CN103418356B - Gas adsorption material and preparation method thereof - Google Patents
Gas adsorption material and preparation method thereof Download PDFInfo
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- CN103418356B CN103418356B CN201210155234.4A CN201210155234A CN103418356B CN 103418356 B CN103418356 B CN 103418356B CN 201210155234 A CN201210155234 A CN 201210155234A CN 103418356 B CN103418356 B CN 103418356B
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- 239000000463 material Substances 0.000 title claims abstract description 115
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000412 dendrimer Substances 0.000 claims abstract description 78
- 229920000736 dendritic polymer Polymers 0.000 claims abstract description 78
- 150000001412 amines Chemical class 0.000 claims abstract description 65
- 239000007787 solid Substances 0.000 claims abstract description 59
- 239000007789 gas Substances 0.000 claims abstract description 52
- -1 small molecule amine Chemical class 0.000 claims abstract description 39
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 78
- 239000001569 carbon dioxide Substances 0.000 claims description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 39
- 125000003277 amino group Chemical group 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 25
- 238000001802 infusion Methods 0.000 claims description 24
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 238000007306 functionalization reaction Methods 0.000 claims description 18
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 18
- 125000003368 amide group Chemical group 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 14
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 14
- 230000006837 decompression Effects 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 238000003541 multi-stage reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229940043237 diethanolamine Drugs 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 230000003993 interaction Effects 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000002956 ash Substances 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims description 3
- 229910000275 saponite Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000002912 waste gas Substances 0.000 abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 17
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- 239000008246 gaseous mixture Substances 0.000 description 6
- 239000011343 solid material Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000006845 Michael addition reaction Methods 0.000 description 3
- 239000011358 absorbing material Substances 0.000 description 3
- 238000011938 amidation process Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000012678 divergent method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
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- 150000002605 large molecules Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 241001044369 Amphion Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a gas adsorption material and a preparation method thereof, wherein the gas adsorption material comprises 40-70 wt% of a solid carrier with a porous surface, 25-50 wt% of at least one dendrimer amine source loaded on the surface of the solid carrier and in a pore channel and/or combined with an active site of the solid carrier, and 1-10 wt% of a small molecule amine source for modifying the surface of the adsorption material and the pore channel, wherein the small molecule amine source is loaded on the surface of the solid carrier and in the pore channel after the dendrimer amine source is loaded and/or combined with the dendrimer amine source, so that the amine sites, the concentration and the activity on the adsorption material are uniformly increased, and the capacity and the speed of the adsorption material for adsorbing or capturing gas are improved. The gas adsorption material has excellent adsorption performance, and can be used for separating and purifying specific gas in mixed gas or waste gas.
Description
Technical field
The present invention relates to a kind of gas adsorption material and preparation method thereof, more particularly, relate to a kind of comprise there is porous surface solid carrier, dendrimer amine source and small molecule amine source gas adsorption material and preparation method thereof.
Background technology
Widely use the fuel such as oil, natural gas, coal along with in industry, sphere of life, the toxic emission problem that these fuel produce in combustion receives publicity for a long time as the environmental problem of global scale.Containing great amount of carbon dioxide in above-mentioned waste gas, and global warming main cause is because atmospheric carbon dioxide levels increases.And for example, also may comprise other toxic gases such as oxysulfide, nitrogen oxide, hydrogen sulfide in the waste gas of many industrial discharges, severe contamination will be caused to environment if be directly discharged in air, very harmful.Due to still considerable to the demand of above-mentioned fuel from now on, therefore how processing carbon dioxide in the waste gas of generation or gaseous mixture or other toxic gas will be a severe problem.
In fact, some gas in waste gas or gaseous mixture is the raw material needing supply in some industrial process, such as, can be used as Product recycling after the separated purification of carbon dioxide and utilizes.Catch and store (CCS) at carbon and improve carbon dioxide in oil recovering (EOR) field and to be absolutely necessary raw material, in order to obtain high concentration carbon dioxide or reduce the cost buying carbon dioxide, from gaseous mixture or waste gas, be separated and reclaim carbon dioxide is expediently the important channel solved the problem.
In the past few decades, be separated and reclaim some specific gas from burnt gas or gaseous mixture is the problem that people study always, wherein how a lot of research is from being separated carbon dioxide in waste gas, these researchs in early days for be that so-called carbon dioxide " wet " and is separated and recovery method, namely using can the appropriate solution of selective absorption carbon dioxide or solvent wash gaseous mixture or waste gas, and reclaim adsorbed carbon dioxide by heating adsorption solution or solvent, conventional alcamines solution is as so liquid adsorbent, such as monoethanolamine (MEA), diethanol amine (DEA), methyl diethanolamine (MDEA).But the problem that the method runs into is that wash solution is comparatively strong to the corrosivity of equipment, and easily oxidative phenomena occurs.In addition, because usually also comprising sulphur and nitrogen oxide (SO in waste gas or gaseous mixture
xand NO
x), some component reaction in they and wash solution, can produce stable salt and be difficult to remove and other hazardous compound of process, therefore, needing often to replace wash solution.
