CN114682297A - Low-temperature denitration catalyst and preparation method and application thereof - Google Patents
Low-temperature denitration catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a low-temperature denitration catalyst, and a preparation method and application thereof. The low-temperature denitration catalyst consists of a carrier, an active component, an active auxiliary agent and a water-resistant, sulfur-resistant and dust-resistant coating film; the carrier is a composite carrier; the mass of the active component accounts for 0.001-0.6 of the mass of the carrier; the mass of the active auxiliary agent accounts for 0.001-0.6 of the mass of the carrier; the mass of the water-resistant, sulfur-resistant and dust-resistant coating film accounts for 0.001-0.3 of the mass of the catalyst. The invention also provides a preparation method of the catalyst. The catalyst can be used for catalyzing denitration reaction of low-temperature (300 ℃) flue gas, has excellent water resistance, sulfur resistance and smoke dust resistance at low temperature, and is suitable for selective catalytic reduction of nitrogen oxide in low-temperature flue gas.
Description
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to a low-temperature denitration catalyst and a preparation method thereof, and belongs to the technical field of catalysts.
Background
Nitrogen Oxides (NO)x) The nitrogen oxide is one of main pollutants generated by combustion of fossil fuels, particularly coal, is harmful to human health, and can generate serious environmental problems such as photochemical smog, acid rain and the like, so that the nitrogen oxide treatment is always a hot point of domestic and foreign research. The best means for removing nitrogen oxides is to use NH3SCR denitration system, wherein V2O5type/Ti and type V2O5-WO3the/Ti type catalyst has been successfully introduced in China and is mature and applied in various factories such as large fire coal and the like. However, the vanadium catalyst has a working temperature of 320-410 ℃, belongs to a medium-high temperature section, and in order to obtain an ideal denitration effect, a high-temperature high-ash process is mostly adopted, i.e. an SCR device is arranged in front of a dust removal system and a desulfurization system, but the high-temperature section device has higher operation cost, and has higher requirements on the sulfur resistance and dust resistance of the catalyst, and a lot of factories without the additional denitration system need huge modification cost. If the catalyst is placed behind a desulfurization system, the concentration of sulfur dioxide and dust can be effectively reduced, so that the catalyst operates in a cleaner atmosphere, the service life is prolonged, a low-temperature SCR system is improved, a large amount of cost cannot be consumed, and the method is more in line with the national conditions of China. However, the low temperature section temperature typically drops below 250 ℃, at which conventional vanadium-based catalysts cannot operate.
Researchers have made many studies on low-temperature denitration catalysts, such as manganese-based catalysts, carbon-based catalysts, and vanadium-based catalysts added with Mo, Mn, Ce, etc., all have good low-temperature activity, but many of the low-temperature catalysts disclosed so far generally have the problem that the activity of the catalyst continuously decreases when a small amount of sulfur dioxide is introduced, and some sulfur-resistant catalysts are difficult to maintain their sulfur resistance in an atmosphere with water.
CN104056658A immersion of Mn in 3A molecular sieve by using tetraethoxysilane0.1-0.8Mg0.2-0.9Ox，Mn0.1- 0.8Mg0.2-0.9OxThe catalyst only carries silicon dioxide on the active component, and the carrying method adopts ultrasonic impregnation and is only suitable for a small amount of active componentsA powder catalyst, and the catalyst is not supported on the entire surface of the catalyst, and the catalyst support is a carbon support. CN104525275A adopts the method of drawing-dipping to cover polysiloxane on the SCR denitration catalyst surface, and its purpose is to improve the contact area of flue gas and SCR denitration catalyst reaction surface and guarantee denitration reaction reduction efficiency.
CN105214679A reports that the surface of a catalyst is covered with a silica coating, but only relates to the preparation of a powder catalyst, the catalyst does not contain vanadium element, and the covering of the silica coating is not the purpose of improving the smoke poisoning resistance of the honeycomb catalyst which is integrally formed.
The development difficulty of the low-temperature denitration catalyst is three points: firstly, how to have good denitration efficiency at low temperature; second, the flue gas contains a certain amount of SO2And water vapor, SO2And O in flue gas2And H2The O combination can generate ammonium bisulfate, the dew point temperature of the ammonium bisulfate is 270 ℃, the ammonium bisulfate has strong viscosity, and the flue dust in the flue gas can be adhered to the surface of the catalyst to inactivate the catalyst. Thirdly, even if the pre-dedusting treatment is carried out under the condition of low-temperature flue gas, the flue gas still has certain content of smoke dust (usually 10-30 mg/Nm) during low-temperature denitration3Soot), which may contain some alkali metals, alkaline earth metals and heavy metals, which generally have a poisoning effect on the denitration catalyst, so that the low-temperature denitration catalyst having a certain poisoning resistance against the soot is still a key point.
