WO2017100933A1 - Procédé de traitement de minerai de terre rare par mélange d'acide, sulfatage et décomposition - Google Patents

Procédé de traitement de minerai de terre rare par mélange d'acide, sulfatage et décomposition Download PDF

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Publication number
WO2017100933A1
WO2017100933A1 PCT/CA2016/051489 CA2016051489W WO2017100933A1 WO 2017100933 A1 WO2017100933 A1 WO 2017100933A1 CA 2016051489 W CA2016051489 W CA 2016051489W WO 2017100933 A1 WO2017100933 A1 WO 2017100933A1
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Prior art keywords
mineral concentrate
calcine
acid
gangue
rees
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PCT/CA2016/051489
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English (en)
Inventor
Dirk Naumann
John Richard GOODE
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Quest Rare Minerals Ltd.
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Priority to CA3008040A priority Critical patent/CA3008040C/fr
Publication of WO2017100933A1 publication Critical patent/WO2017100933A1/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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C22B1/06—Sulfating roasting
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • 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 processes and methods for the purification of rare earth metals and metal oxides from ore deposits.
  • rare earth elements such as europium, gadolinium, dysprosium, terbium, holmium, erbium, thulium, ytterbium, lutetium, and yttrium or Eu-Lu+Y, are critical inputs to many clean technologies and generally in short supply.
  • REEs are found around the world in varying concentrations in mineral deposits (for example, as fluorocarbonates, phosphates, or silicates) and often in association with various undesirable metals such as iron, aluminum, zirconium and niobium that require complex and uneconomical processing methods.
  • Rare earth minerals can sometimes be substantially separated from associated gangue minerals to a degree sufficient to produce a mineral concentrate that is suitable for processing by methods well known by the industry, such as acid or caustic attacks. With state of the art processing methods, however, not all deposits are amenable to sufficient pre-concentration and separation of rare earth metals from gangue metals to enable economical extraction of rare earth metals. Separation of gangue metals from the rare earths is a major challenge for many types of rare earth bearing mineral deposits and is required for economic viability.
  • CN Publication No. 1029121 17B describes a system and provides at a high level, a continuous acid roasting process for the decomposition of REE ore powder and iron powder ore. Given the focus of this reference on describing the configuration of the industrial system for decomposing REE ores and recycling heat and sulphuric acid, the acid roasting process supported by the system is not disclosed in any detail and no information is provided about the composition of the REE ore which may be processed by the system and process. [0008] As described in CN Publication No. 102912117B, REE ore may be mixed with sulphuric acid and heated to 300°C until a dried calcine is obtained comprising soluble rare earth ore sulphates.
  • This material is then continuously and gradually heated to 800°C to complete the roasting decomposition which entails the decomposition of sulphuric acid and ferric pyrophosphate, to facilitate removing iron, phosphorus, thorium and other impurities (not specifically elaborated on), enhance the decomposition of rare earth ore and improve the recovery of REEs.
  • a dissolution step is applied to the decomposed roasted material to facilitate further processing.
  • PCT/BR2013/000148 a process for purifying heavy REEs (HREEs) from ore is described wherein sub-stoichiometric amounts of sulphuric acid are used to obtain sulphates of iron and/or aluminum from partially processed ore materials and then submitting the mixture to temperatures of between 620°C and 750°C which triggers the sulphation of HREEs at the same time as iron and aluminum sulphates are decomposed.
  • the process is demonstrated using ore samples containing high levels of iron and very low levels of dysprosium, europium, erbium, holmium and lutetium. It is contemplated for the exploitation of low grade rare earth ores not amenable to conventional concentrating processes and acid baking techniques, due to the requirement for high amounts of acid and the resulting leachates containing too many impurities which would require costly removal processes.
  • mass ratios of sulphuric acid to dry ore materials are described as ranging from 100 kg acid/t of dry ore material to 3000 kg acid/t of dry ore material.
  • the pre -treatment of ore is contemplated to physically concentrate or enrich the ore materials subjected to acid baking.
  • the process is described as being carried out on material exhibiting a particle size of less than 700 microns and advantageously less than 400 microns.
  • the effective separation of REEs from one another and from gangue elements following acid roasting may be enhanced by using and combining various purification steps as described in CN 101012499 (such as ultrasonic extraction in combination with electrochemical oxidation and chemical treatments).
  • the purification step protocols disclosed in this reference have been described as effective for the purification of cerium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium and yttrium oxides, but are numerous and cumbersome from an industrial applicability standpoint.
  • the present invention relates generally to processes and methods for selectively recovering rare earth metals from ore or mineral concentrates such as, but not limited to, those containing rare earth oxides, silicate, carbonate, fluorcorbonate, fluoride, or phosphate minerals.
  • heavy rare earth elements europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium
  • iron aluminum, thorium
  • scandium and the light rare earth elements
  • the processes and methods disclosed herein represent four stages of processing including a first stage comprising the beneficiation of ore to prepare a mineral concentrate (i.e. concentrated and/or enriched in REEs), a second stage comprising acid-ore (concentrate) mixing to substantial homogeneity and heating to sulphate the REEs and gangue elements in the mineral concentrate, a third stage comprising the selective decomposition of gangue element sulphates at high temperatures into insoluble gangue element compounds; and a fourth stage to separate soluble REE compounds from insoluble gangue element compounds, comprising a leaching step and further downstream processing to extract REE oxides with a high recovery rate from the mineral concentrate with substantially reduced gangue element impurities.
  • a first stage comprising the beneficiation of ore to prepare a mineral concentrate (i.e. concentrated and/or enriched in REEs)
  • a second stage comprising acid-ore (concentrate) mixing to substantial homogeneity and heating to sulphate the REEs and gangue
  • a process for purifying REEs from an ore also comprising gangue elements comprising the steps of: (i) preparing a mineral concentrate from ore material containing REEs and gangue elements; ii) combining and mixing concentrated sulphuric acid in a super-stoichiometric amount to the mineral concentrate to produce a homogeneous agglomerate or powder mixture; iii) heating the homogeneous agglomerate or powder mixture to temperatures between about 150°C and about 330°C to sulphate the REEs and gangue elements and produce a first calcine; iv) heating the first calcine to temperatures between about 400°C to about 800°C to decompose the sulphates of the gangue elements and produce a second calcine comprising insoluble gangue element compounds, soluble REE sulphates, and a gas stream comprising S0 3 and/or S0 2 ; and v) subjecting
  • the ore material comprises a mixture of LREEs, HREEs and one or more gangue elements selected from the group of iron, aluminum, niobium and zirconium.
  • the ore material is derived from a silicate, monazite, or bastnaesite deposit.
  • the mineral concentrate is prepared by beneficiation of the ore material by one or more physical methods selected from sensor based sorting, flotation, magnetic separation, and gravity separation.
  • the concentrated sulphuric acid and the mineral concentrate are combined and mixed in a manner so as to obtain and maintain a granular mixture consistency throughout mixing
  • the concentrated sulphuric acid is combined and mixed in batches or a stage-wise manner with the mineral concentrate.
