Preparation method of wear-resistant denitration catalyst for cement denitration and prepared denitration catalyst
阅读说明：本技术 一种水泥脱硝用耐磨式脱硝催化剂制备方法及制得的脱硝催化剂 (Preparation method of wear-resistant denitration catalyst for cement denitration and prepared denitration catalyst ) 是由 潘有春 梁燕 王光应 许晓龙 赵羽 崔鹏 于 2020-12-25 设计创作，主要内容包括：本发明公开一种水泥脱硝用耐磨式脱硝催化剂制备方法,涉及环保材料技术领域,是基于水泥行业烟气含尘量高,催化剂堵塞、磨损严重的问题提出的。本发明使用磷酸改性氧化镁改性过的二氧化钛为载体,使用表面具有氧化铝涂层的废弃三元催化剂废料及碳化硅等强度助剂,通过引入镁成分,使得二氧化钛载体更易低温烧结,采用磷酸水热预处理,增强载体的整体酸性,抵消烧结助剂镁成分带来的酸性削减作用,引入表面具有氧化铝涂层的废弃三元催化剂废料和碳化硅进一步增强催化剂的机械强度剂耐磨性,引入磷酸铝,增强各催化剂中各组分的结合强度,得到具有高强度和耐磨性的催化剂,然后在此基础上改变蜂窝催化剂的表观架构,增强催化剂的防堵性。(The invention discloses a preparation method of a wear-resistant denitration catalyst for cement denitration, relates to the technical field of environment-friendly materials, and is provided based on the problems of high dust content in flue gas, and serious blockage and abrasion of the catalyst in the cement industry. The invention uses titanium dioxide modified by phosphoric acid modified magnesium oxide as a carrier, uses waste three-way catalyst waste with an aluminum oxide coating on the surface and strength additives such as silicon carbide and the like, leads the titanium dioxide carrier to be easier to sinter at low temperature by introducing magnesium components, adopts phosphoric acid hydrothermal pretreatment to enhance the overall acidity of the carrier and counteract the acidity reduction effect brought by the magnesium components of the sintering additives, further enhances the mechanical strength agent wear resistance of the catalyst by introducing the waste three-way catalyst waste with the aluminum oxide coating on the surface and the silicon carbide, introduces aluminum phosphate to enhance the bonding strength of each component in each catalyst to obtain the catalyst with high strength and wear resistance, then changes the apparent framework of the honeycomb catalyst on the basis and enhances the anti-blocking property of the catalyst.)
1. The preparation method of the wear-resistant denitration catalyst for cement denitration is characterized by comprising the following steps:
(1) adding magnesium chloride into deionized water to obtain a magnesium chloride solution; adding TiO into the mixture2Adding into magnesium chloride solution, gradually dripping ammonia water under stirring until pH is 11, stirring for reaction for 20-30min, vacuum filtering, drying at 60-80 deg.C, and calcining at 200-300 deg.C for 5-6h to obtain MgO modified TiO2；
(2) Taking the modified TiO in the step (1)2Grinding and sieving, and selecting 200-300 mesh modified TiO2Adding the particles into a phosphoric acid solution, carrying out hydrothermal treatment at 180 ℃ for 14-16h, filtering, drying at 60-80 ℃, and roasting at 200-300 ℃ for 5-6h to obtain the phosphoric acid modified TiO2-a MgO composite component a;
(3) taking a proper amount of 200-mesh 300-mesh waste three-way catalyst powder, immersing the waste three-way catalyst powder into 25 wt% of aluminum sol for 10-15min, then carrying out freeze drying at the temperature of-50 to-60 ℃, wherein the freeze drying time is 24-48h, and finally roasting at 400 ℃ to obtain waste three-way catalyst powder B of an alumina coating;
(4) dissolving a proper amount of ammonium metavanadate and ammonium metatungstate in water to obtain an active component precursor solution B;
(5) taking a proper amount of the composite component A, aluminum phosphate, a wear-resistant additive and powder B, uniformly mixing to obtain a mixed carrier, then adding the composite precursor solution B into the mixed carrier, adding hydroxymethyl cellulose, stearic acid and glass fiber, mixing after deionization, and ageing to obtain mixed plastic pug;
(6) and (5) carrying out integral extrusion molding on the catalyst obtained in the step (5) by adopting a die, drying and calcining to obtain the anti-blocking wear-resistant denitration catalyst for cement denitration.
