WO2022233341A1 - Method for purifying fluoroethylene carbonate and product obtained therefrom - Google Patents
Method for purifying fluoroethylene carbonate and product obtained therefrom Download PDFInfo
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- WO2022233341A1 WO2022233341A1 PCT/CN2022/098800 CN2022098800W WO2022233341A1 WO 2022233341 A1 WO2022233341 A1 WO 2022233341A1 CN 2022098800 W CN2022098800 W CN 2022098800W WO 2022233341 A1 WO2022233341 A1 WO 2022233341A1
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000000746 purification Methods 0.000 claims abstract description 20
- 239000012043 crude product Substances 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims description 38
- 230000008025 crystallization Effects 0.000 claims description 37
- 238000010992 reflux Methods 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 14
- 239000011552 falling film Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 abstract description 39
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000010413 mother solution Substances 0.000 abstract 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 2
- 238000001640 fractional crystallisation Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C07D317/42—Halogen atoms or nitro radicals
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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
Definitions
- the application belongs to the technical field of preparation of electronic-grade reagents, and in particular relates to a purification method of fluoroethylene carbonate and a product obtained therefrom.
- Fluorinated ethylene carbonate is an important electrolyte film-forming additive for lithium-ion batteries, which can decompose in preference to other components of the electrolyte, forming a stable and continuous solid electrolyte interface film (SEI (solid electrolyte interface) at the electrode/electrolyte interface. interphase) membrane).
- SEI solid electrolyte interface
- the membrane has a small impedance, can effectively inhibit the decomposition of other components of the electrolyte, and can significantly improve the specific capacity and cycle stability of the battery. Therefore, fluoroethylene carbonate has been widely used in the battery industry.
- Chinese patent application CN105801554A discloses "the purification method of high-purity fluoroethylene carbonate". After decolorization and water removal of crude fluoroethylene carbonate, distillation, dissolution and crystallization are carried out to obtain refined fluoroethylene carbonate. However, the above purification process is complicated and difficult to operate.
- the present application provides a method for purifying fluoroethylene carbonate and a product obtained therefrom.
- a purification method of fluoroethylene carbonate comprising the steps:
- the fluoroethylene carbonate crude product is subjected to pressure crystallization to obtain crystallized and uncrystallized mother liquors;
- the crystals are successively dissolved and deweighted to obtain deweighted components
- the uncrystallized mother liquor is delighted to obtain delighted components
- the pressure during the pressurized crystallization is 1.5-5Mpa, and the temperature is 10-35°C.
- the melting method is reduced pressure melting, and the pressure of the reduced pressure melting is 0.05-0.1 MPa.
- the operating temperature during deweighting is 80-110° C.
- the pressure is 0.01-0.05 MPa
- the reflux ratio is 3-5.
- the operating temperature during delighting is 40-70° C.
- the pressure is 0.01-0.05 MPa
- the reflux ratio is controlled to 4-9.
- the mixed solution is crystallized by means of falling film crystallization.
- the temperature of the falling film crystallization is -10 ⁇ 10° C.
- the pressure is 0.001 ⁇ 0.02 MPa.
- the present application provides a fluoroethylene carbonate, which is prepared by the purification method described in the above scheme.
- the purity of the fluoroethylene carbonate is above 99.97%.
- the method for purifying fluoroethylene carbonate provided in the examples of the present application does not need to introduce a third-party organic solvent, reduces process procedures and costs, and reduces environmental pollution.
- the pressurized crystallization process in the examples of the present application enables the product to be crystallized at a relatively high temperature, with low energy consumption, and simultaneously only requires a depressurization operation to cause the crystals to sweat and melt, thereby further effectively reducing energy consumption.
- the heavy components and the light components in the product are separated through the crystallization process, and enter into the weight-removing tower and the light-removing tower respectively, so as to effectively improve the rectification purification efficiency and product purity.
- Fig. 1 is the purification process flow diagram of the fluoroethylene carbonate provided by the embodiment of the application.
- the embodiments of the present application provide a method for purifying fluoroethylene carbonate, comprising the following steps:
- the fluoroethylene carbonate crude product is subjected to pressure crystallization to obtain crystallized and uncrystallized mother liquors;
- the crystals are successively dissolved and deweighted to obtain deweighted components
- the uncrystallized mother liquor is delighted to obtain delighted components
- the pressure during the pressurized crystallization is 1.5-5Mpa, and the temperature is 10-35°C.
