CN116422285A - High adsorption capacity porous MgO/ZrO 2 Composite adsorbent and preparation method thereof - Google Patents
High adsorption capacity porous MgO/ZrO 2 Composite adsorbent and preparation method thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 60
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000011240 wet gel Substances 0.000 claims abstract description 44
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 34
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 claims abstract description 19
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 14
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 239000002270 dispersing agent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 12
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001338 self-assembly Methods 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 68
- 239000001569 carbon dioxide Substances 0.000 abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 34
- 150000001412 amines Chemical class 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 125000002091 cationic group Chemical group 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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Abstract
The invention relates to a porous MgO/ZrO with high adsorption capacity 2 The composite adsorbent is MgO/ZrO prepared by mixing long-chain aliphatic dicarboxylic acid dodecanedioic acid serving as a dispersing agent, cetyl trimethyl ammonium bromide serving as a cationic template agent with an organic zirconium source in an ethanol aqueous solution, volatilizing and self-assembling the solvent to form zirconium-containing wet gel, adding magnesium salt, uniformly mixing to obtain zirconium-magnesium wet gel, and roasting at high temperature 2 And (3) a composite adsorption material. The porous MgO/ZrO prepared by the invention 2 The composite adsorbent has higher specific surface area, and does not load amine substancesOn the premise of good selective adsorption effect on carbon dioxide under normal pressure, and good regeneration performance of the adsorbent.
Description
Technical Field
The invention belongs to the technical field of gas trapping, relates to an adsorbent for trapping carbon dioxide, and particularly relates to a zirconia-based composite adsorbent for adsorbing carbon dioxide under normal pressure.
Background
Carbon dioxide (CO) 2 ) Global warming and climate change problems caused by the massive emission of greenhouse gases have become the focus of global attention. Developing CO 2 Is to reduce the CO of greenhouse gas in the technical research of trapping and sealing 2 One of the important ways of discharging and protecting the environment.
Coal-fired power plant as CO 2 Is the most important fixed source of emissions, CO emitted from its flue gas 2 The content is usually between 3 and 30% (volume fraction), so that CO is required to be added 2 Separating and concentrating CO from its flue gas to a higher purity 2 The gas is transported to a specific place by a pipeline and the like for long-term sealing.
Currently, CO in flue gas 2 The separation and recovery of (a) is mainly based on the chemical adsorption of an amino solid adsorbent, and the adsorption operation is usually carried out under the pressure of 0.1-0.17 MPa. If the direct recovery of CO under normal pressure can be realized 2 The CO can be directly captured from the source 2 The cost required.
Sohail et al (Adsorption behavior of tetraethylenepentamine functionalized Si-MCM-41 for CO) 2 adsorption[J]Chemical Engineering Research and Design, 2017, 122:34-42.) modified Si-MCM-41 with Tetraethylenepentamine (TEPA), solid amine adsorbents were prepared, which showed that the adsorbent was in the form of adsorption strips at 75℃under normal pressure when the TEPA loading was 50 wt.%Exhibits a maximum CO of 1.6mmol/g under the piece 2 Adsorption amount.
Recently, zhao Peiyu et al (preparation of amine functional adsorbents and study of carbon dioxide adsorption Performance [ D ]]University of Tai principle works, 2020, 35-42.) reported that an adsorbent having good thermal stability was prepared by supporting TEPA on the surface of a porous silica support, and it was found that when the TEPA supporting amount reached 60wt%, an atmospheric adsorption performance test was performed at 75℃to obtain the maximum CO 2 The adsorption amount was 5.01mmol/g.
The solid amine adsorbents reported in the above documents, although obtaining a certain amount of CO under a certain adsorption condition 2 The adsorption effect, but the amine substances are loaded on the surface of the carrier, so that the preparation process link is increased, and on the other hand, according to the current massive researches, the structural characteristics of the carrier determine the amine loading effect and the CO loading effect to a great extent 2 Is a natural gas, and is an adsorption effect of the catalyst.
Therefore, the necessary improvement of the carrier structure is to solve the problem of CO from the adsorbent under normal pressure 2 An effective means of adsorption effect.
