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WO2008036824A1 - Procédé et moyens d'utilisation de l'énergie micro-onde pour oxyder un minerai de cuivre sulfurique dans un produit oxyde - sulfate prescrit - Google Patents

Procédé et moyens d'utilisation de l'énergie micro-onde pour oxyder un minerai de cuivre sulfurique dans un produit oxyde - sulfate prescrit Download PDF

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Publication number
WO2008036824A1
WO2008036824A1 PCT/US2007/079045 US2007079045W WO2008036824A1 WO 2008036824 A1 WO2008036824 A1 WO 2008036824A1 US 2007079045 W US2007079045 W US 2007079045W WO 2008036824 A1 WO2008036824 A1 WO 2008036824A1
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Prior art keywords
selected metal
oxidized
sulfide sulfur
microwave energy
bed
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English (en)
Inventor
James Tranquilla
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HW ADVANCED TECHNOLOGIES Inc
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HW ADVANCED TECHNOLOGIES Inc
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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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C22B1/10—Roasting processes in fluidised form
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0002—Preliminary treatment
    • C22B15/001—Preliminary treatment with modification of the copper constituent
    • C22B15/0013—Preliminary treatment with modification of the copper constituent by 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • 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
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/22—Remelting metals with heating by wave energy or particle radiation
    • C22B9/221—Remelting metals with heating by wave energy or particle radiation by electromagnetic waves, e.g. by gas discharge lamps
    • C22B9/225—Remelting metals with heating by wave energy or particle radiation by electromagnetic waves, e.g. by gas discharge lamps by microwaves
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates generally to the recovery of selected transition metals from sulfidic materials and particularly to the recovery of base metals, particularly copper, from sulf ⁇ dic materials.
  • Chalcopyrite is a commonly occurring sulf ⁇ dic copper ore which must be oxidized to liberate the copper and make it amenable to conventional recovery techniques, which include smelting and solvent extraction (SX/EW). Due to the modest value of the finished copper metal, there is always a need for lower-cost methods of production. Coupled with this is the environmental concern over historical smelter operations, which has resulted in the recognition of SX/EW as the most environmentally attractive and economically viable method of treating sulfidic copper ores. However, for any of these processes to be economically successful, the ores must first be concentrated to increase the value per ton processed. Sulfide content may thus be increased many fold up to the order of 30% or greater to form a viable "smelter grade" concentrate.
  • chalcopyrite oxidizes according to the following reactions:
  • reaction (3) is actually an intermediate reaction which, upon further oxidation, produces CuO-Fe 2 O 3 which is an insoluble spinel product and is therefore undesirable. Since reaction (3) is only favored at temperatures greater than about 690 0 C, it is therefore necessary to restrict the operating temperature below this level to produce the desired oxide (CuO) and sulfate (CuSO 4 ) products.
  • a process which operates on the basis of reactions (1) and (2) is essentially a roasting operation with a calcine product which is amenable to SX/EW recovery. If the roaster operation is carried to higher temperatures sufficient to liquefy the products, the result is a smelter which produces a metallic matte containing relatively impure copper as well as other products. Refining of the copper matte is carried out by dissolving the matte and performing an electrowinning operation.
  • Kruesi (US Patent 4,324,582) discloses the microwave heating of copper ores and the formation of oxide and sulfate products. More specifically, his disclosure relates to a situation in which these products are produced separately under different operating conditions (different temperature regimes). As well, Kruesi does not disclose an applicator or device in which the microwave process can be practiced such that the process variables (temperature, feed rate, gas composition, gas/solids intermixing) can be controlled as in an industrial process. SUMMARY OF THE INVENTION
  • the present invention is directed generally to microwave-induced oxidation of selected metal sulfides to render the selected metal sulfides recoverable inexpensively by suitable selected metal recovery techniques.
  • a process for recovering a selected metal from a sulfidic material includes the steps:
  • the selected metal is preferably one or more of copper, nickel, cobalt, and manganese, with copper being more preferred.
  • the sulfide sulfur is oxidized to sulfates and/or sulfur dioxide, and the selected metal to selected metal sulfates or non-sulfur containing selected metal oxides, such as the compound XO, where X is the selected metal.
  • the ratio of selected (sulfur- free) metal oxides to selected metal sulfates in the removed oxidized selected metal-containing material preferably ranges from about 0.3:1 to about 8:1, and the removed oxidized material preferably has a sulfide sulfur content of no more than about 0.5 wt. %.
  • most of the selected metal in the removed oxidized material is in the form of a sulfate.
