Separation method

Abstract

To provide a novel method for separating fluorocarbon.SOLUTION: A method for separating, from a first mixture containing fluorocarbon A with carbon number n having one or more double bonds and fluorocarbon B with carbon number m having no double bonds, a second mixture in which the composition ratio of fluorocarbon A to fluorocarbon B is different from that of the first mixture, the separation being conducted by bringing the first mixture into contact with an adsorbent comprising a metal-organic framework.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a separation method. [Background technology]

[0002] A method of distilling a mixture of fluorocarbons is known as a method for separating fluorocarbons. Patent Document 1 describes a method of mixing a mixture containing 2,3,3,3-tetrafluoropropene and hexafluoropropene with an extraction solvent to obtain a mixture for extraction, and then distilling the mixture for extraction to obtain a distillate containing hexafluoropropene as a main component and a bottom product containing 2,3,3,3-tetrafluoropropene. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2018-002602 Summary of the Invention [Problem to be solved by the invention]

[0004] It has been found that the distillation method described in Patent Document 1 has difficulty in separating compounds with similar boiling points or compounds that form an azeotrope, and that when separating fluorocarbons, for example, fluorocarbons that differ in the presence or absence of a double bond, the method may be unable to sufficiently separate them.

[0005] The problem in this disclosure is to provide a new method for separating fluorocarbons. [Means for solving the problem]

[0006] The present disclosure includes the following aspects. [1] A first mixture containing fluorocarbon A having n carbon atoms and one or more double bonds and fluorocarbon B having m carbon atoms and no double bond, separating a second mixture having a different composition ratio of the fluorocarbon A and the fluorocarbon B from that of the first mixture; The method for separating fluorocarbons, wherein the separation is carried out by contacting the first mixture with an adsorbent including a metal-organic framework. [2] The separation method according to [1], wherein the first mixture is contacted with the adsorbent containing the metal organic framework at a temperature of −10° C. or higher and 80° C. or lower. [3] The separation method according to [1] or [2], wherein n is 2 or more and 3 or less. [4] The separation method according to any one of [1] to [3], wherein m is 1 or more and 3 or less. [5] The separation method according to any one of [1] to [4], wherein the fluorocarbon A contains R1234yf. [6] The separation method according to any one of [1] to [5], wherein the fluorocarbon B includes one or more selected from R134a, R143, R143a, R32, and R125. [7] The separation method according to any one of [1] to [6], wherein the metal organic framework contains a metal ion. [8] The separation method according to any one of [1] to [7], wherein the metal-organic framework comprises one or more organic ligands, and the organic ligand comprises two or more groups capable of forming a coordinate bond to a metal ion in one molecule. [9] The separation method according to any one of [1] to [8], wherein the metal-organic framework comprises a metal ion and one or more organic ligands, and the organic ligand comprises two or more groups capable of forming a coordinate bond with the metal ion in one molecule.

[10] The separation method according to any one of [1] to [9], wherein the metal organic framework has open metal sites consisting of coordinatively unsaturated metal ions.

[11] The separation method according to any one of [1] to

[10] , wherein the adsorbent containing the metal organic framework further contains a resin.

[12] The separation method according to any one of [1] to

[11] , wherein the adsorbent containing the metal organic framework is in the form of powder, granules, flakes, or pellets.

[13] The separation method according to any one of [1] to

[12] , wherein the first mixture is an azeotropic mixture or a pseudo-azeotropic mixture of fluorocarbons.

[14] The separation method according to any one of [1] to

[13] , further comprising contacting the separated second mixture with an adsorbent containing the metal organic framework.

[15] The separation method according to any one of [1] to

[14] , further comprising purifying the separated second mixture.

[16] After contacting the first mixture with the adsorbent containing the metal organic framework, The separation method according to any one of [1] to

[15] , further comprising desorbing, from the adsorbent comprising the metal organic framework, the fluorocarbon A adsorbed to the adsorbent comprising the metal organic framework.

[17] A fluorocarbon purification system that carries out the separation method according to any one of [1] to

[16] .

[18] A first mixture containing fluorocarbon A having n carbon atoms and one or more double bonds and fluorocarbon B having m carbon atoms and no double bond, separating a third mixture having a reduced concentration of fluorocarbon A relative to the first mixture; A method for separating fluorocarbons, wherein the separation is carried out by contacting the first mixture with an adsorbent.

[19]

[18] The separation method according to

[18] , wherein the contact of the first mixture with the adsorbent is carried out at a temperature of -10°C or higher and 80°C or lower.

[20] The separation method according to

[18] or

[19] , wherein n is 2 or more and 3 or less. [twenty one] The separation method according to any one of

[18] to

[20] , wherein m is 1 or more and 3 or less. [twenty two] The separation method according to any one of

[18] to

[21] , wherein the fluorocarbon A contains R1234yf. [twenty three] The separation method according to any one of

[18] to

[22] , wherein the fluorocarbon B includes one or more selected from R134a, R143, R143a, R32, and R125. [twenty four] The separation method according to any one of

[18] to

[23] , wherein the adsorbent comprises a porous material. [twenty five] The separation method according to any one of

[18] to

[24] , wherein the adsorbent contains a metal-organic framework.

[26] The separation method according to

[25] , wherein the metal organic framework contains a metal ion.

[27] The separation method according to

[25] , wherein the metal-organic framework comprises one or more types of organic ligands, and the organic ligand comprises two or more groups capable of forming a coordinate bond to a metal ion in one molecule.

[28] The separation method according to

[25] , wherein the metal-organic framework comprises a metal ion and one or more organic ligands, and the organic ligand comprises two or more groups capable of forming a coordinate bond to the metal ion in one molecule.

[29] The separation method according to

[25] , wherein the metal organic framework has open metal sites consisting of coordinatively unsaturated metal ions.

[30] The separation method according to any one of

[18] to

[29] , wherein the adsorbent further contains a resin.

[31] The separation method according to any one of

[18] to

[30] , wherein the adsorbent is in the form of powder, granules, flakes or pellets.

[32] The separation method according to any one of

[18] to

[31] , wherein the first mixture is an azeotropic mixture or a pseudo-azeotropic mixture of fluorocarbons.

[33] The separation method according to any one of

[18] to

[32] , further comprising contacting the separated third mixture with an adsorbent.

[34] The separation method according to any one of

[18] to

[33] , further comprising purifying the separated third mixture.

[35] After contacting the first mixture with the adsorbent, The separation method according to any one of

[18] to

[34] , further comprising desorbing, from the adsorbent, the fluorocarbon A adsorbed to the adsorbent.

[36] A fluorocarbon purification system that implements the separation method according to any one of

[18] to

[35] .

[37] A metal-organic framework and a fluorocarbon A having one or more double bonds and n carbon atoms, The metal organic framework is a composite material having open metal sites composed of coordinatively unsaturated metal ions. [Effects of the Invention]

[0007] The present disclosure may provide a new method for separating fluorocarbons. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram depicting a fluorocarbon purification system in one embodiment of the present disclosure. [Figure 2] FIG. 2 is a schematic diagram illustrating a fluorocarbon purification system in accordance with another embodiment of the present disclosure. [Figure 3] FIG. 3 shows the adsorption breakthrough curves of Example 1 and Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0009] (First embodiment: first separation method) The first separation method of the present disclosure comprises: A first mixture containing fluorocarbon A having n carbon atoms and one or more double bonds and fluorocarbon B having m carbon atoms and no double bond, separating a second mixture having a different composition ratio of fluorocarbon A to fluorocarbon B than the first mixture; The separation is carried out by contacting the first mixture with an adsorbent containing a metal-organic framework.

