[go: up one dir, main page]

WO2012065253A1 - Procédé d'extraction d'aluminium à partir de minerais alumineux - Google Patents

Procédé d'extraction d'aluminium à partir de minerais alumineux Download PDF

Info

Publication number
WO2012065253A1
WO2012065253A1 PCT/CA2011/001271 CA2011001271W WO2012065253A1 WO 2012065253 A1 WO2012065253 A1 WO 2012065253A1 CA 2011001271 W CA2011001271 W CA 2011001271W WO 2012065253 A1 WO2012065253 A1 WO 2012065253A1
Authority
WO
WIPO (PCT)
Prior art keywords
ions
iron
composition
aluminum
base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CA2011/001271
Other languages
English (en)
Inventor
Richard Boudreault
Fabienne Biasotto
Joel Fournier
Serge Alex
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Orbite Technologies Inc
Original Assignee
Orbite Aluminae Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Orbite Aluminae Inc filed Critical Orbite Aluminae Inc
Priority to EP11841479.6A priority Critical patent/EP2640862A4/fr
Priority to US13/885,922 priority patent/US20130233130A1/en
Priority to AU2011331861A priority patent/AU2011331861A1/en
Priority to CA2812309A priority patent/CA2812309C/fr
Publication of WO2012065253A1 publication Critical patent/WO2012065253A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
    • 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
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • 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
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • 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
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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 disclosure relates to improvements in the field of chemistry applied to extraction of aluminum from aluminous ores.
  • processes are useful for extracting aluminum from aluminous ores comprising various types of metals such as Fe, K, Mg, Na, Ca, Mn, Ba, Zn, Li, Sr, V, Ni, Cr, Pb, Cu, Co, Sb, As, B, Sn, Be, Mo, or mixtures thereof.
  • alumina More than 96 % of the alumina which is produced worldwide is obtained from bauxite, which is a mineral that is particularly rich in alumina (40 - 60 %) and whose main suppliers are from Jamaica, Australia, Brazil, Africa and Russia.
  • aluminous ores which are aluminosilicates (for example argillite, nepheline, etc.) that are relatively rich in alumina (20 - 28 %).
  • aluminous ores which are aluminosilicates (for example argillite, nepheline, etc.) that are relatively rich in alumina (20 - 28 %).
  • aluminum oxide is associated with silicated or sulfated phases.
  • a process for extracting aluminum ions from argillite comprising : leaching the argilite with HCI; at least partially removing iron from the argillite by substantially selectively precipitating at least a portion of the iron ions by reacting the iron ions with a base so as to obtain an Al-rich composition or by substantially complexing the iron ions with an extracting agent; and optionally purifying said Al-rich composition by : substantially selectively precipitating said aluminum ions;
  • a process for extracting aluminum ions from argillite comprising : leaching the argillite with HCI so as to obtain a composition comprising the aluminum ions and iron ions; at least partially removing the iron ions from the composition by substantially selectively precipitating at least a portion of the iron ions by reacting the composition with a base and at least partially removing the precipitated iron ions so as to obtain an Al-rich composition; and optionally purifying said Al-rich composition by :
  • a process for extracting aluminum ions from an aluminous ore comprising : leaching the aluminous ore with HCI; at least partially removing iron from the aluminous ore by substantially selectively precipitating at least a portion of the iron ions by reacting the iron ions with a base so as to obtain an Al-rich composition or by substantially complexing the iron ions with an extracting agent; and optionally purifying said Al-rich composition by :
  • a process for extracting aluminum ions from an aluminous ore comprising : leaching the aluminous ore with an acid so as to obtain a composition comprising the aluminum ions and iron ions; at least partially removing the iron ions from the composition by substantially selectively precipitating at least a portion of the iron ions by reacting the composition with a base and at least partially removing the precipitated iron ions so as to obtain an Al-rich composition; and optionally purifying said Al-rich composition by :
  • a process for extracting aluminum ions from a mixture comprising iron ions and the aluminum ions comprises recovering the aluminum ions from a composition comprising the aluminum ions, the iron ions, an organic solvent and an extracting agent adapted to form an organometallic complex substantially selectively with the iron ions or with the aluminum ions which is soluble in the organic solvent.
