WO2011047070A1 - Carbon-dioxide mineral sequestration using mine waste - Google Patents

Carbon-dioxide mineral sequestration using mine waste Download PDF

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Publication number
WO2011047070A1
WO2011047070A1 PCT/US2010/052532 US2010052532W WO2011047070A1 WO 2011047070 A1 WO2011047070 A1 WO 2011047070A1 US 2010052532 W US2010052532 W US 2010052532W WO 2011047070 A1 WO2011047070 A1 WO 2011047070A1
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Prior art keywords
mine waste
slurry
mine
reacted
minerals
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PCT/US2010/052532
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French (fr)
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Daniel Colton
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Daniel Colton
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/24—Magnesium carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/60—Preparation of carbonates or bicarbonates in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • This invention relates to carbon-dioxide mineralogical sequestration using mine waste.
  • Mining is an industry that produces metals essential to maintaining and improving this country's high standard of living but has in many instances a negative environmental legacy due to the water and air pollution created by the voluminous amount of mine waste it generates and the large amount of power it consumes in extracting and beneficiating ore, respecitively.
  • Mine Waste is known to produce acid mine drainage and leach heavy metals to surface and groundwaters.
  • the conversion of fossil fuels to power mining operations, as well as industry in general, results in emission of a large amount of CO 2 into the atmosphere.
  • Carbon dioxide is a primary greenhouse gas. It is believed that much of the observed temperature increases since the early to mid-20th century has been caused by increasing concentrations of greenhouse gases, primarily CO 2 , generated from human activity such as the burning of fossil fuels.
  • Carbon management involves steps including capturing, transporting, and securely storing carbon emitted from sources.
  • the storing of carbon is a process known as carbon sequestration.
  • Any viable system for sequestering carbon must be effective and cost-competitive, stable for long-term storage, and environmentally benign.
  • CO 2 capture and sequestration appears to be the most feasible method for reducing carbon emissions while maintaining the continued large-scale usage of fossil fuels and the supply of vital minerals and metals. See, e.g., U.S. Patent Application Publication 2005/0180910.
  • a method for mineralogically sequestering carbon dioxide (CO 2 ) using mine waste includes: (a) contacting a mine waste stream and water to form a slurry, (b) contacting, in a reaction vessel, the slurry and CO 2 , to provide a reacted slurry, (c) separating the reacted slurry into solids, liquid, and gas and (d) recycling CO 2 from the separated gas.
  • the method can optionally include at least one of (e)-(g): (e) recovering metal from the separated liquid, (f) recycling water from the liquid, and (g) utilizing the separated solids as a value product.
  • An apparatus for sequestering mine waste includes: (a) a source of a slurry of a mine waste stream and water, wherein the mine waste stream comprises at least one of dry mine waste, dry tailings, wet tailings or wet hydrometallurgical residue (HMR); (b) a source of carbon dioxide; (c) a reaction vessel, wherein the slurry and CO 2 , are heated at a temperature of about 100°F (37.8°C) to about 750°F (399°C), and at a pressure of at least about 1100 psi
  • the apparatus may further include at least one or more of the following (e) a recyclor for recycling CO 2 from the separator back to the mine waste stream; (f) a recoveror for recovering metal from the separated liquid; or (g) a recyclor for recycling water from the liquid back to the mine waste stream.
  • the method effectively: (a) utilizes CO 2 produced by an electric power plant that relies upon the combustion of fossil fuels, (b) utilizes CO 2 produced by a facility that burns fossil fuels, (c) utilizes CO 2 generated by a power generation plant or captured from the atmosphere by a CO2 extraction process, (d) lowers the carbon footprint of a mining operation, (e) lowers the carbon footprint of an electric power plant, (f) lowers the carbon footprint of a facility that burns fossil fuels, (g) converts non-reacted mine waste to high value metal, (h) converts non- reacted mine waste to useful material, (i) converts non-reacted mine waste to a value product, (j) recycles water in a mining operation, (k) recycles
  • hydrometallurgical residue produced from ore beneficiation, tailings from ore beneficiation, and mine waste produced from mining operations (1) provides for mineral sequestration of CO 2 , whereby CO 2 reacts with metal cations and minerals in a mine waste stream to form solid carbonate minerals, (m) provides for mineral carbonation of CO 2 , (n) provides for carbon sequestration, (0) provides for environmentally safe and stable materials (e.g., solid carbonate minerals) over a geological time frame, (p) produces mineral carbonates from non-reacted mine waste, (q) provides for a mineralogical fixation of CO 2 over a geological time frame, (r) transfers or trades carbon credit, (s) collects, processes, transports, manages and recycles mines wastes (e.g., tailings) generated at a mine, or any combination thereof, thereby avoiding the negative environmental legacy issues associated with the disposal of mine waste or (u) produces useable or valuable metals and minerals after all chemical reactions relating to the mineral sequestration of CO 2 has taken place in
  • Figure 1 illustrates a block flow diagram depicting carbon-dioxide sequestration in recovering high value metals from mine waste.
  • FIG. 2 illustrates a block flow diagram depicting carbon-dioxide sequestration in recovering high value metals from mine waste.
  • references in the specification to "one embodiment”, “an embodiment”, “an example embodiment”, etc., indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.
  • the presently disclosed subject matter relates to carbon-dioxide sequestration using mine waste and the recovery of high value metals or minerals from mine waste.
  • the following terms have the following meanings, unless otherwise indicated.
  • the sequestration of C0 2 using mine waste comprises a method of extracting and beneficiating ore to produce metals in a sustainable and environmentally friendly manner by locating, for example in the same geographical area, a carbon dioxide producing power plant and a metal mine; using the electricity generated by the power plant to crush, grind, beneficiate the ore.
  • the electricity and carbon dioxide can be provided by a remote power plant.
  • the ore is ground to a particle size of about 125 ⁇ (microns) or less.
  • the metal is then recovered from the finely ground ore by means known in the art and often specific for any one particular metal.
  • An aqueous slurry of the finely ground tailings and the carbon dioxide are then mixed and heated under pressure in a flow reactor.
  • Unrecovered or undesired minerals in the tailings such as magnesium, iron, and calcium silicates (e.g., olivine, pyroxene, and plagioclase), react with the carbon dioxide to form insoluble, thermodynamically stable metal carbonate minerals.
  • the insoluble carbonate minerals sequester both the carbon dioxide and metals (e.g., magnesium, iron, calcium).
  • the insoluble magnesium, iron, and calcium carbonate minerals are non-reactive and can be safely recycled or disposed of (e.g., by filling in old mine pits).
  • the carbonate minerals in the reacted mine waste may neutralize any existing sulfide mineral component of the reacted carbonate-based mine waste (e.g., tailings).
  • This method provides an environmentally friendly and sustainable way to mine and produce valuable metals and minerals while safely disposing of two of the most environmentally unfriendly by-products of mining: the carbon dioxide and non- reacted mine waste (e.g., non-reacted tailings).
  • no additional power is generally required to treat the tailings before reaction with carbon dioxide in the flow reactor as this has already been done by the mining operation during the beneficiation process.
  • the reaction takes place at an elevated temperature (e.g., 100-750°F), and at an elevated pressure (e.g., at least about 1100 psi).
  • an elevated temperature e.g., 100-750°F
  • an elevated pressure e.g., at least about 1100 psi
  • the ore is an ultramafic or basalt cumulate with associated segregations of metals or minerals containing one or more value metals like nickel, copper, cobalt, platinum group elements (PGE), and gold.
  • PGE platinum group elements
  • a specific embodiment includes an apparatus for sequestering C(3 ⁇ 4 using mine waste comprising: (a) a source of a slurry of a mine waste stream and water, wherein the mine waste stream comprises at least one of dry mine waste, dry tailings, wet tailings, dry hydrometallurgical residue, and wet
  • hydrometallurgical residue (b) a source of carbon dioxide; (c) a reaction vessel, wherein the slurry and C0 2 , are heated at a temperature of about 100°F (37.8°C) to about 750°F (399°C), and at a pressure of at least about 1 100 psi (74.9 atm), for a period of time of about 1 minute to about 10 hours, to provide a reacted slurry; and (d) a separator for separating the reacted slurry into solids, liquid and gas.
  • the apparatus may further include one or more of the following (e) a recyclor for recycling CO 2 from the separator back to the mine waste stream; (f) a recoveror for recovering metal from the separated liquid; or (g) a recyclor for recycling water from the liquid back to the mine waste stream.
  • the source of at least some of the C02 is an electric power plant that relies upon the combustion of fossil fuels, another facility that burns fossil fuels, by extraction from the atmosphere, or any combination thereof.
  • the reaction vessel is a pipeline that is of sufficient length, strength, and capacity to permit the reaction among the carbon dioxide, water, and mine waste to occur.
  • calcium, iron and magnesium silicates within the mine waste react with carbon dioxide to form calcium, iron, or magnesium carbonate.
  • a reaction vessel capable of withstanding a temperature of about 100°F (37.8°C) to about 750°F (399°C), and at a pressure of at least about 1100 psi (74.9 atm) is useful.
  • the water is separated from the solid and gas using a separator.
  • the separator comprises a settling pond.
  • the liquid may be discharged into, for example, a settling pond to allow the solids and liquid to separate.
  • the liquid may then be treated to recover suspended or dissolved metals or minerals— such as by filtration or precipitation using various compounds.
  • the water may then be purified and recycled via pipeline to the mine waste stream and used to form additional slurry.
  • the separator may also include a device for separating the gas from solid and liquid. These devices may be storage tanks fed, for example, by bleed valves that reduce the pressure in the reaction vessel.
  • the various gasses formed by the reaction may be separated, for example, by fractionation, condensation, or by further reaction with added materials.
  • the carbon dioxide may be recovered, purified and recycled via pipeline back to the mine waste stream and used to react with additional mine waste.
  • Acid refers to a compound that donates a hydrogen ion (H + ) to another compound (called a base). When dissolved in water, acids give a solution with a hydrogen ion activity greater than that of pure water, i.e. a pH less than 7.0.
  • Common mineral acids include, e.g., sulfuric acid, hydrochloric acid, nitric acid, and perchloric acid.
  • Common organic acids include, e.g., acetic acid (in vinegar), citric acid, ascorbic acid, and toluene sulfonic acid.
  • an acid can refer to a substance that accepts a pair of electrons (Lewis Acid) from another compound. Additional suitable acids include, e.g., orthophosphoric acid, oxalic acid, formic acid, lactic acid ammonium hydrogen sulfate, acetic acid, and mixtures thereof.
