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WO2024020548A2 - Procédés d'obtention de métaux carboneutres ou carbonégatifs à partir de plantes, et compositions associées - Google Patents

Procédés d'obtention de métaux carboneutres ou carbonégatifs à partir de plantes, et compositions associées Download PDF

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Publication number
WO2024020548A2
WO2024020548A2 PCT/US2023/070710 US2023070710W WO2024020548A2 WO 2024020548 A2 WO2024020548 A2 WO 2024020548A2 US 2023070710 W US2023070710 W US 2023070710W WO 2024020548 A2 WO2024020548 A2 WO 2024020548A2
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WIPO (PCT)
Prior art keywords
rock
weatherable
metal
nickel
soil
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Ceased
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PCT/US2023/070710
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WO2024020548A3 (fr
Inventor
Eric Jason MATZNER
Laura R. WASSERSON
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Metalplant Public Benefit Corp
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Metalplant Public Benefit Corp
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Priority to EP23843926.9A priority Critical patent/EP4558651A2/fr
Publication of WO2024020548A2 publication Critical patent/WO2024020548A2/fr
Publication of WO2024020548A3 publication Critical patent/WO2024020548A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium

Definitions

  • the present disclosure relates generally to methods of extracting metals from rocks and sequestering carbon dioxide, and more specifically to methods of using phytomining to extract metals from ultramafic rocks while sequestering carbon dioxide.
  • Carbon dioxide is the dominant greenhouse gas released by human activities and the major contributor to global warming. Carbon sequestration is the process of capturing and storing atmospheric carbon dioxide. It is the only approach that humans can use to actively reduce the amount of carbon dioxide in the atmosphere.
  • geologic carbon sequestration and biologic carbon sequestration two main types of carbon sequestration.
  • Enhanced weathering which includes terrestrial enhanced weathering and oceanic enhanced weathering, is weathering accelerated by spreading finely ground silicate rock onto surfaces. This helps to accelerate chemical reactions between rocks, water and air.
  • Phytomining refers to the use of hyperaccumulator plant species to concentrate metals from soils and subsequently processing the hyperaccumulator biomass to generate useful metal products. Hyperaccumulators are rare plants that draw up metal from the soil on which they grow, and accumulate high levels of metals in their biomass.
  • the metals may comprise nickel, cobalt, chromium or any combination thereof.
  • the methods and systems provided sequester carbon dioxide through a chemical weathering process that results in the release of Mg 2+ ions.
  • the metals are phytomined from serpentinite.
  • Serpentinite is a rock comprising one or more of the serpentine group minerals. Minerals in this group are rich in magnesium and iron. Serpentinite has been called serpentine or serpentine rock, particularly in older geographical texts and in wider cultural settings.
  • serpentinite is a rock comprising one or more of the serpentine group minerals.
  • serpentinite is a rock comprising one or more minerals having the chemical formula D3[Si2Os](OH)4, wherein D is selected from the group consisting of Mg, Fe, Ni, Mn, Al, and Zn.
  • serpentinite is a rock comprising one or more mineral selected from the group consisting of amesite, antigorite, berthierine, brindleyite, caryopilite, chrysotile, cronstedtite, fraipontite, guidottiite, kellyite, lizardite, constructiveuite, and pecoraite.
  • the methods and systems provided utilize plant species that are tolerant to soils having high metal contents.
  • the plants are tolerant of high pH soils.
  • the plants are tolerant of low nutrient soils.
  • the plants are hyperaccumulators of nickel.
  • provided is a method comprising transporting weatherable rock from a quarry, using mechanical activation to grind the weatherable rock to particles to increase reactive mineral surface area, dispersing the weatherable rock particles into the soil within a plot of land, planting nickel hyperaccumulating plants onto the plot of land to capture the nickel released from the weatherable rock during chemical weathering.
  • the presence of the nickel hyperaccumulating plants accelerates the chemical weathering of the weatherable rock.
  • the nickel hyperaccumulating plants may be harvested and further processed to yield a purified nickel composition.
  • the weatherable rock is ground to a particle size suitable to optimize both the rate of chemical weathering and the rate of nickel accumulation in the hyperaccumulating plant.
  • grinding the rock to particles comprises grinding the rock to a size of between about 1 pm and about 10 cm.
  • the weatherable rock comprises serpentine.
  • the weatherable rock comprises serpentinite.
  • the nickel may be nickel metal in oxidation state 0, or any suitable nickel salts and nickel complexes, such as Ni 2+ salts.
  • the nickel is a Ni 2+ salt or complex.
  • the nickel may be in an oxidation state of -1, 0, 1, 2, 3, or 4, or any combination thereof.
  • the weatherable rock may be obtained from the tailings, waste, or overburden from traditional nickel mines.
  • the weatherable rock comprises serpentine.
  • the nickel hyperaccumulating plants are directly irrigated.
  • the irrigation is accomplished using a continuous irrigation system.
  • the irrigation is accomplished using an automated irrigation system.
  • the methods and systems employ hyperaccumulator plants that are capable of growing in high and even pure levels of serpentine and that are be able to survive and accelerate the weathering rate of the serpentine minerals, especially when fertilized and irrigated.
  • a method for obtaining nickel metal comprising mechanically grinding a weatherable rock comprising at least 20% by weight of magnesium, and at least 0.1% by weight of nickel to provide a particulate weatherable rock composition, combining the particulate weatherable rock composition with a soil to provide a weatherable rock-enriched soil, growing a nickel hyperaccumulator plant in the weatherable rock-enriched soil, harvesting the nickel hyperaccumulator plant, and processing the harvested nickel hyperaccumulator plant to provide a substantially pure nickel.
  • processing the harvested nickel hyperaccumulator plant comprises ashing the harvested nickel hyperaccumulator plant to provide a nickel-enriched ash comprising at least 5% nickel by weight, and refining the nickel-enriched ash composition to provide a substantially pure nickel.
  • processing the harvested nickel hyperaccumulator plant comprises heat treating the harvested nickel hyperaccumulator plant to provide a nickel- enriched ash comprising at least 5% nickel by weight, and refining the nickel-enriched ash composition to provide a substantially pure nickel.
  • Mg 2+ is leached from the weatherable rock-enriched soil at a rate faster than the observed rate of stationary ultramafic minerals, or minerals without plants growing in them. In certain embodiments, Mg 2+ is leached at a rate of at least 1% by weight of the total Mg 2+ in the weatherable rock per year from the weatherable rock-enriched soil while the nickel hyperaccumulator plant is growing.
  • the method may be employed for obtaining one or more metals, including nickel, cobalt, chromium or any combination thereof.
  • a plurality of metals are obtained, multiple hyperaccumulator plants suitable for harvesting the metals are employed in the process.
  • a nickel hyperaccumulator plant and a cobalt hyperaccumulator plant are used in the weatherable rock-enriched soil to harvest a combination of nickel and cobalt.
  • At least 10 tonnes of carbon dioxide are sequestered for every tonne of nickel metal that is produced.
  • the weatherable rock comprises ultramafic rock. In some embodiments, the weatherable rock comprises mafic rock. In some embodiments, the weatherable rock comprises less than about 55% silica by weight. In some embodiments, the weatherable rock comprises less than about 45% silica by weight. In some embodiments, the weatherable rock comprises between about 45% and about 55% silica by weight. In some embodiments the weatherable rock comprises one or more minerals selected from the serpentine group. In some embodiments, the weatherable rock comprises olivine. In some embodiments, the weatherable rock comprises serpentinite. In some embodiments, the weatherable rock comprises gabbro or basalt, or a combination. In some embodiments, the weatherable rock comprises a combination of mafic rocks or minerals.
  • the method comprises mining the weatherable rock. In some embodiments, the method comprises transporting the mined weatherable rock from a mining location to a grinding location. In some embodiments, the method comprises mechanically grinding the weatherable rock comprises crushing and/or milling the weatherable rock.
  • the particulate weatherable rock composition has a particle size between 1 pm and 10 cm.
  • the weatherable rock-enriched soil comprises between 10% and 100% particulate weatherable rock composition by weight.
