Systems and methods for hydrogen and ammonia production

Abstract

Provided herein are systems and methods for producing hydrogen and ammonia. Hydrogen is produced in an anion exchange membrane-based electrochemical stack. The hydrogen produced in the stack may be used to produce ammonia or for other applications requiring hydrogen. The feedstock for the anion exchange membrane-based electrochemical stack may be salt water, such as seawater. A desalination module or chlor-alkali stack may be used to treat the salt water prior to electrolysis in the anion exchange membrane-based electrochemical stack.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 63 / 444,808, entitled "SYSTEM AND METHODS FOR MODULAR WATER DESALINATION SYSTEM USING WATER ELECTROLYZER WASTE HEAT," filed February 10, 2023, and U.S. Provisional Application No. 63 / 338,971, entitled "SYSTEMS AND METHODS OF AMMONIA SYNTHESIS," filed May 6, 2022, the entire contents of each of which are incorporated herein by reference. [Background technology]

[0002] 2. Background of the Invention Hydrogen is a common gas that has many industrial uses, such as oil refining, metal processing, food processing, and ammonia production. One method of producing hydrogen involves electrolysis of water to produce oxygen and hydrogen gas. This process can be carried out in an electrolyzer that contains a polymer membrane that separates the oxygen and hydrogen. Generally, very pure water is required in electrolyzer systems. Summary of the Invention [Means for solving the problem]

[0003] Summary of the Invention Provided herein is a system for producing hydrogen and ammonia that uses salt water or other non-purified water sources to produce hydrogen.

[0004] The system generally comprises: an electrochemical stack for producing hydrogen, the electrochemical stack comprising an inlet operable to receive water from a water source and an anion exchange membrane, the first electrochemical stack electrolyzing water to produce hydrogen; and a reactor for producing ammonia, the reactor comprising an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack, and an energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen. In some embodiments, the water source comprises salt water. In some additional embodiments, the salt water comprises sodium and chloride salts.

[0005] In some embodiments, the energy source comprises a synthesis cell having a cathode, an anode, and a proton exchange membrane disposed between the cathode and the anode. In some additional embodiments, the proton exchange membrane comprises a perfluorosulfonic acid polymer or copolymer, a sulfonated poly(ether ether ketone) (sPEEK), a sulfonated phenylated poly(phenylene) (sPPP), a sulfonated polyether(sulfone) (SPES), a sulfonated polystyrene-b-poly(ethylene-r-butylene-b-polystrene) (S-SEBS), or a combination thereof.

[0006] In some embodiments, the electrochemical stack further comprises a cathode and an anode, and the anion exchange membrane is disposed between the cathode and the anode. In some additional embodiments, the anion exchange membrane comprises an imidazolium-functionalized styrene polymer, polysulfone and its derivatives, a polymer having a quaternary phosphonium group, or a combination thereof. In yet further embodiments, the electrochemical stack further comprises a first outlet operable to deliver hydrogen from the electrochemical stack, and a second outlet operable to deliver a secondary gas comprising oxygen from the electrochemical stack.

[0007] In some embodiments, the system further comprises a desalination system fluidly coupled to the electrochemical stack for supplying desalted water to the electrochemical stack, hi some embodiments, the system further comprises an ion exchange system fluidly coupled to the water source and to the electrochemical stack.

[0008] In some embodiments, the system further comprises a chlor-alkali stack fluidly coupled to the water source and to the electrochemical stack. In some aspects, the chlor-alkali stack comprises an anode, a cathode, and a proton exchange membrane. In some embodiments, the system further comprises a hydrogen storage system fluidly coupled to the electrochemical stack.

[0009] In some embodiments, the system further comprises an electrochemical hydrogen pump fluidly connected to the outlet of the ammonia reactor for removing unreacted hydrogen gas. In some aspects, the electrochemical hydrogen pump comprises an anode, a cathode, and a proton exchange membrane.

[0010] In some embodiments, the system further comprises a phase separator fluidly connected to an outlet of the electrochemical stack for removing water from the produced hydrogen. In some aspects, the phase separator is fluidly connected to an inlet of the ammonia reactor.

[0011] Further provided herein is a system for producing hydrogen and ammonia. The system generally comprises: a desalination system operable to remove salt from salt water, thereby producing desalted water; an electrochemical stack for producing hydrogen, the electrochemical stack comprising an inlet operable to receive water from a water source, and an anion exchange membrane, the electrochemical stack for producing hydrogen, the electrochemical stack comprising a first electrochemical stack electrolyzing water to produce hydrogen; and a reactor for producing ammonia, the reactor comprising an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack, and an energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen.

[0012] Further provided herein is a system for producing hydrogen and ammonia.The system generally comprises: a chlor-alkali stack operable to remove chlorine from salt water, thereby producing dechlorinated water; an electrochemical stack for producing hydrogen, the electrochemical stack comprising an inlet operable to receive water from a water source, and an anion exchange membrane, the electrochemical stack for producing hydrogen, the first electrochemical stack comprises an electrochemical stack that electrolyzes water to produce hydrogen; and a reactor for producing ammonia, the reactor comprising an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack, and an energy source.

[0013] In some embodiments, the system further comprises an ion exchange system in fluid communication with the chlor-alkali stack and the electrochemical stack, the ion exchange system receiving a quantity of dechlorinated water produced by the chlor-alkali stack to produce deionized water. In some aspects, the deionized water is combined with a quantity of dechlorinated water not received by the ion exchange system prior to entering the electrochemical stack. In some aspects, the system further comprises a valve operable to regulate an amount of sodium hydroxide solution delivered to the ion exchange system.

[0014] Further provided herein is a system for producing hydrogen. The system generally comprises an electrochemical stack for producing hydrogen, the electrochemical stack comprising an inlet operable to receive water from a water source; an anion exchange membrane; and an outlet fluidly connected to a reactor for producing ammonia, wherein a first electrochemical stack electrolyzes water to produce hydrogen.

[0015] Further provided herein is a method for producing hydrogen and ammonia. The method generally includes: producing hydrogen in an electrochemical stack comprising an inlet operable to receive water from a water source and an anion exchange membrane, where a first electrochemical stack electrolyzes water to produce hydrogen; and producing ammonia in a reactor comprising an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack, and an energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen. In some embodiments, the water comprises salt water. In some embodiments, the method includes storing the hydrogen produced by the electrochemical stack.

[0016] In some embodiments, the method further includes dechlorinating the saltwater in a chlor-alkali stack and delivering the dechlorinated water to an inlet of an electrochemical stack.

[0017] In some embodiments, the method further includes desalination of the salt water and delivering the desalinated water to an inlet of the electrochemical stack, hi some embodiments, the method further includes transferring heat generated by the electrochemical stack to a desalination system via a heat exchange fluid.

[0018] In some embodiments, the method further includes deionizing the water in an ion exchange system and delivering the deionized water to an inlet of the electrochemical stack. [Brief description of the drawings]

[0019] [Figure 1A] 1A-1B show an exemplary system of the present disclosure including an AEM electrolyzer stack and an ammonia reactor, with FIG 1A showing the overall system and FIG 1B showing another view of the AEM electrolyzer stack and associated components. [Figure 1B] Same as above.

[0020] [Figure 2A]2A-2B show an exemplary system of the present disclosure including an AEM electrolyzer stack, an ammonia reactor, and a chlor-alkali stack, with Figure 2A showing the overall system and Figure 2B showing another view of the AEM electrolyzer stack, the chlor-alkali stack, and associated components. [Figure 2B] Same as above.

[0021] [Figure 3A] 3A-3B show an exemplary system of the present disclosure including an AEM electrolyzer stack, an ammonia reactor, a chlor-alkali stack, and a desalination system, with Figure 3A showing the overall system and Figure 3B showing another view of the AEM electrolyzer stack, chlor-alkali stack, desalination system, and associated components. [Figure 3B] Same as above.

[0022] [Figure 4A] 4A-4B show an exemplary system of the present disclosure including an AEM electrolyzer stack, an ammonia reactor, and a desalination system, with Figure 4A showing the overall system and Figure 4B showing another view of the AEM electrolyzer stack, desalination system, and associated components. [Figure 4B] Same as above. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] Detailed Description of the Invention Provided herein are systems and methods for producing hydrogen and ammonia. The systems and methods described herein use an anion exchange membrane (AEM) electrochemical stack to produce hydrogen via electrolysis. Ammonia can be produced by a variety of means as described herein using hydrogen produced in the AEM stack. Alternatively or in addition, hydrogen produced in the AEM stack may be stored and used for purposes other than producing ammonia. Because the AEM stack can use salt water (e.g., seawater) as the water source for electrolysis without further purification, the use of an AEM stack to produce hydrogen may be preferred over other hydrogen production methods.

