CN114100583A - Composite material, preparation method thereof, method for removing benzene series by using composite material and application of composite material - Google Patents
Composite material, preparation method thereof, method for removing benzene series by using composite material and application of composite material Download PDFInfo
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- CN114100583A CN114100583A CN202010906206.6A CN202010906206A CN114100583A CN 114100583 A CN114100583 A CN 114100583A CN 202010906206 A CN202010906206 A CN 202010906206A CN 114100583 A CN114100583 A CN 114100583A
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- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 69
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 239000013082 iron-based metal-organic framework Substances 0.000 claims abstract description 46
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 12
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 150000001555 benzenes Chemical class 0.000 claims description 32
- 238000001179 sorption measurement Methods 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 22
- 239000013144 Fe-MIL-100 Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
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- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
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- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012855 volatile organic compound Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 22
- 239000007787 solid Substances 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 16
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- 229910052742 iron Inorganic materials 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
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- 238000000926 separation method Methods 0.000 description 4
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013148 Cu-BTC MOF Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000006359 acetalization reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 244000208060 Lawsonia inermis Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- MUBKMWFYVHYZAI-UHFFFAOYSA-N [Al].[Cu].[Zn] Chemical compound [Al].[Cu].[Zn] MUBKMWFYVHYZAI-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
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- 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
- 238000001308 synthesis method Methods 0.000 description 1
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- 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
- 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
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- 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
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- 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
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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- 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
- B01J20/28078—Pore diameter
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- 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
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3206—Organic carriers, supports or substrates
- B01J20/3208—Polymeric carriers, supports or substrates
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- 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
- B01D2253/25—Coated, impregnated or composite adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
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Abstract
The invention relates to the field of material synthesis, and discloses a composite material, a preparation method thereof, a method for removing benzene series by using the composite material and application of the composite material. The composite material comprises a polymer and an iron-based metal organic framework material, wherein the weight ratio of the polymer to the iron-based metal organic framework material is 1: (1-25), wherein the polymer is polyvinyl butyral and/or polyvinyl acetal. The composite material has a stable skeleton structure, has large pore volume, pore diameter and specific surface area, has strong mechanical strength, thermal stability and chemical stability, has large particle size, is not easy to block process equipment in the subsequent use process, has good heat and mass transfer effects and low pressure drop, can be used for adsorbing low-concentration VOCs in the environment, and simultaneously has the advantages of simple and environment-friendly preparation method, low synthetic raw material price and easy large-scale production and application.
Description
Technical Field
The invention relates to the field of material synthesis, in particular to a composite material, a preparation method thereof, a method for removing benzene series by using the composite material and application of the composite material.
Background
Metal Organic Frameworks (MOFs) are framework materials formed by self-assembly of metal ions (iron, aluminum, copper, zinc, chromium, etc.) and functional organic ligands. MOFs as a new porous material, the specific surface area and pore volume of which can be respectively up to 10000m2G and 4.40cm3In addition, the structural diversity and adjustability of MOFs materials enable the MOFs materials to have wide application prospects in the fields of gas adsorption and separation, catalysis, sensing, drug separation and the like.
Currently, the research on the MOFs materials by scientists is mainly focused on the design and synthesis of new structures, and more than 6000 MOFs materials with new structures are reported to be generated every year. However, since most MOFs materials are synthesized on a small scale (from milligrams to grams) and are usually in powder form, their industrial scale applications in the fields of adsorptive separation, catalysis, etc. are limited. Therefore, it is necessary to process MOFs powders into millimeter-sized blocks because the shaped materials can have higher mechanical strength and lower pressure drop in a fixed bed adsorption process.
The extrusion method is one of the main methods for granulation molding of the traditional adsorbents and catalysts such as commercial activated carbon and molecular sieve at present, and the research on the molding of MOFs materials is less. In the extrusion granulation process, a binder, a solvent, or the like is often added to the material. Common granulation binders are inorganic binders such as alumina, but the small particle size of the binders can block the pore channels of porous materials, so that the specific surface area and the pore volume of the materials are greatly reduced.
For this reason, the existing technologies for preparing MOFs materials are in need of further improvement.
Disclosure of Invention
The invention aims to overcome the technical problems of blocking porous material pore channels and causing great reduction of specific surface area and pore volume in the granulation process of inorganic binders in the prior art, and provides a composite material, a preparation method thereof and a method for removing benzene series substances by using the composite material.
