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CN112844428B - Vanadium-free modified manganese-based NH 3 SCR denitration catalyst and preparation method and application thereof - Google Patents

Vanadium-free modified manganese-based NH 3 SCR denitration catalyst and preparation method and application thereof Download PDF

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CN112844428B
CN112844428B CN201911187528.3A CN201911187528A CN112844428B CN 112844428 B CN112844428 B CN 112844428B CN 201911187528 A CN201911187528 A CN 201911187528A CN 112844428 B CN112844428 B CN 112844428B
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李春晓
邱明英
王建华
张宇鑫
崔岩
任乐
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Capital Engineering & Research Inc Ltd
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract

The invention provides a vanadium-free modified manganese-based NH 3 -SCR denitration catalyst, and preparation method and application thereof. The denitration catalyst active component comprises MnO of 1.0-10.0wt% based on 100% of the catalyst mass 2 WO 0.1-12wt% 3 0.1-9wt% of NiO and 0-0.3wt% of P 2 O 5 And MnO 2 The mass is larger than that of NiO. The preparation method of the catalyst comprises the following steps: and loading the precursor of each active component on a carrier, and roasting to obtain the catalyst. The catalyst is suitable for flue gas denitration treatment. The method for carrying out flue gas denitration treatment by using the catalyst can realize the high SO at a lower and wider temperature window 2 The high denitration efficiency is maintained for a long time under the concentration. The catalyst provided by the invention has the performance of good catalytic denitration efficiency in a wider low-temperature range and excellent sulfur resistance equivalent to that of a V-series catalyst.

Description

Vanadium-free modified manganese-based NH 3 SCR denitration catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of low-temperature denitration catalytic materials, and relates to vanadium-free modified manganese-based NH 3 -SCR denitration catalyst, and preparation method and application thereof.
Background
Nitrogen oxides are a major atmospheric pollutant, with NO accounting for 90% of the total nitrogen oxides. Selective Catalytic Reduction (SCR) technology is the most widely used and mature denitration technology internationally, NO x With NH 3 Conversion to nonhazardous N under oxygen-containing conditions and the action of a catalyst 2 And H 2 O。
Commercial catalysts currently mainly used in industry are mostly V 2 O 5 -WO 3 /TiO 2 Or V 2 O 5- MoO 3 /TiO 2 The catalyst, however, has an operating temperature of 300-400 ℃, so that a high-dust arrangement is adopted in most industrial applications, and the high-dust arrangement places the denitration module before dust removal and desulfurization, which can greatly reduce the mechanical and chemical life of the SCR catalyst and greatly increase the denitration cost. Mn-based catalysts have relatively good NH as alternative catalysts to V-based catalysts 3 SCR has low Wen Tuoxiao activity, however its sulfur resistance is poor. The sulfur resistance of the multi-element metal oxide catalyst formed by Mn-Ni synergy is improved compared with that of a single Mn oxide catalyst, however, compared with a V-series catalyst, the sulfur resistance effect still cannot meet the sulfur resistance requirement in the denitration process, so that the practical application of Mn is relatively less in China at present. In order to reduce the influence of sulfur on the catalyst, the first-stage project of the coking limited company of Tangshan Fengda adopts a process route of waste heat recovery, dry desulfurization, dust removal and SCR denitration, thereby effectively reducing dust and SO 2 The influence on the catalyst greatly prolongs the service life of the catalyst, however, the temperature of the flue gas is lower, and extremely high requirements are put on the low-temperature denitration capability of the catalyst.
Coke oven gas produced by coking process has low flue gas temperature and NO x High content of SO 2 The content is relatively low. Current commercial catalyst V 2 O 5 -WO 3 /TiO 2 And V 2 O 5- MoO 3 /TiO 2 The catalyst cannot be well applied due to the overhigh reaction temperature, and the Mn system comprises the existing multi-element metal oxide catalyst formed by Mn-Ni synergy, which can meet the temperature requirement but severely restricts the application prospect due to poor sulfur resistance.
On one hand, in view of the urgent requirements of the prior art on low-temperature catalytic environment, but the problem that the existing low-temperature catalyst cannot be popularized and used due to poor sulfur resistance, on the other hand, in view of the pollution problem of toxic components of the V-series catalyst, the research on the V-free low-temperature sulfur-resistant catalyst which has good catalytic denitration efficiency and good sulfur resistance effect under the low-temperature condition is of great significance.
