氧化法合成环己酮（醇）的研究
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摘要
本文制备了三种不同催化剂,并将其用于以30 %过氧化氢为氧化剂的环己烷选择性氧化合成环己酮和环己醇的反应,考察了催化剂制备条件和氧化反应条件对环己烷选择性氧化反应性能的影响。
用离子交换法Cu/HZSM-5分子筛催化剂,并对催化剂进行了XRD、FT-IR、BET、ICP、TG/DTA等表征。表征结果表明,CuO的晶化发生在300和400℃之间;分散在HZSM-5分子筛中的Cu物种与分子筛存在多种配位键合作用。Cu/HZSM-5催化剂的最佳制备条件为:Cu担载量10 %,离子交换温度80℃,离子交换时间8 h,焙烧温度600℃。在环己烷0.5 mL,乙腈10 mL,Cu/HZSM-5催化剂0.03 g,H_2O_24 mL,反应温度65℃下反应6 h,环己烷转化率为43.1 %,环己酮和环己醇的总选择性为95.7 %。
用浸渍法制备了Co-Mo/V_2O_5复合催化剂,并对催化剂进行了XRD、FT-IR、BET等表征。表征结果表明,掺杂组分Co和Mo与纯V_2O_5作用生成了具有催化活性但晶相不完整的复合金属氧化物CoMoO4(2θ=28.51°)和CoMoO3(2θ=18.06°)的特征峰。Co-Mo/V_2O_5催化剂的最佳制备条件为:Mo的掺入量为20 %,Co的掺入量为5 %,浸渍时间为1 h,焙烧温度为600℃。在环己烷0.5 mL,乙腈10 mL,Co-Mo/V_2O_5催化剂0.03 g,H_2O_23 mL,反应温度为55℃下反应3 h,环己烷的转化率为39.1 %,环己酮和环己醇的总选择性为100 %。
用浸渍法制备了CuPMo/V_2O_5复合催化剂,并对催化剂进行了XRD、FT-IR、BET等表征。表征结果表明,组合改性并没有破坏V_2O_5的结构,PMo和CuO都高度分散于V_2O_5上。CuPMo/V_2O_5催化剂的最佳制备条件为:浸渍时间12 h,焙烧温度320℃。在环己烷0.5 mL,乙腈10 mL,CuPMo/V_2O_5催化剂0.03 g,H_2O_2 3 mL,反应温度65℃下反应3 h,环己烷转化率为53.6 %,环己酮和环己醇的总选择性为100 %。
In this paper, three catalysts were successfully prepared, and which were applied to catalyze selective oxidation of cyclohexane to cyclohexanone and cyclohexanol using oxygen. These catalysts were characterized by a series of methods, the effects of catalyst preparation conditions and oxidation reaction parameters on their catalytic performances were investigated in cyclohexane oxidation to cyclohexanone and cyclohexanol using oxygen as the oxidant.
A catalyst comprising Cu/HZSM-5 molecular sieves was prepared by ion exchange and characterized by XRD, BET, ICP, FT-IR and TG/DTA. Crystallization of CuO occurs between 300 and 400℃. The presence of various ligand bonds between the support and the copper species scattered in the molecular sieve matrix. Cu/HZSM-5 subjected to ion exchange with 10 % copper nitrate solution at 80℃for 8 h and calcination at 600℃exhibited the best performance. Using 0.5 mL of cyclohexane,10 mL of acetonitrile, 4 mL of hydrogen peroxide and 0.03 g of catalyst at a reaction temperature of 65℃for 6 h, the cyclohexane conversion was 43.1 % and the total selectivity to cyclohexanol and cyclohexanone was 95.7 %.
New type composite catalyst of V_2O_5 comprising Co-Mo/V_2O_5 was prepared by immersion method and characterized by XRD, BET and FT-IR. CoMoO4 and CoMoO3 are the incomplete crystalline phase complex metal oxides which have catalytic activity, demonstrating that there is interaction between pure V_2O_5 and doped components. Co-Mo/V_2O_5 subjected to immersion method with 5 % Co and 20 % Mo mixed solution at room temperature for 1 h and calcination at 600℃exhibited the best performance. Using 0.5 mL of cyclohexane, 3 mL of hydrogen peroxide and 30 mg of catalyst at a reaction temperature of 55℃for 3 h, the cyclohexane conversion was 39.1 % and the total selectivity to cyclohexanol and cyclohexanone was 100 %.
CuPMo/V_2O_5 catalyst was prepared by immersion method and characterized by XRD, BET and FT-IR. The doping components had no obvious effect on the structure of V_2O_5 and were highly dispersed on the surface of V_2O_5. CuPMo/V_2O_5 subjected to immersion method at room temperature for 12 h and calcination at 320℃exhibited the best performance. Using 0.5 mL of cyclohexane, 3 mL of hydrogen peroxide and 30 mg of catalyst at a reaction temperature of 65℃for 3 h, the cyclohexane conversion was 53.6 % and the total selectivity to cyclohexanol and cyclohexanone was 100 %.
