CN113663649A - Application of MOF (Metal organic framework) molding material in low-temperature carbon dioxide capture - Google Patents
Application of MOF (Metal organic framework) molding material in low-temperature carbon dioxide capture Download PDFInfo
- Publication number
- CN113663649A CN113663649A CN202110895812.7A CN202110895812A CN113663649A CN 113663649 A CN113663649 A CN 113663649A CN 202110895812 A CN202110895812 A CN 202110895812A CN 113663649 A CN113663649 A CN 113663649A
- Authority
- CN
- China
- Prior art keywords
- metal
- porous ceramic
- adsorbent
- carbon dioxide
- mof
- 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.)
- Pending
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 54
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 44
- 239000012621 metal-organic framework Substances 0.000 title description 22
- 239000012778 molding material Substances 0.000 title description 2
- 239000003463 adsorbent Substances 0.000 claims abstract description 52
- 239000000919 ceramic Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 15
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 150000004985 diamines Chemical class 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 2
- 239000013078 crystal Substances 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical group 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 34
- 239000000843 powder Substances 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 2
- 230000001413 cellular effect Effects 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 19
- 239000000395 magnesium oxide Substances 0.000 description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 238000003795 desorption Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000012917 MOF crystal Substances 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000006262 metallic foam Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- UISWLBIMLGAHMF-UHFFFAOYSA-N 5-(3-carboxy-4-hydroxyphenyl)-2-hydroxybenzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC(C=2C=C(C(O)=CC=2)C(O)=O)=C1 UISWLBIMLGAHMF-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035040 seed growth Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—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
- 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
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- 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
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The application discloses a preparation, modification and forming method of an MOF adsorbent and application of the MOF adsorbent to low-temperature carbon dioxide capture. The preparation method of the adsorbent comprises the following steps: firstly, after the surface of the porous ceramic is treated and cleaned, the metal M is uniformly loaded on the surface of the porous ceramic. Second, calcination results in an oxide-supported porous ceramic of the metal M. Thirdly, H is added4dobpdc, growing MOF seeds on the oxide surface. After cooling, the metal M nitrate and H are added4dobpdc, making MOF grow over the honeycomb ceramic surface. Fourth, treatment with a diamine yields an amine modified shaped adsorbent material. Compared with powder MOF, the monolithic adsorption material grown in situ on the porous ceramic has excellent mechanical strength and cellular porousThe structure obviously reduces the bed pressure drop of the adsorption bed, and simultaneously has high adsorption capacity and circulation stability. 15% CO at 70-150 deg.C2/N2Adsorbing and separating CO from the mixed gas2In the experiment (2), the CO of 11 wt% is still maintained after 1000 cycles2The adsorption capacity and the purity can reach more than 99 percent.
Description
Technical Field
The application relates to the technical field of carbon dioxide capture, in particular to preparation, forming and modification of an adsorbent applied to low-temperature carbon dioxide capture.
Background
Global warming due to elevated atmospheric carbon dioxide concentrations is one of the most serious environmental problems in the 21 st century. Carbon capture is an important method of slowing down the carbon dioxide content of the atmosphere. Chemical absorption is the most common carbon capture technology in industry. Among them, amines and carbon dioxide have an acid-base interaction, and exhibit an excellent ability to capture carbon dioxide. Such as an aqueous ethanolamine solution, is a carbon dioxide adsorbent widely used in the industry at present. But the specific heat capacity of the aqueous solution is large, the energy consumption in the temperature-variable carbon dioxide adsorption and desorption process is high, and meanwhile, the amine substances are also easy to volatilize and corrode equipment. (Apply Energy,2016,165:648-
In order to overcome the defects of the organic amine aqueous solution, the patent CN112892160A proposes the application of a phase change absorbent in carbon dioxide capture. N-aminoethyl piperazine is used as a main absorbent, N-propanol is used as a phase separation agent, and water is used as a solvent. After the phase change absorbent absorbs carbon dioxide, the uniform liquid phase is converted into a liquid-liquid two phase, most of the carbon dioxide is concentrated in the lower liquid phase, and only the carbon dioxide rich phase needs to be heated during analysis, so that the heating solution amount can be reduced, and the regeneration energy consumption can be reduced. The method has the defects that the separation operation of two liquid phases is required in the analysis process, and the process is complex. In addition, the time for carbon dioxide to reach saturated adsorption in the process is as long as 1h, and the separation aging is low. N-aminoethylpiperazine also has a problem of being easily decomposed and oxidized by heat.
