CN101695652A - Gas separation functional material and preparation method and application thereof - Google Patents
Gas separation functional material and preparation method and application thereof Download PDFInfo
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- CN101695652A CN101695652A CN200910197868A CN200910197868A CN101695652A CN 101695652 A CN101695652 A CN 101695652A CN 200910197868 A CN200910197868 A CN 200910197868A CN 200910197868 A CN200910197868 A CN 200910197868A CN 101695652 A CN101695652 A CN 101695652A
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Abstract
The invention belongs to the technical field of nanometer porous materials, and particularly relates to a gas separation functional material, and a preparation method and application thereof. The functional material comprises aqueous inorganic nanoparticles, monodisperse aqueous polymer microspheres and a nonessential auxiliary agent, wherein functional modification groups capable of being combined with gas molecules are modified on the surfaces of the polymer microspheres or (and) the inorganic nanoparticles; a polymer/inorganic nanoparticle composite emulsion with adsorbable gas functional modification groups can be obtained by adopting an in situ polymerization method or a blending method; and after the moisture is volatilized, the polymer and the inorganic nanoparticles are self-assembled to form the gas separation functional material with a nanometer porous structure. The method and the application realize identification, adsorption and adsorption-desorption adjustment of the nanometer porous structure to gas molecules if CO2, H2S, SO2, HCl, Cl2, NO2, H2O, NH3 and the like by regulating and controlling the types of the polymer or (and) the inorganic nanoparticles, the particle diameters and the bore diameters of the functional modification groups, the microspheres and the inorganic nanoparticles on the surface, and the like.
Description
Technical field
The invention belongs to the nano-porous materials technical field, be specifically related to a kind of gas separation functional material and its production and application.
Background technology
Ordered nano porous material demonstrates great application prospect because of its special performance that has in photoelectric conversion material, catalysis material, medicine release and fields such as biochemistry, parting material.The nearly more than ten years it has been found that and prepared many inorganic or organic nano hole materials, wherein inorganic nano hole strength of materials height, order is good but easily crisp, flexible poor; Polymer-nano-porous material flexibility height but intensity is low, be difficult to obtain ordered structure.How large tracts of land obtains eco-friendly mano-porous material, make its structurally ordered controlled, have high flexibility and high strength, remain the key issue of field of nanometer technology research.
Adsorption and separation material is widely used in chemical industry, biology and field of medicaments, as CO in the atmosphere
2The greenhouse gases effect that causes is serious day by day, the CO in the narrow and small or confined space survival system (as space station, underground fortification, nuclear submarine, floor ventilation etc.)
2NH Deng waste gas absorption, petrochemical enterprise
3, H
2S, SO
2Deng the separation and the recycling of gas, the SO in power plant
2, NO
2Deng the absorption and the recovery of gas, the recovery of gasoline vapour, reclaim freon and replacement fluorine Leon, and porous material is used in natural gas purification and organic steam recovery etc. in a large number.But at present the inorganic porous separation sorbing material that uses have high temperature resistant, chemical stability good, mechanical strength is big, the separative efficiency advantages of higher, but fragility is greatly, break easily.But polyalcohol stephanoporate separate sorbing material have pliability good, be easy to advantage such as finishing large tracts of land use, but compare with inorganic porous material, synthetic difficulty is big, heat endurance and mechanical stability are relatively poor.Therefore, develop new gas separation functional material, become the key of extensive separation and concentration gas, the various countries researcher is exploring synthesizing high-strength, high tenacity, high efficiency always, the porous of adsorption-desorption is separated sorbing material easily, has not yet to see relevant report.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology simple, high strength, high tenacity, the gas separation functional material of safety non-toxic, it be utilize polymer microballoon or (with) the inorganic nano-particle finishing has the functionalized modification group such as the amino that can combine with gas molecule, imido grpup, carboxyl, sulfydryl, hydroxyl, the carbonic acid foundation, metal oxide based, adopt situ aggregation method or blending method to obtain single water-based polymer microballoon/inorganic nano-particle complex emulsions that disperses, behind the moisture evaporation, polymer and inorganic nano-particle self assembly form the gas separation functional material with nano-porous structure.Gas separation functional material of the present invention can be used for gas molecule such as CO
2, H
2S, SO
2, HCl, Cl
2, NO
2, H
2O, NH
3Deng adsorbing separation.
