System and method for production of gaseous products using cyclic reactors

Abstract

Systems and methods for production of gaseous products utilizing reaction vessels that integrate catalytic reaction and sorbent -based separation processes. The systems and methods may include introducing a reactant gas within a vessel containing a catalyst and sorbent, whereby the catalyst facilitates conversion of the reactant gas into a product species and the product species is selectively sorbed by the sorbent; withdrawing a first effluent stream from the vessel; and withdrawing a second effluent stream from the vessel that is enriched in the product species relative to the first effluent stream. The systems and methods may additionally be implemented using multiple reaction vessels operating in coordinated cycles to allow for continuous production and may be used in some variations for ammonia production where nitrogen and hydrogen reactants are converted to ammonia.

Description

SYSTEM AND METHOD FOR PRODUCTION OF GASEOUS PRODUCTSUSING CYCLIC REACTORSRELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Application 63 / 673,414 filed on July 19, 2024 and U.S. Provisional Application 63 / 694,561 filed on September 13, 2024, both of which are incorporated in their entirety by this reference.TECHNICAL FIELD

[0002] This invention relates generally to the field of production of gaseous products such as ammonia, and more specifically to new and useful systems and methods for production of gaseous products using cyclic reactors.BACKGROUND

[0003] Gaseous industrial products are typically produced in large, capital-intensive, centralized facilities. For example, the prevailing ammonia synthesis process in the market is the Haber-Bosch (H-B) process. The H-B process is capital intensive, resulting in its implementation via massive, centralized plants: there are approximately 400 plants worldwide, each producing approximately 1000 tons NH3 / day.

[0004] The current approach to producing ammonia is expensive and resource intensive. It has traditionally not been practical to build out small scale H-B process plants. Additionally, the process can be energy intensive and because of the large scale, it makes it challenging to use renewable energy sources. Because of the centralization of ammonia production, it also means ammonia must be transported to its destination further adding to the energy cost of ammonia use.

[0005] The current approach uses a steady state reactor that is limited by steady state reaction equilibrium. In particular, a low per-pass conversion results in a low concentration of ammonia exits the reactor, mandating an energy and capital intensive recycle process to separate the product from unreacted feedstocks.

[0006] Thus, there is a need in the field to create a new and useful system and method for production of ammonia and other gaseous industrial products.BRIEF DESCRIPTION

[0007] The present disclosure provides systems and methods with improved per pass conversions and product purities for the production of ammonia and other gaseous industrial products. Surprisingly, as described herein, closely coupling reaction synthesis and sorption of the product gas can improve per pass conversions and product purities.

[0008] In one aspect, the disclosed method for making a gaseous product comprises introducing a reactant gas within a vessel containing a catalyst and sorbent, whereby the catalyst facilitates a conversion of the reactant gas into a product species and the product species is selectively sorbed by the sorbent, withdrawing a first effluent stream from the vessel, and withdrawing a second effluent stream from the vessel, wherein the second effluent stream is enriched in the product species relative to the first effluent stream.

[0009] In some variations, the method further comprises, prior to introducing the reactant gas within the vessel, pressurizing the vessel. In some variations, the reactant gas comprises a first reactant species and a second reactant species, wherein the product species is formed from a reaction between the first reactant species and the second reactant species. In some variations, the vessel is pressurized with the first reactant species, an inert gas, or any combination thereof. In some variations, the vessel is pressurized with the first reactant species. In some variations, a pressure of the vessel is regulated at an outlet of the vessel while the reactant gas is introduced into the vessel.

[0010] In some variations, introducing a reactant gas into a vessel and withdrawing a first effluent stream from the vessel occur simultaneously. In some variations, withdrawing a second effluent stream from the vessel is performed subsequent to withdrawing a first effluent stream from the vessel. In some variations, the first effluent stream contains substantially no second reactant species. In some variations, the reactant gas is introduced into the vessel until the first effluent stream contains more than 1 vol% of the second species. In some variations, the first effluent stream containssubstantially no product gas. In some variations, the reactant gas is introduced into the vessel until the first effluent stream contains more than 1 vol% of the product gas.[oon] In some variations, the reactant gas is introduced into the vessel until a flow rate of the first effluent stream is substantially constant. In some variations, the reactant gas is introduced into the vessel until a pressure drop across the vessel is substantially constant. In some variations, the reactant gas is introduced into the vessel for a period of time between about 1 and about 100 residence times. In some variations, the reactant gas is introduced into the vessel for a period of time between about 1 and about 20 residence times. In some variations, the reactant gas flow has a gas hourly space velocity less than about 10,000 / hr. In some variations, the reactant gas flow has a gas hourly space velocity less than about 5,000 / hr. In some variations, the Reynold's number of the reactant gas in the vessel is greater than about 5. In some variations, the reactant gas is introduced at a pressure between about 10 and about 50 bar.

[0012] In some variations, the method further comprises introducing a rinse gas comprising the product species into the vessel prior to withdrawing a second effluent stream from the vessel. In some variations, the method further comprises subsequently to withdrawing the first effluent stream from the vessel reducing a pressure of the vessel to a blowdown pressure and withdrawing a blowdown stream from the vessel, and optionally prior to reducing the pressure to the blowdown pressure, reducing a pressure of the vessel to a depressurization pressure which is greater than the blowdown pressure and withdrawing a depressurization stream from the vessel. In some variations, the pressure is reduced to the depressurization pressure before being reduced to the blowdown pressure. In some variations, the depressurization stream comprises primarily the reactant gas. In some variations, the blowdown stream comprises at least 5% of the product gas.

[0013] In some variations, the second effluent stream is withdrawn in a direction substantially co-current to a direction at which the reactant gas is introduced into the vessel. In some variations, the second effluent stream is withdrawn from the vessel through multiple outlets. In some variations, at least one outlet is configured such that a flow path of the second effluent stream is substantially co-current to a direction at which the reactant gas flows through the vessel. In some variations, the reactant gas isintroduced through a first material port in the vessel, and the second effluent stream is withdrawn from a second material port of the vessel. In some variations, the reactant gas is introduced through a first material port in the vessel, and the second effluent stream is withdrawn from the first material port.

[0014] In some variations, the method further comprises introducing a sweep gas into the vessel while withdrawing the second effluent stream from the vessel. In some variations, the sweep gas comprises a reactant species. In some variations, the sweep gas comprises primarily H2. In some variations, the sweep gas has a velocity greater than that of the reactant gas. In some variations, the first effluent stream is at a pressure greater than or equal to the second effluent stream. In some variations, the method further comprises directing the first effluent stream to a recompression operation. In some variations, the method further comprises directing the second effluent stream to a separation operation. In some variations, the sweep gas is introduced until an outlet partial pressure of the product species is less than about 0.4 bar at an outlet from the vessel. In some variations, a temperature in the vessel is reduced prior to withdrawing the second effluent stream. In some variations, the sweep gas is introduced at a flowrate less than or equal to a fluidization velocity of the catalyst and sorbent. In some variations, the reactant gas has at least about 5% of the product species.

[0015] In some variations, the method further comprises introducing the first effluent stream to a second vessel containing a catalyst and a sorbent, whereby the first effluent stream is a reactant gas for the second vessel. In some variations, the method further comprises introducing the first effluent stream to a second vessel containing a catalyst and a sorbent, whereby the first effluent stream is used to pressurize the second vessel. In some variations, the method further comprises introducing the first effluent stream to a second vessel containing a catalyst and a sorbent, whereby the first effluent stream is used as the sweep gas the second vessel. In some variations, the method further comprises introducing the depressurization stream to a second vessel containing a catalyst and a sorbent, whereby the depressurization stream is a reactant gas for the second vessel. In some variations, the method further comprises introducing the depressurization stream to a second vessel containing a catalyst and a sorbent, whereby the depressurization stream is used to pressurize the second vessel. In some variations,the method further comprises introducing the depressurization stream to a second vessel containing a catalyst and a sorbent, whereby the depressurization stream is used as the sweep gas the second vessel.

[0016] In some variations, the product species is ammonia. In some variations, the vessel is pressurized with a pressurizing gas comprising H2, N2, an inert gas, or any combination thereof. In some variations, the first effluent stream contains primarily nitrogen gas. In some variations, the first effluent stream contains substantially no hydrogen. In some variations, the first effluent stream contains primarily hydrogen gas. In some variations, the first effluent stream contains substantially no nitrogen. In some variations, the first effluent stream has substantially the same composition as the reactant gas. In some variations, the first effluent stream has substantially the same composition as the pressurization gas. In some variations, the sorbent sorbs ammonia. In some variations, the catalyst converts H2 and N2 into NH3. In some variations, the reactant gas comprises a reactant species that is H2. In some variations, the reactant gas comprises a reactant species that is N2. In some variations, the reactant gas comprises H2 and N2. In some variations, the reactant gas comprises H2 and N2 and NH3.

[0017] In one aspect, the disclosed system for production of a product species comprises a set of reaction vessels, each reaction vessel comprising a vessel body comprising an input material port for receiving a reactant gas and an exit material port for withdrawing an effluent stream, a reaction bed within the vessel that comprises a sorbent and / or a catalyst, wherein the catalyst facilitates a conversion of the reactant gas to a product species and the sorbent sorbs the product species, a material conduit system configured to introduce the reactant gas to each of the set of reaction vessels through the input material ports and withdraw the effluent stream from each of the set of reaction vessels through their exit material ports, a control system configured to, for each of the reaction vessels, iteratively, introduce the reactant gas to the reaction vessel and withdraw the effluent stream from the reaction vessel, wherein, the reactant gas provided to the set of reaction vessels has a substantially constant flow rate.

[0018] In some variations, the product gas withdrawn from the set of reaction vessels has a substantially constant flow rate. In some variations, the material conduit system is further configured to transfer materials between vessels of the set of reaction vessels. Insome variations, the vessels in the set of reaction vessels are interconnected by a shared header and by a shared footer. In some variations, the system further comprises a surge tank in fluidic communication with the vessels. In some variations, a portion of the set of reaction vessels comprises a cluster of vessels. In some variations, a cluster of vessels share an inlet gas feed. In some variations, the vessels are configured such that an outlet gas of one vessel is directed to another vessel. In some variations, said directing does not use a compressor. In some variations, a portion of the set of reaction vessels are heated and cooled by a shared reservoir of a heat transfer fluid. In some variations, the effluent streams from the exit material ports of the set of reaction vessels are combined into a combined effluent stream that provides substantially continuous product gas production from the set of reaction vessels.

[0019] In some variations, the control system is configured to decrease production of the product species by selectively reducing or eliminating flow of the reactant gas to one or more vessels. In some variations, vessels undergo stages of a reactive PSA process in a scheduled sequence. In some variations, the stages of the reactive PSA process comprise a synthesis operation and a desorption operation. In some variations, vessels simultaneously undergoing the same stage of the reactive PSA process do not pass a gas between each other. In some variations, the control system is configured to coordinate the stages across multiple reaction vessels such that inputs from one stage are at least partially supplied by an output of a reaction vessel in a different stage. In some variations, the reaction bed in a vessel comprises a catalyst and a sorbent in a mass ration of about 1:4 to 4:1 catalyst to sorbent. In some variations, the reaction bed in a vessel comprises a catalyst and a sorbent in a mass ration of about 1:1 catalyst to sorbent. In some variations, the reaction vessels comprise tubular reaction beds. In some variations, the reaction vessels are configured for heat transfer between a reaction zone and a heat transfer fluid. In some variations, at least one reaction vessel includes a reaction bed with both a catalyst and a sorbent.

[0020] In some variations, the sorbent comprises an absorbent. In some variations, the sorbent comprises an adsorbent. In some variations, the adsorbent comprises a material selected from the group consisting of zeolite, silica, alumina, metal-organic framework (MOF), covalent organic framework (COF), and zeolitic imidazolateframework (ZIF). In some variations, the catalyst comprises an active component selected from the group consisting of Ru, Fe, and oxides thereof. In some variations, each reaction vessel uses a substantially similar sorbent and catalyst. In some variations, the reaction vessels comprise sub-chambers, wherein each sub-chamber acts as its own reaction vessel. In some variations, the reaction vessels comprise distinct system components that are housed separately and interconnected through the conduit system.

[0021] In one aspect, the disclosed method for making a gaseous product comprises iteratively performing a synthesis operation, wherein a reactant gas comprising a reactant species is introduced to a reaction vessel containing a catalyst and a sorbent, wherein the catalyst facilitates conversion of reactant species into a product species and the sorbent sorbs the product species, and performing a desorption operation, wherein the product species desorbs from the sorbent and a product gas comprising the product species is withdrawn from the reaction vessel.

[0022] In some variations, a set of reaction vessels each iteratively perform the synthesis operation and the desorption operation. In some variations, the desorption operation comprises performing a blowdown operation, wherein a pressure of the vessel is reduced to a blowdown pressure and a blowdown stream is withdrawn from the vessel, and optionally prior to reducing the pressure to the blowdown pressure, performing a depressurization operation, wherein a pressure of the vessel is reduced to a depressurization pressure which is greater than the blowdown pressure and a depressurization stream is withdrawn from the vessel. In some variations, the depressurization operation is performed. In some variations, the blowdown stream is a product gas stream. In some variations, the depressurization stream is a product gas stream. In some variations, the method further comprises performing a repressurization operation in which a re-pressurization gas is introduced to the reaction vessel. In some variations, the desorption operation comprises a sweep operation, comprising introducing a sweep gas to the vessel and withdrawing a sweep stream from the vessel. In some variations, the sweep stream is a product gas stream. In some variations, the method further comprises performing a rinse operation subsequent to the synthesis operation, wherein performing the rinse operation comprises introducinga rinse gas comprising the product species to the vessel. In some variations, a synthesis effluent stream is withdrawn from the reaction vessel during the synthesis stage.

[0023] In some variations, a first reaction vessel of the set of reaction vessels is performing the synthesis operation while a second reaction vessel of the set of reaction vessels is performing the desorption operation. In some variations, about one third of the set of reaction vessels are performing the synthesis operation at a given time. In some variations, more than about one third of the set of reaction vessels are performing the synthesis operation at a given time. In some variations, about half of the set of reaction vessels are performing the synthesis operation at a given time. In some variations, the reactant gas is introduced to the set of reaction vessels with a substantially constant flowrate. In some variations, the product gas is withdrawn from the set of reaction vessels at a substantially constant flowrate. In some variations, a portion of the set of reaction vessels comprise a cluster of reaction vessels, and wherein each vessel of a cluster undergoes a same process operation at a given time. In some variations, the synthesis operation and the desorption operation are performed for an approximately equal length of time. In some variations, the synthesis operation and the sweep operation are performed for an approximately equal length of time. In some variations, the synthesis operation is performed for a longer length of time than the desorption operation. In some variations, the synthesis operation and the repressurization operation are performed for an approximately equal length of time.

[0024] In some variations, the method further comprises terminating the synthesis stage upon satisfying a synthesis saturation condition. In some variations, iteration between synthesis and desorption operations is controlled by length of time. In some variations, iteration between synthesis and desorption operations is controlled by a variation in pressure. In some variations, the synthesis saturation condition is satisfied when an inlet pressure reaches a substantially constant value. In some variations, iteration between synthesis and desorption operations is controlled by a variation in an outlet flowrate. In some variations, the synthesis saturation condition is satisfied when an outlet flowrate begins to increase after reaching a substantially minimum value. In some variations, iteration between synthesis and desorption operations is controlled by a variation in a gas composition. In some variations, the synthesis saturation conditionis satisfied when a concentration of unreacted feedstock in an outlet stream begins to increase after reaching a substantially minimum value.

[0025] In some variations, the depressurization stream from a first reaction vessel is used as the reactant gas to a second reaction vessel. In some variations, the depressurization stream from a first reaction vessel is used as the re-pressurization gas to a second reaction vessel. In some variations, the depressurization stream from a first reaction vessel is used as the sweep gas to a second reaction vessel. In some variations, the synthesis effluent stream from a first reaction vessel is used as the reactant gas to a second reaction vessel. In some variations, the synthesis effluent stream from a first reaction vessel is used as the re-pressurization gas to a second reaction vessel. In some variations, the synthesis effluent stream from a first reaction vessel is used as the sweep gas to a second reaction vessel.

[0026] In some variations, each vessel of the set of vessels is maintained at a temperature within about 5O°C of an average temperature. In some variations, a first vessel of the set of vessels is maintained at a temperature within about 5O°C of a second vessel of the set of vessels. In some variations, the synthesis operation is performed at about 35O-45O°C. In some variations, the desorption operation is performed at about 35O-45O°C. In some variations, the synthesis operation and the desorption operation are performed at about the same temperature. In some variations, a reaction vessel is cooled during the synthesis operation. In some variations, a reaction vessel exchanges heat with a reactant gas. In some variations, a reaction vessel is heated during the desorption operation. In some variations, a reaction vessel is substantially adiabatic during the desorption operation. In some variations, the desorption operation is performed at about 1O-5O°C above the synthesis operation. In some variations, performing the desorption process comprises desorbing into a hydrogen rich gas.

[0027] In one aspect, the disclosed method comprises managing material communication between a set of reaction vessels and thereby cycling a set of reaction vessels through different stages of ammonia synthesis and separation, which comprises for each reaction vessel reacting nitrogen and hydrogen with a catalyst to capture ammonia in a sorbent of the reaction vessel, rinsing the reaction vessel, performingdesorption process in the reaction vessel, purging the reaction vessel, and / or repressurizing the reaction vessel.

[0028] In one aspect, the disclosed system comprises a set of reaction vessels, with each reaction vessel including at least a sorbent or catalyst, a material stream conduit system, the set of reaction vessels integrated through material stream conduit system, and a control system configured to cooperatively manage cycling of the set of reaction vessels and material flow between reaction vessels through the conduit system.BRIEF DESCRIPTION OF DRAWINGS

[0029] FIGURE 1 and 2 are schematic representations of system variations.

[0030] FIGURE 3 is a detailed schematic representation of a reaction vessel.

[0031] FIGURE 4 is a detailed cross-sectional view of integrated reaction vessels.

[0032] FIGURE 5 is a flowchart representation of a method.

[0033] FIGURES 6A-6D are flowchart representations of exemplary vessel cycle sequence variations.

[0034] FIGURES 7-14 are detailed diagrams of vessels undergoing different cycle state variations.

[0035] FIGURES 15-18 are detailed diagrams of a set of vessels and the interactions between vessels for a first exemplary implementation.

[0036] FIGURES 19-21 are detailed diagrams of a set of vessels and the interactions between vessels for a second exemplary implementation.

[0037] FIGURE 22 includes two exemplary charts illustrating measured equilibrium ammonia capacity vs ammonia pressure for (a) zeolite NaX and (b) zeolite Mg- ZSM-5.

[0038] FIGURE 23 is an exemplary representation of data results from cycle with Na- X sorbent and Ru catalyst.

[0039] FIGURE 24 is a schematic representation of a process scheme variation including recycle compressor.

[0040] FIGURE 25 is a schematic representation of a process scheme variation including three reaction vessels.

[0041] FIGURE 26 is a schematic representation of an operations schedule for a process scheme variation including three reaction vessels.

[0042] FIGURE 27 is a schematic representation of a process scheme variation including six reaction clusters.

[0043] FIGURE 28 is a schematic representation of an operations schedule for a process scheme variation including six reaction clusters.

[0044] FIGURE 29 is an exemplary representation of data results from a cycle with re-pressurization, synthesis, blowdown, and purge operations.

[0045] FIGURE 30 is an exemplary representation of data results for percent conversion of H2 for ten cycles.

[0046] FIGURES 31-33 are flowchart representations of method variations for gaseous product production.

[0047] FIGURE 34 is a schematic representation of a reaction vessel of a system variation.DETAILED DESCRIPTION

[0048] The following description of the embodiments of the invention is not intended to limit the invention to these embodiments but rather to enable a person skilled in the art to make and use this invention.Overview

[0049] The systems and methods described herein provide approaches for production of gaseous products using reaction vessels that integrate catalytic reaction and sorbent-based separation processes. The systems and methods utilize reaction vessels containing reaction beds with catalysts and / or sorbents to facilitate conversion of reactant gases into product species that may be sorbed into the reaction bed and subsequently withdrawn in an effluent stream as a product stream. The disclosed systems and methods allow for reaction vessels to produce multiple distinct effluent streams with different compositions depending on the operational state of the vessel.

[0050] The systems and methods may be particularly well-suited for ammonia production, where nitrogen (N2) and hydrogen (H2) reactant species maybe introducedas a reactant gas within a reaction vessel and converted to ammonia (NH3) product species through catalytic reaction, and the ammonia may then be selectively sorbed by sorbents within the same reaction bed. In ammonia production applications, the systems and methods may produce first effluent streams enriched in unreacted nitrogen and / or hydrogen, and a second effluent stream enriched in ammonia product.

[0051] More broadly, reactant gases containing one or more reactant species may be introduced to reaction vessels, either simultaneously or in stages through input streams of different compositions. Catalysts within the reaction vessel facilitate conversion of the reactant gas into product species, which are then selectively sorbed by sorbents within the reaction bed. Through controlled cycling of operational states, including synthesis operations and desorption operations, the reaction vessels can produce multiple distinct effluent streams with different compositions. In one application of the systems and methods, the reactant gas may include reactant species nitrogen and hydrogen for the synthesis and sorbing of ammonia, wherein an effluent stream may include product gas containing ammonia as a product species, but his approach may alternatively be used for other gaseous product applications.

[0052] The systems and methods may be implemented using single reaction vessels but the systems and method may additionally be used in a multi -vessel configuration. In multi-vessel variations, material streams (input material streams or output effluent streams) can be shared between vessels, enabling coordinated operation where effluent streams from vessels in one operational state serve as input streams for vessels in different operational states. For ammonia production, this can include using nitrogenrich effluent streams from one vessel to pressurize another vessel, or using hydrogenrich streams as sweep gases. Control systems can manage these multi-vessel configurations to provide substantially continuous ammonia production while enabling scalable operations that can be adjusted based on available inputs, desired outputs, energy capacities, or other operational requirements.