- the crude fluoroethylene carbonate is subjected to pressure crystallization to obtain crystallized and uncrystallized mother liquors.
- the pressure during the pressurized crystallization is 1.5-5Mpa, preferably 3-4Mpa, and the temperature is 10-35°C, preferably 15-30°C.
- the present application sequentially dissolves and deweights the crystals to obtain a deweighted component; delights the uncrystallized mother liquor to obtain a deweighted component.
- the melting method is preferably reduced pressure melting, and the pressure of the reduced pressure melting is preferably 0.05-0.1 MPa.
- the operating temperature during deweighting is preferably 80-110°C, more preferably 90-100°C; the pressure during deweighting is preferably 0.01-0.05MPa, more preferably 0.03- 0.045Mpa, the reflux ratio is preferably 3 to 5, more preferably 4.
- the operating temperature during the de-lighting is preferably 40-70° C., more preferably 55-65° C.; the pressure during the de-lighting is preferably 0.01-0.05 MPa, more preferably 0.03- 0.04Mpa, the reflux ratio is preferably 4-9, more preferably 5-7.
- the deweighted component and the delighted component are obtained, in the examples of the present application, the deweighted component and the delighted component are mixed, and the obtained mixed solution is crystallized to obtain purified fluoroethylene carbonate.
- the temperature of the falling film crystallization is preferably -10-10° C., more preferably 0-5° C.
- the pressure is preferably 0.001-0.02 Mpa, more preferably 0.005-0.01 Mpa.
- the method for purifying fluoroethylene carbonate provided in the examples of the present application adopts a pressurized method for crystallization, which can be crystallized at a relatively high temperature, has low energy consumption, does not need to introduce a third-party solvent, reduces process procedures and costs, and reduces environment Pollution. At the same time, only the depressurization operation can make the crystal sweat and melt, which further effectively reduces energy consumption.
- the crystallized product is then separated from heavy components and light components, and then enters the weight-removing tower and the light-removing tower respectively, which effectively improves the efficiency of rectification and purification and the purity of the product.
- Figure 1 it is a process flow diagram of the purification process of the fluoroethylene carbonate in the embodiment of the application.
- the embodiment of the present application also provides a fluoroethylene carbonate, which is prepared by the purification method described in the above embodiment.
- the purity of the fluoroethylene carbonate is above 99.97%.
- Fluorinated ethylene carbonate crude product (purity of fluorinated ethylene carbonate crude product is 90%) is sent into the pressurized crystallization process, the control pressure is 4MPa, the crystallization temperature is 30 ° C, and the crystallization product A, mother liquor B are obtained ;
- the mother liquor B is sent to the light-removing tower, and the operating temperature in the control tower is 40 ° C, the pressure is 0.01 MPa, and the reflux ratio is 6, and the light component is removed to obtain the product D;
- Fluorinated ethylene carbonate crude product (purity of fluorinated ethylene carbonate crude product is 89%) is sent into pressurized crystallization process, control pressure is 4MPa, crystallization temperature is 30 °C, obtain crystallization product A, mother liquor B ;
- the mother liquor B is sent into the light-removing tower, and the operating temperature in the control tower is 40 ° C, the pressure is 0.03 MPa, and the reflux ratio is 5, and the light component is removed to obtain the product D;
- fluorinated ethylene carbonate crude product (purity of fluorinated ethylene carbonate crude product is 93%) is sent into pressurized crystallization process, control pressure is 3MPa, crystallization temperature is 20 °C, obtain crystallization product A, mother liquor B ;
- fluorinated ethylene carbonate crude product (purity of fluorinated ethylene carbonate crude product is 93%) is sent into pressurized crystallization process, control pressure is 3MPa, crystallization temperature is 20 °C, obtain crystallization product A, mother liquor B ;
- the crude product of fluoroethylene carbonate (the purity of the crude product of fluoroethylene carbonate is 95%) is sent to the pressurized crystallization process, the control pressure is 3MPa, and the crystallization temperature is 15° C. to obtain crystalline product A and mother liquor B ;
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Abstract
Provided in the present application are a method for purifying fluoroethylene carbonate and a product obtained therefrom, which belong to the technical field of preparation of electronic-grade reagents. The purification method comprises the following steps: subjecting a crude product of fluoroethylene carbonate to piezocrystallization to obtain crystals and an uncrystallized mother solution; sequentially subjecting the crystals to melting and heavy component removal to obtain a heavy-component-removed component; subjecting the uncrystallized mother solution to light component removal to obtain a light-component-removed component; and mixing the heavy-component-removed component with the light-component-removed component, and crystallizing the resulting mixed solution to obtain purified fluoroethylene carbonate. The purification method provided in the present application has a simple process and a high efficiency, and can effectively reduce energy consumption and cost, and is green and environmentally friendly.