  • the step of combining and mixing the concentrated sulphuric acid and the mineral concentrate is done in whole or in part concurrently with the step of heating the homogeneous agglomerate or powder mixture to sulphate REEs and gangue elements to produce the first calcine.
  • the homogeneous agglomerate or powder mixture is produced by adding a recycled amount of first calcine during mixing of the concentrated sulphuric acid and the mineral concentrate.
  • the step of combining and mixing the concentrated sulphuric acid and the mineral concentrate is done in a high sheer mixer, pug mill, paddle mixer, ribbon mixer, or rotary drum mixer.
  • the homogeneous agglomerate or powder mixture has a substantially uniform pellet diameter or particle size, produced in whole or in part by applying a pelletizing mixing action and particle removal method during mixing of the concentrated acid and mineral concentrate.
  • the homogenous agglomerate or powder mixture has a substantially uniform particle size, produced in whole or in part by one or more cycles of grinding and screening.
  • the homogenous agglomerate or powder mixture is heated to between about 150°C and about 330°C for about 15 to about 240 minutes.
  • the homogenous agglomerate or powder mixture is continuously fed into a first thermal vessel for heating to produce the first calcine.
  • the first calcine is heated to between about 400°C to about 800°C for about 15 to about 240 minutes.
  • the first calcine is continuously fed from the first thermal vessel into a second thermal vessel for heating to produce the second calcine.
  • concentrated sulphuric acid is produced or recovered from the gas stream and recycled to produce the homogeneous agglomerate or powder mixture.
  • leaching of the second calcine is done with dilute acid or water.
  • the sulphated REEs in the leachate solution are recovered out of solution as REE solids by pH adjustment, precipitation reactions and/or solvent extraction methods.
  • a process for purifying REEs from an ore also comprising gangue elements comprising the steps of: (i) preparing a mineral concentrate from ore material containing REEs and gangue elements; ii) combining and mixing concentrated sulphuric acid in a super-stoichiometric amount to the mineral concentrate in a manner so as to obtain and maintain a granular mixture consistency throughout mixing to produce a homogeneous agglomerate or powder mixture; iii) heating the homogeneous agglomerate or powder mixture to temperatures between about 150°C and about 330°C to sulphate the REEs and gangue elements and produce a first calcine; iv) heating the first calcine to temperatures between about 400°C to about 800°C to decompose the sulphates of the gangue elements and produce a second calcine comprising insoluble gangue element compounds, soluble REE sulphates, and a gas stream comprising insoluble gangue element compounds, soluble
  • a process for purifying REEs from an ore also comprising gangue elements comprising the steps of: (i) preparing a mineral concentrate from ore material containing REEs and gangue elements, using a combination of sensor-based sorting and flotation; ii) combining and mixing concentrated sulphuric acid in a super-stoichiometric amount to the mineral concentrate in a manner so as to obtain and maintain a granular mixture consistency throughout mixing to produce a homogeneous agglomerate or powder mixture; iii) heating the homogeneous agglomerate or powder mixture to temperatures between about 200°C and about 300°C for one to two hours to sulphate the REEs and gangue elements and produce a first calcine; iv) heating the first calcine to temperatures between about 600°C to about 700°C for one to two hours to decompose the sulphates of the gangue elements and produce a second calcine compris
  • a process for producing a homogeneous agglomerate or powder mixture of concentrated sulphuric acid and mineral concentrate containing REEs and gangue elements comprising the step of combining and mixing concentrated sulphuric acid in a super-stoichiometric amount to a mineral concentrate in a manner so as to obtain and maintain a granular mixture consistency throughout mixing to produce a homogeneous agglomerate or powder mixture.
  • the concentrated sulphuric acid is combined and mixed in batches or a stage- wise manner with the mineral concentrate.
  • the concentrated sulphuric acid is combined and mixed with the mineral concentrate in dosage amounts each ranging from about 200 kg to about 900 kg of acid per tonne of mineral concentrate until the super-stoichiometric amount of concentrated sulphuric acid has been combined and mixed with the mineral concentrate.
  • the super-stoichiometric amount of acid is about 800 kg to 1500 kg of acid per tonne of mineral concentrate.
  • the homogeneous agglomerate or powder mixture is produced by adding an amount of calcine during mixing of the concentrated sulphuric acid and the mineral concentrate.
  • the mixing of concentrated sulphuric acid and mineral concentrate is carried out at temperatures ranging from about 150°C to about 330°C.
  • Figures 1 is a schematic representation of an X-ray sensor based sorting system for the separation of ore material into fractions that are high and low in REE content. Sensor systems other than X-ray may be effective on other ores.
  • Figures 2 is a graphical representation of the data of Table 1, namely a comparison of the extraction of gangue metal elements using a two-step selective thermal sulphation process (represented by the circular data points plot) versus a nonselective single step acid bake process (represented by the triangular data points plot).
  • Figure 3 Block flow diagram of an exemplary process for purifying REEs from gangue elements staring with ore materials from Strange Lake Deposit (Zone B) in Quebec, Canada containing one of the largest rare earth, yttrium and zirconium deposits in the world. The Strange Lake Deposit has a HREO:TREO ratio of 50% in the enriched zone.
  • Figure 4 Graphical representation of the effect of ore material grind size on flotation recovery of REE in mineral concentrate. The data was generated using a Flotinor 1682 Collector (and reagent scheme).
  • Figure 5 Graphical representation of Mass Pull versus REE recovery using a Flotinor 1682 reagent scheme, comprising a sodium silicate depressant and citric/oxalic acid modifiers.
  • Figure 6 Effect of acid dosage on the consistency of concentrated sulphuric acid/mineral concentrate mixtures. At single stage acid dosages above 625 kg/T the consistency of the resulting mixtures becomes increasingly sticky and paste-like.
  • Figure 7 Formation of agglomerates using a multi-stage acid addition (A) and recycled calcine (B) methods and low intensity acid mixing.
  • the recycled calcine method reduces stickiness and is therefore beneficial to the process.
  • Figure 8 Effect of mineral concentrate (particle) grind size on sulphated element recovery, including REEs (including Y) (diamond data points plot), iron, zirconium and niobium (triangular data points plot), after thermal sulphation under the following conditions: 300°C, 3 hour bake time, 600kg H2S04/t ore, and followed by a 1 h leach at 22°C.
  • the lower plot with square data points depicts the recovery of iron and the upper plot of square data points depicts zirconium recovery.
  • Figure 9 An exemplary kiln configuration for carrying out a thermal sulphation protocol according to the disclosure.
  • Figure 10 An elemental breakdown of the effect of mineral concentrate (particle) grind size on sulphated element recovery, following single stage, low temperature sulphation under the following conditions: 300°C, 3 hour bake time, 600kg H2S04/t ore, and followed by a 1 h leach at 22°C.
