CN117228681A - Preparation method of potassium fluoborate - Google Patents
Preparation method of potassium fluoborate Download PDFInfo
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- CN117228681A CN117228681A CN202311259343.5A CN202311259343A CN117228681A CN 117228681 A CN117228681 A CN 117228681A CN 202311259343 A CN202311259343 A CN 202311259343A CN 117228681 A CN117228681 A CN 117228681A
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000011591 potassium Substances 0.000 title claims abstract description 38
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012071 phase Substances 0.000 claims abstract description 27
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 239000003112 inhibitor Substances 0.000 claims abstract description 8
- 239000001103 potassium chloride Substances 0.000 claims abstract description 8
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004327 boric acid Substances 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 28
- 229920000570 polyether Polymers 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- -1 potassium fluoroborate Chemical compound 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- HDMXIELEUKTYFR-UHFFFAOYSA-N bis(2-ethylhexyl) butanedioate;sodium Chemical group [Na].CCCCC(CC)COC(=O)CCC(=O)OCC(CC)CCCC HDMXIELEUKTYFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 4
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229940079868 disodium laureth sulfosuccinate Drugs 0.000 claims description 2
- YGAXLGGEEQLLKV-UHFFFAOYSA-L disodium;4-dodecoxy-4-oxo-2-sulfonatobutanoate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOC(=O)CC(C([O-])=O)S([O-])(=O)=O YGAXLGGEEQLLKV-UHFFFAOYSA-L 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000008346 aqueous phase Substances 0.000 abstract 2
- 239000002245 particle Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of chemical synthesis technology, in particular to a preparation method of potassium fluoborate, which comprises the steps of adding boric acid into waste acid liquid containing hydrofluoric acid, stirring and reacting, adding sodium hydroxide to obtain aqueous phase containing sodium fluoborate, uniformly mixing an oil phase and the aqueous phase to obtain microemulsion A, dissolving potassium chloride in water, mixing with the oil phase to obtain microemulsion B, adding the microemulsion B into the microemulsion A, stirring and reacting for 30-60min, adding a crystallization inhibitor, continuing to react for 1-3h, and centrifuging, washing and drying.
Description
Technical Field
The invention relates to the field of chemical synthesis technology, in particular to a preparation method of potassium fluoborate.
Background
Potassium fluoborate can be used as an abrasive of a thermosetting resin grinding wheel, a raw material for producing boron-containing alloy by pouring aluminum and magnesium, a flux for hot welding and brazing, a raw material for preparing boron trifluoride and other fluoride salts, an analysis reagent for electrochemical synthesis and the like, and has great market demand potential.
On one hand, the domestic potassium fluoborate manufacturers mostly use a hydrofluoric acid method, hydrofluoric acid is mainly derived from strategic resource fluorite at present, resources are limited, and on the other hand, fluorine-containing wastewater is used as one of main wastewater generated in the chemical industry, so that the pollution to the environment is huge. Enterprises often spend funds to treat the waste water before discharging the waste water, and the waste of resources is also caused.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides a preparation method of potassium fluoborate.
The technical scheme adopted is as follows:
the preparation method of the potassium fluoborate comprises the following steps:
adding boric acid into the waste acid liquid containing hydrofluoric acid, stirring and reacting, adding sodium hydroxide to obtain a water phase containing sodium fluoborate, and uniformly mixing the oil phase and the water phase to obtain a microemulsion A;
dissolving potassium chloride in water, and then mixing with the oil phase to obtain microemulsion B;
adding the microemulsion B into the microemulsion A, stirring for reaction for 30-60min, adding a crystallization inhibitor, continuing to react for 1-3h, centrifuging, washing and drying to obtain potassium fluoborate.
Further, the mass fraction of hydrofluoric acid in the waste acid liquid is more than or equal to 15%.
Further, the oil phase includes a surfactant, n-butanol, and cyclohexane.
Further, the surfactant is disodium bis (2-ethylhexyl) succinate and/or disodium laureth sulfosuccinate.
Further, the weight ratio of the surfactant to the n-butanol to the cyclohexane is 5-10:3-6:35-55.
Further, the crystallization inhibitor is a hyperbranched block polyether.
Further, the hyperbranched block polyether is obtained by reacting hyperbranched polytriethanolamine with chlorinated block polyether.