2. The preparation method of the wear-resistant denitration catalyst for cement denitration according to claim 1, characterized by comprising the following steps: the weight ratio of the magnesium chloride to the deionized water in the step (1) is 1: 30.
3. The preparation method of the wear-resistant denitration catalyst for cement denitration according to claim 1, characterized by comprising the following steps: magnesium chloride and TiO in the step (1)2The weight portion ratio of (A) to (B) is 0-5: 100.
4. The preparation method of the wear-resistant denitration catalyst for cement denitration according to claim 1, characterized by comprising the following steps: the phosphoric acid solution and the modified TiO in the step (2)2In a weight ratio of 1: 1.
5. The preparation method of the wear-resistant denitration catalyst for cement denitration according to claim 1, characterized by comprising the following steps: and (3) the ratio of the sum of the parts by weight of the ammonium metavanadate and the ammonium metatungstate to the part by weight of the deionized water in the step (4) is 1: 5.
6. The preparation method of the wear-resistant denitration catalyst for cement denitration according to claim 1, characterized by comprising the following steps: and (5) the wear-resistant auxiliary agent is silicon carbide.
7. The preparation method of the wear-resistant denitration catalyst for cement denitration according to claim 1, characterized by comprising the following steps: in the step (5), the weight part ratio of the composite component A, the aluminum phosphate, the wear-resistant additive and the powder B is 100:1-5:3-8: 10-20.
8. The preparation method of the wear-resistant denitration catalyst for cement denitration according to claim 1, characterized by comprising the following steps: in the step (5), the weight part ratio of the hydroxymethyl cellulose to the stearic acid to the glass fiber to the deionized water is 1:1:5: 50.
9. The preparation method of the wear-resistant denitration catalyst for cement denitration according to claim 1, characterized by comprising the following steps: v in the catalyst obtained in the step (6)2O5In an amount of 1%, WO3The loading of (b) was 5%.
10. The wear-resistant denitrification catalyst for cement denitrification, which is prepared by the preparation method of the wear-resistant denitrification catalyst for cement denitrification according to any one of claims 1-9.
Technical Field
The invention relates to the technical field of environment-friendly materials, and particularly relates to a preparation method of a wear-resistant denitration catalyst for cement denitration and a prepared denitration catalyst.
Background
Nitrogen oxides (NOx) are one of the causes of pollution phenomena such as haze and acid rain, and are the main targets of air pollution control. According to statistics, the national cement cumulative yield in 2019 is 23.3 hundred million tons, and the NOx emission of the cement industry accounts for about 10% -12% of the national NOx emission total amount, so that the cement industry is the third pollution source after fire power and motor vehicles. With the successive discharge of ultralow emission standard from partial provinces and cities, the emission standard of nitrogen oxides in each province and city is from 50mg/m3To 150mg/m3All have coverage, and the ultra-low emission becomes a necessary trend. Meanwhile, the SCR catalyst is generally discarded after 2.4 ten thousand hours of use. In the national hazardous waste records issued in 2016, waste vanadium-titanium catalysts (HW50-772 and 007-50) generated in the flue gas denitration process are definitely listed as hazardous wastes. The regeneration of the waste SCR catalyst can obviously reduce the use cost of the SCR catalyst and realize the high-value utilization of waste resources, and the premise of the regeneration of the catalyst is that the catalyst needs to have mechanical properties meeting the regeneration requirements. Therefore, the improvement of the mechanical properties such as compressive strength of the catalyst is of great significance to the cement denitration catalyst.
Patent CN103846094A discloses a catalyst for denitration of cement kiln flue gas and a preparation method thereof. The dust content in the tail flue gas of the cement kiln is extremely high and can reach 80-120mg/Nm3Meanwhile, the fly ash has small particle size, which causes large dust viscosity; the adhesion is strong. Is easy to be adsorbed on the surface of the catalyst to cause the catalyst to be blocked, so that the catalyst can not play the catalysis roleAnd (4) acting. Meanwhile, the dust content in the tail flue gas of the cement kiln is extremely high, and the windward end of the catalyst is easy to wear under the flushing of the high-dust flue gas, so that the catalyst loses the mechanical property and directly loses the usability.