Therefore, recent domestic research mainly concentrates on solid adsorption material, such as zeolite, active carbon, molecular sieve, and its method of operating is comparatively simple, with low cost, and to equipment non-corrosiveness.But these solid adsorption materials exist usually because of the interference of other gas poor selectivity, less to the adsorbance of specific gas, raise with temperature and adsorbance such as obviously to reduce at the shortcoming.Relatively, solid amine can highly selective absorbing carbon dioxide by chemical action, other gas and water less on its impact, and it is compared with liquid amine solution, because having higher amino density, thus improves adsorption efficiency.Importantly, these be loaded with amine functional group solid adsorption materials this as porous adsorbing material, when described sorbing material contacts with the gas that adsorbs of needs, by the synergy of physical absorption and chemisorbed, substantially increase its adsorption efficiency.
US2010/0263534A1 discloses a kind of amine absorber and preparation and application thereof, adsorbent in this invention is used for selective absorption carbon dioxide and/or sulphur compound, this adsorbent comprises the amine source of cellular solid and alkane or aromatics, wherein, solid material is contacted with amine source, amine source is carried on solid material surface.In addition, when the amine functional group on solid material surface contacts with carbon dioxide or sulphur compound, carbon dioxide or sulphur compound are combined with amine functional group, reduce amine functional group and the interactional possibility of solid material surface in amine source, and add the amine portion position that can be used for catching carbon dioxide or sulphur compound.Therefore, in an embodiment of this invention preparation method, solid material is contacted with amine source with carbon dioxide simultaneously, reach the amine functional group and the interactional object of solid material surface that reduce amine source.Although solid amine adsorbent disclosed in this invention provides a kind of method that can improve carbon dioxide or sulphur compound adsorption rate, but still need to improve the adsorption efficiency of amine functional group quantity and enhancing sorbing material in adsorbent, to optimize sorbing material performance.
For improving adsorptive selectivity and the adsorption capacity of solid adsorption material further, select new grafting functional molecule, preparation has the composite of high density active amino group, and researchers have done again some researchs in functional material.1985, the people such as D.A.Tomalia successfully synthesized dendrimer (Dendrimer) first time, this dendrimer have stable, height geometry is symmetrical, amount of functional groups is large, molecule internal cavity and strand increase the plurality of advantages such as controlled.Such as US5,560,929 disclose a kind of structured copolymers as the use of adsorbent, gel and carriers of metal ions and preparation method thereof, and the structured copolymers in this invention has highly branched internal structure and the external structure be made up of the monomeric unit forming hydrophobic enclosure of a combination or chelating at least one monomeric unit.Wherein, disclose in this invention with polyamide-amide (PAMAM) the type dendrimer of amine ending and PPI (PPI) type dendrimer and preparation method.
Thus, the people such as BandarFadhel are at " Stepwisegrowthofmelamine-baseddendrimersintomesoporesand theirCO2adsorptionproperties " (MicroporousandMesoporousMaterials, 111 (2008) 536-543) describe the carbon dioxide absorbing material obtained after the large molecule of mesopore molecular sieve surface in situ synthesizing tree-like in literary composition, on the surface of mesoporous molecular sieve SBA-15, repeatedly Michael addition reaction and amidation process is carried out with branching unit Cyanuric Chloride (CC) and for amine unit ethylenediamine (EDA) in order in this article, final acquisition is bonded to the sorbing material that algebraically is the melamine-based dendrimer of 1-4.And the people such as BandarFadhel are also at " CO2adsorptionbyPAMAMdendrimers:Significanteffectofimpreg nationintoSBA-15 " (MicroporousandMesoporousMaterials, 123 (2009) 140-149) describe the carbon dioxide absorbing material loading dendrimer in mesopore molecular sieve duct in literary composition, synthesized with branching unit methyl acrylate (MA) and for amine unit ethylenediamine (EDA) polyamide-amide (PAMAM) the type dendrimer that algebraically is 1-3 in this article, be carried in the duct of SBA-15 by infusion process again.
In selection solid carrier, some researchers are also at other porous carrier, nano material such as, also test, the people such as StephaneCampidelli are at " Dendrimer-funtionalizedsingle-wallcarbonnanotubes:synthe sis, characterization, andphotoinducedelectrontransfer " (JournalofAmericanChemicalSociety, 128 (2006) 12544-12552) describe the method using SWCN as the immobilized polyamide-amide of solid carrier (PAMAM) type dendrimer in literary composition, this research functional group reported in above-mentioned material interacts and does not destroy conjugated pi-system, thus define stable dendrimer in carbon nano tube surface.
But the adsorption effect of the solid adsorption material introduced in above-mentioned document is unsatisfactory, its carbon dioxide adsorption rate is generally only 6(weight) about % or lower.Reason may be compared with theoretical value, and in actual conditions, the distribution of dendrimer is even not, and the amine functional group of dendrimer end fails in the surface of solids and duct, to form effective carbon dioxide capture point equably; Or the amine functional group on dendrimer and the avtive spot on solid carrier surface interact, and cause have impact on effectively catching carbon dioxide molecule.
