CN114669275B - 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 PDFInfo
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- CN114669275B CN114669275B CN202210467845.6A CN202210467845A CN114669275B CN 114669275 B CN114669275 B CN 114669275B CN 202210467845 A CN202210467845 A CN 202210467845A CN 114669275 B CN114669275 B CN 114669275B
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- carbon aerogel
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- microporous material
- carbon
- drying
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- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 58
- 239000012229 microporous material Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 19
- 238000003860 storage Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920002749 Bacterial cellulose Polymers 0.000 claims description 11
- 239000005016 bacterial cellulose Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000004964 aerogel Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000017 hydrogel Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002210 supercritical carbon dioxide drying Methods 0.000 claims description 3
- 238000000352 supercritical drying Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 108010022355 Fibroins Proteins 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000004965 Silica aerogel Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229920002494 Zein Polymers 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229940072056 alginate Drugs 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229920001221 xylan Polymers 0.000 claims description 2
- 150000004823 xylans Chemical class 0.000 claims description 2
- 239000005019 zein Substances 0.000 claims description 2
- 229940093612 zein Drugs 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims 1
- 229920001800 Shellac Polymers 0.000 claims 1
- 239000004208 shellac Substances 0.000 claims 1
- 229940113147 shellac Drugs 0.000 claims 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims 1
- 235000013874 shellac Nutrition 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- 239000003463 adsorbent Substances 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000003345 natural gas Substances 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000013084 copper-based metal-organic framework Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QDOMGXNVMDTECS-UHFFFAOYSA-N [C].O=C.OC1=CC=CC(O)=C1 Chemical compound [C].O=C.OC1=CC=CC(O)=C1 QDOMGXNVMDTECS-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 description 1
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000013094 zinc-based metal-organic framework Substances 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
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 consists 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 without a binder can effectively adsorb methane gas and store the methane gas, so that the microporous material/carbon aerogel composite material has good practical application value.
Description
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 disclosure of this background section is only intended to increase the 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 already known to those of ordinary skill in the art.
The Adsorption Natural Gas (ANG) has the advantages of light dead weight of the storage tank, good safety, low operation cost and the like, and is considered to be the safest and most economical storage method at present. ANG is mainly to use a porous material with high specific surface area as a medium to realize efficient storage of methane under lower pressure (35-65 bar). The high-performance adsorbent material is the core of the ANG technology, and aims at the key problem that the storage capacity is limited at present, and the popularization and the use of the natural gas adsorption storage technology are promoted to a great extent after the breakthrough and the improvement of the powder adsorbent are difficult to process, recycle and reuse.
The microporous material is mostly powder adsorbent, and is filled in a storage tank, a plurality of gaps are reserved among particles, and the density of natural gas in the gaps is actually the density of pure compressed natural gas under the pressure of the storage tank (3-6 MPa), and the microporous material does not contribute to increasing the storage density of the ANG.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a microporous material/carbon aerogel composite material, and a preparation method and application thereof. The composite material consists 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 clean energy gas such as methane and store the clean energy gas, so that the composite adsorbent 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 crosslinking agent into a solvent, and uniformly stirring; pouring the obtained solution into a porous mold, sealing, and then performing gel and drying; carbonizing the aerogel with honeycomb shape obtained by different drying modes at high temperature to obtain honeycomb carbon aerogel;
(2) Filling microporous materials into holes of honeycomb carbon aerogel; wherein, the middle big round hole is not added; the surface is encapsulated at the port by using a heat conducting sheet, and a middle hole is reserved.
The porous mold is a cylindrical container with the inside 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 inside of the cylinder is composed 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, the small cylinders are consistent with the height of the periphery, and the small cylinders are combined according to different arrangement modes according to requirements.
Further, the mold is made of polytetrafluoroethylene material.
Further, the carbon source material of the carbon aerogel comprises zein, silk fibroin, bacterial cellulose, xylan, lacca, 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%; solvents include water, methanol, ethanol, DMF, ethylene glycol, glycerol, pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, pyridine, piperidine, furan, tetrahydrofuran, dioxane, and dimethylsulfoxide.
Further, the gel temperature and the gel time are determined according to the specific components, the gel temperature can be 20-90 ℃, and the aging time is 2-72 h.
