- Effect of sodium chloride on the solubility and hydrolysis of epichlorohydrin in water
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The mutual solubility of the components in the epichlorhydrin–water–sodium chloride system was studied in the temperature range of 20–90 °С. It was found that epichlorohydrin is salted out as the concentration of NaCl increases. The Sechenov coefficient was determined to be equal to 0.29. It was found that epichlorohydrin reacts with an aqueous solution of sodium chloride to form glycerol dichlorohydrins. Alkali formed during this reaction catalyzes the hydrolysis of epichlorohydrin to glycerol monochlorohydrin, acts as a reagent in the glycidol formation and accelerates its subsequent conversion to glycerol.
- Dmitriev,Zanaveskin,Khadzhiev
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Read Online
- 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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- A safer and greener chlorohydrination of allyl chloride with H2O2 and HCl over hollow titanium silicate zeolite
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Industrial production of dichloropropanols through chlorohydrination of allyl chloride suffers from a series of disadvantages such as use of hazardous Cl2, low atom economy, low dichloropropanol concentration and serious pollution. In this work, a safer and greener route for chlorohydrination of allyl chloride with H2O2 and HCl over hollow titanium silicate (HTS) at mild condition is developed. Unlike the traditional Cl2-based chlorohydrination, this novel method is initiated via synergistic effect of Lewis acidity (HTS) and Br?nsted acidity (HCl) to promote occurrence of oxidation, protonation and nucleophilic reaction of allyl chloride simultaneously and hence dichloropropanols are generated. Owing to a completely different reaction route, the formation of 1,2,3-trichloropropane by-product is depressed and the content of dichloropropanol exceeded 22?wt%, which increase by about 4 times compared with traditional Cl2-based chlorohydrination (the content of dichloropropanol is below 4?wt%). At the optimized conditions, both of the allyl chloride conversion and dichloropropanol selectivity could approach 99% simultaneously and the waste is minimized. What's more, the HTS was reusable. Concentrated HCl solution treatment was adopted to test HTS's stability. The characterization and catalytic evaluation results reveal that, although parts of the framework Ti species have transformed into non-framework Ti and then leached into the solution, HTS remains structural stable, and the allyl chloride conversion and dichloropropanol selectivity didn't decrease obviously during the treatment.
- Peng, Xinxin,Xia, Changjiu,Lin, Min,Shu, Xingtian,Zhu, Bin,Wang, Baorong,Zhang, Yao,Luo, Yibin,Mu, Xuhong
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- Method for comprehensive utilization of hexachloroethane
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The invention relates to a comprehensive utilization method of a dichloroethane chlorination byproduct namely hexachloroethane. The comprehensive utilization method comprises the following steps: adding a hexachloroethane solution, glycerin, a hydrogenation catalyst and a chlorination catalyst into a high-pressure kettle; after feeding is finished, performing hydrodechlorination and glycerin chlorination reaction at the same time at certain temperature and under certain hydrogen pressure; after reaction is finished, maintaining the temperature for 4h, and then reducing the temperature to the room temperature; performing filtering separation to obtain the hydrogenation catalyst, layering reaction liquid to obtain a solvent layer and a glycerin layer, wherein the solvent layer contains a solvent, pentachloroethane, pentachloroethane and trichloroethane, and the glycerin layer contains the glycerin, dichloropropanol, water, the chlorination catalyst and monochlorohydrin.
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Paragraph 0015; 0017-0019; 0021; 0023; 0025; 0027; 0030
(2017/10/27)
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- Chlorohydrination of allyl chloride with HCl and H2O2 catalyzed by hollow titanium silicate zeolite to produce dichloropropanol
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Overall, over 95% of epichlorohydrin is industrially manufactured via the chlorohydrination route with hazardous Cl2 as a reagent, which brings serious operation and pollution problems. Herein, we describe a novel Cl2-free process for the synthesis of dichloropropanols from allyl chloride with H2O2 and HCl catalyzed by hollow titanium silicate zeolite under mild conditions. A high conversion and overall dichloropropanol selectivity exceeding 95% are simultaneously achieved, and the heterogeneous catalyst is highly stable and amenable for reuse. Comprehensive experimental and spectroscopic data suggest that the Lewis acidity of the framework Ti species has a synergistic effect with the Br?nsted acidity of HCl that promotes the epoxidation of allyl chloride and the ring opening of the epoxy groups.
