CN107188188A - A kind of preparation method and adsorption applications of amino modified aerosil - Google Patents
A kind of preparation method and adsorption applications of amino modified aerosil Download PDFInfo
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- CN107188188A CN107188188A CN201710584759.2A CN201710584759A CN107188188A CN 107188188 A CN107188188 A CN 107188188A CN 201710584759 A CN201710584759 A CN 201710584759A CN 107188188 A CN107188188 A CN 107188188A
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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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- 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
- C01B33/16—Preparation of silica xerogels
- C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
Pass through the in-situ modified technology for preparing amino modified aerosil of collosol and gel co-precursor method under supercritical drying the present invention relates to a kind of, the modified aerogels skeleton particle of preparation is small, being translucent property of sample, with higher specific surface area and porosity.The present invention is with tetraethyl orthosilicate etc. for silicon source presoma, amino containing silane prepares amino modified silica wet gel as co-precursor modifying agent and gel catalyst simultaneously, carries out that amino modified aeroge is directly made after aging under supercritical drying in ethanol solution.This method is simple, and easy to operate, whole process is easy to control, can be continuously produced, and obtained product not only has excellent physical property, while having excellent absorption property to GHG carbon dioxide.
Description
Technical field
The present invention relates to a kind of sol-gel co-precursor method is in-situ modified and obtain amino modified with reference to supercritical drying
The preparation method of aerosil, and it is used as efficient absorption materials application.
Background technology
Aerosil is considered as in recent years as a kind of high porosity and the nano-porous materials of high-specific surface area
It is a kind of preferable carbon dioxide absorber carrier.Aerosil is a kind of solid phase particulates and hole is nanometer amount
The novel porous functional material of level, with lightweight (0.003 ~ 0.35 g/cm3), translucent (light transmittance>60 %), high-ratio surface
Product (600 ~ 1500 m2/ g), high porosity (88 ~ 99.8 %), in a low voice spread speed (~ 100 m/s), low-k (1.01 ~
1.1) and the excellent properties such as extremely low thermal conductivity factor (12 ~ 20 mW/ (m K)), led in chemistry, calorifics, acoustics, optics, electricity etc.
Domain, particularly has broad application prospects in terms of high efficiency heat insulation material, sorbing material, chemical catalyst and its carrier.It is logical
It is the adsorptive selectivity and adsorption capacity for improving it at present to target contaminant to cross the modification to aerosil skeleton
Main method.
It is one of focus of research as the capture and sealing up for safekeeping in the last few years on carbon dioxide increasingly attracts attention,
With important commercial value.Carbon dioxide is a kind of main greenhouse gases, and the contribution rate to Global climate change exceedes
60%, and it is main largely from combustion of fossil fuel, is the main component in the waste gas such as flue.While tellurian resource
Growing tension, and carbon dioxide also serves as a kind of potential carbon resource, the capture isolation technics of current carbon dioxide mainly includes
For liquid flux absorption method, solid absorption method, membrane separation process, low-temperature freezing and biological treatment.In the above method, Gu
Body absorption method is to act on capturing carbon dioxide for the selective reversible adsorption of carbon dioxide in waste gas using solid absorbent, is had
Have easy to operate, equipment requirement is low and corrosion-free, free of contamination advantage is a kind of competitive technology.Therefore solid gas
Absorption method has important Research Significance as the target contaminant in a kind of simple, efficient process gas, and pass has been studied at present
Mainly include in the adsorbent species of carbon dioxide：Activated carbon, CNT, zeolite, molecular sieve, metal oxide and solid-state
Amine etc..Solid amine is that a kind of chemosorbent combines to trap point by the chemical group of adsorbent surface and carbon dioxide
From carbon dioxide.Amido type organic is mainly combined by solid amine, grafting or modified on porous material carrier.But, always
For knot, the specific surface area of current drikold sorbing material is low, porosity is low, micropore and mesoporous pore volume are low, compound
Effect is poor, the low reason of functional groups utilization rate causes the absorption property of material is difficult to outstanding.