  • Fig. 1 shows a bloc diagram of a process according to one embodiment of a process for extracting aluminum from an aluminous ore.
  • the acid used for leaching the aluminous ore can be HCI, H 2 S0 4 , HN0 3 or mixtures thereof. More than one acid can be used as a mixture or separately. Solutions made with these acids can be used at various concentration. For example, concentrated solutions can be used. For example, 6 M or 12 M HCI can be used. For example, up to 100 % wt H 2 S0 4 can be used. [0012]
  • the processes of the present disclosure can be effective for treating various aluminous ores or aluminum-bearing ores. For example, clays, argillite, mudstone, beryl, cryolite, garnet, spinel, bauxite, or mixtures thereof can be used as starting material.
  • the leaching can be carried out under pressure into an autoclave. For example, it can be carried out at a pressure of about 5 KPa to about 850 KPa, about 50 KPa to about 800 KPa, about 100 KPa to about 750 KPa, about 150 KPa to about 700 KPa, about 200 KPa to about 600 KPa, or about 250 KPa to about 500 KPa.
  • the leaching can be carried out at a temperature of at least 80 °C, at least 90 °C, or about 100 °C to about 1 0 °C. In certain cases, it can be done at higher temperatures.
  • the leaching can also be carried out under pressure.
  • the pressure can be about 100 to about 300 or about 150 to about 200 psig.
  • the leaching can be carried out for about 30 minutes to about 5 hours. It can be carried out at a temperature of about 60 °C to about 200 °C.
  • the process can comprise: leaching the argillite with HCI so as to obtain a leachate comprising the aluminum ions and the iron ions, and a solid residue; separating the leachate from the solid residue; at least partially removing the iron ions from the leachate by substantially selectively precipitating at least a portion of the iron ions by reacting the base with the leachate and removing a so-formed precipitate, so as to obtain an Al-rich aqueous composition; and purifying the Al-rich aqueous composition by substantially selectively precipitating the aluminum ions by reacting the composition with an acid or base, and by recovering the precipitated aluminum ions.
  • the process can comprise: leaching the argillite with HCI so as to obtain a leachate comprising the aluminum ions and the iron ions, and a solid residue; separating the leachate from the solid residue; at least partially removing the iron ions from the leachate by substantially selectively precipitating at least a portion of the iron ions by reacting the base with the leachate and removing a so-formed precipitate, so as to obtain the Al-rich aqueous composition; and purifying the Al-rich aqueous composition by means of a hollow fiber membrane membrane, or by a liquid-liquid extraction.
  • the process can comprise: leaching the argillite with HCI so as to obtain a leachate comprising the aluminum ions and the iron ions, and a solid residue; separating the leachate from the solid residue; at least partially removing the iron ions from the leachate by substantially selectively precipitating at least a portion of the iron ions by reacting the base with the leachate and removing a so-formed precipitate, so as to obtain the Al-rich aqueous composition; and purifying the Al-rich aqueous composition by substantially selectively precipitating the aluminum ions and recovering the precipitated aluminum ions.
  • the Al-rich aqueous composition can be purified by complexing the aluminum ions with an extracting agent so as to obtain a complex, separating the complex form the composition and precipitating the aluminum ions.
  • the extracting agent can be bis(2,4,4- trimethylpentyl) phosphinic acid.
  • the Al-rich aqueous composition can be purified by complexing impurities contained in Al-rich aqueous composition with an extracting agent, at least partially removing the complexed impurities from the composition and precipitating the aluminum ions.
  • the extracting agent can be chosen from di-2-ethylhexyl phosphoric acid (HDEHP), bis(2,4,4-trimethylpentyl) phosphinic acid and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester.
  • HDEHP di-2-ethylhexyl phosphoric acid
  • bis(2,4,4-trimethylpentyl) phosphinic acid 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester.
  • the base that can be used for substantially selectively precipitating the iron ions can be KOH, NaOH, or a mixture thereof.
  • the base that can be used for substantially selectively precipitating the aluminum ions can be KOH, NaOH, or a mixture thereof.
