CN104030301B - A kind of silica aerogel material and preparation method thereof - Google Patents
A kind of silica aerogel material and preparation method thereof Download PDFInfo
- Publication number
- CN104030301B CN104030301B CN201410270352.9A CN201410270352A CN104030301B CN 104030301 B CN104030301 B CN 104030301B CN 201410270352 A CN201410270352 A CN 201410270352A CN 104030301 B CN104030301 B CN 104030301B
- Authority
- CN
- China
- Prior art keywords
- acid
- fiber
- drying
- gel
- water glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Silicon Compounds (AREA)
Abstract
Invention relates to a kind of silica aerogel material and preparation method thereof, in particular to taking water glass as silicon source, by add not chloride ion-containing and fluorion containing sour organic solvent, generate the precipitation of sodium ion, potassium ion and other ionizable metal salts, filtered mode removes precipitation again, obtain high-purity silicasol, after through sol-gel, aging, acidifying, modification, drying process, obtain silica aerogel material.Acidification before modified improves the reactive behavior on Silica hydrogel surface, thus significantly improves effect and the efficiency of modification.The present invention is with low cost, technique is simply efficient, be conducive to high efficiency production in enormous quantities, whole technological process is not containing chlorion and fluorion, improve the safety and reliability that equipment runs, product can be used for the heat-insulation and heat-preservation to the higher nuclear power of protection against corrosion requirement and liquefied natural gas facility and pipeline, can also be used for the insulation in the fields such as aerospace, petrochemical industry chemical industry, track traffic, boats and ships automobile, building.
Description
Technical field
The present invention relates to a kind of silica aerogel material and preparation method thereof, in particular to taking water glass as silicon source, sour organic solvent is contained by adding not chloride ion-containing and fluorion, quick desalination thus obtain high-purity silicasol, again through sol-gel, aging, acidifying, modification, drying process, thus obtain aerogel material.This aerogel material is chloride ion-containing and fluorion not, can be used for the heat-insulation and heat-preservation to the higher nuclear power of protection against corrosion requirement and liquefied natural gas facility and pipeline, the insulation in the fields such as aerospace, petrochemical industry chemical industry, track traffic, boats and ships automobile, refrigerator freezer, building can also be used for.
Background technology
Aerogel is a kind of novel nano thermal insulation material, within 1931, invented by U.S. Kistler.S., be otherwise known as " blue smoke ", " cigarette freezed ", be known as the magical material changing the world, since being classified as the nineties in 20th century, one of 10 big hot topic science and technology, are the dual-use technology with huge applications value.
Aerogel has mutually to assemble with nanometer scale ultrafine particle and is formed nanoporous network structure, and porosity is up to 80 ~ 99.8%, and density lowly can reach 0.003g/cm
3, room temperature thermal conductivity lowly can reach 0.013w/ (mk), and use temperature can reach 1300 DEG C, is solid material the lightest up to now and heat-insulating property best material, is called as super insulating material, can be widely used in the adiabatic heat-insulation in each field.
The aerogel material sold in the market, many employings tetraethoxy is silicon source, trimethylchlorosilane does hydrophobic modifier, although technical maturity, quality is better, but organosilicon fancy price has still had a strong impact on application and the popularization of aerogel material, and the aerogel material of the high-efficiency insulated needs in the field such as nuclear power and natural gas liquids not chloride ion-containing and fluorion, on current market, product is also difficult to meet the demands.
Water glass silicon source to be easy to get cheapness due to raw material, is subject to researchist's extensive concern, especially prepares in aerogel material process how to remove sodium ion and all kinds of impurity has carried out a large amount of developments for water glass silicon source.
Patent CN1087271C(ZL96198951.3) disclose the preparation method of the organically-modified aerogel that the salt of formation can be made to precipitate, its method removing salinity in water glass is, now by water glass and acid-respons, generate the acidic silicasol contained salt, then this silicon sol is cooled to 0 ~ 30 DEG C, particularly preferably 0 ~ 5 DEG C, then separate out from silicon sol because the solubleness in aqueous of salinity under low temperature reduces.Then filtration unit is used to divide isolated precipitation.
Patent CN1126591C(ZL97181105.9) disclose the method for organically-modified aerogel, its method removing salinity in water glass is, first under the effect of acidic ion exchange resin, mineral acid or hydrochloric acid solution, water glass solution is adjusted to pH<3, carrying out the silicic acid of polycondensation gained by adding alkali, forming aerosil.Wash gel with water afterwards, to dissociate wherein all ionogen.
Patent CN200710175741.3 discloses a kind of low cost and prepares SiO
2the method of aerogel microball, its method removing salinity in water glass is, dilute by the volume ratio 35 ~ 3:1 of water and water glass, then join in sodium form strong acid type styrene type cation exchange resin and stir 10 minutes, then through deionized water or distilled water wash extremely neutrality.
Patent CN200880010090.5 discloses the method and hydrophobic aerogel prepared therefrom of preparing hydrophobic aerogel, its method removing salinity in water glass is, at room temperature water glass (water glass) is joined in hydrochloric acid l, until the pH of solution is adjusted to 3 ~ 4; Again by under adding nonionogenic tenside and water glass and making solution be in the acidic conditions of pH4 ~ 6, form Silica hydrogel, then with the Silica hydrogel that distilled water wash is formed.
Patent CN200810011646.4 discloses a kind of TiO
2-SiO
2composite aerogel and preparation method thereof, it is removed method of salinity in water glass and is, by the industrial waterglass of modulus 3.38 and deionized water by volume 1:4 dilute, then carry out ion-exchange with strongly acidic styrene's Zeo-karb.
Patent CN201110107204.1 discloses a kind of method preparing aerosil, and its method removing salinity in water glass is: water glass is joined in hydrochloric acid and reacts, until the pH of solution is adjusted to 3 ~ 4, form silica hydrogel; Described silica hydrogel is placed in one to be placed with in the container of water, and described container two ends connect positive and negative electrode and the desalination that is energized respectively.
