CN112808277A - Low-temperature SCR denitration catalyst, preparation method and application thereof - Google Patents

Low-temperature SCR denitration catalyst, preparation method and application thereof Download PDF

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CN112808277A
CN112808277A CN202011613126.8A CN202011613126A CN112808277A CN 112808277 A CN112808277 A CN 112808277A CN 202011613126 A CN202011613126 A CN 202011613126A CN 112808277 A CN112808277 A CN 112808277A
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钟圣俊
黄哲彪
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01D53/8625—Nitrogen oxides
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Abstract

The invention relates to a low-temperature SCR denitration catalyst, and a preparation method and application thereof. The low-temperature SCR denitration catalyst is TiO2The carrier is Mn and Fe as active components, the mass ratio of the active components Fe to Mn is 1: 3-4: 3, and the active components Fe and the carrier TiO2The mass ratio of (A) to (B) is 1: 20-1: 5. The preparation method adopts an impregnation method to prepare the catalyst, and the catalyst is obtained by baking the catalyst in the air atmosphere. The catalyst obtained by the invention has the advantages of measurement temperature of 240 ℃, ammonia-nitrogen ratio of 1:1 and space velocity of 30000h‑1And the denitration efficiency is 5 percent under the condition of oxygen concentrationCan reach 100 percent. The catalyst prepared by the method is safe and green, can meet the denitration requirement in actual production activities, and has great economic and ecological benefits.

Description

Low-temperature SCR denitration catalyst, preparation method and application thereof
Technical Field
The invention relates to a low-temperature SCR denitration catalyst, a preparation method and application thereof, and belongs to the technical field of application environment protection and catalysts.
Background
At present, the control of nitrogen oxides mainly comprises the following three methods: the method comprises the steps of denitrification treatment of fuel before combustion, improvement of a combustion mode in a combustion process and denitrification treatment of flue gas after combustion. The technology for denitration of flue gas after combustion can realize high-efficiency removal of nitrogen oxides and reach low emission standard, and is also the most main method for controlling emission of nitrogen oxides at present.
The most mature of the flue gas denitration technology is the Selective Catalytic Reduction (SCR) technology. The selective catalytic reduction device can be directly arranged behind a boiler, and also can be arranged behind an electric dust remover or a flue gas desulfurization device. If the catalyst is directly arranged behind a boiler and in front of an air preheater and a dust remover, the flue gas containing a large amount of smoke dust and sulfur dioxide can corrode and poison the catalyst, and the service life of the catalyst is shortened. If the catalyst is placed behind a desulfurization and dust removal device, the temperature of the flue gas after desulfurization treatment is greatly reduced and is far lower than the activity temperature window of the existing catalyst. Therefore, the method needs to be provided with a gas reheater, and has high energy consumption and high economic cost. At present, research and development of high-efficiency low-temperature denitration catalysts become a hot point of domestic and foreign research. The high-efficiency low-temperature denitration catalyst mainly comprises a noble metal catalyst, a molecular sieve catalyst, a metal catalyst, a carbon-based catalyst and the like, wherein the research on the metal catalyst is the most extensive. At present, V2O5-WO3/TiO2The catalyst is the most common catalyst in industry, but the catalyst is expensive and V2O5Has certain biological toxicity, and can cause pollution to the surrounding environment and even harm to human health when being used or treated improperly.
Disclosure of Invention
Technical problem to be solved
In order to solve the current use situation and the existing defects of the selective catalytic reduction catalyst in the prior art, the invention provides a warm SCR denitration catalyst, and a preparation method and application thereof.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a low-temperature SCR denitration catalyst which is TiO2The carrier is Mn and Fe as active components, the mass ratio of the active components Fe to Mn is 1: 3-4: 3, and the active components Fe and the carrier TiO2Mass ofThe ratio is 1: 20-1: 5.
The preparation method of the low-temperature SCR denitration catalyst comprises the following steps:
s1, dissolving manganese salt and iron-containing salt in deionized water to prepare impregnation liquid, and then adding TiO into the impregnation liquid2；
S2, stirring the mixture obtained in the step S1 in a water bath heating magnetic stirrer to fully mix the components therein, uniformly dipping the components, and evaporating water until the mixture is sticky;
s3, placing the mixture obtained in the step S2 in a drying box for drying, and removing moisture;
and S4, placing the sample obtained in the step S3 in a muffle furnace for roasting to obtain the low-temperature SCR denitration catalyst.
