CN107128933A - A kind of supercritical drying preparation method of aerosil heat-barrier material - Google Patents
A kind of supercritical drying preparation method of aerosil heat-barrier material Download PDFInfo
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- CN107128933A CN107128933A CN201710454634.8A CN201710454634A CN107128933A CN 107128933 A CN107128933 A CN 107128933A CN 201710454634 A CN201710454634 A CN 201710454634A CN 107128933 A CN107128933 A CN 107128933A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
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Abstract
The present invention relates to a kind of supercritical drying preparation method of aerosil heat-barrier material：Comprise the following steps：1) water glass solution is diluted first by a certain amount of deionized water；2) water glass solution after dilution is added at a slow speed in concentrated hydrochloric acid solution, be stirred continuously, be allowed to well mixed, obtain the Ludox of highly acid；3) the acid silicon dioxide sol solution rotating is evaporated into part moisture, taken out, add the water soluble polar solvent of low surface tension, stirring is allowed to well mixed, add water glass solution regulation pH value of solution, you can form gel；4) water soluble polar solvent age gelation is added into gel, gained wet gel is placed in extraction kettle afterwards, it is high-pressure sealed, it is passed through supercritical CO2, contacted with wet gel, carry out extraction drying.The beneficial effects of the present invention are：Present invention process can be completed within half a day.
Description
Technical field
The invention belongs to technical field of macromolecules, and in particular to a kind of supercritical drying of aerosil heat-barrier material
Dry preparation method.
Background technology
Aerosil is a kind of light nanoporous material of structure-controllable, with many excellent performances, such as
High porosity, high-specific surface area, low-density, lower thermal conductivity etc..Aerosil is prepared both at home and abroad generally all with positive silicic acid
Methyl esters, tetraethyl orthosilicate or " waterglass " are raw material, using sol-gel processing, are made through constant pressure and dry, such as Chinese patent
200810042222.4,200910042159.5,201210123519.X, CN201210121968.0,
CN201210114691.9 etc. is prepared for meso-porous titanium dioxide Silica Aerogels by presoma of organic or inorganic silicon source.Its is general
Store-through the problem of be that manufacturing cycle is longer, hydrophilic material can not be prepared, continuous production capacity is weaker etc., is unfavorable for scale
Operation.
Chen Guo, Mr. Zhang etc. (Chinese patent, application number 201210078237.2) are disclosed with tetraethyl orthosilicate and Ludox
For raw material, the method that supercritical drying prepares aerosil after aging.But the temperature of this kind of supercritical drying mode
Up to 250 DEG C of degree, pressure is 22MPa, expends mass energy, operational hazards, and using tetraethyl orthosilicate as silicon source, significantly
The cost of aeroge is added, and is unfavorable for large-scale production；Similar, Chinese patent (application number 201510911661.4) is adopted
With the supercritical drying drying method of solvent, pressure is also of a relatively high with temperature, and silicon source also equally employs organic silicon source of costliness,
So as to which the production cost of aeroge can be caused to increase.
To sum up, the technology that supercritical drying prepares aerosil at this stage is made using organic silicon source as presoma
Standby cost is higher, so as to cause holding at high price for aerosil in the market.
The content of the invention
It is an object of the invention to provide a kind of supercritical drying preparation method of the aerosil of low-density, greatly
The exchange of solvent time is reduced greatly, production cost is reduced, while supercritical drying shortens manufacturing cycle.
