CN102994780A - Method for purifying tantalum powder - Google Patents
Method for purifying tantalum powder Download PDFInfo
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- CN102994780A CN102994780A CN2012105480082A CN201210548008A CN102994780A CN 102994780 A CN102994780 A CN 102994780A CN 2012105480082 A CN2012105480082 A CN 2012105480082A CN 201210548008 A CN201210548008 A CN 201210548008A CN 102994780 A CN102994780 A CN 102994780A
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- tantalum powder
- alkali metal
- mixture
- filter cake
- aqueous solution
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 239000012065 filter cake Substances 0.000 claims abstract description 48
- 229910001508 alkali metal halide Inorganic materials 0.000 claims abstract description 42
- 150000008045 alkali metal halides Chemical class 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005554 pickling Methods 0.000 claims abstract description 22
- 230000002378 acidificating effect Effects 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- -1 alkali metal salts Chemical class 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000011026 diafiltration Methods 0.000 claims description 43
- 229910052728 basic metal Inorganic materials 0.000 claims description 37
- 150000003818 basic metals Chemical class 0.000 claims description 37
- 239000011734 sodium Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 20
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 11
- APLLYCDGAWQGRK-UHFFFAOYSA-H potassium;hexafluorotantalum(1-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[Ta+5] APLLYCDGAWQGRK-UHFFFAOYSA-H 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical group [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract 4
- 150000001340 alkali metals Chemical class 0.000 abstract 3
- 150000004820 halides Chemical class 0.000 abstract 1
- 238000012544 monitoring process Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000000047 product Substances 0.000 description 21
- 239000007795 chemical reaction product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000009833 condensation Methods 0.000 description 12
- 230000005494 condensation Effects 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 238000005070 sampling Methods 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 229910052715 tantalum Inorganic materials 0.000 description 8
- 238000007873 sieving Methods 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a method for purifying tantalum powder. The method comprises the following step of washing a mixture containing tantalum powder, alkali metal and alkali halide by using an aqueous solution of acidic electrolyte and further comprises the following specific steps of: providing the mixture comprising the tantalum powder, the alkali metal and the alkali metal halide; putting the mixture comprising the tantalum powder, the alkali metal and the alkali metal halide into a filtering and washing tank containing the aqueous solution of the acidic electrolyte, washing out impurities, such as alkali metal halides as well as K, Na and oxides thereof by using the aqueous solution of the acidic electrolyte, monitoring pH of the aqueous solution at the same time, and filtering to obtain a first filter cake till no mixture particle of alkali metal salts can be seen by naked eyes and pH value of the aqueous solution is unchanged; putting the first filter cake to a deionized-water-containing stirring and washing tank, carrying out stirring and washing, and then filtering to obtain a second filter cake; putting the second filter cake to a pickling bath and pickling for 2-4 hours, and then filtering to obtain a third filter cake, wherein the pickling bath contains 10wt% of aqueous mixture solution prepared from hydrochloric acid, nitric acid, hydrofluoric acid and hydrogen peroxide; and drying the third filter cake to obtain raw tantalum powder.
Description
Technical field
The present invention relates to a kind of method of the tantalum powder of purifying, particularly the method for purification tantalum powder from the mixture that comprises tantalum powder, basic metal and alkali metal halide.
Background technology
Tantalum is a kind of rare metal, is mainly used in the industries such as electronic industry, chemical industry equipment, metal cutting processing, aerospace, the consumption rapid growth of tantalum in recent years, but scarcity of resources.Therefore, effectively utilizing the waste of tantalum resource, minimizing tantalum is a kind of development trend of tantalum industry.
In electronic industry, the main application of tantalum powder is to make electrolytic condenser, the development trend of tantalum electrolytic capacitor is that requirement has high-capacitance, low-leakage current and low equivalent series resistance (for anode low loss), as the tantalum powder of making tantalum electrolytic capacitor anode main raw, then require foreign matter content low, particularly lower O, C, K, Na, Fe, Ni are because the existence of O, C, K, Na, Fe, Ni can cause that condenser leakage current increases, voltage breakdown reduces in the tantalum powder.