  • the nickel hyperaccumulator plant is a plant belonging to the genus Odontarrhena. In some embodiments, the nickel hyperaccumulator plant is grown inside of a greenhouse. In some embodiments, the nickel hyperaccumulator plant is grown under polyethylene film (e.g., a polytunnel).
  • growing a nickel hyperaccumulator plant in the weatherable rock-enriched soil further comprises continuously irrigating the weatherable rock-enriched soil.
  • the pH of the weatherable rock-enriched soil is at least 7.
  • growing a nickel hyperaccumulator plant in the weatherable rock-enriched soil further comprises intermittently irrigating the weatherable rock-enriched soil.
  • growing a nickel hyperaccumulator plant in the weatherable rock-enriched soil further comprises fertilizing the plant.
  • nitrogen, phosphorus, and potassium (NPK) fertilizers are used to fertilize the plant.
  • calcium is added to the soil.
  • boron is used to stimulate flowering in the plant.
  • soil analysis is used to determine which nutrients are lacking in the soil.
  • fertilizer is used to provide the plant with one or more of the nutrients that are determined as lacking in the soil.
  • exogenous additives are used to increase the available levels of metals in the soil.
  • the exogenous additive comprises citric acid.
  • potassium is added to the soil.
  • sulphur-containing compounds are added to the soil.
  • ashing the harvested nickel hyperaccumulator plant comprises drying the nickel hyperaccumulator plant to provide a dried biomass composition, crushing the dried biomass composition to provide a crushed biomass composition, and burning the crushed biomass composition to provide a nickel-enriched ash composition.
  • processing the harvested nickel hyperaccumulator plant comprises directly leaching the harvested nickel hyperaccumulator plant using sulfuric acid to provide an acid leachate; purifying the acid leachate using column chromatography to provide a Ni-enriched acid leachate; and further processing the Ni-enhanced acid leachate to provide a substantially pure nickel.
  • processing the harvested nickel hyperaccumulator plant comprises leaching the nickel-enriched ash composition to provide a leachate; recovering nickel from the leachate using solvent extraction or an ion exchange resin to obtain a recovered nickel composition; and purifying the recovered nickel composition using electrowinning to obtain a substantially pure nickel.
  • the embodiments of the method described above for harvesting nickel may be modified to harvest one or more other metals, such as cobalt and chromium, or any combinations of such metals.
  • refining the nickel-enriched ash composition comprises: acid leaching the nickel-enriched ash composition to provide an acid leachate; neutralizing the acid leachate with Ca(OH)2 to provide a first treated leachate; adding NaF to the neutralized leachate to provide a second treated leachate; adding ammonium sulfate to the second treated leachate to provide a third treated leachate; drying the third treated leachate to provide ammonium Ni sulfate hexahydrate (ANSH); and processing the ANSH to obtain a substantially pure nickel.
  • ANSH ammonium Ni sulfate hexahydrate
  • the method further comprises quantifying the amount of carbon dioxide that is released or sequestered in one or more steps of the method.
  • nickel metal prepared according to any of the foregoing methods.
  • a processed nickel composition comprising substantially pure nickel, and one or more of the following: (i) precipitated gypsum, (ii) one or more low weight carboxylic acids, (iii) one or more Ni-containing compounds selected from the group consisting of NiO, Ni(OH)2, nickel sulfides, nickel hydroxides, nickel oxalate, and nickel sulfate, or (v) one or more carbonates selected from the group consisting of K2CO3, CaCO 3 , K 2 Ca(CO 3 )2.
  • a nickel-enriched ash comprising at least 5% nickel by weight, and one or more of the following: (i) one or more elements selected from the group consisting of Ca, Fe, K, Mg, P, C, H, N, and O, (ii) one or more carbonates selected from the group consisting of K2CO 3 , CaCO 3 , K2Ca(CO 3 )2, (iii) plant cells, (iv) hydroxyapatite or oxyhydroxyapatite, or (v) one or more oxides selected from the group consisting of NiO, CaO, MgO, and MgNiO2.
  • a metal-enriched ash obtained by any of the methods described herein.
  • the metal is nickel, cobalt, or chromium, or a combination thereof.
  • FIG. 1 depicts an exemplary process for obtaining metal using weatherable rock and phytomining.
  • FIG. 2 depicts the different growing conditions employed in the assessment of weathering rates for different soil and plant configurations.
  • FIG. 3 depicts the total amount of magnesium leached under each of the conditions of FIG. 2 over the course of 4 months.
  • FIGS. 4 depicts a diagram of an exemplary field- scale randomized complete block design used to investigate the synergistic combination of nickel phytomining and enhanced weathering.
  • FIG. 5 depicts the pH analysis of topsoils for five application rates approximately eight months after crushed serpentinite rock was applied.
  • FIG. 6 depicts the electrical conductivity analysis of topsoils for five application rates approximately eight months after crushed serpentinite rock was applied.
  • FIG. 7 depicts the amount of nickel in the shoot tissues of hyperaccumulator plants grown on soils treated with eight different application rates of serpentinite rock.
  • FIG. 8 depicts the results from a time-series analysis of topsoil Ni concentrations for five application rates using a Mehlich 1 reagent.
  • FIGS. 9 and 10 depicts the results of statistical analysis of the pH of the soil with respect to application rate and sampling time, respectively.
  • FIGS. 11 and 12 depicts the results of statistical analysis of the electrical conductivity of the soil with respect to application rate and sampling time, respectively.
  • FIGS. 13 and 14 depicts the results of statistical analysis of the ammonium acetate extractable nickel content of the soil with respect to application rate and sampling time, respectively.
  • FIG. 15 depicts the results of statistical analysis of the ammonium acetate extractable magnesium content of the with respect to application rate and sampling time.
  • FIG. 16 depicts a multivariate correlation of the statistical analysis of the soil data.
  • FIG. 17 depicts a diagram of another exemplary field-scale randomized complete block design used to investigate the synergistic combination of nickel phytomining and enhanced weathering.
  • FIG. 18 depicts the life cycle assessment model for an exemplary 1 kilotonne-scale production.
  • FIGS. 19A and 19B depict the life cycle assessment model for an exemplary 1 megatonne-scale production.
  • FIG. 20 depicts additional data used in the life cycle assessment of an exemplary process.
  • a method of sequestering carbon dioxide comprising providing a weatherable rock comprising one or more metals, subjecting the weatherable rock to conditions sufficient to cause the rock to undergo a chemical weathering process at an accelerated rate relative to natural chemical weathering, wherein the chemical weathering process generates alkalinity and releases the one or more metals, and wherein the alkalinity facilitates the sequestration of carbon dioxide through the conversion of carbon dioxide to bicarbonate or carbonate, and extracting and processing the released metals to provide a metal-enriched composition.
  • the conditions cited above comprise growing one or more metal hyperaccumulator plants in a medium comprising the weatherable rock.
  • the conditions comprise growing one or more metal hyperaccumulator plants in a medium comprising the weatherable rock and continuously irrigating the one or more metal hyperaccumulator plants using a drip irrigation system.
  • the extracting and processing the released one or more metals comprises growing one or more metal hyperaccumulator plants in a medium comprising the weatherable rock, wherein the one or more metal hyperaccumulator plants accumulate the released one or more metals.
  • the extracting and processing the released one or more metals further comprises processing the metal hyperaccumulator biomass using any suitable technique known in the art to prepare a metal-enriched composition.
  • the one or more metals comprise a heavy metal.
  • the one or more metals comprise a toxic metal.
  • the one or more metals comprise a metal selected from the group consisting of Ni, Cr, Co, Al, Ag, Cu, Mn, Mo, Hg, Mo, Pb, or Zn, or any combination thereof. In some embodiments, the one or more metals comprise cobalt. In some embodiments, the one or more metals comprise chromium. In some embodiments, the one or more metals comprise nickel. In some embodiment the one or more metals comprise any metal that can be hyperaccumulated by a hyperaccumulator plant. In some embodiments, providing the weatherable rock comprises mining the weatherable rock. In some embodiments, providing the weatherable rock further comprises mechanically processing the weatherable rock to reduce the particle size of the weatherable rock to between about 1 pm and about 10 cm. In some embodiments, providing the weatherable rock further comprises admixing the weatherable rock with one or more additional growing media including, for example, soil.