The disclosure of above-mentioned all documents is introduced with for referencial use in full at this.
For solving institute's problems faced in above-mentioned prior art, the present inventor is by careful technical conceive, at least one dendrimer amine source and at least one small molecule amine source are combined with each other, their uniteds are adsorbed and/or is combined in porous solid carrier surface and duct, namely the amine functional group on dendrimer is effectively hindered and the avtive spot on solid carrier surface interacts, in solid carrier surface and duct, effectively increase amine functional group again, thus facilitate its effective seizure to specific gas.Particularly, for selection dendrimer amine source and small molecule amine source side face, can adjust according to the physical property of porous solid carrier and chemical property, to reach desirable gas absorption effect.In the present invention, the synergic sorption in dendrimer amine source and small molecule amine source had both added the adsorbance of sorbing material to adsorbed gas, accelerated the rate of adsorption again, thus sorbing material can be made to obtain more stable, more efficient absorption property.
Summary of the invention
According to a first aspect of the present invention, a kind of gas adsorption material is provided, comprises:
40-70 % by weight has the solid carrier of porous surface;
At least one dendrimer amine source that 25-50 % by weight loads and/or combines with its avtive spot in described solid carrier surface and duct, wherein, described dendrimer amine source is obtained through multistep reaction with the branching unit for becoming geometry doubly to increase amine functional group by the amido unit containing amine functional group, and described amido unit is selected from ethylenediamine, butanediamine, hexamethylene diamine and/or tren, and described branching unit is selected from acrylonitrile, Cyanuric Chloride, diisopropylethylamine and/or methyl acrylate; With
1-10 % by weight inhales the small molecule amine source on described enclosure material surface and duct for modifying, comprise at least one binary or polynary chain alkanamine or aromatic amine;
Wherein, described small molecule amine source is loaded in solid carrier surface after loading dendrimer amine source and/or after being combined with dendrimer amine source and duct, thus increase amine portion position on described sorbing material, concentration and/or activity equably, to improve the absorption of described sorbing material or to catch ability and/or the speed of gas.
Preferably, described dendrimer amine source is selected from polyamidoamine dendrimers (PAMAM), PPI type dendrimer (PPI), melamine-based dendrimer, tren base dendrimer and their mixture.Wherein, the algebraically in described dendrimer amine source is 1 ~ 5, and more preferably, its algebraically is 2 ~ 4, and most preferably, its algebraically is 3.And in selection small molecule amine source side face, preferably, be tetren (TEPA), penten (PEHA) and/or phenylenediamine.
The solid carrier of porous surface can be selected from: silica, zeolite, saponite, float stone, bentonite, kaolin, convex-concave rod clay, silicon ash, molecular sieve, calcium oxide, magnesia, aluminium oxide, silica gel, diatomite, CNT, flying dust, white carbon, active carbon, coal tar and their mixture; It is preferably mesopore molecular sieve, such as, be selected from SBA-15, MCM-41, MCM-48, HMS and their mixture.For improving heat endurance and chemical stability, described solid carrier first can carry out pretreatment by 3-aminopropyl trimethoxy siloxane (APTS), active amino is formed, so that the interaction between the amine functional group reduced on amine source and solid carrier surface avtive spot at solid carrier surface.
For improving gas absorption efficiency and the adsorption capacity of unit amino, described sorbing material also can comprise the source of hydroxyl groups for modifying sorbing material surface and duct, and described source of hydroxyl groups can join separately in sorbing material or use as organic solvent when loading small molecule amine source and then stay in sorbing material, described source of hydroxyl groups is preferably polyethylene glycol, MEA, diethanol amine, or their mixture.
The specific gas that in the present invention, gas adsorption material adsorbed or was separated can be CO
2, SO
x, NO
xor H
2one or more gases in S, particularly, described gas adsorption material is the most remarkable to the adsorption effect of carbon dioxide.
According to a second aspect of the present invention, provide a kind of preparation method of described gas adsorption material, it comprises the following steps successively:
1) by divergent method amido unit and branching unit through the large molecule of multistep reaction synthesizing tree-like, subsequently with rotary distillation, decompression distillation or with organic solvent washing, remove unnecessary amido unit or branching unit, obtain the dendrimer amine source that at least one algebraically is 1-5;
2) by infusion process, the dendrimer amine source obtained in step 1) is carried in solid carrier surface and duct, dry also except desolventizing, obtain the sorbing material of preliminary amino-functionalization;
3) by infusion process or chemical grafting, at least one small molecule amine source is carried in step 2) in obtain preliminary amino-functionalization sorbing material surface and duct in, with carry out surface and duct modification, obtain final gas adsorption material.
Optionally, repeat above-mentioned steps 2) and/or step 3) once to five times, to increase the amine functional group on described sorbing material.
