CN107446137B - Method for preparing iron-based metal organic framework material MIL-100(Fe) - Google Patents
Method for preparing iron-based metal organic framework material MIL-100(Fe) Download PDFInfo
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- 239000013144 Fe-MIL-100 Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 17
- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 41
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- 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 18
- 238000003756 stirring Methods 0.000 claims description 17
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical group [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 6
- 239000007788 liquid Substances 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003546 flue gas Substances 0.000 abstract description 12
- 239000013291 MIL-100 Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000001514 detection method Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010453 quartz Substances 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
- 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 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
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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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- 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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- 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]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B01D—SEPARATION
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- B01D2258/0283—Flue gases
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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
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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 a method for preparing an iron-based metal organic framework material MIL-100 (Fe). In the invention, the surfactant is added in the process of preparing the iron-based metal organic framework material, so that MIL-100(Fe) with uniform components and particle size and more regular crystal morphology is synthesized in an auxiliary manner. Through flue gas denitration detection and analysis, the denitration temperature is reduced by 10-60 ℃ when the catalytic denitration rate reaches 99.9% compared with a sample without the surfactant.
Description
Technical Field
The invention belongs to the technical field of flue gas denitration materials and preparation thereof, and relates to a method for preparing an iron-based metal organic framework material MIL-100 (Fe).
Background
Low-temperature denitration of flue gas is one of the problems which are urgently needed to be solved in the field of flue gas environmental protection at present. Currently, NH is used in industry3Is a reducing agent and V2O5+WO3(MoO3)/TiO2For the selective catalytic reduction of the catalyst, the active temperature window is 300-400 ℃, and the service life is influenced by SO2And ash content. For example, in patent document No. 201310307034.0, metal organic framework MIL-100(Fe) is used as a catalyst, and in the examples, the ammonia gas denitration activity at a relatively low temperature of 270 ℃ is only 90%.
If the denitration temperature of the metal-organic framework MIL-100(Fe) is further reduced, the collapse of the metal-organic framework material catalyst (280-350 ℃) in the denitration process can be avoided. Therefore, the surfactant is added in the process of preparing the metal organic framework material MIL-100(Fe), so that the MIL-100(Fe) with uniform components and particle sizes and more regular crystal morphology is synthesized in an auxiliary manner, and the catalyst which has high catalytic activity in a low temperature range and can be recycled is found.
Disclosure of Invention
The invention aims to provide a method for preparing an iron-based metal organic framework material MIL-100 (Fe). The surfactant is added in the process of preparing the iron-based metal organic framework material MIL-100(Fe), so that the MIL-100(Fe) with uniform components and particle size and more regular crystal morphology is synthesized in an auxiliary manner, and the temperature for catalytic denitration is reduced on the premise of reaching 99.9% of catalytic denitration rate.
A method for preparing an iron-based metal organic framework material MIL-100(Fe) is characterized in that a surfactant is added in the process of preparing the iron-based metal organic framework material MIL-100 (Fe).
The surfactant comprises: one or more of tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, sodium dodecylsulfate, polyvinylpyrrolidone, and polyvinyl alcohol.
The surfactant is preferably tetradecyltrimethylammonium bromide or hexadecyltrimethylammonium bromide.
The surfactant is more preferably cetyltrimethylammonium bromide.
The concentration of the surfactant in the whole reaction system is 1-24 g/L. Preferably 18 g/L.
The method for preparing the iron-based metal organic framework material MIL-100(Fe) comprises the following steps: the preparation method of the iron-based metal organic framework material MIL-100(Fe) comprises the following steps: firstly, adding trimesic acid into ultrapure water, and uniformly stirring to obtain a solution A; then adding a certain amount of surfactant into the solution A, and uniformly stirring to obtain solution B; sequentially adding hydrofluoric acid and nitric acid into the solution B, and uniformly stirring to obtain a solution C; and adding iron powder into the solution C, then placing the solution C into a reaction kettle, heating for reaction, cooling after the reaction is finished, pouring out a supernatant, washing the remaining turbid liquid to remove impurities, drying the obtained sample, and grinding to obtain an orange solid product.
The concentration of the trimesic acid in the whole reaction system is 10-50g/L, preferably 30 g/L; the concentration of hydrofluoric acid is 10-100ml/L, preferably 18 ml/L; the concentration of nitric acid is 5-50ml/L, preferably 10 ml/L; the addition ratio of the iron powder is 8-20g/L, preferably 12 g/L.