Disclosure of Invention
The invention aims to provide a low-temperature sulfur-resistant NH which does not contain V 3 An SCR denitration catalyst having good catalytic denitration efficiency in a wide low temperature range and having sulfur resistance comparable to that of a V-based catalyst.
In order to achieve the aim, the invention provides a vanadium-free modified manganese-based NH 3 SCR denitration catalyst, wherein the active component of the catalyst is supported and comprises MnO in an amount of 1.0-10.0wt%, based on 100% of the total mass of the catalyst (i.e. based on 100% of the total mass of the carrier and the components supported on the carrier) 2 WO 0.1-12wt% 3 0.1-9wt% of NiO and 0-0.3wt% of P 2 O 5 。
In the above denitration catalyst, when phosphorus element is added (i.e., when P is calculated based on 100% of the support mass of the catalyst) 2 O 5 When the content of the Mn-W-Ni-P is below 0.3wt percent), the synergistic effect of Mn-W-Ni-P four elements on vanadium-free modified manganese-based NH can be realized 3 The SCR low-temperature activity and the catalytic denitration capacity of the SCR denitration catalyst have a further improvement effect.
In the above denitration catalyst, preferably, the catalyst supports P in the active component based on 100% by mass of the total catalyst 2 O 5 The mass is WO 3 2.55% of (C). (i.e., P element mass is 1.4% of W element mass)
In the above denitration catalyst, preferably, the mass of NiO does not exceed MnO 2 0.8 times of the mass. The quality of NiO is controlled to be not more than MnO 2 0.8 times of the mass, is favorable for further and obvious improvement of the denitration performance of the catalyst, and has more than 75 percent of NO at 120-300 DEG C x Removal efficiency.
In the above denitration catalyst, preferably, the carrier of the catalyst is TiO 2 。
In one embodiment of the above denitration catalyst, the catalyst is used for catalyzingThe total mass of the carrier raw material and the active component raw material of the catalyst is 100%, the active component raw material of the catalyst comprises 1.0-10.0wt% of Mn source, 0.1-12wt% of W source, 0.1-9wt% of Ni source and 0-0.3wt% of P source, and the mass of Mn source is larger than that of Ni source; wherein the mass of Mn source in the active component raw material is MnO 2 Mass, W source mass as in WO 3 Mass, ni source mass is calculated by NiO mass, P source mass is calculated by P 2 O 5 Mass meter. The mass of the P source is preferably 2.55% of the mass of the W source (i.e., the mass of the P element is 1.4% of the mass of the W element), wherein the mass of the W source is WO 3 Mass, P source mass, P 2 O 5 Mass meter. The mass of the Ni source is preferably not more than 0.8 times the mass of the Mn source (mass of the Mn source is represented by MnO 2 Mass, ni source mass is based on NiO mass). The carrier of the catalyst is preferably TiO 2 。
The mass of Mn source is MnO 2 Mass, i.e. mass of Mn source, of MnO that can be produced from this Mn source 2 The mass of Mn element in the Mn source is considered herein to be equal to the MnO that the Mn source can produce 2 The amount of the Mn element; mass of W source in WO 3 Mass, i.e. mass of W source, in accordance with WO that W source can produce 3 Is considered herein to be the same as the Wn source can produce WO 3 The amount of element W; the mass of the Ni source is the mass of NiO, i.e., the mass of the Ni source is the mass of NiO that the Ni source can produce, and here the amount of Ni element in the Ni source is considered to be equal to the amount of Ni element in NiO that the Ni source can produce; p source mass to P 2 O 5 Mass, i.e. mass of P source, with P obtainable by the P source 2 O 5 The amount of P element in the P source is herein considered to be equal to the amount of P that the P source can produce 2 O 5 The amount of P element in (b).
In the above-described embodiment of the denitration catalyst, when phosphorus element is added, that is, the catalyst-supported active component contains MnO 2 、WO 3 NiO and P 2 O 5 When the content of the P source is less than 0.3wt% based on 100% of the total mass of the carrier raw material and the active component raw material of the catalyst, the coordination of four elements Mn-W-Ni-P can be realizedCo-pair vanadium-free modified manganese-based NH 3 The SCR low-temperature activity and the catalytic denitration capacity of the SCR denitration catalyst have a further improvement effect. When the mass of the Ni source mass is controlled to be not more than 0.8 times of the Mn source mass, the denitration performance of the catalyst is further remarkably improved, and the NOx removal efficiency is over 75% at 120-300 ℃.
