WO2023195553A1 - Procédé de séparation d'isotopes utilisant une différence de diffusion entre des isotopes - Google Patents

Procédé de séparation d'isotopes utilisant une différence de diffusion entre des isotopes Download PDF

Info

Publication number
WO2023195553A1
WO2023195553A1 PCT/KR2022/004895 KR2022004895W WO2023195553A1 WO 2023195553 A1 WO2023195553 A1 WO 2023195553A1 KR 2022004895 W KR2022004895 W KR 2022004895W WO 2023195553 A1 WO2023195553 A1 WO 2023195553A1
Authority
WO
WIPO (PCT)
Prior art keywords
isotopes
separation method
breathing
pore
pores
Prior art date
Application number
PCT/KR2022/004895
Other languages
English (en)
Korean (ko)
Inventor
오현철
박재우
정민지
Original Assignee
경상국립대학교 산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 경상국립대학교 산학협력단 filed Critical 경상국립대학교 산학협력단
Publication of WO2023195553A1 publication Critical patent/WO2023195553A1/fr

Links

Images

Classifications

    • 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
    • B01D59/22—Separation by extracting
    • B01D59/26—Separation by extracting by sorption, i.e. absorption, adsorption, persorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • 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
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/10—Nuclear fusion reactors

Definitions

  • the present invention relates to a method of isotope separation using diffusion differences between isotopes as temperature increases.
  • Deuterium or tritium can be used in a variety of industrial fields, including nuclear fusion, nuclear power generation, semiconductors, and bio, and can be discharged as a by-product after processing, so the separation of these isotopes is an important issue.
  • isotopes have almost the same physical and chemical properties, if they are mixed as by-products of industrial processes, it may be difficult to separate them due to the low separation coefficient. For example, if deuterium is contained in high concentrations, it can be harmful to the human body, so separating it into pure deuterium is an important issue.
  • the quantum sieving (QS) property can be used, where relatively heavier isotopes diffuse more quickly within the pores of a porous material.
  • the present invention can provide an isotope separation method using a flexible metal-organic framework.
  • the isotope separation method of the present invention can have high isotope separation selectivity due to increased diffusivity at high temperatures (near the liquid nitrogen temperature of -196°C) as the temperature increases, contrary to the existing tendency at high injection amounts.
  • the isotope separation method of the present invention includes an injection step in which a first element and a second element are injected into a porous material, and the diffusion rate of the second element in the pores of the porous material increases compared to the first element to form the second element.
  • the first element and the second element are isotopes, and the mass of the second element may be greater than that of the first element.
  • the pores of the porous material may be changed to one of a closed structure, a first breathing structure, and a second breathing structure.
  • the first element and the second element may diffuse into the pores of the closed structure and the pores of the first breathing structure, and the second element may diffuse into the pores of the second breathing structure.
  • Isotope separation using the flexible metal-organic framework (FMOF) of the present invention increases the temperature at a high injection amount (above 18 mmol/g) and requires a pressure (above 1 bar) higher than the secondary respiration effect pressure range (within 1 bar). It can be created, and at this time, the difference in diffusion between isotopes can be large (more than 3 times), and by using this, high selectivity can be obtained even at high temperatures (near the liquid nitrogen temperature of -196°C).
  • the present invention utilizes a flexible metal-organic framework whose pore structure has a respiration effect that changes depending on external stimuli such as temperature or pressure, and can efficiently separate isotopes by differences in hydrogen isotope diffusion within the pores.
  • the present invention can separate heavier isotopes at a relatively high temperature (around 77K) compared to existing isotope separation methods, allowing hydrogen isotope separation to be performed at low cost.
  • the present invention enables the separation of heavier isotopes within an isotope mixture simply by controlling the flexibility of the flexible metal-organic framework and external conditions, making it efficient without building a complex system such as preparing separate complex materials for isotope separation.
  • Deuterium can be separated using
  • Figures 1 (a) to (c) are graphs of the diffusivity of the flexible metal organic framework (FMOF) used in the isotope separation method of the present invention for deuterium and hydrogen according to temperature.
  • Figure 1(d) is a graph of the diffusivity of Takeda 3A, a hard metal organic metal body (RMOF), for deuterium and hydrogen according to temperature.