The present invention solves the technical scheme that is used of above-mentioned technical problem：A kind of aerosil heat-barrier material
Supercritical drying preparation method, it is characterised in that：Comprise the following steps：
1) water glass solution is diluted first by a certain amount of deionized water；
2) water glass solution after dilution is added at a slow speed in concentrated hydrochloric acid solution, be stirred continuously, be allowed to well mixed, obtain
To the Ludox of highly acid；
3) the acid silicon dioxide sol solution rotating is evaporated into part moisture, taken out, add the water of low surface tension
Soluble polar solvent, stirring be allowed to well mixed, add a certain amount of step 1) in water glass solution regulation pH value of solution arrive
5.5-6, you can form gel；
4) to step 3) water soluble polar solvent age gelation is added 2~12 hours in gained gel, it is afterwards that gained is wet
Gel is placed in extraction kettle, high-pressure sealed, is passed through supercritical CO2, contacted with wet gel, carry out extraction drying, drying time is
2-5h。
By such scheme, step 1) described in water glass solution be sodium silicate, lithium silicate or KP1, its modulus
For 2.5~3.55, described water glass solution and the volume ratio of deionized water are 1:0.5 to 1:3,.
By such scheme, step 2) in the concentration of concentrated hydrochloric acid used be 8-12mol/L, speed of agitator is 300~600r/
min。
By such scheme, step 2) in the concentration of concentrated hydrochloric acid used be 12mol/L.
By such scheme, step 2) in gained highly acid Ludox pH value be less than 1.5.
By such scheme, step 3) in rotary evaporation temperature be 40-75 DEG C, the rotary evaporation time be 2-15min.
By such scheme, step 3) and step 4) in water soluble polar solvent be ethanol, methanol, isopropanol, propyl alcohol, third
Ketone.
By such scheme, step 3) described in water glass solution be sodium silicate, lithium silicate or KP1, its concentration
Can be 3~5.5mol/L.
By such scheme, step 4) in temperature in extraction kettle can be 35-45 DEG C, pressure can be 7.4-8.5MPa.
The present invention as silicon source, is enabled with ethanol etc. using cheap waterglass by the transformation to Ludox pH value
Organic solvent dissolves each other, and forms colloidal sol, gel using organic solvent as main solvent.And by consult pertinent literature can find it is overcritical
The carbon dioxide of state has the ratio between solubility of solvent and water to ethanol etc. 10 or so, just can be disposably by organic solvent
Taken out with water extraction, so as to reach the purpose of exchange of solvent.Fluid after extraction is completed in gel pore is all changed into CO2,
By changing temperature and pressure, CO can be made2Directly it is changed into gaseous state from above-critical state, again period, capillary pressure is always 0,
So as to obtain the aerosil of high-quality.
The beneficial effects of the present invention are：Using cheap industrial waterglass as presoma, using innovative technological process,
With organic solvent as its primary solvent, wet gel is obtained, the exchange of solvent time is greatly shortened with preparing cost.It is presently commercially available
The aerosil overwhelming majority be prepared from using supercritical drying modes, and the silicon source used in them is positive silicic acid four
Ethyl ester, this kind of reagent is expensive, is more than 100 times of waterglass.Part aeroge is prepared using constant pressure and dry mode, although
This mode equally can be using waterglass as silicon source, but this kind of method can only prepare hydrophobic type aeroge (non-refractory, 250 DEG C
Used when following), it is impossible to prepare resistant to elevated temperatures clear water type aeroge, and its long preparation period (more than 1.5 days), and work of the present invention
Skill can be completed within half a day.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
Embodiment 1
1) 70mL sodium silicates (3.55 moulds, 32.16%) are taken, is diluted with 70mL deionized waters, is stirred, obtain solution
A.Solution A is poured slowly into the not diluted concentrated hydrochloric acids of 20mL (12mol/L) afterwards, stirs while adding that (speed of agitator is 300
~600r/min), the silicon sol solution B of highly acid is obtained, the Ludox pH value of the highly acid of gained is less than 1.5；
2) the 100mL acidic silicasols are taken, are placed in Rotary Evaporators, design temperature is 50 DEG C, the revolving time is 10 points
Clock, obtains 70mL Ludox, takes out colloidal sol, and 70mL absolute ethyl alcohols are added thereto, and magnetic agitation is allowed to well mixed.It is backward
A is wherein added dropwise, regulation pH value of solution is to 6 ,~20min formation gels；
3) absolute ethyl alcohol aging 4 hours is added into the gel of formation, gel is placed in autoclave afterwards,
7.4Mpa, carries out supercritical CO under the conditions of 35 DEG C22h is dried in extraction.Finally obtain the heat-insulated material of hydrophilic aerosil
Material.Its density：0.088g/cm3, porosity：96%, thermal conductivity：0.019W/m·K.
