CN114505071A - Preparation method and application of MnTi-MOFs derived denitration catalyst - Google Patents
Preparation method and application of MnTi-MOFs derived 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 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 69
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 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 43
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 27
- 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 10
- 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
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 30
- 239000011521 glass Substances 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000012216 screening 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 14
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 23
- 229910052748 manganese Inorganic materials 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000000843 powder Substances 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
- 230000002195 synergetic effect Effects 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 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
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 239000012495 reaction gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 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
- 238000003915 air pollution Methods 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health 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
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 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
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- 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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- 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
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Abstract
The invention discloses a preparation method and application of a MnTi-MOFs-based derived denitration catalyst, and belongs to the field of atmospheric pollution control. The preparation method comprises the following steps: dissolving organic ligand (terephthalic acid) in mixed solution of methanol and DMF (dimethyl formamide), adding manganese nitrate tetrahydrate and isopropyl titanate serving as a Mn source and a Ti source into the mixed solution under the condition of stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 150 ℃, centrifuging, washing, drying, and performing one-step reactionPreparing a yellow MnTi-MOFs precursor material in situ, and calcining the MnTi-MOFs precursor material at a certain temperature to obtain the composite catalyst. The catalyst obtained by the invention is used in NH3The SCR has excellent catalytic activity (the denitration efficiency at 360 ℃ of 150-.
Description
Technical Field
The invention relates to a preparation method and application of a MnTi-MOFs derived denitration catalyst, belonging to the technical field of air pollution prevention and control.
Background
Nitrogen Oxides (NO)x) As one of the most serious air pollutants, causes a lot of serious environmental problems, and as people's environmental awareness increases and legislation policies become stricter, efficient removal and emission reduction of nitrogen oxides have been proposed in the schedule of environmental protection departments and various production units. NH (NH)3SCR is currently the most widely used NOxEffective control means. In order to meet the more complex practical application requirements in the field of denitration, efficient catalysts with excellent low-temperature activity and certain sulfur resistance have received extensive attention of researchers. Oxides of manganese NH at low temperatures due to their variable cationic valency, surface labile oxygen and excellent redox properties3-shows great potential in SCR reactions. However, the efficiency of manganese-based denitration catalysts is still limited by NOxConversion of (2), N2Selectivity, operating temperature window, and the effect of deactivating species. And TiO 22The 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 exert the synergistic effect of the manganese-titanium bimetal is the key point of research. The metal organic framework Materials (MOFs) are porous crystal materials synthesized by coordination and connection of metal ions and organic ligands, and have the advantages of large specific surface area, large pore volume, regular structure, dispersed metal active sites and the like. The metal ions can be used as the vertexes of the skeleton to provide a central pivot and form branches at the central pivot, so that the skeleton of the material is extended to form a multi-dimensional framework structure. It is the unique structure and configuration of the material that determines its unique characteristics that are not shared with other materials.
Disclosure of Invention
For existing NH3The invention relates to a defect of SCR catalyst application, and provides an in-situ preparation method and application of a MnTi-MOFs derived denitration catalyst. According to the invention, MIL-125(Ti) is used as a matrix, and Mn element is introduced into the MIL-125 structure in situ, so that Mn and Ti are effectively assembled. Calcining MnTi-MOFs precursor to prepare N with good low-temperature activity, wide temperature window2High-selectivity, water-resistant and sulfur-resistant NH3-an SCR catalyst.
According to the invention, MOFs is used as a catalyst precursor, and Mn and Ti are introduced into the same MOFs frame, so that the characteristics of large specific surface area and highly dispersed active centers of the MOFs material can be utilized, and the synergistic catalytic action of two metals can be exerted to the maximum extent; the work efficiency of the derivative catalyst at low temperature is greatly improved on the premise of fully utilizing the advantages of the manganese oxide. Specifically, the MnTi-MOFs precursor material is successfully prepared by taking the advantages of Mn and Ti as an entry point, effectively assembling Mn and Ti in situ through the MOFs precursor, and optimizing the oxidation-reduction property and the acidity-basicity of the derivative denitration catalyst by modulating the ratio of a ligand to a metal element and the ratio between the two metal elements.