  • a method of sequestering carbon dioxide comprising providing a weatherable rock comprising a metal, subjecting the weatherable rock to conditions sufficient to cause the rock to undergo a chemical weathering process at an accelerated rate relative to natural chemical weathering, wherein the chemical weathering process generates alkalinity and releases the metal, and wherein the alkalinity facilitates the sequestration of carbon dioxide through the conversion of carbon dioxide to bicarbonate or carbonate, and extracting and processing the released metal to provide a metal-enriched composition.
  • the conditions cited above comprise growing a metal hyperaccumulator plant in a medium comprising the weatherable rock.
  • the conditions comprise growing a metal hyperaccumulator plant in a medium comprising the weatherable rock and continuously irrigating the metal hyperaccumulator plant using a drip irrigation system.
  • the extracting and processing the released metal comprises growing a metal hyperaccumulator plant in a medium comprising the weatherable rock, wherein the metal hyperaccumulator plant accumulates the released metal.
  • the extracting and processing the released metal further comprises processing the metal hyperaccumulator biomass using any suitable technique known in the art to prepare a metal-enriched composition.
  • the metal is a heavy metal.
  • the metal is a toxic metal.
  • the metal is selected from the group consisting of Ni, Cr, Co, Al, Ag, Cu, Mn, Mo, Hg, Mo, Pb, or Zn, or any combination thereof.
  • the metal comprises cobalt.
  • the metal comprises chromium.
  • the metal comprises nickel.
  • the metal is any metal that can be hyperaccumulated by a hyperaccumulator plant.
  • the weatherable rock comprises a magnesium-bearing silicate mineral.
  • the magnesium-bearing silicate mineral is in the olivine mineral group.
  • the magnesium-bearing silicate mineral is in the serpentinite mineral group.
  • any combination of suitable weatherable rocks described herein may be used.
  • providing the weatherable rock comprises mining the weatherable rock. In some embodiments, providing the weatherable rock further comprises mechanically processing the weatherable rock to reduce the particle size of the weatherable rock to between about 1 pm and about 10 cm. In some embodiments, providing the weatherable rock further comprises admixing the weatherable rock with one or more additional growing media including, for example, soil.
  • a method that utilizes plants that are not only tolerant to serpentine, but that evolved especially to live in high alkalinity (e.g., high pH) soils, composed of high percentages of low nutrient and metal heavy soils. These plants that typically take up nickel as a means of protection can be utilized to produce commercial yields of nickel.
  • high alkalinity e.g., high pH
  • the methods provided herein overcome the previous blockers that prevented the deployment of terrestrial enhanced weathering for the purposes of carbon removal, and by increasing the revenue streams available to the process are able to make direct and intentional phytomining possible.
  • the methods provided make phytomining a primary mining technique.
  • the methods can also use tailings, waste, or overburden from traditional nickel mines.
  • the methods involve actively grinding minerals to below a certain size in order to specifically increase the reactive surface area.
  • direct irrigation can be utilized to both enhance the weathering rate, and increase the plant growth, the plant then releases acids that further break down the rocks, releasing magnesium that leads to carbon removal and drawing nickel into the plants, preventing its release into the environment.
  • the chemical weathering process results in the formation of new soil minerals.
  • the chemical weathering process results in fully weathered rock.
  • the weathering process results in fully weathered rock within about 20 years; or between 1 year and 20 years; or within about 1 year, about 2 years, about 3 years, about 4 years, about 5 years, about 6 years, about 7 years, about 8 years, about 9 years, about 10 years, about 11 years, about 12 years, about 13 years, about 14 years, about 15 years, about 16 years, about 17 years, about 18 years, about 19 years, or about 20 years.
  • Step 102 involves mechanically grinding a weatherable rock to provide a particulate weatherable rock composition.
  • step 104 the particulate weatherable rock composition is combined with a soil to provide a weatherable rock-enriched soil.
  • step 106 a plant that is a hyperaccumulator of the metal in the weatherable rock-enriched soil is grown.
  • step 108 the metal hyperaccumulator plant is harvested.
  • step 110 the harvested metal hyperaccumulator plant is processed using any suitable techniques or methods known in the art to provide a substantially pure metal. In some variations of the process, step 110 may be optional.
  • the process described herein does not require harvesting of the metal from the plant to obtain a substantially pure metal.
  • the process further includes harvesting of the metal from the plant to obtain a substantially pure metal.
  • a method for preparing a metal comprising mechanically grinding a weatherable rock comprising magnesium, and a metal to provide a particulate weatherable rock composition; combining the particulate weatherable rock composition with a soil to provide a weatherable rock-enriched soil; growing a plant that is a hyperaccumulator of the metal in the weatherable rock-enriched soil; harvesting the metal hyperaccumulator plant; and processing the harvested metal hyperaccumulator plant to provide a substantially pure metal.
  • processing the harvested metal hyperaccumulator plant comprises ashing the harvested metal hyperaccumulator plant to provide a metal-enriched ash and refining the metal-enriched composition to provide a substantially pure metal by weight.
  • processing the harvested metal hyperaccumulator plant to provide a substantially pure metal may be accomplished using any suitable techniques known in the art.
  • the weatherable rock comprises at least 20% by weight of magnesium and 0.1% by weight of the metal.
  • the metal-enriched ash comprises at least 5% of the metal by weight.
  • a method for preparing one or more metals comprising mechanically grinding a weatherable rock comprising magnesium, and one or more metals to provide a particulate weatherable rock composition; either combining the particulate weatherable rock composition with a soil to provide a weatherable rock-enriched soil or using the particulate weatherable rock composition directly as a weatherable rock- enriched soil without combining it with any additional media; growing one or more metal hyperaccumulator plants in the weatherable rock-enriched soil, wherein each of the one or more plants is a hyperaccumulator of at least one of the one or more metals; harvesting the one or more metal hyperaccumulator plants; and processing the one or more harvested metal hyperaccumulator plants to provide one or more substantially pure metals.
  • processing the one or more harvested metal hyperaccumulator plants comprises ashing the harvested metal hyperaccumulator plant to provide a metal-enriched ash and refining the metal-enriched composition to provide one or more substantially pure metals by weight.
  • processing the harvested metal hyperaccumulator plant to provide one or more substantially pure metals may be accomplished using any suitable techniques known in the art.
  • the weatherable rock comprises at least 20% by weight of magnesium and 0.1% by weight of each of the one or more metals.
  • the metal-enriched ash comprises at least 5% of each of the one or more metals by weight.
  • a method for obtaining one or more substantially pure metals comprising mechanically grinding a weatherable rock comprising at least 20% by weight of magnesium and at least 0.1% by weight of each of the one or more metals to provide a particulate weatherable rock composition; combining the particulate weatherable rock composition with a soil to provide a weatherable rock-enriched soil; growing one or more metal hyperaccumulator plants in the weatherable rock-enriched soil, wherein each of the one or more plants is a hyperaccumulator of at least one of the one or more metals; harvesting the one or more metal hyperaccumulator plants; and processing the one or more harvested metal hyperaccumulator plants to provide one or more substantially pure metals.
  • substantially pure metal refers to a metal that is at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.9%, at least 99.99%. at least 99.999%, or at least 99.9999% pure by weight.
  • Mg 2+ is leached at a rate of at least 1% by weight of the total Mg 2+ in the weatherable rock per year from the weatherable rock-enriched soil while the metal hyperaccumulator plant is growing.
  • about 10% of the Mg by weight is weathered per year.
  • about 90% of the Mg by weight is weathered per month.
  • at least about 90% of the weatherable Mg 2+ ions by weight are liberated.
  • at least about 90% of the weatherable Mg 2+ ions by weight are liberated over a period of about 20 years.
  • the weight of Mg 2+ refers to the weight of the magnesium component alone, and does not include, for example, the weight of any ligands or counter ions in any complexes or salts that the Mg 2+ is a part of.
  • a method for preparing a metal comprising mechanically grinding a weatherable rock comprising calcium and a metal to provide a particulate weatherable rock composition; combining the particulate weatherable rock composition with a soil to provide a weatherable rock-enriched soil; growing a plant that is a hyperaccumulator of the metal in the weatherable rock-enriched soil; harvesting the metal hyperaccumulator plant; and processing the harvested metal hyperaccumulator plant to provide a substantially pure metal.
