CN116726888B - Surface modified hydrophobic triazole zinc salt material and preparation and application thereof - Google Patents
Surface modified hydrophobic triazole zinc salt material and preparation and application thereof Download PDFInfo
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- CN116726888B CN116726888B CN202310955347.0A CN202310955347A CN116726888B CN 116726888 B CN116726888 B CN 116726888B CN 202310955347 A CN202310955347 A CN 202310955347A CN 116726888 B CN116726888 B CN 116726888B
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 30
- -1 triazole zinc salt Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 23
- LJUQGASMPRMWIW-UHFFFAOYSA-N 5,6-dimethylbenzimidazole Chemical compound C1=C(C)C(C)=CC2=C1NC=N2 LJUQGASMPRMWIW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 14
- OKSPRJLVFYQXQS-UHFFFAOYSA-N 2H-triazole zinc Chemical class N1N=NC=C1.[Zn] OKSPRJLVFYQXQS-UHFFFAOYSA-N 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000011491 glass wool Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229910052665 sodalite Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 229920005594 polymer fiber Polymers 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 86
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 43
- 239000001569 carbon dioxide Substances 0.000 abstract description 43
- 238000001179 sorption measurement Methods 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003546 flue gas Substances 0.000 abstract description 16
- 239000003446 ligand Substances 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 4
- 241000255925 Diptera Species 0.000 abstract description 3
- 238000011278 co-treatment Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000012986 modification Methods 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003958 fumigation Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 230000009919 sequestration Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical group CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- 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
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic 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 invention relates to a surface modified hydrophobic triazole zinc salt material and preparation and application thereof, firstly, a crystalline porous material hydrophilic triazole zinc salt ZnMTZ is obtained by a rapid stirring mode; and then modifying the hydrophobic molecules 5, 6-dimethyl-benzimidazole on the surfaces of the ZnMTZ particles by a ligand exchange mode assisted by a solvent through coordination, so as to obtain the surface modified hydrophobic triazole zinc salt ZnMTZ material. The invention skillfully selects the DMBIM as the hydrophobic molecule, and reasonably controls the mass ratio of the hydrophilic ZnMTZ to the DMBIM to ensure that the DMBIM of the hydrophobic molecule is wrapped at a local position on the surface of the ZnMTZ and does not block pores of the ZnMTZ, thereby improving the hydrophobicity of the hydrophilic ZnMTZ material and simultaneously carrying out CO treatment 2 The adsorption performance remains unchanged. The ZnMTZ with the surface modified is more stable under water vapor, does not adsorb water vapor in a low humidity environment, and is particularly suitable for being used as CO in the low humidity environment 2 The capturing material can be used for mosquito killing and also can be used for separating and capturing carbon dioxide in flue gas.
Description
Technical Field
The invention belongs to the field of gas separation, and particularly relates to a surface modified hydrophobic triazole zinc salt material, and preparation and application thereof.
Background
Carbon dioxide (CO) 2 ) Is the main gas for generating greenhouse effect. Carbon capture and sequestration (carbon capture and storage, CCS) technology is currently the primary solution for reducing carbon dioxide emissions to the atmosphere from the combustion of fossil fuels. The issued national assessment report of climate change and national scheme of climate change for China clearly and definitely also uses CO 2 The study of capture and sequestration technology (CCS) is a primary task for slowing down climate change and controlling greenhouse gas emissions. In combination with the current requirements of 'carbon reaching peak', 'carbon neutralization', the great development of carbon capture technology is a strategic choice for guaranteeing energy safety, and is also an important means for constructing ecological civilization and realizing sustainable development. The key point of the carbon trapping technology is a novel carbon trapping device and a carbon trapping material.
