CN101862652A - Preparation method of SCR flue gas denitration catalyst and product thereof - Google Patents
Preparation method of SCR flue gas denitration catalyst and product thereof Download PDFInfo
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- CN101862652A CN101862652A CN201010100867A CN201010100867A CN101862652A CN 101862652 A CN101862652 A CN 101862652A CN 201010100867 A CN201010100867 A CN 201010100867A CN 201010100867 A CN201010100867 A CN 201010100867A CN 101862652 A CN101862652 A CN 101862652A
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Abstract
The invention relates to a preparation method of an SCR flue gas denitration catalyst and a product thereof. The method comprises the following steps: taking slag with potassium manganate extracted as a main raw material, washing the slag with 2mol/L salpeter solution, and filtering, drying and crushing the slag; fully mixing filter residue powder, porous agent powder and electrolytic manganese anode mud, adding in distilled water rubbed strip to prepare particles; and sequentially drying, calcining to carry out activation, and finally preparing the SCR flue gas denitration catalyst. The invention not only saves the raw material cost, but also eliminates the pollution of the waste containing high-valent manganese to the environment, and has the advantage of simple preparation process. Verification proves that the catalyst can play a catalysis role when the flue gas temperature is about 200DEG C, and the service life of the activity catalyzed by the catalyst is also prolonged. Therefore, the invention is a preparation method and a product which have low cost, are beneficial to the environment and can turn the waste into valuable.
Description
Technical field
The present invention relates to the catalyst of SCR denitrating flue gas.
Background technology
In the discharged flue gas such as thermal power plant, (NOx mainly comprises NO, NO to contain a large amount of nitrogen oxide
2, N
2O etc.).NOx is the main atmosphere pollution that produces acid rain, brings photochemical fog, causes greenhouse effects and ozone layer is damaged.One of main method of administering the NOx pollution is that NOx in the flue gas is reduced to nitrogen (N
2, this process is called denitrating flue gas), ammonia (NH
3) be again the most effective reducing agent of having found so far.Wherein, catalytic unit and selection of catalysts catalytic reduction (SCR) method of denitration thereof in denitrification apparatus, have been set up, than only using reducing agent NH
3Non-selective catalytic reduction (SNCR) method of denitration much superior, the former not only denitration rate is much higher but also NH than the latter
3Consumption and escape amount all be lower than the latter again.In other words, catalyst is the key that improves the denitration rate, reduces improvement NOx cost.This known class catalyst all is metal oxides, especially with V
2O
5Catalytic activity the highest.Can be for commercial applications at present, with TiO
2For carrier, with V
2O
5For loading on the catalyst system and catalyzing of the main active component on this carrier, application number is 200810224389.2, name is called " a kind of with TiO
2Be denitrating catalyst of raw material and preparation method thereof " scheme be exactly one of them.Yet this class catalyst exists but that the cost of raw material is higher, the deficiency of preparation technology's relative complex of catalyst itself; Because this class catalyst need descend the competence exertion effect in higher flue-gas temperature (being generally 300 ℃～400 ℃), and impels down SO in high concentrate dust and the flue gas at higher temperature
2Cause this class catalyst poisoning again easily, so this class catalyst also has the deficiency of service life than weak point.In a word, it is higher to use the cost that this class catalyst administers NOx.
Summary of the invention
First purpose of the present invention is, the preparation method of the cheap and simple SCR catalyst for denitrating flue gas of preparation technology of a kind of cost of material is provided.
Second purpose of the present invention is that the SCR catalyst for denitrating flue gas that a kind of cost of material is cheap, can bring into play catalytic action under lower flue-gas temperature is provided.
The scheme that realizes described first goal of the invention is a kind of like this preparation method of SCR catalyst for denitrating flue gas, and this method is a primary raw material with the slag that extracts behind the potassium manganate, and it comprises the steps:
(1) washery slag: with the salpeter solution of 2mol/L with extract potassium manganate after slag mix fully stirring at normal temperatures by 5: 1.1～1.3 mass ratio; Then, leave standstill, filter, wash filter residue, powder is dried and be ground into to washing times then with filter residue can not detect potassium ion degree of being;
(2) moulding: get step (1) gained filter residue powder and fully mix, add distilled water then gradually with the pore creating material powder, and be adjusted to can rubbing, make the degree of particle; Wherein, pore creating material is any in active carbon, polyethylene glycol, ammonium nitrate, ammonium sulfate and the ammonium carbonate, and the mass ratio of filter residue powder and this pore creating material is 100: 5～7.5; Particle grain size 0.8～1.2cm;
(3) activate: step (2) gained particle is placed on earlier respectively dried by the fire under 70～90 ℃ and 90～100 ℃ 2 hours, and then these particles are placed on 250～270 ℃ of roastings 1 hour, 2 hours, 590～610 ℃ roastings of 440～460 ℃ of roastings 2 hours earlier, after this, naturally cool to room temperature, resulting solid particle is the SCR catalyst for denitrating flue gas.
