CN113813927B - 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
- CN113813927B CN113813927B CN202111226312.0A CN202111226312A CN113813927B CN 113813927 B CN113813927 B CN 113813927B CN 202111226312 A CN202111226312 A CN 202111226312A CN 113813927 B CN113813927 B CN 113813927B
- Authority
- CN
- China
- Prior art keywords
- carbon
- coal
- foam
- temperature
- foam carbon
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 115
- 239000006260 foam Substances 0.000 title claims abstract description 107
- 150000001412 amines Chemical class 0.000 title claims abstract description 92
- 239000003463 adsorbent Substances 0.000 title claims abstract description 81
- 239000007787 solid Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003245 coal Substances 0.000 claims abstract description 146
- 238000001179 sorption measurement Methods 0.000 claims abstract description 80
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 40
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 40
- 239000004079 vitrinite Substances 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000003763 carbonization Methods 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 9
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 55
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 52
- 239000011148 porous material Substances 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 34
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 28
- 238000005187 foaming Methods 0.000 claims description 25
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000012141 concentrate Substances 0.000 claims description 19
- 238000003795 desorption Methods 0.000 claims description 18
- 239000004088 foaming agent Substances 0.000 claims description 16
- 238000001994 activation Methods 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000003546 flue gas Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 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
- 239000012298 atmosphere Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000003513 alkali 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
- 229920000742 Cotton Polymers 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 12
- 238000011069 regeneration method Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 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
- 210000004027 cell Anatomy 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 239000002184 metal Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000011056 performance test Methods 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002336 sorption--desorption measurement Methods 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 238000004939 coking Methods 0.000 description 7
- 210000003429 pore cell Anatomy 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 amine carbon dioxide Chemical class 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
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 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
- 238000000227 grinding Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 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
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 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
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011336 carbonized pitch Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 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
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 208000037972 tropical disease Diseases 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a foam carbon-based solid amine adsorbent, a preparation method and application thereof, and relates to the technical field of gas trapping materials, wherein the method comprises the following steps: the vitrinite enrichment of different coalification degrees is used as a precursor, a supercritical foaming technology is adopted to prepare primary coal-based foam carbon, the coal-based foam carbon is obtained after carbonization, the coal-based foam carbon carrier with a hierarchical porous structure is prepared through activation heat treatment, and the solid adsorbent is prepared through amine functionalization. The invention has the advantages that the source of raw materials is wide, the invention 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 carbon dioxide capture, the operation is simple, the corrosion to equipment is small, and excellent carbon dioxide adsorption performance and regeneration capability are exhibited.
Description
Technical Field
The invention relates to the technical field of gas trapping materials, in particular to a foam carbon-based solid amine carbon dioxide adsorbent, a preparation method and application thereof.
Background
The continual rise in greenhouse gas concentrations in the atmosphere has raised unprecedented concerns about global warming, which can lead to a series of disasters such as the growth 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 for effectively contributing to global warming. Capturing carbon dioxide from the flue gas of fossil fuels is a direct solution to reduce carbon dioxide emissions. In the last decade, a number of advanced carbon dioxide capture and sequestration processes have been developed. Among these capture methods, the liquid amine absorption method captures CO 2 Has been put to practical use. The method has the advantages of high efficiency, large adsorption capacity and the like. However, this method still has a number of disadvantages, limiting its wide application. For example, degradation of liquid amines can easily reduce the absorption properties of liquid amines; the strong alkalinity of the amine liquid has serious corrosion to equipment, and the regeneration consumption of the amine liquid is large.
To overcome these disadvantages, solid adsorbents using porous materials as adsorbents have been proposed to adsorb and trap CO instead of liquid ammonia 2 Is a method of (2). Common 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 valued for 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 improve CO 2 The adsorption capacity and the selectivity of the porous material are improved, the problem of poor water resistance of the porous material is solved, and the solid amine adsorbent which takes 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, easy regeneration and the like for capturing carbon dioxide, and can reduce the emission of carbon dioxide The surface has potential application prospect. 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 typically accomplished by physical loading of the amine into a supporting porous matrix material by impregnation, which fills the pores with amine chemisorbers and forms many carbon dioxide adsorbing active sites.
However, the pore structure of the porous material supports amine and CO 2 The trapping of the amine has important influence, the existing solid amine adsorbent is easy to agglomerate in the matrix material, so that pores are blocked, how to realize the effective load of the amine on the porous matrix material, introduce a large amount of amine groups while keeping the amine groups highly dispersed on the carrier, and realize CO 2 Is a difficult research point in the field of solid adsorbents.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of a foam carbon-based solid amine adsorbent, which is used for solving the problems that the existing solid amine adsorbent amine cannot be effectively loaded on a porous matrix material and cannot efficiently trap carbon dioxide.
The second object of the invention is to provide a carbon foam-based solid amine adsorbent prepared by the preparation method of the carbon foam-based solid amine adsorbent.
The invention further aims to provide an application of the carbon foam-based solid amine adsorbent in carbon dioxide capturing.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a preparation method of a foam carbon-based solid amine adsorbent, which comprises the following steps:
s1: the vitrinite enrichment of the same or different coal types is used as a precursor, and a supercritical foaming method is adopted to prepare the primary coal-based foam carbon;
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: amine-based functionalization is carried out on the hierarchical porous coal-based foam carbon by using an amine modifier, so that the foam carbon-based solid amine adsorbent is obtained.
The solid amine adsorbent is formed by loading organic amine into porous carrier pore channels. The foam carbon-based solid amine adsorbent refers to a solid amine adsorbent taking foam carbon as a carrier, namely amine functionalized foam carbon.
Step S1
The invention uses coal vitrinite as a precursor, and combines supercritical foaming to prepare the primary coal-based foam carbon with special cell and pore size distribution.
Coal includes, but is not limited to, gas coal, fat coal, coking coal, and the like. The source of the vitrinite concentrate is not limited, and can be a commercially available product or can be prepared by the existing enrichment method (for example, patent CN 102849723A).
