Recombination reactor
The reactor design addresses the scarcity and cost of isotopic gases by enabling efficient production of isotopically labeled waters through a catalytic process with a pre-heating, reaction, and effluent zone, achieving high yields and purity in isotopic water production.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- CAMBRIDGE ISOTOPE LAB
- Filing Date
- 2026-01-20
- Publication Date
- 2026-07-23
AI Technical Summary
Isotopic gases, such as deuterium oxide (D2O), are scarce and expensive to recover and purify, necessitating the development of more efficient recombination reactors and systems for their production.
A reactor design comprising a pre-heating zone, reaction zone with a catalyst, and effluent zone, utilizing a nickel-chromium-iron alloy and platinum catalyst, with specific geometries and materials to facilitate high-temperature catalytic conversion of isotopic gases into isotopically labeled water species, including a thermowell for temperature measurement and automated control systems.
The reactor achieves high yields and deuterium extent of reaction exceeding 99%, handling increased flow rates and pressures, and ensures efficient production of isotopically labeled waters like D2O with improved throughput and purity.
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Abstract
Description
Atorney Docket No. CISL 200002W001RECOMBINATION REACTOR
[0001] This application claims the priority benefit of U.S. Provisional Application No.63 / 746,362 filed January 17, 2025, which is incorporated by reference in its entirety.BACKGROUND
[0002] The present exemplary embodiment relates to recombination reactors and associated systems and methods. It finds particular application in conjunction with the production of heavy water or other isotopic waters (deuterium oxide; D2O) and will be described with particular reference thereto. However, it is to be appreciated that the present exemplary embodiment is also amenable to similar applications.
[0003] Isotopic gases are utilized throughout many industries for varying applications. Non-limiting examples of fields include semi-conductors, medicine, and research. However, such gases are scarce and expensive to recover and purify.
[0004] It would be desirable to develop new recombination reactors and associated systems and methods, particularly, but not exclusively, for the production of D2O and other isotopic waters.BRIEF DESCRIPTION
[0005] The present disclosure relates to recombination reactors, systems including the reactors, and methods utilizing the reactors.
[0006] Disclosed, in some embodiments, is a reactor including: a reactor vessel containing in sequence vertically from bottom to top: a pre-heating zone having a plurality of beads; a reaction zone having a catalyst; and an effluent zone. The reactor further includes a carrier inlet configured to provide a carrier gas to the pre-heating zone; an isotopic gas inlet configured to provide an isotopic gas above the pre-heating zone and below or at the reaction zone; an oxidizing or reducing agent inlet configured to provide an oxidizing or reducing agent above the pre-heating zone and below the reaction zone; and a vapor outlet for recovering product gas from the effluent zone.
[0007] The reactor may contain a nickel-chromium iron alloy. In some embodiments, the nickel-chromium-iron alloy contains: at least 72 wt% nickel plus optional cobalt; 14.0to 17.0 wt% chromium; 6.0 to 10.0 wt% iron; up to 0.15 wt% carbon; up to 1.0 wt% manganese; up to 0.015 wt% sulfur; up to 0.50 wt% silicon; and up to 0.50 wt% copper.
[0008] In some embodiments, the reactor further includes a thermowell extending through a wall of the reactor vessel into the reaction zone and configured to measure a temperature in the reaction zone.
[0009] The reactor vessel may include a cylindrical or substantially cylindrical main body portion located between a hemispherical or substantially hemispherical lower end portion and a hemispherical or substantially hemispherical upped end portion.
[0010] In some embodiments, the beads contain a metal or a metal alloy, such as stainless steel.
[0011] The beads may number from about 500 to about 10,000 or from about 4,000 to about 6,000.
[0012] In some embodiments, the beads have a diameter of from about 0.01 to about 0.05 inches or about 0.02 to about 0.03 inches.
[0013] The catalyst may contain one or more precious metals (e.g., platinum and / or palladium).
