CN103157448B - A kind of preparation method of the amido modified multi-stage porous sorbent material for Harm reduction techniques - Google Patents
A kind of preparation method of the amido modified multi-stage porous sorbent material for Harm reduction techniques Download PDFInfo
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- CN103157448B CN103157448B CN201310103701.3A CN201310103701A CN103157448B CN 103157448 B CN103157448 B CN 103157448B CN 201310103701 A CN201310103701 A CN 201310103701A CN 103157448 B CN103157448 B CN 103157448B
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Abstract
The present invention relates to Field of Tobacco, be specifically related to a kind of preparation method of a kind of amino functional multi-stage porous sorbent material for Harm reduction techniques.The invention provides a kind of preparation method of macropore-mesoporous silicon dioxide sorbent material, comprise the steps: to take raw material by proportioning, be dispersed in by organic high polymer microsphere in the ethanol of the silicon source that is dissolved with, acidic aqueous solution and surfactant, then at room temperature stirring a period of time makes the prehydrolysis of silicon source; Mixed solution is carried out solvent volatilization in substrate, the composite film material obtained is after burin-in process, be placed in solvent reflow treatment further, polymer microsphere template and surfactant are removed in extraction, obtain described macropore-mesoporous silicon dioxide sorbent material.The preparation method of macropore-mesoporous silicon dioxide sorbent material provided by the present invention synthesizes this material obtained to be had compared with high specific area, hole body greatly, and hole wall has modified a large amount of amino.
Description
Technical field
The present invention relates to Field of Tobacco, be specifically related to a kind of preparation method of a kind of amino functional multi-stage porous sorbent material for Harm reduction techniques.
Background technology
Along with the development of modern science and technology, people have had more deep understanding for cigarette smoke composition and harm thereof.According to bibliographical information, identify more than 4000 kinds of materials in cigarette smoke, wherein, except causing addiction thing nicotine, from the main component tar of main flume, also detected out that kind more than 40 has polycyclic aromatic hydrocarbon compounds that is carcinogenic, oncogenic activity.In order to reduce the content of the harmful components in flue gas, domestic many researchers have carried out a large amount of cigarette harm-reducing research work.The approach that special adsorbent is considered to a kind of more promising cigarette harm-reducing is added in filter tip.People have attempted using to be had active carbon with high specific surface area, zeolite molecular sieve, a porous fibre etc. and is added on as adsorbent used for filter tip in the research of this respect, but the aperture of these adsorbents is too little and irregular, as easy as rolling off a log by the aerosol of macromolecule in flue gas, in addition the skeleton of these materials does not possess specific functional group, therefore efficiently, optionally cannot reduce the harmful components in flue gas.
Recent study shows, the material with regular pore canal structure and hierarchical porous structure is being very suitable for studying in adsorbing separation.In fact, at occurring in nature hierarchical porous structure ubiquity.People find that the remains (i.e. diatomite) of marine microalgae plant have flourishing hierarchical porous structure very early, and its macropore presents high-sequential arrangement, and these macropores are communicated with each other by little nano-pore or micropore.Multilevel hole material, because of its unique hierarchical porous structure, the feature such as porosity is large, specific area is large, has broad application prospects in fields such as Industrial Catalysis, gas purification, water treatment, ultracapacitor, solar cells.Such as such as, have gradient pore distribution foramen magnum-mesoporous-the combined multi-stage Porous materials of micropore can be used as high-efficiency heavy oil catalytic cracking catalyst [Q.Tan, X.Bao, T.Song .JournalofCatalysis, 2007,251,69].Adopt isolated air roasting process biological material can obtain the activated carbon of multi-stage porous, but its aperture size and duct connectivity are difficult to control, and the absorption behavior of these materials does not have significantly selective.Adopt template synthesis method creative can prepare the multilevel