CN108126715A - A kind of denitrating catalyst - Google Patents
A kind of denitrating catalyst Download PDFInfo
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- CN108126715A CN108126715A CN201711398761.7A CN201711398761A CN108126715A CN 108126715 A CN108126715 A CN 108126715A CN 201711398761 A CN201711398761 A CN 201711398761A CN 108126715 A CN108126715 A CN 108126715A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 31
- 230000000694 effects Effects 0.000 claims abstract description 25
- 239000000919 ceramic Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 18
- 239000011149 active material Substances 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 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
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012298 atmosphere Substances 0.000 abstract description 16
- 239000000779 smoke Substances 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 229910016978 MnOx Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
-
- B01J35/397—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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 discloses a kind of denitrating catalyst, which provides matrix foamed ceramics and the catalyst composite oxides MnO being supported in matrixx- CuSO4, preparation method prepares back loading on foamed ceramics for Ti colloidal sols, then by drying and calcining, the activating substance in load, most afterwards through calcining molding again, with N in preparation process2As prepared atmosphere, the catalyst low-temperature denitration activity prepared is high；And active temperature windows are wider；There is good anti-SO2Poisoning capability；Product is integral catalyzer, can be suitably used for the practical smoke gas treatment of industry.
Description
Technical field
The present invention relates to field of denitration catalyst more particularly to a kind of denitrating catalysts.
Background technology
The usage amount of the fossil fuels such as oil and coal also increases year by year, so that the nitrogen oxides released, oxysulfide
And the pollutants such as dust cause air serious pollution, and in following a very long time, the combustion of the fossils such as coal
Material is still the main energy sources in China, and such as Thermal Power Generation Industry, more than 95% is all based on burning coal.The emission reduction of nitrogen oxides
Work starts to be paid high attention to by people.
In numerous denitration technologies, since SCR methods are higher to the removal efficiency of nitrogen oxides, it can meet increasingly harsh
NOxDischarge standard, in addition denitration reaction do not need to very high reaction temperature, equipment is easy for installation, and the escaping of ammonia rate is low, and (escape ammonia is dense
Degree is generally less than 3ppm), secondary pollution will not be caused to environment, so technique is widely used in coal-burning power plant etc. at present
Industry-by-industry.
Since the exhaust temperature of many industrial tail gas is relatively low, less than 200 DEG C are reached.So in order to meet more multiple enterprises work
The discharge of industry tail gas, the research of low-temperature denitration catalyst are essential.Manganese oxide catalyst with good low temperature due to taking off
Nitre activity, is widely paid close attention to by people.But since the impurity such as oxysulfide present in flue gas can make catalyst that poisoning occur instead
Should, lead to catalyst inactivation.Experiment finds CuSO4There is very high high temperature activity, additionally, due to CuSO4There is no be sulphated
The problem of, so it is with good sulfur poisoning resistance.By manganese and CuSO4It is combined with each other, can play in a particular manner
Annex the effect of the two advantage.
Invention content
In view of this, the present invention provides a kind of denitrating catalysts, and the low-temperature denitration activity of gained catalyst is high, and activity
Temperature window mouth width has good anti-SO2Poisoning capability, product are integral catalyzer, can be suitably used for the practical smoke gas treatment of industry.
The technological means that the present invention uses is as follows：
A kind of denitrating catalyst, including matrix foamed ceramics and coated in the matrix be used as catalyst carrier
TiO2, further include coated in the supported catalyst active material MnOx- CuSO4；
The catalyst activity substance MnOx- CuSO4The molar ratio of middle manganese element and copper is about：1：4~1：27.
Preferably, the carrier TiO2Divide multiple coating in the matrix, the composite oxides MnOx- CuSO4Point
Multiple coating is in the carrier TiO2On coating.
Preferably, the carrier TiO2Coating is continuous coated, the composite oxides MnOx- CuSO4Coating is continuous
Coating.
Preferably, the MnOx- CuSO4Structure be CuSO4After manganese ion being doped into lattice, CuSO4Lattice occurs
The structure of distortion.
Preferably, the hole of the foamed ceramics is more than 50nm.
Preferably, carrier TiO is prepared2Raw material and proportioning be：Butyl titanate：15wt% -22wt%, cetyl
Trimethylammonium bromide：2wt% -7wt%, absolute ethyl alcohol：60wt% -72wt%, distilled water：8wt% -13wt%.
Preferably, catalyst activity substance MnO is preparedx- CuSO4Raw material and proportioning be：CuSO4·5H2O：
60wt% -92wt%, Mn (cA)2·4H2O：8wt% -40wt%.