Disclosure of Invention
The invention aims to solve the technical problems of high dust content in flue gas, and serious blockage and abrasion of a catalyst in the cement industry.
The invention solves the technical problems through the following technical means:
a preparation method of a wear-resistant denitration catalyst for cement denitration comprises the following steps:
(1) adding magnesium chloride into deionized water to obtain a magnesium chloride solution; adding TiO into the mixture2Adding into magnesium chloride solution, gradually dripping ammonia water under stirring until pH is 11, stirring for reaction for 20-30min, vacuum filtering, drying at 60-80 deg.C, and calcining at 200-300 deg.C for 5-6h to obtain MgO modified TiO2；
(2) Taking the modified TiO in the step (1)2Grinding and sieving, and selecting 200-300 mesh modified TiO2Adding the particles into a phosphoric acid solution, carrying out hydrothermal treatment at 180 ℃ for 14-16h, filtering, drying at 60-80 ℃, and roasting at 200-300 ℃ for 5-6h to obtain the phosphoric acid modified TiO2-a MgO composite component a;
(3) taking a proper amount of 200-mesh 300-mesh waste three-way catalyst powder, immersing the waste three-way catalyst powder into 25 wt% of aluminum sol for 10-15min, then carrying out freeze drying at the temperature of-50 to-60 ℃, wherein the freeze drying time is 24-48h, and finally roasting at 400 ℃ to obtain waste three-way catalyst powder B of an alumina coating;
(4) dissolving a proper amount of ammonium metavanadate and ammonium metatungstate in water to obtain an active component precursor solution B;
(5) taking a proper amount of the composite component A, aluminum phosphate, a wear-resistant additive and powder B, uniformly mixing to obtain a mixed carrier, then adding the composite precursor solution B into the mixed carrier, adding hydroxymethyl cellulose, stearic acid and glass fiber, mixing after deionization, and ageing to obtain mixed plastic pug;
(6) and (5) carrying out integral extrusion molding on the catalyst obtained in the step (5) by adopting a die, drying and calcining to obtain the anti-blocking wear-resistant denitration catalyst for cement denitration.
According to the invention, the magnesium component is introduced, so that the titanium dioxide carrier is easier to sinter at a low temperature, the overall strength of the catalyst is improved from the roasting angle, the overall acidity of the carrier is enhanced by adopting hydrothermal pretreatment of phosphoric acid, the acidity reduction effect brought by the magnesium component serving as a sintering aid is offset, the mechanical strength agent abrasion resistance of the catalyst is further enhanced by introducing waste three-way catalyst waste materials with an alumina coating on the surface and silicon carbide, the aluminum phosphate is introduced, the bonding strength of each component in each catalyst is enhanced, the catalyst with high strength and abrasion resistance is obtained, then the apparent framework of the honeycomb catalyst is changed on the basis, the anti-blocking property of the catalyst is enhanced, and the catalyst has excellent mechanical strength, abrasion resistance and anti-blocking property.
Preferably, the weight part ratio of the magnesium chloride to the deionized water in the step (1) is 1: 30.
Preferably, the magnesium chloride and TiO in the step (1)2The weight portion ratio of (A) to (B) is 0-5: 100.
Preferably, the phosphoric acid solution and the modified TiO in the step (2)2In a weight ratio of 1: 1.
Preferably, the ratio of the sum of the parts by weight of the ammonium metavanadate and the ammonium metatungstate to the part by weight of the deionized water in the step (4) is 1: 5.
Preferably, the wear-resistant assistant in the step (5) is silicon carbide.
Preferably, the weight part ratio of the composite component A, the aluminum phosphate, the wear-resisting assistant and the powder B in the step (5) is 100:1-5:3-8: 10-20.