How to resist SO of denitration catalyst under low-temperature flue gas2A great deal of research is carried out, the existing patents and documents mainly focus on modulating active components and carriers of the catalyst, no technical research report related to blocking and inhibiting the generation of ammonium bisulfate exists, and on the other hand, a technical report on how to improve the smoke resistance of the low-temperature denitration catalyst is very rare.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a denitration catalyst having excellent water resistance and sulfur resistance at the same time in a low temperature environment, and a preparation method thereof.
In order to achieve the technical purpose, the invention provides a low-temperature denitration catalyst, which consists of a carrier, an active component, an active assistant and a water-resistant, sulfur-resistant and dust-resistant coating film;
wherein, the carrier is a composite carrier of titanium dioxide and a molecular sieve; the molecular sieve is a ZSM-5 molecular sieve and/or a beta molecular sieve;
the active component is one or a combination of more of Cu oxide, Mn oxide and V oxide; the mass of the active component accounts for 0.001-0.6 of the mass of the carrier;
the active additive is the combination of two or more of Ni oxide, Cr oxide, Fe oxide, Co oxide, Ce oxide and Mo oxide; the mass of the active auxiliary agent accounts for 0.001-0.6 of the mass of the carrier;
the mass of the water-resistant, sulfur-resistant and dust-resistant coating film accounts for 0.001-0.3 of the mass of the catalyst.
The low-temperature denitration catalyst of the invention can be present in the form of: the active component and the active auxiliary agent are loaded on the carrier, and the water-resistant, sulfur-resistant and dust-resistant coating film is coated on the carrier.
The low-temperature denitration catalyst takes a composite carrier of titanium dioxide and a molecular sieve as a carrier, and active components, an active auxiliary agent and a water-resistant, sulfur-resistant and dust-resistant auxiliary agent are loaded on the carrier. The formation of ammonium sulfate salt crystals in the low-temperature denitration reaction can be limited by microporous pore channels of the molecular sieve on the surface of the composite carrier, so that catalytic active sites distributed in the pore channels are protected; the water-resistant, sulfur-resistant and dust-resistant auxiliary agent can block and reduce SO2And the catalyst acts with oxygen, water and ammonia gas to inhibit the formation of ammonium sulfate salt. The low-temperature denitration catalyst provided by the invention inhibits the formation of ammonium sulfate by introducing a water-resistant, sulfur-resistant and dust-resistant coating film means, so that the water-resistant, sulfur-resistant and dust-resistant performances of the catalyst are improved. The low-temperature denitration catalyst has the advantages that the activity of the catalyst is not obviously reduced at low temperature (150-300 ℃) in the presence of sulfur dioxide and water, the low-temperature denitration catalyst has excellent low-temperature water-resistant and sulfur-resistant performance, and the low-temperature denitration catalyst has wide application prospect in low-temperature flue gas denitration reaction. The invention discloses that the water-resistant, sulfur-resistant and smoke-resistant coating film is introduced by surface modification for the first time, so that the coating film can be obviously formedThe water resistance, sulfur resistance and smoke resistance of the low-temperature denitration catalyst are improved.
In one embodiment of the invention, the water-resistant, sulfur-resistant and dust-resistant coating film is obtained by coating a solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent on a carrier. Wherein, the mass content of the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent is 0.5-80% (preferably 1-30%); the solvent adopted by the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent is one or a combination of more of cyclohexane, n-heptane and ethanol; the solution of the water-resistant, sulfur-resistant and dust-resistant additive adopts solute of one or a combination of a plurality of fluorine-containing polyacrylate, dimethyl cyclosiloxane and silicone oil.
Specifically, the fluorine-containing polyacrylate is selected from one or a combination of more of poly (hexafluorobutyl acrylate), poly (hexafluorobutyl methacrylate), poly (2, 2, 2-trifluoroethyl methacrylate), poly (dodecafluoro heptyl acrylate), poly (tridecyl octyl methacrylate), poly (tridecyl octyl fluoride) and poly (perfluoroalkyl ethyl acrylate).
Specifically, the dimethyl cyclosiloxane is selected from one or a combination of more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.
Specifically, the silicone oil is selected from one or more of methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxy silicone oil, ethyl hydrogen-containing silicone oil, hydroxy hydrogen-containing silicone oil and methyl silicone oil.
In the invention, one or a combination of a plurality of fluorine-containing polyacrylate, dimethyl cyclosiloxane and silicone oil is used as a water-resistant, sulfur-resistant and dust-resistant auxiliary agent to prepare a coating solution, and the coating solution is coated on catalyst powder or an integrally formed catalyst to form a water-resistant, sulfur-resistant and dust-resistant coating film, so that the stability of the catalyst in the atmosphere of simultaneous existence of water and sulfur dioxide is effectively improved; the method can treat various solid catalysts such as particles, honeycombs, plates and the like, and has a wide application range.
In one embodiment of the invention, the titanium dioxide is anatase titanium dioxide.
In one embodiment of the present invention, the ZSM-5 molecular sieve has a silica to alumina molar ratio of 20-200: 1.
in one embodiment of the present invention, the mole ratio of silica to alumina of the beta molecular sieve is 20-200: 1.
in a specific embodiment of the invention, in the composite carrier, the mass ratio of the titanium dioxide, the ZSM-5 molecular sieve and the beta molecular sieve is 100: (0.01-100): (0.01-100).
