CN114432738A - Method for separating xylene isomers by liquid phase adsorption - Google Patents
Method for separating xylene isomers by liquid phase adsorption Download PDFInfo
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- CN114432738A CN114432738A CN202011221767.9A CN202011221767A CN114432738A CN 114432738 A CN114432738 A CN 114432738A CN 202011221767 A CN202011221767 A CN 202011221767A CN 114432738 A CN114432738 A CN 114432738A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 63
- 150000003738 xylenes Chemical class 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000007791 liquid phase Substances 0.000 title claims abstract description 7
- 239000003463 adsorbent Substances 0.000 claims abstract description 60
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 52
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 31
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 24
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 12
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 11
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical class C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012527 feed solution Substances 0.000 claims description 8
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 229910004074 SiF6 Inorganic materials 0.000 claims description 7
- 150000001449 anionic compounds Chemical class 0.000 claims description 7
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 239000013110 organic ligand Substances 0.000 claims description 7
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Chemical class C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- LGXAANYJEHLUEM-UHFFFAOYSA-N 1,2,3-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1C(C)C LGXAANYJEHLUEM-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004914 cyclooctane Substances 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 239000000523 sample Substances 0.000 description 23
- 238000002474 experimental method Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
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- 230000003068 static effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- -1 polyethylene terephthalate Polymers 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229940078552 o-xylene Drugs 0.000 description 5
- 230000035515 penetration Effects 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
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- 238000009835 boiling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- ALDOUWLIYKWJTN-UHFFFAOYSA-N fluoro(dioxido)borane;nickel(2+) Chemical compound [Ni+2].[O-]B([O-])F ALDOUWLIYKWJTN-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- 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
Abstract
The application discloses a method for separating xylene isomers by adsorbent liquid phase adsorption, which comprises the steps of carrying out adsorption separation on the xylene isomers by using an adsorbent; the adsorbent is selected from metal organic framework materials; the anhydrous chemical formula of the metal organic framework material is shown as a formula I, the selectivity of the adsorbent provided by the application to m-xylene and p-xylene is 2, the adsorption capacity is more than 10 wt% g/g, and the adsorbent is expected to adsorb trace m-xylene in high-purity p-xylene material flow and further purify the material.
Description
Technical Field
The application relates to a method for separating xylene isomers by liquid phase adsorption, belonging to the technical field of chemical separation.
Background
In recent years, the polyester industry in China is rapidly developed, the consumption of corresponding raw material aromatic hydrocarbons (benzene, toluene and xylene) is rapidly increased, and the supply gap is increased year by year. Mixtures of xylene isomers are commercially derived primarily from catalytic reforming, steam cracking, toluene disproportionation, and coal tar. Among them, p-xylene is the most industrially valuable monomer for further production of various polyester products such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). Three isomers of xylene isomers: o-xylene (ox), m-xylene (mx) and p-xylene (px), wherein o-xylene has a relatively high boiling point and is industrially available by rectification, whereas m-and p-xylene have boiling points that differ by only 0.75 ℃, and thus the separation difficulty is greatest for p-xylene and m-xylene. The adsorption separation method is a main method for separating the xylene at present due to high efficiency and low energy consumption. The development and design of the adsorbent in the xylene isomer adsorption separation method are a hot direction, and researchers are focusing on gradually transferring the zeolite molecular sieve adopted in the traditional industry to the metal organic framework material with stronger design. The metal organic framework material is a highly ordered porous organic material formed by coordination of metal ions and inorganic/organic ligands.
Disclosure of Invention
According to one aspect of the application, a liquid phase adsorption separation method of xylene isomers is provided, and SIFSIX series materials in anion-containing metal organic framework materials are used as adsorbents to achieve adsorption separation of the xylene isomers.
