CN1010579B - Recovering scandium from titanium-iron ore - Google Patents
Recovering scandium from titanium-iron oreInfo
- Publication number
- CN1010579B CN1010579B CN 87101034 CN87101034A CN1010579B CN 1010579 B CN1010579 B CN 1010579B CN 87101034 CN87101034 CN 87101034 CN 87101034 A CN87101034 A CN 87101034A CN 1010579 B CN1010579 B CN 1010579B
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- scandium
- tio
- extraction
- ethylhexyl
- acidity
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Abstract
The present invention relates to a method for extracting an oxide of scandium metal. The 0.5MP204+4-8%TBP-kerosene with a phase ratio of O/A=1/20 for balancing 15 minutes is used for extracting coordinately and initially enriching scandium from sulfuric acid decomposition titanium-removal liquid with the acidity of 5 to 8 mol H2SO4 and 5 to 20 milligrams/liter of scandium content. After extraction, the scandium is reversely extracted by NaOH by an organic phase without impurities, and then is dissolved by hydrochloric acid; finally, the scandium is separated and purified by an extraction chromatography of extraction resin containing 55 to 62% of TBP (or P350). The resin particles are sieved by 100 to 150 meshes, the flow speed is 1 milliliter/centimeter<2> per minute; finally, Sc2O3 with the purity of larger than 99.9% is obtained by the refining of oxalic acid. In the method, the scandium yield is more than 70%.
Description
A kind of oxide extraction method of metal scandium.
The abundance of scandium in the earth's crust is very low, is about 6 * 10
-4%.Independently the industrial mineral resource is few for it.Industrial mainly from the processing treatment uranium ore, tungsten ore reclaims scandium in the processes such as tin ore and ilmenite.Because scandium content is very low, reclaims scandium from mineral, generally need through three phases: (1) initial stage enrichment stage; (2) isolation of purified stage and (3) are refining greater than 99%SC
2O
3Stage.
Enrichment in the early stage and isolation of purified scandium stage, solvent extration is a main method.According to document (1) comment, from the low scandium amount (10 that contains
-3-5 * 10
-2Grams per liter SC
2O
3) vitriol or hydrochloride solution in the enrichment scandium, proper with two-(2-ethylhexyl) phosphoric acid (be called for short D2EHPA).And from containing greater than 1%SC
2O
3Isolation of purified scandium in the enriched substance, then available butyl ester extracting scandium from hydrochloric acid or salpeter solution.After oxalic acid precipitation is refining greater than 99%Sc
2O
3
When sulfuric acid process was decomposed ilmenite, hydrolysis was except that containing scandium in the waste sulfuric acid behind the titanium.Reclaim this part scandium, document (1) though in the Soviet Union is arranged with (di-(2-ethylhexyl)phosphoric acid) extracting and enriching scandium example, ilmenite place of production difference, scandium is different with other constituent content, the result of (di-(2-ethylhexyl)phosphoric acid) extracting and enriching scandium is difference also.As, the ilmenite in Guangxi, China Guangdong contains the 0.004-0.006% scandium approximately.When sulfuric acid process was decomposed the manufacturing titanium dioxide, hydrolysis was except that containing 10-20 mg/litre scandium, impurity F e, TiO in the sulfuric acid liquid behind the titanium
