CN1246069C - Method for preparing selective catalytic reduction and denitration catalyst by boiler coal ash - Google Patents
Method for preparing selective catalytic reduction and denitration catalyst by boiler coal ash Download PDFInfo
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- CN1246069C CN1246069C CN 200310100420 CN200310100420A CN1246069C CN 1246069 C CN1246069 C CN 1246069C CN 200310100420 CN200310100420 CN 200310100420 CN 200310100420 A CN200310100420 A CN 200310100420A CN 1246069 C CN1246069 C CN 1246069C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 23
- 239000010883 coal ash Substances 0.000 title abstract 4
- 239000010881 fly ash Substances 0.000 claims abstract description 76
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 230000004913 activation Effects 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 239000004480 active ingredient Substances 0.000 claims abstract 2
- 239000002245 particle Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 239000011398 Portland cement Substances 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 229910052602 gypsum Inorganic materials 0.000 claims description 4
- 239000010440 gypsum Substances 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 6
- 239000002253 acid Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000003517 fume Substances 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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Abstract
The present invention discloses a method for preparing a denitration catalyst for selective catalytic reduction (SCR) by using pulverized coal ash from a boiler, which relates to the technical field of fume purification in environmental protection. The method comprises the following steps: (1) after the granules of the pulverized coal ash and additive agents are mixed and stirred, the mixture is sent into a pretreatment kettle for the pretreatments of shaping and activation to form the solid shaped blocks of flyash, and the solid shaped blocks of the flyash are broken and sieved to obtain the shaped granules of the flyash; (2) after the shaped granules of the flyash are immersed in strong acid with high concentration, the filtered and shaped granules of the flyash are flushed by distilled water until the granules are neutral, and then the carrier of the flyash modified denitration catalyst for SCR is generated by the primary drying of the shaped granules of the flyash; (3) the carrier of the flyash modified denitration catalyst for SCR is immersed in the salt solution of metal oxides, and the denitration catalyst for SCR is prepared by the secondary drying and the calcination of the carrier. The present invention utilizes the waste pulverized coal ash of a boiler as the carrier, and the denitration catalyst for SCR is prepared by loading the metal oxides as active ingredients; therefore, technique cost is reduced, the reliability of the catalyst is enhanced, and the catalyst has good SO2 resistance.
Description
Technical Field
The invention relates to the technical field of environmental protection of flue gas purification, in particular to a method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash.
Background
With the acceleration of the industrialization process, the emission of nitrogen oxides (NOx) into the atmosphere by human activities is increasing. NOx can cause a series of problems such as acid rain and photochemical smog, etc., which destroy the earth's ecological environment and damage human health. Therefore, how to effectively remove NOx has become a very interesting issue in the field of environmental protection.
At present, measures for reducing NOx emission are mainly divided into two types: namely, combustion control and post-combustion control. Among them, a Selective Catalytic Reduction (SCR) method for controlling the combustion of flue gas is widely used because of its low cost and high efficiency. In order to convert NOx to nitrogen, a reductant must be added. Currently, the most common use in stationary combustion devices is the use of ammonia as the reductant, NH3The formula for selective reaction with NOx is as follows:
during the reaction, NH3Can selectively react with NOx to generate N2And H2O instead of by O2Oxidized and thus is "selective". The reaction can be carried out at a temperature in the range of 250 ℃ to 450 ℃ in NH by using a suitable catalyst3Under the condition that NO is 1 (the mass ratio of the substances), the denitration rate is 80-90%. In the prior art, a common catalyst generally uses titanium dioxide as a carrier, vanadium pentoxide as an active component and a ternary component of tungsten oxide. The catalyst is invented in Japan in the seventies of the twentieth century at the earliest time, and has the advantages of high denitration activity and small side reaction. However, such catalysts are relatively expensive to manufacture,and is easy to be poisoned and failed in use under severe working environment, so that the replacement is required regularly, and the replacement time is generally one to five years. If the SCR denitration reaction occurs in the presence of SO2In flue gas of (2), SO2Will be oxidized to SO under the action of this catalyst3. Because of SO3Can be mixed with water and NH in the flue gas3Reacting to produce ammonia sulfate and ammonium bisulfate. These sulfate deposits may accumulate on the surface of the catalyst, resulting in a decrease in the denitration activity of the catalyst. It is due to the high cost, unreliability and SO resistance of this SCR denitration process2The defect of poor performance hinders the large-scale application and popularization of the composite material.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash. The selective catalytic reduction denitration catalyst is prepared by using waste boiler fly ash as a carrier and loading metal oxide as an active component, SO that the process cost is reduced, the reliability is improved, and SO resistance is realized2The performance is good.
