CN115624968B - Method for preparing denitration catalyst by using waste wind power blades and application - Google Patents

Method for preparing denitration catalyst by using waste wind power blades and application Download PDF

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CN115624968B
CN115624968B CN202211418605.3A CN202211418605A CN115624968B CN 115624968 B CN115624968 B CN 115624968B CN 202211418605 A CN202211418605 A CN 202211418605A CN 115624968 B CN115624968 B CN 115624968B
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wind power
mixing
waste wind
denitration catalyst
preparing
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CN115624968A (en
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刘向辉
何发泉
路光杰
陈鸥
王洪亮
郑鹏
王永政
霍子钰
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Guoneng Longyuan Environmental Protection Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J23/30—Tungsten
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention relates to the field of solid waste treatment, and discloses a method for preparing a denitration catalyst by using waste wind power blades and application thereof. The method comprises the following steps: (1) Cutting and crushing the waste wind power blades to 80-400 meshes to obtain waste wind power blade crushed aggregates; (2) Mixing tungsten source with ammonia water to obtain mixed solution a, mixing mixed solution a with TiO 2 Mixing to obtain a titanium tungsten powder mixture; (3) Mixing ammonium metavanadate with ammonia water and alcohol substances to obtain a mixed solution b, and mixing the mixed solution b with a titanium tungsten powder mixture; (4) Mixing the mixture with a lubricant, a binder, a plasticizer and crushed waste wind power blades, and then mixing and ageing; (5) Extruding and molding the mixture after ageing to obtain honeycomb catalyst blanks; (6) drying, calcining and cutting the honeycomb catalyst blank. The denitration catalyst obtained by the method has high denitration rate, excellent physical properties and large specific surface, can save preparation cost, and has great industrialized prospect.

Description

Method for preparing denitration catalyst by using waste wind power blades and application
Technical Field
The invention relates to the field of solid waste treatment, in particular to a method for preparing a denitration catalyst by using waste wind power blades and application thereof.
Background
In recent years, wind power has been rapidly developed in China as a clean and environment-friendly energy source. The blade is a core component of the wind turbine generator, and the manufacturing material of the blade is mainly glass fiber or carbon fiber reinforced resin composite material, is difficult to degrade, is white garbage after retirement, and not only pollutes the environment, but also causes resource waste. However, the glass fiber in the waste wind power blade still has a large application scene.
Nitrogen oxides are important precursors causing a series of atmospheric pollution problems (haze, photochemical smog and acid rain), industrial boiler tail gas is a main source of nitrogen oxides, and aiming at the pollution problems of nitrogen oxides in industrial boiler tail gas, the technology mainly comprising Selective Catalytic Reduction (SCR) is used for removing nitrogen oxides and is widely applied to technological processes of coal-fired power plants, industrial kilns and the like. In the SCR process, a denitration catalyst plays a vital role, and the denitration catalyst commonly used in industry at present is mainly a vanadium-titanium denitration catalyst.
The glass fiber and silicate materials have the reinforcing effect in the preparation process of the denitration catalyst, the strength life of the denitration catalyst can be improved to a certain extent, the glass fiber for preparing the denitration catalyst at present has higher price, and in addition, the glass fiber in the wind power blade can still have certain strength and microstructure. The waste wind power blade has very important significance in preparing the denitration catalyst.
Disclosure of Invention
The invention aims to solve the problems of high preparation cost, further improvement of activity of a denitration catalyst and the like in the prior art, and provides a method for preparing the denitration catalyst by using waste wind power blades and application of the method.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a denitration catalyst using waste wind power blades, the method comprising the steps of:
(1) Cutting and crushing the waste wind power blades to 80-400 meshes to obtain waste wind power blade crushed aggregates;
(2) Mixing tungsten source with ammonia water solution to obtain mixed solution a, and mixing mixed solution a with TiO 2 Mixing to obtain a titanium tungsten powder mixture;
(3) Mixing ammonium metavanadate, an ammonia water solution and an alcohol substance to obtain a mixed solution b, and then mixing the mixed solution b with a titanium tungsten powder mixture;
(4) Mixing the mixture obtained in the step (3) with a lubricant, a binder, a plasticizer and crushed waste wind power blades, and then mixing and ageing;
(5) Extruding and forming the aged mixture to obtain honeycomb catalyst blanks;
(6) Drying the honeycomb catalyst blank, calcining at least once, and cutting;
wherein, tiO 2 The weight ratio of the tungsten source to the ammonium metavanadate to the dosage of the lubricant to the binder to the dosage of the waste wind power blade crushed aggregates to the plasticizer is (12-115) 1-10 1-15-1-20-1-10;
the tungsten source is selected from ammonium metatungstate and/or tungsten trioxide;
the alcohol substance is monoethanolamine and/or ethylene glycol.
