CN116835596A - Method for preparing potassium fluosilicate by using fluorine-containing waste acid in photovoltaic industry - Google Patents
Method for preparing potassium fluosilicate by using fluorine-containing waste acid in photovoltaic industry Download PDFInfo
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- fluorine
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- 239000002253 acid Substances 0.000 title claims abstract description 134
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 103
- 239000011737 fluorine Substances 0.000 title claims abstract description 103
- 239000002699 waste material Substances 0.000 title claims abstract description 101
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000011591 potassium Substances 0.000 title claims abstract description 66
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000706 filtrate Substances 0.000 claims abstract description 78
- 239000007787 solid Substances 0.000 claims abstract description 60
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000005406 washing Methods 0.000 claims abstract description 39
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 23
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000000967 suction filtration Methods 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000004064 recycling Methods 0.000 claims abstract description 17
- 239000000376 reactant Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 235000007686 potassium Nutrition 0.000 claims description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 235000012239 silicon dioxide Nutrition 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 27
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 14
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 14
- 235000011151 potassium sulphates Nutrition 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- 230000001131 transforming effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 32
- 238000001914 filtration Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 18
- 238000005303 weighing Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 238000005530 etching Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 238000010248 power generation Methods 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 229910003638 H2SiF6 Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical group F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 hydrofluoric acid compound Chemical class 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910021655 trace metal ion Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a method for preparing potassium fluosilicate by using fluorine-containing waste acid in the photovoltaic industry, which comprises the following steps: (1) Converting, namely slowly adding a conversion agent into the photovoltaic fluorine-containing waste acid to perform stirring reaction, and performing suction filtration and separation to obtain filter residues and a filtrate A, wherein the filter residues are recycled; (2) Preparing fluosilicic acid, namely adding a reactant into the filtrate A for stirring reaction, and carrying out suction filtration to separate solid and liquid after the reaction is finished to obtain a solid and filtrate B, and washing and drying the solid to obtain potassium fluosilicate; the reactant is one of potassium salt and potassium hydroxide; and (3) recycling. The invention can efficiently recycle the photovoltaic fluorine-containing resource to obtain potassium fluosilicate with higher added value, not only can promote the green production of the photovoltaic industry and realize the green economic development of the clean energy full-industry chain, but also can provide necessary conditions and basis for promoting the comprehensive utilization of the fluorine resource in the fluorine-containing waste acid of the photovoltaic industry in China and also provide a great amount of important available fluorine resource for the chemical industry.
Description
Technical Field
The invention relates to the technical field of resource recovery in waste liquid, in particular to a method for preparing potassium fluosilicate by using fluorine-containing waste acid in the photovoltaic industry.
Background
Along with the continuous progress of human civilization, the development of technology is continuous, and various energy sources are continuously exhausted. In recent years, scientific researchers have largely explored the energy field, and solar energy is favored by people because of safety, environmental protection, inexhaustibility and inexhaustibility, and solar power generation comprises photovoltaic power generation, photochemical power generation and photo-induction power generation, wherein photovoltaic power generation is the main stream of solar power generation nowadays.
The fluorine-containing waste acid in the photovoltaic production is a main waste liquid generated in the photovoltaic industry, and is mainly generated in the working procedures of texturing and etching of the polycrystalline silicon solar cell, pickling and etching of the monocrystalline silicon solar cell and the like. The content of the fluorine-containing waste acid component of the photovoltaic cell can be different according to the type and the process of the photovoltaic cell, but the generated waste acid component is basically the same, and generally contains a large amount of fluosilicic acid, hydrofluoric acid, nitric acid, sulfuric acid, hydrochloric acid and a very small amount of metal salt. Unlike fluoride-containing waste water produced in smelting, fluoridation, acid washing of steel, phosphate fertilizer and other industries, the photovoltaic fluoride-containing waste acid has the outstanding disadvantages of large water quantity, extremely high fluoride concentration, complex pollution components, high treatment difficulty, low metal impurity content and the like. The research on recycling of the high-concentration fluorine-containing waste acid can relieve the pollution of the waste acid generated by the photovoltaic manufacturing industry to the environment, and simultaneously, a large amount of important fluorine resources can be effectively regenerated, so that the green production of the photovoltaic industry is promoted, the green economic development of the clean energy full-industry chain is realized by assistance, and a large amount of important available fluorine resources can be provided for the chemical industry of China.