2Each about 30-40 grams per liter of content, the Ca that also has every liter of number to restrain, Mg.And Si, Al, the Ln series elements, As, the V equal size is also than scandium height.At Flos Bombacis Malabarici 60%TiO
2Titanium slag in, Al
2O
3+ SiO
2The content of+Mg accounts for 30%, and CaO accounts for 3%, and ∑ Fe accounts for 2%, V
2O
5Account for 0.5%, even Cr
2O
3Content (about 0.02%) also than the high order of magnitude of scandium.When it decomposed the manufacturing titanium dioxide through sulfuric acid, hydrolysis was except that containing only 5-8 mg/litre of scandium in the solution behind the titanium.Forming so complicatedly, with (di-(2-ethylhexyl)phosphoric acid) extracting and enriching scandium, the result is unsatisfactory in the high again sulfuric acid medium of foreign matter content.As:
As water (H
+)=5-7MOL, Sc=8.0 mg/litre, TiO
2During=5.4 grams per liters (other impurity are not analyzed, and are as follows),, compare O/A=1/20 with 0.5M (di-(2-ethylhexyl)phosphoric acid)-kerosene extraction scandium, balance 15 minutes, the percentage extraction of scandium not high (table 1):
Table 1 acidity is to 0.5M (di-(2-ethylhexyl)phosphoric acid)
The influence of-kerosene extraction scandium
Water balance acidity Sc percentage extraction TiO
2Percentage extraction
〔H
+〕，MOL % %
5.1 87.50 12.96
5.8 81.25 11.11
6.1 62.50 12.96
6.6 62.50 14.81
Simultaneously, along with aqueous phase Sc, Ti content increases, and the percentage extraction of Sc obviously descends.When the content height of Sc to about 20 mg/litre, TiO
2Content is during greater than 10 grams per liters, under same (di-(2-ethylhexyl)phosphoric acid) extraction conditions, and the percentage extraction of Sc only about 50%.And, when using H
2SO
4Deng in the organic phase of washing collection back during titanium,, Sc can not be enriched to 10% even add hydrogen peroxide complexing titanium.In washing process repeatedly, Sc has lost 5-10% on the contrary.Equally, when tributyl phosphate isolation of purified scandium (HCl medium), the scandium that collection is gone into organic phase need remove titanium with many washings of about 7MOL HCl.Add H during washing
2O
2After, detersive efficiency has improved, but operating environment has degenerated (effusion chlorine).
In order to improve extracting scandium from ilmenite sulfuric acid decomposed solution, the washing that reduces after extracting removes the titanium operation, and then the yield of raising scandium, invented acid Phosphorus and neutral phosphonic acid extraction agent synergistic extraction initial stage enrichment scandium, collection back organic phase is removed impurity such as titanium without washing, directly use the sodium hydroxide back extraction, dissolving with hydrochloric acid, the extracting resin of forming through neutral phosphorus extractant (a kind of macromolecule resin that is made by liquid suspension polymerization principle under the initiator effect by neutral phosphorus extractant and polymer carrier) is gone up extraction-chromatography isolation of purified scandium again, last oxalic acid make with extra care purity greater than 99.9%Sc
2O