The invention provides a preparation method of a MnTi-MOFs derived denitration catalyst, which takes manganese nitrate tetrahydrate and isopropyl titanate as raw materials, takes terephthalic acid as a ligand, and takes a mixed solution of methanol and DMF (N, N-dimethylformamide) as a solvent, and prepares a MnTi-MOFs precursor through the steps of solution preparation, uniform stirring, hydrothermal treatment, centrifugation, washing and drying; and calcining the precursor 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 continuously stirring until the terephthalic acid is completely dissolved, so that the solution is clear;
the volume ratio of the mixed solution of the methanol and the N, N-Dimethylformamide (DMF) is controlled to be DMF: methanol = 8-18: 2;
(2) preparation of MOFs precursors
Weighing manganese nitrate tetrahydrate solid, adding the solid into the solution in which the ligand is dissolved in the step (1), placing the solution on a magnetic stirrer, uniformly stirring the solution until the solution is clear, then adding isopropyl titanate, continuing stirring the solution for 20-30 min until the mixed solution becomes viscous paste, then sealing the mixed solution in 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) centrifugation
Cooling the reaction kettle to room temperature, transferring the turbid solution in the reaction kettle into a 50 mL centrifugal tube, centrifuging in a centrifuge for 10-20 min, pouring out the supernatant after the centrifugation is finished, and keeping the precipitate;
(4) washing machine
Adding 20-40 mL of N, N-dimethylformamide into a centrifuge tube, shaking until bottom sediment is uniformly dispersed, then placing the centrifuge tube into a centrifuge for centrifuging again, repeating the operation twice, then replacing N, N-dimethylformamide with methanol, and repeating the operation of centrifuging and washing once again;
(5) drying
Placing the centrifuged and washed product in a watch glass, and putting the watch glass and the washed product together in an oven at 80 ℃ for drying for 8-24 h to prepare a MnTi-MOFs precursor;
(6) calcination of
Putting the prepared MnTi-MOFs precursor into a muffle furnace, and carrying out air atmosphere at the temperature of 2-10 ℃ for min-1And setting the temperature rise process to be from room temperature to 400 ℃ in the temperature rise rate, and obtaining the MnTi-MOFs derived denitration catalyst after the furnace temperature is cooled to 20 ℃.
In the method, the organic ligand in the step (1) is terephthalic acid, 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) is2BDC (c) c (M) is controlled to be 3: 1-4: 1 (c (M) = c (Mn)2+) + c(Ti4+)). I.e. a molar ratio of terephthalic acid to metal M of 3: 1-4: 1. wherein c (H)2BDC) refers to H in the mixed solution2BDC (terephthalic acid)) Amount concentration of substance, c (Mn)2+) Refers to Mn in the mixed solution2+Mass concentration of substance, c (Ti)4+) Means Ti in the mixed solution4+The quantitative concentration of the substance.
Further, in the step (2), c (Mn)2+):c(Ti4+) And =1: 10-3: 10, namely the molar ratio of manganese nitrate tetrahydrate to isopropyl titanate is 1: 10-3: 10. wherein c (Mn)2+) Refers to Mn in the mixed solution2+Mass concentration of substance, c (Ti)4+) Refers to Ti in the mixed solution4+The quantitative concentration of the substance.
The invention provides a MnTi-MOFs derived denitration catalyst prepared by the preparation method.
The invention provides application of the MnTi-MOFs derived denitration catalyst in NH3-use in an SCR reaction.
When in application, the MnTi-MOFs derived denitration catalyst is firstly tableted: and tabletting the calcined sample, and screening into particles of 40-60 meshes to obtain the prepared denitration catalyst.
The invention provides a method for preparing the denitration catalyst in NH3-use in SCR reactions, specific reaction conditions are as follows: the total flow rate of gas is 120 mL min-1，[NO]=500 ppm， [NH3]=500 ppm，[O2]=5.0 %，N2As balance gas, the space velocity is 36000 h-1The temperature range of the activity test is 90-360 ℃. Activity data were collected after the reaction reached equilibrium. Product analysis by MultiGas 6030 FTIR (MKS) detection, NO conversion and N2The 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 easily available, are harmless to human health and ecological environment, and belong to an environment-friendly catalytic system.
(2) The invention provides a method for constructing a catalyst with highly dispersed catalyst surface active centers (Mn): mn is introduced into the framework structure of MIL-125 in situ, and the properties of Mn and Ti are coordinated by means of the characteristics of the multi-dimensional framework structure of the MOFs material, so that the synergistic effect of the two metals is exerted.