Further, the preparation method of the hyperbranched block polyether comprises the following steps:
mixing triethanolamine and sodium hydroxide, heating to 240-260 ℃, starting to receive water generated by the reaction, stopping heating until a certain amount is reached, cooling to 80-100 ℃, adding acetic acid solution, stirring uniformly, cooling to room temperature, dialyzing by using a dialysis bag to remove inorganic salt, performing reduced pressure distillation to remove water, and freeze-drying to obtain hyperbranched polytriethanolamine;
adding hydroxyl-terminated linear block polyether and triethylamine into dichloromethane, uniformly mixing, adding chloroacetyl chloride, reacting for 12-24 hours, adding water into the reaction solution for quenching, separating the solution, drying an organic phase, and distilling under reduced pressure to remove dichloromethane to obtain chlorinated linear block polyether;
and (3) mixing hyperbranched polytriethanolamine, chlorinated linear block polyether and ethanol, sealing and heating to 60-70 ℃ under the protection of nitrogen, reacting for 24-48h, and distilling under reduced pressure after the reaction is finished to remove the ethanol, thus obtaining the hyperbranched block polyether.
Further, the crystallization inhibitor is used in an amount of 0.1 to 0.5% by weight based on the weight of potassium chloride.
The invention has the beneficial effects that:
the invention provides a preparation method of potassium fluoborate, which comprises the steps of firstly reacting boric acid with hydrofluoric acid in waste acid liquid to generate fluoboric acid, then reacting the fluoboric acid with sodium hydroxide to obtain sodium fluoborate, and finally separating out the potassium fluoborate from a reaction system through double decomposition reaction by utilizing the solubility difference;
the inventor researches find that if the potassium fluoborate is directly produced by the reaction of fluoboric acid and potassium hydroxide, the obtained potassium fluoborate has lower purity and larger loss when recrystallized, and by adopting the process of the invention, the consumption of potassium hydroxide with higher price can be saved, the obtained potassium fluoborate has the purity of more than 99 percent directly, the recrystallization step is omitted, and the yield is also improved;
the reverse microemulsion method has the advantages of simple operation and stable system, can effectively control the size and morphology of the prepared particles of the reverse microemulsion method, but cannot reach the nano-scale, and the inventor further researches that hyperbranched block polyether is added as a crystallization inhibitor, is dispersed in a reaction system to prevent ions from diffusing among crystal grains, can prevent the formation and growth of crystal particles, and finally obtains nano-scale high-purity potassium fluoborate.
The invention uses the fluorine-containing wastewater generated in the chemical industry as one of the main raw materials, saves the cost of the raw materials, also has the effect of recycling waste, protects the environment, and also saves the capital cost of the chemical enterprises for additionally treating the fluorine-containing wastewater.
Drawings
FIG. 1 is a photograph of potassium fluoroborate prepared in example 1.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The technology not mentioned in the present invention refers to the prior art, and unless otherwise indicated, the following examples and comparative examples are parallel tests, employing the same processing steps and parameters.
Example 1:
a preparation method of potassium fluoborate:
the waste acid liquid containing hydrofluoric acid is from the semiconductor industry, wherein the mass fraction of the hydrofluoric acid is 17.2%, boric acid is added into 1kg of the waste acid liquid, the pH of a system is adjusted to 9 by slowly adding sodium hydroxide after stirring and reacting for 5 hours, and the temperature of the system is controlled to be always lower than 40 ℃ to obtain a water phase containing sodium fluoborate;
sodium bis (2-ethylhexyl) succinate, n-butanol and cyclohexane are mixed according to the weight ratio of 8:5:50, uniformly mixing to obtain an oil phase, adding the water phase into 10kg of the oil phase, and uniformly mixing to obtain a microemulsion A;
160g of potassium chloride is dissolved in 840ml of water and then added into 10kg of oil phase, and the mixture is uniformly mixed to obtain microemulsion B;
adding the microemulsion B into the microemulsion A, stirring and reacting for 40min, adding 0.5g of hyperbranched block polyether, continuing to react for 2h, centrifuging, leaching the obtained product with water and ethanol, transferring to a vacuum drying oven, drying at 60 ℃ for 24h, wherein the total yield is 60.5%, the purity of the measured potassium fluoborate is 99.3%, all indexes meet the national standard GB/T22667-2008 requirements, the potassium fluoborate can be directly sold, dispersing the potassium fluoborate by adopting a circulating dispersion sample injection system, and carrying out particle size test by using a laser particle size distribution instrument, and the particle size of the prepared potassium fluoborate is between 10 nm and 50 nm.
