CN103816857A - Preparation method of SiO2/TiO2 aerogel for gas absorption as well as product and application of SiO2/TiO2 aerogel - Google Patents
Preparation method of SiO2/TiO2 aerogel for gas absorption as well as product and application of SiO2/TiO2 aerogel Download PDFInfo
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- CN103816857A CN103816857A CN201410039167.9A CN201410039167A CN103816857A CN 103816857 A CN103816857 A CN 103816857A CN 201410039167 A CN201410039167 A CN 201410039167A CN 103816857 A CN103816857 A CN 103816857A
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Abstract
The invention discloses a preparation method of SiO2/TiO2 aerogel for gas absorption. The preparation method comprises the steps: preparing SiO2 alcosol by using a split-phase method and preparing TiO2 alcosol by using a sol-gel method, respectively ageing the SiO2 alcosol and the TiO2 alcosol and then mixing, adding formamide for reaction to obtain SiO2/TiO2 alcosol, and carrying out postprocessing to obtain the SiO2/TiO2 aerogel, wherein the volume ratio of the formamide to the SiO2 alcosol is 0.04-0.08 and the mole ratio of the SiO2 alcosol to the TiO2 alcosol is (1.5-4.5): 1. Through changing the silicon-titanium ratio and controlling the dosage of the chemical additive formamide, the SiO2/TiO2 aerogel which has large specific surface area, uniform adjustable mesoporous aperture, a stable skeleton structure and a continuous double open-framework structure is prepared; when being used as a gas adsorbent, the SiO2/TiO2 aerogel has high selectivity, high adsorption capacity and low desorption power consumption.
Description
Technical field
The present invention relates to safety of coal mines, greenhouse effects and field of environment protection, relate in particular to a kind of SiO for GAS ABSORPTION
2/ TiO
2preparation method of aeroge and products thereof and application.
Background technology
Along with scientific and technological progress and universal, it is current more than 70 hundred million that world population has reached, and everything is also accompanied by huge energy resource consumption.CH
4, CO
2be important greenhouse gases, because it enters unusual weather conditions that atmosphere causes and the destruction to ozone layer, become the significant problem of whole world facing.By 2011, Chinese CO
2discharge capacity has reached 7,500,000,000 tons, account for the world then total release 25%, be first discharge state of the world today.Coal mine methane is maximum methane industrial emission source, has three kinds of main gas: CH
4, N
2and O
2, wherein CH
4aerial explosion limit is 5～15%.Because coal mine methane exists that flow is large, gas density is low, methane-rich is difficult and the problem such as potential safety hazard, make Collection and use coal mine wind-lack gas, reduce greenhouse gas emission, become the urgent task that China faces.
Various types of porous materials because of its specific skeleton structure, bigger serface and good heat endurance become absorption various gases first choice.Before twentieth century nineties, the porous materials such as the general first-selected active carbon of scientist or molecular sieve are as the adsorbent of gas, and their skeleton forms by inorganic compound.Facts have proved, even if the shared percentage of the active carbon of bigger serface or molecular sieve micropore, mesoporous even macropore is high again, adsorption gas molecule effectively.Because it is several that the dynamic radius of gas molecule only has
it can not be caught in the unfavorable single surface of pore size.This feature also becomes the obstacle of adsorption gas molecule.Document shows, the quality of porous material to gas absorption performance, and not only relevant with skeleton structure and the specific area of material, duct polarity, pore size and pore volume are also the major reasons that affects gas absorption.Particularly to CO
2, CH
4, N
2this class non-polar gas molecule, has the pore volume that matches with the dynamic radius of both gas molecules and the orderly adjustable porous aeroge in aperture and is only desirable adsorbent.
Compared with traditional inorganic porous material, ordered porous SiO
2/ TiO
2aeroge all has impayable advantage on specific area, duct is adjustable sex change or structure diversity.The more important thing is ordered porous SiO
2/ TiO
2the feature of aeroge provides thinking for constructing novel porous material.
Publication number is that the Chinese patent literature of CN103406114A discloses a kind of preparation method and application of putting the adsorbent of wastewater treatment for height, and (1) adopts split-phase method to prepare SiO
2alcosol, adopts sol-gel process to prepare TiO
2alcosol; (2) by described SiO
2alcosol and TiO
2alcosol is ageing 20～28h respectively, then by SiO
2alcosol splashes into TiO in proportion
2in alcosol, after mixing, add formamide to obtain SiO
2/ TiO
2alcogel, described alcosol is carried out to post processing after constant pressure and dry obtain composite modified SiO
2/ TiO
2aeroge; (3) by described composite modified SiO
2/ TiO
2aeroge is added to height and puts in waste water, adsorbs.
Ordered porous SiO
2/ TiO
2aeroge is a kind of novel absorption material, and this patent has only been studied it and put the application in waste water at height, and its absorption property also needs to further investigate, and at present, for by ordered porous SiO
2/ TiO
2research and practical application that aeroge separates for gas absorption are less.
Summary of the invention
The invention provides a kind of SiO for GAS ABSORPTION
2/ TiO
2preparation method of aeroge and products thereof and application.By changing the consumption of silicon titanium ratio and control chemical addition agent formamide, prepare order mesoporous SiO
2/ TiO
2aeroge; Described SiO
2/ TiO
2aeroge has bigger serface and pore volume, mesoporous aperture that homogeneous is adjustable and stable skeleton structure, and its continuous double hole channel structure makes gas upon adsorption can enter smoothly SiO
2/ TiO
2the inner surface of aeroge, guarantees the higher rate of adsorption, and simultaneously cavernous structure is clear, and mechanical performance is high, and thermodynamics, chemical stability are high; By described SiO
2/ TiO
2aeroge has high selectivity, high-adsorption-capacity, low desorb energy consumption for greenhouse gases absorption.