Currently, CO capture 2 The method mainly comprises a liquid amine absorption method, a low-temperature distillation method, a membrane separation method and a solid adsorption method. The solid adsorption method has the characteristics of simple operation, low process requirement, short flow, less investment, low energy consumption, good environmental benefit and the like, and is paid attention to. However, the capture and separation of CO using solid adsorption in complex industrial environments 2 It is often difficult to avoid the presence of moisture. Due to the water molecules being combined with CO 2 Generating competitive adsorption, resulting in adsorbent CO 2 The trapping ability is reduced and moisture may even destroy the structure of the crystalline porous material. Although most of the water vapor can be removed with a condenser, complete drying cannot be achieved, so that the carbon capture device is required to operate at a lower humidity. Design is stable at low humidity and CO 2 Porous adsorbents with unaffected trapping capacity would be an effective solution.
Crystalline porous materials, including zeolites, metal organic frameworks, covalent organic frameworks, and the like, have great potential in the technical field of carbon capture due to the advantages of higher specific surface area, regular and adjustable pore diameters, unique adsorption sites, and the like. Based on the crystalline porous material, a novel device for carbon capture is constructed by utilizing a solid adsorption method, which is beneficial to popularization and development of carbon capture technology.
Disclosure of Invention
The invention aims to provide a surface modified hydrophobic triazole zinc salt material and a preparation method thereof, so as to solve the problem of CO under low humidity 2 Trapping and separating and the like.
A preparation method of a surface modified hydrophobic triazole zinc salt material comprises the following steps:
(1) Preparing hydrophilic triazole zinc salt;
(2) Mixing hydrophilic ZnMTZ, 5, 6-dimethyl-benzimidazole, an organic alcohol solvent and organic fatty amine, stirring and reacting at 50-70 ℃ for 18-36 h, wherein the 5, 6-dimethyl-benzimidazole is used as a surface modification ligand, methanol is used as an auxiliary solvent, and triethylamine is used as a catalyst to accelerate ligand exchange, so that the surface modification of the hydrophilic ZnMTZ is realized; the solid precipitate obtained by the above operation is washed 3 to 5 times with methanol solvent, then is washed 1 to 3 times with dichloromethane, and is dried in vacuum at 50 to 100 ℃.
Further, the mass ratio of the hydrophilic ZnMTZ to the 5, 6-dimethyl-benzimidazole to the organic alcohol solvent to the organic fatty amine is 1 (1-2) (160-200) (0.7-1.4).
Further, the organic alcohol solvent includes methanol, ethanol and isopropanol.
Further, the organic fatty amine includes triethylamine, trimethylamine, tripropylamine and triisopropylamine.
Further, the organic alcohol solvent is methanol, the organic fatty amine is triethylamine, and the mass ratio of the hydrophilic ZnMTZ to the 5, 6-dimethyl-benzimidazole to the methanol to the triethylamine is 1:1:160:0.7.
Further, preparing the hydrophilic ZnMTZ in step (1) includes: mixing 25% ammonia water, 0.02-0.04 mol/L zinc acetate water solution and 0.02-0.04 mol/L1-hydrogen-3-methyl-1, 2, 4-triazole water solution in the volume ratio of 0.125 (0.75-1.25): (1.5-2.5), stirring at room temperature for reaction at the rotating speed of 400-700 rpm for 3-7 h, filtering after the reaction is finished, washing the obtained white solid precipitate with methanol solvent for 3-5 times, and vacuum drying at the temperature of 50-80 ℃.
The invention firstly obtains crystalline porous material hydrophilic triazole zinc salt ZnMTZ by a rapid stirring mode, and the composition of the crystalline porous material is Zn (MTZ) 2 Wherein HMTZ is 1-hydrogen-3-methyl-1, 2, 4-triazole. ZnMTZ has sodalite topology network with BET specific surface area reaching 1147 and 1147 m 2 And/g. And then modifying hydrophobic molecules 5, 6-dimethyl-benzimidazole (HDMBIM) on the surfaces of ZnMTZ particles by a ligand exchange mode assisted by a solvent through coordination, so as to obtain the surface modified hydrophobic triazole zinc salt ZnMTZ material.