Description
本申请要求在2021年07月26日提交中国专利局、申请号为202110844035.3、申请名称为“一种氟代碳酸乙烯酯的纯化方法及其所得产品”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on July 26, 2021 with the application number of 202110844035.3 and the application title of "a method for purifying fluoroethylene carbonate and the products obtained therefrom", the entire contents of which are Incorporated herein by reference.
本申请属于电子级试剂的制备技术领域,尤其涉及一种氟代碳酸乙烯酯的纯化方法及其所得产品。The application belongs to the technical field of preparation of electronic-grade reagents, and in particular relates to a purification method of fluoroethylene carbonate and a product obtained therefrom.
氟代碳酸乙烯酯是一种重要的锂离子电池电解液成膜添加剂,能够优先于电解液其他组分分解,在电极/电解液界面处形成稳定且连续的固体电解质界面膜(SEI(solid electrolyte interphase)膜)。该膜具有较小的阻抗,且能够有效的抑制电解液其他组分分解,能明显的提升电池比容量和循环稳定性。因此,氟代碳酸乙烯酯已被广泛的应用于电池工业。Fluorinated ethylene carbonate is an important electrolyte film-forming additive for lithium-ion batteries, which can decompose in preference to other components of the electrolyte, forming a stable and continuous solid electrolyte interface film (SEI (solid electrolyte interface) at the electrode/electrolyte interface. interphase) membrane). The membrane has a small impedance, can effectively inhibit the decomposition of other components of the electrolyte, and can significantly improve the specific capacity and cycle stability of the battery. Therefore, fluoroethylene carbonate has been widely used in the battery industry.
然而,作为电解液添加剂,氟代碳酸乙烯酯的纯度要求为电子级。因此需要将氟代碳酸乙烯酯粗产品进行提纯精制才能满足使用要求。目前氟代碳酸乙烯酯提纯工艺主要为精馏-结晶法。如中国专利申请CN110878078A公开了“一种分级结晶制备电子级氟代碳酸乙烯酯的方法”将氟代碳酸乙烯酯粗产品精馏后得到不同纯度的馏分,然后将不同馏分进行分级结晶、干燥得到高纯度氟代碳酸乙烯酯。中国专利申请CN105801554A公开了“高纯度氟代碳酸乙烯酯的提纯方法”将氟代碳酸乙烯酯粗产品进行脱色、除水后,进行蒸馏、溶解、结晶工序获得精制氟代碳酸乙烯酯。然而以上提纯工艺工艺流程复杂,操作难度高。However, as an electrolyte additive, the purity of fluoroethylene carbonate is required to be electronic grade. Therefore, it is necessary to purify and refine the crude product of fluoroethylene carbonate to meet the requirements for use. At present, the purification process of fluoroethylene carbonate is mainly rectification-crystallization method. For example, Chinese patent application CN110878078A discloses "a method for preparing electronic grade fluoroethylene carbonate by fractional crystallization". After rectifying the crude product of fluoroethylene carbonate, fractions of different purities are obtained, and then different fractions are subjected to fractional crystallization and drying to obtain High-purity fluoroethylene carbonate. Chinese patent application CN105801554A discloses "the purification method of high-purity fluoroethylene carbonate". After decolorization and water removal of crude fluoroethylene carbonate, distillation, dissolution and crystallization are carried out to obtain refined fluoroethylene carbonate. However, the above purification process is complicated and difficult to operate.
发明内容SUMMARY OF THE INVENTION
本申请提供了一种氟代碳酸乙烯酯的纯化方法及其所得产品。The present application provides a method for purifying fluoroethylene carbonate and a product obtained therefrom.
