CN103667749B - Method for enriching scandium in anatase raw ore - Google Patents
Method for enriching scandium in anatase raw ore Download PDFInfo
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- CN103667749B CN103667749B CN201310740585.6A CN201310740585A CN103667749B CN 103667749 B CN103667749 B CN 103667749B CN 201310740585 A CN201310740585 A CN 201310740585A CN 103667749 B CN103667749 B CN 103667749B
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Abstract
The invention discloses a method for enriching scandium in anatase raw ore. The method comprises the following steps: 1) mixing the anatase raw ore with inorganic acid to obtain a scandium leachate and tailings; 2) mixing an extraction agent with an organic solvent and an additive, so as to obtain an organic phase; 3) extracting the scandium leachate by use of the organic phase, so as to obtain a first extract liquor; 4) washing the first extract liquor by use of a washing liquid, and then back-extracting scandium element in the first extract liquid by use of a back-extracting solution, so as to obtain a coarse scandium solution. The method disclosed by the invention can be used for improving the grade of the scandium in the raw ore by more than 150 times and ensuring that the total scandium yield is greater than 80%; back-extracting of scandium is easy, and loss of the organic phase is less; the chemical raw material consumption is less, and the method is clean and environment-friendly.
Description
Technical field
The present invention relates to the enriching method of anatase raw ore scandium, in particular to taking anatase raw ore as raw material, first with chemical method by scandium Elements Leaching, then extract the technique of scandium with solvent extration.
Background technology
Scandium, as one of strategic element, can be applied to high-tech area.The independent mineral reserve of scandium almost do not have, and main association is in rare-earth mineral, bauxite, iron ore, navajoite, titanium ore, tungsten ore, uranium ore etc.China mainly reclaims scandium at present from the mineral such as rare earth ore containing sc, titanium ore (titanium white waste acid), tungsten slag.Also the report reclaiming scandium from bauxite (red mud) is had in recent years.
It is raw material that Li Jiucheng discloses rare-earth mineral (comprising association rare-earth mineral, rich scandium subsiliceous rock saprolite, rich scandium bauxite and red mud, mixed rare-earth oxide muriate), select hydrochloric acid, sulfuric acid, ammonium chloride, ammonium sulfate, sodium-chlor to leach and carry scandium and rare earth mother solution, select the method (CN85106255) of the extraction process scandium-enricheds such as naphthenic acid HA, P204, P507, P350, TBP.Hunan rare-earth technique company and east scandium industry individually disclose the method (CN201010230723.2, CN201210208769.3) that P204-TBP and P507-TBP reclaims scandium titanium from titanium dioxide wastewater.Now part scandium being reclaimed Patents enumerates in table 1:
Anatase raw ore, weathering is comparatively complete, and outward appearance be khaki color, light brown, grey, loose soil bulk, containing ferric oxide about 20%, titanium oxide about 5%, particularly Scium trioxide reach 65ppm and more than, far above the Abundances (about 25ppm) of scandium in soil.The occurrence status research of scandium element shows, the scandium of 86% is that ionic species is adsorbed or is wrapped in the mineral such as kaolinite, limonite, has very high extraction and is worth, but there is not yet examples of industrial application.Therefore need to seek scandium-enriched in a kind of applicable anatase raw ore, and remove the method for the impurity such as iron, aluminium, titanium.
Summary of the invention
The object of the invention is the enriching method providing scandium element in a kind of anatase raw ore, is namely raw material with anatase raw ore, first with chemical method by scandium Elements Leaching, then extract scandium with solvent extration.During chemical method leaching scandium, because most of scandium is ionic species, be easy to leaching; And the concentration of scandium is high in leaching liquid, reduce industrial chemicals consumption; Leaching liquid impurity is few, and extraction phenomenon is good.Specifically comprise the following steps:
1) anatase raw ore is mixed with mineral acid, obtain scandium leach liquor and tailings;
2) extraction agent is mixed with organic solvent and additive, obtain organic phase;
3) use described organic phase to extract scandium leach liquor, obtain the first extraction liquid;
4), after washing the first extraction liquid with washings, with the scandium element in described first extraction liquid of anti-stripping agent reextraction, thick scandium solution is obtained.
Preferably, in anatase raw ore, the grade of Scium trioxide is 40 ~ 400ppm.
