1,4-丁炔二醇选择性加氢催化剂:Pd/ZrO2及其碱金属改性
Selective hydrogenation of 1,4-butynediol to 1,4-butenediol:Pd/ZrO2 catalyst and alkali metals modification
周港 1谭平华 2吴潘 1何坚 1蒋炜 1刘长军 1梁斌3
作者信息
- 1. 四川大学 化学工程学院,四川 成都 610207
- 2. 重庆理工大学 化学化工学院,重庆 400054
- 3. 四川大学 化学工程学院,四川 成都 610207;四川大学 新能源与低碳技术研究院,四川 成都 610207
- 折叠
摘要
以Zr(OH)4 焙烧得到的ZrO2 为载体,采用等体积浸渍法制备了负载型Pd/ZrO2 和碱金属(M)改性的催化剂(Pd/M/ZrO2),通过XRD、BET、TEM及HRTEM、CO2-TPD、XPS对催化剂进行了表征,并评价了其在1,4-丁炔二醇(BYD)选择性加氢制1,4-丁烯二醇(BED)反应中的活性、选择性和稳定性,探究了反应气氛及碱金属改性对其活性和稳定性的影响.结果表明,1.0%Pd/ZrO2(1.0%为Pd的质量分数)在50℃,2.40 MPa H2下,能够催化BYD选择性加氢生成BED,有较高的催化活性[0.048 molBYD/(gPd·s)],在BYD完全转化的条件下,BED的选择性为91.2%.氨的引入能够显著抑制催化剂加氢活性,提高BED的选择性.在BYD接近完全转化时,BED的选择性可达95.6%.向ZrO2载体中引入少量碱金属(Li、Na、K、Rb、Cs),能够提高BED的选择性,其中,Rb的影响最为显著,BED的选择性可达94.1%.
Abstract
Pd/ZrO2 and alkali metals(M)modified Pd/M/ZrO2 catalysts were prepared by incipient-wetness impregnation with ZrO2 obtained from Zr(OH)4 calcination as support,and characterized by XRD,BET,TEM and HRTEM,CO2-TPD,XPS.The activity,selectivity and stability of the catalysts in the selective hydrogenation of 1,4-butynediol(BYD)to 1,4-butenediol(BED)were evaluated,and the influence of reaction atmosphere and alkali metals modification on the activity and stability of the catalysts were analyzed.The results showed that under 50℃and 2.40 MPa H2 pressure,1.0%Pd/ZrO2(1.0%being the mass fraction of Pd)exhibited high catalytic activity of 0.048 molBYD/(gPd·s),and BED selectivity of 91.2%with complete conversion of BYD.The introduction of ammonia into the reaction mixture inhibited the hydrogenation activity and improved the BED selectivity to 95.6%with complete conversion of BYD.Modification of Pd/ZrO2 with alkali metals(Li,Na,K,Rb,Cs)improved the selectivity of BED with Rb the most effective modifier showing BED selectivity up to 94.1%.
关键词
Pd/ZrO2催化剂/改性/1,4-丁炔二醇/选择性加氢/1,4-丁烯二醇Key words
Pd/ZrO2 catalyst/modification/1,4-butynediol/selective hydrogenation/1,4-butenediol引用本文复制引用
出版年
2024
NETL
NSTL
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