CN116422352A - Preparation method and application of phosphotungstic acid modified iron-based MOF derivative material - Google Patents
Preparation method and application of phosphotungstic acid modified iron-based MOF derivative material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 24
- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 19
- -1 phosphotungstic acid modified iron Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000000694 effects Effects 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 114
- 239000008247 solid mixture Substances 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 28
- 229910015189 FeOx Inorganic materials 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 23
- 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 22
- 239000012298 atmosphere Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 12
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012692 Fe precursor Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 39
- 239000013291 MIL-100 Substances 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 26
- 239000011259 mixed solution Substances 0.000 description 13
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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 group 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 231100000828 respiratory toxicity Toxicity 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 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
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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Abstract
The invention relates to the field of catalysts, in particular to a preparation method and application of a phosphotungstic acid modified iron-based MOF derivative material. The invention is applied to NH 3 In the SCR reaction, the method mainly aims at improving the problem that the iron-based catalyst is not strong in acidity and not ideal in low-temperature activity, improves the acidity by doping phosphotungstic acid with rich acidity, and simultaneously designs and synthesizes MIL-100 (Fe) with a porous structure as an iron source to increase the specific surface area and disperse active sitesThe dots promote high dispersion and close coupling of the active sites to promote catalytic activity.
Description
Technical Field
The invention relates to the field of catalysts, in particular to preparation and application of a phosphotungstic acid modified iron-based MOF derivative material.
Background
NOx causes serious environmental problems such as photochemical smog, dust haze, acid rain, greenhouse effect, ozone layer destruction and the like, and meanwhile, has stronger biological respiratory toxicity, and causes great harm to ecological environment and human health. Therefore, the control of NOx emissions is enhanced in countries around the world, and the methods for effectively removing NOx at present mainly comprise an absorption method, a catalytic decomposition method, a storage reduction method, a non-selective catalytic denitration method (SNCR), a selective catalytic denitration method (SCR) and the like. With NH 3 SCR technology, which is the most effective NOx removal technology currently accepted, has found industrial application in stationary source flue gas denitration and diesel vehicle exhaust denitration. Agent system in NH 3 Plays a critical role in SCR technology. At present, more catalysts are researched and mainly comprise two main types of molecular sieve catalysts and oxide catalysts, wherein the molecular sieve catalysts have good hydrothermal stability but are easy to SO (sulfur oxide) 2 Poisoning, the oxide catalyst mainly comprises V-base, mn-base, ce-base and Fe-base catalysts, at present V 2 O 5 -WO 3 (MoO 3 )/TiO 2 The catalyst has been successfully applied to denitration of fixed sources and mobile sources, however, the traditional vanadium catalyst has the defects of insufficient low-temperature activity, poor thermal stability and the like in practical application, and vanadium has biotoxicity. Therefore, the research and development of the non-vanadium-based high-efficiency high-resistance SCR catalyst without toxicity and pollution has profound research significance. From an academic and industrial point of view, SCR catalysts should have the following characteristics: (1) a wide operating temperature window; the catalyst has a wide operating temperature window and can adapt to various working conditions. For example, the low-temperature catalyst can be applied to a denitration device after an electric dust removing and desulfurizing device of a power plant, and can be maximally usedDegree of reduction of SO 2 And toxic metals in dust, diesel denitration devices are usually installed after DOC and DPF devices, and DPF systems raise the reaction temperature of exhaust gas, which puts demands on catalysts with good high-temperature activity and stability. (2) SO resistance at low temperature 2 /H 2 The O capacity is strong; h present in flue gas or tail gas 2 O and SO 2 The existence of the catalyst can lead to the deposition of ammonium sulfate, ammonium bisulfate and metal sulfate, further leads to the deactivation of the catalyst, and the decomposition temperature of the sulfate is higher, SO that the development of low-temperature SO resistance is required 2 /H 2 And O to inhibit the formation of sulfate or promote the decomposition of sulfate at low temperature. (3) strong alkali resistance; alkali metal deposition in the flue gas not only reduces the number and strength of the acid sites, but also reduces the redox properties of the active components, which must be protected from these poisoning effects in order to meet various complex operating conditions. While iron oxide catalysts are due to good N 2 Selectivity and SO resistance 2 The ability, coupled with the inherent environmental friendly properties, outstanding thermal stability and low cost, has a broad research prospect. However, pure Fe 2 O 3 The temperature window of the catalyst is narrow, and particularly the low-temperature activity is not ideal. The metal organic framework Material (MOFs) is a novel material composed of organic ligands and inorganic metal center clusters, has the characteristics of larger specific surface area, high porosity, easy adjustment and modification, and the like, has rich and dispersed metal center active sites, and is especially an ideal material for selective catalytic oxidation. Heteropoly acid is a kind of polyoxy group with good oxidation-reduction and acidity, etc. and can be used for catalytic reaction.