[0014] In some embodiments, the reaction zone includes a cross structure supporting catalytic sites (e.g., 4 catalyst sites) comprising the catalyst.
[0015] The reactor vessel may have a wall thickness of about 0.6 to about 1.1 inches or about 0.864 inches.
[0016] In some embodiments, the main body portion has an outer diameter in a range of about 5.5 to about 7.5 inches or about 6.625 inches.
[0017] The main body portion may have an inner diameter in a range of about 5 to about 6.5 inches or about 5.761 inches.
[0018] In some embodiments, the isotopic gas inlet and the oxidizing or reducing agent inlet are provided about 0.5 to about 1.0 inches, or about 0.75 inches above the preheating zone.
[0019] Disclosed, in other embodiments, is a process (batch or continuous) for producing a product using the reactor. The process includes providing carrier gas to the carrier inlet; providing an isotopic gas to the isotopic gas inlet; providing an oxidizing orreducing agent to the oxidizing or reducing agent inlet; and recovering product gas through the vapor outlet.
[0020] The process may further include purifying the recovered product.
[0021] In some embodiments, the carrier gas is a noble gas, such as argon (Ar).
[0022] The isotopic gas may be deuterium gas (D2) or any other isotopic gas of H2.
[0023] In some embodiments, the oxidizing or reducing agent comprises oxygen (O2) or any other isotopic gas of O2.
[0024] The product gas may be heavy water (D2O) or any other isotopically labeled water species.
[0025] In some embodiments, a temperature in the reaction zone is at least 700 °C.
[0026] These and other non-limiting aspects of the disclosure are more particularly set forth below.BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The following is a brief description of the drawings, which are presented for the purposes of illustrating the exemplary embodiments disclosed herein and not for the purposes of limiting the same.
[0028] FIG. 1 is a process flow diagram of a system in accordance with some embodiments of the present disclosure, wherein the gas species are fed, and the reactor produces a product (e.g., D2O) or other isotopically labeled water species.
[0029] FIG. 2 is a side profile view of a reactor in accordance with some embodiments of the present disclosure.
[0030] FIG. 3 illustrates the reactor with zones labeled.
[0031] FIG. 4 is a view of the reactor emphasizing the catalyst support structure in accordance with some embodiments of the present disclosure.DETAILED DESCRIPTION
[0032] The present disclosure may be understood more readily by reference to the following detailed description of desired embodiments and the examples included therein. In the following specification and the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings.
[0033] Although specific terms are used in the following description for the sake of clarity, these terms are intended to refer only to the particular structure of the embodiments selected for illustration in the drawings and are not intended to define or limit the scope of the disclosure. In the drawings and the following description below, it is to be understood that like numeric designations refer to components of like function.
[0034] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.
[0035] The term “comprising” is used herein as requiring the presence of the named components / steps and allowing the presence of other components / steps. The term “comprising” should be construed to include the term “consisting of’, which allows the presence of only the named components / steps.
[0036] Numerical values should be understood to include numerical values which are the same when reduced to the same number of significant figures and numerical values which differ from the stated value by less than the experimental error of conventional measurement technique of the type described in the present application to determine the value.
[0037] All ranges disclosed herein are inclusive of the recited endpoint and independently combinable (for example, the range of “from 2 grams to 10 grams” is inclusive of the endpoints, 2 grams and 10 grams, and all the intermediate values). The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value; they are sufficiently imprecise to include values approximating these ranges and / or values.
[0038] As used herein, the term “about” when used in conjunction with a stated numerical value or range denotes somewhat more or somewhat less than the stated value or range, to within a range of ±10% of that stated.
[0039] The present disclosure relates to a catalytic, flameless reactor that reacts to isotopic gas in the presence of an oxidizing or reducing agent to generate a water product. Equation 1 is written for the deuterium gas recovery pathway:(Eq. 1)
[0040] However, it should be understood that other isotopic gases of H2 and / or O2 may similarly be utilized. For example, Hydrogen-1 (protium) and / or Hydrogen-3 (tritium) maybe used in combination with or as an alternative to Hydrogen-2 (deuterium). Similarly, the oxygen component may be Oxygen-16, Oxygen-17, and / or Oxygen-18.