In the preparation method, in step S1, preferably, the iron salt and the manganese salt are added according to the mass ratio of the iron element to the manganese element of 1: 3-4: 3, and the Fe element and the carrier TiO are added2The mass ratio of the water to the water is 1: 20-1: 5, and the amount of the deionized water is according to the TiO22 to 3 times the mass of (A) is added. A large number of experiments prove that if the contents of Mn and Fe in active components in the prepared low-temperature SCR denitration catalyst are too low, the denitration performance of the obtained catalyst is poor. The content of the active component is too high, so that more metal oxide can be formed in the roasting process and covers the surface of the catalyst, and the denitration performance of the catalyst is influenced.
When the mass ratio of the active components Mn and Fe is too low, excessive iron oxide is formed in the roasting process and covers the surface of the catalyst, so that the denitration performance of the catalyst is reduced. When the mass ratio of Mn to Fe as the active components is too high, the denitration performance of the catalyst is poorer than that of the catalyst with lower mass ratio. Therefore, the iron salt and the manganese salt are preferably added according to the mass ratio of the iron to the manganese element of 1: 3-4: 3.
In the preparation method as described above, preferably, in step S1, the manganese salt is manganese acetate tetrahydrate, and the iron-containing salt is ferric nitrate.
In the preparation method, in step S2, the temperature of the water bath heating is preferably 60 to 80 ℃ for 30 to 60 min.
In the preparation method, in step S3, the drying temperature is preferably 100 to 120 ℃, and the drying time is preferably 10 to 12 hours.
In the preparation method, in step S4, the baking temperature is preferably 350 to 800 ℃, and the baking time is preferably 3 to 5 hours.
Further, the roasting temperature is preferably 350-650 ℃.
The application of the low-temperature SCR denitration catalyst in removing nitrogen in flue gas is disclosed.
According to the application, preferably, the flue gas has the ammonia-nitrogen ratio of 1:1 at 200-280 ℃ and the space velocity of 30000h-1And under the condition that the oxygen concentration is 5%, the denitration rate reaches over 95%.
When the ammonia-nitrogen ratio in the simulated flue gas is 1:1, the prepared low-temperature SCR denitration catalyst shows the best denitration performance. According to the low-temperature SCR equation, when the ammonia concentration is low, the denitration reaction cannot be completely performed. When the ammonia gas concentration is high, the leakage of the ammonia gas in the treatment process can cause great harm to the surrounding environment, so the flue gas with the ammonia-nitrogen ratio of 1:1 is preferred.
The space velocity of the simulated flue gas is 30000h-1When the catalyst is used, the prepared low-temperature SCR denitration catalyst shows the best denitration performance. If the air speed of the flue gas is too low, the treatment time is longer, and the denitration speed is slower. If the air speed of the flue gas is too high, the reaction is not complete enough, and the removal rate of the nitric oxide is low.
The catalyst showed the best denitration performance at a concentration of 5% oxygen in the simulated flue gas. If the oxygen concentration is low, the denitration performance of the catalyst may be reduced. If the oxygen concentration is high, the nitric oxide removal rate still remains 100%, but excess oxygen is wasted.
(III) advantageous effects
The invention has the beneficial effects that:
the low-temperature SCR denitration catalyst provided by the invention is simple in preparation method, low in cost and suitable for practical application of industrial production activities, and the preparation process does not cause harm to human and environment. The application conditions of the obtained low-temperature SCR denitration catalyst accord with the actual conditions of industrial production, the denitration effect is good, the nitrogen oxides in the flue gas can be effectively removed, and the harm of the nitrogen oxides to the surrounding environment and the human health is prevented.
Drawings
FIG. 1 is a graph showing the relationship between denitration performance and temperature of a catalyst having different ratios of active components in the example of the present invention;
FIG. 2 is a graph showing the relationship between the denitration performance and the temperature of the catalyst when the calcination temperatures are different in the example of the present invention.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The flue gas used in the following examples of the invention is simulated flue gas consisting of N2(balance gas, 99.999%), zero-order air (N)2/O2) NO (5000ppm) and NH3(5000ppm) are mixed. The total flow of the simulated smoke is 1000mL/min, wherein N is2550mL/min, 250mL/min zero-level air, 100mL/min NO, NH3Is 100 mL/min. The method for measuring the denitration efficiency comprises the following steps: the prepared catalyst is placed above a filter screen in the middle of a quartz tube with the inner diameter of 15.5mm, simulated flue gas is introduced after the quartz tube is heated to a specific temperature, the NO concentrations at the inlet and the outlet of the quartz tube are measured by a flue gas analyzer, and the denitration rate is obtained through calculation. The specific calculation formula of the denitration efficiency is as follows:
Figure BDA0002875432920000041
wherein: eta is denitration efficiency; cinIs the NO inlet concentration; coutIs the NO outlet concentration.