[0053] In particular, the systems and methods described herein may provide a method of ammonia production using sorbent -based reactors, which as discussed may have applications to other gaseous product production. The systems and methods can use a multistage ammonia synthesis process. The multistage synthesis process mayadditionally be used across multiple reaction vessels such that cycle management of the synthesis process orchestrated across the reaction vessels can further enhance production.

[0054] The systems and methods may result in a low temperature, low pressure thermochemical ammonia synthesis process. The systems and methods may lead to a reduced capital expenditure for ammonia production or other gaseous product production depending on configuration and application of the systems and methods.

[0055] The systems and methods can use a synthesis process that integrates use of a catalyst and a sorbent. A catalyst can facilitate reacting nitrogen (N2) and hydrogen (H2) to form ammonia (NH3), which then is sorbed into and / or onto a sorbent. More generally, catalysts can facilitate reacting reactant species of a reactant gas established within the reaction vessel to form product species, which may then be sorbed by sorbents. In the case of ammonia production, the near-instantaneous removal of NH3 (or other product species) by the sorbent may keep the reaction from reaching gas-phase equilibrium, improving rates of ammonia production or other product species production and conversion efficiencies at low temperature and pressure.

[0056] The systems and methods described herein may make use of a reaction vessel with an integrated reaction bed, which can include a sorbent (e.g., an absorbent or an adsorbent). In some variations, the reaction bed of at least some reaction vessels may include a catalyst.

[0057] The synthesis process may be performed in a semi-batch and / or flow-through manner where ammonia may be initially produced and sorbed into a sorbent bed until reaching some saturation level. Then, the pressure can be reduced, triggering desorbing of the ammonia thereby releasing an ammonia enriched output stream from the reaction.

[0058] Coordinated production may be used to make continuous gaseous product production such as ammonia production. The systems and methods may implement the synthesis process across multiple reaction vessels. Different subsets of the reaction vessels may be cycled through the synthesis cycle stages (also referred to herein as operations) so that they coordinate different cycle stages for enhanced performance.This may include managing alignment of exothermic and endothermic reactions and / or sharing of output feeds for example.

[0059] The system and method may provide a number of potential benefits. The system and method are not limited to always providing such benefits and are presented only as exemplary representations for how the system and method may be put to use. The list of benefits is not intended to be exhaustive and other benefits may additionally or alternatively exist.

[0060] As one potential benefit, the systems and methods may reduce the cost of ammonia synthesis. Current Haber-Bosch ammonia production is capital intensive and can depend on having massive, centralized plants. The systems and methods described herein can result in ammonia synthesis using lower temperature and pressures which can reduce material and compression demands. This can reduce cost of implementation. Additionally, the systems and methods may be implemented at smaller scales. Such benefits may similarly be used for other gaseous product production.

[0061] As another related benefit, the systems and methods may reduce the system requirements traditionally needed during ammonia production or other gaseous product production. For example, the systems and methods may reduce or eliminate the need of a recycle compressor and may downgrade condensation separation duty.

[0062] As another benefit, the systems and methods, partially due to their ability to lower cost, may be built at smaller scales allowing for better integration with renewable electricity sources. In some variations, ammonia or other gaseous product production using the systems and methods described herein may scale production to match renewable power outputs to avoid needing or at least minimizing non-renewable energy sources. Additionally or alternatively, the smaller scale and more cost-effective system may make ammonia production possible onsite at customer locations. This can allow for ammonia production near where source materials are produced and / or where ammonia output is used. This may eliminate or reduce transportation costs and energy expenditures.

[0063] As another potential benefit, the use of a sorbent in combination with a catalyst may lead to enhancements of catalyst kinetics.

[0064] As another potential benefit, the systems and methods may allow for condensing and production of high-purity ammonia or other gaseous products.

[0065] As another potential benefit, the systems and methods may enhance efficiencies by using effluent from one reactor within another reactor.

[0066] As another potential benefit, the systems and methods may allow for scalable production. Parallelization of different reaction vessels by a system or method can allow production to ramped up or down to meet material supply and / or output demand. This may be particularly helpful when operating with variable energy sources such as renewable resources. The systems and methods may be able to run at varying degrees of production and these could be scaled up and down depending on energy availability.

[0067] As another potential benefit, the systems and methods maybe substantially isothermal in their sorbing and desorbing. This may allow an operating system to avoid large temperature swings, especially between cycle modes (e.g., a synthesis operation, a desorption operation). The systems and methods may have exothermic and endothermic reactions that are implemented in a complementary way so that the overall system can be kept nearly isothermal. In some variations, a system may run isothermally, where all vessels are at a substantially constant temperature at all times, wherein “constant” temperature maybe characterized as maintaining a temperature with + / - io°C or alternatively within + / - 3O°C or alternatively within + / - 5O°C. In some embodiments, the temperature is maintained within about + / - 5O°C. In general, the systems and methods maybe operated and / or maintained in a temperature range of 25O-4OO°C, 28O-34O°C, 35O-4OO°C, 35O°C - 5OO°C, 35O°C-45O°C, or 25O-45O°C. In some embodiments the systems and methods maybe operated and / or maintained at a temperature of about 375°C. In some embodiments the systems and methods maybe operated and / or maintained at a temperature of about 4OO°C. In some embodiments the systems and methods may be operated and / or maintained at a temperature of about 35O°C. In some embodiments the systems and methods maybe operated and / or maintained at a temperature of from about 375°C to about 425°C. In some embodiments the systems and methods maybe operated and / or maintained at a temperature of from about 35O°C to about 4OO°C. Lower temperatures may have an added benefit of added sorbent capacity and reduced vessel and pipe costs. Highertemperatures, such as temperatures above 3OO°C or 35O°C may enhance catalyst kinetics but reduce the equilibrium driving force for reaction. Catalysts with lower reaction temperature ranges maybe used.

[0068] In addition to these potential benefits, some system and method variations may make use of sorbents within a reaction vessel. As used herein, sorbents include adsorbents and absorbents. A sorbent used within a reaction bed maybe cheaper and more commercially available. A sorbent may also exhibit higher durability such as better cycle life, thermal stability, and / or less moisture sensitivity. A sorbent in some variations may also provide faster kinetics for sorption and desorption. Also, sorbents may exhibit linear phase relationship allowing better control over pressure for liquifying. Sorbing and desorbing may happen proportionally to a varied pressure and / or temperature. This may open more options for calibrating pressure and temperature for enhanced efficiencies.Systems for gaseous product production

[0069] The systems described herein provide physical infrastructure and control capabilities necessary to implement the methods for gaseous product production described herein. The systems may be implemented with a single reaction vessel or multiple reaction vessels. The system components include reaction vessels containing catalysts and / or sorbents, material conduit systems for managing gas flow, and control systems for coordinating operational states. These systems allow for the cyclic operational processes, material flow management strategies, and inter-vessel coordination that achieve enhanced gaseous product production through integrated reaction-sorption approaches.

[0070] Referring to FIGURE 34, presented herein is a system for production of a product gas may include a set of reaction vessels 110, a material conduit system 120, and a control system 130. Each reaction vessel of the set of reaction vessels 110 may include a vessel body comprising an input material port for receiving a reactant gas and an exit material port for withdrawing an effluent stream, and a reaction bed within the vessel that comprises a sorbent and / or a catalyst, wherein the catalyst facilitates a conversion of the reactant gas into product species and the sorbent sorbs the product species. Thematerial conduit system 120 is configured to introduce the reactant gas to each of the set of reaction vessels through the input material ports and withdraw the effluent stream from each of the set of reaction vessels through their exit material ports. The control system 130 is configured to, for each of the reaction vessels, iteratively introduce the reactant gas to the reaction vessel and withdraw the effluent stream from the reaction vessel, wherein the effluent stream in at least one operation state comprises a product gas, wherein the reactant gas provided to the set of reaction vessels has a substantially constant flow rate. In a multi -vessel system, different reaction vessels may have different configurations such as different reaction beds.

[0071] The set of reaction vessels 110 function as a plurality of individually operated reaction vessels for gaseous product production. Each reaction vessel includes the physical infrastructure necessary to implement the synthesis, desorption, and other operational states described in the method sections herein. The reaction vessels provide the contained environment where reactant gases undergo catalytic conversion to product species, where product species are sorbed by sorbents, and where product species are subsequently desorbed and recovered as product gas streams.

[0072] A portion of the set of reaction vessels may comprise a cluster of vessels, allowing for capacity scaling while maintaining manageable individual vessel sizes and simplifying control systems. A cluster of vessels functions as a group of vessels that share inlet gas feeds and undergo the same process operations at the same time, essentially operating as parallel vessels. Clustering provides an alternative to upsizing individual reaction vessels to increase system capacity, which may be advantageous for maintaining vessel sizes within manufacturing and shipping constraints, such as keeping vessel diameters less than about 2.5 meters for ease of manufacturing and transportation for example.

[0073] The reaction bed in a vessel may comprise a catalyst and a sorbent in various mass ratios to optimize performance for specific applications. The mass ratio of catalyst to sorbent maybe about 1:4 to 4:1, preferably about 1:1, or about 2:1, depending on the specific gaseous product being produced and the desired balance between reaction rate and sorption capacity.

[0074] The reaction vessels may comprise tubular reaction beds, providing an elongated flow path that allow for sufficient residence time for both reaction and sorption processes. The tubular configuration facilitates uniform flow distribution and allows for efficient heat and mass transfer throughout the reaction bed. The reaction vessels may be configured for heat transfer between a reaction zone and a heat transfer fluid, enabling thermal management during the exothermic synthesis and endothermic desorption operations described in the method sections.

[0075] At least one reaction vessel includes a reaction bed with both a catalyst and a sorbent, enabling the integrated reaction-sorption process that achieves enhanced conversion efficiencies. The sorbent may comprise an adsorbent or an absorbent, depending on the specific application and desired sorption characteristics. The adsorbent may comprise a material selected from the group consisting of zeolite, silica, alumina, metal-organic framework (MOF), covalent organic framework (COF), and zeolitic imidazolate framework (ZIF), with zeolites being particularly effective for ammonia sorption applications. In some embodiments the sorbent may comprise an adsorbent. In some embodiments the sorbent may comprise a zeolite. The absorbent may comprise a metal-halide, MOF, COF, or combination of absorbent and adsorbent, with MgBr2 supported on silica being particularly effective for ammonia sorption applications.

[0076] The catalyst may comprise an active component selected from the group consisting of Ru, Fe, Co, and oxides thereof, which are effective for various gaseous product synthesis reactions including ammonia synthesis. In ammonia production applications, ruthenium-based and iron-based catalysts may be used for converting nitrogen and hydrogen to ammonia under the operating conditions described herein. Any catalyst configured for ammonia synthesis may be suitable.

[0077] Each reaction vessel may use a substantially similar sorbent and catalyst to ensure consistent performance across the set of reaction vessels, simplifying system operation and maintenance. Here substantially similar sorbent and catalyst compositions may include the same materials with mass ratios that vary by no more than 5-10%. The reaction vessels may comprise sub-chambers, wherein each subchamber acts as its own reaction vessel, enabling multiple parallel reaction zones withina single physical vessel structure. This configuration can provide operational flexibility and allow for different portions of a vessel to operate in different phases of the operational cycle.

[0078] The reaction vessels may comprise distinct system components that are housed separately and interconnected through the conduit system, providing flexibility in system layout and enabling modular system construction. This separated housing approach facilitates maintenance, allow for independent operation of vessels, and allows for system expansion by adding additional vessels as needed.

[0079] The material conduit system 120 functions to manage flow of reactant gas streams to the set of reaction vessels and effluent streams from the set of reaction vessels. The conduit system may provide the piping, valving, and / or flow control infrastructure necessary to implement the material flow strategies described in the method sections, including the ability to direct different stream compositions to and from reaction vessels based on their operational states. The material conduit system allows for both single vessel operations and coordinated multi -vessel operations through controlled routing of material streams.

[0080] The system maybe configured such that the reactant gas introduced to the set of reaction vessels has a substantially constant flow rate, enabling steady delivery of gaseous feedstocks from upstream operations. The system may be configured such that the product gas withdrawn from the set of reaction vessels has a substantially constant flow rate, enabling steady delivery of gaseous products to downstream operations. This substantially constant reactant gas and / or product gas flow is achieved through coordinated scheduling of vessel operations, where different vessels are in different operational states such that product gas withdrawal from some vessels compensates for periods when other vessels are not producing product gas.

[0081] The material conduit system may be further configured to transfer materials between vessels of the set of reaction vessels, enabling the material sharing strategies described in the method sections. This inter-vessel material transfer capability allows effluent streams from vessels in one operational state to serve as input streams for vessels in different operational states, improving overall material utilization and systemefficiency. The material transfer configuration allows for the cascaded material flows and pressure equalization strategies that enhance overall system performance.

[0082] The vessels in the set of reaction vessels may be interconnected by one or more shared header and by one or more shared footers, providing a common infrastructure for material distribution and collection. The shared header system allows for distribution of reactant gas and other input streams to multiple vessels, while the shared footer system allow for collection of effluent streams from multiple vessels. This shared infrastructure simplifies system design and operation while enabling flexible material routing between vessels in different operational states.

[0083] The system may further include one or more surge tanks in fluidic communication with the vessels, providing buffering capacity to smooth flow variations and allow for more stable operation. The surge tank can accommodate the pulsed nature of some operational states, such as blowdown operations, while maintaining more continuous flow to and from the overall system. In ammonia production applications, surge tanks can provide buffering for both reactant gas supply and ammonia product collection, enabling substantially constant flow rates despite the cyclic nature of individual vessel operations.

[0084] The vessels maybe configured such that an outlet gas of one vessel is directed to another vessel, enabling the inter-vessel material sharing described in the method sections. This direct vessel-to-vessel connection allow for efficient material transfer without intermediate storage or processing. In some variations, this directing of outlet gas from one vessel to another vessel does not use a compressor, enabling direct pressure-driven flow between vessels when pressure differentials are suitable for the desired material transfer.

[0085] The direct interconnection without compression is particularly advantageous when the outlet pressure of a first vessel exceeds the inlet pressure condition of a second vessel, such as when directing depressurization streams or synthesis effluent streams to vessels undergoing re-pressurization or sweep operations. This configuration minimizes energy consumption and system complexity while enabling effective material reuse.

[0086] The control system 130 functions to coordinate the operational states of the reaction vessels and manage the material flow through the conduit system. The controlsystem allows for the iterative cycling of reaction vessels through synthesis, desorption, and other operational states while maintaining substantially constant reactant gas flow rates to the system. The control system coordinates the timing and sequencing of operations to allow for the enhanced gaseous product production achievable through the integrated reaction-sorption approach. The control system may also manage gaseous product production within an individual reaction vessel.

[0087] The effluent streams from the exit material ports of the set of reaction vessels may be combined into a combined effluent stream that provides substantially continuous product gas production from the set of reaction vessels. The control system manages the timing and coordination of vessel operations, for example, to ensure that product gas is continuously available from at least some vessels in the set, even as individual vessels cycle through operational states that do not produce a product gas, such as repressurization and in some cases synthesis.

[0088] The control system may be configured to decrease production of the product species by selectively reducing or eliminating flow of the reactant gas to one or more vessels. This production control capability allows for the system to respond to varying demand for product gas, changes in feedstock availability, or variations in energy supply such as from renewable energy sources. The ability to selectively control individual vessels provides operational flexibility and allow for load following operation.

[0089] The vessels may undergo stages of a reactive pressure swing adsorption / absorption (PSA) process in a scheduled sequence, with the control system managing the progression through synthesis, desorption, re-pressurization, and other operational stages. The stages of the reactive PSA process may include a synthesis operation and a desorption operation as primary stages, with additional stages such as rinse, purge, and re-pressurization operations as described in the method sections. The control system coordinates these stages across multiple vessels to maintain continuous operation.

[0090] In some variations, vessels simultaneously undergoing the same stage of the reactive PSA process may not pass a gas between each other, maintaining independence during parallel operations. However, the control system may be configured to coordinate the stages across multiple reaction vessels such that inputs from one stageare at least partially supplied by an output of a reaction vessel in a different stage. This coordinated staging may allow for the material sharing and thermal integration strategies described in the method sections.

[0091] The control system may manage the scheduling and sequencing to optimize or enhance both individual vessel performance and overall system efficiency. The coordination may allow for vessels in exothermic synthesis operations to provide thermal energy for vessels in endothermic desorption operations, while vessels producing reactant -rich effluent streams can supply other vessels requiring reactant gas input.

[0092] In some variations, a portion of the set of reaction vessels may be heated and cooled by a shared reservoir of a heat transfer fluid, enabling thermal integration between vessels undergoing different operational states. The shared heat transfer fluid system allows exothermic operations in some vessels to provide heating for endothermic operations in other vessels, improving overall energy efficiency. The heat transfer fluid may circulate between vessels to transfer heat from vessels in synthesis mode to vessels in desorption mode, enabling more isothermal operation across the system while reducing external heating and cooling requirements.

[0093] In a variation of the systems described herein, as shown in FIGURE 1, a system for production of ammonia using sorbent -based reactors may include a set of reaction vessels 110 integrated through a material stream conduit system 120 and a control system 130 configured to cooperatively manage cycling of the set of reaction vessels and material flow between reaction vessels through the conduit system.

[0094] The system may include different alternative variations that may make use of differing configuration variables such as number reaction vessels, types of reaction vessels (e.g., reaction bed type, sorbent type, etc.), and / or interconnections between reaction vessels, and / or auxiliary equipment such as compressors and condensers, for example such as shown in FIGURE 2.

[0095] As described above, the set of reaction vessels function as a plurality of individually cycled reaction vessels. Each of the reaction vessels may be used in at least some portion of sorbent-based production and / or refinement of ammonia.

[0096] The set of reaction vessels may, in one variation, be distinct separated reaction vessels, which are preferably interconnected through the conduit system or at least share source inputs and / or stream outputs.

[0097] In some variations, the plurality of reaction vessels may be homogeneous.

[0098] During operation, the set of reaction vessels can be controlled such that production cycling is staggered and coordinated such that subsets (referred to herein as clusters) of the reaction vessels are operated at different cycle states (i.e., with non- homogeneous cycle-state). This maybe used to allow sharing of material effluence from one reaction vessel as an input stream for another reaction vessel. However, in some variations, the set of reaction vessels may be operated with parallel synchronized cycle states (i.e., homogenous cycle state).

[0099] In some variations, at least a portion of the set of reaction vessels may be configured as a cluster. A cluster of vessels undergoes the same reaction operations at the same time and are essentially parallel vessels. A cluster is an alternative to upsizing a reaction vessel to increase capacity. A cluster might be advantageous to upsizing vessels to keep vessel sizes constant while increasing system capacity, especially to keep vessel sizes within manufacturing constraints. For example, it maybe desirable to keep vessel diameters <2.5m for ease of manufacturing and shipping, so here we would use a cluster of multiple vessels. In other scenarios, where manufacturing and shipping aren’t constraints, one may instead use a larger reaction vessel with >2.5111 diameter. A cluster of vessels can have a common header and footer, such that implementing a cluster utilizes the same piping and valving configuration as implementing a single, larger vessel. Vessels within a cluster generally receive the same inlet gas and have a shared outlet stream.

[0100] Some variations of the system may also be implemented with a single reaction vessel.

[0101] In one variation, the set of reaction vessels may be substantially uniform in their design with each reaction vessel using a similar sorbent type and all including a similar catalyst.

[0102] In some variations, the set of reaction vessels may include different reaction vessel types. Accordingly, the set of reaction vessels may include a first subset ofreaction vessels and a second subset of reaction vessels that differ in type of reaction vessels. Some reaction vessels may include a reaction bed with a sorbent and a catalyst, which may function to facilitate promoting reaction of nitrogen (N2) and hydrogen (H2) to produce ammonia and then sorbing the ammonia. Some reaction vessels may include a reaction bed with only a catalyst, which may function to facilitate promoting reaction of nitrogen (N2) and hydrogen (H2) to produce ammonia. Some reaction vessels may include a reaction bed with only a sorbent, which maybe used for sorbing and / or purifying an ammonia stream. As yet another variable, reaction vessels may have different types of sorbents. For example, the set of reaction vessels may include some reaction vessels using adsorbents and some using absorbents.

[0103] A reaction vessel functions as a subsystem for (sorbent-based) production or processing of ammonia. A reaction vessel can include a vessel body, a reaction bed within the vessel body, that includes at least a sorbent or at least a catalyst, and a set of material ports for receiving and outputting material streams as shown in FIGURE 3. Referring to FIGURE 3, a sorbent (301) and catalyst (302) are disposed within a reaction bed (303). In some variations, the reaction bed further includes a catalyst.

[0104] The vessel body may be a substantially rigid structure within which reactions are contained. Accordingly, the vessel body can include a defined internal cavity providing fluid communication to at least one material port, and generally fluid communication between two or more material ports. The vessel body can be a steel or other metal structure. In some variations, the vessel body may be a structure formed as a tube or long passageway. The reaction vessel may be linear with the vessel body formed as a substantially straight path, but the reaction vessel may alternatively be configured into a non-linear path. In some alternatives, the reaction vessel may not even form a path but maybe some alternative chamber or container. For example, a reaction vessel may have a reaction bed that is a three-dimensional structure (e.g., a lattice) structured within some defined chamber of the vessel body, where the chamber can receive and expel materials through material ports.