The invention discloses a kind of SiO for GAS ABSORPTION
2/ TiO
2the preparation method of aeroge, comprises the steps:
(1) adopt split-phase method to prepare SiO
2alcosol, adopts sol-gel process to prepare TiO
2alcosol;
(2) SiO being prepared by step (1)
2alcosol and TiO
2alcosol is ageing 12～36h respectively, under vigorous stirring, by SiO
2alcosol is added drop-wise to TiO
2in alcosol, then add formamide, after reaction, obtain SiO
2/ TiO
2alcosol, then obtain described SiO through post processing
2/ TiO
2aeroge;
Described formamide and SiO
2the volume ratio of alcosol is 0.04～0.08;
Described SiO
2alcosol and TiO
2the mol ratio of alcosol is 1.5～4.5:1.
Because the hydrolysis rate of ethyl orthosilicate is much slower than butyl titanate, ethyl orthosilicate, butyl titanate are directly mixed with ethanol, water, catalyst etc., butyl titanate is easily first hydrolyzed and forms precipitation, obtains SiO pockety
2/ TiO
2gel.For guaranteeing that ethyl orthosilicate is hydrolyzed and synchronizes with butyl titanate, need 5 hours in advance hydrolysis ethyl orthosilicates, prepare respectively silicon, titanium colloidal sol.
The described split-phase method of step (1) is prepared SiO
2the detailed process of alcosol is:
Under stirring condition, polyethylene glycol is dissolved in aqueous hydrochloric acid solution, is stirred to polyethylene glycol and is uniformly dissolved, in described polyglycol solution, add ethyl orthosilicate, continue to stir the uniform SiO of acquisition
2colloidal sol, after ageing 20～30h, adds expoxy propane to obtain SiO
2alcosol.
As preferably, the concentration of described aqueous hydrochloric acid solution is 0.05～0.5mol/L.
The present invention utilizes oligomer polymerization that phase-splitting is incorporated in sol-gel transition abreast, obtains the cavernous structure of co-continuous.Use ethyl orthosilicate (TEOS) as organosilicon source, the polyethylene glycol (PEG) that average viscosity average molecular weigh is 10,000 is induced phase-splitting as non-ionic surface active agent.
In the process of growing up at silicon oligomer, part PEG chain by Hydrogen Binding Adsorption in its surface, is accompanied by the carrying out of this absorption, and surface has the connected non-type state silicon polymer of hydrogen bond and the direct compatibility of solvent constantly to reduce.Control suitable PEG molecular weight and addition, can make solution before solvent-gel conversion, be separated into different two-phases.Along with the change of PEG content in colloidal sol, gel structure changes, and is in fact the result of vying each other between phase process and Gel-sol transition process.Conventionally, the co-continuous that phase-splitting forms is a temporary stable state mutually, if now this structure is not solidified,, under capillary driving, Ostwald maturing process can occur, and continuous two meet towards the spherical transformation of surface tension minimum.If when phase-splitting produces the two-phase of co-continuous, parallel generation sol-gel transition, can preserve this structure, wherein contain solvent more one in dry run, will form because of the volatilization of solvent phase continuous hole.If before sol-gel transition occurs in phase-splitting, now phase-splitting has little time fully to carry out, and will form the block structure in few hole; Otherwise what phase-splitting formed two meets and be transformed into spheric granules and be cured, the final pattern obtaining is ball particle heaped-up.After sol-gel transition in the present invention occurs in phase-splitting, the final pattern therefore obtaining is ball particle heaped-up.
The mass volume ratio of described polyethylene glycol, ethyl orthosilicate, aqueous hydrochloric acid solution and expoxy propane is: 1～3g:10～20ml:20～50ml:4～10ml.
The described sol-gel process of step (2) is prepared TiO
2the detailed process of alcosol is:
Butyl titanate and absolute ethyl alcohol are mixed to get to solution A, acetic acid, redistilled water and absolute ethyl alcohol are mixed to get to solution B, under stirring, solution B is added drop-wise in solution A, obtain TiO
2alcosol;
In described solution A, the concentration of butyl titanate is 30～40%;
In described solution B, acetate concentration is 10～15%;
The volume ratio of described solution A and solution B is 1～2.
As preferably, the described last handling process of step (2) is:
By SiO
2/ TiO
2alcosol with soaked in absolute ethyl alcohol 20～30h, is removed moisture content unnecessary in alcogel to replace at 50～70 ℃, after repeating to soak once, with ethanolic solution and the absolute ethyl alcohol repetition aforesaid operations of ethyl orthosilicate, finally by the SiO after immersion treatment
2/ TiO
2alcosol is dry 60～80h at 60～80 ℃, obtains described SiO
2/ TiO
2aeroge, has realized SiO
2/ TiO
2the non-supercritical of aeroge is dry.
Formamide (DCCA) is a kind of drying control chemical additive, adding formamide can make gel pore road structure more well-balanced, it is concentrated that pore-size distribution is tending towards, and reduces when gel drying due to stress difference is brought everywhere cracking and fragmentation, and this is highly beneficial to preparing the Monolithic aerogel of high porosity.In addition, add the DCCA aperture that can also increase gel network, and the increase in aperture is conducive in the process of the alcohol solution dipping of ethyl orthosilicate, ethyl orthosilicate molecule enters the each position in gel duct, with gel surface-OH reacts, generation-Si-O-Si (OC
2h
5)
2the structure of-O-Si-, and play the effect in duct supported, thus the perfect network structure of gel has been avoided the excess shrinkage in dry run.
