CN113908842B - Denitration catalyst for CO-SCR flue gas denitration and preparation method thereof - Google Patents

Denitration catalyst for CO-SCR flue gas denitration and preparation method thereof Download PDF

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CN113908842B
CN113908842B CN202111214834.9A CN202111214834A CN113908842B CN 113908842 B CN113908842 B CN 113908842B CN 202111214834 A CN202111214834 A CN 202111214834A CN 113908842 B CN113908842 B CN 113908842B
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catalyst
denitration
hours
mullite
carrier
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CN113908842A (en
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于锋
李文健
但建明
代斌
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Shihezi University
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B01J35/56—
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/204—Carbon monoxide

Abstract

The invention relates to a denitration catalyst for CO-SCR flue gas denitration and a preparation method thereof. The preparation method of the denitration catalyst for CO-SCR flue gas denitration comprises the following steps: (1) preparing a catalyst powder; (2) Adding an additive and the catalyst powder into water, and uniformly mixing to obtain slurry; the additive is an inorganic binder, an organic polymer solution and a surfactant; (3) And (3) immersing the pretreated honeycomb mullite carrier in the slurry, and then drying and calcining to obtain the denitration catalyst for CO-SCR flue gas denitration. According to the denitration catalyst for CO-SCR flue gas denitration and the preparation method thereof, the powder catalyst is mixed with the additive with adhesiveness, so that the adhesiveness of the catalyst coating on the mullite carrier is enhanced, and the coating catalyst with low cost and high adhesiveness is obtained.

Description

Denitration catalyst for CO-SCR flue gas denitration and preparation method thereof
Technical Field
The invention belongs to the technical field of CO-SCR flue gas denitration, and particularly relates to a denitration catalyst for CO-SCR flue gas denitration and a preparation method thereof.
Background
Fossil energy sources such as coal, petroleum and natural gas can generate a lot of nitrogen oxides which are harmful to the environment and human body when being used, such as common nitrous oxide, nitric Oxide (NO) and dioxygenNitrogen (NO) 2 ) Etc. The nitrogen oxides exist in a large amount in the environment, so that the influence on animals and plants can be caused, the visibility of air can be reduced, the trip safety of people is seriously influenced, meanwhile, an ozone layer can be destroyed, the environment is polluted by acid rain, the immune system, the respiratory system, the cardiovascular and cerebrovascular systems and the like of a human body can be endangered when the content of the nitrogen oxides in the air is too high, and the death of the human body can be caused when the content of the nitrogen oxides in the air is serious.
More than 95% of nitrogen oxides in the air are artificially produced and mainly comprise the exhaust of flue gas of power plants, cement kilns and the like. The selective catalytic reduction method is widely used for removing NO because of the advantages that nitrogen oxides can be removed at a low temperature and the amount of the required reducing agent is relatively small. CO is used as one of the components of the tail gas, and the CO-SCR flue gas denitration can save the production, transportation and storage costs and can generate harmless N by a selective catalytic reduction method 2 And CO 2 。
The existing preparation methods of the monolithic catalyst for factory flue gas denitration mainly comprise two methods, namely a honeycomb monolithic denitration catalyst prepared by loading active components on the surface of a cordierite carrier and a honeycomb monolithic denitration catalyst prepared by adopting an extrusion molding method. When the integral denitration catalyst is prepared by adopting a method of loading active components on the surface of a cordierite carrier, the adhesion of the active components is poor, the active components are easy to fall off, and the denitration efficiency is reduced. The extrusion molding method is adopted, so that the amount of the required active components is too much, the production cost is high, the honeycomb monolithic catalyst is easy to crack during calcination, the honeycomb monolithic catalyst is difficult to manufacture, the cost is high, and the catalyst cannot achieve higher low-temperature denitration efficiency.
In view of the above, the invention provides a new denitration catalyst for CO-SCR flue gas denitration and a preparation method thereof, and the denitration catalyst has the advantages of strong adhesiveness and low cost.
Disclosure of Invention
The invention aims to provide a preparation method of a denitration catalyst for CO-SCR flue gas denitration, which is characterized in that a powder catalyst with an active component and an additive with adhesiveness are mixed and then coated on a mullite carrier, so that adhesiveness is improved, and meanwhile, the problem that mullite serving as the carrier is easy to crack in a low-temperature calcination process is solved, so that production cost is reduced.
In order to achieve the above purpose, the technical scheme adopted is as follows:
the preparation method of the denitration catalyst for CO-SCR flue gas denitration comprises the following steps:
(1) Preparing catalyst powder;
(2) Adding an additive and the catalyst powder into water, and uniformly mixing to obtain slurry; the additive is an inorganic binder, an organic polymer solution and a surfactant;
(3) And (3) immersing the pretreated honeycomb mullite carrier in the slurry, and then drying and calcining to obtain the denitration catalyst for CO-SCR flue gas denitration.
Further, in the step (1), a coprecipitation method is adopted to prepare catalyst powder;
the slurry in the step (2) comprises the following components in percentage by mass: 50-70% of water, 10-20% of additive and 20-40% of catalyst powder;
the pretreatment in the step (3) is as follows: soaking the cleaned mullite carrier in a mixed solution containing urea and aluminum salt for 24 hours, drying at 80 ℃, and calcining.