  • the precipitation of iron ions can be carried out at a pH of about 3 to about 6, about 3.0 to about 5.5, about 3 to about 5, about 3 to about 4, about 3.0 to about 3.5, about 3.5 to about 4.0, about 4.0 to about 5.0, about 4.0 to about 4.5, or about 4.5 to about 5.0.
  • the Al-rich composition can be purified by reacting the Al-rich composition with a base for substantially selectively precipitating the aluminum ions at a pH of about 5 to about 6, about 5.0 to about 5.5, or about 5.5 to about 6.0.
  • a process for producing alumina comprising : obtaining aluminum ions by means of a process as defined in the present disclosure; and converting the aluminum ions into alumina.
  • tha aluminum ions can be converted into alumina by heating AI(OH) 3 at a temperature of about 800 °C to about 1200 °C.
  • a process for producing alumina comprising : converting the alumina into aluminum.
  • a process for producing aluminum comprising : obtaining alumina by means of a process as defined in the present disclosure; and converting the alumina into aluminum.
  • a process for extracting aluminum from an aluminous ore comprising: leaching the aluminous ore with an acid so as to obtain a leachate and a solid residue; removing at least a portion of iron ions contained in the leachate by:
  • the acid can be HCI.
  • the aluminuous ore can be leached with HCI at a temperature of at least 80 °C, at least 90 °C, or about 100 °C to about 1 10 °C.
  • HCI can have a concentration of about 6 M.
  • the alunimuous ore / acid ratio can be about 1 / 10 in weight by volume.
  • the removal of the at least portion of iron ions can be carried out by precipitating the iron ions from a basic aqueous composition.
  • the composition can comprise comprising NaOH or KOH.
  • the removal of the at least portion of iron ions can be carried out by reacting the leachate with a base in order to obtain a pH of at least 10 and precipitating the iron ions.
  • the precipitated iron ions can be separated from the rest of the leachate by carrying out a filtration, a decantation, a centrifugation, or mixtures thereof.
  • the processes can further comprise rinsing the obtained precipitated iron ions with a basic solution.
  • the basic solution can have a concentration of about 0.01 M to about 0.02 M.
  • the pH can be at least 1 1 , at least 12, about 10.8 to about 1 1.2, or about 11.5 to about 12.5.
  • the process can further comprise purifying the precipitated iron ions by means of a hollow fiber membrane.
  • the removal of the at least portion of iron ions can be carried out by reacting the leachate, under acidic conditions, with the extracting agent and an organic solvent in order to obtain a composition comprising an acidic aqueous phase comprising aluminum ions and an organic phase comprising iron ions complexed with the extracting agent.
  • the aluminum enriched composition can be obtained by separating the aqueous phase from the organic phase.
  • the aqueous phase can have a pH of about 1 to about 2.5, or about 2.
  • the extracting agent can be chosen from di-2-ethylhexyl phosphoric acid (HDEHP), bis(2,4,4-trimethylpentyl) phosphinic acid and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester).
  • the extracting agent can have a concentration of about 0.5 M to about 1.5 M in the organic phase or about 1 M in the organic phase.
  • the organic solvent can be chosen from C 5 -C 12 alkanes and mixtures thereof.
  • the organic solvent can be heptane.
  • the composition can have a volumic ratio organic phase : aqueous phase of about 1 :1.
  • the organic phase and the aqueous phase can be separated by means of a filtration membrane.
  • the membrane can be a hollow fiber membrane.
  • the membrane can comprise polypropylene, polyvinylidene difluoride, or a mixture thereof.
  • the aqueous phase can separated from the organic phase.
  • the aluminum ions can be recovered in the aqueous phase and the aqueous phase is treated with a base (such as NaOH or KOH).
  • the aqueous phase can be treated with the base so as to obtain a pH of at least about 4.
  • the process can further comprise a separation by filtration to obtain AI(OH)3, which can be eventually washed.
  • the aluminous ore can be crushed and roasted before being leached.
  • the leachate is treated with a base.
  • the leachate before removal of the iron ions, the leachate can be distilled so as to reduce its volume.
  • the process can further comprise at least partially recovering the aluminum ions present in the aluminum enriched composition.
  • the aluminum enriched composition can be treated with an extracting agent adapted to form an organometallic complex substantially selectively with the aluminum ions in the presence of an organic solvent and an acid solution in order to form a composition comprising an acidic aqueous phase comprising impurities and an organic phase comprising aluminum ions complexed with the extracting agent.
