Reactor system for gas synthesis

Abstract

A reactor system for gas synthesis is provided, comprising a batch, pseudo-batch, or dynamic reactor of one or more individual catalytic reactors for gas synthesis, one or more fluid control mechanisms consisting of shared pipes and manifolds for delivering reactants to the chemical reactor system and collecting reaction products from the chemical reactor system, and a control system that can open one or more fluid control mechanisms for controlling the inflow of reactants to the chemical reactor system and the outflow of reaction products from the chemical reactor system. Methods for the use of these systems in gas synthesis, and in particular in ammonia synthesis, as well as for improving ammonia synthesis plants, are also provided. The disclosed chemical reactor systems are particularly well suited for use in ammonia (NH3) synthesis and enable established gas catalytic chemistry, such as that used in most Haber-Bosch processes, to be adapted to variable or intermittent renewable energy sources.

Description

Technical Field

[0001] This application claims the benefit of U.S. Patent Application No. 18 / 587,816, filed Feb. 26, 2024, and Provisional Patent Application No. 63 / 506,815, filed Jun. 7, 2023, under 35 U.S.C. § 119(e), the teachings of each of which are incorporated herein by reference.

Background Art

[0002] The discovery in the early 1900s by German chemists Fritz Haber and Carl Bosch of a process for synthetically producing ammonia is perhaps one of the most important in recent years. Their invention involves reacting nitrogen and hydrogen under high temperature and high pressure in the presence of a catalyst, following this exothermic, reversible reaction:

Number

[0003] The first commercial production was in 1913 at the BASF plant in Ludwigshafen with a productivity of about 25 tons of ammonia per day (see BASF's history at www.basf.com / ca / en / who - we - are / history / 1902 - 1924.html). The size of ammonia plants and the worldwide productivity have since grown significantly, reaching approximately 200 billion tons per year globally with the latest purification facilities capable of producing over 3000 tons of anhydrous ammonia per day. It is estimated that 50% of the food consumed by humans is cultivated using fertilizers based on synthetically produced ammonia.

[0004] Currently, over 95% of synthetic ammonia production uses fossil fuels as the source of hydrogen (H2) needed for the reaction. "Gray ammonia" uses natural gas as the raw material, and "brown ammonia" uses fuel oil or coal as the raw material. The consumption of fossil fuels for the production of gray and brown ammonia currently accounts for about 2% of global greenhouse gas emissions.

[0005] "Green ammonia" (generating hydrogen from water using renewable energy) shows significant potential as a high-density, carbon-free energy carrier for storing and transporting renewable energy. In addition to storing and transporting renewable energy, the world needs to shift current ammonia demand from gray / brown to green in order to reduce greenhouse gas emissions.

[0006] While the green ammonia production process is widely known, the intermittency of the most popular renewable energy sources, such as wind turbines and photovoltaic (PV) solar, poses problems for large-scale ammonia production. For economic and efficiency reasons, renewable energy plants prefer to sell electricity directly to customers as it is produced, but this often results in "suppression," where undesirable surplus energy is generated during periods of low consumer demand (e.g., peak output of solar PV in the middle of the day). This means that surplus energy for ammonia production from non-dedicated renewable power sources often has an even narrower availability.

[0007] In contrast, modern ammonia refining facilities operate 24 hours a day, 365 days a year to maximize production, revenue, and efficiency; they are not suited to being powered by intermittent renewable energy sources with utilization rates below 40%. Combining renewable energy generation technology with classical synthetic ammonia production technology would require extremely large energy storage (batteries), large hydrogen storage, or perhaps a combination of both, for more than half of any production volume.

[0008] Regardless of intermittency or timing, industrial-scale ammonia refining facilities, if converted to green ammonia, would require more energy input than the world's largest renewable energy power plants. Currently, the vast majority of solar power plants in the United States have a peak output of less than 5 MW (see Ammonia as a Medium for Renewable Energy Transport in pubs with the extension www.acs.org / doi / 10.1021 / acssuschemeng.7b02219). Green ammonia is expected to require 10–12 MWh / ton (see Bhadla Solar Park in en with the extension www.wikipedia.org / wiki / Bhadla_Solar_Park), meaning even the first small BASF ammonia plant at 25 tons / day required an average power of 12 MW and a peak solar plant output of over 40 MW (based on a 25% utilization rate or 6 hours / day of solar output). The 3,000-ton-per-day ammonia plant requires an estimated rated power of 5.5 GW, which is more than double the rated power of the world's largest solar plant as of early 2023 (see Bhadla Solar Park in English with the extension www.wikipedia.org / wiki / Bhadla_Solar_Park) and nearly four times the rated power of the world's largest wind farm (see Hornsea Project Two in English with the extension www.wikipedia.org / wiki / Hornsea_Wind_Farm#Hornsea_Project_Two).

[0009] To adapt to existing renewable energy sources, ammonia synthesis reactors (and their associated systems) in industrial ammonia production need to be significantly redesigned in terms of scale, turndown capability, and discontinuous operation, both in terms of scale and intermittency.

[0010] Ammonia synthesis reactors have traditionally been designed as steady-state, adiabatic, plug-flow, packed-bed reactors packed with solid catalyst beads with a diameter of 1-10 mm. Catalyst materials are typically magnetite (Fe3O4), woostite (Fe3O4), and others. 1-X It is oxygen (O) or ruthenium (Ru) based.

[0011] The stoichiometric gas ratio and exothermic reaction, according to Le Chatelier's principle (see Le Chatelier's principle in English with the extension www.wikipedia.org / wiki / Le_Chatelier%27s_principle), mean that ammonia production is thermodynamically preferred at higher pressures and lower temperatures, although lower reaction temperatures create difficulties in activating nitrogen, resulting in slower reaction rates. Industrial Haber-Bosch synthesis is typically carried out using a compromise between medium to high pressures (150–400 bar) and higher temperatures (400–600°C) favorable for ammonia conversion, in order to increase the reaction rate at the expense of conversion.

[0012] The higher operating temperatures of industrial Haber-Bosch reactors imply an equilibrium product conversion limit of less than 100%; this, combined with the catalytic performance limit, typically results in less than 30% conversion of reactants to ammonia per pass through the reactor, which involves three or more passes required to completely convert the reactants. This leads to higher compression requirements, larger equipment sizes, and lower overall energy efficiency.

[0013] The use of plug-flow reactors with either exothermic or endothermic reactions introduces complexity to their design and operation; exothermic reactions require good temperature control to avoid high-temperature spots in the reactor and catalyst sintering. In a single-bed plug-flow reactor, the conversion of reactants progresses toward equilibrium as each reactant “plug” moves along the axial length of the reactor; in exothermic reactions, the temperature profile rises along the length of the reactor. Without a reliable heat removal mechanism, the reactant / product gas, reactor, and catalyst will continue to rise in temperature along the catalyst bed path until either catalyst sintering or the design temperature (whichever comes first) is reached. The catalyst positioned toward the reactor bed outlet is always at a higher temperature than the catalyst near the reactant inlet; the temperature limit effectively restricts the length of the catalyst bed and, therefore, the residence time in the reactor. Typically, an ammonia purification facility has a single reactor pressure vessel housing multiple catalyst beds with a coolant “quenching gas” added between the beds for temperature control and to increase reactant concentration as ammonia is produced. An example of this is shown in Figure 1A.

[0014] Figure 1A illustrates a general-purpose multi-bed single-vessel plug-flow reactor using rapid cooling, commonly used in industrial ammonia production. In this system, a pressure vessel (1) houses multiple axial-flow catalyst beds (2) sized to match the target residence time or gas-hourly space volume (GHSV) at the design flow rate. A mixture of partially preheated hydrogen and nitrogen reactant feed gases flows into the reactor (3), with several variations using colder feed gases to cool the catalyst bed walls above the inlet (4). The reactant gases are guided to an internal heat exchanger (5) to heat the reactants (and simultaneously cool the hot product gases released from the last catalyst bed) before passing through an internal pipe (6) to the first catalyst bed (2). Ammonia is produced in the catalyst beds via the exothermic reaction of the reactant feed gases; the released heat raises the temperature inside the reactor, slowing the forward progress of the reaction and limiting the reaction equilibrium product concentration. The product concentration is diluted to keep the catalyst below the sintering temperature, and a moderate reaction temperature is maintained for better conversion. A quenched gas (7) consisting of lower-temperature reactant gases is directly added between the catalyst beds. After passing through the last catalyst bed, the gas is led to an internal heat exchanger (5) before flowing out of the reactor (8).

[0015] Figure 1B illustrates a general-purpose three-bed adiabatic quenching reactor system similar to that shown in Figure 1A, but using a dedicated reactor vessel in series for each catalyst bed; space or height constraints may necessitate dividing a single reactor into multiple vessels. In this system, each reactor pressure vessel (21, 26, 29) contains a catalyst (22), and a mixture of preheated hydrogen and nitrogen feed gas flows into the first reactor (23). The catalyst beds of the reactors are sized to produce a target residence time or GHSV for the entire system at the design flow rate. Detailed depictions of the interiors of the required reactor vessels, such as gas distributors or catalyst baskets, are not shown. As the reactants flow through each catalyst bed and ammonia is produced in an exothermic reaction, heat is released, slowing the forward progress of the reaction while simultaneously raising the temperatures of the reactor vessels, catalyst, and gas. The high-temperature gas is withdrawn from reactors (24, 27) and diluted with a lower-temperature hydrogen / nitrogen reactant (25, 28), known as the “quenched gas,” at the inlets of reactors 26 and 29 to prevent catalyst overheating and further dilute the product gas (to increase ammonia yield). The output of the multi-bed multi-reactor system (30) is a mixture of unreacted hydrogen and nitrogen gases, accompanied by gaseous ammonia products. In this configuration, an overall conversion efficiency of approximately 30% is typical. The product gas (30) is typically cooled to separate the ammonia products from the unreacted feed gas, which is then recycled to the first reactor (21).

[0016] A key consideration when designing any vessel is the ratio of the reactor's length (L) to its diameter (D), which affects the distribution of reactants across the catalyst bed and the pressure drop through the reactor. In a plug-flow reactor with a given total reactor volume, a higher L / D ratio (i.e., a narrower and longer reactor) generally results in better reactant distribution across the catalyst bed with less channeling, a lower risk of catalyst "hot spots" due to localized reactions, a lower need for complex inlet distribution design, increased catalytic efficiency, and better performance during turndown. However, a higher L / D ratio, due to the smaller diameter, leads to increased gas velocity through the catalyst bed, and this, combined with the increased bed length, results in a greater pressure drop along the reactor and higher compression energy costs.

[0017] To overcome issues such as fluid distribution, catalyst hotspots, and pressure drops, modern reactor designs have added complexity such as radiant flow beds (Figure 1C), axial / radiant flow combinations, external heat exchangers, and uniform multi-tube reactor arrangements; these also help to smooth and control the reactor's temperature profile. Despite the latest improvements, turndown is typically limited to about 50% of the reactor's design flow due to potential problems such as channeling, inefficient catalyst use, and the resulting undesirable temperature gradients, hotspots, and catalyst sintering.

[0018] Figure 1C illustrates a general-purpose multi-bed radiant flow reactor with an integrated feed gas heat exchanger, commonly used in existing commercial ammonia synthesis processes. In this system, a pressure vessel (41) houses multiple radiant flow catalyst beds (42, 43, 44) sized to match the target residence time or gas-hourly space volume (GHSV) at the design flow rate. A mixture of partially preheated hydrogen and nitrogen reactant feed gases flows into the reactor (45), with several variations using colder feed gases to cool the catalyst bed walls above the inlet (4). The reaction gases are guided through an internal heat exchanger (47) to heat the reactants (and simultaneously cool the hot product gases as they leave the final catalyst bed) before passing through an internal pipe (48) to the first catalyst bed (42). Ammonia is produced within the catalyst beds via an exothermic reaction of the reactant feed gases; the released heat raises the temperature within the reactor, slowing the forward progress of the reaction and limiting the reaction equilibrium product concentration. To keep the catalyst below the sintering temperature, the product concentration is diluted, and to maintain a moderate reaction temperature for better conversion, a quenched gas (49) consisting of lower-temperature reactant gases is added between the catalyst beds. After the gas has passed through the last catalyst bed, it is led to an internal heat exchanger (47) before flowing out of the reactor (50).

[0019] Catalyst life is typically 5–10 years, but shorter than the reactor life, requiring replacement. More complex configurations, such as multi-bed reactors with intricate internal structures, create access and design difficulties in catalyst removal and refilling. One recent study showed that catalyst replacement in a typical multi-bed ammonia synthesis reactor took over 450 hours, partly due to the physical complexity of the reactor (catalyst replacement time; ISSN 0149-3701; and see ammoniaknowhow at www.extension.com / optimizing-the-installation-and-operation-of-a-new-3-bed-ammonia-synthesis-converter-basket / ).

[0020] While there have been several attempts to design isothermal (constant temperature) reactors instead of adiabatic reactors, this involves significant internal and external mechanical complexity because even moderately exothermic reactions like ammonia synthesis require even heat removal across the entire catalyst bed.

[0021] The reason that most ammonia synthesis reactors at the technical level still rely on adiabatic plug-flow designs is primarily because they are suited to the high, constant flow rates required in modern, custom-built ammonia purification facilities designed for mass ammonia production. The advantages of the technical level design include high production rates per unit of catalyst weight, increased contact between reactants and the catalyst surface under the design conditions, and a lower ratio of reactor metal weight to catalyst (a proxy for reactor manufacturing costs).

[0022] In parallel, the technology of the current level is specifically designed and capable of operating in a steady-state control mode, which significantly simplifies the process control mechanism. It should not be forgotten that the trajectory of the current ammonia synthesis reactor dates back to 1913, before the availability of the current automated process control mechanisms; reactors had to be designed for high flow rates with as little external (and often manual) intervention as possible. Without the use of plug-flow reactors operating in a steady state, it would have been impossible for the industry to reach the remarkably high levels of production rates that it achieved even before the advent of computerized and automated process control systems.

[0023] The need for steady-state operation has been increased by two additional factors influencing the current state of technology. As previously mentioned, over 95% of ammonia production (and therefore synthetic reactors) is integrated into plants that use fossil fuels as their hydrogen feedstock. The upstream plants of ammonia synthetic reactors are either steam methane reforming (SMR) systems for natural gas feedstock or coal gasification systems for coal feedstock. Both SMRs and coal gasification systems are highly complex in design, construction, and operation, and have limited turndown capacity; all efforts are made to ensure steady-state flowthrough through the downstream Haber-Bosch system to minimize deviations in operating conditions and product specifications in the complex upstream system. In parallel, the use of centrifugal compressors for feed gas compression is becoming widespread in high-throughput facilities due to improvements in performance and economics at high flow rates; high-rate gas compression systems perform best in steady-state operation, suffer from the limitations of turndown capacity, and reinforce current reactor designs that focus on steady-state operation.

[0024] Reactors designed for green ammonia production are freed from the steady-state constraints and high-velocity compressed gas systems required for economics at scale in upstream SMR or coal gasification systems; in parallel, engineers can take advantage of the benefits of high-performance automated computer-controlled systems. Modern ammonia synthesis reactor designs, therefore, can take advantage of the opportunities for systems that rely on variable throughput, higher turndown ratios, and highly complex process control.

