CN111617807A - Fe modified nano manganese oxide/MIL-125 (Ti) catalyst and preparation method thereof - Google Patents
Fe modified nano manganese oxide/MIL-125 (Ti) catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 229910016978 MnOx Inorganic materials 0.000 claims abstract description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 229910001868 water Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 14
- 229940099596 manganese sulfate Drugs 0.000 claims description 10
- 239000011702 manganese sulphate Substances 0.000 claims description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims description 10
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 15
- 238000004108 freeze drying Methods 0.000 abstract description 7
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 208000005374 Poisoning Diseases 0.000 description 9
- 231100000572 poisoning Toxicity 0.000 description 9
- 230000000607 poisoning effect Effects 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Classifications
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- B01J35/60—
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
Abstract
The invention belongs to the technical field of composite material preparation, and particularly relates to a Fe modified nano manganese oxide/MIL-125 (Ti) catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: A. mixing MnSO4、NaClO3Ultrasonically mixing with NaCl in deionized water; adding ferric trichloride hexahydrate for ultrasonic treatment; then, dripping concentrated sulfuric acid into the solution under the condition of ice bath stirring, and reacting in a reaction kettle; B. centrifugally washing the precipitate with absolute ethyl alcohol and deionized water, drying, grinding, and calcining in a muffle furnace to obtain iron-modified nano MnOx; C. DMSO and C3H8Mixing O, adding 1,3,5-BTC and nano MnOx for ultrasonic treatment, stirring at room temperature, and adding C dropwise12H28O4Ti; putting the solution into a reaction kettle for reaction; and finally, centrifugally washing with isopropanol and water, and freeze-drying to obtain the composite catalyst. The composite catalyst can effectively reduce the conversion temperature of nitrogen oxides, improve the toxicity resistance and prolong the service life of the catalyst.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a Fe modified nano manganese oxide/MIL-125 (Ti) catalyst and a preparation method thereof.
Background
In recent years, the problem of air pollution is more and more seriousHas received high attention from government departments and the public. And strict policy criteria are established. The atmospheric pollutants in China mainly come from the combustion process of fossil fuels such as coal, petroleum and the like, SO the atmospheric pollutants have SO2NOx, VOC, CO, PM2.5, etc. NOx is secondary dust, SO2The important emission reduction object is to a great extent that NOx causes damage to the natural environment such as acid rain, photochemical smog, ozone layer damage, greenhouse effect and the like, and also poses a threat to human health. The development of NOx control technology has had a considerable history, generally classified into 3 categories: pre-combustion NOx control techniques, in-combustion NOx control techniques, and post-combustion NOx control techniques. However, the NOx control technology before and during combustion has a limited effect on NOx emission reduction, and especially, two methods before and during combustion cannot meet the requirements after the ultralow emission standard is implemented in industries such as coal-fired power plants, steel enterprises and the like in China. And the NOx control technology after combustion has the advantage of high removal efficiency and is the most powerful guarantee for reducing NOx pollution.
Post-combustion NOx control techniques include ammonia selective catalytic reduction (NH)3-SCR), selective non-catalytic reduction (SNCR), activated carbon adsorption, liquid absorption, etc. Among the methods, the Selective Catalytic Reduction (SCR) technology has the advantages that the purification rate can reach more than 90 percent and the process equipment is compact, so that the SCR technology obtains the approval of countries with strict smoke emission standards such as Japan, Europe, America and the like and is widely used; after China pays attention to the atmospheric environment treatment, SCR is also a main technology adopted by the flue gas denitration in China at present.
The catalyst mainly used in the SCR technology is V2O5As the main active ingredient, WO3Or MoO3As an auxiliary agent, TiO2The catalyst is a carrier system and has a good catalytic effect at 300-450 ℃. However, in order to achieve the optimal catalytic temperature of the catalyst, the temperature of the gas needs to be raised to a temperature range of 300-450 ℃, which results in high energy consumption and high treatment cost.
