Abstract:The reactions involved in epichlorohydrin industrial production have been studied. The reactions can be divided into two groups: ring closure (dehydrochlorination) and ring opening (epoxide hydrolysis). Two analytical techniques, potentiometry and gas chromatography, have been employed in order to follow the time evolution of the reagents. The kinetic parameters of the reactions have been determined and a kinetic model of the overall system is offered.
“…This is manifested in the 1,3-DCH/2,3-DCH ratio, which is 30 -50 in the GTE process, but only about 3:1 in the incumbent process. The value of improved 1,3-regioselectivity is that 1,3-DCH undergoes cyclization with base to form epichlorohydrin about 300 times faster than does 2,3-DCH [12]. This translates into smaller process equipment and/or shorter residence times.…”
A significant improvement in a process to produce epichlorohydrin through the use of glycerin as renewable feedstock is presented. The glycerin to epichlorohydrin (GTE) process proceeds in two chemical steps. In the first step, glycerin is hydrochlorinated with hydrogen chloride gas at elevated temperature and pressure to a mixture of 1,3-DCH (1,3-dichlorohydrin, 1,3-dichloropropan-2-ol) and 2,3-DCH (2,3-dichlorohydrin, 2,3-dichloropropan-1-ol), using a carboxylic acid catalyst. In the second step, the mixture of dichlorohydrins is converted to epichlorohydrin with a base. This solventless process represents an economically and environmentally advantageous, atom-efficient process to an existing commodity chemical that can employ a renewable resource for its primary feedstock.
“…This is manifested in the 1,3-DCH/2,3-DCH ratio, which is 30 -50 in the GTE process, but only about 3:1 in the incumbent process. The value of improved 1,3-regioselectivity is that 1,3-DCH undergoes cyclization with base to form epichlorohydrin about 300 times faster than does 2,3-DCH [12]. This translates into smaller process equipment and/or shorter residence times.…”
A significant improvement in a process to produce epichlorohydrin through the use of glycerin as renewable feedstock is presented. The glycerin to epichlorohydrin (GTE) process proceeds in two chemical steps. In the first step, glycerin is hydrochlorinated with hydrogen chloride gas at elevated temperature and pressure to a mixture of 1,3-DCH (1,3-dichlorohydrin, 1,3-dichloropropan-2-ol) and 2,3-DCH (2,3-dichlorohydrin, 2,3-dichloropropan-1-ol), using a carboxylic acid catalyst. In the second step, the mixture of dichlorohydrins is converted to epichlorohydrin with a base. This solventless process represents an economically and environmentally advantageous, atom-efficient process to an existing commodity chemical that can employ a renewable resource for its primary feedstock.
“…The following modeling assumptions are made in this paper: [3,4,14,16] (1) the concentration of HAC is constant due to its catalytic function in the reaction system, (2) the concentration of HCl is constant and can be obtained according to its saturation in the organic phase due to its weak/difficult dissolution ability in the organic phase, (3) the concentration of H 2 O is constant due to its surplus in the reaction system, and (4) the quasi-stationary-state assumption is applied. Therefore, according to the reaction steps shown in Scheme 2, the mass balance equations can be worked out.…”
Section: Kinetic Modelmentioning
confidence: 99%
“…1,3-Dichloro-2-propanol (1,3-DCP) is an intermediate for the production of epichlorohydrin (ECH, 1-chloro-2,3-epoypropane) [1], which is an important intermediate for the chemical industry [1][2][3]. Recently, a direct process to prepare 1,3-DCP consisting of the chlorination of glycerol (GLY) with hydrochloric acid (HCl) was developed [2,3], and the process has been widely applied in the industry.…”
Section: Introductionmentioning
confidence: 99%
“…Recently, a direct process to prepare 1,3-DCP consisting of the chlorination of glycerol (GLY) with hydrochloric acid (HCl) was developed [2,3], and the process has been widely applied in the industry. However, previous studies on the process mainly focused on the patent data and technical feasibility [1][2][3][4][5][6][7][8][9][10][11][12][13].…”
A kinetic model for the chlorination of glycerol with hydrochloric acid in the use of acetic acid as catalyst is presented in this study. The model is based on a comprehensive chlorination mechanism, taking the formation of 1,3-dichloro-2-propanol and 2,3-dichloro-1-propanol into account while ignoring the formation of any intermediate in the chlorination system. Simulations were carried out under different chlorination conditions to calculate the concentrations of the main chemical species in the reaction system. The validity of the model was examined via a comparison of the calculated data with the experimental data on the chlorination of glycerol with hydrochloric acid at 363-393 K. The results show the model is capable of describing the chlorination performance with good agreement with experimental data.Yantai Wanhua Polyurethanes Co., Ltd
“…Details on some of the reaction kinetics of this type of reaction system can be found in Carra, Santacesaria, and Morbidelli (1979). However, the model presented in Carra et al (1979) requires many parameters, such as reaction rates, to be determined when applied to practical systems so that only qualitative information is taken in this paper.…”
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.