CN110697767B - Method for preparing alkali metal fluorotitanate by using alkali metal titanate - Google Patents
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Abstract
The invention relates to a method for preparing alkali metal fluotitanate by using alkali metal titanate, which comprises the following steps: (1) mixing alkali metal titanate with hydrofluoric acid to obtain alkali metal fluorotitanate solution; (2) and (2) adding alkali metal hydroxide and/or alkali metal salt into the alkali metal fluorotitanate solution obtained in the step (1), and cooling and crystallizing to obtain the alkali metal fluorotitanate. According to the invention, the alkali metal titanate is adopted to directly react with hydrofluoric acid, the purity of the raw material and the molar ratio of hydrogen fluoride in the hydrofluoric acid to titanium in the alkali metal titanate are controlled, the alkali metal titanate is fully utilized by combining with the adjustment of the concentration of alkali metal ions, the recovery rate of titanium is more than 92.00%, the grade of the obtained alkali metal fluorotitanate is more than 98.00%, and the obtained alkali metal fluorotitanate meets the national standards of GBT22668-2008 potassium fluotitanate and the like. The method has the advantages of simple process flow, low production cost, obvious economic and environmental benefits and higher application value.
Description
Technical Field
The invention relates to the field of titanation, in particular to a method for preparing alkali metal fluotitanate by using alkali metal titanate.
Background
The alkali metal fluorotitanate comprises sodium fluorotitanate, potassium fluorotitanate, lithium fluorotitanate and the like, and the molecular formula is respectively Na 2 TiF 6 、K 2 TiF 6 And LiTiF 6 . Sodium fluorotitanate and potassium fluorotitanate are mainly used as catalysts for polypropylene synthesis in industry, as pesticides, metal welding agents and metal titanium production raw materials in kiln industry, and lithium fluorotitanate is mainly used as electrolyte of lithium battery electrolyte. The traditional preparation method of alkali metal titanate is mainly to prepare fluotitanic acid firstly and then react with alkali metal salt。
CN101838016A discloses a preparation process and a preparation device of potassium fluotitanate, which comprises the following steps: (1) adding ilmenite powder into a reaction kettle, adding refined hydrofluoric acid and a peroxide solution, and fully infiltrating to prepare fluotitanic acid; (2) after the fluotitanic acid is cooled, adding a potassium chloride solution to generate a potassium fluotitanate precipitate; (3) adding potassium carbonate solution into the new reaction system consisting of the filtrate, and allowing iron element to pass through to form Fe (OH) 3 Removing flocculent precipitate, and recovering potassium chloride and potassium fluoride solution. In the reaction system of the invention, proper amount of peroxide is added to lead Fe in the ilmenite powder 2+ Total oxidation to Fe 3+ Then by adding a suitable amount of K 2 CO 3 Solution of Fe 3+ With Fe (OH) 3 Removing and recycling the precipitate; the reaction device is reasonably improved, so that hydrofluoric acid in the reaction system is fully condensed and recovered, and zero emission of pollutants can be basically realized in the whole reaction system.
CN105668621A discloses a method for preparing potassium fluotitanate from fluorine-containing wastewater, which comprises the following steps: (1) adding titanium dioxide into the fluorine-containing wastewater, wherein the mass ratio of the fluorine-containing wastewater to the titanium dioxide is 3:1, reacting at normal temperature and normal pressure, and stirring for 1-2 hours to generate a fluotitanic acid solution; (2) adding a saturated potassium carbonate solution into the fluotitanate solution at normal temperature and normal pressure, and adopting methyl orange as an indicator until the methyl orange is discolored to separate out potassium fluotitanate; (3) centrifugally separating the suspension containing the potassium fluotitanate to separate potassium fluotitanate solid and residual mother liquor; (4) and (3) primarily heating and drying the potassium fluotitanate solid for 4 hours at the heating temperature of 80-150 ℃, and then heating and drying the primarily heated and dried potassium fluotitanate solid by adopting a double-cone dryer at the heating temperature of 80-50 ℃ for 10 hours to finally obtain a finished product of the potassium fluotitanate.
CN102586628A discloses a cyclic preparation method for producing sponge titanium and synchronously producing sodium cryolite by taking sodium fluotitanate as an intermediate raw material, wherein the method mentions that the preparation process of the sodium fluotitanate comprises the following steps: (1) adding hydrofluoric acid into the titanic iron concentrate to react to generate fluotitanic acid; (2) sodium carbonate and sodium hydroxide are added to fluotitanic acid to obtain sodium fluotitanate.