3Method.The used acidic phosphorus extractant of the present invention is (di-(2-ethylhexyl)phosphoric acid) and 2-ethylhexyl phosphoric acid single 2-ethyl polyhexamethylene (2-ethylhexyl phosphoric acid single 2-ethyl polyhexamethylene); Neutral phosphorus extractant is tributyl phosphate and methyl acid phosphate diformazan heptyl ester).Extracting resin contains neutral phosphorus extractant 55-62%(weight ratio).Now details are as follows with the inventive method:
(di-(2-ethylhexyl)phosphoric acid)+tributyl phosphate extracting scandium from the HCl medium is a kind of counter-cooperative-ing extraction (2).The present invention adopts (di-(2-ethylhexyl)phosphoric acid) (or 2-ethylhexyl phosphoric acid single 2-ethyl polyhexamethylene)+tributyl phosphate from H
2SO
4Extraction Sc is a kind of positive coorperativity extraction (table 2, table 3) in the medium:
Table 2 acidity is to 0.5M (di-(2-ethylhexyl)phosphoric acid+10% tributyl phosphate-kerosene extraction scandium influence
Water: H
2SO
4Medium contains the Sc=8.0 mg/litre, TiO
2=5.4 grams per liters
Organic phase: 0.5M (di-(2-ethylhexyl)phosphoric acid)+10% tributyl phosphate-kerosene
Compare O/A=1/20, starting time: 15 minutes
Water balance acidity Sc percentage extraction TiO
2Percentage extraction β Sc/TiO
2
〔H
+〕，MOL % %
5.0 93.75 12.96 100
6.0 87.50 14.81 40
6.5 75.00 14.81 17.1
Table 3 tributyl phosphate addition is to the influence of (di-(2-ethylhexyl)phosphoric acid) or 2-ethylhexyl phosphoric acid single 2-ethyl polyhexamethylene extracting scandium
Water: 6MOL H
2SO
4, contain the Sc=17.5 mg/litre, TiO
2=12.5 grams per liters
Compare O/A=1/20, starting time: 10 minutes
Organic phase title TBP add-on Sc percentage extraction TiO
2Percentage extraction β Sc/TiO
2
% % %
0 53.1 - -
2 60.0 1.5 96.8
0.5M〔＝（2- 4 82.9 1.8 268.5
Ethylhexyl) phosphoric acid)
-kerosene 6 91.4 2.5 418.3
8 85.7 1.8 73.6
10 82.9 1.0 381
0 50.3 - -
2 61.7 1.4 111.2
0.5M2-ethyl oneself 4 64.3 1.2 150
Base phosphoric acid single 2-ethyl
Ester-kerosene 6 60.0 2.5 58.8
8 54.3 1.8 66.0
10 51.4 2.5 41.5
Organic phase after the extraction is removed TiO without washing
2Deng impurity, its Sc
2O
3About about 300 mg/litre of content, Sc
2O
3/ TiO
2=1-2%(weight ratio).Directly, get Sc(OH) with Sc in the NaOH back extraction organic phase
3Precipitation.With Sc(OH)
3Be dissolved in HCl, be adjusted to (the tributyl phosphate extracting resin is 6-8MOL HCl, and methyl acid phosphate diformazan heptyl ester extracting resin is 4.5-6MOL HCl) behind the certain acidity, through extracting resin absorption scandium, and titanium does not adsorb substantially.Remove impurity such as titanium through HCl drip washing then, use again less than 0.5MOL HCl drip washing scandium, in the leacheate of collecting, TiO
2/ Sc
2O
3＜1%(weight ratio).The yield of whole extraction-chromatography isolation of purified scandium is greater than 90%.TiO among the Sc
2Degree of purification greater than 10000 times.
The results list 4 of extraction-chromatography, table 5.
Table 4 Sc, the separation of Ti on the tributyl phosphate extracting resin
The tributyl phosphate extracting resin, resin size 100-150 sieve mesh.
Extraction-chromatography post post footpath: 16 millimeters, post height: 110 millimeters
Flow velocity: 1 milliliter/centimetre
2Divide
Charging: 50 milliliters of 7.6MOL HCl feed liquids contain Sc altogether
2O
340 milligrams, TiO
24.16 gram.