  • “Agitates” refers to the act of putting a material into motion with a turbulent force. Agitation can be accomplished by various means, as for example, by rotation, vibration, shaking, or stirring. Agitation can also refer to the contacting of two or more materials to insure mixing.
  • Amphiboles refers to a group of generally dark-colored rock- forming inosilicate minerals, composed of double chain Si0 4 tetrahedra, linked at the vertices and generally containing ions of iron and/or magnesium in their structures. Amphiboles crystallize into two crystal systems, monoclinic and orthorhombic. In chemical composition and general characteristics, they are similar to the pyroxenes. The chief differences from pyroxenes are that (i) amphiboles contain essential hydroxyl (OH) or halogen (F, CI) and (ii) the basic structure is a double chain of tetrahedra (as opposed to the single chain structure of pyroxene).
  • “Atmosphere” refers to the layer of gases that surround the earth by gravity, and such gases are retained for a longer duration if gravity is high and the atmosphere's temperature is low.
  • the atmospheric composition on Earth is largely governed by the by-products of the very life that it sustains. Earth's atmosphere contains roughly (by molar content/volume) 78.08% nitrogen, 20.95% oxygen, a variable amount (average around 0.247%, National Center for Atmospheric Research) water vapor, 0.93% argon, 0.038% carbon dioxide, and traces of hydrogen, helium, and other "noble" gases (and of volatile pollutants).
  • Base refers to a chemical compound that provides a hydroxyl ion (OFT) when dissolved in water.
  • a base gives a solution with a hydrogen ion activity less than that of pure water, i.e. a pH greater than 7.0.
  • Common mineral bases include, e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide.
  • Common organic bases include, e.g., amines, such as triethylamine.
  • a base can refer to a substance that donates a pair of electrons (Lewis Base).
  • "Beneficiation” in mining refers to a variety of processes whereby extracted ore from mining is separated into desired metals or minerals and tailings, the metals and minerals are suitable for further processing or direct use. The tailings are discarded.
  • Carbon dioxide or “CO 2” refers to a chemical compound composed of two oxygen atoms covalently bonded to a single carbon atom. It is believed that carbon dioxide is a “greenhouse” gas that is a source of global warming.
  • Carbon footprint refers to the total set of greenhouse gas (GHG) emissions caused directly and indirectly by an individual, organization, event, or product. For simplicity of reporting, it is often expressed in terms of the amount of carbon dioxide, or its equivalent of other GHGs, emitted.
  • the carbon footprint is a subset of the ecological footprint. Typically, the larger the carbon footprint, the more greenhouse gasses are emitted.
  • Catalyst refers to a chemical substance that increases (or decreases) the rate of a chemical reaction. A catalyst is not consumed by the reaction itself.
  • “Chelating agent” refers to compounds that form bonds (or other attractive interactions) between two or more separate binding sites within the same ligand and a single central atom.
  • An example of a chelating agent is EDTA (ethylenediamine tetraacetic acid, which is a chelating agent for Ca 2+ and Fe 3+ cations.
  • Additional suitable chelating agents include, e.g., acetic acid, oxalic acid, ascorbic acid, phthalic acid, and salts thereof.
  • the chelating agent is chosen from one or more compounds that provide anionic groups in aqueous solution selected from the group of ethylene- diamine, acetate, glycolate, S2O 3 "2 , F “ , SO4 “2 , OH “ , picolinate, glycine, glutamate, and malonate.
  • Crystallinopyroxene refers to monoclinic crystalline form of pyroxene.
  • CO 2 sequestration refers to the storage of carbon dioxide in a solid material or mineral through chemical, biological, or physical processes. It is a geoengineering technique for the long-term storage of carbon dioxide or other forms of carbon, for the mitigation of global warming. Methods of CO 2 sequestration include using subsurface saline aquifers, reservoirs, ocean water, aging oil fields, and mineralogical reactions to form insoluble
  • thermodynamically stable carbonates “Combustion” or “burning” refers to the complex sequence of exothermic chemical reactions between a fuel (usually a hydrocarbon) and an oxidant accompanied by the production of heat or both heat and light in the form of either a glow or flames, appearance of light flickering. Burning of coal, natural gas, or wood are examples of combustion.
  • Contacting refers to the coming together or touching, as of objects or surfaces.
  • Dry tailings refers to the remaining portion of an ore consisting of finely ground rock after some or all of the desired material, such as a metal, has been extracted. Dry tailings are typically considered a waste product of mining.
  • “Dry mine waste” refers to rock which contains little if any of the desired material in economically recoverable quantities and containing virtually no (e.g., less than about 5 wt.%) process liquid.
  • Mine Waste e.g., non-ore rock or overburden
  • Dry mine waste is typically considered a waste product of mining.
  • “Duluth Complex” refers to a geologic formation in northern Minnesota. It is one of the largest intrusions of gabbro on earth, and one of the largest layered ultramafic and basaltic intrusions known. It covers an area of 4715 km 2 . The lower portion of the intrusion consists of ultramafic cumulates with associated segregations of nickel, copper, cobalt, platinum group elements
  • PGE gold, and silver along with deposits of other valuable metals.
  • Many of these metals are in the form of sulfide minerals. Where the Duluth Complex hosts these metals and/or minerals in concentrations that make then
  • Electric power plant or “power generation plant” refers to an industrial facility for the generation of electric power. They are also often referred to as a generating station, power plant, or powerhouse.
  • the energy needed to operate a power plant can be provided in many ways, by falling water (hydroelectric power plants), by burning fossil fuels (fossil fuel power plants), by radioactive decay (nuclear power plants), by wind (wind farms).
  • Electro resistance refers to the measure of an object's opposition to the passage of a steady electric current. The unit of resistance is the ohm.
  • Electric winning also called electroextraction, refers to the
  • Electrowinning a current is passed from an inert anode through a liquid leach solution containing the metal so that the metal is extracted as it is deposited in an electroplating process onto the cathode.
  • Ferous oxide refers to iron(II) oxide, also known as iron
  • iron oxide/oxidized iron or more commonly rusted iron is one of the iron oxides. It is a black-colored powder with the chemical formula FeO. It consists of the chemical element iron in the oxidation state of 2+ bonded to oxygen.
  • Fossil fuel refers to fuels formed by natural resources such as anaerobic decomposition of buried dead organisms. These fuels contain high percentage of carbon and hydrocarbons. Fossil fuels range from volatile materials with low carbon:hydrogen ratios like methane (natural gas), to liquid petroleum (oil), to nonvolatile materials composed of almost pure carbon (anthracite coal). The age of the buried dead organisms and their resulting fossil fuels is typically millions of years, and sometimes exceeds 650 million years.
  • Gangue in mining refers to the commercially worthless material (i.e., minerals and metals) that overlies, surrounds, or is closely mixed with, a wanted mineral or metal in an ore deposit. Such materials that were once thought of as gangue were dumped as tailings.
  • Gas refers to a state of matter, consisting of a collection of particles (molecules, atoms, ions, electrons, etc.) without a definite shape or volume that are in more or less random motion. Steam is an example of a gas.
  • Geological time frame refers to the period of time that denotes Earth's history, past, present, and future. It is used by geologists, paleontologists, and other earth scientists to describe the timing and relationships between events that have occurred during the history of the Earth. It is composed of eons. Eons are divided into eras, which are in turn divided into periods, epochs, and ages.
  • Gdient refers to the rate of change with respect to distance of a variable quantity, as temperature or pressure, in the direction of maximum change.
  • An example is a pipe heated at one end in which a temperature gradient would be present along the length of the pipe.
  • Another example is a pipe elevated at one end in which a height gradient would be present along the length of the pipe. The presence of any suitable gradient will create a pressure differential due to gravity along a gradient to effectively traverse the slurry within (or along) the reaction vessel.
  • High pressure refers to a pressure equal to or greater than about 1,000 psi (74.9 atm). High pressure can result in chemical reactions occurring that would not occur to an appreciable degree at atmospheric pressure or that would take longer to occur.
  • High temperature refers to a temperature equal to or greater than about 100°F (37.8°C). High temperature can result in chemical reactions occurring that would not occur to an appreciable degree at ambient temperature or that would take longer to occur.
  • Induction refers to the production of voltage across a conductor situated in a changing magnetic field or a conductor moving through a stationary magnetic field.
  • Liquid refers to a state of matter characterized by particles that are loose and can freely form a distinct surface at the boundaries of its bulk material.
  • a liquid has a definite volume but its shape is determined by the container it fills. Water is an example of a liquid.
  • Mafic silicate refers to silicate minerals, magmas, and rocks which are relatively high in the heavier elements. The term is derived from using the MA from magnesium and the FIC from the Latin word for iron, but mafic magmas also are relatively enriched in calcium and sodium.
  • Metal cation refers to a positively charged metal atom that moves toward the cathode (or negative pole) during electrolysis. Thus, a metal cation is a positively charged ion with more protons than electrons.
  • Fe 2+ and Fe 3+ are examples of cations.
  • Metal refers to an element, compound, or alloy characterized by high electrical conductivity. In a metal, atoms readily lose electrons to form positive ions (cations); those ions are surrounded by delocalized electrons, which are responsible for the conductivity. The compound thus produced is held by electrostatic interactions between the ions and the electron cloud, which are called metallic bonds. Metals usually form cations through electron loss. Metals are further classified by elemental position on the periodic table with certain groups of metals exhibiting similar chemical behavior.
  • Sodium (Na), potassium (K), and lithium (Li) are examples of alkali metals
  • Calcium (Ca), magnesium (Ng), and Barium (Ba) are examples of alkali earth metals
  • chromium (Cr), iron (Fe), copper (Cu), nickel (Ni), platinum (Pt), silver (Ag), and gold (Au) are examples of transition metals, (we can incorporate "Rare earth metal” here or leave it as is later in this section)
  • Microwave refers to electromagnetic waves with frequencies between
  • 300MHz (0.3 GHz) and 300 GHz typically between 1 GHz and 300 GHz.
  • Mine waste stream refers to the aggregate flow of mine waste material from generation to treatment to final disposition. Tailings and dry mine waste are typically part of the mine waste stream. In specific embodiments, the mine waste stream is processed (e.g., by grinding) to an average particle size of less than about 500 microns, or is physically activated by application of ultrasonic energy or microwave energy.
  • Mine refers to a site where the extraction of minerals, metals, or other geological materials from the earth, usually from an ore body, vein, or (coal) seam takes place.
