US3058825A - Process for recovering columbium and tantalum from ores and ore concentrates containing same - Google Patents
Process for recovering columbium and tantalum from ores and ore concentrates containing same Download PDFInfo
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- US3058825A US3058825A US762386A US76238658A US3058825A US 3058825 A US3058825 A US 3058825A US 762386 A US762386 A US 762386A US 76238658 A US76238658 A US 76238658A US 3058825 A US3058825 A US 3058825A
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- 239000010955 niobium Substances 0.000 title claims description 24
- 239000012141 concentrate Substances 0.000 title claims description 21
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 19
- 229910052715 tantalum Inorganic materials 0.000 title claims description 17
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 87
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 17
- 229910052700 potassium Inorganic materials 0.000 claims description 17
- 239000011591 potassium Substances 0.000 claims description 17
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 16
- 230000029087 digestion Effects 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 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 5
- 239000000706 filtrate Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000012535 impurity Substances 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
- 239000000203 mixture Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003866 digestant Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 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
- 239000002244 precipitate Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003388 sodium compounds Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000011464 Pachycereus pringlei Nutrition 0.000 description 1
- 240000006939 Pachycereus weberi Species 0.000 description 1
- 235000011466 Pachycereus weberi Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000004326 stimulated echo acquisition mode for imaging Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/24—Obtaining niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
-
- 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
Definitions
- MIXER PREClPlTATE I sodium columbcie-toniolute
- CAKE sidlum columbute-iumolcte
- PAUL B. CARDON flZM ATTORNEYS -it is often given the United etates Patent 3,058,325 PRGCESS FOR RECGVERING COLUMBIUM AND TANTALUM FROM ORES AND ORE CONQEN- TRATES CONTADIING SAME Paul B. Cardon, 4815 Memory Lane, Murray, Utah Filed Sept. 22, E58, Ser. No. 762,336 Claims. (Cl.
- This invention relates to metallurgical processes for the recovery of columbium and tantalum from ores and ore concentrates in which these metals are found, and, in particular, to processes for recovering columbium and tantalum in the form of substantially pure compounds which may be used for various purposes, especially the production of the metals as such.
- Columbium has become important as a strategic material in the field of high temperature metallurgy, particularly as an alloying ingredient in the production of super alloys for jet aircraft and the like, such, for example, as heat-resistant alloys based on nickel and/or cobalt and containing chromium and one or more strengthening ingredients, for example, titanium, zirconium or aluminum.
- the addition of a small amount of columbium has a marked beneficial effect on the resistance to creep of such alloys at elevated temperatures.
- columbium is particularly useful as a carbide sta bilizer in stainless steel. Thus, a process which will recover columbium easily and substantially free from impurities, such as iron, manganese, titanium, tungsten, and silicon, is highly desirable.
- columbium and tantalum The most important source of columbium and tantalum at the present time is ore containing the minerals columbite and tantalite, although ores containing other columbium-tantalum minerals are known and becoming increasingly available.
- the ore is generally available as a high grade columbite-tantalite concentrate containing about ten times as much columbium oxide (Cb O as tantalum oxide (Ta O the main impurity being iron. Chemically, broad designation FeO(Cb,Ta) O even though other impurities than iron are present, for example SnO TiO and MnO An analysis of a typical concentrate shows about 66.10% Cb O 7.30% T3205, F60, S1102, Tioz,
- an aqueous solution of potassium hydroxide may be employed as a digestant under conditions of heat and pressure to break down the ore materials and yield salts of columbium and tantalum which may be relatively easily recovered.
- the reactants can be proportioned to yield a potassium columbatetantalate which is soluble in the digestant "solution, so as to be readily separable from insoluble waste materials, and that too much of the KOH will result in the formation of insoluble potassium columbate-tantalate salts.
- a principal object of the invention is to provide a new and relatively simple process for recovering columbium and/or tantalum values from ore and ore concentrates containing same.
- the invention is concerned with the breaking down of refractory types of columbium-tantalum ore materials, such as those containing the minerals columbite, tantalite, fergusonite, samarskite, and euxenite, by digestion thereof with KOH
- a highly important aspect is the obtaining of a particular, soluble, potassium columbate-tantalate salt by limiting the quantity of KOH employed.
- X-ray diffraction analysis has indicated that the particular salt desired is potassiummeta-columbate-tantalate, and that its production, as against other potassium columbates-tantalates which are insoluble in the leach solution, e.g. potassium-pyro-columbate-tantalate, depends upon the ratio between the potassium hydroxide in the digestant and the columbium-tantalum oxides in the ore material.