[0025] In summary, current state-of-the-art reactors are not at all suitable for relatively small-scale green ammonia production using the intermittent power provided by most clean energy sources (possibly excluding geothermal). Current state-of-the-art reactors are designed for custom-built, high-throughput, continuous, steady-state operation; green ammonia reactors must be designed for small-scale (low-throughput), variable output, high turndown, rapid startup, and high efficiency while remaining effective under high temperature and pressure.

[0026] There is a need for improvements in chemical reactor systems for gas synthesis, particularly systems that can be coupled with intermittent or variable energy production technologies.

Summary of the Invention

[0027] One aspect of the present disclosure relates to a reactor system for gas synthesis.

[0028] The system of the present disclosure includes one or more individual catalytic batch, semi-batch, or dynamic reactors for gas synthesis. The use of the highly simplified or modular reactors described in the present invention, especially when constructed from standardized parts as described herein, makes the overall system cost competitive.

[0029] In one non-limiting aspect, the chemical reactor system includes a batch, semi-batch, or dynamic temperature swing gas synthesis reactor system of one or more individual catalytic reactors for gas synthesis.

[0030] In one non-limiting alternative aspect, the chemical reactor system includes a multi-vessel batch, semi-batch, or dynamic reactor of connected individual catalytic reactors for gas synthesis.

[0031] The chemical reactor system further includes one or more fluid control mechanisms connecting individual catalyst reactors of one or more multi-container batch or pseudo-batch reactors, and a control system that can open one or more fluid control mechanisms to control the inflow of reactants into the system and the outflow of reaction products from the system.

[0032] In one non-limiting embodiment, the control system can control the reactor inflow and outflow mechanisms within the system to facilitate the flow of fluid through individual catalytic reactors in series, parallel, or a combination thereof, thereby ensuring that the fluid in each individual reactor is stable or near-stable for a portion of the residence time, while the fluid flow through the chemical reactor system is nearly continuous.

[0033] The control system may be automated and / or the individual or collective catalytic reactors may be operated in batch operation mode, or in continuous, steady-state, or plug-flow operation mode.

[0034] Individual catalytic reactors used in a chemical reactor system may be equipped with sensors, detectors, or controllers that transmit information to an internal or external heat transfer system and / or one or more control systems, thereby changing the reactor temperature as the reaction progresses, so that the chemical reactor system operates to allow for a continuous inflow of reactants and outflow of reaction products through the chemical reactor system.

[0035] The individual catalyst reactors used in the chemical reactor system of this disclosure may be designed as pipe-in-pipe heat exchangers.

[0036] The control systems used in the chemical reactor systems of this disclosure may be computerized, connected to remote or cloud-based control devices, and / or use algorithms, predictive control, artificial intelligence, or machine learning to optimize the performance of individual or collective catalytic reactor vessels and chemical reactor systems.

[0037] In one non-limiting embodiment, a chemical reactor system is used for ammonia synthesis.

[0038] Another aspect of this disclosure relates to energy waste reduction systems, including chemical reactor systems as disclosed herein, coupled with variable or intermittent energy production technologies. In one non-limiting embodiment, coupling the chemical reactor systems of the present invention with variable or intermittent energy production technologies enables a Power-to-X (also known as P2X or P2Y) system.

[0039] Another aspect of this disclosure relates to a method for producing gas by coupling intermittent energy production technology with a chemical reactor system as disclosed herein.

[0040] Another aspect of this disclosure relates to a method for producing a gas via the following steps: supplying a synthesis feed gas to a chemical reactor system as disclosed herein; opening one or more fluid control mechanisms of individual catalytic reactors or collective reactors to allow sufficient synthesis feed gas to flow into each reactor so that each reactor is filled with the feed gas; closing one or more fluid control mechanisms after the reactors have been filled with the feed gas to stop or sufficiently slow the flow of gas in contact with the catalyst, allowing the reaction to occur; timing, predicting, and / or monitoring temperature, pressure, and / or other measurable conditions within each closed or partially closed reactor to determine the progress of the reaction; and discharging the reaction products after the reaction has reached a desired progress.

[0041] Another aspect of the present disclosure relates to a method for improving an ammonia plant having a synthesis loop in which fresh ammonia synthesis gas containing hydrogen and nitrogen is combined with an arbitrary recycle stream to form a mixed ammonia synthesis gas, and the mixed ammonia synthesis gas reacts on a catalyst to form an ammonia product gas converted. The improvement method includes the steps of: replacing an existing ammonia synthesis reactor (single) or reactor (plural) with a reactor system as disclosed; incorporating a feed gas heat exchanger capable of heating the synthesis gas to a target or controlled temperature required for reactor batch operation upstream of the chemical reactor system; incorporating a heat exchanger and gas-liquid separator for condensing and recovering ammonia from the reactor discharge stream to form a low ammonia stream; and incorporating a pressure control system that enables control and operation of the operating pressure of the chemical reactor system.

[0042] Another aspect of this disclosure relates to a method for producing ammonia from synthesis gas containing hydrogen and nitrogen combined with any recycled streams. In this production method, a synthesis feed gas is supplied to a system comprising one or more catalyst-filled pressure vessel reactors, each catalyst-filled pressure vessel reactor being connected to one or more manifolds at the inlet and one or more manifolds at the outlet of the system, and each catalyst-filled pressure vessel reactor having independently operating mechanisms for controlling, directing, and stopping the flow of fluid to and from individual vessels and catalyst beds via the inlet and outlet manifolds. A control mechanism of a selected catalyst-filled pressure vessel reactor, or a group of catalyst-filled pressure vessel reactors, is then opened to allow sufficient synthesis feed gas to flow into each catalyst-filled pressure vessel reactor from its inlet manifold so that each catalyst-filled pressure vessel reactor is filled with feed gas and pressurized to a selected operating pressure. After being filled with feed gas, control mechanisms at each end of the selected catalyst-filled pressure vessel reactor or group of reactors are then closed to stop or sufficiently slow the flow of gas in contact with the catalyst, allowing the reaction to occur. The temperature, pressure, and / or other measurable conditions within each closed or partially closed catalyst-filled pressure vessel reactor are then timed, predicted, or monitored to determine the progress of the reaction. After the reaction reaches the desired state, transformation, or equilibrium transformation, the catalyst-filled pressure vessel reactor (single) or reactor(s) is then allowed to cool below the critical point or dew point temperature of the ammonia product. After sufficient cooling, the liquid ammonia product accumulated at the bottom of the catalyst-filled pressure vessel reactor (single) or reactor(s) is discharged without most of the unreacted gases leaking from the catalyst-filled pressure vessel reactor (single) or reactor(s). The filling process is then repeated by adding new synthetic feed gas to any remaining unreacted gases within the catalyst-filled pressure vessel reactor (single) or reactor(s).

[0043] In this production method, one or more catalyst-filled reactor vessels may be used to store the reactants at high pressure before introducing a second reactant, in order to initiate the ammonia production process in a controlled manner.

[0044] In this production method, hydrogen and / or nitrogen can be stored at sufficiently high pressure in one or more catalyst-filled pressure vessel reactors during periods when electricity is available, thereby being transferred to one or more catalyst-filled pressure vessel reactors during periods when electricity is unavailable, such as at night or when there is no wind or sunlight, to produce ammonia.

[0045] In this production method, one or more catalyst-filled pressure vessel reactors may be sequentially filled with supply gas so as to allow batch or near-batch residence times within each reactor, while having a continuous or near-continuous flow of supply gas through the entire system of reactor vessels.

[0046] In this production method, one or more catalyst-filled pressure vessel reactors may be equipped with sensors, detectors, or control devices that transmit information to one or more control systems, so that the system of reactors, mechanisms, sensors, and control systems can operate to allow for a continuous inflow of feed gas and a continuous outflow of products through the entire reactor system.

[0047] In this production method, one or more catalyst-filled pressure vessel reactors may be equipped with a control system that can operate the reactors and their fluid control mechanisms so that they are sequentially filled with synthesis gas, allowing for batch or near-batch residence times within each reactor, while having a continuous or near-continuous flow of supply gas through the entire reactor vessel system.

[0048] In this production method, one or more catalyst-filled pressure vessel reactors may be equipped with a control system capable of controlling the temperature of the synthesis feed gas.

[0049] In this production method, one or more catalyst-filled pressure vessel reactors may be equipped with a control system capable of controlling the reactor system operating pressure.

[0050] In this production method, one or more catalyst-filled pressure vessel reactors may be equipped with internal or external heat transfer systems to regulate the temperature of the reactor as the reaction progresses.

[0051] In this production method, one or more catalyst-filled pressure vessel reactors may be designed as pipe-in-pipe heat exchangers.

[0052] In some embodiments of the present invention, the ratio of reactants entering the container is modified to control the progress of the reaction and the heat released through the reactor container wall. In one non-limiting embodiment, the reactor is first filled to a desired pressure with only high-temperature compressed hydrogen, and then nitrogen is gradually added in sufficient quantities to match the heat produced by the exothermic reaction that is released into the atmosphere through the reactor wall. In this non-limiting embodiment, the reaction temperature is kept constant by controlling the heat of the exothermic reaction released by controlling the inflow of nitrogen to match the amount of ammonia produced and the heat released from the reactor into the atmosphere. An additional advantage of this non-limiting embodiment of the present invention is the use of Le Chatelier's principle, in which a high (or excess) concentration of reactants pushes the reaction toward the product side, resulting in a higher equilibrium transformation at a given operating temperature and pressure. The ability to remove liquid products without unreacted feed gas allows for the use of stoichiometrically incorrect or non-stoichiometric reactant ratios without the drawback of increased compression due to a high recycling rate. [Brief explanation of the drawing]

[0053] The accompanying drawings illustrate various other aspects of the present disclosure, including systems, methods, and various other embodiments. Any person with ordinary skill in the art will understand that the element boundaries illustrated in the drawings (e.g., boxes, boxes of groups, or other shapes) are examples of boundaries. In some examples, one element may be designed as multiple elements, or multiple elements may be designed as one element. In some examples, an element shown as an internal component of one element may be implemented as an external component of another element, and vice versa. Furthermore, elements do not have to be drawn to scale. Non-limiting and non-exclusive descriptions are provided with reference to the following drawings. Components in the drawings are not necessarily drawn to scale, and instead the emphasis is on illustrating the principle. Some embodiments of the present invention are illustrated as examples and are not limited to the drawings in the accompanying drawings, and the same reference numerals in the drawings may indicate similar components.

[0054] [Figure 1A] Figure 1A illustrates a typical multi-bed insulated quenching reactor, a prior art example with an integrated feed gas heat exchanger commonly used in ammonia synthesis processes.

[0055] [Figure 1B] Figure 1B illustrates a typical multi-bed radiant flow reactor, a prior art example with an integrated feed gas heat exchanger commonly used in ammonia synthesis processes.

[0056] [Figure 1C] Figure 1C illustrates a prior art three-bed insulated rapid cooling reactor system similar to that shown in Figure 1A, but using a dedicated reactor vessel in series for each catalyst bed, as is commonly used in ammonia synthesis processes.

[0057] [Figure 2]Figure 2 illustrates a chemical reactor system for gas synthesis as an example of a non-limiting aspect of the present invention: a multi-vessel temperature swing reactor system with a common inlet for reactants and a common outlet for reaction products.

[0058] [Figure 3] Figure 3 illustrates a chemical reactor system for gas synthesis as an example of a non-limiting aspect of the present invention: a multi-container temperature swing reactor system with a common inlet for reactants and a common outlet for reaction products using a multi-port valve.

[0059] [Figure 4] Figure 4 illustrates a chemical reactor system for gas synthesis as an example of a non-limiting aspect of the present invention: a multi-container temperature swing reactor system with a common inlet for reactants and a common outlet for reaction products, accompanied by multiple inlet manifolds.

[0060] [Figure 5] Figure 5 illustrates a non-limiting cross-sectional view of an individual reactor pressure vessel used in the temperature swing reactor system of the present invention.

[0061] [Figure 6] Figure 6 illustrates a non-limiting cross-sectional view of an individual reactor pressure vessel used in the temperature swing reactor system of the present invention, which includes an integrated active cooling system.

[0062] [Figure 7] Figure 7 illustrates a non-limiting cross-sectional view of an individual reactor used in the temperature swing reactor system of the present invention, where a typical pressurized gas storage tank is filled or partially filled with a catalyst for use as a reactor pressure vessel, as illustrated in Figures 2, 3, and 4.

[0063] [Figure 8]Figure 8 is a schematic process diagram of a non-limiting example of an ammonia production system, illustrating how the temperature swing reactor system of the present invention interacts with other parts of the production system.

[0064] [Figure 9] Figure 9 is a schematic process diagram of a non-limiting embodiment of a control system for a temperature swing reactor system according to the present invention.

[0065] [Figure 10] Figure 10 is a schematic process diagram of a non-limiting embodiment of the temperature swing reactor system of the present invention for an ammonia production system during periods of low power availability (e.g., overnight ammonia production in a solar power system).

[0066] [Figure 11] Figure 11 illustrates an alternative and non-limiting embodiment of the chemical reactor system for gas synthesis of the present invention: a simplified multi-vessel pseudo-batch reactor system of connected individual catalytic reactors for gas synthesis, with inlets for separated reactants and outlets for reaction products.

[0067] [Figure 12] Figure 12 illustrates this alternative and non-limiting aspect of the chemical reactor system for gas synthesis of the present invention: a representation of a multi-vessel pseudo-batch reactor system of connected individual catalytic reactors for gas synthesis, with an inlet for separated reactants and an outlet for reaction products, as well as backflow capability.

[0068] [Figure 13] Figure 13 illustrates this alternative and non-limiting aspect of the chemical reactor system for gas synthesis of the present invention: a multi-vessel pseudo-batch reactor system of connected individual catalytic reactors for gas synthesis, with inlets for separated reactants and outlets for reaction products, as well as individually selectable backflow capabilities.

[0069] [Figure 14] Figure 14 illustrates this alternative and non-limiting aspect of the chemical reactor system for gas synthesis of the present invention: a multi-vessel pseudo-batch reactor system of connected individual catalytic reactors for gas synthesis, with inlets for separated reactants and outlets for reaction products, as well as backflow capabilities that can be individually selected using multi-port valves.

[0070] [Figure 15] Figure 15 illustrates a non-limiting cross-sectional view of one of the individual reactor pressure vessels used in the present invention and shown in Figures 11-14.

[0071] [Figure 16] Figure 16 illustrates a non-limiting cross-sectional view of an individual reactor pressure vessel used in the present invention as illustrated in Figures 11-14, which incorporates an active cooling system.

[0072] [Figure 17] Figure 17 is a schematic process diagram of a non-limiting example of an ammonia production system, showing how the chemical reactor systems in Figures 11-14 interact with other parts of the system.

[0073] [Figure 18] Figure 18 is a schematic process diagram of a non-limiting embodiment of the control system for the chemical reactor system of Figures 11-14 of the present invention. [Modes for carrying out the invention]

[0074] The terms used herein are for the sole purpose of describing specific aspects and are not intended to limit the invention. When used herein, the term "and / or" encompasses any combination with one or more related enumerated items. When used herein, the singular forms "a," "an," and "the" are intended to encompass both the plural and singular forms unless the context clearly indicates otherwise. When used herein, the terms "contains" and / or "contains" identify the presence of a described feature, step, action, element, and / or component, but are not intended to exclude the presence or addition of one or more other features, steps, actions, elements, components, and / or sets thereof.