Often need to be from the mixture that comprises the tantalum powder in the industrial production purification tantalum powder.Particularly need purification tantalum powder from the mixture that comprises tantalum powder, basic metal and alkali metal halide.For instance, a kind of such mixture is to adopt sodium Metal 99.5 (Na) reduction tantalum potassium fluoride (K
2TaF
7) resulting reaction product, tantalum powder (Ta), Sodium Fluoride (NaF) and Potassium monofluoride (KF) are wherein arranged.This chemical reaction can be expressed as:
K
2TaF
7+5Na=Ta+5NaF+2KF
Adopting sodium Metal 99.5 (Na) reduction tantalum potassium fluoride (K
2TaF
7) process in, be the control reaction, often when reaction, add alkali metal halide, such as one or more mixture of sodium-chlor (NaCl), Repone K (KCl) and Potassium monofluoride (KF) as thinner; In order to ensure above-mentioned sodium Metal 99.5 (Na) reduction tantalum potassium fluoride (K
2TaF
7) sufficient reacting is thorough, often needs to add excessive sodium Metal 99.5, excessive sodium Metal 99.5 (Na) can be reduced to potassium metal (K) with potassium ion (K+) under this condition, and this reaction equation is
(l).Above-mentioned reaction is generally being carried out more than 700 ℃, after above-mentioned reaction finishes, the tantalum powder that generates is suspended in the melt of alkali metal halide that Sodium Fluoride (NaF), Potassium monofluoride (KF) and diluting salt form and remaining alkali metallic sodium (Na), potassium (K) and oxide compound or superoxide, becomes tantalum powder and above-mentioned alkali metal halide mixture after the cooling and is entrained with the alkali metallic sodium (Na) of surplus, the condensed product of potassium (K).This condensed product is exactly a kind of mixture that comprises tantalum powder, basic metal and alkali metal halide.
There has been the method that comprises the mixture purification tantalum powder of tantalum powder, basic metal and alkali metal halide from this in the prior art.Generally speaking, this mixture that comprises tantalum powder, basic metal and alkali metal halide is generally the condensed product of bulk form.Condensed product is broken into small-particle, usually washs with deionized water, separate alkali metal halide soluble in water and remaining sodium Metal 99.5, the potassium of reaction, afterwards again through obtaining being suitable for the tantalum powder of subsequent disposal after agitator treating, pickling, the oven dry.
When washing with deionized water, remaining sodium Metal 99.5, potassium meeting and the steeping in water for reconstitution of reaction given birth to following reaction: 2K+2H
2O=2KOH+H
2
2Na+2H
2O=2NaOH+H
2
Form strong alkali solution, the tantalum powder generates alkaline tantalate or inclined to one side tantalate in the medium-term and long-term immersion of strong alkali solution.Yet there are the following problems for the technique of this prior art: the potassium tantalate that generates on the one hand is soluble in water, makes the part tantalum enter waste liquid, and tantalum powder yield reduces; On the other hand, inclined to one side potassium tantalate and the sodium tantalate/sodium metatantalate of generation are insoluble in water, are difficult for flush away, cause K, Na content in the tantalum powder high.
Chinese patent CN102191389A attempts to provide a kind of solution: arrive neutrality with 15 ℃～35 ℃ cold deionized water diafiltration first, and then carry out diafiltration with the deionized water of 40 ℃～100 ℃ of heat, make lower electrical conductivity of water be lower than 10 μ s/cm.Yet there are a lot of shortcomings in the method.
Summary of the invention
The invention provides a kind of from the mixture that comprises the tantalum powder method of purification tantalum powder.Especially, this mixture that comprises the tantalum powder is the mixture that comprises tantalum powder, basic metal and alkali metal halide.More particularly, this mixture that comprises the tantalum powder is for reducing tantalum potassium fluoride (K with sodium Metal 99.5 (Na)
2TaF
7) resulting reaction product.
The present invention provide especially a kind of from the mixture that comprises tantalum powder, basic metal and alkali metal halide the method for purification tantalum powder, the method comprises the steps: the described mixture of tantalum powder, basic metal and alkali metal halide that comprises with the solution washing of acidic electrolyte bath.
In a specific embodiment of the present invention, described method may further comprise the steps:
1) provides the mixture that comprises tantalum powder, basic metal and alkali metal halide;
The mixture that 2) will comprise tantalum powder, basic metal and alkali metal halide drops in the diafiltration groove of the aqueous solution that contains acidic electrolyte bath, the impurity such as aqueous solution eccysis basic metal haloid, K, Na and oxide compound thereof with acidic electrolyte bath, monitor simultaneously the pH of the aqueous solution, until when no longer changing without the compound particles of the visible an alkali metal salt of naked eyes and pH value of water solution, filter and obtain the first filter cake;
3) above-mentioned the first filter cake input is contained in the agitator treating groove of deionized water, carry out agitator treating, filter afterwards, obtain the second filter cake;
4) the second filter cake was put into the pickling tank pickling 2-4 hour, this pickling tank contains the aqueous solution of the mixture of hydrochloric acid, nitric acid, hydrofluoric acid and hydrogen peroxide, filters afterwards and obtains the 3rd filter cake;
5) oven dry of the 3rd filter cake is obtained the former powder of tantalum powder.