(3) According to the invention, Mn is introduced in situ, a small amount of Mn element enables the derived catalyst not to easily agglomerate, the ratio of Mn and Ti is optimized, the high dispersibility of the catalyst can be ensured, the synergistic effect of Mn and Ti can be exerted to the maximum 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 from MOFs precursor has large specific surface area and high activity on NH3Excellent catalytic performance in SCR reaction, good activity under medium and low temperature (150-330 ℃) and high N2Selectivity and excellent water-resistant and sulfur-resistant performance.
Drawings
FIG. 1 is an FT-IR spectrum of MnTi-MOFs precursor obtained in example 1.
Fig. 2 is an X-ray diffraction pattern (XRD) of the precursor and the final product obtained in example 1 of example 1: (A) is a MnTi-MOFs precursor before roasting; (B) is the derivative catalyst obtained after final calcination.
FIG. 3 is a Scanning Electron Microscope (SEM) image of MnTi-MOFs precursor in example 1.
FIG. 4 is a Transmission Electron Microscope (TEM) image of the MnTi-MOFs-derived denitration catalyst of example 1.
FIG. 5 is an adsorption isotherm plot of MnTi-MOFs precursors in example 2.
FIG. 6 is NH of MnTi-MOFs derived catalyst of application example 13-SCR activity test results: a is NOxConversion rate; b is N2And (4) selectivity.
FIG. 7 shows the results of the sulfur resistance test of the MnTi-MOFs derived catalyst of application example 2.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1: c (H)2BDC):c(Mn2+) + c(Ti4+) = 3:1，c(Mn2+):c(Ti4+) = 1:10
(1) 216ml of N, N-dimethylformamide and 30 ml of anhydrous methanol were measured, and the mixture was placed in a 500 ml beaker and stirred with a magnetic stirrer for 10 min to be completely mixed.
(2) 10.965 g of terephthalic acid is weighed and added into the mixed solution of DMF and methanol in the step (1), and the mixture is stirred evenly by magnetic force until the terephthalic acid is completely dissolved, and the solution is clear.
(3) Adding 0.502 g of manganese nitrate tetrahydrate into the clear solution obtained in the step (2) under the condition of stirring, adding 6ml of isopropyl titanate after the manganese nitrate is dissolved, and continuing stirring for 10 min.
(4) And then the obtained mixed solution is hermetically placed in a stainless steel reaction kettle with a polytetrafluoroethylene lining, and is subjected to hydrothermal treatment for 18 hours in an oven at the temperature of 150 +/-2 ℃.
(5) And after the reaction kettle is naturally cooled, centrifuging the solution after reaction to obtain a precipitate, washing the precipitate for 2 times by using N, N-dimethylformamide, washing the precipitate for 1 time by using methanol, transferring the precipitate into a watch glass, then drying the watch glass in an oven at the temperature of 80 +/-2 ℃ for 12 hours, taking out the watch glass, and grinding the watch glass to obtain a yellow fine powder product, wherein the product is the MnTi-MOFs precursor.
(6) Placing the prepared yellow MnTi-MOFs precursor in a crucible, placing the crucible in a muffle furnace, and heating at 2 ℃ for min-1And setting the temperature rise process to be from room temperature to 400 ℃ in a programmed manner, and finally obtaining the MnTi-MOFs derived denitration catalyst. The prepared catalyst is tabletted and sieved to 40-60 mesh particles.
FIG. 1 shows the FT-IR spectrum of the MnTi-MOFs precursor obtained in this example at 400-600cm-1The absorption peak at (b) is due to stretching vibration of M-O (M = Mn, Ti) in the MnTi-MOFs precursor. The appearance of this peak demonstrates the successful synthesis of MnTi-MOFs precursors.
This example characterizes the crystal structure of the product prepared by means of an X-ray diffractometer. Performing X-ray diffraction analysis on the yellow fine powder product obtained in the step (5), wherein the diffraction spectrum of the product is shown in figure 2A, and figure 2A shows that the MOFs material is 5°-20°The characteristic diffraction peak has sharp peak shape, and the MO can be determined by combining the infrared rays of figure 1Fs materials were successfully prepared. And (3) carrying out X-ray diffraction analysis on the denitration catalyst in the step (6), wherein the diffraction spectrogram is shown as figure 2B, and figure 2B shows the diffraction peak of the MnTi composite metal oxide, and the denitration catalyst has a single crystal phase and high crystallinity.
