WO2015012263A1 - Procédé d'adsorption d'hydrocarbures saturés ne comportant pas plus de trois atomes de carbone, procédé de séparation et dispositif de séparation - Google Patents

Procédé d'adsorption d'hydrocarbures saturés ne comportant pas plus de trois atomes de carbone, procédé de séparation et dispositif de séparation Download PDF

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WO2015012263A1
WO2015012263A1 PCT/JP2014/069315 JP2014069315W WO2015012263A1 WO 2015012263 A1 WO2015012263 A1 WO 2015012263A1 JP 2014069315 W JP2014069315 W JP 2014069315W WO 2015012263 A1 WO2015012263 A1 WO 2015012263A1
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metal complex
saturated hydrocarbon
ligand
group
adsorption
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PCT/JP2014/069315
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Japanese (ja)
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真一郎 野呂
進 北川
東村　秀之
勝紀 望月
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住友化学株式会社
国立大学法人北海道大学
国立大学法人京都大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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]
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3491—Regenerating or reactivating by pressure treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/18—Bridged systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1122—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons

Definitions

  • the present invention relates to a selective adsorption method for saturated hydrocarbons having 3 or less carbon atoms, a separation method using the same, and a separation apparatus for performing the separation method.
  • a method using activated carbon or zeolite generally known as an adsorbent is known, but saturated hydrocarbons, particularly saturated hydrocarbons having 3 or less carbon atoms are used. It is difficult to adsorb highly selectively, and no practical adsorption method capable of adsorbing such saturated hydrocarbons with high selectivity has been provided.
  • Non-patent Document 1 Japanese Patent Application Laidiol et al. , J. Am. Chem. Soc. 2010, 132, p. In 17704-17706 (Non-patent Document 1), it has been found that, in a specific porous metal complex, the affinity for a saturated hydrocarbon is higher than the affinity for an unsaturated hydrocarbon.
  • a practically excessively low pressure for example, less than 1 kPa at 25 ° C.
  • 8832-8840 (Non-patent Document 2) describes a relatively high pressure as a pressure for recovering propane, there is a problem that in this case, it is necessary to excessively raise the temperature.
  • the present invention has been made in view of the above-described problems of the prior art, and selectively selects saturated hydrocarbons in a mixture even if they are hydrocarbons having 3 or less carbon atoms such as propylene and propane. Gas adsorbed in a temperature and pressure range (for example, 1 kPa or more at 25 ° C.) that can be used without requiring an excessive temperature rise or an excessively low pressure in practice. It is an object of the present invention to provide a saturated hydrocarbon adsorption method, a separation method using the same, and a separation apparatus for performing the separation method.
  • the saturated hydrocarbon adsorption method of the present invention has the following formula (1):
  • P is a saturated hydrocarbon group which may have a substituent other than R a ;
  • R a is a functional group having a coordination property to a metal ion;
  • m is an integer of 2 or more, a plurality of R a may be the same or different from each other.
  • first ligand represented by the formula (hereinafter also referred to as “first ligand”) and a metal ion, a saturated hydrocarbon having 3 or less carbon atoms, an unsaturated hydrocarbon
  • P of the first ligand may be substituted with a saturated hydrocarbon group having 1 to 8 carbon atoms, and has 3 to 12 carbon atoms having a cyclic structure.
  • the saturated hydrocarbon group is preferable.
  • R a of the first ligand is “—CO 2 ⁇ ”, “—CS 2 ⁇ ”, “—C ( ⁇ O) S ⁇ ”.
  • the metal ions are preferably ions of at least one metal selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper, and zinc. .
  • the metal complex further includes a second ligand that satisfies the condition that it is a “heterocyclic compound containing 2 to 4 heteroatoms”. It is preferable to include. Furthermore, the second ligand is more preferably a heterocyclic compound containing 2 or more and 4 or less heteroatoms and no double bond.
  • the metal complex is represented by the following formula (2):
  • Q is an R a substituent other than may have an unsaturated hydrocarbon group; R a and m R a and each of the first in the ligand independently It is synonymous with m.
  • the 3rd ligand represented by these is further included.
  • the molar ratio represented by [first ligand]: [third ligand] is 100: 0 to 5:95. It is preferable that it is the range of these.
  • the metal complex is represented by the following formula (3):
  • a first ligand A represented by: A second ligand B which is a heterocyclic compound containing 2 to 4 heteroatoms and no double bond; Following formula (4):
  • Q 1 is a halogen atom or an unsaturated hydrocarbon group having 12 or less carbon atoms which may be substituted by a saturated hydrocarbon group having 1 to 8 carbon atoms; m 1 is 1 to 2; Is an integer.
  • the hydrocarbon separation method of the present invention is a hydrocarbon separation method including a step of separating the saturated hydrocarbon and the unsaturated hydrocarbon using the saturated hydrocarbon adsorption method of the present invention.
  • a desorption step of changing the pressure to a second predetermined pressure and desorbing the saturated hydrocarbon adsorbed on the metal complex is included.
  • the separation apparatus of the present invention comprises a separation means comprising a metal complex containing a ligand represented by the above formula (1) and a metal ion, An introduction means for introducing a mixture containing a saturated hydrocarbon having 3 or less carbon atoms and an unsaturated hydrocarbon into the separation means,
  • the hydrocarbon separation apparatus separates the saturated hydrocarbon from the unsaturated hydrocarbon by selectively adsorbing the saturated hydrocarbon to the metal complex by bringing the mixture into contact with the metal complex.
  • “selectively adsorbing saturated hydrocarbons to a metal complex” means saturation when saturated hydrocarbons and unsaturated hydrocarbons are adsorbed to metal complexes under the same temperature and pressure conditions. It means that the amount of adsorption of hydrocarbons is greater than the amount of adsorption of unsaturated hydrocarbons.