[0010] According to the first separation method of the present disclosure, by contacting an adsorbent containing a metal-organic framework with a first mixture containing two or more fluorocarbon gases, it is possible to separate a second mixture in which the proportion of either the fluorocarbon gas having a double bond or the fluorocarbon gas having no double bond is reduced. Although the present disclosure should not be interpreted as being limited to a particular theory, it is believed that the pore structure of the metal-organic framework can control the adsorption behavior between the metal-organic framework and fluorocarbon A having a double bond or fluorocarbon B having no double bond, thereby obtaining a mixture with a different composition ratio. Note that the second mixture may also include a case in which either fluorocarbon A or fluorocarbon B is not contained.

[0011] In one embodiment, the first separation method comprises: A first mixture containing fluorocarbon A having n carbon atoms and one or more double bonds and fluorocarbon B having m carbon atoms and no double bond, separating a second mixture having a reduced concentration of fluorocarbon A relative to the first mixture; The separation is carried out by contacting the first mixture with an adsorbent containing a metal-organic framework.

[0012] In another embodiment, the first separation method comprises: A first mixture containing fluorocarbon A having n carbon atoms and one or more double bonds and fluorocarbon B having m carbon atoms and no double bond, separating a second mixture having a reduced concentration of fluorocarbon B relative to the first mixture; The separation is carried out by contacting the first mixture with an adsorbent containing a metal-organic framework.

[0013] (First mixture) The first mixture contains fluorocarbon A having n carbon atoms and one or more double bonds, and fluorocarbon B having m carbon atoms and no double bonds. In this embodiment, fluorocarbon A or fluorocarbon B is also referred to as an adsorbate.

[0014] In the fluorocarbon A, the number of double bonds may be 1 or more, preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and even more preferably 1 or more and 2 or less.

[0015] The number of carbon atoms n of the fluorocarbon A is preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, and even more preferably 2 or more and 3 or less.

[0016] The boiling point of the fluorocarbon A may be, for example, −80° C. or higher and −20° C. or lower, and may further be −60° C. or higher and −30° C. or lower. In one embodiment, the fluorocarbon having a carbon number n exists as a gas in the first mixture.

[0017] Examples of the fluorocarbon A include hydrochlorofluoroolefins and hydrofluoroolefins.

[0018] Examples of the hydrofluoroolefin include 1,1-difluoroethylene, 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, hexafluoropropene, 1,1,1,4,4,4-hexafluorobutene, etc. The fluorocarbon A is preferably a hydrofluorocarbon, and more preferably 2,3,3,3-tetrafluoropropene (R1234yf).

[0019] Examples of the hydrochlorofluoroolefin include 1-chloro-3,3,3-trifluoropropene and 1-chloro-2,3,3,3-tetrafluoropropene. The fluorocarbon A may contain one or more compounds.

[0020] The concentration of fluorocarbon A in the first mixture may be, for example, 0.0001 mol % or more and 90 mol % or less, and may further be 0.0001 mol % or more and 20 mol % or less, in the entire first mixture.

[0021] The carbon number m of the fluorocarbon B is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and even more preferably 1 or more and 3 or less.

[0022] The difference between the number of carbon atoms of the fluorocarbon A and the number of carbon atoms of the fluorocarbon B may be, for example, from 0 to 5, further from 0 to 3, and particularly from 0 to 1. According to the separation method of the present disclosure, even when the carbon numbers of the fluorocarbon A and the fluorocarbon B are similar, a second mixture having a different composition ratio can be separated.

[0023] The boiling point of the fluorocarbon B may be, for example, −80° C. or higher and −20° C. or lower, and may further be −60° C. or higher and −30° C. or lower. In one embodiment, the fluorocarbon having a carbon number n is present as a gas in the first mixture.

[0024] The difference between the boiling point of the fluorocarbon A and the boiling point of the fluorocarbon B may be, for example, 0° C. or more and 20° C. or less, and may further be 0° C. or more and 10° C. or less. According to the separation method of the present disclosure, even when the boiling points of the fluorocarbon A and the fluorocarbon B are close to each other, a second mixture having a different composition ratio can be separated.

[0025] Examples of the fluorocarbon B include hydrochlorofluorocarbons and hydrofluorocarbons.

[0026] Examples of the hydrofluorocarbon include difluoromethane, 1,1-difluoroethane, 1,2-difluoroethane, 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, and pentafluoroethane.

[0027] Examples of the hydrochlorofluorocarbon include chlorodifluoromethane and chlorotrifluoroethane.

[0028] The fluorocarbon B is preferably a hydrofluorocarbon, more preferably one or more selected from 1,1,1,2-tetrafluoroethane (R134a), 1,1,1-trifluoroethane (R143a) and 1,1,1,2,2-pentafluoroethane (R125). The fluorocarbon B may comprise one or more compounds.

[0029] The concentration of fluorocarbon B in the first mixture may be, for example, 0.0001 mol % or more and 90 mol % or less, and may further be 0.0001 mol % or more and 20 mol % or less, in the entire first mixture.

[0030] If the composition ratio of fluorocarbon A to fluorocarbon B in the first composition (A / (A+B)×100) is C1, C1 may be, for example, 0.0001 or more and 90 or less, more preferably 0.0001 or more and 50 or less, and even more preferably 0.0001 or more and 20 or less, on a molar basis.

[0031] The first mixture may be an azeotropic or pseudo-azeotropic mixture of fluorocarbons. According to the separation method of the present disclosure, even an azeotropic or pseudo-azeotropic mixture can separate fluorocarbons with a specific carbon number. Examples of such azeotropic or pseudo-azeotropic mixtures include mixtures in which the difference in boiling point between the fluorocarbon to be separated (in this embodiment, fluorocarbon A or fluorocarbon B) and the boiling point of the other fluorocarbon is 1°C or more and 20°C or less, or even 3°C or more and 18°C ​​or less, at 1 atmosphere (1,013 hPa).

[0032] In one embodiment, fluorocarbon A can be 2,3,3,3-tetrafluoropropene (R1234yf) and fluorocarbon B can be one or more selected from 1,1,1,2-tetrafluoroethane (R134a), 1,1,1-trifluoroethane (R143a), and 1,1,1,2,2-pentafluoroethane (R125).

[0033] The first mixture may contain other compounds in addition to fluorocarbon A and fluorocarbon B. The boiling point of such other compounds may be, for example, −100° C. or lower, or −150° C. or lower. In one embodiment, such other compounds are contained in the first mixture as a gas.

[0034] The other compounds include nitrogen, oxygen, carbon dioxide, water, and the like.

[0035] (adsorbent) The adsorbent includes a metal-organic framework (PCP: Porous Coordination Polymer, or MOF: Metal-Organic Framework). Hereinafter, in this embodiment, the adsorbent including the metal-organic framework will also be simply referred to as the adsorbent.

[0036] The metal-organic framework may typically be an organic-inorganic composite structure having a regularly continuous three-dimensional framework. The metal-organic framework preferably includes metal ions and one or more organic ligands. The organic ligand typically includes two or more groups capable of forming coordinate bonds with the metal ions per molecule. When the organic ligands coordinate to the metal ions, a highly regular, three-dimensionally continuous structure (e.g., a network structure) is formed, and pores are formed between the metal ions and the organic ligands. In such a three-dimensional structure, the effective pore size and flexibility of the metal-organic framework, as well as the interaction between the metal-organic framework and the adsorbate, can be controlled by combining the type of metal ions and the organic ligands. Furthermore, the metal-organic framework exhibits high durability against repeated adsorption and desorption, with no decrease in the adsorption amount (maximum adsorption amount) even after repeated adsorption and desorption of the adsorbate. Furthermore, the metal-organic framework is not easily affected by temperature (heat) or humidity, and the adsorption amount does not decrease even when stored under high-temperature and high-humidity conditions for a long period of time, with high durability against high temperatures and high humidity.

