WO2014061445A1 - 酸素同位体の濃縮方法 - Google Patents
酸素同位体の濃縮方法 Download PDFInfo
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- WO2014061445A1 WO2014061445A1 PCT/JP2013/076738 JP2013076738W WO2014061445A1 WO 2014061445 A1 WO2014061445 A1 WO 2014061445A1 JP 2013076738 W JP2013076738 W JP 2013076738W WO 2014061445 A1 WO2014061445 A1 WO 2014061445A1
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- oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/02—Separation by phase transition
- B01D59/04—Separation by phase transition by distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/50—Separation involving two or more processes covered by different groups selected from groups B01D59/02, B01D59/10, B01D59/20, B01D59/22, B01D59/28, B01D59/34, B01D59/36, B01D59/38, B01D59/44
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/24—Nitric oxide (NO)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B5/00—Water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B5/00—Water
- C01B5/02—Heavy water; Preparation by chemical reaction of hydrogen isotopes or their compounds, e.g. 4ND3 + 7O2 ---> 4NO2 + 6D2O, 2D2 + O2 ---> 2D2O
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/08—Separating gaseous impurities from gases or gaseous mixtures or from liquefied gases or liquefied gaseous mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
- H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/28—Separation by chemical exchange
- B01D59/32—Separation by chemical exchange by exchange between fluids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention when a specific oxygen isotope is concentrated in a large amount by distilling nitric oxide, it is not necessary to regularly replenish a large amount of nitric oxide as a raw material, and the liquid NO hold-up amount is small.
- the present invention relates to an oxygen isotope enrichment method capable of concentrating oxygen isotopes without reducing the oxygen isotope separation efficiency.
- Non-Patent Document 1 a distillation method using nitric oxide (NO) described in Non-Patent Document 1 as a raw material (hereinafter referred to as “NO distillation method”), water ( H 2 O) as a raw material (hereinafter referred to as “water distillation method”), oxygen (O 2 ) as a raw material (hereinafter referred to as “oxygen distillation method”), carbon monoxide (CO) Methods such as a distillation method using raw materials (hereinafter referred to as “CO distillation method”) are used.
- Table 1 shows a comparison table of the NO distillation method, the water distillation method, the oxygen distillation method, and the CO distillation method.
- Relative volatility corresponds to the separation factor.
- the number of theoretical plates necessary for the separation and enrichment of oxygen isotopes is roughly proportional to the reciprocal of (separation factor-1) when the relative volatility is small.
- the NO distillation method is necessary for the separation of oxygen isotopes as compared with other distillation methods (specifically, the water distillation method, the oxygen distillation method, and the CO distillation method). It is possible to reduce the number of theoretical plates to about 1/10. Therefore, the NO distillation apparatus can be reduced in size and the energy required for the separation of oxygen isotopes can be reduced.
- the NO distillation apparatus used in the NO distillation method has a problem that the liquid NO hold-up amount becomes large when the scale of nitric oxide distillation is large. Nitric oxide is highly reactive, so if the hold-up amount is large, it may lead to a major disaster if it leaks.
- the present invention eliminates the need to periodically replenish a large amount of nitric oxide as a raw material when a large amount of nitric oxide as a raw material is distilled, and with a small liquid NO hold-up amount, It is an object of the present invention to provide an oxygen isotope enrichment method capable of obtaining a large amount of oxygen isotopes without reducing the separation efficiency.
- a first distillation column group in which a plurality of distillation columns are cascade-connected is used as the first distillation apparatus.
- the oxygen isotope enrichment method according to (1) or (2) is provided.
- the second distillation apparatus uses a second distillation column group in which a plurality of distillation columns are cascade-connected (1) to ( The method for concentrating oxygen isotopes according to any one of 3) is provided.
- the process which acquires the water by which the water which contains an oxygen isotope is roughly concentrated by distilling the water which is a raw material using the 1st distillation apparatus, and the 2nd distillation apparatus is used.
- obtaining water having a reduced concentration of oxygen isotope and water having a reduced concentration of oxygen isotope, and the second distillation of nitric oxide having an increased concentration of oxygen isotope A method for concentrating oxygen isotopes is provided, wherein the oxygen isotopes are supplied to the apparatus and the water in which the concentration of the oxygen isotopes is reduced is refluxed to the first distillation apparatus.
- the first distillation column group in which a plurality of distillation columns are cascade-connected is used as the first distillation device.
- the oxygen isotope enrichment method according to (5) is provided.
- a second distillation column group in which a plurality of distillation columns are cascade-connected is used as the second distillation apparatus (5) or ( The oxygen isotope enrichment method according to 6) is provided.
- oxygen obtained by roughly concentrating the target oxygen isotope by oxygen distillation is hydrogenated to form water, and the concentration of the oxygen isotope is reduced by nitrogen monoxide distillation. It is not necessary to periodically replenish a large amount of nitric oxide as a raw material by chemically exchanging water with the water and returning nitric oxide having a higher oxygen isotope concentration to the nitric oxide distillation apparatus. Compared to the case where everything is concentrated by distillation with nitric oxide, a large amount of nitric oxide enriched with the desired oxygen isotope is obtained without reducing the separation efficiency while reducing the amount of liquid nitric oxide hold-up. can do.
- the oxygen isotope separation process described above that is, “water distillation (or oxygen distillation) ⁇ chemical exchange reaction ⁇ NO distillation” is used, so that the separation efficiency of oxygen isotopes can be reduced with a small liquid NO hold-up amount. A large amount of oxygen isotopes can be obtained without reduction.
- the nitric oxide extracted as a product when performing NO distillation is replenished (supplemented with a small flow of nitric oxide). Just do it. For this reason, in order to obtain a large amount of oxygen isotopes, it is necessary to distill a large amount of nitric oxide as a raw material, but it is not necessary to regularly prepare a large amount of nitric oxide (raw material). Thereby, safety can be ensured.
- FIG. 1 is a diagram schematically showing a schematic configuration of an oxygen isotope enrichment apparatus used when performing the oxygen isotope enrichment method according to the first embodiment of the present invention.
- an oxygen isotope enrichment apparatus 10 used when performing the oxygen isotope enrichment method of the first embodiment will be described with reference to FIG.
- the oxygen isotope concentrator 10 according to the first embodiment includes a first distillation device 11, a second distillation device 12, a hydrogenation unit 14, a water splitting unit 15, a chemical exchange column 16, a dehydration unit, The unit 17, the oxygen reflux path 18, the water reflux path 19, and the water supply path 20 are included.
- the first distillation apparatus 11 is an apparatus that performs distillation using oxygen (O 2 ) as a raw material, and includes a first distillation column group 21, a first condenser 23, a first evaporator 24, and a second evaporator.
- the first distillation column group 21 has a configuration in which first to third distillation columns 21A, 21B, and 21C are cascade-connected. Cascade connection means that the first to third distillation columns 21A, 21B, and 21C are connected in series.