Open and the enforcement of above-mentioned patent will be conducive to the propelling of water glass silicon source aerogel material exploitation, but still there is many problems.Aerogel material is prepared in above-mentioned disclosed water glass silicon source, and the salinity in removing water glass and the method for impurity must have following four kinds: 1) low temperature crystallization method.This method needs to carry out refrigeration cool-down to colloidal sol, and energy consumption is comparatively large, and can not ensure that salinity is separated out completely under low temperature, even if at 0 DEG C, the solubleness of sodium sulfate in water also has 4.9g/100g water simultaneously; 2) ion exchange method.Storng-acid cation exchange resin is adopted to remove the metal ions such as the sodium ion in water glass.Due to Zeo-karb finite capacity (being generally 5mmol/g), this method test rank still can, if suitability for industrialized production, the sodium at high concentration ion (content is 7.5 ~ 12.8%wt) in water glass can cause ion exchange resin exchange capacity saturated rapidly, at all cannot continuous seepage; 3) deionized water or distillation washing.This method is by salinity in washing constantly dilution removal gel after gel formation.Can realize suitability for industrialized production, shortcoming is large, the consuming time length of water loss, and the brackish water treatment capacity washed out is large.4) electrode desalination.This method is also after gel formation, utilizes the electrolytical characteristic of salinity to carry out positive and negative electrode desalination.The difficulty that this method faces and the sea water desaltination of electrode method similar, be difficult to find jumbo cheap electrode.
Preparation method disclosed in above-mentioned patent goes back the situation that ubiquity uses hydrochloric acid or hydrofluoric acid, and properties-correcting agent also generally adopts the chloro-containing reagents such as trimethylchlorosilane.According to national relevant industries specification, the lagging material of chloride ion-containing and fluorion is strictly limited the use of in the heat insulating work of austenitic steel equipment and pipeline, forbid especially to use in the project such as nuclear power and natural gas liquids, this will have impact on the promotion and application of aerogel material.
Prepare the deficiency of the desalination mode of aerogel material for above-mentioned water glass, the present invention proposes new desalination mode, method is simple, efficiency is high, cost is low.The whole technological process of the present invention is not simultaneously containing chlorion and fluorion, the product made can be applicable to the insulation of the e-quipment and pipe in nuclear power and natural gas liquids field, can also be used for the insulation in the fields such as aerospace, petrochemical industry chemical industry, track traffic, boats and ships automobile, building.
Summary of the invention
Prepare in aerogel material technique for solving traditional water glass silicon source, impurity be more, except salinity process loaded down with trivial details consuming time, containing problems such as chlorion fluorions, propose a kind of silica aerogel material and preparation method thereof, it comprises following step:
(1), after water glass being diluted with pure water, mix with the organic solvent containing acid, then remove the precipitation of generation, obtain high-purity acidic silicasol;
(2) finely tune the pH value of above-mentioned acidic silicasol with alkali, directly leave standstill and form gel or be compounded to form plural gel with fiber, opalizer, leave standstill aging;
(3) above-mentioned gel acidic substance are soaked, carry out acidifying;
(4) by hydrophobic modifier, hydrophobically modified is carried out to the gel after acidifying;
(5) drying is carried out to gel and obtain aerogel material, comprise supercritical drying or constant pressure and dry or microwave vacuum drying.
Water glass pure water described in step (1) dilutes, and the volume ratio of water glass and pure water is 1:0.1 ~ 20, preferred 1:0.5 ~ 10; Water glass comprises potash water glass and sodium silicate.
Acid described in step (1) be the mineral acid of not chloride ion-containing and fluorion or organic acid one or more.Mineral acid comprises oxygen acid, oxygen-free acid, complex acid, preferably sulfuric acid and phosphoric acid; Organic acid comprises carboxylic acid (-COOH), sulfonic acid (-SO
3h),-sulfinic acid (RSOOH), thionothiolic acid (RCOSH), preferred oxalic acid, acetic acid, formic acid, propionic acid, butanic acid, positive valeric acid.
Organic solvent described in step (1) is one or more in alcohol, ether, ester, ketone, aliphatic series or aromatic hydrocarbon, in preferred molecular structure, carbonatoms is less than 8, particularly preferably methyl alcohol, ethanol, ethylene glycol, propyl alcohol, glycerol, vinylcarbinol, acetone, formaldehyde, acetaldehyde, propionic aldehyde.
Mix with containing sour organic solvent after the dilution of step (1) described water glass, can be first mix with acid after water glass dilution, then mix with organic solvent, also can be that acid first mixes with organic solvent, then mix with water glass after dilution.
The precipitation of step (1) described generation adopts the mode of filtering to remove, and comprises centrifuging, vacuum filtration, pressure filtration.
The pH value mixing the acidic silicasol of afterwards gained after the dilution of step (1) described water glass with containing sour organic solvent is 0.1 ~ 4, preferably 1.5 ~ 3.5.
Step (2) described alkali finely tune above-mentioned acidic silicasol pH value, pH value is 3.0 ~ 7.0, and alkali is one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide and ammoniacal liquor.
Step (2) described alkali finely tune above-mentioned acidic silicasol pH value after, form plural gel with fiber composite, described fiber comprise inorganic fibre and organic fibre one or more, and above-mentioned fiber makes felt, plate, cloth etc.; Organic fibre comprises terylene, polyamide fibre, spandex, acrylic fibers, aramid fiber, tynex, pre-oxidized polyacrylonitrile fiber, Kafra fiber, cellulosic fibre, carbon fiber, and inorganic fibre comprises silica fiber, high silica fiber, aluminum silicate fiber, glass fibre, mullite fiber, silicon carbide fiber, silicon nitride fiber, sapphire whisker, boron nitride fibre, basalt fibre, brucite fiber, atapulgite fibres.
After step (2) described alkali finely tunes the pH value of above-mentioned acidic silicasol, be compounded to form plural gel with opalizer, described opalizer is one or more in titanium dioxide, metatitanic acid, titanyl sulfate, zirconia titanate, zirconium dioxide, zirconium silicate, carbon black.