Another object of the present invention be to provide above-mentioned to gas separation functional material in the application aspect gas absorption, separation, the enrichment.
Gas separation functional material proposed by the invention, form by aqueous inorganic nano particle, single water-based polymer microballoon and nonessential auxiliary agent of disperseing, wherein, the inorganic nano-particle consumption is the 2-70wt% of gas separation functional material, polymer volume is the 30-98wt% of gas separation functional material, and auxiliary dosage is the 0-10.0wt% of gas separation functional material.
Each amounts of components is preferably: the inorganic nano-particle consumption is the 10-50wt% of gas separation functional material, and the monodisperse polymer consumption is the 50-80wt% of gas separation functional material, and auxiliary dosage is the 0-10.0wt% of gas separation functional material.
Aqueous inorganic nano particle described in the present invention refers to hydrophilic inorganic nano-particle, is metal oxide nanoparticles, nonmetal oxide nano particle, insoluble hydroxide nano particle or insoluble carbonate nano particle.
Inorganic nano-particle described in the present invention is specially in nano zirconia particles, nano zinc oxide particles, nano oxidized magnesium particle, nano-silicon dioxide particle, nano oxidized titanium particle, nano alumina particles, nano oxidized iron particle, nano europium oxide particle, nano-cerium oxide particle, nano oxidized iridium particle, nano-aluminum hydroxide particle, nanometer iron hydroxide particle, nanometer barium hydroxide particle, nano-calcium carbonate, nano-calcium carbonate zinc and the nano barium carbonate any one.
The average grain diameter of the inorganic nano-particle described in the present invention is 10-300nm, is preferably 10-150nm.
Monodisperse polymer described in the present invention is single water-based polymer microballoon that disperses, and its average grain diameter 100-5000nm is preferably 100-1000nm.
Single water-based polymer microballoon that disperses described in the present invention, 10-150 ℃ of its glass transition temperature is preferably 10-100 ℃.
Single water-based polymer microballoon that disperses described in the present invention is under 60-90 ℃ temperature, adopts emulsion polymerization, thin newborn polymerization, suspension polymerization to prepare.
Waterborne polymeric described in the present invention is one or more compositions of acrylic polymer, phenylethene-ACR polymer, vinyl acetate esters polymer, ethene-vinyl acetate base polymer, butadiene-styrene base polymer, organic silicon-acrylate base polymer, polyurethane-acrylate base polymer, epoxy-acrylate base polymer.
Waterborne polymeric described in the present invention, be specially acrylic acid-methyl methacrylate-butyl acrylate polymer, own ester-the methyl methacrylate of metering system-propenoic methyl carbamate polymer, cinnamic acrylic ester-methacrylate polymer, vinyl acetate polymer, the ethene-vinyl acetate polymer, the butadiene-styrene polymer, butadiene-alpha-methyl styrene polymer, butadiene-styrene-propyl methacrylate polymer, organosilicon-BA-St polymer, organosilicon-N hydroxymethyl acrylamide-methacrylic acid phenyl hexamethylene ester polymer, organosilicon-hexyl methacrylate-methacrylic acid urethane polymer, polyurethane-methacrylic acid-1,2-two phenethyl esters-vinyl acetate polymer, polyurethane-styrene-cyclohexyl methacrylate polymer, polyurethane-methyl methacrylate-hydroxyethyl methacrylate polymer, epoxy-benzyl methacrylate-methyl acrylate polymer, epoxy-methyl methacrylate-acrylate copolymer, epoxy-butyl acrylate-methylmethacrylate polymer etc.
Gas separation functional material proposed by the invention, be with the aqueous inorganic nano particle, it is single that to disperse water-based polymer microballoon and nonessential auxiliary agent be raw material, adopt the single water-based polymer/inorganic nanometer particle complex emulsions that disperses of situ aggregation method or blending method preparation, the baking temperature of control complex emulsions is at 0-300 ℃, behind the moisture evaporation, polymer and inorganic oxide nanoparticles self assembly form the gas separation functional material of nano-porous structure.
