CN1032871C - Method of extracting and separating zirconium from scandium oxide - Google Patents
Method of extracting and separating zirconium from scandium oxide Download PDFInfo
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- CN1032871C CN1032871C CN90108823A CN90108823A CN1032871C CN 1032871 C CN1032871 C CN 1032871C CN 90108823 A CN90108823 A CN 90108823A CN 90108823 A CN90108823 A CN 90108823A CN 1032871 C CN1032871 C CN 1032871C
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- scandium
- zirconium
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- scium trioxide
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- 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
Abstract
The present invention relates to a technological method for extracting and separating zirconium from scandium oxides. 100% of TBP is used as an extractant, 3 to 7 mol/l of perchloric acid solution containing 9.0 to 50.0 grams/l of scandium is used as feed solution, and extraction is carried out. An extraction phase ratio (O/A) is from 1/2 to 3/1. The present invention has the advantages of the good separation effects of the scandium and the zirconium, the high recovery rate of the scandium, high productive capacity, obvious economic benefits, the low consumption of chemical materials, short productive cycle, convenient operation and convenient generalization and application without any special equipment, a separation coefficient is as high as 10+(3), a direct yield is from 90 to 96%, a total recovery rate is bigger than 97%, and the unit consumption of chemical industry materials is smaller than 1100 yuan/kilogram of the scandium oxides.
Description
The present invention relates to from Scium trioxide (Sc
2O
3) in the extracting and separating processing method of removing zirconium.
Scandium is typical rare and scatter element, is present in the mineral such as ilmenite, tungsten ore, uranium ore, bauxite, zircon concentrate in the most association of nature.Its content is generally 0.00X%, reclaims difficulty, the complex process of purification Scium trioxide, so it costs an arm and a leg.
At present, the production of Scium trioxide both at home and abroad mainly is to extract in the hydrolysising mother liquid from titanium white production, chlorination flue dust that the chlorination titanium slag is produced titanium tetrachloride and chloride residue and the tungsten slag.But all contain zirconium in these raw materials to some extent.
Reclaim to extract method of scandium oxide and mainly contain ion exchange method, solvent extration and chromes etc., the purity of the Scium trioxide of producing is looked the difference of purifying technique and difference is generally 98.0-99.99%.But with regard to present existing flow process, the separating effect of scandium and zirconium is all undesirable, always contain the impurity zirconium in the product, reaches 0.X-1% at most, contains 0.0X% at least, is exactly the High-purity Sc Oxide more than 99.99%, and the zirconium of tens of PPm is also arranged.
As everyone knows, High-purity Sc Oxide is mainly used in high-tech areas such as nuclear technique, laser technology, electronic technology, and the application in optical field also causes people's attention.But in these Application Areass, high especially to the requirement of some impurity in the Scium trioxide, zirconium is a kind of impurity element wherein.The Scium trioxide zirconium impurity that for example is used for preparing GSGG and GSAG laser bar in the laser technology is less than 5PPm, also needs less than 10PPm for the content of zirconium in the 99.999% Scium trioxide product.High like this requirement, the process for separating and purifying of Scium trioxide is difficult to reach at present.So many research workers are constantly exploring the method that zirconium in the Scium trioxide is removed in new separation.
Firm people (the Guo Gong Yi et al Rare Earths that waits of cuckoo, Extraction, preparation and applications, 163, Editedby R.G.Bautista and M.M.Wong, The Minerals, Metalsand materials Society, 1988) proposed with tributyl phosphate (tributylphosphate, hereinafter to be referred as TBP) chromes purification method of scandium oxide, this method is to make the citric acid solution that contains 2-4 grams per liter Scium trioxide, at room temperature by containing the extracting chromatographic column of TBP stationary phase, it is 3-4 mol perchloric acid that its effluent liquid is adjusted to its acidity with perchloric acid, again by containing the extracting chromatographic column of TBP stationary phase, and scandium is separated with its impurity.The Scium trioxide that contains 70% can be purified to 99.99% with this method, the zirconium amount that contains after the purification also can from 0.025% reduce to＜0.001%.This method separating impurity effective, however but exist following weak point: (1) need carry out twice extraction chromatography and separates, could separate impurity wherein effectively in two media, complex operation, and the production cycle is long.(2) concentration of scandium too low (2-4 grams per liter Scium trioxide) in the feed liquid, treatment capacity is little, and production capacity is low, the cost height, the rate of recovery only is 90%, and is lower.
