CN113842885A - Metal anchoring organic amine CO2Adsorbent, preparation and application thereof - Google Patents
Metal anchoring organic amine CO2Adsorbent, preparation and application thereof Download PDFInfo
- Publication number
- CN113842885A CN113842885A CN202111048455.7A CN202111048455A CN113842885A CN 113842885 A CN113842885 A CN 113842885A CN 202111048455 A CN202111048455 A CN 202111048455A CN 113842885 A CN113842885 A CN 113842885A
- Authority
- CN
- China
- Prior art keywords
- solution
- organic amine
- adsorbent
- metal
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001412 amines Chemical class 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 238000004873 anchoring Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003463 adsorbent Substances 0.000 claims abstract description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 25
- 238000001291 vacuum drying Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000007598 dipping method Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 94
- 239000011148 porous material Substances 0.000 claims description 60
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 34
- 238000001179 sorption measurement Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 229920002873 Polyethylenimine Polymers 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000003546 flue gas Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 18
- 238000005303 weighing Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005411 Van der Waals force Methods 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- -1 amine carbon dioxide Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to a metal anchoring organic amine CO2The preparation method of the adsorbent mainly comprises the following steps: (1) preparation of anchoring site-containing precursor: adding metal salt into deionized water, heating and stirring to obtain a solution A; adding a carrier into the solution A, and drying after dipping to obtain a precursor B containing a metal anchoring site; (2) metal anchored organic amine CO2Preparation of the adsorbent: adding organic amine into an ethanol solution, uniformly stirring to obtain a solution C, then adding a precursor B containing a metal anchoring site into the solution C, and after the organic amine in the solution C is anchored on the precursor B, carrying out vacuum drying to obtain metal anchoring organic amine CO2An adsorbent. The invention providesProviding a metal anchoring organic amine CO2The preparation method enhances the stability of the organic amine adsorbent, thereby improving CO2The circulating stability of the adsorbent is CO which is ultra-stable and has industrial application prospect2Adsorbing the material.
Description
Technical Field
The invention relates to the field of carbon dioxide capture, adsorption and purification, in particular to metal-anchored organic amine CO2A preparation method and application of the adsorbent.
Background
In recent years, global warming and the resultant global climate deterioration have been receiving increased attention. CO22Is the most important artificial greenhouse gas, and the national oceanic and atmospheric administration has recorded CO in the atmosphere since 19582The concentration is continuously rising, and up to now 417ppm has been reached. CO22The increase in the content causes global warming and thus may cause serious ecological problems, thereby reducing CO2Emission suppression global warming is a focus issue facing people.
Research shows that CO2The trapping technology can effectively reduce CO2Emission of CO, and thus CO is vigorously developed2Capture technology, CO reduction2The emission and the delay of global warming have important significance. In recent years, solid amine adsorbents have become a hot spot and a focus of research due to the advantages of low energy consumption, low corrosion to equipment, low cost and the like. Solid amine adsorbents also face the problem of stability in recycle. Patent CN103861557A discloses a new solid amine carbon dioxide adsorbent. The patent reduces the diffusion resistance of carbon dioxide in a solid amine adsorbent by adding a surfactant, improves the utilization rate of amine, but reduces the adsorption amount of the adsorbent and does not consider the cycle stability of the adsorbent. Patent CN112403441A describes a CO loaded with an organic amine by a chemical bond2A preparation method of a solid adsorbent. The patent prepares CO with high capacity, high stability and good cyclicity by introducing chemical bonding of carboxyl and amino of organic amine2An adsorbent. Compared with the common impregnation method, the method has the advantages of complex process, high cost and no contribution to scale-up production. Therefore, the CO with simple preparation operation, low price and good cycle stability is developed2Adsorbent of, for CO2The field of trapping is of great practical significance.
Disclosure of Invention
The invention aims to provide a metal anchoring organic amine CO2The preparation method and the application of the adsorbent solve the problems in the prior art.
