WO2012002647A2 - 클로로히드린류의 제조방법 및 그 방법에 의해 제조된 클로로히드린류를 사용하는 에피클로로히드린의 제조방법 - Google Patents
클로로히드린류의 제조방법 및 그 방법에 의해 제조된 클로로히드린류를 사용하는 에피클로로히드린의 제조방법 Download PDFInfo
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- WO2012002647A2 WO2012002647A2 PCT/KR2011/004167 KR2011004167W WO2012002647A2 WO 2012002647 A2 WO2012002647 A2 WO 2012002647A2 KR 2011004167 W KR2011004167 W KR 2011004167W WO 2012002647 A2 WO2012002647 A2 WO 2012002647A2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/64—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by simultaneous introduction of -OH groups and halogens
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/34—Halogenated alcohols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
Definitions
- a method for producing chlorohydrins and a method for producing epichlorohydrin using chlorohydrins prepared by the method are disclosed. More specifically, reacting a multi-acid aliphatic hydrocarbon with a chlorinating agent in the presence of a catalyst, comprising a plurality of reaction steps and a water removing step interposed between the plurality of reaction steps, wherein the plurality of reaction steps.
- a method for producing chlorohydrins, in which at least a part of the reaction mixture discharged in at least one reaction step of the above is mixed with the chlorinating agent and then recycled to the reaction step in which the reaction mixture is discharged, and chlorohex produced by the method Disclosed is a method for preparing epichlorohydrin comprising reacting aspirin with an alkaline agent.
- chlorohydrins such as dichloropropanol are used as raw materials for producing epichlorohydrin, and most of the chlorohydrins currently supplied to the market are made from propylene.
- the method for producing chlorohydrins is a step of preparing allyl chloride by high temperature chlorination of propylene and using the excess industrial water to react the allyl chloride again with a chlorinating agent to give chlorohydrins. It consists of two steps of preparing a step.
- a process of directly preparing chlorohydrins by a one-step preparation method of reacting a multiacid aliphatic hydrocarbon including glycerol, which is a by-product of biodiesel, with a chlorinating agent has secured economic feasibility.
- the production method of this one-stage chlorohydrin which uses a polycarboxylic acid aliphatic hydrocarbon including glycerol as a reaction raw material, uses a low-cost polycarboxylic acid aliphatic hydrocarbon, which not only reduces raw material costs but also does not use industrial water during the process. Since the amount of wastewater and waste can be significantly reduced, it is environmentally advantageous, and the initial investment cost is low because process and environment related investment costs can be reduced.
- the method for producing chlorohydrins produces water as a by-product, and the produced water inhibits the chlorination reaction of the polycarboxylic acid aliphatic hydrocarbons including glycerol, and as the reaction proceeds, the reaction rate gradually decreases and the reaction time becomes longer. There is a problem that the selectivity of chlorohydrins is lowered.
- One embodiment of the present invention is to react a multi-acid aliphatic hydrocarbon with a chlorinating agent in the presence of a catalyst, comprising a plurality of reaction steps and a water removal step interposed between the plurality of reaction steps, wherein the plurality of reactions
- a method for preparing chlorohydrins in which at least a portion of the reaction mixture discharged in at least one of the reaction stages is mixed with an additional chlorinating agent and then recycled to the reaction stage in which the reaction mixture is discharged.
- Another embodiment of the present invention provides a method for preparing epichlorohydrin comprising the step of reacting chlorohydrins prepared by the method for producing chlorohydrins with an alkaline agent.
- a method for producing chlorohydrins by reacting a polyacid aliphatic hydrocarbon with a chlorinating agent in the presence of a catalyst,
- At least one combination of a series of unit operations comprising in said sequence a second reaction step of reacting at least one component of said reaction mixture from which said water has been removed with at least one of said chlorinating agent and further chlorinating agent,
- At least a portion of the reaction mixture discharged in at least one of the plurality of reaction stages of the chlorohydrin further comprises the step of mixing with the additional chlorinating agent and then recycling the reaction mixture to the discharged reaction stage It provides a manufacturing method.
- It provides a method for producing chlorohydrin comprising the step of injecting the first reactor effluent from which the water is removed into a second reactor maintained at a temperature of 80 ⁇ 200 °C.
- the method for preparing chlorohydrins may further comprise mixing at least a portion of the second reactor effluent with an additional chlorinating agent and then recycling the mixture to the second reactor.
- the polycarboxylic acid aliphatic hydrocarbon may be a compound having 2 to 20 carbon atoms, including two or more hydroxyl groups bonded to different carbon atoms.
- the polycarboxylic acid aliphatic hydrocarbon is 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol, glycerol , 1,2,4-butanetriol, 1,4-butanediol and at least one compound selected from the group consisting of esters of the above compounds.
- the chlorohydrins produced by the above production method may be a compound including at least one hydroxyl group and at least one chlorine atom bonded to different carbon atoms.
- the chlorohydrins are composed of 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol, 1,3-dichloropropan-2-ol and 2,3-dichloro propan-1-ol At least one compound selected from the group.
- the catalyst may include at least one selected from the group consisting of an organic acid catalyst, a carboxylic acid catalyst, a nitrile catalyst and a solid catalyst.
- a reaction product of the catalyst and the polycarboxylic acid aliphatic hydrocarbon is produced as an intermediate product, and the intermediate product may catalyze the chlorination reaction of the polycarboxylic acid aliphatic hydrocarbon.
- the polycarboxylic acid aliphatic hydrocarbon may include glycerol
- the catalyst may include acetic acid
- the intermediate may include glycerol acetates.
- the chlorinating agent and / or further chlorinating agent may comprise hydrogen chloride gas or hydrochloric acid aqueous solution.
- the first reactor effluent injected into the water removal apparatus may be discharged when the conversion rate of the polycarboxylic acid aliphatic hydrocarbon is 30 to 100% and the yield of the chlorohydrin is 30 to 95% in the first reactor.
- the first reactor effluent injected into the water removal device is a polycarboxylic acid aliphatic hydrocarbon, chlorohydrin and the intermediate product, 0 to 90 parts by weight of the polycarboxylic acid aliphatic hydrocarbon: 5 to 95 weight of the chlorohydrin Part: may be included in a ratio of 5 to 12 parts by weight of the intermediate product.
- the first reactor effluent injected into the water removal apparatus may include a chlorinating agent and water in a ratio of 10 to 25 parts by weight: 75 to 90 parts by weight of water.
- At least a portion of the first reactor effluent and the additional chlorinating agent may be mixed in an ejector, an inline mixer, an ultrasonic mixer or a mixing device comprising two or more of them.
