CN114100580B - Composite material with light hydrocarbon adsorption function, preparation method thereof, method for removing light hydrocarbon by using composite material and application of composite material - Google Patents
Composite material with light hydrocarbon adsorption function, preparation method thereof, method for removing light hydrocarbon by using composite material and application of composite material Download PDFInfo
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- CN114100580B CN114100580B CN202010904777.6A CN202010904777A CN114100580B CN 114100580 B CN114100580 B CN 114100580B CN 202010904777 A CN202010904777 A CN 202010904777A CN 114100580 B CN114100580 B CN 114100580B
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- 239000002131 composite material Substances 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 43
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 42
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 42
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 63
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- 239000013084 copper-based metal-organic framework Substances 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 15
- 239000004952 Polyamide Substances 0.000 claims abstract description 7
- 229920000491 Polyphenylsulfone Polymers 0.000 claims abstract description 7
- 239000004743 Polypropylene Substances 0.000 claims abstract description 7
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- -1 polypropylene Polymers 0.000 claims abstract description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 69
- 239000002904 solvent Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 13
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- 239000002245 particle Substances 0.000 claims description 7
- 239000001294 propane Substances 0.000 claims description 5
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- 239000002184 metal Substances 0.000 claims description 4
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- 239000001273 butane Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
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- 230000008569 process Effects 0.000 claims description 3
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- 235000019441 ethanol Nutrition 0.000 description 21
- 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
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 238000002791 soaking Methods 0.000 description 14
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- 238000006243 chemical reaction Methods 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000002336 sorption--desorption measurement Methods 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000013291 MIL-100 Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- 239000004695 Polyether sulfone Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 238000000748 compression moulding Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000007873 sieving Methods 0.000 description 1
Classifications
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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
- 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
-
- 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
-
- 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
-
- 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
- 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
- B01J20/32—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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the field of material synthesis, and discloses a composite material with a light hydrocarbon adsorption function, a preparation method thereof, a method for removing light hydrocarbons by using the composite material and application of the composite material. The composite material comprises an association structure formed by a polymer and a copper-based metal-organic framework material loaded in the association structure, wherein the weight ratio of the polymer to the copper-based metal-organic framework material is 1: (1-15) the polymer is at least one selected from the group consisting of polyvinyl formal, polypropylene, polyphenylsulfone and polyamide. The composite material has stable skeleton structure, strong mechanical stability, large pore volume, large pore diameter and large specific surface area, and high light hydrocarbon adsorption capacity, and the preparation method of the composite material is simple and environment-friendly, and the synthetic raw materials are low in cost and easy to produce and apply on a large scale.
Description
Technical Field
The invention relates to the field of material synthesis, in particular to a composite material with a light hydrocarbon adsorption function, a preparation method thereof, a method for removing light hydrocarbons by using the composite material and application of the composite material.
Background
With the increasing emphasis of the national environmental protection, the emission standards of atmospheric pollutants for refining industry and oil reservoirs are becoming more and more strict. The refining industry and the oil storage warehouse mainly adopt an adsorption process to recycle oil gas, and common adsorption materials include active carbon, silica gel and the like. The existing problems of oil gas recovery are mainly that small molecular hydrocarbons are difficult to adsorb and remove, namely, the adsorption effect of activated carbon and silica gel adsorption materials obtained in the existing oil gas recovery device on macromolecular VOCs is better, but the adsorption effect on the small molecular VOCs is poor. Thus, for non-methane light hydrocarbons (C) 2 -C 4 ) Development of high-efficiency adsorption materials is developed, and the method has important significance for solving the problem that light hydrocarbons are difficult to adsorb and recover in the prior oil gas recovery and meeting the stricter and stricter VOCs emission standards.
Metal Organic Frameworks (MOFs) as novel porous materials with specific surface areas and pore volumes up to 10000m respectively 2 /g and 4.40cm 3 In addition, the MOFs material has wide application prospect in the fields of gas adsorption and separation, catalysis, sensing, medicine separation and the like due to structural diversity and adjustability.
Currently, scientists' research on MOFs materials is mainly focused on the design and synthesis of new structures, and it is reported that > 6000 new structures of MOFs materials are produced each year. However, since most MOFs materials are synthesized on a scale of mainly small amounts (from milligrams to several grams) and are usually in powder form, the industrial scale application of MOFs materials in the fields of adsorption separation, catalysis, etc. is limited. Particles prepared by extrusion or compression of simple MOFs materials can damage the specific surface area and pore volume of MOFs materials.
