CN112441600A - Separation method of industrial mixed potassium salt - Google Patents
Separation method of industrial mixed potassium salt Download PDFInfo
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- CN112441600A CN112441600A CN201910813934.XA CN201910813934A CN112441600A CN 112441600 A CN112441600 A CN 112441600A CN 201910813934 A CN201910813934 A CN 201910813934A CN 112441600 A CN112441600 A CN 112441600A
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- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
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Abstract
The invention discloses a separation method of industrial mixed potassium salt. The separation method of the mixed potassium salt comprises the following steps: step (1), recrystallizing the mixed potassium salt in water and methanol to obtain potassium chloride and mother liquor A; and (2) concentrating the mother liquor A obtained in the step (1) to obtain mother liquor A ', recrystallizing the obtained mother liquor A' in methanol to obtain a potassium chloride enriched product, collecting the mother liquor B, and concentrating to obtain potassium fluoride. The potassium chloride and the potassium fluoride obtained by the separation method have higher purity.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a separation method of industrial mixed potassium salt.
Background
The potassium chloride and the potassium fluoride have wide application, wherein the potassium chloride is mainly used in the inorganic industry and is a basic raw material for preparing various potassium salts, such as potassium hydroxide, potassium sulfate, potassium nitrate, potassium chlorate, potassium bichromate and the like, and the potassium chloride is used as a potassium fertilizer in agriculture; the potassium fluoride is mainly used as a fluorinating agent in organic synthesis, and can also be used as a glass carving agent, a catalyst, an insecticide and the like.
In general, waste residues (also referred to as "industrial mixed potassium salts") generated by organic fluorination reaction contain about 80% of potassium chloride, about 10% of potassium fluoride, and the balance of tar, sulfolane and the like. The application field of such industrial mixed potassium salts is very limited due to the presence of fluoride, a dangerous chemical, in the above-mentioned waste residues.
For the above waste residues, it is a common practice for enterprises to sell the waste residues as solid chemical wastes, or to burn the waste residues directly and then enter a sewage system. Although the latter can reduce the production cost, the environment is easily polluted, and the waste of potassium resources is easily caused.
At present, there are also some patent documents disclosing methods for treating industrially mixed potassium salts.
Chinese patent application CN106006679A discloses a method for recovering high purity potassium chloride from fluorination reactor by-products, which comprises the following steps: firstly, heat treatment is carried out to remove attached organic matters, then potassium fluoride is leached out by liquid ammonia in a pressurizing mode to realize the separation of potassium chloride and potassium fluoride, liquid ammonia solution of potassium fluoride is leached out, and separation and recovery are realized through vaporization. The method needs two different solvent systems to separate potassium fluoride and potassium chloride respectively, and needs conditions of high temperature and high pressure, and liquid ammonia is easy to generate unfriendly influence on the environment, is difficult to recover and is difficult to popularize in industrial production. In the scheme, the recovery rate of KF is 98%, the purity is 99%, the recovery rate of KCl is 94.4%, and the purity is 99.95%.
Chinese patent CN102730710B also discloses a method for separating a mixture of potassium chloride and potassium fluoride, which comprises the following specific operations: treating the mixture of potassium chloride and potassium fluoride at 300-500 deg.C for 1-5 hr to remove organic waste, introducing boron trifluoride/acetonitrile system, making potassium chloride insoluble in the above system, and making potassium fluoride enter the system and react with potassium fluorideAnd (3) according to the principle of converting the potassium tetrafluoroborate into potassium tetrafluoroborate, filtering to separate potassium chloride and potassium tetrafluoroborate filtrate, and further processing the filtrate to obtain the potassium tetrafluoroborate as a byproduct for sale. The scheme converts KF into medium KBF4Recovery 97.3%, purity not mentioned; KCl purity and recovery are also not mentioned. The method has simple process, but needs high-temperature treatment on the byproduct mixed potassium salt, and has the problems of large consumption of acetonitrile solvent, high cost and certain environmental pollution.
Therefore, the present invention is needed to provide a method for efficiently separating industrial mixed potassium salts, so as to solve the above-mentioned significant problems in the chemical industry.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the problems that in the prior art, two different types of solvent systems are needed, the conditions of high temperature and high pressure are needed, the environment is not friendly, the solvent is difficult to recover and the industrial production is difficult to apply, or the defects of high solvent consumption, high environmental pollution and high cost exist in a process method for separating the industrial mixed potassium salt, so that the method for separating the industrial mixed potassium salt is provided. By the separation method, high-purity potassium chloride and potassium fluoride can be separated from industrial mixed potassium salt in a single solvent system; the separation method can be further combined with process equipment to recover the solvent for reuse, thereby realizing continuous production, and the method has the advantages of simple process, mild condition, low energy consumption, strong operability, no pollution, reduction of production cost, remarkable economic benefit and social benefit and suitability for industrial production.
The present invention solves the above-mentioned problems by the following means.
The invention provides a separation method of mixed sylvite, which comprises the following steps:
step (1), recrystallizing the mixed potassium salt in water and methanol to obtain potassium chloride and mother liquor A;
and (2) concentrating the mother liquor A obtained in the step (1) to obtain mother liquor A ', recrystallizing the obtained mother liquor A' in methanol to obtain a potassium chloride enriched product, collecting the mother liquor B, and concentrating to obtain potassium fluoride.