CN10320451A discloses a synthesis method and a new application of hexafluoro lithium titanate, which comprises the following steps: first, transparent fluorotitanic acid H is prepared 2 TiF 6 A solution; secondly, preparing a lithium fluoride suspension; filtering the lithium fluoride suspension, taking a filter cake, namely lithium fluoride, and preparing the lithium fluoride into 20-30% of lithium fluoride suspension by using pure water; thirdly, dropwise adding the lithium fluoride suspension liquid prepared in the second step into the transparent fluotitanic acid solution prepared in the first step to prepare a transparent hexafluorolithium titanate solution; and fourthly, stirring and heating the hexafluorolithium titanate solution prepared in the third step, washing and crystallizing a filter cake by using pure water, heating and drying the crystal, naturally cooling, and grinding and crushing to obtain hexafluorolithium titanate powder.
The above-mentioned method adopts the method of firstly preparing fluotitanic acid and then adding alkali metal salt to prepare alkali metal fluotitanate, and in the course of production the impurity element content must be strictly controlled, and the control of impurity element is more complex, so that the domestic market fluotitanate is different in quality, obvious in price difference, and high-purity and high-quality alkali metal fluotitanate is higher in price. Therefore, how to develop a method for preparing high-grade alkali metal fluorotitanate with simple control of impurity elements becomes a problem to be solved urgently.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a method for preparing alkali metal fluorotitanate by using alkali metal titanate, which comprises the steps of directly reacting the alkali metal titanate with hydrofluoric acid to obtain an alkali metal fluorotitanate solution, adding alkali metal hydroxide or alkali metal salt, and cooling and crystallizing to realize short-process preparation of high-grade alkali metal fluorotitanate; the process flow is simple, and the method has a good application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for preparing an alkali metal fluorotitanate using an alkali metal titanate, said process comprising the steps of:
(1) mixing alkali metal titanate with hydrofluoric acid to obtain alkali metal fluorotitanate solution;
(2) and (2) adding alkali metal hydroxide and/or alkali metal salt into the alkali metal fluorotitanate solution obtained in the step (1), and cooling and crystallizing to obtain the alkali metal fluorotitanate.
According to the method for preparing the alkali metal fluorotitanate by using the alkali metal titanate, the alkali metal titanate and hydrofluoric acid are directly reacted, the reaction process is violent, a large amount of heat is released, the temperature of the solution is increased, the alkali metal hydroxide and/or the alkali metal salt are/is added, the concentration of alkali metal ions in the alkali metal fluorotitanate is adjusted, the crystallization rate of the alkali metal fluorotitanate is ensured, and the high-grade alkali metal fluorotitanate is prepared.
Preferably, the purity of the alkali metal titanate in the step (1) is 85-98%, for example, 85%, 88%, 90%, 92%, 95%, 98%, etc., the purity is less than 85%, and the content of impurity elements is too high, which affects the product purity; the purity is more than 98%, and the cost for producing the alkali metal titanate is too high.
Preferably, the alkali metal titanate further comprises a titanium-containing mineral obtained by reacting a titanium-containing mineral with an alkali metal hydroxide and/or an alkali metal salt.
Preferably, the alkali metal titanate is sodium titanate, lithium titanate or potassium titanate.
Preferably, the sodium titanate comprises Na 2 Ti 3 O 7 、Na 4 Ti 3 O 8 、Na 4 Ti 5 O 12 、Na 4 TiO 4 、Na 2 TiO 3 、Na 2 Ti 8 O 17 Or Na 2 Ti 2 O 4 (OH) 2 Any one or a combination of at least two of the following, wherein typical but non-limiting combinations: na (Na) 2 Ti 3 O 7 And Na 4 Ti 3 O 8 ，Na 2 Ti 3 O 7 And Na 2 TiO 3 ，Na 4 Ti 3 O 8 And Na 4 TiO 4 ，Na 4 TiO 4 、Na 2 TiO 3 And Na 2 Ti 2 O 4 (OH) 2 ，Na 2 Ti 3 O 7 、Na 2 TiO 3 And Na 2 Ti 2 O 4 (OH) 2 ，Na 4 Ti 3 O 8 、Na 4 Ti 5 O 12 And Na 4 TiO 4 And the like.
