CN103572046A - Method for dissolving niobium-tantalum ore with KOH for extracting niobium and tantalum - Google Patents
Method for dissolving niobium-tantalum ore with KOH for extracting niobium and tantalum Download PDFInfo
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- CN103572046A CN103572046A CN201210256859.XA CN201210256859A CN103572046A CN 103572046 A CN103572046 A CN 103572046A CN 201210256859 A CN201210256859 A CN 201210256859A CN 103572046 A CN103572046 A CN 103572046A
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Abstract
The invention relates to a method for dissolving niobium-tantalum ore with KOH for extracting niobium and tantalum. The method comprises two key steps of: dissolving the niobium-tantalum ore with a KOH solution (35-50 wt%), and dissolving out niobium and tantalum from the ore with a low-density HF solution (5-25 wt%) by leaching. The niobium-tantalum ore generates insoluble solid-phase potassium metaniobate (KNbO3) and insoluble solid-phase potassium metaniobate (KTaO3) after dissolved by KOH, and the dissolution rate on the niobium-tantalum ore is close to 100%; solid-phase potassium metaniobate and solid-phase potassium metaniobate are processed by the low-density HF solution with a use amount close to theoretic use amount, so that a solution containing fluorine-complexed niobium and fluorine-complexed tantalum is obtained; and the separation of niobium and tantalum can be realized by employing an extraction separating technology for processing the solution, and also the niobium product and the tantalum product can be prepared. Compared with conventional high-density HF solution (60-80 wt%) production technology, in the method provided by the invention, the high-density HF solution is replaced by the non-polluted KOH solution for dissolving the niobium-tantalum ore, so that the problems that a large amount of fluorine-containing waste residue, waste water and waste gas is generated during dissolution are overcome, and also the efficient recovery on niobium and tantalum is realized.
Description
Technical field
The present invention relates to a kind of niobium tantalum ore method for transformation, specifically relating to a kind of employing KOH medium is inclined to one side potassium niobate (KNbO by niobium tantalum ore decomposition and inversion
3), potassium tantalate (KTaO partially
3), and further adopt the method for lower concentration HF acid extraction niobium and tantalum.
Background technology
Niobium (Nb) and tantalum (Ta) belong to important rare metal.Now, industrial main employing high density HF acid (60 ~ 80wt%) or high density HF+H
2sO
4mixing acid is processed niobium tantalum ore and is further made niobium tantalum product.Because HF acid boiling point is low, in decomposition course, there is 6 ~ 7% HF to vapor away with toxicity waste gas form, not only can cause serious injury the healthy of people, and can cause equipment corrosion; In addition, in whole decomposition course, will produce a large amount of fluorine-containing waste residue, waste water, environmental pollution is serious.
In recent years, development along with electronic information technology industry and Iron And Steel Industry, niobium tantalum consumers demand sustainable growth, for the development of niobium tantalum hydrometallurgy provides good opportunity, but because current technology exists serious problem of environmental pollution, seriously restrict the sustainable development of niobium tantalum hydrometallurgy, urgently developed new niobium tantalum process for cleanly preparing at present.
For solving the problem of environmental pollution in niobium tantalum production process, Chinese patent CN1605639A has proposed a kind of novel process of processing niobium tantalum ore---the sub-fused salt process for cleanly preparing of KOH.The sub-fused salt of this process using KOH substitutes HF acid treatment niobium tantalum ore, processing condition are: 280 ~ 340 ℃ of temperature of reaction, concentration of potassium hydroxide 75 ~ 85wt%, potassium hydroxide and niobium tantalum ore mass ratio are 3 ~ 7:1, reaction times 1 ~ 8h, obtained good decomposition effect, but the temperature of reaction of this technique and alkaline concentration are higher, to conversion unit have relatively high expectations and alkaline media internal circulating load large, energy consumption is higher.
In US Patent No. 3058825, a kind of method of KOH solution-treated niobium tantalum ore is disclosed, the method adopts KOH solution to react with niobium tantalum ore, and the niobium tantalum compound that makes niobium tantalum generate solubility enters in solution, thereby realizes the extraction of niobium tantalum.But in this reaction process, niobium tantalum ore single rate of decomposition is lower, need repeatedly return to processing, and technique is more complicated, fails to be applied industrial.