The prior China patent (CN 113083371B) discloses a phosphotungstic acid loaded iron-based MOF material, which is prepared by adding phosphotungstic acid into a MOF material precursor solution taking ferric salt and 1,3, 5-benzene tricarboxylic acid as raw materials and adopting a hydrothermal synthesis method, wherein the MOF material is prepared by encapsulating the phosphotungstic acid in a hole cage of MIL-100 (Fe), and the phosphotungstic acid loaded mass percentage is 20-40%. The invention is used for fine desulfurization catalysis and realizes H at normal temperature 2 Selective catalysis of SOxidizing; the phosphotungstic acid component and the unsaturated metal center coordinate with each other to promote the catalytic activity.
Chinese patent (CN 106582874A) discloses a high temperature resistant phosphotungstic acid adsorption type iron-based oxide catalyst and a preparation method thereof, wherein ferroferric oxide is adopted to adsorb and calcine phosphotungstic acid to form an iron-based oxide catalyst which uniformly adsorbs phosphotungstic acid, but the obtained catalyst NH 3 SCR catalytic effect is poor.
Disclosure of Invention
To solve the problem that the iron-based catalyst is applied to NH 3 The invention provides preparation and application of a phosphotungstic acid modified iron-based MOF derivative material, which have the problems of weak acidity and unsatisfactory low-temperature activity in SCR reaction.
In one aspect, the invention provides a method for preparing a phosphotungstic acid modified iron-based MOF derivative material, comprising the following steps:
s1, preparing a solution A: dissolving 1,3, 5-benzene tricarboxylic acid in sodium hydroxide solution, stirring at room temperature to obtain
Solution A;
s2, preparing a solution B: dissolving an iron precursor in water to obtain a solution B;
s3, preparing solid mixture powder D: dropwise adding the solution B into the solution A, stirring at room temperature, and centrifugally washing
Washing, drying and grinding to obtain powder solid D;
s4, preparing a solution C: adding the powder solid D into the aqueous solution, and stirring to obtain a solution C;
s5, preparing a solid mixture E: dissolving phosphotungstic acid hydrate in water to prepare phosphotungstic acid solution, adding the phosphotungstic acid solution into the solution C, stirring at room temperature, completing the reaction in a reaction kettle, and centrifugally washing to obtain solid mixture
An object E;
s6, drying and roasting: drying the solid mixture E at N 2 Roasting under atmosphere, and then roasting under air atmosphere to obtain HPW-FeO x(MOFs) Composite oxide catalysts.
More specifically, in the step S2, the precursor of iron is selected to be ferrous sulfate heptahydrate.
Specifically, in the step S1, the mass concentration of the sodium hydroxide solution substance is 1-5 mol/L.
Specifically, in the step S3, stirring is carried out at room temperature for 20-36 h, and the drying temperature is 100-120 ℃.
More specifically, in the step S3, a mortar grinding manner is selected to improve the grinding quality.
Specifically, in the step S5, the mass ratio of the phosphotungstic acid hydrate to the aqueous solution is 7:100-200.