In one embodiment of the present invention, the molar ratio of V oxide, Cu oxide, Mn oxide in the active component is 100: (0.01-100): (0.01-100).
In one embodiment of the present invention, the molar ratio of Mo oxide, Cr oxide, Fe oxide, Co oxide, Ce oxide, and Ni oxide in the Co-agent is 100: (0.01-100): (0.01-100): (0.01-100): (0.01-100): (0.01-100).
In order to achieve the technical purpose, the invention also provides a preparation method of the low-temperature denitration catalyst, which comprises the following steps:
dissolving a precursor of an active component and a precursor of an active auxiliary agent in water, stirring and dissolving at room temperature or 30-60 ℃, and adding oxalic acid (to better disperse and dissolve the precursors) to form an impregnation solution; the mass of the oxalic acid is 0.001-1 time of the total mass of the precursor of the active component and the precursor of the active auxiliary agent;
soaking the carrier into the soaking solution, drying for 3-12 h at 60-110 ℃, and roasting for 3-12 h in an air atmosphere at 300-500 ℃ to obtain powder;
coating the powder or the formed powder in a manner of completely soaking in a solution of a water-resistant, sulfur-resistant and dust-resistant auxiliary agent directly or after the powder is formed, wherein the soaking time is 0.01h-24h (preferably 0.5h-12h), drying for 3h-72h at the temperature of 20-110 ℃, and roasting for 0h-12h (0 h is shown in the condition that roasting is not needed) at the temperature of 200-500 ℃ to obtain the low-temperature denitration catalyst.
The preparation method of the low-temperature catalyst comprises the step of preparing the impregnation liquid.
In a specific embodiment of the invention, the precursor of the active component is one or a combination of manganese salt, vanadium salt and copper salt;
specifically, the manganese salt is one or a combination of manganese nitrate, manganese sulfate, manganous chloride and manganous acetate;
specifically, the vanadium salt is one or a combination of more of ammonium metavanadate, vanadyl oxalate and vanadyl sulfate;
specifically, the copper salt is one or a combination of copper nitrate, copper chloride, copper sulfate and copper oxalate.
In a specific embodiment of the invention, the precursor of the adopted active assistant is a combination of two or more of iron salt, cobalt salt, cerium salt, molybdenum salt, chromium salt and nickel salt;
specifically, the iron salt is one or a mixture of at least two of ferric nitrate, ferric chloride, ferric sulfate and ferric phosphate;
specifically, the cobalt salt is one or a mixture of at least two of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt oxalate;
specifically, the cerium salt is one or a mixture of at least two of cerium nitrate, cerium sulfate and cerium chloride;
specifically, the molybdenum salt is one or a mixture of at least two of ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate and ammonium octamolybdate;
specifically, the chromium salt is one or a mixture of at least two of chromium nitrate, chromium chloride and chromium acetate;
specifically, the nickel salt is one or a mixture of at least two of nickel nitrate, nickel chloride and nickel acetate.
The preparation method of the low-temperature denitration catalyst comprises the step of mixing the impregnation liquid and the carrier. Mixing the impregnation liquid and the carrier by adopting an equal-volume impregnation method or an over-volume impregnation method; wherein, the carrier is evenly soaked in the soaking solution by equal volume of soaking; the carrier is soaked in the soaking solution after the volume soaking, the ultrasonic dispersion is carried out for 30min to 3h, the carrier is dried for 3h to 12h at the temperature of 60 ℃ to 110 ℃ after standing overnight, and the carrier is roasted for 3h to 12h in the air atmosphere at the temperature of 300 ℃ to 500 ℃ to obtain the powder.
Dipping a precursor of the carrier into the dipping solution, dropwise adding the dipping solution to the surface of the carrier at a slow speed, stirring properly after each dropwise adding until the surface color of the carrier is uniform, then continuously dropwise adding, and finally uniformly mixing the dipping solution and the carrier.
The preparation method of the low-temperature denitration catalyst also comprises the step of powder molding.
In one embodiment of the present invention, the powder forming may be honeycomb forming, and the forming process includes pugging, aging, pre-extrusion and extrusion forming, drying and roasting. The powder forming method specifically comprises the following steps:
dry-mixing the powder and the solid forming auxiliary agent, adding the liquid forming auxiliary agent for wet mixing, adding water and stirring to obtain a material;
fully mixing the materials (in a vacuum pug mill) and ageing for 6-48 h to obtain a formed blank;
extruding and molding the molded blank into a honeycomb shape to obtain a honeycomb-shaped blank;
and drying and calcining the honeycomb formed blank body to obtain honeycomb formed powder.
