CA2090919C - Process for isolating tantalum and niobium - Google Patents
Process for isolating tantalum and niobium Download PDFInfo
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- CA2090919C CA2090919C CA 2090919 CA2090919A CA2090919C CA 2090919 C CA2090919 C CA 2090919C CA 2090919 CA2090919 CA 2090919 CA 2090919 A CA2090919 A CA 2090919A CA 2090919 C CA2090919 C CA 2090919C
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- 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
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Abstract
The present invention relates to a hydrometallurgical process for isolating tantalum and niobium from raw materials containing tantalum and niobium by treatment with pure hydrofluoric acid or a mixture of hydrofluoric acid and sulphuric acid, followed by solvent extraction of the tantalum and niobium fluoro-complexes from the treatment solution using methylisobutyl ketone (MIBK) and steam distillation of the organic ketone phase containing tantalum and niobium, to produce a new aqueous which is contactable by fresh MIBK to selectively extract tantalum.
Description
St/bo/2E-w A process for isolating tantalum and niobium Field and Bac~ound of the Invention The present invention relates to a hydrometallurgical process for isolating tantalum and niobium from raw materials which contain tantalum and niobium by treatment with pure hy~ofluoric acid or a mixture of hydrofluoric acid and sulphuric acid, followed by solvent extraction of the tantalum and niobium complexes from the treatment solution using methylisobutyl ketone and steam distillation of the organic ketone phase containing tantalum and niobium.
'Tantalum and niobium occur together in most natural sources. Different proportions of the two elements, however, characterise the ores and their geological deposits. Niobium is in principle obtained from columbite ore and/or pyrochlore ore from Brazil and Canada and other regions. These ores, however contain only small amounts of tantalum.
Tantalum-rich ores, such as e.g. tantalite, contain correspondingly small amounts of ~o~um.
To isolate tantalum and niobium, however, it is mainly slags which are produced during the isolation of tin (Thailand, Brazil) which are also used. These tin slags are now regarded as the most important raw material source for the two elements, although they only contain small amounts of niobium and tantalum. Also, very variable Ta/Nb ratios are encountered in these tin stags.
Normally, the two metals and their compounds are isolated indirectly from raw materials containing very little tantalum and niobium, such as e.g. tin stags, by fusion metallurgical enrichment methods for the two elements. Only the synthetic tantalum/niobium concentrates obtained in this way are available for economic wet chemical processing.
Among these tin stags there are now also those which, like natural columbite, contain tantalum in a very unfavourable Ta/Nb ratio, i.e. they contain small amounts of tantalum but are rich in niobium. The normal hydrometallurgical treatment and separation processes cannot be applied to these, for economic reasons, because these processes require a Ta/Nb ratio of at least 1:3 in the concentrate which is used.
S,~A 37-Foreign Countries - 1 -20909~J
The conventional hydrometallurgical process for isolating tantalum or niobium, disclosed in US Patent 3,117,833, comprises treatment of the tantalum/niobium raw material in mineral acids, preferably hydrofluoric/sulphuric acid mixtures. Tantalum and niobium are thereby dissolved together as fluoro-complexes and subsequently separated first from accompanying elements and then from each other, using a mufti-stage solvent extraction with MIBK (methylisobutyl ketone, 2-methyl-pentan -4- one). Here, the fluoroniobates or fluorotantalates are selectively re-extracted in sequence and further processed to give pure tantalum or niobium compounds.
In detail, this takes place by selectively removing the niobium from the organic ketone phi ~'~'~ch contains niobium and tantalum, e.g. with dilute sulphuric acid, while tantalum remaining in the organic phase may be re-extracted from that using water.
However, if materials which are rich in niobium but contain very little tantalum are used, then at this point the tantalum is present in very low concentration in the organic ketone phase. This means that there is a very poor volume/time yield, which makes the process uneconomical.
In addition, US Patent 3,403,983 discloses a process for the preparation of an aqueous solution of niobium and/or tantalum fluoro-complexes from a solution of fluoro-complexes of these metals in a steam-volatile, organic solvent which is virtually miscible with water, wherein a solution of the fluoro-complexes of these metals in the organic solvent, which is obtained using the known mufti-stage extraction of the metals from ores, is subjected to a steam distillation process with quantitative evaporation of the solvent to produce a non-distilled aqueous solution which contains the fluoro-complexes in a higher concentration than was present in the organic solvent.