[0024] I. System The system of the present disclosure comprises one or more electrochemical stacks comprising an AEM electrolyzer stack. When more than one AEM electrolyzer stack is included in the system, the AEM electrolyzer stacks may be connected in parallel. Electrolyzer stacks for membrane-based electrolysis of water to produce hydrogen are generally known and described in the related art. An AEM electrolyzer cell comprises a cathode, an anode, and an anion exchange membrane disposed between the cathode and the anode. An AEM electrolyzer stack may comprise multiple AEM electrolyzer cells, i.e., multiple cathode-AEM-anode cells. An AEM electrolyzer stack may further comprise pumps, valves, conduits, exhaust systems, power electronics, and other components necessary to provide safe and efficient production of hydrogen.

[0025] In use, as described in more detail below, water and electricity may be supplied to the AEM-based electrolyzer stack, and a portion of the water may be electrochemically electrolyzed to form hydrogen (e.g., via hydrogen ion diffusion through the AEM electrolyte from the cathode side of the electrolyzer to the anode side of the AEM electrolyzer). For example, a water circuit comprising pumps, valves, piping, etc. may be operable to deliver water to the AEM-based electrochemical stack. The water may be delivered, for example, by pumping, using methods known in the art. As the water moves through the AEM-based electrochemical stack, electrical power delivered to the AEM-based electrochemical stack may move at least a portion of the protons of the water through the AEM electrolyte to form hydrogen. Anions, such as hydroxyl anions, may be captured at the anion exchange membrane and may move to the anode of the AEM-based electrochemical stack.

[0026] Anion exchange membrane and the method of making and procuring anion exchange membrane are generally known to those skilled in the art.In some embodiments, anion exchange membrane may comprise imidazolium functionalized styrene polymer, polymer containing quaternary ammonium group, polysulfone and its derivatives, polymer with quaternary phosphonium group, polymer with anion exchange group incorporated in polymer backbone, and other anion exchange materials known in the art.

[0027] The water delivered to the AEM-based electrochemical stack may be purified water, tap water, well water, industrial wastewater, non-industrial wastewater, deionized water, fresh water (e.g., water from lakes, rivers, ponds, streams, etc.; <0.05% salt content), salt water (e.g., seawater; 3%-5% salt content), or brackish water (0.05%-3% salt content). In general, the water may have a salt content of about 5% by weight or less, about 4% by weight or less, about 3% by weight or less, about 2% by weight or less, about 1% by weight or less, about 0.1% by weight or less, or about 0.05% by weight or less. The water may be derived from a single source or from multiple sources of varying quality.

[0028] When using salt water or brackish water, one skilled in the art will recognize that the chemical composition of the salt content of salt water or brackish water can vary depending on where the water is collected. Generally, salt water contains salts of chloride, sodium, magnesium, sulfate, calcium, and potassium. Anions (i.e., chloride and sulfate ions) can be conducted by an anion exchange membrane.

[0029] The water delivered to the AEM electrolyzer stack may be purified using an ion exchange system. The ion exchange system comprises an ion exchange column. The water is delivered to the ion exchange column via methods known in the art, such as pumping, where the water contacts an ion exchange medium that captures and removes ionized impurities from the water. The ion exchange column may be a co-current, counter-current, or mixed-phase ion exchange column. Suitable ion exchange media include cation resins and anion resins. Examples of suitable media for ion exchange are generally known in the art and include polymers with sulfonic acid groups, polymers with quaternary amino groups, polymers with carboxylic acid groups, and polymers with primary, secondary, and tertiary amines. Specific polymers for use in ion exchange resins include crosslinked polystyrene (e.g., polystyrene crosslinked with divinylbenzene), sodium polystyrene sulfonate, polyAMPS, polyAPTAC, and other polymers known in the art. The system may include multiple ion exchange columns connected in parallel so that if the ion exchange medium in one column no longer has ion exchange capacity, another column can be used while the medium in the first column is being regenerated.

[0030] Deionized water may be delivered directly to the AEM-based electrolyzer stack or may be combined with a quantity of non-deionized water to optimize the water properties (e.g., conductivity, pH, concentration of specific ions, etc.) to improve the efficiency of the electrolysis reaction.

[0031] The electricity supplied to the AEM electrolyzer stack preferably includes renewable energy sources, such as solar, wind, hydroelectric, geothermal, and the like. The electricity supplied to the AEM electrolyzer stack may be sourced from a power grid, such as a regional, city, or private grid. The electricity supplied to the AEM electrolyzer stack may be sourced from an energy storage mechanism or multiple energy storage mechanisms. The energy storage mechanism may comprise any mechanism or device operable to store energy, such as electricity, thermal energy, and the like. For example, the energy storage mechanism may include batteries (e.g., lead acid batteries, lithium ion batteries, lithium iron batteries, etc.), ice, water, flywheels, compressed air, pumped hydro, or other energy storage mechanisms known in the art, and combinations thereof.

[0032] The hydrogen produced by the AEM electrolyzer stack may be stored in a hydrogen storage system, the hydrogen may be delivered to a customer for use, or the hydrogen may be fed to an ammonia reactor as further described herein.

[0033] The AEM electrolyzer stack may include two outlets. A first outlet may be fluidly coupled to the cathode side of the AEM electrolyzer stack and is operable to deliver hydrogen produced in the AEM electrolyzer stack. The hydrogen may be delivered by methods known in the art for transporting hydrogen. A second outlet may be fluidly coupled to the anode side of the AEM electrolyzer stack and is operable to deliver oxygen gas produced in the AEM electrolyzer stack. The hydrogen may be delivered by methods known in the art for transporting oxygen.

[0034] Hydrogen produced in the AEM electrolyzer stack may be delivered to a phase separator. The phase separator is operable to condense water and other impurities to purify hydrogen gas. The phase separator may be a two-phase separator. The phase separator preferably comprises a vertical knock-out drum. Methods for making and sizing a knock-out drum suitable for separating water from hydrogen gas are well known to those skilled in the art.

[0035] The phase separator comprises an inlet portion and an outlet portion. The inlet portion is operable to receive wet hydrogen from the AEM electrolyzer stack. The hydrogen gas may have a purity of about 95% to about 98%, with the primary impurity being water. The outlet portion may comprise a first outlet operable to deliver dry hydrogen. The dry hydrogen may be low pressure hydrogen, for example, at about 1 bar to about 2 bar. The outlet portion may further comprise a second outlet to deliver water separated from the wet hydrogen. The water may be delivered by methods known in the art, for example, by pumping. The second outlet may be fluidly coupled to the AEM electrolyzer stack to recycle water and reduce the total amount of water required by the system.

[0036] Additionally or alternatively, the hydrogen may be directed to a dryer to remove excess water and increase the purity of the hydrogen. The dryer may include, for example, a pressure swing adsorption (PSA) system, a temperature swing adsorption (TSA) system, a hybrid PSA-TSA system, or a membrane purification device. The dryer comprises an inlet portion and an outlet portion. The inlet portion is operable to receive wet hydrogen. The hydrogen gas may have a purity of about 95% to about 98%, with the primary impurity being water. The outlet portion comprises a first outlet operable to deliver dry hydrogen. The dry hydrogen may be low pressure hydrogen, for example, at about 1 bar to about 2 bar. The dryer may further comprise a second outlet that delivers water separated from the wet hydrogen. The water may be delivered by methods known in the art, for example, by pumping. The water stream may include a portion of the hydrogen gas produced in the AEM electrolyzer stack. The water stream may include hydrogen having a concentration of about 0% to about 25% by weight. The second outlet may be fluidly connected to the AEM electrolyzer stack to recycle water and reduce the total amount of water required by the system.

[0037] The dryer may comprise one or more layers of a water sorbent material, such as activated carbon, silica, zeolite, or alumina. The dryer may comprise a membrane, such as a PEM electrolyte. As the gas consisting essentially of hydrogen and water moves from the inlet portion to the outlet portion of the dryer, at least some water may be removed from the product mixture by adsorption of either water or hydrogen in the layer of water sorbent material. If hydrogen is adsorbed, it is removed to the outlet conduit during the pressure and / or temperature swing cycle. If water is adsorbed, it is removed to the pump conduit during the pressure and / or temperature swing cycle. In some examples, the adsorption performed by the dryer may be passive, without the addition of heat or electricity that could otherwise act as an ignition source for the pyrophoric hydrogen-containing mixture. However, in such examples, considerations related to the back pressure created by the dryer in fluid communication with the electrochemical stack may limit the size of the dryer to remove moisture from the product stream, and therefore the effectiveness of a single pass.

[0038] In some embodiments, the hydrogen may be directed to a hydrogen pump that increases the purity and / or pressure of the hydrogen. In certain embodiments where hydrogen is delivered to an ammonia reactor, a hydrogen pump may not be used, as the hydrogen may be used at ambient pressure. Delivery may be accomplished by methods known in the art for transporting hydrogen. In other embodiments where hydrogen is used for storage or other purposes, higher pressures of hydrogen may be required.

