WO2011065528A1 - エチレンカーボネート及びエチレングリコールの製造方法 - Google Patents
エチレンカーボネート及びエチレングリコールの製造方法 Download PDFInfo
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- WO2011065528A1 WO2011065528A1 PCT/JP2010/071251 JP2010071251W WO2011065528A1 WO 2011065528 A1 WO2011065528 A1 WO 2011065528A1 JP 2010071251 W JP2010071251 W JP 2010071251W WO 2011065528 A1 WO2011065528 A1 WO 2011065528A1
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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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
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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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
- C07D303/06—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms in which the oxirane rings are condensed with a carbocyclic ring system having three or more relevant rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a method for producing ethylene carbonate and / or ethylene glycol.
- Ethylene carbonate is used as a solvent for various polymer compounds, a reaction solvent for various chemical reactions, an electrolyte solvent for lithium ion secondary batteries, an extractant, a foaming agent, and a lubricant stabilizer.
- Ethylene carbonate is usually synthesized by reacting ethylene oxide and carbon dioxide at high temperature and high pressure. For this reason, ethylene carbonate contains diols such as ethylene glycol and diethylene glycol derived from these synthetic raw materials. In addition, ethylene carbonate contains a small amount of moisture together with the above impurities, but this moisture reacts with ethylene carbonate to further produce ethylene glycol.
- Ethylene carbonate used as various solvents preferably contains as little impurities as possible, and various methods such as distillation and crystallization have been proposed as methods for purifying ethylene carbonate.
- the distillation method is the most widely used purification method industrially.
- ethylene carbonate has a high boiling point of 246 ° C. (normal pressure)
- thermal degradation occurs even if distillation is performed under reduced pressure, and ethylene carbonate reacts with diol and moisture.
- high molecular weight is further, in the study conducted by the present inventors, some bonds of the high molecular weight ethylene carbonate were broken and returned to diol, so that even after distillation, about 100 ppm of diol remained in ethylene carbonate.
- the distillation method requires energy for the latent heat of vaporization of the substance, and the reflux ratio must be increased. Therefore, the energy consumption is very large compared to the crystallization method that only requires cooling by sensible heat removal.
- the crystallization method is a purification method that utilizes the fact that an impurity component that does not crystallize at that temperature does not enter the crystal when the target component is crystallized. Since the crystallization method can be purified only by crystallization by cooling and dissolution by slight heating, deterioration due to side reactions hardly occurs and energy consumption is low.
- Patent Document 1 discloses that 99.999% or more of high-purity ethylene carbonate can be obtained by applying the crystallization method described in this document.
- Patent Documents 4 to 4 Also known is a method for producing ethylene glycol by adding water to an ethylene carbonate reaction solution obtained by reacting ethylene oxide and carbon dioxide at high temperature and high pressure to cause a hydrolysis reaction. 7).
- Patent Documents 4 to 4 7
- the outlet control valve and the like are blocked in the hydrolysis reaction tank.
- JP 2007-284427 A British Patent No. 2098985 JP 2004-262767 A Japanese Patent Publication No. 55-47617 JP 59-13741 A JP 2000-128814 A JP 2004-196722 A
- the present invention provides a method for producing ethylene carbonate from which the coloring component contained in the ethylene carbonate is removed, and a method for producing ethylene glycol that can be stably operated for a long time while preventing clogging in the ethylene glycol production process.
- the issue is to provide
- the present inventors obtained a reaction liquid containing ethylene carbonate by reacting carbon dioxide with ethylene oxide in the presence of a catalyst, and the produced ethylene carbonate was crystallized.
- an ethylene carbonate production method by a process including a step of purifying by analysis (this may be referred to as “EC production process” in the present specification)
- an ethylene carbonate reaction solution (in this specification, “ A part of the carbonated reaction solution ”is extracted, and 20 weight times or more of water is added to the catalyst dissolved in the extracted solution to precipitate insoluble components, and the precipitated insoluble components are extracted. After removing from the liquid, it was found that ethylene carbonate from which the coloring component was removed was produced by circulating in the process. It was.
- the present inventors further added water to the carbonated reaction solution to produce ethylene glycol (hereinafter sometimes referred to as “hydrolysis step”). Extracting and adding 20 weight times or more of water to the catalyst dissolved in the extraction liquid to precipitate insolubles, removing the precipitated insolubles from the extraction liquid, and circulating to the process, 1 It has been found that even in the continuous operation for a year, the outlet control valve of the reaction tank does not clog in the hydrolysis step, and the present invention has been completed.
- the present invention (1) In the manufacturing method of ethylene carbonate including the step of reacting carbon dioxide and ethylene oxide in the presence of a catalyst to obtain a reaction solution containing ethylene carbonate, and purifying the produced ethylene carbonate by crystallization, from the reaction solution Extracting the liquid containing the catalyst, adding 20 weight times or more of water to the catalyst dissolved in the extracted liquid to precipitate insolubles, removing the precipitated insolubles, and circulating to the reaction liquid A process for producing ethylene carbonate, (2) The method according to (1) above, wherein the liquid containing the catalyst is a part of a reactor outlet liquid that reacts carbon dioxide and ethylene oxide to produce ethylene carbonate.