Some solid carbon dioxide adsorbents and corresponding processes are used for carbon capture attempts. For example, patent CN112316902A discloses a composite MgO adsorbent, which is prepared by mixing an organic magnesium precursor with water to form an aqueous solution, adding porous activated carbon, mixing uniformly, and drying to obtain an intermediate; and calcining and decomposing the obtained intermediate in a muffle furnace in an air atmosphere to obtain the magnesium oxide active component dispersed in the porous activated carbon carrier. The composite MgO adsorbent realizes the synergistic effect of physical adsorption and chemical adsorption, the activated carbon carrier is physical adsorption, and the magnesium oxide adsorbent is chemical adsorption. However, magnesium oxide is a strongly basic site and carbon dioxide desorption needs to be carried out at high temperatures of 300-. The high operating temperature makes the process energy intensive, while the high temperature magnesium oxide readily sinters resulting in a decrease in adsorption performance.
Patent CN107998829A discloses a method for CO2Trapped calcium-based solid absorbents. The mass fraction of CaO in the calcium-based absorbent is 70-90%; the preparation method comprises the following steps: dissolving soluble calcium salt in deionized water to obtain a precursor solution, and sequentially freezing, vacuum drying and grinding the precursor solution to obtain precursor powder; fully calcining the precursor powder at 850 deg.C and 950 deg.C to obtain CaO powder, mixing the CaO powder with SiO2The calcium-based absorbent is obtained after the powders are fully mixed and fully calcined at the temperature of 600 ℃ and 950 ℃. The adsorption of the carbon dioxide is carried out at 700 ℃, the temperature is raised to 850 ℃ for desorption after 20min of adsorption, and the high-temperature cycle operation causes the sintering of CaO or calcium carbonate generated by adsorption, thereby weakening the adsorption capacity. The adsorbent has the phenomenon that the adsorption quantity is reduced after 20 adsorption and desorption cycles.
From the above research background, solid adsorbents such as magnesium oxide and calcium oxide are promising candidates, because the solid has a small heat capacity and can reduce sensible heat required for regeneration. Furthermore, if a solid adsorbent is used instead, the solvent loss and corrosion problems of the aqueous amine system can be minimized. However, the ultra-high operating temperature makes them easy to sinter, and increases the operating difficulty, which limits their application. The industrialization process of capturing carbon dioxide by the solid adsorbent is still hindered, and the main reason is that the adsorbent with high low-temperature adsorption capacity and excellent cycle stability is lacked.
Metal Organic Framework (MOF) materials are a class of porous crystalline adsorbents that have been widely used in recent years for low temperature gas separation. (chem. rev.2012,112,724.) some metal organic framework materials have coordinatively unsaturated metal centers, these penta-coordinated metal cations have open metal sites and can act as lewis acids, one amine in the diamine molecule can bind to the metal cation in the form of lewis base, while the other amine can still act as a chemically reactive adsorption site, and a functionalized high performance carbon dioxide adsorbent is synthesized. However, MOFs obtained by traditional synthesis methods are generally in powder form, and MOF materials are difficult to form into particles with certain mechanical strength, such as the MOF structures are directly damaged by adding a binder to form by traditional methods, so that the channels completely collapse, and the adsorption capacity for carbon dioxide is completely lost.
Disclosure of Invention
The application provides a preparation, forming and modification method of an adsorbent applied to low-temperature carbon dioxide capture.
