CN116062777A - Production process for improving purity of fluoroethylene carbonate byproduct potassium chloride - Google Patents
Production process for improving purity of fluoroethylene carbonate byproduct potassium chloride Download PDFInfo
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- CN116062777A CN116062777A CN202310222608.8A CN202310222608A CN116062777A CN 116062777 A CN116062777 A CN 116062777A CN 202310222608 A CN202310222608 A CN 202310222608A CN 116062777 A CN116062777 A CN 116062777A
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- potassium chloride
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- fluoroethylene carbonate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention belongs to the technical field of chemical by-product recovery treatment, and particularly relates to a production process for improving the purity of fluoroethylene carbonate by-product potassium chloride, which comprises the following steps: s1, drying under reduced pressure; s2, adding water for dissolution; s3, salt solution filter pressing; s4, adjusting the PH; s5, oxidative decomposition; s6, adsorbing and decoloring; s7, precisely filtering; s8, mixing reaction: s9, filtering; s10, concentrating and crystallizing filtrate; s11, centrifuging; s12, drying. The method has the advantages of simple process, short flow, low investment and high efficiency, and can well solve the product quality problem of the byproduct potassium chloride in the fluoroethylene carbonate production process.
Description
Technical Field
The invention belongs to the technical field of chemical by-product recovery treatment, and particularly relates to a production process for improving the purity of fluoroethylene carbonate by-product potassium chloride.
Background
Fluoroethylene carbonate is used as a film forming additive of lithium ion battery electrolyte, and is popularized due to the application of flame retardant property. The method for producing fluoroethylene carbonate mainly comprises a fluorine gas direct fluorination method and a halogen exchange method, and for direct fluorination, the byproduct potassium chloride is brown or reddish brown due to the fact that the purification difficulty is high and the decolorization is not thorough because the byproduct potassium chloride contains fluorine-containing polymer and excessive KF in the production process, and the application of the potassium chloride is limited because the obtained byproduct potassium chloride (KCL) contains excessive impurities. The partial treatment technology has the advantages of complex process, long flow, large investment and low efficiency, and therefore, the expansion of the production scale of fluoroethylene carbonate is limited.
For the prior art, the invention patent application with publication number of CN114314611A mentions that the steam stripping technology is used for removing the fluorine-containing organic matter from the brine solution, and has the advantages of large equipment investment and high energy consumption; and then the fluosilicic acid is added, so that the treatment process is long and the efficiency is low.
The invention patent application with publication number of CN112300111A mentions that the potassium chloride is obtained by adopting strong alkali to decompose fluorocarbon and recrystallization, the performance is not high, the particle size of GaF2 generated under the condition that activated carbon adsorbs organic matters unstably and chlorine is too small, and the quality of KCL products is not high;
the invention patent with publication number of CN106006679B mentions that organic matters are decomposed by high-temperature treatment, then liquid ammonia and potassium fluoride are used for preparing potassium fluoride liquid ammonia solution, and then the solution is filtered and separated. The solvent regeneration treatment operation in the process is complex, and the economic benefit is poor.
The invention patent application publication No. CN111392732A mentions the use of quartz sand and fluosilicic acid treatment, and does not consider the problem of organofluorinated polymer side residues;
the invention patent publication No. CN102730710B mentions that the high temperature treatment is carried out firstly, and then boron trifluoride acetonitrile solution is used for reaction to generate potassium tetrafluoroborate, which does not consider the residue of organofluorine polymer; much KCL remains in KBF4 and BF3 is consumed with high efficiency.