- the catalyst-containing liquid is extracted from the reaction liquid, and 20 weight times or more of water is added to the catalyst dissolved in the extracted liquid to precipitate insoluble matter. After removing the solvent, circulating in the reaction solution, ethylene glycol production method, (4)
- the liquid containing the catalyst reacts with carbon dioxide, ethylene oxide, and water to produce ethylene carbonate and ethylene glycol. A part of the outlet liquid of the reactor and / or water is added to the reaction liquid to add ethylene carbonate.
- a method for producing high-purity ethylene carbonate from which coloring components have been removed is provided. Moreover, the manufacturing method of the ethylene glycol which can be drive
- the coloring component in ethylene carbonate to be removed by the method for producing ethylene glycol of the present invention is a substance that emits fluorescence when irradiated with ultraviolet rays.
- carbon dioxide and ethylene oxide are reacted to form ethylene carbonate, and the origin of the presence is traced by fluorescence analysis in the ethylene carbonate production process of the present invention including the step of purifying the produced ethylene carbonate by crystallization.
- the coloring component is circulated and concentrated in the process together with the catalyst.
- This concentrated colored component is mixed with the product ethylene carbonate and becomes reddish when the produced ethylene carbonate is recovered with high purity by a crystallization method.
- this colored component is composed of components composed of polyethylene glycol, polyethylene, and aromatics.
- the coloring component is soluble in a polar solvent such as methanol, but has low solubility in water. Therefore, the coloring component is a substance that can be precipitated and removed by adding a certain amount of water.
- the ethylene carbonate production method of the present invention comprises the production of ethylene carbonate by reacting carbon dioxide and ethylene oxide in the presence of a catalyst (in the present specification, this is referred to as "carbonation reaction"). This is due to a process including a step of purifying the produced ethylene carbonate by crystallization.
- Examples of the catalyst used in the ethylene carbonate reaction include alkali metal bromides or iodides (for example, those described in JP-B No. 23175), alkaline earth metal halides (for example, US Pat. No. 2,667). , 497), alkylamines, quaternary ammonium salts (for example, those described in US Pat. No. 2,773,070), organotins or germanium or tellurium compounds (for example, JP The one described in JP-A-57-183784) and halogenated organic phosphonium salts (for example, those described in JP-A-58-126884) may be appropriately selected and used.
- alkali metal bromides or iodides, or phosphonium salts are preferably used.
- Preferred examples include potassium iodide, potassium bromide, quaternary phosphonium iodide or quaternary phosphonium bromide, such as triphenylmethylphosphonium iodide, triphenylpropylphosphonium iodide, triphenylbenzylphosphonium iodide, tributylmethylphosphonium iodide. Id or bromide thereof.
- the compound which forms an alkali metal carbonate can also be used together with a phosphonium salt.
- Alkali metal carbonates are preferred because they suppress the formation of by-products other than ethylene glycol and ethylene carbonate in the carbonation reaction.
- a potassium salt having high solubility is preferable.
- a preferable example in the case of using a catalyst together is as described in JP-A-2000-128814.
- Ethylene oxide used as a raw material for the carbonation reaction of the present invention may be commercially available high-purity ethylene oxide, for example, Ullmanns Encyclopedia of Industrial Chemistry, 5thEd., VolA10, p117 and below.
- a gas composed mainly of ethylene and oxygen as raw materials and methane as a diluent gas is passed through a multi-tubular reactor filled with a silver catalyst to perform a reaction, For example, it can be purified and used as described below.
- the selectivity of ethylene to ethylene oxide is about 80%, and the remaining 20% is converted to carbon dioxide and water by a complete oxidation reaction.
- the oxidation reaction gas flowing out of the reactor is composed of generated ethylene oxide and unreacted ethylene, carbon dioxide gas, oxygen, dilution gas, and the like.
- the produced ethylene oxide is absorbed in the liquid phase by an absorption tower using water as an absorption liquid.
- the ethylene oxide absorbed in the absorption liquid is diffused in an ethylene oxide stripping tower, recovered as a high-concentration ethylene oxide aqueous solution from the top of the tower, and further subjected to dehydration purification in a distillation tower.
- an aqueous solution of high-concentration ethylene oxide obtained from the top of the tower as described above can be directly used as a raw material.
- Carbonation reaction can be performed using any apparatus.
- the reaction temperature is controlled by circulating the reaction liquid in the tower through the liquid circulation conduit using a bubble tower having a liquid circulation conduit equipped with a heat exchanger for heat removal and a circulation pump in the middle.
- the raw material ethylene oxide, carbon dioxide, and catalyst can be continuously supplied from the bottom of the column to continuously react. It is also preferable to use a reactor equipped with an ejector type nozzle as disclosed in JP-A-11-269110.
- the reaction temperature is usually 70 to 200 ° C, preferably 100 to 170 ° C.
- the reaction pressure is usually 0.6 to 5.0 MPa, but 1.0 to 3.0 MPa is preferable.
