Methods, systems, and apparatus for in-situ production of compounds via subsurface geothermal chemical reactions

Abstract

Systems and methods for in situ production of ammonia and / or ammonium salt compounds using subsurface geochemistry are provided. In some embodiments, one or more reactants can be delivered to a subsurface region for in situ formation of ammonia and / or ammonium salts. The reactants can be reacted with an ultramafic rock bed to form hydrogen gas (H2). The hydrogen gas can then be reacted with a nitrogen source to form ammonia that can be collected. In another embodiment, nitrogen gas can be pumped into contact with hydrogen gas released from the rock bed to form ammonium salts in the earth's crust that can be mined. In some other embodiments, a catalyst can be delivered with the reactants or the reaction can be facilitated by a catalyst in the rock bed to form ammonia gas in situ without the need for hydrogen gas formation.

Description

[0001] Cross-reference to related applications

[0002] This disclosure claims priority to and benefits from U.S. Provisional Application No. 63 / 547,898, filed November 9, 2023, entitled “Method, System, and Apparatus for In-situ Production of Ammonia and Ammonium Salts from Nitrogen via Subsurface Geothermal Chemical Reactions” and U.S. Provisional Application No. 63 / 644,489, filed May 8, 2024, entitled “Method, System, and Apparatus for In-situ Production of Geological Ammonia via Subsurface Geothermal Chemical Reactions”, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to the in-situ production of geological ammonia and / or ammonium salts, and more specifically to methods and apparatus for providing optimal conditions for the formation of ammonia and / or ammonium salts using a catalyst by utilizing subsurface geochemical reactions. Background Technology

[0004] In recent years, the use of ammonia (NH3) as an energy source has increased significantly, becoming a substitute for fossil fuels. Furthermore, ammonia has begun to be used as fertilizer and as fuel to power various plants and machinery. For example, ammonia is produced annually from dinitrogen (N2) or nitrogen gas and dihydrogen (H2) or hydrogen gas via the Haber-Bosch process, with an annual output of approximately 150 million tons. Current ammonia production technologies have several drawbacks. First, ammonia production is highly energy-intensive. For instance, the Haber-Bosch process requires high pressure (approximately 200 atm to approximately 400 atm) and high temperature (approximately 400°C to approximately 650°C), and indirectly generates millions of tons of CO2 based on the consumption of natural gas and other fossil fuels as energy sources. Second, implementing the Haber-Bosch process is very expensive because the acquisition of hydrogen (a reactant in the process) accounts for more than 30% of the overall production cost of ammonia and / or ammonium salts. In addition, facilities for the Haber-Bosch process tend to be large in size, containing numerous storage tanks, reactors and / or other facilities to facilitate the reaction and manage the output of the resulting ammonia and / or ammonium salts.

[0005] Therefore, there is a need for alternative methods and systems for ammonia production that allow for scalability and widespread adoption while minimizing energy consumption. Summary of the Invention

[0006] This application relates to methods, systems, and apparatus for producing ammonia and / or ammonium salts. For example, the disclosed methods, systems, and apparatus generate ammonia (NH3) by using a hot and iron-rich (Fe) ultramafic material (e.g., rock) (including but not limited to peridotite, olivine ((Mg, Fe)₂SiO₄), pyroxene ((Mg, Fe)CaSi₂O₆), and / or fir olivine (Fe₂SiO₄)) in an aqueous reaction beneath the earth's surface. Bond cleavage. The disclosed methods, systems, and apparatus produce and collect sufficient products without the excessive energy consumption seen in the Haber-Bosch process by reacting under elevated temperatures and pressures provided from beneath the Earth's surface. In-situ production of ammonia and / or ammonium salts can be achieved using a reactor with external channels receiving inflow fluids (H2O and N2) from a supply source and a supply line pumped by a pressure pump into a vertical borehole extending to the surface. The fluids can undergo accelerated reactions with ultramafic bedrock below the borehole, for example, releasing NH3 with iron oxide (FeO)-containing rocks. The NH3 then flows upward along internal channels to settling or collection tanks and / or other discharge lines. In some embodiments, the system can control flow rate, pH, and rock surface depassivation to maximize reaction rate and yield. A catalyst can be added along with the inflow fluid via the vertical borehole or extracted from the bedrock in the reaction zone to promote ammonia production without first forming an intermediate hydrogen product, thereby reducing energy consumption and lowering the temperature and pressure requirements of the reaction zone to facilitate the reaction.

[0007] A method for producing at least one of ammonia or an ammonium salt via geochemistry includes transporting an aqueous solution and a nitrogen source below the Earth's surface to facilitate a reaction, thereby forming at least one of ammonia or an ammonium salt.

[0008] The method may further include reacting an aqueous solution with ultramafic rock to produce hydrogen (H2). The hydrogen can be collected in a storage tank. In some embodiments, geothermal energy can be used to react hydrogen with a nitrogen source to form at least one of ammonia or an ammonium salt. The ammonium salt can be collected from the ultramafic rock, wherein the ammonium salt may include one or more of saline sands (NH4Cl) and ammonium bicarbonate (NH4HCO3). One or more secondary reactants can be transported below the surface to promote the formation of the ammonium salt.

[0009] The aqueous solution can be transported to a rock bed containing ultramafic rocks located beneath the Earth's surface. Nitrogen sources can include N2, NO, N2O, NO2, and NO. x Or NO3 -One or more of the following. Hydrogen can react with a nitrogen source at pressures ranging from about 1 atm to about 400 atm. Hydrogen can react with nitrogen in a reaction vessel. The reaction can occur from about 1 foot to about 5 miles below the surface. Ammonia can be collected in a collection tank.

[0010] In some embodiments, delivering the aqueous solution and nitrogen source through the surface may include passing the aqueous solution and nitrogen source through multiple boreholes located on the surface. Delivery may include pumping or co-injecting the aqueous solution and nitrogen source through multiple boreholes below the surface.

[0011] An aqueous solution and a nitrogen source can flow through a single borehole among multiple boreholes located on the surface. In some embodiments, the reaction occurs in the presence of one or more catalysts to produce ammonia. Ammonia can be produced without the formation of hydrogen (H2). One or more catalysts can be transported below the surface to increase the yield or rate of ammonia production. In some embodiments, one or more catalysts can be transported through a single borehole among multiple boreholes. One or more catalysts may include one or more of nickel, copper, cobalt, sodium, magnesium, calcium, titanium, chromium, iron, zinc, platinum, ruthenium, osmium, alumina, calcium oxide, molybdenum, ruthenium, alloys of different metals, or organic and metalorganic catalysts. In some embodiments, one or more catalysts may be naturally present below the surface.

[0012] In some implementations, droplets of the aqueous solution can be generated before it is delivered below the surface, the droplets being generated using an electrospray device attached to multiple boreholes. A controller can be used to adjust at least one of the following: the flow rate of one or more of the aqueous solution or nitrogen source delivered below the surface, or the composition of one or more of the aqueous solution or nitrogen source.

[0013] The conversion rate from iron beneath the surface to ammonia can range from approximately 5% to approximately 80%. Ammonia production can range from approximately 10 g NH3 / t olivine to approximately 500 g NH3 / t olivine. Ammonia can be extracted from beneath the surface and collected in collection tanks.

[0014] One method to increase ammonia production involves exposing an aqueous solution and a nitrogen source beneath the surface to an iron-bearing bedrock in the presence of a catalyst to promote a reaction that forms ammonia.

