CN106622380B - A kind of denitrating catalyst and its preparation method and application - Google Patents
A kind of denitrating catalyst and its preparation method and application Download PDFInfo
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- CN106622380B CN106622380B CN201611227701.4A CN201611227701A CN106622380B CN 106622380 B CN106622380 B CN 106622380B CN 201611227701 A CN201611227701 A CN 201611227701A CN 106622380 B CN106622380 B CN 106622380B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 22
- 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 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 11
- 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 11
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000013019 agitation Methods 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
- 238000009938 salting Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 238000000034 method 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
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-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
- 238000004090 dissolution Methods 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
- 239000000843 powder Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims 1
- -1 ferriferous oxide Chemical compound 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 3
- 230000023556 desulfurization Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052684 Cerium Inorganic materials 0.000 abstract 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 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
- ZGMCLEXFYGHRTK-UHFFFAOYSA-N [Fe].[Ce] Chemical compound [Fe].[Ce] ZGMCLEXFYGHRTK-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 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
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000000903 blocking effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding 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
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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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
- B01J31/26—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
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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
-
- 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
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- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of denitrating catalysts and its preparation method and application, belong to catalyst technical field.Catalyst of the invention is using ZIFs mesopore molecular sieve as carrier, and active principle includes the oxide of zinc, the oxide of iron, cerium.Denitrating catalyst of the invention is carrier using ZIFs mesopore molecular sieve, and specific surface greatly increases, and is conducive to adsorb and activate more flue gases, improves denitration efficiency；Carrier and active component while one-step synthesis when preparation, can be enhanced the composite attribute of ferro element and Ce elements, improve active component in the dispersion degree and bond strength of carrier surface, the mechanical strength and thermal stability of catalyst；Catalyst granules is thinner, and active component is uniformly dispersed, denitration activity, wider denitration temperature range and anti-SO with higher2Activity；Reduce energy consumption without 100% desulfurization without heating when denitrating catalyst is applied to denitrating flue gas.
Description
Technical field
The present invention relates to denitrating catalysts, and in particular to a kind of denitrating catalyst and its preparation method and application belongs to and urges
Agent technical field.
Background technique
Reacting removing atmosphere pollution NO with selective catalytic reduction (SCR) is an effective method.SCR denitrating flue gas
The key of technology is the excellent catalyst of selection.SCR catalyst answer it is active it is high, anti-poisoning capability is strong, mechanical strength and resistance to
Polishing machine is good, has the characteristics that suitable operation temperature section.Preferably it is with most widely used industrial SCR catalyst at present
V2O5/TiO2And V2O5-WO3/TiO2Catalyst, major advantage show high activity and high antisulphuric ability, but such catalyst
(> 350 DEG C) applications at a higher temperature are needed, to avoid the SO in flue gas2With NH3React the NH generated4HSO4(NH4)2S2O7The pore structure of blocking catalyst.But high-temperature operation results in the increase of energy consumption and operating cost, low temperature in many cases,
SCR device be conducive to China's most of Industrial Boiler matching at present, therefore, the low temperature of SCR catalyst causes generally
Attention.Though current many low-temperature denitration catalysts have good denitration efficiency, vulnerable to SO2Poison and be difficult to practical application.
And these catalyst mainly use coprecipitation, sol-gel method preparation these preparation methods, are easy to cause the work of catalyst
Property component on carrier dispersibility it is poor, temperature window is also relatively narrow, and stability is poor.Therefore, it is necessary to develop others
Low temperature sulfur resistive denitrating catalyst.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide one kind to have the high sulfur resistive of bigger serface low temperature de-
Denox catalyst, the denitrating catalyst can be improved anti-SO2Toxicity and low-temperature catalytic activity expand operation temperature window, thus
Be conducive to industrial applications.
