Classifications

• • 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
• • 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 present invention relates to an extractive metallurgical process for low grade rare earth ores containing high levels of iron and/or aluminum.
• Rare earth elements are defined as a set of seventeen chemical elements from the periodic table, the fifteen lanthanides plus yttrium and scandium.
• Light rare earths are defined as the first five lanthanides (lanthanum, cerium, praseodymium, neodymium and promethium - the last one being unstable in nature) plus yttrium and scandium.
• Medium rare earths, or SEG are samarium, europium and gadolinium, leaving the other seven (terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium) as heavy rare earths.
• Rare earths are moderately available in the earth crust. Some light rare earths are even more abundant than nickel, cobalt or lead.
• rare earth-bearing minerals There are many rare earth-bearing minerals, from primary or secondary formation. Usually, rare earths are explored as by or co-product of another operation. Commercial operations of rare earths as the main product are usually from monazite or bastnasite deposits, being those two the main minerals for the industry.
• Rare earths extraction from these minerals is widely known by the industry and is considered state-of-the-art processing. After they are submitted to a mineral concentration stage, known by those skilled in the art, a pure rare earth concentrate is submitted to acid or caustic attacks. These processes work well for monazite or bastnasite concentrates, where the rare earth minerals have a good degree of separation from other impurities, like iron or aluminum. These processes, however, cannot be applied to a deposit where poor mineral concentration is achieved.
• Caustic cracking one of the available processes for attacking monazite concentrates, uses caustic soda to attack the rare earth phosphates, producing rare earth hydroxides and soluble TSP (tri-sodium phosphate), a valuable by- product. This operation usually occurs at 120-150°C using agitated tanks. After solid-liquid separation, the rare earth hydroxides are leached in HCl and sent to further processing, usually solvent extraction. TSP is removed from the solution by crystallization methods. This process cannot cope with high silicon, aluminum and/or iron concentrates. Aluminum and silicon can be leached by caustic soda consuming reagents and increasing solution viscosity. Iron and these elements can also produce colloids. These effects make operations very difficult as solid- liquid separation becomes a challenge and caustic soda consumption increases considerably.
• Rare earth sulfates are formed and later dissolved by adding water.
• the rare earth sulfates are removed from solution as sodium double sulfates or as oxalates. These are attacked with caustic soda, forming hydroxides that are leached with HCl.
• the HCl solution is usually taken to solvent extraction for proper elements separation. High levels of impurities like iron, aluminum or alkali and earth-alkali elements will increase acid consumption and make solution purification more difficult and costly.
• the mechanism involved is to convert all species in the ore into sulfates (including the impurities) and decomposing them at high temperatures into insoluble oxides, releasing SOx.
• This invention takes care of reducing the amount of impurities added but still needs a high amount of sulfuric acid to be added and high temperatures to decompose some of the sulfates formed.
• Rare earth sulfates may also decompose to some extent, reducing overall extraction rate. It may produce a pure rare earth solution but does not take care of the high acid consumption.
• the invention presented in this document differs from state of art processing and these other two inventions.
• the present document brings a process that indirectly attacks rare earth minerals using aluminum and iron sulfates that are formed by adding small quantities of sulfuric acid, enough to attack the said rare earth minerals.
• This process produces stable species of iron and aluminum, leaving rare earths as soluble species. It is, therefore, an indirect leaching process that attacks rare earth minerals not with sulfuric acid, but with iron and aluminum sulfates.
• FIG. 1 shows that neither of the discussed inventions are able to obtain similar results, as either iron is not converted into phosphates at low temperatures or rare earth sulfates start to decompose, together with impurities, at higher temperatures.
• a method for recovering rare earth elements from low grade ore, such as, but not limited to, monazite deposits, is provided by the present disclosure.
• the material must include at least one of the rare earth elements (lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, added to yttrium and scandium) and at least one of iron or aluminum.
• the method includes steps of: (i) reducing the ore particle size to a desirable target, (ii) obtaining a concentrate that still carries the mentioned elements, (iii) drying the obtained concentrate or upgraded ore if necessary, (iv) adding sulfuric acid in a sub- stoichiometric amount to obtain sulfates of iron and/or aluminum, (v) submitting the mixture to a high temperature operation, where iron and/or aluminum sulfates react with rare earth minerals, forming soluble rare earth sulfates, (vi) Adding this mix of rare earth sulfates and impurities to water in order to solubilize such compounds selectively and (vii) use any of the known methods available for rare earth separation, such as, but not limited to, solvent extraction.
• FIG. 1 is a graph illustrating the effect of temperature and time to iron extraction as a function of temperature and time, thus showing conversion of iron from sulfate into phosphate.
• FIG. 2 is a graph illustrating the effect of temperature and time to aluminum extraction as a function of temperature and time, thus showing conversion of aluminum from sulfate into phosphate.
• FIG. 3 is a graph illustrating Gibbs free energy of formation of lanthanum sulfate and ferric phosphate using ferric sulfate and lanthanum phosphate;
• FIG. 4 is a graph illustrating Gibbs free energy of formation of lanthanum sulfate and aluminum phosphate using aluminum sulfate and lanthanum phosphate;
• FIG. 5 is a flow chart of a process for extracting rare earth elements from low grade ores according to one embodiment of the present disclosure;
• FIG. 6 is a graph illustrating the correlation of phosphate and iron extraction.
• FIG. 7 is a graph illustrating the correlation of phosphate and aluminum extraction.
• FIG. 8 is a figure of an X-ray difractometry, showing the formation of ferric and aluminum phosphates after submitting the low grade ore to the proposed invention.