[0015] The catalyst can be transported below the surface. The reaction can form ammonia without the formation of hydrogen (H2). The catalyst can be naturally present below the surface. In some embodiments, the catalyst can be naturally present within iron-bearing rock beds. One or more catalysts may include nickel, copper, cobalt, sodium, magnesium, calcium, titanium, chromium, iron, zinc, platinum, ruthenium, osmium, alumina, calcium oxide, molybdenum, ruthenium, alloys of different metals, or organic and organometallic catalysts. The reaction can occur at a temperature ranging from about room temperature to about 500°C. In some embodiments, the reaction can occur at a temperature ranging from about room temperature to about 300°C. The reaction can occur at a pressure ranging from about 1 atm (0.1 MPa) to greater than 30 MPa.

[0016] An embodiment of a system for producing at least one of ammonia or ammonium salts via geochemistry includes one or more channels extending from the Earth's surface and equipment in fluid communication with a bedrock via said one or more channels. The equipment is configured to deliver an aqueous solution and a nitrogen source to a bedrock located close to the Earth's surface, thereby reacting with the bedrock to form the product.

[0017] The product may be at least one of an ammonium salt or hydrogen gas. The system may include a storage device configured to collect the product. The storage device may be located below the surface. In some embodiments, the system may include a controller in communication with at least one of one or more channels or devices, the controller being configured to regulate at least one of the following: the flow rate of one or more of an aqueous solution or a nitrogen source delivered below the surface, or the composition of one or more of an aqueous solution or a nitrogen source.

[0018] In some implementations, the system may include a reaction vessel in fluid communication with one or more channels and configured to facilitate a reaction between the product and a nitrogen source to form a gas. The reaction vessel may be located below ground level.

[0019] The system may include a collection well in fluid communication with the reaction vessel and configured to collect gases. In some embodiments, the gas may include ammonia. Attached Figure Description

[0020] This disclosure will be more fully understood from the following detailed description taken in conjunction with the accompanying drawings, wherein:

[0021] Figure 1 This is a schematic diagram of an example implementation of a system and method for producing ammonia from underground geothermal energy, wherein water reacts with the bedrock to form hydrogen, and then the hydrogen reacts with nitrogen injected underground to form ammonia in an underground reaction tank;

[0022] Figure 2AThis is a schematic diagram of an example implementation of a system and method for producing ammonia from underground geothermal energy, wherein water reacts with a rock bed in the presence of a catalyst to form ammonia, which is then collected in a surface collection tank.

[0023] Figure 2B yes Figure 2A A schematic diagram of the system;

[0024] Figure 3A yes Figure 2A A schematic enlarged view of the reaction zone of a method for producing ammonia from underground geothermal energy, in which nitrogen reacts with water in the presence of a catalyst;

[0025] Figure 3B yes Figure 2A A schematic enlarged view of the reaction zone of a method for producing ammonia from underground geothermal energy, in which nitrates react with water in the presence of a catalyst;

[0026] Figure 4A This is a gas chromatogram showing the generation of hydrogen gas during the reaction between the synthetic mineral (Fe(OH)2) in the rock and the fluid;

[0027] Figure 4B It is the nuclear magnetic resonance (NMR) spectrum of ammonium produced by the synthesis of minerals and fluids from ferrous hydroxide (II)(Fe(OH)2) in rocks;

[0028] Figure 4C This is a diagram illustrating the generation of hydrogen from actual mineral rocks using a nickel catalyst;

[0029] Figure 4D The NMR spectrum of ammonium formed from olivine;

[0030] Figure 4E The NMR spectrum of ammonium produced by the synthesis of minerals from ferrous hydroxide (II)(Fe(OH)2) from rocks using a copper catalyst;

[0031] Figure 4F It shows the NMR spectrum of isotopes formed using nitrate sources of ammonium;

[0032] Figure 5A This shows the X-ray diffraction (XRD) pattern of the synthetic rock in its Fe(OH)2 state before the reaction;

[0033] Figure 5B It is shown Figure 5A XRD pattern of synthetic rock after it is transformed into Fe3O4 following the reaction;

[0034] Figure 5C It is shown Figure 5A Image of synthetic rock before reaction using X-ray photoelectron spectroscopy (XPS);

[0035] Figure 5D It is shown Figure 5A The X-ray photoelectron spectroscopy (XPS) spectrum of the synthetic rock after it was transformed into Fe3O4 following the reaction;

[0036] Figure 6A It is made from NO3 and the nearest surface hydroxide ions (OH) - The reaction produces HNO3 A schematic diagram of the molecular structure;

[0037] Figure 6B It is made from NO3 The second nearest surface hydroxide ion (OH) - The reaction produces HNO3 A schematic diagram of the molecular structure;

[0038] Figure 6C It is composed of adsorbed water (H2O) and adsorbed NO3. A schematic diagram of the molecular structure of the product generated by the reaction, showing the production of HNO3. and OH ;

[0039] Figure 6D This is a free energy diagram of ammonia formation on Fe(OH)₂ and nickel-doped Fe(OH)₂ surfaces, where the hydrogen in ammonia originates from... Figure 6C Water molecules;

[0040] Figure 6E A graph showing a comparative analysis of the effects of various catalysts on the amount of geological ammonia produced; and

[0041] Figure 7 This is a schematic diagram of an example implementation of a system and method for producing ammonium salts from underground geothermal energy, wherein water reacts with the bedrock to form hydrogen, and then the hydrogen reacts with nitrogen injected underground and secondary reactants to form ammonium salts. Detailed Implementation

[0042] Certain exemplary embodiments are now described to provide a general understanding of the principles of the systems and methods disclosed herein. This specification covers all descriptions, including any drawings, whether they are present in this document and / or in any material or other information incorporated herein by reference. One or more examples of these embodiments are illustrated in the drawings. Those skilled in the art will understand that the systems, methods, and apparatuses specifically described herein and illustrated in the drawings are non-limiting exemplary embodiments, and the scope of this disclosure is defined only by the claims. Features shown or described in one embodiment may be combined with features of other embodiments. These modifications and variations are intended to be included within the scope of this disclosure. Within the scope of this disclosure, which includes illustrative descriptions of systems, apparatuses, devices, techniques, and methodologies, those skilled in the art will be able to appreciate how systems, apparatuses, setups, techniques, and methodologies can be integrated according to this disclosure into products, systems, production processes, methods, etc., for the in-situ production of ammonia. Furthermore, within the scope of the various terms used in this disclosure to refer to components and / or processes in the disclosed systems, devices, apparatuses, technologies, and methodologies, those skilled in the art, in conjunction with the claims, this disclosure, and their own expertise, will understand that such terms are merely examples of the relevant components and / or processes, and that other components, designs, processes, and / or operations are also possible.

[0043] At least one novel feature of this embodiment includes the use of geothermal chemistry for the production of ammonia and / or ammonium salts. For example, one or more reactants can be transported to a subsurface region, such as in or within the crust, for in-situ formation of ammonia and / or ammonium salts. The reactants may include, for example, water (H2O) and nitrogen (N2), wherein water is transported to contact with an ultramafic bedrock to react and generate hydrogen (H2). The hydrogen can then be trapped in a subsurface container permeable only to H2 and reacted therewith with nitrogen to form ammonia that can be transported to the surface. In an alternative embodiment, nitrogen can be pumped in to contact with hydrogen released from the bedrock, thereby forming ammonium salts in the crust. The ammonium salts can then be mined, for example, using conventional mining and / or fracturing techniques. Alternatively, a catalyst can be transported with the reactants, or the reaction can be promoted by a catalyst within the bedrock to form ammonia in situ. The formation of ammonia and / or ammonium salts via the methods, systems and apparatus disclosed herein can utilize the increased temperature and pressure in the Earth's crust (which has been shown to be the temperature and pressure required for the Haber-Bosch reaction, but is now provided by the subsurface at a certain depth) to provide the energy required for the reaction to occur.