hole material with preset aperture size, various surface nature, duct height UNICOM.Its synthesis usually relies on and uses surfactant to be aperture pore creating material, utilizes spherical high polymer microballoon (or emulsion droplets) or natural material as pore creating material [M.Antonietti, the B.Berton of macropore; C.Geltner; H.P.Hentze.Adv.Mater.1998,10,154; A.Dong, Y.Wang, Y.Tang, Y.Zhang, N.Ren, Z.Gao, Adv.Mater.2002,14:1506; T.Sen, G.T.Gordon, T.T.John, J.L.Casci, M.W.Anderson, Angew.Chem.Int.Ed.2003,42,4649; B.T.Holl, L.Abrams, A.Stein.J.Am.Chem.Soc.1999,121,4308; Y.S.Shin, C.M.Wang, G.J.Exarhos, Adv.Mater.2005,17,73.; B.J.Zhang, S.A.Davis, S.Mann.Chem.Mater.2002,14,1369.; M.W.Andeson, S.M.Holmes, N.Hanif, C.S.Cundy.Angew.Chem.Int.Ed., 2000,39,2707.; C.Shinye, U.Jun, FuyuhikoT., Bruce, I.Z.Jeffrey, J.Am.Chem.Soc., 2000,122,6488.].But all previously prepared orderly hard template template (as colloidal crystal) of these existing synthetic methods, form route long, and often need in building-up process to adopt high-temperature roasting to remove template, the decomposition of organic functional group can be caused in roasting process, directly cannot obtain the multistage material having and enrich functional group, therefore develop simple method and directly synthesize multi-stage artery structure, the attached agent material of macropore-mesoporous silicon dioxide cigarette filter enriching functional group has important research and is worth, the low harmful new cigarette of development is also had important practical significance.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of preparation method of the amido modified multi-stage porous sorbent material for Harm reduction techniques, for solving the problems of the prior art, described multi-stage porous sorbent material is a kind of macropore-mesoporous silicon dioxide sorbent material having multi-stage artery structure, enrich amino-functional group.
Multi-stage porous sorbent material involved in the present invention has multi-stage artery structure, enriches the macropore-mesoporous silicon dioxide sorbent material of amino-functional group, synthetic method is simply novel, use amino silane as the raw material of functional group, polymer microsphere and surfactant do template, remove template by the solvent extraction of gentleness and just can create hierarchical porous structure, can guarantee that amino silane is retained in the adsorption hole material skeleton of gained in good condition, the content of its functional group is easy to control simultaneously; Simultaneously, the macroporous structure of its three-dimensional UNICOM is conducive to fast transport and the diffusion of flue gas composition, and its mesopore orbit can provide superhigh specific surface area (amino with abundant) in addition, its silicon dioxide skeleton has nonhazardous feature, and the amino on its surface can form stable schiff bases (Schiffbase) with aldehydes molecule, therefore can be used as safe filtration additives for the aldehydes harmful components in selective removal flue gas.
For achieving the above object and other relevant objects, first aspect present invention provides the preparation method of described macropore-mesoporous silicon dioxide sorbent material, comprises the steps:
1) take the raw material of described macropore-mesoporous silicon dioxide sorbent material by proportioning, the raw material of described macropore-mesoporous silicon dioxide sorbent material by percentage to the quality, comprises following component:
2) be dispersed in by organic high polymer microsphere in the ethanol of the silicon source that is dissolved with, acidic aqueous solution and surfactant, then at room temperature stirring a period of time makes the prehydrolysis of silicon source;
3) mixed solution of step 2 gained is carried out solvent volatilization in substrate, the composite film material obtained is after burin-in process, be placed in solvent reflow treatment further, polymer microsphere template and surfactant are removed in extraction, obtain described macropore-mesoporous silicon dioxide sorbent material.
The macropore-mesoporous silicon dioxide sorbent material having multi-stage artery structure, enrich amino-functional group provided by the present invention, the macropore of the material of gained, mesoporous, amino content and mesoporous shape can be regulated by Control release condition and formula.
Preferably, described silicon source is selected from ethyl orthosilicate, γ-aminopropyltrimethoxysilane, aminopropyl triethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, γ-divinyl triammonium hydroxypropyl methyl dimethoxysilane wherein one or more.