In the step (1), the mixed potassium salt refers to waste residues generated by conventional organic fluorination reaction in the field of chemical industry, wherein potassium chloride accounts for 80 +/-5%, potassium fluoride accounts for 10 +/-5%, the total amount of other inorganic salts is not higher than 1%, and the percentage is the mass percentage of each component in the mixed potassium salt in the total mass of the mixed potassium salt. Specifically, the present invention may refer to a potassium salt residue obtained by an organic fluorination reaction using a fluorinating agent as potassium fluoride.
In the step (1), the mixed potassium salt may be subjected to a pretreatment step before recrystallization. When the mixed potassium salt is subjected to the pretreatment step, the mass ratio of the methanol in the step (1) to the crude mixed potassium salt obtained in the pretreatment step may be 1.0: 1.0-3.0: 1.0, may be 1.5: 1.0-3.0: 1.0, and may also be 2.0: 1.0-3.0: 1.0, for example, 2.0:1.0, and 2.5: 1.0.
Wherein, the pretreatment comprises the following steps: pulping and filtering.
In the pretreatment step, the slurrying solvent may be one or more of toluene, dichloromethane, sulfolane and methanol, or sulfolane, methanol or dichloromethane, or sulfolane. The amount of the solvent may be used conventionally in the art for the beating operation. The mass ratio of the solvent to the mixed sylvite can be less than or equal to 3:1 and can also be 2:1-1: 1.
In the pretreatment step, the pulping is conventional in the field, and can be specifically carried out by adopting conventional pulping operation and parameters, and more specifically, the mixed potassium salt can be refluxed and stirred in a solvent.
In the pretreatment step, the filtration may be a hot filtration.
In the pretreatment step, the filtrate obtained after filtration can be applied to the pulping step.
In the step (1), the mass ratio of the methanol to the mixed potassium salt may be 0.9:1.0 to 2.7:1.0, or may be 1.7:1.0 to 2.7:1.0, or may be 1.8:1.0 to 2.7:1.0, for example, 2.0:1.0, or 2.3: 1.0.
In step (1), the water is used conventionally in such operations in the art, and is not particularly limited.
In the step (1), the mass ratio of the methanol to the water may be 0.6: 1.0-1.8: 1.0, or may be 1.2: 1.0-1.8: 1.0, such as 1.3:1.0, or 1.5: 1.0.
In the step (1), the recrystallization temperature can be 0-30 ℃ and can also be 0-15 ℃.
In step (1), the operation and conditions for recrystallization may be those conventional in the art. The recrystallization preferably comprises the following steps: dissolving the mixed potassium salt in the water to obtain a mixed solution; and mixing the mixed solution with the methanol, and cooling.
In the recrystallization step, the dissolving temperature can be 60-90 ℃.
In the recrystallization step, the temperature for mixing the mixed solution with the methanol is preferably 65 to 55 ℃, for example, 60 ℃.
In the step (1), after the recrystallization is finished, the method also comprises the steps of filtering, washing a filter cake and drying. The filtration may be suction filtration under reduced pressure, for example suction filtration. The solvent for washing the filter cake may be methanol. The drying may be drying.
Wherein the mass ratio of the mixed potassium salt in the step (1) to the mother liquor A' in the step (2) can be 0.6: 1.0-1.0: 1.0, preferably 0.8: 1.0-0.9: 1.0.
In the invention, the mother liquor A is concentrated, so that the purity of potassium chloride and sodium chloride can be improved, and particularly, when the mass ratio of the mixed potassium salt in the step (1) to the mother liquor A' in the step (2) is 0.8: 1.0-0.9: 1.0, the purity and yield of the potassium chloride and the sodium chloride are improved.
In the step (2), the mass ratio of the methanol to the mother liquor A' may be 0.6: 1.0-1.0: 1.0, or may be 0.8: 1.0-1.0: 1.0, for example, 0.9: 1.0.
In the step (2), the recrystallization temperature can be 0-30 ℃ and can also be 0-15 ℃.
In step (2), the operation and conditions for recrystallization may be those conventional in the art. The recrystallization preferably comprises the following steps: mixing the mother liquor A' obtained in the step (1) with methanol to obtain a mixed solution II; and (3) obtaining a hot solution from the mixed solution II under a reflux state, and cooling.
In the step (2), after the recrystallization is finished, the method also comprises the steps of filtering and washing a filter cake. The filtration may be suction filtration under reduced pressure, for example suction filtration. The solvent for washing the filter cake may be methanol.
In step (2), the operation and conditions of the concentration may be those conventional in the art.
And (2) concentrating the filtrate to obtain the potassium fluoride. The purity of the obtained potassium fluoride can be more than 95.0%, the recovery rate can be more than 95.0%, and the potassium fluoride can be recycled and applied to organic fluorination reaction to be used as a fluorinating agent.
And (2) recycling the potassium chloride-enriched product, optionally the potassium chloride-enriched product, into the step (1). And (3) recycling the potassium chloride enriched product to the step (1) so as to further improve the recovery rate and purity of potassium chloride.
In the method for separating mixed potassium salt according to the present invention, the solvents used in the steps can be recycled and reused in the steps of the present invention, for example:
in the step (1), when the mixed potassium salt is subjected to a pretreatment step before recrystallization, the filtrate obtained after filtration in the pretreatment step can be applied to a pulping step.
In the step (1), the methanol can be partially or completely obtained by concentrating and recovering the mother liquor B in the step (2).
In the step (2), the methanol can be partially or completely obtained by concentrating and recovering the mother liquor B subjected to the step (2).
In one embodiment of the present invention, in the step (1), the mass ratio of the methanol to the mixed potassium salt may be 0.9:1.0 to 2.7: 1.0; the mass ratio of the methanol to the water can be 0.6: 1.0-1.8: 1.0; 0.6: 1.0-1.0: 1.0.