The method for disposing the fluorine-containing waste liquid in China has clear requirements, and the method for recycling the etching waste acid in the photovoltaic industry is mentioned in national standard GB/T34697-2017 of the people's republic of China. The method comprises the following steps: (1) recycling the waste liquid: treating fluorine-containing etching solution by using an impurity removing agent, filtering to remove main impurity fluosilicic acid, concentrating filtrate after primary and secondary membrane treatment, introducing the filtrate into a mixing reaction kettle, adding a certain amount of hydrofluoric acid compound acid to obtain etching solution meeting applicable conditions, and returning the etching solution to an etching tank for use, wherein filter residues and waste residues generated by filtering and primary membrane treatment can be used for producing fluosilicate; (2) For etching waste liquid with low hydrofluoric acid and fluosilicic acid content: removing sulfate radical, chloride ion and the like by using corresponding impurity removing agents, and adding liquid ammonia to generate ammonium fluoride and ammonium bifluoride products; or adding calcium hydroxide or magnesium hydroxide to obtain calcium fluoride or magnesium fluoride products; (3) For etching waste liquid with lower hydrofluoric acid content and fluosilicic acid content higher than 5%, adding impurity removing agent to remove sulfate radical, chloride ion, fluoride ion, etc. to obtain pure fluosilicic acid solution, then adding potassium chloride or potassium sulfate, sodium chloride or ammonia water to produce potassium fluosilicate, sodium fluosilicate and fluosilicic acid.
At present, the research on the treatment of fluorine-containing waste acid in the photovoltaic industry by domestic related enterprises is more and more emphasized, and Chinese patent CN 113816405A discloses a method for recycling the fluorine-containing waste acid in the photovoltaic industry, wherein fluorine in the fluorine-containing waste acid is extracted into fluosilicic acid and then mixed with magnesium nitrate solution, nitric acid as a byproduct is obtained after the procedures of stripping, rectifying bleaching, condensing and the like, and magnesium fluoride crude product is obtained by pyrolysis of mixed salt at the bottom of a kettle, and the magnesium nitrate solution is recycled.
Chinese patent CN 111592144a discloses a method for treating waste acid in photovoltaic industry, which comprises adding sodium salt into waste acid to react to obtain sodium fluosilicate precipitate and filtrate, adding calcium salt into filtrate to obtain calcium fluoride precipitate and mixed acid solution, separating the obtained mixed acid solution to obtain nitric acid solution and sulfuric acid solution, mixing the obtained calcium fluoride precipitate with the obtained sulfuric acid solution or nitric acid solution, and reacting to obtain hydrofluoric acid and calcium salt.
Chinese patent CN 113461017A discloses a recycling method of fluorine-containing waste acid applied to the photovoltaic industry, which comprises the steps of firstly converting hydrofluoric acid in the fluorine-containing waste acid of the photovoltaic industry into fluosilicic acid by utilizing silicon dioxide, filtering and separating, adding sodium sulfate or sodium nitrate into filtrate, reacting, separating, washing and drying to obtain sodium fluosilicate and filtrate 2, adding the filtrate 2 into ferrous sulfate solution, and introducing oxygen for catalytic oxidation to obtain polymeric ferric sulfate.
The above all teach the utilization method of fluorine-containing waste acid in the photovoltaic industry, wherein the fluosilicic acid and hydrofluoric acid have lower component concentration, the sulfuric acid and nitric acid have higher concentration, and the sulfuric acid and nitric acid do not contain hydrochloric acid, so that the purity of the obtained product is limited.
Disclosure of Invention
The invention provides a method for preparing potassium fluosilicate by using fluorine-containing waste acid in the photovoltaic industry.
The scheme of the invention is as follows:
a method for preparing potassium fluosilicate by using fluorine-containing waste acid in the photovoltaic industry comprises the following steps:
(1) Converting, namely slowly adding a conversion agent into the photovoltaic fluorine-containing waste acid to perform stirring reaction, and performing suction filtration and separation to obtain filter residues and a filtrate A, wherein the filter residues are recycled;
(2) Preparing fluosilicic acid, namely adding a reactant into the filtrate A for stirring reaction, and carrying out suction filtration to separate solid and liquid after the reaction is finished to obtain a solid and filtrate B, and washing and drying the solid to obtain potassium fluosilicate; the reactant is one of potassium salt and potassium hydroxide;
(3) Recycling, namely recycling the washing liquid obtained by washing the filtrate B and the solid with water.
