WO2016209178A1 - Récupération de scandium et de dérivés de celui-ci à partir d'une solution de lixiviation chargée avec des métaux obtenus en conséquence de la lixiviation de minerais latéritiques comprenant du nickel, du cobalt et du scandium, et des sources secondaires comprenant du scandium - Google Patents

Récupération de scandium et de dérivés de celui-ci à partir d'une solution de lixiviation chargée avec des métaux obtenus en conséquence de la lixiviation de minerais latéritiques comprenant du nickel, du cobalt et du scandium, et des sources secondaires comprenant du scandium Download PDF

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Publication number
WO2016209178A1
WO2016209178A1 PCT/TR2015/050161 TR2015050161W WO2016209178A1 WO 2016209178 A1 WO2016209178 A1 WO 2016209178A1 TR 2015050161 W TR2015050161 W TR 2015050161W WO 2016209178 A1 WO2016209178 A1 WO 2016209178A1
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Prior art keywords
scandium
solution
process step
organic
dehpa
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PCT/TR2015/050161
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English (en)
Inventor
Ali Safder İPLİKÇİOĞLU
Yavuz Ali TOPKAYA
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Meta Ni̇kel Kobalt Madenci̇li̇k Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇
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Publication of WO2016209178A1 publication Critical patent/WO2016209178A1/fr

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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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • 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