  • Figure 2 is an explanatory diagram of the closed structure, the first breathing structure, and the second breathing structure of the present invention.
  • Figure 3 is an explanatory diagram of respiratory transition (BT1, BT2) and concentration (injection amount, L1, L2, L3) of the present invention.
  • FIG 4 is an illustration of the interaction between force and energy applied to the pores of the flexible metal organic framework (FMOF) used in the isotope separation method of the present invention.
  • FMOF flexible metal organic framework
  • Figure 5 (a) is the QENS of deuterium and hydrogen for the flexible metal organic framework (FMOF) used in the isotope separation method of the present invention.
  • FMOF flexible metal organic framework
  • Figure 6 is a graph of the momentum transfer (Q) and half width at half maximum (HWHM) of deuterium and hydrogen for the flexible metal organic framework (FMOF) used in the isotope separation method of the present invention.
  • Figure 7 is a graph of the temperature and diffusivity of the Arrhenius type (Arrhenius plot) of deuterium and hydrogen for the flexible metal organic framework (FMOF) used in the isotope separation method of the present invention.
  • isotope injected into the porous material will be described as an example of hydrogen (H 2 ) or deuterium (D 2 ), but the information discussed herein can be extended and applied to the separation of other isotopes regardless of the type of isotope. there is.
  • the isotope separation method of the present invention includes the steps of injecting a first element and a second element into a porous material 10, and the diffusion rate of the second element within the pores 100 of the porous material 10 is lower than that of the first element. Further increases may include a step in which the second element is selectively separated.
  • the first element and the second element of the present invention may be isotopes, and the mass of the second element may be greater than that of the first element.
  • the first element and the second element may include one or more types selected from the group consisting of isotopes of hydrogen, isotopes of helium, isotopes of oxygen, isotopes of nitrogen, and isotopes of carbon.
  • the first element may be hydrogen (H2)
  • the second element may be deuterium (D2).
  • the porous material 10 used for isotope separation of the present invention may include a metal organic metal body (MOF).
  • MOF metal organic metal body
  • the porous material 10 may include a flexible metal organic framework (FMOF).
  • FMOF flexible metal organic framework
  • Flexible metal organic metal bodies can be used for isotope separation using the Kinetic Quantum Seiving (KQS) effect.
  • KQS Kinetic Quantum Seiving
  • KQS dynamic quantum sieve effect
  • the flexible metal organic framework (FMOF) used in the present invention may have a molecular transport tendency of isotopes that is different from that of the rigid metal organic framework (RMOF) during breathing transition (BT).
  • Respiratory transition may be a structural change in the structure of the pore 100 under certain conditions.
  • the porous material 10 of the present invention may be MIL-53(M), a type of FMOF.
  • M may include at least one of Al, V, Cr, Fe, In, Co, Ga, Mn, SC, and Ni.
  • the pores 100 of the porous material 10 may be changed to one of a closed structure (P1), a first breathing structure (P2), and a second breathing structure (P3). there is.
  • the closed structure (P1) and the first breathing structure (P2) allow the first element (H2) or the second element (D2) to diffuse, and the second breathing structure (P3) allows only the second element (D2) to diffuse. You can.
  • the pores 100 of the porous material 10 can undergo a structural transition to the second breathing structure (P3) that allows the heavier isotope (D2) of the isotope mixture to pass through.
  • the step of selectively separating the second element of the present invention may include the following three steps.
  • the step of selectively separating the second element (D2) is a step in which, when the first element or the second element is injected below the first concentration, the pores 100 of the porous material 10 become a closed structure (P1). It can be included.
  • the step in which the second element (D2) is selectively separated is when the first or second element is injected at a concentration greater than or equal to the first concentration and less than or equal to the second concentration, the pores 100 of the porous material 10 form a closed structure (P1). It may include a step of becoming the first respiratory structure (P2).
  • the step in which the second element (D2) is selectively separated is that when the second element is injected at a second concentration or higher, the pores 100 of the porous material 10 are changed from the first breathing structure (P2) to the second breathing structure (P3). ) may include the step of.
  • the pores 100 of the porous material 10 change from the first breathing structure (P2) to the second breathing structure (P3)
  • the second element (D2) is injected at a second concentration or higher