As a preferable technical means, the photovoltaic fluorine-containing waste acid in the step (1) is slowly added with a conversion agent for stirring reaction, the reaction temperature is 0-100 ℃, the reaction time is 10-240min, and the molar ratio of the fluorine waste acid to the conversion agent is 6.0:1.0-2.0; the transforming agent is one of silicon dioxide, silicic acid and potassium silicate. The silicon dioxide is silicon dioxide powder or silicon dioxide emulsion; the silicic acid is silicic acid powder or silicic acid emulsion.
As a preferable technical means, the photovoltaic fluorine-containing waste acid comprises fluosilicic acid, hydrofluoric acid, sulfuric acid, hydrochloric acid and nitric acid; wherein the fluosilicic acid content is 2-30wt%, the hydrofluoric acid content is 2-30wt%, the sulfuric acid content is 0-8wt%, the hydrochloric acid content is 0-15wt%, and the nitric acid content is 0-15wt%.
As a preferable technical means, in the step (2), the reaction temperature is 10-80 ℃ and the reaction time is 30-300min.
As a preferable technical means, the reactant is potassium salt, and the molar ratio of fluosilicic acid to potassium salt is 1.0:1.0-3.6; the potassium salt is potassium salt powder or potassium salt solution; the potassium salt comprises any one or a combination of at least two of potassium sulfate, potassium chloride, potassium nitrate, potassium carbonate and potassium bicarbonate.
As a preferable technical means, the reactant is potassium hydroxide, and the molar ratio of fluosilicic acid to potassium hydroxide is 1.0:2.0-3.0. The potassium hydroxide is potassium hydroxide solid or potassium hydroxide powder.
As a preferable technical means, the circulating water suction filters are adopted for solid-liquid separation in the steps (1) and (2).
As a preferable technical means, washing is carried out by using a washing liquid, wherein the mass of the washing liquid is 2-8 times of that of the solid matters, and the washing liquid is deionized water.
As a preferable technical means, the drying mode is drying at 80-180 ℃ for 5-24h.
Due to the adoption of the technical scheme, the method for preparing the potassium fluosilicate by using the fluorine-containing waste acid in the photovoltaic industry comprises the following steps of: (1) Converting, namely slowly adding a conversion agent into the photovoltaic fluorine-containing waste acid to perform stirring reaction, and performing suction filtration and separation to obtain filter residues and a filtrate A, wherein the filter residues are recycled; (2) Preparing fluosilicic acid, namely adding a reactant into the filtrate A for stirring reaction, and carrying out suction filtration to separate solid and liquid after the reaction is finished to obtain a solid and filtrate B, and washing and drying the solid to obtain potassium fluosilicate; the reactant is one of potassium salt and potassium hydroxide; (3) Recycling, namely recycling the washing liquid obtained by washing the filtrate B and the solid with water.
The invention has the advantages that:
the fluorine-containing waste acid component is more complex, the concentration range of the main component is larger, the defects can be overcome by improving the reaction conditions and the washing treatment method, and the product with higher concentration is obtained. The fluorine-containing waste acid in the photovoltaic industry contains fluosilicic acid, hydrofluoric acid, sulfuric acid, nitric acid, hydrochloric acid and trace metal ion impurities, and the method changes waste into valuable and turns harmful into useful things by treatment, thereby realizing the comprehensive recycling of fluorine resources in the fluorine-containing waste acid in the photovoltaic industry, and obtaining high-purity potassium fluosilicate, wherein the purity of the product potassium fluosilicate is more than or equal to 99.0 percent.
The method for preparing the potassium fluosilicate by utilizing the fluorine-containing waste acid in the photovoltaic industry can efficiently recover the fluorine-containing resource of the photovoltaic to obtain the potassium fluosilicate with higher added value, can promote the green production of the photovoltaic industry, realize the green economic development of the clean energy full-industry chain by assistance, provide necessary conditions and basis for promoting the comprehensive utilization of the fluorine resource in the fluorine-containing waste acid in the photovoltaic industry in China, and provide a large amount of important available fluorine resources for the chemical industry.