[0105] A reaction vessel may be configured for heat exchange. One example is a reaction vessel that is a shell and tube heat exchanger, where the tube side forms the reaction bed and the shell side holds a heat transfer fluid. Alternatively, the shell sidecan be the reaction bed, and the tube side can contain a heat transfer fluid. Other types of reaction vessel with heat exchange can include the use of plates, fins, coils, tubes, electrodes, band heaters, and similar.

[0106] A heat transfer fluid may circulate throughout vessels in the set of reaction vessels. The heat transfer fluid may convey heat from vessels in one mode to vessels in another mode. Similarly, the heat transfer fluid may run parallel through vessels in a cluster. The heat transfer fluid could be hot oil, gas, water, or other. The heat transfer fluid could also convey heat to / from vessels to heat sources and sinks in other parts of the larger ammonia plant. The heat transfer fluid may have several reservoirs, where, in one example, each reservoir is not in thermal communication. For example, a cluster of reactors may have its own heat transfer fluid.

[0107] The reaction bed functions to facilitate sorbent-based production and / or processing of ammonia. The reaction bed can be contained within an internally defined channel through the vessel body. The reaction bed may be contained along the length of the vessel body. An extended length of multiple meters may provide sufficient surface space for materials to react as they pass through the reaction vessel. There may be multiple beds within a vessel, and flow through a bed may be axial, radial, or combinations thereof. If there are multiple beds within a vessel, each bed maybe considered an individual reaction vessel and undergo process operations separate of other beds in the same vessel.

[0108] The catalyst may include an active material and inert supporting structure, or an active supporting structure, or solely an active material. The active catalyst material may be a metal, alloy, metal oxide, or similar. In some embodiments the catalyst may be iron based. The sorbent may be a porous material, for example, a zeolite, silica, alumina, metal-organic framework (MOF), covalent organic framework (COF), zeolitic imidazolate framework (ZIF), and / or another suitable sorbent. In one variation, the sorbent may be a zeolite, wherein the zeolite may include a metal cation, may include one of 4A, 5A, Y, X, ZSM-5. In some embodiments the sorbent maybe from the FAU (Faujasite) family. In some embodiments the sorbent maybe zeolite X. In some embodiments the sorbent maybe zeolite Y As shown in FIGURE 22, one potential benefit and novel discovery reveals some zeolites reversibly adsorb ammonia at mildammonia synthesis conditions, that is, 200-500C at partial pressures of 0-3+ bar ammonia and 10-50 bar total pressure. Referring to FIGURE 22, the sorbent adsorbs ammonia with a rapid increase in NH3capacity at pNH3 <ibar (2201) and continues to adsorb ammonia above about 1 bar (2202). In some variations, different sorbents may be used in such conditions to permit a multi-step cycle tailored to the sorbent (e.g., adsorbent) of choice to increase ammonia yields. Different cycles maybe customized for different sorbents. The sorbent may be any sorbent configured to sorb ammonia.

[0109] The sorbent may comprise an active absorbent disposed within a porous support material, of which the support material may further be a sorbent or inert. The catalyst and / or sorbent maybe formed as a powder, granule, pellet, tablet, extrudate or similar. The catalyst and / or sorbent may be formed as a monolithic structure. The catalyst and sorbent maybe distinct structures, or integrated within a common structure, for example, an extrudate containing the catalyst and sorbent materials intermixed, which may be homogenous or non-homogenous in nature. The catalyst and / or sorbent maybe doped, impregnated, ion-exchanged, or similar with active materials or promoters, for example, other metals or metal oxides. The catalyst and / or sorbent structures may include binder materials or other additives to enhance heat and mass transfer properties. The reactor bed maybe fixed, fluidized, or a combination thereof.

[0110] The catalyst may function to initiate or promote reaction of nitrogen with hydrogen. In some variations, the active component may comprise Ru, Fe, or oxides thereof. Cs, K, AI2O3, Co maybe promoters to the active catalyst. The catalyst maybe supported on AI2O3, CeO2, or an Fe-oxide. The catalyst maybe any catalyst configured for ammonia production. As mentioned, some reaction vessels may not include a catalyst.

[0111] Additional details on suitable catalysts and sorbents can be found in PCT Patent Application PCT / US2024 / 032834, which is incorporated herein by reference in its entirety for all purposes.

[0112] A reaction vessel may have a ratio of catalyst to sorbent by mass of about 1:4 to about 4:1. In some cases the ratio is about 1:1. In some cases the ratio is about 2:1. In some cases the ratio is about 1:2.

[0113] The sorbent can function to sorb ammonia. The sorbent in one variation is an adsorbent. The sorbent in another variation maybe an absorbent.

[0114] In one variation of a reaction vessel, the reaction bed includes a combined catalyst and sorbent (i.e., a “catalyst plus sorbent” reaction vessel).

[0115] In one variation, at least one reaction vessel may include only a catalyst (i.e., a catalyst without a sorbent).

[0116] In some variations of the reaction vessels, the reaction bed may include sorbent without a catalyst (i.e., a “sorbent-only” reaction vessel). A sorbent-only reaction vessel may function to help purify an ammonia stream. For example, it maybe used to remove residual unreacted H2 and N2 in desorbed ammonia from another reaction vessel.

[0117] The dimensions of various reaction vessels may be considerably different, for example a catalyst only vessel may be much smaller than a catalyst plus sorbent vessel. The reaction vessels could be different lengths, aspect ratios, have different types of reaction beds, or other design variations.

[0118] As another variation, a reaction bed may include a reaction bed patterned with differing regions of catalyst and / or sorbents. In one such variation, a first portion (e.g., nearest a feed input material port) may include a catalyst and sorbent, while a portion nearest an output material port may include only a sorbent. The sorbent-only region may similarly function to purify an ammonia stream. In another variation, a sorbent-only region maybe nearest a feed input material port and configured to purify an inlet gas stream. A reaction bed may also include different regions or combinations of sorbent types such as including adsorbents in combination with absorbents.

[0119] The reaction vessel can include at least two material ports. The material ports may include one or more dedicated material input port and material output port. In some variations, however, one or more material ports may be used as either an input or an output. In this way, material maybe supplied and flowed through the reaction vessel in different directions. In some instances, the direction for the blowdown operation is counter-current to a synthesis direction. At least two material ports can be oriented on opposing ends of a reaction bed. In some variations, there may be additional material ports. For example, a reaction vessel may include intermediary material ports, whichmay function to allow for material to be introduced at a point along the length of the reaction bed. This may be used to address adsorption fronts where material is not fully reacted, possibly because of a pressure differential along the length of the reaction bed.

[0120] In some variations, the system may include a heat exchanger that may be a dedicated heat exchanger for each reaction vessel but may alternatively be a shared heat exchanger that is shared by two or more reaction vessels.

[0121] The material stream conduit system functions to manage flow of supply material streams to the set of reaction vessels and output streams from the set of reaction vessels. The conduit system can include tubing, piping or other connections that establish fluid communication with and / or between the set of reaction vessels. The conduit system in some variations includes inter-connections between at least a subset of reaction vessels. These interconnections maybe controllably valved such that inputs to and outputs from a given reaction vessel may be directed dynamically. There may be compressor, fan, or similar operations between vessels in the system to manipulate flowrates and pressures. One or more surge tanks maybe included in the system, for example on the feed end or outlet end of the system. A surge tank may be in fluid communication with one or more vessels at a time.

[0122] One can reduce cost by limiting the number of valves and pipes. To do so, one may want to use the minimum number of reactor interconnections. One such approach is to use a shared header and footer system, where vessels are connected via shared inlet and outlet headers. There maybe multiple inlet and outlet headers. For example, there may be a header / footer for each operation in the cyclic operation. This may include a reactant gas header, a sweep gas header, a first effluent footer, and a second effluent footer, and a product footer. The footers may connect to surge tanks, as may the headers.

[0123] As shown in FIGURE 1, some variations may be configured such that the input and output streams may be interchangeably directed between any reaction vessel. In alternative variations, the conduit system may be configured such that not all reaction vessels are interchangeable and there may be defined types of material flows that can be conveyed through the conduit system.

[0124] By scheduling reactors, the system can function as a steady state black box with respect to the process that surrounds it - i.e., for the reactor system to be fed a constant flowrate of gas and output a constant flowrate of gas. A schedule may provide substantially constant inlet gas to the system and withdraw substantially constant outlet gas. A surge tank can function as a buffer to damp out fluctuations, especially on the outlet side, where blowdown has a characteristically “pulsed” profile. Headers combine inlets of multiple reaction vessels into a common stream for, as do footers for outlets of reaction vessels. Headers and footers therefore can allow continuous gas supply and withdrawal from the system even while individual vessels valve open / closed.

[0125] In some variations, the operation of the reaction vessels is staged such different reaction vessels are operated in different cycle states, which may be done so that materials may be reused through fluid communication between the vessels.

[0126] The material conduit system may be configured for the outlet of a vessel to be connected (directly or through a header / footer) to the inlet of another vessel, such that material transfer from vessel to vessel is possible. In some cases, a fan, blower, compressor, or similar, may be present to increase the pressure of gas to maintain flow from a vessel outlet at a pressure lower than the pressure at the inlet of another vessel. In other examples, the outlet pressure of a vessel may be higher than the inlet pressure of another vessel such that the compressor is not needed.

[0127] Vessels configured for fluid communication may or may not be in fluid communication at different times in a scheduled cycle. Vessels undergoing the same operation, for example, in a cluster, may share a common inlet and outlet gas but act in parallel rather than in series, and therefore maybe considered out of fluid communication.

[0128] To allow for fluid communication, the vessels in previous stages of the cycle maybe connected with pipes / tubes, and there maybe valves between these vessels that can open or close. This allows shared operation across ammonia reaction vessels.

[0129] Additionally or alternatively, the system may allow for flowing materials in multiple ways through a reaction vessel. For example, material may be flowed through a reaction vessel in two opposing directions between material ports. In this way, the system may feed or desorb vessels from either end of the reaction vessels. A sorbent bedmay fill up (i.e., saturate) first from a feed end, and the downstream end of the bed is less saturated. The system may address this by desorbing from the feed end, because there is more ammonia on that side. This may result in faster desorbing times. In other variations, flow of materials may even be alternated between different ends of a bed at which material is fed / desorbed - essentially pushing the sorption front back and forth through the bed. Accordingly, each end of each reaction vessel could be connected and valved between.

[0130] Additionally, fluid communication between vessels may allow for re-use of unreacted effluent as well as purification of desorbed ammonia. The input to a reaction vessel in one cycle stage could be at least partially supplied an output of another reaction vessel in a different stage.

[0131] In some variations, reaction vessels may be included that only contain a sorbent (in contrast to each reaction bed including a catalyst and sorbent). This sorbent can “clean up” impure ammonia leaving a reaction vessel that has a catalyst. This configuration and inter-connection between a catalyst plus sorbent reaction vessel and a sorbent-only reaction vessel may address the challenge that ammonia exiting a reactor that contains a catalyst may be subject to decomposition back to the equilibrium concentration of N2 and H2. However, if a “clean up” reaction vessel with a sorbent-only bed is used, desorbed ammonia from the catalyst-sorbent reaction vessel may be sorbed within the sorbent-only reaction vessel, which when desorbed can be substantially free of catalyst. Other approaches may alternatively be used to address such challenges such as reducing residence time of gases during desorption, decreasing temperature during desorption, or using a sweep gas.

[0132] In one variation, the conduit system and the set of reaction vessels are integrated within a single reaction system. As shown in FIGURE 4, a reaction system may have multiple distinct tubes that each serve as distinct reaction vessel. This functions to integrate parts of the system into a unified system.

[0133] In other variations, one or more of the reaction vessels may be distinct system components that are housed separately. The conduit system maybe connected to establish fluid communication between these distinct reaction vessels.

[0134] Reaction vessels maybe oriented vertically, horizontally, diagonally, or any combination thereof.

[0135] The system may additionally include other support components such as surge vessels, material supply sources, a pressurizing / depressurizing system, and / or other components used in processing and handling of the materials. A pressurizing system may, for example, include a surge vessel a compressor, and a condenser. Pumps maybe additionally included for pressure manipulation and fluid conveyance, for example, a vacuum pump to speed depressurization.

[0136] As shown in FIGURE 24 in some variations, the outlet of the reaction / sorbent bed system may comprise a mixture of N2, H2, and NH3 and it maybe beneficial to condense the NH3 into a liquid as described elsewhere. In some variations, the system may be configured to recycle the remaining N2 and H2, for example, by passing the gas through a boost compressor to at least the pressure of S210 and feeding into the first vessel. One may appreciate that with such a scheme, recycle rates may be much reduced as compared to a traditional Haber-Bosch reactor system due to the increased concentration of ammonia in the effluent gas prior to recycle. The negative effect of residual NH3 recycled is also minimized compared to a conventional scheme, as the NH3 will be adsorbed at the upstream end of first adsorbent-containing vessel it passes through and will not be present in the gas stream to slow catalyst kinetics or influence equilibrium.

[0137] The net single-pass conversion of H2or N2 (that is, from the feed to the outlet of the reactor system) of the described system maybe between 15% and 99.999%. The single pass conversion prior to recycle compression maybe above 20%, above 30%, above 40%, more preferably, above 45%, 50%, 60%, 70%, 80%, 90%

[0138] By introducing the recycle, the net overall conversion (from feedstock to liquid NH3 output) maybe above 90%, above 95%, above 96%, above 97%, above 98%, or above 99%.

[0139] The control system functions to manage operation of the system. The control system may be communicatively connected to control valves, material feed controls, and sensors, for example, pressure transducers, temperature gauges, and gas composition measurement apparats. The control system can manage fluid and thermalcommunication to and from reaction vessels. In this way, the control system may control cycling the reaction vessels through different cycle processes and coordinating those processes between the different reaction vessels.Method for Gaseous Product Production

[0140] The systems and methods described herein may be implemented using reaction vessels that cycle through operational states to produce gaseous products. The method allows for production of multiple distinct effluent streams with different compositions through controlled cycling of operational states within a reaction vessel containing catalysts and / or sorbents.

[0141] As shown in a method variation of FIGURE 31, a method for making a gaseous product may include introducing a reactant gas within a vessel containing a catalyst and sorbent S110, withdrawing a first effluent stream from the vessel S120, and withdrawing a second effluent stream from the vessel S130, wherein the second effluent stream is enriched in the product species relative to the first effluent stream.

[0142] Referring to FIGURE 32, the method may further include pressurizing the vessel prior to introducing the reactant gas S100, and subsequently performing desorption processes that include reducing the vessel pressure. In one variation, the method includes pressurizing the vessel S100, introducing a reactant gas comprising a first reactant species and a second reactant species within the pressurized vessel S110, withdrawing a first effluent stream S120, and withdrawing a second effluent stream enriched in product species S130. The method may further include reducing a pressure of the vessel to a depressurization pressure and withdrawing a depressurization stream S140, and / or reducing the pressure to a blowdown pressure that is lower than the depressurization pressure and withdrawing a blowdown stream comprising the product species S150 as shown in FIGURE 32.

[0143] The method may alternatively be described as a method for making a gaseous product that includes iteratively performing a synthesis operation S112 and a desorption operation S132 as shown in FIGURE 33. The synthesis operation S112 includes introducing a reactant gas comprising reactant species to a reaction vessel containing a catalyst and a sorbent, wherein the catalyst facilitates conversion of reactant species intoa product species and the sorbent sorbs the product species. The desorption operation S132 includes desorbing the product species from the sorbent and withdrawing a product gas comprising the product species from the reaction vessel.

[0144] Referring to FIGURE 31, Block S110, which includes introducing a reactant gas within a vessel containing a catalyst and sorbent, functions to facilitate synthesis of a product species through conversion of reactant species in a reactant gas into product species and selective sorption of those product species within the reaction vessel. The reactant gas may comprise one or more reactant species that undergo catalytic conversion to form product species. The catalyst facilitates the conversion of the reactant gas into the product species, and the product species is selectively sorbed to the sorbent within the same reaction bed. This integrated approach of reaction and sorption within a single vessel allow for enhanced conversion efficiencies and selective separation.

[0145] In some variations, the reactant gas introduced in block S110 or S112 may comprise a first reactant species and a second reactant species, wherein the product species is formed from a reaction between the first reactant species and the second reactant species. In ammonia production applications, the first reactant species may be hydrogen (H2) and the second reactant species maybe nitrogen (N2), or vice versa. The vessel may be pressurized with the first reactant species, an inert gas, or any combination thereof prior to introducing the reactant gas. In one variation, the vessel is pressurized with the first reactant species, and the reactant gas comprises the second reactant species, such that introducing the second reactant species triggers the synthesis reaction or at least establishes the reactant gas composition for the synthesis reaction.

[0146] In some variations, the reactant gas may have at least about 1%, 2%, 4%, 5%, 8%, or 10% of the product species. In some embodiments the reactant gas may have at least about 1% of the product species. In some embodiments the reactant gas may have at least about 4% of the product species.

[0147] The combination of reactant species in the presence of the catalyst, along with conditions of the reaction vessel, can result in the synthesis of the desired product species. The process by which the reactant gas is introduced maybe adjusted to control or facilitate occurrence of synthesis. The introduction of the reactant gas may beperformed through flowing or otherwise introducing an input material stream or streams that establishes a reactant gas that comprises a set of reactant species for the catalytic synthesis of the desired product species. In one variation, introducing the reactant gas within the vessel is performed by first flowing an input stream into the vessel with a first reactant species and subsequently flowing a second input stream into the vessel with at least a second reactant species thereby establishing within the reaction vessel a mixture of the first reactant species and the second reactant species that form the reactant gas. This maybe performed for any number of reactant species. In some variations, all or a subset of reactant species maybe introduced simultaneously. In some variations, the flowing of the first reactant species maybe used when pressurizing the reaction vessel in preparation for introducing the other reactant species. Other approaches for introducing the reactant gas, such as different staged adding or blended adding of input streams, may alternatively be used.

[0148] In ammonia production applications, block S110 involves introducing a reactant gas comprising nitrogen (N2) and hydrogen (H2) into a vessel containing an ammonia synthesis catalyst and an ammonia-selective sorbent. The catalyst facilitates the reaction of nitrogen and hydrogen to form ammonia (NH3), which is then sorbed into and / or onto the sorbent. This process can achieve higher per-pass conversions than conventional Haber-Bosch processes by removing the ammonia product from the gas phase, thereby preventing the reaction from reaching gas-phase equilibrium (or, put otherwise, shifting the equilibrium point by including the sorbent). The introduction of the reactant gas within the reaction vessel maybe performed in stages. For example, introducing the reactant gas may include flowing a hydrogen or nitrogen enriched gaseous stream into the reaction vessel (possibly when pressurizing the reaction vessel), and then subsequently flowing a complementary enriched gaseous stream (e.g., a nitrogen or hydrogen enriched stream) into the reaction vessel. Alternatively, a gaseous mixture of hydrogen and nitrogen maybe flowed or supplied as an input into the vessel.

[0149] The synthesis operation may be controlled through various process parameters to facilitate and / or optimize conversion and production rates. In one variation, a pressure of the vessel maybe regulated at an outlet of the vessel while the reactant gas is introduced into the vessel, maintaining substantially constant outletpressure while allowing inlet pressure to vary. Accordingly, the method may include maintaining pressure at an outlet of the reaction vessel (e.g., an outlet for the first effluent stream) In some variations, the pressure maybe back regulated. In other variations, the pressure maybe forward regulated. A variation that includes back regulating pressure at an outlet may be used to maintain pressure while withdrawing the first effluent stream. Introducing the reactant gas into the vessel (or introducing of a material stream with one or more reactant species to establish the reactant gas) and withdrawing the first effluent stream from the vessel may occur simultaneously during the synthesis operation. Withdrawing a second effluent stream from the vessel is performed subsequent to withdrawing a first effluent stream from the vessel.

[0150] The reactant gas maybe introduced into the vessel until specific breakthrough conditions are met, such as when the first effluent stream contains more than 1 vol% of the second reactant species or more than 1 vol% of the product gas, indicating approach to saturation of the sorbent bed. In some variations, the first effluent stream contains substantially no second reactant species, and in some variations, the first effluent stream contains substantially no product gas. The method may include monitoring or sensing of effluent stream compositions such that introduction of the reactant gas may be controlled based on such conditions.

[0151] Alternatively, the synthesis operation may be controlled by monitoring process indicators such as flow rate or pressure drop. The reactant gas may be introduced until a flow rate of the first effluent stream is substantially constant, or until a flow rate of the first effluent stream reaches a desired flowrate, for example, 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% of the reactant gas flowrate. In some embodiments the reactant gas maybe introduced until a flow rate of the first effluent stream reaches about 50% of the reactant gas flowrate. In some embodiments the reactant gas may be introduced until a flow rate of the first effluent stream reaches about 10% of the reactant gas flowrate. In another variation the reactant gas maybe introduced until a pressure drop across the vessel or reaction bed is substantially constant. Time-based control may also be employed, where the reactant gas is introduced for a period of time between about 1 and about 100 residence times, preferably between about 1 and about 20 residence times, to optimize conversion whilepreventing breakthrough of unreacted materials. In some embodiments the reactant gas maybe introduced for a period of time between about 1 and 20 residence times.

[0152] The synthesis operation may be conducted under specific operating conditions to enhance reaction rates and sorbent performance. The reactant gas flow may have a gas hourly space velocity (GHSV) less than about 10,000 / hr, preferably less than about 5,000 / hr, to provide sufficient residence time for reaction and sorption. In some embodiments the reactant gas flow may have a gas hourly space velocity (GHSV) less than about 10,000 / hr. The reactant gas flow may have a gas hourly space velocity (GHSV) less than about 5,000 / hr. The reactant gas flow may have a gas hourly space velocity (GHSV) less than about 3,000 / hr. The Reynolds number of the reactant gas in the vessel may be greater than about 5, preferably greater than about 3, to ensure adequate heat and mass transfer. In particular embodiments the Reynold’s number of the reactant gas flow may be greater than about 5. In particular embodiments the Reynold’s number of the reactant gas flow may be greater than about 10. The reactant gas maybe introduced at a pressure between about 10 and about 50 bar, preferably between about 20 and about 35 bar, to balance reaction thermodynamics with equipment costs. In particular embodiments, the reactant gas pressure may be introduced at about 20 bar. In particular embodiments, the reactant gas pressure may be introduced at about 30 bar. In particular embodiments, the reactant gas pressure may be introduced at about 30 bar.