In order to achieve the purpose, the following technical scheme is adopted:
metal anchoring organic amine CO2The preparation method of the adsorbent mainly comprises the following steps:
(1) preparation of metal salt solution: adding metal salt into deionized water, heating and stirring to obtain a solution A;
(2) preparation of the anchoring site: adding a certain amount of carrier into the solution A, soaking for a period of time, and drying to obtain a precursor B containing a metal anchoring site;
(3) preparation of organic amine solution: adding organic amine into an ethanol solution, and uniformly stirring to obtain a solution C;
(4) metal anchored organic amine CO2Preparation of the adsorbent: then adding a precursor B containing a metal anchoring site into the solution C (if metal salt is directly added into the solution C, the organic amine cannot be anchored into a carrier pore channel because precipitation is generated in the solution C), after the organic amine in the solution C is anchored onto the precursor B, carrying out vacuum drying to obtain the metal-anchored organic amine CO2An adsorbent.
Preferably, the metal salt is Ni (NO)3)2·6H2O、NiCl2·6H2O、Co(NO3)2·6H2O、CoCl2·6H2O、Cu(NO3)2·3H2O、CuCl2·2H2O、Zn(NO3)2·6H2O、ZnCl2、MgCl2·6H2O, and the like.
Preferably, the carrier is one or more of porous materials such as mesoporous alumina, SAB-15 molecular sieve, porous resin, coconut shell activated carbon, coal-based activated carbon, silica gel and the like; the pore diameter of the carrier is more than 2 nm.
Preferably, the heating temperature is 35-80 ℃, the immersion time is 2-48h, and the drying temperature is 80-120 ℃.
Preferably, the organic amine is one or more of polyethyleneimine, polyvinylamine, polypropyleneimine, pentaethylenehexamine, tetraethylenepentamine, triethylenetetramine, diethylenetriamine, ethylenediamine, diethanolamine and the like.
Preferably, the mass ratio of the carrier to the solution A is 1: 2-20; the mass ratio of the organic amine to the solvent is 1: 2-50; the mass ratio of the precursor B to the solution C is 1: 2 to 100.
Preferably, the vacuum drying temperature is 45-100 ℃.
Metal anchoring organic amine CO2An adsorbent prepared according to the above-mentioned preparation method.
The metal anchoring organic amine CO2The application of the adsorbent is mainly used as a carbon dioxide absorbent to be applied to a carbon dioxide removing device, a closed air purifying device and a direct air capture CO device for tail gas of a power plant2Other CO of plant or the like2A trapping device.
Compared with the prior art, the invention introduces the anchoring site of the organic amine, so that the organic amine is anchored by the anchoring site in the carrier pore channel structure, the stability of the organic amine adsorbent is enhanced, and the volatilization of the organic amine in the high-temperature use process is avoided. The adsorption performance of the adsorbent is basically kept unchanged after 20 times of adsorption and desorption cycles, and the adsorbent has higher cycle stability, and is CO with great industrial application prospect2An adsorbent.
Drawings
Fig. 1 is a schematic model diagram of a metal-anchored organic amine solid adsorbent in example 1.
FIG. 2 is a schematic model of the organic amine solid adsorbent in comparative example 1.
Fig. 3 is a SEM comparison photograph of the adsorbents prepared in example 1 and comparative example 1.
FIG. 4 is a schematic view of TG-DSC curves of samples of the solid adsorbents obtained in example 1 and comparative example 1.
FIG. 5 shows CO of the solid adsorbents obtained in example 1 and comparative example 12And (4) a schematic diagram of adsorption performance cycle.