- the first distillation column group 21 continuously concentrates a specific component in the raw material, so that the specific component concentrated in the first distillation column 21A is concentrated in the second distillation column 21B.
- the specific component concentrated in the second distillation column 21B is concentrated in the third distillation column 21C. This one continuous distillation process is called a cascade process.
- the first distillation column 21A to which oxygen (O 2 ) as a raw material is supplied has a low isotope concentration, it is necessary to process a large amount of oxygen. Since the isotope concentration is increased by the distillation operation, the oxygen treatment amount in the column decreases in the order of the second distillation column 21B and the third distillation column 21C. For this reason, the diameter of the first distillation column 21A is the largest, and the diameter of the third distillation column 21C is the smallest.
- the first distillation column group 21 is constituted by three distillation columns (in this case, the first to third distillation columns 21A, 21B, and 21C). Although the case has been described as an example, the number of distillation columns constituting the first distillation column group 21 is not limited to this.
- the first condenser 23 is connected to the top of the first distillation column 21A and is provided in a top gas path 34 for transporting gas.
- the first condenser 23 is connected to the reflux liquid path 35.
- the first condenser 23 has a path through which the heat medium fluid passes.
- the first condenser 23 cools and liquefies the gas derived from the top of the first distillation column 21A by heat exchange with the heat medium fluid.
- the liquefied condensate is returned to the upper part of the first distillation column 21A via the reflux liquid path 35.
- the first evaporator 24 is provided in a supply gas path 39 connected to the bottom of the first distillation column 21A and the top of the second distillation column 21B.
- the first evaporator 24 has a path through which the heat medium fluid passes.
- the first evaporator 24 realizes a distillation operation by heat-exchanging the liquid led out from the bottom of the first distillation column 21A with the heat medium fluid and heating and evaporating the liquid.
- 18 O and 17 O are concentrated at the bottom of the distillation column 21A.
- the oxygen isotope concentrator 10 includes a plurality of distillation columns (specifically, first to third distillation columns 21A, 21B, and 21C), this stage (first concentration) Then, 18 O and 17 O are not sufficiently concentrated.
- the oxygen enriched with 18 O and 17 O is supplied to the upper portion of the second distillation column 21B via the supply gas passage 39.
- the second condenser 26 is connected to the top of the second distillation column 21B and is provided in the top gas path 42 for transporting gas.
- the second condenser 26 is connected to the liquid path 43.
- the reflux liquid path 45 is branched from the liquid path 43 and connected to the upper part of the second distillation column 21B.
- the second condenser 26 has a path through which the heat medium fluid passes.
- the second condenser 26 cools and liquefies the gas derived from the top of the second distillation column 21B by heat exchange with the heat medium fluid.
- the liquefied condensate is returned to the upper part of the second distillation column 21B via the liquid path 43 and the reflux liquid path 45.
- the second evaporator 27 is provided in a supply gas path 46 connected to the bottom of the second distillation column 21B and the top of the third distillation column 21C.
- the second evaporator 27 has a path through which the heat medium fluid passes.
- the second evaporator 27 causes the liquid derived from the bottom of the second distillation column 21B to exchange heat with the heat medium fluid, and heats and vaporizes the liquid to generate rising gas.
- 18 O and 17 O are concentrated.
- 18 O and 17 O are more concentrated than after the first concentration.
- the oxygen enriched with 18 O and 17 O is supplied to the upper portion of the third distillation column 21 ⁇ / b> C through the supply gas path 46.
- the third condenser 29 is connected to the top of the third distillation column 21C and is provided in a tower top gas path 49 that transports gas.
- the third condenser 29 is connected to the liquid path 51.
- the reflux liquid path 52 is branched from the liquid path 51 and connected to the upper part of the third distillation column 21C.
- the third condenser 29 has a path through which the heat medium fluid passes.
- the third condenser 29 cools and liquefies the gas derived from the top of the third distillation column 21C by heat exchange with the heat medium fluid.
- the liquefied condensate is returned to the upper part of the third distillation column 21 ⁇ / b> C via the liquid path 51 and the reflux liquid path 52.
- the third evaporator 31 is provided in the supply gas path 54 connected to the bottom of the third distillation column 21 ⁇ / b> C and the hydrogenation unit 14.
- the third evaporator 31 has a path through which the heat medium fluid passes.
- the third evaporator 31 causes the liquid derived from the bottom of the third distillation column 21C to exchange heat with the heat medium fluid, and heats and vaporizes the liquid, thereby increasing the concentration of 18 O and 17 O. Generate gas.
- 18 O and 17 O are more concentrated than after the second concentration.
- Oxygen obtained by roughly concentrating 18 O and 17 O is supplied to the hydrogenation unit 14 via the supply gas path 54.
- the second distillation apparatus 12 is an apparatus that performs distillation using nitric oxide (NO) as a raw material, and includes a second distillation column group 61, a heat exchanger 63, a reflux gas path 64, and a raw material supply path 66.
- a liquid supply path 81 to the fourth evaporator 69, a liquid path 84, and a liquid supply path 88 to the fifth evaporator 73 are included.
- the second distillation column group 61 has a configuration in which the fourth and fifth distillation columns 61A and 61B are cascade-connected. That is, since the second distillation column group 61 continuously concentrates a specific component in the raw material, the specific component concentrated in the fourth distillation column 61A is concentrated in the fifth distillation column 61B.
- the fourth distillation column 61A supplied with the raw material nitric oxide (NO) has a larger distillation load than the fifth distillation column 61B. For this reason, the column diameter of the fourth distillation column 61A is larger than the column diameter of the fifth distillation column 61B.
- the second distillation column group 61 a case where the second distillation column group 61 is configured by two distillation columns (in this case, the fourth and fifth distillation columns 61A and 61B). Although described as an example, the number of distillation columns constituting the second distillation column group 61 is not limited to this.
- the heat exchanger 63 brings the normal temperature gas of the chemical exchange column 16 close to the temperature in the fourth distillation column 61A (for example, a low temperature of about 120K) before introducing it into the distillation column 61A by heat exchange with the exhaust gas.
- the reflux gas path 64 is a path through which nitrogen monoxide (NO) as a raw material is supplied, and supplies nitrogen monoxide, which is an exhaust gas generated when distilling the nitric oxide, to the bottom of the chemical exchange tower 16. It is a route for.
- NO nitrogen monoxide
- the raw material supply path 66 supplies nitric oxide having an increased concentration of oxygen isotopes ( 18 O and 17 O) to the fourth distillation column 61 A constituting the second distillation apparatus 12.
- the fourth condenser 68 is connected to the top of the fourth distillation column 61A, and is provided in the top gas path 75 for transporting gas.
- the fourth condenser 68 is connected to the reflux liquid path 77.
- the fourth condenser 68 has a path through which the heat medium fluid passes.
- the fourth condenser 68 cools and liquefies the gas derived from the top of the fourth distillation column 61A by heat exchange with the heat medium fluid.
