WO2016104760A1 - 炭酸エステルの精製方法、炭酸エステル溶液の製造方法、及び炭酸エステルの精製装置 - Google Patents
炭酸エステルの精製方法、炭酸エステル溶液の製造方法、及び炭酸エステルの精製装置 Download PDFInfo
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- WO2016104760A1 WO2016104760A1 PCT/JP2015/086359 JP2015086359W WO2016104760A1 WO 2016104760 A1 WO2016104760 A1 WO 2016104760A1 JP 2015086359 W JP2015086359 W JP 2015086359W WO 2016104760 A1 WO2016104760 A1 WO 2016104760A1
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- carbonate ester
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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
- C07C68/08—Purification; Separation; Stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
Definitions
- the present disclosure relates to a carbonate ester purification method, a carbonate ester solution production method, and a carbonate ester purification apparatus.
- Carbonic acid ester is a compound useful as a synthetic raw material for aromatic polycarbonate, medical and agricultural chemicals and the like.
- a process for producing a carbonate ester a process is known in which synthesis is performed by a gas phase reaction using carbon monoxide and a nitrite ester in the presence of a platinum group metal-based solid catalyst (for example, Patent Document 1, 2).
- a desired compound is produced by a catalytic reaction while recycling alkyl nitrite as a raw material.
- the target compound can be mass-produced by scaling up the apparatus.
- Patent Document 2 proposes a technique for suppressing a decrease in catalyst activity by detecting the concentration of nitric oxide in a supply gas and adjusting the supply amount of molecular oxygen based on the concentration.
- Patent document 3 the technique of removing the by-product halide is proposed (for example, refer patent document 3).
- the carbonate solution obtained by such a process contains a trace amount of impurities derived from side reactions that are difficult to reduce with a distillation column.
- the present invention provides an alkali treatment step of mixing a first solution containing a carbonate ester and an acidic substance with an alcohol solution of a metal alcoholate to obtain a mixed liquid containing a reaction product of the acidic substance and the metal alcoholate.
- a distillation step for removing different components, wherein the content of the metal alcoholate in the alcohol solution is 5 to 18% by mass.
- an alkali treatment step is performed using an alcohol solution containing a metal alcoholate.
- a metal salt is produced as a reaction product of an acidic substance and a metal alcoholate.
- the removal step by removing the metal salt, it is possible to obtain a second solution in which the content of the acidic substance is reduced as compared with the first solution.
- impurities different from the carbonate ester can be reduced from the second solution.
- the content of the metal alcoholate in the alcohol solution is within a predetermined range, the reaction between the acidic substance and the metal alcoholate is sufficiently advanced, and the generation of by-products that are impurities in the second solution is suppressed. Can do. Therefore, the impurities of carbonate ester can be reduced.
- the present invention provides an alkaline treatment step of mixing a first solution containing a carbonate ester and an acidic substance with an alcohol solution of a metal alcoholate to obtain a mixed liquid containing a reaction product of the acidic substance and the metal alcoholate.
- a distillation step of removing a different component to obtain a carbonate ester solution, and a method for producing a carbonate ester solution, wherein the content of metal alcoholate in the alcohol solution is 5 to 18% by mass.
- the alkali treatment step is performed using an alcohol solution containing a metal alcoholate.
- an acidic substance and a metal alcoholate can be reacted to form a metal salt.
- the removal step by removing the metal salt, it is possible to obtain a second solution in which the content of the acidic substance is reduced as compared with the first solution.
- impurities different from the carbonate ester can be reduced from the second solution.
- content of the metal alcoholate in the said alcohol solution exists in a predetermined range, the production
- the content of methoxymethyl methyl carbonate in the carbonate solution may be less than 2 ppm by mass.
- the carbonate solution can be used for various applications.
- the present invention provides a processing unit for mixing a first solution containing a carbonate ester and an acidic substance with an alcohol solution of a metal alcoholate to obtain a mixed liquid containing a reaction product of the acidic substance and the metal alcoholate. And a separation unit for removing the metal salt contained in the reaction product from the mixed solution to obtain the second solution, and fractionating the second solution to remove components having a boiling point different from that of the carbonate ester from the second solution. And an apparatus for purifying carbonate, wherein the content of the metal alcoholate in the alcohol solution is 5 to 18% by mass.
- the above-described purification apparatus includes a processing unit that mixes the first solution with an alcohol solution containing a metal alcoholate.
- a processing unit that mixes the first solution with an alcohol solution containing a metal alcoholate.
- an acidic substance and a metal alcoholate can be reacted to generate a metal salt.
- the separation part by removing the metal salt, it is possible to obtain the second solution in which the content of the acidic substance is reduced as compared with the first solution.