MOFs materials (Meta organic frameworks), i.e., metal organic framework structures, are composed of organic ligands and metal ions or ion clusters, and are ordered by coordinationA porous material having a network structure. Because the skeleton of the MOFs is formed by combining a large number of metal sites and organic ligands with adjustable structures, the MOFs can be self-assembled through different organic ligands, and strong interaction exists between metal ions and the organic ligands, so that the MOFs have the advantages of high specific surface area, more pore channel structures, high thermal stability, various and variable structures and the like. The MOFs is adopted as the catalyst to be applied to the SCR system, SO that the SCR system has a good low-temperature denitration effect and strong SO resistance2anti-H2And (4) O performance. MIL-125(Ti) is one of MOFs materials, is formed by self-assembling an octamer of Ti-O octahedrons formed by titanium atoms and six oxygen atoms and organic acid, and has a three-dimensional porous structure. The metal atoms are tightly combined with the ligand, and the framework structure can still keep not collapsing after the solvent or guest molecules are removed.
Disclosure of Invention
Aiming at the technical defects that gas needs to be heated to 300-450 ℃ when nitrogen oxides are treated by SCR (selective catalytic reduction), energy consumption is high and cost is high, the invention provides a preparation method of a composite catalyst material which takes an MIL-125(Ti) material as a substrate and takes an iron modified nano manganese oxide as a reinforcement to be loaded on the substrate. The composite catalyst has a lower reaction temperature range and has a good prevention effect on catalyst poisoning.
In order to achieve the purpose, the invention adopts the following technical scheme:
A. mixing a certain amount of manganese sulfate solution and sodium chlorate (NaClO)3) Dissolving NaCl and the NaCl in deionized water according to a certain proportion, and carrying out ultrasonic treatment for 5min to uniformly mix; then adding a certain amount of ferric chloride hexahydrate, and carrying out ultrasonic treatment for 10min again. Then, concentrated sulfuric acid was added dropwise slowly with constant stirring in an ice bath to form a clear solution. After the dripping is finished, putting the mixture into a reaction kettle to react for 5 to 8 hours at the temperature of between 120 and 150 ℃.
B. And after the reaction, centrifugally washing the obtained precipitate twice by using absolute ethyl alcohol and deionized water respectively, drying at 70 ℃, grinding the washed and dried precipitate, putting the ground and dried precipitate into a muffle furnace, calcining at 400 ℃ for 10min, and quickly heating to 600 ℃ for calcining for 2-3 h to obtain the iron-doped modified nano MnOx.
C. Adding trimesic acid (1,3,5-BTC) and a certain amount of modified nano MnOx into a mixed solution of dimethyl sulfoxide and isopropanol, and ultrasonically mixing for 20 min; then adding a certain amount of tetraisopropyl titanate (C)12H28O4Ti), stirring at room temperature for 20 min. After stirring, the solution was transferred to a polytetrafluoroethylene liner and synthesized in a reaction kettle. After the reaction, the reaction mixture was washed with isopropanol and water by centrifugation. And finally, freeze-drying in a vacuum freeze dryer to obtain the Fe modified nano manganese oxide/MIL-125 (Ti) catalyst.
Preferably, the molar ratio of manganese sulfate to sodium chlorate in the step A is 1: 2.5-1: 4; the molar ratio of the manganese sulfate to the ferric trichloride hexahydrate is 10-20; the mole number of NaCl is 5-10 times that of manganese sulfate; the molar ratio of the manganese sulfate to the concentrated sulfuric acid is 1: 15-1: 20.
Preferably, the temperature rise speed of the muffle furnace in the step B is 8 ℃/min; and C, the temperature of the reaction kettle in the step C is 160-180 ℃, and the reaction time is 4-6 h.
Preferably, C in step C12H28O4The addition amount of Ti is 1.5 ml-2.7 ml; adding 0.45g to 1.8g of MnOx prepared in the step B; c12H28O4The molar ratio of Ti to 1,3,5-BTC is 1: 2.2-1: 8; 1,3,5-BTC and C3H8The molar ratio of O is 1: 3.75-1: 10; c3H8The molar ratio of O to DMSO is 1: 3-1: 5.3.
The invention also provides a catalyst prepared by the preparation method of the Fe modified nano manganese oxide/MIL-125 (Ti) catalyst.
