Methods and apparatuses for in-SITU and integrated production of clean fuels, carbon dioxide mineralization, and mining

Abstract

Apparatuses, systems, and methods for leveraging subsurface geochemical reactions to provide optimal conditions for chemical extraction, hydrogen gas and / or ammonia formation and collection, carbon dioxide mineralization, and mining. In some embodiments, an integrated system can be used to simultaneously 1) produce hydrogen (H2) and ammonia (NH3) in-situ by injecting H2O and nitrogen (N)-sources onto ultramafic rocks; 2) mineralization of carbon dioxide (CO2) by injecting CO2 gas onto ultramafic rocks; and 3) collection and separation of percolated fluid form water- ultramafic rocks to extract valuable trace elements therefrom. The integrated system can deliver reactants through a subsurface for reaction with rocks disposed below ground, and outlets for collecting the products from the earth.

Description

Attorney Docket No.: MIT 25812 PCT | 88212-414784METHODS AND APPARATUSES FOR IN-SITU AND INTEGRATED PRODUCTION OF CLEAN FUELS, CARBON DIOXIDE MINERALIZATION, AND MINING CROSS REFERENCE TO RELATED APPLICATION

[0001] The present disclosure claims priority to and the benefit of U.S. Provisional Application No.63 / 635,608, entitled “Methods and Apparatuses for In-Situ and Integrated Production of Clean Fuels, Carbon Dioxide Mineralization, and Mining,” filed on April 17, 2024, the content of which is incorporated by reference herein in its entirety. FIELD

[0002] The present disclosure relates to in-situ production of hydrogen gas and / or ammonia, and more particularly relates to methods and apparatuses for leveraging subsurface geochemical reactions to provide optimal conditions for chemical extraction, hydrogen gas, and / or ammonia formation and collection, carbon dioxide mineralization, and mining. BACKGROUND

[0003] There is a widely held belief in the scientific community that the world currently stands at a precipice of a pivotal shift in the energy landscape, and the quest for sustainable and environmentally friendly energy sources has never been more pressing. The global effort to transition to green energy can hinge on three objectives: the harnessing of hydrogen (H2) as a clean energy carrier; the effective sequestration of carbon dioxide (CO2); and the efficient / green mining of critical minerals to supply clean energy technologies, such as batteries. These objectives form a triad that underpins the transformation of energy systems and the attainment of a low-carbon future. However, their implementation has been difficult, if not impossible, as they are either too expensive and / or inefficient to replace the world’s current fossil fuel-dependent practices.

[0004] Accordingly, there is a need for systems and techniques that can improve efficiency of production of various clean fuels while reducing environmental impacts during production of such fuels.Attorney Docket No.: MIT 25812 PCT | 88212-414784 SUMMARY

[0005] The present application is directed to systems, methods, and apparatuses that are capable of: 1) production of hydrogen gas (H2) and ammonia (NH3) by injecting H2O and N- sources onto ultramafic rocks; 2) mineralization of CO2 by injecting CO2 gas onto ultramafic rocks; and / or 3) collection and separation of percolated fluid form water-ultramafic rocks to extract valuable trace elements such as lithium (Li), cobalt (Co), and nickel (Ni), among others. The systems of the present embodiments can be integrated such that one or more of 1) to 3) discussed above can occur simultaneously. The system can include a passage that can introduce reactants to the ultramafic rock bed to promote reactions with said rock bed to form the various gases and minerals discussed herein, and collect the liquid water containing the extracted trace elements therein. These techniques allow for harnessing a clean energy carrier (such as hydrogen gas (H2) and ammonia (NH3)), the effective sequestration of carbon dioxide (CO2), and the efficient / green mining of critical minerals to supply clean energy technologies, such as batteries.

[0006] One method of producing at least one of hydrogen gas or ammonia via geochemistry includes transporting one or more reactants below a surface of the earth to facilitate a reaction to form at least one of hydrogen gas or ammonia in-situ.

[0007] One or more reactants can be transported to a rock bed comprising ultramafic rock that is disposed below the surface of the earth. One or more of the reactants can be reacted with the ultramafic rock to produce hydrogen gas (H2). The one or more reactants can include one or more of water (H2O) and N-sources. The reaction can include oxidation of iron (Fe) in the ultramafic rock and reducing the water and nitrogen sources to produce at least one of hydrogen gas or ammonia.

[0008] The method can further include controlling a flow rate and composition of the one or more reactants to below the surface of the earth. In some embodiments, one or more catalysts or additives can be added to the one or more reactants. A pressure of the reaction can be greater than or equal to 1 atm and a temperature of the reaction can be greater than or equal to room temperature.

[0009] The at least one of hydrogen gas or ammonia can be collected in a collection well. The collection well can be disposed above a surface of the earth.Attorney Docket No.: MIT 25812 PCT | 88212-414784

[0010] One or more of the reactants can include carbon dioxide (CO2). The carbon dioxide can react with the rock bed to form a solid precipitate. The solid precipitate can be collected from below the surface of the earth.

