CN115532240A - For CO 2 Trapped novel composite materials and methods of making the same - Google Patents

For CO 2 Trapped novel composite materials and methods of making the same Download PDF

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CN115532240A
CN115532240A CN202211139211.4A CN202211139211A CN115532240A CN 115532240 A CN115532240 A CN 115532240A CN 202211139211 A CN202211139211 A CN 202211139211A CN 115532240 A CN115532240 A CN 115532240A
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mof
biomass
composite material
solution
trapped
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朱刚
张旭鹏
雷洪
席雪东
李凯钱
张朝岭
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Southwest Forestry University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
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    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract

The invention discloses a method for preparing CO 2 A novel trapped composite material and a preparation method thereof, relating to the technical field of gas separation. The preparation method specifically comprises the following steps: the method comprises the following steps that firstly, the surface of a biomass matrix is chemically modified to obtain the biomass matrix with an active surface, and then the biomass matrix is immersed in a metal salt solution for synthesizing the MOF material; and step two, after the modified biomass base is fully infiltrated by the metal ions, adding an organic ligand solution for synthesizing the MOF material, and further loading MOF particles on the modified biomass base according to the synthesis process of the MOF to obtain the MOF/biomass base material. The invention adopts a simple and easy method with low cost to prepare the environment-friendly MOF/organismThe biomass-based surface modified by the biomass-based aminated composite material is easy to load MOF nanoparticles, the crystal morphology is kept well, the composite material has a large amount of microporous structures and high porosity, and the adsorption ratio is high.

Description

For CO 2 Trapped novel composite materials and methods of making the same
Technical Field
The invention belongs to the technical field of gas separation, and particularly relates to a method for separating CO 2 A captured novel composite material and a preparation method thereof.
Background
In recent years, the greenhouse gas CO 2 The global temperature is continuously raised, and great challenges are brought to the living environment of human beings. Under the background that the 'double-carbon' target of carbon peak reaching and carbon neutralization is formulated in China, the carbon capture and sequestration (CCUS) technology has great significance for realizing the target. Current plant to post combustion CO 2 The collecting means of (2) is generally a solvent absorption method, a membrane separation method, a cryogenic distillation method, an adsorption separation method or the like. Wherein the adsorption separation method has the advantages of low regeneration energy consumption, simple and convenient operation and the like in CO 2 There is considerable interest in capture technology. The MOF material is a physical adsorption material with stable performance, but the MOF material is difficult to form due to the self particle property, the performance is seriously reduced in practical application, and the MOF material is difficult to recover; industrial separation of CO from amine solvent for chemical adsorption 2 The reaction rate is high, the stability is good, however, the loss of the absorbent is serious, and the regeneration energy consumption is high.
The invention provides a preparation technology of a novel composite material aiming at inherent defects of MOF materials and chemical amine reagents in a carbon capture link, MOF particles are loaded on a biomass matrix and are aminated, so that novel CO is obtained 2 And (4) trapping the composite material.
Disclosure of Invention
The invention aims to provide a method for using CO 2 The trapped novel composite material and the preparation method thereof solve the problems of difficult operation, difficult recovery, serious loss of amine absorbent and high regeneration energy consumption of the existing MOF material.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a method for preparing CO 2 Trapped byThe novel composite material specifically comprises the following raw materials required by production of the composite material:
the method comprises the following steps of a biomass matrix, a metal salt solution for synthesizing the MOF material, an organic ligand solution for synthesizing the MOF material and an amine reagent.
For CO 2 A process for the preparation of a trapped novel composite material, said process comprising in particular the steps of:
the method comprises the following steps that firstly, the surface of a biomass matrix is chemically modified to obtain the biomass matrix with an active surface, and then the biomass matrix is immersed in a metal salt solution for synthesizing the MOF material;
step two, after the metal ions fully infiltrate the modified biomass base, adding an organic ligand solution for synthesizing the MOF material, and further loading MOF particles on the modified biomass base according to the synthesis process of the MOF to obtain an MOF/biomass base material;
dissolving an amine reagent in a proper solvent to prepare an amine solution with a certain concentration, immersing the MOF/biomass-based material in the step one in the solution, and completing amination treatment under certain conditions;
step four, washing and drying to obtain the MOF/biomass-based aminated composite material capable of reacting on CO 2 And (4) collecting.
