CN113772707A - Treatment method of fluorine-containing potassium chloride - Google Patents
Treatment method of fluorine-containing potassium chloride Download PDFInfo
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- C01F11/20—Halides
- C01F11/22—Fluorides
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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
- C01D3/04—Chlorides
- C01D3/08—Preparation by working up natural or industrial salt mixtures or siliceous minerals
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Abstract
The invention discloses a treatment method of fluorine-containing potassium chloride, and relates to the field of chemical industry. Dissolving an organic byproduct fluorine-containing potassium chloride raw material in water, standing and settling after the dissolution is finished to obtain a supernatant; adding a precipitator Ca (OH) into the supernatant2After growing the crystal, stirring for reaction, and adjusting the pH value; then adding an APAM aqueous solution, stirring for reaction, standing and settling to obtain a supernatant and a lower slurry. Compared with the prior art, the defluorination method has the advantages that the cost of the precipitator is low, the problems of difficult filtration and difficult solid-liquid separation are solved, complicated and high-cost separation equipment is not required, the cost is obviously reduced, and the defluorination method has a better application prospect in the field of chemical industry and environmental protection.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a treatment method of fluorine-containing potassium chloride.
Background
Potassium fluoride (KF) is widely used in organic fluorination reactions as a common fluorinating agent. During the production of fluroxypyr, KF is converted to potassium chloride (KCl) as a by-product of the reaction into fluorination reaction residue with the production of organic fluorination products. The residue contains KCl as main component, unreacted KF, small amount of sulfolane as solvent, organic impurities, iron filings, etc. Since the residue contains fluoride which is a dangerous chemical belonging to dangerous solid waste, the application field of the fluorine-containing potassium chloride mixed salt is very limited.
With the progress of social economy, the national environmental protection requirements for various industries are more strict, and the focus of research personnel on recycling the salt in the by-product and reducing the discharge of three wastes is important. At present, enterprises generally sell the potassium-enriched potassium directly, commission the potassium-enriched potassium to treat the potassium-enriched potassium or burn the potassium-enriched potassium and then enter a sewage treatment system, the commission treatment increases the production cost of the enterprises, and the potassium-enriched potassium is burnt to enter the sewage treatment system, so that the environment is polluted and the precious potassium resource is wasted. Therefore, the salt in the by-product is recycled, so that the environment-friendly production concept can be practiced, the greater economic advantage can be generated, the production cost is reduced, and how to improve the purity of the KCl in the by-product is a main bottleneck for restricting the recycling.
The KCl in the byproduct must be removed by improving the purity of the KCl. At present, the defluorination method can be divided into a chemical precipitation method and an adsorption method according to the fluorine content in the raw materials, wherein the former is mainly used for treating the wastewater with high fluorine content, and the latter is mainly used for treating the wastewater with lower concentration. The chemical precipitation method has the advantages of simple process, low cost, obvious fluorine removal effect and the like, and is widely applied in industry.
However, in practical practice, due to the complex components in the wastewater containing fluorine, the fluorine removal effect is often not satisfactory, and the subsequent separation process is also due to calcium fluoride (CaF)2) The particle size is tiny, leads to filtering the difficulty, and the problem that cross filtration, filter membrane block up takes place occasionally, has seriously influenced defluorination efficiency, consequently how to improve subsequent solid-liquid separation process under the prerequisite of guaranteeing the defluorination effect, is the difficult problem that needs to solve urgently.
At present, some patents also disclose methods for defluorination purification or resource utilization of fluorine-containing potassium chloride.
