The present invention relates to a system, method and apparatus for separating a tritiated heavy water stream into a tritium-lean heavy water stream and a tritium-enriched heavy water stream.
In nuclear power reactors of the type using heavy water as coolant and moderator, there is a progressive build-up of tritiated heavy water (DTO) in the D2O because this DTO is continuously produced from neutron capture in deuterium. At present, the removal of tritium from water is accomplished by various hydrogen separation techniques, e.g. water distillation, cryogenic distillation of hydrogen, etc. which will immobilize tritium.
However, known methods and systems for removing tritium from heavy water are deficient. For instance, methods and systems using vapour phase catalytic exchange (VPCE) and cryogenic distillation are not able to remove tritium from heavy water moderator water to levels low enough to avoid environmental contamination and also these methods and systems can cause a buildup of 17O which results in accumulation of 14C in the reactor moderator (which is undesirable for occupational exposure for personnel). Accordingly, there is a need for improved methods and systems for that can remove tritium from heavy water in order to provide sufficiently low levels to avoid environmental contamination and to reduce the buildup of 17O and the accumulation of 14C in the reactor moderator.
It is an embodiment of the present invention to provide a system, an apparatus, and process for removing tritium from heavy water to at least near environment levels that are virtually free of all other radioactive elements. In some aspects, the present invention relates to a system, an apparatus, and process for use with a CANDU (Canada Deuterium Uranium) plant with an existing TRF (Tritium Removal Facility) to further detritiate heavy water and provide beneficial tritium and 14C management.
It is an embodiment of the present invention to provide a process for separating a tritiated heavy water stream into a tritium-lean heavy water stream and a tritium-enriched heavy water stream, the process comprising:
In one aspect the process further comprises refluxing a portion of the tritium-lean heavy water stream back into the second end of the column.
In one aspect the process further comprises
In one aspect the source of the tritiated heavy water stream comprises a vapor phase catalytic exchange column (VPCE) configured to receive the tritium-enriched heavy water stream.
In one aspect the hydrophobic solid catalyst is a platinum-based hydrophobic solid catalyst.
In one aspect the process the D2/O2 recombiner is a D2/O2 overhead recombiner.
In one aspect the process the feed point is about mid-way between the first end and the second end.
In one aspect the process the forming, in the electrolysis cell, produces an oxygen gas.
In one aspect the process further comprises diverting the produced oxygen gas away from the electrolysis cell.
In one aspect the produced oxygen gas comprises 17O.
In one aspect the isotope exchange column comprises a plurality of isotope exchange columns.
In one aspect the plurality of isotope exchange columns comprise: a first LCPE configured for receiving the tritiated heavy water (DTO/D2O) feed and flowing the tritium-rich heavy water out the first end of the column, a second LPCE emplaced between the first LPCE and the second end and fluidly connected to the first LPCE, and a third LPCE emplaced between the second LPCE and the second end and fluidly connected to the second LPCE and configured for flowing the tritium-lean deuterium gas into the D2/O2 recombiner and for receiving the portion of the tritium-lean heavy water stream from the D2/O2 recombiner.
It is an embodiment of the present invention to provide a process for separating a tritiated heavy water stream into a tritium-lean heavy water stream and a tritium-enriched heavy water stream, the process comprising:
It is an embodiment of the present invention to provide a process for producing a tritium-lean heavy water stream, the process comprises: providing a source of tritiated heavy water; flowing the tritiated heavy water into an isotope exchange column; enriching tritium concentration in the tritiated heavy water to produce, in the isotope exchange column, a tritium-enriched heavy water stream and a tritium-lean deuterium gas; combining the tritium-lean deuterium gas with oxygen gas to produce a tritium-lean heavy water stream.
It is an embodiment of the present invention to provide a system for producing a tritium-lean heavy water stream comprising:
Reference will be made below in detail to exemplary embodiments of the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numerals used throughout the drawings refer to the same or like parts.
The primary heat transport system 22 circulates pressurized heavy water coolant through the reactor fuel channels (not shown) to remove heat produced by fission of natural uranium fuel. The heavy water upgrader 24 separates heavy water from a mixture of light water and heavy water to yield a product containing a sufficiently high isotopic concentration of heavy water to be used in the moderator 26. The moderator 26 can be a standard CANDU (Canada Deuterium Uranium) moderator for heavy water, used to control/moderate the neutrons released from the fission reaction to sustain the chain reaction.
As shown in
The LPCE 104 is a countercurrent column that is packed with a hydrophobic solid catalyst. In one aspect, the hydrophobic solid catalyst is a platinum-based hydrophobic solid catalyst. In some aspects, the LPCE 104 is packed with any type of catalyst that is water-repellent and consists of at least one catalytically active metal selected from Group VIII of the Periodic Table having a substantially liquid-water-repellant organic resin or polymer coating thereon which is permeable to water vapour and hydrogen gas. In some aspects, the liquid-water-repellant organic resin or polymer coating are polyflurocarbons, hydrophobic hydrocarbon polymers of medium to high molecular weight, or silicones. Examples of catalysts include group VIII metals: Pt, Ni, Ir, Rh and Pd and Catalyst support: carbon, graphite, charcoal, alumina (Al2 O3), magnesia, silica (SiO2), silica gel, chromia (Cr2 O3), nickel oxide (NiO); and substantially liquid-water-repellent coating: polytetrafluoroethylene is a preferred waterproof coating. Other waterproof coatings are for example, silicone resins consisting of semi-polymerized methyl siloxanes with some percentage of silanol, methoxy or ethoxy, groups attached to the siloxane structure. Usually, a polyalkylsiloxane is preferred, substituted with sufficient hydroxyl (silanol), methoxy/or ethoxy/groups for post-application crosslinking, and chemisorption or chemical bonding to the support with the catalyst thereon, and optionally, with some higher alkyl (ethyl, propyl, isopropyl, t-butyl) groups for improved stability. See also Canadian patent no. 1137025 and U.S. Pat. No. 4,190,515, which are incorporated herein by reference.
