CN100554445C - A kind of inclined to one side potassium tantalate, method of tantalum and niobium in the potassium niobate mixture partially of separating - Google Patents

A kind of inclined to one side potassium tantalate, method of tantalum and niobium in the potassium niobate mixture partially of separating Download PDF

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CN100554445C
CN100554445C CNB2007100632694A CN200710063269A CN100554445C CN 100554445 C CN100554445 C CN 100554445C CN B2007100632694 A CNB2007100632694 A CN B2007100632694A CN 200710063269 A CN200710063269 A CN 200710063269A CN 100554445 C CN100554445 C CN 100554445C
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tantalum
niobium
potassium
separating
tantalate
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CN101215635A (en
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郑诗礼
王晓辉
张懿
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Institute of Process Engineering of CAS
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Abstract

The present invention relates to a kind of inclined to one side potassium tantalate, method of tantalum and niobium in the potassium niobate mixture partially of separating, its method is to decompose inclined to one side potassium tantalate, inclined to one side potassium niobate mixture with hydrofluoric acid and silicofluoric acid mixing solutions, and degradation production obtains containing the solution and the potassium silicofluoride crystal of tantalum niobium after filtration.The solution that contains the tantalum niobium directly enters tantalum niobium extracting and separating operation and finishes separating of tantalum and niobium; The potassium silicofluoride crystal becomes a kind of valency byproduct that has through washing, filtration, drying.This method has solved inclined to one side potassium tantalate that the inferior fused salt process for cleanly preparing of KOH of tantalum niobium concentrate obtains, the problem that can't effectively utilize of potassium niobate mixture partially, perfect technical process, and the utilization ratio of tantalum niobium in the tantalum niobium concentrate brought up near 100%.