The invention also provides the vanadium-free modified manganese-based NH 3 -a method for preparing an SCR denitration catalyst, wherein the method comprises the steps of:
loading the raw materials of each active component on a carrier, and roasting to obtain the vanadium-free modified manganese-based NH 3 -an SCR denitration catalyst;
the active component raw materials comprise 1.0-10.0wt% of Mn source, 0.1-12wt% of W source, 0.1-9wt% of Ni source and 0-0.3wt% of P source, wherein the mass of Mn source is larger than that of Ni source, based on 100% of the total mass of the carrier and each active component raw material; wherein the mass of Mn source is MnO 2 Mass, W source mass as in WO 3 Mass, ni source mass is calculated by NiO mass, P source mass is calculated by P 2 O 5 Mass meter.
In the above preparation method, preferably, the Mn source (i.e., mnO 2 The active component precursor) is manganese salt, wherein only manganese oxide enters the catalyst after the manganese salt is roasted; such as manganese oxalate.
In the above preparation method, preferably, the W source in the active ingredient raw material (i.e., WO 3 Active component precursor) is phosphotungstic acid.
In the above preparation method, preferably, the Ni source (i.e., niO active component precursor) in the active component raw material is a nickel salt, wherein the nickel salt is subjected to the calcination, and only the oxide of nickel enters the catalyst; such as nickel oxalate; nickel nitrate is generally not an option because nickel nitrate presents an explosion hazard in the present reaction.
In the above preparation method, preferably, the Mn source (i.e., P 2 O 5 Active component precursor) is phosphotungstic acid.
In the above preparation method, preferably, the active ingredient raw materials include a Mn source, a Ni source, and phosphotungstic acid.
In the above preparation method, preferably, the baking temperature is 400-600 ℃ and the baking time is 1-6h.
In the above preparation method, it is preferable that drying is performed before baking is performed. For example, it may be dried at 105℃for 8-24h.
In the above preparation method, preferably, the loading of each active ingredient raw material on the carrier is achieved by: preparing solutions of the active component raw materials, and loading the solutions of the active component raw materials on a carrier by adopting an impregnation method; wherein a one-step impregnation method or a stepwise impregnation method can be used.
In one embodiment, the vanadium-free modified manganese-based NH is as described above 3 The preparation method of the SCR denitration catalyst comprises the following steps: dissolving Mn source, ni source and phosphotungstic acid in deionized water at 40-80 ℃ to obtain impregnating solution; then adding TiO into the impregnating solution 2 A carrier, stirring to be sticky; baking at 400-600 ℃ for 1-6h after drying to obtain the vanadium-free modified manganese-based NH 3 -an SCR denitration catalyst.
In the above application, preferably, the flue gas is coke oven flue gas. The coke oven flue gas has SO 2 Relatively low concentration of NO x The vanadium-free modified manganese-based NH provided by the invention has the characteristics of high concentration and low flue gas temperature 3 The SCR denitration catalyst has good sulfur resistance and good low-temperature SCR activity, and shows great advantages in coke oven smoke treatment.
The invention also provides a flue gas denitration treatment method, wherein the method uses the vanadium-free modified manganese-based NH 3 -the SCR denitration catalyst performs a flue gas denitration treatment.
In the flue gas denitration treatment method, preferably, the flue gas denitration treatment temperature is 120-300 ℃.
In the above flue gas denitration treatment method, preferably, the flue gas subjected to denitration treatment is SO 2 The maximum concentration was 500ppm. Using the vanadium-free modified manganese-based NH 3 The flue gas denitration treatment of the SCR denitration catalyst can be in the range of 120-300 ℃ and SO 2 In the range of 500ppm maximum concentration, high denitration efficiency is achieved for a long time (for example, 72 hours or more).
The invention starts from the research and development of the denitration catalyst without V and aims at the sulfur resistance and the low-temperature denitration performance, and firstly proposes to contain MnO 2 -WO 3 Vanadium-free catalyst comprising a complex oxide of NiO as active component and further comprising MnO 2 -WO 3 -NiO-P 2 O 5 Vanadium-free catalysts comprising a complex oxide as active component. Compared with the prior art, the technical scheme provided by the invention has the following beneficial technical effects:
1. the vanadium-free modified manganese-based NH provided by the invention 3 The SCR denitration catalyst has good low-temperature activity and high NOx removal efficiency at 120-300 ℃.
