CN106268952A - The preparation method of a kind of load type double-metal organic framework material MIL 100 (Fe Cu) and denitration application - Google Patents
The preparation method of a kind of load type double-metal organic framework material MIL 100 (Fe Cu) and denitration application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000013291 MIL-100 Substances 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 13
- 239000013384 organic framework Substances 0.000 claims description 10
- 230000008569 process Effects 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
- 239000002243 precursor Substances 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
- 238000001994 activation Methods 0.000 claims description 6
- 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
- 230000004913 activation Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 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
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000004448 titration Methods 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
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 229910002549 Fe–Cu Inorganic materials 0.000 claims 5
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 14
- 238000013461 design Methods 0.000 abstract description 3
- 239000006193 liquid solution Substances 0.000 abstract description 2
- 238000002715 modification method Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis 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 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000013082 iron-based metal-organic framework Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000004044 response Effects 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
- 239000002912 waste gas Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009432 framing 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
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000376 reactant Substances 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
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
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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 invention provides preparation method and the 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.Synthetic modification method after utilization, is successfully introduced into Cu element to the framework of original MOFs, builds the novel MOFs material with bimetallic active site.It is characterized in that utilizing hydrothermal process, be effectively combined with Fe MOFs by utilizing stabilizer to prepare metal front liquid solution, prepare MIL 100 (Fe Cu) material and for denitration reaction.Catalyst prepared by the present invention, in advance compared with original single-metal reforming catalyst, has Fe simultaneously3+And Cu+Unsaturated active sites, denitration activity has the raising of about 15%, and material scatter is good, and productivity is higher, shows excellent catalysis 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.Also relate to it as catalysis material in denitrating flue gas
Actual application.
Background technology
Nitrogen oxides (NOx) is one of main source of atmospheric pollution.Along with the propelling of China's industrial process, Industry Waste
Gas, vehicle exhaust discharge quantity are increasing, and the environmental problem that nitrogen oxides contained in waste gas is caused gradually manifests.Wherein,
Acid rain and photochemical fog that discharged nitrous oxides causes become the problem of environmental pollution that China is the most serious.
At present, NH3-SCR method gas denitrifying technology is industrial one widely used nitrogen oxides control technology, has
The advantages such as denitration efficiency is high, non-secondary pollution.The V that SCR uses at present2O5-WO3/TiO2It is ripe commercial catalysts, but also
There is many defects such as: reaction temperature is high, and temperature window is narrow, and under high temperature, vanadium has toxicity etc..Present stage seek to be catalyzed activity high,
Avtive spot is abundant and nontoxic Novel SCR catalyst becomes the study hotspot in this field.
Organic framework material (Metal-Organic Frameworks, MOFs) is metal-organic self assembly that a class is new
Framework material.And in catalysis, gas stores and separates, the field such as drug delivery is studied widely.Multiple MOFs material can
To be processed by vacuum activation, make the solvent molecule with metal-complexing remove from its framework, thus occur that substantial amounts of catalysis is lived
Property site.These unsatuated metal active sites can be that denitration catalyst reaction provides corresponding adsorption potential, is favorably improved denitration
Reaction efficiency.Additionally, MOFs material is generally of controlled pore size, high-specific surface area and metal unsaturation coordination quantity
Numerous and have the advantages such as polymolecularity, these structures and physical and chemical performance are that it is applied to denitration reaction and provides important theory
Foundation.And improve and expand the denitration catalyst activity of MOFs material the most further, it is that solution is needed in industry denitration field badly at present
Technical problem.The present invention is based on the basis of experiment and theory analysis, it is proposed that a kind of novel Fe-Cu double-core MOFs sets
Meter and preparation method, on the premise of keeping MOFs framing structure complete, form Fe by self-assembling technique in MOFs material
With two kinds of transition metal active centres of Cu, and utilize the synergism of both metal active centres to realize MOFs to NO's
High selectivity, improves its catalysis activity, it is achieved process the low-temperature denitration of industrial smoke, to solving China's nitrogen oxides (NOx)
Pollution problem significant.