Gas separation functional material proposed by the invention, be the aqueous inorganic nano particle to be mixed the back adopt situ aggregation method to prepare polymer/inorganic nanometer particle complex emulsions with polymer monomer, water, add nonessential auxiliary agent again, under 0-300 ℃ of baking temperature, treat to form behind the moisture evaporation.
Gas separation functional material proposed by the invention, or under 0-100 ℃ of condition, adopt blending method in aqueous polymer emulsion, to add nano particle and nonessential auxiliary agent, preparation has the polymer/inorganic nanometer particle complex emulsions that can combine the functionalized modification group with gas molecule, under 0-300 ℃ of baking temperature, treat to form behind the moisture evaporation.
Gas separation functional material described in the present invention, the baking temperature of preferred complex emulsions is 60-200 ℃.
Gas separation functional material described in the present invention, aqueous inorganic nano particle both can be used as the hole support frame of gas separation functional material, can strengthen the mechanical strength of gas separation functional material again.
Described gas separation functional material, by the regulation and control polymer or (with) the functionalized modification group on the kind of inorganic nano-particle and surface, realize the identification of gas separation functional material to the gas with various molecule.
Described gas separation functional material described in the present invention, baking temperature, polymer microballoon by the regulation and control complex emulsions or (with) kind of inorganic nano-particle and the particle diameter of function of surface modification group, microballoon and inorganic nano-particle, pore size etc., realize that nano-pore structure is adjustable to absorption, the adsorption-desorption of gas molecule.
Gas separation functional material described in the present invention, polymer or (with) the inorganic nano-particle finishing has the functionalized modification group that can combine with gas molecule as amino, imido grpup, carboxyl, sulfydryl, hydroxyl, carbonic acid foundation, oxide-base.
Described gas separation functional material by content, loose structure pore size and the pore-size distribution etc. of regulation and control baking temperature, inorganic nano-particle, is realized the adjusting of nano-pore structure gas separation functional material to the gas molecule adsorption capacity.
Described gas separation functional material can be applied to gas molecule such as CO
2, H
2S, SO
2, HCl, Cl
2, NO
2, H
2O, NH
3Deng absorption, separation and enrichment.
If desired (as hope increase denseness, the levelability of polymer/inorganic nanometer particle complex emulsions, when being lowered into film temperature etc.), polymer/inorganic nanometer particle complex emulsions of the present invention can also comprise various suitable auxiliary agents, as long as they bring adverse influence to material of the present invention indistinctively.The non-limiting example of described auxiliary agent comprises defoamer, coalescents, thickener, levelling agent, age resister, ultraviolet absorber, pH conditioning agent and combination arbitrarily thereof.
The acquisition of gas separation functional material of the present invention does not have special requirement to pressure, as long as it can not influence the preparation process of gas separation functional material of the present invention significantly unfriendly.Other process conditions of not mentioning in the procurement process of the invention described above gas separation functional material but may relating to can be with the acquisition condition of conventional gas separation functional material.
Gas separation functional material and application thereof that the present invention proposes, have the following advantages: compare with traditional polymer gas separation function material, gas separation functional material of the present invention is a raw material with aqueous inorganic nano particle, single dispersion water-based polymer microballoon and nonessential auxiliary agent, acquisition has the polymer microballoon/inorganic nano-particle complex emulsions of adsorbable gas functionalized modification group, behind the moisture evaporation, both can form gas separation functional material with nano-porous structure.Preparation technology is simple, easy to operate, safety non-toxic.Baking temperature, polymer by the regulation and control complex emulsions or (with) functionalized modification group, microspherulite diameter, loose structure pore size and the pore-size distribution etc. of inorganic nano-particle sub-surface, polymer and inorganic nano-particle self assembly form orderly nano-porous structure, realize nano-pore structure to gas molecule (as CO
2, H
2S, SO
2, HCl, Cl
2, NO
2, H
2O, NH
3Deng) identification, absorption, adsorption-desorption adjustable.Adopt the inventive method, gas absorption functionalized modification group is combined on the material with chemical bonded refractory, is not easy to cause coming off and the dusty gas phenomenon of micro-molecular gas adsorption function modification group.Gas separation functional material have heat resistance good, can prolonged and repeatedly use, can be applied to absorption, separation and the enrichment of gas molecule.