[0153] In ammonia production applications, the product species is ammonia (NH3), and the synthesis operation involves converting hydrogen (H2) and nitrogen (N2) reactant species into ammonia. The vessel may be pressurized with a pressurizing gas comprising H2, N2, an inert gas, or any combination thereof. The sorbent is configured to sorb ammonia, and the catalyst is configured to convert H2 and N2 into NH3. The reactant gas may comprise H2 and N2, and may additionally comprise NH3 from recycled streams.

[0154] When alternatively described as a synthesis operation S112, the operation may be controlled by various termination criteria to optimize sorbent utilization and production rates. The synthesis operation maybe terminated upon satisfying a synthesis saturation condition, which may be determined by monitoring inlet pressure reaching asubstantially constant value, outlet flowrate beginning to increase after reaching a substantially minimum value, or concentration of unreacted feedstock in an outlet stream beginning to increase after reaching a substantially minimum value. The iteration between synthesis and desorption operations may be controlled by length of time, variation in pressure, variation in outlet flowrate, or variation in gas composition.

[0155] The synthesis operation and desorption operation may be performed for approximately equal lengths of time to balance production rates with cycle efficiency. Alternatively, the synthesis operation may be performed for a longer length of time than the desorption operation to maximize sorbent utilization. When implemented with a sweep operation during desorption, the synthesis operation and the sweep operation may be performed for approximately equal lengths of time to optimize material balance and production consistency.

[0156] Temperature control during the synthesis operation is important for maintaining catalyst activity and sorbent capacity. Each vessel may be maintained at a temperature within about 5O°C of an average system temperature, and different vessels maybe maintained within about 5O°C of each other to facilitate thermal integration. The synthesis operation maybe performed at about 35O-45O°C, optimizing the balance between reaction kinetics and thermodynamic driving force. The synthesis operation and any subsequent desorption operation maybe performed at about the same temperature to allow for isothermal or near-isothermal operation.

[0157] In some variations, the method includes thermally coupling a reaction vessel to another system, such as another vessel, a passive heating or cooling system, or an active heating and / or cooling system) A reaction vessel maybe cooled during the synthesis operation to remove the heat of reaction and maintain desired temperature conditions. The reaction vessel may exchange heat with the reactant gas, using the incoming reactant gas as a cooling medium while preheating the gas for optimal reaction conditions. This thermal integration can improve overall energy efficiency and maintain more uniform temperature conditions throughout the process.

[0158] Block S120, which includes withdrawing a first effluent stream from the vessel, functions to remove materials from the vessel that are not sorbed by the sorbent or that are displaced by incoming reactant gas. The first effluent stream typicallycontains unreacted reactant species and maybe withdrawn during or after the introduction of the reactant gas in block Sno. The composition of the first effluent stream depends on the operational state of the vessel and the extent of reaction and sorption occurring within the vessel.

[0159] In ammonia production applications, the first effluent stream from block S120 typically contains unreacted nitrogen and / or hydrogen that was not converted to ammonia or that was displaced from the vessel. This first effluent stream can be substantially free of ammonia product since the ammonia is selectively sorbed by the sorbent. The first effluent stream maybe enriched in one reactant species over another, depending on the reaction stoichiometry and the timing of reactant gas introduction and the composition of the reactant and pressurization gases. In some variations, trace quantities of the product species may be contained in the first effluent stream. Such trace quantities in the first effluent stream may be used or processed differently from that of the second stream for retrieval of the product species.

[0160] The first effluent stream may be characterized by being at a pressure greater than or equal to the second effluent stream, reflecting the different operational states during which these streams are withdrawn. The first effluent stream may be directed to various downstream operations to maximize system efficiency. In one variation, the first effluent stream is directed to a recompression operation, where unreacted reactant species can be recycled back to the synthesis process, thereby improving overall conversion efficiency and reducing feedstock consumption. Accordingly, the method may include recycling or otherwise flowing the first effluent stream to the input of the vessel (or to another vessel). The first effluent stream maybe directed to the inlet of a second vessel.

[0161] In ammonia production applications the method may include prior to introducing the reactant gas within the vessel pressuring the vessel with a pressurizing gas which may include H2, N2, an inert gas, or combinations thereof. More generally for other gaseous product production, the pressurizing gas may be one of the reactant species, a non-reactive combination of reactant species, an inert gas, or a combination thereof.

[0162] In one variation, the first effluent stream contains primarily nitrogen gas when the vessel is pressurized with nitrogen or when nitrogen is the predominant unreacted species. In this case, the first effluent stream contains substantially no hydrogen, creating a nitrogen-rich stream that can be reused for pressurization or sweep operations in other vessels. Alternatively, the first effluent stream may contain primarily hydrogen gas when the vessel is pressurized with hydrogen or when hydrogen is the predominant unreacted species, resulting in a first effluent stream that contains substantially no nitrogen.

[0163] The first effluent stream may have substantially the same composition as the reactant gas initially introduced to the vessel. Similarly, when pressurization is employed, the first effluent stream may have substantially the same composition as the pressurization gas, especially when the pressurization gas comprises a single reactant species. This compositional control may be used for precise management of material streams and facilitate material stream reuse strategies in multi-vessel systems.

[0164] During the synthesis operation, a synthesis effluent stream may be withdrawn from the reaction vessel, which represents the continuous outlet stream during active synthesis. This synthesis effluent stream is essentially the first effluent stream withdrawn during the synthesis operational state, and its composition evolves as the synthesis progresses and the sorbent approaches saturation. Initially, the synthesis effluent may be predominantly unreacted feedstock or pressurization gas, but as synthesis progresses, it may contain increasing amounts of unconverted reactant species or even trace amounts of product species.

[0165] Block S130, which includes withdrawing a second effluent stream from the vessel that is enriched in the product species relative to the first effluent stream, functions to recover the product species that was previously sorbed by the sorbent. The second effluent stream is typically withdrawn during a desorption operational state where conditions are changed to promote desorption of the product species from the sorbent. A desorption operational state may include performing pressure swing operations (such as depressurization or blowdown), temperature swing operations, or combinations thereof to drive desorption through thermodynamic manipulation. The second effluent stream may serve as a primary product stream from the reaction vessel.

[0166] In ammonia production applications, block S130 involves withdrawing an ammonia-enriched effluent stream from the vessel. This is typically accomplished by reducing the pressure in the vessel, which promotes desorption of ammonia from the sorbent. The second effluent stream can contain significantly higher concentrations of ammonia compared to what would be achievable in conventional steady-state reactors operating at the same temperature and pressure conditions.

[0167] The method may further include introducing a rinse gas comprising the product species into the vessel prior to withdrawing the second effluent stream. The rinse operation may also be subsequent to synthesis operation. The rinse operation functions to displace unreacted reactant species from the vessel and increase the concentration of product species in the vessel prior to desorption. In ammonia production applications, the rinse gas may comprise ammonia, which displaces residual nitrogen and hydrogen from the vessel interstices and pores, resulting in a subsequently desorbed stream with higher ammonia purity. The rinse operation maybe performed at elevated pressure to minimize desorption of the sorbed product species during the rinse process.

[0168] The second effluent stream may be withdrawn in various configurations to optimize desorption efficiency and product purity. The second effluent stream maybe withdrawn in a direction substantially co-current to the direction at which the reactant gas flows through the vessel during synthesis, or it may be withdrawn counter-currently to optimize desorption from the most saturated regions of the sorbent bed. The second effluent stream maybe withdrawn from the vessel through multiple outlets to reduce the effective desorption path length and accelerate product recovery.

[0169] When multiple outlets are used, at least one outlet may be configured such that the flow path of the second effluent stream is substantially co-current to the direction of reactant gas flow during synthesis. The reactant gas and / or material input streams with reactant species to establish the reactant gas maybe introduced through a first material port in the vessel, and the second effluent stream may be withdrawn from a second material port of the vessel to establish a flow-through configuration.Alternatively, the second effluent stream may be withdrawn from the same first materialport used for reactant gas introduction, enabling counter-current desorption that may be advantageous for certain sorbent bed configurations.

[0170] The method may further include introducing a sweep gas into the vessel while withdrawing the second effluent stream to enhance desorption efficiency and product purity. The sweep gas functions to reduce the effective concentration of product species in the gas phase, promoting continued desorption from the sorbent and minimizing residence time of the product species in the vessel. This can reduce back-reactions and improve overall product recovery.

[0171] In ammonia production applications, the sweep gas may comprise a reactant species such as hydrogen (H2) or nitrogen (N2), which may provide the additional benefit of inhibiting the back-reaction of ammonia to nitrogen and hydrogen. In one variation, the sweep gas may comprise primarily H2 to maximize this inhibition effect. The sweep gas may have a velocity greater than that of the reactant gas used during synthesis to minimize residence time and maximize desorption driving force, while remaining less than or equal to the fluidization velocity of the catalyst and sorbent materials. In another variation, the sweep gas may have a velocity higher than the fluidization of the catalyst and sorbent materials. In some variations, the sweep gas may have a velocity higher than that of the reactant gas in the synthesis operation.

[0172] The second effluent stream may be directed to various downstream operations for product recovery and purification. The second effluent stream may be directed to a separation operation, such as condensation, distillation, absorption, or adsorption, to recover the product species in pure form. In ammonia production applications, the second effluent stream maybe directed to a condensation operation where ammonia is liquefied for storage and transport.

[0173] The sweep gas may be introduced until specific desorption completion criteria are met, such as when an outlet partial pressure of the product species is less than about 0.4 bar at an outlet from the vessel. This criterion may indicate that the sorbent bed has been substantially regenerated and is ready for the next synthesis cycle.

[0174] The alternatively described desorption operation S132 may comprise multiple sub-operations to optimize product recovery. The desorption operation may include performing a blowdown operation, where the pressure of the vessel is reduced to ablowdown pressure and a blowdown stream is withdrawn from the vessel. Prior to the blowdown operation, the desorption may optionally include performing a depressurization operation, where the pressure is reduced to a depressurization pressure that is greater than the blowdown pressure, and a depressurization stream is withdrawn.

[0175] The blowdown stream serves as a product gas stream enriched in the product species, while the depressurization stream may also serve as a product gas stream or may be recycled depending on its composition. The desorption operation may further comprise a sweep operation, where a sweep gas is introduced to the vessel and a sweep stream is withdrawn, with the sweep stream also serving as a product gas stream. Each of these sub-operations contributes to the overall desorption and product recovery process.

[0176] The desorption operation may be performed substantially adiabatically, allowing natural temperature variations. Alternatively, the temperature of the vessel may be reduced prior to withdrawing the second effluent stream to slow potential back- reactions and improve product stability. Alternatively, the desorption operation may be performed with active heating to maintain the temperature prior to desorption. The desorption operation may also be performed at elevated temperature compared to synthesis to accelerate desorption kinetics, though this may require additional heating input.

[0177] Block S140, which includes performing a depressurization operation, functions to facilitate initial recovery of unreacted materials while preparing for full product desorption. During depressurization, the pressure of the vessel is reduced to a depressurization pressure that is greater than a final blowdown pressure used in block S150. This staged pressure reduction allows for selective withdrawal of different gas compositions and may in some variations allow for reuse of unreacted reactant species. A staged pressure reduction may also allow re-use of unreacted gases. For example, the outlet gas from an initial pressure reduction may be directed as an inlet gas to a second vessel.

[0178] Block S150, which includes performing a blowdown operation, functions to achieve final desorption of the product species from the sorbent by reducing the vesselpressure to a low blowdown pressure. The blowdown operation creates conditions that favor desorption of the product species, enabling recovery of the sorbed material as a concentrated product stream. The blowdown pressure is selected to optimize the balance between desorption efficiency and downstream processing requirements.

[0179] In ammonia production applications, block S140 involves reducing the vessel pressure to remove unreacted nitrogen and hydrogen while leaving most of the sorbed ammonia in place. The depressurization stream withdrawn during this operation is primarily composed of unreacted reactant gases and can be directed to other vessels or recycled for reuse, thereby improving overall system efficiency. Block S150 involves reducing the vessel pressure to a blowdown pressure that promotes ammonia desorption from the sorbent, with the blowdown stream being enriched in ammonia and serving as the primary product stream.

[0180] The method may include performing both depressurization and blowdown operations in sequence to optimize material recovery and reuse. The depressurization operation is performed prior to reducing the pressure to the blowdown pressure, creating a staged pressure reduction process. The depressurization stream comprises primarily the reactant gas, containing unreacted nitrogen and hydrogen in ammonia production applications, making it suitable for recycle or reuse in other process operations.

[0181] In some variations, the blowdown stream may contain at least 5 mol% of the product gas, and typically much higher concentrations, making it the primary product recovery stream. In ammonia production applications, the blowdown stream may contain significant concentrations of ammonia desorbed from the sorbent. The sequential depressurization and blowdown operations allow for separation of unreacted feedstock from product, improving overall process efficiency and enabling material reuse strategies.

[0182] Block S100, which includes pressurizing the vessel prior to introducing the reactant gas, functions to prepare the vessel for the synthesis operation and to establish optimal conditions for reaction and sorption. Pressurizing the vessel can involve introducing a pressurizing gas that may comprise one or more reactant species, inert gases, or combinations thereof. The pressurization establishes a baseline pressure thatfacilitates subsequent introduction of reactant gases and can influence the thermodynamics of both the catalytic reaction and the sorption process. Pressurizing the vessel may be performed as part of introducing the reactant gas within the reaction vessel Sno, as the reactant species may be introduced in part or in whole during the pressurization step. Furthermore, the pressurization of the vessel maybe performed following completion of withdrawing the second effluent stream or otherwise following product gas recovery as part of repressurizing the vessel for the next processing cycle.

[0183] In ammonia production applications, block S100 typically involves pressurizing the vessel with hydrogen (H2), nitrogen (N2), an inert gas, or combinations thereof. When the vessel is pressurized with a first reactant species such as hydrogen, the subsequent introduction of a second reactant species such as nitrogen in block S110 can trigger the ammonia synthesis reaction. This staged introduction of reactant species allows for better control over the reaction initiation and progression. The repressurization operation may utilize gas streams from other vessels in the system, such as depressurization streams or synthesis effluent streams, to improve material utilization and system integration.

[0184] Different vessels in the set of reaction vessels may operate in different operational states at any given time, allowing for coordinated material flow and thermal integration between vessels. This approach may allow for substantially continuous input and output streams.

[0185] A method for making a gaseous product may include using a set of reaction vessels that each iteratively perform the synthesis operation and the desorption operation described herein (e.g., S100, S110, S120, S130, S140, S150, S112 and / or S132). The set of reaction vessels may be coordinated such that different subsets of vessels are in different operational states, enabling material sharing and continuous production. In ammonia production applications, this multi-vessel approach allows for continuous ammonia production or continuous feedstock intake while maintaining the enhanced per-pass conversions achievable through the integrated reaction-sorption process.

[0186] The coordination of multiple vessels allows for optimized production scheduling where a first reaction vessel of the set performs the synthesis operation while a second reaction vessel simultaneously performs the desorption operation. In somevariations, the exothermic synthesis operation in one vessel can provide heat for the endothermic desorption operation in another vessel. The multi -vessel approach also allows for load balancing and production rate control based on feedstock availability and product demand.

[0187] The distribution of vessels across operational states may be optimized for production efficiency and material utilization. In one variation, about one third of the set of reaction vessels (e.g., 33%) maybe performing the synthesis operation at a given time, with the remaining vessels distributed among desorption, re-pressurization, and other operational states. Alternatively, more than about one third of the set of reaction vessels (e.g., 33%) maybe performing the synthesis operation at a given time to maximize catalyst utilization. In particular embodiments about half (e.g., 50%) of the set of reaction vessels maybe performing the synthesis operation to balance synthesis and desorption capacities. Alternatively, more than about half of the set of reaction vessels may be performing the synthesis operation. In particular embodiments, about 60% of the set of reaction vessels may be performing the synthesis operation.

[0188] The multi-vessel system allows for substantially constant flow rates for both inputs and outputs. The reactant gas maybe introduced to the set of reaction vessels with a substantially constant flowrate, providing steady feedstock consumption that facilitates integration with upstream processes such as electrolytic hydrogen generation. Similarly, the product gas may be withdrawn from the set of reaction vessels at a substantially constant flowrate, enabling steady product delivery to downstream processing operations.

[0189] A portion of the set of reaction vessels may comprise a cluster of reaction vessels, where each vessel of a cluster undergoes the same process operation at a given time. Clustering may function to allow for capacity scaling while maintaining manageable individual vessel sizes and simplifying control systems. Clusters can be operated in parallel to increase throughput or provide redundancy, and different clusters can be operated in different phases of the production cycle to maintain continuous operation.

[0190] The timing relationships between operational states may be optimized or enhanced for different production objectives. The synthesis operation and thedesorption operation may be performed for approximately equal lengths of time to balance production rates with cycle efficiency. When sweep operations are employed during desorption, the synthesis operation and the sweep operation maybe performed for approximately equal lengths of time to optimize material balance. Alternatively, the synthesis operation may be performed for a longer length of time than the desorption operation(s) to maximize reaction vessel utilization.

[0191] The multi-vessel approach allows for sophisticated material sharing strategies that improve overall system efficiency and material utilization. Effluent streams from vessels in one operational state can serve as input streams for vessels in different operational states, creating an integrated process network. This material sharing reduces waste, improves conversion efficiency, and allow for better material balance across the system.

[0192] The depressurization stream from a first reaction vessel may be used as the reactant gas for a second reaction vessel, enabling direct reuse of unreacted feedstock without external recompression. This is particularly advantageous when the depressurization stream has a composition suitable for synthesis, such as when it contains both nitrogen and hydrogen in appropriate ratios for ammonia synthesis. Alternatively, the depressurization stream may be used as the re-pressurization gas for a second reaction vessel, providing a method for pressure equalization between vessels while conserving material.

[0193] The depressurization stream from a first reaction vessel may also be used as the sweep gas for a second reaction vessel undergoing desorption. This creates a cascaded material flow where the unreacted feedstock from one vessel assists in product recovery from another vessel. Similarly, the synthesis effluent stream from a first reaction vessel may be used as the reactant gas, re-pressurization gas, or sweep gas for a second reaction vessel, depending on its composition and pressure.

[0194] These material sharing strategies are particularly effective in ammonia production applications, where nitrogen-rich or hydrogen-rich streams from one vessel can be selectively directed to other vessels based on their operational needs. For example, a hydrogen-rich depressurization stream may be used as a sweep gas to inhibitammonia back-reactions, while a nitrogen-rich stream may be used for repressurization or as a component of reactant gas for other vessels.

[0195] The first effluent stream from a single reaction vessel may be utilized in various ways. The first effluent stream contains valuable unreacted materials that can be recovered and reused, improving overall material efficiency.

[0196] The first effluent stream may be introduced to a second vessel containing a catalyst and a sorbent, where the first effluent stream serves as the reactant gas for the second vessel. This approach allows for staged processing where partially converted materials from one vessel undergo further processing in subsequent vessels. In ammonia production applications, a first effluent stream containing unreacted nitrogen and hydrogen can serve as feedstock for additional synthesis operations.

[0197] Alternatively, the first effluent stream may be used to pressurize a second vessel containing a catalyst and a sorbent, providing both pressure energy and reactant material for subsequent operations. This pressurization reuse is particularly valuable when the first effluent stream has suitable pressure and composition for establishing initial conditions in other vessels. The first effluent stream may also be used as a sweep gas for a second vessel, where its composition and flow characteristics assist in product recovery from the second vessel.

[0198] These reuse strategies extend beyond the first effluent stream to other process streams. The depressurization stream may be introduced to a second vessel as reactant gas, re-pressurization gas, or sweep gas, depending on its pressure and composition characteristics. These reuse concepts demonstrate the versatility of the process streams and provide the basis for developing integrated multi-vessel systems with enhanced material efficiency and reduced waste generation.

[0199] As shown in FIGURE 5, a method for production of a gaseous product such as ammonia using cyclic reactors (e.g., sorbent-utilizing reactors as described herein) may include managing material communication between a set of reaction vessels and thereby cycling a set of reaction vessels through different stages of ammonia synthesis S200, which comprises for each reaction vessel: reacting nitrogen and hydrogen with a catalyst to capture ammonia in a sorbent of the reaction vessel S210, rinsing the reaction vessel S220, performing desorption process in the reaction vessel S230, purging the reactionvessel S240, and repressurizing the reaction vessel S250. These different cycle process states (some of them optional) may be performed across multiple reaction vessels. Furthermore, sequencing of the cycle states may be coordinated such that inputs from one cycle state may be supplied by an output of a reaction vessel in a different cycle state. The method for ammonia production shown in FIGURE 5 and described herein may alternatively be used as a method for gaseous product production more generally

[0200] Block S200, which includes managing material communication between a set of reaction vessels and thereby cycling a set of reaction vessels through different stages of ammonia synthesis, functions to operate multiple sorbent-based reaction vessels in coordination in the production of ammonia.

[0201] Cycling a set of reaction vessels through different stages of ammonia synthesis comprises cycling each reaction vessel through a sequence of states or stages substantially similar to those in described herein (e.g., S210, S220, and S230). In general, the set of reaction vessels are not all in the same cycle state at a given time. Managing material communication between the set of reaction vessels can be performed so as to coordinate them such that material transfer is scheduled for enhanced efficiency. Reaction time, balancing of exothermic and endothermic portions of the cycles, material processing (e.g., pressurizing), material reuse (e.g., using nitrogen output from one reaction vessel as input for a cycle of another reaction vessel) and / or other aspects maybe accounted for in managing the materials. The method can be implemented by a system such as described herein, but any suitable system may alternatively be used.

