KR101667956B1 - Method for extrating scandium - Google Patents

Method for extrating scandium Download PDF

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KR101667956B1
KR101667956B1 KR1020150181167A KR20150181167A KR101667956B1 KR 101667956 B1 KR101667956 B1 KR 101667956B1 KR 1020150181167 A KR1020150181167 A KR 1020150181167A KR 20150181167 A KR20150181167 A KR 20150181167A KR 101667956 B1 KR101667956 B1 KR 101667956B1
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scandium
extract
solution
acid
sodium
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KR1020150181167A
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Korean (ko)
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이병필
이창규
김병원
장승규
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재단법인 포항산업과학연구원
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A method for extracting scandium comprising the steps of: preparing a leach solution by injecting an extractant into a slurry containing scandium (Sc); Introducing a sodium salt into the leaching solution to remove iron (Fe) in the leaching solution; Adding an extract to the leach solution to obtain a scandium extract; And extracting the scandium from the scandium solution, and separating the scandium solution from the extract.

Description

{METHOD FOR EXTRATING SCANDIUM}

The present invention relates to a method for extracting scandium.

Scandium (Sc) is usually distributed in large areas. Typically, trace amounts are contained in red mud or limonite light generated in the aluminum smelting process. The nickel extraction process is a process of leaching or directly leaching the raw ore, and if it contains scandium (Sc) in the process, it is leached together. Or a small amount of red mud generated in the aluminum smelting process is leached to recover a small amount of scandium (Sc). In both processes, a trace amount of Sc is leached and recovered. Usually, after the leaching, concentrated Sc or high purity Sc is obtained through solvent extraction.

Sc is generally contained in a small amount in raw materials (such as limonite or red mud), and when Sc is recovered through solvent extraction, acids (sulfuric acid, nitric acid, hydrochloric acid and the like) and bases (caustic soda, ammonia water, etc.) Is consumed in a large amount.

Provides an effective scandium extraction method.

According to an embodiment of the present invention, there is provided a method of preparing a slurry comprising: preparing a leach solution by injecting an leaching agent into a slurry containing Scandium (Sc); Introducing a sodium salt into the leaching solution to remove iron (Fe) in the leaching solution; Adding an extract to the leach solution to obtain a scandium extract; And extracting the scandium from the scandium extract and separating the scandium purified product from the extract.

The precipitant may include hydrochloric acid, sulfuric acid, nitric acid, acetic acid or hydrofluoric acid.

In preparing the leachate, the pH of the leachate may be from 0 to 2.

In the step of removing iron (Fe) in the leach solution, the sodium salt may comprise sodium chloride, sodium sulfate, sodium nitrate, sodium acetate or sodium fluoride. Specifically, the sodium salt may include sodium sulfate.

In the step of removing iron (Fe) in the leaching solution, 0.01 to 10 parts by weight of the sodium salt may be added per 100 parts by weight of the leaching solution.

The extract may comprise an extractant and the extractant may be a phosphonic acid based compound. Specifically, the extracting agent is selected from the group consisting of Di (2-ethylhexyl) phosphoric acid (D2EHPA), Bis (2,4,4-trimethylpentyl) phosphinic acid (CYANEX 272), 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester . ≪ / RTI >

The concentration of the extracting agent may be from 0.005 to 1 mol / liter.

The extract may comprise an additive and the additive may be tributyl phosphate (TBP), n-hexane, iso-butanol, iso-decanol, or a combination thereof.

The concentration of the additive may be 1 to 15% by weight in the whole extract.

The extract may comprise a diluent and the diluent may be a hydrocarbon liquid.

The step of separating the extract may further comprise washing the scandium extract.

Stripping solution may include NaOH, NH 4 OH, or a combination thereof.

The concentration of NaOH, NH 4 OH, or a combination thereof in the stripping liquid may be from 1 to 10% by weight.

According to one embodiment of the present invention, iron (Fe) is removed prior to the extraction process, and Fe extracted with the extract in the extraction process is significantly reduced. In order to remove Fe in the extract, a scandium It is unnecessary to perform scrubbing.

As a result, solvent extraction can be performed more effectively.

1 is a flowchart of a scandium extraction method according to an embodiment of the present invention.

The terms first, second and third, etc. are used to describe various portions, components, regions, layers and / or sections, but are not limited thereto. These terms are only used to distinguish any moiety, element, region, layer or section from another moiety, moiety, region, layer or section. Thus, a first portion, component, region, layer or section described below may be referred to as a second portion, component, region, layer or section without departing from the scope of the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The singular forms as used herein include plural forms as long as the phrases do not expressly express the opposite meaning thereto. Means that a particular feature, region, integer, step, operation, element and / or component is specified and that the presence or absence of other features, regions, integers, steps, operations, elements, and / It does not exclude addition.

Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Commonly used predefined terms are further interpreted as having a meaning consistent with the relevant technical literature and the present disclosure, and are not to be construed as ideal or very formal meanings unless defined otherwise.

In one embodiment of the present invention, iron (Fe) is removed prior to the extraction process in the solvent extraction process, and Fe extracted with the extract in the extraction process is significantly reduced to recover Sc more economically.

FIG. 1 schematically shows a flow chart of a scandium extraction method according to an embodiment of the present invention. The flow chart of the scandium extraction method of FIG. 1 is merely for illustrating the present invention, and the present invention is not limited thereto. Therefore, the extraction method of scandium can be variously modified.

As shown in FIG. 1, a method of extracting scandium according to an embodiment of the present invention includes: (S10) preparing a leaching solution by injecting an leaching agent into a slurry containing Scandium (Sc); (S20) of injecting sodium salt into the leaching solution to remove iron (Fe) in the leaching solution; Adding an extract to the leach solution to obtain a scandium extract (S30); And a step (S40) of separating the scandium purified product and the extract solution by injecting a deionized solution into the scandium extract.

The conventional method does not include the step of removing iron (Fe) in the leaching solution (S20), and the iron component in the extract is also extracted and scrubbed with strong acid or oxalic acid to remove iron in the extract. In one embodiment of the present invention, it is not necessary to scrub using strong acid or oxalic acid by removing sodium (Fe) in the leaching solution by adding sodium salt to the leaching solution and then extracting Sc from the leaching solution from which iron has been removed, Solvent extraction can be performed effectively.

Returning to FIG. 1, in step S10, an immersion liquid is put into a slurry containing Scandium (Sc) to prepare an immersion liquid. In this case, the slurry containing the scandium is a slurry obtained by adding 2 to 3 times the process water to the leaching residues in the step of extracting nickel from the limonite light or the leaching residues of red mud generated in the aluminum smelting process . In addition to Sc, magnesium, calcium, manganese, iron, cobalt, nickel, chromium, silicon, copper and the like may be added to the slurry. Are included as impurities.

The reason for adding 2 to 3 times the process water based on the residue weight of leaching is that when the amount of process water is increased more than 3 times due to the characteristic of the process of extracting solvent after leaching, the Sc concentration in the leaching solution is remarkably low, There is a disadvantage in that the disposal step is difficult to carry out due to the lack of slurry when the process water is supplied at a rate of less than 2 times.

The precipitant may include hydrochloric acid, sulfuric acid, nitric acid, acetic acid or hydrofluoric acid. When the leaching agent corresponding to 7 to 9% by weight of the chemical equivalent is added and the leaching reaction is performed for 5 minutes or more, the pH of the leaching solution becomes 0 to 2. In the above-mentioned range, Sc may be selectively leached, and other impurities may not be leached. More specifically, the pH of the leach solution may be 0.5 to 1.

If the amount of the precipitant to be added is too small, the amount of Sc dissolved in the solution becomes small. Even if the amount of Sc is large, the amount of Sc leached is limited and impurities such as Fe and Mg are further leached. % Of the precipitating agent.

When the leaching reaction time is less than 5 minutes, Sc does not dissolve. When the leaching time is more than 5 minutes, Sc is the same level, and other impurities such as Fe and Mg are dissolved in the solution.

Next, in step S20, sodium salt is added to the leaching solution to remove iron (Fe) in the leaching solution. At this time, the sodium salt may include sodium chloride, sodium sulfate, sodium nitrate, sodium acetate or sodium fluoride. More specifically, it may include sodium sulfate.

For example, when sodium sulfate is used as the sodium salt, sodium sulfate reacts with iron to form jarosite, and iron in the leach is removed.

2Fe 2 (SO 4 ) 3 + Na 2 SO 4 + 12H 2 O -> Na 2 Fe 6 (SO 4 ) 4 (OH) 12 + 6H 2 SO 4

In the step of removing iron (Fe) in the leaching solution, 0.01 to 10 parts by weight of the sodium salt may be added per 100 parts by weight of the leaching solution. If too little sodium salt is added, the removal amount of iron will be reduced. Even if too much sodium salt is added, the removal amount of iron is limited. Therefore, the sodium salt can be introduced into the above-mentioned range.