Summary of the invention
The object of this invention is to provide a kind of existing Technology energy solution to the problems described above of being better than.Its key is to overcome the with serious pollution problem of existing high density HF acid process environments,
A kind of discharge that reduces high toxicity HF acid waste gas, waste water, waste residue is provided, from beginning of production, cuts down fluoride pollution, and can realize the niobium tantalum ore cleaning transforming method of niobium, tantalum high efficiency extraction.
The object of the invention is to realize by the following technical solutions:
The invention provides a kind of KOH solution and decompose niobium tantalum ore and extract niobium and the cleaning transforming method of tantalum, the method is that niobium tantalum ore is decomposed in potassium hydroxide solution, generates insoluble inclined to one side potassium niobate (KNbO
3) and inclined to one side potassium tantalate (KTaO
3), partially the sour potassium of niobium (tantalum) is further got with lower concentration HF acidleach, obtains joining containing niobium and tantalum fluorine the solution of thing, and this solution can adopt extraction and separation technology realize niobium, tantalum separation and make niobium, tantalum product.As shown in Figure 1, the method comprises the steps:
1) decompose niobium tantalum ore: at 210 ~ 300 ℃, under the condition of stirring, it is in 35 ~ 50wt%KOH solution that niobium tantalum ore is added to concentration, carries out decomposition reaction 1 ~ 7h, and the mass ratio of KOH and niobium tantalum ore is 2 ~ 6:1;
Described KOH decomposes the reaction of niobium tantalum ore to carry out in temperature controllable sealed reactor;
2) filtering separation: the product obtaining through decomposition in step 1) is cooled to 30 ~ 120 ℃, and filtering separation, obtains solid phase and KOH solution containing inclined to one side potassium niobate and inclined to one side potassium tantalate; Step 2) the KOH solution filtering to isolate in can directly return to step 1) for decomposition reaction;
3) leaching niobium and tantalum: at 20 ~ 80 ℃, by step 2) obtain containing inclined to one side potassium niobate and partially potassium tantalate solid phase add in the HF acid of 5 ~ 25wt%, the resolving time is 0.5 ~ 3h, solid masses is 1:1 ~ 5kgL with the ratio of liquid volume
-1;
4) filtering separation: at 10 ~ 60 ℃, step 3) is leached to product filtering separation, obtain the slag phase containing impurity such as the clear liquid of niobium and tantalum and insoluble Fe, Mn, Sn;
5) separating-purifying: join the solution of thing by what obtain in step 4) containing niobium and tantalum fluorine, send into the purification separation that existing niobium tantalum extracting and separating operation completes niobium and tantalum.
Compared with the prior art, the advantage of niobium tantalum ore cleaning transforming method provided by the invention is:
1, the present invention uses KOH solution and a small amount of lower concentration HF acid treatment niobium tantalum ore, compares with traditional high density HF acid system, has greatly reduced consumption and the F of HF acid
-, fluorochemical pollution, there is good environmental benefit;
2, the present invention is converted into inclined to one side potassium niobate and potassium tantalate partially by the niobium tantalum in niobium tantalum ore, compares with US Patent No. 3058825, and niobium tantalum ore single rate of decomposition can reach more than 99%, has greatly improved decomposition efficiency can simplification of flowsheet;
3, the present invention adopts low concentration KOH solution to decompose niobium tantalum ore, with Chinese patent CN1605639A and document 1: difficult decompose the research of niobium tantalum ore concentrated potassium hydroxide Leaching Mechanism of Refractory, colleges and universities' chemical engineering journal, V.19, the disclosed method of No.2 is compared with the obvious advantage, the alkaline concentration of decomposition reaction is reduced to 35 ~ 50wt% from 75-85wt%, and reaction conditions is optimized greatly, the recycle of easier realization response process alkaline media;
Accompanying drawing explanation
Fig. 1 is the process flow sheet of niobium tantalum ore cleaning transforming method provided by the invention.
Embodiment
Below by implementation process and the step of further setting forth in conjunction with the accompanying drawings and embodiments this technique.
Embodiment 1
Mass ratio 4:1 by KOH and niobium tantalum ore powder takes a certain amount of KOH, adds the potassium hydroxide solution that water is made into 35wt%, adds-200 object niobium tantalum ore powder, opens and stirs and be warming up to 260 ℃, and reaction 1h, obtains degradation production.