为了达到上述目的,本申请采用的技术方案为:In order to achieve the above purpose, the technical scheme adopted in this application is:
一种氟代碳酸乙烯酯的纯化方法,包括如下步骤:A purification method of fluoroethylene carbonate, comprising the steps:
将氟代碳酸乙烯酯粗品进行加压结晶,得到结晶和未结晶母液;The fluoroethylene carbonate crude product is subjected to pressure crystallization to obtain crystallized and uncrystallized mother liquors;
将结晶依次进行溶化、脱重,得到脱重组分;The crystals are successively dissolved and deweighted to obtain deweighted components;
将未结晶母液进行脱轻,得到脱轻组分;The uncrystallized mother liquor is delighted to obtain delighted components;
将脱重组分和脱轻组分混合,将得到的混合液进行结晶,得到纯化后的氟代碳酸乙烯酯;Mixing the deweighting component and the delighting component, and crystallizing the obtained mixed solution to obtain purified fluoroethylene carbonate;
所述加压结晶时的压力为1.5~5Mpa,温度为10~35℃。The pressure during the pressurized crystallization is 1.5-5Mpa, and the temperature is 10-35°C.
在本申请一些实施例中,所述溶化的方式为降压溶化,所述降压溶化的压力为0.05~0.1MPa。In some embodiments of the present application, the melting method is reduced pressure melting, and the pressure of the reduced pressure melting is 0.05-0.1 MPa.
在本申请一些实施例中,所述脱重时的操作温度为80~110℃,压力为0.01~0.05MPa,回流比为3-5。In some embodiments of the present application, the operating temperature during deweighting is 80-110° C., the pressure is 0.01-0.05 MPa, and the reflux ratio is 3-5.
在本申请一些实施例中,所述脱轻时的操作温度为40~70℃,压力为0.01~0.05MPa,回流比控制4-9。In some embodiments of the present application, the operating temperature during delighting is 40-70° C., the pressure is 0.01-0.05 MPa, and the reflux ratio is controlled to 4-9.
在本申请一些实施例中,采用降膜结晶的方式对混合液进行结晶。In some embodiments of the present application, the mixed solution is crystallized by means of falling film crystallization.
在本申请一些实施例中,所述降膜结晶的温度为-10~10℃,压力为0.001~0.02MPa。In some embodiments of the present application, the temperature of the falling film crystallization is -10˜10° C., and the pressure is 0.001˜0.02 MPa.
本申请提供了一种氟代碳酸乙烯酯,由上述方案所述的纯化方法制备得到。The present application provides a fluoroethylene carbonate, which is prepared by the purification method described in the above scheme.
在本申请一些实施例中,所述氟代碳酸乙烯酯的纯度在99.97%以上。In some embodiments of the present application, the purity of the fluoroethylene carbonate is above 99.97%.
与现有技术相比,本申请的优点和积极效果在于:Compared with the prior art, the advantages and positive effects of the present application are:
(1)本申请实施例提供的氟代碳酸乙烯酯纯化方法无需引入第三方有机溶剂,降低过程工序及成本,减少环境污染。(1) The method for purifying fluoroethylene carbonate provided in the examples of the present application does not need to introduce a third-party organic solvent, reduces process procedures and costs, and reduces environmental pollution.
(2)本申请实施例中加压结晶工序使得产品能够较高温度下结晶,能耗小,同时只需降压操作即可使得晶体发汗、融化,进一步有效降低能耗。(2) The pressurized crystallization process in the examples of the present application enables the product to be crystallized at a relatively high temperature, with low energy consumption, and simultaneously only requires a depressurization operation to cause the crystals to sweat and melt, thereby further effectively reducing energy consumption.
(3)本申请实施例通过结晶工序将产品中重组分与轻组分分离,分别进入到脱重塔与脱轻塔,有效提升精馏提纯效率及产品纯度。(3) In the embodiment of the present application, the heavy components and the light components in the product are separated through the crystallization process, and enter into the weight-removing tower and the light-removing tower respectively, so as to effectively improve the rectification purification efficiency and product purity.
图1为本申请实施例所提供的氟代碳酸乙烯酯的提纯工艺流程图。Fig. 1 is the purification process flow diagram of the fluoroethylene carbonate provided by the embodiment of the application.
下面将对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本申请保护的范围。The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application.
