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新型双功能Cu(Ⅰ)/沸石羰基化催化剂的制备与表征
PREPARATION AND CHARACTERIZATION OF A NEW TYPE OF BIFUNCTIONAL Cu(Ⅰ)/ZEOLITE CARBONYLATION CATALYST
【摘要】 报道了双功能Cu( Ⅰ)/ 沸石羰基化催化剂的制备及其FTIR 和XPS表征结果. 催化剂兼具酸性和金属羰基两类活性中心,能够在较温和的条件( ~523 K, 常压) 下催化醇与CO的羰基化合成反应. 以异丁醇为原料时,其C5 羧酸和异戊酸异丁酯的总收率可达20-4 % . 催化剂的XPS和IR表征结果证实,铜以Cu( Ⅰ) 价态存在,吸附CO后,形成金属羰基活性中心Cu(CO) +2 . 可能的反应机理是: 母体沸石Hβ或HZSM5 中的酸性中心使醇质子化,形成碳正离子,随后邻近的金属羰基中心Cu(CO)+2 提供CO, 协同催化使之生成羧酸或最后转变为羧酸酯.
【Abstract】 The preparation of a bifunctional Cu(Ⅰ)/zeolite carbonylation catalyst as well as its FT IR and XPS characterization results are described for the first time. This catalyst possesses both acid and metal carbonyl active sites and catalyzes successfully the synthesis of carbonyl compound from alcohol and CO under mild conditions (~523 K and 0 1 MPa). The total yield 20 4% of both carboxylic acids and carboxylic esters could ve reached when i butanol was used as starting material. It is demonstrated by IR and XPS characterization that the copper exists in Cu(Ⅰ) and from which the metal carbonyl active site of Cu(CO) + 2 is formed by CO adsorption. The alcohol is protonized at acidic sites of the parent zeolites HZSM 5 or Hβ, so that the carbonium ion is formed, then the carboxylic acids are synthesized or the carboxylic esters are finally produced by cooperative catalysis of the adjacent metal carbonyl sites from which the CO is supplied.
【Key words】 zeolite; i butanol; carbonylation; bifunctional catalyst; cuprous ammonia complex cation;
- 【文献出处】 催化学报 ,CHINESE JOURNAL OF CATALYSIS , 编辑部邮箱 ,1999年02期
- 【分类号】O643
- 【被引频次】5
- 【下载频次】129