  • the aluminum ions can be recovered by separating the aqueous phase from the organic phase.
  • the aqueous phase can have a pH of about 2.5 to about 3.5.
  • the extracting agent can be a phosphinic acid or a derivative thereof.
  • the extracting agent can be bis(2,4,4-trimethylpentyl) phosphinic acid.
  • the extracting agent can have a concentration of about 10 % to about 25 % v/v or about 20 % v/v with respect to the organic solvent.
  • the organic solvent can be chosen from C5-C12 alkanes and mixtures thereof.
  • the organic solvent can be heptane.
  • the composition can have a volumic ratio aqueous phase : organic phase of about 1 :1 to about 1 :3.
  • the organic phase and the aqueous phase can be separated by means of a membrane (for example a hollow fiber membrane).
  • the membrane can comprise polypropylene, polyvinylidene difluoride, or a mixture thereof.
  • the composition can be at a temperature of about 30 °C to about 50 °C, or about 35 °C to about 45 °C.
  • the aqueous phase can be separated from the organic phase.
  • the complexed aluminum ions can be recovered in the organic phase.
  • the organic phase can then be treated with HCI so as to obtain an aqueous composition comprising the aluminum ions.
  • the aluminum ions can be converted into AI(OH)3 by contacting it with a base.
  • AI(OH) 3 can then be converted into Al 2 0 3 .
  • Such a conversion of AI(OH)3 into Al 2 0 3 can be carried out at a temperature of about 800 °C to about 1200 °C.
  • the composition can comprise an acidic aqueous phase comprising aluminum ions and an organic phase comprising iron ions complexed with the extracting agent and wherein the aluminum ions are recovered by separating the aqueous phase from the organic phase.
  • the aqueous phase can have a pH of about 1 to about 2.5 or of about 2.
  • the extracting agent can be chosen from phosphoric acids and derivatives thereof, and phosphinic acids and derivatives thereof.
  • the extracting agent can be chosen from di-2-ethylhexyl phosphoric acid (HDEHP), bis(2,4,4-trimethylpentyl) phosphinic acid and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester.
  • the extracting agent can have a concentration of about 0.5 M to about 1.5 M in the organic phase or of about 1 M in the organic phase.
  • the composition can have a volumic ratio organic phase : aqueous phase of about 1 : 1.
  • the aqueous phase can be separated from the organic phase, and the aluminum ions can recovered in the aqueous phase and the aqueous phase can be treated with a base (for example NaOH, KOH, or a mixture thereof).
  • the aqueous phase can be treated with the base so as to obtain a pH of at least about 4.
  • the process can further comprise treating the organic phase with HCI and isolating the iron ions in the form of Fe 3+ .
  • the composition can comprise an acidic aqueous phase comprising iron ions and an organic phase comprising aluminum ions complexed with the extracting agent, and wherein the aluminum ions are recovered by separating the aqueous phase from the organic phase.
  • the aqueous phase can have a pH of about 2.5 to about 3.5.
  • the extracting agent can be a phosphinic acid or a derivative thereof.
  • the extracting agent can be bis(2,4,4-trimethylpentyl) phosphinic acid.
  • the extracting agent can have a concentration of about 10 % to about 25 % v/v with respect to the organic solvent or of about 20 % v/v with respect to the organic solvent.
  • the composition can have a volumic ratio aqueous phase : organic phase of about 1 : 1 to about 1 :3.
  • the composition can be at a temperature of about 30 °C to about 50 °C or at a temperature of about 35 °C to about 45 °C.
  • the aqueous phase can be separated from the organic phase.
  • the complexed aluminum ions can be recovered in the organic phase.
  • the organic phase can then be treated with HCI so as to obtain an aqueous composition comprising the aluminum ions.
  • the organic solvent can be chosen from hydrocarbons.
  • the organic solvent can be chosen from C5-C12 alkanes and mixtures thereof.
  • the organic solvent can also be hexane or heptane.
  • the organic phase and the aqueous phase can be separated by means of a filtration membrane, for example a hollow fiber membrane.
  • a filtration membrane for example a hollow fiber membrane.
  • Such membrane can comprise polypropylene, polyvinylidene difluoride, or a mixture thereof.
  • the aqueous phase can be treated with the base so as to obtain a pH of at least about 4.
  • the process can also further comprise a separation by filtration so as to obtain AI(OH) 3 .
  • the process can also comprise washing the AI(OH) 3 .
