- Investigation of the kinetics and mechanism of the glycerol chlorination reaction using gas chromatography-mass spectrometry
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As a primary by-product in biodiesel production, glycerol can be used to prepare an important fine chemical, epichlorohydrin, by the glycerol chlorination reaction. Although this process has been applied in industrial production, unfortunately, less attention has been paid to the analysis and separation of the compounds in the glycerol chlorination products. In this study, a convenient and accurate method to determine the products in glycerol chlorination reaction was established and based on the results the kinetic mechanism of the reaction was investigated. The structure of main products, including 1,3-dichloropropan-2-ol, 2,3-dichloropropan-1-ol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol and glycerol was ascertained by gas chromatography-mass spectrometry and the isomers of the products were distinguished. Apidic acid was considered as the best catalyst because of its excellent catalytic effect and high boiling point. The mechanism of the glycerol chlorination reaction was proposed and a new kinetic model was developed. Kinetic equations of the process in the experimental range were obtained by data fitting and the activation energies of each tandem reaction were 30.7, 41.8, 29.4 and 49.5 kJ mol-1, respectively. This study revealed the process and mechanism of the kinetics and provides the theoretical basis for engineering problems. 2009 copyright (CC) SCS.
- Ling, Xiuquan,Lu, Dingqiang,Wang, Jun,Liang, Mingxin,Zhang, Shumin,Ren, Wei,Chen, Jianhui,Ouyang, Pingkai
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Read Online
- A simplified early stage assessment of process intensification: Glycidol as a value-added product from epichlorohydrin industry wastes
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The present work deals with the production of glycidol through a new synthetic approach based on the conversion of 2-chloro-1,3-propanediol (β-MCH), a by-product in the epichlorohydrin production plant. β-MCH was converted with high yield (90%) and selectivity (99%) to glycidol using an alcoholic solution of KOH at room temperature in only 30 minutes. A simplified early stage assessment based on the use of the green metrics and a life cycle analysis were adopted in order to evaluate the environmental feasibility of this innovative route if compared with the traditional chain to epichlorohydrin. The waste recovery and the maximization of the overall process efficiency lead to sensible reductions per each indicator considered in the assessment, suggesting the possibility of developing on a full industrial scale. In addition, in order to verify the potentialities behind the substitution of the fossil-based glycidol with the product resulted from the recovery of the β-MCH, a cradle-to-gate analysis and the GREENMOTION tool were adopted.
- Cespi,Cucciniello,Ricciardi,Capacchione,Vassura,Passarini,Proto
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Read Online
- Novel method for producing 2-amino-1, 3-propylene glycol by JIT method
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The invention belongs to the field of fine chemical engineering, and relates to a novel method for producing 2-amino-1, 3-propylene glycol by a JIT method, the novel method is composed of a catalytic chlorination reaction and a catalytic amination reaction, glycerol is chlorinated by hydrogen chloride under the catalysis of zinc chloride to obtain 2-chloro-1, 3-propylene glycol, and the 2-chloro-1, 3-propylene glycol is subjected to a catalytic reaction by urotropin to obtain 2-chloro-1, 3-propylene glycol.
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Paragraph 0042-0047
(2021/11/26)
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- Preparation method for 1,3-propylene glycol from glycerol
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The invention relates to a preparation method for 1,3-propylene glycol from glycerol, wherein the preparation method comprises the steps of chlorohydrination reaction, cyclization reaction, hydrogenation reaction and the like. The glycerin conversion rate of the preparation method reaches 99% or above, the yield of 1,3-propylene glycol reaches 65% or above, and the preparation method has the advantages of being simple in process, mild in reaction condition, small in investment, high in technical safety and easy to operate and control.