  • the first element (H2 ) The pore through which it passes remains in the first breathing structure (P2), and the pore through which the second element (D2) passes can be changed from the first breathing structure (P2) to the second breathing structure (P3).
  • the concentrations at which the first element and the second element are injected into the porous material 10 can be divided into three first concentration sections, second concentration sections, and third concentration sections.
  • the first concentration section may be below the first concentration
  • the second concentration section may be between the first concentration and below the second concentration
  • the third concentration section may be above the second concentration
  • the pores 100 of the porous material 10 may be changed from a closed structure (P1) to a first breathing structure (P2), and the pores of the porous material 10 may be changed based on the second concentration.
  • (100) may be structurally changed from the first breathing structure (P2) to the second breathing structure (P3).
  • the first respiratory transition (BT1) may be a change in the pores 100 from the first respiratory structure (P2) to the second respiratory structure (P3).
  • the second respiratory transition (BT2) may be a change in the pores 100 from the first respiratory structure (P2) to the second respiratory structure (P3).
  • the second concentration of the second element D2 may be 18 mmol/g or more.
  • the difference in diffusion rates of the first element (H2) and the second element (D2) is in the second breathing structure (P3) among the closed structure (P1), the first breathing structure (P2), and the second breathing structure (P3). It could be the biggest.
  • the temperature is a temperature that is between the first temperature and the second temperature. It can be set to . The difference in diffusion rates of the first element and the second element may be greatest at the second temperature.
  • the first temperature may be around 25K, and the second temperature may be 77K or higher.
  • the size of the pore 100 may further increase in the order of the closed structure (P1), the first breathing structure (P2), and the second breathing structure (P3).
  • the pore 100 has a closed structure (P1), a first breathing structure (P2), and a second breathing structure (P3). ) can be structurally changed.
  • the second pressure may be 1 bar or more.
  • Flexible metal-organic framework may be a porous material whose pore structure can be changed by external stimulation among coordination compounds composed of organic ligands and metal building blocks.
  • Flexible metal-organic frameworks can be designed to change their pore structure in selective response to specific external stimuli by selecting appropriate organic ligands and metal building blocks.
  • flexible metal organic framework can be used to separate substances of different sizes or shapes, but in the case of isotopes, the size and shape are almost the same, so it can be used to selectively separate heavy isotopes such as deuterium. There is a difficult problem.
  • the present invention can selectively separate only deuterium by using a structural change in which the pores of the flexible metal organic framework (FMOF) are opened only by deuterium under external conditions of specific temperature and pressure.
  • FMOF flexible metal organic framework
  • Hydrogen (H2) was selected as the first element and deuterium (D2) was selected as the second element.
  • 1 (a) to (c) may be a graph of the diffusivity of MIL-53(Al) for deuterium and hydrogen according to temperature.
  • (d) of FIG. 1 may be a graph of the diffusion rate of Takeda 3A, a rigid metal organic framework (RMOF), for deuterium and hydrogen according to temperature.
  • RMOF rigid metal organic framework
  • the vertical double-headed arrows shown in (a) to (c) of Figures 1 may indicate the difference in diffusivity between deuterium and hydrogen. It can be seen that the difference in diffusivity between deuterium and hydrogen of the second breathing structure (P2) is the largest.
  • the difference in diffusivity between deuterium and hydrogen can be maximized at low temperature (around 25K) and minimum at high temperature (around 77K).
  • the difference in diffusivity between deuterium and hydrogen gradually increases as the temperature increases from low temperature (around 25K) to high temperature (around 77K). A trend may be seen.
  • the difference in diffusivity between deuterium and hydrogen may be the largest at high temperature (around 77K).
  • the isotope separation method of the present invention can selectively separate/collect only specific isotopes by using the large diffusion rate difference between isotopes of the second respiratory structure (P3).
  • the difference in diffusivity between deuterium and hydrogen in a solid metal organic metal body (RMOF) may appear in a low temperature range. As the temperature increases from 30K to 100K, the diffusivity gradually decreases, and the diffusivity of a hard metal organic metal body (RMOF) may actually decrease in the high temperature range.
  • the diffusion tendency of isotopes as the temperature increases in the closed structure (P1) of the flexible metal organic structure (FMOF) of the present invention may be similar to that of the rigid metal organic metal structure (RMOF).