- Peng, Xinxin,Xia, Changjiu,Lin, Min,Yuan, Hui,Zhu, Bin,Zhang, Yao,Wang, Baorong,Shu, Xingtian
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supporting information
p. 1221 - 1225
(2017/08/15)
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- Production method for epichlorohydrin
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The invention relates to a production method for epichlorohydrin. The method mainly solves the problems of large amounts of waste water and waste residues, serious pollution and strong corrosiveness to equipment in the prior art. A technical scheme of the invention adopts the production method which comprises the following steps: with chloropropene and ethylbenzene hydroperoxide as raw materials and ethylbenzene as a solvent, subjecting the raw materials and a titanium-contained porous silicon dioxide catalyst to contact reaction so as to obtain epichlorohydrin and alpha-methylbenzyl alcohol under the conditions that reaction temperature is 25 to 200 DEG C; reaction absolute pressure is 0.1 to 8.0 MPa; a molar ratio of chloropropene to ethylbenzene hydroperoxide is 1 to 15; and weight-space velocity of ethylbenzene hydroperoxide is 0.01 to 20 h. Thus, the problem is well solved, and the method can be applied in industrial production of epichlorohydrin.
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Paragraph 0070-0071
(2017/03/18)
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- Method for synthesizing chloropropylene oxide from glycerin
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The invention discloses a method for synthesizing chloropropylene oxide from glycerin. The method comprises a glycerin chlorination reaction and a dichloropropanol saponification reaction. The method comprises the following steps: carrying out a reaction on glycerin at 105DEG C with adipic acid as a catalyst according to a molar ratio of the catalyst to glycerin of 1:23 to obtain highest-yield dichloropropanol, putting a flask with three necks in an oil bath pot, adding dichloropropanol and sodium hydroxide to the flask according to a molar ratio of sodium hydroxide to dichloropropanol of 1:1-1.4:1, carrying out a cyclization reaction at 40-65DEG C for 20-40min, neutralizing the above obtained reaction product with hydrochloric acid, carrying out water vapor distillation, condensing the obtained mixed steam in order to layer the mixed steam, drying the obtained lower layer liquid with anhydrous sodium chloride overnight, carrying out reduced pressure distillation, and collecting a 83-85DEG C/34000Pa fraction. The method for synthesizing chloropropylene oxide, provided by the invention, has the advantages of short time, high income, few steps, simple requirements of the catalyst, low production cost, energy recycling, reduction of the energy consumption and the material consumption, and improvement of the quality of the product.
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Paragraph 0017
(2017/01/17)
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- Method for producing dichlorohydrin through glycerol chlorination
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The invention belongs to the technical field of compound preparation, and particularly relates to a method for producing dichlorohydrin through glycerol chlorination. The method comprises the steps that a catalytic chlorination reaction is conducted by taking glycerol as a raw material and taking HCl as gas through an existing conventional technology, and an active catalyst is prepared by taking compounds of cobalt, compounds of manganese and compounds of iron as active components, taking compounds of zinc as active auxiliaries and applying the active components and the active auxiliaries to the surface of a catalyst carrier. According to the method, positive catalysis of a dichlorohydrin reaction can be effectively catalyzed, and obtained dichlorohydrin (including 1,3-dichlorohydrin and 1,2-dichlorohydrin) is good in selectivity and high in target product yield.
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Paragraph 0025-0027; 0031-0033; 0037-0039; 0043-0045
(2017/04/22)
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- 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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supporting information
p. 4559 - 4570
(2016/08/18)
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- PROCESS FOR HYDROGENATING DICHLOROISOPROPYL ETHER
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Convert dichloroisopropyl ether into a halogenated derivative by contacting the dichloroisopropyl ether with a source of hydrogen and a select heterogeneous hydrogenation catalyst under process conditions selected from a combination of a temperature within a range of from 50 degrees centigrade (oC) to 350 oC, a pressure within a range of from atmospheric pressure (0.1 megapascals) to 1000 pounds per square inch (6.9 MPa), a liquid feed volume flow to catalyst mass ratio between 0.5 and 10 L/Kg*h and a volume hydrogen / volume liquid ratio between 100 and 5000 ml gas/ ml liquid. The halogenated derivative is at least one of 1-chloro-2-propanol and 1,2-dichloropropane 1, and glycerin monochlorohydrin.
