CN106622380A - Denitration catalyst and preparation method as well as application of denitration catalyst - Google Patents
Denitration catalyst and preparation method as well as application of denitration catalyst Download PDFInfo
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- CN106622380A CN106622380A CN201611227701.4A CN201611227701A CN106622380A CN 106622380 A CN106622380 A CN 106622380A CN 201611227701 A CN201611227701 A CN 201611227701A CN 106622380 A CN106622380 A CN 106622380A
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- denitrating catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 23
- 239000003546 flue gas Substances 0.000 claims abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 230000003009 desulfurizing effect Effects 0.000 claims 2
- 235000019504 cigarettes Nutrition 0.000 claims 1
- -1 ferriferous oxide Chemical compound 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 5
- ZGMCLEXFYGHRTK-UHFFFAOYSA-N [Fe].[Ce] Chemical compound [Fe].[Ce] ZGMCLEXFYGHRTK-UHFFFAOYSA-N 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
Classifications
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
-
- B01J35/61—
-
- 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
Abstract
The invention relates to a denitration catalyst and a preparation method as well as application of the denitration catalyst, belonging to the technical field of catalysts. According to the catalyst, a ZIFs mesoporous molecular sieve is taken as a carrier and the catalyst comprises the effective components of oxides of zinc and iron and the oxide of cerium. According to the denitration catalyst, the ZIFs mesoporous molecular sieve is taken as the carrier, the specific surface is greatly increased, adsorption and activation of more flue gases are facilitated and the denitration efficiency is improved. The carrier and the active components are simultaneously synthesized in one step during preparation, so that the compound characteristics of an iron element and a cerium element can be strengthened, the dispersity and the bonding strength of the active components on the surface of the carrier and the mechanical strength and the thermal stability of the catalyst are improved. The catalyst is relatively fine in particles, the active components are evenly dispersed, and the denitration catalyst has relatively high denitration activity, a relatively wide denitration temperature range and anti-SO2 activity; and the denitration catalyst does not need to be heated when applied to flue gas denitration, 100% denitration is not needed and the energy consumption is reduced.
Description
Technical field
The present invention relates to denitrating catalyst, and in particular to a kind of denitrating catalyst and its preparation method and application, belong to and urge
Agent technical field.
Background technology
It is an effective method with SCR (SCR) reaction removing atmosphere pollution NO.SCR denitrating flue gas
The key of technology is to select excellent catalyst.SCR catalyst answers strong active high, anti-poisoning capability, mechanical strength and resistance to
Polishing machine is good, with suitable operation temperature it is interval the features such as.Preferably it is with most widely used industrial SCR catalyst at present
V2O5/TiO2And V2O5-WO3/TiO2Catalyst, its major advantage shows high activity and high antisulphuric ability, but such catalyst
Need at a higher temperature (>350 DEG C) application, to avoid flue gas in SO2With NH3The NH that reaction is generated4HSO4(NH4)2S2O7The pore structure of blocking catalyst.But under many circumstances, high-temperature operation result in the increase of energy consumption and running cost, low temperature
SCR device is conducive to and China's most Industrial Boiler matching at present, therefore, the low temperature of SCR catalyst is caused generally
Attention.Though at present many low-temperature denitration catalysts have good denitration efficiency, SO is easily received2Poison and be difficult to practical application.
And these catalyst mainly prepare these preparation methods using coprecipitation, sol-gel process, are easily caused the work of catalyst
Property component is dispersed poor on carrier, and temperature window is also narrower, and less stable.Accordingly, it would be desirable to develop others
Low temperature sulfur resistive denitrating catalyst.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of de- with the high sulfur resistive of bigger serface low temperature
Denox catalyst, the denitrating catalyst can improve anti-SO2Toxicity and low-temperature catalytic activity, expand operation temperature window, so as to
Be conducive to industrial applications.
Above-mentioned purpose is achieved through the following technical solutions：
A kind of denitrating catalyst, the catalyst is that, with ZIFs mesopore molecular sieves as carrier, its active principle includes zinc, iron
Oxide, cerium oxide, the content of the zinc, ferriferous oxide and cerium oxide is with the mol ratio of elemental metal as Zn：Fe：Ce
=0.01：0.0001：0.0001～0.01：0.0007：0.0001.
Preferably, the zinc is simple substance zinc, and the ferriferous oxide is Fe2O3, the cerium oxide is CeO2And Ce2O3In
One or two；The zinc doping forms carrier in the ZIFs mesopore molecular sieves, to load the iron oxygen as active component
Compound and cerium oxide.