Example 1
A preparation method of a low-temperature SCR denitration catalyst comprises the following steps:
2.0730g of manganese acetate tetrahydrate and 4.0000g of titanium dioxide were added to 9mL of deionized water at room temperature, and the mixture was stirred in a water bath magnetic stirrer at a temperature of 70 ℃ for 40min to thoroughly mix the components and evaporate the water. The stirred sample was dried in a drying oven for 12h at 110 ℃. And roasting the dried sample in a muffle furnace at 450 ℃ for 4h, and grinding to 40-60 meshes to obtain the low-temperature SCR denitration catalyst.
The obtained catalyst Mn, Fe and TiO2Has a mass ratio of 3:0:20 and is marked as Mn/TiO2。
The denitration performance of the catalyst of the embodiment is measured by using simulated flue gas, and the denitration efficiency at different temperatures is shown in fig. 1. As can be seen from fig. 1: the denitration efficiency of the catalyst is increased along with the increase of the temperature, the ammonia-nitrogen ratio is 1:1 at 240 ℃, and the space velocity is 30000h-1And the denitration efficiency reaches 87.5% under the condition that the oxygen concentration is 5%. Example 2
A preparation method of a low-temperature SCR denitration catalyst comprises the following steps:
2.0730g of manganese nitrate tetrahydrate, 0.5050g of iron nitrate nonahydrate and 4.0000g of titanium dioxide were added to 9mL of deionized water at room temperature, and the mixture was stirred in a water bath magnetic stirrer at a water bath temperature of 70 ℃ for 40min to thoroughly mix the components and evaporate the water. The stirred sample was dried in a drying oven for 12h at 110 ℃. And roasting the dried sample in a muffle furnace at 450 ℃ for 4h, and grinding to 40-60 meshes to obtain the low-temperature SCR denitration catalyst.
The obtained catalyst Mn, Fe and TiO2The mass ratio of (1: 20) is 3:20, and is marked as Mn-Fe (5 wt%)/TiO2。
The denitration performance of the catalyst of the embodiment is measured by using simulated flue gas, and the denitration efficiency at different temperatures is shown in fig. 1. As can be seen from fig. 1: the denitration efficiency of the catalyst is increased along with the increase of the temperature, the ammonia-nitrogen ratio is 1:1 at 240 ℃, and the space velocity is 30000h-1And the denitration efficiency reaches 89.25% under the condition that the oxygen concentration is 5%.
Example 3
A preparation method of a low-temperature SCR denitration catalyst comprises the following steps:
2.0730g of manganese nitrate tetrahydrate, 1.0100g of ferric nitrate nonahydrate and 4.0000g of titanium dioxide were added to 9mL of deionized water at room temperature, and the mixture was stirred in a water bath magnetic stirrer at 70 ℃ for 40min to thoroughly mix the components and evaporate the water. The stirred sample was dried in a drying oven for 12h at 110 ℃. And roasting the dried sample in a muffle furnace at 450 ℃ for 4h, and grinding to 40-60 meshes to obtain the low-temperature SCR denitration catalyst.
The obtained catalyst Mn, Fe and TiO2The mass ratio of (1)/(2)/(20) is expressed as Mn-Fe (10 wt%)/TiO2。
The denitration performance of the catalyst of the embodiment is measured by using simulated flue gas, and the denitration efficiency at different temperatures is shown in fig. 1. As can be seen from fig. 1: the denitration efficiency of the catalyst is increased along with the increase of the temperature, the ammonia-nitrogen ratio is 1:1 at 240 ℃, and the space velocity is 30000h-1And the denitration efficiency reaches 97.75 percent under the condition that the oxygen concentration is 5 percent.
Example 4
A preparation method of a low-temperature SCR denitration catalyst comprises the following steps:
2.0730g of manganese nitrate tetrahydrate, 1.5150g of iron nitrate nonahydrate and 4.0000g of titanium dioxide were added to 9mL of deionized water at room temperature, and the mixture was stirred in a water bath magnetic stirrer at a water bath temperature of 70 ℃ for 40min to thoroughly mix the components and evaporate the water. The stirred sample was dried in a drying oven for 12h at 110 ℃. And roasting the dried sample in a muffle furnace at 450 ℃ for 4h, and grinding to 40-60 meshes to obtain the low-temperature SCR denitration catalyst.
