Production of renewable nitrogen products

Abstract

Provided herein are systems and methods for producing renewable nitrogen products.

Description

[Background technology]

[0001] Nitrogen chemical products have many potential uses, but the primary use is in agricultural fertilizers (approximately 88% of total NH3 production in 2018). Nitrogen fertilizers are typically produced from ammonia (NH3) by the Haber-Bosch process. In this energy-intensive process, natural gas (CH4) usually supplies hydrogen (H2), and nitrogen (N2) comes from air. The ammonia produced by the reaction of H2 and N2 is separated from the reaction elutes via mechanical cooling and condensation, which produces anhydrous liquid ammonia, typically stored at ambient pressure and low temperatures (e.g., -33°C) in suitably designed cryogenic tanks.

[0002] Anhydrous ammonia is used as a raw material in all downstream conversion processes, including the production of ammonium nitrate (NH4NO3) and other nitrogen fertilizers such as urea (CO(NH2)2).

[0003] A mixture of ammonium nitrate and urea is stable and is known as UAN. In UAN, the combined solubility of ammonium nitrate and urea is much higher than that of either component alone, approaching that of solid ammonium nitrate (33.5%), and the total nitrogen content (e.g., about 32%). Given the ongoing safety and reliability concerns surrounding fertilizer-grade solid ammonium nitrate, UAN offers a considerably safer alternative without completely sacrificing the agricultural properties that make ammonium nitrate an attractive fertilizer. It is also more convenient to store and handle than the solid product and is easier to apply precisely to the land by mechanical means. [Overview of the project] [Means for solving the problem]

[0004] According to some means, the production of ammonia and its derivatives accounts for approximately 3–5% of global greenhouse gas (GHG) emissions. Therefore, there is a critical need for the sustainable production of nitrogen compounds (i.e., GHG emissions are reduced or negligible). Such systems and methods are provided herein, which utilize renewable inputs such as water, air, CO2, and renewable electricity. In some cases, the systems and methods provided herein can be used to produce nitrogen products starting from H2 (regardless of how such H2 is produced), CO2, air, and water.

[0005] In some cases, H2 is supplied from a geological source (e.g., accessed through one or more wells drilled into the soil for the purpose of extracting hydrogen or as a byproduct of other geological extraction). In other cases, renewable electricity can be used to electrolyze water into H2 and O2, with H2 being the reactant in the production of NH3. H2 is reacted with N2 separated from the air to produce NH3 via an equilibrium reaction. Such NH3 can be separated from unreacted H2 and N2 by absorption in water to form an aqueous ammonia solution. This solution may be sold as a product (e.g., 20% aqueous ammonia) or supplied to a downstream ammonia conversion process. Alternatively, water may be distilled from such a solution to produce commercially available anhydrous ammonia (>99.5 wt% NH3) or aqueous ammonia solutions with higher NH3 concentrations, which may be sold as high-concentration nitrogen products or supplied to downstream processes for further conversion of NH3 into other nitrogen products such as nitric acid, ammonium nitrate, other nitrates, urea, UAN, or any combination of such products. The heat required for the distillation of the aqueous ammonia solution may come from ammonia synthesis, downstream ammonia conversion processes (e.g., exothermic oxidation of NH3 to nitrates), any external energy source (including renewable electricity), or any combination of all the aforementioned sources.

[0006] Using O2 from electrolysis, NH3 can be oxidized to nitric acid and other nitrogen compounds such as ammonium nitrate.

[0007] Urea can be produced by the reaction of NH3 and CO2 in a series of two equilibrium reactions. The first equilibrium is a rapid, exothermic conversion of (liquid) ammonia with CO2 at high temperature and pressure, forming a carbamate (H2N-COONH4). The second equilibrium is the slower endothermic decomposition of ammonium carbamate into urea and water. By using a large reaction vessel, the slow urea formation reaction time is allowed to reach equilibrium, and because the urea conversion is incomplete, the product can be separated from unresolved ammonium carbamate, product water, and unreacted NH3 and CO2.

[0008] UAN is typically produced by blending pure urea and ammonium nitrate with water. However, counterintuitively, the inventors of this disclosure have recognized that, since much of the water required for UAN may come from urea intermediates (urea solution, about 75-80% aqueous urea solution) and concentrated aqueous ammonium nitrate solution, which is a typical intermediate in the production of solid ammonium nitrate, producing pure urea and ammonium nitrate can be counterproductive if the desired target product is UAN. Therefore, a system and method for directly, efficiently, and synergistically producing UAN in a renewable process having air, water, CO2, and renewable power inputs are provided herein.

[0009] Overall, the systems and methods described herein can replace unsustainable, fossil fuel-based ammonia, urea, nitrate, ammonium nitrate, and / or UAN production plants with renewable alternatives.

[0010] Therefore, in one embodiment, a method for producing ammonia is provided, and the method is a. Mixing (H2) with nitrogen (N2) to generate a mixed flow, and selectively processing the mixed flow in a deoxidation reactor to remove residual oxygen (O2), b. Dehydrating a combination of a mixed flow and a recycled flow to generate a dry flow, c. Reacting H2 and N2 contained in the dry flow in a synthesis reactor to form an elute flow containing ammonia (NH3), d. The process involves absorbing NH3 from the elute flow in water to generate an aqueous ammonia solution and a recycled flow, wherein the recycled flow contains unreacted H2 and N2 and is combined with the mixed flow. e. To control the accumulation of inert species in the system, separate the recycling flow fraction and generate a purge flow, f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Power supply for dehydration and / or distillation using the heat generated by the ammonia synthesis reactor.

[0011] In certain embodiments of the embodiments described above, hydrogen (H2) is supplied from a geological source. In some other different embodiments, hydrogen (H2) is supplied from an electrolytic cell powered using renewable energy, for example, by electrolyzing water to produce hydrogen and oxygen. In some further embodiments, the electrolytic cell further produces oxygen (O2), and the method further includes mixing H2 with N2 and treating such mixed flow in a deoxidation reactor to remove the remaining O2.

[0012] In any of the embodiments described above, the rate of ammonia production increases or decreases depending on the price or availability of renewable electricity.

[0013] In different exemplary embodiments, N2 is produced by cryogenic air liquefaction and distillation; in different embodiments, N2 is produced by pressure swing adsorption (PSA); or in other embodiments, N2 is produced by a selectively permeable membrane.

[0014] In any other embodiment of the embodiments described above, dehydration is carried out using thermal swing adsorption (TSA), or in a different embodiment, dehydration is carried out by contacting the wet gas mixture with a molecular sieve material, or in another different embodiment, dehydration is carried out by contacting the wet gas mixture with an aqueous solution of ammonia or liquid ammonia.

[0015] In yet another embodiment of any of the embodiments described above, NH3 is synthesized in the reactor at a pressure of less than about 80 bar, less than about 60 bar, about 40 bar, or less than about 40 bar. In a different embodiment, NH3 is synthesized in the presence of a catalyst, which is in direct contact with the pressure vessel, or NH3 is synthesized in the presence of a catalyst, which is contained inside a tube within the vessel.

[0016] In the further different embodiments described above, a portion of the NH3 contained in the elute stream is condensed and separated, the remainder is absorbed into water, and / or the NH3 in the elute stream is absorbed into water using a packing-filled column, and / or the NH3 in the elute stream is absorbed into water using a tray-equipped column.

[0017] In other different embodiments, the aqueous ammonia solution is distilled using a column packed with packing material, and / or the aqueous ammonia solution is distilled using a column equipped with a tray. In other related embodiments, the distillation of the aqueous ammonia solution is at least partially powered by an external heat source.

[0018] In the more different embodiments described above, the formation of NH3 generates heat, which is then captured in a hot oil, hot water, or vapor system.

[0019] In other embodiments, the H2 contained in the purge stream is separated, recycled to ammonia synthesis, and / or the H2 contained in the purge stream is separated, further compressed, and recycled to ammonia synthesis.

[0020] In still different embodiments of any of the foregoing methods, the method comprises a. separating the purge stream into a concentrated H2 stream and a tail gas stream comprising non-reactive species (e.g., N2, CH4 if present in the system, and noble gases Ar and He); b. recycling the purge stream to the ammonia synthesis; c. further comprising concentrating Ar and / or He from the tail gas stream to produce a product stream.

[0021] Another embodiment provides a method of making ammonia, the method comprising a. mixing H2 with N2 to produce a mixed stream; b. dehydrating the mixed stream and the recycle stream to produce a dry stream; c. reacting H2 and N2 contained in the dry stream in a synthesis reactor to form an eluate stream containing ammonia (NH3); d. absorbing NH3 from the eluate stream in water to produce an aqueous ammonia solution and a recycle stream containing unreacted H2 and N2; e. separating a fraction of the recycle stream to produce a purge stream to control the accumulation of any inert species in the system; f. distilling the aqueous ammonia solution to produce a more concentrated ammonia product; g. using heat generated by the ammonia synthesis reactor to power the dehydration and / or distillation; h. separating the purge stream into a concentrated H2 stream and a tail gas stream comprising all non-reactive species (N2, CH4 if present in the system, and noble gases Ar and He); i. Recycling the purge flow for ammonia synthesis, The method further comprises enriching j.Ar and / or He from the tail gas flow to generate a product flow.

[0022] In certain embodiments of the above embodiments, H2 is separated from the purge flow via cryogenic distillation; in other embodiments, H2 is separated from the purge flow via pressure swing adsorption (PSA); or in different embodiments, H2 is separated from the purge flow by a selectively permeable membrane.

[0023] In some other different embodiments, Ar and / or He are separated from the tail gas stream via cryogenic distillation, or Ar and / or He are separated from the tail gas stream via pressure swing adsorption (PSA), and / or Ar or He are separated from the tail gas stream by a selectively permeable membrane, for example, in some embodiments the tail gas stream is recycled for ammonia synthesis after the removal of Ar and / or He.

[0024] In certain other embodiments, the method is a. Supplying a purge flow to a power generation unit, wherein the H2 in the flow reacts with O2 to generate an exhaust flow. b. The method further comprises enriching Ar and / or He from the exhaust flow to generate a product flow and a tail gas flow.

[0025] Another different embodiment provides a method for producing ammonia, the method is a. Mixing H2 with N2 to generate a mixed flow, b. Dehydrating a combination of a mixed flow and a recycled flow to generate a dry flow, c. In the synthesis reactor, H2 and N2 contained in the dry stream are reacted to form ammonia (NH3) contained in the elute stream, d. From the eluted stream, absorb NH3 in water to generate a recycled stream containing aqueous ammonia solution, and unreacted H2 and N2. e. To control the accumulation of any inert species within the system, separate the recycling flow fraction and generate a purge flow, f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor to power dehydration and / or distillation, h. The purge flow is supplied to the power generation unit, where H2 reacts with O2 to generate exhaust flow. i. Enriching Ar and / or He from the exhaust flow to generate a product flow and a tail gas flow, and including these.

[0026] In certain embodiments of the above embodiments, the power is generated in a fuel cell, or in an internal combustion engine, or in a gas turbine, or in a linear generator, or is utilized in a process.