Preferably, the surface area of the denitrating catalyst is 800～1200m2/g。
It is a further object to provide the preparation method of the denitrating catalyst, comprises the following steps：
(1) salt solution containing zinc is obtained into the first solution in solvent 1；
(2) methylimidazole is dissolved in solvent 2, in being then added to the first solution, is stirred, obtain mixed liquor；
(3) after by molysite and the dissolving of cerium salt, the second solution containing ferriferous oxide and cerium oxide is prepared；
(4) the second solution is added in the mixed liquor of step (2), then magnetic agitation is aged；
(5) material after ageing in step (4) is filtered, is washed, is dried, is ground, then calcined again, oxygen
Change, obtain pressed powder, i.e. denitrating catalyst.
Preferably, step (1) salting liquid containing zinc includes Zn (NO3)2.5H2O、Zn(CH3COO)2In at least one
Kind；The solvent 1 includes at least one in ethanol, methyl alcohol, water, DMF；The concentration of the salting liquid containing zinc in first solution
For 0.03～0.04mol/L；Solvent 2 described in step (2) includes at least one in ethanol, methyl alcohol, DMF；Step (2) it is mixed
The concentration for closing methylimidazole described in liquid is 0.26～0.35mol/L；Step (3) molysite include ferric nitrate, ferric acetate,
At least one in ferric sulfate, the cerium salt includes at least one in cerous nitrate, cerous acetate, cerium chloride；Second solution
The total concentration of middle ferro element and Ce elements is 0.0002～0.0007mol/L.
Preferably, the rotating speed of step (4) magnetic agitation is 1000～2000r/min, and the time is 2～4h；It is described old
The time of change is 8～12h.
Preferably, described being filtered into of step (5) is filtered with the sintered glass filter that filter sizes are 0.22～0.45 μm；
The drying is vacuum drying, and baking temperature is 100～140 DEG C, and the time is 4～8h.
Preferably, the temperature of step (5) calcining is 350～500 DEG C, and the time is 3～5h.
It is also another object of the present invention to provide the application of the denitrating catalyst, de- to dedusting with the denitrating catalyst
Flue gas after sulphur carries out selective catalytic reduction reaction.First to flue-gas dust-removing and desulfurization, it is less than sulfur dioxide in flue gas concentration
400ppm, then low-temperature denitration is carried out, without the need for reheating to flue gas during denitration, energy resource consumption can be reduced and denitration effect is improved
Rate.
Preferably, SO in the flue gas after the dust-removal and desulfurizing2Concentration is 0～400ppm, and the SCR is anti-
The temperature answered is 80～300 DEG C.
Compared with prior art, the beneficial effects of the present invention is：
1. the denitrating catalyst of the present invention is carrier using ZIFs mesopore molecular sieves, compares and uses TiO2For carrier when, than
Surface greatly increases, and is conducive to Catalyst Adsorption and the more flue gases of activation, improves denitration efficiency；
2. the preparation method of the denitrating catalyst of the present invention is carrier and active component while one-step synthesis, can strengthen iron
The composite attribute of element and Ce elements, improves decentralization and bond strength of the active component in carrier surface, improves catalyst
Mechanical strength and heat endurance；
3. the denitrating catalyst of the present invention is prepared as one-step synthesis, and catalyst granules is thinner, active component is uniformly dispersed,
With higher denitration activity, wider denitration temperature range and anti-sulfur dioxide activity, at 80～300 DEG C, SO in flue gas2It is dense
Spend for 0～400ppm when, more than 85% denitration efficiency can be reached；
4. the denitrating catalyst of the present invention is applied to denitrating flue gas, without the need for heating before denitration, without the need for 100% desulfurization, reduces
Energy resource consumption.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of denitrating catalyst prepared by embodiment 1.
Specific embodiment
The present invention is described in further detail with reference to example is embodied as, but it is not as a limitation of the invention.
Embodiment 1
Weigh 3gZn (NO3)2·5H2O is dissolved into wiring solution-forming in 150mL methyl alcohol；8g methylimidazoles are dissolved into 150mL
Wiring solution-forming in ethanol, after two kinds of solution are well mixed, adds in the solution 50.1mg Fe (NO3)3·9H2O and
38.2mgCe(NO3)2·9H2O, stirs 2h under magnetic stirring apparatus rotating speed 1000r/min, stands 10 minutes, is then aged 8h；
With 0.22 μm of sintered glass filter suction filtration of filter membrane diameter, then 6h is dried in 140 DEG C of vacuum constant temperature drying boxes, is ground after taking-up
40-60 mesh powders are worn into, 500 DEG C of calcining 5h, are obtained the ZIFs mesopore molecular sieve denitration catalysts of iron cerium load in Muffle furnace
Agent, the specific surface of the catalyst is 1000m2/g。
Denitrating catalyst denitrating flue gas reaction condition obtained above is：Catalyst grain size is 40-60 mesh, and consumption is
200mg, reacting gas is consisted of：NO 500ppm、NH3500ppm, 3% (percent by volume) O2、SO2400ppm, using N2
For Balance Air, the gas space velocity in reaction is 30000mL/ (gh), and 80 DEG C of reaction temperature, catalyst denitration efficiency is 86%.
