CN114669275A - Microporous material/carbon aerogel composite material and preparation method and application thereof - Google Patents

Microporous material/carbon aerogel composite material and preparation method and application thereof Download PDF

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CN114669275A
CN114669275A CN202210467845.6A CN202210467845A CN114669275A CN 114669275 A CN114669275 A CN 114669275A CN 202210467845 A CN202210467845 A CN 202210467845A CN 114669275 A CN114669275 A CN 114669275A
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carbon aerogel
carbon
microporous material
microporous
drying
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CN114669275B (en
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张晶
孙金强
伊希斌
赵新富
刘思佳
于诗摩
袁志鹏
刘晓婵
沈晓冬
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New Material Institute of Shandong Academy of Sciences
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28095—Shape or type of pores, voids, channels, ducts
    • B01J20/28097—Shape or type of pores, voids, channels, ducts being coated, filled or plugged with specific compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding

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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

The invention relates to a microporous material/carbon aerogel composite material and a preparation method and application thereof. The microporous material/carbon aerogel composite material is composed of a microporous material with better adsorption capacity and a carbon aerogel framework material, wherein the microporous material is directly assembled into the framework of the carbon aerogel as a guest material, and a composite adsorbent material of a binder is not needed, so that methane gas can be effectively adsorbed and stored, and the microporous material/carbon aerogel composite material has good value in practical application.