Preferably, tiO 2 The weight ratio of the tungsten source, ammonium metavanadate, lubricant, binder, glass fiber powder and plasticizer is (40-80): 3-8): 1 (3-8): 3-7): 4-8): 2-5.
Preferably, the liquid-solid ratio of the alcohol substance to the ammonium metavanadate is 1-4mL:1g.
Preferably, in step (4), the mixing conditions include: the mixing temperature is 200-300 ℃, and the mixing time is 5-12h.
Preferably, the time for the aging is 24-72 hours.
Preferably, in step (6), the calcination is carried out at a temperature of 400-700 ℃ for a time of 1-8 hours.
Preferably, the lubricant is selected from one or more of glycerin, triethanolamine and stearic acid.
Preferably, the plasticizer is selected from phthalic acid and/or dioctyl phthalate.
Preferably, the binder is one or more selected from polyvinyl alcohol, methylcellulose, hydroxymethyl cellulose, polyacrylamide and polyethylene glycol.
The second aspect of the invention provides a denitration catalyst prepared by the method.
The invention also provides a preparation method of the denitration catalyst or application of the denitration catalyst in removing nitrogen oxides in industrial boiler tail gas.
The method can successfully use the waste wind power blades for preparing the denitration catalyst, effectively reduce the preparation cost of the denitration catalyst, and can recycle the waste wind power blades in a recycling way, and simultaneously reduce the recycling cost of the waste wind power blades. More importantly, the performance of the denitration catalyst prepared by taking the crushed waste wind power blades as the additive is not affected, the denitration catalyst still has high denitration rate, specific surface area and compressive strength, and the specific surface area of the prepared denitration catalyst can be improved in the process of calcining the denitration catalyst by resin contained in the waste wind power blades, so that the overall performance of the denitration catalyst is improved. The denitration catalyst obtained by the method has the denitration rate up to 98.22%, still has very excellent denitration catalytic performance, can be well applied to denitration reaction for removing nitrogen oxides, and has the specific surface area up to 70.43m 2 /g, can provide more active sites in the denitration reaction, and the denitration catalystThe catalyst also has excellent physical properties, can be better applied to industrial denitration reaction, and has axial compressive strength of 2.72MPa and radial compressive strength of 0.88MPa.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Herein, the honeycomb shape refers to a shape whose catalyst blank surface resembles a "honeycomb".
In this context, the waste wind power blade refers to a wind power blade whose main component is a composite material of glass fiber and resin, and whose service life is over or damaged by accident.
The invention provides a method for preparing a denitration catalyst by using waste wind power blades, which comprises the following steps:
(1) Cutting and crushing the waste wind power blades to 80-400 meshes to obtain waste wind power blade crushed aggregates;
(2) Mixing tungsten source with ammonia water solution to obtain mixed solution a, and mixing mixed solution a with TiO 2 Mixing to obtain a titanium tungsten powder mixture;
(3) Mixing ammonium metavanadate with an ammonia water solution and monoethanolamine to obtain a mixed solution b, and then mixing the mixed solution b with a titanium tungsten powder mixture;
(4) Mixing the mixture obtained in the step (3) with a lubricant, a binder, a plasticizer and crushed waste wind power blades, and then mixing and ageing;
(5) Extruding and forming the aged mixture to obtain honeycomb catalyst blanks;
(6) Drying the honeycomb catalyst blank, calcining at least once, and cutting;
wherein, tiO 2 The weight ratio of the tungsten source to the ammonium metavanadate to the dosage of the lubricant to the binder to the dosage of the waste wind power blade crushed aggregates to the plasticizer is (12-115) 1-10 1-15-1-20-1-10;
in a specific embodiment, the tungsten source is selected from ammonium metatungstate and/or tungsten trioxide.
In a specific embodiment, the alcohol is monoethanolamine and/or ethylene glycol.
