以PdCl2为前驱体,采用浸渍法制备了Pd/C催化剂,并在发烟硫酸中考察了其催化甲烷选择氧化反应的性能,采用X射线粉末衍射、X射线光电子能谱、高分辨透射电镜和CO吸附等方法对催化剂进行了表征. 甲烷选择氧化反应得到的主产物硫酸单甲酯经水解后得到甲醇,在5%Pd/C催化剂、Pd用量30 μmol、反应温度180 ℃、反应压力4.0 MPa、反应时间 4 h 和发烟硫酸中SO3含量为50%的优化工艺条件下,甲烷转化率为23.6%, 甲醇的选择性和收率分别为69.5%和16.4%, 在一定程度上可实现催化剂的多次重复使用. Pd/C催化剂上的甲烷选择氧化反应可能遵循亲电取代机理,催化性能与Pd负载量、Pd粒子尺寸和分散度等有关.
参考文献
| [1] | Gol'dshleger N F;Tyabin M B;Shilov A E;Shteinman A A .[J].Zhurnal Fizicheskoi Khimii,1969,43(08):2174. |
| [2] | Shilov A E;Shul'pin G B .[J].Chemical Reviews,1997,97(08):2879. |
| [3] | Sen A .[J].Accounts of Chemical Research,1998,31(09):550. |
| [4] | Labinger J A;Bercaw J E .[J].Nature,2002,417(6888):507. |
| [5] | Michalkiewicz B;Kalucki K .[J].Chemical Papers,2003,57(06):393. |
| [6] | Periana R A;Bhalla G;TennⅢ W J;Young K J H Liu X Y Mironov O Jones C J Ziatdinov V R .[J].Journal of Molecular Catalysis A:Chemical,2004,220(01):7. |
| [7] | Michalkiewicz B .[J].Chemical Papers,2006,60(05):371. |
| [8] | Conley B L;TennⅢ W J;Young K J H;Ganesh S K Meier S K Ziatdinov V R Mironov O Oxgaard J Gonzales J Goddard Ⅲ W A Periana R A .[J].Journal of Molecular Catalysis A:Chemical,2006,251(1-2):8. |
| [9] | Shilov A E;Shul'pin G B .[J].Russian Chemical Reviews,1987,56(05):442. |
| [10] | Kao L C;Hutson A C;Sen A .[J].Journal of the American Chemical Society,1991,113(02):700. |
| [11] | Lin M R;Sen A .[J].Nature,1994,368(6472):613. |
| [12] | Yuan Q;Deng W P;Zhang Q H;Wang Y .[J].Advanced Synthesis and Catalysis,2007,349(07):1199. |
| [13] | Periana R A;Taube D J;Evitt E R;Loffler D G Wentrcek P R Voss G Masuda T .[J].Science,1993,259:340. |
| [14] | Periana R A;Taube D J;Gamble S;Taube H Satoh T Fuji H .[J].Science,1998,280:560. |
| [15] | Michalkiewicz B;Kalucki K;Sosnicki J G .[J].Journal of Catalysis,2003,215(01):14. |
| [16] | Jones C J;Taube D;Ziatdinov V R;Periana R A Nielsen R J Oxgaard J Goddard Ⅲ W A .[J].Angewandte Chemie International Edition,2004,43(35):4626. |
| [17] | Mukhopadhyay S;Zerella M;Bell A T .[J].Advanced Synthesis and Catalysis,2005,347(09):1203. |
| [18] | 邹鸣,颜宁,侯思聪,肖超贤,寇元.硫酸体系中金属盐类对甲烷低温转化的催化活性[J].催化学报,2005(08):669-671. |
| [19] | Kua J.;Xu X.;Periana RA.;Goddard WA. .Stability and thermodynamics of the PtCl2 type catalyst for activating methane to methanol: A computational study[J].Organometallics,2002(3):511-525. |
| [20] | Mukhopadhyay S;Bell A T.[J].Chemical Communications,2003(13):1590. |
| [21] | Periana R A;Mirinov O;Taube D J;Gamble S.[J].Chemical Communications,2002(20):2376. |
| [22] | 尹国川;奚祖威;曹国英;张秀峰 李萌 .[J].催化学报,1997,18(05):402. |
| [23] | 张秀成,曹凯,陈立宇,韩玉英.V2O5催化剂液相选择性氧化甲烷合成甲醇[J].石油化工,2004(09):813-815. |
| [24] | 陈立宇,杨伯伦,张秀成,董武,张小平.含钒杂多酸催化发烟硫酸中甲烷液相部分氧化反应[J].催化学报,2006(06):462-464. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%