CN113134391A - Metal organic complex catalytic material with vanadium-tungsten bimetallic coordination - Google Patents
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 20
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 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 30
- 239000013215 MIL-88B Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000013110 organic ligand Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000004729 solvothermal method Methods 0.000 claims abstract description 4
- -1 tungsten ions Chemical class 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000011056 performance test Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims 5
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 abstract 1
- 239000010937 tungsten Substances 0.000 abstract 1
- 229910001456 vanadium ion Inorganic materials 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 5
- 229910003091 WCl6 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229940125753 fibrate Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/56—Vanadium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/66—Tungsten
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Abstract
The invention discloses a metal organic complex catalytic material with vanadium-tungsten bimetallic coordination, which is characterized in that a novel MIL-88B (V) -W-like metal organic complex is synthesized by a solvothermal method that terephthalic acid organic ligand, trivalent vanadium ions and hexavalent tungsten ions take absolute ethyl alcohol as a solvent, and the metal organic complex has high thermal stability and excellent NOxThe catalytic conversion performance is a novel metal organic complex catalytic material with excellent performance.
Description
Technical Field
The invention relates to a metal organic complex catalytic material with vanadium-tungsten bimetallic coordination, in particular to a bimetallic organic complex generated by combining V metal, W metal and terephthalic acid and a preparation method thereof, and the bimetallic organic complex can be used as a catalytic material. Relates to the synthesis of a metal organic complex, and has good catalytic reaction performance as a novel catalytic material.
Background
The metal organic complex has highly dispersed metal nodes and adjustable denaturation, and has great application potential in the fields of gas adsorption and separation, optics, electricity, magnetism, chemical sensing, heterogeneous catalysis and the like. The Metal Organic Framework (MOFs) material can be directly used as a catalyst, and the huge specific surface area enables the MOFs material to be used as an excellent catalyst carrier. In recent years, modulation and modification of metal organic framework materials have become one of the research hotspots, and many modified metal organic framework materials exhibit more excellent performance.
V with V as active component2O5/TiO2The oxide catalyst has good oxygen storage capacity and excellent oxidation-reduction property on NH3High denitration activity in SCR reaction, wide reaction window and the like (DOI:10.1016/j. apcatb.2007.04.021). In the subsequent studies W ion was added as a cocatalyst to V2O5/TiO2In the oxide catalyst, the addition of W ions enables new B acid sites to be formed in the catalyst, so that the catalytic activity of the catalyst is further improved (DOI: 10.1016/j.jre.2017.06.004). In previous researches, MIL-88B (V) of MOFs material with V ions as metal nodes is in NH3Good catalytic activity in the SCR reaction (DOI: 10.1002/cctc.202001622). In view of the above, the invention uses trivalent V ion and hexavalent W ion as metal node sources to connect with terephthalic acid organic ligand to form a novel MIL-88B (V) -W metal organic complex with high thermal stability, and uses the complex as NH3-novel NO excellent in SCR activityxA conversion catalyst material.
Disclosure of Invention
The invention aims to synthesize a novel MIL-88B (V) -W-like metal organic complex with high thermal stability by using trivalent V ions and hexavalent W ions as metal node sources and connecting the complex with a terephthalic acid organic ligand, and the complex is used as NH3-novel NO excellent in SCR activityxA conversion catalyst material. The invention synthesizes a novel MIL-88B (V) -W metal organic complex by a terephthalic acid organic ligand, trivalent V ions and hexavalent W ions by a solvothermal method, which is compared with the MIL-88B (V) metal organic complexHas better low-temperature NO catalytic conversion activity and can be used as novel NO with excellent SCR activityxA conversion catalyst material.
