CN114505071B - Preparation method and application of MnTi-MOFs derivative denitration catalyst - Google Patents
Preparation method and application of MnTi-MOFs derivative denitration catalyst Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 65
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 239000011572 manganese Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 61
- 239000000243 solution Substances 0.000 claims description 27
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 26
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 102000020897 Formins Human genes 0.000 claims description 6
- 108091022623 Formins Proteins 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000003915 air pollution Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 23
- 239000000843 powder Substances 0.000 description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/618—Surface area more than 1000 m2/g
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- B01J37/08—Heat treatment
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Abstract
The invention discloses a preparation method and application of a MnTi-MOFs-based derivative denitration catalyst, and belongs to the field of air pollution control. The preparation method comprises the following steps: dissolving an organic ligand (terephthalic acid) in a mixed solution of methanol and DMF, adding manganese nitrate tetrahydrate and isopropyl titanate serving as Mn sources and Ti sources into the mixed solution under the stirring condition, transferring into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 150 ℃, centrifuging, washing, drying, preparing a yellow MnTi-MOFs precursor material in situ in one step, and calcining the MnTi-MOFs precursor material at a certain temperature to obtain the composite catalyst. The catalyst obtained by the invention is prepared in NH 3 The SCR has excellent catalytic activity (denitration efficiency reaches more than 90% at 150-360 ℃), good nitrogen selectivity and sulfur resistance, and has good application prospect.
Description
Technical Field
The invention relates to a preparation method and application of a MnTi-MOFs derivative denitration catalyst, and belongs to the technical field of air pollution control.
Background
Nitrogen Oxides (NO) x ) As one of the most serious air pollutants, a number of serious environmental problems are caused, and with the enhancement of environmental awareness and the increasing strictness of regulatory policies, the efficient removal and emission reduction of nitrogen oxides have been proposed by environmental protection departments and schedules of various production units. NH (NH) 3 SCR is the most widely used NO at present x Effective control means. In order to meet the more complex practical application requirements in the denitration field, a high-efficiency catalyst with excellent low-temperature activity and certain sulfur resistance is widely paid attention to by researchers. Manganese oxide has variable cation valence state, surface unstable oxygen and excellent oxidation-reduction performance, and is prepared by using the method 3 Exhibit great potential in SCR reactions. However, the efficiency of manganese-based denitration catalysts is still limited by NO x Conversion of (N) 2 Selectivity, operating temperature window, and the effect of inactivating species. While TiO 2 The doped manganese oxide can effectively reduce the formation of ammonium sulfate or ammonium bisulfate and inhibit the vulcanization of metal active sites, thereby improving the sulfur resistance of the catalyst. Therefore, how to combine the redox characteristics of manganese and titanium and fully develop the synergistic effect of manganese-titanium bimetallic has become an important point of research. The Metal Organic Frameworks (MOFs) are porous crystal materials synthesized by coordination connection of metal ions and organic ligands, and have the advantages of large specific surface area, large pore volume, regular structure, metal active site dispersion and the like. The metal ions can be used as vertexes of the framework to provide a center and form branches in the center, so that the framework of the material is extended to form a multi-dimensional framework structure. It is the unique structure and configuration of a material that determines its characteristics that are not possessed by other materials.
Disclosure of Invention
For the existing NH 3 The invention provides an in-situ preparation method and application of a MnTi-MOFs derivative denitration catalyst. According to the invention, MIL-125 (Ti) is used as a matrix, mn element is in-situ introduced into the MIL-125 structure, and Mn and Ti are effectively assembled. Calcining the MnTi-MOFs precursor to prepare the catalyst with good low-temperature activity, wide temperature window and N 2 NH with high selectivity and high water-resistance and sulfur-resistance 3 SCR catalysisAnd (3) an agent.