Has the advantages that: the SCR catalyst prepared by the invention effectively widens the operating temperature window for treating nitrogen oxides, and has good conversion rate to NOx within the temperature range of 200-385 ℃. On the one hand, MIL-125(Ti) as a metal organic framework compound has abundant holes and specific surface area, and the preparation of MIL-125(Ti) enables more Ti active sites to be exposed and treated, thereby being beneficial to the conversion of NOx. On the other hand, the Mn element has rich variable valence and strong oxidation-reduction capability, and can treat nitrogen oxideThe determinant of (1); whereas oxides of manganese have a high surface acid content and a high proportion of Lewis acids that act at relatively low temperatures, and are well suited for NOx catalysis at relatively low temperatures. Manganese oxide is excellent in catalytic performance, but is inferior in sulfur resistance performance, and is liable to undergo sulfur poisoning. The sulfur poisoning of the manganese oxide at a lower temperature is mainly caused by accumulation of ammonium sulfate or ammonium bisulfate covering active sites of the catalyst or blocking catalyst channels, so that the manganese oxide is compounded with MIL-125(Ti) with larger and more pores to reduce the conditions of blocking the channels and covering the active sites on the one hand, and the generation of metal sulfate is prevented by doping Fe on the other hand, and (NH) is inhibited simultaneously4)2SO4And NH4HSO4The deposition of the catalyst improves the antitoxic performance of the catalyst. And the introduction of the iron substance can also interact with Ti to increase the number of surface oxygen vacancies and improve the oxidation-reduction capability of the iron substance at a low temperature stage. In summary, MIL-125(Ti), MnOx and Fe can interact with each other to generate a synergistic effect, and the reaction temperature and the toxicity probability of the composite catalyst are reduced.
Drawings
FIG. 1 is a flow chart of the preparation of the composite catalyst according to the present invention;
FIG. 2 is a 500nm Scanning Electron Microscope (SEM) image of a composite catalyst prepared in example 1 according to the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) image of 50nm of a composite catalyst prepared in example 1 according to the present invention;
FIG. 4 shows the temperature-NO for examples 1 to 4 according to the invention and comparative examples 1 and 22A schematic of conversion;
FIG. 5 shows the results of example 1 of the present invention and comparative example 1 in use H2O and SO2NO before and after poisoning2A conversion comparison graph;
FIG. 6 shows the results of example 1 of the present invention and comparative example 1 in use H2O and SO2Maximum NO before and after poisoning2Bar graph of conversion.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The method comprises the following steps: 0.01mol of MnSO40.025mol of sodium chlorate NaClO3And 2.925g of NaCl are dissolved in 50ml of deionized water, and the mixture is evenly mixed by ultrasonic for 5 min; then 0.135g of ferric chloride hexahydrate is added and the mixture is sonicated again for 10 min. Then 8ml of concentrated sulfuric acid was added slowly dropwise with constant stirring in an ice bath to form a clear solution. After the dropping is finished, the mixture is put into a reaction kettle to react for 8 hours at the temperature of 120 ℃.
Step two: after 8h, centrifugally washing the precipitate of the solution by using absolute ethyl alcohol, and then centrifugally washing by using deionized water; and then putting the mixture into an oven at 70 ℃ for drying. And after drying, putting the mixture into a mortar for grinding, then calcining the mixture in a muffle furnace at 400 ℃ for 10min, and then heating the mixture to 600 ℃ at the speed of 8 ℃/min for calcining for 2h to obtain the iron-doped modified nano MnOx.
Step three: 42.5ml of DMSO and 15.3ml of C3H8Mixing O, adding 4.2g of trimesic acid (1,3,5-BTC) and 0.45g of modified nano MnOx into the mixed solution, and performing ultrasonic treatment for 20min to uniformly distribute the solute; 2.7ml of tetraisopropyl titanate (C) are then added12H28O4Ti), stirring at room temperature for 20 min. After stirring, the solution is transferred to a polytetrafluoroethylene lining and reacted for 6 hours at the temperature of 160 ℃ by a reaction kettle. After the reaction is finished, washing twice by using an isopropanol core and washing once by using deionized water in a centrifugal mode; and (3) after washing, putting the mixture into a vacuum freeze dryer for freeze drying to obtain the Fe modified nano manganese oxide/MIL-125 (Ti) catalyst.
Example 2
The method comprises the following steps: 0.008mol of MnSO40.032mol of sodium chlorate NaClO3Dissolving 4.69g of NaCl in 50ml of deionized water, and carrying out ultrasonic treatment for 5min to uniformly mix; then 0.216g of ferric chloride hexahydrate is added and the mixture is sonicated again for 10 min. Then continuously stirring in an ice bath and slowly dropping 8.6ml of concentrated sulfuric acid,a clear solution was formed. After the dripping is finished, the mixture is put into a reaction kettle to react for 5 hours at the temperature of 150 ℃.