  • the process can also comprise converting AI(OH) 3 into Al 2 0 3 . Conversion of AI(OH) 3 into Al 2 0 3 can be carried out at a temperature of about 800 °C to about 1200 °C.
  • composition comprising aluminum ions, iron ions, an organic solvent and an extracting agent adapted to form an organometallic complex substantially selectively with the iron ions or with the aluminum ions which is soluble in the organic solvent.
  • composition comprising an acidic aqueous phase comprising aluminum ions and an organic phase comprising iron ions complexed with an extracting agent.
  • composition comprising an acidic aqueous phase comprising iron ions and an organic phase comprising aluminum ions complexed with an extracting agent.
  • a process for at least partially separating aluminum ions from iron ions comprised in a composition comprising substantially selectively precipitating at least a portion of the iron ions in basic conditions in which the pH is of at least 10.
  • the iron ions can be precipitated from a basic aqueous composition comprising NaOH or KOH.
  • the base can be reacted with the composition so as to obtain a mixture in which the pH is of at least 10, and then, the at least portion of precipitated iron ions can be separated from the rest of the mixture.
  • the precipitated iron ions can be separated from the rest of the mixture by carrying out a filtration, a decantation, a centrifugation, or combinations thereof.
  • the process can further comprise rinsing the obtained precipitated iron ions with a basic solution.
  • the basic solution can have a concentration of about 0.01 M to about 0.02 M.
  • the pH can be at least 1 1 , at least 12, about 10.8 to about 1 1.2, or about 11.5 to about 12.5.
  • the process can further comprise purifying the precipitated iron ions by means of a hollow fiber membrane.
  • such a process can comprise various steps, and each of these steps can eventually be individually considered has being a process.
  • Argillite can be finely crushed in order to help along during the following steps. For example, micronization can shorten the reaction time by few hours (about 2 to 3 hours).
  • a leaching step at room temperature is optionally carried out between the crushing step and the roasting step (see option 1 ). This operation is, for ex ample, carried out with hydrochloric acid HCI (12 M) and an argillite / acid ratio (weight / volume) of 1 :5 is used. Depending on experimental conditions (sizes of the particles, time of treatment, agitation system), about 65 % to about 93 % of the iron can then be removed. However, this leaching step can also bring in a certain percentage of the aluminum (0 - 5 %).
  • the last step of the preparation of argillite comprises roasting the pretreated argillite. This can be accomplished at a temperature greater than 550 °C for a period of about 1 to 2 hours. For example, a heat treatment makes it possible to increase the quantity of extracted aluminum by about 30 % to about 40 % for the same period of time. In others words, the quantity of extracted aluminum is doubled.
  • a phase separation before roasting can be made in order to recover the acid and reduce heating costs. Acid leaching
  • Acid leaching comprises reacting the crushed and roasted argillite with a hydrochloric acid solution at elevated temperature during a given period of time.
  • the argillite / acid ratio can be of about of 1 :10 (weight / volume)
  • the HCI concentration can be of about 6
  • the temperature can be of about 100 °C to about 10 °C
  • the reaction time can be of about 5 to about 7 hours. Under such conditions, more than about 90 % of the aluminum and about 100 % of the iron can be extracted in addition to impurities.
  • a portion of the acid can be recovered by condensation.
  • the solid argillite impoverished in metals
  • the solid can be separated from the liquid by decantation or by filtration, after which it is washed.
  • the residual leachate and the washing water may be completely evaporated.
  • the corresponding residue can thereafter be washed many times with water so as to decrease acidity and to lower the quantities of sodium hydroxide (NaOH) that are required to adjust the pH during iron removal.
  • Final volume accounts for 10 % to 20 % of initial volume.
  • the acid recovered will can be re-utilized after having adjusted its titer either by adding gaseous HCI, or by adding concentrated HCI (12 M).
  • the titer of the acid can vary from about 4 M to about 6 M depending on experimental conditions. With respect to the solid, it represents about 65 % to about 75 % of the initial mass of argillite, it can be valorized and be used again either as an ion exchange resin, or as an adsorbent.
  • Removal of iron can be carried out by precipitation of the iron ions in (i) basic medium or ( ⁇ ) an acidic medium.