- the second solution can be fractionally distilled to further reduce impurities different from the carbonate ester from the second solution. Since the content of the metal alcoholate in the alcohol solution is within a predetermined range, the by-product that is an impurity in the second solution is generated while the reaction between the acidic substance and the metal alcoholate is sufficiently advanced in the processing unit. Can be suppressed. Therefore, the impurities of carbonate ester can be reduced.
- the content of methoxymethyl methyl carbonate in the carbonate ester solution may be less than 2 ppm by mass.
- carbonate ester can be used for various uses by fully reducing the content of methoxymethyl methyl carbonate.
- a carbonate ester purification method and a carbonate ester purification apparatus capable of reducing impurities can be provided. Further, in another aspect, a production method capable of producing a carbonate solution with reduced impurities can be provided.
- FIG. 1 is a diagram schematically illustrating an embodiment of a carbonate ester purification apparatus.
- FIG. 2 is an example of an apparatus for producing a first solution containing carbonate ester and formaldehyde.
- FIG. 1 is a diagram schematically showing an embodiment of a purification apparatus for purifying carbonate ester.
- One embodiment of the carbonate ester purification method and the carbonate ester solution production method can use the carbonate ester purification device 200 (carbonate ester solution production device 200) shown in FIG.
- a first solution containing a carbonate ester and an acidic substance is mixed with an alcohol solution of a metal alcoholate to obtain a mixed solution containing a reaction product of the acidic substance and the metal alcoholate.
- the distillation step has a first distillation step and a second distillation step.
- the carbonate ester purification apparatus 200 includes a processing unit 100 that performs an alkali treatment step, a separation unit 110 that performs a removal step, and a first distillation unit 101 and a second distillation unit 102 that perform a distillation step.
- the first solution can be obtained by condensing a product obtained by subjecting carbon monoxide and a nitrite to a gas phase reaction in the presence of a platinum group metal solid catalyst.
- the first solution contains an organic compound such as alcohol and ether, and an acidic substance such as a chlorine compound and a nitric acid compound as subcomponents in addition to the carbonic acid ester as the main component.
- the concentration of the subcomponent having a large boiling point difference from the carbonate ester can be adjusted using a distillation column or the like.
- Carbonate ester is, for example, dialkyl carbonate.
- the two alkyl groups in the dialkyl carbonate molecule may be the same or different.
- Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, dinonyl carbonate, ethyl methyl carbonate, and ethyl propyl carbonate.
- dialkyl carbonates having a linear or branched alkyl group having 1 to 10 carbon atoms are preferable from the viewpoint of the reaction rate of the transesterification reaction and the ease of removing the by-produced alkyl alcohol. More preferred is dimethyl carbonate or diethyl carbonate.
- the content of the carbonate ester in the first solution is, for example, 98.0 to 99.998% by mass.
- the first solution contains an acidic substance or an ester of an acidic substance in addition to the carbonate ester.
- Acidic materials include hydrochloric acid, nitric acid, nitrous acid, and formic acid, and mixtures thereof.
- Examples of the acidic substance ester include nitrate esters and chloroformates.
- the total content of the chlorine compound and the nitric acid compound (including the nitrous acid compound) in the first solution is, for example, 5 to 100 ppm by mass in terms of Cl and NO 3 or NO 2 , respectively.
- the first solution may contain about 1 to 100 ppm by mass of alcohol. Examples of the alcohol include methanol and ethanol.
- an alkali metal alcoholate is preferably used from the viewpoint of increasing the reactivity with acidic substances and esters of acidic substances.
- the alkali metal alcoholate include sodium methoxide, sodium ethoxide, potassium methoxide, potassium methoxide, and the like. These 1 type can be used individually or in combination of 2 or more types.
- the alcohol solution of metal alcoholate is obtained by dissolving the above-mentioned metal alcoholate in alcohol.
- Various alcohols can be used, and for example, a monoalcohol such as methanol, ethanol, propanol, or butanol can be used. These 1 type can be used individually or in combination of 2 or more types.
- the content of the metal alcoholate in the alcohol solution is 5 to 18% by mass, preferably 5 to 10% by mass. If the content of the metal alcoholate becomes too high, side reactions tend to proceed in the alkali treatment step. This tends to easily generate impurities different from the carbonate ester. On the other hand, if the content of the metal alcoholate is too low, the amount of the alcohol solution for neutralizing the acidic substance becomes too large, and the load on the distillation column for separating the carbonate and alcohol tends to increase. is there.
- the processing unit 100 includes a processing tank 10 for mixing the first solution and the alcohol solution of the metal alcoholate. Pipes 13 and 14 are connected to the processing tank 10.