[0202] As shown in FIGURE 1, managing material communication between a set of reaction vessels may include valves to allow for dynamically adjusting material flow to orchestrate cycle progression across a plurality of reaction vessels. Some reaction vessels of the set of reaction vessels may have different beds. Some beds may be beds with catalyst and a sorbent while some beds may only be a sorbent while some beds may only be a catalyst. Additionally, some sorbents maybe adsorbents while some maybe absorbents. The production cycles used for a reaction vessel may vary depending on the type and configuration of a reaction vessel and / or current conditions (e.g., timing / production considerations).

[0203] Some configurations of valves and conduits may be used to establish possible material fluid communication between reaction vessels and / or other system components.

[0204] As described herein, managing the material communication can be used to allow interaction between reaction vessels in differing cycle steps. For example, the effluent from a first cycle state may be fed into a vessel that is in a second cycle state. In general, effluent from a reaction vessel is at a lower pressure exiting the reactor than when it was fed into the reactor. So, unreacted synthesis effluent gases from a vessel in synthesis mode can’t be fed as the inlet to another vessel in synthesis mode without additional compression. We introduce a variation of the separate step of “repressurization,” where the unreacted synthesis effluent from a reactor in synthesis or “reaction” mode is fed into a recently evacuated vessel to re-pressurize it. This vessel is at very low pressure, having just undergone desorption. Re-pressurization can occur with a reactant gas or re-pressurization gas fed from the synthesis effluent of another reactor or from any other gas sources, for example, an upstream gas generator.

[0205] This may also be applied in de-pressurization. A vessel that is saturated with sorbed ammonia may have some amount of unreacted gas in the interstices between pellets and / or the pores of the pellets. It maybe beneficial to do an initial depressurization of this reactor to remove this unreacted gas, which can more readily exit the vessel than the sorbed ammonia, since it is not bound in any significant way to the sorbent. To avoid loss of this unreacted gas, the method may route the initial depressurization into a second vessel so long as the second vessel is at a lower pressure, such as a recently evacuated vessel. This may also include a “re-pressurization” step, purge step, sweep step, or a sub-step.

[0206] In addition to or as part of managing material communication, the method may include managing thermal communication between reaction vessels. This may be performed through system configuration and / or arrangement of the reaction vessels such that they passively have thermal communication. Also, how the reaction vessels are cycled through different states may be performed based in part on managing thermal communication. In other variations, a heat exchanger or other thermal system may be used to actively manage and / or alter thermal conditions of one or more reaction vessels.

[0207] The method may be used in connection with various multi-reactor configurations. The exact configuration may alter how ammonia processing is coordinated across the different reaction vessels. The set of reaction vessels may include at least one reaction vessel with a catalyst and sorbent reaction bed. In some variations, each reaction vessel has a reaction bed with catalyst and sorbent. In some variations, the set of reaction vessels may include a first subset of reaction vessels that each include a reaction bed with a catalyst and sorbent and a second subset of reaction vessels that each include a sorbent-only reaction bed (e.g., no catalyst). In some variations, the set of reaction vessels may include a first subset of reaction vessels that each include a reaction bed with only a catalyst, an optional second subset of catalyst and sorbent reaction bed and an optional third subset of reaction vessels that each include a sorbent- only reaction bed (e.g., no catalyst). Catalyst-only reaction vessels may be used for producing high concentrations of ammonia at a subsequent reaction vessel material port, thus influencing the adsorption front as the reaction / sorption progresses. Sorbent- only reaction vessels may be used for purifying ammonia streams (sorbing and desorbing) and may not be used as part of a reaction cycle state.

[0208] The material flow and sequence of cycles between reaction vessels may vary with respect to time, material availability, and desired output. For example, material flow maybe adjusted based on whether a utilized renewable energy source produces increasing or decreasing amounts of power. In these cases, certain vessels and cycles may be put into or taken out of the material progression so as to influence cycle times and movement of the adsorption front within vessels. In one aspect, a vessel may be directed a reduced flow, for example, in the synthesis mode, the flow may be reduced to approach zero where the reaction will continue until feed gas is locally consumed. Upon restart, the feed gas may increase to continue the synthesis mode. In another aspect, the vessel may proceed into a subsequent mode.

[0209] The method may include providing, configuring, or otherwise using a system such as described and shown herein. The method alternatively may be used with alternative systems and system variations.

[0210] Depending on configuration of the system and / or the particular configuration of a particular reaction vessel, cycling the set of reaction vessels through different stagesof ammonia synthesis comprises cycling through one or more of the cycle states described herein. In some variations, this may include: cycling at least one vessel through S210 and S230; cycling at least a second vessel through S210, S230, S240; and / or cycling at least a second vessel through S210, S220, S230, S240. S250 may additionally be used as a subsequent cycle state, which may follow S230 or S240 as shown in FIGURES 6A-6D. S250 and S210 maybe substantially similar, and some variations may different combinations of either S210 and / or S250. For example, in some variations, the functions of S250 and S210 maybe performed through a combined step or some hybrid combination of the variations described for S210 and S250.

[0211] As described herein, one surprising discovery of the systems and methods finds that markedly different desorption kinetics by different sorbents (e.g., adsorbents) in these conditions permits a multi-step cycle tailored to the sorbent (e.g., adsorbent) of choice to increase ammonia yields.

[0212] In one example, with an Na-X zeolite, one variation may use a cycle of S210- S230-S240-S250 or S210-S230-S250, that is, without a rinse step. This maybe done because the kinetics of desorption for Na-X maybe such that ammonia is spontaneously released absent the presence of pressurized reacting N2 and H2, that is, a rinse step, in particular one with a low concentration of NH3and / or a single reactant species, would desorb ammonia. FIGURE 22 shows one exemplary system configuration.

[0213] In another example, with a ZSM-5 zeolite, one may use the cycle of S210- S220-S230-S240-S250 or S210-S220-S230-S250, that is, with a rinse step. This is because the kinetics of desorption for ZSM-5 are such that ammonia is not significantly released in a pressurized rinse step even if the rinse has a low concentration of NH3or a single reactant species.

[0214] Without being bound or limited by theory, the larger pore sizes on Na-X may allow faster release of ammonia than a smaller pore size such as ZSM-5 and with less rate dependence on total pressure.

[0215] Because of differing times and material requirements the coordinated timing of cycle states may be addressed by having multiple reaction vessels in the same cycle states. For example, there maybe two reaction vessels in one cycle state, two morereaction vessels in a different cycle state, and then one other reaction vessel in yet a third cycle state.

[0216] In connection with managing material communication between a set of reaction vessels, the method may include adjusting temperature of the operating system. The method may be executed by a system such that the system runs substantially isothermally, where all vessels are a constant temperature at all times. Practically, this “constant” temperature may include variations in temperature (e.g., + / io°C, + / - 30C, + / - 50C). The method may maintain temperature within targeted temperature ranges. The temperature range of some implementations maybe 25O-4OO°C, 300-500C, and more preferably 28o-34O°C. In another example, the temperature maybe about 400C.

[0217] Practically, each vessel in the set of vessels will undergo some non-zero fluctuation. Temperature will increase during synthesis and decrease during desorption. As used herein, "isothermal" generally means one is trying to maintain a substantially constant average temperature (as opposed to an intentional temperature swing system), but the use of the term isothermal allows for a temperature variation across time. E.g., each step is performed at about the same temperature. In one example, synthesis and desorption steps are performed at about the same temperature. This provides benefits of being able to transfer the heat of reaction plus sorption to the desorption (as a conventional temperature swing would swing temperature higher in desorption, thus leaving one unable to provide heat from reaction to the higher temperature desorption).

[0218] To maintain the temperature about isothermal, active heating or cooling may be implemented. In one example, cooling may be provided to the synthesis mode to remove the heat of reaction. Cooling may be performed against an external heat transfer medium which maybe a hot oil, gas, or other. In one example, the synthesis mode is cooled by a reactant gas stream, preheating the reactant gas. In another example, heating may be provided to the desorption mode to replace the heat of desorption that is lost. This heat may be provided by heat transfer to an external media of by using a hot sweep gas.

[0219] In one example, the unavoidable variation in temperature with time may be utilized to perform a passive temperature swing. The temperature at the end of synthesis (thus, start of desorption) may be higher than the temperature at the end ofdesorption by about 10-50C. A high temperature at the start of desorption may benefit the rate of desorption.

[0220] In an alternate variation, heating / cooling duty may be reduced or eliminated to operate substantially adiabatically or near adiabatically, allowing a temperature rise and fall during time. Some heat can still be removed from the system, or the temperature will increase over time. This heat can be removed by the gas effluent, as is typical of an adiabatic reactor. This can reach an adiabatic temperature dictated by the conversion and flowrates of the process, around 400-600C, and will include fluctuations in temperature around this point - thus ending up substantially isothermal.

[0221] To help in maintaining temperature, the set of reaction vessels may be thermally coupled. Adsorption releases heat, whereas desorption requires heat. These are reversible, so if each bed is in thermal communication and the steps are at the same temperature, there may be no additional energy demand to power desorption. Reaction to form ammonia releases heat, providing heat in excess of what is required for reversible sorption / desorption and maybe used to compensate for losses in the heat transfer system. However, some variations may have varying temperature. Varying temperature may be used in some alternative variations to impact processing for one or more cycle states.

[0222] Block S210 which includes reacting nitrogen and hydrogen with a catalyst to capture ammonia in a sorbent of the reaction vessel, functions to create ammonia through a reaction. As used herein, this is the synthesis operation. In block S210, nitrogen (N2) and hydrogen (H2) gas are introduced in a high-pressure state to react with a catalyst to form ammonia and then sorbed to a sorbent in the reaction vessel as shown in FIGURE 7. Trace amounts of nitrogen and hydrogen may be outputted at a reduced pressure. This stage of the cycle process can be exothermic thereby outputting heat.

[0223] The sorbent can be un-saturated at the initiation of this step. Pressurized feedstock can be fed into the bed of the reaction vessel. The feed pressure (i.e., the pressure of the feedstock) may be the highest pressure experienced by the system across other cycle states (i.e., denoted as P_high). P_high maybe 10-50 bar, or 20-35 bar. For example, P_high maybe about 20 bar. In particular embodiments, P_high maybeabout 30 bar. It maybe beneficial to have P_high less than 30-35 bar, as this is the pressure at which H2 is typically output by electrolyzers. If the reaction pressure is lower than that, then the method may avoid or reduce compression of the hydrogen.

[0224] Within the bed of a reaction vessel, N2 and H2 react over the catalyst to form NH3, which is sorbed to the sorbent of the bed. Both processes are exothermic, so heat may be removed to maintain the bed at a constant temperature.

[0225] Pressure may be non-uniform within the reaction vessel. In some variations, a pressure gradient may exist within the reaction vessel. In one example, pressure may decrease down the length of the bed as a result of physical pressure drop from forcing gas through a packed bed, as well as by loss of molecules from the reaction and sorption (e.g., N2 + H2 enter and most react, and only trace unreacted nitrogen and hydrogen leaves because NH3 is adsorbed). The reaction vessel maybe designed to minimize unreacted output from the reaction vessel. In some variations, substantially nothing leaves the reaction bed, possibly venting the small amounts of unreacted gases. In some variations, the reaction vessel may be implemented to have a long bed. For example, a reaction bed that is 8-10 meters in length may consume >95% of feedstock. Alternative reaction bed configurations may alternatively be used.

[0226] During most of the S210 cycle process, either nothing leaves the reaction vessel or a reduced flow rate of N2 and H2 is outputted (e.g., all NH3 will be adsorbed). The S210 cycle process may be ended by cutting off feedstock flow before “breakthrough” - which is the point where the sorbent is effectively saturated and NH3 is no longer completely adsorbed.

[0227] Synthesis mode S210 can be operated in a flow through mode. At the beginning of the operation, the reaction bed is at a pressurized state, pressurized by a gas. This pressurization gas preferably comprises one of multiple reaction species (in this case, H2or N2but not both), such that the pressurization occurs without causing reaction at the catalyst. An inert pressurization gas can also be used, or a combination of gases. Product gas may also be present in the reactant gas provided to the synthesis mode, eg, NH3remaining in a recycled gas stream. This maybe <25%, <15%, <10%, or <5% NH3. In particular embodiments, there may be less than about 5% product gas in the reactant gas stream. In particular embodiments, there maybe less than about 10%product gas in the reactant gas stream. A benefit of the sorbent plus catalyst reactor is an improved resistance to product gas in the feed gas, which normally inhibits the reaction and limits to about <4%.

[0228] Synthesis mode begins when a second reactant species is then introduced such that a reactant gas is present in the bed. For example, by introducing a second reactant species N2to a bed charged with a first reactant species H2. In another example, the first reactant species is N2and the second reactant species in H2. The introduction of the second reactant gas causes formation of a product species (NH3) at the catalyst, which causes sorption of the product species to the sorbent. In one example, H2and N2are introduced as the reactant gas. While reactant gas is introduced at the vessel inlet, there may or may not be flow at the vessel outlet. This depends on the rate of reaction plus sorption, a process which consumes molecules such that the outlet flow is less (on a molar basis) than the inlet flow and can be zero. The outlet flow is termed the synthesis effluent. In the initial part of synthesis, the outlet flow comprises primarily or exclusively the pressurization gas, as the reactant species has not yet reached the outlet of the reactor, and / or any product gas has been sorbed. In one example, the synthesis effluent flow is primarily N2. In another example, it is H2. In another example, it is N2and H2. It maybe beneficial for the synthesis outlet gas to contain only the first reactant species so the outlet gas can be directly re-used (either with or without compression) as a gas for other cycle operations. That is, it is beneficial for the effluent stream to have substantially the same composition as the reactant gas or the pressurization gas. As synthesis progresses, the second reactant gas and the product may “breakthrough”, becoming present in the synthesis effluent. Before breakthrough, the synthesis effluent is useful as a sweep gas or repressurization gas to another vessel, being substantially pure and at high pressure. In one example, the pressure of the vessel in the synthesis operation is regulated at the outlet such that the inlet pressure is greater than the outlet and the outlet pressure is substantially constant. In this example, the inlet pressure may vary over time, and therefore so does the pressure drop across the reaction bed. The outlet flow rate also varies with time, initially being as low as zero while the reactant gas is fully consumed by reaction and sorption, and increasing over time. Any of these signals of outlet gas flowrate, inlet gas pressure, pressure drop, and outlet gasconcentration may be used to control the operation. Each may mark the desired end of the synthesis step and prompt controlling the system to advance its schedule. The length of the synthesis step can be controlled to maximize the reactant gas conversion and reaction rate over the length of the operation. We have surprisingly found that the conversion is maximized when the reactant gas is introduced to the vessel for a certain length of time less than too residence times, and typically between 3-15 residence times. In one example, the synthesis step is performed where the reactant gas is introduced for a set period of time related to the residence time. In another example, the reactant gas is introduced until the outlet flowrate and / or bed pressure drop are substantially constant. In another example, the reactant gas is introduced until the outlet flowrate has reached a certain rate as a function of the reactant gas flowrate, e.g., 20%, 40%, 50%, 60%, 70%, 80%, 90%. In another example, the reactant gas is introduced until the synthesis effluent shows substantial presence of the product gas or second reactant gas, which maybe 1%. The sorbent progressively saturates with the product species during synthesis, and ends in a saturated state that is greater than the saturation level before synthesis. This may include an increase in saturation from 0-100%, or 10-90%, starting at any one of 0%, 10%, 20%, 30%, 40%, or 50%, ending at any one of 40%, 50%, 60%, 70%, 80%, 90%, or 100%.

[0229] Inlet flowrates are chosen to maximize conversions and production rates. These preferably correspond to GHSV of <io,ooo / hr, or <5,ooo / hr, or between 50- 4000 / hr. In a particular embodiment, the inlet flowrate maybe between about 50-4000 / hr. The flowrates in combination with the pressure, catalyst / sorbent size, vessel size and aspect ratio are also chosen to maintain heat and mass transfer for the exothermic synthesis process. These influence linear velocity and in particular the Reynolds number (Re) which describes heat and mass transport. In some cases, the Re is greater than 1, greater than 3, greater than 5, or greater than 10. It may be desirable to maximize Re at a given gas hourly space velocity (GHSV).

[0230] The synthesis pressure is chosen to balance reaction equilibrium and system cost. This pressure can be 10-50 bar, 20-45 bar, or about 30 bar.

[0231] Block S210 is a cycle process preferably used as a cycle state for each reaction vessel with a catalyst and sorbent. S210 may not be a cycle state used for reaction vessels with a sorbent-only reaction bed.

[0232] Block S220, a rinse operation, which includes rinsing the reaction vessel, functions to cleanse a sorbent bed or catalyst plus sorbent of the reaction vessel to remove residual materials and increase the concentration of product gas in a vessel prior to desorption. S220 can be after the sorbent bed of a reaction bed is saturated with ammonia or at least in a sufficiently saturated state (e.g., satisfying some threshold condition of saturation such as 95% saturated). Accordingly, S220 maybe a process directly after S210. This may alternatively be a cycle state following sorbing of ammonia in a reaction vessel with a sorbent-only reaction bed. When a reaction bed is in some saturated state, there maybe residual nitrogen (N2) and hydrogen (H2) within pores of the bed. Rinsing the reaction vessel may push or flush the nitrogen and hydrogen out before desorbing ammonia from the reaction bed such that eventually desorbed ammonia is more enriched. The rinse gas can comprise the product species. In one example, the rinse gas is substantially 100% of the product species (NH3). The rinse gas can be any content of product species such that the partial pressure of the product species in the rinse gas greater than the vapor pressure of the sorbent; and such that the concentration of the product species in the rinse gas is greater than the gas phase concentration of product species in the vessel at the start of the rinse operation (such that the rinse increases the product gas concentration). In another example, the rinse gas can comprise a reactant species, reactant gas, or an inert gas. The rinse gas may be pure H2to flush a bed of N2prior to blowdown. The rinse gas may be a combination of H2and N2to ensure a controlled ratio of H2and N2prior to blowdown.

[0233] In one variation shown in FIGURE 8, rinsing the reaction vessel comprises rinsing the sorbent bed with NH3. Pure NH3 maybe flowed through the reaction vessel at a high pressure (e.g., P_high). Pure NH3 maybe fed to the reaction bed at a pressure higher than the bed pressure. This pressure may be near or at P_high. This rinse feed can carry out residual nitrogen and hydrogen so a mix of mostly ammonia with trace N2 and H2 may be outputted from the reaction vessel. Pressure may decrease slightly down the bed from the forced flow pressure drop.

[0234] To reduce possibility for decomposition of the product gas in the rinse gas over the catalyst or otherwise, the method may include cooling the reaction bed to a temperature to render a used catalyst as effectively inactive for decomposition. This may include cooling below 200°C. This maybe useful for reaction vessels with a catalyst and sorbent reaction bed to prevent decomposition of the ammonia rinse feed. Cooling may or may not be used with a reaction vessel with a sorbent-only reaction bed.

[0235] In another variation shown in FIGURE 9, rinsing the reaction vessel may include rinsing the sorbent bed with nitrogen. Pure nitrogen gas (N2) maybe flowed through the reaction vessel at a high pressure (e.g., P_high). Rinse gas maybe fed to the reaction bed at a pressure higher than the bed pressure. In a similar manner, the nitrogen rinse feed carries out the residual N2 and H2 but leaves behind N2 in the pores since N2 is the motive fluid. Residual nitrogen in pores maybe preferably to residual hydrogen (H2), as N2 maybe easier to separate downstream than residual hydrogen. Hydrogen may be more expensive to recompress. A rinse step with a non-product gas requires a sorbent with sufficiently slow desorption kinetics in the rinse condition, as lack of product species in the gas phase will induce desorption.

[0236] A high pressure may be used to facilitate mitigating occurrences of ammonia desorbing. During the rinse, the sorbed (e.g., adsorbed) NH3 will want to desorb as there is no NH3 in the gas phase. At sufficiently high pressures (e.g., similar to P_high), NH3 desorption may be slowed enough to be minimal. This may be because gas diffusivity decreases at increased pressures.

[0237] In another variation, rinsing the reaction vessel may occur with a gas that reversibly adsorbs, especially chemisorbs, to the catalyst, for example, H2, H2O, O2, air, H2S, or other, including mixtures thereof. This adsorbed gas may reduce decomposition of ammonia in subsequent desorption steps as in block 130 by blocking catalytically active sites for ammonia decomposition and / or influencing the equilibrium composition of the mixture. Different sorbents may benefit from using different types of rinse cycles.

[0238] In some variations, multiple gases may be used for the rinse stage either as mixtures or sequentially.

[0239] Block S230, which includes performing desorption process in the reaction vessel, functions to perform a blowdown process and extract the sorbed ammonia fromthe reaction bed as an output of the reaction vessel. Desorption can include blowdown, depressurization, purge, sweep, or analogous operations.

[0240] Desorbing may be a cycle state that is initiated following S210 or S220. When initiating the desorption process, the reaction bed is preferably in a saturated state with ammonia, has a high pressure (e.g., pressurized to P_high), and may have N2, H2, and / or NH3 in the interstices depending on preceding cycling processes used.

[0241] Desorption is endothermic, so heat must be added to remain at a constant temperature. In some variations, the desorption process may be performed in parallel with an exothermic cycle of thermally coupled reaction vessel. For example, S210 may be performed in a reaction vessel adjacent to a reaction vessel where S230 is occurring.

[0242] Alternatively, the reaction bed may be allowed to decrease in temperature by the desorption step.