  • most of the selected metal in the oxidized material is in the form of XO, where X is the selected metal.
  • the sulfide sulfur content of the sulfidic material, before oxidation is at least about 7 wt. %.
  • the sulfide sulfur concentration of the sulfidic material, before oxidation is no more than about 6 wt. %.
  • a maximum temperature of the bed of sulfidic material and of the selected metal sulfides, during microwave irradiation and fluidization is no more than about 690 0 C. Below this temperature selected metal ferrite formation is discouraged.
  • the oxidized material, when removed from the fluidized bed reactor includes no more than about 5 wt. % selected metal ferrites.
  • the selected metal-containing components of the selected metal-containing material are heated to a temperature ranging from about 580 to about 680 0 C.
  • the microwave energy source comprising one or more individual generating units generating the microwave energy preferably has a power level ranging from about 1 kw to about 150 kw per generating unit and operates at a frequency ranging from about 300 MHz to about 3 GHz.
  • the reaction chamber preferably has an unloaded Q value ranging from about 1,000 to about 25,000, and the microwave energy delivered to the carbon-containing and gold-containing material preferably ranges from about 250 to about 300,000 Joules/gm. Most, if not all, of the microwave energy has a preferred frequency of about 915 MHz.
  • the fluidized bed of sulfidic material is positioned above an inert bed of particulate material.
  • the inert bed of particulate material is too heavy to be fluidized by the fluidizing gas and is substantially inert chemically during microwave irradiation and bed fluidization.
  • the particulate sulfidic material preferably has a P 80 size ranging from about 35 microns to about 75 microns, and the particulate material in the inert bed a P 80 size ranging from about 200 microns to about 300 microns.
  • the fluidized bed reactor can operate as a bubbling bed fluidized system, and the microwave interaction with the material can occur primarily within the lean phase medium (i.e., the bed of sulfidic material).
  • the present invention is particularly effective for the microwave treatment of a class of copper ores and concentrates known as chalcopyrite, whereby the end product is a mixture of copper oxide and copper sulfate, both of which are highly soluble in solvents, such as water and mineral acid, and directly amenable to solvent extraction electrowinning (SX/EW) copper recovery techniques.
  • solvents such as water and mineral acid
  • SX/EW solvent extraction electrowinning
  • the ratio or relative proportions of (sulfur-free) copper oxides and copper sulfates in the removed oxidized material may be tailored for a selected downstream metal recovery process because of the precise process control afforded by the microwave process. For example, controlling the ratio can be a significant feature in the downstream metal recovery process because it provides a methodology for controlling excess acid generation during chemical pressure oxidation, such as in an autoclave. This can be particularly important in high and medium temperature pressure oxidation applications.
  • An added advantage of the disclosed process is that it is most efficient in treating low concentration ores and concentrates known as "rough concentrates". As will be appreciated, these materials are commonly more coarsely ground than copper ores and concentrates subjected to conventional pressure oxidation, thereby avoiding very significant grinding and concentrating costs and making it possible to economically process copper ores which would otherwise be subeconomic.
  • the present invention can provide a number of advantages depending on the particular configuration.
  • the use of microwave energy rather than radiant thermal energy can provide substantial energy savings.
  • Microwaves heat and activate primarily the selected metal component of the sulfidic material and not the gangue (or other components). Microwave heating can extremely rapidly heat the selected metal components.
  • the present invention can produce the selected metal oxide and sulfate end products more rapidly than by using either a simple batch process (as disclosed by Kruesi) or a conventional bubbling fluidized bed device.
  • the microwave-controlled fluidized bed reactor of the present invention can beneficially operate as a "lean phase" (i.e. high gas to solids ratio) fluidized system similar to the elutriated (cyclone) product stream described herein.
  • each of the expressions “at least one of A, B and C”, “at least one of A, B, or C”, “one or more of A, B, and C", “one or more of A, B, or C" and "A, B, and/or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B and C together.
  • Sulfidic refers to materials containing sulfide sulfur.
  • the sulfide sulfur can be present as many types of compounds or minerals, including marcasite, pyrrhotite, chalcopyrite, arsenopyrite, bornite, chalcocite, covellite, galena, molybdenite, sphalerite, and tetrahedrite, to name but a few.
  • Fig. 1 is a cross-sectional view of a fluidized bed reactor according to an embodiment of the invention
  • Figs. 2A and 2B are plots of percent copper recovery (vertical axis) against temperature (horizontal axis);
  • Figs. 3 A and 3B are plots of percent copper recovery (vertical axis) against temperature (horizontal axis);
  • Figs. 4A and 4B are plots of percent copper recovery (vertical axis) against lbs. sulfur/cubic foot of air (horizontal axis); and Figs. 5A and 5B are plots of percent copper recovery (vertical axis) against lbs. sulfur/cubic foot of air (horizontal axis).