  • processing the harvested metal hyperaccumulator plant comprises ashing the harvested metal hyperaccumulator plant to provide a metal-enriched ash and refining the metal-enriched composition to provide a substantially pure metal by weight.
  • processing the harvested metal hyperaccumulator plant to provide a substantially pure metal may be accomplished using any suitable techniques known in the art.
  • the weatherable rock comprises at least 10% by weight of calcium and at least 0.1% by weight of the metal.
  • the metal-enriched ash comprises at least 5% of the metal by weight.
  • Ca 2+ is leached at a rate of at least 1% by weight of the total Ca 2+ in the weatherable rock per year from the weatherable rock-enriched soil while the metal hyperaccumulator plant is growing.
  • about 10% of the Ca by weight is weathered per year.
  • about 90% of the Ca by weight is weathered per month.
  • at least about 90% of the weatherable Ca 2+ ions by weight are liberated.
  • at least about 90% of the weatherable Ca 2+ ions by weight are liberated over a period of about 20 years.
  • at least about 90% of the weatherable Ca 2+ ions by weight are liberated over a period of less than about 20 years.
  • the weight of Ca 2+ refers to the weight of the calcium component alone, and does not include, for example, the weight of any ligands or counter ions in any complexes or salts that the Ca 2+ is a part of.
  • the rate at which Mg 2+ is leached is measured by measuring the concentration of the Mg 2+ in the water used to irrigate the hyperaccumulator plant. In some embodiments, the rate at which Ca 2+ is leached is measured by measuring the concentration of Ca 2+ in the water used to irrigate the hyperaccumulator plant.
  • the weatherable rock comprises between 0.01% and 20% of the metal by weight. In some embodiments, the weatherable rock comprises between 0.2% and 0.4% of the metal by weight. In some embodiments, the weatherable rock comprises at least about 0.2% metal by weight. In some embodiments, the weatherable rock comprises about 0.01%, about 0.1%, about 0.2%, about 0.3%, about 0.4%, about 0.5%, about 0.6%, about 0.7%, about 0.8%, about 0.9%, about 1%, about 2%, about 3%, about 4%, about 5%, about 10%, about 15%, about 20%, or about 25% by weight of the metal.
  • the metal comprises Ni, Cr, Co, Al, Ag, Cu, Mn, Mo, Hg, Mo, Pb, or Zn, or any combination thereof.
  • the metal comprises a rare earth metal.
  • the metal comprises nickel.
  • the metal comprises cobalt.
  • the metal comprises chromium.
  • the metal is a metal that can be hyperaccumulated by a hyperaccumulator plant.
  • the metal is a metal found in a weatherable rock.
  • the metal is a metal found in a weatherable rock that can be hyperaccumulated by a hyperaccumulator plant.
  • a method for preparing a metal comprising mechanically grinding a weatherable rock comprising magnesium and nickel to provide a particulate weatherable rock composition; combining the particulate weatherable rock composition with a soil to provide a weatherable rock-enriched soil; liberating nickel from the weatherable rock by subjecting the weatherable rock-enriched soil to conditions sufficient to cause the weatherable rock to undergo a chemical weathering process at an accelerated rate relative to natural chemical weathering, wherein acid is not added to the weatherable rock- enriched soil; growing a plant that is a hyperaccumulator of nickel in the weatherable rock- enriched soil; harvesting the nickel hyperaccumulator plant; and processing the harvested nickel hyperaccumulator plant to provide substantially pure nickel.
  • the amount of carbon dioxide emitted from the weathering of the weatherable rock is less than amount of carbon dioxide sequestered from the weathering of the weatherable rock. In some embodiments, the amount of carbon dioxide emitted from the weathering of the weatherable rock, harvesting the nickel hyperaccumulator plant, and processing the harvested nickel hyperaccumulator plant is less than amount of carbon dioxide sequestered from the weathering of the weatherable rock.
  • a method for preparing nickel metal comprising mechanically grinding a weatherable rock comprising magnesium, and nickel to provide a particulate weatherable rock composition; combining the particulate weatherable rock composition with a soil to provide a weatherable rock-enriched soil; growing a nickel hyperaccumulator plant in the weatherable rock-enriched soil; harvesting the nickel hyperaccumulator plant; and processing the harvested nickel hyperaccumulator plant to provide a substantially pure nickel.
  • processing the harvested nickel hyperaccumulator plant comprises ashing the harvested nickel hyperaccumulator plant to provide a nickel-enriched ash and refining the nickel-enriched composition to provide a substantially pure nickel by weight.
  • processing the harvested nickel hyperaccumulator plant to provide a substantially pure nickel may be accomplished using any suitable techniques known in the art.
  • the weatherable rock comprises at least 10% by weight of magnesium and at least 0.1% by weight of nickel.
  • the nickel-enriched ash comprises at least 5% nickel by weight.
  • Mg 2+ is leached at a rate of at least 1% by weight of the total Mg 2+ in the weatherable rock per year from the weatherable rock-enriched soil while the nickel hyperaccumulator plant is growing.
  • the weatherable rock comprises between 5% and 60% Mg by weight. In some embodiments, the weatherable rock comprises between 25% and 50% Mg by weight. In some embodiments, the weatherable rock comprises about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, or about 70% Mg by weight.
  • the weatherable rock comprises between 5% and 60% Ca by weight. In some embodiments, the weatherable rock comprises between 25% and 50% Ca by weight. In some embodiments, the weatherable rock comprises about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, or about 70% Ca by weight.
  • the weatherable rock comprises between 0.01% and 20% of nickel by weight. In some embodiments, the weatherable rock comprises between 0.2% and 0.4% of nickel by weight. In some embodiments, the weatherable rock comprises at least about 0.2% metal by weight. In some embodiments, the weatherable rock comprises about 0.01%, about 0.1%, about 0.2%, about 0.3%, about 0.4%, about 0.5%, about 0.6%, about 0.7%, about 0.8%, about 0.9%, about 1%, about 2%, about 3%, about 4%, about 5%, about 10%, about 15%, about 20%, or about 25% by weight of nickel.
  • the weatherable rock comprises nickel and Mg. In some embodiments, the weatherable rock comprises between 0.01% and 25% of nickel by weight and between 5% and 60% of Mg by weight. In some embodiments, the weatherable rock comprises between 0.01% and 25% of nickel by weight and between 25% and 50% of Mg by weight.
  • the weatherable rock comprises between 0.2% and 0.4% of nickel by weight. In some embodiments, the weatherable rock comprises at least about 0.2% metal by weight. In some embodiments, the weatherable rock comprises about 0.01%, about 0.1%, about 0.2%, about 0.3%, about 0.4%, about 0.5%, about 0.6%, about 0.7%, about
  • the nickel-enriched ash composition comprises between 1% and 99.8% nickel by weight. In some embodiments, the nickel-enriched ash composition comprises between 1% and 35% nickel by weight. In some embodiments, the nickel-enriched ash composition comprises between 1% and 30% nickel by weight. In some embodiments, the nickel-enriched ash composition comprises between 0.1% and 30% nickel by weight. In some embodiments, the nickel-enriched ash composition comprises between 0.1% and 20% nickel by weight. In some embodiments, the nickel-enriched ash composition comprises between 0.1% and 15% nickel by weight.
  • the nickel- enriched ash composition comprises about 0.1%, about 0.5%, about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 4%, about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, or about 40% nickel by weight.
  • refining the nickel-enriched composition provides a nickel that is at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98%, at least 99%, at least 99.9%, at least 99.9%, at least 99.99%, at least 99.999%, or at least 99.9999% pure by weight.
  • refining the nickel-enriched composition provides a nickel that is between 15% and 100% pure by weight.
  • ashing the harvested nickel hyperaccumulator plant comprises drying the nickel hyperaccumulator plant to provide a dried biomass composition, crushing the dried biomass composition to provide a crushed biomass composition; and burning the crushed biomass composition to provide a nickel-enriched ash composition.
  • the ashing is performed at a temperature of about 500 °C.
  • processing the harvested nickel hyperaccumulator plant comprises directly leaching the harvested nickel hyperaccumulator plant to provide a leachate; purifying the leachate to provide a Ni-enriched leachate; and further processing the Ni-enhanced leachate to provide a substantially pure nickel.