Acidic substance described in step (3) can be the acid that step (1) is mentioned, and also can be the mixtures of the organic solvent that the acid mentioned of step (1) and step (1) are mentioned.
Gel hydrophobic modifier described in step (4), for the waterproofing agent of organosilicon with silicon methyl structural of not chloride ion-containing and fluorion, preferred hexamethyldisilazane, hexamethyldisiloxane, methyltrimethylsilane, Union carbide A-162, dimethyldiethoxysilane, dimethyldimethoxysil,ne, trimethylethoxysilane, trimethylmethoxysilane.
Supercritical drying described in step (5), drying medium comprises ethanol or carbonic acid gas; Described constant pressure and dry, comprises warm air drying and infrared drying, and the drying medium of warm air drying is air, nitrogen or carbonic acid gas, preferred nitrogen and carbonic acid gas; Described microwave vacuum drying, before dry, equipment vacuum degree lower than 100 holders, preferably should hold in the palm lower than 10.
As previously mentioned, water glass prepares aerogel material as silicon source, remove the direction that sodium ion or potassium ion and other impurity are researchist's unremitting efforts always, the present invention utilizes most of sodium salt, sylvite, molysite and aluminium salt to be all insoluble to the characteristic of organic solvent, afterwards form salinity and separate out by diluted water glass mix with acid in organic solvent, precipitate, filter, thus obtain deionized acidic silicasol.
In the described organic solvent preferred molecular structure of step (1), carbonatoms is less than 8, particularly preferably methyl alcohol, ethanol, ethylene glycol, propyl alcohol, glycerol, vinylcarbinol, acetone, formaldehyde, acetaldehyde, propionic aldehyde, it is water-soluble to be preferably that above-mentioned organic solvent has, and can dissolve each other into be integrated while precipitation salinity with silicon sol.
For convenience of understanding, be described with the situation of sodium silicate and sulfuric acid mixing here.The main component of sodium silicate is water glass, and containing a small amount of iron ion, aluminum ion and other metal ions.After water glass mixes with sulfuric acid, nano level hydrated SiO 2 can be generated, i.e. silicon sol, generate a large amount of sodium sulfate and a small amount of ferric sulfate, Tai-Ace S 150 simultaneously.These three kinds of vitriol are all soluble salts in water, its solubleness in 20 DEG C of water is respectively 19.5g/100g water, 440g/100g water, 36.4g/100g water, but these three kinds of salt are dissolved in the organic solvents such as ethanol all hardly, just have a large amount of vitriol separate out when ethanol content in silicon sol reaches more than 5%, even if content is that the sodium sulfate of 200ppm also can be separated out when alcohol concn reaches 70%.Just the salt of silicon sol can be analyzed by organic solvents such as ethanol like this, then remove precipitation by filtering, thus reach the object except freshen impurity.
The silicon sol containing organic solvent prepared in the present invention must be acid system, otherwise organic solvent may cause the rapid gel of silicon sol and cannot separate out salinity.It is to obtain the silicon sol that can preserve the long period that the pH value of silicon sol controls 0.1 ~ 4, so that follow-up filtration desalination work.PH value 1.5 ~ 3.5 is preferably facilitate during gel in order to following adjust ph introducing alkali less as far as possible, avoids producing new impurity effect quality product.
Solvent exchange in aerogel preparation process and modifying process are often very loaded down with trivial details, consume a large amount of manpower and materials, and have seriously elongated the cycle of producing, and affect production efficiency.In the present invention, organic solvent just introduces in the process preparing silicon sol, and avoiding in traditional technology after desalination also will solvent exchange repeatedly.
In the present invention, the gel of acquisition is carried out acidifying in advance before hydrophobically modified, acidization not only can play the effect promoting that gel is aging, also can improve the activity of gel surface silicone hydroxyl, forms H on silicone hydroxyl surface
+electric charge, properties-correcting agent can generate highly active silanol (containing-OH) in sour environment simultaneously, thus accelerates the reaction of properties-correcting agent and silicone hydroxyl, and express delivery completes gel modification up hill and dale, realizes the production of high-efficiency high-quality.
In most of water glass is the research invention of preparing aerogel of silicon source and document, acid used mostly is hydrochloric acid or hydrofluoric acid, hydrophobic modifier used mostly is trimethylchlorosilane, although the aerogel of heat-proof quality excellence also can be prepared, but due to the impact of chlorion and fluorion, application cannot be obtained in the field such as nuclear power, natural gas liquids.The acid that the present invention is used and hydrophobic modification agent be not containing chlorion and fluorion, and this just avoids the corrosion of these two kinds of elements to the field devices such as nuclear power, natural gas liquids and pipeline from source, be conducive to the safety in production of client.The preferred acid of the present invention is sulfuric acid and phosphoric acid, and reason is the most common and safety of this two classes acid, and price inexpensively.Preferably nitric acid reason is not that nitric acid character is too active, and easy and organic solvent generation vigorous reaction is dangerous.
Pure aerogel foreign matter content prepared by the present invention is few, transparency is high, and indices is suitable with organosilicon source aerogel.The aerogel composite of various form and purposes can be obtained after silicon sol and filamentary material and opalizer compound in the present invention.
During constant pressure and dry employing warm air drying of the present invention, medium preferred nitrogen or carbonic acid gas two kinds of inert medias, be in order to avoid the organic solvent in aerogel contacts with oxygen, improve security; The present invention adopts microwave drying can obtain higher drying efficiency, adds that vacuum combination can avoid microwave in a reservoir because point discharge effect occurs that spark brings potential safety hazard, and under vacuum, dry efficiency improves further simultaneously.
beneficial effect.
Compared with prior art, the aerogel material that prepared by the present invention has following significant advantage.
(1) most salt is utilized all to be insoluble to the characteristic of organic solvent, the a large amount of sodium ion contained in removal water glass silicon source that can be simple and quick or potassium ion, the a small amount of iron ion, aluminum ion etc. that contain in water glass also can be removed rapidly, thus obtain the higher aerogel material of purity.