Porous silica material is solid amine carrier material widely studied at present.And in recent years more studies have reported that two
The functional modification of silica aerogel be used for carbon dioxide adsorption, but the adsorption capacity of material only have 1.95 mmol/g and
1.2 mmol/g, this be due to adsorbent be often the aerosil or wet gel that have prepared are modified or
Person is combined, and modified effect is poor, modification is difficult to control to, the loose structure destruction of aeroge is serious, hole is blocked.And by amido
When silane introduces the preparation process of aerosil, amino containing silane can cause silicon source rapid polycondensation to cause precipitation can not shape again
Wet gel into stable homogeneous is so as to further prepare modified aerogels.Such as current patent（Grant number：CN101973558B）In
The preparation method of the amino modified aerosil of report is also that the amino modified solution of preparation is wet for silica
The modification of gel, then pass through exchange of solvent and the amino modified aerosil of supercritical drying.This method is not only
Cause substantial amounts of solvent consumption, and need prolonged modifying process, the physical property of obtained amino modified aeroge and
Carbon dioxide adsorption performance is all remained to be further improved.Patent（Publication number：CN103432985A）The amino modified two of middle report
The preparation method of silica aerogel equally employs identical method and carries out amino modified to silica wet gel, with reference to two
Carbonoxide supercritical drying prepares the absorption of amino modified aerosil and application Heavy Metals in Waters ion.
The content of the invention
It is an object of the invention to provide a kind of technique is simple, the production cycle is extremely short, course of reaction is controllable, and can serialization
The co-precursor of production is modified the method that method prepares transparent amino modified aerosil block.
The preparation method of transparent amino modified aerosil block of the present invention comprises the following steps：
1）The hydrolysis of organic amino group silane sol
Modified co-precursor organosilan and deionized water, absolute ethyl alcohol are mutually mixed by proportioning, before long agitation makes altogether
Body amino containing silane is driven to be fully hydrolyzed；
In step 1）In, by material molar ratio, organosilan: absolute ethyl alcohol: water=1:（15~30）∶（0.2~0.6）, amido silicon
Mixing time described in when alkane is hydrolyzed was controlled between 5 ~ 12 hours.
2）The preparation of amino modified silica wet gel
By the solution of above-mentioned configuration and unhydrolysed silicon source tetraethyl orthosilicate（TEOS）Or positive quanmethyl silicate（TMOS）Put
Enter in refrigerating chamber and cool, then silicon source is directly poured into the amino containing silane colloidal sol after hydrolysis, by mixed silicon dioxide gel
It is transferred in mould and stands and be put into sustained response in refrigerating chamber, that is, the silica wet gel of amino modified is made；
In step 2）In, by material molar ratio, the solution of the configuration, amino containing silane: TEOS（TMOS）=0.2 ~ 1, the freezing
The temperature of room should be controlled between -15 ~ -22 DEG C.
3）The aging of amino modified silica wet gel and supercritical drying
Amino modified silica wet gel is immersed in a small amount of ethanol solution, the aging of wet gel is carried out, after aging
Wet gel directly dried by CO 2 supercritical after, that is, obtain amino modified silica wet gel block；
In step 3）In, the temperature of the aging can be 25 ~ 60 DEG C, and the time can be 2 ~ 12 hours.Described carbon dioxide is super to be faced
Boundary's drying process is：Wherein supercritical drying temperature is 30 ~ 35 DEG C, and pressure is 8 ~ 10 MPa.
The preparation method of transparent amino modified aerosil of the present invention is simple, easily-controllable.Colloidal sol-
Gel phase adds organosilan and silicon source one reacts, can form silica dioxide gel skeleton by the method for co-precursor
It is uniform modifies, finally CO 2 supercritical drying under prepare the silica gas with functional amido group
Gel.The amino modified aerosil of preparation is blockiness preferably, pore-size distribution Relatively centralized（0~50nm）, size is equal
It is even.Aerosil is nano-porous structure, the g/cm of density 0.1 ~ 0.23, porosity 90 ~ 96%, specific surface area 650 ~
850 m2/g。
The present invention, which prepares transparent amino modified aerosil, must regulate and control the sol-gel process of silica,
The rapid polycondensation to silicon source due to modified amino containing silane presoma is avoided, the quick up to formation wadding of silica dioxide granule is caused
Shape precipitates and can not form the three dimensional gel skeleton structure of stable homogeneous, or the low shortcoming of the gel physical property formed.Cause
This, control two kinds of silicon source presomas polycondensation speed and and rational solution ratio to preparing transparent amino modified silica
Aeroge is most important.The present invention suppresses the polycondensation reaction of silicon source by temperature control first, then passes through silicone hydroxyl content in colloidal sol
Control, and it is significantly less than polycondensation speed between silicone hydroxyl using the polycondensation speed of unhydrolysed silicon source silane epoxide and silicone hydroxyl
So as to avoid the quick progress of polycondensation reaction from forming homogeneous gel rubber system.