- Water may be added to the carbonation reaction of the present invention. In the presence of water, ethylene oxide is converted not only to ethylene carbonate but also to ethylene glycol. The reaction proceeds easily even with the supply amount.
- the molar ratio of carbon dioxide to ethylene oxide is 5 or less, preferably 0.5 to 3.0.
- the molar ratio of water to ethylene oxide is usually 10 or less, preferably 0.5 to 5.0.
- the addition amount of the catalyst is 1/1000 to 1/20, preferably 1/200 to 1/50 in molar ratio with respect to ethylene oxide.
- a part of the reaction solution obtained in the carbonation reaction is sent to a purification step of ethylene carbonate described later, and the rest is preferably subjected to a coloring component removal operation described later after performing a catalyst recovery operation described later.
- the catalyst recovery operation and the color component removal operation may be performed as separate operations.
- Examples of the catalyst recovery operation performed to prevent the deterioration of the catalyst include the methods described in JP-A-2004-262767, JP-A-2004-284976, JP-A-2004-292384, and the like.
- a crude ethylene carbonate crystal may be produced by cooling the carbonated reaction solution.
- a cooling method it can cool by a well-known method. Specifically, for example, as described in Japanese Patent Application Laid-Open No. 7-89905, a crystal is deposited on a cold vertical wall, and then heated to melt a part of the crystal and flow down. A method of recovering crystals having a higher purity by separating them can be used.
- a countercurrent contact method is also known (Japanese Patent Laid-Open No. 2007-284427 and British Patent No. 1086028, Separation Technology, Vol. 35, No. 6, pages 45 to 49 (2005). Etc.).
- the counter-current contact method is a method for increasing the purity of ethylene carbonate by bringing ethylene carbonate crystals into contact with a liquid.
- a solution containing the catalyst is extracted from the reaction solution, and 20 wt times or more of water is added to the catalyst dissolved in the extract solution to precipitate insoluble matter. Is removed from the extracted liquid to remove the colored component (this may be referred to as “colored component removing operation” in the present specification).
- the place for extracting the liquid containing the catalyst may be any place as long as it contains the circulating catalyst. For example, it is preferable to extract a part of the outlet liquid of the carbonation reactor.
- the amount to be withdrawn can be recirculated to the EC production process after removing the colored components, so long as the colored components are not concentrated in this process, but it is 1/500 to 1/5 of the carbonated reactor outlet liquid. The ratio is preferably 1/100 to 1/10.
- the amount of water added to the liquid containing the extracted catalyst needs to be added in an amount necessary for the coloring substance to precipitate, and is 20 times by weight or more, preferably 50 times by weight or more, relative to the contained catalyst. Most preferably, it is 60 weight times or more.
- the maximum amount when the amount of water contained in the process increases, it takes a lot of energy to finally remove the water, so 1000 weight times or less, preferably 200 weight times the catalyst amount contained. The following are appropriate.
- the above-described catalyst recovery operation and colored component removal operation can be continued.
- the catalyst is recovered from the liquid containing the extracted catalyst as described above, and the recovered catalyst is used as it is or dissolved in ethylene glycol as a liquid containing the catalyst. Can also be removed. The amount of water added at this time is the same as above.
- the catalyst concentration when the catalyst concentration is low, no special device is necessary.
- a solution containing the catalyst and a water pipe may be connected and mixed in the pipe.
- the catalyst concentration is as high as 40% by weight, for example, the catalyst is temporarily precipitated when water is added.
- a colored component is precipitated, which is separated and removed by an appropriate method.
- the separation and removal method may be any method such as stationary separation, filtration, and adsorption separation.
- stationary separation it is necessary to maintain the time necessary for the coloring components to precipitate, and the supernatant is recovered as a catalyst solution after preferably standing for 0.5 hour or longer, more preferably 1 hour or longer.
- an apparatus for the stationary separation for example, an apparatus in which an inlet pipe and an outlet pipe are installed at opposite positions in a normal container to reduce the flow velocity therein may be used as a precipitation tank.
- filtration separation it may be separated using a normal filtration device, but after adding water, the colored components gradually agglomerate, and filtration becomes easier. Therefore, preferably 5 minutes or more, more preferably 30 minutes. Filtration after holding the above is preferable from the viewpoint of filterability of the coloring component.
- a filtration device a commercially available filtration device may be used.
- adsorption separation may be performed using ordinary adsorbents such as activated carbon and zeolite, but glass wool, polypropylene wool, cotton, metal wool because the colored components easily physically adhere. A cotton-like material such as is preferable.
- an apparatus to be used specifically, for example, by passing a liquid containing a catalyst to which water has been added as described above through an adsorption tank filled with glass wool, it is possible to satisfactorily remove colored substances.
- the passage time is not particularly limited, but when the density of the adsorbent is low, it is necessary to slowly flow the liquid. However, if the adsorbent is densely packed, the adsorption treatment should be performed in a short time. I can do it. Although it may take time for the colored components to agglomerate before being supplied to the adsorption tank, an adsorption time of about 15 minutes to 3 hours is required in order to perform both adsorption and aggregation in the adsorption tank at the same time. Two effects are achieved by applying.