For this reason, the existing technology for preparing MOFs materials needs to be further improved.
Disclosure of Invention
The invention aims to solve the technical problems that the light hydrocarbon is difficult to adsorb and recycle and the porous material skeleton and pore canal collapse and the specific surface area and pore volume are greatly reduced in the compression molding method of the adsorption material in the prior art, and provides a composite material, a preparation method thereof and a method for removing the light hydrocarbon by using the composite material.
In order to achieve the above object, the present invention provides, in one aspect, a composite material having a light hydrocarbon adsorbing function, the composite material comprising an association structure formed of a polymer and a copper-based metal-organic framework material supported in the association structure, wherein a weight ratio between the polymer and the copper-based metal-organic framework material is 1: (1-15) the polymer is at least one selected from the group consisting of polyvinyl formal, polypropylene, polyphenylsulfone and polyamide.
In the invention, the copper-based metal organic framework material is loaded (dispersed and wrapped) in an association structure formed by the polymer to form the composite material, the composite material has a stable framework structure and stronger mechanical strength, and the composite material has larger pore volume, pore diameter and specific surface area and higher light hydrocarbon adsorption capacity.
In a second aspect, the invention provides a method of preparing a composite material, the method comprising: mixing a polymer and a copper-based metal-organic framework material under conditions that cause the polymer to undergo intramolecular association and/or intermolecular association, wherein the polymer and the copper-based metal-organic framework material are used in amounts such that the weight ratio between the polymer and the copper-based metal-organic framework material is 1: (1-15) the polymer is at least one selected from the group consisting of polyvinyl formal, polypropylene, polyphenylsulfone and polyamide.
In a third aspect of the present invention, there is provided a composite material produced by the above-described production method.
In a fourth aspect of the present invention, there is provided a method for removing light hydrocarbons using the above-described composite material, wherein a sample to be treated containing light hydrocarbons is contacted with the above-described composite material; or preparing the composite material by adopting the method, and then contacting the sample to be treated containing light hydrocarbon with the obtained composite material.
The method for preparing the composite material provided by the invention comprises the steps of firstly dissolving a polymer in a solvent, then adding a copper-based metal organic framework material to obtain a mixed solution, then adding the mixed solution into water or alcohol which is an anti-phase solvent, and utilizing the hydrophobic organic polymer to generate intramolecular and intermolecular association reaction in the water or alcohol to form the MOF-polymer composite material.
The invention contacts the sample to be treated containing light hydrocarbon with the composite material to adsorb the light hydrocarbon in the sample to be treated, and the composite material has higher light hydrocarbon adsorption capacity, so the effect of removing the light hydrocarbon is better.
In a fifth aspect of the invention, the application of the composite material or the preparation method thereof in light hydrocarbon adsorption is provided.
In summary, the beneficial effects of the present invention compared with the prior art are as follows:
(1) Compared with the traditional adsorption materials such as active carbon, the composite material provided by the invention has large specific surface area and higher light hydrocarbon adsorption capacity;
(2) The preparation method of the composite material provided by the invention is simple, and the skeleton structure is stable; solves the problems of collapse of the framework and the pore canal and great reduction of the specific surface area and the pore volume existing in the existing powder compression molding method.
(3) The composite material provided by the invention has low cost of synthetic raw materials and is easy for large-scale production and application.
Drawings
FIG. 1 is a nitrogen adsorption isotherm (77K) of a composite material obtained in accordance with one embodiment of the present invention;
FIG. 2 is a nitrogen adsorption isotherm (77K) of an activated carbon material;
FIG. 3 is a scanning electron micrograph of a composite material obtained according to one embodiment of the invention;
FIG. 4 is an ethane adsorption isotherm plot of a composite obtained in accordance with one embodiment of the invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In one aspect, the invention provides a composite material with a light hydrocarbon adsorption function, which comprises an association structure formed by a polymer and a copper-based metal-organic framework material loaded in the association structure, wherein the weight ratio of the polymer to the copper-based metal-organic framework material is 1: (1-15) the polymer is at least one selected from the group consisting of polyvinyl formal, polypropylene, polyphenylsulfone and polyamide.