  • the amount of adsorption can be measured by a volumetric method using, for example, an automatic specific surface area / pore distribution measuring apparatus (BELSORP-miniII manufactured by Nippon Bell Co., Ltd.), and the temperature (adsorption temperature) condition at that time is as follows: It is preferably 173 to 373 K, and the pressure (adsorption pressure) condition is preferably 3 kPa to 3 MPa.
  • the unsaturated hydrocarbon at that time preferably has the same carbon number as that of the saturated hydrocarbon.
  • saturated hydrocarbons in a mixture can be selectively adsorbed even if they are hydrocarbons having 3 or less carbon atoms such as propylene and propane, and practically.
  • Saturated hydrocarbon adsorption method capable of recovering gas (hydrocarbon) adsorbed in a temperature and pressure range (for example, 1 kPa or more at 25 ° C.) that can be used without requiring excessive temperature rise or excessive pressure reduction It is possible to provide a separation method using the same, and a separation apparatus for performing the separation method.
  • FIG. 4 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 1.
  • 5 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 2.
  • 6 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 3.
  • 6 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 4.
  • 6 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 5.
  • 10 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 6.
  • 10 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 7.
  • 10 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 8.
  • 10 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 9.
  • 6 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Comparative Synthesis Example 1. It is a graph which shows the adsorption / desorption isotherm of propane and propylene measured in Example 1 using the metal complex obtained in Synthesis Example 1.
  • FIG. 6 is a graph showing adsorption / desorption isotherms of propane and propylene measured in Example 7 using the metal complex obtained in Synthesis Example 7.
  • FIG. It is a graph which shows the adsorption / desorption isotherm of propane and propylene measured in Example 8 using the metal complex obtained in Synthesis Example 8.
  • 10 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 10.
  • Example 10 is a graph showing a powder X-ray diffraction pattern of the metal complex obtained in Synthesis Example 11. It is a graph which shows the adsorption-and-desorption isotherm of the propane and propylene which were measured in Example 10 using the metal complex obtained in the synthesis example 10. It is a graph which shows the adsorption / desorption isotherm of propane and propylene measured in Example 11 using the metal complex obtained in Synthesis Example 11. It is a graph which shows the breakthrough curve of the mixed gas of the propane, propylene, and nitrogen which were measured in Example 12 using the metal complex obtained by the synthesis example 3.
  • a saturated hydrocarbon having 3 or less carbon atoms and a non-carbon having 3 or less carbon atoms are added to the metal complex containing the ligand represented by the formula (1) and a metal ion.
  • the saturated hydrocarbon is brought into contact with a mixture containing a saturated hydrocarbon (in this specification, it may be referred to as “a mixture containing a saturated hydrocarbon having 3 or less carbon atoms and an unsaturated hydrocarbon”).
  • a method for adsorbing saturated hydrocarbons that is selectively adsorbed on the metal complex is selectively adsorbed on the metal complex.
  • a plurality of things “may be the same as or different from each other” means that a plurality of things “may be the same or all may be different, Only may be the same ".
  • P in the first ligand is a group formed by removing m hydrogen atoms from a saturated hydrocarbon compound that may have a substituent other than Ra , and is an acyclic hydrocarbon group. Alternatively, it may be a cyclic hydrocarbon group.
  • P in such a first ligand is preferably a saturated hydrocarbon group having 12 or less carbon atoms which may be substituted with a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms. Further, it is more preferably a saturated hydrocarbon group having 3 to 12 carbon atoms having a cyclic structure, which may be substituted by a saturated hydrocarbon group having 1 to 8 carbon atoms, and a saturated hydrocarbon having 1 to 3 carbon atoms. It is more preferably a saturated hydrocarbon group having 5 to 10 carbon atoms having a cyclic structure which may be substituted with a group.
  • saturated hydrocarbon compound in which m hydrogen atoms are removed to form P include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, cyclopropane, cyclobutane, and cyclopentane.
  • the metal complex obtained can be expected to have a relatively higher affinity for saturated hydrocarbons
  • heptane, octane, cyclopentane, cyclohexane, cycloheptane, decalin, [2.2.2] -bicyclo Octane and adamantane are preferred, cyclohexane, decalin, [2.2.2] -bicyclooctane and adamantane are more preferred, and cyclohexane and adamantane are even more preferred.
  • R a of the first ligand may be a functional group having a coordination property to a metal ion, and includes “—CO 2 ⁇ ”, “—CS 2 ⁇ ”, “—C ( ⁇ O) S ⁇ . , “—C ( ⁇ O) N (R A ) ⁇ ”, “—SO 3 ⁇ ”, “—PO 4 (R A ) ⁇ ”, “—C ⁇ N”, “—S ⁇ ”, “— Examples thereof include a group represented by any one selected from the group consisting of “O ⁇ ”, “—N (R A ) ⁇ ”, “pyridyl group” and “imidazole group”.
  • M of the first ligand may be an integer of 1 to 4, but a low-dimensional metal complex (the description of the low-dimensional metal complex will be described later) can be easily obtained. Since expression can be expected, it is preferably an integer of 1 to 2, more preferably 1. When m is an integer of 2 or more, a plurality of Ra may be the same or different from each other.
  • P of the first ligand may have a substituent other than Ra , and when the number of substituents is 2 or more, these substituents are the same as each other. May be different.
  • substituent other than R a include a halogen atom and a saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a halogen atom.
  • Such a saturated hydrocarbon group is preferably a saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and more preferably one having 1 to 3 carbon atoms which may be substituted with a halogen atom.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom and a chlorine atom are preferable, and a fluorine atom is more preferable.
  • a substituent other than the R a is, which may be linear or branched or cyclic, cyclic In some cases, it may be monocyclic or polycyclic.
  • the saturated hydrocarbon group having 1 to 6 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group.
  • Isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group are preferred, methyl group, ethyl group, n-propyl group, isopropyl group Group, cyclopentyl group, and cyclohexyl group are more preferable, methyl group, ethyl group, n-propyl group, and isopropyl group are more preferable, and methyl group is particularly preferable.
