WO2024253046A1 - エチル基を有するカーボネートの製造方法及びエチル基を有するカーボネートの製造装置 - Google Patents

エチル基を有するカーボネートの製造方法及びエチル基を有するカーボネートの製造装置 Download PDF

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WO2024253046A1
WO2024253046A1 PCT/JP2024/020116 JP2024020116W WO2024253046A1 WO 2024253046 A1 WO2024253046 A1 WO 2024253046A1 JP 2024020116 W JP2024020116 W JP 2024020116W WO 2024253046 A1 WO2024253046 A1 WO 2024253046A1
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carbonate
ethyl group
producing
reaction composition
solvent
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French (fr)
Japanese (ja)
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美弥子 榎本
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Priority to JP2025526094A priority Critical patent/JPWO2024253046A1/ja
Priority to EP24819276.7A priority patent/EP4725935A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/08—Purification; Separation; Stabilisation

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  • the present invention relates to a method for producing carbonates having ethyl groups and an apparatus for producing carbonates having ethyl groups.
  • Carbonates with an ethyl group such as ethyl methyl carbonate (EMC) and diethyl carbonate (DEC), are used as organic solvents for battery electrolytes. It is known that these carbonate compounds are obtained by the transesterification reaction of dimethyl carbonate (DMC) and ethanol (EtOH).
  • DMC dimethyl carbonate
  • EtOH ethanol
  • an alkali metal compound such as an alkali metal alkoxide compound, is used as a catalyst because of its excellent activity (for example, Patent Document 1 and Patent Document 2).
  • an alkali metal compound is used as a catalyst for the transesterification reaction.
  • the catalyst used is sodium methoxide or sodium hydroxide (hereinafter also referred to as "NaOH").
  • alkali metal compounds have low solubility in organic solvents, such as DMC, EMC, and DEC, and precipitation of alkali metal compounds can cause process problems.
  • Patent Document 1 proposes a method of supplying an alkali metal compound dissolved in dimethyl sulfoxide, but the solubility of alkali metal compounds in dimethyl sulfoxide is low at less than 1% by mass, and impurities are produced when the raw material alkali metal compound is mixed with dimethyl sulfoxide and heated.
  • Patent Document 2 discloses a method of removing unwanted materials by installing a filtration device after the reaction process, but the filtration device has problems such as the need for cleaning and maintenance work, and the risk of clogging the piping leading to the filtration device. Furthermore, the solid waste derived from the catalyst is highly alkaline and water-inhibiting, making it highly dangerous and difficult to dispose of.
  • the objective of the present invention is to provide a method and an apparatus for producing carbonate having an ethyl group that suppresses the formation of precipitates during the distillation process and enables the distillation process to be operated continuously for a long period of time.
  • the inventors have found that the above-mentioned problems can be solved by ensuring that the concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition immediately before being introduced into the distillation column in the distillation process is equal to or less than a predetermined value.
  • the present invention includes the following embodiments.
  • a method for producing a carbonate having an ethyl group comprising the steps of: A reaction step of transesterifying dimethyl carbonate and ethanol in a reactor in the presence of a catalyst containing an alkali metal compound to obtain a reaction composition; a solvent addition step of adding a solvent to the reaction composition; and distilling the reaction composition in a distillation column.
  • a method for producing carbonates having an ethyl group comprising the steps of: A reaction step of transesterifying dimethyl carbonate and ethanol in a reactor in the presence of a catalyst containing an alkali metal compound to obtain a reaction composition; a solvent addition step of adding a solvent to the reaction composition; and distilling the reaction composition in a distillation column.
  • a method for producing a carbonate having an ethyl group comprising the steps of: A reaction step of transesterifying dimethyl carbonate and ethanol in a reactor in the presence of a catalyst containing an alkali metal compound to obtain a reaction composition; and distilling the reaction composition in a distillation column.
  • concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition immediately before being introduced into the distillation column in the distillation step is 50 ppm by mass or less.
  • a solvent addition step is included in which a solvent is added to the reaction composition;
  • the solvent addition step dissolves insoluble matter in the reaction composition.
