钴取代Dawson型磷钼钒催化氧化环己烷制环己酮和环己醇

合成了Dawson型磷钼钒钴杂多酸盐,用傅立叶变换红外光谱、X射线衍射和31P核磁共振等方法表征了磷钼钒钴的结构。以环己烷为原料、H2O2为氧化剂、磷钼钒钴杂多酸盐为催化剂催化氧化制备了环己醇和环己酮,考察了催化剂的钒含量和反应条件(催化剂用量、H2O2用量、反应时间、反应温度)对环己烷氧化反应的影响。实验结果表明,钒含量适中的Co2H5P2Mo15V3O62催化剂活性最高。在Co2H5P2Mo15V3O62用量0.20 mmol、w(H2O2)=50%的双氧水用量13.6 g(0.2 mol)、反应时间10 h、反应温度75℃、叔丁醇用量30 mL的优化反应条件下,环己烷的转化率为88.37%,环己醇和环己酮的总收率可达16.56%。

Preparation of Cyclohexanol and Cyclohexanone through Oxidation of Cyclohexane Over Cobalt Substitute for Dawson P-Mo-V as Catalyst

Synthesized Dawson P-Mo-V Cobalt Heteropolyacid Salts were characterized by FTIR,XRD and ~(31)PNMR.Cyclohexane was oxidated to cyclohexanol and cyclohexanone under the conditions with cyclohexane as the raw material,H_2O_2 as the oxidant and the cobalt substitute for dawson P-Mo-V cobalt heteropolyacid salts as catalysts.The reaction conditions such as the type of catalyst,the amount of catalyst and H_2O_2,reaction time and temperature were investigated.Experimental results show that Co_2H_5P_2Mo_(15)V_3O_(62) has the highest activity of catalysts,The conversion of cyclohexane was 88.37% and the total yield of cyclohexanol and cyclohexanone was 16.56% under the conditions of the amount of Co_2H_5P_2Mo_(15)V_3O_(62)catalyst 0.20 mmol,H_2O_2 with w(H_2O_2)=50% amounting to 0.2 mol,reaction time 10 h,the temperature 75 ℃.