- the liquid containing the catalyst after removing the coloring components is circulated to the carbonation reaction of the EC production process.
- the position where the liquid containing the catalyst is returned may be anywhere as long as the catalyst is circulated, and examples thereof include an inlet of the carbonation reactor, an outlet of the carbonation reactor, a catalyst separation step, and the like.
- ethylene carbonate produced by the EC production process of the present invention is not colored and has high purity, it is preferably used as a raw material for non-aqueous electrolytes and the like. That there is no coloring specifically means that the Hazen number is 10 or less.
- the present invention also includes ethylene carbonate having a Hazen number of 10 or less and a purity of 99.999% or more, and a nonaqueous electrolytic solution containing the ethylene carbonate.
- the non-aqueous electrolyte solution of the present invention contains an electrolyte and a non-aqueous solvent that dissolves the electrolyte, as is the case with conventional non-aqueous electrolyte solutions. Manufactured by.
- Ethylene glycol production method Another aspect of the present invention is to react a carbon dioxide, ethylene oxide, and water in the presence of a catalyst to obtain a reaction liquid containing ethylene carbonate and ethylene glycol, and further add water to the reaction liquid.
- a process in this specification, this may be referred to as “EG production process”
- EG production process which includes a step (hydrolysis step) of converting ethylene carbonate to ethylene glycol by adding
- the liquid containing the catalyst is extracted from the liquid, and 20 weight times or more of water is added to the catalyst dissolved in the extracted liquid to precipitate the insoluble matter, and the precipitated insoluble matter is removed from the extracted liquid.
- a method for producing ethylene glycol characterized by being circulated.
- the colored component of ethylene carbonate removed in the ethylene carbonate production method is a cause of clogging in the hydrolysis step of the ethylene glycol production method.
- ethylene glycol can be produced stably over a long period of time.
- the step of reacting carbon dioxide, ethylene oxide, and water in the presence of a catalyst to produce ethylene carbonate and ethylene glycol is the same as the EC production process.
- the carbonated reaction solution is supplied to the hydrolysis step, from which part of the ethylene carbonate can be separated and purified by an appropriate method.
- the purification method of ethylene carbonate is not limited to the above-described crystallization method, and a known distillation method or the like can also be used. Naturally, when purified by the above crystallization method, high-purity ethylene carbonate without coloring can be obtained.
- the hydrolysis step it is advantageous to carry out the reaction at a high temperature from the viewpoint of the reaction rate. However, if the temperature is too high, the quality of ethylene glycol may be deteriorated.
- the reaction pressure is arbitrary as long as it is in the range up to the boiling point of the liquid, but it is usually preferable to carry out at normal pressure to 2.1 MPa. Also, as the hydrolysis proceeds, the reaction temperature is raised or the reaction pressure is lowered. It is also preferable to promote hydrolysis. Specifically, for example, the methods described in JP-A-59-13741 and JP-A-2000-128814 can be used, such as the amount of raw material and water added.
- Ethylene glycol produced by hydrolysis can be obtained by a known method. Usually, after separating water by distillation, preferably distillation under reduced pressure to obtain crude ethylene glycol composed of ethylene glycol, diethylene glycol, other high-boiling components and carbonated catalyst, etc., the catalyst and ethylene glycol are separated. In addition, it is supplied to an evaporator, and a large part of ethylene glycol and a part of high-boiling components are evaporated and recovered, and a residual liquid consisting of a catalyst and the remaining ethylene glycol, high-boiling components is obtained. The liquid "is supplied to the carbonation reaction.
- This catalyst recovery step is also performed under reduced pressure in order to promote evaporation of ethylene glycol and high-boiling components.
- an evaporation apparatus an apparatus equipped with a reboiler is used to replenish energy required for evaporation and control the evaporation amount.
- the liquid containing the catalyst in the reaction liquid is extracted, and 20 wt times or more of water is added to the catalyst dissolved in the extracted liquid to precipitate insoluble matter. After the minute is removed from the extract, it is recycled to the process again.
- the catalyst-containing liquid may be any liquid as long as it contains the catalyst in the EG production process, but preferably, the outlet liquid of the carbonation reactor, the reaction liquid of the hydrolysis step, etc. are preferably used. It is done.
- the catalyst recovered in the catalyst recovery step is further subjected to a catalyst recovery operation to prevent deterioration of the catalyst, and a solution obtained by dissolving the recovered catalyst in ethylene glycol or the like is used as a liquid containing the catalyst. It can also be used. Also in this case, examples of the position for returning the circulating liquid include a carbonation reactor and a hydrolysis reactor.
- EG ethylene glycol
- a part of the reaction solution obtained by the carbonation reaction is cooled to 17 ° C. by a crystallization apparatus with a cooling jacket described in JP-A-6-91103 to produce a slurry containing ethylene carbonate crystals. It was supplied from the crystal supply tube of the analyzing apparatus. The crystals settled in the crystallizer, and the excess mother liquor was recovered as an overflow from the top of the crystallizer and circulated to the hydrolysis reactor.