  • the present invention discloses a means by which microwave energy is used to initiate and sustain the reactions described in (1) and (2) above.
  • these reactions once initiated, will continue autogeneously using the heat generation from the burning sulfur; below 7 wt. % concentration, the process requires additional energy, which is herein disclosed as being microwave energy.
  • the temperature may be controlled by a variety of means preferably to less than about 690 0 C and more preferably within the range of about 580°C-680°C so as to prevent the formation of insoluble spinel and to control the oxide-sulfate ratio of the calcine product.
  • Microwave energy is particularly attractive because it heats selectively certain components of the material more than others.
  • the gangue is weakly microwave absorptive, microwave reflective, or substantially transparent to microwave radiation while minerals containing certain metals, particularly copper, are highly absorbent of microwave energy.
  • Other transition metals that form minerals absorptive of microwave energy include nickel, cobalt, and manganese from their oxide and silicate minerals and molybdenum and rhenium from their sulfide minerals.
  • transition metals that are not too microwave absorptive include sphalerite and the oxide ores of zinc and iron.
  • FIG. 1 shows a first embodiment of the present invention.
  • a fluidized bed reactor includes a metallic cavity (1) to which is connected a waveguide port (2) through which microwave energy is introduced into the cavity (1).
  • the waveguide (3) is partitioned from the cavity by means of a window (4), which is transparent to the microwave energy but prevents gas and solids from entering the waveguide (3).
  • a tuning device (5) is inserted into the waveguide (3) to maximize microwave energy transfer into the reactor vessel. Both the window (4) and tuner (5) devices are well known to those knowledgeable in the usage of microwave energy.
  • the microwave containment walls of the reactor 10 are preferably constructed of a microwave reflective material.
  • the reaction vessel may optionally include an inner vessel which is constructed of essentially microwave -transparent material.
  • suitable materials include alumina, aluminum silicate, quartz, and low-metal ceramics (which are substantially transparent to microwave energy) and stainless steel, carbon steel, nickel alloys and aluminum alloys (which are reflective of microwave energy).
  • the metal-containing material which is commonly chalcopyrite ore or concentrate, is introduced into the reactor vessel by means of a screw fed duct (6).
  • the rate at which material is fed into the reactor is determined by the speed of the screw feeder.
  • the metal-containing material is fed into the vessel at a rate sufficient to provide a desired average residence time of the material in the reactor cavity.
  • the metal-containing material has a variety of components.
  • the material comprises at least about 5 wt. % sulfide sulfur and more typically from about 7 to about 35 wt. % sulfide sulfur, at least about 5 wt. % and more typically from about 10 to about 30 wt. % selected base metal, and no more than about 5 wt. % selected base metal oxides, with the remainder being one or more of silicates, carbonates, and other oxides.
  • the material contains no more than about 6 wt. % sulfide sulfur and is therefore not capable of autogenous oxidation.
  • the material may be in the form of an ore, concentrate, tailings, or combinations thereof.
  • the material be dried before processing the reactor cavity (1). This is preferably done by heating the material at low temperature and/or exposing the material to sunlight or dry air for a prolonged period.
  • the water content of the material is no more than about 10 wt. % and even more preferably no more than about 1 wt. %. Excess water in the material can increase microwave energy requirements.
  • the metal-containing material to be processed is finely ground before introduction into the reactor vessel.
  • the material is comminuted to a P 80 size preferably ranging from about 35 microns to about 75 microns and introduced through the screw fed duct (6) at a material flow rate ranging from about 4 lbs. sulfur/hr/square foot of fluidizing grate area to about 12 lbs. sulfur/hr/square foot of fluidizing grate area.
  • a molecular oxygen-containing fluidizing gas is introduced into the reactor vessel by means of an inlet duct (7), which is connected to a fluidizer distribution plate (8) located near the bottom of the reactor vessel. Gas velocity is controlled by means of a fan (9) installed in the gas inlet duct. Fluidizing gas preferably comprises at least about 15 mole% molecular oxygen and even more preferably is ambient air. Ambient air includes other components, primarily including water vapor, nitrogen, and carbon dioxide. Solid materials within the reactor vessel include the material (10) to be treated and a resident sand bed (11). The sand bed (11) within the reactor vessel comprises heavier particles than the particulate material and is not fluidized by the gas stream.