Still further, in the step (1), cerium salt and copper salt are adopted as raw materials, and the molar ratio of Ce to Cu is 6.67:1;
in the step (2), the adhesive is silica sol, the organic polymer comprises polyethylene glycol and sodium carboxymethyl cellulose, and the surfactant is tween-20;
in the step (3), the aluminum salt is aluminum nitrate or aluminum sulfate.
Still further, in the step (1), the copper salt is at least one of copper sulfate, copper chloride and copper nitrate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium sulfate;
in the step (2), the mass ratio of polyethylene glycol, acidic silica gel, sodium carboxymethylcellulose and tween-20 is 8:10:8:1, a step of;
in the mixed solution in the step (3), urea is 3.335mol/L, and aluminum nitrate is 1mol/L.
Still further, in the step (1), the cerium salt is cerium nitrate, and the copper salt is copper nitrate;
in the step (2), the mass fraction of the slurry is 30-40%;
in the step (3), the slurry is immersed for 2 hours.
Still further, in the step (2), the mass fraction of the slurry is 30%;
in the step (3), the drying temperature is 80 ℃ and the time is 48 hours; the calcination temperature was 550℃and the time was 4 hours.
Still further, in the step (2), the mixing temperature is 60-70 ℃;
in the step (3), the weight increase of the pretreated mullite carrier is not less than 5% of the mass of the carrier which is not pretreated;
the mass of the denitration catalyst is 110-130% of the mass of the pretreated mullite carrier.
The invention also aims to provide a denitration catalyst for CO-SCR flue gas denitration, which is prepared by adopting the method and has the advantages of low cost, difficult falling off and good low-temperature denitration performance.
It is still another object of the present invention to provide the use of the above denitration catalyst, which performs CO selective catalytic reduction.
Further, the temperature of the CO selective catalytic reduction reaction is 150-300 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the cerium-based catalyst prepared by the invention has high denitration activity at 150-300 ℃, and is suitable for CO denitration under the condition of low temperature oxygen-free or low oxygen.
2. The denitration catalyst disclosed by the invention has the advantages that the loading rate of the catalyst active components on the carrier is higher, the airflow resistance strength of the coating is high, and the mechanical strength of the carrier is high.
3. The preparation method is simple, convenient to operate and low in production cost.
4. According to the technical scheme, the powder catalyst with the active components and the additive with the adhesiveness are mixed and then coated on the mullite carrier, so that the adhesiveness is improved, and meanwhile, the problem that the mullite serving as the carrier is easy to crack in the low-temperature calcination process (lower than 600 ℃) is solved, and the mullite serving as the integral catalyst carrier is realized, so that the production cost can be reduced.
Detailed Description
In order to further illustrate a denitration catalyst for denitration of CO-SCR flue gas and a preparation method thereof according to the present invention, to achieve the intended purpose of the present invention, the following description will be given in detail with reference to the preferred embodiments, with reference to the specific embodiments, structures, features and effects of a denitration catalyst for denitration of CO-SCR flue gas according to the present invention. In the following description, different "an embodiment" or "an embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
The following describes in further detail a denitration catalyst for denitration of CO-SCR flue gas and a preparation method thereof, with reference to specific examples:
the invention relates to a method for coating a powder catalyst on a mullite honeycomb carrier and application thereof. The preparation method comprises the steps of coating a powder catalyst with active components on a 15 cm-15 cm mullite honeycomb carrier under the action of slurry to obtain a formed denitration carrier with holes and surface layers attached with oxide active components such as copper, cerium, aluminum and the like. The preparation process needs to pretreat the mullite carrier; then, preparing slurry by using polyethylene glycol, sodium carboxymethyl cellulose, acidic silica gel, tween-20 and a powder catalyst, and finally, performing dip coating by using a die. The integrally formed catalyst has stronger mechanical strength and airflow sweeping strength after being dried and calcined, and the powder catalyst prepared by adopting cerium nitrate and copper nitrate through a coprecipitation method is coated on a mullite carrier and then applied to CO-SCR, so that the integrally formed catalyst has excellent low-temperature denitration performance.
The technical scheme of the invention is as follows:
the preparation method of the denitration catalyst for CO-SCR flue gas denitration comprises the following steps:
(1) Preparing catalyst powder;
(2) Adding an additive and the catalyst powder into water, and uniformly mixing to obtain slurry; the additive is an inorganic binder, an organic polymer solution and a surfactant;
(3) And (3) immersing the pretreated honeycomb mullite carrier in the slurry, and then drying and calcining to obtain the denitration catalyst for CO-SCR flue gas denitration.
Preferably, in the step (1), a coprecipitation method is adopted to prepare catalyst powder;
the slurry in the step (2) comprises the following components in percentage by mass: 50-70% of water, 10-20% of additive and 20-40% of catalyst powder;
the pretreatment in the step (3) is as follows: soaking the cleaned mullite carrier in a mixed solution containing urea and aluminum salt for 24 hours, drying at 80 ℃, and calcining.
Further preferably, in the step (1), cerium salt and copper salt are adopted as raw materials, and the molar ratio of Ce to Cu is 6.67:1;
in the step (2), the adhesive is silica sol, and is used as an inorganic adhesive, the organic polymer comprises polyethylene glycol and sodium carboxymethyl cellulose which are respectively used as a mixture and a tackifier, and the surfactant is Tween-20 and is used as a surfactant;
in the step (3), the aluminum salt is aluminum nitrate or aluminum sulfate.