本申请实施例提供了一种氟代碳酸乙烯酯的纯化方法,包括如下步骤:The embodiments of the present application provide a method for purifying fluoroethylene carbonate, comprising the following steps:
将氟代碳酸乙烯酯粗品进行加压结晶,得到结晶和未结晶母液;The fluoroethylene carbonate crude product is subjected to pressure crystallization to obtain crystallized and uncrystallized mother liquors;
将结晶依次进行溶化、脱重,得到脱重组分;The crystals are successively dissolved and deweighted to obtain deweighted components;
将未结晶母液进行脱轻,得到脱轻组分;The uncrystallized mother liquor is delighted to obtain delighted components;
将脱重组分和脱轻组分混合,将得到的混合液进行结晶,得到纯化后的氟代碳酸乙烯酯;Mixing the deweighting component and the delighting component, and crystallizing the obtained mixed solution to obtain purified fluoroethylene carbonate;
所述加压结晶时的压力为1.5~5Mpa,温度为10~35℃。The pressure during the pressurized crystallization is 1.5-5Mpa, and the temperature is 10-35°C.
本申请实施例将氟代碳酸乙烯酯粗品进行加压结晶,得到结晶和未结晶母液。在本申请实施例中,所述加压结晶时的压力为1.5~5Mpa,优选为 3~4Mpa,温度为10~35℃,优选为15~30℃。In the examples of the present application, the crude fluoroethylene carbonate is subjected to pressure crystallization to obtain crystallized and uncrystallized mother liquors. In the examples of the present application, the pressure during the pressurized crystallization is 1.5-5Mpa, preferably 3-4Mpa, and the temperature is 10-35°C, preferably 15-30°C.
得到结晶和未结晶母液后,本申请将所述结晶依次进行溶化、脱重,得到脱重组分;将未结晶母液进行脱轻,得到脱轻组分。在本申请一些实施例中,所述溶化的方式优选为降压溶化,所述降压溶化的压力优选为0.05~0.1MPa。在本申请一些实施例中,所述脱重时的操作温度优选为80~110℃,更优选为90~100℃;所述脱重时的压力优选为0.01-0.05MPa,更优选为0.03~0.045Mpa,回流比优选为3~5,更优选为4。After the crystallized and uncrystallized mother liquors are obtained, the present application sequentially dissolves and deweights the crystals to obtain a deweighted component; delights the uncrystallized mother liquor to obtain a deweighted component. In some embodiments of the present application, the melting method is preferably reduced pressure melting, and the pressure of the reduced pressure melting is preferably 0.05-0.1 MPa. In some embodiments of the present application, the operating temperature during deweighting is preferably 80-110°C, more preferably 90-100°C; the pressure during deweighting is preferably 0.01-0.05MPa, more preferably 0.03- 0.045Mpa, the reflux ratio is preferably 3 to 5, more preferably 4.
在本申请一些实施例中,所述脱轻时的操作温度优选为40~70℃,更优选为55~65℃;所述脱轻时的压力优选为0.01~0.05MPa,更优选为0.03~0.04Mpa,回流比优选为4~9,更优选为5~7。In some embodiments of the present application, the operating temperature during the de-lighting is preferably 40-70° C., more preferably 55-65° C.; the pressure during the de-lighting is preferably 0.01-0.05 MPa, more preferably 0.03- 0.04Mpa, the reflux ratio is preferably 4-9, more preferably 5-7.
得到脱重组分和脱轻组分后,本申请实施例将所述脱重组分和脱轻组分混合,将得到的混合液进行结晶,得到纯化后的氟代碳酸乙烯酯。在本申请中,优选采用降膜结晶的方式对混合液进行结晶。在本申请一些实施例中,所述降膜结晶的温度优选为-10~10℃,更优选为0~5℃,压力优选为0.001~0.02Mpa,更优选为0.005~0.01Mpa。After the deweighted component and the delighted component are obtained, in the examples of the present application, the deweighted component and the delighted component are mixed, and the obtained mixed solution is crystallized to obtain purified fluoroethylene carbonate. In the present application, it is preferable to crystallize the mixed solution by means of falling film crystallization. In some embodiments of the present application, the temperature of the falling film crystallization is preferably -10-10° C., more preferably 0-5° C., and the pressure is preferably 0.001-0.02 Mpa, more preferably 0.005-0.01 Mpa.
本申请实施例提供的氟代碳酸乙烯酯的纯化方法,采用加压的方式进行结晶,可以在较高温度下结晶,能耗小,且无需引入第三方溶剂,降低过程工序及成本,减少环境污染。同时只需降压操作即可使得晶体发汗、融化,进一步有效降低能耗。再将结晶后的产物进行重组分与轻组分分离,分别进入到脱重塔与脱轻塔,有效提升精馏提纯效率及产品纯度。如图1所示,为本申请实施例氟代碳酸乙烯酯的提纯工艺流程图。The method for purifying fluoroethylene carbonate provided in the examples of the present application adopts a pressurized method for crystallization, which can be crystallized at a relatively high temperature, has low energy consumption, does not need to introduce a third-party solvent, reduces process procedures and costs, and reduces environment Pollution. At the same time, only the depressurization operation can make the crystal sweat and melt, which further effectively reduces energy consumption. The crystallized product is then separated from heavy components and light components, and then enters the weight-removing tower and the light-removing tower respectively, which effectively improves the efficiency of rectification and purification and the purity of the product. As shown in Figure 1, it is a process flow diagram of the purification process of the fluoroethylene carbonate in the embodiment of the application.