Disclosure of Invention
The invention aims to provide a porous MgO/ZrO with high adsorption capacity 2 Composite adsorbent and preparation method thereof, under the premise of no amine and other modified substances, CO of zirconia adsorbent is further improved under normal pressure 2 Adsorption amount.
The invention relates to a high adsorption quantity porous MgO/ZrO 2 The composite adsorbent is prepared by taking long-chain aliphatic dicarboxylic acid dodecanedioic acid as a dispersing agent, forming a mixed solution with a cationic template agent hexadecyl trimethyl ammonium bromide in an ethanol water solution, adding an organic zirconium source for solvent volatilization and self-assembly to form a zirconium-containing wet gel, adding a magnesium salt, uniformly mixing to obtain a zirconium-magnesium wet gel, and roasting at a high temperature to obtain MgO/ZrO 2 And (3) a composite adsorption material.
Wherein, specifically, the organic zirconium source is any one of zirconium n-butoxide, zirconium n-propoxide or zirconium isopropoxide.
Furthermore, the invention also further provides the porous M with high adsorption capacitygO/ZrO 2 The specific preparation method of the composite adsorbent comprises the following steps:
1) Dissolving dodecanedioic acid in ethanol water solution, and adding cetyltrimethylammonium bromide to obtain a mixed solution;
2) Dropwise adding an organic zirconium source into the mixed solution, and continuously stirring to carry out solvent volatilization self-assembly reaction to obtain zirconium-containing wet gel;
3) Continuously adding magnesium salt into the zirconium-containing wet gel to obtain zirconium-magnesium wet gel;
4) Drying the zirconium-magnesium wet gel, heating to 550-600 ℃ and roasting to obtain high-adsorption-amount porous MgO/ZrO 2 And (3) a composite adsorbent.
Wherein, the molar ratio of the dodecanedioic acid and the hexadecyl trimethyl ammonium bromide to the organic zirconium source and the magnesium salt is 1:2-2.5:12-15:3-12.
Further, in the aqueous ethanol solution, the volume ratio of ethanol to water is preferably 8-12:1, more preferably 10:1.
Furthermore, the reaction time for performing the solvent volatilization self-assembly to obtain the zirconium-containing wet gel is preferably 20-24 hours, and the solvent volatilization self-assembly process is preferably performed at 40 ℃.
Wherein, in order to enable the magnesium salt to be added into the zirconium-containing wet gel more uniformly, a small amount of water is preferably added into the magnesium salt until the magnesium salt is just dissolved and then added into the zirconium-containing wet gel.
More preferably, the present invention is to dry the obtained zirconium magnesium wet gel at 60 to 65 ℃.
Preferably, the invention is used for preparing the porous MgO/ZrO with high adsorption capacity 2 The calcination time of the composite adsorbent is preferably 4 to 6 hours.
More preferably, the invention is to heat up to the roasting temperature at a heating rate of 1-5 ℃/min for heat-preserving roasting to prepare the porous MgO/ZrO with high adsorption capacity 2 And (3) a composite adsorbent.
The invention prepares the porous MgO/ZrO 2 Composite adsorbent passingIn the process, simultaneously introducing dicarboxylic acid with carboxyl groups and a cationic template agent cetyl trimethyl ammonium bromide, and forming a novel super-large molecular substance with a larger space structure by utilizing the interaction between polar base groups contained in the head part of an alkyl chain of the template agent and the carboxyl groups, thereby effectively preventing a great deal of agglomeration of zirconia particles, and simultaneously, the incorporation of magnesium substances further enhances the structural stability of zirconia in a tetragonal phase, thereby preparing the porous MgO/ZrO with higher specific surface area, uniform and controllable pore diameter and high adsorption quantity 2 And (3) a composite adsorbent.