Preferably, the biomass matrix in the first step is one of balsa wood, poplar, fir wood, basswood, bamboo, cotton, sugarcane, shaddock peel, straw and wood aerogel.
Preferably, the chemical modification method in the first step comprises treatment means such as Tempo (2, 6-tetramethylpiperidine nitroxide free radical) mediated oxidation, naOH alkalization, carboxylation and the like, and the chemical modification process has the temperature of 10-100 ℃, the pH of 2-14 and the time of 4-48h.
Preferably, the metal salt solution for synthesizing the MOF in the first step includes a solution prepared from acetate, nitrate, sulfate or chloride salt of Cu, mg, zn, cr, co, ce, ni or Zr; in the second step, the organic ligand solution is a solution prepared from terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2, 5-diamino terephthalic acid, trimesic acid, pyromellitic acid, dimethyl imidazole and the like, and the solvent is N, N-Dimethylformamide (DMF), methanol, ethanol, deionized water and the like.
Preferably, in the step one, the method for fully infiltrating the modified biomass base in the metal salt solution for synthesizing the MOF comprises vacuum impregnation, mechanical stirring, ultrasonic dispersion, microwave heating and the like, wherein the infiltration process is performed for 1-24 hours at a temperature of 10-150 ℃.
Preferably, the preparation process of the MOF/biomass-based material in the second step comprises an in-situ growth method and a solvothermal method, wherein the reaction temperature of the in-situ growth method is 10-200 ℃, the pH value is 2-12, and the reaction time is 1-72h; the reaction temperature of the solvothermal method is 100-200 ℃, the pH is 2-12, and the reaction time is 1-72h.
Preferably, the amine reagent in step three comprises 3- (2-aminoethylamino) propyl methyl dimethoxy silane (APS), ethylenediamine (EDA), ethanolamine (MEA), diethylamine (DEA), etc., the solvent comprises ethanol, t-butanol, n-hexane, deionized water, etc., and the amine solution is prepared at a concentration of 1-10wt%.
Preferably, the amination process in the third step is carried out at the temperature of 10-100 ℃, the pH value of 2-7 and the time of 10-48h, the amination process is washed for 1-5 times by deionized water, and the drying method in the fourth step is freeze drying, the temperature is-30 to-70 ℃ and the time of 1-24h.
The invention has the following beneficial effects:
1. the invention adopts a simple and easy method with low cost to prepare the environment-friendly biomass-based surface modified by the MOF/biomass-based aminated composite material, the MOF/biomass-based aminated composite material is easy to load MOF nano particles, the crystal morphology is kept well, the composite material has a large amount of microporous structures and higher porosity, and the adsorption ratio is high.
2. The preparation method has simple requirements and simple and feasible process, and can be used for preparing CO 2 Has great potential in trapping application, good mechanical performance, repeatability and flexible operability for novel industrial CO 2 The adsorbent material is of critical importance.
3. The invention is directed to novel CO 2 The research on the adsorption separation of the adsorption material and other gases has great significance and application value.
Of course, it is not necessary for any product to achieve all of the above advantages at the same time in the practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM image of an APS/MOF-199/Tempo-ized wood aerogel composite;
FIG. 2 is DEA/UiO-66/Tempo wood aerogel composite and EDA/ZIF-8/Tempo wood composite vs. CO 2 Adsorption isotherm of (2).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "upper", "middle", "outer", "inner", "lower", "around", and the like, indicate an orientation or positional relationship for the convenience of description and simplicity of description, but do not indicate or imply that the referenced components or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus are not to be construed as limiting the present invention.
Referring to FIGS. 1-2, the present invention is a method for CO 2 The novel captured composite material specifically comprises the following raw materials required by the production of the composite material:
the method comprises the following steps of a biomass matrix, a metal salt solution for synthesizing the MOF material, an organic ligand solution for synthesizing the MOF material and an amine reagent.