According to the invention, MOFs is used as a catalyst precursor, mn and Ti are introduced into the same MOFs frame, so that the characteristics of large specific surface area and high dispersion of active centers of MOFs materials can be utilized, and the synergistic catalysis of two metals can be exerted to the greatest extent; the derivative catalyst greatly improves the working efficiency of the catalyst at low temperature on the premise of fully utilizing the advantages of the manganese oxide. Specifically, mn and Ti are effectively assembled in situ through MOFs precursor by taking the advantages of Mn and Ti as the cut-in points in a synergistic way, and the oxidation-reduction property and the acid-base property of the derivative denitration catalyst are optimized by adjusting the proportion of a ligand to metal elements and the proportion between the two metal elements, so that the MnTi-MOFs precursor material is successfully prepared.
The invention provides a preparation method of a MnTi-MOFs derivative denitration catalyst, which comprises the steps of taking manganese nitrate tetrahydrate and isopropyl titanate as raw materials, taking terephthalic acid as a ligand, taking a mixed solution of methanol and DMF (N, N-dimethylformamide) as a solvent, preparing the solution, uniformly stirring, carrying out hydrothermal treatment, centrifuging, washing and drying to obtain a MnTi-MOFs precursor; the precursor is then calcined to obtain the derivative denitration catalyst.
The preparation method specifically comprises the following steps:
(1) Preparing organic ligand solution
Adding N, N-dimethylformamide and methanol into a beaker, stirring for 5-15 min by using a magnetic stirrer to uniformly mix, adding terephthalic acid into the beaker, and continuing stirring until the terephthalic acid is completely dissolved, so that the solution is clear;
the volume ratio of the methanol to the N, N-Dimethylformamide (DMF) mixed solution is controlled to be DMF, wherein methanol=8-18:2;
(2) Preparation of MOFs precursors
Weighing manganese nitrate tetrahydrate solid, adding the manganese nitrate tetrahydrate solid into the solution for dissolving the ligand in the step (1), placing the solution on a magnetic stirrer for stirring uniformly until the solution is clear, then adding isopropyl titanate, continuously stirring for 20-30 min until the mixed solution becomes a viscous paste, then sealing the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and heating the mixed solution in an oven at 120-150 ℃ for 8-24 h;
(3) Centrifuging
Cooling the reaction kettle to room temperature, transferring the turbid solution in the reaction kettle into a 50 mL centrifuge tube, centrifuging in the centrifuge for 10-20 min, pouring out the supernatant after the centrifugation is finished, and reserving the precipitate;
(4) Washing
Adding 20-40 mL of N, N-dimethylformamide into a centrifuge tube, shaking until the sediment at the bottom is uniformly dispersed, putting the centrifuge tube into a centrifuge for re-centrifugation, repeating the operation twice, changing the N, N-dimethylformamide into methanol, and repeating the centrifugal washing operation once again;
(5) Drying
Placing the centrifuged and washed products into a surface dish, and drying the products in an oven at 80 ℃ for 8-24 h to prepare a MnTi-MOFs precursor;
(6) Calcination
The prepared MnTi-MOFs precursor is put into a muffle furnace and is treated for 2-10 ℃ for min under the air atmosphere -1 Setting the temperature rising rate of the furnace temperature to be 400 ℃ from the room temperature program, and obtaining the MnTi-MOFs derivative denitration catalyst after the furnace temperature is cooled to 20 ℃.
In the above method, the organic ligand in the step (1) is terephthalic acid, and the stirring speed is 500 rpm when the organic ligand is dissolved, and the temperature is 30+ -2 ℃.
In the above method, in the step (2), c (H) 2 BDC) c (M) is controlled to be 3:1-4:1 (c (M) =c (Mn) 2+ ) + c(Ti 4+ )). I.e. the molar ratio of terephthalic acid to metal M is 3: 1-4: 1. wherein c (H) 2 BDC) means H in a mixed solution 2 The mass concentration of BDC (terephthalic acid) species, c (Mn) 2+ ) Means Mn in the mixed solution 2+ The mass concentration of the substance, c (Ti 4+ ) Refers to Ti in the mixed solution 4+ The concentration of the substance in the amount.