In one embodiment of the present invention, the drying includes two processes of primary drying and secondary drying. Wherein, the primary drying adopts a constant humidity and temperature mode. Wherein the temperature of primary drying is 30-70 ℃, the humidity is 10-95%, and the time is 12h-10 days. The temperature of the secondary drying is 70-110 ℃, and the time is 12-48 h
In one embodiment of the present invention, the solid forming aid and the liquid forming aid used are selected from a mixture of two or more of a reinforcing agent, an inorganic binder, an organic binder, a pore-forming agent and a lubricant;
specifically, the content of the reinforcing agent is 10-50% of the mass of the powder; the reinforcing agent is glass fiber or titanium dioxide.
Specifically, the content of the inorganic binder is 5-15% of the mass of the powder; the inorganic binder is preferably one or the combination of at least two of pseudo-boehmite, nitric acid, water glass and silica sol; the inorganic binder is preferably used in a molar ratio of 2-10: 1 and nitric acid.
Specifically, the content of the organic binder is 1-5% of the mass of the powder; the organic binder is preferably one or a combination of at least two of polyvinyl alcohol, hydroxypropyl methylcellulose, and polyethylene oxide.
Specifically, the content of the pore-forming agent is 8-10% of the mass of the powder; the pore-forming agent is preferably activated carbon or sesbania powder.
Specifically, the content of the lubricant is 10-15% of the mass of the powder; the lubricant is preferably glycerol. The low-temperature denitration catalyst comprises the step of preparing a coating liquid (a solution of a water-resistant, sulfur-resistant and dust-resistant auxiliary agent). The solute in the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent is mixed with the solvent to prepare the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent with the solute content of 0.5-80 percent (preferably 1-30 percent).
In a specific embodiment of the invention, the solvent used in the solution of the water-resistant sulfur-resistant dust-resistant additive is one or a combination of cyclohexane, n-heptane and ethanol. The solution of the water-resistant, sulfur-resistant and dust-resistant additive adopts solute of one or a combination of a plurality of fluorine-containing polyacrylate, dimethyl cyclosiloxane and silicone oil.
Specifically, the fluorine-containing polyacrylate is selected from one or a combination of more of hexafluorobutyl polyacrylate, hexafluorobutyl polymethacrylate, 2,2, 2-trifluoroethyl polymethacrylate, dodecafluoroheptyl polyacrylate, tridecafluorooctyl polymethacrylate, tridecafluorooctyl polyacrylate and perfluoroalkyl ethyl acrylate;
specifically, the dimethyl cyclosiloxane is selected from one or a combination of more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane;
specifically, the silicone oil is selected from one or more of methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxy silicone oil, ethyl hydrogen-containing silicone oil, hydroxy hydrogen-containing silicone oil and methyl silicone oil.
The preparation method of the low-temperature denitration catalyst comprises the step of coating a water-resistant, sulfur-resistant and dust-resistant coating film.
The preparation method specifically comprises the steps of directly soaking the powder or after the powder is formed, in a solution of a water-resistant, sulfur-resistant and dust-resistant auxiliary agent for 0.5-12 h, drying in the air for 10min-72h, drying at 20-110 ℃ for 3-12 h, and roasting at 200-500 ℃ for 0-12 h. According to the actual situation, the coated catalyst can be dried and then coated for multiple times by the same method.
The low-temperature denitration catalyst has high water-resistant and sulfur-resistant performance and smoke-resistant performance in low-temperature flue gas, and is suitable for selective catalytic reduction of nitrogen oxides in the low-temperature flue gas. For example, the SCR denitration catalyst can be used for catalyzing SCR denitration reaction of low-temperature flue gas (flue gas with the temperature lower than 300 ℃), and is particularly suitable for controlling the emission of nitrogen oxides of the low-temperature flue gas in garbage incinerators, glass, steel, coking coke ovens, petrochemical process heating furnaces, cement industry, alumina clinker kilns and the like.
The low-temperature denitration catalyst provided by the invention has the advantage that the activity reduction rate of the vanadium-titanium catalyst is obviously slowed down at low temperature in the presence of sulfur dioxide and water. The reaction conditions are harsh (laboratory simulated NH)3:1000ppm，NOx:1000ppm，O2:8％，SO2:250ppm-1000ppm，H2O:20％，N2Balance gas, temperature is 170 ℃, volume space velocity is 60000h-1The gas flow is 120mL/min) still has better water resistance, sulfur resistance and smoke dust resistance.
The preparation method of the low-temperature denitration catalyst has the advantages of easily obtained raw materials, simple preparation process, easy industrial amplification, easily obtained raw materials required by the coating liquid, simple preparation, less coating liquid loss at one time of coating, repeated use of the coating liquid, low cost, suitability for industrial amplification production and provision for subsequent industrial application.
Drawings
FIG. 1 is a comparison of the activities of the catalysts prepared in examples 1 to 4 under the same reaction conditions.
FIG. 2 is a graph showing the comparison of the activity of the catalysts prepared in example 2 and comparative example 1 under the same reaction conditions.
