CN106268952B - A kind of preparation method and denitration application of load type double-metal organic framework material MIL-100 (Fe-Cu) - Google Patents
A kind of preparation method and denitration application of load type double-metal organic framework material MIL-100 (Fe-Cu) Download PDFInfo
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- 239000013291 MIL-100 Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910002549 Fe–Cu Inorganic materials 0.000 title claims abstract 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000013384 organic framework Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 239000003546 flue gas Substances 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 238000004448 titration Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 3
- 239000013082 iron-based metal-organic framework Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000006193 liquid solution Substances 0.000 abstract 1
- 238000002715 modification method Methods 0.000 abstract 1
- 238000002407 reforming Methods 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 20
- 102100033069 Histone acetyltransferase KAT8 Human genes 0.000 description 16
- 101000944170 Homo sapiens Histone acetyltransferase KAT8 Proteins 0.000 description 16
- 239000010949 copper Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
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- 229960004756 ethanol Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- 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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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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Abstract
The present invention provides the preparation methods and denitration application of a kind of load type double-metal organic framework material MIL-100 (Fe-Cu), belong to new material design and preparation field.Using rear synthetic modification method, Cu element is successfully introduced into the frame of original MOFs, constructs the novel MOFs material with bimetallic active site.It is characterized in that being effectively combined by preparing metal front liquid solution using stabilizer with Fe-MOFs using hydrothermal process, MIL-100 (Fe-Cu) material is prepared and for denitration reaction.Catalyst prepared by the present invention has Fe in advance compared with original single-metal reforming catalyst3+And Cu+Unsaturated active sites, denitration activity has 15% or so raising, and material scatter is good, and yield is higher, shows excellent catalytic activity.
Description
Technical field
The present invention relates to a kind of new double-core metal-organic framework materials MIL-100 (Fe- with certain catalytic performance
Cu technology of preparing) belongs to new material design and preparation field.It is also related to as catalysis material in denitrating flue gas
Practical application.
Background technique
Nitrogen oxides (NOx) is one of main source of atmosphere pollution.With the propulsion of China's industrial process, Industry Waste
Gas, vehicle exhaust discharge quantity are increasing, and environmental problem caused by nitrogen oxides contained in exhaust gas gradually shows.Wherein,
Acid rain caused by discharged nitrous oxides and photochemical fog become China's problem of environmental pollution very serious at present.
Currently, NH3- SCR method gas denitrifying technology is a kind of industrial widely used nitrogen oxides control technology, is had
The advantages that denitration efficiency is high, without secondary pollution.The currently used V of SCR2O5-WO3/TiO2It is mature commercial catalysts, but
There are many defects such as: reaction temperature is high, and temperature window is narrow, and vanadium has toxicity etc. under high temperature.Seek at this stage catalytic activity it is high,
The abundant and nontoxic Novel SCR catalyst of active site becomes the research hotspot in the field.
Organic framework material (Metal-Organic Frameworks, MOFs) is the organic self assembly of a new class of metal-
Framework material.And catalysis, gas storage with separate, the fields such as drug delivery are widely studied.A variety of MOFs materials can
It to handle by vacuum activating, removes the solvent molecule being coordinated with metal from its frame, lives to a large amount of catalysis occur
Property site.These unsatuated metal active sites can react for denitration catalyst provides corresponding adsorption potential, helps to improve denitration
Reaction efficiency.In addition, MOFs material usually has controllable pore size, high-specific surface area and metal unsaturation coordination quantity
Numerous and have many advantages, such as polymolecularity, these structures and physical and chemical performance are applied to denitration reaction for it and provide important theory
Foundation.And the denitration catalyst activity of MOFs material how is further increased and expands, it is current industrial denitration field urgent need to resolve
The technical issues of.The present invention is based on the basis of experiment and theory analysis, a kind of setting for novel Fe-Cu double-core MOFs is proposed
Meter and preparation method form Fe in MOFs material by self-assembling technique under the premise of keeping MOFs skeleton structure complete
With Cu two kinds of transition metal active centres, and realize MOFs to NO's using the synergistic effect of both metal active centres
It is highly selective, its catalytic activity is improved, realizes and the low-temperature denitration of industrial smoke is handled, to solution China's nitrogen oxides (NOx)
Pollution problem be of great significance.
