13X分子筛负载Fe催化剂上1,4-二氧六环在空气中完全氧化

doi:10.1016/S1872-2067(15)61030-0

摘要/Abstract

摘要：

采用浸渍法制备了不同Fe含量的13X分子筛负载的Fe催化剂(Fe/X13), 运用N₂吸附-脱附法测得其BET比表面积和BJH孔径分布, 采用X射线衍射、扫描电镜、程序升温还原和NH₃程序升温脱附法表征了该催化剂的织构性质. 在固定床流动反应器中, 以空气为氧化剂、在100-400℃范围内考察了Fe/X13催化剂上1,4-二氧六环的完全氧化反应性能, 研究了反应温度、金属担载量和气体空速(GHSV)等条件对催化氧化降解二氧六环反应性能的影响, 并在400℃测定了该催化剂反应50 h的稳定性. 结果表明, 6 wt% Fe/13X催化剂表现出最高的催化性能, 在400℃, GHSV = 24000 h^-1的条件下, 二氧六环转化率为97%, 生成CO和CO₂的选择性达95%, 降解产物还包括少量的乙醛、乙二醇-甲酸酯、乙二醇二甲酸、1,4-二氧六环-2醇、1,4-二氧六环-2酮及2-甲氧基1,3二氧戊环. 基于这些经色谱-质谱联用仪检测出的产物, 提出了可能的1,4-二氧六环降解机理.

关键词: 铁, 13X分子筛, 1,4-二氧六环, 催化降解, 完全氧化, 降解机理

Abstract:

Zeolite-13X-supported Fe (Fe/zeolite-13X) catalysts with various Fe contents were prepared by the wet impregnation method. The catalysts were characterized by N₂ adsorption-desorption isotherms to estimate the Brunauer-Emmett-Teller surface areas and Barrett-Joyner-Hanlenda pore size distributions. X-ray diffraction, scanning electron microscopy, temperature-programmed reduction, and temperature-programmed desorption of NH₃ were used to investigate the textural properties of the Fe/zeolite-13X catalysts. Their catalytic activities were determined for the complete oxidation of 1,4-dioxane using air as the oxidant in a fixed‐bed flow reactor in the temperature range 100-400℃. The influences of various process parameters, such as reaction temperature, metal loading, and gas hourly space velocity (GHSV), on the dioxane removal efficiency by catalytic oxidation were investigated. The stability of the catalyst was tested at 400℃ by performing time-on-stream analysis for 50 h. The Fe/zeolite-13X catalyst with 6 wt% Fe exhibited the best catalytic activity among the Fe/zeolite-13X catalysts at 400℃ and a GHSV of 24000 h^-1, with 97% dioxane conversion and 95% selectivity for the formation of carbon oxides (CO and CO₂). Trace amounts (< 3%) of acetaldehyde, ethylene glycol monoformate, ethylene glycol diformate, 1,4-dioxane-2-ol, 1,4-dioxane-2-one, and 2-methoxy-1,3-dioxalane were also formed as degradation products. A plausible degradation mechanism is proposed based on the products identified by GC-MS analysis.

Key words: Iron, Zeolite-13X, 1,4-Dioxane, Catalytic degradation, Complete oxidation, Degradation mechanism

C. Ramakrishna, R. Krishna, T. Gopi, G. Swetha, Bijendra Saini, S. Chandra Shekar, Anchal Srivastava. 13X分子筛负载Fe催化剂上1,4-二氧六环在空气中完全氧化[J]. 催化学报, 2016, 37(2): 240-249.

C. Ramakrishna, R. Krishna, T. Gopi, G. Swetha, Bijendra Saini, S. Chandra Shekar, Anchal Srivastava. Complete oxidation of 1,4-dioxane over zeolite-13X-supported Fe catalysts in the presence of air[J]. Chinese Journal of Catalysis, 2016, 37(2): 240-249.

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