[0044] Figure 1An example embodiment of ammonia geothermal production system 100 according to this embodiment is shown. Ammonia geothermal production may include a reaction that produces hydrogen from an inflowing fluid or aqueous solution, such as water, beneath the surface. This reaction may occur on the surface of an iron-rich ultramafic rock (referred to as an FeO bedrock or bedrock 102 because iron is in the Fe II valence state). In the reaction, bedrock 102 may be oxidized, while water may be reduced to form hydrogen. Iron within the rock may be in the Fe II valence state, for example, ferrous oxide (FeO), where iron acts as a catalyst to form FeO bedrock 102. When water comes into contact with the ultramafic bedrock (FeO bedrock 102), Fe is oxidized to Fe-IV, while water (H2O) is reduced to gas (H2). For the purposes of this disclosure, the site where the reaction occurs is referred to as reaction zone 108, which in some embodiments may have a pressure in the range of approximately 1 atm to approximately 400 atm.

[0045] System 100 for ammonia subsurface geothermal production may include multiple components in various combinations. For example, system 100 may include one or more of the following: a fluid delivery device 110, a storage tank 120, a reactor or reaction vessel 130, and multiple channels 140 and / or collection tanks 150 for transporting reactants and / or products between the surface and the earth's crust. As shown, various parts of system 100 may be strategically connected and fluidly communicated with each other, such as storage tank 120, reaction vessel 130, collection tank 150, and / or auxiliary components (not shown) that provide nitrogen discharge through one or more channels 140 into the area between storage tank 120 and reaction vessel 130. Those skilled in the art will understand from this disclosure other fluid communications that may be utilized in alternative embodiments. One or more pumps (not shown) may be used in conjunction with these components to deliver compounds and / or regulate the flow rate of compounds transported to and from the surface. It will be understood that system 100 may be modular, allowing various components to be added and / or removed based on desired reaction products.

[0046] As shown, water can be delivered through one or more boreholes 106 via multiple channels 140 to below the surface or subsurface 104. Each channel 140 may be connected to one or more components of system 100, such as device 110, collection tank 150, etc. Compounds may flow through the channels 140 in either direction, with some compounds flowing to subsurface 104 to react with bedrock 102, and products may flow back above the surface for collection. It will be understood that channels 140 may include pipes, conduits, and / or other similar structures for conveying fluids. Channels may be made of one or more materials known to those skilled in the art, such as stainless steel, carbon steel, nickel alloys, titanium alloys, ceramics, copper, polyvinyl chloride, aluminum, etc.

[0047] System 100 may include a controller 160 for adjusting one or more system parameters. For example, the flow rate and / or composition of the inflow fluid may be adjusted. In some embodiments, the flow rate of water through borehole 106a may be adjusted to be in the range of approximately 5 cubic meters per second to approximately 50 cubic meters per second, and more specifically, in the range of approximately 20 cubic meters per second to approximately 30 cubic meters per second.

[0048] The fluid delivery device 110 may be and / or similar to a water tank, hose, or stainless steel borehole pipe. As described above, water may be delivered using one or more pumps, injection devices, and / or flow devices, and / or supplied by gravity through channel 140. In some embodiments, the water may include one or more additives capable of catalyzing surface reactions and / or promoting free flow of water through the borehole. The additives may include chemical additives or catalysts capable of: 1) controlling pH to increase the reaction rate and yield with olivine rock; and / or 2) providing chemicals to depassivate the ultramafic rock after the reaction, making the rock surface available for multiple hydrogen production cycles. Those skilled in the art will appreciate that the depassivation of ultramafic rock is used because the rock surface is covered with an Fe3O4 passivation layer (which prevents further reactions). Chemicals may be added to the surface to prevent the formation of the passivation layer, which may make the surface available for multiple reaction cycles. Some non-limiting examples of additives may include acids and fluorinated chemicals. In some embodiments, the additives may be used to control pH.

[0049] In use, the fluid delivery device 110 can be configured to generate, pump, co-inject, and / or deliver a mixture of water and additives through borehole 106 via channel 140. Water can be delivered in the form of individual droplets, thereby increasing the evaporation rate in the reaction zone. In some embodiments, droplets can be generated using an electrospray device attached to the downflow channel. In some embodiments, without using electrospraying, the liquid water injected below the surface 104 can be vaporized at high temperatures in channel 140.

[0050] The channel 140 may extend below the surface 104 (e.g., within the crust) to the depth at which ultramafic rock 102 is found. For example, ultramafic rock enrichment zones in the crust can be detected by remote sensing techniques, seismic surveys, borehole and well logging, and geochemical analysis, as known to those skilled in the art, and therefore a detailed discussion of detection is omitted from this disclosure. While the depth at which ultramafic rock is found within the crust can depend on factors including, but not limited to, geography and climate, the depths of boreholes 106a and 106b used in this disclosure may be approximately 1 foot to approximately 10 miles below the surface, approximately 1 foot to approximately 5 miles below the surface, approximately 3 feet to approximately 10 miles below the surface, approximately 3 feet to approximately 10 miles below the surface, approximately 5 feet to approximately 10 miles below the surface, and / or approximately 5 miles to approximately 5 miles below the surface.

[0051] Once the mixture is injected into and / or comes into contact with the FeO bedrock 102, a reaction can occur to release hydrogen gas. For example, in some embodiments, FeO in the ultramafic rock can be oxidized while water from the inflowing fluid is reduced to produce H2. (This is a generalized and simplified reaction, explaining the process occurring in ultramafic rocks.) Water can be liquid or gaseous, depending on the reaction configuration (e.g., injection of droplets in the form of liquid water and / or gas). Specific reactions can vary depending on the type of ultramafic rock. Two examples of specific reactions are given below: The released hydrogen can be captured in a reservoir 120 located below the surface. As shown, the reservoir 120 can be placed near the bedrock 102 and close to the reaction zone 108 to maximize the amount of gas collected and help manage the flammability of the hydrogen, thus maximizing efficiency and safety. The reservoir 120 can be and / or similar to a flask with a porous membrane to allow hydrogen to pass through the porous membrane (not shown) and into the reservoir 120. The porous membrane can be configured to retain the hydrogen captured within the reservoir 120, as shown, for subsequent delivery for interaction in the reaction vessel 130. In some embodiments, the membrane can be configured to selectively allow hydrogen permeation to maximize the amount and / or purity of the hydrogen captured in the reservoir.

[0052] Hydrogen from storage 120 can be mixed with nitrogen supplied below the surface. For example, nitrogen can be supplied to storage 120 via a second borehole 106b through a flow channel 140 to allow mixing with hydrogen. Mixing can occur at the outlet of storage 120, although in some embodiments, as shown, a separate tank can be used for the reaction. For example, storage 120 can be in fluid communication with a reaction vessel 130 configured to facilitate the reaction of hydrogen and nitrogen to form ammonia (NH3). An example reaction is as follows: .

[0053] In some embodiments, reaction vessel 130 may be coated with a catalyst to facilitate the reaction between reactants. Some non-limiting examples of catalysts may include iron and ruthenium. The catalyst may differ from those discussed below for facilitating the reaction to form ammonia, but it will be understood that in some embodiments, the catalyst may be the same.