It is of the invention it is innovative be to prepare a kind of new double-core MIL-100 (Fe-Cu) catalysis material, and be applied to real
In the denitration reaction on border.The main thought of this method is by Cu2O passes through a kind of new rear synthesis directed modification under cryogenic
Method be introduced into the frame of MIL-100 (Fe).I.e. after MOFs structure is formed, by that will have stability and well dispersed
Copper metal precursor solution be mixed in a certain ratio with MIL-100 (Fe) material, ultrasound simultaneously carry out low-temperature epitaxy, to make Cu+Modification makes it exist simultaneously Fe, two kinds of gold of Cu into organic frame under the premise of not changing MIL-100 (Fe) frame structure
Belong to active site, prepares novel MIL-100 (Fe-Cu) catalysis material.By carrying out active testing to the sample synthesized
And compared with the active testing result of MIL-100 (Fe) carries out, catalytic efficiency of discovery MIL-100 (Fe-Cu) in test process
It is higher than MIL-100 (Fe).Test characterization result proves: relative to monokaryon transition metal M IL-100 (Fe) material, Cu element
It introduces, the quantity of metal active position is not only increased, and there is a synergy between with original Fe active sites, to make
MIL-100 (Fe-Cu) has highly selective and low temperature ammonia-method denitration catalytic activity, has good prospects for commercial application.
Summary of the invention
The present invention is based on the layout strategies using synthetic modification after crystal, propose the design side of novel dual metal MOFs a kind of
Method is used to prepare novel dual metal MOFs catalysis material, and for the NOx in catalytic elimination flue gas.
Present inventors found that using certain proportion surfactant such as CTAB, the mixture of PVP and citric acid
As structure directing agent, can prepare and stablize and finely dispersed Cu metal front liquid, by with MIL-100 (Fe) material
The growth response in reaction kettle under ultrasonic treatment and cryogenic conditions, can be such that Cu metallic element successfully loads into MOFs frame
In, so that preparation has the Fe-Cu dinuclear metal MOFs material of good selectivity and low temperature ammonia-method denitration catalytic activity.The present invention
Determining structure directing agent is to influence Cu2An important factor for O pattern and size, while the introducing of the structure directing agent can make instead
Should during the particle with identical charges that is formed occur to repel, reformation and regrowth effect, thus make it is intermolecular due to
Competition caused by set effect and diffusion is reduced, and is more advantageous to dispersion and the diauxic growth of molecule particles, and added one
The glucose solution for determining concentration can make the Cu generated on the basis of maintaining solution reduction2O grain diameter is uniform, final to make
For novel dual metal MOFs catalysis material required out.
Technical solution of the present invention:
A kind of preparation method of load type double-metal organic framework material MIL-100 (Fe-Cu), steps are as follows:
(1) metal precursor CuSO is prepared4Solution
To CuSO4Structure directing agent is added in solution, and excessive reductant is added dropwise, reducing agent and CuSO4The body of solution
Product carries out ultrasound and magnetic agitation in titration process, adds the 1.5M glucose solution (partial size of control product than being 1:1
With pattern), dripping quantity and CuSO4The volume ratio of solution is 1:1, obtains stable metal precursor CuSO by sufficiently reacting4It is molten
Liquid；
The CuSO4The concentration of solution is 0.5-1M；
The CuSO4Molar ratio with structure directing agent is 14:1；
The reducing agent is 1-1.5M NaOH solution or sodium borohydride solution；
The structure directing agent includes CTAB, PVP and citric acid, and the molar ratio of three is 1:1:1-4；
(2) organic framework material MIL-100 (Fe) is prepared: in molar ratio by Fe(NO3)39H2O, trimesic acid and water
1:1:8 mixing, obtains mixed solution；Mixed solution reacts 10-20min under the conditions of 160 DEG C of temperature, obtains finely dispersed orange
Color solid；High purity water and the dehydrated alcohol processing that orange solids are used to 60-80 DEG C respectively, remove impurity, dry；Vacuum condition
Under, 100-150 DEG C of activation 10-12h is to get organic framework material MIL-100 (Fe)；
(3) load type double-metal organic framework material MIL-100 (Fe-Cu) is synthesized: in the metal front that step (1) obtains
Body CuSO4The organic framework material MIL-100 (Fe) that step (2) obtain is added in solution, controls organic framework material MIL-100
(Fe) with metal precursor CuSO4The mass ratio of solution is 1:15-65, magnetic agitation 2-4h；It is heated under the conditions of 100 DEG C of temperature
6-12h, vacuum filtration, and it is handled with dehydrated alcohol；It is drying to obtain brownish-yellow powder, i.e. load type double-metal organic backbone
Material MIL-100 (Fe-Cu).