[0011] In some embodiments, the one or more reactants can form a percolated fluid containing one or more trace elements when contacting the ultramafic rock. The one or more trace elements can include one or more of lithium (Li), cobalt (Co), platinum (Pt), iron (Fe), chromium (Cr), magnesium (Mg), silicon (Si), calcium (Ca), palladium (Pd), and rhodium (Rh), vanadium (V), nickel (Ni) or, Rare Earth Elements (such as yttrium (Y) lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), or lutetium (Lu). In some embodiments, the percolated fluid can collect in a collection well that is connected to one or more of electrochemical-based separation methods and / or membrane-based separation methods. The percolated fluid can be separated from the one or more trace elements to form an aqueous solution.

[0012] In some embodiments, the aqueous solution can be recycled. Recycling can include re-injecting the recycled aqueous solution below the surface of the earth. The aqueous solution can be recycled repeatedly until it is saturated for further resource extraction. Using a controller, at least one of a flow rate of the aqueous solution below the surface of the earth can be adjusted or a composition of the aqueous solution. Formation of at least two of the at least one of hydrogen gas or ammonia, the solid precipitate, and the percolated fluid can occur simultaneously. In some embodiments, formation of each of the at least one of hydrogen gas or ammonia, the solid precipitate, and the percolated fluid can occur simultaneously. The reaction can occur at a pressure approximately in a range from about 1 atm (0.1 MPa) to about greater than 30 MPa.

[0013] One embodiment of a system includes a reactor, a separation device, and one or more flow passages extending from the surface of the earth. The reactor includes one or more conduits disposed within the ground. The one or more conduits are configured to deliver one or more reactants below a surface of the earth to form a product in-situ. The separation device is configured to receive a solution therethrough for extraction of one or more compounds therefrom. The one or more flow passages are configured to deliver a solution to the separation device.Attorney Docket No.: MIT 25812 PCT | 88212-414784

[0014] The system can be configured to perform formation of the product in-situ and extraction simultaneously. The product can include at least one of hydrogen gas or ammonia. The separation device can be configured to extract one or more trace minerals from the solution.

[0015] The one or more reactants can include carbon dioxide (CO2). The reactor can react the carbon dioxide below the surface of the earth to mineralize a solid precipitate. In some embodiments, the system can be configured to perform mineralization simultaneously with one or more of formation of the product in-situ and extraction. The one or more passages can be configured to flow compounds above the surface of the earth.

[0016] In some embodiments, the system can include a collection well for collecting the product in-situ. The collection well can be disposed above the surface of the earth. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] This disclosure will be more fully understood from the following detailed description, taken in conjunction with the accompanying drawings, in which:

[0018] FIG. 1A is a schematic representation of an example embodiment of an integrated system of the present embodiments configured for simultaneous 1) in-situ generation of geological hydrogen, 2) carbon dioxide (CO2) sequestration, and 3) electrochemical extraction of critical minerals from ultramafic rocks;

[0019] FIG. 1B is an alternate schematic representation of the integrated system of FIG.1A showing a collection and extraction system;

[0020] FIG.1C is an alternate schematic representation of the integrated system of FIG.1B disposed below the subsurface;

[0021] FIG.2 is a schematic representation of a reaction for production of in-situ natural hydrogen at an ultramafic rock using the integrated system of FIG.1A;

[0022] FIG. 3 is a schematic representation of components and corresponding flows through an integrated system of the present embodiments;

[0023] FIG.4 is a schematic representation of a reaction for CO2 sequestration at an ultramafic rock using the integrated system of FIG.1A; andAttorney Docket No.: MIT 25812 PCT | 88212-414784

[0024] FIG.5 is a schematic representation of electrochemical extraction of critical minerals from ultramafic rocks using the integrated system of FIG.1A. DETAILED DESCRIPTION

[0025] Certain exemplary embodiments will now be described to provide an overall understanding of the principles of the systems and methods disclosed herein. The description is inclusive of all descriptions, including any accompanying figures, whether in the present document and / or any materials or other information incorporated by reference herein. One or more examples of these embodiments are illustrated in the accompanying drawings. Those skilled in the art will understand that the systems, methods, and apparatuses specifically described herein and illustrated in the accompanying drawings are non-limiting exemplary embodiments and that the scope of the present disclosure is defined solely by the claims. The features illustrated or described in connection with one exemplary embodiment may be combined with the features of other embodiments. Such modifications and variations are intended to be included within the scope of the present disclosure. To the extent the present disclosure includes illustrations and descriptions that include schematic illustrations of systems, apparatuses, set-ups, techniques, methodologies, and the like, a person skilled in the art will recognize how to reply upon the present disclosure to integrate the systems, apparatuses, set-ups, techniques, methodologies, and the like into a product, system, production, method, etc. of effecting in-situ production of ammonia. Additionally, to the extent the present disclosure includes various terms for components and / or processes of the disclosed systems, apparatuses, set-ups, techniques, methodologies, and the like, one skilled in the art, in view of the claims, present disclosure, and knowledge of the skilled person, will understand such terms are merely examples of such components and / or processes, and other components, designs, processes, and / or actions are possible.

