The Research On Selective Aerobic Oxidation Of Cyclohexane And Cyclohexanone To Adipic Acid Catalyzed By Metalloporphyrin

Selective oxidation of alkanes is primarily important to petrochemistry,drug design,stuff and synthetical chemistry,and selective oxidation from cyclohexane to adipic acid is one of very important reactions. Adipic acid is extensively used in the man-made fiber industry along with hexamethylenediamine for manufacturing nylon 66,in addition to its innumerable applications as plasticizers, synthetic lubricants.There are more than 2.8 million tons adipic acid was produced per year.Now adipic acid is manufactured from cyclohexane in two major reactions with low conversion and selectivity and the consequent production of large quantities of nitrous oxide. This nitrous oxide emission measurably contributes to global warming.So it were important and interesting to study green and efficient methods of selective oxidation from cyclohexane to adipic acid . This thesis reported a system with different simple metalloporphyrins as catalyst, without any solvents, aerial oxygenated cyclohexane or cyclohexanone to adipic acid,and found an improved method of oxidation of cyclohexane to adipic acid. The contents of this thesis are presented as follows: 1.Firstly, a reversed phase high performance liquid chromatography (RP-HPLC) method with internal standard was proposed for the simultaneous determination of adipic acid,glutaric acid,succinic acid and malonic acid.We get the optimal reaction conditions.The method is simple,rapid and accurate. 2. Sencondly,one-pot liquid phase oxidation of cyclohexane to adipic acid with air catalyzed by different simple metalloporphyrins under different conditions such as reaction temperature,reaction time and air pressure were studied.All parameters revealed significantly influence the conversion of cyclohexane and selectivity of adipic acid. We got the optimal reaction conditions. 3. For more studies of the potential mechanism of the oxidation of cyclohexane and new methods of synthesis of adipic acid ,we introduced the studies of the catalytic oxidation of cyclohexanone or cyclohexanol.We found the oxidation of cyclohexanone reacted fastly but the reaction of oxidation of cyclohexanol did not. The selective catalysis of simple metalloporphyrins for the oxidation of cyclohexanone with air was studied in the absence of cocatalyst and solvents for the first time. The effects of various parameters such as reaction temperature, reaction time and air pressure were explored and we got the optimal reaction conditions. 4. In the end of this thesis we discussed the potential mechanism of the oxidation of cyclohexane or cyclohexanone catalyzed by metalloporphyrins according to the results of some comparative experiments and literature reports. The selective catalysis of simple metalloporphyrins for the oxidation of cyclohexane to adipic acid with air was studied in the presence of a few cyclohexanone as a promoter and without any solvents.