- the theoretical ratio for the reaction is two moles of the potassium hydroxide to one mole of the oxides. However, at this ratio, the solution isnt strong enough to yield an economic recovery in digestion of reasonable duration. Thus, an excess must be used. In accordance with preferred practice, the allowable excess prior to formation of such insoluble compounds as potassium-pyrocolumbate-tantalate provides the upper limit of the range of ratios permissible.
- Digestion of the raw ore material is ordinarily carried out in an autoclave at a temperature of about 400 F. and a pressure of about psi.
- the temperature andpressure may be varied somewhat depending upon the nature of the ore, the more refractory ores benefitting by higher temperatures.
- the time will also vary somewhat, depending both upon the nature of the ore and the ratio of KOH to the ore, the lowest possible ratio being, of course, the theoretical 2 to l mentioned above.
- a period of from one to three hours in the autoclave is generally sufficient to accomplish a satisfactory breaking down of the ore material, given a satisfactory excess of the KOH reactant.
- the character of the digestion product will depend largely upon the ratio of KOH to the columbium and tantalum oxides contained by the ore, as'will the recovery procedure following the digestion stage.
- insoluble potassium columbates-tantalates are formed by utilizing too much of the KOH reactant, it will be necessary to treat the resulting slurry for their separation from the insoluble waste materials
- Each mixture in turn was present, as, for example, by filtering and by treating the resulting filter cake with a mineral acid, to solubilize the iron, manganese, and other waste materials and to hydrolyze the potassium columbate-tantalate to hydrated columbium-tantalum oxides.
- the resulting oxide slurry can then be treated by known procedures, such as 801-; vent extraction, to obtain separated and purified columbium and tantalum oxides.
- a workable ratio of KOH to the combined columbium-tantalum oxides in the ore material is substantially within the molar range of from a ratio of about 4.47 to 1 to a ratio of about 5.26 to 1, while best results in most instances will be had with a ratio of about 4.72 to 1, all as is indicated by the table of typical test results appearing hereinafter.
- the digested slurry is filtered and the resulting pregnant filtrate solution is treated with a soluble sodium compound (NaOH, NaCl, etc.), preferably by mixing the filtrate solution with an aqueous solution of the sodium compound while introducing steam to heat the mixture, thereby producing a precipitate of sodium columbate-tantalate, which is inspective mixtures were treated for various times ranging from 1 hour to 3 hours.
- a soluble sodium compound NaOH, NaCl, etc.
- the digested material was filtered and washed, the filtrate and cake washings being allowed to cool and then being treated by the addition of an excess of the stoichiometric ratio of NaOH, to bring down a precipitate of sodium columbate-tantalate.
- a process for recovering columbium and tantalum from columbium-tantalum oxide ores and ore concentrates the step of digesting such an ore or ore concentrate under superatmospheric pressure with a hot aqueous solution of potassium hydroxide, to break down the ore or ore concentrate and form a potassium colum-bate-tantalate salt, the potassium hydroxide being present a ratio range of from a ratio of about 4.47 moles thereof to 1 mole of the combined columbium-tantalum oxides to a ratio of about 5.26 to 1, and the digestion product being a slurry in which the potassium columbate-tantalate salt is dissolved.
- this product can be subjected to hydrolysis with a 'mineral acid (preferably nitric) and to further treatment in known manner to yield separate, exceptionally high purity oxides for further treatment to produce the metals.
- a 'mineral acid preferably nitric
- a process for recovering columbium and tantalum from columbium-tantalum oxide ores and ore concentrates comprising digesting such an 'ore or ore concentrate under superatmospheric pressure with a hot aqueous solution of potassium hydroxide, to break down the ore or ore concentrate and form a potassium columbate-tantalate salt, the potassium hydroxide being present within a ratio range of from a ratio of about 4.47 moles thereof to 1 mole of the combined columbium-tantalum oxides to a ratio of about 5.26 to 1, and the digestion product being a slurry in which the potassium columbate-tantalate salt is dissolved; treating said slurry to separate the liquid phase from the solid phase; and precipitating sodium columbate-tantalate of exceptionally high purity from said slurry by introducing thereinto an excess of the stoichiometric amount of sodium ions.
- the ratio range is about 4.72 to 1.