Silicon source in the present invention comprises positive esters of silicon acis and amino silicone source, if do not use amino silicone source, so amino content is 0.
Preferably, described surfactant is selected from Brij series of products, PEO-b-PPOX-b-PEO (PEO-PPO-PEO) series.
The block copolymer of described (PEO-PPO-PEO) series is selected from EO
20pO
70eO
20(P123), EO
106pO
70eO
106(F127), EO
132pO
50eO
132(F108) wherein one or more.
Described Brij series of products and alkyl ether molecule, be selected from Brij78C
16eO
20, Brij56C
16eO
10, Brij76C
18eO
10, Brij98C
18h
35eO
20deng.
Preferably, described acidic aqueous solution is selected from aqueous hydrochloric acid solution, aqueous sulfuric acid, aqueous solution of nitric acid, aqueous acetic acid one wherein.
Preferred further, the concentration of acidic aqueous solution is 2M.
Described organic high polymer microsphere is selected from one or more in polystyrene microsphere (PSSphere), poly (methyl methacrylate) micro-sphere (PMMASphere) etc., and the particle diameter of described organic high polymer microsphere is 200-8000nm.
Preferably, the particle diameter of described organic high polymer microsphere is 200-2000nm.
More have choosing, in described step 1, organic high polymer microsphere is monodispersed organic high polymer microsphere.
Preferably, in described step 2, the condition of prehydrolysis is at room temperature stir 2-12 hour.
Preferably, in described step 2, the actual conditions carrying out solvent volatilization is carry out 6-24h at 30-70 DEG C.
Preferably, the extractant used in described step 3 is selected from one or more the mixing wherein of oxolane, acetone, dimethyl formamide, dimethyl sulfoxide (DMSO), carrene, toluene, dioxane.
Preferably, in described step 3, the actual conditions of burin-in process is: under 60-80 ° of C, toast 8-24 hour in an oven.
Preferably, in described step 3, the actual conditions of reflow treatment is: under 50-80 ° of C, heat 12-24 hour under laminated film being placed in extractant normal pressure.
More have choosing, in described step 3, the solvent of reflow treatment is selected from toluene.
The skeleton of the silica adsorbent materials prepared by the present invention is amido modified silica, and its macropore is mainly spherical pore, and it is mesoporous is spherical or tubulus, and the specific area of material is 300-700m
2/ g, hole body are 0.3-2.5cm
3/ g, in skeleton, amino content is 0-16mmol/g, and the aperture of macropore is adjustable in 200-8000nm, mesoporous aperture is adjustable in 2-30nm.In addition, holes all in silica adsorbent materials provided by the present invention is all interconnected, and the adsorbance of its crotonaldehyde can reach 5mg/g.
Second aspect present invention provides the application of preparation method in field of tobacco preparation of described macropore-mesoporous silicon dioxide sorbent material.
Macropore-mesoporous silicon dioxide sorbent material provided by the present inventionly a kind ofly have multi-stage artery structure, enriching amino-functional group and preparation method thereof combines solvent evaporation induction assembling and solvent extraction port-creating method altogether, the various features such as the multilevel hole material obtained has that aperture is adjustable, pore passage structure height is communicated with, specific area is high, surface functional group is abundant, can be used for cigarette filter sorbent material, with harmful organic substances such as crotonaldehydes in selectively reduction flue gas.In building-up process, first monodispersed organic high polymer microsphere is dispersed in and is dissolved with silicon source, in the acidic ethanol/aqueous solution of amino silicone source and surfactant, then at room temperature stirring a period of time makes the prehydrolysis of silicon source, the mixed solution of gained is carried out solvent volatilization in certain substrate, the composite film material obtained is after burin-in process, be placed in solvent reflow treatment further, polymer microsphere template and surfactant are removed in extraction, acquisition has multi-stage artery structure, enrich the macropore-mesoporous silicon dioxide sorbent material of amino-functional group.Synthesize this material obtained and there is higher specific area (300-700m
2/ g), the large (0.3-2.5cm of hole body
3/ g), its macropore diameter is adjustable in 200-8000nm, and its mesoporous pore size is adjustable in 2-30nm, and hole link is good, and hole wall has modified a large amount of amino.