In an embodiment of the present invention, in the step (1), the mass ratio of the methanol to the mixed potassium salt may be 1.8:1.0 to 2.7: 1.0; the mass ratio of the methanol to the water is 1.2: 1.0-1.8: 1.0; 0.8: 1.0-0.9: 1.0.
In one embodiment of the invention, in the step (1), the mass ratio of the methanol to the mixed potassium salt is 1.7: 1.0-2.7: 1.0; the recrystallization temperature is 0-15 ℃.
In one embodiment of the present invention, in step (1), the mixed potassium salt is subjected to a pretreatment step before being subjected to recrystallization; the mass ratio of the methanol to the mixed potassium salt is 1.8: 1.0-2.7: 1.0; the mass ratio of the methanol to the water is 1.2: 1.0-1.8: 1.0; the crystallization temperature is 0-15 ℃; the mass ratio of the mixed potassium salt in the step (1) to the mother liquor A' in the step (2) is 0.8: 1.0-0.9: 1.0;
in the step (2), the recrystallization temperature is 0-15 ℃.
In the present invention, the "crude mixed potassium salt" refers to a mixed potassium salt containing no tar.
In the invention, the potassium chloride concentrate refers to a product which mainly contains potassium chloride and contains a small amount of potassium fluoride.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the separation method of the invention can realize the one-time separation of the potassium chloride and the potassium fluoride in the mixed potassium salt without any chemical reaction, the purity of the potassium chloride can reach more than 98.42 percent, and the purity of the potassium fluoride can reach more than 94.46 percent.
(2) The solvent used in the separation method is a common reagent in industrial production, has high recovery rate and can be recycled.
(3) The separation equipment can be used for continuous production, has the advantages of simple process, mild conditions, low energy consumption, strong operability and no pollution, reduces the production cost, has obvious economic and social benefits and is suitable for industrial production.
Drawings
Fig. 1 is a flowchart of a recycling process of an industrial byproduct mixed potassium salt according to the present invention, wherein R201 is a potassium salt crude product tar removal tank, R202 is a KCl separation tank, R203 is a potassium salt concentrate separation tank, R204 is a KF separation tank, R301 is a sulfolane recovery tank, R302 is a methanol recovery tank, D101 is a potassium salt crude product separation centrifuge, D102 is a KCl separation centrifuge, D103 is a potassium salt concentrate separation centrifuge, D104 is a KF separation centrifuge, V101 is a sulfolane filtrate receiving tank, V102 is a potassium salt concentrate filtrate receiving tank, V103 is a crude distilled methanol fraction receiving tank, V104 is a KF filtrate receiving tank, V105 is a fraction receiving tank, V106 is a KF concentrate filtrate transfer tank, V201 is a front fraction receiving tank, V202 is a sulfolane fraction receiving tank, V203 is a methanol main fraction receiving tank, V204 is a middle fraction receiving tank, V301 is a sulfolane tank, V302 is a methanol tank 1, and V303 is a methanol tank 2.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The mixed potassium salt used in the following examples is potassium salt residue obtained by organic fluorination reaction in which potassium fluoride is used as a fluorinating agent, wherein potassium chloride accounts for 80 + -5%, potassium fluoride accounts for 10% + -5%, and the sum of other inorganic salts is not higher than 1%, and the "%" represents the mass percentage of each component in the mixed potassium salt to the total mass of the mixed potassium salt.
Detection method
And (3) detecting the content of potassium chloride: referring to a general method potentiometric titration method for measuring the content of chloride in GB/T3050-2000 inorganic chemical products, the adopted equipment is a Mettler S220 multifunctional ion determinator
And (3) detecting the content of potassium fluoride: referring to a general method ion selective electrode method for measuring the fluorine content in GB/T21057-2007 inorganic chemical products, the adopted equipment is a Mettler S220 multifunctional ion determinator for detecting the moisture content: referring to a general method Karl Fischer method for measuring the moisture of GB/T606-.
Example 1
Adding 150g of byproduct mixed potassium salt and 300g of sulfolane into a 500mL four-mouth bottle, preserving heat at 90 ℃ for 2h, filtering to obtain 151.0g of crude mixed potassium salt (dry weight is 135.9g), and detecting: wt (kcl)% (88.19%), Wt (kf)% (10.89%), and Wt (water)% (0.21%), then dissolved in 231.6g of 90 ℃ hot water, after complete dissolution, cooled to 60 ℃, then 271.8g of methanol was slowly added, crystallized (end point temperature 15 ℃), filtered, the filter cake was rinsed with a small amount of methanol, and dried to give 104.1g of a dried potassium chloride product, appearance: white crystals, detected: wt (kcl)% > 99.30%, Wt (kf)% > 0.23%, Wt (water)% > 0.15%; concentrating 535.8g of filtrate after crystallization under reduced pressure until the content of the initial mixed potassium salt is 90%, adding 31.8g of methanol, crystallizing (the end point temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 14.8g of a potassium fluoride dry product, wherein the appearance is as follows: white crystals, detected: wt (kcl)% (3.45%), Wt (kf)% (95.72%), Wt (water)% (0.55%).