Above-mentioned load type double-metal organic framework material MIL-100 (Fe-Cu) denitration reaction being prepared, reaction condition
Are as follows: 500ppm NO, 500ppm NH3, 5%O2, N2For Balance Air；Mixed gas is passed into the reaction tube equipped with catalyst,
And the stability number of NO concentration at different temperature is recorded by flue gas analyzer.
Beneficial effects of the present invention: the method for synthetic modification bimetallic MOFs, obtained sample crystal form after the present invention proposes
Uniform, cellular structure is regular, and specific surface area reaches 958m2g-1, metal source of the present invention is cheap, and catalytic activity is higher, to environment
It is nontoxic.And combine the technical fields such as Coordinative Chemistry, nanotechnology, denitrating flue gas, it proposes and prepares catalyst
New approaches have important application value.A kind of purposes of MOFs catalyst as described above, is used to effectively remove in flue gas
NOx harmful components.Catalyst has Fe abundant simultaneously3+And Cu+Unsaturated active sites show excellent catalytic activity.
Detailed description of the invention
Fig. 1 (a) is MIL-100 (Fe-Cu) XRD diagram that the angle of diffraction is 3-30 °；
Fig. 1 (b) is MIL-100 (Fe-Cu) XRD diagram that the angle of diffraction is 20-65 °.
Fig. 2 (a) is the scanning electron microscope (SEM) photograph of MIL-100 (Fe)；
The scanning electron microscope (SEM) photograph of Fig. 2 (b) MIL-100 (Fe-Cu).
Fig. 3 is the hot weight curve of MIL-100 (Fe-Cu).
Fig. 4 is MIL-100 (Fe-Cu) EDX spectrogram.
Fig. 5 is MIL-100 (Fe-Cu) H2- TPR figure.
Fig. 6 is the infrared characterization chart of MIL-100 (Fe-Cu), MIL-100 (Fe).
Fig. 7 is the NH of the MIL-100 (Fe-Cu) and MIL-100 (Fe) of different proportion3SCR activity test curve.
Specific embodiment
Below in conjunction with technical solution and technical solution, it is further discussed below a specific embodiment of the invention.
Embodiment 1: the preparation method of stable metal precursor solution.
Prepare 5mL, 0.7mol/LCuSO4·5H2O solution is dissolved in the ultrapure water of 60mL, and CTAB, PVP and lemon is added dropwise
The mixed solution (molar ratio 1:1:3) of acid, magnetic agitation 10min.5mL, 1.2mol/L NaOH solution or 1.2mol/L's
NaBH4In the above-mentioned solution of the instillation of solution at the uniform velocity.It is ultrasonically treated 30min in titration, after all having titrated, magnetic force is placed in and stirs
It mixes and stirs 30min on device.
The preparation method of embodiment 2:MIL-100 (Fe) catalyst.
Fe(NO3)39H2O (3.35mmol), trimesic acid (3.35mmol) are dissolved in the ultrapure water of 25mL.It will
Uniformly mixed solution is placed in closed glass container, and is heated using frequency electromagnetic waves concussion microwave to mixed liquor,
Via the heating-up time of 25s, temperature is made to appreciate 160 DEG C, and maintain 15min, has obtained finely dispersed orange solids.
Product being used respectively 60 DEG C of high purity water and dehydrated alcohol carry out water bath processing, (about 150mL is added in 1g catalyst
High purity water or ethyl alcohol), impurity is removed.And it is dried under 70 DEG C of thermostatic drying chamber.Sample after drying is carried out
Vacuum activating processing, is made catalyst.
The preparation method of embodiment 3:MIL-100 (Fe-Cu) catalyst.