Further, in the step (2), c (Mn 2+ ):c(Ti 4+ ) =1:10 to 3:10, i.e. the molar ratio of manganese nitrate tetrahydrate to isopropyl titanate is 1: 10-3: 10. wherein c (Mn) 2+ ) Refers to mixingMn in solution 2+ The mass concentration of the substance, c (Ti 4+ ) Refers to Ti in the mixed solution 4+ The concentration of the substance in the amount.
The invention provides a MnTi-MOFs derivative denitration catalyst prepared by the preparation method.
The invention provides the MnTi-MOFs derivative denitration catalyst in NH 3 -use in SCR reactions.
When the catalyst is applied, the MnTi-MOFs derivative denitration catalyst is firstly pressed into tablets: and tabletting the calcined sample, and sieving the sample into particles with 40 to 60 meshes to obtain the denitration catalyst.
The invention provides the denitration catalyst in NH 3 The application in SCR reactions, the specific reaction conditions are as follows: the total flow of the gas is 120 mL min -1 ，[NO]=500 ppm， [NH 3 ]=500 ppm，[O 2 ]=5.0 %，N 2 As balance gas, airspeed is 36000 h -1 The activity test temperature range is 90-360 ℃. Activity data were collected after the reaction reached equilibrium. The products were analyzed by MultiGas 6030 FTIR (MKS) detection, NO conversion and N 2 The selectivity is calculated by the following formula:
。
the invention has the beneficial effects that:
(1) The raw materials used in the invention are cheap and easy to obtain, and are harmless to human health and ecological environment, and belong to an environment-friendly catalytic system.
(2) The method of the invention provides a method for constructing a catalyst with highly dispersed catalyst surface active centers (Mn): mn is introduced into the skeleton structure of MIL-125 in situ, and the properties of Mn and Ti are coordinated by means of the characteristics of the multidimensional skeleton structure of MOFs, so that the synergistic effect of two metals is exerted.
(3) According to the invention, mn is introduced in situ, a small amount of Mn element ensures that the derived catalyst is not easy to agglomerate, the proportion of Mn and Ti is optimized, so that the high dispersibility of the catalyst can be ensured, the synergistic effect of Mn and Ti can be exerted to the greatest extent, and the denitration efficiency of the derived catalyst at low temperature is greatly improved on the premise of fully utilizing the advantages of manganese oxide.
(4) The catalyst prepared by MOFs precursor has large specific surface area and is prepared by NH 3 Excellent catalytic performance in SCR reaction, good activity under medium and low temperature conditions (150-330 ℃) and high N 2 Selectivity and excellent water-resistance and sulfur-resistance.
Drawings
FIG. 1 is a FT-IR spectrum of a MnTi-MOFs precursor obtained in example 1.
Fig. 2 is an X-ray diffraction pattern (XRD) of the precursor and final product obtained in example 1 of example 1: (A) is a MnTi-MOFs precursor before roasting; and (B) is a derivative catalyst obtained after final calcination.
FIG. 3 is a Scanning Electron Microscope (SEM) map of MnTi-MOFs precursor in example 1.
FIG. 4 is a Transmission Electron Microscope (TEM) spectrum of a MnTi-MOFs derived denitration catalyst in example 1.
FIG. 5 is an adsorption isotherm plot of the MnTi-MOFs precursor in example 2.
FIG. 6 is a schematic representation of NH of a MnTi-MOFs derived catalyst of application example 1 3 SCR activity test results: ANO x Conversion rate; b: N 2 Selectivity.
FIG. 7 shows the results of sulfur resistance test of MnTi-MOFs derived catalysts in application example 2.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1: c (H) 2 BDC):c(Mn 2+ ) + c(Ti 4+ ) = 3:1，c(Mn 2+ ):c(Ti 4+ ) = 1:10
(1) N, N-dimethylformamide 216, ml was measured, anhydrous methanol 30, ml was placed in a 500 ml beaker and stirred with a magnetic stirrer for 10 minutes to complete the mixing.
(2) Terephthalic acid 10.965 g is weighed, added into the mixed solution of DMF and methanol in (1), and stirred evenly by magnetic force until terephthalic acid is completely dissolved, and the solution is clear.