.Lms should mean that the problem of emulsion formation is avoided, the organic solvents are easily recovered and recycled, an aqueous solution of niobium and/or tantalum fluoro-complexes with three- to four-fold higher concentrations than in solution in the organic solvent is obtained and the aqueous product solution is highly suitable for the economic crystallisation of K2TaF7.
This does n<at <~pply :i.n part: ici:~lar, therefore, to niobium/tantalum complexes which conta.ir; very little tantalum.
'Therefore, t hei_~e is a need t:o~: a process for economically isolating tantalum from starting materials which contain very lit~tlE, tantalum arn~ pat the same time are rich in niobium, using a wet chemi.ca7_ treatment and extraction process, without an indirect fusion metallurgical process being required beforehand. xn aGddition, all the niobium should also be i:;olated..
S umm.a r~
According tc trze invention, thie raw material containing tantalum and niobium, e.g. t::i.n slugs, niobium ores and/or concentrat:es, is treaty=c~ wit h pure hydrofluoric acid or a mixture of ~nydx-ofluoricv ac:,~:id and sulphuric acid and the acid solution is extracted fi_r~st with MTBK
(methylisobutyl ket.one), wherein rriob:iunc and tantalum pass into the organi~~ phase together. No:r-mally, t: he sum of the transition meta:is, ca:lcul.ated as their c.xides, is expressed as "combined oxides" ~;abf>rev.: "C".O."n. The niobium is not now selectively re-extracted from the organic phase using mineral acids or watew, as is usual, but: the ketone phase containing the C.O. i:~ subjected to ~~team distillation.
This measure means that both valuab=LEa sL:bstances are converted into an aqueeou~~ pha~~e in <~ kzighly concentrated form. The tantalum is now select:ivel.y extracted from this aqueous phase using fresh ketone (MIBK), while the niobium remains in the aqueou~~ phase.
This .invention thus comprises a hydrometal7_urgical process for isolating tarutalurn and niobium from :raw materials containing tarrt.alum and n:i.ob.~.L:~m by treatment with pure hydrofluor_Lc acid o:r a m:i_xture of lydrof_luo.ric acid and 3 ._ sulphuric acid, followed by solvent extraction of the tantalum and niobium flu~~ro-complexes f~:~om the treatment solution using methylisobut.yl ketc~ne an~:i steam distillation of the organic ketone ph;~sF~ containing ;.:antalum and .niobium, wherein the tantalum is selective'y extrvacted from the newly produced aqueous phase witru fresru metriy.isobutyl ketone, while all the niobium remains ~.n:~ the aqueous phase.
3 <~ ._ By selecting the ratio between the organic and aqueous phases, the amount of tantalum in the new MIBK phase may be adjusted to the desired concentration. If this organic phase is subjected to a further steam distillation process, there is another increase in the concentration of tantalum in the new aqueous phase. A preferred embodiment of the process according to the invention comprises treating the new organic ketone phase ~n~g ~~~ ~~ steam and thereby re-extracting the tantalum. The new concentrated tantalum solution may then be further processed in known ways.
The process according to the invention is advantageously useable for various ' tantalum/niobium raw materials. It confers particular advantages if there is a Ta:Nb ratio i 5 of 50.2 in the raw materials containing tantalum and niobium. Preferably, the process may be applied to columbite ores and/or tin stags with a Ta:Nb ratio of 1:5 to 1:15.
Detailed Description of Preferred Embodements The invention is explained in more detail in the following by way of example, without this being regarded as a limitation.
~o~oo~o Example A columbite ore with 35% by weight of Nb205 and 4% by weight of Ta205, the remainder being Si02, FeO, Mn02, Ti02 and other impurities, was treated with ?0%
strength pure hydrofluoric acid. This produced a solution with 135 g/1 of G.O.
