CN114314611A - Method for recycling salt generated after fluorination reaction of fluoroethylene carbonate - Google Patents
Method for recycling salt generated after fluorination reaction of fluoroethylene carbonate Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims abstract description 31
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title claims abstract description 17
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 123
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 79
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 62
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 48
- 239000001103 potassium chloride Substances 0.000 claims abstract description 38
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 38
- 238000001816 cooling Methods 0.000 claims abstract description 25
- 238000001694 spray drying Methods 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000004821 distillation Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 76
- 239000000706 filtrate Substances 0.000 claims description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000001704 evaporation Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 2
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004334 fluoridation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- -1 potassium fluorosilicate Chemical compound 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The invention discloses a method for recycling salt after fluorination reaction of fluoroethylene carbonate, relates to a chemical recycling technology, and aims to solve the problems that potassium fluoride is excessively used to improve the conversion rate of chloroethylene carbonate, potassium chloride salt and potassium fluoride after the reaction are difficult to separate, and fluorine-containing salt is difficult to treat, and the technical scheme is characterized in that: the method comprises the following steps: dissolving and stirring; step two: filtering; step three: steam stripping and distillation; step four: cooling and dripping fluorosilicic acid solution; step five, concentrating and dehydrating; step six, adding potassium hydroxide and stirring; step seven: secondary concentration; step eight: and (5) spray drying. The method can separate potassium fluoride and potassium chloride after fluorination of fluoroethylene carbonate, and recover the potassium fluoride, so that the excessive potassium fluoride in the reaction process can be continuously used in the subsequent reaction process, the waste of resources is avoided, and the influence on the environment caused by random discharge of the potassium fluoride is also prevented.
Description
Technical Field
The invention relates to a chemical recovery technology, in particular to a method for recycling salt generated after fluorination of fluoroethylene carbonate.
Background
The fluoroethylene carbonate is a chemical substance, is a main lithium ion battery electrolyte additive, has better performance of forming an SEI film, forms a compact structure layer without increasing impedance, can prevent the electrolyte from being further decomposed, and improves the low-temperature performance of the electrolyte.
When fluoroethylene carbonate is synthesized, anhydrous potassium fluoride and fluoroethylene carbonate (a purified product) are put into a flask according to a certain proportion, a certain amount of aprotic solvent is added, after nitrogen is introduced for ten minutes, the temperature is raised to the reaction temperature, after reaction for a certain time, the reactants are filtered, a filter cake is washed by ethyl acetate, combined filtrates are collected, reduced pressure distillation is firstly carried out by a water ring vacuum pump under low vacuum (3000 plus 6000Pa) to recover the solvent, reduced pressure distillation is carried out by a rotary vane vacuum pump under high vacuum condition, and 74-75 ℃ fraction under 200Pa is collected. A colorless transparent oily liquid (solid in winter) was obtained.
Among them, in the synthesis of fluoroethylene carbonate, potassium fluoride is usually selected as a fluorinating agent, and in order to achieve a higher conversion of chloroethylene carbonate, potassium fluoride is generally required to be excessive, so that potassium fluoride is contained in a content of not less than 10% in potassium chloride salt after the completion of the reaction. Potassium fluoride is difficult to separate from potassium chloride and fluoride-containing salts are not easily handled, so a more preferred solution is needed.
Therefore, a new solution is needed to solve this problem.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for recycling the salt after the fluorination reaction of fluoroethylene carbonate, which can be used for conveniently separating potassium chloride salt and potassium fluoride of the salt after the fluorination reaction of fluoroethylene carbonate, obtaining purer potassium fluoride and facilitating the subsequent fluorination reaction of fluoroethylene carbonate.