In step 1) in, can obtain to comprise in multiple different mode the mixture of tantalum powder, basic metal and alkali metal halide.For example, have a mind to or by mistake tantalum powder, basic metal and alkali metal halide are mixed.
Usually, this mixture that comprises tantalum powder, basic metal and alkali metal halide can be by reducing tantalum potassium fluoride (K with sodium Metal 99.5 (Na)
2TaF
7) after the reaction product that obtains.Thereby, can prepare in the following way the mixture that comprises tantalum powder, basic metal and alkali metal halide: reducing tantalum potassium fluoride (K with sodium Metal 99.5 (Na)
2TaF
7) after, naturally cooling namely obtains comprising the mixture of tantalum powder, basic metal and alkali metal halide.At this moment, the mixture that comprises tantalum powder, basic metal and alkali metal halide mostly is the form of condensation block.
Because when this reduction reaction, often add excessive sodium Metal 99.5, so usually have excessive sodium Metal 99.5 and inevitable na oxide in the reaction product that obtains.And this reduction reaction may be attended by side reaction, and for example excessive sodium is reduced into potassium metal with potassium ion.Thereby, except tantalum powder, Sodium Fluoride and Potassium monofluoride, also may there be for example potassium metal and oxide compound thereof and the additive diluting salt of sodium-chlor, Repone K and Potassium monofluoride form for example of reaction incomplete sodium Metal 99.5 and oxide compound thereof, various side reaction product in this reduction reaction product.But the degree of reaction does not affect enforcement of the present invention.Because this reduction reaction is carried out under comparatively high temps, so in the process of cool to room temperature, the reduction reaction product can become the form of block condensation block usually.Certainly, this condensation block also comprises tantalum powder, Sodium Fluoride and Potassium monofluoride, and reacts for example potassium metal and oxide compound thereof and the various additive diluting salt of sodium-chlor, Repone K and Potassium monofluoride form for example of incomplete sodium Metal 99.5 and oxide compound thereof, various side reaction product.Therefore, this condensation block is mixture a kind of who comprises tantalum powder, basic metal and alkali metal halide.
Those skilled in the art should know, and can also original position cool off reaction product after reduction reaction, thereby obtain the condensation block.
Preferably, can be first with the mixture that comprises tantalum powder, basic metal and alkali metal halide for example the described condensation block fritter that is broken into yardstick≤20mm drop into again in the diafiltration groove.More preferably, can with the mixture that comprises tantalum powder, basic metal and alkali metal halide for example described condensation block be ground into powder.
Preferably, in step 1) in basic metal be Na and/or potassium.Preferably, 1) in alkali metal halide be sodium-chlor, Repone K and/or Potassium monofluoride.
In step 2) in, described acidic electrolyte bath can be mineral acid and/or organic acid; Be preferably mineral acid; Further preferably, described acidic electrolyte bath is a kind of or two or more mixture that is selected from hydrochloric acid, nitric acid, sulfuric acid, the hydrofluoric acid.More preferably, described ground acidic electrolyte bath is hydrochloric acid.
The pH value of the aqueous solution of described acidic electrolyte bath preferably＜6 is more preferably 3-5.
In step (2), described diafiltration groove can be any type of diafiltration groove static diafiltration groove (namely without stirring rake static diafiltration) for example, be preferably the dynamic diafiltration groove (namely being with the dynamic diafiltration of stirring rake) with stirring rake, and its mixing speed preferably＜60 rev/min, is more preferably＜30 rev/mins.
As for the agitator treating of step (3), its stirring velocity is not added special restriction.Preferably but not necessarily mixing speed is 0-300 rev/min, is more preferably 90-150 rev/min.
In step 4) in, the total concn of preferred hydrochloric acid, nitric acid, hydrofluoric acid and hydrogen peroxide is 10wt%, and can be arbitrary proportion between them.