Effluent liquid
Elution volume
TiO
2Concentration: TiO
2Total amount: Sc
2O
3Concentration: Sc
2O
3Total amount:
(millimeter)
Mg/ml milligram mg/ml milligram
Charging 10 0.0306 0.306
10 40.75 407.5
10 79.67 796.7
10 80.63 806.3
13 79.92 1039
7MOL·HCl 10 79.28 792.8
10 42.38 423.8
10 3.56 35.6
10 0.43 4.3
13 0.325 4.3 0.136 1.78
0.3MOL HCl 20 0.014 0.28 1.87 37.45
10 0.0428 0.428
10 0.0071 0.071
10 0.0036 0.036
10 0.0036 0.036
13 0 0
Total amount 4,310 39.8
Material balance 103% 99.5%
Sc on the table 5 methyl acid phosphate diformazan heptyl ester extracting resin, the separation of Ti
Methyl acid phosphate diformazan heptyl ester extracting resin, resin size 100-150 sieve mesh
Extraction-chromatography post post footpath: 16 millimeters, post height: 110 millimeters
Flow velocity: 1 milliliter/centimetre
2Divide
Totally 50 milliliters of feeding liquid 5.5MOL HCl contain the Sc12.3 milligram, TiO altogether
21.09 gram
Effluent liquid
Elution volume
TiO
2Concentration: TiO
2Total amount: Sc
2O
3Concentration: Sc
2O
3Total amount:
(milliliter)
Mg/ml milligram mg/ml milligram
Electrical materials and appliances 10 0000
10 9.0 90 8.8×10
-40.009
10 19.62 196.2 3.9×10
-40.004
10 22.12 221.2 5.1×10
-40.005
10 22.48 224.8 4.1×10
-40.004
5.0MOLHCl 10 22.48 224.8 5.8×10
-40.006
10 8.36 83.6 4.7×10
-40.005
10 2.41 24.1 5.3×10
-40.005
10 1.19 11.9 3.9×10
-40.004
10 0.23 2.3 4.7×10
-40.005
Water wash 10 0.01 0.1
10 - - 1.23 12.3
Extraction-chromatography is separating obtained contains scandium solution and promptly gets greater than 99.9%Sc through oxalic acid precipitation is refining
2O
3
According to the description of the inventive method, the hydrolysis of decomposing ilmenite from sulfuric acid except that the condition that reclaims scandium the solution behind the titanium is:
Solution solution acidity: 5-8MOL H
2SO
4(best 5-5.5MOL), scandium content 5-20 mg/litre, (best 0.5M (di-(2-ethylhexyl)phosphoric acid)+5% tributyl phosphate-kerosene) compares O/A=1/20 with 0.5M (di-(2-ethylhexyl)phosphoric acid)+4-8% tributyl phosphate-kerosene synergistic extraction scandium, starting time is 15 minutes, and the percentage extraction of Sc is greater than 87%.The Sc(OH of NaOH back extraction gained)
3With molten Jie of HOl, extraction-chromatography isolation of purified scandium.When adopting 55-62% tributyl phosphate extracting resin (granularity 100-150 sieve mesh), the best 7.5MOL HCl of charging acidity 7.5-8MOL HCl(), 1 milliliter/centimetre of flow velocity
2Divide, use 7.0-7.5MOL HCl drip washing titanium then, less than the best water of 0.5MOL HCl() the drip washing scandium; When perhaps using 55-62% methyl acid phosphate diformazan heptyl ester extracting resin (granularity 100-150 sieve mesh), the best 5.5-5.8MOL HCl of charging acidity 5-6MOL HCl(), 1 milliliter/centimetre of flow velocity
2Divide, use 5-6MOL HCl drip washing titanium then, less than the best water of 0.5MOL HCl() the drip washing scandium, the yield of scandium is greater than 90%.Extraction-chromatography gained scandium solution is refining greater than 99.9%Sc through oxalic acid precipitation
2O
3The yield of entire method scandium is greater than 70%.
Embodiment 1
1000 liters (waste liquid dissociated H after hydrolysis removed titanium
2SO
4Acidity 5MOL, Sc=16.75 mg/litre, TiO
2=8.8 grams per liters) and 0.5M (di-(2-ethylhexyl)phosphoric acid)+5% tributyl phosphate-kerosene 50 liftings go in 1.5 cubic metres the single stage extractor, stir 15 minutes (120 rev/mins of rotating speeds), static layering.Gained balance aqueous phase Sc is 1.88 mg/litre, TiO
28.0 grams per liter; Sc is 303.5 mg/litre in the balance organic phase, TiO
216.2 grams per liter.The single-stage extraction rate that calculates Sc in view of the above is 88%, TiO
2Be 9.1%.