The porous MgO/ZrO prepared by the invention 2 The composite adsorbent not only has the advantages of higher specific surface area and uniform pore size distribution, but also has no agglomeration of the adsorbent particles, and maintains a highly uniform dispersion state, and is directly used as CO 2 Compared with the prior art, the adsorption material has the following technical effects on the premise of not loading amine substances:
1. CO in flue gas 2 The separation and recovery of (C) is mainly based on chemical adsorption of modified solid adsorbent, while the porous MgO/ZrO of the invention 2 The composite adsorbent can be directly used as CO 2 The adsorption material is not required to load amine substances, so that the amine load process links are reduced;
2. the current adsorption operating pressure is usually 0.1-0.17 MPa, the porous MgO/ZrO of the present invention 2 The composite adsorbent can directly recycle CO under normal pressure 2 The recovery cost is greatly saved;
3. solves the problem of CO adsorption due to the prior high pressure 2 Resulting in subsequent CO 2 The trapping cost is increased, the existing adsorbent loading process is complex, and the CO is prepared 2 The adsorption quantity is lower;
4. the composite adsorbent has high stability and strong regeneration capability, and is repeatedly regenerated and used through a plurality of cycles, and the reduction range of the adsorption quantity is smaller.
Drawings
FIG. 1 is a schematic diagram of the preparation of porous MgO/ZrO 2 XRD pattern of the composite adsorbent.
FIG. 2 is a porous MgO/ZrO 2 SEM image of composite adsorbent.
FIG. 3 is a schematic diagram of the preparation of porous MgO/ZrO as per the examples 2 Penetration curve and adsorption capacity of composite adsorbent.
FIG. 4 is a porous MgO/ZrO of example 3 2 And (3) a cyclic regeneration performance diagram of the composite adsorbent.
Description of the embodiments
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are presented only to more clearly illustrate the technical aspects of the present invention so that those skilled in the art can better understand and utilize the present invention without limiting the scope of the present invention.
The production process, the experimental method or the detection method related to the embodiment of the invention are all conventional methods in the prior art unless otherwise specified, and the names and/or the abbreviations thereof are all conventional names in the field, so that the related application fields are very clear and definite, and a person skilled in the art can understand the conventional process steps according to the names and apply corresponding equipment to implement according to conventional conditions or conditions suggested by manufacturers.
The various instruments, equipment, materials or reagents used in the examples of the present invention are not particularly limited in source, and may be conventional products commercially available through regular commercial routes or may be prepared according to conventional methods well known to those skilled in the art.
Examples
Example 1
0.16g (0.7 mmol) of dodecanedioic acid was weighed, added to a mixed solution of 20ml of absolute ethanol and 2ml of deionized water, stirred at 40℃for 15 minutes to obtain a colorless acidic transparent solution, and 0.5g (1.4 mmol) of cetyltrimethylammonium bromide was added thereto, and stirred at 40℃for 2 hours to obtain a colorless transparent solution.
To the solution, 3.84g (10 mmol) of zirconium n-butoxide was added dropwise, and the reaction was stirred at 40℃for 20 hours to obtain a wet gel containing zirconium.
0.095g (1 mmol) of magnesium chloride was weighed, added with water until just dissolved, added to the above zirconium-containing wet gel, and stirred at 40℃for 4 hours to obtain a zirconium-magnesium wet gel.
And (3) carrying out suction filtration on the zirconium magnesium wet gel, washing 3 times by using absolute ethyl alcohol, and drying for 2 hours at 65 ℃ to obtain white powder.
Heating the white powder to 550 ℃ at the speed of 1 ℃/min, and carrying out heat preservation roasting for 5 hours to obtain the porous MgO/ZrO with high adsorption capacity 2 The composite adsorbent was designated MZ-0.1.
Example 2
0.16g (0.7 mmol) of dodecanedioic acid was weighed, added to a mixed solution of 20ml of absolute ethanol and 2ml of deionized water, stirred at 40℃for 15 minutes to obtain a colorless acidic transparent solution, and 0.5g (1.4 mmol) of cetyltrimethylammonium bromide was added thereto, and stirred at 40℃for 2 hours to obtain a colorless transparent solution.
To the solution, 3.84g (10 mmol) of zirconium n-butoxide was added dropwise, and the reaction was stirred at 40℃for 20 hours to obtain a wet gel containing zirconium.