Above-mentioned purpose is achieved through the following technical solutions:
A kind of denitrating catalyst, the catalyst are using ZIFs mesopore molecular sieve as carrier, and active principle includes zinc, iron
Oxide, cerium oxide, the content of the zinc, ferriferous oxide and cerium oxide are Zn:Fe:Ce with the molar ratio of elemental metal
=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
It is one or two kinds of；The zinc doping forms carrier into the ZIFs mesopore molecular sieve, 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 methods of the denitrating catalyst, comprising the following steps:
(1) by the salt solution containing zinc in solvent 1, the first solution is obtained；
(2) methylimidazole is dissolved in solvent 2, is then added in the first solution, stirs evenly, obtains mixed liquor；
(3) by after molysite and cerium salt dissolution, 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, washed, dried, ground, then calcined again, oxygen
Change, obtains solid powder, i.e. denitrating catalyst.
Preferably, the salting liquid containing zinc described in step (1) includes Zn (NO3)2.5H2O、Zn(CH3COO)2In at least one
Kind；The solvent 1 includes at least one of ethyl alcohol, methanol, water, DMF；The concentration of salting liquid containing zinc in first solution
For 0.03~0.04mol/L；Solvent 2 described in step (2) includes at least one of ethyl alcohol, methanol, DMF；Step (2) is mixed
The concentration for closing methylimidazole described in liquid is 0.26~0.35mol/L；Step (3) described molysite include ferric nitrate, ferric acetate,
At least one of ferric sulfate, the cerium salt include at least one of 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 revolving speed of step (4) described 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 be 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 drying temperature is 100~140 DEG C, and the time is 4~8h.
Preferably, the temperature of step (5) described calcining is 350~500 DEG C, and the time is 3~5h.
It is also another object of the present invention to provide the applications 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 lower than sulfur dioxide in flue gas concentration
400ppm, then carry out low-temperature denitration, without being reheated to flue gas, energy consumption can be reduced and improving denitration effect when denitration
Rate.
Preferably, SO in the flue gas after the dust-removal and desulfurizing2Concentration is 0~400ppm, and the selective catalytic reduction is anti-
The temperature answered is 80~300 DEG C.
Compared with prior art, the beneficial effects of the present invention are:
1. denitrating catalyst of the invention is carrier using ZIFs mesopore molecular sieve, compares and use TiO2When for carrier, than
Surface greatly increases, and is conducive to Catalyst Adsorption and activates more flue gases, improves denitration efficiency；
2. the preparation method of denitrating catalyst of the invention is carrier and active component one-step synthesis simultaneously, iron can be enhanced
The composite attribute of element and Ce elements improves active component in the dispersion degree and bond strength of carrier surface, improves catalyst
Mechanical strength and thermal stability；
3. denitrating catalyst of the invention is prepared as one-step synthesis, catalyst granules is thinner, and active component is uniformly dispersed,
Denitration activity with higher, wider denitration temperature range and anti-sulfur dioxide activity, at 80~300 DEG C, SO in flue gas2It is dense
When degree is 0~400ppm, 85% or more denitration efficiency can be reached；
4. denitrating catalyst of the invention is applied to denitrating flue gas, without heating before denitration, it is not necessarily to 100% desulfurization, is reduced
Energy consumption.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of denitrating catalyst prepared by embodiment 1.
Specific embodiment
Below with reference to specific implementation example, present invention is further described in detail, but not as a limitation of the invention.