[0026] The solutions to the anthropogenic effects of global warming may lie beneath the Earth's subsurface and might be the singular remedy that simultaneously achieves the objectives of: 1) in-situ generation of geological hydrogen; 2) carbon dioxide (CO2) sequestration; and / or 3) electrochemical extraction of critical minerals from ultramafic rocks. For the first objective, hydrogen can be an important energy carrier that can play a significant role in reaching net zero emission (NZE). There are several known pathways for producing hydrogen including: 1) steam-methane reforming (CH4+ 2H2O → 4H2+ CO2(Eq.1)), which emits CO2; and 2) the use of renewable energy to split water (H2O → H2 + ½ O2 (Eq.2)),Attorney Docket No.: MIT 25812 PCT | 88212-414784 with the latter equation relying on sufficient renewable energy generation, storage, and transmission. According to the International Energy Agency, to meet NZE, 17,000 TWh of hydrogen-based energy can be used, which is about 60% of today’s global electricity production, and which uses significant effort in efficient and cost-effective batteries, electrolyzers, and renewable energy harvesting. However, there is an even cleaner, cheaper, and exceedingly abundant form of hydrogen which is geological or natural hydrogen, and its source is Earth’s subsurface. In fact, the Earth emits about 20 million tons (Mt) of hydrogen to the atmosphere from its subsurface. The reaction that creates natural hydrogen involves the reduction of water upon oxidation of ferrous iron containing mineral rocks (called ultramafic rocks) to ferric iron, with a simplified version of the reaction being as follows: (2FeO + H2O → Fe3O4+ H2(Eq.3)). A calculation for the first seven (7) kilometers of the earth’s crust estimates that there is enough ultramafic rocks that can produce hydrogen for about 250,000 years (about 100 trillion tons of hydrogen at a rate of about 400 Mt annually, achieving NZE with hydrogen as a primary fuel). High temperature (about 300 °C) and pressure (up to about 35 MPa) is typically used for this reaction to happen and is naturally provided by the Earth sub-surface free of cost. Therefore, the Earth is a de facto hydrogen factory waiting to be tapped, but no current technologies exist to harness the hydrogen.

[0027] The present disclosure provides for an apparatus and integrated system, e.g., a reactor, which can both stimulate natural hydrogen generation reaction and collection. Natural hydrogen can be extracted in two ways. The first may be passive in its nature, which can involve trapping natural hydrogen from regions where native hydrogen (white hydrogen) spontaneously seeps from subsurface. These regions are plentiful and can span from Mali, West Africa to Kansas, USA and beyond, for example. White hydrogen may be geographically limited and unpredictable, however due to its propensity to leak and the need for extensive exploration to pinpoint its location. As a result, ideal rock formations that trap the gas in the subsurface may be desirable when trapping white hydrogen, thereby narrowing a number of locations that its trapping is efficient and / or economically feasible. Thus, a second mode of extraction can be used, which involves proactive (active) formation of natural hydrogen by injecting a water solution in-situ into subsurface ultramafic rocks to induce reduction of the water (Eq.3) and collect the emitted hydrogen gas (Orange hydrogen), which is henceforth referred to as hydrogen production INH (for in-situ natural hydrogen). At least because the Earth provides the natural condition for the reaction (the rock, high temperature, and pressure), INH may allow hydrogen to be produced atAttorney Docket No.: MIT 25812 PCT | 88212-414784 unprecedently lower costs, which can provide a pathway that can replace fossil fuel dependent H2production (steam reforming).

[0028] At least one novel feature of the present embodiments includes apparatuses and integrated systems that are configured to harness a clean energy carrier (such as hydrogen (H2) and ammonia NH3), sequester carbon dioxide (CO2), and green mine critical minerals to supply clean energy technologies, such as batteries. For example, the instantly disclosed apparatuses and systems can be used for simultaneous: 1) in-situ production of H2 and NH3 by injecting H2O and nitrogen (N)-sources, e.g., N2or NO3-, onto ultramafic rocks; 2) mineralization of CO2 by injecting CO2 gas onto ultramafic rocks; and / or 3) collection and separation of percolated fluid form water-ultramafic rocks to extract valuable elements such as lithium (Li), cobalt (Co), and / or nickel (Ni). Each of these techniques will be discussed in detail below, with continued reference to the elements of FIG. 1A as they are discussed. It will be appreciated that while the present disclosure discusses each of these techniques discussed can occur simultaneously, though it will be appreciated that one or more of these techniques can occur independently, or two can occur simultaneously. For the purposes of the present disclosure, the term simultaneously can refer to techniques that occur with some overlap between one another, e.g., in-situ production of H2, NH3and / or CO2mineralization can start to occur at the same time, or, in some embodiments, collection and separation of the critical minerals can take place after in-situ production of H2, NH3and / or CO2has begun, and / or when one of in-situ production and / or mineralization has concluded.