In order to achieve the above object of the invention, the technical solution of the present invention is achieved as follows.
A method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash comprises the following steps:
① fly ash molding, mixing and stirring the boiler fly ash particles and an additive consisting of lime and gypsum powder, ordinary portland cement and aluminum oxide powder particles, standing, feeding into a pretreatment kettle, molding and activating the mixture by using high-temperature and high-pressure steam with the temperature of 850-950 ℃ and the pressure of 80-100 standard atmospheres, crushing and screening fly ash solid blocks to obtain molded fly ash particles;
② acid treatment, namely soaking the formed fly ash particles in a nitric acid solution with the concentration of more than 99.9 percent, washing the filtered formed fly ash particles to be neutral by distilled water, and then sending the particles into a drying box to generate a carrier of the fly ash modified SCR denitration catalyst through primary drying;
③ soaking and loading, namely soaking the carrier of the fly ash modified SCR denitration catalyst into a metal oxide salt solution consisting of unsaturated copper nitrate solution to load metaloxide serving as an active component on the carrier of the fly ash modified SCR denitration catalyst, and then carrying out secondary drying in a drying box and calcining in a calcining furnace to prepare the selective catalytic reduction denitration catalyst.
According to the technical scheme, the fly ash particles and the additive comprise the following components in percentage by mass: 80-82% of fly ash particles, 15-16% of powder consisting of lime and gypsum, 3-4% of ordinary portland cement and 0.04-1% of aluminum oxide powder particles.
According to the technical scheme, the standing time of the mixture of the fly ash particles and the additive is 30-60 minutes.
According to the technical scheme, the forming and activating pretreatment time of the fly ash particles and the additive mixture in the pretreatment kettle is more than 8 hours.
According to the technical scheme, the particle size range of the screened molded fly ash particles is 0.3-1 mm.
According to the technical scheme, the material proportion of the nitric acid solution and the formed fly ash particles is that 1 g of formed fly ash particles is mixed in every 5 ml of nitric acid solution.
According to the technical scheme, the temperature of the nitric acid solution and the immersion forming fly ash particles is 50-90 ℃ during stirring, and the acid treatment time is 30-60 minutes.
According to the technical scheme, the temperature of the primary drying is 200-400 ℃, and the time of the primary drying is more than 3 hours.
According to the technical scheme, the carrier of the fly ash modified SCR denitration catalyst is immersed in a copper nitrate solution, and after the carrier is fully stirred, the immersion time at room temperature is 1 hour.
According to the technical scheme, the mass of the metal oxide as an active component loaded on the carrier of the fly ash modified SCR denitration catalyst is 1%, 5% or 10%.
According to the technical scheme, the temperature of the secondary drying is 120 ℃.
According to the technical scheme, the calcining temperature is 300-400 ℃, and the calcining time is more than 3 hours.
The boiler fly ash is the main solid waste generated by the combustion of industrial coal-fired boilers in China for a long timeThe waste causes serious environmental pollution. In the past, the common treatment of boiler fly ash waste has been by landfilling or used to prepare building materials. However, the former causes environmental risks, while the latter brings about very limited benefits. According to the invention, the boiler fly ash is used as a carrier, and the selective catalytic reduction denitration catalyst is prepared according to the steps, so that not only is the waste effectively utilized, but also the cost of the SCR denitration process is reduced, and the environmental hidden trouble is eliminated. Experimental tests show that the catalytic activity of the catalyst applied to the ammonia SCR denitration in a fixed bed active reaction device has a denitration rate higher than 90%, and the continuous catalytic denitration activity can be maintained for a long time. Experimental tests also prove that the fly ash modified carrier loaded copper oxide SCR denitration catalyst has better SO resistance2And (4) performance. When the working temperature is higher than 280 ℃, the catalyst can continuously work for more than 100 hours under the condition of ensuring that the catalytic denitration rate is higher than 90 percent.
The following further describes embodiments of the present invention with reference to the drawings.
Drawings
The attached drawing is a preparation flow chart of the invention.