- the residence time of the reactor contents in the first reactor may be 20 minutes to 1 hour, and the residence time of the reactor contents in the second reactor may be 1 hour to 3 hours.
- the water removal apparatus may be operated by a distillation operation that utilizes the boiling point difference between the components of the first reactor effluent.
- the first reactor and the second reactor may be maintained at a pressure above atmospheric pressure, and the water removal apparatus may be maintained at a pressure below atmospheric pressure.
- the first reactor and the second reactor may be maintained at 1 to 20 atm, the water removal device may be maintained at 10 ⁇ 760mmHg.
- the water removal device may include a reduced pressure distillation column having a theoretical stage of 2 to 50.
- the first reactor effluent may be injected into the water removal device after being depressurized in the pressure reducing device.
- the pressure reducing device may include a pressure reducing valve.
- the first reactor and the second reactor independently of each other, a continuous stirred tank reactor (CSTR), a batch reactor (batch reactor), a semi-batch reactor or a tubular reactor (plug flow) reactor).
- CSTR continuous stirred tank reactor
- batch reactor batch reactor
- semi-batch reactor semi-batch reactor
- tubular reactor tubular reactor
- the first reactor effluent injected into the water removal device may be separated into a water-rich layer and a water-lack layer.
- the method for preparing chlorohydrins may include purifying chlorohydrins from a portion of the second reactor effluent not recycled to the second reactor to obtain a chlorohydrin concentrate, and the water-rich layer and Mixing the chlorohydrin concentrate may further comprise obtaining a first composition of chlorohydrins (first composition of chlorohydrins).
- the portion of the second reactor effluent not recycled to the second reactor is 0 to 10 parts by weight of a polycarboxylic acid aliphatic hydrocarbon, 80 to 98 parts by weight of chlorohydrin, 0 to 10 parts by weight of chlorinating agent and water 1 to 20 It may include parts by weight.
- the first chlorohydrin composition may include 0 to 10 parts by weight of a polycarboxylic acid aliphatic hydrocarbon, 60 to 96 parts by weight of chlorohydrins, 0 to 20 parts by weight of a chlorinating agent, and 0 to 30 parts by weight of water.
- the method for preparing chlorohydrin may further include diluting the first chlorohydrin composition with water to obtain a second chlorohydrin composition.
- the water may be added in a ratio of 100 to 500 parts by weight based on 100 parts by weight of the first chlorohydrin composition.
- the second chlorohydrin composition is composed of epichlorohydrin containing 0 to 5 parts by weight of a polycarboxylic acid aliphatic hydrocarbon, 10 to 40 parts by weight of chlorohydrins, 0 to 5 parts by weight of chlorinating agent and 50 to 90 parts by weight of water. It provides a manufacturing method.
- the second chlorohydrin composition may further include a catalyst, and the catalyst may react with the alkali agent to form an alkali metal salt.
- a method for preparing chlorohydrins with improved selectivity of chlorohydrins may be provided.
- a method for preparing epichlorohydrin comprising the step of reacting the chlorohydrins prepared by the method for producing chlorohydrins with an alkali agent.
- 1 is a process chart for implementing a method for producing chlorohydrin and a method for preparing epichlorohydrin according to an embodiment of the present invention.
- the 'manufacturing method of chlorohydrins' may mean a method of preparing a composition of chlorohydrins.
- a polyacid aliphatic hydrocarbon is reacted with a chlorinating agent in the presence of a catalyst.
- the method for preparing chlorohydrins may include a first reaction step of reacting a multi-acid aliphatic hydrocarbon with a chlorinating agent, a water removal step of dehydrating a reaction mixture containing water as a by-product as discharged from the first reaction step, and the dehydration. At least one combination of a series of unit operations comprising in said sequence a second reaction step of reacting at least one component of said reaction mixture with at least one of said chlorinating agent and further chlorinating agent.
- at least a part of the reaction mixture withdrawn from at least one of the plurality of reaction stages is mixed with a further chlorinating agent and then recycled to the reaction stage with which the reaction mixture is withdrawn.
- the chlorinating agent is not added in the water removal step.
- chlorohydrins means chlorohydrin, esters of chlorohydrin or mixtures thereof.
- the chlorohydrin may be a compound in which at least one hydroxyl group and at least one chlorine atom are bonded to different carbon atoms.
- the chlorohydrins are 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol, 1,3-dichloropropan-2-ol and 2,3-dichloropropane- It may comprise at least one compound selected from the group consisting of 1-ol.
- 3-chloro-1,2-propanediol and 2-chloro-1,3-propanediol are collectively referred to as 'monochloropropanediol', and 1,3-dichloropropan-2-ol and 2, 3-dichloropropan-1-ol is collectively referred to as 'dichloropropanol'.
- the method for producing chlorohydrins according to one embodiment of the present invention mainly produces 1,3-dichloropropan-2-ol, which is particularly suitable as a reaction material for the preparation of epichlorohydrin. .
- the multiacid aliphatic hydrocarbons and catalyst are injected into the first reactor 110 via line 1.
- chlorinating agent is also injected into the first reactor 110 via line 2 and / or other routes.
- the polycarboxylic acid aliphatic hydrocarbon may be a compound having 2 to 20 carbon atoms, including two or more hydroxyl groups bonded to different carbon atoms.
- the multi-acid aliphatic hydrocarbons include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 3-chloro-1,2-propanediol, 2-chloro-1,3- At least one compound selected from the group consisting of propanediol, glycerol, 1,2,4-butanetriol, 1,4-butanediol and esters of the above compounds.
- the catalyst may be an organic acid catalyst, a carboxylic acid catalyst, a nitrile catalyst, a solid catalyst, and a mixture thereof.
- the organic acid catalyst is, for example, at least one member selected from the group consisting of monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, malonic acid, levulinic acid, citric acid, succinic acid, propionic acid and derivatives of the organic acids described above. It may include a compound of.
- the carboxylic acid catalyst is, for example, monocarboxylic acid ester, polycarboxylic acid ester, monocarboxylic acid anhydride, polycarboxylic acid anhydride, monocarboxylic acid chloride, polycarboxylic acid chloride, monocarboxylic It may include at least one compound selected from the group consisting of acid salts, polycarboxylic acid salts and derivatives of the respective carboxylic acid compounds.
- the nitrile-based catalysts are acetonitrile, propionitrile, acrylonitrile, valeronitrile, isobutyronitrile, hydroxyacetonitrile, chloroacetonitrile, succinonitrile, glutaronitrile, adiponitrile and phenylacetonitrile. It may include at least one compound selected from the group consisting of.