Innovative being of the present invention prepares a kind of new double-core MIL-100 (Fe-Cu) catalysis material, and is applied to reality
In the denitration reaction on border.The main thought of the method is by Cu2O is under cryogenic by a kind of new rear synthesis directed modification
Method introduce MIL-100 (Fe) framework in.I.e. after MOFs structure is formed, by having stability and good dispersion
Copper metal front liquid solution mix by a certain percentage with MIL-100 (Fe) material, ultrasonic and carry out low-temperature epitaxy, so that Cu+Modify in organic frame on the premise of not changing MIL-100 (Fe) frame structure so that it is there are two kinds of gold of Fe, Cu simultaneously
Belong to avtive spot, prepare novel MIL-100 (Fe-Cu) catalysis material.By the sample synthesized is carried out active testing
And compared with carrying out with the active testing result of MIL-100 (Fe), find the MIL-100 (Fe-Cu) catalytic efficiency at 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
Introduce, not only increase the quantity of metal active position, and there is a synergy between with original Fe active sites, so that
MIL-100 (Fe-Cu) has high selectivity and low temperature ammonia-method denitration catalysis activity, has good prospects for commercial application.
Summary of the invention
The present invention, based on utilizing the layout strategy of synthetic modification after crystal, proposes the design side of a kind of novel dual metal MOFs
Method, is used for preparing novel dual metal MOFs catalysis material, and the NOx in catalytic elimination flue gas.
Present inventors found that, use certain proportion surfactant such as CTAB, PVP, and the mixture of citric acid
As structure directing agent, stable and finely dispersed Cu metal front liquid can be prepared, by with MIL-100 (Fe) material
Growth response in reactor under supersound process, and cryogenic conditions, can make Cu metallic element successfully load into MOFs framework
In, thus preparation has good selectivity and the Fe-Cu dinuclear metal MOFs material of low temperature ammonia-method denitration catalysis activity.The present invention
The structure directing agent determined is to affect Cu2O pattern and the key factor of size, the introducing of this structure directing agent simultaneously can make instead
During Ying formed the granule with identical charges repel, reform and regrowth effect, thus make intermolecular due to
The competition that set effect and diffusion cause reduces, and is more beneficial for dispersion and the diauxic growth of molecule particles, added
Determine the glucose solution of concentration, the Cu of generation can be made on the basis of maintaining solution reduction2O grain diameter is homogeneous, finally makes
For going out required novel dual metal MOFs catalysis material.
Technical scheme:
A kind of preparation method of load type double-metal organic framework material MIL-100 (Fe-Cu), step is as follows:
(1) metal precursor CuSO is prepared4Solution
To CuSO4Solution adds structure directing agent, and is added dropwise over excessive reductant, reducing agent and CuSO4The body of solution
Long-pending ratio is 1:1, carries out ultrasonic and magnetic agitation in titration process, adds 1.5M glucose solution and (controls the particle diameter of product
With pattern), dripping quantity and CuSO4The volume ratio of solution is 1:1, obtains stable metal precursor CuSO through fully reaction4Molten
Liquid；
Described CuSO4The concentration of solution is 0.5-1M；
Described CuSO4It is 14:1 with the mol ratio of structure directing agent；
Described reducing agent is 1-1.5M NaOH solution or sodium borohydride solution；
Described structure directing agent includes CTAB, PVP and citric acid, and the mol ratio of three is 1:1:1-4；
(2) organic framework material MIL-100 (Fe) is prepared: you compare by Fe(NO3)39H2O, trimesic acid and hydromassage
1:1:8 mixes, and obtains mixed solution；Mixed solution reacts 10-20min under 160 DEG C of temperature conditionss, obtains finely dispersed orange
Color solid；By orange solids respectively with high purity water and the dehydrated alcohol process of 60-80 DEG C, go the removal of impurity, be dried；Vacuum condition
Under, 100-150 DEG C of activation 10-12h, obtain organic framework material MIL-100 (Fe)；
(3) synthesis load type double-metal organic framework material MIL-100 (Fe-Cu): the metal front obtained in step (1)
Body CuSO4Solution adds the organic framework material MIL-100 (Fe) that step (2) obtains, controls organic framework material MIL-100
(Fe) with metal precursor CuSO4The mass ratio of solution is 1:15-65, magnetic agitation 2-4h；Heat under 100 DEG C of temperature conditionss
6-12h, vacuum filtration, and with dehydrated alcohol, it is processed；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 prepared, reaction condition
For: 500ppm NO, 500ppm NH3, 5%O2, N2For Balance Air；Mixed gas is passed into equipped with in the reaction tube of catalyst,
And by the stability number of flue gas analyzer record NO concentration at different temperature.