The scheme that realizes described second goal of the invention is a kind of like this catalyst of SCR denitrating flue gas, and this catalyst is by prepared the forming of method of realizing first goal of the invention.
As can be seen, the source of the primary raw material of preparation catalyst of the present invention does not need special preparation or purchase, has extracted the slag that gone out of use usually behind the potassium manganate but select for use from the scheme that realizes first goal of the invention and second goal of the invention.Owing to still contain a certain amount of manganese element (existing) in these slags, so the part that catalyst of the present invention plays a role is actually the oxide of manganese with high price manganese form.After having extracted the slag behind the potassium manganate having gone out of use usually and being prepared into catalyst, not only saved the cost of material of this catalyst, but also eliminated the pollution of the discarded object that contains high price manganese environment.It can also be seen that from scheme compared with prior art, the present invention also has the simple advantage of preparation technology.
Experimental verification shows, catalyst of the present invention can be brought into play catalytic action under flue-gas temperature is situation about 200 ℃, and so, Yin Wendu is higher in the prior art, and impels SO in high concentrate dust and the flue gas
2Cause the condition of its poisoning also to weaken greatly, so the life-span of its catalytic activity is also prolonged.
In a word, the present invention be a kind of with low cost, help environment, preparation method that can turn waste into wealth and product.
The present invention is further illustrated below in conjunction with the specific embodiment.
The specific embodiment
A kind of preparation method of SCR catalyst for denitrating flue gas, this method is a primary raw material with the slag that extracts behind the potassium manganate, it comprises the steps:
(1) washery slag: with the salpeter solution of 2mol/L with extract potassium manganate after slag mix by 5: 1.1～1.3 mass ratio, fully stir at normal temperatures and (those skilled in the art know that, concrete proportioning and mixing time all should be can fully remove the impurity degree of being in this slag), then, leave standstill, filter, wash filter residue (the most handy distilled water during washing), powder is dried and be ground into to washing times then with filter residue can not detect potassium ion degree of being;
(2) moulding: get step (1) gained filter residue powder and fully mix, add distilled water then gradually with the pore creating material powder, and be adjusted to can rubbing, make the degree of particle; Wherein, pore creating material is any in active carbon, polyethylene glycol, ammonium nitrate, ammonium sulfate and the ammonium carbonate, and the mass ratio of filter residue powder and this pore creating material is 100: 5～7.5; Particle grain size 0.8～1.2cm;
It will be apparent to those skilled in the art that make particle before, the particle diameter of filter residue powder and this pore creating material powder also should be as the criterion with easy rubbing and the degree of making particle.
(3) activate: step (2) gained particle is placed on earlier respectively dried by the fire under 70～90 ℃ and 90～100 ℃ 2 hours, and then these particles are placed on 250～270 ℃ of roastings 1 hour, 2 hours, 590～610 ℃ roastings of 440～460 ℃ of roastings 2 hours earlier, after this, naturally cool to room temperature, resulting solid particle is the catalyst of SCR denitrating flue gas.
Further, in step (2), can also be mixed into electrolytic manganese anode mud equably; The mass ratio of its filter residue powder and this electrolytic manganese anode mud is 100: 8～44.
Useful component in the electrolytic manganese anode mud is a manganese dioxide, adds electrolytic manganese anode mud in step (2) moulding pelletization, has not only increased the content of this catalyst activity component, has further improved its catalytic activity; And be again a kind of utilization to discarded object, saved the expense of special disposal electrolytic manganese anode mud.In other words, for should extracting (production) potassium manganate, produce the enterprise of electrolytic manganese again, the discarded object that is utilized in the catalyst of the SCR denitrating flue gas of its preparation had both comprised and has extracted the slag behind the potassium manganate, also comprises electrolytic manganese anode mud.
Catalyst by the prepared SCR denitrating flue gas of the inventive method has passed through experimental verification.During checking, its preparation method is divided into two kinds of situations electrolytic manganese anode mud and that include electrolytic manganese anode mud that do not include.Afterwards, be put in these catalyst in the fixed-bed tube reactor respectively earlier; Be 10000h in air speed then
-1, temperature is under 195 ℃～210 ℃ the condition, will contain the simulated flue gas of 200ppm NO and the reducing gas NH of 200ppm concentration
3, feed reactor with 1: 1 ratio; Simulated flue gas (NO) concentration of last detection reaction device outlet, thus calculate the denitration rate.The checking example sees the following form.
Specify that related temperature range in preparation process is all in the mentioned scope of the specific embodiment, those skilled in the art know that, in most of the cases, the big or small end value of these temperature ranges also can be thought the permissible variation of its median temperature value.
From verify example, as can be seen, do not include the catalyst of the present invention of electrolytic manganese anode mud, under the flue-gas temperature about 210 ℃ (promptly 195 ℃～210 ℃) condition, can obtain denitration preferably; And added electrolytic manganese anode mud, particularly suitably increased after its addition, the better effects if of denitrating flue gas.So, for the enterprise that also produces electrolytic manganese simultaneously, should be utilizing this originally will discard electrolytic manganese anode mud fully, to obtain the effect of killing two birds with one stone.