Preferably, the lithium titanate comprises Li 2 Ti 3 O 7 、Li 4 Ti 3 O 8 、Li 4 Ti 5 O 12 、Li 4 TiO 4 Or Li 2 TiO 3 Any one of, or a combination of at least two of, typical but non-limiting combinations of: li 2 Ti 3 O 7 And Li 2 TiO 3 ，Li 4 Ti 3 O 8 And Li 4 TiO 4 ，Li 4 Ti 3 O 8 、Li 4 Ti 5 O 12 And LiLi 4 TiO 4 And the like.
Preferably, the potassium titanate comprises K 2 Ti 3 O 7 、K 4 Ti 3 O 8 、K 4 Ti 5 O 12 、K 4 TiO 4 、K 2 TiO 3 、K 2 Ti 8 O 17 Or K 2 Ti 2 O 4 (OH) 2 Any one of, or a combination of at least two of, typical but non-limiting combinations of: k 2 Ti 3 O 7 And K 4 Ti 3 O 8 ，K 2 Ti 3 O 7 And K 2 TiO 3 ，K 4 Ti 3 O 8 And K 4 TiO 4 ，K 4 TiO 4 、K 2 TiO 3 And K 2 Ti 2 O 4 (OH) 2 ，K 2 Ti 3 O 7 、K 2 TiO 3 And K 2 Ti 2 O 4 (OH) 2 ，K 4 Ti 3 O 8 、K 4 Ti 5 O 12 And K 4 TiO 4 And the like.
In the invention, alkali metal titanate and hydrofluoric acid are reacted to prepare alkali metal fluotitanate, taking sodium titanate as an example, the chemical reaction equation is as follows:
Na 2 TiO 3 +6HF＝Na 2 TiF 6 +3H 2 O
Na 4 TiO 4 +6HF＝Na 2 TiF 6 +2H 2 O+2NaOH
Na 2 Ti 8 O 17 +48HF＝Na 2 TiF 6 +17H 2 O+7H 2 TiF 6
Na 2 Ti 2 O 4 (OH) 2 +12HF＝Na 2 TiF 6 +6H 2 O+H 2 TiF 6
Na 4 Ti 3 O 8 +18HF＝2Na 2 TiF 6 +8H 2 O+H 2 TiF 6
Na 2 Ti 3 O 7 +18HF＝Na 2 TiF 6 +7H 2 O+2H 2 TiF 6
Na 4 Ti 5 O 12 +30HF＝2Na 2 TiF 6 +12H 2 O+3H 2 TiF 6
preferably, the molar ratio of hydrogen fluoride in the hydrofluoric acid to titanium in the alkali metal titanate in step (1) is 4-8:1, and may be, for example, 4:1, 4.5:1, 5:1, 6:1, 7:1, 7.5:1, or 8:1, etc. The molar ratio is less than 4:1, so that the reaction cannot be fully performed, and waste of titanate is caused; the molar ratio is more than 8:1, which causes the waste of hydrofluoric acid.
Preferably, the hydrofluoric acid has a mass fraction of 5-30%, for example, 5%, 6%, 8%, 10%, 15%, 20%, 25%, 28%, 30%, or the like. The mass fraction of the hydrofluoric acid is less than 5%, the reaction speed is slow, reaction equipment with a large volume is needed, and the production efficiency is low; the mass fraction is more than 30 percent, the reaction is violent in heat release, and the safety operability is poor.
Preferably, the mixing time in step (1) is 10-60min, such as 10min, 12min, 15min, 18min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60 min.
Preferably, the mixing is by stirring.
Preferably, the stirring rate is 100-500rpm, and may be, for example, 100rpm, 110rpm, 120rpm, 150rpm, 180rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 480rpm, 500rpm, or the like.
Preferably, in step (2), the alkali metal hydroxide is sodium hydroxide, lithium hydroxide or potassium hydroxide. The alkali metal ion in the alkali metal hydroxide should be the same as that of the alkali metal titanate in step (1), for example, Na is used in step (1) 2 Ti 3 O 7 In step (2), Na (OH) should be added.
Preferably, the alkali metal salt comprises a sodium, lithium or potassium salt. The alkali metal ion in the alkali metal salt should be the same as that of the alkali metal titanate in step (1), for example, sodium titanate is used in step (1) and sodium salt should be added in step (2).