  • the method includes an acid addition step of adding an acidic substance having a pKa of 6.0 or less to the reaction composition before the solvent addition step; A method for producing a carbonate having an ethyl group according to any one of ⁇ 1> and ⁇ 3> to ⁇ 4>.
  • the acidic substance is at least one selected from the group consisting of carboxylic acids and sulfonic acids.
  • the acidic substance is at least one selected from the group consisting of propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and oleic acid.
  • the solvent has a solubility of 10 mass% or more at 30°C for the alkali metal compound and the reaction product of the alkali metal compound and the acidic compound;
  • the boiling point of the solvent is higher than the boiling point of diethyl carbonate under normal pressure.
  • ⁇ 1> and ⁇ 3> to ⁇ 8> a method for producing a carbonate having an ethyl group.
  • the solvent comprises a compound having at least one hydroxyl group.
  • a method for producing a carbonate having an ethyl group according to any one of ⁇ 1> and ⁇ 3> to ⁇ 9>.
  • the solvent contains at least one selected from the group consisting of monoethylene glycol, diethylene glycol, triethylene glycol, 1-hexanol, 2-hexanol, 1-heptanol, and 2-heptanol.
  • ⁇ 1> and ⁇ 3> to ⁇ 10> a method for producing a carbonate having an ethyl group.
  • the amount of the solvent added in the solvent addition step is 0.1 parts by mass to 20 parts by mass relative to 100 parts by mass of the reaction composition; ⁇ 1> and ⁇ 3> to ⁇ 10>, a method for producing a carbonate having an ethyl group.
  • the alkali metal compound is a sodium-containing compound.
  • the concentration of the alkali metal compound is 1 ppm by mass to 30,000 ppm by mass based on the total amount of the reaction composition; ⁇ 14> A method for producing a carbonate having an ethyl group according to any one of ⁇ 1> to ⁇ 13>.
  • the reactor is a stirred reactor or a distillation column; ⁇ 15> A method for producing a carbonate having an ethyl group according to any one of ⁇ 1> to ⁇ 14>.
  • the distillation step is a step of separating a fraction containing 99.9% by mass or more of a carbonate having an ethyl group.
  • ⁇ 16> A method for producing a carbonate having an ethyl group according to any one of ⁇ 1> to ⁇ 15>.
  • the carbonate having an ethyl group is ethyl methyl carbonate or dimethyl carbonate.
  • ⁇ 17> A method for producing a carbonate having an ethyl group according to any one of ⁇ 1> to ⁇ 16>.
  • An apparatus for producing a carbonate having an ethyl group comprising: A reaction apparatus in which dimethyl carbonate and ethanol are subjected to a transesterification reaction in a reactor in the presence of a catalyst containing an alkali metal compound to obtain a reaction composition; a solvent adding section for adding a solvent to the reaction composition; a distillation apparatus for distilling the reaction composition; An apparatus for producing a carbonate having an ethyl group, comprising:
  • the present invention makes it possible to provide a method and an apparatus for producing carbonate having an ethyl group that suppresses the formation of precipitates during the distillation process and enables the distillation process to be operated continuously for a long period of time.
  • FIG. 1 is a block diagram of an apparatus for producing a carbonate having an ethyl group according to this embodiment.
  • FIG. 2 is a schematic diagram of an apparatus A for producing a carbonate having an ethyl group according to this embodiment.
  • FIG. 3 is a schematic diagram of an apparatus B for producing a carbonate having an ethyl group according to this embodiment.
  • FIG. 4 is a schematic diagram of an apparatus C for producing a carbonate having an ethyl group according to this embodiment.
  • the present embodiment an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail with reference to the drawings as necessary, but the present invention is not limited to this, and various modifications are possible without departing from the gist of the present invention.
  • the positional relationships such as up, down, left, and right in the embodiment shown in the drawings are based on the positional relationships shown in the drawings.
  • the dimensional ratios in the drawings are not limited to those shown in the drawings.