FIG. 6 is a photograph showing that the metal anchor sites added to the solution C in comparative example 2 cause precipitation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
0.105g of NiCl was weighed2·6H2Adding O into a beaker, adding 3.5ml of deionized water into the beaker, heating to 40 ℃, and stirring for 0.5h to completely dissolve the O to obtain a solution A;
to the solution A, 0.7g of an activated carbon carrier (carrier pore volume of 0.58 cm) was added3The volume of a pore channel with the pore diameter of more than 2nm is more than 95 percent relative to the total pore volume), soaking for 2 hours, drying at 120 ℃ for 6 hours, and removing water to obtain a precursor B containing a metal anchoring site;
weighing 0.3g of tetraethylenepentamine solution in a beaker, adding 3.5ml of ethanol, and stirring to completely dissolve the mixture to obtain solution C;
adding 0.71g of prepared precursor B containing the anchoring site into the solution C, stirring for reaction for 12h, removing ethanol by using a rotary evaporator, then placing the solution in a vacuum drying oven for vacuum drying for 6h at the temperature of 80 ℃, and cooling to room temperature after drying is finished to obtain the metal-anchored organic amine CO2An adsorbent. FIG. 1 is a schematic model diagram of an organic amine solid adsorbent anchored by metal in a carrier pore structure. As can be seen, the organic amine is anchored in the support pore channels by coordination bonds; compared with the common impregnation method, the organic amine is supported in the pore channels through Van der Waals force or hydrogen bonds, and the organic amine anchored by the metal has more stable performance. Fig. 3 is an SEM photograph of the prepared metal-anchored organic amine adsorbent, and it can be seen that the surface of the prepared adsorbent shows a thin layer of anchored organic amine, while the surface of the adsorbent prepared by the general impregnation method (comparative example 1) shows a convex irregular accumulated organic amine. FIG. 4 is a TG-DSC curve chart of the prepared metal-anchored organic amine adsorbent, which shows that the exothermic peak temperature of the thermal analysis curve of tetraethylenepentamine after anchoring is increased from 211 ℃ to 466 ℃, and the stability is increasedIs strong. FIG. 5 is a schematic representation of a metal-anchored organoamine adsorbent (CO) prepared2The adsorption performance test conditions are as follows: and (3) testing temperature: 65 ℃; atmosphere (volume ratio): 15% CO2/85％N2(ii) a Gas flow rate: 100ml/min), the adsorption performance (1.76mmol/g adsorbent) of which is basically kept unchanged after 20 times of cycle tests, and the high cycle stability is shown.
Example 2
Weighing 0.105g of nickel chloride hexahydrate, adding the nickel chloride hexahydrate into a beaker, adding 3.5ml of deionized water into the beaker, and stirring to completely dissolve the nickel chloride hexahydrate to obtain a solution A; to the solution A, 0.75g of an activated carbon carrier (carrier pore volume of 0.58 cm) was added3The volume of a pore channel with the pore diameter of more than 2nm is more than 95 percent relative to the total pore volume), and a precursor B containing a metal anchoring site is obtained after soaking for 2 hours and drying;
weighing 0.3g of tetraethylenepentamine solution in a beaker, adding 3.5ml of ethanol, and stirring to completely dissolve the mixture to obtain solution C;
adding 0.71g of prepared precursor B containing the anchoring site into the solution C, stirring for reaction for 12h, removing ethanol by using a rotary evaporator, then placing the solution in a vacuum drying oven for vacuum drying for 6h at the temperature of 80 ℃, and cooling to room temperature after drying is finished to obtain the metal-anchored organic amine CO2An adsorbent. The adsorbent (CO)2The adsorption performance test conditions are as follows: and (3) testing temperature: 65 ℃; atmosphere: 15% CO2/85％N2(ii) a Gas flow rate: 100ml/min) is tested to keep the adsorption performance (1.68mmol/g adsorbent) basically unchanged after 10 cycles, and shows higher recycling stability.
Example 3
Weighing 0.105g of nickel nitrate hexahydrate, adding the nickel nitrate hexahydrate into a beaker, adding 3.5ml of deionized water into the beaker, and stirring to completely dissolve the nickel nitrate hexahydrate to obtain a solution A; to the solution A was added 0.75g of a silica gel carrier (pore volume of carrier: 0.82 cm)3The volume of a pore channel with the pore diameter of more than 2nm is more than 90 percent relative to the total pore volume), and a precursor B containing a metal anchoring site is obtained after soaking for 2 hours and drying; 0.3g of tetraethylenepentamine solution is weighed into a beaker, then 3.5ml of ethanol is added, and stirring is carried outStirring to completely dissolve the mixture to obtain a solution C; adding 0.71g of prepared precursor B containing the anchoring site into the solution C, stirring for reaction for 12h, removing ethanol by using a rotary evaporator, then placing the solution in a vacuum drying oven for vacuum drying for 6h at the temperature of 80 ℃, and cooling to room temperature after drying is finished to obtain the metal-anchored organic amine CO2An adsorbent. The adsorbent (CO)2The adsorption performance test conditions are as follows: and (3) testing temperature: 65 ℃; atmosphere: 15% CO2/85％N2(ii) a Gas flow rate: 100ml/min) is tested to keep the adsorption performance (1.66mmol/g adsorbent) basically unchanged after 10 cycles, and shows higher recycling stability.