- the treatment tank 10 is provided with a jacket 12 for circulating a heat medium.
- the first solution is supplied to the processing tank 10 through the pipe 13.
- the alcohol solution of the metal alcoholate is supplied to the treatment tank 10 through the pipe 14.
- the first solution and the alcohol solution of the metal alcoholate are mixed by the stirrer 16.
- the mixed solution is heated to a temperature not higher than the boiling point of alcohol, for example.
- An acidic substance such as a chlorine compound and a nitric acid compound contained in the first solution and a metal alcoholate alcohol solution are neutralized. In this way, acidic substances and the like can be reduced in the alkali treatment step.
- the alcohol solution of the metal alcoholate is mixed with the first solution so that the amount is equal to or more than the amount (neutralization equivalent) necessary for neutralizing the acidic substance contained in the first solution. It is preferable to do.
- the alcohol contained in the alcohol solution can be removed by a distillation column provided on the downstream side.
- a reaction product is generated in the treatment tank 10 by a neutralization reaction between the acidic substance and the metal alcoholate.
- the reaction product include metal salts such as inorganic chlorides and inorganic nitrate compounds.
- the metal salt precipitates as a solid content when the mixed solution in the treatment tank 10 is cooled to about 30 ° C., for example.
- the removing step the solid content is removed from the mixed solution containing the solid content and the carbonate ester to obtain a second solution containing the carbonate ester.
- the mixed solution is introduced into the separation unit 110 through the pipe 18 and the pump 19 connected to the bottom of the processing tank 10.
- a cooler may be provided between the processing unit 100 and the separation unit 110.
- the separation unit 110 includes a filter 17 having a filter. Separation unit 110 is not particularly limited as long as it is configured to be able to remove solids contained in the mixed solution.
- the 2nd solution containing carbonate ester as a main component is obtained by removing solid content.
- the second solution may contain impurities such as alcohol and water. As an impurity, the trace component contained in a 1st solution may be included.
- the carbonate ester content in the second solution is, for example, 90 to 99.998% by mass. That is, the second solution may contain about 0.002 to 10% by mass of impurities. Examples of impurities include nitric acid compounds and organic compounds.
- first distillation step and the second distillation step impurities contained in the second solution are removed by fractional distillation. Thereby, impurities having a boiling point different from that of the carbonate ester can be removed.
- the first distillation step and the second distillation step can be performed using a normal distillation tower.
- the first distillation step and the second distillation step are performed using two distillation columns, but the distillation column is not limited to two, and only one distillation step is used. Or three or more distillation steps using three or more groups.
- the second solution obtained in the removing step is introduced into the first distillation column 20 of the first distillation unit 101 through the pipe 15.
- impurities such as alcohol and carbonates are fractionated by a difference in boiling points.
- a distillate containing an alcohol having a boiling point lower than that of the carbonic acid ester is introduced from the top 20 a of the first distillation column 20 to the reflux unit 20 A provided in the first distillation column 20.
- the reflux unit 20A includes a condenser 22 for cooling the distillate, a tank 24, a pump 27, and piping for connecting these devices.
- the distillate discharged from the top 20a of the first distillation column 20 through the pipe 21 is cooled by the condenser 22 to become a condensed liquid, and then stored in the tank 24.
- the condensate containing alcohol or the like in the tank 24 is returned from the tank 24 to the upper portion of the first distillation column 20 via the pump 27 and the pipe 26.
- a part of the condensate in the tank 24 is discharged to the outside of the first distillation column 20 continuously or intermittently via the pump 27 and the pipe 25.
- the discharged liquid from the pipe 25 may contain, for example, a carbonic ester as a main component and alcohol, ether, water, and the like as subcomponents.
- the composition of the discharged liquid is the same as the composition of the reflux liquid circulating in the reflux unit 20A.
- the content of the organic compound different from dimethyl carbonate in the effluent is, for example, 0.01 to 10% by mass.
- the carbonate ester content in the effluent is, for example, 90 to 99.3% by mass.
- the discharged liquid from the tower top 20a discharged via the pipe 25 may be joined to the alcohol flowing through the pipe 316 or the pipe 319 of the manufacturing apparatus 300 in FIG.
- the third solution containing the carbonate ester is discharged from the pipe 30 connected to the column bottom 20b of the first distillation column 20.
- the third solution has a lower boiling point than the first solution. For this reason, the purity of the carbonate ester in the third solution is higher than that of the first solution.
- the purity of the carbonate of the third solution is, for example, 99.99% by mass or more. That is, in the third solution, the content of trace components such as acidic substances, alcohols and ethers is sufficiently reduced as compared with the first solution.