(2) precipitation filtered out directly becomes solid materials, can as solid waste process, also can sell as technical grade industrial chemicals, avoid that tradition washing deionization consumes a large amount of water resourcess, the saline pollution need for environment that washes out carries out wastewater treatment again, wastewater treatment concentrated solution also needs evaporate to dryness to become the series of problems such as solid again.
(3) organic solvent is just introduced at sol phase, can save the solvent exchange link of traditional water glass silicon source technique after deionization, save the time, also greatly reduced replacement solvent amount simultaneously, reduce cost.
(4) the present invention first carries out acidification to gel before hydrophobically modified, improves the reactive behavior on Silica hydrogel surface, thus significantly improves effect and the efficiency of modification, is conducive to high efficiency production in enormous quantities.
(5) the aerogel material whole process that prepared by the present invention does not contain chlorion and fluorion, fundamentally avoid chlorion and fluorion to the corrosion of e-quipment and pipe, both improve the safety and reliability that in aerogel production process, equipment runs, and made again acquisition aerogel products can be applied to the field to protection against corrosion requirement harshness such as nuclear power, natural gas liquids.
(6) gel that hydrophobically modified of the present invention completes can carry out supercritical drying or constant pressure and dry or microwave vacuum drying, and preparation technology has stronger adaptive faculty to different drying modes.
(7) the pure aerogel of silicon-dioxide prepared of the present invention, density is 50 ~ 120kg/m
3, specific surface area is 530 ~ 850m
2/ g, the pure aerogel that transparency is prepared close to organosilicon silicon source; Aerosil fibre composite prepared by the present invention, density is 150 ~ 360kg/m
3, thermal conductivity is 0.017 ~ 0.025w/mk, and water-intake rate is less than 2%.
Embodiment
Provided below is the embodiment of silica aerogel material, as the present invention is described in more detail.
Embodiment 1.
Take the sodium silicate 80g of modulus 3.3, add pure water 60g and stir, obtain dilution water glass.Take the sulfuric acid 20g that concentration is 40%wt, then while stirring dilution water glass is joined in sulfuric acid, until pH value is 3.Continue the ethanol 300g adding 95%wt while stirring.By the precipitation in centrifugal filter removing colloidal sol, obtain the silicon sol of transparent clarification.In silicon sol, drip the ammoniacal liquor that concentration is 1%wt, gel after adjustment pH to 4.1,50min, room temperature leaves standstill aging 5h.Aging good gel is inserted 500ml, and mass ratio is soaking at room temperature 3h in the 40%wt sulfuric acid of 2:8 and 95% alcohol mixeding liquid, carries out acidifying.The gel completing acidifying is inserted in the hexamethyldisilazane of 500ml, under room temperature, carries out hydrophobic modification.6h post-modification completes, and gel is carried out supercritical drying 10h, and drying medium is ethanol, and temperature is 260 DEG C, and pressure is 8Mpa.Gained aerogel is translucent particle, density 60kg/m
3, specific surface area 760m
2/ g.
Embodiment 2.
Take the sodium silicate 80g of modulus 3.6, add pure water 80g and stir, obtain dilution water glass.Take the phosphoric acid 25g that concentration is 30%wt, then while stirring dilution water glass is joined in phosphoric acid, until pH value is 2.3.Continue the methyl alcohol 300g adding 95%wt while stirring.By the precipitation in vacuum filter removing colloidal sol, obtain the silicon sol of transparent clarification.In silicon sol, drip the sodium hydroxide that concentration is 1%wt, gel after adjustment pH to 4.3,30min, 40 DEG C leave standstill aging 6h.Aging good gel is inserted 500ml, and mass ratio is soak 3h at 35 DEG C in the 40%wt sulfuric acid of 3:7 and propyl alcohol mixed solution, carries out acidifying.The gel completing acidifying is inserted in the dimethyldiethoxysilane of 500ml, at 50 DEG C, carries out hydrophobic modification.8h post-modification completes, and gel is carried out nitrogen warm air drying 5h, and nitrogen temperature is 80 DEG C.Gained aerogel is translucent particle, density 70kg/m
3, specific surface area 640m
2/ g.
Embodiment 3.
Take the potash water glass 80g of modulus 3.3, add pure water 100g and stir, obtain dilution water glass.Take the acetic acid 10g that concentration is wt50%, then while stirring dilution water glass is joined in acetic acid, until pH value is 3.Continue to add acetone 300g while stirring.By the precipitation in pressurization titanium rod filter removing colloidal sol, obtain the silicon sol of transparent clarification.In silicon sol, drip the potassium hydroxide that concentration is 1%, regulate pH to 3.7, add titanium dioxide opacifier and stir, pour into and be covered with in the box of fiberglass needled mat, gel after 90min, 25 DEG C of aging 7h.Aging good gel is inserted 500ml, and mass ratio is soak 3.5h at 25 DEG C in 40% oxalic acid of 2:8 and dehydrated alcohol mixed solution, carries out acidifying.Insert in the hexamethyldisiloxane of 500ml by the gel completing acidifying, 50 DEG C are carried out hydrophobic modification.7h post-modification completes, and gel is carried out microwave vacuum drying, is evacuated down to 10 before drying to microwave vacuum dryer
-below holder.Obtain aerogel glass composite felt, density 210kg/m
3, thermal conductivity 0.018w/mk, water-intake rate 1.8%.
Embodiment 4.