In a preferred embodiment, first the condensation block is broken into fritter less than 20mm; Then adding 3/4 groove pH value in the diafiltration groove is the acidic electrolyte bath aqueous solution (for example aqueous hydrochloric acid) of 3-5, wash in the fritter adding diafiltration groove that fragmentation is good, in front 1 hour of washing, with pH value of water solution in the pH detection paper diafiltration groove, such as the pH value〉6, then add an amount of acidic electrolyte bath, guarantee that pH value of water solution is 3-5 in the diafiltration groove, avoid producing alkali corrosion tantalum powder; Treat that afterwards compound particles and the pH value without the visible an alkali metal salt of naked eyes no longer changes in the diafiltration groove, filter and obtain the first filter cake; Filter cake drops into and uses deionized water agitator treating 5-10 time in the agitator treating groove after will washing, and filters afterwards and obtains the second filter cake; To carry out pickling in the second filter cake input pickling tank, further remove the impurity such as Fe, Ni in the tantalum powder, Si with containing the aqueous solution in hydrochloric acid, nitric acid, hydrofluoric acid and the hydrogen peroxide, resulting material after the pickling gone in the diafiltration groove filter, be lower than 5 μ s/cm with deionized water wash to specific conductivity, filter and obtain the 3rd filter cake; With the 3rd filter cake oven dry, sieving obtains the tantalum powder.
During the method according to this invention has the following advantages one or more:
1) the method fundamentally significantly weakens even has eliminated the disadvantageous effect that strong alkali solution corrosion tantalum powder brings;
2) tantalum powder yield is high;
3) the former powder purity of the tantalum powder that obtains is high;
The leakage current of the product tantalum powder that 4) obtains is low.
Embodiment
Below in conjunction with embodiment embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only is used for explanation the present invention, and should not be considered as limiting scope of the present invention.Unreceipted actual conditions person among the embodiment carries out according to the condition of normal condition or manufacturers's suggestion.The unreceipted person of production firm of agents useful for same or instrument, being can be by the conventional products of commercial acquisition.
For the purpose of this specification sheets, the numeral of the amount of all expression compositions, reaction conditions etc. should be understood to be modified by term " about " in all cases in specification sheets and claims, unless otherwise specified.Correspondingly, the numerical parameter that provides in the following description book and the appended claims is approximation, and it can be attempted according to the present invention the desirable character that obtains and change, unless opposite indication is arranged.At least, and do not plan to limit the application of doctrine of equivalents on the claim scope, each numerical parameter should be explained according to the figure place of the significant figure of reporting and according to the common technology of rounding up at least.
Only for more clearly describing purpose of the present invention, following examples adopt sodium Metal 99.5 (Na) reduction tantalum potassium fluoride (K
2TaF
7) resulting reaction product is as the mixture that comprises tantalum powder, basic metal and alkali metal halide.Yet method of the present invention also goes for the mixture that comprises tantalum powder, basic metal and alkali metal halide that other modes obtain.
Embodiment 1
The mixture that comprises tantalum powder, basic metal and alkali metal halide is provided at first in the following way: the 100kg sodium-chlor (NaCl) of in reaction vessel, packing into, be heated to 900 ℃, in reaction vessel, add 100kg tantalum potassium fluoride (K again
2TaF
7), add again about 30kg liquid metal sodium, 900 ℃ of insulations 2 hours, be cooled to the mixture that comprises tantalum powder, basic metal and alkali metal halide that room temperature obtains the condensation block form, in reaction vessel, take out this condensation block, be broken into the fritter less than 20mm, and be divided into two parts.
Then, adding 3/4 groove pH value is 4.0 aqueous hydrochloric acid in the diafiltration groove, will wash in first part of fritter adding diafiltration groove, guarantees in the washing process that aqueous solution liquid level is higher than more than the 10cm of reaction mass surface; In front 1 hour of washing, with pH value of water solution in the pH detection paper diafiltration groove, such as the pH value〉6, then add the appropriate hydrochloric acid aqueous solution, guarantee that pH value of water solution is 3-5 in the diafiltration groove, avoid producing alkali corrosion tantalum powder; After no longer changing without the compound particles of the visible an alkali metal salt of naked eyes and pH value, filter and obtain the first filter cake afterwards;
Then, with also using deionized water agitator treating 5 times in the first filter cake input agitator treating groove, filter afterwards and obtain the second filter cake;
Next, the second filter cake was dropped into the 10wt% mixing acid pickling that is made into hydrochloric acid, nitric acid, hydrofluoric acid and hydrogen peroxide in the pickling tank 4 hours, the material that obtains after the pickling gone in the diafiltration groove filter, being lower than 5 μ s/cm(specific conductivity with deionized water wash to specific conductivity tests with HANNA digital electrical conductivity instrument (HI8733)), filter and obtain the 3rd filter cake.
At last, with the 3rd filter cake oven dry, sieving obtains the former powder of tantalum powder.