Chinese patent CN104477942A discloses a method for treating potassium chloride residue in organic fluorination reaction, which comprises the following steps: extracting KCl residue with water in leaching kettle, dissolving KCl, KF and sulfolane in water, filtering to separate carbide and cokeOil and other water-insoluble organic impurities, washing the impurities with hot water, and then sending the impurities to qualified solid waste treatment plants, wherein the washing water is used for leaching residues; the leaching solution enters an extraction kettle, organic solvent is used for extracting sulfolane dissolved in water, standing and layering are carried out, oil phase is desolventized, organic solvent is recovered and then returned for extraction, and the remainder is sulfolane; the water phase enters a precipitation kettle, and a precipitator is added under stirring to ensure that the precipitation reaction is complete; separating the precipitate, washing and drying to obtain calcium fluoride, and leaching the residue with washing water; and (4) concentrating and crystallizing the separated liquid in an evaporator, and centrifugally drying to obtain KCl. The KCl product obtained in the patent has the purity of 98 percent, and the CaF obtained in the patent2The separation still faces the problem of difficult filtration and is difficult to industrialize.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a treatment method of fluorine-containing potassium chloride, which has the advantages of simple process flow, mild condition, low energy consumption, obvious economic benefit and environmental protection benefit and can be applied to industrial scale popularization.
In the invention, the raw materials are byproducts generated by fluorination reaction by taking KF as a fluorination reagent in the production of fluroxypyr, mainly comprise KCl and KF and contain a small amount of sulfolane.
In the present invention, PAM refers to polyacrylamide, and PAM includes three types, i.e., Anionic Polyacrylamide (APAM), Cationic Polyacrylamide (CPAM), and Nonionic Polyacrylamide (NPAM), unless otherwise specified.
The treatment method of fluorine-containing potassium chloride provided by the invention comprises the following steps:
(1) adding a precipitant Ca (OH) to an aqueous solution containing potassium chloride fluoride2Standing for crystal growth and then stirring for reaction;
(2) after the reaction in the step (1) is finished, regulating the pH value of the reaction system to be 1-11 by using hydrochloric acid;
(3) adding anionic polyacrylamide or an aqueous solution of anionic polyacrylamide into the reaction system in the step (2), stirring for reaction, and standing and settling after the stirring reaction is finished to obtain lower-layer slurry and upper-layer clear liquid;
(4) performing post-treatment on the lower layer slurry obtained in the step (3) to obtain CaF2(ii) a Supernatant obtained in step (3)The liquid is post-treated to obtain KCl.
And (4) the post-treatment step of the lower-layer slurry obtained in the step (3) comprises the steps of washing, filtering, drying and the like.
The post-treatment step of the supernatant obtained in the step (3) comprises the steps of adjusting the pH value to be neutral by hydrochloric acid, evaporating and crystallizing, centrifugally separating, drying and the like.
In specific examples, the inventors tried calcium hydroxide (Ca (OH)2) Calcium chloride (CaCl)2) Calcium carbonate (CaCO)3) Or calcium sulfate (CaSO)4) As precipitant, CaCl is used2Although the optimal treatment effect can be achieved, the subsequent flocculation condition is poor, and the filtration is difficult; using Ca (OH)2When the flocculant is a precipitator, a better flocculation effect and smaller filtration resistance can be considered under a better treatment effect; using CaCO3Or CaSO4In the case of a precipitant, the treatment effect is general, and the problems of poor flocculation and difficult filtration also exist.
The above-mentioned precipitating agent Ca (OH)2Is calculated according to the KF content in the fluorine-containing potassium chloride water solution, wherein, the precipitator Ca (OH)2The molar ratio of KF to the aqueous solution of fluorine-containing potassium chloride is 1 to 2.
In the aforementioned step (1), the reaction temperature is 10 to 90 ℃.
Further, in the aforementioned step (1), the reaction temperature is 10 to 30 ℃.
Further, in the step (1), the reaction temperature is 25 ℃.
In the step (1), the standing and crystal growing time is not less than 3 minutes. Adding a precipitator into an aqueous solution containing fluorine potassium chloride, wherein the precipitator can react with KF; on the other hand, the precipitant can be used as seed crystal for crystal growth. The increase of the time for growing the crystals is beneficial to forming large particles, and the treatment efficiency is influenced if the time is too long.
Further, in the step (1), the standing and crystal growth time is 5 to 20 minutes.
Furthermore, in the step (1), the standing time for growing the crystal is 5 to 10 minutes.
In the step (2), the pH value of the system is adjusted to 3.10 to 9.03.
Further, in the step (2), the pH value of the system is adjusted to 6.00 to 7.01.
Further, in the step (2), the pH value of the system is adjusted to 7.01.
