Reactor system for gas synthesis

Abstract

There is provided a chemical reactor system for gas synthesis, comprising: a batch, quasi-batch, or dynamic reactor for gas synthesis, the batch, quasi-batch, or dynamic reactor being formed from one or more individual catalytic reactors; one or more fluid control mechanisms, the one or more fluid control mechanisms being formed from common conduits and headers, the one or more fluid control mechanisms for delivering reactants to the chemical reactor system and collecting reaction products from the chemical reactor system; and a control system capable of opening the one or more fluid control mechanisms to control reactant entry into the chemical reactor system and reaction product exit from the chemical reactor system. Also provided are methods of using these systems in gas synthesis, and in particular ammonia synthesis, as well as methods to retrofit ammonia synthesis plant equipment. The disclosed chemical reactor systems are particularly suited for ammonia (NH) synthesis and enable the adaptation of mature and stable gas phase catalytic chemistry used in the majority of Haber-Bosch processes to variable or discontinuous renewable energy power sources.

Description

Technical Field

[0001] This patent application claims the benefit of priority to U.S. Patent Application No. 18 / 587,816, filed February 26, 2024, and U.S. Provisional Application No. 63 / 506,815, filed June 7, 2023, which are incorporated herein by reference in their entirety. Background Technology

[0002] At the beginning of the 20th century, German chemists Fritz Haber and Carl Bosch discovered a process for the synthetic production of ammonia, perhaps one of the most important discoveries in modern history. Their invention involved the exothermic, reversible reaction of nitrogen and hydrogen under high temperature and pressure conditions in the presence of a catalyst:

[0003] N2 + 3H2 ⇋ 2NH3 + ~92 kJ

[0004] The first commercial production took place in 1913 at the BASF plant in Ludwigshafen, with a production capacity of approximately 25 tons of ammonia per day (see BASF history, basf.com / ca / en / who-we-are / history / 1902-1924.html). Since then, the scale of ammonia plants and global production capacity have grown significantly, with current global annual production reaching approximately 200 billion tons. Modern refineries are capable of producing over 3,000 tons of anhydrous ammonia per day. It is estimated that about 50% of the food consumed by humans is grown using fertilizers produced based on synthetic ammonia.

[0005] Currently, over 95% of ammonia synthesis uses fossil fuels as the source of hydrogen (H2) required for the reaction; "grey ammonia" uses natural gas, and "brown ammonia" uses fuel oil or coal. Currently, fossil fuels consumed in the production of gray and brown ammonia account for approximately 2% of global greenhouse gas emissions.

[0006] "Green ammonia" (hydrogen produced from water using renewable energy) shows great potential as a high-density, carbon-free energy carrier, and can be used for storing and transporting renewable energy. In addition to its use in the storage and transportation of renewable energy, the world also needs to shift its existing ammonia demand from gray / brown ammonia to green ammonia in order to reduce greenhouse gas emissions.

[0007] While the process of green ammonia production is well-known, the intermittent nature of the most popular renewable energy sources—such as wind turbines and photovoltaic (PV) solar power—poses challenges for large-scale ammonia production. For economic and efficiency reasons, renewable energy power plants tend to sell electricity directly to customers as it is generated, but this often results in curtailment—the surplus of unused energy during periods of lower customer demand (e.g., during peak midday solar PV output). This means that the available window for using surplus energy from non-dedicated renewable energy sources for ammonia production is even narrower.

[0008] In contrast, modern ammonia refineries operate 24 / 7, 365 days a year to maximize output, revenue, and efficiency; they are not well-suited for powering intermittent renewable energy sources with capacity factors below 40%. Matching renewable energy power technologies with conventional synthetic ammonia production processes would likely require very large energy storage facilities (such as batteries), large hydrogen storage facilities, or a combination of both, for any output exceeding half.

[0009] Regardless of intermittency and timing, the energy input required for most industrial-scale ammonia refineries to switch to green ammonia production would exceed that of the world's largest renewable energy power plants. Currently, most solar power plants in the United States have an installed capacity of less than 5 MW of peak power output (see "Ammonia as a Renewable Energy Transportation Media," pubs.acs.org / doi / 10.1021 / acssuschemeng.7b02219). Green ammonia is projected to require 10–12 MWh / tonne (see Bhadla SolarPark, en.wikipedia.org / wiki / Bhadla_Solar_Park), meaning that even a small-scale (25 tonnes / day) BASF ammonia plant would require an average power output of 12 MW and a peak solar power output of >40 MW (based on a 25% capacity factor or 6 hours of solar output per day). A 3,000-ton / day ammonia plant would require an estimated 5.5 GW of rated capacity, more than double the rated capacity of the world’s largest solar power plant as of early 2023 (see Bhadla SolarPark, en.wikipedia.org / wiki / Bhadla_Solar_Park) and nearly four times the rated capacity of the world’s largest wind farm (see Hornsea Project Two, en.wikipedia.org / wiki / Hornsea_Wind_Farm#Hornsea_Project_Two).

[0010] To adapt industrial ammonia production to existing renewable energy sources (in terms of both scale and intermittency), ammonia synthesis reactors (and their associated systems) require significant redesign in terms of scale, turndown capacity, and discontinuous operation.

[0011] Historically, ammonia synthesis reactors have been designed as steady-state, adiabatic, plug-flow, packed-bed reactors, filled with solid catalyst beads with a diameter of 1–10 mm. The catalyst materials are typically magnetite (Fe3O4) or stearite (Fe1₋₀). X O) or based on ruthenium (Ru).

[0012] The stoichiometric gas ratios and the exothermic reaction mean that, according to Le Chatelier's principle (see Le Chatelier's Principle, en.wikipedia.org / wiki / Le_Chatelier%27s_principle), ammonia production is thermodynamically more favorable at higher pressures and lower temperatures. However, lower reaction temperatures pose challenges to nitrogen activation and lead to slower reaction rates. Industrial Haber-Bosch synthesis typically employs a compromise: using medium to high pressures (150–400 bar) that favor ammonia conversion, while employing higher temperatures (400–600 °C) to increase the reaction rate, but at the expense of conversion.

[0013] The high operating temperatures of industrial Haber-Bosch reactors mean that their equilibrium product conversion limits are below 100%. Combined with catalyst performance limitations, this typically results in less than 30% of the reactants being converted to ammonia per pass through the reactor, requiring three or more passes to achieve complete conversion. This leads to higher compression requirements, larger equipment size, and lower overall energy efficiency.

[0014] The use of plug flow reactors in exothermic or endothermic reactions introduces design and operational complexities; for exothermic reactions, good temperature control is required to avoid reactor hotspots and catalyst sintering. In a single-bed plug flow reactor, the reactant conversion gradually approaches equilibrium as each "plug" of reactant moves along the axial length of the reactor; for exothermic reactions, the temperature distribution increases along the length of the reactor. Without a reliable mechanism for heat removal, the temperatures of the reactant / product gases, the reactor, and the catalyst will continue to rise along the catalyst bed path until the catalyst sintering temperature or the design temperature (whichever comes first) is reached. The catalyst positioned towards the reactor bed outlet is always at a higher temperature than the catalyst closer to the reactant inlet; temperature constraints effectively limit the length of the catalyst bed and thus also the residence time in the reactor. Typically, ammonia refineries use a single reactor pressure vessel to house multiple catalyst beds, with cooler "quench gases" introduced between the beds for temperature control and to increase reactant concentration during ammonia production. Figure 1A An example of this situation is shown in the figure.

[0015] Figure 1AAn example is illustrated of a general-purpose multi-bed single-vessel plug flow reactor commonly used in industrial ammonia production, employing quench cooling. In this system, a pressure vessel (1) houses multiple axially flowing catalyst beds (2), the dimensions of which are determined based on the target residence time or gas hourly space velocity (GHSV) at the design flow rate. A partially preheated mixture of hydrogen and nitrogen reactant feed gases enters the reactor (3), with some variants using cold feed gas to cool the catalyst bed walls at the inlet (4). The reactant gases are directed to an internal heat exchanger (5) to heat the reactants (while simultaneously cooling the hot product gases leaving the last catalyst bed), and then transferred via internal piping (6) to the first catalyst bed in the catalyst beds (2). 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 reaction and limiting the equilibrium product concentration. To keep the catalyst below the sintering temperature, dilute the product concentration, and maintain a suitable reaction temperature for better conversion, a quench gas (7) consisting of cooler reactant gases is added directly between the catalyst beds. After the gas has passed through the final catalyst bed, it is guided to the internal heat exchanger (5) before leaving the reactor (8).

[0016] Figure 1B An example of a general three-bed adiabatic quench reactor system is illustrated, and... Figure 1A The system shown is similar, but each catalyst bed uses a dedicated reactor vessel arranged in series; due to space or height constraints, a single reactor may need to be split into multiple vessels. In this system, each reactor pressure vessel (21, 26, 29) is equipped with a catalyst bed (22), and a mixture of preheated hydrogen and nitrogen feed gases enters the first reactor (23). The dimensions of the reactor catalyst beds are set such that the entire system achieves the target residence time or GHSV at the design flow rate. Detailed illustrations of necessary reactor vessel internal components (e.g., gas distributors or catalyst baskets) are not shown. As the reactant stream flows through each catalyst bed and ammonia is produced in an exothermic reaction, the released heat both slows the forward reaction and increases the temperature of the reactor vessel, catalyst, and gases. The hot gases are removed from reactors (24, 27) and diluted at the inlets of reactors 26 and 29 with a cooler hydrogen / nitrogen reactant known as “quench gas” (25, 28) to prevent catalyst overheating and further dilute the product gases (to increase ammonia output). The output (30) of this multi-bed, multi-reactor system is a mixture of unreacted hydrogen and nitrogen gases with gaseous ammonia products. The overall conversion efficiency of the unit is typically about 30%. The product gas (30) is typically cooled to separate the ammonia products from the unreacted feed gas, which is then recycled back to the first reactor (21).

[0017] A crucial consideration when designing any vessel is the reactor length (L) to diameter (D) ratio, which affects reactant distribution on the catalyst bed and the pressure drop across the reactor. For a plug flow reactor with a given overall reactor volume, a higher L / D ratio (i.e., a narrower but longer reactor) typically results in better reactant distribution on the catalyst bed, reduced channeling, lower risk of catalyst "hot spots" due to localized reactions, reduced need for complex inlet distribution designs, improved catalyst efficiency, and better performance during load conditioning. However, a higher L / D ratio leads to increased gas velocity through the catalyst bed (due to the smaller diameter) and an increased bed length, which causes a greater pressure drop along the reactor, resulting in higher compression energy costs.

[0018] To overcome issues related to fluid distribution, catalyst hotspots, and pressure drop, modern reactor designs have incorporated features such as radial flow beds ( Figure 1C Complex structures such as axial / radial flow combinations, external heat exchangers, and even multi-tubular reactor devices are used; these designs also help to smooth and control the reactor temperature distribution. Despite modern improvements, load regulation capability is usually limited to about 50% of the reactor's design flow rate due to channeling, low catalyst utilization efficiency, and the resulting unfavorable temperature gradients, hot spots, and catalyst sintering.

[0019] Figure 1C An example of a general multi-bed radial flow reactor integrating a feed gas heat exchanger is illustrated, commonly used in existing commercial ammonia synthesis processes. In this system, a pressure vessel (41) houses multiple radial flow catalyst beds (42, 43, 44), the dimensions of which are determined based on the target residence time or GHSV at the design flow rate. A partially preheated mixture of hydrogen and nitrogen reactant feed gases enters the reactor (45), with some variants using cold feed gas to cool the catalyst bed walls at the inlet (46). The reactant gases are directed to an internal heat exchanger (47) to heat the reactants (while simultaneously cooling the hot product gases leaving the last catalyst bed), and then transferred to the first catalyst bed (42) via internal piping (48). 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 reaction and limiting the equilibrium product concentration. To keep the catalyst below the sintering temperature, dilute the product concentration, and maintain a suitable reaction temperature for better conversion, quenching gases (49) consisting of cooler reactant gases are added between the catalyst beds. After the gases have passed through the final catalyst bed, they are directed to the internal heat exchanger (47) before leaving the reactor (50).

[0020] While catalyst lifespan is typically 5-10 years, this is shorter than the reactor's lifespan, necessitating replacement. More complex units, such as multi-bed reactors with intricate internal structures, present access and design challenges for catalyst removal and loading. A recent study showed that catalyst replacement in a typical multi-bed ammonia synthesis reactor takes over 450 hours, partly due to the reactor's physical complexity (see Catalyst Replacement Time; ISSN 0149-3701; and ammoniaknowhow.com / optimizing-the-installation-and-operation-of-a-new-3-bed-ammonia-synthesis-converter-basket / ).

[0021] While there have been some attempts to design isothermal (constant temperature) rather than adiabatic reactors, for moderately exothermic reactions such as ammonia synthesis, this involves significant internal and external mechanical complexities due to the need to remove heat uniformly throughout the catalyst bed.

[0022] The main reason most state-of-the-art ammonia synthesis reactors are still based on adiabatic plug flow designs is that these designs are suited to the high, constant flow rates required by modern, custom-built ammonia refineries designed for large-scale ammonia production. The advantages of these state-of-the-art designs include high productivity per unit weight of catalyst, increased contact area between reactants and catalyst surfaces under design conditions, and a lower reactor metal weight to catalyst ratio (as a proxy for reactor manufacturing costs).

[0023] Meanwhile, the most advanced technologies available today are specifically designed to operate in steady-state control mode, which greatly simplifies process control systems. It should be remembered that the development trajectory of current ammonia synthesis reactors began in 1913, before the availability of today's automated process control mechanisms; reactors needed to be designed to achieve high flow rates with as little external (and often manual) control intervention as possible. Such high levels of productivity would not have been possible without the use of plug flow reactors operating in steady state, even before the advent of computerized and automated process control systems.

[0024] The need for steady-state operation is reinforced by two additional factors that influence current state-of-the-art technology. As previously mentioned, over 95% of ammonia production (and therefore synthesis reactors) is installed in plant facilities that obtain hydrogen feedstocks from fossil fuels. The upstream plants for ammonia synthesis reactors are either steam methane reforming (SMR) systems for natural gas feedstocks or coal gasification systems for coal feedstocks. Both SMR and coal gasification systems are highly complex to design, construct, and operate, and have limited load regulation capabilities; all efforts are focused on ensuring steady-state flow through the downstream Haber-Bosch system to minimize fluctuations in operating conditions and product specifications within the complex upstream systems. Simultaneously, centrifugal compressors are widely used in high-throughput facilities to compress feed gases due to their improved performance and economics at high flow rates; high-speed gas compression systems operate optimally under steady-state conditions, and their limited load regulation capabilities further reinforce the focus on steady-state operation in current reactor design.

[0025] Reactors designed for green ammonia production are freed from the constraints of upstream SMR or coal gasification systems for steady-state operation and do not require reliance on high-flow-rate compressed gas systems for large-scale economics; meanwhile, engineers can now utilize highly automated computer control systems. Therefore, modern ammonia synthesis reactor designs can take advantage of varying throughputs, higher load regulation ratios, and the opportunities offered by systems that rely on highly complex process controls.