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Paragraph 0066-0076
(2021/04/10)
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- Synthesis of 2-Monochloropanol Fatty Acid Esters and Their Acute Oral Toxicities in Swiss Mice
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A novel synthetic route was designed, developed, and utilized to synthesize six high-purity 2-monochloropropanediol fatty acid esters (2-MCPD esters), a group of potential processing-induced food contaminants. A chlorine atom was introduced to C-2 of a diethyl malonate molecule, which was reduced by NaBH4 and followed by esterification using fatty acids. The reaction products were isolated and purified using silica gel columns to obtain three 2-MCPD monoesters and three diesters at about 50-54% and 56-59% yields, respectively. In addition, 2-MCPD monopalmitate and dipalmitate were examined for their acute oral toxicities in Swiss mice. The LD50 values of 2-MCPD mono- and dipalmitate were greater than 5000 mg/kg body weight (BW), along with detectable nephrotoxicity and testicular toxicity. The results of this study may promote future investigation of MCPD ester toxicology and detection.
- Zhang, Zhongfei,Yang, Puyu,Gao, Boyan,Huang, Guoren,Liu, Man,Yu, Liangli Lucy
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p. 3789 - 3795
(2019/04/10)
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- PROCESS FOR THE PRODUCTION OF DICHLOROHYDRONS
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This invention is related to the process of dichlorohydrins production starting from glycerol by hydrochlorination with hydrochloric acid in the presence of a new class of catalysts consisting in the acyl chlorides.
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Page/Page column 25; 26
(2015/03/28)
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- CONVERSION OF GLYCERINE TO DICHLOROHYDRINS AND EPICHLOROHYDRIN
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The present invention relates to a process for the production of dichlorohydrin by catalyzed hydrochlorination of glycerine where the reaction is performed in at least two subsequent stages operating continuously at different pressures with both vapor and liquid recycle. The first reactor, low pressure (L. P.) reactor, operating at a pressure ranging from 1 to 4 bar and at a temperature from 900C to 1300C converts most of GLY to MHC. The second reactor, medium pressure (M. P. ) reactor, operating at a pressure ranging from 5 to 20 bar and at temperature from 90 °c to 1300C converts the effluent from the L. P. reactor to DCH with an adequate degree of conversion. Each reactor is followed by a stripping unit.
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Paragraph 0077-0082
(2017/01/02)
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- METHOD FOR PREPARING CHLOROHYDRINS AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS PREPARED THEREBY
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A method of preparing chlorohydrins and a method of preparing epichlorohydrin by using chlorohydrins prepared using the method are provided. The method of preparing chlorohydrins by reacting polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst includes at least one combination of a series of unit operations including a first reaction step, a water removal step, and a second reaction step, in that respective order, and after mixing at least a portion of a reaction mixture discharged from at least one reaction steps from among the plurality of reaction steps with an additional chlorination agent, recirculating the resulting mixture to the reaction step from which the reaction mixture was discharged. The method of preparing epichlorohydrin includes a step of reacting chlorohydrins prepared using the method of preparing chlorohydrins, with an alkaline agent.
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Paragraph 0105-0106
(2013/04/13)
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- METHOD FOR PREPARING CHLOROHYDRINS AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS PREPARED THEREBY
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A method of preparing chlorohydrins and a method of preparing epichlorohydrin by using chlorohydrins prepared using the method are provided. The method of preparing chlorohydrins by reacting polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst includes at least one combination of a series of unit operations including a first reaction step, a water removal step, and a second reaction step, in that respective order, wherein the method further includes purifying chlorohydrins from a reaction mixture discharged from a final reaction step of the plurality of reaction steps. The method of preparing epichlorohydrin includes reacting chlorohydrins prepared using the method of preparing chlorohydrins, with an alkaline agent.
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Paragraph 0105-0106
(2013/04/24)
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- METHOD FOR PREPARING CHLOROHYDRINS COMPOSITION AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS COMPOSITION PREPARED THEREBY
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Disclosed are a method for preparing chlorohydrins composition and a method for preparing epichlorohydrin using chlorohydrins prepared thereby. The disclosed method for preparing chlorohydrins composition reacts polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst, comprises at least one combination of a series of unit operations including a first reaction step, a water removal step, and a second reaction step in the respective order, and additionally comprises a step for reacting the chlorohydrins composition derived from a plurality of reaction mixtures discharged from the plurality of reaction steps with an alkaline chemical, and removing the catalyst included in the chlorohydrins composition in the form of an alkali metal salt. The disclosed method for preparing epichlorohydrin includes a step for contacting the chlorohydrins composition, which was prepared using the method for preparing chlorohydrins composition, with an alkaline chemical.