(3) Adding 0.502 g tetrahydrate manganese nitrate into the clear solution obtained in the step (2) under stirring, adding 6ml isopropyl titanate after the manganese nitrate is dissolved, and stirring for 10 min.
(4) The resulting mixed solution was then sealed in a polytetrafluoroethylene-lined stainless steel reaction kettle and hydrothermally treated in an oven at 150±2 ℃ for 18 h.
(5) After the reaction kettle is naturally cooled, centrifuging the reacted solution to obtain a precipitate, washing the precipitate with N, N-dimethylformamide for 2 times, washing the precipitate with methanol for 1 time, transferring the precipitate into a surface dish, then placing the surface dish into an oven for drying at 80+/-2 ℃ for 12 h, taking out the surface dish, and grinding the surface dish to obtain a yellow fine powder product, wherein the yellow fine powder product is a MnTi-MOFs precursor.
(6) Placing the prepared yellow MnTi-MOFs precursor into a crucible, placing the crucible into a muffle furnace, and heating at 2 ℃ for min -1 Setting the temperature rising process to rise to 400 ℃ from room temperature programming, and finally obtaining the MnTi-MOFs derivative denitration catalyst. Tabletting and sieving the prepared catalyst to 40-60 mesh particles.
FIG. 1 shows the FT-IR spectrum of the MnTi-MOFs precursor obtained in this example at 400-600cm -1 The absorption peak at this point is due to the stretching vibration of M-O (m=mn, ti) in the MnTi-MOFs precursor. The occurrence of this peak demonstrates successful synthesis of MnTi-MOFs precursors.
The crystal structure of the prepared product was characterized by means of an X-ray diffractometer. X-ray diffraction analysis is carried out on the yellow fine powder product obtained in the step (5), the diffraction pattern is shown in figure 2A, and figure 2A shows that MOFs material is arranged at 5 ° -20 ° The unique diffraction peaks, sharp peak shape, combined with the infrared of fig. 1, confirm the successful preparation of MOFs materials. And (3) performing X-ray diffraction analysis on the denitration catalyst in the step (6), wherein a diffraction spectrum is shown in a figure 2B, and the figure 2B shows diffraction peaks of the MnTi composite metal oxide, and has single crystalline phase and higher crystallinity.
A Scanning Electron Microscope (SEM) map of the MnTi-MOFs precursor of this example is shown in FIG. 3. The map shows that: the prepared MnTi-MOFs material presents a uniform square sheet morphology.
A Transmission Electron Microscope (TEM) spectrum of the MnTi-MOFs derived catalyst of this example is shown in FIG. 4. The map shows that: compared with the morphology presented in fig. 3, the MnTi-MOFs derived denitration catalyst obtained by calcination still maintains the basic structure of MOFs.
Example 2: c (H) 2 BDC):c(Mn 2+ ) + c(Ti 4+ ) = 4:1，c(Mn 2+ ):c(Ti 4+ ) = 1:10
(1) N, N-dimethylformamide 216, ml was measured, anhydrous methanol 30, ml was placed in a 500 ml beaker and stirred with a magnetic stirrer for 10 minutes to complete the mixing.
(2) Terephthalic acid 14.62, 14.62 g was weighed and added to the mixed solution of DMF and methanol in (1) and stirred magnetically until the terephthalic acid was completely dissolved, and the solution was clear.
(3) Adding 0.502 g tetrahydrate manganese nitrate into the clear solution obtained in the step (2) under stirring, adding 6ml isopropyl titanate after the manganese nitrate is dissolved, and stirring for 10 min.
(4) The resulting mixed solution was then sealed in a polytetrafluoroethylene-lined stainless steel reaction kettle and hydrothermally treated in an oven at 150±2 ℃ for 18 h.
(5) After the reaction kettle is naturally cooled, centrifuging the reacted solution to obtain a precipitate, washing the precipitate with N, N-dimethylformamide for 2 times, washing the precipitate with methanol for 1 time, transferring the precipitate into a surface dish, then placing the surface dish into an oven for drying at 80+/-2 ℃ for 12 h, taking out the surface dish, and grinding the surface dish to obtain a yellow fine powder product, wherein the yellow fine powder product is a MnTi-MOFs precursor.