Take the sodium silicate 80g of modulus 2.4, add pure water 10g and stir, obtain dilution water glass.Take the sulfuric acid 20g that concentration is 40%wt, then while stirring dilution water glass is joined in acid, until pH value is 3.Continue to add anhydrous acetaldehyde 400g while stirring.By the precipitation in centrifugal filter removing colloidal sol, obtain the silicon sol of transparent clarification.In silicon sol, drip the ammoniacal liquor that concentration is 2%wt, regulate pH to 4.5, to pour in the box being covered with polyster fibre eedle-punched non-wovens gel after 20min into, leave standstill aging 15h.On aging good gel, pour 100ml into, 40% acetic acid soaks 3h, carries out acidifying.The gel completing acidifying is inserted in the trimethylmethoxysilane of 500ml, carries out hydrophobic modification.6h post-modification completes, and gel is carried out supercritical drying 10h, and drying medium is carbonic acid gas, and temperature is 40 DEG C, and pressure is 10Mpa.Obtain aerogel terylene composite felt, density 180kg/m
3, thermal conductivity 0.017w/mk, water-intake rate 1.2%.
Embodiment 5.
Take the sodium silicate 80g of modulus 3.3, add pure water 160g and stir, obtain dilution water glass.Take the sulfuric acid 20g that concentration is oxalic acid 10g and 40%wt of 10%wt, then while stirring dilution water glass is joined in acid, until pH value is 3.Continue the ethanol 300g adding 95%wt while stirring.By the precipitation in vacuum filter removing colloidal sol, obtain the silicon sol of transparent clarification.In silicon sol, drip the sodium hydroxide that concentration is 2%wt, regulate pH to 4.1, add titanyl sulfate opalizer and stir in the box pouring into and be covered with sapphire whisker plate, gel after 50min, 90 DEG C leave standstill aging 10h.Aging good gel is inserted 500ml, and mass ratio is soak 3h at 70 DEG C in the 40%wt phosphoric acid of 1:9 and propyl alcohol mixed solution, carries out acidifying.The gel completing acidifying is inserted in the methyltrimethylsilane of 500ml, at 60 DEG C, carries out hydrophobic modification.6h post-modification completes, dry 5h under gel being placed in infrared lamp.Obtain aerogel sapphire whisker composition board, density 350kg/m
3, thermal conductivity 0.023w/mk, water-intake rate 1.9%.
The above is only preferred embodiment of the present invention, not does any type of restriction to the present invention.Every above embodiment is done according to techniques and methods essence of the present invention any simple modification, equivalent variations and modification, all still belong in the scope of techniques and methods scheme of the present invention.
Claims (10)
1. a preparation method for silica aerogel material, is characterized in that, this silica aerogel material preparation process comprises the following steps:
(1), after water glass being diluted with pure water, mix with the organic solvent containing acid, then remove the precipitation of generation, obtain high-purity acidic silicasol;
Described water glass comprise in potash water glass and sodium silicate one or both;
Described acid is one or more in the mineral acid of not chloride ion-containing and fluorion or organic acid;
Mineral acid comprises one or more in oxygen acid, oxygen-free acid, complex acid; Organic acid comprises carboxylic acid (-COOH), sulfonic acid (-SO
3h) one or more, in-sulfinic acid (RSOOH), thionothiolic acid (RCOSH);
Described organic solvent comprises one or more in alcohol, ether, ester, ketone, aldehyde, aliphatic series and aromatic hydrocarbon;
The pH value of described acidic silicasol is 0.1 ~ 4;
(2) finely tune the pH value of above-mentioned acidic silicasol with alkali, directly leave standstill and form gel, aging;
Described alkali comprises one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide and ammoniacal liquor;
Described pH value is 3.0 ~ 7.0;
(3) above-mentioned gel acidic substance are soaked, carry out acidifying;
Described acidic substance can be the acid that step (1) is mentioned, and also can be the mixtures of the organic solvent that the acid mentioned of step (1) and step (1) are mentioned;
(4) by hydrophobic modifier, hydrophobically modified is carried out to the gel after acidifying;
Described gel hydrophobic modifier, for the waterproofing agent of organosilicon with silicon methyl structural of not chloride ion-containing and fluorion, comprise one or more in hexamethyldisilazane, hexamethyldisiloxane, methyltrimethylsilane, Union carbide A-162, dimethyldiethoxysilane, dimethyldimethoxysil,ne, trimethylethoxysilane, trimethylmethoxysilane;
(5) carry out drying to gel and obtain aerogel material, drying mode comprises supercritical drying or constant pressure and dry or microwave vacuum drying;
Described supercritical drying, drying medium comprises ethanol or carbonic acid gas;
Described constant pressure and dry, comprise in warm air drying and infrared drying one or both, the drying medium of warm air drying comprises one or more in air, nitrogen, carbonic acid gas;
Described microwave vacuum drying, before dry, equipment vacuum degree should lower than 100 holders.
2. a preparation method for silica aerogel material, is characterized in that, this silica aerogel material has fiber reinforcement, and preparation process comprises the following steps:
(1), after water glass being diluted with pure water, mix with the organic solvent containing acid, then remove the precipitation of generation, obtain high-purity acidic silicasol;
Described water glass comprise in potash water glass and sodium silicate one or both;
Described acid is one or more in the mineral acid of not chloride ion-containing and fluorion or organic acid;
Mineral acid comprises one or more in oxygen acid, oxygen-free acid, complex acid; Organic acid comprises carboxylic acid (-COOH), sulfonic acid (-SO
3h) one or more, in-sulfinic acid (RSOOH), thionothiolic acid (RCOSH);
Described organic solvent comprises one or more in alcohol, ether, ester, ketone, aldehyde, aliphatic series and aromatic hydrocarbon;
The pH value of described acidic silicasol is 0.1 ~ 4;
(2) finely tune the pH value of above-mentioned acidic silicasol with alkali, be compounded to form plural gel with fiber, opalizer, leave standstill aging;
Described alkali comprises one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide and ammoniacal liquor;
Described pH value is 3.0 ~ 7.0;
Described fiber comprises one or more in inorganic fibre and organic fibre, and felt, plate, one or more in cloth that above-mentioned fiber is made;
Described organic fibre comprises one or more in terylene, polyamide fibre, spandex, acrylic fibers, aramid fiber, tynex, pre-oxidized polyacrylonitrile fiber, Kafra fiber, cellulosic fibre, carbon fiber;
Described inorganic fibre comprises one or more in silica fiber, high silica fiber, aluminum silicate fiber, glass fibre, mullite fiber, silicon carbide fiber, silicon nitride fiber, sapphire whisker, boron nitride fibre, basalt fibre, brucite fiber and atapulgite fibres;
Described opalizer comprises one or more in titanium dioxide, metatitanic acid, titanyl sulfate, zirconia titanate, zirconium dioxide, zirconium silicate, carbon black;
(3) above-mentioned gel acidic substance are soaked, carry out acidifying;
Described acidic substance can be the acid that step (1) is mentioned, and also can be the mixtures of the organic solvent that the acid mentioned of step (1) and step (1) are mentioned;
(4) by hydrophobic modifier, hydrophobically modified is carried out to the gel after acidifying;
Described gel hydrophobic modifier, for the waterproofing agent of organosilicon with silicon methyl structural of not chloride ion-containing and fluorion, comprise one or more in hexamethyldisilazane, hexamethyldisiloxane, methyltrimethylsilane, Union carbide A-162, dimethyldiethoxysilane, dimethyldimethoxysil,ne, trimethylethoxysilane and trimethylmethoxysilane;
(5) carry out drying to gel and obtain aerogel material, drying mode comprises supercritical drying or constant pressure and dry or microwave vacuum drying;
Described supercritical drying, drying medium comprises ethanol or carbonic acid gas;
Described constant pressure and dry, comprise in warm air drying and infrared drying one or both, the drying medium of warm air drying comprises one or more in air, nitrogen and carbonic acid gas;
Described microwave vacuum drying, before dry, equipment vacuum degree should lower than 100 holders.