  • the present invention can separate heavier isotopes at a relatively high temperature (around 77K) compared to existing isotope separation methods. Therefore, the present invention has the advantage of being able to separate hydrogen isotopes at low cost by being able to use liquid nitrogen around -196°C instead of liquid helium around -254°C.
  • MIL-53(Al) was prepared according to a previously reported method.
  • MIL-53(Al) is in an appropriate state
  • the phase purity of MIL-53(Al) confirmed through this is MIL-53(Al) It matched the simulated pattern of the hydrated form of (Al).
  • the pore cross section of MIL-53(Al) may have a diamond-shaped hole shape.
  • MIL-53(Al) can have a respiration effect in which the pore cross-section changes reversibly in response to external stimuli.
  • MIL-53(Al) may be in the shape of a tube that is open at both ends and extends long in the longitudinal direction.
  • MIL-53(Al) can make the first respiration transition (BT1) from a narrow pore (np) to a large pore (lp) and from a large pore (lp) to a very large pore (
  • the second respiratory transition (BT2) can occur with a very large pore (vlp).
  • the narrow pore (np) may be identical to the closed structure (P1), the large pore (lp, large pore) may be identical to the first breathing structure (P2), and the large pore (lp, large pore) may be identical to the third breathing structure (P2). It may be the same as the respiratory structure (P3).
  • MIL-53(Al) can be useful in hydrogen isotope separation.
  • the ability of MIL-53(Al) to selectively separate a specific isotope may be independent of the type of isotope.
  • Hydrogen isotope adsorption and desorption isotherms were measured at 25-77 K by an Autosorb iQ, 2MP-Xr with the Cryocooler (Quantachrome, USA) physisorption analysis instrument.
  • Figure 2 is an adsorption isotherm for hydrogen and deuterium of MIL-53(Al), an example of a flexible metal organic framework (FMOF) used in the isotope separation method of the present invention.
  • Figure 2 is an explanatory diagram of the closed structure (P1), the first breathing structure (P2), and the second breathing structure (P3) of the present invention.
  • Figure 3 may be isotherms of hydrogen (H2) and deuterium (D2) for MIL-53(Al) at various temperatures from 25 to 77 K.
  • a closed symbol may indicate adsorption, and an open symbol may indicate desorption.
  • the black lines in the isotherms can represent the respective respiratory transition points for QENS measurements: 0.7, 6.4, and 18 mmol g-1 injection.
  • a clear hysteresis loop can be observed in MIL-53(Al) due to structural changes induced by respiratory transition.
  • FMOFs flexible metal-organic frameworks
  • externally stimulated gases can induce dynamic changes, including S-shaped sorption, which can be referred to as a breathing phenomenon.
  • Respiratory pressure can change to higher pressure areas with increasing temperature.
  • the increase in the kinetic energy of gas molecules can be greater than the intermolecular potential energy, and higher respiratory pressures may be required for the gas molecules to be absorbed.
  • FIG. 4 is an explanatory diagram of the change in vibrational energy and molecular kinetic energy for the pores 100 of MIL-53 (Al), and contraction force with respect to temperature.
  • the injected isotope can be equally captured by the contractile force of the transferred structure during the first breathing structure (P2).
  • P2 first breathing structure
  • the thermal kinetic energy of these adsorption systems can overcompensate for the shrinkage forces. This may result in the creation of diffusion walls for each isotope, possibly due to the different zero point energies.
  • the gas absorption capacity of MIL-53(Al) can be maximized.
  • the saturated hydrogen (H2) absorption amount at 25K may be 16 mmol g -1 .
  • the saturated deuterium (D2) uptake can be nearly 23 mmol g -1 . This may be due to the structural transition of the MIL-53(Al) pores (100) in the second stage. This may be due to structural diffusion propagation for hydrogen and deuterium in MIL-53(Al).
  • the concentration of the first or second element introduced into the porous material 10 may be expressed as a first injection amount (L1), a second injection amount (L2), and a third injection amount (L3).
  • the first injection amount (L1) may be any value included in the first concentration range.
  • the second injection amount (L2) may be any value included in the second concentration range.
  • the third injection amount (L3) may be any value included in the third concentration range.
  • the first injection amount (L1) may be set to 0.7 mmol g -1
  • the second injection amount (L2) may be set to 6.4 mmol g -1
  • the third injection amount (L3) may be set to 18 mmol g -1 .
  • MIL-53(Al) may include at least one of a first phase, a second phase, and a third phase that can be classified according to the size of the pores 100 or the amount of gas injected.
  • the closed structure (P1) may be the dominant structure within MIL-53(Al)
  • the first breathing structure (P2) may be the dominant structure within MIL-53(Al)
  • the second respiratory structure (P3) may be dominant within MIL-53(Al).
  • the first phase may appear at the first injection amount (L1), and the first respiratory transition (BT1) from the first phase (L1) to the second phase (L2) may occur at the second injection amount (L2). there is.
  • BT1 first respiratory transition
  • L2 second injection amount
  • BT2 second respiratory transition
  • the third phase and second respiratory transition (BT2) can only occur in deuterium.
  • QENS measurements of the hydrogen isotope of MIL-53(Al) were performed using the time-of-flight NEAT spectrometer at the neutron source at BER-II, Helmholtz-Zentrum Berlin.
  • QENS spectra were recorded by the NEAT instrument using neutron wavelengths 2, 6, and 8 ⁇ . It has a momentum transfer range of 100 ⁇ eV energy resolution from 0.375 to 2.025 ⁇ -1 with a step size of 0.15 ⁇ -1 .
  • MIL-53(Al) was activated by heating to 400 K at a rapid rate of 1 K min1 for 13 h to remove moisture and absorbed gases. Approximately 930 mg of activated MIL-53(Al) was transferred to a cylindrical sample holder cell made of aluminum in a glovebox filled with inert gas to prevent exposure to air. Then, the sample cells were transferred to the NEAT apparatus.
  • the gas injection system available for NEAT was MIL-53(Al) gas with pressures of 0.7, 6.4, and 18 mmol g1 of the hydrogen isotope at various temperatures (25, 40, 60, and 77 K). Used for injection. Ambient influences and experimental distortions were corrected by measuring the sample holder and MIL-53 (Al) in the absence of any gas.
  • Quasi-Elastic Neutron Scattering (QENS) experiments can be a microscopic observation of isotope molecular transport during the separation process under dynamic respiratory transitions.
  • Quasi-elastic neutron scattering (QENS) experiments show that deuterium diffuses much faster than hydrogen in flexible pore structures at higher temperatures.
  • the present invention can be effective in isotope separation even at high temperatures using a flexible metal organic framework system.
  • the diffusion pattern of deuterium and hydrogen in MIL-53(Al) can be temperature or concentration dependent.
  • the diffusion pattern of hydrogen isotopes can be measured by QENS, and concentrations can be performed from low to high isotope concentrations.
  • Figure 5 (a) shows that when injected at a pressure of 18 mmol g -1 in MIL-53 (Al), a momentum of 0.375 ⁇ -1 is transferred and the hydrogen isotope absorbed at temperatures of 25, 40, 60, and 77 K. It may be a QENS spectrum.
  • Figure 5 (b) may be a fitting of QENS data of 0.375 ⁇ -1 momentum transfer (Q) absorbed at 77 K and pressure injection of 18 mmol g -1 in MIL-53(Al).
  • Q may be momentum transfer, which may mean, for example, the difference in momentum between the incident wave and the scattered wave in wave scattering.
  • the Lorentzian function, Gaussian function, and a combination of the two functions can be displayed as a blue dotted line, a green dotted line, and a red thick line, respectively.
  • the intensity of the QENS signal may be proportional to the self-correlation function (S(Q, ⁇ )), and the autocorrelation function may describe at least one of diffusion, vibration, and rotational motion.
  • S(Q, ⁇ ) self-correlation function
  • the autocorrelation function may describe at least one of diffusion, vibration, and rotational motion.
  • the Gaussian distribution can describe the continuous diffusion of reflected elastic scattering signals, while the Laurentian distribution can describe complex diffusion processes with diffusion times much larger than the neutron experimental time scale.
  • the width of the Laurentian distribution for deuterium may be wider than that for hydrogen, which may mean that diffusion of deuterium is faster than that of hydrogen in MIL-53(Al).
  • the QENS signal may originate from the self-diffusion motion of hydrogen and deuterium. Therefore, the self-diffusivity of hydrogen and deuterium can be investigated by extracting the half-width at half maximum (HWHM) of the Laurentian function at each Q from the measured QNES data.
  • HWHM half-width at half maximum
  • Figure 6 shows the raw QENS signal of hydrogen isotopes in MIL-53(Al) versus the Lorenzian half-width at half maximum (HWHM) for fits to Q 2 .
  • the solid line (black is hydrogen (H2) and red is deuterium (D2)) can be aligned with data using a jump diffusion model.
  • the hydrogen isotope dynamics of MIL-53(Al) obtained from HWHM data may be a characteristic of a jump diffusion model without a clear spatial orientation of the jump direction in nanoporous materials.
  • Full width at half maximum may be a characteristic regarding the width of a specific function.
  • the full width at half maximum can mean the difference between the values of two independent variables, which is half the maximum value of the function.
  • Half-width at half maximum may relate to the width of a specific function.
  • the half maximum width may mean half the full width at half maximum.
  • the QENS expansion follows a linear dependence on Q2. This may be called Fickian diffusion and may be caused by Brownian motion.
  • the distance at which it is detected becomes increasingly smaller and intramolecular interactions can become more pronounced.
  • the Q2 dependence can have more complex behavior and can be largely characterized by jump length and remaining time.
  • a jump-diffusion model can be used for diffusion between different adsorption points or into a sphere.
  • Q2-dependent HWHM values for hydrogen and deuterium can be fitted using the liquid-like jump diffusion model given by equation 1.
  • ⁇ 0 may be the remaining time at a given point, l 0 may be the intrinsic jump length, and ⁇ may be Planck's constant.
  • Equation 2 The exponential distribution of jump length ⁇ (l) can be given by Equation 2.
  • l may be the jump length, and the square of l 0 may be equal to 1/6* ⁇ l 2 >.
  • the HWHMs of hydrogen and deuterium can be similar at 25 K. However, these may begin to vary as temperature increases.
  • Self-diffusivity (D) can be obtained from Equation 3 using the parameters obtained from Equation 1.
  • the temperature-dependent diffusivity (D) of MIL-53(Al) at various temperatures can be based on the injection pressure of the gas.
  • MIL-53(Al) can have a very small axial opening and a rigid, closed structure (P1). there is.
  • the KQS effect can dominate at low temperatures and confined pore structures, which can lead to large diffusion differences between hydrogen and deuterium.
  • the difference in diffusivity of hydrogen isotopes may decrease as the temperature reaches 77 K. That is, the difference in diffusivity between H2 and D2 in a solid porous material can be observed only at low temperatures.
  • the pore 100 may begin to transform into the second respiratory structure (P2).
  • the diffusivity of hydrogen isotopes may increase with an increase in temperature, and the diffusivity of the second breathing structure (P2) may be higher than that of the closed structure (P1).
  • phase difference between hydrogen and deuterium can be attributed to the very large diffusion difference between the isotopes at the high temperature of 77 K.
  • the saturated absorption amount of hydrogen (H2) may be 16.0 mmol g-1, and over-injection of 2.0 mmol g-1 may lower the mobility of hydrogen (H2) and interfere with the path of other hydrogen (H2) molecules. , can even have a diffusivity lower than the hydrogen mobility of 6.4 mmol g-1.
  • the saturated absorption amount of hydrogen may be the second injection amount, and when a hydrogen injection amount exceeding the second injection amount is introduced into the isotope adsorbent, an over-injection amount equal to the difference between the injected amount and the second injection amount will lower the mobility of hydrogen. You can.
  • the over-injected amount may interfere with the movement path of hydrogen, and as a result, even though more hydrogen is injected, the over-injected hydrogen may have a lower diffusivity than the second injected amount.
  • the diffusivity of deuterium can remain high, which can be explained by the second respiratory structure (P2), which is only exhibited by deuterium.
  • Figure 7 shows an Arrhenius type plot of temperature-dependent diffusivity at a third dose (L3) of hydrogen isotope.
  • Equation 4 The maximum diffusivity (D 0 ) and activation energy (E a ) of a hydrogen isotope may be calculated by Equation 4, and Equation 4 may be the Arrhenius equation.
  • R can be the gas constant, and for deuterium, the D 0 value can be 7.75 ⁇ 108 m2 s-1, and for hydrogen it can be 2.93 ⁇ 108 m2 s-1. Therefore, it can be seen that at the same injection amount, the D0 values of hydrogen and deuterium are different. This difference in D0 values may be due to the difference between the first phase of hydrogen and the second phase of deuterium in MIL-53(Al).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un procédé de séparation d'isotopes qui utilise une structure organométallique flexible (FMOF) capable de séparer/collecter sélectivement des isotopes au moyen de l'effet de tamis quantique cinétique (KQS), et peut ainsi séparer sélectivement un isotope spécifique d'un mélange d'isotopes dans des conditions spécifiques. Cet effet de séparation peut être attribué à la différence de taux de diffusion entre des isotopes dans les pores d'un matériau poreux. La différence de taux de diffusion entre les isotopes de la présente invention peut être déterminée par une expérience de diffusion de neutrons quasi-élastique (QENS) pour l'observation microscopique du transport moléculaire isotopique pendant la transition respiratoire (BT) des pores (100). Il peut être déterminé par QENS que le deutérium diffuse plus rapidement que l'hydrogène dans les pores (100), et la différence de taux de diffusion entre les isotopes peut augmenter avec l'augmentation de la température. La présente invention peut être appliquée à un adsorbant capable de séparer des Isotopes au moyen de l'effet KQS même à une température élevée de 77K ou plus.
PCT/KR2022/004895 2021-05-27 2022-04-05 Procédé de séparation d'isotopes utilisant une différence de diffusion entre des isotopes WO2023195553A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR20210068435 2021-05-27
KR1020220042388A KR20220160472A (ko) 2021-05-27 2022-04-05 동위원소 간의 확산 차이를 이용한 동위원소 분리 방법
KR10-2022-0042388 2022-04-05

Publications (1)

Publication Number Publication Date
WO2023195553A1 true WO2023195553A1 (fr) 2023-10-12

Family

ID=84407528

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2022/004895 WO2023195553A1 (fr) 2021-05-27 2022-04-05 Procédé de séparation d'isotopes utilisant une différence de diffusion entre des isotopes

Country Status (2)

Country Link
KR (1) KR20220160472A (fr)
WO (1) WO2023195553A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101421224B1 (ko) * 2012-09-18 2014-07-22 한국과학기술연구원 동위원소 희석법 및 기체 크로마토그래피-이중 질량분석기를 이용한 산성제초제의 분석방법
US8940905B2 (en) * 2009-10-23 2015-01-27 Cnrs Method for preparing organic/inorganic hybrid functionalized solids having a triazole ring
WO2017003660A1 (fr) * 2015-07-01 2017-01-05 Sabic Global Technologies B.V. Modification de réseaux d'imidazolate zéolitique et membranes à matrice mélangée réticulées d'azide produites à partir de celles-ci
KR20190080619A (ko) * 2017-12-28 2019-07-08 울산과학기술원 동위 원소 분리를 위한 금속-유기 골격체, 동위 원소 분리 시스템, 동위 원소 분리 방법 및 제조방법
KR20190106582A (ko) * 2018-03-09 2019-09-18 울산과학기술원 플렉시블　금속 유기 골격체를 이용한 동위원소 혼합물의 분리 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8940905B2 (en) * 2009-10-23 2015-01-27 Cnrs Method for preparing organic/inorganic hybrid functionalized solids having a triazole ring
KR101421224B1 (ko) * 2012-09-18 2014-07-22 한국과학기술연구원 동위원소 희석법 및 기체 크로마토그래피-이중 질량분석기를 이용한 산성제초제의 분석방법
WO2017003660A1 (fr) * 2015-07-01 2017-01-05 Sabic Global Technologies B.V. Modification de réseaux d'imidazolate zéolitique et membranes à matrice mélangée réticulées d'azide produites à partir de celles-ci
KR20190080619A (ko) * 2017-12-28 2019-07-08 울산과학기술원 동위 원소 분리를 위한 금속-유기 골격체, 동위 원소 분리 시스템, 동위 원소 분리 방법 및 제조방법
KR20190106582A (ko) * 2018-03-09 2019-09-18 울산과학기술원 플렉시블　금속 유기 골격체를 이용한 동위원소 혼합물의 분리 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JUNG MINJI, PARK JAEWOO, MUHAMMAD RAEESH, KIM JIN YEONG, GRZIMEK VERONIKA, RUSSINA MARGARITA, MOON HOI RI, PARK JITAE T., OH HYUNC: "Elucidation of Diffusivity of Hydrogen Isotopes in Flexible MOFs by Quasi‐Elastic Neutron Scattering", ADVANCED MATERIALS, VCH PUBLISHERS, DE, vol. 33, no. 20, 1 May 2021 (2021-05-01), DE , XP093097151, ISSN: 0935-9648, DOI: 10.1002/adma.202007412 *

Also Published As

Publication number Publication date
KR20220160472A (ko) 2022-12-06

Similar Documents

Publication Publication Date Title
WO2017061804A1 (fr) Dispositif d'analyse d'échantillon gazeux à grande vitesse par chromatographie en phase gazeuse, et procédé associé
WO2015023039A1 (fr) Membrane d'adsorption perméable en fibres creuses, procédé de fabrication de celle-ci et système de séparation de gaz par absorption et désorption utilisant celle-ci
JPS586906B2 (ja) 金属中ガス分析装置
WO2023195553A1 (fr) Procédé de séparation d'isotopes utilisant une différence de diffusion entre des isotopes
Wang et al. Dynamic separation of Xe and Kr by metal-organic framework and covalent-organic materials: a comparison with activated charcoal
CN106442823A (zh) 一种具有载气再生功能的挥发性有机物分析仪
US5162301A (en) Separation of paramagnetic and diamagnetic gases
CN111579694A (zh) 一种氘氚混合气中微量杂质含量的分析系统及方法
WO2009154374A9 (fr) Armatures métal-organique poreuses permanentes présentant une structure topologique nbo-net renfermant un groupe azo donneur d’électrons et contenant de gaz comprenant ces armatures
CN106940353A (zh) 多传感色谱检测仪及其检测方法
Baker et al. Tritium purification via zirconium–manganese–iron alloy getter St 909 in flow processes
Ricapito et al. Tritium processing systems for the helium cooled pebble bed test blanket module
JP2006023137A (ja) 微量水素分子及び水素同位体分子分離分析装置
CN111983062B (zh) 一种空气中微量dmaea的检测方法
WO2022231222A1 (fr) Adsorbant isotopique et procédé de séparation d'isotopes utilisant une structure organométallique
JPH11345545A (ja) ガス回収装置及びガス回収方法
CN208125870U (zh) 一种气体燃弧特性和灭弧性能的多参量检测系统
Toyoda et al. Application of pressure swing adsorption to SF/sub 6/separation and liquefaction from SF/sub 6//N/sub 2/mixtures
Ogawa et al. Measurement of radon emanation and impurity adsorption from argon gas using ultralow radioactive zeolite
Nakamura et al. Adsorption characteristics of water vapor on gear-pellet and honeycomb-pellet types of adsorbents containing A-type zeolite
FORD Recommended operating procedure No. 45: Analysis of nitrous oxide from combustion sources(Final Report, Sep. 1989- May 1990)
CN211043267U (zh) 一种带有等离子放电检测器的气相色谱装置
Ji et al. Study on the Method of Analyzing Low Concentration SF 6 Gas Decomposition Products Using Cryogenic Enrichment-gas Chromatography
WO2023113273A1 (fr) Structure organométallique pour collecter du krypton ou du xénon, et appareil pour collecter du krypton ou du xénon, comprenant celle-ci
RU2492914C2 (ru) Молекулярный фильтр для извлечения гелия из гелийсодержащих газовых смесей

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22936607

Country of ref document: EP

Kind code of ref document: A1