[0054] The location of the reaction vessel 130 may depend, at least in part, on the temperature and / or pressure at that depth to facilitate optimal reaction conditions. For example, ammonia formation may utilize the increased temperature and pressure within the Earth's crust to provide the energy required for the reaction. Therefore, in some embodiments, the reaction vessel 130 may be located at a depth within the Earth's crust such that the ambient pressure can be above approximately 200 atm, or in some embodiments, in the range of approximately 200 atm to approximately 400 atm, approximately 1 atm to approximately 400 atm, or approximately in the range of approximately 1 MPa to approximately 30 MPa. The reaction vessel 130 may be located at a depth within the Earth's crust such that the ambient temperature can be above approximately 90°C, or in some embodiments, in the range of approximately 90°C to approximately 400°C, or approximately in the range of approximately 250°C to approximately 600°C. At this depth, the reaction can proceed smoothly while avoiding the release of carbon dioxide and other harmful gases (as part of the Haber-Bosch process discussed above). The temperatures and pressures discussed herein can be found, depending on their location in the world, at depths ranging from approximately 1 mile to approximately 5 miles below the Earth's surface and / or from approximately 3 miles to approximately 5 miles below the Earth's surface.

[0055] Reactor 130 may be in fluid communication with collection tank 150 for receiving ammonia therein. As shown, once ammonia is formed, it can flow from reactor 130 through channel 140 and borehole 106c to collection tank 150 for storage and / or transport. Although collection tank 150 is shown above surface 104, in some embodiments, underground collection tanks may be used to replace and / or supplement collection tank 150. It will be understood that the distance between reactor 130 and collection tank 150 may be greater than the distance between bedrock 102 and storage tank 120, and between storage tank 120 and reactor 130, due to the increased stability of ammonia compared to hydrogen during transport. In some embodiments, as an alternative or supplement to having one or more collection tanks 150, the resulting ammonia may be pumped or otherwise transported to a location for subsequent use without first storing (sit) the ammonia in the collection tank. Such locations may be near the location of system 100, and / or such locations may be located at a remote location of system 100, for example, ammonia may be delivered to a remote location via a network of pipes or channels 140.

[0056] Figures 2A-2B An example embodiment of a system 200 for geothermal production of ammonia according to this embodiment is shown, wherein ammonia is produced without the prior formation of hydrogen. For the sake of brevity, detailed analysis is omitted where certain characteristics of ammonia production are the same as or similar to those of the system 100 described above.

[0057] Ammonia production in System 200 can occur on a nominally zero CO2 scale, without mineral supply chain constraints, while aiming for cost competitiveness with the Haber-Bosch process. To date, “natural hydrogen,” or “geological hydrogen,” has emerged as an alternative approach to alleviate the challenges associated with the electrochemical production of hydrogen. Natural hydrogen can be produced through a chemical redox reaction known as serpentinization, in which iron-bearing rocks (ultramafic rocks) are oxidized while reducing groundwater to H2, where the necessary heat and pressure (approximately in the range of about 90°C to about 270°C and up to approximately 20 MPa to about 35 MPa) can be provided below the surface for this thermochemical reaction. During low-temperature serpentinization reactions (e.g., in the range of about 90°C to about 200°C), ultramafic rocks such as olivine ((Fe,Mg)₂SiO₄) can undergo a series of chemical transformations when exposed to water. First, the reaction can lead to the dissolution of ions such as Mg²⁺. 2+ and Fe 2+ The release of Fe. 2+ It can undergo a transformation to form Fe(OH)₂. Furthermore, Fe(OH)₂ contains Fe 2+ Hydrogen gas (H2) can be generated during the oxidation process to form Fe3O4 (magnetite).

[0058] The pathway for producing hydrogen from rocks is known as serpentinization, which can currently be mainly explained by the following reaction process (Equations 1-4):

[0059]

[0060] In principle, hydrogen production can rely on ferrous iron (Fe²⁺). 2+ The redox reaction between ferrous iron and water. Inspired by this, the reduction potential of ferrous iron in rocks can be used, but instead of reducing water, nitrogenous substances (nitrates or nitrogen) can be reduced to produce ammonia. The following reaction formula (Equation 5) describes the chemical basis of ammonia production in geology: nitrates in aqueous solution are reduced to ammonia by Fe(OH)2 present in rocks, while Fe(OH)2 can be oxidized to Fe3O4, and its related components are also present. Figure 2B The text appears to be a mix of Chinese characters and symbols, possibly representing a corrupted or incomplete translation. A direct translation wouldn't be meaningful without further context.

[0061]

[0062] At least one novel feature of this embodiment may include adding a catalyst to the geothermal reaction. For example, system 200 may add a catalyst (Cu) to the reaction. 2+ or Ni 2+ The presence of nitrogen (NO3) exposes ultramafic bed 102 to water and nitrogen sources. - Ammonia can be synthesized from nitrogen gas (N2) and nitrous oxide (N2O). Other non-limiting examples of nitrogen sources include nitrogen gas (N2), nitrous oxide (N2O), nitric oxide (NO), and NO₂. x And / or nitrogen dioxide (NO2), and some other non-limiting examples of catalysts may include nickel, copper, cobalt, sodium, magnesium, calcium, titanium, chromium, iron, zinc, platinum, ruthenium and osmium, alumina, calcium oxide, molybdenum, ruthenium, alloys of different metals, organic and organometallic catalysts, etc. The catalyst may be co-injected with water and / or a nitrogen source via device 110, although in some embodiments, the bedrock 102 may include one or more of these catalysts to help promote the reaction. It will be understood that the catalyst need not be expensive or difficult to obtain, which can further increase the scalability and ease of use of this method. The presence of a catalyst in the bedrock 102 can be determined by methods known to those skilled in the art, such as rock sampling, aeration, magnetic imaging, etc.

[0063] As shown, an aqueous solution containing a nitrogen source, excluding water and / or additives (e.g., catalysts), as in system 100, can be pumped or co-injected underground to react with iron-bearing rocks, producing an ammonia-containing solution that will be collected back on the surface. The nitrogen source and water can be co-injected underground via device 110 through a channel 140 disposed within borehole 106a to react with the rocks formed therein. Additional equipment, such as pumps, can be incorporated to efficiently manage the flow of the compounds. The process begins with the delivery of water and a nitrogen source (N2 or NO) to the ultramafic bedrock via the first borehole 106a. 3- Various additives—such as catalysts and pH adjusters—are used to promote redox reactions on the rock surface. Following this reaction, ammonia (NH3) can be produced, which then exits the subsurface 104 via a flow channel 106c through a borehole 106c, where it is subsequently collected at the surface. Collection can occur in a collection tank 150 or in other containers known to those skilled in the art. In some embodiments, system 200 may include an injection well (not shown) comprising introducing device 110 into the subsurface 104, and a production well (not shown) for collecting ammonia. In some embodiments, pumps may be used to regulate the compound flow.

[0064] In the system 200 described above, reaction vessel 130 is not required, but it will be understood that one or more of these components may be used as needed. Unlike the separate injection of nitrogen through the subsurface 104 in system 100 to react with hydrogen as a result of the reaction with bedrock 102, system 200 exposes bedrock 102 to a nitrogen source, thereby utilizing compounds in the earth to produce ammonia. As shown, in system 200, reservoir 120 may be placed near bedrock 102 and close to reaction zone 108 to maximize the amount of ammonia collected rather than hydrogen and to help manage the flammability of ammonia, thereby maximizing efficiency and safety. Similar to system 100 described above, reservoir 120 may be and / or resemble a flask with a porous membrane to allow ammonia to pass through the porous membrane (not shown) and enter reservoir 120. The porous membrane may be configured to retain ammonia trapped within reservoir 120, as shown, for subsequent delivery for interaction in collection vessel 150. In some embodiments, the membrane may be configured to selectively allow ammonia to permeate through in order to maximize the amount and / or purity of ammonia captured in the reservoir 120.

