CN115814769A - For CO 2 Trapped ALF composites and methods of making the same - Google Patents
For CO 2 Trapped ALF composites and methods of making the same Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 239000004005 microsphere Substances 0.000 claims abstract description 37
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 10
- 239000007858 starting material Substances 0.000 claims abstract description 8
- 238000003541 multi-stage reaction Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012071 phase Substances 0.000 claims description 63
- 238000002156 mixing Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- -1 polyethylene Polymers 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 229920000428 triblock copolymer Polymers 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 239000003361 porogen Substances 0.000 claims description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 27
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 class 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a method for preparing CO 2 A captured ALF composite material and a preparation method thereof, relating to CO 2 The technical field of trapping. For CO 2 A captured ALF composite having a raw material composition comprising: porous polyacrylate microspheres and ALF raw materials; the ALF starting material includes an ALF metal source and an organic ligand. The preparation method of the ALF composite material comprises the following steps: preparing the porous polyacrylate microspheres embedded with the ALF raw material, and then carrying out a composite reaction to obtain the acrylic microsphere. The ALF composite material provided by the invention can react on CO under the same condition 2 The adsorption capacity is obviously improved, and compared with the prior art, the raw materials used by the preparation method are cheaper and easily obtained, and are effectively controlledThe cost of industrial production is reduced, the preparation process is simple and controllable, the safety coefficient is high, the energy consumption is low, and the method has a wide application prospect.
Description
Technical Field
The invention belongs to CO 2 The technical field of trapping, in particular to a method for trapping CO 2 A captured ALF composite and a method of making the same.
Background
High efficiency CO 2 The capture and storage technology can reduce the environmental impact of fossil fuel use. Post combustion CO 2 The traditional trapping method is a chemical absorption method based on a water-amine solution, but has the problems of thermal degradation, corrosion, oxidation reaction, amine escape and the like. CO capture by physical adsorption 2 The porous solid adsorption material needs less regeneration energy and has huge low-cost CO 2 Trapping potential.
Metal organic frame Al (HCOO) 3 ALF, capable of exhibiting potent CO 2 The adsorption capacity, which shows excellent carbon dioxide selectivity even in the presence of carbon dioxide and nitrogen, and which can absorb carbon dioxide from a dry stream of carbon dioxide at high temperature, is very excellent CO 2 Adsorbing the material.
But it also has its own limitations such as sensitivity to humidity, poor mechanical properties, and especially the preparation of ALF materials using the conventional methods of the prior art does not utilize large-scale industrialization, since ALF is generally present in powder form; after the raw powder is amplified, bonded, molded and processed into industrial products, pore channel blockage and lattice collapse are caused under a high accumulation state, so that the adsorption quantity, selectivity and adsorption/desorption rate of the raw powder are greatly reduced.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for preparing CO 2 A captured ALF composite and a method for preparing the same to solve the above problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
for CO 2 A captured ALF composite having a raw material composition comprising: porous polyacrylate microspheres and ALF raw materials;
the ALF starting material includes an ALF metal source and an organic ligand.
Optionally, the mass percent of the porous polyacrylate microspheres is 40-50%;
preferably, the mass percentage of the ALF metal source is 20-40%;
preferably, the mass percent of the organic ligand is 10-30%.
The porous polyacrylate microspheres are used as a matrix of the composite material, and if the embedded ALF metal source is too little, the growth requirement of ALF raw materials cannot be met, so that the composite material cannot reach high carbon dioxide adsorption capacity; if the quantity of the embedded ALF metal source is too much, the subsequent organic ligand is not favorably entered, so that the load of ALF raw materials is not high, and therefore, the optimization of the raw material proportion has important influence on the performance of the composite material.
Optionally, the ALF metal source includes one or more of aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum oxalate, nano aluminum hydroxide and a dispersion thereof, and nano aluminum oxide and a dispersion thereof.
Optionally, the organic ligand comprises one or more of sodium formate, potassium formate, ammonium formate, formic acid.
