WO2010004925A1 - Procédé de récupération de silicium, de titane et de fluor - Google Patents

Procédé de récupération de silicium, de titane et de fluor Download PDF

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Publication number
WO2010004925A1
WO2010004925A1 PCT/JP2009/062095 JP2009062095W WO2010004925A1 WO 2010004925 A1 WO2010004925 A1 WO 2010004925A1 JP 2009062095 W JP2009062095 W JP 2009062095W WO 2010004925 A1 WO2010004925 A1 WO 2010004925A1
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titanium
silicon
aqueous solution
precipitate
fluoride
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PCT/JP2009/062095
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English (en)
Japanese (ja)
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滋 木谷
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Kiya Shigeru
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Priority to JP2010519752A priority Critical patent/JP5392576B2/ja
Publication of WO2010004925A1 publication Critical patent/WO2010004925A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • 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
    • C01B33/02—Silicon
    • 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
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/186—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof from or via fluosilicic acid or salts thereof by a wet process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/20—Fluorine
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/02—Halides of titanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Definitions

  • the present invention relates to a method for recovering silicon, titanium and fluorine from an aqueous solution containing silicon and / or titanium fluoride.
  • Hydrofluoric acid is used for etching processing and surface cleaning of silicate glass (that is, silicate-based glass: hereinafter simply referred to as glass).
  • silicate glass that is, silicate-based glass: hereinafter simply referred to as glass.
  • silicon dioxide (SiO 2 ) which is the main component of glass, reacts and dissolves with hydrofluoric acid (HF) as shown in the following formula (1) to form hexafluorosilicic acid (H 2 SiF 6 ) and water (H 2 O) are produced.
  • the concentration of hydrofluoric acid in the aqueous solution used to dissolve the glass decreases as the amount of glass dissolved increases, and the dissolving ability of the aqueous solution also decreases. Therefore, as a result of research on a method for recovering the dissolving ability, for example, in JP-A-2000-72482 and JP-T-2005-534595, an electrolyte such as fluoride is added to restore the dissolving ability. Is disclosed.
  • potassium hexafluorosilicate produced as a by-product by the above method is used as an enamel or as a preservative, but its amount is not so large, so when it is produced in large quantities from glass etching and cleaning processes Can only consume part of it. Furthermore, since potassium hexafluorosilicate is a toxic substance, it requires a great deal of cost to be disposed of without causing pollution.
  • the treatment for recovering the dissolving ability of the mixed acid waste liquid is not performed and the waste is disposed after the neutralization treatment with an alkali. Then, when this inventor performed the process which adds electrolytes, such as a fluoride, instead of the neutralization process by an alkali, it turned out that the melt
  • nitric hydrofluoric acid a mixed acid of nitric acid and hydrofluoric acid (hereinafter referred to as nitric hydrofluoric acid) or hydrofluoric acid is performed. Yes.
  • nitric hydrofluoric acid titanium dissolves as a tetravalent fluoride, and when it is pickled with an aqueous solution of hydrofluoric acid not containing nitric acid, it dissolves as a trivalent fluoride.
  • Titanium alloys are alloys containing metals such as aluminum, vanadium, tin, and palladium in addition to titanium, but most of the composition is titanium, so pickling with nitric hydrofluoric acid or hydrofluoric acid is possible. As in the case of pure titanium, titanium dissolves as a tetravalent or trivalent fluoride.
  • the present inventor has studied various means for precipitating titanium while maintaining the acidity without neutralizing the aqueous solution containing the fluoride of titanium with an alkali such as ammonia.
  • an alkali such as ammonia.
  • the titanium dissolved when pickled with nitric hydrofluoric acid is usually contained in part or in large part as hexafluorotitanic acid (H 2 TiF 6 ). It has been found that it can be precipitated as hexafluorotitanate by reacting with a cation.
  • titanium when potassium fluoride (KF) or potassium nitrate (KNO 3 ) is used as the electrolyte, titanium is converted to potassium hexafluorotitanate (K 2 TiF 6 ) by the reaction of the following formulas (4) and (5). ). Moreover, since the hydrogen fluoride (HF) and nitric acid (HNO 3 ) are produced by this precipitation reaction, the pickling ability of titanium is enhanced. H 2 TiF 6 + 2KF ⁇ K 2 TiF 6 + 2HF (4) Formula H 2 TiF 6 + 2KNO 3 ⁇ K 2 TiF 6 + 2HNO 3 (5)
  • TiF 3 trivalent fluoride
  • various oxidizing agents can be used.
  • nitric acid or oxygen (O 2 ) when used, nitric acid or oxygen (O 2 ) is used, hexafluorotitanic acid is produced by the reaction of the following formulas (6) and (7). Presumed to be generated.
  • Formula 4TiF 3 + O 2 + 12HF ⁇ 4H 2 TiF 6 + 2H 2 O (7) Formula
  • potassium hexafluorotitanate produced by the reaction of the above formulas (4) and (5) is used for toxicity, etc., it is not necessary, so a large amount from the pickling process of titanium or titanium alloy. However, only a part of it can be consumed. Furthermore, since potassium hexafluorotitanate is a toxic substance, it requires a great deal of cost to be disposed of without causing pollution.
  • the problem to be solved by the present invention is hexafluorosilicate produced by dissolving glass, silicon, titanium, titanium alloy, etc. in an aqueous solution containing hydrofluoric acid, and then adding an electrolyte or a cation. And hexafluorotitanate is changed to a versatile substance to expand the usage and usage.