Preferably, during roasted ore leaching scandium, mineral acid is selected from one or more in hydrochloric acid, nitric acid and sulfuric acid, and volumetric concentration is 5 ~ 30%.Leach liquor composition is Sc
2o
35 ~ 150ppm, TiO
20.05 ~ 5 grams per liter, Fe
2o
35 ~ 50 grams per liters, free H
+0.2 ~ 8.0 mol/L.
Preferably, described extraction agent is selected from one or more in higly branched chain hexadecyl primary amine (code name N116), heptadecyl-9-amine (code name N179), 19 ~ pentacosyl-(10 ~ 13)-amine (code name N1923), Primene JM-T; Described organic solvent be selected from sulfonated kerosene, dimethylbenzene, hexanaphthene one or more; Described additive is selected from isooctyl alcohol or TBP; In organic phase, the volume ratio of extraction agent additive and organic solvent is 1 ~ 20:1 ~ 20:60 ~ 98.
Preferably, described washings is hydrochloric acid, nitric acid or sulfuric acid, and volumetric concentration is 0.1 ~ 4 mol/L; Described strip liquor is hydrochloric acid or nitric acid, and volumetric concentration is 0.2 ~ 4 mol/L.
Preferably, described organic phase, stock liquid, washings and anti-stripping agent throughput ratio are 0.5 ~ 1.5:2 ~ 10:0.25 ~ 2:0.25 ~ 2; Extraction progression is 1 ~ 6 grade, and washing progression is 1 ~ 6 grade; Reextraction progression is 1 ~ 6 grade.
According to the method for scandium-enriched from anatase raw ore of the present invention, Sc in described anatase raw ore
2o
3grade be 40 ~ 400ppm, separately containing TiO
2about 5%, Fe
2o
3about 20%, Al
2o
3about 23%, other component group will be silicate.Raw ore and mineral acid are mixed to get leach liquor, and after leaving standstill, supernatant liquid is as the stock liquid of extracting operation.Described mineral acid is preferably nitric acid, hydrochloric acid or sulfuric acid.In a preferred embodiment, leaching rate is greater than 85%, and near leaching storage tank, radioactivity is lower than 0.25 μ Sv/h, without the need to radioactivity protection.
In the method for scandium-enriched from anatase raw ore according to the present invention, described extraction agent be selected from N116, N179, N1923, Primene JM-T one or more.Described organic solvent be selected from sulfonated kerosene, dimethylbenzene, hexanaphthene one or more, be more preferably sulfonated kerosene; Described additive is selected from isooctyl alcohol or TBP; In organic phase, the volume ratio of extraction agent, additive and organic solvent is 1 ~ 20:1 ~ 20:60 ~ 98, is more preferably 3 ~ 8:3 ~ 8:84 ~ 94.
In the method for scandium-enriched from anatase raw ore according to the present invention, described washings is for removing the impurity such as iron, titanium carried secretly in the first extraction liquid, be not particularly limited it, but be preferably hydrochloric acid, nitric acid or sulfuric acid, volumetric concentration is 0.1 ~ 4 mol/L.Described strip liquor is used for the back extraction of scandium in the first extraction liquid, and make organic phase regenerate simultaneously and be convenient to recycle, be preferably hydrochloric acid or nitric acid, concentration is 0.2 ~ 4 mol/L.
In the method for scandium-enriched from anatase raw ore according to the present invention, the extraction equipment implementing fractional-distillation extraction is not specifically limited, as long as it can realize extraction object of the present invention.Described extraction equipment can select equipment well known in the art, as separating funnel, mixed settler extractor, centrifugal extractor etc.In a preferred embodiment, mixed settler extractor is used to carry out fractionation extraction.
Fig. 1 is shown in technical process of the present invention.
As shown in Figure 1, wherein n, m, j are fractionation extraction progression sequence number, n=1 ~ 6; M=n+ (1 ~ 6); J=m+n+ (1 ~ 4).Organic phase adds from the 1st grade, and stock liquid adds by n-th grade, and after organic extractant phase, raffinate is discharged from the 1st grade of below, washings adds from m level, and anti-stripping agent adds from jth level, is stripped by the first extraction liquid after washing, obtain thick scandium, discharge from m+1 level.Organic phase after reextraction is discharged from jth level, recycle.