Preferably, the catalyst activity substance MnOx- CuSO4The molar ratio of middle manganese element and copper is further about
For：1：4~1：17.
Preferably, the denitration activity temperature range of the denitrating catalyst is 120 DEG C -400 DEG C.
Preferably, the denitrating catalyst is prepared with infusion process, including Ti colloidal sols prepare and coat, active material prepare and
Coating is dried and is calcined.
Using a kind of denitrating catalyst provided by the present invention, there is following technique effect：
(1) the catalyst low-temperature denitration activity that prepared by the present invention is high, and at 200 DEG C, denitration rate can be close to 100%；
(2) in preparation process of the present invention, the process for preparing Ti colloidal sols is passed through dry N2Effect be to prevent colloidal sol from shifting to an earlier date water
Solution, prepared by active material and last roasting is in N2Atmosphere in, be conducive to make MnOxOxidizability reduces, and reduces MnOx's
The introducing of crystallinity and foreign gas improves the out of stock activity of entirety of catalyst, makes the catalytic activity higher of active material, prepares
Process preferably allows on Ti colloidal sols and active material repeated boad to matrix.
(3) catalyst activity temperature window is wider, more common manganese-based catalyst has preferable anti-SO2Poisoning capability can fit
Answer the smoke components of actual industrial flue gas complexity.
(4) foamed ceramics plays the role of integrated support in the catalyst prepared, and is carried in actual industrial flue gas to apply
For possible.CuSO4For main high active material, wherein Cu efficiently can prevent S to be poisoned in the catalyst.MnOxTo adulterate auxiliary agent,
The low temperature active of the catalytic activity of catalyst, especially catalyst can be significantly improved.Mn ions can be doped in preparation process
In CuSO4 lattices, it is distorted lattice, this is conducive to the promotion of catalytic activity.In addition, when denitration reaction occurs, Mn from
Son acts synergistically with Cu ions, can also promote the generation of reaction, and product is integral catalyzer, can be suitably used for industrial practical
Smoke gas treatment.
Description of the drawings
Fig. 1 is the denitration activity test chart of the present invention
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
Embodiment one：
It is prepared by S1.Ti colloidal sols：15wt% butyl titanates, 2wt% cetyl trimethylammonium bromides, 72wt% are taken respectively
Absolute ethyl alcohol mixing be placed in being sufficiently stirred 0.5h in 90kHz ultrasonic waves, taken after stirring 11wt% distilled water dropwise plus
Enter above-mentioned mixed solution to be placed in continuing to stir 0.5h in ultrasonic wave, above-mentioned two agitation phases are passed through with flow velocity 10mL/min
N2, whipping temp are 20 DEG C；
It S2. will be through step S1 treated Ti colloidal sols are placed on temperature in 5 DEG C of environment, by forming that hole is 50nm
Foamed ceramics is immersed in Ti colloidal sols and is impregnated for 24 hours, is taken out foamed ceramics later and is placed on 4h in vacuum drying chamber, drying temperature 110
℃；
S3. sample after step S2 processing is continued to immerse in Ti colloidal sols prepared by step S1, repeats time of step S2
Number is 2 times, then goes to sample in Muffle furnace with 200 DEG C of roastings；
S4. prepared by active material：Suitable 92wt%CuSO is taken respectively4·5H2O, 8wt%Mn (cA)2·4H2O is added to
In distilled water, in N22h is stirred under atmosphere；
S5. it by the solution prepared through the immersion of step S3 treated samples through step S4, impregnates for 24 hours, then by sample
Taking-up is put into vacuum drying chamber dry 4h, and drying temperature is 110 DEG C；
S6. by the solution through step S5 treated sample is immersed in again step S4 preparations, step S5 is repeated, is repeated
Dipping 3 times；
It S7. will treated that sample is placed on N through step S62Atmosphere kiln roasting, with the rate of 2 DEG C/min by atmosphere furnace
Temperature rises to 490 DEG C, keeps the temperature 4h.
The molar ratio of manganese and copper is about in catalyst obtained in the present embodiment：1：24~1：27, electronics mirror image is shown
CuSO4Doped with manganese ion in lattice.