The obtained catalyst Mn, Fe and TiO2The mass ratio of (1) is 3:3:20, and is marked as Mn-Fe (15 wt%)/TiO2。
The denitration performance of the catalyst of the embodiment is measured by using simulated flue gas, and the denitration efficiency at different temperatures is shown in fig. 1. As can be seen from fig. 1: the denitration efficiency of the catalyst is increased along with the increase of the temperature, the ammonia-nitrogen ratio is 1:1 at 240 ℃, and the space velocity is 30000h-1And the denitration efficiency reaches 100% under the condition that the oxygen concentration is 5%.
Example 5
A preparation method of a low-temperature SCR denitration catalyst comprises the following steps:
2.0730g of manganese nitrate tetrahydrate, 2.0200g of iron nitrate nonahydrate and 4.0000g of titanium dioxide were added to 9mL of deionized water at room temperature, and the mixture was stirred in a water bath magnetic stirrer at a water bath temperature of 70 ℃ for 40min to thoroughly mix the components and evaporate the water. The stirred sample was dried in a drying oven for 12h at 110 ℃. And roasting the dried sample in a muffle furnace at 450 ℃ for 4h, and grinding to 40-60 meshes to obtain the low-temperature SCR denitration catalyst.
The obtained catalyst Mn, Fe and TiO2The mass ratio of (1) to (2) is 3:4:20, and is marked as Mn-Fe (20 wt%)/TiO2。
The denitration performance of the catalyst of the embodiment is measured by using simulated flue gas, and the denitration efficiency at different temperatures is shown in fig. 1. As can be seen from fig. 1: the denitration efficiency of the catalyst is increased along with the increase of the temperature, the ammonia-nitrogen ratio is 1:1 at 240 ℃, and the space velocity is 30000h-1And the denitration efficiency reaches 100% under the condition that the oxygen concentration is 5%.
Example 6
A preparation method of a low-temperature SCR denitration catalyst comprises the following steps:
2.0730g of manganese nitrate tetrahydrate, 1.5150g of iron nitrate nonahydrate and 4.0000g of titanium dioxide were added to 9mL of deionized water at room temperature, and the mixture was stirred in a water bath magnetic stirrer at a water bath temperature of 70 ℃ for 40min to thoroughly mix the components and evaporate the water. The stirred sample was dried in a drying oven for 12h at 110 ℃. And roasting the dried sample in a muffle furnace at 350 ℃ for 4h, and grinding to 40-60 meshes to obtain the low-temperature SCR denitration catalyst.
The obtained catalyst Mn, Fe and TiO2The mass ratio of (1) to (2) is 3:3:20, and the mark is Mn-Fe/TiO2(350℃)。
The denitration performance of the catalyst of the embodiment is measured by using simulated flue gas, and the denitration efficiency at different temperatures is shown in fig. 2. As can be seen from fig. 2: denitration efficiency of catalyst increases with temperatureIncreasing the ammonia nitrogen ratio at 240 ℃ to 1 and the space velocity at 30000h-1And the denitration efficiency reaches 81.75% under the condition that the oxygen concentration is 5%.
Example 7
A preparation method of a low-temperature SCR denitration catalyst comprises the following steps:
2.0730g of manganese nitrate tetrahydrate, 1.5150g of iron nitrate nonahydrate and 4.0000g of titanium dioxide were added to 9mL of deionized water at room temperature, and the mixture was stirred in a water bath magnetic stirrer at a water bath temperature of 70 ℃ for 40min to thoroughly mix the components and evaporate the water. The stirred sample was dried in a drying oven for 12h at 110 ℃. And roasting the dried sample in a muffle furnace at 550 ℃ for 4h, and grinding to 40-60 meshes to obtain the low-temperature SCR denitration catalyst.
The obtained catalyst Mn, Fe and TiO2The mass ratio of (1) to (2) is 3:3:20, and the mark is Mn-Fe/TiO2(550℃)。
The denitration performance of the catalyst of the embodiment is measured by using simulated flue gas, and the denitration efficiency at different temperatures is shown in fig. 2. As can be seen from fig. 2: the denitration efficiency of the catalyst is increased along with the increase of the temperature, the ammonia-nitrogen ratio is 1:1 at 240 ℃, and the space velocity is 30000h-1And the denitration efficiency reaches 96.00% under the condition that the oxygen concentration is 5%.