- the crystals settled and the crystals deposited on the bottom of the tower were heated with a heater to melt the crystals to form a melt.
- the molten liquid first rose while coming into contact with the precipitated crystals as a reflux liquid in countercurrent, extracted from the upper extraction tube, and returned to the hydrolysis reaction via the crystallizer.
- ethylene carbonate was not extracted from the product extraction tube, and a crystal deposition layer was formed on the melt.
- the thickness of the crystal deposition layer was confirmed from the viewing window, and the extraction amount from the product extraction tube was adjusted so that the thickness of the crystal deposition layer was 95% of the crystallizer.
- the quality of the product ethylene carbonate was evaluated using a gas chromatograph and a Karl Fischer moisture meter.
- the ethylene glycol concentration in the product was 1 ppm, and the water content was 2 ppm. . That is, the purity of the product ethylene carbonate was 99.999% or more.
- the hue was 10 or less in terms of Hazen number (APHA).
- Comparative Example 1 Ethylene carbonate was produced in the same manner as in Example 1 except that the reaction solution obtained from the carbonated reaction was taken out and the step of removing water by adding water was not performed. After one year of operation, the product ethylene carbonate obtained had the same ethylene glycol concentration and water content as in Example 1, but the hue was slightly reddish, and the color intensity was set to the Hazen number ( APHA) was about 25.
- Examples 2 to 6 In the step of extracting the reaction solution obtained from the above carbonation reaction and removing the precipitate by adding water, the same as in Example 1 except that the amount of water to be added and the method for removing insoluble components were changed. The process of removing the insoluble component which precipitated was performed. The results are shown in Table 1. As is clear from Table 1, when the amount of water added to the liquid containing the catalyst is 20 times the weight of the catalyst, the liquid after removing the insoluble components from the liquid containing the catalyst is colored. I could't see it.
- Comparative Example 2 In the step of extracting the reaction liquid obtained from the carbonate reaction and removing the precipitate by adding water, the amount of water to be added is 10 times the catalyst amount, and a method for removing insoluble components The step of removing the insoluble components precipitated was carried out in the same manner as in Example 1 except that was changed to filtration. The results are shown in Table 1. As is clear from Table 1, when the amount of water added to the liquid containing the catalyst is 10 times the amount of the catalyst, the liquid after removing the insoluble components from the liquid containing the catalyst is not filtered. The coloring component was not removed.
- Example 7 Production Method of Ethylene Glycol
- the carbonation reaction is carried out in the same manner as in Example 1, and the above carbonated reaction solution is transferred to a second reactor having a residence time of 2 hours, a pressure of 0.5 MPa, and 150 ° C.
- the ethylene carbonate was hydrolyzed to obtain 66.5 parts by weight of an aqueous solution of ethylene glycol / Hr containing a catalyst.
- An adsorption tank filled with wool manufactured by DCM Japan Co., Ltd.
- the obtained reaction liquid of the hydrolysis reaction was distilled by distillation under reduced pressure at 140 ° C. and 80 torr at the bottom of the column to obtain a dehydrated liquid from the bottom of the column, which was further reduced by a vacuum evaporator operated at 140 ° C. and 60 torr. Most of the ethylene glycol was evaporated, and 13 parts by weight / hr of the catalyst solution in which the catalyst was concentrated was recovered from the bottom of the evaporator. The recovered catalyst liquid was recycled to the first reactor as a catalyst. The catalyst solution that was the color of vinegar at the start of operation did not show a significant change in the color of the catalyst solution after one year of continuous operation. In addition, the control valve at the outlet of the hydrolysis reactor was not blocked and stable operation was possible.
- Comparative Example 3 The operation was carried out for 1 year in the same manner as in Example 7 except that the carbonated reaction solution was extracted, water was added, and the precipitated insoluble components were removed, and then the circulation was not performed.
- the catalyst liquid which was the color of vinegar at the start of operation changed the color of the catalyst liquid to wine red after one year of continuous operation.
- the control valve at the outlet of the hydrolysis reactor was clogged, making stable operation difficult.
- Example 8 The hydrolysis reaction is performed in the same manner as in Example 7.
- the above-mentioned hydrolysis reactor outlet liquid is taken out, 60 weight times of water is added to the amount of catalyst in the solution, and the precipitated insoluble component is filtered with 5C filter paper. As a result of filtration, the turbidity was removed and an uncolored catalyst solution could be recovered.
- Example 9 The catalyst solution obtained by evaporating most of the ethylene glycol from the hydrolysis reaction solution and recovering 13 parts by weight / hr of the catalyst solution in which the catalyst was concentrated from the bottom of the evaporator was carried out in the same manner as in Example 7.