[0026] In summary, current state-of-the-art reactors are completely unsuitable for relatively small-scale green ammonia production using intermittent electricity supplied by most clean energy sources (geothermal energy may be an exception). Current state-of-the-art reactors are designed for custom construction, high throughput, continuous, steady-state operation; while green ammonia reactors must be designed for small-scale (low throughput), variable output, high load regulation, rapid start-up, and high efficiency, while still maintaining effectiveness under high temperature and pressure.

[0027] There is a need in the field for improved chemical reactor systems for gas synthesis, particularly systems that can be coupled to intermittent or variable energy production technologies. Summary of the Invention

[0028] One aspect of this disclosure relates to a chemical reactor system for gas synthesis.

[0029] The systems disclosed herein include batch, quasi-batch, or dynamic reactors formed by one or more individual catalytic reactors for gas synthesis. The use of the highly simplified or modular reactors described herein (especially when constructed with standardized components as described herein) makes the overall system cost competitive.

[0030] In one non-limiting embodiment, the chemical reactor system includes a batch, quasi-batch, or dynamic temperature-oscillating gas synthesis reactor system formed by one or more individual catalytic reactors for gas synthesis.

[0031] In an alternative, non-limiting embodiment, the chemical reactor system comprises a multi-container batch, quasi-batch, or dynamic reactor for gas synthesis, formed by interconnected individual catalytic reactors.

[0032] The chemical reactor system further includes: one or more fluid control mechanisms connected to individual catalytic reactors of one or more multi-vessel batch or quasi-batch reactors; and a control system capable of activating the one or more fluid control mechanisms to control the entry of reactants into the system and the exit of reaction products from the system.

[0033] In a non-limiting embodiment, the control system is capable of controlling the reactor inlet and outlet mechanisms in the system to cause fluid to flow through the individual catalytic reactors in a serial, parallel, or combined manner, thereby making the fluid flow through the chemical reactor system nearly continuous, while the fluid in each individual reactor is stationary or nearly stationary for a portion of its residence time.

[0034] The control system may be automated and / or enable individual or grouped catalytic reactors to operate in a batch operation mode, or in a continuous, steady-state or plug flow operation mode.

[0035] Individual catalytic reactors used in the chemical reactor system may be equipped with internal or external heat transfer systems to modify the reactor temperature during the reaction, and / or with one or more sensors, detectors, or controllers that transmit information to the control system, thereby enabling the chemical reactor system to operate in a manner that allows for a continuous inflow of reactants and a continuous outflow of reaction products through the chemical reactor system.

[0036] The individual catalytic reactors used in the chemical reactor systems described in this disclosure can be designed as tube-in-tube heat exchangers.

[0037] The control system used in the chemical reactor system described in this disclosure may be computerized and connected to a remote or cloud-based controller, and / or algorithms, predictive control, artificial intelligence, or machine learning may be used to optimize the performance of individual or grouped catalytic reactor vessels and the chemical reactor system.

[0038] In one non-limiting embodiment, the chemical reactor system is used for ammonia synthesis.

[0039] Another aspect of this disclosure relates to energy waste reduction systems comprising a chemical reactor system as disclosed herein, coupled to a variable or intermittent energy production technology. In one non-limiting embodiment, coupling the chemical reactor system of the present invention with a variable or intermittent energy production technology realizes a power-to-X (also known as P2X or P2Y) system.

[0040] Another aspect of this disclosure relates to a method for producing gas by coupling an intermittent energy production technology with a chemical reactor system as disclosed herein.

[0041] 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 an individual catalytic reactor or a group of reactors to allow sufficient synthesis feed gas to be delivered to each reactor, thereby filling it with feed gas; once filled with feed gas, closing the one or more fluid control mechanisms to stop or sufficiently slow the flow of gas in contact with the catalyst, thereby allowing the reaction to occur; timing, predicting, and / or monitoring the temperature, pressure, and / or other measurable states within each closed or partially closed reactor to determine reaction progress; and once the reaction has reached the desired progress, discharging the reaction products.

[0042] Another aspect of this disclosure relates to a method for modifying an ammonia plant unit with a synthesis loop, wherein fresh ammonia synthesis gas containing hydrogen and nitrogen is combined with any circulating stream to form a combined ammonia synthesis gas, and said combined ammonia synthesis gas is reacted over a catalyst to form a converted ammonia product gas. The modification method involves the following steps: replacing one or more existing ammonia synthesis reactors with a chemical reactor system as disclosed herein; installing a feed gas heat exchanger upstream of said chemical reactor system, the feed gas heat exchanger being capable of heating the synthesis gas to a target and controlled temperature required for batch operation of the reactor; installing a heat exchanger and a gas-liquid separator for condensing and recovering ammonia from the reactor effluent stream and forming an ammonia-lean stream; and installing a pressure control system to enable control and manipulation of the operating pressure of said chemical reactor system.

[0043] Another aspect of this disclosure relates to a method for producing ammonia from a synthesis gas containing hydrogen and nitrogen, combined with any circulating stream. In this production method, the 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 at an inlet to one or more manifolds and at an outlet to one or more manifolds. Each catalyst-filled pressure vessel reactor is equipped with independently operating mechanisms to control, direct, and stop the flow of fluid through the inlet manifold to the individual vessel and catalyst bed, or the flow of fluid through the outlet manifold to the individual vessel and catalyst bed. The control mechanisms of the selected catalyst-filled pressure vessel reactor or group of catalyst-filled pressure vessel reactors are then opened to allow sufficient synthesis feed gas to be delivered from its inlet manifold to each catalyst-filled pressure vessel reactor, thereby filling it with feed gas and pressurizing it to a selected operating pressure. Then, once filled with feed gas, the control mechanisms at each end of the selected catalyst-filled pressure vessel reactor or group of reactors are closed to stop or sufficiently slow the flow of gas in contact with the catalyst, thereby allowing the reaction to occur. Subsequently, the temperature, pressure, and / or other measurable states within each closed or partially closed catalyst-filled pressure vessel reactor are timed, predicted, and / or monitored to determine reaction progress. Once the reaction has reached the desired state, conversion, or equilibrium conversion, the one or more catalyst-filled pressure vessel reactors are allowed to cool below the critical point temperature or dew point temperature of the ammonia product, and once sufficiently cooled, the liquid ammonia product collected in the lower portion of the one or more catalyst-filled pressure vessel reactors is drained, while preventing the majority of unreacted gas from escaping the one or more catalyst-filled pressure vessel reactors. This filling process is then repeated by adding new synthesis feed gas to any remaining unreacted gas in the one or more catalyst-filled pressure vessel reactors.

[0044] In this production method, one or more catalyst-filled reactor vessels can be used to store the reactants at high pressure before the ammonia production process is started in a controlled manner by introducing a second reactant.

[0045] In this production method, hydrogen and / or nitrogen can be stored at sufficiently high pressure in the one or more catalyst-filled pressure vessel reactors during periods when electricity is available, so that they can be transferred to a portion of the one or more catalyst-filled pressure vessel reactors during periods when electricity is unavailable (e.g., but not limited to nighttime, windless, or without sunlight) to produce ammonia.

[0046] In this production method, the one or more catalyst-filled pressure vessel reactors may be sequentially filled with feed gas to allow for intermittent or near-intermittent residence times in each reactor, while having a continuous or near-continuous flow of feed gas through the entire system of the reactor vessel.

[0047] In this production process, the one or more catalyst-filled pressure vessel reactors may be equipped with sensors, detectors, or controllers that transmit information to one or more control systems, thereby enabling the system consisting of the reactor, mechanisms, sensors, and control systems to operate in a manner that allows for a continuous inflow of feed gas and a continuous outflow of products through the overall reactor system.

[0048] In this production process, the one or more catalyst-filled pressure vessel reactors may be equipped with a control system capable of manipulating the reactors and their fluid control mechanisms to sequentially fill them with synthesis gas, allowing for intermittent or near-intermittent residence times in each reactor, while having a continuous or near-continuous flow of feed gas through the entire system of the reactor vessel.

[0049] In this production process, the one or more catalyst-filled pressure vessel reactors may be equipped with a control system that can control the temperature of the synthesis feed gas.

[0050] In this production process, the one or more catalyst-filled pressure vessel reactors may be equipped with a control system that can control the operating pressure of the reactor system.

[0051] In this production process, the one or more catalyst-filled pressure vessel reactors may be equipped with internal or external heat transfer systems to regulate the reactor temperature during the reaction.

[0052] In this production process, the one or more catalyst-filled pressure vessel reactors can be designed as tube-in-tube heat exchangers.

[0053] In some embodiments of the invention, the ratio of reactants entering the vessel is modified to control reaction progress and the heat released through the reactor vessel walls. In one non-limiting embodiment, the reactor is first filled to the desired pressure with only hot, compressed hydrogen, and then nitrogen is added gradually and sufficiently so that the heat generated by the exothermic reaction matches the heat released to the atmosphere through the reactor walls. In this non-limiting embodiment, the amount of ammonia produced is controlled by controlling the nitrogen inflow, thereby controlling the heat released by the exothermic reaction to match the heat released from the reactor to the atmosphere, keeping the reaction temperature constant. An additional advantage of this non-limiting embodiment of the invention is the use of Le Chatelier's principle, whereby a high concentration (or excess) of reactants drives the reaction toward the product side, resulting in a higher equilibrium conversion at a given operating temperature and pressure. The ability to remove liquid products without unreacted feed gas allows the use of stoichiometric or non-stoichiometric reactant ratios without the penalty of increased compression due to high circulation rates. Attached Figure Description

[0054] The accompanying drawings illustrate various embodiments of the systems and methods of this disclosure, as well as various other aspects thereof. Those skilled in the art will understand that the element boundaries (e.g., boxes, groups of boxes, or other shapes) shown in the drawings represent one example of these boundaries. In some examples, it is possible that 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 in another example, and vice versa. Furthermore, these elements may not be drawn to scale. The following description, with reference to the accompanying drawings, illustrates non-limiting and non-exhaustive embodiments. Components in the drawings are not necessarily drawn to scale, but rather the focus is on illustrating principles. Some embodiments of the invention are shown by way of example and are not limited by the illustrations in the drawings, in which the same reference numerals may denote similar elements:

[0055] Figure 1A A standard multi-bed adiabatic quench reactor of the prior art is described, which integrates a feed gas heat exchanger and is commonly used in ammonia synthesis processes.

[0056] Figure 1B A standard multi-bed radial flow reactor of the prior art is described, which integrates a feed gas heat exchanger and is commonly used in ammonia synthesis processes.

[0057] Figure 1C A prior art three-bed adiabatic quench reactor system is described, which, together with Figure 1A The quench reactor shown is similar, but each catalyst bed uses a dedicated reactor vessel arranged in series, which is commonly used in ammonia synthesis processes.

[0058] Figure 2 An example of a chemical reactor system for gas synthesis is illustrated as a non-limiting embodiment of the invention: a multi-container temperature swing reactor system having a common inlet for reactants and a common outlet for reaction products.

[0059] Figure 3 An example of a chemical reactor system for gas synthesis is illustrated as a non-limiting embodiment of the invention: a multi-container temperature swing reactor system having a common inlet for reactants and a common outlet for reaction products, and using a multi-port valve.

[0060] Figure 4 An example of a chemical reactor system for gas synthesis is illustrated as a non-limiting embodiment of the invention: a multi-container temperature swing reactor system having a common inlet for reactants and a common outlet for reaction products, and with multiple inlet manifolds.

[0061] Figure 5 A cross-sectional view illustrating a non-limiting embodiment of an individual reactor pressure vessel used in the temperature swing reactor system of the present invention is shown.

[0062] Figure 6 A cross-sectional view illustrating a non-limiting embodiment of an individual reactor pressure vessel used in the temperature swing reactor system of the present invention is shown, including an active cooling system.

[0063] Figure 7 A cross-sectional view illustrating a non-limiting embodiment of an individual reactor used in the temperature swing reactor system of the present invention is shown, wherein a typical pressurized gas storage tank is filled or partially filled with catalyst to serve as a reactor pressure vessel, and as... Figure 2 , Figure 3 and Figure 4 As shown.

[0064] Figure 8 This is a process schematic 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.

[0065] Figure 9 This is a process schematic diagram of a non-limiting embodiment of the control system for the temperature swing reactor system of the present invention.

[0066] Figure 10 This is a process schematic diagram of a non-limiting embodiment of the temperature swing reactor system of the present invention, used in chlorine production systems (e.g., nighttime ammonia production in solar-powered systems) during periods of low power availability.

[0067] Figure 11 An alternative, non-limiting embodiment of the chemical reactor system for gas synthesis of the present invention is illustrated: a simplified multi-container quasi-batch reactor system for gas synthesis, which is formed by connected individual catalytic reactors with separate reactant inlets and product outlets.

[0068] Figure 12 An alternative, non-limiting embodiment of the invention for gas synthesis is illustrated: a multi-container quasi-batch reactor system for gas synthesis, formed by interconnected individual catalytic reactors, having separate reactant inlets and product outlets, and possessing reverse flow capability.

[0069] Figure 13 An alternative, non-limiting embodiment of the chemical reactor system for gas synthesis of the present invention is illustrated: a multi-container quasi-batch reactor system for gas synthesis, which is formed by connected individual catalytic reactors, having separate reactant inlets and product outlets, and possessing individually selectable reverse flow capability.

[0070] Figure 14 This illustrates an alternative, non-limiting embodiment of the chemical reactor system for gas synthesis according to the present invention: a multi-container quasi-batch reactor system for gas synthesis, formed by interconnected individual catalytic reactors, having separate reactant inlets and product outlets, individually selectable reverse flow capability, and using multi-port valves.

[0071] Figure 15 Examples of its use and application in this invention are illustrated. Figures 11 to 14 A cross-sectional view of a non-limiting embodiment of the individual reactor pressure vessel shown.

[0072] Figure 16 Examples of its use and application in this invention are illustrated. Figures 11 to 14 The diagram shows a cross-sectional view of a non-limiting embodiment of an individual reactor pressure vessel, which includes an active cooling system.

[0073] Figure 17 This is a process diagram illustrating a non-limiting example of an ammonia production system. Figures 11 to 14 How does the chemical reactor system interact with other parts of the system?

[0074] Figure 18 It is used in the present invention Figures 11 to 14 A process schematic diagram of a non-limiting embodiment of the control system of a chemical reactor system. Detailed Implementation

[0075] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used herein, the term "and / or" includes any one or more of the associated listed items and all combinations thereof. As used herein, the singular forms "a," "an," and "the" are intended to include both singular and plural forms unless the context clearly indicates otherwise. It should be further understood that when "comprises" and / or "comprising" are used in this specification, they indicate the presence of the stated features, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, elements, components, and / or combinations thereof.

[0076] Unless otherwise defined, all terms used herein (including technical and scientific terms) shall have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It should be further understood that terms such as those defined in common dictionaries shall be interpreted as having the same meaning as they have in the relevant technical field and in the context of this disclosure, and shall not be interpreted in an idealized or overly formal manner unless expressly defined herein.