In the preparation method, the reaction kettle is placed in an oven, the temperature is raised to 200 ℃ at 100 ℃, the temperature is preferably 150 ℃, and the constant temperature is kept for 10-30h, preferably 24 h.
The preparation method comprises the following further specific processes: firstly, adding trimesic acid into ultrapure water, and ultrasonically stirring for 15min to obtain a solution A; then adding a surfactant into the solution A, and stirring for 15min by ultrasonic waves to obtain solution B; sequentially adding hydrofluoric acid and nitric acid into the solution B, and ultrasonically stirring for 15min to obtain a solution C; adding iron powder into the solution C, then placing the solution C into a steel reaction kettle, placing the reaction kettle in an oven, and uniformly controlling the reaction temperature; after the reaction is finished, placing the steel reaction kettle in the air and cooling to room temperature; after cooling, the reaction kettle is opened, the supernatant is poured off, the remaining turbid liquid is transferred to a beaker and then circularly washed in 70 ℃ ultrapure water and 70 ℃ alcohol until impurities are removed, and the obtained sample is dried at 70 ℃ for 12 hours and then ground to obtain an orange solid product.
The control of various conditions, the adding sequence, the concentration and the adding proportion of the raw materials in the preparation method greatly influence whether the final product can be successfully prepared. For example, the addition proportion of the raw materials is out of the range of the invention, the light product generates impurities, the product color is not normal, the performance is seriously influenced, and the heavy product fails to react and generates flocculent precipitate. The reaction does not proceed smoothly without following the order of addition of the raw materials of the present invention, the octahedral substance of the present invention is not produced, or the target denitration rate cannot be achieved even if octahedral is produced, and the like.
The denitration detection analysis step of the iron-based metal organic framework material MIL-100(Fe) as a catalyst comprises the following steps:
(1) opening a flue gas analyzer and a gas distribution instrument for preheating for 30 min;
(2) weighing 0.50g of a catalyst sample, fixing the catalyst sample in a quartz tube reactor by using quartz cotton, and putting the quartz tube reactor into a tubular resistance furnace;
(3) connecting a laboratory instrument and a pipeline, setting parameters of a gas distribution instrument, starting an air inlet valve of reaction gas at the integral gas flow rate of 100mL/min which is well explored by a laboratory;
(4) setting a temperature control program, starting the tubular resistance furnace, and heating to a preset value;
(5) starting a counting system of the flue gas analyzer, recording the NO concentration at the outlet once every minute, and stopping recording when the NO concentration at the outlet is basically stable;
(6) stopping introducing the reaction gas, and closing the experimental equipment.
In the method, the flue gas comprises flue gas discharged by a power plant and a metallurgical plant.
The iron-based metal organic framework material catalyst prepared by the surfactant in an auxiliary manner can achieve the purpose of efficient denitration at a lower temperature, and the catalyst is lower in use temperature on the premise of ensuring high denitration rate, so that support is provided for the next step of carrying out an engineering flue gas denitration treatment test. The method has great significance for realizing large-scale industrial application of catalytic denitration of the flue gas.