  • the method for producing a carbonate having an ethyl group includes the steps of: A reaction step of transesterifying dimethyl carbonate and ethanol in a reactor in the presence of a catalyst containing an alkali metal compound to obtain a reaction composition; a solvent addition step of adding a solvent to the reaction composition; and distilling the reaction composition in a distillation column.
  • a reaction step of transesterifying dimethyl carbonate and ethanol in a reactor in the presence of a catalyst containing an alkali metal compound to obtain a reaction composition a solvent addition step of adding a solvent to the reaction composition
  • distilling the reaction composition in a distillation column According to the above-mentioned configuration, it is possible to provide a method for producing a carbonate having an ethyl group, which can suppress the formation of precipitates in the distillation step and enable the distillation step to be operated continuously for a long period of time.
  • the method for producing a carbonate having an ethyl group includes the steps of: A reaction step of transesterifying dimethyl carbonate and ethanol in a reactor in the presence of a catalyst containing an alkali metal compound to obtain a reaction composition; and distilling the reaction composition in a distillation column.
  • the reaction composition has an insoluble matter concentration of 50 ppm by mass or less immediately before being introduced into a distillation column in the distillation step.
  • the distillation process can be continuously operated for a long period of time by setting the concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition immediately before being introduced into the distillation column to 50 ppm by mass or less.
  • Catalysts containing alkali metal compounds have low solubility in organic solvents such as dimethyl carbonate, so insoluble matter is likely to occur in the reaction composition.
  • the reaction composition is distilled in a state in which it contains a large amount of insoluble matter, precipitates occur in the distillation column, making it difficult to operate for a long period of time.
  • the concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition is preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, even more preferably 5 ppm by mass or less, and still more preferably 1 ppm by mass or less.
  • concentration of insoluble matter in the reaction composition is measured by the method described in the Examples.
  • a solvent in which the alkali metal compound is highly soluble can be added in the reaction step described below, thereby dissolving the alkali metal compound in the reaction composition and keeping the insoluble matter concentration low.
  • a step of adding a solvent described below can be mentioned.
  • an effective method for using the solvent is to add an acidic substance in the acid addition step described below, and dissolve the alkali metal compound in the reaction composition in a deactivated state.
  • the method for producing a carbonate having an ethyl group according to this embodiment may include a raw material supplying step of supplying a raw material containing dimethyl carbonate and ethanol to the reactor before the reaction step.
  • the method for producing a carbonate having an ethyl group according to this embodiment may also include a reaction composition withdrawing step of withdrawing the reaction composition from the reactor after the reaction step.
  • the method for producing carbonate having an ethyl group may be a continuous reaction by including a raw material supplying step of continuously supplying raw materials containing dimethyl carbonate and ethanol to the reactor, and a reaction composition withdrawing step of continuously withdrawing the reaction composition from the reactor.
  • a continuous reaction no blockage occurs in the reactor, and a high conversion rate of the raw materials can be achieved.
  • alkali metal compounds used as catalysts include sodium hydroxide, potassium hydroxide, and alkali metal alkoxides.
  • alkali metal alkoxides include lithium methoxide, lithium ethoxide, sodium methoxide, sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide.
  • alkali metal compounds are highly active, and therefore economical operation at low catalyst concentrations is possible. Therefore, sodium-containing compounds are preferred, and sodium methoxide or sodium ethoxide are more preferred, and sodium methoxide is even more preferred.
  • the concentration of the alkali metal compound is preferably 1 ppm by mass to 30,000 ppm by mass, more preferably 10 ppm by mass to 1,000 ppm by mass, and even more preferably 25 ppm by mass to 500 ppm by mass, relative to the total amount of the reaction composition.
  • reaction step dimethyl carbonate and ethanol are transesterified in a reactor in the presence of a catalyst containing an alkali metal compound to obtain a reaction composition containing a carbonate having an ethyl group. That is, the methoxy group of dimethyl carbonate is transesterified with ethanol to obtain a carbonate having an ethyl group.
  • Examples of carbonates having an ethyl group include ethyl methyl carbonate and diethyl carbonate.