The technical purpose of the invention is realized by the following technical scheme: a method for recycling the salt generated by fluoridation of fluoroethylene carbonate includes
The method comprises the following steps: dissolving potassium chloride and potassium fluoride mixed salt in water, and fully stirring;
step two: filtering the solution to separate insoluble substances;
step three: carrying out steam stripping distillation on the filtrate to remove organic matters in the filtrate;
step four: cooling, slowly dripping into a fluosilicic acid solution after cooling, stirring, and finishing when no precipitate is generated;
step five: concentrating the reaction solution to reduce the water content by 50-60%;
step six: adding a potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, stopping dripping when the reaction solution is alkaline, and finishing the reaction;
step seven: filtering, and concentrating the filtrate for the second time;
step eight: spray drying to obtain potassium fluoride.
Through adopting above-mentioned technical scheme, can make people comparatively easily separate to potassium chloride and the potassium fluoride that obtains after the fluoroethylene carbonate fluorination through above-mentioned method to can convert potassium chloride into potassium fluoride to the utmost, can not have impurity when guaranteeing follow-up recovery, and the reaction is comparatively convenient rapid, avoids potassium chloride and the potassium fluoride after the fluoroethylene carbonate fluorination to suffer abandonment because of the separation difficulty, also avoids potassium fluoride to discharge at will and causes environmental pollution and safety problem.
The invention is further configured to: the mass ratio of the potassium chloride to the potassium fluoride to the water is 1: 2-5.
By adopting the technical scheme, the mass ratio of the potassium chloride to the potassium fluoride to the water is 1:2-5, so that the potassium chloride and the potassium fluoride can be fully dissolved in the water when being dissolved, and the situation that the potassium chloride and the potassium fluoride are filtered due to insufficient dissolution is avoided.
The invention is further configured to: the stripping temperature in the third step is 60-100 ℃.
The invention is further configured to: the temperature of the filtrate in step four was cooled to 30 ℃.
The invention is further configured to: in the fourth step, the filtrate is dripped into the fluosilicic acid and the temperature is controlled between 60 and 80 ℃ when the mixture is stirred.
The invention is further configured to: and the moisture is reduced in the fifth step by heating and evaporating.
The invention is further configured to: and in the sixth step, the content of the potassium hydroxide is 48 percent.
The invention is further configured to: in the sixth step, the temperature of the solution is maintained at 60-70 ℃.
The invention is further configured to: the temperature is maintained at 400-600 ℃ during spray drying in the step eight.
In conclusion, the invention has the following beneficial effects:
by the method, people can easily separate potassium chloride and potassium fluoride obtained after fluorination of fluoroethylene carbonate, the potassium chloride can be converted into the potassium fluoride to the greatest extent, impurities cannot exist during subsequent recovery, the reaction is rapid and convenient, the potassium chloride and the potassium fluoride after fluorination of fluoroethylene carbonate are prevented from being discarded due to difficulty in separation, and the problem of environmental pollution and safety caused by random discharge of the potassium fluoride is also avoided.
Detailed Description
The present invention will be described in detail with reference to examples.
The first embodiment is as follows:
a method for recycling the salt generated by fluoridation of fluoroethylene carbonate includes
Dissolving a potassium chloride and potassium fluoride mixed salt in water through a stirring kettle, wherein the mass ratio of the potassium chloride to the potassium fluoride to the water is 1:2, and fully stirring, wherein the potassium chloride and the potassium fluoride are dissolved in the formed solution, and in addition, some insoluble substances exist.
And step two, filtering the solution, separating insoluble substances, and then obtaining filtrate to ensure that no insoluble substances exist in the filtrate.
And step three, carrying out steam stripping distillation on the filtrate, wherein the steam stripping temperature is 60 ℃, and enabling the filtrate to be in contact with water vapor, so that the organic matters dissolved in the filtrate can be removed through different volatility of the filtrate.
And step four, cooling the temperature of the filtrate to 30 ℃, slowly dripping the filtrate into fluorosilicic acid solution after cooling, stirring, controlling the temperature to be 60-80 ℃, ending when no precipitate is generated, reacting fluorosilicic acid with potassium chloride in the process to generate potassium fluorosilicate and hydrochloric acid, and ending when no precipitate is generated to ensure that the potassium chloride in the filtrate is completely reacted to generate potassium fluorosilicate.
