CN1607027A - 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 PDF

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CN1607027A
CN1607027A CN 200310100420 CN200310100420A CN1607027A CN 1607027 A CN1607027 A CN 1607027A CN 200310100420 CN200310100420 CN 200310100420 CN 200310100420 A CN200310100420 A CN 200310100420A CN 1607027 A CN1607027 A CN 1607027A
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fly ash
denitration catalyst
catalytic reduction
selective catalytic
preparing
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CN1246069C (en
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宣小平
姚强
赵旭东
曹慧芳
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TONGFANG ENVIRONMENT CO Ltd
Tsinghua University
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Tsinghua University
Qinghua Tongfang Co Ltd
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Abstract

A process for preparing selective catalytic reduction denitration catalyst containes following steps, 1, fly ash and additive are mixed and stirred, active shaping pretreated in reactor, shaped fly ash grain is obtained by pulverizing and sieving fly ash block. 2, soaking shaped fly ash grain by high-concentration strong acid, flushing it to neutrality by distilled water, to form modified SCR denitration catalyst carrier through drying once more. 3, soaking modified SCR denitration catalyst carrier into metal oxide salt solution to obtain the selective catalytic reduction denitration catalyst through two time drying and calcinating.

Description

Method for preparing selective catalytic reduction denitration catalyst by using boiler fly ash
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 atthe 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 additives, standing, feeding into a pretreatment kettle, performing molding activation pretreatment on the mixture by using high-temperature and high-pressure steam, and crushing and sieving fly ash solid blocks to obtain molded fly ash particles;
② acid treatment, namely soaking the formed fly ash particles in high-concentration strong acid, washing the filtered formed fly ash particles to be neutral by distilled water, and then sending the fly ash particles into a drying box to generate a carrier of the fly ash modified SCR denitration catalyst through primary drying;
③ dipping and loading, namely dipping the carrier of the fly ash modified SCR denitration catalyst into a metal oxide salt solution to load the 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.
According to the technical scheme, the additive consists of lime, gypsum powder, ordinary portland cement and aluminum oxide powder particles.
According to the technical scheme, the fly ash particles and the additive comprise the following components in proportion: 80-82% of fly ash particles, 15-16% of lime and gypsum powder, 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 temperature of the high-temperature and high-pressure steam is 850-950 ℃, and the pressure is 80-100 standard atmospheric pressures.
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 high-concentration strong acid is a nitric acid solution with the concentration of more than 99.9 percent.
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 metal oxide salt solution is unsaturated copper nitrate solution.
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.
Boiler fly ash has been a main solid waste generated by the combustion of industrial coal-fired boilers in China for a long time, and has caused 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, mixing 80-82%, 15-16%, 3-4% and 0.04-1% of fly ash, lime and gypsum powder in additive, common Portland cement and alumina powder particles according to mass ratio, standing the mixture for 30-60 min, sending into a pretreatment kettle, performing forming activation pretreatment on the mixture for more than 8 h by using high-temperature high-pressure water vapor with temperature of 850-950 ℃ and pressure of 80-100 standard atmospheric pressure, mechanically crushing and sieving the formed fly ash solid block to obtain formed fly ash particles with particle size range 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 drying box 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 (16)

