CN105457659A - Efficient denitration catalyst applied to coal-fired flue gas and preparation method thereof - Google Patents
Efficient denitration catalyst applied to coal-fired flue gas and preparation method thereof Download PDFInfo
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- CN105457659A CN105457659A CN201510927085.2A CN201510927085A CN105457659A CN 105457659 A CN105457659 A CN 105457659A CN 201510927085 A CN201510927085 A CN 201510927085A CN 105457659 A CN105457659 A CN 105457659A
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- denitrating catalyst
- catalyst
- flue gas
- preparation
- coal
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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
- 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
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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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
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- 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 an efficient denitration catalyst applied to coal-fired flue gas and a preparation method thereof. The denitration catalyst is prepared from or by mixing CeO2, SO4<2->and one of a TiO2 carrier, a Al2O3 carrier and a ZrO2 carrier. The denitration catalyst can be widely applied to coal-fired power plants under the condition of brown coal firing or high-sulfur flue gas and selective catalytic reduction of industrial boiler nitrogen oxide. The catalyst has the good denitration activity at the temperature ranging from 200 DEG C to 500 DEG C, the denitration activity can reach 89% or above and is much higher than that of an existing commercial vanadium-based catalyst, and the applicable temperature window is wider. The catalyst does not contain vanadium, cannot bring about secondary pollution to the environment, is not influenced by SO2 in the flue gas and is high in anti-poisoning capacity and long in service life.
Description
Technical field
The present invention relates to the nitrogen oxide control technology field in environmental protection, be specifically related to a kind of denitrating catalyst be applied under medium and high temperature flue gas condition and preparation method thereof.
Background technology
At present, the country of China's to be one with coal be main energy sources, account for 74% of national primary energy total output, in considerable time, the thermal power generation of internal combustion coal will be occupied an leading position at China's power field.Because China's coal is various, ature of coal is poor, containing a large amount of nitrogen oxide in the flue gas causing coal-burning power plant to be discharged, causes severe contamination to environment.In recent years, China is to the NO of coal-fired flue-gas
xemission control standard is more and more stricter.Ammonia selective catalyst reduction of nitrogen oxides (NH
3-SCR) be most widely used nitrogen oxide control technology, catalytic component based on vanadium is the most frequently used catalyst system.
At present, China's coal-fired plant flue gas temperature is generally at 250-420 DEG C, and the especially brown coal that use in a large number of China, the flue-gas temperature after burning is up to 450 DEG C, and simultaneously due to high-sulfur existence, the denitration activity of catalytic component based on vanadium and service life receive and has a strong impact on.Existing catalyst, due to the existence of active component vanadium, can cause secondary pollution to human body and environment.Therefore the environmentally friendly catalyst of exploitation adaptation China coal-fired flue-gas condition NO_x Reduction by Effective is very urgent.
Summary of the invention
In order to solve above-mentioned prior art Problems existing, the object of the present invention is to provide a kind of high-efficiency denitration catalyst be applied under coal-fired flue-gas condition and preparation method thereof, this catalyst long service life, little by the impact of sulfur, and its denitration rate is high, the SCR of coal-burning power plant under combusting brown coal or sulphur coal flue gas condition and Industrial Boiler nitrogen oxide can be widely used in.
In order to achieve the above object, the present invention adopts following technical scheme:
Be applied to the high-efficiency denitration catalyst under coal-fired flue-gas condition, it is characterized in that: described denitrating catalyst comprises following compositions or is mixed by following compositions: (I) CeO
2; (II) SO
4 2-; (III) TiO
2, Al
2o
3and ZrO
2one in carrier.
Preferably, in described denitrating catalyst, CeO
2weight to account for denitrating catalyst gross weight percentage composition be 3%-10%, SO
4 2-weight to account for denitrating catalyst gross weight percentage composition be 5%-10%, TiO
2, Al
2o
3or ZrO
2it is 80%-92% that the weight of carrier accounts for denitrating catalyst gross weight percentage composition.
In addition, the invention provides a kind of preparation method of denitrating catalyst, it is characterized in that: described method comprises the steps:
Step 1: titanium dioxide, zirconium dioxide or alumina carrier powder are joined in deionized water solution and stirs the scheduled time, cerous nitrate and ammonium sulfate is added in the aqueous solution, become solution 1, the addition of cerous nitrate and ammonium sulfate makes active component CeO in denitrating catalyst
2account for the 3%-10% of denitrating catalyst gross weight, SO
4 2-account for the 5%-10% of denitrating catalyst gross weight;
Step 2: carry out heating to solution 1 and be stirred in the pasty state, then carries out drying process, after drying terminates, pulverizes and carries out high-temperature calcination and obtain corresponding composite catalyst and be described denitrating catalyst.
Preferably, in described step 1, mixing time is 0.5-2 hour.
Preferably, in described step 2, dry temperature used is 60-80 DEG C.
Preferably, in described step 2, calcining temperature used is 400-600 DEG C.
Preferably, in described step 2, calcining temperature used is 500 DEG C.