  • the sand in the sand bed (11) preferably remains in the reactor vessel and provides a thermal ballast (or heat retention media) for the reactor and a means for assisting in the cleanout of the reactor vessel.
  • the sand typically has a P 80 size preferably ranging from about 200 microns to about 300 microns.
  • other inert materials may be employed in the bed (11) in lieu of or in addition to sand.
  • the material (10) to be treated is fluidized by the gas stream and carried by the fluidizing gas to the exhaust port (12) to which is attached a cyclonic filter or similar device (13).
  • the device (13) separates the solids from the gas stream. Separated solids are removed as a calcine product (14).
  • the exhaust gas stream (15) may then by further filtered as necessary and vented. A portion of the exhaust gas stream may be recirculated (16) and mixed with the inlet fluidizing gas as a means of controlling molecular oxygen content in the gas stream to the reactor vessel.
  • the molecular oxygen is present in an amount that is at least stoichiometric relative to the sulfide sulfur content of the material (10) and even more preferably in an amount that is at least about 110 to about 200% of the stoichiometric amount, and the molecular oxygen content of the fluidizing gas when introduced into the bottom of the vessel is at least about 10 mole % and even more preferably ranges from about 15 to about 20 mole %.
  • the fluidizing velocity of the gas is preferably sufficient to suspend the material
  • the velocity of the fluidizing gas ranges from about the minimum fluidization velocity of the largest ore material particle size to about the fluidization terminal velocity of the smallest ore particle size.
  • the material While the material is fluidized in the bed, it is irradiated with microwave energy.
  • the microwave energy is absorbed by the selected metal sulfides, thereby rapidly heating the bed.
  • the heating mechanism results from a combination of dielectric and ohmic heating, whereby both electrical displacement and conduction currents are used to convert the electromagnetic energy directly into heat within the material (10). The efficiency of this energy conversion is dependent upon the dielectric properties of the material to be treated.
  • Microwave receptor elements principally selected metal sulfides, are rapidly heated in a controlled manner.
  • the fluidized bed operates as a lean phase fluidized system, and the microwave interaction with material occurs substantially within the lean phase medium.
  • a lean phase system has a relatively high gas-to-solids ratio.
  • the volumetric fluidizing gas-to-solids ratio is at least about 1 : 1 and even more commonly ranges from about 2:1 to about 10:1.
  • the microwave energy heats the metal-containing materials to a temperature sufficiently high to oxidize the sulfide sulfur in the metal-containing material according to equations (1) and (2) above but insufficient to oxidize a significant amount of the sulfide sulfur according to equation (3) above.
  • no more than about 5 wt. % and even more preferably no more than about 1.0 wt. % of the sulfide sulfur is oxidized according to equation (3). At least most, and preferably at least about 90 wt.
  • %, of the remaining sulfide sulfur is oxidized according to equations (1) and/or (2).
  • at least most, more preferably at least about 90%, and even more preferably at least about 95% of the selected metal is in the form of XO or XSO 4 (where X is the selected metal) and no more than about 5%, more preferably no more than about 2.5%, and even more preferably no more than about 1.0% of the selected metal is in the form of a ferrite.
  • the operating temperature of the bed is preferably no more than about 690 0 C, more preferably ranges from about 350 to about 680 0 C, even more preferably ranges from about 550 to about 680 0 C, and even more preferably ranges from about 580 to about 680 0 C.
  • the material outputted via output (12) from the reactor cavity has a preferred maximum sulfide sulfur content of no more than about 1 wt. % and even more preferably of no more than about 0.5 wt. %. Stated another way, preferably at least 80% and even more preferably at least about 95% of the sulfide sulfur is converted to a sulfate or other type of sulfur oxide.
  • Temperature, heating rate, and/or microwave coupling can be controlled in a number of ways.
  • dielectric loss factors of the material constituents can be temperature dependent. Accordingly, it is desirable to optimize dynamically the coupling between the magnetron or other microwave generating source and the cavity (1) and the resonant tuning of the cavity (1).
  • the degree of coupling or matching of the cavity with the magnetron determines the efficiency with which energy is delivered to the cavity (1).
  • Preferred coupling is as close to unity as possible.
  • the power of the microwaves and the time of application of the microwaves are controlled. In another approach, the power of the microwaves is adjusted according to the heating temperature.
  • an aperture size of a variable iris and/or the tuner device (5) positioned in the waveguide is adjusted in response to the temperature of the bed and/or the power of the reflected microwaves (relative to the microwaves entering the reactor). Coupling is optimized as reflected energy is minimized.