Disclosure of Invention
The invention aims to provide a production process for improving the purity of fluoroethylene carbonate byproduct potassium chloride, so as to solve at least one problem in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions: a production process for improving the purity of fluoroethylene carbonate byproduct potassium chloride comprises the following steps:
s1, drying under reduced pressure: filtering fluoroethylene carbonate to produce solid waste, decompressing, heating and drying; the method comprises the steps of carrying out a first treatment on the surface of the
S2, adding water for dissolution: adding water into the dried filter residue (containing potassium chloride, potassium fluoride, carbonates, fluorine-containing polymer and polycarbonate), stirring and dissolving to obtain slurry;
s3, salt hydraulic filtration: performing plate-frame filter pressing on the slurry until the filtrate is colorless and transparent to remove carbonic acid esters, fluorine-containing polymers and polycarbonate substances;
s4, adjusting the PH: adding inorganic acid into the filtrate to enable the pH value of the filtrate to be 1-5;
s5, oxidative decomposition: adding a strong oxidant and a catalyst into the filtrate, heating and raising the temperature, and oxidizing the organic matters remained in the filtrate to decompose the organic matters into water, carbon dioxide and low-molecular fluoride;
s6, adsorption decolorization: performing adsorption removal by using activated carbon to enable the mixed solution in the step S5 to be in a colorless transparent state;
s7, precise filtration: removing the activated carbon in the decolored mixed solution through a filter;
s8, mixing reaction: adding calcium chloride into the mixed solution in the step S7, stirring to react the calcium chloride with potassium fluoride, and generating calcium fluoride precipitate:
2KF+CaCl 2 →2KCl+CaF 2 ↓；
s9, filtering: carrying out filter pressing treatment on the reacted mixed solution;
s10, concentrating and crystallizing the filtrate: the filtrate containing calcium chloride in the step S9 is sent into an MVR system for concentration and crystallization treatment, and a potassium chloride byproduct is obtained;
s11, centrifuging: centrifugally dewatering the concentrated solution, and returning water generated by centrifugation to an MVR system for treatment;
s12, drying: and (5) vacuumizing and drying under negative pressure to ensure that the water content reaches the index requirement, and finally obtaining the high-purity byproduct potassium chloride.
In the above technical scheme, in step S2, a vertical single-kettle dissolution kettle or a horizontal continuous dissolution kettle is used as a container for dissolving filter residues (including potassium chloride, potassium fluoride, carbonates, fluoropolymers and polycarbons).
In any of the above embodiments, in step S4, the inorganic acid is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, or hypochlorous acid.
In any of the above embodiments, further, in step S4, the PH of the filtrate is 2 to 5.
In any of the above technical solutions, in step S5, the strong oxidizing agent is hydrogen peroxide, sodium hypochlorite or bleaching powder.
In any of the above embodiments, further, in step S5, the temperature at which the filtrate is heated is controlled to be 40 to 80 ℃.
In any of the above embodiments, further, in step S7, the filter is a membrane filter.
In any of the above embodiments, further, in step S8, the added calcium chloride may be replaced with a hydroxide or oxide of calcium.
In any of the above embodiments, in step S8, the reaction end point PH of the mixed solution is 6 to 9.
In any of the above embodiments, further, the distilled water generated during step S10 is returned to the container in step S2 to be recycled.
The beneficial effects of the invention are as follows: the method has the advantages of simple process, short flow, low investment and high efficiency, and can well solve the product quality problem of the byproduct potassium chloride in the fluoroethylene carbonate production process.
Specifically, 1, the source of the related raw materials is wide, simple and easy to obtain; 2. the fluorine-containing organic matter can be decomposed and treated thoroughly; 3. the water is recycled; 4. the treatment process is relatively simple, and the comprehensive energy consumption is low; 5. the purity of the byproduct KCL can reach 99.95 percent, and the product is good in quality.
Drawings
FIG. 1 is a process flow diagram of the present invention;
Detailed Description
Technical solutions in the embodiments of the present application will be clearly described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some of the embodiments of the present application, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application are within the scope of the protection of the present application.
In the description of the present application, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. For ease of description, the dimensions of the various features shown in the drawings are not drawn to actual scale. Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further discussion thereof is necessary in subsequent figures.
It should be noted that, in this application, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. Furthermore, it should be noted that the scope of the methods and apparatus in the embodiments of the present application is not limited to performing the functions in the order shown or discussed, but may also include performing the functions in a substantially simultaneous manner or in an opposite order depending on the functions involved, e.g., the described methods may be performed in an order different from that described, and various steps may also be added, omitted, or combined. Additionally, features described with reference to certain examples may be combined in other examples.
Example 1:
the embodiment provides a production process for improving the purity of fluoroethylene carbonate byproduct potassium chloride, wherein the process comprises the following steps:
s1, drying under reduced pressure: filtering fluoroethylene carbonate to produce solid waste, decompressing, heating and drying; the solvent (DEC) and residual fluoroethylene carbonate (FEC) were recovered and reused after purification.
S2, adding water for dissolution: adding water into the dried filter residue (containing potassium chloride, potassium fluoride, carbonates, fluorine-containing polymer and polycarbonate), and stirring to dissolve into slurry. For the container, a vertical single-kettle dissolution kettle or a horizontal continuous dissolution kettle can be adopted to dissolve filter residues.
S3, salt hydraulic filtration: and carrying out plate-frame filter pressing on the slurry until the filtrate is colorless and transparent, so as to remove carbonic esters, fluorine-containing polymers and polycarbonate substances. And (5) burning the filter residues as waste solids.