Accompanying drawing explanation
Fig. 1. be shown as electron scanning micrograph (a) and transmission electron microscope photo (b) of amino functional multi-stage porous silica adsorbent materials, show multilevel ordered pore passage structure feature, wherein macropore is the arrangement of 3-D face-centered cubic, and mesoporous is 2-D Hexagonal array.The illustration of figure a is the macropore arranged model figure of material pictorial diagram photo and material respectively.
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention are described, those skilled in the art the content disclosed by this description can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by detailed description of the invention different in addition, and the every details in this description also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Notice, in the following example, the concrete process equipment that indicates or device all adopt conventional equipment in this area or device; All force value and scope all refer to absolute pressure.
In addition should be understood that the one or more method steps mentioned in the present invention do not repel and can also to there is additive method step or can also insert additive method step before and after described combination step between these steps clearly mentioned, except as otherwise noted; Will also be understood that, the relation that is connected between the one or more equipment/devices mentioned in the present invention is not repelled and can also to be there are other equipment/devices or can also insert other equipment/devices before and after described unit equipment/device between these two equipment/devices clearly mentioned, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1:
0.25gP123,0.4g ethyl orthosilicate, 0.18g γ-aminopropyltrimethoxysilane and 0.5g aqueous hydrochloric acid solution (2M) are dissolved in 15g ethanol, and at room temperature stir 4h, by the ethanolic solution (10% of the solution that obtains and 10gPMMA microballoon, particle diameter 220nm) ultrasonic mix after, pour in culture dish and be placed on solvent flashing in 30 DEG C of baking ovens, after solvent volatilization 24h, burin-in process 8h in 60 DEG C of baking ovens, obtains uniform laminated film further.The 12h and ultrasonic disperse (60mL) in oxolane refluxes under 50 ° of C is broken a little into pieces after film scrapes, granular disintegration is after filtration washing, dry in 50 DEG C of vacuum drying ovens, namely obtain that there is multi-stage artery structure, macropore-mesoporous silicon dioxide sorbent material.The macropore diameter of material is 200nm, and mesoporous pore size is 10.5nm, and specific area is 328m2/g, hole body is 0.25cm3/g, and in skeleton, amino content is 5.2mmol/g, and this material is 2.8mg/g for the adsorbance of crotonaldehyde.
Embodiment 2:
0.42gF127,0.75g ethyl orthosilicate, 0.22gN-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane and 0.8g aqueous hydrochloric acid solution (2M) are dissolved in 10g ethanol, and at room temperature stir 4h, by the ethanolic solution (10% of the solution that obtains and 15gPS microballoon, particle diameter 530nm) ultrasonic mix after, pour in culture dish and be placed on solvent flashing in 50 DEG C of baking ovens, after solvent volatilization 18h, burin-in process 16h in 80 DEG C of baking ovens, obtains uniform laminated film further.Grind and ultrasonic disperse (100mL) in toluene refluxes under 80 ° of C 24h a little after film scrapes, granular disintegration, after filtration washing, is dried in 50 DEG C of vacuum drying ovens, must have multi-stage artery structure, macropore-mesoporous silicon dioxide sorbent material.The macropore diameter of material is 512nm, and mesoporous pore size is 12.3nm, and specific area is 302m2/g, hole body is 0.33cm3/g, and in skeleton, amino content is 8.8mmol/g, and this material is 4.1mg/g for the adsorbance of crotonaldehyde.