[0077] In describing this invention, it should be understood that several techniques and steps have been disclosed. Each of these techniques and steps has its own advantages, and each can be used in combination with one or more of the other disclosed techniques, and in some cases even with all of the other disclosed techniques. Therefore, for clarity, this specification will avoid unnecessarily repeating all possible combinations of individual steps. However, a reading of the specification and claims should be understood as meaning that such combinations are fully within the scope of this invention and the claims.

[0078] This disclosure provides a chemical reactor system for gas synthesis, comprising: a batch, quasi-batch, temperature-oscillating, or dynamic reactor for gas synthesis, the reactor being formed by one or more individual catalytic reactors; one or more fluid control mechanisms, formed by shared piping and manifolds, for delivering reactants to the chemical reactor system and collecting reaction products from the chemical reactor system; and a control system capable of opening the one or more fluid control mechanisms to control the entry of reactants into the chemical reactor system and the exit of reaction products from the chemical reactor system. These chemical reactor systems can be coupled to variable or intermittent energy production technologies, making them particularly suitable for 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 realizes a Power-to-X (also known as P2X or P2Y) system. Power-to-X (P2X or P2Y) can be defined as a system that utilizes renewable energy for electricity conversion, energy storage, and / or reconversion. Non-limiting examples of such energy production technologies include solar, wind, hydro, and geothermal energy production technologies. This disclosure also provides methods for using these systems in gas synthesis (and particularly ammonia synthesis), and methods for retrofitting ammonia synthesis plant equipment. When the disclosed chemical reactor systems are used for ammonia (NH3) synthesis, the well-established gas-phase catalytic chemistry used in most Haber-Bosch processes can be adapted to variable or intermittent renewable energy power sources.

[0079] Figures 2 to 10 A non-limiting embodiment of the chemical reactor system 200 of this disclosure is illustrated, which is equipped with a multi-vessel temperature swing reactor system 230. However, those skilled in the art will understand upon reading this disclosure that alternative embodiments, including single-vessel reactors, may also be used in these chemical reactor systems and are considered to be within the scope of this invention.

[0080] refer to Figure 2 Multiple reactor vessels 202a, 202b, 202c…202n are connected to a common inlet manifold 201 and outlet manifold 209 via piping 205, and are equipped with mechanisms to control the flow of reactants into vessel 206 and out of vessel 207. In a non-limiting embodiment, each reactor vessel is equipped with an inlet valve 206 and an outlet valve 207 as these mechanisms. The inlet manifold 201 may be equipped with valves 201a and 201b to control the composition of the reactants within the inlet manifold. Other embodiments may have repeating inlet manifolds 201 and associated inlet valves 206 dedicated to each reactant. The orientation of the vessels, manifolds, and piping system can be optimized based on characteristics such as the reaction, reactants, catalyst, and heat transfer, as well as other constraints.

[0081] Each reactor vessel 202 is constructed of a hollow cylindrical segment containing a catalyst 203 and equipped with a fixed dome or end cap 204 at each end. Some embodiments may employ removable or detachable end caps at each end of the hollow cylinder. In a non-limiting embodiment, the reactor vessel 202 is constructed of a standard hydrogen storage tank (see [link to documentation]). Figure 7 (Details). In another non-limiting embodiment, reactor vessel 202 is constructed using a section of nominal piping (NPS or DN), and end cap 204 is constructed using standard pipe flanges (e.g., ASME, DIN, or EN) (see details). Figure 5 or Figure 6 (Details).

[0082] Individual reactor vessels are filled with synthesis feed gas by opening their dedicated inlet valve 206, which connects the reactor pressure vessel to the inlet manifold 201. Inlet valve 206 is open for a sufficient time to allow inflow fluid from inlet manifold 201 to enter the vessel and pressurize it to the desired operating point, after which valve 206 is closed. For systems employing serial intermittent filling, the time required to fill a given reactor vessel is approximately equal to the mass of gas within that individual reactor vessel 202 at peak operating pressure divided by the total mass flow rate of the system through these reactors.

[0083] At the start of a given reactor's filling sequence, its internal pressure will be lower than at the end of the filling sequence; therefore, at the start of the filling sequence, the pressure difference across inlet valve 206 will be higher than at the end.

[0084] For reactor vessels operating in a serial filling manner, each reactor is filled sequentially using the same method, with a degree of overlap in the opening of the inlet valves 206 between reactors to ensure continuous flow at the inlet manifold 201, meeting the requirements of the upstream compression system or other constraints. As the inlet valves open and close, the pressure in the inlet manifold may fluctuate slightly, but will typically remain at or near the desired operating pressure within the reactor. The inlet valve 206 and outlet valve 207 of each reactor remain closed when that particular reactor is not filled or emptied.

[0085] Once the reactor is filled with reactant gases, a given reaction will proceed as long as conditions are favorable. As a non-limiting example, for ammonia synthesis, this requires the reactants to be under sufficiently high pressure and temperature, and in the presence of a suitable catalyst. In some non-limiting embodiments of the invention, the incoming reactants are heated before entering the reactor; this may be due to a temperature rise caused by reactant compression (before entering the reactor vessel), or as a result of a temperature rise caused by some other heat source. In some non-limiting embodiments of the invention, a heat source located inside or connected to the reactor body can be used to heat the reactants after they have been added to the reactor vessel (see [link to invention]). Figure 5 or Figure 6 (Details).

[0086] For ammonia synthesis, heat is released as the reaction proceeds and as nitrogen and hydrogen reactants are converted into ammonia products. Depending on the volume of each reactor vessel, it may be necessary to control the heat release to prevent exceeding the actual or designed temperature conditions. Furthermore, according to Le Chatelier's principle (see en.wikipedia.org / wiki / Le_Chatelier%27s_principle), higher reactor temperatures for ammonia synthesis reduce the equilibrium conversion rate. To control the reactor temperature, one or more reactants can be added to the reactor slowly, for example at a rate that allows convective heat dissipation from the reactor body to match the released heat.

[0087] In a non-limiting embodiment of the invention, valve 201a is connected to a high-pressure hydrogen supply source, and valve 201b is connected to a high-pressure nitrogen supply source. The reactor vessels are first sequentially filled with hydrogen to the desired pressure via valve 201a (while valve 201b is closed); once all vessels are filled with hydrogen at the operating pressure and temperature, valve 201a is closed. Subsequently, valve 201b is opened, and nitrogen is added to each vessel (via valve 206) at a sufficiently low rate to maintain a constant reaction temperature within each vessel.

[0088] For ammonia synthesis, a product-to-reactant molar ratio of 0.5 means that the pressure within the adiabatic system may decrease as the reaction proceeds (depending on the system temperature); this allows nitrogen to be added to the reactor as the reaction proceeds while maintaining approximately the same operating pressure without removing the product. Once equilibrium conversion has been reached under given reactor conditions, nitrogen feeding is stopped, and the reactor is cooled below the dew point or critical temperature of the ammonia product (approximately 132 degrees Celsius), after which the liquid ammonia product can be evacuated from the reactor. Some non-limiting embodiments of the invention may first fill the container holding the catalyst with nitrogen and then gradually add hydrogen in a manner similar to the procedure described above.

[0089] In some non-limiting embodiments of the invention, all reactants are added when the reactor is initially filled and reacted until equilibrium conversion is reached. For ammonia synthesis, energy is released as products are produced until equilibrium conversion is reached, and no further ammonia products are formed. Depending on the rate at which nitrogen is added to the reactor, the heat generated by the reaction may cause the reactor temperature to rise or remain constant; after reaching equilibrium, the reactor temperature will stabilize as the reaction slows or stops. Once the reactor begins to cool due to atmospheric heat dissipation or any applied cooling, the reaction can be restarted and advanced to a new equilibrium conversion according to Le Chatelier's principle (see en.wikipedia.org / wiki / Le_Chatelier%27s_principle). When the final equilibrium conversion has been reached, the reactor is cooled below the dew point or critical temperature of the ammonia products (approximately 132 degrees Celsius), whereby, according to the partial pressure of ammonia, gaseous ammonia will be converted to liquid, and this liquid product can then be discharged from the reactor.

[0090] The purpose of reactor evacuation in this invention is to remove as much liquid ammonia product as possible, while preventing unreacted reactant gases from leaving the vessel through the outlet manifold. Once the ammonia is cooled below the critical temperature (or, depending on the operating pressure, below the dew point / bubble point), it will change from a gaseous phase to a liquid phase and settle to the bottom of the reactor vessel; while the reactants remain in the gaseous phase even at typical system operating pressures and temperatures far below atmospheric temperature. Therefore, the vessel outlet piping system must be positioned towards the bottom of the vessel (e.g., Figures 2 to 7 (As shown, it may be located externally, or internally using some kind of bottom collector). The removal of liquid products allows for the extraction of relatively pure, high-quality ammonia products from the reactor vessel under high pressure without significant product cooling or the recirculation of unreacted reactant gases (and related equipment), which are currently necessary for state-of-the-art technologies.

[0091] The operation of emptying the product from the reactor is accomplished by opening the mechanism or valve 207 connecting the reactor to the outlet manifold 209 after the reactor has been sufficiently cooled to allow for the formation of a liquid product; in most embodiments, the inlet valve 206 remains closed during container evacuation. The pressure in the outlet manifold is lower than the operating pressure of the reactor vessel, possibly at or near the product storage pressure (which can be as low as 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 decreases from the reactor pressure to the outlet manifold pressure.

[0092] At the start of the venting sequence, the pressure differential across the outlet mechanism or valve 207 will be at its highest and will decrease as the reactor vents. The outlet valve 207 should be closed before all liquid product is removed from each reactor to prevent unreacted gas from entering the outlet manifold 209. Various types of vessel level gauges may be needed to determine when sufficient liquid product has been removed (and unreacted gas escape minimized). Once sufficient liquid product has been removed from the reactor, it can be refilled with reactants (heated externally or internally) to the operating pressure, which will allow for the production of more product.

[0093] In some non-limiting embodiments, depending on the rates of filling, reaction, cooling, and evacuation, the first reactor 202a is refilled once the last reactor 202n has been filled, thereby maintaining continuous flow through the entire system. The control system must account for the time spent evacuating the reactors; to achieve continuous flow, the next reactor to be filled must be actively evacuated before filling. Therefore, the non-moving residence time of each reactor vessel is approximately equal to the filling time of the individual reactor multiplied by the number of subsequent reactors.

[0094] For systems operating via serial packing, the available average residence time is a function of the sum of catalyst volumes in all reactors to the total fluid flow rate through the system. For a given flux and target residence time (and thus catalyst volume), the number of serially packed reactors selected in the system is an optimization between the desired non-moving residence time and reactor packing constraints.

[0095] The filling and evacuation of the reactor will be limited by some maximum rate, which is determined by the acceptable pressure drop through the catalyst bed, limitations on potential catalyst damage or entrainment, limitations on vessel pressure changes, or other physical criteria (e.g., the rate at which valves open / close in the filling sequence). For some non-limiting embodiments of the invention, reactors filled in parallel in groups would be desirable.

[0096] This non-limiting embodiment of the invention can also be used to allow flow between reactors during downtime (e.g., at night or during periods of low wind speed when variable or intermittent renewable energy is unavailable). In one non-limiting example, at the upstream compressor ( Figure 2 During shutdown periods (not shown), reactor 202a is vented to reactor 202b via the inlet manifold. For this purpose (and in other scenarios), the flow must be from the high-pressure reactor to the low-pressure reactor. In this example scenario, reactor 202a operates at a higher pressure than reactor 202b, and all reactors operate in batch mode (all reactor inlet / outlet valves are closed).

[0097] In a non-limiting embodiment of the invention, several reactors are filled during the day with only one reactant (e.g., hydrogen) to a pressure higher than the normal reactor operating pressure (e.g., 350 barg or 700 barg), while a portion of the reactors are filled with both reactants to the normal operating pressure. During periods when no power is available, once a reactor has been emptied of product, gas is vented from the high-pressure reactor into the inlet manifold to refill the empty reactor, and so on; once all the high-pressure-filled reactors have been emptied to the normal operating pressure, the product can be produced using all reactors by gradually adding nitrogen. This operating scenario allows for the use of a smaller number of reactors to store reactants at a higher density for “offline” production.

[0098] To complete the reactor-to-reactor gas transfer, valve 206a is opened to connect inlet manifold 201 to line 205a, while valve 207 is closed. On reactor 202b, valve 206b is positioned to connect inlet manifold 201 to line 205b; valve 207b is closed. Gas flows from reactor 202a through line 205a and valve 206a to inlet manifold 201, and then through valve 206b and line 205b into reactor 202b. When the pressure differential is exhausted, gas flow between reactors 202a and 202b will cease; the final operating pressure will be between the two initial pressures, depending on the relative volumes of the two reactors, the catalyst porosity, and the gas composition. In some non-limiting embodiments of the invention, a single multi-port valve replaces valves 206 and 207.

[0099] Figure 3 This non-limiting embodiment of the invention is illustrated by a multi-container temperature swing ammonia synthesis reactor system 230 using a multi-port valve.

[0100] refer to Figure 3 This illustrates a non-limiting embodiment of the invention, which is related to... Figure 2 Similar, but using multi-port valves for filling and emptying individual reactor vessels. Compared to Figure 2 The embodiment shown, Figure 3 The advantage of the non-limiting embodiment shown is that individual reactors can be filled or emptied at any time, and only a single valve or mechanism is used for this purpose.

[0101] As a non-limiting example, to fill individual reactor 202a, reactant gases flow in via manifold 201 through valve 206, which is positioned to connect the inlet manifold reactor line 201 to the reactor via inlet piping 205; in this position, the connection between line 205 and outlet manifold 209 is closed. As the reactor is filled, the inflowing gas pressurizes reactor vessel 202 from its initial pressure to its operating pressure. While other reactors (202b, 202c…202n) are being filled, reactor 202a can be vented at any point by changing the position of valve 206, opening line 205 to outlet manifold 209 and closing inlet manifold 201. The high pressure in reactor 202 pushes the reacted product gases through valve 206 via the manifold towards the lower outlet manifold 209, which operates at a lower pressure.

[0102] Figure 4 Another non-limiting embodiment of the invention is illustrated: a multi-container temperature swing ammonia synthesis reactor system 230 with multiple inlet manifolds.

[0103] refer to Figure 4 This illustrates a non-limiting embodiment of the invention, which is related to... Figure 2 Similar, but equipped with multiple manifolds for filling individual reactor vessels. Compared to Figure 2 The embodiment shown, Figure 4 The advantage of the non-limiting embodiment shown is that one reactant (e.g., nitrogen) can be added to an individual reactor while other reactors are filled with different reactants (e.g., hydrogen).