Association (association) refers to the phenomenon that the same or different molecules do not cause a change in chemical properties, but rely on weaker bonding forces (e.g., coordinate covalent bonds, hydrogen bonds) to bond, without causing a change in covalent bonds. An "associative structure" is a network structure formed by the intramolecular or intermolecular bonding of the polymer by weak bond forces (e.g., coordinate covalent bonds, hydrogen bonds). In a solution such as water, hydrophobic groups of the polymer used in the present invention aggregate due to hydrophobic action, and the macromolecular chains are associated intramolecularly and intermolecularly.
In the present invention, the source of the polymer is not particularly limited and may be commercially available or prepared by itself using the prior art, for example, polyvinyl formal is obtained by acetalizing polyvinyl alcohol with formaldehyde in the presence of an acidic catalyst, or polyvinyl acetate is dissolved in acetic acid or alcohol and hydrolyzed and acetalized with formaldehyde under the action of an acidic catalyst. The weight average molecular weight of the polymer is preferably 40000-100000.
In the present invention, the copper-based metal-organic framework material may be obtained commercially or by self-preparation, and preferably, the copper-based metal-organic framework material is preferably selected from HKUST-1. In a solvent, a copper source is contacted with trimesic acid to react, and the obtained solid after the reaction is washed and dried in sequence. Preferably, the copper source is dissolved in a solvent, which may be water (preferably deionized water) and ethanol, prior to the contact reaction. Wherein the mol ratio of the copper source, trimesic acid, water and ethanol is 1:0.5-3:40-60:30-50 based on Cu. The copper source may be a common substance capable of providing copper ions, preferably copper hydroxide. The contacting conditions may include: the temperature is 20-40 ℃ and the time is 15-30h. The washing conditions may include: the temperature is 50-70 ℃. The drying conditions may include: the temperature is 70-90 ℃. More specifically, the method for self-preparing HKUST-1 is as follows: uniformly stirring a copper source, trimesic acid, water and ethanol according to a molar ratio of 1:0.5-3:40-60:30-50 in the room temperature, reacting the mixed solution at 20-40 ℃ for 15-30h, and separating solids (centrifuging at a rotating speed of 2000-4000rpm for 10-30 min). Washing with absolute ethyl alcohol at 50-70 ℃, and drying at 70-90 ℃ to obtain the HKUST-1 material used in the invention. The copper source can be mixed with water in advance to obtain a mixed solution A, and trimesic acid can be mixed with ethanol in advance to obtain a mixed solution B, and when the mixed solution A is contacted with ethanol, the mixed solution A is slowly introduced into the mixed solution B.
In the present invention, preferably, the weight ratio between the polymer and the copper-based metal organic frame material is 1: (4-10), e.g., 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, or any value therebetween.
In the present invention, preferably, the specific surface area of the composite material is 700 to 3000m 2 And/g. Preferably, the pore size distribution of the composite material is 0.6-0.9nm. Preferably, the composite material has an average particle size of 2-2.5mm. Preferably, the composite material has an ethane saturation adsorption amount of 80-180mL/g. Preferably, the composite material has a propane saturation adsorption amount of 80-160mL/g. Preferably butane of the composite materialThe saturated adsorption quantity is 70-150mL/g.
In a second aspect, the invention provides a method of preparing a composite material, the method comprising: mixing a polymer and a copper-based metal-organic framework material under conditions that cause the polymer to undergo intramolecular association and/or intermolecular association, wherein the polymer and the copper-based metal-organic framework material are used in amounts such that the weight ratio between the polymer and the copper-based metal-organic framework material is 1: (1-15) the polymer is at least one selected from the group consisting of polyvinyl formal, polypropylene, polyphenylsulfone and polyamide.
In the invention, the polymer and the copper-based metal organic framework material are used in an amount such that the weight ratio between the polymer and the copper-based metal organic framework material is 1: (4-10), e.g., 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, or any value therebetween.
In the present invention, preferably, the weight average molecular weight of the polymer is 40000 to 100000.
In the present invention, preferably, the copper-based metal organic framework material is selected from HKUST-1
In the present invention, preferably, the conditions of the mixing include a temperature of 50 to 100 ℃, more preferably 60 to 80 ℃; the mixing conditions also preferably include: the time is 0.5 to 6 hours, more preferably 1 to 2 hours.