  • the reaction temperature in the reaction step is preferably 40°C to 150°C, more preferably 50°C to 130°C, and even more preferably 60°C to 120°C.
  • the reaction temperature is increased to increase the reaction rate, or the residence time in the reactor is increased to extend the reaction time.
  • a high raw material conversion rate can be achieved by lowering the reaction temperature and reducing the residence time in the reactor in order to minimize the effect of reduced catalyst activity.
  • the reaction composition is withdrawn from the reactor.
  • the withdrawal of the reaction composition may be carried out continuously. It is preferable that the withdrawal rate of the reaction composition is set so as to achieve the above-mentioned residence time in the reactor.
  • the method for producing carbonate having an ethyl group according to the present embodiment may include an acid addition step of adding an acidic substance having a pKa of 6.0 or less to the reaction composition.
  • an acid addition step By providing the acid addition step, the alkali metal compound remaining in the reaction composition can be deactivated.
  • the acid addition step before the solvent addition step described below By performing the acid addition step before the solvent addition step described below, the production of by-products is suppressed even if a compound having a hydroxyl group that can cause transesterification is used as a solvent.
  • the pKa of the acidic substance is preferably 5.8 or less, more preferably 5.6 or less, and even more preferably 5.4 or less. There is no particular upper limit to the pKa of the acidic substance, but it is preferably 0.1 or more, more preferably 1.0 or more, and even more preferably 2.0 or more.
  • Examples of acidic substances include organic acids.
  • Examples of organic acids include carboxylic acids and sulfonic acids.
  • Examples of carboxylic acids include carboxylic acids having 2 to 30 carbon atoms, more specifically, acetic acid, dichloroacetic acid, propionic acid, butanoic acid, hexanoic acid, and oleic acid.
  • At least one selected from the group consisting of carboxylic acids is preferable, and at least one selected from the group consisting of propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and oleic acid is more preferable.
  • the amount of acidic substance added in the acid addition step is preferably 2.0 to 15.0, more preferably 2.5 to 12.0, and even more preferably 3.0 to 10.0, in terms of the molar ratio of acidic substance/catalyst.
  • the acidic substance may be added in a stirring tank, or the reaction composition and the acidic substance may be combined and then mixed using a static mixer.
  • the solvent to be added preferably has a solubility of 10% by mass or more for the alkali metal compound and the reaction product of the alkali metal compound and the acidic compound at 30° C.
  • a solubility of 10% by mass or more for the alkali metal compound and the reaction product of the alkali metal compound and the acidic compound at 30° C.
  • the solubility of the solvent in the alkali metal compound and the reaction product of the alkali metal compound and the acidic compound is more preferably 10% by mass or more, and even more preferably 15% by mass or more, at 30° C.
  • the solubility may be, for example, 50% by mass or less at 30° C.
  • the solvent (a) has a boiling point higher than the boiling point of diethyl carbonate under normal pressure, or (b) has an azeotropic point with diethyl carbonate under normal pressure.
  • the boiling point of the solvent under normal pressure is preferably 136°C or higher, more preferably 140°C to 400°C, and even more preferably 150°C to 300°C.
  • the solvent has a boiling point higher than that of diethyl carbonate under normal pressure and does not form an azeotrope with diethyl carbonate. It is more preferable that the solvent has a boiling point 10°C or higher than that of diethyl carbonate, even more preferable that the solvent has a boiling point 20°C or higher than that of diethyl carbonate, and even more preferable that the solvent has a boiling point 30°C or higher. In addition, when the solvent has the above boiling point, it is preferable that the solvent does not form an azeotrope with diethyl carbonate under normal pressure.
  • the added solvent can be left in the distillation column until the end of the distillation process and can be distilled from the bottom of the column after the distillation process, which is advantageous in that it is not necessary to separate the target compound, carbonate having an ethyl group, distilled from the top of the column from the solvent.
  • the solvent has a boiling point lower than that of diethyl carbonate under normal pressure, and that the composition of diethyl carbonate and solvent has an azeotropic point at a high diethyl carbonate concentration and a low solvent concentration, and it is preferable that the solvent does not have an azeotropic point with dimethyl carbonate or ethyl methyl carbonate, or, even if it has an azeotropic point, it has an azeotropic point at a high carbonate concentration and a low solvent concentration.
