CN113813927A - Foam carbon-based solid amine adsorbent and preparation method and application thereof - Google Patents
Foam carbon-based solid amine adsorbent and preparation method and application thereof Download PDFInfo
- Publication number
- CN113813927A CN113813927A CN202111226312.0A CN202111226312A CN113813927A CN 113813927 A CN113813927 A CN 113813927A CN 202111226312 A CN202111226312 A CN 202111226312A CN 113813927 A CN113813927 A CN 113813927A
- Authority
- CN
- China
- Prior art keywords
- carbon
- coal
- based foam
- foam carbon
- adsorbent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 144
- 239000006260 foam Substances 0.000 title claims abstract description 112
- 150000001412 amines Chemical class 0.000 title claims abstract description 89
- 239000003463 adsorbent Substances 0.000 title claims abstract description 81
- 239000007787 solid Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003245 coal Substances 0.000 claims abstract description 141
- 238000001179 sorption measurement Methods 0.000 claims abstract description 78
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 73
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000004079 vitrinite Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 230000004913 activation Effects 0.000 claims abstract description 17
- 239000012141 concentrate Substances 0.000 claims abstract description 16
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 52
- 239000011148 porous material Substances 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 35
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 28
- 238000005187 foaming Methods 0.000 claims description 26
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 24
- 238000001994 activation Methods 0.000 claims description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 238000003795 desorption Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 17
- 239000004088 foaming agent Substances 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 10
- 239000003546 flue gas Substances 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 claims description 3
- 239000012494 Quartz wool Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000009919 sequestration Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000008676 import Effects 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 229960001124 trientine Drugs 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 10
- 238000011069 regeneration method Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000013012 foaming technology Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 239000000243 solution Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 22
- 210000004027 cell Anatomy 0.000 description 21
- 239000007789 gas Substances 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000002184 metal Substances 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000011068 loading method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000002336 sorption--desorption measurement Methods 0.000 description 9
- 238000007605 air drying Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 210000003429 pore cell Anatomy 0.000 description 6
- 238000004939 coking Methods 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013310 covalent-organic framework Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- -1 amine carbon dioxide Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 230000036619 pore blockages Effects 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 208000037972 tropical disease Diseases 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- 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
- B01D53/30—Controlling by gas-analysis apparatus
-
- 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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- 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
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a foamy carbon-based solid amine adsorbent and a preparation method and application thereof, relating to the technical field of gas trapping materials, wherein the method comprises the following steps: the method comprises the steps of taking vitrinite concentrates with different coalification degrees as precursors, preparing primary coal-based foam carbon by adopting a supercritical foaming technology, carbonizing to obtain the coal-based foam carbon, preparing a coal-based foam carbon carrier with a hierarchical porous structure through activation heat treatment, and preparing the solid adsorbent through amine functionalization. The invention has the advantages that the raw material source is wide, the method is suitable for industrial production, and the carrier with the hierarchical porous structure can effectively load organic amine. When the solid adsorbent is used for capturing carbon dioxide, the operation is simple, the corrosion to equipment is small, and the excellent carbon dioxide adsorption performance and regeneration capacity are shown.
Description
Technical Field
The invention relates to the technical field of gas trapping materials, in particular to a foamy carbon-based solid amine carbon dioxide adsorbent and a preparation method and application thereof.
Background
The continuing rise in atmospheric greenhouse gas concentrations has raised unprecedented attention to global warming, which can lead to a range of disasters, such as the breeding and spread of tropical diseases, land degradation, flooding, and species extinction. In addition, carbon dioxide released during the combustion of fossil fuels and their derivatives has become one of the most important sources of greenhouse gases. Therefore, efficient capture and separation of carbon dioxide has become a primary task to effectively cope with global warming. The capture of carbon dioxide from fossil fuel flue gases is a direct solution to reduce carbon dioxide emissions. Over the past decade, many advanced carbon dioxide capture and sequestration processes have been developed. Among these capture methods, liquid amine absorption method captures CO2Has been put into practical use. The method has the advantages of high efficiency, large adsorption capacity and the like. However, this method still has many disadvantages, which limit itIs widely applied. For example, degradation of the liquid amine can easily degrade the absorption properties of the liquid amine; strong basicity of the amine liquid seriously corrodes equipment, and the amine liquid is greatly regenerated and consumed.
In order to overcome the defects, a solid adsorbent using a porous material as an adsorbent instead of liquid ammonia is proposed for adsorbing and capturing CO2The method of (1). Commonly used porous materials include Activated Carbon (AC), zeolites, layered hydroxides, metal oxides, Metal Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs), and mesoporous silica-based materials. Solid adsorbents are regarded as important because of their simple method of operation and low corrosiveness to equipment. However, these porous material adsorbents generally have the disadvantages of poor selectivity, low adsorption capacity, and poor water resistance. To increase the CO2The adsorption capacity and selectivity of the porous material are improved, the problem of poor water resistance of the porous material is solved, and the solid amine adsorbent taking the porous material as a carrier and organic amine as a modifier is widely applied. The solid amine adsorbent has the characteristics of high selectivity, easiness in regeneration and the like when used for capturing carbon dioxide, and has a potential application prospect in the aspect of reducing carbon dioxide emission. Compared with liquid amine solution, the solid amine adsorption method has the advantages of simple operation, low regeneration energy consumption, small corrosion to equipment, high adsorption/desorption speed and the like. Amine functionalization of porous materials is usually achieved by an impregnation method, wherein amines are loaded into a supporting porous matrix material through physical action, and the pores can be filled with amine chemisorption agents by the impregnation method, and a plurality of carbon dioxide adsorption active centers are formed.
However, the loading of amine and CO by the pore structure of the porous material2The trapping has important influence, the prior solid amine adsorbent amine is easy to agglomerate in a matrix material to cause pore blockage, how to realize the effective load of the amine on the porous matrix material, introduce a large amount of amine groups while keeping the high dispersion of the amine groups on a carrier, and realize the CO2The high-efficiency trapping of (2) is a research difficulty in the field of solid adsorbents.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a foamy carbon-based solid amine adsorbent, which is used for solving the problems that the existing solid amine adsorbent cannot be effectively loaded on a porous matrix material and cannot efficiently capture carbon dioxide.
The invention also aims to provide the foamy carbon-based solid amine adsorbent prepared by the preparation method of the foamy carbon-based solid amine adsorbent.
The invention also aims to provide an application of the carbon foam-based solid amine adsorbent in carbon dioxide capture.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a preparation method of a foamy carbon-based solid amine adsorbent, which comprises the following steps:
s1: using vitrinite concentrates of the same or different coal types as precursors to prepare primary coal-based foam carbon by a supercritical foaming method;
s2: carbonizing the primary coal-based foam carbon to obtain coal-based foam carbon;
s3: carrying out activation heat treatment on the coal-based foam carbon to prepare graded porous coal-based foam carbon with micropore, mesopore and macropore structures;
s4: and performing amino functionalization on the graded porous coal-based foam carbon by using an amine modifier to obtain a foam carbon-based solid amine adsorbent.
The solid amine adsorbent is formed by loading organic amine into pore channels of a porous carrier. The foamy carbon-based solid amine adsorbent is a solid amine adsorbent taking foamy carbon as a carrier, namely amine functionalized foamy carbon.