Further preferably, in the step (1), the copper salt is at least one of copper sulfate, copper chloride and copper nitrate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium sulfate;
in the step (2), the mass ratio of polyethylene glycol, acidic silica gel, sodium carboxymethylcellulose and tween-20 is 8:10:8:1, a step of;
in the mixed solution in the step (3), urea is 3.335mol/L, and aluminum nitrate is 1mol/L.
Further preferably, in the step (1), the cerium salt is cerium nitrate, and the copper salt is copper nitrate;
in the step (2), the mass fraction of the slurry is 30-40%;
in the step (3), the slurry is immersed for 2 hours.
Further preferably, in the step (2), the mass fraction of the slurry is 30%;
in the step (3), the drying temperature is 80 ℃ and the time is 48 hours; the calcination temperature was 550℃and the time was 4 hours.
Further preferably, in the step (2), the mixing temperature is 60-70 ℃;
in the step (3), the weight increase of the pretreated mullite carrier is not less than 5% of the mass of the carrier which is not pretreated;
the mass of the denitration catalyst is 110-130% of the mass of the pretreated mullite carrier.
Example 1.
The specific operation steps are as follows:
(1) Dissolving Cu salt and Ce salt in water to form a metal salt solution, preparing catalyst powder by a coprecipitation method, crushing to more than 100 meshes by a crusher, and sieving for later use.
The copper salt adopts at least one of copper sulfate, copper chloride and copper nitrate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium sulfate, and the molar ratio of Ce to Cu is 6.67:1.
In the preparation of the catalyst powder by the coprecipitation method: stirring the metal salt solution, then dropwise adding a precipitant (one of sodium hydroxide and ammonia water is adopted as the precipitant) until the pH value is 9-11, stirring, standing for precipitation, suction filtration, drying and calcining to obtain the powder catalyst.
Preferably, the catalyst prepared by adopting cerium nitrate and copper nitrate has the best catalytic performance and is the best choice.
(2) Mixing the additive and water uniformly, and adding the catalyst powder to obtain slurry. The slurry comprises the following components in percentage by mass: 50-70 percent of additive: 10-20 percent of catalyst: 20-40%, the sum of the components is 100%.
The additive is inorganic binder, organic polymer solution and surfactant.
Preferably, the binder is silica sol, the organic polymer comprises polyethylene glycol and sodium carboxymethyl cellulose, the surfactant is Tween-20, and the water is purified water.
The adding sequence is as follows: sequentially adding polyethylene glycol, acidic silica gel, sodium carboxymethyl cellulose and tween-20 into a constant temperature interlayer stirring pot with a certain amount of purified water at 60-70 ℃, stirring uniformly, adding a certain amount of powder catalyst, and stirring for 6 hours for later use; during the addition, each material was stirred for 30min after entering until the next material was added after dissolution.
The slurry concentration is 30-40wt%.
Further preferably, the mass ratio of polyethylene glycol, acidic silica gel, sodium carboxymethyl cellulose and tween-20 is 8:10:8:1.
(3) Washing the mullite carrier with ultrasonic water for more than 30min, drying, soaking in a mixed solution containing urea and aluminum salt for 24h, drying at 80 ℃ and calcining to obtain the pretreated mullite honeycomb carrier.
The aluminum salt may be at least one of aluminum nitrate and aluminum sulfate.
The mixed solution is formed by mixing urea solution and aluminum salt solution according to the volume ratio of 1:1, and the mixing process needs to be stirred for 6 hours at normal temperature so as to achieve the purpose of fully dissolving and uniformly mixing.
The quality of the coating on the mullite carrier after drying and calcining is not less than 5 weight percent of the mullite carrier. I.e. the weight gain of the pretreated mullite carrier is not lower than 5 percent of the mass of the carrier which is not pretreated.
Preferably, the aluminum salt is aluminum nitrate;
the urea in the mixed solution is 3.335mol/L, and the aluminum nitrate is 1mol/L.
(4) Placing the pretreated mullite honeycomb carrier into an iron mold box with the length of 20cm and the length of 20cm, injecting prepared slurry into the iron mold box, covering the mullite carrier, soaking for 2 hours, drying at 80 ℃ for 48 hours, and calcining at 550 ℃ for 4 hours to obtain the honeycomb shaped denitration catalyst carrier.
The mass of the denitration catalyst is 110-130% of the mass of the pretreated mullite carrier.
Example 2.
The specific operation steps are as follows:
(1) By Al (NO) 3 ) 3 ·9H 2 And (3) preparing an aluminum salt solution with the volume of 1L and 2mol/L by O, preparing a urea solution with the volume of 1L and 6.67mol/L, and adding the two solutions into a sandwich stirring pot and stirring for 4 hours at normal temperature. And pouring the uniformly stirred mixed solution into an iron mold box with the length of 20cm and the length of 20cm, soaking the mullite honeycomb carrier for 24 hours, drying at 80 ℃, and calcining to obtain the pretreated mullite carrier (the weight increase of the pretreated mullite carrier is not less than 5% of the mass of the carrier which is not subjected to pretreatment).