[0039] The hydrogen pump may include a hydrogen recirculation stack. The hydrogen recirculation stack includes an inlet portion and an outlet portion. The first inlet is operable to receive hydrogen produced in the AEM electrolyzer stack. The hydrogen may be wet hydrogen, or the hydrogen may be dry hydrogen that has been passed through a dryer or phase separator. The outlet portion includes a first outlet operable to provide a purified hydrogen stream. The first outlet may be fluidly connected to a hydrogen storage system or a system or process that requires purified hydrogen, such as a fuel cell stack. In a preferred embodiment, the first outlet of the hydrogen recirculation stack is fluidly connected to the fuel cell stack. The second outlet may include a purge stream that includes hydrogen, oxygen, and / or water. The second outlet may be recycled in the system of the present disclosure, or the second outlet may be vented to the atmosphere. For example, the water in the purge stream may be recycled to the AEM electrolyzer stack for electrolysis.

[0040] The pressure of the hydrogen supplied to the hydrogen pump is typically about 1 bar to about 2 bar, however the pressure may be higher or lower depending on the requirements of the system and equipment used.

[0041] The AEM electrolyzer stack may include a heat exchanger. The heat exchanger is thermally coupled to the AEM electrolyzer stack to absorb heat generated by the AEM electrolyzer. The heat exchanger may include any heat exchanger known in the art. For example, the heat exchanger may include a shell-and-tube heat exchanger, a double tube heat exchanger, a tube-in-tube heat exchanger, a plate heat exchanger, a plate-and-shell heat exchanger, an adiabatic wheel heat exchanger, a plate-fin heat exchanger, a finned tube heat exchanger, a pillow plate heat exchanger, or combinations thereof. The heat exchanger may include a heat exchange fluid that absorbs heat generated by the electrolyzer. The heat exchange fluid may include air, water, steam, a mixture of water and glycol, silicon liquid, molten salt, or other fluids known in the art useful for heat exchange. The heat may then be delivered to another component of the system, for example, a desalination module. Delivery may be accomplished using methods commonly known in the art, for example, by pumping the heated heat exchange fluid to another component of the system.

[0042] The ammonia reactor may be fluidly connected to a nitrogen source and to a hydrogen source. Preferably, the hydrogen source comprises an AEM electrolyzer stack as described herein, but may alternatively or additionally be fluidly connected to a hydrogen storage system, which is in turn fluidly connected to the AEM electrolyzer stack. The ammonia reactor may have a single pass yield of less than 100 percent, and in some cases may be below the single pass yield levels associated with Haber-Bosch reactors (e.g., metal catalysts such as Fe catalysts) operated at high temperatures (e.g., about 400° C.) and pressures (e.g., about 200 atm). In some embodiments, the reactor may have a single pass yield of greater than 0% and less than 15%. The output from the ammonia reactor may include ammonia (NH3), as well as unreacted nitrogen and hydrogen gas. As further described below, the unreacted hydrogen may be recovered using an electrochemical hydrogen pump and recycled to the ammonia reactor to improve the overall efficiency of the system.

[0043] The nitrogen source may comprise a nitrogen storage vessel, e.g., a nitrogen tank or a device that separates oxygen and nitrogen. In one embodiment, the nitrogen source may remove nitrogen from air (e.g., from compressed air) to form nitrogen and nitrogen-diluted air. For example, the nitrogen source may comprise one or more of a pressure swing adsorber, a temperature swing adsorber, a hybrid pressure and thermal swing adsorber, or a cooling unit. Additionally or alternatively, the nitrogen source may comprise an electrochemical cell operable to electrochemically pump nitrogen or oxygen from air. The output of the nitrogen source may include nitrogen and nitrogen-depleted air (e.g., air having more than 21 percent oxygen). In certain implementations, the nitrogen-depleted air may be directed to one or more cascaded stages of a nitrogen removal process to further separate nitrogen from the nitrogen-depleted air to form more nitrogen.

[0044] In another embodiment, the nitrogen source may remove oxygen from air (e.g., from compressed air) to form nitrogen-diluted air and oxygen. For example, the nitrogen source may comprise an electrochemical cell operable to electrochemically pump oxygen from air. The output of the nitrogen source may include oxygen and oxygen-depleted air (e.g., air having less than 21 percent oxygen) that is supplied to the reactor 102. In certain implementations, the oxygen-depleted air may be directed to one or more cascaded stages of an oxygen removal process to further separate oxygen from the oxygen-depleted air to increase its nitrogen concentration.

[0045] Nitrogen produced by the nitrogen source (or oxygen-depleted air) may be directed to the inlet of the reactor via the nitrogen stream. The nitrogen that can flow from the nitrogen source to the reactor may contain certain non-oxygen impurities from the compressed air and / or from the process used to separate oxygen from the compressed air. Such impurities (e.g., carbon dioxide and / or argon) may be acceptable to the extent that a given impurity does not prevent ammonia formation in the system and does not degrade any one or more of the various parts of the system.

[0046] The reactor may comprise an electrochemical ammonia reactor (i.e., a membrane electrochemical reactor). The reactor comprises an energy source comprising a proton exchange membrane (PEM) operable to electrochemically synthesize ammonia from hydrogen and nitrogen. The electrochemical ammonia reactor may comprise an anode, a cathode, and a proton exchange membrane disposed between the anode and the cathode. The electrochemical ammonia reactor may comprise a power supply connected to the anode and to the cathode to create an electric field (i.e., apply a voltage between the anode and the cathode) in the PEM disposed between the anode and the cathode.

[0047] Hydrogen may be introduced into the anode of the electrochemical ammonia reactor, where it decomposes into protons. Under an electric field created by a power source, the protons may flow from the anode to the cathode through a proton exchange membrane. At the cathode, nitrogen may be introduced into the reactor and flow over the cathode, where it may react with the protons to form ammonia. If desired, in addition to the hydrogen pumped through the proton exchange membrane, additional hydrogen may also be fed directly to the cathode.

[0048] The proton exchange membrane may comprise a perfluorosulfonic acid polymer or copolymer, such as a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer. The proton exchange membrane may alternatively or additionally comprise a sulfonated poly(ether ether ketone) (sPEEK), a sulfonated phenylated poly(phenylene) (sPPP), a sulfonated polyether(sulfone) (SPES), a sulfonated polystyrene-b-poly(ethylene-r-butylene-b-polystyrene (S-SEBS), or a combination thereof. In some examples, the proton exchange membrane may comprise a perfluorosulfonic acid polymer or copolymer, such as a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer. 13 In some further examples, the proton exchange membrane may include Selemion CMV, Neosepta CMS, Fumasep FKS 30, or a combination thereof.

[0049] In other embodiments, the ammonia reactor may be equipped with a low yield catalyst (e.g., a catalyst operated at temperatures and pressures below those associated with the conventional Haber-Bosch process) or a plasma-driven reactor. Ammonia reactors of this type are generally known in the relevant art.

[0050] The output of the ammonia reactor can be fluidly connected to an electrochemical hydrogen pump that can take unreacted hydrogen flowing along with the product stream and recycle the unreacted hydrogen to the inlet of the reactor. Recycling hydrogen in this manner can increase the overall yield of the reactor by replacing at least a portion of the hydrogen that would otherwise need to be produced by the hydrogen source to meet the input requirements of the reactor.

[0051] The hydrogen pump may be an electrochemical membrane hydrogen pump comprising one or more electrochemical cells. Each of the electrochemical cells may comprise an anode, a cathode, and a proton exchange membrane disposed between the anode and the cathode. Electric power supplied to the hydrogen pump creates an electric field, which may result in a concentration of high pressure along the cathode compared to the anode. At the anode, the lower pressure hydrogen may separate into protons and electrons, and the electric field may drive the protons across the proton exchange membrane to the cathode. The protons may then recombine at higher pressure at the cathode to form hydrogen.

[0052] A cascade of hydrogen pumps connected in series can increase the output hydrogen to a desired pressure. This hydrogen can be delivered back to the ammonia reactor to react with nitrogen gas, or the hydrogen can be stored or used for other purposes. Delivery can be achieved by methods known in the art. In general, the target pressure can be at least above the minimum pressure required to deliver the hydrogen recovered at or upstream of the inlet of the ammonia reactor to one or more reactant streams. Pressures above the minimum pressure can be useful, among other things, to control the ratio of recycled hydrogen to non-recycled hydrogen from the hydrogen source. That is, increasing the pressure above the minimum pressure increases the relative amount of recycled hydrogen used to meet the total hydrogen need of the ammonia reactor. The upper limit of the pressure range useful for controlling the fraction of recycled hydrogen in the total hydrogen can be bound by considerations such as, but not limited to, the total power required by the electrochemical hydrogen pump compared to the power required by the hydrogen source, hardware, safety, or a combination thereof.