Description

Microporous material/carbon aerogel composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of gas storage, and particularly relates to a microporous material/carbon aerogel composite material, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Adsorbed Natural Gas (ANG) has the advantages of light storage tank dead weight, good safety, low operating cost and the like, and is considered to be the safest and most economical storage method at present. ANG mainly uses a porous material with high specific surface area as a medium, and realizes efficient storage of methane under low pressure (35-65 bar). The high-performance adsorbent material is the core of the ANG technology, and aims at the key problems existing at present, namely limited storage capacity, difficulty in processing and recycling of the powder adsorbent for breakthrough and improvement, and promotion and application of the natural gas adsorption storage technology are promoted to a great extent.
The microporous materials are mostly powder adsorbents and are filled in the storage tank, a plurality of gaps are left among particles, the density of natural gas in the gaps is actually the pure compressed natural gas density under the pressure of the storage tank (3-6MPa), and the natural gas density does not contribute to increasing the storage density of ANG.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a microporous material/carbon aerogel composite material and a preparation method and application thereof. The composite material is composed of a microporous material with better adsorption capacity and a carbon aerogel framework material, wherein the microporous material is directly assembled into the framework of the carbon aerogel as a guest material, a binder is not needed, and the assembled composite adsorbent material can effectively adsorb and store clean energy gases such as methane and the like, so that the composite material has good practical application value.
Specifically, the invention provides the following technical scheme:
a preparation method of a microporous material/carbon aerogel composite material comprises the following steps:
(1) adding a carbon source material and a cross-linking agent into a solvent, and uniformly stirring; pouring the obtained solution into a porous mold, sealing, and then gelling and drying; carbonizing the honeycomb-shaped aerogel obtained by different drying modes at high temperature to obtain honeycomb-shaped carbon aerogel;
(2) filling the microporous material into the pores of the honeycomb-shaped carbon aerogel; wherein, the middle big round hole is not added; the surface is encapsulated at the port by a heat-conducting fin, and a middle hole is reserved.
The porous mold is a cylindrical container with the interior composed of a plurality of small cylinders and a middle cylinder.
Further, the porous mold has a structure that: the periphery is a cylinder with the height of 5-10cm, the outer diameter of 5-10cm and the inner diameter of 4.8-9.8cm (the size and the height can be adjusted according to the size of the ANG storage tank), the interior consists of a plurality of small cylinders with the diameter of 0.2-0.5cm and a middle cylinder with the diameter of 0.6cm, the middle cylinder is 6-11cm high, the small cylinders are consistent with the periphery in height, and the small cylinders and the periphery are combined according to different arrangement modes according to requirements.
Furthermore, the mould is made of polytetrafluoroethylene materials.
Further, the carbon source material of the carbon aerogel comprises corn protein, silk fibroin, bacterial cellulose, xylan, shellac, alginate, chitosan oligosaccharide, resorcinol, polyvinyl alcohol, melamine and the like, and the cross-linking agent comprises N, N-methylenebis (acrylamide), ethylenediamine, polyacrylic acid, formaldehyde, polyacrylamide, polyethylene glycol and the like; controlling the mass concentration of the cross-linking agent to be 0.1-5%; the solvent includes water, methanol, ethanol, DMF, ethylene glycol, glycerol, pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, pyridine, piperidine, furan, tetrahydrofuran, dioxane, and dimethylsulfoxide.
Furthermore, the gel temperature and the gel time are determined according to different specific components, the gel temperature can be 20-90 ℃, and the aging time is 2-72 h.
Further, the drying treatment includes two methods:
by using CO2Supercritical drying method: forming hydrogel by the sol at a specific temperature, aging, replacing the solvent, and then performing supercritical drying; the gel temperature and time are determined according to different specific components, the temperature can be 20-90 ℃, the aging time is 2-72 h, and the solvent replacement time is 1-7 days.
A freeze drying method is adopted: freezing for a certain time and then carrying out freeze-drying treatment. Wherein, the directional freezing is carried out for 5-60min, the non-directional freezing is carried out for 24-72h, and the freeze-drying time is 3-7 days.
Further, the high-temperature carbonization specifically comprises: heating in a tubular furnace at a heating rate of 3-6 deg.C/min to 600 deg.C and 1000 deg.C, maintaining for 1-4h, naturally cooling to room temperature, and taking out, wherein a protective gas (nitrogen or argon) is introduced.
