CN114100580A - Composite material with light hydrocarbon adsorption function, preparation method thereof, method for removing light hydrocarbon by using composite material and application - Google Patents
Composite material with light hydrocarbon adsorption function, preparation method thereof, method for removing light hydrocarbon by using composite material and application Download PDFInfo
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- CN114100580A CN114100580A CN202010904777.6A CN202010904777A CN114100580A CN 114100580 A CN114100580 A CN 114100580A CN 202010904777 A CN202010904777 A CN 202010904777A CN 114100580 A CN114100580 A CN 114100580A
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Images
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
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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
- 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
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- 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)
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- 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 hydrocarbon by using the composite material and application thereof. 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 selected from at least one of polyvinyl formal, polypropylene, polyphenylsulfone and polyamide. The composite material has the advantages of stable skeleton structure, high mechanical stability, large pore volume, pore diameter and specific surface area, high light hydrocarbon adsorption capacity, simple and environment-friendly preparation method, low price of synthetic raw materials, 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 with a light hydrocarbon adsorption function, a preparation method thereof, a method for removing light hydrocarbon by using the composite material and application thereof.
Background
With the increasing importance of the country on environmental protection, the emission standard of the atmospheric pollutants related to the refining industry and oil storage reservoirs becomes stricter. The refining industry and oil storage reservoirs mainly adopt an adsorption process to recover oil gas, and commonly used adsorption materials comprise activated carbon, silica gel and the like. And the problem that present oil gas recovery exists is mainly that the micromolecular hydrocarbon is difficult to be adsorbed and is got rid of, gets among the present oil gas recovery unit active carbon, silica gel adsorption material promptly and is better to macromolecule VOCs's adsorption effect, but is not good enough to micromolecular VOCs's adsorption effect. Therefore, aiming at non-methane light hydrocarbon (C) in oil gas2-C4) The development of efficient adsorption materials is carried out, and the method has important significance for solving the problem that light hydrocarbons are difficult to adsorb and recover in the existing oil gas recovery and meeting the increasingly strict discharge standard of VOCs.
Metal Organic Frameworks (MOFs) as a new porous material with specific surface area and pore volume up to 10000m, respectively2G and 4.40cm3In addition, the structural diversity and tunability of MOFs materials allows for their use in gas adsorption and separation,Has wide application prospect in the fields of catalysis, sensing, medicine 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. The specific surface area and pore volume of the MOFs material are destroyed by the particles prepared by the simple MOFs material through an extrusion method or a pressurization method.
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 difficult light hydrocarbon adsorption and recovery and collapse of porous material frameworks and pore canals and great reduction of specific surface area and pore volume in the pressure molding method of an adsorption material in the prior art, and provides a composite material, a preparation method thereof and a method for removing light hydrocarbon by using the composite material.
In order to achieve the above object, one aspect of the present invention provides a composite material with light hydrocarbon adsorption function, the composite material 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.
In the invention, the copper-based metal organic framework material is loaded (dispersed and wrapped) in an association structure formed by a polymer to form the composite material, the composite material has a stable skeleton 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.
A second aspect of the invention provides a method of making a composite material, the method comprising: mixing a polymer and a copper-based metal organic framework material under conditions that allow the polymer to undergo intramolecular 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.
In a third aspect of the present invention, there is provided a composite material obtained by the above-mentioned production method.
In the fourth aspect of the invention, a method for removing light hydrocarbon by using the composite material is provided, wherein a sample to be treated containing light hydrocarbon is contacted with the 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 a reversed-phase solvent water or alcohol, and forming the MOF-polymer composite material by utilizing intramolecular and intermolecular association reaction of a hydrophobic organic polymer in the water or alcohol.
The sample to be treated containing light hydrocarbon is contacted 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 that the effect of removing the light hydrocarbon is better.