- a carbonic acid ester solution is particularly useful for applications (for example, an electrolytic solution for a lithium ion battery) in which it is necessary to sufficiently reduce trace components.
- the third solution discharged from the bottom 20b of the first distillation column 20 may contain trace components such as water and alcohol. Such trace components can be reduced in the second distillation step.
- the third solution is supplied to the second distillation column 40 of the second distillation unit 102 via the pipe 30, the pump 34 and the pipe 36. A part of the third solution may be heated by heat exchange with the heat medium in the heat exchanger 32 and then returned to the lower portion of the first distillation column 20 as a heat source for the first distillation column 20.
- the carbonate ester and the trace component contained in the third solution are fractionated by the difference in boiling points.
- a fluid containing a trace component having a boiling point higher than that of the carbonate ester flows through the pipe 60 connected to the tower bottom 40 b of the second distillation tower 40, and is discharged via the pump 64 and the pipe 66.
- a part of the fluid may be heated by heat exchange with the heat medium in the heat exchanger 62 and then returned to the lower portion of the second distillation column 40 as a heat source for the second distillation column 40.
- Water is mentioned as a trace component which has a boiling point higher than carbonate ester.
- the third solution contains a minor component (eg, alcohol) having a boiling point lower than that of a carbonic acid ester such as alcohol
- these minor components are added to the condenser 42 connected to the top 40a of the second distillation column 40 and It is introduced into a reflux unit 40 ⁇ / b> A having a tank 44.
- the fluid from the top of the second distillation column 40 is cooled by the condenser 42 to become a condensed liquid, and then stored in the tank 44.
- the condensate containing trace components such as alcohol in the tank 44 is refluxed from the tank 44 to the second distillation column 40 via the pump 47 and the pipe 46.
- a part of the condensate in the tank 44 may be returned to the treatment tank 10 through the piping 50 or may be used for other purposes.
- the carbonate ester contained in the third solution is extracted by a side cut through a pipe 49 connected between the center of the second distillation column 40 and the top of the column.
- the carbonate solution extracted by the side cut is cooled by the heat exchanger 48 connected to the pipe 49. In this way, the content of impurities different from the carbonate ester can be sufficiently reduced.
- the carbonate ester purity of the carbonate ester solution obtained in the second distillation column 40 is, for example, 99.995% by mass or more.
- the second distillation column 40 of the second distillation unit 102 By using the second distillation column 40 of the second distillation unit 102 to fractionate the third solution, it is possible to obtain a carbonate solution in which the content of impurities is lower than that of the third solution. Since the purification apparatus 200 of carbonate ester has arrange
- the production of by-products such as methoxymethyl methyl carbonate can be suppressed in the alkali treatment step.
- generation of the by-product which has a boiling point comparable as a carbonate ester is suppressed, the carbonate ester solution in which content of impurities was fully reduced can be manufactured.
- the content of methoxymethyl methyl carbonate in the carbonate solution may be, for example, less than 2 mass ppm or less than 1 mass ppm.
- the carbonate solution in which impurities are sufficiently reduced is particularly useful for applications (for example, an electrolyte solution for a lithium ion battery) that needs to sufficiently reduce trace components.
- FIG. 2 is an example of an apparatus for producing a first solution containing carbonate ester and formaldehyde.
- the first solution manufacturing apparatus 300 includes a catalyst that reacts carbon monoxide and alkyl nitrite to generate dialkyl carbonate and nitric oxide, and includes carbon monoxide, alkyl nitrite, and nitric oxide.
- the first reactor 310 that generates the second gas containing dialkyl carbonate and nitric oxide from the first gas that is contained is brought into contact with the second gas and the absorbing liquid that absorbs the dialkyl carbonate, thereby containing the dialkyl carbonate.
- Absorption tower 320 for separating condensate and non-condensable gas containing nitric oxide, mixed gas of non-condensed gas and molecular oxygen and alcohol are introduced to react nitrogen monoxide, molecular oxygen and alcohol.
- a second reactor 330 for generating a third gas containing alkyl nitrite and nitric oxide.
- the first reactor 310 has a carbonic acid ester production catalyst that reacts carbon monoxide and alkyl nitrite to generate carbonic acid ester and nitric oxide.
- the carbonic acid ester production catalyst include a solid catalyst in which a platinum group metal and / or a compound thereof is supported on a carrier.
- the supported amount of the platinum group metal and its compound in the solid catalyst is 0.1 to 10% by weight, preferably 0.5 to 2% by weight, based on the support.
