采用燃烧法制备了Sr掺杂钙钛矿型氧化物La1-xSrxFeO3(x =0,0.3,0.5,0.9)载氧体,对载氧体分别进行X射线衍射、扫描电镜和H2程序升温还原反应表征,在热重循环装置和固定床反应装置上考察甲烷与载氧体晶格氧的部分氧化反应.结果表明, La1-xSrxFeO3氧化物中的晶格氧适用于甲烷部分氧化制合成气,晶格氧的得失是一个可逆过程, Sr的掺杂提高了载氧体的供氧能力,5次循环后载氧体得失晶格氧的能力没有明显的衰减.从甲烷转化率、n(H2)/n(CO)比以及H2和CO的选择性等方面来考虑, x =0.3-0.5比较理想,甲烷转化率维持在70%左右,气体产物中n(H2)/n(CO)约为2, CH4没有发生明显的裂解.
We prepared perovskite-type oxides La1-xSrxFeO3 (x = 0, 0.3, 0.5, 0.9) by a combustion method and used these as oxygen carriers for the partial oxidation of methane. X-ray diffration, scanning elec-tron microscopy and H2 temperature-programmed reduction techniques were used to characterize the samples. Their reduction and oxidation activities were investigated using a thermogravimetric analysis reactor and fixed-bed reaction equipment, respectively. The results showed that the lattice oxygen in La1-xSrxFeO3 was suitable for the partial oxidation of methane to produce syngas. Their capacity to provide oxygen was enhanced by the partial substitution of La3+ by Sr2+ and the synthe-sized materials have good regenerability. The optimal degree of Sr substitution was found to be x =0.3-0.5 for La1-xSrxFeO3 with regard to reactivity, selectivity, and oxygen-donating ability. CH4 con-version was higher than 70%, and the n(H2)/n(CO) ratio remained about 2:1 and no obvious de-composition of CH4 occurred.
参考文献
| [1] | 周总瑛.从石油供需缺口论中国石油安全策略[J].资源科学,2004(06):111-117. |
| [2] | 许珊,王晓来,赵睿.甲烷催化制氢气的研究进展[J].化学进展,2003(02):141-150. |
| [3] | 徐占林,毕颖丽,甄开吉.甲烷催化二氧化碳重整制合成气反应研究进展[J].化学进展,2000(02):121-130. |
| [4] | 姜洪涛,Li Huiquan,李会泉,张懿.甲烷三重整制合成气[J].化学进展,2006(10):1270-1277. |
| [5] | 孙长庚,刘宗章,张敏华.甲烷催化部分氧化制合成气的研究进展[J].化学工业与工程,2004(04):276-280. |
| [6] | Fathi M;Hofstad H K;SPerie T;Rokstad O A Holmen A .[J].Catal To-day,1998,42:205. |
| [7] | Richter H;KnocheK .[J].ACS SYMPOSIUM SERIES,1983,235:71. |
| [8] | Ryde′n M;Lyngfelt A;Mattisson T;Chen D Hdmen A Bj?rgum E .[J].Greenhouse Gas Control,2008,2:21. |
| [9] | Pimenidou, P.;Rickett, G.;Dupont, V.;Twigg, M.V. .Chemical looping reforming of waste cooking oil in packed bed reactor[J].Bioresource Technology: Biomass, Bioenergy, Biowastes, Conversion Technologies, Biotransformations, Production Technologies,2010(16):6389-6397. |
| [10] | Ryden M;Lyngfelt A;Mattisson T .[J].Energy and Fuels,2008,22:2585. |
| [11] | Luis F;De Diego;Ortiz M;Garcia-Labiano F Adanez J Abad A Gayan P .[J].power Source,2009,192:27. |
| [12] | Zhu X;Wang H;Wei Y G;Li K Z.Cheng X M .[J].Rare Earths,2010,28:907. |
| [13] | 李然家,余长春,代小平,沈师孔.钙钛矿型La0.8Sr0.2FeO3中的晶格氧用于甲烷选择氧化制取合成气[J].催化学报,2002(06):549-554. |
| [14] | 李然家,余长春,朱光荣,沈师孔,张志翔.AFeO3（A=La,Nd,Sm,Eu）钙钛矿中的晶格氧用于天然气部分氧化制合成气[J].石油与天然气化工,2004(z1):5-8. |
| [15] | Dai X P;Yu C C;Li R J;Wu Q Shi K Hso Z .[J].Rare Earths,2008,26:341. |
| [16] | 张晓静,李华举,李勇,申文杰.Sr取代LaFeO3钙钛矿的结构性质和催化性能[J].催化学报,2012(07):1109-1114. |
| [17] | 刘源;胡泽善;钟炳;彭少逸 .[J].催化学报,1996,17:256. |
| [18] | Zhang R D;Villanueva A;Alamdari H;Kaliaguine S .[J].Journal of Catalysis,2006,237:368. |
| [19] | Zhang H M;Yamazoe N;Teraoka Y .[J].Materials Science Letters,1989,8:995. |
| [20] | Saracco G;Geovaldo F;Baldi G .[J].Applied Catalysis B:Environmental,1999,20:277. |
| [21] | 陈永红,魏亦军,刘杏芹,孟广耀.La1-xSrxFeO3-δ系钙钛矿材料的表征和性能[J].无机化学学报,2006(01):31-36. |
| [22] | 钟子宜;陈立刚;颜其洁;傅献彩 .[J].分子催化,1996,54:585. |
| [23] | 李然家,余长春,代小平,沈师孔.以晶格氧为氧源的甲烷部分氧化制合成气[J].催化学报,2002(04):381-387. |
| [24] | He F;Wei Y G;Li H B;Wang H .[J].Energy and Fuels,2009,23:2095. |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%