[0075] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as those commonly understood by those skilled in the art to the extent of the present invention. Terms as defined in commonly used dictionaries should be interpreted as having the same meaning as their meaning in the relevant technical field and in the context of this disclosure, and it should be further understood that they should not be interpreted in an ideal or overly formal sense unless explicitly defined herein.

[0076] It will be understood that numerous techniques and steps have been disclosed in describing this invention. Each of these has its own merits, and each can be used in conjunction with one or more, or in some cases, all of the disclosed techniques. Therefore, for the sake of clarity, this description will refrain from unnecessarily repeating all possible combinations of the individual steps. Nevertheless, this specification and claims should be read with the understanding that such combinations are entirely within the scope of the invention and claims.

[0077] Provided by this disclosure is a reactor system for gas synthesis comprising a batch, pseudo-batch, temperature swing, or dynamic reactor of one or more individual catalytic reactors for gas synthesis, one or more fluid control mechanisms for shared pipes and manifolds for the delivery of reactants to the chemical reactor system and the collection of reaction products, and a control system that can open one or more fluid control mechanisms for controlling the inflow of reactants to the chemical reactor system and the outflow of reaction products. These chemical reactor systems can be coupled with variable or intermittent energy production technologies, making them particularly useful as energy waste reduction systems. In one non-limiting embodiment, coupling the chemical reactor system of the present invention with a variable or intermittent energy production technology enables a Power-to-X (also known as P2X or P2Y) system. Power-to-X, P2X, or P2Y can be defined as a power conversion, energy storage, and / or reconversion system from renewable energy. Non-limiting examples of such energy production technologies include solar, wind, hydro, and geothermal energy production technologies. Methods are provided for the use of these systems in gas synthesis, and in particular in ammonia synthesis, as well as for improving ammonia synthesis plants. When used in ammonia (NH3) synthesis, the disclosed chemical reactor systems enable the adaptation of established gas catalytic chemistry, such as that used in most Haber-Bosch processes, to fluctuating or intermittent renewable energy power sources.

[0078] Figures 2 to 10 illustrate non-limiting embodiments of the chemical reactor system 200 of this disclosure, which includes a multi-container temperature swing reactor system 230. As those skilled in the art will understand from reading this disclosure, however, alternative embodiments including a single-container reactor can be used in these chemical reactor systems and are considered to be within the scope of the present invention.

[0079] Referring to Figure 2, multiple reactor vessels 202a, 202b, 202c…202n are connected to a common inlet 201 and outlet 209 manifold by pipes 205 having mechanisms for controlling the inflow 206 and outflow 207 of reactants into the vessels. In one non-limiting embodiment, each reactor vessel is provided with inlet 206 and outlet 207 valves as these mechanisms. The inlet manifold 201 may be provided with valves 201a, 201b for controlling the composition of reactants within the inlet manifold. Other embodiments may have duplicate inlet manifolds 201 and associated inlet valves 206 dedicated to each reactant. The orientation of the vessels, manifolds, and pipes may be optimized according to the characteristics of the reaction, reactants, catalyst, and heat transfer, among other constraints.

[0080] Each reactor vessel 202 comprises a hollow cylindrical section containing a catalyst 203 and having domes or heads 204 fixed to each end. Some embodiments may feature detachable or removable heads at each end of the hollow cylinder. In one non-limiting embodiment, the reactor vessel 202 is constructed from a standard hydrogen storage tank (see details in Figure 7). In another non-limiting embodiment, the reactor vessel 202 is constructed using the length of a nominal pipe (NPS or DN), and the heads 204 are constructed using standard pipe (e.g., ASME, DIN, or EN) flanges (see details in Figure 5 or Figure 6).

[0081] Each reactor vessel is filled with a synthetic feed gas by opening a dedicated inlet valve 206 that connects the reactor pressure vessel to the inlet manifold 201. The inlet valve 206 allows the fluid flowing in from the inlet manifold 201 to enter the vessel and is open for a sufficient amount of time to pressurize the vessel to the desired operating point, after which the valve 206 is closed. For a series batch filling system, the time spent filling a given reactor vessel is approximately equal to the mass of gas in each reactor vessel 202 at the peak operating pressure divided by the total mass flow rate of the reactor system.

[0082] At the start of a filling sequence for a given reactor, the internal pressure is lower than at the end of the filling sequence; therefore, at the start of the filling sequence, there is a larger pressure difference across the entire inlet valve 206 than at the end.

[0083] In a system of reactor vessels operating in series filling, each reactor is sequentially filled via the same methodology, with some overlap in opening the inlet valves 206 between reactors, to ensure continuous flow in the inlet manifold, depending on the requirements of the upstream compression system or other constraints. The pressure in the inlet manifold fluctuates slightly with the opening and closing of the inlet valves, but is typically at or near the desired reactor operating pressure within the reactor. The inlet valves 206 and outlet valves 207 of each reactor remain closed unless that particular reactor is being filled or discharged.

[0084] After the reactor is filled with the reactant gas, the reaction proceeds as long as the conditions are favorable for the given reaction. In a non-limiting example, in ammonia synthesis, this requires that the reactants be at sufficiently high pressure and temperature and in the presence of a suitable catalyst. In some non-limiting embodiments of the present invention, the incoming reactants are heated before entering the reactor; this may be the result of compression of the reactants (before inflow into the reactor vessel) or a temperature increase due to another heat source. In some non-limiting embodiments of the present invention, an internal or connected heat source may be used to heat the reactants after they have been added to the reactor vessel (see Figure 5 or Figure 6 for details).

[0085] In ammonia synthesis, heat is released as the reaction progresses, and nitrogen and hydrogen reactants are transformed into ammonia products. Depending on the volume of each reactor vessel, heat release may need to be controlled so as not to exceed either practical or design temperature conditions. In addition, according to Le Chatelier's principle in ammonia synthesis (see Le Chatelier's principle in English with the extension www.wikipedia.org / wiki / Le_Chatelier%27s_principle), high reactor temperatures reduce equilibrium transformation. To control the reactor temperature, one or more reactants can be added to the reactor slowly, for example, at a rate that matches the heat released by the atmospheric cooling of the reactor body.

[0086] In a non-limiting embodiment of the present invention, valve 201a is connected to a high-pressure hydrogen supply, and valve 201b is connected to a high-pressure nitrogen supply. The reactor vessels are sequentially filled with hydrogen to a desired pressure through valve 201a while valve 201b is closed; after all vessels have been filled with hydrogen at the operating pressure and temperature, valve 201a is closed. Subsequently, valve 201b is opened, and each vessel has nitrogen (through valve 206) added at a rate low enough to maintain a constant reaction temperature within each vessel.

[0087] In ammonia synthesis, a product-to-reactor molar ratio of 0.5 means that the pressure in the adiabatic system can decrease as the reaction proceeds (depending on the system temperature); this allows nitrogen to be added to the reactor as the reaction progresses while maintaining approximately the same operating pressure without removing the product. After equilibrium transformation is achieved for the given reactor conditions, the nitrogen inflow is stopped, and the reactor is allowed to cool below the dew point or critical temperature of the ammonia product (approximately 132 degrees Celsius), after which the liquid ammonia product can be discharged from the reactor. In some non-limiting aspects of the present invention, the catalyst-containing vessel may be initially filled with nitrogen, and hydrogen may be added stepwise in a manner similar to that described above.

[0088] In some non-limiting embodiments of the present invention, the reactor is initially filled, and all reactants are added as the reaction proceeds until an equilibrium transformation is reached. In ammonia synthesis, as products are formed, energy is released until an equilibrium transformation is achieved and no more ammonia is produced. Depending on the rate at which nitrogen is added to the reactor, the heat generated by the reaction may cause the reactor temperature to increase or remain the same; after the reaction equilibrium is achieved, the reactor temperature stabilizes as the reaction slows down or stops. After the reactor begins to cool by either the atmosphere or any applied cooling, the reaction may begin to move forward again toward a new equilibrium transformation, according to Le Chatelier's principle (see Le Chatelier's principle in English with the extension www.wikipedia.org / wiki / Le_Chatelier%27s_principle). Once the final equilibrium transformation is achieved, the reactor is cooled to below the dew point or critical temperature of the ammonia products (approximately 132 degrees Celsius), allowing the gaseous ammonia to condense into a liquid depending on the partial pressure of ammonia, after which the liquid products can be discharged from the reactor.

[0089] The purpose of emptying the reactor in this invention is to remove as much liquid-phase ammonia product as possible without allowing unreacted reactant gases to flow out of the vessel through the outlet manifold. After the ammonia cools below its critical temperature (or dew point / bubble point, depending on the operating pressure), it undergoes a phase change from gas to liquid and precipitates at the bottom of the reactor vessel; the reactants remain in the gaseous phase even well below ambient temperature at typical system operating pressures. The outlet pipe of the vessel therefore needs to be positioned toward the bottom of the vessel (either externally, as shown in Figures 2 to 7, or internally, using some kind of bottom collector). Liquid-phase product removal allows relatively pure and high-quality ammonia products to be extracted from the reactor vessel under high pressure without the need for significant product cooling, recycling of unreacted reactant gases (and associated equipment), as is the case in the current state of the art.

[0090] Discharging the product from the reactor is completed by opening a mechanism or valve 207 that connects the reactor to the outlet manifold 209 after the reactor has cooled sufficiently for the liquid product to form; in most embodiments, the inlet valve 206 remains closed during container discharge. The pressure in the outlet manifold is lower than the operating pressure of the reactor container and is potentially equal to or near the product storage pressure, which can be as low as about 15 bar depending on the ambient temperature. The pressure difference between the reactor and the outlet manifold is the driving force for emptying the container. In some non-limiting embodiments of the invention, energy can be recovered as the product liquid is reduced in pressure from the reactor pressure to the outlet manifold pressure.

[0091] At the start of the discharge sequence, the pressure difference across the outlet mechanism or valve 207 is at its maximum, and this pressure difference decreases as the reactor is discharged. The outlet valve 207 is closed before all liquid products have been removed from each reactor to prevent unreacted gases from flowing into the outlet manifold 209. Various types of container level gauges may be needed to determine when sufficient liquid products have been removed (and to minimize the outflow of unreacted gases). After sufficient liquid products have been removed from the reactor, the reactor can be refilled with reactants (heated externally or internally) up to the operating pressure, which allows for the production of more products.

[0092] In some non-limiting embodiments, depending on the rates of filling, reaction, cooling, and discharge, after the last reactor 202n is filled, the first reactor 202a is refilled, which maintains a continuous flow throughout the system. The control system must account for the time required to empty the reactors; because of the continuous flow, the next reactor to be filled must be emptied in advance before filling. The non-moving residence time of each reactor vessel is therefore approximately equal to the individual reactor filling time multiplied by the number of subsequent reactors.

[0093] In a system operating with series filling, the available average residence time is a function of the sum of the catalyst volumes of all reactors divided by the total system flow rate. For a given throughput and target residence time (and therefore catalyst volume), the number of series-filled reactors selected for the system is an optimization between the desired non-moving residence time and the limit on reactor filling.

[0094] The filling and discharging of the reactors are limited to several maximum speeds determined by the allowable pressure drop and potential catalyst damage or entrainment through the catalyst bed, the pressure change limits of the vessel, or several other physical criteria (such as the valve opening and closing speed during the filling sequence). In some non-limiting embodiments of the present invention, it is desirable to fill a group of reactors in parallel.

[0095] This non-limiting aspect of the present invention can also be used to have flow between reactors using either an inlet or outlet manifold during downtime periods (e.g., nights or periods of low wind when no variable or intermittent renewable energy is available). In one non-limiting example, reactor 202a is discharged to reactor 202b via an inlet manifold during periods when upstream compression (not shown in Figure 2) is shut down. For this (and other scenarios) to work, flow must be generated from the high-pressure reactor to the low-pressure reactor. In this exemplary scenario, reactor 202a operates at a higher pressure than reactor 202b, accompanied by all reactors operating in batch mode (all reactor inlet / outlet valves are closed).

[0096] In a non-limiting embodiment of the present invention, several reactors are filled with only one reactant (e.g., hydrogen) during the day to a pressure higher than the normal reactor operating pressure (e.g., 350 bar or 700 bar), while some reactors are filled with both reactants to the normal operating pressure. During periods when no power is available, after a given reactor has discharged its product, gas from the higher-pressure reactors is discharged into the inlet manifold to refill empty reactors, etc.; after all the higher-pressure filled reactors have been discharged to their normal operating pressure, they can all be used to produce products by progressively adding nitrogen. This operating scenario allows fewer reactors to be used to store reactants at higher densities for "offline" production.

[0097] To complete the transfer of gas from reactor to reactor, valve 206a is opened, connecting inlet manifold 201 to line 205a, while valve 207 is closed. In reactor 202b, valve 206b is positioned to connect inlet manifold 201 to line 205b; valve 207b is closed. Gas flows from reactor 202a to inlet manifold 201 via pipe 205a and valve 206a, and then into reactor 202b via valve 206b and pipe 205b. The gas stops flowing between reactors 202a and 202b when the pressure difference is exhausted; the final operating pressure will be one of two starting pressures, depending on the relative volumes of both reactors, the catalyst void ratio, and the gas composition. In some non-limiting embodiments of the present invention, a single multiport valve replaces valves 206 and 207.

[0098] Figure 3 illustrates a non-limiting aspect of the present invention: a multi-container temperature swing ammonia synthesis reactor system 230 using a multi-port valve.

[0099] Referring to Figure 3, a non-limiting embodiment of the present invention is illustrated, similar to Figure 2, in which a multi-port valve is used for filling and discharging individual reactor vessels. The advantage of the non-limiting embodiment shown in Figure 3, beyond that shown in Figure 2, is that each reactor can be selected at any time for filling or discharging, while using a single valve or mechanism for that purpose.

[0100] As an unspecified example of filling individual reactors 202, the reactant gas flows through a manifold 201 and a valve 206, which is positioned to connect the inlet manifold reactor line 201 to the reactor via an inlet pipe 205; in this position, the connection between line 205 and outlet manifold 209 is closed. As the reactor is filled, the incoming gas pressurizes the reactor vessel 202 from the initial pressure to the operating pressure. As the other reactors (202b, 202c…202n) are filled, reactor 202a can be emptied from any point by repositioning valve 206 so that line 205 is open to outlet manifold 209 and closed to inlet manifold 201. The high pressure in reactor 202 pushes the reacted product gas through valve 206 and the manifold toward the lower outlet manifold 209, which operates at a lower pressure.

[0101] Figure 4 illustrates another non-limiting aspect of the present invention: a multi-container temperature swing ammonia synthesis reactor system 230 with multiple inlet manifolds.

[0102] Referring to Figure 4, an unlimiting embodiment of the invention is illustrated similarly to Figure 2, except that it includes multiple manifolds for filling individual reactor vessels. The advantage of the unlimiting embodiment shown in Figure 4, beyond that shown in Figure 2, is that one reactant (e.g., nitrogen) can be added to individual reactors, while other reactors can be filled with a different reactant (e.g., hydrogen).