(6) Placing the prepared yellow MnTi-MOFs precursor into a crucible, placing the crucible into a muffle furnace, and heating at 2 ℃ for min -1 Setting the temperature rising process to rise to 400 ℃ from room temperature programming, and finally obtaining the MnTi-MOFs derivative denitration catalyst. Tabletting and sieving the prepared catalyst to 40-60 mesh particles.
FIG. 5 is an adsorption isotherm plot of the MnTi-MOFs precursor in this example. In the figure, the adsorption and desorption curve of the MnTi-MOFs precursor shows an I-type isotherm, presents an H4-type hysteresis loop, has the characteristics of microporous materials and has a specific surfaceThe product is up to 1193m 2 And/g, which is in accordance with the characteristics of MOFs materials.
Example 3: c (H) 2 BDC):c(Mn 2+ ) + c(Ti 4+ ) =3:1，c(Mn 2+ ):c(Ti 4+ ) = 2:10
(1) N, N-dimethylformamide (216 ml) was measured, dehydrated methanol (30) ml was placed in a 500 ml beaker, and stirred with a magnetic stirrer for 10 minutes to complete the mixing.
(2) Terephthalic acid 11.962 g is weighed, added into the mixed solution of DMF and methanol in (1), and stirred evenly by magnetic force until terephthalic acid is completely dissolved, and the solution is clear.
(3) Adding 1.005. 1.005 g tetrahydrate manganese nitrate into the clear solution obtained in the step (2) under stirring, adding 6ml isopropyl titanate after the manganese nitrate is dissolved, and stirring for 10 min.
(4) The resulting mixed solution was then sealed in a polytetrafluoroethylene-lined stainless steel reaction kettle and hydrothermally treated in an oven at 150±2 ℃ for 18 h.
(5) After the reaction kettle is naturally cooled, centrifuging the reacted solution to obtain a precipitate, washing the precipitate with N, N-dimethylformamide for 2 times, washing the precipitate with methanol for 1 time, transferring the precipitate into a surface dish, then placing the surface dish into an oven for drying at 80+/-2 ℃ for 12 h, taking out the surface dish, and grinding the surface dish to obtain a yellow fine powder product, wherein the yellow fine powder product is a MnTi-MOFs precursor.
(6) Placing the prepared yellow MnTi-MOFs precursor into a crucible, placing the crucible into a muffle furnace, and heating at 2 ℃ for min -1 Setting the temperature rising process to rise to 400 ℃ from room temperature programming, and finally obtaining the MnTi-MOFs derivative denitration catalyst. Tabletting and sieving the prepared catalyst to 40-60 mesh particles.
Example 4: c (H) 2 BDC):c(Mn 2+ ) + c(Ti 4+ ) =3:1，c(Mn 2+ ):c(Ti 4+ ) = 3:10
(1) N, N-dimethylformamide (216 ml) was measured, dehydrated methanol (30) ml was placed in a 500 ml beaker, and stirred with a magnetic stirrer for 10 minutes to complete the mixing.
(2) Terephthalic acid 12.96 and g are weighed, added into the mixed solution of DMF and methanol in (1), and stirred evenly by magnetic force until terephthalic acid is completely dissolved, and the solution is clear.
(3) Adding 1.506-g-tetrahydrate manganese nitrate into the clear solution obtained in the step (2) under stirring, adding 6-ml isopropyl titanate after the manganese nitrate is dissolved, and stirring for 10 min.
(4) The resulting mixed solution was then sealed in a polytetrafluoroethylene-lined stainless steel reaction kettle and hydrothermally treated in an oven at 150±2 ℃ for 18 h.
(5) After the reaction kettle is naturally cooled, centrifuging the reacted solution to obtain a precipitate, washing the precipitate with N, N-dimethylformamide for 2 times, washing the precipitate with methanol for 1 time, transferring the precipitate into a surface dish, then placing the surface dish into an oven for drying at 80+/-2 ℃ for 12 h, taking out the surface dish, and grinding the surface dish to obtain a yellow fine powder product, wherein the yellow fine powder product is a MnTi-MOFs precursor.