Example 4
Weighing 0.105g of nickel nitrate hexahydrate, adding the nickel nitrate hexahydrate into a beaker, adding 3.5ml of deionized water into the beaker, and stirring to completely dissolve the nickel nitrate hexahydrate to obtain a solution A; to the solution A was added 0.75g of a silica gel carrier (pore volume of carrier: 0.82 cm)3The volume of a pore channel with the pore diameter of more than 2nm is more than 90 percent relative to the total pore volume), and a precursor B containing a metal anchoring site is obtained after soaking for 2 hours and drying; weighing 0.27g of tetraethylenepentamine solution in a beaker, adding 3.73ml of ethanol, and stirring to completely dissolve the mixture to obtain solution C; adding 0.71g of prepared precursor B containing the anchoring site into the solution C, stirring for reaction for 12h, removing ethanol by using a rotary evaporator, then placing the solution in a vacuum drying oven for vacuum drying for 6h at the temperature of 80 ℃, and cooling to room temperature after drying is finished to obtain the metal-anchored organic amine CO2An adsorbent. The adsorbent (CO)2The adsorption performance test conditions are as follows: and (3) testing temperature: 65 ℃; atmosphere: 15% CO2/85％N2(ii) a Gas flow rate: 100ml/min) is tested to keep the adsorption performance (1.64mmol/g adsorbent) basically unchanged after 10 cycles, and shows higher recycling stability.
Example 5
Weighing 0.105g of nickel nitrate hexahydrate, adding the nickel nitrate hexahydrate into a beaker, adding 3.5ml of deionized water into the beaker, and stirring to completely dissolve the nickel nitrate hexahydrate to obtain a solution A; to the solution A was added 0.75g of a silica gel carrier (pore volume of carrier: 0.82 cm)3The volume of the pore channel with the pore diameter of more than 2nm is large relative to the total pore volumeSoaking for 2h at 90%), and drying to obtain a precursor B containing a metal anchoring site; weighing 0.27g of polyethyleneimine solution with the weight-average molecular weight of 600 in a beaker, adding 3.73ml of ethanol, and stirring to completely dissolve the polyethyleneimine solution to obtain solution C; adding 0.71g of prepared precursor B containing the anchoring site into the solution C, stirring for reaction for 12h, removing ethanol by using a rotary evaporator, then placing the solution in a vacuum drying oven for vacuum drying for 6h at the temperature of 80 ℃, and cooling to room temperature after drying is finished to obtain the metal-anchored organic amine CO2An adsorbent. The adsorbent (CO)2The adsorption performance test conditions are as follows: and (3) testing temperature: 65 ℃; atmosphere: 15% CO2/85％N2(ii) a Gas flow rate: 100ml/min) is tested to keep the adsorption performance (1.36mmol/g adsorbent) basically unchanged after 10 cycles, and shows higher recycling stability.
Example 6
Weighing 0.105g of nickel nitrate hexahydrate, adding the nickel nitrate hexahydrate into a beaker, adding 3.5ml of deionized water into the beaker, and stirring to completely dissolve the nickel nitrate hexahydrate to obtain a solution A; to the solution A was added 0.75g of a silica gel carrier (pore volume of carrier: 0.82 cm)3The volume of a pore channel with the pore diameter of more than 2nm is more than 90 percent relative to the total pore volume), and a precursor B containing a metal anchoring site is obtained after soaking for 2 hours and drying; weighing 0.27g of polyethyleneimine solution with the weight-average molecular weight of 600 in a beaker, adding 3.73ml of ethanol, and stirring to completely dissolve the polyethyleneimine solution to obtain solution C; adding 0.71g of prepared precursor B containing the anchoring site into the solution C, stirring for reaction for 10h, removing ethanol by using a rotary evaporator, then placing the solution in a vacuum drying oven for vacuum drying for 6h at the temperature of 80 ℃, and cooling to room temperature after drying is finished to obtain the metal-anchored organic amine CO2An adsorbent. The adsorbent (CO)2The adsorption performance test conditions are as follows: and (3) testing temperature: 65 ℃; atmosphere: 15% CO2/85％N2(ii) a Gas flow rate: 100ml/min) is tested to keep the adsorption performance (1.36mmol/g adsorbent) basically unchanged after 10 cycles, and shows higher recycling stability.