Step two: same as in example 1.
Step three: 56.7ml of DMSO and 11.5ml of C3H8Mixing O, adding 8.4g of trimesic acid (1,3,5-BTC) and 1.8g of modified nano MnOx into the mixed solution, and performing ultrasonic treatment for 20min to uniformly distribute the solute; then 1.5ml of tetraisopropyl titanate (C) were added12H28O4Ti), stirring at room temperature for 20 min. After stirring, the solution is transferred to a polytetrafluoroethylene lining and reacted for 4 hours in a reaction kettle at the temperature of 180 ℃. After the reaction is finished, washing twice by using an isopropanol core and washing once by using deionized water in a centrifugal mode; and (3) after washing, putting the mixture into a vacuum freeze dryer for freeze drying to obtain the Fe modified nano manganese oxide/MIL-125 (Ti) catalyst.
Example 3
The method comprises the following steps: 0.01mol of MnSO40.032mol of sodium chlorate NaClO3Dissolving 3.5g of NaCl in 50ml of deionized water, and carrying out ultrasonic treatment for 5min to uniformly mix; then 0.2g of ferric chloride hexahydrate is added and the mixture is sonicated again for 10 min. Then, 9ml of concentrated sulfuric acid was added dropwise slowly with constant stirring in an ice bath to form a clear solution. After the dripping is finished, the mixture is put into a reaction kettle to react for 5.5 hours at the temperature of 140 ℃.
Step two: same as in example 1.
Step three: 50ml of DMSO and 14ml of C3H8Mixing O, adding 6.3g of trimesic acid (1,3,5-BTC) and 1.5g of modified nano MnOx into the mixed solution, and performing ultrasonic treatment for 20min to uniformly distribute the solute; then 2ml of tetraisopropyl titanate (C) were added12H28O4Ti), stirring at room temperature for 20 min. After stirring, the solution is transferred to a polytetrafluoroethylene lining and reacted for 5 hours at the temperature of 170 ℃ by a reaction kettle. After the reaction is finished, washing twice by using an isopropanol core and washing once by using deionized water in a centrifugal mode; and (3) after washing, putting the mixture into a vacuum freeze dryer for freeze drying to obtain the Fe modified nano manganese oxide/MIL-125 (Ti) catalyst.
Example 4
The method comprises the following steps: 0.01mol ofMnSO of40.04mol of sodium chlorate NaClO3Dissolving 4.2g of NaCl in 50ml of deionized water, and carrying out ultrasonic treatment for 5min to uniformly mix; then 0.18g of ferric chloride hexahydrate is added and the mixture is sonicated again for 10 min. Then, 9ml of concentrated sulfuric acid was added dropwise slowly with constant stirring in an ice bath to form a clear solution. After the completion of the dropwise addition, the mixture was placed in a reaction vessel to react at 130 ℃ for 7 hours.
Step two: same as in example 1.
Step three: mixing 45ml of DMSO and 13.5ml of C3H8Mixing O, adding 7.2g of trimesic acid (1,3,5-BTC) and 1.2g of modified nano MnOx into the mixed solution, and performing ultrasonic treatment for 20min to uniformly distribute the solute; then 2ml of tetraisopropyl titanate (C) were added12H28O4Ti), stirring at room temperature for 20 min. After stirring, the solution was transferred to a teflon liner and reacted for 6h at 165 ℃. After the reaction is finished, washing twice by using an isopropanol core and washing once by using deionized water in a centrifugal mode; and (3) after washing, putting the mixture into a vacuum freeze dryer for freeze drying to obtain the Fe modified nano manganese oxide/MIL-125 (Ti) catalyst.
Comparative example 1
The comparative example is a conventional commercial V available from Hebei2O5-WO3/TiO2A catalyst.
Comparative example 2
The method comprises the following steps: 0.01mol of MnSO40.015mol of sodium chlorate NaClO3Dissolving 4.5g of NaCl in 50ml of deionized water, and carrying out ultrasonic treatment for 5min to uniformly mix; then 0.4g of ferric chloride hexahydrate is added and the mixture is sonicated again for 10 min. Then, 15ml of concentrated sulfuric acid was added dropwise slowly with constant stirring in an ice bath to form a clear solution. After the completion of the dropwise addition, the mixture was put into a reaction kettle to react at 110 ℃ for 9 hours.