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- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Description
Oct. 16, 1962 P. B. CARDON 3,058,825
PROCESS FOR RECOVERING COLUMBIUM AND TANTALUM FROM ORES AND ORE CONCENTRATES CONTAINING SAME Filed Sept. 22, 1958 COLUMBIUM-TANTALUM OXIDE ORE CONCENTRATE (approx. 200 mesh) AQUEOUS SOLUTION OF KOH (50%) (dAUTfO CL'AVE leslon o o rox.
400 F and I00 @551. CflGk d for about 2 hours) z gc e I SLURRY PREGNANT FILTRATE (pomssxum-metu-columbofe-'runtcla1e) AQUEOUS SOLUTION LIVE STEAM TO HEAT OF NOOH TO APPROX. 80C
MIXER PREClPlTATE I (sodium columbcie-toniolute) CAKE (sodlum columbute-iumolcte) FILTRATE FINAL PRODUCT TO WASTE INVENTOR. PAUL B. CARDON flZM ATTORNEYS -it is often given the United etates Patent 3,058,325 PRGCESS FOR RECGVERING COLUMBIUM AND TANTALUM FROM ORES AND ORE CONQEN- TRATES CONTADIING SAME Paul B. Cardon, 4815 Memory Lane, Murray, Utah Filed Sept. 22, E58, Ser. No. 762,336 Claims. (Cl. 75121) This invention relates to metallurgical processes for the recovery of columbium and tantalum from ores and ore concentrates in which these metals are found, and, in particular, to processes for recovering columbium and tantalum in the form of substantially pure compounds which may be used for various purposes, especially the production of the metals as such.
Columbium has become important as a strategic material in the field of high temperature metallurgy, particularly as an alloying ingredient in the production of super alloys for jet aircraft and the like, such, for example, as heat-resistant alloys based on nickel and/or cobalt and containing chromium and one or more strengthening ingredients, for example, titanium, zirconium or aluminum. The addition of a small amount of columbium has a marked beneficial effect on the resistance to creep of such alloys at elevated temperatures. Moreover, columbium is particularly useful as a carbide sta bilizer in stainless steel. Thus, a process which will recover columbium easily and substantially free from impurities, such as iron, manganese, titanium, tungsten, and silicon, is highly desirable.
The most important source of columbium and tantalum at the present time is ore containing the minerals columbite and tantalite, although ores containing other columbium-tantalum minerals are known and becoming increasingly available.
The ore is generally available as a high grade columbite-tantalite concentrate containing about ten times as much columbium oxide (Cb O as tantalum oxide (Ta O the main impurity being iron. Chemically, broad designation FeO(Cb,Ta) O even though other impurities than iron are present, for example SnO TiO and MnO An analysis of a typical concentrate shows about 66.10% Cb O 7.30% T3205, F60, S1102, Tioz,
Attempts at solubilizing the columbium-tantalum values have not been satisfactory in the past, although potassium hydroxide has been successfully employed in a fusion procedure requiring high temperatures and complicated treatment of the fusion product.
In accordance with this invention, I have found that an aqueous solution of potassium hydroxide may be employed as a digestant under conditions of heat and pressure to break down the ore materials and yield salts of columbium and tantalum which may be relatively easily recovered. In addition, I have found that the reactants can be proportioned to yield a potassium columbatetantalate which is soluble in the digestant "solution, so as to be readily separable from insoluble waste materials, and that too much of the KOH will result in the formation of insoluble potassium columbate-tantalate salts.
A principal object of the invention is to provide a new and relatively simple process for recovering columbium and/or tantalum values from ore and ore concentrates containing same.
3,658,825 Patented Oct. 16, 1962 ice which is a flow sheet indicating the presently preferred procedure in detail.
While, broadly speaking, the invention is concerned with the breaking down of refractory types of columbium-tantalum ore materials, such as those containing the minerals columbite, tantalite, fergusonite, samarskite, and euxenite, by digestion thereof with KOH, a highly important aspect is the obtaining of a particular, soluble, potassium columbate-tantalate salt by limiting the quantity of KOH employed. X-ray diffraction analysis has indicated that the particular salt desired is potassiummeta-columbate-tantalate, and that its production, as against other potassium columbates-tantalates which are insoluble in the leach solution, e.g. potassium-pyro-columbate-tantalate, depends upon the ratio between the potassium hydroxide in the digestant and the columbium-tantalum oxides in the ore material.
I have found that the reason ratio range is critical, so far as solubility of the resulting columbium-tantalum salt is concerned, is because excess potassium hydroxide at an elevated temperature reacts with the soluble potassiummeta-columbate-tantalate formed, to produce potassium columbate-tantalate salts (particularly potassium-pyrocolumbate-tantalate) which are insoluble in the leach liquid.