[0103] As a non-limiting example, inlet manifold 201a is dedicated to hydrogen gas, while inlet manifold 201b is dedicated to nitrogen gas. In this scenario, reactor 202a is initially filled with hydrogen reactants, which flow into the reactor through manifold 201a, valve 206, and pipe 205, while the nitrogen inlet valve 210 and outlet manifold valve 207 remain closed. The incoming hydrogen gas pressurizes reactor vessel 202a from a lower initial pressure to a higher operating pressure as the reactor is filled. After reactor 202a is filled, nitrogen reactants can be introduced into reactor 202a through a dedicated nitrogen inlet valve 210 and nitrogen manifold 201b. An advantage of the non-limiting aspects of the present invention illustrated in Figure 4 is that while other reactors (e.g., 202a) are filled with nitrogen, other reactors (e.g., 202b, 202c…202n) can be filled with hydrogen either in series or in parallel using their dedicated hydrogen manifold inlet valves. A further advantage of this non-limiting aspect of the present invention is that hydrogen and nitrogen can be added to individual reactors in parallel and in different ratios as needed, depending on either the current state of the reaction or a particularly desired reactant ratio.

[0104] After the reaction has proceeded sufficiently, no further nitrogen is added, and the reactor is allowed to cool below critical temperature, thereby allowing the ammonia product to condense from gaseous to liquid. Each reactor can discharge the liquid ammonia product to the outlet manifold 209 by closing its dedicated inlet valves 206, 210 and opening the outlet valve 207. The high pressure in reactor 202 pushes the reacted product gas through valve 207 and the manifold towards the lower outlet manifold 209, which operates at a lower pressure.

[0105] Figure 5 illustrates a non-limiting cross-sectional view of an individual reactor pressure vessel used in the present invention.

[0106] Referring to Figure 5, in this embodiment, the reactor vessel 202 is a pressure vessel comprising a cylindrical shell that fits into flanges 216 at each end to which the heads 208 are attached. In one non-limiting embodiment, the heads 208 are removable. The pressure vessel heads include one or more means 215, such as nozzles, for connecting pipes for fluid inflow and outflow; some non-limiting embodiments may have one or more means 215, such as nozzles, at both ends. The shell of the pressure vessel is contained within a catalyst bed 203 between the pressure vessel heads. In some non-limiting embodiments, the catalyst bed completely fills the vessel, while in other non-limiting embodiments, the catalyst occupies only a portion of the vessel volume, allowing for a higher average void ratio and increased gas capacity. The catalyst is prevented from flowing out of the pressure vessel during operation by a catalyst holder or a grate 217 at each end. One head may be equipped with a standard flange gasket 218.

[0107] In one non-limiting embodiment, the catalyst grid 217 is positioned between the pressure vessel flange 216, the gasket 218, and the head 208; in another non-limiting embodiment, the grid may be integrated with the gasket, which creates a seal between the pressure vessel flange and the head. In a preferred embodiment, to reduce cost and the requirements for custom design, manufacturing, and testing, the reactor vessel 202 is constructed using nominal pipe lengths (NPS or DN), and the flange 208 and head 508 are constructed using standard pipe flanges (e.g., ASME, DIN, or EN). The multi-vessel reactor system described in the present invention enables the use of nominal pipes and standard flanges.

[0108] Figure 6 illustrates a non-limiting cross-sectional view of an individual reactor pressure vessel used in the present invention, which includes an integrated active cooling or heating system.

[0109] Referring to Figure 6, similar to Figure 5, non-limiting embodiments of individual reactor vessels used in the present invention with the addition of an active heat transfer system are illustrated. As shown in Figure 5, the reactor vessel 202 is a pressure vessel comprising a cylindrical shell that fits into flanges 216 at each end to which a head 208 is attached. The pressure vessel head comprises one or more nozzles 215 for connecting pipes for fluid inflow and outflow; some embodiments may have one or more nozzles 215 at both ends. In one non-limiting embodiment, a hollow outer pipe 220 with inlet nozzles 221 and outlet nozzles 222 covers a portion of the cylindrical shell of the reactor vessel 202. A heat transfer medium flows into the outer pipe 220 through the nozzles 221, into which the heat transfer medium contacts the pressure vessel shell. In one non-limiting embodiment used for reactor cooling, a cooling heat transfer medium is passed through the nozzles 221 through a heat transfer system in the outer pipe 220, into which the cooling heat transfer medium is heated, to cool the reactor vessel 202 and its contents. The flow of the heat transfer medium is controlled either continuously or by batch flow using a valve (not shown here) above the outlet. In some embodiments, the addition of heat transfer medium to the jacket can be used to increase the thermal inertia during reactor operation, even if the medium does not flow during normal operation.

[0110] Figure 7 illustrates cross-sectional views of individual reactor configurations used in the present invention, where a typical pressurized gas storage tank is filled with a catalyst for use as a reactor pressure vessel, as shown in Figures 2, 3, and 4.

[0111] Referring to Figure 7, in this embodiment, the pressure vessel consists of a typical gas storage tank, such as the type used for compressed hydrogen storage. The system presented herein is applicable to all types of hydrogen storage, from Type 1 (metal only) to Type 5 (composite).

[0112] In a non-limiting embodiment of the present invention, the cylindrical shell of the reactor vessel 202 is fitted with fixed domes or heads 204 at each end. One head of the reactor vessel is equipped with a collar 223 and a nozzle 215, facilitating the connection of valves 224 and / or valve pipes 225 for inflow and outflow. The pressure vessel shell is filled either completely or partially by a catalyst bed 203 between the pressure vessel heads. In a preferred embodiment, catalyst filling is completed through a tank nozzle after cylinder fabrication, but before the installation of valves or pipes. The catalyst is prevented from flowing out of the pressure vessel during operation or blocking the gas outlet hole by some grate, shield, perforated or grooved cover 217 near or over the nozzle.

[0113] In one non-limiting embodiment, the catalytic grid 217 is positioned around a pipe 225, which is typically threaded into a cylinder or tank nozzle. In some non-limiting embodiments, a portion of the valve pipe 225 is reduced in diameter to allow for a sheath of the grid 217 around the pipe, which allows for gas flow at one or more points along the pipe without the risk of catalytic beads blocking the pipe (as in the case of a single outlet hole without a grid). In this non-limiting embodiment, the narrower portion of the pipe and the grid are sized smaller than the internal diameter of the cylinder nozzle to allow for fitting and removal after the cylinder is manufactured.

[0114] The ability to use standard high-pressure gas storage cylinders (Type 1 to Type 5) is enabled by the multi-container reactor system described in the present invention, as it allows for smaller reactor vessels with a single inlet / outlet nozzle used for greater overall processing rates without the need for large custom-designed reactor vessels, enabling the use of periodic "static gas catalytic action".

[0115] Figure 8 is a schematic process diagram of a non-limiting example of an ammonia production system, illustrating how the present invention interacts with other parts of the system. As will be understood by those skilled in the art upon reading this disclosure, the chemical reactor system of the present invention can be routinely integrated in a similar manner into gas synthesis systems other than ammonia.

[0116] Referring to Figure 8, in a non-limiting embodiment of this ammonia production system using the present invention, hydrogen and nitrogen feed gases are supplied to system 801 and combined with recycled unreacted feed gas 820 before being supplied to the feed gas compression system 802. In one non-limiting embodiment, the feed gas compressor 802 may be driven by a variable speed motor 804 and controlled by a flow control 803 above the compressor outlet. In some non-limiting embodiments, hydrogen and nitrogen are supplied to the gas compressor system 802 by separate inlet manifolds and compressed sequentially; in other embodiments, a separate compressor may be used for each reactant feed gas.

[0117] The operating pressure of the reactor system is typically controlled by a pressure control device within the synthetic reactor unit 200; in a non-limiting embodiment, this is controlled by output pressure via a compressor 802, flow velocity 803, and therefore motor control 804. Details of the non-limiting embodiment are shown in Figure 9.

[0118] The pressurized supply gas passes through an optional supply gas heat exchanger 805, which heats or cools the supply gas to the desired temperature as needed. In one non-limiting embodiment, a temperature control device 806 controls a bypass 807 around the supply gas heat exchanger to optimize the temperature of the supply gas flowing into the chemical reactor system 200; the reactant gas is further heated within the gas synthesis reactor system 200. In some non-limiting embodiments, a lower operating temperature required within a longer residence time of the pseudo-batch reactor system allows the supply gas to be heated by the gas compression stage 802 without the need for a preheater 805 (805). In other non-limiting embodiments, the reactors in the system are heated individually by jackets or by other means (as shown in, for example, Figure 6) again without the need for a preheater 805.

[0119] The products and any unreacted feed gases within the synthesis reactor system 200 are cooled primarily by the ambient temperature while remaining in the reactor (to allow the products to change from gaseous to liquid phase), but may be further cooled or supercooled in the product gas cooler 809. In one non-limiting embodiment, this may be an air cooler driven by a variable drive motor 812 controlled by a downstream temperature control device 811.

[0120] The cooled product fluid is passed to a gas-liquid separator 813 where the liquid is separated into unreacted hydrogen gas and nitrogen gas. The level in the gas-liquid separator is controlled by a level control device 814 equipped with a level control valve 815; the liquid ammonia product is released from the system 816.

[0121] In some non-limiting embodiments of the present invention, the pressure of the downstream system of the reactor system 200, which includes a product gas-liquid separator, is controlled by a pressure control device 817 and a control valve 818 with separate operating conditions (pressure and temperature) set to ensure that ammonia is in a liquid state while any unreacted hydrogen and nitrogen are in a gaseous state. The unreacted hydrogen and nitrogen gases are recycled to an inlet supply gas compressor 820.

[0122] In this non-limiting embodiment of the invention within an ammonia production system, the reactor system 200 receives data from the supply gas compressor flow control 803, the supply gas heat exchanger bypass temperature control device 806, and the downstream system pressure 810, and controls their setpoints. In a non-limiting example, the reactor system 200 may interact with the compressor flow control 803 by increasing the compressor flow rate setpoint to reduce the reactor residence time, or vice versa. Similarly, the reactor system 200 may lower the supply gas heater temperature control setpoint to reduce the supply gas inlet temperature as the system throughput decreases and the reactor residence time (and thus the reaction conversion) increases.

[0123] Further details of various non-limiting embodiments of the control system of the present invention are outlined in Figure 9, which shows a schematic process diagram of one non-limiting embodiment of the control system for a temperature swing reactor, as described in Figure 2.

[0124] Referring to Figure 9, in a non-limiting embodiment of this ammonia production system, the gas flow through a series of pressure vessel reactors 202a-n is controlled by a local system control device 930 in response to input from a remote control device 931, using a series of inlet 206a-n and outlet 207a-n mechanisms and various sensors 925.

[0125] Non-limiting embodiments of this invention include two separate inlet manifolds 201a, 201b, as shown in Figure 4; alternative embodiments of the invention may include only a single inlet manifold (as shown in Figure 2).

[0126] During normal operation, pressurized synthetic supply gas is supplied to inlet manifolds 201a and 201b. The flow velocity and temperature of the fluid flowing into the system are set by upstream system control units 920a, 920b, 921a, and 921b in response to input from the local system control unit 930. The flow velocity and pressure in inlet manifolds 201a and 201b are monitored via pressure transmitters 922a and 922b and flow transmitters 920a and 920b to determine that the flow into the system matches the system's capacity. For example, an increase in inlet manifold pressure signals the local control unit 930 to lower the output flow velocity setpoint of any upstream compression system in the flow control unit 920.

[0127] In a non-definitive exemplary sequence (as shown in Figure 4) in which the reactor is first filled with hydrogen and then with nitrogen, after the hydrogen inlet manifold 201a reaches operating pressure, the local control unit 930 opens the hydrogen inlet valve 206a on the first reactor 202a, allowing hydrogen gas to flow in and increasing the internal pressure within each reactor. The temperature of the hydrogen in the manifold depends on the efficiency of the upstream compression system and approaches the desired reactor operating temperature of about 200-300°C.

[0128] In some non-limiting embodiments, the local control unit 930 can measure the reactor status from sensors such as inlet pressure 925a, manifold temperature, reactor temperature 925a, and gas flow to the reactors 920a, 920b, and use this data to calculate the remaining time to fill the reactor with new synthesis gas. The inlet valve 206a is programmed to close after the reactor reaches its operating pressure; the valve begins to close completely at the target operating pressure. As the inlet valve 206a closes over the first reactor 202a, the system begins to open the inlet valve 206b over the second reactor 202b. This sequence is repeated for reactors 202c, etc., until the last reactor 202n is filled; this completes one filling cycle. In some embodiments, depending on the residence time required for filling, reaction, and system cooling, once each cycle is complete, the first reactor 202a is emptied and refilled using the same technique.

[0129] Once a designated reactor (202a in this example) is sufficiently filled with hydrogen gas from manifold 201a and reaches operating pressure (and valve 206a is closed), nitrogen gas can be gradually introduced into the reactor by opening valve 210a. After nitrogen is added to the high-temperature hydrogen-filled reactor, an exothermic reaction begins, releasing heat as ammonia is produced, raising the temperature of the reactants, products, catalyst, and reactor vessel.

[0130] Some of the heat generated by the exothermic reaction is lost to the environment through the reactor walls, depending on the reactor materials, design, and any insulation. The reactor temperature must be maintained at an operating temperature high enough to sustain the reaction but low enough to achieve good equilibrium transformation. Nitrogen is added to the reactor at a controlled rate to maintain the temperature at the desired temperature; it can be added continuously, in pulses, or in other ways. In ammonia synthesis, a molar ratio of 0.5 product to reactant means that the pressure in the adiabatic system decreases as the reaction proceeds; nitrogen can therefore be added to maintain a sufficient operating pressure.

[0131] A local control device 930 monitors the progress of the reaction via temperature and pressure measurements 925a-n; some non-limiting aspects of the invention may have more than one temperature indicator to ensure accurate monitoring of the entire length of the reactor. The inflow of nitrogen into the reactor is controlled to maintain a desired set of operating conditions. Some non-limiting aspects of the invention may initially add significant nitrogen to induce a high temperature (and therefore initial reaction rate) before allowing the reactor to cool slightly towards the end of the batch production cycle and enhance the equilibrium transformation.

[0132] When the reaction has progressed to the desired point (for example, when the equilibrium shift is reached), the nitrogen inlet valve is closed, the reaction slows down, and more heat is lost to the environment than is generated by the exothermic reaction, so eventually the reactants, products, catalyst, and reactor vessel begin to cool. As the reactor temperature falls below either the critical temperature (approximately 132°C) or the dew point temperature of ammonia at a given internal pressure, the liquid ammonia product condenses within the reactor. The liquid condenses toward the bottom of the reactor, allowing drainage to the outlet manifold 209.

[0133] Emptying the reactor (e.g., the first reactor 202a shown in the figure) involves opening the outlet valve 207a for a sufficient time to allow as much liquid ammonia as possible to flow out without allowing unreacted gas to escape. Some non-limiting embodiments may include a level measuring system on the reactor (not shown in Figure 9) to ensure that the outlet valve is closed after a low liquid level is reached; other non-limiting embodiments may use an algorithm to predict the liquid level and discharge rate. Any gas released with the liquid ammonia is recycled through a gas-liquid separator downstream of the reactor operating at a lower pressure.