For CO 2 The preparation method of the trapped novel composite material specifically comprises the following steps:
the method comprises the following steps that firstly, the surface of a biomass matrix is chemically modified to obtain the biomass matrix with an active surface, and then the biomass matrix is immersed in a metal salt solution for synthesizing the MOF material;
step two, after the metal ions fully infiltrate the modified biomass base, adding an organic ligand solution for synthesizing the MOF material, and further loading MOF particles on the modified biomass base according to the synthesis process of the MOF to obtain an MOF/biomass base material;
dissolving an amine reagent in a proper solvent to prepare an amine solution with a certain concentration, immersing the MOF/biomass-based material in the step one in the solution, and completing amination treatment under certain conditions;
step four, washing and drying to obtain the MOF/biomass-based aminated composite material capable of reacting on CO 2 And (4) collecting.
Further, the biomass matrix in the first step is one of balsa wood, poplar, cedar, basswood, bamboo, cotton, sugarcane, shaddock peel, straw and wood aerogel.
Further, the chemical modification method in the first step comprises treatment means such as Tempo (2, 6-tetramethyl piperidine nitroxide free radical) mediated oxidation, naOH alkalization, carboxylation and the like, wherein the temperature of the chemical modification process is 10-100 ℃, the pH value is 2-14, and the time is 4-48h.
Further, the metal salt solution for synthesizing the MOF in the first step comprises a solution prepared from acetate, nitrate, sulfate or chloride of Cu, mg, zn, cr, co, ce, ni or Zr; in the second step, the organic ligand solution is a solution prepared from terephthalic acid, 2, 5-dihydroxy terephthalic acid, 2, 5-diamino terephthalic acid, trimesic acid, pyromellitic acid, dimethyl imidazole and the like, and the solvent is N, N-Dimethylformamide (DMF), methanol, ethanol, deionized water and the like.
Further, the method for fully soaking the modified biomass base in the metal salt solution for synthesizing the MOF in the step one comprises vacuum impregnation, mechanical stirring, ultrasonic dispersion, microwave heating and the like, wherein the soaking process is carried out for 1-24 hours at the temperature of 10-150 ℃.
Further, the preparation process of the MOF/biomass-based material in the second step comprises an in-situ growth method and a solvothermal method, wherein the reaction temperature of the in-situ growth method is 10-200 ℃, the pH value is 2-12, and the reaction time is 1-72 hours; the reaction temperature of the solvothermal method is 100-200 ℃, the pH is 2-12, and the reaction time is 1-72h.
Further, in the third step, the amine reagent comprises 3- (2-aminoethylamino) propyl methyl dimethoxy silane (APS), ethylenediamine (EDA), ethanolamine (MEA), diethylamine (DEA) and the like, the solvent comprises ethanol, tert-butanol, n-hexane, deionized water and the like, and the amine solution is prepared to have a concentration of 1-10wt%.
Further, the temperature of the amination process in the third step is 10-100 ℃, the pH value is 2-7, the time is 10-48h, the amination process is washed for 1-5 times by deionized water, and the drying method in the fourth step is freeze drying, the temperature is-30 to-70 ℃, and the time is 1-24h.
The first embodiment is as follows:
referring to FIG. 1, 10g of block-shaped balsawood aerogel was placed in a 0.8wt% TEMPO mediated oxidation solution system at a pretreatment temperature of 60 ℃ for 48 hours. Immersing the obtained biomass matrix in a copper acetate solution for synthesizing MOF-199, fully soaking copper ions in the solution for 12 hours, and adding a trimesic acid ligand solution, wherein the solvents are DMF, ethanol and H 2 O, volume ratio 1:1: and 1, further carrying out reaction according to an in-situ growth method, wherein the temperature is room temperature, the pH value is controlled to be 6.8, and the time is 24 hours. And immersing the obtained material into an APS-containing tert-butyl alcohol aqueous solution with the concentration of 6.9wt%, adjusting the pH value to be 4, treating for 4 hours at 90 ℃, washing for 4 times by using deionized water, and freeze-drying for 24 hours at-50 ℃ to obtain the APS/MOF-199/Tempo wood aerogel composite material. The specific surface area of the material is 90.02m 2 Per g, to CO at atmospheric ambient conditions 2 The adsorption capacity of (2) was 2.1mmol/g.