[0041] FIG. 1 is a process flow diagram of a system in accordance with some embodiments of the present disclosure. The gas species are provided to a mass flow control system which controls flow rates to the reactor. A product produced in the reactor may be recovered.
[0042] The reactor design is useful for high-temperature catalytic conversion reactions of gaseous isotopic species at much higher flowrates than previous system sizes. For example, while previous systems may have been operated at a D2 flow rate of 5 to 10 standard liters per minute (SLPM), the reactors of the present application may be operated at higher D2 flow rates (e.g., 20 to 50, 25 to 40, or 30 to 35 SLPM). An increase in sizing of all system components as well as increased reactor dimensions was performed to handle increased throughput and heat transfer.
[0043] The reactor is not limited to use with D2. Another non-limiting example involves the conversion of hydrogen and oxygen-18 to high purity H2O18.
[0044] The oxidizing or reducing agent (e.g., O2) may be fed in excess of the stoichiometric amount to ensure full conversion. The excess may be at least or about 10%, at least or about 20%, at least or about 30%, at least or about 40%, at least or about 50%, or at least or about 60%.
[0045] Each of the isotopic gas, oxidizing or reducing agent, and carrier gas may be independently provided to the reactor at temperatures in a range of about 0 to about 30 °C and pressures in a range of about 5 to about 40 psig.
[0046] Carrier gas depends on the flow rate of deuterium selected. Preheating occurs at 3 SLPM of inert gas flow. At 30 SLPM, inert flow of 5 SLPM is required.
[0047] Yields and deuterium extent of reaction of over 99% have been achieved via this reactor design. The carrier gas is fed from the bottom of the reactor to a pre-heating zone (FIGS. 2 and 3). The combustion species (e.g., oxygen and deuterium) enter the reactor just above the pre-heating zone where they are mixed with carrier gas. The incorporated gas then rises and meets the catalytic platinum surface where the reaction takes place. The effluent gas then exits the reactor for purification and collection. The reactor temperature is designed to run above 700 °C and at any operating pressure.
[0048] In some embodiments, the reactor is operated at a temperature of about 500 to about 1100 °C, including from about 650 to about 825 °C. The reactor pressure may be in a range of from 0 to about 1 psig.
[0049] The materials of construction for the isotopic recombination system are designed to handle very high temperatures.
[0050] Non-limiting examples of high temperature alloys which may be used for the reactor and / or inlet lines and / or outlet line include Inconel 600, nickel alloys, and titanium alloys.
[0051] The reactor and components are designed to handle the corrosive effects of high purity liquids and vapors.
[0052] The reactor has 4 process connections as illustrated in FIG. 2.
[0053] The feed gases are all located at the bottom of the reactor (below the catalytic surface).
[0054] The effluent leaves the top of the reactor and is sent to product collection. The reactor effluent gas exists and is sent to be condensed in a heat exchanger that is custom designed for this application to handle high purity D2O. Pressure drop is maximized in the design in order to recover all of the D2O vapor. Temperature of the trap is maintained at 6 °C to ensure that the D2O does not freeze. Autonomous collection of the exchanger and trap contents occurs at an operator specified timeframe. Water purification may occur via a process involving resin exchange and multiple distillation systems.
[0055] The gas feed locations are configured to achieve the correct exothermic reaction conditions.
[0056] The internal reactor geometry (see FIG. 3) includes a pre-heating zone, a reaction zone, and an effluent zone.