According to a third aspect of the present invention, provide the preparation method of another kind of described gas adsorption material, it comprises the following steps successively:
1) in solid carrier surface and duct, use amido unit and branching unit through multistep reaction by in-situ synthesis, fabricated in situ dendrimer, subsequently with rotary distillation, decompression distillation or with organic solvent washing, remove unnecessary amido unit or branching unit also drying, acquisition at least one algebraically is the sorbing material of the preliminary amino-functionalization that the dendrimer amine source of 1-5 combines with its avtive spot;
2) in sorbing material surface at least one small molecule amine source being carried in the preliminary amino-functionalization obtained in step 1) by infusion process or chemical grafting and duct, to carry out surface and duct modification, obtain final gas adsorption material, wherein optionally repeat step 1) and/or step 2) once to five times, to increase the amine functional group on described sorbing material.
According to the present invention second and the third aspect, preferably, in loading dendrimer amine source and/or before being combined with dendrimer amine source, available 3-aminopropyl trimethoxy siloxane (APTS) pre-treated solid carrier.
According to the present invention second and the third aspect, equally preferably, in sorbing material surface small molecule amine source being carried in preliminary amino-functionalization by infusion process and duct, and the solvent used is at least partially for having the alcohol higher than the boiling point of 120 DEG C, to be retained in described sorbing material, be used as the source of hydroxyl groups of modifying sorbing material surface and duct, thus improve gas absorption efficiency and the adsorption capacity of unit amino.
In the present invention, when selecting the preparation method of described sorbing material, amido unit, branching unit, dendrimer amine source algebraically and/or small molecule amine source can be selected according to the specific area of solid carrier, pore passage structure and aperture.
Detailed description of the invention
The present invention will be further explained in detail through the following describes, but below comprise the description of embodiment only for enabling general technical staff of the technical field of the invention clearly understand principle of the present invention and marrow, and do not mean that any type of restriction is carried out to the present invention.
Gas adsorption material of the present invention mainly comprises: 40-70 % by weight has the solid carrier of porous surface, 25-50 % by weight at least one dendrimer amine source and 1-10 % by weight at least one for modifying the small molecule amine source on sorbing material surface and duct; Wherein, dendrimer amine source loads and/or combines with its avtive spot in solid carrier surface and duct, for improving solid carrier surface and pore passage structure and characteristic, increase and catch the amine portion position of gas, concentration and/or activity, to improve sorbing material absorption or to catch the speed of gas, ability and/or performance; And small molecule amine source is used for modifying sorbing material surface and duct further, to make amine functional group be uniformly distributed in sorbing material surface and duct, above-mentioned two kinds of amine sources synergy makes final sorbing material when adsorbing specific gas, the adsorbance to gas can be increased substantially, simultaneously the rate of adsorption also be improved significantly.In the present embodiment, exemplarily, carbon dioxide is set as the specific gas needing to carry out adsorption treatment.
In selection dendrimer (Dendrimer) amine source side face, dendrimer amine source is obtained through multistep reaction with the branching unit for becoming geometry doubly to increase amine functional group by the amido unit containing amine functional group, wherein, amido Unit selection long-chain of the present invention, and the amine functional group of catching carbon dioxide molecule is the amido unit of primary amine, such as ethylenediamine (EDA), butanediamine, hexamethylene diamine, and/or tren (TREN), both to have increased considerably amine portion position, concentration, and/or it is active, reduce again amine functional group on dendrimer in solid carrier surface and duct with the crosslinked of other amine functional group or the hydroxyl reaction with sorbing material surface and duct.Amido unit is preferably ethylenediamine (EDA) and/or tren (TREN).Meanwhile, branching unit is selected from: acrylonitrile, Cyanuric Chloride (CC), diisopropylethylamine (DIEA) and/or methyl acrylate (MA), itself and amido unit carry out multistep reaction, by amine functional group load on dendrimer end.Described dendrimer can be loaded in described solid carrier surface and duct by infusion process, or combines (i.e. grafting) by in-situ synthesis with the avtive spot in solid carrier surface and duct.Dendrimer is because having above-mentioned unique texture, through loading or after being combined with avtive spot, very uniform amine functional group network structure is formed in the surface and/or duct of porous adsorbing material, carbon dioxide molecule can be caught or be adsorbed on network structure inside, also more carbon dioxide molecules can be absorbed in inlet hole road by capillary effect simultaneously.
But, to load or the dendrimer of grafting often has the situation that amine functional group skewness or different amine functional group be cross-linked etc., therefore, the present invention introduces small molecule amine source, for modifying sorbing material surface and duct further, to make amine functional group be uniformly distributed in sorbing material surface and duct, and by the interaction between the amine functional group of different chain length, the interactional phenomenon of amine functional group on effective control absorption carrier, above-mentioned two kinds of amine sources synergy makes final sorbing material when adsorbing specific gas, significantly can improve the adsorbance to gas, simultaneously the rate of adsorption also be improved significantly.Wherein, small molecule amine source comprises at least one binary or polynary chain alkanamine or aromatic amine, is preferably tetren (TEPA), penten (PEHA) and/or phenylenediamine, is more preferably tetren (TEPA).