The SEM image of the obtained APS/MOF-199/Tempo-modified wood aerogel sample is shown in FIG. 1, and it can be seen from FIG. 1 (a) that a large amount of MOF-199 nanoparticles are loaded in the lumen of the Tempo-mediated oxidized wood aerogel, and an organic unity in the shape of a 'coral reef' is formed. As can be seen from fig. 1 (b), the MOF-199 particles in the composite material have a size of about 250nm and uniform particle size, and present a clear polyhedral structure, providing a certain mechanical support for the tubular microporous structure of the wood aerogel, and more interestingly, a large amount of nanofibers can be seen on the tubular surface of the wood aerogel through Tempo-mediated oxidation, and present a random interlaced network structure, which may be the result of APS amination.
Example two:
10g of blocky sugarcane aerogel is put into NaOH solution with the concentration of 15wt% for pretreatment, the temperature is room temperature, and the time is 6 hours. Immersing the obtained modified biomass base into a tetrahydrate magnesium acetate salt solution for synthesizing Mg-MOF-74, fully soaking magnesium ions in the solution by mechanical stirring for 4 hours, adding a 2, 5-dihydroxyterephthalic acid ligand solution, wherein the solvents are DMF, ethanol and H 2 O, volume ratio 2:1:1, further carrying out reaction according to a solvothermal synthesis method, wherein the temperature is 125 ℃, the pH value is controlled to be 6, and the reaction time is 24h. And then soaking the composite material into an ethanol solution containing EDA, wherein the concentration is 10wt%, adjusting the pH value to be buffered to 4.8, vigorously stirring for 4h at room temperature, washing for 6 times by using deionized water, and freeze-drying for 36h at-60 ℃ to obtain the EDA/Mg-MOF-74/sugarcane aerogel composite material. The specific surface area of the material is 105.26m 2 Per g, at 50 ℃ and 5bar for CO 2 The adsorption capacity of (A) was 3.3mmol/g.
Example three:
10g of blocky balsawood is put into a 1.0wt% Tempo mediated oxidation solution system for pretreatment, the modification temperature is 60 ℃, and the time is 48 hours. Immersing the obtained modified biomass base into a zinc nitrate hexahydrate solution for synthesizing MOF-5, performing ultrasonic dispersion at 100 ℃ for 6 hours to fully soak zinc ions, and then adding a terephthalic acid ligand solution, wherein the solvents are DMF and H 2 O, volume ratio 2:1, further carrying out reaction according to a solvothermal synthesis method, wherein the temperature is 120 ℃, the pH value is controlled to be 6.8, and the reaction time is 24 hours. Then immersed in an ethanol solution containing EDA at a concentration of 10wt%, and buffered by adjusting pHAnd 4.8, vigorously stirring for 6h at room temperature, washing with deionized water for 6 times, and freeze-drying for 24h at-65 ℃ to obtain the EDA/MOF-5/Tempo modified balsawood composite material. The specific surface area of the material is 70.63m 2 Per g, at 80 ℃ and 10bar for CO 2 The adsorption capacity of (2) was 1.3mmol/g.
Example four:
cotton Nanocelluloses (CNFs) were pretreated using a 0.3wt% Tempo mediated oxidation solution system at 60 ℃ for 48h. Filtering the obtained Tempo cellulose suspension, immersing the solid part into zinc nitrate hexahydrate solution for synthesizing MOF-5 without infiltration, adding terephthalic acid ligand solution, wherein the solvents are DMF and H 2 O, volume ratio 2:1, further carrying out the reaction according to a solvothermal synthesis method, wherein the temperature is 120 ℃, the pH value is controlled to be 6.8, and the time is 48h. And after washing and filtering, immersing the membrane into an ethanol solution containing EDA, adjusting the pH value to be 4.8, violently stirring for 6h at room temperature, washing for 4 times, carrying out vacuum filtration on filter paper, and freeze-drying for 24h at-50 ℃ to obtain the EDA/MOF-5/Tempo-CNFs membrane composite material. The specific surface area of the material is 120.30m 2 Per g, at 0 ℃ and 1bar for CO 2 The adsorption capacity of (B) was 2.1mmol/g.