The theoretical reaction between a columbite-tantalite ore material and potassium hydroxide is:
The theoretical ratio for the reaction is two moles of the potassium hydroxide to one mole of the oxides. However, at this ratio, the solution isnt strong enough to yield an economic recovery in digestion of reasonable duration. Thus, an excess must be used. In accordance with preferred practice, the allowable excess prior to formation of such insoluble compounds as potassium-pyrocolumbate-tantalate provides the upper limit of the range of ratios permissible.
Digestion of the raw ore material is ordinarily carried out in an autoclave at a temperature of about 400 F. and a pressure of about psi. The temperature andpressure may be varied somewhat depending upon the nature of the ore, the more refractory ores benefitting by higher temperatures. The time will also vary somewhat, depending both upon the nature of the ore and the ratio of KOH to the ore, the lowest possible ratio being, of course, the theoretical 2 to l mentioned above. A period of from one to three hours in the autoclave is generally sufficient to accomplish a satisfactory breaking down of the ore material, given a satisfactory excess of the KOH reactant.
The character of the digestion product, as pointed out hereinbefore, will depend largely upon the ratio of KOH to the columbium and tantalum oxides contained by the ore, as'will the recovery procedure following the digestion stage. Where insoluble potassium columbates-tantalates are formed by utilizing too much of the KOH reactant, it will be necessary to treat the resulting slurry for their separation from the insoluble waste materials Each mixture in turn was present, as, for example, by filtering and by treating the resulting filter cake with a mineral acid, to solubilize the iron, manganese, and other waste materials and to hydrolyze the potassium columbate-tantalate to hydrated columbium-tantalum oxides. The resulting oxide slurry can then be treated by known procedures, such as 801-; vent extraction, to obtain separated and purified columbium and tantalum oxides.
The purity of the oxides so obtained, however, is not exceptionally high. Moreover, the procedure'is expensive. It is much preferable to control the KOH-oxides ratio to insure the formation of the soluble potassium-metacolumbate-tantalate, as previously indicated.
1 have found that a workable ratio of KOH to the combined columbium-tantalum oxides in the ore material is substantially within the molar range of from a ratio of about 4.47 to 1 to a ratio of about 5.26 to 1, while best results in most instances will be had with a ratio of about 4.72 to 1, all as is indicated by the table of typical test results appearing hereinafter.
In connection with the above, it should be noted that various factors have an influence upon workability near the upper limit of the specified workable range. Temperature and time variations, purity of the water and reagents, and the columbium-tantalum ratio and total composition of the ore all have an eifect upon the results. Thus, higher temperatures and prolonged time of treatment tend to lower recovery, while increased purity of water and reagents tend to raise the recovery. Increase in the ratio of columbium to tantalum tends to increase recovery, as does also high iron and low manganese, tin, and similar impurities.
' When the quantity of KOH exceeds the workable range noted above, breaking down of the ore by digestion with KOH will yield insoluble potassium columbate-tantalates not susceptible of recovery by the simple and advantageous procedure about to be described nor of yielding the exceptionally pure product otherwise obtainable. Ac cordingly, the percent recovery from any given run of an ore or ore concentrate through the autoclave will not be particularly high, although repeated runs will succeed in removing substantially all the columbium-tantalum present.
When digestion has been such as to yield a soluble potassium tantalate, as is preferred, the digested slurry is filtered and the resulting pregnant filtrate solution is treated with a soluble sodium compound (NaOH, NaCl, etc.), preferably by mixing the filtrate solution with an aqueous solution of the sodium compound while introducing steam to heat the mixture, thereby producing a precipitate of sodium columbate-tantalate, which is inspective mixtures were treated for various times ranging from 1 hour to 3 hours. The digested material was filtered and washed, the filtrate and cake washings being allowed to cool and then being treated by the addition of an excess of the stoichiometric ratio of NaOH, to bring down a precipitate of sodium columbate-tantalate.
