CN108910949B - Preparation method of high-purity potassium fluotantalate - Google Patents
Preparation method of high-purity potassium fluotantalate Download PDFInfo
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- CN108910949B CN108910949B CN201810786881.2A CN201810786881A CN108910949B CN 108910949 B CN108910949 B CN 108910949B CN 201810786881 A CN201810786881 A CN 201810786881A CN 108910949 B CN108910949 B CN 108910949B
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 74
- 239000011591 potassium Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000000243 solution Substances 0.000 claims abstract description 89
- 238000000605 extraction Methods 0.000 claims abstract description 79
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000001816 cooling Methods 0.000 claims abstract description 67
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 63
- 239000002253 acid Substances 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 19
- 239000010955 niobium Substances 0.000 claims abstract description 19
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 19
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 17
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 229910001729 niobium mineral Inorganic materials 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 48
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 34
- 239000003960 organic solvent Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000001103 potassium chloride Substances 0.000 claims description 17
- 235000011164 potassium chloride Nutrition 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 13
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000484 niobium oxide Inorganic materials 0.000 description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 3
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 2
- BVOKCSKTSALAFW-UHFFFAOYSA-N [F].[Ta] Chemical compound [F].[Ta] BVOKCSKTSALAFW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- ZHFJNPAQMFQQRE-UHFFFAOYSA-D niobium(5+) tantalum(5+) decafluoride Chemical compound [F-].[Nb+5].[Ta+5].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-] ZHFJNPAQMFQQRE-UHFFFAOYSA-D 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- -1 tantalum fluoride acid Chemical class 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
- C01G35/006—Compounds containing tantalum, with or without oxygen or hydrogen, and containing two or more other elements
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a preparation method of high-purity potassium fluotantalate. The method is characterized by comprising the following steps: (1) and (3) decomposition: adding tantalum-niobium minerals into hydrofluoric acid and sulfuric acid for decomposition; (2) extracting ore pulp: performing countercurrent extraction by using an MIBK solvent or an octanol solvent, and extracting fluoroniobic acid and fluorotantalic acid into the solvent; (3) acid washing: a sulfuric acid solution is adopted to contact with the solvent obtained after extraction in the step (2) in a countercurrent manner; (4) extracting tantalum by using reverse niobium: carrying out countercurrent extraction on a sulfuric acid solution and the obtained solvent in an extraction tank to extract fluoroniobic acid into a water phase to form a fluoroniobic acid aqueous solution; (5) anti-tantalum: the residual organic solution is put in another extraction tank, and the fluorine tantalic acid organic solution is back extracted into pure water by using the pure water to form a fluorine tantalic acid aqueous solution; (6) synthesizing: (7) and (5) cooling and crystallizing. The invention provides a method for preparing high-purity potassium fluotantalate by a sectional back extraction and a sectional crystallization method, which can effectively remove impurities in the potassium fluotantalate.
Description
Technical Field
The invention relates to a preparation method of high-purity potassium fluotantalate.
Background
In the current tantalum-niobium metallurgy, a classical potassium fluotantalate preparation process is formed. Adding hydrofluoric acid into ore to decompose tantalum and niobium into fluorotantalic acid or fluoroniobic acid, extracting the fluorotantalic acid or fluorotantalic acid in an aqueous solution by using an MIBK or sec-octanol solution, further removing impurities in a tantalum and niobium loaded organic solution by using low-acidity sulfuric acid, back-extracting the tantalum and niobium loaded organic solution by using a sulfuric acid solution with hydrogen ion concentration of 1.2-1.6mol/L, and allowing the fluoroniobic acid to enter an acid solution. The purpose of separating the fluorine tantalum acid from the organic solution is achieved. And (2) allowing the organic solution containing the fluotantalic acid to enter a tantalum-back working procedure, adopting pure water as a back-extraction solution, back-extracting the fluotantalic acid solution into the pure water to form a fluotantalic acid solution, heating the fluotantalic acid solution (92 ℃), adding hydrofluoric acid and potassium chloride, and cooling to 15 ℃ to obtain the potassium fluotantalate crystal.