Step two: after 9h, centrifugally washing the precipitate of the solution by using absolute ethyl alcohol, and then centrifugally washing by using deionized water; and then putting the mixture into an oven at 70 ℃ for drying. And after drying, putting the mixture into a mortar for grinding, then calcining the mixture in a muffle furnace at 400 ℃ for 10min, and then heating the mixture to 600 ℃ at the speed of 5 ℃/min for calcining for 1h to obtain the iron-doped modified nano MnOx.
Step three: 30ml of DMSO and 20ml of C3H8Mixing O, adding 5g of trimesic acid (1,3,5-BTC) and 1g of modified nano MnOx into the mixed solution, and performing ultrasonic treatment for 20min to uniformly distribute the solute; 4ml of tetraisopropyl titanate (C) are then added12H28O4Ti), stirring at room temperature for 20 min. After stirring, the solution is transferred to a polytetrafluoroethylene lining and reacted for 5 hours at the temperature of 150 ℃ by a reaction kettle. After the reaction is finished, washing twice by using an isopropanol core and washing once by using deionized water in a centrifugal mode; after washing, the obtained product is put into a vacuum freeze dryer for freeze-drying to obtain the composite catalyst without the preferred scheme of the invention.
Examples 1-4 were prepared using the method for preparing the composite catalyst according to the present invention, comparative example 1 being an SCR catalyst produced in the prior art, and comparative example 2 being a composite catalyst not prepared according to the preferred conditions of the present invention. For the analysis of their reaction temperature and the conversion of nitrogen oxides, the treatment of industrial waste gases was simulated in the laboratory, with NO2The gases mixed according to a certain proportion obtain NO of six catalysts in the temperature rising process2And (4) conversion rate. The composite catalyst prepared by the invention can improve the toxicity resistance of the composite catalyst, so that the example 1 obtained by the preparation method of the invention and the comparative example 1 obtained by the prior art are placed in the maximum NO shown in the figure2At the temperature corresponding to the conversion rate, simultaneously introducing H into the system2O-SO2Poisoning the mixed gas for 12 h; NO is carried out again after poisoning2The conversion was tested and compared to the data before poisoning to obtain a comparison of FIGS. 4 and 5.
Fig. 2 is an SEM image of example 1, and it can be seen that the MIL-125(Ti) has a mean diameter of about 60nm, which is small enough to accommodate nano-oxides of manganese, while it can be seen from the 50nm TEM image of fig. 3 that the cage of MIL-125 is indeed loaded with nano-species. This shows that the Fe modified nanometer manganese oxide/MIL-125 (Ti) catalyst is successfully prepared according to the preparation method of the invention.
FIG. 4 is a graph of examples 1-4 and comparative examples 1, 2 versus temperature-NO2Schematic representation of conversion. It can be seen from the figure that examples 1-4 and comparative example 2 are at around 150 deg.CHas already started to do with NO2Wherein examples 1-4 are approximately at about 31% and comparative example 2 is approximately 13%, whereas comparative example 1 starts the conversion at 180 ℃ and requires approximately 250 ℃ to achieve 30% conversion; the conversion rates of examples 1-4 rose rapidly, reaching 80% conversion rates at around 170 c and then increased rapidly by more than 90%, with the lowest effective process temperature being controlled at around 200 c. The rate of increase of the conversion rate of comparative example 2 is significantly inferior to that of example, and the highest conversion rate is only about 82%; it can be seen that the material prepared according to the preferred embodiment of the present invention performs better than the non-preferred embodiment. The final conversion of comparative example 1 is not much different from that of the examples, but the increase of the conversion curve of comparative example 1 is smoother in view of the whole and is not as good as that of the composite catalyst of the present invention; moreover, temperatures of about 320 ℃ and 360 ℃ are required to achieve 80% and 90% conversion respectively. Therefore, the Fe modified nano manganese oxide/MIL-125 (Ti) catalyst can greatly reduce the temperature required by the reaction, and achieves the aim of the invention.