A Scanning Electron Microscope (SEM) spectrum of the MnTi-MOFs precursor of the present example is shown in FIG. 3. The map shows that: the prepared MnTi-MOFs material presents a uniform square sheet shape.
A Transmission Electron Microscopy (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)2BDC):c(Mn2+) + c(Ti4+) = 4:1，c(Mn2+):c(Ti4+) = 1:10
(1) 216ml of N, N-dimethylformamide and 30 ml of anhydrous methanol were measured, and the mixture was placed in a 500 ml beaker and stirred with a magnetic stirrer for 10 min to be completely mixed.
(2) 14.62 g of terephthalic acid was weighed, added to the mixed solution of DMF and methanol in (1), and stirred by magnetic force until the terephthalic acid was completely dissolved, and the solution was clarified.
(3) Adding 0.502 g of manganese nitrate tetrahydrate into the clear solution obtained in the step (2) under the condition of stirring, adding 6ml of isopropyl titanate after the manganese nitrate is dissolved, and continuing stirring for 10 min.
(4) And then the obtained mixed solution is hermetically placed in a stainless steel reaction kettle with a polytetrafluoroethylene lining, and is subjected to hydrothermal treatment for 18 hours in an oven at the temperature of 150 +/-2 ℃.
(5) And after the reaction kettle is naturally cooled, centrifuging the solution after reaction to obtain a precipitate, washing the precipitate for 2 times by using N, N-dimethylformamide, washing the precipitate for 1 time by using methanol, transferring the precipitate into a watch glass, then drying the watch glass in an oven at the temperature of 80 +/-2 ℃ for 12 hours, taking out the watch glass, and grinding the watch glass to obtain a yellow fine powder product, wherein the product is the MnTi-MOFs precursor.
(6) Placing the prepared yellow MnTi-MOFs precursor in a crucible, placing the crucible in a muffle furnace, and heating at 2 ℃ for min-1The rate of temperature rise of (a) is,and setting the temperature rise process to raise the temperature from room temperature to 400 ℃ in a programmed manner, and finally obtaining the MnTi-MOFs derived denitration catalyst. The prepared catalyst is tabletted and sieved to 40-60 mesh particles.
FIG. 5 is an adsorption isotherm diagram of MnTi-MOFs precursors in this example. In the figure, the adsorption and desorption curve of the MnTi-MOFs precursor shows an I-type isothermal line, shows an H4-type hysteresis loop, has the characteristics of a microporous material, and has a specific surface area up to 1193m2And/g, the characteristics of the MOFs materials are met.
Example 3: c (H)2BDC):c(Mn2+) + c(Ti4+) =3:1，c(Mn2+):c(Ti4+) = 2:10
(1) 216ml of N, N-dimethylformamide and 30 ml of anhydrous methanol were measured, and the mixture was placed in a 500 ml beaker and stirred with a magnetic stirrer for 10 min to be completely mixed.
(2) 11.962 g of terephthalic acid is weighed and added into the mixed solution of DMF and methanol in the step (1), and the mixture is stirred evenly by magnetic force until the terephthalic acid is completely dissolved, and the solution is clear.
(3) Adding 1.005 g of manganese nitrate tetrahydrate into the clear solution obtained in the step (2) under the condition of stirring, adding 6ml of isopropyl titanate after the manganese nitrate is dissolved, and continuing stirring for 10 min.
(4) And then the obtained mixed solution is hermetically placed in a stainless steel reaction kettle with a polytetrafluoroethylene lining, and is subjected to hydrothermal treatment for 18 hours in an oven at the temperature of 150 +/-2 ℃.
(5) And after the reaction kettle is naturally cooled, centrifuging the solution after reaction to obtain a precipitate, washing the precipitate for 2 times by using N, N-dimethylformamide, washing the precipitate for 1 time by using methanol, transferring the precipitate into a watch glass, then drying the watch glass in an oven at the temperature of 80 +/-2 ℃ for 12 hours, taking out the watch glass, and grinding the watch glass to obtain a yellow fine powder product, wherein the product is the MnTi-MOFs precursor.
(6) Placing the prepared yellow MnTi-MOFs precursor in a crucible, placing the crucible in a muffle furnace, and heating at 2 ℃ for min-1And setting the temperature rise process to be from room temperature to 400 ℃ in a programmed manner, and finally obtaining the MnTi-MOFs derived denitration catalyst. The prepared catalyst is tableted and sieved to 40-60 meshes of particles.