In order to achieve the above object, an aspect of the present invention provides a composite material including a polymer and an iron-based metal organic framework material, wherein a weight ratio between the polymer and the iron-based metal organic framework material is 1: (1-25), wherein the polymer is polyvinyl butyral and/or polyvinyl acetal.
In the invention, the iron-based metal organic framework material is loaded (dispersed and wrapped) in the polymer to form the composite material, the composite material has a stable framework structure, has strong mechanical strength, thermal stability and chemical stability, has large particle size, is not easy to block process equipment in the subsequent use process, has good heat and mass transfer effects and small pressure drop, and can be used for adsorbing low-concentration benzene series in the environment.
A second aspect of the invention provides a method of making a composite material, the method comprising: mixing a polymer and an iron-based metal organic framework material for extrusion molding, wherein the polymer and the iron-based metal organic framework material are used in an amount that the weight ratio of the polymer to the iron-based metal organic framework material is 1: (1-25), wherein the polymer is polyvinyl butyral and/or polyvinyl acetal.
In a third aspect of the present invention, there is provided a composite material obtained by the above-mentioned production method.
In a fourth aspect of the present invention, there is provided a method for removing benzene series, the method comprising: contacting a sample to be treated containing benzene series with the composite material; or preparing the composite material by adopting the method, and then contacting the sample to be treated containing the benzene series with the obtained composite material.
In a fifth aspect of the invention, the composite material or the preparation method thereof is applied to benzene series adsorption.
The method for preparing the composite material comprises the steps of firstly dissolving a polymer in a solvent, then dropwise adding the obtained solution containing the polymer into an iron-based metal organic framework material, uniformly stirring to obtain a mixture, and then conveying the mixed material to an extrusion device for molding treatment to obtain the material particles with different sizes. In the preparation process, the polymer and the iron-based metal organic framework material are mixed and then extruded for molding, the iron-based metal organic framework material powder is re-granulated, the obtained composite material has larger particle size, so that the iron-based metal organic framework material can also be applied in the fields of adsorption separation, catalysis and the like on an industrial scale, the application range of the iron-based metal organic framework material is enlarged, the obtained composite material has stable framework structure, larger pore volume, pore diameter and specific surface area, stronger mechanical strength, thermal stability and chemical stability, larger particle size, difficult blockage of process equipment in the subsequent use process, better heat and mass transfer effect and lower pressure drop, can be used for adsorption of low-concentration VOCs in the environment, and simultaneously, the method for preparing the composite material is simple and environment-friendly, and the synthetic raw material has low price, is easy for large-scale production and application.
The sample to be treated containing the benzene series is contacted with the composite material to adsorb the benzene series in the sample to be treated, and the composite material has higher benzene series adsorption capacity, so that the effect of removing the benzene series is better.
Drawings
FIG. 1 is a nitrogen sorption isotherm (77K) of a composite material obtained according to one embodiment of the invention;
FIG. 2 is a nitrogen sorption isotherm (77K) of a composite obtained according to another embodiment of the invention;
FIG. 3 is a nitrogen adsorption isotherm (77K) for an activated carbon material;
FIG. 4 is a scanning electron micrograph of a composite material obtained according to an embodiment of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a composite material, which comprises a polymer and an iron-based metal organic framework material, wherein the weight ratio of the polymer to the iron-based metal organic framework material is 1: (1-25), wherein the polymer is polyvinyl butyral and/or polyvinyl acetal.
In the present invention, the source of the polymer is not particularly limited and can be obtained by commercial or self-production, and for example, in the case of polyvinyl butyral, it can be produced in the following manner: dissolving polyvinyl alcohol in water, adding butyraldehyde and a catalyst such as hydrochloric acid and/or sulfuric acid under stirring, carrying out an acetalization reaction at a temperature of 15-50 ℃, washing, centrifuging and drying the generated acetal to obtain the polyvinyl butyral. For polyvinyl acetal, it can be prepared in the following manner: the vinyl acetate is prepared by using methanol or ethanol as a medium, reacting to generate polyvinyl acetate in the presence of benzoyl peroxide, hydrolyzing in the presence of methanol and sulfuric acid, adding acetaldehyde for acetalization, neutralizing, precipitating, filtering and drying. Preferably, the weight average molecular weight of the polymer is 40000-120000.