The former powder of tantalum powder is weighed calculated yield; Foreign matter content in the former powder of sampling analysis tantalum powder.Foreign matter content is listed in the table 1 in yield and the former powder of tantalum powder.
Comparative example 1
In the diafiltration groove, add 3/4 groove deionized water, get in second part of fritter adding diafiltration groove among the embodiment 1 and wash, guarantee in the washing process that aqueous solution liquid level is higher than more than the 10cm of reaction mass surface, regularly stirs in the washing process; After no longer changing without the compound particles of the visible an alkali metal salt of naked eyes and pH value, filter and obtain filter cake afterwards; With this filter cake by embodiment 1 same process condition dry, sieving obtains the former powder of tantalum powder.
The former powder of tantalum powder is weighed calculated yield; Foreign matter content in the sampling analysis tantalum powder.Foreign matter content is listed in the table 1 in yield and the tantalum powder.
Embodiment 2
At first, provide in the following way the mixture that comprises tantalum powder, basic metal and alkali metal halide: the mixture of in reaction vessel, pack into 100kg Repone K (KCl) and 100kg Potassium monofluoride (KF), be heated to 900 ℃, in reaction vessel, add first 100kg tantalum potassium fluoride (K again
2TaF
7), add again about 30kg liquid metal sodium, 900 ℃ of insulations 1 hour, after being cooled to room temperature, taking out reaction product in the reaction vessel is the mixture that comprises tantalum powder, basic metal and alkali metal halide of condensation block form, be broken into the fritter less than 20mm, the material that fragmentation is good is divided into two parts.
Then, adding 3/4 groove pH value is 4.0 aqueous hydrochloric acid in the diafiltration groove of stirring rake, opens stirring rake, and rotating speed of agitator is 10 rev/mins; With washing in first part of fritter adding diafiltration groove, in front 1 hour of washing, detect pH value of water solution in the diafiltration groove, such as the pH value〉6, then add the appropriate hydrochloric acid aqueous solution, guarantee that pH value of water solution is 3-5 in the diafiltration groove, avoid producing alkali corrosion tantalum powder; After no longer changing without the compound particles of the visible an alkali metal salt of naked eyes and pH value, filter and obtain the first filter cake afterwards.
Then, the first filter cake is dropped into deionized water agitator treating 7 times of agitator treating groove, filter afterwards and obtain the second filter cake;
Next, the second filter cake was dropped into the 10wt% mixing acid pickling that is made into hydrochloric acid, nitric acid, hydrofluoric acid and hydrogen peroxide in the pickling tank 4 hours, material goes in the diafiltration groove and filters after the pickling, spends ion-cleaning to specific conductivity and is lower than 5 μ s/cm, filters and obtains the 3rd filter cake.
At last, with the 3rd filter cake oven dry, sieving obtains the former powder of tantalum powder.
The tantalum powder is weighed calculated yield; Foreign matter content in the sampling analysis tantalum powder.Foreign matter content is listed in the table 1 in tantalum powder yield and the tantalum powder.
Comparative example 2
In the diafiltration groove, add 3/4 groove deionized water, get among the embodiment 2 and wash in second part of fritter adding diafiltration groove, guarantee in the washing process that aqueous solution liquid level is higher than more than the 10cm of reaction mass surface, regularly stirs in the washing process; After afterwards after no longer changing without the compound particles of the visible an alkali metal salt of naked eyes and pH value, filter and obtain filter cake; With filter cake after the washing according to the processing condition oven dry identical with embodiment 2, sieving obtains the former powder of tantalum powder.
The tantalum powder is weighed calculated yield; Foreign matter content in the sampling analysis tantalum powder.Foreign matter content is listed in the table 1 in tantalum powder yield and the tantalum powder.
Embodiment 3
At first, provide in the following way the mixture that comprises tantalum powder, basic metal and alkali metal halide: the mixture of in reaction vessel, pack into 150kg Repone K (KCl) and 150kg Potassium monofluoride (KF), be heated to 880 ℃, in reaction vessel, add first 30kg tantalum potassium fluoride (K again
2TaF
7), add again about 10kg liquid metal sodium, 880 ℃ of insulations 0.5 hour, be cooled to room temperature after, the taking-up reaction product is the condensation block in the reaction vessel, is broken into the fritter less than 20mm, the material that fragmentation is good is divided into two parts.