[0053] The output of the ammonia reactor may alternatively or additionally be fluidly connected to a phase separator. The phase separator may be operable to condense at least a portion of the ammonia from the output of the ammonia reactor before or after the excess hydrogen is removed. The ammonia may be condensed by the phase separator, drained, or stored for further use. The remaining nitrogen gas and any additional excess hydrogen may be vented to the atmosphere or recycled to the ammonia reactor to improve process efficiency.

[0054] In some embodiments, the system may include a water desalination system. The water desalination system is capable of reducing the salt content of salt water or brackish water. The water desalination system may be operable to supply purified water to the AEM electrolyzer stack. Preferably, the purified water produced from the desalination system has a salt content of about 10 μS / m 3 ~about 50μS / m 3 It has a conductivity of

[0055] The desalination system may utilize one or more desalination methods known in the art, such as distillation (e.g., solar distillation, evaporation, vacuum distillation, multi-stage flash distillation, membrane distillation), osmosis (e.g., reverse osmosis), freeze-thaw, electrodialysis or microbial distillation, or combinations thereof. Preferably, the desalination system utilizes a membrane-based distillation method, such as a reverse osmosis desalination system or an electrodialysis desalination system.

[0056] Generally, water desalination systems require heating to move water through a membrane that separates impurities from the water. Thus, the desalination system may include a heat exchanger thermally coupled to one or more components of the systems described herein, such as an AEM electrolyzer stack, an ammonia reactor, or a chlor-alkali stack, or a combination thereof. Preferably, the desalination system is thermally coupled to the AEM electrolyzer stack via a heat exchanger.

[0057] The heat exchanger may include any heat exchanger known in the art. For example, the heat exchanger may comprise a shell-and-tube heat exchanger, a double-tube heat exchanger, a tube-in-tube heat exchanger, a plate heat exchanger, a plate-and-shell heat exchanger, an adiabatic wheel heat exchanger, a plate-fin heat exchanger, a finned-tube heat exchanger, a pillow plate heat exchanger, or a combination thereof. The heat exchanger may include a heat exchange fluid that absorbs heat generated by the electrolytic cell. The heat exchange fluid may include air, water, steam, a mixture of water and glycol, silicon liquid, molten salt, or other fluids known in the art useful for heat exchange.

[0058] The desalted water produced by the desalination system may be fed directly to the AEM electrolyzer stack. Alternatively, a portion of the desalted water may be fed to an ion exchange system as described herein. The portion of the desalted water fed to the ion exchange system may be predetermined based on the conductivity of the water entering the AEM electrolyzer stack as measured by one or more conductivity meters. Conductivity meters and methods of measuring conductivity are generally known in the art. One or more flow control valves may regulate the flow rate of desalted water and deionized water entering the AEM electrolyzer stack based on the input received from the conductivity meters. The flow control valves may be any valves known in the art suitable for controlling the flow rate of water. In another embodiment, the desalted water may be combined with raw water from a water source (e.g., salt water). The flow rate of raw water may also be regulated by the flow control valves based on the conductivity of the water entering the AEM electrolyzer stack.

[0059] In some embodiments, the system may include a chlor-alkali electrolyzer stack (also referred to herein as a "chlor-alkali stack"). The chlor-alkali process is known in the art for electrolyzing an aqueous solution of sodium chloride to form hydrogen, chlorine (Cl2), and aqueous sodium hydroxide (NaOH). The process operates in a similar manner for solutions containing calcium chloride or potassium chloride.

[0060] The chlor-alkali stack comprises an electrolyzer comprising an anode, a cathode, and a proton exchange membrane disposed between the anode and the cathode. Electricity is passed through the stack to generate an electric field. Brine is delivered to the anode side of the chlor-alkali stack using methods commonly known in the art, for example, by pumping. Chloride ions in the brine are oxidized at the anode to form chlorine gas and cations (e.g., sodium, potassium, or calcium cations). Chlorine gas dissolves from the solution and is collected. The cations pass through the polymer exchange membrane to the cathode side of the stack. At the cathode, hydrogen ions are reduced to form hydrogen gas and hydroxyl ions. The hydroxyl ions react with the cations to produce a basic solution. The basic solution may include sodium hydroxide, potassium hydroxide, or calcium hydroxide.

[0061] Hydrogen gas may be collected from the chlor-alkali stack and pressurized and / or stored for further use. Alternatively, hydrogen may be purified for use in the ammonia reactor described herein by use of an electrochemical hydrogen pump.

[0062] The chlor-alkali stack may include a heat exchanger. The heat exchanger is thermally coupled to the chlor-alkali stack to absorb heat generated by the chlor-alkali stack. The heat exchanger may include a heat exchange fluid, such as propylene glycol or water, that absorbs heat generated by the electrolyzer. The heat can then be delivered to another component of the system, such as a heat sink, or more preferably, an ammonia reactor as described herein, to improve the efficiency of the ammonia reaction. Alternatively or in addition, the heat may be delivered to a desalination module as described herein to improve the efficiency of the desalination. Delivery may be accomplished by methods known in the art, such as pumping a heat exchange fluid from one system component to another.

[0063] The water delivered to the chlor-alkali stack may be salt water (e.g., seawater; 3%-5% salt content) or brackish water (0.05%-3% salt content). Generally, the water may have a salt content of about 5% by weight or less, about 4% by weight or less, about 3% by weight or less, about 2% by weight or less, about 1% by weight or less, about 0.1% by weight or less, or about 0.05% by weight or less.

[0064] The dechlorinated water produced by the chlor-alkali stack may be fed directly to the AEM electrolyzer stack. Alternatively, a portion of the dechlorinated water may be fed to an ion exchange system as described herein. The portion of the dechlorinated water fed to the ion exchange system may be predetermined based on the conductivity of the water entering the AEM electrolyzer stack as measured by one or more conductivity meters. Conductivity meters and methods for measuring conductivity are generally known in the art. One or more flow control valves may regulate the flow rate of the dechlorinated and deionized water entering the AEM electrolyzer stack based on the input received from the conductivity meter. The flow control valve may be any valve known in the art suitable for controlling the flow rate of water.

[0065] The system may further include one or more heat sinks to absorb excess heat generated by the system. The heat sinks may include seawater, air radiators, geothermal cooling, or other cooling systems known in the art. The heat sinks may be thermally coupled to one or more heat exchangers of the system.

[0066] The system may further comprise a hydrogen storage system. Systems and methods for storing hydrogen are generally known in the art, for example, storage tanks. The hydrogen storage system may be in fluid communication with the AEM electrolyzer stack, which stores the hydrogen produced by the stack. The hydrogen storage system may include pressurized hydrogen. The pressurized hydrogen may be stored at a pressure of about 350 bar to about 700 bar; for example, about 350 bar, 400 bar, 450 bar, 500 bar, 550 bar, 600 bar, 650 bar, or about 700 bar. Compressors and / or electrochemical hydrogen pumps, such as those described herein, may be used to pressurize the hydrogen for storage.

[0067] The system may further comprise a chlorine storage system. Systems and methods for storing chlorine are generally known in the art, for example, storage tanks.

[0068] The system may further comprise an oxygen storage system. Systems and methods for storing oxygen are generally known in the art, for example storage tanks.

[0069] The system may further comprise power electronics. The power electronics may be formed or provided in a single assembly that electrically connects one or more system components with an electrical supply. For example, the power electronics may be electrically coupled to one or more of the AEM electrolyzer stack, the ammonia reactor, the hydrogen recirculation pump, the chlor-alkali stack, the desalination module, or to other system components described herein. The power electronics may be operable to be electrically connected to a DC energy input, an AC energy input, and combinations thereof. The power electronics may further be operable to be connected to a DC energy load, an AC energy load, and combinations thereof. The power electronics may comprise a GaN inverter substrate, and an integrated power board, a control card, a display board, and / or a DAB converter. In some embodiments, the power electronics may be the power electronics described in U.S. Application No. 17 / 360,153, entitled "IMPEDANCE MONITORING OF A MODULAR ELECTROLYSIS SYSTEM," the contents of which are incorporated herein by reference in their entirety.

[0070] The system may further comprise a controller. The controller may be operatively connected to one or more of the system components described herein above. The controller is operable to regulate various parameters of the system based on various inputs received, such as temperature, flow rate, pressure, current, voltage, conductivity, humidity, etc. The controller may also be operable to shut down or start up one or more system components.