Examples4：c(H2BDC):c(Mn2+) + c(Ti4+) =3:1，c(Mn2+):c(Ti4+) = 3:10
(1) 216ml of N, N-dimethylformamide and 30 ml of anhydrous methanol were measured, and the mixture was placed in a 500 ml beaker and stirred with a magnetic stirrer for 10 min to be completely mixed.
(2) 12.96 g of terephthalic acid is weighed and added into the mixed solution of DMF and methanol in the step (1), and the mixture is stirred evenly by magnetic force until the terephthalic acid is completely dissolved, and the solution is clear.
(3) Adding 1.506 g of manganese nitrate tetrahydrate into the clear solution obtained in the step (2) under the condition of stirring, adding 6ml of isopropyl titanate after the manganese nitrate is dissolved, and continuing stirring for 10 min.
(4) And then the obtained mixed solution is hermetically placed in a stainless steel reaction kettle with a polytetrafluoroethylene lining, and is subjected to hydrothermal treatment for 18 hours in an oven at the temperature of 150 +/-2 ℃.
(5) And after the reaction kettle is naturally cooled, centrifuging the solution after reaction to obtain a precipitate, washing the precipitate for 2 times by using N, N-dimethylformamide, washing the precipitate for 1 time by using methanol, transferring the precipitate into a watch glass, then drying the watch glass in an oven at the temperature of 80 +/-2 ℃ for 12 hours, taking out the watch glass, and grinding the watch glass to obtain a yellow fine powder product, wherein the product is the MnTi-MOFs precursor.
(6) Placing the prepared yellow MnTi-MOFs precursor in a crucible, placing the crucible in a muffle furnace, and heating at 2 ℃ for min-1And setting the temperature rise process to be from room temperature to 400 ℃ in a programmed manner, and finally obtaining the MnTi-MOFs derived denitration catalyst. The prepared catalyst is tabletted and sieved to 40-60 mesh particles.
Application example 1: conversion of catalyst and N2Selectivity is selected
The catalysts obtained in examples 1, 2, 3 and 4 were each placed in a quartz reaction tube. And (4) taking a test point every 30 ℃ from 90-360 ℃, and keeping the test point for 20 minutes respectively. The NOx conversion is shown in fig. 6, and it can be seen that the NOx conversion of the catalyst of example 3 can reach 90% or more at 150 ℃.
FIG. 6 shows NH of the MnTi-MOFs derived catalyst of this example3-SCResults of the R Activity test: a is NOxConversion rate; b is N2And (4) selectivity. As can be seen from the figure, N is within the range of 90-240 DEG C2Selectivity higher than 90%, the catalyst N2The selectivity showed some decrease.
Application example 2: catalyst SO resistance2Evaluation of Performance
MnTi-MOFs derived catalyst prepared in example 3. To resist SO2The results of the performance evaluation are shown in FIG. 7. The catalyst has excellent sulfur resistance when the SO content is 100ppm2When the catalyst is added, the NOx conversion rate can still be maintained to be about 50 percent, and the NOx conversion rate can be maintained to be about SO2After removal, NOxThe conversion rate was recovered to about 56%, and after the catalyst was thermally regenerated, the NOx conversion rate was recovered to about 82%. The specific reaction conditions are as follows: the test apparatus and catalyst were used in the same manner as in application example 1. The composition of the reaction gas was 500 ppm NO, 500 ppm NH3，5% O2，100 ppm SO2，N2As balance gas, the space velocity of the reaction gas is 36000 h-1The reaction temperature was 210 ℃.
FIG. 7 shows the results of the sulfur resistance test of the MnTi-MOFs derived catalyst in this example. In the initial stage, no SO is added into the flue gas2The catalytic activity of the MnTi-MOFs derivative catalyst is kept at about 94 percent. Subsequently, 100ppm SO was added to the flue gas2SO resistance over 6h2Testing, NO of the final MnTi-MOFs derived catalystxThe conversion rate is reduced to about 50 percent, and when SO is removed2After that, MnTi-MOFs derived catalyst NOxThe conversion rate is recovered to a certain extent, and then the conversion rate is subjected to thermal regeneration treatment, so that the catalyst NO isxThe conversion rate is greatly improved and finally maintained at about 80 percent. This indicates that MnTi-MOFs derived catalysts exhibit excellent SO resistance2And (4) performance.