[0057] The preheating zone is filled with beads (e.g., metal beads such as stainless steel 316 beads that undergo special cleaning). Non-limiting alternative to stainless steel 316 include nickel, nickel-chromium-iron alloys, and nickel-copper alloys. The nickelcopper alloys may contain 52-57 wt% nickel, or at least 63 wt% nickel. The cleaning may include citric acid passivation followed by heat treatment. The quantity of the beads may be in a range of about 500 to about 10,000, including from about 1,000 to about 9,000, from about 2,000 to about 8,000, from about 3,000 to about 7,000, from about 4,000 toabout 6,000, and about 5000. The beads provide heat transfer of the inert carrier gas to ensure pre-heating. They also increase mixing of the gas species in the reaction.
[0058] The beads may have a diameter in a range of from about 0.005 to about 0.045 inches, including from about 0.010 to about 0.040 inches, from about 0.015 to about 0.035 inches, from about 0.020 to about 0.030 inches, and about 0.025 inches.
[0059] The reaction zone may contain a cross “T” pattern which supports 4 catalytic sites made from platinum of 99.6% purity. A non-limiting example of this structure is illustrated in FIG.4. 4 sites of catalytic conversion across the entire length of the reaction zone, helps to spread heat load across the whole reactor system instead of in localized heat zones, which can have a negative effect on material integrity and other system components. However, the number of catalytic sites is not limited to four. Other examples include one, two, three, five, six, seven, eight, nine, ten, or more. Palladium can be used but is not preferable due to palladium having a higher ability to absorb oxygen, leading to PdO stable oxide formation over time. Prolonged exposure to heat and oxygen can create structure changes in palladium that do not occur with platinum.
[0060] The geometry of the reactor is designed to create minimum backpressure in order that the reaction can be run at various temperatures and pressure ranges.
[0061] The staggered gas feeds and feed locations provide mixing below the catalytic surface ensure that a complete extent of reaction of the H2 isotope and the O2 isotope occurs.
[0062] In particular embodiments, the reaction vessel includes a (generally) cylindrical main body portion located between a (generally) hemispherical lower end portion and a (generally) hemispherical upper end portion.
[0063] The wall of the reactor vessel may have a thickness in a range of from about 0.6 to about 1.1 inches, including about 0.7 to about 1.0 inches, about 0.8 to about 0.9 inches, and about 0.864 inches.
[0064] The main body portion may have an outer diameter in a range of about 5.5 to about 7.5 inches, including from about 6.0 to about 7.0 inches, and about 6.25 inches.
[0065] The main body portion may have an inner diameter in a range of about 4.0 to about 7.5 inches, including from about 5.0 to about 6.5 inches, and about 5.761 inches.
[0066] A thermowell is present in the reactor and located directly in the mixing / reacting zone to accurately monitor reactor conditions. This is rated for 1200 °C. A control system and scheme for reactor temperature, pressure, and flow rate control may utilize DeltaV control systems.
[0067] Temperature of the Reactor may be controlled via PID FF control (modulating the reactor gas H2 isotope / 02 isotope feed flow rates)
[0068] Automated Valves and Mass flow controllers allow for other process control functions including D2O or any other isotopically labeled water species, collection, system isolation, system venting, etc.
[0069] Safety systems and interlocks are also controlled via the control system.
[0070] Any documents mentioned herein are hereby incorporated by reference for the purpose of disclosing and describing the particular materials and methodologies for which the document was cited.
[0071] Although the present invention has been described in connection with preferred embodiments thereof, it will be appreciated by those skilled in the art that additions, deletions, modifications, and substitutions not specifically described may be made without departing from the spirit and scope of the invention. Terminology used herein should not be construed as being “means-plus-function” language unless the term “means” is expressly used in association therewith.
[0072] The exemplary embodiment has been described with reference to the preferred embodiments. Obviously, modifications and alterations will occur to others upon reading and understanding the preceding detailed description. It is intended that the exemplary embodiment be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims
CLAIMS;1. A reactor comprising:a reactor vessel containing in sequence vertically from bottom to top: a pre-heating zone comprising a plurality of beads;a reaction zone comprising a catalyst; andan effluent zone;a carrier inlet configured to provide a carrier gas to the pre-heating zone; an isotopic gas inlet configured to provide an isotopic gas above the preheating zone and below or at the reaction zone;an oxidizing or reducing agent inlet configured to provide an oxidizing or reducing agent above the pre-heating zone and below the reaction zone; anda vapor outlet for recovering product gas from the effluent zone.