- the solid catalyst may be, for example, an inorganic oxide, an inorganic halide, a strongly acidic organic compound, and a mixture of two or more thereof.
- the inorganic oxide may include at least one compound selected from the group consisting of metal oxides, complex oxides, oxyacids and oxyacid salts.
- the metal oxide may be, for example, SiO 2 , Al 2 O 3 , TiO 2 , Fe 2 O 3 , ZrO 2 , SnO 2 , CeO 2 , Ga 2 O 3 , La 2 O 3 .
- the complex oxide may be, for example, SiO 2 -Al 2 O 3 , SiO 2 -TiO 2 , TiO 2 -ZrO 2 , SiO 2 -ZrO 2 , MoO 3 -ZrO 2 , zeolites, heteropolyacids (ie, P, Mo Polyacids containing elements such as, V, W, Si, and the like) and heteropolyacids.
- the oxy acid and oxy acid salt may be, for example, BPO 4 , AlPO 4 , polyphosphoric acid, acidic phosphate, H 3 BO 3 , acidic borate, niobic acid.
- the inorganic halide may be, for example, a Group 3A element on the periodic table such as scandium, yttrium, lanthanum, actinium; Group 4A elements on the periodic table, such as titanium, zirconium and hafnium; Elements of Group 5A on the periodic table such as vanadium, niobium, and tantalum; Group 8 elements on the periodic table, such as iron, cobalt, nickel, palladium, and platinum; Group 2B elements on the periodic table such as zinc; Group 3B elements on the periodic table such as aluminum and gallium; Metal halides such as metal fluorides, chlorides, bromide and iodides of Group 4B elements on the periodic table such as germanium and tin.
- a Group 3A element on the periodic table such as scandium, yttrium, lanthanum, actinium
- Group 4A elements on the periodic table such as titanium, zirconium and hafnium
- Elements of Group 5A on the periodic table such as
- the strongly acidic organic compound may be, for example, an organic sulfonic acid compound such as a sulfonic acid group-containing ion exchange resin and a sulfonic acid compound including a condensed carbon ring.
- an organic sulfonic acid compound such as a sulfonic acid group-containing ion exchange resin and a sulfonic acid compound including a condensed carbon ring.
- the injection amount of the catalyst may be 1 to 10 parts by weight based on 100 parts by weight of the multi-acid aliphatic hydrocarbon. If the injection amount of the catalyst is within the above range, a good reaction speed improving effect can be obtained at an appropriate catalyst amount.
- the first reactor 110 may be maintained at a temperature of 50 ⁇ 200 °C. When the temperature of the first reactor 110 is within the above range, a high reaction rate can be obtained by appropriate energy input.
- the first reactor 110 may be maintained at a pressure above atmospheric pressure, for example, 1 to 20 atmospheres. If the pressure of the first reactor 110 is within the above range, a relatively high reaction activity can be obtained. In this case, even if the pressure of the first reactor 110 exceeds 20 atm, the effect of increasing the reaction activity according to the increase in pressure is not large.
- the first reactor 110 may be a continuous stirred tank reactor (CSTR).
- the first reactor 110 may be a batch reactor, a semi-batch reactor, or a plug flow reactor.
- a reaction product of the catalyst and the polycarboxylic acid aliphatic hydrocarbon is produced as an intermediate product, as well as chlorohydrins, which are main products, and the intermediate product is a chlorination reaction of the polycarboxylic acid aliphatic hydrocarbon (eg, For example, catalysis may be performed in the chlorohydrin generation reaction occurring in the first reactor 110 and / or the second reactor 150.
- the intermediate may comprise glycerol acetates.
- 'glycerol acetates means substituted or unsubstituted glycerol monoacetate, substituted or unsubstituted glycerol diacetate, substituted or unsubstituted glycerol triacetate, or a mixture thereof.
- substituted means that the hydrogen atom in the compound is substituted with a halogen group, a hydroxy group, an alkyl group, an alkoxy group, an amine group or a combination thereof.
- the residence time of the reactor contents in the first reactor 110 may be 20 minutes to 1 hour. If the residence time of the first reactor contents is within the above range, a high conversion rate of the polycarboxylic acid aliphatic hydrocarbon can be obtained within a suitable time.
- the chlorinating agent may include hydrogen chloride gas or hydrochloric acid aqueous solution.
- reaction that takes place in the first reactor 110 is the chlorination reaction of a polycarboxylic acid aliphatic hydrocarbon (eg, glycerol) represented by Scheme 1 below.
- a polycarboxylic acid aliphatic hydrocarbon eg, glycerol
- Conversion of glycerol, yield of monochloropropanediol (MCP) in the reaction, yield of dichloropropanol (DCP), selectivity of monochloropropanediol (MCP) and selectivity of dichloropropanol (DCP) are represented by the following formulas 1 to 5 Can be calculated respectively.
- MCP monochloropropanediol
- the first reactor effluent is discharged from the first reactor 110 and flows into line 3 and / or line 4. That is, at least a portion of the first reactor effluent flows into the first mixing device 120 through the line 3, and the remaining portion of the first reactor effluent is decompressed in the decompression device 131 and then the line ( 4) is introduced into the water removal device 140.
- the first reactor effluent comprises a catalyst; Chlorohydrins; Intermediate products such as glycerol acetates; water; Unreacted polyacid aliphatic hydrocarbon; And / or chlorinating agents.
- the chlorinating agent is also injected into the first mixing device 120 via line 2. In the first mixing device 120, the first reactor effluent is mixed with the chlorinating agent and then recycled to the first reactor 110.
- the first mixing device 120 may include an ejector, an inline mixer, an ultrasonic mixer, or two or more thereof.
- the first reactor effluent may act as a motive fluid and the chlorinating agent may act as a suction fluid.
- the pressure reducing device 131 may include a pressure reducing valve.
- the additional chlorinating agent may comprise hydrogen chloride gas or hydrochloric acid aqueous solution.
- the water removal device 140 may be operated by a distillation operation using the boiling point difference between the components of the first reactor effluent.
- the water removal device 140 may be maintained at a pressure below atmospheric pressure, for example, 10 ⁇ 760mmHg. If the pressure of the water removal device 140 is within the above range, the temperature of the lower effluent (that is, the water-poor layer) becomes moderate, so that the amount of high-boiling substances is reduced and the water removal device 140 and the pipe blockage phenomenon. This can be prevented.
- the water removal device 140 may include a reduced pressure distillation column (ie, the dehydration tower 141) having a theoretical number of 2 to 50. When the theoretical number of stages of the vacuum distillation column is within the range, it is possible to minimize the residual amount of water in the water-deficient layer.