[0027] In the other different embodiments described above, heat is recovered from the exhaust flow; for example, in some embodiments, the heat is captured in a hot oil, hot water, or steam system, while in other embodiments, the recovered heat is utilized within the process.

[0028] In other different embodiments of the method, water is separated from the exhaust stream before concentrating Ar and / or He.

[0029] In more embodiments, Ar and / or He are separated from the exhaust flow via cryogenic distillation, or Ar and / or He are separated from the exhaust flow via pressure swing adsorption (PSA), or Ar and / or He are separated from the exhaust flow by a selectively permeable membrane.

[0030] In other, more specific embodiments, the method is: a. Oxidizing any combination of aqueous ammonia solution and concentrated ammonia product to form a NOx-rich stream of nitrogen oxides (NOx), b. Further comprising absorbing NO2 from a NOx stream in water to produce an aqueous solution of nitric acid (HNO3) and a vapor stream.

[0031] Further embodiments relate to methods for producing ammonia, the method being: a. Mixing H2 with N2 to generate a mixed flow, b. Dehydrating a combination of a mixed flow and a recycled flow to generate a dry flow, c. H contained in the dry stream 2、 And N2 are reacted in a synthesis reactor to form an elute stream containing ammonia (NH3), d. Absorbing NH3 from the elute stream to generate an aqueous ammonia solution containing unreacted H2 and N2, and a recycled stream. e. To control the accumulation of any inert species within the system, separate the recycling flow fraction and generate a purge flow, f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor to power dehydration and / or distillation, h. Oxidizing any combination of aqueous ammonia solution and concentrated ammonia product to form a NOx-rich stream of nitrogen oxides (NOx), i. This includes absorbing NO2 from a NOx stream in water to produce an aqueous solution of nitric acid (HNO3) and a vapor stream.

[0032] In certain embodiments of these embodiments, the oxidation of NH3 generates heat, which is captured in a hot oil, hot water, or steam system, and in some embodiments, for example, the captured heat is utilized within the process.

[0033] In other different embodiments, NH3 is oxidized with oxygen in the presence of a catalyst, for example, in some embodiments the catalyst comprises a platinum group metal and optionally rhodium, and in other embodiments the catalyst comprises cobalt.

[0034] In other embodiments of the methods described above, the method further comprises cooling the NOx stream while enabling the continuous oxidation of nitrogen compounds to NO2, or the method further comprises using O2 derived from electrolysis to further oxidize nitrogen oxides such as nitrous oxide (N2O) and nitric oxide (NO) to nitrogen dioxide (NO2), or the method further comprises using O2 derived from electrolysis to ozonate a portion of the O2 and using a partially ozonated stream to further oxidize nitrogen oxides such as nitrous oxide (N2O) and nitric oxide (NO) to nitrogen dioxide (NO2), or the method further comprises using O2 derived from air separation to further oxidize nitrogen oxides such as nitrous oxide (N2O) and nitric oxide (NO) to nitrogen dioxide (NO2), or the method further comprises using O2 derived from air separation to ozonate a portion of the O2 and using a partially ozonated stream to further oxidize nitrogen oxides such as nitrous oxide (N2O) and nitric oxide (NO) to nitrogen dioxide (NO2).

[0035] In many further embodiments, an aqueous solution of HNO3 is neutralized in any combination of flows of a vapor aqueous ammonia solution and a concentrated ammonia product to form an aqueous solution of ammonium nitrate (NH4NO3). For example, in some embodiments, the neutralization of HNO3 generates heat, which is captured in a hot oil, hot water, or vapor system and can be utilized in the process. Alternatively, in different embodiments, the neutralization of HNO3 generates heat, which is used to evaporate the water contained in the aqueous solution of HNO3.

[0036] In some more different embodiments, the vapor stream is treated to separate N2 from other compounds, and in some embodiments, for example, the separated N2 is recycled for ammonia synthesis.

[0037] In other embodiments, the aqueous solution of ammonium nitrate is further concentrated or diluted by removing or adding water, or the aqueous solution of ammonium nitrate is granulated or otherwise converted into solid ammonium nitrate. For example, in some embodiments, a more concentrated or diluted aqueous solution of ammonium nitrate is granulated or otherwise converted into solid ammonium nitrate.

[0038] In any other embodiment of the aforementioned method, the method is a. Reacting any combination of aqueous ammonia products and concentrated ammonia products with CO2 to form a urea (CH4N2O)-rich eluate stream, b. Further comprising separating the aqueous urea solution from the eluent stream.

[0039] Other different embodiments provide a method for producing ammonia, the method is a. Mixing H2 with N2 to generate a mixed flow, b. Dehydrating a combination of a mixed flow and a recycled flow to generate a dry flow, c. Reacting H2 and N2 contained in the dry flow in a synthesis reactor to form an elute flow containing ammonia (NH3), d. From the elute flow, in water, NH3 is absorbed, and the aqueous ammonia solution and unreacted H 2、 and generating a recycled flow containing N2, e. To control the accumulation of any inert species within the system, separate the recycling flow fraction and generate a purge flow, f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reaction to power dehydration and / or distillation, h. Reacting any combination of aqueous ammonia solution and concentrated ammonia product with CO2 to form a urea (CH4N2O)-rich eluate stream, i. Separating an aqueous solution of urea from the eluent stream, and the above-mentioned method.

[0040] For example, in some embodiments, the CO2 may originate from flue gas, or from the fermentation of biomass or waste, or from the fermentation of biomass (e.g., corn) for the production of ethanol, or from an industrial facility (e.g., natural gas processing), or be supplied from a pipeline, or be supplied from direct air recovery (DAC).

[0041] In other different embodiments, the CO2 has a purity of less than 99% and more than 80%. In more embodiments, urea synthesis is carried out at a pressure greater than 150 bar, but in different embodiments, the molar ratio of NH3 to CO2 in the feed flow for urea synthesis is greater than about 2.

[0042] In further embodiments, an aqueous solution of urea is further concentrated in urea by removing water, and in some embodiments, for example, the concentrated urea solution is granulated or otherwise converted into solid urea.

[0043] In other different embodiments, an aqueous solution of urea is further diluted with urea by removing water to form diesel exhaust fluid (DEF).

[0044] Any other embodiment of the aforementioned method is a. Oxidizing an aqueous ammonia solution and a portion of the concentrated ammonia to form a NOx-rich stream of nitrogen oxides (NOx), b. From the NOx flow, NO2 is absorbed in water to generate an aqueous solution of nitric acid (HNO3) and a vapor flow. c. The remaining portion of the aqueous ammonia solution and the concentrated ammonia are reacted with CO2 to form a urea (CH4N2O)-rich stream, d. Separating the urea aqueous solution from the urea-rich flow, e. This includes combining an aqueous solution of urea with an aqueous solution of nitric acid (HNO3) to form an ammonium urea nitrate (UAN) solution.

[0045] Different embodiments relate to methods for producing ammonia, and the method is a. Mixing H2 with N2 to generate a mixed flow, b. Dehydrating a combination of a mixed flow and a recycled flow to generate a dry flow, c. H contained in the dry stream 2、 And N2 are reacted in a synthesis reactor to form an elute stream containing ammonia (NH3), d. From the elute flow, in water, NH3 is absorbed, and the aqueous ammonia solution and unreacted H 2、 and generating a recycled flow containing N2, e. To control the accumulation of any inert species within the system, separate the recycling flow fraction and generate a purge flow, f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor to power dehydration and / or distillation, h. Oxidizing a portion of an aqueous ammonia solution and concentrated ammonia to form a NOx-rich stream of nitrogen oxides (NOx), i. From the NOx flow, NO2 is absorbed in water to generate an aqueous solution of nitric acid (HNO3) and a vapor flow. j. The remaining portion of the flow, aqueous ammonia solution, and concentrated ammonia are reacted with CO2 to form a urea (CH4N2O)-rich eluate flow. k. Separating the urea aqueous solution from the urea-rich flow, l. This includes combining an aqueous solution of urea with an aqueous solution of nitric acid (HNO3) to form a urea-ammonium nitrate (UAN) solution.

[0046] Furthermore, a system configured to carry out any of the methods described above is also provided. Naturally, all combinations of the concepts described above, and any additional concepts discussed in more detail below (provided that such concepts are not contradictory), are intended to be part of the subject matter of the invention disclosed herein. In particular, all combinations of the subject matter in this disclosure are intended to be part of the subject matter of the invention disclosed herein.

[0047] Further embodiments, examples, and advantages of these exemplary embodiments and examples will be discussed in detail below. Furthermore, it should be understood that both the information stated herein and the detailed description below are merely illustrative of various embodiments and examples and are intended to provide an overview or framework for understanding the nature and features of the claimed embodiments and examples. Any embodiment disclosed herein may be combined with any other embodiment in any manner that is consistent with at least one of the purposes, objectives, and needs disclosed herein. When referring to “examples,” “several examples,” “alternative examples,” “various examples,” “one example,” “at least one example,” “this embodiment and other embodiments,” or similar terms, they are not necessarily mutually exclusive, and a particular feature, structure, or characteristic described in relation to an embodiment may be included in at least one embodiment. The appearance of such terms herein does not necessarily refer to all the same embodiment. [Brief explanation of the drawing]

[0048] [Figure 1] Figure 1 shows an example of a system and method described herein for the production of renewable ammonia. [Figure 2]Figure 2 shows another example of the system and method described herein for the production of renewable ammonia, with the co-production of noble gases. [Figure 3] Figure 3 shows another example of the systems and methods described herein for the production of renewable ammonia, with the co-generation of electricity and heat. [Figure 4] Figure 4 shows examples of the systems and methods described herein for the production of renewable nitric acid and / or ammonium nitrate solutions. [Figure 5] Figure 5 shows an example of a system and method described herein for the production of urea. [Figure 6] Figure 6 shows an example of the system and method described herein for generating a UAN. [Figure 7] Figure 7 shows an example of a system and method described herein for the production of UAN using exogenously generated urea. [Figure 8] Figure 8 shows an example of the system and method described herein for the production of UAN using exogenously generated ammonium nitrate. [Figure 9] Figure 9 shows an example of the system and method described herein for the production of UAN using exogenously generated nitric acid. [Figure 10] Figure 10 shows an example of a system and method described herein for the production of UAN using exogenously generated nitrate and urea. [Modes for carrying out the invention]

[0049] The production of synthetic ammonia and its derivatives has been a key driving force behind the global development of intensive agriculture. Without synthetic nitrogen fertilizers, it is estimated that the world would need three to four times more arable land to maintain current food production requirements.

[0050] The commercial production of synthetic ammonia was made possible by the discovery of iron-based catalysts that allow hydrogen to react with nitrogen under industrially viable conditions, typically at pressures of several hundred atmospheres and temperatures exceeding 400°C. In this conventional process, hydrogen is supplied via the steam reforming of hydrocarbons, with natural gas being the most common hydrocarbon used. Nitrogen is introduced into the process in the form of air, and oxygen is burned with the hydrocarbon fraction to produce a portion of the heat required by steam reforming.