The technical scheme adopted by the application is as follows: a method for preparing, forming and modifying an adsorbent applied to low-temperature carbon dioxide capture. The adsorbent is MOF material M2(dobpdc) is adsorbent (M is one or more of metal Mg, Mn, Zn, Fe, Co and Ni, H4dobpdc: 4, 4 '-dihydroxy-3, 3' -biphenyldicarboxylic acid), a process for preparing M2(dobpdc) in-situ growth on porous ceramics (alumina ceramics, cordierite ceramics, etc.) or metal fibers, metal foams. The MOF adsorbent material having a certain mechanical strength is mainly obtained by the following several steps.
First, uniform coating of the metal precursor on the porous ceramic. Firstly, the honeycomb porous ceramic is subjected to ultrasonic treatment by using a 1M NaOH aqueous solution and then is dried in vacuum overnight, so that the surface of the honeycomb porous ceramic is clean. Taking metal M nitrate as a precursor, and uniformly loading the metal M nitrate on the surface of the porous ceramic by using methods such as dipping, deposition precipitation or hydrothermal method;
secondly, calcining to obtain porous ceramic loaded with the oxide of the metal M;
third, M2(dobpdc) seed growth. Using M oxide-coated ceramic as metal source, adding H4And (3) dobpdc, taking methanol and N, N-dimethylformamide as solvents, and reacting for 12h at the temperature of 200 ℃ in a hydrothermal kettle at 120 ℃ to grow MOF crystal seeds on the surface of the oxide. After cooling, adding metal M nitrate and H into the hydrothermal kettle4Continuing the reaction to enable the MOF to grow over the surface of the honeycomb ceramic;
fourthly, diamine treatment is used to obtain the amine modified formed high-performance adsorbing material M2(dobpdc) -amine/honeycombA ceramic.
The method comprises the following steps:
(1) the honeycomb-shaped alumina ceramic is treated by ultrasonic treatment with 1M NaOH aqueous solution for 30min and then dried in vacuum overnight, so that the surface of the ceramic is clean.
(2) Mixing Mg (NO)3)2·6H2Dissolving O in deionized water, adding urea, refluxing at 90 deg.C for 24 hr to deposit Mg on the surface of cellular alumina.
(3) Calcining in a 400 ℃ muffle furnace to obtain the MgO-loaded honeycomb alumina.
(4) MgO-loaded honeycomb alumina is taken as a Mg source, and H is added4dobpdc, adding the mixture in a volume ratio of 55: 45 of methanol and DMF to give solution a.
(5) Transferring the solution A into a hydrothermal kettle to react for 12h at 120 ℃ so that MOF crystal seeds grow on the surface of MgO. Cooling, adding Mg (NO) into the hydrothermal kettle3)2·6H2O and H4And dobpdc, and continuing the reaction to grow the MOF on the surface of the honeycomb ceramic.
(6) Using diamine to treat to obtain the amine modified formed high-performance adsorbing material M2(dobpdc) -amine/honeycomb ceramic.
In the step (1), one of honeycomb alumina ceramics or aluminum fibers is used.
The above-mentioned at least one technical scheme that this application adopted can reach following beneficial effect:
MOF material M used in the application2(dobpdc) As an adsorbent, a method of adsorbing M is proposed2(dobpdc) in-situ growth on porous ceramics (alumina ceramics, cordierite ceramics, etc.) or metal fibers, metal foams. The MOF adsorbent material having a certain mechanical strength was obtained by four steps. M grown in situ on porous ceramics compared to powdered MOF2The (dobpdc) -amine/honeycomb ceramic monolithic adsorption material has excellent mechanical strength, the honeycomb porous structure obviously reduces the bed pressure drop of the adsorption bed, and simultaneously has high adsorption capacity and cycle stability. 15% CO at 70-150 deg.C2/N2In the experiment of adsorbing and separating carbon dioxide in the mixed gas, 1000 cycles of circulation are realizedThe absorption amount of carbon dioxide of 11 wt% is kept, and the purity of the separated carbon dioxide reaches more than 99%.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 shows a powdered MOF adsorbent Mg2(dobpdc) adsorption performance test chart.
FIG. 2 shows untreated (left) honeycomb alumina ceramic and M2(dobpdc) -amine/honeycomb alumina ceramic (right panel).