Preferably, the sodium salt comprises any one of sodium carbonate, sodium bicarbonate, sodium chloride, sodium fluoride, sodium sulfate, sodium bisulfate, sodium sulfite, sodium bisulfite, or sodium nitrate, or a combination of at least two thereof, with a typical but non-limiting combination: sodium carbonate and sodium bicarbonate, sodium carbonate and sodium chloride, sodium chloride and sodium fluoride, sodium chloride and sodium nitrate, sodium carbonate, sodium chloride and sodium nitrate, and the like.
Preferably, the lithium salt comprises any one of lithium carbonate, lithium bicarbonate, lithium chloride, lithium fluoride, lithium sulfate, lithium bisulfate, lithium sulfite, lithium bisulfite, or lithium nitrate, or a combination of at least two thereof, with a typical but non-limiting combination: lithium carbonate and bicarbonate, lithium chloride and fluoride, lithium sulfate and bisulfate, lithium sulfite and bisulfite, lithium carbonate, lithium sulfate and lithium nitrate, and the like.
Preferably, the potassium salt comprises any one of potassium carbonate, potassium bicarbonate, potassium chloride, potassium fluoride, potassium sulfate, potassium bisulfate, potassium sulfite, potassium bisulfite, or potassium nitrate, or a combination of at least two thereof, with a typical but non-limiting combination: potassium carbonate and bicarbonate, potassium carbonate and chloride, potassium chloride and fluoride, potassium chloride and nitrate, potassium carbonate, chloride and nitrate, and the like.
Preferably, the alkali metal hydroxide and/or alkali metal salt is added in step (2) so that the ratio of the molar amount of the alkali metal element to the molar amount of the titanium element in the solution is 2-2.4: 1. For example, it may be 2:1, 2.1:1, 2.2:1, 2.3:1, or 2.4:1, etc. The molar weight ratio is less than 2:1, which causes waste of titanium raw materials; addition amounts greater than 2.4:1 result in waste of alkali metal hydroxide or alkali metal salt.
In the invention, the theoretical value of the ratio of the molar weight of the alkali metal element to the molar weight of the titanium element in the fluotitanate is 2, and in order to ensure high crystallization rate of the fluotitanate, alkali metal hydroxide and/or alkali metal salt is added in the step (2) to adjust the concentration of alkali metal ions.
Preferably, the cooling temperature in step (2) is 5-30 deg.C, such as 5 deg.C, 8 deg.C, 10 deg.C, 15 deg.C, 20 deg.C, 25 deg.C or 30 deg.C.
Preferably, the cooling mode is natural cooling and/or cooling liquid cooling, and the natural cooling and the cooling liquid cooling only affect the temperature reduction rate and do not affect the purity of the prepared alkali metal salt and the like.
Preferably, the mixing in step (1) is followed by separation to remove solid phase impurities and reduce the content of impurities in the alkali metal fluorotitanate solution, thereby further improving the purity of the fluorotitanate.
Preferably, the cooling in step (2) is followed by separation.
Preferably, the manner of separation is any one or a combination of at least two of filtration, suction filtration or centrifugation, with typical but non-limiting combinations: centrifuging and filtering, centrifuging and filtering.
Preferably, the method comprises the steps of:
(1) adding alkali metal titanate into hydrofluoric acid with the mass fraction of 5-30%, controlling the molar ratio of hydrogen fluoride in the hydrofluoric acid to titanium in the alkali metal titanate to be 4-8:1, stirring for reaction for 10-60min at the stirring speed of 100-500rpm, and then separating to obtain alkali metal fluorotitanate solution;
(2) adding alkali metal hydroxide or alkali metal salt into the alkali metal fluorotitanate solution obtained in the step (1) to ensure that the molar weight ratio of alkali metal elements to titanium elements in the solution is 2-2.4:1, cooling to 5-30 ℃, crystallizing, and separating to obtain the alkali metal fluorotitanate.
In a second aspect, the present invention provides an alkali metal fluorotitanate as prepared by the process of the first aspect above, having a grade of > 98%.
The invention adopts the raw material with the purity of 85-98 percent, controls the content of impurities from a source, and combines the adjustment of alkali metal ions to ensure that the grade of the prepared alkali metal fluotitanate is higher.