In a fifth aspect of the invention, the composite material or the preparation method thereof is applied to light hydrocarbon adsorption.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) compared with traditional adsorbing materials such as activated carbon and the like, the composite material provided by the invention has large specific surface area and higher light hydrocarbon adsorption capacity;
(2) the composite material provided by the invention has the advantages of simple preparation method and stable framework structure; solves the problems of collapse of the skeleton and the pore canal, and great reduction of the specific surface area and the pore volume in the existing powder pressure forming method.
(3) The composite material provided by the invention is cheap in synthetic raw materials and easy to produce and apply on a large scale.
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 adsorption isotherm (77K) of an activated carbon material;
FIG. 3 is a scanning electron micrograph of a composite material obtained according to an embodiment of the present invention;
fig. 4 is an ethane sorption isotherm diagram of a composite obtained according to an embodiment of the 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 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 selected from at least one of polyvinyl formal, polypropylene, polyphenylsulfone and polyamide.
Association refers to the phenomenon of bonding by means of weaker bonding forces (e.g., coordinate covalent bonds, hydrogen bonds) without causing a change in chemical properties between the same or different molecules. "association structure" means a network structure formed by bonding within or between the polymer molecules by means of weak bonding force (such as coordinate covalent bond, hydrogen bond). In water and the like, the hydrophobic groups of the polymer used in the present invention aggregate due to hydrophobic interaction, causing intramolecular and intermolecular association of macromolecular chains.
In the present invention, the source of the polymer is not particularly limited, and it can be obtained commercially or by self-preparation using the prior art, for example, polyvinyl formal is obtained by acetalization of polyvinyl alcohol with formaldehyde in the presence of an acidic catalyst, or polyvinyl acetate is dissolved in acetic acid or alcohol, and is hydrolyzed and acetalized with formaldehyde in the presence 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 by commercial or 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 for reaction, 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, in advance before the contact reaction is performed. Wherein the molar ratio of the copper source, the trimesic acid, the water and the ethanol is 1:0.5-3:40-60:30-50 in terms of Cu. The copper source may be a common substance capable of providing copper ions, preferably copper hydroxide. The conditions of the contacting may include: the temperature is 20-40 deg.C, and the time is 15-30 h. 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 terms of Cu at room temperature, reacting the mixed solution at 20-40 ℃ for 15-30h, and separating solids (centrifuging at a rotation speed of 2000-4000rpm for 10-30 min). Washing with absolute ethyl alcohol at 50-70 deg.c, and drying at 70-90 deg.c to obtain HKUST-1 material. Wherein, the copper source can be mixed with water in advance to obtain a mixed solution A, the trimesic acid can be mixed with ethanol in advance to obtain a mixed solution B, and the mixed solution A is slowly introduced into the mixed solution B when the copper source is contacted with the ethanol.
In the present invention, preferably, the weight ratio between the polymer and the copper-based metal organic framework material is 1: (4-10), for example, 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 700-3000m2(ii) in terms of/g. Preferably, the pore size distribution of the composite material is 0.6-0.9 nm. Preferably, the composite material has an average particle size of 2 to 2.5 mm. Preferably, the ethane saturation adsorption capacity of the composite material is 80-180 mL/g. Preferably, the propane saturation adsorption capacity of the composite material is 80-160 mL/g. Preferably, the butane saturation adsorption capacity of the composite material is 70-150 mL/g.
A second aspect of the invention provides a method of making a composite material, the method comprising: mixing a polymer and a copper-based metal organic framework material under conditions that allow the polymer to undergo intramolecular 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.
In the invention, the polymer and the copper-based metal organic framework material are used in such amounts that the weight ratio of the polymer to the copper-based metal organic framework material is 1: (4-10), for example, 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 40000-100000.