In a preferred embodiment, the TiO 2 The weight ratio of the tungsten source, ammonium metavanadate, lubricant, binder, glass fiber powder and plasticizer is (40-80): 3-8): 1 (3-8): 3-7): 4-8): 2-5.
In a more preferred embodiment, the TiO 2 The weight ratio of the tungsten source to the ammonium metavanadate to the usage amount of the lubricant to the usage amount of the binder to the usage amount of the waste wind power blade crushed aggregates to the usage amount of the plasticizer is (40-60), wherein (3-5) is (3-5), and (5-7) is (2-4).
In a further preferred embodiment, the TiO 2 The weight ratio of the tungsten source to the ammonium metavanadate to the usage amount of the lubricant to the usage amount of the binder to the usage amount of the waste wind power blade crushed aggregates to the usage amount of the plasticizer is (40-50), wherein (3-4) is (3-3.5), and (3.5-4) is (5-6) is (2-3).
In the specific embodiment, in the step (1), the weight ratio of the crushed aggregates with the particle size of 80-200 meshes in the crushed aggregates of the waste wind power blades is more than or equal to 30wt percent based on the total weight of the crushed aggregates of the waste wind power blades.
In the method, the content of glass fiber in the waste wind power blade is 50-80wt% and the content of resin is 20-50wt%.
In the method, the waste wind power blades are directly used for preparing the denitration catalyst after being cut and crushed, the particle size of the waste wind power blade crushed aggregates is strictly controlled, and the addition amount of the waste wind power blades, the calcination temperature of the catalyst and the addition amount of other raw materials are matched, so that the waste wind power blades can be well recycled, the preparation cost of the denitration catalyst can be further reduced, and the particle size of the waste wind power blade crushed aggregates is controlled, so that the obtained denitration catalyst has excellent compressive strength.
In the method, the resin contained in the waste wind power blade can also provide energy in the calcining process of the denitration catalyst, and the specific surface area of the prepared denitration catalyst is larger, so that the overall performance of the denitration catalyst is improved.
In a specific embodiment, in step (2), the mixed solution a is mixed with TiO 2 After mixing, ball milling can be carried out on the mixture to obtain the titanium tungsten powder mixture.
In a preferred embodiment, the conditions of the ball milling include: the ball milling speed is 800-1000r/min, and the ball milling time is 20-40min. Specifically, the rotation speed of the ball milling can be 800r/min, 900r/min or 1000r/min, and the time of the ball milling can be 20min, 30min or 40min.
In a specific embodiment, in step (2) and step (3), the concentration of the aqueous ammonia solution is 5 to 10%, preferably 5 to 8%.
In a specific embodiment, the weight ratio of the alcohol substance to the ammonium metavanadate is 1-4mL:1g. Specifically, the liquid-solid ratio of the alcohol substance to the ammonium metavanadate is 1mL to 1g, 2mL to 1g, 3mL to 1g or 4mL to 1g.
In a specific embodiment, in step (4), the mixing conditions include: the mixing temperature is 200-300 ℃, and the mixing time is 5-12h. Specifically, the temperature of the mixing may be 200 ℃, 250 ℃ or 300 ℃; the mixing time may be 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.
In a specific embodiment, in step (4), the ageing time is 24-72 hours, preferably 36-48 hours. Specifically, it may be 24h, 30h, 36h, 40h, 48h, 50h, 60h or 72h.
In the method, the ageing temperature is normal temperature, and the ageing temperature is not required to be additionally increased.
In the method of the present invention, in order to provide the prepared denitration catalyst with excellent catalytic performance, the temperature and time of the calcination process need to be strictly controlled. Thus, in step (6), the calcination temperature is 400-700 ℃ and the calcination time is 1-8 hours. Specifically, the temperature of the calcination may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, or 700 ℃; the calcination time may be 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h.
In the method of the present invention, in step (6), in order to make the performance of the denitration catalyst obtained more excellent, the dried honeycomb catalyst blank may be calcined at least once, preferably 2 to 3 times; more preferably, the temperature at which at least one calcination is present during calcination is 600-700 ℃.
In a specific embodiment, in the step (6), when the calcination is performed for a plurality of times, the temperature can be directly raised to the next calcination temperature without cooling after the previous calcination is finished.
In a preferred embodiment, in step (6), the calcination is carried out at a temperature of 600 to 700 ℃ for a time of 4 to 8 hours.