[0065] Figure 3A The reaction at the rock-fluid interface is shown in more detail, where Fe in the rock is oxidized and (N2 + H2O) is reduced to NH3. Simultaneously, this oxidation process leads to the reaction of nitrogen source and water (NO3). -The nitrogen source (N2 + H2O) is reduced to ammonia (NH3). Utilizing the natural properties of ultramafic rocks and the strategic configuration of system components, this complex reaction demonstrates a controlled and efficient process for converting nitrogen sources into valuable ammonia products. Compared to the Haber-Bosch process, this subsurface ammonia production method offers potential advantages, including no need for additional hydrogen, no need for heating and high pressure, in-situ utilization of geothermal and pressure potential, and zero or near-zero CO2 emissions. The decentralized nature of this method also provides a more scalable and sustainable approach for ammonia production utilizing the temperature and pressure occurring in reaction zone 108 below surface level 104. Figure 3B The reaction at the rock-fluid interface is shown in more detail, where, as the accompanying reaction indicates, Fe in the rock is oxidized to (NO3). - +H2O) is reduced to NH3.

[0066] Figures 4A to 4F This demonstrates the capacity for ammonia and hydrogen production under controlled conditions. To increase the rate and yield of hydrogen production, 1% Ni (equivalent to the mass of Fe(OH)₂) can be added. 2+ Introducing it into the Fe(OH)2 matrix as a catalyst can significantly accelerate hydrogen production. For example... Figure 4A As shown in the enlarged illustration, the initial reaction of Fe(OH)₂ with water at 90°C and atmospheric pressure produces trace amounts of hydrogen gas, detectable by gas chromatography (GC). The catalyst can be one or more transition metals, added to the reaction as an additive via drilling and / or naturally present in the bedrock. For example, small amounts of Ni... 2+ Adding sodium nitrate to the Fe(OH)₂ matrix as a catalyst can accelerate hydrogen production and increase the rate and yield of hydrogen production by 50 times. Adding sodium nitrate to the mixture reduces hydrogen production to almost zero but increases the production of geological ammonia, thus demonstrating that ammonia can be produced from representative rock-like chemicals, further evidenced by the presence of NH₄⁺ in its associated nuclear magnetic resonance (NMR) spectrum. + The characteristic spectral lines can be used to confirm this, such as Figure 4B As shown.

[0067] Figures 4C-4F Other characteristics of hydrogen and ammonia production are shown in the presence of a catalyst, where both the rate and yield of ammonia production are significantly increased. For example, in some embodiments, per tonne of Fe 2+It can produce approximately 7.8 kg of NH3, which translates to a conversion rate of 49.2% according to the main chemical formula (Formula 5). The conversion rate from iron beneath the surface to ammonia can range from approximately 5% to approximately 80%, a value that varies within a certain range based on various differences, such as rock types in different regions. In some embodiments, the ammonia yield can be from approximately 10 g NH3 / t olivine to approximately 500 g NH3 / t olivine. Furthermore, hydrogen can be obtained from actual rocks, such as olivine, at a rate of approximately 3.23 μmol g / t. -1 h -1 The production rate is nearly 100 times higher than the rate usually reported, and could be as high as 300 times higher.

[0068] The introduction of nitrates into this system can lead to the detection of NH4 in the NMR spectrum. + ,like Figure 4D As shown, this demonstrates that approximately 29.9 g of NH3 can be produced per ton of olivine. The catalyst was transferred from Ni... 2+ Replace with Cu 2+ The yield of NH3 can be further increased to approximately 63.3 g NH3 / ton of olivine, indicating that Fe(OH)2, as a simulated rock, can produce large amounts of NH3 in just about 10 minutes at room temperature (temperature (25°C)) and about 1 atm. Figure 4E As shown. This conversion can occur at temperatures ranging from approximately room temperature to above approximately 300°C, for example, approximately 300°C, approximately 400°C, approximately 500°C, or higher. The pressure range can be from approximately 1 atm (0.1 MPa) to greater than approximately 30 MPa. Without the addition of a catalyst, the amount of NH3 produced by the reaction between olivine and nitrate solution can be approximately 15.8 g NH3 / t olivine.

[0069] As mentioned earlier, geological ammonia can be generated through a novel "modified serpentinization" reaction via Fe (i.e., Fe) in the rock (both olivine and synthetic materials). 2+ ) oxidized to Fe 3+ (To produce Fe3O4) Figures 5A to 5D This illustrates the chemical and structural transformations of the rock during the reaction. For example, Figure 5A The synthetic rock shows that it can be in the Fe(OH)2 phase (without any significant impurity peaks), where, as detected by X-ray diffraction (XRD), Fe is in its +2 oxidation state. Following the reaction that produces NH3, the Fe in the synthetic rock... 2+ It can be oxidized to Fe 3+ And it can form Fe3O4, as shown in the XRD results of the synthetic rocks (see...). Figure 5BThis can show the transformation from Fe(OH)₂ (before the reaction) to Fe₃O₄ (after the reaction), in which some Fe is oxidized to the +3 oxidation state. To further confirm and accurately study the oxidation state of Fe in the synthesized rocks before and after the reaction, X-ray photoelectron spectroscopy can be performed before and after the reaction, as shown below. Figure 5C and Figure 5D As shown in the figure. XPS supports XRD results, which can also indicate the amount of Fe (from Fe before the reaction). 2+ See also Figure 5C It can be oxidized to +3 oxide during the serpentinization reaction (forming Fe3O4 after the reaction; see also...) Figure 5D ).

[0070] Furthermore, the reaction mechanism (Equation 5) can be studied using density functional theory (DFT) calculations. For the reaction in Equation 5, the hydrogen source in NH3 can be either H2O or Fe(OH)2. First, we consider Fe(OH)2 as the hydrogen source. When NO3... - When ions are adsorbed on a surface, they react with surface OH groups. - The reaction produces HNO3. , as follows Figures 6A-6B As shown. In Figure 6A In the middle, by NO3 and the nearest surface OH - HNO3 generated (as indicated by the arrow) The structure can have a ΔG of 1.77 eV. This structure is HNO4. The stable tetrahedral unit makes it unfavorable for subsequent reactions. Figure 6B In the middle, by the second nearest surface OH - HNO3 (as indicated by the arrow) is formed The structure has a ΔG of 2.62 eV, which is too high. When considering hydrogen originating from H₂O, the adsorbed H₂O can react with the adsorbed NO₃⁻. The reaction produces HNO3. and OH ,like Figure 6C As shown. This reaction has a ΔG of 1.66 eV, making it more energy-favorable than the previous two cases (with...). Figure 6A and 6B The energy differences are ~40 KbT and ~4 KbT, respectively. Based on these observations, the hydrogen in the ammonia product (NH3) originates from H2O rather than Fe(OH)2. Therefore, in the following calculations, we consider H2O as the hydrogen source for NH3 (as shown in Equation 6):

[0071]

[0072] That is, at least one unexpected feature of the reaction mechanism for ammonia formation in this embodiment is actually a one-step process rather than a two-step process. Specifically, the hydrogen atoms that combine with N2 to form ammonia come from water co-injected 104 times below the Earth's surface, rather than forming hydrogen gas that subsequently reacts with N2 to form NH3. In fact, since the nitrogen source reacts directly with H+ in the water via a redox reaction... + or OH - The reaction therefore does not form hydrogen as an intermediate product. Thus, since hydrogen is not formed in a batch reaction, the presence of a nitrogen source changes the reaction mechanism from a conventional two-step process to a one-step process. This change allows for more efficient ammonia production and a reduced need for high pressures and temperatures to produce ammonia (as in the Haber-Bosch process), while allowing the reaction to occur at the temperatures and pressures discussed above. This allows for a lower kinetic energy barrier and deeper drilling, which can reduce the cost of the machinery and piping used to facilitate the delivery of compounds to reaction zone 108.

