CN117623241A - Extraction method and extraction system for helium-3 in high tritium heavy water mixed gas - Google Patents
Extraction method and extraction system for helium-3 in high tritium heavy water mixed gas Download PDFInfo
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- SWQJXJOGLNCZEY-BJUDXGSMSA-N helium-3 atom Chemical compound [3He] SWQJXJOGLNCZEY-BJUDXGSMSA-N 0.000 title claims abstract description 88
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 title claims abstract description 84
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 title claims abstract description 52
- 229910052722 tritium Inorganic materials 0.000 title claims abstract description 52
- 238000000605 extraction Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000000746 purification Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 223
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 106
- 239000001307 helium Substances 0.000 claims description 105
- 229910052734 helium Inorganic materials 0.000 claims description 105
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 70
- 238000001179 sorption measurement Methods 0.000 claims description 69
- 229910052739 hydrogen Inorganic materials 0.000 claims description 67
- 239000001257 hydrogen Substances 0.000 claims description 67
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000012528 membrane Substances 0.000 claims description 35
- 229910052763 palladium Inorganic materials 0.000 claims description 35
- 230000003197 catalytic effect Effects 0.000 claims description 25
- 230000003647 oxidation Effects 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims description 24
- 229930195733 hydrocarbon Natural products 0.000 claims description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- 239000003463 adsorbent Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000006479 redox reaction Methods 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 19
- 238000000926 separation method Methods 0.000 abstract description 11
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 4
- 239000000945 filler Substances 0.000 description 17
- 238000012856 packing Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000012546 transfer Methods 0.000 description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910052805 deuterium Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 239000012466 permeate Substances 0.000 description 2
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- 239000010935 stainless steel Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
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- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 1
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Abstract
The embodiment of the application provides an extraction method and an extraction system for helium-3 in high tritium heavy water mixed gas. Wherein the extraction method comprises a purification treatment, a low-temperature pre-rectification treatment and a dehydrogenation treatment. The extraction method of the embodiment of the application can realize the extraction of helium-3 generated in the storage process of high tritium heavy water, namely provides a new way for obtaining helium-3, so that the yield of helium-3 can be improved, and in addition, the extraction method of the embodiment of the application has the advantages of advanced flow, high separation degree, high helium-3 gas quality and the like, and the helium-3 generated in the storage process of high tritium heavy water can be fully obtained, so that the energy utilization rate is improved.
Description
Technical Field
The application relates to the technical field of chemical industry, in particular to a method and a system for extracting helium-3 from high tritium heavy water mixed gas.
Background
Helium-3 is an isotope of helium, helium-3 has unique physical properties, and is increasingly used in various fields such as neutron detection, low-temperature engineering, nuclear energy development, medicine, geography, astronomy and the like, helium-3 is called one of the most precious rare gases, and stable supply of high-quality helium-3 gas is one of important support technologies for developing quantum technologies.
Helium-3 is extremely rare in the related art, and helium-3 is obtained in a relatively small number of ways and with relatively large difficulty, so that helium-3 yield is relatively low.
Disclosure of Invention
In view of this, the embodiments of the present application provide a method and a system for extracting helium-3 from a high tritium heavy water mixed gas, which aims to provide a new way for obtaining helium-3 with low difficulty, so as to improve the yield of helium-3.
In order to achieve the above objective, an aspect of the embodiments of the present application provides a method for extracting helium-3 from a high tritium heavy water mixed gas, where the mixed gas includes a cover gas, and the cover gas is nitrogen, and the method is characterized in that the method includes:
purifying: purifying the mixed gas containing helium-3 to remove water, steam and CO in the mixed gas 2 Hydrocarbon, hydrocarbon,Part N 2 Part O 2 Combining a part of the hydrogen isotopes and obtaining a first-stage crude helium;
cryogenic pre-rectification treatment: subjecting said first stage crude helium to cryogenic pre-rectification to remove residual N from said first stage crude helium 2 And O 2 And obtaining coarse helium gas in the second stage;
and (3) dehydrogenizing: and carrying out dehydrogenization treatment on the second-stage crude helium gas to remove residual hydrogen isotope combination gas in the second-stage crude helium gas.