[0134] As liquid ammonia is released from the reactor, the pressure within the reactor decreases; the temperature of the catalyst and reactor body may decrease during the discharge process due to the reduction in pressurized gas (depending on the hydrogen content in the unreacted gas due to the inverse Joule-Thomson effect). After discharging as much liquid ammonia as possible from the reactor, the refilling process described above can be restarted. Some non-limiting embodiments of the present invention may have a reactor capacity (or number of reactors) sufficient to store all the available hydrogen and available daily energy in a given upstream hydrogen production system. In this non-limiting embodiment, once a given reactor is filled to a desired operating pressure, only enough nitrogen to maintain a desired operating temperature is added, accompanied by a slow-moving reaction during periods of low energy availability (e.g., overnight in a solar energy system) to enhance the equilibrium transformation. In this operating scenario, reactor refilling occurs only after sufficient energy is available for hydrogen production (e.g., after sunrise in a solar energy system).

[0135] In some non-limiting embodiments, the reactors may have different operating pressures to optimize ammonia production and equilibrium conversion. In some non-limiting embodiments, some reactors may be used for hydrogen storage at high pressure, while others may be used for ammonia production at lower operating pressures. In a non-limiting example, reactor 202a is filled with hydrogen to 700 bar without nitrogen addition, while reactor 202b is filled with hydrogen to 250 bar with nitrogen introduction to produce ammonia. As reactor 202b goes through the filling, reaction, and discharge cycle, the reactor pressure will be lower than the desired operating pressure of 250 bar; it can be refilled from reactor 202a during compressor shutdown periods by opening valve 206a, which allows the gas in reactor 202a to pressurize the hydrogen inlet manifold 201a. This can be repeated until the internal pressure of reactor 202a is low enough to allow it to operate as a reactor vessel (with nitrogen introduction to produce ammonia). In some non-limiting embodiments, a portion of the reactor vessel may be used for high-pressure hydrogen storage, while the remainder may be used for ammonia production.

[0136] Some non-limiting embodiments of this system may have an additional heat transfer mechanism filled with a heat transfer fluid connected to a cooling or heating loop that enables active reactor temperature control, such as a hollow outer pipe 220, sleeve, or jacket on a reactor, as illustrated on one vessel 202n. The heat transfer jacket has an inlet pipe 221, an outlet pipe 222, and a valve 224 for controlling the flow of the heat transfer medium. In some non-limiting embodiments of the reactor system, all reactors are equipped with this active cooling mechanism; in other non-limiting embodiments, only some of the reactors are equipped with active cooling. The active cooling system may also be used to rapidly cool the products after the desired reaction progress has been achieved, or to heat the reactor during system startup.

[0137] To operate the reactor heat transfer system, the local control unit 930 opens the heat transfer medium control valve 224 to ensure a flow of heat transfer medium at a rate sufficient to maintain control, increase, or decrease of the reactor temperature. In some non-limiting embodiments, an active heating or cooling system may be used to maintain a constant reactor temperature (isothermal operation). After a predetermined temperature has been reached, the local control unit 930 may configure the active heat transfer system to cool the reactor or to slow the increase in reactor temperature. This allows for increased equilibrium transformation beyond purely adiabatic operation, which requires the discharge of reactor contents at a predetermined temperature, in order to maintain the reactor and catalyst temperatures below a specific value (such as the catalyst sintering temperature).

[0138] Some non-limiting embodiments of this system may include the connection of the local control unit 930 to a remote control unit 931 that receives and transmits data from numerous systems operating in parallel. In some non-limiting embodiments, the remote control unit may be cloud-based. The remote control unit 931 can be used to collect data from non-system-specific sources, such as a weather tracking system or database, performance data from other reactor systems operating nearby, or a local renewable energy power demand curve, and utilizes these inputs to predict the required reactor system performance state or setpoints. Some non-limiting embodiments of the system may use artificial intelligence within or through the remote control unit 931 to help generate predictive control setpoints for the local control unit 930; other non-limiting embodiments may use the remote control unit for central computing power, enabling a lower-cost local control unit.

[0139] Figure 10 is a schematic diagram of a process in one non-limiting aspect of the present invention for an ammonia synthesis system that enables production during periods of low power availability (e.g., overnight ammonia production in a solar energy system). As will be understood by those skilled in the art by reading this disclosure, this process using the chemical reactor system of the present invention can be similarly and conventionally adapted for gas synthesis processes other than ammonia.

[0140] Referring to Figure 10, in a non-limiting embodiment of an ammonia production system using the present invention, the compression system 802 is supplied by hydrogen 1001 and nitrogen 1002 feed gases via separate manifolds. The hydrogen feed gas source (typically from some water electrolysis system) is combined with recycled unreacted feed gas 820. In a non-limiting embodiment, the feed gas compressor 802 is driven by a variable speed motor 804 and controlled by a flow control 803 above the compressor outlet. The non-limiting embodiments shown herein have a single compressor used interchangeably for both hydrogen and nitrogen; some non-limiting embodiments may use separate compressors for each reactant feed gas.

[0141] When electricity is available, hydrogen is produced (upstream in this schematic diagram), supplied to the supply gas compressor 802 via the hydrogen manifold 1001, directed to the reactor manifold (for hydrogen 206), and used in series, parallel, or a combination thereof to fill the ammonia reactor 230. In this non-limiting embodiment, the reactor vessel is a standard hydrogen tank, filled or partially filled with an ammonia synthesis catalyst. The hydrogen tank has a single inlet and outlet nozzle located at the bottom of the tank and is inverted to allow drainage of liquid ammonia without the need for an internal standpipe. Some other embodiments may use an internal standpipe with a non-inverting tank.

[0142] After sufficient hydrogen has been pressurized and stored in the reactor, and while power is still available, nitrogen is generated (upstream in this schematic diagram), sent to a compressor via a dedicated nitrogen compression manifold 1002, compressed by a supply gas compressor 802, and directed to a nitrogen reactor manifold 210, where it is used to fill the nitrogen storage cylinder 1010. The nitrogen is compressed to a pressure well above the normal reactor operating pressure, allowing the flow of nitrogen from the storage cylinder 1010 to the temperature swing reactor 230 without the need for further compression. Several methods may allow nitrogen to be compressed and stored before hydrogen; systems with a dedicated or parallel compressor can choose to perform both tasks simultaneously.

[0143] When the initial ammonia reactor is sufficiently filled with hydrogen (and recycled unreacted gas) to reach the minimum desired operating pressure, and before the hot compressed gas cools within the reactor, nitrogen can begin to be introduced into the reactor from a nitrogen manifold. The amount of nitrogen introduced into a given reactor should be sufficient to maintain the reactor at the desired operating temperature through the heat released by the ammonia synthesis reaction; the heat released from the reactor into the atmosphere should be replaced by the heat released from the synthesis reaction. As ammonia is produced, the pressure within the reactor decreases and the temperature increases, and nitrogen can be added using feedback or predictive control based on temperature, pressure, or a combination of both.

[0144] During periods of low or no power availability (such as after sunset at a solar power plant), nitrogen can be gradually introduced into the reactor, allowing ammonia production to continue without the need for ongoing compressed power. The only power requirements are for the control system 1011 and valve actuators (not shown in this schematic – see Figure 9), which can also be driven by compressed air or nitrogen. Due to the low utilization rate of systems coupled to intermittent renewable energy (typically around 30% utilization, or 12-17 hours without full power), the reaction rate can be significantly reduced by lowering the reaction temperature to match the available time. Lowering the temperature also increases the equilibrium transformation. The use of the pseudo-batch packed-bed reactor of the present invention enables this significant advantage over plug-flow steady-state reactor systems of the current state of technology.

[0145] When the reaction reaches the desired equilibrium transition, the addition of nitrogen to the reactor can be stopped, allowing the reactor to cool while it remains closed; the pressure may decrease slightly due to the decrease in temperature. After the reactor, catalyst, and gas have cooled below the critical temperature of ammonia (or the bubble / dew point depending on the partial pressure of ammonia), the ammonia changes to the liquid phase and is drained from the reactor to the outlet manifold 207. Depending on the operating conditions, catalyst, reactor size, reaction rate, and desired equilibrium transition, multiple temperature swing cycles may be completed during periods of available power (e.g., daytime in a solar power facility). The use of the method described herein is not limited to periods of low or no power.

[0146] Liquid ammonia flows out of the reactor to the outlet manifold 207 through a dedicated control valve (not shown) for each reactor. In this non-limiting embodiment, the outlet manifolds are controlled at a pressure 817, 818, 810 lower than the operating conditions of the reactors, meaning that some dissolved or unreacted gases may flash out from the ammonia. The liquid is sent to a gas-liquid separator 813, where any unreacted gases are recycled 820 to the compression system 802 via a hydrogen supply manifold 1001. The remaining liquid ammonia passes from the separator under level control 814 through a control valve 815 to an ammonia storage tank (not shown) via a liquid outlet manifold 816. Depending on efficiency and environmental concerns, some embodiments may choose to withhold recycling of any unreacted gases during low-power periods and to exhaust any unreacted gases from the gas-liquid separator 813 during periods when compression is not available.

[0147] Some non-limiting embodiments of the present invention, using high-pressure hydrogen storage tanks (standard 700 bar type 1 to 5 hydrogen tanks), allow some reactors to be filled to significantly higher pressures than normal reactor operating conditions (as shown in Figure 9). This allows the flow from the high-pressure reactor to refill an empty low-pressure reactor without requiring the compression system to operate. Storing hydrogen at higher pressures also allows for the use of smaller overall reactor systems; some non-limiting embodiments may have multiple types of reactors, some designed for low-pressure ammonia production and others designed for high-pressure storage and ammonia production.

[0148] The use of this non-limiting embodiment of the temperature swing reactor in the chemical reactor system of the present invention involves enabling longer residence times and slower reaction rates within individual reactors, and after reaction equilibrium is reached, cooling the product gas to ambient temperature below the liquefaction temperature. This reactor design of the present invention allows liquid ammonia to be extracted from the reactor separately from unreacted feed gas without the need for complex cooling or high recycling rates.

[0149] Figures 11 to 18 illustrate alternative and non-limiting embodiments of the chemical reactor system 200 of this disclosure, which includes a multi-vessel pseudo-batch reactor system of the present invention having inlets for separate reactants and outlets 235 for reaction products.

[0150] Referring to Figure 11, a plurality of simplified reactor vessels 202a, 202b, 202c…202n are connected at each end of the vessels to a common inlet 201 and outlet 209 manifold by pipes 205. In one embodiment, each reactor vessel is provided with valves at the inlet 206 and outlet 207. The orientation of the vessels, manifold, and pipes may be optimized depending on the characteristics of the reaction, reactants, catalyst, and heat transfer, among other constraints.

[0151] Similar to the temperature swing reactor system described above, each reactor vessel 202 of this system 235 consists of a hollow cylindrical section filled with catalyst 203 and has heads 204 at each end. In one non-limiting embodiment, the reactor vessel 202 is constructed using the length of a nominal pipe (NPS or DN), and the heads 204 are constructed using standard pipe flanges (e.g., ASME, DIN, or EN). In one non-limiting embodiment, the heads 204 at each end of the reactor vessel 202 are provided with a grate 217 to prevent catalyst from flowing out of the vessel. In one non-limiting embodiment, the grate and head gasket are integral (see details in Figure 15).

[0152] The reactor vessels are individually filled with the synthesized supply gas by opening dedicated inlet valves 206 and outlet valves 207 with sufficient time and overlap to allow the contents of the reactor vessels to be discharged to the outlet manifold 209 as the fluid flowing in from the inlet manifold 201 into the vessels, and then allowing the valves to be closed. For a series batch filling system, the time spent filling / emptying a given reactor vessel is approximately equal to the volume of the reactor vessel divided by the total volumetric flow rate of the reactor system.

[0153] In a system of reactor vessels operating in series filling, each reactor is sequentially filled via the same methodology, with some overlap in valve opening between reactors, to ensure continuous flow at the inlet and outlet manifolds, depending on the requirements of the upstream compression system or other constraints; the inlet and outlet valves of each reactor remain closed unless that particular reactor is filled. In a non-definitive exemplary sequence, after the last reactor 202n is filled, the first reactor 202a is refilled, thereby discharging the reaction products to the outlet manifold 209 and maintaining continuous flow throughout the system. The non-moving batch residence time of each reactor vessel is therefore approximately equal to the individual reactor filling time multiplied by the number of subsequent reactors.

[0154] By design, there is little pressure change throughout the entire system, and therefore the inlet and outlet valves do not have a significant pressure difference; also, they do not need to provide a completely impermeable seal when closed. The role of the inlet and outlet valves is not primarily to contain pressure, but to direct the gas to the desired reactors in the desired order and to ensure the minimum residence time in each reactor vessel. This allows the system to be adapted to a multi-port valve, as illustrated in Figure 14.

[0155] In a system operating with series filling, the average residence time is a function of the sum of the catalyst volumes of all reactors divided by the total system flow rate. For a given throughput and target residence time (and therefore catalyst volume), the number of series-filled reactors selected for the system is an optimization between the desired non-moving residence time and the limit on reactor filling.

[0156] The filling of the reactor is limited to several maximum rates determined by the allowable pressure drop through the catalyst bed and limitations on potential catalyst damage or entrainment, or by several other physical criteria (such as the valve opening and closing speed during the filling sequence). In some embodiments of the present invention, it is desirable to fill a group of reactors in parallel.

[0157] Figure 12 shows a non-limiting embodiment of a multi-container pseudo-batch reactor system 235 with backflow capability.

[0158] Referring to Figure 12, non-limiting embodiments of the present invention are illustrated by a plurality of reactor vessels 202a, 202b, 202c…202n, each having a catalyst bed 203 and a head 204 connected at each end of the vessel to a shared inlet 201 and outlet 209 manifold by pipe 205, with additional equipment to enable backflow through the reactor vessel. Backflow through the reactor vessel may be desired for a number of reasons, including better heat exchange cycles, better product removal, or more efficient use of the catalyst. Backflow requires a reversible reactor design as described in the present invention; one embodiment is described in detail in Figure 15.

[0159] Compared to Figure 11 shown above, the additional equipment includes additional manifolds 310, 311 that connect the inlet 201 and outlet 209 manifolds to both ends of the reactor vessel 202. In one embodiment, additional valves on the inlet 312, 313 and outlet 314, 315 manifolds determine the direction of flow through the reactor.

[0160] In a non-restrictive example of "forward flow," valves 312 and 314 are open, while valves 313 and 315 are closed; to fill the individual reactors 202a, the reactant gas flows from the inlet manifold 201 through manifold 311 and valve 206, pushing the reacted product gas through valve 207 and manifold 310 toward the outlet manifold 209.

[0161] In a non-limiting example of "backflow," valves 312 and 314 are closed, while valves 313 and 315 are open; to fill the individual reactors 202a, the reactant gas flows from the inlet manifold 201 through manifold 310 and through valve 207, pushing the reacted product gas through valve 206 and through manifold 311 toward the outlet manifold 209.

[0162] The forward and reverse configurations described above can be used to fill all reactors in the system in the same manner. During system configuration changes (for example, from forward to reverse, or vice versa), overlapping closures of valves 314 and 315 may be necessary to prevent bypassing the reactor system.