[0037] It is believed that the pore structure of the metal-organic framework makes it possible to control the adsorption behavior between the metal-organic framework and fluorocarbon A having a double bond or fluorocarbon B having no double bond, and to change the composition ratio of fluorocarbon A and fluorocarbon B in the first mixture.

[0038] The metal ions are not particularly limited, but are, for example, ions of metals selected from the group consisting of Group Ia, Group IIa, Group IIIa, Groups IVa to VIII, and Groups Ib to VIb. Such metals may preferably be one or more selected from the group consisting of Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Ti, Si, Ge, Sn, Pb, As, Sb, Bi, La, Ce, Pr, Nd, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm, and Yb, and more preferably be one or more selected from the group consisting of Zn, Cu, Ti, Co, Mn, Ni, Al, Ca, Zr, and Mg.

[0039] Specifically, such metal ions include Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ ,Sc. 3+ , Y 3+ , Ln 3+ , Ti 4+ , Zr 4+ , Hf 4+ , V 4+ , V 3+ , V 2+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Mn 2+ ,Re 3+ ,Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh + , Ir 2+ , Ir + , Ni 2+ , Ni + , Pd 2+ , Pd+ , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , Au + , Zn 2+ , Cd 2+ , Hg 2+ , Al 3+ , Ga 3+ , ln 3+ , T.I. 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As + , Sb 5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ , Bi + , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Pm 3+ , Sm 3+ , En 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ and Yb 3+ and more preferably, Cr 3+ , Zn 2+ , Cu 2+ , Cu+, Ti 4+ , Ti 3+ , Co 3+ , Co 2+ , Mn 3+ , Mn 2+ , Fe 3+ , Fe 2+ , Ni 2+ , Ni + , Al 3+ , Ca 2+ , Zr4+ and Mg 2+ The compound may be one or more compounds selected from the group consisting of:

[0040] The metal ions may be of one type or two or more types, but preferably are of one type.

[0041] In a preferred embodiment, the metal ions are one or more selected from Fe ions, Cu ions, Ni ions, Mg ions, Co ions, Cr ions, Zr ions and Zn ions, and preferably Fe 2+ , Fe 3+ , Cu 2+ , Ni 2+ , Mg 2+ , Co 2+ , Cr 3+ and Zn 2+ One or more selected from the above.

[0042] The organic ligand is not particularly limited as long as it contains two or more groups capable of forming a coordinate bond with a metal ion in one molecule. The coordinate bond is formed, for example, by a functional group capable of forming a coordinate bond with a metal ion.

[0043] Examples of functional groups capable of forming the above-mentioned coordinate bonds include -COOH, -CS2H, -NO2, -B(OH)2, -SO3H, -Si(OH)3, -Ge(OH)3, -Sn(OH)3, -Si(SH)4, -Ge(SH)4, -Sn(SH)3, -PO3H, -AsO3H, -AsO4H, -P(SH)3, -As(SH)3, -CH(RSH)2, -C(RSH)3, -CH(RNH2)2, -C(RNH2)3, -CH(ROH)2, -C(ROH)3, -CH(RCN)3, and -C(RCN)3. In the above formula, R is a single bond, an alkylene group having 1 to 5 carbon atoms (e.g., methylene, ethylene, n-propylene, i-propylene, n-butylene, i-butylene, tert-butylene, or n-pentylene), a divalent aromatic group having 6 to 14 carbon atoms (e.g., phenylene), or a combination of the above alkylene group and an aromatic group (e.g., -phenylene-alkylene-phenylene-). In addition, the functional group capable of forming a coordinate bond may be a heteroatom (e.g., N, O, S, B, P, Si, or Al) contained in a heterocycle, and preferably a nitrogen atom contained in a heterocycle.

[0044] In a preferred embodiment, the functional group capable of forming a coordinate bond may be -COOH, a nitrogen atom contained in a heterocycle, or the like.

[0045] The organic ligand preferably has the functional groups so as to be bidentate or higher. In such an organic ligand, the portion other than the functional groups is not limited as long as the organic ligand can form a coordinate bond with a metal ion.

[0046] In one embodiment, the organic ligand is derived from a saturated or unsaturated aliphatic or aromatic compound. Alternatively, the ligand may be derived from a compound in which such an aliphatic compound and an aromatic compound are combined (hereinafter also referred to as an "aliphatic aromatic compound").

[0047] The aliphatic moiety of the aliphatic compound or aliphatic aromatic compound may be linear, branched, or cyclic. When the aliphatic moiety is cyclic, it may have multiple rings. The aliphatic moiety of the aliphatic compound or aliphatic aromatic compound preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. In a preferred embodiment, the aliphatic moiety is derived from methane, adamantane, acetylene, ethylene, or butadiene.

[0048] The aromatic moiety of the aromatic compound or aromatic aliphatic compound may have one or more rings, for example, 2, 3, 4, or 5 rings. These rings may be fused or unfused. The aromatic moiety of the aromatic compound or aliphatic aromatic compound preferably has 1, 2, or 3 rings, more preferably 1 or 2 rings. Each ring of the compound may also have at least one heteroatom in the ring, such as N, O, S, B, P, Si, or Al, preferably N, O, or S. The aromatic moiety of the aromatic compound or aromatic aliphatic compound preferably contains one or two rings containing 6 carbon atoms. When the aromatic moiety has two rings, the two rings may be fused or unfused. In a preferred embodiment, the aromatic moiety is derived from benzene, naphthalene, biphenyl, bipyridyl, or pyridyl.

[0049] In one embodiment, the organic ligand is derived from a dicarboxylic acid, tricarboxylic acid, or tetracarboxylic acid.

[0050] Examples of the dicarboxylic acid include oxalic acid, succinic acid, tartaric acid, maleic acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, and 1,3-butadiene-1,4-dicarboxylic acid. carboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidedicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid Acid, Thiophene-3,4-dicarboxylic acid, 2-Isopropylimidazole-4,5-dicarboxylic acid, Tetrahydropyran-4,4-dicarboxylic acid, Perylene-3,9-dicarboxylic acid, Perylenedicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-Dioxaoctanedicarboxylic acid, 3,5-Cyclohexadiene-1,2-dicarboxylic acid, Octanedicarboxylic acid, Pentane-3,3-dicarboxylic acid, 4,4'-Diamino-1,1'-biphenyl-3,3'-dicarboxylic acid, 4,4'-Diaminobiphenyl-3,3'-dicarboxylic acid, Benzidicarboxylic acid 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-binaphthyldicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilino-anthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran 250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-Hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, hydroxybenzophenone Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, Pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, 4,4'-diamino(diphenyl ether)diimidedicarboxylic acid, 4,4'-diaminodiphenylmethanediimidedicarboxylic acid, 4,4'-diamino(diphenyl sulfone)diimidedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantine Benzenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2',3'-diphenyl-p-terphenyl-4,4"-dicarboxylic acid, (diphenyl ether)-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxithiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzene dicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosenedicarboxylic acid, 4,4'-dihydroxy-3,3'-biphenyldicarboxylic acid, 4,4'-Dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorubin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid , 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazole dicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecane dicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridine dicarboxylic acid, and camphor dicarboxylic acid.

[0051] Examples of the tricarboxylic acid include 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,3-,1,2,4-benzenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 4,4′,4″-(1,3,5-benzenetriyl)trisbenzoic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, and aulintricarboxylic acid.

[0052] Examples of the tetracarboxylic acid include perylene tetracarboxylic acids such as 1,1-dioxidoperillo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, and (perylene-1,12-sulfone)-3,4,9,10-tetracarboxylic acid; butane tetracarboxylic acids such as 1,2,3,4-butane tetracarboxylic acid and meso-1,2,3,4-butane tetracarboxylic acid; decane-2,4,6,8-tetracarboxylic acid; and 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11 ,13-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, and cyclopentanetetracarboxylic acids such as cyclopentane-1,2,3,4-tetracarboxylic acid.

