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Direct Hydration Of β-Caryophyllene And Cyclohexene

Posted on:2014-06-08Degree:MasterType:Thesis
Country:ChinaCandidate:P K WuFull Text:PDF
GTID:2181330467487895Subject:Applied Chemistry
Abstract/Summary:PDF Full Text Request
β-Caryophyllene alcohol is a food additive approved by FDA. Because of its wide potential use in food and pharmaceuticals industry, market demand of β-Caryophyllene alcohol has become huger and huger. Currently, β-Caryophyllene alcohol is produced via the β-Caryophyllene hydration catalyzed by liquid acids such as sulfuric acid and chloroacetic acid. However, catalysis performance of these catalysts is unsatisfying. Besides, equipment corrosion, environment pollution and large energy consumption are the serious problems associated with liquid acids catalysts. New catalysts such as H-β zeolites and heteropoly acids have the drawbacks of complicated to prepare, low conversion, long reaction time and high cost. Therefore, it is very necessary to intensively investigate the hydration reaction in order to lay a solid foundation for the industrial production of P-Caryophyllene alcohol and meet its growing demand.Cyclohexanol is an indispensable intermediates for the production of pharmaceuticals, coatings and dyes and is widely used as a solvent for many polymers. It is conventionally produced via the oxidation of cyclohexane. Due to presence of oxygen, this process is prone to explosion, thus brings about safety issue. As the maturing of a new process for cyclohexene production via benzene hydrogenation invented by Asahi Chemical Co., cyclohexanol production by the direct hydration of cyclohexene becomes more and more promising. Much research has been focused on the direct hydration of cyclohexene. Unfortunately, circumscribed by the low solubility of cyclohexene in water, researchers still are not able to achieve desirable results. Consequently, it is essential to select ideal co-solvent to increase the solubility of cyclohexene in water and subsequently facilitate the hydration process.This thesis studied the direct hydration of β-Caryophyllene and cyclohexene in detail and optimized operation parameters of these processes. By correlation experimental data, reaction kinetic parameters were derived. This work provides experimental evidence and theoretical foundation for these two processes. Achievements obtained are as follows:1. Study on the direct hydration of β-CaryophylleneNKC-9was sifted as a suitable catalyst. Through the effect analysis of different operation parameters, the reaction condition was optimized as following:catalysts loading of20%(w/w); reaction temperature of363.15K; reactants mole ratio of1:1. Under this optimized condition, the hydration reached equilibrium in40min. The conversion of β-Caryophyllene is93%, while the yield and selectivity of β-Caryophyllene alcohol is29%and31%, respectively.A Pseudo-Homogenous (PH) kinetic model was introduced to correlate experimental data for the purpose of deriving kinetic parameters. Calculated results from PH model are in satisfactory agreement with the experimental ones.Under experiment condition, the PH kinetic model can be written as: Where:This hydration process was also scaled up in a5L stirred glass reactor and a20L jet reactor and obtained pleasing reaction performance. 2. Study on the direct hydration of cyclohexeneAmberlyst35wetwas used as catalyst for this hydration reaction. Effect of various parameters on the direct hydration of cyclohexene was thoroughly investigated. The optimized reaction condition was as following:co-solvent of dioxane, catalysts loading of7.8%(w/w); reaction temperature of393.15K; reactants mass ratio (cycloehexene:H2O:dioxane) of1:8:1. Under this optimized condition, the reaction reached equilibrium in5hr. The conversion of cyclohexene is39.95%, and selectivity of cyclohexanol is98.71%.A PH model was also introduced to correlate experimental data for the purpose of deriving kinetic parameters. Calculated results from PH model are in approximate accordance with the experimental ones.Under experiment condition, the PH model can be written as: Where:Besides, the expression of reaction equilibrium constant Keq was also obtained as following:Also the enthalpy and entropy of this reaction:...
Keywords/Search Tags:β-Caryophyllene, cyclohexene, direct hydration, co-solvent, reactionkinetics
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