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Abstract
Description
蒸留法は、工業的に最も汎用的に実施されている精製方法である。しかしながら、エチレンカーボネートは沸点が246℃(常圧)と高いため、蒸留法によりエチレンカーボネートの精製を行うと、たとえ減圧で蒸留を行っても熱劣化が起こり、エチレンカーボネートがジオールや水分と反応して高分子量化しやすい。また、本発明者らが行った検討では、高分子量化したエチレンカーボネートの一部の結合が切れて、ジオールに戻ってしまうために、蒸留を行っても、エチレンカーボネート中にジオールが約100ppm残留してしまうことがわかった。また、蒸留法は、当該物質の蒸発潜熱分のエネルギーが必要な上に、還流比も大きくしなければならない。従って、顕熱除去による冷却のみで済む晶析法と比較して、消費エネルギーが非常に大きい。
これらの着色成分は、例えば触媒の回収のために、触媒を含む反応液を一部取得して、水を添加し、触媒を回収した後にプロセスへ循環させる方法(特許文献2及び3)によっては除去されず、プロセスに循環される触媒溶液に残存して連続運転をするにつれ濃縮されることが本発明者等の検討によりわかってきた。
(1)触媒の存在下、二酸化炭素とエチレンオキシドとを反応させてエチレンカーボネートを含む反応液を得、生成したエチレンカーボネートを晶析により精製する工程を含むエチレンカーボネートの製造方法において、前記反応液から触媒を含む液を抜き出し、抜き出し液中に溶解している触媒に対して20重量倍以上の水を加えて不溶分を析出させ、析出した不溶分を除去した後、前記反応液に循環させることを特徴とする、エチレンカーボネートの製造方法、
(2)触媒を含む液が、二酸化炭素とエチレンオキシドとを反応させてエチレンカーボネートを生成させる反応器の出口液の一部であることを特徴とする上記(1)に記載の方法、
(3)触媒の存在下、二酸化炭素とエチレンオキシド、及び水とを反応させてエチレンカーボネート及びエチレングリコールを含む反応液を得、該反応液にさらに水を加えてエチレンカーボネートをエチレングリコールに変換する工程を含むエチレングリコールの製造方法において、前記反応液から触媒を含む液を抜き出し、抜き出し液に溶解している触媒に対して20重量倍以上の水を加えて不溶分を析出させ、析出した不溶分を除去した後、前記反応液に循環させることを特徴とする、エチレングリコールの製造方法、
(4)触媒を含む液が、二酸化炭素とエチレンオキシド、及び水とを反応させてエチレンカーボネート及びエチレングリコールを生成させる反応器の出口液の一部及び/または該反応液に水を加えてエチレンカーボネートをエチレングリコールに変換する反応器の出口液の一部であることを特徴とする上記(3)に記載の方法、
(5)不溶分の除去が、静置分離又はろ過分離又は吸着物質による吸着除去によることを特徴とする上記(1)~(4)のいずれかに記載の方法、
(6)触媒が、4級ホスホニウムヨ-ダイド及び又はブロマイドであることを特徴とする上記(1)~(5)のいずれかに記載の方法、
(7)ハーゼンナンバー色が10以下でかつ純度が99.999%以上であるエチレンカーボネート、
(8)上記(7)に記載のエチレンカーボネートを含むことを特徴とする非水系電解液、
である。
本発明のエチレングリコールの製造方法で除去しようとするエチレンカーボネート中の着色成分は、紫外線を当てると蛍光を発する物質である。触媒の存在下、二酸化炭素とエチレンオキシドとを反応させてエチレンカーボネートを生成させ、生成したエチレンカーボネートを晶析により精製する工程を含む本発明のエチレンカーボネート製造プロセスにおいて蛍光分析によりその存在の由来をたどると、原料のエチレンオキシドを製造するための酸化反応器の出口ガスのドレン中にすでに存在し、その後のエチレンオキシド吸収塔、エチレンオキシド放散塔を経由して、本発明のEC製造プロセスの原料であるエチレンオキシド中にも含まれている。また、EC製造プロセスおいては、この着色成分は触媒と共に該プロセスに循環されて濃縮される。
この着色成分は構造解析の結果、ポリエチレングリコール、ポリエチレン、芳香族からなる成分で構成されている。また、着色成分はメタノールなどの極性溶媒に可溶であるが、水に対する溶解性が低い為、ある程度の水を添加すると、析出・除去できる物質である。
本発明のエチレンカーボネート製造方法は、触媒の存在下、二酸化炭素とエチレンオキシドとを反応させてエチレンカーボネートを生成させ(本明細書中では、これを「カーボネート化反応」と称することがある)、生成したエチレンカーボネートを晶析により精製する工程を含むプロセスによるものである。
