CN113731353A - Carbon absorption material and synthesis method thereof - Google Patents
Carbon absorption material and synthesis method thereof Download PDFInfo
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- CN113731353A CN113731353A CN202110885757.3A CN202110885757A CN113731353A CN 113731353 A CN113731353 A CN 113731353A CN 202110885757 A CN202110885757 A CN 202110885757A CN 113731353 A CN113731353 A CN 113731353A
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- 239000000463 material Substances 0.000 title claims description 27
- 238000010521 absorption reaction Methods 0.000 title claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 6
- 229910052799 carbon Inorganic materials 0.000 title claims description 6
- 238000001308 synthesis method Methods 0.000 title description 2
- 150000001412 amines Chemical class 0.000 claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001179 sorption measurement Methods 0.000 claims abstract description 37
- 239000003463 adsorbent Substances 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 20
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 20
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 20
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920002873 Polyethylenimine Polymers 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000009849 vacuum degassing Methods 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 229940043237 diethanolamine Drugs 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 238000011068 loading method Methods 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 19
- 229910021485 fumed silica Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- -1 alcohol amine Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
-
- 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
- B01D53/04—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 with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/3071—Washing or leaching
-
- 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
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
CO (carbon monoxide)2Preparation method and application of adsorbent prepared from SiO2Loading amine and CO to raw material by dipping and freeze drying2Adsorption and aluminum source addition synthesis of amine-loaded ZSM-5 molecular sieve composite material for CO2Adsorption of (3). The method realizes the accurate and uniform modification of the three-dimensional pore channel surface of the amine in the carrier, and has the advantages of aluminum-based and silicon-based materials. In the preparation method, no organic solvent is used in the preparation process, and the method has the advantages of environmental friendliness, safety, easiness in operation and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of adsorbents, and relates to a method for adsorbing CO2Preparation method of high-efficiency adsorbent
Background
CO in the atmosphere2The continuous rise of concentration brings a series of environmental problems, and under the era background of 'carbon neutralization and carbon peak reaching', CO is generated2The capture and sequestration techniques are of great importance.
At present, an alcohol amine solution absorption method, a metal compound absorption method, a low-temperature storage method, a membrane separation method, and the like are applied to CO2However, the chemical reagents and equipment used are expensive, and the increase in production cost due to difficulty in regeneration, etc. limits the large-scale application of the above-mentioned method.
The solid amine adsorption technology has the advantages of strong adsorption capacity, low regeneration energy consumption, excellent cycle stability and the like, and becomes ideal CO2Trapping and sealing techniques.
The solid amine adsorption technology takes a solid porous material as a carrier, and amine is loaded on the surface of the solid material to increase the number of alkaline sites, so that CO is increased2Adsorption capacity, therefore, the pore structure and surface properties of the solid porous material will be towards CO2The adsorption performance has a significant impact.
The solid amine adsorption material mainly focuses on single silicon-based and single aluminum-based organic amine loaded. CN110551317A introduces a silica-based aerogel CO loaded with organic amine prepared by a sol-gel method through copolycondensation reaction2Adsorbent for CO at normal pressure and 40 deg.C2The maximum adsorption amount of the adsorbent reaches 24 mg/g. CN104148020B introduces CO which takes alumina-based mesoporous composite oxide as a carrier to load tetraethylenepentamine2An adsorbent for CO at room temperature and normal pressure2The maximum adsorption amount of (A) reaches 89 mg/g. Synthesis of porous nano Al by Zhang Joita professor2O3Support in Al2O3The solid amine material is prepared by loading PEI on a carrier, and CO is successfully prepared2The adsorption capacity of the adsorbent reaches 136 mg/g. The adsorbent is used in the actual CO2The cyclic regeneration under the atmosphere still maintains very stable adsorption capacity, and CO is recycled for 10 times 2The adsorption capacity is still as high as 111mg/g, which is obviously improved by 5.5 times compared with the traditional silicon-based solid amine material.
The supports used in the above reported methods are all three-dimensional porous structures, increasing the specific surface area of the adsorbent, but not conducive to precise and uniform modification using amines. Therefore, the carbon absorption material capable of accurately and uniformly loading amine is developed for the solid amine absorption technology for CO2The trapping and the sealing have great significance.