  • a basic medium precipitation can be carried out at a pH of at least 10 or at a pH of about 11.5 to about 12.5.
  • the precipitation in an acidic medium, can be carried out at a pH of about 3 to about 6, about 3 to about 5, about 3 to about 4, about 3.0 to about 3.5, about 3.5 to about 4.0, about 4.0 to about 5.0, about 4.0 to about 4.5, or about 4.5 to about 5.0, by adding the base.
  • Such a step under basic or acidic conditions can be made by adding NaOH or KOH for example at a concentration of about 0.1 M to about 18 M.
  • a concentration of 0.1 M, 1 M, 6 M or 10 M can be used. Then, all that is required is to separate the solid portion from the liquid portion by filtration, decantation or centrifugation and to rinse the solid by means of a diluted base, such as a solution of NaOH (for example NaOH at a concentration of 0.01 M to 0.02 M). Then, the solid is washed with distilled water.
  • the liquid portion comprises aluminum and alkaline-earths A substantially complete removal of the iron and of nearly all the impurities (other metals) can thus be achieved.
  • it is possible to recover iron by using a refining step by liquid-liquid extraction through a hollow fiber membrane (see option 2).
  • removal of iron can be carried out by using an extracting agent and a hollow fiber membrane.
  • Various extracting agents that could substantially selectively complex iron ions over aluminum ions (or aluminum ions over iron ions) could be used in such a step depending an Al / Fe ratio.
  • extraction can be carried out by using HDEHP (diethylhexylphosphoric acid) as an extracting agent adapted to complex iron ions.
  • a concentration of about 1 M of HDEHP can be used in an organic solvent, such as heptane or any hydrocarbon solvent.
  • Such an extraction can require relatively short contact times (few minutes).
  • the pH of the order of 2 can be used and aqueous phase / organic phase ratio can be of about 1 :1.
  • the solution obtained from the previous step using either the precipitation or the extraction technique is relatively clean and mainly contains aluminum for example about 90 % to 95 % (without the alkaline-earths in the case of precipitation).
  • Recovery of the latter can be carried out by liquid-liquid extraction for example by using a same hollow fiber membrane and an extracting agent that is adapted to complex at least substantially selectively aluminum over other metals or residues.
  • bis(2,4,4-trimethylpentyl) phosphinic acid can be used as an extracting agent specific to aluminum.
  • this extracting agent can be used at a concentration of about 20 % v/v in an organic solvent such as heptane.
  • the ratios between the aqueous phase and the organic phase can be of about 1 :1 to about 1 :3.
  • the extraction temperatures can be of about 40 °C and the pH can be maintained at about 2.5 to about 3.5. It was observed that such a technique makes it possible to extract more than 70 - 90 % of the aluminum.
  • the aluminum After the aluminum has been trapped in the organic phase, it can berecovered in the form of a concentrate of Al 3+ ions by using a back extraction.
  • the reverse extraction can be carried out at a temperature of about 40 °C with hydrochloric acid (for example at a concentration of 6 M). Under this condition, more than 90 % of aluminum can be recovered.
  • Al 3+ can be converted into aluminum hydroxide AI(OH)3 by addition of NaOH.
  • AI(OH) 3 can be converted into alumina (alumina Al 2 0 3 ) by roasting AI(OH) 3 for example at a temperature of about 800 °C to1200 °C.
  • the residual volume was slightly diluted (+ 25 %) and concentrated hydroxide sodium (10 M) was added until a pH higher than 11.5 was reached.
  • the formed precipitate was separated from the solution by standard filtration and was washed several times with NaOH dilued and hot ultra-pure water.
  • the precipitate contained all the iron and the majority of the metal impurities.
  • the filtrate contained in addition to ions Al 3+ mainly alkaline-earths and some following impurities:
  • the filtrate is adjusted at a pH of 2.5 to 3.5 by addition of HCI 6 M.
  • the resulting solution is extracted by means of the complexing agent, Cyanex 272, at a concentration of 20 % volume / volume in an organic solvent with a volumetric ratio of 1 :1.
  • the extraction is carried out at a temperature of 40 °C in a membrane contactor with hollow fibers. In less than about 30 to 60 min, more than 85 % of aluminum is extracted.
  • the pH adjustment is performed by a regulation loop controling the NaOH (10 M) addition.
  • Complexed Al 3+ in Cyanex are then recovered by carrying out a back extraction with HCI (6 M) at 40 °C and an organic phase / acid phase volumetric ratio of 1:0.5. After the back extraction, the composition of the recovered acid phase is :

