| At present the most important industrial method of production of phenol is cumene oxidation process. In the sec-butyl benzene oxidation process, sec-butyl benzene is oxidated to sec-butyl benzene hydroperoxide, and then sec-butyl benzene hydroperoxide is decomposed to phenol and methyl ethyl ketone.This production process can be an effective supplement that can effectively regulate the supply and demand of phenol and acetone. Our country is short of petroleum resources and has low utilization rate of C4-product so it is very important to develop the sec-butyl benzene oxidation process. Developing the sec-butyl benzene oxidation process to produce phenol and methyl ethyl ketone has great economic, social and environmental benefits.In the industrial production sec-butyl benzene and cumene is normally obtained by the alkylation of benzene with olefins. In the products after alkylation sec-butyl benzene and cumene may both exist. If butyl benzene and cumene can be oxided together, the olefin separation process will be saved before alkylation, and a process route co-production of phenol, acetone and methyl ethyl ketone can be designed.In this paper, the method of production of phenol and methyl ethyl ketone by the sec-butyl benzene was studie. And the reaction process conditions of the oxidation and decomposition reaction were discussed; the process conditions of mixed oxidation of sec-butyl benzene and cumene was researched.A qualitative correlation and quantitative method to analysis the oxidation products was established. High performance liquid chromatography (HPLC) to was used to analysis of reaction products. And the conditions of the quantitative analysis of HPLC were:mobile phase flow was 1.0mL/min; the ratio of hexane and isopropanol was 98:2; detection wavelength was 257nm; column temperature was room temperature; a single injection volume was 3μL; analysis time was 10min. Under these conditions, sec-butyl benzene (sBB) and its oxidation production such as acetophenone (AP), sec-butyl benzene, hydrogen peroxide (sBBHP), and methyl ethyl benzyl alcohol (EMBA) can be separated well.The process conditions of the oxidation of sec-butyl benzene were studied. The experiment datas showed that the optimum conditions were:the self-made glass reactor was used as the reactor; the amount of raw materials sBB was 40g; the weight of CHP was 2%; the reaction temperature was 120℃; the pressure was atmospheric pressure; the stirring speed was 1000r/min; air flow was 150cc/min; the reaction time was controlled in 12h. In these conditions sBB conversion was 14%, sBBHP selectivity rate was 92%. Using azobisisobutyronitrile (AIBN), N-hydroxy phthalimide (NHPI), sBBHP and ionic liquids as catalysts for oxidation reactions had a certain effect. Using the ionic liquids as the catalyst, sBB conversion rate can reach 38%, using NHPI as catalyst sBBHP maximum selectivity rate can reach 95%.The oxidation kinetics of sec-butyl benzene were studied, a sec-butyl benzene hydrogen peroxide formation rate of macro dynamics equation. Was established:rsBBHP=dcsBBHP/dt=0.023-0.002csBBHPThe process conditions of mixed oxide sec-butyl benzene and cumene were studied. The results showed that under the conditions without catalyst, under 120℃after 12h of reation, when the sec-butyl benzene/cumene=0.25, sec-butyl benzene and cumene conversion rate can reach 24%, the selectivity rate of acetophenone was 14%; when the sec-butyl benzene/cumene= 4, the benzene conversion rate can reach 14%, and the selectivity rate of acetophenone was 4%; when the reaction temperature was 90℃, sBBHP+CHP selectivity rate can reach 97%; if using ionic liquids as catalyst, the reaction conversion rate can reach 40%, sBBHP+CHP selectivity rate was about 60% and the selectivity rate of benzyl alcohol was 30%.Acid decomposition reaction conditions of sec-butyl benzene hydrogenperoxide (sBBHP) were investigated. The experiment results showed that the optimum conditions of acid decomposition reaction were:using the three 50ml bottle as the reactor; sBB oxidation liquid dosage was 10g; the amount of concentrated sulfuric acid was 0.75% of the sBBHP quality; use methyl ethyl ketone as solvent to dilute sulfuric acid, the concentration of sulfuric acid was 0.5%; reaction temperature was 50℃; the reaction time was 20min. In this condition the conversion rate of sBBHP was close to 100%, and the yield of phenol was 95.5%In summary, this study implements the production of phenol and methyl ethyl ketone through oxidation and decomposition by sec-butyl benzene and obtained optimum process conditions. Sec-butyl benzene and cumene mixed oxided was studied and the optimum processing conditions were obtained. |