How to make structure and the quality of aeroge further optimize and be significant, particularly, under constant pressure and dry condition, make the particle diameter of the nanoparticle that forms aeroge network more aligned, pore distribution is more even.This aeroge through structure optimization will improve absorption property greatly.Adding appropriate organic additive to contribute to improve structure and the performance of the gel that formed with ethyl orthosilicate (TEOS) in for basic sol system.Wherein, adding of drying control chemical additive formamide can make gel time slow down, gel time increases, and along with the increase of formamide addition, gel time is more and more longer, this is because added formamide is polar organic solvent, their easy and sol system Semi-polarity organic component ethanol generation affinity interactions, reduce the strong hydration of ethanol and water in reaction system, in the situation that other component proportion is constant, in the sol system that contains formamide, contain relatively many Free water, therefore with the increase of formamide, the amount of Free water also correspondingly increases, thereby limit the polycondensation reaction of Ludox system, cause gel time to increase, this reduces with ethanol addition that can to make gel time increase be consistent.In addition, the structure of another kind of additive PEG and the structure of ethanol are quite similar, between it and ethanol, affinity interaction also can occur.Therefore this law is incorporated into PEG after sol system, and polycondensation reaction speed also can reduce to a certain extent.
SiO
2/ TiO
2between the density of aeroge and the addition of formamide, there is relation, as formamide and SiO
2the volume ratio of alcosol is 0.04～0.08 o'clock, SiO
2/ TiO
2the density of aeroge is 200～300kg/cm
3.Along with the increase of formamide addition, SiO
2/ TiO
2the density of aeroge first reduces rear rising, and this may be that formamide is difficult to the caused result that plays a role completely due under this preparation condition.As preferably, described formamide and SiO
2the volume ratio of alcosol is 0.07 o'clock, SiO
2/ TiO
2the density of aeroge touches the bottom, and is 217.1kg/cm
3, now, SiO
2/ TiO
2performance the best of aeroge.
Along with the increase of Si content, composite aerogel network structure is intensive gradually.As preferably, described SiO
2alcosol and TiO
2the mol ratio of alcosol is 3～4.5:1.The SiO that silicon titanium mol ratio is 3～4.5:1
2/ TiO
2the loose structure of aeroge is relatively intensive, and the hole degree of order is obviously better than the SiO that silicon titanium mol ratio that structure loosens is relatively 1:1～2
2/ TiO
2composite aerogel.
The invention also discloses the SiO that adopts described preparation method to obtain
2/ TiO
2aeroge, described SiO
2/ TiO
2aeroge has double hole channel structure, and specific area is 500～1000m
2/ g, pore volume is 0.1～1.1cm
3/ g, average pore size is 1～15nm.By the SiO to Different Silicon titanium ratio
2/ TiO
2it is known that aeroge carries out the test of nitrogen adsorption desorption, the SiO that adopts this method to prepare
2/ TiO
2aeroge has the pore passage structure of double-deck time; Observe the SiO of Different Silicon titanium ratio
2/ TiO
2the graph of pore diameter distribution of aeroge is known, all has micropore, mesoporous, three kinds of pore structures of macropore.
The invention also discloses described SiO
2/ TiO
2aeroge is as the application of gas absorbent, and step is as follows:
Described SiO
2/ TiO
2aeroge, after pulverizing, washing, drying and processing, contacts with pending gas.
SiO prepared by the present invention
2/ TiO
2aeroge has continuous double hole channel structure, makes gas upon adsorption can enter smoothly SiO
2/ TiO
2the inner surface of aeroge, guarantees the higher rate of adsorption, and as preferably, described gas is CO
2, N
2or CH
4.
CO
2dynamic radius be
ordered porous SiO prepared by the present invention
2/ TiO
2the micropore size of aeroge is distributed in
scope, is a bit larger tham CO
2the dynamic radius of gas, is conducive to CO
2absorption.
Ordered porous SiO prepared by the present invention
2/ TiO
2aeroge and CH
4and N
2the dynamic radius of the molecule (CH that matches
4and N
2the dynamic radius of molecule is respectively
with
), micropore size is distributed in
scope.Therefore, to N
2and CH
4all there is excellent adsorption effect.
As preferably, described SiO
2/ TiO
2the silicon titanium mol ratio of aeroge is 3～4.5:1.
The SiO that silicon titanium mol ratio is 3～4.5:1
2/ TiO
2aeroge has higher specific area and micro content, and these micropores are to affect SiO
2/ TiO
2aeroge CO absorption
2the primary factor of gas, because the gesture synergy of micropore should also make SiO
2/ TiO
2interaction potential between aeroge and gas strengthens greatly.Therefore, preferred SiO
2/ TiO
2aeroge and CO
2gravitation between gas molecule is larger, SiO
2/ TiO
2aeroge is to CO
2the adsorbance of gas is just larger.
What the present invention adopted is WY-98A type absorption constant analyzer, and this instrument experiment principle is Langmuir equation, and experimental technique is high pressure content method.Be 30 ℃ of constant temperature measuring default, the gases at high pressure of 1.5MPa are passed in system.Then observe week internal pressure and represent whether value changes.If there is decline, whole air-channel system gas leakage is described, need detect equipment sealing; If change not obviously, increase and pass into the pressure of gas, repeat above-mentioned checking process, reach the required maximum pressure of experiment until pass into gas pressure value, now show that equipment seal is good, start the SiO to Different Silicon titanium ratio
2/ TiO
2ordered porous aeroge carries out isothermal adsorption experiment, can draw the adsorbance of each sample under different pressures.
In low pressure range, pore-size distribution and ionic radius are to CH
4and N
2absorption property impact larger; Along with the increase of pressure, specific area becomes the main cause that affects two kinds of gas absorption.