The kind of the reverse solvent is not limited as long as it can cause aggregation of the hydrophobic organic polymer in the reverse solvent due to the hydrophobic effect, and cause intramolecular and intermolecular association reaction of the macromolecular chains, and preferably, the reverse solvent is selected from water and/or ethanol, and according to a preferred embodiment of the present invention, the reverse solvent is a mixed solvent of water and ethanol. Further preferably, the volume ratio of water to ethanol is 1:0.5 to 10, more preferably 1:0.5 to 3. There is no particular requirement for the amount of the anti-phase solvent, as long as it enables the polymer to form an association structure, so that the ratio of the amount of the polymer to the amount of the anti-phase solvent may be (0.2-2 g): 100mL, preferably (0.3-0.6 g): 100mL.
In the present invention, preferably, the mixing means is: the polymer is premixed with the copper-based metal organic framework material in the form of a solution at 50-100 c, more preferably 60-80 c, and the resulting premix is added to the reverse solvent (the addition rate of the premix is 0.025-0.2mL/s relative to 100mL of reverse solvent), and left to stand for 0.5-6h, more preferably 1-2h after the addition is completed.
In the present invention, the concentration of the polymer in the solution is preferably 20 to 60g/L, preferably 40 to 50g/L.
In the present invention, the kind of 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 N, N-Dimethylformamide (DMF) and/or N, N-diethylformamide.
In the method of the present invention, in order to dissolve the polymer, the solvent may be mixed with the polymer under heating conditions, and the heating temperature may be 50 to 100 ℃, preferably 60 to 80 ℃.
In the present invention, the method may further include washing and drying steps. The washing mode is not particularly required, and the water in the composite material can be replaced by repeatedly soaking the composite material in water (preferably deionized water) for 2-5 times to replace the organic solvent in the composite material and promote the polymer in the composite material to be further associated completely and then soaking the composite material in ethanol for 2-5 times. The drying mode is not particularly limited, and a natural drying or drying mode by a drying device can be adopted.
In the present invention, in order to sufficiently associate the polymers in the mixed solution to form uniform MOF/polymer particles, it is preferable that the resulting composite material is left to stand in the reverse phase solvent for a period of 0.5 to 6 hours, more preferably 1 to 2 hours, after the completion of the addition.
In a third aspect of the present invention, there is provided a composite material produced by the above-described production method.
In a fourth aspect of the present invention, there is provided a method for removing light hydrocarbons using the above composite material, comprising contacting a sample to be treated containing light hydrocarbons with the above composite material; or preparing the composite material by adopting the method, and then contacting the sample to be treated containing light hydrocarbon with the obtained composite material.
In the present invention, the amount of the composite material is not particularly limited, and preferably the amount of the composite material is 0.5 to 2g per gram of the sample to be treated in terms of light hydrocarbon.
Preferably, the contacting conditions include: the temperature is 15-40 ℃.
The composite material is particularly suitable for adsorbing light hydrocarbons, and the light hydrocarbons can be various common light hydrocarbons, in particular C 2 -C 4 For example, ethane, propane, butane, etc. The sample to be treated containing light hydrocarbon can be oil gas generated by refining industry and/or an oil storage warehouse.
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 characteristic of the material to the greatest extent, the method further comprises activating the composite material before contacting with the sample to be treated, wherein the activating condition can comprise the temperature of 140-160 ℃ and the activating time can be 2-5h.
In a fifth aspect of the invention, the application of the composite material or the preparation method thereof in light hydrocarbon adsorption is provided.
The present invention will be described in detail by examples.
The reagents used in the examples and comparative examples are shown below: polyvinyl formal (weight average molecular weight 70000, shanghai Meilin Biochemical technologies Co., ltd.); activated carbon (Henan Zhengzhou bamboo forest activated carbon development Co., ltd.); room temperature refers to "25 ℃; the deionized water soaking time is 30 min/time; the soaking time of the absolute ethyl alcohol is 60 min/time.