The present invention can select any one or multiple porous material as solid carrier, preferably, solid carrier is selected from: silica, zeolite, saponite, float stone, bentonite, kaolin, convex-concave rod clay, silicon ash, molecular sieve, calcium oxide, magnesia, aluminium oxide, silica gel, diatomite, CNT, flying dust, white carbon, active carbon, coal tar and their mixture.Wherein, due to the aperture of mesopore molecular sieve and pore passage structure relatively stable, and surface hydroxyl is also more, and therefore, solid carrier of the present invention is preferably the mesopore molecular sieves such as SBA-15, MCM-41, MCM-48, HMS or their mixture.And above-mentioned solid carrier can carry out pretreatment by 3-aminopropyl trimethoxy siloxane (APTS), its surface silanol group and APTS are reacted formation covalent bond, and form active amino on solid carrier surface, so that the interaction on the amine functional group reduced on amine source and solid carrier surface and between the avtive spot in duct.
In the present embodiment, sorbing material can also comprise the source of hydroxyl groups for modifying sorbing material surface and duct, and hydroxyl can change the mechanism of action of amine functional group and carbon dioxide, can improve the gas absorption efficiency of unit amino.Carbaminate amphion can be formed because amino with carbon dioxide effect, and when hydroxyl exists, carbaminate can further with hydroxyl and carbon dioxide reaction, form stable acyl group structure.Therefore, when in mist besides co 2, even if also containing steam, the absorption property of amine functional group not only can not be affected, can improve adsorption effect on the contrary, increase adsorbance.Source of hydroxyl groups in the present invention can additionally or separately add, also can by infusion process when adding small molecule amine source not only as organic solvent, but also to add as source of hydroxyl groups, and described source of hydroxyl groups or solvent for use are at least partially for having the alcohol higher than the boiling point of 120 DEG C, to be retained in described sorbing material the source of hydroxyl groups being used as to modify sorbing material surface and duct, thus to be improved the gas absorption efficiency of unit amino.Above-mentioned source of hydroxyl groups is preferably polyethylene glycol, MEA, diethanol amine, or their mixture.
As mentioned above, for the preparation method of described sorbing material, to combine with infusion process by divergent method or by in-situ synthesis dendrimer amine source is carried in solid carrier surface and duct or with its avtive spot and combine, obtain the sorbing material of preliminary amino-functionalization; In the sorbing material surface simultaneously small molecule amine source being carried in preliminary amino-functionalization by infusion process or chemical grafting and duct, to carry out surface and duct modification, thus obtain final gas adsorption material.
Performance that above-mentioned sorbing material is described by exemplary and nonrestrictive embodiment and preparation method thereof below.
Embodiment
Embodiment 1: infusion process prepares 65.6SBA-15/30.2PAMAM-G3-4.2TEPA(parts by weight) sorbing material
Step (1): preparation PAMAM-G3 dendrimer
Prepare polyamide-amide (PAMAM) type dendrimer, with ethylenediamine (EDA) for kernel, first step reaction (a): 27.0mL methyl acrylate (MA) is dissolved in 20.0mL methyl alcohol, after 25 DEG C of lower magnetic forces stir 1 hour, slow dropping 5.0mL ethylenediamine, reacts 24 hours at 25 DEG C.Use Rotary Evaporators decompression distillation subsequently, remove unreacted methyl acrylate and methyl alcohol, obtain yellow viscous liquid (PAMAM-G0.5); Second step reaction (b): be dissolved in by 6.0mL ethylenediamine in 8mL methyl alcohol, after 25 DEG C of lower magnetic forces stir 6 hours, the PAMAM-G0.5 obtained in slow dropwise reaction (a), reacts 24 hours at 25 DEG C.Use Rotary Evaporators decompression distillation subsequently, remove unreacted ethylenediamine and methyl alcohol, obtain yellow viscous liquid (PAMAM-G1).Repeat the Michael addition in twice (a) and (b) and amidation process, obtain PAMAM-G3 dendrimer.
Step (2): infusion process prepares 65.6SBA-15/30.2PAMAM-G3 sorbing material
By 2.0gSBA-15 mesopore molecular sieve, (specific area is 800m
2/ g) be suspended in 36.0mL methyl alcohol, then add the 1.0mL(0.921 gram obtained from above-mentioned steps (1)) PAMAM-G3, vigorous stirring, after forming uniform suspension, ambient temperatare puts 24 hours.Use Rotary Evaporators decompression distillation subsequently, removing methyl alcohol, obtains the sorbing material of the preliminary amino-functionalization of the 65.6SBA-15/30.2PAMAM-G3 loading PAMAM-G3.
Step (3): infusion process prepares 65.6SBA-15/30.2PAMAM-G3-4.2TEPA sorbing material
The sorbing material of the preliminary amino-functionalization of the 1.5g65.6SBA-15/30.2PAMAM-G3 obtained from above-mentioned steps (2) is suspended in 30.0mL methyl alcohol, then add 0.066mL(0.066 gram) tetren (TEPA), vigorous stirring, after forming uniform suspension, ambient temperatare puts 24 hours.Use Rotary Evaporators decompression distillation subsequently, removing methyl alcohol, obtains the 65.6SBA-15/30.2PAMAM-G3-4.2TEPA sorbing material being loaded with PAMAM-G3 dendrimer amine source and TEPA small molecule amine source.