And step five, concentrating the reaction liquid, reducing the water content by 50-60% in a heating evaporation mode, and then continuing to perform subsequent reaction.
Step six, slowly adding a 48% potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, maintaining the solution temperature at 60 ℃, detecting the pH value of the solution by using a pH detector, stopping dropwise adding and finishing the reaction when the reaction solution is alkaline, namely the pH value is between 8 and 9, wherein the potassium fluosilicate and the potassium hydroxide react to generate silicon fluoride, silicon dioxide and water, and the reaction equation is as follows: k2SiF6+4K0H---- 6KF+Si02+4H20。
And step seven, filtering, performing secondary concentration on the filtrate, and evaporating water by heating and the like.
And step eight, performing spray drying to obtain the potassium fluoride, wherein the temperature of the spray drying is between 400 ℃.
Example two:
dissolving potassium chloride and potassium fluoride mixed salt in water through a stirring kettle, wherein the mass ratio of potassium chloride to potassium fluoride to water is 1:3, and fully stirring.
And step two, filtering the solution, separating insoluble substances, and then obtaining filtrate.
And step three, carrying out steam stripping distillation on the filtrate, wherein the steam stripping temperature is 60 ℃, and removing organic matters in the filtrate.
And step four, cooling the temperature of the filtrate to 30 ℃, slowly dripping the filtrate into the fluorosilicic acid solution after cooling, stirring, controlling the temperature to be 60-80 ℃, and finishing when no precipitate is generated.
And step five, concentrating the reaction liquid, reducing the water content by 50-60% in a heating evaporation mode, and then continuing to perform subsequent reaction.
And step six, slowly adding a 48% potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, maintaining the temperature of the solution at 60 ℃, detecting the pH value of the solution by using a pH detector, and stopping dropwise adding and finishing the reaction when the reaction solution is alkaline, namely the pH value is between 8 and 9.
And seventhly, performing secondary concentration on the filtered filtrate.
And step eight, performing spray drying to obtain the potassium fluoride, wherein the temperature of the spray drying is between 400 ℃.
Example three:
dissolving potassium chloride and potassium fluoride mixed salt in water through a stirring kettle, wherein the mass ratio of potassium chloride to potassium fluoride to water is 1:4, and fully stirring.
And step two, filtering the solution, separating insoluble substances, and then obtaining filtrate.
And step three, carrying out steam stripping distillation on the filtrate, wherein the steam stripping temperature is 60 ℃, and removing organic matters in the filtrate.
And step four, cooling the temperature of the filtrate to 30 ℃, slowly dripping the filtrate into the fluorosilicic acid solution after cooling, stirring, controlling the temperature to be 60-80 ℃, and finishing when no precipitate is generated.
And step five, concentrating the reaction liquid, reducing the water content by 50-60% in a heating evaporation mode, and then continuing to perform subsequent reaction.
And step six, slowly adding a 48% potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, maintaining the temperature of the solution at 60 ℃, detecting the pH value of the solution by using a pH detector, and stopping dropwise adding and finishing the reaction when the reaction solution is alkaline, namely the pH value is between 8 and 9.
And seventhly, performing secondary concentration on the filtered filtrate.
And step eight, performing spray drying to obtain the potassium fluoride, wherein the temperature of the spray drying is between 400 ℃.
Example four:
dissolving potassium chloride and potassium fluoride mixed salt in water through a stirring kettle, wherein the mass ratio of potassium chloride to potassium fluoride to water is 1:5, and fully stirring.
And step two, filtering the solution, separating insoluble substances, and then obtaining filtrate.
And step three, carrying out steam stripping distillation on the filtrate, wherein the steam stripping temperature is 60 ℃, and removing organic matters in the filtrate.