Example 8
A preparation method of a low-temperature SCR denitration catalyst comprises the following steps:
2.0730g of manganese nitrate tetrahydrate, 1.5150g of iron nitrate nonahydrate and 4.0000g of titanium dioxide were added to 9mL of deionized water at room temperature, and the mixture was stirred in a water bath magnetic stirrer at a water bath temperature of 70 ℃ for 40min to thoroughly mix the components and evaporate the water. The stirred sample was dried in a drying oven for 12h at 110 ℃. And roasting the dried sample in a muffle furnace at 650 ℃ for 4h, and grinding to 40-60 meshes to obtain the low-temperature SCR denitration catalyst.
The obtained catalyst Mn, Fe and TiO2The mass ratio of (1) to (2) is 3:3:20, and the mark is Mn-Fe/TiO2(650℃)。
The denitration performance of the catalyst of the embodiment is measured by using simulated flue gas, and the denitration efficiency at different temperatures is shown in fig. 2. As can be seen from fig. 2: the denitration efficiency of the catalyst is increased along with the increase of the temperature, the ammonia-nitrogen ratio is 1:1 at 240 ℃, and the space velocity is 30000h-1And the denitration efficiency reaches 83.00% under the condition that the oxygen concentration is 5%.
Example 9
A preparation method of a low-temperature SCR denitration catalyst comprises the following steps:
2.0730g of manganese nitrate tetrahydrate, 1.5150g of iron nitrate nonahydrate and 4.0000g of titanium dioxide were added to 9mL of deionized water at room temperature, and the mixture was stirred in a water bath magnetic stirrer at a water bath temperature of 70 ℃ for 40min to thoroughly mix the components and evaporate the water. The stirred sample was dried in a drying oven for 12h at 110 ℃. And roasting the dried sample in a muffle furnace at 800 ℃ for 4h, and grinding to 40-60 meshes to obtain the low-temperature SCR denitration catalyst.
The obtained catalyst Mn, Fe and TiO2The mass ratio of (1) to (2) is 3:3:20, and the mark is Mn-Fe/TiO2(800℃)。
The denitration performance of the catalyst of the embodiment is measured by using simulated flue gas, and the denitration efficiency at different temperatures is shown in fig. 2. As can be seen from fig. 2: the denitration efficiency of the catalyst is increased along with the increase of the temperature, the ammonia-nitrogen ratio is 1:1 at 240 ℃, and the space velocity is 30000h-1And the denitration efficiency reaches 59.50% under the condition that the oxygen concentration is 5%.
Examples 6 to 9 were conducted to investigate the influence of different calcination temperatures on the denitration performance of the catalyst, and 350 ℃, 450 ℃, 550 ℃, 650 ℃ and 800 ℃ in parentheses after the catalyst obtained in examples 6 to 9 mean the calcination temperatures used for obtaining the catalyst. It can be seen from fig. 2 that the higher the calcination temperature is, the better, the denitration performance obtained is the best when the calcination temperature is 450 ℃, and the calcination temperature is preferably 350 ℃ to 650 ℃, and the most preferably 450 ℃ when the catalyst is prepared for obtaining the better denitration performance.
The invention uses Mn and Fe as active components of the catalyst, TiO2As a carrier, aThe material is easy to obtain and the cost is low. The invention uses the equal-volume impregnation method to prepare the catalyst, and has simple process and convenient operation. The catalyst prepared under the optimal condition has strong denitration performance and a wider temperature window, and the denitration efficiency can reach 100% under certain application conditions. In the temperature range of 160-280 ℃, the denitration efficiency obtained by using the catalyst is kept above 90%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art can change or modify the technical content disclosed above into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.

Claims (9)

1. The low-temperature SCR denitration catalyst is characterized by being prepared from TiO2The carrier is Mn and Fe as active components, the mass ratio of the active components Fe to Mn is 1: 3-4: 3, and the active components Fe and the carrier TiO2The mass ratio of (A) to (B) is 1: 20-1: 5.
2. The preparation method of the low-temperature SCR denitration catalyst according to claim 1, comprising the steps of:
s1, dissolving manganese salt and iron-containing salt in deionized water to prepare impregnation liquid, and then adding TiO into the impregnation liquid2；
S2, stirring the mixture obtained in the step S1 in a water bath heating magnetic stirrer to fully mix the components therein, uniformly dipping the components, and evaporating water until the mixture is sticky;
s3, placing the mixture obtained in the step S2 in a drying box for drying, and removing moisture;
and S4, placing the sample obtained in the step S3 in a muffle furnace for roasting to obtain the low-temperature SCR denitration catalyst.