- the term "theoretical stage” refers to the number of virtual regions or stages in which two phases such as gaseous phase and liquid phase are in equilibrium with each other in a separation process using the vacuum distillation column.
- the first reactor effluent injected into the water removal device 140 the conversion rate of the multi-acid aliphatic hydrocarbon in the first reactor 110 is 30 to 100%, the yield of the chlorohydrin is 30 to 95% May have been discharged.
- the reaction rate in the first reactor 110 is The problem of deterioration does not occur and the water removal apparatus 140 can obtain a remarkable water removal effect.
- high selectivity of chlorohydrins can be obtained.
- the first reactor effluent injected into the water removal device 140 may include 0 to 90 parts by weight of the polycarboxylic acid aliphatic hydrocarbon, the chlorohydrin and the intermediate product, the polycarboxylic acid aliphatic hydrocarbon. 5 to 95 parts by weight of chlorohydrins: the intermediate product (eg glycerol acetate) may be included in a ratio of 5 to 12 parts by weight.
- the intermediate product eg glycerol acetate
- the first reactor effluent injected into the water removal apparatus 140 may include the chlorinating agent and water in a ratio of 10 to 25 parts by weight of the chlorinating agent: 75 to 90 parts by weight of water.
- the first reactor effluent forms an azeotrope, thereby increasing the solubility of the chlorinating agent in water, thereby minimizing the loss of the chlorinating agent.
- the material discharged to the top of the dewatering tower 141 and condensed in the condenser 143 and introduced into the line 5 (hereinafter referred to as a water-rich layer) includes water and a chlorinating agent, and the dewatering tower Substances flowing into the line 6 after being discharged to the bottom of 141 and not vaporized from the reboiler 142 (hereinafter referred to as the water-lack layer) are unreacted polycarboxylic acid aliphatic hydrocarbons, chlorohydrins and / or the like. Or it may include the above-described intermediate product. Since the intermediate product is injected into the second reactor 150 to catalyze the reaction represented by Scheme 1, the reaction may occur smoothly in the second reactor 150 without additional catalyst.
- Reboiler 142 and condenser 143 may be maintained at a temperature of 100 ⁇ 200 °C and 0 ⁇ 60 °C, respectively.
- the second reactor 150 may be maintained at a temperature of 70 ⁇ 200 °C. When the temperature of the second reactor 150 is within the above range, a high yield of chlorohydrin can be obtained with suitable energy.
- the second reactor 150 may be maintained at a pressure above atmospheric pressure, for example, 1 to 20 atmospheres. When the pressure of the second reactor 150 is within the above range, the solubility of the chlorinating agent in the second reactor contents may be improved.
- the second reactor 150 may be a continuous stirred tank reactor (CSTR).
- CSTR continuous stirred tank reactor
- the present invention is not limited thereto, and the second reactor 150 may be a batch reactor, a semi-batch reactor, or a plug flow reactor.
- the above-described intermediate product and the chlorinating agent separately injected into the second reactor 150 are contacted to further generate chlorohydrins.
- the residence time of the reactor contents in the second reactor 150 may be 1 hour to 3 hours. If the residence time of the second reactor contents is within the above range, a high yield of chlorohydrins can be obtained within a suitable time.
- the reaction that occurs in the second reactor 150 is the same or similar to the reaction that occurs in the first reactor 110.
- the second reactor effluent is discharged from the second reactor 150 and flows into line 7 and / or line 9. That is, at least a portion of the second reactor effluent enters the second mixing device 160 via line 7, and the remaining portion of the second reactor effluent is depressurized in the depressurizer 132 and then line 9.
- the second reactor effluent comprises a catalyst; Chlorohydrins; Intermediate products such as glycerol acetates; water; Unreacted polyacid aliphatic hydrocarbon; And / or chlorinating agents.
- the chlorinating agent is injected into the second mixing device 160 via line 8.
- the second reactor effluent is mixed with the chlorinating agent and then recycled to the second reactor 150.
- the chlorinating agent can also be injected into the second reactor 150 via other routes than line 8.
- the second mixing device 160 may include an ejector, an inline mixer, an ultrasonic mixer, or two or more thereof.
- the mixing device 160 is an ejector, the second reactor effluent may act as a motive fluid and the chlorinating agent may act as a suction fluid.
- the pressure reducing device 132 may include a pressure reducing valve.
- the first distillation apparatus 170 may be operated by a distillation operation using the boiling point difference between the components of the second reactor effluent.
- the first distillation apparatus 170 may be maintained at a pressure below atmospheric pressure, for example, 10 ⁇ 760mmHg.
- the first distillation apparatus 170 may include a reduced pressure distillation column (ie, separation tower 171) having a theoretical stage of 2 to 50. If the theoretical stage of the vacuum distillation column is within the above range, chlorohydrin can be separated with high efficiency.
- the second reactor effluent injected into the first distillation apparatus 170 may include 0 to 10 parts by weight of a polycarboxylic acid aliphatic hydrocarbon, 80 to 98 parts by weight of chlorohydrin, 0 to 10 parts by weight of chlorinating agent, and 1 to 20 parts of water. It may include parts by weight. If the component ratio of the second reactor effluent is within the above range, it means that the reaction is terminated and the yield of chlorohydrin is maximized.
- the gaseous substance is condensed in the condenser 173 and the line ( 10)
- the liquid material is distilled from the reboiler 172 and separated back into the gaseous material and the liquid material again
- the gaseous material is recycled to the separation tower 171 and the liquid material is stripped through the line 11 ( 180).
- the material discharged to the top of the separation tower 171 and condensed in the condenser 173 and introduced into the line 10 includes chlorohydrin, water and / or chlorinating agent, and the separation tower 171.
- the high boiling point material introduced into the line 11 without being vaporized in the reboiler 172 after being discharged to the bottom of the may include an intermediate product such as glycerol acetates. At this time, a significant amount of chlorohydrins may be introduced into the line 11 together with the intermediate product.
- the reboiler 172 and the condenser 173 may be maintained at a temperature of 100 ⁇ 200 °C and 0 ⁇ 60 °C, respectively.
- the chlorination reaction of the multi-acid aliphatic hydrocarbon that is, the production reaction of the chlorohydrins may further occur.
- the stripping device 180 separates low boiling point materials such as chlorohydrins introduced with the high boiling point material through the line 11 using steam injected through the line 12.
- the low boiling point material recovered from the stripping device 180 flows into the line 13, and the high boiling point material is discharged to the outside through the line 14.
- the first distillation apparatus 170 and the stripping apparatus 180 are collectively referred to as a purification apparatus for chlorohydrins.
