CN108889305A - A kind of denitrating catalyst and preparation method thereof - Google Patents
A kind of denitrating catalyst and preparation method thereof Download PDFInfo
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- CN108889305A CN108889305A CN201810742020.4A CN201810742020A CN108889305A CN 108889305 A CN108889305 A CN 108889305A CN 201810742020 A CN201810742020 A CN 201810742020A CN 108889305 A CN108889305 A CN 108889305A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000919 ceramic Substances 0.000 claims abstract description 33
- 241000264877 Hippospongia communis Species 0.000 claims abstract description 20
- 239000011149 active material Substances 0.000 claims abstract description 12
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 4
- 235000012907 honey Nutrition 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 10
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910002852 Sm(NO3)3·6H2O Inorganic materials 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- -1 F127 Chemical compound 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 6
- 231100000252 nontoxic Toxicity 0.000 abstract description 6
- 230000003000 nontoxic effect Effects 0.000 abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 5
- 206010027439 Metal poisoning Diseases 0.000 abstract description 4
- 239000000779 smoke Substances 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002604 ultrasonography 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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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Abstract
The invention discloses a kind of denitrating catalysts, including carrier ceramic honey comb and the TiO being compounded on the carrier ceramic honey comb2With the oxide of active material Sm, Ce, Fe, the molar ratio of Ce element, Fe element and Sm element is about in the active material：1：(2.0~7.1)：(0.8~1.6).And preparation method thereof, include the following steps：One layer of TiO is adhered on ceramic honey comb surface first2, then passing through the presoma of impregnation Fe, Ce, Sm, finally dry, roasting can obtain finished catalyst.The out of stock activity of the method for integrated low temperature denitrating catalyst prepared by the present invention, resulting integral catalyzer is high, and temperature window is wide, and product is nontoxic, there is certain anti-SO2It is strong with alkaline-earth metal poisoning capability, it can be applied directly in actual industrial smoke gas treatment.
Description
Technical field
The present invention relates to field of denitration catalyst more particularly to a kind of denitrating catalyst and preparation method thereof.
Background technique
Selective catalytic reduction flue gas denitration technology is current NO most widely used in the worldxRemoval methods, the technology
It refers mainly under the conditions of certain temperature, makes reducing agent selectively by the NO in flue gas using the catalytic performance of catalystxConversion
For harmless N2And H2O.The part of SCR denitration technology most critical is exactly SCR catalyst.Nowadays it is commercialized in denitration field
The V of application2O5/ TiO2 series catalysts, denitrification rate when industrial application can achieve 90% or more, but V2O5With toxicity,
Production, use process and it is discarded after can generate pollution.
Summary of the invention
In view of this, the present invention provides denitrating catalysts and preparation method thereof nontoxic and with greater activity.
The technological means that the present invention uses is as follows：
A kind of denitrating catalyst, including ceramic honey comb and the carrier TiO being compounded on the ceramic honey comb2And active matter
The oxide of matter Sm, Ce, Fe, the molar ratio of Ce element, Fe element and Sm element is about in the active material：1：(2.0~
7.1)：(0.8~1.6).The out of stock activity of the integral catalyzer is high, and product is nontoxic, there is certain anti-SO2In alkaline-earth metal
Malicious ability is strong, can be applied directly in actual industrial smoke gas treatment.