[0163] Figure 13 shows a non-limiting embodiment of a multi-container pseudo-batch reactor system 235 with simultaneous backflow capability for each reactor.

[0164] Referring to Figure 13, an aspect of the present invention is illustrated by a plurality of reactor vessels 202a, 202b, 202c…202n, each having a catalyst bed 203 and head 204 connected at each end of the vessel to a shared inlet 201 and outlet 209 manifold by pipe 205, with additional equipment enabling selectable backflow through the individual reactor vessels. The advantage of the non-limiting aspects shown in Figure 13, beyond those shown in Figure 12, is that each individual reactor can be selected for backflow at any time without the need to reverse the flow in the shared pipe or manifold. Backflow through the reactor vessels may be desired for a number of reasons, including better heat exchange cycles, better mixing of reactants, better removal of products, or more efficient use of catalysts.

[0165] Additional equipment includes additional manifolds 310, 311 that connect inlet 201 and outlet 209 manifolds to both ends of the reactor vessel. Additional valves 312, 313 on each reactor connect both ends of each reactor to both inlet and outlet shared pipes or manifolds. In a non-limiting example of filling individual reactors 202a, the reactant gas flows through manifold 201 and valve 206, pushing the reacted product gas through valve 207 toward outlet manifold 209. After all the other reactors 202b, 202c…202n are filled, reactor 202a can be refilled / discharged by backflow; by opening valves 313 and 312, new reactant material flows in from manifold 310, pushing the reacted product gas through valve 312 and manifold 311 toward outlet manifold 209.

[0166] Figure 14 shows a non-limiting aspect of the present invention: a multi-container pseudo-batch reactor system 235 with individually selectable backflow capabilities using a multi-port valve.

[0167] Referring to Figure 14, non-limiting embodiments of the present invention are illustrated by a plurality of reactor vessels 202a, 202b, 202c…202n, each having a catalyst bed 203 and a head 204 connected at each end of the vessel to a shared inlet 201 and outlet 209 manifold by pipe 205, using a multiport valve that allows selectable backflow through the individual reactor vessels. The advantage of the non-limiting embodiments shown in Figure 14, beyond those shown in Figure 13, is that each individual reactor can be selected at any time for backflow, while still using a single valve or mechanism at the end of each reactor for that purpose.

[0168] In an unspecified example of filling individual reactors 202, the reactant gas flows through a manifold 201 and a valve 206, which is positioned to connect the inlet manifold reactor line 201 to the reactor via an inlet pipe 506; in this position, the connection between line 506 and outlet manifold 311 is closed. The incoming gas pushes any product gas through line 505 to a valve 207, which is open toward the outlet manifold 209 and closed toward the inlet manifold 310. After all the other reactors 202b, 202c…202n have been filled, reactor 202a can be refilled / discharged by backflow; by repositioning valve 207 so that line 505 opens to inlet manifold 310 and closes to outlet manifold 209; similarly, valve 206 is positioned so that line 506 opens to outlet manifold 311 and closes to inlet manifold 201. New reaction fluid flows in from manifold 310 through valve 207, and the reacted product gas is pushed through valve 206 and through manifold 511 toward outlet manifold 209.

[0169] This non-limiting aspect of the present invention can also be used to have flow between reactors using a parallel manifold. In an exemplary scenario, reactor 202a is discharged to reactor 202b via an outlet manifold. In reactor 202a, valve 206a is positioned to connect inlet manifold 201 to line 506, while valve 207a is positioned to connect line 505 to outlet manifold 209. Valve 314 is closed, and valve 315 is open to outlet 209. In reactor 502b, valve 206b is positioned to connect manifold 511 to line 506; valve 207b is positioned to connect line 505 to manifold 209. The incoming gas flows from the inlet manifold 201 through pipe 506a and valve 206a, down through reactor 202a, and then through pipe 505a and valve 207a to manifold 209. The gas then flows from line 509 through valve 207b and pipe 505b to reactor 202b, and up through reactor 202b through pipe 506b and valve 206b to outlet manifold 511. This process can be repeated and reversed by alternating the open and closed positions of valves 512 and 513 for each filling cycle. In some non-limiting embodiments of the present invention, a single multiport valve may replace valves 512 and 513. In the non-limiting embodiments described above, a small differential pressure may be required between the inlet and outlet manifolds.

[0170] Figure 15 illustrates non-limiting cross-sectional views of individual reactor pressure vessels used in the present invention and shown in Figures 11, 12, 13, and 14.

[0171] Referring to Figure 15, in this non-limiting embodiment, the reactor 202 consists of a cylindrical shell that fits into flanges 216 at each end to which the heads 208 are attached. In one non-limiting embodiment, the heads 208 are removable and identical at each end. The heads include means such as nozzles 215 for connecting pipes for fluid inflow and outflow. The reactor 202 is filled with a catalyst bed 203 between the heads; the catalyst is prevented from flowing out of the pressure vessel during operation by catalyst holders 217 or grids at each end. In one non-limiting embodiment, the catalyst grid is positioned between the pressure vessel flange 216 and the heads 208; in another non-limiting embodiment, the grid may be integrated with a gasket that creates a seal between the flange and the head. To reduce cost and custom design, manufacturing, and testing requirements, the reactor vessel may be constructed using the length of the nominal pipe (NPS or DN), and the flanges and heads (605) may be constructed using standard pipe flanges (e.g., ASME, DIN, or EN). The multi-container pseudo-batch reactor system described in the present invention enables the use of nominal pipes and standard flanges.

[0172] Figure 16 illustrates a non-limiting cross-sectional view of an individual reactor pressure vessel used in the present invention, which includes an integrated active heat transfer system.

[0173] Referring to Figure 16, similar to Figure 15, non-limiting embodiments of individual reactor vessels used in the present invention, with the addition of an active heat transfer system, are illustrated. As shown in Figure 15, the reactor pressure vessel consists of a cylindrical shell that fits into flanges 216 at each end to which a head 208 is attached. The pressure vessel head is equipped with means such as nozzles 215 for connecting pipes for the inflow and outflow of fluid. The shell of the pressure vessel is filled with a catalyst bed 203 between the pressure vessel heads; the catalyst is prevented from flowing out of the pressure vessel during operation by catalyst holders 217 or grates at each end.

[0174] In one non-limiting embodiment, a hollow outer pipe 220 with inlet nozzles 221 and outlet nozzles 222 covers a portion of the cylindrical shell. A heat transfer medium flows through the nozzles 221 into the outer pipe 220, where the heat transfer medium contacts the pressure vessel shell. In one non-limiting embodiment used for reactor cooling, a cooling heat transfer medium is passed through the nozzles 221 through a heat transfer system in which the cooling heat transfer medium is heated, cooling the pressure vessel 202 and its contents. The flow of the heat transfer medium can be controlled either continuously or by batch flow using a valve (not shown) above the outlet. In some embodiments, additional heat transfer medium can be used due to thermal inertia in batches, even if no medium is flowing during normal operation.

[0175] Figure 17 is a schematic process diagram of a non-limiting example of an ammonia production system, illustrating how the present invention interacts with other parts of the system. As will be understood by those skilled in the art upon reading this disclosure, this process using the chemical reactor system of the present invention can be similarly and conventionally adapted to gas synthesis processes other than ammonia.

[0176] Referring to Figure 17, in this embodiment of the ammonia production system, hydrogen and nitrogen feed gases are supplied to system 801 and combined with recycled unreacted feed gas 820 before being supplied to the feed gas compression system 802. In one embodiment, the feed gas compressor 802 is driven by a variable speed motor 804 and can be controlled by a compressor outlet flow control 803. The pressurized feed gas passes through a feed gas heat exchanger 805 that uses hot gas flowing out of the reactor system 200 of the present invention to heat the feed gas to a desired temperature. In one embodiment, a temperature control device 806 controls a bypass 807 around the feed gas heat exchanger to optimize the temperature of the feed gas flowing into the reactor system 200; the product gas is further heated within the gas synthesis reactor system 200 of the present invention. The product and any unreacted feed gases departing from the reactor system 235 are cooled in the feed gas heat exchanger 805 before being further cooled in a product gas cooler 809. In a non-limiting embodiment, this may be an air cooler driven by a variable drive motor 812 controlled by a downstream temperature control device 811. The pressure of the reactor system is controlled by a pressure control device 810 and a control valve 818; in a non-limiting embodiment, this is located after a product gas cooler 809. The cooled product gas is passed to a gas-liquid separator 813 where the liquid is separated into unreacted hydrogen and nitrogen gases. The level in the gas-liquid separator is controlled by a level control device 814 with a level control valve 815; the liquid ammonia product leaves the system 816. The pressure in the product gas-liquid separator is controlled by a pressure control device 817 and a control valve 818 with separate operating conditions (pressure and temperature) set to ensure that the ammonia is in liquid state, while any unreacted hydrogen and nitrogen are in a gaseous state. The unreacted hydrogen and nitrogen gases are recycled to an inlet supply gas compressor 820.

[0177] In this non-limiting embodiment of the ammonia production system, the reactor system 200 receives data from the supply gas compressor flow control 803, the supply gas heat exchanger bypass temperature control device 806, and the system pressure control device 810, and controls their setpoints. In a non-limiting example, the reactor system 200 may interact with the compressor flow control 803 by increasing the compressor flow rate setpoint to reduce the batch residence time, or vice versa. Similarly, the reactor system 200 may lower the supply gas heater temperature control setpoint to reduce the supply gas inlet temperature as the system throughput decreases and the batch residence time (and thus the reaction conversion) increases.

[0178] Further details of various aspects of the control system of the present invention are outlined in Figure 18.

[0179] Figure 18 is a schematic process diagram of a non-limiting embodiment of a control system for a chemical reactor system as illustrated in Figure 11 or described above.

[0180] Referring to Figure 18, in a non-limiting embodiment of this ammonia production system, the gas flow through a multi-vessel batch reactor including multiple pressure vessel reactors 202a-n equipped with catalyst beds 203a-n is controlled by a local system control device 930 in response to input from a remote control device 931, using a series of inlet 206a-n and outlet 207a-n mechanisms and various sensors.

[0181] During normal operation, pressurized synthetic supply gas is supplied to the inlet manifold 201. As shown in Figure 17, the flow velocity and temperature of the fluid flowing into the system are set by the upstream system control units 920, 921 in response to input from the local system control unit 930. The flow velocity and pressure at the inlet manifold 201 are monitored via the pressure / flow transmitter 922 to determine that the flow to the system matches the system's capacity; an increase in the inlet manifold pressure signals the local control unit 930 to lower any output flow velocity setpoint of the upstream compression system.

[0182] As the gas arrives and the pressure rises, the local control unit 930 opens the inlet and outlet valves 206a, 207a on the first reactor 202a, allowing the gas to flow into the individual reactors and discharging any product gas to the outlet manifold 209. In one non-limiting embodiment, the local control unit 930 can measure the characteristics of the reactor 202a (such as the gas space volume), the inlet pressure 922 and temperature 921, the outlet pressures 925, 926, the reactor temperature 924, 927, and the gas flow through the reactor; using this data, it calculates the time required to fill the reactor with new synthesis gas.

[0183] The inlet and outlet valves 206a and 207a are programmed to close after the product gas has been discharged; the valves begin to close completely after the majority of the product gas has been discharged. In one embodiment, a small amount of product gas may be retained in the system to prevent unreacted synthesis gas from flowing out into the outlet manifold. As the valves close on the first reactor 202a, the system begins to open valves 206b and 207b on the second reactor 202b. This sequence is repeated for reactors 202c, etc., until the last reactor 202n is filled; this completes one filling cycle. After each cycle is completed, the first reactor 202a is filled / discharged using the same technique.

[0184] As each reactor is filled and subsequently closed to allow the exothermic reaction to proceed, it releases heat as ammonia is produced, raising the temperature of the reactants, products, catalyst, and reactor vessel. Some non-limiting embodiments of the reactor system may operate adiabatically without significant or intentional removal of heat or material from the system during the reaction period. A local control device 930 monitors the progress of the reaction via temperature 924 and pressure 925 measurements; some non-limiting embodiments of the invention may have more than one temperature indicator to ensure accurate monitoring of the entire length of the reactor. After the reaction has progressed to the desired point, the reactor is refilled in the same sequence as described above, draining the hot reactor contents toward the outlet manifold 209.

[0185] During the filling process, the incoming cooling supply gas lowers the temperature of the catalyst and reactor body; the incoming synthesis gas is heated as it enters the reactor. The local control unit 930 ensures that the setting of the inlet manifold gas temperature control unit 921 is low enough so that the heating of the reactor during the batch reaction is adequately offset by sufficient cooling during each filling cycle. In parallel, the local control unit 930 sets the reactor residence time to ensure that the maximum temperature reached in the reactor does not continue to rise over time. In some non-limiting embodiments of the system, if the reactor temperature rises over time, the local control unit 930 can increase the overall system flow rate 920 to reduce the residence time (and thus the reaction conversion and heat release) in each reactor cycle. Another method that the local control unit 930 can employ to reduce or increase the residence time is to use fewer or more reactors in a given filling cycle.

[0186] To accommodate the diverse performance of catalysts, including different catalyst materials, sizes, shapes, and ages, as well as different reactor sizes, several embodiments of the reactor system may enable parallel reactor batch cycles with varying residence times and filling rates. This ensures that the local control unit 930 does not need to wait for a full cycle of series-filled reactors before refilling reactors that are approaching their temperature limits after a given reactor's maximum temperature has been reached.

[0187] Some non-limiting embodiments of this system may have an additional heat transfer mechanism filled with a heat transfer fluid connected to a cooling or heating loop that enables active reactor temperature control, such as a hollow outer pipe 220, sleeve, or jacket on a reactor, as illustrated on a single vessel 202n. The heat transfer jacket has an inlet pipe 221, an outlet pipe 222, and a valve 224 for controlling the flow of the heat transfer medium. In some embodiments of the reactor system, all reactors are equipped with this active cooling mechanism; in other embodiments, only some of the reactors are equipped with active cooling. The active cooling system may also be used for heating the reactor during system startup. To operate the reactor heat transfer system, the local control unit 930 opens the heat transfer medium control valve 224 to ensure that the heat transfer medium flows at a sufficient rate and that the reactor temperature is kept constant (isothermal operation); after a predetermined temperature is reached, the local control unit 930 may set the operating heat transfer system to cool the reactor or slow the rise in reactor temperature. This allows for increased equilibrium transformation beyond purely adiabatic operation, which requires the discharge of reactor contents at a predetermined temperature, in order to maintain the reactor and catalyst temperatures below a specific value.

[0188] Some non-limiting embodiments of this system may include the connection of the local control unit 930 to a remote control unit 931 that receives and transmits data from numerous systems operating in parallel. In some embodiments, the remote control unit may be cloud-based. The remote control unit 931 can be used to collect data from non-system-specific sources, such as weather tracking systems or databases, performance data from other reactor systems operating nearby, or local renewable energy power demand curves, and utilizes these inputs to predict the required reactor system performance state or setpoints. Some embodiments of the system may use artificial intelligence within or through the remote control unit 931 to help generate predictive control setpoints for the local control unit 930; other embodiments may use the remote control unit for central computing power, enabling a lower-cost local control unit.