- the carrier include inert carriers such as activated carbon, alumina ( ⁇ -alumina, etc.), zeolite, molecular sieve, spinel (lithium aluminate spinel, etc.).
- the platinum group metal and its compound are supported on the carrier using a known method such as an impregnation method or an evaporation to dryness method.
- platinum group metal and its compound examples include platinum metal, palladium metal, rhodium metal, and iridium metal.
- Platinum group metal compounds include inorganic acid salts (nitrates, sulfates, phosphates, etc.), halides (chlorides, bromides, etc.), organic acid salts (acetates, oxalates, benzoic acids) of these metals. Salt), complexes (lithium tetrachloropalladate, sodium tetrachloropalladate, etc.) and the like.
- palladium chloride or a chlorine-containing complex of palladium is preferable.
- the amount of platinum group metal and / or compound thereof supported on the support is preferably 0.01 to 10% by mass, more preferably 0.2 to 2% by mass.
- platinum group metal and its compound copper, iron, bismuth, or these compounds can be contained in the catalyst for producing a carbonate ester.
- chlorides cuprous chloride, cupric chloride, ferrous chloride, ferric chloride, bismuth chloride, etc.
- the amount of these supported on the carrier is preferably 1: 0.1 to 1:50 as “platinum group metal and compound thereof”: “copper, iron, bismuth and compound thereof” (molar ratio of metal atoms), A ratio of 1: 1 to 1:10 is more preferable.
- the method for preparing the catalyst is not particularly limited.
- the platinum group metal compound can be supported on a support by a known method such as an impregnation method or an evaporation to dryness method, and then the support can be dried.
- R represents an alkyl group.
- the alkyl group preferably has 1 to 3 carbon atoms.
- the content of nitric oxide in the first gas is, for example, 5 to 50% by volume based on the total of carbon monoxide, alkyl nitrite and nitric oxide.
- the first gas contains nitric oxide at a higher concentration than molecular oxygen. For this reason, the concentration of nitric oxide in the first gas can be detected easily and with high accuracy.
- the content of carbon monoxide in the first gas is, for example, 30 to 70% by volume based on the sum of carbon monoxide, alkyl nitrite, and nitric oxide.
- the content of alkyl nitrite in the first gas is, for example, 10 to 50% by volume based on the total of carbon monoxide, alkyl nitrite and nitric oxide.
- the first gas may contain an inert gas together with carbon monoxide, alkyl nitrite, and nitric oxide.
- concentration of nitric oxide in the first gas is preferably 1 to 20% by volume based on the entire first gas.
- concentration of carbon monoxide in the first gas is, for example, 10 to 40% by volume based on the entire first gas.
- a second gas containing carbonate and nitric oxide is generated by the reaction shown in the above formula (1).
- the concentration of the carbonate ester in the second gas is, for example, 1 to 50% by volume with respect to the entire second gas, and the concentration of nitric oxide is, for example, 1 to 20% by volume.
- Volume% in this specification shows the volume ratio in a standard state (25 degreeC, 100 kPa).
- the second gas generated in the first reactor 310 is introduced into the absorption tower 320 through the pipe 312.
- the absorption tower 320 only needs to be capable of gas-liquid contact, for example, a shelf type such as a sieve tray, a bubble bell tray, or a valve tray, or an irregular packing material such as a pole ring or a Raschig ring, a sheet shape, Examples thereof include a packed tower type absorption tower filled with a regular packing material such as a gauze plate or a composite plate obtained by combining them.
- the second gas introduced into the lower part of the absorption tower 320 from the first reactor 310 via the pipe 312 is an absorbent for absorbing carbonate (hereinafter simply referred to as “absorption liquid”) introduced from the upper part of the absorption tower 320. ) And countercurrent contact.
- the second gas and the absorbing liquid are brought into gas-liquid contact, and at least a part of the carbonate ester contained in the second gas is absorbed by the absorbing liquid.
- the condensate which absorbed the carbonate ester and the non-condensable gas containing nitric oxide are obtained.
- Examples of the absorbing solution used in the absorption tower 320 include alcohols, carbonates, and oxalates corresponding to the alkyl group of the carbonate.
- the supply amount of the absorption liquid to the absorption tower 320 is, for example, 1 to 30% on a mass basis with respect to the carbonate ester in the second gas.
- the alcohol is preferably an aliphatic alcohol having 1 to 3 carbon atoms such as methanol or ethanol. From the viewpoint of easy recovery, an alcohol having the same alkyl group as the alkyl nitrite introduced into the first reactor 310 together with carbon monoxide is preferable.
- the condensate containing the absorption liquid and the carbonate obtained in the absorption tower 320 is extracted from a pipe 314 connected to the bottom of the absorption tower 320.