2. The vanadium-free modified manganese-based NH provided by the invention 3 The SCR denitration catalyst has better sulfur resistance, and can basically reach commercial V 2 O 5 Sulfur resistance level of the catalyst.
3. The vanadium-free modified manganese-based NH provided by the invention 3 The preparation method of the SCR denitration catalyst has simple process and is easy to realize industrialized popularization.
4. The vanadium-free modified manganese-based NH provided by the invention 3 The SCR denitration catalyst has the sulfur resistance of an industrial V-series catalyst and a lower denitration temperature window, does not contain V, and greatly reduces the toxicity of the catalyst and the harm to the environment.
5. The vanadium-free modified manganese-based NH provided by the invention 3 The SCR denitration catalyst realizes the low-temperature denitration activity and the improvement of sulfur resistance of the catalyst by utilizing the synergistic effect of three elements of Mn-W-Ni, and has obvious advantages compared with the performances of Mn-Ni and Mn-W double-active-component catalysts.
6. The flue gas denitration treatment method provided by the invention can realize the effect of higher SO at a lower and wider temperature window 2 The high denitration efficiency is maintained for a long time under the condition of concentration.
Drawings
Fig. 1 is an XRD pattern of the catalyst provided in example 1.
FIG. 2 is a vanadium-free modified manganese-based NH provided in example 1-example 3 3 -a graph of NOx removal results for an SCR denitration catalyst.
Fig. 3 is a graph showing the NOx removal efficiency of each catalyst in experimental example 2.
Fig. 4 is a graph showing the NOx removal efficiency of each catalyst in experimental example 3.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
This example provides a vanadium-free modified manganese-based NH 3 SCR denitration catalyst, which is based on TiO 2 As a carrier, the catalyst-supported active component contains MnO in an amount of 8% by weight based on 100% by theoretical total mass of the catalyst (i.e., based on 100% by mass of the sum of the carrier mass and the mass of the active component theoretically producible by the raw materials of the active component) 2 WO with a theoretical content of 6wt% 3 NiO with theoretical content of 2wt% and trace P 2 O 5 Wherein the theoretical mass of the phosphorus element accounts for about 1.4% of the theoretical mass of the W element (i.e. P 2 O 5 Theoretical mass of WO 3 2.55% of theory, i.e. 0.2% by weight of the total mass); the catalyst is prepared by the following steps:
weighing 2.63g of manganese oxalate, 1.31g of phosphotungstic acid, 0.79g of nickel oxalate and 16.80g of TiO according to the theoretical content of each active component in the catalyst 2 The method comprises the steps of carrying out a first treatment on the surface of the 2.63g of manganese oxalate, 1.31g of phosphotungstic acid and 0.79g of nickel oxalate are taken, added into 50ml of deionized water and heated in a water bath at 60 ℃ until the solution is completely dissolved to obtain an impregnating solution; 16.80g TiO was added to the impregnation 2 Stirring thoroughly to be sticky, and then drying in a drying oven at 105 ℃ for 12 hours; the dried product is put into a muffle furnace to be roasted for 3 hours at 500 ℃ to prepare vanadium-free modified manganese-based NH 3 SCR denitration catalyst, designated 8Mn6W2Ni/TiO 2 。
The vanadium-free modified manganese provided in the embodimentRadical NH 3 XRD results for the SCR denitration catalyst are shown in FIG. 1. From FIG. 1, only anatase forms of TiO can be observed 2 From this, it can be seen that the active component is in the catalyst TiO 2 The support surface is highly dispersed or in an amorphous state.