Description

A kind of inclined to one side potassium tantalate, method of tantalum and niobium in the potassium niobate mixture partially of separating
Invention field
The present invention relates to the method for a kind of isolating tantalum and niobium, specifically relate to the inclined to one side potassium tantalate (KTaO of a kind of dissolving 3), potassium niobate (KNbO partially 3) mixture and separate the wherein contained tantalum and the method for niobium.
Background technology
Tantalum, niobium belong to rare noble metal.At present, high dense HF acid of industrial extensive employing (60-70%) or the dense H of high dense HF- 2SO 4The method of mixing acid is decomposed tantalum niobium concentrate stone, and this method has the HF of 6-7% to vapor away with the waste gas form in decomposition course, and high volatile volatile, high toxicity HF make operating environment very abominable, have also caused topsoil; And one ton of tantalum niobium concentrate of every processing can produce the fluorine residue that contains of 10-15 ton, caused very serious environmental to pollute.In addition, the niobium tantalum ore that widely distributes in China belongs to the low difficulty of grade and decomposes the ore deposit, as adopts existing HF acid decomposition, and the tantalum niobium concentrate rate of decomposition is low, only is about 85%, and this will cause the great wasting of resources.
For addressing the above problem, Chinese Academy Of Sciences Process Engineering Research Institute has proposed a kind of novel process of handling tantalum niobium concentrate---the inferior fused salt process for cleanly preparing (Chinese patent CN1605639A) of KOH.This technology substitutes HF with the inferior fused salt of KOH and handles the difficult tantalum niobium concentrate that decomposes, mineral rate of decomposition height, and from source reduction fluoride pollution, have excellent industrial application foreground.But some end product of this technology is KTaO 3, KNbO 3Mixture, owing to there is not a kind of effective means tantalum in this mixture and niobium can be separated, this mixture still can't effectively utilize at present.The reduction that this has caused the mineral utilization ratios has caused the wasting of resources, and then has seriously restricted the development of this technology.Therefore, how to realize KTaO 3, KNbO 3The separating of tantalum and niobium in the mixture, become a problem demanding prompt solution.
Current technology mainly adopts method of extraction isolating tantalum and niobium, its method is open in United States Patent (USP) 3117833, the raw material that promptly contains the tantalum niobium with the HF dissolving, make tantalum and niobium enter liquid phase with the form of fluorine title complex respectively, use extraction agent (MIBK etc.) that tantalum in the liquid phase and niobium are extracted jointly then, thereby separate with associated element, realize separated from one another by the substep back extraction again.This technology is very ripe, is widely used in the industrial production.But this technology is not suitable for handling KTaO 3, KNbO 3Mixture is because KTaO 3And KNbO 3To generate the very little tantalum potassium fluoride (K of solubleness with the HF reaction 2TaF 7) and potassium niobate fluoride (K 2NbF 7), tantalum potassium fluoride (K 2TaF 7) and potassium niobate fluoride (K 2NbF 7) can from solution, crystallization separate out, make that extraction process is difficult to carry out.About KTaO 3, KNbO 3The separating of tantalum and niobium in the mixture, report is not arranged as yet at present.
Summary of the invention
The purpose of this invention is to provide a kind of dissolving KTaO 3, KNbO 3Mixture and the method for separating wherein contained tantalum and niobium, this method can be used for handling the resulting KTaO of the inferior fused salt process for cleanly preparing of KOH of tantalum niobium concentrate 3, KNbO 3Mixture solves the problem that it can not effectively utilize, thereby improves the utilization ratio of tantalum niobium concentrate, replenishment of process flow process.
The objective of the invention is to realize by the following technical solutions:
1) with KTaO 3, KNbO 3Mixture adds HF and H 2SiF 6Mixed acid solution in, at 20～80 ℃, decomposition reaction 15～60min under the stirring condition.
The concentration of HF is 5～22mol/L in the described mixed acid solution, H 2SiF 6Consumption be 1.0～1.5 times of theoretical amount.
The volume of described mixed acid solution and KTaO 3, KNbO 3The ratio (liquid-solid ratio) of the quality of mixture is 2.0～6.5: 1.
This reaction process was undertaken by following two steps:
a.2KTaO 3+14HF＝H 2TaF 7+K 2TaF 7+6H 2O
2KNbO 3+14HF＝H 2NbF 7+K 2NbF 7+6H 2O
b.K 2TaF 7+H 2SiF 6＝H 2TaF 7+K 2SiF 6
K 2NbF 7+H 2SiF 6＝H 2NbF 7+K 2SiF 6
The reaction of second step has utilized K 2SiF 6Solubleness less than K 2TaF 7And K 2NbF 7Character, according to the precipitation transforming principle, the K of indissoluble 2TaF 7And K 2NbF 7In K will be converted into the more K of indissoluble 2SiF 6Precipitation, tantalum and niobium are then with H 2TaF 7And H 2NbF 7Form 100% enter liquid phase.
2) after product to be decomposed was cooled to normal temperature, filtering separation obtained containing H 2TaF 7And H 2NbF 7Clear liquid and K 2SiF 6Crystal.K 2SiF 6Crystal is through washing, filter and after 30～80 ℃ of oven dry, becoming a kind of valency byproduct that has.
3) contain H 2TaF 7And H 2NbF 7Clear liquid can finish separating of tantalum and niobium by existing tantalum niobium extraction and separation technology, promptly with methyl iso-butyl ketone (MIBK) (MIBK) tantalum in the clear liquid and niobium are extracted jointly earlier, then with the dilute sulphuric acid niobium of from organic phase, stripping, at last with the pure water tantalum of from organic phase, stripping.Thereby realize separating of tantalum and niobium.