In the step (3), the flocculant is APAM or an aqueous solution of APAM.
Further, in the step (3), the flocculant is an aqueous solution of APAM.
In the specific examples, the inventors tried to use an aqueous solution of CPAM or an aqueous solution of NPAM as a flocculant and did not find a flocculation effect.
Further, in the specific examples, the inventors tried to use zinc chloride, aluminum potassium sulfate dodecahydrate, polyaluminum chloride, and polyferric sulfate as flocculants, and still have no flocculation effect.
The concentration of the aforementioned aqueous solution of APAM is 0.05 wt% to 0.2 wt%.
Further, the concentration of the aqueous solution of the aforementioned APAM was 0.1 wt%.
The amount of the above-mentioned APAM is calculated based on the amount of KF in an aqueous solution of a fluorine-containing potassium chloride, and the mass ratio of the APAM to the KF in the aqueous solution of the fluorine-containing potassium chloride is 0.03 to 0.10% to 1, preferably 0.06% to 1.
The molecular weight of the aforementioned APAM is 300 to 2000 ten thousand. The APAM molecular weight is not suitable to be too small, so that the use amount is increased; the molecular weight of the APAM is not suitable to be too large, which increases the dissolution time of the APAM to be prepared into an aqueous solution, and also makes the viscosity of the aqueous solution too large to be practical.
Further, the molecular weight of the aforementioned APAM is 500 to 1600 ten thousand.
Further, the aforementioned APAM has a molecular weight of 800 to 1200 ten thousand.
The flocculant may be PAM as it is, without using an aqueous solution of PAM. Because PAM has a slow dissolving process in water, the inventor prepares PAM into an aqueous solution with a certain concentration in advance, and then directly adopts the aqueous solution of PAM as a flocculating agent.
The preparation method of the fluorine-containing potassium chloride aqueous solution comprises the following steps: dissolving the raw material containing fluorine potassium chloride in water, standing and settling, and taking supernatant as the water solution containing fluorine potassium chloride.
In the above method for producing an aqueous solution of potassium fluorochloride, the mass ratio of the raw material of potassium fluorochloride to water is 1: 3.0 to 3.5.
The aqueous solution of the foregoing fluorine-containing potassium chloride may have a KCl content of 15 wt% to 30 wt%, and in certain embodiments, may have a KCl content of 15 wt%, 17 wt%, 19 wt%, 21 wt%, 23 wt%, 25 wt%, 30 wt%. In a specific embodiment of the present invention, the KCl content in the aqueous solution of fluorine-containing potassium chloride was 21.16 wt%.
The aqueous solution of fluorine-containing potassium chloride may contain KF in an amount of 1 wt% to 10 wt%, and in certain embodiments, may contain KF in an amount of 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 10 wt%. In a specific example of the present invention, the content of KF in the aqueous solution of fluorine-containing potassium chloride was 3.14 wt%.
The aqueous solution of the foregoing fluorinated potassium chloride may contain TMS in an amount of 0.1 wt.% to 1 wt.%, and in certain embodiments, the amount of TMS may be 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.%. In a specific embodiment of the invention, the TMS content of the aqueous solution of potassium fluorochlorides is 0.6 wt%.
In the step (1), the rotation speed of the stirring is 100 to 120 rpm.
In the step (2), the stirring speed is 30 to 60rpm, and in this step, too high stirring speed is disadvantageous to flocculation.
Compared with the prior art, the method solves the problems of difficult filtration, difficult solid-liquid separation and the like in the precipitation defluorination method, reduces the cost, has simple process operation steps, and improves the purity of the recovered KCl by the technical scheme of the invention.
Compared with the prior art, the invention has the advantages that:
(1) low cost, no need of special precipitant, and only cheap and easily available Ca (OH)2Can achieve excellent defluorinationThe effect is achieved;
(2) compared with the existing precipitation defluorination method, the method has the advantages of no problems of difficult filtration, difficult solid-liquid separation and the like, no need of introducing complicated and high-cost separation equipment, obviously reduced equipment investment and reduced cost.