  • the present inventors have studied a method of chemically decomposing and separating hexafluorosilicate or hexafluorotitanate, which has been precipitated and separated, into a versatile substance. I found a way. One of these is the addition of ammonia (NH 3 ) and water to these salts to convert them into precipitates of colloidal silicic acid (SiO 2 .nH 2 O) or titanium hydroxide (Ti (OH) 4 ). Is separated from the aqueous solution, washed with water, etc., and then heated and baked to change to silicon dioxide (SiO 2 ) or titanium dioxide (TiO 2 ). Ammonia may be added either as an aqueous solution or as a gas.
  • silicon contained in potassium hexafluorosilicate precipitates as glued silicic acid
  • titanium contained in potassium hexafluorotitanate is titanium hydroxide.
  • fluorine and potassium are converted into potassium fluoride (KF) or ammonium fluoride (NH 4 F) and dissolved in the aqueous solution
  • silicic acid or titanium hydroxide can be separated from the aqueous solution by a method such as filtration. .
  • the separated silicic acid or titanium hydroxide can be changed into silicon dioxide or titanium dioxide by washing with water or the like and then heating and baking. Silicon dioxide can be reused for additives such as glass raw materials and rubber, and titanium dioxide can be reused for applications such as white pigments and photocatalysts.
  • Ammonia produced by these reactions is separated and recovered by a method such as steam distillation and can be reused for the reaction of the above formula (8) or (9). Further, the precipitate of calcium fluoride produced by the reaction of the formula (13) can be separated by a method such as filtration and reused as a raw material for hydrofluoric acid production. Further, the aqueous solution after separation of silicic acid, titanium hydroxide, ammonia and calcium fluoride produced by the reactions of the above formulas (8), (9), (12) and (13) is fluorided. Since only potassium is included, it can be reused for the reactions of formulas (2) and (4).
  • an aqueous solution of hydrofluoric acid and potassium hydroxide can be obtained by subjecting this aqueous solution to electrodialysis treatment or ion exchange treatment. By these treatments, one molecule of hydrogen fluoride and one molecule of potassium hydroxide are generated from one molecule of potassium fluoride.
  • the obtained aqueous solution of hydrogen fluoride (that is, hydrofluoric acid) can be reused for dissolution of glass and silicon metal, and potassium hydroxide can be reused for the reaction of the above formula (12). .
  • Another method that the present inventors have found as a useful method for chemically decomposing hexafluorosilicate or hexafluorotitanate is by decomposing these salts by heating to tetrafluorosilicate.
  • This is a method of generating a gas of elemental (SiF 4 ) or titanium tetrafluoride (TiF 4 ).
  • the decomposition reaction when these salts are potassium salts is presumed to be according to the following formula (14) or (15).
  • K 2 TiF 6 ⁇ TiF 4 + 2KF (15)
  • Hexafluorosilicate precipitated from a hydrofluoric acid-containing aqueous solution in which glass is dissolved may be contaminated by metal elements such as aluminum, iron, and zinc contained in the glass.
  • the treatment method including hexafluorosilicic acid with less impurities can be obtained. Therefore, if an electrolyte or a cation is added to the obtained aqueous solution of hexafluorosilicate, potassium hexafluorosilicate that does not contain aluminum or the like can be precipitated, for example, by the reaction of the above formula (2).
  • hexafluorotitanate precipitated from an aqueous solution of nitric hydrofluoric acid obtained by pickling a titanium alloy containing a large amount of aluminum may be contaminated with elements such as aluminum.
  • hexafluorotitanic acid with less impurities can be obtained. Therefore, if an electrolyte or a cation is added to the obtained aqueous solution of hexafluorotitanate, for example, potassium hexafluorotitanate that does not contain aluminum or the like can be precipitated by the reaction of the above formula (4).
  • high purity silicon dioxide or high purity titanium dioxide can be obtained by heating and baking.
  • potassium hydroxide or calcium hydroxide is added to an aqueous solution from which colloidal silicic acid or titanium hydroxide is separated, and ammonium fluoride is converted to ammonia and fluoride by the reaction of the above formulas (12) and (13). It can be changed to potassium or calcium fluoride and reused.
  • the present invention has been completed on the basis of the above studies, and is summarized in the following methods (1) to (7) for recovering silicon, titanium and fluorine.
  • Silicon or / and titanium fluoride produced by dissolving a substance containing silicon or / and titanium using an aqueous solution containing hydrofluoric acid is converted to hexafluorosilicate or / and hexafluoro.
  • Step A Step of changing the valence of titanium contained in the aqueous solution to tetravalent as necessary:
  • Step B Step of adding hydrogen fluoride and / or fluoride to the aqueous solution as necessary :
  • Step C A step of adding an electrolyte or / and a cation to the aqueous solution as required: and
  • Step D a step of separating the precipitate generated in the steps A to C.
  • Step E Step of recovering elemental, titanium and fluorine
  • Step F The process of isolate
  • step K Method for recovering elemental, titanium and fluorine (step K): heating to a temperature higher than the temperature at which silicon tetrafluoride or / and titanium tetrafluoride is generated: (Step L) Absorbing and / or absorbing the gas generated by Step K or / and the solid formed by the condensation thereof into an aqueous solution or water containing hydrogen fluoride or / and fluoride or / and electrolyte or / and cation.
  • Step M Step of adding hydrogen fluoride or / and fluoride as required:
  • Step N Step of adding electrolyte or / and cation as required:
  • Step O After separating the precipitate generated by the above-mentioned Step L and Steps M and N, which are performed as necessary, the precipitate is partially or entirely of Steps E to J of (3) above.
  • the process processed by the method including the process of.