Example 2
Adding 150g of byproduct mixed potassium salt and 300g of dichloromethane into a 500mL four-mouth bottle, preserving the temperature at 40 ℃ for 2h, filtering to obtain 150.1g of crude mixed potassium salt (135.1 g of dry weight), and detecting: wt (k cl)% (88.78%, Wt (kf)%, Wt (water)% (0.15%), followed by dissolving in 232.3g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, then slowly adding 270.2g of methanol, crystallizing (end point temperature 15 ℃), suction filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 103.3g of a dried potassium chloride product, appearance: white crystals, detected: wt (kcl)% (99.36%), Wt (kf)% (0.06%), Wt (water)% (0.06%); and (3) decompressing and concentrating 534.3g of filtrate after crystallization until the content of the initial mixed potassium salt is 90%, adding 31.8g of methanol, crystallizing (the end temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain the filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 14.7g of a potassium fluoride dry product, wherein the appearance is as follows: white crystals, detected: wt (kcl)% (3.36%), Wt (kf)% (96.17%), and Wt (water)% (0.39%).
Example 3
150g of byproduct mixed potassium salt and 300g of toluene are added into a 500mL four-mouth bottle, the temperature is kept at 90 ℃ for 2h, and the mixture is filtered to obtain 154.0g of crude mixed potassium salt (dry weight is 135.5g), and the detection shows that: wt (kcl)% (88.56%), Wt (kf)% (10.98%), Wt (water)% (0.31%), dissolving the mixture in 232.6g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, slowly adding 271.0g of methanol, crystallizing (end point temperature 15 ℃), filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 103.7g of a dried potassium chloride product with appearance: white crystals, detected: wt (kcl)% (99.34%), Wt (kf)% (0.06%), Wt (water)% (0.06%); concentrating 535.4g of filtrate after crystallization under reduced pressure until the content of the initial mixed potassium salt is 90%, adding 31.8g of methanol, crystallizing (the end point temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 14.9g of a potassium fluoride dry product, wherein the appearance is as follows: white crystals, detected: wt (kcl)% (3.39%, Wt (kf)% (96.10%, Wt (water)% (0.44%).
Example 4
Adding 150g of byproduct mixed potassium salt and 300g of methanol into a 500mL four-mouth bottle, preserving the temperature at 65 ℃ for 2h, filtering to obtain 144.8g of crude mixed potassium salt (130.3 g of dry weight), and detecting: wt (k cl)% (90.08%, Wt (kf)% (9.55%, Wt (water)%) 0.27%, then dissolved in 226.1g of 90 ℃ hot water, after complete dissolution, cooled to 60 ℃, then 260.6g of methanol was slowly added, crystallized (end point temperature 15 ℃), filtered, the filter cake rinsed with a small amount of methanol, dried to give 103.6g of a dried potassium chloride product, appearance: white crystals, detected: wt (kcl)% (99.90%), Wt (kf)% (0.05%), Wt (water)% (0.04%); concentrating 513.5g of filtrate after crystallization under reduced pressure until the content of the initial mixed potassium salt is 90%, adding 26.7g of methanol, crystallizing (the end point temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 10.9g of a potassium fluoride dry product, wherein the appearance is as follows: white crystals, detected: wt (kcl)% (3.61%), Wt (kf)% (95.70%), Wt (water)% (0.58%).
Example 5
Adding 150g of byproduct mixed potassium salt and 300g of sulfolane into a 500mL four-mouth bottle, preserving heat at 90 ℃ for 2h, filtering to obtain 151.0g of crude mixed potassium salt (dry weight is 135.9g), and detecting: wt (k cl)% (88.19%), Wt (kf)% (10.89%), and Wt (water)% (0.21%), followed by dissolving in 232.2g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, then slowly adding 203.9g of methanol, crystallizing (end point temperature 15 ℃) and suction filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 100.4g of a dried potassium chloride product, appearance: white crystals, detected: wt (kcl)% (99.07%, Wt (kf)% (0.15%, Wt (water)% (0.12%); concentrating 471.6g of filtrate after crystallization under reduced pressure until the content of the initial mixed potassium salt is 90%, adding 35.5g of methanol, crystallizing (the end temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain the filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 14.1g of a potassium fluoride dry product, wherein the appearance is as follows: white crystals, detected: wt (kcl)% (3.71%), Wt (kf)% (95.35%), and Wt (water)% (0.66%).
Example 6
150g of byproduct mixed potassium salt and 300g of sulfolane are added into a 500mL four-mouth bottle, the temperature is kept at 90 ℃ for 2h, and the mixture is filtered to obtain 154.0g of crude mixed potassium salt (dry weight is 135.5g), and the detection result shows that: wt (kcl)% (88.19%), Wt (kf)% (10.89%), and Wt (water)% (0.21%), followed by dissolving in 231.6g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, then slowly adding 135.5g of methanol, crystallizing (end point temperature 15 ℃), suction filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 98.3g of a dried potassium chloride product with appearance: white crystals, detected: wt (kcl)% (98.70%), Wt (kf)% (0.36%), Wt (water)% (0.21%); and (3) decompressing and concentrating 405.7g of filtrate after crystallization until the content of the initial mixed potassium salt is 90%, adding 37.2g of methanol, crystallizing (the end temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 13.4g of a potassium fluoride dry product, wherein the appearance is as follows: white crystals, detected: wt (kcl)% (3.66%, Wt (kf)% (95.49%, Wt (water)% (0.60%).