  • the direct leaching is performed using a hydrothermal process.
  • the direct leaching is performed in acid.
  • the acid is sulfuric acid.
  • the acid is hydrochloric acid.
  • purifying the leachate comprises purifying the leachate using column chromatography.
  • purifying the leachate comprises purifying the leachate using solvent extraction.
  • purifying the leachate comprises purifying the leachate using ion exchange chromatography.
  • further processing the Ni-enhanced leachate comprises electrowinning the nickel.
  • processing the harvested nickel hyperaccumulator plant comprises ashing the harvested nickel hyperaccumulator plant to provide a nickel-enriched ash, leaching the nickel-enriched ash composition to provide a leachate, treating the leachate to provide ammonium Ni sulfate hexahydrate (ANSH), and processing the ANSH to obtain a substantially pure nickel.
  • the leaching is performed in acid.
  • treating the leachate comprises neutralizing the leachate using a base to provide a first treated leachate, adding a fluoride source to the first treated leachate to provide a second treated leachate, adding ammonium sulfate to the second treated leachate to provide a third treated leachate, and drying the third treated leachate to provide ANSH.
  • the base is Ca(OH)2.
  • the fluoride source is NaF.
  • treating the leachate comprises purifying the ANSH via recrystallization.
  • a method for preparing nickel catalysts comprising mechanically grinding a weatherable rock comprising magnesium, and nickel to provide a particulate weatherable rock composition; combining the particulate weatherable rock composition with a soil to provide a weatherable rock-enriched soil; growing a nickel hyperaccumulator plant in the weatherable rock-enriched soil; harvesting the nickel hyperaccumulator plant; and processing the harvested nickel hyperaccumulator plant to provide nickel catalysts.
  • processing the harvested nickel hyperaccumulator plant comprises ashing the harvested nickel hyperaccumulator plant to provide a nickel-enriched ash, leaching the nickel-enriched ash to provide a leachate, and further processing the leachate to provide nickel catalysts.
  • the ashing is performed at a temperature of 500 °C.
  • the leaching is performed in acid.
  • the acid is hydrochloric acid.
  • further processing the leachate to provide nickel catalysts comprises dispersing the leachate onto montromorillonite K10.
  • the weatherable rock comprises at least 10% by weight of magnesium and at least 0.1% by weight of nickel.
  • the amount of carbon dioxide sequestered is on the tonne scale for every tonne of nickel metal that is produced.
  • At least 1 tonne, at least 5 tonnes, at least 10 tonnes, at least 20 tonnes, at least 30 tonnes, or at least 40 tonnes of carbon dioxide are sequestered for every tonne of nickel metal that is produced. In some embodiments, between 1 tonne and 100 tonnes, or between 10 tonnes and 100 tonnes of carbon dioxide are sequestered for every tonne of nickel metal that is produced. In some embodiments, between 100 tonnes and 500 tonnes, or between 300 tonnes and 500 tonnes of carbon dioxide are sequestered for every tonne of nickel metal that is produced.
  • the weatherable rock comprises an ultramafic rock. In some embodiments, the weatherable rock comprises serpentine. In some embodiments, the weatherable rock comprises serpentinite. In some embodiments, the weatherable rock comprises olivine. In some embodiments, the weatherable rock contains less than 1% by weight of nickel. In some embodiments, the weatherable rock contains a metal that can be hyperaccumulated by a hyperaccumulator plant.
  • the method further comprises mining the weatherable rock. In other embodiments, the method further comprises transporting the mined weatherable rock from a mining location to a grinding location.
  • mechanically grinding the weatherable rock comprises crushing and/or milling the weatherable rock.
  • the energy used to mechanically grind the rock comes from renewable sources.
  • the particulate weatherable rock composition has an average particle size between about 1 pm and about 10 mm, between about 1 pm and about 10 cm, between about 1 pm and about 20 cm, between about 1 pm to about 5 mm, between about 1 pm to about 3 mm, or between about 100 pm to about 3 mm.
  • the weatherable rock-enriched soil comprises between 10% and 100%, between 70% and 100%, between 70% and 90%, between 70% and 80%, or between 80% and 90% particulate weatherable rock composition by weight. In certain embodiments, the weatherable rock-enriched soil comprises about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, or about 100% particulate weatherable rock composition by weight.
  • the weatherable rock-enriched soil is formed by natural weathering of silicate rocks. In some embodiments, the weatherable rock-enriched soil is formed by natural weathering of serpentinite rocks. In some embodiments, the weatherable rock-enriched soil is formed by natural weathering of olivine rocks. In some embodiments, natural weathering of serpentinite rocks results in weatherable rock-enriched soil with high nickel concentrations.
  • the nickel hyperaccumulator plant is a plant belonging to the genus Odontarrhena.
  • the plant belongs to the genus Alyssum.
  • the plant belongs to the family Brassicacaea.
  • the plant belongs to the genus Bornmuellera.
  • the plant belongs to the genus Thlaspi.
  • the plant is Alyssum Murale.
  • the plant is of the genus Odontarrhena.
  • the plant is Odontarrhena chalcidica.
  • the plant is Odontarrhena decipiens.
  • the plant is Berkheya coddii.
  • the plant is B. emarginata. In some embodiments, the plant is Stackhousia tryonii. In some embodiments, the plant is Phyllanthus balgooyi. In some embodiments, the plant is Rinorea bengalensis. In some embodiments, the plant may be a tree, bush, or vine. In some embodiments, the plant is a genetically modified plant. In some embodiments, the plant is any plant capable of hyperaccumulating a metal found in a weatherable rock. In some embodiments, the plant is any plant capable of hyperaccumulating nickel. In some embodiments, the plant is any hyperaccumulator plant species of the class known as a hypernickelophores, containing more than 1,000 pg Ni g 1 .
  • the nickel hyperaccumulator plant is grown inside of a greenhouse. In some embodiments, the nickel hyperaccumulator plant is grown inside of a vertical farm. In some embodiments, the nickel hyperaccumulator plant is grown hydroponically. In some embodiments, the nickel hyperaccumulator plant is grown under a polyethylene film (e.g., a polytunnel).
  • a polyethylene film e.g., a polytunnel
  • the environmental conditions under which the nickel hyperaccumulator plant is grown are optimized to maximize the weathering rate of the weatherable rock. In some embodiments, the environmental conditions under which the nickel hyperaccumulator plant is grown are optimized to maximize the efficiency of nickel uptake by the plant. In some embodiments, the environmental conditions under which the nickel hyperaccumulator plant is grown are optimized to maximize the weathering rate of the weatherable rock and the efficiency of nickel uptake by the plant.
  • the environmental conditions of the weatherable rock- enriched soil are controlled to cause the weatherable rock to undergo a chemical weather process at an accelerated rate relative to natural chemical weathering environmental conditions.
  • the conditions cited above comprise growing one or more metal hyperaccumulator plants in the weatherable rock-enriched soil.
  • the conditions comprise growing one or more metal hyperaccumulator plants in a weatherable rock-enriched soil and continuously irrigating the one or more metal hyperaccumulator plants using a drip irrigation system.
  • the temperature, pH, irrigation, or bioactivity of the weatherable rock-enriched is controlled.
  • the rate of weathering of the weatherable rock is between about 0% and about 40% by mass of the weatherable rock between about 12 months and about 72 months from the date of combining the particulate weatherable rock composition with a soil to provide a weatherable rock-enriched soil and planting the hyperaccumulator plant in the weatherable rock-enriched soil.
  • Any suitable methods known in the art may be used to determine the rate of weathering of the weatherable rock.
  • the foregoing rates of weathering may be calculated using the Arrhenius equation.
  • the weathering rate is calculated by measuring the accumulation of rock-derived cations (e.g., Ca, Mg, Na, and K) in plant, soil, and/or aqueous effluent associated within a certain plot of land and subtracting the baseline amount of the corresponding cation measured in a corresponding control plot.
  • rock-derived cations e.g., Ca, Mg, Na, and K
  • the net accumulation of Ca-cations due to mineral dissolution of weatherable rock can be calculated by subtracting the amount of Ca-cations measured in a control plot from the total amount of Ca-cations calculated by totaling the amount of Ca-cations in the water and/or effluent, the Ca-cations in plant tissues, and Ca-cations in the soil cation exchange pool.