This method has realized KTaO 3, KNbO 3The separating of tantalum and niobium in the mixture, solved the inferior fused salt process for cleanly preparing part of the KOH product (KTaO of tantalum niobium concentrate 3, KNbO 3Mixture) problem that can't effectively utilize, thereby perfect technical process, and make the difficult utilization ratio of tantalum niobium in the tantalum niobium concentrate of decomposing near 100%.This method technology is simple, easy handling, does not need special means and equipment, the separation efficiency height of tantalum niobium, and can obtain valency byproduct K 2SiF 6Crystal.
Embodiment
Embodiment 1:
With KTaO 3, KNbO 3Mixture adds HF and H 2SiF 6Mixed acid solution in, KTaO in the mixture 3And KNbO 3Mol ratio be 1: 1, HF concentration is 5mol/L in the mixed acid solution, H 2SiF 6Consumption is 1.5 times of theoretical amount, and liquid-solid ratio is 6.5: 1, stirs down at 80 ℃ and decomposes 60min, and after reaction finished, product to be decomposed was cooled to normal temperature, filtered, and obtained containing the clear liquid and the infusible precipitate of tantalum niobium.The clear liquid that contains the tantalum niobium can directly be delivered to separation and the purifying that existing tantalum niobium extracting and separating operation is finished the tantalum niobium; Infusible precipitate filters, 30 ℃ of oven dry after washing with pure water.
Analyze KTaO through ICP-AES 3, KNbO 3Tantalum in the mixture and niobium 100% enters the charging requirement that the clear liquid that contains the tantalum niobium and this clear liquid meet existing tantalum niobium extraction and separation technology fully.Analyze the K that gained is precipitated as through XRD and ICP-AES 2SiF 6Crystal, purity reaches 99%.
Embodiment 2:
With KTaO 3And KNbO 3Mixture adds HF and H 2SiF 6Mixed acid solution in, KTaO in the mixture 3And KNbO 3Mol ratio be 5: 1, HF concentration is 8mol/L in the mixed acid solution, H 2SiF 6Consumption is 1.2 times of theoretical amount, and liquid-solid ratio is 4.0: 1, stirs down at 60 ℃ and decomposes 30min, and after reaction finished, product to be decomposed was cooled to normal temperature, filtered, and obtained containing the clear liquid and the infusible precipitate of tantalum niobium.The clear liquid that contains the tantalum niobium can directly be delivered to separation and the purifying that existing tantalum niobium extracting and separating operation is finished the tantalum niobium; Infusible precipitate filters, 50 ℃ of oven dry after washing with pure water.
Analyze KTaO through ICP-AES 3And KNbO 3Tantalum in the mixture and niobium 100% enters the charging requirement that the clear liquid that contains the tantalum niobium and this clear liquid meet existing tantalum niobium extraction and separation technology fully.Analyze through XRD and ICP-AES, gained is precipitated as pure K 2SiF 6Crystal, purity reaches 99%.
Embodiment 3:
With KTaO 3And KNbO 3Mixture adds in the mixed acid solution of HF and H2SiF6, KTaO in the mixture 3And KNbO 3Mol ratio be 10: 1, HF concentration is 12mol/L in the mixed acid solution, H 2SiF 6Consumption is 1.0 times of theoretical amount, and liquid-solid ratio is 3.0: 1, stirs down at 30 ℃ and decomposes 15min, and after reaction finished, product to be decomposed was cooled to normal temperature, filtered, and obtained containing the clear liquid and the infusible precipitate of tantalum niobium.The clear liquid that contains the tantalum niobium can directly be delivered to separation and the purifying that existing tantalum niobium extracting and separating operation is finished the tantalum niobium; Infusible precipitate filters, 40 ℃ of oven dry after washing with pure water.
Analyze KTaO through ICP-AES 3And KNbO 3Tantalum in the mixture and niobium 100% enters the charging requirement that the clear liquid that contains the tantalum niobium and this clear liquid meet existing tantalum niobium extraction and separation technology fully.Analyze through XRD and ICP-AES, gained is precipitated as pure K 2SiF 6Crystal, purity reaches 99%.
Embodiment 4:
With KTaO 3And KNbO 3Mixture adds in the mixed acid solution of HF and H2SiF6, KTaO in the mixture 3And KNbO 3Mol ratio be 1: 5, HF concentration is 14mol/L in the mixed acid solution, H 2SiF 6Consumption is 1.1 times of theoretical amount, and liquid-solid ratio is 2.5: 1, stirs down at 40 ℃ and decomposes 20min, and after reaction finished, product to be decomposed was cooled to normal temperature, filtered, and obtained containing the clear liquid and the infusible precipitate of tantalum niobium.The clear liquid that contains the tantalum niobium can directly be delivered to separation and the purifying that existing tantalum niobium extracting and separating operation is finished the tantalum niobium; Infusible precipitate filters, 60 ℃ of oven dry after washing with pure water.
Analyze KTaO through ICP-AES 3And KNbO 3Tantalum in the mixture and niobium 100% enters the charging requirement that the clear liquid that contains the tantalum niobium and this clear liquid meet existing tantalum niobium extraction and separation technology fully.Analyze through XRD and ICP-AES, gained is precipitated as pure K 2SiF 6Crystal, purity reaches 99%.
Embodiment 5:
With KTaO 3And KNbO 3Mixture adds HF and H 2SiF 6Mixed acid solution in, KTaO in the mixture 3And KNbO 3Mol ratio be 1: 10, HF concentration is 20mol/L in the mixed acid solution, H 2SiF 6Consumption is 1.3 times of theoretical amount, and liquid-solid ratio is 2.0: 1, stirs down at 20 ℃ and decomposes 40min, and after reaction finished, product to be decomposed was cooled to normal temperature, filtered, and obtained containing the clear liquid and the infusible precipitate of tantalum niobium.The clear liquid that contains the tantalum niobium can directly be delivered to separation and the purifying that existing tantalum niobium extracting and separating operation is finished the tantalum niobium; Infusible precipitate filters, 80 ℃ of oven dry after washing with pure water.
Analyze KTaO through ICP-AES 3And KNbO 3Tantalum in the mixture and niobium 100% enters the charging requirement that the clear liquid that contains the tantalum niobium and this clear liquid meet existing tantalum niobium extraction and separation technology fully.Analyze through XRD and ICP-AES, gained is precipitated as pure K 2SiF 6Crystal, purity reaches 99%.