In a preferred embodiment, in step (6), the rate of temperature increase during calcination is controlled to be less than or equal to 6 ℃/min, such as a rate of temperature increase of 3-6 ℃/min.
In specific embodiments, the lubricant is selected from one or more of glycerol, triethanolamine, and stearic acid.
In a specific embodiment, the plasticizer is selected from phthalic acid and/or dioctyl phthalate.
In a specific embodiment, the binder is one or more selected from the group consisting of polyvinyl alcohol, methylcellulose, hydroxymethyl cellulose, polyacrylamide and polyethylene glycol.
The invention also provides a denitration catalyst prepared by the method.
In the invention, the carrier of the denitration catalyst is anatase titanium dioxide, the active component is vanadium oxide, the active auxiliary agent is tungsten oxide, and the additive comprises crushed waste wind power blades, a binder, a plasticizer and a lubricant.
The invention further provides a preparation method of the denitration catalyst or application of the denitration catalyst in removing nitrogen oxides in industrial boiler tail gas.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, tiO 2 Ammonium acetate, ammonium metatungstate, ammonium metavanadate, monoethanolamine, ethylene glycol, triethanolamine, polyvinyl alcohol and phthalic acid are purchased from chemical industry limited of tiger in Guangzhou, and the waste wind power blades are from a Longyuan Liaoning wind power plant.
The contents of glass fibers and resins in the waste wind blades in the following examples 1-3 are shown in Table 1:
TABLE 1
Examples numbering Glass fiber content (wt%) Resin content (wt%)
Example 1 71.24 28.76
Example 2 70.12 29.88
Example 3 72.33 27.67
Example 1
(1) Cutting and crushing 100g of waste wind power blades to obtain waste wind power blade crushed aggregates with the particle size of 80-400 meshes (the weight ratio of the 80-200 meshes of wind power blade crushed aggregates is 40 percent, and the weight ratio of the 200-400 meshes of wind power blade crushed aggregates is 60 percent);
(2) 53.4g of ammonium metatungstate was dissolved in 25ml of an aqueous ammonia solution (concentration 5%) to obtain a mixed solution a1, and 650g of TiO was added to the mixed solution a1 2 Then ball milling is carried out for half an hour, the ball milling speed is 800r/min, and the titanium tungsten powder mixture is obtained;
(3) Dissolving 12.8g of ammonium metavanadate in 50mL of ammonia water solution (with concentration of 5%), then adding 30mL of monoethanolamine, uniformly mixing to obtain a mixed solution b1, and then adding the mixed solution b1 into the titanium tungsten powder mixture;
(4) Mixing the mixture obtained in the step (3) with 40g of lubricant (triethanolamine), 40g of binder (polyvinyl alcohol), 50g of plasticizer (phthalic acid), 70g of waste wind power blade crushed aggregates and 160g of water, mixing at 200 ℃ for 5 hours, and aging and placing for 36 hours;
(5) Extruding and forming the aged mixture to obtain honeycomb catalyst blanks;
(6) Drying the honeycomb catalyst blank for 10 hours at 80 ℃ and then carrying out twice calcination, wherein the first calcination temperature is 400 ℃, the calcination time is 1 hour, the second calcination is carried out after the calcination is finished, the calcination temperature is 650 ℃, the heating rate is controlled to be 6 ℃/min, the calcination time is 4 hours, and the denitration catalyst (9 multiplied by 9 holes, and the aperture is 6.4 mm) is obtained after the calcination is finished.
Example 2
(1) Cutting and crushing 100g of waste wind power blades to 80-400 meshes to obtain waste wind power blade crushed aggregates (the weight ratio of the 80-200 meshes of wind power blade crushed aggregates is 60 percent, and the weight ratio of the 200-400 meshes of wind power blade crushed aggregates is 40 percent);
(2) 47.5g of tungsten trioxide was dissolved in 50ml of an aqueous ammonia solution (concentration 5%) to obtain a mixed solution a2Then 550g of TiO was added to the mixed solution a2 2 Then ball milling is carried out for half an hour, the ball milling speed is 800r/min, and the titanium tungsten powder mixture is obtained;
(3) Dissolving 12.5g of ammonium metavanadate in 50mL of ammonia water solution (with the concentration of 6%), then adding 30mL of monoethanolamine, uniformly mixing to obtain a mixed solution b3, and then adding the mixed solution b3 into the titanium tungsten powder mixture;
(4) Mixing the mixture obtained in the step (3) with 40g of lubricant (triethanolamine), 50g of binder (polyvinyl alcohol), 30g of plasticizer (phthalic acid), 70g of waste wind power blade crushed aggregates and 150g of water, mixing at 200 ℃ for 12 hours, and aging and placing for 48 hours;
(5) Extruding and forming the aged mixture to obtain honeycomb catalyst blanks;
(6) Drying the honeycomb catalyst blank for 10 hours at 80 ℃ and then calcining, wherein the calcining temperature is 650 ℃, the heating rate is 5 ℃/min, the calcining time is 5 hours, and the denitration catalyst (9 multiplied by 9 holes with the aperture of 6.4 mm) is obtained by cutting after the calcining is finished.