According to a first aspect of the present application, there is provided a method for liquid phase adsorptive separation of xylene isomers, comprising subjecting xylene isomers to adsorptive separation using an adsorbent;
the adsorbent is selected from metal organic framework materials;
the anhydrous chemical formula of the metal organic framework material is shown as formula I:
MA2q formula I
In formula I, M is a metal ion; the metal ion is selected from Cu2+、Zn2+、Ni2+、Co2+、Mg2+、Al2+、Fe2+At least one of;
a is an inorganic anion; the inorganic anion is selected from SiF6 2-、TiF6 2-、PF6 -、BF4 -、SnF6 2-、ZrF6 2-、GeF6 2-At least one of;
q is a nitrogen-containing organic ligand.
Optionally, the nitrogen-containing organic ligand is selected from at least one of 4,4 '-bipyridine, substituted 4, 4' -bipyridine and pyrazine.
Alternatively, the substituents in the substituted 4, 4' -bipyridine are selected from C1～C10Alkynyl of (A), C1～C10At least one of alkenyl groups of (a).
Optionally, the adsorbent is a cylindrical three-dimensional framework material.
Optionally, the adsorbent is in the form of a powder or film.
Optionally, the particle size of the powdered adsorbent is 5-10 μm.
Alternatively, the powdered adsorbent has an upper particle size independently selected from 10 μm, 9 μm, 8 μm, 7 μm, 6 μm and a lower particle size independently selected from 5 μm, 6 μm, 7 μm, 8 μm, 9 μm.
Optionally, the specific surface area of the adsorbent is 800-1300 m2/g。
Optionally, the upper limit of the specific surface area of the adsorbent is independently selected from 1300m2/g、1000m2/g、900m2(ii)/g, the lower limit being independently selected from 800m2/g、1000m2/g、900m2/g。
Optionally, the external specific surface area of the adsorbent is 100-200 m2/g。
Optionally, the upper limit of the external specific surface area of the adsorbent is independently selected from 200m2/g、180m2/g、160m2/g、140m2/g、120m2(ii)/g, the lower limit being independently selected from 100m2/g、180m2/g、160m2/g、140m2/g、120m2/g。
Optionally, the xylene isomers are selected from at least two of para-xylene, meta-xylene, and ortho-xylene.
Alternatively, the molar ratio of any two isomers of xylene isomers is 1: 1-10: 1.
alternatively, the upper limit of the molar ratio of any two isomers of xylene isomers is independently selected from 10: 1. 9: 1. 8: 1. 7: 1. 6: 1. 5: 1. 4: 1. 3: 1. 2: 1, the lower limit is independently selected from 1: 1. 9: 1. 8: 1. 7: 1. 6: 1. 5: 1. 4: 1. 3: 1. 2: 1.
optionally, the method comprises: the adsorbent is filled into a packed column, then the feed liquid containing the xylene isomers is introduced into the packed column, and the xylene isomers can be separated by controlling the time of the effluent liquid.
Optionally, the feed solution containing xylene isomers has a concentration of 0.001 to 10 wt%.
Alternatively, the upper concentration limit of the feed solution containing xylene isomers is independently selected from 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, and the lower limit is independently selected from 0.001 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%.
Optionally, the flow rate of the feeding liquid into the packed column is 0.1-2 mL/min.
Optionally, the upper flow rate limit of the feed solution into the packed column is independently selected from 2mL/min, 1.5mL/min, 1mL/min, 0.5mL/min, and the lower flow rate limit is independently selected from 0.1mL/min, 1.5mL/min, 1mL/min, 0.5 mL/min.
Optionally, the feed solution containing xylene isomers contains a solvent; the solvent is at least one selected from mesitylene, p-diethylbenzene, triisopropylbenzene, cyclooctane, n-heptane and n-hexane.
Optionally, the method comprises: the adsorbent is filled into a packed column, the packed column is flushed by a solvent, then a feed liquid containing the xylene isomers is introduced into the packed column, and the xylene isomers can be separated by controlling the time of an effluent liquid.
Optionally, the flow rate of the solvent for flushing the packed column is 0.1-2 mL/min.
Alternatively, the solvent for preparing the xylene isomer-containing solution may be an alkane such as n-hexane, n-heptane, isooctane, cyclooctane or the like, and an aromatic compound such as p-diethylbenzene, triisopropylbenzene, mesitylene or the like.