The invention provides a W-doped V-based metal organic complex catalytic material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) terephthalic acid (H)2BDC) and V salts (VCl)3) And W salt (WCl)6) Dissolving in anhydrous alcohol, stirring at room temperature until all the three are dissolved, adding hydrochloric acid regulator, and stirring. Wherein H2BDC and VCl3And WCl6The feeding molar ratio of (A) to (B) is 0.9-1.1: 0.9-1.1: 0.05 to 0.15, volume of absolute ethyl alcohol and H2The BDC mass proportion is about 20-50 mL:1g, hydrochloric acid concentration of 1mol/L, hydrochloric acid volume dosage and H2The mass ratio of the BDC is about 4-7 mL to 1 g.
(2) And (2) transferring the mixed solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene substrate, transferring the reaction kettle into an oven, raising the temperature to 120-150 ℃ by a program, standing for crystallization for 36-48 hours, then lowering the temperature to room temperature by the program, and taking out the reaction kettle. Wherein the programmed heating and cooling rates are 0.5-1 ℃/min.
(3) And (3) centrifugally separating the green precipitate obtained in the step (2), washing the precipitate with absolute ethyl alcohol for three times, and removing unreacted raw materials. Wherein the volume dosage of the absolute ethyl alcohol used for each washing is about one half of the dosage of the absolute ethyl alcohol used in the synthesis reaction.
(4) And (4) drying the solid product obtained in the step (3) in an oven at 120 ℃ for 24 hours to obtain the MIL-88B (V) -W-like metal organic complex with the solvent removed.
(5) Carrying out NO treatment on the MIL-88B (V) -W-like metal organic complex obtained in the step (4) under certain reaction conditionsxNH of (2)3Reduction to N2The catalytic performance test of (2).
Drawings
FIG. 1 shows NH of MIL-88B (V) -W-like metal-organic complexes obtained in the examples3Reduction elimination of NOxCatalytic performance.
FIG. 2 shows the PXRD crystal phase structure of MIL-88B (V) -W-like metal organic complex obtained in the example.
FIG. 3 shows TG thermal stability of MIL-88B (V) -W-like organometallic complexes obtained in the examples.
FIGS. 4 and 5 show XPS spectra of MIL-88B (V) -W-like metal organic complexes obtained in the examples.
Detailed Description
The present invention will be described in detail below with reference to specific examples, but it should be understood that the present invention is not limited to the examples.
Example 1
(1) Raw materials
Terephthalic acid (H)2BDC) was produced by makelin biochemical science and technology ltd, shanghai, analytically pure (99%); the absolute ethyl alcohol is produced by Tianjin Fuyu fine chemical industry Co., Ltd, and is analytically pure (99.8%); VCl3Analytically pure (99.9%) for Across Orcanics; WCl6Was analytically pure (99.9%) for the production of Aladdin Biotechnology Ltd.
(2) Preparation of synthetic fluid
Terephthalic acid (10mmol,1.6610g), VCl3(10mmol,1.5730g)、WCl6(1mmol,0.3970g) is dissolved in 50mL of absolute ethyl alcohol, and the three are magnetically stirred at normal temperature until the three are completely dissolved, and finally 10mL of hydrochloric acid is added and the mixture is uniformly stirred.
(3) Metal organic complex synthesis
Transferring the mixed solution obtained in the step (2) to a reaction kettle with a 100mL polytetrafluoroethylene substrate, transferring the reaction kettle to a drying oven, carrying out temperature programming to 120 ℃ at a temperature rising rate of 1 ℃/min, standing for crystallization for 48 hours, and then carrying out temperature programming to room temperature at a temperature lowering rate of 0.5 ℃/min to take out the reaction kettle.
(4) Washing and filtration of the product
And (4) centrifugally separating the green precipitate obtained in the step (3), washing the precipitate with absolute ethyl alcohol for three times (20 mL/time), removing unreacted raw materials, and centrifugally filtering.
(5) Work-up of the product
And (3) drying the solid product obtained in the step (4) in an oven at 120 ℃ for 24 hours to obtain the MIL-88B (V) -W metal organic complex with the solvent removed.