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Page/Page column 6
(2016/04/20)
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- A kind of glycerin method of preparing dichlorohydrine chloride
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The invention relates to a method of preparing dichloropropanol by glycerol chlorination, belonging to the field of application of biomas glycerol. The method comprises the following step of: by using a hydrogen chloride gas as a chlorinating agent, by using malic acid, citric acid and lactic acid as a catalyst to catalyze glycerol chlorination to prepare the dichloropropanol. The material glycerol adopted by the method disclosed by the invention is cheap in price, and chloridized to have important industrial significance in developing downstream products. Hydroxyl carboxylic acid is easy to obtain and does not need further treatment; while being used as the catalyst for chlorination, the hydroxyl carboxylic acid has no pollution to environment, is high in catalytic activity, simple in process, gentle in reaction condition, less in dosage of the catalyst and less in reaction byproducts.
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Paragraph 0021-0023
(2017/05/12)
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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 24; 25
(2015/03/28)
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- Rate coefficients for the gas-phase reactions of chlorine atoms with cyclic ethers at 298 K
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Rate coefficients of reactions of Cl atoms with cyclic ethers, tetrahydropyran (THP), tetrahydrofuran (THF), and dihydrofurans (2,5-DHF and 2,3-DHF) have been measured at 298 K using a relative rate method. The relative rate ratios for THP and THF are 0.80 ± 0.05 and 0.80 ± 0.08, respectively, with n-hexane as the reference molecule. The relative rate ratios for THF and 2,5-DHF with n-pentane as the reference molecule are 0.95 ± 0.07 and 1.73 ± 0.06, respectively, and for 2,5-DHF with 1-butene as reference is 1.38 ± 0.05. The average values of the rate coefficients are (2.52 ± 0.36), (2.50 ± 0.39), and (4.48 ± 0.59) × 10-10 cm3 molecule-1 s-1 for THP, THF, and 2,5-DHF, respectively. The errors quoted here for relative rate ratios are 2σ of the statistical variation in different sets of experiments. These errors, combined with the reported errors of the reference rate coefficients using the statistical error propagation equation, are the quoted errors for the rate coefficients. In the case of 2,3-DHF, after correcting for the dark reaction with CH3COCl and assuming no interference from other radical reactions, a relative rate ratio of 0.85 ± 0.16 is obtained with respect to cycloheptene, corresponding to a rate coefficient of (4.52 ± 0.99) × 10-10 cm3 molecule-1 s-1. Unlike cyclic hydrocarbons, there is no increase with increasing number of CH2 groups in these cyclic ethers whereas there is an increase in the rate coefficient with unsaturation in the ring. An attempt is also made to correlate the rate coefficients of cyclic hydrocarbons and ethers with the molecular size as well as HOMO energy.
- Alwe,Walawalkar,Sharma,Pushpa,Dhanya,Naik
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p. 295 - 305
(2013/08/25)
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- Biocatalytic preparation of dichloropropyl acrylates. Application to the synthesis of poly(dichloropropyl acrylates)
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The synthesis of dichloropropyl acrylates from dichloropropyl dodecanoates through a transesterification process using diverse commercial lipases and whole cells (fungal resting cells) is presented. The synthesis was carried out in a solvent-free media using a conventional batch system and a packed bed reactor (PBR). The effect of water activity on the process depended on the lipase used. The commercial enzyme CALB (Candida antarctica lipase B immobilized onto a macroporous acrylic resin) showed the best performance as a biocatalyst, achieving a yield of 50% and productivity of 7.2 μmol min-1 g -1 in the batch reactor and 33% and 35.8 μmol min-1 g-1 in the PBR. Finally, polymeric material was prepared by suspension polymerization of the dichloropropyl acrylates synthesized using PBR. Particles with diameters between 170 and 380 μm were obtained with a yield of 85% after 18 h reaction. AbbreviationsPBRpacked bed reactorCALBCandida antarctica lipase B immobilized onto a macroporous acrylic resin.