Embodiment 2
1) 70mL lithium silicates (3.4 moulds, 30.64%) are taken, is diluted with 70mL deionized waters, is stirred, obtain solution
A.Mixed solution is poured slowly into the not diluted concentrated hydrochloric acids of 20mL (12mol/L) afterwards, stirs while adding that (speed of agitator is
300~600r/min), the silicon sol solution of highly acid is obtained, the Ludox pH value of the highly acid of gained is less than 1.5；
2) the 100mL acidic silicasols are taken, are placed in Rotary Evaporators, design temperature is 60 DEG C, the revolving time is 5 points
Clock, obtains 70mL Ludox, takes out colloidal sol, and 70mL absolute methanols are added thereto, and magnetic agitation is allowed to well mixed.It is backward
Step 1 is wherein added dropwise) in solution A, regulation pH value of solution to 6 ,~15min formation gel；
3) absolute methanol aging 3 hours is added into the gel of formation, gel is placed in autoclave afterwards,
7.6Mpa, carries out supercritical CO under the conditions of 38 DEG C23h is dried in extraction.Finally obtain the heat-insulated material of hydrophilic aerosil
Material.Its density：0.092g/cm3, porosity：95.82%, thermal conductivity：0.020W/m·K.
Embodiment 3
1) 70mL KP1s (3.2 moulds, 29.8%) are taken, is diluted with 70mL deionized waters, is stirred, obtain solution A.
Mixed solution is poured slowly into 20mL concentrated hydrochloric acids (10mol/L) afterwards, stir while adding (speed of agitator be 300~600r/
Min), the silicon sol solution of highly acid is obtained, the Ludox pH value of the highly acid of gained is less than 1.5；
2) the 100mL acidic silicasols are taken, are placed in Rotary Evaporators, design temperature is 70 DEG C, the revolving time is 3 points
Clock, obtains 70mL Ludox, takes out colloidal sol, and 70mL acetone is added thereto, and magnetic agitation is allowed to well mixed.Afterwards thereto
Step 1 is added dropwise) in solution A, regulation pH value of solution to 6 ,~20min formation gel；
3) acetone aging 6 hours is added into the gel of formation, gel is placed in autoclave afterwards, in 8Mpa, 45 DEG C
Under the conditions of carry out supercritical CO24h is dried in extraction.Finally obtain hydrophilic aerosil heat-barrier material.Its density：
0.103g/cm3, porosity：95.32%, thermal conductivity：0.022W/m·K.
Embodiment 4
1) 70mL sodium silicates (3.24 moulds, 31.89%) are taken, is diluted with 70mL deionized waters, is stirred, obtain solution
A.Mixed solution is poured slowly into the not diluted concentrated hydrochloric acids of 20mL (12mol/L) afterwards, stirs while adding that (speed of agitator is
300~600r/min), the silicon sol solution of highly acid is obtained, the Ludox pH value of the highly acid of gained is less than 1.5；
2) the 100mL acidic silicasols are taken, are placed in Rotary Evaporators, design temperature is 50 DEG C, the revolving time is 10 points
Clock, obtains 70mL Ludox, takes out colloidal sol, and 70mL absolute ethyl alcohols are added thereto, and magnetic agitation is allowed to well mixed.It is backward
Step 1 is wherein added dropwise) in solution A, regulation pH value of solution to 5.5 ,~25min formation gel；
3) absolute ethyl alcohol aging 4 hours is added into the gel of formation, gel is placed in autoclave afterwards,
8.5Mpa, carries out supercritical CO under the conditions of 35 DEG C24h is dried in extraction.Finally obtain the heat-insulated material of hydrophilic aerosil
Material.Its density：0.095g/cm3, porosity：95.68%, thermal conductivity：0.023W/m·K.