A kind of preparation method of denitrating catalyst, includes the following steps：
The preparation of S1.Ti colloidal sol：Butyl titanate, F127, dehydrated alcohol mixing is taken to be placed in ultrasonic wave and sufficiently stir respectively
2h-4h is mixed, the above-mentioned mixed solution of the addition of ionized water dropwise is removed after stirring and is placed in ultrasonic wave and continues to stir 0.5h-
1h；
S2. ceramic honey comb is immersed through step S1 treated Ti colloidal sol and is put into togerther the ring that temperature is 10 DEG C -30 DEG C
In border, 4h-8h is impregnated, foamed ceramics is taken out later and puts 4h-12h in a vacuum drying oven, drying temperature is 105 DEG C -125 DEG C,
It repeats this step 2~3 times；
S3. prepared by active material：Fe (NO respectively3)3·9H2O、Ce(NO3)3·6H2O and Sm (NO3)3·6H2O is added to
Mixed solution is made in deionized water, is placed in ultrasonic wave and continues to stir 2h-3h；
S4. sample after step S2 processing is immersed in the solution prepared through step S3, controlled at 40-60 DEG C,
2h-5h is impregnated, taking-up is put into N2Dry 2h-10h in atmosphere dry box, drying temperature are 120 DEG C -145 DEG C, are then placed in and are passed through
N2Atmosphere kiln roasting；
S5. step S3 and step S4 will be repeated through step S4 treated sample, duplicate number is 3~5 times, finally may be used
Obtain Sm-Ce-Fe/TiO2/ ceramic honey comb denitrating catalyst.
A kind of above-mentioned utilization collosol and gel-infusion process preparation Sm-Ce-Fe/TiO2/ ceramic honey comb integrated low temperature denitration is urged
The out of stock activity of the method catalyst of agent is high, and temperature window is wide, and product is nontoxic, there is certain anti-SO2 and alkaline-earth metal poisoning energy
Power is strong, can be applied directly in actual industrial smoke gas treatment, and preparation method is simple to operation, industrial production easy to accomplish.
Preferably, step S1, quality proportioning shared by each component described in step S3 is：Butyl titanate：50wt%~
70wt%, F127：0.5wt%~3.5wt%, deionized water：6wt%~10wt%, Fe (NO3)3·9H2O：15wt%~
25wt%, Ce (NO3)3·6H2O：2wt%~7wt%, Sm (NO3)3·6H2O：3wt%~10wt%；The volume of dehydrated alcohol
Account for five times or more of other substance total volumes.
Preferably, the frequency of ultrasonic wave is 50kHz-90kHz in the step S1.It is molten in fully dispersed Ti colloidal sol
Matter guarantees the uniform of dipping.
Preferably, the pore diameter of foamed ceramics is greater than 50nm in the step S2.The foamed ceramics of large aperture is conducive to
The homogeneous impregnation of colloidal sol and liquid improves the effect of catalyst entirety.
Preferably, the PH to 4~5 of mixed solution is adjusted in the step S3 with acetic acid.The acidic site for improving solution, mentions
The performance of the alkali resistant poisoning of high catalyst.
Preferably, in the step S4, the temperature for controlling solution is 40 DEG C -60 DEG C.
Preferably, sample is placed in rot in sample drying process in the step S2 and/or S4 and keeps 50-80
Rev/min revolving speed at the uniform velocity spin upside down.Rot guarantees the colloidal sol impregnated in porous ceramic honey comb and molten anyway up and down
The uniform attachment of liquid.
Preferably, in the step S4, the N of atmosphere furnace2Rate be 100sccm~1000sccm.
Preferably, in the step S4, maturing temperature section is：200 DEG C are risen to from room temperature with 2 DEG C~3 DEG C/min, heat preservation
1h~2h；It is risen to again with 5 DEG C~6 DEG C/min as 400 DEG C, keeps the temperature 3h~4h.
Using a kind of denitrating catalyst provided by the present invention and preparation method thereof, there is following technical effect：
(1) the out of stock activity of integral catalyzer prepared by the present invention is high, has higher catalytic activity at 200 DEG C or less,
And in 200~300 DEG C of denitrification rates close to 100%；
(2) catalyst prepared by the present invention have the wider activity of temperature, extend the application range of catalyst, have compared with
Good market prospects.
(3) this product product is nontoxic, will not cause secondary hazards to environment after discarded, meets modern " green " theory.
(4) this product has certain anti-SO2It is strong with alkaline-earth metal poisoning capability, actual industrial flue gas can be applied directly to and controlled
In reason.
Detailed description of the invention
Fig. 1 is denitration activity test chart of the 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 invention.
