采用原位Raman光谱技术,在原料气中的O2未完全耗尽的条件下,对CH4部分氧化制合成气反应的gh/SiO2催化剂床层前部贵金属物种的化学态以及由CH4解离所生成的碳物种进行了表征.在此基础上采用脉冲反应和同位素示踪技术,比较了CH4的部分氧化及其与H2O和CO2的重整等反应对催化剂床层氧化区内CO和H2生成的相对贡献,并将实验结果与Ra-man光谱表征结果进行了关联.结果表明,在600℃下将还原后的4％Rh/SiO2催化剂切入CH4∶O2∶Ar=2∶1∶45原料气,催化剂床层前部未检测到铑氧化物的Raman谱峰,但可清晰检测到源于CH4解离的碳物种；在700℃和接触时间小于1ms的条件下,催化剂床层的氧化区内已有大量CO和H2生成,在相同的实验条件下,CH4与H2O或CO2重整反应对氧化区内合成气生成的贡献则很小；以CH4∶16O2∶H218O∶He=2∶1∶2∶95为原料气的同位素示踪实验结果表明,在原料气中16O2未完全耗尽的情况下,反应产物中C16O的含量占CO生成总量的92.3％,表明CO主要来自CH4的部分氧化反应.上述结果均表明,在O2存在下Rh/SiO2催化剂上CO和H2可以通过CH4直接解离和部分氧化机理生成.
参考文献
| [1] | Rostrup-Nielsen J R .[J].Catalysis Today,1993,18:305. |
| [2] | Ashcroft A T;Vheetham A K;Green M L H;Vernon P D F .[J].Nature,1991,352:225. |
| [3] | Hickman D A;Schmidt L D .[J].Science,1993,259:343. |
| [4] | York A P E;Xiao T C;Green M L H .[J].Topics in Catalysis,2003,22:345. |
| [5] | 杨民,Helmut PAPP.Pt/MgO 催化剂上甲烷部分氧化制合成气反应[J].催化学报,2008(03):228-232. |
| [6] | 陈永东,陈耀强,梅大江,张丽娟,董文萍,曹红岩,陈宏,龚茂初.超高温焙烧的Ni/Al2O3对甲烷部分氧化反应的催化活性[J].催化学报,2008(05):477-481. |
| [7] | 鲁辉,佟建华,楚文玲,杨维慎,林励吾.加压条件下BaNi0.3Al11.7O19-δ催化剂上甲烷部分氧化制合成气[J].催化学报,2005(08):683-687. |
| [8] | Prettre M;Eichner C;Perrin M .[J].Transactions of the Faraday Society,1946,42:335. |
| [9] | Hickman D A;Schmidt L D .[J].Journal of Catalysis,1992,138:267. |
| [10] | Hu Y H;Ruckenstein E .[J].Advances in Catalysis,2004,48:297. |
| [11] | Ji H;Feng D;He Y .[J].Journal of Natural Gas Chemistry,2010,19:575. |
| [12] | Lodeng R;Bjorgum E;Enger B C;Eilertsen J L Holmen A Krogh B Boe I A Ronnekleiv M Rytter E .[J].Topics in Catalysis,2011,54:873. |
| [13] | Dissanayake D;Rosynek M P;Kharas K C C;Lunsford J H .[J].Journal of Catalysis,1991,132:117. |
| [14] | Buyevskaya O V;Wolf D;Baerns M .[J].Catalysis Letters,1994,29:249. |
| [15] | Mallens EPJ.;Marin GB.;Hoebink JHBJ. .THE REACTION MECHANISM OF THE PARTIAL OXIDATION OF METHANE TO SYNTHESIS GAS - A TRANSIENT KINETIC STUDY OVER RHODIUM AND A COMPARISON WITH PLATINUM[J].Journal of Catalysis,1997(1):43-56. |
| [16] | Hofstad K H;Hoebink J H B J;Holmen A;Marin G B .[J].Catalysis Today,1998,40:157. |
| [17] | Fathi M.;Schuurman Y.;Holmen A.;Mirodatos C.;Monnet F. .Reactive oxygen species on platinum gauzes during partial oxidation of methane into synthesis gas[J].Journal of Catalysis,2000(2):439-445. |
| [18] | Wang D;Dewaele O;de Groote A M;Froment G F .[J].Journal of Catalysis,1996,159:418. |
| [19] | Weng W Z;Yan Q G;Luo C R;Liao Y Y Wan H L .[J].Catalysis Letters,2001,74:37. |
| [20] | Weng W Z;Chen M S;Wan H L .[J].Chemical Record,2002,2:102. |
| [21] | Chin Y H;Iglesia E .[J].JPhys Chem C,2011,115:17845. |
| [22] | Chin, Y.-H.;Buda, C.;Neurock, M.;Iglesia, E. .Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH_4-O_2 catalysis on supported Pt clusters[J].Journal of the American Chemical Society,2011(40):15958-15978. |
| [23] | Chin, Y.-H.;Buda, C.;Neurock, M.;Iglesia, E. .Selectivity of chemisorbed oxygen in C-H bond activation and CO oxidation and kinetic consequences for CH_4-O_2 catalysis on Pt and Rh clusters[J].Journal of Catalysis,2011(1):10-24. |
| [24] | Weng W Z;Pei X Q;Li J M;Luo C R Liu Y Lin H Q Huang C J Wan H L .[J].Catalysis Today,2006,117:53. |
| [25] | Tolia A A;Smiley R J;Delgass W N;Takoudis C G Weaver M J .[J].Journal of Catalysis,1994,150:56. |
| [26] | Guerrero-Ruiz A;Ferreira-Aparicio P;Bachiller-Baeza M B;Rodriguez-Ramos I .[J].Catalysis Today,1998,46:99. |
| [27] | Tsuji H;Shishido T;Okamura A;Gao Y Z,Hattori H,Kita H .[J].Journal of the Chemical Society,Faraday Transactions,1994,90:803. |
| [28] | Guerrero-Ruiz A;Rodriguez-Ramos I.Heterogeneous Hydrocarbon Oxidation[A].Madrid,Spain,1996:347. |
| [29] | Tsuji H.;Okamura-Yoshida A.;Shishido T.;Hattori H. .Dynamic behavior of carbonate species on metal oxide surface: Oxygen scrambling between adsorbed carbon dioxide and oxide surface[J].Langmuir: The ACS Journal of Surfaces and Colloids,2003(21):8793-8800. |
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%