Step S1
The invention uses coal vitrinite as a precursor and combines a supercritical foaming method to prepare the primary coal-based foam carbon with special pore cells and pore size distribution.
Coal includes, but is not limited to, gas coal, fat coal, and coking coal, among others. The source of the vitrinite concentrate is not limited, and the vitrinite concentrate can be obtained by a commercial product or an existing enrichment method (for example, patent CN 102849723A).
Further, step S1 includes: a high-pressure reaction kettle is used as a reactor, coal separation vitrinite enrichment with the particle size of 60-80 meshes (178-254 microns) or a mixture of vitrinite enrichment of different coal types is placed in a container, and then the vitrinite enrichment is carried out according to the following steps: adding the supercritical foaming agent at a mass ratio of 5: 1-200 (e.g., 5:1, 5:2, 1:10, 1:12, 1:16, 1:20, 1:24, 1:30, 1:40), heating at a speed of 1-20 ℃/min to a foaming temperature of Tc-Tc +200 ℃, keeping the final foaming pressure of Pc-Pc +4MPa constant (Tc is the critical temperature of the supercritical foaming agent, and Pc is the critical pressure of the supercritical foaming agent), foaming at a constant temperature for 0.5-4 h (e.g., 0.5, 1, 2, 3, 4h) under the supercritical condition of the foaming agent, releasing the pressure at a pressure release speed of 4-100 MPa/min to the normal pressure, and cooling (preferably naturally cooling) to the room temperature to obtain the primary coal-based foam carbon.
Particularly, in step S1, after the pressure in the high-pressure reaction kettle is relieved to the normal pressure, the air outlet valve is closed, the temperature is continuously increased to 550-600 ℃ at the speed of 2-5 ℃/min, the temperature is kept constant for 15-30 min, and then the temperature is reduced, preferably naturally reduced to the room temperature, so as to obtain the primary coal-based foam carbon.
The supercritical foaming agent is a special fluid which is simultaneously in the conditions of critical pressure (Pc) and critical temperature (Tc) or above, the supercritical fluid is in a liquid or solid state at normal temperature and normal pressure, and the supercritical foaming agent is preferably toluene or naphthalene.
The invention uses vitrinite enrichment as a precursor, uses naphthalene and toluene as supercritical foaming agents, applies a supercritical foaming method to the coal-based foam carbon, and has more industrialization possibility on the premise of China lean oil and rich coal.
Step S2
And (3) carbonizing the primary coal-based foam carbon obtained by taking the vitrinite enrichment of coal as a precursor.
Step S2 includes: and transferring the primary coal-based foam carbon obtained in the step S1 to a tubular furnace for carbonization treatment, heating to 800-1000 ℃ at a speed of 2-5 ℃/min under a protective atmosphere, keeping the temperature for 60-120 min, and naturally cooling to room temperature to obtain the coal-based foam carbon.
Through the high-temperature carbonization process, light components in the coal-based foam carbon are removed, the volatile components of the coal-based foam carbon are reduced, and more pore structures are formed.
The pore cell and pore distribution of the coal-based foam carbon prepared by carbonization are as follows: the diameter distribution of the cells is 35 to 425 μm (e.g., 36.55 to 422.75 μm), and the bulk density is 0.5 to 0.7g/cm3(e.g., 0.54 to 0.66 g/cm)3) The porosity is 55 to 70% (for example, 58.6 to 67.51%).
The pore cells are of obvious cellular structures on the surface of the coal-based foam carbon, and the diameter distribution of the pore cells is obtained by counting SEM pictures by using Nano Measurer 1.2 particle size analysis software.
Grinding the coal-based foam carbon before activation (the coal-based foam carbon after carbonization) to the granularity of less than 0.2mm, and then testing the true density (rho) by adopting a pycnometer method (GB/T21721996)T) (unit: g/cm3). The carbon foam was processed into a rectangular parallelepiped having a length, width and height of about 20mm, 20mm and 10mm, respectively, the average length (a), width (b) and height (h) (unit: cm) of the sample were precisely measured with a vernier caliper, the mass (M) (unit: g) of the sample was weighed, and the bulk density (. rho.) of the sample was calculated according to the formula (1)V) (unit: g/cm3) The porosity (P) of the sample (unit: %).
Step S3
Activating the coal-based foam carbon obtained in S2 (such as KOH/K)2CO3Activating by an alkaline activator) and performing heat treatment (pore-forming) to obtain the graded porous coal-based foam carbon with micropore, mesopore and macropore structures.
The pores in the powder material are divided into Micropores (Micropores) according to size: the aperture is less than 2 nm; mesopores or Mesopores (mesopors): the aperture is 2-50 nm; macropores (Macropores): pore diameters > 50nm (International Union of pure and applied chemistry (IUPAC)). The hierarchical porous structure herein refers to a hierarchical porous structure having micropores, mesopores, and macropores at the same time.
Further, step S3 includes: and (2) putting the coal-based foam carbon obtained in the step (S2) into a KOH solution, stirring a solid base (such as KOH) and the coal-based foam carbon at a mass ratio of 1-6: 1 (such as 1:1, 2:1, 3:1, 4:1, 5:1 and 6:1) for 30 minutes, soaking at 60-90 ℃ for 4-10 hours, drying, heating to 700-1050 ℃ at a constant rate of 2-5 ℃/min under a protective atmosphere for 1-4 hours, washing with hydrochloric acid and distilled water until the pH value is 7, filtering and drying to obtain the graded porous coal-based foam carbon. FIG. 1 shows a schematic flow diagram of an alkali activation process for producing graded porous coal-based foam carbon in one embodiment.
The coal-based foam carbon has a relatively single pore structure, and a part of microporous structure is manufactured on the basis of the original pore structure of the coal-based foam carbon through a further activation process, so that the foam carbon matrix is promoted to have a hierarchical porous structure of micropores, mesopores and macropores.
The graded porous coal-based foam carbon prepared by the activation heat treatment has a specific graded porous structure and a larger specific surface area: the specific surface area is 1050-2048 m2G (e.g. 1087.11 m)2/g～2048m2Per gram) and pore volume of 0.8 to 1.5cm3In grams (e.g., 0.89 cm)3/g～1.48cm3In terms of/g). The ratio of micropores, mesopores and macropores is 23-26% (e.g. 23.1-25.3%), 50-56% (e.g. 51.2-56%) and 18-26% (e.g. 18.6-25.6%).
The ratio of micropores, mesopores and macropores is the BET statistic divided by the number of pores in a certain pore space divided by the total number of pores.
The invention adopts the means of supercritical foaming, chemical activation and the like of coal vitrinite to prepare the coal-based foam carbon with a specific hierarchical porous structure, the foam carbon has larger specific surface area, the structural characteristics are favorable for realizing the loading of organic amine on the surface of a matrix, and the mass transfer resistance in the process of adsorbing carbon dioxide by the organic amine is effectively reduced.
Step S4
And performing amine functionalization on the graded porous coal-based foam carbon obtained in the step S3 by using an amine modifier.
The amine modifier is mainly organic amine, including but not limited to Diethylenetriamine (DETA), Tetraethylenepentamine (TEPA), triethylenetetramine (TETA), Polyethyleneimine (PEI), ethanolamine (MEA), 2, 6-Diethylaniline (DEA).