- Edinson, Yara-Varon,Jordi, Eras Joli,Merce, Torres,Merce, Balcells,Gemma, Villorbina,Ramon, Canela-Garayoa
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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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- PROCESS FOR THE CHLORINATION OF A HYDROXYLATED ORGANIC COMPOUND
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Process for the chlorination of an organic compound comprising at least one aliphatic hydroxyl group, said process comprising the steps of actively adding to said organic compound (i) hydrogen chloride and (ii) a HCl desolubilizer or a precursor thereof, and heating the resulting mixture at a reaction temperature in the range 20°-160°C, wherein said chlorination is performed in the presence of a catalyst selected from the group consisting of (a) ketones, (b) aldehydes, (c) carboxylic acids with 1-8 carbon atoms, (d) organic compounds comprising a β-diketone moiety or a β-keto aldehyde moiety, and (e) organic polymers comprising at least one carbonyl group, having a vapour pressure at the reaction temperature of less than 1 mbar, a weight average molecular weight Mw of 500 g/mole or more, and are soluble in the reaction mixture at the reaction temperature, and wherein the HCl desolubilizer is an alkali metal chloride salt, an alkaline earth metal chloride salt, or an acid.
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Page/Page column 17; 18
(2013/03/26)
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- METHOD FOR PRODUCTION OF DICHLOROPROPANOLS FROM GLYCEROL
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Method for production of dichloropropanols from glycerol using continuous method, in the presence of acetic acid as a catalyst, with the catalyst concentration in the reacting mass varying in the range of 0.0005 to 0.007 mol/L, and the process of hydrochlorina? tion is carried out in the temperature range from 80 to 160°C, consists in the fact that hydrochlorination of glycerol is carried out in two stages, while in the first stage, glycer? ol is subjected to wet hydrochlorination using hydrochloric acid contained in the stream of acidic dichloropropanols, then the post-reaction mass from the first stage of hydro? chlorination is directed to a reactive column, in which completing the reaction of resi? dues of dissolved hydrogen chloride is carried out, as well as separation of the post- reaction mixture to stream of diluted dichloropropanols and decoction stream, which is directed to the second stage of dry hydrochlorination under pressure with gaseous hy? drogen chloride; after the second stage of hydrochlorination, the post-reaction mixture is directed to a distillation column, in which dewatering is carried out, while the distillate from the distillation column is directed to the first stage of glycerol hydrochlorination as a stream of acidic dichloropropanols, and the decoction being a stream of concentrated dichloropropanols is subjected to rectification.
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Page/Page column 9-10
(2012/07/28)
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- Directed Evolution Strategies for Enantiocomplementary Haloalkane Dehalogenases: From Chemical Waste to Enantiopure Building Blocks
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We used directed evolution to obtain enantiocomplementary haloalkane dehalogenase variants that convert the toxic waste compound 1,2,3-trichloropropane (TCP) into highly enantioenriched (R)- or (S)-2,3-dichloropropan-1-ol, which can easily be converted into optically active epichlorohydrins-attractive intermediates for the synthesis of enantiopure fine chemicals. A dehalogenase with improved catalytic activity but very low enantioselectivity was used as the starting point. A strategy that made optimal use of the limited capacity of the screening assay, which was based on chiral gas chromatography, was developed. We used pair-wise site-saturation mutagenesis (SSM) of all 16 noncatalytic active-site residues during the initial two rounds of evolution. The resulting best R- and S-enantioselective variants were further improved in two rounds of site-restricted mutagenesis (SRM), with incorporation of carefully selected sets of amino acids at a larger number of positions, including sites that are more distant from the active site. Finally, the most promising mutations and positions were promoted to a combinatorial library by using a multi-site mutagenesis protocol with restricted codon sets. To guide the design of partly undefined (ambiguous) codon sets for these restricted libraries we employed structural information, the results of multiple sequence alignments, and knowledge from earlier rounds. After five rounds of evolution with screening of only 5500 clones, we obtained two strongly diverged haloalkane dehalogenase variants that give access to (R)-epichlorohydrin with 90% ee and to (S)-epichlorohydrin with 97% ee, containing 13 and 17 mutations, respectively, around their active sites.