FIG. 3 is a comparison of the activities of the catalysts prepared in example 5 and comparative example 2 under the same reaction conditions.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a low-temperature denitration catalyst, which is prepared by the following steps:
0.113g of ammonium metavanadate and 0.11g of oxalic acid are weighed and added into a certain mass of water, stirred in a water bath at 60 ℃ until the ammonium metavanadate and the oxalic acid are dissolved uniformly, and 0.235g of ammonium molybdate tetrahydrate is added and dissolved and stirred continuously at 60 ℃ to form a uniform solution.
0.906g of copper nitrate trihydrate, 0.246g of manganese sulfate and dissolved are weighed and added into the solution to prepare impregnation liquid.
3g of HZSM-5 (the silica-alumina ratio is 50) and 5g of titanium dioxide are weighed and uniformly mixed to be used as a carrier, and the carrier is uniformly impregnated with the impregnation solution by adopting an impregnation method.
And (3) standing the impregnated powder overnight, drying the powder for 6h at 80 ℃, and roasting the powder for 3h at 500 ℃ in a muffle furnace to obtain the powder.
Tabletting the powder, crushing and sieving to 20-40 mesh. A40 mL beaker was charged with 5g of hexafluorobutyl polyacrylate and 40g of cyclohexane and stirred until uniform mixing occurred. And placing the powder on an iron wire filter screen with certain pores, soaking the powder in hexafluorobutyl acrylate solution for 5 hours, taking out the powder, standing the powder at room temperature for 12 hours, drying the powder at 110 ℃ for 3 hours, and roasting the powder at 300 ℃ for 3 hours to obtain the catalyst.
Test methods for catalyst performance:
the catalyst is loaded into a fixed bed reactor with the inner diameter of 8mm, and the simulated flue gas comprises the following components: NH (NH)3:1000ppm、NOx:1000ppm、O2:8％、SO2:250ppm、H2O:20％、N2Balance gas, temperature is 170 ℃, space velocity is 60000h-1The gas flow rate was 120 mL/min.
Example 2
The embodiment provides a low-temperature denitration catalyst, which is prepared by the following steps:
weighing 0.368g of nickel nitrate hexahydrate, 0.240g of chromium nitrate nonahydrate, 0.232g of ammonium metavanadate and 0.363g of ammonium molybdate tetrahydrate, adding 0.92g of oxalic acid and a proper amount of water, and fully dissolving in a water bath at 50 ℃ under stirring to form an impregnation solution.
1g of titanium dioxide and 2g of beta zeolite (the silicon-aluminum ratio is 38) are weighed and fully mixed, and the impregnation liquid is uniformly impregnated on the carrier by an impregnation method.
And (3) standing the impregnated powder overnight, drying the powder for 6h at 80 ℃, and roasting the powder for 3h at 500 ℃ in a muffle furnace to obtain the powder.
Tabletting the powder, crushing and sieving to 20-40 mesh. A40 mL beaker was charged with 10g of tridecafluorooctyl polymethacrylate and 20g of cyclohexane and stirred until uniform mixing occurred. Placing the powder on an iron wire filter screen with certain pores, soaking the powder in a solution of the poly (tridecyl octyl methacrylate) for 12 hours, taking out the powder, standing the powder for 12 hours at room temperature, drying the powder for 3 hours at 110 ℃, and roasting the powder for 3 hours at 300 ℃. The catalyst was obtained and tested for its performance as in example 1.
Example 3
The embodiment provides a low-temperature denitration catalyst, which is prepared by the following steps:
weighing 0.256g of cobalt nitrate hexahydrate, 0.680g of copper nitrate trihydrate, 0.570g of cerium nitrate hexahydrate, 0.232g of ammonium metavanadate and 0.363g of ammonium molybdate tetrahydrate, adding 0.92g of oxalic acid, adding a proper amount of water, and stirring in a water bath at 40 ℃ to fully dissolve to form an impregnation solution.
2.5g of TiO are weighed2And 0.5g of beta zeolite (the ratio of silicon to aluminum is 25) are fully mixed, the impregnating solution and the carrier are mixed into slurry by adopting an over-volume impregnation method, and ultrasonic dispersion is carried out for 2 hours.
Standing overnight, drying at 110 deg.C for 10h, and calcining in muffle furnace at 500 deg.C for 5h to obtain powder.
Tabletting the powder, crushing and sieving to 20-40 mesh. A40 mL beaker was taken and 10g of silicone oil and 40g of n-heptane were added and stirred until uniform mixing occurred. Placing the powder on an iron wire filter screen with certain pores, soaking in the coating liquid for 30min, taking out, standing at room temperature for 20min, drying at 110 ℃ for 1h, then soaking in the coating liquid for 30min again, repeating the steps twice, and finally drying at 110 ℃ for 3h to obtain the catalyst. The evaluation conditions were as in example 1.
Example 4
The embodiment provides a low-temperature denitration catalyst, which is prepared by the following steps:
0.193g of ammonium metavanadate, 0.08g of cobalt acetate and 0.193g of oxalic acid are weighed and added into a certain mass of water, stirred in a water bath at 60 ℃ until the ammonium metavanadate, the cobalt acetate and the oxalic acid are dissolved uniformly, and 0.368g of ammonium molybdate tetrahydrate is added and dissolved continuously at 60 ℃ to form uniform impregnation liquid.