Example 7
0.105g of nickel nitrate hexahydrate is weighed into a beaker, and then added into the beakerAdding 3.5ml of deionized water, and stirring to completely dissolve the deionized water to obtain a solution A; to the solution A was added 0.75g of activated carbon (pore volume of support 0.58 cm)3The volume of a pore channel with the pore diameter of more than 2nm is more than 95 percent relative to the total pore volume), and a precursor B containing a metal anchoring site is obtained after soaking for 2 hours and drying; weighing 0.25g of polyethyleneimine solution with the weight-average molecular weight of 600 in a beaker, adding 3.73ml of ethanol, and stirring to completely dissolve the polyethyleneimine solution to obtain solution C; adding 0.71g of prepared precursor B containing the anchoring site into the solution C, stirring for reaction for 11h, removing ethanol by using a rotary evaporator, then placing the solution in a vacuum drying oven for vacuum drying for 6h at the temperature of 80 ℃, and cooling to room temperature after drying is finished to obtain the metal-anchored organic amine CO2An adsorbent. The adsorbent (CO)2The adsorption performance test conditions are as follows: and (3) testing temperature: 65 ℃; atmosphere: 15% CO2/85％N2(ii) a Gas flow rate: 100ml/min) is tested to keep the adsorption performance (1.38mmol/g adsorbent) basically unchanged after 10 cycles, and shows higher recycling stability.
Example 8
Weighing 0.116g of nickel nitrate hexahydrate, adding the nickel nitrate hexahydrate into a beaker, adding 3.6ml of deionized water into the beaker, and stirring to completely dissolve the nickel nitrate hexahydrate to obtain a solution A; to the solution A was added 0.75g of activated carbon (pore volume of support 0.58 cm)3The volume of a pore channel with the pore diameter of more than 2nm is more than 95 percent relative to the total pore volume), and a precursor B containing a metal anchoring site is obtained after soaking for 2 hours and drying; weighing 0.25g of polyethyleneimine solution with the weight-average molecular weight of 600 in a beaker, adding 3.73ml of ethanol, and stirring to completely dissolve the polyethyleneimine solution to obtain solution C; adding 0.71g of prepared precursor B containing the anchoring site into the solution C, stirring for reaction for 11h, removing ethanol by using a rotary evaporator, then placing the solution in a vacuum drying oven for vacuum drying for 6h at the temperature of 80 ℃, and cooling to room temperature after drying is finished to obtain the metal-anchored organic amine CO2An adsorbent. The adsorbent (CO)2The adsorption performance test conditions are as follows: and (3) testing temperature: 65 ℃; atmosphere: 15% CO2/85％N2(ii) a Gas flow rate: 100ml/min) was tested for 10 cycles and the adsorption performance (1.36mmol/g adsorbent) remained essentially unchanged,shows higher recycling stability.