In the LPCE 104, the deuterium/water exchange equilibrium reaction shown in Equation 1 below takes place, in which the formation of liquid DTO is favored when heavy water is contacted with tritiated deuterium gas (DT). By virtue of the countercurrent flow, the tritium moves from the gaseous D2/DT stream to the liquid D2O/DTO stream. Consequently, the tritium content is concentrated in the water (DTO/D2O) in the LPCE column 104 below the feed point 106.
DT(g)+D2O(l)↔DTO(l)+D2(g) [Equation 1]
Without any limitation and not being limited to any particular theory, the exchange of hydrogen isotopes between hydrogen gas and liquid water comprises the following steps: evaporation of water isotopologues at the liquid/gas-vapor interface from liquid water flowing down the column over inert packing; mixing of water isotopologues within the liquid water phase from the liquid/gas-vapor interface into the bulk of the liquid water; transport of water vapor to the catalyst particle through the upward flowing gas-vapor stream; diffusion of reactants (water and hydrogen isotopologues) into the catalyst particle; chemisorption of the reactants, isotope exchange reaction, and desorption of the reaction products (isotopically equilibrated water vapor and hydrogen); diffusion of the reaction products out of the catalyst particle; transport of isotopically equilibrated water vapor to the liquid surface through the upward flowing gas-vapor stream; mixing of isotopically equilibrated hydrogen into the upward flowing gas-vapor stream; and condensation of water isotopologues at the liquid/gas-vapor interface into liquid water flowing down the column over inert packing.
Exiting the LPCE column 104 at the first end 108 is a tritium-rich heavy water stream (D2O/DTO) 112. The tritium-rich heavy water stream 112 is fed to an electrolysis cell 114.
The electrolysis cell 114 separates the tritium-rich heavy water 112 stream into deuterium, tritiated deuterium and oxygen gases. Heavy water is depleted from the liquid as it is more easily electrolyzed. In other words, the lighter component is preferentially evolved with the gas, enriching the heavy component in the electrolysis cell liquid. Therefore, the concentration of the tritium in the electrolyser liquid further increases, according to Equations 2 and 3 below.
2DTO(l)→2DT(g)+O2(g) [Equation 2]
2D2O(l)→D(g)+O2(g) [Equation 3]
As shown in
Exiting the electrolysis cell 114 will be a tritium-enriched water 116 which is returned to the VPCE 14 of the TRF 12 (as shown in
According to one aspect of the present disclosure, the oxygen gas 120 produced in the electrolysis cell 114 comprises 17O isotope, and this produced oxygen gas 120 can be removed (as opposed to being recycled) according to the process 100. The removal of 17O isotope beneficially avoids accumulation of 14C that would otherwise occur and therefore addresses numerous regulatory, safety, and environmental emissions concerns.
Exiting the LPCE 104 at the second end 110 is a tritium-lean deuterium gas 122 which is flowed into a D2/O2 recombiner 124. Oxygen gas 126 comprising 16O from an external source (not shown) is also flowed into the D2/O2 recombiner 124. The tritium-lean deuterium gas 122 is recombined with the oxygen gas 126 to produce a tritium-lean D2O liquid 128. This tritium-lean D2O liquid 128 is “virgin grade” or “virgin grade” equivalent heavy water containing tritium levels near environmental levels. A portion 128a of the tritium-lean D2O liquid 128 is diverted back into the LPCE 104 for reflux and another portion 128b is diverted away as a product.
In some aspects, the D2/O2 recombiner 124 is an overhead recombiner.
In some aspects, the portion 128b can be diverted back to the heat transport system 22 to replenish any heavy water loss and where portion 128b is intended for circulation through the reactor fuel channels to remove heat produced by fission of natural uranium fuel. Therefore, virgin heavy water 128b is a marketable product_with broad applications including makeup water of a heat transport system (as part of ongoing operation, a small percentage of heavy water is lost). Such is one application of the produced virgin heavy water 128 by heavy water utilities.
The present process is a high-efficiency system that removes tritium in heavy water to near environmental level, and virtually free of all other radioactive elements. In some embodiments, the detritiation factor (DF) which is a ratio of tritium concentration in the input stream over the output stream is at least 400,000. By comparison, the DF of the existing TRF is 35.
It will be seen that in the present example of the invention as shown in
The embodiments of the present application described above are intended to be examples only. Those of skill in the art may effect alterations, modifications and variations to the particular embodiments without departing from the intended scope of the present application. In particular, features from one or more of the above-described embodiments may be selected to create alternate embodiments comprised of a subcombination of features which may not be explicitly described above. In addition, features from one or more of the above-described embodiments may be selected and combined to create alternate embodiments comprised of a combination of features which may not be explicitly described above. Features suitable for such combinations and subcombinations would be readily apparent to persons skilled in the art upon review of the present application as a whole. Any dimensions provided in the drawings are provided for illustrative purposes only and are not intended to be limiting on the scope of the invention. The subject matter described herein and in the recited claims intends to cover and embrace all suitable changes in technology.
This application claims priority to U.S. Provisional application No. 63/231,090 filed Aug. 9, 2021, which is hereby incorporated by reference in its entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/CA2022/051208 | 8/8/2022 | WO |
Number | Date | Country | |
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63231090 | Aug 2021 | US |