The BET specific surface area of the surface modified hydrophobic triazole zinc salt ZnMTZ is not obviously reduced, and reaches 1137 and 1137 m 2 And/g. CO at 298K of ZnMTZ before and after surface modification 2 Adsorption isotherms have substantially coincident. The modification of the hydrophobic molecule HDMIM changes the surface of the particle from hydrophile to hydrophile, and ZnMTZ after surface modification is performed at low humidityRH=20%) does not adsorb water vapor, avoids water molecules and CO 2 Competitive adsorption of molecules, i.e. maintaining CO at low humidity 2 Is provided.
Wherein the hydrophilic triazole zinc salt ZnMTZ is zinc acetate (Zn (CH) 3 COO) 2 ) Is prepared by dissolving HMTZ in water at room temperature and stirring for reaction.
Wherein, the filler takes hydrophilic triazole zinc salt ZnMTZ as an inner core, and then the hydrophobic molecule 5, 6-dimethyl-benzimidazole is modified on the surface of the particle by a solvent auxiliary ligand exchange mode to obtain the hydrophobic triazole zinc salt ZnMTZ material.
The surface modified hydrophobic triazole zinc salt material obtained by the preparation method.
Further, the surface modified hydrophobic zinc triazole salt is covered by 5, 6-dimethyl-benzimidazole through coordination by microporous sodalite type 3-methyl-1, 2, 4-zinc triazole salt.
Application of the surface modified hydrophobic triazole zinc salt material in CO 2 Is a capture of (a). Is especially suitable for being used as CO in low humidity environment 2 The capturing material can be used for mosquito killing and also can be used for separating and capturing carbon dioxide in flue gas.
CO based on surface modified hydrophobic triazole zinc salt material 2 The capturing device comprises a condenser 1 at the front end of a separation column, a glass wool 2, a surface modified hydrophobic zinc triazole salt filler 3 and a fixed bed filler column 4, wherein the condenser is connected with the separation column through a pipeline, and the glass wool 2 and the surface modified hydrophobic zinc triazole salt filler 3 are filled in the separation column.
Further, the glass wool 2 may be one of quartz fiber, aluminum silicate fiber or polymer fiber.
The condenser 1 is only required to reduce the humidity of the flue gas to below 20%. The BET specific surface area of the surface modified hydrophobic triazole zinc salt material reaches 1100 m 2 And/g. The contact angle of the water drop reaches more than 130 ℃, the water drop is stable in water at 65 ℃, and the water drop does not adsorb water vapor under the humidity of 20 percent. The surface modified hydrophobic triazole zinc salt material per gram can effectively purify more than 5 mL of simulated flue gas and capture most CO in the simulated flue gas 2 . And regenerate moreThe secondary performance is not reduced.
At present, a hydrophobic material is generally coated on the surface of a material.
Compared with the prior art, the invention skillfully selects the DMBIM as the hydrophobic molecule, and reasonably controls the mass ratio of the hydrophilic ZnMTZ to the DMBIM to ensure that the DMBIM of the hydrophobic molecule is wrapped at a local position on the surface of the ZnMTZ and does not block pores of the ZnMTZ, thereby improving the hydrophobicity of the hydrophilic ZnMTZ material and simultaneously carrying out CO treatment 2 The adsorption performance remains unchanged. The ZnMTZ with the surface modified by the invention is more stable under water vapor, does not adsorb water vapor under low humidity environment, and has good CO resistance 2 Has stronger adsorption performance, and is especially suitable for being used as CO in low humidity environment 2 The capturing material can be used for mosquito killing and also can be used for separating and capturing carbon dioxide in flue gas.