[0029] IN-SITU HYDROGEN PRODUCTION

[0030] FIG.1A illustrates one example embodiment of an integrated system 100 of the present embodiments. The integrated system 100 can provide for high-yield in-situ natural hydrogen gas and / or ammonia production, which can include proactive (active) formation of natural hydrogen and ammonia by delivering, e.g., injecting, a water solution in-situ into subsurface ultramafic rocks to induce reduction of the water and collection of the emitted hydrogen gas, such as orange hydrogen, and ammonia with high rate and yield. In some embodiments, controlling a flow rate and composition of the aqueous solution to below a surface of the earth 102 can allow for increased hydrogen gas and / or ammonia yield, as well as improvement of efficiency of said collection.Attorney Docket No.: MIT 25812 PCT | 88212-414784

[0031] As shown, the system 100 can include a passage or apparatus 104 having an inlet 106 for receiving the aqueous solution therethrough. The passage 104 can extend below the surface of the earth 102 to the ultramafic rocks 106 down below. For example, ultramafic- rich regions of the earth’s crust can be detected by remote sensing, seismic survey, borehole and well logging, geochemical analysis, and the like as known to one skilled in the art, and as such a detailed discussion of detection is omitted from this disclosure. While the depth of the location within the earth’s crust that ultramafic is found can depend on factors including but not limited to geography, climate, and so forth, a depth of boreholes used in the present disclosure can be approximately in a range of about 1 foot to about 10 miles below the earth’s surface, approximately in a range of about 1 foot to about 5 miles below the earth’s surface, approximately in a range of about 3 feet to about 10 miles below the earth’s surface, approximately in a range of about 3 feet to about 10 miles below the earth’s surface, approximately in a range of about 5 feet to about 10 miles below the earth’s surface, and / or approximately in a range of about 5 miles to about 5 miles below the earth’s surface.

[0032] The passage 104 can receive a mixture of one or more of a nitrogen source, a catalyst, carbon dioxide, and so forth. For example, the system 100 can expose the ultramafic rock bed 106 to water and a nitrogen source (NO3−and N2) in the presence of a catalyst (Cu2+or Ni2+) to synthesize ammonia. Some additional non-limiting examples of the nitrogen source can be one or more of N2, NO, N2O, NO2, NOx, NO3−, among others, and some additional non-limiting examples of catalysts can include nickel, copper, cobalt, sodium, magnesium, calcium, titanium, chromium, iron, zinc, platinum, ruthenium, and osmium, aluminum oxide, calcium oxide, molybdenum, ruthenium, alloys of different metals, organic and metalorganic catalysts, and so forth. Compounds can flow in either direction through the flow passages or conduits 104, with some compounds flowing to the subsurface 102 to react with the rock bed 106, and product can flow back above the surface for collection. It will be appreciated that the flow passages 104 can include tubes, pipes, and / or other similar structures used to transport fluid. The flow passages can be made from one or more materials know to one skilled in the art, such as stainless steels, carbon steels, nickel alloys, titanium alloys, ceramic, copper, polyvinyl chloride, aluminum, and so forth. Catalysts and their uses in subsurface geothermal chemical reactions can be found in PCT Application No. PCT / US2024 / 055583, entitled “Methods, Systems, and Apparatuses for In-Situ Production of Compounds via Subsurface Geothermal Chemical Reactions,” filed on an even date herewith, the entire content of which is incorporated herein by reference.Attorney Docket No.: MIT 25812 PCT | 88212-414784

[0033] In some embodiments, the aqueous solution can include one or more additives that can catalyze subsurface reactions and / or promote free-flow of the water through the borehole. The additives can include chemical additives or catalysts that can: 1) control the pH to enhance the rate and yield of the reaction with the olivine rock; and / or 2) provide chemicals that depassivate ultramafic rocks after the reaction so that the surface of the rock can be available for several cycles of hydrogen gas production. A person skilled in the art will recognize that depassivation of the ultramafic rocks can be used due to the surface of the rock being covered with a Fe3O4 passivation layer, which can prevent further reaction. Chemicals can be added to the surface to prevent formation of the passivation layer, which can make the surface available for several reaction cycles. Some non-limiting examples of the additives can include some acids and fluorine containing chemicals. In some embodiments, the additives can be used to control pH.

[0034] The reaction of the water with the rock 106 can occur in a reaction zone 109, as shown in FIGS.1A-1C, and schematically illustrated in FIG.2 below. Once the mixture is injected into, and / or otherwise contacts, the FeO rock bed 106, a reaction can occur to release hydrogen gas. This reaction can occur at a temperature that is approximately in a range from about room temperature to above about 300 °C, or about 70 °C to above about 300 °C, e.g., about 300 °C, about 400 °C, about 500 °C, or more. A range of pressure can be approximately in a range from about 1 atm (0.1 MPa) to about greater than 30 MPa. When no catalyst was added, the amount of NH3 produced by the reaction between the olivine and the nitrate solution can be above about 20 g NH3 / t olivine, and when catalyst is used, the amount of NH3 produced by the reaction between the olivine and the nitrate solution can be above about 2kg NH3 / t olivine.

[0035] For example, in some embodiments, FeO in the ultramafic rock can be oxidized while the water from the influent fluid is reduced to produce H2: 2FeO(s)+ H2O(l / g)→ Fe2O3(s)+ H2(g) (which is a generic and simplified reaction that explains what is going in the ultramafic rock). The water can be a liquid or a gas, depending on the reaction set-up (e.g., injecting liquid water and / or droplets in vapor form). The specific reaction may depend on the type of ultramafic rock. The following are two examples of specific reactions: 6 Fe2SiO4(s) [fayalite] + 7 H2O(l / g) → 3Fe3Si2O5(OH)4(s) [lizardite] + Fe3O4(s) [magnetite] + H2(g).