Example 2
This example provides a vanadium-free modified manganese-based NH 3 SCR denitration catalyst, which is based on TiO 2 As a carrier, the catalyst-supported active component contains MnO in an amount of 8% by weight based on 100% by theoretical total mass of the catalyst (i.e., based on 100% by mass of the sum of the carrier mass and the mass of the active component theoretically producible by the raw materials of the active component) 2 WO with a theoretical content of 6wt% 3 NiO with theoretical content of 1wt% and trace P 2 O 5 Wherein the theoretical mass of the phosphorus element accounts for about 1.4% of the theoretical mass of the W element (i.e. P 2 O 5 Theoretical mass of WO 3 2.55% of theory); the catalyst is prepared by the following steps:
2.63g of manganese oxalate, 1.31g of phosphotungstic acid and 0.40g of nickel oxalate are taken and added into 50ml of deionized water, and the mixture is heated in a water bath at 60 ℃ until the mixture is completely dissolved to obtain an impregnating solution; 17.00g TiO was added to the impregnation 2 Stirring thoroughly to be sticky, and then drying in a drying oven at 105 ℃ for 12 hours; the dried product is put into a muffle furnace to be roasted for 3 hours at 500 ℃ to prepare vanadium-free modified manganese-based NH 3 SCR denitration catalyst, designated 8Mn6W1Ni/TiO 2 。
Example 3
This example provides a vanadium-free modified manganese-based NH 3 SCR denitration catalyst, which is based on TiO 2 As a carrier, the catalyst-supported active component contains MnO in an amount of 8% by weight based on 100% by theoretical total mass of the catalyst (i.e., based on 100% by mass of the sum of the carrier mass and the mass of the active component theoretically producible by the raw materials of the active component) 2 WO with a theoretical content of 6wt% 3 NiO with theoretical content of 4wt% and trace P 2 O 5 Wherein the theoretical mass of the phosphorus element accounts for about 1.4% of the theoretical mass of the W element (i.e. P 2 O 5 Theoretical mass of WO 3 2.55% of theory); the catalyst is prepared by the following steps:
2.63g of manganese oxalate, 1.31g of phosphotungstic acid and 1.58g of nickel oxalate are taken, added into 50ml of deionized water and heated in a water bath at 60 ℃ until the solution is completely dissolved to obtain an impregnating solution; 16.40g TiO was added to the impregnation 2 Stirring thoroughly to be sticky, and then drying in a drying oven at 105 ℃ for 12 hours; the dried product is put into a muffle furnace to be roasted for 3 hours at 500 ℃ to prepare vanadium-free modified manganese-based NH 3 SCR denitration catalyst, designated 8Mn6W4Ni/TiO 2 。
Example 4
This example provides a vanadium-free modified manganese-based NH 3 SCR denitration catalyst, which is based on TiO 2 As a carrier, the catalyst-supported active component contains MnO in an amount of 8% by weight based on 100% by theoretical total mass of the catalyst (i.e., based on 100% by mass of the sum of the carrier mass and the mass of the active component theoretically producible by the raw materials of the active component) 2 WO with a theoretical content of 6wt% 3 NiO with theoretical content of 3wt% and trace P 2 O 5 Wherein the theoretical mass of the phosphorus element accounts for about 1.4% of the theoretical mass of the W element (i.e. P 2 O 5 Theoretical mass of WO 3 2.55% of theory); the catalyst is prepared by the following steps:
2.63g of manganese oxalate, 1.31g of phosphotungstic acid and 1.19g of nickel oxalate are taken, added into 50ml of deionized water and heated in a water bath at 60 ℃ until the solution is completely dissolved to obtain an impregnating solution; 16.40g TiO was added to the impregnation 2 Stirring thoroughly to be sticky, and then drying in a drying oven at 105 ℃ for 12 hours; the dried product is put into a muffle furnace to be roasted for 3 hours at 500 ℃ to prepare vanadium-free modified manganese-based NH 3 SCR denitration catalyst, designated 8Mn6W3Ni/TiO 2 。
Example 5
This example provides a vanadium-free modified manganese-based NH 3 SCR denitration catalyst, which is based on TiO 2 As support, based on 100% of the theoretical total mass of the catalyst (i.e. the mass of the support plus the active component starting materials of the individual components can theoretically be calculatedThe total mass of the active components obtained is 100%, and the active components loaded on the catalyst comprise MnO with the theoretical content of 8wt% 2 WO with a theoretical content of 6wt% 3 NiO with theoretical content of 4wt% and trace P 2 O 5 Wherein the theoretical mass of the phosphorus element accounts for about 1.4% of the theoretical mass of the W element (i.e. P 2 O 5 Theoretical mass of WO 3 2.55% of theory); the catalyst is prepared by the following steps:
2.63g of manganese oxalate, 1.31g of phosphotungstic acid and 2.53g of nickel oxalate are added into 50ml of deionized water and heated in a water bath at 60 ℃ until the nickel oxalate is completely dissolved to obtain an impregnating solution; 16.40g TiO was added to the impregnation 2 Stirring thoroughly to be sticky, and then drying in a drying oven at 105 ℃ for 12 hours; the dried product is put into a muffle furnace to be roasted for 3 hours at 500 ℃ to prepare vanadium-free modified manganese-based NH 3 SCR denitration catalyst, designated as 8Mn6W6.4Ni/TiO 2 。
Comparative example 1
The comparative example provides a vanadium-free modified manganese-based NH 3 SCR denitration catalyst, which is based on TiO 2 As a carrier, the catalyst-supported active component contains MnO in an amount of 8% by weight based on 100% by theoretical total mass of the catalyst (i.e., based on 100% by mass of the sum of the carrier mass and the mass of the active component theoretically producible by the raw materials of the active component) 2 WO with a theoretical content of 6wt% 3 NiO with theoretical content of 4wt% and trace P 2 O 5 Wherein the theoretical mass of the phosphorus element accounts for about 1.4% of the theoretical mass of the W element (i.e. P 2 O 5 Theoretical mass of WO 3 2.55% of theory); the catalyst is prepared by the following steps:
2.63g of manganese oxalate, 1.31g of phosphotungstic acid and 3.16g of nickel oxalate are taken, added into 50ml of deionized water and heated in a water bath at 60 ℃ until the nickel oxalate is completely dissolved to obtain an impregnating solution; 16.40g TiO was added to the impregnation 2 Stirring thoroughly to be sticky, and then drying in a drying oven at 105 ℃ for 12 hours; the dried product is put into a muffle furnace to be roasted for 3 hours at 500 ℃ to prepare vanadium-free modified manganese-based NH 3 SCR denitration catalyst, designated as 8Mn6W8Ni/TiO 2 。
Comparative example 2
This comparative example provides a modified manganese-based NH 3 SCR denitration catalyst, which is based on TiO 2 As a carrier, the catalyst-supported active component contains MnO in an amount of 8% by weight based on 100% by theoretical total mass of the catalyst (i.e., based on 100% by mass of the sum of the carrier mass and the mass of the active component theoretically producible by the raw materials of the active component) 2 NiO with theoretical content of 2 wt%; the catalyst is prepared by the following steps:
2.63g of manganese oxalate and 0.79g of nickel oxalate are added into deionized water and heated in a water bath at 60 ℃ until the solution is completely dissolved to obtain an impregnating solution; 16.80g TiO was added to the impregnation 2 Stirring thoroughly to be sticky, and then drying in a drying oven at 105 ℃ for 12 hours; the dried product is put into a muffle furnace to be roasted for 3 hours at 500 ℃ to prepare modified manganese-based NH 3 SCR denitration catalyst, designated Mn-Ni.
Comparative example 3
This comparative example provides a modified manganese-based NH 3 SCR denitration catalyst, which is based on TiO 2 As a carrier, the catalyst-supported active component contains MnO in an amount of 8% by weight based on 100% by theoretical total mass of the catalyst (i.e., based on 100% by mass of the sum of the carrier mass and the mass of the active component theoretically producible by the raw materials of the active component) 2 WO with a theoretical content of 6wt% 3 The method comprises the steps of carrying out a first treatment on the surface of the The catalyst is prepared by the following steps:
2.63g of manganese oxalate and 1.47g of ammonium tungstate are taken and added into deionized water, and the mixture is heated in a water bath at 60 ℃ until the mixture is completely dissolved to obtain an impregnating solution; 16.80g TiO was added to the impregnation 2 Stirring thoroughly to be sticky, and then drying in a drying oven at 105 ℃ for 12 hours; the dried product is put into a muffle furnace to be roasted for 3 hours at 500 ℃ to prepare modified manganese-based NH 3 SCR denitration catalyst, designated Mn-W.
Comparative example 4
This comparative example provides a modified manganese-based NH 3 SCR denitration catalyst, which is based on TiO 2 As a carrier for the carrier,the active component carried by the catalyst comprises MnO with a theoretical content of 8wt%, based on 100% of the theoretical total mass of the catalyst (i.e. based on 100% of the sum of the mass of the carrier plus the mass of the active component that can be prepared theoretically from the active component raw materials of each component) 2 P with a theoretical content of 0.2wt% 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the The catalyst is prepared by the following steps:
2.63g of manganese oxalate and 0.065g of triammonium phosphate are added into deionized water and heated in a water bath at 60 ℃ until the solution is completely dissolved to obtain an impregnating solution; 16.80g TiO was added to the impregnation 2 Stirring thoroughly to be sticky, and then drying in a drying oven at 105 ℃ for 12 hours; the dried product is put into a muffle furnace to be roasted for 3 hours at 500 ℃ to prepare modified manganese-based NH 3 SCR denitration catalyst, designated Mn-P.