Disclosure of Invention
The invention aims to provide a method for CO aiming at the defects of the prior art2A preparation method and application of an efficient adsorbent for adsorption.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
CO (carbon monoxide)2The preparation method of the adsorbent comprises the following steps:
firstly, carrying out impregnation and freeze-drying to load amine;
mixing SiO2Ultrasonically dispersing the powder in deionized water, adding amine into the dispersion liquid, and then violently stirring for 0.5-1.5 hours to enable SiO to be dissolved2Mixing with amine, stirring, and freeze drying for 48 hr to obtain amine/SiO2。
The amine is one or more than two of tetraethylenepentamine, triethylenetetramine, diethanolamine, polyethyleneimine, tripropylamine, triisopropanolamine, formamide, p-phenylenediamine and phthalimide.
The SiO2Is precipitated white carbon black and gas-phase white carbon black.
The mass of the loaded amine is SiO in stable dispersion liquid20.2-50% of the mass.
Second step, CO2Adsorption;
the amine/SiO obtained in the first step2Subjecting the material to CO2And (3) adsorbing under the following adsorption conditions: vacuum degassing at 150 deg.C for 12 hr, and performing CO at 40 deg.C under 0-50bar2And (4) adsorbing.
Thirdly, synthesizing a ZSM-5 molecular sieve material without a solvent;
adsorbing the saturated CO obtained in the second step2After amine/SiO2The material is mixed with aluminum source, ZSM-5 seed crystal and Na2SiO3·9H2O、NH4And fully mixing Cl, putting the mixed raw materials into a closed reactor, and heating and reacting for a certain time to obtain the amine/ZSM-5 composite material.
The ZSM-5 seed crystal is SiO in the raw material21-20% of the mass.
The aluminum source can be aluminum-containing salt, aluminum oxide, etc., or Al2O3Meter, SiO2/Al2O3The molar ratio is 25- + infinity.
Compared with the prior art, the invention has the advantages and beneficial effects that: the invention uses SiO2Loading amine and CO to raw material by dipping and freeze drying2Adsorption and solvent-free synthesis of ZSM-5 molecular sieve material to obtain amine-loaded ZSM-5 molecular sieve composite material for CO2And (4) adsorbing. Due to SiO2Carrying out CO by loading amine at the early stage of raw material2Adsorption, and CO is carried out after material synthesis2Desorption of the resulting CO 2The adsorption point positions are all effective point positions, and the ZSM-5 molecular sieve used as the carrier has abundant three-dimensional pore channels and acid point positions, so that the surface of the three-dimensional pore channel carrier is accurately and uniformly modified by amine. In the preparation method, no organic solvent is used in the preparation process of the amine-loaded ZSM-5 molecular sieve composite material, and the method has the advantages of environmental friendliness, safety, easiness in operation and the like. CO Using the composite Material of the invention2The adsorption capacity is large, the method is simple and applicable, green and environment-friendly, and the carbon dioxide is CO2The emission reduction work provides new technical support.
Drawings
Figure 1 XRD pattern of the composite obtained in example 1.
Figure 2 XRD pattern of the composite obtained in example 2.
Figure 3 XRD pattern of the composite obtained in example 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples.
SiO in the examples of the invention2The precipitated silica and the fumed silica are preferably used, but not limited thereto. The supported amine is one or more selected from tetraethylenepentamine, triethylenetetramine, diethanolamine, polyethyleneimine, tripropylamine, triisopropanolamine, formamide, p-phenylenediamine, and phthalimide, and Polyethyleneimine (PEI) is preferable, but not limited thereto.
Example 1:
CO (carbon monoxide)2The preparation method of the adsorbent comprises the following steps:
s1 amine loading by impregnation and freeze drying
1 g of fumed silica and 200 ml of deionized water are mixed and then placed in ultrasonic equipment for treatment for 30 minutes, and the mass of the fumed silica is added into the ultrasonic dispersion liquidAfter 0.2% of PEI, vigorously stirring for 1 hour to fully mix the white carbon black and the PEI, and after stirring, carrying out freeze drying treatment for 48 hours to obtain the PEI/SiO2A material.