Compared with the prior art, the present invention has following outstanding advantages：
The present invention dries the transparent amino modified aerosil prepared using CO 2 supercritical, both maintains dioxy
The high and translucent advantage of SiClx aeroge low-density, porosity, while having excellent carbon dioxide adsorption performance again.This hair
Bright used preparation technology is simple, easily-controllable, is replaced and prolonged gel without complicated multiple solvent in preparation process
Post-modification process, therefore, the consumption without solvent, it is to avoid the generations of a large amount of waste liquids of gel, while significantly reducing preparation
In the cycle, synthesis technique is simplified, significantly reduce the cost for preparing amino modified aerosil.Importantly,
This amino containing silane that the present invention is used the method for modifying of aerosil can be formed it is uniform it is modifies avoid after
The modified hole to silica dioxide gel is blocked, while modified-reaction is slow, the uniform content of modified group skewness is difficult to control to
Shortcoming have it so that improved silica aeroge shows its exclusive physical characteristic when being applied as sorbing material
There is excellent adsorption capacity.The last present invention employs mild condition titanium dioxide when preparing amino modified aerosil
Carbon supercritical drying process, it is to avoid harsh, the dangerous ethanol supercritical drying of drying condition.
Brief description of the drawings
The photo for the block transparent amino modified aerosil that Fig. 1 is prepared for the present invention.
The stereoscan photograph for the block transparent amino modified aerosil that Fig. 2 is prepared for the present invention.
The infrared spectrogram for the flexible silica aerogel that Fig. 3 is prepared for the present invention.In figure 3, abscissa is ripple
Number（cm-1）；Ordinate is transmitance（%）.The chemical bond from left to right marked is followed successively by-CH3,-CH2, Si-C, Si-O-Si,
Si-C, Si-O-Si.
Fig. 4 is the nitrogen adsorption desorption curve of transparent amino modified aerosil prepared by the embodiment of the present invention 1
And graph of pore diameter distribution.
Fig. 5 is dynamic carbon dioxide adsorption breakthrough curve prepared by the embodiment of the present invention 1, in Figure 5, when abscissa is
Between（min）；Ordinate is relative concentration.
Embodiment
Below by embodiment combination accompanying drawing, the invention will be further described.
Embodiment 1
Volume feed：Tetraethyl orthosilicate：γ-aminopropyl triethoxysilane：Ethanol：Water=5：3：10：2.7, by 3ml's
γ-aminopropyl triethoxysilane and 10ml absolute ethyl alcohol is mixed, and adds 2.7ml water, persistently stir 12h with
The amido colloidal sol after hydrolysis is mixed while stirring with the unhydrolysed tetraethyl orthosilicates of 5ml after promoting the hydrolysis of amido silicon source, 12h
Close, stop stirring after 10min, obtained silicon dioxide gel is stood in the refrigerating chamber with -20 DEG C and treats sample gel.Again will be wet
Gel, which is placed in ethanol solution, carries out aging, and aging temperature is 60 DEG C, and wet gel is directly super by carbon dioxide after aging
Critical drying.
Drying condition is：Pressure carbon dioxide control is 35 DEG C in 10 MPa, temperature, and drying time is 48h, that is, is obtained
Bright amino modified aerosil.
The density of the amino modified aerosil of the preparation is 0. 12g/cm3。
Fig. 5 is Kinetic penetration curve of the amino modified aerosil to carbon dioxide, by the 0.3g of preparation amine
Base improved silica aeroge is filled in adsorption column, before test sample, and by sample at 150 DEG C, flow velocity is 100ml/
Pre-processed in the adsorbent bed of min High Purity Nitrogen.Carbon dioxide Dynamic Adsorption condition is then 25 DEG C in temperature, and measurement atmosphere is
10% volume fraction C O2,90% volume fraction N2, while being passed through 1% vapor in adsorbed gas, gas flow rate is 30ml/min's
Flow velocity is lower to be carried out.Corresponding breakthrough curve is obtained by the composition of gas after adsorption column by gas chromatograph test.By wearing
Saturating curve can calculate dynamic adsorption capacity of the amino modified aerosil at 25 DEG C can reach it is excellent
5.59mmol/g。
Embodiment 2
Volume feed：Tetraethyl orthosilicate：N- aminoethyls-γ-aminopropyltrimethoxysilane：Ethanol：Water=5：2：15：
1.8,2ml γ-aminopropyl triethoxysilane and 15ml absolute ethyl alcohol are mixed, 1.8ml water is added, holds
It is continuous to stir 6h to promote the amido colloidal sol after hydrolysis and the unhydrolysed tetraethyl orthosilicates of 5ml after the hydrolysis of amido silicon source, 12h
Mix while stirring, stop stirring after 10min, obtained silicon dioxide gel is stood in the refrigerating chamber with -22 DEG C and treats sample
Gel.Wet gel is placed in ethanol solution again and carries out aging, aging temperature is 30 DEG C, and wet gel directly passes through after aging
CO 2 supercritical is dried.