  • the amount of Ca-cations attributable to the weathering of weatherable rock can then be converted into spatially-averaged cation weathering rates (per unit of land area) or rates related to mineral surface area.
  • the weatherable rock is calculated in the number of moles of calcium, magnesium, sodium, and/or potassium released from the weatherable rock material into the soil per hectare of treated land per annum.
  • the weathering rate of the weatherable rock increases when the average particle size of the weatherable rock decreases.
  • the environmental conditions under which the nickel hyperaccumulator plant is grown are optimized to increase the weathering rate of the weatherable rock.
  • the environmental parameter that is optimized to increase the weathering rate of the weatherable rock is temperature.
  • the temperature of the surrounding air e.g., climate
  • the temperature of the topsoil e.g., where the weatherable rock is admixed into the soil
  • the amount of irrigation of the soil admixed with the weatherable rock is increased to increase the weathering rate of the weatherable rock.
  • the pH of the soil admixed with the weatherable rock is increased to decrease the weathering rate of the weatherable rock. In some embodiments, the pH of the soil admixed with the weatherable rock is decreased to increase the weathering rate of the weatherable rock.
  • the weathering rate of the weatherable rock is increased by increasing the amount of biological activity of the soil admixed with the weatherable rock.
  • the increased biological activity of the soil is measured by the amount of carbon dioxide produced by the microbes per a given amount of the soil.
  • the increased biological activity of the soil is measured by the amount of nitrogen-cycling and secretion of organic acids by plant roots and mycorrhizal fungi present in the soil.
  • increasing the concentration of Mg 2+ ions in the soil admixed with the weatherable rock increases the weathering rate of the weatherable rock.
  • increasing the concentration of Ca 2+ ions in the soil admixed with the weatherable rock increases the weathering rate of the weatherable rock.
  • higher soil Ca and Mg content may decrease the weathering rate of rock material added to the soil, because chemical conditions in the groundwater may approach saturation for certain Ca- (and Mg-) bearing minerals.
  • the environmental conditions under which the nickel hyperaccumulator plant is grown are optimized to maximize the accumulation of nickel by the plant. In some embodiments, the environmental conditions under which the nickel hyperaccumulator plant is grown are optimized to maximize the growth rate of the plant. In some embodiments, the humidity, temperature, or lighting of the environment in which the nickel hyperaccumulator plant is grown are controlled. In some embodiments, the nickel hyperaccumulator plant is grown in an outdoor field.
  • the amount of weatherable rock mixed into the soil for every hectare on which the hyperaccumulator plant is grown is optimized to maximize the accumulation of nickel by the hyperaccumulator plant.
  • the amount of weatherable rock mixed into the soil to maximize the accumulation of nickel by the hyperaccumulator plant is between about 5 tonnes and 300 tonnes.
  • the amount of weatherable rock mixed into the soil to maximize the accumulation of nickel by the hyperaccumulator plant is between about 10 tonnes and 50 tonnes.
  • the amount of weatherable rock mixed into the soil to maximize the accumulation of nickel by the hyperaccumulator plant is about 37 tonnes.
  • the amount of nickel accumulated by a nickel hyperaccumulator plant increases proportionally with the amount of weatherable rock mixed into the soil in which the plant is grown. In some embodiments, increasing the amount of weatherable rock mixed in the soil does not result in an increase in the amount of nickel accumulated by a hyperaccumulator plant growing in the soil. In certain embodiments, high amounts of weatherable rock mixed into the soil result in high alkaline (e.g., high pH) soils which can negatively impact the mobility of the one or more metals released from the weatherable rock during the weathering process.
  • high alkaline e.g., high pH
  • the amount of weatherable rock mixed into the soil for every hectare on which the hyperaccumulator plant is grown and the environmental conditions under which the hyperaccumulator plant is grown are optimized to control the pH of the soil.
  • the amount of weatherable rock mixed into the soil for every hectare on which the hyperaccumulator plant is grown is optimized to control the pH of the soil.
  • an increase in the pH of the soil decreases the mobility of the one or metals released by the weatherable rock mixed in the soil.
  • decreased mobility of the one or more metals in the soil results in lower accumulation of the metals by a hyperaccumulator plant of the same metal growing in the soil.
  • an increase of the pH of the soil decreases the amount of metal accumulated by the hyperaccumulator plant growing in the soil, the mobility of the one or metals released by the weatherable rock, or both.
  • the amount of weatherable rock mixed into the soil for every hectare on which the hyperaccumulator plant is grown is optimized to maximize the growth rate of the hyperaccumulator plant.
  • At least 5 tonnes of weatherable rock are mixed into the soil for every hectare on which the nickel hyperaccumulator plant is grown.
  • at least 10 tonnes of weatherable rock are mixed into the soil for every hectare on which the nickel hyperaccumulator plant is grown.
  • between 10 tonnes and 100 tonnes of weatherable rock are mixed into the soil for every hectare on which the nickel hyperaccumulator plant is grown.
  • between 5 tonnes and 10 tonnes of weatherable rock are mixed into the soil for every hectare on which the nickel hyperaccumulator plant is grown.
  • between 25 tonnes and 50 tonnes of weatherable rock are mixed into the soil for every hectare on which the nickel hyperaccumulator plant is grown.
  • between 35 tonnes and 40 tonnes of weatherable rock are mixed into the soil for every hectare on which the nickel hyperaccumulator plant is grown. In some embodiments, between 100 tonnes and 200 tonnes of weatherable rock are mixed into the soil for every hectare on which the nickel hyperaccumulator plant is grown. In some embodiments, about 150 tonnes of weatherable rock are mixed into the soil for every hectare on which the nickel hyperaccumulator plant is grown. In some embodiments, between 400 tonnes and 800 tonnes of weatherable rock are mixed into the soil for every hectare on which the nickel hyperaccumulator plant is grown. . In some embodiments, about 600 tonnes of weatherable rock are mixed into the soil for every hectare on which the nickel hyperaccumulator plant is grown.
  • At least about 20 tonnes of nickel hyperaccumulator biomass is grown per hectare.
  • at least about 400 kg, at least about 500 kg of nickel, at least about 600 kg, at least about 700 kg, at least about 800 kg, at least about 900 kg, or at least about 1,000 kg of nickel is produced per hectare.
  • between about 100 kg and 5000 kg, or between 250 kg and 1000 kg, or between 400 kg and 1000 kg of nickel is produced per hectare.
  • between about 5 tonnes and about 50 tonnes, between about 100 tonnes and about 700 tonnes, between about 500 tonnes and about 700 tonnes, between about 100 tonnes and about 600 tonnes, between about 200 tonnes and about 600 tonnes, between about 300 tonnes and about 600 tonnes, between about 400 tonnes and about 600 tonnes, between about 500 tonnes and about 600 tonnes, between about 100 tonnes and about 500 tonnes, between about 200 tonnes and about 500 tonnes, between about 300 tonnes and about 500 tonnes, between about 400 tonnes and about 500 tonnes, between about 100 tonnes and about 400 tonnes, between about 200 tonnes and about 400 tonnes, between about 300 tonnes and about 400 tonnes, between about 100 tonnes and about 300 tonnes, between about 200 tonnes and about 300 tonnes, or between about 100 tonnes and about 200 tonnes of weatherable rock are mixed into the soil for every hectare on which the hyperaccumulator plant is grown.
  • about 500 tonnes about 600 tonnes, or about 700 tonnes of weatherable rock are mixed into the soil for every hectare on which the hyperaccumulator plant is grown.
  • the amount of carbon dioxide sequestered is proportional to the number of Mg 2+ ions liberated from the weathering of the weatherable rock. In some embodiments, the amount of carbon dioxide sequestered per hectare is proportional to the number of Mg 2+ ions liberated from the weathering of the weatherable rock mixed into the soil for every hectare.
  • the amount of carbon dioxide sequestered is proportional to the number of Ca 2+ ions liberated from the weathering of the weatherable rock. In some embodiments, the amount of carbon dioxide sequestered per hectare is proportional to the number of Ca 2+ ions liberated from the weathering of the weatherable rock mixed into the soil for every hectare.