4.44g of TiO were weighed2(anatase type) and 1.3g of HZSM-5, uniformly impregnating the carrier with the impregnation liquid in equal volume, and uniformly stirring.
Standing overnight, drying at 110 deg.C for 12h, and calcining in muffle furnace at 500 deg.C for 5h to obtain powder.
Tabletting the powder, crushing and sieving to 20-40 mesh. A40 mL beaker was charged with 5g hexamethylcyclotrisiloxane and 30g cyclohexane and stirred until mixed well. And placing the powder on an iron wire filter screen with certain pores, soaking the powder in the coating liquid for 30min, taking out the powder, standing the powder at room temperature for 10min, and drying the powder at 110 ℃ for 3h to obtain the catalyst.
Example 5
The embodiment provides a low-temperature denitration catalyst, which is prepared by the following steps:
31.42g of ferric nitrate nonahydrate, 19.76g of manganese nitrate solution (50 wt%) and 15.14g of cerous nitrate hexahydrate are weighed and dissolved in 68g of deionized water to prepare a uniform solution.
30.08g of ammonium metavanadate, 51.9g of ammonium molybdate tetrahydrate and 62.16g of oxalic acid are weighed into the solution, and stirred in a water bath at 50 ℃ for 2 hours until the solution is dissolved uniformly to form impregnation liquid.
120g of TiO are weighed2(anatase type) and 96g of HZSM-5, and uniformly impregnating the carrier with the impregnating solution in equal volume and stirring uniformly.
Standing overnight, drying at 110 deg.C for 12h, and calcining in muffle furnace at 500 deg.C for 5h to obtain powder.
Weighing 100g of powder, and sequentially adding 6g of pseudo-boehmite, 32.6g of silica sol and 20g of dilute nitric acid (HNO)310 percent of sesbania powder and 8g of sesbania powder, then mechanically mixing, sequentially adding 12.5g of glass fiber and 11.6g of glycerol, continuously mechanically mixing until the mixture is uniform, ageing for 24 hours, and then extruding into a honeycomb catalyst with the diameter of 18mm by using a hydraulic forming machine. Then drying in shade at room temperature for 24h, drying at 60 ℃ and 50% humidity for 6h, then drying at 120 ℃ for 6h, and roasting at 500 ℃ for 12 h.
Preparing a solution of dodecamethylcyclohexasiloxane and cyclohexane according to the mass ratio of 1:5, and ensuring that the powder can be completely immersed. Soaking a certain volume of the formed powder into a dodecamethylcyclohexasiloxane solution for 30min, taking out, standing at room temperature for 20min, drying at 110 ℃ for 1h, then soaking into the dodecamethylcyclohexasiloxane solution again for 30min, taking out, standing for 20min, drying at 110 ℃ for 3h, and roasting at 250 ℃ for 12 h. The catalyst is obtained.
The catalyst evaluation conditions were: NOx:1000ppm、NH3:1000ppm、O2:8％、SO2:250ppm、H 220 percent of O, 1.89L/min of flow rate and 8000h of volume space velocity-1。
Example 6
The preparation method of the catalyst is the same as that of example 5, 15g of the formed honeycomb catalyst is taken, 450mg of smoke dust collected from coal-fired boiler flue gas is taken and dissolved in 5g of deionized water, then the mixture is fully and uniformly stirred, a dropper is used for dropwise adding the mixture to the surface of the honeycomb catalyst, the surface of the honeycomb catalyst is uniformly dropwise added, then the honeycomb catalyst is dried in the shade, then the honeycomb catalyst is dried at 120 ℃ for 6h, and is roasted at 400 ℃ for 12h, and the catalyst with the smoke dust attached to the surface is obtained.
Comparative example 1
The powder prepared in example 2 was evaluated directly under the same conditions without coating with polytrifluorooctyl polymethacrylate and compared with the results of example 2.
Comparative example 2
The shaped catalyst prepared in example 5 was evaluated directly under the same conditions without coating decadimethylcyclohexasiloxane and compared with the results of example 5.
Comparative example 3
The support being TiO only2The other catalysts were prepared in the same manner as in example 5 and evaluated under the same reaction conditions as in example 5.
Comparative example 4
The support was only HZSM-5, and other catalysts were prepared in the same manner as in example 5, and evaluated under the same reaction conditions as in example 5.
Comparative example 5
The procedure and method were exactly the same as in example 6 except that no water-resistant, sulfur-resistant, and soot-resistant coating film was used in the preparation of the honeycomb catalyst, i.e., no treatment with decamethylcyclohexasiloxane and cyclohexane solution was used.
In order to investigate the smoke resistance of the catalyst prepared by the technology, smoke in the smoke of a coal-fired boiler is dissolved in water, stirred to form a uniform mixture, then the uniform mixture is dripped on the surface of a formed honeycomb catalyst, and then the uniform mixture is dried and roasted to investigate the denitration performance of the catalyst. The result proves that the low-temperature denitration catalyst prepared by the invention has good smoke resistance.