  • Step P The method described in (1) and (2) above, wherein the method including the chemical decomposition step is a method including a part or all of the following steps P to V.
  • Method for recovering elemental, titanium and fluorine step P: heating to a temperature higher than the temperature at which silicon tetrafluoride or / and titanium tetrafluoride is generated:
  • Step Q The step of reacting the gas produced in the step P or / and the solid produced by the condensation with water and ammonia:
  • Step R Step of separating the precipitate generated in the step Q:
  • Step S Steps of heating and baking after washing the precipitate separated in the step R:
  • Step T Step of separating ammonia after adding an alkali metal hydroxide and / or an alkaline earth metal hydroxide, if necessary, to the aqueous solution from which the precipitate has been separated in the step R:
  • Step U Step of separating the precipitate generated in the step T:
  • Silicon of the present invention the separation of titanium and fluorine, by the recovery method, an aqueous solution containing etching or surface cleaning of the glass, the etching of Shirikon'u et Doha, or hydrofluoric acid used in the pickling of titanium or a titanium alloy Titanium dioxide, glass, silicon, which is useful as a raw material for glass, white pigments, etc., as well as by-products generated during the recycling process.
  • hydrofluoric acid used for dissolving titanium, etc., or calcium fluoride used as a raw material for producing hydrofluoric acid can be obtained. Further, along with this, the amount of industrial waste generated is greatly reduced, and the burden on the environment is reduced. Therefore, a great industrial and social effect can be obtained.
  • FIG. 1 is an explanatory view showing an example of a procedure of a method for recovering silicon and fluorine after melting glass with a hydrofluoric acid-containing aqueous solution.
  • Example 1 FIG. 2 is an explanatory view showing an example of a procedure of a method for recovering silicon and fluorine after dissolving silicon metal with a hydrofluoric acid-containing aqueous solution.
  • FIG. 3 is an explanatory view showing an example of a procedure of a method for recovering titanium and fluorine from an aqueous solution obtained by pickling titanium with nitric hydrofluoric acid. (Example 3) FIG.
  • FIG. 4 is an explanatory view showing an example of a procedure of a method for recovering titanium and fluorine from an aqueous solution obtained by pickling titanium with hydrofluoric acid.
  • FIG. 5 is an explanatory view showing an example of a procedure of a method for separating and recovering silicon and fluorine after melting glass with a hydrofluoric acid-containing aqueous solution.
  • Example 4 6 after pickling of titanium with et Tsu quenching effluent Shirikon'u et Doha, silicon, titanium and fluorine separation is an explanatory view showing an example of a procedure of a method of recovering.
  • FIG. 4 is an explanatory view showing an example of a procedure of a method of recovering.
  • FIG. 7 is a cross-sectional view schematically showing the structure of an apparatus used for chemical reaction and distillation.
  • FIG. 8 is a cross-sectional view schematically showing the structure of an apparatus for thermally decomposing hexafluorosilicate and hexafluorotitanate and recovering them as a fluoride of silicon and titanium.
  • FIG. 9 is a cross-sectional view schematically showing the structure of the electrodialysis apparatus.
  • FIG. 10 is a cross-sectional view schematically showing the structure of an ion exchange column.
  • the hydrofluoric acid concentration of the aqueous solution used for dissolving glass, silicon, titanium and titanium alloy is usually a concentration used industrially, and does not need to be strictly limited.
  • silicon and titanium in order for silicon and titanium to dissolve as hexafluorosilicic acid and hexafluorotitanic acid, 6 mol of hydrogen fluoride is required for 1 mol of silicon and titanium.
  • an aqueous solution containing only hydrofluoric acid can be used, but an acid such as sulfuric acid may be included in addition to the aqueous solution.
  • Sulfuric acid has no direct effect on the formation of hexafluorosilicic acid, but when glass containing barium or lead is dissolved, it reacts with sulfuric acid in aqueous solution to form a poorly soluble sulfate. , The formation of fluoride is suppressed and the consumption of hydrofluoric acid is saved.
  • the hexafluorosilicate is prevented from being contaminated with barium or lead. be able to.
  • Doha single crystal usually, high concentrations (e.g., 10 ⁇ 40 mass%) hydrofluoric acid, although mixed acid of nitric acid and acetic acid are used, the polycrystal silicon metal In order to dissolve, a high concentration of mixed acid is not necessarily required, and addition of acetic acid is not essential. Conditions such as the acid concentration and processing temperature may be appropriately selected in consideration of the purpose of etching and dissolution.
  • a mixed acid of hydrofluoric acid and sulfuric acid can be used in addition to nitric hydrofluoric acid and hydrofluoric acid.
  • aluminum fluoride and the like may precipitate, so before adding the electrolyte to precipitate hexafluorotitanate, separate and remove these insolubles. If so, the hexafluorotitanate can be prevented from being contaminated with aluminum or the like.
  • oxidizing agent such as nitric acid or oxygen.
  • the appropriate addition amount of these oxidizing agents is desirably determined using the redox potential of the solution as a guideline, and the redox potential can be measured using a commercially available redox potential meter.
  • the step of changing the valence of titanium contained in the aqueous solution to tetravalent the step of adding hydrofluoric acid or fluoride, the electrolyte and the positive If a step of adding ions is necessary, these steps may be performed in any order. If the reaction of the step of changing the valence of titanium to tetravalent is difficult to proceed, this step is performed. This should be done last.
  • an alkali metal fluoride having a high solubility in water is preferable.
  • Alkali metal fluorides are not only electrolytes but also fluorides.