In the present invention, the source of the iron-based metal organic framework material is not particularly limited and may be obtained by commercial or self-preparation, and preferably, the iron-based metal organic framework material is selected from MIL-100(Fe) and/or MIL-101 (Fe).
According to one embodiment of the invention, a method of making MIL-101(Fe) comprises: in a solvent, an iron source is contacted with terephthalic acid for reaction, and the obtained solid after the reaction is washed and dried in sequence. Wherein the molar ratio of the iron source to the terephthalic acid, calculated as Fe, may be 1: 0.2-1. The dosage of the solvent is 0.1-0.5mol/L of the content of the iron source in the contact system counted by Fe. The solvent is preferably N, N-Dimethylformamide (DMF). The iron source may be a common substance capable of providing iron ions, preferably ferric chloride. The conditions of the contacting may include: the temperature is 100-120 ℃, and the time is 15-30 h. More specifically, the process for the self-preparation of MIL-101(Fe) is as follows: mixing the following components in parts by weight: 0.2-1 FeCl3·6H2Adding O and terephthalic acid into N, N-Dimethylformamide (DMF) solvent, wherein the content of an iron source in terms of Fe in a reaction system is 0.1-0.5mol/L, and uniformly stirring at room temperature. Heating the mixed solution at the temperature of 100 ℃ and 120 ℃ for 15-30 h. Cooling to room temperature, separating the solid (centrifugation, 2000-4000rpm, time 10-30 min). The solid is washed by heating with DMF, water (preferably deionized water), and ethanol at 50-70 deg.C, respectively. And drying the solid to obtain the MIL-101(Fe) material used by the invention.
According to one embodiment of the invention, a method of making MIL-100(Fe) comprises: in a solvent, an iron source is contacted with trimesic acid for reaction, and the obtained solid after the reaction is orderly subjected to reactionWashing and drying are carried out. Wherein, the mol ratio of the iron source to the trimesic acid calculated by Fe can be 1: 0.5-1. The solvent is used in such an amount that the molar ratio of the iron source to the solvent, in terms of Fe, is 1: 120-180. The solvent is preferably water (especially deionized water). The iron source may be a common substance capable of providing iron ions, and is preferably ferric nitrate. The conditions of the contacting may include: the temperature is 90-120 ℃, and the time is 20-30 h. More specifically, the process for the self-preparation of MIL-100(Fe) is as follows: mixing Fe (NO)3)3·9H2Adding O, organic ligand trimesic acid into deionized water, and adding FeCl3·6H2O/trimesic acid/H2The molar ratio of O is 1:0.5-1:120-180, and the mixture is stirred uniformly at room temperature. Heating the mixed solution at 90-120 deg.C for 20-30 h. After the reaction, the reaction mixture was cooled to room temperature, and the solid was separated (centrifugation at 2000-. The solid is washed separately with N, N-Dimethylformamide (DMF), water (preferably deionized water), ethanol. Drying the solid (heating and activating at the temperature of 120-160 ℃ for 10-15h) to obtain the MIL-100(Fe) material used by the invention.
In the present invention, preferably, the weight ratio between the polymer and the iron-based metal organic framework material is 1: (4-20), e.g., 1:4, 1:5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:15, 1:17, 1:18, 1:19, 1:20, or any value therebetween.
In the present invention, preferably, the specific surface area of the composite material is 700-3000m2(ii) in terms of/g. Preferably, the pore size distribution of the composite material is 2-2.8 nm. Preferably, the composite material has an average particle size of 1 to 10mm, more preferably 1 to 3 mm. Preferably, the benzene vapor saturation adsorption amount of the composite material is 300-1200 mg/g. Preferably, the toluene vapor saturation adsorption capacity of the composite material is 250-1100 mg/g.
A second aspect of the invention provides a method of making a composite material, the method comprising: mixing a polymer and an iron-based metal organic framework material for extrusion molding, wherein the polymer and the iron-based metal organic framework material are used in an amount that the weight ratio of the polymer to the iron-based metal organic framework material is 1: (1-25), wherein the polymer is polyvinyl butyral and/or polyvinyl acetal.