Drying condition is：Pressure carbon dioxide control is 30 DEG C in 8 MPa, temperature, and drying time is 48h, that is, is obtained
Bright amino modified aerosil.
The density of the amino modified aerosil of the preparation is 0. 15g/cm3.Its at 25 DEG C dynamic suction
Attached capacity can reach 5.32mmol/g.
Embodiment 3
Volume feed：Positive quanmethyl silicate：Diethylenetriamine base propyl trimethoxy silicane：Ethanol：Water=5：1：20：0.9,
1ml diethylenetriamine base propyl trimethoxy silicane and 20ml absolute ethyl alcohol are mixed, 0.9ml water is added,
5h is persistently stirred to promote the amido colloidal sol after hydrolysis and the unhydrolysed positive silicic acid tetramethyls of 5ml after the hydrolysis of amido silicon source, 5h
Ester is mixed while stirring, stops stirring after 10min, and obtained silicon dioxide gel is stood in the refrigerating chamber with -15 DEG C and treats sample
Product gel.Wet gel is placed in ethanol solution again and carries out aging, aging temperature is 60 DEG C, wet gel directly leads to after aging
Cross supercritical drying.
Drying condition is：Pressure carbon dioxide control is 30 DEG C in 10 MPa, temperature, and drying time is 48h, that is, is obtained
Bright amino modified aerosil.
The density of the amino modified aerosil of the preparation is 0. 10g/cm3.Its at 25 DEG C dynamic suction
Attached capacity can reach 5.90mmol/g.
Embodiment 4
Volume feed：Tetraethyl orthosilicate：γ-aminopropyl triethoxysilane：Ethanol：Water=5：5：10：2.7, by 5ml's
γ-aminopropyl triethoxysilane and 10ml absolute ethyl alcohol is mixed, and adds 2.7ml water, persistently stir 12h with
The amido colloidal sol after hydrolysis is mixed while stirring with the unhydrolysed tetraethyl orthosilicates of 5ml after promoting the hydrolysis of amido silicon source, 12h
Close, stop stirring after 10min, obtained silicon dioxide gel is stood in the refrigerating chamber with -22 DEG C and treats sample gel.Again will be wet
Gel, which is placed in ethanol solution, carries out aging, and aging temperature is 60 DEG C, and wet gel is directly super by carbon dioxide after aging
Critical drying.
Drying process be the same as Example 1.
The density of the amino modified aerosil of the preparation is 0. 2g/cm3。
Embodiment 5
Volume feed：Positive quanmethyl silicate：γ-aminopropyl triethoxysilane：Ethanol：Water=5：3：15：1.8, by 3ml's
γ-aminopropyl triethoxysilane and 15ml absolute ethyl alcohol are mixed, and add 1.8ml water, persistently stir 6h to promote
Enter after the hydrolysis of amido silicon source, 6h and to mix the amido colloidal sol after hydrolysis while stirring with the unhydrolysed positive quanmethyl silicates of 5ml,
Stop stirring after 10min, obtained silicon dioxide gel is stood in the refrigerating chamber with -20 DEG C and treats sample gel.Again will be wet solidifying
Glue, which is placed in ethanol solution, carries out aging, and aging temperature is 50 DEG C, and wet gel directly faces by the way that carbon dioxide is super after aging
Dry on boundary.
Drying condition is：Pressure carbon dioxide control is 30 DEG C in 10 MPa, temperature, and drying time is 72h, that is, is obtained
Bright amino modified aerosil.
The density of the amino modified aerosil of the preparation is 0. 10g/cm3。
Embodiment 6
Volume feed：Positive quanmethyl silicate：N- aminoethyls-γ-aminopropyltrimethoxysilane：Ethanol：Water=5：5：20：
2.7,5ml N- aminoethyls-γ-aminopropyltrimethoxysilane and 20ml absolute ethyl alcohol are mixed, 20ml is added
Water, persistently stir 12h to promote the amido colloidal sol after hydrolysis and the unhydrolysed positive silicon of 5ml after the hydrolysis of amido silicon source, 12h
Sour four methyl esters are mixed while stirring, stop stirring after 10min, and obtained silicon dioxide gel is stood into the refrigerating chamber with -22 DEG C
In treat sample gel.Wet gel is placed in ethanol solution again and carries out aging, aging temperature is 60 DEG C, wet gel after aging
Directly dried by CO 2 supercritical.
Drying process be the same as Example 1.