Unless otherwise, all percentages used herein and ratio all by weight, each components contents is all in the gross weight of gas separation functional material in the gas separation functional material.
Description of drawings
Fig. 1 is the typical surface SEM photo of gas separation functional material, and as can be seen from the figure material has nano-porous structure.
Fig. 2 is the typical section SEM photo of gas separation functional material, and as can be seen from the figure material has three-D nano-porous structure.
The specific embodiment
The following example has further described and has proved the preferred embodiment in the scope of the invention.These embodiment that given only are illustrative, and are unintelligible for being limitation of the present invention.
Below among each embodiment each step of preparation gas separation functional material all under normal pressure, carry out, unless otherwise.
Embodiment 1:
In 250ml round bottom three-necked bottle, the water-based styrene-propene acid butyl ester-propenoic methyl carbamate emulsion (monomer mole ratio 3: 3: 1) that has the amino functional modification group that adds 30 gram water nano iron oxide colloidal sols, 70 gram employing emulsifier-free emulsion polymerization methods acquisitions, be warming up to 60-80 ℃, stirred 2 hours, obtain styrene-propene acid butyl ester-propenoic methyl carbamate polymer/nano-sized iron oxide complex emulsions, with this emulsion 100 ℃ of dryings 5 hours, obtain can be used for CO with amino nanoporous gas separation functional material
2, H
2S, SO
2, NO
2Separation and concentration Deng sour gas.
Embodiment 2:
In 250ml round bottom three-necked bottle, add 20 gram nano-calcium carbonate calcium sols, 100 and restrain the polyurethane-acrylate hydroxyl ethyl ester-styrene emulsion (monomer mole ratio 2: 1: 7) that adopts emulsion polymerizations to obtain, ultrasonic agitation 30 minutes, obtain polyurethane-acrylate hydroxyl ethyl ester-styrene polymer/nano-calcium carbonate complex emulsions, with this emulsion 200 ℃ of dryings 5 minutes, obtain having the nanoporous gas separation functional material of carbonate, can be used for H
2O, NH
3Separation and concentration Deng gas.
Embodiment 3:
In 250ml round bottom three-necked bottle, add 70 gram nano titanic oxide sols, 100 and restrain the epoxy-benzyl methacrylate-styrene-propene acid amides emulsion (monomer mole ratio 4: 1: 3: 2) that adopts fine emulsion polymerizations to obtain, stirring at room 24 hours, obtain epoxy-benzyl methacrylate-styrene-propene amide polymer/nanometer barium hydroxide complex emulsions, with this emulsion 80 ℃ of dryings 10 hours, obtain having the nanoporous gas separation functional material of amido, can be used for CO
2Separation and concentration gas Deng gas.
Embodiment 4:
In 250ml round bottom four-necked bottle, at N
2Protection down; add 100 and restrain water, the acidic aqueous nano silicon dioxide sol of 60 grams, 50 gram 3-methacryloxypropyl trimethoxy silane, 40 gram methyl methacrylates, 10 gram methacrylic acids mixing; 60-80 ℃ of control temperature; adopt emulsion polymerization in situ to prepare organosilicon-methyl methacrylate-methacrylate polymer/nano-silicon dioxide composite emulsion; with this emulsion 30 ℃ of dryings 24 hours; obtain having the nanoporous gas separation functional material of carboxyl, can be used for CO
2, H
2S, HCl, SO
2, NO
2Separation and concentration Deng gas.
Embodiment 5:
The nano-aluminium oxide colloidal sol, adding 20 gram cyclohexyl methacrylates, 60 gram styrene, the 20 gram methacrylic acid carbamates that in 250ml round bottom four-necked bottle, add 150 gram water, 5 gram water-based band amino, under 70-90 ℃ of condition, adopt original position emulsifier-free emulsion polymerization legal system to be equipped with cyclohexyl methacrylate-styrene-methacrylic acid urethane polymer/nano-aluminium oxide complex emulsions, with this emulsion 150 ℃ of dryings 3 hours, obtain having amino nanoporous gas separation functional material, can be used for NH
3The separation and concentration of gas.