Further, the microporous material as a filler comprises MOF (zinc-based MOF, cobalt-based MOF, copper-based MOF, zirconium-based MOF, etc.), silica aerogel, zeolite molecular sieves (3A (potassium A type), 4A (sodium A type), 5A (calcium A type), 10Z (calcium Z type), 13X (sodium X type), etc., microporous carbon (coconut shell carbon, bamboo carbon, etc.), etc., and the specific surface area of the microporous material is controlled to be 1000-2Per g, its pore volume is 0.5-2.0cm3(ii) in terms of/g. And (2) adding a microporous material into the holes of the honeycomb carbon aerogel (the adding mode is that the microporous material is directly filled into the holes of the honeycomb carbon aerogel, and the large round hole in the middle is not added).
The microporous material/carbon aerogel composite material is applied to gas storage. The specific application method is that the microporous material/carbon aerogel composite material is connected in series by the gas guide pipe in the storage tank, the bottommost layer is pre-provided with a heat conducting sheet, and the heat conducting sheet on the composite material is arranged between every two layers, so that the heat generated during adsorption can be dissipated, and the microporous material can be prevented from being separated. And finally, packaging the storage tank for gas storage. The adsorbed gas may be methane, acetylene, hydrogen, carbon monoxide, carbon dioxide, or the like.
The beneficial technical effects of the invention are as follows:
(1) according to the invention, the cellular carbon aerogel is prepared by the porous mold, the diameter of the cylinder in the mold can control the size of macro pores of the aerogel, so that the amount of the microporous material added is controlled, and the arrangement mode can control the dispersion condition of the microporous material. The microporous material is loaded in the holes of the aerogel, so that the problem (such as moisture) related to structural instability of the microporous material in the environment can be solved, and the heat conducting fins additionally arranged at the ports can effectively disperse heat generated during adsorption, so that the adsorption value is improved.
(2) In the microporous material/carbon aerogel composite material prepared by the invention, the microporous material has a larger specific surface area for gas storage, the carbon aerogel has microscopic mesopores and macropores for gas transmission, the synergistic effect of the microporous material and the carbon aerogel provides strong host-guest interaction in the pores, and due to the rapid mass transfer of the microscopic mesopores and macropores of the carbon aerogel framework, the adsorption kinetics is faster, and meanwhile, the microporous material/carbon aerogel composite material also has an integral block shape which is beneficial to processing and easy to recover and good mechanical properties.
(3) The microporous material/carbon aerogel composite material prepared by the method is an integral block material, and a binder is not required to be added in the preparation and forming process, and only the binder is simply filled, so that the phenomenon of hole plugging caused by the addition of the binder is avoided; and the carbon aerogel framework material has good thermal conductivity, can accelerate the adsorption and desorption rates, is favorable for reducing the cost and prolonging the service life of the adsorbent.
(4) The invention reports for the first time that simple composite preparation based on the microporous material and the carbon aerogel can not only provide an integral block-shaped carrier for the microporous material, but also generate synergistic effect by compounding the microporous material and the carbon aerogel, so that the microporous material has the function of adsorbing and storing clean energy gases such as methane, and experiments prove that the microporous material has excellent adsorption and storage performance on the clean energy gases such as methane, and meanwhile, the selected raw material resources are wide, the cost is low, the composite material accords with the green chemical production concept, and is beneficial to development of actual industrialization and industrialization.
(5) The microporous material/carbon aerogel prepared by the invention is compoundedComposite material pair CO2The greenhouse gas also has excellent adsorption performance, can effectively capture carbon and reduce CO2The discharge has a certain positive effect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a perspective view of a porous mold prepared in example 1 of the present invention.
Fig. 2 is a front view and a top view of a porous mold prepared in example 1 of the present invention.
Fig. 3 is a block diagram of an ANG tank of the matched composite of the present invention.
Fig. 4 is a perspective view of a honeycomb carbon aerogel prepared by the porous mold of the present invention.
FIG. 5 is a microscopic electron micrograph of a carbon aerogel according to example 1 of the present invention.
Fig. 6 is a structural view of a micro-framework and a nanopore of the carbon aerogel in example 1 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1 (Cu-MOF/resorcinol carboxaldehyde aerogel)
The die is made of polytetrafluoroethylene materials, and has the following dimensions: the periphery is a cylinder with the height of 5cm, the outer diameter of 5cm and the inner diameter of 4.8cm, the inside is a plurality of cylinders with the diameter of 0.2cm, the diameter of the middle cylinder is 0.6cm and the height of 6cm, and the cylinders are combined in a matrix layout arrangement mode (the structure is shown in figures 1 and 2).