[0071] Referring now to the drawings, FIG. 1 illustrates an exemplary system 100 of the present disclosure. The system 100 includes a water source 120 fluidly coupled to the AEM electrolyzer stack 102 to supply water to the AEM electrolyzer stack 102. The water may be deionized in a deionization layer 114 (see FIG. 1B ) of the subsystem 110 as described herein to remove salts and other impurities in the water. The oxygen produced by the AEM electrolyzer stack 102 may be vented to the atmosphere or the oxygen may be collected. The AEM electrolyzer stack 102 is fluidly coupled to an ammonia reactor 104. The hydrogen gas produced by the AEM electrolyzer stack 102 may be delivered to the ammonia reactor 104 or may be stored or supplied for another use. The ammonia reactor 104 is fluidly coupled to a nitrogen source 108. The nitrogen source 108 supplies nitrogen gas to the ammonia reactor 104. The ammonia reactor 104 produces a mixture of ammonia, hydrogen, and nitrogen. Unreacted hydrogen is separated from the ammonia and nitrogen via a hydrogen pump 106 fluidly connected to the ammonia reactor. The hydrogen is recycled to the inlet portion of the ammonia reactor 104 for reuse. Alternatively, the hydrogen may be stored or supplied for another use. The nitrogen and ammonia are collected for processing and use.

[0072] In FIG. 1B, subsystem 110 illustrates an exemplary system for deionizing water before delivering it to the AEM electrolyzer stack 102. The water is fluidly coupled to the AEM electrolyzer stack 102 and to an ion exchange system 114. The water is split into two streams, each of which is controlled by flow control valves 122a, 122b. Flow control valve 122a controls the flow rate of water that is fed directly to the AEM electrolyzer stack 102. Flow control valve 122b controls the flow rate of water that is fed to the ion exchange system 114. The AEM electrolyzer stack 102 is also fluidly coupled to a phase separator 116, which is operable to remove excess water and other impurities from the hydrogen gas produced by the AEM electrolyzer stack 102. The phase separator 116 recycles excess water back to the AEM electrolyzer stack 102 for electrolysis. Alternatively, water may be purged from the system 100. A conductivity meter 118 determines the conductivity of the water exiting the phase separator 116. Flow control valves 122a, 122b allow the flow rates of water and deionized water delivered to the AEM electrolyzer stack 102 to be adjusted to increase or decrease the conductivity of the water supplied to the AEM electrolyzer stack 102 in order to optimize performance of the AEM electrolyzer stack 102.

[0073] FIG. 2A illustrates another exemplary system 200 of the present disclosure. The system 200 includes a water source 120 fluidly connected to the chlor-alkali stack 112 to supply brine to the chlor-alkali stack 112. The chlor-alkali stack 112 removes chlorine from the brine in the form of chlorine gas, which may be stored or supplied for use. The chlor-alkali stack 112 is fluidly connected to the AEM electrolyzer stack 102 to supply dechlorinated water to the AEM electrolyzer stack 102. The dechlorinated water may be deionized in a deionization layer 114 (see FIG. 2B) described herein to remove salts and other impurities in the brine. The oxygen produced by the AEM electrolyzer stack 102 may be vented to the atmosphere or the oxygen may be collected. The AEM electrolyzer stack 102 is fluidly connected to an ammonia reactor 104. The hydrogen gas produced by the AEM electrolyzer stack 102 may be delivered to the ammonia reactor 104 or may be stored or supplied for another use. The ammonia reactor 104 is fluidly connected to a nitrogen source 108. The nitrogen source 108 supplies nitrogen gas to the ammonia reactor 104. The ammonia reactor 104 produces a mixture of ammonia, hydrogen, and nitrogen. Unreacted hydrogen is separated from the ammonia and nitrogen via a hydrogen pump 106 that is fluidly connected to the ammonia reactor. The hydrogen is recycled to the inlet portion of the ammonia reactor 104 for reuse. Alternatively, the hydrogen may be stored or supplied for another use. The nitrogen and ammonia are collected for processing and use.

[0074] In FIG. 2B, subsystem 210 illustrates an exemplary system for deionizing water and then delivering it to the AEM electrolyzer stack 102. The chlor-alkali stack 112 is fluidly coupled to the AEM electrolyzer stack 102 and to the ion exchange system 114. The dechlorinated water produced from the chlor-alkali stack 112 is split into two streams, each of which is controlled by a flow control valve 122a, 122b. The flow control valve 122a controls the flow rate of the dechlorinated water fed to the AEM electrolyzer stack 102. The flow control valve 122b controls the flow rate of the dechlorinated water fed to the ion exchange system 114. The AEM electrolyzer stack 102 is also fluidly coupled to a phase separator 116, which is operable to remove excess water from the hydrogen gas produced by the AEM electrolyzer stack 102. The phase separator 116 recycles the excess water back to the AEM electrolyzer stack 102 for electrolysis. Alternatively, water may be purged from the system 200. A conductivity meter 118 determines the conductivity of the water exiting the phase separator 116. Flow control valves 122a, 122b allow the flow rates of dechlorinated and deionized water delivered to the AEM electrolyzer stack 102 to be adjusted to increase or decrease the conductivity of the water supplied to the AEM electrolyzer stack 102 in order to optimize performance of the AEM electrolyzer stack 102.

[0075] FIG. 3A illustrates an exemplary system 300 of the present disclosure. The system 300 includes a water source 120 fluidly connected to the chlor-alkali stack 112 to supply the brine to the chlor-alkali stack 112 and to the desalination system 124 to supply the brine to the desalination system 124. The chlor-alkali stack 112 removes chlorine from the brine in the form of chlorine gas, which may be stored or supplied for use. The chlor-alkali stack 112 is fluidly connected to the AEM electrolyzer stack 102 to supply the desalination water to the AEM electrolyzer stack 102. The desalination system 124 is also fluidly connected to the AEM electrolyzer stack 102 to supply the desalination water to the AEM electrolyzer stack 102. The desalination water may be deionized in a deionization layer 114 (see FIG. 3B) of the subsystem 310 as described herein to remove salt and other impurities in the brine. The oxygen produced by the AEM electrolyzer stack 102 may be vented to the atmosphere or the oxygen may be collected. The AEM electrolyzer stack 102 is fluidly connected to an ammonia reactor 104. The hydrogen gas produced by the AEM electrolyzer stack 102 may be delivered to the ammonia reactor 104 or may be stored or supplied for another use. The ammonia reactor 104 is fluidly connected to a nitrogen source 108. The nitrogen source 108 supplies nitrogen gas to the ammonia reactor 104. The ammonia reactor 104 produces a mixture of ammonia, hydrogen, and nitrogen. Unreacted hydrogen is separated from the ammonia and nitrogen via a hydrogen pump 106 fluidly connected to the ammonia reactor. The hydrogen is recycled to the inlet portion of the ammonia reactor 104 for reuse. Alternatively, the hydrogen may be stored or supplied for another use. The nitrogen and ammonia are collected for processing and use.

[0076] In FIG. 3B, subsystem 310 illustrates an exemplary system for deionizing water before delivering it to the AEM electrolyzer stack 102. The chlor-alkali stack 112 is fluidly coupled to the AEM electrolyzer stack 102 and to the ion exchange system 114. The dechlorinated water produced from the chlor-alkali stack 112 is split into two streams, each of which is controlled by a flow control valve 122a, 122b. The desalination system 124 is also fluidly coupled to the AEM electrolyzer stack 102. The flow rate of the desalination water provided by the desalination system 124 is controlled by a flow control valve 122c. The flow control valve 122a controls the flow rate of the desalination water provided to the AEM electrolyzer stack 102. The flow control valve 122b controls the flow rate of the desalination water provided to the ion exchange system 114. The flow control valve 122c controls the flow rate of the desalination water provided to the AEM electrolyzer stack 102. The AEM electrolyzer stack 102 is also fluidly coupled to a phase separator 116, which is operable to remove excess water from the hydrogen gas produced by the AEM electrolyzer stack 102. The phase separator 116 recycles the excess water back to the AEM electrolyzer stack 102 for electrolysis. Alternatively, the water may be purged from the system 300. A conductivity meter 118 determines the conductivity of the water exiting the phase separator 116. Flow control valves 122a, 122b, 122c allow the flow rate of dechlorinated and deionized water delivered to the AEM electrolyzer stack 102 to be adjusted to increase or decrease the conductivity of the water supplied to the AEM electrolyzer stack 102 in order to optimize performance of the AEM electrolyzer stack 102.

[0077] FIG. 4A illustrates an exemplary system 400 of the present disclosure. The system 300 includes a water source 120 fluidly connected to a desalination system 124 to supply salt water to the desalination system 124. The desalination system 124 is fluidly connected to the AEM electrolyzer stack 102 to supply desalination water to the AEM electrolyzer stack 102. The desalination water may be deionized in a deionization layer 114 (see FIG. 4B) of a subsystem 410 as described herein to remove salt and other impurities in the salt water. The oxygen produced by the AEM electrolyzer stack 102 may be vented to the atmosphere or the oxygen may be collected. The AEM electrolyzer stack 102 is fluidly connected to an ammonia reactor 104. The hydrogen gas produced by the AEM electrolyzer stack 102 may be delivered to the ammonia reactor 104 or may be stored or supplied for another use. The ammonia reactor 104 is fluidly connected to a nitrogen source 108. A nitrogen source 108 supplies nitrogen gas to the ammonia reactor 104. The ammonia reactor 104 produces a mixture of ammonia, hydrogen, and nitrogen. Unreacted hydrogen is separated from the ammonia and nitrogen via a hydrogen pump 106 fluidly connected to the ammonia reactor. The hydrogen is recycled to the inlet portion of the ammonia reactor 104 for reuse. Alternatively, the hydrogen may be stored or supplied for another use. The nitrogen and ammonia are collected for processing and use.