In the present invention, preferably, the copper-based metal organic framework material is selected from HKUST-1
In the present invention, preferably, the mixing conditions 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 phase solvent is not limited as long as it can cause aggregation of the hydrophobic organic polymer in the reverse phase solvent due to hydrophobic interaction, and cause intramolecular and intermolecular association reaction of the macromolecular chains, and preferably, the reverse phase solvent is selected from water and/or ethanol, and according to a preferred embodiment of the present invention, the reverse phase solvent is a mixed solvent of water and ethanol. Further preferably, the volume ratio of water to ethanol is 1:0.5 to 10, and more preferably 1:0.5 to 3. The amount of the reverse phase solvent used is not particularly limited as long as it is capable of forming an association structure with the polymer, and may be such that the ratio of the amount of the polymer to the amount of the reverse phase solvent used may be (0.2 to 2 g): 100mL, preferably (0.3-0.6 g): 100 mL.
In the present invention, preferably, the mixing manner is: the polymer is premixed with the copper-based metal organic framework material in the form of a solution at 50 to 100 ℃, more preferably 60 to 80 ℃, and the resulting premix is added to the reverse phase solvent (the addition rate of the premix is 0.025 to 0.2mL/s relative to 100mL of the reverse phase solvent), and is allowed to stand for 0.5 to 6 hours, more preferably 1 to 2 hours, after the addition is finished.
In the present invention, it is preferable that the concentration of the polymer in the solution is 20 to 60g/L, preferably 40 to 50 g/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 present invention, in the method, the solvent may be mixed with the polymer under heating in order to dissolve the polymer, and the heating temperature may be 50 to 100 ℃, preferably 60 to 80 ℃.
In the present invention, the method may further comprise the steps of washing and drying. The washing mode has no special requirement, and the organic solvent in the composite material can be replaced by repeatedly soaking the composite material for 2 to 5 times by water (preferably deionized water), the polymer in the composite material can be promoted to be completely associated further, and the composite material can be replaced by soaking the composite material for 2 to 5 times by ethanol. The drying method is not particularly limited, and a natural airing method or a drying method using a drying apparatus may be used.
In the present invention, in order to make the polymers in the mixed solution fully associate to form uniform MOF/polymer particles, the time for the obtained composite material to stand in the reverse phase solvent after the addition is completed is preferably 0.5 to 6 hours, more preferably 1 to 2 hours.
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 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 is preferably 0.5 to 2g per gram of the sample to be treated in terms of light hydrocarbon.
Preferably, the conditions of the contacting include: the temperature is 15-40 ℃.
The composite material of the invention is particularly suitable for adsorbing light hydrocarbons which can be various common light hydrocarbons, in particular C2-C4For example, ethane, propane, butane, etc. The sample to be treated containing light hydrocarbon can be oil gas produced by refining industry and/or oil storage.
In the invention, in order to fully 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 light hydrocarbon 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 formal (Shanghai Michelin Biochemical technology, Ltd., weight average molecular weight 70000); activated charcoal (Henan Zheng Zhou bamboo forest activated charcoal development Co., Ltd.); room temperature means "25 ℃; soaking in deionized water for 30 min/time; soaking in anhydrous ethanol for 60 min/time.
Preparation example 1
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 proved by 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.
Example 1
Polyvinyl formal (PVFM, 0.3g) was added to DMF organic solvent (6ml) and heated to 60 deg.C to dissolve it and stir it well, HKUST-1 material (2.7g) was added and stirred well. And (2) dropwise adding the MOF-polymer mixed solution into 100mL of reverse phase solvent deionized water/ethanol mixed solution (volume ratio is 1:2) at room temperature (dropwise adding speed is 0.1mL/s), standing the formed composite material in the reverse phase solvent for 1h, soaking the composite material for 3 times by using fresh deionized water (50mL), finally soaking the composite material for 2 times by using absolute ethyl alcohol (50mL), and airing to obtain the composite material.
Example 2
Polyvinyl formal (PVFM, 0.45g) is added into DMF organic solvent (10ml), heated and dissolved at 70 ℃ and stirred uniformly, HKUST-1 material (2.55g) is added and stirred uniformly. And (2) dropwise adding the MOF-polymer mixed solution into 100mL of reverse phase solvent deionized water/ethanol mixed solution (volume ratio is 2:1) at room temperature (dropwise adding speed is 0.075mL/s), standing the formed composite material in the reverse phase solvent for 1.5h, soaking the composite material for 3 times by using fresh deionized water (50mL), finally soaking the composite material for 2 times by using absolute ethyl alcohol (50mL), and airing to obtain the composite material.