A preparation method of the ALF composite material comprises the following steps: preparing the porous polyacrylate microspheres embedded with the ALF raw material, and then carrying out a composite reaction to obtain the acrylic microsphere.
Optionally, the preparation of the porous polyacrylate microspheres embedded with the ALF raw material comprises,
preparation of the first phase: mixing a polyacrylate monomer, an emulsifier, a pore-forming agent and an initiator A;
preparing a second phase: mixing the ALF starting material and water;
preparation of a third phase: mixing the first phase, the second phase and a reducing agent a;
preparation of a fourth phase: mixing an initiator B, a reducing agent B, a dispersing agent and water;
mixing the third phase and the fourth phase, and carrying out polymerization reaction to obtain porous polyacrylate microspheres embedded with ALF raw materials;
preferably, the temperature of the polymerization reaction is 60-70 ℃, and the reaction time is 10-25min.
Preferably, the polymerization is carried out with stirring. A first phase formed by mixing a polyacrylate monomer, an emulsifier, a pore-forming agent and an initiator A is an oil phase, a second phase formed by mixing an ALF raw material and deionized water is a water phase, an aqueous phase dispersion liquid is added into the oil phase, a reducing agent A is added into the oil phase to prepare an emulsion, and an initiator B, a reducing agent B, a dispersing agent and water are mixed to prepare a fourth phase system; and then adding the emulsion into a fourth phase system, forming the emulsion into spherical particles under the action of the tension formed by the oil-water interface of the emulsion and the shear stress formed by the rotation of the stirring paddle, and finishing polymerization at the temperature of 60-70 ℃ to obtain the porous polyacrylate microspheres embedded with the ALF raw material.
Optionally, the polyacrylate monomer comprises one or more of acrylate, glycidyl methacrylate, t-butyl methacrylate, and trimethylolpropane triacrylate.
Optionally, the emulsifier comprises one or more of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P-123), tween and Span 80;
preferably, the porogen comprises toluene;
preferably, the initiator a comprises benzoyl peroxide;
preferably, the reducing agent a comprises N, N-dimethylaniline;
preferably, the initiator B comprises ammonium persulfate;
preferably, the reducing agent B comprises N, N' -tetramethylethylenediamine;
preferably, the dispersant comprises polyvinyl alcohol.
The reaction raw materials selected by the invention are cheap and easily available chemical products, and are favorable for controlling the synthesis cost, simplifying the preparation process and reducing the process conditions, thereby being favorable for industrial popularization and use.
Optionally, the amounts of the raw materials for preparing the first phase are respectively: 50.0-55.0wt.% of acrylate monomer, 3.0-5.0wt.% of emulsifier, 40.0-45.0wt.% of pore-forming agent, 1.0-1.5wt.% of initiator A, 1.0-1.5wt.% of reducing agent A;
preferably, the ALF starting material used to prepare the second phase is present in an amount of from 20 to 60wt% of the solid phase components used to prepare the first phase;
preferably, the amount of water used to prepare the second phase is 80-85vol.% of the volume of the first phase;
preferably, the amounts of the raw materials for preparing the fourth phase are respectively as follows: 0.3-0.5wt.% of initiator B, 0.3-0.5wt.% of reducing agent B, 0.5-1.0wt.% of dispersant, 98.0-98.5wt.% of water.
Optionally, the temperature of the composite reaction is 50-150 ℃, and the time is 18-48h.
Due to the strong hydrophobic property of the porous polyacrylate microsphere skeleton surface and the low water vapor adsorption capacity of the ALF raw material, the invention provides the method for CO 2 The trapped ALF composite material does not need to be subjected to composite material re-hydrophobic modification, so that the complex operation steps are omitted, and the problem of carbon dioxide adsorption performance reduction caused by hydrophobic treatment of the composite material is avoided.
The invention has the beneficial effects that:
the invention provides a method for CO 2 Trapped ALF composites, making full use of the ALF raw material itself for CO 2 The composite material has excellent adsorption capacity and selectivity, and the structural advantages of the porous polyacrylate microspheres are combined, so that the CO content of the composite material is further improved 2 The adsorption performance of (c); and different from the prior art that expensive ligands need to be used, the organic ligands used in the invention are relatively cheaper, and the cost of the ALF composite material is effectively reduced.
