NHPI催化分子氧氧化α-O-4型木质素模型分子  

Aerobic Oxidation of α-O-4 Bond Type Lignin Model Compound Using N-Hydroxyl Phthalimide

作　　者：陈宁[1] 刘颖颖 鲁厚芳[1,2] 刘长军 梁斌[1,2] 

机构地区：[1]四川大学化学工程学院,四川成都610065 [2]四川大学新能源与低碳技术研究院,四川成都610065

出　　处：《精细化工》2017年第12期1379-1384,共6页Fine Chemicals

基　　金：国家自然科学青年基金项目(21406146);国家自然科学基金面上项目(21476150);国家自然科学基金重点项目(21336008)~~

摘　　要：以苄基苯基醚为模型分子,氧气为氧化剂,考察了N-羟基邻苯二甲酰亚胺(NHPI)对分子氧氧化木质素醚键(α-O-4)的催化作用和多种可溶性过渡金属盐的助催化作用,探究了NHPI和硝酸铜用量、反应温度、反应时间和氧气分压对反应的影响。结果表明:NHPI催化分子氧氧化苄基苯基醚生成苯甲醛和苯酚,在可溶性的钴、锰、镍和铜盐中,铜盐对NHPI的助催化作用最好。在NHPI/Cu(NO3)2催化下,当氧分压高于0.5 MPa时,苄基苯基醚的氧化反应对氧气为0级。过高温度会加剧目标产物苯甲醛和苯酚的深度氧化。优化的工艺条件为,以乙酸为溶剂,n(苄基苯基醚)∶n(NHPI)∶n(硝酸铜)=1.0∶0.2∶0.02,氧气分压为1.0 MPa时,在110℃下反应15h,苄基苯基醚的转化率为37.2%。The catalytic effects of N-hydroxyl phthalimide combined with various transition metal salts on the oxidative cleavage of α-O-4 ether bond in lignin by oxygen were studied,and benzyl phenyl ether was used as α-O-4 lignin model compound. Meanwhile,the factors affecting catalytic activity of NHPI,such as dosage of NHPI and copper nitrate,reaction temperature,reaction time and partial pressure of oxygen were discussed. It is found that NHPI could make benzyl phenyl ether generate the benzaldehyde and phenol. The cupric salts showed the highest promotion effect on the catalytic activity of NHPI among the soluble cobaltous,manganous,nickel and cupric salts. The oxidation reaction of benzyl phenyl ether was zero-order reaction for oxygen using NHPI and cupric nitrate as catalysts when partial pressure of oxygen exceeded 0. 5 MPa Additively,too high reaction temperature would lead to over oxidation of benzaldehyde and phenol. The conversion of benzyl phenyl ether was 37. 2%,respectively,in acetic acid under the conditions of 110 ℃ for 15 hours,1. 0 MPa O2 and using 20%NHPI and 2% Cu（ NO3）2 based on amount of benzyl phenyl ether（ mole fraction） as catalysts.

关 键 词：N-羟基邻苯二甲酰亚胺(NHPI) 催化氧化 氧气 木质素 苯甲醛 催化与分离提纯技术 

分 类 号：O643.32[理学—物理化学] O625[理学—化学]