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Paragraph 0103-0104
(2013/05/08)
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- METHOD FOR PREPARING CHLOROHYDRINS COMPOSITION AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS COMPOSITION PREPARED THEREBY
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Provided are a method of preparing a chlorohydrin composition and a method of preparing epichlorohydrin by using a chlorohydrin composition prepared by using the method. The method of preparing chlorohydrins in which polyhydroxy aliphatic hydrocarbon is reacted with a chlorination agent in the presence of a catalyst includes performing at least one combination of a series of unit operations comprising a first reaction step, a water removal step, and a second reaction step in this stated order, wherein the method further includes mixing a chlorohydrin concentrate obtained by purifying the reaction mixture discharged from the final reaction step from among the reaction steps and a water-rich layer discharged from the water-removal step and diluting the mixture with water. The method of preparing epichlorohydrin includes contacting the chlorohydrin composition prepared by using the method of preparing a chlorohydrin composition with an alkaline agent.
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Paragraph 0101-0102
(2013/05/08)
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- METHOD FOR PREPARING CHLOROHYDRINS AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS PREPARED THEREBY
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A method of preparing chlorohydrins and a method of preparing epichlorohydrin using chlorohydrins prepared by using the same method are provided. The method is to prepare chlorohydrins by reacting polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst, and the method includes at least one combination of a series of unit operations including the following steps in the following stated order: a first reaction step; a water removal step; and a second reaction step, wherein the water removing step is performed by distillation operation based on a boiling point difference between constituents of a reaction mixture. The method of preparing epichlorohydrin includes reacting chlorohydrins prepared by using the method of preparing chlorohydrins with an alkaline agent.
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Paragraph 0101-0103
(2013/05/08)
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- METHOD FOR PREPARING CHLOROHYDRINS COMPOSITION AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS COMPOSITION PREPARED THEREBY
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A method of preparing a chlorohydrin composition and a method of preparing epichlorohydrin by using a chlorohydrin composition prepared by using the method are provided. The method of preparing a chlorohydrin composition in which a polyhydroxy aliphatic hydrocarbon is reacted with a chlorination agent in the presence of a catalyst includes performing at least one combination of a series of unit operations comprising a first reaction step, a water removal step, and a second reaction step in this stated order, wherein the method further includes mixing a chlorohydrin concentrate obtained by purifying the reaction mixture discharged from the final reaction step from among the plurality of reaction steps and a water-rich layer discharged from the water-removal step. The method of preparing epichlorohydrin includes contacting the chlorohydrin composition prepared by using the method of preparing a chlorohydrin composition with an alkaline agent
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Paragraph 0099-0100
(2013/05/08)
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- METHOD FOR PREPARING CHLOROHYDRINS AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS PREPARED THEREBY
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A method of preparing chlorohydrins and a method of preparing epichlorohydrin by using chlorohydrins prepared using the method are provided. The method of preparing chlorohydrins by reacting polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst includes at least one combination of a series of unit operations including a first reaction step, a water removal step, and a second reaction step, in that respective order, wherein the method further includes purifying chlorohydrins from a reaction mixture discharged from a final reaction step of the plurality of reaction steps. The method of preparing epichlorohydrin includes reacting chlorohydrins prepared using the method of preparing chlorohydrins, with an alkaline agent.