The preparation method of the hyperbranched block polyether comprises the following steps:
adding 149g of triethanolamine and 2g of sodium hydroxide into a flask, mixing and heating to 250 ℃ under stirring, at the moment, starting to receive water generated by reaction by a water separator, stopping heating until the volume of the mixture reaches 20ml, naturally cooling the reaction liquid to 100 ℃, adding 30g of 5w% acetic acid solution, stirring uniformly, cooling to room temperature, removing inorganic salt by dialysis through a dialysis bag, distilling under reduced pressure to remove water, freeze-drying to obtain hyperbranched polytriethanolamine, adding 15g of hydroxyl-terminated linear block polyether SD901 and 0.506g of triethylamine into 30ml of dichloromethane, uniformly mixing, adding 0.565g of chloroacetyl chloride, reacting for 12h, adding 30ml of water for quenching, stirring for 30min, separating the liquid, drying a dichloromethane phase by anhydrous sodium sulfate, distilling under reduced pressure to remove dichloromethane to obtain the chlorinated linear block polyether, and adding the hyperbranched polytriethanolamine and the chlorinated linear block polyether into a molar ratio of 6:1 adding a proper amount of absolute ethyl alcohol, uniformly mixing, introducing nitrogen for 10min, sealing, heating to 65 ℃ for reaction for 36h, and distilling under reduced pressure to remove the ethanol after the reaction is finished, thus obtaining the hyperbranched block polyether.
Example 2:
a preparation method of potassium fluoborate:
the waste acid liquid containing hydrofluoric acid is from the semiconductor industry, wherein the mass fraction of the hydrofluoric acid is 17.2%, boric acid is added into 1kg of the waste acid liquid, the pH of a system is adjusted to 9 by slowly adding sodium hydroxide after stirring and reacting for 5 hours, and the temperature of the system is controlled to be always lower than 40 ℃ to obtain a water phase containing sodium fluoborate;
sodium bis (2-ethylhexyl) succinate, n-butanol and cyclohexane are mixed according to the weight ratio of 10:6:55 to obtain an oil phase, adding the water phase into 10kg of the oil phase, and uniformly mixing to obtain a microemulsion A;
160g of potassium chloride is dissolved in 840ml of water and then added into 10kg of oil phase, and the mixture is uniformly mixed to obtain microemulsion B;
adding the microemulsion B into the microemulsion A, stirring for reaction for 60min, adding 0.5g of hyperbranched block polyether, continuing to react for 3h, centrifuging, leaching the obtained product with water and ethanol, transferring to a vacuum drying oven, and drying at 60 ℃ for 24h, wherein the total yield is 58.2%, the purity of the measured potassium fluoborate is 99.4%, all indexes meet the national standard GB/T22667-2008 requirements, the potassium fluoborate can be directly sold, the potassium fluoborate can be dispersed by adopting a circulating dispersion sample injection system, and the particle size of the potassium fluoborate is 10-50nm by using a laser particle size distribution instrument.
Wherein the preparation method of the hyperbranched block polyether is the same as in example 1.
Example 3:
a preparation method of potassium fluoborate:
the waste acid liquid containing hydrofluoric acid is from the semiconductor industry, wherein the mass fraction of the hydrofluoric acid is 17.2%, boric acid is added into 1kg of the waste acid liquid, the pH of a system is adjusted to 9 by slowly adding sodium hydroxide after stirring and reacting for 5 hours, and the temperature of the system is controlled to be always lower than 40 ℃ to obtain a water phase containing sodium fluoborate;
sodium bis (2-ethylhexyl) succinate, n-butanol and cyclohexane are mixed according to a weight ratio of 5:3:35, adding the water phase into 10kg of oil phase, and uniformly mixing to obtain microemulsion A;
160g of potassium chloride is dissolved in 840ml of water and then added into 10kg of oil phase, and the mixture is uniformly mixed to obtain microemulsion B;
adding the microemulsion B into the microemulsion A, stirring for reaction for 30min, adding 0.5g of hyperbranched block polyether, continuing to react for 2h, centrifuging, leaching the obtained product with water and ethanol, transferring to a vacuum drying oven, drying at 60 ℃ for 24h, wherein the total yield is 56.6%, the purity of the measured potassium fluoborate is 99.0%, all indexes meet the national standard GB/T22667-2008 requirements, the potassium fluoborate can be directly sold, the potassium fluoborate can be dispersed by adopting a circulating dispersion sample injection system, and the particle size of the potassium fluoborate is 10-50nm by using a laser particle size distribution instrument for particle size test.
Wherein the preparation method of the hyperbranched block polyether is the same as in example 1.