Embodiment two：
It is prepared by S1.Ti colloidal sols：Take respectively 17wt% by butyl titanate, 5wt% cetyl trimethylammonium bromides,
The mixing of 65wt% absolute ethyl alcohols is placed in being sufficiently stirred 1h in 70kHz ultrasonic waves, and 13wt% distilled water is taken after stirring dropwise
The above-mentioned mixed solution of addition be placed in continuing in ultrasonic wave stirring 0.5h, above-mentioned two agitation phases are with flow velocity 30mL/min
It is passed through N2, whipping temp is 20 DEG C；
It S2. will be through step S1 treated Ti colloidal sols are placed on temperature in 5 DEG C of environment, by forming that hole is 60nm
Foamed ceramics immerses in Ti colloidal sols and impregnates 20h, takes out foamed ceramics later and is placed on 6h in vacuum drying chamber, drying temperature 120
℃；
S3. sample after step S2 processing is continued to immerse in Ti colloidal sols prepared by step S1, repeats time of step S2
Number is 3 times, then goes to sample in Muffle furnace with 190 DEG C of roastings；
S4. prepared by active material：Suitable 80wt%CuSO is taken respectively4·5H2O, 20wt%Mn (cA)2·4H2O dissolves in
Into distilled water, in N23h is stirred under atmosphere；
S5. by the solution prepared through the immersion of step S3 treated samples through step S4, dipping 20h, then by sample
Taking-up is put into vacuum drying chamber dry 6h, and drying temperature is 120 DEG C；
S6. by the solution through step S5 treated sample is immersed in again step S4 preparations, step S5 is repeated, is repeated
Dipping 4 times；
It S7. will treated that sample is placed on N through step S62Atmosphere kiln roasting, with the rate of 4 DEG C/min by atmosphere furnace
Temperature rises to 530 DEG C, keeps the temperature 5h.
The molar ratio of manganese and copper is about in catalyst obtained in the present embodiment：1：9~1：13, electronics mirror image is shown
CuSO4Doped with manganese ion in lattice.
Embodiment three：
It is prepared by S1.Ti colloidal sols：20wt% butyl titanates, 7wt% cetyl trimethylammonium bromides, 60wt% are taken respectively
Absolute ethyl alcohol mixing is placed in being sufficiently stirred 1h in 100kHz ultrasonic waves, and the addition of 13wt% distilled water dropwise is taken after stirring
Above-mentioned mixed solution is placed in continuing to stir 1h in ultrasonic wave, and above-mentioned two agitation phases are passed through N with flow velocity 50mL/min2,
Whipping temp is 25 DEG C；
It S2. will be through step S1 treated Ti colloidal sols are placed on temperature in 15 DEG C of environment, by the forming that hole is 50nm
Foamed ceramics immerse Ti colloidal sols in impregnate 15h, later take out foamed ceramics be placed on 8h in vacuum drying chamber, drying temperature is
130℃；
S3. sample after step S2 processing is continued to immerse in Ti colloidal sols prepared by step S1, repeats time of step S2
Number is 5 times, then goes to sample in Muffle furnace with 200 DEG C of roastings；
S4. prepared by active material：Suitable 60wt%CuSO is taken respectively4·5H2O, 40wt%Mn (cA)2·4H2O dissolves in
Into distilled water, in N23h is stirred under atmosphere；
S5. by the solution prepared through the immersion of step S3 treated samples through step S4, dipping 18h, then by sample
Taking-up is put into vacuum drying chamber dry 8h, and drying temperature is 120 DEG C；
S6. by the solution through step S5 treated sample is immersed in again step S4 preparations, step S5 is repeated, is repeated
Dipping 5 times；
It S7. will treated that sample is placed on N through step S62Atmosphere kiln roasting, with the rate of 5 DEG C/min by atmosphere furnace
Temperature rises to 500 DEG C, keeps the temperature 4h.
The molar ratio of manganese and copper is about in catalyst obtained in the present embodiment：1：4~1：6, electronics mirror image shows CuSO4
Doped with manganese ion in lattice.
Example IV：
It is prepared by S1.Ti colloidal sols：22wt% butyl titanates, 5wt% cetyl trimethylammonium bromides, 65wt% are taken respectively
Absolute ethyl alcohol mixing is placed in being sufficiently stirred 2h in 120kHz ultrasonic waves, and the addition of 8wt% distilled water dropwise is taken after stirring
Above-mentioned mixed solution is placed in continuing to stir 1h in ultrasonic wave, and above-mentioned two agitation phases are passed through N with flow velocity 70mL/min2,
Whipping temp is 30 DEG C；
It S2. will be through step S1 treated Ti colloidal sols are placed on temperature in 10 DEG C of environment, by the forming that hole is 70nm
Foamed ceramics immerse Ti colloidal sols in impregnate 10h, later take out foamed ceramics be placed on 10h in vacuum drying chamber, drying temperature is
140℃；
S3. sample after step S2 processing is continued to immerse in Ti colloidal sols prepared by step S1, repeats time of step S2
Number is 4 times, then goes to sample in Muffle furnace with 220 DEG C of roastings；
S4. prepared by active material：70wt%CuSO is taken respectively4·5H2O、30wtMn(cA)2·4H2O is added to distilled water
In, in N24h is stirred under atmosphere；
S5. by the solution prepared through the immersion of step S3 treated samples through step S4, dipping 12h, then by sample
Taking-up is put into vacuum drying chamber dry 10h, and drying temperature is 130 DEG C；
S6. by the solution through step S5 treated sample is immersed in again step S4 preparations, step S5 is repeated, is repeated
Dipping 3 times；
It S7. will treated that sample is placed on N through step S62Atmosphere kiln roasting, with the rate of 6 DEG C/min by atmosphere furnace
Temperature rises to 510 DEG C, keeps the temperature 4h.