FIG. 3 is M2Carbon dioxide adsorption performance test chart of (dobpdc) -amine/honeycomb alumina ceramic adsorbent.
FIG. 4 is M2Carbon dioxide adsorption performance test chart of (dobpdc) -amine/aluminum fiber adsorbent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the following specific embodiments of the present application and the accompanying drawings. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1 powdered MOF adsorbent Mg2(dobpdc) preparation and adsorption Performance testing
(1) Adsorbent preparation
1. Weighing H4dobpdc 9.89g，Mg(NO3)2·6H2O11.5 g was placed in a 500mL flask and added to 200mL of a 55: 45, in a mixed solution of methanol and DMF, the solid is quickly dissolved by ultrasonic treatment for 30 min.
2. The solution is transferred to a hydrothermal reaction kettle with the volume of 350mL, and the reaction is carried out for 14h at the temperature of 120 ℃.
3. After the reaction is finished, cooling to room temperatureThe product is filtered, washed three times with 250mL DMF and dried in vacuo at 180 ℃ for 2 h. The obtained white solid powder is Mg2(dobpdc)。
(2) Adsorption Performance test
And testing the carbon dioxide adsorption performance of the powder MOF adsorbent by using a thermogravimetric analyzer. Weighing 10mg of adsorbent, placing into a crucible of a thermogravimetric analyzer, and introducing the adsorbent into a crucible of the thermogravimetric analyzer at 150 deg.C under N2Activating for 1h under atmosphere, then reducing the temperature to 70 ℃, and cutting in 15% CO2/N2After adsorbing for 7min, stopping introducing 15% CO2/N2Heating the mixed gas to 150 ℃ for CO2Desorption of (3). After 10 cycles of the powder adsorbent, the carbon dioxide adsorption amount was maintained at about 12 wt%, as shown in FIG. 1.
EXAMPLE 2 in situ growth of Mg on Honeycomb alumina ceramic2(dobpdc)
(1) Adsorbent preparation
1. The surface of honeycomb alumina ceramic (diameter about 20mm, height about 8mm, see fig. 1) was cleaned by ultrasonic treatment with 1M aqueous NaOH for 30min and vacuum drying overnight.
2. 2.0g of Mg (NO)3)2·6H2Dissolving O in 50mL of water, adding 6.0g of urea, refluxing at 90 ℃ for 24h, and uniformly depositing Mg on the surface of the honeycomb-shaped alumina by a precipitation method.
Calcining in a muffle furnace at the temperature of 2.400 ℃ to obtain the MgO-loaded honeycomb alumina.
3. MgO-loaded honeycomb alumina is taken as an Mg source, and 4.8g H is added4dobpdc, in a 100mL volume ratio of 55: 45 of mixed solution of methanol and DMF, and reacting for 12 hours in a hydrothermal kettle at 120 ℃ to grow MOF crystal seeds on the surface of MgO. After cooling, 3.8g Mg (NO) was added to the hydrothermal kettle3)2·6H2O and 3.3g H4And dobpdc, and continuing the reaction to grow the MOF on the surface of the honeycomb ceramic.
4. Using diamine to treat to obtain the amine modified formed high-performance adsorbing material M2(dobpdc) -amine/honeycomb ceramic. Obtained M2A photograph of (dobpdc) -amine/honeycomb alumina is shown in fig. 2.
(2) Sorbent performance testing
M test Using thermogravimetric Analyzer2Carbon dioxide adsorption performance of the (dobpdc) -amine/honeycomb alumina ceramic adsorbent. Weighing 10mg of adsorbent, placing into a crucible of a thermogravimetric analyzer, and introducing the adsorbent into a crucible of the thermogravimetric analyzer at 150 deg.C under N2Activating for 1h under atmosphere, then reducing the temperature to 70 ℃, and cutting in 15% CO2/N2After adsorbing for 7min, stopping introducing 15% CO2/N2Heating the mixed gas to 150 ℃ for CO2Desorption of (3). After the adsorbent is circulated for 1000 times, the carbon dioxide adsorption amount is kept around 11 wt%, as shown in FIG. 3.