[0078] In FIG. 4B, subsystem 410 illustrates an exemplary system for deionizing water before delivering it to the AEM electrolyzer stack 102. The desalination system 124 is fluidly coupled to the AEM electrolyzer stack 102 and to the ion exchange system 114. The desalination system 124 produces desalination water that is split into two streams, each of which is controlled by a flow control valve 122a, 122b. The flow control valve 122a controls the flow rate of the desalination water that is fed to the AEM electrolyzer stack 102. The flow control valve 122b controls the flow rate of the desalination water that is fed to the ion exchange system 114. The AEM electrolyzer stack 102 is also fluidly coupled to a phase separator 116, which is operable to remove excess water from the hydrogen gas produced by the AEM electrolyzer stack 102. The phase separator 116 recycles the excess water back to the AEM electrolyzer stack 102 for electrolysis. Alternatively, water may be purged from the system 400. A conductivity meter 118 determines the conductivity of the water exiting the phase separator 116. Flow control valves 122a, 122b allow the flow rate of demineralized and deionized water delivered to the AEM electrolyzer stack 102 to be adjusted to increase or decrease the conductivity of the water supplied to the AEM electrolyzer stack 102 in order to optimize performance of the AEM electrolyzer stack 102.

[0079] II. Method Further provided herein is a method for producing hydrogen and ammonia. The method can be carried out using any of the systems described in Section I above.

[0080] The method includes producing hydrogen in an AEM electrolyzer stack. The production can be achieved via electrolysis of water, for example, salt water, fresh water, brackish water, desalinated water, dechlorinated water, purified water, and combinations thereof. Water is pumped from a water source to the AEM electrolyzer stack.

[0081] The method may further include purifying and / or pressurizing the hydrogen produced by the AEM electrolyzer stack. This may be accomplished via an electrochemical hydrogen pump fluidly connected to the AEM electrolyzer stack. The pressurized and / or purified hydrogen may be stored for later use or supplied for further use. Alternatively or additionally, the hydrogen may be purified via separation in a phase separator or by drying the hydrogen gas.

[0082] The method further includes producing ammonia in an ammonia reactor. The production can be accomplished by any of the ammonia reactors described herein. Preferably, the production is accomplished by an electrochemical ammonia reactor. Nitrogen is supplied to the ammonia reactor from a nitrogen source fluidly connected to the ammonia reactor. Hydrogen may be supplied to the ammonia reactor directly from an AEM electrolyzer stack fluidly connected to the ammonia reactor, or from a hydrogen storage system fluidly connected to the ammonia reactor. In addition, unreacted hydrogen and / or nitrogen may be recycled to the ammonia reactor to improve process efficiency. In some additional embodiments, the ammonia may be purified via separation in a phase separator, such as a condenser.

[0083] The method may further include providing the water to an AEM electrolyzer stack after purifying the water. In some embodiments, purification may be achieved via electrolysis in a chlor-alkali stack, via desalination in a desalination system, via deionization in an ion exchange system, or a combination thereof.

[0084] Electrolysis in the chlor-alkali stack results in the formation of chlorine gas and hydrogen gas. The chlorine gas may be collected and stored. The hydrogen gas may be collected and stored. If desired, the hydrogen gas may be pressurized and / or purified via an electrochemical hydrogen pump as described herein. The dechlorinated water produced by the chlor-alkali stack may be fed directly to the AEM electrolyzer stack for use or may be further purified.

[0085] The result of desalination is the formation of desalinated water. The salt impurities removed by the desalination system may be disposed of as waste. The desalted water produced by the desalination system may be fed directly to the AEM electrolyzer stack for use or may be further purified.

[0086] The deionization of water in the ion exchange system results in the formation of deionized water. The ionic impurities removed by the ion exchange system may be disposed of as waste when the ion exchange system is regenerated. The deionized water produced by the ion exchange system may be provided directly to the AEM electrolyzer stack for use or may be further purified.

[0087] Although many system components are described herein as single units, those skilled in the art will recognize that multiples of each system component described herein may be present in a system to improve processes and efficiencies, to scale efficiently, and / or to provide redundancy.

[0088] Exemplary embodiments Embodiment 1: 1. A system for producing hydrogen and ammonia, comprising: 1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive water from a water source; and Anion Exchange Membrane an electrochemical stack comprising: 1. A reactor for producing ammonia, comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen A reactor comprising: A system comprising:

[0089] Embodiment 2: 2. The system of embodiment 1, wherein the energy source comprises a synthesis cell having a cathode, an anode, and a proton exchange membrane disposed between the cathode and the anode.

[0090] Embodiment 3: 3. The system of embodiment 1 or 2, wherein the proton exchange membrane comprises a perfluorosulfonic acid polymer or copolymer, a sulfonated poly(ether ether ketone) (sPEEK), a sulfonated phenylated poly(phenylene) (sPPP), a sulfonated polyether(sulfone) (SPES), a sulfonated polystyrene-b-poly(ethylene-r-butylene-b-polystyrene (S-SEBS), or a combination thereof.

[0091] Embodiment 4: 4. The system of any one of the preceding claims, wherein the electrochemical stack further comprises a cathode and an anode, and the anion exchange membrane is disposed between the cathode and the anode.

[0092] Embodiment 5: 5. The system of any one of the preceding embodiments, wherein the anion exchange membrane comprises an imidazolium-functionalized styrene polymer, a polysulfone and its derivatives, a polymer having quaternary phosphonium groups, or a combination thereof.

[0093] Embodiment 6: 6. The system of any one of the preceding claims, wherein the water source comprises salt water.

[0094] Embodiment 7: 7. The system of embodiment 6, wherein the saltwater comprises sodium and chloride salts.

[0095] Embodiment 8: 8. The system of any one of the preceding claims, wherein the electrochemical stack further comprises a first outlet operable to deliver hydrogen from the electrochemical stack, and a second outlet operable to deliver a secondary gas comprising oxygen from the electrochemical stack.

[0096] Embodiment 9: 9. The system of any one of the preceding embodiments, further comprising a desalination system fluidly connected to the electrochemical stack for supplying desalted water to the electrochemical stack.

[0097] Embodiment 10: 10. The system of any one of the preceding embodiments, further comprising an ion exchange system fluidly connected to the water source and to the electrochemical stack.

[0098] Embodiment 11: 11. The system of any one of the preceding claims, further comprising a chlor-alkali stack fluidly connected to the water source and to the electrochemical stack.

[0099] Embodiment 12: 12. The system of embodiment 11, wherein the chlor-alkali stack comprises an anode, a cathode, and a proton exchange membrane.

[0100] Embodiment 13: 13. The system of any one of the preceding embodiments, further comprising a hydrogen storage system fluidly connected to the electrochemical stack.

[0101] Embodiment 14: 14. The system of any one of the preceding embodiments, further comprising an electrochemical hydrogen pump fluidly connected to the outlet of the ammonia reactor for removing unreacted hydrogen gas.

[0102] Embodiment 15: 14. The system of embodiment 13, wherein the electrochemical hydrogen pump comprises an anode, a cathode, and a proton exchange membrane.

[0103] Embodiment 16: 16. The system of any one of the preceding embodiments, further comprising a phase separator fluidly connected to an outlet of the electrochemical stack for removing water from the produced hydrogen.

[0104] Embodiment 17: 17. The system of embodiment 16, wherein the phase separator is fluidly connected to the inlet of the ammonia reactor.

[0105] Embodiment 18: 1. A system for producing hydrogen and ammonia, comprising: a desalination system operable to remove salt from the salt water, thereby producing desalinated water; 1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive the desalinated water from the desalination module; and Anion Exchange Membrane an electrochemical stack comprising: 1. A reactor for producing ammonia, comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen A reactor comprising: A system comprising:

[0106] Embodiment 19: 1. A system for producing hydrogen and ammonia, comprising: a chlor-alkali stack operable to remove chlorine from the saltwater, thereby producing dechlorinated water; 1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive the dechlorinated water from the chlor-alkali stack; and Anion Exchange Membrane an electrochemical stack comprising: 1. A reactor for producing ammonia, comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen A reactor comprising: A system comprising:

[0107] Embodiment 20: 20. The system of embodiment 19, further comprising an ion exchange system in fluid communication with the chlor-alkali stack and the electrochemical stack, the ion exchange system receiving a quantity of the dechlorinated water produced by the chlor-alkali stack and producing deionized water.

[0108] Embodiment 21: 21. The system of embodiment 20, wherein the deionized water is combined with the amount of the dechlorinated water not received by the ion exchange system prior to entering the electrochemical stack.