[0051] The basic processes described above have not changed in any significant way since the first commercial production of synthetic ammonia several decades ago. Over the years, technological development has progressed in two main directions: (a) continuous optimization to achieve progressively improved utilization of energy contained in hydrocarbon feedstocks through more advanced thermal and mass integration, and (b) continuous scale-up efforts to increase the maximum single-train size to a capacity exceeding 3,500 metric tons per day (MTD) on a global scale today.

[0052] The commercial manufacturing processes resulting from these two development strategies cannot be readily adapted and deployed for the production of renewable ammonia, particularly when the hydrogen supply is generated via water electrolysis powered by renewable energy. In fact, ammonia production from renewable energy does not involve a hydrocarbon supply and is typically highly dispersed in nature.

[0053] In contrast, the process described herein generates hydrogen (H2) (e.g., from a geological source or using electrolysis), concentrates nitrogen (N2) to a concentration of at least about 95%, deoxygenates and combines the H2 and N2 to generate a feedstock flow, and synthesizes NH3 from the feedstock flow in a synthesis reactor at a pressure of less than about 80 bar.

[0054] In one embodiment, a method for producing nitrogen products is provided herein. The method may include providing hydrogen (H2). Hydrogen can be obtained from a geological source or by electrolyzing water (H2O) to produce hydrogen (H2) and oxygen (O2). The process involves reacting H2 with nitrogen (N2) to form ammonia (NH3), using O2 from electrolysis (in addition to O2 from air), and oxidizing NH3 to produce nitrate (NO3). - The method may include forming nitrates. The nitrates may be in the form of ammonium nitrate (NH4NO3) and / or nitric acid (HNO3). In some embodiments, the method involves reacting carbon dioxide (CO2) with ammonia (NH3) to form urea, and then converting such urea into nitrates (NO3). - The further step involves mixing with ) to form a UAN solution.

[0055] In another embodiment, a system for producing nitrogen products is provided herein. The system comprises an electrolytic cell configured to electrolyze water (H2O) to produce hydrogen (H2) and oxygen (O2), a reactor configured to react H2 with nitrogen (N2) to form ammonia (NH3), and a system for oxidizing NH3 to nitrate (NO3) using O2 from air, and optionally O2 from electrolysis. - It may comprise an oxidizer configured to form a ) and

[0056] Referring to Figure 1, the system described herein for nitrogen products may include an air separation unit 101, an electrolytic cell 106, an ammonia synthesis module 113, an ammonia absorption module 114, and an ammonia distillation module 117.

[0057] The air separation module 101 may be configured to separate air 100 into a first flow 102 containing oxygen (O2) and a second flow 103 containing nitrogen (N2). The air separation module may be based on membranes, pressure swing adsorption, cryogenic liquefaction, and distillation, or any other technique for separating nitrogen and / or oxygen from air. The system may include an electrolysis module 106 configured to use power 105 to split water (H2O) 104 into a third flow 108 containing O2 and a fourth flow 107 containing hydrogen (H2). The system may further include a deoxygenation module 109 configured to remove oxygen from the second and / or fourth flows. The mixture of H2 and N2 (wet synthesis gas) from the deoxygenation module still contains water, which can be removed by a dehydration module 111. Dehydration can be carried out by adsorbing water onto the absorbent material or by contacting a wet gas flow with a pure ammonia flow (ammonia washing). In the first example, module 111 typically consists of several containers containing a water absorbent, e.g., molecular sieves, which are alternatively operated to dry or regenerate the wet synthesis gas. Regeneration of the dehydration module is carried out by heating the absorbent material by flowing a high-temperature fluid (e.g., a purge gas flow 120) or by directly heating the absorbent bed with an immersed heating element. When an ammonia washing design is employed, module 111 typically consists of a concentrated ammonia solution and a gas-liquid contactor (e.g., a packed column or a simple in-line mixer) in which a fraction of liquid ammonia 119 comes into contact with a wet gas flow to produce ammonia-containing dry vapor, and this is combined with a concentrated aqueous ammonia solution 116.

[0058] Ammonia can be synthesized by reacting a dry mixture of N2 and H2 in an ammonia synthesis module 113, which is equipped with a synthesis reactor configured to operate at a pressure of less than approximately 80 bar.

[0059] The system may further comprise an absorption module 114 configured to absorb NH3 contained in the synthesis module eluent flow into a dilute aqueous flow 118 of ammonia. The absorption module can use any typical gas-liquid contactor, such as a packed column or a tower with trays, and must provide adequate cooling to remove the heat of the reaction produced by the dissolution of NH3 into H2O. Such cooling may be provided via a coil immersed in the absorption module 114 or via an external heat exchanger (around the pump) which cools a fraction of the liquid flowing within the absorption module. The absorption module produces a concentrated aqueous solution 116 of ammonia with a typical concentration of 15% to 30% by weight of ammonia, as well as a gas flow 115 (wet recycle) containing unconverted H2, N2, water, and trace amounts of ammonia. Such flows are recycled to a dewatering module 111 via a simple compressor, typically a one-stage centrifugal or reciprocating unit.

[0060] The system may further comprise an ammonia distillation module 117 configured to remove water from a concentrated aqueous solution 116 to produce a product stream 119 which may have a high ammonia concentration of 99.95% by weight. The distillation module also produces a dilute aqueous solution 118 for use in the absorption module. The distillation module may partially evaporate the lower liquid stream using any typical gas-liquid contactor, such as a packed column or tray tower with a suitable reboiler, and condense the vapor at the top using an overhead condenser.

[0061] The energy required by the distillation module 117 is supplied from any combination of reaction heat from the synthesis module 113 (the reaction between H2 and N2 is exothermic) and heat supplied from an external source, such as an electric heater or a gas emission heater. Energy can also be supplied to the distillation module from waste heat generated by another process, such as a power generation unit.

[0062] A hydrogen recovery unit (HRU module 121) can be added to the system to recover H2 contained in the purge flow 120. Typically, such a module consists of a membrane unit that permeates the H2 flow (low-pressure product) and rejects all other molecules in the purge flow, usually N2, CH4 (if present), and inert gases such as helium (He) and argon (Ar). The H2 product flow is compressed and recycled to an ammonia synthesis module 113, and such compression may be powered by the expansion of the rejection flow 123. Alternatively, module 121 may consist of a different type of unit operation, e.g., pressure swing adsorption (PSA), where the H2 product flow is at the same pressure as the purge flow 120 (excluding the pressure drop of the unit itself). In this case, the H2 product flow may be supplied directly to the ammonia synthesis module 113 if the purge flow is extracted downstream of the circulator, while the H2 flow is recycled upstream of such a circulator. In yet another design, the HRU module 121 could be a cryogenic unit in which H2, and possibly N2, are separated from other molecules such as Ar, He, and CH4 via distillation and recycled to an ammonia synthesis module.

[0063] The systems and methods described herein may be used to produce aqueous solutions of ammonia having any desired ammonia concentration, and the distillation module 117 may be designed to concentrate ammonia to anhydrous ammonia having any desired concentration, optionally, of commercial specifications (>99.5% NH3, >0.1% H2O). Distillation requires an energy input, however, energy can be supplied from exothermic reactions in the process, and such heat can be captured in a hot oil, hot water, or steam system, or supplied directly to the distillation reboiler by supplying a heat flow to the reboiler itself from which heat can be recovered (e.g., reactor elutes from module 113).

[0064] In some cases, the pressure at the electrolytic cell outlet is lower than the pressure in the ammonia synthesis reactor. In such cases, a boost compressor can be used to increase the pressure before the ammonia synthesis reactor. The pressure at the electrolytic cell outlet can be any preferred pressure, such as approximately 5 bar, 15 bar, 20 bar, 25 bar, 30 bar, 35 bar, 40 bar, 50 bar, 60 bar, or 80 bar. In some cases, the electrolytic cell outlet pressure is approximately 20 to 30 bar. The electrolytic cell can be a polymer electrolyte membrane (PEM) or an alkaline electrolytic cell.

[0065] The hydrogen required for ammonia synthesis may be supplied by an electrolytic cell that utilizes electricity to convert water into hydrogen and oxygen. Ammonia products may be considered renewable if part of the electricity supplied to the electrolytic cell originates entirely or partially from a renewable power source or a carbon-free power source such as nuclear power, or if such electricity is supplied from the grid or any other power source, or in combination with the acquisition of renewable power credits or similar financial instruments. In the systems and methods described herein, final oxygen removal is carried out in a deoxygenation (also known as hydrogenation) reactor, so the electrolytic cell does not require a hydrogen purification unit to remove oxygen impurities. However, in some embodiments, a hydrogen purification unit may be beneficial.

[0066] The nitrogen required for ammonia synthesis can be produced from the separation of nitrogen from air or from the concentration of nitrogen in the air. For example, such concentration can be achieved through the use of membranes, which can produce a flow with nitrogen exceeding 80% mol. Alternatively, a pressure swing adsorbent (PSA) or vacuum PSA (VPSA) can be used to produce a nitrogen-enriched flow with a nitrogen concentration exceeding 80% mol. Alternatively, an air separation unit (ASU) can be used to separate nitrogen from air via air liquefaction and / or distillation. Any other means of separating nitrogen from air or concentrating nitrogen in the air can be used in this process, such that the nitrogen concentration in the resulting flow exceeds 80% mol.

[0067] In some cases, nitrogen concentrations are approximately 80%, 85%, 90%, 95%, 97%, 99%, 99.5%, 99.9%, 99.95%, or 99.99%. In some cases, nitrogen concentrations are at least approximately 80%, at least approximately 85%, at least approximately 90%, at least approximately 95%, at least approximately 97%, at least approximately 99%, at least approximately 99.5%, at least approximately 99.9%, at least approximately 99.95%, or at least approximately 99.99%.

[0068] The hydrogen and nitrogen streams can be mixed together to produce a raw synthesis gas ("synthesis gas") stream containing oxygen in addition to hydrogen, nitrogen, and other trace impurities. As used herein, the term "synthesis gas" refers to the gas stream used to produce ammonia. The synthesis gas as used herein typically does not contain significant amounts of carbon monoxide (CO). The raw synthesis gas is preheated to a temperature between ambient temperature and 300°C, depending on the inlet temperature required by the deoxygenation reactor, usually the exact type of hydrogenation catalyst used, and its composition. Preheating can be carried out using an external energy source (e.g., an electric heater) or by recovering heat from a suitable stream in the process via heat exchange.

[0069] A deoxygenation reactor can be a fixed-bed reactor using a standard hydrogenation catalyst, such as those used for hydrogen purification from electrolyte cells. For example, catalysts containing platinum or palladium have been conventionally used in these applications. The reactor design can be a single-stage adiabatic reactor, for example, a vessel containing one type of catalyst. Alternatively, it can be a multi-stage adiabatic reactor having multiple sections of catalyst (either the same catalyst optimized for each section of the reactor, or optionally different catalysts) in series with heat exchangers between each catalyst bed. It can also be an isothermal reactor or a pseudo-isothermal reactor, including any means of providing heat exchange within the catalyst beds. In some embodiments, the reactor can also be a combination of such designs.