Claims (9)
1. a kind of supercritical drying preparation method of aerosil heat-barrier material, it is characterised in that：Comprise the following steps：
1) water glass solution is diluted first by a certain amount of deionized water；
2) water glass solution after dilution is added at a slow speed in concentrated hydrochloric acid solution, be stirred continuously, be allowed to well mixed, obtain strong
Acid Ludox；
3) the acid silicon dioxide sol solution rotating is evaporated into part moisture, taken out, add the water solubility of low surface tension
Polar solvent, stirring be allowed to well mixed, add a certain amount of step 1) in water glass solution adjust pH value of solution to 5.5-6,
Gel can be formed；
4) to step 3) water soluble polar solvent age gelation is added 2~12 hours in gained gel, afterwards by gained wet gel
It is placed in extraction kettle, it is high-pressure sealed, it is passed through supercritical CO2, contacted with wet gel, carry out extraction drying, drying time is 2-5h.
2. the supercritical drying preparation method of aerosil heat-barrier material according to claim 1, its feature exists
In：Step 1) described in water glass solution be sodium silicate, lithium silicate or KP1, its modulus be 2.5~3.55, it is described
Water glass solution and deionized water volume ratio be 1:0.5 to 1:3.
3. the supercritical drying preparation method of aerosil heat-barrier material according to claim 1, its feature exists
In：Step 2) in the concentration of concentrated hydrochloric acid used be 8-12mol/L, speed of agitator is 300~600r/min.
4. the supercritical drying preparation method of aerosil heat-barrier material according to claim 3, its feature exists
In：Step 2) in the concentration of concentrated hydrochloric acid used be 12mol/L.
5. the supercritical drying preparation method of aerosil heat-barrier material according to claim 1, its feature exists
In：Step 2) in gained highly acid Ludox pH value be less than 1.5.
6. the supercritical drying preparation method of aerosil heat-barrier material according to claim 1, its feature exists
In：Step 3) in rotary evaporation temperature be 40-75 DEG C, the rotary evaporation time be 2-15min.
7. the supercritical drying preparation method of aerosil heat-barrier material according to claim 1, its feature exists
In：Step 3) and step 4) in water soluble polar solvent be ethanol, methanol, isopropanol, propyl alcohol, acetone.
8. the supercritical drying preparation method of aerosil heat-barrier material according to claim 1, its feature exists
In：Step 3) described in water glass solution be sodium silicate, lithium silicate or KP1, its concentration can be 3~5.5mol/L.
9. the supercritical drying preparation method of aerosil heat-barrier material according to claim 1, its feature exists
In：Step 4) in temperature in extraction kettle can be 35-45 DEG C, pressure can be 7.4-8.5MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108862286A (en) * | 2018-07-05 | 2018-11-23 | 江苏泛亚微透科技股份有限公司 | The elastic silica aerogel sheet material and automobile lithium-ion-power cell heat management system thin slice of anti-flaming thermal-insulation |
| CN113401910A (en) * | 2021-07-30 | 2021-09-17 | 江苏泛亚微透科技股份有限公司 | Silicon dioxide aerogel and low-corrosion preparation method thereof |
| CN115806427A (en) * | 2022-12-13 | 2023-03-17 | 中化学华陆新材料有限公司 | Low-cost SiO 2 Method for producing aerogels |
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| CN108862286A (en) * | 2018-07-05 | 2018-11-23 | 江苏泛亚微透科技股份有限公司 | The elastic silica aerogel sheet material and automobile lithium-ion-power cell heat management system thin slice of anti-flaming thermal-insulation |
| CN113401910A (en) * | 2021-07-30 | 2021-09-17 | 江苏泛亚微透科技股份有限公司 | Silicon dioxide aerogel and low-corrosion preparation method thereof |
| CN115806427A (en) * | 2022-12-13 | 2023-03-17 | 中化学华陆新材料有限公司 | Low-cost SiO 2 Method for producing aerogels |
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