  • the microwave source comprising one or more individual generating units generates power levels in the range of about 1 kw to about 150 kw per generating unit.
  • a preferred power level is from about 10 to about 120 kw per generating unit.
  • the specific energy delivered to the bed in the cavity (1) ranges from about 250 to about 300,000 Joules/gm or from about 2 to about 20 kW-h/t.
  • the unloaded Q factor in the cavity (1) preferably ranges from about 1,000 to about 25,000, but most preferably is at least about 200,000.
  • the frequency of the microwave source preferably ranges from about 300 MHz to about 3 GHz, with preferred microwave frequencies being within the Industrial, Scientific, and Medical (ISM) bands of about 915 MHz and about 2,450 MHz, with the ISM band of about 915 MHz being particularly preferred.
  • ISM Industrial, Scientific, and Medical
  • Process control is normally effected using a variety of instrumentation positioned in the cavity (1).
  • temperature probes are installed at various positions within the fluidized bed and all feed and discharge lines, including the gas inlet and outlet lines.
  • Gas pressure and product monitors are installed in all gas lines.
  • Material flow through the reactor cavity is measured either through flow meters or by mass measurements.
  • a microwave reflection detector is positioned in the waveguide. In a batch operation, completion of sulfide sulfur oxidation can be indicated by a substantial drop in bed temperature even though microwave energy is still being passed through the bed. This is so because the microwave absorptivities of the gangue components of the material and of the selected metal oxides are substantially less than that of selected metal sulfides.
  • the oxidized material is removed from the cavity when the bed temperature decreases, even more typically when the bed temperature decreases by at least about 50 0 C, even more typically by at least about 100 0 C, and even more typically by at least about 200 0 C.
  • the residence time of the material in the reactor cavity is no more than about 30 minutes and even more preferably ranges from about 5 to about 10 minutes, though the precise residence time depends on the power of the microwave source and the nature of the gangue associated with the selected metal sulfide.
  • the fluidized bed reactor can be operated in any desirable manner, including as a bubbling bed fluidized system.
  • Conditions within the reactor vessel may be controlled by the screw feed rate, gas velocity, microwave power intensity and fluidizing gas composition, the latter of which includes a provision to inject an inert gas (17) such as nitrogen to quickly starve the reactions.
  • All of the control mechanisms may be actuated electronically and integrated into the overall reactor control system, which may be used to maintain a desired set of reactor operating conditions. By this means, for example, the reaction temperature may be maintained within a specified range to ensure the formation of desired products.
  • the molar or weight ratio of selected metal oxide to selected metal sulfates in the final oxidized material is controlled. This is done by controlling the power of the microwave generator and residence time. Controlling the ratio can be important to the downstream metal recovery process. Ratio control, for example, provides a methodology to control excess acid generation from sulfide sulfur.
  • the ratio of selected metal oxide to selected metal sulfates ranges from about 0.3:1 to about 8:1 and more preferably ranges from about 1 : 1 to about 8:1, and, when further sulfide sulfur oxidation is to be performed chemically, such as in an autoclave, the sulfide sulfur content of the oxidized material (after removal from the fluidized bed reactor) is preferably no more than about 1 wt. % and even more preferably ranges from about 1 to about 0.5 wt. %.
  • the selected metal may be recovered from the oxidized material using known hydrometallurgical methods.
  • the selected metal may be leached, such as using sulfuric acid or water, from the oxidized material to form a pregnant leach solution including the selected metal.
  • the selected metal may be precipitated from the pregnant leach solution, electrochemically collected by cementation, or adsorbed onto an organic sorbent, solvent, or resin.
  • the selected metal-loaded sorbent, solvent, or resin may be stripped using a mineral acid eluant, such as sulfuric acid, and the loaded eluant subjected to electrowinning.
  • the selected metal may be directly electrowon from the pregnant leach solution without an intermediate sorbtion/desorbtion step.
  • Chalcopyrite concentrate was used in a series of experiments to demonstrate the oxidation reactions. Feed material was analyzed and was found to consist of chalcopyrite (dominant), pyrite, minor isocubanite (CuFe 2 S 3 ) and covellite (CuS). Chemical analysis is shown below.
  • the fluidized bed microwave reactor was operated such that the product discharge comprised two separate streams.
  • One stream consisted of material which was discharged from the reactor bed by means of an overflow weir through an air locked valve; this is designated as the calcine product.