Comparative example 1
Weighing 0.3g of tetraethylenepentamine solution in a beaker, then adding 3.5ml of ethanol solution, and stirring to completely dissolve the solution; 0.71g of activated carbon carrier (carrier pore volume of 0.58 cm) was taken3And/g, the volume ratio of the pore canal with the pore diameter of more than 2nm to the total pore volume is more than 95 percent), pouring the mixture into the solution, stirring and soaking the mixture for 12 hours, removing ethanol by using a rotary evaporator, then placing the mixture into a vacuum drying oven for vacuum drying for 6 hours at the temperature of 80 ℃, and cooling the mixture to room temperature after the drying is finished to obtain the common solid organic amine CO2 adsorbent. Fig. 2 is a model schematic diagram of a common solid organic amine adsorbent in a carrier pore channel structure, wherein organic amine is supported in the pore channel through van der waals force or hydrogen bond. Fig. 3 is an SEM photograph of the prepared adsorbent, and compared to the metal-anchored organic amine adsorbent prepared in comparative example 1, the adsorbent prepared by the conventional impregnation method has irregular stacked organic amine having corrugation-like protrusions (as red circles in fig. 3) on the surface thereof, the corrugation-like protrusions account for more than 70% of the surface of the adsorbent sphere, the thickness of the corrugation-like protrusions is about 5-20nm, and the organic amine has instability due to stacking on the carrier only by van der waals force or hydrogen bonding. FIG. 4 is a TG-DSC curve of the adsorbent, which shows that the exothermic peak temperature of the adsorbent is 211 ℃ which is much lower than 466 ℃ in example 1, and shows that the stability of the adsorbent in example 1 is better. FIG. 5 is a cycle test curve of the adsorption performance of the prepared metal-anchored organic amine adsorbent at 65 ℃, compared with the metal-anchored organic amine CO prepared in example 12Adsorbent, normally solid organic amine CO2Adsorbent (CO)2The adsorption performance test conditions are as follows: and (3) testing temperature: 65 ℃; atmosphere: 15% CO2/85％N2(ii) a Gas flow rate: 100ml/min) after 20 times of cycle tests, the adsorption performance is reduced by about 14 percent, and the cycle stability is far lower than that of the metal anchoring organic amine CO prepared by the invention2An adsorbent.
Comparative example 2
Weighing 0.3g of tetraethylenepentamine solution in a beaker, then adding 3.5ml of ethanol solution, and stirring to completely dissolve the solution; 0.116g of nickel nitrate hexahydrate was weighed into the above solution, and the above solution immediately appeared to be flocculent precipitate as shown in FIG. 6.
That is, the organic amine precipitated rapidly (about 0.5 min) in ethanol solution and could not impregnate the nickel-anchored TEPA into the pores of the support, resulting in failure to prepare single-site anchored TEPA solid CO2 adsorbent.
Comparative example 3
Weighing 0.3g of tetraethylenepentamine solution in a beaker, then adding 3.5ml of ethanol solution, and stirring to completely dissolve the solution; 0.116g of nickel nitrate hexahydrate and 0.71g of activated carbon carrier (carrier pore volume of 0.58 cm) were weighed3The volume ratio of pore channels with the pore diameter of more than 2nm to the total pore volume is more than 95 percent) is added into the solution at the same time, flocculent precipitates appear in the solution after about 0.5min, a small part of the flocculent precipitates fall on the surface of the carrier, and the majority of the flocculent precipitates fall on the bottom of the beaker, so that the single-site anchored TEPA solid CO2 adsorbent cannot be prepared.
Comparative example 4
0.105g of NiCl was weighed2·6H2Adding O into a beaker, adding 3.5ml of deionized water into the beaker, heating to 40 ℃, and stirring for 0.5h to completely dissolve the O to obtain a solution A;
to the solution A, 0.7g of an activated carbon carrier (carrier pore volume of 0.58 cm) was added3The volume of a pore channel with the pore diameter of more than 2nm is more than 95 percent relative to the total pore volume, and soaking for 2h to obtain a precursor B;
weighing 0.3g of tetraethylenepentamine solution in a beaker, adding 3.5ml of ethanol, and stirring to completely dissolve the mixture to obtain solution C;
and adding the precursor B into the solution C, wherein a large amount of floccules appear on the surface and around the carrier, so that organic amine is prevented from diffusing into the carrier pore channel, and the single-site anchored TEPA solid CO2 adsorbent cannot be prepared.
The invention as described above is further described in detail by way of the detailed procedures and tests which are intended to be illustrative of the invention and not limiting, and thus, all changes and modifications which can be made without departing from the spirit of the invention are intended to be embraced therein.
Claims (9)
1. Metal anchoring organic amine CO2The preparation method of the adsorbent is characterized by mainly comprising the following steps:
(1) preparing a metal salt aqueous solution: adding metal salt into deionized water, heating and stirring to dissolve the metal salt to obtain a solution A; the mass concentration range of the metal salt solution is 1-15%, and the preferred range is 2-8%;
(2) preparation of anchoring site-containing precursor: adding a carrier into the solution A, soaking, and drying to remove water to obtain a precursor B containing the metal anchoring site; the mass ratio of the carrier to the solution A is 1: 3-20, preferably 1: 3-10;
(3) preparing an organic amine ethanol solution: adding organic amine into an ethanol solution, and uniformly stirring to obtain a solution C; the mass ratio of the organic amine to the ethanol is 1: 2-50, preferably 1: 4-20;
(4) metal anchored organic amine CO2Preparation of the adsorbent: adding a precursor B containing a metal anchoring site into the solution C, and drying to remove ethanol after the organic amine in the solution C is anchored on the precursor B to obtain metal-anchored organic amine CO2The mass ratio of the precursor B to the solution C is 1: 2-100, preferably 1: 2 to 40.