i 0 (- Combined Oxides, Nb205 and Ta205) and an acidity of 20 N. The Ta:Nb ratio in this starting solution was about 1:9, corresponding to the starting material. This feed solution was passed against an organic phase consisting of methylisobutyl ketone (MIBK) in a counter-stream solvent extraction unit. The raffinate was sufficiently free of valuable material, with 0.3 g/1 of C.O. The ketone phase containing 89 g/1 of C.O. was now '"shed with a little 12 normal sulphuric acid, in order to remove residual impurities of other elements which had also been extracted. The ketone phase containing niobium and tantalum was sluiced out and subjected to steam distillation. 1301/h TaNb MIBK
were continuously fed to the top of a destillation column whereas 501/h steam were fed to the bottom of this column. The MIBK was totally distilled off and 35-401/h of a concentrated 2o Niobium- and Tantalum solution remained behind. These elements were present as fluoro-complexes in a concentration ratio of 20 g/1 Ta205 and 180 g/1 Nb205 (Ta:Nb =
1:9). Due to the relatively low acidity of the aqueous phase of this steam distillation process the tantalum now was selectively extracted by contacting 401/h of this aqueous solution with 51/h of fresh unloaded MIBK while the niobium (180 g/1 Nb205) remained m the aqueous phase and was worked up separately. The resulting organic phase containing tantalum (with 140 g/1 Ta205) was again treated with steam (31 Ta MIBK /
11 steam) which totally removed the MIBK from the system and produced the concentrated aqueous solution of tantalum fluorid (with >200 g/1 of Ta205 equivalent).
This was converted into the endproduct potassium hepta fluorotantalate (1,4 kg) by the addition of KCl in the usual way as described for example in US Patent 3,051,547.
Comparison example (according to US Patent 3,117,833) The niobium/tantalum solution produced from treatment of the ore used in example 1 was, as in example 1, passed against an organic phase consisting of methylisobutyl ketone (MIBK) in a counter-stream solvent extraction unit. The ketone phase, containing 90 g/1 of C.O., was now washed with a little 12 normal sulphuric acid, in order to remove residual impurities of other elements which had also been extracted. The niobium was selectively and completely converted into an aqueous phase, in the usual way, by stripping it from the ketone phase containing niobium and tantalum with 2 N
sulphuric acid and this was used as a sulphuric acid niobium fluoride solution to isolate niobium hydroxide. The ketone phase, now only containing tantalum, with 7.5 g/1 of Ta205, was freed of ketone by steam distillation and converted into an aqueous phase containing Q5 g/1 of Ta205. This solution, with the relatively low tantalum content, is not suitable for economic further processing since it either requires too much heat energy for evaporation or leaves behind too much salt-laden waste water, if tantalum hydroxide is produced from it.
'Tantalum and niobium occur together in most natural sources. Different proportions of the two elements, however, characterise the ores and their geological deposits. Niobium is in principle obtained from columbite ore and/or pyrochlore ore from Brazil and Canada and other regions. These ores, however contain only small amounts of tantalum.
Tantalum-rich ores, such as e.g. tantalite, contain correspondingly small amounts of ~o~um.
To isolate tantalum and niobium, however, it is mainly slags which are produced during the isolation of tin (Thailand, Brazil) which are also used. These tin slags are now regarded as the most important raw material source for the two elements, although they only contain small amounts of niobium and tantalum. Also, very variable Ta/Nb ratios are encountered in these tin stags.
Normally, the two metals and their compounds are isolated indirectly from raw materials containing very little tantalum and niobium, such as e.g. tin stags, by fusion metallurgical enrichment methods for the two elements. Only the synthetic tantalum/niobium concentrates obtained in this way are available for economic wet chemical processing.
Among these tin stags there are now also those which, like natural columbite, contain tantalum in a very unfavourable Ta/Nb ratio, i.e. they contain small amounts of tantalum but are rich in niobium. The normal hydrometallurgical treatment and separation processes cannot be applied to these, for economic reasons, because these processes require a Ta/Nb ratio of at least 1:3 in the concentrate which is used.
S,~A 37-Foreign Countries - 1 -20909~J
The conventional hydrometallurgical process for isolating tantalum or niobium, disclosed in US Patent 3,117,833, comprises treatment of the tantalum/niobium raw material in mineral acids, preferably hydrofluoric/sulphuric acid mixtures. Tantalum and niobium are thereby dissolved together as fluoro-complexes and subsequently separated first from accompanying elements and then from each other, using a mufti-stage solvent extraction with MIBK (methylisobutyl ketone, 2-methyl-pentan -4- one). Here, the fluoroniobates or fluorotantalates are selectively re-extracted in sequence and further processed to give pure tantalum or niobium compounds.
In detail, this takes place by selectively removing the niobium from the organic ketone phi ~'~'~ch contains niobium and tantalum, e.g. with dilute sulphuric acid, while tantalum remaining in the organic phase may be re-extracted from that using water.
However, if materials which are rich in niobium but contain very little tantalum are used, then at this point the tantalum is present in very low concentration in the organic ketone phase. This means that there is a very poor volume/time yield, which makes the process uneconomical.