Drawings
FIG. 1 is a scanning electron micrograph (5000 times magnification) of MIL-100(Fe) synthesized with different amounts of TTAB and CTAB; along with increasing addition amount, the shape of the regular octahedron of the sample is better, and the denitration rate is higher;
FIG. 2 is an XRD spectrum of MIL-100(Fe) synthesized with the aid of TTAB (0.9g) and CTAB (0.9g), respectively;
FIG. 3 shows MIL-100(Fe)(0.9gTTAB)、MIL-100(Fe)(0.9gCTAB)And thermogram of MIL-100 (Fe);
FIG. 4 shows MIL-100(Fe)(0.9gTTAB)、MIL-100(Fe)(0.9gCTAB)And an infrared spectrum of MIL-100 (Fe);
FIG. 5 shows MIL-100(Fe)(0.9gTTAB)、MIL-100(Fe)(0.9gCTAB)And Raman spectra of MIL-100 (Fe);
FIG. 6 shows MIL-100(Fe)(0.9gTTAB)、MIL-100(Fe)(0.9gCTAB)And denitration curve for MIL-100 (Fe);
at a reaction temperature of 280 ℃, MIL-100(Fe) and MIL-100(Fe)(0.9gTTAB)And MIL-100(Fe)(0.9gCTAB)The optimum denitration rates of the catalyst are respectively 98%, 99.9% and 99.9%, wherein MIL-100(Fe)(0.9gCTAB) 99.9% at 220 deg.C, which is reduced by 60% compared with MIL-100 (Fe); MIL-100(Fe)(0.9gTTAB)And MIL-100(Fe)(0.9gCTAB)The denitration capacity is obviously enhanced in a low-temperature section, the required temperatures for reaching 90 percent of the denitration rate are 215 ℃ and 184 ℃, and the denitration rate is respectively reduced by 25 ℃ and 56 ℃ compared with the temperature of MIL-100 (Fe);
FIG. 7 shows denitration curves for MIL-100(Fe) at different synthesis times,
it is found that the optimal denitration rates of the iron-based metal organic framework prepared by respectively synthesizing 6h, 12h, 18h, 24h and 30h at 280 ℃ in the catalytic denitration detection are respectively 60%, 77%, 86%, 98% and 69%.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1: MIL-100(Fe)(0.9gCTAB)Catalytic denitration by catalyst
1.42g (0.67mmol) of trimesic acid (1,3,5-BTC, 98%) is added into 50mL of ultrapure water, and ultrasonic stirring is carried out for 15min to obtain a solution A. Then 0.90g CTAB is added into the solution A, and the solution B is obtained after ultrasonic stirring for 15 min. Then 0.90mL of hydrofluoric acid (HF, 40%) and 0.42mL of nitric acid (HNO) were added to the solution B in that order 360%), ultrasonically stirring for 15min to obtain solution C. The solution C was poured into 60mL of Teflon liner, and 0.58g (1mmol) of iron powder (Fe) was added0). Putting the polytetrafluoroethylene lining into a 60ml steel reaction kettle, putting the reaction kettle into an oven, and uniformly controlling the reaction temperature to be constant at 150 ℃ for 24 hours. After the reaction is finished, the steel reaction kettle is placed in the air and cooled to the room temperature. After cooling, the reaction kettle is opened, the supernatant is poured off, the remaining turbid liquid is transferred into a beaker and then circularly washed in ultrapure water (70 ℃) and alcohol (70 ℃) until impurities are removed, the obtained sample is dried for 12 hours at 70 ℃ and then ground to obtain an orange solid product MIL-100(Fe)(0.9gCTAB)。
The reactor of a tubular resistance furnace was charged with 10g of catalyst MIL-100(Fe)(0.9gCTAB)Introducing nitrogen for 5 minutes, then starting to heat, simultaneously introducing a mixed gas of carbon monoxide and nitrogen monoxide (the volume percentage of carbon monoxide is 30%, the volume percentage of nitrogen monoxide is 30%, and the balance is nitrogen), wherein the space velocity is 12000 mL/(g.h), the tail gas is detected by a flue gas analyzer and then is introduced into lime water for recycling, the tail gas is kept at a constant temperature when the denitration rate is close to 100%, the denitration efficiency is 99.9% when the temperature is 220 ℃, the denitration efficiency is 90% when the temperature is 184 ℃, the denitration efficiency is 98% when MIL-100(Fe) is 280 ℃, the denitration efficiency is 90% when MIL-100(Fe) is 240 ℃, and the description shows that MIL-100(Fe)(0.9gCTAB)Has better low-temperature catalytic denitration effect.