In one embodiment, the purifying step specifically includes:
catalytic oxidation treatment: carrying out catalytic oxidation treatment on the mixed gas containing helium-3 to remove trace hydrocarbon and partial hydrogen isotope combination gas in the mixed gas and obtain a first mixture;
and (3) low-temperature cooling treatment: performing low-temperature cooling treatment on the first mixture to remove water and part of water vapor in the first mixture and obtain a second mixture;
and (3) low-temperature adsorption treatment: subjecting the second mixture to low-temperature adsorption treatment to remove CO in the second mixture 2 Part N 2 Part O 2 And residual water vapor and obtaining said first stage crude helium.
In one embodiment, the catalytic oxidation treatment step specifically includes:
and under the high temperature condition, controlling the mixed gas to be introduced into the copper oxide so as to enable the copper oxide to generate oxidation-reduction reaction with the hydrocarbon and hydrogen isotope combined gas in the mixed gas.
In one embodiment, the cryogenically cooling treatment step specifically includes:
the first mixture is controlled to flow through chilled water for sub-cooling.
In one embodiment, the low-temperature adsorption treatment step specifically includes:
and (3) carrying out low-temperature adsorption on the second mixture by adopting a low-temperature adsorption material at the temperature of liquid nitrogen.
In one embodiment, the low temperature adsorbent material comprises at least one of a molecular sieve and activated carbon.
In one embodiment, the dehydrogenizing step specifically includes:
and (3) palladium membrane permeation treatment: performing palladium membrane permeation treatment on the second-stage crude helium gas to remove part of hydrogen isotope combination gas in the second-stage crude helium gas and obtain third-stage crude helium gas;
and (3) ultralow temperature adsorption treatment: and carrying out ultralow-temperature adsorption treatment on the third-stage crude helium gas to remove residual hydrogen isotope combination gas in the third-stage crude helium gas.
In one embodiment, the palladium membrane permeation treatment step specifically comprises the following steps:
adding quantitative hydrogen into the coarse helium gas of the second stage;
and (3) palladium membrane permeation is carried out on the second-stage crude helium added with quantitative hydrogen so as to remove part of hydrogen isotope combination gas in the second-stage crude helium.
In one embodiment, the ultra-low temperature adsorption treatment step specifically includes:
and under the condition that the temperature is lower than 0.1K, adopting an ultralow temperature adsorption material to carry out ultralow temperature adsorption on the crude helium gas in the third stage.
In another aspect, an embodiment of the present application provides a system for extracting helium-3 from a high tritium heavy water mixed gas, where the method for extracting helium-3 from a high tritium heavy water mixed gas according to any one of the embodiments is applicable, and the extraction system includes:
the purification treatment unit comprises a catalytic oxidation treatment unit, a low-temperature cooling treatment unit and a low-temperature adsorption treatment unit, wherein the catalytic oxidation treatment unit is used for carrying out catalytic oxidation treatment on the mixed gas containing helium-3 so as to remove trace hydrocarbon and partial hydrogen isotope combined gas in the mixed gas and obtain a first mixture; the cryogenically cooling treatment unit is used for performing cryogenically cooling treatment on the first mixture to remove the first mixtureWater and part of the water vapor in the first mixture and obtaining a second mixture; the low-temperature adsorption treatment unit is used for carrying out low-temperature adsorption treatment on the second mixture so as to remove CO in the second mixture 2 Part N 2 Part O 2 And residual water vapor and obtaining said first stage crude helium;
a cryogenic pre-rectification processing unit for performing cryogenic pre-rectification processing on the first stage crude helium gas to remove residual N in the first stage crude helium gas 2 And O 2 And obtaining coarse helium gas in the second stage;
the hydrogenation removing treatment unit comprises a palladium membrane permeation treatment unit and an ultralow temperature adsorption treatment unit, wherein the palladium membrane permeation treatment unit is used for carrying out palladium membrane permeation treatment on the second-stage crude helium gas so as to remove part of hydrogen isotope combined gas in the second-stage crude helium gas and obtain third-stage crude helium gas; the ultralow temperature adsorption treatment unit is used for carrying out ultralow temperature adsorption treatment on the third-stage crude helium gas so as to remove residual hydrogen isotope combination gas in the third-stage crude helium gas.
According to the extraction method of helium-3 in the high tritium heavy water mixed gas, nitrogen is used as the covering gas, the mixed gas formed by mixing the covering gas with the helium-3 and other gases obtained after tritium decay is used as the raw material in the storage process, and the mixed gas is subjected to purification treatment, low-temperature pre-rectification treatment and dehydrogenation treatment in sequence, so that water, water vapor and CO are gradually removed 2 、N 2 、O 2 The hydrocarbon and hydrogen isotopes combine gas to give a high quality helium-3 gas. The mixed gas formed by the top layer of the high tritium heavy water in the storage process can be fully utilized, so that the energy utilization rate is improved, meanwhile, the embodiment of the application provides a new way for obtaining helium-3, so that the yield of helium-3 can be improved, and in addition, the extraction method of helium-3 has the advantages of advanced flow, high separation degree, high helium-3 gas quality and the like.