In addition, US Patent 3,403,983 discloses a process for the preparation of an aqueous solution of niobium and/or tantalum fluoro-complexes from a solution of fluoro-complexes of these metals in a steam-volatile, organic solvent which is virtually miscible with water, wherein a solution of the fluoro-complexes of these metals in the organic solvent, which is obtained using the known mufti-stage extraction of the metals from ores, is subjected to a steam distillation process with quantitative evaporation of the solvent to produce a non-distilled aqueous solution which contains the fluoro-complexes in a higher concentration than was present in the organic solvent.
.Lms should mean that the problem of emulsion formation is avoided, the organic solvents are easily recovered and recycled, an aqueous solution of niobium and/or tantalum fluoro-complexes with three- to four-fold higher concentrations than in solution in the organic solvent is obtained and the aqueous product solution is highly suitable for the economic crystallisation of K2TaF7.
This does n<at <~pply :i.n part: ici:~lar, therefore, to niobium/tantalum complexes which conta.ir; very little tantalum.
'Therefore, t hei_~e is a need t:o~: a process for economically isolating tantalum from starting materials which contain very lit~tlE, tantalum arn~ pat the same time are rich in niobium, using a wet chemi.ca7_ treatment and extraction process, without an indirect fusion metallurgical process being required beforehand. xn aGddition, all the niobium should also be i:;olated..
S umm.a r~
According tc trze invention, thie raw material containing tantalum and niobium, e.g. t::i.n slugs, niobium ores and/or concentrat:es, is treaty=c~ wit h pure hydrofluoric acid or a mixture of ~nydx-ofluoricv ac:,~:id and sulphuric acid and the acid solution is extracted fi_r~st with MTBK
(methylisobutyl ket.one), wherein rriob:iunc and tantalum pass into the organi~~ phase together. No:r-mally, t: he sum of the transition meta:is, ca:lcul.ated as their c.xides, is expressed as "combined oxides" ~;abf>rev.: "C".O."n. The niobium is not now selectively re-extracted from the organic phase using mineral acids or watew, as is usual, but: the ketone phase containing the C.O. i:~ subjected to ~~team distillation.
This measure means that both valuab=LEa sL:bstances are converted into an aqueeou~~ pha~~e in <~ kzighly concentrated form. The tantalum is now select:ivel.y extracted from this aqueous phase using fresh ketone (MIBK), while the niobium remains in the aqueou~~ phase.
This .invention thus comprises a hydrometal7_urgical process for isolating tarutalurn and niobium from :raw materials containing tarrt.alum and n:i.ob.~.L:~m by treatment with pure hydrofluor_Lc acid o:r a m:i_xture of lydrof_luo.ric acid and 3 ._ sulphuric acid, followed by solvent extraction of the tantalum and niobium flu~~ro-complexes f~:~om the treatment solution using methylisobut.yl ketc~ne an~:i steam distillation of the organic ketone ph;~sF~ containing ;.:antalum and .niobium, wherein the tantalum is selective'y extrvacted from the newly produced aqueous phase witru fresru metriy.isobutyl ketone, while all the niobium remains ~.n:~ the aqueous phase.
3 <~ ._ By selecting the ratio between the organic and aqueous phases, the amount of tantalum in the new MIBK phase may be adjusted to the desired concentration. If this organic phase is subjected to a further steam distillation process, there is another increase in the concentration of tantalum in the new aqueous phase. A preferred embodiment of the process according to the invention comprises treating the new organic ketone phase ~n~g ~~~ ~~ steam and thereby re-extracting the tantalum. The new concentrated tantalum solution may then be further processed in known ways.
The process according to the invention is advantageously useable for various ' tantalum/niobium raw materials. It confers particular advantages if there is a Ta:Nb ratio i 5 of 50.2 in the raw materials containing tantalum and niobium. Preferably, the process may be applied to columbite ores and/or tin stags with a Ta:Nb ratio of 1:5 to 1:15.
Detailed Description of Preferred Embodements The invention is explained in more detail in the following by way of example, without this being regarded as a limitation.