- the liquefied condensate is returned to the upper part of the fourth distillation column 61A via the reflux liquid path 77.
- the fourth evaporator 69 is provided in a supply gas path 81 connected to the bottom of the fourth distillation column 61A and the top of the fifth distillation column 61B.
- the fourth evaporator 69 has a path through which the heat medium fluid passes.
- the fourth evaporator 69 causes the liquid derived from the bottom of the fourth distillation column 61A to exchange heat with the heat medium fluid, and heats and vaporizes the liquid to generate rising gas. Thereby, the concentration of oxygen isotopes ( 18 O and / or 17 O) is increased at the bottom of the fourth distillation column 61A. Nitric oxide (NO) enriched with oxygen isotopes ( 18 O and / or 17 O) is supplied to the upper portion of the fifth distillation column 61 B via the supply gas path 81.
- NO Nitric oxide
- the fifth condenser 72 is connected to the top of the fifth distillation column 61B and is provided in the top gas path 83 for transporting gas.
- the fifth condenser 72 is connected to the liquid path 84.
- the reflux liquid path 86 is branched from the liquid path 84 and connected to the upper part of the fifth distillation column 61B.
- the fifth condenser 72 has a path through which the heat medium fluid passes.
- the fifth condenser 72 cools and liquefies the gas derived from the top of the fifth distillation column 61B by heat exchange with the heat medium fluid.
- the liquefied condensate is returned to the upper part of the fifth distillation column 61B via the liquid path 84 and the reflux liquid path 86.
- the fifth evaporator 73 is provided in the supply gas path 88 connected to the bottom of the fifth distillation column 61B.
- the fifth evaporator 73 has a path through which the heat medium fluid passes.
- the fifth evaporator 73 causes the liquid derived from the bottom of the fifth distillation column 61B to exchange heat with the heat medium fluid, and heats and vaporizes the liquid to generate rising gas.
- the product nitric oxide N 18 O and / or N 17 O (gas)
- the hydrogenation unit 14 is connected to the upper part of the chemical exchange tower 16 through a water supply path 20.
- the water generation unit 14 adds hydrogen to oxygen in which oxygen isotopes ( 18 O and 17 O) are roughly concentrated via the supply gas path 54, and reacts them to make water.
- oxygen isotopes 18 O and 17 O
- water may be obtained by reacting oxygen in which oxygen isotopes are roughly concentrated and hydrogen.
- the water is supplied to the upper part of the chemical exchange column 16 via the water supply path 20.
- the water splitting unit 15 is connected to the oxygen reflux path 18 and the water reflux path 19. Water having a reduced concentration of oxygen isotopes ( 18 O and 17 O) is supplied to the water splitting unit 15 from the bottom of the chemical exchange column 16 via the water reflux path 19.
- the water splitting unit 15 electrolyzes water having a reduced oxygen isotope concentration. At this time, water generated by using a hydrogen fuel cell in the hydrogenation unit 14 is electrolyzed using water having a reduced oxygen isotope concentration.
- the water splitting unit 15 supplies oxygen obtained when electrolyzing water having a reduced oxygen isotope concentration to the third distillation column 21 ⁇ / b> C constituting the first distillation apparatus 11 via the oxygen reflux path 18. Supply.
- the chemical exchange column 16 is disposed between the first distillation apparatus 11 and the second distillation apparatus 12.
- the top of the chemical exchange column 16 is connected to a raw material gas supply path 66.
- the upper part of the chemical exchange column 16 is connected to the water supply path 20.
- the bottom of the chemical exchange column 16 is connected to the reflux gas path 64.
- the chemical exchange tower 16 is supplied with water via the water supply path 20 and with nitrogen monoxide discharged from the second distillation apparatus 12 via the reflux gas path 64.
- oxygen isotopes ( 18 O and 17 O are obtained by chemically exchanging water supplied via the water supply path 20 and nitrogen monoxide discharged from the second distillation apparatus 12. ) To obtain nitrogen monoxide having an increased concentration of oxygen) and water having a reduced concentration of oxygen isotopes ( 18 O and 17 O).
- the dehydration unit 17 is provided in a raw material supply path 66 located between the chemical exchange tower 16 and the heat exchanger 63.
- the dehydrating unit 17 has a function of removing moisture contained in the nitric oxide gas after chemical exchange.
- the oxygen reflux path 18 is for separating oxygen separated from water by the water splitting unit 15 (specifically, oxygen obtained by electrolyzing water in which the concentration of oxygen isotopes ( 18 O and 17 O) is reduced).
- the first distillation apparatus 11 is refluxed to the configuration.
- the water reflux path 19 extracts water with a reduced concentration of oxygen isotopes ( 18 O and 17 O) from the bottom of the chemical exchange column 16 and supplies the water to the bottom of the water splitting unit 15.
- the water supply path 20 has one end connected to the hydrogenation unit 14 and the other end connected to the upper part of the chemical exchange tower 16.
- the water supply path 20 is a path for supplying the water generated in the hydrogenation unit 14 to the upper part of the chemical exchange tower 16.
- N 17 O as a product is taken out from the middle of the fifth distillation column 61B, and N 18 O as a product is taken out from the bottom of the fifth distillation column 61B. Is possible.
- N 18 O extraction line is illustrated as an example.
- oxygen which is a raw material
- first distillation apparatus 11 to obtain oxygen in which oxygen isotopes ( 18 O and 17 O) are roughly concentrated.
- the raw material oxygen is supplied to the first distillation column 21A, and the first distillation column group 21 in which the first to third distillation columns 21A, 21B, and 21C are cascade-connected is used. Distill the oxygen that is. Thereby, oxygen in which oxygen isotopes are roughly concentrated is generated. The oxygen in which the oxygen isotope is roughly concentrated is supplied to the hydrogenation unit 14.
- the hydrogenation unit 14 water is obtained by adding hydrogen to oxygen in which the oxygen isotope is roughly concentrated.
- the hydrogenation unit 14 for example, using hydrogen fuel cell, or when the oxygen isotope (18 O and 17 O) to obtain the water by reacting the crude enriched oxygen and hydrogen.
- the water splitting unit 15 as the electricity for electrolyzing the water in which the oxygen isotope concentration is reduced, the hydrogen fuel cell is used to react oxygen and hydrogen in which the oxygen isotope is roughly concentrated. It is possible to use electricity generated when
- the water generated by the hydrogenation unit 14 is supplied to the upper part of the chemical exchange tower 16 via the water supply path 20.
- nitric oxide as a raw material is distilled using the second distillation apparatus 12 to generate nitric oxide as a product (specifically, N 17 O and N 18 O).
- nitrogen monoxide as a raw material is supplied to the fourth distillation column 61A, and the second distillation column group 61 in which the fourth and fifth distillation columns 61A and 61B are cascade-connected is used. Distill off the nitric oxide.
- Nitric oxide discharged from the second distillation apparatus 12 is supplied to the bottom of the chemical exchange column 16.