Embodiment 2: Graft Method and infusion process prepare 66.4SBA-15/29.4PAMAM-G3-4.2TEPA(parts by weight) sorbing material
Step (1): Graft Method prepares 66.4SBA-15/29.4PAMAM-G3 sorbing material
With Graft Method, PAMAM-G3 dendrimer amine source add in-place is loaded on SBA-15 sorbing material, first step reaction (a): by 2.0gSBA-15 mesopore molecular sieve and 17.2mL methyl acrylate, (specific area is 800m
2/ g) be placed in 100mL methyl alcohol, at N
2stirred under argon refluxes, and then slowly adds 4.0mL ethylenediamine, back flow reaction 24 hours at 15 DEG C, then uses 80mL oxolane and 80mL washed with dichloromethane, obtain being grafted to SBA-15 on the surface with the PAMAM-G0.5 in duct; Second step reaction (b): the 1.5g obtained from reaction (a) is grafted to SBA-15 and is placed in 100.0mL methyl alcohol with the PAMAM-G0.5 in duct on the surface, at N
2stirred under argon refluxes, and then slowly adds 16.0mL ethylenediamine, back flow reaction 20 hours at 15 DEG C, then uses 80.0mL oxolane and 80.0mL washed with dichloromethane, obtain being grafted to SBA-15 on the surface with the PAMAM-G1 in duct.Repeat the Michael addition in twice (a) and (b) and amidation process, obtain being loaded be grafted to SBA-15 on the surface with the sorbing material of the preliminary amino-functionalization of the 66.4SBA-15/29.4PAMAM-G3 of the PAMAM-G3 in duct.
Step (2): infusion process preparation be loaded with TEPA and be grafted to SBA-15 on the surface with the 66.4SBA-15/29.4PAMAM-G3-4.2TEPA sorbing material of the PAMAM-G3 in duct
The 1.5g obtained from above-mentioned steps (1) is loaded with and is grafted to SBA-15 and is suspended in 30.0mL methyl alcohol with the sorbing material of the preliminary amino-functionalization of the 66.4SBA-15/29.4PAMAM of the PAMAM-G3 in duct on the surface, repeat the step (3) in embodiment 1, obtain being loaded with TEPA and be grafted to SBA-15 on the surface with the 66.4SBA-15/29.4PAMAM-G3-4.2TEPA sorbing material of the PAMAM-G3 in duct.
Embodiment 3: infusion process prepares 64.5(SBA-15-APTS)/30.2(PAMAM-G3-TREN-G3:PAMAM-G3,17.2; TREN-G3,13.0)-5.3TEPA(parts by weight) sorbing material
Step (1): with APTS pretreatment SBA-15 solid carrier
By 5.0gSBA-15 mesopore molecular sieve, (specific area is 800.0m
2/ g) join in 500.0mL toluene, stir and slowly add 68.0mL3-aminopropyl trimethoxy siloxane (APTS), back flow reaction 24 hours at 80 DEG C, dry by 50.0mL toluene wash twice and at 80 DEG C, obtain with APTS pretreated (SBA-15-APTS) solid carrier.
Step (2): preparation PAMAM-G3 dendrimer and TREN-G3 dendrimer
Repeat the step (1) in embodiment 1, obtain PAMAM-G3 dendrimer.
Prepare tren (TREN) base dendrimer, with tren (TREN) for kernel, first step reaction (a): 8.0mL tren is dissolved in 100.0mL oxolane, after 0 DEG C of lower magnetic force stirs 20 hours, slow dropping 4.2mL Cyanuric Chloride and 2.8mL diisopropylethylamine, back flow reaction 48 hours at 15.0 DEG C.Use Rotary Evaporators decompression distillation subsequently, remove unreacted tren and oxolane, obtain TREN-G0.5; Second step reaction (b): be dissolved in 7.8mL oxolane by 4.2mL Cyanuric Chloride and 2.8mL diisopropylethylamine, after 0 DEG C of lower magnetic force stirs 20 hours, the TREN-G0.5 obtained in slow dropwise reaction (a), reacts 48 hours at 15.0 DEG C.Use Rotary Evaporators decompression distillation subsequently, remove unreacted Cyanuric Chloride, diisopropylethylamine and oxolane, obtain TREN-G1.Repeat the reaction in twice (a) and (b), obtain TREN-G3 dendrimer.
Step (3): infusion process prepares 64.5(SBA-15-APTS)/30.2(PAMAM-G3-TREN-G3:PAMAM-G3,17.2; TREN-G3,13.0) sorbing material
(specific area is 800.0m to (SBA-15-APTS) mesopore molecular sieve obtained in above-mentioned steps 1 by 2.0g
2/ g) be suspended in 100.0mL methyl alcohol, then add the 1.0mL(0.936g obtained from above-mentioned steps (2)) (0.545gPAMAM-G3 and 0.439gTREN-G3), vigorous stirring, after forming uniform suspension, ambient temperatare puts 24 hours.Use Rotary Evaporators decompression distillation subsequently, removing methyl alcohol, obtains 64.5(SBA-15-APTS)/30.2(PAMAM-G3-TREN-G3) the sorbing material of preliminary amino-functionalization.
