偏铝酸四(4-羧基)苯基铁卟啉催化氧化环己烷

为考察偏铝酸MAA]负载四(4-羧基)苯基铁卟啉Fe TCPP]选择性催化氧化环己烷生成环己酮和环己醇(K/A油)的能力,采用溶胶-凝胶-煅烧法制备了偏铝酸负载四(4-羧基)苯基铁卟啉Fe TCPP/MAA]催化剂,采用紫外(UV-Vis)、傅立叶红外(FT-IR)、X射线衍射(XRD)、热重分析(TG)以及透射电镜(TEM)等技术手段对该固体催化材料进行结构表征。研究其在无外加溶剂和助催化剂的条件下选择性催化空气氧化环己烷生成K/A油的产率。结果显示:在较优的催化条件下(155℃和0.8 MPa),用仅含1.14×10-6mol四(4-羧基)苯基铁卟啉的负载催化剂,既可回收又可重复有效催化11次,平均的环己烷转化率达到13.6%,K/A油的产率为10.8%,转化数为2.4×105,比未负载的四(4-羧基)苯基铁卟啉催化效率高11倍,也比当今工业用钴盐催化空气氧化环己烷生产环己酮和环己醇的收率(3.2%)高。

Catalytic oxidation of cyclohexane over meta-aluminic acid supported iron meso-tetra (4-caboxylpheny1) porphyrin

To investigate the catalytic ability of iron meso-tetra(4-carboxylpheny1) porphyrin(Fe TCPP) supported on meta aluminic acid(MAA) for selective oxidation of cyclohexane to cyclohexanone and cyclohexanol(K/A oil),Fe TCPP/MAA was prepared via a method of gelation and calcination and characterized by the techniques of UV-Visible spectroscopy,Fourier transform infrared spectroscopy,X-ray diffraction,Thermogravimetric analysis,Transmission electron microscopy.The catalytic oxidation of cyclohexane with air was carried out in absence of any solvent and co-catalyst.The results show that with a quantity of catalyst containing only 1.14×10-6 mol of Fe TCPP,13.6 % of average conversion rate,10.8 % of yield(K/A oil) and a catalyst turnover number of 2.4 ×105 were reached under the optimum reaction conditions of 155 ℃ and 0.8 MPa.The catalytic efficiency of the supported catalyst is 11 times higher than that of Fe TCPP and the yield of K/A oil is higher than that obtained from the cyclohexane oxidation(3.2 %) by soluble cobalt catalyst used in industry at present.