CN107446137A - The method that one kind prepares ferrous metals organic framework material MIL 100 (Fe) - Google Patents
The method that one kind prepares ferrous metals organic framework material MIL 100 (Fe) Download PDFInfo
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- CN107446137A CN107446137A CN201710659923.1A CN201710659923A CN107446137A CN 107446137 A CN107446137 A CN 107446137A CN 201710659923 A CN201710659923 A CN 201710659923A CN 107446137 A CN107446137 A CN 107446137A
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- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 19
- -1 ferrous metals Chemical class 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 239000013384 organic framework Substances 0.000 title claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 54
- 239000013291 MIL-100 Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 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 16
- 239000007788 liquid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 2
- 230000031709 bromination Effects 0.000 claims 2
- 238000005893 bromination reaction Methods 0.000 claims 2
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 claims 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003546 flue gas Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 239000013144 Fe-MIL-100 Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- 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
-
- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention proposes the method that one kind prepares ferrous metals organic framework material MIL 100 (Fe).The present invention adds surfactant, the MIL 100 (Fe) that auxiliary has synthesized composition and grain graininess is uniform, crystal morphology is more regular during ferrous metals organic framework material is prepared.Tested and analyzed by denitrating flue gas, its denitration temperature is not than adding the sample of surfactant to reduce 10 60 DEG C when reaching 99.9% catalytic denitration rate.
Description
Technical field
The invention belongs to denitrating flue gas material and its preparing technical field, is related to one kind and prepares ferrous metals organic backbone material
Expect MIL-100 (Fe) method.
Background technology
Flue gas low-temperature denitration is one of current fume environment protection field urgent problem.It is at present industrially with NH3For
Reducing agent and V2O5+WO3(MoO3)/TiO2For the SCR of catalyst, 300 DEG C~400 DEG C of active temperature windows, and
Life-span is by SO2Grade influence with ash.Metal-organic framework materials are one of current study hotspots as low-temperature denitration catalyst,
Such as the patent document that number of patent application is 201310307034.0 be using metal organic framework MIL-100 (Fe) be catalysis
Agent, ammonia denitration activity also only reaches 90% during 270 DEG C of relatively lower temp in embodiment.
If further reducing metal organic framework MIL-100 (Fe) denitration temperature, will avoid causing in denitrification process
Metal-organic framework materials catalyst caves in (280-350 DEG C).Therefore, by preparing metal-organic framework materials MIL-100
(Fe) add surfactant during, auxiliary synthesized composition and grain graininess uniformly, crystal morphology it is more regular
MIL-100 (Fe), find one kind has high catalytic activity, the catalyst that and can recycles in low temperature range.
The content of the invention
It is an object of the invention to provide the method that one kind prepares ferrous metals organic framework material MIL-100 (Fe).Making
Surfactant is added during standby ferrous metals organic framework material MIL-100 (Fe), auxiliary has synthesized composition and particle
The MIL-100 (Fe) that degree is uniform, crystal morphology is more regular, it is de- that catalysis is reduced on the premise of 99.9% catalytic denitration rate is reached
The temperature of nitre.
The method that one kind prepares ferrous metals organic framework material MIL-100 (Fe), prepare ferrous metals organic backbone material
Surfactant is added during material MIL-100 (Fe).
Described surfactant includes：TTAB, cetyl trimethylammonium bromide, dodecane
One or more in base benzene sulfonic acid sodium salt, lauryl sodium sulfate, polyvinylpyrrolidone and polyvinyl alcohol.
Described surfactant is preferably TTAB or cetyl trimethylammonium bromide.
Described surfactant is more preferably cetyl trimethylammonium bromide.
Concentration of the described surfactant in whole reaction system is 1-24g/L.It is preferred that 18g/L.