Step (4): infusion process prepares 64.5(SBA-15-APTS)/30.2(PAMAM-G3-TREN-G3)-5.3TEPA sorbing material
By above-mentioned for 1.5g 64.5(SBA-15-APTS)/30.2(PAMAM-G3-TREN-G3) the sorbing material of preliminary amino-functionalization be suspended in 80.0mL methyl alcohol, then add 0.084mL(0.084 gram) tetren (TEPA), vigorous stirring, after forming uniform suspension, ambient temperatare puts 24 hours.Use Rotary Evaporators decompression distillation subsequently, removing methyl alcohol, obtains the 64.5(SBA-15-APTS being loaded with PAMAM-G3 and TREN-G3 dendrimer amine source and TEPA small molecule amine source)/30.2(PAMAM-G3-TREN-G3)-5.3TEPA sorbing material.
Embodiment 4: infusion process prepares 68.1(SBA-15-APTS)/29.6(PAMAM-G3-TREN-G3:PAMAM-G3,16.8; TREN-G3,12.8)-2.3(TEPA-PEG) (parts by weight) sorbing material
Step (1): infusion process prepares 68.1(SBA-15-APTS)/29.6(PAMAM-G3-TREN-G3) sorbing material
Except (SBA-15-APTS) is become except 68.1:29.6 with (PAMAM-G3-TREN-G3) weight ratio, repeat step (1) ~ (3) in embodiment 3, obtain 68.1(SBA-15-APTS)/29.6(PAMAM-G3-TREN-G3) the sorbing material of preliminary amino-functionalization
Step (2): infusion process prepares 68.1(SBA-15-APTS)/29.6(PAMAM-G3-TREN-G3)-2.3(TEPA-PEG) sorbing material
By above-mentioned 1.5g68.1(SBA-15-APTS)/29.6(PAMAM-G3-TREN-G3) the sorbing material of preliminary amino-functionalization be suspended in 80.0mL polyethylene glycol (PEG), then add 0.036mL(0.036 gram) tetren (TEPA), vigorous stirring, after forming uniform suspension, ambient temperatare puts 24 hours.Use Rotary Evaporators decompression distillation subsequently, remove unnecessary polyethylene glycol (PEG), obtain being loaded with the 68.1(SBA-15-APTS of PAMAM-G3 and TREN-G3 dendrimer amine source, TEPA small molecule amine source and PEG source of hydroxyl groups)/29.6(PAMAM-G3-TREN-G3)-2.3(TEPA-PEG) sorbing material.
Comparative example 1: infusion process prepares 65.6SBA-15/34.4PAMAM-G3(parts by weight) sorbing material
Except SBA-15 and PAMAM-G3 weight ratio is become except 65.6:34.4, repeat the step (1) in embodiment 1 and (2), obtain the 65.6SBA-15/34.4PAMAM sorbing material being loaded with PAMAM-G3 dendrimer.
Comparative example 2: Graft Method prepares 66.4SBA-15/33.6PAMAM-G3(parts by weight) sorbing material
Except becoming except 66.4:33.6 by SBA-15 and PAMAM-G3 weight ratio, repeat the step (1) in embodiment 2, obtain being loaded be grafted to SBA-15 on the surface with the 66.4SBA-15/33.6PAMAM-G3 sorbing material of the PAMAM-G3 in duct.
Comparative example 3: infusion process prepares 67.7SBA-15/32.3TEPA(parts by weight) sorbing material
By 1.5gSBA-15 mesopore molecular sieve, (specific area is 800.0m
2/ g) be suspended in 80.0mL methyl alcohol, then add 2.0mL(0.716 gram) tetren (TEPA), vigorous stirring, after forming uniform suspension, ambient temperatare puts 24.0 hours.Use Rotary Evaporators decompression distillation, removing methyl alcohol, obtains the 67.7SBA-15/32.3TEPA sorbing material being loaded with TEPA small molecule amine source.
Test case
Be determined at the physical property of the carbon dioxide absorbing material of preparation in embodiment 1 ~ 4 and comparative example 1 ~ 3, characterization of adsorption and amine load capacity, and after carrying out the operation of several adsorption-desorption cycle, observe the change of amine load capacity and carbon dioxide capture amount.The physical property of above-mentioned sorbing material, characterization of adsorption and amine load capacity are shown in table 1 below.
Table 1
The test condition of absorbing carbon dioxide is: mist composition (percent by volume): 15%CO
2, 4%O
2, 5%H
2o and 76%N
2; Gas flow rate: 80cm
3/ min; Adsorption temp: 40 DEG C and desorption temperature: 120 DEG C.
Table 2 result of carbon dioxide capture amount that gives the amine load capacity of described various sorbing material under above-mentioned adsorption conditions respectively after first time absorption and after adsorption-desorption cycle 50 times and measure with thermogravimetric-differential scanning calorimeter (TG-DSC) below.