[0053] In one embodiment, the organic ligand is derived from a heterocycle capable of forming a coordinate bond through a ring heteroatom, such as the following heterocycle: The heterocycle may be unsubstituted or substituted:

[0054] [ka]

[0055] In one embodiment, the organic ligand is derived from an azole, such as a diazole or triazole, preferably a triazole.

[0056] In a preferred embodiment, the organic ligand includes an organic ligand derived from a polycarboxylic acid and an organic ligand derived from an azole, and preferably includes an organic ligand derived from an aromatic polycarboxylic acid.

[0057] In a preferred embodiment, the organic ligand is selected from 1,4-benzenedicarboxylic acid, 1,2-benzenedicarboxylic acid, maleic acid, 1,3,5-benzenetricarboxylic acid, 4,4',4"-(1,3,5-benzenetriyl)trisbenzoic acid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid, oxalic acid, 4,4'-dihydroxy-3,3'-biphenyldicarboxylic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 4,4'-bipyridine, triazole, imidazole, 3,3'-bipyrazole, benzimidazole, and 3,5-pyridinedicarboxylic acid. In a more preferred embodiment, the organic ligand is selected from 1,4-benzenedicarboxylic acid, 4,4'-dihydroxy-3,3'-biphenyldicarboxylic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, and 2,5-dihydroxy-1,4-benzenedicarboxylic acid.

[0058] The organic ligand may be of one type only, or of two or more types.

[0059] In the present disclosure, "derived from a compound" includes not only the compound itself, but also a form in which the compound is partially protonated or a form in which the compound is completely protonated.

[0060] The metal organic framework preferably has an open metal site consisting of a coordinatively unsaturated metal ion. The open metal site refers to a site where the metal contained in the metal organic framework is in a coordinatively unsaturated state and any molecule can be coordinated. The presence or absence of an open metal site does not depend on the types of metal ion and organic ligand.

[0061] Examples of metal-organic frameworks having open metal sites include HKUST-1, MIL-100(Fe), MIL-101(Cr), MOF-74(Ni), MOF-74(Mg), MOF-74(Co), MOF-74(Cu), Mg2(dobpdc), and UTSA-16(Zn).

[0062] The metal-organic framework can be produced by contacting metal ions with organic ligands. The contacting of the metal ion with the organic ligand may be carried out in the presence of a solvent, which may be water, ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethylsulfoxide, water, hydrogen peroxide, methylamine, sodium hydroxide solution, N-methylpyrrolidone ether, acetonitrile, benzyl chloride, triethylamine, or ethylene glycol, or a mixture thereof.

[0063] The contact of the metal ion with the organic ligand may be carried out under increased pressure or under normal pressure. The temperature during the contact may be, for example, 10 to 200° C. or 10 to 150° C. The mixture may be stirred during the contact.

[0064] The effective pore diameter is, for example, 0.30 nm or more and 5.00 nm or less, preferably 0.4 nm or more and 4.00 nm or less, and more preferably 1.00 nm or more and 2.50 nm or less. In one embodiment, the effective pore diameter of the porous body is, for example, 0.30 nm or more, preferably 0.4 nm or more, and more preferably 1.00 nm or more, and for example, 5.00 nm or less, preferably 4.00 nm or less, and more preferably 2.00 nm or less.

[0065] The effective pore diameter is the pore diameter of a porous body, such as a metal-organic framework, that is determined from the degree of adsorption and the molecular diameter of the adsorbate when the porous body is brought into contact with the adsorbate. Specifically, the effective pore diameter can be determined by converting the relative pressure of the nitrogen adsorption isotherm into the effective pore diameter using the Horvath-Kawazoe method. The conversion formula may be the calculation formula described in J. Chem. Eng. Jpn., 1983, 16, 6, 470-475, and the parameter values ​​in the conversion formula may be values ​​based on a combination of carbon and nitrogen.

[0066] The specific surface area of ​​the metal organic framework is, for example, 40 m 2 / g or more, preferably 100m 2 / g or more, more preferably 300m 2 / g or more, for example 3,000m 2 / g or less, and 2 The specific surface area of ​​the metal organic framework is calculated from the nitrogen gas adsorption isotherm using the BET method.

[0067] The equilibrium adsorption amount of fluorocarbon A or fluorocarbon B in the metal organic framework may be, for example, 1 g / 10 g or more and 100 g / 10 g or less, when measured at a temperature of 298 K and a pressure in the range of 0.4 PaG to 1 MPaG (gauge pressure).

[0068] The content of the metal organic framework in the adsorbent is, for example, 50% by mass or more and 100% by mass or less, preferably 70% by mass or more and 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less.

[0069] The adsorbent may contain a resin in addition to the metal organic framework, such as an acrylic resin, a polyurethane resin, a polyolefin resin, a polyester resin, a polyamide resin, a vinyl chloride resin, a styrene resin, a vinyl ether resin, a polyvinyl alcohol resin, a polycarbonate resin, or a polysulfone resin.

[0070] The adsorbent may contain additives such as emulsifiers, antifoaming agents, surfactants, leveling agents, thickeners, viscoelasticity modifiers, defoamers, wetting agents, dispersants, preservatives, plasticizers, penetrants, fragrances, bactericides, miticides, mildewcides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments, etc. The adsorbent may be in the form of powder, granules, flakes, or pellets.

[0071] (Contacting the First Mixture with the Adsorbent) By contacting the first mixture with the adsorbent, fluorocarbon A or fluorocarbon B can be adsorbed onto the metal organic framework contained in the adsorbent, and a second mixture can be separated from the first mixture, the second mixture having a composition ratio of fluorocarbon A to fluorocarbon B different from that of the first mixture. In one embodiment, when the first mixture is contacted with the adsorbent, the first mixture is preferably contacted as a gas (vapor).

[0072] The contact of the first mixture with the adsorbent may be carried out, for example, by a batch method or a column method. The batch method is a method in which the adsorbent and the first mixture are placed in a sealable container and allowed to stand for a certain period of time under conditions of a predetermined temperature and a predetermined pressure, thereby bringing the first mixture into contact with the adsorbent. The column method is a method in which the adsorbent is filled in a container (column), and the first mixture is allowed to flow through the container (column), thereby bringing the first mixture into contact with the adsorbent.

[0073] In one embodiment, the temperature during the contact may be, for example, 0°C or higher and 100°C or lower, or even 0°C or higher and 50°C or lower. In another embodiment, the temperature during the contact may be, for example, 10°C or higher and 50°C or lower, 15°C or higher and 50°C or lower, or 15°C or higher and 30°C or lower. Furthermore, the pressure (gauge pressure) during the contact may be 0 MPaG or higher and 2 MPaG or lower, or 0.2 MPaG or higher and 1.5 MPaG or lower. When the pressure during the contact is within the above range, the adsorbate is more easily adsorbed by the adsorbent, which can improve separation efficiency and maintain the pore structure of the adsorbent.

[0074] When the contacting is carried out by a column method, the linear velocity of the first mixture may be 0.01 cm / sec or more and 100 cm / sec or less, or 0.05 cm / sec or more and 10 cm / sec or less.

[0075] (Second mixture) The second mixture contains one or more selected from the fluorocarbon A and the fluorocarbon B, and the composition ratio of the fluorocarbon A to the fluorocarbon B is different from that of the first mixture. The second mixture preferably contains the fluorocarbon A and the fluorocarbon B.

[0076] If the composition ratio of fluorocarbon A to fluorocarbon B in the second mixture (A / (A+B)×100) is C2, C2 may be, for example, 0.0001 or more and 10 or less, more preferably 0.0001 or more and 5 or less, and even more preferably 0.0001 or more and 1 or less, on a molar basis.

[0077] the molar concentration C of fluorocarbon A in the second mixture A2 may be, for example, 0.0001 mol % or more and 1 mol % or less, and further may be 0.0001 mol % or more and 0.01 mol % or less, in the entire second mixture.