As preferably, the pressure in described adsorption tanks is 3～4.5MPa.
With CH
4gas is example, along with the increase of pressure, SiO
2/ TiO
2aeroge hole surface and CH
4the probability that gas molecule clashes into increases, the CH being adsorbed
4gas molecule increases, and adsorption rate is accelerated, SiO
2/ TiO
2the CH arranging on aeroge hole surface
4density of gas molecules increases.At a certain temperature, SiO
2/ TiO
2aeroge absorption CH
4the amount of gas increases along with the increase of pressure, in the time that pressure reaches certain value, adsorbs the state that reaches capacity, then continues to increase pressure, and adsorbance can not increase again.
Compared with prior art, tool of the present invention has the following advantages:
1, by the consumption of regulation and control silicon titanium ratio and chemical addition agent formamide, can prepare order mesoporous SiO
2/ TiO
2aeroge;
2, the SiO of preparation
2/ TiO
2aeroge has bigger serface and pore volume, mesoporous aperture that homogeneous is adjustable and stable skeleton structure, its continuous double hole channel structure makes adsorbate can enter smoothly the inner surface of porous adsorbent, guarantee the higher rate of adsorption, cavernous structure is clear simultaneously, mechanical performance is high, and thermodynamics, chemical stability are high;
3, by the SiO of preparation
2/ TiO
2aeroge is as adsorbent, for CO
2, N
2or CH
4absorption, there is high selectivity, high-adsorption-capacity, low desorb energy consumption;
4, by the CO collecting
2arrive SiO Deng gas inject
2/ TiO
2in aeroge, gas is at SiO
2/ TiO
2in the co-continuous duct of aeroge and Hierarchical porosity structure, spread, be finally adsorbed on inside, aeroge duct, reach storage, reduce CO in atmosphere
2the object of isothermal chamber gas.The features such as it is simple that the method has preparation, and cost is low, safe and reliable, so this composite aerogel becomes underground storage CO
2deng the first-selected sorbing material of gas.
Accompanying drawing explanation
Fig. 1 is preparation method's of the present invention flow chart;
Fig. 2 is the SiO that silicon titanium mol ratio prepared by embodiment 1 is 4.5:1
2/ TiO
2aeroge scanning electron microscope (SEM) photograph;
Fig. 3 is the SiO that silicon titanium mol ratio prepared by embodiment 2 is 3:1
2/ TiO
2aeroge scanning electron microscope (SEM) photograph;
Fig. 4 is the SiO that silicon titanium mol ratio prepared by embodiment 3 is 1.5:1
2/ TiO
2aeroge scanning electron microscope (SEM) photograph;
Fig. 5 is the SiO that silicon titanium mol ratio prepared by comparative example 1 is 1:1
2/ TiO
2aeroge scanning electron microscope (SEM) photograph;
Fig. 6 is the SiO that silicon titanium mol ratio prepared by comparative example 2 is 1.5:3
2/ TiO
2aeroge scanning electron microscope (SEM) photograph;
Fig. 7 is the SiO that embodiment 2,3 and comparative example 2 are prepared respectively
2/ TiO
2the nitrogen adsorption desorption curve map of aeroge;
Fig. 8 is the SiO that embodiment 2,3 and comparative example 2 are prepared respectively
2/ TiO
2the graph of pore diameter distribution of aeroge.
The specific embodiment
Further illustrate the present invention below in conjunction with example, technical solution of the present invention is not limited to following lifted instantiation.
Press the technological process shown in Fig. 1:
(1) SiO
2the preparation of alcosol
Under stirring condition, PEG is dissolved in the aqueous hydrochloric acid solution of 0.1mol/L, continue to stir 90min PEG is uniformly dissolved, then add TEOS, at room temperature continue to stir 30min and obtain even SiO
2colloidal sol.Ageing 24h, adds expoxy propane (PO), this colloidal sol good seal is placed in to 40 ℃ of baking ovens stand-by.Its raw material weight proportioning is as follows:
PEG：4g
TEOS：30ml
Aqueous hydrochloric acid solution: 80ml
PO：15ml。
(2) TiO
2the preparation of alcosol
10mL butyl titanate is mixed and obtains solution A with 18mL absolute ethyl alcohol; 3mL acetic acid, 3.3mL redistilled water and 18mL absolute ethyl alcohol are mixed and obtain solution B.Under strong agitation, B liquid is dropwise added in solution A, butyl titanate hydrolysis obtains TiO
2colloidal sol.
(3) SiO
2/ TiO
2the preparation of aeroge
Two kinds of colloidal sols that step (1) and (2) are obtained are prepared complex sol after the about 24h of ageing respectively, compound tense, SiO
2the addition of alcosol is 30ml, the mol ratio 4.5:1 of two kinds of alcosol.Under vigorous stirring slowly by SiO
2colloidal sol is dropwise added drop-wise to TiO with dropper
2in colloidal sol, and add 2.1ml formamide, continue strong mixing until form the SiO that uniform particles is disperseed
2/ TiO
2alcosol.At room temperature leave standstill to condensing, obtain silicon titanium than the SiO for 4.5:1
2/ TiO
2alcogel.
By the SiO obtaining
2/ TiO
2alcogel is first used soaked in absolute ethyl alcohol 24h at 60 ℃, removes moisture content unnecessary in alcogel to replace, and repeats once, then uses the ethanolic solution (1:3 volume ratio) of ethyl orthosilicate and absolute ethyl alcohol to repeat above operation; Finally by the SiO of immersion treatment
2/ TiO
2alcogel is placed directly in dry 72h in 70 ℃ of baking ovens, can obtain the SiO that silicon titanium mol ratio is 4.5:1
2/ TiO
2aeroge sample.