[0036] The pathway of hydrogen production from rocks, called a serpentinization process, can be currently explained mainly by the following reaction processes (Eq.4–7):Attorney Docket No.: MIT 25812 PCT | 88212-414784 (Fe,Mg)2SiO4 (olivine) + H2O → (Fe,Mg)6Si4O10(OH)8 (olivine) + (Mg1−x,Fex)(OH)2 (Fe- bearing brucite) + Fe3O4(magnetite)+ H2(Eq.4) (Mg1−x,Fex)(OH)2 + H2O → (1−x) Mg2++ x Fe2++ 2OH−(Eq.5) Fe2++ 2OH−→ Fe(OH)2 (Eq.6) 3Fe(OH)2 + 2 H2O → Fe3O4 + H2 + 4H2O (Eq.7)

[0037] In principle, the production of hydrogen can rely on the redox reaction between the ferrous iron (Fe2+) and water. Inspired by this, the reduction potential of ferrous iron in rocks can be utilized, but instead of reducing water, nitrogenous substances (nitrate or nitrogen gas) can be reduced in the expectation of producing ammonia. The following reaction equation (Eq.8) describes the chemistry basis of geological ammonia production: Nitrate in aqueous solution is reduced by Fe(OH)2 present in (or transformed from) the rock to generate ammonia, while Fe(OH)2can be oxidized to Fe3O4: 12Fe(OH)2+ XNO3→ NH3+ 4Fe3O4+ 10H2O + XOH (X=Na, K, etc.) (Eq.8)

[0038] As mentioned above, each of the production, mineralization, and collection techniques discussed herein to operate both above ground, e.g., by utilizing already extracted rocks or mining tailings, as shown in FIG.1B, and within the sub-surface, e.g., by directly injecting into a vertical hole in the earth to access the rocks, as shown in FIG.1C. When used below the subsurface, a portion of the passage 104 can be disposed below ground, as shown in FIG.1B, though it will be appreciated that an entirety of the passage can also be disposed below ground in some embodiments.

[0039] The system 100 can include a controller 160 for adjusting one or more system parameters. For example, one or more of the flow rate and / or the composition of the influent fluid can be adjusted. In some embodiments, a flow rate of the water through the boreholes can be adjusted to be approximately in a range of about 5 cubic meters per second to about 50 cubic meters per second, and more particularly approximately in a range of about 20 cubic meters per second to about 30 cubic meters per second.

[0040] Once the reactions have taken place, hydrogen and ammonia can be passed via an outlet 108 to a collection tank or collection well 110. The collection tank 110 can beAttorney Docket No.: MIT 25812 PCT | 88212-414784 disposed above the subsurface 104, though in some embodiments, the collection tank 110 can be below the subsurface 104. An existing challenge to in-situ hydrogen production can be that the reaction rate of the reaction is low. Moreover, methods to accurately probe, quantify, optimize, and / or determine factors affecting the reaction rate of geological hydrogen may not currently exist. In the present embodiments, spectroscopic tools such as Gas Chromatography–Mass Spectrometer can be used to measure hydrogen generated. Given the diversity of rock types and external stimuli, a customized reactor for in situ hydrogen extraction utilizing autonomous and high-throughput platform for rate optimization reactor design can be used.

[0041] One example for an integrated system 200 used to simultaneously: 1) produce hydrogen (H2) and ammonia (NH3) in-situ by injecting H2O and nitrogen (N)-sources onto ultramafic rocks; 2) mineralize carbon dioxide (CO2) by injecting CO2 gas onto ultramafic rocks; and / or 3) collect and separate of percolated fluid form water-ultramafic rocks to extract valuable trace elements therefrom. The system 200 can include a plurality of tanks configured to deliver the reactants below the surface of the earth 102 to the ultramafic rocks 106 down below. As shown, the plurality of tanks can include an aqueous solution / water tank 130, a carbon dioxide tank 132, and the collection tank or collection well 110. Each of the reactants can be pumped from the aqueous solution / water tank 130 and the carbon dioxide tank 132 via a plurality of pumps 134 towards the ultramafic rock 106 to facilitate the desired reaction.

[0042] For example, in a first method application of the system 200, the reaction can be allowed to proceed for a pre-determined period, based on factors like reaction kinetics, rock- fluid permeability, fluid transport rate, and / or other parameters that can be optimized beforehand for a specific borehole system. After the designated time, which can be regulated by the controller 160, the reaction to produce H₂ / NH₃ and / or CO₂ mineralization can take place as planned, after which water can be retrieved from the subsurface of the earth 102 for trace element separation and purification.

[0043] A second application of the system can include monitoring and quantifying the production of H₂ and NH₃ gases. As these gases form, they can migrate naturally to the surface due, at least in part, to the pressure gradient (from high pressure in the reaction zone 109 near the rock 106 to lower pressure at the Earth’s surface). The collection tank 110 can be equipped with sensors for gas, light, and / or electrochemical detection, or otherAttorney Docket No.: MIT 25812 PCT | 88212-414784 quantification methods to detect and measure gas formation. The volume of gas produced can be recorded over time, and when gas production saturates, this can serve as an indication that the reaction has completed. At this point, water can be retrieved from the subsurface for trace element separation and purification.