The metal precursor for taking aforementioned stable is respectively 5mL, and the Fe-MOF material of 0.2g is added in 10mL, 15mL, and magnetic force stirs
Mix 2h.Then reactant is moved in the reaction kettle of polyvinyl chloride liner, sealing, which is put into baking oven, heats, 100 DEG C of heating 12h.
It is cooled to room temperature to reaction kettle and centrifugal treating 3-5 times (solution is high purity water) is carried out to product, and with ethanol solution to it
It impregnates and cleans repeatedly.Product is heated overnight in 70 DEG C of thermostatic drying chambers finally, pure brownish-yellow powder is obtained, that is, has
Machine framework material MIL-100 (Fe-Cu), yield 78%.
The purifying of embodiment 4:MIL-100 (Fe-Cu) catalyst.
MIL-100 (Fe-Cu) powder is further purified with dehydrated alcohol, the complete ligand of removal unreacted.Firstly, will
The sample arrived is mixed with a certain amount of dehydrated alcohol (ethyl alcohol of 1g MIL-100 (Fe-Cu) addition about 150mL), in 80 DEG C of constant temperature
Magnetic agitation 3h in water-bath.It is cooled to room temperature rear centrifugal drying.MIL-100 (Fe-Cu) powder-like after purification can be obtained
Product.
The activation of embodiment 5:MIL-100 (Fe-Mn) catalyst.
Sample is placed in a vacuum drying oven 100 DEG C, 12h is dried.Mainly there are two purposes for this step: first is that
Further remove solvent molecule extra in MOFs material hole；Second is that the metal cation Fe in frameⅢ、CuIPart occurs
The variation of valence state may advantageously facilitate the progress of catalysis reaction.
The test of embodiment 6:MIL-100 (Fe-Mn) catalyst denitration activity.
Sample after weighing the above-mentioned activation of 0.1g after compressing tablet process (pressure about 5MPa) is added to the stone that internal diameter is 6mm
In English reaction tube.Reaction condition are as follows: 500ppm NO, 500ppm NH3, 5%O2, N2For Balance Air.Above-mentioned gas mixing is passed into
In reaction tube equipped with catalyst, and pass through the stability number of flue gas analyzer record NO concentration at different temperature.290~
At 310 DEG C, denitration activity can be of about 78%, higher than the Fe-MOF of monometallic active sites.
Claims (2)
1. a kind of preparation method of load type double-metal organic framework material MIL-100 (Fe-Cu), which is characterized in that step is such as
Under:
(1) metal precursor CuSO is prepared4Solution
To CuSO4Structure directing agent is added in solution, and excessive reductant is added dropwise, reducing agent and CuSO4The volume ratio of solution
For 1:1, ultrasound and magnetic agitation are carried out in titration process；Be added dropwise 1.5M glucose solution again, glucose solution dripping quantity with
CuSO4The volume ratio of solution is 1:1, obtains stable metal precursor CuSO by sufficiently reacting4Solution；
The structure directing agent includes CTAB, PVP and citric acid, and the molar ratio of three is 1:1:1-4；
The CuSO4Molar ratio with structure directing agent is 14:1；
(2) organic framework material MIL-100 (Fe) is prepared: by Fe(NO3)39H2O, trimesic acid and water 1:1:8 in molar ratio
Mixing, obtains mixed solution；Mixed solution reacts 10-20min under the conditions of 160 DEG C of temperature, obtains finely dispersed orange solid
Body；High purity water and the dehydrated alcohol processing that orange solids are used to 60-80 DEG C respectively, remove impurity, dry；Under vacuum condition,
100-150 DEG C of activation 10-12h is to get organic framework material MIL-100 (Fe)；
(3) load type double-metal organic framework material MIL-100 (Fe-Cu) is synthesized: in the metal precursor that step (1) obtains
CuSO4The organic framework material MIL-100 (Fe) that step (2) obtain is added in solution, controls organic framework material MIL-100
(Fe) with metal precursor CuSO4The mass ratio of solution is 1:15-65, magnetic agitation 2-4h；It is heated under the conditions of 100 DEG C of temperature
6-12h, vacuum filtration, and it is handled with dehydrated alcohol；It is drying to obtain brownish-yellow powder, i.e. load type double-metal organic backbone
Material MIL-100 (Fe-Cu)；
The CuSO4The concentration of solution is 0.5-1M；
The reducing agent is 1-1.5M sodium borohydride solution.