Detailed Description
Referring to fig. 1, the steps of the method of the present invention are as follows:
① fly ash forming, which is to mix 80-82 wt%, 15-16 wt%, 3-4 wt% and 0.04-1 wt% of fly ash in a dust removing device at the tail of a pulverized coal combustion boiler, ordinary portland cement and aluminum oxide powder particles in order to effectively increase the specific surface area and the number of fly ash micropores, to put the stirred mixture into a pretreatment kettle after standing for 30-60 minutes, to perform forming activation pretreatment on the mixture for more than 8 hours by using high-temperature and high-pressure steam with the temperature of 850-950 ℃ and the pressure of 80-100 standard atmospheres, to mechanically crush and screen the formed solid blocks of fly ash to obtain formed fly ash particles with the particle size of 0.3-1 mm.
② acid treatment, in order to use the formed fly ash particles as the carrier of SCR catalyst, it needs to further improve its micropore structure to make it more beneficial to the SCR denitration reaction of ammonia process, therefore, at 50-90 deg.C, the formed fly ash particles are soaked in nitric acid solution with the concentration>99.9% for 1 hour, the material proportion between them is 1 g formed fly ash particles per 5 ml concentrated nitric acid solution, then the formed fly ash particles filtered out by the filter device are washed for more than 3 times by distilled water with the volume about twice of the volume until they become neutral, then the particles are sent into a dryingbox with the temperature of 200-400 deg.C to be dried for more than 3 hours, and the carrier of fly ash modified SCR denitration catalyst is produced.
③ soaking and loading, namely soaking the carrier of the fly ash modified SCR denitration catalyst into unsaturated copper nitrate solution corresponding to copper oxide for 1 hour at normal temperature to load metal copper oxide serving as an active component on the carrier of the fly ash modified SCR denitration catalyst, then sending the carrier into a drying box at the temperature of 120 ℃ for secondary drying, and then calcining the carrier in a calcining furnace at the temperature of 300-400 ℃ for more than 3 hours to decompose nitrate on the carrier to generate copper oxide active substances, thus finally preparing the selective catalytic reduction denitration catalyst.
Claims (12)
1. A method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash is characterized by comprising the following steps:
① fly ash molding, mixing and stirring the boiler fly ash particles and an additive consisting of lime and gypsum powder, ordinary portland cement and aluminum oxide powder particles, standing, feeding into a pretreatment kettle, molding and activating the mixture by using high-temperature and high-pressure steam with the temperature of 850-950 ℃ and the pressure of 80-100 standard atmospheres, crushing and screening fly ash solid blocks to obtain molded fly ash particles;
② acid treatment, namely soaking the formed fly ash particles in a nitric acid solution with the concentration of more than 99.9 percent, washing the filtered formed fly ash particles to be neutral by distilled water, and then sending the particles into a drying box to generate a carrier of the fly ash modified SCRdenitration catalyst through primary drying;
③ soaking and loading, namely soaking the carrier of the fly ash modified SCR denitration catalyst into a metal oxide salt solution consisting of unsaturated copper nitrate solution to load metal oxide serving as an active component on the carrier of the fly ash modified SCR denitration catalyst, and then carrying out secondary drying in a drying box and calcining in a calcining furnace to prepare the selective catalytic reduction denitration catalyst.
2. The method for preparing the selective catalytic reduction denitration catalyst by using the boiler fly ash as claimed in claim 1, wherein the mass percentages of the components in the fly ash particles and the additive are as follows: 80-82% of fly ash particles, 15-16% of powder consisting of lime and gypsum, 3-4% of ordinary portland cement and 0.04-1% of aluminum oxide powder particles.
3. The method for preparing the selective catalytic reduction denitration catalyst by using the boiler fly ash as claimed in claim 1 or 2, wherein the standing time of the mixture of the fly ash particles and the additive is 30-60 minutes.
4. The method for preparing the SCR denitration catalyst according to claim 1, wherein the time of the molding activation pretreatment of the fly ash particle and the additive mixture in the pretreatment tank is more than 8 hours.
5. The method for preparing the selective catalytic reduction denitration catalyst by using the boiler fly ash as claimed in claim 1, wherein the particle size range of the screened shaped fly ash particles is 0.3-1 mm.
6. The method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash as claimed in claim 1, wherein the material ratio of the nitric acid solution to the formed fly ash particles is 1 g per 5 ml of the nitric acid solution.