Embodiment 1
Weigh 3gZn (NO3)2·5H2O is dissolved into wiring solution-forming in 150mL methanol；8g methylimidazole is dissolved into 150mL
After mixing by two kinds of solution 50.1mg Fe (NO is added in wiring solution-forming in ethyl alcohol in the solution3)3·9H2O and
38.2mgCe(NO3)2·9H2O stirs 2h at magnetic stirring apparatus revolving speed 1000r/min, stands 10 minutes, is then aged 8h；
It is filtered with 0.22 μm of sintered glass filter of filter membrane diameter, then the dry 6h in 140 DEG C of vacuum constant temperature drying boxes, grinds after taking-up
It is powdered to wear into 40-60 mesh, the ZIFs mesopore molecular sieve denitration catalyst of iron cerium load is made in 500 DEG C of calcining 5h in Muffle furnace
Agent, the specific surface of the catalyst are 1000m2/g。
Denitrating catalyst denitrating flue gas reaction condition obtained above are as follows: catalyst grain size is 40-60 mesh, and dosage is
200mg, reaction gas composition are as follows: NO 500ppm, NH3500ppm, 3% (percent by volume) O2、SO2400ppm uses 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 ethyl alcohol；6.5g methylimidazole is dissolved into
After mixing by two kinds of solution 100.2mg Fe (NO is added in wiring solution-forming in 150mLDMF in the solution3)3·9H2O and
38.2mgCe(NO3)2·9H2O stirs 2h at magnetic stirring apparatus revolving speed 1500r/min, stands 10 minutes, is aged 10h；With filter
The sintered glass filter that 0.22 μm of film diameter filters, and then dry 6h, taking-up are ground into 140 DEG C of vacuum constant temperature drying boxes
40-60 mesh is powdered, 400 DEG C of calcining 4h in Muffle furnace, and the ZIFs mesopore molecular sieve denitrating catalyst of iron cerium load is made, should
The specific surface of catalyst is 900m2/g。
Denitrating catalyst denitrating flue gas reaction condition obtained above are as follows: catalyst grain size is 40-60 mesh, and dosage is
200mg, reaction gas composition are as follows: NO 500ppm, NH3500ppm, 3% (percent by volume) O2、SO2400ppm uses 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 methylimidazole is dissolved into
After mixing by two kinds of solution 125.3mg Fe (NO is added in wiring solution-forming in 150mLDMF in the solution3)3·9H2O and
38.2mgCe(NO3)2·9H2O stirs 2h at magnetic stirring apparatus revolving speed 2000r/min, stands 10 minutes, is aged 12h；With filter
0.22 μm of sintered glass filter of film diameter filters, and then in 8h dry in 140 DEG C of vacuum constant temperature drying boxes, taking-up is ground into
40-60 mesh is powdered, 450 DEG C of calcining 4h in Muffle furnace, and the ZIFs mesopore molecular sieve denitrating catalyst of iron cerium load is made, should
The specific surface of catalyst is 1200m2/g。
Denitrating catalyst denitrating flue gas reaction condition obtained above are as follows: catalyst grain size is 40-60 mesh, and dosage is
200mg, reaction gas composition are as follows: NO 500ppm, NH3500ppm, 3% (percent by volume) O2, SO2 400ppm, use 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 methylimidazole is dissolved into
After mixing by two kinds of solution 150.3mg Fe (NO is added in wiring solution-forming in 150mL ethyl alcohol in the solution3)3·9H2O and
38.2mg Ce(NO3)2·9H2O stirs 2h at magnetic stirring apparatus revolving speed 2000r/min, stands 10 minutes, is aged 12h；With
The sintered glass filter that 0.40 μm of filter membrane diameter filters, and then in 6h dry in 140 DEG C of vacuum constant temperature drying boxes, takes out grinding
Powdered at 40-60 mesh, the ZIFs mesopore molecular sieve denitrating catalyst of iron cerium load is made in 350 DEG C of calcining 5h in Muffle furnace,
The specific surface of the catalyst is 1100m2/g。
Denitrating catalyst denitrating flue gas reaction condition obtained above are as follows: catalyst grain size is 40-60 mesh, and dosage is
200mg, reaction gas composition are as follows: NO 500ppm, NH3500ppm, 3% (percent by volume) O2、SO2400ppm uses 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 methylimidazole is dissolved into 150mL
After mixing by two kinds of solution 250.5mg Fe (NO is added in wiring solution-forming in methanol in the solution3)3·9H2O and
38.2mgCe(NO3)2·9H2O stirs 2h at magnetic stirring apparatus revolving speed 1500r/min, stands 10 minutes, is aged 10h；With filter