[0189] The use of several forms of batch reactors and parallel batch reactors has been employed to date in wastewater treatment systems, bioreactors, and laboratory experiments; however, a system has yet to be designed that would allow batch reactors to be used in production-scale gas-phase catalytic reactions involving solid catalysts, fixed-bed reactors, or high-pressure gas systems, which are requirements for industrial-scale ammonia synthesis. The current levels of speed, accuracy, and predictive computer automation required for reliable output and safe system operation facilitate new approaches to reactor design, placement, and automated process control described in this invention.

[0190] The chemical reactor system of the present invention offers several advantages in gas synthesis.

[0191] For example, reactants can be added individually to the reactor at a controlled rate, allowing for control of the reaction rate and reactor temperature, and adapting to the available time when powered by intermittent renewable energy. The use of a batch reactor according to this embodiment allows hydrogen to be "stored" in the reactor under high pressure until it is suitable for ammonia production; a non-limiting example of this is daytime hydrogen production and high-pressure storage in the reactor accompanied by ammonia production after the peak period of renewable energy.

[0192] The ability to add reactants individually enhances equilibrium transformations according to Le Chatelier's principle, allowing the use of ratios different from the 3:1 stoichiometric standard for ammonia reactions. The ability to remove liquid products without unreacted feed gas allows the use of non-stoichiometric feed gas ratios without the drawback of increased compression due to high recycling rates.

[0193] Furthermore, each reactor in the system may be a pressure vessel containing a catalyst suitable for gas synthesis, such as ammonia. In one non-limiting embodiment, each reactor vessel consists of a standard hydrogen storage tank containing the catalyst and having an opening at one end. In a complete system, each individual packed-bed reactor is connected to a shared inlet and outlet manifold and comprises one or more mechanisms that control the inflow of reactants from the inlet manifold and the outflow of reaction products to the outlet manifold; in a preferred embodiment, the mechanisms are automated and allow for the control of individual, but coordinated and harmonized, conditions within a single reactor, but with all reactors in the entire system. Opening and closing the mechanisms in the correct sequence across multiple reactors allows individual vessels to operate as batch reactors with a controllable residence time or GHSV, while the entire reactor system operates with stable and continuous throughput. More specifically, operation of a catalyst reactor as a batch reactor allows for a “non-moving,” “stable,” “non-flowing,” or “static” residence time of reactants and products within the catalyst bed; in a given reactor vessel in the present invention, this is the time between bulk filling and discharging. During the period when the inlet and outlet mechanisms are closed, the reactant gas is allowed to distribute itself throughout the reactor without being pushed along the reactor axial direction (towards the outlet), as in the case of plug flow or other steady-state reactors. The techniques described herein are known as “static gas catalysis” or “non-fluid gas catalysis” and enable a more uniform distribution of the catalytic reaction throughout the catalyst bed without the need for an internal fluid inlet distribution mechanism or a large gas volume at the reactor inlet; and also enable the spread of the reaction and any heat released or absorbed over the entire volume of the catalyst bed.

[0194] In a system where all reactors are filled in series, the non-moving batch or “static” residence time of each reactor vessel is approximately equal to the individual reactor filling time in the system multiplied by the number of subsequent reactors. At a predetermined desired maximum residence time, a “cycle” is defined as the process of filling all of a given series of reactors and then returning to refilling / emptying the first reactor.

[0195] At the start of the batch sequence, each reactor has an internal pressure lower than the pressure in the inlet manifold; as the reactants flow from the inlet manifold into the reactor, the pressure inside the reactor increases. Once the desired reaction pressure is reached and sufficient reactants have been added to the reactor vessel, the inflow mechanism is closed to allow the reaction to proceed.

[0196] In some non-limiting embodiments of the present invention, the ratio of reactants entering the container is modified to control the progress of the reaction and the heat released through the reactor container wall. One non-limiting example of this is to first fill the container with high-temperature compressed hydrogen alone to a desired pressure, and then gradually add nitrogen so that the heat produced by the exothermic reaction matches the heat released into the atmosphere through the reactor wall. In this embodiment, the reaction temperature is kept constant by controlling the heat of the exothermic reaction released by controlling the inflow of nitrogen to match the amount of ammonia being utilized and, thereby, the amount of heat released from the reactor to the atmosphere. An additional advantage of this embodiment of the present invention is the use of Le Chatelier's principle, in which a high (or excess) concentration of reactants pushes the reaction toward the product side, resulting in a higher equilibrium transformation at a given operating temperature and pressure.

[0197] When the reaction has progressed to the desired point, the reactant inflow mechanism is closed, stopping the reaction and the release of exothermic heat within the reactor vessel, and the vessel begins to cool. After the reactor and its contents have cooled below the critical temperature of the ammonia product, the gaseous product becomes liquid. The vessel can then discharge the liquid product by opening a mechanism that connects the reactor to an outlet manifold, allowing the liquid product to be released from the pressure vessel. As the liquid product is discharged from the vessel, the internal pressure drops, which allows the reactor to be refilled with reactant gas after a sufficient amount of product has been released.

[0198] Depending on the available reaction residence time, several aspects of the present invention may actively modify the operating conditions of temperature, pressure, and reactant ratios within the reactor to optimize conversion, energy use, or other factors to match the available time for the reaction to proceed. A non-limiting example of this is lowering the operating temperature to ensure a slower, more controlled reaction rate with higher equilibrium conversion. Another non-limiting example is lowering the operating pressure to reduce compression energy requirements, while simultaneously lowering the reaction temperature or changing the stoichiometric reactant ratio to offset the equilibrium conversion losses at lower reaction pressures.

[0199] The filling and discharging rates of individual reactors within a system are limited to maximum values ​​defined by pressure drop, catalyst entrainment, catalyst damage, or other physical criteria. It is impossible to add an infinite number of batch reactors within the same cycle while maintaining the same target filling time; this requires reducing the filling time of individual reactors toward zero seconds in each reactor. Beyond a certain filling rate to individual reactors, parallel filling of multiple reactors (i.e., filling a group of reactors simultaneously) becomes necessary. Thus, the present invention enables the parallel filling of a group of reactors, limiting the filling rate of individual reactors, and even allowing the entire system to operate with reactants flowing into and out of the reactors in some form of continuous parallel flow, such as staggered overlapping parallel filling, as needed for best system performance.

[0200] In the case of parallel or pseudo-parallel continuous flow, the use of the external mechanisms, manifolds, and associated control systems described in the present invention can ensure an optimal and controlled distribution of reactant gases across multiple reactors.

[0201] The individual reactors and the entire reactor system in the present invention are also designed so that each reactor can operate in a “pseudo-batch” mode by using an automated inflow mechanism, where the reactors can be partially filled, refilled / repressurized during the reaction, operate at independent temperatures and pressures, or filled with reactants of different compositions, potentially optimizing the reaction rate and equilibrium transformation.

[0202] Some aspects of the present invention enable an advanced control system that achieves different residence times for individual or collective reactors; achieved by either different arrangements of series-filled or parallel-filled reactors. This feature of the present invention allows for the use of different catalyst materials, sizes, or shapes within individual or collective reactors, which may require different fluid residence times; this is also useful for dynamic operating conditions such as cold reactor startup or changing reactor operating temperature and pressure.

[0203] The use of an external mechanism that enables individual reactors to operate in batch (or pseudo-batch) mode allows design engineers to decouple the dimensional constraints of individual reactors from the target residence time or GHSV. The use of batch mode with catalytic reactors enables high residence times without significantly increasing reactor length or having to worry about radial fluid distribution or plug flow deviations. This satisfies the ability to size reactors to fit into small spaces while achieving high residence times without requiring complex internal gas distribution systems, large inflow volumes, and excessive pressure drops over long catalyst bed lengths.

[0204] The use of a properly designed catalytic reactor operating in batch (or pseudo-batch) mode overcomes the disadvantages of using plug-flow reactor vessels at high turndown (low overall system throughput), where current state-of-the-art technology faces problems such as poor reactant distribution, channeling, catalyst hotspots, and inefficient catalyst use at rates far below the peak design operating point.

[0205] A further advantage of the present invention is the simplification of reactor temperature control by distributing the reaction (and any heat thus released or absorbed) throughout the catalyst bed and reactor body, thereby avoiding catalyst hot spots and sintering. In this case, a higher metal-to-catalyst weight ratio in the reactor is advantageous in terms of the system's thermal inertia, preventing overheating of the fluid and catalyst.

[0206] A further advantage of the present invention, particularly for use in green ammonia production systems coupled to intermittent renewable energy sources, is that, due to the increased controlled residence time in each reactor vessel, system performance (including equilibrium transformation) actually increases as the overall system throughput decreases (i.e., a higher turn-down ratio) due to batch or pseudo-batch operation; this is the opposite of plug-flow reactor designs of the current state of technology.

[0207] A further advantage of some aspects of the present invention is that the use of a long-duration batch reactor allows for the cooling of the ammonia produced under high pressure to below critical temperature, thereby enabling the separation of gaseous reactants from liquid ammonia without the need for a significant pressure drop or large heat exchanger to cool the ammonia products.

[0208] A further advantage in some aspects of the present invention is that ammonia production can occur during periods when renewable energy is unavailable, such as overnight or when there is no wind or sun. In some embodiments, the reactor vessel can be filled during the day and left to produce ammonia overnight, and then discharged the following morning. In this example of the present invention, when energy is available, hydrogen is produced and compressed into an empty or partially empty reactor vessel, and nitrogen is produced and stored under pressure in a separate storage tank. After the reactor is filled (or when intermittent energy becomes unavailable, whichever comes first), the reaction is initiated in the hydrogen-filled reactor by slowly adding nitrogen as described above. The small amount of power required for control can be supplied by a battery, by operating the electrolytic cell in reverse (using some of the previously compressed hydrogen), or by using stored compressed nitrogen for pneumatic control.

[0209] A further advantage of the present invention in the production of green ammonia using electricity from intermittent renewable energy sources is that the operating conditions (pressure and temperature) can be varied, allowing batch reactions to proceed at a slower rate and optimizing reaction transformation and overall energy utilization.

[0210] Furthermore, while the use of multiple smaller reactors with external gas distribution mechanisms increases the metal / catalyst weight or volume ratio (higher ratios are a proxy for higher overall system manufacturing costs), the use of the highly simplified reactors described in this invention makes the overall system cost competitive, especially when constructed from standardized components as described herein. In parallel, the invention allows system designers to leverage the modularity of the reactors in terms of both throughput and residence time without having to custom design each reactor vessel. This allows both manufacturing and production costs to be amortized across multiple facilities, lowering the average cost of each individual system. manner

[0211] Aspects of the present invention relate to a chemical reactor system for gas synthesis, the system comprising: a batch, pseudo-batch, or dynamic reactor of one or more individual catalytic reactors for gas synthesis; one or more fluid control mechanisms comprising shared pipes and manifolds for the delivery of reactants to the chemical reactor system and the collection of reaction products from the chemical reactor system; and a control system that can open one or more fluid control mechanisms for controlling the inflow of reactants to the chemical reactor system and the outflow of reaction products from the chemical reactor system.

[0212] In the embodiments described above, the batch, pseudo-batch, or dynamic reactor may be a temperature swing gas synthesis reactor.

[0213] In any of the preceding embodiments described above, one or more individual catalyst reactors may include a single means located at one end that allows a fluid to flow into and out of the individual reactor and into contact with the catalyst.

[0214] In any of the preceding embodiments described above, each individual catalyst reactor may have separate inflow and outflow means that allow fluid to flow into and out of the individual reactor and into contact with the catalyst.

[0215] In any of the preceding embodiments described above, the control system can control the reactor inflow and outflow mechanisms within the system via one or more fluid control mechanisms to facilitate continuous, parallel, or combined flow of fluid through individual catalyst reactors, thereby ensuring that the fluid in each individual catalyst reactor is stable or nearly stable for a portion of the residence time, while the fluid flow through the chemical reactor system is nearly continuous.

[0216] In any of the preceding embodiments described above, each individual catalyst reactor may include a cylindrical shell pressure vessel having pressure vessel heads at each end; a catalyst bed between the pressure vessel heads; a catalyst holder positioned within at least one pressure vessel head to prevent the catalyst from flowing out of the vessel during operation; and means to allow a fluid to flow into and out of the pressure vessel and into contact with the catalyst.

[0217] In any of the preceding embodiments described above, a portion of one or more individual catalytic reactors can be used for storing hydrogen, nitrogen, ammonia, or other gases.

[0218] In any of the preceding embodiments described above, a batch, pseudo-batch, or dynamic reactor may include a plurality of individual catalytic reactors for gas synthesis, as well as additional mechanisms adapted to shared pipes or manifolds that connect the individual catalytic reactors to allow backflow to individual or collective individual catalytic reactors, while simultaneously allowing forward flow to other individual catalytic reactors within the same reactor system.

[0219] In any of the preceding embodiments described above, the control system may be automated and / or the individual or collective catalytic reactors may be operated in batch mode.

[0220] In any of the preceding embodiments described above, the control system may be automated and / or capable of operating individual or collective catalytic reactors in continuous, steady-state, or plug-flow mode.

[0221] In any of the preceding embodiments described above, one or more individual catalytic reactors may be equipped with internal and / or external heat exchanges that change the temperature of the reactor as the reaction proceeds.

[0222] In any of the preceding embodiments described above, one or more individual catalytic reactors may be designed as pipe-in-pipe heat exchangers.

[0223] In any of the preceding embodiments described above, the control system may be computerized and connected to a remote or cloud-based control device.

[0224] In any of the preceding embodiments described above, the control system may use algorithms, artificial intelligence, or machine learning to optimize the performance of individual or collective catalytic reactor vessels and chemical reactor systems.

[0225] In any of the preceding embodiments described above, one or more individual catalytic reactors may be equipped with sensors, detectors, or control devices that transmit information to a control system, thereby enabling the chemical reactor system to operate in a manner that allows for a continuous inflow of reactants and outflow of reaction products through the chemical reactor system.

[0226] In any of the preceding embodiments described above, the gas synthesis may be ammonia synthesis.

[0227] Another aspect of the present invention relates to an energy waste reduction system, which includes any of the preceding embodiments, on top of a chemical reactor system coupled to a variable or intermittent energy production technology.

[0228] Another aspect of the present invention relates to a method for producing gas via variable or intermittent energy production techniques, via one of the preceding aspects on top of a chemical reactor system.

[0229] Another aspect of the present invention relates to a method for producing a gas via the following steps: supplying a synthesis feed gas to a chemical reactor system of any of the preceding embodiments above a chemical reactor system; opening one or more fluid control mechanisms of individual catalyst reactors or collective reactors to allow sufficient synthesis feed gas to flow into each reactor so that each reactor is filled with the feed gas; closing one or more fluid control mechanisms after the reactors have been filled with the feed gas to stop or sufficiently slow the flow of gas in contact with the catalyst and allow the reaction to occur; timing, predicting, and / or monitoring temperature, pressure, and / or other measurable conditions in each closed or partially closed reactor to determine the progress of the reaction; and discharging the reaction products after the reaction has reached a desired progress.