- the condensate is introduced into the distillation column 360 through the pipe 314.
- the solution is separated into a solution containing an absorbing solution and a first solution containing a carbonate ester due to a difference in boiling point.
- a low-boiling point alcohol such as methanol or ethanol
- the alcohol is supplied from the pipe 362 connected to the top of the distillation tower 360, and the first solution is supplied from the pipe 13 connected to the bottom of the distillation tower 360. Discharged.
- the first solution may be supplied to the treatment tank 10 in FIG. 1 or may be supplied to the first distillation column 20. By adjusting the operating conditions of the distillation column 360, the alcohol content in the first solution can be changed.
- the carbonate ester content in the first solution is, for example, 98.0 to 99.998 mass%.
- the non-condensed gas containing carbon monoxide obtained in the absorption tower 320 flows through a pipe 313 connected to the upper part of the absorption tower 320.
- a pipe 322 for introducing molecular oxygen is connected to the pipe 313.
- Molecular oxygen supplied from the pipe 322 is mixed with a non-condensed gas to become a mixed gas.
- the mixed gas is introduced into the second reactor 330 through the pipe 313.
- the side reaction represented by the reaction formula (II) may proceed. From the viewpoint of improving the efficiency of the entire facility, it is preferable to promote the reaction formula (I) rather than the reaction formula (II).
- the mixing ratio of nitrogen monoxide and molecular oxygen in the mixed gas may be a ratio of 0.08 to 0.2 mol with respect to 1 mol of nitrogen monoxide contained in the mixed gas.
- the alcohol introduced from the pipe 316 an alcohol having an alkyl group of carbonate ester produced by the production apparatus 300 is used.
- examples of such alcohols include aliphatic alcohols having 1 to 3 carbon atoms such as methanol or ethanol.
- the supply amount of alcohol to the second reactor 330 is, for example, 0.5 molar ratio with respect to the supply amount of nitric oxide contained in the mixed gas. ⁇ 1.5.
- the reaction temperature in the second reactor 330 can be appropriately set according to the type of alcohol introduced from the pipe 316.
- the temperature is, for example, 0 to 80 ° C.
- the reaction pressure is, for example, 0.1 to 1 MPa, and the gas-liquid contact time is, for example, 0.5 to 30 seconds.
- the third gas extracted from the upper part of the second reactor 330 contains, in addition to the alkyl nitrite generated in the reaction formula (I), nitrogen monoxide, and trace components such as dinitrogen monoxide and carbon dioxide. . These trace components can be appropriately discharged out of the system by a pipe 317 branched from the pipe 311 as off-gas.
- the content of nitric oxide in the third gas is, for example, 5 to 50% by volume with respect to the total of nitric oxide and alkyl nitrite.
- the third gas flows through the pipe 311 toward the first reactor 310.
- the pipe 311 has a joining part with the pipe 318 for supplying carbon monoxide, and the third gas and carbon monoxide are mixed in the joining part. Thereby, the first gas is obtained.
- the first gas is supplied to the first reactor 310.
- the analysis apparatus and analysis method in each example described below are as follows.
- a gas chromatograph GC-2014 manufactured by Shimadzu Corporation was used. (Trade name) was used.
- HP-INNOWAX (trade name) manufactured by Agilent Technologies, Inc. was used.
- a trace moisture measuring device CA-05 type (trade name) manufactured by Mitsubishi Chemical Corporation was used.
- a sample was pretreated using an oxyhydrogen flame type sulfur / halogen determination device manufactured by Toshin Seiki Co., Ltd.
- the Cl ⁇ content was measured using an ion chromatograph measuring device ICS-1600 (trade name) manufactured by Nippon Dionex Co., Ltd. using the pretreated sample.
- Ion Pac AS12A (trade name) manufactured by Thermo Fisher Scientific Co., Ltd. was used. Cl of this analysis - the measuring limit (lower limit) was 0.01 mass ppm.
- nitrate compounds including nitrite compound
- NO in the sample 3 - and NO 2 - was extracted with distilled water was performed using an ion chromatographic measurement apparatus used in the analysis of chlorine.
- the measurement limit (lower limit) of the nitric acid compound (including the nitrous acid compound) in this analysis was 0.01 mass ppm.
- the metal (Fe) first, the sample was incinerated with a quartz dish, and then the incinerated product was dissolved in distilled water and high-purity nitric acid (content: 69 to 70% by mass) to prepare a measurement sample.
- the measurement sample was analyzed using an ICP-MS analyzer Agilent 7700 (trade name) manufactured by Agilent Technologies.