Preparation example 1
Cu (OH) 2 (19.5 g,0.2 mol) added into deionized water and stirred uniformly; trimesic acid (42 g,0.2 mol) was added to ethanol and stirred well. Cu (OH) 2 The molar ratio of trimesic acid/deionized water/ethanol is 1:1:50:40. Cu (OH) 2 Slowly introducing the aqueous solution of (2) into an ethanol solution of trimesic acid, and stirring at room temperature for 24 hours. The solid was separated by centrifugation (3500 rpm,20 min) and washed twice with absolute ethanol at 60 ℃. Drying the solid in a drying oven at 80 ℃, and obtaining the product through X-ray powder diffraction detectionThe product was HKUST-1 material used in the examples. The X-ray powder diffraction test conditions were: a Bruker-AXSD8 type X-ray full-automatic diffractometer in Germany is adopted, a light source adopts a radiation source Cu target K alpha 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-20 degrees.
Example 1
Polyvinyl formal (PVFM, 0.3 g) was added to DMF organic solvent (6 ml) and heated at 60℃to dissolve and stir well, HKUST-1 material (2.7 g) was added and stirred well. And (3) dropwise adding the MOF-polymer mixture (dropwise adding speed is 0.1 mL/s) into 100mL of reverse solvent deionized water/ethanol mixed solution (volume ratio is 1:2) at room temperature, standing and maintaining the formed composite material in the reverse solvent for 1h, soaking the composite material in fresh deionized water (50 mL) for 3 times, soaking the composite material in absolute ethyl alcohol (50 mL) for 2 times, and airing the composite material to obtain the composite material.
Example 2
Polyvinyl formal (PVFM, 0.45 g) was added to DMF organic solvent (10 ml) and heated at 70℃to dissolve and stir well, HKUST-1 material (2.55 g) was added and stirred well. And (3) dropwise adding the MOF-polymer mixture (dropwise adding speed is 0.075 mL/s) into 100mL of reverse solvent deionized water/ethanol mixed solution (volume ratio is 2:1) at room temperature, standing the formed composite material in the reverse solvent for 1.5h, soaking the composite material in fresh deionized water (50 mL) for 3 times, soaking the composite material in absolute ethyl alcohol (50 mL) for 2 times, and airing the composite material to obtain the composite material.
Example 3
Polyvinyl formal (PVFM, 0.6 g) was added to DMF organic solvent (12 ml) and heated at 80℃to dissolve and stir well, HKUST-1 material (2.4 g) was added and stirred well. And (3) dropwise adding the MOF-polymer mixture (dropwise adding speed is 0.05 mL/s) into 100mL of reverse solvent deionized water/ethanol mixed solution (volume ratio is 5:4) at room temperature, standing and maintaining the formed composite material in the reverse solvent for 2 hours, soaking the composite material in fresh deionized water (50 mL) for 3 times, soaking the composite material in absolute ethyl alcohol (50 mL) for 2 times, and airing the composite material to obtain the composite material.
Example 4
Polyvinyl formal (PVFM, 0.9 g) was added to DEF organic solvent (30 ml) and heated at 90℃to dissolve and stir well, HKUST-1 material (2.1 g) was added and stirred well. And (3) dropwise adding the MOF-polymer mixture into 100mL of ethanol which is an anti-phase solvent at room temperature (dropwise adding speed is 0.025 mL/s), standing the formed composite material in the anti-phase solvent for 3 hours, soaking the composite material in fresh deionized water (50 mL) for 3 times, soaking the composite material in absolute ethyl alcohol (50 mL) for 2 times, and airing the composite material to obtain the composite material.
Example 5
Polyvinyl formal (PVFM, 1.5 g) was added to DMF organic solvent (25 ml) and heated at 100deg.C to dissolve and stir well, HKUST-1 material (1.5 g) was added and stirred well. And (3) dropwise adding the MOF-polymer mixture (dropwise adding speed is 0.05 mL/s) into 100mL of reverse solvent deionized water/ethanol mixed solution (volume ratio is 1:9) at room temperature, standing and maintaining the formed composite material in the reverse solvent for 1h, soaking the composite material in fresh deionized water (50 mL) for 3 times, soaking the composite material in absolute ethyl alcohol (50 mL) for 2 times, and airing the composite material to obtain the composite material.
Comparative example 1
A composite was prepared as in example 1, except that the polymer was replaced with polyethersulfone (Stuwei, PES A-101, melt index (380 ℃ C./2.16 kg) 13g/10 min).