However, the main problem with this process is that the purity of the potassium fluorotantalate produced is limited. When the pure tantalum metal is used for sputtering a target material, the purity is required to be 99.9999%, wherein high-melting-point metals such as tungsten, molybdenum, niobium and the like are main impurity elements, and if the high-melting-point metals cannot be removed in the process of producing potassium fluotantalate, the high-melting-point metals are difficult to remove in the subsequent production process. Therefore, the preparation of high-purity tantalum metal can be ensured only by preparing the potassium fluotantalate with high purity. In the prior art, a commonly adopted one-time tantalum-resisting operation is adopted, and trace niobium and trace tungsten in a solution can enter a product. The single crystallization adopted in the prior art is also a method for preparing high-purity potassium fluotantalate crystals or high-purity potassium fluoniobate crystals, wherein partial impurity elements such as silicon, niobium and the like are easy to form crystals and crystallize together with potassium fluotantalate, and a Chinese patent application No. 02801094.9 reports a method for preparing the high-purity potassium fluotantalate crystals or the high-purity potassium fluoniobate crystals, but the adopted method only adopts different cooling rates in different intervals to achieve the purpose of uniform particles, and how to remove impurities in the potassium fluotantalate is not mentioned. Application No.: 201110316023.X, however, this method has a major problem, and has a limited effect of extracting impurities such as niobium. The product contains part of high boiling point metals such as tungsten, molybdenum and the like, and the content is generally about 0.5-10.0 ppm.
Disclosure of Invention
The invention aims to provide a preparation method of high-purity potassium fluotantalate, which can obtain the high-purity potassium fluotantalate with low impurity elements.
The preparation method of the high-purity potassium fluotantalate is characterized by comprising the following steps of:
(1) and (3) decomposition: adding tantalum-niobium minerals into hydrofluoric acid and sulfuric acid for decomposition;
(2) extracting ore pulp: performing countercurrent extraction by using an MIBK solvent or an octanol solvent, and extracting fluoroniobic acid and fluorotantalic acid into the solvent;
(3) acid washing: a sulfuric acid solution is adopted to contact with the solvent obtained after extraction in the step (2) in a countercurrent manner;
(4) extracting tantalum by using reverse niobium: carrying out countercurrent extraction on a sulfuric acid solution and the obtained solvent in an extraction tank to extract fluoroniobic acid into a water phase to form a fluoroniobic acid aqueous solution;
(5) anti-tantalum: the residual organic solution is put in another extraction tank, and the fluorine tantalic acid organic solution is back extracted into pure water by using the pure water to form a fluorine tantalic acid aqueous solution;
(6) synthesizing: heating the obtained fluotantalic acid aqueous solution, and adding potassium chloride and hydrofluoric acid;
(7) cooling and crystallizing: and cooling the synthetic liquid to obtain potassium fluotantalate crystals, centrifuging and drying to obtain the high-purity potassium fluotantalate crystals.
And (5) specifically adopting two sections of anti-tantalum, wherein the anti-tantalum liquid of the first section of anti-tantalum is a sulfuric acid, hydrochloric acid or hydrofluoric acid solution with the hydrogen ion concentration of 0.05-0.6mol/L, the anti-tantalum liquid of the second section of anti-tantalum is pure water, and the anti-tantalum liquid of the second section of anti-tantalum is used as a raw material for synthesizing the potassium fluotantalate in the step (6).
And (7) specifically adopting three-stage cooling, controlling the cooling temperature of the first stage to be 70-80 ℃, then putting the liquid obtained after the first stage is cooled into the second stage for cooling, collecting the crystal obtained after the first stage is cooled, controlling the cooling temperature of the second stage to be 40-70 ℃, then putting the liquid obtained after the second stage is cooled into the third stage for cooling, collecting the crystal obtained after the second stage is cooled, controlling the cooling temperature of the third stage to be 10-40 ℃, collecting the crystal obtained after the third stage is cooled, utilizing the potassium fluotantalate obtained after the second stage is cooled, recrystallizing the potassium fluotantalate once again, adding the crystal into pure water, adding high-purity hydrofluoric acid and high-purity potassium chloride, and finally obtaining the high-purity potassium fluotantalate.
The anti-tantalum extraction in the step (5) is carried out in a counter-current extraction tank with 8 stages to 12 stages.
Controlling the flow ratio of the extraction organic solvent to the stripping agent in the step (5) to be 1: 2 to 3: 1.
and (7) controlling the rotating speed of the stirring paddle in the cooling tank to be 30-90 revolutions per minute.