本申请实施例还提供了一种氟代碳酸乙烯酯,由上述实施例所述的纯化方法制备得到。在本申请一些实施例中,所述氟代碳酸乙烯酯的纯度在 99.97%以上。The embodiment of the present application also provides a fluoroethylene carbonate, which is prepared by the purification method described in the above embodiment. In some embodiments of the present application, the purity of the fluoroethylene carbonate is above 99.97%.
为了进一步说明本申请,下面结合实施例对本申请提供的技术方案进行详细地描述,但不能将它们理解为对本申请保护范围的限定。In order to further illustrate the present application, the technical solutions provided by the present application are described in detail below with reference to the examples, but they should not be construed as limiting the protection scope of the present application.
实施例1Example 1
(1)将氟代碳酸乙烯酯粗产品(氟代碳酸乙烯酯粗产品的纯度为90%)送入加压结晶工序,控制压力为4MPa、结晶温度为30℃,获得结晶产品A、母液B;(1) Fluorinated ethylene carbonate crude product (purity of fluorinated ethylene carbonate crude product is 90%) is sent into the pressurized crystallization process, the control pressure is 4MPa, the crystallization temperature is 30 ° C, and the crystallization product A, mother liquor B are obtained ;
(2)将压力降压到0.1MPa,使得结晶产品A降压融化后送入到脱重塔,控制塔内操作温度90℃、压力0.02MPa、回流比3,脱出重组分获得产品C;(2) depressurizing the pressure to 0.1MPa, so that the crystalline product A is depressurized and melted and then sent to the weight-removing tower, and the operating temperature in the tower is controlled at 90° C., the pressure is 0.02MPa, and the reflux ratio is 3, and the heavy component is removed to obtain the product C;
(3)将母液B送入脱轻塔,控制塔内操作温度40℃、压力0.01MPa、回流比为6,脱出轻组分获得产品D;(3) the mother liquor B is sent to the light-removing tower, and the operating temperature in the control tower is 40 ° C, the pressure is 0.01 MPa, and the reflux ratio is 6, and the light component is removed to obtain the product D;
(4)将产品C与产品D混合,进入降膜结晶工序,控制温度10℃、压力0.01MPa,获得高纯度氟代碳酸乙烯酯,产品色谱纯度达99.97%。(4) Mixing product C and product D, entering the falling film crystallization process, and controlling the temperature to 10° C. and the pressure to 0.01 MPa to obtain high-purity fluoroethylene carbonate with a chromatographic purity of 99.97%.
实施例2Example 2
(1)将氟代碳酸乙烯酯粗产品(氟代碳酸乙烯酯粗产品的纯度为89%)送入加压结晶工序,控制压力为4MPa、结晶温度为30℃,获得结晶产品A、母液B;(1) Fluorinated ethylene carbonate crude product (purity of fluorinated ethylene carbonate crude product is 89%) is sent into pressurized crystallization process, control pressure is 4MPa, crystallization temperature is 30 ℃, obtain crystallization product A, mother liquor B ;
(2)将压力降压到0.07MPa,使得结晶产品A降压融化后送入到脱重塔,控制塔内操作温度85℃、压力0.03MPa,回流比4,脱出重组分获得产品C;(2) depressurize the pressure to 0.07MPa, make the crystalline product A depressurize and melt and then send it to the weight-removing tower, control the operating temperature in the tower at 85 ° C, the pressure at 0.03MPa, the reflux ratio of 4, and remove the heavy components to obtain product C;
(3)将母液B送入脱轻塔,控制塔内操作温度40℃、压力0.03MPa、回流比为5,脱出轻组分获得产品D;(3) the mother liquor B is sent into the light-removing tower, and the operating temperature in the control tower is 40 ° C, the pressure is 0.03 MPa, and the reflux ratio is 5, and the light component is removed to obtain the product D;
(4)将产品C与产品D混合,进入降膜结晶工序,控制温度0℃、压力 0.01MPa,获得高纯度氟代碳酸乙烯酯,产品色谱纯度达99.97%。(4) Mixing product C and product D, entering the falling film crystallization process, and controlling the temperature to 0°C and the pressure to 0.01MPa to obtain high-purity fluoroethylene carbonate with a chromatographic purity of 99.97%.