In addition, the present invention also provides a kind of application of above-mentioned denitrating catalyst, it is characterized in that, described denitrating catalyst is used for centering, high-temperature flue gas carries out denitration process, and described application comprises: by medium and high temperature flue gas and NH
3the mist of gas contacts with described denitrating catalyst.
Preferably, the temperature of described high-temperature flue gas is 150-500 DEG C.
Compared with prior art, tool of the present invention has the following advantages:
1. Catalyst Production technique of the present invention can adapt to present stage catalyst manufacturer production.This technology is improved original technique, and can use existing preparation method's large-scale production.
2. catalyst of the present invention is at 40000h
-1air speed, NH
3500ppm, NO500ppm, O
2under the simulated flue gas condition of 3%, alumina carrier load acidifying cerium oxide catalyst has good denitration activity (more than 89%) the temperature range of 250-500 DEG C, and denitration activity is better than commercial catalytic component based on vanadium.Not containing vanadium in catalyst of the present invention, secondary pollution can not be brought to environment, and not by SO in flue gas
2impact, long service life.
3. it is emphasized that the Applicable temperature window of catalyst of the present invention is wider in addition, especially CeS/Al
2o
3catalyst, it can all realize denitration activity well within the scope of 200-500 DEG C.
Accompanying drawing explanation
Fig. 1 is the acidifying CeO of different carriers load
2nO on denitrating catalyst
xconversion rate curve figure.
Fig. 2 is the acidifying CeO of different carriers load
2n on denitrating catalyst
2selectivity curve figure.
Detailed description of the invention
Below in conjunction with accompanying drawing, specific embodiments of the invention are described in detail.
Embodiment one
In the present embodiment, three kinds of denitrating catalysts have been prepared respectively.
Specifically, by three kinds of carrier TiO
2, Al
2o
3and ZrO
2the each 8.5g of powder join respectively in three parts of 45mL deionized water solutions and stir 1h, in every a aqueous solution, add six water cerous nitrate 0.76g and ammonium sulfate 0.69g, the two can react in aqueous and generate the mixture of cerous sulfate and ammonium nitrate.Can control or suitably adjust the proportioning of raw material, the active component CeO that after making subsequent sulphuric acid cerium and ammonium nitrate calcining, reaction obtains
2account for the 3wt% of denitrating catalyst gross weight, SO
4 2-account for the 5wt% of denitrating catalyst gross weight.Then, respectively three parts of solution are heated to 70 DEG C and continue to be stirred to pasty state, dry at 120 DEG C, be dried into bulk and smash to pieces, calcine in atmosphere after 4 hours for 500 DEG C and obtain three kinds of denitrating catalysts, the main component of the first is CeO
2, SO
4 2-and TiO
2, we are referred to as CeS/TiO
2denitrating catalyst, the main component of the second is CeO
2, SO
4 2-and Al
2o
3, we are referred to as CeS/Al
2o
3denitrating catalyst, the third main component is CeO
2, SO
4 2-and ZrO
2, we are referred to as or CeS/ZrO
2denitrating catalyst.
Denitrating catalyst of the present invention carries out the catalyst in denitrification process mainly as centering, high-temperature flue gas.
In order to verify the transformation efficiency of denitrating catalyst of the present invention, inventor simulates conversion process, and simulated conditions are: temperature 150-500 DEG C, normal pressure, reaction velocity 40000h
-1, flue gas concentration is 500ppmNH
3, 500ppmNO, 10%H
2o, 100ppmSO
2, 3%O
2.
As shown in Figure 1, sets forth the Sulfated CeO of different carriers load in figure
2the denitration efficiency of catalyst.At 250-500 DEG C, CeS/Al
2o
3catalyst all has very high removal of nitrogen oxide efficiency.At 300-500 DEG C of temperature, CeS/TiO
2the catalytic activity of catalyst is almost up to more than 90%.All things considered, their catalytic activity order is: CeS/Al
2o
3>CeS/TiO
2>CeS/ZrO
2.
As shown in Figure 2, sets forth the Sulfated CeO of different carriers load in figure
2the N of catalyst
2selective.At 150-500 DEG C, CeS/Al
2o
3, CeS/TiO
2, CeS/ZrO
2catalyst all has very high N
2selective.
Embodiment two
By carrier TiO
2, Al
2o
3and ZrO
2the each 10g of powder join respectively in three parts of 50mL deionized water solutions and stir 1h, in every a aqueous solution, add six water cerous nitrate and ammonium sulfate, make to react the active component CeO obtained
2account for the 5wt% of denitrating catalyst gross weight, SO
4 2-account for the 6wt% of denitrating catalyst gross weight.Then, respectively three parts of solution are heated to 70 DEG C and continue to be stirred to pasty state, dry at 120 DEG C, be dried into bulk and smash to pieces, calcining in atmosphere after 4 hours for 500 DEG C and obtain three kinds of denitrating catalysts.
Through experimental verification, catalyst and the embodiment one of this kind of proportioning have similar desulfurized effect.