Catalytic perfomance data are tested in fixed-bed quartz reactor.
Embodiment 2
Weigh 2.5gZn (NO3)2·5H2O is dissolved into wiring solution-forming in 150mL ethanol；6.5g methylimidazoles are dissolved into
Wiring solution-forming in 150mLDMF, after two kinds of solution are well mixed, adds in the solution 100.2mg Fe (NO3)3·9H2O and
38.2mgCe(NO3)2·9H2O, stirs 2h under magnetic stirring apparatus rotating speed 1500r/min, stands 10 minutes, is aged 10h；With filter
The sintered glass filter suction filtration of 0.22 μm of film diameter, is then dried 6h in 140 DEG C of vacuum constant temperature drying boxes, and taking-up grinds to form
40-60 mesh powders, 400 DEG C of calcining 4h, are obtained the ZIFs mesopore molecular sieve denitrating catalysts of iron cerium load in Muffle furnace, should
The specific surface of catalyst is 900m2/g。
Denitrating catalyst denitrating flue gas reaction condition obtained above is：Catalyst grain size is 40-60 mesh, and consumption is
200mg, reacting gas is consisted of：NO 500ppm、NH3500ppm, 3% (percent by volume) O2、SO2400ppm, using N2
For Balance Air, the gas space velocity in reaction is 30000mL/ (gh), and 100 DEG C of reaction temperature, catalyst denitration efficiency is 88%.
Catalytic perfomance data are tested in fixed-bed quartz reactor.
Embodiment 3
Weigh 3gZn (NO3)2·5H2O is dissolved into wiring solution-forming in 150mL DMF；8g methylimidazoles are dissolved into
Wiring solution-forming in 150mLDMF, after two kinds of solution are well mixed, adds in the solution 125.3mg Fe (NO3)3·9H2O and
38.2mgCe(NO3)2·9H2O stirs 2h under magnetic stirring apparatus rotating speed 2000r/min, stands 10 minutes, is aged 12h；With filter
0.22 μm of sintered glass filter suction filtration of film diameter, is then dried 8h in 140 DEG C of vacuum constant temperature drying boxes, and taking-up grinds to form
40-60 mesh powders, 450 DEG C of calcining 4h, are obtained the ZIFs mesopore molecular sieve denitrating catalysts of iron cerium load in Muffle furnace, should
The specific surface of catalyst is 1200m2/g。
Denitrating catalyst denitrating flue gas reaction condition obtained above is：Catalyst grain size is 40-60 mesh, and consumption is
200mg, reacting gas is consisted of：NO 500ppm、NH3500ppm, 3% (percent by volume) O2, SO2 400ppm, using N2
For Balance Air, the gas space velocity in reaction is 30000mL/ (gh), and 150 DEG C of reaction temperature, catalyst denitration efficiency is 95%.
Catalytic perfomance data are tested in fixed-bed quartz reactor.
Embodiment 4
Weigh 3.5gZn (NO3)2·5H2O is dissolved into wiring solution-forming in 150mL distilled water；7.5g methylimidazoles are dissolved into
Wiring solution-forming in 150mL ethanol, after two kinds of solution are well mixed, adds in the solution 150.3mg Fe (NO3)3·9H2O and
38.2mg Ce(NO3)2·9H2O, stirs 2h under magnetic stirring apparatus rotating speed 2000r/min, stands 10 minutes, is aged 12h；With
The sintered glass filter suction filtration of 0.40 μm of filter membrane diameter, is then dried 6h in 140 DEG C of vacuum constant temperature drying boxes, takes out grinding
Into 40-60 mesh powders, 350 DEG C of calcining 5h, are obtained the ZIFs mesopore molecular sieve denitrating catalysts of iron cerium load in Muffle furnace,
The specific surface of the catalyst is 1100m2/g。
Denitrating catalyst denitrating flue gas reaction condition obtained above is：Catalyst grain size is 40-60 mesh, and consumption is
200mg, reacting gas is consisted of：NO 500ppm、NH3500ppm, 3% (percent by volume) O2、SO2400ppm, using N2
For Balance Air, the gas space velocity in reaction is 30000mL/ (gh), and 200 DEG C of reaction temperature, catalyst denitration efficiency is 92%.
Catalytic perfomance data are tested in fixed-bed quartz reactor.