[0104] As a non-limiting example, inlet manifold 201a is dedicated to hydrogen, while inlet manifold 201b is dedicated to nitrogen. In this scenario, reactor 202a is initially filled with hydrogen reactants, which flow into the reactor via manifold 201a through valve 206 and piping 205, while nitrogen inlet valve 210 and outlet manifold valve 207 remain closed. During reactor filling, the incoming hydrogen pressurizes reactor vessel 202a from a lower initial pressure to a higher operating pressure. Once reactor 202a is filled, nitrogen reactants can be introduced into reactor 202a via nitrogen manifold 201b through a dedicated nitrogen inlet valve 210. Figure 4 An advantage of this non-limiting embodiment of the invention shown is that other reactors (e.g., 202b, 202c…202n) can be filled with hydrogen in series or in parallel using their dedicated hydrogen manifold inlet valves, while other reactors (e.g., 202a) are filled with nitrogen. Another advantage of this non-limiting embodiment of the invention is that hydrogen and nitrogen can be added to individual reactors in parallel and at different ratios, depending on the current reaction state or a specific desired reactant ratio.

[0105] Once the reaction has proceeded sufficiently, no more nitrogen is added, and the reactor is cooled below the critical temperature, causing the ammonia product to condense from a gaseous state to a liquid state. The liquid ammonia product in each individual reactor can be vented to the outlet manifold 209 by closing the dedicated inlet valves 206 and 210 of each reactor and opening the outlet valve 207. The high pressure within 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.

[0106] Figure 5 A cross-sectional view illustrating a non-limiting embodiment of an individual reactor pressure vessel used in this invention is shown.

[0107] refer to Figure 5 In this embodiment, the reactor vessel 202 is a pressure vessel consisting of a cylindrical shell with flanges 216 at each end, to which end caps 208 are attached. In a non-limiting embodiment, the end caps 208 are removable. The end caps of the pressure vessel are equipped with one or more components 215 (e.g., nozzles) for connecting piping systems for fluid inlet and outlet; some non-limiting embodiments may have one or more components 215 (such as nozzles) at both ends. A catalyst bed 203 is housed within the pressure vessel shell between the two end caps. In some non-limiting embodiments, the catalyst bed completely fills the vessel; in other non-limiting embodiments, the catalyst occupies only a portion of the vessel volume to achieve a higher average porosity and increased gas capacity. Catalyst retainers or grids 217 located at each end prevent the catalyst from leaving the pressure vessel during operation. One end cap may be equipped with a standard flange gasket 218.

[0108] In one non-limiting embodiment, the catalyst grid 217 is located between the pressure vessel flange 216, the gasket 218, and the head 208; in another non-limiting embodiment, the grid may be integral with the gasket, which forms a seal between the pressure vessel flange and the head. In a preferred embodiment, to reduce the cost and requirements of custom design, manufacturing, and testing, the reactor vessel 202 is made using a section of nominal piping (NPS or DN), while the flange 208 and head 508 are made using standard piping flanges (e.g., ASME, DIN, or EN). The multi-vessel reactor system described in this invention enables the use of nominal piping and standard flanges.

[0109] Figure 6 A cross-sectional view of a non-limiting embodiment of an individual reactor pressure vessel used in the present invention is shown, including an active cooling or heating system.

[0110] refer to Figure 6This illustrates a non-limiting embodiment of an individual reactor vessel used in the present invention, which is similar to... Figure 5 Similar, but with the addition of an active heat transfer system. For example... Figure 5 As shown, reactor vessel 202 is a pressure vessel consisting of a cylindrical shell with flanges 216 at each end to which end caps 208 are attached. The end caps of the pressure vessel are equipped with one or more nozzles 215 for connecting piping systems for fluid inlet and outlet; some embodiments may have one or more nozzles 215 at both ends. In a non-limiting embodiment, a hollow external conduit 220 covers a portion of the cylindrical shell of reactor vessel 202 and is equipped with an inlet nozzle 221 and an outlet nozzle 222. A heat transfer medium flows into the external conduit 220 via nozzle 221 and contacts the pressure vessel shell thereon. In a non-limiting embodiment for reactor cooling, a cold heat transfer medium is transferred via nozzle 221 to the heat transfer system formed by the external conduit 220, where it is heated to cool reactor vessel 202 and its contents. The flow of the heat transfer medium is controlled continuously or intermittently using a valve (not shown) at the outlet. In some embodiments, adding a heat transfer medium to the jacket can also be used to increase thermal inertia during reactor operation, even if the medium does not flow during normal operation.

[0111] Figure 7 A cross-sectional view illustrating one embodiment of the individual reactor used in this invention is shown, wherein a typical pressurized gas storage tank is filled with a catalyst for use as such Figure 2 , Figure 3 and Figure 4 The reactor pressure vessel shown.

[0112] refer to Figure 7 In this embodiment, the pressure vessel is constructed from a typical gas storage tank, such as those used for storing compressed hydrogen. The system described herein is applicable to all types of hydrogen storage devices, from Type 1 (all-metal) to Type 5 (composite materials).

[0113] In a non-limiting embodiment of the invention, the cylindrical shell of reactor vessel 202 is fitted with a fixed dome or end cap 204 at each end. One end cap of the reactor vessel is equipped with a collar 223 and a nozzle 215 for connecting a valve 224 and / or valve piping 225 for fluid inlet and outlet. The pressure vessel shell is completely or partially filled with a catalyst bed 203 between the pressure vessel ends. In a preferred embodiment, catalyst filling is completed through the tank nozzle after the cylinder is manufactured, but before the valves or piping are installed. A grid, baffle, perforated, or slotted cover 217 of some form is provided near or above the nozzle to prevent the catalyst from leaving the pressure vessel or clogging the gas outlet during operation.

[0114] In one non-limiting embodiment, the catalyst grid 217 is positioned around the piping 225, which is typically screwed into the nozzle of a cylinder or tank. In some non-limiting embodiments, a portion of the valve piping 225 has a reduced diameter to allow for a sleeve of the grid 217 to be positioned around that portion. This allows gas to enter along the piping at more than one location, preventing catalyst particles from clogging the piping (which could occur with a single outlet without a grid). In this non-limiting embodiment, the narrower section of the piping and the grid are designed to be smaller than the inner diameter of the cylinder nozzle to allow for installation and removal after the cylinder is manufactured.

[0115] The multi-container reactor system described in this invention enables the use of standard high-pressure gas storage cylinders (Type 1 to Type 5) because the use of circulating "static gas catalysis" allows for higher overall processing rates using small reactor vessels with a single inlet / outlet nozzle, without the need for large, custom-designed reactor vessels.

[0116] Figure 8 This is a process flow diagram of a non-limiting example of an ammonia production system, illustrating how the invention interacts with other parts of the system. As those skilled in the art will understand upon reading this disclosure, the chemical reactor system of the present invention can be conventionally integrated into gas synthesis systems other than ammonia in a similar manner.

[0117] refer to Figure 8In this non-limiting embodiment of the ammonia production system of the present invention, hydrogen and nitrogen feed gases are supplied to system 801 and mixed with circulating unreacted feed gas 820 before being fed into feed gas compressor system 802. In one non-limiting embodiment, feed gas compressor 802 may be driven by variable speed motor 804 and controlled by flow controller 803 at compressor outlet. In some non-limiting embodiments, hydrogen and nitrogen may be supplied to gas compressor system 802 through separate inlet manifolds and compressed sequentially; other embodiments may use separate compressors for each reactant feed gas.

[0118] The operating pressure of the reactor system is typically controlled by a pressure controller within the synthesis reactor unit 200; in a non-limiting embodiment, this operating pressure is controlled by a flow controller 803 of the compressor 802 and thus by an output pressure regulated via a motor control 804. Details of a non-limiting embodiment are provided below. Figure 9 As shown in the image.

[0119] The pressurized feed gas is passed through an optional feed gas heat exchanger 805 to heat or cool the feed gas to a desired temperature as needed. In one non-limiting embodiment, a temperature controller 806 controls a bypass 807 that bypasses the feed gas heat exchanger to optimize the temperature of the feed gas entering the chemical reactor system 200; the reactant gas is further heated within the gas synthesis reactor system 200. In some non-limiting embodiments, the lower operating temperatures required for the longer residence time in a quasi-batch reactor system allow the feed gas to be heated through a gas compression stage 802 without the need for a preheater 805. In other non-limiting embodiments, the reactor within the system is jacketed or otherwise constructed (e.g., as... Figure 6 The heat is individually applied, and no preheater 805 is required.

[0120] The products within the synthesis reactor system 200, as well as any unreacted feed gases, are primarily cooled by ambient temperature while still remaining in the reactor (to convert the products from a gaseous phase to a liquid phase), but additionally, they may also be cooled or subcooled in the product gas cooler 809. In a non-limiting embodiment, this could be an air cooler driven by a variable drive motor 812, which is controlled by a downstream temperature controller 811.

[0121] The cooled product fluid is passed to a gas-liquid separator 813, where the liquid is separated from unreacted hydrogen and nitrogen. The liquid level in the gas-liquid separator is controlled by a level controller 814 with a level control valve 815; the liquid ammonia product exits the system 816.

[0122] In some non-limiting embodiments of the invention, the pressure of the system downstream of reactor system 200 (including the product gas-liquid separator) is controlled by pressure controller 817 and control valve 818, wherein the operating conditions (pressure and temperature) of the separator are set to ensure that ammonia is liquid while any unreacted hydrogen and nitrogen are in a gaseous state. The unreacted hydrogen and nitrogen are recycled back to the inlet feed gas compressor 820.

[0123] In this non-limiting embodiment of the invention, within an ammonia production system, reactor system 200 receives data and controls the setpoints of feed gas compressor flow control 803, feed gas heat exchanger bypass temperature controller 806, and downstream system pressure 810. As a non-limiting example, reactor system 200 can reduce reactor residence time or vice versa by increasing the compressor flow setpoint in interaction with compressor flow controller 803. Similarly, when system throughput decreases and reactor residence time (and therefore reaction conversion rate) increases, reactor system 200 can decrease the feed gas heater temperature control setpoint to reduce the feed gas inlet temperature.

[0124] Further details of the control systems of various non-limiting embodiments of the present invention are provided in Figure 9 Listed in Figure 9 As shown Figure 2 A process flow diagram of a non-limiting embodiment of the control system of the temperature swing reactor described above.

[0125] refer to Figure 9 In this non-limiting embodiment of the ammonia production system, the flow of gas through multiple pressure vessel reactors 202a–n is controlled by a local system controller 930 using a series of inlet mechanisms 206a–n and outlet mechanisms 207a–n, as well as various sensors 925, in conjunction with inputs from a remote controller 931.

[0126] This non-limiting embodiment of the invention includes two separate inlet manifolds 201a and 201b, as shown below. Figure 4 The alternative embodiments of the present invention may include only a single inlet manifold (e.g. Figure 2 (as described).

[0127] During normal operation, pressurized synthesis feed gas is supplied to inlet manifolds 201a and 201b. The flow rate and temperature of the fluid entering the system are set by upstream system controllers 920a, 920b, 921a, and 921b in conjunction with input from the local system controller 930. Flow rate and pressure at inlet manifolds 201a and 201b are monitored by pressure transmitters 922a and 922b and flow transmitters 920a and 920b to determine whether the flow rate entering the system matches the system capacity. For example, an increase in inlet manifold pressure will notify the local controller 930 to lower the output flow rate setpoint of any upstream compression system in the flow controller 920.

[0128] In a non-limiting example sequence, the reactor is first filled with hydrogen and then with nitrogen (e.g.) Figure 4 Once the inlet manifold 201a for hydrogen reaches the operating pressure, the local controller 930 opens the hydrogen inlet valve 206a on the first reactor 202a, allowing hydrogen to flow into that individual reactor and increasing the internal pressure within it. The temperature of the hydrogen in the manifold will approach the desired reactor operating temperature, approximately 200–300°C, depending on the efficiency of the upstream compression system.

[0129] In some non-limiting embodiments, the local controller 930 can measure reactor conditions via sensors such as inlet pressure 925a, manifold temperature, reactor temperature 925a, and gas flow rates 920a, 920b to the reactor; using this data, it calculates the remaining time required to fill the reactor with fresh synthesis gas. Inlet valve 206a is programmed to close once the reactor operating pressure has been reached; the valve begins to close completely at the target operating pressure. When inlet valve 206a closes on the first reactor 202a, the system begins to open inlet valve 206b on the second reactor 202b. This sequence is repeated for reactors 202c, etc., until the last reactor 202n is filled; this completes a single filling cycle. In some embodiments, once each cycle is complete, the first reactor 202a is emptied and refilled using the same technique, depending on the residence time required for filling, reaction, and system cooling.

[0130] When a given reactor (202a in this example) is filled with sufficient hydrogen from manifold 201a to reach the operating pressure (and valve 206a is closed), nitrogen can be gradually introduced into the reactor by opening valve 210a. Once nitrogen is added to the reactor filled with hot hydrogen, an exothermic reaction will begin, releasing heat as ammonia is produced, resulting in an increase in temperature of the reactants, products, catalyst, and reactor vessel.

[0131] Some of the heat generated by the exothermic reaction will be dissipated into the environment through the reactor walls, depending on the reactor materials, design, and any insulation. The reactor temperature must be maintained high enough to sustain the reaction, but low enough to achieve a good equilibrium conversion. Nitrogen is added to the reactor at a controlled rate to maintain the temperature at the desired level; it can be added continuously, in pulses, or otherwise. For ammonia synthesis, a product-to-reactant molar ratio of 0.5 means that the pressure in the adiabatic system will decrease as the reaction proceeds; therefore, nitrogen can be added to maintain sufficient operating pressure.

[0132] The local controller 930 monitors the reaction progress via temperature and pressure measurements 925a–n; some non-limiting embodiments of the invention may include more than one temperature indicator to ensure accurate monitoring over the entire reactor length. Nitrogen inflow into the reactor is controlled to maintain a desired set of operating conditions. Some non-limiting embodiments of the invention may initially introduce a large amount of nitrogen to induce a high temperature (and thus a high initial reaction rate), subsequently allowing the reactor to cool slightly at the end of a batch production cycle and improving the equilibrium conversion.

[0133] Once the reaction has proceeded to the desired point (e.g., reaching equilibrium conversion), the nitrogen inlet valve closes, the reaction slows down, and eventually, because the heat generated by the exothermic reaction is less than the heat lost to the environment, the reactants, products, catalyst, and reactor vessel begin to cool. When the reactor temperature drops to the critical temperature (approximately 132°C) or below the ammonia dew point temperature at a given internal pressure, the liquid ammonia product will condense within the reactor. The liquid will condense towards the bottom of the reactor, allowing it to drain into outlet manifold 209.

[0134] The venting reactor (e.g., the first reactor 202a shown) includes opening the outlet valve 207a for a sufficient time to allow as much liquid ammonia as possible to leave, while preventing unreacted gas from escaping. Some non-limiting embodiments may include a level measurement system on the reactor. Figure 9 (Not shown in the diagram) so that the outlet valve is closed once a low liquid level is reached. Other non-limiting embodiments may use algorithms to predict the liquid level and venting rate. Any gas released with the ammonia liquid will be recovered through a gas / liquid separator located downstream of the reactor, operating at a lower pressure.