Embodiment one：
The preparation of S1.Ti colloidal sol：50wt% butyl titanate, 3.5wt%F127, dehydrated alcohol mixing is taken to be placed in respectively
2h is sufficiently stirred in the ultrasonic wave of 50kHz, the above-mentioned mixed solution juxtaposition of the addition of 6wt% deionized water dropwise is taken after stirring
Continue to stir 0.5h in 50kHz ultrasonic wave；
S2. the ceramic honey comb by pore diameter greater than 50nm immerses through step S1 treated Ti colloidal sol and is put into togerther temperature
Degree takes out foamed ceramics later and puts 4h in a vacuum drying oven to impregnate 4h in 10 DEG C of environment, and drying temperature is 105 DEG C, is done
Sample, which is placed in rot, during dry keeps 50 revs/min of revolving speed at the uniform velocity to spin upside down, and repeats this step 3 times；
S3. prepared by active material：25wt%Fe (NO respectively3)3·9H2O, 7wt%Ce (NO3)3·6H2O and 8wt%Sm
(NO3)3·6H2O, which is added in deionized water, is made mixed solution, and the PH of mixed solution is adjusted to 8, is placed in 80kHz ultrasonic wave
In continue stir 3h；
S4. sample after step S2 processing is immersed in the solution prepared through step S3, controlled at 40, is impregnated
5h；Taking-up is put into N2Dry 2h in atmosphere dry box, drying temperature are 145 DEG C, and sample is placed in rot in drying process
50 revs/min of revolving speed is kept at the uniform velocity to spin upside down, being then placed in rate is that 100sccm is passed through N2Atmosphere kiln roasting,
Maturing temperature section is：200 DEG C are risen to from room temperature with 2 DEG C/min, keeps the temperature 2h；It is risen to again with 6 DEG C/min as 400 DEG C, keeps the temperature 3h；
S5. step S3 and step S4 will be repeated through step S4 treated sample, duplicate number is 3 times, can finally be obtained
Sm-Ce-Fe/TiO2/ ceramic honey comb denitrating catalyst.
In the present embodiment, mole of Ce element, Fe element S m element in the catalyst activity substance of prepared catalyst
Than about：1：(3.1~3.4)：(1.1~1.2).
Embodiment two：
The preparation of S1.Ti colloidal sol：70wt% butyl titanate, 0.5wt%F127, dehydrated alcohol mixing is taken to be placed in respectively
2.5h is sufficiently stirred in 60kHz ultrasonic wave, the above-mentioned mixed solution juxtaposition of the addition of 8wt% deionized water dropwise is taken after stirring
Continue to stir 0.5h in 60kHz ultrasonic wave；
S2. the ceramic honey comb by pore diameter greater than 50nm immerses through step S1 treated Ti colloidal sol and is put into togerther temperature
Degree takes out foamed ceramics later and puts 6h in a vacuum drying oven to impregnate 5h in 10 DEG C of environment, and drying temperature is 110 DEG C, is done
Sample, which is placed in rot, during dry keeps 60 revs/min of revolving speed at the uniform velocity to spin upside down, and repeats this step 3 times；
S3. prepared by active material：15wt%Fe (NO respectively3)3·9H2O, 2wt%Ce (NO3)3·6H2O and 3wt%Sm
(NO3)3·6H2O, which is added in deionized water, is made mixed solution, and the PH of mixed solution is adjusted to 10, is placed in 90kHz ultrasound
Continue to stir 2h in wave；
S4. sample after step S2 processing is immersed in the solution prepared through step S3, controlled at 45 DEG C, dipping
2h；Taking-up is put into N2Dry 4h in atmosphere dry box, drying temperature are 145 DEG C, and sample is placed in rot in drying process
60 revs/min of revolving speed is kept at the uniform velocity to spin upside down, being then placed in rate is that 300sccm is passed through N2Atmosphere kiln roasting,
Maturing temperature section is：200 DEG C are risen to from room temperature with 3 DEG C/min, keeps the temperature 1h；It is risen to again with 5 DEG C/min as 400 DEG C, keeps the temperature 4h；
S5. step S3 and step S4 will be repeated through step S4 treated sample, duplicate number is 5 times, can finally be obtained
Sm-Ce-Fe/TiO2/ ceramic honey comb denitrating catalyst.