Specifically, in the step S5, the stirring time at room temperature is 0.5-3 h, the temperature in the reaction kettle is maintained at 120-200 ℃, and the reaction time is 5-36 h.
Specifically, the drying temperature is 100-120 ℃.
Specifically, in the step S6, N 2 The roasting temperature is 300-800 ℃ under the atmosphere, the roasting time is 2-8 h, and the heating rate is5 ℃/min.
Specifically, in the step S6, the roasting temperature is 300-800 ℃ under the air atmosphere, the roasting temperature is 300-800 ℃, the roasting time is 5h, and the heating rate is5 ℃/min.
In the second aspect, the phosphotungstic acid modified iron-based MOF derivative material prepared by the invention is HPW-FeO x(MOFs) Composite oxide catalyst, HPW-FeO x(MOFs) The composite oxide catalyst is used for ammonia selective catalytic reduction of nitrogen oxides, wherein the catalyst with the best activity is used for 50,000h -1 Under airspeed, the conversion rate of nitrogen oxide can reach 80% in the temperature range of 195-485 ℃.
The beneficial effects are that: the invention is applied to NH 3 In the SCR reaction, the method mainly aims at improving the problem that the iron-based catalyst is not strong in acidity and not ideal in low-temperature activity, improves the acidity by doping phosphotungstic acid which contains abundant acidity, and simultaneously designs and synthesizes MIL-100 (Fe) with a porous structure as an iron source to increase the specific surface area, disperse active sites, promote the high dispersion of the active sites and improve the catalytic activity by tight coupling.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and together with the description serve to explain the invention.
FIG. 1 is a graph showing the performance test of catalytic reaction in examples 1-4 and comparative examples 1-2 of the present invention;
FIG. 2 is a graph showing the performance test of the catalytic reaction in examples 5 to 8 of the present invention.
Detailed Description
The following examples further illustrate the invention.
Example 1: HPW (HPW) 0.0076 Preparation of FeOx (MOFs) catalysts
Solution a:1.676g of 1,3, 5-benzene tricarboxylic acid is dissolved in 24mL of 1mol/L sodium hydroxide solution at room temperature and stirred for dissolution to form solution A; solution B:0.011mol of ferrous sulfate heptahydrate is dissolved in 97mL of water to form a solution B; dropwise adding the solution B into 24mL of the solution A, stirring at room temperature for 24h, centrifugally washing for 3 times to obtain a solid mixture MIL-100 (Fe), and drying at 100 ℃; grinding a solid mixture MIL-100 (Fe) into powder by using a mortar, dissolving 1.25g of the powder solid in 40mL of water, and uniformly stirring to obtain a solution C; dissolving 0.125g of phosphotungstic acid hydrate in 10mL of water to prepare a phosphotungstic acid solution, adding the phosphotungstic acid solution into the solution C, stirring at room temperature for 30min to obtain a mixed solution F, transferring the mixed solution F into a 100mL reaction kettle, reacting for 12h at 150 ℃, centrifugally washing for 3 times to obtain a solid mixture E, drying the solid mixture at 100 ℃, and then adding N at 500 DEG C 2 Roasting for 2 hours under the atmosphere, wherein the heating rate is5 ℃/min, then roasting for 5 hours at 500 ℃ under the air atmosphere, and obtaining the HPW 0.0076 -FeOx (MOFs) -500 composite oxide catalysts.