2. The reactor of claim 1, wherein the reactor comprises a nickel-chromium- iron alloy.
3. The reactor of claim 2, wherein the alloy comprises:at least 72 wt% nickel plus optional cobalt;14.0 to 17.0 wt% chromium;6.0 to 10.0 wt% iron;up to 0.15 wt% carbon;up to 1.0 wt% manganese;up to 0.015 wt% sulfur;up to 0.50 wt% silicon; andup to 0.50 wt% copper.
4. The reactor of claim 1 , further comprising:a thermowell extending through a wall of the reactor vessel into the reaction zone and configured to measure a temperature in the reaction zone.
5. The reactor of claim 1 , wherein the reactor vessel comprises a cylindrical or substantially cylindrical main body portion located between a hemispherical orsubstantially hemispherical lower end portion and a hemispherical or substantially hemispherical upped end portion.
6. The reactor of claim 1, wherein the plurality of beads comprises a metal or a metal alloy.
7. The reactor of claim 1 , wherein the plurality of beads comprises stainless steel.
8. The reactor of claim 1 , wherein the plurality of beads comprises from about 500 to about 10,000 beads.
9. The reactor of claim 1 , wherein the plurality of beads comprises from about 4,000 to about 6,000 beads.
10. The reactor of claim 1 , wherein the beads have a diameter of about 0.01 to about 0.05 inches.
11. The reactor of claim 1 , wherein the beads have a diameter of about 0.02 to about 0.03 inches.
12. The reactor of claim 1, wherein the catalyst comprises platinum and / or palladium.
13. The reactor of claim 1, wherein the reaction zone comprises a cross structure supporting catalytic sites comprising the catalyst.
14. The reactor of claim 13, wherein the catalytic sites comprise 4 catalytic sites.
15. The reactor of claim 1 , wherein the reactor vessel has a thickness of about 0.6 to about 1.1 inches.
16. The reactor of claim 1 , wherein the reactor vessel has a thickness of about 0.864 inches.
17. The reactor of claim 5, wherein the main body portion has an outer diameter in a range of about 5.5 to about 7.5 inches.
18. The reactor of claim 5, wherein the main body portion has an outer diameter of about 6.625 inches.
19. The reactor of claim 5, wherein the main body portion has an inner diameter in a range of about 5 to about 6.5 inches.
20. The reactor of claim 5, wherein the main body portion has an inner diameter of about 5.761 inches.
21. The reactor of claim 1, wherein the isotopic gas inlet and the oxidizing or reducing agent inlet are provided about 0.5 to about 1.0 inches above the pre-heating zone.
22. The reactor of claim 1, wherein the isotopic gas inlet and the oxidizing or reducing agent inlet are provided about 0.75 inches above the pre-heating zone.
23. A process for producing a product using the reactor of any one of claims 1- 22, the process comprising:providing carrier gas to the carrier inlet;providing an isotopic gas to the isotopic gas inlet;providing an oxidizing or reducing agent to the oxidizing or reducing agent inlet; andrecovering product gas through the vapor outlet.
24. The process of claim 23, further comprising:purifying the recovered product.
25. The process of claim 23, wherein the carrier gas comprises a noble gas.
26. The process of claim 23, wherein the carrier gas comprises argon (Ar).
27. The process of claim 23, wherein the isotopic gas comprises deuterium gas (D2).
28. The process of claim 23, wherein the oxidizing or reducing agent comprises oxygen (O2).
29. The process of claim 23, wherein the product gas comprises heavy water (D2O).
30. The process of claim 23, wherein a temperature in the reaction zone is at least 700 °C.