  • one of the first ligands may be contained alone or in combination of two or more, and in the case of containing in combination of two or more, the first P of one ligand is a saturated hydrocarbon group having 3 to 10 carbon atoms having a cyclic structure (PI) and a saturated hydrocarbon group having a cyclic structure having more carbon atoms than PI and having 12 or less carbon atoms ( More preferred is a combination with PII).
  • the molar ratio represented by [PI]: [PII] is more preferably 25:75 to 99: 1, particularly preferably 50:50 to 98: 2, and 75:25 to 95: 5 is particularly preferred.
  • the metal ion contained in the metal complex may be an ion of an arbitrary metal element, but is preferably an ion of a metal element selected from Groups 2 to 13 of the periodic table.
  • metal complexes As such metal ions, the synthesis of metal complexes is relatively easy, so magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, strontium, yttrium. More preferred is an ion of at least one metal selected from the group consisting of niobium, molybdenum, ruthenium, rhodium, cadmium, barium, lanthanum, tantalum and tungsten. As said metal complex, 1 type in the said metal ion may be included independently, or 2 or more types may be included in combination.
  • metal ions since the metal salt as a raw material is relatively inexpensive, the group consisting of magnesium, aluminum, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc At least one metal ion selected from is more preferable, and since the synthesis of the metal complex is relatively easy, at least one selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper and zinc Metal ions are particularly preferred. Furthermore, as such a metal ion, since the synthesis of a metal complex is very easy, a copper or zinc ion is particularly preferred, and a copper ion is particularly preferred.
  • the metal ions are usually 1 to 7 valent cations.
  • the cation is preferably divalent to hexavalent, more preferably divalent to tetravalent, and even more preferably divalent to trivalent since it is necessary to form a metal complex with a plurality of ligands. And particularly preferably divalent.
  • the metal complex used in the present invention includes “a heteroatom having 2 to 4 atoms (for example, at least one atom selected from the group consisting of N, O and S). It is preferable to further include a second ligand that is a heterocyclic compound containing, and it is preferable that the second ligand does not include a double bond.
  • the second ligand may be a monocyclic group, a condensed ring group, or a group in which monocyclic groups are linked.
  • triethylenediamine that is, 1, 4-diazabicyclo [2.2.2] octane
  • piperazine 2,5-dimethylpiperazine, 3,3′-bipiperidine, 4,4′-bipiperidine, 1,3-di- (4-piperidyl) propane, hexa
  • Examples include methylenetetramine, 1,4-dioxane, and 1,4-dithiane. One of these may be used alone, or two or more may be used in combination.
  • Such a second ligand is at least one compound selected from the group consisting of triethylenediamine, piperazine, 4,4′-bipiperidine and hexamethylenetetramine because the stability of the metal complex is further increased. It is preferable that triethylenediamine, hexamethylenetetramine or piperazine is more preferable, and triethylenediamine is more preferable.
  • the metal complex used in the present invention may further include a third ligand represented by the formula (2) in addition to the first ligand.
  • the absolute difference between the number of carbon atoms in the P structure of the first ligand and the number of carbon atoms in the Q structure of the third ligand is preferably an integer of 0 to 6, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 2.
  • Q of the third ligand is a group formed by removing m hydrogen atoms from an unsaturated hydrocarbon compound which may have a substituent other than Ra , and is an acyclic hydrocarbon group. Or a cyclic hydrocarbon group.
  • Q of such a third ligand is preferably an unsaturated hydrocarbon group having 12 or less carbon atoms, which may be substituted by a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms. .
  • a C 3-12 unsaturated hydrocarbon group having a cyclic structure which may be substituted by a halogen atom or a C 1-8 saturated hydrocarbon group, and a fluorine atom or a carbon number
  • an unsaturated hydrocarbon group having 5 to 10 carbon atoms having a cyclic structure which may be substituted by 1 to 3 saturated hydrocarbon groups.
  • the unsaturated hydrocarbon compound in which m hydrogen atoms are removed to form Q include butene, pentene, hexene, heptene, octene, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and cyclopentadiene.
  • 1,2,3,4-tetrahydronaphthalene benzene, naphthalene, anthracene, etc., preferably cyclopentene, cyclohexene, cycloheptene, cyclopentadiene, benzene, naphthalene, more preferably cyclohexene, benzene, naphthalene. More preferably, it is benzene.
  • Q of the third ligand may have a substituent other than Ra , and preferred examples thereof include a halogen atom (more preferably a fluorine atom) or P of the first ligand. Are the same as those of the preferred examples of the substituent other than Ra .
  • 1 type in the said 3rd ligand may be included independently, or 2 or more types may be included in combination.
  • the selectivity of saturated hydrocarbons during hydrocarbon adsorption is further improved, or a more suitable pressure is adsorbed. Since it can be applied to gas recovery, it is preferable that the following relationships are satisfied.
  • the molar ratio represented by [metal ion]: [first ligand] is 1.0: 0.
  • the range is preferably 5 to 1.0: 4.0, more preferably 1.0: 0.8 to 1.0: 3.0, and 1.0: 1.0 to 1 More preferably, it is in the range of 0.0: 2.0.
  • the said metal complex further contains the said 3rd ligand in addition to the said 1st ligand, about the said metal ion, the said 1st ligand, and the said 3rd ligand, [
  • the molar ratio represented by [metal ion]: [first ligand + third ligand] is preferably in the range of 1.0: 0.5 to 1.0: 4.0, The range is more preferably 1.0: 0.8 to 1.0: 3.0, and still more preferably 1.0: 1.0 to 1.0: 2.0.
  • the ratio of the third ligand in the metal complex is such that the molar ratio represented by [first ligand]: [third ligand] is in the range of 100: 0 to 5:95. Preferably, it is in the range of 100: 0 to 20:80, more preferably in the range of 100: 0 to 50:50. Further, considering that selective adsorption characteristics of saturated hydrocarbons are further increased, the molar ratio represented by [first ligand]: [third ligand] is 85:15 to 50:50. Is particularly preferably in the range of 80:20 to 50:50, and particularly preferably in the range of 80:20 to 60:40.