The method for preparing ferrous metals organic framework material MIL-100 (Fe) is specially：Ferrous metals organic framework material
MIL-100 (Fe) preparation process is：First trimesic acid is added in ultra-pure water, is uniformly mixing to obtain solution A；Then toward A liquid
Middle to add a certain amount of surfactant, stir to obtain B liquid；Hydrofluoric acid and nitric acid are sequentially added into B solution, is stirred
Obtain C solution；It is put into after iron powder will be added in C solution in reactor, temperature reaction, after reaction terminates, cooling, outwells supernatant
Liquid, by remaining troubled liquor washing impurity-removing, after gained sample drying grinding obtain Chinese red solid product.
Above-mentioned preparation method trimesic acid concentration in whole reaction system is 10-50g/L, preferably 30g/L；Hydrofluoric acid
Concentration is 10-100ml/L, preferably 18ml/L；Concentration of nitric acid is 5-50ml/L, preferably 10ml/L；The adding proportion of iron powder is 8-
20g/L, preferably 12g/L.
Above-mentioned preparation method, reactor are placed in an oven, are warming up to temperature as 100-200 DEG C, preferably 150 DEG C, constant temperature
10-30h, preferably 24h.
The above-mentioned further detailed process of preparation method is as follows：First trimesic acid is added in ultra-pure water, ultrasonic wave stirring
15min obtains solution A；Then toward surfactant is added in A liquid, ultrasonic wave stirring 15min obtains B liquid；Add successively into B solution
Enter hydrofluoric acid and nitric acid, ultrasonic wave stirring 15min obtains C solution；It is put into after iron powder will be added in C solution in steel bomb,
Baking oven is placed in, is uniformly controlled reaction temperature；After reaction terminates, steel bomb is placed in air and is cooled to room temperature；After cooling
Reactor is opened, supernatant is outwelled, remaining troubled liquor is transferred in beaker, then in 70 DEG C of ultra-pure waters and 70 DEG C of alcohol
Middle circulation washing is until impurity eliminates, and grinding obtains Chinese red solid product to gained sample after dry 12h at 70 DEG C.
The control of terms and conditions, the order of addition of raw material, concentration and its adding proportion are by pole in the preparation method of the present invention
Whether big influence final products can be successfully prepared.Such as the adding proportion of raw material is not within the scope of the present invention, the lighter produces
Impurity, product colour just, do not have a strong impact on performance, heavy then reaction failure, produce flocculent deposit.Do not add according to the raw material of the present invention
Add order, reaction can not be smoothed out, and not generate the octahedra material of the present invention, or be also unable to reach even if generation octahedron
Target denitration rate etc..
Above-mentioned ferrous metals organic framework material MIL-100 (Fe) materials test and analyze step as catalyst denitration：
(1) flue gas analyzer and distributing instrument preheating 30min are opened；
(2) 0.50g catalyst samples are weighed to be fixed in quartz tube reactor with silica wool, then quartzy tube reaction
Device is put into tube type resistance furnace；
(3) laboratory apparatus and pipeline are connected, sets distribution instrument parameter, gas entirety flow velocity has been explored using laboratory
Preferable 100mL/min, open the intake valve of reacting gas；
(4) program of temperature control is set and opens tube type resistance furnace, heats to preset value；
(5) flue gas analyzer number system is opened, an exit NO concentration was recorded every one minute, treats that exit NO is dense
Spend basicly stable rear stop recording；
(6) stop being passed through reacting gas, close experimental facilities.
Above-mentioned method, the flue gas that flue gas includes power plant and metallurgical works is discharged.
The ferrous metals organic framework material catalyst that the present invention is prepared using surfactant auxiliary can reach more
The purpose of NO_x Reduction by Effective is carried out under low temperature, on the premise of high denitration rate is ensured, catalyst temperature in use is lower, in next step
Carry out engineering denitrating flue gas processing experiment and support is provided.Heavy industrialization application of the invention to realizing smoke catalytic denitration
It is significant.