2. the load type double-metal organic framework material MIL-100 (Fe-Cu) that method of claim 1 is prepared is used for denitration
Reaction, which is characterized in that reaction condition are as follows: 500ppm NO, 500ppm NH3, 5%O2, N2For Balance Air, it is passed into equipped with negative
In the reaction tube of load type bimetallic organic framework material MIL-100 (Fe-Cu), and different temperature is recorded in by flue gas analyzer
Spend the stability number of lower NO concentration.
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| CN107446137B (en) * | 2017-08-04 | 2020-05-26 | 中南大学 | Method for preparing iron-based metal organic framework material MIL-100(Fe) |
| CN109225339B (en) * | 2018-09-28 | 2021-05-25 | 合肥工业大学 | Hierarchical assembly method and application of high-activity synergistic MOF catalyst |
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| CN110368991B (en) * | 2019-08-05 | 2022-05-20 | 安徽元琛环保科技股份有限公司 | SCR low-temperature denitration catalyst based on ZIF-67 porous carbon skeleton modification and preparation method thereof |
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| CN111410749B (en) * | 2020-03-17 | 2022-04-08 | 广西民族大学 | Application of nano-carrier MIL-100(Fe) in loading nitidine chloride |
| CN111468190A (en) * | 2020-05-21 | 2020-07-31 | 福州大学 | Preparation of MI L-100 (Fe) metal organic framework material doped with different metals and photocatalysis nitrogen fixation |
| CN111701622A (en) * | 2020-06-29 | 2020-09-25 | 西安科技大学 | Preparation method of Cu-MOF-Fe fly ash catalyst for denitration and demercuration |
| CN112536070A (en) * | 2020-12-02 | 2021-03-23 | 浙江大学 | Preparation method of visible light response type MIL-100(Fe) photocatalytic composite material |
| CN114682223A (en) * | 2020-12-30 | 2022-07-01 | 中国石油化工股份有限公司 | Metal-loaded modified Cu-BTC material and preparation method thereof |
| CN113134391A (en) * | 2021-03-28 | 2021-07-20 | 桂林理工大学 | Metal organic complex catalytic material with vanadium-tungsten bimetallic coordination |
| CN113999398B (en) * | 2021-08-16 | 2022-11-08 | 北控水务(中国)投资有限公司 | Fe-MOF composite polymer targeted flocculant, preparation method and application |
| CN114223671A (en) * | 2021-12-21 | 2022-03-25 | 广东药科大学 | Bimetal nano-structure antibacterial composition and preparation method thereof |
| CN117362660B (en) * | 2023-08-31 | 2024-04-26 | 中山大学 | Metal organic framework material Zr-MOF, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752168A (en) * | 2014-01-10 | 2014-04-30 | 大连理工大学 | Application method for MIL-100(Fe) catalyst in NH3-SCR (Selective Catalytic Reduction) reaction |
| CN105237586A (en) * | 2015-10-15 | 2016-01-13 | 大连理工大学 | Preparation and application of novel dual-core organic skeleton material MIL-100(Fe-Mn) |
-
2016
- 2016-07-20 CN CN201610574780.XA patent/CN106268952B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752168A (en) * | 2014-01-10 | 2014-04-30 | 大连理工大学 | Application method for MIL-100(Fe) catalyst in NH3-SCR (Selective Catalytic Reduction) reaction |
| CN105237586A (en) * | 2015-10-15 | 2016-01-13 | 大连理工大学 | Preparation and application of novel dual-core organic skeleton material MIL-100(Fe-Mn) |
Non-Patent Citations (2)
| Title |
|---|
| A supported Cu(I)@MIL-100(Fe) adsorbent with high CO adsorption capacity and CO/N2 selectivity;Junjie Peng et al.;《Chemical Engineering Journal》;20150207;第270卷;282-289 |
| Low-temperature loading of Cu+ species over porous metal-organic frameworks (MOFs) and adsorptive desulfurization with Cu+-loaded MOFs;Nazmul Abedin Khan et al.;《Journal of Hazardous Materials》;20120819;第237-238卷;180-185 |
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