The present invention be a kind of from Scium trioxide the processing method of extracting and separating zirconium, tributyl phosphate with 100% (TBP) is that extraction agent is as organic phase, solution with the 3-7 mol perchloric acid that contains 9.0-50 grams per liter scandium is that feed liquid is as water, extract, scandium is come together in the organic phase, and separate with zirconium, the organic phase solution that contains scandium is carried out back extraction.
In the process of extracting scandium, just reach and the fine isolating purpose of zirconium through carrying out liquid-liquid single-stage extraction as extraction agent with 100% TBP.The extraction equilibrium time is generally the 5-30 branch and plants.The percentage extraction of scandium is 92-99%.Its organic phase is good with compare (O/A) of water with 1/2-3/1 (volume ratio) during extracting scandium.The value of comparing O/A is less than 1/2, and the scandium percentage extraction is low, inferior separating effect.Along with the increase of comparing the O/A value, the percentage extraction of scandium uprises, and it is big that separation factor β value becomes; But the value of comparing O/A is greater than 3/1, and the organic phase volume is big, and the consumption of TBP extraction agent increases, and product cost is increased, and makes troubles for the operation of later reextraction scandium.The compound method of feed liquid is, Scium trioxide is used the high chloro acid dissolution, and during the dissolved oxygen scandium, with 1: 1-1: the perchloric acid solution of 3 (volume ratio of perchloric acid and water, the proportion of perchloric acid are 1.67, down with) is advisable.The amount of the perchloric acid that is added during dissolving adds 1: 1 (volume ratio of perchloric acid and water by 1 gram Scium trioxide, down with) perchloric acid 12-24 milliliter for well, less than 12 milliliters, the Scium trioxide dissolving not exclusively, the rate of recovery of scandium is lowered,, then increase the cost of Scium trioxide if greater than 24 milliliters, 1 gram Scium trioxide is used 1: 1 high chloro acid dissolution of 12-24 milliliter, and its dissolution rate is all greater than 99.9%.
During with high chloro acid dissolution's Scium trioxide of 1: 1 (volume ratio of perchloric acid and water), should on electric furnace, slowly heat while stirring, make its reaction 2-4 hour, Scium trioxide is dissolved fully, solution is limpid state, stop heating, cooling, the acidity that transfers to solution with perchloric acid contains 3-7 mol perchloric acid, and the solution that contains scandium 9.0-50.0 grams per liter is as feed liquid.
The acidity of feed liquid is less than 3 mol perchloric acid, and its separation factor β value is little, inferior separating effect, and also the percentage extraction of scandium is low.Along with the increase of acidity in the feed liquid, the percentage extraction of scandium increases, and separation factor β value also uprises, but the acidity in the feed liquid is greater than 7 mol perchloric acid, and organic phase viscosity is big, operation inconvenience, even influence phase-splitting, and the big consumption perchloric acid of acidity is many, and product cost increases.
The concentration of the scandium in the feed liquid is less than 9 grams per liters, because scandium concentration is little, plant factor reduces greatly, production capacity is little, but the concentration of scandium is greater than 50 grams per liters, and separation factor β value diminishes, it is big that organic phase viscosity becomes, percentage extraction is low, so the concentration of scandium is advisable with the 9.0-50 grams per liter in the feed liquid, 9.0-40 grams per liter scandium is better.
The resulting scandium organic phase solution that contains in TBP extraction back with 100% is carried out back extraction, make scandium change aqueous phase over to.Concrete grammar is to strip as reverse-extraction agent with the hydrochloric acid soln of 0.5-1.5 mol, and the starting time of reextraction is 10-30 minute.The O/A that compares of organic phase and water is 1/2-3/1 (volume ratio) during reextraction, the value of comparing O/A is too little, the water volume is big, the concentration of scandium is low, make troubles for later oxalic acid precipitation, it is too big to compare O/A, and the organic phase volume is big, the number of times of stripping will increase, and is good so compare O/A with 1/2-3/1 (volume ratio).