According to the preparation method provided by the invention, firstly, the obtained intermediate product is embedded with the porous polyacrylate microspheres of the ALF raw material, the intermediate product has a unique tertiary pore structure, and macropores of the tertiary pore structure provide a growth space of ALF crystals; meanwhile, the interconnection channel among the mesopores, the micropores and the macropores is beneficial to ALF and CO 2 The ALF raw material can be quickly and fully contacted, and the high load rate and uniform dispersion of the ALF raw material in the pores of the porous material polymer can be realized by combining the embedded metal source and the organic ligand mixture, so that the adsorption active sites of the composite material are increased. Then smaller by in-situ growthCrystal of particle size, shortening of CO 2 The diffusion path improves the absorption/desorption efficiency, and the ALF nano-crystals are evenly and orderly anchored in the porous polyacrylate microspheres, so that the stability of the composite material is enhanced, and the service life is prolonged.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 (a) is an electron microscope scanning image of the surface pore structure of the intermediate product PAA-Al (OH) 3-2 prepared in example 2;
FIG. 1 (b) is an electron microscope scan of the internal pore structure of the intermediate product PAA-Al (OH) 3-2 prepared in example 2;
fig. 1 (c) is an electron microscope scanning image of the internal pore structure of the ALF composite prepared in example 2;
FIG. 1 (d) is an electron micrograph of ALF powder as a control;
FIG. 2 is a graph of the ALF composite material prepared in example 2 at 25 ℃ in CO 2 Adsorption isotherm.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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. 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.
Example 1
The method provided by the invention is adopted to prepare the catalyst for CO 2 The trapped ALF composite material comprises the following specific steps:
s1: preparation of a first phase:
mixing acrylate (TBA, 20.0 wt.%), tert-butyl methacrylate (TBMA, 10.0 wt.%), trimethylolpropane triacrylate (TMPTA, 20.0 wt.%), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P-123, 3.0 wt.%), toluene (45.0 wt.%), and benzoyl peroxide (BPO, 2.0 wt.%) in a beaker;
s2: preparation of the second phase:
mixing 1.7g of nano aluminum hydroxide powder and 15ml of deionized water to prepare a second phase;
s3: preparation of a third phase:
adding the second phase prepared in S2 into the first phase prepared in S1, and stirring at 8000rpm for 10min to maintain the stability of the emulsion, and adding N, N-dimethylaniline (DMA, 1.0 wt.%) into the emulsion during stirring;
s4: preparation of a fourth phase:
mixing ammonium persulfate (APS, 0.5 wt.%), N' -tetramethylethylenediamine (TMEDA, 0.5 wt.%), polyvinyl alcohol (PVA, 1 wt.%), and deionized water (98.0 wt.%);
s5: slowly pouring the third phase obtained in the step S3 into a three-neck round-bottom flask containing the fourth phase obtained in the step S4, continuously stirring for 15min at the constant temperature of 65 ℃ to ensure that the emulsion is dispersed into uniform liquid drops, finishing polymerization, and drying in an oven at the temperature of 65 ℃ for 4h to obtain porous polyacrylate microspheres embedded with ALF raw materials, wherein the porous polyacrylate microspheres are named PAA-Al (OH) 3 -1；
S6: soaking the product obtained in 0.3g S5 in 5ml formic acid solution, reacting at 150 deg.C for 48h, taking out the pellet, washing twice with ethanol as solvent, and drying in oven at 65 deg.C for 4h to obtain ALF @ PAA-1.
The ALF raw material loading was calculated to be 42%.