Beneficial effects of the present invention: the method for synthetic modification bimetallic MOFs, the sample crystal formation obtained after present invention proposition
Homogeneous, pore passage structure is regular, and specific surface area reaches 958m2g-1, metal source of the present invention is cheap, and catalysis activity is higher, to environment
Nontoxic.And the technical fields such as Coordinative Chemistry, nanotechnology, denitrating flue gas are combined, it is proposed that prepare catalyst
New approaches, have important using value.The purposes of a kind of MOFs catalyst as above, it is for effectively removing in flue gas
NOx harmful components.Catalyst has abundant Fe simultaneously3+And Cu+Unsaturated active sites, shows excellent catalysis activity.
Accompanying drawing explanation
Fig. 1 (a) be the angle of diffraction be MIL-100 (Fe-Cu) XRD figure of 3-30 °；
Fig. 1 (b) be the angle of diffraction be MIL-100 (Fe-Cu) XRD figure of 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 thermogravimetric curve figure of MIL-100 (Fe-Cu).
Fig. 4 is MIL-100 (Fe-Cu) EDX spectrogram.
Fig. 5 is MIL-100 (Fe-Cu) H2-TPR schemes.
Fig. 6 is MIL-100 (Fe-Cu), the Infrared Characterization figure of MIL-100 (Fe).
Fig. 7 is the MIL-100 (Fe-Cu) and the NH of MIL-100 (Fe) of different proportion3-SCR activity test curve.
Detailed description of the invention
Below in conjunction with technical scheme and technical scheme, it is further discussed below the detailed description of the invention of the present invention.
Embodiment 1: the preparation method of stable metal precursor solution.
Preparation 5mL, 0.7mol/LCuSO4·5H2O solution is dissolved in the ultra-pure water of 60mL, and drips CTAB, PVP and Fructus Citri Limoniae
The mixed solution (molar ratio is 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 solution instillation at the uniform velocity.Titration limit, limit supersound process 30min, after all having titrated, is placed in magnetic force and stirs
Mix stirring 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 ultra-pure water of 25mL.Will
The solution of mix homogeneously is positioned in closed glass container, and utilizes frequency electromagnetic waves concussion microwave to heat mixed liquor,
Via the heating-up time of 25s, make temperature appreciate 160 DEG C, and maintain 15min, obtained finely dispersed orange solids.
Product uses the high purity water of 60 DEG C and dehydrated alcohol carry out water bath processing respectively, and (1g catalyst adds about 150mL
High purity water or ethanol), by Impurity removal.And be dried under the thermostatic drying chamber of 70 DEG C.Dried sample is carried out
Vacuum activation processes, and makes catalyst.
The preparation method of embodiment 3:MIL-100 (Fe-Cu) catalyst.
The metal precursor taking aforementioned stable is respectively 5mL, and 10mL, 15mL add the Fe-MOF material of 0.2g, and magnetic force stirs
Mix 2h.Then reactant is moved in the reactor of polrvinyl chloride inner bag, seal to put in baking oven and heat, 100 DEG C of heating 12h.
Product is centrifuged processing 3-5 time (solution is high purity water) after being down to room temperature by question response still, and with ethanol solution to it
Soak and repeatedly clean.Finally by product heated overnight in 70 DEG C of thermostatic drying chambers, obtain pure brownish-yellow powder, i.e. have
Machine framework material MIL-100 (Fe-Cu), productivity 78%.
The purification of embodiment 4:MIL-100 (Fe-Cu) catalyst.