Further, step S1 includes: taking a high-pressure reaction kettle as a reactor, firstly separating vitrinite enrichment from coal with the particle size of 60-80 meshes (178-254 mu m) or a mixture of vitrinite enrichment of different coal types into a container, and then placing the vitrinite enrichment into the container according to the following steps: the method comprises the steps of adding a supercritical foaming agent in a mass ratio of (i.e. 5:1-200) (e.g. 5:1, 5:2, 1:10, 1:12, 1:16, 1:20, 1:24, 1:30 and 1:40), heating to a foaming temperature of Tc-Tc+200 ℃ at a speed of 1-20 ℃/min, keeping a final foaming pressure Pc-Pc+4 Mpa constant (Tc is the critical temperature of the supercritical foaming agent and Pc is the critical pressure of the supercritical foaming agent), performing constant-temperature foaming for 0.5-4 h (e.g. 0.5, 1, 2, 3 and 4 h) under the supercritical condition of the foaming agent, then performing pressure relief to normal pressure at a pressure relief speed of 4-100 MPa/min, and cooling (preferably naturally cooling) to room temperature to obtain the primary coal-based foam carbon.
Specifically, in step S1, after the pressure of the high-pressure reaction kettle is relieved to normal pressure, the air outlet valve is closed, the temperature is continuously raised to 550-600 ℃ at 2-5 ℃ per minute, the temperature is kept for 15-30 minutes, and then the temperature is reduced, preferably naturally reduced to room temperature, so as to obtain the primary coal-based foam carbon.
The supercritical foaming agent is a special fluid which is simultaneously in a condition of critical pressure (Pc) and critical temperature (Tc) or above, and 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 the supercritical foaming method to coal-based foam carbon, and has more possibility of industrialization under the precondition of Chinese lean oil and rich coal.
Step S2
And carbonizing the primary coal-based foam carbon obtained by taking the coal vitrinite enrichment as a precursor.
The step S2 comprises the following steps: and (3) transferring the primary coal-based foam carbon obtained in the step (S1) into a tubular furnace for carbonization treatment, heating to 800-1000 ℃ at 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.
The light components in the coal-based foam carbon are removed through the high-temperature carbonization process, and the volatile components of the coal-based foam carbon are reduced, so that more pore structures are formed.
Pore cell and pore distribution of the coal-based foam carbon prepared by carbonization: the pore diameter distribution is 35-425 μm (for example 36.55-422.75 μm), and the bulk density is 0.5-0.7 g/cm 3 (e.g., 0.54 to 0.66 g/cm) 3 ) The porosity is 55 to 70% (e.g., 58.6 to 67.51%).
The pore cells are obvious cell structures on the surface of the coal-based foam carbon, and the pore cell diameter distribution is obtained by adopting Nano Measurer 1.2 particle size analysis software statistical SEM (scanning electron microscope) pictures.
Grinding coal-based foam carbon before activation (carbonized coal-based foam carbon) to a particle size of less than 0.2mm, and testing its true density (ρ) by the pycnometer method (GB/T217 21996) T ) (units: g/cm 3 ). Processing carbon foam into cuboid with length, width and height of about 20mm, 20mm and 10mm, and accurately measuring average length (a), width (b) and average length (b) of sample by vernier caliperHigh (h) (unit: cm), the mass (M) (unit: g) of the sample is weighed, and the bulk density (ρ) of the sample is calculated according to the formula (1) V ) (units: g/cm 3 ) The porosity (P) of the sample was calculated according to formula (2) (unit: % of the total weight of the composition.
Step S3
Activating the coal-based carbon foam obtained in S2 (e.g. KOH/K) 2 CO 3 And activating by an alkaline activator) and performing heat treatment (pore forming) to obtain the hierarchical porous coal-based foam carbon with micropore, mesopore and macropore structures.
The pores in the powder material are divided into Micropores (Micropores) by size: the aperture is less than 2nm; mesopores or Mesopores (Mesopores): the aperture is 2-50 nm; macropores (macropore): pore size > 50nm (International Union of pure and applied chemistry (IUPAC)). Herein, the hierarchical porous means a hierarchical porous structure having micropores, mesopores, and macropores at the same time.
Further, step S3 includes: placing the coal-based foam carbon obtained in the step S2 into a KOH solution, wherein the mass ratio of solid alkali (such as KOH) to the coal-based foam carbon is 1-6:1 (such as 1:1, 2:1, 3:1, 4:1, 5:1 and 6:1), stirring for 30 minutes, then soaking for 4-10 hours at 60-90 ℃, drying, then heating to 700-1050 ℃ at a constant rate of 2-5 ℃/min under a protective atmosphere, activating for 1-4 hours, washing with hydrochloric acid and distilled water until the pH=7, and then filtering and drying to obtain the graded porous coal-based foam carbon. FIG. 1 shows a schematic flow chart of an alkali activation process for preparing a hierarchical porous coal-based carbon foam in one embodiment.
The coal-based foam carbon has a relatively single pore structure, and a part of micropore structure is formed 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 hierarchical porous coal-based foam carbon prepared by the activation heat treatment has a specific hierarchical porous structure and a larger specific surface area: the specific surface area is 1050-2048 m 2 /g (e.g. 1087.11m 2 /g～2048m 2 Per g), pore volume of 0.8-1.5 cm 3 /g (e.g. 0.89 cm) 3 /g～1.48cm 3 /g). The micropores, mesopores and macropores Kong Zhanbi are 23 to 26% (e.g., 23.1% to 25.3%), 50 to 56% (e.g., 51.2% to 56%), and 18 to 26% (e.g., 18.6% to 25.6%), respectively.
Micropores, mesopores and macropores Kong Zhanbi are BET statistics of a certain pore number divided by the total pore number.
The invention adopts the means of supercritical foaming, chemical activation and the like of a coal vitrinite to prepare the coal-based foam carbon with a specific hierarchical porous structure, and the foam carbon has larger specific surface area.
Step S4
And (3) performing amine functionalization on the hierarchical porous coal-based foam carbon obtained in the step (S3) by using an amine modifier.