实施例3Example 3
(1)将氟代碳酸乙烯酯粗产品(氟代碳酸乙烯酯粗产品的纯度为93%)送入加压结晶工序,控制压力为3MPa、结晶温度为20℃,获得结晶产品A、母液B;(1) fluorinated ethylene carbonate crude product (purity of fluorinated ethylene carbonate crude product is 93%) is sent into pressurized crystallization process, control pressure is 3MPa, crystallization temperature is 20 ℃, obtain crystallization product A, mother liquor B ;
(2)将压力降压到0.1MPa,使得结晶产品A降压融化后送入到脱重塔,控制操作温度90℃、压力0.03MPa,回流比4,脱出重组分获得产品C;(2) depressurizing the pressure to 0.1MPa, so that the crystalline product A is depressurized and melted and then sent to the weight-removing tower, and the operating temperature is controlled to 90 ° C, the pressure is 0.03MPa, the reflux ratio is 4, and the heavy component is removed to obtain the product C;
(3)将母液B送入脱轻塔,控制操作温度55℃、压力0.01MPa、回流比为7,脱出轻组分获得产品D;(3) sending mother liquor B into light-removing tower, controlling operating temperature 55 ℃, pressure 0.01MPa, reflux ratio to be 7, and removing light components to obtain product D;
(4)将产品C与产品D混合,进入降膜结晶工序,控制温度5℃、压力0.003MPa,获得高纯度氟代碳酸乙烯酯,产品色谱纯度达99.98%。(4) Mixing product C and product D, entering the falling film crystallization process, and controlling the temperature to 5° C. and the pressure to 0.003 MPa to obtain high-purity fluoroethylene carbonate with a chromatographic purity of 99.98%.
实施例4Example 4
(1)将氟代碳酸乙烯酯粗产品(氟代碳酸乙烯酯粗产品的纯度为93%)送入加压结晶工序,控制压力为3MPa、结晶温度为20℃,获得结晶产品A、母液B;(1) fluorinated ethylene carbonate crude product (purity of fluorinated ethylene carbonate crude product is 93%) is sent into pressurized crystallization process, control pressure is 3MPa, crystallization temperature is 20 ℃, obtain crystallization product A, mother liquor B ;
(2)将压力降压到0.05MPa,使得结晶产品A降压融化后送入到脱重塔,控制操作温度95℃、压力0.03MPa,回流比5,脱出重组分获得产品C;(2) depressurize the pressure to 0.05MPa, so that the crystalline product A is depressurized and melted and then sent to the weight-removing tower, and the operating temperature is controlled at 95 ° C, the pressure is 0.03MPa, the reflux ratio is 5, and the heavy component is removed to obtain the product C;
(3)将母液B送入脱轻塔,控制操作温度70℃、压力0.04MPa、回流比为5,脱出轻组分获得产品D;(3) sending mother liquor B into light-removing tower, controlling operating temperature of 70 ° C, pressure of 0.04 MPa, and reflux ratio of 5, and removing light components to obtain product D;
(4)将产品C与产品D混合,进入降膜结晶工序,控制温度5℃、压力0.003MPa,获得高纯度氟代碳酸乙烯酯,产品色谱纯度达99.98%。(4) Mixing product C and product D, entering the falling film crystallization process, and controlling the temperature to 5° C. and the pressure to 0.003 MPa to obtain high-purity fluoroethylene carbonate with a chromatographic purity of 99.98%.