[0070] The elutes from the deoxygenation reactor may be a wet synthesis gas flow containing hydrogen, nitrogen, trace impurities, and water produced by the combination of hydrogen and oxygen in the reactor. The wet synthesis gas flow may be cooled to ambient temperature by heat exchange with other process flows, water cooling, air cooling, direct quenching with water, or even by heat exchange with another cold fluid (such as ammonia or an ammonia-containing flow), or any combination thereof. The wet synthesis gas flow may be dried.

[0071] Water can be removed from the wet synthesis gas. In some cases, the synthesis gas is dried in a dehydration unit operating in a temperature swing adsorption (TSA) cycle. Two or more containers may be filled with an absorbent material (e.g., molecular sieves) that has a high affinity for water. One or more containers may operate in adsorption mode, where water in the wet synthesis gas is adsorbed by the absorbent while the gas flow flows through the floor. When the absorbent becomes saturated with water, the containers may be switched to regeneration mode. Some containers operate in adsorption mode, while the others operate in regeneration mode, and the purge gas flow is heated to a suitable temperature (typically 150-350°C) and passes through the saturated absorbent material to evaporate the water contained in the absorbent. The location of the purge extraction within the synthesis loop may vary depending on the specific design and operating conditions. For example, the purge may be extracted from elutes downstream of the absorbent or from the dry synthesis gas produced by the dehydration unit itself.

[0072] A dry synthesis gas flow can be supplied to an ammonia synthesis reactor without the risk of damaging or contaminating ammonia synthesis and / or catalysts, which may be susceptible to oxygenated compounds. Several designs can be employed for ammonia synthesis reactors. In some cases, a multi-stage adiabatic reactor with multiple layers of catalyst may be separated by heat exchangers. The catalyst bed may be contained in a separate vessel or in a single vessel, and the heat exchanger may be outside the vessel or housed inside them. The catalyst bed may have an axial, axial-radial, or radial design. In some cases, the reactor is an axial reactor.

[0073] In some cases, the reactor is a pseudo-isothermal reactor having one or more layers of catalyst, characterized by heat exchange elements inserted into a catalyst bed such as tubes or plates. The catalyst bed may be contained in a separate vessel or a single vessel, and may have an axial, axial-radial, or radial design. In some cases, the reactor is an axial reactor.

[0074] The synthesis reactor used in the method described herein may have a hot shell. In a hot shell reactor, the catalyst is in direct contact with the pressure vessel. This can be achieved here for synthesis operation at lower pressures (and lower temperatures). This is in contrast to the more expensive cold shell reactor, which separates the catalyst from the pressure vessel. The pressure vessel can safely contain hydrogen at the equilibrium temperature of the ammonia synthesis reaction. The synthesis reactor may be an axial reactor. In an axial reactor, gas may flow downwards relative to the catalyst bed.

[0075] Ammonia synthesis catalysts may contain iron oxide. In some cases, the iron oxide contains wustite. The catalyst may contain any suitable accelerators, diluents, binders, and excipients and may be formed into any suitable form. In some cases, the catalyst has a pellet diameter of about 10 mm, about 7 mm, about 5 mm, about 3 mm, about 2 mm, or about 1 mm. In some cases, the catalyst has a pellet diameter of less than about 10 mm, less than about 7 mm, less than about 5 mm, less than about 3 mm, less than about 2 mm, or less than 1 mm. In contrast, global designs typically use radial reactors to achieve high cross-sections. The reactor designs described herein are particularly available for use with these smaller catalyst forms.

[0076] The synthesis of NH3 can be carried out at any suitable pressure. In some cases, the synthesis reactor operates at pressures of approximately 100 bar, 80 bar, 70 bar, 60 bar, 50 bar, 40 bar, or 30 bar. In some cases, the synthesis reactor operates at pressures of less than approximately 100 bar, less than approximately 80 bar, less than approximately 70 bar, less than approximately 60 bar, less than approximately 50 bar, less than approximately 40 bar, or less than approximately 30 bar.

[0077] Ammonia synthesis reactor elutes can be cooled by heat exchange with another process flow, or with an external flow such as water or air, or any combination thereof. Additional cooling can be provided by direct injection of cold ammonia into the reactor elutes (i.e., direct quenching), or by an ammonia cooler (e.g., indirect cooling produced by ammonia evaporation by vapor).

[0078] Depending on the operating pressure and temperature of the ammonia reactor eluent, a portion of the ammonia contained in the reactor eluent, ranging from 0% to 80%, can condense to form a liquid flow of anhydrous ammonia, which is separated from the synthesis gas flow in the gas-liquid separator. The remaining ammonia contained in the reactor eluent is absorbed into the water absorption system, which produces a concentrated aqueous ammonia flow with an ammonia concentration of at least 5% by weight. This aqueous ammonia flow can be distilled to produce a more concentrated aqueous ammonia flow with a concentration ranging from 20% to 99.5% by weight. The operating pressure of the distillation section is selected so that the boiling point of the overhead vapor flow is higher than the typical ambient temperature or the temperature of the most readily available cooling flow, such as cooling water. In this way, the concentrated aqueous ammonia flow leaving the distillation overhead can simply condense in either air or a water cooler. The dilute aqueous ammonia flow exiting the bottom of the column is partially vaporized in a reboiler to produce the required vapor reflux, while the separated boiling liquid is cooled and recycled into the absorption system or otherwise discarded.

[0079] The process may operate using a recycling loop, for example, by recirculating unreacted H2 and N2, and returning the absorption system to the synthesis reactor. The recirculated H2 and N2 may be pressurized to the synthesis reactor pressure using a single-stage compressor called a circulator, and then heated to the required temperature by the ammonia synthesis reactor. By employing an absorption method to separate NH3 from the synthesis reactor elutes, the recirculated flow may contain less than 1%, typically less than 0.1%, of NH3, thereby enabling the reactor to achieve high conversion even at pressures below 80 bar.

[0080] The method shown in Figure 2 can produce aqueous ammonia, or ammonia, as a product of the generation of noble gases such as Ar and / or He, originally contained in either the H2 or N2 feed stream, and the recovery of N2 from the purge stream. In Figure 2, similar figures represent similar elements in Figure 1. However, here, the purge stream 120 may be fed to a hydrogen recovery unit (HRU) 121, where the H2 contained in the purge is separated from other molecules and recycled to an ammonia synthesis reactor. Depending on the HRU design, more than 40%, usually more than 80%, of the H2 in the purge is recovered and recycled to the ammonia synthesis reactor. In cases where the HRU module 121 is a membrane, or PSA, or similar separation device, the off-gas stream 123 may be further processed in a new separation unit 124 designed to separate N2 from all other molecules. For example, unit 124 may be a PSA designed to separate Ar and / or He from N2, in which case the N2 elute stream is recycled to an ammonia synthesis module, while the other elute stream is recovered as a product gas concentrated in Ar and / or He. For example, a conventional PSA may produce a product gas stream with a concentration of at least 30%, typically over 90%, of Ar and / or He.

[0081] In some cases, a combustion unit (e.g., a burner or catalytic oxidizer) can be added downstream of the HRU 121 and upstream of the separation module 124 to convert all remaining H2 into water, which can then be separated via phase condensation and dehydration before processing the rejected flow 123 in the separation unit 124.

[0082] In Figure 3, similar figures represent elements similar to those in Figures 1 and 2. However, here the purge flow 120 may also be supplied to a power generation unit 121, where H2 contained in the purge reacts with O2-containing flow 127 to generate electricity, and the O2-containing flow can be air, concentrated air, e.g., an air separation unit, or an N2 production unit (N2PSA) tail gas. H2 combustion may occur within a fuel cell, internal combustion engine, gas turbine, or linear generator (e.g., a Mainspring unit). Depending on the power generation module design, heat may be recovered from the module's exhaust, and such heat can be used to supply energy to modules 111 or 117. Once cooled to approximately ambient temperature, the exhaust flow 123 may be supplied to a suitably designed separation module 124 to first dehydrate the flow (if required by downstream units), and then separate N2 from all remaining molecules, mainly Ar and / or noble gases such as He, which are recovered as a product flow 126. For example, a conventional PSA may produce a product gas stream with a concentration of at least 30%, typically over 90%, of Ar and / or He. The N2 stream 125 is recycled to an ammonia synthesis module. In a particular case, the power generation unit 121 can be sized such that all the N2 required for ammonia synthesis is supplied from the stream 127 via module 124, thus eliminating the need for the stream 102 and any upstream equipment required to generate it.

[0083] Figure 4 shows a method for producing nitric acid (HNO3) or ammonium nitrate (NH4NO3). In Figure 4, similar figures represent the same elements as in Figures 1, 2, and 3. When diluting the reactants in the NH3 oxidation module 130, particularly using an inert substance different from N2 (for example, when NH3 is supplied to module 130 in combination with CO2, which can act as an inert in the NH3 oxidation process), NH3 can be oxidized to nitrogen oxides (NOx) by using O2 from the electrolytic cell (and / or from the air separation unit) in addition to or as air replacement. NH3 can be oxidized by reacting with oxygen in the presence of a catalyst. The catalyst may include a platinum-based metal and, optionally, rhodium. In some cases, the catalyst includes cobalt. The reaction of NH3 with O2 is highly exothermic and usually takes place at temperatures above 600°C. Such reaction heat can be recovered in a suitably designed heat exchanger to heat an intermediate heat storage medium (such as hot oil or water) or to generate steam. Such recovered heat can be supplied to unit 111 or 117, or to any other point in the process where heat is required.

[0084] In some embodiments, as shown in Figure 4, the method further includes cooling the eluent from module 130 and absorbing it in water in a suitable absorption tower 132. In some embodiments, O2 derived from electrolysis can be used to oxidize and / or ozonate nitrogen oxides, such as nitrous oxide (N2O) and nitric oxide (NO), to nitrogen dioxide (NO2). In these embodiments, the O2 may be partially converted to ozone in a separate ozonator before being injected downstream of module 130.

[0085] The HNO3 solution produced by the dissolution of NO2 in water can be reacted with NH3 in the neutralization reactor 134 to produce an NH4NO3 solution 135. Such a neutralization reaction is also highly exothermic, and the heat of reaction can be recovered and supplied to other sections of the process. Alternatively, it can be recognized that the heat of neutralization can be used to supply a concentrated aqueous ammonia stream 116 to the oxidation module 130, since such heat of reaction evaporates a large amount of water contained in stream 116, thus producing a concentrated aqueous solution 135 of NH4NO3. In some embodiments, stream 135 is further supplied to a downstream module, such as a granulation tower, to evaporate all the water and produce a solid ammonium nitrate product.

[0086] The vapor flow 136 exiting module 132 contains N2, N2O, and insoluble NOx. A purification module 137 can be added to the system to convert all nitrogen compounds in the flow 136 to N2 and / or separate N2 from all remaining molecules, for example, via a catalytic converter and / or a selective catalytic reduction (SCR) system. This pure N2 flow can then be recycled to the ammonia synthesis system.