Further, step S4 includes: the organic amine is dissolved in methanol (20mL) with stirring, for example, using a magnetic stirrer. After the organic amine is completely dissolved, the graded porous coal-based carbon foam obtained in S3 is added to the mixed solution, and refluxed at 50 to 80 ℃ (for example, 70 ℃) for 6 to 10 hours. The resulting product is air dried at 80 ℃, for example in a forced air drying oven for 12h to 36h, to remove the methanol from the sample. Then, the organic impregnated sample was vacuum-dried at 60 ℃ for 12 hours to obtain a foamy carbon-based solid amine adsorbent.
The graded porous coal-based foam carbon is used as a carrier of organic amine, and can be customized according to requirements (the structure of the carrier can be adjusted). After the graded porous coal-based foam carbon obtained in S3 is placed in a mixed solution of organic amine and methanol, organic amines such as Diethylenetriamine (DETA), Tetraethylenepentamine (TEPA), triethylenetetramine (TETA), Polyethyleneimine (PEI), ethanolamine (MEA), 2, 6-Diethylaniline (DEA), or a mixture of a plurality of organic amines are carried according to the actual working condition of capturing carbon dioxide.
Preferably, the organic amine loading amount in the foamy carbon-based solid amine adsorbent is 0.1-60 wt%.
How to introduce a large amount of amine groups while maintaining a high dispersion of amine groups on the support is a challenge in preparing a highly efficient solid amine adsorbent. In order to solve the problem of organic pollution, the amine is easy to agglomerate in the solid amine adsorbent, the adsorption of cheap and efficient carbon dioxide capture is realized, coal-based foam carbon with rich hierarchical porous structure is used as a support, and the organic amine is impregnated to prepare the novel solid adsorbent.
In one embodiment, a method for preparing a typical solid amine adsorbent based on carbon foam comprises:
the dried gas coal, fat coal and coking coal are ground into coal powder with 60-80 meshes. The vitrinite enriched substances of gas coal, fat coal and coking coal are separated by adopting a patent CN102849723A method for preparing graphitized carbon foam by utilizing pretreated bituminous coal, and are respectively marked as GV, FV and CV. Mixing the vitrinite enrichment or a mixture of three vitrinite enrichments of GV, FV and CV with a supercritical foaming agent, wherein the vitrinite enrichment is as follows: and (3) putting the supercritical foaming agent into a metal die, wherein the mass ratio of the supercritical foaming agent is 5: 1-200. The supercritical foaming agent can be toluene (99.9%; Tc:318.7 deg.C; Pc:4.11MPa) or naphthalene (99% or more; Tc:475.2 deg.C; Pc:4.05MPa), etc., and is heated to 480 deg.C at 5 deg.C/min. Keeping the final foaming pressure constant, and keeping the temperature constant for 60min under the supercritical condition of the foaming agent. And after the constant temperature is finished, releasing the pressure to the normal pressure at the speed of 4MPa/min, closing the gas outlet valve, continuously heating to 550 ℃ at the speed of 2 ℃/min, keeping the temperature for 20min, and naturally cooling to the room temperature to obtain the primary coal-based foam carbon.
Transferring the primary coal-based foam carbon into a tubular furnace for carbonization treatment, heating to 800-1000 ℃ at a speed of 2-5 ℃/min under the protection of high-purity nitrogen, keeping the temperature for 60-120 min, and naturally cooling to room temperature to obtain the coal-based foam carbon, wherein the coal-based foam carbon is respectively marked as GVCF, FVCF and CVCF.
Impregnating coal-based foam carbon with a required amount of KOH (KOH/carbon mass ratio of 1-6: 1), stirring for 30 minutes, then performing hot soaking at 80 ℃ for 4 hours, drying the mixture at 105 ℃ for 4 hours, and then performing hot soaking at 2 ℃ for 2 min -1～5℃min-1The temperature is raised to 750-1000 ℃, and the activation is carried out for 1-4 hours under the protection of nitrogen. Washed with hydrochloric acid and distilled water until pH 7, then filtered and dried to obtain graded porous coal-based foamy carbon (GPCF) for further study.
A certain amount of organic amine is dissolved in methanol (20mL) by using a magnetic stirrer to prepare a solution with the concentration of 0.1-80 wt%. After the organic amine was completely dissolved, an amount of GPCF was added to the solution and refluxed at 70 ℃ for 6 hours. Drying the obtained product in a forced air drying oven at 80 ℃ for 12-36 h to remove the formazan from the sampleAn alcohol. The organic amine impregnated sample was then dried under vacuum at 60 ℃ for 12 hours. The resulting sample was named GPCF-xTe, where x represents the loading of organic amine in the adsorbent. The value of x is calculated as follows: x ═ weight of (organic amine)/(weight of organic amine + weight of GPCF). The synthesized samples were stored in a dry sample box for further characterization and CO2And (5) adsorption research.
The invention also provides a foamy carbon-based solid amine adsorbent which is prepared by the preparation method.
The foamy carbon-based solid amine adsorbent has the same advantages as the preparation method, and the details are not repeated.
The invention further provides an application of the carbon foam-based solid amine adsorbent in carbon dioxide capture.
Further, the application includes: adopting a carbon dioxide capture fixed bed reactor to absorb and desorb carbon dioxide;
the structure of the carbon dioxide capturing fixed bed reactor is shown in fig. 2, and comprises a fixed bed 100, a flue gas storage tank 200 and a carbon dioxide infrared analyzer 300, wherein a reaction tube is arranged in the middle of the fixed bed 100 along the axial direction, the foamy carbon-based solid amine adsorbent 101 is filled in the middle of the reaction tube, and quartz wool is filled in the remaining upper part and the lower part of the reaction tube; the outer wall of the reaction tube is provided with a heater (heating by adopting a heat tracing band, heating wires can be arranged on the wall of a solid adsorbent packing material tube, or heating with steam and the like) and is connected with a temperature control device 102 for controlling the adsorption and desorption temperature, a smoke gas storage tank 200 is communicated with an inlet of the fixed bed 100 through a pipeline, the pipeline is provided with a mass flow meter 201 for controlling the flow rate of smoke, and a carbon dioxide infrared analyzer 300 is connected with an outlet of the fixed bed 100 for detecting the concentration of carbon dioxide.
The adsorption/desorption test method is as follows:
carbon dioxide (99.999%) and nitrogen (99.999%) were purchased from Hebei Anyi gas, Inc. CO of samples in the above-mentioned homemade carbon dioxide capturing fixed bed reactor2And (5) testing adsorption and desorption performances. The reactor is filled with adsorbent by mass flow with stainless steel with inner diameter of 10mmThe flow rate of the simulated flue gas is controlled by a meter, the adsorption and desorption temperature is controlled by a heater, and CO is introduced into and discharged from an inlet and an outlet of the fixed bed reactor2Model GHX-520 CO, manufactured by Beijing Xibi instruments Ltd2And (4) carrying out online measurement by using an infrared analyzer. All adsorption tests were performed at atmospheric pressure.