~o~oo~o Example A columbite ore with 35% by weight of Nb205 and 4% by weight of Ta205, the remainder being Si02, FeO, Mn02, Ti02 and other impurities, was treated with ?0%
strength pure hydrofluoric acid. This produced a solution with 135 g/1 of G.O.
i 0 (- Combined Oxides, Nb205 and Ta205) and an acidity of 20 N. The Ta:Nb ratio in this starting solution was about 1:9, corresponding to the starting material. This feed solution was passed against an organic phase consisting of methylisobutyl ketone (MIBK) in a counter-stream solvent extraction unit. The raffinate was sufficiently free of valuable material, with 0.3 g/1 of C.O. The ketone phase containing 89 g/1 of C.O. was now '"shed with a little 12 normal sulphuric acid, in order to remove residual impurities of other elements which had also been extracted. The ketone phase containing niobium and tantalum was sluiced out and subjected to steam distillation. 1301/h TaNb MIBK
were continuously fed to the top of a destillation column whereas 501/h steam were fed to the bottom of this column. The MIBK was totally distilled off and 35-401/h of a concentrated 2o Niobium- and Tantalum solution remained behind. These elements were present as fluoro-complexes in a concentration ratio of 20 g/1 Ta205 and 180 g/1 Nb205 (Ta:Nb =
1:9). Due to the relatively low acidity of the aqueous phase of this steam distillation process the tantalum now was selectively extracted by contacting 401/h of this aqueous solution with 51/h of fresh unloaded MIBK while the niobium (180 g/1 Nb205) remained m the aqueous phase and was worked up separately. The resulting organic phase containing tantalum (with 140 g/1 Ta205) was again treated with steam (31 Ta MIBK /
11 steam) which totally removed the MIBK from the system and produced the concentrated aqueous solution of tantalum fluorid (with >200 g/1 of Ta205 equivalent).
This was converted into the endproduct potassium hepta fluorotantalate (1,4 kg) by the addition of KCl in the usual way as described for example in US Patent 3,051,547.
Comparison example (according to US Patent 3,117,833) The niobium/tantalum solution produced from treatment of the ore used in example 1 was, as in example 1, passed against an organic phase consisting of methylisobutyl ketone (MIBK) in a counter-stream solvent extraction unit. The ketone phase, containing 90 g/1 of C.O., was now washed with a little 12 normal sulphuric acid, in order to remove residual impurities of other elements which had also been extracted. The niobium was selectively and completely converted into an aqueous phase, in the usual way, by stripping it from the ketone phase containing niobium and tantalum with 2 N
sulphuric acid and this was used as a sulphuric acid niobium fluoride solution to isolate niobium hydroxide. The ketone phase, now only containing tantalum, with 7.5 g/1 of Ta205, was freed of ketone by steam distillation and converted into an aqueous phase containing Q5 g/1 of Ta205. This solution, with the relatively low tantalum content, is not suitable for economic further processing since it either requires too much heat energy for evaporation or leaves behind too much salt-laden waste water, if tantalum hydroxide is produced from it.
Claims (5)
1. ~A hydrometallurgical process for isolating tantalum and niobium from a raw material containing tantalum and niobium by an aqueous treatment solution comprising pure hydrofluoric acid or a mixture of hydrofluoric acid and sulphuric acid, followed by; (a) solvent extraction of the resultant tantalum and niobium fluoro-complexes from the aqueous treatment solution using methylisobutyl ketone (MIBK) (b) steam distillation of the MIBK phase which contains tantalum and niobium to produce an aqueous phase, and (c) the tantalum is selectively extracted from aqueous phase thus produced, using fresh MIBK, while all the niobium remains in the aqueous phase.
2. ~A process according to claim 1, wherein the fresh MIBK phase containing tantalum is treated again with steam and the tantalum is thereby re-extracted.
3. ~A process according to claim 1 or 2, wherein a Ta/Nb ratio of <=0.2 is present in the raw material which contains tantalum and niobium.
4. ~A process according to claim 1 or 2, wherein the raw material is columbite, tin slag or a mixture thereof with a Ta:Nb ratio of from 1:5 to 1;15.
5. ~A process according to any one of claims 1 to 4, wherein the distilled-off MIBK phase is condensed and reused in steps (a), (c) or both.