  • Materials recovered by mining include base metals, precious metals, iron, uranium, coal, diamonds, limestone, oil shale, rock salt, and potash. Any material that cannot be grown through agricultural processes, or created artificially in a laboratory or factory, is usually mined. Mines can be subsurface (underground mines) or surface (strip or open pit mines).
  • Standard refers to an element or chemical compound that is normally crystalline and that has been formed as a result of geological processes. It has a characteristic chemical composition, a highly ordered atomic structure, and specific physical properties. Minerals range in composition from pure elements and simple salts to very complex silicates with thousands of known forms. The study of minerals is called mineralogy.
  • a rock is an aggregate of one or more minerals. For example, limestone is a sedimentary rock composed almost entirely of the mineral calcite (the most stable polymorph of calcium carbonate (CaCOs).
  • the Duluth Complex is host to ore which contains, among other minerals, chalcopyrite, cubanite, pentlandite, pyrite, magnetite, ilmenite, olivine, pyroxene, and plagioclase. Most of the copper in the Duluth Complex ore is in the sulfide minerals chalcopyrite and cubanite. Most of the nickel in the Duluth Complex ore is in the sulfide mineral pentlandite.
  • Mine waste refers to any waste material, including but not limited to surface overburden, non-ore rock, lean ore, tailings, or hydrometallurgical residue generated during the process of excavation and beneficiation of ore that is stored, discarded, or disposed of.
  • Mine waste is a known source of pollution due to its potential to generate acid mine drainage and leach metals into the environment polluting soils, surface water, and groundwater.
  • Nuclear power reactor refers to a device in which nuclear chain reactions are initiated, controlled, and sustained at a steady rate. Nuclear power reactors are often used in electric power plants as the energy source for the generation of electricity. Heat generated from radioactive decay is used to heat water to provide steam to drive a turbine that generates electricity.
  • “Olivine” refers to a series of magnesium and iron silicate minerals with the formula (Mg,Fe) 2 Si0 4 . They can range from forsterite, Mg 2 Si0 4 to fayalite, Fe 2 Si0 4 .
  • “Ore beneficiation” refers to a variety of process whereby extracted ore from mining is reduced to particles that can be separated into minerals or metals and waste material (e.g., tailings), the former suitable for further processing or direct use.
  • Orthopyroxene refers to the orthorhombic crystalline form of pyroxene.
  • Outlet protrusion refers to something projecting or jutting out from which material flows out or can be obtained.
  • Pipe refers to a tube or hollow cylinder used to convey materials or as a structural component. Both pipe and tube imply a level of rigidity and permanence, whereas a hose is usually portable and flexible.
  • the pipe can be manufactured from any suitable material. For example, when the contents of the pipe are heated at an elevated temperature, the pipe can be manufactured from materials that are suitable for high temperatures. Likewise, the pipe can be manufactured from materials that are suitable for high pressures.
  • Pogioclase refers to a series of tectosilicate minerals within the feldspar family. Rather than referring to a particular mineral with a specific chemical composition, plagioclase is a solid solution series, more properly known as the plagioclase feldspar series The series ranges from albite to anorthite endmembers (with respective compositions NaAlSisOs to CaAl 2 Si208), where sodium and calcium atoms can substitute for each other in the mineral's crystal lattice structure. Plagioclase in hand samples is often identified by its polysynthetic twinning or 'record-groove' effect.
  • Platinum group metal or “platinum group element” (PGE) refers to one or more of six metallic elements clustered together in the periodic table. These elements are all transition metals, lying in the d-block (groups 8, 9, and 10, periods 5 and 6).
  • the six platinum group metals are ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt). They have similar physical and chemical properties, and tend to occur together in the same mineral deposits. They have outstanding catalytic properties, are highly resistant to wear and tarnish, resistant to chemical attack, have excellent high-temperature characteristics, and stable electrical properties. All these properties have are useful for industrial applications.
  • Pyroxene refers to a group of rock- forming silicate minerals found in many igneous and metamorphic rocks. They share a common structure consisting of single chains of silica tetrahedra and they crystallize in the monoclinic and orthorhombic systems. Pyroxenes have the general formula XY(Si,Al) 2 0 6 , where X represents calcium, sodium, iron +2 and magnesium and more rarely zinc, manganese and lithium and Y represents ions of smaller size, such as chromium, aluminum, iron +3 , magnesium, manganese, scandium, titanium, vanadium and even iron +2 .
  • Radiofrequency refers to a portion of the electromagnetic spectrum within the range of about 3 Hz to 300 GHz. This range corresponds to the frequency of alternating current electrical signals used to produce and detect radio waves.
  • Rare earth metal or “rare earth element” refers to one or more of seventeen chemical elements in the periodic table, namely scandium (Sc), yttrium (Y), and the fifteen lanthanoids; Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb), and Lutetium (Lu).
  • Reaction vessel refers to a reactor designed to contain a reaction, such as a chemical reaction. Pipes, tanks, and carboys are types of reaction vessels.
  • Recycle refers to the act of employing a material or substance that is obtained in a chemical reaction or process (i.e., as a starting material, reagent, solvent or catalyst) for a preceding step in that reaction or process. Thus, that material or substance is reused in the overall process. The material or substance can be reused or recycled as many times as the overall process is carried out. It is widely accepted that recycling prevents the waste of potentially useful materials, reduces the consumption of fresh raw materials, reduces energy usage, reduces air pollution (from incineration) and water pollution (from landfilling) by reducing the need for "conventional" waste disposal, and lower greenhouse gas emissions as compared to virgin production.
  • “Sequestration” refers to the storage of a material in a solid material through chemical, biological, or physical processes.
  • carbon dioxide can be sequestered by reaction with a mineral to form an insoluble carbonate salt.
  • Another example is sequesteration of metals by reaction to form insoluble salts.
  • Spenttine refers to a group of common rock- forming hydrous magnesium iron phyllosilicate ((Mg, Fe) 3 Si 2 0s(OH) 4 ) minerals; they may contain minor amounts of other elements including chromium, manganese, cobalt, and nickel.
  • Solid refers to a thick suspension of solids in a liquid. Solid materials are often transported in a pipeline as a slurry.
  • Carbonate mineral refers to minerals containing the carbonate (CO 3 2 ) anion. Examples are calcium carbonate (CaC0 3 , limestone),calcium magnesium carbonate (CaMg(C03)2, dolomite), magnesium carbonate (MgC03, magnesite), and iron carbonate (FeCC ⁇ , siderite). Many carbonate salts are insoluble in water. Notable exceptions include sodium, potassium, and ammonium carbonates.
  • Solids refers to the state of matter characterized by a distinct structural rigidity and resistance to deformation (that is changes of shape and/or volume).
  • the particles in a solid ions, atoms or molecules
  • the forces between particles are strong enough so that the particles cannot move freely but can only vibrate.
  • a solid has a stable, definite shape, and a definite volume. Ice is an example of a solid.
  • Tailings in mining refers to gangue or the fine grained mineral remains of ore, once most of the valuable metals and minerals have been removed in the ore beneficiation process. Tailings often contain desired metals or minerals but at amounts that are uneconomical to recover. As economics change and new technologies develop, tailings can be recycled to recover additional desired materials. Tailings are a known source of pollution due to their potential to generate acid mine drainage and leach metals into the environment.
  • Value product refers to a waste material that has been turned into a material that is either useful or can be sold at a profit, for example by recovery of additional metals from the mine waste.
  • Weight chemical method refers to methods of extracting metals from their ores using chemicals and solutions in one or more steps. Typical steps include leaching, solution concentration of the metal, and metal recovery. Metal recovery can be by precipitation.
  • Hydrometallurgical residue or “HMR” refers to the residual aqueous solution, rock, and tailings left over after an aqueous solution has been used to extract the desired material, such as a metal, from an ore.
  • the wet aqueous solution can be the leachate from which the desired metal or metal chelate has been removed.
  • Wet tailings refers to the remaining portion of an ore consisting of finely ground rock and process liquid after some or all of the desired material, such as a metal, has been extracted. Wet tailings are a waste product of mining.
  • separating refers to the process of removing solids, liquid and/or a gas from at least one of the other.
  • the process can employ any technique known to those of skill in the art, e.g., decanting the mixture, filtering the solids from the mixture, or a combination thereof.
  • filtering refers to the process of removing solids from a mixture by passing the liquid through a filter, thereby suspending the solids on the filter.
  • decanting refers to the process of pouring off a liquid without disturbing the sediment, or the process of pouring off a liquid with a minimal disturbance of the sediment.
  • purifying refers to the process of ridding a solid substrate (e.g., a metal) of impurities. Suitable methods of purifying include, e.g., washing, recrystallizing, and drying.
  • alkali metal refers to metals of Group LA of the Periodic Table of Elements, e.g., sodium (Na) and potassium (K).
  • alkaline earth metal refers to metals of Group IIA of the Periodic Table of Elements, e.g., magnesium (Mg) and calcium (Ca).
  • Figures 1 and 2 illustrate a block flow diagram depicting mineralogical carbon-dioxide sequestration using mine waste and the recovery of high value metals from mine waste.
  • a slurry (103) is formed from the mine waste stream (101). While any suitable and appropriate substance can be employed to form the slurry (103) from the mine waste stream (101), water is a particularly suitable substance.
  • the mine waste stream (101) will include the requisite amount of water such that the mine waste stream (101) is effectively a slurry (103). In such an embodiment, the addition of water is not needed.
  • water can be added to the rock waste stream (101) to form the slurry (103).
  • any suitable amount of water can be employed.
  • the mine waste stream In a specific embodiment of the present invention, the mine waste stream
  • the mine waste stream (101) includes at least one of dry mine waste, dry tailings, wet tailings and wet hydrometallurgical residue (HMR).
  • the mine waste stream (101) includes olivine, orthopyroxene, clinopyroxene, plagioclase, amphiboles, ferrous oxide, serpentine minerals, or a combination thereof.
  • the mine waste stream (101) includes silicon dioxide (S1O2), aluminium oxide (AI2O 3 ), titanium(IV) oxide (T1O2), calcium oxide (CaO), iron (Fe), magnesium oxide (MgO), manganese(II) oxide (MnO), sodium oxide ( a 2 0), potassium oxide (K 2 0), sulfur (S), or a combination thereof.
  • Some of the oxides may be too reactive to exist in a waste stream, e.g., (Na 2 0), (K 0).
  • the slurry (103) includes naturally occurring magnesium (Mg) and calcium (Ca) containing minerals.
  • the slurry (103) includes magnesium carbonate minerals, iron carbonate minerals, calcium carbonate minerals, or a combination thereof.