  • the metal complex further contains the second ligand in addition to the first ligand, the metal ion and the second ligand contained in the metal complex ]:
  • the molar ratio represented by [second ligand] is preferably in the range of 1.0: 0.2 to 1.0: 3.0, and 1.0: 0.3 to 1 More preferably, it is in the range of 0.0: 2.0, and more preferably in the range of 1.0: 0.5 to 1.0: 1.0.
  • the selectivity of saturated hydrocarbons at the time of hydrocarbon adsorption can be further improved, or more suitable pressure can be applied to recovering the adsorbed gas, so that the metal complex has ionic bonds and coordination.
  • It is preferably a metal complex that forms an integrated structure having one-dimensional (linear) or two-dimensional (planar) dimensionality by being connected by a bond, and forms a one-dimensional integrated structure. More preferred is a metal complex.
  • a one-dimensional integrated structure is such that the metal complex has a divalent metal ion, the first ligand having one functional group coordinated to the metal ion, and a heteroatom.
  • such a one-dimensional integrated structure has a structure in which the metal complex includes a divalent metal ion, the first ligand having one functional group coordinated to the metal ion, and a heterogeneous structure.
  • auxiliary ligands other than said 1st ligand, said 2nd ligand, and said 3rd ligand.
  • auxiliary ligands include triethylamine, water, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, acetone, Examples include pyridine, tetrahydrofuran, diethyl ether, dimethoxyethane, and methyl ethyl ether, and water, N, N-dimethylformamide, and N, N-diethylformamide are preferable.
  • These auxiliary ligands may be one kind or two or more kinds.
  • the metal complex used in the present invention preferably has a regular structure and a flexible structure because the separation efficiency between unsaturated hydrocarbons and saturated hydrocarbons can be further increased.
  • the regular structure here means that at least one peak derived from the unit cell is observed at 15 ° (2 ⁇ ) or less, preferably 12 ° or less, more preferably 10 ° or less by measurement of powder X-ray diffraction.
  • the ordered structure is characterized, and the peak is preferably 3 ° (2 ⁇ ) or more, more preferably 4 ° or more.
  • the flexible structure here is characterized in that the structure is changed by an external stimulus (for example, adsorption of guest molecules).
  • the powder X-ray diffraction pattern of the metal complex having a flexible structure changes with the adsorption of small molecules.
  • the metal complex having a flexible structure changes its structure again when the adsorbed small molecules are desorbed, and usually recovers the structure before adsorbing the small molecules.
  • the metal complex includes a first ligand A represented by the formula (3), A second ligand B which is a heterocyclic compound containing 2 to 4 heteroatoms and no double bond; A third ligand C represented by the formula (4); Ions of at least one metal selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper and zinc; It is preferable that it is a metal complex containing.
  • P 1 of the ligand A is a saturated hydrocarbon having 12 or less carbon atoms which may be substituted with a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms in the P of the first ligand.
  • a group formed by removing m hydrogen atoms from a compound, and a preferable example is as described in the first ligand.
  • m 1 of the ligand A is an integer of 1 to 2 out of m of the first ligand, and a low-dimensional compound is easily obtained and better selective adsorption characteristics are exhibited. , Preferably 1.
  • the metal ion contained in the metal complex is an ion of at least one metal selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper and zinc among the above metal ions.
  • a metal ion since the synthesis of a metal complex is very easy, a copper or zinc ion is particularly preferred, and a copper ion is particularly preferred.
  • the preferable example of the said ligand B is synonymous with the preferable example of said 2nd ligand.
  • Q 1 of the ligand C is an unsaturated carbon atom having 12 or less carbon atoms which may be substituted with a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms in the Q of the third ligand.
  • a group obtained by removing m hydrogen atoms from a hydrogen compound, and a preferable example is as described in the third ligand.
  • the method for producing the metal complex used in the present invention is not particularly limited, but the ligand or a precursor thereof (the precursor of the first ligand and the second ligand as necessary).
  • a ligand and / or a precursor of a third ligand) are reacted in a solvent with a metal salt comprising the metal ion (and, if necessary, a counter ion and crystal water) or a hydrate thereof. It is preferable to manufacture by.
  • solvents such as water, methanol, ethanol, 2-propanol, tetrahydrofuran, acetone, acetonitrile, N, N-dimethylacetamide, N, N-diethylacetamide, chloroform and the like can be used. May further add another auxiliary ligand.
  • the functional groups in the precursor of the first ligand and the precursor of the third ligand include “—CO 2 A”, “—CS 2 A”, “—C ( ⁇ O)”. “SA”, “—C ( ⁇ O) N (R A ) A”, “—SO 2 A”, “—PO 4 (R A ) A”, “—C ⁇ N”, “—SA”, “— Examples are groups represented by any one selected from the group consisting of “OA” and “—N (R A ) A”.
  • A is a hydrogen atom, an alkali metal atom or an ammonium ion which may be substituted with an alkyl group, preferably a hydrogen atom.
  • the molar ratio of the precursor of the first ligand, the second ligand, the precursor of the third ligand, and the metal salt to be reacted is the same as that of each metal salt. It is necessary to adjust according to the coordination ability of the ligand.
  • the preferred ratio of the precursor of the first ligand and the precursor of the third ligand to be reacted is the ratio of the first ligand contained in the metal complex to be produced to the above-mentioned It is also necessary to adjust based on the ratio with the third ligand. Further, the yield of the ligand or the precursor thereof to be reacted may be improved by making the ligand or the precursor thereof in excess of the stoichiometric ratio compared to the metal salt. In some cases, the amount of ligand used excessively can be reduced by carrying out the reaction at a high concentration.
  • the metal salt is preferably fluoride, chloride, bromide, nitrate, sulfate, perchlorate, acetate, tetrafluoroborate, tetraphenylborate, hexafluorophosphate, hexafluorosilicic acid. Salts, hydrates thereof, or combinations thereof. Nitrate, sulfate, perchlorate, acetate, tetrafluoroborate are preferred because they are highly available and the coordinating power of the counter anion is preferably low enough not to interfere with the intended reaction. , Hexafluorophosphates or hydrates thereof, more preferably nitrates, sulfates, acetates or hydrates thereof.