なかでも、アルカリ金属の臭化物またはヨウ化物、あるいはホスホニウム塩を用いるのが好ましい。好ましい例として、ヨウ化カリウム、臭化カリウム、4級ホスホニウムヨーダイドあるいは4級ホスホニウムブロマイド、例えば、トリフェニルメチルホスホニウムヨーダイド、トリフェニルプロピルホスホニウムヨーダイド、トリフェニルベンジルホスホニウムヨーダイド、トリブチルメチルホスホニウムヨーダイドあるいはこれらのブロマイド等が挙げられる。また、ホスホニウム塩にアルカリ金属炭酸塩を形成する化合物を併用することもできる。アルカリ金属炭酸塩はカーボネート化反応においてエチレングリコール、エチレンカーボネート以外の副生物が生成するのを抑制するので好ましい。アルカリ金属としては、溶解度の大きいカリウム塩が好ましい。触媒を併用する場合の好ましい例としては、特開2000-128814号公報に記載のとおりである。
水を添加した後、着色成分が析出してくるので、これを適当な方法で分離除去する。具体的には、分離除去方法は、静置分離、濾過、吸着分離等のいずれの方法でもよい。静置分離の場合は、着色成分が沈澱するのに必要な時間保持する必要があり、好ましくは0.5時間以上、更に好ましくは1時間以上静置した後に、上澄みを触媒溶液として回収する。静置分離する場合の装置は、例えば、通常の容器に入り口配管と出口配管を反対の位置に設置し中での流速を小さくする装置を沈殿槽として用いればよい。
また、吸着分離は、通常の活性炭やゼオライトといった吸着剤を使用してもかまわないが、着色成分が容易に物理的に付着する性質を持っていることから、グラスウール、ポリプロウール、綿、金属ウール等の綿状の物が好ましい。用いる装置として、具体的には、例えば、グラスウールが充填された吸着槽に、上記の様に水を添加した触媒を含む液を通過させることにより良好に着色物の除去が出来る。
本発明の別の態様は、触媒の存在下、二酸化炭素とエチレンオキシド、及び水とを反応させてエチレンカーボネート及びエチレングリコールを含む反応液を得、該反応液にさらに水を加えてエチレンカーボネートをエチレングリコールに変換する工程(加水分解工程)を含むプロセス(本明細書中では、これを「EG製造プロセス」と称することがある)によるエチレングリコールの製造方法において、前記反応液から触媒を含む液を抜き出し、抜き出し液に溶解している触媒に対して20重量倍以上の水を加えて不溶分を析出させ、析出した不溶分を抜き出し液から除去した後、前記プロセスに循環させることを特徴とする、エチレングリコールの製造方法である。上記エチレンカーボネートの製造方法において除去したエチレンカーボネートの着色成分は、一方で、上記エチレングリコール製造方法の加水分解工程において閉塞を生じさせる原因となっているため、これを同様の方法で除去することにより、長期安定的にエチレングリコールの製造を行うことができる。
(1)カーボネート化反応
二酸化炭素で2.0MPaで加圧された滞留時間1時間、100℃の第1反応器にトリブチルメチルホスホニウムヨーダイド5重量部/Hr、炭酸カリウム0.8重量部/Hr、原料エチレンオキシド水溶液(60重量%)78重量部/Hrを供給することによりエチレンカーボネート及びエチレングリコール(EG)を含むカーボネート化反応液を得た。得られた反応液を3重量部/Hrで抜き出し、含有される触媒量に対し60重量倍の水を添加し、SV=1でポリプロピレン製のウール(DCM japan株式会社製)が充填された吸着槽を通過させた。通過した触媒溶液の色は薄い黄色い色であった。この液を、カーボネート化反応器に循環使用した。
(2)エチレンカーボネートの精製
上記運転を1ヶ月継続後、カーボネート化反応液からWO2007/108213号公報に記載の方法に従ってエチレンカーボネートを晶析精製した。具体的には、晶析装置として特開平6-91103号公報に記載の縦型の溶融精製装置を使用した。精製装置は攪拌装置を備え、攪拌装置についている攪拌翼として、水平の攪拌棒を有する攪拌軸を使用した。また、晶析装置の側面には結晶の堆積を確認するためのスリット状の覗き窓を設置したものを用いた。
この時点では製品抜き出し管からエチレンカーボネートを抜き出さず、溶融液の上に結晶の堆積層を形成させた。そして、結晶の堆積層の厚みを覗き窓から確認し、結晶の堆積層の厚みを晶析装置の95%の高さになるように、製品抜き出し管からの抜き出し量を調整した。
上記カーボネート化反応から得られた反応液を抜き出し、水を添加して析出物を除去する工程を行わなかったこと以外は、実施例1と同様にしてエチレンカーボネートを製造した。1年間の運転の後、得られた製品エチレンカーボネートは、エチレングリコール濃度及び水の含有量は実施例1と変わらなかったが、色相が少し赤みを帯びており、色の濃さをハーゼンナンバー(APHA)で表すと約25であった。
上記カーボネート化反応から得られた反応液を抜き出し、水を添加して析出物を除去する工程において、添加する水の量、及び不溶成分の除去方法を変えたこと以外は、実施例1と同様にして析出する不溶成分を除去する工程を行った。この結果を表1に示す。表1から明らかなように、触媒を含む液に添加した水の量が、触媒量に対して20重量倍である場合には、触媒を含む液から不溶成分を除去した後の液は着色は見られなかった。
上記カーボネート化反応から得られた反応液を抜き出し、水を添加して析出物を除去する工程において、添加する水の量を触媒量に対して10重量倍としたこと、及び不溶成分の除去方法をろ過に変えたこと以外は、実施例1と同様にして析出する不溶成分を除去する工程を行った。この結果を表1に示す。表1から明らかなように、触媒を含む液に添加した水の量が、触媒量に対して10重量倍である場合には、触媒を含む液から不溶成分を除去した後の液はろ過前と変わらず、着色成分の除去がされなかった。