Landscapes

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

Abstract

La présente invention se rapporte à un procédé d'extraction d'ions d'aluminium à partir de minerais alumineux, tel que de l'argilite. Le procédé consiste à lixivier l'argilite avec un acide tel que le HCl de sorte à obtenir une composition comprenant des ions d'aluminium et des ions de fer; à éliminer au moins partiellement les ions de fer de la composition par précipitation sensiblement sélective des ions de fer à un pH d'environ 3 à environ 6 par ajout d'une base et par élimination au moins partielle des ions de fer précipités de sorte à obtenir une composition riche en Al; et, éventuellement, à purifier la composition riche en Al par ajout d'une base afin de précipiter de manière sensiblement sélective les ions d'aluminium au moyen d'une membrane en fibre creuse ou par extraction liquide-liquide.
PCT/CA2011/001271 2010-11-19 2011-11-18 Procédé d'extraction d'aluminium à partir de minerais alumineux Ceased WO2012065253A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP11841479.6A EP2640862A4 (fr) 2010-11-19 2011-11-18 Procédé d'extraction d'aluminium à partir de minerais alumineux
US13/885,922 US20130233130A1 (en) 2010-11-19 2011-11-18 Process for extracting aluminum from aluminous ores
AU2011331861A AU2011331861A1 (en) 2010-11-19 2011-11-18 Process for extracting aluminum from aluminous ores
CA2812309A CA2812309C (fr) 2010-11-19 2011-11-18 Procede d'extraction d'aluminium a partir de minerais alumineux

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41547310P 2010-11-19 2010-11-19
US61/415,473 2010-11-19

Publications (1)

Publication Number Publication Date
WO2012065253A1 true WO2012065253A1 (fr) 2012-05-24

Family

ID=46083447

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2011/001271 Ceased WO2012065253A1 (fr) 2010-11-19 2011-11-18 Procédé d'extraction d'aluminium à partir de minerais alumineux

Country Status (5)

Country Link
US (1) US20130233130A1 (fr)
EP (1) EP2640862A4 (fr)
AU (1) AU2011331861A1 (fr)
CA (1) CA2812309C (fr)
WO (1) WO2012065253A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023279151A1 (fr) * 2021-07-05 2023-01-12 HiPurA Pty Ltd Procédé de production de matériaux d'aluminium de haute pureté

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2588960C2 (ru) 2011-03-18 2016-07-10 Орбит Элюминэ Инк. Способы извлечения редкоземельных элементов из алюминийсодержащих материалов
EP2705169A4 (fr) 2011-05-04 2015-04-15 Orbite Aluminae Inc Procédés d'extraction d'éléments de terres rares dans divers minerais
CA2848751C (fr) 2011-09-16 2020-04-21 Orbite Aluminae Inc. Procedes de preparation d'alumine et de divers autres produits
RU2016104423A (ru) 2012-01-10 2018-11-22 Орбит Текнолоджис Инк. Способы обработки красного шлама
AU2013203808B2 (en) 2012-03-29 2016-07-28 Aem Technologies Inc. Processes for treating fly ashes
WO2014047728A1 (fr) 2012-09-26 2014-04-03 Orbite Aluminae Inc. Procédés pour la préparation d'alumine et de chlorure de magnésium par lixiviation par hcl de divers matériaux
CN105189357A (zh) 2012-11-14 2015-12-23 奥佰特氧化铝有限公司 纯化铝离子的方法
WO2019222602A1 (fr) 2018-05-18 2019-11-21 California Institute Of Technology Procédé de conversion d'espèces de soufre réduit et d'eau en hydrogène et en acide sulfurique
KR20220058908A (ko) 2019-08-13 2022-05-10 캘리포니아 인스티튜트 오브 테크놀로지 칼슘 보유 암석 및 광물로부터 칼슘 산화물 또는 일반 포틀랜드 시멘트를 제조하는 방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1956139A (en) * 1930-07-26 1934-04-24 Alterra A G Process for treating argillaceous material
US2489309A (en) * 1946-04-30 1949-11-29 Houdry Process Corp Preparation of an iron-freed acid treated kaolin catalyst
US3966909A (en) * 1974-02-20 1976-06-29 The Anaconda Company Solvent extraction of aluminum
US6468483B2 (en) * 2000-02-04 2002-10-22 Goldendale Aluminum Company Process for treating alumina-bearing ores to recover metal values therefrom
WO2008141423A1 (fr) * 2007-05-21 2008-11-27 Exploration Orbite Vspa Inc. Procédés d'extraction de l'aluminium et du fer à partir de minerais alumineux