Example 7
150g of byproduct mixed potassium salt and 300g of sulfolane are added into a 500mL four-mouth bottle, the temperature is kept at 90 ℃ for 2h, and the mixture is filtered to obtain 154.0g of crude mixed potassium salt (dry weight is 135.5g), and the detection result shows that: wt (kcl)% (88.19%), Wt (kf)% (10.89%), and Wt (water)% (0.21%), followed by dissolving in 231.6g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, then slowly adding 338.8g of methanol, crystallizing (end point temperature 15 ℃), suction filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 104.1g of a dried potassium chloride product with appearance: white crystals, detected: wt (kcl)% (99.21%), Wt (kf)% (0.09%, Wt (water)% (0.15%); concentrating 603.8g of filtrate after crystallization under reduced pressure until the content of the initial mixed potassium salt is 90%, adding 31.4g of methanol, crystallizing (the end temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 14.7g of a potassium fluoride dry product, wherein the appearance is as follows: white crystals, detected: wt (kcl)% (3.48%), Wt (kf)% (95.66%, Wt (water)% (0.55%).
Example 8
150g of byproduct mixed potassium salt and 300g of sulfolane are added into a 500mL four-mouth bottle, the temperature is kept at 90 ℃ for 2h, and the mixture is filtered to obtain 154.0g of crude mixed potassium salt (dry weight is 135.5g), and the detection result shows that: wt (kcl)% (88.19%), Wt (kf)% (10.89%), Wt (water)% (0.21%), dissolving the product in 231.6g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, slowly adding 406.6g of methanol, crystallizing (end point temperature 15 ℃), filtering, leaching the filter cake with a small amount of methanol, and drying to obtain 104.4g of a dried potassium chloride product, which is detected: wt (kcl)% (99.30%), Wt (kf)% (0.07%, Wt (water)% (0.15%); and (3) decompressing and concentrating 671.4g of filtrate after crystallization until the content of the initial mixed potassium salt is 90%, adding 31.1g of methanol, crystallizing (the end temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 14.7g of a potassium fluoride dry product, wherein the appearance is as follows: white crystals, detected: wt (kcl)% (3.45%), Wt (kf)% (95.73%, Wt (water)% (0.59%).
Example 9
150g of byproduct mixed potassium salt and 300g of sulfolane are added into a 500mL four-mouth bottle, the temperature is kept at 90 ℃ for 2h, and the mixture is filtered to obtain 154.0g of crude mixed potassium salt (dry weight is 135.5g), and the detection result shows that: wt (kcl)% (88.19%), Wt (kf)% (10.89%), and Wt (water)% (0.21%), followed by dissolving in 232.3g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, then slowly adding 271.0g of methanol, crystallizing (end point temperature 0 ℃) and suction filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 104.4g of a dried potassium chloride product with appearance: white crystals, detected: wt (kcl)% > 99.11%, Wt (kf)% > 0.20%, Wt (water)% > 0.25%; concentrating 535.5g of filtrate after crystallization under reduced pressure until the content of the initial mixed potassium salt is 90%, adding 31.1g of methanol, crystallizing (the end point temperature is 0 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 15.1g of a dried potassium fluoride product with the appearance: white crystals, detected: wt (kcl)% (3.78%), Wt (kf)% (95.33%), and Wt (water)% (0.63%).
Example 10
150g of byproduct mixed potassium salt and 300g of sulfolane are added into a 500mL four-mouth bottle, the temperature is kept at 90 ℃ for 2h, and the mixture is filtered to obtain 154.0g of crude mixed potassium salt (dry weight is 135.5g), and the detection result shows that: wt (kcl)% (88.19%), Wt (kf)% (10.89%), and Wt (water)% (0.21%), then dissolved in 231.6g of 90 ℃ hot water, after complete dissolution, cooled to 60 ℃, then 271.0g of methanol was slowly added, crystallized (end point temperature 30 ℃), filtered, the filter cake was rinsed with a small amount of methanol, and dried to give 99.8g of a dried potassium chloride product, appearance: white crystals, detected: wt (kcl)% > 99.15%, Wt (kf)% > 0.35%, Wt (water)% > 0.12%; concentrating 540.1g of filtrate after crystallization under reduced pressure until the content of the initial mixed potassium salt is 90%, adding 35.7g of methanol, crystallizing (the end point temperature is 30 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 13.6g of a dried potassium fluoride product with the appearance: white crystals, detected: wt (kcl)% (3.24%), Wt (kf)% (95.92%), Wt (water)% (0.54%).
Example 11
150g of byproduct mixed potassium salt is added into a 500mL four-mouth bottle, and detection shows that: wt (kcl)% (81.00%), Wt (kf)% (10.00%), and Wt (water)% (0.91%), followed by dissolving in 235.4g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, then slowly adding 300.0g of methanol, crystallizing (end point temperature 15 ℃), suction filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 108.1g of a dried potassium chloride product with an appearance: off-white crystals, detected: wt (kcl)% (98.42%), Wt (kf)% (0.50%), Wt (water)% (0.16%); concentrating 577.3g of filtrate after crystallization under reduced pressure until the content of the initial mixed potassium salt is 90%, adding 41.9g of methanol, crystallizing (the end point temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 13.7g of a potassium fluoride dry product, wherein the appearance is as follows: off-white crystals, detected: wt (kcl)% (3.17%), Wt (kf)% (95.47%, Wt (water)% (0.41%).