  • potassium fluoride when potassium fluoride is used, potassium hexafluorosilicate or potassium hexafluorotitanate having a relatively low solubility is generated, so that separation from an aqueous solution can be performed relatively easily.
  • hydrofluoric acid is produced
  • rubidium fluoride (RbF) and cesium fluoride (CsF) can also be suitably used, but the price is relatively high.
  • potassium sulfate (K 2 SO 4 ), rubidium sulfate (Rb 2 SO 4 ), and cesium sulfate (Cs 2 SO 4 ) can be suitably used for an aqueous solution containing sulfuric acid.
  • potassium nitrate (KNO 3 ), rubidium nitrate (RbNO 3 ), and cesium nitrate (CsNO 3 ) can be preferably used.
  • sodium fluoride (NaF) or ammonium fluoride (NH 4 F) can be used as an electrolyte other than these compounds.
  • the former has a considerably low solubility, it is necessary to adjust the addition amount so that it does not precipitate together with sodium hexafluorosilicate (Na 2 SiF 6 ) or sodium hexafluorotitanate (Na 2 TiF 6 ).
  • the solubility of ammonium hexafluorosilicate ((NH 4 ) 2 SiF 6 ) and ammonium hexafluorotitanate ((NH 4 ) 2 TiF 6 ) is high, Separation tends to be incomplete.
  • the appropriate amount of electrolyte added depends on the type of electrolyte and the types of hexafluorosilicate and hexafluorotitanate to be precipitated, but when potassium hexafluorosilicate is deposited using potassium fluoride, potassium and silicate are added. It is desirable that the molar ratio (K / Si molar ratio) of the element is 3 or more and the concentration of potassium in the aqueous solution is 0.3 mol / dm 3 or more. When potassium hexafluorotitanate is precipitated, the molar ratio of potassium to titanium (K / Ti molar ratio) is 6 or more and the concentration of potassium in the aqueous solution is 0.6 mol / dm 3 or more.
  • potassium hexafluorosilicate or potassium hexafluorotitanate precipitates (the amount of precipitation is relatively small).
  • potassium fluoride in an aqueous solution having a concentration of about 1 to 2 mol / dm 3 , but in order to reduce the concentration of the aqueous solution as much as possible, it can be added and dissolved with potassium fluoride chemicals. Also good.
  • a filtration separation method which is usually used industrially can be applied.
  • hexafluorosilicate has a relatively strong caking property, it solidifies when strongly compressed by suction filtration or the like, and the process of dispersing it in water and reacting with ammonia does not proceed smoothly.
  • Solid-liquid separation methods other than filtration can also be applied, but it is necessary to select a separation method and conditions so that the precipitated hexafluorosilicate is not solidified.
  • the purity of silicon dioxide produced in the subsequent step can be increased by washing with an appropriate washing solution.
  • hexafluorosilicate is partly dissolved by washing, in order to reduce the loss due to dissolution, it is better to wash with the aqueous electrolyte solution used to precipitate these salts than to wash with water. Good.
  • Hexafluorosilicate and hexafluorotitanate separated from the aqueous solution and optionally washed can be chemically decomposed by treatment with ammonia and water as described above.
  • these salts are transferred to a suitable container, and water is added and mixed.
  • the amount of water to be added does not need to be particularly strictly defined, but about 200 to 1000 times the weight of silicon or titanium in the precipitate is appropriate.
  • ammonia is added while stirring the solution, and the pH of the solution is adjusted to 9 or higher (preferably 10 or higher).
  • Ammonia is conveniently added in a 10 to 28% aqueous solution, but ammonia gas generated in a later step may be blown.
  • the solution After adding and mixing ammonia, the solution needs to be heated to 60 to 100 ° C. and held for about 30 minutes to 2 hours. Then, after cooling to room temperature to about 50 ° C. and measuring the pH again, if the pH is less than 9, the ammonia is added after adding ammonia so that it is 9 or more (preferably 10 or more).
  • the acid or titanium hydroxide precipitate is separated by a method such as filtration. These separated precipitates are thoroughly washed with water and then converted to silicon dioxide (SiO 2 ) or titanium dioxide (TiO 2 ) by heating at 800 to 1000 ° C. for 1 to 5 hours using an electric furnace or the like. Can do.
  • FIG. 7 An apparatus having a schematic cross-sectional view shown in Fig. 7 is recommended.
  • a mixture of hexafluorosilicate or hexafluorotitanate precipitate and water After that, the solution is stirred by the stirrer 2-1, and at the same time, the pH of the solution is measured using the pH sensor 5 and ammonia water is added from the feed pipe 10.
  • ammonia water or together with ammonia water
  • ammonia gas may be blown from the gas inlet pipe 12.
  • the solution When the pH of the solution reaches 9-10, the solution is heated using the heater 3 and held at 60-100 ° C. for 30 minutes to 2 hours. Thereafter, the pH is measured while cooling to room temperature to around 50 ° C., and when the pH is less than 9, after adding ammonia so that it becomes 9 or more, the generated silicic acid or titanium hydroxide is precipitated.
  • the solution is discharged from the discharge pipe 11 together with the solution and transferred to a filtration device or the like.
  • the ammonia gas evaporated together with the water vapor from the liquid level is led from the gas discharge pipe 13 to the cooler 6 to become ammonia water, which is stored in the distillate receiving tank 8.
  • the apparatus in FIG. 7 can also be used for ammonia distillation. That is, the solution after separating the precipitate of silicic acid or titanium hydroxide is charged into the treatment tank 1 from the feed pipe 10, and then the temperature of the solution is used using the heater 3 while stirring the solution with the stirrer 2-1. Is heated to 80-100 ° C. Further, air and water vapor at around 100 ° C. are sent from the gas charging pipe 12 to evaporate the ammonia dissolved in the solution together with the water vapor. Store in the drainage tank 8.