Example 3
Polyvinyl formal (PVFM, 0.6g) was added to DMF organic solvent (12ml) and heated to 80 deg.C to dissolve and stir well, HKUST-1 material (2.4g) was added and stirred well. And (2) dropwise adding the MOF-polymer mixed solution into 100mL of reverse phase solvent deionized water/ethanol mixed solution (volume ratio is 5:4) at room temperature (dropwise adding speed is 0.05mL/s), standing the formed composite material in the reverse phase solvent for 2 hours, soaking the composite material for 3 times by using fresh deionized water (50mL), finally soaking the composite material for 2 times by using absolute ethyl alcohol (50mL), and airing to obtain the composite material.
Example 4
Polyvinyl formal (PVFM, 0.9g) was added to DEF organic solvent (30ml), heated to 90 deg.C to dissolve and stir well, and HKUST-1 material (2.1g) was added and stirred well. And (3) dropwise adding the MOF-polymer mixed solution into 100mL of reverse phase solvent ethanol at room temperature (the dropwise adding speed is 0.025mL/s), standing the formed composite material in the reverse phase solvent for 3 hours, soaking the composite material for 3 times by using fresh deionized water (50mL), finally soaking the composite material for 2 times by using absolute ethyl alcohol (50mL), and airing to obtain the composite material.
Example 5
Polyvinyl formal (PVFM, 1.5g) is added into DMF organic solvent (25ml), heated and dissolved at 100 ℃ and stirred uniformly, HKUST-1 material (1.5g) is added and stirred uniformly. And (2) dropwise adding the MOF-polymer mixed solution into 100mL of reverse phase solvent deionized water/ethanol mixed solution (volume ratio is 1:9) at room temperature (dropwise adding speed is 0.05mL/s), standing the formed composite material in the reverse phase solvent for 1h, soaking the composite material for 3 times by using fresh deionized water (50mL), finally soaking the composite material for 2 times by using absolute ethyl alcohol (50mL), and airing to obtain the composite material.
Comparative example 1
A composite was prepared as in example 1 except that the polymer was replaced with polyethersulfone (PES A-101, Suwei, USA, 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 MIL-100(Fe) was prepared as follows:
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 centrifuged. The solid was washed with N, N-Dimethylformamide (DMF), deionized water, ethanol, respectively. Heating and activating the solid in a vacuum oven at 150 ℃ for 12h, and testing by X-ray powder diffraction to prove that the obtained product is the MIL-100(Fe) material.
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; the pore size distribution of the samples was calculated by the Barrett-Joyner-Halenda (BJH) method. The average particle size is determined by the sieving method.
N of composite sample obtained in example 32The adsorption-desorption isotherms are shown in figure 1.
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 4 is shown in fig. 3. Scanning Electron Microscope (SEM) images were collected using a FEI Teneo SEM instrument at 5-20kv acceleration voltage. All samples were deposited on a carbon ribbon and covered with a 7 nm thick layer of iridium prior to imaging.
The samples of the examples were tested for their adsorption-desorption curves on a specific surface apparatus of model ASAP2020, mck usa, degassed under vacuum at 150 ℃ for 12h, weighed and transferred to an analysis station, and subjected to adsorption-desorption curve measurements at 298K in the pressure range of 0-2bar for ethane and propane, from which the maximum adsorption of the sample in this pressure range was obtained. The isotherm diagram of the ethane adsorption of the composite obtained in example 1 is shown in fig. 4.
(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. 2.
TABLE 1
Comparing the test results of examples 1 to 3 with those of examples 4 to 5, it can be seen that the composite material with better adsorption performance can be obtained by controlling the weight ratio between the polyvinyl formal and the copper-based metal organic framework material and other parameters within the preferred range.