Embodiment 6:
In 250ml round bottom four-necked bottle, add 100 gram water, 30 gram water nano zirconia sols, add 30 gram 3-sulfydryl Isooctyl acrylate monomers, 30 gram EMAs, 40 gram vinylacetates, under 80-100 ℃ of condition, adopt emulsion polymerization in situ to prepare sulfydryl Isooctyl acrylate monomer-EMA-vinyl acetate polymer/nano zirconia complex emulsions, with this emulsion 50 ℃ of dryings 24 hours, obtain having the nanoporous gas separation functional material of sulfydryl, can be used for NH
3Separation and concentration Deng gas.
Claims (12)
1. gas separation functional material, it is characterized in that forming by aqueous inorganic nano particle, single water-based polymer microballoon and nonessential auxiliary agent of disperseing, polymer microballoon and inorganic nano-particle surperficial arbitrary or all be modified with the functionalized modification group that can combine with gas molecule, adopt situ aggregation method or blending method to obtain to have the polymer microballoon/inorganic nano-particle complex emulsions of adsorbable gas functionalized modification group, behind the moisture evaporation, polymer and inorganic nano-particle self assembly form the gas separation functional material with nano-porous structure.
2. gas separation functional material according to claim 1, it is characterized in that: the inorganic nano-particle consumption is the 2-70wt% of gas separation functional material, single dispersion water-based polymer volume is the 30-98wt% of gas separation functional material, auxiliary dosage is the 0-10.0wt% of gas separation functional material, the average grain diameter of single dispersion water-based polymer microballoon is 100-5000nm, glass transition temperature 10-150 ℃, and the average grain diameter of nano particle is 10-300nm.
3. gas separation functional material according to claim 1, it is characterized in that: polymer microballoon and inorganic nano-particle surperficial arbitrary or all have the functionalized modification group that combines with gas molecule, for amino, imido grpup, carboxyl, sulfydryl, hydroxyl, carbonic acid foundation or metal oxide based in one or more.
4. gas separation functional material according to claim 1 is characterized in that: described single water-based polymer microballoon that disperses, its average grain diameter is preferably 100-1000nm.
5. gas separation functional material according to claim 1 is characterized in that: described single water-based polymer microballoon that disperses is under 60-90 ℃ temperature, adopts emulsion polymerization, thin newborn polymerization, suspension polymerization to obtain.
6. gas separation functional material according to claim 1, it is characterized in that: described waterborne polymeric is one or more compositions in acrylic polymer, phenylethene-ACR polymer, vinyl acetate esters polymer, ethene-vinyl acetate base polymer, butadiene-styrene base polymer, organic silicon-acrylate base polymer, polyurethane-acrylate base polymer and the epoxy-acrylate base polymer.
7. gas separation functional material according to claim 1, it is characterized in that: described inorganic nano-particle is hydrophilic inorganic nano-particle, is metal oxide nanoparticles, nonmetal oxide nano particle, insoluble hydroxide nano particle, insoluble carbonate nano particle.
8. gas separation functional material according to claim 7 is characterized in that: described inorganic nano-particle is any one in nano zirconia particles, nano zinc oxide particles, nano oxidized magnesium particle, nano-silicon dioxide particle, nano oxidized titanium particle, nano alumina particles, nano oxidized iron particle, nano europium oxide particle, nano-cerium oxide particle, nano oxidized iridium particle, nano-aluminum hydroxide particle, nanometer iron hydroxide particle, nanometer barium hydroxide particle, nano-calcium carbonate, nano-calcium carbonate zinc and the nano barium carbonate.
9. gas separation functional material according to claim 1 is characterized in that: described auxiliary agent is defoamer commonly used, coalescents, thickener, levelling agent, age resister, ultraviolet absorber, pH conditioning agent and combination arbitrarily thereof in the water paint.
10. the preparation method of a gas separation functional material as claimed in claim 1, it is characterized in that: the aqueous inorganic nano particle is mixed the back adopt situ aggregation method to prepare polymer/inorganic nanometer particle complex emulsions with polymer monomer, water, add nonessential auxiliary agent again, under 0-300 ℃ of baking temperature, after treating moisture evaporation, make described gas separation functional material;
Or
Under 0-100 ℃ of condition, adopt blending method in aqueous polymer emulsion, to add nano particle and nonessential auxiliary agent, preparation has the polymer/inorganic nanometer particle complex emulsions that can combine the functionalized modification group with gas molecule, under 0-300 ℃ of baking temperature, after treating moisture evaporation, make described gas separation functional material.