  • the reaction temperature at the time of reacting the ligand or the precursor thereof with the metal salt is preferably 0 ° C. or higher and 200 ° C. or lower, more preferably 10 ° C. or higher and 150 ° C. or lower, further preferably 10 ° C. or higher and 100 ° C. or lower, 20 degreeC or more and 60 degrees C or less are especially preferable.
  • the reaction is preferably carried out under a pressure of 0.01 to 10 MPa, more preferably carried out under a pressure of 0.05 to 1 MPa, further preferably carried out under a pressure of 0.08 to 0.12 MPa. Usually, it is performed under normal pressure.
  • the reaction time is usually 1 minute to 1 week, preferably 5 minutes to 120 hours.
  • reaction vessel used for such a reaction an open vessel or a closed vessel such as an autoclave can be used.
  • the reaction vessel can be heated by using a liquid or gaseous heat medium, or by irradiating microwaves or ultrasonic waves.
  • the generated metal complex is precipitated in the reaction solution as a precipitate.
  • the precipitated metal complex can be washed with the same type of solvent used for the reaction or a solvent that is more volatile than the solvent used for the reaction. preferable.
  • the obtained metal complex is porous, since the solvent may be adsorbed in the pores, it is preferable to dry the metal complex in order to remove these. As such drying, vacuum drying under room temperature or heating conditions is preferable.
  • the precursor of the first ligand (and the precursor of the third ligand as necessary) and the metal salt It is also possible to adopt a stepwise synthesis method in which an intermediate is synthesized in advance, and then the second ligand is added to the intermediate to obtain the metal complex.
  • the saturated hydrocarbon is selectively brought into contact with the metal complex by contacting the metal complex with a mixture containing a saturated hydrocarbon having 3 or less carbon atoms and an unsaturated hydrocarbon. Adsorbed.
  • metal complexes may be one kind or may contain two or more kinds.
  • the saturated hydrocarbon is ethane, propane, or cyclopropane, and ethane or propane is preferable.
  • unsaturated hydrocarbons include ethylene, propylene, cyclopropene, and acetylene, with ethylene and propylene being preferred.
  • the saturated hydrocarbon and saturated hydrocarbon to be brought into contact with the metal complex are a mixture containing a saturated hydrocarbon having 3 or less carbon atoms and an unsaturated hydrocarbon, and the mixture is preferably a gas.
  • carbon number of saturated hydrocarbon and unsaturated hydrocarbon is the same, or there are many carbon numbers of saturated hydrocarbon. Specific examples include a mixture of ethane and ethylene, a mixture of propane and ethylene, and a mixture of propane and propylene, more preferably a mixture of propane and propylene.
  • the hydrocarbon separation method of the present invention is a hydrocarbon separation method including a step of separating the saturated hydrocarbon and the unsaturated hydrocarbon using the saturated hydrocarbon adsorption method of the present invention.
  • the saturated hydrocarbon or unsaturated hydrocarbon obtained by separation by the separation method of the present invention may have a composition ratio different from that of the mixture before the separation, but either one of the separated obtained products is 80 mol% or more. It is preferably 90 mol% or more, more preferably 95% or more, and particularly preferably 98% or more.
  • the metal complex can be used as it is or in a powder form by appropriate pulverization, but it may be molded by an appropriate molding means and used as a molded body.
  • the type of molding agent and the type of the molding agent are selected so that the hydrocarbon gas adsorption characteristics and the hydrocarbon gas desorption characteristics after adsorption are not significantly impaired. It is preferable to determine the amount used.
  • An example of such a molding means is press molding.
  • the shape of the molded body when used as an adsorbent is desirably a shape that can maintain the strength required for the adsorbent.
  • rate is improved, it is preferable that the surface area of a molded article is large.
  • specific processes for separating the unsaturated hydrocarbon and the saturated hydrocarbon using the metal complex described above include, for example, a pressure swing adsorption method (pressure swing adsorption method) and a temperature swing adsorption.
  • Method temperature fluctuation adsorption method: Temperature Swing Adsorption
  • permeation separation method membrane separation
  • the metal complex is brought into contact with a mixture of the unsaturated hydrocarbon and the saturated hydrocarbon under a first predetermined pressure (adsorption pressure), and the saturated hydrocarbon is selected as the metal complex.
  • adsorption pressure a first predetermined pressure
  • the saturated hydrocarbon is selected as the metal complex.
  • the pressure in the space where the metal complex is arranged (for example, in the adsorption tank) is raised or reduced to a desired adsorption pressure in advance, and then the mixture is subjected to the adsorption pressure under the adsorption pressure.
  • saturated hydrocarbons are adsorbed and concentrated on the metal complex with high selectivity, and the hydrocarbon depletion and unsaturated hydrocarbons are discharged from the space.
  • the pressure is changed to a second predetermined pressure (desorption pressure) to desorb hydrocarbons adsorbed on the metal complex. More preferably, the method further includes a step.
  • a desorption process regeneration process
  • the pressure in the space where the metal complex that selectively adsorbs one of the hydrocarbons is reduced to a desired desorption pressure, and is adsorbed by the metal complex.
  • the saturated hydrocarbon concentrate is discharged from the space by desorbing from the metal complex.
  • the unsaturated hydrocarbons in the space may be replaced with saturated hydrocarbons by feeding a small amount of saturated hydrocarbons before changing the pressure to the second predetermined pressure (desorption pressure).
  • the purity of the obtained saturated hydrocarbon or unsaturated hydrocarbon is low, and a device for obtaining the higher purity saturated hydrocarbon or unsaturated hydrocarbon is necessary.
  • the adsorption step and the desorption step are repeated twice or more.