Drawings
FIG. 1 is a schematic flow chart of a method for extracting helium-3 from a high tritium heavy water mixed gas according to an embodiment of the present application;
FIG. 2 is a schematic flow chart of a method for extracting helium-3 from a high tritium heavy water mixed gas according to another embodiment of the present application;
FIG. 3 is a schematic diagram of a helium-3 extraction system in a high tritium heavy water mixed gas according to one embodiment of the present application.
Description of the reference numerals
10. A purification treatment unit; 11. a catalytic oxidation treatment unit; 12. a low-temperature cooling treatment unit; 13. a low-temperature adsorption treatment unit; 20. a cryogenic pre-rectification process unit; 30. a dehydrogenization unit; 31. a palladium membrane permeation treatment unit; 32. an ultralow temperature adsorption treatment unit.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and technical features in the embodiments may be combined with each other, and the detailed description in the specific embodiments should be interpreted as an explanation of the gist of the present application and should not be construed as undue limitation to the present application.
The present application will now be described in further detail with reference to the accompanying drawings and specific examples.
In the related art, heavy water is used as a moderator and a coolant in the heavy water nuclear power unit, and deuterium in the heavy water absorbs neutrons to become tritium in the operation process of the reactor (tritium in the heavy water nuclear power unit is mainly in the moderator). Because the heavy water nuclear power unit needs to replace the pressure pipe in the service life period, in view of personnel radiation dose and environmental influence, tritium removal treatment is needed to be carried out on the heavy water moderator containing tritium before the pressure pipe is replaced, so that considerable high tritium heavy water is obtained. In addition to helium-3 generated by decay of tritium in the storage process of the high tritium heavy water, a certain amount of hydrogen isotope combination gas and oxygen are generated due to the radiation decomposition effect of the tritium in the high tritium heavy water, a cover gas is required to be added into the cavity part of the high tritium heavy water storage container based on the safety aspect of hydrogen, and the helium-3 generated by the decay of the tritium is mixed into the cover gas to form mixed gas, so that an alternative raw material source is provided for obtaining the helium-3 gas.
Based on this, as shown in fig. 1, an aspect of the embodiment of the present application provides a method for extracting helium-3 from a high tritium heavy water mixed gas.
Heavy water is a compound consisting of deuterium and oxygen, also known as deuterium oxide, formula D 2 O。
Three common isotopes of hydrogen in nature: protium (element symbol is H), deuterium (element symbol is D), tritium (element symbol is T).
The deuterium absorbs neutrons to form tritium when the heavy water is irradiated, thereby forming high tritium heavy water.
The mixed gas forms on top of the high tritium heavy water. The mixed gas includes a blanket gas of nitrogen (N) 2 ) I.e., nitrogen is located at the cavity at the top of the high tritium heavy water storage vessel.
Nitrogen is an inert gas that generally does not react with other materials. With nitrogen as the blanket gas, the separation between nitrogen and helium-3 is easier than with helium (helium-4) in heavy water reactors.
It will be appreciated that during storage of high tritium heavy water, the mixed gas includes, in addition to nitrogen (N 2 ) In addition, helium-3, water, steam and trace hydrocarbon (C) introduced into nitrogen gas used as blanket gas x H y )、O 2 、H 2 、CO 2 In addition, it includes the formation of a quantity of O due to the radiolysis of water by tritium 2 、D 2 (DT、HD、HT)。
Specifically, the extraction method for helium-3 in the high tritium heavy water top layer mixed gas comprises the following steps:
s100, purifying: purifying the mixed gas containing helium-3 to remove water, steam and CO in the mixed gas 2 Hydrocarbon, part N 2 Part O 2 And combining a portion of the hydrogen isotopes to obtain a first stage crude helium.
The hydrogen isotope combination gas comprises HD, HT and H 2 、D 2 、DT。
S200, low-temperature pre-rectification treatment: for the first stage coarseCryogenic pre-rectification of helium to remove residual N from first stage crude helium 2 And O 2 And obtaining the crude helium gas of the second stage.