In the present embodiment, mole of Ce element, Fe element S m element in the catalyst activity substance of prepared catalyst
Than about：1：(7.1~7.0)：(1.5~1.6).
Embodiment three：
The preparation of S1.Ti colloidal sol：68wt% butyl titanate, 2wt%F127, dehydrated alcohol mixing is taken to be placed in respectively
3h is sufficiently stirred in 70kHz ultrasonic wave, the above-mentioned mixed solution juxtaposition of the addition of 10wt% deionized water dropwise is taken after stirring
Continue to stir 1h in 70kHz ultrasonic wave；
S2. the ceramic honey comb by pore diameter greater than 50nm immerses through step S1 treated Ti colloidal sol and is put into togerther temperature
Degree takes out foamed ceramics later and puts 8h in a vacuum drying oven to impregnate 6h in 20 DEG C of environment, and drying temperature is 120 DEG C, is done
Sample, which is placed in rot, during dry keeps 70 revs/min of revolving speed at the uniform velocity to spin upside down, and repeats this step 3 times；
S3. prepared by active material：20wt%Fe (NO respectively3)3·9H2O, 5wt%Ce (NO3)3·6H2O and 5wt%Sm
(NO3)3·6H2O, which is added in deionized water, is made mixed solution, and the PH of mixed solution is adjusted to 8, is placed in 50kHz ultrasonic wave
In continue stir 3h；
S4. sample after step S2 processing is immersed in the solution prepared through step S3, controlled at 50 DEG C, dipping
4h；Taking-up is put into N2Dry 8h in atmosphere dry box, drying temperature are 140 DEG C, and sample is placed in rot in drying process
70 revs/min of revolving speed is kept at the uniform velocity to spin upside down, being then placed in rate is that 500sccm is passed through N2Atmosphere kiln roasting,
Maturing temperature section is：200 DEG C are risen to from room temperature with 3 DEG C/min, keeps the temperature 2h；It is risen to again with 5 DEG C/min as 400 DEG C, keeps the temperature 3h；
S5. step S3 and step S4 will be repeated through step S4 treated sample, duplicate number is 4 times, can finally be obtained
Sm-Ce-Fe/TiO2/ ceramic honey comb denitrating catalyst.
In the present embodiment, mole of Ce element, Fe element S m element in the catalyst activity substance of prepared catalyst
Than about：1：(3.7~3.8)：(1.0~1.1).
Example IV：
The preparation of S1.Ti colloidal sol：68wt% butyl titanate, 3wt%F127, dehydrated alcohol mixing is taken to be placed in respectively
4h is sufficiently stirred in 80kHz ultrasonic wave, the above-mentioned mixed solution of the addition of 7wt% deionized water dropwise is taken to be placed in after stirring
Continue to stir 0.5h in 80kHz ultrasonic wave；
S2. the ceramic honey comb by pore diameter greater than 50nm immerses through step S1 treated Ti colloidal sol and is put into togerther temperature
Degree takes out foamed ceramics later and puts 10h in a vacuum drying oven to impregnate 8h in 30 DEG C of environment, and drying temperature is 120 DEG C,
Sample, which is placed in rot, in drying process keeps 70 revs/min of revolving speed at the uniform velocity to spin upside down, and repeats this step 2 times；
S3. prepared by active material：15wt%Fe (NO respectively3)3·9H2O, 7wt%Ce (NO3)3·6H2O and 10wt%Sm
(NO3)3·6H2O, which is added in deionized water, is made mixed solution, and the PH of mixed solution is adjusted to 9, is placed in 60kHz ultrasonic wave
In continue stir 3h；
S4. sample after step S2 processing is immersed in the solution prepared through step S3, controlled at 60 DEG C, dipping
3h；Taking-up is put into N2Dry 10h in atmosphere dry box, drying temperature are 145 DEG C, and sample is placed in rot in drying process
570 revs/min of revolving speed is kept at the uniform velocity to spin upside down, being then placed in rate is that 800sccm is passed through N2Atmosphere kiln roasting,
Maturing temperature section is：200 DEG C are risen to from room temperature with 2 DEG C/min, keeps the temperature 1h；It is risen to again with 6 DEG C/min as 400 DEG C, keeps the temperature 4h；
S5. step S3 and step S4 will be repeated through step S4 treated sample, duplicate number is 3 times, can finally be obtained
Sm-Ce-Fe/TiO2/ ceramic honey comb denitrating catalyst.