Dissolving 5.5g resorcinol in 10ml formaldehyde solution (37 wt%), adding 50ml water for dilution, adding anhydrous sodium carbonate as catalyst, stirring to obtain light yellow solution, pouring into porous mold, and placing in 80 deg.C ovenPerforming gel overnight, placing the hydrogel into ethanol for 7 days to obtain alcogel, and subjecting the alcogel to CO2And (4) performing supercritical drying to obtain the resorcinol formaldehyde aerogel. Under the protection of nitrogen, heating resorcinol formaldehyde carbon aerogel to 800 ℃ at the speed of 5 ℃/min in a tube furnace, preserving heat for 2h, naturally cooling to room temperature, and taking out to obtain resorcinol formaldehyde carbon aerogel (the structure is shown in figure 4, an electron microscope picture is shown in figure 5, and a structure diagram of a micro framework and a nanopore is shown in figure 6). The prepared Cu-MOF powder was filled into the hollow of the above-described carbon aerogel, and the port was encapsulated with a heat conductive sheet and filled into an ANG tank (see fig. 3).
The resorcinol formaldehyde carbon aerogel material has better mechanical toughness. When the pressure reached the maximum, no significant crushing of the sample occurred and the strain and stress of the carbon aerogel sample were 80% and 1.5Mpa, respectively. After 3000 times of cyclic processes of gas adsorption and desorption are carried out on the performance of the adsorbent, the adsorption volume of the natural gas is reduced by less than 10%.
Example 2(13X molecular sieves/gelatin-based carbon aerogels)
The die is made of polytetrafluoroethylene materials, and has the following dimensions: the periphery is a cylinder with the height of 5cm, the outer diameter of 5cm and the inner diameter of 4.8cm, the inside is a plurality of cylinders with the diameter of 0.4cm, the diameter of the middle cylinder is 0.6cm and the height of 6cm, and the cylinders are combined in an annular arrangement mode.
Dissolving 15g of gelatin in 85ml of water, placing the mixture in a 60-DEG C water bath kettle, stirring until the gelatin is completely dissolved, then adding 0.7ml of 37-40 wt% of formaldehyde solution, stirring for 5h at 60 ℃, transferring the mixture to the mold of the invention, standing for one day in a normal temperature environment to obtain hydrogel, performing directional freezing, transferring the hydrogel to a freeze dryer, freeze-drying until all water is removed, heating the composite material to 900 ℃ in a tubular furnace at the speed of 5 ℃/min under the protection of argon, preserving the heat for 3h, naturally cooling to room temperature, and taking out to obtain the gelatin-based carbon aerogel.
And filling the prepared 13X molecular sieve powder into the hollow cavity of the carbon aerogel, sealing the port by using a heat conducting sheet, and filling the mixture into an ANG storage tank.
The gelatin-based carbon aerogel material has better mechanical toughness. When the pressure reached the maximum, no significant crushing of the sample occurred and the strain and stress of the carbon aerogel sample were 75% and 0.561Mpa, respectively. After 3000 times of cyclic processes of gas adsorption and desorption are carried out on the performance of the adsorbent, the adsorption volume of the natural gas is reduced by less than 10%.
Example 3 (ZIF-67/bacterial cellulose based carbon aerogel)
The die is made of polytetrafluoroethylene materials, and has the following dimensions: the periphery is a cylinder with the height of 10cm, the outer diameter of 10cm and the inner diameter of 9.8cm, the inside is a plurality of cylinders with the diameter of 0.5cm, the diameter of the middle cylinder is 0.6cm and the height of 11cm, and the combination is combined by adopting an annular layout arrangement mode.
Adding 5 percent (relative to the mass fraction of the alkaline-urea system) of bacterial cellulose into an alkaline-urea system (NaOH: urea: water: 7:12:81), dissolving at low temperature until no particles exist (the rotating speed is low), and clarifying the solution. And (3) subpackaging the bacterial cellulose solution into a mould, heating the water dissolving pot to 72 ℃, putting the mould cup into the water bath pot, carrying out water bath for 2h, and taking out. After water bath forming, soaking the sample in deionized water until the replacement liquid of the sample is changed from yellow to transparent, removing redundant impurities, and replacing for about 5 days to finally obtain the bacterial cellulose hydrogel (the surface soaked in water can be provided with a layer of oil which emerges, namely alkali liquor to be removed). Then replacing the bacterial fiber hydrogel with absolute ethyl alcohol, and carrying out CO2And (4) performing supercritical treatment to obtain the bacterial cellulose aerogel. And then under the protection of nitrogen, heating the composite material to 1000 ℃ in a tubular furnace at the speed of 5 ℃/min, preserving the heat for 4 hours, naturally cooling to room temperature, and taking out to obtain the bacterial cellulose-based carbon aerogel.
And filling the prepared ZIF-67 powder into the hollow hole of the bacterial cellulose-based carbon aerogel, sealing the port by using a heat conducting sheet, and filling the opening into an ANG storage tank.
The bacterial cellulose-based carbon aerogel material has better mechanical toughness. When the pressure reached the maximum, no significant crushing of the sample occurred and the strain and stress of the carbon aerogel sample were 78% and 0.582Mpa, respectively. After 3000 times of cyclic gas adsorption and desorption processes are carried out on the performance of the adsorbent, the natural gas adsorption volume is reduced by less than 10%.
Finally, it should be noted that, although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (10)

