A denitration catalyst top end wear-resistant agent and a preparation method thereof

Abstract

The present application relates to the field of environmental protection denitration, especially to a kind of denitration catalyst top wear-resistant agent and preparation method thereof.The wear-resistant agent includes the following mass parts of raw materials: binder 10-30 parts, stabilizer 0.1-5 parts, anti-wear agent 0.1-5 parts, waterproof agent 0.05-2 parts, active agent 0.1-2 parts, solvent 100 parts;Active agent includes first active agent and / or second active agent, first active agent is selected from one or more of V2O5, MnO, MnO2 and Fe2O3, and second active agent is calcined catalyst powder;Anti-wear agent is selected from one or more of SiO2, Al2O3, ZrO2 and silicone oil.The top wear-resistant agent provided by the present application improves the wear resistance and erosion resistance of the catalyst end, ensures the activity of the end face, reduces the production cycle, the preparation method is simple, and the denitration catalyst has high wear resistance, stable properties, relatively high activity, excellent waterproof performance and the like.

Description

TECHNICAL FIELD

[0001] The application relates to the field of environment-friendly denitration technology, and in particular to a denitration catalyst top end wear-resistant agent and a preparation method thereof. BACKGROUND

[0002] Nitrogen oxides (NO x ) are one of the main atmospheric pollutants, including NO, NO2 and various nitrogen oxides, which can cause harm to human health and plants, such as the formation of photochemical smog, acid rain and haze precursors and other environmental pollution problems. With the enhancement of people's environmental protection consciousness, the emission standard of nitrogen oxides is becoming more and more strict, and how to effectively remove nitrogen oxides has become a problem to be solved. At present, the selective catalytic reduction technology (SCR) is one of the most effective technologies for realizing ultra-low emission of nitrogen oxides, and the core of the SCR denitration technology is the catalyst. At present, there are mainly three types of honeycomb, plate and corrugated plate, among which the honeycomb catalyst is the most widely used and has a market share of up to 70%, ranking first in China. The honeycomb catalyst generally uses titanium dioxide as the carrier, and is directly extruded after mixing with main active and auxiliary active substances, and is formed into a finished catalyst for market application after high-temperature calcination. In the application process, since the catalyst activity is limited by temperature, the catalyst is generally placed in a proper temperature range, and the dust in the flue gas under high space velocity conditions will wash the catalyst, especially in cement plants with high dust concentration, the dust content in the C1 outlet flue gas is basically 100 g / Nm 3 , which causes the catalyst to appear non-renewable wear and collapse, resulting in a sharp decrease in catalyst activity and shortening the service life of the catalyst. The end wear problem of the honeycomb denitration catalyst has seriously restricted the popularization and application of the catalyst, and solving the problem is very important for the denitration catalyst industry.

[0003] The existing end hardening method is to immerse one end of the denitration catalyst into a hardening liquid, and use the adsorption and adhesion of the hardening liquid to adhere the hardening liquid to the surface of the denitration catalyst, so as to achieve the purpose of hardening. For example, the Chinese invention with the application number 201210520947.6 discloses a hardening liquid for the top end reinforcement of a low-temperature SCR denitration catalyst module and application, wherein the hardening liquid comprises a hardening agent, a waterproof agent and a stabilizer. The hardening agent is polyethylene oxide, the waterproof agent is sodium methyl silicate, and the stabilizer is sodium carboxymethyl cellulose. The top end of the calcined denitration catalyst is immersed into the prepared hardening liquid, then the excess liquid is blown away by using compressed air, and the hardening is completed by air drying for 24-48 hours under natural conditions. Although this process achieves the hardening effect of the top end of the catalyst, it causes the loss of activity of the catalyst in the hardened part, increases the use amount of the catalyst, and uses compressed air to blow away the excess hardening liquid, so that the hardening liquid is difficult to uniformly adhere to the surface of the catalyst, the hardening time is long, and the production cycle is prolonged. The Chinese invention with the application number 201410482090.2 discloses a honeycomb type SCR catalyst end hardening liquid and a hardening treatment method. The hardening liquid is formed by dissolving sodium metaaluminate, sodium borate, an adhesive and ammonium metavanadate in deionized water. One end of the denitration catalyst is immersed into the hardening liquid and then naturally air dried. Then, the solidified catalyst is calcined at a temperature of 200-400℃ for 1-3 hours. The end part of the catalyst after the hardening process has denitration activity, but the process is complex, and the hardening liquid on the end surface does not have waterproofness and stability.