Example 2: HPW (HPW) 0.023 Preparation of FeOx (MOFs) catalysts
Solution a:1.676g of 1,3, 5-benzene tricarboxylic acid is dissolved in 24mL of 1mol/L sodium hydroxide solution at room temperature and stirred for dissolution to form solution A; solution B:0.011mol of ferrous sulfate heptahydrate is dissolved in 97mL of water to form a solution B; dropwise adding the solution B into 24mL of the solution A, stirring at room temperature for 24h, centrifugally washing for 3 times to obtain a solid mixture MIL-100 (Fe), and drying at 100 ℃; grinding a solid mixture MIL-100 (Fe) into powder by using a mortar, dissolving 1.25g of the powder solid in 40mL of water, and uniformly stirring to obtain a solution C; 0.375g of phosphotungstic acid hydrate was dissolved inPreparing a phosphotungstic acid solution by 10mL of water, adding the phosphotungstic acid solution into the solution C, stirring for 30min at room temperature to obtain a mixed solution F, transferring the mixed solution F into a 100mL reaction kettle, reacting for 12h at 150 ℃, centrifugally washing for 3 times to obtain a solid mixture E, drying the solid mixture at 100 ℃, roasting at 500 ℃ for 2h under N2 atmosphere at a heating rate of 5 ℃/min, roasting at 500 ℃ for 5h under air atmosphere at a heating rate of 5 ℃/min to obtain HPW 0.023 -FeOx (MOFs) composite oxide catalysts.
Example 3: HPW (HPW) 0.046 Preparation of FeOx (MOFs) catalysts
Solution a:1.676g of 1,3, 5-benzene tricarboxylic acid is dissolved in 24mL of 1mol/L sodium hydroxide solution at room temperature and stirred for dissolution to form solution A; solution B:0.011mol of ferrous sulfate heptahydrate is dissolved in 97mL of water to form a solution B; dropwise adding the solution B into 24mL of the solution A, stirring at room temperature for 24h, centrifugally washing for 3 times to obtain a solid mixture MIL-100 (Fe), and drying at 100 ℃; grinding a solid mixture MIL-100 (Fe) into powder by using a mortar, dissolving 1.25g of the powder solid in 40mL of water, and uniformly stirring to obtain a solution C; dissolving 0.7g of phosphotungstic acid hydrate in 10mL of water to prepare a phosphotungstic acid solution, adding the phosphotungstic acid solution into the solution C, stirring at room temperature for 30min to obtain a mixed solution F, transferring the mixed solution F into a 100mL reaction kettle, reacting for 12h at 150 ℃, centrifugally washing for 3 times to obtain a solid mixture E, drying the solid mixture at 100 ℃, roasting the solid mixture at 500 ℃ under N2 atmosphere for 2h at a heating rate of 5 ℃/min, and roasting the solid mixture at 500 ℃ for 5h at an air atmosphere at a heating rate of 5 ℃/min to obtain HPW 0.046 -FeOx (MOFs) composite oxide catalysts.
Comparative example 1: preparation of FeOx (MOFs) catalysts
1.676g of 1,3, 5-benzene tricarboxylic acid is dissolved in 24mL of 1mol/L sodium hydroxide solution at room temperature and stirred for dissolution to form solution A; solution B:0.011mol of ferrous sulfate heptahydrate is dissolved in 97mL of water to form a solution B; dropwise adding the solution B into 24mL of the solution A, stirring at room temperature for 24h, centrifugally washing for 3 times to obtain a solid mixture MIL-100 (Fe), and drying at 100 ℃;
the preparation method of FeOx (MOFs) comprises the following steps: dispersing the MIL-100 (Fe) in water, stirring for half an hour, transferring to a reaction kettle, reacting for 12 hours at 150 ℃, washing and drying, roasting for 2 hours at 500 ℃ in a nitrogen atmosphere, heating at a rate of 5 ℃/min, roasting for 5 hours at 500 ℃ in an air atmosphere, and heating at a rate of 2 ℃/min to obtain FeOx (MOFs).
Comparative example 2: HPW (HPW) 0.023 Preparation of FeOx catalyst
The preparation method of Fe (OH) x comprises the following steps: 24mL of 1mol/L sodium hydroxide solution is taken as solution A, and 0.011mol of ferrous sulfate heptahydrate is dissolved in 97mL of water to form solution B; and (3) dropwise adding the solution B into 24mL of the solution A, stirring at room temperature for 24h, centrifugally washing for 3 times, and drying at 100 ℃ to obtain Fe (OH) x.