S2、CO2Adsorption
The PEI/SiO obtained in S12Subjecting the material to CO2And (3) adsorbing under the following adsorption conditions: vacuum degassing at 150 deg.C for 12 hr, and performing CO at 40 deg.C under 0-50bar2And (4) adsorbing.
S3 solvent-free synthesis of ZSM-5 molecular sieve material
Adsorbing the saturated CO obtained in S22Post PEI/SiO2Materials with Na2SiO3·9H2O、NH4Cl、NaAlO2And ZSM-5 seed crystals are fully mixed, the mixed raw materials are placed into a closed reactor to be heated and reacted for a certain time, and the PEI/ZSM-5 composite material, SiO in the ZSM-5 molecular sieve, is obtained after washing and drying2/Al2O3The molar ratio is 50, and the XRD is shown in figure 1. The obtained PEI/ZSM-5 composite material is used for CO2And (4) adsorbing.
CO of the above 0.2% PEI/ZSM-5(50) composite2Adsorption application: putting the PEI/ZSM-5 composite material into a fixed bed reactor, degassing for 12 hours at 150 ℃ in vacuum, and then respectively carrying out CO at 20 ℃, 40 ℃, 60 ℃ and the pressure range of 0-50bar 2And (4) adsorbing. The results showed that the maximum adsorption amounts of the adsorbents were 88mg/g, 79mg/g, and 67mg/g, respectively, at adsorption temperatures of 30 deg.C, 40 deg.C, and 60 deg.C.
Example 2:
CO (carbon monoxide)2The preparation method of the adsorbent comprises the following steps:
s1 amine loading by impregnation and freeze drying
Mixing 1 g of fumed silica and 200 ml of deionized water, placing the mixture in ultrasonic equipment for treatment for 30 minutes, adding PEI (polyetherimide) with the mass being 2% of the mass of the fumed silica into ultrasonic dispersion liquid, then violently stirring for 1 hour to fully mix the fumed silica and the PEI, and after stirring, carrying out freeze drying treatment for 48 hours to obtain PEI/SiO2A material.
S2、CO2Adsorption
The PEI/SiO obtained in S12Subjecting the material to CO2And (3) adsorbing under the following adsorption conditions: vacuum degassing at 150 deg.C for 12 hr, and performing CO at 40 deg.C under 0-50bar2And (4) adsorbing.
S3 solvent-free synthesis of ZSM-5 molecular sieve material
Adsorbing the saturated CO obtained in S22Post PEI/SiO2Materials with Na2SiO3·9H2O、NH4Cl、NaAlO2And ZSM-5 seed crystals are fully mixed, the mixed raw materials are placed into a closed reactor to be heated and reacted for a certain time, and the PEI/ZSM-5 composite material, SiO in the ZSM-5 molecular sieve, is obtained after washing and drying2/Al2O3The molar ratio is 50, and the XRD is shown in figure 2. The obtained PEI/ZSM-5 composite material is used for CO 2And (4) adsorbing.
CO of the above 2% PEI/ZSM-5(50) composite2Adsorption application: putting the PEI/ZSM-5 composite material into a fixed bed reactor, degassing for 12 hours at 150 ℃ in vacuum, and then respectively carrying out CO at 20 ℃, 40 ℃, 60 ℃ and the pressure range of 0-50bar2And (4) adsorbing. The results showed that the maximum adsorption amounts of the adsorbents were 118mg/g, 110mg/g, and 97mg/g, respectively, at adsorption temperatures of 30 ℃, 40 ℃, and 60 ℃.
Example 3:
CO (carbon monoxide)2The preparation method of the adsorbent comprises the following steps:
s1 amine loading by impregnation and freeze drying
Mixing 1 g of fumed silica and 200 ml of deionized water, placing the mixture in ultrasonic equipment for treatment for 30 minutes, adding PEI (polyetherimide) with the mass being 2% of the mass of the fumed silica into ultrasonic dispersion liquid, then violently stirring for 1 hour to fully mix the fumed silica and the PEI, and after stirring, carrying out freeze drying treatment for 48 hours to obtain PEI/SiO2A material.