The sintered glass filter that 0.45 μm of film diameter filters, and then in 6h dry in 140 DEG C of vacuum constant temperature drying boxes, taking-up is ground into
40-60 mesh is powdered, 350 DEG C of calcining 3h in Muffle furnace, and the ZIFs mesopore molecular sieve denitrating catalyst of iron cerium load is made, should
The specific surface of catalyst is 800m2/g。
Denitrating catalyst denitrating flue gas reaction condition obtained above are as follows: catalyst grain size is 40-60 mesh, and dosage is
200mg, reaction gas composition are as follows: NO 500ppm, NH3500ppm, 3% (percent by volume) O2、SO2400ppm uses 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 (8)
1. a kind of denitrating catalyst, which is characterized in that the catalyst is the active principle using ZIFs mesopore molecular sieve as carrier
Including zinc, ferriferous oxide, cerium oxide, the content of the zinc, ferriferous oxide and cerium oxide is with the molar ratio of elemental metal
For Zn:Fe:Ce=0.01:0.0001:0.0001~0.01:0.0007:0.0001；
Wherein the zinc is simple substance zinc, and the ferriferous oxide is Fe2O3, the cerium oxide is CeO2And Ce2O3One of or
Two kinds；
The denitrating catalyst is prepared by the following method:
(1) by the salt solution containing zinc in solvent 1, the first solution is obtained；
(2) methylimidazole is dissolved in solvent 2, is then added in the first solution, stirs evenly, obtains mixed liquor；
(3) by after molysite and cerium salt dissolution, the second solution containing molysite and cerium salt 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, washed, dried, ground, then calcined again, aoxidized, obtain
To solid powder, i.e. denitrating catalyst.
2. denitrating catalyst according to claim 1, which is characterized in that the specific surface area of the denitrating catalyst is 800
~1200m2/g。
3. denitrating catalyst according to claim 1, which is characterized in that the salting liquid containing zinc described in step (1) includes Zn
(NO3)2·5H2O、Zn(CH3COO)2At least one of；The solvent 1 includes at least one of ethyl alcohol, methanol, water, DMF；
The concentration of the salting liquid containing zinc is 0.03~0.04mol/L in first solution；Step (2) solvent 2 includes ethyl alcohol, first
At least one of alcohol, DMF；The concentration of methylimidazole is 0.26~0.35mol/L in the mixed liquor of step (2)；Step (3)
The molysite includes at least one of ferric nitrate, ferric acetate, ferric sulfate, and the cerium salt includes cerous nitrate, cerous acetate, cerium chloride
At least one of；The total concentration of ferro element and Ce elements is 0.0002~0.0007mol/L in second solution.
4. denitrating catalyst according to claim 1, which is characterized in that the revolving speed of step (4) described magnetic agitation is
1000~2000r/min, time are 2~4h；The time of the ageing is 8~12h.
5. denitrating catalyst according to claim 1, which is characterized in that described be filtered into of step (5) be with filter sizes
0.22~0.45 μm of sintered glass filter filtering；The drying is vacuum drying, and drying temperature is 100~140 DEG C, the time
For 4~8h.
6. denitrating catalyst according to claim 1, which is characterized in that the temperature of step (5) described calcining be 350~
500 DEG C, the time is 3~5h.
7. application of the denitrating catalyst described in claim 1 in denitrating flue gas, which is characterized in that with the denitrating catalyst
Selective catalytic reduction reaction is carried out to the flue gas after dust-removal and desulfurizing.
8. application according to claim 7, which is characterized in that SO in the flue gas after the dust-removal and desulfurizing2Concentration be 0~
400ppm, the temperature of the selective catalytic reduction reaction are 80~300 DEG C.
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| CN109395710B (en) * | 2018-08-20 | 2021-05-25 | 浙江师范大学 | Preparation method of cerium and carbon co-doped zinc oxide |
| CN111185242B (en) * | 2020-01-09 | 2022-12-13 | 五邑大学 | Co 3 O 4 -mMO x ZIFs composite material and preparation and application thereof |
| CN112023908B (en) * | 2020-08-04 | 2023-03-17 | 华北电力大学 | Nitrogen oxide removing catalyst and preparation method thereof |
| KR102474152B1 (en) * | 2020-10-16 | 2022-12-02 | 성균관대학교산학협력단 | Ceria nanoparticles and method for preparing the same |
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