[0004] In summary, the top end wear problem of the SCR catalyst has become one of the main factors restricting the long-term stable operation of the catalyst engineering. SUMMARY

[0005] In order to solve the above technical problems, the present application provides a denitration catalyst top end wear-resistant agent and a preparation method thereof.

[0006] In a first aspect, the present application provides a denitration catalyst top end wear-resistant agent, which comprises the following raw materials by mass:

[0007]

[0008] The active agent comprises a first active agent and / or a second active agent. The first active agent is selected from one or more of V2O5, MnO, MnO2 and Fe2O3, and the second active agent is a calcined catalyst powder. The anti-wear agent is selected from one or more of SiO2, Al2O3, ZrO2 and silicone oil.

[0009] The application can solve the problems of catalyst defect, activity reduction, strength reduction, low hardening end activity and the like caused by abrasion problems for high-concentration dust in the cement industry and irregular particles and high-silicon dust. The denitration catalyst top wear-resistant agent provided by the application improves the wear resistance and erosion resistance of the wear-resistant denitration catalyst end, ensures the end surface activity, reduces the production cycle and has excellent comprehensive performance. The wear-resistant denitration catalyst has excellent properties such as high wear resistance, stability, relatively high activity and water resistance.

[0010] Preferably, the binder is aluminum dihydrogen phosphate and / or aluminum sulfate.

[0011] Preferably, the wear-resistant agent is one or two of SiO2, ZrO2 and silicone oil.

[0012] Further preferably, the wear-resistant agent is ZrO2 and silicone oil, and the mass ratio of the ZrO2 and the silicone oil is 1:1-3.

[0013] In the application, on the basis of the binder, one or two of SiO2 and ZrO2 is used as the wear-resistant agent in combination with silicone oil, which has a synergistic effect, further improves the wear resistance of the catalyst by about 5-8%, and improves the comprehensive performance of the catalyst in combination with other raw materials.

[0014] Preferably, the first active agent is V2O5 powder and / or MnO powder; and the second active agent is calcined vanadium-based catalyst powder and / or calcined manganese-based catalyst powder.

[0015] In the application, the first active component and the second active component are added to improve the denitration activity of the wear-resistant agent to a certain extent.

[0016] Further preferably, the second active agent is calcined vanadium-based catalyst powder and / or calcined manganese-based catalyst powder. The end material of the catalyst can be used, and the preparation cost is low.

[0017] Further preferably, the stabilizer is CMC and / or HPMC and / or bentonite and / or diatomite and / or attapulgite.

[0018] Preferably, the water-proof agent is sodium methyl silicate.

[0019] Preferably, the aluminum dihydrogen phosphate and the aluminum sulfate used as the binder are powder or liquid; the CMC, HPMC, bentonite, diatomite and attapulgite used as the stabilizer are powder; the SiO2, Al2O3 and ZrO2 used as the wear-resistant agent are powder, and the silicone oil is liquid; and the sodium methyl silicate used as the water-proof agent is liquid.

[0020] Further preferably, the denitration catalyst top wear-resistant agent is composed of the following raw materials in mass parts:

[0021]

[0022] In a second aspect, the application provides a preparation method of the denitration catalyst tip wear-resistant agent, comprising:

[0023] 1) preparation of the active agent, the active agent is made into powder;

[0024] 2) mixing the powder materials in the active agent, binder, stabilizer, and anti-wear agent in step 1), stirring, and making the hardener powder;

[0025] 3) mixing the liquid materials in the binder, anti-wear agent, and waterproof agent, and stirring with water;

[0026] 4) adding the liquid obtained in step 3) to the hardener powder obtained in step 2), and stirring with water.

[0027] As a preferred, in step 1), the first active agent is directly prepared into powder, and the preparation of the second active agent comprises preparing powder by using the calcined vanadium-based or manganese-based catalyst or using the tip material generated in the cutting process by using the calcined vanadium-based or manganese-based catalyst.

[0028] As a preferred, the stirring time in step 2) is 0.5-2h.

[0029] As a preferred, in step 4), the water is added for 3-4 times.