The specific experimental steps are as follows: firstly, filling 0.9-1.0g of adsorbent in the middle of a reaction tube, filling quartz wool at the upper part and the lower part of the adsorbent, then introducing 100mL/min of nitrogen, then heating a reactor to 100 ℃ at a constant rate of 5 ℃/min, pretreating the adsorbent for 60min to remove impurity gas adsorbed by a sample at the early stage, then reducing the temperature of the reactor to a testing temperature (75 ℃), and converting the nitrogen into simulated flue gas (containing 85 vol.% of N) after the temperature is stable2And 15 vol.% CO2) Carrying out CO2Adsorption test and CO opening2Infrared ray divides minute detector record reaction tube export CO2The concentration of (c). When the outlet of the reaction tube is CO2The concentration reaches the CO in the inlet simulation smoke2After the initial concentration, the adsorption process is complete. Then the temperature of the adsorbent is raised to 100 ℃, nitrogen is introduced for desorption of the adsorbent, and CO in the infrared analyzer is detected2When the concentration reading is zero, the desorption is completed. Then the temperature of the adsorbent is reduced to the required temperature, and the nitrogen is switched back to the simulated flue gas, so that the CO can be carried out again2And (4) an adsorption process. Repeating the above CO2The cyclic regeneration performance of the adsorbent can be inspected in the adsorption and desorption process.
CO of the adsorbent was calculated by the formula (1-1)2The amount of adsorption.
Wherein F is the mixed gas inlet flow (mL/min); w is the mass of adsorbent (g); t is CO2Adsorption time(s); c0And C is CO at the inlet and the outlet of the reaction tube respectively2Concentration (vol.%); vmMolar volume of gas at standard state (mL/mmol); q. q.saIs CO at adsorption time t2Adsorption amount (mmol/g).
The technical scheme of the invention has the following beneficial effects:
(1) the invention utilizes a supercritical foaming method to prepare coal-based foam carbon, obtains a carrier with a hierarchical porous structure through simple chemical activation, and obtains a solid amine adsorbent through amine functionalization. The method adopts vitrinite enrichment substances with different coalification degrees as precursors, realizes the preparation of the graded porous coal-based foam carbon carrier through a simple carbonization/activation process, obtains the solid amine adsorbent through amine functionalization, and the prepared solid amine adsorbent base material has a graded porous structure and a larger specific surface area, while the base material with a single pore structure is easy to be blocked by organic amine, increases the dynamic barrier of carbon dioxide, and reduces the mass transfer rate in the carbon dioxide trapping process. Has wide application prospect in the field of carbon dioxide capture.
(2) The raw materials of the invention have wide sources, and are suitable for industrial production, and when the solid adsorbent is used for capturing carbon dioxide, the operation is simple, and the corrosion to equipment is small.
The present invention has been described in detail hereinabove, but the above embodiments are merely illustrative in nature and are not intended to limit the present invention. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary or the following examples.
Unless expressly stated otherwise, a numerical range throughout this specification includes any sub-range therein and any numerical value incremented by the smallest sub-unit within a given value. Unless expressly stated otherwise, numerical values throughout this specification represent approximate measures or limitations to the extent that such deviations from the given values, as well as embodiments having approximately the stated values and having the exact values stated, are included. Other than in the operating examples provided at the end of the detailed description, all numbers expressing quantities or conditions of parameters (e.g., quantities or conditions) used in the specification (including the appended claims) are to be understood as being modified in all instances by the term "about" whether or not "about" actually appears before the number. "about" means that the numerical value so stated is allowed to be somewhat imprecise (with some approach to exactness in that value; about or reasonably close to that value; approximately). As used herein, "about" refers to at least variations that can be produced by ordinary methods of measuring and using such parameters, provided that the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning. For example, "about" can include variations of less than or equal to 10%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, or less than or equal to 0.5%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic flow chart of an activation process for preparing graded porous coal-based foam carbon according to an embodiment of the present invention;
FIG. 2 is a schematic view of the structure of a carbon dioxide capturing fixed bed reactor according to the present invention;
FIG. 3 is a SEM image of the cell morphology of the coal-based carbon foam prepared in example 1;
FIG. 4 is a SEM image of the cell morphology of the coal-based carbon foam prepared in example 2;
FIG. 5 is a SEM image of the cell morphology of the coal-based carbon foam prepared in example 3;
FIG. 6 is a SEM image of the cell morphology of the coal-based carbon foam prepared in example 4;
FIG. 7 is a SEM image of the cellular morphology of the coal-based carbon foam prepared in example 5;
FIG. 8 is a SEM image of the cell morphology of the coal-based carbon foam prepared in example 6;
FIG. 9 is an SEM image of GPCF-1 activated coal-based foam carbon of example 1;
FIG. 10 is a TEM image of the graded porous morphology of the GPCF-1 activated coal-based foam carbon of example 1;
FIG. 11 is a graph of the specific surface area test results for the GPCF-1 activated coal-based foam carbon of example 1;
FIG. 12 is a pore size distribution plot of the hierarchical porous structure of the GPCF-1 activated coal-based foam carbon of example 1;
FIG. 13 is a plot of pore cell diameter distribution for coal-based foam carbon prepared in examples 1-3;
FIG. 14 is a graph of the specific surface area test results for the GPCF-4 activated coal-based foam carbon of example 4;
FIG. 15 is a graph of the gas density and porosity of the coal-based foam carbon prepared in examples 1-3;
FIG. 16 is a plot of pore cell diameter distribution for coal-based foamy carbons prepared in examples 4-6;
FIG. 17 is a graph of the gas density and porosity of coal-based foam coals prepared in examples 4-6;
FIG. 18 is a SEM image of the cell morphology of the coal-based carbon foam prepared in example 7;
FIG. 19 is a SEM image of the cell morphology of the coal-based carbon foam prepared in example 8;
FIG. 20 is a SEM image of cell morphology of mesophase pitch-based carbon foam of comparative example 1;
FIG. 21 is a SEM image of the cell morphology of coal-based foam carbon prepared by the spontaneous foaming method in comparative example 2;
FIG. 22 is a graph showing the results of a specific surface area test of comparative example 3 in comparison with example 1 in which the activation process was omitted to produce coal-based foam carbon;
FIG. 23 is a pore size distribution diagram for comparative example 3 with respect to example 1 for the preparation of coal-based foam carbon omitting the activation process.
The figure is as follows: 100-fixed bed; 101-a foamy carbon-based solid amine adsorbent; 102-temperature control means; 200-a flue gas storage tank; 201-mass flow meter; 300-carbon dioxide infrared analyzer.
Detailed Description
The present invention is further illustrated by the following examples, which are provided for illustrative purposes only and are not to be construed as limiting the scope of the invention.
The materials, reagents, methods and the like used in the examples are those conventional in the art, and the drugs used in the experiment were obtained from Michelin reagent, TEM was JEM-2100 from JEOL, Japan, SEM was a field emission SU-70 microscope, and BET test was performed at 350 ℃ using ASAP 2020(Micromeritics, Inc.), unless otherwise specified.
In the examples CO2Adsorption performance test method reference is made to the adsorption/desorption test method described above.
Examples sources of coking coal vitrinite enrichment (CV) refer to example 3 disclosed in patent CN 102849723A; source of vitrinite enrichment (GV) of gascoal refer to example 1 disclosed in patent CN 102849723A; for the source of rich coal vitrinite concentrate (FV) reference is made to example 2 disclosed in patent CN 102849723A.