(2) 241.6g of Cu (NO) 3 ) 2 ·3H 2 O and 2896.25g of Ce (NO 3 ) 3 ·6H 2 O was added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. Adding 1mol/L sodium hydroxide solution to adjust the pH to 10-11, stirring for 4 hours, standing for 24 hours, filtering to neutrality with purified water, filtering with ethanol for 30 minutes, drying the filtered solid at 80 ℃, calcining for 4 hours at 550 ℃ with a muffle furnace, pulverizing, and sieving to 100 meshes to obtain the powder catalyst.
(3) 6kg of purified water is taken in a sandwich stirring pot, stirring is started after the temperature of an oil bath is raised to 70 ℃, 148.15g of polyethylene glycol (the molar mass is 6000), 148.15g of sodium carboxymethylcellulose (the viscosity is 600-3000), 185.19g of acidic silica sol (the mass fraction is 30%) and 18.52g of tween-20 are sequentially taken and mixed, and each substance is added until the substance is dissolved in the process of adding, and then the next substance is added. Finally, 1kg of powder catalyst is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry, wherein the concentration of the slurry is 20%, and the pH value is 3.6.
(4) Placing the mullite honeycomb carrier into a mould with the thickness of 20cm and the thickness of 20cm, pouring the prepared slurry into a mould box, and soaking for 2 hours;
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24 hours, then heating to 550 ℃ in a muffle furnace at a speed of 10 ℃/min, and calcining for 4 hours to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the mass after coating is increased by 15 percent (namely, the mass of the denitration catalyst is 115 percent of the mass of the pretreated mullite carrier).
Example 3.
The specific operation steps are as follows:
(1) By Al (NO) 3 ) 3 ·9H 2 And (3) preparing an aluminum salt solution with the volume of 1L and 2mol/L by O, preparing a urea solution with the volume of 1L and 6.67mol/L, and adding the two solutions into a sandwich stirring pot and stirring for 4 hours at normal temperature. And pouring the uniformly stirred mixed solution into an iron mold box with the length of 20cm and the length of 20cm, soaking the mullite honeycomb carrier for 24 hours, drying at 80 ℃, and calcining to obtain the pretreated mullite carrier (the weight increase of the pretreated mullite carrier is not less than 5% of the mass of the carrier which is not subjected to pretreatment).
(2) 241.6g of Cu (NO) 3 ) 2 ·3H 2 O and 2896.25g of Ce (NO 3 ) 3 ·6H 2 O was added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. Adding 1mol/L sodium hydroxide solution to adjust the pH to 10-11, stirring for 4 hours, standing for 24 hours, filtering to neutrality with purified water, filtering with ethanol for 30 minutes, drying the filtered solid at 80 ℃, calcining for 4 hours at 550 ℃ with a muffle furnace, pulverizing, and sieving to 100 meshes to obtain the powder catalyst.
(3) 4926g of purified water is taken in a sandwich stirring pot, stirring is started after the temperature of an oil bath is raised to 70 ℃, 197.53g of polyethylene glycol (molar mass is 6000), 197.53g of sodium carboxymethylcellulose (viscosity is 600-3000), 246.91g of acidic silica sol (mass fraction is 30%), 24.70g of tween-20 are sequentially taken and mixed, and each substance is added until the substance is dissolved in the process of adding, and then the next substance is added. Finally, 1kg of powder catalyst is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry, wherein the concentration of the slurry is 25%, and the pH value is 4.
(4) The mullite honeycomb carrier is placed into a mold with the thickness of 20cm and the thickness of 20cm, and then the prepared slurry is poured into a mold box and soaked for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24 hours, then heating to 550 ℃ in a muffle furnace at a speed of 10 ℃/min, and calcining for 4 hours to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the mass after coating is increased by 17 percent (namely, the mass of the denitration catalyst is 117 percent of the mass of the pretreated mullite carrier).
Example 4.
The specific operation steps are as follows:
(1) By Al (NO) 3 ) 3 ·9H 2 And (3) preparing an aluminum salt solution with the volume of 1L and 2mol/L by O, preparing a urea solution with the volume of 1L and 6.67mol/L, and adding the two solutions into a sandwich stirring pot and stirring for 4 hours at normal temperature. And pouring the uniformly stirred mixed solution into an iron mold box with the length of 20cm and the length of 20cm, soaking the mullite honeycomb carrier for 24 hours, drying at 80 ℃, and calcining to obtain the pretreated mullite carrier (the weight increase of the pretreated mullite carrier is not less than 5% of the mass of the carrier which is not subjected to pretreatment).
(2) 241.6g of Cu (NO) 3 ) 2 ·3H 2 O and 2896.25g of Ce (NO 3 ) 3 ·6H 2 O was added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. Adding 1mol/L sodium hydroxide solution to adjust the pH to 10-11, stirring for 4 hours, standing for 24 hours, filtering to neutrality with purified water, filtering with ethanol for 30 minutes, drying the filtered solid at 80 ℃, calcining for 4 hours at 550 ℃ with a muffle furnace, pulverizing, and sieving to 100 meshes to obtain the powder catalyst.
(3) 4334g of purified water is taken in a sandwich stirring pot, stirring is started after the temperature of an oil bath is raised to 70 ℃, 253.97g of polyethylene glycol (the molar mass is 6000), 253.97g of sodium carboxymethylcellulose (the viscosity is 600-3000), 317.46g of acidic silica sol (the mass fraction is 30%), 31.75g of tween-20 are sequentially taken and mixed, and each substance is added until the substance is dissolved in the process of adding, and then the next substance is added. Finally, 1kg of powder catalyst is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry, wherein the concentration of the slurry is 30%, and the pH value is 4.1.