Example 3
(1) Cutting and crushing 100g of waste wind power blades to 80-400 meshes to obtain waste wind power blade crushed aggregates (the weight ratio of the 80-200 meshes of wind power blade crushed aggregates is 50%, and the weight ratio of the 200-400 meshes of wind power blade crushed aggregates is 50%);
(2) 50g of tungsten trioxide was dissolved in 50ml of an aqueous ammonia solution (concentration 5%) to obtain a mixed solution a3, and 550g of TiO was added to the mixed solution a3 2 Then ball milling is carried out for half an hour, the ball milling speed is 800r/min, and the titanium tungsten powder mixture is obtained;
(3) Dissolving 12.8g of ammonium metavanadate in 50mL of ammonia water solution (concentration is 5%), then adding 30mL of ethylene glycol, uniformly mixing to obtain a mixed solution b3, and then adding the mixed solution b3 into the titanium tungsten powder mixture;
(4) Mixing the mixture obtained in the step (3) with 40g of lubricant (triethanolamine), 50g of binder (polyvinyl alcohol), 30g of plasticizer (phthalic acid), 70g of waste wind power blade crushed aggregates and 150g of water, mixing at 200 ℃ for 12 hours, and aging and placing for 48 hours;
(5) Extruding and forming the aged mixture to obtain honeycomb catalyst blanks;
(6) Drying the honeycomb catalyst blank for 10 hours at 80 ℃ and then calcining, wherein the calcining temperature is 600 ℃, the heating rate is 6 ℃/min, the calcining time is 5 hours, and the denitration catalyst (9 multiplied by 9 holes with the aperture of 6.4 mm) is obtained after the calcining is finished.
Example 4
The procedure was carried out as described in example 2, except that in step (6), the calcination temperature during calcination was changed to 300 ℃.
Comparative example 1
The process of example 1 was followed, except that no scrap wind blade pieces were added in step (4).
Comparative example 2
The process described in example 2 was carried out, in contrast to this, in step (4) no waste wind blade particles were added.
Comparative example 3
The method of example 1 was performed, except that, in step (4), a commercially available glass fiber powder was added instead of the waste wind turbine blade particles obtained in step (1), and the commercially available glass fiber powder was added in the same amount and in the same particle size range as the waste wind turbine blade particles.
Comparative example 4
The method of example 1 was performed, except that in step (1), the waste wind power blades were cut and crushed to a particle size of 500 to 600 mesh.
Test case
Test example 1
The denitration catalysts obtained in examples 1 to 4 and the products obtained in comparative examples 1 to 4 were tested with a TYE-300 type pressure tester having a measuring range of 300KN and a pressurizing rate of 250N/s, and the test results are shown in Table 2.
Test example 2
The denitration catalyst obtained in examples 1 to 4 and the product obtained in comparative examples 1 to 4 were taken in a small block, and after pulverization, the specific surface areas of the denitration catalyst and the product were tested by using a full-automatic nitrogen adsorption and desorption instrument (microphone 2020), and the test results are shown in table 2.