[0087] Figure 5 illustrates the urea (CH4N2O) method. In Figure 5, similar figures represent elements similar to those in Figures 1, 2, 3, and 4. Any combination of concentrated aqueous ammonia stream 116 and NH3 stream 119 can be supplied to the urea synthesis module 140. In this module, NH3 readily reacts with CO2 to form carbamates, which are then spontaneously converted to urea until thermodynamic equilibrium is achieved. The CO2 stream 141 can originate from several sources, including, but not limited to, pipelines, natural gas processing plants, hydrocarbon ammonia plants, flue gas, biomass fermentation (e.g., corn for ethanol production), waste incineration or gasification, direct air recovery (DAC), or any other industrial or natural sources.

[0088] The urea synthesis module 140 typically consists of a reactor operating at a pressure greater than 150 bar, up to 300 bar, using a stoichiometric mixture of NH3 and CO2. In some embodiments, excess CO2 can be utilized to maximize the conversion of NH3 to carbamates and urea. In some embodiments, module 140 also contains unconverted NH3. 3、 It also includes a high-pressure stripper and / or condenser for separating and directly recycling CO2 into a urea synthesis reactor.

[0089] The product of module 140 is a mixture of urea, carbamate, NH3, CO2, and water. Modules 142 and 144 utilize a sequence of several different unit operations under reduced pressure, such as a carbamate decomposer, stripper, and other separation units, to recover a concentrated urea solution 143 (typically having a concentration of 70-80% of the urea in water) and recycle the unconverted CO2 and NH3 into a reactor with any remaining carbamate. In some embodiments, the urea solution 143 is further concentrated, usually in a vacuum condenser, and then continuously granulated or granulated to produce a solid urea product.

[0090] In Figure 6, similar figures represent elements similar to those in Figures 1, 2, 3, 4, and 5. Here, the methods described in Figures 4 and 5 are combined to produce urea-ammonium nitrate (UAN) product 151 by mixing ammonium nitrate solution 135 and urea solution 143 in a suitably designed mixing module 150. Module 150 typically consists of a mixing tank and is sometimes cooled by an immersion cooling element (such as a coil) or an external exchanger. Corrosion inhibitors and other additives may be added to the UAN product 151 to improve its stability and reduce its corrosiveness.

[0091] The methods described herein provide a more efficient pathway to nitrogen products such as UAN than mixing solid urea and solid ammonium nitrate in water. In another embodiment, a method for producing nitrogen products is provided herein, comprising forming a solution comprising a composition substantially similar to 20% by mass of water (H2O), 40% by mass of ammonium nitrate (NH4NO3), and 40% by mass of urea (CH4N2O), wherein the solution is formed without mixing solid urea with solid ammonium nitrate. In some cases, the concentrations of H2O, NH4NO3, and CH4N2O do not change by more than 30% in the solution. In some embodiments, the concentrations of H2O, NH4NO3, and CH4N2O do not change by more than 10% in the solution.

[0092] The ammonium nitrate required for the process shown in Figure 6 can be supplied from an external source. Similarly, the urea required for the process shown in Figure 6 can be supplied from an external source. For example, in Figures 7, 8, 9, and 10, similar figures represent the same elements as in Figures 1, 2, 3, 4, 5, and 6.

[0093] Referring to Figure 7, an example of the system and method described herein for the production of UAN using exogenously produced urea is shown here. Here, urea 152 (e.g., supplied exogenously and / or produced from the system and method described herein) may be used for the production of UAN by the system and method described herein, for example. Urea 152 may be mixed with water 156 (154) to produce a urea solution 143. The process then proceeds as described herein.

[0094] Referring to Figure 8, an example of the system and method described herein for producing UAN using exogenously produced ammonium nitrate is shown here. Here, ammonium nitrate 158 (e.g., supplied exogenously and / or produced from the system and method described herein) may be used, for example, for the production of UAN by the system and method described herein. Ammonium nitrate (AN) 158 may be mixed with water 160 to produce ammonium nitrate (NH4NO3) solution 135. The process then proceeds as described herein.

[0095] Referring to Figure 9, an example of the system and method described herein for producing UAN using exogenously generated nitric acid is shown herein. Here, nitric acid 162 (e.g., supplied exogenously and / or produced from the system and method described herein) may be used for the production of UAN, for example, according to the system and method described herein. Nitric acid (HNO3) 162 may be mixed with water 164 to produce a nitric acid (NNO3) solution 133. The process then proceeds as described herein.

[0096] Referring to Figure 10, examples of the system and method described herein for the production of UAN using exogenously produced nitric acid and urea are shown herein. Here, nitric acid 162 (e.g., supplied exogenously and / or produced from the system and method described herein) may be used for the production of UAN, for example, according to the system and method described herein. Nitric acid (HNO3) 162 may be mixed with water 164 to produce a nitric acid (NNO3) solution 133. Furthermore, urea 152 (e.g., supplied exogenously and / or produced from the system and method described herein) may be used for the production of UAN, for example, according to the system and method described herein. Urea 152 may be mixed with water 156 to produce a urea solution 143. The process then proceeds as described herein.

[0097] In some cases, the only inputs in this process are air, water, CO2, and electricity, and the final products are aqueous and anhydrous ammonia, which can be produced in any combination depending on the design and operating parameters selected for the process.

[0098] The system may consume approximately 300 megawatts (MW), 200 MW, 100 MW, 80 MW, 80 MW, 60 MW, 40 MW, 20 MW, or 10 MW of power per year. In some cases, the system will consume less than approximately 300 megawatts (MW), 200 MW, 100 MW, 80 MW, 80 MW, 60 MW, 40 MW, 20 MW, or 10 MW of power per year.

[0099] The systems described herein may have any suitable capacity for producing nitrogen products. In some cases, the system has a capacity for producing NH3 of about 1,000, about 5,000, about 10,000, about 50,000, about 100,000, or about 1,000,000 metric tons per year. In some embodiments, the system has a capacity for producing nitrogen products of at least about 1,000, at least about 5,000, at least about 10,000, at least about 50,000, or at least about 100,000 metric tons per year. In some cases, the system has a capacity for producing nitrogen products of at most about 1,000, at most about 5,000, at most about 10,000, at most about 50,000, or at most about 100,000 metric tons per year.

[0100] The embodiments described above can be implemented in any of a number of ways. For example, the embodiments can be implemented using hardware, software, or a combination thereof. If implemented in software, the software code can run on any suitable processor, or set of processors, whether provided on a single computer or distributed across multiple computers. Naturally, any component, or set of components, that performs the functions described above can generally be considered as one or more controllers that control the functions described above. One or more controllers can be implemented in a number of ways, such as using dedicated hardware or using one or more processors programmed with microcode or software to perform the functions described above.

[0101] In this regard, naturally, one implementation of an embodiment of the present invention comprises at least one non-temporary computer-readable storage medium (e.g., computer memory, portable memory, compact disk, etc.) coded in a computer program (i.e., a set of instructions) that, when executed on a processor, performs the functions of the embodiments of the present invention. The computer-readable storage medium may be movable so that the program stored thereon can be loaded onto any computer resource to implement the embodiments of the present invention discussed herein. Furthermore, naturally, reference to a computer program that, when executed, performs the functions described above is not limited to an application program executed on a host computer. Rather, the term computer program is used herein in a general sense to refer to any type of computer code (e.g., software, or microcode) that may be employed to program a processor to implement the embodiments of the present invention described above.

[0102] Various aspects of the present invention may be used individually, in combination, or in various arrangements not specifically considered in the embodiments described above, and therefore, in those applications, they are not limited to the details and arrangements of components described in the above description or illustrated in the drawings. For example, an aspect described in one embodiment may be combined in any way with an aspect described in another embodiment.

[0103] Furthermore, embodiments of the present invention may be carried out as one or more methods as provided in the examples. Actions carried out as part of a method may be ordered in any preferred manner. Thus, although the exemplary embodiments are shown as sequential actions, embodiments may be constructed in which actions are carried out in a different order than those shown, which may include some actions being carried out simultaneously.

[0104] The use of common terms such as "first," "second," and "third" in the claims to modify claim elements does not in itself imply a temporal order in which one claim element takes precedence, precedes another claim element, or is in a sequence or method of action. Such terms are used solely as labels to distinguish one claim element having a particular name from another element having the same name (for the sake of common terminology).

[0105] The words and terms used herein are for illustrative purposes only and should not be considered limiting. The use of “including,” “comprising,” “having,” “containing,” “involving,” and variations thereof means to include the items listed thereafter, and any additional items.

[0106] Further embodiments may be provided by combining the various embodiments described above. All U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications, and non-patent publications referenced herein and / or listed in the application datasheet, including U.S. Provisional Patent Application No. 63 / 508,226, filed on 14 June 2023, for which this application claims priority, are incorporated herein by reference in their entirety. The aspects of the embodiments may be modified as necessary to adopt concepts from various patents, applications, and publications in order to provide further embodiments.

[0107] While several embodiments of the present invention have been described in detail, various modifications and improvements will readily occur for those skilled in the art. Such modifications and improvements are intended to be within the spirit and scope of the present invention. Therefore, the foregoing description is for illustrative purposes only and is not intended to limit it. The present invention is limited only to the following claims and equivalents.

[0108] (Note) (Note 1) A method for producing ammonia, wherein the method is a. Mixing (H2) with nitrogen (N2) to generate a mixed flow, and optionally processing the mixed flow in a deoxidation reactor to remove residual oxygen (O2), b. Dewatering the combination of the mixed flow and the recycled flow to generate a dry flow, c. The H2 and N2 contained in the drying flow are reacted in a synthesis reactor to form an elute flow containing ammonia (NH3), d. The process involves absorbing NH3 from the eluted stream in water to generate an aqueous ammonia solution and the recycled stream, wherein the recycled stream contains unreacted H2 and N2 and is combined with the mixed stream. e. To control the accumulation of inert species in the system, the fraction of the recycle flow is separated and a purge flow is generated, f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor, power is supplied for the dehydration and / or distillation. Methods that include...

[0109] (Note 2) The method according to Appendix 1, wherein the hydrogen (H2) is supplied from a geological source.

[0110] (Note 3) The method according to Appendix 1, wherein the hydrogen (H2) is supplied from an electrolytic cell powered using renewable electricity.

[0111] (Note 4) The method according to Appendix 3, wherein the electrolytic cell further generates oxygen (O2), and the method further comprises mixing H2 with N2 and treating such mixed flow in a deoxidation reactor to remove residual O2.

[0112] (Note 5) The method according to Appendix 1, wherein the rate of ammonia production increases or decreases in response to the price or availability of renewable electricity.

[0113] (Note 6) The method according to Appendix 1, wherein the N2 is produced by cryogenic air liquefaction and distillation.

[0114] (Note 7) The method according to Appendix 1, wherein the N2 is generated by pressure swing adsorption (PSA).

[0115] (Note 8) The method according to Appendix 1, wherein the N2 is a selectively permeable membrane.

[0116] (Note 9) The method according to Appendix 1, wherein the dehydration is carried out using thermal swing adsorption (TSA).

[0117] (Note 10) The method according to Appendix 1, wherein the dehydration is carried out by bringing the wet gas mixture into contact with a molecular sieve material.

[0118] (Note 11) The method according to Appendix 1, wherein the dehydration is carried out by contacting the wet gas mixture with an aqueous solution of ammonia or liquid ammonia.

[0119] (Note 12) The method according to Appendix 1, wherein the NH3 is synthesized in a reactor at a pressure of less than approximately 80 bar.