  • the slurry (103) includes mafic silicate materials.
  • any dry mine waste present in the mine waste stream (101) is ground or crushed, prior to contacting with water.
  • the slurry is made up of mine waste (e.g., tailings) from the excavation and beneficiation of Duluth Complex ore,
  • the temperature of about 100°F (37.8°C) to about 750°F (399°C) in step (104) is achieved utilizing electric resistance, induction, microwave, radiofrequency, or a combination thereof.
  • the slurry (103) includes liquid and solids, in a weight ratio of about 1 :3, respectively, to about 3:2, respectively.
  • a reacted slurry (105) is formed from the slurry (103).
  • CO 2 is employed at a relatively elevated temperature (e.g., 100-750°F), and at an elevated pressure (e.g., at least about 1100 psi).
  • the CO 2 can contact the slurry (103) to provide the reacted slurry (105), for any suitable period of time.
  • the C(3 ⁇ 4 can contact the slurry (103) to provide the reacted slurry (105), for at least about 1 minute, for at least about 1 hour, or for about 1 minute to about 10 hours.
  • the CO 2 in step (104) chemically reacts with the slurry (103), creates a pressure differential along a gradient to traverse the slurry (103) within the reaction vessel, agitates the slurry (103) within the reaction vessel, provides a reactant medium for the slurry (103) thereby fluidizing the slurry (103), or any combination thereof.
  • the source of at least some of the CO 2 in step (104) is an electric power plant that relies upon the combustion of fossil fuels, another facility that burns fossil fuels, or extracts CO 2 from the atmosphere, or any combination thereof.
  • the slurry (103) and the CO 2 are contacted in the presence of at least one of an acid, base, chelating agent, and catalyst.
  • an outlet protrusion e.g., pipe that can be about 100 meters in length
  • the pipe will typically be suitable for high temperature, high pressure conditions, or a combination thereof.
  • the pipe is suitable for high temperature and/or high pressure conditions, such that the reacted slurry (105) that is formed is recovered at a geographical location different from the geographical location where step (104) is carried out.
  • the reacted slurry (105) is separated, such the gas (H I), liquids (109) and solids (107) are separated from one another.
  • the separation can employ any suitable and appropriate methods and materials that are commonly used in the industry, and well-known to those of skill in the art.
  • the gas (11 1) that is obtained from the separating (106) can be processed such that at least a portion of CO 2 present therein can be recycled or reused in subsequent step (104). That is, in subsequent processing in which reacted slurry (105) is formed from slurry (103), the CO 2 that is employed therein can include, at least in part, CO 2 that is present in the gas (11 1). It is appreciated that it will be understood by those of skill in the art that such a recycling of CO 2 will present numerous environmental, cost and technical advantages.
  • the solids (107) obtained from the separation (106) can be converted to value products (1 13).
  • the liquid (109) obtained from the separation (106) can optionally be further separated into water (117) and metal (1 15).
  • the metal (1 15) can optionally be further purified (1 16) to provide purified metal (1 19).
  • the water (117) can optionally be recycled or reused in subsequent step (102). That is, in subsequent processing in which a slurry (103) is formed from mine waste stream (101) employing water, that the water employed therein can include, at least in part, water (117) that is present in liquids (109) that was subsequently separated from the metal (115). It is appreciated that it will be understood by those of skill in the art that such a recycling of water (1 17) will present numerous environmental, cost and technical advantages.
  • the metal includes at least one of copper (Cu), nickel (Ni), lead (Pb), silver (Ag), gold (Au), chromium (Cr), cobalt (Co), a rare earth metal, and a platinum group metal.
  • the separation of the metal (115) from the water (117) is achieved utilizing electrowinning, a wet chemical method, or a combination thereof.
  • steps (102), (104), (106), (108) and (112) are carried out at the same geographical location (e.g., within about 2 miles of one another).
  • steps (102), (104), (106), (108) and (112) are carried out at different geographical locations (e.g., at least about 2 miles from one another).
  • the product carbonates from these reactions may provide neutralization to sulfide compounds or minerals present in the reacted mine waste (e.g., reacted tailings), producing oxides and sulfate minerals and thus reducing the potential for the generation of acid drainage and metal leachate from the reacted mine wastes (e.g., reacted tailings).
  • the present invention provides for one or more utilities and benefits in the mine industry. For example, the present invention effectively:
  • (1) provides for mineral sequestration of CO 2 , whereby CO 2 reacts with metal cations in a mine waste stream to form carbonate minerals,
  • mine wastes e.g., tailings

Abstract

A method of carbon-dioxide mineral sequestration using mine waste and recovering valuable metal from the mine waste that includes: (a) contacting a mine waste stream and water to form a slurry; (b) contacting, in a reaction vessel, the slurry and CO2 to provide a reacted slurry; (c) separating the reacted slurry into solids, liquid and gas; (d) recovering metals from the reacted slurry, and (e) recycling CO2 from the separated gas.

Description

CARBON-DIOXIDE MINERAL SEQUESTRATION USING MINE
WASTE
Cross-Reference to Related Applications
This application claims the priority of U.S. Ser. No. 61/252,289, filed Oct. 16, 2009, which is incorporated herein by reference in its entirety. Field of the Invention
This invention relates to carbon-dioxide mineralogical sequestration using mine waste.
Background of the Invention
Mining is an industry that produces metals essential to maintaining and improving this country's high standard of living but has in many instances a negative environmental legacy due to the water and air pollution created by the voluminous amount of mine waste it generates and the large amount of power it consumes in extracting and beneficiating ore, respecitively. Mine Waste is known to produce acid mine drainage and leach heavy metals to surface and groundwaters. The conversion of fossil fuels to power mining operations, as well as industry in general, results in emission of a large amount of CO2 into the atmosphere. Carbon dioxide is a primary greenhouse gas. It is believed that much of the observed temperature increases since the early to mid-20th century has been caused by increasing concentrations of greenhouse gases, primarily CO2, generated from human activity such as the burning of fossil fuels.
Considering the vital role of both fossil fuels and mining to the national economy and security, there is an urgent need to develop an effective methodology for carbon dioxide and overall carbon management. Carbon management involves steps including capturing, transporting, and securely storing carbon emitted from sources. The storing of carbon is a process known as carbon sequestration. Any viable system for sequestering carbon must be effective and cost-competitive, stable for long-term storage, and environmentally benign. Given the magnitude of carbon reductions needed to stabilize the atmosphere (nearly 1 gigaton of carbon/year by 2025 and 4 gigatons of carbon/year by 2050), CO2 capture and sequestration appears to be the most feasible method for reducing carbon emissions while maintaining the continued large-scale usage of fossil fuels and the supply of vital minerals and metals. See, e.g., U.S. Patent Application Publication 2005/0180910.
Summary of the Invention
A method for mineralogically sequestering carbon dioxide (CO2) using mine waste includes: (a) contacting a mine waste stream and water to form a slurry, (b) contacting, in a reaction vessel, the slurry and CO2, to provide a reacted slurry, (c) separating the reacted slurry into solids, liquid, and gas and (d) recycling CO2 from the separated gas. The method can optionally include at least one of (e)-(g): (e) recovering metal from the separated liquid, (f) recycling water from the liquid, and (g) utilizing the separated solids as a value product.
An apparatus for sequestering mine waste includes: (a) a source of a slurry of a mine waste stream and water, wherein the mine waste stream comprises at least one of dry mine waste, dry tailings, wet tailings or wet hydrometallurgical residue (HMR); (b) a source of carbon dioxide; (c) a reaction vessel, wherein the slurry and CO2, are heated at a temperature of about 100°F (37.8°C) to about 750°F (399°C), and at a pressure of at least about 1100 psi
(74.9 atm), for a period of time of about 1 minute to about 10 hours, to provide a reacted slurry; and (d) a separator for separating the reacted slurry into solids, liquid and gas.
The apparatus may further include at least one or more of the following (e) a recyclor for recycling CO2 from the separator back to the mine waste stream; (f) a recoveror for recovering metal from the separated liquid; or (g) a recyclor for recycling water from the liquid back to the mine waste stream.
The method effectively: (a) utilizes CO2 produced by an electric power plant that relies upon the combustion of fossil fuels, (b) utilizes CO2 produced by a facility that burns fossil fuels, (c) utilizes CO2 generated by a power generation plant or captured from the atmosphere by a CO2 extraction process, (d) lowers the carbon footprint of a mining operation, (e) lowers the carbon footprint of an electric power plant, (f) lowers the carbon footprint of a facility that burns fossil fuels, (g) converts non-reacted mine waste to high value metal, (h) converts non- reacted mine waste to useful material, (i) converts non-reacted mine waste to a value product, (j) recycles water in a mining operation, (k) recycles
hydrometallurgical residue produced from ore beneficiation, tailings from ore beneficiation, and mine waste produced from mining operations, (1) provides for mineral sequestration of CO2, whereby CO2 reacts with metal cations and minerals in a mine waste stream to form solid carbonate minerals, (m) provides for mineral carbonation of CO2, (n) provides for carbon sequestration, (0) provides for environmentally safe and stable materials (e.g., solid carbonate minerals) over a geological time frame, (p) produces mineral carbonates from non-reacted mine waste, (q) provides for a mineralogical fixation of CO2 over a geological time frame, (r) transfers or trades carbon credit, (s) collects, processes, transports, manages and recycles mines wastes (e.g., tailings) generated at a mine, or any combination thereof, thereby avoiding the negative environmental legacy issues associated with the disposal of mine waste or (u) produces useable or valuable metals and minerals after all chemical reactions relating to the mineral sequestration of CO2 has taken place in the mine waste (e.g., tailings), or any combination thereof.
Brief Description of the Drawings
Embodiments of the invention may be best understood by referring to the following description and accompanying drawings which illustrate such embodiments. The numbering scheme for the Figures included herein are such that the leading number for a given reference number in a Figure is associated with the number of the Figure. Reference numbers are the same for those elements that are the same across different Figures. For example, a block flow diagram depicting the mine waste stream (101) can be located in Figure 1. However, reference numbers are the same for those elements that are the same across different Figures. In the drawings:
Figure 1 illustrates a block flow diagram depicting carbon-dioxide sequestration in recovering high value metals from mine waste.
Figure 2 illustrates a block flow diagram depicting carbon-dioxide sequestration in recovering high value metals from mine waste. Detailed Description of the Invention
Reference will now be made in detail to certain claims of the invention, examples of which are illustrated in the accompanying structures and formulas. While the invention will be described in conjunction with the enumerated claims, it will be understood that they are not intended to limit the invention to those claims. On the contrary, the invention is intended to cover all alternatives, modifications, and equivalents, which may be included within the scope of the invention as defined by the claims.