- the oxygen isotope ( 18 O and the oxygen supplied through the water supply path 20 and the nitrogen monoxide discharged from the second distillation apparatus 12 are chemically exchanged. 17 O) nitric oxide concentration is increased, and the concentration of oxygen isotope (18 O and 17 O) to obtain the water drops.
- the above “chemical exchange” means that oxygen atoms (O) are isotope-exchanged between different kinds of chemical species, for example, H 2 O and NO in gas-liquid contact.
- the nitric oxide produced in the chemical exchange tower 16 and having a higher concentration of oxygen isotopes ( 18 O and 17 O) passes through the dehydration unit 17, the heat exchanger 63, and the raw material supply path 66. It is supplied to the upper part of the fourth distillation column 61A. Further, the water produced in the chemical exchange tower 16 and having a reduced concentration of oxygen isotopes ( 18 O and 17 O) is supplied to the bottom of the water splitting section 15 via the water reflux path 19.
- the water splitting unit 15 electrolyzes water in which the concentration of oxygen isotopes ( 18 O and 17 O) is reduced. At this time, water generated by using a hydrogen fuel cell in the hydrogenation unit 14 is electrolyzed using water having a reduced oxygen isotope concentration.
- the water splitting unit 15 supplies oxygen obtained when electrolyzing water having a reduced oxygen isotope concentration to the third distillation column 21 ⁇ / b> C constituting the first distillation apparatus 11 via the oxygen reflux path 18. Supply.
- oxygen isotopes ( 18 O and 17 O) are roughly concentrated by distilling oxygen as a raw material using the first distillation apparatus 11.
- the step of acquiring the oxygen the step of acquiring water by adding hydrogen to the oxygen in which the oxygen isotopes ( 18 O and 17 O) are roughly concentrated, Chemical exchange between the process of obtaining nitric oxide, which is discharged when the raw material nitric oxide is distilled and whose oxygen isotope ( 18 O and 17 O) concentration is reduced, and the discharged nitric oxide
- FIG. 2 is a diagram schematically showing a schematic configuration of an oxygen isotope enrichment apparatus used when performing the oxygen isotope enrichment method according to the second embodiment of the present invention. 2, the same components as those in the oxygen isotope enrichment apparatus 10 according to the first embodiment shown in FIG.
- the oxygen isotope enrichment apparatus 100 used when performing the oxygen isotope enrichment method of the second embodiment will be described with reference to FIG.
- the oxygen isotope enrichment apparatus 100 of the second embodiment is provided with a first distillation apparatus 101 in place of the first distillation apparatus 11 provided in the oxygen isotope enrichment apparatus 10 of the first embodiment.
- the oxygen isotopes except that the hydrogenation part 14, the water splitting part 15, the oxygen reflux path 18 and the water supply path 20 constituting the oxygen isotope enrichment apparatus 10 are excluded from the constituent elements and the water reflux path 103 is further provided.
- the configuration is the same as that of the isotope concentrator 10.
- the first distillation apparatus 101 is an apparatus that performs distillation using water (H 2 O) as a raw material, and includes a first distillation column group 105, a first condenser 108, a first evaporator 109, The second condenser 112, the second evaporator 113, the third condenser 115, the third evaporator 116, the top gas path 118, 125, 132, and the reflux liquid path 119, 128, 135. And supply gas passages 123, 129, and 136 and liquid passages 126 and 133.
- H 2 O water
- the first distillation column group 105 is configured such that the first to third distillation columns 105A, 105B, and 105C are cascade-connected.
- the first distillation column group 105 continuously concentrates a specific component in the raw material, so that the specific component concentrated in the first distillation column 105A is concentrated in the second distillation column 105B.
- the specific component concentrated in the second distillation column 105B is concentrated in the third distillation column 105C.
- the first distillation column 105A to which water (H 2 O) as a raw material is supplied has a low isotope concentration, it is necessary to process a large amount of water. Since the isotope concentration is increased by the distillation operation, the water treatment amount in the column decreases in the order of the second distillation column 105B and the third distillation column 105C. For this reason, the column diameter of the first distillation column 105A is the largest, and the column diameter of the third distillation column 105C is the smallest.
- the first distillation column group 105 is configured by three distillation columns (in this case, the first to third distillation columns 105A, 105B, and 105C). Although the case has been described as an example, the number of distillation columns constituting the first distillation column group 105 is not limited to this.
- the first condenser 108 is connected to the top of the first distillation column 105A, and is provided in the top gas path 118 for transporting gas.
- the first condenser 108 is connected to the reflux liquid path 119.
- the first condenser 108 has a path through which the heat medium fluid passes.
- the first condenser 108 cools and liquefies the gas derived from the top of the first distillation column 105A by heat exchange with the heat medium fluid.
- the liquefied condensate is returned to the upper part of the first distillation column 105A via the reflux liquid path 119.
- the first evaporator 109 is provided in a supply gas path 123 connected to the bottom of the first distillation column 105A and the top of the second distillation column 105B.
- the first evaporator 109 has a path through which the heat medium fluid passes.
- the first evaporator 109 exchanges the liquid derived from the bottom of the first distillation column 105A with the heat medium fluid, and heats the liquid to vaporize it, whereby water in which 18 O and 17 O are concentrated is obtained. To get. At this stage (first concentration), 18 O and 17 O are not yet fully concentrated.
- the water enriched with 18 O and 17 O is supplied to the upper portion of the second distillation column 105B via the supply gas path 123.
- the second condenser 112 is connected to the tower top of the second distillation tower 105B and is provided in the tower top gas path 125 for transporting gas.
- the second condenser 112 is connected to the liquid path 126.
- the reflux liquid path 128 is branched from the liquid path 126 and connected to the upper part of the second distillation column 105B.
- the second condenser 112 has a path through which the heat medium fluid passes.
- the second condenser 112 cools and liquefies the gas derived from the top of the second distillation column 105B by heat exchange with the heat medium fluid.
- the liquefied condensate is returned to the upper part of the second distillation column 105B via the liquid path 126 and the reflux liquid path 128.
- the second evaporator 113 is provided in the supply gas path 129 connected to the bottom of the second distillation column 105B and the top of the third distillation column 105C.
- the second evaporator 113 has a path through which the heat medium fluid passes.
- the second evaporator 113 exchanges the liquid led out from the bottom of the second distillation column 105B with the heat medium fluid, and heats and vaporizes the liquid, so that water in which 18 O and 17 O are concentrated is obtained. To get. In this stage (second concentration), 18 O and 17 O are more concentrated than after the first concentration.
- the water enriched with 18 O and 17 O is supplied to the upper portion of the third distillation column 105C via the supply gas path 129.
- the third condenser 115 is connected to the top of the third distillation column 105C, and is provided in the top gas path 132 for transporting gas.
- the third condenser 115 is connected to the liquid path 133.
- the reflux liquid path 135 is branched from the liquid path 133 and connected to the upper part of the third distillation column 105C.