[0078] (Regeneration of adsorbent) The separation method of the present disclosure may further include desorbing fluorocarbon A or fluorocarbon B adsorbed on the adsorbent from the adsorbent after contacting the first mixture with the adsorbent. By desorbing fluorocarbon A or fluorocarbon B adsorbed on the adsorbent from the adsorbent, the adsorption capacity can be restored and the adsorbent can be regenerated. This also allows fluorocarbon A or fluorocarbon B to be recovered.

[0079] In one embodiment, the fluorocarbon desorbed from the adsorbent can be fluorocarbon A. In another embodiment, the fluorocarbon desorbed from the adsorbent can be fluorocarbon B.

[0080] The desorption of fluorocarbon A or fluorocarbon B can be carried out by reducing pressure, increasing temperature, flowing air and nitrogen, or flowing heated air and heated nitrogen, or the like.

[0081] The pressure (gauge pressure) during the desorption may be preferably 0.1 MPaG or less, more preferably 0 MPaG or less, and even more preferably -0.10 MPaG or less. The temperature during the desorption may be preferably 15 to 200°C, more preferably 50 to 180°C, and even more preferably 100 to 150°C.

[0082] (Contacting the second mixture with the adsorbent) The separation method of the present disclosure may further include contacting the separated second mixture with the adsorbent. Such an operation may yield a new mixture having a composition ratio of fluorocarbon A to fluorocarbon B different from that of the second mixture. In one embodiment, when the concentration of fluorocarbon A in the second mixture is reduced compared to the concentration of fluorocarbon A in the first mixture, it is preferable that the concentration of fluorocarbon A in the new mixture is reduced compared to the concentration of fluorocarbon A in the second mixture. In another embodiment, when the concentration of fluorocarbon B in the second mixture is reduced compared to the concentration of fluorocarbon B in the first mixture, it is preferable that the concentration of fluorocarbon B in the new mixture is reduced compared to the concentration of fluorocarbon B in the second mixture.

[0083] The number of times the adsorbent and the mixture are brought into contact with each other is not particularly limited, and may be preferably 1 to 5 times, and more preferably 1 to 3 times. In the present disclosure, the first contact corresponds to the contact of the first mixture with the adsorbent, and the mth contact with the adsorbent corresponds to the contact of the mixture obtained by the (m-1)th contact with the adsorbent with the adsorbent (where m is an integer of 2 or more). In this embodiment, the adsorbent used in the second or subsequent contacts is an adsorbent containing a metal organic framework, but is not limited thereto and may be an adsorbent containing a porous material as described in the second embodiment. In addition, the adsorbents used in two or more contacts may be the same or different from each other.

[0084] The procedure and conditions for contacting the mixture obtained in the m-1th contact with the adsorbent can be the same as those for contacting the first mixture with the adsorbent.

[0085] (purification) The separation method of the present disclosure may further include purifying the separated second mixture. Such purification may include obtaining a new mixture having a composition ratio of fluorocarbon A to fluorocarbon B different from that of the second mixture. In one embodiment, when the concentration of fluorocarbon A in the second mixture is reduced compared to the concentration of fluorocarbon A in the first mixture, it is preferable that the concentration of fluorocarbon A in the new mixture is reduced compared to the concentration of fluorocarbon A in the second mixture. In another embodiment, when the concentration of fluorocarbon B in the second mixture is reduced compared to the concentration of fluorocarbon B in the first mixture, it is preferable that the concentration of fluorocarbon B in the new mixture is reduced compared to the concentration of fluorocarbon B in the second mixture.

[0086] The number of purification steps is not particularly limited, and may be preferably 1 to 5, more preferably 1 to 3. In the present disclosure, the nth purification step refers to the step of purifying the (n-1)th new mixture obtained by the (n-1)th purification step (where n is an integer of 2 or greater).

[0087] In one embodiment, the purification can be carried out by distillation or rectification. Such distillation can be carried out using a commonly used distillation column, for example, a packed column or a plate column. The purified product is distilled as a distillate from the top of the distillation column, and the remainder is distilled as a bottom product from the bottom of the distillation column. The number of theoretical plates of the distillation column can be, for example, 1 to 100. The pressure (gauge pressure) during distillation or rectification can be 0 MPaG or more and 5 MPaG or less. The temperature at the top of the distillation column can be, for example, -60°C or more and 100°C or less, and the temperature at the bottom of the distillation column can be, for example, 50°C or more and 200°C or less. An extraction solvent can be present during distillation.

[0088] The distillate can be distilled again (two or more times) to carry out rectification.

[0089] In this embodiment, the second mixture is purified, but the present disclosure is not limited thereto. For example, the first mixture may be purified before contacting the first mixture with the adsorbent containing the metal-organic framework. That is, the mixture purified by the above operation may be contacted with the adsorbent containing the metal-organic framework.

[0090] (system) A fluorocarbon purification system (hereinafter also simply referred to as "system") that implements the first separation method described above is also included within the technical scope of the present disclosure.

[0091] The system preferably comprises: an adsorbent including a metal organic framework; The adsorbent containing the metal organic framework is prepared by: A second mixture having a different composition ratio of fluorocarbon A to fluorocarbon B than the first mixture can be separated.

[0092] FIG. 1 is a schematic diagram illustrating a two-stage system as an example of a system according to this embodiment.

[0093] In the system of Fig. 1, the first mixture is stored in a gas tank 1. The first mixture is supplied to a first-stage separation module 4a via a pressure regulator 2a and a mass flow controller 3a. In one embodiment, the back pressure of the first mixture supplied to the separation module 4a can be pressurized and controlled by the pressure regulator 2a, but this is not a limitation. The pressure regulator 2a may also be omitted.

[0094] The separation module 4a includes an adsorbent 10a containing a metal-organic framework, and the first mixture is supplied to the adsorbent 10a containing the metal-organic framework.

[0095] In the two-stage separation device, after contact with the adsorbent 10a containing the metal-organic framework, the flow rate of the second mixture is measured by a mass flow meter 5, and the second mixture is supplied to a second-stage separation module 4b via a pressure regulator 2b and a mass flow controller 3b. In one embodiment, the back pressure of the second mixture supplied to the second-stage separation module 4b can be pressurized and controlled by the pressure regulator 2b, but this embodiment is not limited thereto. The pressure regulator 2b can also be omitted.

[0096] The second-stage separation module 4b includes an adsorbent 10b containing a metal-organic framework, and the second mixture is supplied to the adsorbent 10b containing the metal-organic framework.

[0097] A new mixture separated by contact between the second mixture and adsorbent 10b containing the metal-organic framework passes through pressure regulator 2c, has its gas composition analyzed by gas composition analyzer 8b, and is then recovered in recovery pipe 9. In one embodiment, a mass flow meter may be used to measure the flow rate of the new mixture separated by contact with adsorbent 10b containing the metal-organic framework. In another embodiment, gas composition analyzer 8a can be omitted.

[0098] In this embodiment, a two-stage separation device has been described, but the present invention is not limited to this and can be modified as appropriate. For example, the separation device may be a one-stage, three-stage, four-stage or more stage type.

[0099] In the case of a p-stage system (p is 3 or more), the p-1th mixture separated by contact with the adsorbent in the p-1th separation module may be supplied to the separation module via a pressure regulator and a mass flow controller, and brought into contact with the adsorbent contained in the separation module to separate a new pth mixture. The pth mixture can be recovered after gas composition analysis, which may be performed as necessary, to perform the pth separation.

[0100] (composite material) A composite material comprising a metal organic framework and the fluorocarbon A or the fluorocarbon B is also encompassed within the technical scope of the present disclosure. In such a composite material, the metal organic framework preferably has an open metal site. In one aspect, the composite material preferably comprises a metal organic framework and the fluorocarbon A. In another aspect, the composite material preferably comprises a metal organic framework and the fluorocarbon B.