The invention has the advantages compared with the prior art:
(1) Firstly, silica or silicic acid is reacted with hydrofluoric acid in fluorine-containing waste acid to obtain filter residues and filtrate, wherein the main component of the filter residues is silica, and the filter residues can be further recycled into the process; then adding potassium salt or potassium hydroxide into the filtrate, stirring, reacting, washing and drying to obtain potassium fluosilicate, wherein the purity of the potassium fluosilicate is more than or equal to 99.0%.
(2) When acid such as hydrochloric acid, sulfuric acid, nitric acid and the like exists in the fluorine-containing waste acid in the photovoltaic industry, the method basically has no influence on the content of the potassium fluosilicate and the recovery rate of fluorine resources.
(3) The invention aims at treating and utilizing the high-concentration fluorine-containing waste acid in the photovoltaic industry, converts fluorine resources into a high-purity potassium fluosilicate product, changes waste into valuable, changes the harm into benefit, and provides necessary conditions and basis for promoting the comprehensive utilization of the fluorine resources in the photovoltaic fluorine-containing waste acid.
(4) The invention realizes the high-efficiency recycling of fluorine resources in fluorine-containing waste acid in the photovoltaic industry, and can obtain high-purity potassium fluosilicate products. The operation method is simple and reliable, does not generate new solid waste, and has the characteristics of safety and environmental protection.
Drawings
FIG. 1 is a schematic diagram of a process flow for preparing a product potassium fluosilicate by utilizing photovoltaic fluorine-containing waste acid.
Detailed Description
The invention provides a method for preparing potassium fluosilicate by using fluorine-containing waste acid in the photovoltaic industry, which aims to solve the problems in the background technology.
A method for preparing potassium fluosilicate by using fluorine-containing waste acid in the photovoltaic industry comprises the following steps:
(1) Converting, namely slowly adding a conversion agent into the photovoltaic fluorine-containing waste acid to perform stirring reaction, and performing suction filtration and separation to obtain filter residues and a filtrate A, wherein the filter residues are recycled;
(2) Preparing fluosilicic acid, namely adding a reactant into the filtrate A for stirring reaction, and carrying out suction filtration to separate solid and liquid after the reaction is finished to obtain a solid and filtrate B, and washing and drying the solid to obtain potassium fluosilicate; the reactant is one of potassium salt and potassium hydroxide;
(3) Recycling, namely recycling the washing liquid obtained by washing the filtrate B and the solid with water.
Slowly adding a conversion agent into the photovoltaic fluorine-containing waste acid in the step (1) for stirring reaction, wherein the reaction temperature is 0-100 ℃, the reaction time is 10-240min, and the molar ratio of the fluorine waste acid to the conversion agent is 6.0:1.0-2.0; the transforming agent is one of silicon dioxide, silicic acid and potassium silicate. The silicon dioxide is silicon dioxide powder or silicon dioxide emulsion; the silicic acid is silicic acid powder or silicic acid emulsion.
The photovoltaic fluorine-containing waste acid comprises fluosilicic acid, hydrofluoric acid, sulfuric acid, hydrochloric acid and nitric acid; wherein the fluosilicic acid content is 2-30wt%, the hydrofluoric acid content is 2-30wt%, the sulfuric acid content is 0-8wt%, the hydrochloric acid content is 0-15wt%, and the nitric acid content is 0-15wt%.
In the step (2), the reaction temperature is 10-80 ℃ and the reaction time is 30-300min.
The reactant is potassium salt, and the molar ratio of fluosilicic acid to potassium salt is 1.0:1.0-3.6; the potassium salt is potassium salt powder or potassium salt solution; the potassium salt comprises any one or a combination of at least two of potassium sulfate, potassium chloride, potassium nitrate, potassium carbonate and potassium bicarbonate.
The reactant is potassium hydroxide, and the molar ratio of fluosilicic acid to potassium hydroxide is 1.0:2.0-3.0. The potassium hydroxide is potassium hydroxide solid or potassium hydroxide powder.