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Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4207145.3-24 | 1992-03-06 | ||
| DE19924207145 DE4207145C1 (en) | 1992-03-06 | 1992-03-06 | Hydro:methallurgical process for recovery of tantalum and niobium - by digesting material e.g. columbite ore with hydrofluoric acid followed by solvent extn. of formed fluoro:complexes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2090919A1 CA2090919A1 (en) | 1993-09-07 |
| CA2090919C true CA2090919C (en) | 2004-09-21 |
Family
ID=6453416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2090919 Expired - Fee Related CA2090919C (en) | 1992-03-06 | 1993-03-03 | Process for isolating tantalum and niobium |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH0610074A (en) |
| CN (1) | CN1041753C (en) |
| AT (1) | AT398209B (en) |
| AU (1) | AU653674B2 (en) |
| BE (1) | BE1006385A3 (en) |
| BR (1) | BR9300739A (en) |
| CA (1) | CA2090919C (en) |
| DE (1) | DE4207145C1 (en) |
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| RU2623570C1 (en) * | 2016-07-06 | 2017-06-27 | Федеральное государственное бюджетное учреждение науки Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук (ИХТРЭМС КНЦ РАН) | Method of processing of the tantalone-biobase concentrate |
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| CN115109948B (en) * | 2022-06-20 | 2023-10-27 | 北京工业大学 | Tantalum-niobium extraction and separation method and application thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3117833A (en) * | 1958-09-25 | 1964-01-14 | Fansteel Metallurgical Corp | Process of purifying and separating columbium and tantalum values from each other |
| US3403983A (en) * | 1965-01-11 | 1968-10-01 | Mallinckrodt Chemical Works | Steam distillation of metal values in solution |
| DE1767674C2 (en) * | 1968-06-04 | 1982-04-22 | Mallinckrodt, Inc., 63134 St. Louis, Mo. | Process for the preparation of an aqueous solution of niobium and / or tantalum fluorine complexes |
| US3712939A (en) * | 1971-03-29 | 1973-01-23 | Union Carbide Corp | Method for recovering tantalum and/or columbium |
| CA1144376A (en) * | 1980-06-02 | 1983-04-12 | Gilles Legault | Leaching process for niobium and (or) tantalum minerals |
| US4518570A (en) * | 1983-11-07 | 1985-05-21 | Cabot Corporation | Process for separating antimony from columbium solutions |
| FR2636939B1 (en) * | 1988-09-06 | 1991-08-30 | Inst Nat Rech Chimique | IMPROVED PROCESS FOR OBTAINING TA AND / OR NB COMPOUNDS FREE OF IMPURITIES FROM MATERIALS CONTAINING THESE METALS |
| DE4021207A1 (en) * | 1990-07-03 | 1992-01-16 | Starck Hermann C Fa | PROCESS FOR OBTAINING AND SEPARATING TANTAL AND NIOB |
-
1992
- 1992-03-06 DE DE19924207145 patent/DE4207145C1/en not_active Expired - Fee Related
-
1993
- 1993-02-04 AT AT19193A patent/AT398209B/en not_active IP Right Cessation
- 1993-03-01 AU AU33906/93A patent/AU653674B2/en not_active Expired
- 1993-03-02 JP JP6481293A patent/JPH0610074A/en active Pending
- 1993-03-03 BE BE9300201A patent/BE1006385A3/en not_active IP Right Cessation
- 1993-03-03 CA CA 2090919 patent/CA2090919C/en not_active Expired - Fee Related
- 1993-03-04 BR BR9300739A patent/BR9300739A/en not_active IP Right Cessation
- 1993-03-06 CN CN93102409A patent/CN1041753C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7431782B2 (en) | 1998-11-25 | 2008-10-07 | Cabot Corporation | High purity tantalum, products containing the same, and methods of making the same |
| US7585380B2 (en) | 1998-11-25 | 2009-09-08 | Cabot Corporation | High purity tantalum, products containing the same, and methods of making the same |
| RU2576562C1 (en) * | 2014-11-25 | 2016-03-10 | Закрытое акционерное общество "ТЕХНОИНВЕСТ АЛЬЯНС" (ЗАО "ТЕХНОИНВЕСТ АЛЬЯНС") | Method for columbite concentrate processing |
| RU2623570C1 (en) * | 2016-07-06 | 2017-06-27 | Федеральное государственное бюджетное учреждение науки Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук (ИХТРЭМС КНЦ РАН) | Method of processing of the tantalone-biobase concentrate |
Also Published As
| Publication number | Publication date |
|---|---|
| AU653674B2 (en) | 1994-10-06 |
| DE4207145C1 (en) | 1993-04-29 |
| CA2090919A1 (en) | 1993-09-07 |
| JPH0610074A (en) | 1994-01-18 |
| ATA19193A (en) | 1994-02-15 |
| CN1076731A (en) | 1993-09-29 |
| BE1006385A3 (en) | 1994-08-09 |
| CN1041753C (en) | 1999-01-20 |
| AT398209B (en) | 1994-10-25 |
| AU3390693A (en) | 1993-09-09 |
| BR9300739A (en) | 1993-09-28 |
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