References in the specification to "one embodiment", "an embodiment", "an example embodiment", etc., indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.
The presently disclosed subject matter relates to carbon-dioxide sequestration using mine waste and the recovery of high value metals or minerals from mine waste. When describing the carbon-dioxide sequestration process and the recovery of high value metals or minerals from mine waste, the following terms have the following meanings, unless otherwise indicated.
In a specific embodiment, the sequestration of C02 using mine waste comprises a method of extracting and beneficiating ore to produce metals in a sustainable and environmentally friendly manner by locating, for example in the same geographical area, a carbon dioxide producing power plant and a metal mine; using the electricity generated by the power plant to crush, grind, beneficiate the ore. In another embodiment, the electricity and carbon dioxide can be provided by a remote power plant. Typically, the ore is ground to a particle size of about 125 μιη (microns) or less. The metal is then recovered from the finely ground ore by means known in the art and often specific for any one particular metal. An aqueous slurry of the finely ground tailings and the carbon dioxide are then mixed and heated under pressure in a flow reactor. Unrecovered or undesired minerals in the tailings, such as magnesium, iron, and calcium silicates (e.g., olivine, pyroxene, and plagioclase), react with the carbon dioxide to form insoluble, thermodynamically stable metal carbonate minerals. The insoluble carbonate minerals sequester both the carbon dioxide and metals (e.g., magnesium, iron, calcium). The insoluble magnesium, iron, and calcium carbonate minerals are non-reactive and can be safely recycled or disposed of (e.g., by filling in old mine pits). The carbonate minerals in the reacted mine waste (e.g., reacted tailings) may neutralize any existing sulfide mineral component of the reacted carbonate-based mine waste (e.g., tailings). This method provides an environmentally friendly and sustainable way to mine and produce valuable metals and minerals while safely disposing of two of the most environmentally unfriendly by-products of mining: the carbon dioxide and non- reacted mine waste (e.g., non-reacted tailings). In addition, no additional power is generally required to treat the tailings before reaction with carbon dioxide in the flow reactor as this has already been done by the mining operation during the beneficiation process.
In a specific embodiment, the reaction takes place at an elevated temperature (e.g., 100-750°F), and at an elevated pressure (e.g., at least about 1100 psi).
In a specific embodiment the ore is an ultramafic or basalt cumulate with associated segregations of metals or minerals containing one or more value metals like nickel, copper, cobalt, platinum group elements (PGE), and gold. One location of this ore is in the Duluth Complex of northern Minnesota.
A specific embodiment includes an apparatus for sequestering C(¾ using mine waste comprising: (a) a source of a slurry of a mine waste stream and water, wherein the mine waste stream comprises at least one of dry mine waste, dry tailings, wet tailings, dry hydrometallurgical residue, and wet
hydrometallurgical residue; (b) a source of carbon dioxide; (c) a reaction vessel, wherein the slurry and C02, are heated at a temperature of about 100°F (37.8°C) to about 750°F (399°C), and at a pressure of at least about 1 100 psi (74.9 atm), for a period of time of about 1 minute to about 10 hours, to provide a reacted slurry; and (d) a separator for separating the reacted slurry into solids, liquid and gas.
The apparatus may further include one or more of the following (e) a recyclor for recycling CO2 from the separator back to the mine waste stream; (f) a recoveror for recovering metal from the separated liquid; or (g) a recyclor for recycling water from the liquid back to the mine waste stream.
In specific embodiments of the invention, the source of at least some of the C02 is an electric power plant that relies upon the combustion of fossil fuels, another facility that burns fossil fuels, by extraction from the atmosphere, or any combination thereof.
In a specific embodiment the reaction vessel is a pipeline that is of sufficient length, strength, and capacity to permit the reaction among the carbon dioxide, water, and mine waste to occur. In one embodiment, calcium, iron and magnesium silicates within the mine waste react with carbon dioxide to form calcium, iron, or magnesium carbonate. For example, a reaction vessel capable of withstanding a temperature of about 100°F (37.8°C) to about 750°F (399°C), and at a pressure of at least about 1100 psi (74.9 atm) is useful.
In a specific embodiment, the water is separated from the solid and gas using a separator. In one embodiment the separator comprises a settling pond. Upon exiting the reaction pipeline the liquid may be discharged into, for example, a settling pond to allow the solids and liquid to separate. The liquid may then be treated to recover suspended or dissolved metals or minerals— such as by filtration or precipitation using various compounds. The water may then be purified and recycled via pipeline to the mine waste stream and used to form additional slurry.
The separator may also include a device for separating the gas from solid and liquid. These devices may be storage tanks fed, for example, by bleed valves that reduce the pressure in the reaction vessel. The various gasses formed by the reaction may be separated, for example, by fractionation, condensation, or by further reaction with added materials. The carbon dioxide may be recovered, purified and recycled via pipeline back to the mine waste stream and used to react with additional mine waste.
Unless stated otherwise, the following terms and phrases as used herein are intended to have the following meanings:
"Acid" refers to a compound that donates a hydrogen ion (H+) to another compound (called a base). When dissolved in water, acids give a solution with a hydrogen ion activity greater than that of pure water, i.e. a pH less than 7.0. Common mineral acids include, e.g., sulfuric acid, hydrochloric acid, nitric acid, and perchloric acid. Common organic acids include, e.g., acetic acid (in vinegar), citric acid, ascorbic acid, and toluene sulfonic acid. Alternatively, an acid can refer to a substance that accepts a pair of electrons (Lewis Acid) from another compound. Additional suitable acids include, e.g., orthophosphoric acid, oxalic acid, formic acid, lactic acid ammonium hydrogen sulfate, acetic acid, and mixtures thereof.
"Agitates" refers to the act of putting a material into motion with a turbulent force. Agitation can be accomplished by various means, as for example, by rotation, vibration, shaking, or stirring. Agitation can also refer to the contacting of two or more materials to insure mixing.
"Amphiboles" refers to a group of generally dark-colored rock- forming inosilicate minerals, composed of double chain Si04 tetrahedra, linked at the vertices and generally containing ions of iron and/or magnesium in their structures. Amphiboles crystallize into two crystal systems, monoclinic and orthorhombic. In chemical composition and general characteristics, they are similar to the pyroxenes. The chief differences from pyroxenes are that (i) amphiboles contain essential hydroxyl (OH) or halogen (F, CI) and (ii) the basic structure is a double chain of tetrahedra (as opposed to the single chain structure of pyroxene).
"Atmosphere" refers to the layer of gases that surround the earth by gravity, and such gases are retained for a longer duration if gravity is high and the atmosphere's temperature is low. The atmospheric composition on Earth is largely governed by the by-products of the very life that it sustains. Earth's atmosphere contains roughly (by molar content/volume) 78.08% nitrogen, 20.95% oxygen, a variable amount (average around 0.247%, National Center for Atmospheric Research) water vapor, 0.93% argon, 0.038% carbon dioxide, and traces of hydrogen, helium, and other "noble" gases (and of volatile pollutants).
"Base" refers to a chemical compound that provides a hydroxyl ion (OFT) when dissolved in water. A base gives a solution with a hydrogen ion activity less than that of pure water, i.e. a pH greater than 7.0. Common mineral bases include, e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonium hydroxide. Common organic bases include, e.g., amines, such as triethylamine. Alternatively, a base can refer to a substance that donates a pair of electrons (Lewis Base). "Beneficiation" in mining refers to a variety of processes whereby extracted ore from mining is separated into desired metals or minerals and tailings, the metals and minerals are suitable for further processing or direct use. The tailings are discarded.
"Carbon dioxide" or "CO2" refers to a chemical compound composed of two oxygen atoms covalently bonded to a single carbon atom. It is believed that carbon dioxide is a "greenhouse" gas that is a source of global warming.
"Carbon footprint" refers to the total set of greenhouse gas (GHG) emissions caused directly and indirectly by an individual, organization, event, or product. For simplicity of reporting, it is often expressed in terms of the amount of carbon dioxide, or its equivalent of other GHGs, emitted. The carbon footprint is a subset of the ecological footprint. Typically, the larger the carbon footprint, the more greenhouse gasses are emitted.
"Catalyst" refers to a chemical substance that increases (or decreases) the rate of a chemical reaction. A catalyst is not consumed by the reaction itself.
"Chelating agent" refers to compounds that form bonds (or other attractive interactions) between two or more separate binding sites within the same ligand and a single central atom. An example of a chelating agent is EDTA (ethylenediamine tetraacetic acid, which is a chelating agent for Ca2+ and Fe3+ cations. Additional suitable chelating agents include, e.g., acetic acid, oxalic acid, ascorbic acid, phthalic acid, and salts thereof. In specific embodiments, the chelating agent is chosen from one or more compounds that provide anionic groups in aqueous solution selected from the group of ethylene- diamine, acetate, glycolate, S2O3 "2, F", SO4"2, OH", picolinate, glycine, glutamate, and malonate.
"Clinopyroxene" refers to monoclinic crystalline form of pyroxene.
"CO2 sequestration" refers to the storage of carbon dioxide in a solid material or mineral through chemical, biological, or physical processes. It is a geoengineering technique for the long-term storage of carbon dioxide or other forms of carbon, for the mitigation of global warming. Methods of CO2 sequestration include using subsurface saline aquifers, reservoirs, ocean water, aging oil fields, and mineralogical reactions to form insoluble
thermodynamically stable carbonates. "Combustion" or "burning" refers to the complex sequence of exothermic chemical reactions between a fuel (usually a hydrocarbon) and an oxidant accompanied by the production of heat or both heat and light in the form of either a glow or flames, appearance of light flickering. Burning of coal, natural gas, or wood are examples of combustion.
"Contacting" refers to the coming together or touching, as of objects or surfaces.
"Dry tailings" refers to the remaining portion of an ore consisting of finely ground rock after some or all of the desired material, such as a metal, has been extracted. Dry tailings are typically considered a waste product of mining.
"Dry mine waste" refers to rock which contains little if any of the desired material in economically recoverable quantities and containing virtually no (e.g., less than about 5 wt.%) process liquid. Mine Waste (e.g., non-ore rock or overburden) is often used to build an embankment to retain tailings. Dry mine waste is typically considered a waste product of mining.