  • the other product stream consists of material which was directly elutriated by the fluidizing gas from the reactor and captured and separated from the gas in a cyclone filter; this stream is designated as the cyclone product.
  • the significant difference between these streams is that the calcine product has an average residence time within the reactor vessel of several minutes (depending upon the weir height and feed rate) whereas the cyclone product has an average residence time of only a few seconds (depending upon the gas velocity and reactor height).
  • Figures 2-5 present data relating the operation of the process over a range of operating conditions for a sulfur concentration of 6 wt. % which was determined to be at or slightly below the autogeneous sulfur concentration. Copper extractions averaged 96.7 wt. % and 89.3 wt. % across all tests for calcine and cyclone products respectively.
  • Material feed rate control is used to control operating temperature which must be limited to below 690 0 C to prevent the formation of insoluble products.
  • the fluidized bed reactor is used to heat selected metals in non-sulfide form, such as oxides, hydroxyl carbonates, and silicates.
  • the selected metal sulfides are heated in the presence of molecular oxygen to convert them primarily to sulfates (a "sulfation roast") or primarily to oxides and sulfur dioxide. Heating to convert the selected metal sulfides primarily to selected metal sulfates is preferred as the reaction requires less energy than complete conversion to selected metal oxides and sulfur dioxide. In addition, there will be a lesser amount of sulfur dioxide to scrub from the off-gas.
  • the present invention in various embodiments, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various embodiments, subcombinations, and subsets thereof. Those of skill in the art will understand how to make and use the present invention after understanding the present disclosure.
  • the present invention in various embodiments, includes providing devices and processes in the absence of items not depicted and/or described herein or in various embodiments hereof, including in the absence of such items as may have been used in previous devices or processes, e.g., for improving performance, achieving ease and ⁇ or reducing cost of implementation.

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Abstract

La présente invention concerne le traitement par micro-ondes d'une catégorie de minerais métalliques et de concentrés sélectionnés, en particulier ceux connus sous le nom de chalcopyrite, dans un réacteur à lit fluidisé. Le produit final est couramment un mélange d'oxyde de cuivre et de sulfate de cuivre, les deux étant solubles dans un liquide et directement récupérables par des techniques connues. Le rapport du produit final du mélange oxyde - sulfate peut être contrôlé par le contrôle adapté des paramètres des micro-ondes.
PCT/US2007/079045 2006-09-20 2007-09-20 Procédé et moyens d'utilisation de l'énergie micro-onde pour oxyder un minerai de cuivre sulfurique dans un produit oxyde - sulfate prescrit Ceased WO2008036824A1 (fr)

Applications Claiming Priority (2)

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US82635006P 2006-09-20 2006-09-20
US60/826,350 2006-09-20

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WO2008036824A1 true WO2008036824A1 (fr) 2008-03-27

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US (1) US20080118421A1 (fr)
CL (1) CL2007002700A1 (fr)
PE (1) PE20080719A1 (fr)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016180624A1 (fr) * 2015-05-12 2016-11-17 Outotec (Finland) Oy Procédé de grillage partiel de concentrés contenant du cuivre et/ou de l'or

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2606190A1 (fr) * 2005-04-27 2006-11-02 Hw Process Technologies, Inc. Traitement d'eaux de forage
US20070235447A1 (en) * 2006-04-03 2007-10-11 King Yan Kwok Apparatus and process for extraction of constituents from alternative medicinal material
WO2008036820A2 (fr) * 2006-09-20 2008-03-27 Hw Advanced Technologies, Inc. Procédé d'oxydation de minerais carbonés afin de faciliter l'extraction de métaux précieux
CL2007002699A1 (es) * 2006-09-20 2008-02-29 Hw Advanced Technologies Inc Metodo que comprende lixiviar metal valioso de material que lo contiene, obtener fase liquida con ion y oxido ferrico y uno de ion u oxido ferroso, pasar por membrana de nanofiltracion, obtener retentato mas concentrado en ion u oxido ferrico y menos
US20080069746A1 (en) * 2006-09-20 2008-03-20 Hw Advanced Technologies, Inc. Method and apparatus for microwave induced pyrolysis of arsenical ores and ore concentrates
US20080128354A1 (en) * 2006-11-30 2008-06-05 Hw Advanced Technologies, Inc. Method for washing filtration membranes