  • the particle sizes in the legend from top to bottom correspond to the order of bar groupings from left to right.
  • Figure 11 Exemplary Dy recovery following single stage, low temperature sulphation at different concentrated sulphuric acid (kg) /mineral concentrate (T) ratios, temperatures and heating times (A: 600kg/T; B: 750 kg/T; C: 1200 kg/T; D: 1500 kg/T).
  • Figure 12 Exemplary HREE recovery following single stage, low temperature sulphation at different concentrated sulphuric acid (kg) /mineral concentrate (T) ratios, temperatures and heating times (A: 600kg/T; B: 750 kg/T; C: 1200 kg/T; D: 1500 kg/T).
  • Figure 13 Exemplary TREE recovery following single stage, low temperature sulphation at different concentrated sulphuric acid (kg) /mineral concentrate (T) ratios, temperatures and heating times (A: 600kg/T; B: 750 kg/T; C: 1200 kg/T; D: 1500 kg/T).
  • Figure 14 High strength acid recovery at condensation temperatures between 180°C and 220°C.
  • the results with respect to the bake (BK) samples listed in the legend from top to bottom correspond to the order of bars in each bar grouping from left to right.
  • Figure 15 An exemplary acid recovery gas condenser train configuration.
  • Figure 16 Schematic representation of an industrial system flow implementation for a two-step sulphation and selective sulphate decomposition process including multi-stage acid/mineral concentrate mixing. Also shown is a two stage acid bake with a first stage carried out at 280°C and a second stage carried out at 300°C. The abbreviations "LT” and "HT” stand for low temperature and high temperature, respectively.
  • Figure 17 Schematic representation of an industrial system flow implementation of a calcine recycling protocol in acid/mineral concentrate mixing.
  • the present disclosure relates to processes and methods for separating REEs from gangue metals and other materials found in rare earth ores to provide substantially pure REEs which can be further processed for industrial application.
  • a selective thermal sulphation process for separating REEs from gangue minerals and non-REE metals that can be applied to ore sources rich in REEs, but with varying compositions of LREEs, HREEs and gangue-related elements.
  • An overall process and method flow diagram is provided at Figure 3. The process can also be applied for recovering REEs from secondary sources such as phosphor powder from fluorescent lighting devices.
  • the terms “comprising,” “having,” “including” and “containing,” and grammatical variations thereof, are inclusive or open-ended and do not exclude additional, unrecited elements and/or method steps.
  • the term “consisting essentially of when used herein in connection with an apparatus, system, use or method, denotes that additional elements and/or method steps may be present, but that these additions do not materially affect the manner in which the recited apparatus, system, method or use functions.
  • the term “consisting of when used herein in connection with an apparatus, system, use or method excludes the presence of additional elements and/or method steps.
  • An apparatus, system, use or method described herein as comprising certain elements and/or steps may also, in certain embodiments consist essentially of those elements and/or steps, and in other embodiments consist of those elements and/or steps, whether or not these embodiments are specifically referred to.
  • rare earths refer to the industrially relevant elements of the periodic table including lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), as well as scandium (Sc) and yttrium (Y).
  • La lanthanum
  • Ce cerium
  • Pr praseodymium
  • Nd neodymium
  • Sm samarium
  • Eu europium
  • Gd gadolinium
  • Tb terbium
  • Dy dysprosium
  • Ho holmium
  • Er erbium
  • Tm thulium
  • Yb ytterbium
  • Lu scandium
  • Promethium (Pm) is not included as it has no stable isotopes and does not exist in nature.
  • These elements may be further referred to as "light” and “heavy” REEs to further delineate subsets of REEs based on their respective unpaired and paired electron configurations, namely (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd) as light rare earth elements (“LREE(s)”) and terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), as heavy rare earth elements ("HREE(s)”).
  • Yttrium is regarded as a HREE due to the similarity of its similar chemical properties, whereas scandium's properties are not similar enough to any LR
  • REEs, LREEs and HREEs may be a reference to the element, oxide or other compound forms of these elements as they may be found in ores, in the solid product of purification processes, or in a solubilized state in solution.
  • REO(s) may be used interchangeably with REE(s) and reference to light and heavy REOs may be made as "LREO(s)” and "HREO(s)”, and used interchangeably with LREE(s) and HREE(s), respectively.
  • TREE(s) and “TREO(s)” may be interchangeably used to refer to the total REE/REO present in a given sample, batch or load of ore material, mineral concentrate, or recovered amount of solid material from one or more ore processing steps.
  • ore(s) or “ore material(s)” as used herein refer to (mining output) material as received from a mine before beneficiation, chemical treatment, or other selection and purification procedures applied to change the relative content of, composition, or chemical form of REEs in a given ore sample, batch or load received from the mine.
  • Ore or mining output material may also include material which has been subjected to physical processing to break it up into smaller pieces for ease of management in transportation and for application in beneficiation procedures, such as, but not limited to, flotation, and/or (X-ray) sensor based separation techniques.
  • partially processed ore material(s) refer to ore material(s) which have been partially processed, but wherein substantially all or a portion of REEs are in their naturally occurring or original mineralized states, whether or not such mineralized states include matrix integration or composite structures with gangue and/or other non- REE elements.
  • Partially processed ore materials can arise following physical processing (e.g. crushing or grinding into small particulate matter or powder), beneficiation to concentrate and/or enrich the REE content in the ore material (e.g. using recycled materials). In other words, partially processed ore materials have not undergone any substantial chemical processing to chemically modify, solubilize, extract or precipitate REEs.
  • Partially processed ore material may have undergone limited chemical treatments as part of flotation methods to chemically alter ore mineral surfaces in order to facilitate the physical separation of desirable REEs minerals from undesirable sands/silica, silicate gangue or non-REE silicates.
  • the term "beneficiation” refers to processes which can result in partially processed ore(s) where the content of REEs is concentrated or enriched. Concentration or enrichment can be achieved by the application of one or more processes or procedures which effect the physical separation of undesirable materials, such as sands, which are loosely associated with mineral matrices of REEs or REE composite structures in ore materials.
  • concentration of REE content may be achieved by magnetic separation, sensor based systems which scan pieces of ore for REE content and which can selectively sort and separate low REE content pieces from high REE content pieces (e.g. sensor based systems), and the removal of sands and non-REE silicates or other gangue minerals (e.g. through flotation procedures).
  • REE content in a given sample of partially processed ore material can be further enriched by the addition of partially processed ore material from distinct sources, or the addition of recycled materials with REE content.
  • the term "mineral concentrate” refers to partially processed ore material that is the product of one or more beneficiation processes that has resulted in the removal of gangue material, such as iron, aluminum and silicon compounds. It is characterized by having a higher concentration of desirable REEs compared to the ore or mine output material it was derived from, and the material which is subjected to chemical processing, for example, acid baking with concentrated sulphuric acid.