S2、CO2Adsorption
The PEI/SiO obtained in S12Subjecting the material to CO2And (3) adsorbing under the following adsorption conditions: vacuum degassing at 150 deg.C for 12 hr, and performing CO at 40 deg.C under 0-50bar2And (4) adsorbing.
S3 solvent-free synthesis of ZSM-5 molecular sieve material
Adsorbing the saturated CO obtained in S22Post PEI/SiO2Materials with Na 2SiO3·9H2O、NH4Cl、NaAlO2And ZSM-5 seed crystals are fully mixed, the mixed raw materials are placed into a closed reactor to be heated and reacted for a certain time, and then the PEI/ZSM-5 composite material, SiO in the ZSM-5 molecular sieve, is obtained by washing and drying2/Al2O3The molar ratio is 25, and the XRD is shown in figure 3. The obtained PEI/ZSM-5 composite material is used for CO2And (4) adsorbing.
CO of the above 2% PEI/ZSM-5(25) composite2Adsorption application: putting the PEI/ZSM-5 composite material into a fixed bed reactor, degassing for 12 hours at 150 ℃ in vacuum, and then respectively carrying out CO at 20 ℃, 40 ℃, 60 ℃ and the pressure range of 0-50bar2And (4) adsorbing. The results showed that the maximum adsorption amounts of the adsorbents were 132mg/g, 124mg/g, and 109mg/g, respectively, at adsorption temperatures of 30 deg.C, 40 deg.C, and 60 deg.C.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. The preparation method of the carbon absorption material is characterized by comprising the following steps:
firstly, carrying out impregnation and freeze-drying to load amine;
mixing SiO2Mixing the powder and deionized water according to a ratio of 5g/L, carrying out ultrasonic dispersion treatment, adding amine into the dispersion liquid, and then violently stirring for 0.5-1.5 hours to enable SiO to be generated 2Mixing with amine, stirring, and freeze drying for 48 hr to obtain amine/SiO2。
Second step, CO2Adsorption;
the amine/SiO2Subjecting the material to CO2And (3) adsorbing under the following adsorption conditions: vacuum degassing at 150 deg.C for 12 hr, and performing CO at 40 deg.C under 0-50bar2And (4) adsorbing.
Thirdly, synthesizing a ZSM-5 molecular sieve material without a solvent;
adsorbing the saturated CO obtained in the second step2After amine/SiO2The material is mixed with aluminum source, ZSM-5 seed crystal and Na2SiO3·9H2O、NH4Fully mixing Cl, putting the mixed raw materials into a closed reactor, heating and reacting for a certain time, washing and drying to obtain the amine/ZSM-5 composite material for CO2And (4) adsorbing.
2. CO according to claim 12The preparation method of the adsorbent is characterized in that the SiO2The powder is one of precipitated white carbon black and gas-phase white carbon black.
3. CO according to claim 12The preparation method of the adsorbent is characterized in that the amine is one or more than two of tetraethylenepentamine, triethylenetetramine, diethanol amine, polyethylene imine, tripropylene amine, triisopropanol amine, formamide, p-phenylenediamine and phthalimide.
4. CO according to claim 12The preparation method of the adsorbent is characterized in that the mass of the loaded amine is SiO in stable dispersion liquid 20.2-50% of the mass.
5. CO according to claim 12The preparation method of the adsorbent is characterized in that the ZSM-5 seed crystal is SiO in the raw material21-20% of the mass, the aluminum source can be aluminum salt, aluminum oxide and the like, and Al is used2O3Meter, SiO2/Al2O3The molar ratio is 25- + infinity.
6. CO according to claim 12Use of an adsorbent, characterized in that the CO is introduced2Placing the adsorbent in a fixed bed reactor, vacuum degassing at 150 deg.C for 12 hr under absolute pressure of 0.013bar, and then under pressure of 0-50bar and 30-60 deg.CBy carrying out CO2And (4) adsorbing.
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