[0243] In one variation herein referred to as a “total blowdown” variation shown in FIGURE 10, the reaction vessel is opened to a low-pressure environment, likely a substantially empty header or surge vessel, which may be an extra defined volume to hold the gas that desorbs. Accordingly, performing desorption process in the reaction vessel may include exposing the reaction vessel to a low-pressure condition.Alternatively stated, block S230 may be performed by or include de-pressurizing to a P_low pressure. The gas in the interstices will preferably exit rapidly, followed by sorbed ammonia (e.g., adsorbed NH3), which desorbs in this process. The exiting gas will be at a pressure of the exposed environment, referred to as P_ low. This may be the lowest pressure of the system. The exiting gas is termed a blowdown stream.

[0244] Depressurizing to a P_low pressure as part of the “total blowdown” variation may continue until the reaction bed reaches the P_low. At this point the reaction bed may be nearly or completely unsaturated with ammonia. The bed may also be partially saturated or fully saturated with ammonia.

[0245] In some variations, P_low is sufficiently high that the partial pressure of NH3 in the desorbed stream (i.e., the output) is above its condensation point at room temperature (e.g., around 8 bar at 20C). In some variations, this maybe between 8-10 bar. A sufficiently high P_low may allow avoiding a step of re-pressurizing the desorbed gas to be able to condense it and output liquid ammonia, which is often a desirablematerial product output of the method. Even if P_low is below the condensation point, maximizing P_low reduces the size and energy demand for recompression. The backreaction to decompose NH3 is also less favored at increasingly high pressures.

[0246] A reduced P_low may have a potential benefit of desorption occurring increasingly fast at decreasing desorption pressures. In other words, lower P_low will desorb NH3 more quickly than a higher P_low. This may have the potential benefit of reducing the residence time of NH3 as it desorbs, which reduces cycle times and reduces the time for the backreaction to occur. Accordingly, a method may select P_low depending on desired performance and conditions. P_low in some variations is 1-40 bar, more preferably around 10 bar (e.g., 8-10 bar). However, depending on implementation, the method may operate using 1 bar for example.

[0247] In a variation using an adsorbent, the relationship between pressure and ammonia loading may have a linear or otherwise smooth continuous relationship allowing the P_low to be selected within a range. Accordingly, P_low may be set to be a moderately lower pressure than P_ high. For example, in one variation, P_ high maybe 15-25 Bar, and P_lowmaybe 8-10 Bar. This can be sufficient to desorb the adsorbed ammonia. This may also be a pressure where gaseous ammonia may be liquified by lowering temperature, thereby avoiding additional pressurization.

[0248] In some variations, performing desorption process in the reaction vessel may be performed by performing a multistage blowdown process wherein during an initial blowdown (i.e., de-pressurization) stage, depressurizing the reaction vessel into a parallel vessel (preferably directing a mostly reactant gas (nitrogen and hydrogen output), and during a final blowdown stage, depressurizing the reaction vessel to P_low to desorb ammonia.

[0249] As an initial blowdown desorption process, the reaction vessel may include depressurizing into a parallel vessel. The parallel vessel is a reaction vessel that recently underwent blowdown.

[0250] As shown in FIGURE 11, the initial blowdown stage that includes depressurizing the reaction vessel into a parallel vessel, functions to initially vacate nitrogen and hydrogen in the interstices and to potentially use the mostly nitrogen and / or hydrogen output in another reaction vessel. The vessel can be opened to a low-pressure environment. The sudden pressure release causes gas to exit the system. The gas in the interstices will exit most rapidly, followed by adsorbed NH3, which desorbs in this process.

[0251] As the residual nitrogen and hydrogen will leave more rapidly than the sorbed ammonia, the initially outputted gas (which is mostly N2 and H2) maybe directed into a parallel reaction bed that has recently undergone blowdown. This provides a method of recycling the feed gas left in the interstices. Accordingly, management of material output of a reaction vessel may include directing gas output to a parallel reaction vessel during when the gas output is mostly nitrogen and hydrogen. This may involve timing redirecting of the output gas. This may alternatively include sensing and dynamically changing directing of output gas. Alternatively, this initial vacated output gas that is mostly nitrogen and hydrogen could be vented or otherwise directed.

[0252] This initial depressurization may also include depressurizing to a pressure lower than P_high and greater than P_low, referred to as P_intermediary.P_ intermediary may be the pressure of the connected parallel vessel P_ vessel, for example, a parallel vessel in the repressurization stage.

[0253] As shown in FIGURE 12, subsequent final blowdown stage may include depressurizing the reaction vessel to a low-pressure threshold (e.g., P_low) and thereby desorbing ammonia. The starting point of this stage is a less-pressurized bed. With the initial blowdown stage, the reaction bed also may have minimal or reduced nitrogen and / or hydrogen in the interstices. The reaction vessel may be opened to a surge vessel at P_low, where P_low is less than P_intermediary. With the release of remaining pressure of the vessel, output gas exits the reaction vessel and is collected in the surge vessel. The blowdown stream may have increased concentration of product gas compared to the depressurization stream.

[0254] A blowdown stream may comprise at least 5% of product species.

[0255] The direction of the blowdown and depressurization streams may influence effluent gas compositions and the end-state of the sorbent / catalyst bed. Blowdown may occur co-current or counter-current to the synthesis stage. If the sorbent portion of the reaction bed is more saturated towards the upstream end, counter-current blowdown ispreferred. If the sorbent portion is more saturated towards the downstream end, cocurrent is preferred.

[0256] Blowdown and desorption, generally, are path dependent phenomena, wherein a shorter desorption path may increase the rate of desorption at a given flowrate. For this reason, it can be beneficial to blowdown (or desorb, generally) through multiple reactor outlets, for example, the top and the bottom of the vessel simultaneously, such that the effective exit path of the desorbing product gas is reduced. To achieve this, the effluent stream maybe withdrawn from either the same port (or port on the same side of the vessel) as the synthesis reactant gas stream, or a different one.

[0257] At the end of the step, the sorbent in the reaction vessel may be effectively unsaturated, and the pressure has equalized at P_low. Depending on the sorbent and operating conditions, the sorbent may still have trace NH3 adsorbed, in which case an optional purging cycle stage (e.g., S240) maybe used. Alternatively, the reaction vessel may proceed to a repressurization cycle stage (e.g., S250).

[0258] In some variations or in some desorption step variations, performing desorption process in the reaction vessel may include introducing a “sweep gas” through the reaction vessel in a sweep operation, also known as a purge operation. The sweep gas may, in some variations, include nitrogen and / or hydrogen and / or argon or other gas inert to the catalyst and / or sorbent (e.g., an H2 / argon mixture). The sweep gas may be fed through a feed end of the reaction bed to help push out ammonia. The sweep gas may also reduce effective concentration of ammonia through the reaction bed during desorption, which may minimize or reduce back-reaction. Including hydrogen (H2) here may benefit minimizing backreaction as well.

[0259] As shown in FIGURE 13, block S240, termed a sweep or purge operation, which includes purging the reaction vessel, functions to remove any remnant materials from the bed in a vessel. After desorbing in S230, trace amounts of ammonia may remain sorbed in the sorbent and / or interstices following depressurization. In some variations, it may be desirable to remove and / or recover these remnant materials before preparing the reaction vessel for a new cycle. Accordingly, the optional cycle stage of purging the reaction vessel may be used. At the beginning of a purging cycle stage, thebed is at P_low and ammonia maybe contained in the interstices and / or sorbent. A sweep / purging feed of any gas, preferably a reactant gas, alternatively an inert gas, for example, pure nitrogen maybe flowed through the bed to purge any residual ammonia. As a result, an output stream of mostly nitrogen with trace ammonia would exit as an output. In some variations, this output may be vented or otherwise discarded. In other variations, the sweep effluent may contain substantial concentrations of product gas that are desirably recovered. The purging stage will result in a reaction bed preferably be completely unsaturated or at least more desaturated with ammonia, which could enhance preparation of the reaction vessel for repressurization.

[0260] In one example, the sweep gas comprises H2. This functions to inhibit the backreaction of desorbing NH3to N2and H2.

[0261] In one example, the sweep gas velocity is chosen to minimize the residence time of desorbing product gas to reduce the backreaction. The sweep gas velocity can be equal to or greater than the velocity of the reactant gas during synthesis. In some variations, the sweep gas velocity is greater than the reactant gas velocity. In other variations, the sweep gas velocity is substantially the same as the reactant gas velocity. The sweep gas velocity may be maximized while avoiding fluidization of the catalyst or sorbent in a reaction bed. The sweep gas velocity maybe maximized while avoiding creating a pressure drop across the bed during the sweep operation, for example, the sweep gas velocity maybe chosen to limit a pressure drop to below about 0.5 bar, 1 bar, 2 bar, 3 bar, or 5 bar. In some aspects, the residence time of the sweep gas can be less than the residence time of the reactant gas. In one variation, the mass flow rate of the sweep gas maybe substantially the same as the reactant gas flow rate. In another variation, the molar flow rate of the sweep gas may be substantially the same as the reactant gas flow rate. It can be beneficial for maintaining constant gas flow to the set of reaction vessels to have sweep gas and synthesis gas streams be substantially identical in composition and flowrate. In one variation, the sweep gas stream maybe provided from a different gas source than the reactant gas stream, such that the sweep and reactant gas streams can differ in flowrate and composition while maintaining a continuous flow of each to the set of reaction vessels. Referencing FIGURE 1 In one variation, there maybeseparate sources and headers for the sweep gas (also referred to as the purge gas) (140) and the reactant gas (also referred to as the feed gas) (150).

[0262] In another example, the sweep gas effluent may be withdrawn from multiple ports as in the blowdown stage. The sweep gas may flow co-current or counter-current to the synthesis reactant gas.

[0263] In some variations, the sweep gas may encourage further desorption of product gas from the sorbent. Substantial product gas may be present in the sweep effluent. The sweep operation may continue until sufficiently low concentrations or partial pressures of product gas are present, for example, until <1 bar, <0.6 bar, <0.4 bar, <0.2 bar, <0.1 bar are present. This partial pressure is a proxy for the level of saturation of the sorbent bed.

[0264] In some variations, the purging step may be used to prepare the catalyst for the block S210 reaction step. The purge gas may serve to reduce or otherwise restructure the catalyst to improve activity and / or to reverse the optional chemisorption described in certain variations of the S220 rinse step. The purge gas in these variations maybe N2, H2, or an H2 containing mixture. The temperature of the vessel in this step maybe increased or decreased to benefit the purging process. In particular, decreasing the temperature in the desorption, blowdown, depressurization, and / or sweep steps may decrease the rate of the backreaction. However, increasing the temperature may aid rates of desorption from the sorbent. In each step, the effluent and inlet gas flowrates may be maintained less than or equal to the fluidization velocity of the particles in the reaction bed. In other variations, the flowrates may be greater than the fluidization velocity of the particles in the reaction bed. In some variations, the velocity in the purging step maybe greater than the velocity of the synthesis step.

[0265] As shown in FIGURE 14, block S250, which includes repressurizing the reaction vessel in a pressurization operation, functions to return a reaction vessel to a suitable pressure for reacting nitrogen and hydrogen with a catalyst. Repressurizing preferably prepares the reaction vessel to perform block S210. Repressurizing may use nitrogen and / or hydrogen, and NH3may be present as well. The repressurization gas may have the same composition as the reactant gas, and may include one or more reactant species and / or product species. In one example, the repressurization gas is N2.In another example, the repressurization gas is H2. In another examples, the repressurization gas is a combination of N2and H2. In one example, the repressurization gas does not contain a full set of reactant species for a reaction to occur. In another example, the repressurization gas does contain a full set of reactant species for a reaction to occur.

[0266] When repressurizing a bed, a reaction vessel may be closed on one end and feed a pressurizing gas on the other end or through one or more other material ports. In general, the bed will initially be at P_low so any pressure higher than the current bed pressure maybe acceptable for the feed. This allows effluent streams from synthesis, depressurization, blowdown, desorption, sweep, and / or rinse to be used as the pressurization gas. The pressurizing feed gas may be fresh gas, but it may be an output of S210, S220, an output from initial blowback step in S230, and / or S240.

[0267] In some variations, repressurizing may use the same or similar gas composition that is intended to be adsorbed from. In a sorbent-only reaction vessel, repressurizing may be performed using NH3 gas. Adsorption capacity may increase with increasing pressure and so it may be beneficial to increase the pressure to a suitable level.

[0268] Repressurizing may happen in a single step. Alternatively, repressurizing the reaction vessel may include repressurizing from a first pressurizing feed gas source and switching to repressurizing from a second pressurizing feed gas source. In this way, pressurizing the reaction vessel may use gas sources from multiple sources. The mixture of gas may also be different across those different sources. For example, one source may be a mix of nitrogen and hydrogen, and another may be pure nitrogen.

[0269] In some variations, repressurizing from multiple sources may include repressurizing with a gas from a source with lowest available pressure and sequentially step up to higher-pressure feeds as the bed pressure rises and lower pressure feeds become inaccessible.

[0270] The pressurizing feed gas may be any makeup of nitrogen and / or hydrogen. If both nitrogen and hydrogen are present, the reaction to NH3 may happen in a bed that also contains a catalyst, in which case this step is similar to the synthesis operation. It may be beneficial to feed with mostly N2 or H2 and not both, such that the reaction isonly triggered in the synthesis operation. Pressurizing the reaction vessel may happen until a pressure of P_high is reached in the bed of the reaction vessel, at which point the synthesis operation begins. There may not be a clear transition between the synthesis operation and re-pressurization operation, especially when a similar composition of H2and N2is provided to each

[0271] These cycle states S210, S220, S230, S240, and / or S250 can be implemented in parallel, at staggered cycles across a plurality of reaction vessels. How the material flow communication is managed can depend on the exact configuration.

[0272] In an exemplary variation with one catalyst-sorbent reaction vessel and two sorbent reaction vessels, cycle states maybe implemented as shown in FIGURES 15-17. As shown in FIGURE 15, ammonia maybe synthesized in a first vessel which will be sorbed by the sorbent. The output stream would contain nitrogen and hydrogen which could be used to backfill such as for a second vessel. As shown in FIGURE 16, ammonia may be used to rinse a first vessel after it has reached saturation. As shown in FIGURE 17, a first vessel may experience blowdown for desorption of ammonia. As shown in FIGURE 18, a first vessel maybe repressurized, possibly using material source from output of a vessel undergoing reaction cycle state (like in a first vessel of Synthesis (step 1 of FIGURE 15)).

[0273] FIGURES 19-21 shows an alternative coordination of production cycle states with fluid communication between reaction vessels. These variations and configurations are not limiting, and other coordination of cycle states and system configurations may be used.

[0274] One potential objective of the method may be to maintain constant production rates, including constant feed gas and product gas rates. Such a variation may use multiple vessels scheduled to allow for continuous operation. A variation may use equal time-length schedule blocks for each operation and one vessel (or cluster) in each operation at a time. Here, synthesis, blowdown, other operations may all be the same length of time. However, synthesis and sweep have a longer characteristic time that the “fast” steps of blowdown and repressurization. To force time-matching, one can artificially slow down the repressurization and blowdown steps, or alternatively allow “idling” where a step is finished but hasn’t progressed to the next step yet.

[0275] Alternatively, the schedule may have steps take different amounts of time, such that different numbers of reactors / clusters are in each step at a time. Such a variation may be configured to maximize or increase the percent time that any given vessel spends in synthesis, as this relates to effective catalyst / sorbent utilization. The percentage of time spent in synthesis may correspond to integer fractions of the total number of vessels in the set. One can have a vessel in synthesis mode 50% of the time, 33% of the time, 40% of the time, or 60% of the time, e.g., corresponding to an integer fraction such as 1 / 2, 1 / 3, 2 / 5, or 3 / 5 of the total number of vessels / clusters in synthesis simultaneously, in some cases less than about 10.

[0276] It can be useful here to define desorption as “everything but synthesis” such that synthesis takes 50% of the time and desorption takes 50% of the time. Or, equal thirds of synthesis, desorption, and re-pressurization. Sweep is typically the longest part of desorption - so, time matching synthesis and sweep can be useful too. In some cases, synthesis takes longer than desorption.

[0277] As used herein, the terms "first", "second", "third", etc. are used to characterize and distinguish various elements, components, regions, layers and / or sections. These elements, components, regions, layers and / or sections should not be limited by these terms. Use of numerical terms may be used to distinguish one element, component, region, layer and / or section from another element, component, region, layer and / or section. Use of such numerical terms does not imply a sequence or order unless clearly indicated by the context. Such numerical references may be used interchangeable without departing from the teaching of the embodiments and variations herein.

[0278] As used herein, the term "residence time" generally refers to any one of (a) the length of time for a molecule to transverse the length of a reaction zone at the inlet conditions and flowrate absent a reaction or sorption (b) the average length of time for a molecule to transverse the length of a reaction zone under reaction and / or sorption conditions.

[0279] As used herein, the term "Reactive PSA process" generally refers to a process for producing a product species from one or more reactant species by an iterative cycle of at least one of synthesis, desorption, blowdown, purge, and / or repressurization

[0280] AS used herein, the term "compressor" generally refers to a device for increasing the pressure of a fluid and includes a blower or fan.

[0281] As used herein, the term “sorption” generally refers to uptake of a molecule onto or into a solid, and may include adsorption, absorption, or combinations thereof.EXAMPLESExample 1 - Three-vessel ammonia production cycle

[0282] A system with three reaction vessels each 6m long and 2” inner diameter with a 1:1 sorbent:catalyst ratio was simulated in gPROMS.

[0283] With reference to FIGURE 25, the system had three reaction vessels, Vessel 1 (2501), Vessel 2 (2502), and Vessel 3 (2503).

[0284] Referring to FIGURE 26, the operation of the Vessels were scheduled to alternate between operations by time blocks 50s long (or multiples thereof). The operations include synthesis (denoted as "S"), blowdown (denoted as "B"), purge (denoted as "P"), and re-pressurization (denoted as "R").

[0285] At time o, Vessel 1 was freshly re-pressurized at 30 bar with a mixture of H2and N2 and an unsaturated bed. Vessel 3 was at 30 bar with a saturated bed.

[0286] At time o valve 2504 was open and reactant gas flowed from the feed header into vessel 1 to initiate synthesis (S in table). Valve 5 and 6 were open so as to maintain a constant outlet pressure at vessel 1 while the synthesis effluent was directed to vessel 2, to perform repressurization (R in table). Valve 10 was open and valve 7, 8, and 9 were closed for vessel 3 to perform blowdown: blowdown gas exits to the desorption header.

[0287] At time 50s, Valve 9 opened to start purge (P) in vessel 3: N2flowed into vessel 3.

[0288] At time 200s, valve 4 and 5 closed and valve 7 opened to initiate blowdown in vessel 1. Valve 11 opened to begin synthesis mode in vessel 2 with valves 13 and 14 open to direct the synthesis effluent to vessel 3. Valves 9, 10 and 12 closed to put vessel 3 in re-pressurization.

[0289] At time 250s valve 4 opened to start purge in vessel 1.

[0290] At time 400 valve 4, 5, and 7 closed and valves 9, 12 and 15 opened to put vessel 1 in re-pressurization and vessel 3 in synthesis with the synthesis effluent used forre-pressurization. Valve n and 14 closed and valve 8 opened to put vessel 2 in blowdown.

[0291] At time 450 valve 11 opened to put vessel 2 in purge.

[0292] At time 600 the system was in substantially the same state as just before time o and the cycle repeated.

[0293] The method was simulated until a cyclic steady state was reached after ~io cycles and a feedstock conversion of 58% was maintained.Example 2 - Six-cluster ammonia production cycle

[0294] A system with six clusters of reaction vessels was simulated in gPROMS. Each cluster iteratively underwent Synthesis, De-pressurization, Blowdown, Purge, and Repressurization. Figure 27 shows the system at time is, referring to Figure 28. Clusters 1 and 2 were in the synthesis operation where reactant gas was introduced to the clusters (2701). Cluster 3 was in Equalization Down (ED), which is an implementation of the depressurization operation. Cluster 3’s outlet was routed to Cluster 6 which is in Equalization Up (EU) (2702), a form of re-pressurization. Clusters 4 and 5 are in Purge mode, receiving purge gas that is the synthesis effluent from Clusters 1 and 2 (2703).

[0295] Referring to Figure 28, as time progresses, there were always two clusters in synthesis, one each in equalization up and equalization down, and two clusters in purge. As such, the flow of reactant gas into the system was constant and the flow of product gas out of the system was constant.