TABLE 1 deposition amount of ammonium sulfate salt on the surface of catalyst after the catalyst was reacted for 100 hours
TABLE 2 NO after 100 hours of reaction of examples 5 and 6 with comparative example 8xConversion rate and deposition amount of ammonium sulfate salt
As can be seen from FIGS. 1, 2, 3 and Table 1, examples 1-5 are under severe flue gas conditions (170 ℃ SO)2:250ppm、H 220 percent of O) has good stability, while the activity of the catalyst is obviously reduced under the same smoke test condition in comparative example 1 and comparative example 2.
As can be seen from the data of the reaction time of 100 hours in table 1, the deposition amount of ammonium sulfate in the catalyst after 100 hours of reaction of the catalysts of examples 1 to 5 prepared by the preparation method of the present invention is significantly smaller than that of the catalyst of the comparative example, which fully indicates that the formation of ammonium sulfate on the surface of the catalyst can be greatly reduced by using the composite carrier and the water-resistant, sulfur-resistant and dust-resistant assistant, so as to improve the denitration activity and stability of the catalyst.
As can be seen from Table 2, the activity of the catalyst of example 6 after soot impregnation is comparable to the activity of the catalyst of example 5 which is not poisoned by soot, with respect to NOxOnly 7% reduction, NO after 100 hours of reactionxThe activity is reduced by only 3 percent, and the deposition amounts of the thiamine salt on the surfaces of the catalyst in the embodiment 5 and the catalyst in the embodiment 6 are not much different and are respectively less than 0.01g, and the results show that the catalyst in the embodiment 6 has good water-resistant, sulfur-resistant and smoke-resistant performances and good stability. In contrast, comparative example 5, which did not employ a water-resistant, sulfur-resistant, smoke-resistant protective film, had 73% NO in spite of the initial activity of the reactionxConversion, but after 100 hours of reaction, NOxThe conversion rate was reduced by half and the amount of deposition of ammonium sulfate salt was increased by about 30 times.
Claims (10)
1. A low-temperature denitration catalyst comprises a carrier, an active component, an active assistant and a water-resistant, sulfur-resistant and dust-resistant coating film;
wherein the carrier is a composite carrier of titanium dioxide and a molecular sieve; the molecular sieve is a ZSM-5 molecular sieve and/or a beta molecular sieve;
the active component is one or a combination of more of Cu oxide, Mn oxide and V oxide; the mass of the active component accounts for 0.001-0.6 of the mass of the carrier;
the active additive is a combination of two or more of Ni oxide, Cr oxide, Fe oxide, Co oxide, Ce oxide and Mo oxide; the mass of the active auxiliary agent accounts for 0.001-0.6 of the mass of the carrier;
the mass of the water-resistant, sulfur-resistant and dust-resistant coating film accounts for 0.001-0.3 of the mass of the catalyst.
2. The low-temperature denitration catalyst according to claim 1, wherein the water-resistant, sulfur-resistant and dust-resistant coating film is obtained by coating a solution of a water-resistant, sulfur-resistant and dust-resistant auxiliary on the surface of the catalyst; the solute of the solution of the water-resistant, sulfur-resistant and dust-resistant additive is one or a combination of a plurality of fluorine-containing polyacrylate, dimethyl cyclosiloxane and silicone oil;
preferably, the titanium dioxide is anatase titanium dioxide;
preferably, the ZSM-5 molecular sieve has a silica to alumina molar ratio of 20-200: 1;
preferably, the mole ratio of silicon to aluminum of the beta molecular sieve is 20-200: 1;
more preferably, the mass ratio of the titanium dioxide, the ZSM-5 molecular sieve and the beta molecular sieve is 100: (0.01-100): (0.01-100).
3. The low-temperature denitration catalyst according to claim 1, wherein the molar ratio of the V oxide, the Cu oxide and the Mn oxide in the active component is 100: (0-100): (0-100);
preferably, the molar ratio of Mo oxide, Cr oxide, Fe oxide, Co oxide, Ce oxide and Ni oxide in the active additive is 100: (0.01-100): (0.01-100): (0.01-100): (0.01-100): (0.01-100).
4. The preparation method of the low-temperature denitration catalyst according to any one of claims 1 to 3, comprising the steps of:
dissolving a precursor of the active component and a precursor of the active auxiliary agent in water, stirring and dissolving at room temperature or 30-60 ℃, and adding oxalic acid to form an impregnation solution; the mass of the oxalic acid is 0.001-1 time of the total mass of the precursor of the active component and the precursor of the active auxiliary agent;
soaking a carrier into the soaking solution, drying for 3-12 h at 60-110 ℃, and roasting for 3-12 h in an air atmosphere at 300-500 ℃ to obtain powder;
coating the powder or the formed powder in a completely soaking mode in a solution of a water-resistant, sulfur-resistant and dust-resistant auxiliary agent directly or after the powder is formed, wherein the soaking time is 0.01h-24h, and the volume ratio of the formed powder or the powder to the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent is 1: 0.5-100, drying for 3-72 h at 20-110 ℃, and roasting for 0-12 h at 200-500 ℃ to obtain the low-temperature denitration catalyst.