In the present invention, it is preferable that the polymer and the iron-based metal organic framework material are used in such amounts that the weight ratio between the polymer and the iron-based metal organic framework material is 1: (4-20), e.g., 1:4, 1:5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:15, 1:17, 1:18, 1:19, 1:20, or any value therebetween.
In the present invention, it is preferred that the weight average molecular weight of the polymer is 40000-120000.
In the present invention, preferably, the iron-based metal-organic framework material is selected from MIL-100(Fe) and/or MIL-101 (Fe).
In the present invention, it is preferable that the polymer is mixed with the iron-based metal organic framework material in the form of a solution.
In the present invention, in order to make the iron-based metal organic framework material more easily formable during extrusion, it is preferable that the concentration of the polymer in the solution is 4 to 11 wt%, more preferably 5 to 8 wt%.
In the present invention, the solvent in the solution is not particularly limited as long as the polymer can be dissolved, and preferably, the solvent in the solution is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-pentanol, benzyl alcohol, butanol, diacetone alcohol, propylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol propyl ether, acetone, methyl ethyl ketone, cyclohexanone, methylene chloride, chloroform, methyl acetate, ethyl acetate, butyl acetate, and acetic acid.
In the present invention, in order to sufficiently mix the iron-based metal organic framework material with the polymer solution, it is preferable that the solution is mixed with the iron-based metal organic framework material in an additive manner (i.e., the solution is added to the iron-based metal organic framework material) at a dropping rate of 0.025 to 0.7mL/s per gram of the iron-based metal organic framework material.
In the present invention, in the method, the solvent and the polymer may be mixed under heating conditions in order to dissolve the polymer, and the heating temperature may be 50 to 100 ℃.
In the present invention, the polymer and the iron-based metal organic framework material may be mixed as necessary and then extrusion-molded to obtain a composite material having a specific size, preferably, the extrusion-molding conditions are such that the average particle size of the obtained composite material is 1 to 10mm, more preferably 1 to 3 mm.
In the present invention, the method may further include a drying step, the drying manner is not particularly limited, and a natural airing manner or a drying manner in a drying device may be adopted, and preferably, the drying conditions include: the temperature is 50-100 deg.C, preferably 60-80 deg.C. The drying conditions further include: the time is 2-24h, preferably 12-24 h.
In a third aspect of the present invention, there is provided a composite material obtained by the above-mentioned production method.
In a fourth aspect of the present invention, there is provided a method for removing benzene compounds using the above composite material, comprising contacting a sample to be treated containing benzene compounds with the above composite material; or preparing the composite material by adopting the method, and then contacting the sample to be treated containing the benzene series with the obtained composite material.
In the present invention, the amount of the composite material is not particularly limited, and is preferably 0.5 to 2g per gram of the sample to be treated in terms of benzene series.
Preferably, the conditions of the contacting include: the temperature is 15-40 ℃.
The composite material of the invention is particularly suitable for adsorbing benzene series, and the benzene series can be various common benzene series, such as benzene series with 6-10 carbon atoms, for example, benzene, toluene, ethylbenzene, xylene and the like. The sample to be treated containing the benzene series can be various common samples needing benzene series adsorption removal, can be a gas sample, and can also be an environment.
In the invention, in order to sufficiently remove the solvent or water vapor adsorbed in the pores of the composite material and exert the adsorption property of the material to the maximum extent, the method further comprises activating the composite material before contacting with the sample to be treated, wherein the activating condition can comprise that the temperature is 140-160 ℃, and the activating time can be 2-5 h.
In a fifth aspect of the invention, the composite material or the preparation method thereof is applied to benzene series adsorption.
The present invention will be described in detail below by way of examples.
The reagents used in the examples and comparative examples are as follows: polyvinyl butyral (alfa aesar, weight average molecular weight 90000), activated carbon (bamboo forest activated carbon development ltd, zheng, henna), room temperature means "25 ℃".