And (3) carrying out solid-liquid separation by adopting a circulating water suction filter in the step (1) and the step (2) respectively.
Washing is carried out by using a washing liquid, the mass of the washing liquid is 2-8 times of that of the solid matters, and the washing liquid is deionized water.
The drying method is drying at 80-180deg.C for 5-24 hr.
The invention is further described in connection with the following embodiments in order to make the technical means, the creation features, the achievement of the purpose and the effect of the invention easy to understand.
The fluorine-containing waste acid in the photovoltaic industry adopted by the embodiment of the invention is from the new energy company of the sialon, and the photovoltaic fluorine-containing waste acid contains 5 kinds of acid, and the specific composition components are as follows: h2SiF6:10-25wt%, HF:3.5-10wt%, H2SO4:0-5wt%, HCl:0-2wt%, HNO3:0-3.5wt%.
Example 1:
provides the composition of H 2 SiF 6 ：17.60％，HF：4.94％，H 2 SO 4 ：3.34％，HCl：0.03％，HNO 3 :2.23 percent and the rest of the photovoltaic fluorine-containing waste acid with water is taken as raw material. 50.00g of fluorine-containing waste acid is weighed, 1.29g of silicon dioxide powder is weighed, 30% silicon dioxide emulsion is prepared, the silicon dioxide emulsion is slowly added into the fluorine-containing waste acid at normal temperature, stirring reaction is carried out for 1 hour, and filtering is carried out to obtain filtrate 1; weighing 14.53g of potassium sulfate, preparing a 20% potassium sulfate solution, adding the solution into the filtrate 1, stirring and reacting for 2 hours at 40 ℃, carrying out suction filtration to obtain filtrate 2 and solid 1, respectively washing the solid 1 twice by deionized water with the theoretical mass 5 times of that of potassium fluosilicate, carrying out suction filtration for 10 minutes, and drying the washed filter cake to constant weight at 105 ℃ to obtain the product potassium fluosilicate.
And (3) through analysis and detection: the fluosilicic acid content in the filtrate 2 is 0, the F-content in the filtrate 2 is 0.121%, and the potassium fluosilicate content in the solid 1 is 99.52%.
Example 2:
example 2 provides a composition of H 2 SiF 6 ：17.60％，HF：4.94％，H 2 SO 4 ：3.34％，HCl：0.03％，HNO 3 :2.23 percent and the rest of the photovoltaic fluorine-containing waste acid with water is taken as raw material. 50.00g of fluorine-containing waste acid and 1.41g of dioxygen are weighedSilicon powder is prepared into 30% silicon dioxide emulsion, the silicon dioxide emulsion is slowly added into fluorine-containing waste acid at normal temperature, stirred and reacted for 1 hour, and filtered to obtain filtrate 1; weighing 15.86g of potassium sulfate, preparing a 20% potassium sulfate solution, adding the solution into the filtrate 1, stirring and reacting for 2 hours at 40 ℃, carrying out suction filtration to obtain filtrate 2 and solid 1, respectively washing the solid 1 twice by deionized water with the theoretical mass 5 times of that of potassium fluosilicate, carrying out suction filtration for 10 minutes, and drying the washed filter cake to constant weight at 105 ℃ to obtain the product potassium fluosilicate.
And (3) through analysis and detection: the fluosilicic acid content in the filtrate 2 is 0, the F-content in the filtrate 2 is 0.076%, and the potassium fluosilicate content in the solid 1 is as high as 99.75%.
Example 3:
example 3 provides a composition of H 2 SiF 6 ：17.60％，HF：4.94％，H 2 SO 4 ：3.34％，HCl：0.03％，HNO 3 :2.23 percent and the rest of the photovoltaic fluorine-containing waste acid with water is taken as raw material. 50.00g of fluorine-containing waste acid is weighed, 1.53g of silicon dioxide powder is weighed, the silicon dioxide powder is slowly added into the fluorine-containing waste acid at normal temperature, the mixture is stirred and reacts for 1 hour, and a filtrate 1 is obtained by filtration; weighing 12.82g of potassium chloride, preparing a 20% potassium chloride solution, adding the solution into the filtrate 1, stirring and reacting for 2 hours at 40 ℃, filtering to obtain filtrate 2 and solid 1, washing the solid 1 twice respectively by deionized water with the theoretical mass 4 times of the potassium fluosilicate, filtering for 10 minutes, and drying the washed filter cake to constant weight at 105 ℃ to obtain the product potassium fluosilicate.