Claims (5)

1, a kind of inclined to one side potassium tantalate, method of tantalum and niobium in the potassium niobate mixture partially of separating comprises the steps:
A). inclined to one side potassium tantalate, inclined to one side potassium niobate mixture are added in the mixed acid solution of hydrofluoric acid and silicofluoric acid, under stirring condition, carry out decomposition reaction;
B). after product to be decomposed was cooled to normal temperature, filtering separation obtained containing the clear liquid and the infusible precipitate of tantalum and niobium, infusible precipitate through washing, filter, after the oven dry, obtain pure potassium silicofluoride crystal;
C). the clear liquid that will contain tantalum and niobium is delivered to tantalum niobium extracting and separating operation and is finished separating of tantalum and niobium.
2, a kind of inclined to one side potassium tantalate, method of tantalum and niobium in the potassium niobate mixture partially of separating according to claim 1, it is characterized in that described inclined to one side potassium tantalate, partially in the potassium niobate mixture partially potassium tantalate and partially the mol ratio of potassium niobate be 0.1～10: 1.
3, a kind of inclined to one side potassium tantalate, method of tantalum and niobium in the potassium niobate mixture partially of separating according to claim 1, it is characterized in that in the mixed acid solution of described hydrofluoric acid and silicofluoric acid, the concentration of hydrofluoric acid is 5～22mol/L, and the consumption of silicofluoric acid is 1.0～1.5 times of theoretical amount.
4, a kind of inclined to one side potassium tantalate, method of tantalum and niobium in the potassium niobate mixture partially of separating according to claim 1 is characterized in that described decomposition reaction temperature is 20～80 ℃, and the decomposition reaction time is 15～60min.
5, a kind of inclined to one side potassium tantalate, method of tantalum and niobium in the potassium niobate mixture partially of separating according to claim 1 is characterized in that described potassium silicofluoride crystal bake out temperature is 30～80 ℃.
CNB2007100632694A 2007-01-05 2007-01-05 A kind of inclined to one side potassium tantalate, method of tantalum and niobium in the potassium niobate mixture partially of separating Expired - Fee Related CN100554445C (en)

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CN102952951A (en) * 2011-08-22 2013-03-06 中国科学院过程工程研究所 Method for extracting tantalum and niobium and producing potassium fluosilicate from tungsten smelting slag
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
CN102586598A (en) * 2012-03-23 2012-07-18 宁夏东方钽业股份有限公司 Method for decomposing tantalum-niobium compound
CN103572045A (en) * 2012-07-23 2014-02-12 中国科学院过程工程研究所 Alkali-acid combined technology for processing low-grade niobium-tantalum 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
CN102888521A (en) * 2012-11-02 2013-01-23 吉林吉恩镍业股份有限公司 Method of sulfuric acid leaching niobium by pressurizing red mud
CN110629048A (en) * 2019-11-04 2019-12-31 常州市耐欧金属材料科技有限公司 Niobium tube production process
CN111690827B (en) * 2020-07-01 2022-07-15 江西拓泓新材料有限公司 Method for recovering tantalum resource from potassium fluotantalate crystallization mother liquor

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US3972710A (en) * 1974-07-23 1976-08-03 Hermann C. Starchk Berlin Method of upgrading tantalum and niobium concentration in slags
WO1990002823A1 (en) * 1988-09-06 1990-03-22 Institut National De Recherche Chimique Appliquee IMPROVED PROCESS FOR OBTAINING IMPURITY-FREE COMPOUNDS OF Ta AND/OR Nb FROM MATERIALS CONTAINING THESE METALS
CN1378604A (en) * 2000-09-12 2002-11-06 三井金属鋐业株式会社 Method for producing metal or metal compound comprising process of treating with fluorine and adjusted raw material used therein
CN1605639A (en) * 2003-10-08 2005-04-13 中国科学院过程工程研究所 Process for clean conversion of tantalum niobium ore

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3972710A (en) * 1974-07-23 1976-08-03 Hermann C. Starchk Berlin Method of upgrading tantalum and niobium concentration in slags
WO1990002823A1 (en) * 1988-09-06 1990-03-22 Institut National De Recherche Chimique Appliquee IMPROVED PROCESS FOR OBTAINING IMPURITY-FREE COMPOUNDS OF Ta AND/OR Nb FROM MATERIALS CONTAINING THESE METALS
CN1378604A (en) * 2000-09-12 2002-11-06 三井金属鋐业株式会社 Method for producing metal or metal compound comprising process of treating with fluorine and adjusted raw material used therein
CN1605639A (en) * 2003-10-08 2005-04-13 中国科学院过程工程研究所 Process for clean conversion of tantalum niobium ore

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