Example 12
Adding 150g of byproduct mixed potassium salt and 300g of recovered sulfolane into a 500mL four-mouth bottle, preserving heat at 90 ℃ for 2h, filtering to obtain 151.0g of crude mixed potassium salt (dry weight is 135.9g), and detecting: wt (kcl)% (88.23%), Wt (kf)% (10.78%), Wt (water)% (0.25%), dissolving the mixture in 232.2g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, slowly adding 271.8g of recovered methanol, crystallizing (end point temperature 15 ℃), filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 104.0g of a dried potassium chloride product, appearance: white crystals, detected: wt (kcl)% (99.33%, Wt (kf)% (0.22%, Wt (water)% (0.18%); and (3) decompressing and concentrating 534.1g of filtrate after crystallization until the content of the initial mixed potassium salt is 90%, adding 31.9g of methanol, crystallizing (the end temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain the filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 14.9g of a potassium fluoride dry product, wherein the appearance is as follows: white crystals, detected: wt (kcl)% (3.46%), Wt (kf)% (95.74%), and Wt (water)% (0.53%).
Example 13
150g of byproduct mixed potassium salt and 300g of sulfolane are added into a 500mL four-mouth bottle, the temperature is kept at 90 ℃ for 2h, and the mixture is filtered to obtain 154.0g of crude mixed potassium salt (dry weight is 135.5g), and the detection result shows that: wt (kcl)% (88.19%), Wt (kf)% (10.89%), and Wt (water)% (0.21%), followed by dissolving in 231.6g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, then slowly adding 271.0g of methanol, crystallizing (end point temperature 15 ℃), suction filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 104.1g of a dried potassium chloride product with an appearance: white crystals, detected: wt (kcl)% > 99.30%, Wt (kf)% > 0.23%, Wt (water)% > 0.15%; concentrating 535.8g of filtrate after crystallization under reduced pressure until the content of the initial mixed potassium salt is 80%, adding 31.4g of methanol, crystallizing (the end point temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain the filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 14.5g of a potassium fluoride dry product, wherein the appearance is as follows: white crystals, detected: wt (kcl)% (3.87%), Wt (kf)% (95.13%), and Wt (water)% (0.65%).
Example 14
150g of byproduct mixed potassium salt and 300g of sulfolane are added into a 500mL four-mouth bottle, the temperature is kept at 90 ℃ for 2h, and the mixture is filtered to obtain 154.0g of crude mixed potassium salt (dry weight is 135.5g), and the detection result shows that: wt (kcl)% (88.19%), Wt (kf)% (10.89%), and Wt (water)% (0.21%), followed by dissolving in 232.2g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, then slowly adding 135.9g of methanol, crystallizing (end point temperature 15 ℃) and suction filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 104.1g of a dried potassium chloride product, appearance: white crystals, detected: wt (kcl)% > 99.30%, Wt (kf)% > 0.23%, Wt (water)% > 0.15%; concentrating 535.8g of filtrate after crystallization under reduced pressure until the content of the initial mixed potassium salt is 100%, adding 31.4g of methanol, crystallizing (the end point temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 7.5g of a dried potassium fluoride product with the appearance: white crystals, detected: wt (kcl)% (2.35%), Wt (kf)% (96.81%), Wt (water)% (0.58%).
Example 15
150g of byproduct mixed potassium salt and 300g of sulfolane are added into a 500mL four-mouth bottle, the temperature is kept at 90 ℃ for 2h, and the mixture is filtered to obtain 154.0g of crude mixed potassium salt (dry weight is 135.5g), and the detection result shows that: wt (kcl)% (88.19%), Wt (kf)% (10.89%), and Wt (water)% (0.21%), followed by dissolving in 231.6g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, then slowly adding 271.0g of methanol, crystallizing (end point temperature 15 ℃), suction filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 104.1g of a dried potassium chloride product with an appearance: white crystals, detected: wt (kcl)% > 99.30%, Wt (kf)% > 0.23%, Wt (water)% > 0.15%; concentrating 535.8g of filtrate after crystallization under reduced pressure until the content of the initial mixed potassium salt is 60%, adding 31.4g of methanol, crystallizing (the end point temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, and concentrating the obtained filtrate to obtain 6.9g of a dried potassium fluoride product with the appearance: white crystals, detected: wt (kcl)% (4.61%), Wt (kf)% (94.46%), and Wt (water)% (0.55%).
Example 16 production run
Removing tar: opening a V301 bottom valve of a sulfolane dripping tank, opening a material transferring pipeline valve from V301 to a reaction kettle R201, adding a certain amount of sulfolane solvent into the reaction kettle R201, closing the V301 bottom valve after transferring is finished, closing the material transferring pipeline valve, opening R201 for stirring, adding a certain amount of mixed sylvite through a solid feeding port, then closing a corresponding valve, opening a circulating water valve of a condenser jacket, introducing circulating water for precooling the condenser, opening a heating medium inlet/outlet valve of the reaction kettle jacket, introducing 90 ℃ hot water, heating the reaction kettle, and stirring for 2 hours under heat preservation; and then opening a bottom valve of the reaction kettle R201, putting the slurry in the R201 into a centrifuge D101 through gravity, filtering, weighing and bagging filter cakes for later use, receiving the filtrate in a sulfolane filtrate receiving tank V101, transferring the solution in the V101 to a recovery kettle R301, and distilling the distillate into the V301 for reuse.