Drawings
FIG. 1 is a schematic diagram of the structure and process of the synthesis and modification of hydrophilic ZnMTZ;
FIG. 2 is an X-ray powder diffraction pattern of hydrophilic ZnMTZ after one day of soaking in 65℃water with the original synthesis of hydrophobic ZnMTZ of the present invention;
FIG. 3 is an X-ray powder diffraction pattern of hydrophilic ZnMTZ in different proportions with hydrophobic ZnMTZ prepared by DMBIM;
FIG. 4 is an X-ray powder diffraction pattern of hydrophobic ZnMTZ prepared in different solvents;
FIG. 5 is an X-ray powder diffraction pattern of hydrophobic ZnMTZ prepared with different organic fatty amines;
the left plot in fig. 6 is the water drop contact angle of hydrophilic ZnMTZ, and the right plot is the water drop contact angle of hydrophobic ZnMTZ of the invention;
FIG. 7 is a thermogravimetric plot of hydrophilic ZnMTZ and hydrophobic ZnMTZ of the present invention after fumigation for one day at different humidities;
FIG. 8 is a graph of hydrophilic ZnMTZ and hydrophobic ZnMTZ of the present invention N at 77K 2 Adsorption isotherm plot;
FIG. 9 is a graph of hydrophilic ZnMTZ CO with the hydrophobic ZnMTZ of the present invention at 298K 2 Single component adsorption isotherm plot;
FIG. 10 is a CO of the hydrophobic ZnMTZ of the present invention 2 Heat of adsorption (Qst) and CO 2 /N 2 A separation ratio;
FIG. 11 is a schematic representation of the hydrophobic ZnMTZ of the present invention at 298K for CO of simulated flue gas 2 Capturing and testing;
FIG. 12 is a CO containing hydrophobic ZnMTZ of the present invention 2 A capture device, wherein: 1-a condenser; 2-glass wool; 3-surface modified hydrophobic zinc triazole salt filler; 4-a fixed bed packing column; 5-hydrophilic ZnMTZ;6-5, 6-dimethyl-benzimidazole.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Example 1
A synthesis method of surface modified triazole zinc salt comprises the following steps:
(1) Preparation of hydrophilic zinc triazoles ZnMTZ: mixing 25% ammonia water, 0.02-0.04 mol/L zinc acetate aqueous solution and 0.02-0.04 mol/L1-hydrogen-3-methyl-1, 2, 4-triazole aqueous solution in a volume ratio of 0.125:1:2, stirring at room temperature for reaction for 3-7-h under the condition of 400-700 revolutions per minute, filtering after the reaction is finished, washing the obtained white solid precipitate with a methanol solvent for 3-5 times, and vacuum drying at 50-80 ℃ to obtain the hydrophilic triazole zinc salt ZnMTZ material.
(2) Preparation of hydrophobic zinc triazole salt ZnMTZ: mixing hydrophilic ZnMTZ, 5, 6-dimethyl-benzimidazole, methanol and triethylamine according to the mass ratio of 1:1:160:0.7, stirring and reacting for 18-36 h at 50-70 ℃, washing the obtained solid precipitate with methanol solvent for 3-5 times, washing with dichloromethane for 1-3 times, and vacuum drying at 50-100 ℃ to obtain the hydrophobic ZnMTZ material.
Characterization of Performance
1. Characterization of the purity and hydrothermal stability of the sample.
As shown in FIG. 2, the X-ray powder diffraction pattern of the hydrophilic ZnMTZ prepared in example 1 was confirmed to be pure phase by agreement with the theoretical simulation. The majority of the hydrophilic ZnMTZ samples were hydrolyzed to zinc oxide after soaking in 65 ℃ water for one day. Whereas example 1 hydrophobic ZnMTZ covered by 5, 6-dimethyl-benzimidazole by complexation remained stable after one day of immersion in water at 65 ℃.
2. Hydrophobicity test of samples.
As shown in fig. 6, the contact angle of the hydrophilic ZnMTZ with the water drop was 41.5 °, the contact angle of the hydrophobic ZnMTZ subjected to surface modification was 133.6 °, and the contact angle was changed from hydrophilic to hydrophobic.