Claims (9)
1. A preparation method of a MnTi-MOFs derived denitration catalyst is characterized by comprising the following steps: 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 the MnTi-MOFs precursor is prepared through the steps of solution preparation, uniform stirring, hydrothermal treatment, centrifugation, washing and drying; and calcining the precursor to obtain the derivative denitration catalyst.
2. The method of preparing a MnTi-MOFs derived denitration catalyst according to claim 1, characterized by comprising the steps of:
(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 continuously stirring until the terephthalic acid is completely dissolved, so that the solution is clear;
the volume ratio of the mixed solution of the methanol and the N, N-Dimethylformamide (DMF) is controlled to be DMF: methanol = 8-18: 2;
(2) preparation of MOFs precursors
Weighing manganese nitrate tetrahydrate solid, adding the solid into the solution in which the ligand is dissolved in the step (1), placing the solution on a magnetic stirrer, uniformly stirring the solution until the solution is clear, then adding isopropyl titanate, continuing stirring the solution for 20-30 min until the mixed solution becomes viscous paste, then sealing the mixed solution in 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) centrifugation
Cooling the reaction kettle to room temperature, transferring the turbid solution in the reaction kettle into a 50 mL centrifugal tube, centrifuging in a centrifuge for 10-20 min, pouring out the supernatant after the centrifugation is finished, and keeping the precipitate;
(4) washing machine
Adding 20-40 mL of N, N-dimethylformamide into a centrifuge tube, shaking until bottom sediment is uniformly dispersed, then placing the centrifuge tube into a centrifuge for centrifuging again, repeating the operation twice, then replacing N, N-dimethylformamide with methanol, and repeating the operation of centrifuging and washing once again;
(5) drying
Placing the centrifuged and washed product in a watch glass, and putting the watch glass and the washed product together in an oven at 80 ℃ for drying for 8-24 h to prepare a MnTi-MOFs precursor;
(6) calcination of
Putting the prepared MnTi-MOFs precursor into a muffle furnace, and carrying out air atmosphere at the temperature of 2-10 ℃ for min-1And setting the temperature rise process to be from room temperature to 400 ℃ in the temperature rise rate, and obtaining the MnTi-MOFs derived denitration catalyst after the furnace temperature is cooled to 20 ℃.
3. The method of preparing a MnTi-MOFs derived denitration catalyst according to claim 2, characterized in that: 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 ℃.
4. The method of preparing a MnTi-MOFs derived denitration catalyst according to claim 2, characterized in that: in the step (2), c (H)2BDC), (M) is controlled at 3:1 to 4:1, i.e. the molar ratio of terephthalic acid to metal M is 3: 1-4: 1; wherein c (H)2BDC) refers to the terephthalic acid H in the mixed solution2Amount concentration of BDC substance, c (m) = c (Mn)2+) + c(Ti4 +)；c(Mn2+) Refers to Mn in the mixed solution2+Mass concentration of substance, c (Ti)4+) Refers to Ti in the mixed solution4+The quantitative concentration of the substance.
5. The method of preparing a MnTi-MOFs derived denitration catalyst according to claim 2, characterized in that: in the step (2), c (Mn)2+):c(Ti4+) =1: 10-3: 10, wherein c (Mn)2+) Refers to Mn in the mixed solution2+Mass concentration of substance, c (Ti)4+) Refers to Ti in the mixed solution4+The quantitative concentration of the substance.
6. A MnTi-MOFs derived denitration catalyst prepared by the preparation method of any one of claims 1 to 5.
7. A MnTi-MOFs derived denitration catalyst as set forth in claim 6 in NH3-use in an SCR reaction.
8. Use according to claim 7, characterized in that: when in application, the MnTi-MOFs derived denitration catalyst is firstly tableted: and tabletting the calcined sample, and screening into particles of 40-60 meshes to obtain the prepared denitration catalyst.
9. Use according to claim 7, characterized in that: the reaction conditions were as follows: the total flow rate of gas is 120 mL min-1，[NO]=500 ppm， [NH3]=500 ppm，[O2]=5.0 %，N2As balance gas, the space velocity is 36000 h-1The activity test temperature range is 90-360 ℃; collecting activity data after the reaction reaches equilibrium; NO conversion and N2The selectivity is calculated by the following formula:
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