- van Leeuwen, Jan G.E.,Wijma, Hein J.,Floor, Robert J.,Van der Laan, Jan-Metske,Janssen, Dick B.
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experimental part
p. 137 - 148
(2012/04/23)
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- Haloalkane dehalogenase catalysed desymmetrisation and tandem kinetic resolution for the preparation of chiral haloalcohols
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Six different bacterial haloalkane dehalogenases were recombinantly produced in Escherichia coli, purified, and used to catalyse the conversion of prochiral short-chain dihaloalkanes and a meso dihaloalkane, yielding enantioenriched haloalcohols. A two-reaction one-enzyme process was established in which the desymmetrisation of a dihaloalkane is followed by kinetic resolution of the chiral haloalcohol that is produced in the first step. In case of 1,3-dibromo-2-methylpropane and 1,3-dibromo-2-phenylpropane, an increase of the enantiomeric excess of the respective haloalcohol was observed in time, leading to ee values of >97%, with analytical yields of 24 and 52%, respectively. The results show that haloalkane dehalogenases can be used for the production of highly enantioenriched haloalcohols and that in some cases product enantiopurity can be improved by allowing a two-step one-enzyme tandem reaction.
- Westerbeek, Alja,Van Leeuwen, Jan G.E.,Szymański, Wiktor,Feringa, Ben L.,Janssen, Dick B.
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experimental part
p. 7645 - 7650
(2012/09/21)
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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 58-60
(2011/02/24)
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- METHOD OF PREPARING DICHLOROPROPANOL USING GLYCEROL WITH IMPROVED SELECTIVITY FOR DICHLOROPROPANOL
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A method of preparing dichloropropanol using glycerol. The method includes: chlorination of glycerol including a plurality of chlorination reaction stages using a catalyst; and a water-removing stage performed between the reaction stages, independently of the reaction stages.
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Page/Page column 2; 4
(2011/11/30)
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- A PROCESS FOR THE PREPARATION OF DICHLOROHYDRIN
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A process for the preparation of dichlorohydrin starting from isobutylene and glycerol is disclosed. Th used glycerol can be derived, as a byproduct, from the transesterification of triglycerides. Dichlorohydrin is produced in a cyclic process, wherein, by reaction of isobutylene and glycerol, mono tert. butyl ether is formed, which is thereafter reacted with hydrogen chloride to produce the desired dichlorohydrin. The byproducts, formed in each step, can be recycled to the first step of the process.
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Page/Page column title page; 4
(2011/08/21)
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- 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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experimental part
p. 101 - 112
(2010/11/05)
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- PROCESS FOR PREPARING CHLOROHYDRIN BY REACTION OF POLYOL WITH HYDROCHLORIC ACID
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The present invention relates to a method for preparing chlorohydrin by chlorination of polyol such as glycerin with hydrogen chloride. The method of the present invention is composed of the following processes: reaction mixture feed comprising polyol, hydrogen chloride and organic acid (catalyst for chlorination) is loaded into the first reactor, in which chlorohydrin is generated by chlorination; the first product mixture feed containing the chlorohydrin and non- reacted reaction mixture discharged from the first reactor and the additional polyol feed are supplied to the second reactor, in which chlorohydrin is generated by additional chlorination; the second product mixture feed containing the chlorohydrin discharged from the second reactor is loaded in distillation column and then distillation product containing chlorohydrin is separated through the top of the distillation column; and some re-circulated feed of distillation residual solution containing chlorohydrin, is re-circulated into the first reactor.
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Page/Page column 40-46
(2009/05/29)
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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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- METHOD OF PREPARING DICHLOROPROPANOL FROM GLYCEROL USING HETEROPOLYACID CATALYSTS
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Provided is a method of preparing dichloropropanol from glycerol. According to the method, glycerol is reacted with a chlorinating agent using a heteropolyacid catalyst to prepare dichloropropanol. Accordingly, dichloropropanol can be directly prepared from glycerol by using heteropolyacid catalysts, and conventional problems such as recovery of the catalyst and separation of an azeotropic mixture including the catalyst and the products can be overcome. In addition, since the catalyst can be easily recovered and reused, the manufacturing process can be simplified and expensive dichloropropanol can be produced at high yield from inexpensive glycerol.