(4) The mullite honeycomb carrier is placed into a mold with the thickness of 20cm and the thickness of 20cm, and then the prepared slurry is poured into a mold box and soaked for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24 hours, then heating to 550 ℃ in a muffle furnace at a speed of 10 ℃/min, and calcining for 4 hours to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the mass after coating is increased by 24 percent (namely, the mass of the denitration catalyst is 124 percent of the mass of the pretreated mullite carrier).
Example 5.
The specific operation steps are as follows:
(1) By Al (NO) 3 ) 3 ·9H 2 And (3) preparing an aluminum salt solution with the volume of 1L and 2mol/L by O, preparing a urea solution with the volume of 1L and 6.67mol/L, and adding the two solutions into a sandwich stirring pot and stirring for 4 hours at normal temperature. And pouring the uniformly stirred mixed solution into an iron mold box with the length of 20cm and the length of 20cm, soaking the mullite honeycomb carrier for 24 hours, drying at 80 ℃, and calcining to obtain the pretreated mullite carrier (the weight increase of the pretreated mullite carrier is not less than 5% of the mass of the carrier which is not subjected to pretreatment).
(2) 241.6g of Cu (NO) 3 ) 2 ·3H 2 O and 2896.25g of Ce (NO 3 ) 3 ·6H 2 O was added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. Adding 1mol/L sodium hydroxide solution to adjust the pH to 10-11, stirring for 4 hours, standing for 24 hours, filtering to neutrality with purified water, filtering with ethanol for 30 minutes, drying the filtered solid at 80 ℃, calcining for 4 hours at 550 ℃ with a muffle furnace, pulverizing, and sieving to 100 meshes to obtain the powder catalyst.
(3) 3857g of purified water is taken in a sandwich stirring pot, stirring is started after the temperature of an oil bath is raised to 70 ℃, 319.09g of polyethylene glycol (molar mass is 6000), 319.09g of sodium carboxymethylcellulose (viscosity is 600-3000), 398.86g of acidic silica sol (mass fraction is 30%), 39.89g of tween-20 are sequentially taken and mixed, and each substance is added until the substance is dissolved in the process of adding, and then the next substance is added. Finally, 1kg of powder catalyst is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry. The slurry concentration was 35% and the pH was 4.2.
(4) The mullite honeycomb carrier is placed into a mold with the thickness of 20cm and the thickness of 20cm, and then the prepared slurry is poured into a mold box and soaked for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24 hours, then heating to 550 ℃ in a muffle furnace at a speed of 10 ℃/min, and calcining for 4 hours to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the mass after coating is increased by 22 percent (namely, the mass of the denitration catalyst is 122 percent of the mass of the pretreated mullite carrier).
Example 6.
The specific operation steps are as follows:
(1) By Al (NO) 3 ) 3 ·9H 2 And (3) preparing an aluminum salt solution with the volume of 1L and 2mol/L by O, preparing a urea solution with the volume of 1L and 6.67mol/L, and adding the two solutions into a sandwich stirring pot and stirring for 4 hours at normal temperature. And pouring the uniformly stirred mixed solution into an iron mold box with the length of 20cm and the length of 20cm, soaking the mullite honeycomb carrier for 24 hours, drying at 80 ℃, and calcining to obtain the pretreated mullite carrier (the weight increase of the pretreated mullite carrier is not less than 5% of the mass of the carrier which is not subjected to pretreatment).
(2) 241.6g of Cu (NO) 3 ) 2 ·3H 2 O and 2896.25g of Ce (NO 3 ) 3 ·6H 2 O was added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. Adding 1mol/L sodium hydroxide solution to adjust the pH to 10-11, stirring for 4 hours, standing for 24 hours, filtering to neutrality with purified water, filtering with ethanol for 30 minutes, drying the filtered solid at 80 ℃, calcining for 4 hours at 550 ℃ with a muffle furnace, pulverizing, and sieving to 100 meshes to obtain the powder catalyst.
(3) 3.5kg of purified water is taken in a sandwich stirring pot, stirring is started after the temperature of an oil bath is raised to 70 ℃, 395.06g of polyethylene glycol (molar mass is 6000), 395.06g of sodium carboxymethylcellulose (viscosity is 600-3000), 493.82g of acidic silica sol (mass fraction is 30%), 49.38g of tween-20 are sequentially taken and mixed, and each substance is added until the substance is dissolved in the process of adding, and then the next substance is added. Finally, 1kg of powder catalyst is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry. The slurry concentration was 40% and the pH was 4.1.
(4) The mullite honeycomb carrier is placed into a mold with the thickness of 20cm and the thickness of 20cm, and then the prepared slurry is poured into a mold box and soaked for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24 hours, then heating to 550 ℃ in a muffle furnace at a speed of 10 ℃/min, and calcining for 4 hours to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the mass after coating is increased by 23 percent (namely, the mass of the denitration catalyst is 123 percent of the mass of the pretreated mullite carrier).
Example 7.