Further, the drying process includes two methods:
The supercritical CO 2 drying method is adopted: forming hydrogel from sol at a specific temperature, aging and replacing the sol with solvent, and performing supercritical drying; the gel temperature and time are determined according to the specific components, the temperature can be 20-90 ℃, the aging time is 2-72 h, and the solvent replacement time is 1-7 days.
The freeze drying method is adopted: freezing for a certain time, and freeze-drying. 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 tube furnace at a heating rate of 3-6deg.C/min to 600-1000deg.C, maintaining for 1-4 hr, naturally cooling to room temperature, and taking out, wherein a protective gas (nitrogen or argon) is directly introduced.
Further, the microporous material is used as a filler and comprises MOF (zinc-based MOF, cobalt-based MOF, copper-based MOF, zirconium-based MOF, etc.), silica aerogel, zeolite molecular sieve (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., the specific surface area of the microporous material is controlled to be 1000-3000m 2/g, the pore volume is 0.5-2.0cm 3/g, the microporous material is added into the pores of the honeycomb carbon aerogel (the adding mode is that the microporous material is directly filled into the pores of the honeycomb carbon aerogel, and the middle large round holes are not added).
The application of the microporous material/carbon aerogel composite material in gas storage. The method for applying the microporous material/carbon aerogel composite material comprises the steps of connecting the air ducts in the storage tanks for the microporous material/carbon aerogel composite material in series, and pre-placing a piece of heat conducting sheet at the bottom layer, wherein the heat conducting sheet on the composite material is arranged between each two layers, so that heat generated during adsorption can be emitted, and separation of the microporous material can be prevented. And finally, packaging the storage tank for gas storage application. 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 honeycomb carbon aerogel is prepared by the porous mold, the diameter of the cylinder in the mold can control the macroscopic pore size of the aerogel, so that the amount of the microporous material added is controlled, and the dispersion condition of the microporous material can be controlled by the arrangement mode. The microporous material is loaded in the holes of the aerogel, so that the problem (such as dampness) related to structural instability of the microporous material in the environment can be solved, and the heat generated during adsorption can be effectively dispersed by the heat conducting fin arranged at the port, so that the adsorption value can be improved.
(2) In the microporous material/carbon aerogel composite material prepared by the invention, the microporous material has 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 interaction between a host and a guest in the pores, and the adsorption kinetics is faster due to rapid mass transfer through the microscopic mesopores and macropores of the carbon aerogel framework, and meanwhile, the microporous material/carbon aerogel composite material also has integral blocks which are beneficial to processing and easy to recycle and good mechanical properties.
(3) The microporous material/carbon aerogel composite material prepared by the method is an integral block material, and the adhesive is not required to be added in the preparation and molding process, so that the microporous material/carbon aerogel composite material is simply filled, and the phenomenon of hole blocking caused by the addition of the adhesive is avoided; and the carbon aerogel framework material has good thermal conductivity, can accelerate the adsorption and desorption rates, is beneficial to reducing the cost and prolonging the service life of the adsorbent.
(4) According to the invention, the simple composite preparation based on the microporous material and the carbon aerogel is reported for the first time, not only can an integral blocky carrier be provided for the microporous material, but also a synergistic effect can be generated by compositing the microporous material and the carbon aerogel, so that the microporous material has the function of absorbing and storing clean energy gases such as methane, and experiments prove that the microporous material has excellent absorbing and storing performances on the clean energy gases such as methane, and meanwhile, the microporous material is wide in raw material resource, low in cost, accords with the green chemical production concept, and is beneficial to the development of actual industrialization and industrialization.
(5) The microporous material/carbon aerogel composite material prepared by the invention has excellent adsorption performance on CO 2 isothermal chamber gas, can effectively capture carbon, and has a certain positive effect on reducing CO 2 emission.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain 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 the porous mold prepared in example 1 of the present invention.
FIG. 3 is a block diagram of an ANG tank of the present invention mated with a composite material.
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 microstructure of the carbon aerogel of example 1 of the present invention with a nanopore structure.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. 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 formaldehyde carbon aerogel)
The die is made of polytetrafluoroethylene materials, and the size is as follows: 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 combination is realized in a matrix layout arrangement mode (the structure is shown in figures 1 and 2).