MIL-100 (Fe-Cu) powder dehydrated alcohol is further purified, removes the part that unreacted is complete.First, incite somebody to action
To sample and a certain amount of dehydrated alcohol ethanol of about 150mL (the 1g MIL-100 (Fe-Cu) add) mix, at 80 DEG C of constant temperature
Magnetic agitation 3h in water-bath.It is cooled to centrifugal drying after room temperature.I.e. available MIL-100 (Fe-Cu) powder-like after purification
Product.
The activation of embodiment 5:MIL-100 (Fe-Mn) catalyst.
Sample is placed in vacuum drying oven 100 DEG C and is dried process 12h.This step mainly has two purposes: one is
Remove solvent molecule unnecessary in MOFs material hole further；Two is the metal cation Fe in frameworkⅢ、CuIPart occurs
The change of valence state, may advantageously facilitate the carrying out of catalytic reaction.
Embodiment 6:MIL-100 (Fe-Mn) catalyst denitration activity is tested.
Weigh the sample after the above-mentioned activation of 0.1g (pressure about 5MPa) after tabletting processes and join the stone that internal diameter is 6mm
In English reaction tube.Reaction condition is: 500ppm NO, 500ppm NH3, 5%O2, N2For Balance Air.Above-mentioned gas mixing is passed into
Equipped with in the reaction tube of catalyst, and by the stability number of flue gas analyzer record NO concentration at different temperature.290～
When 310 DEG C, denitration activity is up to about 78%, higher than the Fe-MOF of monometallic active sites.
Claims (4)
1. the preparation method of load type double-metal organic framework material MIL-100 (Fe-Cu), it is characterised in that step is such as
Under:
(1) metal precursor CuSO is prepared4Solution
To CuSO4Solution adds structure directing agent, and is added dropwise over excessive reductant, reducing agent and CuSO4The volume ratio of solution
For 1:1, titration process carries out ultrasonic and magnetic agitation；Drip 1.5M glucose solution, glucose dripping quantity and CuSO again4Molten
The volume ratio of liquid is 1:1, obtains stable metal precursor CuSO through fully reaction4Solution；
Described structure directing agent includes CTAB, PVP and citric acid, and the mol ratio of three is 1:1:1-4；
Described CuSO4It is 14:1 with the mol ratio of structure directing agent；
(2) organic framework material MIL-100 (Fe) is prepared: Fe(NO3)39H2O, trimesic acid and hydromassage that are compared 1:1:8
Mixing, obtains mixed solution；Mixed solution reacts 10-20min under 160 DEG C of temperature conditionss, obtains finely dispersed orange solid
Body；By orange solids respectively with high purity water and the dehydrated alcohol process of 60-80 DEG C, go the removal of impurity, be dried；Under vacuum condition,
100-150 DEG C of activation 10-12h, obtains organic framework material MIL-100 (Fe)；
(3) synthesis load type double-metal organic framework material MIL-100 (Fe-Cu): the metal precursor obtained in step (1)
CuSO4Solution adds the organic framework material MIL-100 (Fe) that step (2) obtains, controls organic framework material MIL-100
(Fe) with metal precursor CuSO4The mass ratio of solution is 1:15-65, magnetic agitation 2-4h；Heat under 100 DEG C of temperature conditionss
6-12h, vacuum filtration, and with dehydrated alcohol, it is processed；It is drying to obtain brownish-yellow powder, i.e. load type double-metal organic backbone
Material MIL-100 (Fe-Cu).
Preparation method the most according to claim 1, it is characterised in that described CuSO4The concentration of solution is 0.5-1M.
Preparation method the most according to claim 1 and 2, it is characterised in that described reducing agent is 1-1.5MNaOH solution
Or sodium borohydride solution.
4. load type double-metal organic framework material MIL-100 (Fe-Cu) that claim 1 or 2 prepares is anti-for denitration
Should, it is characterised in that reaction condition is: 500ppm NO, 500ppm NH3, 5%O2, N2For Balance Air, it is passed into equipped with load
In the reaction tube of type bimetallic organic framework material MIL-100 (Fe-Cu), and by flue gas analyzer record in different temperature
The stability number of lower NO concentration.
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