Specifically, the difference of boiling points of different gases is utilized to carry out cooling liquefaction treatment on the first-stage crude helium at high pressure, and the residual N in the first-stage crude helium 2 And O 2 Can be liquefied at low temperature, thereby achieving the purpose of separating from the first-stage crude helium.
It will be appreciated that the high pressure is easier to obtain than ultra low temperature, N is greater than normal pressure 2 And O 2 The boiling point is higher at high pressure and as such, it is more easily liquefied.
After cryogenic pre-rectification treatment, all of the heavy components relative to helium-3 in the first stage crude helium gas may be reduced to less than 1ppm (parts per million, parts per million concentration) at which point the resulting second stage crude helium gas already has a higher concentration of helium-3.
The cryogenic pre-rectification process has the unique advantages of high throughput, high separation factor and continuous operation. Therefore, in the embodiments of the present application, the helium-3 yield can be increased, while the quality of the obtained helium-3 gas can be improved.
S300, dehydrogenization treatment: and carrying out dehydrogenization treatment on the second-stage crude helium gas to remove residual hydrogen isotope combination gas in the second-stage crude helium gas.
It will be appreciated that the second stage crude helium gas obtained after step S200, although capable of reducing the total heavy component gas relative to helium-3 to less than 1ppm, cannot remove light component gases such as hydrogen isotope combination gas.
Residual trace hydrogen isotope combination gas in the crude helium gas of the second stage can be removed through the hydrogenation treatment step, so that high-quality helium-3 gas is obtained, the purity of the helium-3 gas is more than or equal to 99.9999%, the abundance is more than or equal to 99.96%, the impurity component content is less than 1ppm, and the tritium content is less than or equal to 1.0x10 -11 ％atom。
According to the extraction method of helium-3 in the high tritium heavy water mixed gas, nitrogen is used as the cover gas for the high tritium heavy waterIn the storage process, the mixed gas formed by mixing the covering gas with the gas such as helium-3 obtained after tritium decay is used as a raw material, and the mixed gas is subjected to purification treatment, low-temperature pre-rectification treatment and dehydrogenation treatment in sequence, so that water, water vapor and CO are gradually removed 2 、N 2 、O 2 The hydrocarbon and hydrogen isotopes combine gas to give a high quality helium-3 gas. The mixed gas formed by the top layer of the high tritium heavy water in the storage process can be fully utilized, so that the energy utilization rate is improved, meanwhile, the embodiment of the application provides a new way for obtaining helium-3, so that the yield of helium-3 can be improved, and in addition, the extraction method of helium-3 has the advantages of advanced flow, high separation degree, high helium-3 gas quality and the like.
In some embodiments, the cryogenic pre-rectification process step comprises:
and (3) carrying out low-temperature pre-rectification on the first-stage crude helium by adopting an adsorption filler at the temperature of liquid nitrogen.
The adsorption filler can adsorb target substances, and the principle of low-temperature rectification is utilized to carry out more thorough separation and removal on heavy component (equivalent to helium-3) gas in the first-stage crude helium gas, so as to obtain the second-stage crude helium gas.
It will be appreciated that the second stage crude helium gas includes a combination of a light component helium-3 gas and a hydrogen isotope gas containing trace amounts of tritium.
It should be noted that the type of the adsorbent filler is not limited. For example, in some embodiments, the adsorbent packing includes at least one of a metal delta spiral packing and a θ ring packing.
That is, the adsorption packing may be all the metal triangle spiral packing, may be all the θ ring packing, or may be a part of the metal triangle spiral packing and a part of the θ ring packing.
Of course, the adsorbent filler may equally be other fillers having the same characteristics.
The metal triangular spiral filler has the advantages of cold and heat resistance, large void ratio, large flux, low pressure reduction, small resistance, good separation effect, long service life and the like, so that the separation of helium-3 gas can be well realized, the recycling can be realized, and the cost for obtaining the helium-3 gas is reduced.
The theta-ring filler is the Dixon filler. The theta-ring packing has larger specific surface area and tortuous flow passage, and can increase the gas-liquid phase mass transfer area and the uniformity of fluid distribution, thereby improving the separation efficiency. In addition, the void ratio of the theta-ring filler is higher, so that the flow resistance can be reduced, the residence time of fluid in the filler is reduced, and the energy consumption is reduced, and the extraction efficiency of helium-3 gas can be improved.
In some embodiments, the adsorptive filler comprises a metal delta-helical filler, the material of the metal delta-helical filler comprising at least one of stainless steel and copper.