- chlorohydrin concentrates The substances introduced into lines 10 and 13 are collectively referred to as chlorohydrin concentrates.
- the substances introduced into line 5, line 10 and line 13 may be combined at one point to form a first composition of chlorohydrins.
- the first chlorohydrin composition may include 0 to 10 parts by weight of a polycarboxylic acid aliphatic hydrocarbon, 60 to 96 parts by weight of chlorohydrins, 0 to 20 parts by weight of a chlorinating agent, and 0 to 30 parts by weight of water.
- the method for producing chlorohydrins having the above structure can remove the reaction byproduct water without loss of the chlorinating agent and / or catalyst, thereby preventing a decrease in the reaction rate and increasing the selectivity of the chlorohydrins. have.
- the first chlorohydrin composition may be used to prepare epichlorohydrin.
- the first chlorohydrin composition may be diluted with water to form a second chlorohydrin composition before being used for the preparation of epichlorohydrin.
- the first chlorohydrin composition introduced into line 15 may be mixed with water introduced into line 16 to form a second chlorohydrin composition.
- the reason why the first chlorohydrin composition is diluted with water to form the second chlorohydrin composition before being used for the production of epichlorohydrin is that epichlorohydrin is used using a high concentration of chlorohydrin. This is because when the production of by-products increases, the selectivity of epichlorohydrin is lowered.
- the water may be added in a proportion of 100 to 500 parts by weight based on 100 parts by weight of the first chlorohydrin composition.
- the amount of water added is within the above range, the yield of by-products can be reduced with an appropriate amount of water to maximize the yield of epichlorohydrin.
- the second chlorohydrin composition may be used as a reaction raw material for epichlorohydrin preparation with an alkali agent.
- the second chlorohydrin composition may include 0 to 5 parts by weight of a multi-acid aliphatic hydrocarbon, 10 to 40 parts by weight of chlorohydrins, 0 to 5 parts by weight of chlorinating agent and 50 to 90 parts by weight of water.
- the component ratio of the second chlorohydrin composition is within the above range, the amount of by-products can be reduced to maximize the yield of epichlorohydrin.
- the second chlorohydrin composition may be brought into contact with the alkali agent (for example, an aqueous sodium hydroxide solution) injected into the line 17.
- the alkali agent for example, an aqueous sodium hydroxide solution
- Two reactions may occur as follows: As the contact time elapses after the 2 chlorohydrin composition is contacted with the alkali agent, the pH of the mixture of the second chlorohydrin composition and the alkali agent is gradually increased. At this time, when the pH is 7 or less, the catalyst in the second chlorohydrin composition may react with the alkali agent to form an alkali metal salt. The formed alkali metal salt may be precipitated and removed in the second distillation apparatus 200 described later.
- chlorohydrin eg, dichloropropanol
- the inline reactor 190 may be maintained at a temperature of 20 ⁇ 100 °C and a pressure of 1 to 2 atm.
- the temperature and pressure of the in-line reactor 190 are each within the above ranges, the reaction may proceed smoothly by input of suitable energy.
- the first chlorohydrin composition may include the catalyst described above, and accordingly, the second chlorohydrin composition may also include the catalyst. Therefore, in the in-line reactor 190, not only a reaction for forming epichlorohydrin as a main product but also a reaction for forming an alkali metal salt by contacting the alkali agent and the catalyst may occur.
- water is added to the first chlorohydrin composition (i.e., the composition of line 15) to form a second chlorohydrin composition, and an alkali agent is added to the formed second chlorohydrin composition.
- an alkali agent is added directly to the first chlorohydrin composition to remove the catalyst first, and then water is added to the first chlorohydrin composition from which the catalyst is removed to prepare a second chlorohydrin composition. You may. That is, in FIG. 1, the positions of the line 16 and the line 17 may be interchanged.
- the second distillation apparatus 200 may be operated by a distillation operation using the boiling point difference between the components of the epichlorohydrin and alkali metal salt containing material.
- the second distillation apparatus 200 may be maintained at a pressure below atmospheric pressure, for example, 10 ⁇ 760mmHg. If the pressure of the second distillation apparatus 200 is within the above range, epichlorohydrin can be separated with high efficiency.
- the second distillation apparatus 200 may include a reduced pressure distillation column (ie, separation tower 201) having a theoretical stage of 2 to 50. If the theoretical stage of the vacuum distillation column is within the above range, epichlorohydrin can be separated with high efficiency.
- the effluent of the in-line reactor 190 introduced into the second distillation apparatus 200 through the line 18 is separated into the gaseous substance and the liquid substance in the separation tower 201, and then the gaseous substance is condensed in the condenser 203.
- the liquid material is distilled from the reboiler 202 and separated back into the gaseous material and the liquid material, the gaseous material is recycled to the separation tower 201 and the liquid material is line 20 It is discharged to the outside through.
- the material discharged to the top of the separation tower 201 and then condensed in the condenser 203 and introduced into the line 19 includes epichlorohydrin and water, and is discharged to the bottom of the separation tower 201.
- the high boiling point material which is not vaporized in the reboiler 202 and then discharged to the outside through the line 20 may include an alkali metal salt.
- the reboiler 202 and the condenser 203 may be maintained at a temperature of 60 ⁇ 110 °C and 0 ⁇ 60 °C, respectively.
- the reaction of generating epichlorohydrin may further occur.
- Chlorohydrin and epichlorohydrin were prepared by reacting glycerol and hydrogen chloride gas in the presence of an acetic acid catalyst using the production process having the configuration as shown in FIG. 1.
- the specifications and operating conditions of each device used in the manufacturing process are shown in Table 1 below:
- the total flow rate of the material conveyed through each line of the manufacturing process, the components of the material and the flow rate of each of the components are measured and shown in Table 2 below.
- the flow rate of each component is calculated by measuring the total flow rate of the material transported through each line, analyzing the component ratio of the material taken from each line by gas chromatography, and then multiplying the total flow rate by the component ratio of the material. It was.