By above-mentioned degradation production cooled and filtered, obtain containing inclined to one side potassium niobate and the solid phase of potassium tantalate and unreacted KOH solution (this solution returns for above-mentioned decomposition reaction) completely partially.
Solid phase slag containing inclined to one side potassium niobate and inclined to one side potassium tantalate joins in the HF acid solution of 25wt%, and solid masses is 1:1kgL with the ratio of liquid volume
-1, Leaching reaction 1h under normal temperature, niobium tantalum leaching yield 97%.
By above-mentioned leaching product filtering separation, obtain the slag phase containing impurity such as the clear liquid of niobium and tantalum and insoluble Fe, Mn, Sn.Clear liquid containing niobium and tantalum can be delivered to existing niobium tantalum extracting and separating operation, carries out niobium and tantalum isolation of purified, and the slag that contains the impurity such as Fe, Mn, Sn can be used for the recovery of the valuable metals such as Sn mutually.
Embodiment 2
Take the difficult niobium tantalum ore that decomposes of a certain amount of-300 objects and add in reactor, add subsequently the KOH solution of 50wt%, this solution, according to alkali ore deposit mass ratio 6:1 preparation, is opened and is stirred and be warming up to 210 ℃, and reaction 7h, obtains degradation production.
By above-mentioned degradation production cooled and filtered, obtain containing inclined to one side potassium niobate and the solid phase of potassium tantalate and unreacted KOH solution (this solution returns for above-mentioned decomposition reaction) completely partially.
Solid phase slag containing inclined to one side potassium niobate and inclined to one side potassium tantalate joins in the HF acid solution of 5wt%, and solid masses is 1:5kgL with the ratio of liquid volume
-1, Leaching reaction 3h at 60 ℃ of temperature, niobium tantalum leaching yield 98%.
By above-mentioned leaching product filtering separation, obtain the slag phase containing impurity such as the clear liquid of niobium and tantalum and insoluble Fe, Mn, Sn.Clear liquid containing niobium and tantalum can be delivered to existing niobium tantalum extracting and separating operation, carries out niobium and tantalum isolation of purified, and the slag that contains the impurity such as Fe, Mn, Sn can be used for the recovery of the valuable metals such as Sn mutually.
Embodiment 3
Mass ratio 2:1 by KOH and niobium tantalum ore powder takes a certain amount of KOH, adds the KOH solution that water is made into 40wt%, adds-200 object niobium tantalum ore powder, opens and stirs and be warming up to 250 ℃, and reaction 1.5h, obtains degradation production.
By above-mentioned degradation production cooled and filtered, obtain containing inclined to one side potassium niobate and the solid phase of potassium tantalate and unreacted KOH solution (this solution returns for above-mentioned decomposition reaction) completely partially.
Solid phase slag containing inclined to one side potassium niobate and inclined to one side potassium tantalate joins in the HF acid solution of 12wt%, and solid masses is 1:4kgL with the ratio of liquid volume
-1, Leaching reaction 2h under normal temperature, niobium tantalum leaching yield 99%.
By above-mentioned leaching product filtering separation, obtain the slag phase containing impurity such as the clear liquid of niobium and tantalum and insoluble Fe, Mn, Sn.Clear liquid containing niobium and tantalum can be delivered to existing niobium tantalum extracting and separating operation, carries out niobium and tantalum isolation of purified, and the slag that contains the impurity such as Fe, Mn, Sn can be used for the recovery of the valuable metals such as Sn mutually.
Embodiment 4
Mass ratio 3:1 by KOH and niobium tantalum ore powder takes a certain amount of KOH, adds the KOH solution that water is made into 47wt%, adds-200 object niobium tantalum ore powder, opens and stirs and be warming up to 300 ℃, and reaction 2h, obtains degradation production.
By above-mentioned degradation production cooled and filtered, obtain containing inclined to one side potassium niobate and the solid phase of potassium tantalate and unreacted KOH solution (this solution returns for above-mentioned decomposition reaction) completely partially.