11. the preparation method of gas separation functional material according to claim 10 is characterized in that, the baking temperature of complex emulsions is 60-200 ℃.
12. one kind as the described gas separation functional material of claim 1～10 at gas molecule CO
2, H
2S, SO
2, HCl, Cl
2, NO
2, H
2O or NH
3Application on absorption, separation, the beneficiation technologies.
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| CN102070152A (en) * | 2010-12-01 | 2011-05-25 | 苏州纳微生物科技有限公司 | Functionalized homogeneous particle porous silicon dioxide microspheres and preparation method and application thereof |
| CN102671513A (en) * | 2012-04-26 | 2012-09-19 | 中国恩菲工程技术有限公司 | Method and device for removing sulfur dioxide in flue gas |
| CN105004715A (en) * | 2015-06-19 | 2015-10-28 | 天津出入境检验检疫局工业产品安全技术中心 | High-sensitivity CO2 identification card |
| CN106475074A (en) * | 2016-12-22 | 2017-03-08 | 苏州楚博生物技术有限公司 | High mechanical properties affinity chromatography medium |
| CN106582580A (en) * | 2016-12-22 | 2017-04-26 | 苏州楚博生物技术有限公司 | High-pressure-resistant affinity chromatography media for chromatographic column |
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| CN113477033A (en) * | 2021-07-20 | 2021-10-08 | 金浦新材料股份有限公司 | Self-emulsifiable organic silicon decarbonization solvent |
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| CN102070152B (en) * | 2010-12-01 | 2013-06-12 | 苏州纳微生物科技有限公司 | Functionalized homogeneous particle porous silicon dioxide microspheres and preparation method and application thereof |
| CN102070152A (en) * | 2010-12-01 | 2011-05-25 | 苏州纳微生物科技有限公司 | Functionalized homogeneous particle porous silicon dioxide microspheres and preparation method and application thereof |
| CN102671513A (en) * | 2012-04-26 | 2012-09-19 | 中国恩菲工程技术有限公司 | Method and device for removing sulfur dioxide in flue gas |
| CN102671513B (en) * | 2012-04-26 | 2015-07-01 | 中国恩菲工程技术有限公司 | Method and device for removing sulfur dioxide in flue gas |
| CN105004715A (en) * | 2015-06-19 | 2015-10-28 | 天津出入境检验检疫局工业产品安全技术中心 | High-sensitivity CO2 identification card |
| CN107174967A (en) * | 2016-03-10 | 2017-09-19 | 天津工业大学 | A kind of PVDF/SiO2Composite membrane and preparation method thereof |
| CN109310981A (en) * | 2016-07-28 | 2019-02-05 | 南洋理工大学 | Composite material, its preparation and gas purification purposes |
| US11247190B2 (en) | 2016-07-28 | 2022-02-15 | Nanyang Technological University | Composite material, its manufacture and use in gas purification |
| CN106582580A (en) * | 2016-12-22 | 2017-04-26 | 苏州楚博生物技术有限公司 | High-pressure-resistant affinity chromatography media for chromatographic column |
| CN106475074A (en) * | 2016-12-22 | 2017-03-08 | 苏州楚博生物技术有限公司 | High mechanical properties affinity chromatography medium |
| CN108129596A (en) * | 2018-01-12 | 2018-06-08 | 浙江东太新材料有限公司 | A kind of hollow porous micro sphere of compound organic uv absorbers and preparation method thereof |
| CN108129596B (en) * | 2018-01-12 | 2019-11-26 | 浙江东太新材料有限公司 | A kind of hollow porous micro sphere and preparation method thereof of compound organic uv absorbers |
| CN113477033A (en) * | 2021-07-20 | 2021-10-08 | 金浦新材料股份有限公司 | Self-emulsifiable organic silicon decarbonization solvent |
| WO2023053803A1 (en) * | 2021-09-28 | 2023-04-06 | 日東電工株式会社 | Acidic gas adsorbent and acidic gas adsorption apparatus |
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Application publication date: 20100421 |