The amine modifiers are mainly organic amines 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 (20 mL) with stirring, for example using a magnetic stirrer. After the organic amine is completely dissolved, the classified porous coal-based carbon foam obtained in S3 is added to the mixed solution, and refluxed at 50 to 80 ℃ (e.g., 70 ℃) for 6 to 10 hours. The resulting product is air dried at 80 c, for example in a forced air drying oven for 12 to 36 hours, to remove methanol from the sample. Then, the organic impregnated sample was dried under vacuum at 60℃for 12 hours to obtain a carbon foam-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 the requirement (the carrier structure can be adjusted). After the hierarchical porous coal-based carbon foam obtained in the step S3 is placed in a mixed solution of organic amine and methanol, organic amine 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 is carried according to the actual working condition of capturing carbon dioxide.
Preferably, the load of the organic amine in the carbon foam-based solid amine adsorbent is 0.1 to 60wt%.
How to introduce large amounts of amine groups while maintaining a high degree of dispersion of the amine groups on the support is a challenge in preparing highly efficient solid amine adsorbents. In order to solve the problem of organic pollution, the amine is easy to agglomerate in the solid amine adsorbent, the carbon dioxide capture with low adsorption cost and high efficiency is realized, coal-based foam carbon with rich hierarchical porous structure is used as a support, and the novel solid adsorbent is prepared by impregnating the organic amine.
In a specific embodiment, a method for preparing a typical carbon foam-based solid amine adsorbent comprises:
grinding dry gas coal, fat coal and coking coal into 60-80 mesh coal powder. The vitrinite concentrates of gas coal, fat coal and coking coal, respectively labeled GV, FV and CV, are separated by patent CN102849723a, method for preparing graphitized carbon foam by pretreatment of bituminous coal. Mixing vitrinite concentrate or a mixture of three vitrinite concentrates GV, FV and CV with a supercritical foaming agent, wherein the vitrinite concentrate is: the supercritical foaming agent is placed in a metal mould according to the mass ratio of = 5:1-200. The supercritical foaming agent can be toluene (99.9%; tc:318.7 ℃ C.; pc:4.11 MPa) or naphthalene (99% or more; tc:475.2 ℃ C.; pc:4.05 MPa) and the like, and is heated to 480 ℃ at 5 ℃/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, the pressure is reduced to normal pressure at the speed of 4MPa/min, the air outlet valve is closed, the temperature is continuously increased to 550 ℃ at the speed of 2 ℃/min, the constant temperature is maintained for 20min, and the temperature is naturally reduced to the room temperature, so that the primary coal-based foam carbon is obtained.
And transferring the primary coal-based foam carbon into a tube furnace for carbonization treatment, heating to 800-1000 ℃ at 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 which is respectively marked as GVCF, FVCF and CVCF.
The coal-based carbon foam was impregnated with the required amount of KOH (KOH/carbon=1 to 6:1 mass ratio), stirred for 30 minutes, then subjected to a heat soak at 80 ℃ for 4 hours, after which the mixture was dried at 105 ℃ for 4 hours, then at 2 ℃ for min -1～ 5℃min -1 The temperature is raised to 750-1000 ℃ and activated for 1-4 hours under the protection of nitrogen. Washing with hydrochloric acid and distilled water until ph=7, then filtering and drying gave a hierarchical porous coal-based foam carbon (GPCF) for further investigation.
An amount of organic amine was dissolved in methanol (20 mL) using a magnetic stirrer and formulated into a solution having a concentration of 0.1 to 80 wt%. After complete dissolution of the organic amine, a certain amount of GPCF was added to the solution and refluxed at 70 ℃ for 6 hours. The resulting product was dried in a forced air oven at 80 ℃ for 12-36 hours to remove methanol from the sample. The organic amine impregnated samples were then dried in vacuo at 60 ℃ for 12 hours. The resulting sample was designated GPCF-xTe, where x represents the loading of the 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 dry sample boxes for further characterization and CO 2 Adsorption studies.
The invention also provides a foam carbon-based solid amine adsorbent which is prepared by the preparation method.
The foam carbon-based solid amine adsorbent has the same advantages as the preparation method, and is not described in detail herein.
In a further aspect, the invention provides an application of the carbon foam-based solid amine adsorbent in carbon dioxide capturing.
Further, the application includes: carbon dioxide is absorbed and desorbed by adopting a carbon dioxide capturing fixed bed reactor;
the structure of the carbon dioxide trapping 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 middle of the reaction tube is filled with the carbon foam-based solid amine adsorbent 101, and the rest upper and lower parts of the reaction tube are filled with quartz cotton; the outer wall of the reaction tube is provided with a heater (heating by a heat tracing belt or heating by heating wires on the wall of a solid adsorbent filler tube or heating by vapor and the like) and is connected with a temperature control device 102 for controlling the adsorption and desorption temperature, a flue gas storage tank 200 is communicated with the inlet of the fixed bed 100 through a pipeline, a mass flowmeter 201 is arranged on the pipeline for controlling the flow rate of flue gas, and a carbon dioxide infrared analyzer 300 is connected with the 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 northwest Anyi gas Inc. Sample CO was performed in the above-described self-made carbon dioxide capture fixed bed reactor 2 And (5) testing the adsorption and desorption performance. Stainless steel with the inner diameter of 10mm is adopted to fill the adsorbent in the reactor, the flow rate of simulated flue gas is controlled by a mass flowmeter, the adsorption and desorption temperature is controlled by a heater, and meanwhile, CO is introduced into an inlet and an outlet of the fixed bed reactor 2 GHX-520 CO produced by Beijing Seibi instruments Co., ltd 2 And (5) measuring the infrared analyzer on line. All adsorption tests were performed at normal 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 cotton in the upper part and the lower part of the adsorbent, then introducing 100mL/min of nitrogen, heating a reactor to 100 ℃ at a constant speed of 5 ℃/min, preprocessing the adsorbent for 60min to remove impurity gas adsorbed by a previous sample, then reducing the temperature of the reactor to a test temperature (75 ℃), and converting the nitrogen into simulated flue gas (containing 85vol.% N after the temperature is stable) 2 And 15vol.% CO 2 ) CO is carried out 2 Adsorption test and turn on CO 2 The infrared ray divides the detector to record the exit CO of the reaction tube 2 Is a concentration of (3). When the reaction tube is out of CO 2 The concentration reaches the CO in the simulated flue gas of the inlet 2 After the initial concentrationThe adsorption process is completed. Then the temperature of the adsorbent is increased to 100 ℃, nitrogen is introduced to carry out the desorption process of the adsorbent, and the CO in the infrared analysis detector is treated 2 When the concentration indication is zero, the desorption is completed. Then the temperature of the adsorbent is reduced to the required temperature, and then the nitrogen is switched back to the simulated flue gas, so that CO can be carried out again 2 And (3) an adsorption process. Repeating the above-mentioned CO 2 The cyclic regeneration performance of the adsorbent can be inspected in the adsorption and desorption process.