用离子交换法Cu/HZSM-5分子筛催化剂,并对催化剂进行了XRD、FT-IR、BET、ICP、TG/DTA等表征。表征结果表明,CuO的晶化发生在300和400℃之间;分散在HZSM-5分子筛中的Cu物种与分子筛存在多种配位键合作用。Cu/HZSM-5催化剂的最佳制备条件为:Cu担载量10 %,离子交换温度80℃,离子交换时间8 h,焙烧温度600℃。在环己烷0.5 mL,乙腈10 mL,Cu/HZSM-5催化剂0.03 g,H_2O_24 mL,反应温度65℃下反应6 h,环己烷转化率为43.1 %,环己酮和环己醇的总选择性为95.7 %。
用浸渍法制备了Co-Mo/V_2O_5复合催化剂,并对催化剂进行了XRD、FT-IR、BET等表征。表征结果表明,掺杂组分Co和Mo与纯V_2O_5作用生成了具有催化活性但晶相不完整的复合金属氧化物CoMoO4(2θ=28.51°)和CoMoO3(2θ=18.06°)的特征峰。Co-Mo/V_2O_5催化剂的最佳制备条件为:Mo的掺入量为20 %,Co的掺入量为5 %,浸渍时间为1 h,焙烧温度为600℃。在环己烷0.5 mL,乙腈10 mL,Co-Mo/V_2O_5催化剂0.03 g,H_2O_23 mL,反应温度为55℃下反应3 h,环己烷的转化率为39.1 %,环己酮和环己醇的总选择性为100 %。
用浸渍法制备了CuPMo/V_2O_5复合催化剂,并对催化剂进行了XRD、FT-IR、BET等表征。表征结果表明,组合改性并没有破坏V_2O_5的结构,PMo和CuO都高度分散于V_2O_5上。CuPMo/V_2O_5催化剂的最佳制备条件为:浸渍时间12 h,焙烧温度320℃。在环己烷0.5 mL,乙腈10 mL,CuPMo/V_2O_5催化剂0.03 g,H_2O_2 3 mL,反应温度65℃下反应3 h,环己烷转化率为53.6 %,环己酮和环己醇的总选择性为100 %。
In this paper, three catalysts were successfully prepared, and which were applied to catalyze selective oxidation of cyclohexane to cyclohexanone and cyclohexanol using oxygen. These catalysts were characterized by a series of methods, the effects of catalyst preparation conditions and oxidation reaction parameters on their catalytic performances were investigated in cyclohexane oxidation to cyclohexanone and cyclohexanol using oxygen as the oxidant.
A catalyst comprising Cu/HZSM-5 molecular sieves was prepared by ion exchange and characterized by XRD, BET, ICP, FT-IR and TG/DTA. Crystallization of CuO occurs between 300 and 400℃. The presence of various ligand bonds between the support and the copper species scattered in the molecular sieve matrix. Cu/HZSM-5 subjected to ion exchange with 10 % copper nitrate solution at 80℃for 8 h and calcination at 600℃exhibited the best performance. Using 0.5 mL of cyclohexane,10 mL of acetonitrile, 4 mL of hydrogen peroxide and 0.03 g of catalyst at a reaction temperature of 65℃for 6 h, the cyclohexane conversion was 43.1 % and the total selectivity to cyclohexanol and cyclohexanone was 95.7 %.
New type composite catalyst of V_2O_5 comprising Co-Mo/V_2O_5 was prepared by immersion method and characterized by XRD, BET and FT-IR. CoMoO4 and CoMoO3 are the incomplete crystalline phase complex metal oxides which have catalytic activity, demonstrating that there is interaction between pure V_2O_5 and doped components. Co-Mo/V_2O_5 subjected to immersion method with 5 % Co and 20 % Mo mixed solution at room temperature for 1 h and calcination at 600℃exhibited the best performance. Using 0.5 mL of cyclohexane, 3 mL of hydrogen peroxide and 30 mg of catalyst at a reaction temperature of 55℃for 3 h, the cyclohexane conversion was 39.1 % and the total selectivity to cyclohexanol and cyclohexanone was 100 %.
CuPMo/V_2O_5 catalyst was prepared by immersion method and characterized by XRD, BET and FT-IR. The doping components had no obvious effect on the structure of V_2O_5 and were highly dispersed on the surface of V_2O_5. CuPMo/V_2O_5 subjected to immersion method at room temperature for 12 h and calcination at 320℃exhibited the best performance. Using 0.5 mL of cyclohexane, 3 mL of hydrogen peroxide and 30 mg of catalyst at a reaction temperature of 65℃for 3 h, the cyclohexane conversion was 53.6 % and the total selectivity to cyclohexanol and cyclohexanone was 100 %.
引文
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