3. the preparation method described in claim 1 or 2, is characterized in that the water glass pure water described in step (1) dilutes, and the volume ratio of water glass and pure water is 1:0.1 ~ 20.
4. the preparation method described in claim 1 or 2, the mineral acid that it is characterized in that described in step (1) comprise in sulfuric acid and phosphoric acid one or both, described organic acid comprises one or more in oxalic acid, acetic acid, formic acid, propionic acid, butanic acid and positive valeric acid.
5. the preparation method described in claim 1 or 2, the organic solvent that it is characterized in that described in step (1) comprises one or more in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, glycerol, vinylcarbinol, acetone, formaldehyde, acetaldehyde and propionic aldehyde.
6. the preparation method described in claim 1 or 2, is characterized in that the precipitation of step (1) described generation adopts the mode of filtering to remove, comprises one or more in centrifuging, vacuum filtration, pressure filtration.
7. the preparation method described in claim 1 or 2, is characterized in that the pH value of step (1) described acidic silicasol is 1.5 ~ 3.5.
8. preparation method according to claim 2, is characterized in that one or more that step (2) described fiber comprises in terylene, pre-oxidized polyacrylonitrile fiber, glass fibre and aluminum silicate fiber.
9. preparation method according to claim 2, is characterized in that one or more that step (2) described opalizer comprises in titanium dioxide, zirconium silicate and carbon black.
10. the preparation method described in claim 1 or 2, is characterized in that the gel hydrophobic modifier described in step (4), comprises one or more in hexamethyldisilazane, hexamethyldisiloxane, dimethyldiethoxysilane.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410270352.9A CN104030301B (en) | 2014-06-18 | 2014-06-18 | A kind of silica aerogel material and preparation method thereof |
| PCT/CN2015/081204 WO2015192731A1 (en) | 2014-06-18 | 2015-06-10 | Silicon-based monobasic or multibasic oxide aerogel material and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410270352.9A CN104030301B (en) | 2014-06-18 | 2014-06-18 | A kind of silica aerogel material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104030301A CN104030301A (en) | 2014-09-10 |
| CN104030301B true CN104030301B (en) | 2016-03-23 |
Family
ID=51461332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410270352.9A Active CN104030301B (en) | 2014-06-18 | 2014-06-18 | A kind of silica aerogel material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104030301B (en) |
Families Citing this family (50)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941538A (en) * | 2015-06-03 | 2015-09-30 | 金承黎 | In-situ composite silicon-based multibasic oxide oxide aerogel material and preparation method thereof |
| WO2015192731A1 (en) * | 2014-06-18 | 2015-12-23 | 金承黎 | Silicon-based monobasic or multibasic oxide aerogel material and preparation method therefor |
| CN104326477B (en) * | 2014-10-10 | 2016-06-01 | 东莞市长安东阳光铝业研发有限公司 | The preparation method of a kind of electrical condenser ultra-pure silicasol |
| CN104556062B (en) * | 2014-12-30 | 2017-02-01 | 纳诺科技有限公司 | Microwave anti-explosion drying and recycling system used for aerogel material preparation |
| KR101789371B1 (en) | 2015-02-13 | 2017-10-23 | 주식회사 엘지화학 | Preparation method of silica aerogel-containing blanket and silica aerogel-containing blanket prepared by using the same |
| CN104876226B (en) * | 2015-05-11 | 2017-11-07 | 爱彼爱和新材料有限公司 | A kind of method for quickly preparing Hydrophobic silica aeroge with the subcritical drying of methanol |
| KR101868682B1 (en) * | 2015-06-01 | 2018-06-19 | 주식회사 엘지화학 | Method for preparing metal oxide-silica complex aerogel and metal oxide-silica complex aerogel prepared by using the same |
| CN104944887A (en) * | 2015-07-01 | 2015-09-30 | 卓达新材料科技集团有限公司 | Preparation method of rigid silicon dioxide aerogel insulating board |
| CN104988658B (en) * | 2015-07-13 | 2017-10-20 | 浙江理工大学 | A kind of preparation method of SiC micro/nano-fibre non-woven materials |
| CN105236912B (en) * | 2015-08-31 | 2017-11-17 | 武汉理工大学 | A kind of composite fibre strengthens hydrophobic SiO2Aeroge and preparation method thereof |
| KR101931569B1 (en) | 2015-11-03 | 2018-12-21 | 주식회사 엘지화학 | Preparation method of hydrophobic metal oxide-silica complex aerogel and hydrophobic metal oxide-silica complex aerogel produced by the same |
| 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 |
| CN105541130A (en) * | 2015-12-18 | 2016-05-04 | 卓达新材料科技集团有限公司 | Airgel composite glass preparation method |
| CN105752999A (en) * | 2016-01-29 | 2016-07-13 | 卓达新材料科技集团有限公司 | Preparation method of sodium metaaluminate modified and resin purified water glass aerogel |