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Abstract
Description
구분 | 장치의 사양 | 운전조건 | |
제1 반응기 | CSTR | 120℃, 4기압 | |
혼합장치(2개) | 진공 이젝터 | - | |
감압장치(2개) | 감압밸브 | 46mmHg | |
물 제거 장치 | 감압증류 | 탈수탑 | 이론단수: 20단, 압력: 23mmHg |
리보일러 | 114℃, 46mmHg | ||
응축기 | 49℃, 23mmHg | ||
제2 반응기 | CSTR | 120℃, 4기압 | |
제1 증류장치(물 제거 장치 후단) | 감압증류 | 분리탑 | 이론단수: 20단,압력: 23mmHg |
리보일러 | 127℃, 46mmHg | ||
응축기 | 56℃, 23mmHg | ||
스트리핑 장치 | 스팀 스트리핑 | 스트리핑 장치 | 압력: 152mmHg |
스팀 | 143℃, 3기압 | ||
인라인 반응기 | 관형 반응기 | 70℃, 1기압 | |
제2 증류장치(인라인 반응기 후단) | 감압증류 | 분리탑 | 이론단수: 20단, 압력: 1기압 |
리보일러 | 104℃, 1기압 | ||
응축기 | 35℃, 1기압 |
라인 번호 | 총 유속(Kg/hr) | 이송 물질의 종류 | 유속(Kg/hr) |
1 | 315 | 글리세롤 | 300 |
아세트산 | 15 | ||
2 | 228 | HCl | 228 |
3 | 5713 | 모노클로로프로판디올 | 555 |
디클로로프로판올 | 3444 | ||
글리세롤아세테이트류 | 229 | ||
물 | 1083 | ||
글리세롤 | 78 | ||
HCl | 269 | ||
아세트산 | 55 | ||
4 | 543 | 모노클로로프로판디올 | 53 |
디클로로프로판올 | 327 | ||
글리세롤아세테이트류 | 22 | ||
물 | 103 | ||
글리세롤 | 7 | ||
HCl | 26 | ||
아세트산 | 5 | ||
5 | 250 | 디클로로프로판올 | 116 |
물 | 103 | ||
HCl | 26 | ||
아세트산 | 5 | ||
6 | 293 | 모노클로로프로판디올 | 53 |
디클로로프로판올 | 211 | ||
글리세롤아세테이트류 | 22 | ||
글리세롤 | 7 | ||
7 | 6382 | 모노클로로프로판디올 | 268 |
디클로로프로판올 | 5431 | ||
글리세롤아세테이트류 | 443 | ||
물 | 188 | ||
글리세롤 | 6 | ||
HCl | 46 | ||
8 | 21 | HCl | 21 |
9 | 314 | 모노클로로프로판디올 | 13 |
디클로로프로판올 | 268 | ||
글리세롤아세테이트류 | 22 | ||
물 | 9 | ||
글리세롤 | 0 | ||
HCl | 2 | ||
10 | 254 | 디클로로프로판올 | 243 |
물 | 9 | ||
HCl | 2 | ||
11 | 60 | 모노클로로프로판디올 | 13 |
디클로로프로판올 | 25 | ||
글리세롤아세테이트류 | 22 | ||
글리세롤 | 0 | ||
12 | 60 | 스팀 | 60 |
13 | 85 | 모노클로로프로판디올 | 2 |
디클로로프로판올 | 24 | ||
물 | 59 | ||
14 | 35 | 모노클로로프로판디올 | 11 |
디클로로프로판올 | 1 | ||
글리세롤아세테이트류 | 22 | ||
물 | 1 | ||
글리세롤 | 0 | ||
15 | 589 | 모노클로로프로판디올 | 2 |
디클로로프로판올 | 383 | ||
물 | 171 | ||
글리세롤 | 0 | ||
HCl | 28 | ||
아세트산 | 5 | ||
16 | 2000 | 물 | 2000 |
17 | 640 | NaOH | 160 |
물 | 480 | ||
18 | 3229 | 디클로로프로판올 | 8 |
에피클로로히드린 | 268 | ||
물 | 2718 | ||
글리세롤 | 3 | ||
아세트산나트륨 | 7 | ||
NaCl | 215 | ||
NaOH | 10 | ||
19 | 274 | 디클로로프로판올 | 0 |
에피클로로히드린 | 272 | ||
물 | 2 | ||
20 | 2955 | 물 | 2718 |
글리세롤 | 4 | ||
아세트산나트륨 | 7 | ||
NaCl | 219 | ||
NaOH | 7 |
시료 채취 지점 | ||
라인(4) | 라인(15) | |
글리세롤의 전환율(%) | 97.5 | 100 |
모노클로로프로판디올의 수율(%) | 14.6 | 0.6 |
디클로로프로판올의 수율(%) | 77.9 | 94.2 |
클로로히드린류의 수율*1(%) | 92.5 | 94.8 |
모노클로로프로판디올의 선택도(%) | 14.6 | 0.6 |
디클로로프로판올의 선택도(%) | 77.9 | 94.2 |
클로로히드린류의 선택도*2(%) | 92.5 | 94.8 |
Claims (31)
- 촉매의 존재하에 다수산기 지방족 탄화수소를 염소화제와 반응시켜 클로로히드린류를 제조하는 방법으로서,다수산기 지방족 탄화수소를 염소화제와 반응시키는 제1 반응단계;상기 제1 반응단계에서 배출된 반응 혼합물에서 부산물인 물을 제거하는 단계; 및상기 단계에서 물이 제거된 반응 혼합물의 적어도 한 구성성분을 상기 염소화제 및 추가 염소화제 중 적어도 하나와 반응시키는 제2 반응단계를 상기 순서로 포함하는 일련의 단위조작들의 조합을 적어도 하나 포함하고,상기 복수의 반응단계들 중 적어도 하나의 반응단계에서 배출된 반응 혼합물의 적어도 일부를 추가 염소화제와 혼합한 후 상기 반응 혼합물이 배출된 반응단계로 재순환시키는 단계를 추가로 포함하는 클로로히드린류의 제조방법.
- 다수산기 지방족 탄화수소 및 촉매를 50~200℃의 온도로 유지되는 제1 반응기로 주입하는 단계;상기 제1 반응기로부터 부산물인 물을 포함하는 제1 반응기 유출물을 배출시키는 단계;상기 제1 반응기 유출물 중의 적어도 일부를 염소화제와 혼합한 후, 이 혼합물을 상기 제1 반응기로 재순환시키는 단계;상기 제1 반응기 유출물 중 상기 제1 반응기로 재순환되지 않는 부분을 물 제거 장치로 주입하는 단계; 및상기 물이 제거된 제1 반응기 유출물을 80~200℃의 온도로 유지되는 제2 반응기로 주입하는 단계를 포함하는 클로로히드린류의 제조방법.
- 제2항에 있어서,상기 제2 반응기 유출물 중의 적어도 일부를 추가 염소화제와 혼합한 후, 이 혼합물을 상기 제2 반응기로 재순환시키는 단계를 추가로 포함하는 클로로히드린류의 제조방법.
- 제1항 또는 제2항에 있어서,상기 다수산기 지방족 탄화수소는, 각기 다른 탄소 원자에 결합된 2 이상의 수산기를 포함하는, 탄소수 2~20의 화합물인 클로로히드린류의 제조방법.