Brief description of the drawings
Fig. 1 is to add the ESEM spectrogram (5000 times of amplification) that different amounts of TTAB and CTAB synthesize MIL-100 (Fe)；
As addition is incremented by, sample regular octahedron pattern is better, and denitration rate is higher；
Fig. 2 is the XRD spectra for being separately added into TTAB (0.9g) and CTAB (0.9g) auxiliary synthesis MIL-100 (Fe)；
Fig. 3 is MIL-100 (Fe)(0.9gTTAB)、MIL-100(Fe)(0.9gCTAB)With MIL-100 (Fe) thermal multigraph；
Fig. 4 is MIL-100 (Fe)(0.9gTTAB)、MIL-100(Fe)(0.9gCTAB)With MIL-100 (Fe) infrared spectrogram；
Fig. 5 is MIL-100 (Fe)(0.9gTTAB)、MIL-100(Fe)(0.9gCTAB)With MIL-100 (Fe) Raman spectrum；
Fig. 6 is MIL-100 (Fe)(0.9gTTAB)、MIL-100(Fe)(0.9gCTAB)With MIL-100 (Fe) denitration curve；
When reaction temperature is 280 DEG C, MIL-100 (Fe), MIL-100 (Fe)(0.9gTTAB)With MIL-100 (Fe)(0.9gCTAB)'s
Optimal denitration rate is respectively 98%, 99.9% and 99.9%, wherein MIL-100 (Fe)(0.9gCTAB) can reach at 220 DEG C
99.9%, 60 DEG C are reduced compared with MIL-100 (Fe)；MIL-100(Fe)(0.9gTTAB)With MIL-100 (Fe)(0.9gCTAB)In low temperature
Degree section denitration ability is remarkably reinforced, and it is respectively 215 DEG C and 184 DEG C that its denitration rate, which reaches temperature needed for 90%, with MIL-100 (Fe)
Compared to 25 DEG C and 56 DEG C of reduction respectively；
Fig. 7 is the denitration curve of different generated time MIL-100 (Fe),
It was found that at 280 DEG C, generated time is respectively the organic bone of ferrous metals obtained by 6h, 12h, 18h, 24h and 30h
For frame in catalytic denitration detection, the optimal denitration rate that can reach is respectively 60%, 77%, 86%, 98%, 69%.
Embodiment：
With reference to embodiment, the invention will be further described, rather than limitation of the present invention.
Embodiment 1：MIL-100(Fe)(0.9gCTAB)Catalyst denitration
First 1.42g (0.67mmol) trimesic acid (1,3,5-BTC, 98%) is added in 50mL ultra-pure waters, ultrasonic wave
Stirring 15min obtains solution A.Then toward 0.90gCTAB is added in A liquid, ultrasonic wave stirring 15min obtains B liquid.Again toward in B solution according to
Secondary addition 0.90mL hydrofluoric acid (HF, 40%) and 0.42mL nitric acid (HNO3, 60%), ultrasonic wave stirring 15min, obtain C solution.Will
C solution is poured into 60mL polytetrafluoroethyllining linings, adds 0.58g (1mmol) iron powders (Fe0).Polytetrafluoroethyllining lining is put
Enter in 60ml steel bombs, be placed in baking oven, be uniformly controlled reaction temperature in 150 DEG C of constant temperature 24h.After reaction terminates, by steel
Reactor processed, which is placed in air, is cooled to room temperature.Reactor is opened after cooling, outwells supernatant, remaining troubled liquor is shifted
Into beaker, then circulation washing is until impurity eliminates in ultra-pure water (70 DEG C) and alcohol (70 DEG C), and gained sample is at 70 DEG C
Grinding obtains Chinese red solid product MIL-100 (Fe) after lower dry 12h(0.9gCTAB)。
Load 10g catalyst MIL-100 (Fe) in the reactor of tube type resistance furnace(0.9gCTAB), first lead to nitrogen 5 minutes,
Then start to warm up, while be passed through carbon monoxide and nitric oxide mixed gas (carbon monoxide percent by volume is 30%, an oxygen
It is 30% to change nitrogen percent by volume, and remaining is nitrogen), air speed is 12000mL/ (gh), and tail gas detects by flue gas analyzer
After be passed through recycling in limewash, constant temperature is kept when denitration rate is close to 100%, denitration efficiency is when temperature is 220 DEG C
99.9%, and denitration efficiency is 90% when temperature is 184 DEG C, and denitration efficiency 98% during 280 DEG C of MIL-100 (Fe), MIL-100
(Fe) 240 DEG C when denitration efficiency 90%, illustrate MIL-100 (Fe)(0.9gCTAB)With preferable low-temperature catalyzed denitration effect.