Embodiment 3:
By 0.5gF108,1.2g ethyl orthosilicate, 0.1g γ-aminopropyltriethoxy diethoxy silane and 0.4g aqueous hydrochloric acid solution (2M) are dissolved in 10g ethanol, and at room temperature stir 12h, by the ethanolic solution (10% of the solution that obtains and 15gPS microballoon, particle diameter 1100nm) ultrasonic mix after, pour in culture dish and be placed on solvent flashing in 30 DEG C of baking ovens, until solvent volatilization 24h after, burin-in process 24h in 60 DEG C of baking ovens, obtains uniform laminated film further.The 12h and ultrasonic disperse (100mL) in carrene refluxes under 60 ° of C is broken a little into pieces after film scrapes, granular disintegration is after filtration washing, dry in 50 DEG C of vacuum drying ovens, namely obtain that there is multi-stage artery structure, macropore-mesoporous silicon dioxide sorbent material.The macropore diameter of material is 1055nm, and mesoporous pore size is 8.0nm, and specific area is 408m2/g, hole body is 0.51cm3/g, and in skeleton, amino content is 8.0mmol/g, and this material is 3.8mg/g for the adsorbance of crotonaldehyde.
Embodiment 4:
By 1.0gBrij78(C
16eO
20), 1.5g ethyl orthosilicate, 0.8g γ-divinyl triammonium hydroxypropyl methyl dimethoxysilane and 0.8g aqueous solution of nitric acid (2M) be dissolved in 15g ethanol, and at room temperature stir 4h, by the ethanolic solution (10% of the solution that obtains and 20gPS microballoon, particle diameter 1600nm) ultrasonic mix after, pour in culture dish and be placed on solvent flashing in 70 DEG C of baking ovens, after solvent volatilization 24h, burin-in process 24h in 80 DEG C of baking ovens, obtains uniform laminated film further.The 12h and ultrasonic disperse (100mL) in carrene refluxes under 60 ° of C is broken a little into pieces after film scrapes, granular disintegration is after filtration washing, dry in 50 DEG C of vacuum drying ovens, must obtain that there is multi-stage artery structure, macropore-mesoporous silicon dioxide sorbent material.The macropore diameter of material is 1550nm, and mesoporous pore size is 2.2nm, and specific area is 750m
2/ g, hole body are 2.5cm
3/ g, in skeleton, amino content is 6.5mmol/g, and this material is 2.4mg/g for the adsorbance of crotonaldehyde.
Embodiment 5:
By 1.5gBrij98(C
18h
35eO
20), 0.5g ethyl orthosilicate, 2.5g γ-aminopropyltriethoxy diethoxy silane and 0.3g dilute sulfuric acid aqueous solution (2M) be dissolved in 10g ethanol, and at room temperature stir 2h, by the ethanolic solution (10% of the solution that obtains and 15gPS microballoon, particle diameter 1200nm) ultrasonic mix after, pour in culture dish and be placed on solvent flashing in 30 DEG C of baking ovens, after solvent volatilization 24h, burin-in process 18h in 80 DEG C of baking ovens, obtains uniform laminated film further.The 12h and ultrasonic disperse (100mL) in dimethyl sulfoxide (DMSO) refluxes under 80 ° of C is broken a little into pieces after film scrapes, granular disintegration is after filtration washing, dry in 50 DEG C of vacuum drying ovens, namely obtain that there is multi-stage artery structure, macropore-mesoporous silicon dioxide sorbent material.The macropore diameter of material is 1130nm, and mesoporous pore size is 2.3nm, and specific area is 785m
2/ g, hole body are 1.78cm
3/ g, in skeleton, amino content is 16mmol/g, and this material is 5.0mg/g for the adsorbance of crotonaldehyde.