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Paragraph 0102-0103
(2013/05/22)
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- METHOD FOR PREPARING CHLOROHYDRINS AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS PREPARED THEREBY
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A method of preparing chlorohydrins and a method of preparing epichlorohydrin using chlorohydrins prepared by using the same method are provided. The method is to prepare chlorohydrins by reacting polyhydroxy aliphatic hydrocarbon with a chlorination agent in the presence of a catalyst, and the method includes at least one combination of a series of unit operations including the following steps in the following stated order: a first reaction step; a water removal step; and a second reaction step, wherein the water removing step is performed by distillation operation based on a boiling point difference between constituents of a reaction mixture. The method of preparing epichlorohydrin includes reacting chlorohydrins prepared by using the method of preparing chlorohydrins with an alkaline agent.
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Paragraph 0101-0102
(2013/05/22)
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- METHOD FOR PREPARING CHLOROHYDRINS COMPOSITION AND METHOD FOR PREPARING EPICHLOROHYDRIN USING CHLOROHYDRINS COMPOSITION PREPARED THEREBY
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A method of preparing a chlorohydrin composition and a method of preparing epichlorohydrin by using a chlorohydrin composition prepared by using the method are provided. The method of preparing a chlorohydrin composition in which a polyhydroxy aliphatic hydrocarbon is reacted with a chlorination agent in the presence of a catalyst includes performing at least one combination of a series of unit operations comprising a first reaction step, a water removal step, and a second reaction step in this stated order, wherein the method further includes mixing a chlorohydrin concentrate obtained by purifying the reaction mixture discharged from the final reaction step from among the plurality of reaction steps and a water-rich layer discharged from the water-removal step. The method of preparing epichlorohydrin includes contacting the chlorohydrin composition prepared by using the method of preparing a chlorohydrin composition with an alkaline agent
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Paragraph 0099-0100
(2013/05/22)
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- METHOD OF PREPARING CHLOROHYDRINS BY REACTING POLYHYDROXY ALIPHATIC HYDROCARBON WITH CHLORINATION AGENT
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A method of preparing chlorohydrins from polyhydroxy aliphatic hydrocarbon such as glycerol. The method includes irradiating an ultrasonic wave to a reaction mixture during reaction.
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Paragraph 61-62
(2011/02/24)
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- PROCESS FOR THE PREPARATION OF A DICHLOROPROPANOL PRODUCT
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The present invention relates to a process for the preparation of a dichloropropanol product, wherein the dichloropropanol product comprises a mixture of 1,2-dichloropropan-3-ol and 1,3-dichloropropan-2-ol, said process comprising the steps of: (a) contacting glycerol with hydrochloric acid in a molar ratio of glycerol to hydrochloric acid of about less than 1 to about 100 to form a first product mixture comprising l-chloropropane-2,3-diol as a major constituent; and (b) contacting said first product mixture comprising 1-chloropropane-2,3-diol as a major constituent with hydrochloric acid in a molar ratio of 1-chloropropane-2,3- diol to hydrochloric acid of about less than 1 to about 100 to form the dichloropropanol product.
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Page/Page column 13-14
(2009/10/18)
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- Process for the Production of Alpha, Gamma-Dichlorohydrin From Glycerin and Hydrochloric Acid
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A process for preparing α,γ-dichlorohydrin starting from glycerin and preferably gaseous anhydrous hydrochloric acid in the presence of low-volatility organic acids as catalysts.
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Page/Page column 3-4
(2009/04/24)
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- METHOD OF PREPARING DICHLOROPROPANOL FROM GLYCEROL IN THE PRESENCE OF HETEROPOLYACID CATALYST AND/OR ABSORBENT UNDER SOLVENT-FREE CONDITIONS
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Provided is a method of preparing dichloropropanol from glycerol. The method includes reacting glycerol with a chlorinating agent, and the reaction is performed in the presence of a heteropolyacid catalyst and/or an absorbent under solvent-free conditions. Thus, according to the method, dichloropropanol can be directly prepared from glycerol. Since a solvent is not used, a process of removing the solvent is not necessary, and thus the volume of a reactor can be reduced. In addition, conventional problems such as recovery of the catalyst and separation of an azeotropic mixture including the catalyst and products can be overcome. In addition, expensive dichloropropanol can be produced at high yield from inexpensive glycerol.