Next, in step S30, the extract is injected into the leach solution to obtain a scandium extract.

To control the leaching solution to the above-mentioned pH range, the leaching solution may contain hydrochloric acid, sulfuric acid, nitric acid, acetic acid or hydrofluoric acid.

The extract may comprise an extractant and the extractant may be a phosphonic acid based compound. Specifically, the extracting agent is selected from the group consisting of Di (2-ethylhexyl) phosphoric acid (D2EHPA), Bis (2,4,4-trimethylpentyl) phosphinic acid (CYANEX 272), 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester . ≪ / RTI >

The concentration of the extracting agent may be from 0.005 to 1 mol / liter. Sc can be extracted at a high extraction ratio within the above-mentioned range.

The extract may comprise an additive and the additive may be tributyl phosphate (TBP), n-hexane, iso-butanol, iso-decanol, or a combination thereof. The additive has an effect of facilitating separation from the extraction filtrate.

The concentration of the additive may be 1 to 15% by weight in the whole extract. If too little of the additive is added, separation of the extractant and the extraction filtrate may be insufficient. If the additive is included too much, the extraction rate of Sc may be lowered. Therefore, the addition amount of the additive can be controlled within the above-mentioned range.

The extract may comprise a diluent and the diluent may be a hydrocarbon liquid.

After step S30, cleaning the scandium extract prior to step S40 may further comprise cleaning the scandium extract.

In step S40, the scallion extract is separated from the scandium purified water by injecting the depigmenting liquid into the scandium extract.

Stripping solution may include NaOH, NH 4 OH, or a combination thereof.

The concentration of NaOH, NH 4 OH, or a combination thereof in the stripping liquid may be from 1 to 10% by weight.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.

Example  One - Leaching residues  analysis

After reducing the limonite light with hydrogen, it is leached with hydrochloric acid. In order to facilitate precipitation of Ni, the pH of the leachate is adjusted, and the Ni leachate is transferred by the precipitation process.

The pH-controlled leaching solution contained a large amount of residue, which was washed twice with water and recovered and used as a raw material for Sc.

This process is a process for obtaining a raw material for use in the verification of the present invention and will not be described in detail. For further information, please refer to the hydrogen reduction process (KR 10-2010-0128249).

Sc residues were partially contained in the residues after the second wash, and leaching residue components are shown in Table 1 below.

Unit: ppm Sc Fe Ni Mg Si Al Cr Cu Ca Mn Co Zn P Leaching residues 144 171419 1730 51901 174736 46782 74946 200 1377 5577 277 1163 244

Example  2 - Leaching reaction

2.5 times as much as the weight of the residue was added to the leach residue to make a slurry, and leaching reaction was carried out to pH 0.5 by leaching reaction for 5 minutes or more after introducing the leaching agent of Table 2 below.

Precipitant Chemical equivalent (%) Leaching time
(minute) Mg (ppm) Fe (ppm) Sc (ppm) Sulfuric acid (97 wt%) 7 5 3,740 1,616 13 12 5 4,106 3,148 14 17 5 4,259 3,899 14 22 5 4,289 4,416 14 Hydrochloric acid (20 wt%) 9 5 3,722 946 10 9 10 3,822 970 10 9 20 3,817 1,192 10 9 30 4,181 1,380 11 9 40 4,206 1,526 11 9 50 4,226 1,519 11 9 60 4,383 1,638 11

As shown in Table 2, even if the amount of leaching agent and the leaching time are increased, the amount of scandium does not increase, but only impurities such as Mg and Fe are increased.

Example  3 - Fe removal reaction

The leached residue was leached with sulfuric acid. The components in the leach solution are summarized in Table 3 below.

20 g, 40 g, and 60 g of sodium sulfate (Na 2 SO 4 ) were added to the leach solution and the components were analyzed and summarized in Table 3 below.

Unit: ppm Mg Ca Mn Fe Co Ni Cr Si Al Cu Zn Sc Leachate 5358 561 68 2183 24 201 107 244 536 20 <10 14 20g 5003 552 63 1996 23 185 98 231 592 20 <10 13 40g 4758 614 61 1576 21 171 85 220 605 19 <10 12 60g 4358 543 55 1421 21 165 79 213 582 18 <10 11

As shown in Table 3, it can be confirmed that Fe 3 + is removed by the addition of Na 2 SO 4 , and the Fe content is reduced by about 28 wt%.