(6) MIL-88B (V) obtained in the step (5)-W organometallic Complex NO under reaction conditionsxNH of (2)3Reduction to N2The catalytic performance test of (2). The reaction conditions are as follows: fixed bed microreactor operating at 0.1MPa with feed gas composition of 0.075 vol.% NOx、NH3mol/NO ratio 1.05, 3.0 vol.% O2The balance gas is N2Space velocity of 5X 104mL/(g.h), with FGA10 type online flue gas analyzer (Shenzhen fibrate analyzer Co., Ltd.) to detect NO before and after reactionxThe conversion was calculated from the concentration. The results of the catalytic performance evaluation are shown in the attached figure 1 of the specification.
(7) Product metal organic complex characterization
Analyzing the MIL-88B (V) -W metal organic complex obtained in the step (5) by the following instrument and method to obtain a crystal phase structure (PXRD), thermal stability (TG) and an element valence state (XPS), and respectively referring to the attached figures 2, 3 and 4 of the specification.
Powder X-ray diffraction analysis (PXRD): the used instrument is a Philips X' pert pro X-ray diffractometer, and the measuring conditions are Cu target, Ni filter, tube pressure 40kV, tube flow 40mA and scanning angle 5-60 degrees; thermogravimetric analysis (TG): adopting an American SDT-Q600 type synchronous TGA/DSC analyzer, and under the atmosphere of nitrogen, wherein the temperature range is between room temperature and 500 ℃, and the heating rate is 10 ℃/min; the instrument used for XPS was ESCALB 250Xi (thermo electric company, USA). MgKa as an X light source and contaminated carbon C1s ═ 284.6eV as a calibration sample charge effect.
(8) EXAMPLES analysis of results
As seen from the crystalline phase structure (PXRD) of the product synthesized by the example, the crystalline phase structure of the MIL-88B (V) -W metal organic complex obtained by the invention is different from the reported and disclosed MIL-88B (V) metal organic complex, and H is different from H2The characteristic peak at BDC of 17.5 degrees is enhanced, which shows that the W element is added to H2BDC is coordinated to generate a brand new crystal phase structure, and the MIL-88B (V) -W metal organic complex obtained by the invention is a novel metal organic complex. From the XPS results of the product, it was found that two W4 f elements appeared in the product7/2Splitting peak with two W4 f5/2And all are 6-valent W ions, and the V element in the product has 4-valent and 5-valentThe form exists, and the content of 5 valence is more. This indicates the presence of two metal nodes in the product. According to PXRD characterization results, a W element is combined with an original ligand and a V metal in synthesis to form a novel bimetallic organic complex. According to the TG result of the product, the weight loss in the temperature range of 20-82 ℃ is the residual ethanol solvent molecules in the material pore channels, the weight loss in the temperature range of 82-235 ℃ is the removal of residual water molecules and-OH groups in the sample, the weight loss in the temperature range of 235-300 ℃ is the decomposition of the ligand which is not completely reacted, the MOFs material structure begins to collapse and decompose in the temperature range higher than 300 ℃ and completely decomposes at 405 ℃, and the MIL-88B (V) -W metal organic complex has high thermal stability. NH applied to MIL-88B (V) -W metal organic complex obtained by the invention3In catalytic reactions for selective catalytic reduction of NO, T50And T90T of 221 ℃ and 253 ℃ respectively, compared with the reference50At 268 ℃ and T90At 334 ℃, the catalyst shows excellent low-temperature denitration performance and stable conversion performance, and is a novel metal organic complex with excellent catalytic performance.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114289017A (en) * | 2022-01-10 | 2022-04-08 | 浙江大学 | Vanadium oxide-supported highly dispersed and structurally distorted nanocluster catalyst and its preparation method and application |
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| CN114289017A (en) * | 2022-01-10 | 2022-04-08 | 浙江大学 | Vanadium oxide-supported highly dispersed and structurally distorted nanocluster catalyst and its preparation method and application |
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