[0073] Figure 6D The calculated free energy changes for ammonia formation on Fe(OH)₂ and Ni-doped Fe(OH)₂(100) surfaces are shown, where the H in NH₃ originates from water. Ni-doped Fe(OH)₂ can exhibit resistance to NO₃⁻. - A stronger adsorption energy (-2.54 eV for Ni-doped Fe(OH)₂ and -1.69 eV for Fe(OH)₂) favors subsequent reactions. Furthermore, the total free energy change for Ni-doped Fe(OH)₂ can be more negative, indicating a thermodynamically more favorable process. Additionally, in Figure 6E The effect of different additives on the amount of geo-NH3 produced is shown. As illustrated, copper ions (Cu...) 2+ Nickel ions (Ni) 2+ ) and / or manganese (Mn 2+ All of these can contribute to the production of geo-NH3, with copper ions being the most effective. Cobalt (Co) 2+ TiO2 suspended particles and / or magnesium (Mg) 2+ The effect of zinc ions (Zn) on ammonia production is negligible. 2+ Conversely, ammonia production can be reduced compared to the absence of zinc. This result could help provide guidance for catalyst addition in subsurface pumped aqueous solutions, thereby further enhancing the rate of geological-NH3 production.

[0074] Figure 7 An example embodiment of a geothermal production system for ammonium salt 170 used in this embodiment is shown. For the sake of brevity, detailed analysis is omitted where certain characteristics of ammonium salt production are the same as or similar to those of ammonia production discussed above.

[0075] As shown, water, or a mixture of water and additives, can be pumped from device 110 or co-injected into bedrock 102 to react and form hydrogen, as described above. However, instead of collecting the hydrogen product, nitrogen and secondary reactants (X') can be separately conveyed to bedrock 102 via flow channel 140, as shown. When hydrogen reacts with nitrogen and secondary reactants (X'), solid ammonium salt 170, such as NH4, can be formed. + (s), which can precipitate in a stable form 104 below the Earth's surface. Example reactions are as follows: (Where a, b, c, and d are reaction-equilibrium coefficients, and X' can be in the liquid or gas phase). Some non-limiting examples of secondary reactants (X') may include hydrochloric acid (HCl), carbonic acid (H₂CO₃), and / or carbon dioxide gas (CO₂). Ammonium salt products 170 may include halide, ammonium chloride, aluminum bicarbonate, ammonium sulfide, ammonium sulfate, and / or ammonium phosphate.

[0076] In the aforementioned system 300, the storage tank 120, reaction vessel 130, or collection tank 150 are not required, but it will be understood that one or more of these components may be used as needed. The ammonium salt 170 can then be mined, extracted, and / or collected using techniques known to those skilled in the art, such as known mining techniques.

[0077] In alternative embodiments of this disclosure, hydrogen can be transported via channel 140 instead of water. For example, in such embodiments, instead of transporting water to react with bedrock 102 to form hydrogen, hydrogen, along with optional one or more additives, can be transported to the reaction zone. Nitrogen, along with optional secondary reactants (X'), can also be transported to reaction zone 108 to react with hydrogen to form ammonia and / or ammonium salts. Iron within the ultramafic rock can serve as a catalyst for this reaction (similar to the Fe catalyst used in the Haber-Bosch process, but here naturally provided by the rock surface where the reaction occurs). In such embodiments, crustal pressure and temperature can be used to provide optimal conditions for the formation of ammonia and / or ammonium salts without severe environmental consequences or the capital costs of the Haber-Bosch process.

[0078] Experimental steps

[0079] Material

[0080] Peridot was purchased from Ward's Science. Chemicals included sodium nitrate (99.995% trace metal standard), sodium nitrate- 15 N (≥98 atoms) 15Ferrous(II) chloride (99.99% trace metal standard), copper(II) chloride (97%), nickel(II) chloride hexahydrate (99.999% trace metal standard), sodium hydroxide (anhydrous, ACS reagent), sulfuric acid (99.999%), maleic acid (quantitative NMR standard), and heavy water (≥99.95 atomic %D) were purchased from Sigma-Aldrich without further purification. Deoxygenated deionized water was purged with argon for approximately 30 minutes to remove dissolved oxygen and stored in an oxygen-free (O2 concentration < approximately 0.5 ppm) but permissible aqueous solution glove box, hereinafter referred to as the water glove box.

[0081] Geological NH3 or H2 production experimental device

[0082] The rock-water reaction system may include an autoclave reactor integrating a gas system and a heating system. The autoclave reactor may be equipped with a gas inlet and a gas outlet, both of which are fitted with gas mass flow controllers to control and record the gas flow. The gas inlet can be connected to an argon cylinder to provide argon as a carrier gas. Furthermore, the gas outlet can be connected to a gas chromatograph (GC) for real-time, in-situ measurement of the gas composition and concentration within the autoclave. The heating system is capable of controlling and measuring the internal temperature of the autoclave reactor. A temperature probe can be tunneled into the interior of the autoclave. Based on temperature feedback from the temperature probe and a set target temperature, the heating base can be adjusted to regulate the temperature.

[0083] For actual mineral reaction experiments, olivine minerals can be processed by hammering, coarse grinding, and fine grinding until a powder sample is obtained for subsequent experiments. In an argon-filled water glove box, a certain amount of olivine powder, deoxygenated deionized water, NaNO3 solution, NaOH solution, and CuCl2 or NiCl2 solution as a catalyst can be sequentially added to an autoclave and sealed. For simulated mineral reaction experiments, a certain amount of FeCl2 solution, NaOH solution, CuCl2 or NiCl2 solution as a catalyst, and NaNO3 can be sequentially added to an autoclave and sealed. In this case, the first added chemicals, FeCl2 and NaOH, can produce Fe(OH)2 precipitate in situ, which can be used as a simulated mineral. The autoclave can then be placed in a heating system and connected to a gas pipeline system, after which the temperature and operating duration can be set to start the experiment. For geo-H2 experiments, NaNO3 is not added for the purposes of the experiment. Instead, an equivalent volume of deionized water is used to ensure the total reaction volume, and the concentrations of other reactants remain constant. For rapid pipeline tests at room temperature, neither autoclaves nor heating systems were used. Instead, simulated rock-water reactions were simply performed within the test pipeline. These rapid pipeline tests were conducted for optimization and mechanistic studies; therefore, the reaction time was set to approximately 10 minutes to improve efficiency, while for actual olivine minerals, the reaction lasted approximately 21 hours to explore NH3- production capacity. Isotope experiments were conducted using... 15 N-NaNO3 replaced 14 N-NaNO3 was used as a reactant under similar experimental conditions.

[0084] Characterization

[0085] Solid samples were obtained after the experiment by separating the solid and liquid phases using a vacuum filtration system built in a water-filled glove box. Powder X-ray diffraction (Panalytical Empyrean, Mo K-α radiation, λ = 0.7107 Å) was used to determine the crystal structures of the model compounds and minerals before and after the reaction. Monochromatic Al K-α (X-ray pass energy = 2.95 eV) was used as the excitation source for X-ray photoelectron spectroscopy (XPS; PHI VersaProbe II X-ray photoelectron spectroscopy) to investigate the oxidation state of Fe near the particle surface. Of all the characterization techniques used, air-free supports were used to protect the samples during all characterizations to capture accurate data before and after the reaction.