And (3) through analysis and detection: the fluosilicic acid content in the filtrate 2 is 0, the F-content in the filtrate 2 is 0.091%, and the potassium fluosilicate content in the solid 1 is as high as 99.46%.
Example 4:
example 4 provides a composition of H2SiF6:17.60%, HF:4.94%, H2SO4:3.34%, HCl:0.03%, HNO3:2.23 percent and the rest of the photovoltaic fluorine-containing waste acid with water is taken as raw material. 50.00g of fluorine-containing waste acid is weighed, 1.41g of silicon dioxide powder is weighed, the silicon dioxide powder is slowly added into the fluorine-containing waste acid at normal temperature, the mixture is stirred and reacts for 1 hour, and a filtrate 1 is obtained by filtration; weighing 9.51g of potassium hydroxide, preparing a 20% potassium hydroxide solution, adding the solution into the filtrate 1, stirring and reacting for 2 hours at 40 ℃, carrying out suction filtration to obtain filtrate 2 and solid 1, respectively washing the solid 1 twice by deionized water with the theoretical mass 4 times of that of potassium fluosilicate, carrying out suction filtration for 10 minutes, and drying the washed filter cake to constant weight at 105 ℃ to obtain the product potassium fluosilicate.
And (3) through analysis and detection: the fluosilicic acid content in the filtrate 2 is 0, the F-content in the filtrate 2 is 0.088%, and the potassium fluosilicate content in the solid 1 is as high as 99.57%.
Example 5:
example 5 provides a composition of H 2 SiF 6 ：17.60％，HF：4.94％，H 2 SO 4 ：3.34％，HCl：0.03％，HNO 3 :2.23 percent and the rest of the photovoltaic fluorine-containing waste acid with water is taken as raw material. 50.00g of fluorine-containing waste acid is weighed, 1.77g of silicic acid solid is weighed, the silicic acid solid is slowly added into the fluorine-containing waste acid at normal temperature, stirring reaction is carried out for 1 hour, and filtering is carried out to obtain filtrate 1; weighing 15.86g of potassium sulfate, preparing a 20% potassium sulfate solution, adding the solution into the filtrate 1, stirring and reacting for 2 hours at 40 ℃, carrying out suction filtration to obtain filtrate 2 and solid 1, respectively washing the solid 1 twice by deionized water with the theoretical mass 4 times of that of potassium fluosilicate, carrying out suction filtration for 10 minutes, and drying the washed filter cake to constant weight at 105 ℃ to obtain the product potassium fluosilicate.
And (3) through analysis and detection: the fluosilicic acid content in the filtrate 2 is 0, the F-content in the filtrate 2 is 0.135%, and the potassium fluosilicate content in the solid 1 is as high as 99.27%.
Example 6:
example 6 provides a composition of 21.16%, HF:8.40%, H2SO4:4.50%, HCl:1.62%, HNO3:1.57 percent of photovoltaic fluorine-containing waste acid with the rest of water as raw material. 50.00g of fluorine-containing waste acid is weighed, 2.31g of silicon dioxide powder is weighed, 30% silicon dioxide emulsion is prepared, the silicon dioxide emulsion is slowly added into the fluorine-containing waste acid at normal temperature, stirring reaction is carried out for 1 hour, and filtering is carried out to obtain filtrate 1; then weighing 18.73g of potassium sulfate, preparing a 20% potassium sulfate solution, adding the solution into filtrate 1, stirring and reacting for 2 hours at 40 ℃, carrying out suction filtration to obtain filtrate 2 and solid 1, respectively washing the solid 1 twice by deionized water with the theoretical mass 5 times of that of potassium fluosilicate, carrying out suction filtration for 10 minutes, and drying the washed filter cake to constant weight at 120 ℃ to obtain the product potassium fluosilicate.
And (3) through analysis and detection: the fluosilicic acid content in the filtrate 2 is 0, the F-content in the filtrate 2 is 0.104%, and the potassium fluosilicate content in the solid 1 is as high as 99.42%.