  • An exemplary mineral concentrate derived from ore material of the Strange Lake Deposit, may contain a mixture of natural granite and pegmatite minerals containing rare earth minerals, zirconium, niobium, iron, calcium, trace beryllium and naturally occurring radiological trace elements.
  • Gangue refers to minerals, non-REE metal and non- metal elements, found in ore materials, which are targeted for separation from REEs.
  • Gangue minerals containing elements such as silicon (Si), iron (Fe), aluminum (Al), zirconium (Zr), niobium (Nb), and titanium (Ti) may form matrices in which desirable REE minerals are embedded, or otherwise form mineral composites with REEs which require chemical or physical processing methods to separate them from REEs.
  • the term "calcine” as used herein refers to the product of chemically processed mineral concentrate which has been subjected to thermally assisted acid treatment or thermally assisted sulphate decomposition process.
  • the terms "acid bake,” “acid roast”, “acid baking” and “acid roasting” refer to a thermal sulphation process consisting of heating a mixture of sulphuric acid and ore (or concentrate). This process may be conducted at temperatures ranging typically between about 150°C up to about 400°C. By contrast thermal sulphate decomposition processes are typically conducted at temperatures above about 500°C to about 800 U C.
  • leaching and leachate refer, respectively, to the process and product of dissolving desirable (REE) minerals into a liquid solution by using a lixiviant reagent of mixture of reagents such as water or a diluted/mild acid (typically, sulphuric acid or hydrochloric acid).
  • Leachates contain solubilized REEs which have been, or can be separated from solubilized gangue elements and other impurities by way of selective decomposition and precipitation processes, such as, but not limited to selective sulphate decomposition.
  • PLS pregnant leach solution
  • extract is used herein with reference to the process of recovering elements in one or more solid forms, such as metal oxides from a liquid or solid mixture.
  • the recovered elements may be in solution or solid materials that have been separated out from liquid suspensions, precipitated from liquid solutions, or mechanically separated from other solids.
  • reductant refers to the solid faction of an ore processing or purification step that contains predominantly undesirable non-REE minerals or salts and is not processed in subsequent or downstream steps to obtain purified, concentrated or enriched REE materials in solid (e.g. oxide) or liquid form (e.g. sulphated in solution).
  • agglomerate refers to the association of smaller (primary) particles to form larger particles in which the identity of the smaller particles is still detectable.
  • the nature of agglomerates is affected by the chemical nature and interaction between primary particles, as well as the mixing time, speed and intensity of a given process or method to produce them.
  • a homogenous agglomerate as used herein denotes a mixture having a consistency amenable for being processed and/or fed continuously through different mineral concentrate processing stages.
  • a homogeneous agglomerate denotes an acid/mineral concentrate mixture that is sufficiently dry so as not to be sticky or cause blockages in equipment it is fed through.
  • homogeneous and homogeneity refer to the uniform composition and distribution of components in a mixture, such as the mixtures of concentrated sulphuric acid and mineral concentrate obtained according to the processes and methods disclosed herein.
  • a mixture of acid and mineral concentrate can be wet and sticky and difficult to handle through process equipment. Under these circumstances, recycling calcine can be very beneficial and permit the relatively trouble-free processing of what would otherwise be material difficult to process. Achieving homogenous mixing of acid and mineral concentrate ensures complete chemical processing of the mineral concentrate during heat-assisted sulphation and selective desulphation processing.
  • Optimal proportions of acid and mineral concentrate that have been uniformly mixed to a state of homogeneity according to the present disclosure are evidenced by the formation of sufficiently dry agglomerates or powders that can be fed continuously and at a controllable rate into one or more thermal vessels without sticking or blockage, and with minimal operational disruptions, stoppages or adjustments to maintain the desired feed rate of material through different processing stages.
  • any embodiment discussed herein can be implemented with respect to any disclosed process, method, use, apparatus or system.
  • an apparatus and/or system provided herein can be applied to carry out the disclosed processes and methods and said processes and methods can delimit the operational parameters and functional characteristics of a disclosed apparatus or system.
  • ore materials are crushed into smaller pieces (comminution) and sorted to reject coarse-grained quartz, feldspar and other pieces of ore material which are relatively low in REE content. Sorting may be done using X-ray sensor-based systems (e.g. the Tomra Com Tertiary XRT production scale sorting system) to remove low REE grade rock from higher grade REE rock.
  • the sorting protocol may include an initial screening to create more homogeneously sized fractions of ore material for sorting. In one embodiment fractions of ore material for sorting comprise rock pieces of about 10-20 mm or 20-40 mm.
  • ore materials may be fractionated into pieces of ore of about 12 to 20 mm, 10 to 19 mm or 19-38 mm in size. It will be understood by one skilled in the art that such ore fractions may also contain fines of ore material (i.e. particles less than 10 mm in size) arising from the crushing process.
  • an exemplary sorting protocol and apparatus comprises a belt feeding system 1 which facilitates the presentation of non-uniform feed, and particle stabilization before scanning with X-ray sensor transmission technology that recognizes and separates ore materials based on specific atomic density.
  • a broad-band electrical x-ray source 3 is applied to the material to be sorted as it is carried on a moving belt.
  • the sensor system including a X-ray camera 2 sits below the belt in the exemplary configuration shown in Figure 1 , and produces a digital image of the material being sorted using two different energy bands. Depending on the thickness and density of the ore materials scanned, an image transformation of the density images of the two bands allows pixel classification relative to a reference atomic density.
  • Scanned ore materials are either ejected or accepted as material streams A or B in a separation chamber 4, respectively.
  • the material that is ejected may be either waste material (barren rock) or ore material targeted for further processing (e.g. beneficiation).
  • the "mass pull" value indicated in Table A denotes the amount of ore material retained following scanning and sorting of an amount of ore material fed into the sorting apparatus system and thus comprises the sorter accept and the fines that bypassed the sorter and were not sorted, i.e., the - 10 mm material in the upper portion of the above table and the -19 mm material in the lower portion of the table.
  • the final amount of material retained for further processing may be the result of multiple rounds of screening and sorting of ore material fractions.
  • a given input of ore material may be separated into fractions categorized as low and high in REE content, respectively.
  • the low REE fraction may be further sorted into fractions categorized as low and barren/waste (in REE content), and the high REE fraction may be further sorted into medium and high REE fractions.
  • ore sorting using such a system may be sufficient to produce ore material which can be ground to a fine particulate consistency to produce a mineral concentrate for chemical treatment (e.g. acid baking). Accordingly, in one embodiment mineral concentrate is produced only by sensor-based sorting. Flotation
  • a mineral concentrate is produced by applying a flotation protocol to (pre-sorted) ore materials.
  • This method for separating desirable minerals from gangue minerals exploits the hydrophobic properties of different minerals using surfactants and wetting agents.
  • Undesirable or gangue particles e.g. sands and other silicon compounds
  • desirable REE minerals are wetted and remain in the liquid phase of a mineral/water slurry or vice versa.
  • ore material prior to subjecting ore material to a flotation protocol, ore material is ground into fine particulate matter (micron sized particles).