- Example 1 ⁇ Alkali treatment process> 250 L of a dimethyl carbonate solution (first solution) shown in Table 1 was placed in a stainless steel jacketed treatment tank (300 L) equipped with a thermometer and a stirrer. While stirring the dimethyl carbonate solution, warm water was passed through the jacket to adjust the liquid temperature to 40 ° C. To this dimethyl carbonate solution was added a methanol solution containing 15% by mass of sodium methylate (containing 1.5 mass ppm of Cl and equimolar Na of the first solution), and then stirring was continued for 1 hour. I went. A part of the obtained treatment liquid was sampled and filtered, and the filtrate was analyzed. The composition of the filtrate was as shown in Table 1.
- the round bottom flask was immersed in an oil bath, and the oil bath was heated and cooked to be fully refluxed. Total reflux was continued until the overall temperature of the distillation column was approximately constant. When the temperature of the entire distillation column became almost constant, the temperature of the reflux liquid was 50 to 55 ° C.
- the filtrate shown in Table 1 was continuously supplied at a flow rate of 150 ml / hour using a supply pipe connected to the middle stage of the distillation column. With the start of feeding, the liquid was continuously discharged from the round bottom flask so as to keep the liquid level of the round bottom flask constant. While maintaining the reflux amount at 130 to 150 ml / hour and the top temperature of the distillation column at 89 ° C.
- ⁇ Second distillation step> The effluent from the bottom obtained in the first distillation step was supplied to a theoretical 16-stage distillation column equipped with regular packing, cooked under normal pressure, and fully refluxed. And the distillate was gradually discharged
- Example 1 methoxymethyl methyl carbonate (MMMC) and methyl vinyl carbonate (MVC) were not detected in any of the filtrate, the distillate from the top of the column, the discharge from the bottom, and the side cut. Thus, it was confirmed that the purification method of Example 1 can produce dimethyl carbonate with sufficiently reduced impurities.
- the purity of dimethyl carbonate in the effluent from the bottom was 99.997% by mass, and the purity of side-cut dimethyl carbonate was 99.998% by mass. From this, it was confirmed that a high purity dimethyl carbonate solution could be produced.
- Example 2 In place of a methanol solution with a sodium methylate content of 15% by mass, a methanol solution with a sodium methylate content of 5% by mass (1.5 mass ppm of Cl in the first solution and equimolar Na
- a methanol solution with a sodium methylate content of 5% by mass 1.5 mass ppm of Cl in the first solution and equimolar Na
- MMMC methoxymethyl methyl carbonate
- the present disclosure it is possible to provide a carbonate ester purification method and a carbonate ester purification apparatus capable of reducing impurities. Moreover, the manufacturing method which can manufacture the carbonate solution with which the impurity was reduced can be provided.