HPW 0.023 -FeOx preparation method: dispersing the prepared Fe (OH) x in water, adding 0.26mmol of phosphotungstic acid hydrate, stirring for half an hour, transferring to a reaction kettle for reaction at 150 ℃ for 12 hours, washing and drying, roasting at 500 ℃ for 2 hours in nitrogen atmosphere, heating at 5 ℃/min, roasting at 500 ℃ for 5 hours in air atmosphere, and heating at 2 ℃/min to obtain HPW 0.023 -FeOx。
Example 4: evaluation of catalyst Performance
Application of the catalysts prepared in examples 1-3 and comparative examples 1-2, respectively, to NH 3 The SCR reaction, the specific reaction conditions are as follows: catalytic reaction tests were performed in a fixed bed continuous flow quartz reactor. The granularity of the catalyst is 40-60 meshes, the catalyst is arranged in a reaction tube with the outer diameter of 8mm and the inner diameter of 6mm, and the height of the catalyst is 2cm. The composition of the reaction gas is as follows: 500ppm NO,500ppm NH 3 ，5％O 2 ，N 2 As balance gas, the gas space velocity in the reaction is 50000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Catalytic reactions were carried out at 100-400 ℃, activity data were collected after the reaction reached equilibrium, the products were analyzed by Thermofisher °is50FTIR detection, NOx conversion and N2 selectivity were calculated by the following formula:
the measurement results are shown in FIG. 1, HPW 0.023 The catalytic performance of the FeOx (MOFs) catalyst is optimal.
Example 5: HPW (HPW) 0.023 Preparation of the catalyst-FeOx (MOFs) -500
Solution a:1.676g of 1,3, 5-benzene tricarboxylic acid is dissolved in 24mL of 1mol/L sodium hydroxide solution at room temperature and stirred for dissolution to form solution A; solution B:0.011mol of ferrous sulfate heptahydrate is dissolved in 97mL of water to form a solution B; dropwise adding the solution B into 24mL of the solution A, stirring at room temperature for 24h, centrifugally washing for 3 times to obtain a solid mixture MIL-100 (Fe), and drying at 100 ℃; grinding a solid mixture MIL-100 (Fe) into powder by using a mortar, dissolving 1.25g of the powder solid in 40mL of water, and uniformly stirring to obtain a solution C; dissolving 0.375g of phosphotungstic acid hydrate in 10mL of water to prepare a phosphotungstic acid solution, adding the phosphotungstic acid solution into the solution C, stirring at room temperature for 30min to obtain a mixed solution F, transferring the mixed solution F into a 100mL reaction kettle, reacting for 12h at 150 ℃, centrifugally washing for 3 times to obtain a solid mixture E, drying the solid mixture at 100 ℃, and then adding N at 500 DEG C 2 Roasting for 2 hours under the atmosphere, wherein the heating rate is5 ℃/min, then roasting for 5 hours at 500 ℃ under the air atmosphere, and obtaining the HPW 0.023 -FeOx (MOFs) -500 composite oxide catalysts.
Example 6: HPW (HPW) 0.023 Preparation of the catalyst FeOx (MOFs) -600
Solution a:1.676g of 1,3, 5-benzene tricarboxylic acid is dissolved in 24mL of 1mol/L sodium hydroxide solution at room temperature and stirred for dissolution to form solution A; solution B:0.011mol of ferrous sulfate heptahydrate is dissolved in 97mL of water to form a solution B; dropwise adding the solution B into 24mL of the solution A, stirring at room temperature for 24h, centrifugally washing for 3 times to obtain a solid mixture MIL-100 (Fe), and drying at 100 ℃; grinding a solid mixture MIL-100 (Fe) into powder by using a mortar, dissolving 1.25g of the powder solid in 40mL of water, and uniformly stirring to obtain a solution C; dissolving 0.375g of phosphotungstic acid hydrate in 10ml of water to prepare a phosphotungstic acid solution, adding the phosphotungstic acid solution into the solution C, stirring for 30min at room temperature to obtain a mixed solution F, transferring the mixed solution F into a 100ml reaction kettle, reacting for 12h at 150 ℃, and centrifugally washing for 3 timesObtaining a solid mixture E, drying the solid mixture at 100 ℃, and then adding N at 500 DEG C 2 Roasting for 2 hours under the atmosphere, wherein the heating rate is5 ℃/min, then roasting for 5 hours under the air atmosphere at 600 ℃, and obtaining the HPW 0.023 -FeOx (MOFs) -600 composite oxide catalysts.