  • ore material is ground to a grind size of 80% passing ("k80") of about 40 ⁇
  • Figure 4 demonstrates a relationship between the grind size of ore material and the flotation recovery of REE in the resulting mineral concentrate where the level of recovery decreases as grind size increases.
  • Figure 5 illustrates a relationship between mass pull and REE recovery following flotation where there is approximately a 10% increase in recovery for the indicated REE oxides when the mass pull is approximately doubled.
  • a 20% mass pull from flotation achieves 80% REE recovery and is used as a source of mineral concentrate in acid baking or a thermal sulphation protocol.
  • a mass pull of 20% to 55% from flotation is used as the source of mineral concentrate in an acid baking or thermal sulphation protocol.
  • one or more beneficiation protocols can be applied to produce a mineral concentrate, such as sensor-based sorting and flotation.
  • the mineral concentrate obtained following ore material beneficiation may require further adjustments to meet transport exemption activity levels for U and Th.
  • flotation recovery is controlled such that the content of U and Th in a mineral (flotation) concentrate is below 10 Bq/g of U and Th combined and below a total calculated activity of 1 10 Bq/g.
  • IAEA CNSC International Atomic Energy Agency/Canadian Nuclear Safety Commission
  • DG transportation and dangerous good
  • the mass pull/recovery can be adjusted by changing flotation reagent dosages, and by dilution with lower REE grade material.
  • An exemplary activity calculation for Strange Lake Mineral Concentrate is provided in Example 3.
  • beneficiated ore material Prior to processing mineral concentrate to purify REEs, drying will prevent dilution of the concentrated sulphuric acid that is added to the mineral concentrate. Accordingly, in one embodiment beneficiated ore material is dried, as required, to reduce moisture content before being mixed with sulphuric acid. In a related embodiment the mineral concentrate moisture level after drying is less than 1%.
  • the step of combining and mixing concentrated sulphuric acid in a super- stoichiometric amount to mineral concentrate is conducted in such a way so as to ensure that there is material (i.e. a mixture of acid and mineral concentrate) that can be and is available to be continuously fed into a heated vessel without sticking or creating blockages.
  • material i.e. a mixture of acid and mineral concentrate
  • Combining and mixing acid and concentrate to obtain and maintain a granular or particulate consistency throughout the mixing process provides for the consistent flowability of material through an industrial processing system (e.g. a plant) for the purification of REEs from mineral concentrate.
  • the amount of acid used is dependent on acid utilization efficiency, while acid/mineral concentrate mixing is integrally linked to acid dosage and the total amount of acid used.
  • Using a super- stoichiometric amount acid to mineral concentrate ensures substantially complete sulphation of REEs, and also accounts for acid usage/consumption by gangue and other elements.
  • One or more of the following strategies can be used to produce acid/mineral concentrate mixing conditions which optimizes acid utilization efficiency: a) Limitation of sulphuric acid addition (i.e. total acid is delivered in batches or dosage amounts for mixing with concentrate) so as to avoid formation of sticky, paste-like material;
  • the modulation of concentrated sulphuric acid addition to mineral concentrate at a rate and/or in dosages that provide for a granular or particulate mixture consistency upon mixing can be done in whole or in part by combining acid and concentrate, and optionally calcine, at intervals in between cycles of thermal sulphation or concurrently with thermal sulphation by controlling the rate of addition of acid to concentrate in a heated vessel.
  • Mixture heating can be done in a single or in multiple thermal vessels (in kilns or fluidized bed reactors) to apply the strategies for optimizing acid utilization efficiencies and for optimizing material flowability during acid/concentrate mixing and thermal sulphation of the resulting mixture.
  • the dosage of acid combined with concentrate is selected from about 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875 and 900 kg of acid per tonne of mineral concentrate.
  • calcine may be added to obtain the desired granular or particulate consistency upon mixing
  • a homogeneous agglomerate or powder In one embodiment about 600 to 625 kg/t of concentrated sulphuric acid to mineral concentrate is used to produce a homogeneous agglomerate or powder.
  • a homogeneous, agglomerate or powder has a sufficient level of mechanical integrity so that it can be continuously fed into a thermal (sulphation) vessel at a consistent flow rate without blockage or sticking.
  • the effect of acid dosage and mixing on the resulting consistency of an acid/mineral concentrate mixture is illustrated in Figures 6 and 7.
  • the formation of a homogeneous agglomerate in one embodiment is prepared by the stage-wise addition of acid at single dosages ranging between about 220 kg to about 625 kg of acid per tonne of mineral concentrate, with continuous mixing.
  • acid dosages for stage-wise mixing range between about 200 kg to about 900 kg of acid per tonne of mineral concentrate.
  • Such protocols comprise making successive additions of acid, concurrently with or followed by thermal processing of acid/concentrate mixture after each stage of acid addition until a total of about 800 kg to about 1500 kg of concentrated sulphuric acid per tonne of mineral concentrate have been mixed.
  • desirable particulate (e.g. agglomerate or powder-like) acid/concentrate mixture properties can be maintained.
  • stages of mixing during acid baking include the step of mixture cooling preceding the addition of successive doses of acid to partially sulphated mineral concentrate.
  • the formation of a homogeneous dry agglomerate or powder that is easy to handle is facilitated and promoted by recycling a portion of sulphated mineral concentrate following acid baking (calcine). Calcine is added into an acid/mineral concentrate mixture and remixed. Use of this protocol may require a larger vessel to achieve target throughputs.
  • concentrated sulphuric acid and mineral concentrate are mixed at a low intensity to form a homogeneous agglomerate or powder.
  • agglomeration is conducted in a concrete or other kind of rotary mixer.
  • acid and concentrate are mixed at about 100 rpm.
  • the grind size of mineral concentrate particles mixed with concentrated sulphuric acid is about 40 ⁇ .
  • Figure 8 illustrates the effect of mineral concentrate (particle) grind size on sulphated element recovery. A more detailed breakdown of element recovery based on grind size is provided in Figure 10.
  • mixing of acid and mineral concentrate is carried out before feeding the mixture into a thermal sulphation vessel.
  • mixing of acid and mineral concentrate is carried out in a thermal sulphation vessel.
  • acid and mineral concentrate mixing is carried out before and after feeding the mixture into a thermal sulphation vessel.
  • temperature may be controlled to optimize the sulphation of mineral concentrate elements.
  • thermal sulphation or acid baking of an acid/mineral concentrate mixture is conducted in a rotary kiln, packed bed reactor, fluidized bed reactor, moving fixed bed or grate, or a continuous stirred tank.
  • An exemplary kiln configuration is provided in Figure 9, including a quartz kiln with lifters 10, operatively associated with an electric furnace 1 1, variable-speed kiln drive 12 and air source 13.
  • Various temperature sensors and controls (14, 15 and 16) are provided for the furnace 14, gas inlet 15 and to track burden temperature 16.