Embodiment 5
Weigh 3gZn (NO3)2·5H2O is dissolved into wiring solution-forming in 150mL DMF；8g methylimidazoles are dissolved into 150mL
Wiring solution-forming in methyl alcohol, after two kinds of solution are well mixed, adds in the solution 250.5mg Fe (NO3)3·9H2O and
38.2mgCe(NO3)2·9H2O, stirs 2h under magnetic stirring apparatus rotating speed 1500r/min, stands 10 minutes, is aged 10h；With filter
The sintered glass filter suction filtration of 0.45 μm of film diameter, is then dried 6h in 140 DEG C of vacuum constant temperature drying boxes, and taking-up grinds to form
40-60 mesh powders, 350 DEG C of calcining 3h, are obtained the ZIFs mesopore molecular sieve denitrating catalysts of iron cerium load in Muffle furnace, should
The specific surface of catalyst is 800m2/g。
Denitrating catalyst denitrating flue gas reaction condition obtained above is：Catalyst grain size is 40-60 mesh, and consumption is
200mg, reacting gas is consisted of：NO 500ppm、NH3500ppm, 3% (percent by volume) O2、SO2400ppm, using N2
For Balance Air, the gas space velocity in reaction is 30000mL/ (gh), and 300 DEG C of reaction temperature, catalyst denitration efficiency is 85%.
Catalytic perfomance data are tested in fixed-bed quartz reactor.
Claims (10)
1. a kind of denitrating catalyst, it is characterised in that the catalyst is its active principle with ZIFs mesopore molecular sieves as carrier
Including zinc, ferriferous oxide, cerium oxide, the content of the zinc, ferriferous oxide and cerium oxide is with the mol ratio of elemental metal
For Zn：Fe：Ce=0.01：0.0001：0.0001～0.01：0.0007：0.0001.
2. denitrating catalyst according to claim 1, it is characterised in that the zinc is simple substance zinc, the ferriferous oxide is
Fe2O3, the cerium oxide is CeO2And Ce2O3In one or two；The zinc doping is in the ZIFs mesopore molecular sieves
Carrier is formed, to load ferriferous oxide and cerium oxide as active component.
3. denitrating catalyst according to claim 1, it is characterised in that the surface area of the denitrating catalyst is 800～
1200m2/g。
4. the preparation method of the denitrating catalyst any one of claim 1-3, it is characterised in that comprise the following steps：
(1) salt solution containing zinc is obtained into the first solution in solvent 1；
(2) methylimidazole is dissolved in solvent 2, in being then added to the first solution, is stirred, obtain mixed liquor；
(3) after by molysite and the dissolving of cerium salt, the second solution containing ferriferous oxide and cerium oxide is prepared；
(4) the second solution is added in the mixed liquor of step (2), then magnetic agitation is aged；
(5) material after ageing in step (4) is filtered, is washed, is dried, is ground, then calcined again, aoxidized, obtained
To pressed powder, i.e. denitrating catalyst.
5. the preparation method of denitrating catalyst according to claim 4, it is characterised in that step (1) salt containing zinc
Solution includes Zn (NO3)2.5H2O、Zn(CH3COO)2In at least one；The solvent 1 is included in ethanol, methyl alcohol, water, DMF
It is at least one；The concentration of the salting liquid containing zinc is 0.03～0.04mol/L in first solution；Step (2) solvent 2 is wrapped
Include at least one in ethanol, methyl alcohol, DMF；The concentration of methylimidazole is 0.26～0.35mol/ in the mixed liquor of step (2)
L；Step (3) molysite includes at least one in ferric nitrate, ferric acetate, ferric sulfate, and the cerium salt includes cerous nitrate, acetic acid
At least one in cerium, cerium chloride；In second solution total concentration of ferro element and Ce elements be 0.0002～
0.0007mol/L。
6. the preparation method of denitrating catalyst according to claim 4, it is characterised in that step (4) magnetic agitation
Rotating speed be 1000～2000r/min, the time be 2～4h；The time of the ageing is 8～12h.
7. the preparation method of denitrating catalyst according to claim 4, it is characterised in that step (5) is described to be filtered into use
Filter sizes are that 0.22～0.45 μm of sintered glass filter is filtered；The drying for vacuum drying, baking temperature be 100～
140 DEG C, the time is 4～8h.
8. the preparation method of denitrating catalyst according to claim 4, it is characterised in that the temperature of step (5) calcining
Spend for 350～500 DEG C, the time is 3～5h.
9. application of the denitrating catalyst described in claim 1-3 in denitrating flue gas, it is characterised in that use the denitration catalyst
Agent carries out selective catalytic reduction reaction to the flue gas after dust-removal and desulfurizing.
10. the application of catalyst for denitrating flue gas according to claim 9, it is characterised in that the cigarette after the dust-removal and desulfurizing
SO in gas2Concentration is 0～400ppm, and the temperature of the selective catalytic reduction reaction is 80～300 DEG C.
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