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Page/Page column 6-7; 8
(2009/07/17)
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- PROCESS FOR MANUFACTURING GLYCIDOL
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Process for manufacturing glycidol comprising at least the following steps: a) glycerol and a chlorinating agent are reacted to form monochloropropanediol in a first reaction medium; and b) at least one part of the reaction medium from step a) is reacted with at least one basic compound to form glycidol and a salt in a second reaction medium, the organic component of which has a monochloropropanediol content before reaction with the basic compound greater than 100 g/kg of organic component.
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Page/Page column 22-23
(2009/03/07)
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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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- 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 14-15
(2009/10/18)
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- MANUFACTURE OF DICHLOROPROPANOL
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Manufacture of dichloropropanol Process for manufacturing dichloropropa nol wherein a glycerol-based product comprising at least one diol containi ng at least 3 carbon atoms other than 1,2- propanediol, is reacted with a chlorinati ng agent, and of products derived from dichloropropanol such as ep ichlorohydrin and epoxy resins. No figure.
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Page/Page column 19-21
(2009/03/07)
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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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- 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; 9
(2008/12/08)
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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 38
(2008/06/13)
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- PROCESS FOR PRODUCING AN ORGANIC COMPOUND
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Process for producing a chlorohydrin by reaction between a multihydroxylated- aliphatic hydrocarbon, an ester of a multihydroxylated-aliphatic hydrocarbon, or a mixture thereof, and a chlorinating agent, according to which the multihydroxylated-aliphatic hydrocarbon, the ester of a multihydroxylated- aliphatic hydrocarbon, or the mixture thereof used contains at least one solid or dissolved metal salt, the process comprising a separation operation to remove at least part of the metal salt.
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Page/Page column 33-34
(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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- METHOD OF PREPARING DICHLOROPROPANOLS FROM GLYCERINE
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A method of highly selective catalytic hydrochlorination of glycerine and/or monochloropropanediols to the dichloropropanol products 1,3-dichloro-2-propanol and 2,3--dichloro-l-propanol, carried out in at least one continuous reaction zone at reaction temperatures in the range of 70-140 °C and with continuous removing of the water of reaction, the liquid feed containing at least 50 % by weight of glycerine and/or monochloropropanediols. The method can be carried out in a continuously operating one-step circulation reactor or a cascade of continuous flow reactors of the liquid-gas type.
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Page/Page column 5-8
(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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- PROCESS FOR PREPARING EPICHLOROHYDRIN FROM ETHANE
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A process for preparing epichlorohydrin comprises (1) converting ethane to 1,2-dichloroethylene (cis/trans mixture) in the presence of a catalyst; (2) producing 2,3-dichloropropanal by (a) hydroformylating the 1,2-- dichloroethylene in the presence of a catalyst, carbon monoxide, and hydrogen, (b) adding MeOH to the 1,2-dichloroethylene, or (c) subjecting the 1,2-dichloroethylene to direct reductive hydroformylation in the presence of a reductive hydroformylation catalyst; and (3) epoxidizing the 2,3-DCH with a base to produce epichlorohydrin.
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Page/Page column 12-14
(2008/06/13)
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- Method for producing 2,3-dichloro-1-propahol and epichlorohyrin
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Methods for continuously producing 2,3-dichloro-1-propanol (2,3-DCH) and epichlorohydrin in high yields and in a stabel manner for a long time are disclosed. In a method where allyl alcohol is chorinated in a hyrochloric acid solution and the reaction solution is introduced into a degassing tower to release hydrogen chloride and 2,3-DCH is obtained from the remaining solution, the concentraton of chlorine in the reaction mixture to be introduced into the degassing tower is maintaining to 0.015 g/ml or less and/or the partial pressure of chlorine gas in the reactor immediately before the degassing tower to 0.08 MPa or less, by monitoring and/or the partial pressure of chlorine gas in the reactor immediately before the degassing tower to 0.08 MPa or less, by monitoring and/or controlling the chlorine concentration of a solution at the outlet of the reactor immediately before the degassing tower and/or the partial pressure of chlorine gas present in the gas phase section of the reactor and the flow rate of chlorine gas immediately before the degassing tower.
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