(3) The prepared KCl has high purity and good defluorination effect;
(4) CaF obtained by subsequent washing, filtering and drying2Can be recycled, and fully utilizes resources.
Detailed Description
The present invention will be explained in more detail with reference to the following examples, which are provided for illustrating the technical solutions of the present invention and are not intended to limit the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adjustments, and still fall within the scope of the present invention.
The experimental equipment, detection conditions, experimental raw materials and the like which are not specifically described in the invention are all conventional technical means and common substances, and can be obtained through a public way.
Example 1
Dissolving 715g of fluorine-containing potassium chloride raw material in 2288g of water at room temperature, standing and settling to obtain 3000g of supernatant, wherein the supernatant has KCl content of 21.16 wt%, KF content of 3.14 wt% and sulfolane content of 0.60 wt% according to ion chromatography detection.
Example 2
100g of the supernatant of example 1 was taken, and the precipitant Ca (OH) was added thereto in one portion22.00g, standing for crystal growth for 5-20 min, setting the stirring speed to 120rpm, stirring and reacting at 25 ℃ for 2h, and detecting the pH value of the reaction system to be 13.80 after the reaction is finished. And then, the rotating speed is reduced to 60rpm, 2.0g of 0.1 wt% APAM aqueous solution is slowly added, the molecular weight of the APAM is 1200 ten thousand, the flocculation condition is observed after the addition is finished until macroscopic flocs are formed, the stirring is stopped, and the mixture is kept stand and settled for 30min to obtain 98g of supernatant and lower layer slurry. The KF content in the supernatant was 0.420 wt% by ion chromatography.
Example 3
The effect of different precipitants on the fluorine removal effect was examined according to the method of example 2, using different precipitants.
TABLE 1 influence of precipitant species on the defluorination effectiveness
It can be seen that a precipitant CaCl is adopted2Although the optimal defluorination effect can be achieved (the KF content in the supernatant is the lowest), the subsequent flocculation condition is poor, and the filtration is not facilitated; instead, Ca (OH) is used2When the flocculant is a precipitator, the defluorination effect can be better, and simultaneously, the flocculation effect is better and the filtration resistance is smaller.
Example 4
100g of the supernatant of example 1 was taken, and the precipitant Ca (OH) was added thereto in one portion22.00g, standing for crystal growth for 5-20 min, setting the stirring speed to 120rpm, stirring and reacting at 25 ℃ for 2h, and detecting the pH value of the reaction system to be 13.80 after the reaction is finished. Hydrochloric acid is added to adjust the pH value of the system to 7.01. And then, the rotating speed is reduced to 60rpm, 2.0g of 0.1 wt% APAM aqueous solution is slowly added, the molecular weight of the APAM is 1200 ten thousand, the flocculation condition is observed after the addition is finished until macroscopic flocs are formed, the stirring is stopped, and the mixture is kept stand and settled for 30min to obtain 98g of supernatant and lower layer slurry. The KF content in the supernatant was 0.025 wt% by ion chromatography.
Washing, filtering and drying wet slag obtained after filtering the lower-layer slurry to obtain CaF2Product, CaF in the product by detection2The content is 98.7 wt%, and the KCl content is 0.63 wt%. And observing the filtration condition in the process, wherein the filtration process adopts a decompression suction filtration device commonly used in chemical experiments.
And (3) adjusting the supernatant to be neutral by hydrochloric acid, then sending the neutral supernatant into a crystallization kettle, evaporating, crystallizing, centrifuging to obtain a KCl wet product, washing and drying to obtain a KCl product, wherein the evaporative crystallization mother liquor can be recycled. The detection shows that the product has KCl content of 99.4 wt%, fluorine ion content of 0.016 wt%, calcium ion content of 0.018 wt% and water content of 0.030 wt%.
As shown in Table 2, the technical requirements of industrial and agricultural potassium chloride (GB/T6549-.
TABLE 2 technical requirements for potassium chloride for industry and agriculture (GB/T6549-
Wherein, the calculation formula of the potassium oxide is as follows:
example 5
The effect of different pH on the defluorination effect was examined by adjusting the pH of the system by adding hydrochloric acid as in example 4.