[0086] Measurement and calculation of NH3 and H2 production rates

[0087] The concentration of NH3 in the solution was measured directly by nuclear magnetic resonance (NMR). All experiments were repeated at least three times. After filtration, maleic acid (MA) (as an internal standard) and H2SO4 were added to the solution to adjust the pH. NH3 concentrations were obtained using a three-channel Bruker Avance Neo spectrometer operating at approximately 400.17 MHz. 1 ¹H NMR spectra. Standard curves were established based on internal standard MA and external standard NH₄Cl. For all NMR results, the NH₃ concentrations were quantitatively calculated based on the standard chemicals (MA as internal standard). NH₃ yield (g NH₃ / t olivine or g NH₃ / kg Fe) 2+ This can be calculated from the concentration of NH3 in the solution and the mass of rock added at the start of the reaction. This is done by dividing the actual NH3 production by the mass of all Fe in the rock. 2+ The theoretical maximum production rate of NH3 is obtained when it is oxidized to Fe3O4 to obtain the NH3 production ratio.

[0088] The composition and concentration of gases in the autoclave were analyzed in situ using a GC (MG#5, SRI) equipped with a high-sensitivity thermal conductivity detector (TCD) directly connected to the autoclave outlet. A standard curve was established based on an external H2 standard, and the concentration of H2 in the gas could be calculated. H2 yield (μmol g) -1 h -1 The H2 concentration at the outlet gas level, the total volume of the autoclave system, and the mass of rock added at the start of the reaction can be obtained by dividing the actual H2 production by the total Fe content of the rock. 2+ The theoretical maximum production rate when oxidized to Fe3O4 is used to obtain the H2 production ratio.

[0089] DFT calculation method

[0090] Spin-polarized DFT calculations were performed using the Vienna ab initio simulation package (VASP 5.4.4). The Perdew, Burke, and Ernzerhof (PBE) generalized gradient approximation (GGA) was used to model the electron exchange-correlation interaction, with a plane-wave cutoff of 400 eV. The Grimme DFT+D3 method was employed to calculate van der Waals interactions. The Hubbard U correction (DFT+U) was introduced to accurately describe the correlation energies of the 3d orbitals in Fe and Ni atoms; referencing the work of Song et al., the effective parameters UJ for Fe and Ni atoms were set to 5.67 eV and 5.23 eV, respectively. The convergence criteria for energy and force were set to 10... -5 eV and 0.03 eV·Å -1A 2×2×1 Monkhorst-Pack grid is used to sample electrons in their Brillouin zone.

[0091] A 4×3 supercell was constructed using two layers of Fe(OH)₂(100) surfaces. For the Ni-doped Fe(OH)₂ case, one surface Fe atom was replaced by Ni. During structural relaxation, the bottom layer remained fixed, while the top layer was allowed to relax. The H₂O adsorption energy was tested on the constructed surface, confirming that the chosen supercell size and number of layers were sufficient to allow the H₂O adsorption energy to converge. The adsorption energy was calculated as follows:

[0092]

[0093] The zero-point energy (ZPE) and entropy correction of the adsorbate are also considered to be known to those skilled in the art.

[0094] Examples of the above implementation schemes may include the following:

[0095] 1. A method for producing at least one of ammonia or an ammonium salt via geochemistry, comprising:

[0096] An aqueous solution and a nitrogen source are transported below the surface to facilitate the reaction, thereby forming at least one of ammonia or an ammonium salt.

[0097] 2. The method according to Example 1, wherein the aqueous solution is delivered to a bedrock containing ultramafic rocks located below the surface.

[0098] 3. The method according to Example 2 further includes reacting the aqueous solution with the ultramafic rock to produce hydrogen (H2).

[0099] 4. The method according to Example 3 further includes collecting hydrogen in a storage tank.

[0100] 5. The method according to any one of Examples 2 to 4, wherein the nitrogen source comprises N2, NO, N2O, NO2, NO x Or NO3 - One or more of them.

[0101] 6. The method according to Example 5 further includes using geothermal energy to react the hydrogen with the nitrogen source to form at least one of ammonia or an ammonium salt.

[0102] 7. The method according to any one of Examples 2 to 6, further comprising collecting ammonium salts from the ultramafic rock, wherein the ammonium salts comprise one or more of halide sands (NH4Cl) and ammonium bicarbonate (NH4HCO3).

[0103] 8. The method according to any one of Examples 1 to 7 further includes delivering one or more secondary reactants below the surface to promote the formation of ammonium salts.

[0104] 9. The method according to Example 4 or Example 5, wherein the hydrogen reacts with the nitrogen source at a pressure ranging from about 1 atm to about 400 atm.

[0105] 10. The method according to any one of Examples 5 to 9, wherein hydrogen and nitrogen react in a reaction vessel.

[0106] 11. The method according to any one of Examples 1 to 10, wherein conveying the aqueous solution and the nitrogen source through the surface comprises passing the aqueous solution and the nitrogen source through a plurality of boreholes located on the surface.

[0107] 12. The method according to any one of Examples 1 to 11, further comprising collecting the ammonium salt in a collection tank.

[0108] 13. The method according to any one of Examples 1 to 12, wherein the reaction occurs approximately 1 foot to approximately 5 miles below the surface.

[0109] 14. The method according to any one of Examples 1 to 13, wherein the delivery comprises pumping or co-injecting the aqueous solution and the nitrogen source through a plurality of boreholes below the surface.

[0110] 15. The method according to any one of Examples 1 to 14, wherein the aqueous solution and the nitrogen source flow through a single borehole among a plurality of boreholes located on the surface.

[0111] 16. The method according to Example 15, wherein the reaction occurs in the presence of one or more catalysts to produce ammonia.

[0112] 17. The method according to Example 15 or Example 16, wherein the ammonia is produced without forming hydrogen (H2).

[0113] 18. The method according to any one of Examples 15 to 17, further comprising delivering one or more of the catalysts below the surface to increase the yield or rate of ammonia production.

[0114] 19. The method according to any one of Examples 15 to 18, further comprising delivering the one or more catalysts through a single borehole of the plurality of boreholes.

[0115] 20. The method according to any one of Examples 16 to 19, wherein the one or more catalysts comprise one or more of the following: nickel, copper, cobalt, sodium, magnesium, calcium, titanium, chromium, iron, zinc, platinum, ruthenium, osmium, alumina, calcium oxide, molybdenum, ruthenium, alloys of different metals, or organometallic catalysts.

[0116] 21. The method according to any one of Examples 16 to 20, wherein the one or more catalysts are naturally present below the earth's surface.

[0117] 22. The method according to any one of Examples 1 to 21, further comprising generating droplets of the aqueous solution before delivering the aqueous solution below the surface, the droplets being generated using an electrospray device attached to a plurality of boreholes.

[0118] 23. The method according to any one of Examples 1 to 22 further includes using a controller to regulate at least one of the following: the flow rate of one or more of the aqueous solution or nitrogen source delivered to the subsurface, or the composition of one or more of the aqueous solution or nitrogen source.

[0119] 24. The method according to any one of Examples 1 to 23, wherein the conversion rate of iron from below the surface to ammonia is in the range of about 5% to about 80%.

[0120] 25. The method according to any one of Examples 1 to 24, wherein the ammonia yield is in the range of about 10 g NH3 / t olivine to about 500 g NH3 / t olivine.

[0121] 26. The method according to any one of Examples 1 to 25 further includes extracting ammonia from below the ground and collecting the ammonia into a collection tank.