WO2008074806A1 (fr) * 2006-12-18 2008-06-26 Alexander Beckmann Procédé de production de cuivre et de métaux nobles à partir de minerais de sulfures d'arsenic et/ou d'antimoine contenant du cuivre ou de concentrés de minerai
CL2019003246A1 (es) * 2019-11-13 2020-04-17 Univ Concepcion Un proceso para producir cobre metálico desde concentrados de cobre sin generación de residuos
CN112853406B (zh) * 2021-01-04 2023-06-09 广西大学 一种微波强化电化学溶出废印刷电路板金属的装置及方法
CN117355485A (zh) * 2021-05-06 2024-01-05 奥罗拉氢气公司 使用微波和/或无线电波由气态烃源制备氢气和固体碳的方法
CN115837393B (zh) * 2022-12-08 2024-04-26 东北大学 基于微波脱硫回收与余硫激发矿渣固化的高硫尾砂资源化利用系统及方法
CN116424891B (zh) * 2023-03-27 2025-06-17 中南大学 驱除球团间隙填充氧装置及使用方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172667A (en) * 1977-06-06 1979-10-30 General Electric Company Method and apparatus for blending powders in a fluidized bed
US4324582A (en) * 1980-06-11 1982-04-13 Kruesi Paul R Process for the recovery of copper from its ores
US4476160A (en) * 1982-06-14 1984-10-09 The Lummus Company Fluidized bed system
WO2004056467A1 (fr) * 2002-12-23 2004-07-08 Outokumpu Technology Oy Traitement de solides granuleux dans un lit fluidise annulaire au moyen de micro-ondes

Family Cites Families (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1092861A (en) * 1912-10-01 1914-04-14 Zeiss Carl Fa Magnifying-glass.
US3261959A (en) * 1962-02-20 1966-07-19 F H Peavey & Company Apparatus for treatment of ore
US3639925A (en) * 1968-05-15 1972-02-08 Us Interior Recovery of gold from carbonaceous ores
US3528179A (en) * 1968-10-28 1970-09-15 Cryodry Corp Microwave fluidized bed dryer
US3761665A (en) * 1972-05-25 1973-09-25 Tokyo Shibaura Electric Co Microwave heating apparatus with looped wave guide and phase shifting means
US3949684A (en) * 1973-08-29 1976-04-13 Copeland Systems, Inc. Method for oxidation of sulfur-containing substances
JPS5823349B2 (ja) * 1975-08-11 1983-05-14 新日本製鐵株式会社 タイカブツノシヨウケツホウホウ
US4188208A (en) * 1978-05-22 1980-02-12 Newmont Exploration Limited Recovery of gold from carbonaceous gold-bearing ores
US4289532A (en) * 1979-12-03 1981-09-15 Freeport Minerals Company Process for the recovery of gold from carbonaceous ores
US4311520A (en) * 1980-02-28 1982-01-19 Cato Research Corporation Process for the recovery of nickel, cobalt and manganese from their oxides and silicates
US4321089A (en) * 1980-06-11 1982-03-23 Cato Research Corporation Process for the recovery of molybdenum and rhenium from their sulfide ores
JPS5745335A (en) * 1980-09-02 1982-03-15 Mitsui Eng & Shipbuild Co Ltd Heating fluidized bed reactor
US4511362A (en) * 1983-08-26 1985-04-16 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Fluidized bed desulfurization
JPS62195892A (ja) * 1986-02-21 1987-08-28 株式会社豊田中央研究所 セラミツクスの加熱制御装置
US4906290A (en) * 1987-04-28 1990-03-06 Wollongong Uniadvice Limited Microwave irradiation of composites
US4919715A (en) * 1988-06-03 1990-04-24 Freeport Mcmoran Inc. Treating refractory gold ores via oxygen-enriched roasting
US4923510A (en) * 1988-10-31 1990-05-08 Gopalan Ramadorai Treatment of refractory carbonaceous sulfide ores for gold recovery
US4902345A (en) * 1989-01-12 1990-02-20 Newmont Gold Co. Treatment of refractory carbonaceous and sulfidic ores or concentrates for precious metal recovery
US4967486A (en) * 1989-06-19 1990-11-06 Glatt Gmbh Microwave assisted fluidized bed processor
US5051456A (en) * 1990-03-30 1991-09-24 Union Carbide Chemicals And Plastics Technology Corporation Process for removing dienes from ethylene propylene diene monomer resins
US5191182A (en) * 1990-07-11 1993-03-02 International Business Machines Corporation Tuneable apparatus for microwave processing
FI89508C (sv) * 1990-12-17 1993-10-11 Ahlstroem Oy Förfarande för rostning av sulfidiska malmer
US5123956A (en) * 1991-04-12 1992-06-23 Newmont Mining Corporation Process for treating ore having recoverable gold values and including arsenic-, carbon- and sulfur-containing components by roasting in an oxygen-enriched gaseous atmosphere
US6143139A (en) * 1992-04-01 2000-11-07 The United States Of America As Represented By The United States Department Of Energy Method for recovering metals from waste
US5382412A (en) * 1992-10-16 1995-01-17 Korea Research Institute Of Chemical Technology Fluidized bed reactor heated by microwaves
US5626447A (en) * 1994-09-14 1997-05-06 Buysman; Jeffrey L. Belt refurbishing method and apparatus
US5536480A (en) * 1994-11-29 1996-07-16 Santa Fe Pacific Gold Corporation Method for treating mineral material having organic carbon to facilitate recovery of gold and silver
US5824133A (en) * 1996-03-12 1998-10-20 Emr Microwave Technology Corporation Microwave treatment of metal bearing ores and concentrates
ZA976925B (en) * 1996-08-06 1998-03-19 Emr Microwave Technology Corp Method and apparatus for optimization of energy coupling for microwave treatment of metal ores and concentrates in a microwave fluidized bed reactor.