Optionally, the performance of the adsorbent for adsorbing and separating xylene isomers in the application can be verified through a static adsorption experiment, and the content of each isomer in the adsorbent can be measured in the static adsorption experiment when adsorption is balanced, so that which isomer has stronger acting force with the adsorbent can be analyzed.
Alternatively, the static adsorption experiment is performed in a shaker.
Optionally, the flow of adsorption separation of xylene isomers in practical application is simulated through a dynamic penetration experiment, the dynamic penetration experiment in the application is closest to the situation in practical application, and if the performance of the adsorbent for adsorption separation of xylene isomers is verified in the dynamic penetration experiment, the performance is enough to prove that the adsorbent has a good application prospect in adsorption separation of xylene isomers.
Optionally, in the static adsorption experiment, the mass ratio of the adsorbent to the adsorbate (xylene isomer) is 0.2-0.6.
Optionally, in a static adsorption experiment, the adsorption temperature is 25-45 ℃; the adsorption time is 1-24 h.
Optionally, the adsorbent is regenerable;
the regeneration method is selected from any one of the following methods:
the method comprises the following steps: putting the adsorbent subjected to xylene isomer adsorption separation under a vacuum condition, and desorbing to obtain a regenerated adsorbent;
the second method comprises the following steps: and (3) placing the adsorbent subjected to xylene isomer adsorption separation in an inactive atmosphere, and desorbing at 30-100 ℃ to obtain the regenerated adsorbent.
Optionally, the inert atmosphere is selected from nitrogen or an inert gas.
Optionally, the adsorption is preceded by a pretreatment activation, and the pretreatment conditions are as follows: vacuumizing for 8-12 h, wherein the pressure is below 100 mmHg; or blowing the mixture for 3-5 hours at 30 ℃ by using nitrogen.
In the present application, "C1～C10"refers to the number of carbon atoms contained in a group.
In the present application, an "alkynyl group" is a group formed by losing any one hydrogen atom on the molecule of an alkyne compound.
In the present application, the external specific surface area refers to the specific surface area of the porous substance obtained by the t-Plot method in the measurement of physical adsorption, that is, the BET total area of the material minus the specific surface area of micropores thereof.
The beneficial effects that this application can produce include:
(1) the adsorbent in the application is a column-shaped three-dimensional framework material and is prepared by six-coordinated metal ions such as Cu2+With nitrogen-containing organic ligands, e.g. 4, 4' -bipyridine, etc., and inorganic anions, e.g. SiF6 2-The bridges form a three-dimensional network structure. The unique pore structure of such porous materials and the inorganic anions therein, such as SiF6 2-The sites allow them to exhibit unique properties in the field of xylene isomer adsorptive separation.
(2) The adsorbent is prepared by reacting inorganic anions, metal ions and nitrogen-containing organic ligands, and the preparation process is mild in reaction conditions, simple to operate and easy to realize.
(3) The selectivity of the adsorbent to m-xylene and p-xylene in the application is 2, the adsorption capacity is more than 10 wt% g/g, and the adsorbent is expected to adsorb trace m-xylene in high-purity p-xylene stream for further purification.
Drawings
Figure 1 is an XRD pattern of the product synthesized according to example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a product synthesized according to example 1 of the present invention.
FIG. 3 is a graph of the physical adsorption isotherm (BET) of the product synthesized according to example 1 of the present invention.
FIG. 4 is a single component adsorption profile of the product synthesized according to example 1 of the present invention.
FIGS. 5-6 are two-component competition graphs for the products synthesized in example 1 according to the present invention.
FIGS. 7-8 are xylene isomer dynamic breakthrough profiles for products synthesized in accordance with example 1 of the present invention.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Synthetic references of SISIX series (S.Noro, R.Kitaura, M.Kondo, S.Kitagawa, T.Ishii, H.Matsuzaka, M.Yamashita, Framework Engineering by equations and ports functional solutions Cu (II)/4, 4' -by Coordination polymers journal of the American Chemical Society 2002,124, 2568-shaped charge 2583.) and (X.Cui, K.Chen, H.Xiing, Q.Yang, R.Krisphenana, Z.Bao, H.Wu, W.Zhou, X.Dong, Y.Han, B.Li, Q.ren, M.J.Zaworkko, B.chemistry, science 353, Porous concrete 141, 2016).