It is 2-3 that resulting strip liquor is regulated its pH value with ammoniacal liquor, is heated to 50-95 ℃, refining with hot oxalic acid solution precipitation, can obtain the Scium trioxide that zirconium content is lower than 10ppm.Regulate the pH value of its strip liquor with ammoniacal liquor, for well, because PH is less than 2, acidity is big, and is incomplete with the oxalic acid precipitation scandium with 2-3 for the pH value of strip liquor.Its PH the scandium hydroxide precipitation can occur greater than 3.
The invention has the advantages that:
1. make extraction agent with 100%TBP, just can obtain containing the Scium trioxide of zirconium less than 10PPm through the single-stage liquid-liquid extraction in the perchloric acid medium, minimum reaching contains the Scium trioxide of zirconium less than 5PPm, the good separating effect of scandium and zirconium, and its separation factor β value can be up to 10
3, for example (weight percentage) Scium trioxide once can be reduced to below the 10PPm with processing method extracting and separating of the present invention down together with containing 0.1% zirconium.Processing method rate of recovery height of the present invention, its direct yield is 90-96%, total yield is greater than 97%.
2. the concentration height of the scandium in the feed liquid can be up to 50 grams per liters, and charging capacity is big, and the production treatment capacity is big in the unit time, the production capacity height.
3. the percentage extraction height of scandium can be up to 92-99%, and chemical materials consumes low, remarkable in economical benefits, and the chemical materials unit consumption is less than 1100 yuan of/kilogram Scium trioxides.
4. only adopt single-stage liquid-liquid-liquid extraction method to remove zirconium in the Scium trioxide with regard to separable, the cycle is short, and is simple to operate, is easy to grasp, and do not need any specific installation, is easy to apply.
Following indefiniteness embodiment is just in order to further specify the present invention, rather than as limiting the scope of the invention, protection scope of the present invention is decided by claim.
Embodiment 1
200 gram Scium trioxides (containing zirconium 0.043%) are placed 3 liters evaporating dish, 2400 milliliters in the perchloric acid that adds 1: 1 (volume ratio of perchloric acid and water), slowly heating on electric furnace, stir, reacted 3 hours, it is limpid to make the solid oxidation scandium be dissolved to solution fully, stops heating, cooling, the dissolution rate of Scium trioxide is greater than 99.9%.
The scandium solution that contains 0.043% zirconium in the Scium trioxide behind 1: 1 (volume ratio of perchloric acid and water) high chloro acid dissolution is adjusted the acidity of feed liquid with perchloric acid, and the acidity that transfers to feed liquid is 6.1 mol perchloric acid.The concentration that feed liquid contains scandium is 32.0 grams per liters, and the water cumulative volume is 12.5 liters,, stirs 15 minutes in 35 liters single-stage extraction groove with 12.5 liters of 100%TBP, extracts, and leaves standstill phase-splitting.The concentration of gained balance aqueous phase scandium is 0.31 grams per liter, and the concentration of scandium is 31.69 grams per liters in the balance organic phase.The percentage extraction of scandium is 99.03%.With the hydrochloric acid soln of 1 mol, organic phase is carried out back extraction, comparing O/A is 1/1, back extraction three times, each back extraction was carried out 10 minutes.Strip liquor is 37.5 liters, and the concentration of scandium is 10.52 grams per liters in the strip liquor, and stripping rate is 99.6%.It is 2.5 that strip liquor is transferred to PH with ammoniacal liquor, about heated solution to 80 ℃, press scandium: oxalic acid (mol ratio)=1: 1.5, add hot oxalic acid solution, leave standstill filtration, the method of all knowing by the one of ordinary skill in the art is put into muffle furnace calcination 1 hour under 800 ℃ temperature with precipitation, and the content of zirconium is 0.001% (weight percentage) in the Scium trioxide.
Embodiment 2
Its operational condition and method are substantially the same manner as Example 1, and only different is to contain zirconium 0.0987% in the Scium trioxide.Feed acidity transfers to 4.09 mol perchloric acid, the concentration of scandium is 9.69 grams per liters in the feed liquid, 13.0 liters of water cumulative volumes, extract with 13.0 liters of 100%TBP, the concentration of gained balance aqueous phase scandium is 0.721 grams per liter, the concentration of scandium is 8.97 grams per liters in the balance organic phase, and the percentage extraction of scandium is 92.57%.Contain zirconium 0.00091% in the Scium trioxide.