Test the SiO that silicon titanium mol ratio prepared by the present embodiment is 4.5:1 by BET method
2/ TiO
2the specific area of aeroge is up to 812.6m
2/ g, pore volume is 0.4385cm
3/ g, average pore size is about 1.125nm.
Embodiment 2
(1) SiO
2the preparation of alcosol
Under stirring condition, PEG is dissolved in the aqueous hydrochloric acid solution of 0.1mol/L, continue stirring and PEG was uniformly dissolved in 90 minutes, then add TEOS, at room temperature continue stirring and within 30 minutes, obtain even SiO
2colloidal sol.Ageing 24h, adds expoxy propane (PO), this colloidal sol good seal is placed in to 40 ℃ of baking ovens stand-by.Its raw material weight proportioning is as follows:
PEG：3g
TEOS：20ml
Aqueous hydrochloric acid solution: 60ml
PO：10ml。
(2) TiO
2the preparation of alcosol
10mL butyl titanate is mixed and obtains solution A with 20mL absolute ethyl alcohol; 3mL acetic acid, 4mL redistilled water and 20mL absolute ethyl alcohol are mixed and obtain solution B.Under strong agitation, B liquid is dropwise added in solution A, butyl titanate hydrolysis obtains TiO
2colloidal sol.
(3) SiO
2/ TiO
2the preparation of aeroge
Two kinds of colloidal sols that step (1), (2) are obtained are prepared complex sol, SiO after the about 24h of ageing respectively
2the addition of alcosol is 30ml, and two kinds of alcosol of compound tense are that 3:1 mixes according to mol ratio.Under vigorous stirring slowly by SiO
2colloidal sol is dropwise added drop-wise to TiO with dropper
2in colloidal sol, and add 2.1ml formamide, continue strong mixing until form the SiO that uniform particles is disperseed
2/ TiO
2alcosol.At room temperature leave standstill to condensing, obtain silicon titanium than the SiO for 3:1
2/ TiO
2alcogel.
The SiO that is 3:1 by the silicon titanium ratio obtaining
2/ TiO
2alcogel is first used soaked in absolute ethyl alcohol 24h at 60 ℃, removes moisture content unnecessary in alcogel to replace, and repeats once, then uses the ethanolic solution (1:3 volume ratio) of ethyl orthosilicate and absolute ethyl alcohol to repeat above operation; Finally by immersion treatment SiO
2/ TiO
2alcogel is placed directly in dry 72h left and right in 70 ℃ of baking ovens can obtain silicon titanium than the SiO for 3:1
2/ TiO
2aeroge sample.
Test the SiO that silicon titanium mol ratio prepared by the present embodiment is 3:1 by BET method
2/ TiO
2the specific area of aeroge is 764.13m
2/ g, pore volume is 0.6974cm
3/ g, average pore size is about 2.057nm.
(1) SiO
2the preparation of alcosol
Under stirring condition, PEG is dissolved in the aqueous hydrochloric acid solution of 0.1mol/L, continue stirring and PEG was uniformly dissolved in 90 minutes, then add TEOS, at room temperature continue stirring and within 30 minutes, obtain even SiO
2colloidal sol.Ageing 24h, adds expoxy propane (PO), this colloidal sol good seal is placed in to 40 ℃ of baking ovens stand-by.Its raw material weight proportioning is as follows:
PEG：1.5g
TEOS：10ml
Aqueous hydrochloric acid solution: 30ml
PO：5ml。
(2) TiO
2the preparation of alcosol;
10mL butyl titanate is mixed and obtains solution A with 20mL absolute ethyl alcohol; 3mL acetic acid, 4mL redistilled water and 20mL absolute ethyl alcohol are mixed and obtain solution B.Under strong agitation, B liquid is dropwise added in solution A, butyl titanate hydrolysis obtains TiO
2colloidal sol.
(3) SiO
2/ TiO
2the preparation of aeroge
Two kinds of colloidal sols that step (1), (2) are obtained are prepared complex sol, SiO after the about 24h of ageing respectively
2the addition of alcosol is 30ml, and two kinds of alcosol of compound tense are that 1.5:1 mixes according to mol ratio.Under vigorous stirring slowly by SiO
2colloidal sol is dropwise added drop-wise to TiO with dropper
2in colloidal sol, and add 2.1ml formamide, continue strong mixing until form the SiO that uniform particles is disperseed
2/ TiO
2alcosol.At room temperature leave standstill to condensing, obtain silicon titanium than the SiO for 1.5:1
2/ TiO
2alcogel.
The SiO that is 1.5:1 by the silicon titanium ratio obtaining
2/ TiO
2alcogel is first used soaked in absolute ethyl alcohol 24h at 60 ℃, removes moisture content unnecessary in alcogel to replace, and repeats once, then uses the ethanolic solution (1:3 volume ratio) of ethyl orthosilicate and absolute ethyl alcohol to repeat above operation; Finally by the SiO of immersion treatment
2/ TiO
2alcogel is placed directly in dry 72h in 70 ℃ of baking ovens can obtain SiO
2/ TiO
2aeroge sample.
Test the SiO that silicon titanium mol ratio prepared by the present embodiment is 1.5:1 by BET method
2/ TiO
2the specific area of aeroge is 623.1m
2/ g, pore volume is 0.9175cm
3/ g, average pore size is about 3.163nm.
Embodiment 4～6
Adopt the preparation process identical with embodiment 1, only the consumption of formamide is replaced with respectively to 1.2ml, 2.5ml, 3ml.