The material prepared in this example was subjected to a performance test: measurement of material to CO Using a fully automated specific surface area Analyzer 2 The adsorption amount, results are: the adsorption capacity of ALF @ PAA-1 at 25 ℃ and 10kPa is 44.8cm 3 /g。
Example 2
Adopt the present inventionProcesses for the preparation of CO 2 The trapped ALF composite material comprises the following specific steps:
s1: preparation of the first phase:
mixing acrylate (TBA, 20.0 wt.%), tert-butyl methacrylate (TBMA, 10.0 wt.%), trimethylolpropane triacrylate (TMPTA, 20.0 wt.%), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P-123, 3.0 wt.%), toluene (45.0 wt.%), and benzoyl peroxide (BPO, 2.0 wt.%) in a beaker;
s2: preparation of the second phase:
mixing 11g of nano aluminum hydroxide dispersion liquid and 7.2ml of deionized water to prepare a second phase;
s3: preparation of a third phase:
adding the second phase prepared in S2 into the first phase prepared in S1, stirring at 8000rpm for 10min to maintain the stability of the emulsion, and adding N, N-dimethylaniline (DMA, 1.0 wt.%) into the emulsion during stirring;
s4: preparation of a fourth phase:
mixing ammonium persulfate (APS, 0.5 wt.%), N' -tetramethylethylenediamine (TMEDA, 0.5 wt.%), polyvinyl alcohol (PVA, 1 wt.%), and deionized water (98.0 wt.%);
s5: slowly pouring the third phase obtained in the step S3 into a three-neck round-bottom flask containing the fourth phase obtained in the step S4, continuously stirring for 15min at a constant temperature of 65 ℃ to ensure that the emulsion is dispersed into uniform droplets, finishing polymerization, and drying in an oven at the temperature of 65 ℃ for 4h to obtain the porous polyacrylate microspheres embedded with the ALF raw material, wherein the porous polyacrylate microspheres are named as PAA-Al (OH) 3 -2；
S6: soaking the product obtained in 0.3g S5 in 5ml formic acid solution, reacting at 150 deg.C for 48h, taking out the pellet, washing twice with ethanol as solvent, and drying in oven at 65 deg.C for 4h to obtain ALF @ PAA-2.
The ALF raw material loading was calculated to be 47%.
The intermediate product PAA-Al (OH) produced in this example 3 2 is shown in FIG. 1 (a) and an electron micrograph of the surface pore structure is shown in FIG. 1 (b),an electron microscope scan of the internal pore structure of the obtained target product ALF @ paa-2 is shown in fig. 1 (c), and an electron microscope scan of the ALF powder as a control is shown in fig. 1 (d).
As can be seen from FIGS. 1 (a) and 1 (b), the intermediate product PAA-Al (OH) 3 -2 has a developed surface pore and internal pore structure, which is advantageous for the subsequent reaction solution and CO 2 Gas molecules enter the material to provide an excellent carrier for producing the ALF composite material serving as a target product. As shown in FIG. 1 (c), the ALF grains in the target product ALF @ PAA-2 are distributed orderly and uniformly in the porous polymer carrier, and the grain size is 200-400nm; as can be seen from FIG. 1 (d), the ALF powder itself is a crystal having a nonuniform size, and the particle size is about 1 to 5 μm. As can be seen from FIGS. 1 (c) and 1 (d), the method provided by the present invention effectively improves the channel structure of ALF, so that it is more favorable for absorbing and capturing CO 2 。
The material prepared in this example was subjected to a performance test: measurement of CO at different temperatures of materials using a fully automated specific surface area analyzer 2 Amount of adsorption of CO at 25 ℃ 2 The adsorption isotherms are shown in FIG. 2, and it can be seen from FIG. 2 that the ALF composite material prepared is a product of CO 2 The adsorption amount of (2) gradually increases with increasing pressure, and the adsorption amount at 10kPa is 53.4cm 3 A specific adsorption capacity at 101.3kPa of 94.8 cm/g 3 /g。
The ALF composite material prepared in this example was calculated to have CO 2 The adsorption capacity was 1.07 times that of the corresponding ALF powder at different pressures.