[0135] As liquid ammonia leaves the reactor, the pressure inside the reactor decreases; during the venting process, the temperature of the catalyst and the reactor body may decrease due to the reduction in pressurized gas (depending on the hydrogen content in the unreacted gas, due to the reverse Joule-Thomson effect). Once the reactor has been vented as much liquid ammonia as possible, the refilling process described above can be restarted. Some non-limiting embodiments of the invention may have sufficient reactor volume (or number of reactors) to store all the hydrogen available from a given upstream hydrogen production system and from available daily energy sources. In this non-limiting embodiment, once a given reactor is filled to the desired operating pressure, only sufficient nitrogen is added to maintain the desired operating temperature, allowing the reaction to proceed at a slower pace during periods of low energy availability (e.g., at night for solar energy systems), thereby improving the equilibrium conversion rate. In this operating scenario, reactor refilling only occurs when sufficient energy is available for hydrogen production (e.g., after sunrise for solar energy systems).

[0136] Some non-limiting embodiments may use different operating pressures between different reactors to optimize ammonia production and equilibrium conversion. Some non-limiting embodiments may use some reactors to store hydrogen at high pressures while using other reactors to produce ammonia at lower operating pressures. In one non-limiting example, reactor 202a is filled with hydrogen to 700 bar without adding nitrogen, while reactor 202b is filled with hydrogen to 250 bar and nitrogen is introduced to produce ammonia. Once reactor 202b has completed a fill, react, and vent cycle, the reactor pressure will be below the desired operating pressure of 250 bar; during compressor shutdown periods, gas in reactor 202a can be allowed to pressurize the hydrogen inlet manifold 201a by opening valve 206a, and then refill reactor 202a. This operation can be repeated until the internal pressure of reactor 202a has decreased sufficiently to allow it to operate as a reaction vessel (i.e., introduce nitrogen to produce ammonia). Some non-limiting embodiments may use a portion of their reactor vessel for high-pressure hydrogen storage and the remainder for ammonia production.

[0137] Some non-limiting embodiments of the system may have additional heat transfer mechanisms, such as those shown on a container 202n, such as a hollow outer pipe 220 or a sleeve or jacket on the reactor, which is filled with a heat transfer fluid and connected to a cooling or heating circuit to achieve active reactor temperature control. The heat transfer jacket is provided with an inlet piping system 221, an outlet piping system 222, and a valve control device 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 a portion of the reactors are equipped with the active cooling mechanism. This active cooling system can also be used to rapidly cool products once the desired reaction progress has been achieved, or to heat the reactor during system startup.

[0138] To operate the reactor heat transfer system, the local controller 930 opens the heat transfer medium control valve 224 to ensure that the heat transfer medium flows at a sufficient rate, thereby controlling, raising, or lowering the reactor temperature. In some non-limiting embodiments, an active heating or cooling system can be used to maintain a constant reactor temperature (isothermal operation). The local controller 930 can be configured to activate the active heat transfer system to cool the reactor or slow the rise in reactor temperature once a given temperature has been reached. This allows the equilibrium conversion rate to exceed that achievable in purely adiabatic operation, where the reactor contents must be discharged at a given temperature to maintain the reactor and catalyst temperatures below a certain value (e.g., the catalyst sintering temperature).

[0139] Some non-limiting embodiments of the system may include connecting a local controller 930 to a remote controller 931, which receives data from and transmits data to multiple systems operating in parallel. In some non-limiting embodiments, the remote controller may be cloud-based. The remote controller 931 may be used to collect data from non-system-specific sources, such as weather tracking systems or databases, performance data from other nearby operating reactor systems, or local renewable energy demand curves, and utilize these inputs to predict desired reactor system performance conditions or setpoints. Some non-limiting embodiments of the system may use artificial intelligence, either within or through the remote controller 931, to help generate predictive control setpoints for the local controller 930; other non-limiting embodiments may leverage the centralized computing power provided by the remote controller to achieve a lower-cost local controller.

[0140] Figure 10This is a process flow diagram of a non-limiting embodiment of the present invention for use in an ammonia synthesis system, which enables production to be carried out during periods of low power availability (e.g., nighttime chlorine production on a solar-powered system). As those skilled in the art will understand upon reading this disclosure, this process using the chemical reactor system of the present invention can be conventionally applied in a similar manner to other gas synthesis processes besides ammonia.

[0141] refer to Figure 10 In this non-limiting embodiment of the ammonia production system using the present invention, the compression system 802 is supplied with hydrogen 1001 and nitrogen 1002 feed gases via separate manifolds. The hydrogen feed gas source (typically from some water electrolysis system) is combined with circulating unreacted feed gas 820. In one non-limiting embodiment, the feed gas compressor 802 is driven by a variable-speed motor 804 and controlled by a flow controller 803 at the compressor outlet. The non-limiting embodiment shown herein uses a single compressor alternately for hydrogen and nitrogen; some non-limiting embodiments may use a separate compressor for each reactant feed gas.

[0142] When electricity is available, hydrogen (generated upstream in this illustration) is supplied via hydrogen manifold 1001 to feed gas compressor 802, directed to reactor manifold 206 for hydrogen, and used to fill reactor 230 for ammonia in series, parallel, or a combination thereof. In this non-limiting embodiment, the reactor vessel is a standard hydrogen storage tank filled or partially filled with ammonia synthesis catalyst. The hydrogen storage tank is inverted to ensure that a single inlet and outlet nozzle is located at the bottom of the tank, thus eliminating the need for an internal riser to discharge liquid ammonia. Other embodiments may use an internal riser in conjunction with a non-inverted tank.

[0143] Once sufficient hydrogen has been pressurized and stored within the reactor, and while power is still available, nitrogen (upstream in this diagram) is produced and delivered via a dedicated nitrogen compression manifold 1002 to a compressor, where it is compressed in a feed gas compressor 802, directed to a reactor manifold 210 for nitrogen, and used to fill the nitrogen storage cylinder 1010. The nitrogen is compressed to a pressure significantly higher than the normal reactor operating pressure so that it can flow from the storage cylinder 1010 into the temperature swing reactor 230 without further compression. Some methods can compress and store nitrogen before hydrogen; systems equipped with dedicated or parallel compressors can optionally perform both tasks simultaneously.

[0144] Once the first ammonia reactor has been adequately filled with hydrogen (along with recirculated unreacted gas) to reach the minimum desired operating pressure, and before the hot compressed gas cools in the reactor, nitrogen can be introduced into the reactor from the 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 exothermic heat released by the ammonia synthesis reaction; the exothermic heat lost from the reactor to the environment should be replaced by the heat released from the synthesis reaction. As ammonia is produced, the pressure inside the reactor will decrease and the temperature will increase; nitrogen can be added based on temperature, pressure, or a combination of both, using feedback or predictive control.

[0145] During periods of low or no power availability (e.g., after sunset on a solar field), nitrogen can be gradually introduced into the reactor to continue ammonia production without the need for continuous compression power. The only power requirement will be used solely for control system 1011 and valve actuators (not shown in this illustration – see [link]). Figure 9 These can also be driven by compressed air or nitrogen. Because systems linked to intermittent renewable electricity have a low capacity factor (typically around 30% capacity factor, 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 will also increase the equilibrium conversion. This invention, using a quasi-batch packed bed reactor, offers this significant advantage over current plug-flow steady-state reactor systems.

[0146] Once the reaction has reached the desired equilibrium conversion, nitrogen feeding into the reactor can be stopped, and the reactor can be cooled while still closed; the pressure may decrease slightly due to the temperature drop. Once the reactor, catalyst, and gas have cooled below the critical temperature of ammonia (or, based on the ammonia partial pressure, bubble point / dew point temperature), the ammonia will become liquid and can be discharged from the reactor into outlet manifold 207. Depending on operating conditions, catalyst, reactor size, reaction rate, and desired equilibrium conversion, multiple temperature swing cycles can be completed during periods when electricity is available (e.g., during the daytime when powered by solar power). The application of the method described herein is not limited to periods of low or no electricity.

[0147] Liquid ammonia exits the reactor via dedicated control valves (not shown) for each reactor and flows to outlet manifold 207. In this non-limiting embodiment, outlet manifolds 817, 818, and 810 are controlled at pressures lower than the reactor operating conditions, meaning that some dissolved or unreacted gases may flash from the ammonia. This liquid is passed to gas / liquid separator 813, from which any unreacted gases are recycled back to compression system 802 via hydrogen feed manifold 1001. The remaining liquid ammonia from the separator, under level control 814, is passed via control valve 815 through liquid outlet manifold 816 to ammonia storage tank (not shown). Depending on efficiency and environmental considerations, some embodiments may forgo the recovery of any unreacted gases during periods of low power and may optionally discharge unreacted gases from gas / liquid separator 813 during periods when compression is unavailable.

[0148] Some non-limiting embodiments of the present invention use high-pressure hydrogen storage tanks (e.g., standard 700 bar type 1 to 5 hydrogen storage tanks), which would allow some reactors to be filled to conditions significantly higher than normal reactor operating conditions (e.g. Figure 9 The pressure (described above) allows the flow from the high-pressure reactor to fill the emptied low-pressure reactor without operating a compression system. Storing hydrogen at higher pressures also allows for a smaller overall reactor system; some non-limiting embodiments may have multiple types of reactors, some designed solely for low-pressure ammonia production, while others are designed for both high-pressure storage and ammonia production.

[0149] This non-limiting embodiment of the chemical reactor system of the present invention, using a temperature swing reactor, allows for longer residence times and slower reaction rates within individual reactors, including cooling the product gas to ambient temperature, below the liquid formation temperature, after reaction equilibrium has been reached. This reactor design of the present invention allows for the extraction of liquid ammonia from the reactor, separating it from the unreacted feed gas, without the need for complex cooling or high recycle ratios.

[0150] Figures 11 to 18 An alternative, non-limiting embodiment of the chemical reactor system 200 of this disclosure is illustrated, which is equipped with the multi-container quasi-batch reactor system 235 of the present invention, having separate inlets for reactants and separate outlets for reaction products.

[0151] refer to Figure 11Multiple simplified reactor vessels 202a, 202b, 202c…202n are connected at each end of the vessel to a common inlet manifold 201 and outlet manifold 209 via piping 205. In one embodiment, each reactor vessel is equipped with an inlet valve 206 and an outlet valve 207. The orientation of the vessels, manifolds, and piping can be optimized based on the properties of the reaction, reactants, catalyst, heat transfer, and other constraints.

[0152] Similar to the temperature swing reactor system described above, each reactor vessel 202 in this system 235 may include a hollow cylindrical section filled with catalyst 203 and equipped with a head 204 at each end. In a non-limiting embodiment, the reactor vessel 202 is made using a section of nominal piping (NPS or DN), while the head 204 is made using standard pipe flanges (e.g., ASME, DIN, or EN). In a non-limiting embodiment, the head 204 at each end of the reactor vessel 202 is equipped with a grid 217 to prevent catalyst from leaving the vessel. In a non-limiting embodiment, the grid is integral with the head gasket (see [link to documentation]). Figure 15 (Details in the text).

[0153] The reactor vessel is individually filled with the synthesis feed gas in such a manner that the dedicated inlet valve 206 and outlet valve 207 of the reactor vessel are opened for a sufficient time and maintained with sufficient overlap, allowing the inflow fluid from the inlet manifold 201 to drain the contents of the reactor vessel into the outlet manifold 209 as it enters the vessel, after which the valves are closed. For systems employing serial intermittent filling, the time required to fill / drain a given reactor vessel is approximately equal to the volume of that reactor vessel divided by the overall volumetric flow rate through the reactor system.

[0154] For a reactor vessel system operating in a serial filling manner, each reactor is filled sequentially in the same manner, with some overlap in valve opening between reactors to ensure continuous flow at the inlet and outlet manifolds (as required by upstream compression systems or other constraints); the inlet and outlet valves of each reactor remain closed unless a particular reactor is being filled. In a non-limiting example sequence, once the last reactor 202n has been filled, the first reactor 202a is refilled, thereby discharging the reaction products into the outlet manifold 209, thus maintaining continuous flow through the overall system. Therefore, the non-moving intermittent residence time of each reactor vessel is approximately equal to the individual reactor filling time multiplied by the number of subsequent reactors.

[0155] Through design, the pressure throughout the system remains almost constant, thus eliminating significant pressure differentials across the inlet and outlet valves; furthermore, they do not require a completely impermeable seal when closed. The primary function of the inlet and outlet valves is not pressure bearing, but rather to guide gas in the desired sequence to the desired reactor and ensure minimal residence time within each reactor vessel. This makes the system suitable for multi-port valves, such as… Figure 14 As shown in the image.

[0156] For systems operating in a serially packed configuration, the average residence time is a function of the sum of the catalyst volumes in all reactors divided by the total fluid velocity flowing through the system. For a given flux and target residence time (and thus catalyst volume), the number of serially packed reactors selected for the system is an optimization between the desired non-moving residence time and reactor packing constraints.

[0157] Reactor filling is limited by certain maximum rates, which are determined by acceptable pressure drop across the catalyst bed, limitations on potential catalyst damage or entrainment, or other physical criteria (e.g., the rate at which valves open / close in a filling sequence). For some embodiments of the invention, it is desirable to fill groups of reactors in a parallel manner.

[0158] Figure 12 A non-limiting embodiment of a multi-container quasi-batch reactor system 235 with reverse flow capability is illustrated.

[0159] refer to Figure 12 The illustration shows a non-limiting embodiment of the invention, comprising a plurality of reactor vessels 202a, 202b, 202c…202n, each equipped with a catalyst bed 203 and end caps 204 at each end of the vessel. The end caps 204 are connected via piping 205 to a common inlet manifold 201 and outlet manifold 209, and have additional devices to allow reverse flow through the reactor vessels. Reverse flow through the reactor vessels may be desired for a variety of reasons, including improved heat exchange cycles, better product removal, or increased catalyst utilization efficiency. Reverse flow requires a reversible reactor design as described in this invention; one embodiment… Figure 15 It contains a detailed description.

[0160] As mentioned above Figure 11 In contrast, the additional equipment includes additional manifolds 310 and 311, which connect the inlet manifold 201 and the outlet manifold 209 to the two ends of the reactor vessel 202, respectively. In one embodiment, additional valves 312 and 313 on the inlet manifold and additional valves 314 and 315 on the outlet manifold determine the flow direction through the reactor.

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

[0162] In a non-limiting example of “reverse flow”, valves 312 and 314 are closed, while valves 313 and 315 are open; to fill individual reactor 202a, reactant gas flows from inlet manifold 201 through manifold 310 through valve 207, thereby pushing the reacted product gas through valve 206 through manifold 311 to outlet manifold 209.

[0163] The aforementioned forward and reverse configurations can be used to fill all reactors in the system in the same manner. During system configuration switching (e.g., switching from forward flow to reverse flow, or vice versa), it may be necessary to establish an overlap between the closure of valves 314 and 315 to prevent reactor system bypass.

[0164] Figure 13 A non-limiting embodiment of a multi-container quasi-batch reactor system 235 is illustrated, which has the capability of concurrent reverse flow for individual reactors.

