采用浸渍法制备了碱土金属氧化物CaO,SrO或BaO改性的ZrO2酸碱双功能催化剂,借助X射线衍射、低温N2物理吸附、NH3和CO2程序升温脱附等手段表征了催化剂的结构、织构以及表面酸碱性质,并考察了其催化1,4-丁二醇选择性脱水合成3-丁烯-1-醇的反应性能.结果表明,碱土金属氧化物的引入显著调变了催化剂表面的酸性和碱性中心,进而对1,4-丁二醇转化率和3-丁烯-1-醇选择性产生重要影响.其中,CaO改性的ZrO2样品中形成了大量的Ca-O-Zr结构,在ZrO2表面形成大量碱性位点的同时,保持了较高的酸密度;而SrO和BaO改性的样品中生成了相应的锆酸盐,ZrO2表面的酸密度呈现不同程度的下降.因此,CaO/ZrO2催化剂表现出最优的催化活性和3-丁烯-1-醇选择性,350℃时,3-丁烯-1-醇收率最高,达60.5%.催化剂表面的酸碱协同作用是选择性合成3-丁烯-1-醇的关键因素.
参考文献
[1] | Negishi E;Tan Z;Ling B;Novak T .[J].Proceedings of the National Academy of Sciences(USA),2004,101:5782. |
[2] | Magnin-Lachaux M;Tan Z;Liang B;Negishi E .[J].Organic Letters,2004,6:1425. |
[3] | Csuk R;Kern A .[J].Tetrahedron,1999,55:8409. |
[4] | Min T;Yi B X;Zhang P;Liu J Zhang C Zhou H P .[J].Medicinal Chemistry Research,2009,18:495. |
[5] | Brace N O .[J].Journal of the American Chemical Society,1955,77:4666. |
[6] | Mueller H;Pfalz F;Overwien H;Pommer H .[P].US Patent 3 574 773,1971. |
[7] | Tsuji J;Shimizu I;Minami I .[J].CHEMISTRY LETTERS,1984,13:1017. |
[8] | McCombs C A .[P].US Patent 6 103 943,2000. |
[9] | 贺永艺,李奇飚,王永钊,赵永祥.不同形貌的CeO2催化1,4-丁二醇选择性脱水合成3-丁烯-1-醇[J].催化学报,2010(06):619-622. |
[10] | Sato S;Takahashi R;Sodesawa T;Honda N Shimizu H .[J].CATALYSIS COMMUNICATIONS,2003,4:77. |
[11] | Igarashi A;Ichikawa N;Sato S;Takahashi R;Sodesawa T .Dehydration of butanediols over CeO2 catalysts with different particle sizes[J].Applied Catalysis, A. General: An International Journal Devoted to Catalytic Science and Its Applications,2006(1):50-57. |
[12] | Takahashi R;Yamada I;Iwata A;Kurahashi N Yoshida S Sato S .[J].Applied Catalysis A:General,2010,383:134. |
[13] | Sato F;Sato S .[J].CATALYSIS COMMUNICATIONS,2012,27:129. |
[14] | Sato F;Okazaki H;Sato S .[J].Applied Catalysis A:General,2012,419-420:41. |
[15] | Sato S;Takahashi R;Sodesawa T;Yamamoto N .[J].CATALYSIS COMMUNICATIONS,2004,5:397. |
[16] | Yamamoto N;Sato S;Takahashi R;Inui K .[J].CATALYSIS COMMUNICATIONS,2005,6:480. |
[17] | igarashi A;Sato S;Takahashi R;Sodesawa T Kobune M .[J].CATALYSIS COMMUNICATIONS,2007,8:807. |
[18] | Inoue H;Sato S;Takahashi R;Izawa Y Ohno H Takahashi K .[J].Applied Catalysis A:General,2009,352:66. |
[19] | Yamamoto N;Sato S;Takahashi R;Inui K .[J].J Mol CatalA,2006,243:52. |
[20] | Sato S;Takahashi R;Kobune M;Inoue H Izawa Y Ohno H Takahashi K .[J].Applied Catalysis A:General,2009,356:64. |
[21] | 韦玉丹,张树国,李贵生,尹双凤,区泽棠.近十年固体超强碱催化剂的研究进展[J].催化学报,2011(06):891-898. |
[22] | Tanabe K;Yamaguchi T .[J].Catalysis Today,1994,20:185. |
[23] | Zhang Y;Pan L;Gao C G;Wang Y Z Zhao Y X .[J].JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY,2010,56:27. |
[24] | Zhang Y;Pan L;Gao C G;Zhao Y X .[J].JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY,2011,58:572. |
[25] | Wu ZG.;Zhao YX.;Xu LP.;Liu DS. .Preparation of zirconia aerogel by heating of alcohol-aqueous salt solution[J].Journal of Non-Crystalline Solids: A Journal Devoted to Oxide, Halide, Chalcogenide and Metallic Glasses, Amorphous Semiconductors, Non-Crystalline Films, Glass-Ceramics and Glassy Composites,2003(1/3):274-277. |
[26] | Bellido J D A;De Souza J E;M'Peko J C;Assaf E M .[J].Applied Catalysis A:General,2009,358:215. |
[27] | 朱晴,梁丽萍,贾志奇,高春光,赵永祥.多钨酸盐修饰ZrO2气凝胶催化四氢呋喃开环聚合[J].物理化学学报,2011(02):491-498. |
[28] | 尹衍升;陈守刚;刘英才.氧化锆陶瓷的掺杂稳定及生长动力学[M].北京:化学工业出版社,2004 |
[29] | 路新瀛;梁开明;顾守仁;方鸿生 郑燕康 刘鹏 .[J].硅酸盐学报,1996,24:670. |
[30] | 王慧,刘水刚,张文郁,赵宁,魏伟,孙予罕.高稳定性CaO-ZrO2固体碱催化剂的表征和催化性能[J].化学学报,2006(24):2409-2413. |
[31] | 刘水刚,张学兰,李军平,赵宁,魏伟,孙予罕.高稳定性介孔 CaO-ZrO2固体碱的结构及碱性研究[J].石油化工,2008(03):226-231. |
[32] | 朱月香,庄伟,江德恩,谢有畅.碱土金属化合物在氧化锆上的分散与碱性[J].催化学报,2000(01):52-54. |
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