0.285g (1 mmol) of magnesium chloride was weighed, added with water until just dissolved, added to the above zirconium-containing wet gel, and stirred at 40℃for 4 hours to obtain a zirconium-magnesium wet gel.
And (3) carrying out suction filtration on the zirconium magnesium wet gel, washing 3 times by using absolute ethyl alcohol, and drying for 2 hours at 65 ℃ to obtain white powder.
Heating the white powder to 550 ℃ at the speed of 1 ℃/min, and carrying out heat preservation roasting for 5 hours to obtain the porous MgO/ZrO with high adsorption capacity 2 The composite adsorbent was designated MZ-0.3.
Example 3
0.16g (0.7 mmol) of dodecanedioic acid was weighed, added to a mixed solution of 20ml of absolute ethanol and 2ml of deionized water, stirred at 40℃for 15 minutes to obtain a colorless acidic transparent solution, and 0.5g (1.4 mmol) of cetyltrimethylammonium bromide was added thereto, and stirred at 40℃for 2 hours to obtain a colorless transparent solution.
To the solution, 3.84g (10 mmol) of zirconium n-butoxide was added dropwise, and the reaction was stirred at 40℃for 20 hours to obtain a wet gel containing zirconium.
0.475g (1 mmol) of magnesium chloride was weighed, added with water until just dissolved, added into the zirconium-containing wet gel, and stirred at 40 ℃ for 4 hours to obtain a zirconium-magnesium wet gel.
And (3) carrying out suction filtration on the zirconium magnesium wet gel, washing 3 times by using absolute ethyl alcohol, and drying for 2 hours at 65 ℃ to obtain white powder.
Heating the white powder to 550 ℃ at the speed of 1 ℃/min, and carrying out heat preservation roasting for 5 hours to obtain the porous MgO/ZrO with high adsorption capacity 2 The composite adsorbent was designated MZ-0.5.
Example 4
0.16g (0.7 mmol) of dodecanedioic acid was weighed, added to a mixed solution of 20ml of absolute ethanol and 2ml of deionized water, stirred at 40℃for 15 minutes to obtain a colorless acidic transparent solution, and 0.5g (1.4 mmol) of cetyltrimethylammonium bromide was added thereto, and stirred at 40℃for 2 hours to obtain a colorless transparent solution.
To the solution, 3.84g (10 mmol) of zirconium n-butoxide was added dropwise, and the reaction was stirred at 40℃for 20 hours to obtain a wet gel containing zirconium.
0.665g (1 mmol) of magnesium chloride was weighed, added with water until just dissolved, added to the above zirconium-containing wet gel, and stirred at 40℃for 4 hours to obtain a zirconium-magnesium wet gel.
And (3) carrying out suction filtration on the zirconium magnesium wet gel, washing 3 times by using absolute ethyl alcohol, and drying for 2 hours at 65 ℃ to obtain white powder.
Heating the white powder to 550 ℃ at the speed of 1 ℃/min, and carrying out heat preservation roasting for 5 hours to obtain the porous MgO/ZrO with high adsorption capacity 2 The composite adsorbent was designated MZ-0.7.
Example 5
0.16g (0.7 mmol) of dodecanedioic acid was weighed, added to a mixed solution of 20ml of absolute ethanol and 2ml of deionized water, stirred at 40℃for 15 minutes to obtain a colorless acidic transparent solution, and 0.5g (1.4 mmol) of cetyltrimethylammonium bromide was added thereto, and stirred at 40℃for 2 hours to obtain a colorless transparent solution.
To the solution, 3.84g (10 mmol) of zirconium n-butoxide was added dropwise, and the reaction was stirred at 40℃for 20 hours to obtain a wet gel containing zirconium.
0.95g (1 mmol) of magnesium chloride was weighed, added with water until just dissolved, added to the above zirconium-containing wet gel, and stirred at 40℃for 4 hours to obtain a zirconium-magnesium wet gel.
And (3) carrying out suction filtration on the zirconium magnesium wet gel, washing 3 times by using absolute ethyl alcohol, and drying for 2 hours at 65 ℃ to obtain white powder.