The molar ratio of manganese and copper is about in catalyst obtained in the present embodiment：1：15~1：17, electronics mirror image is shown
CuSO4Doped with manganese ion in lattice.
Embodiment five：
It is prepared by S1.Ti colloidal sols：Take respectively suitable 15wt% butyl titanates, 7wt% cetyl trimethylammonium bromides,
The mixing of 66wt% absolute ethyl alcohols is placed in being sufficiently stirred 2h in 80kHz ultrasonic waves, and 12wt% distilled water is taken after stirring dropwise
The above-mentioned mixed solution of addition be placed in continuing in ultrasonic wave stirring 1h, above-mentioned two agitation phases are with flow velocity 100mL/min
It is passed through N2, whipping temp is 35 DEG C；
It S2. will be through step S1 treated Ti colloidal sols are placed on temperature in 20 DEG C of environment, by the forming that hole is 60nm
Foamed ceramics immerse Ti colloidal sols in impregnate 6h, later take out foamed ceramics be placed on 12h in vacuum drying chamber, drying temperature is
150℃；
S3. sample after step S2 processing is continued to immerse in Ti colloidal sols prepared by step S1, repeats time of step S2
Number is 5 times, then goes to sample in Muffle furnace with 200 DEG C of roastings；
S4. prepared by active material：Suitable 75wt%CuSO is taken respectively4·5H2O, 25wt%Mn (cA)2·4H2O dissolves in
Into distilled water, in N24h is stirred under atmosphere；
S5. by the solution prepared through the immersion of step S3 treated samples through step S4, then dipping 6h takes sample
Go out to be put into dry 12h in vacuum drying chamber, drying temperature is 130 DEG C；
S6. by the solution through step S5 treated sample is immersed in again step S4 preparations, step S5 is repeated, is repeated
Dipping 5 times；
It S7. will treated that sample is placed on N through step S62Atmosphere kiln roasting, with the rate of 7 DEG C/min by atmosphere furnace
Temperature rises to 520 DEG C, keeps the temperature 5h.
The molar ratio of manganese and copper is about in catalyst obtained in the present embodiment：1：19~1：21, electronics mirror image is shown
CuSO4Doped with manganese ion in lattice.
Activity rating：The denitration activity test of catalyst prepared by embodiment 1-5 is as shown in Figure 1.
Test result shows that the catalyst prepared by each embodiment between 160~360 DEG C there is higher denitration to live
Property, overall a little higher than other several groups of the denitration rate of embodiment 3.
Using a kind of denitrating catalyst provided by the present invention, there is following technique effect：
(1) the catalyst low-temperature denitration activity that prepared by the present invention is high, and at 200 DEG C, denitration rate can be close to 100%；
(2) in preparation process of the present invention, the process for preparing Ti colloidal sols is passed through dry N2Effect be to prevent colloidal sol from shifting to an earlier date water
Solution, prepared by active material and last roasting is in N2Atmosphere in, be conducive to make MnOxOxidizability reduces, and reduces MnOx's
The introducing of crystallinity and foreign gas improves the out of stock activity of entirety of catalyst, makes the catalytic activity higher of active material, prepares
Process preferably allows on Ti colloidal sols and active material repeated boad to matrix.
(3) catalyst activity temperature window is wider, more common manganese-based catalyst has preferable anti-SO2Poisoning capability can fit
Answer the smoke components of actual industrial flue gas complexity.
(4) foamed ceramics plays the role of integrated support in the catalyst prepared, and is carried in actual industrial flue gas to apply
For possible.CuSO4For main high active material, wherein Cu efficiently can prevent S to be poisoned in the catalyst.MnOxTo adulterate auxiliary agent,
The low temperature active of the catalytic activity of catalyst, especially catalyst can be significantly improved.Mn ions can be doped in preparation process
In CuSO4 lattices, it is distorted lattice, this is conducive to the promotion of catalytic activity.In addition, when denitration reaction occurs, Mn from
Son acts synergistically with Cu ions, can also promote the generation of reaction, and product is integral catalyzer, can be suitably used for industrial practical
Smoke gas treatment.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God and any modification, equivalent substitution, improvement and etc. within principle, done, should be included within the scope of protection of the invention.