"Duluth Complex" refers to a geologic formation in northern Minnesota. It is one of the largest intrusions of gabbro on earth, and one of the largest layered ultramafic and basaltic intrusions known. It covers an area of 4715 km2. The lower portion of the intrusion consists of ultramafic cumulates with associated segregations of nickel, copper, cobalt, platinum group elements
(PGE), gold, and silver along with deposits of other valuable metals. Many of these metals are in the form of sulfide minerals. Where the Duluth Complex hosts these metals and/or minerals in concentrations that make then
economically valuable to mine they constitute an ore referred to as the Duluth Complex ore.
"Electric power plant" or "power generation plant" refers to an industrial facility for the generation of electric power. They are also often referred to as a generating station, power plant, or powerhouse. The energy needed to operate a power plant can be provided in many ways, by falling water (hydroelectric power plants), by burning fossil fuels (fossil fuel power plants), by radioactive decay (nuclear power plants), by wind (wind farms).
"Electric resistance" refers to the measure of an object's opposition to the passage of a steady electric current. The unit of resistance is the ohm. "Electro winning" also called electroextraction, refers to the
electrodeposition of metals from their ores that have been put in solution or liquefied. In electrowinning, a current is passed from an inert anode through a liquid leach solution containing the metal so that the metal is extracted as it is deposited in an electroplating process onto the cathode.
"Ferrous oxide" refers to iron(II) oxide, also known as iron
oxide/oxidized iron or more commonly rusted iron. It is one of the iron oxides. It is a black-colored powder with the chemical formula FeO. It consists of the chemical element iron in the oxidation state of 2+ bonded to oxygen.
"Fossil fuel" refers to fuels formed by natural resources such as anaerobic decomposition of buried dead organisms. These fuels contain high percentage of carbon and hydrocarbons. Fossil fuels range from volatile materials with low carbon:hydrogen ratios like methane (natural gas), to liquid petroleum (oil), to nonvolatile materials composed of almost pure carbon (anthracite coal). The age of the buried dead organisms and their resulting fossil fuels is typically millions of years, and sometimes exceeds 650 million years.
"Gangue" in mining refers to the commercially worthless material (i.e., minerals and metals) that overlies, surrounds, or is closely mixed with, a wanted mineral or metal in an ore deposit. Such materials that were once thought of as gangue were dumped as tailings.
"Gas" refers to a state of matter, consisting of a collection of particles (molecules, atoms, ions, electrons, etc.) without a definite shape or volume that are in more or less random motion. Steam is an example of a gas.
"Geological time frame" refers to the period of time that denotes Earth's history, past, present, and future. It is used by geologists, paleontologists, and other earth scientists to describe the timing and relationships between events that have occurred during the history of the Earth. It is composed of eons. Eons are divided into eras, which are in turn divided into periods, epochs, and ages.
"Gradient" refers to the rate of change with respect to distance of a variable quantity, as temperature or pressure, in the direction of maximum change. An example is a pipe heated at one end in which a temperature gradient would be present along the length of the pipe. Another example is a pipe elevated at one end in which a height gradient would be present along the length of the pipe. The presence of any suitable gradient will create a pressure differential due to gravity along a gradient to effectively traverse the slurry within (or along) the reaction vessel.
"High pressure" refers to a pressure equal to or greater than about 1,000 psi (74.9 atm). High pressure can result in chemical reactions occurring that would not occur to an appreciable degree at atmospheric pressure or that would take longer to occur.
"High temperature" refers to a temperature equal to or greater than about 100°F (37.8°C). High temperature can result in chemical reactions occurring that would not occur to an appreciable degree at ambient temperature or that would take longer to occur.
"Induction" refers to the production of voltage across a conductor situated in a changing magnetic field or a conductor moving through a stationary magnetic field.
"Liquid" refers to a state of matter characterized by particles that are loose and can freely form a distinct surface at the boundaries of its bulk material. A liquid has a definite volume but its shape is determined by the container it fills. Water is an example of a liquid.
"Mafic silicate" refers to silicate minerals, magmas, and rocks which are relatively high in the heavier elements. The term is derived from using the MA from magnesium and the FIC from the Latin word for iron, but mafic magmas also are relatively enriched in calcium and sodium.
"Metal cation" refers to a positively charged metal atom that moves toward the cathode (or negative pole) during electrolysis. Thus, a metal cation is a positively charged ion with more protons than electrons. Fe2+ and Fe3+ are examples of cations.
"Metal" refers to an element, compound, or alloy characterized by high electrical conductivity. In a metal, atoms readily lose electrons to form positive ions (cations); those ions are surrounded by delocalized electrons, which are responsible for the conductivity. The compound thus produced is held by electrostatic interactions between the ions and the electron cloud, which are called metallic bonds. Metals usually form cations through electron loss. Metals are further classified by elemental position on the periodic table with certain groups of metals exhibiting similar chemical behavior. Sodium (Na), potassium (K), and lithium (Li) are examples of alkali metals; Calcium (Ca), magnesium (Ng), and Barium (Ba) are examples of alkali earth metals; and chromium (Cr), iron (Fe), copper (Cu), nickel (Ni), platinum (Pt), silver (Ag), and gold (Au) are examples of transition metals, (we can incorporate "Rare earth metal" here or leave it as is later in this section)
"Microwave" refers to electromagnetic waves with frequencies between
300MHz (0.3 GHz) and 300 GHz, typically between 1 GHz and 300 GHz.
"Mine waste stream" refers to the aggregate flow of mine waste material from generation to treatment to final disposition. Tailings and dry mine waste are typically part of the mine waste stream. In specific embodiments, the mine waste stream is processed (e.g., by grinding) to an average particle size of less than about 500 microns, or is physically activated by application of ultrasonic energy or microwave energy.
"Mine" refers to a site where the extraction of minerals, metals, or other geological materials from the earth, usually from an ore body, vein, or (coal) seam takes place. Materials recovered by mining include base metals, precious metals, iron, uranium, coal, diamonds, limestone, oil shale, rock salt, and potash. Any material that cannot be grown through agricultural processes, or created artificially in a laboratory or factory, is usually mined. Mines can be subsurface (underground mines) or surface (strip or open pit mines).
"Mineral" refers to an element or chemical compound that is normally crystalline and that has been formed as a result of geological processes. It has a characteristic chemical composition, a highly ordered atomic structure, and specific physical properties. Minerals range in composition from pure elements and simple salts to very complex silicates with thousands of known forms. The study of minerals is called mineralogy. A rock is an aggregate of one or more minerals. For example, limestone is a sedimentary rock composed almost entirely of the mineral calcite (the most stable polymorph of calcium carbonate (CaCOs). The Duluth Complex is host to ore which contains, among other minerals, chalcopyrite, cubanite, pentlandite, pyrite, magnetite, ilmenite, olivine, pyroxene, and plagioclase. Most of the copper in the Duluth Complex ore is in the sulfide minerals chalcopyrite and cubanite. Most of the nickel in the Duluth Complex ore is in the sulfide mineral pentlandite.
"Mine waste" refers to any waste material, including but not limited to surface overburden, non-ore rock, lean ore, tailings, or hydrometallurgical residue generated during the process of excavation and beneficiation of ore that is stored, discarded, or disposed of. Mine waste is a known source of pollution due to its potential to generate acid mine drainage and leach metals into the environment polluting soils, surface water, and groundwater.
"Nuclear power reactor" refers to a device in which nuclear chain reactions are initiated, controlled, and sustained at a steady rate. Nuclear power reactors are often used in electric power plants as the energy source for the generation of electricity. Heat generated from radioactive decay is used to heat water to provide steam to drive a turbine that generates electricity.
"Olivine" refers to a series of magnesium and iron silicate minerals with the formula (Mg,Fe)2Si04. They can range from forsterite, Mg2Si04 to fayalite, Fe2Si04.
"Ore beneficiation" refers to a variety of process whereby extracted ore from mining is reduced to particles that can be separated into minerals or metals and waste material (e.g., tailings), the former suitable for further processing or direct use.
"Orthopyroxene" refers to the orthorhombic crystalline form of pyroxene.
"Outlet protrusion" refers to something projecting or jutting out from which material flows out or can be obtained.
"Pipe" refers to a tube or hollow cylinder used to convey materials or as a structural component. Both pipe and tube imply a level of rigidity and permanence, whereas a hose is usually portable and flexible. The pipe can be manufactured from any suitable material. For example, when the contents of the pipe are heated at an elevated temperature, the pipe can be manufactured from materials that are suitable for high temperatures. Likewise, the pipe can be manufactured from materials that are suitable for high pressures.
"Plagioclase" refers to a series of tectosilicate minerals within the feldspar family. Rather than referring to a particular mineral with a specific chemical composition, plagioclase is a solid solution series, more properly known as the plagioclase feldspar series The series ranges from albite to anorthite endmembers (with respective compositions NaAlSisOs to CaAl2Si208), where sodium and calcium atoms can substitute for each other in the mineral's crystal lattice structure. Plagioclase in hand samples is often identified by its polysynthetic twinning or 'record-groove' effect.
"Platinum group metal" (PGM) or "platinum group element" (PGE) refers to one or more of six metallic elements clustered together in the periodic table. These elements are all transition metals, lying in the d-block (groups 8, 9, and 10, periods 5 and 6). The six platinum group metals are ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt). They have similar physical and chemical properties, and tend to occur together in the same mineral deposits. They have outstanding catalytic properties, are highly resistant to wear and tarnish, resistant to chemical attack, have excellent high-temperature characteristics, and stable electrical properties. All these properties have are useful for industrial applications.
"Pyroxene" refers to a group of rock- forming silicate minerals found in many igneous and metamorphic rocks. They share a common structure consisting of single chains of silica tetrahedra and they crystallize in the monoclinic and orthorhombic systems. Pyroxenes have the general formula XY(Si,Al)206, where X represents calcium, sodium, iron+2 and magnesium and more rarely zinc, manganese and lithium and Y represents ions of smaller size, such as chromium, aluminum, iron+3, magnesium, manganese, scandium, titanium, vanadium and even iron+2.
"Radiofrequency" refers to a portion of the electromagnetic spectrum within the range of about 3 Hz to 300 GHz. This range corresponds to the frequency of alternating current electrical signals used to produce and detect radio waves.
"Rare earth metal" or "rare earth element" refers to one or more of seventeen chemical elements in the periodic table, namely scandium (Sc), yttrium (Y), and the fifteen lanthanoids; Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb), and Lutetium (Lu).
"Reaction vessel" refers to a reactor designed to contain a reaction, such as a chemical reaction. Pipes, tanks, and carboys are types of reaction vessels.