[0165] refer to Figure 13 The illustration shows an embodiment of the invention comprising a plurality of reactor vessels 202a, 202b, 202c…202n, which are equipped with catalyst beds 203 and end caps 204 at each end of the vessels connected by piping 205 to a common inlet manifold 201 and outlet manifold 209, and includes additional equipment to allow selective reverse flow through individual reactor vessels. Figure 13 The non-limiting embodiments shown are compared to Figure 12 The advantage of the illustrated embodiment is that reverse flow can be selected for individual reactors at any time without reversing the flow direction within a shared pipe or manifold. Reverse flow through the reactor vessel may be desired for a variety of reasons, including improving heat exchange cycles, improving reactant mixing, better product removal, or increasing catalyst utilization efficiency.

[0166] Additional equipment includes additional manifolds 310 and 311 that connect the inlet manifold 201 and the outlet manifold 209 to both ends of the reactor vessel. Additional valves 312 and 313 on each reactor connect both ends of each reactor to a common inlet and outlet pipe or manifold. In a non-limiting example, to fill individual reactor 202a, reactant gas flows through manifold 201 via valve 206, thereby expelling the reacted product gas through valve 207 toward outlet manifold 209. Once all other reactors 202b, 202c…202n are filled, reactor 202a can be refilled / emptied in reverse flow; by opening valves 313 and 312, new reactant stream enters from manifold 310, thereby expelling the reacted product gas through valve 312 via manifold 311 toward outlet manifold 209.

[0167] Figure 14 An example of a non-limiting embodiment of the invention is illustrated: a multi-container quasi-batch reactor system 235 that uses multi-port valves and has individually selectable reverse flow capability.

[0168] refer to Figure 14 The illustration shows a non-limiting embodiment of the invention having multiple reactor vessels 202a, 202b, 202c...202n, which are equipped with catalyst beds 203, and end caps 204 at each end of the vessel are connected by piping 205 to a common inlet manifold 201 and outlet manifold 209, and multi-port valves are used to allow selective reverse flow through the individual reactor vessels. Figure 14 The non-limiting embodiments shown are compared to Figure 13 The advantage of the illustrated embodiment is that reverse flow can be selected for individual reactors at any time, while still using only a single valve or mechanism at the end of each reactor for this purpose.

[0169] In a non-limiting example, to fill individual reactor 202a, reactant gas flows through manifold 201 through valve 206, which is positioned to connect inlet manifold reactor line 201 to the reactor via inlet manifold 506; in this position, the connection between line 506 and outlet manifold 311 is established. The inflowing gas pushes any product gas through line 505 to valve 207, which opens toward outlet manifold 209 and closes toward inlet manifold 310. Once all the remaining reactors 202b, 202c…202n are filled, reactor 202a can be refilled / emptied in reverse flow; by changing the position of valve 207, line 505 is opened toward inlet manifold 310 and closed toward outlet manifold 209; similarly, valve 206 is positioned to open line 506 toward outlet manifold 311 and close inlet manifold 201. The new reaction stream enters from manifold 310 via valve 207, thereby pushing the reacted product gas through valve 206 towards outlet manifold 209 via manifold 511.

[0170] This non-limiting embodiment of the invention can also be used to achieve flow between reactors using parallel manifolds. In one example scenario, reactor 202a vents to reactor 202b via an outlet manifold. On reactor 202a, valve 206a is positioned to connect inlet manifold 201 to its line 506, while valve 207a is positioned to connect its line 505 to outlet manifold 209. Valve 314 is closed, and valve 315 is open to outlet 209. On reactor 202b, valve 206b is positioned to connect manifold 511 to its line 506; valve 207b is positioned to connect its line 505 to manifold 209. Inflow gas flows down from inlet manifold 201 through pipe system 506a and valve 206a through reactor 202a, and through pipe system 505a and valve 207a to manifold 209. Subsequently, gas flows upward from line 509 through its valve 207b and piping system 505b through reactor 202b, and then out through its piping system 506b and valve 206b to outlet manifold 511. This process can be repeated and reversed in each fill cycle by alternately setting the open / closed positions of valves 512 and 513. In some non-limiting embodiments of the invention, a single multi-port valve may replace valves 512 and 513. In the above non-limiting embodiments, a small pressure differential may be required between the inlet manifold and the outlet manifold.

[0171] Figure 15 Examples are shown that are used in this invention and in Figure 11 , Figure 12 , Figure 13 and Figure 14 The diagram shows a cross-sectional view of a non-limiting embodiment of an individual reactor pressure vessel.

[0172] refer to Figure 15 In this non-limiting embodiment, reactor 202 is constructed of a cylindrical shell fitted with flanges 216 at each end, to which end caps 208 are attached. In one non-limiting embodiment, end caps 208 are removable and identical at each end. The end caps are equipped with components 215 (e.g., nozzles) for connecting piping systems for fluid inlet and outlet. Reactor 202 is filled with a catalyst bed 203 between the end caps; catalyst retention devices 217 or grids located at each end prevent the catalyst from leaving the pressure vessel during operation. In one non-limiting embodiment, the catalyst grid is located between flanges 216 and end caps 208; in another non-limiting embodiment, the grid may be integrated with a gasket forming a seal between the pressure vessel flanges and end caps. To reduce the cost and requirements of custom design, manufacturing, and testing, the reactor vessel may be constructed using a section of nominal piping (NPS or DN), while the flanges and end caps (605) may be constructed using standard piping flanges (e.g., ASME, DIN, or EN). The multi-container quasi-batch reactor system described in this invention enables the use of nominal piping and standard flanges.

[0173] Figure 16 A cross-sectional view of a non-limiting embodiment of an individual reactor pressure vessel used in the present invention is shown, which includes an active heat transfer system.

[0174] refer to Figure 16 This illustrates a non-limiting embodiment of an individual reactor vessel used in the present invention, which is similar to... Figure 15 However, it incorporates an active heat transfer system. For example... Figure 15 As shown, the reactor pressure vessel is constructed of a cylindrical shell with flanges 216 at each end, to which end caps 208 are attached. The end caps of the pressure vessel are equipped with components 215 (e.g., nozzles) for connecting piping systems for fluid inlet and outlet. A catalyst bed 203 is filled between the pressure vessel end caps within the pressure vessel shell; catalyst retainers 217 or grids located at each end prevent catalyst from leaving the pressure vessel during operation.

[0175] In one non-limiting embodiment, the hollow external conduit 220 is equipped with an inlet nozzle 221 and an outlet nozzle 222, and covers a portion of the cylindrical shell. The heat transfer medium flows into the external conduit 220 via nozzle 221, where it contacts the pressure vessel shell. In a non-limiting embodiment for reactor cooling, the cooled heat transfer medium is transferred via nozzle 221 to the heat transfer system, where it is heated to cool the pressure vessel 202 and its contents. The flow of the heat transfer medium can be continuously controlled or intermittently controlled using a valve (not shown) at the outlet. In some embodiments, this additional heat transfer medium can be used for thermal inertia during intermittent operation, even if the heat transfer medium does not flow during normal operation.

[0176] Figure 17 The process flow diagram is a non-limiting example of an ammonia production system, illustrating how the invention interacts with other parts of the system. As those skilled in the art will understand upon reading this disclosure, this process using the chemical reactor system of the invention can be conventionally applied in a similar manner to the synthesis of other gases besides ammonia.

[0177] refer to Figure 17In this embodiment of the ammonia production system, hydrogen and nitrogen feed gases are supplied to system 801 and mixed with circulating unreacted feed gas 820 before being fed into feed gas compressor system 802. In one embodiment, feed gas compressor 802 may be driven by variable speed motor 804 and controlled by flow controller 803 at compressor outlet. The pressurized feed gas is passed through feed gas heat exchanger 805, which heats the feed gas to a desired temperature using hot gas leaving reactor system 200 of the invention. In one embodiment, temperature controller 806 controls bypass 807 that bypasses the feed gas heat exchanger to optimize the temperature of the feed gas entering reactor system 200; product gas is further heated within reactor system 200 of the invention. Product gas leaving reactor system 235, along with any unreacted feed gas, is cooled in feed gas heat exchanger 805 and subsequently further cooled in product gas cooler 809. In a non-limiting embodiment, the cooler may be an air cooler, driven by a variable-speed drive motor 812 and controlled by a downstream temperature controller 811. The pressure of the reactor system is controlled by a pressure controller 810 and a control valve 818; in a non-limiting embodiment, this is located after the product gas cooler 809. The cooled product gas is passed to a gas-liquid separator 813, where the liquid is separated from unreacted hydrogen and nitrogen. The liquid level in the gas-liquid separator is controlled by a level controller 814 and a level control valve 815; the liquid ammonia product exits the system 816. The pressure of the product gas-liquid separator is controlled by a pressure controller 817 and a control valve 818, wherein the operating conditions (pressure and temperature) of the separator are set to ensure that ammonia is liquid while any unreacted hydrogen and nitrogen are in a gaseous state. The unreacted hydrogen and nitrogen are recycled back to the inlet feed gas compressor 820.

[0178] In this non-limiting embodiment of the ammonia production system, reactor system 200 receives data and controls the setpoints of feed gas compressor flow control 803, feed gas heat exchanger bypass temperature controller 806, and system pressure controller 810. As a non-limiting example, reactor system 200 can interact with compressor flow controller 803 by increasing the compressor flow setpoint to shorten the intermittent residence time (or vice versa). Similarly, when the system throughput decreases and the intermittent residence time (and therefore the reaction conversion rate) increases, reactor system 200 can decrease the feed gas heater temperature control setpoint to reduce the feed gas inlet temperature.

[0179] Further details of various embodiments of the control system of the present invention are in Figure 18 Overview in Chinese.

[0180] Figure 18 Is it like this? Figure 11The process flow diagram shown is a non-limiting embodiment of the control system of the chemical reactor system described above.

[0181] refer to Figure 18 In this non-limiting embodiment of the ammonia production system, the gas is controlled by a local system controller 930 through a series of inlet mechanisms 206a-n and outlet mechanisms 207a-n, as well as various sensors, in conjunction with inputs from a remote controller 931, via a multi-container batch reactor (which includes multiple pressure vessel reactors 202a-n equipped with catalyst beds 203a-n).

[0182] During normal operation, pressurized synthesis feed gas is supplied to inlet manifold 201. For example... Figure 17 The flow rate and temperature of the fluid entering the system are set by upstream system controllers 920 and 921 in conjunction with input from the local system controller 930. The flow rate and pressure at the inlet manifold 201 are monitored by a pressure / flow transmitter 922 to determine that the flow rate entering the system matches the system capacity; an increase in the inlet manifold pressure will notify the local controller 930 to lower the output flow rate setpoint of any upstream compression system.

[0183] When gas arrives and the pressure increases, the local controller 930 opens the inlet valve 206a and outlet valve 207a on the first reactor 202a, allowing gas to flow into the individual reactor and discharging any product gas to the outlet manifold 209. In a non-limiting embodiment, the local controller 930 is provided with characteristics of the reactor 202a (e.g., gas space volume) and can measure reactor conditions such as inlet pressure 922 and temperature 921, outlet pressures 925, 926, reactor temperatures 924, 927, and the gas flow rate through the reactor; using this data, it calculates the time required to fill the reactor with fresh synthesis gas.

[0184] Inlet valve 206a and outlet valve 207a are programmed to close once the product gas has been discharged; the valves begin to close to ensure complete closure after most 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 escaping to the outlet manifold. While the valve on the first reactor 202a is closing, the system begins to open valves 206b, 207b on the second reactor 202b. This sequence is repeated for reactors 202c, etc., until the final reactor 202n is filled; this completes one filling cycle. Once each cycle is complete, the first reactor 202a is refilled / emptied using the same technique.

[0185] As each reactor is filled and subsequently shut down to allow the exothermic reaction to proceed, heat is released with the production of ammonia, causing a rise in the temperature of the reactants, products, catalyst, and reactor vessel. Some non-limiting embodiments of the reactor system may operate adiabatably, without significant or dedicated heat or material removal during the reaction. A local controller 930 monitors the reaction progress via measurements of temperature 924 and pressure 925; some non-limiting embodiments of the invention may have more than one temperature indicator to ensure accurate monitoring of the entire reactor length. Once the reaction has proceeded to the desired point, the reactor is refilled using the same sequence described above, thereby flushing the hot reactor contents toward the outlet manifold 209.

[0186] During refilling, the incoming cooler feed gas lowers the temperature of the catalyst and reactor body; simultaneously, the incoming synthesis gas is heated upon entering the reactor. The local controller 930 ensures that the setpoint of the inlet manifold gas temperature controller 921 is low enough that sufficient cooling in each fill cycle is sufficient to offset the heating of the reactor during the batch reaction. Simultaneously, the local controller 930 sets the reactor residence time to ensure that the maximum temperature reached within the reactor does not continue to rise over time. In some non-limiting embodiments of the system, if the reactor temperature increases over time, the local controller 930 may increase the overall flow rate 920 through the system to shorten the residence time in each reactor cycle (and thereby reduce the reaction conversion and heat release). The local controller 930 may also shorten or lengthen the residence time by using fewer or more reactors in a given fill cycle.

[0187] To accommodate various catalyst properties (including different catalyst materials, sizes, shapes, and aging degrees) and different reactor sizes, some embodiments of the reactor system allow for parallel intermittent reactor cycles, each with various residence times and fill rates. This ensures that once the maximum temperature of a given reactor is reached, the local controller 930 can refill reactors that are about to reach their temperature limits without waiting for the entire cycle in which all reactors have been sequentially filled.

[0188] Some non-limiting embodiments of the system may have an additional heat transfer mechanism (as shown) on a container 202n, such as a hollow outer pipe 220, or a sleeve or jacket on the reactor, which is filled with a heat transfer fluid and connected to a cooling or heating circuit to achieve active reactor temperature control. The heat transfer jacket has an inlet piping system 221, an outlet piping system 222, and a valve control device 224 to control 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 a portion of the reactors are equipped with the active cooling mechanism. The active cooling system can also be used for reactor heating during system startup. To operate the reactor heat transfer system, the local controller 930 opens the heat transfer medium control valve 224 to ensure that the heat transfer medium flows at a sufficient rate to keep the reactor temperature constant (isothermal operation); the local controller 930 can configure the active heat transfer system to cool the reactor or slow the rise in reactor temperature once a given temperature has been reached. This allows the equilibrium conversion rate to exceed that of purely adiabatic operation, in which the contents of the reactor must be discharged at a given temperature to maintain the reactor and catalyst temperatures below a certain value.

[0189] Some non-limiting embodiments of the system may include connecting a local controller 930 to a remote controller 931, which receives data from and transmits data to multiple systems operating in parallel. In some embodiments, the remote controller may be cloud-based. The remote controller 931 may 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 demand curves, and use these inputs to predict desired reactor system performance conditions or setpoints. Some embodiments of the system may use artificial intelligence, either within or through the remote controller 931, to help generate predictive control setpoints for the local controller 930; other embodiments may leverage the centralized computing power provided by the remote controller to achieve a lower-cost local controller.