Claims (10)
1. a kind of denitrating catalyst, which is characterized in that including matrix foamed ceramics and coated in the matrix be used as urge
The TiO of agent carrier2, further include coated in the supported catalyst active material MnOx- CuSO4；
The catalyst activity substance MnOx- CuSO4The molar ratio of middle manganese element and copper is about：1：4~1：27.
2. denitrating catalyst according to claim 1, which is characterized in that the carrier TiO2Divide multiple coating in the base
In matter, the composite oxides MnOx- CuSO4Divide multiple coating in the carrier TiO2On coating.
3. denitrating catalyst according to claim 2, which is characterized in that the carrier TiO2Coating is described to be continuous coated
Composite oxides MnOx- CuSO4Coating is continuous coated.
4. denitrating catalyst according to claim 1, which is characterized in that the MnOx- CuSO4Structure be CuSO4It is brilliant
After manganese ion being doped into lattice, CuSO4The structure that lattice is distorted.
5. denitrating catalyst according to claim 1, which is characterized in that the hole of the foamed ceramics is more than 50nm.
6. denitrating catalyst according to claim 1, which is characterized in that prepare carrier TiO2Raw material and proportioning be：Metatitanic acid
Four butyl esters：15wt% -22wt%, cetyl trimethylammonium bromide：2wt% -7wt%, absolute ethyl alcohol：60wt%-
72wt%, distilled water：8wt% -13wt%.
7. denitrating catalyst according to claim 1, which is characterized in that prepare catalyst activity substance MnOx- CuSO4's
Raw material and proportioning are：CuSO4·5H2O：60wt% -92wt%, Mn (cA)2·4H2O：8wt% -40wt%.
8. denitrating catalyst according to claim 1, which is characterized in that the catalyst activity substance MnOx- CuSO4In
The molar ratio of manganese element and copper is about further：1：4~1：17.
9. denitrating catalyst according to claim 1, which is characterized in that the denitration activity temperature model of the denitrating catalyst
Enclose is 120 DEG C -400 DEG C.
10. the denitrating catalyst according to according to any one in claim 1-9, which is characterized in that prepared with infusion process
The denitrating catalyst including Ti colloidal sols preparation and coating, active material preparation and coating, drying and is calcined.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111229290A (en) * | 2020-03-24 | 2020-06-05 | 苏州道一至诚纳米材料技术有限公司 | Composite non-noble metal denitration catalyst and preparation method thereof |
| CN112844423A (en) * | 2021-01-12 | 2021-05-28 | 上海大学 | High-sulfur-resistance metal sulfate denitration catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0286845A (en) * | 1988-06-09 | 1990-03-27 | W R Grace & Co | Catalyst for selective catalytic reducing dewaxing technique |
| CN105709719A (en) * | 2016-01-22 | 2016-06-29 | 湖北思搏盈环保科技有限公司 | Integral low-temperature SCR denitration catalyst and preparation method thereof |
-
2017
- 2017-12-21 CN CN201711398761.7A patent/CN108126715A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0286845A (en) * | 1988-06-09 | 1990-03-27 | W R Grace & Co | Catalyst for selective catalytic reducing dewaxing technique |
| CN105709719A (en) * | 2016-01-22 | 2016-06-29 | 湖北思搏盈环保科技有限公司 | Integral low-temperature SCR denitration catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| YANKE YU等: "Facile synthesis of CuSO4/TiO2 catalysts with superior activity and SO2 tolerance for NH 3-SCR：physicochemical properties and reaction mechanism", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
| 赵航 等: "《车用柴油机后处理技术》", 30 November 2010, 中国科学技术出版社 * |
| 黄妍 等: "CuSO4-V2O5/TiO2-SiO2低温NH3还原NO及抗毒性能研究", 《湘潭大学自然科学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111229290A (en) * | 2020-03-24 | 2020-06-05 | 苏州道一至诚纳米材料技术有限公司 | Composite non-noble metal denitration catalyst and preparation method thereof |
| CN111229290B (en) * | 2020-03-24 | 2020-12-15 | 苏州道一至诚纳米材料技术有限公司 | Composite non-noble metal denitration catalyst and preparation method thereof |
| CN112844423A (en) * | 2021-01-12 | 2021-05-28 | 上海大学 | High-sulfur-resistance metal sulfate denitration catalyst and preparation method thereof |
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