  • the acid and mineral mixture may be heated at a sustained temperature of 150°C, 200°C, 250°C, 300°C, or 350°C.
  • acid baking may be carried out over a variety of temperature ranges, including ranges such as 150°C to less than 400°C, 150°C to 330°C, 200°C to 310°C, 250°C to 330°C, 250°C to 300°C, 270°C to 300°C or 280"C to 300°C.
  • rare earth containing minerals react with the sulphuric acid to form water-soluble REE sulphates.
  • the completeness of the sulphation reactions will depend in part on the length of time the acid and mineral concentrate mixture is heated.
  • the acid and mineral concentrate mixture is continuously fed into a first thermal vessel wherein the mixture is heated for a residence time, ranging from 15 to 240 minutes, 30 to 120 minutes or 60 to 90 minutes before the resulting calcine is subjected to a selective thermal sulphate decomposition protocol.
  • thermal sulphation of mineral concentrate elements is carried out at 300°C, using a total of 1400-1500 kg of concentrated sulphuric acid per tonne of mineral concentrate for 120 minutes.
  • thermal sulphation or acid baking of mineral concentrate elements is carried out at 270°C to less than 300°C, using a total of about 1000 kg of concentrate sulphuric acid per tonne of mineral concentrate for 120 minutes to optimize total REE recovery.
  • thermal sulphation or acid baking is carried out by packing agglomerates of acid/mineral concentrate mixtures into a thermal vessel to reduce the evaporation of acid during heating (e.g. a packed bed reactor).
  • thermal sulphation or acid baking is conducted in a closed thermal vessel to reduce acid loss during the sulphation of mineral concentrate elements.
  • the sulphation of mineral concentrate elements may be optimized by controlling the feed rate into and amount of acid/mineral concentrate agglomerate or powder mixture in the thermal vessel, the pressure in the vessel and the atmospheric environment.
  • the heating rate applied to the acid/mineral concentrate mixture may be varied to optimize the completeness of mineral concentrate element sulphation.
  • the mixture of rare earth sulphates and any gangue-derived, or non-REE metal sulphates present in the calcine product of an acid bake are subjected to a higher temperature heating protocol of at least about 400°C but not more than about 800°C.
  • the calcine product resulting from acid baking may be heated at a sustained temperature of 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C or 750°C.
  • the calcine product resulting from acid baking may be heated over a variety of temperature ranges, including ranges of 400°C to no more than 800°C, 550°C to 750°C, 600°C to 750°C, 580°C to 680°C, and 650°C to 700°C.
  • the high temperature provides thermodynamically favourable conditions for the preferential decomposition of the gangue metal sulfates, such as those of iron, aluminum, niobium and zirconium, while minimizing the decomposition of REEs.
  • This thermal sulphate decomposition protocol may be carried out in a separate thermal vessel than the lower temperature acid baking protocol.
  • the first calcine product of thermal sulphation is removed from the thermal sulphation vessel and fed into a selective thermal sulphate decomposition vessel to produce a second calcine product.
  • the first calcine product is pre -heated prior to being fed into the selective thermal sulphate decomposition vessel.
  • Coarser agglomerates containing non-REE sulphates exhibit less complete decomposition and have a grey colouring when crushed. Finer agglomerates of a similar composition have a reddish colour when crushed that is indicative of more complete selective iron sulphate decomposition.
  • the first calcine product is mechanically processed prior to or as it is fed into the selective thermal sulphate decomposition vessel to optimize agglomerate size and to maximize the completeness of selective thermal sulphate decomposition.
  • the optimized agglomerate size is between 3 to 10 mm.
  • selective thermal sulphate decomposition is controlled to achieve maximum Fe sulphate decomposition with less than 5% REE sulphate decomposition. In a further embodiment, selective thermal sulphate decomposition is controlled to achieve 80%-90% Fe sulphate decomposition.
  • Processing costs may also be reduced by incorporating heat recovery and acid recovery methods as part of the processes disclosed herein.
  • heat from the selective thermal decomposition of non-REE sulphates may be captured and recycled to preheat the calcine product of acid baking as it is fed from the acid baking thermal vessel to a another thermal vessel to carry out the selective thermal decomposition of gangue element sulphates.
  • the design of effective acid recovery methods requires consideration of the different processing steps in which acid losses occur. Super-stoichiometric quantities of sulphuric acid are usually required to achieve economic recoveries of rare earths in the typical acid attack process. Excess acid reports to off-gas during acid/mineral concentrate mixing, low temperature acid baking and high temperature selective sulphate decomposition.
  • Residual acid is carried into aqueous solution during leaching, and acid is also consumed by gangue metals.
  • Free acid lost to off-gas and aqueous solutions or reacted with gangue metals is typically neutralized with an alkaline chemical (such as lime or caustic reagents) and replaced with fresh acid.
  • Acid replacement and neutralization represent significant costs and generates waste products that must be disposed of.
  • H2SO4 vapourt ⁇ H 2 S0 4 (liquid) (cooling to 220°C) (12) S0 3 (gas) + H 2 0 (gas) ⁇ H2SO 4 ( ⁇ (cooling to 220°C) (13)
  • the present disclosure provides a method for the recovery of excess acid that is normally lost to the gas phase and PLS and is normally neutralized with alkaline chemicals.
  • the majority of acid that is not used in the sulphation reactions, and S0 3 that is liberated according to reactions (7) and (8) is recovered according to the reactions (10) to (13).
  • the S ⁇ 3 ⁇ 4 recovered can also be used together with concentrated sulphuric acid, or on its own as a sulphation agent.
  • Use of S0 3 in the sulphation stage of the process for REE extraction from mineral concentrate could be carried out using a fluidized bed system configuration.
  • high strength acid is recovered at condensation temperatures of 180°C to 220°C by passing off-gas through a primary condenser (see Figure 14).
  • Figure 14 presents data tracing the presence of sulphur and acid in various process fractions, based on baking acid/concentrate agglomerate mixture to 40 microns, baking and evaporation at 300°C, drying and a 1 h leach at 22°C .
  • Bar graph groupings A-D represent the amount of sulphur to calcine (A), sulphur to calcine titrated as free acid leach (B), sulphur to first condenser (C) and acid concentration in first condenser (D).
  • Values shown above the bar groupings are average parameter values for 600 and 500 kg acid/t mineral concentrate (ore).
  • the strength of the recovered acid is 93-96% (i.e. concentrated sulphuric acid).
  • low strength acid is recovered at temperatures of 40°C to 50°C.
  • acid is recovered using equipment including, but not limited to, condensers, electrostatic precipitators, or absorption columns.
  • an apparatus for the recovery of acid (see Figure 15) is configured as a gas train comprising one or more condensers 20, an electrostatic precipitator 21 operatively associated with a high voltage source, a scrubber 22 and glass fiber mist filter 23 operatively associated with a vacuum pump 24.
  • a gas train comprising one or more condensers 20, an electrostatic precipitator 21 operatively associated with a high voltage source, a scrubber 22 and glass fiber mist filter 23 operatively associated with a vacuum pump 24.