In the step (5), the acidity of the anti-tantalum liquid is controlled to be 0.05-0.6 mol/L.
In the step (5), the second-stage tantalum-reflecting liquid is sulfuric acid, hydrochloric acid or hydrofluoric acid solution with the hydrogen ion concentration of 0.05-0.6 mol/L.
And (5) allowing the anti-tantalum liquid of the second section in the step (5) to pass through a precision filtering device, and controlling the filtering precision to be less than 0.1 micrometer.
Further:
(1) crushing the tantalum-niobium ore to be not more than 200 meshes, adding the crushed ore into hydrofluoric acid, adding sulfuric acid, and performing heat preservation decomposition;
(2) then the mixed solution enters an ore extraction tank, tantalum-niobium is extracted by using an MIBK solvent or an octanol solvent, so that fluorotantalic acid and fluoroniobate acid enter the solvent, then countercurrent extraction is carried out in an acid washing tank by using 3.7-4.2mol/L sulfuric acid, then an organic solvent containing tantalum-niobium enters an anti-niobium tantalum extraction tank, and countercurrent extraction is carried out on the organic solvent containing tantalum-niobium by using 0.6-0.8mol/L sulfuric acid solution and the organic solvent containing tantalum-niobium;
(3) the obtained fluoroniobate solution enters a sulfuric acid solution, and the obtained fluorotantalate solution is left in an organic solvent;
(4) the method comprises the steps of enabling an organic solvent containing the fluorotantalic acid to enter an anti-tantalum extraction tank, adopting a 12-grade anti-tantalum tank as a first-stage back-extraction tank body, adopting a sulfuric acid, hydrochloric acid or hydrofluoric acid solution with hydrogen ion concentration of 0.05-0.6mol/L as a first-stage back-extraction agent, then utilizing the 12-grade anti-tantalum tank as a second-stage back-extraction tank body, and utilizing pure water as a back-extraction agent to obtain a second-stage fluorotantalic acid solution for later use;
(5) adding hydrofluoric acid and potassium chloride into the obtained fluotantalic acid solution, heating to 92 ℃ or above, preserving heat for half an hour, putting the solution into a first cooling tank, cooling to 70-80 ℃, then putting the solution into a second cooling tank, cooling to 40-70 ℃, and finally putting the solution into a third cooling tank, and cooling to 10-40 ℃; collecting potassium fluotantalate crystals in the second cooling tank, adding the crystals into pure water, heating to 92 ℃ or above, adding hydrofluoric acid and potassium chloride, dissolving the potassium fluotantalate crystals, putting the crystals into the cooling tank for crystallization, collecting the potassium fluotantalate crystals, centrifuging, and drying to obtain the high-purity potassium fluotantalate solid.
The invention provides a method for preparing high-purity potassium fluotantalate by a sectional back extraction and a sectional crystallization method, which can effectively remove impurities in the potassium fluotantalate.
Detailed Description
The method comprises the following steps:
firstly, crushing tantalum-niobium ore to 200 meshes or below, adding the crushed ore into hydrofluoric acid, then supplementing sulfuric acid, carrying out thermal insulation decomposition, entering an ore extraction tank, extracting tantalum and niobium by using an MIBK or sec-octanol solution, entering tantalum fluoride acid and niobium fluoride acid into MIBK or sec-octanol, carrying out countercurrent extraction in a pickling tank by using 3.7-4.2mol/L sulfuric acid, entering an organic solvent containing tantalum and niobium into an anti-niobium tantalum extraction tank, and carrying out countercurrent extraction by using a sulfuric acid solution with the acidity of 0.6-0.8mol/L and the organic solvent containing tantalum and niobium.