Then, adding 3/4 groove pH value is 4.0 aqueous hydrochloric acid in the diafiltration groove, first part of fritter is added in the diafiltration groove wash, and guarantees in the washing process that the aqueous solution did not have reaction mass; In front 1 hour of washing, detect pH value of water solution in the diafiltration groove, such as the pH value〉6, then add the appropriate hydrochloric acid aqueous solution, guarantee that pH value of water solution is 3-5 in the diafiltration groove, avoid producing alkali corrosion tantalum powder; After no longer changing without the compound particles of the visible an alkali metal salt of naked eyes and pH value, filter and obtain the first filter cake afterwards.
Then, the first filter cake is dropped into deionized water agitator treating 10 times of agitator treating groove, filter afterwards and obtain the second filter cake.
Next, the second filter cake was dropped into the 10wt% mixing acid pickling that is made into hydrochloric acid, nitric acid, hydrofluoric acid and hydrogen peroxide in the pickling tank 2 hours, material goes in the diafiltration groove and filters after the pickling, spends ion-cleaning to specific conductivity and is lower than 5 μ s/cm, filters and obtains the 3rd filter cake.
At last, with the 3rd filter cake oven dry, sieving obtains the former powder of tantalum powder.
The tantalum powder is weighed calculated yield; Foreign matter content in the sampling analysis tantalum powder.Foreign matter content is listed in the table 1 in tantalum powder yield and the tantalum powder.
Comparative example 3
In the diafiltration groove, add 3/4 groove deionized water, get among the embodiment 3 and wash in second part of fritter adding diafiltration groove, guarantee in the washing process that aqueous solution liquid level is higher than more than the 10cm of reaction mass surface, regularly stirs in the washing process; After no longer changing without the compound particles of the visible an alkali metal salt of naked eyes and pH value, filter and obtain filter cake afterwards; After will washing filter cake by with embodiment 3 same process conditions oven dry, sieving obtains the former powder of tantalum powder.The tantalum powder is weighed calculated yield; Foreign matter content in the sampling analysis tantalum powder.Foreign matter content is listed in the table 1 in tantalum powder yield and the tantalum powder.
Note, among above-described embodiment 1-3 and the comparative example 1-3 in the tantalum powder analysis of foreign matter content undertaken by regulation among GB GB/T15076.1～15076.15 and the industry standard YS/T573-2007.
Can find out that from the result of table 1 embodiment compares with comparative example, it is high that tantalum powder yield is obviously wanted, and foreign matter content is also lower.
Hereinafter, also the former powder of resulting tantalum powder has been carried out other sign.
Embodiment 1 is carried out subsequent disposal with the former powder of comparative example 1 gained tantalum powder simultaneously by the same terms: first pelletizing granulation, afterwards 1480 ℃ of vacuum heat treatment 30 minutes, tantalum powder after the vacuum heat treatment is added 1.5% magnesium powder, 900 ℃ of deoxidations 3 hours, by product after overpickling is removed deoxidation again, obtain product tantalum powder after the washing and drying, foreign matter content in the sampling analysis tantalum powder, foreign matter content is listed in the table 2 in the tantalum powder.Product tantalum powder is pressed into diameter 5mm, and density is 5.0g/cm
3Briquet, 1560 ℃ of sintering formed agglomerate in 30 minutes in vacuum oven.Above-mentioned agglomerate is put into the 0.1vol% phosphate aqueous solution, boost to the 80V constant voltage with the current density of 60mA/g and formed anode block in 180 minutes.With above-mentioned anode block 56V in 10vol% phosphate aqueous solution electric current that leaks hunting, 120Hz surveys electrical capacity and loss in the 38vol% aqueous sulfuric acid, and test result is listed in table 3.
Embodiment 2 is carried out subsequent disposal with the former powder of comparative example 2 gained tantalum powder simultaneously by the same terms: first pelletizing granulation, afterwards 1300 ℃ of vacuum heat treatment 30 minutes, tantalum powder after the vacuum heat treatment is added 2.5% magnesium powder, 860 ℃ of deoxidations 3 hours, by product after overpickling is removed deoxidation again, obtain product tantalum powder after the washing and drying, foreign matter content in the sampling analysis tantalum powder, foreign matter content is listed in the table 2 in the tantalum powder.Product tantalum powder is pressed into diameter 5mm, and density is the briquet of 5.0g/cm3, and 1300 ℃ of sintering formed agglomerate in 30 minutes in vacuum oven.Above-mentioned agglomerate is put into the 0.1vol% phosphate aqueous solution, boost to the 30V constant voltage with the current density of 90mA/g and formed anode block in 120 minutes.With above-mentioned anode block 21V in 0.1vol% phosphate aqueous solution electric current that leaks hunting, 120Hz surveys electrical capacity and loss in the 30vol% aqueous sulfuric acid, and test result is listed in table 3.