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB120035A (en) * 1917-09-25 1919-03-06 Norsk Hydro Elektrisk Improvements in the Production of Alumina Nitrates from Clay, Argillite and similar Minerials.
CN101823742B (zh) * 2010-05-14 2012-05-23 东北大学 一种铝土矿酸法生产氧化铝的方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1956139A (en) * 1930-07-26 1934-04-24 Alterra A G Process for treating argillaceous material
US2489309A (en) * 1946-04-30 1949-11-29 Houdry Process Corp Preparation of an iron-freed acid treated kaolin catalyst
US3966909A (en) * 1974-02-20 1976-06-29 The Anaconda Company Solvent extraction of aluminum
US6468483B2 (en) * 2000-02-04 2002-10-22 Goldendale Aluminum Company Process for treating alumina-bearing ores to recover metal values therefrom
WO2008141423A1 (fr) * 2007-05-21 2008-11-27 Exploration Orbite Vspa Inc. Procédés d'extraction de l'aluminium et du fer à partir de minerais alumineux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2640862A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023279151A1 (fr) * 2021-07-05 2023-01-12 HiPurA Pty Ltd Procédé de production de matériaux d'aluminium de haute pureté
AU2022306695A1 (en) * 2021-07-05 2023-08-24 HiPurA Pty Ltd "process for producing high purity aluminium materials"
AU2022306695B2 (en) * 2021-07-05 2023-10-05 HiPurA Pty Ltd "process for producing high purity aluminium materials"
KR20240031341A (ko) * 2021-07-05 2024-03-07 하이푸라 피티와이 엘티디 고순도 알루미늄 소재의 생산 공정
JP2024525304A (ja) * 2021-07-05 2024-07-12 ハイピュラ・プロプリエータリ・リミテッド 高純度アルミニウム材料を生成するための方法
JP7591172B2 (ja) 2021-07-05 2024-11-27 ハイピュラ・プロプリエータリ・リミテッド 高純度アルミニウム材料を生成するための方法
KR102793410B1 (ko) 2021-07-05 2025-04-09 하이푸라 피티와이 엘티디 고순도 알루미늄 소재의 생산 공정

Also Published As

Publication number Publication date
EP2640862A1 (fr) 2013-09-25
US20130233130A1 (en) 2013-09-12
CA2812309C (fr) 2014-12-09
CA2812309A1 (fr) 2012-05-24
EP2640862A4 (fr) 2017-06-21
AU2011331861A1 (en) 2013-04-18

Similar Documents

Publication Publication Date Title
CA2684696C (fr) Procedes d'extraction de l'aluminium et du fer a partir de minerais alumineux
CA2812309C (fr) Procede d'extraction d'aluminium a partir de minerais alumineux
CA2711013C (fr) Procede d'extraction de l'aluminium des minerais alumineux
AU2012231686B2 (en) Processes for recovering rare earth elements from aluminum-bearing materials
AU2012250460B2 (en) Processes for recovering rare earth elements from various ores
AU2012100165A4 (en) Processes for extracting aluminum and iron from aluminous ores
HK1166355A (en) Processes for extracting aluminum and iron from aluminous ores
HK1147780B (en) Processes for extracting aluminum and iron from aluminous ores
WO2023279151A1 (fr) Procédé de production de matériaux d'aluminium de haute pureté

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11841479

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2812309

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2011331861

Country of ref document: AU

Date of ref document: 20111118

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 13885922

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2011841479

Country of ref document: EP