  • the nickel hyperaccumulator plant is harvested mechanically. In some embodiments, the nickel hyperaccumulator plant is harvested manually. In some embodiments, the nickel hyperaccumulator plant is harvested by an automated process.
  • growing a nickel hyperaccumulator plant in the weatherable rock-enriched soil further comprises continuously irrigating the weatherable rock-enriched soil.
  • the plant is irrigated using a drip irrigation system.
  • the plant is irrigated using sprinkler systems.
  • growing a nickel hyperaccumulator plant in the weatherable rock-enriched soil further comprises intermittently irrigating the weatherable rock-enriched soil.
  • the plant is irrigated using a flood irrigation approach.
  • the plant is irrigated using traditional irrigation.
  • the pH of the weatherable rock-enriched soil is above 7. In some embodiments, the pH of the weatherable rock-enriched soil is between 7 and 14. In some embodiments, the pH of the weatherable rock-enriched soil is between 5 and 14. In some embodiments, increasing the content of the weatherable rock of the weatherable rock- enriched soil increases the pH of the soil.
  • ashing the harvested nickel hyperaccumulator plant comprise drying the nickel hyperaccumulator plant to provide a dried biomass composition; crushing the dried biomass composition to provide a crushed biomass composition; and burning the crushed biomass composition to provide a nickel-enriched composition.
  • the method further comprises quantifying the amount of carbon dioxide that is released or sequestered in one or more steps of any of the methods described herein.
  • the amount of carbon dioxide released or sequestered by a process is measured directly.
  • the amount of carbon dioxide released or sequestered by a process is measured using a proxy.
  • the quantity of Mg 2+ is used as a proxy to quantify the amount of carbon dioxide sequestered by chemical weathering of the weatherable rock.
  • nickel metal prepared according to any of the methods described above.
  • a processed nickel composition comprising a substantially pure nickel, and one or more of the following: Nickel rich ashes also containing K, Ca, oxides (e.g., NiO, MgO), carbonates (e.g., K2CO3, CaCO 3 , K 2 Ca(CO 3 )2), K2SO4, precipitated gypsum, low-mass carboxylic acids, Ni-bearing organic and inorganic compounds.
  • Nickel rich ashes also containing K, Ca, oxides (e.g., NiO, MgO), carbonates (e.g., K2CO3, CaCO 3 , K 2 Ca(CO 3 )2), K2SO4, precipitated gypsum, low-mass carboxylic acids, Ni-bearing organic and inorganic compounds.
  • Ni-based compounds such as NiO, Ni(OH) 2 , nickel sulfides, nickel hydroxides, Ni oxalate, and Ni sulfate.
  • the processed nickel composition is at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98%, at least 99%, at least 99.8%, at least 99.9%, at least 99.99%, at least 99.999%, or at least 99.9999% pure by weight. In some embodiments, the processed nickel composition is between 15% and 100% pure by weight.
  • a nickel-enriched ash comprising at least 5% nickel by weight, and one or more of the following: Nickel rich ashes also containing K, Ca, oxides (e.g., NiO, MgO) and carbonates (e.g., K2CO3, CaCCh, KiCa CCh ), K2SO4, precipitated gypsum, low-mass carboxylic acids, Ni-bearing organic and inorganic compounds.
  • Nickel rich ashes also containing K, Ca, oxides (e.g., NiO, MgO) and carbonates (e.g., K2CO3, CaCCh, KiCa CCh ), K2SO4, precipitated gypsum, low-mass carboxylic acids, Ni-bearing organic and inorganic compounds.
  • Ni-based compounds such as NiO, Ni(OH)2, nickel sulfides, nickel hydroxides, Ni oxalate, and Ni sulfate.
  • a nickel-enriched ash comprising at least 5% nickel by weight, and one or more of the following: Ca, Fe, K, Mg, carbonates (e.g., K2CO3, CaCOs, or K2Ca(CO3 ), P, plant cells, C, H, N, O, hydroxyapatite, oxy -hydroxyapatite, or oxides (e.g., NiO, CaO, MgO, or MgNiO2).
  • the nickel-enriched ash comprises between 5% and 100% nickel by weight.
  • the weight of nickel refers to the weight of the nickel component alone, and does not include, for example, the weight of any ligands or counter ions in any complexes or salts, respectively, that the nickel is a part of.
  • Samples of O. decipiens (a close relative to the hyperaccumulator known in the art as O. chalcidica or A. morale) were shipped to a testing facility. There, the seeds were separated from the remainder of the plant biomass, soaked in water to prepare them for germination, and germinated. The germinated seeds were observed to have root systems. Separately, a sample of serpentinite rock was obtained, and was ground into a fine powder, herein referred to as “serpentine soil”.
  • a 112 m x 168 m field site was selected for this trial based on aerial photography and ground observations.
  • Four permanent reference points for determining precise locations were established by cementing steel posts into the ground at the comers of the field site.
  • the area was then partitioned into four equally-sized rectangular blocks, each measuring 56 m x 84 m.
  • a scale diagram of the randomized complete block design used in the trial is shown in FIG. 4. These blocks represent replicates, such that each block contained eight randomized 12 m x 18 m plots (one for each of the eight rock treatments) separated by an 8 m margin of untreated land.
  • the amount of rock treatment added to each plot as measured in tonnes of serpentinite rock per hectare is shown in FIG. 4.
  • the randomized complete block design accounts for the effects of extraneous variables (e.g. hydrological gradients across the site) and hence, mitigates bias caused by inherent variation.
  • Soils are then passed through a 2 mm mesh size sieve, air dried, and tested for the following physical and chemical parameters: pH (in H2O and IM KC1); organic matter and humus %; plant-available nitrogen, phosphorus and potassium; soil texture (sand/silt/clay %); cation exchange capacity; and, total and plant-available Ca, Mg, K, Na, Fe, Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn. Further soil samples were collected monthly from each of the thirty-two experimental plots and tested for pH, electrical conductivity, cation exchange capacity, and plant-available cations. These data were used to monitor changes in the concentrations of plant-available nutrients and nickel over time, and to estimate rock weathering and carbon dioxide capture rates via a conventional mass balance approach, in combination with novel quantification methods.
  • Aboveground plant tissues are harvested from all plots after a suitable time (e.g., approximately 6-8 months) after the trial began. Plant materials are dried and weighed to determine crop yields, and ground for analysis of nutrients and metals. These data are used to measure the efficiency of nickel uptake by the hyperaccumulator plants, and to evaluate the correlation between rock application and nickel uptake rates. Moreover, values for total uptake of calcium, magnesium, potassium and sodium are fed into mass budget calculations for carbon capture quantification.
  • Aboveground plant tissues were harvested from five different mature hyperaccumulator plant specimens randomly selected from all plots after a suitable time (e.g., approximately 6-8 months) after the trial began. Plant samples were washed with distilled water, dried in a forced-air oven at 60 °C for 48 hours, and powdered separately using a laboratory grinding mill. These plant samples were used to determine total heavy metal concentrations in the plant tissues.
  • pH and the electrical conductivity (EC) of the soil samples determined using a Combined Conductivity /pH Meter equipped with a temperature input, which internally corrects for the effect of temperature on measured values.
  • pH and EC were standardized using a 3-point calibration protocol with certified reference solutions (buffers at pH 4.00, 7.00, and 14.00; EC standards at 12.88 mS, 1413 pS, and 84 pS). To streamline the measurements, pH and EC were tested sequentially from the same sample.
  • the pH electrode was swirled into the soil-water mixture’s supernatant for 10 seconds, and then gently released into the slurry until the instrument identified that a stable pH reading was achieved (or 3 minutes after initial insertion, where stabilization was not achieved). pH measurements were recorded to 0.001 pH units, and the electrode was rinsed thoroughly with ultrapure water between samples.
  • the conductivity electrode was inserted into the soilwater mixture’s supernatant and held until the instrument indicated that a stable EC reading was achieved (or 1 minute after initial insertion, where stabilization was not achieved). EC measurements were recorded to four significant figures, and the electrode was rinsed thoroughly with ultrapure water between samples.