Comparative example 1
(1) SiO
2the preparation of alcosol
By ethyl orthosilicate, absolute ethyl alcohol, deionized water according to a certain volume evenly mix, with nitric acid regulator solution pH value be 0.6, under 353K, be hydrolyzed after 30min, room temperature leave standstill continuation be hydrolyzed, make SiO
2colloidal sol.
Ethyl orthosilicate 14mL
Absolute ethyl alcohol 20mL
Deionized water 4mL
(2) TiO
2the preparation of colloidal sol:
Butyl titanate is mixed and obtains solution A with absolute ethyl alcohol; Acetic acid, redistilled water and equivalent absolute ethyl alcohol are mixed and obtain solution B.Under 200 revs/min, solution B is dropwise added in solution A, butyl titanate hydrolysis obtains TiO
2colloidal sol.Its raw material weight proportioning is as follows:
Butyl titanate 20mL
Absolute ethyl alcohol 50mL
Acetic acid 10mL
Redistilled water 10mL.
(3) SiO
2/ TiO
2the preparation of aeroge:
Two kinds of colloidal sols that step (1), (2) are obtained are prepared complex sol, SiO after the about 24h of ageing respectively
2the addition of alcosol is 30ml, and two kinds of alcosol of compound tense are that 1:1 mixes according to mol ratio.Under vigorous stirring slowly by SiO
2colloidal sol is dropwise added drop-wise to TiO with dropper
2in colloidal sol, and add 2.1ml formamide, continue strong mixing until form the SiO that uniform particles is disperseed
2/ TiO
2alcosol.At room temperature leave standstill to condensing, obtain silicon titanium than the SiO for 1:1
2/ TiO
2alcogel.
The SiO that is 1:1 by the silicon titanium ratio obtaining
2/ TiO
2alcogel is first used soaked in absolute ethyl alcohol 24h at 60 ℃, and unnecessary moisture content in alcogel is removed in displacement, repeats once, then uses the ethanolic solution (1:3 volume ratio) of ethyl orthosilicate and absolute ethyl alcohol to repeat above operation; Finally by the SiO of immersion treatment
2/ TiO
2alcogel is placed directly in dry 72h in 70 ℃ of baking ovens can obtain SiO
2/ TiO
2aeroge sample.
Test the SiO that silicon titanium mol ratio prepared by the present embodiment is 1:1 by BET method
2/ TiO
2the specific area of aeroge is 423.1m
2/ g, pore volume is 0.2155cm
3/ g, average pore size is about 20.472nm.In the time that silicon titanium mol ratio is 1:1, specific area reduces, and average pore size increases, the ideal that adsorption effect is 1.5～4.5:1 not as mol ratio.
Comparative example 2
(1) SiO
2the preparation of alcosol
Under stirring condition, PEG is dissolved in the aqueous hydrochloric acid solution of 0.1mol/L, continue stirring and PEG was uniformly dissolved in 90 minutes, then add TEOS, at room temperature continue stirring and within 30 minutes, obtain even SiO
2colloidal sol.Ageing 24h, adds expoxy propane (PO), this colloidal sol good seal is placed in to 40 ℃ of baking ovens stand-by.Its raw material weight proportioning is as follows:
PEG：1g
TEOS：10ml
Aqueous hydrochloric acid solution: 25ml
PO：4ml。
(2) TiO
2the preparation of alcosol
30mL butyl titanate is mixed and obtains solution A with 50mL absolute ethyl alcohol; 10mL acetic acid, 15mL redistilled water and 50mL absolute ethyl alcohol are mixed and obtain solution B.Under strong agitation, B liquid is dropwise added in solution A, butyl titanate hydrolysis obtains TiO
2colloidal sol.
(3) SiO
2/ TiO
2the preparation of aeroge
Two kinds of colloidal sols that step (1), (2) are obtained are prepared complex sol, SiO after the about 24h of ageing respectively
2the addition of alcosol is 30ml, and two kinds of alcosol of compound tense are that 1.5:3 mixes according to mol ratio.Under vigorous stirring slowly by SiO
2colloidal sol is dropwise added drop-wise to TiO with dropper
2in colloidal sol, and add 2.1ml formamide, continue strong mixing until form the SiO that uniform particles is disperseed
2/ TiO
2alcosol.At room temperature leave standstill to condensing, obtain the SiO that silicon titanium mol ratio is 1.5:3
2/ TiO
2alcogel.
By the SiO obtaining
2/ TiO
2alcogel is first used soaked in absolute ethyl alcohol 24h at 60 ℃, removes moisture content unnecessary in alcogel to replace, and repeats once, then uses the ethanolic solution (1:3 volume ratio) of ethyl orthosilicate and absolute ethyl alcohol to repeat above operation; Finally by the SiO of immersion treatment
2/ TiO
2alcogel is placed directly in dry 72h left and right in 70 ℃ of baking ovens can obtain the SiO that silicon titanium mol ratio is 1.5:3
2/ TiO
2aeroge sample.
Test the SiO that silicon titanium mol ratio prepared by this comparative example is 1.5:3 by BET method
2/ TiO
2the specific area of aeroge is 528.1m
2/ g, pore volume is 1.131cm
3/ g, average pore size is about 9.413nm.
Fig. 2～6 are the SiO of the Different Silicon titanium mol ratio prepared respectively of embodiment 1～3 and comparative example 1,2
2/ TiO
2the SEM figure of aeroge, all can observe obvious co-continuous pore passage structure in Fig. 2～6.Comparison diagram 2～6 is found, the SiO that silicon titanium mol ratio is 4.5:1
2/ TiO
2the SiO that aeroge (Fig. 2) and silicon titanium mol ratio are 3:1
2/ TiO
2the loose structure of aeroge (Fig. 3) is relatively intensive; The SiO that silicon titanium mol ratio is 1:1
2/ TiO
2the SiO that aeroge (Fig. 5) and silicon titanium mol ratio are 1.5:3
2/ TiO
2the loose structure of aeroge (Fig. 6) is relatively loose, and pore structure increases; Silicon titanium is than the SiO for 1.5:1
2/ TiO
2in between, cavernous structure is clear for the loose structure of composite aerogel (Fig. 4).