  • the above-mentioned high diethyl carbonate concentration means 50 mass% or more.
  • the above-mentioned high diethyl carbonate concentration is preferably 60 mass% or more, more preferably 70 mass% or more.
  • the above-mentioned low solvent concentration means 50 mass% or less.
  • the above-mentioned low solvent concentration is preferably 40 mass% or less, more preferably 30 mass% or less. It is preferable to select a solvent that has an azeotropic point with diethyl carbonate in the above concentration range.
  • the solvent added in the solvent addition step preferably contains a compound having at least one hydroxyl group, and more preferably contains a compound having at least two hydroxyl groups.
  • the solvent include monoethylene glycol, diethylene glycol, triethylene glycol, 1-hexanol, 2-hexanol, 1-heptanol, 2-heptanol, and 1-butanol. Among these, monoethylene glycol, diethylene glycol, and triethylene glycol are preferred.
  • the content of the compound having at least one hydroxyl group is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass, based on the total amount of the solvent.
  • the amount of solvent added in the solvent addition step is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1.0 to 10 parts by mass, per 100 parts by mass of the reaction composition, from the viewpoint of more significantly suppressing the formation of precipitates in the distillation step and from the viewpoint of reducing the operating load of the distillation column.
  • the solvent may be added in a stirring tank, or the reaction composition and the solvent may be combined and then mixed using a static mixer.
  • the reaction composition is distilled in a distillation column.
  • the amount of precipitates in the reaction composition immediately before being introduced into the distillation column in the distillation step is preferably 50 mg/L or less, more preferably 30 mg/L or less, and even more preferably 10 mg/L or less. By setting the amount of precipitates within this range, the formation of precipitates in the distillation step can be more significantly suppressed.
  • the carbonate having an ethyl group which is the target compound in the manufacturing method according to this embodiment, is ethyl methyl carbonate or dimethyl carbonate, and is preferably ethyl methyl carbonate.
  • These carbonates having an ethyl group are used, for example, as electrolytes for lithium ion secondary batteries.
  • the manufacturing method according to this embodiment makes it possible to provide a method for manufacturing carbonate having an ethyl group that suppresses the formation of precipitates during the distillation process and enables the distillation process to be operated continuously for a long period of time.
  • FIG. 1 is a block diagram of an apparatus for producing carbonate having an ethyl group according to the present embodiment.
  • the apparatus for producing carbonate having an ethyl group according to the present embodiment includes a reaction apparatus 1, an acid addition section 2, a solvent addition section 3, and a distillation apparatus 4.
  • the production apparatus supplies raw materials to the reaction apparatus 1 and sequentially processes the raw materials, thereby carrying out a reaction step, an acid addition step, a solvent addition step, and a distillation step in this order.
  • FIG. 2 is a schematic diagram of the production apparatus A for producing carbonate having an ethyl group according to this embodiment.
  • the production apparatus A for producing carbonate having an ethyl group has a stirred tank reactor 1a, an acidic substance supply line 21a, a static mixer 2a, a solvent supply line 31a, a stirred mixing tank 3a, and a distillation column 4a.
  • the stirred tank reactor 1a is provided with a raw material supply section 11, through which raw materials are supplied.
  • the raw materials are the above-mentioned raw materials, and contain dimethyl carbonate and ethanol, and may contain a catalyst containing an alkali metal compound.
  • the stirred tank reactor 1a has a stirring device 12. At the bottom of the stirred tank reactor 1a, an extraction section 13 is provided, from which the reaction composition is extracted.
  • the reaction composition extracted from the extraction section 13 is combined with the acidic substance supplied from the acidic substance supply line 21a, and the alkali metal compounds in the reaction composition are deactivated. After being combined with the acidic substance, the reaction composition is introduced into the static mixer 2a, where the reaction composition is mixed.
  • the reaction composition is then introduced into the stirring and mixing tank 3a and mixed with the solvent supplied from the solvent supply line 31a, and the precipitate in the reaction composition is dissolved by the solvent.