Example 1
A preparation method of a foamy carbon-based solid amine adsorbent comprises the following steps:
1. 100g of the coke vitrinite Concentrate (CV) was placed in a metal mold, 50ml of toluene was injected, and then the metal mold was placed in a high-pressure reaction vessel. The temperature is raised to 480 ℃ at a speed of 5 ℃/min. Keeping the final foaming pressure at 8MPa constant, and keeping the temperature constant for 60min under the supercritical condition of toluene. And after the constant temperature is finished, releasing the pressure to the normal pressure at the speed of 4MPa/min, closing the gas outlet valve, continuously heating to 550 ℃ at the speed of 2 ℃/min, keeping the temperature for 20min, and naturally cooling to the room temperature to obtain the primary coal-based foam carbon. Transferring the primary coal-based foam carbon into a tubular furnace for carbonization treatment, heating to 1000 ℃ at a speed of 2 ℃/min under the protection of high-purity nitrogen, keeping the temperature for 120min, and naturally cooling to room temperature to obtain the coal-based foam carbon (CVCF), wherein the morphology of cells is shown in figure 3.
2. 50g of coal-based foam carbon was immersed in a KOH solution (KOH/carbon mass ratio 6:1), stirred for 30 minutes, then subjected to thermal soaking at 80 ℃ for 4 hours, and then the mixture was dried at 105 ℃ for 4 hours, and then subjected to mi at 5 ℃ for 4 hoursn-1The temperature is raised to 750 ℃ at a constant speed, and the activation is carried out for 4 hours at 750 ℃ under the protection of nitrogen. Washing with hydrochloric acid and distilled water until pH 7, and then filtering and drying to obtain graded porous coal-based foam carbon (GPCF-1), the morphology and graded porous morphology of which are shown in fig. 9 and 10; the BET specific surface area of GPCF-1 was determined to be 1087.11m2(ii)/g, as shown in FIG. 11; the pore size distribution of the GPCF-1 hierarchical porous structure is shown in FIG. 12.
3. An amount of TEPA was dissolved in methanol (20mL) using a magnetic stirrer. After TEPA is completely dissolved, adding a certain amount of GPCF-1 into the solution, and refluxing for 6 hours at 50-80 ℃. The resulting product was dried in a forced air drying oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated sample was then dried under vacuum at 60 ℃ for 12 hours. The resulting sample was named GPCF-1-60% Te. The synthesized samples were stored in a dry sample box for further characterization and CO2And (5) adsorption research.
4、CO2And (3) testing the adsorption performance: applying the obtained solid adsorbent to CO2Adsorption/desorption test, GPCF-1-60% Te shows excellent CO by changing the temperature from 75 deg.C (adsorption) to 100 deg.C (desorption)2Adsorption performance and regeneration capacity. First adsorption amount: 5.82mmol/g, second adsorption amount: 5.81 mmol/g.
Example 2
A preparation method of a foamy carbon-based solid amine adsorbent comprises the following steps:
1. 100g of the gas coal vitrinite concentrate (GV) was placed in a metal mold, 100ml of toluene was injected, and then the metal mold was placed in a high-pressure reaction vessel. The temperature is raised to 480 ℃ at a speed of 5 ℃/min. Keeping the final foaming pressure at 8MPa constant, and keeping the temperature constant for 60min under the supercritical condition of toluene. And after the constant temperature is finished, releasing the pressure to the normal pressure at the speed of 4MPa/min, closing the gas outlet valve, continuously heating to 550 ℃ at the speed of 2 ℃/min, keeping the temperature for 20min, and naturally cooling to the room temperature to obtain the primary coal-based foam carbon. Transferring the primary coal-based foam carbon into a tubular furnace for carbonization treatment, heating to 1000 ℃ at a speed of 2 ℃/min under the protection of high-purity nitrogen, keeping the temperature for 120min, and naturally cooling to room temperature to obtain the coal-based foam carbon (GVCF), wherein the morphology of cells is shown in figure 4.
2. 50g of coal-based foam carbon was immersed in a KOH solution (KOH/carbon mass ratio of 4: 1), stirred for 30 minutes, and then subjected to thermal soaking at 80 ℃ for 4 hours, and then the mixture was dried at 105 ℃ for 4 hours, and then dried at 5 ℃ for 5 minutes-1The temperature is raised to 850 ℃ at a constant speed, and the activation is carried out for 4 hours at 850 ℃ under the protection of nitrogen. Washed with hydrochloric acid and distilled water until pH 7, then filtered and dried to obtain graded porous coal-based foam carbon (GPCF-2).
3. An amount of TEPA was dissolved in methanol (20mL) using a magnetic stirrer. After the TEPA was completely dissolved, an amount of GPCF-2 was added to the solution and refluxed at 70 ℃ for 6 hours. The resulting product was dried in a forced air drying oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated sample was then dried under vacuum at 60 ℃ for 12 hours. The resulting sample was named GPCF-2-60% Te. The synthesized samples were stored in a dry sample box for further characterization and CO2And (5) adsorption research.
4、CO2And (3) testing the adsorption performance: applying the obtained solid adsorbent to CO2Adsorption/desorption test, GPCF-2-60% Te shows excellent CO by changing the temperature from 75 deg.C (adsorption) to 100 deg.C (desorption)2Adsorption performance and regeneration capacity. First adsorption amount: 5.73mmol/g, second adsorption amount: 5.71 mmol/g.
Example 3
A preparation method of a foamy carbon-based solid amine adsorbent comprises the following steps:
1. uniformly mixing 50g of gas coal vitrinite concentrate (GV) and 50g of coking coal vitrinite Concentrate (CV), putting the mixture into a metal mold, injecting 100ml of toluene, and then putting the metal mold into a high-pressure reaction kettle. The temperature is raised to 480 ℃ at a speed of 5 ℃/min. Keeping the final foaming pressure at 8MPa constant, and keeping the temperature constant for 60min under the supercritical condition of toluene. And after the constant temperature is finished, releasing the pressure to the normal pressure at the speed of 4MPa/min, closing the gas outlet valve, continuously heating to 550 ℃ at the speed of 2 ℃/min, keeping the temperature for 20min, and naturally cooling to the room temperature to obtain the primary coal-based foam carbon. Transferring the primary coal-based foam carbon into a tubular furnace for carbonization, heating to 1000 ℃ at a speed of 2 ℃/min under the protection of high-purity nitrogen, keeping the temperature for 120min, and naturally cooling to room temperature to obtain the coal-based foam carbon (GVCF/CVCF), wherein the morphology of cells is shown in figure 5.
2. 50g of coal-based foam carbon was immersed in a KOH solution (KOH/carbon mass ratio 6:1), stirred for 30 minutes, and then subjected to thermal soaking at 80 ℃ for 4 hours, after which the mixture was dried at 105 ℃ for 4 hours, and then at 5 ℃ for min-1The temperature is raised to 750 ℃ at a constant speed, and the activation is carried out for 2 hours at 750 ℃ under the protection of nitrogen. Washed with hydrochloric acid and distilled water until pH 7, then filtered and dried to obtain graded porous coal-based foam carbon (GPCF-3).
3. An amount of TEPA was dissolved in methanol (20mL) using a magnetic stirrer. After the TEPA was completely dissolved, an amount of GPCF-3 was added to the solution and refluxed at 70 ℃ for 6 hours. The resulting product was dried in a forced air drying oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated sample was then dried under vacuum at 60 ℃ for 12 hours. The resulting sample was named GPCF-3-60% Te. The synthesized samples were stored in a dry sample box for further characterization and CO2And (5) adsorption research.