S4, adjusting the PH: inorganic acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hypochlorous acid, etc. is added into the filtrate to make the pH value of the filtrate be 1-5. Optimally, the pH value of the filtrate is maintained in the range of 2-5.
S5, oxidative decomposition: adding a strong oxidant and a catalyst into the filtrate, heating and raising the temperature, and oxidizing the organic matters remained in the filtrate to decompose the organic matters into water, carbon dioxide and low-molecular fluoride, wherein the temperature of the filtrate to be heated is controlled to be 40-80 ℃. As the strong oxidizing agent, hydrogen peroxide, sodium hypochlorite or bleaching powder can be used.
S6, adsorption decolorization: and (5) performing adsorption removal by using activated carbon to enable the mixed solution in the step (S5) to be in a colorless transparent state.
S7, precise filtration: removing the activated carbon in the decolored mixed solution through a filter; wherein, the active carbon produced by the removal is used as waste solid for incineration treatment. Optimally, the filter can be a membrane filter, so that the energy consumption can be reduced.
S8, mixing reaction: adding calcium chloride into the mixed solution in the step S7, stirring to react the calcium chloride with potassium fluoride, and generating calcium fluoride precipitate:
2KF+CaCl 2 →2KCl+CaF 2 ↓
specifically, the pH value of the reaction end point of the mixed solution is required to be in the range of 6-9.
S9, filtering: and (3) carrying out filter pressing treatment on the reacted mixed solution, drying filter residue calcium fluoride, and treating the filter residue calcium fluoride as a byproduct.
S10, concentrating and crystallizing the filtrate: and (3) sending the filtrate containing calcium chloride in the S9 into an MVR system, concentrating, crystallizing and obtaining a potassium chloride byproduct. Wherein, distilled water generated during the step S10 can be returned to the container in the step S2, thereby realizing recycling and recycling, and the surplus water is treated as wastewater.
S11, centrifuging: the concentrate is centrifugally dehydrated, and water generated by centrifugation is returned to the MVR system for treatment.
S12, drying: and (5) vacuumizing and drying under negative pressure to ensure that the water content reaches the index requirement, and finally obtaining the high-purity byproduct potassium chloride.
Example 2:
this example provides a process for improving the purity of fluoroethylene carbonate byproduct potassium chloride, which differs from example 1 in that the reactant in S8 is replaced, specifically, the calcium chloride may be replaced with a hydroxide or oxide of calcium.
2KF+Ca(OH) 2 →2KOH+CaF 2 ↓
2KF+Ca0→K 2 O+CaF 2 ↓。
The embodiments of the present application and the features of the embodiments may be combined without conflict, and the present application is not limited to the specific embodiments described above, which are merely illustrative, not restrictive, and many forms may be made by those of ordinary skill in the art, without departing from the spirit of the present application and the scope of the claims, which are also within the protection of the present application.
Claims (10)
1. A production process for improving the purity of fluoroethylene carbonate byproduct potassium chloride is characterized by comprising the following steps:
s1, drying under reduced pressure: filtering fluoroethylene carbonate to produce solid waste, decompressing, heating and drying;
s2, adding water for dissolution: adding water into the dried filter residue (containing potassium chloride, potassium fluoride, carbonates, fluorine-containing polymer and polycarbonate), stirring and dissolving to obtain slurry;
s3, salt hydraulic filtration: performing plate-frame filter pressing on the slurry until the filtrate is colorless and transparent to remove carbonic acid esters, fluorine-containing polymers and polycarbonate substances;
s4, adjusting the PH: adding inorganic acid into the filtrate to enable the pH value of the filtrate to be 1-5;
s5, oxidative decomposition: adding a strong oxidant and a catalyst into the filtrate, heating and raising the temperature, and oxidizing the organic matters remained in the filtrate to decompose the organic matters into water, carbon dioxide and low-molecular fluoride;
s6, adsorption decolorization: performing adsorption removal by using activated carbon to enable the mixed solution in the step S5 to be in a colorless transparent state;
s7, precise filtration: removing the activated carbon in the decolored mixed solution through a filter;
s8, mixing reaction: adding calcium chloride into the mixed solution in the step S7, stirring to react the calcium chloride with potassium fluoride, and generating calcium fluoride precipitate:
2KF+CaCl 2 →2KCl+CaF 2 ↓；
s9, filtering: carrying out filter pressing treatment on the reacted mixed solution;
s10, concentrating and crystallizing the filtrate: the filtrate containing calcium chloride in the step S9 is sent into an MVR system for concentration and crystallization treatment, and a potassium chloride byproduct is obtained;
s11, centrifuging: centrifugally dewatering the concentrated solution, and returning water generated by centrifugation to an MVR system for treatment;
s12, drying: and (5) vacuumizing and drying under negative pressure to ensure that the water content reaches the index requirement, and finally obtaining the high-purity byproduct potassium chloride.