The specific operation steps are as follows:
(1) By Al (NO) 3 ) 3 ·9H 2 And (3) preparing an aluminum salt solution with the volume of 1L and 2mol/L by O, preparing a urea solution with the volume of 1L and 6.67mol/L, and adding the two solutions into a sandwich stirring pot and stirring for 4 hours at normal temperature. And pouring the uniformly stirred mixed solution into an iron mold box with the length of 20cm and the length of 20cm, soaking the mullite honeycomb carrier for 24 hours, drying at 80 ℃, and calcining to obtain the pretreated mullite carrier (the weight increase of the pretreated mullite carrier is not less than 5% of the mass of the carrier which is not subjected to pretreatment).
(2) 241.6g of Cu (NO) 3 ) 2 ·3H 2 O and 2896.25g of Ce (NO 3 ) 3 ·6H 2 Adding O into 2000g of purified water, stirring until the O is dissolved to obtain a metal salt solution, adding 1mol/L sodium hydroxide solution to adjust the pH to 10-11, and stirring for 4 hours to obtain an impregnating solution.
And (3) putting the mullite honeycomb carrier into a mould with the thickness of 20cm and 20cm, and then pouring the prepared impregnating solution into a mould box for soaking for 2 hours.
(3) Drying the impregnated mullite honeycomb carrier at 80 ℃ for 24 hours, then heating to 550 ℃ in a muffle furnace at a speed of 10 ℃/min, and calcining for 4 hours to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the weight of the mullite after coating is increased by 12 percent (namely, the mass of the denitration catalyst is 112 percent of the mass of the pretreated mullite carrier).
Example 8.
The specific operation steps are as follows:
(1) By Al (NO) 3 ) 3 ·9H 2 And (3) preparing an aluminum salt solution with the volume of 1L and 2mol/L by O, preparing a urea solution with the volume of 1L and 6.67mol/L, and adding the two solutions into a sandwich stirring pot and stirring for 4 hours at normal temperature. And pouring the uniformly stirred mixed solution into an iron mold box with the length of 20cm and the length of 20cm, soaking the mullite honeycomb carrier for 24 hours, drying at 80 ℃, and calcining to obtain the pretreated mullite carrier (the weight increase of the pretreated mullite carrier is not less than 5% of the mass of the carrier which is not subjected to pretreatment).
(2) 241.6g of Cu (NO) 3 ) 2 ·3H 2 O and 2896.25g of Ce (NO 3 ) 2 ·6H 2 Adding O into 2000g of purified water, stirring until the O is dissolved to obtain a metal salt solution, adding 1mol/L sodium hydroxide solution to adjust the pH to 10-11, stirring for 4 hours, standing for 24 hours, carrying out suction filtration to neutrality by using the purified water, carrying out suction filtration by using ethanol for 30 minutes, drying the solid after suction filtration at 80 ℃, and crushing and sieving to obtain a catalyst precursor with 100 meshes for later use;
(3) 4333g of purified water is taken in a sandwich stirring pot, stirring is started after the temperature of an oil bath is raised to 70 ℃, 253.97g of polyethylene glycol (the molar mass is 6000), 253.97g of sodium carboxymethylcellulose (the viscosity is 600-3000), 317.46g of acidic silica sol (the mass fraction is 30%), 31.75g of tween-20 are sequentially taken and mixed, and each substance is added until the substance is dissolved in the process of adding, and then the next substance is added. Finally, 1kg of catalyst precursor is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry. The slurry concentration was 30% and the pH was 4.1.
(4) The mullite honeycomb carrier is placed into a mold with the thickness of 20cm and the thickness of 20cm, and then the prepared slurry is poured into a mold box and soaked for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24 hours, then heating to 550 ℃ in a muffle furnace at a speed of 10 ℃/min, and calcining for 4 hours to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the mass after coating is increased by 21 percent (namely, the mass of the denitration catalyst is 121 percent of the mass of the pretreated mullite carrier).
Example 9.
The specific operation steps are as follows:
(1) Soaking the mullite honeycomb carrier in water for 24 hours, and then drying and weighing at 80 ℃ for later use;
(2) 241.6g of Cu (NO) 3 ) 2 ·3H 2 O and 2896.25g of Ce (NO 3 ) 2 ·6H 2 Adding O into 2000g of purified water, stirring until the O is dissolved to obtain a metal salt solution, adding 1mol/L sodium hydroxide solution to adjust the pH to 10-11, stirring for 4 hours, standing for 24 hours, carrying out suction filtration to neutrality by using the purified water, carrying out suction filtration by using ethanol for 30 minutes, drying the solid after suction filtration at 80 ℃, and crushing and sieving to obtain a catalyst precursor with 100 meshes for later use;
(3) 4333g of purified water is taken in a sandwich stirring pot, stirring is started after the temperature of an oil bath is raised to 70 ℃, 253.97g of polyethylene glycol (the molar mass is 6000), 253.97g of sodium carboxymethylcellulose (the viscosity is 600-3000), 317.46g of acidic silica sol (the mass fraction is 30%), 31.75g of tween-20 are sequentially taken and mixed, and each substance is added until the substance is dissolved in the process of adding, and then the next substance is added. Finally, 1kg of catalyst precursor is added, and the mixture is stirred for 4 hours at constant temperature to obtain slurry. The slurry concentration was 30% and the pH was 4.1.
(4) Placing the mullite honeycomb carrier into a mould with the thickness of 20cm and the thickness of 20cm, pouring the prepared slurry into a mould box, and soaking for 2 hours;
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24 hours, then heating to 550 ℃ in a muffle furnace at a speed of 10 ℃/min, and calcining for 4 hours to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, and the weight of the mullite after coating is increased by 12 percent (namely, the mass of the denitration catalyst is 112 percent of the mass of the pretreated mullite carrier).