And (2) the obtained fluoroniobate solution enters a sulfuric acid solution, the fluorotantalic acid is continuously remained in an organic solvent, the organic solvent containing the fluorotantalic acid enters an anti-tantalum extraction tank, a 12-grade anti-tantalum tank is used as a first back-extraction tank body, sulfuric acid or hydrochloric acid or hydrofluoric acid solution with hydrogen ion concentration of 0.05-0.6mol/L is used as a first-stage anti-tantalum agent, then the 12-grade anti-tantalum tank is used as a second back-extraction tank body, pure water is used as a back-extraction agent, a second-stage anti-tantalum potassium fluorotantalate solution is obtained, and the solution is used as a raw material of high-purity potassium fluorotantalate. And then adding hydrofluoric acid and potassium chloride into the obtained fluotantalic acid solution, heating to 92 ℃, preserving heat for half an hour, putting the solution into a first cooling tank, cooling to 70 ℃, then putting the solution into a second cooling tank, cooling to 40 ℃, putting the solution into a third cooling tank, and cooling to 15 ℃. Collecting potassium fluotantalate crystals in the second cooling tank, adding the crystals into pure water, heating to over 92 ℃, adding hydrofluoric acid and potassium chloride, dissolving the potassium fluotantalate crystals, putting the crystals into the cooling tank for crystallization, collecting the potassium fluotantalate crystals, centrifuging, and drying to obtain high-purity potassium fluotantalate solid.
As a preferred scheme of the invention, the anti-tantalum extraction is carried out in a counter-current extraction tank with 8 stages to 12 stages.
In the preferred embodiment of the present invention, the flow ratio of the extraction organic to the stripping agent is 1: 2 to 3: 1.
in the cooling crystallization of the preferred embodiment of the present invention, the rotation speed of the stirring paddle in the cooling tank is 30-90 revolutions per minute.
The acidity of the anti-tantalum liquid in the preferable embodiment of the invention is 0.05-0.6mol/L, and the preferable acidity is 0.1-0.5 mol/L.
The second-stage anti-tantalum liquid is a sulfuric acid or hydrochloric acid or hydrofluoric acid solution with hydrogen ion concentration of 0.05-0.6mol/L, and the selected sulfuric acid or hydrochloric acid or hydrofluoric acid solution is high-purity.
As a preferable scheme of the invention, the anti-tantalum liquid in the second stage passes through a precise filtering device, and the filtering precision is less than 0.1 micron.
Example 1:
1000kg of tantalum-niobium ore (30 percent of tantalum oxide and 20 percent of niobium oxide) is crushed to 200 meshes, added into 1700L of hydrofluoric acid with the mass percent concentration of 55 percent, and then 400L of sulfuric acid with the mass percent concentration of 92 percent is supplemented, and the heat preservation and the decomposition are carried out.
And (2) entering an ore extraction tank, extracting tantalum-niobium by using an MIBK solution, enabling fluorotantalic acid and fluoroniobate acid to enter MIBK, performing countercurrent extraction in a pickling tank by using 3.7mol/L sulfuric acid, entering an organic solvent containing tantalum-niobium into an anti-niobium tantalum extraction tank after extraction, performing countercurrent extraction by using a sulfuric acid solution with acidity of 0.75mol/L and the organic solvent containing tantalum-niobium, entering a fluoroniobate acid solution into the sulfuric acid solution, and continuously remaining the fluorotantalic acid in the organic solvent.
The method comprises the steps of enabling an organic solvent containing the fluotantalic acid to enter an anti-tantalum extraction tank, adopting a 12-grade anti-tantalum tank as a first back-extraction tank body, adopting a sulfuric acid solution with the hydrogen ion concentration of 0.1mol/L as a first-stage anti-tantalum agent, then utilizing the 12-grade anti-tantalum tank as a second back-extraction tank body, utilizing pure water as a back-extraction agent to obtain a second-stage anti-tantalum solution, and taking 1000L of the solution as a raw material of the high-purity potassium fluotantalate.
Then heating the solution to 92 ℃, adding 40% of hydrofluoric acid and 30% of high-grade pure potassium chloride with the high-grade pure mass concentration exceeding 20% of the chemical dose ratio, heating to 92 ℃, preserving the heat for half an hour, putting the solution into a first cooling tank, cooling to 70 ℃, then putting the solution into a second cooling tank, cooling to 40 ℃, finally putting the solution into a third cooling tank, and cooling to 15 ℃.
Collecting 20kg of potassium fluotantalate crystals in the second cooling tank, adding the crystals into 200L of pure water, heating to above 92 ℃, adding superior pure hydrofluoric acid and superior pure potassium chloride which are more than 20% (specifically 30%) of the chemical dose ratio, dissolving the potassium fluotantalate crystals, putting the crystals into the cooling tank for crystallization, collecting the potassium fluotantalate crystals, centrifuging, and drying to obtain 17kg of high-purity potassium fluotantalate solid.