[0030] As a preferred, the proportion of the water used in step 3) and step 4) is 5:95-10:90.

[0031] In a third aspect, the application provides a preparation method of the denitration catalyst, which is treated by using the denitration catalyst tip wear-resistant agent.

[0032] As a preferred, one end of the calcined honeycomb denitration catalyst is immersed in the solution of the denitration catalyst tip wear-resistant agent.

[0033] Further preferably, the soaking time is 20-30s.

[0034] In the application, the preparation method is simple, the specific tip wear-resistant agent and the treatment method can well complete the hardening of the catalyst tip, the wear resistance and the erosion resistance of the denitration catalyst are higher, the activity of the end face is ensured, and the production cycle is reduced. The anti-wear denitration catalyst obtained by the application has high wear resistance, stable properties, relatively high activity, waterproof, and other excellent performances.

[0035] In a fourth aspect, the present application provides a denitration catalyst, wherein a component of a top end wear-resistant layer of the denitration catalyst is the denitration catalyst top end wear-resistant agent; and / or the denitration catalyst is obtained by the preparation method of the denitration catalyst.

[0036] The present application has at least the following beneficial effects: the denitration catalyst top end wear-resistant agent provided by the present application has high strength and good wear resistance, and can ensure better mechanical service life of the catalyst in a high dust environment; the prepared catalyst end has certain denitration activity, and the addition of active substances in the hardening agent can ensure that the end has certain denitration activity, so that the catalyst end has not only wear-resistant characteristics, but also certain denitration function; and the prepared catalyst end has certain water resistance, which can ensure that the hardened end that first contacts flue gas has certain hydrophobicity, thereby prolonging the service life of the catalyst. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme of the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0038] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods. If the specific technology or condition is not specified in the examples, it is carried out by the conventional method or according to the technology or condition described in the literature in the art, or according to the product instruction. If the manufacturer of the reagents and instruments used is not specified, it is a conventional product that can be purchased through a regular channel.

[0039] In the embodiments of the present application, the binder is aluminum sulfate or aluminum dihydrogen phosphate. The aluminum sulfate used is industrial pure with a purity of 95%; the aluminum dihydrogen phosphate is a powder with a purity of 96%.

[0040] The CMC has a purity of 99% and a viscosity of 5000 mPa.s; the HPMC has a purity of 99% and a viscosity of 8000 mPa.s. The bentonite, diatomite and attapulgite have a purity of more than 95%. ZrO2 and silicone oil are chemically pure, both with a purity of 99%; sodium methyl silicate and V2O5 / MnO are analytically pure. The vanadium-based catalyst powder is a V-W-T catalyst, wherein the V content is 3-4%. The water is deionized water.

[0041] In the embodiment of the present application, the wear rate test, compressive strength, denitration activity and other test items are tested according to the method specified in GB / T31587-2015 “Honeycomb Flue Gas Denitration Catalyst”.

[0042] The present application will be further described below with reference to the embodiments.

[0043] Embodiment 1

[0044] The present embodiment provides a denitration catalyst top end wear-resistant agent and a preparation method, the raw materials and the amount of the wear-resistant agent are as follows:

[0045] Table 1 Raw materials and amount of wear-resistant agent of the present embodiment (mass)

[0046] Name Aluminum dihydrogen phosphate CMC SiO2 Sodium methylsiliconate MnO Water Ratio 15 3 2 0.2 1 100

[0047] The preparation method of the wear-resistant agent provided in the present embodiment is as follows:

[0048] Step 1: Preparation of active agent, prepare MnO powder as active agent.

[0049] Step 2: Mix aluminum dihydrogen phosphate powder with CMC, SiO2 and MnO, use a blender to stir for 1 h to prepare a hardening agent powder.

[0050] Step 3: Take sodium methylsilicate, add 5 parts of water and mix well.

[0051] Step 4: Add the solution obtained in Step 3 to the hardening agent powder in Step 2, then add 95 parts of water in 3-4 times. After observing that the dispersion is uniform with the naked eye, stop stirring to obtain the wear-resistant agent.

[0052] Step 5: Dip one end of the calcined honeycomb catalyst into the solution obtained in Step 4, take it out after 20 s, and the catalyst end hardening is completed.