[0120] (Note 13) The method according to Appendix 1, wherein the NH3 is synthesized in a reactor at a pressure of less than approximately 60 bar.

[0121] (Note 14) The method according to Appendix 1, wherein the NH3 is synthesized in a reactor at a pressure of approximately 40 bar.

[0122] (Note 15) The method according to Appendix 1, wherein the NH3 is synthesized in a reactor at a pressure of less than approximately 40 bar.

[0123] (Note 16) The method according to Appendix 1, wherein the NH3 is synthesized in the presence of a catalyst, and the catalyst is in direct contact with a pressure vessel.

[0124] (Note 17) The method according to Appendix 1, wherein the NH3 is synthesized in the presence of a catalyst, and the catalyst is contained on the inside of a tube in a container.

[0125] (Note 18) The method according to Appendix 1, wherein a portion of the NH3 contained in the eluent stream is condensed and separated, and the remaining portion is absorbed into the water.

[0126] (Note 19) The method according to Appendix 1, wherein the NH3 in the eluted stream is absorbed into water using a column packed with packing material.

[0127] (Note 20) The method according to Appendix 1, wherein the NH3 in the eluent stream is absorbed into water using a column equipped with a tray.

[0128] (Note 21) The method according to Appendix 1, wherein the aqueous ammonia solution is distilled using a column packed with packing material.

[0129] (Note 22) The method according to Appendix 1, wherein the aqueous ammonia solution is distilled using a column equipped with a tray.

[0130] (Note 23) The method according to Appendix 1, wherein the distillation of the aqueous ammonia solution is at least partially powered by an external heat source.

[0131] (Note 24) The method according to Appendix 1, wherein the formation of NH3 generates heat, and the heat is captured in a hot oil, hot water, or steam system.

[0132] (Note 25) The method according to Appendix 1, wherein the H2 contained in the purge flow is separated and recycled for ammonia synthesis.

[0133] (Note 26) The method according to Appendix 1, wherein the H2 contained in the purge flow is separated, further compressed, and recycled for ammonia synthesis.

[0134] (Note 27) a. Separating the purge flow into a concentrated H2 flow and a tail gas flow containing non-reactive species (e.g., N2, CH4 (if present in the system), and noble gases Ar and He), b. Recycling the purge flow for ammonia synthesis, c. To concentrate Ar and / or He from the tail gas flow to generate a product flow, The method described in Appendix 1, further including the method described in Appendix 1.

[0135] (Note 28) A method for producing ammonia, wherein the method is a. Mixing H2 with N2 to generate a mixed flow, b. Dewatering the mixed flow and the recycled flow to generate a dry flow, c. The H2 and N2 contained in the drying flow are reacted in a synthesis reactor to form an elute flow containing ammonia (NH3), d. From the eluted material flow, absorb NH3 in water to generate a recycled flow containing an aqueous ammonia solution and the unreacted H2 and N2. e. To control the accumulation of any inert species within the system, the fraction of the recycle flow is separated and a purge flow is generated. f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor to supply power to the dehydration and / or distillation, h. Separating the purge flow into a concentrated H2 flow and a tail gas flow containing all non-reactive species (N2, CH4 (if present in the system), and noble gases Ar and He), i. Recycling the purge flow for ammonia synthesis, j. To concentrate the Ar and / or He from the tail gas flow to generate a product flow, Methods that include...

[0136] (Note 29) The method according to Appendix 28, wherein the H2 is separated from the purge flow via cryogenic distillation.

[0137] (Note 30) The method according to Appendix 28, wherein H2 is separated from the purge flow via pressure swing adsorption (PSA).

[0138] (Note 31) The method according to Appendix 28, wherein the H2 is separated from the purge flow by a selectively permeable membrane.

[0139] (Note 32) The method according to Appendix 28, wherein the Ar and / or He are separated from the tail gas stream via cryogenic distillation.

[0140] (Note 33) The method according to Appendix 28, wherein the Ar and / or He are separated from the tail gas flow via pressure swing adsorption (PSA).

[0141] (Note 34) The method according to Appendix 28, wherein the Ar and / or He are separated from the tail gas flow by a selectively permeable membrane.

[0142] (Note 35) The method according to Appendix 34, wherein the tail gas flow is recycled for ammonia synthesis after the removal of Ar and / or He.

[0143] (Note 36) a. Supplying the purge flow to the power generation unit, wherein the H2 in the flow reacts with O2 to generate an exhaust flow. b. Concentrating Ar and / or He from the exhaust flow to generate a product flow and a tail gas flow, The method described in Appendix 28, further including the method described in Appendix 28.

[0144] (Note 37) A method for producing ammonia, wherein the method is a. Mixing H2 with N2 to generate a mixed flow, b. Dewatering the combination of the mixed flow and the recycled flow to generate a dry flow, c. In the synthesis reactor, the H2 and N2 contained in the drying stream are reacted to form ammonia (NH3) contained in the elute stream, d. From the eluted material flow, absorb NH3 in water to generate a recycled flow containing an aqueous ammonia solution and the unreacted H2 and N2. e. To control the accumulation of any inert species within the system, the fraction of the recycle flow is separated and a purge flow is generated. f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor, power is supplied for the dehydration and / or distillation. h. The purge flow is supplied to a power generation unit in which the H2 reacts with the O2 to generate an exhaust flow. i. Concentrating Ar and / or He from the exhaust flow to generate a product flow and a tail gas flow, Methods that include...

[0145] (Note 38) The method described in Appendix 37, wherein the aforementioned electricity is generated within a fuel cell.

[0146] (Note 39) The method according to Appendix 37, wherein the aforementioned electricity is generated within an internal combustion engine.

[0147] (Note 40) The method according to Appendix 37, wherein the aforementioned electricity is generated in a gas turbine.

[0148] (Note 41) The method described in Appendix 37, wherein the aforementioned power is generated within a linear generator.

[0149] (Note 42) The method described in Appendix 37, wherein electricity is used in the process described above.

[0150] (Note 43) The method according to Appendix 37, wherein the heat is recovered from the exhaust flow.

[0151] (Note 44) The method according to Appendix 43, wherein the heat is captured in a hot oil, hot water, or steam system.

[0152] (Note 45) The method according to Appendix 43, wherein the recovered heat is utilized within the process.

[0153] (Note 46) The method according to Appendix 37, wherein water is separated from the exhaust flow before the concentration of Ar and / or He.

[0154] (Note 47) The method according to Appendix 37, wherein the Ar and / or He are separated from the exhaust stream via cryogenic distillation.

[0155] (Note 48) The method according to Appendix 37, wherein the Ar and / or He are separated from the exhaust flow via pressure swing adsorption (PSA).

[0156] (Note 49) The method according to Appendix 37, wherein the Ar and / or He are separated from the exhaust flow by a selectively permeable membrane.

[0157] (Note 50) a. To oxidize any combination of the aqueous ammonia solution and the concentrated ammonia product to form a NOx-rich stream of nitrogen oxides (NOx), b. From the aforementioned NOx flow, NO2 is absorbed in water to generate an aqueous solution of nitric acid (HNO3) and a vapor flow. The method described in Appendix 1, further including the method described in Appendix 1.

[0158] (Supplementary Note 51) A method for producing ammonia, wherein the method comprises: a. Mixing H2 with N2 to generate a mixed stream; b. Dehydrating the combination of the mixed stream and the recycle stream to generate a dried stream; c. Reacting the H 2、 and N2 contained in the dried stream in a synthesis reactor to form an eluate stream containing ammonia (NH3); d. Absorbing NH3 from the eluate stream in water to generate an aqueous ammonia solution and a recycle stream containing the unreacted H2 and N2; e. Separating a fraction of the recycle stream to generate a purge stream to control the accumulation of any inert species in the system; f. Distilling the aqueous ammonia solution to generate a more concentrated ammonia product; g. Using the heat generated by the ammonia synthesis reactor to supply power to the dehydration and / or the distillation; h. Oxidizing any combination of the aqueous ammonia solution and the concentrated ammonia product to form a NOx-rich NOx stream rich in nitrogen oxides (NOx); i. Absorbing NO2 from the NOx stream in water to generate an aqueous solution of nitric acid (HNO3) and a vapor stream; A method comprising the above.

[0159] (Supplementary Note 52) The method according to Supplementary Note 51, wherein the oxidation of NH3 generates heat, and the heat is captured in a hot oil, hot water, or steam system.

[0160] (Supplementary Note 53) The method according to Supplementary Note 52, wherein the captured heat is utilized within the process.

[0161] (Supplementary Note 54) The method according to Appendix 51, wherein the NH3 is oxidized with oxygen in the presence of a catalyst.

[0162] (Note 55) The method according to Appendix 54, wherein the catalyst comprises a platinum group metal and optionally rhodium.

[0163] (Note 56) The method according to Appendix 54, wherein the catalyst contains cobalt.

[0164] (Note 57) The method according to Appendix 51, further comprising cooling the NOx stream while enabling the continuous oxidation of the nitrogen compound to NO2.

[0165] (Note 58) The method according to Appendix 51, further comprising using O2 derived from electrolysis to further oxidize nitrogen oxides such as nitrous oxide (N2O) and nitric oxide (NO) to nitrogen dioxide (NO2).

[0166] (Note 59) The method according to Appendix 51, further comprising using O2 derived from electrolysis to ozonate a portion of the O2, and using the partially ozonated flow to further oxidize nitrogen oxides such as nitrous oxide (N2O) and nitric oxide (NO) to nitrogen dioxide (NO2).

[0167] (Note 60) The method according to Appendix 51, further comprising using O2 derived from air separation to further oxidize nitrogen oxides such as nitrous oxide (N2O) and nitric oxide (NO) to nitrogen dioxide (NO2).

[0168] (Note 61) The method according to Appendix 51, further comprising using O2 derived from air separation to ozonate a portion of the O2, and using the partially ozonated flow to further oxidize nitrogen oxides such as nitrous oxide (N2O) and nitric oxide (NO) to nitrogen dioxide (NO2).

[0169] (Note 62) The method according to Appendix 51, wherein the aqueous solution of HNO3 is neutralized with any combination of the aqueous ammonia solution and the stream of concentrated ammonia product to form an aqueous solution of ammonium nitrate (NH4NO3).

[0170] (Note 63) The method according to Appendix 62, wherein the neutralization of HNO3 generates heat, and the heat is captured in a hot oil, hot water, or steam system.

[0171] (Note 64) The method according to Appendix 63, wherein the captured heat is utilized within the process.

[0172] (Note 65) The method according to Appendix 62, wherein the neutralization of HNO3 generates heat, and the heat is used to evaporate the water contained in the aqueous solution of HNO3.

[0173] (Note 66) The method according to Appendix 51, wherein the vapor flow is treated to separate N2 from other compounds.

[0174] (Note 67) The method according to Appendix 66, wherein the separated N2 is recycled for ammonia synthesis.

[0175] (Note 68) The method according to Appendix 62, wherein the aqueous solution of ammonium nitrate is further concentrated or diluted by removing or adding water.