In some embodiments, prior to the cryogenic pre-rectification process step, the extraction process further comprises:
hydrophilic treatment is carried out on the adsorption filling material.
By hydrophilic treatment of the adsorption packing, the heat transfer, mass transfer and separation effects in the low-temperature pre-rectification treatment process can be enhanced, and other gases except helium-3 gas can be better removed.
As shown in fig. 2, in some embodiments, the purifying treatment step specifically includes:
s110, catalytic oxidation treatment: and carrying out catalytic oxidation treatment on the mixed gas containing helium-3 to remove trace hydrocarbon and partial hydrogen isotope combination gas in the mixed gas and obtain a first mixture.
When nitrogen is used as the blanket gas, a trace amount of hydrocarbon (C x H y )、O 2 、H 2 、CO 2 Meanwhile, during the storage process of the high tritium heavy water, a certain amount of O is generated due to the decomposition of tritium on the water by radiation 2 、D 2 (DT、HD、HT)。
The hydrocarbon and hydrogen isotope combination gas are organic compounds and are easily catalyzed and oxidized, so that the hydrocarbon and most of the hydrogen isotope combination gas can be removed through the catalytic oxidation treatment step.
S120, low-temperature cooling treatment: the first mixture is subjected to a cryogenically cooling process to remove water and part of the water vapour from the first mixture and to obtain a second mixture.
It will be appreciated that the boiling point of water vapour is equivalent to that of CO in the first mixture 2 The difference in boiling points between other gases is very large, so that the water vapor can be liquefied relatively easily by the low-temperature cooling treatment step, and the water vapor can be condensed with water present in the form of mist in the first mixture to form relatively large droplets, which can be removed.
S130, low-temperature adsorption treatment: subjecting the second mixture to low temperature adsorption treatment to remove CO in the second mixture 2 Part N 2 And part O 2 And residual water vapor and obtaining first stage crude helium.
As shown in fig. 2, in some embodiments, the catalytic oxidation treatment step specifically includes:
under the high temperature condition, the mixed gas is controlled to be introduced into the copper oxide, so that the copper oxide and the hydrocarbon and hydrogen isotope combined gas in the mixed gas generate oxidation-reduction reaction.
The copper oxide has stronger reducibility, and after the hydrogen isotope combination gas, hydrocarbon and copper oxide generate oxidation-reduction reaction, the hydrogen isotope combination gas is converted into water or water vapor, and the hydrocarbon is converted into CO 2 And H 2 O, water, steam and CO 2 The removal may be performed by a subsequent cryogenically cooled process step and a cryoadsorptive process step.
That is, by the catalytic oxidation treatment step, the hydrocarbon and hydrogen isotope combination gas which is difficult to be removed can be converted into a substance which is easier to be removed, thereby reducing the difficulty in obtaining high-quality helium-3 gas.
In some embodiments, the cryogenically cooled process step specifically comprises:
the first mixture is controlled to flow through chilled water for sub-cooling.
That is, in the low-temperature cooling step, the cold source is chilled water. The temperature of the chilled water may be between-10 ℃ and-5 ℃, so that the liquefying efficiency of the water vapor can be improved.
In some embodiments, the low temperature adsorption treatment step specifically comprises:
the second mixture is cryoadsorbed with a cryoadsorbing material at liquid nitrogen temperature.
In particular, the liquid nitrogen temperature can reach below-196 ℃, so that the CO 2 、N 2 、O 2 And residual water vapor after the low-temperature cooling treatment step can be absorbed by the low-temperature adsorption material better.
The type of the low-temperature adsorbent is not limited. For example, in some embodiments, the low temperature adsorbent material comprises at least one of a molecular sieve and activated carbon.
That is, the low-temperature adsorption material may be all molecular sieves, all activated carbon, or a part of molecular sieves and a part of activated carbon.
Illustratively, molecular sieves are used for low temperature adsorption. The small molecular substances can pass through the molecular sieve, thereby enabling CO to pass through 2 And the water vapor can be removed, and at the same time, the molecular sieve can also filter out a part of N due to the low-temperature adsorption treatment under the temperature of liquid nitrogen 2 And O 2 。
As shown in fig. 2, in some embodiments, the dehydrogenizing step specifically includes:
s310, palladium membrane permeation treatment: and carrying out palladium membrane permeation treatment on the second-stage crude helium gas to remove part of hydrogen isotope combination gas in the second-stage crude helium gas and obtain third-stage crude helium gas.