Claims (4)
1. the preparation method of a SCR catalyst for denitrating flue gas is characterized in that, this method is a primary raw material with the slag that extracts behind the potassium manganate, and it comprises the steps:
(1) washery slag: with the salpeter solution of 2mol/L with extract potassium manganate after slag mix fully stirring at normal temperatures by 5: 1.1～1.3 mass ratio; Then, leave standstill, filter, wash filter residue, powder is dried and be ground into to washing times then with filter residue can not detect potassium ion degree of being;
(2) moulding: get step (1) gained filter residue powder and fully mix, add distilled water then gradually with the pore creating material powder, and be adjusted to can rubbing, make the degree of particle; Wherein, described pore creating material is any in active carbon, polyethylene glycol, ammonium nitrate, ammonium sulfate and the ammonium carbonate, and the mass ratio of described filter residue powder and this pore creating material is 100: 5～7.5; Described particle grain size 0.8～1.2cm;
(3) activate: step (2) gained particle is placed on earlier respectively dried by the fire under 70～90 ℃ and 90～100 ℃ 2 hours, and then these particles are placed on 250～270 ℃ of roastings 1 hour, 2 hours, 590～610 ℃ roastings of 440～460 ℃ of roastings 2 hours earlier, after this, naturally cool to room temperature, resulting solid particle is the SCR catalyst for denitrating flue gas.
2. according to the preparation method of the described SCR catalyst for denitrating flue gas of claim 1, it is characterized in that, in described step (2), also be mixed with electrolytic manganese anode mud equably; The mass ratio of described filter residue powder and this electrolytic manganese anode mud is 100: 8～44.
3. the catalyst of a SCR denitrating flue gas is characterized in that, this catalyst is prepared from by the described method of claim 1.
4. the catalyst of a SCR denitrating flue gas is characterized in that, this catalyst is prepared from by the described method of claim 2.
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| CN2010101008676A CN101862652B (en) | 2010-01-26 | 2010-01-26 | Preparation method of SCR flue gas denitration catalyst and product thereof |
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| CN2010101008676A CN101862652B (en) | 2010-01-26 | 2010-01-26 | Preparation method of SCR flue gas denitration catalyst and product thereof |
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| CN101862652A true CN101862652A (en) | 2010-10-20 |
| CN101862652B CN101862652B (en) | 2011-11-09 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105149010A (en) * | 2015-08-20 | 2015-12-16 | 天河（保定）环境工程有限公司 | High-microporosity SCR (selective catalytic reduction) denitrification catalyst and preparation method thereof |
| CN106944040A (en) * | 2017-03-14 | 2017-07-14 | 上海大学 | Utilize the method that catalyst for purification of nitrogen oxides is prepared containing Titanium slag and containing manganese mud |
| CN107866227A (en) * | 2017-09-16 | 2018-04-03 | 史汉祥 | Prepare the method and denitration method for flue gas of denitration catalyst composition |
| CN111185189A (en) * | 2020-01-16 | 2020-05-22 | 中国重型机械研究院股份公司 | Method for preparing yolk-egg white type SCR denitration catalyst and application |
| CN114558567A (en) * | 2022-03-11 | 2022-05-31 | 中南大学 | Granulation molding method of powder demercuration catalyst, product prepared by granulation molding method and application of product |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101028596B (en) * | 2007-04-06 | 2010-09-01 | 昆明理工大学 | Production of oxide nitrogen oxidation catalyst |
| CN101530795A (en) * | 2009-04-24 | 2009-09-16 | 昆明理工大学 | Catalyst for catalyzing and oxidizing nitrogen oxide and preparation method thereof |
-
2010
- 2010-01-26 CN CN2010101008676A patent/CN101862652B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105149010A (en) * | 2015-08-20 | 2015-12-16 | 天河（保定）环境工程有限公司 | High-microporosity SCR (selective catalytic reduction) denitrification catalyst and preparation method thereof |
| CN106944040A (en) * | 2017-03-14 | 2017-07-14 | 上海大学 | Utilize the method that catalyst for purification of nitrogen oxides is prepared containing Titanium slag and containing manganese mud |
| CN106944040B (en) * | 2017-03-14 | 2019-07-23 | 上海大学 | Using containing Titanium slag and the method for preparing catalyst for purification of nitrogen oxides containing manganese mud |
| CN107866227A (en) * | 2017-09-16 | 2018-04-03 | 史汉祥 | Prepare the method and denitration method for flue gas of denitration catalyst composition |
| CN111185189A (en) * | 2020-01-16 | 2020-05-22 | 中国重型机械研究院股份公司 | Method for preparing yolk-egg white type SCR denitration catalyst and application |
| CN114558567A (en) * | 2022-03-11 | 2022-05-31 | 中南大学 | Granulation molding method of powder demercuration catalyst, product prepared by granulation molding method and application of product |
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| CN101862652B (en) | 2011-11-09 |
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