酸甲乙酯

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以水热合成法制备的树突纤维状二氧化硅(KCC-1)为载体、乙酸钾为前驱体,采用等体积浸渍法制备了不同K理论负载量(x,x为K与Si物质的量的比值,分别为0.3、0.5、0.7、0.9、1.1)的固体碱催化剂(xK/KCC-1).采用XRD、FTIR、BET、CO2-TPD和SEM对xK/KCC-1进行了表征,评价了其对碳酸二甲酯(DMC)和乙醇进行酯交换反应合成碳酸甲乙酯(EMC)的催化性能.结果表明,xK/KCC-1具有2种碱性位,分别是由K2SiO3提供的弱碱性位和由K2CO3提供的中强碱性位,且随着K理论负载量的增加,弱碱性位点逐渐下降,中强碱性位点逐渐增强,催化剂的反应活性增强.K理论负载量≤0.9的xK/KCC-1仍保持KCC-1的树突纤维结构,使反应物分子能够较好地扩散到活性位点上,0.9K/KCC-1具有最高的催化活性.在反应温度为80 ℃、反应时间为5 h、乙醇与DMC(4.494 g)的物质的量比为4∶1、0.9K/KCC-1用量为DMC质量的5%的最佳反应条件下,DMC的转化率为91.0%,EMC的选择性为95.5%,且其具有良好的循环稳定性,重复使用5次后,DMC的转化率为86.7%,EMC的选择性为95.2%.
Synthesis of methyl ethyl carbonate by transesterification of dimethyl carbonate and ethanol catalyzed by K/KCC-1
Solid base catalysts(xK/KCC-1)with different K theoretical loading(x,x is the molar ratio of K to Si,x=0.3,0.5,0.7,0.9,1.1)were synthesized by equi-volumetic impregnation method using dendrite fibrous silica(KCC-1)prepared from hydrothermal synthesis as support and potassium acetate as precursor,and characterized by XRD,FTIR,BET,CO2-TPD and SEM.xK/KCC-1 samples were then evaluated for their catalytic performance on the synthesis of methyl ethyl carbonate(EMC)via transesterification of dimethyl carbonate(DMC)and ethanol.The results indicated that xK/KCC-1 had two types of basic sites,the weak basic sites provided by K2SiO3 and the medium strong basic sites provided by K2CO3.With the increase in K theoretical loading,the weak basic sites gradually decreased,while the medium strong basic sites gradually increased,thus enhancing the reaction activity of transesterification.xK/KCC-1 with K theoretical loading ≤0.9 still maintained the dendritic fiber structure of KCC-1,allowing reactant molecules to diffuse well to the active sites.0.9K/KCC-1 exhibited the highest catalytic activity.Under the optimal reaction conditions of reaction temperature 80 ℃,reaction time 5 h,molar ratio of ethanol to DMC(4.494 g)4∶1,and 0.9K/KCC-1 dosage 5%of DMC mass,the conversion rate of DMC was 91.0%,and the EMC selectivity was 95.5%.Furthermore,0.9K/KCC-1 showed good cyclic stability,with a DMC conversion of 86.7%and an EMC selectivity of 95.2%after 5 recycles.

dendritic fibrous silicasolid basesmethyl ethyl carbonatetransesterificationcatalytic technology

钱俊、刘飞、李欢欢、徐鑫、汤吉海、张竹修、乔旭

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东华工程科技股份有限公司,安徽合肥 230024

南京工业大学化工学院材料化学工程国家重点实验室,江苏南京 210009

国家"江苏先进生物与化学制造协同创新中心",江苏南京 210009

树突纤维状二氧化硅 固体碱 碳酸甲乙酯 酯交换 催化技术

国家自然科学基金项目江苏省重点研发计划重大科技示范项目江苏高校"青蓝工程"项目

21676141BE2021710

2024

精细化工
大连化工研究院设计院 中国化工学会精细化工专业委员会 辽宁省化工研究院

精细化工

CSTPCD北大核心
影响因子:0.557
ISSN:1003-5214
年,卷(期):2024.41(10)
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