KCl separation: adding a certain amount of process water into a KCl separation kettle R202 through a process water pipe, starting stirring, adding a certain amount of crude mixed salt (from a tar removal process and a KF separation process) through a solid charging port, then closing corresponding valves, opening a jacket circulating water valve of a R202 condenser, introducing circulating water to pre-cool the condenser, then opening a jacket low-pressure steam inlet-outlet valve, introducing low-pressure steam to heat the R202, closing the low-pressure steam inlet-outlet valve when the thermometer reading of the reaction kettle reaches a certain value, keeping the temperature and stirring until the crude mixed salt is completely dissolved, then opening a methanol dripping tank V302-R202 material transfer pipeline valve, opening a V302 bottom valve, slowly dripping a certain amount of methanol into the R202 through control of a hand valve, closing the corresponding pipeline valve after dripping is finished, then opening the jacket inlet-outlet valve of the R202, introducing a refrigerant, slowly reducing the kettle temperature of the R202 to 15 ℃, stirring for 1h under heat preservation; opening a pipeline valve from R202 to a centrifuge D102, opening a bottom valve of the R202, placing slurry in the R202 into a centrifuge D101 by gravity, filtering, leaching a filter cake by using a small amount of methanol, discharging to an oven for drying, sampling and detecting a dry product, and bagging. The filtrate is removed potassium salt and is enriched, and the filtrate is received in a tank V102.
Transferring the filtrate in the V102 into a potassium salt enriched product separation kettle R203 through a pump P102, starting stirring, opening a circulating water valve of a jacket of a condenser R203, introducing circulating water to pre-cool the condenser, starting a pump P1001, vacuumizing the system to-0.095 MPa, opening a low-pressure steam inlet-outlet valve of the jacket, introducing low-pressure steam to heat up (vacuum distillation) the R203, distilling the distillate to a crude distilled methanol distillate receiving tank V103, ending distillation, opening a methanol dropwise addition tank 2V303 to a material transfer pipeline valve of the R203, opening a V302 bottom valve, slowly dropwise adding a certain amount of methanol into the R203 through manual valve control, closing the corresponding pipeline valve after dropwise adding, then opening a refrigerant inlet-outlet valve of the jacket of the R203, introducing a refrigerant, slowly reducing the temperature of the kettle R203 to 15 ℃, preserving heat and stirring for 1 hour; and opening a pipeline valve from the R203 to the centrifuge D103, opening a bottom valve of the R203, gravitationally placing the slurry in the R203 into the centrifuge D103, removing the filtrate from a KF filtrate receiving tank V104, leaching the filter cake with a small amount of methanol, and bagging for later use.
Transferring the solvent to a crude distilled methanol fraction receiving tank V103 through a pipeline, transferring the crude distilled methanol fraction in the V103 to a methanol recovery kettle R302 through a pump P103, starting stirring, opening a circulating water valve of a jacket of the R302 condenser, introducing circulating water to pre-cool the condenser, opening a low-pressure steam inlet-outlet valve of the jacket of the R302, introducing low-pressure steam to heat the R302 (atmospheric distillation), transferring the front fraction to a main distilled methanol fraction receiving tank V203, and transferring the middle fraction to a middle fraction receiving tank V204.
KF separation: transferring the filtrate in the V104 into a KF separation kettle R204 through a pump P104, starting stirring, opening a circulating water valve of a jacket of a condenser R204, introducing circulating water to pre-cool the condenser, opening a low-pressure steam inlet-outlet valve of the jacket, introducing low-pressure steam to heat the R204 (atmospheric distillation), and ending distillation when the fraction reaches a fraction receiving tank V105; opening an inlet and outlet valve of a refrigerant of the R204 jacket, introducing the refrigerant, slowly reducing the temperature of the R204 kettle to 15 ℃, preserving heat and stirring for 1 h; opening a pipeline valve from R204 to a centrifuge D104, opening a bottom valve of R204, placing slurry in R204 into the centrifuge D104 by gravity, leaching a filter cake by using a small amount of methanol, discharging to an oven for drying, sampling and detecting a dry product, and bagging. And (4) removing the filtrate from a KF enrichment filtrate transfer tank V106, and mechanically applying the filtrate to a KF separation kettle R204.
Comparative example 1
150g of byproduct mixed potassium salt and 300g of sulfolane are added into a 500mL four-mouth bottle, the temperature is kept at 90 ℃ for 2h, and the mixture is filtered to obtain 154.0g of crude mixed potassium salt (dry weight is 135.5g), and the detection result shows that: wt (kcl)% (88.19%), Wt (kf)% (10.89%), Wt (water)% (0.21%), dissolving the product in 231.6g of 90 ℃ hot water, cooling to 60 ℃ after complete dissolution, slowly adding 271.0g of isopropanol, crystallizing (end point temperature 15 ℃), filtering, rinsing the filter cake with a small amount of methanol, and drying to obtain 100.2g of a dried potassium chloride product, which is detected: wt (kcl)% (94.29%), Wt (kf)% (5.44%), Wt (water)% (0.08%); and (3) concentrating the filtrate after crystallization under reduced pressure until the initial content of the mixed potassium salt is 90%, adding 35.3g of isopropanol, crystallizing (the end point temperature is 15 ℃), performing suction filtration, leaching a filter cake with a small amount of methanol to obtain a filter cake which is a potassium chloride enriched product, concentrating the obtained filtrate to obtain 13.1g of a potassium fluoride dry product, and detecting: wt (kcl)% (50.93%, Wt (kf)% (48.92%, Wt (water)% (0.12%).
As can be seen from the above comparative examples, when the methanol obtained in the present invention was replaced with isopropanol, the purity of potassium chloride (wt) (kcl)% (94.29%) and potassium fluoride (wt) (kf)% (48.92%) were low, and particularly the purity of potassium fluoride was extremely low, and the purpose of separating industrial potassium salt at a time could not be achieved.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (10)
1. The separation method of the mixed potassium salt is characterized by comprising the following steps:
step (1), recrystallizing the mixed potassium salt in water and methanol to obtain potassium chloride and mother liquor A;
and (2) concentrating the mother liquor A obtained in the step (1) to obtain mother liquor A ', recrystallizing the obtained mother liquor A' in methanol to obtain a potassium chloride enriched product, collecting the mother liquor B, and concentrating to obtain potassium fluoride.