Preferably, the weight part ratio of the hydroxymethyl cellulose to the stearic acid to the glass fiber to the deionized water in the step (5) is 1:1:5: 50.
Preferably, V in the catalyst obtained in the step (6)2O5In an amount of 1%, WO3The loading of (b) was 5%.
A wear-resistant denitration catalyst for cement denitration, which is prepared by a preparation method of the wear-resistant denitration catalyst for cement denitration.
The invention has the following beneficial effects:
1. according to the invention, the magnesium component is introduced, so that the titanium dioxide carrier is easier to sinter at a low temperature, the overall strength of the catalyst is improved from the roasting angle, the overall acidity of the carrier is enhanced by adopting hydrothermal pretreatment of phosphoric acid, the acidity reduction effect brought by the magnesium component serving as a sintering aid is offset, the mechanical strength agent abrasion resistance of the catalyst is further enhanced by introducing waste three-way catalyst waste materials with an alumina coating on the surface and silicon carbide, the aluminum phosphate is introduced, the bonding strength of each component in the catalyst is enhanced, the catalyst with high strength and abrasion resistance is obtained, then the apparent framework of the honeycomb catalyst is changed on the basis, the anti-blocking performance of the catalyst is enhanced, and the catalyst has excellent mechanical strength, abrasion resistance and anti-blocking performance.
2. The addition of the Mg component, the waste three-way catalyst and the silicon carbide obviously enhances the compressive strength and the wear-resistant strength of the catalyst, and meanwhile, the phosphoric acid pretreatment obviously enhances the catalytic performance of the catalyst; meanwhile, as can be seen from the comparative example, under the condition that the volume of the catalyst is the same, but the catalytic area of the anti-blocking wear-resistant denitration catalyst is obviously smaller than that of the commercial catalyst, the anti-blocking wear-resistant denitration catalyst still has the denitration efficiency which is close to that of the commercial denitration catalyst; meanwhile, according to a blockage experiment, the blockage releasing denitration catalyst has a remarkable anti-blockage effect.
Drawings
FIG. 1 is a schematic cross-sectional view of a shaped catalyst prepared in accordance with an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings and the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A preparation method of a wear-resistant denitration catalyst for cement denitration comprises the following steps:
(1) adding 5 parts of magnesium chloride into 150 parts of deionized water to obtain a magnesium chloride solution, and adding 100 parts of TiO2Gradually dropwise adding ammonia water under stirring to pH 11, stirring for reaction for 30min, vacuum filtering, oven drying at 60 deg.C, roasting at 300 deg.C for 6h, and grinding to below 300 mesh to obtain MgO modified TiO2；
(2) Taking 100 parts of the modified TiO in the step 12Adding the mixture into 100 parts of 25 wt% phosphoric acid solution, carrying out hydrothermal treatment for 16h at 180 ℃, filtering, drying at 60 ℃, and calcining at 300 ℃ to obtain the phosphoric acid modified TiO2-a MgO composite component a;
(3) completely immersing waste three-way catalyst powder below 300 meshes into 25 wt% of aluminum sol for 10min, then freeze-drying at the temperature of minus 55 ℃ for 30h, and finally roasting at the temperature of 400 ℃ to obtain waste three-way catalyst powder B of an alumina coating;
(4) dissolving 1.77 parts of ammonium metavanadate and 4.41 parts of ammonium metatungstate in 30.9 parts of deionized water to obtain an active component precursor solution B;
(5) uniformly mixing 100 parts of composite component A, 3 parts of aluminum phosphate, 8 parts of silicon carbide, 20 parts of powder B, 1.31 parts of hydroxymethyl cellulose, 1.31 parts of stearic acid and 6.55 parts of glass fiber, adding the composite precursor solution B obtained in the step (2), adding 65.5 parts of deionized water, mixing, and aging to obtain mixed plastic pug;
(6) and (3) carrying out integral extrusion molding on the catalyst obtained in the step (5) by using a special die, drying at 60 ℃, and calcining at 550 ℃ for 6 hours to obtain the anti-blocking wear-resistant denitration catalyst for cement denitration.