Example five:
10g of blocky balsawood aerogel is put into a 0.8wt% Tempo mediated oxidation solution system for pretreatment, the temperature is controlled at 60 ℃, the pH value is 6.8, and the time is 48 hours. And step two, putting the obtained modified biomass base into a zirconium chloride metal salt solution for synthesizing UiO-66, soaking for 2 hours, adding a terephthalic acid ligand solution, wherein the solvents are DMF and glacial acetic acid, and further reacting according to a solvothermal synthesis method, wherein the temperature is 120 ℃, the pH is controlled to be 4, and the time is 24 hours. Then, the solution is immersed into an ethanol solution containing DEA, the concentration is 10 weight percent, the pH value is adjusted to be buffered to 4.8, the solution is vigorously stirred for 6 hours at room temperature, and after washing and drying, the DEA/UiO-66/Tempo wood aerogel composite material is obtained. The specific surface area of the material is 45.35m 2 Per g, for CO under atmospheric conditions 2 The adsorption capacity of the adsorbent was 3.05cm3/g.
Example six:
10g of blocky balsawood aerogel is put into a 0.8wt% Tempo mediated oxidation solution system for pretreatment, the temperature is controlled at 60 ℃, the pH value is 6.8, and the time is 48 hours. And (2) putting the obtained modified biomass base into zinc nitrate hexahydrate metal salt solution for synthesizing ZIF-8, fully soaking zinc ions in the zinc nitrate hexahydrate metal salt solution by mechanical stirring for 24 hours, adding dimethyl imidazole ligand solution, taking methanol as a solvent, further carrying out mechanical stirring according to an in-situ synthesis method, and reacting at room temperature, with the pH value controlled to be 6.8 and the time controlled to be 24 hours. And then soaking the wood aerogel composite material into an ethanol solution containing EDA, adjusting the concentration to 10wt%, adjusting the pH value to be buffered to 4.8, violently stirring for 6h at room temperature, washing for 3 times by using deionized water, and drying at the temperature of-65 ℃ to obtain the EDA/ZIF-8/Tempo wood aerogel composite material. The specific surface area of the material is 60.73m 2 Per g, at 0 ℃ and 1bar for CO 2 The adsorption capacity of the adsorbent was 5.68cm3/g.
Example seven:
10g of bamboo blocks are put into ammonium persulfate solution with the concentration of 22.8wt% for carboxylation treatment, the modification temperature is 60 ℃, and the time is 4 hours. Immersing the obtained modified bamboo wood matrix into a chromium nitrate salt solution for synthesizing NH2-Cr-MOF-101, heating for 3H by microwave to fully infiltrate chromium ions, adding a 2, 5-diamino terephthalic acid ligand solution, wherein the solvents are DMF, ethanol and H 2 O, volume ratio 3:1:1, further carrying out the reaction according to a solvothermal synthesis method, wherein the temperature is 120 ℃, the pH value is 6, and the time is 24 hours. Then immersing the bamboo fiber into a solution containing ethanolamine (MEA) with the concentration of 6.9wt%, adjusting the pH value to be buffered to 4, reacting for 4h at the temperature of 90 ℃, washing for 3 times by deionized water, and drying to obtain the MEA/NH 2-Cr-MOF-101/bamboo composite material. The specific surface area of the material is 58.06m 2 Per g, to CO at atmospheric ambient conditions 2 The adsorption capacity of (2) was 0.9mmol/g.
As can be seen from FIG. 2, two composites prepared by the present invention are directed to CO 2 The adsorption of the two materials has a certain effect, the adsorption isotherms of the two materials almost all present a direct proportion straight line, the adsorption quantity is gradually improved along with the increase of the pressure intensity, and the adsorption behavior does not exist under the condition of the standard atmospheric pressure of the same temperatureThe surface is stable and has a large upward space.
In conclusion, the biomass matrix is chemically modified to create a good environment for the growth of the MOF particles, a stable MOF/biomass-based composite structure is constructed, and then amination treatment is performed on the stable MOF/biomass-based composite structure, so that the amine/MOF/biomass-based composite material is prepared, and the material not only inherits the porous characteristics of the MOF and the biomass material, but also has good mechanical properties of the biomass matrix and excellent carbon dioxide capturing performance of the MOF material and amine groups, and has great application potential in the carbon capturing stage in the CCUS technology.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand the invention for and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (9)

1. For CO 2 The captured novel composite material is characterized by specifically comprising the following raw materials required by production of the composite material:
the method comprises the following steps of a biomass matrix, a metal salt solution for synthesizing the MOF material, an organic ligand solution for synthesizing the MOF material and an amine reagent.