Preparation example 1
Mixing Fe (NO)3)3·9H2O (0.03mol, 12g) and organic ligand trimesic acid (0.02mol, 4.2g) are added into a reaction bottle containing deionized water (80ml) and stirred uniformly at room temperature. The mixture was transferred to an oil bath and heated at 95 ℃ for 24 h. After the reaction was completed, it was cooled to room temperature, and the solid was separated by centrifugation (3500rpm, 20 min). The solid was washed with N, N-Dimethylformamide (DMF), deionized water, ethanol, respectively. The solid is heated and activated for 12h at 150 ℃ in a vacuum oven, and the obtained product is proved to be the MIL-100(Fe) material used in the example through X-ray powder diffraction detection. The X-ray powder diffraction test conditions are as follows: the German Bruker-AXSD 8X-ray full-automatic diffractometer is adopted, a light source adopts a radiation source Cu target Kalpha radiation, the tube pressure is 30kV, the tube flow is 30mA, the scanning is continuously carried out, the scanning speed is 2 degrees/min, and the scanning range is 2 degrees to 20 degrees.
Preparation example 2
Separately weighing FeCl3·6H2O (13.5g, 0.05mol) and terephthalic acid (4.2g, 0.025mol) were added to a solvent of N, N-dimethylformamide (DMF, 300ml), and stirred at room temperature. Transferring the mixed solution into a polytetrafluoroethylene lining high-pressure reaction kettle, and heating for 20h at 110 ℃. Cooled to room temperature and centrifuged (3500rpm, 20min) to separate the solid. The solid was washed with DMF, deionized water, ethanol, and heated at 60 deg.C for 12 h. The solid was heated in a vacuum oven at 150 ℃ for 12h, and the resulting product was confirmed to be the MIL-101(Fe) material used in the examples by X-ray powder diffraction detection (conditions same as in preparation example 1).
Example 1
Polyvinyl butyral (PVB, 0.3g) was added to an ethanol solvent (3.5g) and dissolved by heating (temperature 50 ℃), and then the mixture was slowly dropped (dropping speed 0.025mL/s) into MIL-100(Fe) powder (2.7g), and mixed uniformly with stirring. The mixture was extruded into a cylinder having a cross-sectional diameter of 1mm by means of an extruder. And heating and drying the obtained cylinder in an oven at 80 ℃ for 24h to obtain the composite material.
Example 2
Polyvinyl butyral (PVB, 0.45g) was added to an ethanol solvent (5.5g) and dissolved by heating (temperature 55 ℃), and then the mixture was slowly dropped (dropping speed 0.05mL/s) into MIL-100(Fe) powder (2.55g), and mixed uniformly with stirring. The mixture was extruded into a cylinder having a cross-sectional diameter of 2mm by means of an extruder. And heating and drying the solid in an oven at 70 ℃ for 18h to obtain the composite material.
Example 3
Polyvinyl butyral (PVB, 0.6g) was added to an ethanol solvent (8g) and dissolved by heating (temperature 60 ℃), and then the mixture was slowly dropped (dropping speed 0.075mL/s) to MIL-100(Fe) powder (2.4g), and mixed well with stirring. The mixture was extruded into a cylinder having a cross-sectional diameter of 3mm by means of an extruder. And heating and drying the solid in an oven at 60 ℃ for 12h to obtain the composite material.
Example 4
Polyvinyl butyral (PVB, 0.15g) was added to an ethanol solvent (2.5g) and dissolved by heating (temperature 65 ℃), and then the mixture was slowly dropped (dropping speed 0.1mL/s) into MIL-100(Fe) powder (2.85g), and mixed uniformly with stirring. The mixture was extruded into a cylinder having a cross-sectional diameter of 5mm by means of an extruder. And heating and drying the solid in an oven at 50 ℃ for 8h to obtain the composite material.
Example 5
Polyvinyl butyral (PVB, 0.9g) was added to an ethanol solvent (9g) and dissolved by heating (temperature 70 ℃), and then the mixture was slowly dropped (dropping speed 0.025mL/s) into MIL-100(Fe) powder (2.1g), and mixed well with stirring. The mixture was extruded into a cylinder having a cross-sectional diameter of 7mm by means of an extruder. And heating and drying the solid in an oven at 90 ℃ for 4h to obtain the composite material.
Example 6
Polyvinyl butyral (PVB, 1.5g) was added to an ethanol solvent (13g), heated and dissolved (temperature 50 ℃), and then the mixture was slowly dropped (dropping speed 0.05mL/s) into MIL-100(Fe) powder (1.5g), and stirred and mixed uniformly. The mixture was extruded into a cylinder having a cross-sectional diameter of 10mm by means of an extruder. And (3) heating and drying the solid in an oven at 100 ℃ for 2h to obtain the composite material.