Due in this anatase raw ore, the occurrence status of scandium element and the significantly different containing scandium ore (such as ilmenite, artificial rutile) of other type, easily, in leach liquor, the content of impurity titanium is little, is more conducive to extracting operation in leaching.In leach liquor, radioactive activity is low, to operative's safety.Also different by the technique of sodium hydroxide pellets back extraction scandium from traditional P204 or P507 extracting scandium from titanium white waste acid, in the extraction procedure described in this patent, amine extractant extraction ability is good, and the solubleness of organic phase is little; The reextraction of scandium is easy, and organic phase loss is little, reduces cost and improves production efficiency.The results show, use the inventive method that the grade of scandium in raw ore can be made to bring up to more than 150 times, scandium leaching rate is greater than 85%, and total recovery is greater than 80%.
Accompanying drawing explanation
The technical process of Fig. 1 scandium-enriched from anatase raw ore.
Embodiment
In order to understand the present invention further, below the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention instead of limiting to the claimed invention.Wherein, conventional chemical reagent is analytical pure.
Embodiment 1
Preparation raw material liquid: get anatase raw ore that scandium grade is 65ppm and dilute sulphuric acid reacts to obtain leach liquor, as the raw materials used liquid of extraction.By analysis, the composition of stock liquid is: Sc
2o
316.2ppm, TiO
20.66 grams per liter, Fe
2o
3(trivalent) 21 grams per liter, Al
2o
314 grams per liters, free H
+3.7 mol/L.
Preparation organic phase: the N1923 extraction agent getting technical grade is dissolved in sulfonated kerosene, and adds isooctyl alcohol, and now organic phase volume consists of 5 % N1923-5% isooctyl alcohol-90% sulfonated kerosenes.
Fractionation extraction: whole extraction process adopts separating funnel simulation fractionation extraction, comprises 2 grades of extractions, 2 grades of washings and 2 grades of back extractions.Organic phase adds from the 1st grade; Stock liquid adds from the 2nd grade; Washings adopts 0.5 mol/L sulfuric acid, adds from the 4th grade; Anti-stripping agent adopts 1.0 mol/L hydrochloric acid, adds from the 6th grade.The throughput ratio of organic phase, stock liquid, washings, anti-stripping agent is 1:4:0.5:0.3.Mixing time is 8 minutes.Through the enrichment of this flow process, obtain thick scandium solution, extraction yield reaches 97%, and in raw ore, the grade of scandium improves 160 times.Scandium leaching rate is greater than 85%, and total recovery is greater than 82%.Thick scandium solution obtains thick scandium cake through alkali precipitation, and through chemical analysis, scandium accounts for 2.5%, and iron accounts for 95%.Organic phase recycles, and extraction ability is stablized, and carries secretly with solution loss little.
Embodiment 2
Preparation raw material liquid: get scandium grade be the anatase raw ore leach liquor of 105ppm as stock liquid, its composition is: Sc
2o
343ppm, TiO
20.14 grams per liter, ferrous sulfate is (with Fe
2o
3meter) 33 grams per liters, Al
2o
318 grams per liters, free H
+3.1 mol/L.
Preparation organic phase: the N1923 extraction agent getting technical grade is dissolved in sulfonated kerosene, and adds additive TBP, and now organic phase volume consists of 5 % N1923-5%TBP-90% sulfonated kerosenes.
Fractionation extraction: whole extraction process adopts mixed settler extractor to carry out fractionation extraction, extraction progression is adjusted to 4 grades of extractions, 3 grades of washings and 3 grades of back extractions.Washings is 0.1 mol/L hydrochloric acid, and anti-stripping agent adopts 80 grams per liter aqueous sodium hydroxide solutions.The throughput ratio of organic phase, stock liquid, washings, anti-stripping agent is 1:5:0.5:0.25.Mixing time is 8 minutes.Through the enrichment of this flow process, total recovery is greater than 85%.
In the present embodiment, the composition of leach liquor is with ilmenite sulfuric acid decomposition and compared with the composition carrying the titanium white waste liquid after titanium, component is significantly different.The typical composition of titanium white waste liquid is: Sc
2o
323ppm, TiO
27.4 grams per liters, Fe
2o
3(divalence) 33.7 grams per liter, Al
2o
30.46 grams per liter, free sulfuric acid 2.5 ~ 3 mol/L (
nie Li etc., mining metallurgical engineering, 11 (2) 53-57,1991).