• FIG. 9 is a cyclosizer graph.
• the present disclosure relates to a process for recovering rare earth elements from low grade ores, especially those that are not susceptible to proper mineral concentration, containing at least one of aluminum and iron, such as ore from a monazite deposit.
• the low grade rare earth ore is treated with sulfuric acid, added in a sub-stoichiometric manner, and submitted to high temperature in order to produce an iron and aluminum-free solution that carries rare earths as sulfates.
• the low grade ore is initially submitted to a size reduction stage, known by those skilled in the art.
• the objective of this stage is to liberate the rare earth minerals and to take the ore to a suitable size for further processing.
• the ore can be also taken to a concentration stage, such as size classification, to increase the ore grade, as long as iron and aluminum are still found in the concentrate.
• the upgraded ore is added to a small quantity of sulfuric acid, forming ferric and/or aluminum sulfates.
• the ore may need to be dried before adding sulfuric acid, depending on what upgrading techniques are used. This stage would be necessary to avoid dilution of the concentrated sulfuric acid and to improve operation.
• the mixture is submitted to a high temperature operation where rare earth sulfates are formed, along with iron and aluminum insoluble and stable compounds that may vary according to the source of rare earths.
• the calcine is added to water to selectively solubilize the rare earths, leaving iron and aluminum in the residue.
• the clean solution can then be taken to any downstream processing of rare earths known by those skilled in the art.
• FIG. 5 illustrates the proposed process.
• the ore After the ore is extracted from the mine, it must be taken to a size reduction operation. Any operation can be used at this stage, known by those skilled in the art, coupled to concentration techniques, such as, but now limited to, size classification.
• concentration techniques such as, but now limited to, size classification.
• the final concentrate size must be smaller than 0.5 mm to ensure proper mixing during the dissolution stage.
• concentrated sulfuric acid (90-98%) is added to it in a sub-stoichiometric manner. Enough acid must be added to convert the rare earth elements, base and alkaline metals to sulfates. Some acid can be added to convert partially iron and aluminum to sulfates, but no more than 20%, preferably below 5%. This stage is known as sulfation. This operation can be done at any equipment known by those skilled in the art, such as, but not limited to, a pug mill. No heat is required at this stage, although it is not prejudicial. At this stage, sulfuric acid will attack the main elements present in the material, which are aluminum and iron and convert them to sulfates, as described by the following reactions.
• the mixture of rare earth ore and aluminum and ferric sulfates is submitted to an operation where temperature is increased and the mixture is kept in motion for proper solid-solid contact.
• Those skilled in the art may choose the best equipment for this stage, such as, but not limited to, a rotary kiln.
• the mixture must be kept at a temperature between 620°C and 750°C, preferably between 650°C and 720°C for 1 to 8 hours, preferably between 2 and 4 hours.
• iron and aluminum sulfates are converted into stable compounds, forming rare earth sulfates.
• the following reactions show the proposed mechanism for a lanthanum phosphate, but could be applied to other rare earth compound as well
• FIG. 1 and FIG. 2 illustrate the kinetics effect on temperature.
• the kiln produces rare earth sulfates, which are readily soluble in water and stabilizes iron and aluminum, the main impurities usually found at a low grade rare earth ore as insoluble compounds as phosphates.
• FIG. 6 and FIG. 7 show the correlation between phosphate and iron/aluminum extraction and FIG. 8 shows an X-Ray difractometry of the kiln product and the formation of iron phosphate.
• the kiln product is cooled at any way known by those skilled in the art. Cooling down is needed as rare earth sulfates reduce solubility with the increase of temperature. Therefore, cooling the calcine will reduce the increase in temperature during dissolution and reduce risks of losing rare earths due to that effect. Dissolution temperature must be kept below 50°C, preferably at 25°C. Enough water must be added to solubilize all the rare earth elements at the defined temperature and that fact is dependable on both temperature of the pulp and the grade of rare earths in the ore. A pulp with 1 to 50% solids, preferably between 5 and 20% is sufficient to achieve full rare earths dissolution.
• the clean rare earth solution can be taken to any operation known by those skilled in the art, such as, but not limited to, rare earth precipitation as hydroxides, followed by HCl leaching and solvent extraction, as shown at FIG. 5.
• One advantage of the present disclosure is the ability of exploiting low grade rare earth ores, not amenable to conventional mineral concentration. These ores cannot be submitted to conventional rare earth extraction techniques, such as caustic cracking or sulfation as too much acid would be needed and the final PLS would contain too many impurities and their removal would also be very costly.
• This invention brings a process that is able to selectively attack rare earth minerals indirectly, producing a clear solution that is simple to treat and obtain final rare earth products.
• Table 3 indicates the infeasibility of sample upgrading.
• Tables 4 and 5 are related to the complete grain size distribution: Table 4
• the complete grain size distribution tables disclose acid consuming impurities (Fe, Al, Mg, Ca) in sulfation process and possible caustic consuming (Al e Si) in alkaline process.
• the sample was crushed until be 100% less than 0.5 mm. In the next step, it was dried at 120°C.
• R [(H2S04 Mass) / (ROM Mass)] x 1000
• the sulfated mass was transferred to zirconite vessel, which was capped and placed in a muffle following a heating curve of 200°C/h.
• the table indicates that there is a relation between rare earth extraction and time, however there is no relation between iron and aluminum fixation and time.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
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• Life Sciences & Earth Sciences (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Manufacturing & Machinery (AREA)
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• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

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