[0044] Once the water containing trace elements is collected, it can be processed through an electrochemical separation system, e.g., extraction apparatus 114, which can be one or more of electrodialysis, electrocoagulation, and / or electrodeionization, among others. This electrochemical separation system can include the anode 116, the cathode 118, and selective membranes, e.g., anion exchange membrane (AEM) 136 and cation exchange membrane (CEM)138. An external current or voltage can be applied to the anode 116 and the cathode 118, allowing for the selective extraction of trace elements from the water.

[0045] In this system 200, the wastewater can be injected and flow between the anode 116 and the cathode 118 under an applied electric bias. The electric field can drive the movement of ions toward the electrodes: positively charged ions are attracted to the cathode 118, while negatively charged ions move toward the anode. This selective ion migration can lead to the deposition or collection of trace elements on the electrode surfaces, or within specific membrane regions. Each method within the system 200 can have a unique mechanism. For example, electrodialysis can use selective membranes 136 to separate ions by directing them to opposite electrodes, effectively concentrating trace elements in specific compartments. Electrocoagulation can generate flocs through the dissolution of metal ions from the electrodes, which can trap trace elements, allowing them to be removed as solid particles. Electrodeionization can combine ion-exchange resins and membranes, continuously removing ions from the water under the electric field to produce purified water while concentrating trace elements for extraction. Once the trace elements are extracted from the water, they can be sent to a water purification system 140 via path 115, where further purification of organic and inorganic impurities can be performed using one or more of a membrane-based filtration system, a distillation column, reverse osmosis, activated carbon filtration, advanced oxidation processes, ozonation, ion-exchange, and / or others. After purification, the water can be injected back into the borehole along with the CO₂. The control system or controller 160 can control, for example, the flow rate, which can be based on, for example, pre-set values as the water is injected and ejected from the electrochemical system.

[0046] CARBON DIOXIDE SEQUESTRATIONAttorney Docket No.: MIT 25812 PCT | 88212-414784

[0047] The ultramafic rocks 106 into which the aqueous solution is injected can serve as ideal sites for carbon sequestration. Carbon sequestration has a global capacity of 100 trillion tons of CO2, and to put this into perspective, the estimated anthropogenic CO2 emissions in 2020 were around 33 billion tons. The ultramafic rocks 106 not only contain FeO but also include MgO, which can react with injected CO2 upon sequestration to mineralize to produce MgCO3 (MgO + CO2 → MgCO3 (Eq.9)), as shown in FIG.4. That is, as mentioned above, the aqueous solution can include carbon dioxide gas that can flow to the reaction zone to react with magnesium oxide (MgO) in the rocks to form MgCO3 (MgO + CO2 → MgCO3), as shown in FIG.1A and FIG.4. A flow rate of the carbon dioxide through the passage 104 toward the ultramafic rock 106 can be controlled to optimize formation of the magnesium carbonate. In this way, rather than releasing carbon dioxide into the atmosphere, carbon dioxide gas can react to form solid compounds, thereby reducing and / or eliminating carbon dioxide emissions from the reaction process of formation of hydrogen gas or ammonia. The MgCO3 can then be collected by methods known to one skilled in the art.

[0048] ELECTROCHEMICAL EXTRACTION OF CRITICAL MINERALS FROM ULTRAMAFIC ROCKS

[0049] At least another novel feature of the president embodiments is the ability of the system 100 to concurrently perform carbon dioxide sequestration simultaneously with in-situ hydrogen production and electrochemical extraction of minerals, which is discussed in greater detail below. For example, the system 100 can include a second outlet 112 for transporting liquid from the reaction zone 109 in the ultramafic rock 106. The outlet 112 can transport the liquid to an extraction apparatus or system 114, as shown in FIGS.1A-1C. The ultramafic rock 106, in addition to allowing for the production of hydrogen gas and ammonia, can include essential or trace elements for the green transition (lithium (Li), nickel (Ni), and cobalt (Co), among others, which are commonly used components in batteries. That is, when the aqueous solution contacts the ultramafic rocks 106 to react therewith to form at least one of hydrogen gas or ammonia, can dissolve valuable chemicals from the ultramafic rocks 106 to create a percolated fluid containing one or more of the Li, Co, Ni, among others. Some additional non-limiting examples of the trace element can include one or more of lithium (Li), cobalt (Co), platinum (Pt), iron (Fe), chromium (Cr), magnesium (Mg), silicon (Si), calcium (Ca), palladium (Pd), and rhodium (Rh), vanadium (V), nickel (Ni) or, Rare Earth Elements (such as yttrium (Y) lanthanum (La), cerium (Ce), praseodymium (Pr), neodymiumAttorney Docket No.: MIT 25812 PCT | 88212-414784 (Nd), and samarium (Sm), as well as the heavy rare earth elements (RRE): europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and / or lutetium (Lu).