The catalyst (150X 150mm in cross section, 13X 13 holes, 500mm in length) was placed in a fixed bed, and a simulated gas was introduced, and the bed was raisedTesting the performance of the catalyst at a high temperature; the simulated gas composition was: NO (1000ppm), NH3(1000ppm)、O2(6vol.％)、N2As a carrier gas, the test temperature was 290 deg.c, and the test results are shown in table 1.
The attrition strength and the crushing strength of the catalyst were tested according to standard DL/T1286-2013, and the test results are shown in Table 1.
Example 2
A preparation method of a wear-resistant denitration catalyst for cement denitration comprises the following steps:
(1) adding 3 parts of magnesium chloride into 90 parts of deionized water to obtain a magnesium chloride solution, and adding 100 parts of TiO2Gradually dropwise adding ammonia water under stirring to pH 11, stirring for reaction for 30min, vacuum filtering, oven drying at 60 deg.C, roasting at 300 deg.C for 6h, and grinding to below 300 mesh to obtain MgO modified TiO2；
(2) Taking 100 parts of the modified TiO in the step (1)2Adding the mixture into 100 parts of 15 wt% phosphoric acid solution, carrying out hydrothermal treatment for 16h at 180 ℃, filtering, drying at 60 ℃, and calcining at 300 ℃ to obtain the phosphoric acid modified TiO2-a MgO composite component a;
(3) completely immersing waste three-way catalyst powder below 300 meshes into 25 wt% of aluminum sol for 10min, then freeze-drying at the temperature of minus 55 ℃ for 30h, and finally roasting at the temperature of 400 ℃ to obtain waste three-way catalyst powder B of an alumina coating;
(4) dissolving 1.63 parts of ammonium metavanadate and 4.07 parts of ammonium metatungstate in 28.5 parts of deionized water to obtain an active component precursor solution B;
(5) uniformly mixing 100 parts of composite component A, 3 parts of aluminum phosphate, 8 parts of silicon carbide, 10 parts of powder B, 1.21 parts of hydroxymethyl cellulose, 1.21 parts of stearic acid and 6.05 parts of glass fiber, adding the composite precursor solution B obtained in the step (2), adding 60.5 parts of deionized water, mixing, and aging to obtain mixed plastic pug;
(6) and (3) carrying out integral extrusion molding on the catalyst obtained in the step (5) by using a special die, drying at 60 ℃, and calcining at 550 ℃ for 6 hours to obtain the anti-blocking wear-resistant denitration catalyst for cement denitration.
Placing a catalyst (with the cross section of 150mm, the cross section of 13 mm, the length of 500mm) in a fixed bed, introducing simulated gas, and heating to test the performance of the catalyst; the simulated gas composition was: NO (1000ppm), NH3(1000ppm)、O2(6vol.％)、N2As a carrier gas, the test temperature was 290 deg.c, and the test results are shown in table 1.
The attrition strength and the crushing strength of the catalyst were tested according to standard DL/T1286-2013, and the test results are shown in Table 1.
Example 3
A preparation method of a wear-resistant denitration catalyst for cement denitration comprises the following steps:
(1) adding 3 parts of magnesium chloride into 90 parts of deionized water to obtain a magnesium chloride solution, and adding 100 parts of TiO2Gradually dropwise adding ammonia water under stirring to pH 11, stirring for reaction for 30min, vacuum filtering, oven drying at 60 deg.C, roasting at 300 deg.C for 6h, and grinding to below 300 mesh to obtain MgO modified TiO2；
(2) Taking 100 parts of the modified TiO in the step 12Adding the mixture into 100 parts of 15 wt% phosphoric acid solution, carrying out hydrothermal treatment for 16h at 180 ℃, filtering, drying at 60 ℃, and calcining at 300 ℃ to obtain the phosphoric acid modified TiO2-a MgO composite component a;
(3) completely immersing waste three-way catalyst powder below 300 meshes into 25 wt% of aluminum sol for 10min, then freeze-drying at the temperature of minus 55 ℃ for 30h, and finally roasting at the temperature of 400 ℃ to obtain waste three-way catalyst powder B of an alumina coating;
(4) dissolving 1.71 parts of ammonium metavanadate and 4.28 parts of ammonium metatungstate in 29.95 parts of deionized water to obtain an active component precursor solution B;
(5) uniformly mixing 100 parts of composite component A, 3 parts of aluminum phosphate, 4 parts of silicon carbide, 20 parts of powder B, 1.27 parts of hydroxymethyl cellulose, 1.27 parts of stearic acid and 6.35 parts of glass fiber, adding the composite precursor solution B obtained in the step (2), adding 63.5 parts of deionized water, mixing, and aging to obtain mixed plastic pug;
(5) and (3) carrying out integral extrusion molding on the catalyst obtained in the step (5) by using a special die, drying at 60 ℃, and calcining at 550 ℃ for 6 hours to obtain the anti-blocking wear-resistant denitration catalyst for cement denitration.