Calculating CO of the adsorbent by using the formula (1-1) 2 Adsorption amount.
Wherein F is the air inlet flow (mL/min) of the mixed gas; w is the mass (g) of the adsorbent; t is CO 2 Adsorption time(s); c (C) 0 C is CO at the inlet and outlet of the reaction tube 2 Concentration (vol.%); v (V) m Molar volume of gas (mL/mmol) in standard state; q a For CO at adsorption time t 2 Adsorption amount (mmol/g).
The technical scheme of the invention has the following beneficial effects:
(1) The invention prepares coal-based foam carbon by using a supercritical foaming method, 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 concentrates with different coalification degrees as precursors, realizes the preparation of the hierarchical porous coal-based foam carbon carrier through a simple carbonization/activation process, and then obtains the solid amine adsorbent through amine functionalization, wherein the prepared solid amine adsorbent matrix material has a hierarchical porous structure and a larger specific surface area, the matrix material with a single pore structure is easily blocked by organic amine, the dynamic barrier of carbon dioxide is increased, the mass transfer rate in the carbon dioxide capturing process is reduced, the obtained hierarchical porous carbon material with the special structure with different pore size distribution can improve the loading capacity of amine, meanwhile, a way which is easier to approach the active center of the organic amine is provided, the mass transfer rate in the adsorption-desorption process is also improved, the carbon dioxide adsorption quantity and the carbon dioxide adsorption rate are improved, the excellent carbon dioxide adsorption performance and regeneration capacity are shown, and the application prospect in the carbon dioxide capturing field is wide.
(2) The invention has wide raw material sources, is suitable for industrial production, and has simple operation and small corrosion to equipment when the solid adsorbent is used for capturing carbon dioxide.
The present invention has been described in detail hereinabove, but the above embodiments are merely exemplary 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 summary or the following examples.
Unless explicitly stated otherwise, numerical ranges throughout this application include any subrange therein and any numerical value incremented by the smallest subunit in which a given value is present. Unless explicitly stated otherwise, numerical values throughout this application represent approximate measures or limits to include minor deviations from the given value and ranges of embodiments having about the stated value and having the exact value noted. Except in the operating examples provided last, all numerical values of parameters (e.g., amounts or conditions) in this application (including the appended claims) are to be understood in all cases as modified by the term "about" whether or not "about" actually appears before the numerical value. "about" means that the recited value allows for slight imprecision (with some approximation to the exact value; approximately or reasonably close to the value; approximated). "about" as used herein at least means variations that can be produced by ordinary methods of measuring and using these parameters if the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning. For example, "about" may include a change 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 that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of an activation process for preparing a hierarchical porous coal-based carbon foam according to one embodiment of the present invention;
FIG. 2 is a schematic diagram of the structure of a carbon dioxide capture fixed bed reactor of 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 cell 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 carbon foam of example 1;
FIG. 10 is a TEM image of the hierarchical porous morphology of GPCF-1 activated coal based carbon foam of example 1;
FIG. 11 is a graph showing the results of specific surface area measurement of GPCF-1 activated coal based carbon foam in example 1;
FIG. 12 is a pore size distribution plot of the hierarchical porous structure of GPCF-1 activated coal based carbon foam in example 1;
FIG. 13 is a graph showing pore diameter distribution of the coal-based carbon foam prepared in examples 1 to 3;
FIG. 14 is a graph showing the results of specific surface area measurement of GPCF-4 activated coal based carbon foam in example 4;
FIG. 15 is a graph showing the bulk density and porosity of the coal-based carbon foam prepared in examples 1-3;
FIG. 16 is a graph showing pore diameter distribution of the coal-based carbon foam prepared in examples 4 to 6;
FIG. 17 is a graph showing the bulk density and porosity of the coal-based carbon foams 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 the cell morphology of the mesophase pitch-based carbon foam of comparative example 1;
FIG. 21 is an SEM image of the cell morphology of a coal-based carbon foam prepared by the self-foaming method of comparative example 2;
FIG. 22 is a graph showing the results of specific surface area tests for coal-based carbon foam prepared by omitting the activation process in comparative example 3 with respect to example 1;
FIG. 23 is a graph showing pore size distribution of coal-based carbon foam prepared by omitting the activation process in comparative example 3 with respect to example 1.
The diagram is: 100-fixed bed; 101-a carbon-foam-based solid amine adsorbent; 102-a temperature control device; 200-a flue gas storage tank; 201-a mass flowmeter; 300-carbon dioxide infrared analyzer.
Detailed Description
The 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 as claimed.
Except for the specific details, the materials, reagents, methods, etc. used in the examples were those conventional in the art, and the drugs used in the experiments were those obtained from Milin reagent, TEM using JEM-2100 from JEOL corporation, SEM using a field emission SU-70 microscope, and BET test using ASAP 2020 (Micromeritics Co.) at 350 ℃.
In the examples CO 2 Adsorption performance test method the adsorption/desorption test method described above was referred to.
Examples the coke vitrinite Concentrate (CV) source is described in example 3 disclosed in patent CN102849723 a; the gas coal vitrinite concentrate (GV) source is referred to example 1 disclosed in patent CN102849723 a; the source of the vitrinite enrichment (FV) of fat coal is described in example 2 disclosed in patent CN102849723 a.