  • the reaction composition is further sent to the distillation column 4a, where a carbonate having an ethyl group is obtained by distillation purification.
  • the solvent added from the solvent supply line 31a has a higher boiling point than diethyl carbonate under normal pressure and does not have an azeotropic composition
  • the distillation column 4a can be operated at normal pressure and the solvent can be separated from the bottom of the column, which is preferable in terms of both the amount of heat and the recovery rate of the carbonate having an ethyl group.
  • the raw material supply process, reaction process, extraction process, acid addition process, solvent addition process, and distillation process are carried out in this order.
  • FIG. 3 is a schematic diagram of the manufacturing apparatus B for producing carbonate having an ethyl group according to this embodiment.
  • the manufacturing apparatus B for producing carbonate having an ethyl group has a stirred tank reactor 1a, an acidic substance supply line 21b, a stirred mixing tank 2b, a solvent supply line 31b, a static mixer 3b, and a distillation column 4a. Note that parts common to the manufacturing apparatus A are given the same reference numerals and will not be described.
  • the reaction composition extracted from the extraction section 13 of the stirred tank reactor 1a is introduced into the stirred mixing tank 2b and mixed with the acid substance supplied from the acid substance supply line 21b, thereby deactivating the alkali metal compound in the reaction composition.
  • reaction composition is combined with the shared solvent from the solvent supply line 31b, and the reaction composition is introduced into the static mixer 3b, where the reaction composition is mixed and the precipitate in the reaction composition is dissolved by the solvent.
  • the manufacturing apparatus B may be equipped with a cushion tank 5. By arranging the cushion tank 5 downstream of the static mixer 3b, the amount of the reaction composition sent to the distillation column 4a can be adjusted.
  • reaction composition is then sent to distillation column 4a, where it is purified by distillation to obtain carbonates having ethyl groups.
  • the raw material supply process, reaction process, extraction process, acid addition process, solvent addition process, and distillation process are carried out in this order.
  • FIG. 4 is a schematic diagram of the manufacturing apparatus C for producing carbonate having an ethyl group according to this embodiment.
  • the manufacturing apparatus C for producing carbonate having an ethyl group has a reactive distillation column 1b, an acidic substance supply line 21a, a static mixer 2a, a solvent supply line 31b, a static mixer 3b, and a distillation column 4a. Note that parts common to the manufacturing apparatus A or B are given the same reference numerals and will not be described.
  • a catalyst solution is introduced from the top of reactive distillation column 1b.
  • the catalyst solution is prepared by dissolving the above-mentioned catalyst in a solvent such as alcohol.
  • Dimethyl carbonate and ethanol are introduced from the middle of reactive distillation column 1b. This allows the dimethyl carbonate and ethanol to undergo an ester exchange reaction in reactive distillation column 1b, and the reaction composition is extracted from the bottom of the column.
  • the reaction process, the acid addition process, the solvent addition process, and the distillation process are carried out in this order.
  • Example 1 Using the production apparatus A for producing a carbonate having an ethyl group having the configuration shown in FIG. 2, a carbonate having an ethyl group was produced as follows. DMC was supplied to a stirred tank reactor 1a having a capacity of 0.1 m3 at a flow rate of 75 kg/h, EtOH was supplied to a stirred tank reactor 1a having a flow rate of 25 kg/h, and a methanol solution of 28% by mass of sodium methoxide was supplied to the stirred tank reactor 1a having a flow rate of 71 g/h, and reacted under conditions of 70 ° C. and 103 kPaG.
  • reaction product 100 kg/h of the reaction product was extracted from the stirred tank reactor 1a to obtain a reaction composition containing a carbonate having an ethyl group.
  • the amounts of various components in the reaction composition were MeOH 13 kg/h, EtOH 7 kg/h, DMC 43 kg/h, EMC 33 kg/h, and DEC 4 kg/h.
  • concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition extracted from the stirred tank reactor 1a was 112 mass ppm.