- the third condenser 115 has a path through which the heat medium fluid passes.
- the third condenser 115 cools and liquefies the gas derived from the top of the third distillation column 105C by heat exchange with the heat medium fluid.
- the liquefied condensate is returned to the upper part of the third distillation column 105C via the liquid path 133 and the reflux liquid path 135.
- the third evaporator 116 is provided in the supply gas path 136 connected to the bottom of the third distillation column 105 ⁇ / b> C and the chemical exchange column 16.
- the third evaporator 116 has a path through which the heat medium fluid passes.
- the liquid derived from the bottom of the third distillation column 105C is subjected to heat exchange with the heat medium fluid, and the liquid is heated and vaporized, whereby 18 O and 17 O are roughly concentrated. Get water. In this stage (third concentration), 18 O and 17 O are more concentrated than after the second concentration.
- the water in which 18 O and 17 O are roughly concentrated is supplied to the chemical exchange column 16 via the supply gas path 136.
- waste component W 2 is discharged from the top of the first distillation column 105A.
- the water reflux path 103 extracts water having a reduced concentration of oxygen isotopes ( 18 O and 17 O) from the lower end of the chemical exchange column 16 and also supplies water having a reduced concentration of oxygen isotopes ( 18 O and 17 O). It supplies to the lower part of the 3rd distillation column 105C.
- the oxygen isotope concentrator 100 of the second embodiment having the above-described configuration can directly perform chemical exchange of water, it is necessary for the oxygen isotope concentrator 10 of the first embodiment. Further, the hydrogenation unit 14 and the water splitting unit 15 are not necessary. For this reason, the oxygen isotope enrichment apparatus 100 of the second embodiment can have a simpler configuration than the oxygen isotope enrichment apparatus 10 of the first embodiment.
- the oxygen isotope ( 17 O, 18 O) concentration of nitric oxide supplied to the second distillation apparatus 12 can be made substantially the same as that in the first embodiment. Because the relative volatility of water isotopes and the relative volatility of oxygen isotopes (eg, H 2 18 O / H 2 16 O and 16 O 18 O / 16 O 16 O) are almost the same.
- the oxygen isotope concentration of water supplied to the exchange column 16 is the oxygen isotope concentration of water obtained by adding hydrogen to oxygen derived from the second distillation apparatus 12; This is because substantially the same concentration can be obtained.
- the raw material water is supplied to the first distillation column 105A, and the first distillation column group 105 in which the first to third distillation columns 105A, 105B, and 105C are cascade-connected is used. Distill the water that is. Thereby, water in which the oxygen isotope is roughly concentrated is generated. The water in which the oxygen isotope is roughly concentrated is supplied to the upper part of the chemical exchange column 16 via the supply gas path 136.
- nitric oxide as a raw material is distilled to produce nitric oxide as a product (specifically, N 17 O and / or N 18 O).
- nitrogen monoxide as a raw material is supplied to the fourth distillation column 61A, and the second distillation column group 61 in which the fourth and fifth distillation columns 61A and 61B are cascade-connected is used.
- Distill the nitric oxide which is Nitric oxide discharged from the second distillation apparatus 12 is supplied to the bottom of the chemical exchange column 16.
- the oxygen isotope ( 18 O and 17 O) is subjected to chemical exchange between the water in which the oxygen isotopes ( 18 O and 17 O) are roughly concentrated and the nitrogen monoxide discharged from the second distillation apparatus 12.
- body (18 O and 17 O) nitric oxide concentration is increased, and the concentration of oxygen isotope (18 O and 17 O) to obtain the water drops.
- the above “chemical exchange” means that oxygen atoms (O) are isotope-exchanged between different kinds of chemical species, for example, H 2 O and NO in gas-liquid contact.
- the nitric oxide produced in the chemical exchange tower 16 and having a higher concentration of oxygen isotopes ( 18 O and 17 O) passes through the dehydration unit 17, the heat exchanger 63, and the raw material supply path 66. It is supplied to the upper part of the fourth distillation column 61A. Further, the water generated in the chemical exchange column 16 and having a reduced concentration of oxygen isotopes ( 18 O and 17 O) is supplied to the lower portion of the third distillation column 105 C via the water reflux path 103.
- water containing oxygen isotopes ( 18 O and 17 O) is obtained by distilling water as a raw material using the first distillation apparatus 101.
- a step of obtaining water in which molecules are roughly concentrated a step of obtaining nitric oxide discharged when distilling nitric oxide as a raw material using the second distillation apparatus 12, and a step of coarse concentration
- the concentration of oxygen isotopes ( 18 O and 17 O) is increased, and the concentrations of nitrogen isotopes ( 18 O and 17 O) are increased.
- nitric oxide having an increased oxygen isotope concentration to the second distillation apparatus 12 and supplying the reduced water concentration of the oxygen isotope to the first distillation.
- a large amount of nitric oxide, which is a raw material is distilled by refluxing the apparatus 101.
- it is not necessary to regularly replenish a large amount of nitric oxide as a raw material and a large amount of oxygen isotope can be obtained with a small liquid NO hold-up amount without reducing the oxygen isotope separation efficiency. can do.
- oxygen isotopes ( 18 O and 17 O) were concentrated using the oxygen isotope enrichment apparatus 10 of the first embodiment shown in FIG.
- the content of 17 O contained in the product nitric oxide (N 17 O) is 10 atom% or more
- the content of 18 O contained in the product nitric oxide (N 18 O) is 98 atom%. That is all.
- nitric oxide (N 17 O) a process of oxygen isotope enrichment method was constructed assuming that 5 tons of hydrogenated 17 O concentrated water was produced per year. .
- oxygen supplied to the first distillation column 21A, and the first to third distillation columns 21A, 21B, and 21C are cascade-connected.
- oxygen isotope (18 O and 17 O) has generated a crude enriched oxygen .
- concentrations of 17 O and 18 O at the bottom of the third distillation column 21C were determined.
- the concentration of 17 O was 2.23 atom% and the concentration of 18 O was 26.1 atom%.
- the production rate of nitric oxide enriched with oxygen isotopes as the product obtained at this time was 0.58 Nm 3 / h.
- oxygen in which oxygen isotopes were roughly concentrated was supplied to the hydrogenation unit 14.
- hydrogen is obtained by adding hydrogen to oxygen in which the oxygen isotope is roughly concentrated, and the generated water is supplied to the upper part of the chemical exchange tower 16 via the water supply path 20. Supplied.
- nitric oxide as a raw material is distilled to produce nitric oxide as a product (specifically, N 17 O and / or N 18 O).
- the concentration of 17 O contained in N 17 O was determined to be 2 atom%. Further, when the concentration of 18 O contained in N 18 O was determined, it was 23.6 atom%.
- N 17 O as a product was taken out at an intermediate position of the distillation column, and N 18 O as a product was taken out at the bottom of the distillation column.