Embodiment 2：MIL-100(Fe)(0.9gTTAB)Catalyst denitration
First 1.42g (0.67mmol) trimesic acid (1,3,5-BTC, 98%) is added in 50mL ultra-pure waters, ultrasonic wave
Stirring 15min obtains solution A.Then toward 0.90gTTAB is added in A liquid, ultrasonic wave stirring 15min obtains B liquid.Again toward in B solution according to
Secondary addition 0.90mL hydrofluoric acid (HF, 40%) and 0.42mL nitric acid (HNO3, 60%), ultrasonic wave stirring 15min, obtain C solution.Will
C solution is poured into 60mL polytetrafluoroethyllining linings, adds 0.58g (1mmol) iron powder (Fe0).Polytetrafluoroethyllining lining is put
Enter in 60ml steel bombs, be placed in baking oven, be uniformly controlled reaction temperature in 150 DEG C of constant temperature 24h.After reaction terminates, by steel
Reactor processed, which is placed in air, is cooled to room temperature.Reactor is opened after cooling, outwells supernatant, remaining troubled liquor is shifted
Into beaker, then circulation washing is until impurity eliminates in ultra-pure water (70 DEG C) and alcohol (70 DEG C), and gained sample is at 70 DEG C
Grinding obtains Chinese red solid product MIL-100 (Fe) after lower dry 12h(0.9gTTAB)。
Load 10g MIL-100 (Fe) in the reactor of tube type resistance furnace(0.9gTTAB)Catalyst, first leads to nitrogen 5 minutes,
Then start to warm up, while be passed through carbon monoxide and nitrogen dioxide mixed gas (carbon monoxide percent by volume is 60%, dioxy
It is 30% to change nitrogen percent by volume, and remaining is nitrogen), air speed is 12000mL/ (gh), and tail gas detects by flue gas analyzer
After be passed through recycling in limewash, keep constant temperature when denitration rate is close to 90%；Denitration efficiency is 90% when temperature is 215 DEG C,
Denitration efficiency 90% during compared to 240 DEG C of MIL-100 (Fe), illustrates MIL-100 (Fe)(0.9gTTAB)With preferably low-temperature catalyzed de-
Nitre effect.
Claims (9)
1. the method that one kind prepares ferrous metals organic framework material MIL-100 (Fe), it is characterised in that preparing ferrous metals has
Surfactant is added during machine framework material MIL-100 (Fe).
2. according to the method for claim 1, it is characterised in that described surfactant includes：Tetradecyltrimethylammonium
Ammonium bromide, cetyl trimethylammonium bromide, neopelex, lauryl sodium sulfate, polyvinylpyrrolidone and
One or more in polyvinyl alcohol.
3. according to the method for claim 2, it is characterised in that described surfactant is tetradecyltrimethylammonium bromination
Ammonium or cetyl trimethylammonium bromide.
4. according to the method for claim 3, it is characterised in that described surfactant is cetyl trimethyl bromination
Ammonium.
5. according to the method for claim 1, it is characterised in that described surfactant is dense in whole reaction system
Spend for 1-24g/L, preferably 18g/L.
6. according to the method described in claim any one of 1-5, it is characterised in that ferrous metals organic framework material MIL-100
(Fe) preparation process is：First trimesic acid is added in ultra-pure water, is uniformly mixing to obtain solution A；Then toward adding one in A liquid
Quantitative surfactant, stir to obtain B liquid；Hydrofluoric acid and nitric acid are sequentially added into B solution, it is molten to be uniformly mixing to obtain C
Liquid；It is put into after iron powder will be added in C solution in reactor, temperature reaction, after reaction terminates, cooling, outwells supernatant, will be remaining
Troubled liquor washing impurity-removing, after gained sample drying grinding obtain Chinese red solid product.