3. And (3) steam fumigation experiments.
The hydrophilic ZnMTZ and hydrophobic ZnMTZ samples which are completely dried to remove solvent molecules are placed in a sample bottle, transferred into salt solutions with different humidity, sealed and stood for one day. After standing in a salt solution for one day, thermogravimetry is performed, as shown in fig. 7, the left graph shows the thermogravimetry curve of the sample before and after modification at RH 20% humidity, and the right graph shows the thermogravimetry curve of the sample before and after modification at RH 10% humidity. The hydrophilic ZnMTZ has obvious weight loss and absorbs water vapor, while the hydrophobic ZnMTZ has no obvious weight loss and hardly absorbs water vapor.
4. BET specific surface area characterization.
The hydrophilic ZnMTZ and hydrophobic ZnMTZ samples which are completely dried to remove solvent molecules are respectively tested for nitrogen adsorption isotherms at 77K, and as shown in figure 8, BET specific surface areas of the samples are obtained by fitting, and the BET specific surface areas of the samples reach 1100 m 2 And the specific surface area of the sample before and after modification is not obviously changed above/g.
5、CO 2 And (5) adsorption test.
The hydrophilic ZnMTZ and hydrophobic ZnMTZ samples, which were completely dried to remove solvent molecules, were tested for CO at 298K, respectively 2 Adsorption isotherms, as shown in FIG. 9, for CO before and after modification 2 The adsorption performance is not changed obviously.
6. Hydrophobic ZnMTZ heat of adsorption (Qst) and CO 2 /N 2 Separation ratio.
As shown in fig. 10, by CO for the hydrophobic ZnMTZ sample 2 /N 2 Fitting and calculating adsorption data to obtain the hydrophobic ZnMTZ-to-CO 2 The heat of adsorption (Qst) was about 26 kJ/mol, and the theory of ideal adsorption solution was used to predict that the hydrophobic ZnMTZ was effective for simulating flue gas (CO) at 298K and 1 bar 2 :N 2 =15:85) CO in 2 The adsorption selectivity of (2) is about 13.
7. CO simulating flue gas 2 And (5) capturing a test.
The surface modified zinc triazolyl ZnMTZ hydrophobic filler is filled into a separation column, then simulated flue gas with different humidity is introduced, and the components of the effluent gas are detected by gas chromatography. As shown in fig. 11, CO for simulated flue gas 2 The capture test shows that the novel CO based on the surface modified triazole zinc salt ZnMTZ hydrophobic filler is filled 2 The trap device is hydrophobic to CO under the conditions of drying and humidity of 20% 2 Without a decrease in capture capacity, more than 5 mL simulated flue gas per gram of packing can be effectively purified to capture a substantial portion of the CO therein 2 . And the performance of regeneration for many times is not reduced. It is expected to be applied to the treatment of flue gas under low humidity in the industrial environment.
8. CO based on the surface modified Zinc triazoles hydrophobic Filler of example 1 2 Capturing device
As shown in fig. 12, a separation column comprising an outer layer, a glass wool filler, and a surface modified zinc triazole salt filler. The front end of the separation column is provided with a condenser 1 which is connected with the separation column through a pipeline, so that the humidity of flue gas entering the separation column is reduced to below 20 percent, glass wool 2, a surface modified hydrophobic triazole zinc salt filler 3 and a fixed bed filler column 4 are filled in the separation column, and the surface modified triazole zinc salt is covered by microporous sodalite type 3-methyl-1, 2, 4-triazole zinc salt through coordination effect by 5, 6-dimethyl-benzimidazole. The device can effectively treat the flue gas under low humidity and capture CO therein 2 And the flue gas is not required to be completely dried, so that the requirements on a condenser are greatly reduced, and the energy consumption is reduced.
Example 2
The hydrophobic ZnMTZ prepared by mixing hydrophilic ZnMTZ and DMBIM according to the mass ratio of 1:0.5, 1:1, 1:1.5, 1:2 and 1:3 is the same as in example 1. Hydrophobic ZnMTZ can be obtained when the mass ratio of the hydrophilic ZnMTZ to the DMBIM is 1:1, 1:1.5 and 1:2, and the effect is best when the mass ratio of the hydrophilic ZnMTZ to the DMBIM is 1:1, as shown in figure 3. Hydrophobic ZnMTZ cannot be obtained when the mass ratio of hydrophilic ZnMTZ to DMBIM is 1:0.5 and 1:3.