Example 7: HPW (HPW) 0.023 Preparation of the catalyst FeOx (MOFs) -700
Solution a:1.676g of 1,3, 5-benzene tricarboxylic acid is dissolved in 24mL of 1mol/L sodium hydroxide solution at room temperature and stirred for dissolution to form solution A; solution B:0.11mol of ferrous sulfate heptahydrate is dissolved in 97mL of water to form a solution B; dropwise adding the solution B into 24mL of the solution A, stirring at room temperature for 24h, centrifugally washing for 3 times to obtain a solid mixture MIL-100 (Fe), and drying at 100 ℃; grinding a solid mixture MIL-100 (Fe) into powder by using a mortar, dissolving 1.25g of the powder solid in 40mL of water, and uniformly stirring to obtain a solution C; dissolving 0.375g of phosphotungstic acid hydrate in 10mL of water to prepare a phosphotungstic acid solution, adding the phosphotungstic acid solution into the solution C, stirring at room temperature for 30min to obtain a mixed solution F, transferring the mixed solution F into a 100mL reaction kettle, reacting for 12h at 150 ℃, centrifugally washing for 3 times to obtain a solid mixture E, drying the solid mixture at 100 ℃, roasting the solid mixture at 500 ℃ under N2 atmosphere for 2h at a heating rate of 5 ℃/min, and roasting the solid mixture at 700 ℃ for 5h at a heating rate of 5 ℃/min in air atmosphere to obtain HPW 0.023 -FeOx (MOFs) -700 composite oxide catalysts.
Example 8: HPW (HPW) 0.023 Preparation of the-FeOx (MOFs) -800 catalysts
Solution a:1.676g of 1,3, 5-benzene tricarboxylic acid is dissolved in 24mL of 1mol/L sodium hydroxide solution at room temperature and stirred for dissolution to form solution A; solution B:0.011mol of ferrous sulfate heptahydrate is dissolved in 97mL of water to form a solution B; dropwise adding the solution B into 24mL of the solution A, stirring at room temperature for 24h, centrifugally washing for 3 times to obtain a solid mixture MIL-100 (Fe), and drying at 100 ℃; grinding a solid mixture MIL-100 (Fe) into powder by using a mortar, dissolving 1.25g of the powder solid in 40mL of water, and uniformly stirring to obtain a solution C; dissolving 0.375g of phosphotungstic acid hydrate in 10mL of water to prepare a phosphotungstic acid solution, adding the phosphotungstic acid solution into the solution C, and stirring at room temperature for 30min to obtain a mixed solutionF, transferring the mixed solution F into a 100mL reaction kettle, reacting for 12h at 150 ℃, centrifugally washing for 3 times to obtain a solid mixture E, drying the solid mixture at 100 ℃, roasting the solid mixture at 500 ℃ under N2 atmosphere for 2h at a heating rate of 5 ℃/min, and roasting the solid mixture at 800 ℃ for 5h under air atmosphere at a heating rate of 5 ℃/min to obtain HPW 0.023 -FeOx (MOFs) -800 composite oxide catalysts.
Example 9: evaluation of catalyst Performance
Application of the catalysts prepared in examples 5 to 8, respectively, to NH 3 The SCR reaction, the specific reaction conditions are as follows: catalytic reaction tests were performed in a fixed bed continuous flow quartz reactor. The granularity of the catalyst is 40-60 meshes, the catalyst is arranged in a reaction tube with the outer diameter of 8mm and the inner diameter of 6mm, and the height of the catalyst is 2cm. The composition of the reaction gas is as follows: 500ppm NO,500ppm NH 3 ，5％O 2 ，N 2 As balance gas, the gas space velocity in the reaction is 50000h -1 . The catalytic reaction is carried out at 100-400 ℃, and the activity data is collected after the reaction reaches equilibrium. The product was analyzed by Thermofisher°IS50FTIR detection and the results are shown in FIG. 1. HPW when the catalyst roasting temperature is 500 DEG C 0.023 T90 of-FeOx (MOFs) -500. Apprxeq.205℃.