In the examples of the present application, X-ray powder diffractometry phase analysis (XRD) of the product used an X' Pert PRO X-ray diffractometer from PANalytical, netherlands, Cu target, ka radiation source (λ ═ 0.15418nm), voltage 40KV, current 40 mA.
In the examples of the present application, SEM topography analysis of the product was performed using a Hitachi SU8020 scanning electron microscope.
In the examples of the present application, the physical adsorption and pore distribution analysis of the product was performed using a fully automated physical analyzer, ASAP2020 available from Mike corporation.
In the examples of the present application, the adsorption performance was evaluated by an Agilent gas chromatograph under the following conditions: a capillary column: polar polyethylene glycol stationary phase capillary column such as FFAP/DB-WAX is adopted; advancing sample port vaporizing chamber temperature: 150-200 ℃; the column temperature adopts programmed temperature rise; detector temperature: the flow rate of the carrier gas is 1-5 mL/min at 200-220 ℃; h2The flow rate is 10-30 mL/min, and the air flow rate is 200-400 mL/min.
Example 1
The specific batching process is as follows: 4, 4' -bipyridine 1.05g was dissolved in 132mL of ethylene glycol solvent at 65 ℃, ammonium hexafluorosilicate 0.06g and copper tetrafluoroborate 0.18g were dissolved in deionized water at 65 ℃, the two completely dissolved solutions were mixed, and the reaction was continued in a constant temperature water bath at 65 ℃ for 3 hours to obtain a purple solution. Obtaining a purple solid product by suction filtration and washing of a methanol solventSoaking in methanol for activating for three days to obtain SIFSIX ion hybrid skeleton material SISIX-1-Cu [ Cu (bpy-1) ]2(SiF6)]Marked as 1 #. XRD analysis was performed on a sample (1#) of the purple solid, and the result is shown in FIG. 1, from which it can be seen that the sample is SISIX-1-Cu; the Scanning Electron Microscope (SEM) image of the sample is shown in FIG. 2, and it can be seen that the sample has a cylindrical three-dimensional structure; the nitrogen physisorption isotherm of this sample is shown in fig. 3, which shows a typical type i isotherm; the physisorption data of this sample are shown in table 1, from which it can be seen that the sample has 957m2g-1Specific surface area of (2).
TABLE 1 specific surface area and pore volume of the sample of example 1
Example 2
The specific batching process is as follows: weighing 0.018g4, 4' -bipyridyl acetylene and dissolving in 2mL ethanol solvent, weighing 0.21g ammonium hexafluorosilicate and 0.6g copper tetrafluoroborate aqueous solution (wherein the mass content of the copper tetrafluoroborate is 45 wt%) and dissolving in 2mL ethylene glycol, adding 2mL ethylene glycol solution into a glass bottle by an interfacial diffusion method, slowly adding the ethanol solution, standing for two weeks, soaking the crystal in ethanol for activation for 72h, and finally obtaining SISISIX ion hybrid framework material SISISIX-2-Cu [ Cu (bpy-2) ]2(SiF6)]And is labeled 2 #.
Example 3
The specific batching process is as follows: adding 0.104g pyrazine into 2mL methanol, adding 0.134g zinc hexafluorosilicate into 2mL methanol, adding the methanol solution containing pyrazine into the methanol solution containing zinc hexafluorosilicate by interfacial diffusion method, standing for three days, soaking and activating the product in methanol for 72h, and finally obtaining SIFSIX ion hybrid framework material SISIX-3-Zn, [ Zn (bpy-3) ]2(SiF6)]And is marked as 3 #.