- 제4항에 있어서,상기 다수산기 지방족 탄화수소는 1,2-에탄디올, 1,2-프로판디올, 1,3-프로판디올, 3-클로로-1,2-프로판디올, 2-클로로-1,3-프로판디올, 글리세롤, 1,2,4-부탄트리올, 1,4-부탄디올 및 상기 각 화합물의 에스테르로 이루어진 군으로부터 선택된 적어도 1종의 화합물을 포함하는 클로로히드린류의 제조방법.
- 제1항 또는 제2항에 있어서,상기 제조방법에 의해 제조된 클로로히드린류는 각기 다른 탄소 원자와 결합된 적어도 하나의 수산기와 적어도 하나의 염소 원자를 포함하는 화합물인 클로로히드린류의 제조방법.
- 제6항에 있어서,상기 클로로히드린류는 3-클로로-1,2-프로판디올, 2-클로로-1,3-프로판디올, 1,3-디클로로프로판-2-올 및 2,3-디클로로 프로판-1-올로 이루어진 군으로부터 선택된 적어도 1종의 화합물을 포함하는 클로로히드린류의 제조방법.
- 제1항 또는 제2항에 있어서,상기 촉매는 유기산 촉매, 카르복실산계 촉매, 니트릴계 촉매 및 고체 촉매로 이루어진 군으로부터 선택된 적어도 하나를 포함하는 클로로히드린류의 제조방법.
- 제2항에 있어서,상기 제1 반응기에서는 중간생성물로서 상기 촉매와 상기 다수산기 지방족 탄화수소의 반응 생성물이 생성되며, 상기 중간생성물은 상기 다수산기 지방족 탄화수소의 염소화 반응에서 촉매작용을 하는 클로로히드린류의 제조방법.
- 제9항에 있어서,상기 다수산기 지방족 탄화수소는 글리세롤을 포함하고, 상기 촉매는 아세트산을 포함하며, 상기 중간생성물은 글리세롤아세테이트류를 포함하는 클로로히드린류의 제조방법.
- 제1항 또는 제3항에 있어서,상기 염소화제 및 추가 염소화제는 염화수소 가스 또는 염산 수용액을 포함하는 클로로히드린류의 제조방법.
- 제2항에 있어서,상기 물 제거 장치로 주입되는 상기 제1 반응기 유출물은, 상기 제1 반응기에서 다수산기 지방족 탄화수소의 전환율이 30~100%이고 클로로히드린류의 수율이 30~95%일때 배출된 것인 클로로히드린류의 제조방법.
- 제9항에 있어서,상기 물 제거 장치로 주입되는 상기 제1 반응기 유출물은, 다수산기 지방족 탄화수소, 클로로히드린류 및 상기 중간생성물을, 상기 다수산기 지방족 탄화수소 0~90중량부:상기 클로로히드린류 5~95중량부:상기 중간생성물 5~12중량부의 비율로 포함하는 클로로히드린류의 제조방법.
- 제13항에 있어서,상기 물 제거 장치로 주입되는 상기 제1 반응기 유출물은, 염소화제 및 물을, 상기 염소화제 10~25중량부:물 75~90중량부의 비율로 포함하는 클로로히드린류의 제조방법.
- 제2항에 있어서,상기 제1 반응기 유출물 중의 적어도 일부와 상기 추가 염소화제는 이젝터, 인라인 믹서, 초음파 믹서 또는 이들 중 2 이상을 포함하는 혼합장치내에서 혼합되는 클로로히드린류의 제조방법.
- 제2항에 있어서,상기 제1 반응기에서 반응기 내용물의 체류시간은 20분~1시간이고, 상기 제2 반응기에서 반응기 내용물의 체류시간은 1시간~3시간인 클로로히드린류의 제조방법.
- 제2항에 있어서,상기 물 제거 장치는 상기 제1 반응기 유출물의 구성성분들 간의 비등점 차이를 이용하는 증류 조작에 의해 작동되는 클로로히드린류의 제조방법.
- 제2항에 있어서,상기 제1 반응기 및 제2 반응기는 대기압 이상의 압력으로 유지되고, 상기 물 제거 장치는 대기압 이하의 압력으로 유지되는 클로로히드린류의 제조방법.
- 제18항에 있어서,상기 제1 반응기 및 제2 반응기는 1~20기압으로 유지되고, 상기 물 제거 장치는 10~760mmHg로 유지되는 클로로히드린류의 제조방법.
- 제19항에 있어서,상기 물 제거 장치는 이론단수가 2~50인 감압증류탑을 포함하는 클로로히드린류의 제조방법.
- 제18항에 있어서,상기 제1 반응기 유출물은 감압장치에서 감압된 후 상기 물 제거 장치로 주입되는 클로로히드린류의 제조방법.
- 제21항에 있어서,상기 감압장치는 감압밸브를 포함하는 클로로히드린류의 제조방법.
- 제2항에 있어서,상기 제1 반응기 및 제2 반응기는, 서로 독립적으로, 연속교반탱크식 반응기(continuous stirred tank reactor), 회분식 반응기(batch reactor), 반회분식 반응기(semi-batch reactor) 또는 관형 반응기(plug flow reactor)인 클로로히드린류의 제조방법.
- 제2항에 있어서,상기 물 제거 장치로 주입된 상기 제1 반응기 유출물은 물-풍부층 및 물-부족층으로 분리되는 클로로히드린류의 제조방법.
- 제24항에 있어서,상기 제2 반응기 유출물 중 상기 제2 반응기로 재순환되지 않는 부분으로부터 클로로히드린류를 정제하여 클로로히드린류 농축물을 얻는 단계, 및 상기 물-풍부층과 상기 클로로히드린류 농축물을 혼합하여 제1 클로로히드린류 조성물(first composition of chlorohydrins)을 얻는 단계를 추가로 포함하는 클로로히드린류의 제조방법.
- 제25항에 있어서,상기 제2 반응기 유출물 중 상기 제2 반응기로 재순환되지 않는 부분은, 다수산기 지방족 탄화수소 0~10중량부, 클로로히드린류 80~98중량부, 염소화제 0~10중량부 및 물 1~20중량부를 포함하는 클로로히드린류의 제조방법.
- 제26항에 있어서,상기 제1 클로로히드린류 조성물은, 다수산기 지방족 탄화수소 0~10중량부, 클로로히드린류 60~96중량부, 염소화제 0~20중량부 및 물 0~30중량부를 포함하는 클로로히드린류의 제조방법.