In the present embodiment, mole of Ce element, Fe element S m element in the catalyst activity substance of prepared catalyst
Than about：1：(2.0~2.1)：(1.4~1.5).
Embodiment five：
The preparation of S1.Ti colloidal sol：69wt% butyl titanate, 2wt%F127, dehydrated alcohol mixing is taken to be placed in respectively
3h is sufficiently stirred in 90kHz ultrasonic wave, the above-mentioned mixed solution of the addition of 8wt% deionized water dropwise is taken to be placed in after stirring
Continue to stir 0.5h in 90kHz ultrasonic wave；
S2. the ceramic honey comb by pore diameter greater than 50nm immerses through step S1 treated Ti colloidal sol and is put into togerther temperature
Degree takes out foamed ceramics later and puts 10h in a vacuum drying oven to impregnate 6h in 20 DEG C of environment, and drying temperature is 110 DEG C,
Sample, which is placed in rot, in drying process keeps 80 revs/min of revolving speed at the uniform velocity to spin upside down, and repeats this step 3 times；
S3. prepared by active material：20wt%Fe (NO respectively3)3·9H2O, 6wt%Ce (NO3)3·6H2O and 5wt%Sm
(NO3)3·6H2O, which is added in deionized water, is made mixed solution, and the PH of mixed solution is adjusted to 9, is placed in 70kHz ultrasonic wave
In continue stir 2h；
S4. sample after step S2 processing is immersed in the solution prepared through step S3, controlled at 50 DEG C, dipping
3h；Taking-up is put into N2Dry 8h in atmosphere dry box, drying temperature are 120 DEG C, and sample is placed in rot in drying process
80 revs/min of revolving speed is kept at the uniform velocity to spin upside down, being then placed in rate is that 1000sccm is passed through N2Atmosphere kiln roasting,
Maturing temperature section is：200 DEG C are risen to from room temperature with 3 DEG C/min, keeps the temperature 2h；It is risen to again with 6 DEG C/min as 400 DEG C, keeps the temperature 3h；
S5. step S3 and step S4 will be repeated through step S4 treated sample, duplicate number is 5 times, can finally be obtained
Sm-Ce-Fe/TiO2/ ceramic honey comb denitrating catalyst.
In the present embodiment, mole of Ce element, Fe element S m element in the catalyst activity substance of prepared catalyst
Than about：1：(3.1~3.2)：(0.8~0.9).
Activity rating：The denitration activity test of catalyst prepared by embodiment 1-5 is as shown in Figure 1.
Test result shows that the denitration with higher between 160~360 DEG C of catalyst prepared by each embodiment is living
Property, overall a little higher than other several groups of the denitrification rate of embodiment 3.
Anti- SO2 poisoning test：Anti- SO2 is carried out to the SCR catalyst of low temperature in the poisoning of highly resistance obtained by Examples 1 to 5 respectively
Poisoning test, the Activity Results measured are to be passed through the SO containing 250ppm at 300 DEG C2Simulated flue gas SCR catalyst NO
Conversion ratio can be maintained at 75%, 69%, 70%, 76%, 72% or more for a long time respectively.
Using a kind of denitrating catalyst provided by the present invention and preparation method thereof, there is following technical effect：
(1) the out of stock activity of integral catalyzer prepared by the present invention is high, has higher catalytic activity at 200 DEG C or less,
And in 200~300 DEG C of denitrification rates close to 100%；
(2) catalyst prepared by the present invention have the wider activity of temperature, extend the application range of catalyst, have compared with
Good market prospects.