TABLE 3 influence of pH on the defluorination Effect
Example 6
Following the procedure of example 4, with addition of the precipitant Ca (OH)2Growing crystal later, stirring and reacting, controlling the stirring and reacting temperature, and inspecting the influence of different reacting temperatures on the defluorination effect.
TABLE 4 influence of reaction temperature on the efficiency of defluorination
Example 7
The effect of different flocculants on flocculation was examined by varying the flocculant type as in example 4. Wherein, the APAM, CPAM and NPAM are all commercial products, and the molecular weight is 1150 to 1250 ten thousand.
TABLE 5 influence of the flocculant type on the flocculation Effect
The term "better flocculation effect" means that during the flocculation process, as the flocculating agent is added, the turbid system gradually generates flocs, and at this time, the liquid phase in the system becomes clear obviously.
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 method for treating fluorine-containing potassium chloride is characterized by comprising the following steps of:
(1) adding a precipitator calcium hydroxide into the aqueous solution containing fluorine potassium chloride, standing for crystal growth, and then stirring for reaction;
(2) after the reaction in the step (1) is finished, regulating the pH value of the reaction system to be 1-11 by using hydrochloric acid;
(3) adding anionic polyacrylamide or an aqueous solution of anionic polyacrylamide into the reaction system in the step (2), stirring for reaction, and standing and settling after the stirring reaction is finished to obtain lower-layer slurry and upper-layer clear liquid;
(4) carrying out post-treatment on the lower layer slurry obtained in the step (3) to obtain calcium fluoride; and (4) carrying out post-treatment on the supernatant obtained in the step (3) to obtain potassium chloride.
2. The method for treating fluorine-containing potassium chloride according to claim 1, wherein in the step (1), the reaction temperature is 10 to 90 ℃; preferably, the temperature of the reaction is 10 to 30 ℃; more preferably, the temperature of the reaction is 25 ℃.
3. The method for treating fluorine-containing potassium chloride according to claim 1 or 2, wherein in the step (1), the standing crystal growth time is not less than 3 minutes, preferably 5 to 20 minutes, and more preferably 5 to 10 minutes.
4. The method for treating fluorine-containing potassium chloride according to any one of claims 1 to 3, wherein in the step (2), the pH value of the system is adjusted to 3.10 to 9.03; preferably, the pH value of the system is adjusted to be 6.00 to 7.01; more preferably, the pH of the system is adjusted to 7.01.
5. The method of claim 1, wherein the concentration of the aqueous solution of anionic polyacrylamide is 0.05 wt% to 0.2 wt%, preferably 0.1 wt%.
6. The method for treating fluorine-containing potassium chloride according to claim 1, wherein the amount of the anionic polyacrylamide is calculated according to the amount of potassium fluoride in the aqueous solution of fluorine-containing potassium chloride, and the mass ratio of the anionic polyacrylamide to the potassium fluoride is 0.03 to 0.10% to 1, preferably 0.06% to 1.
7. The method of treating fluorine-containing potassium chloride according to claim 1 or 6, wherein the molecular weight of the anionic polyacrylamide is 300 to 2000 ten thousand, preferably 500 to 1600 ten thousand, more preferably 800 to 1200 ten thousand.
8. The method for treating fluorine-containing potassium chloride according to claim 1, wherein the amount of calcium hydroxide as a precipitant is calculated from the amount of potassium fluoride in the aqueous solution of fluorine-containing potassium chloride, and the molar ratio of calcium hydroxide as a precipitant to potassium fluoride in the aqueous solution of fluorine-containing potassium chloride is 1 to 2.
9. The method for treating fluorine-containing potassium chloride according to claim 1, wherein the method for preparing the aqueous solution of fluorine-containing potassium chloride comprises: dissolving the raw material containing fluorine potassium chloride in water, standing and settling, and taking supernatant.
10. The method for treating fluorine-containing potassium chloride according to any one of claims 1 to 9, wherein the content of potassium chloride in the aqueous solution of fluorine-containing potassium chloride is 15 to 30 wt%; the content of the potassium fluoride is 1 to 10 weight percent; the sulfolane content is 0.1 wt% to 1 wt%.
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