CN1061246A - The method of extracting and separating zirconium from Scium trioxide - Google Patents
The method of extracting and separating zirconium from Scium trioxide Download PDFInfo
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- CN1061246A CN1061246A CN90108823A CN90108823A CN1061246A CN 1061246 A CN1061246 A CN 1061246A CN 90108823 A CN90108823 A CN 90108823A CN 90108823 A CN90108823 A CN 90108823A CN 1061246 A CN1061246 A CN 1061246A
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- scandium
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Abstract
The present invention relates to the processing method of extracting and separating zirconium from Scium trioxide, the TBP with 100% is an extraction agent, is feed liquid with the perchloric acid solution of the 3-7 mol that contains 9.0-50.0 grams per liter scandium, extracts.Extraction phase is 1/2-3/1 than (0/A).The invention has the advantages that the good separating effect of scandium and zirconium, its separation factor is up to 10
3The rate of recovery height of scandium, its direct yield is 90-96%, total yield is greater than 97%.The production capacity height, remarkable in economical benefits, chemical materials consumes low, and the chemical materials unit consumption is less than 1100 yuan of/kilogram Scium trioxides, and is with short production cycle, easy to operate, without any need for specific installation, easy to utilize.
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 the hydrolysising mother liquid from titanium white production, extracts in the chlorination flue dust of chlorination titanium slag production 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, Edited by R.G.Bautista and M.M.Wong, The Minerals, Metals and materials Society, 1988) proposed with 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 (tributyl phosphate), 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) in the feed liquid concentration of scandium too low＜2-4 grams per liter Scium trioxide, treatment capacity is little, 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, TBP with 100% is an extraction agent＜as organic phase 〉, be feed liquid＜as water with the solution of the 3-7 mol perchloric acid that contains 9.0-50 grams per liter scandium, extract, scandium is come together in the organic phase, and separate with zirconium.
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 was generally 5-30 minute.The percentage extraction of scandium is 92-99%.Its organic phase and water compares＜O/A during extracting scandium〉be good with 1/2-3/1.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.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: 3 perchloric acid solution is advisable.The amount of the perchloric acid that is added during dissolving adds 1: 1 perchloric acid 12-24 milliliter for well by 1 gram Scium trioxide, less than 12 milliliters, the Scium trioxide dissolving not exclusively, the rate of recovery of scandium is lowered, if greater than 24 milliliters, then increase the cost of Scium trioxide, 1 gram Scium trioxide dissolves with the acid of 1: 1 peracid 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, should on electric furnace, slowly heat while stirring, make its reaction 2-4 hour, Scium trioxide is dissolved fully, solution is limpid state, stops 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, and production capacity is little.But the concentration of scandium is greater than 50 grams per liters, and separation factor β value diminishes, and it is big that organic phase viscosity becomes, and 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 0/A that compares of organic phase and water is 1/2-3/1 during reextraction, and the value of comparing 0/A is too little, and the water volume is big, the concentration of scandium is low, makes troubles for later oxalic acid precipitation, and it is too big to compare 0/A, the organic phase volume is big, and the number of times of reextraction will increase, and is good so compare 0/A with 1/2-3/1.
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, once can reduce to below the 10PPm with processing method extracting and separating of the present invention with the Scium trioxide that contains 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 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 are placed 3 liters evaporating dish at (containing zirconium 0.043%), adds 1: 1 2400 milliliters in perchloric acid, on electric furnace, slowly heat, stir, reacted 3 hours, it is limpid to make the solid oxidation scandium be dissolved to solution fully, stop heating, cooling, the dissolution rate of Scium trioxide is greater than 99.9%.
The scandium solution that contains 0.043% zirconium behind 1: 1 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% 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 (4)
1, a kind of from Scium trioxide the processing method of extracting and separating zirconium, feature of the present invention is that the TBP with 100% is extraction agent (as an organic phase), is feed liquid (as water) with the 3-7 mol perchloric acid solution that contains 9.0-50.0 grams per liter scandium, extract, scandium is come together in the organic phase.
According to the processing method of claim 1 a kind of extracting and separating zirconium from Scium trioxide, it is characterized in that 2, organic phase is 1/2-3/1 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, the organic phase solution that contains scandium is carried out back extraction.
4, according to the processing method of claim 3 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.
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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| Publication Number | Publication Date |
|---|---|
| CN1061246A true CN1061246A (en) | 1992-05-20 |
| CN1032871C CN1032871C (en) | 1996-09-25 |
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| Application Number | Title | Priority Date | Filing Date |
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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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Cited By (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 |
| CN103468979A (en) * | 2013-08-15 | 2013-12-25 | 中国恩菲工程技术有限公司 | Method for recycling scandium from lateritic nickel ore smelted iron aluminum slag |
| CN103468978A (en) * | 2013-08-15 | 2013-12-25 | 中国恩菲工程技术有限公司 | Method for extracting scandium from lateritic nickel ore sulfuric acid leaching solution |
| CN106011485A (en) * | 2016-07-14 | 2016-10-12 | 潮州三环（集团）股份有限公司 | Method for extracting scandium oxide from scandium-containing waste residue |
| CN106430278A (en) * | 2016-09-28 | 2017-02-22 | 益阳鸿源稀土有限责任公司 | Method for preparing high-purity anhydrous scandium acetate and high-purity scandium oxide |
| US11142809B2 (en) | 2015-02-10 | 2021-10-12 | Scandium International Mining Corp. | Systems and processes for recovering scandium values from laterite ores |
-
1990
- 1990-11-07 CN CN90108823A patent/CN1032871C/en not_active Expired - Fee Related
Cited By (7)
| 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 |
| CN103468979A (en) * | 2013-08-15 | 2013-12-25 | 中国恩菲工程技术有限公司 | Method for recycling scandium from lateritic nickel ore smelted iron aluminum slag |
| CN103468978A (en) * | 2013-08-15 | 2013-12-25 | 中国恩菲工程技术有限公司 | Method for extracting scandium from lateritic nickel ore sulfuric acid leaching solution |
| US11142809B2 (en) | 2015-02-10 | 2021-10-12 | Scandium International Mining Corp. | Systems and processes for recovering scandium values from laterite ores |
| CN106011485A (en) * | 2016-07-14 | 2016-10-12 | 潮州三环（集团）股份有限公司 | Method for extracting scandium oxide from scandium-containing waste residue |
| 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 |
| CN106430278A (en) * | 2016-09-28 | 2017-02-22 | 益阳鸿源稀土有限责任公司 | Method for preparing high-purity anhydrous scandium acetate and high-purity scandium oxide |
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| Publication number | Publication date |
|---|---|
| CN1032871C (en) | 1996-09-25 |
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