实施例5Example 5
(1)将氟代碳酸乙烯酯粗产品(氟代碳酸乙烯酯粗产品的纯度为95%) 送入加压结晶工序,控制压力为3MPa、结晶温度为15℃,获得结晶产品A、母液B;(1) The crude product of fluoroethylene carbonate (the purity of the crude product of fluoroethylene carbonate is 95%) is sent to the pressurized crystallization process, the control pressure is 3MPa, and the crystallization temperature is 15° C. to obtain crystalline product A and mother liquor B ;
(2)将压力降压到0.05MPa,使得结晶产品A降压融化后送入到脱重塔,控制操作温度95℃、压力0.04MPa,回流比5,脱出重组分获得产品C;(2) depressurizing the pressure to 0.05MPa, so that the crystalline product A is depressurized and melted and then sent to the weight-removing tower, and the operating temperature is controlled at 95 ° C, the pressure is 0.04MPa, the reflux ratio is 5, and the heavy component is removed to obtain the product C;
(3)将母液B送入脱轻塔,控制操作温度55℃、压力0.05MPa、回流比为7,脱出轻组分获得产品D;(3) sending mother liquor B into light-removing tower, controlling operating temperature 55 ℃, pressure 0.05MPa, reflux ratio to be 7, slough off light component and obtain product D;
(4)将产品C与产品D混合,进入降膜结晶工序,控制温度10℃、压力0.001MPa,获得高纯度氟代碳酸乙烯酯,产品色谱纯度达99.97%。(4) Mixing product C and product D, entering the falling film crystallization process, and controlling the temperature to 10° C. and the pressure to 0.001 MPa to obtain high-purity fluoroethylene carbonate with a chromatographic purity of 99.97%.
以上所述仅是本申请的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本申请原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本申请的保护范围。The above are only the preferred embodiments of the present application. It should be pointed out that for those skilled in the art, without departing from the principles of the present application, several improvements and modifications can also be made. It should be regarded as the protection scope of this application.
Claims (8)
- 一种氟代碳酸乙烯酯的纯化方法,其特征在于,包括如下步骤:A kind of purification method of fluoroethylene carbonate, is characterized in that, comprises the steps:将氟代碳酸乙烯酯粗品进行加压结晶,得到结晶和未结晶母液;The fluoroethylene carbonate crude product is subjected to pressure crystallization to obtain crystallized and uncrystallized mother liquors;将结晶依次进行溶化、脱重,得到脱重组分;The crystals are successively dissolved and deweighted to obtain deweighted components;将未结晶母液进行脱轻,得到脱轻组分;The uncrystallized mother liquor is delighted to obtain delighted components;将脱重组分和脱轻组分混合,将得到的混合液进行结晶,得到纯化后的氟代碳酸乙烯酯;Mixing the deweighting component and the delighting component, and crystallizing the obtained mixed solution to obtain purified fluoroethylene carbonate;所述加压结晶时的压力为1.5~5Mpa,温度为10~35℃。The pressure during the pressurized crystallization is 1.5-5Mpa, and the temperature is 10-35°C.
- 根据权利要求1所述的纯化方法,其特征在于,所述溶化的方式为降压溶化,所述降压溶化的压力为0.05~0.1MPa。The purification method according to claim 1, wherein the melting method is reduced pressure melting, and the pressure of the reduced pressure melting is 0.05-0.1 MPa.
- 根据权利要求1所述的纯化方法,其特征在于,所述脱重时的操作温度为80~110℃,压力为0.01~0.05MPa,回流比为3~5。The purification method according to claim 1, characterized in that, the operation temperature during the deweighting is 80-110°C, the pressure is 0.01-0.05MPa, and the reflux ratio is 3-5.
- 根据权利要求1所述的纯化方法,其特征在于,所述脱轻时的操作温度为40~70℃,压力为0.01~0.05MPa,回流比控制4~9。The purification method according to claim 1, characterized in that, the operating temperature during delighting is 40-70° C., the pressure is 0.01-0.05 MPa, and the reflux ratio is controlled at 4-9.
- 根据权利要求1所述的纯化方法,其特征在于,采用降膜结晶的方式对混合液进行结晶。The purification method according to claim 1, wherein the mixed solution is crystallized by means of falling film crystallization.
- 根据权利要求5所述的纯化方法,其特征在于,所述降膜结晶的温度为-10~10℃,压力为0.001~0.02MPa。The purification method according to claim 5, wherein the temperature of the falling film crystallization is -10-10°C, and the pressure is 0.001-0.02MPa.
- 一种氟代碳酸乙烯酯,其特征在于,由权利要求1~6任意一项所述的纯化方法制备得到。A fluoroethylene carbonate, characterized in that it is prepared by the purification method described in any one of claims 1 to 6.
- 根据权利要求7所述的氟代碳酸乙烯酯,其特征在于,所述氟代碳酸乙烯酯的纯度在99.97%以上。The fluoroethylene carbonate according to claim 7, wherein the purity of the fluoroethylene carbonate is above 99.97%.
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