Example 1
A preparation method of a foam carbon-based solid amine adsorbent comprises the following steps:
1. 100g of coking coal 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 kettle. The temperature was raised to 480℃at 5℃per minute. The final foaming pressure is kept constant at 8MPa, and the temperature is kept constant for 60min under the supercritical condition of toluene. And after the constant temperature is finished, the pressure is reduced to normal pressure at the speed of 4MPa/min, the air outlet valve is closed, the temperature is continuously increased to 550 ℃ at the speed of 2 ℃/min, the constant temperature is maintained for 20min, and the temperature is naturally reduced to the room temperature, so that the primary coal-based foam carbon is obtained. And (3) transferring the primary coal-based foam carbon into a tube furnace for carbonization treatment, heating to 1000 ℃ at 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 carbon foam was immersed in KOH solution (KOH/carbon=6:1 mass ratio), stirred for 30 minutes and then subjected to heat soaking at 80℃for 4 hours, after which the mixture was dried at 105℃for 4 hours and then at 5℃for min -1 Is heated to 750 ℃ at a constant rate, activated at 750 ℃ under nitrogen protection for 4 hours. Washing with hydrochloric acid and distilled water until ph=7, and then filtering and drying to obtain a hierarchical porous coal-based foam carbon (GPCF-1) whose morphology and hierarchical porous morphology are shown in fig. 9 and 10; the BET specific surface area of GPCF-1 was determined to be 1087.11m 2 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 (20 mL) using a magnetic stirrer. After the TEPA was completely dissolved, a certain amount of GPCF-1 was added to the solution and refluxed at 50 to 80℃for 6 hours. The resulting product was dried in a forced air oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated samples were then dried in vacuo at 60 ℃ for 12 hours. The resulting sample was designated GPCF-1-60% Te. The synthesized samples were stored in dry sample boxes for further characterization and CO 2 Adsorption studies.
4、CO 2 Adsorption performance test: fixing the obtained solidBulk adsorbent for CO 2 adsorption/Desorption test GPCF-1-60% Te showed excellent CO by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption) 2 Adsorption performance and regeneration capacity. First adsorption amount: 5.82mmol/g, second adsorption amount: 5.81mmol/g.
Example 2
A preparation method of a foam carbon-based solid amine adsorbent comprises the following steps:
1. 100g of 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 kettle. The temperature was raised to 480℃at 5℃per minute. The final foaming pressure is kept constant at 8MPa, and the temperature is kept constant for 60min under the supercritical condition of toluene. And after the constant temperature is finished, the pressure is reduced to normal pressure at the speed of 4MPa/min, the air outlet valve is closed, the temperature is continuously increased to 550 ℃ at the speed of 2 ℃/min, the constant temperature is maintained for 20min, and the temperature is naturally reduced to the room temperature, so that the primary coal-based foam carbon is obtained. And (3) transferring the primary coal-based foam carbon into a tube furnace for carbonization treatment, heating to 1000 ℃ at 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 carbon foam was immersed in KOH solution (KOH/carbon=4:1 mass ratio), stirred for 30 minutes and then subjected to heat soaking at 80℃for 4 hours, after which the mixture was dried at 105℃for 4 hours and then at 5℃for min -1 Is heated to 850 ℃ at a constant rate, activated at 850 ℃ under nitrogen protection for 4 hours. Washing with hydrochloric acid and distilled water until ph=7, then filtering and drying gave a hierarchical porous coal-based foam carbon (GPCF-2).
3. An amount of TEPA was dissolved in methanol (20 mL) using a magnetic stirrer. After the TEPA was completely dissolved, a certain 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 oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated samples were then dried in vacuo at 60 ℃ for 12 hours. The resulting sample was designated GPCF-2-60% Te. The synthesized samples were stored in dry sample boxes for further characterization and CO 2 Adsorption studies.
4、CO 2 Adsorption performance test: the obtained solid adsorbent is used for CO 2 adsorption/Desorption test GPCF-2-60% Te showed excellent CO by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption) 2 Adsorption performance and regeneration capacity. First adsorption amount: 5.73mmol/g, second adsorption amount: 5.71mmol/g.
Example 3
A preparation method of a foam carbon-based solid amine adsorbent comprises the following steps:
1. 50g of gas coal vitrinite concentrate (GV) and 50g of coking coal vitrinite Concentrate (CV) are uniformly mixed and then placed in a metal mold, 100ml of toluene is injected, and then the metal mold is placed in a high-pressure reaction kettle. The temperature was raised to 480℃at 5℃per minute. The final foaming pressure is kept constant at 8MPa, and the temperature is kept constant for 60min under the supercritical condition of toluene. And after the constant temperature is finished, the pressure is reduced to normal pressure at the speed of 4MPa/min, the air outlet valve is closed, the temperature is continuously increased to 550 ℃ at the speed of 2 ℃/min, the constant temperature is maintained for 20min, and the temperature is naturally reduced to the room temperature, so that the primary coal-based foam carbon is obtained. And (3) transferring the primary coal-based foam carbon into a tube furnace for carbonization treatment, heating to 1000 ℃ at 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 carbon foam was immersed in KOH solution (KOH/carbon=6:1 mass ratio), stirred for 30 minutes and then subjected to heat soaking at 80℃for 4 hours, after which the mixture was dried at 105℃for 4 hours and then at 5℃for min -1 Is heated to 750 ℃ at a constant rate, activated at 750 ℃ under nitrogen protection for 2 hours. Washing with hydrochloric acid and distilled water until ph=7, then filtering and drying gave a hierarchical porous coal-based foam carbon (GPCF-3).
3. An amount of TEPA was dissolved in methanol (20 mL) using a magnetic stirrer. After the TEPA was completely dissolved, a certain 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 oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated samples were then dried in vacuo at 60 ℃ for 12 hours. The resulting sample was designated GPCF-3-60% Te. Closing deviceThe resulting sample is stored in a dry sample tank for further characterization and CO 2 Adsorption studies.