In sum, the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (5)
1. a preparation method for macropore-mesoporous silicon dioxide sorbent material, comprises the steps:
1) take the raw material of described macropore-mesoporous silicon dioxide sorbent material by proportioning, the raw material of described macropore-mesoporous silicon dioxide sorbent material by percentage to the quality, comprises following component:
2) organic high polymer microsphere is dispersed in the ethanol of the silicon source that is dissolved with, acidic aqueous solution and surfactant, then at room temperature stirs and make the prehydrolysis of silicon source;
3) by step 2) mixed solution of gained carries out solvent volatilization in substrate, the composite film material obtained is after burin-in process, be placed in solvent reflow treatment further, polymer microsphere template and surfactant are removed in extraction, obtain described macropore-mesoporous silicon dioxide sorbent material;
Described silicon source is positive esters of silicon acis and amino silicone source, and described positive esters of silicon acis is selected from ethyl orthosilicate, described amino silicone source is selected from γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, γ-divinyl triammonium hydroxypropyl methyl dimethoxysilane wherein one or more;
Described step 3) in the extractant that uses be selected from one or more the mixing wherein of oxolane, acetone, dimethyl formamide, dimethyl sulfoxide (DMSO), carrene, toluene, dioxane;
Described surfactant is selected from Brij series of products, PEO-b-PPOX-b-PEO series;
Described organic high polymer microsphere is selected from one or more in polystyrene microsphere, poly (methyl methacrylate) micro-sphere, and the particle diameter of described organic high polymer microsphere is 200-8000nm.
2. the preparation method of a kind of macropore-mesoporous silicon dioxide sorbent material as claimed in claim 1, is characterized in that, described acidic aqueous solution is selected from aqueous hydrochloric acid solution, aqueous sulfuric acid, aqueous solution of nitric acid, aqueous acetic acid one wherein.
3. the preparation method of a kind of macropore-mesoporous silicon dioxide sorbent material as claimed in claim 1, is characterized in that, described step 3) in, the actual conditions of burin-in process is: at 60-80 DEG C, toast 8-24 hour in an oven.
4. the preparation method of a kind of macropore-mesoporous silicon dioxide sorbent material as claimed in claim 1, it is characterized in that, described step 3) in, the actual conditions of reflow treatment is: at 50-80 DEG C, heat 12-24 hour under laminated film being placed in extractant normal pressure.
5. the preparation method of the macropore-mesoporous silicon dioxide sorbent material as described in claim as arbitrary in claim 1-4 is in the application of field of tobacco preparation.
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| CN104941681B (en) * | 2014-03-31 | 2019-08-13 | 华东理工大学 | Fluorescent sensing material and its application based on naphthalimide derivative |
| CN104174425B (en) * | 2014-07-11 | 2017-08-11 | 中国科学院生态环境研究中心 | It is a kind of for catalyst of volatile organic matter catalysis oxidation and preparation method thereof |
| CN105648657B (en) * | 2015-12-30 | 2018-01-26 | 中国人民解放军国防科学技术大学 | Amination mesopore silicon oxide fiber and its preparation method and application |
| CN105837509B (en) * | 2016-04-01 | 2018-08-31 | 南开大学 | A kind of preparation method of the 2-methylimidazole Zn complex with hierarchical porous structure |
| CN107774238B (en) * | 2016-08-26 | 2020-12-22 | 上海烟草集团有限责任公司 | Process for slowing down sedimentation of nano suspension, product and application thereof |
| CN107855118A (en) * | 2017-12-12 | 2018-03-30 | 成都育芽科技有限公司 | A kind of environment-friendly dye sewage-treating agent and preparation method thereof |
| CN108014756A (en) * | 2017-12-12 | 2018-05-11 | 成都育芽科技有限公司 | A kind of macroporous absorption type water pollution inorganic agent and preparation method thereof |
| CN108607511B (en) * | 2018-05-18 | 2019-05-17 | 浙江新环环保科技有限公司 | A kind of industrial waste-gas purifier using waste-gas adsorbant |
| CN108751372B (en) * | 2018-07-09 | 2021-10-08 | 苏州晏荣煜科技发展有限公司 | Silica aerogel doped calcium zeolite water treatment agent and preparation method thereof |
| CN113998703A (en) * | 2021-10-29 | 2022-02-01 | 华中科技大学 | Hierarchical radiation super-macroporous silicon dioxide nanospheres and preparation method and application thereof |
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