Example 7:
example 7 provides a composition of H 2 SiF 6 ：21.16％，HF：8.40％，H 2 SO 4 ：4.50％，HCl：1.62％，HNO 3 :1.57 percent of photovoltaic fluorine-containing waste acid with the rest of water as raw material. 50.00g of fluorine-containing waste acid is weighed, 2.52g of silicon dioxide powder is weighed, 30% silicon dioxide emulsion is prepared, the silicon dioxide emulsion is slowly added into the fluorine-containing waste acid at normal temperature, stirring reaction is carried out for 1 hour, and filtering is carried out to obtain filtrate 1; weighing 17.39g of potassium nitrate, preparing a 20% potassium nitrate solution, adding the solution into the filtrate 1, stirring and reacting for 2 hours at 40 ℃, filtering to obtain filtrate 2 and solid 1, washing the solid 1 twice respectively by deionized water with the theoretical mass 4 times of the potassium fluosilicate, filtering for 10 minutes, and drying the washed filter cake to constant weight at 120 ℃ to obtain the product potassium fluosilicate.
And (3) through analysis and detection: the fluosilicic acid content in the filtrate 2 is 0, the F-content in the filtrate 2 is 0.083%, and the potassium fluosilicate content in the solid 1 is as high as 99.82%.
Example 8:
example 8 provides a composition of H2SiF6:21.16%, HF:8.40%, H2SO4:4.50%, HCl:1.62%, HNO3:1.57 percent of photovoltaic fluorine-containing waste acid with the rest of water as raw material. Weighing 50.00g of fluorine-containing waste acid, weighing 2.52g of silicon dioxide powder, slowly adding the silicon dioxide powder into the fluorine-containing waste acid at normal temperature, stirring for reacting for 1 hour, and filtering to obtain filtrate 1; weighing 15.72g of potassium chloride, preparing a 20% potassium chloride solution, adding the solution into the filtrate 1, stirring and reacting for 2 hours at 40 ℃, filtering to obtain filtrate 2 and solid 1, washing the solid 1 twice respectively by deionized water with the theoretical mass 4 times of the potassium fluosilicate, filtering for 10 minutes, and drying the washed filter cake to constant weight at 120 ℃ to obtain the product potassium fluosilicate.
And (3) through analysis and detection: the fluosilicic acid content in the filtrate 2 is 0, the F-content in the filtrate 2 is 0.090%, and the potassium fluosilicate content in the solid 1 is as high as 99.60%.
Example 9
Example 9 provides a composition of H2SiF6:21.16%, HF:8.40%, H2SO4:4.50%, HCl:1.62%, HNO3:1.57 percent of photovoltaic fluorine-containing waste acid with the rest of water as raw material. Weighing 50.00g of fluorine-containing waste acid, weighing 3.01g of silicic acid solid, slowly adding the silicic acid solid into the fluorine-containing waste acid at normal temperature, stirring for reaction for 1 hour, and filtering to obtain filtrate 1; weighing 16.03g of potassium chloride, preparing a 20% potassium chloride solution, adding the solution into the filtrate 1, stirring and reacting for 2 hours at 40 ℃, filtering to obtain filtrate 2 and solid 1, washing the solid 1 twice respectively by deionized water with the theoretical mass 4 times of the potassium fluosilicate, filtering for 10 minutes, and drying the washed filter cake to constant weight at 120 ℃ to obtain the product potassium fluosilicate.
And (3) through analysis and detection: the fluosilicic acid content in the filtrate 2 is 0, the F-content in the filtrate 2 is 0.178%, and the potassium fluosilicate content in the solid 1 is as high as 99.08%.
Example 10
Example 10 provides a composition of H2SiF6:21.16%, HF:8.40%, H2SO4:4.50%, HCl:1.62%, HNO3:1.57 percent of photovoltaic fluorine-containing waste acid with the rest of water as raw material. Weighing 50.00g of fluorine-containing waste acid, weighing 3.28g of silicic acid solid, slowly adding the silicic acid solid into the fluorine-containing waste acid at normal temperature, stirring for reaction for 1 hour, and filtering to obtain filtrate 1; and weighing 19.67g of potassium sulfate, preparing a 20% potassium sulfate solution, adding the solution into the filtrate 1, stirring and reacting for 2 hours at 40 ℃, filtering to obtain filtrate 2 and solid 1, washing the solid 1 twice respectively by deionized water with the theoretical mass 4 times of the potassium fluosilicate, filtering for 10 minutes, and drying the washed filter cake to constant weight at 120 ℃ to obtain the product potassium fluosilicate.