[0053] Table 2 Wear-resistant agent performance test results of the present embodiment

[0054]

[0055] Embodiment 2

[0056] The present embodiment provides a denitration catalyst top end wear-resistant agent and a preparation method, the raw materials and the amount of the wear-resistant agent are as follows:

[0057] Table 3 Raw materials and amount of wear-resistant agent of the present embodiment (mass)

[0058]

[0059] The preparation method of the wear-resistant agent provided in the present embodiment is as follows:

[0060] First step: Preparation of active agent, mix V2O5 and vanadium-based catalyst powder as active agent.

[0061] Second step: Mix aluminum sulfate powder, HPMC, ZrO2 and the active agent prepared in the first step, and stir with a blender for 0.6 h to prepare a hardening agent powder.

[0062] Third step: Take sodium methyl silicate and add 5 parts of water and mix well.

[0063] Fourth step: Take silicone oil and add 10 parts of water and mix well.

[0064] Fifth step: Add the solutions obtained in the third and fourth steps to the hardening agent powder of the second step, and then add 85 parts of water in 3-4 portions. Stir with a stirring device until the mixture is uniformly dispersed, and then stop stirring to obtain a wear-resistant agent.

[0065] Sixth step: Dip one end of the calcined honeycomb catalyst into the solution obtained in the fifth step, and take it out after 30 s to complete the hardening of the catalyst end.

[0066] Table 4 Performance test results of the wear-resistant agent of this example

[0067]

[0068] Example 3

[0069] This example provides a denitration catalyst top end wear-resistant agent and a preparation method. The raw materials and amounts of the wear-resistant agent are as follows:

[0070] Table 5 Raw materials and amounts (mass) of the wear-resistant agent of this example

[0071] Name Aluminum dihydrogen phosphate HPMC [ZrO2 + silicone oil] Sodium methylsiliconate [V2O5] Water Ratio 25 3 0.5+1.5 0.3 1.5 100

[0072] The preparation method of the wear-resistant agent provided in this example is as follows:

[0073] First step: Mix aluminum dihydrogen phosphate powder, HPMC, ZrO2 and V2O5, and stir with a blender for 0.8 h to prepare a hardening agent powder.

[0074] Second step: Mix sodium methyl silicate and silicone oil, and add 10 parts of water and mix well.

[0075] Third step: Add the solution prepared in the second step to the hardening agent powder of the first step, and then add 90 parts of water in 3-4 portions. Stir with a stirring device until the mixture is uniformly dispersed, and then stop stirring to obtain a wear-resistant agent.

[0076] Fourth step: immerse one end of the calcined honeycomb catalyst into the solution obtained in the third step, and take it out after 25 seconds, thereby completing the hardening of the end of the catalyst.

[0077] Table 6 Wear-resistant agent performance test results of the present example

[0078]

[0079] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application, and are not limiting; although the present application has been described in detail with reference to the foregoing examples, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing examples, or make equivalent substitutions for part of the technical features; and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A denitration catalyst tip wear resistant agent characterized by, consist of the following raw materials in parts by mass: The active agent is V2O5; the anti-wear agent is ZrO2 and silicone oil, the mass ratio of ZrO2 and silicone oil is 1:3; the binder is aluminum dihydrogen phosphate, the stabilizer is HPMC, and the water repellent is sodium methyl silicate.

2. The method of claim 1, wherein the top end abrasion resistant agent for the de-NOx catalyst is prepared by the steps of: comprising: ​ 1) preparation of the active agent, the active agent is made into powder; 2) mixing, stirring the powder materials in the active agent, binder, stabilizer, anti-wear agent in step 1) to make hardener powder; 3) mixing the liquid materials in the binder, anti-wear agent, water repellent, and stirring with water; 4) adding the liquid obtained in step 3) to the hardener powder obtained in step 2) and stirring with water.

3. A method for producing a denitration catalyst, characterized by, The top anti-wear agent for denitration catalyst of claim 1 is used for treating.

4. The production method according to claim 3, characterized by, The calcined honeycomb denitration catalyst is immersed in the solution of the top anti-wear agent for denitration catalyst.

5. A de-NOx catalyst characterized by, The composition of the top anti-wear layer of the denitration catalyst is the top anti-wear agent for denitration catalyst of claim 1; and / or, the denitration catalyst is obtained by the preparation method of the denitration catalyst of claim 3 or 4.

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