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Abstract
Description
CO+2RONO → ROC(=O)OR+2NO (i)
NO+3/4O2+1/2H2O→ HNO3 (II)
有機化合物[炭酸ジメチル、メタノール、ジメチレングリコールジメチルエーテル(DMME)、メチルビニルカーボネート(MVC)、メトキシメチルメチルカーボネート(MMMC)]の含有量の分析には、株式会社島津製作所製のガスクロマトグラフ GC-2014(商品名)を用いた。キャピラリーカラムは、アジレント・テクノロジー株式会社製のHP-INNOWAX(商品名)を用いた。
<アルカリ処理工程>
温度計と攪拌機を取り付けたステンレス製のジャケット付き処理槽(300L)に、表1に示す炭酸ジメチル溶液(第1溶液)を250L入れた。炭酸ジメチル溶液を攪拌しながら、ジャケットに温水を流通させて、液温を40℃に調整した。この炭酸ジメチル溶液にナトリウムメチラートの含有量が15質量%であるメタノール溶液(第1溶液の1.5質量ppmのClと等モルのNaを含む)を加えた後、攪拌を1時間継続して行った。得られた処理液の一部をサンプリングして濾過し、濾液を分析した。濾液の組成は、表1に示すとおりであった。
還流配管を備えるガラス製の蒸留塔(内径:25mm、充填物:スルザーEX(登録商標)、理論段数:16)を準備した。この蒸留塔の底部には300mlの丸底フラスコを取り付けた。表1の濾液200mlを丸底フラスコ内に入れた。
第1蒸留工程で得られたボトムからの排出液を、規則充填物を備えた理論段16段の蒸留塔に供給して常圧下で炊き上げ、全還流させた。そして、塔頂温度を90℃以上に維持しながら、塔頂から留出液を徐々に排出した。供給した液量の3体積%程度を塔頂から排出した後、還流比を1.5に調整した。その後、蒸留塔の全高をHとしたときに、塔頂から、1/4H下がった位置(塔底から3/4Hの高さ)より、炭酸ジメチル溶液をサイドカットで留出させた。サイドカットで得られた炭酸ジメチル溶液の組成は、表1に示すとおりであった。
ナトリウムメチラートの含有量が15質量%であるメタノール溶液に変えて、ナトリウムメチラートの含有量が5質量%であるメタノール溶液(第1溶液の1.5質量ppmのClと等モルのNaを含む)を用いたこと以外は、実施例1と同様にして、アルカリ処理工程、第1蒸留工程、及び第2蒸留工程を行った。分析結果は、表2に示すとおりであった。
ナトリウムメチラートの含有量が15質量%であるメタノール溶液に変えて、ナトリウムメチラートの含有量が20質量%であるメタノール溶液(第1溶液の1.5質量ppmのClと等モルのNaを含む)を用いたこと以外は、実施例1と同様にして、アルカリ処理工程、第1蒸留工程、及び第2蒸留工程を行った。分析結果は、表3に示すとおりであった。
Claims (5)
- 炭酸エステル及び酸性物質を含む第1溶液と金属アルコラートのアルコール溶液とを混合して、前記酸性物質と前記金属アルコラートとの反応生成物を含む混合液を得るアルカリ処理工程と、
前記混合液から、前記反応生成物に含まれる金属塩を除去して前記炭酸エステルを含む第2溶液を得る除去工程と、
前記第2溶液から前記炭酸エステルとは沸点が異なる成分を除去する蒸留工程と、を有し、
前記アルコール溶液における前記金属アルコラートの含有量が5~18質量%である、炭酸エステルの精製方法。 - 炭酸エステル及び酸性物質を含む第1溶液と金属アルコラートのアルコール溶液とを混合して、前記酸性物質と前記金属アルコラートとの反応生成物を含む混合液を得るアルカリ処理工程と、
前記混合液から、前記反応生成物に含まれる金属塩を除去して、前記炭酸エステルを含む第2溶液を得る除去工程と、
前記第2溶液から前記炭酸エステルとは沸点が異なる成分を除去して炭酸エステル溶液を得る蒸留工程と、を有し、
前記アルコール溶液における前記金属アルコラートの含有量が5~18質量%である、炭酸エステル溶液の製造方法。 - 前記炭酸エステル溶液におけるメトキシメチルメチルカーボネートの含有量が2質量ppm未満である、請求項2に記載の炭酸エステル溶液の製造方法。
- 炭酸エステル及び酸性物質を含む第1溶液と金属アルコラートのアルコール溶液とを混合して、前記酸性物質と前記金属アルコラートとの反応生成物を含む混合液を得る処理部と、
前記混合液から、前記反応生成物に含まれる金属塩を除去して第2溶液を得る分離部と、
前記第2溶液から前記炭酸エステルとは沸点が異なる成分を除去して炭酸エステル溶液を得る蒸留部を備え、
前記アルコール溶液における前記金属アルコラートの含有量が5~18質量%である、炭酸エステルの精製装置。 - 前記炭酸エステル溶液におけるメトキシメチルメチルカーボネートの含有量が2質量ppm未満である、請求項4に記載の炭酸エステルの精製装置。
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JPH03120240A (ja) * | 1989-10-03 | 1991-05-22 | Daicel Chem Ind Ltd | ジアルキルカーボネートの精製方法 |
JPH05201932A (ja) * | 1991-07-17 | 1993-08-10 | Bayer Ag | ジアルキルカーボネートの製造方法 |
JPH0692905A (ja) * | 1991-07-26 | 1994-04-05 | Nippon Polyurethane Ind Co Ltd | ジアルキル炭酸エステルの精製処理方法 |
JP2004323470A (ja) * | 2003-04-28 | 2004-11-18 | Ube Ind Ltd | 炭酸ジアルキルの製造法 |
JP2004323371A (ja) * | 2003-04-22 | 2004-11-18 | Ube Ind Ltd | 炭酸ジアルキルの製造方法 |
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JPH03120240A (ja) * | 1989-10-03 | 1991-05-22 | Daicel Chem Ind Ltd | ジアルキルカーボネートの精製方法 |
JPH05201932A (ja) * | 1991-07-17 | 1993-08-10 | Bayer Ag | ジアルキルカーボネートの製造方法 |
JPH0692905A (ja) * | 1991-07-26 | 1994-04-05 | Nippon Polyurethane Ind Co Ltd | ジアルキル炭酸エステルの精製処理方法 |
JP2004323371A (ja) * | 2003-04-22 | 2004-11-18 | Ube Ind Ltd | 炭酸ジアルキルの製造方法 |
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