  • Butanoic acid (pKa 4.8) was added to the reaction composition obtained by the reaction at 162 g/h, and the mixture was passed through a static mixer 2a and fed to the stirring and mixing tank 3a.
  • Example 2 Using the production apparatus B for producing a carbonate having an ethyl group having the configuration shown in FIG. 3, a carbonate having an ethyl group was produced as follows. 300 kg/h of DMC, 300 kg/h of EtOH, and a 28% by mass methanol solution of sodium methoxide were supplied to a stirred tank reactor 1a having a capacity of 3 m3 at a flow rate of 0.5 kg/h, and reacted under conditions of 50 ° C. and 103 kPaG, and 601 kg/h of the reaction composition was extracted from the stirred tank reactor 1a to obtain a reaction composition containing a carbonate having an ethyl group.
  • the amounts of various components in the reaction composition were MeOH 99 kg/h, EtOH 157 kg/h, DMC 82 kg/h, EMC 186 kg/h, and DEC 77 kg/h.
  • the concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition extracted from the stirred tank reactor 1a was 388 mass ppm.
  • TOG triethylene glycol
  • the reaction composition was then supplied from the cushion tank 5 to the distillation column 4a and distilled.
  • the concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition before being introduced into the distillation column 4a was 0.4 mass ppm. In this operation, no precipitate was present in the liquid extracted from the cushion tank 5 or in the column bottom liquid after distillation.
  • Example 3 Using the production apparatus C for carbonate having an ethyl group having the configuration shown in FIG. 4, carbonate having an ethyl group was produced as follows. DMC 97 kg / h, EtOH 13 kg / h, and a methanol solution of 28 mass% sodium methoxide were supplied to a reactive distillation column 1b having a column diameter of 500 mm and a column height of 60 plates at a flow rate of 0.16 kg / h. The column bottom withdrawal flow rate was 32 kg / h, and the column was operated at a reflux ratio of 1.0 and a column top pressure of 103 kPaA to obtain a reaction composition containing a carbonate having an ethyl group.
  • the amounts of various components in the reaction composition were DMC 2 kg / h, EMC 28 kg / h, and DEC 2 kg / h.
  • the concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition extracted from the distillation column type reactor was 513 mass ppm.
  • the concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition before being introduced into the distillation tower was 1.2 mass ppm. In this operation, no precipitate was present in the liquid extracted from the cushion tank 5 or in the bottom liquid after distillation.
  • the recovery rate of DEC in the distillation tower was 99% or more.
  • Example 4 Using the production apparatus A for producing a carbonate having an ethyl group having the configuration shown in FIG. 2, a carbonate having an ethyl group was produced as follows. 75 kg of DMC, 25 kg of EtOH, and 10 g of a 28% by mass methanol solution of sodium methoxide were fed to a stirred tank reactor 1a having a volume of 0.23 m3 , and after stirring for 5 hours under conditions of 70°C and 103 kPaG, the reaction composition was extracted from the bottom of the stirred tank reactor 1a at a flow rate of 100 kg/h to obtain a reaction composition containing a carbonate having an ethyl group.
  • the amounts of various components in the reaction composition were MeOH 13 kg/h, EtOH 6 kg/h, DMC 44 kg/h, EMC 33 kg/h, and DEC 4 kg/h.
  • Butanoic acid 41 g/h was added to the reaction composition obtained by the reaction and passed through a static mixer 2a, and then the reaction composition and monoethylene glycol 7.3 kg/h were fed to the stirring and mixing tank 3a, and then 107.4 kg/h of the reaction composition was extracted from the stirring tank and fed to the distillation tower 4a for distillation.
  • the concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition before being introduced into the distillation tower 4a was 0.1 mass ppm or less, and no precipitate was confirmed. In this operation, the concentration of insoluble matter in the liquid extracted from the stirring and mixing tank 3a and in the bottom liquid after distillation was 0 mass ppm.