2. For CO 2 A method for preparing a trapped novel composite material, characterized in that the method specifically comprises the steps of:
the method comprises the following steps of firstly, carrying out chemical modification on the surface of a biomass matrix to obtain the biomass matrix with an active surface, and then immersing the biomass matrix into a metal salt solution for synthesizing the MOF material;
step two, after the modified biomass base is fully infiltrated by the metal ions, adding an organic ligand solution for synthesizing the MOF material, and further loading MOF particles on the modified biomass base according to the synthesis process of MOF to obtain an MOF/biomass base material;
dissolving an amine reagent in a proper solvent to prepare an amine solution with a certain concentration, immersing the MOF/biomass-based material in the step one in the solution, and completing amination treatment under certain conditions;
step four, washing and drying to obtain the MOF/biomass-based aminated composite material capable of reacting on CO 2 And (4) collecting.
3. A process for CO according to claim 2 2 The preparation method of the trapped novel composite material is characterized by comprising the following steps: the biomass matrix in the first step is one of balsa wood, poplar, fir, basswood, bamboo, cotton, sugarcane, shaddock peel, straw and wood aerogel.
4. A process for CO according to claim 2 2 A method for preparing a trapped novel composite material, characterized in that: the chemical modification method in the first step comprises the treatment means of Tempo (2, 6-tetramethyl piperidine nitroxide free radical) mediated oxidation, naOH alkalization, carboxylation and the like, and the temperature of the chemical modification process is 10-100 ℃, the pH value is 2-14, and the time is 4-48h.
5. A process for CO according to claim 2 2 The preparation method of the trapped novel composite material is characterized by comprising the following steps: the metal salt solution for synthesizing the MOF in the first step comprises metalIs a solution prepared by acetate, nitrate, sulfate or chloride of Cu, mg, zn, cr, co, ce, ni or Zr; in the second step, the organic ligand solution is a solution prepared from terephthalic acid, 2, 5-dihydroxyterephthalic acid, 2, 5-diaminoterephthalic acid, trimesic acid, pyromellitic acid, dimethyl imidazole and the like, and the solvent is N, N-Dimethylformamide (DMF), methanol, ethanol, deionized water and the like.
6. A process for CO according to claim 2 2 The preparation method of the trapped novel composite material is characterized by comprising the following steps: in the first step, the method for fully soaking the modified biomass base in the metal salt solution for synthesizing the MOF comprises vacuum impregnation, mechanical stirring, ultrasonic dispersion, microwave heating and the like, wherein the soaking process is carried out for 1-24 hours at the temperature of 10-150 ℃.
7. A process for CO according to claim 2 2 The preparation method of the trapped novel composite material is characterized by comprising the following steps: the preparation process of the MOF/biomass-based material in the second step comprises an in-situ growth method and a solvothermal method, wherein the reaction temperature of the in-situ growth method is 10-200 ℃, the pH value is 2-12, and the reaction time is 1-72h; the reaction temperature of the solvothermal method is 100-200 ℃, the pH value is 2-12, and the reaction time is 1-72h.
8. Use for CO according to claim 2 2 The preparation method of the trapped novel composite material is characterized by comprising the following steps: the amine reagent in the third step comprises 3- (2-aminoethylamino) propyl methyl dimethoxy silane (APS), ethylenediamine (EDA), ethanolamine (MEA), diethylamine (DEA) and the like, the solvent comprises ethanol, tert-butyl alcohol, normal hexane, deionized water and the like, and the concentration of the prepared amine solution is 1-10wt%.
9. Use for CO according to claim 2 2 A method for preparing a trapped novel composite material, characterized in that: the temperature of the amination process in the third step is 10-100 ℃, the pH value is 2-7, the time is 10-48h, deionized water is used for washing for 1-5 times, and drying is carried out in the fourth stepThe method comprises freeze drying at-30 deg.C to-70 deg.C for 1-24 hr.