7. The method for preparing the selective catalytic reduction denitration catalyst by using the boiler fly ash as claimed in claim 6, wherein the temperature of the nitric acid solution and the formed fly ash particles is 50-90 ℃ while stirring, and the acid treatment time is 30-60 minutes.
8. The method for preparing the selective catalytic reduction denitration catalyst by using the boiler fly ash as claimed in claim 1, wherein the temperature of the primary drying is 200-400 ℃, and the time of the primary drying is more than 3 hours.
9. The method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash as claimed in claim 1, wherein the carrier of the fly ash modified SCR denitration catalyst is immersed in a copper nitrate solution, and after being sufficiently stirred, the immersion time at room temperature is 1 hour.
10. The method for preparing a selective catalytic reduction denitration catalyst using boiler fly ash according to claim 1, wherein the mass of the metal oxide supported as an active ingredient on the carrier of the fly ash-modified SCR denitration catalyst is 1%, 5% or 10%.
11. The method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash according to claim 1, wherein the temperature of the secondary drying is 120 ℃.
12. The method for preparing the selective catalytic reduction denitration catalyst by using the boiler fly ash as claimed in claim 1 or 11, wherein the calcination temperature is 300-400 ℃ and the calcination time is 3 hours or more.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310100420 CN1246069C (en) | 2003-10-16 | 2003-10-16 | Method for preparing selective catalytic reduction and denitration catalyst by boiler coal ash |
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| CN 200310100420 CN1246069C (en) | 2003-10-16 | 2003-10-16 | Method for preparing selective catalytic reduction and denitration catalyst by boiler coal ash |
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| CN1246069C true CN1246069C (en) | 2006-03-22 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7824574B2 (en) * | 2006-09-21 | 2010-11-02 | Eltron Research & Development | Cyclic catalytic upgrading of chemical species using metal oxide materials |
| CN101940878B (en) * | 2010-05-21 | 2012-12-05 | 中国神华能源股份有限公司 | Method for denitrating gas fume |
| CN201807308U (en) * | 2010-05-21 | 2011-04-27 | 中国神华能源股份有限公司 | Equipment for denitration by selective catalytic reduction of smoke |
| CN102000564B (en) * | 2010-10-27 | 2012-11-07 | 合肥工业大学 | Coal ash and attapulgite compound SCR denitration catalyst and preparation method thereof |
| CN102764671B (en) * | 2012-08-03 | 2014-04-09 | 东北石油大学 | Method for preparing denitration catalyst by coal ash |
| CN102861566B (en) * | 2012-10-20 | 2014-06-11 | 东北石油大学 | Method for preparing bimetallic denitration catalyst by using coal ash |
| CN106423146A (en) * | 2016-09-14 | 2017-02-22 | 北京化工大学 | SCR (selective catalytic reduction) catalyst prepared from red mud taken as carrier and loaded with Mn and Ce and preparation method of SCR catalyst |
| CN106492790A (en) * | 2016-09-23 | 2017-03-15 | 河北工业大学 | A kind of low temperature SCR denitration catalyst and preparation method thereof |
| CN108295856B (en) * | 2018-03-15 | 2020-06-02 | 清华大学 | Method for preparing methane dry reforming bimetallic catalyst from fly ash silicon extraction residues |
| CN111701622A (en) * | 2020-06-29 | 2020-09-25 | 西安科技大学 | Preparation method of Cu-MOF-Fe fly ash catalyst for denitration and demercuration |
| CN114602471A (en) * | 2022-03-23 | 2022-06-10 | 华北电力大学 | High-temperature flue gas denitration catalyst and preparation method thereof |
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Owner name: QINGHUA UNIVERSITY; TONGFANG ENVIRONMENT CO. Free format text: FORMER OWNER: QINGHUA UNIVERSITY; TONGFANG CO., LTD. Effective date: 20080516 |
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Effective date of registration: 20080516 Address after: A, Tsinghua Tongfang science and Technology Square, Beijing 2907, postcode: 100083 Co-patentee after: TONGFANG ENVIRONMENT Co.,Ltd. Patentee after: TSINGHUA University Address before: A, Tsinghua Tongfang science and Technology Square, Beijing 2907, postcode: 100083 Co-patentee before: Tongfang Co.,Ltd. Patentee before: Tsinghua University |
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Granted publication date: 20060322 |
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