Example 2: MIL-100(Fe)(0.9gTTAB)CatalystChemical denitration
1.42g (0.67mmol) of trimesic acid (1,3,5-BTC, 98%) is added into 50mL of ultrapure water, and ultrasonic stirring is carried out for 15min to obtain a solution A. Then 0.90g of TTAB is added into the solution A, and the mixture is stirred for 15min by ultrasonic waves to obtain solution B. Then 0.90mL of hydrofluoric acid (HF, 40%) and 0.42mL of nitric acid (HNO) were added to the solution B in that order 360%), ultrasonically stirring for 15min to obtain solution C. The solution C was poured into 60mL Teflon liner and 0.58g (1mmol) of iron powder (Fe0) was added. Putting the polytetrafluoroethylene lining into a 60ml steel reaction kettle, putting the reaction kettle into an oven, and uniformly controlling the reaction temperature to be constant at 150 ℃ for 24 hours. After the reaction is finished, the steel reaction kettle is placed in the air and cooled to the room temperature. After cooling, the reaction kettle is opened, the supernatant is poured off, the remaining turbid liquid is transferred into a beaker and then circularly washed in ultrapure water (70 ℃) and alcohol (70 ℃) until impurities are removed, the obtained sample is dried for 12 hours at 70 ℃ and then ground to obtain an orange solid product MIL-100(Fe)(0.9gTTAB)。
The reactor of a tubular resistance furnace was charged with 10g of MIL-100(Fe)(0.9gTTAB)Introducing nitrogen into the catalyst for 5 minutes, then starting to heat, simultaneously introducing a mixed gas of carbon monoxide and nitrogen dioxide (the volume percentage of the carbon monoxide is 60%, the volume percentage of the nitrogen dioxide is 30%, and the balance is nitrogen), wherein the space velocity is 12000 mL/(g.h), introducing the tail gas into lime water for recycling after detection by a flue gas analyzer, and keeping constant temperature when the denitration rate is close to 90%; the denitration efficiency is 90% at 215 ℃, compared with 90% at 240 ℃ of MIL-100(Fe), which shows that MIL-100(Fe)(0.9gTTAB)Has better low-temperature catalytic denitration effect.
Claims (7)
1. A method for preparing an iron-based metal organic framework material MIL-100(Fe) is characterized by comprising the following preparation steps: firstly, adding trimesic acid into ultrapure water, and uniformly stirring to obtain a solution A; then adding a certain amount of surfactant into the solution A, and uniformly stirring to obtain solution B; sequentially adding hydrofluoric acid and nitric acid into the solution B, and uniformly stirring to obtain a solution C; adding iron powder into the solution C, then placing the solution C into a reaction kettle, heating for reaction, cooling after the reaction is finished, pouring out supernatant, washing the remaining turbid liquid to remove impurities, drying the obtained sample, and grinding to obtain an orange solid product;
the concentration of the trimesic acid in the whole reaction system is 10-50 g/L; the concentration of hydrofluoric acid is 10-100 ml/L; the concentration of nitric acid is 5-50 ml/L; the adding proportion of the iron powder is 8-20 g/L;
the surfactant is tetradecyl trimethyl ammonium bromide or hexadecyl trimethyl ammonium bromide; the concentration of the surfactant in the whole reaction system is 1-24 g/L.
2. The method of claim 1 wherein the surfactant is cetyltrimethylammonium bromide.
3. The method according to claim 1, wherein the concentration of the surfactant in the whole reaction system is 18 g/L.
4. The method according to claim 1, wherein the concentration of trimesic acid in the whole reaction system is 30 g/L; the concentration of hydrofluoric acid is 18 ml/L; the concentration of nitric acid is 10 ml/L; the addition ratio of the iron powder is 12 g/L.
5. The method as claimed in claim 1, wherein the reaction kettle is placed in an oven and heated to a temperature of 100 ℃ to 200-oAnd C, keeping the temperature for 10-30 h.
6. The method of claim 5, wherein the reaction vessel is placed in an oven and heated to a temperature of 150 degrees CelsiusoAnd C, keeping the temperature for 24 hours.
7. The method of claim 1, wherein the solution A is obtained by adding trimesic acid into ultrapure water and ultrasonically stirring for 15 min; then adding a surfactant into the solution A, and stirring for 15min by ultrasonic waves to obtain solution B; sequentially adding hydrofluoric acid and nitric acid into the solution B, and ultrasonically stirring for 15min to obtain a solution C; adding iron powder into the solution C, putting the solution C into a steel reaction kettle, and placing the reaction kettle in a baking modeThe box is used for uniformly controlling the reaction temperature; after the reaction is finished, placing the steel reaction kettle in the air and cooling to room temperature; after cooling, the reaction vessel was opened, the supernatant decanted, and the remaining cloudy liquid transferred to a beaker at 70 deg.CoC ultrapure water and 70oC, circularly washing in alcohol until impurities are removed, and obtaining a sample at 70 DEGoAnd C, drying for 12h, and grinding to obtain an orange solid product.
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