[0176] (Note 69) The method according to Appendix 62, wherein the aqueous solution of ammonium nitrate is granulated or converted to solid ammonium nitrate by another method.

[0177] (Note 70) The method according to Appendix 68, wherein a more concentrated or diluted aqueous solution of ammonium nitrate is granulated or otherwise converted into solid ammonium nitrate.

[0178] (Note 71) a. Reacting any combination of the aqueous ammonia product and the concentrated ammonia product with CO2 to form a urea (CH4N2O)-rich eluate stream, b. Separating the aqueous urea solution from the aforementioned elution stream, The method described in Appendix 1, including the method described in Appendix 1.

[0179] (Note 72) A method for producing ammonia, wherein the method is a. Mixing H2 with N2 to generate a mixed flow, b. Dewatering the combination of the mixed flow and the recycled flow to generate a dry flow, c. The H2 and N2 contained in the drying flow are reacted in a synthesis reactor to form an elute flow containing ammonia (NH3), d. From the elute stream, NH3 is absorbed in water, and the aqueous ammonia solution and the unreacted H 2、 and generating the aforementioned recycled flow containing N2, e. To control the accumulation of any inert species within the system, the fraction of the recycle flow is separated and a purge flow is generated. f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reaction, power is supplied for the dehydration and / or distillation. h. Reacting any combination of the aqueous ammonia solution and the concentrated ammonia product with CO2 to form a urea (CH4N2O)-rich eluate stream, i. Separating the aqueous urea solution from the aforementioned elution stream, Methods that include...

[0180] (Note 73) The method according to Appendix 72, wherein the CO2 originates from flue gas.

[0181] (Note 74) The method according to Appendix 72, wherein the CO2 is derived from biomass or waste fermentation.

[0182] (Note 75) The method according to Appendix 72, wherein the CO2 is derived from the fermentation of biomass (e.g., corn) for the production of ethanol.

[0183] (Note 76) The method according to Appendix 72, wherein the CO2 originates from an industrial facility (e.g., natural gas processing).

[0184] (Note 77) The method described in Appendix 72, wherein the CO2 is supplied from a pipeline.

[0185] (Note 78) The method described in Appendix 72, wherein the CO2 is supplied directly from air recovery (DAC).

[0186] (Note 79) The method according to Appendix 72, wherein the CO2 has a purity of less than 99% and more than 80%.

[0187] (Note 80) The method according to Appendix 72, wherein the urea synthesis is carried out at a pressure exceeding 150 bar.

[0188] (Note 81) The method according to Appendix 72, wherein the molar ratio of NH3 and CO2 in the supply flow to urea synthesis is greater than approximately 2.

[0189] (Note 82) The method according to Appendix 72, wherein the urea aqueous solution is further concentrated in urea by removing water.

[0190] (Note 83) The method according to Appendix 82, wherein the concentrated urea solution is granulated or otherwise converted into solid urea.

[0191] (Note 84) The method according to Appendix 72, wherein the aqueous solution of urea is further diluted in urea by removing water to form diesel exhaust fluid (DEF).

[0192] (Note 85) a. Oxidizing the aqueous ammonia solution and a portion of the concentrated ammonia to form a NOx-rich stream, b. From the aforementioned NOx flow, NO2 is absorbed in water to generate an aqueous solution of nitric acid (HNO3) and a vapor flow. c. The remaining portion of the aqueous ammonia solution and the concentrated ammonia are reacted with CO2 to form a urea (CH4N2O)-rich flow, d. Separating the urea aqueous solution from the urea-rich flow, e. Combining the aqueous solution of urea with an aqueous solution of nitric acid (HNO3) to form an ammonium urea nitrate (UAN) solution, The method described in Appendix 1, further including the method described in Appendix 1.

[0193] (Note 86) A method for producing ammonia, wherein the method is a. Mixing H2 with N2 to generate a mixed flow, b. Dewatering the combination of the mixed flow and the recycled flow to generate a dry flow, c. The H contained in the drying flow 2、 And N2 are reacted in a synthesis reactor to form an elute stream containing ammonia (NH3), d. From the elute stream, NH3 is absorbed in water, and the aqueous ammonia solution and the unreacted H 2、 and generating the aforementioned recycled flow containing N2, e. To control the accumulation of any inert species within the system, the fraction of the recycle flow is separated and a purge flow is generated. f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor, power is supplied for the dehydration and / or distillation. h. The aqueous ammonia solution and a portion of the concentrated ammonia are oxidized to form a NOx-rich stream, i. From the aforementioned NOx flow, NO2 is absorbed in water to generate an aqueous solution of nitric acid (HNO3) and a vapor flow, j. The remaining portion of the flow, the aqueous ammonia solution, and the concentrated ammonia are reacted with CO2 to form a urea (CH4N2O)-rich eluate flow. k. Separating the urea aqueous solution from the urea-rich flow, l. Combining the aqueous solution of urea with an aqueous solution of nitric acid (HNO3) to form an ammonium urea nitrate (UAN) solution, Methods that further include this.

[0194] (Note 87) A system configured to perform any of the methods described in any one of the preceding appendices.

Claims

1. A method for producing ammonia, wherein the method is a. (H ２ ) to nitrogen (N ２ ) is mixed with to generate a mixed flow, and the mixed flow is optionally processed in the deoxidation reactor to remove residual oxygen (O ２ ) to remove, b. Dewatering the combination of the mixed flow and the recycled flow to generate a dry flow, c. The H contained in the drying flow ２ , and N ２ This is reacted in a synthesis reactor to produce ammonia (NH ３ Forming a elution stream containing ) d. From the eluate stream, absorbing NH ３ in water to produce an aqueous ammonia solution and the recycle stream, the recycle stream containing unreacted H ２ , and N ２ and being combined with the mixed stream. e. To control the accumulation of inert species in the system, the fraction of the recycle flow is separated and a purge flow is generated, f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor to supply power for the dehydration and / or distillation, Methods that include...

2. The hydrogen (H ２ The method according to claim 1, wherein the material is provided from a geological source.

3. The hydrogen (H ２ The method according to claim 1, wherein the electrolytic cell is powered using renewable energy.

4. The electrolytic cell contains oxygen (O ２ ) further generates, and the method is H ２ N ２ It is mixed with and such a mixed flow is treated in a deoxidation reactor to remove residual O ２ The method according to claim 3, further comprising removing

5. The method according to claim 1, wherein the rate of ammonia production increases or decreases in response to the price or availability of renewable electricity.

6. The aforementioned N ２ The method according to claim 1, wherein the product is produced by cryogenic air liquefaction and distillation.

7. The aforementioned N ２ The method according to claim 1, wherein the product is generated by pressure swing adsorption (PSA).

8. The aforementioned N ２ The method according to claim 1, wherein the selectively permeable membrane is produced.

9. The method according to claim 1, wherein the dehydration is carried out using thermal swing adsorption (TSA).

10. The method according to claim 1, wherein the dehydration is carried out by bringing the wet gas mixture into contact with a molecular sieve material.

11. The method according to claim 1, wherein the dehydration is carried out by contacting the wet gas mixture with an aqueous solution of ammonia or liquid ammonia.

12. Said NH ３ The method according to claim 1, wherein the synthesis is carried out in a reactor at a pressure of less than approximately 80 bar.

13. Said NH ３ The method according to claim 1, wherein the synthesis is carried out in a reactor at a pressure of less than approximately 60 bar.

14. Said NH ３ The method according to claim 1, wherein the product is synthesized in a reactor at a pressure of approximately 40 bar.

15. Said NH ３ The method according to claim 1, wherein the synthesis is carried out in a reactor at a pressure of less than approximately 40 bar.

16. Said NH ３ The method according to claim 1, wherein the material is synthesized in the presence of a catalyst, and the catalyst is in direct contact with a pressure vessel.

17. Said NH ３ The method according to claim 1, wherein the product is synthesized in the presence of a catalyst, and the catalyst is contained on the inside of a tube in a container.

18. The NH contained in the aforementioned elute flow ３ The method according to claim 1, wherein a portion is condensed and separated, and the remaining portion is absorbed into water.

19. The NH in the elute flow ３ The method according to claim 1, wherein the material is absorbed into water using a column packed with packing material.

20. The NH in the elute flow ３ The method according to claim 1, wherein the substance is absorbed into water using a column equipped with a tray.

21. The method according to claim 1, wherein the aqueous ammonia solution is distilled using a column packed with packing material.

22. The method according to claim 1, wherein the aqueous ammonia solution is distilled using a column equipped with a tray.

23. The method according to claim 1, wherein the distillation of the aqueous ammonia solution is at least partially powered by an external heat source.

24. Said NH ３ The method according to claim 1, wherein the formation generates heat, and the heat is captured in a hot oil, hot water, or steam system.

25. The H contained in the purge flow ２ The method according to claim 1, wherein the ammonia is separated and recycled for ammonia synthesis.

26. The H contained in the purge flow ２ The method according to claim 1, wherein the material is separated, further compressed, and recycled for ammonia synthesis.

27. a. The purge flow is concentrated H ２ Flow and non-reactive species (e.g., N ２ ,CH ４ (If present in the system), and containing noble gases Ar and He, the tail gas flow is separated into b. Recycling the purge flow for ammonia synthesis, c. To concentrate Ar and / or He from the tail gas flow to generate a product flow, The method according to claim 1, further comprising:

28. A method for producing ammonia, wherein the method is a. H ２ to N ２ To mix with it and generate a mixed flow, b. Dewatering the mixed flow and the recycled flow to generate a dry flow, c. The H contained in the drying flow ２ , and N ２ This is reacted in a synthesis reactor to produce ammonia (NH ３ Forming a elution stream containing ) d. From the aforementioned elution flow, NH in water ３ It absorbs the aqueous ammonia solution and the unreacted H ２ , and N ２ To generate a recycling flow that contains, e. To control the accumulation of any inert species within the system, the fraction of the recycle flow is separated and a purge flow is generated. f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor to supply power to the dehydration and / or distillation, h. The purge flow is concentrated H ２ The flow and all non-reactive species (N ２ ,CH ４ (If present in the system), and containing the noble gases Ar and He, the tail gas flow is separated into i. Recycling the purge flow for ammonia synthesis, j. To concentrate the Ar and / or He from the tail gas flow to generate a product flow, Methods that include...

29. The aforementioned H ２ The method according to claim 28, wherein the material is separated from the purge flow via cryogenic distillation.

30. The aforementioned H ２ The method according to claim 28, wherein the material is separated from the purge flow via pressure swing adsorption (PSA).

31. The aforementioned H ２ The method according to claim 28, wherein the purge flow is separated by a selectively permeable membrane.

32. The method according to claim 28, wherein the Ar and / or He are separated from the tail gas stream via cryogenic distillation.

33. The method according to claim 28, wherein the Ar and / or He are separated from the tail gas flow via pressure swing adsorption (PSA).

34. The method according to claim 28, wherein the Ar and / or He are separated from the tail gas flow by a selectively permeable membrane.

35. The method according to claim 34, wherein the tail gas flow is recycled for ammonia synthesis after the removal of Ar and / or He.