In the present invention, the grade of the alkali metal fluorotitanate is > 98%, and may be, for example, 98.10%, 98.14%, 98.15%, 98.20%, 98.27%, 98.30%, 98.40%, 98.43%, 98.50%, 98.58%, 98.60%, 98.80%, 98.90%, or the like.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the method provided by the invention adopts the steps that alkali metal titanate directly reacts with hydrofluoric acid to obtain alkali metal fluorotitanate solution, alkali metal salt and/or alkali metal hydroxide are added to adjust the content of alkali metal ions, and then cooling crystallization is carried out to obtain the alkali metal fluorotitanate crystal with the grade of more than 98%.
(2) The invention has simple process flow, low production cost, obvious economic and environmental benefits and good application prospect.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a method for preparing alkali metal fluotitanate by using alkali metal titanate, which comprises the following steps:
(1) mixing Na 2 TiO 3 Slowly adding the solid phase into 10% hydrofluoric acid solution for dissolving, wherein the hydrofluoric acid contains hydrogen fluoride and Na 2 TiO 3 The molar ratio of the medium titanium is 5:1, the reaction is carried out for 40min after the feeding is finished, the stirring speed is 400rpm, and then undissolved impurities and a sodium fluotitanate solution are obtained through liquid-solid separation;
(2) adding NaCl solution into the sodium fluotitanate solution to ensure that the molar weight ratio of sodium element to titanium element in the solution is 2.1:1, naturally cooling to 20 ℃ for crystallization, and then carrying out liquid-solid separation to obtain the sodium fluotitanate.
Example 2
The embodiment provides a method for preparing alkali metal fluotitanate by using alkali metal titanate, which comprises the following steps:
(1) mixing Na 4 TiO 4 Slowly adding the solid phase into hydrofluoric acid solution with the mass fraction of 30% for dissolving, wherein hydrogen fluoride and Na in the hydrofluoric acid 4 TiO 4 The molar ratio of the medium titanium is 6:1, the reaction is carried out for 30min after the feeding is finished, the stirring speed is 300rpm, and then undissolved impurities and a sodium fluotitanate solution are obtained through liquid-solid separation;
(2) adding NaCl solution into the sodium fluotitanate solution to ensure that the molar weight ratio of sodium element to titanium element in the solution is 2.0:1, naturally cooling to 10 ℃ for crystallization, and then carrying out liquid-solid separation to obtain the sodium fluotitanate.
Example 3
The embodiment provides a method for preparing alkali metal fluotitanate by using alkali metal titanate, which comprises the following steps:
(1) will K 2 Ti 8 O 7 Slowly adding the solid phase into hydrofluoric acid solution with the mass fraction of 15% for dissolving, wherein the hydrogen fluoride and the K in the hydrofluoric acid 2 Ti 8 O 7 The molar ratio of the medium titanium is 7:1, the reaction is carried out for 40min after the feeding is finished, the stirring speed is 200rpm, and undissolved impurities and a potassium fluotitanate solution are obtained through liquid-solid separation;
(2) adding K to potassium fluotitanate solution 2 CO 3 The solution is naturally cooled to 30 ℃ for crystallization, and then the solution is subjected to liquid-solid separation, wherein the molar weight ratio of the potassium element to the titanium element in the solution is ensured to be 2.4:1And (5) separating to obtain the potassium fluotitanate.
Example 4
The embodiment provides a method for preparing alkali metal fluotitanate by using alkali metal titanate, which comprises the following steps:
(1) will K 2 TiO 3 Slowly adding the solid phase into 10 percent hydrofluoric acid solution for dissolving, wherein the mass fraction of the hydrofluoric acid solution is hydrogen fluoride and K 2 TiO 3 The molar ratio of the medium titanium is 8:1, the reaction is carried out for 40min after the feeding is finished, the stirring speed is 100rpm, and undissolved impurities and a potassium fluotitanate solution are obtained through liquid-solid separation;
(2) and (2) adding a KCl solution into the potassium fluotitanate solution to ensure that the molar weight ratio of alkali metal elements to titanium elements in the solution is 2.2:1, naturally cooling to 25 ℃ for crystallization, and then carrying out liquid-solid separation to obtain the potassium fluotitanate.