Example 3 in situ growth of Mg on Al fibers2(dobpdc)
(1) Adsorbent preparation
1. Firstly, carrying out hydrothermal treatment on aluminum fibers with a 1M NaOH aqueous solution at 120 ℃ for 30min, and then carrying out vacuum drying overnight to form an aluminum oxide structure on the surfaces of the aluminum fibers.
2. 4.0g of Mg (NO)3)2·6H2Dissolving O in 50mL of water, adding 12.0g of urea and 4.0g of the aluminum fiber treated in the step 1, and reacting in a hydrothermal kettle at 90 ℃ for 24 hours to uniformly precipitate Mg on the surface of the aluminum fiber.
And calcining in a muffle furnace at the temperature of 2.400 ℃ to obtain the MgO-loaded aluminum fiber.
3. 2.0g of MgO-loaded aluminum fiber was used as an Mg source, and 2.4g H was added4dobpdc, in a 100mL volume ratio of 55: 45 of mixed solution of methanol and DMF, and reacting for 12 hours in a hydrothermal kettle at 120 ℃ to grow MOF crystal seeds on the surface of MgO. After cooling, 1.9g Mg (NO) was added to the hydrothermal kettle3)2·6H2O and 1.6gH4And dobpdc, and continuing the reaction to grow the MOF over the surface of the aluminum fiber.
4. Using diamine to treat to obtain the amine modified formed high-performance adsorbing material M2(dobpdc) -amine/aluminium fibres.
(2) Testing of catalyst Performance
M test Using thermogravimetric Analyzer2Carbon dioxide adsorption performance of the (dobpdc) -amine/aluminum fiber adsorbent. Weighing 20mg of adsorbent, placing into a crucible of a thermogravimetric analyzer, and introducing the adsorbent into the crucible at 150 deg.C under N2Activating for 1h under atmosphere, then reducing the temperature to 70 ℃, and cutting in 15% CO2/N2After adsorbing for 7min, stopping introducing 15% CO2/N2Heating the mixed gas to 150 ℃ for CO2Desorption of (3). After the adsorbent is circulated for 100 times, the carbon dioxide adsorption amount is kept at about 6 wt%, as shown in FIG. 4.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (9)
1. A preparation method of an adsorbent applied to low-temperature carbon dioxide capture is characterized by comprising the following steps:
step 1, treating porous ceramic or metal fiber with NaOH solution, then drying in vacuum, adding nitrate solution with metal M as cation into the treated porous ceramic or metal fiber, and uniformly precipitating the metal M element in the nitrate solution on the surface of the porous ceramic or metal fiber by using a dipping, deposition precipitation or hydrothermal method;
step 2, calcining the porous ceramic or metal fiber prepared in the step 1 to obtain porous ceramic or metal fiber loaded with the oxide of the metal M;
step 3, taking the metal M in the porous ceramic or metal fiber loaded by the oxide of the metal M as a metal source, taking methanol and N, N-dimethylformamide as solvents, and adding H4dobpdc, reacting at 120-200 deg.C for 11-13 hr to grow MOF seed crystal on the oxide surface of metal M, cooling to 25 deg.C, adding nitrate with cation as metal M and H4Continuing the reaction at 25 ℃ to ensure that the MOF grows over the surface of the porous ceramic or metal fiber;
and 4, treating the porous ceramic or metal fiber prepared in the step 3 with diamine to obtain the amine modified molded high-performance adsorbing material.
2. The method for preparing the adsorbent for low-temperature carbon dioxide capture according to claim 1, wherein:
in the step 1, the method for uniformly precipitating the metal M element in the nitrate solution on the surface of the porous ceramic or metal fiber comprises the following steps: dissolving nitrate of which the cation is metal M in deionized water, adding the treated porous ceramic or metal fiber into a nitrate solution, then adding urea, and heating and refluxing for 23-25 hours to ensure that metal ions M in the nitrate are uniformly deposited and precipitated on the surface of the porous ceramic or metal fiber.