The results obtained are given in the following table:
Molar Ore KOH Water Ratio Time Percent (gm) (85% (cc.) KOH-Ore (hrs.) Extraction 100 118 100 7. 06:1 1 0. 0 125 118 100 5. 65: 1 1 0. O 150. 4 100 100 4. 72:1 2 66. 67 150 100 100 4. 72:1 2 67. 7 150 100 100 4. 72:1 1 66 108 56 50 3. 27:1 3 O. O 130 91 91 4. 47:1 3 52. 3 130 97 97 5. 26 :1 3 52. 3 130 94 94 5. 13:1 3 52. 2
Thus, while KOH digestion of a columbium-tantalum ore is useful with unrestricted ratio of KOH to the columbium-tantalum oxides in the ore above the theoretical necessary to produce a optassium colum'bate-tantalate, it is much preferable, from the standpoint of overall processing, to restrict the ratio substantially in accordance with the above results, which indicate the extent of solubility of the potassium columbates-tantalates produced by the digestion.
Whereas this invention is here disclosed with particular reference to specific procedures, it should be understood that various modifications may be made without departing from the essential inventive concepts.
I claim:
1. In a process for recovering columbium and tantalum from columbium-tantalum oxide ores and ore concentrates, the step of digesting such an ore or ore concentrate under superatmospheric pressure with a hot aqueous solution of potassium hydroxide, to break down the ore or ore concentrate and form a potassium colum-bate-tantalate salt, the potassium hydroxide being present a ratio range of from a ratio of about 4.47 moles thereof to 1 mole of the combined columbium-tantalum oxides to a ratio of about 5.26 to 1, and the digestion product being a slurry in which the potassium columbate-tantalate salt is dissolved.
2. The process of claim 1, wherein the ratio range is about 4.72 to 1.
soluble so long as an excess of sodium ions is maintained during the precipitation step. a
. The precipitate is filtered and the resulting filter cake washed with a dilute solution of the sodium compound to yield a sodium columbate-tantalate product of exceptionally high purity. If desired, this product can be subjected to hydrolysis with a 'mineral acid (preferably nitric) and to further treatment in known manner to yield separate, exceptionally high purity oxides for further treatment to produce the metals.
Typical laboratory procedures and results upon which this invention is based are as follows:
A Nigerian concentrate containing about 73.4% in the aggregate of (317 0 and Ta O (66.1% Cb O 7.3% Ta O 18.53% FeO, 1.84% SnO 2.0%
Given amounts of the ground ore were mixed with a solution comprising about 50% by weight of potassium hydroxide, the amount of solution used in each instance being dependent upon the molar ratio of anhydrous KOH to the combined colunrbium-tantalum oxides in the ore.
put into a high pressure autoclave' and digested at a pressure of about 100 p.s.i. (gauge reading) and a temperature of about 400 F. The re- TiO 1.48% V MnO) was ground to substantially minus 200 mesh.
3. A process for recovering columbium and tantalum from columbium-tantalum oxide ores and ore concentrates, comprising digesting such an 'ore or ore concentrate under superatmospheric pressure with a hot aqueous solution of potassium hydroxide, to break down the ore or ore concentrate and form a potassium columbate-tantalate salt, the potassium hydroxide being present within a ratio range of from a ratio of about 4.47 moles thereof to 1 mole of the combined columbium-tantalum oxides to a ratio of about 5.26 to 1, and the digestion product being a slurry in which the potassium columbate-tantalate salt is dissolved; treating said slurry to separate the liquid phase from the solid phase; and precipitating sodium columbate-tantalate of exceptionally high purity from said slurry by introducing thereinto an excess of the stoichiometric amount of sodium ions. 1 4. The process of claim 3, wherein the ratio range is about 4.72 to 1.
1 5. In a process for recovering columbium and tantalum from columbium-tantalum oxide ores and ore concentrates, the step of digesting such an ore or ore concentrate under superatmospheric pressure with a hot aqueous solution of potassium hydroxide, to break down the ore or ore concentrate and form a potassium colum'bate-tantalate salt, the potassium hydroxide being present in at 2,819,945 Ruhoff et a1. Jan. 14, 1958 least the stoichiometric amount required for the reaction. 2,956,857 Ruhofl. et al. Oct. 18, 1960 References Cited in the file of this patent OTHER REFERENCES Hampel: Rare Metals Handbook, Reinhold Publishing UNITED STATES PATENTS 5 1,908,473 Cunningham et al. May 9, 1933 Corp., New York, 1954, p. 391.