[0050] FIG. 5 illustrates the formation of the percolated fluid upon contact between the aqueous solution and the rock in greater detail. These dissolved elements in the injected fluid can be extracted (mined) by applying electrochemical and / or membrane-based separation methods known to those skilled in the art. For example, electrochemical potential (voltage) can be applied which enables selective and step-by-step extraction of the Li, Co and Ni. Moreover, one or more of electrodialysis, electrochemical deposition, selective ion intercalation, and / or other electrochemical methods can be combined to achieve selective separation of ions. Electrodialysis is a separation process in which ions of different charges are transported through ion exchange membranes when an electrical potential is applied between the anode 116 and the cathode 118 to trap the essential elements in a portion thereof 120. Selectivity can be achieved by optimizing the ion exchange membrane and tuning the rate of ion migration. Through electrolyte engineering and surface functionalization, metal ions’ selectivity can be tuned during electrochemical deposition. For example, in some embodiments, lithium iron phosphate (LiFePO4) and lithium manganese oxide (LiMn2O4) intercalation materials can be used for the direct recovery of lithium ions.

[0051] Raw material supplies can be produced for battery production via the extraction apparatus 114, which can serve as an additional benefit of the in-situ hydrogen production process. The extraction apparatus 114 can be disposed above ground as shown in FIG.1B, though in some embodiments the extraction can be performed below the subsurface. The aqueous solution can be recycled via path 115 and re-introduced below the surface via the passage 104 for further reaction with the ultramafic rock 106 to form more of hydrogen gas and / or ammonia. It will be appreciated that the solution can be repeatedly utilized in the reactor until saturation for further resource extraction.

[0052] Examples of the above-described embodiments can include the following: 1. A method of producing at least one of hydrogen gas or ammonia via geochemistry, comprising: transporting one or more reactants below a surface of the earth to facilitate a reaction to form at least one of hydrogen gas or ammonia in-situ.Attorney Docket No.: MIT 25812 PCT | 88212-414784 2. The method of example 1, wherein the one or more reactants are transported to a rock bed comprising ultramafic rock that is disposed below the surface of the earth. 3. The method of example 1 or example 2, further comprising reacting the one or more reactants with the ultramafic rock to produce hydrogen gas (H2). 4. The method of any of examples 1 to 3, wherein the one or more reactants comprise one or more of water (H2O) and N-sources. 5. The method of example 4, wherein the reaction comprises oxidation of iron (Fe) in the ultramafic rock and reducing the water and nitrogen sources to produce at least one of hydrogen gas or ammonia. 6. The method of any of examples 1 to 5, further comprising controlling a flow rate and composition of the one or more reactants to below the surface of the earth. 7. The method of any of examples 4 to 6, further comprising adding one or more catalysts or additives to the one or more reactants. 8. The method of any of examples 1 to 7, further comprising collecting the at least one of hydrogen gas or ammonia in a collection well. 9. The method of example 8, wherein the collection well is disposed above a surface of the earth. 10. The method of any of examples 1 to 9, wherein a pressure of the reaction is greater than or equal to 1 atm and a temperature of the reaction is greater than or equal to room temperature. 11. The method of example 2, wherein the one or more reactants comprise carbon dioxide (CO2). 12. The method of example 11, wherein the carbon dioxide reacts with the rock bed to form a solid precipitate.Attorney Docket No.: MIT 25812 PCT | 88212-414784 13. The method of example 1, wherein the solid precipitate is collected from below the surface of the earth. 14. The method of any of examples 11 to 13, wherein the one or more reactants form a percolated fluid containing one or more trace elements when contacting the ultramafic rock. 15. The method of example 14, wherein the one or more trace elements comprise one or more of lithium (Li), cobalt (Co), platinum (Pt), iron (Fe), chromium (Cr), magnesium (Mg), silicon (Si), calcium (Ca), palladium (Pd), and rhodium (Rh), vanadium (V), nickel (Ni) or, Rare Earth Elements (such as yttrium (Y) lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), or lutetium (Lu). 16. The method of example 14 or example 15, further comprising collecting the percolated fluid in a collection well that is connected to one or more of electrochemical-based separation methods or membrane-based separation methods. 17. The method of any of examples 14 to 16, further comprising separating the percolated fluid from the one or more trace elements to form an aqueous solution. 18. The method of example 17, further comprising recycling the aqueous solution. 19. The method of example 18, wherein recycling further comprises re-injecting the recycled aqueous solution below the surface of the earth. 20. The method of any of examples 17 to 19, wherein the aqueous solution is recycled repeatedly until it is saturated for further resource extraction. 21. The method of any of examples 1 to 20, further comprising, using a controller, adjusting at least one of a flow rate of the aqueous solution below the surface of the earth or a composition of the aqueous solution.Attorney Docket No.: MIT 25812 PCT | 88212-414784 22. The method of any of examples 14 to 21, wherein formation of at least two of the at least one of hydrogen gas or ammonia, the solid precipitate, and the percolated fluid occurs simultaneously. 23. The method of any of examples 14 to 22, wherein formation of each of the at least one of hydrogen gas or ammonia, the solid precipitate, and the percolated fluid occurs simultaneously. 24. The method of any of examples 1 to 23, wherein the reaction occurs at a pressure approximately in a range from about 1 atm (0.1 MPa) to about greater than 30 MPa. 25. A system, comprising: a reactor including one or more conduits disposed within the ground, the one or more conduits being configured to deliver one or more reactants below a surface of the earth to form a product in-situ; a separation device configured to receive a solution therethrough for extraction of one or more compounds therefrom; and one or more flow passages extending from the surface of the earth, the one or more flow passages being configured to deliver a solution to the separation device. 26. The system of example 25, wherein the system is configured to perform formation of the product in-situ and extraction simultaneously. 27. The system of example 25 or example 26, wherein the product comprises at least one of hydrogen gas or ammonia. 28. The system of any of examples 25 to 27, wherein the separation device is configured to extract one or more trace minerals from the solution. 29. The system of any of examples 25 to 28, wherein the one or more reactants comprise carbon dioxide (CO2). 30. The system of example 29, wherein the reactor reacts the carbon dioxide below the surface of the earth to mineralize a solid precipitate.Attorney Docket No.: MIT 25812 PCT | 88212-414784 31. The system of example 30, wherein the system is configured to perform mineralization simultaneously with one or more of formation of the product in-situ and extraction. 32. The system of any of examples 25 to 31, wherein the one or more passages are configured to flow compounds above the surface of the earth. 33. The system of example 32, further comprising a collection well for collecting the product in-situ. 34. The system of example 33, wherein the collection well is disposed above the surface of the earth.