And step four, cooling the temperature of the filtrate to 30 ℃, slowly dripping the filtrate into the fluorosilicic acid solution after cooling, stirring, controlling the temperature to be 60-80 ℃, and finishing when no precipitate is generated.
And step five, concentrating the reaction liquid, reducing the water content by 50-60% in a heating evaporation mode, and then continuing to perform subsequent reaction.
And step six, slowly adding a 48% potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, maintaining the temperature of the solution at 60 ℃, detecting the pH value of the solution by using a pH detector, and stopping dropwise adding and finishing the reaction when the reaction solution is alkaline, namely the pH value is between 8 and 9.
And seventhly, performing secondary concentration on the filtered filtrate.
And step eight, performing spray drying to obtain the potassium fluoride, wherein the temperature of the spray drying is between 400 ℃.
Example five:
dissolving potassium chloride and potassium fluoride mixed salt in water through a stirring kettle, wherein the mass ratio of potassium chloride to potassium fluoride to water is 1:3, and fully stirring.
And step two, filtering the solution, separating insoluble substances, and then obtaining filtrate.
And step three, carrying out steam stripping distillation on the filtrate, wherein the steam stripping temperature is 70 ℃, and removing organic matters in the filtrate.
And step four, cooling the temperature of the filtrate to 30 ℃, slowly dripping the filtrate into the fluorosilicic acid solution after cooling, stirring, controlling the temperature to be 60-80 ℃, and finishing when no precipitate is generated.
And step five, concentrating the reaction liquid, reducing the water content by 50-60% in a heating evaporation mode, and then continuing to perform subsequent reaction.
And step six, slowly adding a 48% potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, maintaining the temperature of the solution at 60 ℃, detecting the pH value of the solution by using a pH detector, and stopping dropwise adding and finishing the reaction when the reaction solution is alkaline, namely the pH value is between 8 and 9.
And seventhly, performing secondary concentration on the filtered filtrate.
And step eight, performing spray drying to obtain the potassium fluoride, wherein the temperature of the spray drying is between 400 ℃.
Example six:
dissolving potassium chloride and potassium fluoride mixed salt in water through a stirring kettle, wherein the mass ratio of potassium chloride to potassium fluoride to water is 1:3, and fully stirring.
And step two, filtering the solution, separating insoluble substances, and then obtaining filtrate.
And step three, carrying out steam stripping distillation on the filtrate, wherein the steam stripping temperature is 80 ℃, and removing organic matters in the filtrate.
And step four, cooling the temperature of the filtrate to 30 ℃, slowly dripping the filtrate into the fluorosilicic acid solution after cooling, stirring, controlling the temperature to be 60-80 ℃, and finishing when no precipitate is generated.
And step five, concentrating the reaction liquid, reducing the water content by 50-60% in a heating evaporation mode, and then continuing to perform subsequent reaction.
And step six, slowly adding a 48% potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, maintaining the temperature of the solution at 60 ℃, detecting the pH value of the solution by using a pH detector, and stopping dropwise adding and finishing the reaction when the reaction solution is alkaline, namely the pH value is between 8 and 9.
And seventhly, performing secondary concentration on the filtered filtrate.
And step eight, performing spray drying to obtain the potassium fluoride, wherein the temperature of the spray drying is between 400 ℃.
Example seven:
dissolving potassium chloride and potassium fluoride mixed salt in water through a stirring kettle, wherein the mass ratio of potassium chloride to potassium fluoride to water is 1:3, and fully stirring.
And step two, filtering the solution, separating insoluble substances, and then obtaining filtrate.
And step three, carrying out steam stripping distillation on the filtrate, wherein the steam stripping temperature is 90 ℃, and removing organic matters in the filtrate.
And step four, cooling the temperature of the filtrate to 30 ℃, slowly dripping the filtrate into the fluorosilicic acid solution after cooling, stirring, controlling the temperature to be 60-80 ℃, and finishing when no precipitate is generated.