  • an apparatus for electrodialyzing a solution obtained by distilling and separating ammonia and then filtering and separating a precipitate of an alkaline earth metal fluoride as necessary for example, an apparatus as shown in a schematic diagram (side view) in FIG. Is recommended.
  • the electrolytic cell 24 of this apparatus is composed of four cells (chambers) 31 to 34 separated by two cation exchange membranes 27-1 and 27-2 and one anion exchange membrane 28.
  • a DC voltage is supplied to the cathode 26 from a DC power supply 29 through a conducting wire 30.
  • an aqueous solution of acid such as sulfuric acid (H 2 SO 4 ) is placed in the cell 33 provided with the anode 25, and an aqueous solution of low concentration potassium hydroxide (KOH) is placed in the cell 34 provided with the cathode 26.
  • a cell 31 formed between the cation exchange membrane 27-2 and the anion exchange membrane 28 is filled with a solution obtained by distilling and separating ammonia (FIG. 9 shows an example of an aqueous potassium fluoride solution).
  • the cell 32 formed between the cation exchange membrane 27-1 and the anion exchange membrane 28 is filled with a low concentration hydrofluoric acid aqueous solution or pure water.
  • hydroxide ions (OH ⁇ ) are generated on the cathode surface by the electrode reaction shown in the following formula (21) (at the same time, hydrogen gas is generated).
  • the concentration of the potassium hydroxide aqueous solution in the cell 34 becomes higher as electrodialysis proceeds. It can be reused for the ammonia distillation treatment by the reaction of formula).
  • an apparatus for ion-exchange treatment of a solution from which ammonia has been separated for example, an apparatus having a schematic diagram (cross-sectional view) shown in FIG. 10 is recommended.
  • the solution injected from the liquid inlet pipe 37 at the upper part of the apparatus flows out of the liquid discharge pipe 38 at the lower part of the apparatus through the porous plate 36-1, the ion exchange resin 39 and the porous plate 36-2.
  • the ion exchange resin either a cation exchange resin or an anion exchange resin may be used.
  • an anion exchange resin a functional group whose functional group has been converted to OH-type in advance is used.
  • Fluoride ions (F ⁇ ) generated by dissociation of potassium fluoride in a solution obtained by distilling and separating ammonia are hydroxide ions (OH) trapped in the functional groups of the anion exchange resin.
  • - ) Is replaced with potassium hydroxide (KOH) as shown in the following formula (23), which can be reused for the ammonia distillation treatment by the reaction of the formula (12). .
  • R + represents a positively charged anion exchange resin substrate.
  • fluoride ions (F ⁇ ) captured by the functional group of the anion exchange resin are expressed by the following formula (24).
  • hydrofluoric acid (HF) flows out and can be reused to dissolve glass or silicon metal.
  • the anion exchange resin returns to the OH ⁇ type again.
  • these salts separated from an aqueous solution and washed as needed are about 100 to 110 ° C. After sufficiently drying using a drier adjusted to a temperature of 1, it is decomposed by heating to a high temperature of about 600 to 1000 ° C.
  • FIG. 8 schematically shows the structure of an apparatus for performing such a thermal decomposition process.
  • the dried hexafluorosilicate or hexafluorotitanate is put in the thermal decomposition vessel 15, placed on the vessel support 16, and set in the heating section in the heating tube 17.
  • platinum or nickel is recommended as the material for the electrothermal decomposition container 15.
  • the electric furnace 18 is used to heat the heating tube, and at the same time, argon gas, nitrogen gas, air or the like is supplied from the carrier gas supply tube 19, and silicon tetrafluoride or four produced by the thermal decomposition reaction are introduced. Titanium fluoride gas is fed into condenser 21 through conduit 20-1.
  • the conduit 20-1 is heated using an electric heater or the like so that the inner surface temperature is maintained at about 300 ° C. or higher, and the condenser 21 has an inner surface temperature of at least 250 ° C., preferably 50 ° C. It is necessary to cool it to about 100 ° C.
  • silicon tetrafluoride gas is fed into the absorbing liquid 22 through the conduit 20-2.
  • the absorbing solution is stirred using a stirrer 2-2. Water may be used instead of the absorbing liquid.
  • both hexafluorosilicate and hexafluorotitanate are pyrolyzed, and the generated silicon tetrafluoride and titanium tetrafluoride are absorbed or dissolved in separate absorption liquids or water.
  • the condenser 21 is not necessarily required when it is not necessary to separate silicon tetrafluoride and titanium tetrafluoride or when the hexafluorotitanate is not thermally decomposed.
  • an aqueous solution containing 2 moles or more of hydrofluoric acid per mole of silicon or / and titanium or 2 moles Hexafluorosilicate and / or hexafluorotitanate can also be produced by absorption or dissolution in an aqueous solution containing the above hydrofluoric acid and 2 moles or more of cations.
  • silicon tetrafluoride and / or titanium tetrafluoride is reacted with water and ammonia to change to silicic acid or / and titanium hydroxide
  • silicon tetrafluoride and / or titanium tetrafluoride is used.
  • a method of adding or dissolving ammonia in water and then adding ammonia and a method of absorbing or dissolving silicon tetrafluoride and / or titanium tetrafluoride in aqueous ammonia can be applied.
  • ammonia so that the pH of the solution is 9 or more (preferably 10 or more).
  • Ammonia is conveniently added in a 10 to 28% aqueous solution, but ammonia gas generated in a later step may be blown.
