CN115385341A - Method for preparing potassium fluosilicate by recovering acid wastewater from tantalum-niobium hydrometallurgy - Google Patents
Method for preparing potassium fluosilicate by recovering acid wastewater from tantalum-niobium hydrometallurgy Download PDFInfo
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- CN115385341A CN115385341A CN202211184342.4A CN202211184342A CN115385341A CN 115385341 A CN115385341 A CN 115385341A CN 202211184342 A CN202211184342 A CN 202211184342A CN 115385341 A CN115385341 A CN 115385341A
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- 239000002253 acid Substances 0.000 title claims abstract description 91
- 239000002351 wastewater Substances 0.000 title claims abstract description 70
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000011591 potassium Substances 0.000 title claims abstract description 69
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 69
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 41
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 37
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 154
- 239000001103 potassium chloride Substances 0.000 claims abstract description 77
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 77
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 49
- 239000000706 filtrate Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000004111 Potassium silicate Substances 0.000 claims abstract description 16
- QDIYZGWZTHZFNM-UHFFFAOYSA-N [F].[K] Chemical compound [F].[K] QDIYZGWZTHZFNM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 16
- 229910052913 potassium silicate Inorganic materials 0.000 claims abstract description 16
- 239000010865 sewage Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000008399 tap water Substances 0.000 claims abstract description 12
- 235000020679 tap water Nutrition 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000004064 recycling Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 41
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 15
- 229910052731 fluorine Inorganic materials 0.000 description 15
- 239000011737 fluorine Substances 0.000 description 15
- 230000002378 acidificating effect Effects 0.000 description 13
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 150000004673 fluoride salts Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000013064 chemical raw material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- -1 potassium fluorosilicate Chemical compound 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- KXEOSTAFIDYVEF-UHFFFAOYSA-N [Si](O)(O)(O)O.[F] Chemical compound [Si](O)(O)(O)O.[F] KXEOSTAFIDYVEF-UHFFFAOYSA-N 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
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/10—Compounds containing silicon, fluorine, and other elements
- C01B33/103—Fluosilicic acid; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention relates to the technical field of sewage treatment, in particular to a method for recovering and preparing potassium fluosilicate from acid wastewater generated in tantalum-niobium hydrometallurgy. The method comprises the following steps: conveying the potassium chloride solid particles into a dissolving tank, and dissolving with hot tap water to obtain a potassium chloride solution; throwing acid wastewater from tantalum-niobium hydrometallurgy into a stirring tank, adding silicon powder, stirring and reacting for a period of time at 40-60 ℃ to obtain a solution containing fluosilicic acid; filtering the obtained solution containing the fluosilicic acid to obtain filtrate and unreacted silicon powder; at normal temperature, mixing the obtained filtrate and the obtained potassium chloride solution according to a volume ratio of 1:0.55, slowly dripping into a synthesis tank, and reacting for a period of time to obtain liquid containing fluorine potassium silicate; and centrifuging and drying the obtained liquid containing the fluorine potassium silicate to obtain the potassium fluosilicate. The method has simple treatment process and low production cost, the purity of the prepared potassium fluosilicate is up to more than 99 percent, the yield is up to more than 90 percent, and the method has great popularization.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for preparing potassium fluosilicate by recovering acid wastewater from tantalum-niobium hydrometallurgy.
Background
The tantalum-niobium hydrometallurgy acidic wastewater contains a large amount of hydrofluoric acid, silicon tetrafluoride, fluosilicic acid, sulfuric acid, fluotitanic acid, fluoride salt, sulfate and the like, the components are very complex, lime is generally adopted in the traditional treatment process for neutralization, and then the lime is discharged after reaching standards, but a large amount of lime slag containing calcium fluoride, calcium sulfate and other components is generated in the neutralization process, new pollutants are formed, the lime slag needs to be transported to a solid waste treatment place for further treatment, the environmental protection problem is difficult to be thoroughly solved, and meanwhile, fluorine and silicon resources such as hydrofluoric acid, fluosilicic acid and the like in the wastewater are not recycled, so that a large amount of resource waste is caused.
Potassium fluosilicate is an inorganic compound, slightly soluble in water, hydrolyzable in hot water into potassium fluoride, hydrogen fluoride and silicic acid, which decompose into potassium fluoride and silicon tetrafluoride upon firing. The mica powder is commonly used for wood preservation, ceramic glaze manufacture, aluminum and magnesium smelting, agricultural insecticide and optical glass manufacture, and raw materials of synthetic mica and electric welding electrodes, and has wide application.