- water to obtain a final product N 17 O - case 17 O Production of (H 2 17 O) is 5 tons per year, water for obtaining N 18 O - of 18 O in 1 year The production volume will be 10 tons.
- oxygen isotope can be recovered by supplying oxygen generated by electrolyzing water to the first distillation apparatus 11, so that oxygen is not wasted for concentrating the raw materials. Isotope production is possible. Furthermore, in the present invention, it is only necessary to replenish the amount of nitric oxide extracted as a product when performing NO distillation, so that the above-described production rate of 0.58 Nm 3 / h is replenished. In addition, when the oxygen isotope production is set to the same condition and all are performed by the second distillation apparatus 12, the distillation is performed with 1200 stages (in other words, 1200 cascaded distillation columns). It is necessary to supply the raw material at a supply speed of 1600 Nm 3 / h. Considering the liquid hold-up in the distillation column, a large amount of nitric oxide is used.
- the liquid NO hold-up of the second distillation apparatus 12 is compared with an apparatus that performs distillation concentration only with NO. It can be reduced to about 1/10.
- the present invention when a large amount of nitric oxide as a raw material is distilled, it is not necessary to regularly replenish a large amount of nitric oxide as a raw material, and an oxygen isotope separation efficiency can be achieved with a small liquid NO hold-up amount.
- the method can be applied to an oxygen isotope enrichment method capable of concentrating oxygen isotopes without lowering.
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Abstract
Description
本願は、2012年10月18日に、日本に出願された特願2012-230766号に基づき優先権を主張し、その内容をここに援用する。
表1に、NO蒸留法、水蒸留法、酸素蒸留法、及びCO蒸留法の比較表を示す。
このため、表1に示すように、NO蒸留法は、他の蒸留法(具体的には、水蒸留法、酸素蒸留法、及びCO蒸留法)と比較して、酸素同位体の分離に必要な理論段数を約1/10にすることが可能となる。
したがって、NO蒸留装置を小型化でき、かつ酸素同位体の分離に必要なエネルギーを小さくすることができる。
本発明では、濃縮された酸素同位体である18O及び/又は17Oを含む水と、該水と比較して18O及び/又は17Oの濃度が低いNOガス(一酸化窒素)と、を気液接触させることで、酸素原子の化学交換反応を行う。
本発明における「化学交換」とは、異種の化学種間、例えば、H2OとNOとを気液接触させて、酸素原子(O)について同位体交換させることをいう。
NO蒸留(一酸化窒素を原料とする蒸留)を行った際に排出される18Oの濃度が低下した一酸化窒素と、水蒸留(水を原料とする蒸留)または酸素蒸留(酸素を原料とする蒸留)に粗濃縮されたH2 18O(liquid)と、を気液接触させる。粗濃縮されたH2 18Oとの接触で18Oが増加した一酸化窒素をNO蒸留に戻す。17Oの場合も同様な交換反応を行うことができる。
なお、本発明における「粗濃縮」とは、天然存在比から数%まで酸素同位体を濃縮することをいう。
このため、酸素同位体を大量に得るためには原料である一酸化窒素を大量に蒸留する必要があるが、一酸化窒素(原料)を定期的に大量に準備する必要がなくなる。これにより、安全性が確保できる。
図1は、本発明の第1の実施の形態の酸素同位体の濃縮方法を行う際に使用する酸素同位体濃縮装置の概略構成を模式的に示す図である。
始めに、図1を参照して、第1の実施の形態の酸素同位体の濃縮方法を行う際に使用する酸素同位体濃縮装置10について説明する。
第1の実施の形態の酸素同位体濃縮装置10は、第1の蒸留装置11と、第2の蒸留装置12と、水素化部14と、水分解部15と、化学交換塔16と、脱水部17と、酸素還流経路18と、水還流経路19と、水供給経路20と、を有する。
第1の蒸留塔群21は、原料中のある特定の成分を連続的に濃縮するため、第1の蒸留塔21Aで濃縮された特定の成分を第2の蒸留塔21Bで濃縮し、さらに、第2の蒸留塔21Bで濃縮された特定の成分を第3の蒸留塔21Cで濃縮する。この1つの連続した蒸留プロセスをカスケードプロセスという。
このため、第1の蒸留塔21Aの塔径が最も大きく、第3の蒸留塔21Cの塔径が最も小さい。
第1の凝縮器23は、熱媒体流体が通過する経路を有する。第1の凝縮器23は、第1の蒸留塔21Aの塔頂部から導出されたガスを熱媒体流体と熱交換させることにより、該ガスを冷却し液化させる。液化された凝縮液は、還流液経路35を介して、第1の蒸留塔21Aの上部に戻される。
第1の蒸発器24は、第1の蒸留塔21Aの底部から導出した液を熱媒体流体と熱交換させ、該液を加熱して気化させることで蒸留操作を実現し、この結果、第1の蒸留塔21Aの底で18O及び17Oが濃縮される。
図1に示すように、酸素同位体濃縮装置10が複数の蒸留塔(具体的には、第1ないし第3の蒸留塔21A,21B,21C)を含む場合、この段階(1回目の濃縮)では、まだ、十分に18O及び17Oが濃縮されていない。
18O及び17Oが濃縮された酸素は、供給ガス経路39を介して、第2の蒸留塔21Bの上部に供給される。