Comparative example 1:
the method is basically the same as that of example 1, except that hyperbranched block polyether is not added, the total yield is 55.9%, the purity of the measured potassium fluoborate is 98.8%, all indexes meet the requirements of national standard GB/T22667-2008, the potassium fluoborate can be directly sold, a circulating dispersion sample injection system is adopted to disperse the potassium fluoborate, a laser particle size distribution instrument is used for particle size testing, and the particle size of the prepared potassium fluoborate is between 1 and 10 mu m.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. The preparation method of the potassium fluoborate is characterized by comprising the following steps of:
adding boric acid into the waste acid liquid containing hydrofluoric acid, stirring and reacting, adding sodium hydroxide to obtain a water phase containing sodium fluoborate, and uniformly mixing the oil phase and the water phase to obtain a microemulsion A;
dissolving potassium chloride in water, and then mixing with the oil phase to obtain microemulsion B;
adding the microemulsion B into the microemulsion A, stirring for reaction for 30-60min, adding a crystallization inhibitor, continuing to react for 1-3h, centrifuging, washing and drying to obtain potassium fluoborate.
2. The method for preparing potassium fluoborate according to claim 1, wherein the mass fraction of hydrofluoric acid in the waste acid liquid is not less than 15%.
3. The method of preparing potassium fluoroborate according to claim 1, wherein the oil phase comprises a surfactant, n-butanol and cyclohexane.
4. A method of preparing potassium fluoroborate as claimed in claim 3 wherein the surfactant is sodium bis (2-ethylhexyl) succinate and/or disodium laureth sulfosuccinate.
5. The method for preparing potassium fluoborate according to claim 3, wherein the weight ratio of the surfactant, the n-butanol and the cyclohexane is 5-10:3-6:35-55.
6. The method of preparing potassium fluoroborate according to claim 1, wherein the crystallization inhibitor is a hyperbranched block polyether.
7. The method of claim 6, wherein the hyperbranched polyether block is prepared by reacting hyperbranched polytriethanolamine with a chlorinated polyether block.
8. The method of claim 7, wherein the hyperbranched block polyether is prepared by:
mixing triethanolamine and sodium hydroxide, heating to 240-260 ℃, starting to receive water generated by the reaction, stopping heating until a certain amount is reached, cooling to 80-100 ℃, adding acetic acid solution, stirring uniformly, cooling to room temperature, dialyzing by using a dialysis bag to remove inorganic salt, performing reduced pressure distillation to remove water, and freeze-drying to obtain hyperbranched polytriethanolamine;
adding hydroxyl-terminated linear block polyether and triethylamine into dichloromethane, uniformly mixing, adding chloroacetyl chloride, reacting for 12-24 hours, adding water into the reaction solution for quenching, separating the solution, drying an organic phase, and distilling under reduced pressure to remove dichloromethane to obtain chlorinated linear block polyether;
and (3) mixing hyperbranched polytriethanolamine, chlorinated linear block polyether and ethanol, sealing and heating to 60-70 ℃ under the protection of nitrogen, reacting for 24-48h, and distilling under reduced pressure after the reaction is finished to remove the ethanol, thus obtaining the hyperbranched block polyether.
9. The method of preparing potassium fluoroborate according to claim 1, wherein the crystallization inhibitor is used in an amount of 0.1 to 0.5% by weight based on the weight of potassium chloride.
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| CN103332700A (en) * | 2013-07-23 | 2013-10-02 | 森田化工(张家港)有限公司 | Method for preparing potassium borofluoride through fluorine-containing wastewater |
| CN109354034A (en) * | 2018-11-22 | 2019-02-19 | 山东罗欣药业集团股份有限公司 | A kind of fluorine-containing waste liquid borofluoride exchange crystallization recovery technology of cephalo |
| CN110510625A (en) * | 2019-09-20 | 2019-11-29 | 四川师范大学 | The method and potassium fluoborate of the fluorine-containing aqueous slkali separation fluorine of bastnaesite and application |
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2023
- 2023-09-26 CN CN202311259343.5A patent/CN117228681B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3290113A (en) * | 1962-05-15 | 1966-12-06 | Chemical & Phosphates Ltd | Process for the manufacture of alkali metal fluoborates |
| GB1155304A (en) * | 1965-09-02 | 1969-06-18 | Ceskoslovenska Akademie Ved | Process for Preparing Borohydrides. |
| CN103332700A (en) * | 2013-07-23 | 2013-10-02 | 森田化工(张家港)有限公司 | Method for preparing potassium borofluoride through fluorine-containing wastewater |
| CN109354034A (en) * | 2018-11-22 | 2019-02-19 | 山东罗欣药业集团股份有限公司 | A kind of fluorine-containing waste liquid borofluoride exchange crystallization recovery technology of cephalo |
| CN110510625A (en) * | 2019-09-20 | 2019-11-29 | 四川师范大学 | The method and potassium fluoborate of the fluorine-containing aqueous slkali separation fluorine of bastnaesite and application |
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