4-甲氧基环己酮的绿色合成  

Green Synthesis of 4-Methoxycyclohexanone

作　　者：褚晓宁 牛立博[1] 陈波 时晓珍 白国义[1] 

机构地区：[1]河北大学化学与环境科学学院

出　　处：《精细化工》2018年第2期349-356,共8页Fine Chemicals

基　　金：国家自然科学基金(21676068,21376060);河北省自然科学基金(B2014201024)~~

摘　　要：在Al2O3负载的镍基纳米催化剂作用下进行了4-甲氧基苯酚催化加氢反应,然后使用双氧水对加氢反应液进行催化氧化合成4-甲氧基环己酮。在催化加氢反应中,考察了沉积-沉淀法和浸渍法及反应条件对催化剂活性和稳定性的影响。通过XRD、H2-程序升温还原（H2-TPR）及TEM等对催化剂进行了表征,结果发现,沉积-沉淀法制备的Ni/Al2O3-DP催化剂中活性粒子分散度高、粒径较小,并且活性粒子与载体之间有较强的作用力,具有比浸渍法制备的Ni/Al2O3-IMP催化剂更好的活性和稳定性。在4-甲氧基苯酚的加氢反应中,以Ni/Al2O3-DP为催化剂,最佳的反应条件为：反应温度423 K、反应压力4.0 MPa、反应时间1.0 h、m（4-甲氧基苯酚）∶m（Ni/Al2O3-DP）=6∶1。在氧化反应中,探究了氧化条件对反应活性的影响,结果表明：当n（4-甲氧基环己醇）∶n（双氧水）=1.0∶2.5时,353 K反应20 h,目标产物4-甲氧基环己酮的选择性可达95.3%。The catalytic hydrogenation of 4-methoxyphenol was first carried out over supported nickel- based catalysts. Subsequently, the hydrogenation solution was oxidized by hydrogen peroxide to further improve selectivity of 4-methoxycyclohexanone. The influences of preparation methods including deposition-precipitation method and impregnation method, as well as conditions for the catalytic hydrogenation reaction on the activity and stability of catalyst were investigated. The prepared catalysts were characterized by X-ray diffraction （ XRD ）, H2-temperature programmed reduction （ H2-TPR） , transmission electron microscopy （TEM） and so on. The results showed that the Ni/A1203-DP catalyst prepared by deposition-precipitation method exhibited better catalytic activity and stability than the Ni/ A1203-IMP catalyst prepared by impregnation method, which was attributed to the fact that the deposition-precipitation led to active particle higher dispersion, smaller particle size, and stronger interaction between the active particles and the support. The optimum reaction conditions for the hydrogenation of 4-methoxyphenol over Ni/AI203-DP were obtained as follows： reaction temperature 423 K, reaction pressure 4.. 0 MPa, reaction time 1.0 hour, mass ratio of 4-methoxyphenol to Ni/A1203- DP of 6：1. In addition, it was found that the total selectivity of 4-methoxycyclohexanone could reach 95.3% when n （ 4-methoxycyclohexanol ） ： n （ hydrogen peroxide ） was 1.0 ： 2. 5 and the oxidation reaction was conducted at 353 K for 20 hours.

关 键 词：4-甲氧基苯酚 4-甲氧基环己酮 催化加氢 氧化 绿色合成 精细化工中间体 

分 类 号：O621.3[理学—有机化学]