"Recycle" refers to the act of employing a material or substance that is obtained in a chemical reaction or process (i.e., as a starting material, reagent, solvent or catalyst) for a preceding step in that reaction or process. Thus, that material or substance is reused in the overall process. The material or substance can be reused or recycled as many times as the overall process is carried out. It is widely accepted that recycling prevents the waste of potentially useful materials, reduces the consumption of fresh raw materials, reduces energy usage, reduces air pollution (from incineration) and water pollution (from landfilling) by reducing the need for "conventional" waste disposal, and lower greenhouse gas emissions as compared to virgin production.
"Sequestration" refers to the storage of a material in a solid material through chemical, biological, or physical processes. For example carbon dioxide can be sequestered by reaction with a mineral to form an insoluble carbonate salt. Another example is sequesteration of metals by reaction to form insoluble salts.
"Serpentine" refers to a group of common rock- forming hydrous magnesium iron phyllosilicate ((Mg, Fe)3Si20s(OH)4) minerals; they may contain minor amounts of other elements including chromium, manganese, cobalt, and nickel.
"Slurry" refers to a thick suspension of solids in a liquid. Solid materials are often transported in a pipeline as a slurry.
"Carbonate mineral" refers to minerals containing the carbonate (CO3 2 ) anion. Examples are calcium carbonate (CaC03, limestone),calcium magnesium carbonate (CaMg(C03)2, dolomite), magnesium carbonate (MgC03, magnesite), and iron carbonate (FeCC^, siderite). Many carbonate salts are insoluble in water. Notable exceptions include sodium, potassium, and ammonium carbonates.
"Solids" refers to the state of matter characterized by a distinct structural rigidity and resistance to deformation (that is changes of shape and/or volume). The particles in a solid (ions, atoms or molecules) are packed closely together. The forces between particles are strong enough so that the particles cannot move freely but can only vibrate. As a result, a solid has a stable, definite shape, and a definite volume. Ice is an example of a solid.
"Tailings" in mining refers to gangue or the fine grained mineral remains of ore, once most of the valuable metals and minerals have been removed in the ore beneficiation process. Tailings often contain desired metals or minerals but at amounts that are uneconomical to recover. As economics change and new technologies develop, tailings can be recycled to recover additional desired materials. Tailings are a known source of pollution due to their potential to generate acid mine drainage and leach metals into the environment.
"Value product," "value metal," or "value mineral" refers to a waste material that has been turned into a material that is either useful or can be sold at a profit, for example by recovery of additional metals from the mine waste.
"Wet chemical method" refers to methods of extracting metals from their ores using chemicals and solutions in one or more steps. Typical steps include leaching, solution concentration of the metal, and metal recovery. Metal recovery can be by precipitation.
"Hydrometallurgical residue" or "HMR" refers to the residual aqueous solution, rock, and tailings left over after an aqueous solution has been used to extract the desired material, such as a metal, from an ore. For example, the wet aqueous solution can be the leachate from which the desired metal or metal chelate has been removed.
"Wet tailings" refers to the remaining portion of an ore consisting of finely ground rock and process liquid after some or all of the desired material, such as a metal, has been extracted. Wet tailings are a waste product of mining.
As used herein, "separating" refers to the process of removing solids, liquid and/or a gas from at least one of the other. The process can employ any technique known to those of skill in the art, e.g., decanting the mixture, filtering the solids from the mixture, or a combination thereof.
As used herein, "filtering" refers to the process of removing solids from a mixture by passing the liquid through a filter, thereby suspending the solids on the filter.
As used herein, "decanting" refers to the process of pouring off a liquid without disturbing the sediment, or the process of pouring off a liquid with a minimal disturbance of the sediment.
As used herein, "purifying" refers to the process of ridding a solid substrate (e.g., a metal) of impurities. Suitable methods of purifying include, e.g., washing, recrystallizing, and drying.
As used herein, "alkali metal" refers to metals of Group LA of the Periodic Table of Elements, e.g., sodium (Na) and potassium (K). As used herein, "alkaline earth metal" refers to metals of Group IIA of the Periodic Table of Elements, e.g., magnesium (Mg) and calcium (Ca).
Figures 1 and 2 illustrate a block flow diagram depicting mineralogical carbon-dioxide sequestration using mine waste and the recovery of high value metals from mine waste.
As shown in step (102), a slurry (103) is formed from the mine waste stream (101). While any suitable and appropriate substance can be employed to form the slurry (103) from the mine waste stream (101), water is a particularly suitable substance. In specific embodiments, the mine waste stream (101) will include the requisite amount of water such that the mine waste stream (101) is effectively a slurry (103). In such an embodiment, the addition of water is not needed. Alternatively, water can be added to the rock waste stream (101) to form the slurry (103). When water is employed to form the slurry (103) from the mine waste stream (101), any suitable amount of water can be employed.
In a specific embodiment of the present invention, the mine waste stream
(101) includes at least one of dry mine waste, dry tailings, wet tailings and wet hydrometallurgical residue (HMR). In other specific embodiments of the invention, the mine waste stream (101) includes olivine, orthopyroxene, clinopyroxene, plagioclase, amphiboles, ferrous oxide, serpentine minerals, or a combination thereof. In other specific embodiments of the invention, the mine waste stream (101) includes silicon dioxide (S1O2), aluminium oxide (AI2O3), titanium(IV) oxide (T1O2), calcium oxide (CaO), iron (Fe), magnesium oxide (MgO), manganese(II) oxide (MnO), sodium oxide ( a20), potassium oxide (K20), sulfur (S), or a combination thereof. Some of the oxides may be too reactive to exist in a waste stream, e.g., (Na20), (K 0).
In a specific embodiment of the present invention, the slurry (103) includes naturally occurring magnesium (Mg) and calcium (Ca) containing minerals. In other specific embodiments of the invention, the slurry (103) includes magnesium carbonate minerals, iron carbonate minerals, calcium carbonate minerals, or a combination thereof. In other specific embodiments of the invention, the slurry (103) includes mafic silicate materials.
In a specific embodiment of the present invention, any dry mine waste present in the mine waste stream (101) is ground or crushed, prior to contacting with water. In a specific embodiment of the present invention, the slurry is made up of mine waste (e.g., tailings) from the excavation and beneficiation of Duluth Complex ore,
In a specific embodiment of the present invention, the temperature of about 100°F (37.8°C) to about 750°F (399°C) in step (104) is achieved utilizing electric resistance, induction, microwave, radiofrequency, or a combination thereof.
In a specific embodiment of the invention, the slurry (103) includes liquid and solids, in a weight ratio of about 1 :3, respectively, to about 3:2, respectively.
As shown in step (104), a reacted slurry (105) is formed from the slurry (103). In a specific embodiment, CO2 is employed at a relatively elevated temperature (e.g., 100-750°F), and at an elevated pressure (e.g., at least about 1100 psi). The CO2 can contact the slurry (103) to provide the reacted slurry (105), for any suitable period of time. For example, the C(¾ can contact the slurry (103) to provide the reacted slurry (105), for at least about 1 minute, for at least about 1 hour, or for about 1 minute to about 10 hours.
In specific embodiments of the invention, the CO2 in step (104) chemically reacts with the slurry (103), creates a pressure differential along a gradient to traverse the slurry (103) within the reaction vessel, agitates the slurry (103) within the reaction vessel, provides a reactant medium for the slurry (103) thereby fluidizing the slurry (103), or any combination thereof.
In specific embodiments of the invention, the source of at least some of the CO2 in step (104) is an electric power plant that relies upon the combustion of fossil fuels, another facility that burns fossil fuels, or extracts CO2 from the atmosphere, or any combination thereof.
In specific embodiments of the invention, the slurry (103) and the CO2 are contacted in the presence of at least one of an acid, base, chelating agent, and catalyst.
In a specific embodiment of the invention, an outlet protrusion (e.g., pipe that can be about 100 meters in length) is employed as being at least part of the reaction vessel. In such an embodiment, the pipe will typically be suitable for high temperature, high pressure conditions, or a combination thereof. In another specific embodiment, the pipe is suitable for high temperature and/or high pressure conditions, such that the reacted slurry (105) that is formed is recovered at a geographical location different from the geographical location where step (104) is carried out.
As shown in step (106), the reacted slurry (105) is separated, such the gas (H I), liquids (109) and solids (107) are separated from one another. The separation can employ any suitable and appropriate methods and materials that are commonly used in the industry, and well-known to those of skill in the art.
As shown in step (108), the gas (11 1) that is obtained from the separating (106) can be processed such that at least a portion of CO2 present therein can be recycled or reused in subsequent step (104). That is, in subsequent processing in which reacted slurry (105) is formed from slurry (103), the CO2 that is employed therein can include, at least in part, CO2 that is present in the gas (11 1). It is appreciated that it will be understood by those of skill in the art that such a recycling of CO2 will present numerous environmental, cost and technical advantages.
As shown in optional step (110), the solids (107) obtained from the separation (106) can be converted to value products (1 13).
As shown in step (112), the liquid (109) obtained from the separation (106) can optionally be further separated into water (117) and metal (1 15). The metal (1 15) can optionally be further purified (1 16) to provide purified metal (1 19). Likewise, the water (117) can optionally be recycled or reused in subsequent step (102). That is, in subsequent processing in which a slurry (103) is formed from mine waste stream (101) employing water, that the water employed therein can include, at least in part, water (117) that is present in liquids (109) that was subsequently separated from the metal (115). It is appreciated that it will be understood by those of skill in the art that such a recycling of water (1 17) will present numerous environmental, cost and technical advantages.
In a specific embodiment of the invention, at least about 90 wt.% of water that is employed in the process, is subsequently returned to a mine, i.e., is recycled in subsequent step(s) (102). In other specific embodiment of the invention, at least about 95 wt.% of water that is employed in the process, is subsequently returned to a mine, i.e., is recycled in subsequent step(s) (102). In a specific embodiment of the invention, the metal includes at least one of copper (Cu), nickel (Ni), lead (Pb), silver (Ag), gold (Au), chromium (Cr), cobalt (Co), a rare earth metal, and a platinum group metal.
In a specific embodiment of the invention, the separation of the metal (115) from the water (117) is achieved utilizing electrowinning, a wet chemical method, or a combination thereof.
In a specific embodiment of the invention, steps (102), (104), (106), (108) and (112) are carried out at the same geographical location (e.g., within about 2 miles of one another). Alternatively, steps (102), (104), (106), (108) and (112) are carried out at different geographical locations (e.g., at least about 2 miles from one another).