3. The method for preparing the adsorbent for low-temperature carbon dioxide capture according to claim 1, wherein:
in the step 1, the concentration of the NaOH solution is 1 mol/L.
4. The method for preparing the adsorbent for low-temperature carbon dioxide capture according to claim 3, wherein:
in the step 1, when the porous ceramic is used, the porous ceramic is treated by ultrasonic treatment with NaOH solution for at least 30min and then dried in vacuum overnight,
when the metal fiber is used, the metal fiber is hydrothermally treated with NaOH solution at 115-125 deg.c for at least 30min and vacuum dried overnight to form metal oxide structure on the surface.
5. The method for preparing the adsorbent for low-temperature carbon dioxide capture according to claim 1, wherein:
the porous ceramic is honeycomb-shaped alumina ceramic or honeycomb-shaped cordierite ceramic, and the metal fiber is aluminum fiber.
6. The method for preparing the adsorbent for low-temperature carbon dioxide capture according to claim 1, wherein:
in the step 2, the porous ceramic or metal fiber is calcined in a muffle furnace at 350-450 ℃.
7. The method for preparing the adsorbent for low-temperature carbon dioxide capture according to claim 1, wherein:
step 3, the volume ratio of the methanol to the N, N-dimethylformamide is 55: (44-46).
8. The method for preparing the adsorbent for low-temperature carbon dioxide capture according to claim 1, wherein:
the reaction in step 3 is carried out in a hot water kettle.
9. The method for preparing the adsorbent for low-temperature carbon dioxide capture according to claim 1, wherein:
the metal M is Mg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110895812.7A CN113663649A (en) | 2021-08-05 | 2021-08-05 | Application of MOF (Metal organic framework) molding material in low-temperature carbon dioxide capture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110895812.7A CN113663649A (en) | 2021-08-05 | 2021-08-05 | Application of MOF (Metal organic framework) molding material in low-temperature carbon dioxide capture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113663649A true CN113663649A (en) | 2021-11-19 |
Family
ID=78541554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110895812.7A Pending CN113663649A (en) | 2021-08-05 | 2021-08-05 | Application of MOF (Metal organic framework) molding material in low-temperature carbon dioxide capture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113663649A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115671951A (en) * | 2022-07-19 | 2023-02-03 | 原初科技（北京）有限公司 | Carbon dioxide combined capturing method |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226260A (en) * | 2014-09-19 | 2014-12-24 | 湖南大学 | Preparation and modification methods of metal-organic frame material Bi-BTC for adsorbing CO2 |
| CN104437116A (en) * | 2014-12-08 | 2015-03-25 | 大连理工大学 | Method for performing induced synthesis on MOFs (metal-organic frameworks) membrane by implanting homologous metal oxide particles into surface of macroporous carrier by virtue of swabbing process |
| US20150158013A1 (en) * | 2012-08-10 | 2015-06-11 | King Abdullah University Of Science And Technology | Metal-organic materials (moms) for co2 adsorption and methods of using moms |
| WO2015161037A1 (en) * | 2014-04-16 | 2015-10-22 | The Regents Of The University Of California | Very low density metal organic frameworks with large pore volumes |
| CN106040204A (en) * | 2016-06-17 | 2016-10-26 | 华东师范大学 | Magnetic microporous organic nanotube hybrid material and preparation and application thereof |
| CN106268656A (en) * | 2016-09-28 | 2017-01-04 | 中国石油大学(北京) | Porous alumina ceramic loaded Cu MOF adsorbent and preparation method thereof |
| CN106457120A (en) * | 2014-04-22 | 2017-02-22 | 加利福尼亚大学董事会 | Cooperative chemical adsorption of acid gases in functionalized metal-organic frameworks |