2. The method according to claim 1, wherein the metal salt is Ni (NO)3)2·6H2O、NiCl2·6H2O、Co(NO3)2·6H2O、CoCl2·6H2O、Cu(NO3)2·3H2O、CuCl2·2H2O、Zn(NO3)2·6H2O、ZnCl2、MgCl2·6H2One or more than two of O.
3. The preparation method according to claim 1, wherein the carrier is one or two of mesoporous alumina, SAB-15 molecular sieve, porous resin, coconut shell activated carbon, coal activated carbon and silica gel porous materialThe above step (1); preferably, the pore volume of the carrier is more than 0.45cm3(ii)/g; the carrier contains pore channels with the pore diameter larger than 2nm, and the pore channels account for more than 5 percent of the total pore volume.
4. The production method according to claim 1,
the heating temperature in the step (1) is 35-80 ℃, and the time is 0.5-12 h;
the dipping time in the step (2) is 2-48h, the drying temperature is 80-120 ℃, and the drying time is 2-12 h.
5. The method as claimed in claim 1, wherein the organic amine is one or more than two selected from the group consisting of polyethyleneimine having a weight average molecular weight of 600-.
6. The method according to claim 1, wherein the drying in step (4) is vacuum drying at 45-100 ℃ for 2-12 h.
7. A metal-anchored organic amine CO prepared by the preparation method of any one of claims 1 to 62An adsorbent.
8. An adsorbent according to claim 8 in CO2Application in adsorption process.
9. The metal-anchored organic amine CO of claim 82The application of the adsorbent is characterized in that the adsorbent is mainly used as a carbon dioxide absorbent to be applied to a power plant tail gas carbon dioxide capturing device, a flue gas carbon dioxide removing device, an air purifying device or a closed space carbon dioxide removing device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111048455.7A CN113842885B (en) | 2021-09-08 | 2021-09-08 | Metal anchored organic amine CO 2 Adsorbent, preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111048455.7A CN113842885B (en) | 2021-09-08 | 2021-09-08 | Metal anchored organic amine CO 2 Adsorbent, preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113842885A true CN113842885A (en) | 2021-12-28 |
| CN113842885B CN113842885B (en) | 2024-03-08 |
Family
ID=78973456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111048455.7A Active CN113842885B (en) | 2021-09-08 | 2021-09-08 | Metal anchored organic amine CO 2 Adsorbent, preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113842885B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849653A (en) * | 2022-05-12 | 2022-08-05 | 上海交通大学 | Amine modified porous molecular sieve for efficiently trapping carbon dioxide, and preparation method and application thereof |
| CN114950389A (en) * | 2022-06-16 | 2022-08-30 | 四川大学 | Integer CO 2 Adsorption film and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068967A (en) * | 2010-12-14 | 2011-05-25 | 浙江大学 | Supported polypropylene imine material and preparation method and application thereof |
| WO2014082206A1 (en) * | 2012-11-27 | 2014-06-05 | 神华集团有限责任公司 | Method for preparing solid amine gas adsorption material |
| CN104826610A (en) * | 2015-04-02 | 2015-08-12 | 华南理工大学 | Metallic organic skeletal material PEI@UiO-66, preparation method thereof, and application thereof in adsorptive separation of CO2 |
| CN106890621A (en) * | 2017-03-08 | 2017-06-27 | 淮北师范大学 | Organic amino-functionalization macropore holds aluminum oxide CO2Adsorbent and preparation method thereof |
| CN107321317A (en) * | 2017-09-05 | 2017-11-07 | 青岛科技大学 | A kind of solid amine carbon dioxide absorbing material, preparation method and application |
| CN110404521A (en) * | 2019-07-31 | 2019-11-05 | 西北大学 | The adsorbent and its preparation method and application of selective absorption methylene blue |
-
2021
- 2021-09-08 CN CN202111048455.7A patent/CN113842885B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068967A (en) * | 2010-12-14 | 2011-05-25 | 浙江大学 | Supported polypropylene imine material and preparation method and application thereof |