| CN107098354A (en) * | 2016-02-20 | 2017-08-29 | 金承黎 | A kind of preparation method from hydrophobic silicon hydrochlorate aerogel material |
| CN105645921B (en) * | 2016-03-10 | 2018-03-06 | 深圳中凝科技有限公司 | One kind prepares composite S iO2The method of aerogel blanket |
| KR20170110993A (en) | 2016-03-24 | 2017-10-12 | 주식회사 엘지화학 | Silica aerogel manufacturing system |
| CN105967728B (en) * | 2016-05-10 | 2019-05-24 | 航天材料及工艺研究所 | A kind of fiber reinforcement Al2O3-SiO2Aeroge effectively insulating composite material and preparation method |
| CN105833736A (en) * | 2016-05-24 | 2016-08-10 | 华南理工大学 | High-selectivity low-thermal conductivity asymmetric permeable membrane as well as preparation method and application thereof |
| CN106145813A (en) * | 2016-06-28 | 2016-11-23 | 蚌埠市方阵商品混凝土有限公司 | A kind of high-temperature-resistant thermal-insulation concrete |
| US11279622B2 (en) | 2016-09-12 | 2022-03-22 | Lg Chem, Ltd. | Method for producing silica aerogel and silica aerogel produced thereby |
| CN106431168B (en) * | 2016-09-29 | 2018-08-07 | 正一集团有限公司 | A kind of method that constant pressure and dry prepares big blocky flexible air gel |
| CN106430224A (en) * | 2016-09-30 | 2017-02-22 | 昆山蓝胜建材有限公司 | Microwave drying oven and method for preparing sodium silicate aerogel by utilizing microwave drying method |
| CN106450569A (en) * | 2016-10-18 | 2017-02-22 | 华霆（合肥）动力技术有限公司 | Power battery module and power battery pack safety device |
| CN106622107A (en) * | 2016-12-01 | 2017-05-10 | 湖北硅金凝节能减排科技有限公司 | Preparation method of TiO2/SiO2 composite aerogel |
| 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 |
| CN106865558A (en) * | 2017-03-22 | 2017-06-20 | 伊科纳诺（北京）科技发展有限公司 | Normal pressure prepares the method and obtained aerosil of aerosil |
| KR102210029B1 (en) | 2017-05-18 | 2021-02-01 | 주식회사 엘지화학 | Method preparing silicon carbide particle and the silicon carbide particle prepared the same |
| CN107236287A (en) * | 2017-05-27 | 2017-10-10 | 清远初曲智能科技有限公司 | A kind of new aeroge enhancing nylon heat-insulation composite material and preparation method thereof |
| CN109020470A (en) * | 2017-06-08 | 2018-12-18 | 青岛科瑞新型环保材料集团有限公司 | A kind of method that constant pressure and dry prepares aeroge complex heat-preservation felt |
| CN107128933B (en) * | 2017-06-15 | 2020-01-14 | 武汉理工大学 | Supercritical drying preparation method of silicon dioxide aerogel thermal insulation material |
| CN108002395B (en) * | 2017-12-07 | 2020-11-03 | 北京工业大学 | Method for reducing corrosion of silicon dioxide aerogel drying process to equipment |
| CN108314411B (en) * | 2018-01-03 | 2020-02-21 | 深圳中凝科技有限公司 | Method for preparing silicon dioxide aerogel composite material by chlorine-free and alcohol-free process |
| CN108328621B (en) * | 2018-01-30 | 2021-04-13 | 同济大学 | Preparation method of ultra-low-density silicon dioxide nanotube aerogel material |
| CN108408730B (en) * | 2018-05-21 | 2020-01-24 | 山西天一纳米材料科技有限公司 | Preparation method of silica aerogel thermal insulation material with super-large pore volume |
| CN108530017A (en) * | 2018-05-21 | 2018-09-14 | 山西天纳米材料科技有限公司 | A method of producing aerogel composite by silicon source of sodium metasilicate |
| CN108358212A (en) * | 2018-05-25 | 2018-08-03 | 天津二八科技股份有限公司 | The preparation method and silica aerogel particles of silica aerogel particles |
| CN108584965B (en) * | 2018-06-26 | 2021-07-16 | 浙江岩谷科技有限公司 | Method for rapidly preparing aerogel by accelerating solvent extraction |
| CN108775079A (en) * | 2018-07-02 | 2018-11-09 | 新沂博瑞工业设计有限公司 | A kind of telescopic energy-saving environment protection architecture |
| KR102141829B1 (en) * | 2018-09-12 | 2020-08-07 | 주식회사 삼에스코리아 | Manufacturing method of synthetic quartz powder |
| CN109368647B (en) * | 2018-11-26 | 2020-12-22 | 烟台工程职业技术学院 | Preparation of modified nano-silica aerogel |
| CN109607551B (en) * | 2018-12-11 | 2021-07-09 | 航天特种材料及工艺技术研究所 | Silicon dioxide aerogel composite material and preparation method and application thereof |
| CN111099876A (en) * | 2019-12-20 | 2020-05-05 | 山东工业陶瓷研究设计院有限公司 | Preparation method of low-cost silicon dioxide aerogel composite flexible heat insulation material |
| CN111172624B (en) * | 2020-01-18 | 2022-08-23 | 福建拓烯新材料科技有限公司 | Preparation method of carbon/silicon hybrid fiber and carbon-silicon hybrid fiber |
| TWI726638B (en) | 2020-03-02 | 2021-05-01 | 趙國昇 | Preparation method of silica aerogel |
| CN111847463B (en) * | 2020-08-04 | 2022-10-18 | 泰中新材料(山东)有限公司 | Preparation method of silicon dioxide nano aerogel fiber |
| CN113412807B (en) * | 2021-06-18 | 2023-12-05 | 安徽靖淮农业科技有限公司 | Thermal insulation material for land-based fishing ground and installation method thereof |
| CN113620660A (en) * | 2021-07-17 | 2021-11-09 | 启东海中港建材有限公司 | High-strength aerated reproducible concrete and preparation method thereof |
| CN115304066A (en) * | 2022-08-22 | 2022-11-08 | 湖北硅金凝节能减排科技有限公司 | Preparation method of high-temperature-resistant aerogel powder |