Claims (1)
1. IN A PROCESS FOR RECOVERING COLUMBIUM AND TANTALUM FROM COLUMNIUM-TANTALUM OXIDE ORES AND ORE CONCENTRATES, THE STEP OF DIGESTING SUCH AN ORE OR ORE CONCENTRATE UNDER SUPERATMOSPHERIC PRESSURE WITH A HOT AQUEOUS SOLUTION OF POTASSIUM HYDROXIDE, TO BREAK DOWN THE ORE OR ORE CONCENTRATE AND FORM A POTASSIUM COLUMBATE-TANTALATE SALT, THE POTASSIUM HYDROXIDE BEING PRESENT WITHIN A RATIO RANGE OF FROM A RATIO OF ABOUT 4.47 MOLES THEREOF TO 1 MOLE OF THE COMBINED COLUMBIUM-TANTALUM OXIDES TO A RATIO OF ABOUT 5.26 TO 1, AND THE DIGESTION PRODUCT BEING A SLURRY IN WHICH THE POTASSIUM COLUMBATE-TANTALATE SALT IS DISSOLVED.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US762386A US3058825A (en) | 1958-09-22 | 1958-09-22 | Process for recovering columbium and tantalum from ores and ore concentrates containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US762386A US3058825A (en) | 1958-09-22 | 1958-09-22 | Process for recovering columbium and tantalum from ores and ore concentrates containing same |
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| Publication Number | Publication Date |
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| US3058825A true US3058825A (en) | 1962-10-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US762386A Expired - Lifetime US3058825A (en) | 1958-09-22 | 1958-09-22 | Process for recovering columbium and tantalum from ores and ore concentrates containing same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3099526A (en) * | 1961-08-09 | 1963-07-30 | Wah Chang Corp | Recovery of earth acids from slag |
| US3607006A (en) * | 1970-01-05 | 1971-09-21 | Molybdenum Corp | Process for recovery of columbium |
| US3640679A (en) * | 1969-02-06 | 1972-02-08 | Molybdenum Corp | Process for recovery of columbium |
| CN103160684A (en) * | 2011-12-15 | 2013-06-19 | 中国科学院过程工程研究所 | Method for extracting tantalum and niobium through low alkali decomposition of tantalum-niobium ore |
| CN103572046A (en) * | 2012-07-23 | 2014-02-12 | 中国科学院过程工程研究所 | Method for dissolving niobium-tantalum ore with KOH for extracting niobium and tantalum |
| WO2015004375A1 (en) * | 2013-07-09 | 2015-01-15 | Eramet | Method for purifying niobium and/tantalum |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1908473A (en) * | 1931-05-09 | 1933-05-09 | Kemet Lab Co Inc | Separation of tantalum from columbium |
| US2819945A (en) * | 1955-02-15 | 1958-01-14 | Mallinckrodt Chemical Works | Method of separating values of columbium and/or tantalum from a concentrate also containing an element of group iv b |
| US2956857A (en) * | 1957-11-25 | 1960-10-18 | Mallinckrodt Chemical Works | Methods of decomposing complex uranium-rare earth tantalo-columbates |
-
1958
- 1958-09-22 US US762386A patent/US3058825A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1908473A (en) * | 1931-05-09 | 1933-05-09 | Kemet Lab Co Inc | Separation of tantalum from columbium |
| US2819945A (en) * | 1955-02-15 | 1958-01-14 | Mallinckrodt Chemical Works | Method of separating values of columbium and/or tantalum from a concentrate also containing an element of group iv b |
| US2956857A (en) * | 1957-11-25 | 1960-10-18 | Mallinckrodt Chemical Works | Methods of decomposing complex uranium-rare earth tantalo-columbates |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3099526A (en) * | 1961-08-09 | 1963-07-30 | Wah Chang Corp | Recovery of earth acids from slag |
| US3640679A (en) * | 1969-02-06 | 1972-02-08 | Molybdenum Corp | Process for recovery of columbium |
| US3607006A (en) * | 1970-01-05 | 1971-09-21 | Molybdenum Corp | Process for recovery of columbium |
| CN103160684A (en) * | 2011-12-15 | 2013-06-19 | 中国科学院过程工程研究所 | Method for extracting tantalum and niobium through low alkali decomposition of tantalum-niobium ore |
| CN103572046A (en) * | 2012-07-23 | 2014-02-12 | 中国科学院过程工程研究所 | Method for dissolving niobium-tantalum ore with KOH for extracting niobium and tantalum |
| WO2015004375A1 (en) * | 2013-07-09 | 2015-01-15 | Eramet | Method for purifying niobium and/tantalum |
| FR3008425A1 (en) * | 2013-07-09 | 2015-01-16 | Eramet | PROCESS FOR PURIFYING NIOBIUM AND / OR TANTALE |
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