The analysis result of potassium fluotantalate shows that in Table 1, the purity reaches over 99.9999 percent, and the main impurities of niobium, tungsten and molybdenum are less than 0.01 ppm.
Table 1:
example 2:
1000kg of tantalum-niobium ore (30% of tantalum oxide and 20% of niobium oxide) is crushed to below 200 meshes, added into 1700L of hydrofluoric acid with the mass concentration of 55%, and then 400L of sulfuric acid with the mass concentration of 92% is supplemented, and the heat preservation and the decomposition are carried out.
And (2) entering an ore extraction tank, extracting the tantalum and niobium by using a secondary octanol solution, entering the secondary octanol, performing countercurrent extraction by using 4.2mol/L sulfuric acid in a pickling tank, entering an organic solvent containing the tantalum and niobium into a tantalum stripping tank, and performing countercurrent extraction by using a sulfuric acid solution with the acidity of 0.7mol/L and the organic solvent containing the tantalum and niobium.
The method comprises the following steps of (1) enabling a fluoroniobate solution to enter a sulfuric acid solution, continuously remaining fluorotantalic acid in an organic solvent, enabling the organic solvent containing the fluorotantalic acid to enter an anti-tantalum extraction tank, adopting a 12-grade anti-tantalum tank as a first back-extraction tank body, adopting a sulfuric acid solution with hydrogen ion concentration of 0.3mol/L as a first-stage anti-tantalum agent, then utilizing the 12-grade anti-tantalum tank as a second back-extraction tank body, utilizing pure water as a back-extraction agent, and enabling the ratio of an organic phase to a water phase to be 1: 1, the rotating speed of the stirring paddle is 100 revolutions per minute. Obtaining a second-stage anti-tantalum solution, filtering by using a filter membrane with the filtering precision of 0.1 micron, and taking 1000L of the solution as a raw material of high-purity potassium fluotantalate.
Then heating the solution to 92 ℃, adding superior hydrofluoric acid and superior pure potassium chloride which are more than 20 percent of the chemical dose ratio, heating to 92 ℃, preserving the heat for half an hour, putting the solution into a first cooling tank, cooling to 70 ℃, then putting the solution into a second cooling tank, cooling to 40 ℃, putting the solution into a third cooling tank, and cooling to 15 ℃.
Collecting 150kg of potassium fluotantalate crystals in the second cooling tank, adding the crystals into 200L of pure water, heating to over 92 ℃, adding superior pure hydrofluoric acid and superior pure potassium chloride with the chemical dose of more than 20%, dissolving potassium fluotantalate crystals, putting the crystals into the cooling tank for crystallization, collecting potassium fluotantalate crystals, centrifuging and drying to obtain 143kg of high-purity potassium fluotantalate solid. The analysis result of potassium fluotantalate shows in Table 2, the purity reaches over 99.9999%, and the main impurities niobium, tungsten and molybdenum are less than 0.01 ppm.
Table 2:
comparative example 1:
1000kg of tantalum-niobium ore (30% of tantalum oxide and 20% of niobium oxide) is crushed to below 200 meshes, added into 1700L of hydrofluoric acid with the mass fraction of 55%, and then 400L of sulfuric acid with the mass fraction of 92% is supplemented, and the heat preservation and the decomposition are carried out.
The method comprises the steps of entering an ore extraction tank, extracting tantalum-niobium by using MIBK or sec-octanol solution, entering tantalum-niobium fluoride and niobium fluoride into MIBK or sec-octanol, performing countercurrent extraction in a pickling tank by using 4.0mol/L sulfuric acid, entering an anti-niobium tantalum extraction tank by using an organic solvent containing tantalum-niobium, performing countercurrent extraction by using a sulfuric acid solution with the acidity of 0.80mol/L and an organic solvent containing tantalum-niobium, entering a niobium-fluoride solution into a sulfuric acid solution, continuously remaining tantalum fluoride in the organic solvent, entering an anti-tantalum extraction tank by using an anti-tantalum tank stirring paddle with the rotation speed of 10 levels of 90 revolutions per minute as a back extraction tank body, and using pure water as a back extraction agent.