4、CO 2 Adsorption performance test: the obtained solid adsorbent is used for CO 2 adsorption/Desorption test GPCF-3-60% Te showed excellent CO by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption) 2 Adsorption performance and regeneration capacity. First adsorption amount: 5.53mmol/g, second adsorption amount: 5.52mmol/g.
The specific parameters of examples 1-3 are shown in Table 1.
TABLE 1 preparation scheme of toluene supercritical foam carbon
The pore cell diameter distribution of the coal-based foam carbon prepared in examples 1-3 is shown in FIG. 13, and the pore cell distribution ranges from 42.6 to 336.5 μm for three samples, and the statistics of GV: CV samples were taken with a minimum of 42.6 μm cells. As shown in FIG. 15, the porosity and bulk density were 0.57g/cm 3 ～0.66g/cm 3 The porosity is 58.6-66.23%.
Example 4
A preparation method of a foam carbon-based solid amine adsorbent comprises the following steps:
1. 100g of coking coal vitrinite Concentrate (CV) and 20g of refined naphthalene (99.7 percent; tc:475.2 ℃ C.; pc:4.05 Mpa) are uniformly mixed and then placed into a metal mold, and then the metal mold is placed into a high-pressure reaction kettle. The temperature was raised to 480℃at 5℃per minute. Keeping the final foaming pressure 8MPa constant, and keeping the temperature for 60min under the supercritical condition of naphthalene. And after the constant temperature is finished, the pressure is reduced to normal pressure at the speed of 4MPa/min, the air outlet valve is closed, the temperature is continuously increased to 550 ℃ at the speed of 2 ℃/min, the constant temperature is maintained for 20min, and the temperature is naturally reduced to the room temperature, so that the primary coal-based foam carbon is obtained. And (3) transferring the primary coal-based foam carbon into a tube furnace for carbonization treatment, heating to 1000 ℃ at 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 carbon foam was immersed in KOH solution (KOH/carbon=5:1 mass ratio), stirred for 30 minutes and then subjected to heat soaking at 80℃for 4 hours, after which the mixture was dried at 105℃for 4 hours and then at 5℃for min -1 Is heated to 700 ℃ at a constant rate, activated at 700 ℃ under nitrogen protection for 4 hours. Washing with hydrochloric acid and distilled water until ph=7, then filtering and drying to obtain a hierarchical porous coal-based foam carbon (GPCF-4). The BET specific surface area of GPCF-4 was determined to be 2048m 2 /g, as shown in fig. 14.
3. An amount of TEPA was dissolved in methanol (20 mL) using a magnetic stirrer. After the TEPA was completely dissolved, a certain 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 oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated samples were then dried in vacuo at 60 ℃ for 12 hours. The resulting sample was designated GPCF-4-60% Te. The synthesized samples were stored in dry sample boxes for further characterization and CO 2 Adsorption studies.
4、CO 2 Adsorption performance test: the obtained solid adsorbent is used for CO 2 adsorption/Desorption test GPCF-4-60% Te showed excellent CO by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption) 2 Adsorption performance and regeneration capacity. First adsorption amount: 3.98mmol/g, second adsorption amount: 3.96mmol/g.
Example 5
A preparation method of a foam carbon-based solid amine adsorbent comprises the following steps:
1. 100g of gas coal vitrinite concentrate (GV) and 20g of refined naphthalene (99.7%; tc:475.2 ℃ C.; pc:4.05 MPa) were mixed uniformly and placed in a metal mold, and then the metal mold was placed in a high-pressure reaction kettle. The temperature was raised to 480℃at 5℃per minute. Keeping the final foaming pressure 8MPa constant, and keeping the temperature for 60min under the supercritical condition of naphthalene. And after the constant temperature is finished, the pressure is reduced to normal pressure at the speed of 4MPa/min, the air outlet valve is closed, the temperature is continuously increased to 550 ℃ at the speed of 2 ℃/min, the constant temperature is maintained for 20min, and the temperature is naturally reduced to the room temperature, so that the primary coal-based foam carbon is obtained. And (3) transferring the primary coal-based foam carbon into a tube furnace for carbonization treatment, heating to 1000 ℃ at 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 carbon foam was immersed in KOH solution (KOH/carbon=6:1 mass ratio), stirred for 30 minutes and then subjected to heat soaking at 80℃for 4 hours, after which the mixture was dried at 105℃for 4 hours and then at 5℃for min -1 Is heated to 900 ℃, activated at 900 ℃ under the protection of nitrogen, and activated for 3 hours. Washing with hydrochloric acid and distilled water until ph=7, then filtering and drying gave a hierarchical porous coal-based foam carbon (GPCF-5).
3. An amount of TEPA was dissolved in methanol (20 mL) using a magnetic stirrer. After the TEPA was completely dissolved, a certain 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 oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated samples were then dried in vacuo at 60 ℃ for 12 hours. The resulting sample was designated GPCF-5-60% Te. The synthesized samples were stored in dry sample boxes for further characterization and CO 2 Adsorption studies.
4、CO 2 Adsorption performance test: the obtained solid adsorbent is used for CO 2 adsorption/Desorption test GPCF-5-60% Te showed excellent CO by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption) 2 Adsorption performance and regeneration capacity. First adsorption amount: 5.01mmol/g, second adsorption amount: 4.99mmol/g.