- 제25항에 있어서,상기 제1 클로로히드린류 조성물을 물로 희석하여 제2 클로로히드린류 조성물을 얻는 단계를 추가로 포함하는 클로로히드린류의 제조방법.
- 제28항에 있어서,상기 물은 상기 제1 클로로히드린류 조성물 100중량부에 대하여 100~500중량부의 비율로 첨가되는 클로로히드린류의 제조방법.
- 제29항에 따라 제조된 제2 클로로히드린류 조성물을 알칼리제와 20~100℃에서 접촉시키는 단계를 포함하고,상기 제2 클로로히드린류 조성물은 다수산기 지방족 탄화수소 0~5중량부, 클로로히드린류 10~40중량부, 염소화제 0~5중량부 및 물 50~90중량부를 포함하는 에피클로로히드린의 제조방법.
- 제30항에 있어서,상기 제2 클로로히드린류 조성물은 촉매를 추가로 포함하고, 상기 촉매는 상기 알칼리제와 반응하여 알칼리금속염을 형성하는 에피클로로히드린의 제조방법.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/805,738 US8975449B2 (en) | 2010-06-30 | 2011-06-08 | Method for preparing chlorohydrins and method for preparing epichlorohydrin using chlorohydrins prepared thereby |
EP11801054.5A EP2589583B1 (en) | 2010-06-30 | 2011-06-08 | Method for preparing chlorohydrins and method for preparing epichlorohydrin using chlorohydrins prepared thereby |
JP2013518225A JP5837583B2 (ja) | 2010-06-30 | 2011-06-08 | クロロヒドリン類の製造方法及びその方法によって製造されたクロロヒドリン類を使用するエピクロロヒドリンの製造方法 |
CN2011800320930A CN103038201A (zh) | 2010-06-30 | 2011-06-08 | 用于制备氯醇的方法以及使用由所述方法制备的氯醇制备表氯醇的方法 |
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KR1020100063156A KR101705205B1 (ko) | 2010-06-30 | 2010-06-30 | 클로로히드린류의 제조방법 및 그 방법에 의해 제조된 클로로히드린류를 사용하는 에피클로로히드린의 제조방법 |
KR10-2010-0063156 | 2010-06-30 |
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WO2012002647A2 true WO2012002647A2 (ko) | 2012-01-05 |
WO2012002647A3 WO2012002647A3 (ko) | 2012-04-19 |
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PCT/KR2011/004167 WO2012002647A2 (ko) | 2010-06-30 | 2011-06-08 | 클로로히드린류의 제조방법 및 그 방법에 의해 제조된 클로로히드린류를 사용하는 에피클로로히드린의 제조방법 |
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US (1) | US8975449B2 (ko) |
EP (1) | EP2589583B1 (ko) |
JP (1) | JP5837583B2 (ko) |
KR (1) | KR101705205B1 (ko) |
CN (1) | CN103038201A (ko) |
WO (1) | WO2012002647A2 (ko) |
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KR101705206B1 (ko) * | 2010-06-30 | 2017-02-09 | 롯데정밀화학 주식회사 | 클로로히드린류의 제조방법 및 그 방법에 의해 제조된 클로로히드린류를 사용하는 에피클로로히드린의 제조방법 |
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CZ294890B6 (cs) * | 2003-09-01 | 2005-04-13 | Spolek Pro Chemickou A Hutní Výrobu,A.S. | Způsob přípravy dichlorpropanolů z glycerinu |
EP1770081A1 (en) * | 2003-11-20 | 2007-04-04 | SOLVAY (Société Anonyme) | Process for producing dichloropropanol from glycerol , the glycerol coming eventualy from the conversion of animal fats in the manufacture of biodiesel |
KR100917808B1 (ko) * | 2003-11-20 | 2009-09-18 | 솔베이(소시에떼아노님) | 유기 화합물의 제조 방법 |
EP1771403B1 (en) * | 2004-07-21 | 2010-01-06 | Dow Global Technologies Inc. | Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin |
EP1762556A1 (en) * | 2005-05-20 | 2007-03-14 | SOLVAY (Société Anonyme) | Process for producing dichloropropanol from glycerol |
KR20080037618A (ko) * | 2005-05-20 | 2008-04-30 | 솔베이(소시에떼아노님) | 폴리히드록실화 지방족 탄화수소 및 염소화제 간의 반응에의한 클로로히드린 제조 방법 |
TWI332942B (en) * | 2005-05-20 | 2010-11-11 | Solvay | Process for producing a chlorohydrin |
FR2913684B1 (fr) * | 2007-03-14 | 2012-09-14 | Solvay | Procede de fabrication de dichloropropanol |
KR101410019B1 (ko) * | 2007-09-28 | 2014-06-26 | 한화케미칼 주식회사 | 다가알코올과 염화수소의 반응에 의한 클로로히드린화합물의 제조방법 |
EP2219779B1 (en) | 2007-11-19 | 2012-05-30 | Conser S.P.A. | Conversion of glycerine to dichlorohydrins and epichlorohydrin |
KR101705207B1 (ko) * | 2010-06-30 | 2017-02-09 | 롯데정밀화학 주식회사 | 클로로히드린류의 제조방법 및 그 방법에 의해 제조된 클로로히드린류를 사용하는 에피클로로히드린의 제조방법 |
KR101705206B1 (ko) * | 2010-06-30 | 2017-02-09 | 롯데정밀화학 주식회사 | 클로로히드린류의 제조방법 및 그 방법에 의해 제조된 클로로히드린류를 사용하는 에피클로로히드린의 제조방법 |
-
2010
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- 2011-06-08 JP JP2013518225A patent/JP5837583B2/ja not_active Expired - Fee Related
- 2011-06-08 WO PCT/KR2011/004167 patent/WO2012002647A2/ko active Application Filing
- 2011-06-08 EP EP11801054.5A patent/EP2589583B1/en active Active
- 2011-06-08 CN CN2011800320930A patent/CN103038201A/zh active Pending
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Also Published As
Publication number | Publication date |
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US20130090485A1 (en) | 2013-04-11 |
KR20120002333A (ko) | 2012-01-05 |
JP2013535416A (ja) | 2013-09-12 |
EP2589583A4 (en) | 2015-08-05 |
KR101705205B1 (ko) | 2017-02-09 |
CN103038201A (zh) | 2013-04-10 |
JP5837583B2 (ja) | 2015-12-24 |
EP2589583B1 (en) | 2020-07-08 |
US8975449B2 (en) | 2015-03-10 |
EP2589583A2 (en) | 2013-05-08 |
WO2012002647A3 (ko) | 2012-04-19 |
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