Specifically, the hydrogen isotope combination gas in the second-stage crude helium gas can permeate to the other side of the palladium membrane, and helium-3 gas is difficult to pass through the palladium membrane, so that most of the hydrogen isotope combination gas can be removed.
S320, ultra-low temperature adsorption treatment: and performing ultralow-temperature adsorption treatment on the third-stage crude helium to remove residual hydrogen isotope combination gas in the third-stage crude helium.
In order to make the helium-3 gas of higher quality. Trace hydrogen isotope combination gas can also exist in the third-stage crude helium gas obtained after palladium membrane permeation treatment, and the trace hydrogen isotope combination gas in the third-stage crude helium gas can be further removed by adopting ultralow-temperature adsorption treatment, so that the quality of helium-3 gas can be improved.
In some embodiments, the palladium membrane permeation treatment step specifically comprises:
adding quantitative hydrogen into the coarse helium gas in the second stage;
palladium membrane permeation is carried out on the second-stage crude helium added with quantitative hydrogen so as to remove part of hydrogen isotope combination gas in the second-stage crude helium.
The added hydrogen is H 2 . In this way, in the palladium membrane permeation treatment step, the gas pressure on both sides of the palladium membrane can be balanced so that trace tritium in the second stage crude helium gas and the hydrogen isotope combination gas containing hydrogen can pass through the palladium membrane and permeate to the other side of the palladium membrane to be removed.
It will be appreciated that the amount of hydrogen added to the second stage crude helium will remain in trace amounts to the third stage crude helium, and that the residual trace amounts of hydrogen in the third stage crude helium can be removed by the ultra-low temperature adsorption treatment step, thereby ultimately obtaining high quality helium-3 gas.
In some embodiments, the ultra-low temperature adsorption treatment step specifically includes:
and (3) under the condition that the temperature is lower than 0.1K, adopting an ultralow temperature adsorption material to carry out ultralow temperature adsorption on the crude helium gas in the third stage.
The temperature is lower than 0.1K, which means that the temperature is below-273.05 ℃. That is, near the temperature of the liquid helium. Under the working condition, residual trace hydrogen in the crude helium gas in the third stage can be basically removed, and helium-3 gas is reserved, so that the quality of the finally obtained helium-3 gas is improved.
In another aspect, an embodiment of the present application provides a helium-3 extraction system for a high tritium heavy water mixed gas. The helium-3 extraction system is suitable for use in the helium-3 extraction method of any one of the embodiments described above.
As shown in fig. 3, the extraction system includes a purification treatment unit 10, a cryogenic pre-rectification treatment unit 20, and a dehydrogenation treatment unit 30.
The purification unit 10 includes a catalytic oxidation unit 11, a cryocooling unit 12, and a cryoadsorption unit 13.
The catalytic oxidation treatment unit 11 is configured to perform catalytic oxidation treatment on the mixed gas containing helium-3, so as to remove a trace amount of hydrocarbon and a part of hydrogen isotope combination gas in the mixed gas and obtain a first mixture.
Specifically, the catalytic oxidation unit may be a catalytic oxidation column containing copper oxide, and the mixed gas containing helium-3 is passed through the catalytic oxidation column, and at high temperature, copper oxide and hydrocarbon (C x H y ) And hydrogen isotope combination gas, thereby being capable of removing hydrocarbon (C) x H y ) And a hydrogen isotope combination gas (H) 2 、D 2 HD, DT, HT), the mixed gas is passed through a catalytic oxidation column to become a first mixture.
The cryogenically cooled processing unit 12 is configured to cryogenically cool the first mixture to remove water and a portion of water vapor from the first mixture and obtain a second mixture.
Specifically, the cryocooling unit 12 may be a cryocondenser, chilled water flows through the cryocondenser, and the temperature of the chilled water may be between-10 ℃ and-5 ℃, so that water and water vapor in the first mixture may be condensed and separated and removed, and the first mixture becomes the second mixture after passing through the cryocondenser.
The low-temperature adsorption treatment unit 13 is used for performing low-temperature adsorption treatment on the second mixture to remove CO in the second mixture 2 Part N 2 Part O 2 And residual water vapor and obtaining first stage crude helium.
Specifically, the low-temperature adsorption treatment unit 13 may be a low-temperature adsorber or a low-temperature adsorption column. Illustratively, the cryogenic adsorption process unit 13 is a cryogenic adsorber, cryogenic adsorptionAt least one of molecular sieve and active carbon is filled in the appendage, and the water vapor and part of N in the second mixture are further separated and removed by utilizing the low-temperature adsorption principle 2 、O 2 And CO 2 The second mixture separates this portion of the gas to form first stage crude helium.