Example 6
A preparation method of a foam carbon-based solid amine adsorbent comprises the following steps:
1. 100g of rich coal vitrinite enrichment (FV) and 20g of refined naphthalene (99.7%; tc:475.2 ℃ C.; pc:4.05 MPa) are evenly mixed and then placed into a metal mold, and then the metal mold is placed into a high-pressure reaction kettle. The temperature was raised to 480℃at 5℃per minute. Keeping the final foaming pressure 8MPa constant, and keeping the temperature for 60min under the supercritical condition of naphthalene. And after the constant temperature is finished, the pressure is reduced to normal pressure at the speed of 4MPa/min, the air outlet valve is closed, the temperature is continuously increased to 550 ℃ at the speed of 2 ℃/min, the constant temperature is maintained for 20min, and the temperature is naturally reduced to the room temperature, so that the primary coal-based foam carbon is obtained. And (3) transferring the primary coal-based foam carbon into a tube furnace for carbonization treatment, heating to 1000 ℃ at 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 carbon foam was immersed in KOH solution (KOH/carbon=4:1 mass ratio), stirred for 30 minutes and then subjected to heat soaking at 80℃for 4 hours, after which the mixture was dried at 105℃for 4 hours and then at 5℃for min -1 Is heated to 1000 ℃ at a constant rate, activated at 1000 ℃ under the protection of nitrogen and activated for 4 hours. Washing with hydrochloric acid and distilled water until ph=7, then filtering and drying gave a hierarchical porous coal-based foam carbon (GPCF-6).
3. An amount of TEPA was dissolved in methanol (20 mL) using a magnetic stirrer. After the TEPA was completely dissolved, a certain 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 oven at 80 ℃ for 12h to remove methanol from the sample. The TEPA impregnated samples were then dried in vacuo at 60 ℃ for 12 hours. The resulting sample was designated GPCF-6-60% Te. The synthesized samples were stored in dry sample boxes for further characterization and CO 2 Adsorption studies.
4、CO 2 Adsorption performance test: the obtained solid adsorbent is used for CO 2 adsorption/Desorption test GPCF-6-60% Te showed excellent CO by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption) 2 Adsorption performance and regeneration capacity. First adsorption amount: 4.34mmol/g, second adsorption amount: 4.33mmol/g.
The specific parameters of examples 4-6 are shown in Table 2.
Table 2 preparation scheme of naphthalene supercritical carbon foam
The pore cell diameter distribution of the coal-based foam carbon prepared in examples 4 to 6 is shown in FIG. 16, and the pore cell distribution ranges from 36.55 to 422 for three samples.A sample of 75 μm with statistical GV gave the smallest cells 36.55. Mu.m. As shown in FIG. 17, the porosity and bulk density were 0.54g.cm -3 ～0.61g.cm -3 The porosity is 63.63% -67.51%.
Example 7
The difference between this example and example 4 is that the foaming temperature was 400℃and the foaming pressure was 5MPa, and as can be seen from FIG. 18, the uniformity of the cell structure of the carbon foam prepared after carbonization was decreased after the temperature and the foaming pressure were decreased, the cells did not show an approximate circle shape, and the solid adsorbent was prepared by activation and TEPA loading. CO is carried out on the solid adsorbent 2 Adsorption performance test by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption). First adsorption amount: 3.53mmol/g, second adsorption amount: 3.52mmol/g.
Example 8
The difference between this example and example 4 is that the ratio of coal vitrinite concentrate to naphthalene is 10:1, and as can be seen from fig. 19, when the ratio of coal vitrinite concentrate is increased, the cell structure of the foam carbon prepared after carbonization is obviously increased, and the solid adsorbent is prepared through activation and TEPA loading. CO is carried out on the solid adsorbent 2 Adsorption performance test by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption). First adsorption amount: 2.67mmol/g, second adsorption amount: 2.68mmol/g.
Comparative example 1
This comparative example differs from example 1 in that the coking coal vitrinite concentrate was replaced with mesophase pitch. As can be seen from fig. 20, the carbonized pitch-based carbon foam has a larger cell structure, which is more uniform and tends to be circular. And (3) activating and TEPA loading to prepare the solid adsorbent. CO is carried out on the solid adsorbent 2 Adsorption performance test by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption). First adsorption amount: 2.33mmol/g, second adsorption amount: 2.34mmol/g.
Comparative example 2
The difference between this comparative example and example 1 is that the supercritical foaming method is replaced by self-foaming, i.e. other conditions are not presentIn the case of the above, the amount of toluene added was 0mL. As can be seen from fig. 21, the carbonized coal-based foam carbon has a larger cell structure, and is activated and TEPA loaded to prepare the solid adsorbent. CO is carried out on the solid adsorbent 2 Adsorption performance test by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption). First adsorption amount: 2.14mmol/g, second adsorption amount: 2.13mmol/g.
Comparative example 3
This comparative example differs from example 1 in that the BET test was performed on the carbon foam excluding step 2, i.e., the activation process, as shown in FIG. 22, which had a significantly lower specific surface area than example 1, and as shown in FIG. 23, the pores of the carbon foam were mainly concentrated in the mesopores and exhibited a single pore structure. And taking the solid adsorbent as a matrix material, and carrying out TEPA loading to prepare the solid adsorbent. CO is carried out on the solid adsorbent 2 Adsorption performance test by changing the temperature from 75 ℃ (adsorption) to 100 ℃ (desorption). First adsorption amount: 0.98mmol/g, second adsorption amount: 0.99mmol/g.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (16)
1. The preparation method of the foam carbon-based solid amine adsorbent is characterized by comprising the following steps of:
(1) The vitrinite enrichment of the same or different coal types is used as a precursor, and a supercritical foaming method is adopted to prepare the primary coal-based foam carbon;
(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 obtain graded porous coal-based foam carbon with micropore, mesopore and macropore structures;
(4) And performing amine functionalization on the hierarchical porous coal-based foam carbon by using an amine modifier to obtain the foam carbon-based solid amine adsorbent.
2. The method of claim 1, wherein step (1) comprises: placing vitrinite concentrates 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+4 MPa, and then, releasing pressure to normal pressure and cooling to room temperature to obtain the primary coal-based foam carbon;
Wherein the supercritical foaming agent is liquid or solid which presents supercritical fluid state at critical temperature;
tc is the critical temperature of the supercritical foaming agent, and Pc is the critical pressure of the supercritical foaming agent.
3. The method of claim 2, wherein the supercritical blowing agent is toluene or naphthalene.
4. A method of preparation according to claim 2 or 3, wherein the mass ratio of supercritical foaming agent to vitrinite concentrate is from 5:1 to 200.