Experimental example 1
Testing of vanadium-free modified manganese-based NH provided in examples 1-5, comparative example 1, respectively 3 Denitration ability of SCR denitration catalyst under 120-300 ℃ (namely NO) x Removal rate), specific test conditions are as follows:
the concentration of NO in the flue gas to be treated is 700ppm, NO and NH 3 The volume ratio of (1:1), O 2 The concentration of (C) is 5vol%, the rest is N 2 The method comprises the steps of carrying out a first treatment on the surface of the The total airspeed of the flue gas to be treated is 30000h -1 。
The test results are shown in FIG. 2, and it can be seen from FIG. 2 that the vanadium-free modified manganese-based NH provided in examples 1 to 5 3 The SCR denitration catalyst has higher NO at the temperature of 120-300 DEG C x Removal rate, i.e. vanadium-free modified manganese-based NH provided in examples 1-3 3 The SCR denitration catalyst has excellent low-temperature denitration performance and larger temperature window, and particularly the denitration catalysts provided in the examples 1-2 have more than 80% of NO in the range of 120-300 DEG C x The removal rate.
Vanadium-free modified manganese-based NH provided in example 1 3 SCR denitration catalyst, wherein NiO has mass of MnO 2 0.25 times the mass of the vanadium-free modified manganese-based NH provided in example 2 3 SCR denitration catalyst, wherein NiO has mass of MnO 2 0.125 times the mass, the vanadium-free modification provided in example 3Manganese-based NH 3 SCR denitration catalyst, wherein NiO has mass of MnO 2 0.5 times the mass of the vanadium-free modified manganese-based NH provided in example 4 3 SCR denitration catalyst, wherein NiO has mass of MnO 2 0.375 times the mass, the vanadium-free modified manganese-based NH provided in example 5 3 SCR denitration catalyst, wherein NiO has mass of MnO 2 0.8 times of the mass of the vanadium-free modified manganese-based NH provided in comparative example 1 3 SCR denitration catalyst, wherein NiO has mass of MnO 2 1 time of the mass.
Vanadium-free modified manganese-based NH provided by example 1-example 5 and comparative example 1 3 Comparison of denitration performance test results of the SCR denitration catalyst shows that after Ni content is reduced, the denitration performance of the catalyst is slightly reduced in a low-temperature section (120-180 ℃) and is hardly influenced in a medium-high-temperature section.
Vanadium-free modified manganese-based NH provided by example 1-example 5, comparative example 1 3 An SCR denitration catalyst can be seen that too high Ni content has a certain negative effect on the catalyst effect, which can lead to a decrease in the denitration performance of the catalyst in the whole section.
Experimental example 2
Test example 1 provided vanadium-free modified manganese-based NH 3 SCR denitration catalyst, mn-Ni catalyst provided in comparative example 2, mn-W catalyst provided in comparative example 3, and Fang Xinli HuaV 2 O 5 Sulfur and water resistance at 200 ℃ for a basic commercial low temperature SCR catalyst (FXLBMF 3-800), the specific test conditions are as follows:
the concentration of NO in the flue gas to be treated is 700ppm, NO and NH 3 Is 1:1, O 2 Is 5vol% SO 2 The concentration is 500ppm, H 2 The concentration of O is 10vol%, the remainder is N 2 The method comprises the steps of carrying out a first treatment on the surface of the The total airspeed of the flue gas to be treated is 30000h -1 NO within 72 hours of testing x Change in removal rate.
The test results are shown in FIG. 3, and it can be seen that the vanadium-free modified manganese-based NH provided in example 1 3 The strong sulfur resistance of SCR denitration catalyst (shown as Mn-Ni-W in FIG. 3) has been compared with that of conventional V-based catalyst (shown as V in FIG. 3 2 O 5 ) Equivalent. The sulfur resistance of the Mn-Ni and Mn-W catalysts is lower than that of Mn-W-Ni three catalystsComponent catalysts and conventional V-based catalysts; it can be seen from fig. 3 that the Ni element has a more remarkable effect on the sulfur resistance of the catalyst than the W element.