| US20200047114A1 (en) * | 2018-08-09 | 2020-02-13 | King Fahd University Of Petroleum And Minerals | Gas separation membrane containing metal-organic frameworks and methods of making thereof |
| JP2020032325A (en) * | 2018-08-28 | 2020-03-05 | Ｊｆｅエンジニアリング株式会社 | Selective combined gas permeable membrane with metal-organic framework layer and method for manufacturing the same |
| CN111054223A (en) * | 2019-12-27 | 2020-04-24 | 大连理工大学 | Method for preparing defect-free MOF-801 membrane by small crystal seed induced membrane formation-surfactant post-modification strategy and application thereof |
| CN111093824A (en) * | 2017-08-04 | 2020-05-01 | 加利福尼亚大学董事会 | Metal-organic framework with attached cyclic diamine for carbon dioxide capture |
| CN111225730A (en) * | 2017-10-31 | 2020-06-02 | 加利福尼亚大学董事会 | Metal organic framework of additional polyamines for carbon dioxide separation |
| CN111495410A (en) * | 2020-04-29 | 2020-08-07 | 浙江师范大学 | Honeycomb ceramic-porous carbon monolithic catalyst, honeycomb ceramic-porous carbon monolithic adsorbent and preparation method and application thereof |
| WO2020256450A1 (en) * | 2019-06-19 | 2020-12-24 | 한국과학기술원 | Structured metal-organic framework fiber adsorbent for capturing carbon dioxide and manufacturing method therefor |
| WO2021010597A1 (en) * | 2019-07-16 | 2021-01-21 | 삼성전자주식회사 | Carbon dioxide adsorbent and air purification apparatus comprising same |
-
2021
- 2021-08-05 CN CN202110895812.7A patent/CN113663649A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150158013A1 (en) * | 2012-08-10 | 2015-06-11 | King Abdullah University Of Science And Technology | Metal-organic materials (moms) for co2 adsorption and methods of using moms |
| WO2015161037A1 (en) * | 2014-04-16 | 2015-10-22 | The Regents Of The University Of California | Very low density metal organic frameworks with large pore volumes |
| CN106457120A (en) * | 2014-04-22 | 2017-02-22 | 加利福尼亚大学董事会 | Cooperative chemical adsorption of acid gases in functionalized metal-organic frameworks |
| CN104226260A (en) * | 2014-09-19 | 2014-12-24 | 湖南大学 | Preparation and modification methods of metal-organic frame material Bi-BTC for adsorbing CO2 |
| CN104437116A (en) * | 2014-12-08 | 2015-03-25 | 大连理工大学 | Method for performing induced synthesis on MOFs (metal-organic frameworks) membrane by implanting homologous metal oxide particles into surface of macroporous carrier by virtue of swabbing process |
| CN106040204A (en) * | 2016-06-17 | 2016-10-26 | 华东师范大学 | Magnetic microporous organic nanotube hybrid material and preparation and application thereof |
| CN106268656A (en) * | 2016-09-28 | 2017-01-04 | 中国石油大学(北京) | Porous alumina ceramic loaded Cu MOF adsorbent and preparation method thereof |
| CN111093824A (en) * | 2017-08-04 | 2020-05-01 | 加利福尼亚大学董事会 | Metal-organic framework with attached cyclic diamine for carbon dioxide capture |
| CN111225730A (en) * | 2017-10-31 | 2020-06-02 | 加利福尼亚大学董事会 | Metal organic framework of additional polyamines for carbon dioxide separation |
| US20200047114A1 (en) * | 2018-08-09 | 2020-02-13 | King Fahd University Of Petroleum And Minerals | Gas separation membrane containing metal-organic frameworks and methods of making thereof |
| JP2020032325A (en) * | 2018-08-28 | 2020-03-05 | Ｊｆｅエンジニアリング株式会社 | Selective combined gas permeable membrane with metal-organic framework layer and method for manufacturing the same |
| WO2020256450A1 (en) * | 2019-06-19 | 2020-12-24 | 한국과학기술원 | Structured metal-organic framework fiber adsorbent for capturing carbon dioxide and manufacturing method therefor |
| WO2021010597A1 (en) * | 2019-07-16 | 2021-01-21 | 삼성전자주식회사 | Carbon dioxide adsorbent and air purification apparatus comprising same |
| CN111054223A (en) * | 2019-12-27 | 2020-04-24 | 大连理工大学 | Method for preparing defect-free MOF-801 membrane by small crystal seed induced membrane formation-surfactant post-modification strategy and application thereof |