Comparative example 2
A composite material was prepared as in example 1, except that the HKUST-1 material was replaced with MIL-100 (Fe). The preparation method of MIL-100 (Fe) comprises the following steps:
fe (NO) 3 ) 3 ·9H 2 O (0.03 mol,12 g) and organic ligand trimesic acid (0.02 mol,4.2 g) were added to a reaction flask containing deionized water (80 ml) and stirred well at room temperature. The mixture was transferred to an oil bath and heated at 95 ℃ for 24h. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was centrifuged. The solids were washed with N, N-Dimethylformamide (DMF), deionized water, ethanol, respectively. Heating and activating the solid in a vacuum oven at 150 ℃ for 12 hours, and obtaining a product which is MIL-100 (Fe) material through X-ray powder diffraction detection.
Test example 1
(1) The samples obtained in the examples and comparative examples were subjected to performance tests in the following manner, and the results are shown in table 1:
sample N of the example 2 Adsorption-desorption curves were tested on an ASAP2020 specific surface Instrument from America microphone company, vacuum degassing at 150deg.C for 12h, weighing, transferring to an analysis station, and N-carrying out at 77K 2 Measuring adsorption-desorption isotherms; calculating the specific surface area of the sample by a Brunauer-Emett-Teller (BET) method; the pore size distribution of the samples was calculated by the Barrett-Joyner-Halenda (BJH) method. The average particle size is measured by sieving.
N of the composite sample obtained in example 3 2 Adsorption-desorption isotherms are shown in figure 1.
The volume (crush) strength of the composite was determined by a frictionless piston test: a composite particle was placed in a cylindrical vessel (3 cm inside diameter). The piston then applies a mechanical force by gravity, increasing the mechanical force by increasing the weight on the piston until the particles collapse. The compressive strength of the individual particles was expressed as the weight they can bear before pulverization, and the average of 10 measurements was calculated, and the test results are shown in table 1.
In the composite material obtained in example, MOF is loaded in association structure generated by polymer, and scanning electron microscope photograph of the composite material obtained in example 4 is shown in FIG. 3. Scanning Electron Microscope (SEM) images were acquired using a FEI Teneo SEM instrument at an accelerating voltage of 5-20 kv. All samples were deposited on a carbon tape and covered with a 7 nm thick iridium layer prior to imaging.
The ethane, propane adsorption-desorption curves of the samples of the examples were tested on an ASAP2020 specific surface instrument from America microphone company, vacuum degassing was carried out at 150℃for 12h, after weighing, they were transferred to an analysis station, and the adsorption-desorption curves of the ethane, propane at 298K were determined in a pressure range of 0-2bar, from which the maximum adsorption of the samples in this pressure range was obtained. The composite material obtained in example 1 has an ethane adsorption isotherm diagram shown in fig. 4.
(2) The activated carbon was subjected to performance test in the same manner as in (1), and the results are shown in Table 1, N of the activated carbon 2 The adsorption-desorption curves are shown in fig. 2.
TABLE 1
As can be seen from comparing the test results of examples 1-3 with those of examples 4-5, the composite material having better adsorption performance can be obtained by controlling the weight ratio of the polyvinyl formal to the copper-based metal organic frame material and other parameters within the preferred ranges.
As can be seen from a comparison of examples with comparative examples 1-2, only a combination of specific polymers with an iron-based metal-organic framework material allows a composite material to be obtained with optimal overall properties.
Test example 2
(1) A sample to be treated containing benzene-based compounds (specifically composed of benzene) was brought into contact with the composite material obtained in example 1 and comparative example 1, and the benzene adsorption amount of the sample was measured by the following method: the adsorption isotherms of benzene for the samples of example 1 and comparative example 1 were measured using an intelligent gravimetric analyzer (IGA-003) and the saturated adsorption amount of benzene was calculated for each gram of sample. The specific operation process is as follows: firstly, about 50mg of sample is weighed and activated for 3 hours at 150 ℃, and then the activated sample is placed in a processed quartz glass vessel. And (5) measuring the benzene adsorption isotherm of the sample at 298K, and calculating the benzene saturation adsorption quantity of the material. The benzene saturation adsorption amount of the sample of example 1 was 236mg/g, and the benzene saturation adsorption amount of the sample of comparative example 1 was 645mg/g. As can be seen from the results of table 1, the composite material of the present invention is particularly suitable for adsorbing light hydrocarbons.