[0190] Several forms of batch reactors, as well as parallel batch reactors, have been previously used in wastewater systems, bioreactors, and laboratory testing; however, no system has yet been designed to allow batch reactors to be used in production-scale gas-phase catalytic reactions (using solid catalysts), fixed-bed reactors, or high-pressure gas systems, as required for industrial-scale ammonia synthesis. The current speed, accuracy, and level of predictive computerized automation required to achieve reliable output and safe system operation have spurred new approaches to reactor design, apparatus, and automated process control, as described in this invention.

[0191] The chemical reactor system of this invention offers multiple advantages for gas synthesis.

[0192] For example, reactants can be added to the reactor individually and at a controlled rate to allow control of the reaction rate and reactor temperature to suit the available time when powered by intermittent renewable energy. According to this embodiment, an intermittent reactor is used, allowing hydrogen to be “stored” at high pressure within the reactor until the time is suitable for ammonia production; a non-limiting example of this is: hydrogen production is carried out during the day and stored at high pressure within the reactor, followed by ammonia production after the peak period of renewable electricity.

[0193] The ability to add reactants individually also allows for the use of stoichiometric ratios different from the standard 3:1 for ammonia reactions, thereby increasing the equilibrium conversion according to Le Chatelier's principle. The ability to remove liquid products without unreacted feed gas allows for the use of stoichiometrically unreasonable feed gas ratios without the penalty of increased compression due to high recycle rates.

[0194] Furthermore, each reactor in the system can be a pressure vessel containing a catalyst suitable for gas synthesis (e.g., ammonia synthesis). In a non-limiting embodiment, each reactor vessel is constructed from a standard hydrogen storage tank containing the catalyst and equipped with an opening at one end. In a complete system, each individual packed-bed reactor is connected to a common inlet and outlet manifold and is equipped with one or more mechanisms to control the entry of reactants into the inlet manifold and the discharge of reaction products into the outlet manifold; in a preferred embodiment, these mechanisms are automated to achieve individual control of conditions within a single reactor while coordinating operation with all reactors in the system. By opening and closing these mechanisms in the correct sequence in multiple reactors, individual vessels are allowed to operate as batch reactors with controlled residence times or GHSVs, while the overall system of reactors operates at a stable and continuous flux. More specifically, operating the catalytic reactor as a batch reactor allows for “non-moving,” “stationary,” “non-flowing,” or “static” residence times of reactants and products within the catalyst bed; for a given reactor vessel in this invention, this time is the time interval between bulk filling and emptying. During periods when the inlet and outlet mechanisms are closed, the reactant gases are allowed to self-distribute throughout the reactor, rather than being propelled forward along the reactor axis (towards the outlet) as in plug flow reactors or other steady-state reactors. The technique described herein is referred to as “static gas catalysis” or “non-flowing gas catalysis” and allows the catalytic reaction to be distributed more uniformly throughout the catalyst bed without the need for an internal fluid inlet distribution mechanism or a large gas volume at the reactor inlet; simultaneously, it allows the reaction, and any heat it releases or absorbs, to diffuse throughout the entire volume of the catalyst bed.

[0195] For a system in which all reactors are filled sequentially one after another, the non-moving intermittent or "static" residence time of each reactor vessel is approximately equal to the individual reactor's fill time multiplied by the number of subsequent reactors in the system. For a given desired maximum residence time, a "cycle" will be defined as a process of filling all reactors in a given series of reactors and then returning to refill / drain the first reactor.

[0196] At the start of the batch sequence, the internal pressure of each reactor is lower than the pressure in the inlet manifold; as reactants enter the reactor from the inlet manifold, the internal pressure of the reactor increases. Once the desired reaction pressure is reached and sufficient reactants have been added to the reactor vessel, the inlet mechanism is closed to allow the reaction to proceed.

[0197] In some non-limiting embodiments of the invention, the ratio of reactants entering the container is modified to control the reaction progress and the heat released through the reactor container walls. One non-limiting example of this is that the container is first filled to the desired pressure using only hot, compressed hydrogen, and then nitrogen is added sufficiently gradually so that the heat generated by the exothermic reaction matches the heat released to the atmosphere through the reactor walls. In this embodiment, by controlling the amount of nitrogen entering to match the heat released from the reactor to the atmosphere, the amount of ammonia produced is controlled, and consequently the heat released by the exothermic reaction is controlled, keeping the reaction temperature constant. An additional advantage of this embodiment of the invention is the utilization of Le Chatelier's principle: a high concentration (or excess) of reactants drives the reaction toward the product side, thereby achieving a higher equilibrium conversion at a given operating temperature and pressure.

[0198] Once the reaction has reached the desired point, the reactant inlet mechanism is closed, stopping the reaction within the reactor vessel and ceasing the release of exothermic heat. The vessel then begins to cool. Once the reactor and its contents have cooled below the critical temperature for the ammonia products, the gaseous products will liquefy. The liquid product can then be emptied from the vessel by opening the mechanism connecting the reactor to the outlet manifold, allowing the liquid product to exit the pressure vessel. As the liquid product is emptied, the internal pressure decreases, allowing the reactor to be refilled with reactant gas once sufficient product has been discharged.

[0199] Depending on the available reaction residence time, some embodiments of the invention can actively modify the operating conditions within the reactor (temperature, pressure, and reactant ratio) to optimize conversion, energy use, or other factors, thereby matching the reaction progress to the available time. One non-limiting example of this is reducing the operating temperature to ensure a slower, more controlled reaction rate and achieve a higher equilibrium conversion. Another non-limiting example is reducing the operating pressure to decrease compression energy requirements, while offsetting the loss of equilibrium conversion due to lower reaction pressure by reducing the reaction temperature or modifying the stoichiometric reactant ratio.

[0200] The filling and evacuation rates of individual reactors within a system are limited by maximum values ​​determined by pressure drop, catalyst entrainment, catalyst damage, or other physical criteria. It is impossible to add an unlimited number of batch reactors to the same cycle while maintaining the same target fill time; this would require reducing the fill time of each individual reactor to near zero seconds. When the fill rate of individual reactors exceeds a certain fill rate, it will be necessary to use multiple reactors filled in parallel (i.e., simultaneously filling a group of reactors). Therefore, this invention allows for parallel filling of a group of reactors to limit the fill rate of individual reactors, and even allows the entire system to operate with reactants entering and leaving the reactors in some form of continuous parallel flow (such as staggered overlapping parallel filling), as required for optimal system performance.

[0201] In the case of parallel or quasi-parallel continuous flow, the external mechanisms, manifolds and associated control systems described in this invention can ensure optimal and controlled distribution of reactant gases among multiple reactors.

[0202] The individual reactors and overall reactor system of the present invention are also designed such that each reactor can be operated in a “quasi-batch” mode by using an automated inlet mechanism, wherein the reactor can be partially filled, refilled / repressurized midway through the reaction, operated at independent temperature and pressure, or filled with reactants of different compositions, thereby potentially optimizing the reaction rate and balancing the conversion.

[0203] Some embodiments of the present invention allow advanced control systems to achieve different residence times for individual or grouped reactors; this effect is achieved through different sequences of reactors filled in series or in parallel. This feature of the present invention allows for the use of different catalyst materials, sizes, or shapes in individual or grouped reactors (which may require different fluid residence times); this feature is also useful for dynamic operating conditions such as cold reactor start-up or changing reactor operating temperatures and pressures.

[0204] Using external mechanisms to allow individual reactors to operate in batch (or quasi-batch) mode allows design engineers to decouple the size constraints of individual reactors from target residence times or GHSV. Using batch mode in catalytic reactors allows for high residence times without significantly increasing reactor length or worrying about radial fluid distribution or plug flow deviation. This enables reactors to be sized to fit in confined spaces while still achieving large residence times without complex internal gas distribution systems, large inlet volumes, or excessive pressure drops over long catalyst bed lengths.

[0205] Operating a properly designed catalytic reactor in a batch (or quasi-batch) mode overcomes the drawbacks of using plug flow reactor vessels at high load conditions (low overall system flux), where current technologies suffer from poor reactant distribution, channeling, catalyst hotspots, and low catalyst utilization efficiency at rates well below the peak design operating point.

[0206] Another advantage of this invention is that by distributing the reaction (and any heat released or absorbed therefrom) throughout the catalyst bed and reactor body, reactor temperature control is simplified, thereby avoiding catalyst hot spots and sintering. In this case, a higher reactor metal to catalyst weight ratio relative to the system's thermal inertia becomes an advantage, thus preventing excessive heating of the fluid and catalyst.

[0207] Another advantage of the invention, particularly when used in green ammonia production systems connected to intermittent renewable energy power sources, is that, due to the use of intermittent or quasi-intermittent operation, system performance (including equilibrium conversion rate) actually increases with the reduction of overall system flux (i.e., a higher load regulation ratio) due to the increased controlled residence time in each reactor vessel; this is the opposite of the current prior art plug flow reactor design.

[0208] Another advantage of some embodiments of the present invention is that the use of a long-cycle batch reactor allows the generated ammonia to be cooled below the critical temperature under high pressure, which allows for the separation of gaseous reactants from liquid ammonia without the need for significant pressure drops or large heat exchangers to cool the ammonia products.

[0209] Another advantage of some embodiments of the invention is that ammonia production can be carried out during periods when no renewable energy is available, such as at night or during periods of no wind or sunlight. In some embodiments, the reactor vessel can be filled during the day, left to produce ammonia at night, and emptied the following morning. In this example of the invention, hydrogen is produced and compressed into an empty or partially empty reactor vessel during periods when energy is available, while nitrogen is produced and stored at high pressure in a separate storage tank. Once the reactor vessel is full (or no longer has intermittent energy available, whichever comes first), the reaction is initiated in the hydrogen-filled reactor vessel by slowly adding nitrogen, as described above. The small amount of electricity required for control can be provided by batteries, or by running the electrolyzer in reverse (using the previously compressed portion of hydrogen), or by using the stored compressed nitrogen for pneumatic control.

[0210] Another advantage of this invention in producing green ammonia using electricity from intermittent renewable energy sources is that operating conditions (pressure and temperature) can be varied to allow the intermittent reaction to proceed at a slower rate, thereby optimizing reaction conversion and overall energy use.

[0211] Furthermore, while using multiple smaller reactors with external gas distribution mechanisms increases the metal / catalyst weight or volume ratio (a high ratio typically implies higher overall system manufacturing costs), the highly simplified reactor described in this invention, particularly when constructed using standard components as described herein, makes the overall system cost competitive. Simultaneously, this invention allows system designers to fully leverage the modularity of the reactor in terms of both throughput and residence time without requiring customized design for each reactor vessel. This allows engineering and manufacturing costs to be distributed across multiple facilities, thereby reducing the average price of each individual system.

[0212] Example

[0213] One embodiment of the present invention relates to a chemical reactor system for gas synthesis, the system comprising: a batch, quasi-batch, or dynamic reactor for gas synthesis, the batch, quasi-batch, or dynamic reactor being formed by one or more individual catalytic reactors; one or more fluid control mechanisms formed by 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 capable of activating the one or more fluid control mechanisms to control the entry of reactants into the chemical reactor system and the exit of reaction products from the chemical reactor system.

[0214] In the aforementioned previous embodiments, the batch, quasi-batch, or dynamic reactor may be a temperature-oscillating gas synthesis reactor.

[0215] In any of the preceding embodiments described above, the one or more individual catalytic reactors may include a single component located at one end to allow fluid to enter and exit the individual reactor and contact the catalyst.

[0216] In any of the preceding embodiments described above, each individual catalytic reactor may have separate inlet and outlet components to allow fluid to enter and exit the individual reactor and contact the catalyst.

[0217] In any of the preceding embodiments described above, the control system may be able to control the reactor inlet and outlet mechanisms in the system via the one or more fluid control mechanisms to facilitate the flow of fluid through the individual catalytic reactors in a serial, parallel, or combined manner, such that the fluid flow through the chemical reactor system is nearly continuous, while the fluid in each individual catalytic reactor is stationary or nearly stationary for a portion of its residence time.

[0218] In any of the preceding embodiments described above, each individual catalytic reactor may include: a cylindrical shell pressure vessel having a pressure vessel head at each end; a catalyst bed located between the pressure vessel heads; a catalyst retainer positioned within at least one of the pressure vessel heads to prevent catalyst from leaving the vessel during operation; and a component for allowing fluid to enter and exit the pressure vessel and contact the catalyst.

[0219] In any of the preceding embodiments described above, a portion of one or more individual catalytic reactors may be used to store hydrogen, nitrogen, ammonia, or other gases.

[0220] In any of the preceding embodiments described above, the batch, quasi-batch, or dynamic reactor for gas synthesis may include a plurality of individual catalytic reactors and additional mechanisms fitted to a common pipe or manifold connecting the individual catalytic reactors to allow backflow into the individual or group of individual catalytic reactors within the same reactor system, while allowing forward flow into other individual catalytic reactors.

[0221] In any of the preceding embodiments described above, the control system may be automated and / or capable of operating individual or grouped catalytic reactors in an intermittent operation mode.

[0222] In any of the preceding embodiments described above, the control system may be automated and / or capable of operating individual or grouped catalytic reactors in continuous, steady-state, or plug flow operation modes.

[0223] In any of the preceding embodiments described above, one or more individual catalytic reactors may be equipped with internal and / or external heat transfer systems to modify the temperature of the reactor during the reaction.

[0224] In any of the preceding embodiments described above, one or more individual catalytic reactors in the individual catalytic reactors may be designed as tube-in-tube heat exchangers.

[0225] In any of the preceding embodiments described above, the control system may be computerized and connected to a remote or cloud-based controller.

[0226] In any of the preceding embodiments described above, the control system may use algorithms, artificial intelligence, or machine learning to optimize the performance of the individual or group of catalytic reactor vessels and the chemical reactor system.

[0227] In any of the preceding embodiments described above, one or more individual catalytic reactors in the individual catalytic reactors may be equipped with a sensor, detector, or controller that transmits information to the control system, thereby enabling the chemical reactor system to operate in a manner that allows for a continuous inflow of reactants and a continuous outflow of reaction products through the chemical reactor system.

[0228] In any of the preceding embodiments described above, the gas synthesis may be ammonia synthesis.

[0229] Another embodiment of the present invention relates to an energy waste reduction system comprising a chemical reactor system of any of the foregoing embodiments, wherein the chemical reactor system is coupled to a variable or intermittent energy production technology.

[0230] Another embodiment of the invention relates to a method for producing gas via a variable or intermittent energy production technology via any of the aforementioned prior embodiments of a chemical reactor system.

[0231] Another embodiment of the invention relates to a method for producing gas by the following steps: supplying a synthesis feed gas to a chemical reactor system of any of the preceding embodiments of the chemical reactor system described above; opening one or more fluid control mechanisms of an individual catalytic reactor or a group of reactors to allow sufficient synthesis feed gas to be delivered to each reactor such that the reactor is filled with the feed gas; once the feed gas is filled, closing the one or more fluid control mechanisms to stop or sufficiently slow the flow of gas in contact with the catalyst to allow the reaction to occur; timing, predicting, and / or monitoring the temperature, pressure, and / or other measurable states within each closed or partially closed reactor to determine the reaction progress; and once the reaction has reached the desired progress, discharging the reaction products.