| WO2014082206A1 (en) * | 2012-11-27 | 2014-06-05 | 神华集团有限责任公司 | Method for preparing solid amine gas adsorption material |
| CN104826610A (en) * | 2015-04-02 | 2015-08-12 | 华南理工大学 | Metallic organic skeletal material PEI@UiO-66, preparation method thereof, and application thereof in adsorptive separation of CO2 |
| CN106890621A (en) * | 2017-03-08 | 2017-06-27 | 淮北师范大学 | Organic amino-functionalization macropore holds aluminum oxide CO2Adsorbent and preparation method thereof |
| CN107321317A (en) * | 2017-09-05 | 2017-11-07 | 青岛科技大学 | A kind of solid amine carbon dioxide absorbing material, preparation method and application |
| CN110404521A (en) * | 2019-07-31 | 2019-11-05 | 西北大学 | The adsorbent and its preparation method and application of selective absorption methylene blue |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849653A (en) * | 2022-05-12 | 2022-08-05 | 上海交通大学 | Amine modified porous molecular sieve for efficiently trapping carbon dioxide, and preparation method and application thereof |
| CN114950389A (en) * | 2022-06-16 | 2022-08-30 | 四川大学 | Integer CO 2 Adsorption film and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113842885B (en) | 2024-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113842885A (en) | Metal anchoring organic amine CO2Adsorbent, preparation and application thereof | |
| CN106861634B (en) | Metal-organic framework compound @ mesoporous material composite material and preparation method and application thereof | |
| CN109126849A (en) | A method of preparing the monatomic catalyst of Ni-N-C | |
| CN109201007B (en) | Carbon dioxide adsorbent and preparation method and application thereof | |
| WO2014082206A1 (en) | Method for preparing solid amine gas adsorption material | |
| CN111036219B (en) | Foam carbon blended ZIF-67 pyrolysis derived carbon material and preparation method thereof | |
| CN110350205B (en) | ZIFs-derived metal nitride/carbon composite material, and preparation method and application thereof | |
| CN112221530A (en) | Preparation method and application of non-noble metal single-atom dual-function electrocatalyst | |
| CN107293761A (en) | A kind of Co@N C composite positive poles, preparation method and the application in lithium-air battery | |
| CN114210301A (en) | Mesoporous solid amine adsorbent and preparation method and application thereof | |
| CN104475055A (en) | Preparation method of ultralow-concentration carbon dioxide adsorption film material and production thereof | |
| CN113877539B (en) | CO (carbon monoxide) 2 Solid adsorbent and preparation and application thereof | |
| CN113332958A (en) | Forming method of nitrogen-containing aluminum-based metal-organic framework material and air water absorption application thereof | |
| CN108126651A (en) | A kind of lithium ion sieve of fly ash float load and preparation method thereof | |
| Puccini et al. | Removal of CO2 from flue gas at high temperature using novel porous solids | |
| CN113652715A (en) | Preparation method of self-supporting electrocatalytic hydrogen production material without adhesive | |
| CN108963279A (en) | Nitrogen-doped carbon microballoon/Pd composite catalyst and its preparation method and application | |
| CN111569679B (en) | Functionalized ZIF-8/block polyether amide composite membrane and preparation method and application thereof | |
| CN113186560A (en) | Ni-rich alloy3+Nickel cobaltate modified carbon ball electrode catalyst | |
| CN110394145B (en) | Spherical Li4SiO4Radical CO2Method for preparing adsorbent | |
| CN105110311A (en) | Graphene sponge material used for air purification | |
| CN107376916B (en) | C-Co composite nano material and preparation method and application thereof | |
| CN113493204B (en) | Preparation method of nitrogen-doped nano carbon spheres with ultrahigh specific surface area | |
| CN114849653A (en) | Amine modified porous molecular sieve for efficiently trapping carbon dioxide, and preparation method and application thereof | |
| JP2005013952A (en) | Carbon dioxide absorber |
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 |