Example 5
The embodiment provides a method for preparing alkali metal fluotitanate by using alkali metal titanate, which comprises the following steps:
(1) mixing Na 2 Ti 3 O 7 、Na 4 TiO 4 、Na 2 TiO 3 Slowly adding the solid-phase mixture into a hydrofluoric acid solution with the mass fraction of 30% for dissolving, wherein the molar ratio of hydrogen fluoride in hydrofluoric acid to titanium in the mixture is 8:1, reacting for 40min after the feeding is finished, stirring at the speed of 300rpm, and then carrying out liquid-solid separation to obtain undissolved impurities and a sodium fluotitanate solution;
(2) adding NaCl solution into the sodium fluotitanate solution to ensure that the molar weight ratio of sodium element to titanium element in the solution is 2.3:1, naturally cooling to 15 ℃ for crystallization, and then carrying out liquid-solid separation to obtain the sodium fluotitanate.
Example 6
The only difference compared to example 1 is that the molar ratio of hydrogen fluoride in hydrofluoric acid to titanium in the solid phase in step (1) was replaced by 4: 1.
Example 7
The only difference compared to example 1 is that the NaCl solution in step (2) was replaced by NaOH solution.
Example 8
Compared with example 1, the only difference is that NaCl in step (2) was replaced with a mixed solution of NaCl and NaOH.
Example 9
The only difference compared with example 1 is that the molar ratio of hydrogen fluoride in hydrofluoric acid to titanium in the solid phase in step (1) is 3: 1.
Example 10
The only difference compared with example 1 is that the molar ratio of hydrogen fluoride in hydrofluoric acid to titanium in the solid phase in step (1) was set to 9: 1.
Example 11
The embodiment provides a method for preparing alkali metal fluotitanate by using alkali metal titanate, which comprises the following steps:
(1) mixing Li 2 TiO 3 Slowly adding the solid phase into hydrofluoric acid solution with the mass fraction of 20% for dissolving, wherein hydrogen fluoride and Li in the hydrofluoric acid 2 TiO 3 The molar ratio of the medium titanium is 5:1, the reaction is carried out for 20min after the feeding is finished, the stirring speed is 500rpm, and undissolved impurities and lithium fluotitanate solution are obtained through liquid-solid separation;
(2) LiNO was added to the lithium fluorotitanate solution 3 And (3) solution, wherein the molar ratio of the lithium element to the titanium element in the solution is ensured to be 2.1, natural cooling is carried out to 10 ℃ for crystallization, and then liquid-solid separation is carried out to obtain the lithium fluotitanate.
Comparative example 1
In contrast to example 1, this comparative example provides a process for preparing alkali metal fluorotitanate comprising the steps of:
(1) adding a hydrofluoric acid solution into the titanium dioxide dispersion liquid, and controlling the molar ratio of hydrogen fluoride in hydrofluoric acid to titanium in titanium dioxide to be 5:1 to obtain a fluotitanic acid solution;
(2) and (2) adding a NaCl solution into the fluotitanic acid solution obtained in the step (1) to ensure that the molar weight ratio of the sodium element to the titanium element in the solution is 2.1 to obtain a sodium fluotitanate solution, and cooling and crystallizing to obtain the sodium fluotitanate.
Comparative example 2
Compared with example 1, the difference is only that NaCl solution is not added in the step (2), and the sodium fluotitanate is prepared by directly cooling and crystallizing.
Evaluation of method for producing alkali metal fluorotitanate by using alkali metal titanate:
the recovery rate of titanium in the titanium-containing raw materials of examples 1 to 10 and comparative examples 1 to 2 was calculated, and the grade of the alkali metal fluorotitanate obtained was measured by the following method: accurately weighing 0.5-0.6g cosolvent (anhydrous sodium carbonate and sodium tetraborate in a mass ratio of 2:1) by using an analytical balance, adding 0.05-0.08g alkali metal fluorotitanate, stirring to mix uniformly, covering a layer of melting agent on the surface of the mixture, and covering a cover on the platinum crucible. Placing in a muffle furnace at a specified temperature (above 950 deg.C), and melting for 15-20 min. Taking out the crucible, cooling in the air, washing the outer surface of the crucible with deionized water to avoid impurity pollution, putting the crucible into a small beaker filled with 60mL of 20% hydrochloric acid, and heating and dissolving on an electric furnace. Cooling after complete dissolution, transferring into a 100mL volumetric flask for constant volume and shaking up, diluting by 10 times in the volumetric flask, or diluting to a certain concentration range according to the content of elements in slag, performing component analysis by ICP-OES, calculating the content of titanium elements, and calculating the grade of alkali metal fluotitanate:
evaluation criteria for grade of alkali metal fluorotitanate: GBT22668-2008 potassium fluotitanate, and the like.