Obtaining the solution of reverse tantalum, and taking 1000L of the solution as the raw material of the potassium fluotantalate. Then heating the solution to 92 ℃, adding superior pure hydrofluoric acid and superior pure potassium chloride with the stoichiometric ratio of more than 20%, heating to 92 ℃, preserving the heat for half an hour, and cooling to 15 ℃. Collecting 60kg of potassium fluotantalate crystals in the second cooling tank, adding the crystals into 200L of pure water, heating to above 92 ℃, adding superior pure 40% hydrofluoric acid and 20kg of superior pure potassium chloride with the stoichiometric ratio exceeding 20%, dissolving potassium fluotantalate crystals, then placing the crystals into the cooling tank for crystallization, collecting potassium fluotantalate crystals, centrifuging and drying to obtain 56kg of high-purity potassium fluotantalate solid. The purity of the potassium fluotantalate reaches over 99.99 percent through analysis.
Table 3:
the invention mainly adopts multi-stage extraction and multi-stage extraction, can further reduce impurities in the potassium fluotantalate, and prepares the high-purity potassium fluotantalate according to the extraction behavior of the impurities under different acidity and the crystallization behavior of the impurities under different cooling temperatures.
Claims (6)
1. The preparation method of the high-purity potassium fluotantalate is characterized by comprising the following steps of:
(1) and (3) decomposition: adding tantalum-niobium minerals into hydrofluoric acid and sulfuric acid for decomposition;
(2) extracting ore pulp: performing countercurrent extraction by using an MIBK solvent or an octanol solvent, and extracting fluoroniobic acid and fluorotantalic acid into the solvent;
(3) acid washing: a sulfuric acid solution is adopted to contact with the solvent obtained after extraction in the step (2) in a countercurrent manner;
(4) extracting tantalum by using reverse niobium: carrying out countercurrent extraction on the sulfuric acid solution and the organic solvent containing tantalum and niobium obtained in the step (3) in an extraction tank to extract fluoroniobic acid into a water phase to form an acid fluoroniobic acid aqueous solution;
(5) anti-tantalum: the residual organic solution is put in another extraction tank, and the fluorine tantalic acid organic solution is back extracted into pure water by using the pure water to form a fluorine tantalic acid aqueous solution;
(6) synthesizing: heating the obtained fluotantalic acid aqueous solution, and adding potassium chloride and hydrofluoric acid;
(7) cooling and crystallizing: cooling the synthetic liquid to obtain potassium fluotantalate crystals, centrifuging and drying to obtain high-purity potassium fluotantalate crystals;
specifically adopting two sections of anti-tantalum, wherein the anti-tantalum liquid of the first section of anti-tantalum is a sulfuric acid, hydrochloric acid or hydrofluoric acid solution with the hydrogen ion concentration of 0.05-0.6mol/L, the anti-tantalum liquid of the second section of anti-tantalum is pure water, and the fluotantalic acid aqueous solution obtained by the second section of anti-tantalum is used as a raw material for synthesizing the potassium fluotantalate in the step (6);
and (7) specifically adopting three-stage cooling, controlling the cooling temperature of the first stage to be 70-80 ℃, then putting the liquid obtained after the first stage is cooled into the second stage for cooling, collecting the crystal obtained after the first stage is cooled, controlling the cooling temperature of the second stage to be 40-70 ℃, then putting the liquid obtained after the second stage is cooled into the third stage for cooling, collecting the crystal obtained after the second stage is cooled, controlling the cooling temperature of the third stage to be 10-40 ℃, collecting the crystal obtained after the third stage is cooled, utilizing the potassium fluotantalate obtained after the second stage is cooled, recrystallizing the potassium fluotantalate once again, adding the crystal into pure water, adding high-purity hydrofluoric acid and high-purity potassium chloride, and finally obtaining the high-purity potassium fluotantalate.
2. The method for preparing high purity potassium fluotantalate of claim 1, wherein: the anti-tantalum extraction in the step (5) is carried out in a counter-current extraction tank with 8 stages to 12 stages.
3. The method for preparing high purity potassium fluotantalate of claim 1, wherein: controlling the flow ratio of the extraction organic solvent to the stripping agent in the step (5) to be 1: 2 to 3: 1.
4. the method for preparing high purity potassium fluotantalate of claim 1, wherein: and (7) controlling the rotating speed of the stirring paddle in the cooling tank to be 30-90 revolutions per minute.