[0122] 27. A method for increasing the yield of ammonia production, comprising:

[0123] In the presence of a catalyst, an aqueous solution and a nitrogen source beneath the surface are exposed to an iron-bearing bedrock to promote the reaction, thereby forming ammonia.

[0124] 28. The method according to Example 27 further includes co-injecting the aqueous solution and the nitrogen source below the surface.

[0125] 29. The method according to Example 27 or Example 28, wherein the catalyst is delivered below the surface.

[0126] 30. The method according to any one of Examples 27 to 29, wherein the reaction forms ammonia without forming hydrogen gas (H2).

[0127] 31. The method according to any one of Examples 27 to 30, wherein the catalyst is naturally present below the earth's surface.

[0128] 32. The method according to any one of Examples 27 to 31, wherein the catalyst is naturally present in the iron-bearing bedrock.

[0129] 33. The method according to any one of Examples 27 to 32, wherein the one or more catalysts further comprises nickel, copper, cobalt, sodium, magnesium, calcium, titanium, chromium, iron, zinc, platinum, ruthenium, osmium, alumina, calcium oxide, molybdenum, ruthenium, alloys of different metals, or organic and organometallic catalysts.

[0130] 34. The method according to any one of Examples 27 to 33, wherein the reaction occurs at a temperature in the range of about room temperature to about 500°C.

[0131] 35. The method according to any one of Examples 27 to 34, wherein the reaction occurs at a temperature in the range of about room temperature to about 300°C.

[0132] 36. The method according to any one of Examples 27 to 35, wherein the reaction occurs at a pressure in the range of about 1 atm (0.1 MPa) to more than 30 MPa.

[0133] 37. A system for producing at least one of ammonia or an ammonium salt via geochemistry, comprising:

[0134] One or more channels extending from the earth's surface; and

[0135] A device in fluid communication with a rock bed via one or more channels, the device being configured to deliver an aqueous solution and a nitrogen source to the rock bed located close to the surface, thereby reacting with the rock bed to form products.

[0136] 38. The system according to Example 37, wherein the product is at least one of an ammonium salt or hydrogen gas.

[0137] 39. The system according to Example 37 or Example 38 further includes a storage device configured to collect the products.

[0138] 40. The system according to Example 39, wherein the storage is located below the ground surface.

[0139] 41. The system according to any one of Examples 37 to 40, further comprising a reaction vessel in fluid communication with the one or more channels and configured to facilitate the reaction of the product with the nitrogen source to form a gas.

[0140] 42. The system according to Example 41, wherein the reaction vessel is located below the ground surface.

[0141] 43. The system according to Example 41 or Example 42 further includes a collection well in fluid communication with the reaction vessel and configured to collect the gas.

[0142] 44. The system according to any one of Examples 41 to 43, wherein the gas comprises ammonia.

[0143] 45. The system according to any one of Examples 37 to 44, further comprising a controller in communication with at least one of the one or more channels or the device, the controller being configured to regulate at least one of: the flow rate of one or more of the aqueous solution or nitrogen source delivered below the surface, or the composition of one or more of the aqueous solution or nitrogen source.

[0144] Those skilled in the art will further understand the features and advantages of this disclosure based on the provided description and embodiments. Therefore, the invention is not limited to what is specifically shown and described. Within the scope of this disclosure, which includes illustrative descriptions including prototypes, benchtop models, or apparatuses, those skilled in the art will appreciate how the provided systems, devices, components, designs, and methods can be integrated into products and / or manufacturing methods based on this disclosure. All disclosures and references cited herein are expressly and entirely incorporated herein by reference.

[0145] The foregoing provides some non-limiting claims supported by the content of this disclosure.

Claims

1. A method for producing at least one of ammonia or an ammonium salt via geochemistry, comprising: An aqueous solution and a nitrogen source are transported below the surface to facilitate the reaction, thereby forming at least one of ammonia or an ammonium salt.

2. The method of claim 1, wherein the aqueous solution is delivered to a bedrock containing ultramafic rocks located below the surface.

3. The method according to claim 2, further comprising reacting the aqueous solution with the ultramafic rock to produce hydrogen (H2).

4. The method according to claim 2, wherein the nitrogen source includes N2, NO, N2O, NO2, and NO. x Or NO3 - One or more of them.

5. The method of claim 4, further comprising using geothermal energy to react hydrogen with the nitrogen source to form at least one of ammonia or an ammonium salt.

6. The method of claim 2, further comprising collecting ammonium salts from the ultramafic rock, wherein the ammonium salts comprise one or more of halide sands (NH4Cl) and ammonium bicarbonate (NH4HCO3).

7. The method of claim 5, wherein the hydrogen reacts with the nitrogen source at a pressure ranging from about 1 atm to about 400 atm.

8. The method of claim 1, wherein conveying the aqueous solution and the nitrogen source through the surface comprises passing the aqueous solution and the nitrogen source through a plurality of boreholes located on the surface.

9. The method of claim 1, wherein the reaction occurs approximately 1 foot to approximately 5 miles below the surface.

10. The method of claim 1, wherein the aqueous solution and the nitrogen source flow through a single borehole among a plurality of boreholes located on the surface.

11. The method of claim 10, wherein the reaction occurs in the presence of one or more catalysts to produce ammonia.

12. The method of claim 10, further comprising delivering one or more catalysts through a single borehole of the plurality of boreholes.

13. The method according to claim 11, wherein the one or more catalysts comprise one or more of the following: nickel, copper, cobalt, sodium, magnesium, calcium, titanium, chromium, iron, zinc, platinum, ruthenium, osmium, alumina, calcium oxide, molybdenum, ruthenium, alloys of different metals, or organic and organometallic catalysts.

14. The method of claim 11, wherein the one or more catalysts are naturally occurring beneath the Earth's surface.

15. The method of claim 1, further comprising generating droplets of the aqueous solution before delivering the aqueous solution below the surface, the droplets being generated using an electrospray device attached to a plurality of boreholes.

16. The method of claim 1, further comprising using a controller to regulate at least one of the following: the flow rate of one or more of the aqueous solution or the nitrogen source delivered to the subsurface, or the composition of one or more of the aqueous solution or the nitrogen source.

17. A method for increasing the yield of ammonia production, comprising: In the presence of a catalyst, an aqueous solution and a nitrogen source beneath the surface are exposed to an iron-bearing bedrock to promote the reaction, thereby forming ammonia.

18. The method of claim 17, wherein the catalyst is delivered below the surface.

19. The method of claim 18, wherein the catalyst is naturally occurring beneath the Earth's surface.

20. The method of claim 17, wherein the reaction occurs at a pressure ranging from about 1 atm (0.1 MPa) to more than 30 MPa.

21. A system for producing at least one of ammonia or an ammonium salt via geochemical means, comprising: One or more channels extending from the earth's surface; and A device in fluid communication with a rock bed via one or more channels, the device being configured to deliver an aqueous solution and a nitrogen source to the rock bed located close to the surface, thereby reacting with the rock bed to form products.

22. The system of claim 21, further comprising a storage device configured to collect the product.

23. The system of claim 22, further comprising a reaction vessel in fluid communication with the one or more channels and configured to facilitate a reaction between the product and the nitrogen source to form a gas.

24. The system of claim 23, further comprising a collection well in fluid communication with the reaction vessel and configured to collect the gas.

25. The system of claim 21, further comprising a controller in communication with at least one of the one or more channels or the device, the controller being configured to regulate at least one of the following: the flow rate of one or more of the aqueous solution or the nitrogen source delivered below the surface, or the composition of one or more of the aqueous solution or the nitrogen source.

Images