(6) Placing the prepared yellow MnTi-MOFs precursor into a crucible, placing the crucible into a muffle furnace, and heating at 2 ℃ for min -1 Setting the temperature rising process to rise to 400 ℃ from room temperature programming, and finally obtaining the MnTi-MOFs derivative denitration catalyst. Tabletting and sieving the prepared catalyst to 40-60 mesh particles.
Application example 1: conversion of catalyst with N 2 Selectivity of
The catalysts prepared in examples 1, 2, 3 and 4 were each packed in a quartz reaction tube. The test temperature is 90-360 ℃, one test point is taken at intervals of 30 ℃, and each test point is kept for 20 minutes. The NOx conversion is shown in fig. 6, and it can be seen from the graph that the NOx conversion can reach more than 90% at 150 ℃ in the catalyst of embodiment 3.
FIG. 6 shows NH of the present example MnTi-MOFs derived catalyst 3 SCR activity test results: ANO x Conversion rate; b: N 2 Selectivity. As can be seen from the figure, N is in the range of 90-240 DEG C 2 Selectivity is higher than 90%, the catalyst N 2 The selectivity exhibited some decrease.
Application example 2: SO-resistant catalyst 2 Evaluation of Performance
For MnTi-MO prepared in example 3Fs derived catalyst. SO resistance is carried out 2 The results of the performance evaluation are shown in figure 7. The catalyst has excellent sulfur resistance performance when 100ppm SO 2 When added, the NOx conversion rate can be maintained at about 50 percent, and the NOx conversion rate is equal to SO 2 After removal of NO x The conversion was restored to about 56%, and after the catalyst was thermally regenerated, the NOx conversion was restored to about 82%. Specific reaction conditions are as follows: the test apparatus was the same as the catalyst amount and application example 1. The composition of the reaction gas is 500 ppm NO,500 ppm NH 3 ，5% O 2 ，100 ppm SO 2 ，N 2 As balance gas, the space velocity of the reaction gas is 36000 h -1 The reaction temperature was 210 ℃.
FIG. 7 shows the results of sulfur resistance tests of MnTi-MOFs derived catalysts in this example. In the initial stage, no SO is added into the flue gas 2 The catalytic activity of the MnTi-MOFs derivative catalyst is kept at about 94%. Subsequently, 100ppm SO was added to the flue gas 2 SO resistance after 6h 2 Testing of NO of final MnTi-MOFs derived catalyst x The conversion rate is reduced to about 50 percent, when SO is removed 2 After that, mnTi-MOFs derivative catalyst NO x The conversion rate is recovered to a certain extent, and then the conversion rate is subjected to heat regeneration treatment, and the catalyst NO x The conversion rate is greatly improved and finally maintained at about 80%. This demonstrates that MnTi-MOFs derived catalysts exhibit excellent SO resistance 2 Performance.
