Extraction Of Reaction Solution Of Biomimetic Catalyzed Oxidiation Of Cyclohexane By Extractant Water

Air oxidation of cyclohexane is an importantant industrial chemical reaction, KA oil and adipic acid, the main products, are essential organic chemical raw materials. KA oil is used to produce caprolactam and adipic acid. Adipic acid is mainly used to prepare nylon-66and Polyurethane. Currently, the air oxidation of cyclohexane has different methods, catalyzed oxidation with cobalt salt, no catalyzed oxidation and biomimetic oxidation were included. Compared with those traditional methods, the biomimetic oxidation of cyclohexane was catalyzed by porphyrin catalyst at a lower temperature with higher conversion and selectivity. The concentration of cyclohexyl hydroperoxide is low and the organic acid with high value cover great part in the by-products.For the particularity of biomimetic oxidation, extraction was used to not only recover the useful by-products, especially the dicarboxylic acids, but also separate them from the oxidized liquid mixtures in this work. Water is chose as extrctant. This method is good for environmental protection and produces significant economic value.In this work, we researched the extraction of oxidized liquid mixture, related thermodynamic data were measured. A detailed mathematical model of extraction column was established. The extraction process was optimized for the industrial application of extraction. The main works of this thesis are listed as follows:1. Liquid-liquid equilibria (LLE) data for these ternary systems water+cyclohe xane+cyclohexanol, water+cyclohexanol+cyclohexanone and water+cyclohexanol+cyclohexanone were measured at (303.2to333.2) K and atmospheric pressure. The experimental data were correlated with both UNIQUAC and NRTL activity coefficient models. The relevant model parameters were simultaneously regressed with the experimental data by using matlab program. Binary interaction parameters of UNIQUAC and NRTL models of water+cyclohexane, water+cyclohexanol, water+cyclo hexanone, cyclohexane+cyclohexanol, cyclohexane+cyclohexanone and cyclohexanol+cyclohexanone were obtained. The simualted results gave good agreement with the experimentally determined ternary LLE data. The obtained model parameters can be used in the prediction and calculation of LLE for the ternary system water+cyclohexane+cyclohexanol, water+cyclohexane+cyclohexanone and water+cyclohexanol+cyclohexanone as well as for the prediction of LLE of quoaternary system water+cyclohexane+cyclohexanol+cyclohexanone.2. The Solid-liquid equilibria data of succinic acid, glutaric acid, adipic acid in water and binary cyclohexanone+cyclohexanol solvent mixtures were fitted by using NRTL model. Some binary interaction parameters were obtained from the SLE data. Binary NRTL model interaction parameters of water+succinic acid, water+glutaric acid, water+adipic acid, adipic acid+cyclohexanol, glutaric acid+cyclohexanol, succinic acid+cyclohexanol, adipic acid+cyclohexanone, succinic acid+cyclohexanone, glutaric acid+cyclohexanone were obtained. The average relative deviation between the experiment data and caculated data was3.46%. NRTL activity coefficient model can be used to fit the SLE of these systems. The obtained NRTL model binary interaction parameters are of great importancse in the prediction and calculation of solid-liquid equilibrium process.3. Aspen plus was used to simulated the extraction process. Simulated results were were veriricated with the experiment results. By using Aspen plus, the influence of temperature, theorical stage numbers and extractant dosage on the extract process was invesgated. Back-extraction was proposed to restrieve the cyclohexanol and cyclohexanone extracted by water.