The recovery of titanium and the grade of alkali metal fluorotitanate are shown in Table 1.
TABLE 1
| Purity of raw material(％) | Titanium recovery (%) | Grade of alkali metal fluorotitanate (%) | |
| Example 1 | 85 | 95.13 | 98.15 |
| Example 2 | 95 | 96.07 | 98.43 |
| Example 3 | 95 | 96.58 | 98.27 |
| Example 4 | 90 | 96.71 | 98.14 |
| Example 5 | 98 | 97.71 | 98.58 |
| Example 6 | 85 | 93.12 | 98.26 |
| Example 7 | 85 | 93.17 | 98.16 |
| Example 8 | 85 | 95.42 | 98.13 |
| Example 9 | 85 | 92.18 | 98.02 |
| Example 10 | 85 | 95.67 | 98.37 |
| Example 11 | 90 | 95.27 | 98.36 |
| Comparative example 1 | 95 | 94.09 | 97.24 |
| Comparative example 2 | 85 | 93.78 | 97.55 |
The following points can be seen from table 1:
(1) it can be seen from the comprehensive examples 1-10 that the grade of the alkali metal fluorotitanate prepared in examples 1-10 by using the alkali metal titanate with the purity of 85-98% is more than 98%, and meets the standards of GBT22668-2008 potassium fluorotitanate and the like.
(2) By combining example 1 with comparative example 1, it can be seen that example 1 uses Na 2 TiO 3 The grade of the sodium fluotitanate prepared directly is 98.15%, compared with the grade of the sodium fluotitanate prepared by adopting titanium dioxide in the comparative example 1, the grade of the sodium fluotitanate prepared in the example 1 is 97.24%.
(3) It can be seen from the combination of example 1 and examples 9 and 10 that the molar ratio of hydrogen fluoride in hydrofluoric acid to titanium in alkali titanate in example 1 was 5:1, the molar ratio of hydrogen fluoride in hydrofluoric acid to titanium in alkali titanate in example 9 was 3:1, the molar ratio of hydrogen fluoride in hydrofluoric acid to titanium in alkali titanate in example 10 was 9:1, the recovery rate of titanium in example 9 was 92.18%, the grade of sodium fluorotitanate was 98.02%, the recovery rate of titanium in example 10 was 95.67%, the grade of sodium fluorotitanate was 98.37%, the recovery rate of titanium in example 1 was 95.13%, and the grade of sodium fluorotitanate was 98.15%, which indicates that the ratio of hydrogen fluoride in hydrofluoric acid to titanium in alkali titanate affects the recovery rate of titanium.
(4) It can be seen from the combination of example 1 and comparative example 2 that the NaCl solution was added to the sodium fluorotitanate solution in example 1, but the recovery rate of titanium was 93.78% and was lower than that in example 1 in comparative example 2, which indicates that the addition of NaCl makes it possible to adjust the concentration of sodium ions, increase the crystallization rate of sodium fluorotitanate, and improve the recovery rate of titanium.
In conclusion, according to the method for preparing alkali metal fluotitanate by using alkali metal titanate provided by the invention, the alkali metal titanate directly reacts with hydrofluoric acid, the purity of the raw material and the molar ratio of hydrogen fluoride in the hydrofluoric acid to titanium in the alkali metal titanate are controlled, and then the adjustment of the concentration of alkali metal ions is combined, so that the alkali metal titanate is fully utilized, the recovery rate of titanium is above 92.00%, the grade of the obtained alkali metal fluotitanate is above 98.00%, and the method meets the standards of GBT22668-2008 potassium fluotitanate and the like. The method has the advantages of simple process flow, low production cost, obvious economic and environmental benefits and higher application value.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (20)
1. A method for preparing alkali metal fluorotitanate from alkali metal titanate, which is characterized by comprising the following steps:
(1) mixing alkali metal titanate with hydrofluoric acid to obtain alkali metal fluorotitanate solution;
(2) adding alkali metal hydroxide and/or alkali metal salt into the alkali metal fluorotitanate solution obtained in the step (1), and cooling and crystallizing to obtain alkali metal fluorotitanate;
the purity of the alkali metal titanate in the step (1) is 85-98%;
the mass fraction of the hydrofluoric acid in the step (1) is 5-20%;
the alkali metal titanate is obtained by reacting a titaniferous mineral with an alkali metal hydroxide and/or an alkali metal salt;
adding the alkali metal hydroxide and/or alkali metal salt in the step (2) to ensure that the molar weight ratio of the alkali metal element to the titanium element in the solution is 2-2.4: 1;
the recovery rate of titanium in the method is more than or equal to 92.00 percent.