Placing a catalyst (with the cross section of 150mm, the cross section of 13 mm, the length of 500mm) in a fixed bed, introducing simulated gas, and heating to test the performance of the catalyst; the simulated gas composition was: NO (1000ppm), NH3(1000ppm)、O2(6vol.％)、N2As a carrier gas, the test temperature was 290 deg.c, and the test results are shown in table 1.
The attrition strength and the crushing strength of the catalyst were tested according to standard DL/T1286-2013, and the test results are shown in Table 1.
Comparative example 1
Completely immersing waste three-way catalyst powder below 300 meshes into aluminum sol with the mass fraction of 25 wt% d for 10min, then carrying out freeze drying at the temperature of minus 55 ℃ for 30h, and finally roasting at the temperature of 400 ℃ to obtain waste three-way catalyst powder B with an alumina coating; dissolving 1.54 parts of ammonium metavanadate and 3.84 parts of ammonium metatungstate in 26.9 parts of deionized water to obtain an active component precursor solution B; taking 100 parts of TiO21 part of aluminum phosphate, 3 parts of silicon carbide, 10 parts of powder B, 1.14 parts of hydroxymethyl cellulose, 1.14 parts of stearic acid and 5.7 parts of glass fiber, uniformly mixing, adding the obtained composite precursor solution B, adding 57 parts of deionized water, mixing, and ageing to obtain mixed plastic pug; and carrying out integral extrusion molding on the obtained catalyst by using a special die, drying at 60 ℃, and calcining at 550 ℃ for 6 hours to obtain the anti-blocking wear-resistant denitration catalyst for cement denitration.
Placing a catalyst (with the cross section of 150mm, the cross section of 13 mm, the length of 500mm) in a fixed bed, introducing simulated gas, and heating to test the performance of the catalyst; the simulated gas composition was: NO (1000ppm), NH3(1000ppm)、O2(6vol.％)、N2As a carrier gas, the test temperature was 290 deg.c, and the test results are shown in table 1.
The attrition strength and the crushing strength of the catalyst were tested according to standard DL/T1286-2013, the results of which are shown in Table 1.
Comparative example 2
Adding 5 parts of magnesium chloride to 150 parts of magnesium chlorideAdding 100 parts of TiO into deionized water to obtain a magnesium chloride solution2Gradually dropwise adding ammonia water under stirring to pH 11, stirring for reaction for 30min, vacuum filtering, oven drying at 60 deg.C, roasting at 300 deg.C for 6h, and grinding to below 300 mesh to obtain MgO modified TiO2(ii) a Completely immersing waste three-way catalyst powder below 300 meshes into aluminum sol with the mass fraction of 25 wt% d for 10min, then carrying out freeze drying at the temperature of minus 55 ℃ for 30h, and finally roasting at the temperature of 400 ℃ to obtain waste three-way catalyst powder B with an alumina coating; dissolving 1.77 parts of ammonium metavanadate and 4.41 parts of ammonium metatungstate in 30.9 parts of deionized water to obtain an active component precursor solution B; taking 100 parts of TiO2Uniformly mixing 3 parts of aluminum phosphate, 8 parts of silicon carbide, 20 parts of powder B, 1.31 parts of hydroxymethyl cellulose, 1.31 parts of stearic acid and 6.55 parts of glass fiber, adding the obtained composite precursor solution B, adding 65.5 parts of deionized water, mixing, and ageing to obtain mixed plastic pug; and carrying out integral extrusion molding on the obtained catalyst by using a special die, drying at 60 ℃, and calcining at 550 ℃ for 6 hours to obtain the anti-blocking wear-resistant denitration catalyst for cement denitration.