還流液経路45は、液経路43から分岐され、第2の蒸留塔21Bの上部と接続されている。
第2の蒸発器27は、第2の蒸留塔21Bの底部から導出した液を熱媒体流体と熱交換させ、該液を加熱して気化させることで、上昇ガスを発生させる。これにより、18O及び17Oが濃縮される。
この段階(2回目の濃縮)では、1回目の濃縮後よりも18O及び17Oが濃縮されている。18O及び17Oが濃縮された酸素は、供給ガス経路46を介して、第3の蒸留塔21Cの上部に供給される。
還流液経路52は、液経路51から分岐され、第3の蒸留塔21Cの上部と接続されている。
第3の蒸発器31は、第3の蒸留塔21Cの底部から導出した液を熱媒体流体と熱交換させ、該液を加熱して気化させことで、18O及び17Oが濃縮された上昇ガスを発生させる。
この段階(3回目の濃縮)では、2回目の濃縮後よりも18O及び17Oが濃縮されている。18O及び17Oが粗濃縮された酸素は、供給ガス経路54を介して、水素化部14に供給される。
上記構成とされた第1の蒸留装置11を用いて酸素の蒸留を行った際、第1の蒸留塔21Aの塔頂部から廃棄成分W1が排出される。
還流ガス経路64は、原料となる一酸化窒素(NO)が供給される経路であると共に、一酸化窒素を蒸留する際に発生する排ガスである一酸化窒素を化学交換塔16の底部に供給するための経路である。
第4の凝縮器68は、熱媒体流体が通過する経路を有する。第4の凝縮器68は、第4の蒸留塔61Aの塔頂部から導出されたガスを熱媒体流体と熱交換させることにより、該ガスを冷却し液化させる。液化された凝縮液は、還流液経路77を介して、第4の蒸留塔61Aの上部に戻される。
酸素同位体(18O及び/又は17O)が濃縮された一酸化窒素(NO)は、供給ガス経路81を介して、第5の蒸留塔61Bの上部に供給される。
還流液経路86は、液経路84から分岐され、第5の蒸留塔61Bの上部と接続されている。
第5の蒸発器73は、第5の蒸留塔61Bの底部から導出した液を熱媒体流体と熱交換させ、該液を加熱して気化させることで、上昇ガスを発生させる。この結果、製品である一酸化窒素(N18O及び/又はN17O(gas))が濃縮する。
水生成部14は、供給ガス経路54を介して、酸素同位体(18O及び17O)が粗濃縮された酸素に水素を添加し,反応させて水にする。
水素化部14では、例えば、水素燃料電池を用いて、酸素同位体が粗濃縮された酸素と水素とを反応させることで水を取得してもよい。該水は、水供給経路20を介して、化学交換塔16の上部に供給される。
水分解部15では、酸素同位体の濃度が低下した水を電気分解する。このとき、水素化部14において水素燃料電池を用いた際に発生する電気を用いて、酸素同位体の濃度が低下した水を電気分解する。
水分解部15は、酸素同位体の濃度が低下した水を電気分解した際に得られる酸素を、酸素還流経路18を介して、第1の蒸留装置11を構成する第3の蒸留塔21Cに供給する。
化学交換塔16には、水供給経路20を介して、水が供給されると共に、還流ガス経路64を介して、第2の蒸留装置12から排出された一酸化窒素が供給される。
酸素還流経路18は、水分解部15により、水から分離された酸素(具体的には、酸素同位体(18O及び17O)の濃度が低下した水を電気分解して得られる酸素)を第1の蒸留装置11を構成に還流させる。
なお、図1では、一例として、N18Oの取り出しラインを図示している。
始めに、第1の蒸留装置11を用いて、原料である酸素を蒸留することで、酸素同位体(18O及び17O)が粗濃縮された酸素を取得する。
このとき、水素化部14では、例えば、水素燃料電池を用いて、酸素同位体(18O及び17O)が粗濃縮された酸素と水素とを反応させることで水を取得するとよい。これにより、水分解部15において、酸素同位体の濃度が低下した水を電気分解する際の電気として、上記水素燃料電池を用いて、酸素同位体が粗濃縮された酸素と水素とを反応させた際に発生する電気を用いることができる。
また、水素化部14により生成された水は、水供給経路20を介して、化学交換塔16の上部に供給される。
具体的には、第4の蒸留塔61Aに原料となる一酸化窒素を供給し、第4及び第5の蒸留塔61A,61Bがカスケード接続された第2の蒸留塔群61を用いて、一酸化窒素を蒸留する。
第2の蒸留装置12から排出された一酸化窒素は、化学交換塔16の底部に供給される。
なお、上記「化学交換」とは、異種の化学種間、例えば、H2OとNOとを気液接触させて、酸素原子(O)について同位体交換させることをいう。
また、化学交換塔16で生成し、酸素同位体(18O及び17O)の濃度が低下した水は、水還流経路19を介して、水分解部15の底部に供給される。
水分解部15は、酸素同位体の濃度が低下した水を電気分解した際に得られる酸素を、酸素還流経路18を介して、第1の蒸留装置11を構成する第3の蒸留塔21Cに供給する。
図2は、本発明の第2の実施の形態の酸素同位体の濃縮方法を行う際に使用する酸素同位体濃縮装置の概略構成を模式的に示す図である。図2において、図1に示す第1の実施の形態の酸素同位体濃縮装置10と同一構成部分には、同一符号を付す。
第2の実施の形態の酸素同位体濃縮装置100は、第1の実施の形態の酸素同位体濃縮装置10に設けられた第1の蒸留装置11に替えて第1の蒸留装置101を設けると共に、酸素同位体濃縮装置10を構成する水素化部14、水分解部15、酸素還流経路18、及び水供給経路20を構成要素から除き、さらに、水還流経路103を設けたこと以外は、酸素同位体濃縮装置10と同様に構成される。
第1の凝縮器108は、熱媒体流体が通過する経路を有する。第1の凝縮器108は、第1の蒸留塔105Aの塔頂部から導出されたガスを熱媒体流体と熱交換させることにより、該ガスを冷却し液化させる。液化された凝縮液は、還流液経路119を介して、第1の蒸留塔105Aの上部に戻される。
第1の蒸発器109は、第1の蒸留塔105Aの底部から導出した液を熱媒体流体と熱交換させ、該液を加熱して気化させることで、18O及び17Oが濃縮された水を取得する。この段階(1回目の濃縮)では、まだ、十分に18O及び17Oが濃縮されていない。18O及び17Oが濃縮された水は、供給ガス経路123を介して、第2の蒸留塔105Bの上部に供給される。
第2の蒸発器113は、第2の蒸留塔105Bの底部から導出した液を熱媒体流体と熱交換させ、該液を加熱して気化させることで、18O及び17Oが濃縮された水を取得する。この段階(2回目の濃縮)では、1回目の濃縮後よりも18O及び17Oが濃縮されている。18O及び17Oが濃縮された水は、供給ガス経路129を介して、第3の蒸留塔105Cの上部に供給される。
第3の蒸発器116は、第3の蒸留塔105Cの底部から導出した液を熱媒体流体と熱交換させ、該液を加熱して気化させことで、18O及び17Oが粗濃縮された水を取得する。この段階(3回目の濃縮)では、2回目の濃縮後よりも18O及び17Oが濃縮されている。18O及び17Oが粗濃縮された水は、供給ガス経路136を介して、化学交換塔16に供給される。
上記構成とされた第1の蒸留装置101を用いて、水の蒸留を行うことで、第1の蒸留塔105Aの塔頂部から廃棄成分W2が排出される。
このため、第2の実施の形態の酸素同位体濃縮装置100は、第1の実施の形態の酸素同位体濃縮装置10と比較して簡便な構成とすることができる。