3. The method of claim 2, wherein the step of preparing the composition comprisesIn step S1, adding iron salt and manganese salt according to the mass ratio of iron element to manganese element of 1: 3-4: 3, wherein the Fe element and the TiO carrier2The mass ratio of the water to the water is 1: 20-1: 5, and the amount of the deionized water is according to the TiO22 to 3 times the mass of (A) is added.
4. The method according to claim 2, wherein in step S1, the manganese salt is manganese acetate tetrahydrate, and the iron-containing salt is iron nitrate.
5. The method of claim 2, wherein in step S2, the water bath heating temperature is 60-80 ℃ and the time is 30-60 min.
6. The method of claim 2, wherein in step S3, the drying temperature is 100-120 ℃ and the drying time is 10-12 h.
7. The method of claim 2, wherein in step S4, the baking temperature is 350-800 ℃ and the baking time is 3-5 h.
8. Use of the low-temperature SCR denitration catalyst of claim 1 or the low-temperature SCR denitration catalyst obtained by the preparation method of any one of claims 2 to 7 for removing nitrogen from flue gas.
9. The application of claim 8, wherein the flue gas has an ammonia-nitrogen ratio of 1:1 at 200-280 ℃ and a space velocity of 30000h-1And under the condition that the oxygen concentration is 5%, the denitration rate reaches over 95%.
CN202011613126.8A 2020-12-30 2020-12-30 Low-temperature SCR denitration catalyst, preparation method and application thereof Pending CN112808277A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471563A (en) * 2022-02-15 2022-05-13 中国科学院山西煤炭化学研究所 Method for improving SCR denitration activity of iron-based catalyst
CN114984948A (en) * 2022-06-06 2022-09-02 南京沃谱瑞环境研究院有限公司 Preparation method of efficient economical low-temperature catalyst
CN115445660A (en) * 2022-10-09 2022-12-09 浙江浙能技术研究院有限公司 Preparation method of monolithic catalyst using high molecular polymer as carrier and suitable for ultralow-temperature SCR (selective catalytic reduction) reaction

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1724149A (en) * 2005-06-24 2006-01-25 湘潭大学 Low temp. multiple component capalyst for flue gas denitration and its preparation process
US8465714B2 (en) * 2009-02-16 2013-06-18 Cristal Usa Inc. Catalyst promoters in vanadium-free mobile catalyst
CN105854932A (en) * 2016-04-20 2016-08-17 东南大学 Cu-Mn bimetallic composite type low-temperature denitration catalyst and preparation method thereof
CN109126817A (en) * 2018-11-07 2019-01-04 东北大学 A kind of iron, tungsten, zinc improvement cerium oxide/manganese oxide SCR denitration and preparation method thereof
CN111450838A (en) * 2019-01-22 2020-07-28 中国石油化工股份有限公司 Flue gas denitration catalyst and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1724149A (en) * 2005-06-24 2006-01-25 湘潭大学 Low temp. multiple component capalyst for flue gas denitration and its preparation process
US8465714B2 (en) * 2009-02-16 2013-06-18 Cristal Usa Inc. Catalyst promoters in vanadium-free mobile catalyst
CN105854932A (en) * 2016-04-20 2016-08-17 东南大学 Cu-Mn bimetallic composite type low-temperature denitration catalyst and preparation method thereof
CN109126817A (en) * 2018-11-07 2019-01-04 东北大学 A kind of iron, tungsten, zinc improvement cerium oxide/manganese oxide SCR denitration and preparation method thereof
CN111450838A (en) * 2019-01-22 2020-07-28 中国石油化工股份有限公司 Flue gas denitration catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QI, GS ET AL.,: ""Low-temperature selective catalytic reduction of NO with NH3 over iron and manganese oxides supported on titania"", 《APPLIED CATALYSIS B-ENVIRONMENTAL》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471563A (en) * 2022-02-15 2022-05-13 中国科学院山西煤炭化学研究所 Method for improving SCR denitration activity of iron-based catalyst
CN114984948A (en) * 2022-06-06 2022-09-02 南京沃谱瑞环境研究院有限公司 Preparation method of efficient economical low-temperature catalyst
CN115445660A (en) * 2022-10-09 2022-12-09 浙江浙能技术研究院有限公司 Preparation method of monolithic catalyst using high molecular polymer as carrier and suitable for ultralow-temperature SCR (selective catalytic reduction) reaction

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