2. The process of claim 1, wherein the alkali titanate is sodium titanate, lithium titanate, or potassium titanate.
3. The method of claim 2, wherein the sodium titanate comprises Na 2 Ti 3 O 7 、Na 4 Ti 3 O 8 、Na 4 Ti 5 O 12 、Na 4 TiO 4 、Na 2 TiO 3 、Na 2 Ti 8 O 17 Or Na 2 Ti 2 O 4 (OH) 2 Any one or a combination of at least two of them.
4. The process of claim 2, wherein said lithium titanate comprises Li 2 Ti 3 O 7 、Li 4 Ti 3 O 8 、Li 4 Ti 5 O 12 、Li 4 TiO 4 Or Li 2 TiO 3 Any one or a combination of at least two of them.
5. The method of claim 2, wherein the potassium titanate comprises K 2 Ti 3 O 7 、K 4 Ti 3 O 8 、K 4 Ti 5 O 12 、K 4 TiO 4 、K 2 TiO 3 、K 2 Ti 8 O 17 Or K 2 Ti 2 O 4 (OH) 2 Any one or a combination of at least two of them.
6. The process of claim 1, wherein the molar ratio of hydrogen fluoride in the hydrofluoric acid to titanium in the alkali metal titanate in step (1) is 4-8: 1.
7. The method according to claim 1, wherein the mixing time in step (1) is 10-60 min.
8. The method of claim 1, wherein the mixing is by stirring.
9. The method as claimed in claim 8, wherein the stirring rate is 100-500 rpm.
10. The method according to claim 1, wherein the alkali metal hydroxide in step (2) is sodium hydroxide, lithium hydroxide or potassium hydroxide.
11. The method of claim 1, wherein the alkali metal salt in step (2) comprises a sodium, lithium or potassium salt.
12. The method of claim 11, wherein the sodium salt comprises any one of sodium carbonate, sodium bicarbonate, sodium chloride, sodium fluoride, sodium sulfate, sodium bisulfate, sodium sulfite, sodium bisulfite, or sodium nitrate, or a combination of at least two thereof.
13. The method of claim 11, wherein the lithium salt comprises any one of lithium carbonate, lithium bicarbonate, lithium chloride, lithium fluoride, lithium sulfate, lithium bisulfate, lithium sulfite, lithium bisulfite, or lithium nitrate, or a combination of at least two thereof.
14. The method of claim 11, wherein the potassium salt comprises any one of potassium carbonate, potassium bicarbonate, potassium chloride, potassium fluoride, potassium sulfate, potassium bisulfate, potassium sulfite, potassium bisulfite, or potassium nitrate, or a combination of at least two thereof.
15. The method according to claim 1, wherein the temperature of the cooling in the step (2) is 5-30 ℃.
16. The method according to claim 1, wherein the cooling in step (2) is natural cooling and/or liquid cooling.
17. The method of claim 1, wherein the mixing in step (1) is followed by separation to remove solid phase impurities.
18. The method of claim 1, wherein the cooling in step (2) is followed by separation.
19. The method according to claim 18, wherein the separation is by any one or a combination of at least two of filtration, suction filtration or centrifugation.
20. The method of claim 1, comprising the steps of:
(1) adding alkali metal titanate into hydrofluoric acid with the mass fraction of 5-20%, controlling the molar ratio of hydrogen fluoride in the hydrofluoric acid to titanium in the alkali metal titanate to be 4-8:1, stirring for reaction for 10-60min at the stirring speed of 100-500rpm, and then separating to obtain alkali metal fluorotitanate solution;
(2) adding alkali metal hydroxide or alkali metal salt into the alkali metal fluorotitanate solution obtained in the step (1) to enable the molar weight ratio of alkali metal elements to titanium elements in the solution to be 2-2.4:1, cooling, crystallizing and separating to obtain the alkali metal fluorotitanate.
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