Cryogenic pre-rectification process unit 20 is configured to perform a cryogenic pre-rectification process on the first stage raw helium gas to remove residual N from the first stage raw helium gas 2 And O 2 And obtaining the crude helium gas of the second stage.
Specifically, cryogenic pre-rectification process unit 20 may be a cryogenic pre-rectification column with an adsorbent packing material contained therein. The heavy component (relative to helium-3) gas contained in the first-stage crude helium is thoroughly removed by utilizing the principle of cryogenic rectification at the temperature of liquid nitrogen, and the second-stage crude helium can be obtained at the top of the cryogenic pre-rectifying tower.
It will be appreciated that the second stage crude helium gas comprises a light component helium-3 gas and a hydrogen isotope combination gas containing trace amounts of tritium.
The adsorption packing can be subjected to hydrophilic treatment, so that the heat transfer, mass transfer and separation effects of the low-temperature pre-rectification process are enhanced.
The type of the adsorbent filler is not limited. Such as at least one of a metal delta spiral packing and a theta ring packing.
When the adsorption filler comprises a metal triangular spiral filler, the material of the metal triangular spiral filler comprises at least one of stainless steel and copper.
The heavy component (relative to helium-3) gas in the second-stage crude helium gas was 1ppm or less.
The dehydrogenization unit 30 includes a palladium membrane permeation processing unit 31 and an ultra-low temperature adsorption processing unit 32.
The palladium membrane permeation processing unit 31 is used for performing palladium membrane permeation processing on the second-stage crude helium gas so as to remove part of hydrogen isotope combination gas in the second-stage crude helium gas and obtain third-stage crude helium gas.
Specifically, the type of the palladium membrane permeation processing unit 31 is not limited. For example, the palladium membrane may be a self-supporting palladium membrane, a supported palladium membrane, or the like.
A certain amount of hydrogen is added into the coarse helium gas of the second stage at the top of the low-temperature pre-rectifying tower so as to maintain the air pressure balance during the palladium membrane permeation treatment, and trace tritium and hydrogen isotope combination gas containing hydrogen in the coarse helium gas of the second stage can be separated and removed through the palladium membrane permeation treatment unit 31.
The ultra-low temperature adsorption processing unit 32 is configured to perform an ultra-low temperature adsorption process on the third-stage crude helium gas to remove residual hydrogen isotope combination gas in the third-stage crude helium gas.
Specifically, the ultralow temperature adsorption treatment unit 32 may be an ultralow temperature adsorption column, and the ultralow temperature adsorption column is filled with an ultralow temperature adsorption material, and the ultralow temperature adsorption material is used for separating and removing residual trace hydrogen in the third-stage crude helium gas under the condition that the temperature is lower than 0.1K, so that high-quality helium-3 gas is obtained.
According to the helium-3 extraction system provided by the embodiment of the application, the purity of the finally obtained helium-3 gas is more than or equal to 99.9999%, the abundance is more than or equal to 99.96%, the impurity component content is less than 1ppm, and the tritium content is less than or equal to 1.0x10 -11 ％atom。
In the description of the present application, reference to the terms "one embodiment," "in some embodiments," "in other embodiments," "in yet other embodiments," or "exemplary" etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the embodiments of the present application. In this application, the schematic representations of the above terms are not necessarily for the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the various embodiments or examples described herein, as well as the features of the various embodiments or examples, may be combined by those skilled in the art without contradiction.
The foregoing is merely a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and variations may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application are included in the protection scope of the present application.
Claims (10)
1. A method for extracting helium-3 from a high tritium heavy water mixed gas, wherein the mixed gas comprises a cover gas, and the cover gas is nitrogen, and the method is characterized by comprising the following steps:
purifying: purifying the mixed gas containing helium-3 to remove water, steam and CO in the mixed gas 2 Hydrocarbon, part N 2 Part O 2 Combining a part of the hydrogen isotopes and obtaining a first-stage crude helium;
cryogenic pre-rectification treatment: subjecting said first stage crude helium to cryogenic pre-rectification to remove residual N from said first stage crude helium 2 And O 2 And obtaining coarse helium gas in the second stage;
and (3) dehydrogenizing: and carrying out dehydrogenization treatment on the second-stage crude helium gas to remove residual hydrogen isotope combination gas in the second-stage crude helium gas.