  • the amount of water added to adjust the concentration does not need to be strictly defined, but is appropriately about 200 to 1000 times the weight of silicon or titanium in the solution.
  • the solution After adding and mixing ammonia, the solution needs to be heated to 60 to 100 ° C. and held for about 30 minutes to 2 hours. Then, after cooling to room temperature to about 50 ° C. and measuring the pH again, if the pH is less than 9, the ammonia is added after adding ammonia so that it is 9 or more (preferably 10 or more).
  • the acid or titanium hydroxide precipitate is separated by a method such as filtration. These separated precipitates are thoroughly washed with water and then converted to silicon dioxide (SiO 2 ) or titanium dioxide (TiO 2 ) by heating at 800 to 1000 ° C. for 1 to 5 hours using an electric furnace or the like. Can do.
  • Aqueous solution A is a general-purpose plate glass dissolved in a hydrofluoric acid aqueous solution
  • Aqueous solution B is a CRT (cathode ray tube) panel glass dissolved in a mixed aqueous solution of hydrofluoric acid and sulfuric acid
  • aqueous solution C is silicon metal. Is dissolved with a mixed acid of hydrofluoric acid, nitric acid and acetic acid. The content of silicon dioxide in the glass, the amount of glass and metal silicon dissolved, and the composition of the aqueous solution for dissolution are as shown in Table 1. is there.
  • sample solutions was filtered using a filter paper, its 50 cm 3 or 100 cm 3 was fractionated was transferred to a plastic container, and dissolving an electrolyte compound 0.05 ⁇ 0.10 mol of water volume 70cm 3 Things were added and mixed.
  • sample solutions A and B filtration was omitted and 100 cm 3 was immediately collected, and the same operation was performed thereafter.
  • sample solutions A and C were also tested in which the solution was suction filtered to solidify the precipitate and in which the precipitate was dried after filtration.
  • ammonia water having a concentration of about 15% was added to adjust the pH to 6.5 to 10.2.
  • the solution in 19 containers was heated to 90 to 99 ° C., and the solution in 2 containers was kept at room temperature (23 to 25 ° C.) for 1 or 2 hours, then cooled to room temperature and adjusted to pH 6 with aqueous ammonia. Adjusted to .5 to 10.1.
  • the precipitate (silicic acid) on the filter paper was thoroughly washed with water, and then transferred to a platinum crucible together with the filter paper. After heating and firing at 1000 ° C. for 2 hours using an electric furnace, the product was cooled in a drier and the weight of the fired product (silicon dioxide) was measured. Test conditions and measurement results are shown in Table 2. Note that the SiO 2 recovery in the table shows the percentage of SiO 2 weight measurement for the weight when the silicon of the dissolved glass or metal silicon Motochu is all recovered as SiO 2.
  • test numbers 4 and 18 had initial and final pH less than 9 and test numbers 5 and 19 were not heated after the addition of ammonia
  • test numbers 10 and 20 were potassium hexafluorosilicates separated by suction filtration. Since the precipitate solidified, Test Nos. 11 and 21 dried the separated precipitate of potassium hexafluorosilicate, and therefore, no SiO 2 powder was obtained. The reason why the SiO 2 recovery rate of Test No. 8 was slightly lower than that of Test Nos. 3, 6 and 7 was presumed to be that the solubility of the produced sodium hexafluorosilicate was higher than that of potassium salt or rubidium salt.
  • the reason why the SiO 2 recovery rate of Test No. 8 was slightly lower than that of Test Nos. 3, 6 and 7 was presumed to be that the solubility of the produced sodium hexafluorosilicate was higher than that of potassium salt or rubidium salt.
  • the recovery rate under optimum conditions reached 95% or more, whereas in the case of glass, it was less than 82%. This is presumably because alkali metal elements, alkaline earth metal elements, aluminium, and the like contained in the glass formed hexafluorosilicate and deposited, and were removed when the insoluble materials were separated.
  • insoluble materials when the material to be dissolved was glass contained a large amount of calcium fluoride, barium sulfate, lead sulfate and the like in addition to hexafluorosilicate.
  • the solutions of Test Nos. 3, 13 and 17 were made of glass. It was transferred to a container, and air and water vapor at around 100 ° C. were blown in for about 1 hour while heating to around 100 ° C. with a heater. After cooling to room temperature, the pH of each solution was measured (measured value 7.2), diluted to 1 dm 3 accurately with water, and then the ammonium ion concentration was measured by the Nessler method.
  • the filtrate after filtering and separating the calcium fluoride precipitate is put into the cell 31 of the apparatus having the same structure as that shown in FIG. 9.
  • the cell 32 is pure water
  • the cell 33 is sulfuric acid having a concentration of 100 g / dm 3 .
  • a DC voltage of 3.2 V was applied between the anode 25 (titanium plate coated with iridium oxide) and the cathode 26 (nickel plate). Hold for 2 hours.
  • the cation exchange membranes 27-1 and 27-2 are used as Neoceptor CM-1 manufactured by Tokuyama Corporation, and the same AM-1 is used as the anion exchange membrane 28. It was.
  • the hydrofluoric acid concentration in the aqueous solution in the cell 32 was quantitatively analyzed by acetylacetone iron complex absorptiometry, and the amount of hydrogen fluoride produced by the electrodialysis treatment was calculated.
  • all silicon in the aliquot of dissolved material becomes potassium hexafluorosilicate, all of which is converted to potassium fluoride, and 200/1000 of that is recovered as hydrogen fluoride by electrodialysis.