  • the calcine product of selective thermal sulphate decomposition contains a mixture of REE sulphates and water insoluble non-REE compounds.
  • a water or mild acid leaching protocol may be applied by successively adding the calcine to water or mild acidic water according to known methods in the art, for example, as described in Example 1 and 2. Further processing of the leachate to precipitate out purified REE compounds may also be done according to a number of protocols well known in the art to obtain mixtures of REE compounds, or to selectively isolate different REEs from one another.
  • more than 85% of REE content in a mineral concentrate is recovered in a leachate.
  • the leachate is subjected to a hydromet (i.e. hydrometallurgy) protocol that does not require solvent extraction to produce mixed REE oxides.
  • a hydromet i.e. hydrometallurgy
  • the REE containing leachate solution contains 10%- 20% Fe which is precipitated out of solution using MgCC>3.
  • a pilot or industrial scale plant system can be configured to carry out the process for purifying REEs from an ore also comprising gangue elements comprising the steps of: (i) preparing a mineral concentrate from ore material; ii) adding concentrated sulphuric acid in a super-stoichiometric amount to the mineral concentrate and mixing to produce a homogeneous agglomerate or powder mixture; iii) heating the mixture to temperatures between about 150°C and about 330°C to sulphate the REEs and gangue elements and produce a first calcine; iv) heating the first calcine to temperatures between about 400°C to about 800°C to decompose the sulphates of the gangue elements and produce a second calcine comprising insoluble gangue element compounds, soluble REE sulphates, and a gas stream comprising S0 3 and/or S0 2 ; and v) subjecting the second calcine to a leaching process to obtain a leachate solution
  • thermal sulphation and decomposition thermal vessels including the feeding of material in and out of the vessels, temperature control and material residence time in thermal vessels;
  • an exemplary industrial system and implementation protocol may comprise: a. 3 Stages of acid/concentrate mixing @ 889 kg/t total acid addition across the stages to provide the ratios of acid/concentrate indicated in 'b' for each stage b. 436 kg/T in stage 1 ; 665 kg/T stage 2; 889 kg/T stage 3 c. Heating at 273-291 °C (sulphation) following each acid addition stage in sequentially configured thermal vessels for a total of about one hour in each vessel d. Promoting agglomeration in a rotary kiln e. Heating to 673°C in a rotary kiln (selective sulphate decomposition) for about one hour
  • an industrial calcine recycle protocol for acid/mineral concentrate mixing may comprise: a. 809-840 kg/t Acid @ 47% calcine recycle ratio; calcine is obtained from a previous cycle of thermal sulphation and the remaining calcine product (53%) is subjected to further processing (desulphation) b. Heating to 296 °C c. A "one kiln" configuration for acid/concentrate mixing with recycled calcine d. Dry crushing of calcine for recycling e. Approximate calcine hot zone retention time of 99 min f. Low temperature calcine product charged as is for heating to 663-669 °C in a second kiln g. Approximate hot zone retention time of 71 min
  • a system for implementing the above protocols comprises, a feed (concentrate and recycled material) delivery system; heated acid /feed mixing equipment; an acid delivery system; one or more thermal vessels (e.g. kilns or furnaces) for carrying out sulphation and sulphate decomposition reactions on feed materials; an acid recovery and regeneration system; one or more off-gas treatment units; calcine handling equipment; waste material handling systems and storage facilities, and an instrumentation, control and data acquisition system, all operatively associated in such a way so as to carry out the processes and methods of the disclosure.
  • system for carrying out the processes and methods of the disclosure is configured to process about 3,550,000 Mt of mined ore material per year.
  • mine output is controlled to achieve constant flotation concentrate volume or grade.
  • system for carrying out the processes and methods of the disclosure is configured to process about 1 ,850,000 Mt/yr of mill feed.
  • system for carrying out the processes and methods of the disclosure is configured to process about 300,000 Mt/yr of flotation (mineral) concentrate.
  • system for carrying out the processes and methods of the disclosure is configured to input about 10,000 Mt/yr of lamp (phosphor) material.
  • the system for carrying out the processes and methods of the disclosure is configured to produce about 1 1,270 Mt/yr of mixed REE concentrate.
  • the system for carrying out the processes and methods of the disclosure is configured to produce about 1 1,050 Mt/yr of pure REOs.
  • reference to various embodiments of the processes of the present disclosure and related applications thereof, including those described in the Examples and in the Figures are illustrative of certain embodiments of the processes disclosed herein and are not intended to limit the scope of the invention in any way.
  • a bench scale test was conducted to test the effect of multi-stage acid addition and selective thermal sulphation.
  • 35 g of concentrated (96%) sulfuric acid was added to 50 g of dry flotation concentrate.
  • the acid and concentrate were mixed by hand with a plastic stick in a glass crucible to achieve as homogeneous a mixture as possible.
  • the crucible was placed in a muffle furnace where it was heated until the sample reached approximately 280°C, and it was maintained at this temperature for 30 minutes. The sample was removed from the furnace and allowed to cool slightly. An additional 25 g of concentrated sulphuric acid was added and again mixed with the solids by hand. After mixing, the crucible was charged again into the muffle furnace.
  • the sample was heated to 300°C and maintained at this temperature for an additional 30 min. The sample was then heated further to 650°C, and maintained at close to this temperature for 30 minutes, before being removed and allowed to cool. At all stages of the test, the mixture was either in dry powder or granular agglomerate form. Paste formation or adhesion was avoided by adding the acid in multiple stages with heating in between. After baking the sample weighed 60 g and 55 g of this was added to 406 mL of ambient temperature (25 °C) de-ionized (DI) water for leaching. Leaching was conducted in a glass reactor equipped with a PTFE impeller for lhr. The pulp was weighed and filtered, and the cake washed with 75 mL of DI water.
  • DI ambient temperature

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Abstract

La présente invention concerne un procédé pour l'extraction sélective d'éléments terres rares à partir d'un minerai ou d'un matériau concentré minéral contenant un ou plusieurs éléments dérivés de gisement, tels que le fer, l'aluminium, le zirconium et le niobium. Le procédé comprend les étapes de (i) préparation d'un concentré minéral au moyen d'un ou plusieurs procédés d'enrichissement pour réduire la quantité de minerai traité et de maximiser de façon économique la récupération d'éléments terres rares; ii) mélange d'acide sulfurique concentré en une quantité super-stœchiométrique par rapport au concentré minéral pour produire un aggloméré ou un mélange de poudre homogène; (iii) chauffage dudit mélange pour favoriser la sulfatation des métaux terres rares et non-terre rare dans une première cuve thermique; (iv) augmentation de la température pour décomposer sélectivement les sulfates de métal non-terre rare dans une deuxième cuve thermique; (v) lixiviation du matériau formé dans (iv) pour produire une solution de lixiviation contenant les éléments terres rares, qui est sensiblement exempte des éléments de gisement.