[0296] The method was simulated until a cyclic steady state was reached after ~io cycles and a feedstock conversion of 55% was maintained.Example 3 - Concentration swing cycle

[0297] A reactive PSA process was simulated in gPROMS on a 6m long by 2” ID tubular packed bed reactor with a heterogeneous mixture of catalyst and sorbent at a 1:1 mass ratio. The cycle included iterative Synthesis and Purge steps, but did not include a blowdown or depressurization step. In this way, produced ammonia was removed only in the Purge step by a concentration swing. N2was used as the purge gas. Table 1 includes the results.Table 1 - Concentration swing cycleExample 4 - Rinse cycle

[0298] A reaction vessel 6m long and 2” inner diameter with a 1:1 sorbent: catalyst ratio was simulated in gPROMS to cyclic steady state. The cycle included, in order, a Synthesis operation, Rinse operation, Blowdown operation, Purge operation, and RePressurization operation. The composition of the Rinse gas was varied by mol% NH3, with the balance a 3:1 H2 / N2ratio. The results are shown in Table 2. Increasing the %NH3 increased the blowdown stream concentration while decreasing the production rate. Blowdown NH3concentration is less than the %NH3 in rinse gas when 100% NH3is used in rinse, which may indicate decomposition of the rinse gas.Table 2 - Rinse cycleExample 5 - Decomposition in H2vs N2

[0299] We loaded a 1” diameter reaction vessel with a reaction bed of a mixture of 250g of iron catalyst and 250g of zeolite sorbent. We performed Re-Pressurization with H2, then started Synthesis by flowing H2 and N2 at a ratio of 3:1 (triggering the reaction). Pressure was maintained at 30 bar at the reaction vessel outlet. After 10 minutes, we stopped flowing N2, and did Blowdown by releasing the reactor pressure to a surge tank at 1 bar. We then did Purge with H2. We did this at 350C and 395C. We repeated the experiment, but switching the H2 in the pressurization / purge step with N2. Table 3 compares the resulting performance at each temperature and pressurization / purge gas.Table 3 - Pressurization and purge gas testsExample 6 - Basic cycle and comparison to conventional reactor, including NH3in feed tolerance

[0300] We simulated in gPROMS a reactive PSA reactor with a Synthesis, Blowdown, Purge, and Re-pressurization cycle and a conventional catalyst only reactor (with only sustained Synthesis). We varied the concentration of NH3in the reactant gas while balancing the NH3with a 3:1 ratio of H2to N2. The results are shown in Table 4. The reactive PSA demonstrated increased conversions and production rates at the same temperatures and pressures as the conventional reactor, even when the reactant gas included 12% NH3. By comparison, feeding 12% NH3to the catalyst only reaction gas led to no reaction occurring.Table 4 - Comparison of Reactive PSA to conventional reactorExample 7 - First and second effluent stream

[0301] We loaded a 1” diameter reaction vessel with a reaction bed of a mixture of 250g of iron-based catalyst and 250g of zeolite sorbent. A mass spectrometer was placed at the outlet of the reactor. Referring to Figure 29, we performed Re-Pressurization by flowing H2(as the first reactant gas) into the reactor (2901) until an outlet pressure of 30 bar was reached (2902). We reduced the H2flowrate to the desired total reactant gas velocity (2903). We then initiated Synthesis by introducing N2 as the second reactant gas (2904). We then resumed H2flow at the total reactant gas velocity until the reactant species N2was seen at the reactor outlet (2904). Until this time, the synthesis reactor effluent substantially comprised H2, the first reactant gas, which is the synthesis effluent and the first effluent stream (2905). We then performed blowdown by reducing the reactor pressure to 1 bar, causing NH3to leave the reactor (2906) as the second effluent stream and blowdown stream. H2flow continued as the sweep gas. 52% H2conversion was achieved.Example 8 - Temperature swing desorption

[0302] We loaded a 3 / 8” diameter vessel with a reaction bed of a mixture of an Ru- based catalyst and FAU zeolite sorbent. A mass spectrometer was placed downstream of the bed. Two cycles were performed consecutively. In cycle 6A, synthesis was performed with a reactant gas of H2and N2at 300C and 515 psig (2301). Blowdown was performed to o psig (2302), followed by purge with N2(2303). NH3eluted during blowdown and purge, resulting in an effluent stream enriched in NH3product species (2304). The reaction bed and vessel were then repressurized to 515 psig with N2(2305). Synthesis, blowdown, and purge were performed again identically. Then, the temperature of the reaction vessel was raised to 500C (2306). Substantially no NH3eluted during the temperature increase (2307).Example 9 - Cyclic steady state

[0303] We loaded a 1” diameter vessel with a reaction bed of a combined catalyst / sorbent structure with iron catalyst. A mass spectrometer was placed downstream of the bed. 100 cycles were performed consecutively, varying cycle conditions until the last 10 cycles. FIGURE 30 shows the final 10 cycles, which included Synthesis, Blowdown, Purge, and Repressurization. The H2conversion was steady at 66% + / - 1% (3001).Exemplary Embodiments

[0304] Hereafter are described different aspects of various embodiments of the systems and methods. These aspects are not intended to limit the systems and methods and do not include every variation and combination of variations of the systems and methods described herein. Features which are described in the context of separate aspects and embodiments of the invention may be used together and / or be interchangeable. Similarly, features described in the context of a single embodiment may also be provided separately or in any suitable sub-combination.

[0305] Embodiment 1.1: A method for making a gaseous product, the method comprising: a) introducing a reactant gas within a vessel containing a catalyst andsorbent, whereby the catalyst facilitates a conversion of the reactant gas into a product species and the product species is selectively sorbed by the sorbent; b) withdrawing a first effluent stream from the vessel; and c) withdrawing a second effluent stream from the vessel, wherein the second effluent stream is enriched in the product species relative to the first effluent stream.

[0306] Embodiment 2.1: A system for production of a product species, the system comprising: a) a set of reaction vessels, each reaction vessel comprising: I. a vessel body comprising an input material port for receiving a reactant gas and an exit material port for withdrawing an effluent stream, II. a reaction bed within the vessel that comprises a sorbent and / or a catalyst, wherein the catalyst facilitates a conversion of the reactant gas to a product species and the sorbent sorbs the product species, b) a material conduit system configured to (i) introduce the reactant gas to each of the set of reaction vessels through the input material ports and (ii) withdraw the effluent stream from each of the set of reaction vessels through their exit material ports; c) a control system configured to, for each of the reaction vessels, iteratively, (i) introduce the reactant gas to the reaction vessel and (ii) withdraw the effluent stream from the reaction vessel, wherein, the reactant gas provided to the set of reaction vessels has a substantially constant flow rate.

[0307] Embodiment 3.1: A method for making a gaseous product, the method comprising, iteratively: a) performing a synthesis operation, wherein a reactant gas comprising a reactant species is introduced to a reaction vessel containing a catalyst and a sorbent, wherein the catalyst facilitates conversion of reactant species into a product species and the sorbent sorbs the product species; and b) performing a desorption operation, wherein the product species desorbs from the sorbent and a product gas comprising the product species is withdrawn from the reaction vessel.

[0308] Embodiment 4.1: A method comprising: managing material communication between a set of reaction vessels and thereby cycling a set of reaction vessels through different stages of ammonia synthesis and separation, which comprises for each reaction vessel: reacting nitrogen and hydrogen with a catalyst to capture ammonia in a sorbent of the reaction vessel, rinsing the reaction vessel, performing desorption processin the reaction vessel, purging the reaction vessel, and / or repressurizing the reaction vessel.

[0309] Embodiment 5.1: A system comprising: a set of reaction vessels, with each reaction vessel including at least a sorbent or catalyst, a material stream conduit system, the set of reaction vessels integrated through material stream conduit system, and a control system configured to cooperatively manage cycling of the set of reaction vessels and material flow between reaction vessels through the conduit system.

[0310] Embodiment 1.2: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising, prior to introducing the reactant gas within the vessel, pressurizing the vessel.

[0311] Embodiment 1.3: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas comprises a first reactant species and a second reactant species, wherein the product species is formed from a reaction between the first reactant species and the second reactant species.

[0312] Embodiment 1.4: A variation of embodiments 1.1, 1.3, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the vessel is pressurized with the first reactant species, an inert gas, or any combination thereof.

[0313] Embodiment 1.5: A variation of embodiments 1.1, 1.3, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the vessel is pressurized with the first reactant species.

[0314] Embodiment 1.6: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a pressure of the vessel is regulated at an outlet of the vessel while the reactant gas is introduced into the vessel.

[0315] Embodiment 1.7: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein introducing a reactant gas into a vessel and withdrawing a first effluent stream from the vessel occur simultaneously.

[0316] Embodiment 1.8: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein withdrawing a secondeffluent stream from the vessel is performed subsequent to withdrawing a first effluent stream from the vessel.

[0317] Embodiment 1.9: A variation of embodiments 1.1, 1.3, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the first effluent stream contains substantially no second reactant species.

[0318] Embodiment 1.10: A variation of embodiments 1.1, 1.3, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas is introduced into the vessel until the first effluent stream contains more than 1 vol% of the second species.

[0319] Embodiment 1.11: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the first effluent stream contains substantially no product gas.

[0320] Embodiment 1.12: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas is introduced into the vessel until the first effluent stream contains more than 1 vol% of the product gas.

[0321] Embodiment 1.13: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas is introduced into the vessel until a flow rate of the first effluent stream is substantially constant.

[0322] Embodiment 1.14: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas is introduced into the vessel until a pressure drop across the vessel is substantially constant.

[0323] Embodiment 1.15: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas is introduced into the vessel for a period of time between about 1 and about 100 residence times.

[0324] Embodiment 1.16: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas isintroduced into the vessel for a period of time between about i and about 20 residence times.

[0325] Embodiment 1.17: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas flow has a gas hourly space velocity less than about 10,000 / hr.

[0326] Embodiment 1.18: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas flow has a gas hourly space velocity less than about 5,000 / hr.

[0327] Embodiment 1.19: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the Reynold's number of the reactant gas in the vessel is greater than about 5.

[0328] Embodiment 1.20: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas is introduced at a pressure between about 10 and about 50 bar.

[0329] Embodiment 1.21: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising introducing a rinse gas comprising the product species into the vessel prior to withdrawing a second effluent stream from the vessel.

[0330] Embodiment 1.22: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising subsequently to withdrawing the first effluent stream from the vessel: a) reducing a pressure of the vessel to a blowdown pressure and withdrawing a blowdown stream from the vessel; and optionally prior to reducing the pressure to the blowdown pressure, b) reducing a pressure of the vessel to a depressurization pressure which is greater than the blowdown pressure and withdrawing a depressurization stream from the vessel.

[0331] Embodiment 1.23: A variation of embodiments 1.1, 1.22, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the pressure is reduced to the depressurization pressure before being reduced to the blowdown pressure.[O332] Embodiment 1.24: A variation of embodiments 1.1, 1.22, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the depressurization stream comprises primarily the reactant gas.

[0333] Embodiment 1.25: A variation of embodiments 1.1, 1.22, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the blowdown stream comprises at least 5 % of the product gas.

[0334] Embodiment 1.26: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the second effluent stream is withdrawn in a direction substantially co-current to a direction at which the reactant gas is introduced into the vessel.

[0335] Embodiment 1.27: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the second effluent stream is withdrawn from the vessel through multiple outlets.

[0336] Embodiment 1.28: A variation of embodiments 1.1, 1.27, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein at least one outlet is configured such that a flow path of the second effluent stream is substantially co-current to a direction at which the reactant gas flows through the vessel.

[0337] Embodiment 1.29: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas is introduced through a first material port in the vessel, and the second effluent stream is withdrawn from a second material port of the vessel.

[0338] Embodiment 1.30: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas is introduced through a first material port in the vessel, and the second effluent stream is withdrawn from the first material port.

[0339] Embodiment 1.31: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising introducing a sweep gas into the vessel while withdrawing the second effluent stream from the vessel.

[0340] Embodiment 1.32: A variation of embodiments 1.1, 1.31, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the sweep gas comprises a reactant species.

[0341] Embodiment 1.33: A variation of embodiments 1.1, 1.31, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the sweep gas comprises primarily H2.

[0342] Embodiment 1.34: A variation of embodiments 1.1, 1.31, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the sweep gas has a velocity greater than that of the reactant gas.

[0343] Embodiment 1.35: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the first effluent stream is at a pressure greater than or equal to the second effluent stream.

[0344] Embodiment 1.36: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising directing the first effluent stream to a recompression operation.

[0345] Embodiment 1.37: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising directing the second effluent stream to a separation operation.

[0346] Embodiment 1.38: A variation of embodiments 1.1, 1.31, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the sweep gas is introduced until an outlet partial pressure of the product species is less than about 0.4 bar at an outlet from the vessel.

[0347] Embodiment 1.39: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a temperature in the vessel is reduced prior to withdrawing the second effluent stream.

[0348] Embodiment 1.40: A variation of embodiments 1.1, 1.31, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the sweep gas in introduced at a flowrate less than or equal to a fluidization velocity of the catalyst and sorbent.

[0349] Embodiment 1.41: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas has at least about 5% of the product species.

[0350] Embodiment 1.42: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising, introducing the first effluent stream to a second vessel containing a catalyst and a sorbent, whereby the first effluent stream is a reactant gas for the second vessel.

[0351] Embodiment 1.43: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising, introducing the first effluent stream to a second vessel containing a catalyst and a sorbent, whereby the first effluent stream is used to pressurize the second vessel.

[0352] Embodiment 1.44: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising, introducing the first effluent stream to a second vessel containing a catalyst and a sorbent, whereby the first effluent stream is used as the sweep gas the second vessel.

[0353] Embodiment 1.45: A variation of embodiments 1.1, 1.22, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising, introducing the depressurization stream to a second vessel containing a catalyst and a sorbent, whereby the depressurization stream is a reactant gas for the second vessel.

[0354] Embodiment 1.46: A variation of embodiments 1.1, 1.22, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising, introducing the depressurization stream to a second vessel containing a catalyst and a sorbent, whereby the depressurization stream is used to pressurize the second vessel.

[0355] Embodiment 1.47: A variation of embodiments 1.1, 1.22, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising, introducing the depressurization stream to a second vessel containing a catalyst and a sorbent, whereby the depressurization stream is used as the sweep gas the second vessel.

[0356] Embodiment 1.48: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the product species is ammonia.

[0357] Embodiment 1.49: A variation of embodiments 1.1, 1.2, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the vessel is pressurized with a pressurizing gas comprising H2, N2, an inert gas, or any combination thereof.

[0358] Embodiment 1.50: A variation of embodiments 1.1, 1.2, 1.49, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the first effluent stream contains primarily nitrogen gas.

[0359] Embodiment 1.51: A variation of embodiments 1.1, 1.2, 1.49, 1.50, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the first effluent stream contains substantially no hydrogen.

[0360] Embodiment 1.52: A variation of embodiments 1.1, 1.2, 1.49, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the first effluent stream contains primarily hydrogen gas.

[0361] Embodiment 1.53: A variation of embodiments 1.1, 1.2, 1.49, 1.52, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the first effluent stream contains substantially no nitrogen.

[0362] Embodiment 1.54: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the first effluent stream has substantially the same composition as the reactant gas.

[0363] Embodiment 1.55: A variation of embodiments 1.1, 1.2, 1.49, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the first effluent stream has substantially the same composition as the pressurization gas.

[0364] Embodiment 1.56: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the sorbent sorbs ammonia.

[0365] Embodiment 1.57: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the catalyst converts H2 and N2 into NH3.

[0366] Embodiment 1.58: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas comprises a reactant species that is H2.

[0367] Embodiment 1.59: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas comprises a reactant species that is N2.

[0368] Embodiment 1.60: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas comprises H2 and N2.

[0369] Embodiment 1.61: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas comprises H2 and N2 and NH3.

[0370] Embodiment 2.2: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the product gas withdrawn from the set of reaction vessels has a substantially constant flow rate.

[0371] Embodiment 2.3: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the material conduit system is further configured to transfer materials between vessels of the set of reaction vessels.

[0372] Embodiment 2.4: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the vessels in the set of reaction vessels are interconnected by a shared header and by a shared footer.

[0373] Embodiment 2.5: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising a surge tank in fluidic communication with the vessels.

[0374] Embodiment 2.6: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a portion of the set of reaction vessels comprises a cluster of vessels.

[0375] Embodiment 2.7: A variation of embodiments 1.1, 2.1, 2.6, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a cluster of vessels share an inlet gas feed.

[0376] Embodiment 2.8: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the vessels are configured such that an outlet gas of one vessel is directed to another vessel.

[0377] Embodiment 2.9: A variation of embodiments 1.1, 2.1, 2.8, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein said directing does not use a compressor.

[0378] Embodiment 2.10: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a portion of the set of reaction vessels are heated and cooled by a shared reservoir of a heat transfer fluid.

[0379] Embodiment 2.11: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the effluent streams from the exit material ports of the set of reaction vessels are combined into a combined effluent stream that provides substantially continuous product gas production from the set of reaction vessels.

[0380] Embodiment 2.12: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the control system is configured to decrease production of the product species by selectively reducing or eliminating flow of the reactant gas to one or more vessels.

[0381] Embodiment 2.13: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein vessels undergo stages of a reactive PSA process in a scheduled sequence.

[0382] Embodiment 2.14: A variation of embodiments 1.1, 2.1, 2.13, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the stages of the reactive PSA process comprise a synthesis operation and a desorption operation.

[0383] Embodiment 2.15: A variation of embodiments 1.1, 2.1, 2.13, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein vessels simultaneously undergoing the same stage of the reactive PSA process do not pass a gas between each other.

[0384] Embodiment 2.16: A variation of embodiments 1.1, 2.1, 2.13, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the control system is configured to coordinate the stages across multiple reaction vessels such that inputs from one stage are at least partially supplied by an output of a reaction vessel in a different stage.

[0385] Embodiment 2.17: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reaction bed in a vessel comprises a catalyst and a sorbent in a mass ration of about 1:4 to 4:1 catalyst to sorbent.

[0386] Embodiment 2.18: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reaction bed in a vessel comprises a catalyst and a sorbent in a mass ration of about 1:1 catalyst to sorbent.

[0387] Embodiment 2.19: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reaction vessels comprise tubular reaction beds.

[0388] Embodiment 2.20: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reaction vessels are configured for heat transfer between a reaction zone and a heat transfer fluid.

[0389] Embodiment 2.21: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein at least one reaction vessel includes a reaction bed with both a catalyst and a sorbent.

[0390] Embodiment 2.22: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the sorbent comprises an absorbent.

[0391] Embodiment 2.23: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the sorbent comprises an adsorbent.

[0392] Embodiment 2.24: A variation of embodiments 1.1, 2.1, 2.23, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the adsorbent comprises a material selected from the group consisting of zeolite, silica, alumina, metal-organic framework (MOF), covalent organic framework (COF), and zeolitic imidazolate framework (ZIF).

[0393] Embodiment 2.25: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the catalystcomprises an active component selected from the group consisting of Ru, Fe, and oxides thereof.

[0394] Embodiment 2.26: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein each reaction vessel uses a substantially similar sorbent and catalyst.

[0395] Embodiment 2.27: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reaction vessels comprise sub-chambers, wherein each sub-chamber acts as its own reaction vessel.

[0396] Embodiment 2.28: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reaction vessels comprise distinct system components that are housed separately and interconnected through the conduit system.

[0397] Embodiment 3.2: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a set of reaction vessels each iteratively perform the synthesis operation and the desorption operation.

[0398] Embodiment 3.3: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the desorption operation comprises: a) performing a blowdown operation, wherein a pressure of the vessel is reduced to a blowdown pressure and a blowdown stream is withdrawn from the vessel; and optionally prior to reducing the pressure to the blowdown pressure, b) performing a depressurization operation, wherein a pressure of the vessel is reduced to a depressurization pressure which is greater than the blowdown pressure and a depressurization stream is withdrawn from the vessel.

[0399] Embodiment 3.4: A variation of embodiments 1.1, 2.1, 3.1, 3.3, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein (b) is performed.

[0400] Embodiment 3.5: A variation of embodiments 1.1, 2.1, 3.1, 3.3, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the blowdown stream is a product gas stream.

[0401] Embodiment 3.6: A variation of embodiments 1.1, 2.1, 3.1, 3.3, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the depressurization stream is a product gas stream.

[0402] Embodiment 3.7: A variation of embodiments 1.1, 2.1, 3.1, 3.3, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising performing a re-pressurization operation in which a re-pressurization gas is introduced to the reaction vessel.

[0403] Embodiment 3.8: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the desorption operation comprises a sweep operation, comprising introducing a sweep gas to the vessel and withdrawing a sweep stream from the vessel.

[0404] Embodiment 3.9: A variation of embodiments 1.1, 2.1, 3.1, 3.8, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the sweep stream is a product gas stream.

[0405] Embodiment 3.10: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising performing a rinse operation subsequent to the synthesis operation, wherein performing the rinse operation comprises introducing a rinse gas comprising the product species to the vessel.

[0406] Embodiment 3.11: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a synthesis effluent stream is withdrawn from the reaction vessel during the synthesis stage.

[0407] Embodiment 3.12: A variation of embodiments 1.1, 2.1, 3.1, 3.2, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a first reaction vessel of the set of reaction vessels is performing the synthesis operation while a second reaction vessel of the set of reaction vessels is performing the desorption operation.

[0408] Embodiment 3.13: A variation of embodiments 1.1, 2.1, 3.1, 3.2, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein about one third of the set of reaction vessels are performing the synthesis operation at a given time.

[0409] Embodiment 3.14: A variation of embodiments 1.1, 2.1, 3.1, 3.2, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein more thanabout one third of the set of reaction vessels are performing the synthesis operation at a given time.

[0410] Embodiment 3.15: A variation of embodiments 1.1, 2.1, 3.1, 3.2, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein about half of the set of reaction vessels are performing the synthesis operation at a given time.

[0411] Embodiment 3.16: A variation of embodiments 1.1, 2.1, 3.1, 3.2, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the reactant gas is introduced to the set of reaction vessels with a substantially constant flowrate.

[0412] Embodiment 3.17: A variation of embodiments 1.1, 2.1, 3.1, 3.2, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the product gas is withdrawn from the set of reaction vessels at a substantially constant flowrate.

[0413] Embodiment 3.18: A variation of embodiments 1.1, 2.1, 3.1, 3.2, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a portion of the set of reaction vessels comprise a cluster of reaction vessels, and a wherein each vessel of a cluster undergoes a same process operation at a given time.

[0414] Embodiment 3.19: A variation of embodiments 1.1, 2.1, 3.1, 3.2, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis operation and the desorption operation are performed for an approximately equal length of time.

[0415] Embodiment 3.20: A variation of embodiments 1.1, 2.1, 3.1, 3.8, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis operation and the sweep operation are performed for an approximately equal length of time.

[0416] Embodiment 3.21: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis operation is performed for a longer length of time than the desorption operation.