| CN115521096B (en) * | 2022-09-26 | 2023-12-19 | 湖南诚友绿色建材科技有限公司 | Thermal insulation aerogel composite material, preparation method and passive house |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4342548A1 (en) * | 1993-12-14 | 1995-06-22 | Hoechst Ag | Xerogels, processes for their manufacture and their use |
| CN1204300A (en) * | 1995-11-09 | 1999-01-06 | 德国赫彻斯特研究技术两合公司 | Process for preparing organically modified aerogels in which salts formed are precipitated out |
| CN101628804A (en) * | 2008-07-18 | 2010-01-20 | 山东鲁阳股份有限公司 | Aerogel heat insulation composite material and preparation method thereof |
| CN102659120A (en) * | 2012-04-18 | 2012-09-12 | 同济大学 | Preparation method for hydrophobic large-size bulk nanometer porous SiO2 aerogel |
| CN102674374A (en) * | 2012-04-25 | 2012-09-19 | 浙江纳诺科技有限公司 | Preparation method of silica aerogel |
-
2014
- 2014-06-18 CN CN201410270352.9A patent/CN104030301B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4342548A1 (en) * | 1993-12-14 | 1995-06-22 | Hoechst Ag | Xerogels, processes for their manufacture and their use |
| CN1204300A (en) * | 1995-11-09 | 1999-01-06 | 德国赫彻斯特研究技术两合公司 | Process for preparing organically modified aerogels in which salts formed are precipitated out |
| CN101628804A (en) * | 2008-07-18 | 2010-01-20 | 山东鲁阳股份有限公司 | Aerogel heat insulation composite material and preparation method thereof |
| CN102659120A (en) * | 2012-04-18 | 2012-09-12 | 同济大学 | Preparation method for hydrophobic large-size bulk nanometer porous SiO2 aerogel |
| CN102674374A (en) * | 2012-04-25 | 2012-09-19 | 浙江纳诺科技有限公司 | Preparation method of silica aerogel |
Non-Patent Citations (2)
| Title |
|---|
| 亚硝酸钠和硫酸钠在甲醇、水中的溶解度测定与模拟;鲁文质等;《上海化工》;20070131;第32卷(第1期);第18页右栏第2段 * |
| 工业水玻璃制备疏水性SiO2气凝胶;王芳等;《材料导报B：研究篇》;20110331;第25卷(第3期);第107-111页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104030301A (en) | 2014-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104030301B (en) | A kind of silica aerogel material and preparation method thereof | |
| CN108314411B (en) | Method for preparing silicon dioxide aerogel composite material by chlorine-free and alcohol-free process | |
| CN101372337B (en) | Method for preparing transparent silicon dioxide aerogel by co-precursor normal atmosphere drying | |
| CN104941538A (en) | In-situ composite silicon-based multibasic oxide oxide aerogel material and preparation method thereof | |
| CN104129973B (en) | Preparation method of SiO2 aerogel-filled carbon aerogel | |
| CN105236419B (en) | A kind of corrosion-free SiO2The preparation method of aeroge | |
| CN104787772B (en) | A kind of preparation method of hydrophobic nano aerogel composite | |
| CN102897779B (en) | Preparation method of transparent silicon dioxide aerogel | |
| CN104961494A (en) | Aerogel composite powder material and preparation method thereof | |
| CN106867019A (en) | One kettle way prepares SiO2The method of cellulose composite aerogel material | |
| CN102351507B (en) | Method for preparing fiber-reinforced SiO2 aerogel from rice husk ash as raw material | |
| Cui et al. | Preparation of SiO 2 aerogel from rice husk ash | |
| CN105622767B (en) | Preparation method of hydrophobic nano cellulose aerogel | |
| CN101264891A (en) | Method for preparing high-strength low-density silicon dioxide aerogel | |
| WO2019075793A1 (en) | Method for continuously preparing boron-doped sio2 aerogel | |
| CN102320615A (en) | Method for preparing precipitated silica by adopting micro-silica fume as raw material | |
| CN110615663B (en) | Solid wood fiber/SiO2Aerogel composite thermal insulation material and preparation method thereof | |
| CN102807358A (en) | Flexible aerogel block and preparation method thereof | |
| CN104446304A (en) | Aerogel composite material with multi-scale and multi-network composite structure and preparation method of aerogel composite material | |
| CN107151020A (en) | A kind of method that silicon dioxide silica aerogel composite material is prepared with freeze-drying method | |
| CN104761235A (en) | Preparation method of low-temperature-resistant glass-fiber-reinforced SiO2 aerogel composite material | |
| CN102731060A (en) | Preparation method for carbon fiber felt reinforced C-Al2O3 composite aerogel | |
| CN104402197A (en) | Low water content quartz glass material preparation method | |
| CN107935540A (en) | A kind of preparation process of oxidization fiber fiber composite type aerosil insulation blanket | |
| CN109354028A (en) | A method of mixing silicon source copolymerization prepares flexible aeroge compound insulating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180425 Address after: 312366 room 106, building 15, Changhe Road, Lehai Town, Binhai New Town, Shaoxing, Zhejiang Patentee after: Zhejiang San run nanotechnology Co., Ltd. Address before: 312000 Zhejiang, Shaoxing Yuecheng District Wolong Road, new village 25-104 Patentee before: Jin Chengli |
|
| TR01 | Transfer of patent right |