  • the calculated theoretical value and the percentage of the measured value with respect to the theoretical value (recovery rate) were calculated. These numerical values are shown together in Table 3.
  • the solution was filtered using filter paper, and the precipitate (hexafluorotitanate) on the filter paper was washed into water and transferred to a plastic container.
  • Water was added to the precipitate to adjust the liquid volume to about 700 cm 3 , and then aqueous ammonia having a concentration of about 15% was added to adjust the pH to 6.5 to 10.2.
  • the solution in 13 containers was heated to 90-99 ° C., and the solution in 1 container was kept at room temperature (25 ° C.) for 1 or 2 hours, then cooled to room temperature, and the pH was adjusted to 6.5 with aqueous ammonia. Adjusted to ⁇ 10.1.
  • the precipitate (titanium hydroxide) on the filter paper was thoroughly washed with water, and then transferred to a platinum crucible together with the filter paper. After heating and firing at 1000 ° C. for 2 hours using an electric furnace, the product was cooled in a drier and the weight of the fired product (titanium dioxide) was measured. Test conditions and measurement results are shown in Table 5. Note that the TiO 2 recovery in the table shows the percentage of TiO 2 weight measurement for the weight of the case of titanium in the sample solution 100 cm 3 is all recovered as TiO 2.
  • Test No. 4 had an initial and final pH of less than 9, and Test No. 5 was not heated after the addition of ammonia, the TiO 2 recovery rate was significantly lower in both cases. Moreover, the TiO 2 recovery rates of Test Nos. 7 and 8 were lower than those of Test Nos. 3 and 6 because the solubility of the produced sodium hexafluorotitanate and ammonium hexafluorotitanate was higher than that of potassium salt and rubidium salt. Is presumed to be the cause.
  • the TiO 2 recovery rate of Test No. 9 was lower than that of Test No. 10, whereas the latter added 0.30 mol of hydrofluoric acid so that the F / Ti molar ratio was 6 or more, Since the former was not added, it is estimated that the F / Ti molar ratio was 6 or less.
  • the reason why the TiO 2 recovery rate of Test No. 11 was relatively low is assumed to be due to the same reason.
  • the TiO 2 recovery rate of Test Nos. 12 and 13 exceeded 100% because the recovered TiO 2 contained impurities (mainly oxides of aluminum), and the TiO 2 recovery rate of Test No. 14 Is estimated to be about 12% because the addition of nitric acid was omitted.
  • the nickel container was placed on the container support of the thermal decomposition apparatus having the structure shown in FIG. 8 and set in the heating section of the heating tube, and then the heating tube was heated to 900 ° C. using an electric furnace.
  • argon gas was fed from the carrier gas feed pipe, and silicon tetrafluoride or titanium tetrafluoride gas generated by the pyrolysis reaction was sent to the condenser and the absorbing solution.
  • the condenser was water-cooled from the outside so that the inner surface temperature was about 50 to 100 ° C., and pure water was used as the absorbent.
  • the heating tube was turned off and allowed to cool to room temperature.
  • the condenser was removed from the thermal decomposition apparatus, the valve was opened, 500 cm 3 of pure water was injected from the water injection tube, and the condensed titanium tetrafluoride was dissolved while gently shaking.
  • the absorption solution in which silicon tetrafluoride has been absorbed and the solution in which titanium tetrafluoride is dissolved are transferred to separate containers, respectively, and a solution in which the inner surface of the absorption liquid container or the condenser inner surface is washed with about 100 cm 3 of pure water, and After adding pure water to adjust the liquid volume to about 700 cm 3 , ammonia water having a concentration of about 14% was added to adjust the pH of the solution to 6.3 to 10.2.
  • the solution in 18 containers was heated to 90-99 ° C., the solution in 2 containers was kept at room temperature (25 ° C.) for 1 or 2 hours, then cooled to room temperature, and the pH was adjusted to 6.5 with aqueous ammonia. Adjusted to ⁇ 10.1.
  • the mixture was filtered using filter paper, and the precipitate (silicic acid or titanium dioxide) on the filter paper was thoroughly washed with water, and then transferred together with the filter paper into a platinum crucible. After heating and firing at 1000 ° C. for 2 hours using an electric furnace, the product was cooled in a drier and the weight of the fired product (silicon dioxide or titanium dioxide) was measured. Test conditions and measurement results are shown in Tables 7-9. Note that the SiO 2 recovery in the table shows the percentage of SiO 2 recovery amount with respect to the weight of the case of silicon of dissolved glass or metal silicon Motochu is all recovered as SiO 2. Similarly, the TiO 2 recovery shows the percentage of TiO 2 recovery amount with respect to the weight of the case of titanium dissolved titanium or a titanium alloy is all recovered as TiO 2.
  • sample solution A the material to be dissolved is glass
  • metal silicon sample solution B
  • the thermal decomposition treatment was omitted for comparison. That is, potassium hexafluorosilicate and / or potassium hexafluorotitanate separated by filtration is transferred to a plastic container, mixed with about 700 cm 3 of water, and then added with aqueous ammonia having a concentration of about 14%. The pH of the solution was adjusted to 9 or higher. Thereafter, the solution in the container was kept at 90 ° C. for 2 hours, then cooled to room temperature, and the pH was adjusted to 9 or more with aqueous ammonia.
  • the mixture was filtered using filter paper, and the precipitate (silicic acid or / and titanium hydroxide) on the filter paper was thoroughly washed with water, and then transferred together with the filter paper into a platinum crucible.
  • the product was cooled in a drier and the weight of the fired product (silicon dioxide and / or titanium dioxide) was measured.