And step five, concentrating the reaction liquid, reducing the water content by 50-60% in a heating evaporation mode, and then continuing to perform subsequent reaction.
And step six, slowly adding a 48% potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, maintaining the temperature of the solution at 60 ℃, detecting the pH value of the solution by using a pH detector, and stopping dropwise adding and finishing the reaction when the reaction solution is alkaline, namely the pH value is between 8 and 9.
And seventhly, performing secondary concentration on the filtered filtrate.
And step eight, performing spray drying to obtain the potassium fluoride, wherein the temperature of the spray drying is between 400 ℃.
Example eight:
dissolving potassium chloride and potassium fluoride mixed salt in water through a stirring kettle, wherein the mass ratio of potassium chloride to potassium fluoride to water is 1:3, and fully stirring.
And step two, filtering the solution, separating insoluble substances, and then obtaining filtrate.
And step three, carrying out steam stripping distillation on the filtrate, wherein the steam stripping temperature is 100 ℃, and removing organic matters in the filtrate.
And step four, cooling the temperature of the filtrate to 30 ℃, slowly dripping the filtrate into the fluorosilicic acid solution after cooling, stirring, controlling the temperature to be 60-80 ℃, and finishing when no precipitate is generated.
And step five, concentrating the reaction liquid, reducing the water content by 50-60% in a heating evaporation mode, and then continuing to perform subsequent reaction.
And step six, slowly adding a 48% potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, maintaining the temperature of the solution at 60 ℃, detecting the pH value of the solution by using a pH detector, and stopping dropwise adding and finishing the reaction when the reaction solution is alkaline, namely the pH value is between 8 and 9.
And seventhly, performing secondary concentration on the filtered filtrate.
And step eight, performing spray drying to obtain the potassium fluoride, wherein the temperature of the spray drying is between 400 ℃.
Example nine:
dissolving potassium chloride and potassium fluoride mixed salt in water through a stirring kettle, wherein the mass ratio of potassium chloride to potassium fluoride to water is 1:3, and fully stirring.
And step two, filtering the solution, separating insoluble substances, and then obtaining filtrate.
And step three, carrying out steam stripping distillation on the filtrate, wherein the steam stripping temperature is 80 ℃, and removing organic matters in the filtrate.
And step four, cooling the temperature of the filtrate to 30 ℃, slowly dripping the filtrate into the fluorosilicic acid solution after cooling, stirring, controlling the temperature to be 60-80 ℃, and finishing when no precipitate is generated.
And step five, concentrating the reaction liquid, reducing the water content by 50-60% in a heating evaporation mode, and then continuing to perform subsequent reaction.
And step six, slowly adding a 48% potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, maintaining the temperature of the solution at 60 ℃, detecting the pH value of the solution by using a pH detector, and stopping dropwise adding and finishing the reaction when the reaction solution is alkaline, namely the pH value is between 8 and 9.
And seventhly, performing secondary concentration on the filtered filtrate.
And step eight, performing spray drying to obtain the potassium fluoride, wherein the temperature of the spray drying is between 500 ℃.
Example ten:
dissolving potassium chloride and potassium fluoride mixed salt in water through a stirring kettle, wherein the mass ratio of potassium chloride to potassium fluoride to water is 1:3, and fully stirring.
And step two, filtering the solution, separating insoluble substances, and then obtaining filtrate.
And step three, carrying out steam stripping distillation on the filtrate, wherein the steam stripping temperature is 60 ℃, and removing organic matters in the filtrate.
And step four, cooling the temperature of the filtrate to 30 ℃, slowly dripping the filtrate into the fluorosilicic acid solution after cooling, stirring, controlling the temperature to be 60-80 ℃, and finishing when no precipitate is generated.
And step five, concentrating the reaction liquid, reducing the water content by 50-60% in a heating evaporation mode, and then continuing to perform subsequent reaction.