2. The separation method according to claim 1, wherein the mixed potassium salt contains 80 ± 5% of potassium chloride, 10 ± 5% of potassium fluoride and not more than 1% of other inorganic salts, and the "%" is the mass percentage of each component in the mixed potassium salt to the total mass of the mixed potassium salt;
and/or in the step (1), the mass ratio of the methanol to the mixed potassium salt is 0.9: 1.0-2.7: 1.0;
and/or in the step (1), the mass ratio of the methanol to the water is 0.6: 1.0-1.8: 1.0;
and/or the mass ratio of the mixed potassium salt in the step (1) to the mother liquor A' in the step (2) is 0.6: 1.0-1.0: 1.0;
and/or in the step (1), the recrystallization temperature is 0-30 ℃;
and/or in the step (2), the mass ratio of the methanol to the mother liquor A' is 0.05: 1.00-0.09: 1.00;
and/or in the step (2), the recrystallization temperature is 0-30 ℃.
3. The separation method according to claim 2, wherein in the step (1), the mass ratio of the methanol to the mixed potassium salt is 1.7: 1.0-2.7: 1.0;
and/or in the step (1), the mass ratio of the methanol to the water is 1.2: 1.0-1.8: 1.0;
and/or the mass ratio of the mixed potassium salt in the step (1) to the mother liquor A' in the step (2) is 0.8: 1.0-0.9: 1.0;
and/or in the step (1), the recrystallization temperature is 0-15 ℃;
and/or in the step (2), the mass ratio of the methanol to the mother liquor A' is 0.6: 1.0-1.0: 1.0;
and/or in the step (2), the recrystallization temperature is 0-15 ℃.
4. The separation method according to claim 3, wherein in the step (1), the mass ratio of the methanol to the mixed potassium salt is 1.8: 1.0-2.7: 1.0;
and/or in the step (2), the mass ratio of the methanol to the mother liquor A' is 0.8: 1.0-1.0: 1.0.
5. The separation process of claim 1, wherein in step (1), the mixed potassium salt is subjected to a pretreatment step prior to recrystallization;
and/or, in the step (1), the recrystallization comprises the following steps: dissolving the mixed potassium salt in the water to obtain a mixed solution I; mixing the mixed solution I with the methanol, cooling and crystallizing;
and/or, in the step (1), the methanol is partially or completely obtained by concentrating and recovering the mother liquor B in the step (2);
and/or, in the step (2), the recrystallization comprises the following steps: mixing the mother liquor A' with methanol to obtain a mixed solution II; obtaining a hot solution from the mixed solution II under a reflux state, cooling and crystallizing;
and/or, in the step (2), the methanol is partially or completely obtained by concentrating and recovering the mother liquor B in the step (2);
and/or, in the step (2), the potassium chloride enriched product is recycled and applied to the step (1) so as to further improve the recovery rate and purity of potassium chloride.
6. The separation process of claim 5, wherein in step (1), when the mixed potassium salt is subjected to a pretreatment step prior to recrystallization, the pretreatment step comprises the steps of: pulping and filtering;
and/or in the step (1), in the recrystallization step, the dissolving temperature is 60-90 ℃.
7. The separation process of claim 6, wherein in step (1), the slurried solvent in the pretreatment step is one or more of toluene, dichloromethane, sulfolane and methanol, preferably sulfolane, methanol or dichloromethane;
and/or in the step (1), in the pretreatment step, the mass ratio of the solvent to the mixed potassium salt is less than or equal to 3:1, and preferably 2:1-1: 1.
8. The separation method according to any one of claims 1 to 7, wherein in the step (1), the mass ratio of the methanol to the mixed potassium salt is 0.9:1.0 to 2.7: 1.0; the mass ratio of the methanol to the water is 0.6: 1.0-1.8: 1.0; the mass ratio of the mixed potassium salt in the step (1) to the mother liquor A' in the step (2) is 0.6: 1.0-1.0: 1.0.
9. The separation method according to claim 8, wherein in the step (1), the mass ratio of the methanol to the mixed potassium salt is 1.8: 1.0-2.7: 1.0; the mass ratio of the methanol to the water is 1.2: 1.0-1.8: 1.0; the mass ratio of the mixed potassium salt in the step (1) to the mother liquor A' in the step (2) is 0.8: 1.0-0.9: 1.0.
10. The separation method according to any one of claims 1 to 7, wherein in the step (1), the mass ratio of the methanol to the mixed potassium salt is 1.7:1.0 to 2.7: 1.0; the recrystallization temperature is 0-15 ℃;
or, in the step (1), the mixed potassium salt is subjected to a pretreatment step before recrystallization; the mass ratio of the methanol to the mixed potassium salt is 1.8: 1.0-2.7: 1.0; the mass ratio of the methanol to the water is 1.2: 1.0-1.8: 1.0; the recrystallization temperature is 0-15 ℃; the mass ratio of the mixed potassium salt in the step (1) to the mother liquor A' in the step (2) is 0.8: 1.0-0.9: 1.0; in the step (2), the recrystallization temperature is 0-15 ℃.
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| CN116081868A (en) * | 2022-12-21 | 2023-05-09 | 福建省龙德新能源有限公司 | Method for treating wastewater in methylsulfonyl chloride fluorination process |
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