Although not wishing to be bound by theory, Applicant believes that under the conditions of pressure and temperature described herein, the carbon dioxide reacts with the minerals in the mine waste (e.g., tailings) to form insoluble carbonate minerals. The insoluble carbonate minerals thus formed can safely be stored. Thus, carbon dioxide used to generate power to operate a mine can be removed from the environment. For example when fayalite, Fe2Si04 is treated with carbon dioxide, the following reaction is believed to take place:
Fe2Si04 + 2C02 2FeC03 + Si02
When forsterite, Mg2Si04 is treated with carbon dioxide, the following reaction is believed to take place:
2Si04 + 2C02 2MgC03 + Si02
It is recognized that these two reactions and similar reactions producing metal carbonates may take place through one or more intermediate reactions, by a variety of mechanisms and kinetics, in the presence of other materials, some of which may support or catalyze the reaction, and under one or more influential conditions.
The product carbonates from these reactions may provide neutralization to sulfide compounds or minerals present in the reacted mine waste (e.g., reacted tailings), producing oxides and sulfate minerals and thus reducing the potential for the generation of acid drainage and metal leachate from the reacted mine wastes (e.g., reacted tailings). The present invention provides for one or more utilities and benefits in the mine industry. For example, the present invention effectively:
(a) utilizes CO2 produced by an electric power plant that relies upon the combustion of fossil fuels,
(b) utilizes CO2 produced by a facility that burns fossil fuels,
(c) utilizes CO2 generated by a power generation plant,
(d) lowers the carbon footprint of a mining facility,
(e) lowers the carbon footprint of an electric power plant,
(f) lowers the carbon footprint of a facility that burns fossil fuels,
(g) converts non-reacted mine waste to high value minerals and metals,
(h) converts non-reacted mine waste to useful material,
(i) converts non-reacted mine waste to a value product,
(j) recycles water in a mining operation,
(k) recycles hydrometallurgical residue, tailings, and other mine waste generated from the excavation and beneficiation of the ore,
(1) provides for mineral sequestration of CO2, whereby CO2 reacts with metal cations in a mine waste stream to form carbonate minerals,
(m) provides for mineral carbonation of CO2,
(n) provides for carbon sequestration,
(0) provides for sustainable mining by creating environmentally safe and stable mine waste-derived materials over a geological time frame,
(p) produces mineral carbonates from non-reacted mine waste,
(q) provides for a fixation of CO2 over a geological time frame,
(r) transfers or trades carbon credit,
(s) collects, processes, chemically and physically transforms, transports, manages and recycles mine wastes (e.g., tailings) generated at a mine, or any combination thereof, thereby avoiding the negative environmental legacy issues associated with the disposal of mine waste, or
(t) reduces the potential for acid rock drainage generated from the sulfide bearing minerals present in mine waste, thereby reducing the environmental legacy issues associated with the disposal of mine waste.
(u) produces useable or valuable metals and minerals after all chemical reactions relating to the mineral sequestration of CO2 has taken place in the mine waste (e.g., tailings). All publications, patents, and patent applications are incorporated herein by reference. While in the foregoing specification this invention has been described in relation to certain specific embodiments thereof, and many details have been set forth for purposes of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details described herein may be varied considerably without departing from the basic principles of the invention.
The methods described herein can be carried out employing any of the applicable techniques known to those of skill in the art of chemical and/or process engineering.
Numerous modifications and variations of the present invention are possible in light of the teachings herein. It is therefore to be understood that within the scope of the appended claims, the present invention may be practiced otherwise than as specifically described herein.

Claims

Claims
1. A method comprising:
(a) contacting a mine waste stream and water to form a slurry, wherein the mine waste stream comprises at least one of dry mine waste, dry tailings, wet tailings, wet hydrometallurgical residue, or dry hydrometallurgical residue;
(b) contacting, in a reaction vessel, the slurry and CO2, at a temperature of about 100°F (37.8°C) to about 750°F (399°C), and at a pressure of at least about 1100 psi (74.9 atm), for a period of time of about 1 minute to about 10 hours, to provide a reacted slurry;
(c) separating the reacted slurry into solids, liquid and gas;
(d) recycling CO2 from the separated gas;
and at least one of (e)-(h):
(e) recovering metal from the separated liquid;
(f) recycling water from the liquid;
(g) utilizing the separated solids as a value product; and
(h) utilizing the separated solids as inert fill material.
2. The method of claim 1, wherein the slurry in step (a) comprises naturally occurring magnesium (Mg), iron (Fe), and calcium (Ca) containing minerals.
3. The method of claim 1, wherein the reacted slurry in steps (b) and (c) comprise magnesium carbonate minerals, iron carbonate minerals, calcium carbonate minerals, or a combination thereof.
4. The method of claim 1, wherein the mine waste stream comprises mafic silicate materials.
5. The method of claim 1, wherein the mine waste stream comprises olivine, orthopyroxene, clinopyroxene, plagioclase, amphiboles, ferrous oxide, serpentine minerals, or a combination thereof.
6. The method of claim 1, wherein the mine waste stream comprises silicon dioxide (S1O2), aluminium oxide (AI2O3), titanium(IV) oxide (T1O2), calcium oxide (CaO), iron (Fe), magnesium oxide (MgO), manganese(II) oxide (MnO), sodium oxide (Na20), potassium oxide (K20), sulfur (S), or a combination thereof.
7. The method of claim 1, wherein the C02 in step (b) chemically reacts with the slurry, creates a pressure differential along a gradient to traverse the slurry within the reaction vessel, agitates the slurry within the reaction vessel, provides a reactant medium for the slurry thereby fluidizing the slurry, or any combination thereof.
8. The method of claim 1, wherein the source of CO2 in step (b) is an electric power plant that relies upon the combustion of fossil fuels, another facility that burns fossil fuels, by extraction from the atmosphere, or any combination thereof.
9. The method of claim 1, wherein reaction vessel comprises a gradient, to facilitate traversing of the slurry within the reaction vessel.
10. The method of claim 1, wherein in step (b), the slurry and the CO2 are contacted in the presence of a at least one of an acid, base, chelating agent, and catalyst.
11. The method of claim 1, wherein the metal comprises at least one of copper (Cu), nickel (Ni), cobalt (Co), lead (Pb), silver (Ag), gold (Au), chromium (Cr), a rare earth metal, and a platinum group metal.
12. The method of claim 1, wherein any dry waste rock present in the mine waste stream is ground or crushed, prior to contacting with water in step (a).
13. The method of claim 1, wherein the temperature of about 100°F (37.8°C) to about 750°F (399°C) in step (b) is achieved utilizing electric resistance, induction, microwave, radiofrequency, or a combination thereof.
14. The method of claim 1, wherein the recovering of the metal from the separated liquid in step (e) is achieved utilizing electro winning, a wet chemical method, or a combination thereof.
15. The method of claim 1, wherein in step (a), a liquid and solids are formed in a weight ratio of about 1 :3, respectively, to about 3:2, respectively.
16. The process of claim 1, wherein steps (a) - (c) are carried out at the same geographical location.
17. The process of claim 1, wherein steps (a) - (g) are carried out at two or more different geographical locations.
18. The process of claim 17, wherein the two or more different geographical locations are located at least about 2 miles apart.
19. The process of claim 1, wherein step (a) is carried out in a pipe that is suitable for high temperature, high pressure conditions, or a combination thereof.
20. The process of claim 1, wherein step (b) is carried out in a pipe that is suitable for high temperature and/or high pressure conditions, such that the slurry that is formed is recovered at a geographical location different from the geographical location where step (a) is carried out.
21. The process of claim 1 , wherein at least about 90 wt.% of water that is employed in the process, is subsequently returned to a mine.
22. The process of claim 1, wherein the reaction vessel comprises an outlet protrusion.
23. The process of claim 1, wherein the reaction vessel comprises an outlet protrusion, wherein the outlet protrusion comprises a pipe that is at least about 100 meters in length.
24. An apparatus for reacting mine waste comprising:
(a) a source of a slurry of a mine waste stream and water, wherein the mine waste stream comprises at least one of dry mine waste, dry tailings, wet tailings, dry hydrometallurgical residue, or wet hydrometallurgical residue;
(b) a source of carbon dioxide;
(c) a reaction vessel, wherein the slurry and C02, are heated at a temperature of about 100°F (37.8°C) to about 750°F (399°C), and at a pressure of at least about 1 100 psi (74.9 atm), for a period of time of about 1 minute to about 10 hours, to provide a reacted slurry; and
(d) a separator for separating the reacted slurry into solids, liquid and gas.
25. The apparatus of claim 24, further comprising one or more of the following:
(e) a recyclor for recycling CO2 from the separated gas back to the mine waste stream;
(f) a recoveror for recovering metal from the separated liquid; or
(g) a recyclor for recycling water from the liquid back to the mine waste stream.
26. The method of claim 1, that effectively:
(a) utilizes CO2 produced by an electric power plant that relies upon the combustion of fossil fuels,
(b) utilizes CO2 produced by a facility that burns fossil fuels,
(c) utilizes CO2 generated by a power generation plant,
(d) lowers the carbon footprint of a mining facility,
(e) lowers the carbon footprint of an electric power plant,
(f) lowers the carbon footprint of a facility that burns fossil fuels,
(g) converts non-reacted mine waste to high value metal,
(h) converts non-reacted mine waste to useful material,
(i) converts non-reacted mine waste to a value product,
(j) recycles water in a mining operation,
(k) recycles hydrometallurgical residue waste from ore beneficiation and tailings from ore beneficiation, (1) provides for mineral sequestration of CO2, whereby the CO2 reacts with metal cations in a mine waste stream to form solid carbonate minerals,
(m) provides for mineral carbonation of CO2,
(n) provides for carbon sequestration,
(0) provides for environmentally safe and stable materials over a geological time frame,
(p) produces mineral carbonates from non-reacted mine waste,
(q) provides for a fixation of CO2 over a geological time frame,
(r) transfers or trades carbon credit,
(s) collects, processes, transports, manages and recycles mine waste generated at a mine,
(t) reduces the potential for acid rock drainage generated from the sulfide bearing minerals present in mine waste, thereby avoiding the negative environmental legacy issues associated with the disposal of mine waste, or (u) produces useable or valuable metals and minerals after all chemical reactions relating to the mineral sequestration of CO2 has taken place in the mine waste,
or any combination thereof.
PCT/US2010/052532 2009-10-16 2010-10-13 Carbon-dioxide mineral sequestration using mine waste WO2011047070A1 (en)

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