Comparative example 1
A composite material was prepared according to the method of example 4, except that the MOF was replaced with HKUST-1, and the synthesis method was as follows:
mixing Cu (OH)2(19.5g, 0.2mol) is added into deionized water and stirred evenly; trimesic acid (42g, 0.2mol) was added to ethanol and stirred well. Cu (OH)2The molar ratio of/trimesic acid/deionized water/ethanol was 1:1:50: 40. Mixing Cu (OH)2The aqueous solution of (2) was slowly introduced into an ethanol solution of trimesic acid, and stirred at room temperature for 24 hours. The solid was separated by centrifugation (3500rpm, 20min) and washed twice with absolute ethanol at 60 ℃. The solid is dried in a solid oven at 80 ℃, and the obtained product is the HKUST-1 material used in the examples as proved by X-ray powder diffraction detection (the detection conditions are the same as the preparation example 1).
Example 7
A composite material was prepared as in example 4, except that MIL-100(Fe) powder was slowly added dropwise (dropping rate 0.5g/min) to the mixed solution.
Examples 8 to 13
Composite microsphere materials were prepared according to the methods of examples 1-6, respectively, except that MIL-100(Fe) was replaced with MIL-101 (Fe).
Test example 1
(1) The samples obtained in the examples and comparative examples were subjected to the performance test in the following manner, and the results are shown in table 1:
n of sample of example2The adsorption-desorption curve was measured on a specific surface apparatus of model ASAP2020, McMack USA, evacuated and degassed at 150 ℃ for 12h, weighed and transferred to an analysis station, subjected to N at 77K2Determining an adsorption-desorption isotherm; calculating the specific surface area of the sample by the Brunauer-Emett-Teller (BET) method; by the Barrett-Joyner-Halenda (BJH) methodThe pore size distribution of the sample was calculated. The average particle size is determined by the sieving method.
And (3) measuring the adsorption isotherm of the benzene series (benzene and toluene) of the sample by using an intelligent gravimetric analyzer (IGA-003) and calculating the saturated adsorption quantity of the benzene series per gram of the sample. The specific operation process is as follows: firstly, weighing about 50mg of sample, activating for 3h at 150 ℃, and then placing the activated sample in a processed quartz glass vessel. Measuring a benzene series adsorption isotherm of the sample at 298K, wherein the saturated adsorption quantity of the benzene series per gram of the sample is calculated by the following formula:
wherein W (g) is mass after saturation adsorption of the adsorbent, W0(g) For the initial mass of the sample after activation, Q (mg/g) is the saturated adsorption per gram of sample.
N of composite sample obtained in example 32The adsorption-desorption isotherms are shown in FIG. 1, and N is found in the composite sample obtained in example 92The adsorption-desorption isotherm is shown in figure 2.
The volume (crush) strength of the composite was determined by a frictionless piston test: a cylindrical container (internal diameter 3cm) was placed with a pellet of composite material. The piston then exerts a mechanical force by gravity, which is increased by increasing the weight on the piston until the particles collapse. The compressive strength of the individual particles is expressed as the weight they can withstand before crushing and the average of 10 measurements is calculated and the results are shown in table 1.
In the composite material obtained in the example, the MOF is supported in the associated structure generated by the polymer, and the scanning electron micrograph of the composite material obtained in the example 5 is shown in fig. 4. Scanning Electron Microscopy (SEM) images were collected using a FEITeneo SEM instrument at an accelerating voltage of 5-20 kv. All samples were deposited on a carbon ribbon and covered with a 7 nm thick layer of iridium prior to imaging.
(2) The activated carbon was subjected to the performance test in the same manner as in (1), and the results are shown in Table 1, N of the activated carbon2The adsorption-desorption curve is shown in FIG. 3.
TABLE 1
Comparing the test results of examples 1 to 4 with examples 5 to 6 or (examples 8 to 11 with examples 12 to 13) it can be seen that controlling the weight ratio between the polyvinyl butyral and the iron-based metal organic framework material, etc., within the preferred ranges enables to obtain composites with better adsorption properties.
Comparing the examples with comparative example 1, it can be seen that only by combining the polymer with the iron-based metal organic framework material, a composite material with the best overall performance can be obtained.