2. The extraction method according to claim 1, wherein the purification treatment step comprises:
catalytic oxidation treatment: carrying out catalytic oxidation treatment on the mixed gas containing helium-3 to remove trace hydrocarbon and partial hydrogen isotope combination gas in the mixed gas and obtain a first mixture;
and (3) low-temperature cooling treatment: performing low-temperature cooling treatment on the first mixture to remove water and part of water vapor in the first mixture and obtain a second mixture;
and (3) low-temperature adsorption treatment: subjecting the second mixture to low-temperature adsorption treatment to remove CO in the second mixture 2 Part N 2 Part O 2 And residual water vapor and obtaining said first stage crude helium.
3. The extraction method according to claim 2, wherein the catalytic oxidation treatment step specifically comprises:
and under the high temperature condition, controlling the mixed gas to be introduced into the copper oxide so as to enable the copper oxide to generate oxidation-reduction reaction with the hydrocarbon and hydrogen isotope combined gas in the mixed gas.
4. The extraction method according to claim 2, wherein the cryogenically cooling treatment step comprises:
the first mixture is controlled to flow through chilled water for sub-cooling.
5. The extraction method according to claim 2, wherein the low-temperature adsorption treatment step specifically comprises:
and (3) carrying out low-temperature adsorption on the second mixture by adopting a low-temperature adsorption material at the temperature of liquid nitrogen.
6. The extraction method of claim 5, wherein the low temperature adsorbent material comprises at least one of a molecular sieve and activated carbon.
7. The method according to any one of claims 1 to 6, wherein the dehydrogenizing step comprises:
and (3) palladium membrane permeation treatment: performing palladium membrane permeation treatment on the second-stage crude helium gas to remove part of hydrogen isotope combination gas in the second-stage crude helium gas and obtain third-stage crude helium gas;
and (3) ultralow temperature adsorption treatment: and carrying out ultralow-temperature adsorption treatment on the third-stage crude helium gas to remove residual hydrogen isotope combination gas in the third-stage crude helium gas.
8. The extraction method according to claim 7, wherein the palladium membrane permeation treatment step specifically comprises:
adding quantitative hydrogen into the coarse helium gas of the second stage;
and (3) palladium membrane permeation is carried out on the second-stage crude helium added with quantitative hydrogen so as to remove part of hydrogen isotope combination gas in the second-stage crude helium.
9. The extraction method according to claim 7, wherein the ultra-low temperature adsorption treatment step specifically comprises:
and under the condition that the temperature is lower than 0.1K, adopting an ultralow temperature adsorption material to carry out ultralow temperature adsorption on the crude helium gas in the third stage.
10. An extraction system of helium-3 in a high tritium heavy water mixed gas, applicable to the extraction method of helium-3 in a high tritium heavy water mixed gas according to any one of claims 1 to 9, comprising:
the purification treatment unit comprises a catalytic oxidation treatment unit, a low-temperature cooling treatment unit and a low-temperature adsorption treatment unit, wherein the catalytic oxidation treatment unit is used for carrying out catalytic oxidation treatment on the mixed gas containing helium-3 so as to remove trace hydrocarbon and partial hydrogen isotope combined gas in the mixed gas and obtain a first mixture; the low-temperature cooling treatment unit is used for carrying out low-temperature cooling treatment on the first mixture so as to remove water and part of water vapor in the first mixture and obtain a second mixture; the low-temperature adsorption treatment unit is used for carrying out low-temperature adsorption treatment on the second mixture so as to remove CO in the second mixture 2 Part N 2 Part O 2 And residual water vapor and obtaining said first stage crude helium;
a cryogenic pre-rectification processing unit for performing cryogenic pre-rectification processing on the first stage crude helium gas to remove residual N in the first stage crude helium gas 2 And O 2 And obtaining coarse helium gas in the second stage;
the hydrogenation removing treatment unit comprises a palladium membrane permeation treatment unit and an ultralow temperature adsorption treatment unit, wherein the palladium membrane permeation treatment unit is used for carrying out palladium membrane permeation treatment on the second-stage crude helium gas so as to remove part of hydrogen isotope combined gas in the second-stage crude helium gas and obtain third-stage crude helium gas; the ultralow temperature adsorption treatment unit is used for carrying out ultralow temperature adsorption treatment on the third-stage crude helium gas so as to remove residual hydrogen isotope combination gas in the third-stage crude helium gas.
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