Example 3
The method provided by the invention is adopted to prepare the catalyst for CO 2 The trapped ALF composite material comprises the following specific steps:
s1: preparation of the first phase:
acrylate (TBA, 20.0 wt.%), t-butyl methacrylate (TBMA, 10.0 wt.%), trimethylolpropane triacrylate (TMPTA, 20.0 wt.%), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P-123, 3.0 wt.%), toluene (45.0 wt.%), and benzoyl peroxide (BPO, 2.0 wt.%) were mixed in a beaker;
s2: preparation of the second phase:
mixing 17g of nano-alumina dispersion liquid and 2.4ml of deionized water to prepare a second phase;
s3: preparation of a third phase:
adding the second phase prepared in S2 into the first phase prepared in S1, and stirring at 8000rpm for 10min to maintain the stability of the emulsion, and adding N, N-dimethylaniline (DMA, 1.0 wt.%) into the emulsion during stirring;
s4: preparation of the fourth phase:
mixing ammonium persulfate (APS, 0.5 wt.%), N' -tetramethylethylenediamine (TMEDA, 0.5 wt.%), polyvinyl alcohol (PVA, 1 wt.%), and deionized water (98.0 wt.%);
s5: slowly pouring the third phase obtained in the step S3 into a three-neck round-bottom flask containing the fourth phase obtained in the step S4, continuously stirring for 15min at constant temperature of 65 ℃ to ensure that the emulsion is dispersed into uniform droplets to complete polymerization, and drying in a 65 ℃ oven for 4h to obtain the porous polyacrylate microspheres embedded with the ALF raw material, wherein the porous polyacrylate microspheres are named as PAA-Al 2 O 3 ；
S6: soaking the product obtained in 0.3g S5 in 5ml formic acid solution, reacting at 150 deg.C for 48h, taking out the pellet, washing twice with ethanol as solvent, and drying in oven at 65 deg.C for 4h to obtain ALF @ PAA-3.
The ALF raw material loading was calculated to be 42%.
The material prepared in this example was subjected to a performance test: measurement of material to CO Using a fully automated specific surface area Analyzer 2 The adsorption amount, results are: the adsorption capacity of ALF @ PAA-2 at 25 deg.C and 10kPa was 45.6cm 3 /g。
Comparative example 1
The same experimental conditions as those of example 1 were adopted, and the embedded ALF raw material was changed to be impregnated with the same concentration of ALF raw material, i.e., the suspension of aluminum hydroxide and formic acid, specifically:
s1: mixing acrylate (TBA, 20.0 wt.%), tert-butyl methacrylate (TBMA, 10.0 wt.%), trimethylolpropane triacrylate (TMPTA, 20.0 wt.%), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P-123, 3.0 wt.%), toluene (45.0 wt.%), and benzoyl peroxide (BPO, 2.0 wt.%) in a beaker;
s2: 15ml of deionized water was added to the mixed system obtained in S1 and stirred at 8000rpm for 10min, to which N, N-dimethylaniline (DMA, 1.0 wt.%) was added during stirring;
s3: mixing ammonium persulfate (APS, 0.5 wt.%), N' -tetramethylethylenediamine (TMEDA, 0.5 wt.%), polyvinyl alcohol (PVA, 1 wt.%), and deionized water (98.0 wt.%);
s4: slowly pouring the product obtained in the step S2 into a three-neck round-bottom flask containing the product obtained in the step S3, continuously stirring for 15min at constant temperature of 65 ℃ to ensure that the emulsion is dispersed into uniform droplets to complete polymerization, and drying for 4h in a drying oven at the temperature of 65 ℃ to obtain porous polyacrylate microspheres;
s5: and (2) soaking the porous polyacrylate microspheres prepared by 0.2gS4 in a suspension prepared by mixing 1.7g of nano-aluminum hydroxide powder, formic acid and 15ml of deionized water, reacting for 48 hours at 150 ℃, taking out the microspheres, washing twice by using ethanol as a solvent, and drying for 4 hours in a 65 ℃ oven to obtain the ALF composite material.