2. The process according to claim 1, wherein in step S2, a vertical single-vessel dissolution vessel or a horizontal continuous dissolution vessel is used as a vessel for dissolving filter residues (containing potassium chloride, potassium fluoride, carbonates, fluoropolymers, and polycarbolipids).
3. The process for improving the purity of fluoroethylene carbonate byproduct potassium chloride according to claim 1, wherein in step S4, the inorganic acid is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and hypochlorous acid.
4. A process for increasing the purity of fluoroethylene carbonate byproduct potassium chloride according to claim 1 or 3 wherein in step S4 the PH of the filtrate is between 2 and 5.
5. The process for improving the purity of fluoroethylene carbonate byproduct potassium chloride according to claim 1, wherein in step S5, the strong oxidizer is hydrogen peroxide, sodium hypochlorite or bleaching powder.
6. The process for improving the purity of fluoroethylene carbonate byproduct potassium chloride according to claim 1 or 5, wherein in step S5, the temperature of the filtrate is controlled to be 40-80 ℃.
7. The process for improving the purity of fluoroethylene carbonate byproduct potassium chloride according to claim 1, wherein in step S7, the filter is a membrane filter.
8. The process for improving the purity of potassium chloride as defined in claim 1, wherein in step S8, the added calcium chloride is replaced by a hydroxide or oxide of calcium.
9. The process for improving the purity of fluoroethylene carbonate byproduct potassium chloride according to claim 1 or 7, wherein in step S8, the reaction end point PH of the mixed solution is 6 to 9.
10. The process for improving the purity of potassium chloride as defined in claim 1, wherein the distilled water produced during step S10 is returned to the vessel in step S2 for recycling.
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| CN101928017A (en) * | 2009-06-23 | 2010-12-29 | 西南科技大学 | Method for producing potassium chloride by utilizing potassium-bearing waste residues from pesticide plants |
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| CN214734576U (en) * | 2020-12-08 | 2021-11-16 | 江苏瀚康新材料有限公司 | Utilize apparatus for producing of oxidability tail gas promotion by-product potassium chloride quality |
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| CN114804158A (en) * | 2022-04-01 | 2022-07-29 | 浙江大洋生物科技集团股份有限公司 | Method for producing high-purity potassium carbonate by using fly ash washing byproduct potassium chloride |
| CN115108568A (en) * | 2022-04-01 | 2022-09-27 | 浙江大洋生物科技集团股份有限公司 | Method for preparing potassium carbonate from fly ash washing byproduct potassium chloride |
| CN115321558A (en) * | 2022-03-31 | 2022-11-11 | 浙江大洋生物科技集团股份有限公司 | Purification and comprehensive utilization method of fly ash washing byproduct potassium chloride |
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2023
- 2023-03-02 CN CN202310222608.8A patent/CN116062777A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928017A (en) * | 2009-06-23 | 2010-12-29 | 西南科技大学 | Method for producing potassium chloride by utilizing potassium-bearing waste residues from pesticide plants |
| CN110775990A (en) * | 2019-10-27 | 2020-02-11 | 淮安瀚康新材料有限公司 | Method for treating fluoroethylene carbonate solid waste |
| CN112300111A (en) * | 2020-11-10 | 2021-02-02 | 湖北省宏源药业科技股份有限公司 | Method for treating fluoroethylene carbonate solid slag |
| CN214734576U (en) * | 2020-12-08 | 2021-11-16 | 江苏瀚康新材料有限公司 | Utilize apparatus for producing of oxidability tail gas promotion by-product potassium chloride quality |
| CN113479891A (en) * | 2021-07-02 | 2021-10-08 | 多氟多新材料股份有限公司 | Method for treating fluoroethylene carbonate solid waste residue |
| CN114314611A (en) * | 2021-12-16 | 2022-04-12 | 泰兴华盛精细化工有限公司 | Method for recycling salt generated after fluorination reaction of fluoroethylene carbonate |
| CN115321558A (en) * | 2022-03-31 | 2022-11-11 | 浙江大洋生物科技集团股份有限公司 | Purification and comprehensive utilization method of fly ash washing byproduct potassium chloride |
| CN114804158A (en) * | 2022-04-01 | 2022-07-29 | 浙江大洋生物科技集团股份有限公司 | Method for producing high-purity potassium carbonate by using fly ash washing byproduct potassium chloride |
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