  • the soil samples were tested for total heavy metals by first drying a test portion of the soil and reducing the grain size of the soil to below a particle size of 250 microns. Each test portion of the soil was then weighed (0.5 g to 1.0 g based on dry mass) and transferred to a microwave extraction vessel. A few drops of water were then added to the extraction vessel before adding a HC1 and nitric acid solution and mixing well. The temperature of the extraction mixture was increased at a rate of approximately 10 °C/min to 175 ⁇ 5 °C using a microwave digestion system. The amount of total Ni in the soil samples was then determined using ICP-OES.
  • the soil samples were prepared by mixing 5 g of the soil samples with 20 mL of a Mehlich-1 extraction solution consisting of a mixture of HC1 and H2SO4. The mixture was then stirred for 5 min at 180 cycles/min after which the suspension was allowed to rest for 16 h before decanting off the supernatant The total amount of Ni in the soil samples was then determined by testing an aliquot of the supernatant using ICP-OES.
  • one or more additional techniques may be used to determine the amount of Ni in the soil, the amount of rock-derivable cations in the tissue of the hyperaccumulator plants or the soil, the amount of heavy metals in the tissue of the hyperaccumulator plants or the soi, the pH of the soil, the electrical conductivity of the soil, and other aspects of the weatherable rock, soil, and hyperaccumulator plants, including quantification of the weathering rate.
  • quantification of the weathering rate For example, X-ray fluorescence analysis of weathered rock material (retrieved from mesh bags buried in the plots) is used to quantify changes in grain surface chemistry. These data provide an independent method for mineral weathering rate quantification. The loss of cations from the added rocks may serve as a proxy for the accumulation of cations released from this process in the plant and soil.
  • Enhanced weathering of the added rock material is also supported by evidence of elevated soil electrical conductivity (EC) following rock applications as shown in FIG. 6.
  • EC electrical conductivity
  • Higher EC indicates the release of cations due to rock dissolution, and similarly represents evidence for chemical weathering of the serpentinite rock applied to the soil. This chemical weathering leads to carbon dioxide sequestration.
  • Timeseries data for soil-extractable Ni was determined by a Mehlich 1 extraction procedure and confirms that soil concentrations increased in all plots treated with serpentinite rock between when the trial began (0 m) and the following spring ( ⁇ 5 m), when the hyperaccumulators would have exhibited low primary production as shown in FIG. 8.
  • the subsequent steep reduction in soil Ni concentrations between spring ( ⁇ 5 m) and mid-summer ( ⁇ 7 m) is evidence for the uptake of soil Ni and depletion of the soil Ni pool by the hyperaccumulator plants at a time of increasing primary productivity as shown in FIG. 8.
  • FIG. 17 A scale diagram of the randomized complete block design used in the trial is shown in FIG. 17.
  • the trial uses an approximately level 112 m x 208 m field site that is divided into four blocks of equivalent area, each measuring 56 m x 104 m, with every block subdivided into 10 randomly-assigned 12 m x 18 m plots representing the ten treatments as shown in FIG. 17.
  • the amount of rock treatment added to each plot as measured in tonnes of serpentinite rock per hectare is shown in FIG. 17. Neither rock nor hyper- accumulator plants are added to the plots marked with ‘XX’ in FIG. 17. These plots are designed to simulate native soil conditions.
  • the plots are segregated by an 8 m margin of untreated land.
  • rock-free control i.e. 0 tonnes of rock added per hectare
  • XX no plants, rock amendments, or management practices
  • the rock-free control is used to assess the effect of different rock applications on nickel uptake efficiency and carbon capture.
  • the experiments with no plants, rock amendments, or management practices control serves a baseline (the native soil’s background conditions).
  • Soils are then tested for pH (in H2O and IM KC1) and electrical conductivity (in H2O); inorganic/organic carbon and nitrogen %; plant-available nitrogen, phosphorus and potassium; soil texture (sand/silt/clay %), bulk density and water holding capacity; cation exchange capacity and exchangeable acidity; major oxide and soil mineralogy %; and, total and plant-available Ca, Mg, K, Na, Fe, Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn. Further soil samples are taken at bi -monthly intervals and tested to determine changes in fundamental soil parameters (pH, electrical conductivity, organic/inorganic carbon) and the concentration of exchangeable (plant- available) metals. These data are critical for monitoring changes in nickel availability and carbon dioxide capture rates in the plots.
  • shoot tissues are harvested from all plots, and the shoot tissues are dried and weighed to quantify crop performance.
  • plant materials are powdered, digested, and tested to determine metal content and analyze the correlation between rock application rate and nickel uptake efficiency.
  • Total plant calcium, magnesium, potassium, and sodium values are added to the respective values from the soil analyses of exchangeable elements, which together enable the quantification of rock weathering and carbon capture rates.
  • Pore water samples are extracted from the soil using lysimeters installed in the plots. These aqueous samples are analyzed for changes in the following parameters: pH, electrical conductivity, and alkalinity; and dissolved cations (e.g. nickel, magnesium) and anions (e.g. chloride, nitrate). These data are essential for accurate monitoring of rock dissolution, nickel release, and carbon capture rates. Soil-atmosphere greenhouse gas sample collection and measurements
  • a Life Cycle Assessment was employed to ensure that the enhanced rock weathering/hyperaccumulator plant operation is sufficiently CO2 negative at the necessary scale.
  • the aim was to model the net sequestration of 1 kilotonne and 1 megatonne of CO2 per year.
  • the LCA was conducted using SimaPro software which draws data from various databases.
  • the study adopted a cradle-to-gate approach, which includes all the major processes in the life cycle from the mining operation to the production of nickel ore, however the environmental impact of waste treatment was excluded from the LCA due to the ambiguity of its relevance.
  • the two products of the operation are CO2 uptake (carbon dioxide removal through enhanced rock weathering) and the production of nickel ore through phytomining.
  • the major processes within the established system boundaries include the mining, crushing, and milling of serpentine, the transportation of the serpentine rock to the site of placement, the fertilizer used, and harvesting, drying, and combustion of the hyperaccumulator plants.
  • a unit area of land was used as the functional unit for the LCA to account for both the CO2 extraction and the nickel ore production. For example, per every m 2 of area of serpentine soil used for the cultivation of A. Murale (or a similar hyperaccumulator plant), a certain amount of nickel will be produced and a certain amount of CO2 will be sequestered.
  • This functional unit ensures that neither of the two products of the system (i.e. CO2 uptake and the production of nickel ore) are neglected from the LCA analysis and that their amounts are calculated independently of each other.
  • the data used for the LCA was collected from several sources and the model was built on the basis of existing models.
  • the data related to standard transportation, machinery, energy, and materials were kept as they were in the models, apart from several necessary adjustments to bring the model closer in line with the operation. For example, during the whole process, the electricity comes from the grid, where it is mostly produced using hydropower. This feature was reflected in the model. It is not required that hydropower be utilized in the process, though it will lower the net negative efficiency.
  • the information used to determine the parameter values was sourced from a combination of existing literature on similar experiments with hyperaccumulators and mineral weathering. The firm relied on rates of natural weathering processes which resulted in calculations that predict significant CO2 uptake and nickel production.
  • FIG. 18 The models for 1 kilotonne-scale production yearly can be seen in FIG. 18.
  • the 1 megatonne-scale chart can be seen in FIGS. 19A and 19B.
  • the main difference between the operations is the increased transport distance between the serpentine mining site and the farming sites in the megatonne- scale model as compared to thel kilotonne-scale model.
  • utilizing renewable energy for transportation of the rock between the mining site and farming sites would help ensure that the process remains CO2 negative even with long transportation distances.
  • the operation can run at scale at an approximately 90% net efficiency in terms CO2 sequestration; additional details of the LCA study can be found in FIG. 20.

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Abstract

L'invention concerne des procédés d'extraction de métaux à partir de roches et de séquestration de dioxyde de carbone. Dans certains modes de réalisation, l'invention concerne des procédés d'utilisation de phytominage pour extraire des métaux de roches ultramafiques tout en séquestrant le dioxyde de carbone. L'invention concerne également des compositions, y compris des compositions métalliques produites par les procédés de l'invention.
PCT/US2023/070710 2022-07-22 2023-07-21 Procédés d'obtention de métaux carboneutres ou carbonégatifs à partir de plantes, et compositions associées Ceased WO2024020548A2 (fr)

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