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Page/Page column 9-10
(2010/01/07)
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- PROCESS FOR MONOCHLOROHVDRINS PRODUCTION FROM GLYCEROL AND HYDROCHLORIC ACID
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The present invention refers to a process for selectively producing monochloroydrins starting from glycerol and hydrochloric acid carried out in the presence of a catalyst selected in the group of: dicarboxylic, polycarboxylic and hydroxycarboxylic acids capable of converting at least 70% of glycerol with a selectivity in monochlorohydrins of about 80% or higher, preferably 97% or higher. Suitable catalysts are for example: oxalic acid, fumaric acid, maleic acid, tartaric acid and corresponding mixtures.
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Page/Page column 7
(2008/12/08)
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- MULTI-STAGE PROCESS AND APPARATUS FOR RECOVERING DICHLOROHYDRINS
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A process and apparatus for recovering dichlorohydrins from a mixture comprising dichlorohydrins, one or more compounds selected from esters of dichlorohydrins, monochlorohydrins and/or esters thereof, and multihydroxylated- aliphatic hydrocarbon compounds and/or esters thereof, and optionally one or more substances comprising water, chlorinating agents, catalysts and/or esters of catalysts is disclosed. The mixture is distilled or fractionated to separate a lower boiling fraction comprising dichlorohydrin(s) from the mixture to form a higher boiling fraction comprising the residue of the distillation or fractionation. The higher boiling fraction is stripped to recover remaining dichlorohydrins. Advantages include more efficient recovery of dichlorohydrins for a given distillation column, less waste due to avoiding the conditions conducive to the formation of heavy byproducts, and reduced capital investment in recovery equipment.
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Page/Page column 28-32
(2008/12/08)
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- PROCESS AND APPARATUS FOR REDUCING HEAVY BYPRODUCT FORMATION DURING RECOVERY OF DICHLOROHYDRINS
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A process and apparatus for recovering dichlorohydrins from a mixture comprising dichlorohydrins, water, one or more compounds selected from esters of dichlorohydrins, monochlorohydrins and/or esters thereof, and multihydroxylated- aliphatic hydrocarbon compounds and/or esters thereof, and optionally one or more substances comprising chlorinating agents, catalysts and/or esters of catalysts while minimizing formation of heavies is disclosed.
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Page/Page column 25-26
(2008/12/08)
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- PROCESS AND APPARATUS FOR RECOVERY OF DICHLOROHYDRINS VIA CODISTILLATION
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A process and apparatus for recovering dichlorohydrins from a mixture comprising dichlorohydrins, one or more compounds selected from esters of dichlorohydrins, monochlorohydrins and/or esters thereof, and multihydroxylated- aliphatic hydrocarbon compounds and/or esters thereof, and optionally one or more substances comprising water, chlorinating agents, catalysts and/or esters of catalysts is disclosed. The mixture is stripped to recover dichlorohydrin(s) while distilling or fractionating the mixture to separate a lower boiling fraction comprising dichlorohydrin(s) from the mixture in one step. Advantages include more efficient recovery of dichlorohydrins for a given distillation column, less waste due to avoiding the conditions conducive to the formation of heavy byproducts, and reduced capital investment in recovery equipment.
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Page/Page column 28-31
(2008/12/08)
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- PROCESS FOR THE CATALYTIC HALOGENATION OF A HYDROXYLATED ORGANIC COMPOUND
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The present invention relates to a process for the catalytic halogenation of an organic compound comprising at least one aliphatic hydroxyl group which comprises the step of contacting the organic compound comprising at least one aliphatic hydroxyl group with a hydrogen halide in the presence of a catalyst which is an organic polymer which comprises at least one carbonyl group, has a vapour pressure at the reaction temperature of less than 1 mbar, has a weight average molecular weight Mw of 500 g/mole or more, and is soluble in the reaction mixture at the reaction temperature.