Example 4
The specific batching process is as follows: 0.35g of 4, 4' -bipyridine was dissolved0.249g of ammonium hexafluorogermanate and 0.6g of copper tetrafluoroborate (45% by weight aqueous solution) were dissolved in 40mL of ethylene glycol solvent at 65 ℃ in 10mL of deionized water, and the two completely dissolved solutions were mixed and reacted in a constant temperature water bath at 65 ℃ for 2 hours. Filtering, washing with methanol solvent to obtain solid product, soaking in methanol for activating for three days to obtain SIFSIX ion hybrid skeleton material { [ Cu (GeF)6)(4,4′-bpy)2]，8H2O}nAnd is labeled 4 #.
Example 5
The specific batching process is as follows: 0.04g of 4, 4' -bipyridinylacetylene was dissolved in 4mL of methanol solvent, 0.23g of ammonium hexafluorotitanate and 0.5g of an aqueous solution of nickel tetrafluoroborate were dissolved in 4mL of methanol solvent, and the two completely dissolved solutions were mixed and reacted for 4 hours with further stirring at room temperature. Filtering, washing with methanol solvent to obtain solid product, soaking in methanol for activating for three days to obtain SIFSIX ion hybrid skeleton material { [ Ni (BF) { [6)(bpy-2)2]，8H2O}nAnd is marked as # 5.
Example 6
The specific batching process is as follows: 0.25g of 4, 4' -bipyridine was dissolved in 20mL of ethylene glycol solvent, 0.15g of ammonium hexafluorosilicate and 0.4g of ferrous tetrafluoroborate were dissolved in 10mL of deionized water, and the two completely dissolved solutions were mixed and the reaction was continued at room temperature with stirring for 3 hours. Filtering, washing with methanol solvent to obtain solid product, soaking in methanol for activation for three days to obtain SIFSIX ion hybrid skeleton material { [ Fe (SiF) { [6)(bpy-1)2]，8H2O}nAnd is labeled 6 #.
Example 7 evaluation test of static one-component adsorption Properties of different solvents
One-component xylene static adsorption experiments were performed with the samples in examples 1 to 6. And (3) preparing single-component 5 wt% paraxylene and 5 wt% metaxylene adsorption liquid to evaluate the adsorption performance of paraxylene and metaxylene. Different organics will be used as solvents under different pretreatment conditions, as shown in table 2. A series of concentration gradient (1 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%, 15 wt%) single-component p-xylene/m-xylene/o-xylene adsorption solutions were prepared simultaneously. Adding the solid powder adsorbent subjected to vacuum-pumping pretreatment into adsorption solutions of different solvents in batches, performing an adsorption experiment in a shaking table, setting a blank control group, absorbing supernatant after adsorbing for 3 hours, and analyzing the concentration of each component in the blank sample and the concentration of each component in the adsorbed sample by using a gas chromatograph. The adsorption data of the single-component different solvent, as represented by sample # 1 in example 1, are shown in table 2, and it can be seen from table 2 that the adsorbent selectively adsorbs meta-xylene regardless of the solvent, as shown by the fact that the amount of adsorption of meta-xylene is greater than that of para-xylene and the selectivity is maintained at 2 or more. The adsorption curves for the different concentration gradients of the single component are shown in fig. 4. it can be seen that the adsorption of ortho-xylene is highest, followed by meta-xylene and finally para-xylene.
Table 2 adsorption data of example 1 samples in different solvents under different pretreatment conditions
Example 8 static two-component adsorption Performance evaluation test
Two-component (p-xylene/m-xylene and p-xylene/o-xylene) static adsorption experiments were performed with the samples of examples 1 to 6. A series of mixed adsorption solutions of paraxylene/metaxylene with concentration gradients are prepared, wherein the mixed adsorption solutions comprise 1 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt% and 15 wt% (the molar ratio of paraxylene to metaxylene in each mixed adsorption solution is 1: 1). Taking mesitylene as a solvent, adding the solid powder adsorbent subjected to vacuum-pumping pretreatment into adsorption solutions with different concentrations in batches, performing an adsorption experiment in a shaking table, setting a blank control group, absorbing supernatant after adsorbing for one hour, and analyzing the concentration of each component in the blank sample and the concentration of each component in the adsorbed sample by using a gas chromatograph. The adsorption profiles of the two-component competition are shown in FIGS. 5 and 6, which are typically represented by sample No. 1 in example 1. As can be seen from fig. 5 and 6, the m-xylene/p-xylene selectivity is maintained at around 2, and the o-xylene/p-xylene selectivity is maintained at around 3.
Example 9 dynamic penetration Performance evaluation test
The bi-component xylene dynamic breakthrough experiments were performed with the samples from example 1 to example 6. The adsorbent after the vacuum pretreatment was taken, 0.6g of the granular adsorbent was packed in an adsorption column (inner diameter 4mm, length 50mm), and the breakthrough test was started at room temperature of 25 ℃. Before the breakthrough experiment was started, the line and column were flushed with pure mesitylene solvent by a pump at a flow rate of 1mL/min, when the line was completely filled with pure mesitylene solvent, the feed solution was changed from mesitylene to a 0.3 wt% p-xylene/m-xylene equimolar mixture, at a flow rate of 0.2mL/min, one sample was taken every minute from the first drop, 11 samples were taken, and one sample was taken every five minutes until the adsorbent in the column was completely penetrated by the two component xylenes. After completion of the experiment, the column was washed with pure mesitylene solvent at a flow rate of 2mL/min for 2 h. The exit sample concentration was measured by gas chromatography, typically sample # 1 in example 1, and the breakthrough curve of the sample concentration as a function of time was plotted as fig. 7. as can be seen from fig. 7, the first breakthrough of paraxylene was detected out of the bed, the breakthrough after the predominantly adsorbed metaxylene, indicating that the adsorbent can separate paraxylene from metaxylene at 0.3% feed concentration.
Example 10 dynamic penetration Performance evaluation test
Two-component p-xylene/m-xylene dynamic breakthrough experiments were performed with the samples from example 1 to example 6. The adsorbent after the vacuum pretreatment was taken, 0.6g of the granular adsorbent was packed in an adsorption column (inner diameter 4mm, length 50mm), and the breakthrough test was started at room temperature of 25 ℃. Before the breakthrough experiment was started, pure heptane solvent was pumped by a pump at a flow rate of 1mL/min to flush the tubing and column, when the tubing was completely filled with pure n-heptane solvent, the feed solution was changed from n-heptane to a 0.1 wt% xylene two-component equimolar mixture solution at a flow rate of 0.5mL/min, starting with the first drop of liquid flow, taking one sample per minute, and after 11 samples were taken, taking one sample every five minutes until the adsorbent in the column was completely penetrated by the two components of xylene. After the experiment was completed, the column was further flushed with pure heptane solvent at a flow rate of 5mL/min for 3 h. The exit sample concentration was measured by gas chromatography, typically represented by sample # 1 in example 1, and the breakthrough curves of sample concentration over time were plotted as figure 8. as can be seen from figure 8, p-xylene and m-xylene also separated well at 0.1% and feed concentration and the n-heptane solvent system.
Example 11 Single/Multi-component static adsorption Experimental testing of different adsorption times and adsorbate to adsorbent mass ratios
The adsorbents in examples 1 to 4 were evaluated for adsorption performance in the same manner as in example 7, and specific static adsorption experimental conditions were different from those in examples 7 and 8 in tables 3 and 4.
TABLE 3 Condition parameters for Single component xylene static adsorption experiment
TABLE 4 Condition parameters for competitive adsorption experiments on multicomponent xylenes
The test results of the above samples are selective adsorption of meta-xylene.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for separating xylene isomers by liquid phase adsorption is characterized in that an adsorbent is used for carrying out adsorption separation on the xylene isomers;
the adsorbent is selected from metal organic framework materials;
the anhydrous chemical formula of the metal organic framework material is shown as formula I:
MA2q formula I
In formula I, M is a metal ion; the metal ion is selected from Cu2+、Zn2+、Ni2+、Co2+、Mg2+、Al2+、Fe2+At least one of;
a is an inorganic anion; the inorganic anion is selected from SiF6 2-、TiF6 2-、PF6 -、BF4 -、SnF6 2-、ZrF6 2-、GeF6 2-At least one of;
q is a nitrogen-containing organic ligand.