(3) this product product is nontoxic, will not cause secondary hazards to environment after discarded, meets modern " green " theory.
(4) this product has certain anti-SO2It is strong with alkaline-earth metal poisoning capability, actual industrial flue gas can be applied directly to and controlled
In reason.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should be included within the scope of the present invention.
Claims (10)
1. a kind of denitrating catalyst, which is characterized in that including ceramic honey comb and the carrier TiO being compounded on the ceramic honey comb2
With the oxide of active material Sm, Ce, Fe, the molar ratio of Ce element, Fe element and Sm element is about in the active material：1：
(2.0~7.1)：(0.8~1.6).
2. a kind of preparation method of denitrating catalyst, which is characterized in that include the following steps：
The preparation of S1.Ti colloidal sol：Butyl titanate, F127, dehydrated alcohol mixing is taken to be placed in ultrasonic wave and 2h- is sufficiently stirred respectively
4h removes the above-mentioned mixed solution of the addition of ionized water dropwise and is placed in ultrasonic wave and continues to stir 0.5h-1h after stirring；
S2. ceramic honey comb is immersed through step S1 treated Ti colloidal sol and is put into togerther in the environment that temperature is 10 DEG C -30 DEG C,
4h-8h is impregnated, foamed ceramics is taken out later and puts 4h-12h in a vacuum drying oven, drying temperature is 105 DEG C -125 DEG C, repeats this
Step 2~3 time；
S3. prepared by active material：Fe (NO respectively3)3·9H2O、Ce(NO3)3·6H2O and Sm (NO3)3·6H2O be added to from
Mixed solution is made in sub- water, is placed in ultrasonic wave and continues to stir 2h-3h；
S4. sample after step S2 processing is immersed in the solution prepared through step S3, impregnates 2h-5h, taking-up is put into N2Atmosphere
Dry 2h-10h in drying box, drying temperature are 120 DEG C -145 DEG C, are then placed in and are passed through N2Atmosphere kiln roasting；
S5. step S3 and step S4 will be repeated through step S4 treated sample, duplicate number is 3~5 times, can finally be obtained
Sm-Ce-Fe/TiO2/ ceramic honey comb denitrating catalyst.
3. preparation method according to claim 1, which is characterized in that step S1, matter shared by each component described in step S3
Amount matches：Butyl titanate：50wt%~70wt%, F127：0.5wt%~3.5wt%, deionized water：6wt%~
10wt%, Fe (NO3)3·9H2O：15wt%~25wt%, Ce (NO3)3·6H2O：2wt%~7wt%, Sm (NO3)3·6H2O：
3wt%~10wt%；The volume of dehydrated alcohol accounts for five times of other substance total volumes or more.
4. preparation method according to claim 1, which is characterized in that the frequency of ultrasonic wave is in the step S1
50kHz-90kHz。
5. preparation method according to claim 1, which is characterized in that the pore diameter of foamed ceramics is big in the step S2
In 50nm.
6. preparation method according to claim 1, which is characterized in that adjust mixed solution with acetic acid in the step S3
PH to 4~5.
7. preparation method according to claim 1, which is characterized in that in the step S4, the temperature for controlling solution is 40
℃-60℃。
8. preparation method according to claim 1, which is characterized in that sample drying process in the step S2 and/or S4
Middle sample is placed in rot keeps 50-80 revs/min of revolving speed at the uniform velocity to spin upside down.
9. preparation method according to claim 1, which is characterized in that in the step S4, the N of atmosphere furnace2Rate be
100sccm~1000sccm.
10. preparation method according to claim 1, which is characterized in that in the step S4, maturing temperature section is：From
Room temperature rises to 200 DEG C with 2 DEG C~3 DEG C/min, keeps the temperature 1h~2h；It is risen to again with 5 DEG C~6 DEG C/min as 400 DEG C, heat preservation 3h~
4h。
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Cited By (2)
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