Example 10.
The specific operation steps are as follows:
(1) The mullite honeycomb carrier is soaked in water for 24 hours, and then dried and weighed at 80 ℃ for standby.
(2) 241.6g of Cu (NO) 3 ) 2 ·3H 2 O and 2896.25g of Ce (NO 3 ) 3 ·6H 2 O was added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. Adding 1mol/L sodium hydroxide solution to adjust the pH to 10-11, stirring for 4 hours, standing for 24 hours, filtering to neutrality with purified water, filtering with ethanol for 30 minutes, drying the filtered solid at 80 ℃, calcining for 4 hours at 550 ℃ with a muffle furnace, pulverizing, and sieving to 100 meshes to obtain the powder catalyst.
(3) Taking 3.5kg of purified water in a sandwich stirring pot, heating an oil bath to 70 ℃, opening stirring, adding 1kg of powder catalyst, and stirring for 4 hours at constant temperature.
(4) And (3) putting the mullite honeycomb carrier into a die with the thickness of 20cm and 20cm, and then pouring the prepared powder slurry into a die box for soaking for 2 hours.
(5) And drying the impregnated and coated mullite honeycomb carrier at 80 ℃ for 24 hours, then heating to 550 ℃ in a muffle furnace at a speed of 10 ℃/min, and calcining for 4 hours to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The mass of the mullite before and after coating is weighed, the weight of the mullite after coating is increased by 10 percent (namely, the mass of the denitration catalyst is 110 percent of the mass of the pretreated mullite carrier), and the phenomena that the honeycomb mullite is cracked and disintegrated into uneven blocks and the large-area catalyst powder falls off are found.
Example 11.
The specific operation steps are as follows:
(1) By Al (NO) 3 ) 3 ·9H 2 And (3) preparing an aluminum salt solution with the volume of 1L and 2mol/L by O, preparing a urea solution with the volume of 1L and 6.67mol/L, and adding the two solutions into a sandwich stirring pot and stirring for 4 hours at normal temperature. Then pouring the uniformly stirred mixed solution into an iron mold box with the thickness of 20cm and the thickness of 20cm, and pouring the mullite bees into the iron mold box with the thickness of 20cm and the thickness of 20cmAfter soaking the nest carrier for 24 hours, drying and calcining at 80 ℃ to obtain the pretreated mullite carrier (the weight increase of the pretreated mullite carrier is not less than 5% of the mass of the carrier which is not pretreated).
(2) 241.6g of Cu (NO) 3 ) 2 ·3H 2 O and 2896.25g of Ce (NO 3 ) 3 ·6H 2 O was added to 2000g of purified water and stirred until dissolved, to obtain a metal salt solution. Adding 1mol/L sodium hydroxide solution to adjust the pH to 10-11, stirring for 4 hours, standing for 24 hours, filtering to neutrality with purified water, filtering with ethanol for 30 minutes, drying the filtered solid at 80 ℃, calcining for 4 hours at 550 ℃ with a muffle furnace, pulverizing, and sieving to 100 meshes to obtain the powder catalyst.
(3) 3.5kg of purified water is taken in a sandwich stirring pot, stirring is started after the temperature of an oil bath is raised to 70 ℃, 395.06g of polyethylene glycol (molar mass is 6000), 395.06g of sodium carboxymethylcellulose (viscosity is 600-3000), 493.82g of acidic silica sol (mass fraction is 30%), 49.38g of tween-20 are sequentially taken and mixed, and each substance is added until the substance is dissolved in the process of adding, and then the next substance is added. Finally, adding 1kg of powder catalyst, and stirring for 4 hours at constant temperature to obtain slurry. The slurry concentration was 40% and the pH was 4.1.
(4) The mullite honeycomb carrier is placed into a mold with the thickness of 20cm and the thickness of 20cm, and then the prepared slurry is poured into a mold box and soaked for 2 hours.
(5) Drying the impregnated mullite honeycomb carrier at 80 ℃ for 24 hours, coating again in the slurry in the example, drying again, heating to 550 ℃ in a muffle furnace at a speed of 10 ℃/min, and calcining for 4 hours to obtain the mullite honeycomb monolithic CO low-temperature denitration catalyst.
The weight of the mullite before and after coating is weighed, the weight of the mullite after coating is increased by 135 percent (namely, the weight of the denitration catalyst is 135 percent of the weight of the pretreated mullite carrier), but the phenomena of mullite cracking and disintegration into non-uniform four small blocks appear, and the phenomenon of catalyst powder falling occurs.
Example 12.
The procedure of example 12 was identical to that of example 10, except for the pretreatment of the mullite support. The pretreatment step for mullite in example 12 is the same as the pretreatment step for mullite carrier in example 11.
The mass of the mullite before and after coating was weighed and the mass increase after coating was greater than that of example 10. However, in the calcination process, the honeycomb mullite is cracked and disintegrated into uneven blocks, and the large-area catalyst powder falls off.
The shaped catalysts prepared in examples 2-11 were used for the low temperature denitration of CO, and the reaction conditions and the activity results are shown in Table 1.