1. The preparation method of the microporous material/carbon aerogel composite material is characterized by comprising the following steps:
(1) adding a carbon source material and a cross-linking agent into a solvent, and uniformly stirring; pouring the obtained solution into a porous mold, sealing, and then gelling and drying; carbonizing the obtained honeycomb-shaped aerogel at high temperature to obtain honeycomb-shaped carbon aerogel;
(2) filling the microporous material into the pores of the honeycomb-shaped carbon aerogel; wherein, the middle big round hole is not added; packaging the surface of the carbon aerogel composite material at a port by using a heat-conducting fin, and reserving a middle hole to obtain the microporous material/carbon aerogel composite material;
the porous mould is a cylindrical container, the interior of which consists of a plurality of small cylinders and a middle cylinder.
2. The method according to claim 1, wherein the porous mold has a structure of: the periphery of the cylinder is a cylinder with the height of 5-10cm, the outer diameter of 5-10cm and the inner diameter of 4.8-9.8cm, the interior of the cylinder consists of a plurality of small cylinders with the diameter of 0.2-0.5cm and a middle cylinder with the diameter of 0.6cm, the height of the middle cylinder is 6-11cm, and the height of the small cylinders is consistent with the height of the periphery; alternatively, the porous mold is made of a polytetrafluoroethylene material.
3. The method of claim 1, wherein the gelling conditions are: the gel temperature is 20-90 ℃, and the aging time is 2-72 h.
4. The preparation method of claim 1, wherein the carbon source material of the carbon aerogel comprises one or more of zein, silk fibroin, bacterial cellulose, xylan, shellac, alginate, chitosan oligosaccharide, resorcinol, polyvinyl alcohol, and melamine, and the cross-linking agent comprises one or more of N, N-methylenebis (acrylamide), ethylenediamine, polyacrylic acid, formaldehyde, polyacrylamide, and polyethylene glycol; controlling the mass concentration of the cross-linking agent to be 0.1-5%; the solvent comprises one or more of water, methanol, ethanol, DMF, ethylene glycol, glycerol, pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, pyridine, piperidine, furan, tetrahydrofuran, dioxane and dimethylsulfoxide.
5. The method of claim 1, wherein the drying includes two methods:
by using CO2Supercritical drying method: forming hydrogel by the sol at a specific temperature, aging, replacing the solvent, and then performing supercritical drying; preferably, the temperature can be 20-90 ℃, the aging time is 2-72 h, and the solvent replacement time is 1-7 days;
a freeze drying method is adopted: freezing for a certain time and then carrying out freeze-drying treatment; preferably, the directional freezing is carried out for 5-60min, the non-directional freezing is carried out for 24-72h, and the freeze-drying time is 3-7 days.
6. The preparation method according to claim 1, wherein the high-temperature carbonization is specifically: heating in a tubular furnace at a heating rate of 3-6 ℃/min to 600-1000 ℃, preserving heat for 1-4h, naturally cooling to room temperature, and taking out, wherein protective gas is introduced in the whole process, and the protective gas is nitrogen or argon.
7. The method as claimed in claim 1, wherein the microporous material comprises one or more of MOF, silica aerogel, zeolite molecular sieve, microporous carbon, and the specific surface area of the microporous material is controlled to be 1000-3000m2Per g, its pore volume is 0.5-2.0cm3/g。
8. The microporous material/carbon aerogel composite material prepared according to the method of any of the preceding claims.
9. Use of the microporous material/carbon aerogel composite of claim 8 in gas storage.
10. The use of claim 9, wherein the microporous material/carbon aerogel composite is serially connected by gas conduits in the storage tank, and a thermally conductive sheet is pre-positioned in the bottom layer, wherein thermally conductive sheets are positioned on the composite between each layer; preferably, the gas comprises methane, acetylene, hydrogen, carbon monoxide, carbon dioxide.
CN202210467845.6A 2022-04-29 2022-04-29 Microporous material/carbon aerogel composite material and preparation method and application thereof Active CN114669275B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104043435A (en) * 2014-05-07 2014-09-17 杭州师范大学 Porous adsorption plate used for soil heavy metal adsorption and preparation method thereof
CN107020071A (en) * 2017-04-21 2017-08-08 山东省科学院新材料研究所 A kind of super-hydrophobic compound carbon aerogels oil absorption material and preparation method thereof
CN110078048A (en) * 2019-05-23 2019-08-02 山东省科学院新材料研究所 A kind of carbon aerogels natural gas adsorbent and its preparation method and application
CN110143591A (en) * 2019-06-06 2019-08-20 山东省科学院新材料研究所 A kind of compound carbon aerogels of high-specific surface area and preparation method thereof
CN112691645A (en) * 2020-12-23 2021-04-23 山东省科学院新材料研究所 Carbon aerogel/metal organic framework composite material, preparation method thereof and application thereof in gas storage

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104043435A (en) * 2014-05-07 2014-09-17 杭州师范大学 Porous adsorption plate used for soil heavy metal adsorption and preparation method thereof
CN107020071A (en) * 2017-04-21 2017-08-08 山东省科学院新材料研究所 A kind of super-hydrophobic compound carbon aerogels oil absorption material and preparation method thereof
CN110078048A (en) * 2019-05-23 2019-08-02 山东省科学院新材料研究所 A kind of carbon aerogels natural gas adsorbent and its preparation method and application
CN110143591A (en) * 2019-06-06 2019-08-20 山东省科学院新材料研究所 A kind of compound carbon aerogels of high-specific surface area and preparation method thereof
CN112691645A (en) * 2020-12-23 2021-04-23 山东省科学院新材料研究所 Carbon aerogel/metal organic framework composite material, preparation method thereof and application thereof in gas storage

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