[0417] Embodiment 3.22: A variation of embodiments 1.1, 2.1, 3.1, 3.7, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis operation and the re-pressurization operation are performed for an approximately equal length of time.

[0418] Embodiment 3.23: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, further comprising terminating the synthesis stage upon satisfying a synthesis saturation condition.

[0419] Embodiment 3.24: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein iteration between synthesis and desorption operations is controlled by length of time.

[0420] Embodiment 3.25: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein iteration between synthesis and desorption operations is controlled by a variation in pressure.

[0421] Embodiment 3.26: A variation of embodiments 1.1, 2.1, 3.1, 3.23, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis saturation condition is satisfied when an inlet pressure reaches a substantially constant value.

[0422] Embodiment 3.27: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein iteration between synthesis and desorption operations is controlled by a variation in an outlet flowrate.

[0423] Embodiment 3.28: A variation of embodiments 1.1, 2.1, 3.1, 3.23, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis saturation condition is satisfied when an outlet flowrate begins to increase after reaching a substantially minimum value.

[0424] Embodiment 3.29: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein iteration between synthesis and desorption operations is controlled by a variation in a gas composition.

[0425] Embodiment 3.30: A variation of embodiments 1.1, 2.1, 3.1, 3.23, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis saturation condition is satisfied when a concentration of unreacted feedstock in an outlet stream begins to increase after reaching a substantially minimum value.

[0426] Embodiment 3.31: A variation of embodiments 1.1, 2.1, 3.1, 3.4, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the depressurization stream from a first reaction vessel is used as the reactant gas to a second reaction vessel.

[0427] Embodiment 3.32: A variation of embodiments 1.1, 2.1, 3.1, 3.4, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the depressurization stream from a first reaction vessel is used as the re-pressurization gas to a second reaction vessel.

[0428] Embodiment 3.33: A variation of embodiments 1.1, 2.1, 3.1, 3.4, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the depressurization stream from a first reaction vessel is used as the sweep gas to a second reaction vessel.

[0429] Embodiment 3.34: A variation of embodiments 1.1, 2.1, 3.1, 3.11, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis effluent stream from a first reaction vessel is used as the reactant gas to a second reaction vessel.

[0430] Embodiment 3.35: A variation of embodiments 1.1, 2.1, 3.1, 3.11, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis effluent stream from a first reaction vessel is used as the re-pressurization gas to a second reaction vessel.

[0431] Embodiment 3.36: A variation of embodiments 1.1, 2.1, 3.1, 3.11, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis effluent stream from a first reaction vessel is used as the sweep gas to a second reaction vessel.

[0432] Embodiment 3.37: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein each vessel of the set of vessels is maintained at a temperature within about 5O°C of an average temperature.

[0433] Embodiment 3.38: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a first vessel of the set of vessels is maintained at a temperature within about 5O°C of a second vessel of the set of vessels.

[0434] Embodiment 3.39: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis operation is performed at about 35O-45O°C.

[0435] Embodiment 3.40: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the desorption operation is performed at about 35O-45O°C.

[0436] Embodiment 3.41: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the synthesis operation and the desorption operation are performed at about the same temperature.

[0437] Embodiment 3.42: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a reaction vessel is cooled during the synthesis operation.

[0438] Embodiment 3.43: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a reaction vessel exchanges heat with a reactant gas.

[0439] Embodiment 3.44: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a reaction vessel is heated during the desorption operation.

[0440] Embodiment 3.45: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein a reaction vessel is substantially adiabatic during the desorption operation.

[0441] Embodiment 3.46: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein the desorption operation is performed at about 10-50 C above the synthesis operation.

[0442] Embodiment 3.47: A variation of embodiments 1.1, 2.1, 3.1, 4.1, 5.1, and / or any other system or method embodiment variations herein, wherein performing the desorption process comprises desorbing into a hydrogen rich gas.

[0443] As a person skilled in the art will recognize from the previous detailed description and from the figures and claims, modifications and changes can be made to the embodiments of the invention without departing from the scope of this invention as defined in the following claims.

Claims

CLAIMSWhat is Claimed is:

1. A method for making a gaseous product, the method comprising: a) introducing a reactant gas within a vessel containing a catalyst and sorbent, whereby the catalyst facilitates a conversion of the reactant gas into a product species and the product species is selectively sorbed by the sorbent; b) withdrawing a first effluent stream from the vessel; and c) withdrawing a second effluent stream from the vessel, wherein the second effluent stream is enriched in the product species relative to the first effluent stream.

2. The method of Claim 1, further comprising, prior to introducing the reactant gas within the vessel, pressurizing the vessel.

3. The method of Claim 1, wherein the reactant gas comprises a first reactant species and a second reactant species, wherein the product species is formed from a reaction between the first reactant species and the second reactant species.

4. The method of Claim 3, wherein the vessel is pressurized with the first reactant species, an inert gas, or any combination thereof.

5. The method of Claim 3, wherein the vessel is pressurized with the first reactant species.

6. The method of Claim 1, wherein a pressure of the vessel is regulated at an outlet of the vessel while the reactant gas is introduced into the vessel.

7. The method of Claim 1, wherein introducing a reactant gas into a vessel and withdrawing a first effluent stream from the vessel occur simultaneously.

8. The method of Claim 1, wherein withdrawing a second effluent stream from the vessel is performed subsequent to withdrawing a first effluent stream from the vessel.

9. The method of Claim 3, wherein the first effluent stream contains substantially no second reactant species.

10. The method of Claim 3, wherein the reactant gas is introduced into the vessel until the first effluent stream contains more than 1 vol% of the second species.

11. The method of Claim 1, wherein the first effluent stream contains substantially no product gas.

12. The method of Claim 1, wherein the reactant gas is introduced into the vessel until the first effluent stream contains more than 1 vol% of the product gas.

13. The method of Claim 1, wherein the reactant gas is introduced into the vessel until a flow rate of the first effluent stream is substantially constant.

14. The method of Claim 1, wherein the reactant gas is introduced into the vessel until a pressure drop across the vessel is substantially constant.

15. The method of Claim 1, wherein the reactant gas is introduced into the vessel for a period of time between about 1 and about 100 residence times.

16. The method of Claim 1, wherein the reactant gas is introduced into the vessel for a period of time between about 1 and about 20 residence times.

17. The method of claim 1, wherein the reactant gas flow has a gas hourly space velocity less than about 10,000 / hr.

18. The method of claim 1, wherein the reactant gas flow has a gas hourly space velocity less than about 5,000 / hr.

19. The method of Claim 1, wherein the Reynold’s number of the reactant gas in the vessel is greater than about 5.

20. The method of claim 1, wherein the reactant gas is introduced at a pressure between about 10 and about 50 bar.

21. The method of Claim 1, further comprising introducing a rinse gas comprising the product species into the vessel prior to withdrawing a second effluent stream from the vessel.

22. The method of Claim 1, further comprising subsequently to withdrawing the first effluent stream from the vessel: a) reducing a pressure of the vessel to a blowdown pressure and withdrawing a blowdown stream from the vessel; and optionally prior to reducing the pressure to the blowdown pressure,b) reducing a pressure of the vessel to a depressurization pressure which is greater than the blowdown pressure and withdrawing a depressurization stream from the vessel.

23. The method of Claim 22, wherein the pressure is reduced to the depressurization pressure before being reduced to the blowdown pressure.

24. The method of Claim 22, wherein the depressurization stream comprises primarily the reactant gas.

25. The method of Claim 22, wherein the blowdown stream comprises at least 5 % of the product gas.

26. The method of claim 1, wherein the second effluent stream is withdrawn in a direction substantially co-current to a direction at which the reactant gas is introduced into the vessel.

27. The method of claim 1, wherein the second effluent stream is withdrawn from the vessel through multiple outlets.

28. The method of claim 27, wherein at least one outlet is configured such that a flow path of the second effluent stream is substantially co-current to a direction at which the reactant gas flows through the vessel.

29. The method of claim 1, wherein the reactant gas is introduced through a first material port in the vessel, and the second effluent stream is withdrawn from a second material port of the vessel.30.The method of claim 1, wherein the reactant gas is introduced through a first material port in the vessel, and the second effluent stream is withdrawn from the first material port.

31. The method of Claim 1, further comprising introducing a sweep gas into the vessel while withdrawing the second effluent stream from the vessel.

32. The method of Claim 31, wherein the sweep gas comprises a reactant species.

33. The method of Claim 31, wherein the sweep gas comprises primarily H2.

34. The method of Claim 31, wherein the sweep gas has a velocity greater than that of the reactant gas.

35. The method of Claim 1, wherein the first effluent stream is at a pressure greater than or equal to the second effluent stream.

36. The method of Claim 1, further comprising directing the first effluent stream to a recompression operation.

37. The method of Claim 1, further comprising directing the second effluent stream to a separation operation.

38. The method of Claim 31, wherein the sweep gas is introduced until an outlet partial pressure of the product species is less than about 0.4 bar at an outlet from the vessel.

39. The method of Claim 1, wherein a temperature in the vessel is reduced prior to withdrawing the second effluent stream.

40. The method of Claim 31, wherein the sweep gas in introduced at a flowrate less than or equal to a fluidization velocity of the catalyst and sorbent.

41. The method of Claim 1, wherein the reactant gas has at least about 5% of the product species.

42. The method of Claim 1, further comprising, introducing the first effluent stream to a second vessel containing a catalyst and a sorbent, whereby the first effluent stream is a reactant gas for the second vessel.

43. The method of Claim 1, further comprising, introducing the first effluent stream to a second vessel containing a catalyst and a sorbent, whereby the first effluent stream is used to pressurize the second vessel.

44. The method of Claim 1, further comprising, introducing the first effluent stream to a second vessel containing a catalyst and a sorbent, whereby the first effluent stream is used as the sweep gas the second vessel.

45. The method of Claim 22, further comprising, introducing the depressurization stream to a second vessel containing a catalyst and a sorbent, whereby the depressurization stream is a reactant gas for the second vessel.

46. The method of Claim 22, further comprising, introducing the depressurization stream to a second vessel containing a catalyst and a sorbent, whereby the depressurization stream is used to pressurize the second vessel.

47. The method of Claim 22, further comprising, introducing the depressurization stream to a second vessel containing a catalyst and a sorbent, whereby the depressurization stream is used as the sweep gas the second vessel.

48. The method of Claim 1, wherein the product species is ammonia.49 -The method of Claim 2, wherein the vessel is pressurized with a pressurizing gas comprising H2, N2, an inert gas, or any combination thereof.

50. The method of Claim 49, wherein the first effluent stream contains primarily nitrogen gas.

51. The method of Claim 50, wherein the first effluent stream contains substantially no hydrogen.

52. The method of Claim 49, wherein the first effluent stream contains primarily hydrogen gas.

53. The method of Claim 52, wherein the first effluent stream contains substantially no nitrogen.

54. The method of claim 1, wherein the first effluent stream has substantially the same composition as the reactant gas.

55. The method of claim 49, wherein the first effluent stream has substantially the same composition as the pressurization gas.

56. The method of claim 1, wherein the sorbent sorbs ammonia.

57. The method of claim 1, wherein the catalyst converts H2and N2into NH3.

58. The method of claim 1, wherein the reactant gas comprises a reactant species that is H2.

59. The method of claim 1, wherein the reactant gas comprises a reactant species that is N2.

60. The method of claim 1, wherein the reactant gas comprises H2and N2.

61. The method of claim 1, wherein the reactant gas comprises H2and N2and NH3.

62. A system for production of a product species, the system comprising: a) a set of reaction vessels, each reaction vessel comprising:I. a vessel body comprising an input material port for receiving a reactant gas and an exit material port for withdrawing an effluent stream,II. a reaction bed within the vessel that comprises a sorbent and / or a catalyst, wherein the catalyst facilitates a conversion of the reactant gas to a product species and the sorbent sorbs the product species,b) a material conduit system configured to (i) introduce the reactant gas to each of the set of reaction vessels through the input material ports and (ii) withdraw the effluent stream from each of the set of reaction vessels through their exit material ports; c) a control system configured to, for each of the reaction vessels, iteratively, (i) introduce the reactant gas to the reaction vessel and (ii) withdraw the effluent stream from the reaction vessel, wherein, the reactant gas provided to the set of reaction vessels has a substantially constant flow rate.

63. The system of Claim 62, wherein the product gas withdrawn from the set of reaction vessels has a substantially constant flow rate.

64. The system of claim 62, wherein the material conduit system is further configured to transfer materials between vessels of the set of reaction vessels.

65. The system of claim 62, wherein the vessels in the set of reaction vessels are interconnected by a shared header and by a shared footer.

66. The system of claim 62, further comprising a surge tank in fluidic communication with the vessels.

67. The system of claim 62, wherein a portion of the set of reaction vessels comprises a cluster of vessels.

68. The system of claim 67, wherein a cluster of vessels share an inlet gas feed.

69. They system of claim 62, wherein the vessels are configured such that an outlet gas of one vessel is directed to another vessel.

70. The system of claim 69, wherein said directing does not use a compressor.

71. The system of claim 62, wherein a portion of the set of reaction vessels are heated and cooled by a shared reservoir of a heat transfer fluid.

72. The system of Claim 62, wherein the effluent streams from the exit material ports of the set of reaction vessels are combined into a combined effluent stream that provides substantially continuous product gas production from the set of reaction vessels.73- The system of claim 62, wherein the control system is configured to decrease production of the product species by selectively reducing or eliminating flow of the reactant gas to one or more vessels.

74. The system of claim 62, wherein vessels undergo stages of a reactive PSA process in a scheduled sequence.

75. The system of claim 74, wherein the stages of the reactive PSA process comprise a synthesis operation and a desorption operation.

76. The system of claim 74, wherein vessels simultaneously undergoing the same stage of the reactive PSA process do not pass a gas between each other.

77. The system of claim 74, wherein the control system is configured to coordinate the stages across multiple reaction vessels such that inputs from one stage are at least partially supplied by an output of a reaction vessel in a different stage.

78. The system of claim 62, wherein the reaction bed in a vessel comprises a catalyst and a sorbent in a mass ration of about 1:4 to 4:1 catalyst to sorbent.

79. The system of claim 62, wherein the reaction bed in a vessel comprises a catalyst and a sorbent in a mass ration of about 1:1 catalyst to sorbent.

80. The system of claim 62, wherein the reaction vessels comprise tubular reaction beds.

81. The system of claim 62, wherein the reaction vessels are configured for heat transfer between a reaction zone and a heat transfer fluid.

82. The system of claim 62, wherein at least one reaction vessel includes a reaction bed with both a catalyst and a sorbent.

83. The system of claim 62, wherein the sorbent comprises an absorbent.

84. The system of claim 62, wherein the sorbent comprises an adsorbent.

85. The system of claim 84, wherein the adsorbent comprises a material selected from the group consisting of zeolite, silica, alumina, metal-organic framework (MOF), covalent organic framework (COF), and zeolitic imidazolate framework (ZIF).86.The system of claim 62, wherein the catalyst comprises an active component selected from the group consisting of Ru, Fe, and oxides thereof.

87. The system of claim 62, wherein each reaction vessel uses a substantially similar sorbent and catalyst.

88. The system of claim 62, wherein the reaction vessels comprise sub-chambers, wherein each sub-chamber acts as its own reaction vessel.

89. The system of claim 62, wherein the reaction vessels comprise distinct system components that are housed separately and interconnected through the conduit system.

90. A method for making a gaseous product, the method comprising, iteratively: a) performing a synthesis operation, wherein a reactant gas comprising a reactant species is introduced to a reaction vessel containing a catalyst and a sorbent, wherein the catalyst facilitates conversion of reactant species into a product species and the sorbent sorbs the product species; and b) performing a desorption operation, wherein the product species desorbs from the sorbent and a product gas comprising the product species is withdrawn from the reaction vessel.

91. The method of Claim 90, wherein a set of reaction vessels each iteratively perform the synthesis operation and the desorption operation.

92. The method of claim 90, wherein the desorption operation comprises: a) performing a blowdown operation, wherein a pressure of the vessel is reduced to a blowdown pressure and a blowdown stream is withdrawn from the vessel; and optionally prior to reducing the pressure to the blowdown pressure, b) performing a depressurization operation, wherein a pressure of the vessel is reduced to a depressurization pressure which is greater than the blowdown pressure and a depressurization stream is withdrawn from the vessel.

93. The method of claim 92, wherein (b) is performed.

94. The method of claim 92, wherein the blowdown stream is a product gas stream.

95. The method of claim 92, wherein the depressurization stream is a product gas stream.

96. The method of claim 92, further comprising performing a re-pressurization operation in which a re-pressurization gas is introduced to the reaction vessel.

97. The method of claim 90, wherein the desorption operation comprises a sweep operation, comprising introducing a sweep gas to the vessel and withdrawing a sweep stream from the vessel.

98. The method of claim 97, wherein the sweep stream is a product gas stream.

99. The method of claim 90, further comprising performing a rinse operation subsequent to the synthesis operation, wherein performing the rinse operation comprises introducing a rinse gas comprising the product species to the vessel.

100. The method of claim 90, wherein a synthesis effluent stream is withdrawn from the reaction vessel during the synthesis stage.

101. The method of claim 91, wherein a first reaction vessel of the set of reaction vessels is performing the synthesis operation while a second reaction vessel of the set of reaction vessels is performing the desorption operation.

102. The method of claim 91, wherein about one third of the set of reaction vessels are performing the synthesis operation at a given time.

103. The method of claim 91, wherein more than about one third of the set of reaction vessels are performing the synthesis operation at a given time.

104. The method of claim 91, wherein about half of the set of reaction vessels are performing the synthesis operation at a given time.

105. The method of claim 91, wherein the reactant gas is introduced to the set of reaction vessels with a substantially constant flowrate.

106. The method of claim 91, wherein the product gas is withdrawn from the set of reaction vessels at a substantially constant flowrate.

107. The method of claim 91, wherein a portion of the set of reaction vessels comprise a cluster of reaction vessels, and a wherein each vessel of a cluster undergoes a same process operation at a given time.

108. The method of claim 91, wherein the synthesis operation and the desorption operation are performed for an approximately equal length of time.

109. The method of claim 97, wherein the synthesis operation and the sweep operation are performed for an approximately equal length of time.

110. The method of claim 90, wherein the synthesis operation is performed for a longer length of time than the desorption operation.

111. The method of claim 96, wherein the synthesis operation and the repressurization operation are performed for an approximately equal length of time.

112. The method of claim 90, further comprising terminating the synthesis stage upon satisfying a synthesis saturation condition.

113. The method of claim 90, wherein iteration between synthesis and desorption operations is controlled by length of time.

114. The method of claim 90, wherein iteration between synthesis and desorption operations is controlled by a variation in pressure.

115. The method of claim 112, wherein the synthesis saturation condition is satisfied when an inlet pressure reaches a substantially constant value.

116. The method of claim 90, wherein iteration between synthesis and desorption operations is controlled by a variation in an outlet flowrate.

117. The method of claim 112, wherein the synthesis saturation condition is satisfied when an outlet flowrate begins to increase after reaching a substantially minimum value.

118. The method of claim 90, wherein iteration between synthesis and desorption operations is controlled by a variation in a gas composition.

119. The method of claim 112, wherein the synthesis saturation condition is satisfied when a concentration of unreacted feedstock in an outlet stream begins to increase after reaching a substantially minimum value.

120. The method of claim 93, wherein the depressurization stream from a first reaction vessel is used as the reactant gas to a second reaction vessel.

121. The method of claim 93, wherein the depressurization stream from a first reaction vessel is used as the re-pressurization gas to a second reaction vessel.

122. The method of claim 93, wherein the depressurization stream from a first reaction vessel is used as the sweep gas to a second reaction vessel.

123. The method of claim 100, wherein the synthesis effluent stream from a first reaction vessel is used as the reactant gas to a second reaction vessel.

124. The method of claim 100, wherein the synthesis effluent stream from a first reaction vessel is used as the re-pressurization gas to a second reaction vessel.

125. The method of claim 100, wherein the synthesis effluent stream from a first reaction vessel is used as the sweep gas to a second reaction vessel.

126. The method of claim 90, wherein each vessel of the set of vessels is maintained at a temperature within about 5O°C of an average temperature.

127. The method of claim 90, wherein a first vessel of the set of vessels is maintained at a temperature within about 5O°C of a second vessel of the set of vessels.

128. The method of claim 90, wherein the synthesis operation is performed at about 35O-45O°C.

129. The method of Claim 90, wherein the desorption operation is performed at about 35O-45O°C.

130. The method of claim 90, wherein the synthesis operation and the desorption operation are performed at about the same temperature.

131. The method of claim 90, wherein a reaction vessel is cooled during the synthesis operation.

132. The method of claim 90, wherein a reaction vessel exchanges heat with a reactant gas.

133. The method of claim 90, wherein a reaction vessel is heated during the desorption operation.

134. The method of claim 90, wherein a reaction vessel is substantially adiabatic during the desorption operation.

135. The method of claim 90, wherein the desorption operation is performed at about 10-50 C above the synthesis operation.

136. The method of claim 90, wherein performing the desorption process comprises desorbing into a hydrogen rich gas.

137. A method comprising: managing material communication between a set of reaction vessels and thereby cycling a set of reaction vessels through different stages of ammonia synthesis and separation, which comprises for each reaction vessel: reacting nitrogen and hydrogen with a catalyst to capture ammonia in a sorbent of the reaction vessel, rinsing the reaction vessel, performing desorption process in the reaction vessel, purging the reaction vessel, and / or repressurizing the reaction vessel.

38. A system comprising: a set of reaction vessels, with each reaction vessel including at least a sorbent or catalyst, a material stream conduit system, the set of reaction vessels integrated through material stream conduit system, and a control system configured to cooperatively manage cycling of the set of reaction vessels and material flow between reaction vessels through the conduit system.

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