Comparing the examples with comparative examples 1-2, it can be seen that only by combining specific polymers with iron-based metal organic framework materials can composite materials with optimal overall properties be obtained.
Test example 2
(1) A sample to be treated containing a benzene series (specifically, benzene) was brought into contact with the composite materials 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 for benzene were determined for the samples of example 1 and comparative example 1 using an intelligent gravimetric analyzer (IGA-003) and the saturated adsorption of benzene per gram of sample was calculated. 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. 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 645 mg/g. It can be seen from the results in table 1 that the composite material of the present invention is particularly suitable for adsorbing light hydrocarbons.
Further experiments show that the composite material has stable skeleton structure, and has stronger thermal stability and chemical stability. Specifically, the material is heated in air at 250 ℃ for 24h, 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, and 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. The composite material with the light hydrocarbon adsorption function 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.
2. The composite material according to claim 1, wherein the weight ratio between the polymer and the copper-based metal organic framework material is 1: (4-10).
3. The composite material according to claim 1 or 2, wherein the weight average molecular weight of the polymer is 40000-100000;
and/or, the copper-based metal organic framework material is selected from HKUST-1.
4. The composite material according to any one of claims 1 to 3, wherein the specific surface area of the composite material is 700-2000m2The specific adsorption capacity of the catalyst is as follows, the pore size distribution is 0.6-0.9nm, the average particle diameter is 2-2.5mm, the saturated adsorption capacity of ethane is 80-180mL/g, the saturated adsorption capacity of propane is 80-160mL/g, and the saturated adsorption capacity of butane is 70-150 mL/g.
5. A method of making a composite material, the method comprising: mixing a polymer and a copper-based metal organic framework material under conditions that allow the polymer to undergo intramolecular 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.
6. The method of claim 5, 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: (4-10).
7. The method according to claim 5 or 6, wherein the weight average molecular weight of the polymer is 40000-100000;
and/or, the copper-based metal organic framework material is selected from HKUST-1.
8. The method of claim 5, wherein the conditions of the mixing include a temperature of 50-100 ℃, preferably 60-80 ℃; the time is 0.5-6h, preferably 1-2 h.
9. The method of claim 5, wherein the mixing is by: premixing the polymer and the copper-based metal organic framework material in the form of solution at 50-100 ℃, preferably 60-80 ℃, adding the obtained premix into a reverse phase solvent, wherein the adding speed of the premix is 0.025-0.2mL/s relative to 100mL of the reverse phase solvent, and standing for 0.5-6h, preferably 1-2h after the addition is finished;
preferably, the concentration of the polymer in the solution is 20-60g/L, preferably 40-50 g/L;
preferably, the solvent in the solution is selected from N, N-dimethylformamide and/or N, N-diethylformamide;
preferably, the reverse phase solvent is selected from water and/or ethanol, more preferably in a volume ratio of 1: 0.5-10 parts of a mixed solvent of water and ethanol.
10. A composite material obtainable by the process of any one of claims 5 to 9.
11. A method for removing light hydrocarbons, the method comprising: contacting a sample to be treated containing a light hydrocarbon with the composite material of any one of claims 1-4 and 10;
alternatively, a composite material is prepared according to the method of any one of claims 5 to 9, and the sample to be treated containing a light hydrocarbon is then contacted with the resulting composite material.
12. The method according to claim 11, wherein the amount of composite material is between 0.5 and 2g per gram of sample to be treated, calculated as light hydrocarbons;
preferably, the conditions of the contacting include: the temperature is 15-40 ℃.
13. Use of the composite material according to any one of claims 1-4 and 10 or the process according to any one of claims 5-9 for adsorbing light hydrocarbons.
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| CN114849651A (en) * | 2022-05-11 | 2022-08-05 | 中山大学 | Activated carbon packaged carboxylic acid metal organic framework composite material, preparation thereof and gas adsorption separation application |
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