Test example 3
The denitration catalysts obtained in examples 1 to 4 and the products obtained in comparative examples 1 to 4 were tested for denitration rate of nitrogen oxides;
the testing method comprises the following steps: loading a small sample of the denitration catalyst and a small sample of the product into a catalyst performance evaluation reaction device, and introducing simulated gas to evaluate the activity of the denitration catalyst obtained in examples 1-3 and the product obtained in comparative examples 1-4. The simulated gas composition was similar to the industrial boiler tail gas composition, which was as follows: 500ppm NO, 400ppm NH 3 10.00% O 2 12% of water and the balance of nitrogen. Introducing the simulated gas into a denitration reactor for reaction, wherein the reaction temperature is 350 ℃, the concentration of nitrogen oxides in the flue gas before and after the reaction is analyzed by adopting a 42i-HL flue gas analyzer, and then the denitration rate of the denitration catalyst is calculated;
the concentration of nitrogen oxides in the flue gas before the reaction is a, the concentration of nitrogen oxides in the flue gas after the reaction is b, and the calculation formula of the denitration rate of the denitration catalyst is as follows:
η= (a-b)/a×100% and the test results are shown in table 2.
TABLE 2
As can be seen from the results in Table 2, the denitration catalyst with excellent denitration rate is successfully prepared by the method, and the denitration rate is equivalent to that of the denitration catalyst prepared by the glass fiber powder sold in the market, so that the denitration catalyst prepared by the method has no adverse effect on the catalytic performance, waste wind power blades can be recycled, the preparation cost of the denitration catalyst is reduced, and meanwhile, the waste wind power blades are reasonably recycled.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (10)

1. The method for preparing the denitration catalyst by using the waste wind power blades is characterized by comprising the following steps of:
(1) Cutting and crushing the waste wind power blades to 80-400 meshes to obtain waste wind power blade crushed aggregates;
(2) Mixing tungsten source with ammonia water solution to obtain mixed solution a, and mixing mixed solution a with TiO 2 Mixing to obtain a titanium tungsten powder mixture;
(3) Mixing ammonium metavanadate, an ammonia water solution and an alcohol substance to obtain a mixed solution b, and then mixing the mixed solution b with a titanium tungsten powder mixture;
(4) Mixing the mixture obtained in the step (3) with a lubricant, a binder, a plasticizer and crushed waste wind power blades, and then mixing and ageing;
(5) Extruding and forming the aged mixture to obtain honeycomb catalyst blanks;
(6) Drying the honeycomb catalyst blank, calcining at least once, and cutting;
wherein, tiO 2 The weight ratio of the tungsten source to the ammonium metavanadate to the dosage of the lubricant to the binder to the dosage of the waste wind power blade crushed aggregates to the plasticizer is (12-115) 1-10 1-15-1-20-1-10;
the tungsten source is selected from ammonium metatungstate and/or tungsten trioxide;
the alcohol substance is monoethanolamine and/or ethylene glycol;
the content of glass fiber in the waste wind power blade is 50-80wt% and the content of resin is 20-50wt%;
in the step (6), the calcination temperature is 400-700 ℃ and the calcination time is 1-8h.
2. The method for preparing denitration catalyst by using waste wind power blades as claimed in claim 1, wherein the method is characterized by comprising the following steps of 2 The weight ratio of the tungsten source, ammonium metavanadate, lubricant, binder, waste wind power blade crushed aggregates and plasticizer is (40-80): (3-8) 1 (3-8), 3-7, 4-8 and 2-5.
3. The method for preparing a denitration catalyst by using waste wind power blades as claimed in claim 1, wherein the liquid-solid ratio of the alcohol substance to the ammonium metavanadate is 1-4mL:1g.
4. The method for preparing a denitration catalyst by using waste wind blades as claimed in claim 1, wherein in the step (4), the mixing conditions include: the mixing temperature is 200-300 ℃, and the mixing time is 5-12h.
5. The method for preparing a denitration catalyst by using waste wind power blades as claimed in claim 1, wherein the ageing time is 24-72 hours.
6. The method for preparing a denitration catalyst by using waste wind power blades as claimed in claim 1 or 2, wherein the lubricant is one or more selected from glycerol, triethanolamine and stearic acid.
7. The method for preparing a denitration catalyst by using waste wind power blades according to claim 1 or 2, wherein the plasticizer is selected from phthalic acid and/or dioctyl phthalate.
8. The method for preparing a denitration catalyst by using waste wind power blades as claimed in claim 1 or 2, wherein the binder is one or more selected from polyvinyl alcohol, methyl cellulose, hydroxymethyl cellulose, polyacrylamide and polyethylene glycol.
9. The denitration catalyst obtained by the method for preparing a denitration catalyst by using waste wind power blades according to any one of claims 1 to 8.
10. Use of the denitration catalyst as claimed in claim 9 for removing nitrogen oxides from industrial boiler tail gas.
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