化学学报 ›› 2005, Vol. 63 ›› Issue (24): 2205-2210. 上一篇    下一篇

研究论文

新型反相微乳液制备纳米结构甲烷催化燃烧催化剂La0.95Ba0.05MnAl11O19-α的研究

徐金光*,1,腾飞2,田志坚2,曲秀华1, 张培青1,徐云鹏2,熊国兴3,林励吾2,3   

  1. (1烟台大学化学生物理工学院 应用催化研究所 烟台 264005)
  • 投稿日期:2005-04-06 修回日期:2005-08-17 发布日期:2005-12-28
  • 通讯作者: 徐金光

Novel Reverse Microemulsion and Its Application to Synthesis of Nanostructured La0.95Ba0.05MnAl11O19-α Catalyst for Methane Combustion

XU Jin-Guang*,1, TENG Fei2, TIAN Zhi-Jian2, QU Xiu-Hua1, ZHANG Pei-Qing1, XU Yun-Peng2, XIONG Guo-Xing3, LIN Li-Wu2,3   

  1. (1 Institute of Applied Catalysis, Yantai University, Yantai 264005)
    (2 Laboratory of Natural Gas Utilization and Applied Catalysis, Dalian Institute of Chemical Physics,
    Chinese Academy of Sciences, Dalian 116023)
    (3 State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023)
  • Received:2005-04-06 Revised:2005-08-17 Published:2005-12-28
  • Contact: XU Jin-Guang

提出一种由水, 异丙醇, 正丁醇组成的新型微乳液, 并以其为反应介质制备了甲烷高温燃烧La0.95Ba0.05MnAl11O19-a催化剂. 采用1H NMR, FT-IR, 电导法及激光粒度散射法研究了新型微乳液中水的结构及相特性. 新型微乳液中水的体积分数小于一定值时, 电导率与水含量成非线性关系, kφ曲线上存在一临界值(φP=0.15). 水质子的化学位移随水含量的降低移向高场. 加入4% D2O测定的O—D键的伸缩振动随水含量增加而向高波数方向移动. 异丙醇铝在新型微乳液中水解形成的Al(OH)3 胶体粒子的粒径范围为226~329 nm. 采用新型微乳液作为反应介质制备的Ba0.05La0.95MnAl11O19-α催化剂的粒径在30 nm, 明显小于纯水制备的样品(100 nm). BET 比表面积为65 m2/g, 比纯水制备样品高出约一倍. XRD结果显示, 1200 ℃焙烧10 h即可获得含单一β-Al2O3相的催化剂. Ba0.05La0.95MnAl11O19-α催化剂甲烷催化燃烧的T10为420 ℃, 比纯水制备样品下降了90 ℃. 甲烷催化燃烧活性提高是由于含有较多Mnn+纳米结构六铝酸盐的形成.

关键词: 甲烷, 催化燃烧, 反相微乳液, 六铝酸盐, 正丁醇, 异丙醇

A novel type of reverse microemulsion system composed of water, i-propanol and n-butanol was developed as a reaction medium to prepare substituted-hexaaluminate La0.95Ba0.05MnAl11O19-α catalyst for methane combustion. The structure and properties of water in the novel reverse microemulsion system were investigated by means of 1H NMR, FT-IR, electrical conductometry and laser light scattering apparatus. The electric conductivity of the novel reverse microemulsion system followed a nonlinear correlation when the volume fraction of water was low. There existed a critical point of φP (0.15) along the kφ curve. 1H NMR revealed that the chemical shift of the water proton signal moved to upfield with decreasing water content. FTIR showed that the νO-D band was shifted to higher frequency with increasing water concent. The size distribution of the Al(OH)3 gel particles formed by hydrolysis of Al(i-OC3H7)3 in the novel reverse microemulsion ranged from 226 to 329 nm with the average diameter of 267 nm. Substituted hexaaluminate La0.95Ba0.05MnAl11O19-α synthesized in the novel reverse microemulsion system possesses a surface area of 65 m2/g, comparable to 32 m2/g of similar samples prepared with pure water. XRD measurements revealed that β-Al2O3 was the only phase for this catalyst after calcination at 1200 ℃ for 10 h and its particle size measured by TEM is about 30 nm. This nanostructured hexaaluminate, when used as a catalyst for CH4 combustion, allowed a light-off of a stream of 1% CH4 in air at 420 ℃, as compared to 510 ℃ required for similar catalyst prepared with pure water. The excellent low-temperature catalytic activity of this catalyst arised from the formation of nanostrctured hexaaluminate that contained larger amount of manganese.

Key words: methane, catalytic combustion, reverse microemulsion, hexaaluminate, n-butanol, i-propanol