Dissolving 5.5g of resorcinol in 10ml of formaldehyde solution (37 wt%) and adding 50ml of water for dilution, adding anhydrous sodium carbonate as a catalyst, stirring until the solution is light yellow, pouring into the porous mold, placing in an oven at 80 ℃ for overnight gelation, placing the hydrogel into ethanol for replacement for 7 days to obtain alcogel, and carrying out CO 2 supercritical drying on the obtained alcogel to obtain resorcinol formaldehyde aerogel. Under the protection of nitrogen, heating the resorcinol formaldehyde aerogel to 800 ℃ in a tube furnace at a speed of 5 ℃/min, preserving heat for 2 hours, naturally cooling to room temperature, and taking out to obtain the resorcinol formaldehyde carbon aerogel (the structure is shown in fig. 4, the electron microscope diagram is shown in fig. 5, and the microstructure and the nano pore structure diagram are shown in fig. 6). The prepared Cu-MOF powder was filled into the voids of the carbon aerogel described above, and the port was encapsulated with a thermally conductive sheet and filled into an ANG tank (see fig. 3).
The resorcinol formaldehyde carbon aerogel material has good mechanical toughness. When the pressure reached a maximum, the sample did not break significantly, and the strain and stress of the carbon aerogel sample were 80% and 1.5Mpa, respectively. After 3000 cycles of gas adsorption and desorption, the natural gas adsorption volume is reduced by less than 10%.
Example 2 (13X molecular sieve/gelatin-based carbon aerogel)
The die is made of polytetrafluoroethylene materials, and the size is as follows: 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 provided with 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 cylinder is combined in an annular arrangement mode.
15G of gelatin is dissolved in 85ml of water, placed in a water bath kettle at 60 ℃ and stirred until the gelatin is completely dissolved, then 0.7ml of 37-40wt% formaldehyde solution is added, stirred at 60 ℃ for 5 hours and transferred into a die of the invention, the die is static for one day in normal temperature environment to obtain hydrogel, the hydrogel is directionally frozen and then transferred into a freeze dryer for freeze drying until all water is removed, the composite material is heated to 900 ℃ in a tube furnace at a speed of 5 ℃/min under the protection of argon, and the composite material is naturally cooled to room temperature and taken out after heat preservation for 3 hours, thus obtaining the gelatin-based carbon aerogel.
And filling the prepared 13X molecular sieve powder into the hollow of the carbon aerogel, packaging the port by using a heat conducting sheet, and filling the port into an ANG storage tank.
The gelatin-based carbon aerogel material has good mechanical toughness. When the pressure reached a maximum, the sample did not break significantly, and the strain and stress of the carbon aerogel sample were 75% and 0.561Mpa, respectively. After 3000 cycles of gas adsorption and desorption, the natural gas adsorption volume is reduced by less than 10%.
Example 3 (ZIF-67/bacterial cellulose-based carbon aerogel)
The die is made of polytetrafluoroethylene materials, and the size is as follows: 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 provided with 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 cylinder is combined in an annular arrangement mode.
Adding 5% (relative to the mass fraction of the alkaline urea system) of bacterial cellulose into the alkaline urea system (NaOH: urea: water=7:12:81), dissolving at low temperature until no particles (low rotation speed), and clarifying. Subpackaging the bacterial cellulose solution into moulds, heating the water-soluble pot to 72 ℃, putting the mould cup into a water bath pot, and taking out after water bath for 2 hours. After water bath molding, the bacterial cellulose hydrogel is obtained by soaking the bacterial cellulose hydrogel in deionized water until the replacement liquid of the sample changes from yellow to transparent, removing redundant impurities and replacing for about 5 days (the surface of the water soaking has a layer of oil to be emerged, namely alkali liquor to be removed). And replacing the bacterial fiber hydrogel with absolute ethyl alcohol, and performing CO 2 supercritical to obtain the bacterial cellulose aerogel. And then under the protection of nitrogen, heating the composite material to 1000 ℃ in a tube furnace at a speed of 5 ℃/min, preserving heat for 4 hours, naturally cooling to room temperature, and taking out to obtain the bacterial cellulose-based carbon aerogel.