[0101] In the above composite material, the content of fluorocarbon A or fluorocarbon B is, for example, 0.1 part by mass or more and 100 parts by mass or less, and preferably 1 part by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the metal organic framework.

[0102] The composite material may contain a resin in addition to the fluorocarbon and porous organic salt, such as an acrylic resin, a polyurethane resin, a polyolefin resin, a polyester resin, a polyamide resin, a vinyl chloride resin, a styrene resin, a vinyl ether resin, a polyvinyl alcohol resin, a polycarbonate resin, or a polysulfone resin.

[0103] The composite material may contain additives such as emulsifiers, antifoaming agents, surfactants, leveling agents, thickeners, viscoelasticity modifiers, defoamers, wetting agents, dispersants, preservatives, plasticizers, penetrating agents, fragrances, bactericides, miticides, mildewcides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, and pigments.

[0104] (Second embodiment: second separation method) The second separation method of the present disclosure comprises: A first mixture containing fluorocarbon A having n carbon atoms and one or more double bonds and fluorocarbon B having m carbon atoms and no double bond, separating a third mixture having a reduced concentration of fluorocarbon A relative to the first mixture; The separation is carried out by contacting the first mixture with an adsorbent.

[0105] According to the first separation method of the present disclosure, a third mixture in which the proportion of fluorocarbon gases having double bonds is reduced can be separated by contacting an adsorbent with a first mixture containing two or more fluorocarbon gases. Although the present disclosure should not be interpreted as being limited to a particular theory, it is believed that fluorocarbon A having double bonds can be adsorbed by the adsorbent, thereby obtaining a third mixture in which the proportion of fluorocarbon A having double bonds is reduced. Note that the third mixture may not contain fluorocarbon A.

[0106] The first mixture, fluorocarbon A, and fluorocarbon B have the same meanings as the first mixture, fluorocarbon A, and fluorocarbon B in the first embodiment.

[0107] The number of carbon atoms n of the fluorocarbon A is preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, and even more preferably 2 or more and 3 or less.

[0108] The fluorocarbon A is preferably a hydrofluoroolefin, and more preferably 2,3,3,3-tetrafluoropropene (R1234yf). The fluorocarbon A may contain one or more compounds.

[0109] the concentration C of fluorocarbon A in the first mixture A1 may be, for example, 0.0001 mol % or more and 90 mol % or less, and further may be 0.0001 mol % or more and 20 mol % or less, in the entire first mixture.

[0110] The fluorocarbon B is preferably a hydrofluorocarbon, more preferably one or more selected from 1,1,1,2-tetrafluoroethane (R134a), 1,1,1-trifluoroethane (R143a) and 1,1,1,2,2-pentafluoroethane (R125). The fluorocarbon B may comprise one or more compounds.

[0111] The concentration of fluorocarbon B in the first mixture may be, for example, 0.0001 mol % or more and 90 mol % or less, and may further be 0.0001 mol % or more and 20 mol % or less, in the entire first mixture.

[0112] The first mixture may contain other compounds in addition to fluorocarbon A and fluorocarbon B. The boiling point of such other compounds may be, for example, −100° C. or lower, or −150° C. or lower. In one embodiment, such other compounds are contained in the first mixture as a gas.

[0113] The other compounds include nitrogen, oxygen, carbon dioxide, water, and the like.

[0114] (adsorbent) The adsorbent (hereinafter also referred to as "second adsorbent" in this embodiment) can adsorb fluorocarbon A having a double bond and carbon number n. Typically, the second adsorbent adsorbs fluorocarbon A having a double bond, but does not adsorb fluorocarbon B having no double bond. Therefore, by contacting the first mixture with the second adsorbent, a third mixture in which fluorocarbon A has been reduced can be separated from the first mixture.

[0115] The second adsorbent preferably contains a porous body having pores as an adsorbent, and the fluorocarbon having a carbon number n can be separated from the first mixture by adsorbing the fluorocarbon having a carbon number n into the pores.

[0116] The effective pore size of the porous body is, for example, 0.30 nm or more and 5.00 nm or less, preferably 0.4 nm or more and 4.00 nm or less, and more preferably 1.00 nm or more and 2.50 nm or less. In one embodiment, the effective pore size of the porous body is, for example, 0.30 nm or more, preferably 0.40 nm or more, and more preferably 1.00 nm or more, and for example, 5.00 nm or less, preferably 4.00 nm or less, and more preferably 2.00 nm or less.

[0117] The specific surface area of ​​the porous body is, for example, 40 m 2 / g or more, preferably 100m 2 / g or more, more preferably 300m 2 / g or more, for example 3,000m 2 / g or less, and 2 The specific surface area of ​​the porous body is calculated from the nitrogen gas adsorption isotherm using the BET method.

[0118] The equilibrium adsorption amount of fluorocarbon having carbon number n in the porous body may be, for example, 1 g / 10 g or more and 100 g / 10 g or less when measured at a temperature of 298 K and a pressure range of 0.4 PaG to 1 MPaG (gauge pressure).

[0119] The porous body may be in the form of a powder (particulate), film, granules, molded body (pellet, etc.), etc., preferably a molded body, more preferably a pellet. The pellet may be cylindrical or spherical. In the case of a cylindrical shape, the radius of the cylinder is preferably 1.6 mm or more and 6 mm or less, and the thickness of the cylinder is preferably 2 mm or more and 6 mm or less. In the case of a spherical shape, which includes non-spherical shapes, the radius of the sphere is preferably 4 mm or more and 12 mm or less.

[0120] The porous body preferably contains at least one selected from the group consisting of, for example, zeolite, activated carbon, silica gel, and metal-organic frameworks (PCP: Porous Coordination Polymer, or MOF: Metal-Organic Framework), and typically contains a metal-organic framework.

[0121] The metal organic framework has the same meaning as the metal organic framework in the first embodiment.

[0122] The content of the porous body in the second adsorbent is, for example, 50% by mass or more and 100% by mass or less, preferably 70% by mass or more and 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less.

[0123] In addition to the porous body, the second adsorbent may contain a resin, such as an acrylic resin, a polyurethane resin, a polyolefin resin, a polyester resin, a polyamide resin, a vinyl chloride resin, a styrene resin, a vinyl ether resin, a polyvinyl alcohol resin, a polycarbonate resin, or a polysulfone resin.

[0124] The second adsorbent may contain additives such as emulsifiers, antifoaming agents, surfactants, leveling agents, thickeners, viscoelasticity modifiers, defoamers, wetting agents, dispersants, preservatives, plasticizers, penetrants, fragrances, bactericides, miticides, fungicides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments, etc. The second adsorbent may be in the form of powder, granules, flakes, or pellets.

[0125] (Contacting the first mixture with the second adsorbent) By contacting the first mixture with the second adsorbent, fluorocarbon A contained in the first mixture can be adsorbed onto the adsorbent, and a third mixture having a reduced concentration of fluorocarbon A can be separated from the first mixture. In one embodiment, when the first mixture is contacted with the second adsorbent, the first mixture is preferably contacted as a gas.

[0126] The contact of the first mixture with the second adsorbent may be carried out, for example, by a batch method or a column method. The batch method is a method in which the second adsorbent and the first mixture are placed in a sealable container and allowed to stand for a certain period of time under conditions of a predetermined temperature and a predetermined pressure, thereby bringing the first mixture into contact with the second adsorbent. The column method is a method in which the second adsorbent is packed into a container (column), and the first mixture is passed through the container (column), thereby bringing the first mixture into contact with the second adsorbent.