7. according to the method for claim 6, it is characterised in that trimesic acid concentration is 10- in whole reaction system
50g/L, preferably 30g/L；Hydrofluoric acid concentration is 10-100ml/L, preferably 18ml/L；Concentration of nitric acid is 5-50ml/L, preferably
10ml/L；The adding proportion of iron powder is 8-20g/L, preferably 12g/L.
8. according to the method for claim 6, it is characterised in that reactor is placed in an oven, and it is 100- to be warming up to temperature
200 DEG C, preferably 150 DEG C, preferably constant temperature 10-30h, 24h.
9. according to the method for claim 6, it is characterised in that first add trimesic acid in ultra-pure water, ultrasonic wave stirs
Mix 15min and obtain solution A；Then toward surfactant is added in A liquid, ultrasonic wave stirring 15min obtains B liquid；Into B solution successively
Hydrofluoric acid and nitric acid are added, ultrasonic wave stirring 15min obtains C solution；Steel bomb is put into after iron powder will be added in C solution
In, baking oven is placed in, is uniformly controlled reaction temperature；After reaction terminates, steel bomb is placed in air and is cooled to room temperature；Cooling
After open reactor, outwell supernatant, remaining troubled liquor be transferred in beaker, then in 70 DEG C of ultra-pure waters and 70 DEG C of wine
Circulation washing in essence is until impurity eliminates, and grinding obtains Chinese red solid product to gained sample after dry 12h at 70 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108585100A (en) * | 2018-04-18 | 2018-09-28 | 福州大学 | A method of adsorbing water Malachite Green using metal-organic framework materials MIL-100 (Fe) |
| CN110170337A (en) * | 2019-05-20 | 2019-08-27 | 辽宁石油化工大学 | Metal-organic framework materials MIL-53(Fe) hole-closing structure preparation method |
| CN111392742A (en) * | 2020-04-16 | 2020-07-10 | 中南大学 | Molecular sieve material AM-6, and preparation method and application thereof |
| CN111569945A (en) * | 2020-05-28 | 2020-08-25 | 万华化学集团股份有限公司 | Solid sulfonic acid catalyst and application thereof in preparation of cellulose acetate butyrate |
| 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 |
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| 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 |
| WO2015142944A2 (en) * | 2014-03-18 | 2015-09-24 | The Regents Of The University Of California | Mesoscopic materials comprised of ordered superlattices of microporous metal-organic frameworks |
| CN106268952A (en) * | 2016-07-20 | 2017-01-04 | 大连理工大学 | The preparation method of a kind of load type double-metal organic framework material MIL 100 (Fe Cu) and denitration application |
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| 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 |
| WO2015142944A2 (en) * | 2014-03-18 | 2015-09-24 | The Regents Of The University Of California | Mesoscopic materials comprised of ordered superlattices of microporous metal-organic frameworks |
| CN106268952A (en) * | 2016-07-20 | 2017-01-04 | 大连理工大学 | The preparation method of a kind of load type double-metal organic framework material MIL 100 (Fe Cu) and denitration application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108585100A (en) * | 2018-04-18 | 2018-09-28 | 福州大学 | A method of adsorbing water Malachite Green using metal-organic framework materials MIL-100 (Fe) |
| CN110170337A (en) * | 2019-05-20 | 2019-08-27 | 辽宁石油化工大学 | Metal-organic framework materials MIL-53(Fe) hole-closing structure preparation method |
| CN111392742A (en) * | 2020-04-16 | 2020-07-10 | 中南大学 | Molecular sieve material AM-6, and preparation method and application thereof |
| CN111392742B (en) * | 2020-04-16 | 2021-09-07 | 中南大学 | Molecular sieve material AM-6, and preparation method and application thereof |
| CN111569945A (en) * | 2020-05-28 | 2020-08-25 | 万华化学集团股份有限公司 | Solid sulfonic acid catalyst and application thereof in preparation of cellulose acetate butyrate |
| CN111569945B (en) * | 2020-05-28 | 2022-11-08 | 万华化学集团股份有限公司 | Solid sulfonic acid catalyst and application thereof in preparation of cellulose acetate butyrate |
| 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 |
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