The SiO of Different Silicon titanium ratio prepared by the present invention
2/ TiO
2the pore passage structure of aeroge characterizes by nitrogen adsorption desorption method.Fig. 7 is the SiO of Different Silicon titanium mol ratio of preparation respectively in embodiment 2,3 and comparative example 2
2/ TiO
2the nitrogen adsorption desorption curve of aeroge, observes Fig. 7 and can find, polymolecular layer absorption has appearred in part, has obvious hysteresis circle.Just can find out from the adsorbance of low-pressure area, along with nitrogen partial pressure (P/P
0) increase, adsorbance also increases, nitrogen partial pressure can think that below 0.4 multilayer adsorbs the adsorbance that causes and increase, nitrogen partial pressure is at 0.4～0.8 o'clock, can think to exist mesoporous, further makes adsorbance increase; Arrived nitrogen partial pressure and be greater than at 0.8 o'clock, adsorbance starts a large amount of increases, and this slit that can be interpreted as forming between particle causes.Can find out from the size of hysteresis loop, adsorption desorption curve does not overlap, and illustrates that existence is mesoporous in a large number.In addition, higher-pressure region trend is also up being walked, and may be to have part macropore.Prove the SiO of Different Silicon titanium mol ratio prepared by employing this method by Fig. 7
2/ TiO
2aeroge all has multi-level pore passage structure.
Fig. 8 is the SiO of Different Silicon titanium mol ratio of preparation respectively in embodiment 2,3 and comparative example 2
2/ TiO
2the graph of pore diameter distribution of aeroge, as can be seen from Figure 8, three kinds of SiO of preparation
2/ TiO
2all there are micropore, mesoporous, three kinds of pore structures of macropore in aeroge.
Application examples
Adopt high pressure content method to measure SiO
2/ TiO
2ordered porous aeroge absorption property: set 30 ℃ of experimental temperatures, take the drying sample of the about 25g of quality handling well, pack in adsorption tanks, first carry out vacuum outgas, then measure the volume of adsorption tanks residual gas, gas to the adsorption tanks pressure that is filled with again certain volume reaches balance, and the gas part being filled with can be adsorbed, be not adsorbed still with free state in tank.The volume that deducts free state gas in tank with the volume of the gas being filled with is exactly adsorption volume.The variation of adsorption tanks internal pressure and time can be seen in the pressure-time window of program interface.After balance finishes, show that the adsorpting data of the 1st point of sample has been measured, repeat above-mentioned assay method, measure 7 adsorption equilibrium points, just can obtain equalizing pressure and the adsorbent accumulated amount of different pressures section correspondence.Take pressure as abscissa, adsorbance is ordinate, is connected in turn, and this of acquisition curve is adsorption isotherm.
One, CO
2the absorption of gas
The SiO that each embodiment and comparative example are prepared respectively
2/ TiO
2aeroge fragmentation, to neutral, is then placed in baking oven in 103 ℃ of oven dry 48h with deionized water washing, takes through pretreated SiO
2/ TiO
2aeroge sample, as CO
2the adsorbent of gas, the CO under different pressures P
2adsorbance V(cm
3/ g) in table 1～7.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Contrast table 1～7 is known, and silicon titanium prepared by embodiment 1 is than the SiO for 4.5:1
2/ TiO
2aeroge is to CO
2adsorption effect the best of gas.Under same silicon titanium ratio, the content of formamide is also to CO
2the adsorption effect of gas has impact.
Two, CH
4absorption
The SiO that silicon titanium mol ratio prepared by embodiment 2 is 3:1
2/ TiO
2aeroge fragmentation,, is then placed in baking oven and dries 48h in 103 ℃ to neutral with deionized water washing.Take through pretreated aeroge sample, as CH
4the adsorbent of gas.
Table 8
The SiO that table 8 is prepared for embodiment 2
2/ TiO
2the CH of aeroge under different pressures P
4adsorbance V(cm
3/ g).
Two, N
2absorption
The SiO that silicon titanium mol ratio prepared by embodiment 3 is 1.5:1
2/ TiO
2aeroge fragmentation,, is then placed in baking oven and dries 48h in 103 ℃ to neutral with deionized water washing.Take through pretreated aeroge sample, as N
2adsorbent.
Table 9
The SiO that table 9 is prepared for embodiment 3
2/ TiO
2the N of aeroge under different pressures P
2adsorbance V(cm
3/ g).
Claims (10)
1. the SiO for GAS ABSORPTION
2/ TiO
2the preparation method of aeroge, is characterized in that, comprises the steps:
(1) adopt split-phase method to prepare SiO
2alcosol, adopts sol-gel process to prepare TiO
2alcosol;
(2) SiO being prepared by step (1)
2alcosol and TiO
2alcosol is ageing 12～36h respectively, under vigorous stirring, by SiO
2alcosol is added drop-wise to TiO
2in alcosol, then add formamide, after reaction, obtain SiO
2/ TiO
2alcosol, then obtain described SiO through post processing
2/ TiO
2aeroge;
Described formamide and SiO
2the volume ratio of alcosol is 0.04～0.08;
Described SiO
2alcosol and TiO
2the mol ratio of alcosol is 1.5～4.5:1.