  • the obtained SiO 2 recovery amount and / or TiO 2 recovery amount showed a higher numerical value than when the thermal decomposition treatment was performed. In the case of test number 20, silicon dioxide and titanium dioxide could not be separated and recovered.
  • Table 10 shows the results of analyzing the aluminum and potassium contents contained in silicon dioxide or titanium dioxide recovered by the tests of Test Nos. 4, 5, 16, and 17 by ICP emission spectroscopy.
  • the recovered silicon dioxide contained 0.6 mass% of potassium.
  • the silicon dioxide recovered in the test of test number 4 in which the pyrolysis process was performed was used.
  • the potassium content was less than 0.1 mass%.
  • the titanium dioxide recovered in the test No. 17 omitting the thermal decomposition treatment contained 3.1 mass% aluminum and 0.1 mass% potassium, but the test No. 16 in which the thermal decomposition treatment was performed.
  • the aluminum and potassium contents of the titanium dioxide recovered in step 1 were both less than 0.1 mass%.
  • the method for recovering silicon, titanium and fluorine according to the present invention can be used to significantly reduce the cost of melting glass, metal silicon, titanium and a titanium alloy using an aqueous solution containing hydrofluoric acid. It is also highly likely to be used for industrial waste reduction and resource saving.

Abstract

Selon l’invention, le sel d'acide hexafluorosilicique ou le sel d'acide hexafluorotitanique obtenu dans un traitement de régénération d'une solution aqueuse contenant de l'acide fluorhydrique est converti en une substance à usages multiples pour élargir les applications et augmenter la quantité d'utilisation. Le sel d'acide hexafluorosilicique ou le sel d'acide hexafluorotitanique est pyrolysé pour produire du tétrafluorure de silicium ou du tétrafluorure de titane, et le tétrafluorure est mis à réagir avec de l'eau et de l'ammoniac pour convertir le tétrafluorure en un précipité soit d'acide silicique soit d'hydroxyde de titane. En variante, ces sels sont directement mis à réagir avec l'eau et l'ammoniac pour convertir chaque sel en un précipité soit d'acide silicique soit d'hydroxyde de titane. Le précipité est chauffé/brûlé pour fournir du dioxyde de silicium ou du dioxyde de titane. Un alcali est ajouté à la solution aqueuse résultant de la séparation du précipité, et le mélange résultant est distillé pour obtenir de l'eau ammoniacale et le fluorure d'un métal alcalino-terreux. La solution aqueuse obtenue par la distillation est soumise à une électrodialyse ou à un échange d'ions pour obtenir de l'acide fluorhydrique et un alcali.
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JP2013046888A (ja) * 2011-08-29 2013-03-07 Anakku:Kk フッ酸含有処理液の再生方法及び再生装置
WO2014083716A1 (fr) * 2012-11-30 2014-06-05 株式会社 東芝 Procédé de traitement d'eaux usées contenant du fluor, et appareil pour le traitement d'eaux usées contenant du fluor
JP2015142921A (ja) * 2015-03-27 2015-08-06 株式会社東芝 フッ素含有廃水の処理方法及びフッ素含有廃水の処理装置
JP2018080086A (ja) * 2016-11-17 2018-05-24 東邦チタニウム株式会社 チタン化合物の回収方法、酸化チタンの製造方法およびチタン酸アルカリの製造方法
CN110562988A (zh) * 2019-09-12 2019-12-13 青岛美高集团有限公司 一种隔热保温材料及其生产方法
CN114291959A (zh) * 2022-03-09 2022-04-08 中国电子工程设计院有限公司 一种有效去除总有机碳和弱离子化杂质的超纯水制备方法
CN114477280A (zh) * 2020-10-27 2022-05-13 中国科学院过程工程研究所 一种氟化法制备纳米二氧化钛的方法
CN116002691A (zh) * 2022-12-01 2023-04-25 航天特种材料及工艺技术研究所 一种去除硅酸中高价金属离子杂质的方法
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JP2013046888A (ja) * 2011-08-29 2013-03-07 Anakku:Kk フッ酸含有処理液の再生方法及び再生装置
WO2014083716A1 (fr) * 2012-11-30 2014-06-05 株式会社 東芝 Procédé de traitement d'eaux usées contenant du fluor, et appareil pour le traitement d'eaux usées contenant du fluor
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JP2018080086A (ja) * 2016-11-17 2018-05-24 東邦チタニウム株式会社 チタン化合物の回収方法、酸化チタンの製造方法およびチタン酸アルカリの製造方法
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CN110562988B (zh) * 2019-09-12 2023-10-31 青岛美高集团有限公司 一种隔热保温材料及其生产方法
US11767320B2 (en) 2020-10-02 2023-09-26 Incyte Corporation Bicyclic dione compounds as inhibitors of KRAS
CN114477280B (zh) * 2020-10-27 2023-04-28 中国科学院过程工程研究所 一种氟化法制备纳米二氧化钛的方法
CN114477280A (zh) * 2020-10-27 2022-05-13 中国科学院过程工程研究所 一种氟化法制备纳米二氧化钛的方法
CN114291959A (zh) * 2022-03-09 2022-04-08 中国电子工程设计院有限公司 一种有效去除总有机碳和弱离子化杂质的超纯水制备方法
CN114291959B (zh) * 2022-03-09 2022-07-01 中国电子工程设计院有限公司 一种有效去除总有机碳和弱离子化杂质的超纯水制备方法
CN116002691A (zh) * 2022-12-01 2023-04-25 航天特种材料及工艺技术研究所 一种去除硅酸中高价金属离子杂质的方法

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