And step six, slowly adding a 48% potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, maintaining the temperature of the solution at 60 ℃, detecting the pH value of the solution by using a pH detector, and stopping dropwise adding and finishing the reaction when the reaction solution is alkaline, namely the pH value is between 8 and 9.
And seventhly, performing secondary concentration on the filtered filtrate.
And step eight, performing spray drying to obtain the potassium fluoride, wherein the temperature of the spray drying is 600 ℃.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (9)
1. A method for recycling salt generated after fluorination reaction of fluoroethylene carbonate is characterized in that: comprises that
The method comprises the following steps: dissolving potassium chloride and potassium fluoride mixed salt in water, and fully stirring;
step two: filtering the solution to separate insoluble substances;
step three: carrying out steam stripping distillation on the filtrate to remove organic matters in the filtrate;
step four: cooling, slowly dripping into a fluosilicic acid solution after cooling, stirring, and finishing when no precipitate is generated;
step five: concentrating the reaction solution to reduce the water content by 50-60%;
step six: adding a potassium hydroxide aqueous solution into the concentrated reaction solution, stirring, stopping dripping when the reaction solution is alkaline, and finishing the reaction;
step seven: filtering, and concentrating the filtrate for the second time;
step eight: spray drying to obtain potassium fluoride.
2. The method for recycling the salt generated after the fluorination reaction of fluoroethylene carbonate according to claim 1, wherein: the mass ratio of the potassium chloride to the potassium fluoride to the water is 1: 2-5.
3. The method for recycling the salt generated after the fluorination reaction of fluoroethylene carbonate according to claim 1, wherein: the stripping temperature in the third step is 60-100 ℃.
4. The method for recycling the salt generated after the fluorination reaction of fluoroethylene carbonate according to claim 1, wherein: the temperature of the filtrate in step four was cooled to 30 ℃.
5. The method for recycling the salt generated after the fluorination reaction of fluoroethylene carbonate according to claim 1, wherein: in the fourth step, the filtrate is dripped into the fluosilicic acid and the temperature is controlled between 60 and 80 ℃ when the mixture is stirred.
6. The method for recycling the salt generated after the fluorination reaction of fluoroethylene carbonate according to claim 1, wherein: and the moisture is reduced in the fifth step by heating and evaporating.
7. The method for recycling the salt generated after the fluorination reaction of fluoroethylene carbonate according to claim 1, wherein: and in the sixth step, the content of the potassium hydroxide is 48 percent.
8. The method for recycling the salt generated after the fluorination reaction of fluoroethylene carbonate according to claim 1, wherein: in the sixth step, the temperature of the solution is maintained at 60-70 ℃.
9. The method for recycling the salt generated after the fluorination reaction of fluoroethylene carbonate according to claim 1, wherein: the temperature is maintained at 400-600 ℃ during spray drying in the step eight.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115353123A (en) * | 2022-08-16 | 2022-11-18 | 珠海正杏新材料科技有限公司 | Method for recovering potassium fluoride |
| CN116062777A (en) * | 2023-03-02 | 2023-05-05 | 浙江硕而博化工有限公司 | Production process for improving purity of fluoroethylene carbonate byproduct potassium chloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102701236A (en) * | 2012-07-06 | 2012-10-03 | 张家港市华盛化学有限公司 | Preparation method of potassium fluoride |
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| CN115353123A (en) * | 2022-08-16 | 2022-11-18 | 珠海正杏新材料科技有限公司 | Method for recovering potassium fluoride |
| CN115353123B (en) * | 2022-08-16 | 2023-12-05 | 珠海正杏新材料科技有限公司 | Recovery method of potassium fluoride |
| CN116062777A (en) * | 2023-03-02 | 2023-05-05 | 浙江硕而博化工有限公司 | Production process for improving purity of fluoroethylene carbonate byproduct potassium chloride |
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