2. preparation method as claimed in claim 1, is characterized in that,
The described split-phase method of step (1) is prepared SiO
2the detailed process of alcosol is:
Under stirring condition, polyethylene glycol is dissolved in aqueous hydrochloric acid solution, is stirred to polyethylene glycol and is uniformly dissolved, in described polyglycol solution, add ethyl orthosilicate, continue to stir the uniform SiO of acquisition
2colloidal sol, after ageing 20～30h, adds expoxy propane to obtain SiO
2alcosol;
The mass volume ratio of described polyethylene glycol, ethyl orthosilicate, aqueous hydrochloric acid solution and expoxy propane is: 1～3g:10～20ml:20～50ml:4～10ml.
3. preparation method as claimed in claim 1, is characterized in that, the described sol-gel process of step (2) is prepared TiO
2the detailed process of alcosol is:
Butyl titanate and absolute ethyl alcohol are mixed to get to solution A, acetic acid, redistilled water and absolute ethyl alcohol are mixed to get to solution B, under stirring, solution B is added drop-wise in solution A, obtain TiO
2alcosol;
In described solution A, the concentration of butyl titanate is 30～40%;
In described solution B, acetate concentration is 10～15%;
The volume ratio of described solution A and solution B is 1～2.
4. preparation method as claimed in claim 1, is characterized in that, the described last handling process of step (2) is:
By SiO
2/ TiO
2alcosol with soaked in absolute ethyl alcohol 20～30h, after repeating to soak once, uses the ethanolic solution of ethyl orthosilicate and absolute ethyl alcohol to repeat aforesaid operations, finally by the SiO after immersion treatment at 50～70 ℃
2/ TiO
2alcosol is dry 60～80h at 60～80 ℃, obtains described SiO
2/ TiO
2aeroge.
5. the preparation method as described in claim as arbitrary in claim 1～4, is characterized in that described formamide and SiO
2the volume ratio of alcosol is 0.07.
6. preparation method as claimed in claim 5, is characterized in that, described SiO
2alcosol and TiO
2the mol ratio of alcosol is 3～4.5:1.
7. the SiO that the preparation method as described in a claim as arbitrary in claim 1～6 obtains
2/ TiO
2aeroge, is characterized in that, described SiO
2/ TiO
2aeroge has double hole channel structure, and specific area is 500～1000m
2/ g, pore volume is 0.1～1.1cm
3/ g, average pore size is 1～15nm.
8. a SiO as claimed in claim 7
2/ TiO
2aeroge, as the application of gas absorbent, is characterized in that, step is as follows:
Described SiO
2/ TiO
2aeroge, after pulverizing, washing, drying and processing, contacts with pending gas.
9. application as claimed in claim 8, is characterized in that, described pending gas is CO
2, N
2or CH
4.
10. application as claimed in claim 9, is characterized in that, described SiO
2/ TiO
2the silicon titanium mol ratio of aeroge is 3～4.5:1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492370A (en) * | 2014-11-24 | 2015-04-08 | 中国矿业大学 | Modified montmorillonite carbon dioxide adsorption material and preparation method thereof |
| CN105295506A (en) * | 2015-12-04 | 2016-02-03 | 武汉理工大学 | Improved Stober method for preparing tio2/sio2 aerogel microsphere |
| CN105854744A (en) * | 2016-05-17 | 2016-08-17 | 浙江大学 | Magnetic nanoparticle/SiO2 aerogel and preparation method thereof and method for treating high level liquid waste |
| CN106629753A (en) * | 2016-12-01 | 2017-05-10 | 深圳中凝科技有限公司 | Preparation method of SiO2 aerogel and doped TiO2 composite |
| CN110354808A (en) * | 2019-07-18 | 2019-10-22 | 浙江工业大学 | One kind is with SiO2- MTES hybrid aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406114A (en) * | 2013-07-11 | 2013-11-27 | 浙江大学 | Preparation method and application of adsorbent for high-level wastewater treatment |
-
2014
- 2014-01-27 CN CN201410039167.9A patent/CN103816857B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406114A (en) * | 2013-07-11 | 2013-11-27 | 浙江大学 | Preparation method and application of adsorbent for high-level wastewater treatment |
Non-Patent Citations (1)
| Title |
|---|
| 吴俊升等: "纳米多孔气凝胶材料在催化和吸附领域的应用", 《功能材料》, 31 December 2004 (2004-12-31) * |
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| CN104492370A (en) * | 2014-11-24 | 2015-04-08 | 中国矿业大学 | Modified montmorillonite carbon dioxide adsorption material and preparation method thereof |
| CN105295506A (en) * | 2015-12-04 | 2016-02-03 | 武汉理工大学 | Improved Stober method for preparing tio2/sio2 aerogel microsphere |
| CN105295506B (en) * | 2015-12-04 | 2018-06-26 | 武汉理工大学 | A kind of improvement St*ber methods prepare TiO2/SiO2The method of aerogel microball |
| CN105854744A (en) * | 2016-05-17 | 2016-08-17 | 浙江大学 | Magnetic nanoparticle/SiO2 aerogel and preparation method thereof and method for treating high level liquid waste |
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| CN110354808B (en) * | 2019-07-18 | 2022-03-01 | 浙江工业大学 | By SiO2Method for removing thiophene sulfides in fuel oil by using-MTES hybrid aerogel as adsorbent |
| WO2022032338A1 (en) * | 2020-08-10 | 2022-02-17 | Commonwealth Scientific And Industrial Research Organisation | Microporous aerogel |
| CN114774100A (en) * | 2022-03-02 | 2022-07-22 | 中国石油大学(华东) | Method for burying CO2 by using SiO2 aerogel nano fluid and application |
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