  • the adsorption conditions in the pressure swing adsorption method are determined depending on the object to be separated and the metal complex used, and the adsorption temperature is preferably 173 to 373K, more preferably 223 to 353K. More preferably, it is 253 to 353K, and more preferably 273 to 333K.
  • the adsorption pressure varies depending on the working temperature and the metal complex used, but is preferably 3 kPa to 3 MPa, more preferably 10 kPa to 2 MPa. More preferably, it is 30 kPa to 2 MPa, and particularly preferably 100 kPa to 2 MPa.
  • the adsorption pressure is a pressure at which the difference between the adsorption amount of one hydrocarbon and the adsorption amount of the other hydrocarbon is increased, preferably 2 times or more, more preferably 5 times or more, and still more preferably. A pressure of 10 times or more is employed.
  • the desorption pressure a pressure at which the saturated hydrocarbon adsorption amount is 50% or less of the saturated adsorption amount is employed, preferably 20% or less, more preferably 10% or less, and even more preferably 5%. The following pressure is employed.
  • the desorption conditions of the adsorbed components in the pressure swing adsorption method are determined by the separation object and the metal complex used.
  • the desorption pressure varies depending on the object to be separated, the operating temperature, and the metal complex to be used. However, if the gas recovery pressure is too low, a recompression load is required for storage or use of the gas. It is preferable to recover by pressure.
  • Such pressure is preferably 2 kPa or more, and more preferably 5 kPa or more. More preferably, it is 10 kPa to 2 MPa, and particularly preferably 20 kPa to 1.5 MPa. According to the method for adsorbing saturated hydrocarbons of the present invention, the gas adsorbed in the pressure region that can be used without requiring excessive pressure reduction in practice can be recovered.
  • the desorption temperature is preferably 223 to 373K. Although it is not always necessary to positively increase the temperature in the desorption step, it is preferable to compensate for the latent heat necessary for desorption, and it may be preferable to perform temperature control and heat retention.
  • Such a separation apparatus includes separation means including the metal complex described above, and introduction means for introducing a mixture containing a saturated hydrocarbon having 3 or less carbon atoms and an unsaturated hydrocarbon into the separation means, An apparatus for separating the saturated hydrocarbon and the unsaturated hydrocarbon by selectively adsorbing the saturated hydrocarbon to the metal complex by bringing the mixture into contact with the metal complex.
  • the hydrocarbon separation apparatus preferably further comprises pressure control means for controlling the pressure of the space in which the metal complex is disposed in the separation means, and the pressure control means provides a first predetermined pressure. It is preferable that the adsorbing step described above can be performed by bringing the mixture into contact with the metal complex and selectively adsorbing one of the hydrocarbons to the metal complex.
  • the pressure is changed to the second predetermined pressure by the pressure control means, and the saturated hydrocarbon adsorbed on the metal complex is removed. It is preferable that the above-described desorption step can be performed by separating them.
  • FIG. 1 shows a preferred embodiment of this hydrocarbon separation apparatus.
  • an adsorption tank (separation means) 1 filled with the above-described metal complex is disposed, and an inlet pipe P1 having a valve V1 at one end thereof is disposed.
  • the compressor 2 (introducing means) is connected, and the compressor 2 is connected to a feed gas P2 having a valve V2 (the mixture) and a purge gas introducing pipe P3 having a valve V3.
  • a decompressor 3 pressure control means
  • a product gas having a valve V5 is connected to the decompressor 3.
  • Hydrogen) discharge pipe P5 and purge gas discharge pipe P6 having valve V6 are connected.
  • a control means 4 for example, PLC
  • the compressor 2 the decompressor 3
  • the valves V1 to V6 so that their operations can be controlled.
  • the separation apparatus of the present invention further includes a temperature control means capable of controlling the temperature.
  • the following control is performed. That is, first, purge gas is introduced into the adsorption tank 1 by the compressor 2, and then the pressure in the adsorption tank 1 is reduced by the decompressor 3 so as to become the first predetermined pressure (adsorption pressure). Next, the raw material gas is introduced into the adsorption tank 1 by the compressor 2 under the pressure, and the saturated hydrocarbon is selectively adsorbed and concentrated on the metal complex, and the hydrocarbon depletion and unsaturated hydrocarbon are concentrated. Is discharged as the first product gas.
  • the pressure in the adsorption tank 1 is reduced to the second predetermined pressure (desorption pressure) by the decompressor 3 so that the saturated hydrocarbon concentrate adsorbed on the metal complex is desorbed from the metal complex. Separated and discharged as a second product gas.
  • the present invention is not limited to the above-described embodiment.
  • one of the compressor and the decompressor serves as both the introduction unit and the pressure control unit, Either one may be sufficient.
  • adsorption tank filled with the metal complex a plurality of adsorption tanks (adsorption towers) may be connected in parallel or in series.
  • Measurement of adsorption / desorption isotherm Measurement was performed by a volumetric method using an automatic specific surface area / pore distribution measuring device. At this time, the sample was dried at 373 K and 5 Pa for 16 hours prior to measurement to remove adsorbed water and the like. Details of the measurement conditions are shown below. ⁇ Measurement conditions> Apparatus: BELSORP-miniII manufactured by Nippon Bell Co., Ltd. Pressure program: 5 kPa or less ⁇ 120 kPa ⁇ 10 kPa or less Equilibrium waiting time: 300 seconds.
  • [Cu 2 (chc) 4 ], [Cu 2 (bza) 4 ], [Cu 2 (adc) 4 (H 2 O) 2 ], [Cu 2 (Fbza) 4 ] and the like used in the following synthesis examples [Cu 2 (F5bza) 4 ] is the following document: J. et al. Chem. Soc. 1965, p. 6466-6477 According to the method described in 1. Structural formulas of [Cu 2 (chc) 4 ], [Cu 2 (bza) 4 ], [Cu 2 (Fbza) 4 ], and [Cu 2 (F5bza) 4 ] are shown below.
  • Solution B was added to Solution A, and the mixture was stirred at 298 K for 10 minutes, 0.056 g (0.5 mmol) of 1,4-diazabicyclo [2.2.2] octane was added, and the mixture was stirred at 298 K for 24 hours.