Definitions

  • the invention relates to recovering scandium and derivatives thereof from a dirty leach solution having impurity elements therein formed after leaching lateritic ores used during the production of nickel-cobalt, or formed after leaching of secondary scandium sources in which scandium is enriched within the precipitate during a pH controlled solution purification step with solvent extraction and then a precipitation method.
  • US Patent Application No. 2014314639 is one of the applications which appears relating to research in the literature.
  • This application comprises the step of purifying a pH controlled leach solution during the production of nickel-cobalt hydroxide from lateritic ores with hydrometallurgical methods.
  • the element scandium is inclined to precipitate and that is enriched within the solid precipitate formed within this process in the range of pH 2.5 to pH 5.0.
  • scandium may only be obtained with the solvent extraction method from the precipitate rich in scandium, neither the process steps applied during this method nor the reagents used in these steps have been indicated.
  • the scandium-containing solution is obtained after removing leach residues from the system with solid-liquid separation after the leaching process, and comprises therein undesired impurity elements together with scandium at a relatively low concentration.
  • the impurity elements found together with scandium may be Fe, Al, Cr, Mn, Mg, Ni, Co, Ca, Cu, Zn, Si, etc. These said impurity elements contaminate the scandium product and make it harder for the product to be marketed.
  • the present invention aims at applying a solvent extraction method consisting of the steps of pre-conditioning, extraction, scrubbing and stripping to a purified leach solution after excessive impurity elements have been refined in a pH controlled manner, if there are any, from a leach solution loaded with metals obtained as a result of leaching lateritic ores containing nickel, cobalt and scandium and/or secondary scandium sources formed as a result of precipitation which meets the aforementioned needs, eliminates all disadvantages and provides some additional advantages. It is aimed that scandium enriched and purified from impurities after these stages is recovered from the strip solution with the precipitation method.
  • the first object of the invention is to subject the scandium-containing solution obtained by leaching the aforementioned primary and secondary scandium sources to a pH controlled purification process by stepwise precipitating the impurity elements such as Fe, Al, Cr if it comprises excessively.
  • Another object of the invention is to determine the organic based reagent and the pre-conditioning chemical to enable scandium to be selectively extracted to the organic phase through the leach solution during the extraction step and to ease stripping of scandium loaded onto the organic phase to be back-extracted to aqueous phase during the stripping step, after said pre-conditioning process.
  • An ammonium thiocyanate compound was selected as said pre-conditioning reagent, and DEHPA was selected as the organic based reagent.
  • a further object of the invention is to enable the present impurity elements to be left behind in the scandium-containing solution and scandium to be selectively extracted onto the organic reagent, after leaching sources comprising scandium and placing them into a leach solution with minimum impurity elements and maximum scandium yield, with the mentioned extraction process. For this reason, a mixture of pre-conditioned (DEHPA + kerosene) and leach solution-containing scandium is used in the extraction stage.
  • An even further object of the invention is to enable the impurity elements loaded onto the organic phase together with scandium to be removed from the organic such that there is no loss of scandium.
  • this process is called the "scrubbing" process in literature.
  • a reagent selected from the group consisting of HCI, H2SO4, HNO3 and NH 4 F is used.
  • Another object of the invention is to enable the transfer of scandium, loaded onto the organic phase, into a strip solution through the organic phase with the back- extraction process.
  • this process is called the "stripping" process in literature.
  • a reagent selected from the group consisting of HNO3, NaOH and NH 4 F is used to enable this purpose.
  • a further object of the invention is to enable recovering the scandium, taken into a solution phase after the stripping process, from a solution phase as solid scandium compounds with the mentioned precipitation process.
  • a reagent selected from the group consisting of NH 4 F, H2C2O4, (NH 4 )2CO3, Na2CO3 or NaOH is used.
  • Figure 1 is a flow chart of the process of the invention.
  • the invention aims to refine the dirty leach solution obtained after leaching lateritic ores used during the production of nickel-cobalt, or after leaching of secondary scandium sources in which scandium is enriched within the precipitate during a pH controlled solution purification step if there are excessive impurity elements therein, and to enrich the scandium-containing leach solution in scandium with the solvent extraction stages of pre-conditioning, extraction, scrubbing, stripping and to purify this solution, and finally to recover scandium and derivatives thereof with precipitation method.
  • the invention relates to eliminating aforementioned impurity elements, and recovering scandium and derivatives thereof from the mentioned ores or secondary sources. Therefore, there are used process steps, reagents found within these process steps, and parameters, in which these reagents are suitable. Process steps of the invention:
  • This relates to subjecting the scandium-containing solution obtained by leaching primary or secondary scandium sources to a pH controlled purification process by stepwise precipitating impurity elements such as Fe, Al, Cr if it comprises excessive impurity elements.
  • Pre-conditioning This relates to determining an organic based reagent to enable scandium to be selectively extracted to the organic phase through the solution during the extraction step and at the same time to enable stripping of loaded scandium thereon during the stripping step.
  • This organic reagent is conditioned by being passed through a pre-process with a certain chemical.
  • the DEHPA organic reagent used within the pre-process is 2-15% vol. and the remaining 85-98% vol. is kerosene.
  • the pre-conditioning process is carried out with 1 -3 molar NH 4 SCN (preferably 1 .5 molar).
  • the volume ratio of the organic/ammonium thiocyanate solution used in the mixture may be within the range of 1 /1 -10/1 .
  • isodecyl alcohol or TBP tributylphosphate
  • reagents may be added into the (DEHPA + kerosene) mixture if necessary (e.g., if the formation of a third phase is observed or in order to enable a synergistic effect during the extraction step).
  • the volume ratios of the isodecyl alcohol (preferably 5%) or TBP (preferably 1 %) to be added may vary between 1 - 10%. When these reagents are added, the volume ratio of the kerosene within the organic mixture is decreased according to the amount added.