Although embodiments of the present invention have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents.
Claims (10)
1. A preparation method of a phosphotungstic acid modified iron-based MOF derivative material is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a solution A: dissolving 1,3, 5-benzene tricarboxylic acid in sodium hydroxide solution, and stirring at room temperature to obtain solution A;
s2, preparing a solution B: dissolving an iron precursor in water to obtain a solution B;
s3, preparing solid mixture powder D: dropwise adding the solution B into the solution A, stirring at room temperature, centrifugally washing, drying and grinding to obtain powder solid D;
s4, preparing a solution C: adding the powder solid D into the aqueous solution, and stirring to obtain a solution C;
s5, preparing a solid mixture E: dissolving a phosphotungstic acid hydrate in water to prepare a phosphotungstic acid solution, adding the phosphotungstic acid aqueous solution into the solution C, stirring at room temperature, completing the reaction in a reaction kettle, and centrifugally washing to obtain a solid mixture E;
s6, drying and roasting: drying the solid mixture E at N 2 Roasting under atmosphere, and then roasting under air atmosphere to obtain the HPW-FeOx (MOFs) composite oxide catalyst.
2. The method for preparing a phosphotungstic acid modified iron-based MOF derivative material according to claim 1, wherein in the step S1, the concentration of sodium hydroxide solution substance is 1 to 5mol/L.
3. The method for preparing a phosphotungstic acid modified iron-based MOF derivative material according to claim 1, wherein in the step S3, stirring is performed at room temperature for 20-36 h, and drying temperature is 100-120 ℃.
4. The method for preparing a phosphotungstic acid modified iron-based MOF derivative material according to claim 1, wherein in the step S3, a mortar grinding mode is selected to improve grinding quality.
5. The method for preparing a phosphotungstic acid modified iron-based MOF derivative material according to claim 1, wherein in the step S5, the mass ratio of the phosphotungstic acid hydrate to the aqueous solution is 7:100-200.
6. The method for preparing a phosphotungstic acid modified iron-based MOF derivative material according to claim 1, wherein in the step S5, stirring is performed at room temperature for 0.5-3 hours, the temperature in a reaction kettle is maintained at 120-200 ℃, and the reaction time is 5-36 hours.
7. The method for preparing a phosphotungstic acid modified iron-based MOF derivative material according to claim 1, wherein in the step S6, the drying temperature is 100 to 120 ℃.
8. The method for preparing a phosphotungstic acid modified iron-based MOF derivative material according to claim 7, wherein in said step S6, N 2 The roasting temperature is 300-800 ℃ under the atmosphere, the roasting time is 2-8 h, and the heating rate is5 ℃/min.
9. The method for preparing a phosphotungstic acid modified iron-based MOF derivative material according to claim 8, wherein in the step S6, the roasting temperature is 300-800 ℃ under the air atmosphere, the roasting temperature is 300-800 ℃, the roasting time is 5h, and the heating rate is5 ℃/min.
10. An application of a phosphotungstic acid modified iron-based MOF derivative material is characterized in that: the phosphotungstic acid modified iron-based MOF derivative material is the HPW-FeOx (MOFs) composite oxide catalyst prepared by any one of claims 1 to 9, and the HPW-FeOx (MOFs) composite oxide catalyst is used for ammonia selective catalytic reduction of nitrogen oxides, wherein the catalyst with the optimal activity is used for 50,000h -1 Under airspeed, the conversion rate of nitrogen oxide can reach 80% in the temperature range of 195-485 ℃.
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