Embodiment 2
0.5M organic phase behind (di-(2-ethylhexyl)phosphoric acid)+5% tributyl phosphate-kerosene extraction Sc includes 271 mg/litre Sc, 14.83 grams per liter TiO
2With the direct back extraction Sc of 2MOL NaOH, compare=50 liters/50 liters starting time 3 minutes.Contain Sc10.5 mg/litre, TiO after the back extraction in the organic phase
22.77 grams per liter.Oxyhydroxide after filtration, its filtrate contains Sc0.056 mg/litre, TiO
20.33 grams per liter.
Embodiment 3
7.7MOL HCl solution contains Sc
2O
30.22 grams per liter, TiO
224.46 grams per liter, totally 9.86 liters.The extraction-chromatography post that the extracting resin that contains the 55-62% tributyl phosphate of the granularity of flowing through 100-150 sieve mesh is formed.40 * 760 millimeters of chromatographic column post footpath φ, flow 15 ml/min.After treating that feed liquid has flowed, with 7MOL HCl drip washing titanium, totally 4 liters of leacheate volumes.And then use the water wash scandium, totally 10 liters.The gained result is:
By the effusive TiO of feeding liquid
2Totally 219.38 restrain
The effusive TiO of 7MOL HCl leacheate
2Totally 20.17 restrain SC
2O
3Totally 0.10 restrain
The effusive TiO of water wash scandium
20.015 gram, Sc
2O
32.11 gram.
Embodiment 4
55-62% methyl acid phosphate diformazan heptyl ester extracting resin, granularity 100-150 sieve mesh.40 * 760 millimeters of extraction-chromatography post post footpath φ, charging is a 5.5MOL HCl solution, Sc content 0.606 grams per liter, TiO
226.1 grams per liter, input speed 15 ml/min, co-fed 6 liters.Rise the drip washing titanium with 5MOL HCl2 then, 0.9 premium on currency drip washing scandium gets the Sc3.50 gram, TiO
20.021 gram, Sc yield 96.2%.
Embodiment 5
Oxalic acid precipitation is refining.To contain Sc
2O
3～90%, Fe
2O
35-10%, TiO
2＜0.9% solution is regulated acidity to PH2 with ammoniacal liquor, and saturated oxalic acid solution (the oxalic acid dosage is 3 times of theoretical amount) makes oxalic acid scandium precipitation then, and ageing is filtered, oven dry, and 800 ℃ of calcinations get Scium trioxide, wherein contain Sc
2O
3～99%, Fe
2O
3～0.1%, TiO
2～0.05%.With HCl this Scium trioxide is dissolved, oxalic acid precipitation gets Sc again
2O
3＞99.9% oxide compound.Secondary oxalic acid precipitation gained oxide compound major impurity analytical results such as condition, %:
Ae
2O
3CuO Fe
2O
3MgO TiO
2
Oxalic acid precipitation: 0.013 0.002 0.1 0.0016 0.062
Cr
2O
3V
2O
5Sc
2O
3
＜0.003 ＜0.003 99
Ae
2O
3CuO Fe
2O
3MgO TiO
2
Secondary oxalic acid precipitation: 0.0010＜0.0001 0.0056 0.0005 0.003
Cr
2O
3V
2O
5Sc
2O
3
＜0.003 ＜0.003 ＞99.9
Reference
〔1〕С.А.СЕМЕНОВ ДР，чВеТНые МеТаЛЛЫ，12 12（1983）43-47
〔2〕Е·Б·МNХЛNН ДР，
Claims (4)
1, extracts the method for preparing the scandium oxide compound a kind of the branch the releasing titanium liquid from ilmenite sulfuric acid, it is characterized in that, Phosphorus and the neutral phosphorus extractant synergistic extraction enrichment scandium with acidity, collection back organic phase is directly used the sodium hydroxide back extraction without washing, dissolving with hydrochloric acid, extracting resin chromatographic separation through neutral phosphorus extractant purifies scandium again, last extracting and refining Scium trioxide.