Example  4 - Extraction reaction

As the constitution of the extract, 1000 ml of D2EHPA: TBP: ESCAID 110 in a volume ratio of 600: 300: 2100 was prepared.

The pH of the leachate was adjusted to 0.46 using 20% HCl, and the volume of 18.72 times of the organic phase was added to the organic phase for solvent extraction at 26 ml / min for 12 hours. The organic phase was recycled and the water phase was discharged. The total dosage was 18,000 mL. The components of the extracted filtrate were analyzed and summarized in Table 4 below.

Unit: ppm Sc Al Si Cr Fe Mg Mn Ni Cu Co Zn Ca Leachate 18 2318 349 779 4111 4095 102 341 14 25 <10 235 After 1 hour <1 2196 387 837 2483 3766 93 344 13 21 <10 230 After 2 hours <1 2146 367 818 2177 3701 92 331 13 21 <10 290 After 3 hours <1 2249 378 852 2313 3869 95 344 14 21 <10 240 After 4 hours <1 2195 379 842 2666 3800 95 341 13 21 <10 234 After 5 hours <1 2188 397 856 3056 3764 97 348 14 22 <10 274 After 6 hours <1 2200 390 840 3637 3805 97 344 13 21 <10 229 After 7 hours <1 2184 389 834 3656 3731 94 342 13 21 <10 228 After 8 hours <1 2172 391 841 3819 3726 95 345 13 22 <10 232 After 10 hours <1 2095 389 846 3894 3568 95 346 13 22 <10 227 After 11 hours <1 2062 391 841 3881 3494 95 344 13 21 <10 225 After 12 hours <1 2106 397 850 3956 3554 96 349 13 22 <10 229

As shown in Table 4, extraction of other elements except Sc compared to the leaching solution may be considered to be insignificant, and almost all of Sc can be extracted.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (15)

Preparing an immersion liquid by injecting an immersion agent into a slurry containing scandium (Sc);
Adding a sodium salt to the leach solution to remove iron (Fe) from the leach solution;
Adding an extract to the leach solution to obtain a scandium extract; And
And separating the scandium purified product and the extract solution by injecting a deionized solution into the scandium extract.
The method according to claim 1,
The method of extracting scandium comprising hydrochloric acid, sulfuric acid, nitric acid, acetic acid or hydrofluoric acid.
The method according to claim 1,
Wherein the pH of the leach solution is 0 to 2 in the step of preparing the leach solution.
The method according to claim 1,
Wherein the sodium salt is sodium chloride, sodium sulfate, sodium nitrate, sodium acetate or sodium fluoride in the step of removing iron (Fe) in the leaching solution.
5. The method of claim 4,
Wherein the sodium salt comprises sodium sulfate.
The method according to claim 1,
Wherein the sodium salt is added in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the leach solution in the step of removing iron (Fe) in the leach solution.
The method according to claim 1,
Wherein the extract comprises an extractant, and the extractant is a phosphonic acid-based compound.
8. The method of claim 7,
The extractant may be selected from the group consisting of di (2-ethylhexyl) phosphoric acid (D2EHPA), bis (2,4,4-trimethylpentyl) phosphinic acid (CYANEX 272), 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester The method of extracting scandium which is a combination.
8. The method of claim 7,
Wherein the concentration of the extracting agent is 0.005 to 1 mol / liter.
The method according to claim 1,
Said extract comprising an additive,
Wherein the additive is TBP (tributyl phosphate), n-hexane, iso-butanol, iso-decanol, or a combination thereof.
11. The method of claim 10,
Wherein the concentration of the additive is 1 to 15% by weight in the total extract.
The method according to claim 1,
Wherein the extract comprises a diluent,
Wherein the diluent is a hydrocarbon liquid.
The method according to claim 1,
Prior to separating the extract,
And washing the scandium extract. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The method according to claim 1,
The stripping solution is a method for extracting a scandium containing NaOH, NH 4 OH, or a combination thereof.
15. The method of claim 14,
Wherein the concentration of NaOH, NH 4 OH, or a combination thereof in the stripping liquid is 1 to 10 wt%.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130076261A (en) * 2011-12-28 2013-07-08 주식회사 포스코 Extraction method of rare earth elements from monazite
JP2015163729A (en) * 2014-01-31 2015-09-10 住友金属鉱山株式会社 Scandium recovery method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130076261A (en) * 2011-12-28 2013-07-08 주식회사 포스코 Extraction method of rare earth elements from monazite
JP2015163729A (en) * 2014-01-31 2015-09-10 住友金属鉱山株式会社 Scandium recovery method

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