The resulting material was subjected to a performance test under the same conditions as in example 1: CO measurement of materials at 25 ℃ using a fully automated specific surface area analyzer 2 The adsorption capacity was 40cm at 10kPa 3 /g。
Comparative example 2
The same experimental conditions as those of the example 2 are adopted, and the embedded ALF raw material is changed into the aluminum hydroxide dispersion liquid with the same concentration by dipping, and the method specifically comprises the following steps:
s1: mixing acrylate (TBA, 20.0 wt.%), tert-butyl methacrylate (TBMA, 10.0 wt.%), trimethylolpropane triacrylate (TMPTA, 20.0 wt.%), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P-123, 3.0 wt.%), toluene (45.0 wt.%), and benzoyl peroxide (BPO, 2.0 wt.%) in a beaker;
s2: 15ml of deionized water was added to the mixed system obtained in S1 and stirred at 8000rpm for 10min, to which N, N-dimethylaniline (DMA, 1.0 wt.%) was added during stirring;
s3: mixing ammonium persulfate (APS, 0.5 wt.%), N' -tetramethylethylenediamine (TMEDA, 0.5 wt.%), polyvinyl alcohol (PVA, 1 wt.%), and deionized water (98.0 wt.%);
s4: slowly pouring the product obtained in the step S2 into a three-neck round-bottom flask containing the product obtained in the step S3, continuously stirring for 15min at constant temperature of 65 ℃ to ensure that the emulsion is dispersed into uniform droplets to complete polymerization, and drying for 4h in a drying oven at the temperature of 65 ℃ to obtain porous polyacrylate microspheres;
s5: and (2) soaking the porous polyacrylate microspheres prepared by 0.2gS4 in a suspension prepared by mixing 11g of nano aluminum hydroxide dispersion, formic acid and 7.2ml of deionized water, reacting for 48 hours at 150 ℃, taking out the microspheres, washing twice by using ethanol as a solvent, and drying for 4 hours in a 65 ℃ oven to obtain the ALF composite material.
The resulting material was subjected to a performance test under the same conditions as in example 2: CO measurement of materials at 25 ℃ using a fully automated specific surface area analyzer 2 An adsorption capacity of 50.2cm at 10kPa 3 /g。
Comparative example 3
The same experimental conditions as those in example 3 were adopted, and the embedded ALF raw material was changed to be impregnated with the same concentration of aluminum hydroxide dispersion, specifically:
s1: mixing acrylate (TBA, 20.0 wt.%), tert-butyl methacrylate (TBMA, 10.0 wt.%), trimethylolpropane triacrylate (TMPTA, 20.0 wt.%), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P-123, 3.0 wt.%), toluene (45.0 wt.%), and benzoyl peroxide (BPO, 2.0 wt.%) in a beaker;
s2: 15ml of deionized water was added to the mixed system obtained in S1 and stirred at 8000rpm for 10min, to which N, N-dimethylaniline (DMA, 1.0 wt.%) was added during stirring;
s3: mixing ammonium persulfate (APS, 0.5 wt.%), N' -tetramethylethylenediamine (TMEDA, 0.5 wt.%), polyvinyl alcohol (PVA, 1 wt.%), and deionized water (98.0 wt.%);
s4: slowly pouring the product obtained in the step S2 into a three-neck round-bottom flask containing the product obtained in the step S3, continuously stirring for 15min at constant temperature of 65 ℃ to ensure that the emulsion is dispersed into uniform droplets to complete polymerization, and drying for 4h in a drying oven at the temperature of 65 ℃ to obtain porous polyacrylate microspheres;
s5: soaking the porous polyacrylate microspheres prepared by 0.2gS4 in a suspension prepared by mixing 17g of nano-alumina dispersion, formic acid and 2.4ml of deionized water, reacting at 150 ℃ for 48 hours, taking out the microspheres, washing twice by using ethanol as a solvent, and drying in a 65 ℃ oven for 4 hours to obtain the ALF composite material.