  • Example 5 Using the production apparatus B for producing a carbonate having an ethyl group having the configuration shown in FIG. 3, a carbonate having an ethyl group was produced as follows. 300 kg/h of DMC, 300 kg/h of EtOH, and a 28% by mass methanol solution of sodium methoxide were supplied to a stirred tank reactor 1a having a capacity of 3 m3 at a flow rate of 0.5 kg/h, and reacted under conditions of 50 ° C. and 103 kPaG, and 601 kg/h of the reaction composition was extracted from the stirred tank reactor 1a to obtain a reaction composition containing a carbonate having an ethyl group.
  • the amounts of various components in the reaction composition were MeOH 99 kg/h, EtOH 157 kg/h, DMC 82 kg/h, EMC 186 kg/h, and DEC 77 kg/h.
  • the concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition extracted from the stirred tank reactor 1a was 388 mass ppm.
  • the concentration of insoluble matter having a size of 10 ⁇ m or more in the reaction composition before being introduced into the distillation column 4a was less than 0.1 mass ppm. In this operation, no precipitate was present in the liquid extracted from the cushion tank 5 or in the bottom liquid after distillation.
  • the recovery rate of DEC was 40%.
  • Carbonate having an ethyl group was produced as described below using a production apparatus A for producing a carbonate having an ethyl group having the configuration shown in Figure 2, except that the acidic substance supply line 21a, the static mixer 2a, the solvent supply line 31a, and the stirring and mixing tank 3a were removed.
  • DMC was supplied to a 0.1 m3 stirred tank reactor 1a at a flow rate of 75 kg/h, EtOH at 25 kg/h, and a 28% by mass sodium methoxide solution at a flow rate of 71 g/h, and reacted at 70° C. and 103 kPaG.
  • the method for producing carbonates having ethyl groups according to the present invention makes it possible to efficiently produce substances such as ethyl methyl carbonate and diethyl carbonate that are used in electrolytes for lithium secondary batteries.
  • Reference Signs List 1 Reactor 1a: Stirred tank type reactor 11: Raw material supply section 12: Stirring device 13: Withdrawal section 1b: Reactive distillation column 2: Acid addition section 2a: Static mixer 21a: Acidic substance supply line 3: Solvent addition section 3a: Stirred mixing tank 31a: Solvent supply line 4: Distillation device 4a: Distillation column

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/JP2024/020116 2023-06-08 2024-05-31 エチル基を有するカーボネートの製造方法及びエチル基を有するカーボネートの製造装置 Ceased WO2024253046A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09118652A (ja) * 1995-10-25 1997-05-06 Mitsubishi Chem Corp 鎖状炭酸エステルの製造方法
JP2010168365A (ja) * 2008-12-26 2010-08-05 Mitsubishi Chemicals Corp 対称ジアルキルカーボネート及び非対称ジアルキルカーボネートの製造方法
WO2014061678A1 (ja) * 2012-10-15 2014-04-24 宇部興産株式会社 ジエチルカーボネートの製造方法
WO2022114592A1 (ko) 2020-11-26 2022-06-02 롯데케미칼 주식회사 우수한 용해도를 가지는 촉매를 이용한 이종 선형 카보네이트를 제조하는 방법
WO2022114576A1 (ko) 2020-11-26 2022-06-02 롯데케미칼 주식회사 촉매 필터링 단계가 도입된 이종 선형 카보네이트를 제조하는 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09118652A (ja) * 1995-10-25 1997-05-06 Mitsubishi Chem Corp 鎖状炭酸エステルの製造方法
JP2010168365A (ja) * 2008-12-26 2010-08-05 Mitsubishi Chemicals Corp 対称ジアルキルカーボネート及び非対称ジアルキルカーボネートの製造方法
WO2014061678A1 (ja) * 2012-10-15 2014-04-24 宇部興産株式会社 ジエチルカーボネートの製造方法
WO2022114592A1 (ko) 2020-11-26 2022-06-02 롯데케미칼 주식회사 우수한 용해도를 가지는 촉매를 이용한 이종 선형 카보네이트를 제조하는 방법
WO2022114576A1 (ko) 2020-11-26 2022-06-02 롯데케미칼 주식회사 촉매 필터링 단계가 도입된 이종 선형 카보네이트를 제조하는 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4725935A1

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