The density of the amino modified aerosil of the preparation is 0. 15g/cm3。
Claims (8)
1. a kind of preparation method of the silica aerogel material of transparent amino modified, it is characterised in that by step in detail below
Prepare：
Modified co-precursor organosilan and deionized water, absolute ethyl alcohol are mutually mixed by proportioning, stirring fills amino containing silane
Divide hydrolysis；
The solution after hydrolysis and unhydrolysed organic silicon source are put into refrigerating chamber again and cooled, silicon source is directly poured into after hydrolysis
Amino containing silane colloidal sol in, mixed silicon dioxide gel is transferred in mould and stood and be put into refrigerating chamber until gel
The silica wet gel of amino modified is made, wet gel is finally subjected to aging and supercritical drying, that is, obtains amido and changes
The aerosil of property.
2. a kind of preparation method of transparent amino modified aerosil as claimed in claim 1, the colloidal sol presses raw material
Volume ratio, preferred scope is silicon source：Amino containing silane: absolute ethyl alcohol: water=5: 1 ~ 5:（10~20）∶（0.9~2.7）.
3. a kind of preparation method of transparent amino modified aerosil as claimed in claim 1, it is characterised in that described
The species of modified amino containing silane include γ-aminopropyl triethoxysilane, N- aminoethyls-γ-aminopropyltrimethoxysilane or
Diethylenetriamine base propyl trimethoxy silicane.
4. a kind of preparation method of transparent amino modified aerosil as claimed in claim 1, it is characterised in that described
The species of silicon source is unhydrolysed tetraethyl orthosilicate or positive quanmethyl silicate.
5. a kind of preparation method of transparent amino modified aerosil as claimed in claim 1, it is characterised in that described
The temperature of refrigerating chamber should be controlled between -15 ~ -22 DEG C.
6. a kind of preparation method of transparent amino modified aerosil as claimed in claim 1, it is characterised in that described
The temperature of aging is 25 ~ 60 DEG C.
7. prepared by a kind of preparation method of transparent amino modified aerosil as described in claim 1~6 saturating
Bright amino modified aerosil, the porosity of amino modified aeroge is 90%~96%, and density is 0.1~0.2 g/
cm3。
8. prepared by a kind of preparation method of transparent amino modified aerosil as described in claim 1~6 saturating
Bright amino modified aerosil, can be applied to the absorption of GHG carbon dioxide, apply also for the sulphur in waste gas
Change the pollutants such as hydrogen, oxysulfide, the absorption of nitrogen oxides, and anionic dye, heavy metal ion, antibiotic in waste water
Absorption.
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| CN110339814A (en) * | 2018-04-04 | 2019-10-18 | 天津大学 | Modified dioxide composite silica aerogel of methyl with hierarchical porous structure and its preparation method and application |
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| JP6764050B1 (en) * | 2019-02-14 | 2020-09-30 | ティエムファクトリ株式会社 | Airgel and its manufacturing method |
| CN109850909A (en) * | 2019-04-04 | 2019-06-07 | 广州大学 | A kind of atmospheric preparation method of super-hydrophobic silica aeroge |
| CN109850909B (en) * | 2019-04-04 | 2020-11-13 | 广州大学 | Normal-pressure preparation method of super-hydrophobic silica aerogel |
| CN110551317A (en) * | 2019-08-01 | 2019-12-10 | 广东工业大学 | organic amine-loaded silicon-based aerogel and preparation method and application thereof |
| CN113083260A (en) * | 2021-04-29 | 2021-07-09 | 中国科学院城市环境研究所 | Aminated polysiloxane-based aerogel composite membrane, preparation method thereof and gas adsorption application |
| CN113083260B (en) * | 2021-04-29 | 2023-08-01 | 中国科学院城市环境研究所 | Aminated polysiloxane-based aerogel composite membrane, preparation method and gas adsorption application thereof |
| WO2023071410A1 (en) * | 2021-10-29 | 2023-05-04 | 广东邦普循环科技有限公司 | Preparation method for carbon dioxide capture agent, and application thereof |
| GB2619195A (en) * | 2021-10-29 | 2023-11-29 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method for carbon dioxide capture agent, and application thereof |
| US11931722B2 (en) | 2021-10-29 | 2024-03-19 | Guangdong Brunp Recycling Technology Co., Ltd. | Preparation method for carbon dioxide capture agent, and application thereof |
| 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 |
| CN116081630A (en) * | 2022-12-23 | 2023-05-09 | 中科环境科技研究院(嘉兴)有限公司 | Carboxylic acid group modified silica aerogel and preparation method and application thereof |
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