[0127] In one embodiment, the temperature during the contact may be, for example, 0°C or higher and 100°C or lower, or even 0°C or higher and 50°C or lower. In another embodiment, the temperature during the contact may be, for example, 10°C or higher and 50°C or lower, 15°C or higher and 50°C or lower, or 15°C or higher and 30°C or lower. Furthermore, the pressure (gauge pressure) during the contact may be 0 MPaG or higher and 2 MPaG or lower, or 0.2 MPaG or higher and 1.5 MPaG or lower. When the pressure during the contact is within the above range, the adsorbate is more easily adsorbed by the adsorbent, which can improve separation efficiency and maintain the pore structure of the adsorbent.

[0128] When the contacting is carried out by a column method, the linear velocity of the first mixture may be 0.01 cm / sec or more and 100 cm / sec or less, or 0.05 cm / sec or more and 10 cm / sec or less.

[0129] (Third mixture) The third mixture contains at least the fluorocarbon B, and the concentration of fluorocarbon A is reduced compared to the first mixture. The third mixture preferably contains fluorocarbon A and the fluorocarbon B.

[0130] If the composition ratio of fluorocarbon A to fluorocarbon B in the third mixture (A / (A+B)×100) is C3, C3 may be, for example, 0.0001 or more and 10 or less, more preferably 0.0001 or more and 5 or less, and even more preferably 0.0001 or more and 1 or less, on a molar basis.

[0131] the molar concentration C of fluorocarbon A in the third mixture A3 may be, for example, 0.0001 mol % or more and 1 mol % or less, and further may be 0.0001 mol % or more and 0.01 mol % or less, in the entire third mixture.

[0132] (Regeneration of adsorbent) The separation method of the present disclosure may further include desorbing the fluorocarbon A adsorbed on the second adsorbent from the second adsorbent after contacting the first mixture with the second adsorbent. By desorbing the fluorocarbon A adsorbed on the second adsorbent from the second adsorbent, the adsorption capacity can be restored and the second adsorbent can be regenerated. This also makes it possible to recover the fluorocarbon A. The desorption of fluorocarbon A can be carried out by reducing pressure, increasing temperature, flowing air and nitrogen, or flowing heated air and heated nitrogen, or the like.

[0133] The pressure (gauge pressure) during the desorption may be preferably 0.1 MPaG or less, more preferably 0 MPaG or less, and even more preferably -0.1 MPaG or less. The temperature during the desorption may be preferably 15 to 200°C, more preferably 50 to 180°C, and even more preferably 100 to 150°C.

[0134] (Contacting the third mixture with the second adsorbent) The separation method of the present disclosure may further include contacting the separated third mixture with the second adsorbent, which may result in a new mixture having a further reduced concentration of fluorocarbon A.

[0135] The number of times the second adsorbent is brought into contact with the mixture is not particularly limited, and may be preferably 1 to 5 times, more preferably 1 to 3 times. In two or more contacts, the second adsorbents used may be the same or different from each other.

[0136] The procedure and conditions for contacting the mixture obtained in the m-1th contact with the adsorbent can be the same as those for contacting the first mixture with the adsorbent.

[0137] (purification) The separation method of the present disclosure may further include purifying the separated third mixture, which may include obtaining a new mixture having a further reduced concentration of fluorocarbon A compared to the second mixture.

[0138] The number of purification steps is not particularly limited, and may be preferably 1 to 5, more preferably 1 to 3. In the present disclosure, the nth purification step refers to the step of purifying the (n-1)th new mixture obtained by the (n-1)th purification step (where n is an integer of 2 or greater).

[0139] In one embodiment, the purification can be carried out by distillation or rectification. Such distillation can be carried out using a commonly used distillation column, for example, a packed column or a plate column. The purified product is distilled as a distillate from the top of the distillation column, and the remainder is distilled as a bottom product from the bottom of the distillation column. The number of theoretical plates of the distillation column can be, for example, 1 to 100. The pressure (gauge pressure) during distillation or rectification can be 0 MPaG or more and 5 MPaG or less. The temperature at the top of the distillation column can be, for example, -60°C or more and 100°C or less, and the temperature at the bottom of the distillation column can be, for example, 50°C or more and 200°C or less. An extraction solvent can be present during distillation.

[0140] The distillate can be distilled again (two or more times) to carry out rectification.

[0141] In this embodiment, the third mixture is purified, but the present disclosure is not limited thereto. For example, the first mixture may be purified before contacting the first mixture with the adsorbent. That is, the mixture purified by the above procedure may be contacted with the adsorbent.

[0142] (system) A fluorocarbon purification system that implements the second separation method described above is also within the scope of the present disclosure.

[0143] The system preferably comprises: Equipped with an adsorbent, The adsorbent is prepared by separating a fluorocarbon A having n carbon atoms and one or more double bonds from a first mixture containing a fluorocarbon B having m carbon atoms and no double bonds, A third mixture may be separated, the third mixture having a different composition ratio of fluorocarbon A to fluorocarbon B than the first mixture.

[0144] FIG. 2 is a schematic diagram illustrating a two-stage system as an example of a system according to this embodiment.

[0145] In the system of Fig. 2, the first mixture is stored in a gas tank 1. The first mixture is supplied to a first-stage separation module 4c via a pressure regulator 2a and a mass flow controller 3a. In one embodiment, the back pressure of the first mixture supplied to the separation module 4c can be controlled by the pressure regulator 2a, but this is not a limitation. The pressure regulator 2a may also be omitted.

[0146] The separation module 4c includes an adsorbent 11a, and the first mixture is supplied to the adsorbent 11a.

[0147] In a two-stage separation apparatus, after contact with the adsorbent 11a, the flow rate of the third mixture is measured by a mass flow meter 5, and the third mixture is supplied to a second-stage separation module 4b via a pressure regulator 2b and a mass flow controller 3b. In one embodiment, the back pressure of the third mixture supplied to the second-stage separation module 4b can be controlled by pressure regulator 2b, but this is not a limitation. The pressure regulator 2b can also be omitted.

[0148] The second-stage separation module 4d includes an adsorbent 11b, and the third mixture is supplied to the adsorbent 11b.

[0149] The third mixture and a new mixture separated by contact with the adsorbent 11b are passed through a pressure regulator 2c, have their gas composition analyzed by a gas composition analyzer 8b, and are then recovered in a recovery pipe 9. In one embodiment, a mass flow meter may be used to measure the flow rate of the new mixture separated by contact with the adsorbent 11b. In another embodiment, the gas composition analyzer 8a can be omitted.

[0150] In this embodiment, a two-stage separation device has been described, but the present invention is not limited to this and can be modified as appropriate. For example, the separation device may be a one-stage, three-stage, four-stage or more stage type.

[0151] In the case of a p-stage system (p is 3 or more), the p-1th mixture separated by contact with the adsorbent in the p-1th separation module may be supplied to the separation module via a pressure regulator and a mass flow controller, and brought into contact with the adsorbent contained in the separation module to separate a new pth mixture. The pth mixture can be recovered after gas composition analysis, which may be performed as necessary, to perform the pth separation.

[0152] (Third embodiment: composite material) The technical scope of the present disclosure also includes a composite material including the metal organic framework and the above-mentioned fluorocarbon A. The metal organic framework and the fluorocarbon A have the same meanings as the metal organic framework and the fluorocarbon A in the first embodiment.

[0153] In such a composite material, the metal organic framework preferably contains metal ions and one or more organic ligands. The metal ions are one or more selected from Fe ions, Cu ions, Ni ions, Mg ions, Co ions, Cr ions, Zr ions, and Zn ions, and preferably Fe ions. 2+ , Fe 3+ , Cu 2+ , Ni 2+ , Mg 2+ , Co 2+ , Cr 3+ and Zn 2+ The organic ligand is preferably selected from 1,4-benzenedicarboxylic acid, 1,2-benzenedicarboxylic acid, maleic acid, 1,3,5-benzenetricarboxylic acid, 4,4',4"-(1,3,5-benzenetriyl)trisbenzoic acid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid, oxalic acid, 4,4'-dihydroxy-3,3'-biphenyldicarboxylic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 4,4'-bipyridine, triazole, imidazole, 3,3'-bipyrazole, benzimidazole, and 3,5-pyridinedicarboxylic acid, and more preferably selected from 1,4-benzenedicarboxylic acid, 4,4'-dihydroxy-3,3'-biphenyldicarboxylic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, and 2,5-dihydroxy-1,4-benzenedicarboxylic acid. The metal organic framework preferably has an open metal site.