Experimental example 3
Test example 1 provided vanadium-free modified manganese-based NH 3 SCR denitration catalyst, mn-Ni catalyst provided in comparative example 2, mn-W catalyst provided in comparative example 3, mn-P catalyst provided in comparative example 4, and Fang Xinli HuaV 2 O 5 Denitration capability (i.e., NO) of a basic commercial Low temperature SCR catalyst (FXLBMF 3-800) at 120-300 ℃ x Removal rate), specific test conditions are as follows:
the concentration of NO in the flue gas to be treated is 700ppm, NO and NH 3 Is 1:1, O 2 The concentration of (C) is 5vol%, the rest is N 2 The method comprises the steps of carrying out a first treatment on the surface of the The total airspeed of the flue gas to be treated is 30000h -1 。
As shown in fig. 4, it can be seen that the activation temperature of the Mn catalyst is significantly lower than that of the V catalyst, and W in the Mn catalyst has the effect of widening the catalytic temperature window, while Ni reduces the denitration efficiency of the catalyst under high temperature conditions. The Mn-W-Ni elements in the catalyst have obvious synergistic effect. Vanadium-free modified manganese-based NH provided in comparative example 1 3 The denitration ability of the SCR denitration catalyst, the Mn-Ni catalyst provided in comparative example 2, the Mn-W catalyst provided in comparative example 3 and the Mn-P catalyst provided in comparative example 4 under the condition of 120-300 ℃ can be seen that the Mn-W-Ni-P elements in the catalysts have obvious synergistic effect.
Experimental example 4
Taking the vanadium-free modified manganese-based NH provided in example 1 3 The SCR denitration catalyst was subjected to ICP (inductively coupled plasma spectrometer) detection, and the results are shown in table 1 below.
TABLE 1
Figure BDA0002292767110000101
As is clear from Table 1, the ICP measurement result was compared with the theoretical mass (MnO) in example 1 2 8wt％、NiO 2wt％、WO 3 6wt％、P 2 O 5 0.2 wt.%) is substantially uniform, on the one hand, it can be explained that the vanadium-free modified manganese-based NH provided in example 1 3 The SCR denitration catalyst contains MnO 2 、NiO、WO 3 、P 2 O 5 On the other hand, the prepared vanadium-free modified manganese-based NH can be explained 3 MnO in SCR denitration catalyst 2 、NiO、WO 3 、P 2 O 5 Is similar to the actual content. It was also demonstrated that the catalyst performance test in the above experimental examples 1-3 was of practical significance.

Claims (7)

1. Vanadium-free modified manganese-based NH 3 -SCR denitration catalyst, wherein the catalyst-supported active component comprises MnO in an amount of 1.0 to 10.0wt% based on 100% of the mass of the catalyst 2 WO 0.1-12wt% 3 0.1-9wt% NiO, 0-0.3wt% P 2 O 5 And MnO 2 The mass of (2) is greater than that of NiO;
wherein, in the active component loaded by the catalyst, P 2 O 5 Is of the mass of WO 3 2.55% of the mass of (a);
wherein the mass of NiO is not more than MnO 2 0.8 times of the mass;
wherein the carrier of the catalyst is TiO 2 。
2. The vanadium-free modified manganese-based NH of claim 1 3 -a method for preparing an SCR denitration catalyst, wherein the method comprises the steps of:
loading the raw materials of each active component on a carrier, and roasting to obtain the vanadium-free modified manganese-based NH 3 -an SCR denitration catalyst;
wherein, based on 100% of the total mass of the carrier and each active component raw material, the active component raw material comprises 1.0-10.0wt% of Mn source, 0.1-12% of W source, 0.1-9% of Ni source and 0-0.3% of P source, and the mass of Mn source is larger than that of Ni source; wherein the mass of Mn source is MnO 2 Mass, W source mass as in WO 3 Mass, ni source mass is calculated by NiO mass, P source mass is calculated by P 2 O 5 Mass meter.
3. The preparation method according to claim 2, wherein,
mn source in the active component raw material is manganese salt, wherein only manganese oxide enters the catalyst after the manganese salt is roasted;
the W source and the P source in the active component raw material are phosphotungstic acid;
the Ni source in the active component raw material is nickel salt, wherein the nickel salt only enters the catalyst after being roasted.
4. The preparation method according to claim 3, wherein,
the Mn source is manganese oxalate;
the Ni source is nickel oxalate.
5. The preparation method according to claim 2, wherein the baking temperature is 400-600 ℃ and the baking time is 1-6h.
6. A flue gas denitration treatment method, wherein the method uses the vanadium-free modified manganese-based NH according to claim 1 3 -the SCR denitration catalyst performs a flue gas denitration treatment.
7. The flue gas denitration treatment method according to claim 6, wherein the flue gas denitration treatment temperature is 120-300 ℃, and SO in the flue gas subjected to denitration treatment 2 The maximum concentration was 500ppm.
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