Filling the prepared ZIF-67 powder into the hollow space of the bacterial cellulose-based carbon aerogel, packaging the port by using a heat conducting sheet, and filling the port into an ANG storage tank.
The bacterial cellulose-based carbon aerogel material has good mechanical toughness. When the pressure reached a maximum, the sample did not significantly crush, and the strain and stress of the carbon aerogel sample were 78% and 0.582Mpa, respectively. After 3000 cycles of gas adsorption and desorption, the natural gas adsorption volume is reduced by less than 10%.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the above-mentioned embodiments, but may be modified or substituted for some of them by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention. While the foregoing describes the embodiments of the present invention, it should be understood that the present invention is not limited to the embodiments, and that various modifications and changes can be made by those skilled in the art without any inventive effort.
Claims (12)
1. The preparation method of the microporous material/carbon aerogel composite material is characterized by comprising the following steps of:
(1) Adding a carbon source material and a crosslinking agent into a solvent, and uniformly stirring; pouring the obtained solution into a porous mold, sealing, and then performing gel and drying; carbonizing the obtained aerogel with the honeycomb shape at high temperature to obtain honeycomb carbon aerogel;
(2) Filling microporous materials into holes of honeycomb carbon aerogel; wherein, the middle big round hole is not added; packaging the surface by using a heat conducting fin at a port, and leaving a middle hole to obtain the microporous material/carbon aerogel composite material;
the porous mold is a cylindrical container with the inside composed of a plurality of small cylinders and a middle cylinder;
The periphery of the cylinder is cylindrical with the height of 5-10cm, the outer diameter of 5-10cm and the inner diameter of 4.8-9.8cm, the inside of the cylinder is composed 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 in height, and the height of the small cylinders is consistent with the height of the periphery; or, the porous mold is made of polytetrafluoroethylene material;
The diameter of the cylinder in the mould controls the size of the macroscopic hole of the aerogel, thereby controlling the amount of the microporous material added, and the arrangement mode of the cylinder in the mould controls the dispersion condition of the microporous material.
2. The method according to claim 1, wherein the gel conditions are: the gel temperature is 20-90 ℃, and the aging time is 2-72 hours.
3. The 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, resorcinol, polyvinyl alcohol, melamine, and the cross-linking agent comprises one or more of N, N-methylenebis (acrylamide), ethylenediamine, polyacrylic acid, formaldehyde, polyacrylamide, 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 dimethyl sulfoxide.
4. The method of preparation of claim 1, wherein the drying comprises two methods:
the supercritical CO 2 drying method is adopted: forming hydrogel from sol at a specific temperature, aging and replacing the sol with solvent, and performing supercritical drying;
The freeze drying method is adopted: freezing for a certain time, and freeze-drying.
5. The method according to claim 4, wherein the supercritical CO 2 drying process is carried out at a temperature of 20-90 ℃ for 2-72 hours and for 1-7 days.
6. The method according to claim 4, wherein the freeze-drying method comprises directional freezing for 5-60min, non-directional freezing for 24-72h, and freeze-drying for 3-7 days.
7. The method according to claim 1, wherein the high temperature carbonization is specifically: heating in a tube furnace at a heating rate of 3-6 ℃/min, heating to 600-1000 ℃, preserving heat for 1-4h, naturally cooling to room temperature, and taking out, wherein the whole process is filled with protective gas, and the protective gas is nitrogen or argon.
8. The method according to 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 1000-3000m 2/g, and the pore volume thereof is controlled to be 0.5-2.0cm 3/g.
9. A microporous material/carbon aerogel composite prepared according to the method of any of claims 1-8.
10. Use of the microporous material/carbon aerogel composite according to claim 9 in gas storage.
11. The use according to claim 10, characterized in that the method of application is to connect the air ducts in the tanks of microporous material/carbon aerogel composite material in series, the bottommost layer being pre-laid with a thermally conductive sheet, wherein between each layer there is a thermally conductive sheet on the composite material.
12. The use according to claim 10, wherein the gas comprises methane, acetylene, hydrogen, carbon monoxide, carbon dioxide.
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