36. a. Supplying the purge flow to the power generation unit, wherein H in the flow ２ However, O ２ In response, it generates and supplies exhaust flow, b. Concentrating Ar and / or He from the exhaust flow to generate a product flow and a tail gas flow. The method according to claim 28, further comprising:

37. A method for producing ammonia, wherein the method is a. H ２ to N ２ To mix with it and generate a mixed flow, b. Dewatering the combination of the mixed flow and the recycled flow to generate a dry flow, c. In the synthesis reactor, the H contained in the drying flow ２ , and N ２ By reacting the ammonia (NH) contained in the elute stream, ３ ) forming, d. From the aforementioned elution flow, NH in water ３ It absorbs the aqueous ammonia solution and the unreacted H ２ , and N ２ To generate a recycling flow that contains, e. To control the accumulation of any inert species within the system, the fraction of the recycle flow is separated and a purge flow is generated. f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor to supply power for the dehydration and / or distillation, h. The purge flow is H ２ O ２ In response, it generates exhaust flow and supplies it to the power generation unit, i. Concentrating Ar and / or He from the exhaust flow to generate a product flow and a tail gas flow, Methods that include...

38. The method according to claim 37, wherein the electricity is generated within a fuel cell.

39. The method according to claim 37, wherein the aforementioned electricity is generated within an internal combustion engine.

40. The method according to claim 37, wherein the electricity is generated in a gas turbine.

41. The method according to claim 37, wherein the power is generated in a linear generator.

42. The method according to claim 37, wherein electricity is used in the process.

43. The method according to claim 37, wherein the heat is recovered from the exhaust flow.

44. The method according to claim 43, wherein the heat is captured in a hot oil, hot water, or steam system.

45. The method according to claim 43, wherein the recovered heat is utilized within the process.

46. The method according to claim 37, wherein water is separated from the exhaust flow before the Ar and / or He is concentrated.

47. The method according to claim 37, wherein the Ar and / or He are separated from the exhaust flow by cryogenic distillation.

48. The method according to claim 37, wherein Ar and / or He are separated from the exhaust flow via pressure swing adsorption (PSA).

49. The method according to claim 37, wherein the Ar and / or He are separated from the exhaust flow by a selectively permeable membrane.

50. a. To oxidize any combination of the aqueous ammonia solution and the concentrated ammonia product to form a NOx-rich stream of nitrogen oxides (NOx), b. From the NOx flow, NO in water ２ It absorbs nitric acid (HNO ３ ) to generate an aqueous solution and a vapor flow, The method according to claim 1, further comprising:

51. A method for producing ammonia, wherein the method is a. H ２ to N ２ To mix with it and generate a mixed flow, b. Dewatering the combination of the mixed flow and the recycled flow to generate a dry flow, c. The H contained in the drying flow ２、 and N ２ This is reacted in a synthesis reactor to produce ammonia (NH ３ ) forming a elution stream, d. From the aforementioned elution flow, NH in water ３ It absorbs the aqueous ammonia solution and the unreacted H ２ , and N ２ To generate a recycling flow that contains, e. To control the accumulation of any inert species within the system, the fraction of the recycle flow is separated and a purge flow is generated. f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor to supply power for the dehydration and / or distillation, h. To oxidize any combination of the aqueous ammonia solution and the concentrated ammonia product to form a NOx-rich stream of nitrogen oxides (NOx), i. From the aforementioned NOx flow, NO in water ２ It absorbs nitric acid (HNO ３ ) to generate an aqueous solution and a vapor flow, Methods that include...

52. Said NH ３ The method according to claim 51, wherein the oxidation of generates heat, and the heat is captured in a hot oil, hot water, or steam system.

53. The method according to claim 52, wherein the captured heat is utilized within the process.

54. Said NH ３ The method according to claim 51, wherein the material is oxidized with oxygen in the presence of a catalyst.

55. The method according to claim 54, wherein the catalyst comprises a platinum group metal and optionally rhodium.

56. The method according to claim 54, wherein the catalyst comprises cobalt.

57. Nitrogen compounds, NO ２ The method according to claim 51, further comprising cooling the NOx flow while enabling continuous oxidation to the NOx.

58. Oxygen derived from electrolysis ２ Using nitrous oxide (N ２ Nitrogen oxides such as 0), and nitric oxide (NO), and nitrogen oxides such as nitrogen dioxide (NO) ２ The method according to claim 51, further comprising further oxidation to )

59. Oxygen derived from electrolysis ２ Using the O ２ A portion of the flow is ozonated, and the aforementioned partially ozonated flow is used to ozone (N2). ２ Nitrogen oxides such as 0), and nitric oxide (NO), and nitrogen oxides such as nitrogen dioxide (NO) ２ The method according to claim 51, further comprising further oxidation to )

60. O originates from air separation ２ Using nitrous oxide (N ２ Nitrogen oxides such as 0), and nitric oxide (NO), and nitrogen oxides such as nitrogen dioxide (NO) ２ The method according to claim 51, further comprising further oxidation to )

61. O originates from air separation ２ Using the O ２ A portion of the flow is ozonated, and the aforementioned partially ozonated flow is used to ozone (N2). ２ Nitrogen oxides such as 0), and nitric oxide (NO), and nitrogen oxides such as nitrogen dioxide (NO) ２ The method according to claim 51, further comprising further oxidation to )

62. HNO ３ The aqueous solution of is neutralized with any combination of the aqueous ammonia solution and the stream of concentrated ammonia product to form an aqueous solution of ammonium nitrate (NH ４ NO ３ ), the method according to claim 51.

63. The aforementioned HNO ３ The method according to claim 62, wherein the neutralization generates heat, and the heat is captured in a hot oil, hot water, or steam system.

64. The method according to claim 63, wherein the captured heat is utilized within the process.

65. The aforementioned HNO ３ The neutralization generates heat, and this heat is used to... ３ The method according to claim 62, wherein water contained in an aqueous solution is evaporated.

66. The aforementioned steam flow is processed, N ２ The method according to claim 51, wherein the compound is separated from other compounds.

67. The separated N ２ The method according to claim 66, wherein the material is recycled for ammonia synthesis.

68. The method according to claim 62, wherein the aqueous solution of ammonium nitrate is further concentrated or diluted by removing or adding water.

69. The method according to claim 62, wherein the aqueous solution of ammonium nitrate is granulated or converted to solid ammonium nitrate by another method.

70. The method according to claim 68, wherein a more concentrated or diluted aqueous solution of ammonium nitrate is granulated or otherwise converted into solid ammonium nitrate.

71. a. React any combination of the aqueous ammonia product and the concentrated ammonia product with CO ２ to form an eluate stream rich in urea (CH ４ N ２ O). b. Separating the aqueous urea solution from the aforementioned elution stream, The method according to claim 1, including the method described in claim 1.

72. A method for producing ammonia, wherein the method is a. H ２ to N ２ To mix with it and generate a mixed flow, b. Dewatering the combination of the mixed flow and the recycled flow to generate a dry flow, c. The H contained in the drying flow ２ , and N ２ This is reacted in a synthesis reactor to produce ammonia (NH ３ Forming a elution stream containing ) d. From the aforementioned elution flow, NH in water ３ It absorbs the aqueous ammonia solution and the unreacted H ２、 and N ２ To generate the aforementioned recycling flow containing, e. To control the accumulation of any inert species within the system, the fraction of the recycle flow is separated and a purge flow is generated. f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reaction to supply power to the dehydration and / or distillation, h. Any combination of the aqueous ammonia solution and the concentrated ammonia product is CO ２ It reacts with urea (CH ４ N ２ O) forms a rich elution flow, i. Separating the aqueous urea solution from the aforementioned elution stream, Methods that include...

73. The aforementioned CO ２ The method according to claim 72, wherein the exhaust gas is derived from the exhaust gas.

74. The aforementioned CO ２ The method according to claim 72, wherein the method is derived from biomass or waste fermentation.

75. The aforementioned CO ２ The method according to claim 72, wherein the fermentation of biomass (e.g., corn) for the production of ethanol.

76. The aforementioned CO ２ The method according to claim 72, wherein the method originates from an industrial facility (for example, natural gas processing).

77. The aforementioned CO ２ The method according to claim 72, wherein the product is supplied from a pipeline.

78. The aforementioned CO ２ The method according to claim 72, wherein the air is supplied directly from a DAC (Digital Air Recovery) system.

79. The aforementioned CO ２ The method according to claim 72, wherein the purity is less than 99% and greater than 80%.

80. The method according to claim 72, wherein the urea synthesis is carried out at a pressure exceeding 150 bar.

81. NH in the aforementioned supply flow ３ , and CO ２ The method according to claim 72, wherein the molar ratio of to urea synthesis is greater than about 2.

82. The method according to claim 72, wherein the urea aqueous solution is further concentrated in urea by removing water.

83. The method according to claim 82, wherein the concentrated urea solution is granulated or otherwise converted into solid urea.

84. The method according to claim 72, wherein the aqueous solution of urea is further diluted in urea by removing water to form diesel exhaust fluid (DEF).

85. a. Oxidizing the aqueous ammonia solution and a portion of the concentrated ammonia to form a NOx-rich stream of nitrogen oxides (NOx), b. From the NOx flow, NO in water ２ It absorbs nitric acid (HNO ３ ) to generate an aqueous solution and a vapor flow, c. The remaining portion of the aqueous ammonia solution and the concentrated ammonia, CO ２ It reacts with urea (CH ４ N ２ O) forms a rich flow, d. Separating the urea aqueous solution from the urea-rich flow, e. The aqueous solution of urea is converted to nitric acid (HNO ３ By combining it with an aqueous solution of ), a solution of ammonium urea nitrate (UAN) is formed. The method according to claim 1, further comprising:

86. A method for producing ammonia, wherein the method is a. H ２ to N ２ To mix with it and generate a mixed flow, b. Dewatering the combination of the mixed flow and the recycled flow to generate a dry flow, c. The H contained in the drying flow ２、 and N ２ This is reacted in a synthesis reactor to produce ammonia (NH ３ ) forming a elution stream, d. From the aforementioned elution flow, NH in water ３ It absorbs the aqueous ammonia solution and the unreacted H ２、 and N ２ To generate the aforementioned recycling flow containing, e. To control the accumulation of any inert species within the system, the fraction of the recycle flow is separated and a purge flow is generated. f. Distilling the aqueous ammonia solution to produce a more concentrated ammonia product, g. Using the heat generated by the ammonia synthesis reactor to supply power for the dehydration and / or distillation, h. Oxidizing the aqueous ammonia solution and a portion of the concentrated ammonia to form a NOx-rich stream, i. From the aforementioned NOx flow, NO in water ２ It absorbs nitric acid (HNO ３ ) to generate an aqueous solution and a vapor flow, j. The remaining portion of the flow, the aqueous ammonia solution, and the concentrated ammonia are mixed with CO ２ It reacts with urea (CH ４ N ２ O) forms a rich elution flow, k. Separating the urea aqueous solution from a urea-rich flow, l. The aqueous solution of urea is converted to nitric acid (HNO ３ By combining it with an aqueous solution of ), a solution of ammonium urea nitrate (UAN) is formed. Methods that further include this.

87. A system configured to carry out any method described in any one of the prior claims.

Images