Test example 2
(1) A sample to be treated containing a light hydrocarbon (specifically composed of ethane) was contacted with the composite materials obtained in example 1 and comparative example 1, and the ethane adsorption amount of the sample was measured by the following method: the ethane adsorption test is carried out by adopting a specific surface instrument of American Mack company ASAP2020, about 500mg of sample is firstly vacuumized and degassed at 150 ℃ for 12h, the sample is transferred to an analysis station after being reweighed, the adsorption-desorption curve is measured under the pressure range of 298K and ethane 0-2bar, and the maximum ethane adsorption quantity of the sample in the pressure range can be obtained from the curve. The saturated adsorption amount of ethane was 68ml/g for the sample of example 1, and 152ml/g for the sample of comparative example 1. It can be seen from the results in Table 1 that the composite material of the present invention is particularly suitable for adsorbing benzene series.
Further experiments show that the composite material has stable skeleton structure, and has stronger thermal stability and chemical stability. Specifically, the composite material is heated in air at 200 ℃ for 24 hours, is placed in air at room temperature for more than 12 months, and is subjected to specific surface area and pore size analysis and test, so that the structural parameters are basically unchanged.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the individual specific technical features in any suitable way. The invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (13)
1. A composite material is characterized by comprising a polymer and an iron-based metal organic framework material, wherein the weight ratio of the polymer to the iron-based metal organic framework material is 1: (1-25), wherein the polymer is polyvinyl butyral and/or polyvinyl acetal.
2. The composite material of claim 1, wherein the weight ratio between the polymer and the iron-based metal organic framework material is 1: (4-20).
3. The composite material according to claim 1 or 2, wherein the weight average molecular weight of the polymer is 40000-120000;
and/or the iron-based metal organic framework material is selected from MIL-100(Fe) and/or MIL-101 (Fe).
4. The composite material according to any one of claims 1 to 3, wherein the specific surface area of the composite material is 700-3000m2(ii)/g, the pore size distribution is 2-2.8nm, the average particle diameter is 1-10mm, preferably 1-3mm, the benzene vapor saturation adsorption amount is 300-1200mg/g, and the toluene vapor saturation adsorption amount is 250-1100 mg/g.
5. A method of making a composite material, the method comprising: mixing a polymer and an iron-based metal organic framework material for extrusion molding, wherein the polymer and the iron-based metal organic framework material are used in an amount that the weight ratio of the polymer to the iron-based metal organic framework material is 1: (1-25), wherein the polymer is polyvinyl butyral and/or polyvinyl acetal.
6. The method of claim 5, wherein the polymer and the iron-based metal organic framework material are used in amounts such that the weight ratio between the polymer and the iron-based metal organic framework material is 1: (4-20).
7. The method as claimed in claim 5 or 6, wherein the weight average molecular weight of the polymer is 40000-120000;
and/or the iron-based metal organic framework material is selected from MIL-100(Fe) and/or MIL-101 (Fe).
8. The method of claim 5, wherein the polymer is mixed with the iron-based metal organic framework material in the form of a solution;
preferably, the concentration of polymer in the solution is 4-11 wt%, preferably 5-8 wt%;
preferably, the solvent in the solution is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-pentanol, benzyl alcohol, butanol, diacetone alcohol, propylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol propyl ether, acetone, methyl ethyl ketone, cyclohexanone, dichloromethane, chloroform, methyl acetate, ethyl acetate, butyl acetate and acetic acid.
9. The method of claim 8, wherein the solution is additively mixed with the iron-based metal organic framework material at a drop rate of 0.025-0.7mL/s per gram of iron-based metal organic framework material.
10. A composite material obtainable by the process of any one of claims 5 to 9.
11. A method for removing benzene series, which is characterized by comprising the following steps: contacting a sample to be treated containing benzene series with the composite material of any one of claims 1 to 4 and 10;
alternatively, a composite material is prepared according to the method of any one of claims 5 to 9, and then a sample to be treated containing a benzene series is contacted with the resulting composite material.
12. The method according to claim 11, wherein the composite is used in an amount of 0.5-2g per gram of the sample to be treated, expressed as benzene series;
preferably, the conditions of the contacting include: the temperature is 15-40 ℃.
13. Use of a composite material according to any one of claims 1 to 4 and 10 or a method according to any one of claims 5 to 9 for adsorbing benzene-based compounds.
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