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 additives, standing, feeding into a pretreatment kettle, performing molding activation pretreatment on the mixture by using high-temperature and high-pressure steam, and crushing and sieving fly ash solid blocks to obtain molded fly ash particles;
② acid treatment, namely soaking the formed fly ash particles in high-concentration strong acid, washing the filtered formed fly ash particles to be neutral by distilled water, and then sending the fly ash particles into a drying box to generate a carrier of the fly ash modified SCR denitration catalyst through primary drying;
③ dipping and loading, namely dipping the carrier of the fly ash modified SCR denitration catalyst into a metal oxide salt solution to load the 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 a selective catalytic reduction denitration catalyst using boiler fly ash according to claim 1, wherein the additive is composed of lime and gypsum powder, ordinary portland cement, and alumina 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 proportions of the components in the fly ash particles and the additive are as follows: 80-82% of fly ash particles, 15-16% of lime and gypsum powder, 3-4% of ordinary portland cement and 0.04-1% of aluminum oxide powder particles.
4. The method for preparing the selective catalytic reduction denitration catalyst by using the boiler fly ash as claimed in claim 3, wherein the standing time of the mixture of the fly ash particles and the additive is 30-60 minutes.
5. 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 high temperature and high pressure steam is 850-950 ℃ and the pressure is 80-100 standard atmospheres.
6. The method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash as claimed in claim 1 or 5, wherein the time of the molding activation pretreatment of the fly ash particle and additive mixture in the pretreatment tank is more than 8 hours.
7. 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.
8. The method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash as claimed in claim 1, wherein the high-concentration strong acid is a nitric acid solution with a concentration of more than 99.9%.
9. The method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash as claimed in claim 8, 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.
10. The method for preparing the selective catalytic reduction denitration catalyst by using the boiler fly ash as claimed in claim 9, 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.
11. 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.
12. The method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash according to claim 1, wherein the metal oxide salt solution is an unsaturated copper nitrate solution.
13. The method for preparing a selective catalytic reduction denitration catalyst by using boiler fly ash as claimed in claim 1 or 12, 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.
14. The method for preparing a selective catalytic reduction denitration catalyst using boiler fly ash according to claim 1 or 12,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%.
15. 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 ℃.
16. The method for preparing the selective catalytic reduction denitration catalyst by using the boiler fly ash as claimed in claim 1 or 15, wherein the calcination temperature is 300-400 ℃ and the calcination time is 3 hours or more.
CN 200310100420 2003-10-16 2003-10-16 Method for preparing selective catalytic reduction and denitration catalyst by boiler coal ash Expired - Lifetime CN1246069C (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940879A (en) * 2010-05-21 2011-01-12 中国神华能源股份有限公司 Selective catalytic reduction denitration method of flue gas
CN101940878A (en) * 2010-05-21 2011-01-12 中国神华能源股份有限公司 Method for denitrating gas fume
CN102000564A (en) * 2010-10-27 2011-04-06 合肥工业大学 Coal ash and attapulgite compound SCR denitration catalyst and preparation method thereof
CN102764671A (en) * 2012-08-03 2012-11-07 东北石油大学 Method for preparing denitration catalyst by coal ash
CN102861566A (en) * 2012-10-20 2013-01-09 东北石油大学 Method for preparing bimetallic denitration catalyst by using coal ash
CN101534927B (en) * 2006-09-21 2014-02-19 亚创研究发展有限公司 Cyclic catalytic upgrading of chemical species using metal oxide materials
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
CN108295856A (en) * 2018-03-15 2018-07-20 清华大学 Coal ash lifting silicon residue prepares the method that biogas dry type reforms bimetallic catalyst
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

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101534927B (en) * 2006-09-21 2014-02-19 亚创研究发展有限公司 Cyclic catalytic upgrading of chemical species using metal oxide materials
CN101940878A (en) * 2010-05-21 2011-01-12 中国神华能源股份有限公司 Method for denitrating gas fume
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
CN101940879A (en) * 2010-05-21 2011-01-12 中国神华能源股份有限公司 Selective catalytic reduction denitration method of flue gas
CN102000564A (en) * 2010-10-27 2011-04-06 合肥工业大学 Coal ash and attapulgite compound SCR denitration catalyst and preparation method thereof
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
CN102764671A (en) * 2012-08-03 2012-11-07 东北石油大学 Method for preparing denitration catalyst by coal ash
CN102861566A (en) * 2012-10-20 2013-01-09 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
CN108295856A (en) * 2018-03-15 2018-07-20 清华大学 Coal ash lifting silicon residue prepares the method that biogas dry type reforms bimetallic catalyst
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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