2, the Phosphorus and neutral phosphorus extractant synergistic extraction enrichment scandium of the described acidity of claim 1 is characterized in that adopting (di-(2-ethylhexyl)phosphoric acid) (or 2-ethylhexyl phosphoric acid single 2-ethyl polyhexamethylene)+tributyl phosphate from H
2SO
4Extract Sc in the medium, solution acidity 5-8MOLH
2SO
4(best 5-5.5MoL), scandium content 5-20 mg/litre, from 0.5M (di-(2-ethylhexyl)phosphoric acid)+4-8% tributyl phosphate-kerosene (best 0.5M (di-(2-ethylhexyl)phosphoric acid)+5% tributyl phosphate-kerosene), compare O/A=1/20,15 minutes synergistic extraction Sc of starting time.
3, the extracting resin chromatographic separation of the described neutral phosphorus extractant of claim 1 purifies scandium, it is characterized in that using and contain 55-62% tributyl phosphate extracting resin, granularity 100-150 sieve mesh, the best 7.5MoLHCl of charging acidity 7.5-8MoLHCl(), 1 milliliter/centimetre of flow velocity
2Divide, use 7.0-7.5MoLHCl drip washing titanium then, less than the best water of 0.5MoLHCl() the drip washing scandium, make the Sc in the charging
2O
3/ TiO
2=1-2% is purified to the TiO in the drip washing scandium liquid
2/ Sc
2O
3＜1%(weight ratio).
4, the extracting resin chromatographic separation of the described neutral phosphorus extractant of claim 1 purifies scandium, it is characterized in that using and contain 55-62% methyl acid phosphate diformazan heptyl ester extracting resin, granularity 100-150 sieve mesh, the best 5.5-5.8MoLHCl of charging acidity 5-6MoLHCl(), 1 milliliter/centimetre of flow velocity
2Divide, use 5-6MoLHCl drip washing titanium then, less than the best water of 0.5MoLHCl() the drip washing scandium, make the Sc in the charging
2O
3/ TiO
2The TiO of=1-2% passivation in the drip washing scandium liquid
2/ Sc
2O
3＜1%(weight ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87101034 CN1010579B (en) | 1987-05-08 | 1987-05-08 | Recovering scandium from titanium-iron ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87101034 CN1010579B (en) | 1987-05-08 | 1987-05-08 | Recovering scandium from titanium-iron ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87101034A CN87101034A (en) | 1988-11-23 |
| CN1010579B true CN1010579B (en) | 1990-11-28 |
Family
ID=4813126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87101034 Expired CN1010579B (en) | 1987-05-08 | 1987-05-08 | Recovering scandium from titanium-iron ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1010579B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427618C (en) * | 2005-05-19 | 2008-10-22 | 昆明理工大学 | Process for preparing aluminium-scandium intermediate alloy from scandium-containing mineral by one-step method |
| CN102127641B (en) * | 2010-07-20 | 2012-09-12 | 湖南稀土技术开发有限公司 | Method for recovering scandium and titanium in titanium white wastewater |
| CN102071317B (en) * | 2011-01-27 | 2012-12-26 | 太原理工大学 | Composite extracting agent for extracting scandium from red mud hydrochloric acid leachate |
| CN103667748B (en) * | 2013-12-30 | 2015-04-01 | 贵州鑫亚矿业有限公司 | Method for preparing purified scandium from crude scandium enriched in raw anatase and serving as raw material |
| CN106629809B (en) * | 2016-12-20 | 2022-09-16 | 攀枝花市精研科技有限公司 | Method for purifying coarse scandium oxide |
| CN116445750A (en) * | 2017-11-17 | 2023-07-18 | Ii-Vi特拉华有限公司 | Selective recovery of rare earth metals from acidic slurries or acidic solutions |
| CN109609775B (en) * | 2018-12-31 | 2020-08-07 | 南京格洛特环境工程股份有限公司 | Resource comprehensive utilization method of steel slag |
-
1987
- 1987-05-08 CN CN 87101034 patent/CN1010579B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN87101034A (en) | 1988-11-23 |
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