PCT/CA2016/051489 2015-12-16 2016-12-16 Procédé de traitement de minerai de terre rare par mélange d'acide, sulfatage et décomposition WO2017100933A1 (fr)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109013048A (zh) * 2018-09-25 2018-12-18 李梅 一种提高锆精矿品位同时得到稀土富集物的选矿方法
CN109022838A (zh) * 2018-09-14 2018-12-18 包头稀土研究院 含氟的稀土矿物颗粒的处理方法
WO2019210368A1 (fr) * 2018-05-03 2019-11-07 Arafura Resources Limited Processus de récupération de terres rares
CN111285332A (zh) * 2020-02-19 2020-06-16 包头稀土研究院 分解含氟稀土矿物和回收氢氟酸的一体化方法
CN111871594A (zh) * 2020-06-30 2020-11-03 中国地质科学院矿产综合利用研究所 一种从钒钛磁铁矿中回收磷和稀土的选矿工艺
WO2020257849A1 (fr) * 2019-06-25 2020-12-30 Australian Nuclear Science And Technology Organisation Procédé de récupération de terres rares
CN115725868A (zh) * 2022-11-23 2023-03-03 包头华美稀土高科有限公司 热浸槽、提高高温焙烧稀土浸出率的装置及方法
AU2021266303A1 (en) * 2021-08-25 2023-03-16 Australian Nuclear Science And Technology Organisation Processing of mineral sand particulates
AU2021266305A1 (en) * 2021-08-25 2023-03-16 Australian Nuclear Science And Technology Organisation Mineral sand particulate processing
WO2024089526A1 (fr) * 2022-10-27 2024-05-02 The Warb Trust (No.1 Trust 13337/99) Procédé et installation pour la décomposition d'un minéral contenant des terres rares

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2469462A1 (fr) * 1979-11-09 1981-05-22 Rhone Poulenc Ind Procede de traitement d'un minerai complexe de titane, zirconium et terres rares
FR2826667A1 (fr) * 2001-06-29 2003-01-03 Rhodia Elect & Catalysis Procede de traitement d'un minerai de terres rares a teneur elevee en fer
CN102864319A (zh) * 2011-10-08 2013-01-09 中国恩菲工程技术有限公司 从氧化镍矿浸出稀土元素的方法
DE102014201939A1 (de) * 2014-02-04 2015-08-06 Siemens Aktiengesellschaft Verfahren und Einrichtung zum Auftrennen eines Gesteins in taubes Gestein und mindestens ein Wertgestein
JP2015187291A (ja) * 2014-03-26 2015-10-29 三菱マテリアル株式会社 希土類元素の回収方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2469462A1 (fr) * 1979-11-09 1981-05-22 Rhone Poulenc Ind Procede de traitement d'un minerai complexe de titane, zirconium et terres rares
FR2826667A1 (fr) * 2001-06-29 2003-01-03 Rhodia Elect & Catalysis Procede de traitement d'un minerai de terres rares a teneur elevee en fer
CN102864319A (zh) * 2011-10-08 2013-01-09 中国恩菲工程技术有限公司 从氧化镍矿浸出稀土元素的方法
DE102014201939A1 (de) * 2014-02-04 2015-08-06 Siemens Aktiengesellschaft Verfahren und Einrichtung zum Auftrennen eines Gesteins in taubes Gestein und mindestens ein Wertgestein
JP2015187291A (ja) * 2014-03-26 2015-10-29 三菱マテリアル株式会社 希土類元素の回収方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BORRA, C.R. ET AL.: "Selective recovery of rare earths from bauxite residue by combination of sulfation, roasting and leaching.", MINERALS ENGINEERING, vol. 92, 2016, pages 151 - 159, XP029520878 *

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021529263A (ja) * 2018-05-03 2021-10-28 アラフラ・リソーシズ・リミテッドＡｒａｆｕｒａ Ｒｅｓｏｕｒｃｅｓ Ｌｔｄ 希土類の回収のための方法
JP7313430B2 (ja) 2018-05-03 2023-07-24 アラフラ・リソーシズ・リミテッド 希土類の回収のための方法
WO2019210368A1 (fr) * 2018-05-03 2019-11-07 Arafura Resources Limited Processus de récupération de terres rares
AU2019262097B2 (en) * 2018-05-03 2023-12-14 Arafura Resources Limited Process for the recovery of rare earths
US11858824B2 (en) 2018-05-03 2024-01-02 Arafura Resources Limited Process for the recovery of rare earths
CN109022838B (zh) * 2018-09-14 2020-03-06 包头稀土研究院 含氟的稀土矿物颗粒的处理方法
WO2020052311A1 (fr) * 2018-09-14 2020-03-19 包头稀土研究院 Procédé de traitement de particules minérales de terres rares contenant du fluor
CN109022838A (zh) * 2018-09-14 2018-12-18 包头稀土研究院 含氟的稀土矿物颗粒的处理方法
CN109013048A (zh) * 2018-09-25 2018-12-18 李梅 一种提高锆精矿品位同时得到稀土富集物的选矿方法
WO2020257849A1 (fr) * 2019-06-25 2020-12-30 Australian Nuclear Science And Technology Organisation Procédé de récupération de terres rares
CN111285332A (zh) * 2020-02-19 2020-06-16 包头稀土研究院 分解含氟稀土矿物和回收氢氟酸的一体化方法
CN111285332B (zh) * 2020-02-19 2023-03-28 包头稀土研究院 分解含氟稀土矿物和回收氢氟酸的一体化方法
CN111871594A (zh) * 2020-06-30 2020-11-03 中国地质科学院矿产综合利用研究所 一种从钒钛磁铁矿中回收磷和稀土的选矿工艺
AU2021266303A1 (en) * 2021-08-25 2023-03-16 Australian Nuclear Science And Technology Organisation Processing of mineral sand particulates
AU2021221764A1 (en) * 2021-08-25 2023-03-16 Australian Nuclear Science And Technology Organisation Processing of mineral sand particulates
AU2021107678B4 (en) * 2021-08-25 2023-11-30 Australian Nuclear Science And Technology Organisation Processing of mineral sand particulates
AU2021266305A1 (en) * 2021-08-25 2023-03-16 Australian Nuclear Science And Technology Organisation Mineral sand particulate processing
AU2021266305A2 (en) * 2021-08-25 2023-12-21 Australian Nuclear Science And Technology Organisation Mineral sand particulate processing
AU2021221764B2 (en) * 2021-08-25 2024-02-08 Australian Nuclear Science And Technology Organisation Processing of mineral sand particulates
WO2024089526A1 (fr) * 2022-10-27 2024-05-02 The Warb Trust (No.1 Trust 13337/99) Procédé et installation pour la décomposition d'un minéral contenant des terres rares
CN115725868A (zh) * 2022-11-23 2023-03-03 包头华美稀土高科有限公司 热浸槽、提高高温焙烧稀土浸出率的装置及方法

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