Molded catalyst performance comparison: the activity experiments were carried out on a self-made catalyst test platform with a carbon to nitrogen ratio of 2:1, O 2 Concentration of 0% (V/V), GHSV (gas space velocity per hour) = 3333.33h -1 The NO conversion rate was measured at 3 temperature points such as 100℃and 200℃and 300 ℃. When the temperature of the reactor is stabilized to a certain temperature point, the simulated flue gas is introduced, after the reaction is carried out for 30min, the concentration of NO in the gas before and after the reaction is measured by using a flue gas analyzer, the continuous measurement time of each temperature point is 10min, the average value is taken, and the NO conversion rate is calculated according to the formula 3.
Conversion of no= [ (NO) in -NO out )/NO in ]×100％(3)
Table 1. Mullite honeycomb carrier catalysts of different slurry concentrations have the following low temperature CO-SCR denitration efficiencies:
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table 2. Mullite honeycomb carrier catalysts prepared by different coating methods have the following denitration efficiency of low-temperature CO-SCR:
as can be seen from the combination of table 1, the comparison of comparative examples 2 to 6 and 9 shows that the coating effect can be enhanced and the denitration efficiency can be improved after the mullite honeycomb carrier is pretreated in the preparation process; meanwhile, the coating effect can be increased due to the proper slurry concentration, the denitration efficiency is improved, and when the slurry concentration is overlarge, the load capacity can be improved, but the powder catalyst can fall off. And multiple coating increases catalyst loading, but excessive loading can result in cracking of the mullite honeycomb support (example 11). Therefore, the mullite honeycomb carrier is pretreated, and the formed catalyst is prepared by using the slurry concentration of 30 percent, and when the weight gain is not more than 25 percent, the higher denitration efficiency can be achieved.
In addition, the mullite carrier is not pretreated, the loading capacity of the carrier is extremely low when the mullite carrier is coated without slurry, and the carrier is easy to break when calcined, so that the method is adopted for pretreatment of the carrier, and the loading capacity can be increased by slurry coating, and the problem that the carrier is unstable and easy to crack when the mullite carrier is calcined at a low temperature (lower than 600 ℃) can be solved.
As can be seen from table 2, the direct impregnation method and the coprecipitation coating method of the comparative solution find that the prepared catalyst precursor and catalyst powder are coated with a higher coating amount and have better denitration performance.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the embodiment of the present invention in any way, but any simple modification, equivalent variation and modification of the above embodiment according to the technical substance of the embodiment of the present invention still fall within the scope of the technical solution of the embodiment of the present invention.

Claims (10)

1. The preparation method of the denitration catalyst for CO-SCR flue gas denitration is characterized by comprising the following steps of:
(1) Preparing catalyst powder;
(2) Adding an additive and the catalyst powder into water, and uniformly mixing to obtain slurry; the additive is an inorganic binder, an organic polymer solution and a surfactant;
the adhesive is silica sol, the organic polymer comprises polyethylene glycol and sodium carboxymethyl cellulose, and the surfactant is tween-20;
the mass ratio of polyethylene glycol to acidic silica gel to sodium carboxymethylcellulose to tween-20 is 8:10:8:1, a step of;
the slurry comprises the following components in percentage by mass: 50-70% of water, 10-20% of additive and 20-40% of catalyst powder;
(3) Immersing the pretreated honeycomb mullite carrier in the slurry, and then drying and calcining to obtain the denitration catalyst for CO-SCR flue gas denitration;
the pretreatment is as follows: soaking the cleaned mullite carrier in a mixed solution containing urea and aluminum salt for 24 hours, drying at 80 ℃ for 48 hours, and calcining at 550 ℃ for 4 hours;
the aluminum salt is aluminum nitrate or aluminum sulfate; when the aluminum salt is aluminum nitrate, the aluminum nitrate is 1mol/L;
the urea is 3.335mol/L.
2. The method according to claim 1, wherein,
in the step (1), a coprecipitation method is adopted to prepare catalyst powder.
3. The method according to claim 2, wherein,
in the step (1), cerium salt and copper salt are adopted as raw materials, and the molar ratio of Ce to Cu is 6.67:1.
4. A process according to claim 3, wherein,
in the step (1), the copper salt is at least one of copper sulfate, copper chloride and copper nitrate; the cerium salt is at least one of cerium nitrate, cerium chloride and cerium sulfate.
5. The method according to claim 4, wherein,
in the step (1), the cerium salt is cerium nitrate, and the copper salt is copper nitrate;
in the step (2), the mass fraction of the slurry is 30-40%;
in the step (3), the slurry is immersed for 2 hours.
6. The method according to claim 5, wherein,
in the step (2), the mass fraction of the slurry is 30%.
7. The method according to claim 2, wherein,
in the step (2), the mixing temperature is 60-70 ℃;
in the step (3), the weight increase of the pretreated mullite carrier is not less than 5% of the mass of the carrier which is not pretreated;
the mass of the denitration catalyst is 110-130% of the mass of the pretreated mullite carrier.
8. A denitration catalyst for denitration of CO-SCR flue gas, wherein the denitration catalyst is prepared by the preparation method according to any one of claims 1 to 7.
9. The use of the denitration catalyst according to claim 8, wherein the denitration catalyst performs a CO selective catalytic reduction reaction.
10. The use according to claim 9, wherein,
the temperature of the CO selective catalytic reduction reaction is 150-300 ℃.
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