  • the deposited metal complex was collected by suction filtration, washed with chloroform, and further dried at 298 K and 5 Pa for 2 hours to obtain 0.3129 g (yield 83%) of the desired metal complex.
  • the powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From the results shown in FIG. 3, it was confirmed that the obtained metal complex had an ordered structure.
  • Solution B was added to Solution A, and the mixture was stirred at 298 K for 10 minutes, 0.056 g (0.5 mmol) of 1,4-diazabicyclo [2.2.2] octane was added, and the mixture was stirred at 298 K for 24 hours.
  • the precipitated metal complex was collected by suction filtration, washed with chloroform, and further dried at 298 K and 5 Pa for 2 hours to obtain 0.2913 g (yield 78%) of the target metal complex.
  • the powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From the results shown in FIG. 4, it was confirmed that the obtained metal complex had an ordered structure.
  • FIG. 5 shows a powder X-ray diffraction pattern of the obtained metal complex. From the results shown in FIG. 5, it was confirmed that the obtained metal complex had an ordered structure.
  • Solution B was added to Solution A, and the mixture was stirred at 298 K for 10 minutes, 0.056 g (0.5 mmol) of 1,4-diazabicyclo [2.2.2] octane was added, and the mixture was stirred at 298 K for 24 hours.
  • the deposited metal complex was collected by suction filtration, washed with chloroform, and further dried at 298 K and 5 Pa for 2 hours to obtain 0.1933 g (yield 53%) of the desired metal complex.
  • the powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From the results shown in FIG. 6, it was confirmed that the obtained metal complex had an ordered structure.
  • FIG. 7 shows a powder X-ray diffraction pattern of the obtained metal complex. From the results shown in FIG. 7, it was confirmed that the obtained metal complex had an ordered structure.
  • Solution B was added to Solution A, and the mixture was stirred at 298 K for 10 minutes, 0.046 g (0.413 mmol) of 1,4-diazabicyclo [2.2.2] octane was added, and the mixture was stirred at 298 K for 24 hours.
  • the precipitated metal complex was collected by suction filtration, washed with chloroform, and further dried at 298 K and 5 Pa for 2 hours to obtain 0.2259 g (yield 70%) of the target metal complex.
  • the powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From the results shown in FIG. 8, it was confirmed that the obtained metal complex had an ordered structure.
  • Solution B was added to Solution A, and the mixture was stirred at 298 K for 10 minutes, 0.045 g (0.4 mmol) of 1,4-diazabicyclo [2.2.2] octane was added, and the mixture was stirred at 298 K for 24 hours.
  • the precipitated metal complex was collected by suction filtration, washed with chloroform, and further dried at 298 K and 5 Pa for 2 hours to obtain 0.2632 g (yield 85%) of the target metal complex.
  • the powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From the results shown in FIG. 9, it was confirmed that the obtained metal complex had an ordered structure.
  • Solution B was added to Solution A, and the mixture was stirred at 298 K for 10 minutes, 0.045 g (0.4 mmol) of 1,4-diazabicyclo [2.2.2] octane was added, and the mixture was stirred at 298 K for 24 hours.
  • the precipitated metal complex was collected by suction filtration, washed with chloroform, and further dried at 298 K and 5 Pa for 2 hours to obtain 0.2425 g (yield 79%) of the target metal complex.
  • the powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From the results shown in FIG. 10, it was confirmed that the obtained metal complex had an ordered structure.
  • Solution B was added to Solution A, and the mixture was stirred at 298 K for 10 minutes, and then 0.14 g (1.0 mmol) of 1,4-diazabicyclo [2.2.2] octane was added and stirred at 298 K for 24 hours.
  • the precipitated metal complex was collected by suction filtration, washed with a solution of chloroform: methanol 5: 1, and further dried at 298K and 5 Pa for 2 hours to obtain 0.6391 g (yield 84%) of the target metal complex. Obtained.
  • the powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From the results shown in FIG. 21, it was confirmed that the obtained metal complex had an ordered structure.
  • the precipitated metal complex was collected by suction filtration, washed with dehydrated acetone, and further dried at 298 K and 5 Pa for 2 hours to obtain 0.350 g (yield 86%) of the desired metal complex.
  • the powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. From the results shown in FIG. 22, it was confirmed that the obtained metal complex had an ordered structure.
  • Example 1 For the metal complex obtained in Synthesis Example 1, the adsorption and desorption isotherms of propane and propylene at 298 K were measured by the capacitance method. The results are shown in FIG. 12. In the range of 200 to 400 kPa, the propane adsorption amount exceeded the propylene adsorption amount, and the value of propane adsorption amount / propylene adsorption amount was about 3 times at the maximum. It was confirmed that there is sex. Moreover, it was confirmed that the adsorbed propane can be recovered at the pressure by reducing the pressure to 70 kPa.
  • Example 2 For the metal complex obtained in Synthesis Example 2, the adsorption and desorption isotherms of propane and propylene at 273 K were measured by the capacitance method. The results are shown in FIG. 13. In the range of 40 to 90 kPa, the propane adsorption amount exceeded the propylene adsorption amount, and the value of propane adsorption amount / propylene adsorption amount was about 4 times at the maximum. It was confirmed that there is sex. Moreover, it was confirmed that the adsorbed propane can be recovered at the pressure by reducing the pressure to 17 kPa.
  • Example 3 For the metal complex obtained in Synthesis Example 3, the adsorption and desorption isotherms of propane and propylene at 273 K and 303 K were measured by the capacitance method, respectively. The results are shown in FIGS. In the measurement at 273 K, the propane adsorption amount exceeded the propylene adsorption amount in the range of 20 to 30 kPa. In the measurement at 303K, the propane adsorption amount exceeded the propylene adsorption amount in the range of 80 to 120 kPa, and the value of propane adsorption amount / propylene adsorption amount was about 25 times at maximum. It was confirmed that there is. Moreover, it was confirmed that the adsorbed propane can be recovered at the pressure by reducing the pressure to 13 kPa.