The resulting material was subjected to a performance test under the same conditions as in example 3: CO measurement of materials at 25 ℃ using a fully automated specific surface area analyzer 2 The adsorption capacity was 42.1cm at 10kPa 3 /g。
Comparing example 1 and comparative example 1, example 2 and comparative example 2, and example 3 and comparative example 3 respectively, it can be seen that, compared with the conventional impregnation method, the embedding of the ALF raw material is completed during the synthesis of the porous polyacrylate microspheres according to the preparation method provided by the invention, and the prepared ALF composite material is CO-resistant 2 The adsorption capacity is obviously improved, and the adsorption performance is obviously enhanced.
It should be noted that the technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered. The above examples only express several embodiments of the present application, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. For CO 2 Captured ALF composite material, characterized in that the ALF composite material is a raw materialThe material composition comprises: porous polyacrylate microspheres and ALF raw materials;
the ALF starting material comprises an ALF metal source and an organic ligand.
2. The ALF composite material according to claim 1, wherein the porous polyacrylate microspheres are present in an amount of 40-50% by weight;
preferably, the mass percentage of the ALF metal source is 20-40%;
preferably, the mass percent of the organic ligand is 10-30%.
3. The ALF composite material according to claim 1 or 2, wherein the ALF metal source comprises one or more of aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum oxalate, nano aluminum hydroxide and a dispersion thereof, nano aluminum oxide and a dispersion thereof.
4. The ALF composite material according to claim 1 or 2, wherein the organic ligand comprises one or more of sodium formate, potassium formate, ammonium formate, formic acid.
5. A method for preparing the ALF composite material according to any one of claims 1 to 4, comprising: preparing the porous polyacrylate microspheres embedded with the ALF raw material, and then carrying out a composite reaction to obtain the acrylic microsphere.
6. The method of claim 5, wherein the preparing porous polyacrylate microspheres embedded with ALF raw material comprises,
preparation of the first phase: mixing a polyacrylate monomer, an emulsifier, a pore-forming agent and an initiator A;
preparing a second phase: mixing the ALF starting material and water;
preparation of a third phase: mixing the first phase, the second phase and a reducing agent A;
preparation of a fourth phase: mixing an initiator B, a reducing agent B, a dispersing agent and water;
mixing the third phase and the fourth phase, and carrying out polymerization reaction to obtain porous polyacrylate microspheres embedded with ALF raw materials;
preferably, the temperature of the polymerization reaction is 60-70 ℃, and the reaction time is 10-25min.
7. The method according to claim 6, wherein the polyacrylate monomer comprises one or more of acrylate, glycidyl methacrylate, t-butyl methacrylate and trimethylolpropane triacrylate.
8. The method of claim 6, wherein the emulsifier comprises one or more of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P-123), tween, span 80;
preferably, the porogen comprises toluene;
preferably, the initiator a comprises benzoyl peroxide;
preferably, the reducing agent a comprises N, N-dimethylaniline;
preferably, the initiator B comprises ammonium persulfate;
preferably, the reducing agent B comprises N, N' -tetramethylethylenediamine;
preferably, the dispersant comprises polyvinyl alcohol.
9. The method according to claims 6 to 8, wherein the starting materials for the preparation of the first phase are used in the respective amounts: 50.0-55.0wt.% of acrylate monomer, 3.0-5.0wt.% of emulsifier, 40.0-45.0wt.% of pore-forming agent, 1.0-1.5wt.% of initiator A, 1.0-1.5wt.% of reducing agent A;
preferably, the ALF starting material used to prepare the second phase is used in an amount of 20 to 60wt% of the solid phase components used to prepare the first phase;
preferably, the amount of water used to prepare the second phase is from 80 to 85vol.% of the volume of the first phase;
preferably, the amounts of the raw materials for preparing the fourth phase are respectively as follows: 0.3-0.5wt.% of initiator B, 0.3-0.5wt.% of reducing agent B, 0.5-1.0wt.% of dispersant, 98.0-98.5wt.% of water.
10. The preparation method according to claim 5, wherein the temperature of the composite reaction is 50-150 ℃ and the time is 18-48h.
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