FIGS. 5 and 6 are graphs comparing the conversion rates of example 1 and comparative example 1 before and after poisoning, and FIG. 5 is a graph mainly showing a comparison of the increase rates of the conversion rates after poisoning, and it can be seen that the influence of poisoning on the increase rates of the conversion rates of example 1 and comparative example 1 is not large overall, mainly expressed in NO2At maximum conversion. FIG. 6 is maximum NO before and after poisoning2The conversion rate is compared with a graph, and the maximum NO can be seen more visually2The conversion rate is reduced, but the reduction amplitude of example 1 is not large, which indicates that the degree of catalyst poisoning is small; the maximum conversion rate of comparative example 1 is greatly reduced, and the influence is very obvious. This shows that the Fe modified nano manganese oxide/MIL-125 (Ti) catalyst of the invention effectively improves the toxicity resistance of the catalyst.
In general, from a comparison of data analysis of the materials prepared in the examples and comparative examples, the Fe-modified nano-manganese oxide/MIL-125 (Ti) catalyst of the present invention is compared to V of the prior art2O5-WO3/TiO2The catalyst greatly reduces the temperature required when the nitrogen oxide is treated,meanwhile, the poisoning risk of the catalyst is reduced, the service life of the catalyst is prolonged, and the corresponding defects of the prior art are successfully overcome.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention.
Claims (5)
1. A preparation method of a Fe modified nano manganese oxide/MIL-125 (Ti) catalyst is characterized by comprising the following steps:
A. dissolving a certain amount of manganese sulfate solution, sodium chlorate and NaCl in deionized water according to a certain proportion, and carrying out ultrasonic treatment for 5min to uniformly mix; then adding ferric trichloride hexahydrate, and carrying out ultrasonic treatment for 10min again. Then, concentrated sulfuric acid was added dropwise slowly with constant stirring in an ice bath to form a clear solution. After the dripping is finished, putting the mixture into a reaction kettle to react for 5 to 8 hours at the temperature of between 120 and 150 ℃;
B. after reaction, centrifugally washing the obtained precipitate with absolute ethyl alcohol and deionized water, drying, grinding, calcining in a muffle furnace at 400 ℃ for 10min, and quickly heating to 600 ℃ for calcining for 2-3 h to obtain iron-doped modified nano MnOx;
C. adding trimesic acid and modified nano MnOx into a mixed solution of dimethyl sulfoxide and isopropanol, and ultrasonically mixing for 20 min; then adding a certain amount of tetraisopropyl titanate (C)12H28O4Ti), stirring for 20min at room temperature; then transferring the solution into a reaction kettle for reaction; the temperature of the reaction kettle is 160-180 ℃, the reaction time is 4-6 hours, after the reaction is finished, isopropanol and water are used for centrifugally washing the obtained precipitate, and the precipitate is freeze-dried in a vacuum freeze dryer to prepare the Fe modified nano manganese oxide/MIL-125 (Ti) catalyst;
the molar ratio of manganese sulfate to sodium chlorate in the step A is 1: 2.5-1: 4; the molar ratio of the manganese sulfate to the ferric trichloride hexahydrate is 10-20; the mole number of NaCl is 5-10 times that of manganese sulfate; the molar ratio of the manganese sulfate to the concentrated sulfuric acid is 1: 15-1: 20.
2. The method for preparing the Fe-modified nano manganese oxide/MIL-125 (Ti) catalyst according to claim 1, wherein the drying temperature in the step B is 70 ℃, and the temperature rise rate of the muffle furnace is 8 ℃/min.
3. The method of claim 1, wherein in step C, C is the amount of Fe-modified nano manganese oxide/MIL-125 (Ti) catalyst used in the preparation of the catalyst12H28O4The molar ratio of Ti to 1,3,5-BTC is 1: 2.2-1: 8; 1,3,5-BTC and C3H8The molar ratio of O is 1: 3.75-1: 10; c3H8The molar ratio of O to DMSO is 1: 3-1: 5.3.
4. The method for preparing Fe-modified nano manganese oxide/MIL-125 (Ti) catalyst according to any one of claims 1 to 3, wherein C in the step C12H28O4The addition amount of Ti is 1.5 ml-2.7 ml; and adding 0.45g to 1.8g of MnOx prepared in the step B.
5. The catalyst prepared by the preparation method of the Fe modified nano manganese oxide/MIL-125 (Ti) catalyst according to any one of claims 1 to 4.
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