Embodiment 3
Its operational condition and method are substantially the same manner as Example 1, and only different is to contain zirconium 0.029% in the Scium trioxide.Feed acidity transfers to 5.68 mol perchloric acid, the concentration of scandium is 40.0 grams per liters in the feed liquid, 10.0 liters of water cumulative volumes, extract with 10.0 liters of 100%TBP, the concentration of gained balance aqueous phase scandium is 3.08 grams per liters, the concentration of scandium is 36.92 grams per liters in the balance organic phase, and the percentage extraction of scandium is 92.3%.The content of zirconium is less than 0.0005% in the Scium trioxide.
Embodiment 4
Its operational condition and method are substantially the same manner as Example 1, and only different is to contain zirconium 0.029% in the Scium trioxide.Feed acidity transfers to 5.60 mol perchloric acid, the concentration of scandium is 30.0 grams per liters in the feed liquid, 8.0 liters of water cumulative volumes, extract with 16.0 liters of 100%TBP, the concentration of gained balance aqueous phase scandium is 0.473 grams per liter, the concentration of scandium is 14.76 grams per liters in the balance organic phase, and the percentage extraction of scandium is 98.4%.The content of zirconium is 0.00074% in the Scium trioxide.
Claims (5)
1. the processing method of an extracting and separating zirconium from Scium trioxide, feature of the present invention is, tributyl phosphate with 100% is that extraction agent is as organic phase, with the 3-7 mol perchloric acid solution that contains 9.0-50.0 grams per liter scandium is that feed liquid is as water, extract, scandium is come together in the organic phase, the organic phase solution that contains scandium is carried out back extraction.
2. according to the processing method of claim 1 a kind of extracting and separating zirconium from Scium trioxide, it is characterized in that organic phase is 1/2-3/1 (volume ratio) with compare (O/A) of water during extraction.
3. according to the processing method of claim 1 a kind of extracting and separating zirconium from Scium trioxide, it is characterized in that, carry out back extraction as reverse-extraction agent with the hydrochloric acid soln of 0.5-1.5 mol.
4. according to the processing method of claim 3 a kind of extracting and separating zirconium from Scium trioxide, it is characterized in that organic phase is 1/2-3/1 (volume ratio) with compare (O/A) of water during reextraction.
5. according to the processing method of claim 1 a kind of extracting and separating zirconium from Scium trioxide, it is characterized in that, contain zirconium 0.029-0.1% (weight percentage) in the stock liquid Scium trioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90108823A CN1032871C (en) | 1990-11-07 | 1990-11-07 | Method of extracting and separating zirconium from scandium oxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90108823A CN1032871C (en) | 1990-11-07 | 1990-11-07 | Method of extracting and separating zirconium from scandium oxide |
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| CN1061246A CN1061246A (en) | 1992-05-20 |
| CN1032871C true CN1032871C (en) | 1996-09-25 |
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| CN90108823A Expired - Fee Related CN1032871C (en) | 1990-11-07 | 1990-11-07 | Method of extracting and separating zirconium from scandium oxide |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676830A (en) * | 2011-03-08 | 2012-09-19 | 龙颖 | Method for extracting scandium oxide from tungsten steel slag |
| CN103468978B (en) * | 2013-08-15 | 2016-03-30 | 中国恩菲工程技术有限公司 | A kind of method carrying scandium from laterite nickel ore by sulfuric acid leaching liquid |
| CN103468979B (en) * | 2013-08-15 | 2016-02-24 | 中国恩菲工程技术有限公司 | The method of scandium is reclaimed from smelting laterite-nickel ores iron aluminium slag |
| US11142809B2 (en) | 2015-02-10 | 2021-10-12 | Scandium International Mining Corp. | Systems and processes for recovering scandium values from laterite ores |
| CN106011485B (en) * | 2016-07-14 | 2018-11-16 | 潮州三环（集团）股份有限公司 | From the method for extracting scandium oxide in waste residue containing scandium |
| CN106430278B (en) * | 2016-09-28 | 2017-08-25 | 益阳鸿源稀土有限责任公司 | A kind of preparation method of high-pure anhydrous acetic acid scandium and High-purity Sc Oxide |
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| CN1061246A (en) | 1992-05-20 |
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