White powder is mixed withHeating to 550 ℃ at a speed of 1 ℃/min, and carrying out heat preservation and roasting for 5 hours to obtain the porous MgO/ZrO with high adsorption capacity 2 The composite adsorbent was designated as MZ-1.
Comparative example 1
0.16g (0.7 mmol) of dodecanedioic acid was weighed, added to a mixed solution of 20ml of absolute ethanol and 2ml of deionized water, stirred at 40℃for 15 minutes to obtain a colorless acidic transparent solution, and 0.5g (1.4 mmol) of cetyltrimethylammonium bromide was added thereto, and stirred at 40℃for 2 hours to obtain a colorless transparent solution.
To the solution, 3.84g (10 mmol) of zirconium n-butoxide was added dropwise, and the reaction was stirred at 40℃for 20 hours to obtain a wet gel containing zirconium.
And filtering the zirconium-containing wet gel, washing the zirconium-containing wet gel with absolute ethyl alcohol for 3 times, and drying the zirconium-containing wet gel at 65 ℃ for 2 hours to obtain white powder.
Heating the white powder to 550 ℃ at the speed of 1 ℃/min, and carrying out heat preservation and roasting for 5 hours to obtain the nano porous ZrO 2 An adsorbent.
FIG. 1 shows the X-ray diffraction patterns of the above 5 examples for preparing composite adsorbents, and it can be seen that ZrO with a pure tetragonal phase structure having good crystallinity exists in each adsorbent 2 。
Meanwhile, the occurrence of diffraction peaks of MgO was not observed in FIG. 1, thereby proving that the added MgO was uniformly dispersed into ZrO 2 And (3) upper part.
Further, it can be seen from a Scanning Electron Microscope (SEM) image of the adsorbent material provided in fig. 2 under different fields of view that the adsorbent material is composed of uniform spherical fine particles, and the particle voids are significantly increased.
To prove that the invention prepares the porous MgO/ZrO with high adsorption capacity 2 The carbon dioxide adsorption performance of the composite adsorbent was tested under the conditions of normal pressure and an adsorption temperature of 75 ℃ by using the adsorbent materials prepared in each of the above examples and comparative examples, and the results are shown in table 1.
The adsorption data in Table 1 shows that the presentPorous MgO/ZrO further synthesized by examples of the invention 2 Composite adsorbent material and nanoporous ZrO prepared in comparative example 1 2 Adsorbent comparison, CO 2 The selective adsorption performance of the catalyst is obviously improved.
The penetration curve (a) and adsorption amount change trend curve (b) of 5 examples shown in fig. 3 are further given in conjunction with the data of table 1. It can be seen from the figure that as Mg 2+ With Zr 4+ The increase in molar ratio, both the breakthrough time and the adsorption amount showed a trend of increasing and decreasing, and reached a maximum at a ratio of 0.5 in example 3, consistent with the rules of table 1.
Further, the composite adsorbent of example 3 was subjected to 3-cycle regeneration tests, and the results are shown in FIG. 4, which shows the composite adsorbent against CO 2 Has selective adsorptivity of 3.01mmol/g,2.97mmol/g and 2.93mmol/g, respectively, and CO after 3 times of cyclic test 2 The adsorption quantity is not obviously changed, and is reduced by 2.7 percent compared with the initial adsorption quantity, and the adsorption quantity is reduced to CO 2 The selective adsorptivity of the catalyst can still reach the initial 97.3%, which indicates that the adsorbent has better stability and good recycling performance.
The above embodiments of the invention are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Various changes, modifications, substitutions and alterations may be made by those skilled in the art without departing from the principles and spirit of the invention, and it is intended that the invention encompass all such changes, modifications and alterations as fall within the scope of the invention.