Table 2
The data of table 1 and table 2 show: dendrimer amine source on porous support and small molecule amine source synergy, common absorbing carbon dioxide, compared with the independent absorbing carbon dioxide in single dendrimer amine source or small molecule amine source on porous support, the rate of adsorption, adsorbance and absorption stability all obtain obvious improvement.
The term that this description is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, are not intended to by any equivalents thereof exclude of the feature that represents and describe or its part outside when using these terms and form of presentation.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary, those of ordinary skill in the art should recognize can carry out any accommodation and improvement to these embodiments when not departing from principle of the present invention and spirit, and protection scope of the present invention determined by appended claim and equivalent thereof.
Claims (14)
1. a gas adsorption material, comprising:
40-70 % by weight has the solid carrier of porous surface;
At least one dendrimer amine source that 25-50 % by weight combines with the avtive spot in described solid carrier surface and duct, wherein, described dendrimer amine source is obtained through multistep reaction with the branching unit for becoming geometry doubly to increase amine functional group by the amido unit containing amine functional group, and described amido unit is selected from ethylenediamine, butanediamine, hexamethylene diamine and/or tren, and described branching unit is selected from acrylonitrile, Cyanuric Chloride, diisopropylethylamine and/or methyl acrylate; With
1-10 % by weight is for modifying the small molecule amine source on described sorbing material surface and duct, and described small molecule amine source is tetren (TEPA), penten (PEHA) and/or phenylenediamine;
Wherein, described small molecule amine source is loaded in solid carrier surface after its avtive spot is combined with dendrimer amine source and duct, thus increase amine portion position on described sorbing material, concentration and/or activity equably, to improve the absorption of described sorbing material or to catch ability and/or the speed of gas.
2. a preparation method for gas adsorption material according to claim 1, comprises the following steps successively:
1) in solid carrier surface and duct, use amido unit and branching unit through multistep reaction by in-situ synthesis, fabricated in situ dendrimer, subsequently with rotary distillation, decompression distillation or with organic solvent washing, remove unnecessary amido unit or branching unit also drying, acquisition at least one algebraically is the sorbing material of the preliminary amino-functionalization that the dendrimer amine source of 1-5 combines with its avtive spot;
2) by infusion process or chemical grafting, at least one small molecule amine source is carried in step 1) in obtain preliminary amino-functionalization sorbing material surface and duct in, to carry out surface and duct modification, obtain final gas adsorption material, wherein, optionally repeat step 1) and/or step 2) once to five times, to increase the amine functional group on described sorbing material.
3. preparation method according to claim 2, wherein, described dendrimer amine source is selected from: polyamidoamine dendrimers (PAMAM), PPI type dendrimer (PPI), melamine-based dendrimer, tren base dendrimer and their mixture.
4. preparation method according to claim 2, wherein, the algebraically in described dendrimer amine source is 1 ~ 4.
5. preparation method according to claim 2, wherein, described solid carrier is selected from: silica, zeolite, saponite, float stone, bentonite, kaolin, convex-concave rod clay, silicon ash, calcium oxide, magnesia, aluminium oxide, silica gel, diatomite, CNT, flying dust, white carbon, active carbon, coal tar and their mixture.
6. preparation method according to claim 2, wherein, described solid carrier is mesopore molecular sieve further, and described mesopore molecular sieve is selected from: SBA-15, MCM-41, MCM-48, HMS and their mixture.
7. preparation method according to claim 2, wherein, described solid carrier is with the pretreated solid carrier of 3-aminopropyl trimethoxy siloxane (APTS), active amino is formed, so that the interaction between the amine functional group reduced on amine source and solid carrier surface avtive spot at solid carrier surface.
8. according to one of any described preparation method of claim 2-7, wherein, described sorbing material also comprises the source of hydroxyl groups for modifying sorbing material surface and duct, to improve gas absorption efficiency and the adsorption capacity of unit amino.
9. preparation method according to claim 8, wherein, described source of hydroxyl groups is polyethylene glycol, MEA, diethanol amine or their mixture.
10. preparation method according to claim 2, wherein, described gas is CO
2, SO
x, NO
xor H
2one or more gases in S.
11. preparation methods according to claim 10, wherein, described gas is carbon dioxide.
12. preparation methods according to claim 2, wherein, in loading dendrimer amine source and/or before being combined with dendrimer amine source, with 3-aminopropyl trimethoxy siloxane pre-treated solid carrier.
13. preparation methods according to claim 2, wherein, in sorbing material surface small molecule amine source being carried in preliminary amino-functionalization by infusion process and duct, and the solvent used is at least partially for having the alcohol higher than the boiling point of 120 DEG C, to be retained in described sorbing material, be used as the source of hydroxyl groups of modifying sorbing material surface and duct, thus improve gas absorption efficiency and the adsorption capacity of unit amino.
14. preparation methods according to claim 2, wherein, select amido unit, branching unit, dendrimer amine source algebraically and/or small molecule amine source according to the specific area of solid carrier, pore passage structure and aperture.
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