5. The method for preparing high purity potassium fluotantalate of claim 1, wherein: and (5) allowing the anti-tantalum liquid of the second section in the step (5) to pass through a precision filtering device, and controlling the filtering precision to be less than 0.1 micrometer.
6. The method for preparing high purity potassium fluotantalate of claim 1, wherein:
(1) crushing the tantalum-niobium ore to be not more than 200 meshes, adding the crushed ore into hydrofluoric acid, adding sulfuric acid, and performing heat preservation decomposition;
(2) then the mixed solution enters an ore extraction tank, tantalum-niobium is extracted by using an MIBK solvent or an octanol solvent, so that fluorotantalic acid and fluoroniobate acid enter the solvent, then countercurrent extraction is carried out in an acid washing tank by using 3.7-4.2mol/L sulfuric acid, then an organic solvent containing tantalum-niobium enters an anti-niobium tantalum extraction tank, and countercurrent extraction is carried out on the organic solvent containing tantalum-niobium by using 0.6-0.8mol/L sulfuric acid solution and the organic solvent containing tantalum-niobium;
(3) the obtained fluoroniobate solution enters a sulfuric acid solution, and the obtained fluorotantalate solution is left in an organic solvent;
(4) the method comprises the steps of enabling an organic solvent containing the fluorotantalic acid to enter an anti-tantalum extraction tank, adopting a 12-grade anti-tantalum tank as a first-stage back-extraction tank body, adopting a sulfuric acid, hydrochloric acid or hydrofluoric acid solution with hydrogen ion concentration of 0.05-0.6mol/L as a first-stage back-extraction agent, then utilizing the 12-grade anti-tantalum tank as a second-stage back-extraction tank body, and utilizing pure water as a back-extraction agent to obtain a second-stage fluorotantalic acid solution for later use;
(5) adding hydrofluoric acid and potassium chloride into the obtained fluotantalic acid solution, heating to 92 ℃ or above, preserving heat for half an hour, putting the solution into a first cooling tank, cooling to 70-80 ℃, then putting the solution into a second cooling tank, cooling to 40-70 ℃, and finally putting the solution into a third cooling tank, and cooling to 10-40 ℃; collecting potassium fluotantalate crystals in the second cooling tank, adding the crystals into pure water, heating to 92 ℃ or above, adding hydrofluoric acid and potassium chloride, dissolving the potassium fluotantalate crystals, putting the crystals into the cooling tank for crystallization, collecting the potassium fluotantalate crystals, centrifuging, and drying to obtain the high-purity potassium fluotantalate solid.
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| CN110923740B (en) * | 2019-10-17 | 2021-02-19 | 东北大学 | Method for electrochemically deeply removing water-soluble extractant in tantalum liquid in preparation process of potassium fluotantalate |
| CN111690827B (en) * | 2020-07-01 | 2022-07-15 | 江西拓泓新材料有限公司 | Method for recovering tantalum resource from potassium fluotantalate crystallization mother liquor |
| CN112010348B (en) * | 2020-09-14 | 2022-08-19 | 宁夏东方钽业股份有限公司 | Preparation method of high-purity niobium oxide for high-purity niobium sheet for irradiation monitoring tube |
| CN115818714A (en) * | 2022-11-07 | 2023-03-21 | 中信金属股份有限公司 | Method for preparing potassium heptafluoroniobate |
| CN116358253A (en) * | 2023-02-14 | 2023-06-30 | 宁夏东方钽业股份有限公司 | Potassium fluorotantalate drying and preserving equipment and method |
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| CN104480304A (en) * | 2014-04-15 | 2015-04-01 | 宁夏东方钽业股份有限公司 | Method for reducing usage amount of ammonia gas during process of tantalum-niobium hydrometallurgical extraction |
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| CN1460088A (en) * | 2001-04-06 | 2003-12-03 | 三井金属鉱业株式会社 | Method for producing high purity potassium fluorotantalate crystal or high purity potassium fluoroniobate crystal and recrystallization vessel for use in method for production, and potassium |
| CN104480304A (en) * | 2014-04-15 | 2015-04-01 | 宁夏东方钽业股份有限公司 | Method for reducing usage amount of ammonia gas during process of tantalum-niobium hydrometallurgical extraction |
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