2. The method according to claim 1, wherein the nitrogen-containing organic ligand is selected from at least one of 4,4 '-bipyridine, substituted 4, 4' -bipyridine, pyrazine.
3. The method of claim 2, wherein the substituent in the substituted 4, 4' -bipyridine is selected from the group consisting of C1～C10Alkynyl of (A), C1～C10At least one of alkenyl groups of (a).
4. The method of claim 1, wherein the adsorbent is in the form of a powder or film.
5. The method of claim 4, wherein the adsorbent is in a powder form;
the particle size of the adsorbent is 5-10 mu m.
6. The method according to claim 1, wherein the adsorbent has a specific surface area of 800 to 1300m2/g；
The external specific surface area of the adsorbent is 100-200 m2/g。
7. The method of claim 1, wherein the xylene isomers are selected from at least two of para-xylene, meta-xylene, and ortho-xylene.
8. The process of claim 1, wherein the molar ratio of any two isomers of the xylene isomers is 1: 1-10: 1.
9. the method according to claim 1, characterized in that it comprises: the adsorbent is filled into a packed column, then the feed liquid containing the xylene isomers is introduced into the packed column, and the xylene isomers can be separated by controlling the time of the effluent liquid.
10. The method of claim 9, wherein the feed solution containing xylene isomers has a concentration of 0.001 to 10 wt.%;
preferably, the flow rate of the feeding liquid introduced into the packed column is 0.1-2 mL/min;
preferably, the feed solution containing xylene isomers contains a solvent; the solvent is selected from at least one of mesitylene, p-diethylbenzene, triisopropylbenzene, cyclooctane, n-heptane and n-hexane;
preferably, the method comprises: filling an adsorbent into a packed column, flushing the packed column by using a solvent, introducing a feed liquid containing xylene isomers into the packed column, and controlling the time of an effluent liquid to realize the separation of the xylene isomers;
preferably, the adsorbent is regenerable;
the regeneration method is selected from any one of the following methods:
the method comprises the following steps: putting the adsorbent subjected to xylene isomer adsorption separation under a vacuum condition, and desorbing to obtain a regenerated adsorbent;
the second method comprises the following steps: and (3) placing the adsorbent subjected to xylene isomer adsorption separation in an inactive atmosphere, and desorbing at 30-100 ℃ to obtain the regenerated adsorbent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090263621A1 (en) * | 2006-12-13 | 2009-10-22 | Korea Research Institute Of Chemical Technology | Porous organic-inorganic hybrid materials and adsorbent comprising the same |
| WO2016162834A1 (en) * | 2015-04-07 | 2016-10-13 | King Abdullah University Of Science And Technology | Highly stable ni-m f6-nh2o/onpyrazine2(solvent)x metal organic frameworks and methods of use |
| CN111187418A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Zirconium-based organic framework compound and preparation method and application thereof |
| CN111410596A (en) * | 2020-04-02 | 2020-07-14 | 浙江大学 | Separation method of carbon octa-aromatic hydrocarbon isomer mixture |
-
2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090263621A1 (en) * | 2006-12-13 | 2009-10-22 | Korea Research Institute Of Chemical Technology | Porous organic-inorganic hybrid materials and adsorbent comprising the same |
| WO2016162834A1 (en) * | 2015-04-07 | 2016-10-13 | King Abdullah University Of Science And Technology | Highly stable ni-m f6-nh2o/onpyrazine2(solvent)x metal organic frameworks and methods of use |
| CN111187418A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Zirconium-based organic framework compound and preparation method and application thereof |
| CN111410596A (en) * | 2020-04-02 | 2020-07-14 | 浙江大学 | Separation method of carbon octa-aromatic hydrocarbon isomer mixture |
Non-Patent Citations (2)
| Title |
|---|
| 杨玉茜: "金属-有机骨架材料吸附分离二甲苯异构体的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 07, 15 July 2019 (2019-07-15), pages 014 - 893 * |
| 武汉大学化学与分子科学学院实验中心编: "有机化学实验", 武汉：武汉大学出版社, pages: 110 - 111 * |
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