4、CO2And (3) testing the adsorption performance: applying the obtained solid adsorbent to CO2Adsorption/desorption test, GPCF-3-60% Te shows excellent CO by changing the temperature from 75 deg.C (adsorption) to 100 deg.C (desorption)2Adsorption performance and regeneration capacity. First adsorption amount: 5.53mmol/g, second adsorption amount: 5.52 mmol/g.
Specific parameters of examples 1-3 are shown in Table 1.
TABLE 1 preparation scheme of toluene supercritical carbon foam
The pore diameter distribution of the coal-based foam carbon prepared in examples 1-3 is shown in FIG. 13, the pore diameter distribution range of three samples is 42.6-336.5 μm, and the distribution is calculated by GV: CV samples can be taken to a minimum of 42.6 μm. The porosity and bulk density are shown in FIG. 150.57g/cm3～0.66g/cm3The porosity is 58.6-66.23%.
Example 4
A preparation method of a foamy carbon-based solid amine adsorbent comprises the following steps:
1. 100g of the coke vitrinite Concentrate (CV) and 20g of refined naphthalene (99.7%; Tc 475.2 ℃ C.; Pc:4.05MPa) were mixed uniformly and placed in a metal mold, which was then placed in a high-pressure reactor. The temperature is raised to 480 ℃ at a speed of 5 ℃/min. Keeping the final foaming pressure constant at 8MPa, and keeping the temperature constant for 60min under the supercritical condition of naphthalene. And after the constant temperature is finished, releasing the pressure to the normal pressure at the speed of 4MPa/min, closing the gas outlet valve, continuously heating to 550 ℃ at the speed of 2 ℃/min, keeping the temperature for 20min, and naturally cooling to the room temperature to obtain the primary coal-based foam carbon. Transferring the primary coal-based foam carbon into a tubular furnace for carbonization treatment, heating to 1000 ℃ at a speed of 2 ℃/min under the protection of high-purity nitrogen, keeping the temperature for 120min, and naturally cooling to room temperature to obtain the coal-based foam carbon (CVCF), wherein the morphology of cells is shown in figure 6.
2. 50g of coal-based foam carbon was immersed in a KOH solution (KOH/carbon mass ratio: 5: 1), stirred for 30 minutes, and then subjected to thermal soaking at 80 ℃ for 4 hours, and then the mixture was dried at 105 ℃ for 4 hours, and then dried at 5 ℃ for 5 minutes-1The temperature is raised to 700 ℃ at a constant speed, and the activation is carried out for 4 hours at 700 ℃ under the protection of nitrogen. Washed with hydrochloric acid and distilled water until pH 7, then filtered and dried to obtain graded porous coal-based foam carbon (GPCF-4). GPCF-4 was determined to have a BET specific surface area of 2048m2(ii) in terms of/g, as shown in FIG. 14.
3. An amount of TEPA was dissolved in methanol (20mL) using a magnetic stirrer. After the TEPA was completely dissolved, an amount of GPCF-4 was added to the solution and refluxed at 70 ℃ for 6 hours. The resulting product was dried in a forced air drying oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated sample was then dried under vacuum at 60 ℃ for 12 hours. The resulting sample was named GPCF-4-60% Te. The synthesized samples were stored in a dry sample box for further characterization and CO2And (5) adsorption research.
4、CO2And (3) testing the adsorption performance: subjecting the obtained product toSolid adsorbent for CO2Adsorption/desorption test, GPCF-4-60% Te shows excellent CO by changing the temperature from 75 deg.C (adsorption) to 100 deg.C (desorption)2Adsorption performance and regeneration capacity. First adsorption amount: 3.98mmol/g, second adsorption amount: 3.96 mmol/g.
Example 5
A preparation method of a foamy carbon-based solid amine adsorbent comprises the following steps:
1. 100g of the vitrinite enrichment of gas coal (GV) and 20g of refined naphthalene (99.7%; Tc 475.2 ℃ C.; Pc:4.05Mpa) were mixed uniformly and placed in a metal mold, which was then placed in a high-pressure reactor. The temperature is raised to 480 ℃ at a speed of 5 ℃/min. Keeping the final foaming pressure constant at 8MPa, and keeping the temperature constant for 60min under the supercritical condition of naphthalene. And after the constant temperature is finished, releasing the pressure to the normal pressure at the speed of 4MPa/min, closing the gas outlet valve, continuously heating to 550 ℃ at the speed of 2 ℃/min, keeping the temperature for 20min, and naturally cooling to the room temperature to obtain the primary coal-based foam carbon. Transferring the primary coal-based foam carbon into a tubular furnace for carbonization, heating to 1000 ℃ at a speed of 2 ℃/min under the protection of high-purity nitrogen, keeping the temperature for 120min, and naturally cooling to room temperature to obtain the coal-based foam carbon (GVCF), wherein the morphology of cells is shown in figure 7.
2. 50g of coal-based foam carbon was immersed in a KOH solution (KOH/carbon mass ratio 6:1), stirred for 30 minutes, and then subjected to thermal soaking at 80 ℃ for 4 hours, after which the mixture was dried at 105 ℃ for 4 hours, and then at 5 ℃ for min-1Heating to 900 deg.C at constant rate, activating at 900 deg.C under nitrogen protection for 3 hr. Washed with hydrochloric acid and distilled water until pH 7, then filtered and dried to obtain graded porous coal-based foam carbon (GPCF-5).
3. An amount of TEPA was dissolved in methanol (20mL) using a magnetic stirrer. After the TEPA was completely dissolved, an amount of GPCF-5 was added to the solution and refluxed at 70 ℃ for 6 hours. The resulting product was dried in a forced air drying oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated sample was then dried under vacuum at 60 ℃ for 12 hours. The resulting sample was named GPCF-5-60% Te. The synthesized samples were stored in a dry sample box for further characterization and CO2And (5) adsorption research.
4、CO2And (3) testing the adsorption performance: applying the obtained solid adsorbent to CO2Adsorption/desorption test, GPCF-5-60% Te shows excellent CO by changing the temperature from 75 deg.C (adsorption) to 100 deg.C (desorption)2Adsorption performance and regeneration capacity. First adsorption amount: 5.01mmol/g, second adsorption amount: 4.99 mmol/g.
Example 6
A preparation method of a foamy carbon-based solid amine adsorbent comprises the following steps:
1. 100g of rich coal vitrinite concentrate (FV) and 20g of refined naphthalene (99.7 percent; Tc:475.2 ℃ C.; Pc:4.05Mpa) are mixed uniformly and then put into a metal mold, and then the metal mold is put into a high-pressure reaction kettle. The temperature is raised to 480 ℃ at a speed of 5 ℃/min. Keeping the final foaming pressure constant at 8MPa, and keeping the temperature constant for 60min under the supercritical condition of naphthalene. And after the constant temperature is finished, releasing the pressure to the normal pressure at the speed of 4MPa/min, closing the gas outlet valve, continuously heating to 550 ℃ at the speed of 2 ℃/min, keeping the temperature for 20min, and naturally cooling to the room temperature to obtain the primary coal-based foam carbon. Transferring the primary coal-based foam carbon into a tubular furnace for carbonization treatment, heating to 1000 ℃ at a speed of 2 ℃/min under the protection of high-purity nitrogen, keeping the temperature for 120min, and naturally cooling to room temperature to obtain the coal-based foam carbon (FVCF), wherein the morphology of cells is shown in figure 8.