Chinese patent publication No. CN 111732104A discloses a method for preparing potassium fluosilicate from fluorine-containing wastewater, which recovers fluorine resources in the wastewater by a direct mixing reaction of fluosilicic acid and potassium chloride, but in the method, a filtrate containing fluorine silicic acid and a potassium chloride solution are directly mixed when synthesizing potassium fluosilicate, and the synthesis is carried out at a heating temperature, so that the yield of the obtained potassium fluosilicate is not high due to easy hydrolysis of potassium fluosilicate in hot water.
Disclosure of Invention
Based on the above, the invention aims to provide a method for preparing potassium fluosilicate by recycling acid wastewater from tantalum-niobium hydrometallurgy, which solves the problems that in the prior art, lime neutralization is simply carried out on the acid wastewater from tantalum-niobium hydrometallurgy, new pollutants are generated, and fluorine and silicon resources in the acid wastewater from tantalum-niobium hydrometallurgy are wasted. The method can recover hydrofluoric acid, fluosilicic acid, silicon tetrafluoride, fluoride salt and the like in the tantalum-niobium hydrometallurgy acidic wastewater, the recovered potassium fluosilicate has high purity and high yield, can be directly used as a chemical raw material, brings economic benefits to enterprises, and the residual wastewater is discharged after being treated.
In order to solve the technical problems, the invention provides the following technical scheme:
the method for preparing the potassium fluosilicate by recovering the acid wastewater from tantalum-niobium hydrometallurgy comprises the following steps:
s1, conveying potassium chloride solid particles into a dissolving tank, and dissolving with hot tap water to obtain a potassium chloride solution;
s2, pumping the acid wastewater from tantalum-niobium hydrometallurgy into a stirring tank, adding silicon powder, and stirring and reacting for a period of time at 40-60 ℃ to obtain a solution containing fluosilicic acid;
s3, filtering the solution containing the fluosilicic acid obtained in the S2 to obtain filtrate and unreacted silicon powder;
and S4, at normal temperature, mixing the filtrate obtained in the step S3 with the potassium chloride solution obtained in the step S1 according to the volume ratio of 1:0.55, respectively and slowly dripping into a synthesis tank, and reacting for a period of time to obtain liquid containing fluorine potassium silicate;
and S5, centrifuging and drying the liquid containing the fluorine potassium silicate obtained in the step S4 to obtain the potassium fluosilicate.
Further, in S1, the dissolving temperature of the potassium chloride solution is controlled at 40 ℃, and the content of potassium chloride in the potassium chloride solution is controlled at 25-30%.
Further, in S2, the stirring reaction time is 12h.
Further, in S3, the unreacted silicon powder is again put into the stirring tank for reuse.
Further, in S4, the reaction conditions are that the dropping speed of the fluosilicic acid-containing filtrate is controlled to be 15-20L/min, the dropping speed of the potassium chloride solution is controlled to be 8.25-11L/min, the stirring speed of the synthesis tank is controlled to be 100-150 rpm, and the reaction lasts for 0.5h after the dropping is finished.
Further, in S5, the centrifugation condition is 600-1000 rpm, and the time is 30-50 min.
Further, in S5, the filtrate enters a sewage station for further treatment.
The invention has the beneficial effects that:
1. the method directly utilizes hydrofluoric acid, fluotitanic acid, fluoride salt and the like in the acid wastewater from the tantalum-niobium hydrometallurgy to react with silicon powder to generate fluosilicic acid, and the fluosilicic acid reacts with potassium chloride solution to generate potassium fluosilicate, so that the phenomenon that the fluorine-containing wastewater and soda lime are directly neutralized by using the traditional means to form calcium fluoride containing a large amount of impurities and other calcium salt precipitates to generate new solid waste pollution is avoided, the hydrofluoric acid, the fluosilicic acid, the silicon tetrafluoride, the fluoride salt and the like in the acid wastewater from the tantalum-niobium hydrometallurgy are fully utilized, and the waste of fluorine and silicon resources is avoided.
2. In order to improve the utilization rate of fluorine resources, when the acid wastewater from tantalum-niobium hydrometallurgy is pumped into a stirring tank, silicon powder is added to fully stir and react for 12 hours at the temperature of 40-60 ℃, so that most of fluorine resources in the acid wastewater from tantalum-niobium hydrometallurgy can be fully combined with the silicon powder to form fluosilicic acid.
3. In order to improve the utilization rate of fluorine resources and silicon resources, when filtrate containing the fluosilicic acid reacts with potassium chloride solution in a synthesis tank, the dripping speed of the filtrate containing the fluosilicic acid is controlled to be 15-20L/min, the dripping speed of the potassium chloride solution is controlled to be 8.25-11L/min, the stirring speed of the synthesis tank is controlled to be 100-150 rpm, and the reaction lasts for 0.5h after the dripping is finished. The whole reaction is carried out at normal temperature, and simultaneously, by controlling the dripping speed of filtrate containing fluosilicic acid and potassium chloride solution, the reaction is continued for 0.5h after dripping, so that fluosilicic acid and potassium chloride can be fully reacted to generate potassium fluosilicate, the whole dripping reaction is carried out at normal temperature, the consumed time is short, on one hand, the reaction product potassium fluosilicate can be prevented from being easily hydrolyzed under the heating condition, on the other hand, the yield of recovering the potassium fluosilicate from the tantalum-niobium hydrometallurgy acidic wastewater can be remarkably improved, and the yield can reach more than 90%.
4. After the solution containing fluorine potassium silicate is centrifuged and dried, the purity of the obtained potassium fluosilicate is over 99 percent, and the obtained potassium fluosilicate can be directly used as a chemical raw material to generate greater economic benefit. The whole treatment process is simple and the production cost is low.
5. According to the invention, when the potassium fluosilicate is prepared by recycling the acid wastewater generated by tantalum-niobium hydrometallurgy, silicon powder is utilized, and the unreacted silicon powder can be directly filtered and recycled; and the subsequent dropwise adding reaction of the filtrate containing the fluosilicic acid and the potassium chloride solution in the synthesis tank does not need heating, so that the production cost for preparing the potassium fluosilicate is reduced, and the problem of low yield of the potassium fluosilicate caused by the decomposition of the potassium fluosilicate in hot water is avoided.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
In order to make the purpose, technical solution and advantages of the embodiments of the present invention more clear, the technical solution of the present invention will be clearly and completely described below with reference to the drawings and the detailed description in the embodiments of the present invention.
Example 1:
a method for preparing potassium fluosilicate by recovering acid wastewater from tantalum-niobium hydrometallurgy comprises the following steps:
s1, dissolving 1000g of potassium chloride solid by using hot tap water, controlling the dissolving temperature of a potassium chloride solution at 40 ℃ and controlling the potassium chloride content at 25%;
s2, adding silicon powder into the acid wastewater generated in the tantalum-niobium hydrometallurgy, controlling the reaction temperature at 40 ℃, and stirring for reaction for 12 hours to enable free hydrofluoric acid (HF) and silicon powder (SO) in the acid wastewater to react 2 ) Reacting to generate fluosilicic acid;
s3, filtering the solution containing the fluosilicic acid obtained in the S2 to obtain filtrate and unreacted silicon powder;
s4, at normal temperature, mixing the filtrate obtained in the step S3 with the potassium chloride solution obtained in the step S1 according to a volume ratio of 1:0.55, slowly adding the mixture dropwise into a synthesis tank, controlling the dropwise adding speed of the fluosilicic acid-containing wastewater to be 15L/min, controlling the dropwise adding speed of a potassium chloride solution to be 8.25L/min, controlling the stirring speed of the synthesis tank to be 150rpm, and reacting for 0.5h after the dropwise adding is finished to generate potassium fluosilicate;
s5, centrifuging the liquid containing the fluorine potassium silicate obtained in the step S4 for 30min at 600rpm of a centrifuge to separate solid from liquid, and drying to obtain 1337.89g of potassium fluosilicate.
And the residual defluorinated acidic wastewater enters a sewage station for further treatment.
Example 2:
a method for preparing potassium fluosilicate by recovering acid wastewater from tantalum-niobium hydrometallurgy comprises the following steps:
s1, dissolving 1000g of potassium chloride solid by using hot tap water, controlling the dissolving temperature of a potassium chloride solution at 40 ℃ and controlling the potassium chloride content at 30%;
s2, adding silicon powder into the acid wastewater generated in tantalum-niobium hydrometallurgy, controlling the reaction temperature at 55 ℃, and stirring for reaction for 12 hours to enable free hydrofluoric acid (HF) and silicon powder (SO) in the acid wastewater to react 2 ) Reacting to generate fluosilicic acid;
s3, filtering the solution containing the fluosilicic acid obtained in the step S2 to obtain filtrate and unreacted silicon powder;
s4, at normal temperature, mixing the filtrate obtained in the step S3 with the potassium chloride solution obtained in the step S1 according to a volume ratio of 1:0.55, slowly dripping the mixture into a synthesis tank, controlling the dripping speed of the fluorine-containing silicic acid wastewater to be 18L/min, controlling the dripping speed of a potassium chloride solution to be 9.9L/min, controlling the stirring speed of the synthesis tank to be 100rpm, and reacting for 0.5h after the dripping is finished to generate potassium fluosilicate;
s5, centrifuging the liquid containing the fluorine potassium silicate obtained in the step S4 for 35min at 800rpm of a centrifuge to separate solid from liquid, and drying to obtain 1377.48g of potassium fluosilicate.
And the residual defluorinated acidic wastewater enters a sewage station for further treatment.
Example 3:
a method for preparing potassium fluosilicate by recycling acid wastewater generated in tantalum-niobium hydrometallurgy comprises the following steps:
s1, dissolving 1000g of potassium chloride solid by using hot tap water, controlling the dissolving temperature of a potassium chloride solution at 40 ℃ and controlling the potassium chloride content at 27%;
s2, adding silicon powder into the acid wastewater generated in tantalum-niobium hydrometallurgy, controlling the reaction temperature at 60 ℃, and stirring for reaction for 12 hours to enable free hydrofluoric acid (HF) in the acid wastewater to react with the free hydrofluoric acid (HF)Silicon powder (SO) 2 ) Reacting to generate fluosilicic acid;
s3, filtering the solution containing the fluosilicic acid obtained in the step S2 to obtain filtrate and unreacted silicon powder;
s4, at normal temperature, mixing the filtrate obtained in the step S3 with the potassium chloride solution obtained in the step S1 according to a volume ratio of 1:0.55, slowly dripping the mixture into a synthesis tank, controlling the dripping speed of the fluorine-containing silicic acid wastewater to be 19L/min, controlling the dripping speed of a potassium chloride solution to be 10.45L/min, controlling the stirring speed of the synthesis tank to be 100rpm, and reacting for 0.5h after the dripping is finished to generate potassium fluosilicate;
s5, centrifuging the liquid containing the fluorine potassium silicate obtained in the step S4 for 42min at 700rpm by using a centrifuge to separate solid from liquid, and drying to obtain 1356.80g of potassium fluosilicate.
And the residual defluorinated acidic wastewater enters a sewage station for further treatment.
Example 4:
a method for preparing potassium fluosilicate by recycling acid wastewater generated in tantalum-niobium hydrometallurgy comprises the following steps:
s1, dissolving 1000g of potassium chloride solid by using hot tap water, controlling the dissolving temperature of a potassium chloride solution at 40 ℃ and controlling the potassium chloride content at 26%;
s2, adding silicon powder into the acid wastewater generated in the tantalum-niobium hydrometallurgy, controlling the reaction temperature at 50 ℃, and stirring for reaction for 12 hours to enable free hydrofluoric acid (HF) and silicon powder (SO) in the acid wastewater to react 2 ) Reacting to generate fluosilicic acid;
s3, filtering the solution containing the fluosilicic acid obtained in the S2 to obtain filtrate and unreacted silicon powder;
s4, at normal temperature, mixing the filtrate obtained in the step S3 with the potassium chloride solution obtained in the step S1 according to a volume ratio of 1:0.55, slowly adding the mixture dropwise into a synthesis tank, controlling the dropwise adding speed of the fluosilicic acid-containing wastewater to be 17L/min, controlling the dropwise adding speed of a potassium chloride solution to be 9.35L/min, controlling the stirring speed of the synthesis tank to be 150rpm, and reacting for 0.5h after the dropwise adding is finished to generate potassium fluosilicate;
s5, centrifuging the liquid containing the fluorine potassium silicate obtained in the step S4 for 47min at 900rpm of a centrifuge to separate solid from liquid, and drying to obtain 1348.08g of potassium fluosilicate.
And the residual defluorinated acidic wastewater enters a sewage station for further treatment.
Example 5:
a method for preparing potassium fluosilicate by recovering acid wastewater from tantalum-niobium hydrometallurgy comprises the following steps:
s1, dissolving 1000g of potassium chloride solid by using hot tap water, controlling the dissolving temperature of a potassium chloride solution at 40 ℃ and controlling the potassium chloride content at 28%;
s2, adding silicon powder into the acid wastewater generated in tantalum-niobium hydrometallurgy, controlling the reaction temperature at 48 ℃, and stirring for reaction for 12 hours to enable free hydrofluoric acid (HF) and silicon powder (SO) in the acid wastewater to react 2 ) Reacting to generate fluosilicic acid;
s3, filtering the solution containing the fluosilicic acid obtained in the step S2 to obtain filtrate and unreacted silicon powder;
s4, at normal temperature, mixing the filtrate obtained in the step S3 with the potassium chloride solution obtained in the step S1 according to a volume ratio of 1:0.55, slowly dripping the mixture into a synthesis tank, controlling the dripping speed of the fluorine-containing silicic acid wastewater to be 16L/min, controlling the dripping speed of a potassium chloride solution to be 8.8L/min, controlling the stirring speed of the synthesis tank to be 100rpm, and reacting for 0.5h after the dripping is finished to generate potassium fluosilicate;
s5, centrifuging the liquid containing the fluorine potassium silicate obtained in the step S4 for 40min at 700rpm by using a centrifuge to separate solid from liquid, and drying to obtain 1359.75g of potassium fluosilicate.
And the residual defluorinated acidic wastewater enters a sewage station for further treatment.
Example 6:
a method for preparing potassium fluosilicate by recycling acid wastewater generated in tantalum-niobium hydrometallurgy comprises the following steps:
s1, dissolving 1000g of potassium chloride solid by using hot tap water, controlling the dissolving temperature of a potassium chloride solution at 40 ℃ and controlling the potassium chloride content at 29%;
s2, adding silicon powder into the acid wastewater generated in tantalum-niobium hydrometallurgy, controlling the reaction temperature at 52 ℃, and stirring for reaction for 12 hours to enable free hydrofluoric acid (HF) and silicon powder (SO) in the acid wastewater to react 2 ) Reacting to generate fluosilicic acid;
s3, filtering the solution containing the fluosilicic acid obtained in the S2 to obtain filtrate and unreacted silicon powder;
s4, at normal temperature, mixing the filtrate obtained in the step S3 with the potassium chloride solution obtained in the step S1 according to a volume ratio of 1:0.55, slowly dripping the mixture into a synthesis tank, controlling the dripping speed of the fluorine-containing silicic acid wastewater to be 20L/min, controlling the dripping speed of a potassium chloride solution to be 11L/min, controlling the stirring speed of the synthesis tank to be 150rpm, and reacting for 0.5h after the dripping is finished to generate potassium fluosilicate;
s5, centrifuging the liquid containing the fluorine potassium silicate obtained in the step S4 for 50min at 1000rpm by using a centrifuge to separate solid from liquid, and drying to obtain 1370.69g of potassium fluosilicate.
The residual defluorinated acidic wastewater enters a sewage station for further treatment
Comparative example 1:
a method for preparing potassium fluosilicate by recovering acid wastewater from tantalum-niobium hydrometallurgy comprises the following steps:
s1, dissolving 1000g of potassium chloride solid by using hot tap water, controlling the dissolving temperature of a potassium chloride solution at 40 ℃, and controlling the content of potassium chloride at 30%;
s2, adding silicon powder into the acid wastewater generated in tantalum-niobium hydrometallurgy, controlling the reaction temperature at 55 ℃, and stirring for reaction for 12 hours to enable free hydrofluoric acid (HF) and silicon powder (SO) in the acid wastewater to react 2 ) Reacting to generate fluosilicic acid;
s3, filtering the solution containing the fluosilicic acid obtained in the step S2 to obtain filtrate and unreacted silicon powder;
s4, at normal temperature, mixing the filtrate obtained in the step S3 with the potassium chloride solution obtained in the step S1 according to a volume ratio of 1:0.55, directly mixing and reacting for 0.5h to generate potassium fluosilicate;
s5, centrifuging the liquid containing the fluorine potassium silicate obtained in the step S4 for 35min at 1000rpm by using a centrifuge to separate solid from liquid, and drying to obtain 1183.65g of potassium fluosilicate.
And the residual defluorinated acidic wastewater enters a sewage station for further treatment.
Comparative example 2:
a method for preparing potassium fluosilicate by recycling acid wastewater generated in tantalum-niobium hydrometallurgy comprises the following steps:
s1, dissolving 1000g of potassium chloride solid by using hot tap water, controlling the dissolving temperature of a potassium chloride solution at 40 ℃ and controlling the potassium chloride content at 30%;
s2, adding silicon powder into the acid wastewater generated in the tantalum-niobium hydrometallurgy, controlling the reaction temperature at 55 ℃, and stirring for reaction for 12 hours to enable free hydrofluoric acid (HF) and silicon powder (SO) in the acid wastewater to react 2 ) Reacting to generate fluosilicic acid;
s3, filtering the solution containing the fluosilicic acid obtained in the S2 to obtain filtrate and unreacted silicon powder;
s4, under the condition of 48 ℃, mixing the filtrate obtained in the step S3 with the potassium chloride solution obtained in the step S1 according to the volume ratio of 1:0.55, directly mixing and reacting for 0.5h to generate potassium fluosilicate;
s5, centrifuging the liquid containing the fluorine potassium silicate obtained in the step S4 for 35min at 1000rpm by using a centrifuge to separate solid from liquid, and drying to obtain 964.41g of potassium fluosilicate.
And the residual defluorinated acidic wastewater enters a sewage station for further treatment.
Comparative example 3:
a method for preparing potassium fluosilicate by recovering acid wastewater from tantalum-niobium hydrometallurgy comprises the following steps:
s1, dissolving 1000g of potassium chloride solid by using hot tap water, controlling the dissolving temperature of a potassium chloride solution at 40 ℃ and controlling the potassium chloride content at 30%;
s2, adding silicon powder into the acid wastewater generated in tantalum-niobium hydrometallurgy, controlling the reaction temperature at 55 ℃, and stirring for reaction for 12 hours to enable free hydrofluoric acid (HF) and silicon powder (SO) in the acid wastewater to react 2 ) Reacting to generate fluosilicic acid;
s3, filtering the solution containing the fluosilicic acid obtained in the step S2 to obtain filtrate and unreacted silicon powder;
s4, at normal temperature, mixing the filtrate obtained in the step S3 with the potassium chloride solution obtained in the step S1 according to a volume ratio of 1:1, slowly dripping the mixture into a synthesis tank, controlling the dripping speed of the fluosilicic acid-containing wastewater to be 18L/min, controlling the dripping speed of a potassium chloride solution to be 9.9L/min, controlling the stirring speed of the synthesis tank to be 100rpm, and reacting for 0.5h after the dripping is finished to generate potassium fluosilicate;
s5, centrifuging the liquid containing the fluorine potassium silicate obtained in the step S4 for 35min at 1000rpm by using a centrifuge to separate solid from liquid, and drying to obtain 1259.29g of potassium fluosilicate.
And the residual defluorinated acidic wastewater enters a sewage station for further treatment.
The process flow charts of the above examples 1 to 6 are shown in FIG. 1, and the purity of potassium fluorosilicate obtained in 6 examples and 3 comparative examples was examined and the yield thereof was calculated based on the amount of potassium chloride used, and the results are shown in Table 1.
TABLE 1 detection results of acid wastewater treatment in tantalum-niobium hydrometallurgy
As a result: as can be seen from the detection results in Table 1, the purity of the potassium fluosilicate obtained by the preparation method of the invention by dropwise adding reaction at normal temperature in 6 examples is 99.24-99.82%, the average value is 99.49%, and the yield of the potassium fluosilicate is above 90%, which indicates that the method of the invention can effectively utilize fluorine and silicon resources in the tantalum-niobium hydrometallurgy acidic wastewater, and simultaneously, the raw material potassium chloride is not wasted.
In comparative example 1, the filtrate obtained in S3 and the potassium chloride solution obtained in S1 were mixed in a volume ratio of 1:0.55, the purity of the generated potassium fluosilicate is 98.12 percent and the yield is 80.12 percent after direct mixing reaction is carried out for 0.5h, and the purity and the yield of the generated potassium fluosilicate are reduced compared with those of the potassium fluosilicate in example 2, which indicates that the direct mixing reaction of the fluosilicic acid and the potassium chloride solution is insufficient and impurities are easily brought in.