Placing a catalyst (with the cross section of 150mm, the cross section of 13 mm, the length of 500mm) in a fixed bed, introducing simulated gas, and heating to test the performance of the catalyst; the simulated gas composition was: NO (1000ppm), NH3(1000ppm)、O2(6vol.％)、N2As a carrier gas, the test temperature was 290 deg.c, and the test results are shown in table 1.
The attrition strength and the crushing strength of the catalyst were tested according to standard DL/T1286-2013, and the test results are shown in Table 1.
Comparative example 3
Dissolving 1.35 parts of ammonium metavanadate and 3.37 parts of ammonium metatungstate in 23.6 parts of water to obtain an active component precursor solution B; taking 100 parts of TiO2Uniformly mixing 1.05 parts of hydroxymethyl cellulose, 1.05 parts of stearic acid and 5 parts of glass fiber, adding the obtained composite precursor solution B, adding 52.5 parts of deionized water, mixing, and ageing to obtain mixed plastic pug; the obtained catalyst is subjected to integral extrusion molding by adopting a special die, dried at 60 ℃ and calcined at 550 ℃ for 6 hours to obtain waterThe anti-blocking wear-resistant denitration catalyst is used for denitration of mud.
Placing a catalyst (with the cross section of 150mm, the cross section of 13 mm, the length of 500mm) in a fixed bed, introducing simulated gas, and heating to test the performance of the catalyst; the simulated gas composition was: NO (1000ppm), NH3(1000ppm)、O2(6vol.％)、N2As a carrier gas, the test temperature was 290 deg.c, and the test results are shown in table 1.
The attrition strength and the crushing strength of the catalyst were tested according to standard DL/T1286-2013, and the test results are shown in Table 1.
Comparative example 4
Placing a commercial cement conventional honeycomb catalyst (with the cross section of 150 x 150mm, the cross section of 13 x 13 holes and the length of 500mm) with 13 holes in a fixed bed, introducing simulated gas, and heating to test the performance of the catalyst; the simulated gas composition was: NO (1000ppm), NH3(1000ppm)、O2(6vol.％)、N2As a carrier gas, the test temperature was 290 deg.c, and the test results are shown in table 1.
The abrasion strength of a conventional honeycomb catalyst with 13 cells for commercial cement was tested according to standard DL/T1286-2013 (no strength comparison test was performed due to inconsistent honeycomb structure) and the test results are shown in table 1.
A catalyst of example 2, comparative example 3 and comparative example 4 (cross section 150X 150mm, 13 pores, length 500mm) was placed in a simulated flue at a flow rate of 5m/s in the catalyst pores and a dust content of 100g/Nm3(the dust is real cement kiln tail dust), simulating flue gas to vertically pass through a catalyst pore channel from top to bottom, ventilating for 5 hours under the condition of no soot blowing, and testing the anti-blocking performance of the catalyst by measuring the pressure difference of the upper end and the lower end of the catalyst, wherein the test results are shown in table 1.
Table 1 shows the compressive strength, abrasion strength, catalytic performance and pore blocking of the catalysts of examples 1 to 3 and comparative examples 1 to 4
According to the data in the table 1, the compressive strength and the wear resistance of the catalyst are obviously enhanced by adding the Mg component, the waste three-way catalyst and the silicon carbide, and meanwhile, the catalytic performance of the catalyst is obviously enhanced by the phosphoric acid pretreatment; meanwhile, as can be seen from the comparative example, under the condition that the volume of the catalyst is the same, but the catalytic area of the anti-blocking wear-resistant denitration catalyst is obviously smaller than that of the commercial catalyst, the anti-blocking wear-resistant denitration catalyst still has the denitration efficiency which is close to that of the commercial denitration catalyst; meanwhile, according to a blockage experiment, the blockage releasing denitration catalyst has a remarkable anti-blockage effect.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.