Claims (8)
1. The preparation method of the MnTi-MOFs derivative denitration catalyst is characterized by comprising the following steps of: manganese nitrate tetrahydrate and isopropyl titanate are used as raw materials, terephthalic acid is used as a ligand, and a mixed solution of methanol and DMF is used as a solvent, and MnTi-MOFs precursor is prepared through the steps of solution preparation, uniform stirring, hydrothermal treatment, centrifugation, washing and drying; then calcining the precursor to obtain a derivative denitration catalyst;
the preparation method of the MnTi-MOFs derivative denitration catalyst comprises the following steps:
(1) Preparing organic ligand solution
Adding N, N-dimethylformamide and methanol into a beaker, stirring for 5-15 min by using a magnetic stirrer to uniformly mix, adding terephthalic acid into the beaker, and continuing stirring until the terephthalic acid is completely dissolved, so that the solution is clear;
the volume ratio of the methanol to the N, N-Dimethylformamide (DMF) mixed solution is controlled to be DMF, wherein methanol=8-18:2;
(2) Preparation of MOFs precursors
Weighing manganese nitrate tetrahydrate solid, adding the manganese nitrate tetrahydrate solid into the solution for dissolving the ligand in the step (1), placing the solution on a magnetic stirrer for stirring uniformly until the solution is clear, then adding isopropyl titanate, continuously stirring for 20-30 min until the mixed solution becomes a viscous paste, then sealing the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and heating the mixed solution in an oven at 120-150 ℃ for 8-24 h;
(3) Centrifuging
Cooling the reaction kettle to room temperature, transferring the turbid solution in the reaction kettle into a 50 mL centrifuge tube, centrifuging in the centrifuge for 10-20 min, pouring out the supernatant after the centrifugation is finished, and reserving the precipitate;
(4) Washing
Adding 20-40 mL of N, N-dimethylformamide into a centrifuge tube, shaking until the sediment at the bottom is uniformly dispersed, putting the centrifuge tube into a centrifuge for re-centrifugation, repeating the operation twice, changing the N, N-dimethylformamide into methanol, and repeating the centrifugal washing operation once again;
(5) Drying
Placing the centrifuged and washed products into a surface dish, and drying the products in an oven at 80 ℃ for 8-24 h to prepare a MnTi-MOFs precursor;
(6) Calcination
The prepared MnTi-MOFs precursor is put into a muffle furnace and is treated for 2-10 ℃ for min under the air atmosphere -1 Setting the temperature rising rate of the furnace temperature to be 400 ℃ from the room temperature program, and obtaining the MnTi-MOFs derivative denitration catalyst after the furnace temperature is cooled to 20 ℃.
2. The method for preparing the MnTi-MOFs-derived denitration catalyst according to claim 1, wherein the method comprises the following steps: the organic ligand terephthalic acid in the step (1) is completely dissolved, the stirring speed is 500 rpm when the organic ligand is dissolved, and the temperature is 30+/-2 ℃.
3. The method for preparing the MnTi-MOFs-derived denitration catalyst according to claim 1, wherein the method comprises the following steps: in the step (2), c (H) 2 BDC) c (M) is controlled to be 3:1-4:1, namely the mol ratio of terephthalic acid to metal M is 3: 1-4: 1, a step of; wherein c (H) 2 BDC) means terephthalic acid H in a mixed solution 2 The mass concentration of BDC species, c (M) =c (Mn 2+ ) + c(Ti 4 + )；c(Mn 2+ ) Means Mn in the mixed solution 2+ The mass concentration of the substance, c (Ti 4+ ) Refers to Ti in the mixed solution 4+ The concentration of the substance in the amount.
4. The method for preparing the MnTi-MOFs-derived denitration catalyst according to claim 1, wherein the method comprises the following steps: in the step (2), c (Mn) 2+ ):c(Ti 4+ ) =1:10 to 3:10, where c (Mn 2+ ) Means Mn in the mixed solution 2+ The mass concentration of the substance, c (Ti 4+ ) Refers to Ti in the mixed solution 4+ The concentration of the substance in the amount.
5. A MnTi-MOFs derived denitration catalyst prepared by the preparation method of any one of claims 1 to 4.
6. A MnTi-MOFs derivative denitration catalyst as defined in claim 5 in NH 3 -use in SCR reactions.
7. The use according to claim 6, characterized in that: when the catalyst is applied, the MnTi-MOFs derivative denitration catalyst is firstly pressed into tablets: and tabletting the calcined sample, and sieving the sample into particles with 40 to 60 meshes to obtain the denitration catalyst.
8. The use according to claim 6, characterized in that: the reaction conditions were as follows: the total flow of the gas is 120 mL min -1 ，[NO]=500 ppm， [NH 3 ]=500 ppm，[O 2 ]=5.0 %，N 2 As balance gas, airspeed is 36000 h -1 The activity test temperature range is 90-360 ℃; acquiring activity data after the reaction reaches equilibrium; conversion of NO and N 2 The selectivity is calculated by the following formula:
。
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