[0230] Another aspect of the present invention relates to a method for improving an ammonia plant having a synthesis loop, wherein fresh ammonia synthesis gas containing hydrogen and nitrogen is combined with an optional recycle stream to form a mixed ammonia synthesis gas, the mixed ammonia synthesis gas is reacted on a catalyst to form a converted ammonia product gas, the improvement method comprising the steps of: replacing an existing ammonia synthesis reactor or reactor with a chemical reactor system of any preceding aspect on top of a chemical reactor system having a control system that enables: (i) operating one or more batches, pseudo-batches, or dynamic reactors and their fluid control mechanisms so that each reactor is sequentially filled with synthesis gas to allow batch or approximate batch residence times, while having a continuous or substantially continuous flow of supply gas throughout the entire system of reactor vessels; (ii) controlling the synthesis supply gas temperature; and (iii) controlling the operating pressure of the reactor system; and installing a supply gas heat exchanger capable of heating the synthesis gas to target and controlled temperatures as required for the reactor batch operation upstream of the chemical reactor system; The steps include installing heat exchangers and gas-liquid separators to condense and recover ammonia from the reactor outflow stream to form a low ammonia stream; and installing a pressure control system that allows the operating pressure of the chemical reactor system to be controlled and operated.

[0231] Another aspect of the present invention relates to a method for producing ammonia from synthesis gas containing hydrogen and nitrogen combined with an arbitrary recycling stream via the following steps: (a) supplying a synthesis feed gas to a system comprising one or more catalyst-filled pressure vessel reactors, each catalyst-filled pressure vessel reactor connected to one or more manifolds at the inlet and one or more manifolds at the outlet of the system, each catalyst-filled pressure vessel reactor comprising independently operating equipment for controlling, directing and stopping the flow of fluid to and from individual vessels and catalyst beds via the inlet and outlet manifolds; opening the control mechanism of a selected catalyst-filled pressure vessel reactor or a group of catalyst-filled pressure vessel reactors, allowing sufficient synthesis feed gas to be delivered from the inlet manifold to each catalyst-filled pressure vessel reactor so that it is filled with feed gas and pressurized to a selected operating pressure; and opening the control mechanism at each end of the selected catalyst-filled pressure vessel reactor or a group of reactors, allowing sufficient synthesis feed gas to be delivered from the inlet manifold to each catalyst-filled pressure vessel reactor so that it is filled with feed gas and pressurized to a selected operating pressure; and opening the control mechanism at each end of the selected catalyst-filled pressure vessel reactor or a group of reactors, Steps include: closing the reactor after filling to stop or sufficiently slow the flow of gas in contact with the catalyst and allow the reaction to occur; timing, predicting, or monitoring the temperature, pressure, or other measurable conditions in each closed or partially closed catalyst-filled pressure vessel reactor to determine the progress of the reaction; allowing the catalyst-filled pressure vessel reactor (single) or reactor(s) to cool below the critical point or dew point temperature of the ammonia product after the reaction has reached a desired state, transformation, or equilibrium transformation; discharging the liquid ammonia product that has accumulated at the bottom of the catalyst-filled pressure vessel reactor (single) or reactor(s) after sufficient cooling without allowing the majority of the unreacted gas to leak out of the catalyst-filled pressure vessel reactor (single) or reactor(s); and repeating the filling process by adding a new synthesis feed gas to any unreacted gas remaining in the catalyst-filled pressure vessel reactor (single) or reactor(s).

[0232] In the embodiments of the preceding method described above, one or more reactants are introduced sufficiently gradually into each catalyst-filled pressure vessel reactor, enabling controlled ammonia production and temperature release, and allowing desired operating temperature and pressure conditions to be maintained within each catalyst-filled pressure vessel reactor.

[0233] In any of the embodiments of the preceding methods described above, one or more catalyst-filled reactor vessels may be used to store the reactants at high pressure before the introduction of a second reactant, so as to initiate the ammonia production process in a controlled manner.

[0234] In any of the embodiments of the preceding methods described above, hydrogen and / or nitrogen may be stored at a sufficiently high pressure in one or more catalyst-filled pressure vessel reactors during periods when electricity is available, so that the hydrogen and nitrogen can be transferred to a portion of the one or more catalyst-filled pressure vessel reactors during periods when electricity is not available to produce ammonia.

[0235] In any of the preceding embodiments of the methods described above, one or more catalyst-filled pressure vessel reactors may be sequentially filled with supply gases to allow batch or near-batch residence times within each reactor, while having a continuous or near-continuous flow of supply gases through the entire system of reactor vessels.

[0236] In any of the preceding embodiments, one or more catalyst-filled pressure vessel reactors may be equipped with sensors, detectors, or control devices that transmit information to one or more control systems, so that the reactor, mechanism, sensors, and control systems can operate to enable a continuous inflow of feed gas and a continuous outflow of products through the entire reactor system.

[0237] In any of the embodiments of the preceding methods described above, one or more catalyst-filled pressure vessel reactors may be equipped with a control system that can operate the reactors and their fluid control mechanisms so as to sequentially fill each reactor with synthesis gas, allowing for batch or nearly batch residence times, while having a continuous or nearly continuous flow of supply gas through the entire system of reactor vessels.

[0238] In any of the embodiments of the preceding methods described above, one or more catalyst-filled pressure vessel reactors may be equipped with a control system capable of controlling the synthesis feed gas temperature.

[0239] In any of the embodiments of the preceding methods described above, one or more catalyst-filled pressure vessel reactors may be equipped with a control system capable of controlling the reactor system operating pressure.

[0240] In any of the embodiments of the preceding methods described above, one or more catalyst-filled pressure vessel reactors may be equipped with an internal or external heat transfer system to regulate the temperature of the reactor as the reaction progresses.

[0241] In any of the embodiments of the preceding methods described above, one or more catalyst-filled pressure vessel reactors may be designed as pipe-in-pipe heat exchangers.

Claims

1. A chemical reactor system for gas synthesis, which includes: A batch, pseudo-batch, or dynamic reactor of one or more individual catalytic reactors for gas synthesis; One or more fluid control mechanisms consisting of shared pipes and manifolds for delivering reactants to a chemical reactor system and collecting reaction products from the chemical reactor system; and A control system that can open one or more fluid control mechanisms to control the inflow of reactants into a chemical reactor system and the outflow of reaction products from a chemical reactor system: The chemical reactor system including the above.

2. The chemical reactor system according to claim 1, wherein the batch, pseudo-batch, or dynamic reactor is a temperature swing gas synthesis reactor.

3. The chemical reactor system according to claim 2, wherein one or more individual catalyst reactors have a single means positioned at one end for allowing fluid to flow into and out of the individual reactors and into contact with the catalyst.

4. The chemical reactor system according to claim 1, wherein each individual catalyst reactor has separate inflow and outflow means that allow fluid to flow into and out of the individual reactor and into contact with the catalyst.

5. A chemical reactor system according to claim 1, comprising a batch, pseudo-batch, or dynamic reactor with a plurality of individual catalytic reactors for gas synthesis, wherein the control system can control reactor inflow and outflow mechanisms in the system via one or more fluid control mechanisms to facilitate series, parallel, or combination thereof of fluid flow through the individual catalytic reactors, thereby causing the fluid in each individual catalytic reactor to be stable or near-stable for a portion of the residence time, while the fluid flow through the chemical reactor system is substantially continuous.

6. Each individual catalytic reactor: A cylindrical shell pressure vessel having a pressure vessel head at each end; Catalyst bed between pressure vessel heads; A catalyst holder located within at least one pressure vessel head to prevent the catalyst from flowing out of the container during operation; and Means for allowing fluid to flow into and out of a pressure vessel and into contact with the catalyst: A chemical reactor system according to claim 1, comprising:

7. The chemical reactor system according to claim 1, wherein a portion of one or more individual catalytic reactors is used for the storage of hydrogen, nitrogen, ammonia, or other gases.

8. A batch, pseudo-batch, or dynamic reactor comprising a plurality of individual catalytic reactors for gas synthesis, and an additional mechanism adapted to a shared pipe or manifold for connecting the individual catalytic reactors to allow backflow to individual or collective individual catalytic reactors while simultaneously allowing forward flow to other individual catalytic reactors within the same reactor system, according to claim 1.

9. The chemical reactor system according to claim 1, wherein the control system is automated and can operate individual or collective catalytic reactors in batch operation mode.

10. The chemical reactor system according to claim 1, wherein the control system is automated and can operate individual or collective catalytic reactors in continuous, steady-state, or plug-flow operating modes.

11. The chemical reactor system according to claim 1, wherein one or more individual catalytic reactors are equipped with an internal or external heat transfer system that changes the temperature of the reactor as the reaction proceeds.

12. The chemical reactor system according to claim 1, wherein one or more individual catalytic reactors are designed as pipe-in-pipe heat exchangers.

13. The chemical reactor system according to claim 1, wherein the control system is computerized and connected to a remote or cloud-based control device.

14. The chemical reactor system according to claim 1, wherein the control system optimizes the performance of individual or collective catalyst reactor vessels and chemical reactor systems using algorithms, artificial intelligence, predictive control, or machine learning.

15. The chemical reactor system according to claim 1, wherein one or more individual catalytic reactors are equipped with sensors, detectors, or control devices that transmit information to a control system, thereby operating to allow a continuous inflow of reactants and outflow of reaction products through the chemical reactor system.

16. The chemical reactor system according to claim 1, wherein the gas synthesis is ammonia synthesis.

17. An energy waste reduction system comprising the chemical reactor system according to claim 1, coupled with variable or intermittent energy production technology.

18. A method for producing gas via intermittent energy production technology, comprising coupling the intermittent energy production technology with the chemical reactor system described in claim 1.

19. A method for producing gas, consisting of the following steps: A step of supplying a synthesis feed gas to the chemical reactor system according to claim 1; The steps include opening one or more fluid control mechanisms of individual catalytic reactors or a group of reactors, thereby allowing sufficient synthesis feed gas to flow into each reactor so that each reactor is filled with feed gas; After being filled with supply gas, one or more fluid control mechanisms are closed to stop or sufficiently slow down the flow of gas in contact with the catalyst, allowing the reaction to occur; Steps include timing, predicting, and / or monitoring the temperature, pressure, and / or other measurable conditions within each closed or partially closed reactor to determine the progress of the reaction; and Steps to remove reaction products after the reaction has reached the desired stage: The method, including the method described above.

20. A method for improving an ammonia plant having a synthesis loop in which fresh ammonia synthesis gas containing hydrogen and nitrogen is mixed with any recycled stream to form mixed ammonia synthesis gas, and the mixed ammonia synthesis gas reacts on a catalyst to form converted ammonia product gas, the following steps: The current ammonia synthesis reactor (single) or reactor (multiple) is as follows: (i) Operating one or more batches, pseudo-batches, or dynamic reactors and their fluid control mechanisms so as to sequentially fill each reactor with synthesis gas, allowing for batch or near-batch residence times, while having a continuous or near-continuous flow of supply gas through the entire system of reactor vessels; (ii) Controlling the synthesis feed gas temperature; and (iii) Controlling the operating pressure of the reactor system; Steps to replace the chemical reactor system according to claim 16, which has a control system capable of: A step of incorporating a feed gas heat exchanger capable of heating synthesis gas to target and control temperatures as required for batch operation of reactors upstream of a chemical reactor system; Steps include incorporating a heat exchanger and a gas-liquid separator to condense and recover ammonia from the reactor eluent stream to form a low-ammonia stream; and Steps to incorporate a pressure control system so that the operating pressure of the chemical reactor system can be controlled and operated: A method for improvement, including the above.

21. A method for producing ammonia from synthesis gas containing hydrogen and nitrogen combined with any recycling stream, comprising the following steps: (a) Each catalyst-filled pressure vessel reactor is connected to one or more manifolds at the inlet and one or more manifolds at the outlet of the system, and each catalyst-filled pressure vessel reactor supplies a synthesis feed gas to a system comprising one or more catalyst-filled pressure vessel reactors, each having independently operating mechanisms for controlling, directing, and stopping the flow of fluid to and from individual vessels and catalyst beds via the inlet and outlet manifolds; (b) Open the control mechanism of a selected catalyst-filled pressure vessel reactor or a group of catalyst-filled pressure vessel reactors so that each catalyst-filled pressure vessel reactor is filled with supply gas and pressurized to a selected operating pressure; (c) After the reactor has been filled with the supply gas, the step of closing the control mechanisms located at each end of the selected catalyst-filled pressure vessel reactor or collective reactor to stop or sufficiently slow the flow of gas in contact with the catalyst and allow the reaction to occur; (d) A step of timing, predicting, or monitoring the temperature, pressure, or other measurable conditions in each closed or partially closed catalyst-filled pressure vessel reactor to determine the progress of the reaction; (e) After the reaction has reached a desired state, transformation, or equilibrium transformation, a step that allows a catalyst-filled pressure vessel reactor (single) or reactor(s) to cool to below the critical point or dew point temperature for ammonia production; (f) After allowing the majority of the unreacted gas to cool sufficiently without allowing leakage from the catalyst-filled pressure vessel reactor (single) or reactor(s), the step of discharging the liquid ammonia product collected at the bottom of the catalyst-filled pressure vessel reactor (single) or reactor(s); and (g) A step of repeating the filling process by adding new synthesis feed gas to any unreacted gas remaining in the catalyst-filled pressure vessel reactor (single) or reactor (multiple): The method, including the method described above.

22. The method according to claim 21, wherein one or more reactants are sufficiently and progressively introduced into each catalyst-filled pressure vessel reactor to enable controlled ammonia production and temperature release, and to maintain desired operating temperature and pressure operating conditions within each catalyst-filled pressure vessel reactor.

23. The method according to claim 21, wherein one or more catalyst-filled reactor vessels are used to store reactants at high pressure before introducing a second reactant so that the ammonia production process is initiated in a controlled manner.

24. The method according to claim 21, wherein hydrogen and nitrogen are stored at a sufficiently high pressure in one or more catalyst-filled pressure vessel reactors during periods when electricity is available, so that the hydrogen and nitrogen can be transferred to a portion of the one or more catalyst-filled pressure vessel reactors during periods when electricity is not available to produce ammonia.

25. The method according to claim 21, wherein one or more catalyst-filled pressure vessel reactors are sequentially filled with supply gases to allow batch or nearly batch residence times within each reactor, while having a continuous or nearly continuous flow of supply gases through the entire system of reactor vessels.

26. The method according to claim 21, wherein one or more catalyst-filled pressure vessel reactors are equipped with sensors, detectors, or control devices that transmit information to one or more control systems, so that a system comprising the reactor, mechanism, sensors, and control systems can operate to allow a continuous inflow of supply gas and outflow of products through the entire system of the reactor.

27. The method according to claim 21, comprising a control system capable of operating one or more catalyst-filled pressure vessel reactors and their fluid control mechanisms so that they are sequentially filled with synthesis gas, allowing batch or near-batch residence times within each reactor, while having a continuous or near-continuous flow of supply gas through the entire system of reactor vessels.

28. The method according to claim 21, wherein one or more catalyst-filled pressure vessel reactors are equipped with a control system capable of controlling the synthesis feed gas temperature.

29. The method according to claim 21, wherein one or more catalyst-filled pressure vessel reactors are equipped with a control system capable of controlling the reactor system operating pressure.

30. The method according to claim 21, wherein one or more catalyst-filled pressure vessel reactors include an internal or external heat transfer system that changes the temperature of the reactor as the reaction progresses.

31. The method according to claim 21, wherein one or more catalyst-filled pressure vessel reactors are designed as pipe-in-pipe heat exchangers.

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