  • Example 4 When the adsorption and desorption isotherms of propane and propylene at 298K were measured by the volumetric method for the metal complex obtained in Synthesis Example 4, the propane adsorption amount exceeded the propylene adsorption amount in a certain pressure range, and the adsorption property was selective. It is confirmed that there is. Moreover, it is confirmed that the adsorbed propane can be recovered at 1 kPa or more by reducing the pressure.
  • Example 5 When the adsorption and desorption isotherms of propane and propylene at 298K were measured by the volumetric method for the metal complex obtained in Synthesis Example 5, the propane adsorption amount exceeded the propylene adsorption amount in a certain pressure range, and the adsorption property was selective. It is confirmed that there is. Moreover, it is confirmed that the adsorbed propane can be recovered at 1 kPa or more by reducing the pressure.
  • Example 6 For the metal complex obtained in Synthesis Example 6, the adsorption and desorption isotherms of propane and propylene at 273 K were measured by the capacitance method. The results are shown in FIG. 16. In the range of 60 to 120 kPa, the propane adsorption amount exceeded the propylene adsorption amount, and the value of propane adsorption amount / propylene adsorption amount was about 4 times at the maximum. It was confirmed that there is sex. Moreover, it was confirmed that the adsorbed propane can be recovered at the pressure by reducing the pressure to 30 kPa.
  • Example 7 For the metal complex obtained in Synthesis Example 7, the adsorption and desorption isotherms of propane and propylene at 273 K were measured by the capacitance method. The results are shown in FIG. 17. In the range of 42 to 60 kPa, the propane adsorption amount exceeded the propylene adsorption amount, and the value of propane adsorption amount / propylene adsorption amount was about 20 times at the maximum. It was confirmed that there is sex. Moreover, it was confirmed that the adsorbed propane can be recovered at the pressure by reducing the pressure to 25 kPa.
  • Example 8 For the metal complex obtained in Synthesis Example 8, the adsorption and desorption isotherms of propane and propylene at 273 K were measured by the capacitance method. The results are shown in FIG. 18. In the range of 35 to 55 kPa, the propane adsorption amount exceeded the propylene adsorption amount, and the value of propane adsorption amount / propylene adsorption amount was about 23 times at the maximum. It was confirmed that there is sex. Moreover, it was confirmed that the adsorbed propane can be recovered at the pressure by reducing the pressure to 25 kPa.
  • Example 9 For the metal complex obtained in Synthesis Example 9, the adsorption and desorption isotherms of propane and propylene at 273 K were measured by the capacitance method. The results are shown in FIG. 19. In the range of 32 to 50 kPa, the propane adsorption amount exceeded the propylene adsorption amount, and the value of propane adsorption amount / propylene adsorption amount was about 35 times at the maximum. It was confirmed that there is sex. Moreover, it was confirmed that the adsorbed propane can be recovered at the pressure by reducing the pressure to 24 kPa.
  • Example 10 For the metal complex obtained in Synthesis Example 10, the adsorption and desorption isotherms of propane and propylene at 273 K were measured by the capacitance method. The results are shown in FIG. 23. In the range of 20 to 60 kPa, the propane adsorption amount exceeded the propylene adsorption amount, and the value of propane adsorption amount / propylene adsorption amount was about 28 times at the maximum. It was confirmed that there is sex. Moreover, it was confirmed that the adsorbed propane can be recovered at the pressure by reducing the pressure to 5 kPa.
  • Example 11 For the metal complex obtained in Synthesis Example 11, the adsorption and desorption isotherms of propane and propylene at 273 K were measured by the capacitance method. The results are shown in FIG. 24. In the range of 80 to 120 kPa, the propane adsorption amount exceeded the propylene adsorption amount, and the value of the propane adsorption amount / propylene adsorption amount was about 5 times at the maximum. It was confirmed that there is sex. Moreover, it was confirmed that the adsorbed propane can be recovered at the pressure by reducing the pressure to 20 kPa.
  • a gas chromatograph detector: TCD, carrier gas: Ar
  • a gas chromatograph detector: TCD, carrier gas: Ar
  • Comparative Example 1 For the metal complex obtained in Comparative Synthesis Example 1, the adsorption and desorption isotherms of propane and propylene at 273 K were measured by the volumetric method. The results are shown in FIG. 20, and no significant difference was observed in the adsorption characteristics.
  • a saturated hydrocarbon (even a minor component) in a mixture is selected even if it is a hydrocarbon having 3 or less carbon atoms such as propylene and propane and having the same carbon number.
  • Gas adsorbed in a temperature and pressure region for example, 1 kPa or more at 25 ° C.
  • a saturated hydrocarbon adsorption method capable of recovering (hydrogen), a separation method using the same, and a separation apparatus for performing the separation method.
  • the present invention is very useful as a technique for reducing the size of an apparatus for separating saturated hydrocarbons having 3 or less carbon atoms and saving energy for separation.
  • SYMBOLS 1 Adsorption tank (separation means), 2 ... Compressor (introduction means), 3 ... Decompression machine (pressure control means), 4 ... Control means, V1-V6 ... Valve, P1-P6 ... Piping.

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Abstract

La présente invention concerne un procédé d'adsorption d'hydrocarbures saturés entraînant l'absorption sélective d'un hydrocarbure saturé ne comportant pas plus de trois atomes de carbone par un complexe métallique comportant un ligand de formule (1) et un ion métallique, et ce, suite à la mise en contact d'un mélange comportant l'hydrocarbure saturé et un hydrocarbure insaturé avec ledit complexe métallique. Dans la formule (1), P représente un groupe hydrocarbure saturé pouvant comporter un substituant autre que Ra, Ra représente un groupe fonctionnel ayant des propriétés de coordination en relation avec les ions métalliques, m représente un nombre entier de 1 à 4, et quand m représente un nombre entier supérieur ou égal à 2, les Ra peuvent être identiques ou différents.
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