[0053] One skilled in the art will appreciate further features and advantages of the disclosures based on the provided for descriptions and embodiments. Accordingly, the inventions are not to be limited by what has been particularly shown and described. To the extent the present disclosure includes illustrations and descriptions that include prototypes, bench models, or schematic illustrations of set-ups, a person skilled in the art will recognize how to rely upon the present disclosure to integrate the techniques, systems, composition, designs, and methods provided for into a product and / or production method. All publications and references cited herein are expressly incorporated herein by reference in their entirety.

[0054] Some non-limiting claims that are supported by the contents of the present disclosure are provided below.

Claims

Attorney Docket No.: MIT 25812 PCT | 88212-414784 What is claimed is:

1. A method of producing at least one of hydrogen gas or ammonia via geochemistry, comprising: transporting one or more reactants below a surface of the earth to facilitate a reaction to form at least one of hydrogen gas or ammonia in-situ.

2. The method of claim 1, wherein the one or more reactants are transported to a rock bed comprising ultramafic rock that is disposed below the surface of the earth.

3. The method of claim 1, wherein the one or more reactants comprise one or more of water (H2O) and N-sources.

4. The method of claim 1, further comprising controlling a flow rate and composition of the one or more reactants to below the surface of the earth.

5. The method of claim 2, wherein the one or more reactants comprise carbon dioxide (CO2).

6. The method of claim 5, wherein the carbon dioxide reacts with the rock bed to form a solid precipitate.

7. The method of claim 5, wherein the one or more reactants form a percolated fluid containing one or more trace elements when contacting the ultramafic rock.

8. The method of claim 7, wherein the one or more trace elements comprise one or more of lithium (Li), cobalt (Co), platinum (Pt), iron (Fe), chromium (Cr), magnesium (Mg), silicon (Si), calcium (Ca), palladium (Pd), and rhodium (Rh), vanadium (V), nickel (Ni) or, Rare Earth Elements (such as yttrium (Y) lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), or lutetium (Lu).

9. The method of claim 7, further comprising collecting the percolated fluid in a collection well that is connected to one or more of electrochemical-based separation methods or membrane-based separation methods.Attorney Docket No.: MIT 25812 PCT | 88212-414784 10. The method of claim 7, further comprising separating the percolated fluid from the one or more trace elements to form an aqueous solution.

11. The method of claim 7, wherein formation of at least two of the at least one of hydrogen gas or ammonia, the solid precipitate, and the percolated fluid occurs simultaneously.

12. The method of claim 7, wherein formation of each of the at least one of hydrogen gas or ammonia, the solid precipitate, and the percolated fluid occurs simultaneously.

13. A system, comprising: a reactor including one or more conduits disposed within the ground, the one or more conduits being configured to deliver one or more reactants below a surface of the earth to form a product in-situ; a separation device configured to receive a solution therethrough for extraction of one or more compounds therefrom; and one or more flow passages extending from the surface of the earth, the one or more flow passages being configured to deliver a solution to the separation device.

14. The system of claim 13, wherein the system is configured to perform formation of the product in-situ and extraction simultaneously.

15. The system of claim 13, wherein the product comprises at least one of hydrogen gas or ammonia.

16. The system of claim 13, wherein the separation device is configured to extract one or more trace minerals from the solution.

17. The system of claim 13, wherein the one or more reactants comprise carbon dioxide (CO2).

18. The system of claim 17, wherein the reactor reacts the carbon dioxide below the surface of the earth to mineralize a solid precipitate.

19. The system of claim 18, wherein the system is configured to perform mineralization simultaneously with one or more of formation of the product in-situ and extraction.Attorney Docket No.: MIT 25812 PCT | 88212-414784 20. The system of claim 13, wherein the one or more flow passages are configured to flow compounds above the surface of the earth.

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