采用原位魔角旋转固体核磁共振技术研究了2-~(13)-异丁烷在SO_4~(2-)/ZrO_2上的重构化反应机理,考察了反应温度和H_2气氛对反应的影响.结果表明,反应初期,异丁烷在SO_4~(2-)/ZrO_2上的重构化反应以单分子机理为主,之后向双分子机理转变;反应温度的升高有利于单分子机理向双分子机理的转变;H_2的存在抑制了异丁烷的重构化反应,特别对其双分子机理的反应有较强的抑制作用.
In situ ~(13)3C MAS NMR was employed to study the reaction mechanism of isobutane rearrangement over sulfated zirconia using 2-~(13)C-isobutane as a reactant. The effects of temperature and hydrogen atmosphere on the reaction were investigated. The results showed that the reaction of isobutane proceeded mainly via a monomolecular mechanism in its early stage, and then a bimolecular mechanism became dominant. Increasing temperature also led to the reaction from monomolecular to bimolecular mechanism. In the presence of hydrogen, the reaction of isobutane rearrangement, in particular that through the bimolecular pathway, was significantly inhibited.
参考文献
| [1] | Li X B;Nagaoka K;Simon L J;Olindo R Lercher J A .[J].Journal of Catalysis,2005,232:456. |
| [2] | Li X B;Nagaoka K;Simon L J;Olindo R Lercher J A Hofmann A Sauer J .[J].Journal of the American Chemical Society,2005,127:16159. |
| [3] | Stepanov, AG;Luzgin, MV;Arzumanov, SS;Wang, W;Hunger, M;Freude, D .n-Butane conversion on sulfated zirconia: in situ C-13 MAS NMR monitoring of the kinetics of the C-13-label scrambling and isomerization[J].Catalysis Letters,2005(3/4):181-185. |
| [4] | 缪长喜;华伟明;高滋 .[J].催化学报,1997,18:13. |
| [5] | Lohitharn N;Lotero E;Goodwin JG .A comprehensive mechanistic pathway for n-butane isomerization on sulfated zirconia[J].Journal of Catalysis,2006(2):328-341. |
| [6] | Matsuhashi H;Shibata H;Nakamura H;Arata K .[J].Applied Catalysis A:General,1999,187:99. |
| [7] | Ma Zh N;Zou Y;Hua W M;He H Y Gao Z .[J].Topics in Catalysis,2005,35:141. |
| [8] | Suzuki T;Okuhara T .[J].Catalysis Letters,2001,72:111. |
| [9] | Echizen T;Suzuki T;Kamiya Y;Okuhara T .[J].Journal of Molecular Catalysis A:Chemical,2004,209:145. |
| [10] | Yang TS.;Lin CH.;Yeh CT.;Chang TH. .Mechanisms of n-butane isomerization over superacidic sulfated metal oxides[J].Journal of molecular catalysis, A. Chemical,2000(2):397-402. |
| [11] | Garin F.;Girard P.;Maire G.;Abdulsamad A.;Sommer J.;Seyfried L. .A SKELETAL REARRANGEMENT STUDY OF LABELLED BUTANES ON A SOLID SUPERACID CATALYST - SULFURIC ACID TREATED ZIRCONIUM OXIDE[J].Journal of Catalysis,1995(1):26-32. |
| [12] | Luzgin M V;Arzumanov S S;Shmachkova V P;Kotsarenko N S Rogov V A Stepanov A G .[J].Journal of Catalysis,2003,220:233. |
| [13] | Wang W;Jiang Y J;Hunger M .[J].Catalysis Today,2006,113:102. |
| [14] | Zeng D L;Yang J;Wang J Q;Xu J Yang Y X Ye C H Deng F .[J].Microporous and Mesoporous Materials,2007,98:214. |
| [15] | Ma D.;Zhang WP.;Han XW.;Xu YD.;Bao XH.;Shu YY. .In situ H-1 MAS NMR spectroscopic observation of proton species on a Mo-modified HZSM-5 zeolite catalyst for the dehydroaromatization of methane[J].Angewandte Chemie International Edition,2000(16):2928-2931. |
| [16] | Ma Zh N;Hua W M;Ren Y;He H Y Gao Z .[J].Applied Catalysis A:General,2003,256:243. |
| [17] | Derouane EG.;Hamid SBDA.;Lambert D.;Ivanova I.;He HY. .In situ MAS NMR spectroscopy study of catalytic reaction mechanisms[J].Journal of molecular catalysis, A. Chemical,2000(1):5-17. |
| [18] | 马卓娜,胡军成,范康年,曹勇,贺鹤勇,高滋.表征固体超强酸性的新方法--正丁烷异构化反应的原位13C MAS NMR谱[J].化学学报,2003(09):1352-1356. |
| [19] | Tran M T;Gnep N S;Guisnet M;Nascimento P .[J].Catalysis Letters,1997,47:57. |
| [20] | Kim S Y;Goodwin J G;Hammache S;Auroux A Galloway D .[J].Journal of Catalysis,2001,201:1. |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%