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Page/Page column 13-14; 15; sheet 1
(2008/12/06)
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- CONVERSION OF A MULTIHYDROXYLATED-ALIPHATIC HYDROCARBON OR ESTER THEREOF TO A CHLOROHYDRIN
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The present invention relates to a process for converting a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin, by contacting the multihydroxylated-aliphatic hydrocarbon or ester thereof starting material with a source of a superatmospheric partial pressure of hydrogen chloride for a sufficient time and at a sufficient temperature, and wherein such contracting step is carried out without substantial removal of water, to produce the desired chlorohydrin product; wherein the desired product or products can be made in high yield without substantial formation of undesired overchlorinated byproducts. In addition, certain catalysts of the present invention may be used in the present process at superatmospheric, atmospheric and subatmospheric pressure conditions with improved results.
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Page/Page column 35-37
(2008/06/13)
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- PROCESS FOR THE PRODUCTION OF ALPHA, GAMMA-DICHLOROHYDRIN FROM GLYCERIN AND HYDROCHLORIC ACID
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A process for preparing α,γ-dichlorohydrin starting from glycerin and preferably gaseous anhydrous hydrochloric acid in the presence of low- volatility organic acids as catalysts.
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Page/Page column 11-13; 3/7; 4/7; 7/7
(2008/06/13)
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- PROCESS FOR PRODUCING DICHLOROPROPANOL FROM GLYCEROL, THE GLYCEROL COMING EVENTUALLY FROM THE CONVERSION OF ANIMAL FATS IN THE MANUFACTURE OF BIODIESEL
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Use of glycerol obtained from renewable raw materials, as starting product for producing organic compounds. Process for producing dichloropropanol, according to which glycerol is subjected to a reaction with a chlorinating agent, with the exception of a batch reaction carried out in the presence of acetic acid or its derivatives.
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Page/Page column 25
(2008/06/13)
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- Oxidation of olefins by palladium(II): Part 17. An asymmetric chlorohydrin synthesis catalyzed by a bimetallic palladium(II) complex
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Previous studies showed that oxidation of α-olefins with monometallic catalysts containing chiral diphosphines and diamines gave chlorohydrins with poor to good enantioselectivites (28-82% ee). The present studies demonstrate that bimetallic catalysts containing a β-triketone and bridging chiral diphosphine and diamines are excellent catalysts for this reaction giving enantioselectivites considerably higher than the monometallic catalysts. Enantioselectivities were more than 50% for most olefins tested. The highest optical purities were 94% ee for propene and 93% ee for allylphenyl ether. A useful feature of this asymmetric synthesis is the fact it is a net air oxidation.
- El-Qisairi, Arab,Henry, Patrick M.
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- The Effects of β-Alkoxy Substituents on Radical Reactions: Halogen-atom Abstraction from Alkyl Chlorides
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EPR spectroscopy has been used to measure the relative rates of halogen-atom abstraction from RCH2Cl by the metalloid-centred radicals Me3N->B(radical)HBu, Et3N->B(radical)H2 and Et3Si(radical) (M(radical)) in cyclopropane and in oxirane solvents at 160-260 K. β-Methoxy substituents increase the rate of reaction, especially for chlorine abstraction by the highly nucleophilic amine-boryl radicals.The accelerating influence of the β-oxygen substituents is attributed to a polar effect which operates in the transition state andinvolves charge transfer from M(radical) to the CH2-Cl group.The relative reactivities of the cis- and trans-isomers of 5-chloro-2-tert-butyl-1,3-dioxane indicate that the substituent effect of a β-alkoxy group does not depend markedly on the orientation of the β-C-O bond with respect to the rupturing C-Cl bond.It is concluded that the β-C-O bond dipole interacts electrostatically through space with the dipolar C...Cl...M grouping in the transition state and thus stabilises the latter relative to the reactants.This interpretation is supported by the results of ab initio molecular calculations for model systems.The EPR spectra of the β-alkoxyalkyl radicals are discussed in relation to their preferred conformations as deduced on the basis of the Heller-McConnell equation.The applicability of the latter equation is confirmed by ab initio calculations for the ethyl radical.
- Roberts, Brian P.,Steel, Andrew J.
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p. 2411 - 2422
(2007/10/02)
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