5. The preparation method of claim 4, wherein the mass content of solute in the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent is 0.5% -80%;
the solvent adopted by the solution of the water-resistant, sulfur-resistant and dust-resistant auxiliary agent is cyclohexane, n-heptane or ethanol;
the solution of the water-resistant sulfur-resistant dust-resistant auxiliary agent adopts a solute which is one or a combination of a plurality of fluorine-containing polyacrylate, dimethyl cyclosiloxane and silicone oil.
6. The preparation method of claim 5, wherein the fluorine-containing polyacrylate is selected from one or more of hexafluorobutyl polyacrylate, hexafluorobutyl polymethacrylate, 2, 2-trifluoroethyl polymethacrylate, dodecafluoroheptyl polyacrylate, tridecafluorooctyl polymethacrylate, tridecafluorooctyl polyacrylate and perfluoroalkyl ethyl acrylate;
preferably, the dimethyl cyclosiloxane is selected from one or a combination of more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane;
preferably, the silicone oil is selected from one or more of methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, methyl chlorphenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxyl silicone oil, ethyl hydrogen-containing silicone oil, hydroxyl hydrogen-containing silicone oil and methyl silicone oil.
7. The preparation method of claim 4, wherein the precursor of the active component is one or a combination of manganese salt, vanadium salt and copper salt;
preferably, the manganese salt is one or a combination of manganese nitrate, manganese sulfate, manganous chloride and manganous acetate;
preferably, the vanadium salt is one or a combination of more of ammonium metavanadate, vanadyl oxalate and vanadyl sulfate;
preferably, the copper salt is one or a combination of more of copper nitrate, copper chloride, copper sulfate and copper oxalate;
the precursor of the active auxiliary agent is a combination of two or more of ferric salt, cobalt salt, cerium salt, molybdenum salt, chromium salt and nickel salt;
preferably, the iron salt is one or a mixture of at least two of ferric nitrate, ferric chloride, ferric sulfate and ferric phosphate;
preferably, the cobalt salt is one or a mixture of at least two of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt oxalate;
preferably, the cerium salt is one or a mixture of at least two of cerium nitrate, cerium sulfate and cerium chloride;
preferably, the molybdenum salt is one or a mixture of at least two of ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate and ammonium octamolybdate;
preferably, the chromium salt is one or a mixture of at least two of chromium nitrate, chromium chloride and chromium acetate;
preferably, the nickel salt is one or a mixture of at least two of nickel nitrate, nickel chloride and nickel acetate.
8. The production method according to claim 4, wherein the powder molding includes the steps of:
dry-mixing the powder and the solid forming auxiliary agent, adding the liquid forming auxiliary agent for wet mixing, adding water and stirring to obtain a material;
fully mixing and refining the materials, and ageing for 6-48 h to obtain a formed blank;
extruding and molding the molded blank into a honeycomb shape to obtain a honeycomb-shaped blank;
drying and calcining the honeycomb-shaped forming blank to obtain honeycomb-shaped forming powder;
preferably, the drying comprises two procedures of primary drying and secondary drying; the temperature of primary drying is 30-70 ℃, the humidity is 10-95%, and the time is 12h-10 days; the temperature of the secondary drying is 70-110 ℃, and the time is 12-48 h.
9. The production method according to claim 8, wherein the solid forming aid and the liquid forming aid are selected from a mixture of two or more of a reinforcing agent, an inorganic binder, an organic binder, a pore-forming agent, and a lubricant;
preferably, the content of the reinforcing agent is 10-50% of the mass of the powder; the reinforcing agent is glass fiber or titanium dioxide;
preferably, the content of the inorganic binder is 5-15% of the mass of the powder; the inorganic binder is one or the combination of at least two of pseudo-boehmite, nitric acid, water glass and silica sol;
preferably, the content of the organic binder is 1-5% of the mass of the powder; the organic binder is one or the combination of at least two of polyvinyl alcohol, hydroxypropyl methylcellulose, methylcellulose and polyethylene oxide;
preferably, the content of the pore-forming agent is 8-10% of the mass of the powder; the pore-forming agent is activated carbon or sesbania powder;
preferably, the content of the lubricant is 10-15% of the mass of the powder; the lubricant is glycerol.
10. Use of the low temperature denitration catalyst according to any one of claims 1 to 3 for selective catalytic reduction of nitrogen oxides in low temperature flue gas, particularly for nitrogen oxide emission control in low temperature flue gas of garbage incinerators, glass, steel, coke ovens, furnaces for petrochemical processes, cement industry and alumina clinker kilns.
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| CN117427628A (en) * | 2023-10-12 | 2024-01-23 | 杭州玺富环保科技有限公司 | Catalytic slurry for anti-falling water-resistant ceramic fiber filter tube, preparation method and application |
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