[0109] Embodiment 22: 22. The system of embodiment 20 or 21, further comprising a valve operable to regulate the amount of sodium hydroxide solution delivered to the ion exchange system.

[0110] Embodiment 23: 1. A system for producing hydrogen, comprising: 1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive water from a water supply; anion exchange membrane; and an outlet fluidly connected to a reactor for producing ammonia wherein the first electrochemical stack electrolyzes the water to produce hydrogen.

[0111] Embodiment 24: 1. A method for producing hydrogen and ammonia, comprising: an inlet operable to receive water from a water source; and Anion Exchange Membrane generating hydrogen in an electrochemical stack comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen Producing ammonia in a reactor comprising: A method comprising:

[0112] Embodiment 25: 25. The method of embodiment 24, wherein the water comprises salt water.

[0113] Embodiment 26: 26. The method of embodiment 24 or 25, wherein the water comprises dechlorinated water.

[0114] Embodiment 27: 27. The method of embodiment 26, further comprising dechlorinating saltwater in a chlor-alkali stack and delivering the dechlorinated water to the inlet of the electrochemical stack.

[0115] Embodiment 28: 28. The method of any one of embodiments 24-27, wherein the water comprises demineralized water.

[0116] Embodiment 29: 29. The method of embodiment 28, further comprising desalting the water and delivering the desalted water to the inlet of the electrochemical stack.

[0117] Embodiment 30: 30. The method of embodiment 28 or 29, further comprising transferring heat generated by the electrochemical stack to a desalination system via a heat exchange fluid.

[0118] Embodiment 31: 31. The method of any one of embodiments 24-30, wherein the water comprises deionized water.

[0119] Embodiment 32: 32. The method of embodiment 31, further comprising deionizing the water in an ion exchange system and delivering the deionized water to the inlet of the electrochemical stack.

[0120] Embodiment 33: 33. The method of any one of embodiments 24-32, further comprising storing hydrogen produced by the electrochemical stack.

[0121] As used herein, "wet hydrogen" refers to hydrogen that is saturated with water. One of ordinary skill in the art will recognize that the amount and / or concentration of water in the wet hydrogen depends on the temperature and pressure of the wet hydrogen.

[0122] As used herein, "dry hydrogen" refers to hydrogen having a water content of about 10 ppm or less. For example, dry hydrogen may have a water content of about 10 ppm, about 9 ppm, about 8 ppm, about 7 ppm, about 6 ppm, about 5 ppm, about 4 ppm, about 3 ppm, about 2 ppm, about 1 ppm, or less than about 1 ppm. Preferably, dry hydrogen has a water content of about 5 ppm or less.

[0123] All documents mentioned herein are incorporated herein by reference in their entirety. Reference to a singular item should be understood to include the plural item, and vice versa, unless expressly stated or evident from the text to the contrary. Grammatical conjunctions are intended to represent any and all disjunctive and conjunctive combinations of joined clauses, sentences, words, etc., unless stated or evident from the context to the contrary. Thus, the term "or" should generally be understood to mean "and / or," and the term "and" should generally be understood to mean "and / or."

[0124] The recitation of ranges of values ​​herein is not intended to be limiting, unless otherwise indicated herein, but instead refers individually to any and all values ​​falling within the range, and each separate value within such range is incorporated herein as if it were individually recited herein. The words "about", "approximately", and the like, when accompanying numerical values, should be construed to include any deviation as would be recognized by a person skilled in the art to operate satisfactorily for the intended purpose. Values ​​and / or numerical ranges are provided herein only as examples and do not constitute limitations on the scope of the described embodiments. The use of any and all examples, or illustrative words (such as "for example", "etc.", etc.) are merely intended to better clarify the embodiments, and do not constrain the scope of those embodiments. No language in this specification should be construed as indicating that any non-claimed element is essential to the practice of the disclosed embodiments.

[0125] The above-mentioned systems, devices, methods, processes, etc. may be implemented in hardware, software, or any combination thereof suitable for control, data acquisition, and data processing as described herein. This includes implementation in one or more microprocessors, microcontrollers, embedded microcontrollers, programmable digital signal processors, or other programmable devices or processing circuits, together with internal and / or external memory. This may also, or instead, include one or more application specific integrated circuits, programmable gate arrays, programmable array logic components, or any other device(s) that may be configured to process electronic signals. It is further recognized that implementation of the above-mentioned processes or devices may include computer executable code created using structured programming languages ​​such as C, object-oriented programming languages ​​such as C++, or any other high-level or low-level programming languages ​​(including assembly languages, hardware description languages, and database programming languages ​​and techniques), which may be stored, compiled, or interpreted and executed on one of the above-mentioned devices, as well as heterogeneous combinations of processors, processor architectures, or combinations of different hardware and software. At the same time, processing may be distributed across devices such as the various systems described above, or all functions may be integrated into a dedicated standalone device. All such permutations and combinations are intended to fall within the scope of the present disclosure.

[0126] The embodiments disclosed herein may include a computer program product including computer executable or computer usable code that, when executed on one or more computer devices, performs any and / or all steps of the control system described above. The code may be stored in a non-transitory manner in computer memory, which may be the memory (e.g., random access memory associated with a processor) where the program is executed, or in a storage device, such as a disk drive, flash memory, or any other optical, electromagnetic, magnetic, infrared or other device, or combination of devices. In another aspect, any of the control systems described above may be embodied in any suitable transmission or propagation medium that conveys the computer executable code and / or any input or output therefrom.

[0127] The method steps of implementation described herein are intended to include any suitable manner of having such method steps implemented, consistent with the patentability of the following claims, unless a different meaning is clearly provided or otherwise clear from the context. Thus, for example, implementing step X includes any suitable manner of having another party, such as a remote user, a remote processing resource (e.g., a server or cloud computer), or a machine, implement step X. Similarly, implementing steps X, Y, and Z may include any manner of directing or controlling any combination of such other individuals or resources to implement steps X, Y, and Z and obtain the benefit of such steps. Thus, the method steps of implementation described herein are intended to include any suitable manner of having one or more other parties or entities implement steps, consistent with the patentability of the following claims, unless a different meaning is clearly provided or otherwise clear from the context. Such parties or entities need not be under the direction or control of any other parties or entities, nor need they be located within any particular jurisdiction.