2. 50g of coal-based foam carbon was immersed in a KOH solution (KOH/carbon mass ratio of 4: 1), stirred for 30 minutes, and then subjected to thermal soaking at 80 ℃ for 4 hours, and then the mixture was dried at 105 ℃ for 4 hours, and then dried at 5 ℃ for 5 minutes-1The temperature is raised to 1000 ℃ at a constant speed, and the activation is carried out for 4 hours at 1000 ℃ under the protection of nitrogen. Washed with hydrochloric acid and distilled water until pH 7, then filtered and dried to obtain graded porous coal-based foam carbon (GPCF-6).
3. An amount of TEPA was dissolved in methanol (20mL) using a magnetic stirrer. After the TEPA was completely dissolved, an amount of GPCF-6 was added to the solution and refluxed at 70 ℃ for 6 hours. The resulting product was dried in a forced air drying oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated sample was then dried under vacuum at 60 ℃ for 12 hours. The obtained sampleThe name is GPCF-6-60% Te. The synthesized samples were stored in a dry sample box for further characterization and CO2And (5) adsorption research.
4、CO2And (3) testing the adsorption performance: applying the obtained solid adsorbent to CO2Adsorption/desorption test, GPCF-6-60% Te shows excellent CO by changing the temperature from 75 deg.C (adsorption) to 100 deg.C (desorption)2Adsorption performance and regeneration capacity. First adsorption amount: 4.34mmol/g, second adsorption amount: 4.33 mmol/g.
Specific parameters for examples 4-6 are shown in Table 2.
TABLE 2 preparation scheme of naphthalene supercritical carbon foam
The pore diameter distribution of the coal-based foam carbon prepared in examples 4-6 is shown in FIG. 16, the pore distribution range of the three samples is 36.55-422.75 μm, and the GV sample can reach the minimum pore size of 36.55 μm by statistics. The porosity and bulk density are shown in FIG. 17, and the bulk density is 0.54g.cm-3～0.61g.cm-3The porosity is 63.63-67.51%.
Example 7
The difference between this example and example 4 is that the foaming temperature is 400 ℃ and the foaming pressure is 5MPa, and as can be seen from fig. 18, when the temperature and the foaming pressure are reduced, the uniformity of the structure of the foam carbon cells prepared after carbonization is reduced, the cells do not show similar round shapes, and the solid adsorbent is prepared by activation and TEPA loading. Subjecting the solid adsorbent to CO2Adsorption performance was tested by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption). First adsorption amount: 3.53mmol/g, second adsorption amount: 3.52 mmol/g.
Example 8
The difference between this example and example 4 is that the ratio of vitrinite concentrate to naphthalene is 10:1, as can be seen from fig. 19, when the ratio of vitrinite concentrate is increased, the cell structure of the foam carbon prepared after carbonization is obviously increased,and (3) preparing the solid adsorbent through activation and TEPA loading. Subjecting the solid adsorbent to CO2Adsorption performance was tested by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption). First adsorption amount: 2.67mmol/g, second adsorption: 2.68 mmol/g.
Comparative example 1
The present comparative example differs from example 1 in that the coke vitrinite concentrate is replaced with mesophase pitch. As can be seen from fig. 20, the pitch-based foam carbon after carbonization has a larger cell structure, and the cell structure is more uniform and tends to be circular. And (3) preparing the solid adsorbent through activation and TEPA loading. Subjecting the solid adsorbent to CO2Adsorption performance was tested by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption). First adsorption amount: 2.33mmol/g, second adsorption amount: 2.34 mmol/g.
Comparative example 2
This comparative example differs from example 1 in that the supercritical foaming process was replaced by self-foaming, i.e. the amount of toluene added was 0mL without changing other conditions. As can be seen from fig. 21, the carbonized coal-based foam carbon has a larger pore structure, and the solid adsorbent is prepared by activation and TEPA loading. Subjecting the solid adsorbent to CO2Adsorption performance was tested by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption). First adsorption amount: 2.14mmol/g, second adsorption amount: 2.13 mmol/g.
Comparative example 3
This comparative example is different from example 1 in that, without step 2, i.e., the activation process, the BET test was performed on the carbon foam, as shown in FIG. 22, which has a significantly lower specific surface area than example 1, and as shown in FIG. 23, which has pores mainly concentrated in mesopores, exhibiting a single pore structure. The solid adsorbent is prepared by taking the solid adsorbent as a matrix material and carrying the matrix material through TEPA. Subjecting the solid adsorbent to CO2Adsorption performance was tested by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption). First adsorption amount: 0.98mmol/g, second adsorption amount: 0.99 mmol/g.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the foamy carbon-based solid amine adsorbent is characterized by comprising the following steps:
(1) using vitrinite concentrates of the same or different coal types as precursors to prepare primary coal-based foam carbon by a supercritical foaming method;
(2) carbonizing the primary coal-based foam carbon to obtain coal-based foam carbon;
(3) performing activation heat treatment on the coal-based foam carbon to prepare graded porous coal-based foam carbon with micropore, mesopore and macropore structures;
(4) and performing amino functionalization on the graded porous coal-based foam carbon by using an amine modifier to obtain a foam carbon-based solid amine adsorbent.
2. The method according to claim 1, wherein the step (1) comprises: placing vitrinite enrichment substances of the same or different coal types into a container, adding a supercritical foaming agent, placing the container into a reactor, foaming for 0.5-4 h at a foaming temperature of Tc-Tc +200 ℃ and a foaming pressure of Pc-Pc +4MPa, and after foaming, pressing to normal pressure and cooling to room temperature to obtain the primary coal-based foam carbon;
wherein, the supercritical foaming agent is a liquid or a solid which presents a supercritical fluid state at a critical temperature, and toluene or naphthalene is preferred;
tc is the critical temperature of the supercritical foaming agent, and Pc is the critical pressure of the supercritical foaming agent.
3. The preparation method of claim 2, wherein the mass ratio of the supercritical foaming agent to the vitrinite concentrate is 5: 1-200.
4. The method according to claim 1, wherein the step (2) comprises: transferring the primary coal-based foam carbon into a tubular furnace for carbonization treatment, heating to 800-1000 ℃ at a speed of 2-5 ℃/min under a protective atmosphere, keeping the temperature for 60-120 min, and then cooling to room temperature to obtain the coal-based foam carbon;
particularly, the pore diameter distribution of the coal-based foam carbon after carbonization treatment is 35-425 mu m, and the bulk density is 0.5-0.7 g/cm3The porosity is 55 to 70%.
5. The method according to claim 1, wherein the step (3) comprises: subjecting the coal-based carbon foam to an alkaline (e.g., KOH and/or K)2CO3) Soaking in an aqueous solution at 60-90 ℃ for 4-10 h, drying, then heating to 700-1050 ℃ at a constant rate of 2-5 ℃/min under a protective atmosphere, activating for 1-4 h, washing, filtering and drying to obtain the graded porous coal-based foam carbon;
particularly, the specific surface area of the graded porous coal-based foam carbon is 1050-2048 m2Per g, pore volume of 0.8-1.5 cm3(ii)/g; particularly, the ratio of micropores, mesopores and macropores is 23-26%, 50-56% and 18-26%, respectively.