  • Extraction This relates to carrying out an extraction process to selectively extract and load scandium onto the organic reagent from impurity elements in the solution which is obtained by leaching scandium containing sources with minimum impurity elements and maximum scandium yield.
  • a (DEHPA + kerosene) mixture which has been pre-conditioned or has/has not had isodecyl alcohol or TBP added is used.
  • scandium is transferred to the organic phase as a result of ion exchange by mixing the organic phase comprised of the (DEHPA + kerosene) mixture with a leach solution containing scandium.
  • the organic/ solution phase ratio may vary between 1 /3 - 1 /20 (preferably 1 /10) by volume depending on scandium concentration within the solution.
  • the solution obtained after the extraction step is termed a raffinate.
  • the organic phase having the possibility of polluting this solution is cleaned by means of active carbon and valuable metals such as Ni, Co which remain in the Organic removed raffinate' are recovered with known methods.
  • Scrubbing After the extraction process with an organic based reagent, the reagents enabling the removal of impurity elements loaded onto the organic phase together with scandium such that there is a little or no loss of scandium; are H2SO4, HCI, HNO3 and NH 4 F.
  • One selected from these reagents is mixed such that the scandium loaded organic phase/solution phase ratio is 1 /1 -15/1 (preferably 10/1 ) by volume by preparing the solution thereof at the concentrations stated below.
  • the impurities such as Fe, Al, Ca, etc. polluting the organic phase loaded with scandium are transferred to the scrub solution phase, and the organic scrubbing step for removal of the impurities is completed.
  • the solution of one of the reagents indicated below is mixed with the organic phase loaded with scandium and scrubbed from impurities by being prepared in specified concentrations.
  • the organic/solution phase ratio is selected as 1 /1 -30/1 (preferably 15/1 ) by volume.
  • Precipitation The precipitation process enabling the selective recovery of scandium from a solution enriched in terms of scandium obtained by stripping of scandium on the organic reagent, is carried out by preparing the solution with one of the following selected reagents at specified concentrations.
  • DEHPA organic reagent which is diluted with kerosene
  • the DEHPA chemical is prepared by being diluted such that there is 2-15% DEHPA and 85-98% kerosene by volume, and conditioned by mixing the NH 4 SCN chemical at a concentration of 1 -3 molar and the organic/solution phase ratio in the range of 1 /1 -10/1 by volume.
  • the conditioned organic is then separated from the solution phase comprising NH 4 SCN with the help of a settler due to the difference in density.
  • the separated conditioned organic phase is used in the following extraction step.
  • an isodecyl alcohol or TBP reagent may be added to the (DEHPA + kerosene) mixture if necessary (e.g., if the formation of a third phase is observed or in order to enable a synergistic effect during the extraction step).
  • the pre-conditioned DEHPA + kerosene) mixture prepared in the previous step is mixed with a scandium-containing leach solution for about 1 -15 minutes by means of a mixer such that the organic/solution phase ratio is in the range of 1 /3-1 /20 by volume.
  • the scandium within the solution is selectively extracted onto the organic phase and enriched.
  • the organic phase and the raffinate phase of which the scandium has been removed are separated from each other in a settler unit due to the difference in density by letting the two phases to settle for about 1 -15 minutes.
  • the scandium loaded organic phase which is separated from the raffinate phase is then transferred to the following scrubbing step.
  • the scrubbing step is applied for scrubbing impurity elements such as Fe, Al, Ca, etc. loaded onto the organic reagent together with scandium.
  • impurity elements such as Fe, Al, Ca, etc. loaded onto the organic reagent together with scandium.
  • HCI, H2SO4, HNO3 and NH 4 F is used.
  • a minimum or no loss of scandium from the organic phase to the scrub solution is aimed.
  • the organic/solution phase ratio is selected within the range of 1 /1 -15/1 by volume and mixing time during scrubbing is controlled between 1 -15 minutes.
  • the organic and scrub solution are separated from each other with a settler unit within about 1 -15 minutes.
  • the organic phase loaded with scandium which is scrubbed from impurity elements thereon is transferred to the stripping step so that scandium is returned to the solution phase.
  • the stripping step scandium present on the loaded and scrubbed organic phase is transferred into a strip solution.
  • the solution of a stripping reagent selected from the group consisting of HNO3, NaOH and NH 4 F is used to enable this.
  • the scandium loaded organic/solution phase ratio is selected within the range of 1/1 -30/1 by volume and is mixed for 1 -15 minutes.
  • the organic phase and strip solution phase are separated from each other in a settler unit due to the difference in density by letting the two phases to settle for about 1 -15 minutes.
  • the separated organic phase is then returned to the extraction step by being conditioned again if necessary to be used again in the solvent extraction stage.
  • a new scandium rich solution is obtained with the stripping process afterwards by separating the stripped organic and strip solution from each other by the help of settler unit.
  • This solution may generally comprise 500-8000 ppm scandium depending on the lateritic ore, or the secondary scandium source tenor or its concentration, respectively. Said stripping solution is then subjected to a precipitation process to obtain the scandium therein.
  • the precipitation step recovers scandium from the strip solution phase in the form of solid scandium compounds.
  • the solution of a reagent selected from the group consisting of NH 4 F, H2C2O4, (NH 4 )2CO3, Na2CO3 or NaOH is used.
  • the solution of the mentioned reagents reacts with a solution rich in scandium obtained as a result of stripping. Scandium fluoride, scandium hydroxide, scandium oxalate, or scandium carbonate are obtained after the reaction depending on the precipitating reagent used. Also, if desired, SC2O3 is produced from these compounds.
  • the aforementioned solvent extraction process steps are generally performed at room temperature.
  • the maximum temperature is controlled so as to prevent the organic phase from catching fire.
  • a washing step is applied to the organic phase by adding purified water or by adding 5-15 g/L ammonium sulphate to purified water when necessary to prevent pollution in transitions between the mentioned solvent extraction process steps.
  • a ventilation system, a fume hood or a similar system should be continually operated in order to provide protection from the smells which chemicals having adverse health effects and high vapour pressure may produce in a work environment,
  • MSDS safety sheets

Abstract

L'invention comprend la lixiviation de minerais latéritiques utilisés pendant la production de nickel-cobalt, ou la lixiviation de sources secondaires de scandium, dans laquelle le scandium est enrichi dans le précipité pendant un processus de purification en solution à pH contrôlé. L'invention concerne l'application d'un procédé d'extraction par solvant et la récupération de scandium et de dérivés de celui-ci à partir des sources mentionnées pour enrichir et purifier la solution de lixiviation, ayant des éléments d'impuretés dans celle-ci, en termes de scandium.
PCT/TR2015/050161 2015-06-22 2015-11-06 Récupération de scandium et de dérivés de celui-ci à partir d'une solution de lixiviation chargée avec des métaux obtenus en conséquence de la lixiviation de minerais latéritiques comprenant du nickel, du cobalt et du scandium, et des sources secondaires comprenant du scandium WO2016209178A1 (fr)

Applications Claiming Priority (2)

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TR2015/07658 2015-06-22
TR201507658 2015-06-22

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WO2016209178A1 true WO2016209178A1 (fr) 2016-12-29

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020181607A1 (fr) * 2019-03-13 2020-09-17 荆门市格林美新材料有限公司 Procédé d'extraction d'ions dans une solution de minerai
CN113046580A (zh) * 2021-03-12 2021-06-29 中国恩菲工程技术有限公司 钪萃取预处理系统及含钪溶液的处理方法
CN113387402A (zh) * 2021-07-08 2021-09-14 四川顺应动力电池材料有限公司 利用氢氧化镍钴原料结晶法生产硫酸镍钴盐的方法
CN114441258A (zh) * 2021-12-30 2022-05-06 云锡文山锌铟冶炼有限公司 检测有机萃取剂中p204含量的方法

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WO2015009254A2 (fr) * 2013-07-18 2015-01-22 Meta Ni̇kel Kobalt Madenci̇li̇k Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇ Lessivage acide à haute pression de minerais latéritiques réfractaires comprenant du nickel, du cobalt et du scandium, et récupération du scandium à partir de la solution mère de lixiviation et des précipités de purification

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020181607A1 (fr) * 2019-03-13 2020-09-17 荆门市格林美新材料有限公司 Procédé d'extraction d'ions dans une solution de minerai
CN113046580A (zh) * 2021-03-12 2021-06-29 中国恩菲工程技术有限公司 钪萃取预处理系统及含钪溶液的处理方法
CN113387402A (zh) * 2021-07-08 2021-09-14 四川顺应动力电池材料有限公司 利用氢氧化镍钴原料结晶法生产硫酸镍钴盐的方法
CN113387402B (zh) * 2021-07-08 2023-04-18 四川顺应动力电池材料有限公司 利用氢氧化镍钴原料结晶法生产硫酸镍钴盐的方法
CN114441258A (zh) * 2021-12-30 2022-05-06 云锡文山锌铟冶炼有限公司 检测有机萃取剂中p204含量的方法
CN114441258B (zh) * 2021-12-30 2023-08-04 云锡文山锌铟冶炼有限公司 检测有机萃取剂中p204含量的方法

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