As can be seen from further experiments, the composite material has a stable skeleton structure and has high thermal stability and chemical stability. Specifically, the material is heated for 24 hours in the air at 250 ℃, placed for more than 12 months in the air at room temperature, and then subjected to analysis and test of specific surface area and pore diameter, and the structural parameters are basically unchanged.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of individual specific technical features in any suitable way. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition. Such simple variations and combinations are likewise to be regarded as being within the scope of the present disclosure.
Claims (18)
1. A composite material with a light hydrocarbon adsorption function, which is characterized by comprising an association structure formed by a polymer and a copper-based metal-organic framework material loaded in the association structure, wherein the weight ratio of the polymer to the copper-based metal-organic framework material is 1: (1-15) the polymer is selected from at least one of polyvinyl formal, polypropylene, polyphenylsulfone and polyamide;
the specific surface area of the composite material is 700-2000m 2 Per gram, the pore size distribution is 0.6-0.9nm, the average particle diameter is 2-2.5mm, the ethane saturated adsorption capacity is 80-180mL/g, the propane saturated adsorption capacity is 80-160mL/g, and the butane saturated adsorption capacity is 70-150mL/g;
the weight average molecular weight of the polymer is 40000-100000;
the copper-based metal organic framework material is selected from HKUST-1.
2. The composite of claim 1, wherein the weight ratio between the polymer and the copper-based metal-organic framework material is 1: (4-10).
3. A method of making a composite material, the method comprising: mixing a polymer and a copper-based metal-organic framework material under conditions that cause the polymer to undergo intramolecular association and/or intermolecular association, wherein the polymer and the copper-based metal-organic framework material are used in amounts such that the weight ratio between the polymer and the copper-based metal-organic framework material is 1: (1-15) the polymer is selected from at least one of polyvinyl formal, polypropylene, polyphenylsulfone and polyamide;
the weight average molecular weight of the polymer is 40000-100000;
the copper-based metal organic framework material is selected from HKUST-1.
4. A method according to claim 3, wherein the polymer and copper-based metal-organic framework material are used in amounts such that the weight ratio between polymer and copper-based metal-organic framework material is 1: (4-10).
5. A method according to claim 3, wherein the mixing conditions include a temperature of 50-100 ℃ for a time of 0.5-6 hours.
6. The method of claim 5, wherein the mixing conditions comprise a temperature of 60-80 ℃ for a time of 1-2 hours.
7. A method according to claim 3, wherein the mixing is by: premixing the polymer with the copper-based metal organic frame material in the form of a solution at 50-100 ℃, adding the obtained premix into the reverse solvent, wherein the adding speed of the premix is 0.025-0.2mL/s relative to 100mL of the reverse solvent, and standing for 0.5-6h after the adding is finished.
8. The method of claim 7, wherein the mixing is by: premixing the polymer with the copper-based metal organic frame material in the form of a solution at 60-80 ℃, adding the obtained premix into the reverse solvent, wherein the adding speed of the premix is 0.025-0.2mL/s relative to 100mL of the reverse solvent, and standing for 1-2h after the adding is finished.
9. The method of claim 7, wherein the concentration of polymer in the solution is 20-60g/L.
10. The method of claim 9, wherein the concentration of polymer in the solution is 40-50g/L.
11. The method of claim 7, wherein the solvent in the solution is selected from N, N-dimethylformamide and/or N, N-diethylformamide.
12. The method of claim 7, wherein the reverse phase solvent is selected from water and/or ethanol.
13. The method of claim 12, wherein the reverse phase solvent is present in a volume ratio of 1:0.5-10 of water and ethanol.
14. A composite material obtainable by the process of any one of claims 3 to 13.
15. A method for removing light hydrocarbons, the method comprising: contacting a sample to be treated comprising light hydrocarbons with the composite material of any one of claims 1 or 2 and 14;
alternatively, a composite material is prepared according to the method of any one of claims 3-13, and then a sample to be treated containing light hydrocarbons is contacted with the resulting composite material.
16. The method of claim 15, wherein the composite is used in an amount of 0.5-2g per gram of sample to be treated in light hydrocarbons.
17. The method of claim 15, wherein the contacting conditions comprise: the temperature is 15-40 ℃.
18. Use of the composite material of any one of claims 1 or 2 and 14 or the method of any one of claims 3 to 13 for the adsorption of light hydrocarbons.
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