6. The preparation method according to claim 5, wherein the mass ratio of the solid alkali to the coal-based foam carbon is 1-6: 1.
7. The method according to claim 1, wherein the step (4) comprises: adding the graded porous coal-based foam carbon into an amine modifier-methanol mixed solution, refluxing for 6-10 hours at 50-80 ℃, removing methanol, and drying to obtain the foam carbon-based solid amine adsorbent;
preferably, the amine modifier is one or a mixture of more selected from diethylenetriamine, tetraethylenepentamine, triethylene tetramine, polyethyleneimine, ethanolamine or 2, 6-diethylaniline;
preferably, the content of the amine modifier in the foamy carbon-based solid amine adsorbent is 0.1-60 wt%.
8. A foamy carbon-based solid amine adsorbent, characterized in that it is prepared by the preparation method of any one of claims 1-7.
9. Use of the carbon foam-based solid amine adsorbent according to claim 8 for carbon dioxide sequestration.
10. The use according to claim 9, characterized in that carbon dioxide is subjected to adsorption and desorption by using a carbon dioxide capturing fixed bed reactor;
the carbon dioxide capturing fixed bed reactor comprises a fixed bed, a flue gas storage tank and a carbon dioxide infrared analyzer, wherein a reaction tube is arranged in the middle of the fixed bed along the axial direction, the middle of the reaction tube is filled with the foamy carbon-based solid amine adsorbent, and the rest upper part and the rest lower part of the reaction tube are filled with quartz wool; the outer wall of reaction tube is equipped with the heater and connects temperature regulating device for desorption temperature is inhaled in the control, the flue gas storage tank pass through the pipeline with the import intercommunication of fixed bed is equipped with mass flow meter on the pipeline for the velocity of flow of control flue gas, carbon dioxide infrared analyzer with the exit linkage of fixed bed for detect the concentration of carbon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111226312.0A CN113813927B (en) | 2021-10-21 | 2021-10-21 | Foam carbon-based solid amine adsorbent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111226312.0A CN113813927B (en) | 2021-10-21 | 2021-10-21 | Foam carbon-based solid amine adsorbent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113813927A true CN113813927A (en) | 2021-12-21 |
| CN113813927B CN113813927B (en) | 2024-03-01 |
Family
ID=78920585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111226312.0A Active CN113813927B (en) | 2021-10-21 | 2021-10-21 | Foam carbon-based solid amine adsorbent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113813927B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114522505A (en) * | 2022-02-14 | 2022-05-24 | 上海交通大学 | Direct air carbon dioxide capture system based on amine-loaded solid adsorbent |
| WO2023246281A1 (en) * | 2022-06-22 | 2023-12-28 | 苏州西热节能环保技术有限公司 | Flue gas carbon dioxide adsorbent performance detection apparatus and detection method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849723A (en) * | 2012-09-27 | 2013-01-02 | 辽宁科技大学 | Preparation method of coal-based carbon foam from pre-treated bituminous coal |
| CN105478082A (en) * | 2016-01-14 | 2016-04-13 | 四川大学 | Carbon-aerogel-based supported organic amine CO2 absorbent and preparation method thereof |
| CN109201007A (en) * | 2018-09-27 | 2019-01-15 | 太原理工大学 | A kind of carbon dioxide absorber and its preparation method and application |
-
2021
- 2021-10-21 CN CN202111226312.0A patent/CN113813927B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849723A (en) * | 2012-09-27 | 2013-01-02 | 辽宁科技大学 | Preparation method of coal-based carbon foam from pre-treated bituminous coal |
| CN105478082A (en) * | 2016-01-14 | 2016-04-13 | 四川大学 | Carbon-aerogel-based supported organic amine CO2 absorbent and preparation method thereof |
| CN109201007A (en) * | 2018-09-27 | 2019-01-15 | 太原理工大学 | A kind of carbon dioxide absorber and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114522505A (en) * | 2022-02-14 | 2022-05-24 | 上海交通大学 | Direct air carbon dioxide capture system based on amine-loaded solid adsorbent |
| WO2023246281A1 (en) * | 2022-06-22 | 2023-12-28 | 苏州西热节能环保技术有限公司 | Flue gas carbon dioxide adsorbent performance detection apparatus and detection method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113813927B (en) | 2024-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Water caltrop shell-derived nitrogen-doped porous carbons with high CO2 adsorption capacity | |
| Li et al. | Preparation of a dual pore structure activated carbon from rice husk char as an adsorbent for CO2 capture | |
| Shao et al. | Enhance SO2 adsorption performance of biochar modified by CO2 activation and amine impregnation | |
| Shi et al. | Nitrogen-doped activated carbons derived from microalgae pyrolysis by-products by microwave/KOH activation for CO2 adsorption | |
| Zhang et al. | Micro-mesoporous activated carbon simultaneously possessing large surface area and ultra-high pore volume for efficiently adsorbing various VOCs | |
| Li et al. | Pine cone shell-based activated carbon used for CO 2 adsorption | |
| Wang et al. | Carbon dioxide capture using polyethylenimine-loaded mesoporous carbons | |
| Yaumi et al. | Reusable nitrogen-doped mesoporous carbon adsorbent for carbon dioxide adsorption in fixed-bed | |
| CN113813927A (en) | Foam carbon-based solid amine adsorbent and preparation method and application thereof | |
| Rios et al. | Adsorption of methane in activated carbons obtained from coconut shells using H 3 PO 4 chemical activation | |
| Rodríguez et al. | Low-cost hierarchical micro/macroporous carbon foams as efficient sorbents for CO2 capture | |
| Luo et al. | The effects of nitrogen functional groups and narrow micropore sizes on CO2 adsorption onto N-doped biomass-based porous carbon under different pressure | |
| CN106829957A (en) | A kind of low desorption residual particles method for preparation of active carbon of VOCs high adsorption rates | |
| Luo et al. | Preparation of N-doped activated carbons with high CO 2 capture performance from microalgae (Chlorococcum sp.) | |
| CN110015662A (en) | A kind of CO absorption2With the preparation method of nitrogen-doped porous carbon material | |
| CN103041774B (en) | Microwave adaptive composite active carbon and preparation method thereof | |
| Zhang et al. | MOF-derived 3D porous carbon aerogels as an efficient adsorbent for toluene in humid air | |
| Jia et al. | Activated carbon preparation based on the direct molten-salt electro-reduction of CO2 and its performance for VOCs adsorption | |
| Wu et al. | Preparation of microporous carbonaceous CO2 adsorbents by activating bamboo shoot shells with different chlorides: Experimental and theoretical calculations | |
| Zhang et al. | Facile preparation of nitrogen-doped microporous carbon from potassium citrate/urea for effective CH4 separation and uptake | |
| CN102728320B (en) | Preparation method for modified porous bamboo charcoal materials used for separating carbon dioxide and methane | |
| Li et al. | Diethylene glycolamine-assisted rapid synthesis of mechanically robust pyrogallol-based carbon monoliths for CO2 capture and separation | |
| Wang et al. | The development of activated carbon from corncob for CO 2 capture | |
| Ariyanto et al. | Nanoporous carbon based palm kernel shell and its characteristics of methane and carbon dioxide adsorption | |
| CN106944001B (en) | Preparation method of biological carbon adsorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |