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Study On The Chemical Production Of 1,2-Cyclohexanediol From Cyclohexylene

Posted on:2004-06-08Degree:DoctorType:Dissertation
Country:ChinaCandidate:C R ZhouFull Text:PDF
GTID:1101360125957310Subject:Chemical processes
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"The study of New Technology study of Synthesizing 1,2-cyclohexanediol " is one of subjects funded by Henan Outstanding Person Foundation. Aiming at demand of national economy and linking the actual condition of domestic refinery chemical , a routine with cyclohexene as main raw material was developed in the thesis.To prepare O-dihydroxybenzene with cyclohexene, trans-1.2- cyclohexanediol is a very important organic intermediate. As a kind of important fine chemical product, O-dihydroxybenzene has a prosperous future in the field of medicine, pesticide, spice and fine organic synthesis. Firstly, there is quite a few reports on the synthetic technology of trans-1,2-cyclohexanediol in the country and the reports are even less about cyclohexene abroad. So thie thesis developed and obtained the new technology routine which adopts the original position method to synthesize 1,2-cyclohexanediol directly.At first, on the base of the formula structure of cyclohexene and correlative organic synthesis theory, we draw up the experimental scheme of the synthesis of trans-1.2-cyclohexanediol. Then with the orthogonal design method and single-factor-experiment, the key factors affecting this complicate reaction were determined,. Furthurmore we refocused the influence of temperature, acetic acid, hydrogen peroxide, the ratio of acetic acid and acetic anbydride. The ideal synthetic process conditions are acquired.In this better condition, the yield is 74 % for acetic acid and is 90% for formic acid, but the unused cyclohexene and catalyst as well as ethyl acetate can be recycled for the reaction. In addition, the most pivotal is the selectivity, and not the percentage yield. The selectivity in the reaction is up to 95 percent calculated with unitary method. The technology can be regard as a environmental protection process because the excessive organic acid and uncreative cyclohexylene, and as well as solvent can be cycled used for Synthesis of 1,2-cyclohexanediol, and the organic salt is by-product.On basis of the work in this paper, we have gotten melting point, melting heat and heat capacities for 1,2-cyclohexanediol by DSC, standard combustion enthalpy have obtained by calorimeter, standard formation enthalpy, standard reaction enthalpy of1,2-cyclo-hexanediol have been calculated according to thermodynamic principle. Then, we have studied the relationship on melting temperature and component of trans-1,2-cyclohexanediol , melting heat and component of trans-1,2-cyclohexanediol in the mixture of cis- and trans-1,2-cyclohexanediol, as well as heat capacities of 1,2-cyclohexanediol as a function of temperature.A set of laser monitoring observation system to be used for measure the solubility with a high speed, which is programmed heating apparatus , have designed. The solubility of 1,2-cyclohexanediol were measured in water, methyl acetate, acetic ester, propyl acetate, butyl acetate, methyl acrylate, ethyl acrylate, acetoacetic ester at different temperature. There are 114 data points which are reported first time.A modified UNIFAC model is set up by defining new functional groups which are CHD and CH2=CHCOO. And, group volume parameters, group surface-aera parameters and group interaction parameters are optimized by means of computer program. This new modified UNIFAC model can perfectly predict the solubility on the above systems .The total mean relative error is 7.48% for solubility, The total mean relative errors are respectively 0.37% and 3.18% for the solubility of ideal equation and h equation. The result of ideal equation, h equation and the new model are similar. These show that the new model is successful. By means of new modified UNIFAC model can perfectly predict solid-liquid equilibriums on the above systems. The total mean relative errors are respectively 10.77% and 9.80% for ternary system solid-liquid equilibrium data of water+l,2-cyclohaxanediol + acetic ester and water+l,2-cyclohaxanediol+ butyl acetate between the experimental results and the values predicted by the...
Keywords/Search Tags:1.2-Cyclohexanediol, Dynamics, Thermodynamics properties, Solid-Liquid phase equilibrium, Solubility, UNIFAC group contribution model, Solution extraction.
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