なぜなら、水の同位体の相対揮発度と酸素の同位体の相対揮発度(例えば、H2 18O/H2 16Oと16O18O/16O16O)とがほとんど変わらないため、化学交換塔16に供給される水の酸素同位体濃度は、第1の実施の形態において、第2の蒸留装置12から導出された酸素に水素を添加して得た水の酸素同位体濃度と、略同じ濃度とすることができるためである。
始めに、第1の蒸留装置101を用いて、原料である水を蒸留することで、酸素同位体(18O及び17O)が粗濃縮された水を取得する。
具体的には、第4の蒸留塔61Aに原料となる一酸化窒素を供給し、第4及び第5の蒸留塔61A,61Bがカスケード接続された第2の蒸留塔群61を用いて、原料である一酸化窒素を蒸留する。
第2の蒸留装置12から排出された一酸化窒素は、化学交換塔16の底部に供給される。
なお、上記「化学交換」とは、異種の化学種間、例えば、H2OとNOとを気液接触させて、酸素原子(O)について同位体交換させることをいう。
また、化学交換塔16で生成され、かつ酸素同位体(18O及び17O)の濃度が低下した水は、水還流経路103を介して、第3の蒸留塔105Cの下部に供給される。
実施例では、図1に示す第1の実施の形態の酸素同位体濃縮装置10を用いて、酸素同位体(18O及び17O)を濃縮した。
実施例では、製品である一酸化窒素(N17O)に含まれる17Oの含有率が10atom%以上、製品である一酸化窒素(N18O)に含まれる18Oの含有率が98atom%以上とした。
製品である一酸化窒素(N17O)を得るために、水素化した17Oを濃縮した水を1年間に5トン生産する場合を想定して、酸素同位体の濃縮方法のプロセスを構築した。
始めに、第1の蒸留塔21Aに原料となる酸素(供給量;5500Nm3/h)を供給し、第1ないし第3の蒸留塔21A,21B,21Cがカスケード接続された第1の蒸留塔群21を用いて、原料である酸素を蒸留して、酸素同位体(18O及び17O)を濃縮することで、酸素同位体(18O及び17O)が粗濃縮された酸素を生成した。
このとき、第3の蒸留塔21Cの底部における17O及び18Oの濃度を求めたところ、17Oの濃度が2.23atom%であり、18Oの濃度が26.1atom%であった。
このとき得られた製品である酸素同位体が濃縮した一酸化窒素の生産速度は、0.58Nm3/hであった。
その後、酸素同位体が粗濃縮された酸素を水素化部14に供給した。
この化学交換後、N17Oに含まれる17Oの濃度を求めたところ、2atom%であった。また、N18Oに含まれる18Oの濃度を求めたところ、23.6atom%であった。
なお、最終製品となるN17Oを得るための水-17O(H2 17O)の生産量が1年間に5トンの場合、N18Oを得るための水-18Oの1年間の生産量は、10トンとなる。
また、本発明では、NO蒸留を行う際の製品として抜き出された一酸化窒素量を補充するだけでよいので、上記した生産速度である0.58Nm3/hを補充することとなる。
なお、酸素同位体の生産量を同一の条件とし、全てを第2の蒸留装置12で実施する場合には、段数1200段(言い換えれば、カスケード接続された1200個の蒸留塔)とされた蒸留装置、1600Nm3/hの供給速度で原料を供給することが必要となる。蒸留塔内の液体ホールドアップを考慮すると大量の一酸化窒素を使用することになる。
また、第2の蒸留装置12を構成する蒸留塔の塔径を小さくすることが可能となるため、第2の蒸留装置12の液体NOホールドアップは、NOのみで蒸留濃縮する装置と比較して、10分の1程度にすることができる。
11,101 第1の蒸留装置
12 第2の蒸留装置
14 水素化部
15 水分解部
16 化学交換塔
17 脱水部
18 酸素還流経路
19 水還流経路
20 水供給経路
21,105 第1の蒸留塔群
21A,105A 第1の蒸留塔
21B,105B 第2の蒸留塔
21C,105C 第3の蒸留塔
23,108 第1の凝縮器
24,109 第1の蒸発器
26,112 第2の凝縮器
27,113 第2の蒸発器
29,115 第3の凝縮器
31,116 第3の蒸発器
34,42,49,75,83,118,125,132 塔頂ガス経路
35,45,52,77,86,119,128,135 還流液経路
39,46,54,123,129,136 供給ガス経路
43,51,84,126,133 液経路
61 第2の蒸留塔群
61A 第4の蒸留塔
61B 第5の蒸留塔
63 熱交換器
64 還流ガス経路
66 原料供給経路
68 第4の凝縮器
69 第4の蒸発器
72 第5の凝縮器
73 第5の蒸発器
81,88 液供給経路
103 水還流経路
W1,W2 廃棄成分
Claims (7)
- 第1の蒸留装置を用いて、原料である酸素を蒸留することで、酸素同位体が粗濃縮された酸素を取得する工程と、
前記酸素同位体が粗濃縮された酸素に水素を添加することで、水を取得する工程と、
第2の蒸留装置を用いて、原料である一酸化窒素を蒸留した際に排出される一酸化窒素を取得する工程と、
前記水と前記排出された一酸化窒素とを化学交換させることで、前記酸素同位体の濃度が高められた一酸化窒素、及び前記酸素同位体の濃度が低下した水を取得する一酸化窒素及び水取得工程と、
を有し、
前記酸素同位体の濃度が高められた一酸化窒素を前記第2の蒸留装置に供給し、前記酸素同位体の濃度が低下した水を電気分解して得られる酸素を前記第1の蒸留装置に還流させることを特徴とする酸素同位体の濃縮方法。 - 前記水を取得する工程では、水素燃料電池を用いて、前記粗濃縮された酸素に水素を添加し反応させることで水を取得し、
前記水素燃料電池を用いて、前記粗濃縮された酸素に水素を添加し反応させることで水を取得する際に発生する電気により、前記酸素同位体の濃度が低下した水を電気分解することを特徴とする請求項1記載の酸素同位体の濃縮方法。 - 前記酸素同位体が粗濃縮された酸素を取得する工程では、前記第1の蒸留装置として、複数の蒸留塔がカスケード接続された第1の蒸留塔群を用いることを特徴とする請求項1または2記載の酸素同位体の濃縮方法。
- 前記一酸化窒素を取得する工程では、前記第2の蒸留装置として、複数の蒸留塔がカスケード接続された第2の蒸留塔群を用いることを特徴とする請求項1ないし3のうち、いずれか1項記載の酸素同位体の濃縮方法。
- 第1の蒸留装置を用いて、原料である水を蒸留することで、酸素同位体を含む水分子が粗濃縮された水を取得する工程と、
第2の蒸留装置を用いて、原料である一酸化窒素を蒸留した際に排出される一酸化窒素を取得する工程と、
前記粗濃縮された水と前記排出された一酸化窒素とを化学交換させることで、前記酸素同位体の濃度が高められた一酸化窒素、及び前記酸素同位体の濃度が低下した水を取得する工程と、
を有し、
前記酸素同位体の濃度が高められた一酸化窒素を前記第2の蒸留装置に供給し、前記酸素同位体の濃度が低下した水を前記第1の蒸留装置に還流させることを特徴とする酸素同位体の濃縮方法。 - 前記酸素同位体を含む水分子が粗濃縮された水を取得する工程では、前記第1の蒸留装置として、複数の蒸留塔がカスケード接続された第1の蒸留塔群を用いることを特徴とする請求項5記載の酸素同位体の濃縮方法。
- 前記一酸化窒素を取得する工程では、前記第2の蒸留装置として、複数の蒸留塔がカスケード接続された第2の蒸留塔群を用いることを特徴とする請求項5または6記載の酸素同位体の濃縮方法。
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