[0232] Another embodiment of the invention relates to a method for retrofitting an ammonia plant with a synthesis loop, wherein fresh ammonia synthesis gas containing hydrogen and nitrogen is combined with any circulating stream to form a combined ammonia synthesis gas, and the combined ammonia synthesis gas is reacted over a catalyst to form a converted ammonia product gas. The retrofitting method includes the steps of replacing one or more existing ammonia synthesis reactors with a chemical reactor system of any of the preceding embodiments described above, wherein the chemical reactor system has a control system capable of: (i) manipulating one or more batch, quasi-batch, or dynamic reactors and their fluid control mechanisms such that these reactors are sequentially filled with synthesis gas to allow batch or near-batch residence times in each reactor, while having a continuous or near-continuous flow of feed gas through the entire system of reactor vessels; (ii) controlling the temperature of the synthesis feed gas; and (iii) Controlling the operating pressure of the reactor system; installing a feed gas heat exchanger upstream of the chemical reactor system, the feed gas heat exchanger being able to heat the synthesis gas to a target and controlled temperature required for the batch operation of the reactor; installing a heat exchanger and a gas-liquid separator for condensing and recovering ammonia from the reactor effluent stream and forming an ammonia-lean stream; and installing a pressure control system to enable control and manipulation of the operating pressure of the chemical reactor system.

[0233] Another embodiment of the invention relates to a method for producing ammonia from a synthesis gas containing hydrogen and nitrogen, in combination with any circulating stream, via the following steps: supplying synthesis feed gas to a system comprising one or more catalyst-filled pressure vessel reactors, each catalyst-filled pressure vessel reactor being connected at an inlet to one or more manifolds and at an outlet to one or more manifolds, each catalyst-filled pressure vessel reactor being equipped with independently operating mechanisms to control, guide, and stop the flow of fluid through the inlet manifold to the individual vessel and catalyst bed, or the flow of fluid through the outlet manifold to the individual vessel and catalyst bed; opening the control mechanisms of selected catalyst-filled pressure vessel reactors or groups of catalyst-filled pressure vessel reactors to allow sufficient synthesis feed gas to be delivered from its inlet manifold to each catalyst-filled pressure vessel reactor, thereby filling the catalyst-filled pressure vessel reactor with feed gas and pressurizing it to a selected operating pressure; once filled... For the feed gas, the control mechanism located at each end of the selected catalyst-filled pressure vessel reactor or group of reactors is shut off to stop or sufficiently slow the flow of gas in contact with the catalyst, thereby allowing the reaction to occur; the temperature, pressure, or other measurable states within each closed or partially closed catalyst-filled pressure vessel reactor are timed, predicted, or monitored to determine the reaction progress; once the reaction has reached the desired state, conversion, or equilibrium conversion, the one or more catalyst-filled pressure vessel reactors are cooled to below the critical point temperature or dew point temperature of the ammonia product; once sufficiently cooled, the liquid ammonia product collected in the lower portion of the one or more catalyst-filled pressure vessel reactors is discharged, without allowing most of the unreacted gas to escape from the one or more catalyst-filled pressure vessel reactors; and the filling process described above is repeated by adding new synthesis feed gas to any unreacted gas remaining in the one or more catalyst-filled pressure vessel reactors.

[0234] In the aforementioned prior method embodiments, one or more reactants may be introduced sufficiently gradually into each catalyst-filled pressure vessel reactor to allow controlled ammonia production and temperature release, thereby maintaining the desired operating temperature and pressure operating conditions within the individual catalyst-filled pressure vessel reactor.

[0235] In any of the preceding method embodiments described above, one or more of the catalyst-filled reactor vessels may be used to store the reactants at high pressure before the ammonia production process is started in a controlled manner by introducing a second reactant.

[0236] In any of the preceding method embodiments described above, hydrogen and / or nitrogen may be stored at sufficiently high pressure in the one or more catalyst-filled pressure vessel reactors during periods when electricity is available, so that during periods when electricity is unavailable, hydrogen and nitrogen can be transferred to a portion of the one or more catalyst-filled pressure vessel reactors to produce ammonia.

[0237] In any of the preceding method embodiments described above, the one or more catalyst-filled pressure vessel reactors may be sequentially filled with feed gas to achieve intermittent or near-intermittent residence times in each reactor, while having a continuous or near-continuous flow of feed gas through the entire system of the reactor vessel.

[0238] In any of the preceding method embodiments described above, the one or more catalyst-filled pressure vessel reactors may be equipped with sensors, detectors, or controllers that transmit information to one or more control systems, enabling the system formed by the reactor, mechanisms, sensors, and control systems to operate in a manner that allows for a continuous inflow of feed gas and a continuous outflow of products through the overall system of the reactor.

[0239] In any of the preceding method embodiments described above, the one or more catalyst-filled pressure vessel reactors may be equipped with a control system capable of manipulating the reactors and their fluid control mechanisms such that they are sequentially filled with synthesis gas to achieve intermittent or near-intermittent residence times in each reactor, while having a continuous or near-continuous flow of feed gas through the entire system of the reactor vessel.

[0240] In any of the preceding method embodiments described above, the 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.

[0241] In any of the preceding method embodiments described above, the one or more catalyst-filled pressure vessel reactors may be equipped with a control system capable of controlling the operating pressure of the reactor system.

[0242] In any of the preceding method embodiments described above, the one or more catalyst-filled pressure vessel reactors may be equipped with internal or external heat transfer systems to modify the temperature of the reactor during the reaction.

[0243] In any of the preceding method embodiments described above, one or more catalyst-filled pressure vessel reactors in the catalyst-filled pressure vessel reactor may be designed as tube-in-tube heat exchangers.

Claims

1. A chemical reactor system for gas synthesis, the system comprising: A batch, quasi-batch, or dynamic reactor for gas synthesis, wherein the batch, quasi-batch, or dynamic reactor is formed by one or more individual catalytic reactors; One or more fluid control mechanisms, formed by shared pipes and manifolds, for delivering reactants to the chemical reactor system and collecting reaction products from the chemical reactor system; as well as A control system capable of activating one or more fluid control mechanisms to control the entry of reactants into the chemical reactor system and the exit of reaction products from the chemical reactor system.

2. The chemical reactor system according to claim 1, wherein, The intermittent, quasi-intermittent, or dynamic reactor is a temperature-oscillating gas synthesis reactor.

3. The chemical reactor system according to claim 2, wherein, One or more individual catalytic reactors have a single component located at one end to allow fluid to enter and exit the individual reactor and to contact the catalyst.

4. The chemical reactor system according to claim 1, wherein, Each individual catalytic reactor has separate inlet and outlet components to allow fluid to enter and exit the individual reactor and come into contact with the catalyst.

5. The chemical reactor system according to claim 1, comprising a batch, quasi-batch, or dynamic reactor for gas synthesis, wherein the batch, quasi-batch, or dynamic reactor has multiple individual catalytic reactors, wherein, The control system is capable of controlling the reactor inlet and outlet mechanisms in the system via the one or more fluid control mechanisms to facilitate the flow of fluid through the individual catalytic reactors in a serial, parallel, or combined manner, such that the fluid flow through the chemical reactor system is nearly continuous, while the fluid in each individual catalytic reactor is stationary or nearly stationary for a portion of its residence time.

6. The chemical reactor system according to claim 1, wherein, Each individual catalytic reactor includes: A pressure vessel with a cylindrical shell, wherein the pressure vessel has a pressure vessel head at each end; A catalyst bed located between the pressure vessel heads; A catalyst retainer, positioned within at least one pressure vessel head in the pressure vessel head, such that it prevents the catalyst from leaving the vessel during operation; and A component that allows fluid to enter and exit the pressure vessel and come into contact with the catalyst.

7. The chemical reactor system according to claim 1, wherein, One or more individual catalytic reactors are used to store hydrogen, nitrogen, ammonia or other gases.

8. The chemical reactor system of claim 1, comprising a batch, quasi-batch, or dynamic reactor for gas synthesis, said batch, quasi-batch, or dynamic reactor having a plurality of individual catalytic reactors, and Additional mechanisms are fitted into a common pipe or manifold connecting the individual catalytic reactors to enable backflow into individual or grouped individual catalytic reactors within the same reactor system, while allowing forward flow into other individual catalytic reactors.

9. The chemical reactor system according to claim 1, wherein, The control system is automated and enables individual or grouped catalytic reactors to operate in an intermittent mode.

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

11. The chemical reactor system according to claim 1, wherein, One or more of the individual catalytic reactors are equipped with internal or external heat transfer systems to modify the temperature of the reactor during the reaction.

12. The chemical reactor system according to claim 1, wherein, One or more of the individual catalytic reactors are designed as tube-in-tube 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 controller.

14. The chemical reactor system according to claim 1, wherein, The control system uses algorithms, artificial intelligence, predictive control, or machine learning to optimize the performance of the individual or grouped catalytic reactor vessels and the chemical reactor system.

15. The chemical reactor system according to claim 1, wherein, One or more of the individual catalytic reactors are equipped with sensors, detectors, or controllers that transmit information to the control system, thereby enabling the chemical reactor system to operate in a manner that allows for a continuous inflow of reactants and a continuous 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 a chemical reactor system according to claim 1, wherein the chemical reactor system is coupled to a variable or intermittent energy production technology.

18. A method for producing gas via an intermittent energy production technology, the method comprising coupling the intermittent energy production technology with a chemical reactor system according to claim 1.

19. A method for producing a gas, the method comprising the following steps: Supply synthesis feed gas to the chemical reactor system according to claim 1; Open one or more fluid control mechanisms of individual catalytic reactors or groups of reactors to allow sufficient synthesis feed gas to be delivered to each reactor so that the reactor is filled with the feed gas; Once the feed gas has been filled, the one or more fluid control mechanisms are shut off to stop or sufficiently slow the flow of gas in contact with the catalyst to allow the reaction to occur. Timing, prediction, and / or monitoring of temperature, pressure, and / or other measurable conditions within each closed or partially closed reactor are performed to determine reaction progress; and Once the reaction has reached the desired progress, the reaction products are discharged.

20. A method for modifying an ammonia plant unit with a synthesis loop, wherein, Fresh ammonia synthesis gas containing hydrogen and nitrogen is combined with any circulating stream to form a combined ammonia synthesis gas, and the combined ammonia synthesis gas is reacted over a catalyst to form a converted ammonia product gas. The modification method includes the following steps: Replace one or more existing ammonia synthesis reactors with the chemical reactor system according to claim 16, wherein the chemical reactor system has a control system capable of the following operations: (i) Manipulating one or more batch, quasi-batch, or dynamic reactors and their fluid control mechanisms such that the reactors are sequentially filled with synthesis gas to allow a batch or near-batch residence time in each reactor while having a continuous or near-continuous flow of feed gas through the entire system of the reactor vessel. (ii) Controlling the temperature of the synthesis feed gas; and (iii) Controlling the operating pressure of the reactor system; A feed gas heat exchanger is installed upstream of the chemical reactor system, which is capable of heating the synthesis gas to a target and controlled temperature required for the batch operation of the reactor. Install heat exchangers and gas-liquid separators to condense and recover ammonia from the reactor effluent stream, and to form an ammonia-lean stream; and Install a pressure control system to enable control and manipulation of the operating pressure of the chemical reactor system.

21. A method for producing ammonia from a synthesis gas containing hydrogen and nitrogen in combination with any circulating stream, the method comprising the steps of: (a) Supplying synthesis feed gas 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 of the system and to one or more manifolds at the outlet of the system, each catalyst-filled pressure vessel reactor being equipped with independently operated mechanisms to control, direct, and stop the flow of fluid through the inlet manifold to the individual vessel and the catalyst bed or the flow of fluid through the outlet manifold to the individual vessel and the catalyst bed. (b) Open the control mechanism of the selected catalyst-filled pressure vessel reactor or group of catalyst-filled pressure vessel reactors so that sufficient synthesis feed gas can be delivered from its inlet manifold to each catalyst-filled pressure vessel reactor, thereby filling the catalyst-filled pressure vessel reactor with feed gas and pressurizing it to the selected operating pressure. (c) Once the feed gas has been filled, the control mechanism located at each end of the selected catalyst-filled pressure vessel reactor or group of reactors is shut off to stop or sufficiently slow the flow of gas in contact with the catalyst, thereby allowing the reaction to occur; (d) Timing, predicting or monitoring the temperature, pressure or other measurable conditions within each closed or partially closed catalyst-filled pressure vessel reactor to determine reaction progress; (e) Once the reaction has reached the desired state, conversion or equilibrium conversion, the one or more catalyst-filled pressure vessel reactors are cooled to below the critical point temperature or dew point temperature of the ammonia products. (f) Once sufficiently cooled, the liquid ammonia product collected in the lower portion of the one or more catalyst-filled pressure vessel reactors is discharged, while preventing most of the unreacted gas from escaping the one or more catalyst-filled pressure vessel reactors; and (g) Repeat the filling process described above by adding new synthesis feed gas to any unreacted gas remaining in the one or more catalyst-filled pressure vessel reactors.

22. The method according to claim 21, wherein, One or more reactants are gradually introduced into each catalyst-filled pressure vessel reactor to allow controlled ammonia production and temperature release, thereby maintaining the desired operating temperature and pressure conditions within the individual catalyst-filled pressure vessel reactor.

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

24. The method according to claim 21, wherein, Hydrogen and nitrogen are stored at sufficiently high pressure in the one or more catalyst-filled pressure vessel reactors during periods when electricity is available, so that during periods when electricity is unavailable, hydrogen and nitrogen can be transferred to a portion of the one or more catalyst-filled pressure vessel reactors to produce ammonia.

25. The method according to claim 21, wherein, The one or more catalyst-filled pressure vessel reactors are sequentially filled with feed gas to achieve intermittent or near-intermittent residence times in each reactor, while having a continuous or near-continuous flow of feed gas throughout the entire system of the reactor vessel.

26. The method according to claim 21, wherein, The one or more catalyst-filled pressure vessel reactors are equipped with sensors, detectors, or controllers that transmit information to one or more control systems, enabling the system formed by the reactor, mechanisms, sensors, and control systems to operate in a manner that allows for a continuous inflow of feed gas and a continuous outflow of products through the overall system of the reactor.

27. The method according to claim 21, wherein, The one or more catalyst-filled pressure vessel reactors are equipped with a control system capable of manipulating the reactors and their fluid control mechanisms such that they are sequentially filled with synthesis gas to achieve intermittent or near-intermittent residence times in each reactor, while having a continuous or near-continuous flow of feed gas through the entire system of the reactor vessel.

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

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

30. The method according to claim 21, wherein, The one or more catalyst-filled pressure vessel reactors are equipped with internal or external heat transfer systems to modify the temperature of the reactor during the reaction.

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

Images