And (3) through analysis and detection: the fluosilicic acid content in the filtrate 2 is 0, the F-content in the filtrate 2 is 0.133%, and the potassium fluosilicate content in the solid 1 is as high as 99.36%.
The invention realizes the high-efficiency recycling of fluorine resources in fluorine-containing waste acid in the photovoltaic industry, and the purity of the obtained sample potassium fluosilicate is more than or equal to 99.0%.
The operation method is simple and reliable, does not generate new solid waste, and has the characteristics of safety and environmental protection.
The foregoing has shown and described the basic principles, main features and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The method for preparing the potassium fluosilicate by using the fluorine-containing waste acid in the photovoltaic industry is characterized by comprising the following steps of:
(1) Converting, namely slowly adding a conversion agent into the photovoltaic fluorine-containing waste acid to perform stirring reaction, and performing suction filtration and separation to obtain filter residues and a filtrate A, wherein the filter residues are recycled;
(2) Preparing fluosilicic acid, namely adding a reactant into the filtrate A for stirring reaction, and carrying out suction filtration to separate solid and liquid after the reaction is finished to obtain a solid and filtrate B, and washing and drying the solid to obtain potassium fluosilicate; the reactant is one of potassium salt and potassium hydroxide;
(3) Recycling, namely recycling the washing liquid obtained by washing the filtrate B and the solid with water.
2. The method for preparing potassium fluosilicate by utilizing fluorine-containing waste acid in the photovoltaic industry as claimed in claim 1, which is characterized in that: slowly adding a conversion agent into the photovoltaic fluorine-containing waste acid in the step (1) for stirring reaction, wherein the reaction temperature is 0-100 ℃, the reaction time is 10-240min, and the molar ratio of the fluorine waste acid to the conversion agent is 6.0:1.0-2.0; the transforming agent is one of silicon dioxide, silicic acid and potassium silicate.
3. The method for preparing potassium fluosilicate by utilizing fluorine-containing waste acid in the photovoltaic industry as claimed in claim 1, which is characterized in that: the photovoltaic fluorine-containing waste acid comprises fluosilicic acid, hydrofluoric acid, sulfuric acid, hydrochloric acid and nitric acid.
4. The method for preparing potassium fluosilicate by utilizing fluorine-containing waste acid in the photovoltaic industry as claimed in claim 1, which is characterized in that: in the step (2), the reaction temperature is 10-80 ℃ and the reaction time is 30-300min.
5. The method for preparing potassium fluosilicate by utilizing fluorine-containing waste acid in the photovoltaic industry as claimed in claim 1, which is characterized in that: the reactant is potassium salt, and the molar ratio of fluosilicic acid to potassium salt is 1.0:1.0-3.6; the potassium salt comprises one or more of potassium sulfate, potassium chloride, potassium nitrate, potassium carbonate and potassium bicarbonate.
6. The method for preparing potassium fluosilicate by utilizing fluorine-containing waste acid in the photovoltaic industry as claimed in claim 1, which is characterized in that: the reactant is potassium hydroxide, and the molar ratio of fluosilicic acid to potassium hydroxide is 1.0:2.0-3.0.
7. The method for preparing potassium fluosilicate by utilizing fluorine-containing waste acid in the photovoltaic industry as claimed in claim 1, which is characterized in that: and (3) carrying out solid-liquid separation by adopting a circulating water suction filter in the step (1) and the step (2) respectively.
8. The method for preparing potassium fluosilicate by utilizing fluorine-containing waste acid in the photovoltaic industry as claimed in claim 1, which is characterized in that: washing is carried out by using a washing liquid, the mass of the washing liquid is 2-8 times of that of the solid matters, and the washing liquid is deionized water.
9. The method for preparing potassium fluosilicate by utilizing fluorine-containing waste acid in the photovoltaic industry as claimed in claim 1, which is characterized in that: the drying method is drying at 80-180deg.C for 5-24 hr.
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