Embodiment 3 is carried out subsequent disposal with the former powder of comparative example 3 gained tantalum powder simultaneously by the same terms: first pelletizing granulation, afterwards 1100 ℃ of vacuum heat treatment 30 minutes, tantalum powder after the vacuum heat treatment is added 3.5% magnesium powder, 800 ℃ of deoxidations 3 hours, by product after overpickling is removed deoxidation again, obtain product tantalum powder after the washing and drying, foreign matter content in the sampling analysis tantalum powder, foreign matter content is listed in the table 2 in the tantalum powder.Product tantalum powder is pressed into diameter 5mm, and density is 4.5g/cm
3Briquet, 1250 ℃ of sintering formed agglomerate in 20 minutes in vacuum oven.Above-mentioned agglomerate is put into the 0.1vol% phosphate aqueous solution, boost to the 20V constant voltage with the current density of 110mA/g and formed anode block in 120 minutes.With above-mentioned anode block 14V in 0.1vol% phosphate aqueous solution electric current that leaks hunting, 120Hz surveys electrical capacity and loss in the 30vol% aqueous sulfuric acid, and test result is listed in table 3.
The test of leakage current, electrical capacity and loss is undertaken by the regulation of GB/T3137 in the above-mentioned tantalum powder.
Can find out that from table 2,3 result embodiment compares with comparative example, the foreign matter content of product tantalum powder is low, and leakage current is lower.
Table 1: the foreign matter content in yield and the former powder of tantalum powder
Table 2: product tantalum powder foreign matter content (ppm)
| ? | O | C | K | Na | Fe | Ni | F |
| Embodiment 1 product sample | 1420 | 10 | 3 | 4 | 4 | 5 | 10 |
| Comparative example 1 product sample | 1950 | 13 | 4 | 6 | 6 | 7 | 15 |
| Embodiment 2 product samples | 2900 | 11 | 12 | 3 | 4 | 8 | 12 |
| Comparative example 2 product samples | 3240 | 16 | 18 | 5 | 8 | 10 | 18 |
| Embodiment 3 product samples | 7200 | 12 | 35 | 5 | 5 | 6 | 15 |
| Comparative example 3 product samples | 8120 | 24 | 48 | 5 | 8 | 12 | 20 |
Table 3: the electrical analytical results of product tantalum powder
Claims (11)
1. method from the mixture purification tantalum powder that comprises tantalum powder, basic metal and alkali metal halide, the method comprise the steps: to comprise the mixture of tantalum powder, basic metal and alkali metal halide with the solution washing of acidic electrolyte bath.
2. method from the mixture purification tantalum powder that comprises tantalum powder, basic metal and alkali metal halide may further comprise the steps:
1) provides the mixture that comprises tantalum powder, basic metal and alkali metal halide;
The mixture that 2) will comprise tantalum powder, basic metal and alkali metal halide drops into the diafiltration groove of the aqueous solution contain acidic electrolyte bath, and (this diafiltration groove is preferably static diafiltration groove or with the dynamic diafiltration groove of stirring rake, be particularly preferably the dynamic diafiltration groove with stirring rake) in, the impurity such as aqueous solution eccysis basic metal haloid, K, Na and oxide compound thereof with acidic electrolyte bath, monitor simultaneously the pH of the aqueous solution, until when no longer changing without the compound particles of the visible an alkali metal salt of naked eyes and pH value of water solution, filter and obtain the first filter cake;
3) above-mentioned filter cake input is contained in the agitator treating groove of deionized water, carry out agitator treating, filter afterwards, obtain the second filter cake;
4) the second filter cake was put into the pickling tank pickling 2-4 hour, this pickling tank contains the aqueous solution of the mixture of hydrochloric acid, nitric acid, hydrofluoric acid and hydrogen peroxide, filter afterwards and obtain the 3rd filter cake, preferably, the total concn of hydrochloric acid, nitric acid, hydrofluoric acid and hydrogen peroxide is 10wt%, and can be arbitrary proportion between them;
5) oven dry of the 3rd filter cake is obtained the former powder of tantalum powder.
3. claim 1 or 2 method, wherein said acidic electrolyte bath is mineral acid or organic acid; Be preferably mineral acid; Further preferably, described acidic electrolyte bath is to be selected from a kind of in hydrochloric acid, nitric acid, sulfuric acid, the hydrofluoric acid or two or more mixture wherein, and more preferably, described acidic electrolyte bath is hydrochloric acid.