CN202211139211.4A 2022-09-19 2022-09-19 For CO 2 Trapped novel composite materials and methods of making the same Pending CN115532240A (en)

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103372420A (en) * 2012-04-20 2013-10-30 南京理工大学 Metal organic frameworks (MOFs)-amine modified/oxidized graphite composite material and preparation method thereof
CN104056598A (en) * 2014-06-20 2014-09-24 浙江大学 MOFs based carbon dioxide adsorbent, preparation method and application thereof
CN108745417A (en) * 2018-04-17 2018-11-06 东华大学 A kind of cellulose/UiO-66-NH2Porous material and its preparation and application
CN108786755A (en) * 2018-05-30 2018-11-13 浙江大学 A kind of metal organic frame-porous polymer composite material and preparation method of organic amine load and application
CN112959446A (en) * 2021-02-01 2021-06-15 国际竹藤中心 Metal organic framework/wood composite material and preparation method and application thereof
CN113083243A (en) * 2021-04-06 2021-07-09 南京林业大学 Wood-based CO2Preparation method of adsorbing material
CN113831749A (en) * 2021-10-21 2021-12-24 西南林业大学 Preparation method of double MOF/biomass-based multifunctional composite material
CN113842790A (en) * 2021-09-28 2021-12-28 太原理工大学 Based on intercalation type montmorillonite/Cu3(BTC)2Mixed matrix membrane of composite material and preparation method and application thereof
WO2022040072A1 (en) * 2020-08-17 2022-02-24 Susteon Inc. Co2 capture sorbents with low regeneration temperature and high desorption rates
CN114225910A (en) * 2021-12-06 2022-03-25 桂林理工大学 Aminated modified Co-MOFs material with NO adsorption separation performance
CN114375224A (en) * 2019-06-19 2022-04-19 韩国科学技术院 Structured metal-organic framework fiber adsorbents for carbon dioxide capture and methods of making same
CN114797798A (en) * 2022-04-14 2022-07-29 中国科学院青岛生物能源与过程研究所 Preparation method and application of MOF/corn straw composite material and device
CN114849665A (en) * 2022-04-29 2022-08-05 浙江大学 Amino metal organic framework adsorbent capable of adsorbing carbon dioxide in air and preparation and application thereof

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103372420A (en) * 2012-04-20 2013-10-30 南京理工大学 Metal organic frameworks (MOFs)-amine modified/oxidized graphite composite material and preparation method thereof
CN104056598A (en) * 2014-06-20 2014-09-24 浙江大学 MOFs based carbon dioxide adsorbent, preparation method and application thereof
CN108745417A (en) * 2018-04-17 2018-11-06 东华大学 A kind of cellulose/UiO-66-NH2Porous material and its preparation and application
CN108786755A (en) * 2018-05-30 2018-11-13 浙江大学 A kind of metal organic frame-porous polymer composite material and preparation method of organic amine load and application
CN114375224A (en) * 2019-06-19 2022-04-19 韩国科学技术院 Structured metal-organic framework fiber adsorbents for carbon dioxide capture and methods of making same
WO2022040072A1 (en) * 2020-08-17 2022-02-24 Susteon Inc. Co2 capture sorbents with low regeneration temperature and high desorption rates
CN112959446A (en) * 2021-02-01 2021-06-15 国际竹藤中心 Metal organic framework/wood composite material and preparation method and application thereof
CN113083243A (en) * 2021-04-06 2021-07-09 南京林业大学 Wood-based CO2Preparation method of adsorbing material
CN113842790A (en) * 2021-09-28 2021-12-28 太原理工大学 Based on intercalation type montmorillonite/Cu3(BTC)2Mixed matrix membrane of composite material and preparation method and application thereof
CN113831749A (en) * 2021-10-21 2021-12-24 西南林业大学 Preparation method of double MOF/biomass-based multifunctional composite material
CN114225910A (en) * 2021-12-06 2022-03-25 桂林理工大学 Aminated modified Co-MOFs material with NO adsorption separation performance
CN114797798A (en) * 2022-04-14 2022-07-29 中国科学院青岛生物能源与过程研究所 Preparation method and application of MOF/corn straw composite material and device
CN114849665A (en) * 2022-04-29 2022-08-05 浙江大学 Amino metal organic framework adsorbent capable of adsorbing carbon dioxide in air and preparation and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHENNAN WANG ET AL: "Strong Foam-like Composites from Highly Mesoporous Wood and Metal-Organic Frameworks for Efficient CO2 Capture", 《ACS APPLIED MATERIALS & INTERFACES》, vol. 13, pages 29949 - 29959 *

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