Claims (9)
1. High adsorption capacity porous MgO/ZrO 2 The composite adsorbent is prepared by taking long-chain aliphatic dicarboxylic acid dodecanedioic acid as a dispersing agent, forming a mixed solution with a cation template agent hexadecyl trimethyl ammonium bromide in an ethanol water solution, adding an organic zirconium source for solvent volatilization and self-assembly to form a zirconium-containing wet gel, adding a magnesium salt, uniformly mixing to obtain a zirconium-magnesium wet gel, and roasting at a high temperature to obtain MgO/ZrO 2 And (3) a composite adsorption material.
2. The high adsorption amount porous MgO/ZrO according to claim 1 2 Composite adsorptionThe catalyst is characterized in that the organic zirconium source is any one of zirconium n-butoxide, zirconium n-propoxide or zirconium isopropoxide.
3. The porous MgO/ZrO with high adsorption capacity according to claim 1 2 The preparation method of the composite adsorbent comprises the following steps:
1) Dissolving dodecanedioic acid in ethanol water solution, and adding cetyltrimethylammonium bromide to obtain a mixed solution;
2) Dropwise adding an organic zirconium source into the mixed solution, and continuously stirring to carry out solvent volatilization self-assembly reaction to obtain zirconium-containing wet gel;
3) Continuously adding magnesium salt into the zirconium-containing wet gel to obtain zirconium-magnesium wet gel;
4) Drying the zirconium-magnesium wet gel, heating to 550-600 ℃ and roasting to obtain high-adsorption-amount porous MgO/ZrO 2 And (3) a composite adsorbent.
4. The high adsorption amount porous MgO/ZrO according to claim 3 2 The preparation method of the composite adsorbent is characterized in that the molar ratio of the dodecanedioic acid to the hexadecyl trimethyl ammonium bromide to the organic zirconium source to the magnesium salt is 1:2-2.5:12-15:3-12.
5. The high adsorption amount porous MgO/ZrO according to claim 3 2 The preparation method of the composite adsorbent is characterized in that the volume ratio of ethanol to water in the ethanol water solution is 8-12:1.
6. The high adsorption amount porous MgO/ZrO according to claim 3 2 The preparation method of the composite adsorbent is characterized in that the solvent volatilization self-assembly reaction time is 20-24 hours.
7. The high adsorption amount porous MgO/ZrO according to claim 3 2 The preparation method of the composite adsorbent is characterized in that the magnesium salt is added with water until just dissolved and then added into the zirconium-containing wet gel.
8. The high adsorption amount porous MgO/ZrO according to claim 3 2 The preparation method of the composite adsorbent is characterized in that the zirconium-magnesium wet gel is dried at 60-65 ℃.
9. The high adsorption amount porous MgO/ZrO according to claim 3 2 The preparation method of the composite adsorbent is characterized in that the roasting time is 4-6 h.
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| CN101497019A (en) * | 2009-01-19 | 2009-08-05 | 中国科学院山西煤炭化学研究所 | Carbon dioxide adsorption material in high-temperature flue gas as well as production method and use |
| CN112457005A (en) * | 2020-12-11 | 2021-03-09 | 景德镇陶瓷大学 | Composite preparation method of submillimeter-level zirconia ceramic microspheres |
| CN112774660A (en) * | 2020-12-21 | 2021-05-11 | 江门市科恒实业股份有限公司 | Preparation method of cerium-zirconium solid solution with adjustable pore group proportion |
| CN114873640A (en) * | 2022-04-15 | 2022-08-09 | 滁州学院 | Method for preparing fibrous zirconium dioxide aerogel |
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| CN101497019A (en) * | 2009-01-19 | 2009-08-05 | 中国科学院山西煤炭化学研究所 | Carbon dioxide adsorption material in high-temperature flue gas as well as production method and use |
| CN112457005A (en) * | 2020-12-11 | 2021-03-09 | 景德镇陶瓷大学 | Composite preparation method of submillimeter-level zirconia ceramic microspheres |
| CN112774660A (en) * | 2020-12-21 | 2021-05-11 | 江门市科恒实业股份有限公司 | Preparation method of cerium-zirconium solid solution with adjustable pore group proportion |
| CN114873640A (en) * | 2022-04-15 | 2022-08-09 | 滁州学院 | Method for preparing fibrous zirconium dioxide aerogel |
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