| CN111495410A (en) * | 2020-04-29 | 2020-08-07 | 浙江师范大学 | Honeycomb ceramic-porous carbon monolithic catalyst, honeycomb ceramic-porous carbon monolithic adsorbent and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YUEPING BAO ET AL.: "A Novel Metal-Organic Framework (MOF)-Mediated Interfacial Polymerization for Direct Deposition of Polyamide Layer on Ceramic Substrates for Nanofiltration", 《ADV.MATER.INTERFACES》 * |
| 孙增智 等: "金属有机骨架化合物的二氧化碳吸附性能的研究进展", 《材料导报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115671951A (en) * | 2022-07-19 | 2023-02-03 | 原初科技（北京）有限公司 | Carbon dioxide combined capturing method |
| CN115671951B (en) * | 2022-07-19 | 2023-04-07 | 原初科技（北京）有限公司 | Carbon dioxide combined capturing method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101158456B1 (en) | Porous organic-inorganic hybrid materials with crystallinity and method for preparing thereof | |
| CN107362807B (en) | Mn/Co-based low-temperature SCO catalyst and preparation method thereof | |
| CN106215869B (en) | Porous silica ceramic load Cu-MOF adsorbent and preparation method thereof | |
| KR102267930B1 (en) | Novel aluminum-based metal-organic framework having a 3-dimensinal porous structure comprising 2 or more ligands, and preparation method therefor and uses thereof | |
| CN112892489B (en) | MOFs/carbon aerogel adsorption filtering material and preparation method thereof | |
| US11045785B2 (en) | Metal-organic framework, method for preparing the same, and adsorption device employing the same | |
| CN111974444A (en) | Preparation method and application of small-pore molecular sieve supported noble metal material prepared by one-pot method | |
| Zhang et al. | Preparation of metal organic frameworks MIL-101 (Cr) with acetic acid as mineralizer | |
| KR20110019804A (en) | Method for preparing organic-inorganic hybrid nanoporous material, organic-inorganic hybrid nanoporous materials obtained by said method and use thereof | |
| CN113231009B (en) | Ammonia adsorbent and preparation method thereof | |
| CN115676896B (en) | Amorphous manganese oxide composite material and preparation method and application thereof | |
| KR100865974B1 (en) | Ag impregnated porous antibiosis adsorbent and a process of preparing the same | |
| CN114713233A (en) | Non-noble metal coating-carrier catalyst, preparation method and application thereof | |
| CN113663649A (en) | Application of MOF (Metal organic framework) molding material in low-temperature carbon dioxide capture | |
| CN105903458A (en) | Preparation method and application of calcium-based adsorbent | |
| CN113750961A (en) | Carbon dioxide adsorbent and preparation method thereof | |
| CN110327887B (en) | Al-MOFS/charcoal composite material and preparation method and application thereof | |
| Ling et al. | Molybdenum trioxide impregnated carbon aerogel for gaseous elemental mercury removal | |
| CN110040714A (en) | A kind of absorption carbon dioxide nitrogen phosphorus doping porous carbon materials and preparation method thereof | |
| CN113171758B (en) | Carbon dioxide adsorbent and preparation method and application method thereof | |
| Feng et al. | Photocatalytic activity of porous magnesium oxychloride cement combined with AC/TiO 2 composites | |
| KR100803325B1 (en) | Titanium dioxide added alkali-carbonate regenerable sorbent for carbon dioxide removal | |
| CN114849652A (en) | Activated carbon-encapsulated imidazole metal organic framework composite material with high gas separation selectivity and preparation method thereof | |
| CN112755953B (en) | Adsorbent for removing nitrogen oxides in fluid, preparation method and application | |
| CN110013826A (en) | The preparation method and application of aluminium pillared montmorillonite load K-Nb or Mg-Nb compound 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211119 |
|
| RJ01 | Rejection of invention patent application after publication |