Solid phase slag containing inclined to one side potassium niobate and inclined to one side potassium tantalate joins in the HF acid solution of 20wt%, and solid masses is 1:2kgL with the ratio of liquid volume
-1, Leaching reaction 0.5h under normal temperature, niobium tantalum leaching yield 96%.
By above-mentioned leaching product filtering separation, obtain the slag phase containing impurity such as the clear liquid of niobium and tantalum and insoluble Fe, Mn, Sn.Clear liquid containing niobium and tantalum can be delivered to existing niobium tantalum extracting and separating operation, carries out niobium and tantalum isolation of purified, and the slag that contains the impurity such as Fe, Mn, Sn can be used for the recovery of the valuable metals such as Sn mutually.
Claims (3)
1. KOH solution decomposes the method that niobium tantalum ore extracts niobium and tantalum, comprises following step:
1) decompose niobium tantalum ore: at 210 ~ 300 ℃, under the condition of stirring, it is in 35 ~ 50wt%KOH solution that niobium tantalum ore is added to concentration, carries out decomposition reaction 1 ~ 7h, and the mass ratio of potassium hydroxide and niobium tantalum ore is 2 ~ 6:1;
2) filtering separation: the product obtaining through decomposition in step 1) is cooled to 30～120 ℃, and filtering separation, obtains solid phase and KOH solution containing inclined to one side potassium niobate and inclined to one side potassium tantalate;
3) leaching niobium and tantalum: at 20 ~ 80 ℃, by step 2) obtain containing inclined to one side potassium niobate and partially potassium tantalate solid phase add in the HF acid of 5 ~ 25wt%, the resolving time is 0.5 ~ 3h, solid masses is 1:1 ~ 5kgL with the ratio of liquid volume
-1;
4) filtering separation: at 10 ~ 60 ℃, step 3) is leached to product filtering separation, obtain the slag phase containing impurity such as the clear liquid of niobium and tantalum and insoluble Fe, Mn, Sn;
5) separating-purifying: join the solution of thing by what obtain in step 4) containing niobium and tantalum fluorine, enter niobium tantalum extracting and separating operation and complete the separated of niobium and tantalum.
2. the method that niobium and tantalum are got in KOH solution decomposition niobium tantalum ore as claimed in claim 1 and low acidleach, is characterized in that: in described step 1), decomposition reaction is carried out in temperature controllable sealed reactor.
3. KOH solution as claimed in claim 1 decomposes the method that niobium and tantalum are got in niobium tantalum ore and low acidleach, it is characterized in that: step 2) in the KOH solution that filters to isolate can directly return to step 1) for decomposition reaction.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3058825A (en) * | 1958-09-22 | 1962-10-16 | Paul B Cardon | Process for recovering columbium and tantalum from ores and ore concentrates containing same |
| 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 |
| CN101191161A (en) * | 2006-11-22 | 2008-06-04 | 中国科学院过程工程研究所 | Mechanical activating strengthening alkali decomposition cleaning transforming method for hard-decomposition tantalum niobium concentrate |
| CN101215635A (en) * | 2007-01-05 | 2008-07-09 | 中国科学院过程工程研究所 | Method for separating tantalum and niobium from potassium metatantalate and potassium metaniobate mixture |
| CN101440429A (en) * | 2008-12-18 | 2009-05-27 | 广州有色金属研究院 | Method for decomposing ore concentrate containing tantalum, niobium and rare-earth element |
-
2012
- 2012-07-23 CN CN201210256859.XA patent/CN103572046A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3058825A (en) * | 1958-09-22 | 1962-10-16 | Paul B Cardon | Process for recovering columbium and tantalum from ores and ore concentrates containing same |
| 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 |
| CN101191161A (en) * | 2006-11-22 | 2008-06-04 | 中国科学院过程工程研究所 | Mechanical activating strengthening alkali decomposition cleaning transforming method for hard-decomposition tantalum niobium concentrate |
| CN101215635A (en) * | 2007-01-05 | 2008-07-09 | 中国科学院过程工程研究所 | Method for separating tantalum and niobium from potassium metatantalate and potassium metaniobate mixture |
| CN101440429A (en) * | 2008-12-18 | 2009-05-27 | 广州有色金属研究院 | Method for decomposing ore concentrate containing tantalum, niobium and rare-earth element |
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Application publication date: 20140212 |