Embodiment three
By carrier TiO
2, Al
2o
3and ZrO
2the each 10g of powder join respectively in three parts of 50mL deionized water solutions and stir 1h, in every a aqueous solution, add six water cerous nitrate and ammonium sulfate, make to react the active component CeO obtained
2account for the 8wt% of denitrating catalyst gross weight, SO
4 2-account for the 10wt% of denitrating catalyst gross weight.Then, respectively three parts of solution are heated to 70 DEG C and continue to be stirred to pasty state, dry at 120 DEG C, be dried into bulk and smash to pieces, calcining in atmosphere after 4 hours for 500 DEG C and obtain three kinds of denitrating catalysts.
Through experimental verification, catalyst and the embodiment one of this kind of proportioning also have similar desulfurized effect.In addition, present inventor also tests the proportioning outside claim limited range, and effect all can not show a candle to the effect within limited range of the present invention.
Although be described in detail principle of the present invention in conjunction with the preferred embodiments of the present invention, it should be appreciated by those skilled in the art that above-described embodiment is only the explanation to exemplary implementation of the present invention above, not the present invention is comprised to the restriction of scope.Details in embodiment does not form limitation of the scope of the invention; when not deviating from the spirit and scope of the present invention; the apparent changes such as any equivalent transformation based on technical solution of the present invention, simple replacement, all drop within scope.
Claims (9)
1. be applied to the high-efficiency denitration catalyst under coal-fired flue-gas condition, it is characterized in that: described denitrating catalyst comprises following compositions or is mixed by following compositions: (I) CeO
2; (II) SO
4 2-; (III) TiO
2, Al
2o
3and ZrO
2one in carrier.
2. denitrating catalyst according to claim 1, is characterized in that: in described denitrating catalyst, CeO
2weight to account for denitrating catalyst gross weight percentage composition be 3%-10%, SO
4 2-weight to account for denitrating catalyst gross weight percentage composition be 5%-10%, TiO
2, Al
2o
3or ZrO
2it is 80%-92% that the weight of carrier accounts for denitrating catalyst gross weight percentage composition.
3. a preparation method for denitrating catalyst, is characterized in that: described method comprises the steps:
Step 1: titanium dioxide, zirconium dioxide or alumina carrier powder are joined in deionized water solution and stirs the scheduled time, add cerous nitrate and ammonium sulfate in the aqueous solution, become solution 1;
Step 2: carry out heating to solution 1 and be stirred in the pasty state, then carries out drying process, and after drying terminates, pulverizing is carried out high-temperature calcination and obtained containing CeO
2and SO
4 2-composite catalyst be described denitrating catalyst,
Wherein, the addition of cerous nitrate and ammonium sulfate will make calcining in step 2 terminate active component CeO in the denitrating catalyst of rear acquisition
2account for the 3%-10% of denitrating catalyst gross weight, SO
4 2-account for the 5%-10% of denitrating catalyst gross weight.
4. the preparation method of denitrating catalyst described in claim 3, is characterized in that: in described step 1, and mixing time is 0.5-2 hour.
5. the preparation method of denitrating catalyst described in claim 3, is characterized in that: in described step 2, and dry temperature used is 60-80 DEG C.
6. the preparation method of denitrating catalyst described in claim 3, is characterized in that: in described step 2, and calcining temperature used is 400-500 DEG C.
7. the preparation method of denitrating catalyst described in claim 6, is characterized in that: in described step 2, and calcining temperature used is 450 DEG C.
8. an application for denitrating catalyst according to claim 1, is characterized in that, described denitrating catalyst is used for centering, high-temperature flue gas carries out denitration process, and described application comprises: by medium and high temperature flue gas and NH
3the mist of gas contacts with described denitrating catalyst.
9. application according to claim 8, is characterized in that, the temperature of described medium and high temperature flue gas is 150-500 DEG C.
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|---|---|---|---|
| CN201510927085.2A CN105457659B (en) | 2015-12-11 | 2015-12-11 | A kind of high-efficiency denitration catalyst applied to coal-fired flue-gas and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259009A (en) * | 2011-06-13 | 2011-11-30 | 华北电力大学 | Sulfate radical promoted TiO2 carrier based SCR (Selective Catalytic Reduction) flue gas denitration catalyst and preparation method thereof |
| CN102658172A (en) * | 2012-04-20 | 2012-09-12 | 浙江大学 | SCR denitration catalyst as well as preparation method and application thereof |
| CN104014324A (en) * | 2014-05-14 | 2014-09-03 | 华东理工大学 | Cerium oxide-based loaded smoke denitrification catalyst and preparation method thereof |
-
2015
- 2015-12-11 CN CN201510927085.2A patent/CN105457659B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259009A (en) * | 2011-06-13 | 2011-11-30 | 华北电力大学 | Sulfate radical promoted TiO2 carrier based SCR (Selective Catalytic Reduction) flue gas denitration catalyst and preparation method thereof |
| CN102658172A (en) * | 2012-04-20 | 2012-09-12 | 浙江大学 | SCR denitration catalyst as well as preparation method and application thereof |
| CN104014324A (en) * | 2014-05-14 | 2014-09-03 | 华东理工大学 | Cerium oxide-based loaded smoke denitrification catalyst and preparation method thereof |
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