[0128] It is recognized that the above described method and system are shown by way of example and not by way of limitation. Numerous variations, additions, omissions and other modifications will be apparent to those skilled in the art. In addition, the order or presentation of the method steps in the above description and drawings is not intended to require this order of performance of the listed steps, unless a particular order is expressly required or otherwise evident from the context. Thus, although specific embodiments have been shown and described, those skilled in the art will recognize that various changes and modifications in form and details may be made therein without departing from the scope of the present disclosure. (Item 1) 1. A system for producing hydrogen and ammonia, comprising: 1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive water from a water source; and Anion Exchange Membrane an electrochemical stack comprising: 1. A reactor for producing ammonia, comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen A reactor comprising: A system comprising: (Item 2) 2. The system of claim 1, wherein the energy source comprises a synthesis cell having a cathode, an anode, and a proton exchange membrane disposed between the cathode and the anode. (Item 3) 3. The system of claim 2, wherein the proton exchange membrane comprises a perfluorosulfonic acid polymer or copolymer, a sulfonated poly(ether ether ketone) (sPEEK), a sulfonated phenylated poly(phenylene) (sPPP), a sulfonated polyether(sulfone) (SPES), a sulfonated polystyrene-b-poly(ethylene-r-butylene-b-polystyrene (S-SEBS), or a combination thereof. (Item 4) Item 1, the electrochemical stack further comprising a cathode and an anode, the anion exchange membrane being disposed between the cathode and the anode. (Item 5) Item 1, wherein the anion exchange membrane comprises an imidazolium-functionalized styrene polymer, a polysulfone and its derivatives, a polymer having quaternary phosphonium groups, or a combination thereof. (Item 6) Item 1 . The system of item 1 , wherein the water source comprises salt water. (Item 7) 7. The system of claim 6, wherein the saltwater comprises sodium and chloride salts. (Item 8) 2. The system of claim 1, wherein the electrochemical stack further comprises a first outlet operable to deliver hydrogen from the electrochemical stack and a second outlet operable to deliver a secondary gas comprising oxygen from the electrochemical stack. (Item 9) 2. The system of claim 1, further comprising a desalination system fluidly connected to the electrochemical stack to supply desalted water to the electrochemical stack. (Item 10) 2. The system of claim 1, further comprising an ion exchange system fluidly connected to the water source and to the electrochemical stack. (Item 11) 2. The system of claim 1, further comprising a chlor-alkali stack fluidly connected to the water source and to the electrochemical stack. (Item 12) Item 12. The system of item 11, wherein the chlor-alkali stack comprises an anode, a cathode and a proton exchange membrane. (Item 13) Item 10. The system of item 1, further comprising a hydrogen storage system fluidly connected to the electrochemical stack. (Item 14) 2. The system of claim 1, further comprising an electrochemical hydrogen pump fluidly connected to an outlet of the ammonia reactor for removing unreacted hydrogen gas. (Item 15) Item 15. The system of item 14, wherein the electrochemical hydrogen pump comprises an anode, a cathode and a proton exchange membrane. (Item 16) 2. The system of claim 1, further comprising a phase separator fluidly connected to an outlet of the electrochemical stack for removing water from the produced hydrogen. (Item 17) 17. The system of claim 16, wherein the phase separator is fluidly connected to the inlet of the ammonia reactor. (Item 18) 1. A system for producing hydrogen and ammonia, comprising: a desalination system operable to remove salt from the salt water, thereby producing desalinated water; 1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive the desalinated water from the desalination module; and Anion Exchange Membrane an electrochemical stack comprising: 1. A reactor for producing ammonia, comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen A reactor comprising: A system comprising: (Item 19) 1. A system for producing hydrogen and ammonia, comprising: a chlor-alkali stack operable to remove chlorine from the saltwater, thereby producing dechlorinated water; 1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive the dechlorinated water from the chlor-alkali stack; and Anion Exchange Membrane an electrochemical stack comprising: 1. A reactor for producing ammonia, comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen A reactor comprising: A system comprising: (Item 20) 20. The system of claim 19, further comprising an ion exchange system in fluid communication with the chlor-alkali stack and the electrochemical stack, the ion exchange system receiving a quantity of the dechlorinated water produced by the chlor-alkali stack and producing deionized water. (Item 21) 21. The system of claim 20, wherein the deionized water is combined with the amount of the dechlorinated water not received by the ion exchange system prior to entering the electrochemical stack. (Item 22) 21. The system of claim 20, further comprising a valve operable to regulate the amount of sodium hydroxide solution delivered to the ion exchange system. (Item 23) 1. A system for producing hydrogen, comprising: 1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive water from a water supply; anion exchange membrane; and an outlet fluidly connected to a reactor for producing ammonia wherein the first electrochemical stack electrolyzes the water to produce hydrogen. (Item 24) 1. A method for producing hydrogen and ammonia, comprising: an inlet operable to receive water from a water source; and Anion Exchange Membrane generating hydrogen in an electrochemical stack comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen Producing ammonia in a reactor comprising: A method comprising: (Item 25) 25. The method of claim 24, wherein the water comprises salt water. (Item 26) 25. The method of claim 24, wherein the water comprises dechlorinated water. (Item 27) 27. The method of claim 26, further comprising the steps of dechlorinating salt water in a chlor-alkali stack and delivering the dechlorinated water to the inlet of the electrochemical stack. (Item 28) 25. The method of claim 24, wherein the water comprises demineralized water. (Item 29) 30. The method of claim 28, further comprising the steps of desalting the water and delivering the desalted water to the inlet of the electrochemical stack. (Item 30) 30. The method of claim 28, further comprising transferring heat generated by the electrochemical stack to a desalination system via a heat exchange fluid. (Item 31) 25. The method of claim 24, wherein the water comprises deionized water. (Item 32) 32. The method of claim 31, further comprising the steps of deionizing the water in an ion exchange system and delivering the deionized water to the inlet of the electrochemical stack. (Item 33) 25. The method of claim 24, further comprising storing hydrogen produced by the electrochemical stack.

Claims

1. 1. A system for producing hydrogen and ammonia, comprising:

1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive water from a water source; and Anion Exchange Membrane an electrochemical stack comprising: an ion exchanger fluidly connected to the water source and to the electrochemical stack for purifying the water; 1. A reactor for producing ammonia, comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen A reactor comprising: A system comprising:

2. 10. The system of claim 1, wherein the energy source comprises a synthesis cell having a cathode, an anode, and a proton exchange membrane disposed between the cathode and the anode.

3. 3. The system of claim 2, wherein the proton exchange membrane comprises a perfluorosulfonic acid polymer or copolymer, sulfonated poly(ether ether ketone) (sPEEK), sulfonated phenylated poly(phenylene) (sPPP), sulfonated polyether(sulfone) (SPES), sulfonated polystyrene-b-poly(ethylene-r-butylene-b-polystyrene (S-SEBS), or a combination thereof.

4. The system of claim 1 , wherein the electrochemical stack further comprises a cathode and an anode, the anion exchange membrane being disposed between the cathode and the anode.

5. 10. The system of claim 1, wherein the anion exchange membrane comprises an imidazolium-functionalized styrene polymer, a polysulfone and its derivatives, a polymer having quaternary phosphonium groups, or a combination thereof.

6. The system of claim 1 , wherein the water source comprises salt water.

7. The system of claim 6 , wherein the saltwater comprises sodium and chloride salts.

8. 10. The system of claim 1, wherein the electrochemical stack further comprises a first outlet operable to deliver hydrogen from the electrochemical stack and a second outlet operable to deliver a secondary gas comprising oxygen from the electrochemical stack.

9. The system of claim 1 , further comprising a desalination system fluidly connected to the electrochemical stack to supply desalted water to the electrochemical stack.

10. 10. The system of claim 1, further comprising a chlor-alkali stack fluidly connected to the water source and to the electrochemical stack.

11. 11. The system of claim 10, wherein the chlor-alkali stack comprises an anode, a cathode, and a proton exchange membrane.

12. The system of claim 1 further comprising a hydrogen storage system fluidly connected to the electrochemical stack.

13. 10. The system of claim 1, further comprising an electrochemical hydrogen pump fluidly connected to an outlet of the ammonia reactor for removing unreacted hydrogen gas.

14. The system of claim 13 , wherein the electrochemical hydrogen pump comprises an anode, a cathode, and a proton exchange membrane.

15. 10. The system of claim 1, further comprising a phase separator fluidly connected to an outlet of the electrochemical stack for removing water from the produced hydrogen.

16. 16. The system of claim 15, wherein the phase separator is fluidly connected to the inlet of the ammonia reactor.

17. 1. A system for producing hydrogen and ammonia, comprising: a desalination system operable to remove salt from the salt water, thereby producing desalinated water; 1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive the desalinated water from the desalination module; and Anion Exchange Membrane an electrochemical stack comprising:

1. A reactor for producing ammonia, comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen A reactor comprising: A system comprising:

18. 1. A system for producing hydrogen and ammonia, comprising: a chlor-alkali stack operable to remove chlorine from the saltwater, thereby producing dechlorinated water; 1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive the dechlorinated water from the chlor-alkali stack; and Anion Exchange Membrane an electrochemical stack comprising:

1. A reactor for producing ammonia, comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen A reactor comprising: A system comprising:

19. 20. The system of claim 18, further comprising an ion exchange system in fluid communication with the chlor-alkali stack and the electrochemical stack, the ion exchange system receiving a quantity of the dechlorinated water produced by the chlor-alkali stack and producing deionized water.

20. 20. The system of claim 19, wherein the deionized water is combined with the amount of the dechlorinated water not received by the ion exchange system prior to entering the electrochemical stack.

21. 20. The system of claim 19, further comprising a valve operable to regulate the amount of sodium hydroxide solution delivered to the ion exchange system.

22. 1. A system for producing hydrogen, comprising:

1. An electrochemical stack for producing hydrogen, comprising: an inlet operable to receive water from a water supply; an anion exchange membrane; and an outlet fluidly connected to a reactor for producing ammonia wherein the first electrochemical stack electrolyzes the water to produce hydrogen.

23. 1. A method for producing hydrogen and ammonia, comprising: an inlet operable to receive water from a water source; and Anion Exchange Membrane generating hydrogen in an electrochemical stack comprising: an inlet operable to receive nitrogen and hydrogen produced in the electrochemical stack; and An energy source activatable to reduce nitrogen to ammonia in the presence of hydrogen Producing ammonia in a reactor comprising: A method comprising:

24. 24. The method of claim 23, wherein the water comprises salt water.

25. 24. The method of claim 23, wherein the water comprises dechlorinated water.

26. 26. The method of claim 25, further comprising dechlorinating saltwater in a chlor-alkali stack and delivering the dechlorinated water to the inlet of the electrochemical stack.

27. 24. The method of claim 23, wherein the water comprises demineralized water.

28. 30. The method of claim 27, further comprising the steps of desalting the water and delivering the desalted water to the inlet of the electrochemical stack.

29. 30. The method of claim 27, further comprising transferring heat generated by the electrochemical stack to a desalination system via a heat exchange fluid.

30. 24. The method of claim 23, wherein the water comprises deionized water.

31. 31. The method of claim 30, further comprising the steps of deionizing the water in an ion exchange system and delivering the deionized water to the inlet of the electrochemical stack.

32. 24. The method of claim 23, further comprising storing hydrogen produced by the electrochemical stack.

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