In comparative example 2, the filtrate obtained in S3 and the potassium chloride solution obtained in S1 were mixed in a volume ratio of 1:0.55, at the temperature of 48 ℃, after directly mixing and reacting for 0.5h, the purity of the generated potassium fluosilicate is 95.32%, and the yield is 65.28%, compared with the potassium fluosilicate obtained in the example 2, the purity and the yield are both reduced, especially the yield is obviously reduced, which indicates that the potassium fluosilicate is easy to hydrolyze due to heating, and the yield is influenced.
In comparative example 3, the volume ratio of the filtrate obtained in S3 to the potassium chloride solution obtained in S1 was set to 1: after 1, the purity of the generated potassium fluosilicate is 99.02%, the yield is 85.24%, and the yield is obviously reduced compared with the yield of the potassium fluosilicate in the example 2, which shows that the purity and the yield of the potassium fluosilicate are not improved by excessively adding the potassium chloride solution, that is, the control of a reasonable reaction rate and the addition amount of raw materials is very important for the purity and the yield of the prepared potassium fluosilicate.
In conclusion, the purity of the potassium fluosilicate obtained by the method is high, and is more than 99%, the potassium fluosilicate can be directly used as a chemical raw material, the yield of the treated potassium fluosilicate is high, and is more than 90% by calculating the using amount of potassium chloride, and therefore, fluorine and silicon resources in the acid wastewater of tantalum-niobium hydrometallurgy and the raw material potassium chloride are effectively utilized.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various other modifications and changes can be made within the knowledge of those skilled in the art. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. A method for preparing potassium fluosilicate by recovering acid wastewater from tantalum-niobium hydrometallurgy is characterized by comprising the following steps:
s1, conveying potassium chloride solid particles into a dissolving tank, and dissolving with hot tap water to obtain a potassium chloride solution;
s2, pumping the acid wastewater from the tantalum-niobium hydrometallurgy into a stirring tank, adding silicon powder, and stirring and reacting for a period of time at the temperature of 40-60 ℃ to obtain a solution containing fluosilicic acid;
s3, filtering the solution containing the fluosilicic acid obtained in the step S2 to obtain filtrate and unreacted silicon powder;
and S4, mixing the filtrate obtained in the step S3 and the potassium chloride solution obtained in the step S1 at normal temperature according to the volume ratio of 1:0.55, respectively and slowly dripping into a synthesis tank, and reacting for a period of time to obtain liquid containing fluorine potassium silicate;
and S5, centrifuging and drying the liquid containing the fluorine potassium silicate obtained in the step S4 to obtain the potassium fluosilicate.
2. The method according to claim 1, wherein in S1, the dissolution temperature of the potassium chloride solution is controlled at 40 ℃, and the potassium chloride content of the potassium chloride solution is controlled at 25-30%.
3. The method according to claim 1, wherein in S2, the stirring reaction time is 12 hours.
4. The process according to claim 1, wherein in S3, the unreacted silicon powder is again put into the stirring tank for recycling.
5. The method of claim 1, wherein in S4, the reaction conditions are: the dripping speed of the fluosilicic acid-containing filtrate is controlled to be 15-20L/min, the dripping speed of the potassium chloride solution is controlled to be 8.25-11L/min, the stirring speed of the synthesis tank is controlled to be 100-150 rpm, and the reaction lasts for 0.5h after the dripping is finished.
6. The method according to claim 1, wherein in S5, the centrifugation conditions are 600 to 1000rpm and the time is 30 to 50min.
7. The method of claim 1, wherein in S5 the filtrate is passed to a sewage station for further treatment.
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| CN1396113A (en) * | 2002-07-03 | 2003-02-12 | 夏克立 | Process for continuously preparing big-crystal sodium (or potassium) fluosilicate |
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| CN1396113A (en) * | 2002-07-03 | 2003-02-12 | 夏克立 | Process for continuously preparing big-crystal sodium (or potassium) fluosilicate |
| CN103159218A (en) * | 2011-12-14 | 2013-06-19 | 常熟市新华化工有限公司 | Production method of potassium fluosilicate |
| CN103145131A (en) * | 2013-02-26 | 2013-06-12 | 贵州金正大生态工程有限公司 | Resource comprehensive utilization method for recovering fluorine from wet-process phosphoric acid |
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