5. The method of claim 1, wherein step (2) comprises: and transferring the primary coal-based foam carbon into a tubular furnace for carbonization treatment, heating to 800-1000 ℃ at 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.
6. The method according to claim 5, wherein the pore diameter distribution of the coal-based foam carbon after carbonization is 35 to 425 μm and the bulk density is 0.5 to 0.7g/cm 3 The porosity is 55 to 70 percent.
7. The method of claim 1, wherein step (3) comprises: the coal-based foam carbon is placed in solid alkaline water solution, immersed for 4 to 10 hours at the temperature of 60 to 90 ℃, dried, then heated to 700 to 1050 ℃ at a constant rate of 2 to 5 ℃/min under a protective atmosphere, activated for 1 to 4 hours, washed, filtered and dried to obtain the graded porous coal-based foam carbon, wherein the solid alkali is KOH and/or K 2 CO 3 。
8. The method according to claim 7, wherein the specific surface area of the hierarchical porous coal-based carbon foam is 1050 to 2048m 2 Per gram, pore volume of 0.8-1.5 cm 3 /g。
9. The method of claim 8, wherein the micro-, meso-, and macro-cells Kong Zhanbi in the hierarchical porous coal-based carbon foam are 23-26%, 50-56%, and 18-26%, respectively.
10. The preparation method according to claim 7, wherein the mass ratio of the solid alkali to the coal-based foam carbon is 1-6:1.
11. The method of claim 1, wherein step (4) comprises: and 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.
12. The method according to claim 11, wherein the amine modifier is one or a mixture of several selected from diethylenetriamine, tetraethylenepentamine, triethylenetetramine, polyethyleneimine, ethanolamine or 2, 6-diethylaniline.
13. The method of claim 11 or 12, wherein the amine modifier is present in the carbon foam-based solid amine adsorbent in an amount of 0.1 to 60wt%.
14. A carbon foam-based solid amine adsorbent prepared by the method of any one of claims 1-13.
15. Use of the carbon-based solid amine adsorbent of claim 14 in carbon dioxide capture.
16. The use according to claim 15, wherein carbon dioxide is desorbed using a carbon dioxide capture fixed bed reactor;
the carbon dioxide trapping fixed bed reactor comprises a fixed bed, a flue gas storage tank and a carbon dioxide infrared analyzer, wherein a reaction tube is axially arranged in the middle of the fixed bed, the middle of the reaction tube is filled with the foam carbon-based solid amine adsorbent, and the rest upper part and the lower part of the reaction tube are filled with quartz cotton; the outer wall of the reaction tube is provided with a heater and is connected with a temperature control device for controlling the adsorption and desorption temperature, the flue gas storage tank is communicated with the inlet of the fixed bed through a pipeline, a mass flowmeter is arranged on the pipeline for controlling the flow rate of flue gas, and the carbon dioxide infrared analyzer is connected with the outlet of the fixed bed for detecting 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 CN113813927A (en) | 2021-12-21 |
| CN113813927B true 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) |
Families Citing this family (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 |
| CN115219381A (en) * | 2022-06-22 | 2022-10-21 | 苏州西热节能环保技术有限公司 | Device and method for detecting performance of carbon dioxide adsorbent for flue gas |
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113813927A (en) | 2021-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Biomass derived nitrogen and sulfur co-doped porous carbons for efficient CO2 adsorption | |
| He et al. | Facile preparation of N-doped activated carbon produced from rice husk for CO2 capture | |
| Choi et al. | Pollen-derived porous carbon by KOH activation: effect of physicochemical structure on CO2 adsorption | |
| Zhao et al. | Water caltrop shell-derived nitrogen-doped porous carbons with high CO2 adsorption capacity | |
| CN113813927B (en) | Foam carbon-based solid amine adsorbent and preparation method and application thereof | |
| Xu et al. | Excellent CO2 adsorption performance of nitrogen-doped waste biocarbon prepared with different activators | |
| Wickramaratne et al. | Importance of small micropores in CO 2 capture by phenolic resin-based activated carbon spheres | |
| Shi et al. | Nitrogen-doped activated carbons derived from microalgae pyrolysis by-products by microwave/KOH activation for CO2 adsorption | |
| Chen et al. | CO 2 adsorption on crab shell derived activated carbons: contribution of micropores and nitrogen-containing groups | |
| Zhang et al. | Preparation of nitrogen-doped microporous modified biochar by high temperature CO 2–NH 3 treatment for CO 2 adsorption: effects of temperature | |
| Huang et al. | Adsorption of carbon dioxide onto activated carbon prepared from coconut shells | |
| 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 | |
| Rodríguez et al. | Low-cost hierarchical micro/macroporous carbon foams as efficient sorbents for CO2 capture | |
| CN110734049B (en) | Method for preparing nitrogen-doped carbon material with high specific surface area by using potassium phthalimide | |
| Tiwari et al. | Epoxy based oxygen enriched porous carbons for CO2 capture | |
| CN105854801A (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
| Luo et al. | Preparation of N-doped activated carbons with high CO 2 capture performance from microalgae (Chlorococcum sp.) | |
| Dong et al. | Ultramicroporous carbon granules with narrow pore size distribution for efficient CH4 separation from coal‐bed gases | |
| CN112897525A (en) | For capturing CO2Preparation method of nitrogen-rich carbon material | |
| Tiwari et al. | Synthesis of nitrogen enriched porous carbons from urea formaldehyde resin and their carbon dioxide adsorption capacity | |
| CN113842884B (en) | Medium-temperature hydrophobic decarbonization adsorbent and preparation method thereof | |
| Huang et al. | From fish scales to highly porous N-doped carbon: a low cost material solution for CO 2 capture | |
| Lu et al. | Nitrogen and sulfur co-doped porous carbons from polyacrylonitrile fibers for CO2 adsorption | |
| Ma et al. | Nitrogen‐doping microporous adsorbents prepared from palm kernel with excellent CO2 capture property | |
| Maruccia et al. | Revealing the competitive effect of N2 and H2O towards CO2 adsorption in N-rich ordered mesoporous carbons |
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 |