[0154] In the above composite material, the content of fluorocarbon A is, for example, 1 part by mass or more and 100 parts by mass or less, and preferably 10 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the metal organic framework.

[0155] The composite material may contain a resin in addition to the fluorocarbon and porous organic salt, such as an acrylic resin, a polyurethane resin, a polyolefin resin, a polyester resin, a polyamide resin, a vinyl chloride resin, a styrene resin, a vinyl ether resin, a polyvinyl alcohol resin, a polycarbonate resin, or a polysulfone resin.

[0156] The composite material may contain additives such as emulsifiers, antifoaming agents, surfactants, leveling agents, thickeners, viscoelasticity modifiers, defoamers, wetting agents, dispersants, preservatives, plasticizers, penetrating agents, fragrances, bactericides, miticides, mildewcides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, and pigments. [Example]

[0157] The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0158] Example 1, Comparative Example 1 The adsorbents used were HKUST-1 (manufactured by Atomis) and CALF-20 (manufactured by Atomis) shown in Table 1. The adsorbents were pretreated by vacuum treatment at 130° C. for 2 hours.

[0159] (Adsorption breakthrough measurement of mixed gases) A 10 mol% R1234yf / 90 mol% R134a mixed gas was passed through an adsorption tower packed with the adsorbent shown in Table 1 at a total pressure of 0.4 MPaG, a temperature of 298 K, and a linear velocity of 0.4 cm / sec, and the R1234yf concentration at the outlet of the adsorption tower was measured. Figure 3 shows the adsorption breakthrough curve, which shows the change in R1234yf concentration. The R1234yf adsorption amount (amount per gram of adsorbent) obtained from the adsorption breakthrough curve is shown in Table 1 as the Gas A adsorption amount. [Table 1] [Explanation of symbols]

[0160] 1 gas tank 2a, 2b, 2c pressure regulator 3a, 3b Mass flow controller 4a, 4b, 4c, 4d Separation modules 5 Mass flow meter 7 Pressure reducing booster 8a, 8b Gas composition analyzer 9 Recovery piping 10a, 10b Adsorbent containing metal organic framework 11a, 11b Adsorbent

Claims

1. A first mixture containing fluorocarbon A having n carbon atoms and one or more double bonds and fluorocarbon B having m carbon atoms and no double bond, separating a second mixture having a composition ratio of said fluorocarbon A to said fluorocarbon B different from that of said first mixture; the separation is carried out by contacting the first mixture with an adsorbent comprising a metal-organic framework; The n is 2 or more and 3 or less, and the m is 1 or more and 10 or less, The method for separating fluorocarbons, wherein the metal-organic framework comprises one or more selected from HKUST-1, MIL-100(Fe), MIL-101(Cr), MOF-74(Ni), MOF-74(Mg), MOF-74(Co), MOF-74(Cu), Mg 2 (dobpdc), and UTSA-16(Zn).

2. 2. The separation method according to claim 1, wherein the first mixture is contacted with the adsorbent containing the metal-organic framework at a temperature of −10° C. or higher and 80° C. or lower.

3. The separation method according to claim 1, wherein m is 1 or more and 3 or less.

4. 2. The separation method of claim 1, wherein the fluorocarbon A comprises R1234yf.

5. 2. The separation method according to claim 1, wherein the fluorocarbon B comprises one or more selected from R134a, R143, R143a, R32 and R125.

6. 2. The separation method according to claim 1, wherein the metal-organic framework comprises one or more types of organic ligands, and the organic ligand comprises two or more groups capable of forming a coordinate bond to the metal ion in one molecule.

7. The separation method according to claim 1 , wherein the metal-organic framework has open metal sites consisting of coordinatively unsaturated metal ions.

8. The separation method according to claim 1 , wherein the adsorbent comprising the metal-organic framework further comprises a resin.

9. The separation method according to claim 1 , wherein the adsorbent comprising the metal-organic framework is in the form of powder, granules, flakes, or pellets.

10. 10. The method of claim 1, wherein the first mixture is an azeotrope or near-azeotrope of fluorocarbons.

11. The separation method according to any one of claims 1 to 8, further comprising contacting the separated second mixture with another adsorbent.

12. The separation method according to any one of claims 1 to 8, further comprising purifying the separated second mixture.

13. After contacting the first mixture with the adsorbent containing the metal organic framework, The separation method according to any one of claims 1 to 8, further comprising desorbing, from the adsorbent comprising the metal organic framework, the fluorocarbon A adsorbed to the adsorbent comprising the metal organic framework.

14. A fluorocarbon purification system that implements the separation method according to any one of claims 1 to 8.

15. A first mixture containing fluorocarbon A having n carbon atoms and one or more double bonds and fluorocarbon B having m carbon atoms and no double bond, separating a third mixture having a reduced concentration of fluorocarbon A relative to the first mixture; the separation is carried out by contacting the first mixture with an adsorbent comprising a metal-organic framework; The n is 2 or more and 3 or less, and the m is 1 or more and 10 or less, The method for separating fluorocarbons, wherein the metal-organic framework comprises one or more selected from HKUST-1, MIL-100(Fe), MIL-101(Cr), MOF-74(Ni), MOF-74(Mg), MOF-74(Co), MOF-74(Cu), Mg 2 (dobpdc), and UTSA-16(Zn).

16. 16. The separation method according to claim 15, wherein the contacting of the first mixture with the adsorbent is carried out at a temperature of −10° C. or higher and 80° C. or lower.

17. The separation method according to claim 15, wherein m is 1 or more and 3 or less.

18. 16. The separation method of claim 15, wherein the fluorocarbon A comprises R1234yf.

19. 16. The separation method according to claim 15, wherein the fluorocarbon B comprises one or more selected from R134a, R143, R143a, R32 and R125.

20. The separation method according to claim 15, wherein the metal-organic framework comprises one or more types of organic ligands, and the organic ligand comprises two or more groups capable of forming a coordinate bond to the metal ion in one molecule.

21. The separation method according to claim 15, wherein the metal-organic framework has open metal sites consisting of coordinatively unsaturated metal ions.

22. The separation method of claim 15 , wherein the adsorbent further comprises a resin.

23. 16. The separation method according to claim 15, wherein the adsorbent is in the form of a powder, granules, flakes or pellets.

24. 16. The method of claim 15, wherein the first mixture is an azeotrope or near-azeotrope of fluorocarbons.

25. The separation method according to any one of claims 15 to 24, further comprising contacting the separated third mixture with another adsorbent.

26. The separation method of any one of claims 15 to 24, further comprising purifying the separated third mixture.

27. After contacting the first mixture with the adsorbent, The separation method according to any one of claims 15 to 24, further comprising desorbing, from the adsorbent, the fluorocarbon A adsorbed to the adsorbent.

28. A fluorocarbon purification system that implements the separation method according to any one of claims 15 to 24.

29. A metal organic framework and a fluorocarbon A having one or more double bonds and n carbon atoms, The metal organic framework includes one or more selected from HKUST-1, MIL-100 (Fe), MIL-101 (Cr), MOF-74 (Cu), Mg 2 (dobpdc), and UTSA-16 (Zn); The n is 3 or more and 10 or less, The composite material, wherein the boiling point of the fluorocarbon A is −80° C. or higher and −20° C. or lower.

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