Example 3
Hydrophobic ZnMTZ was prepared using different solvents ethanol, n-butanol and n-propanol, the other conditions being the same as in example 1, as shown in fig. 4. Ethanol, n-butanol and n-propanol are all less efficient solvents than methanol.
Example 4
Hydrophobic ZnMTZ prepared using different organic fatty amines trimethylamine, dimethylamine, triethylamine, diethylamine and ethylamine, other conditions were the same as in example 1, as shown in fig. 5, with triethylamine as the organic fatty amine having the best efficiency.
Comparative example 1
The procedure of example 1 was followed except that 5, 6-dimethyl-benzimidazole in step (2) of example 1 was replaced with 2-methylimidazole. As a result, it was found that the ligand substitution on the hydrophilic ZnMTZ was successful, but all the ligands were replaced, CO 2 The capture capacity is reduced by half.
Comparative example 2
The procedure of example 1 was followed except that 5, 6-dimethyl-benzimidazole in step (2) of example 1 was replaced with 2-ethylimidazole. As a result, it was found that the ligand substitution on the hydrophilic ZnMTZ failed, the coordination ability was weaker than that of the original MTZ, and the reaction could not be spontaneously conducted.
Comparative example 3
The 5, 6-dimethyl-benzimidazole of step (2) of example 1 was replaced with benzimidazole, with the other conditions being the same as in example 1. As a result, it was found that ligand substitution was successful but converted to a new complex, which could not be used for CO 2 Capturing.
Claims (5)
1. The preparation method of the surface modified hydrophobic triazole zinc salt material is characterized by comprising the following steps of:
(1) Preparation of hydrophilic zinc triazoles ZnMTZ: mixing 25% ammonia water, 0.02-0.04 mol/L zinc acetate aqueous solution and 0.02-0.04 mol/L1-hydrogen-3-methyl-1, 2, 4-triazole aqueous solution at a volume ratio of 0.125 (0.75-1.25): (1.5-2.5), stirring at room temperature at a rotating speed of 400-700 rpm for reaction of 3-7 h, filtering after the reaction is finished, washing 3-5 times with methanol solvent, and vacuum drying at 50-80 ℃;
(2) Mixing hydrophilic ZnMTZ, 5, 6-dimethyl-benzimidazole, an organic alcohol solvent and organic fatty amine, stirring at 50-70 ℃ for reaction 18-36 h, washing the obtained solid precipitate with a methanol solvent for 3-5 times, washing with dichloromethane for 1-3 times, and vacuum drying at 50-100 ℃;
the mass ratio of the hydrophilic ZnMTZ to the 5, 6-dimethyl-benzimidazole to the organic alcohol solvent to the organic fatty amine is 1 (1-2) (160-200) (0.7-1.4);
the organic alcohol solvent is methanol; the organic fatty amine is triethylamine.
2. The surface-modified hydrophobic zinc triazole material obtained by the preparation method according to claim 1, wherein the surface-modified hydrophobic zinc triazole material is covered with 5, 6-dimethyl-benzimidazole by coordination of microporous sodalite type 3-methyl-1, 2, 4-zinc triazole.
3. Use of a surface-modified hydrophobic zinc triazole salt material according to claim 2, characterized in that it is used for CO 2 Is a capture of (a).
4. CO based on the surface modified hydrophobic zinc triazole salt material of claim 2 2 The capturing device is characterized by comprising a condenser (1) at the front end of a separation column, a glass wool (2), a surface modified hydrophobic triazole zinc salt material filler (3) and a fixed bed filler column (4) which are connected with the separation column through pipelines.
5. The CO of claim 4 2 The capturing device is characterized in that the glass wool (2) is one of quartz fiber, aluminum silicate fiber or polymer fiber.
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