Embodiment 3
Preparation raw material liquid: with embodiment 1.
Preparation organic phase: the Primene JM-T extraction agent getting technical grade is dissolved in sulfonated kerosene, and adds isooctyl alcohol, and now organic phase volume consists of 6 % Primene JM-T-6 % isooctyl alcohol-88% sulfonated kerosenes.
Fractionation extraction: whole extraction process adopts centrifugal extractor to carry out fractionation extraction, extraction progression is 4 grades of extractions, 6 grades of washings, 3 grades of back extractions.Washings is 0.5mol/L sulfuric acid, and anti-stripping agent adopts 1.0 mol/L hydrochloric acid.The throughput ratio of organic phase, stock liquid, washings, anti-stripping agent is 1:8:0.5:0.5.Through the enrichment of this flow process, extraction yield reaches 92%, and total recovery is greater than 80%.
Above to provided by the invention from anatase raw ore the method for scandium-enriched be described in detail; apply specific case herein to set forth principle of the present invention and embodiment; the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention; can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (1)
1. the enriching method of scandium in anatase raw ore, comprises the following steps:
1) anatase raw ore is mixed with mineral acid, obtain scandium leach liquor and tailings;
2) extraction agent is mixed with organic solvent and additive, obtain organic phase;
3) use described organic phase to extract scandium leach liquor, obtain the first extraction liquid;
4), after washing the first extraction liquid with washings, with the scandium element in described first extraction liquid of anti-stripping agent reextraction, thick scandium solution is obtained;
Described extraction agent be selected from N116, N179, Primene JM-T one or more, in anatase raw ore, the grade of Scium trioxide is 40 ~ 400ppm, described mineral acid be selected from hydrochloric acid, nitric acid and sulfuric acid one or more, volumetric concentration is 5 ~ 30%; Leach liquor composition is Sc
2o
35 ~ 150ppm, TiO
20.05 ~ 5 grams per liter, Fe
2o
35 ~ 50 grams per liters, free H
+0.2 ~ 8.0 mol/L, described organic solvent be selected from sulfonated kerosene, dimethylbenzene, hexanaphthene one or more; Described additive is selected from isooctyl alcohol or TBP; In organic phase, the volume ratio of extraction agent, additive and organic solvent is 1 ~ 20:1 ~ 20:60 ~ 98, described washings is hydrochloric acid, nitric acid or sulfuric acid, volumetric concentration is 0.2 ~ 4 mol/L, described anti-stripping agent is hydrochloric acid or nitric acid, volumetric concentration is 0.2 ~ 4 mol/L, and described extraction progression is 1 ~ 6 grade, and washing progression is 1 ~ 6 grade; Reextraction progression is 1 ~ 6 grade.
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| CN106367622B (en) * | 2016-09-13 | 2018-12-07 | 南昌大学 | It is a kind of using aluminum sulfate as the ion adsorption type re efficient green extracting method of leaching agent |
| CN106367620A (en) * | 2016-09-13 | 2017-02-01 | 南昌大学 | Method for extracting and recycling rare earth from low-content rare earth solution with primary amine extracting agent |
| CN106636686B (en) * | 2016-11-17 | 2018-09-18 | 攀枝花学院 | Hydrochloric acid method produces synthetic rutile and leaches the method for extracting scandium in mother liquor |
| CN107675000B (en) * | 2017-09-05 | 2019-07-02 | 中国科学院长春应用化学研究所 | The method for regulating and controlling heavy rare-earth extraction separating technology extraction equilibrium acidity and extracting series |
| CN110331289B (en) * | 2019-07-02 | 2021-01-12 | 广西大学 | Method for recovering scandium and sodium sulfate from Bayer process red mud |
| CN113493874B (en) * | 2020-04-08 | 2022-12-13 | 福建省长汀金龙稀土有限公司 | Method for purifying high-purity scandium salt |
| CN112458294B (en) * | 2020-11-20 | 2023-03-14 | 河南荣佳钪钒科技有限公司 | Method for recovering vanadium from titanium white waste acid produced by chlorination process |
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| CN85106255A (en) * | 1985-08-15 | 1987-02-11 | 李久成 | Method of extract scandium from rare-earth mineral |
| 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 |
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