カーボネート化反応までは、実施例1と同様にして行い、上記カーボネート化反応液を滞留時間2時間、圧力0.5MPa、150℃の第2反応器に移して含有されるエチレンカーボネートを加水分解して、触媒を含有するエチレングリコールの水溶液66.5重量部/Hrを得た。このとき、第1反応器からカーボネート化反応液の一部を3重量部/Hrで、抜き出し、該溶液に含まれる触媒量に対し60重量倍の水を添加し、SV=1でポリプロピレン製のウール(DCM japan株式会社製)が充填された吸着槽を通過させ、通過液を、カーボネート化反応工程に循環使用した。
カーボネート化反応液を抜き出して水を添加し、析出した不溶成分を除去した後に循環させることを行わないこと以外は実施例7と同様にして1年間運転を行った。運転開始時に食酢の色であった触媒液は、1年間の連続運転の後、触媒液の色はワインレッドに変わっていた。また、加水分解反応器の出口の調節弁に閉塞が起こり、安定した運転が困難となった。
加水分解反応までを実施例7と同様に行い、上記加水分解反応器出口液を抜き出し、該溶液中の触媒量に対し、水60重量倍を添加した後、析出した不溶成分を5Cのろ紙で濾過したところ、濁りが除去され、着色の無い触媒溶液が回収できた。
実施例9
加水分解反応液からエチレングリコールの大部分を蒸発させ、蒸発器底部より触媒が濃縮された触媒液を13重量部/Hrを回収するまでを実施例7と同様に行い、得られた触媒液に含有される触媒量に対し、180重量倍の水を添加したところ、元々ワインレッド色であった液が、濁り、析出した不溶成分を5Cのろ紙で濾過したところ、濁りが除去され、着色の無い触媒溶液が回収できた。また、ろ紙に付着した沈殿を、水で洗浄し、その後、メタノールで洗浄したところ、メタノールは濃いワインレッドに着色し、触媒溶液に含まれていた着色成分が分離された。
Claims (8)
- 触媒の存在下、二酸化炭素とエチレンオキシドとを反応させてエチレンカーボネートを含む反応液を得、生成したエチレンカーボネートを晶析により精製する工程を含むエチレンカーボネートの製造方法において、前記反応液から触媒を含む液を抜き出し、抜き出し液中に溶解している触媒に対して20重量倍以上の水を加えて不溶分を析出させ、析出した不溶分を除去した後、前記反応液に循環させることを特徴とする、エチレンカーボネートの製造方法。
- 触媒を含む液が、二酸化炭素とエチレンオキシドとを反応させてエチレンカーボネートを生成させる反応器の出口液の一部であることを特徴とする請求項1に記載の方法。
- 触媒の存在下、二酸化炭素とエチレンオキシド、及び水とを反応させてエチレンカーボネート及びエチレングリコールを含む反応液を得、該反応液にさらに水を加えてエチレンカーボネートをエチレングリコールに変換する工程を含むエチレングリコールの製造方法において、前記反応液から触媒を含む液を抜き出し、抜き出し液中に溶解している触媒に対して20重量倍以上の水を加えて不溶分を析出させ、析出した不溶分を除去した後、前記反応液に循環させることを特徴とする、エチレングリコールの製造方法。
- 触媒を含む液が、二酸化炭素とエチレンオキシド、及び水とを反応させてエチレンカーボネート及びエチレングリコールを生成させる反応器の出口液の一部及び/または該反応液に水を加えてエチレンカーボネートをエチレングリコールに変換する反応器の出口液の一部であることを特徴とする請求項3に記載の方法。
- 不溶分の除去が、静置分離又はろ過分離又は吸着物質による吸着除去によることを特徴とする請求項1~4のいずれかに記載の方法。
- 触媒が、4級ホスホニウムヨ-ダイド及び又はブロマイドであることを特徴とする請求項1~5のいずれかに記載の方法。
- ハーゼンナンバー色が10以下でかつ純度が99.999%以上であるエチレンカーボネート。
- 請求項7に記載のエチレンカーボネートを含むことを特徴とする非水系電解液。
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BR112012012895B1 (pt) | 2018-01-02 |
CN102656156B (zh) | 2014-03-12 |
TWI449690B (zh) | 2014-08-21 |
SG181079A1 (en) | 2012-07-30 |
KR20120086352A (ko) | 2012-08-02 |
KR101699575B1 (ko) | 2017-02-13 |
TW201139363A (en) | 2011-11-16 |
BR112012012895A2 (pt) | 2015-09-08 |
JP5660048B2 (ja) | 2015-01-28 |
CN102656156A (zh) | 2012-09-05 |
JPWO2011065528A1 (ja) | 2013-04-18 |
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