US5972302A (en) * 1996-08-27 1999-10-26 Emr Microwave Technology Corporation Method for the microwave induced oxidation of pyritic ores without the production of sulphur dioxide
US6277168B1 (en) * 2000-02-14 2001-08-21 Xiaodi Huang Method for direct metal making by microwave energy
DE10294262D2 (de) * 2001-09-14 2004-08-12 Alexander Beckmann Verfahren zur Gewinnung von Cobalt und Nickel aus Erzen und Erzkonzentraten
CA2363762A1 (fr) * 2001-11-23 2003-05-23 Golden Wave Resources Inc. Metallurgie par pyrolyse electromagnetique
WO2004096456A2 (fr) * 2003-04-24 2004-11-11 Cato Research Corporation Procede pour recuperer de l'energie a partir de dechets organiques
WO2004101832A2 (fr) * 2003-05-08 2004-11-25 Belle Watkins Mines, Inc. Amelioration de la calcination par segregation au moyen des micro-ondes
CA2523465A1 (fr) * 2003-05-08 2004-11-25 Belle Watkins Mines, Inc. Procede de production de gaz hydrogene et d'electricite a partir du carbone
US7214254B2 (en) * 2003-10-28 2007-05-08 Hendrix Holding Company, Inc. Method of removing mercury from mercury contaminated materials
US20080069746A1 (en) * 2006-09-20 2008-03-20 Hw Advanced Technologies, Inc. Method and apparatus for microwave induced pyrolysis of arsenical ores and ore concentrates
WO2008036820A2 (fr) * 2006-09-20 2008-03-27 Hw Advanced Technologies, Inc. Procédé d'oxydation de minerais carbonés afin de faciliter l'extraction de métaux précieux

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172667A (en) * 1977-06-06 1979-10-30 General Electric Company Method and apparatus for blending powders in a fluidized bed
US4324582A (en) * 1980-06-11 1982-04-13 Kruesi Paul R Process for the recovery of copper from its ores
US4476160A (en) * 1982-06-14 1984-10-09 The Lummus Company Fluidized bed system
WO2004056467A1 (fr) * 2002-12-23 2004-07-08 Outokumpu Technology Oy Traitement de solides granuleux dans un lit fluidise annulaire au moyen de micro-ondes

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016180624A1 (fr) * 2015-05-12 2016-11-17 Outotec (Finland) Oy Procédé de grillage partiel de concentrés contenant du cuivre et/ou de l'or
KR20170140357A (ko) * 2015-05-12 2017-12-20 오토텍 (핀랜드) 오와이 구리 및/또는 금 함유 정광의 부분 배소 방법
CN107810282A (zh) * 2015-05-12 2018-03-16 奥图泰(芬兰)公司 含铜和/或金的精矿的部分焙烧方法
AU2016259652B2 (en) * 2015-05-12 2019-03-14 Metso Metals Oy Method for partial roasting of copper and/or gold bearing concentrates
EA032531B1 (ru) * 2015-05-12 2019-06-28 Оутотек (Финлэнд) Ой Способ частичного обжига содержащих медь, никель и/или золото концентратов
KR101995658B1 (ko) 2015-05-12 2019-07-02 오토텍 (핀랜드) 오와이 구리 및/또는 금 함유 정광의 부분 배소 방법
CN107810282B (zh) * 2015-05-12 2020-03-27 奥图泰(芬兰)公司 含铜和/或金的精矿的部分焙烧方法

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