4. claim 1 or 2 method, the pH value of the aqueous solution of wherein said acidic electrolyte bath preferably＜6 is more preferably 3-5.
5. the process of claim 1 wherein that the diafiltration troughed belt has stirring rake, the mixing speed of stirring arm is＜60 rev/mins, is preferably＜30 rev/mins.
6. the process of claim 1 wherein the mixture that comprises tantalum powder, basic metal and alkali metal halide is provided in the following way: with sodium Metal 99.5 (Na) reduction tantalum potassium fluoride (K
2TaF
7), then cooling.
7. the process of claim 1 wherein step 1) comprise that also the mixture that will comprise tantalum powder, basic metal and alkali metal halide is broken into the fritter of size≤20mm, or be ground into powder.
8. claim 1 or 2 method, wherein basic metal is Na and/or potassium.
9. claim 1 or 2 method, wherein alkali metal halide is sodium-chlor, Repone K and/or Potassium monofluoride.
10. obtain the tantalum powder by each method among the claim 1-9.
11. obtain the purposes of tantalum powder in making electrolytic condenser by each method among the claim 1-9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105583406A (en) * | 2016-03-29 | 2016-05-18 | 宁夏东方钽业股份有限公司 | Preparation method of metal powder with low oxygen content |
| CN109468473A (en) * | 2018-12-29 | 2019-03-15 | 株洲硬质合金集团有限公司 | A kind of method of tantalum metallurgy by-product complex salt recycling and reusing |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4483819A (en) * | 1981-07-31 | 1984-11-20 | Hermann C. Starck Berlin | Production of highly capacitive agglomerated valve metal powder and valve metal electrodes for the production of electrolytic capacitors |
| JPS60145304A (en) * | 1984-01-09 | 1985-07-31 | Showa Kiyabotsuto Suupaa Metal Kk | Manufacture of tantalum powder |
| CN1052070A (en) * | 1989-11-20 | 1991-06-12 | 宁夏有色金属冶炼厂 | The production method of Ta powder used in capacitor |
| CN1240688A (en) * | 1998-07-07 | 2000-01-12 | 宁夏有色金属冶炼厂 | Technology for making tantalum powder |
| CN1382548A (en) * | 2002-03-30 | 2002-12-04 | 宁夏东方钽业股份有限公司 | Method for producing niobium and/or tantalum powder |
| CN101182602A (en) * | 2006-11-14 | 2008-05-21 | 宁夏东方钽业股份有限公司 | Tantalum and/or powder for powder metallurgy and method of producing the same |
-
2012
- 2012-12-18 CN CN201210548008.2A patent/CN102994780B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4483819A (en) * | 1981-07-31 | 1984-11-20 | Hermann C. Starck Berlin | Production of highly capacitive agglomerated valve metal powder and valve metal electrodes for the production of electrolytic capacitors |
| JPS60145304A (en) * | 1984-01-09 | 1985-07-31 | Showa Kiyabotsuto Suupaa Metal Kk | Manufacture of tantalum powder |
| CN1052070A (en) * | 1989-11-20 | 1991-06-12 | 宁夏有色金属冶炼厂 | The production method of Ta powder used in capacitor |
| CN1240688A (en) * | 1998-07-07 | 2000-01-12 | 宁夏有色金属冶炼厂 | Technology for making tantalum powder |
| CN1382548A (en) * | 2002-03-30 | 2002-12-04 | 宁夏东方钽业股份有限公司 | Method for producing niobium and/or tantalum powder |
| CN101182602A (en) * | 2006-11-14 | 2008-05-21 | 宁夏东方钽业股份有限公司 | Tantalum and/or powder for powder metallurgy and method of producing the same |
Non-Patent Citations (1)
| Title |
|---|
| 何季麟: "世界钽粉生产工艺的发展", 《中国工程科学》, vol. 3, no. 12, 31 December 2001 (2001-12-31), pages 85 - 89 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105583406A (en) * | 2016-03-29 | 2016-05-18 | 宁夏东方钽业股份有限公司 | Preparation method of metal powder with low oxygen content |
| CN105583406B (en) * | 2016-03-29 | 2018-12-11 | 宁夏东方钽业股份有限公司 | A kind of preparation method of low oxygen content metal powder |
| CN109468473A (en) * | 2018-12-29 | 2019-03-15 | 株洲硬质合金集团有限公司 | A kind of method of tantalum metallurgy by-product complex salt recycling and reusing |
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