CN114307634A - Granular denitration agent and preparation method and application thereof - Google Patents
Granular denitration agent and preparation method and application thereof Download PDFInfo
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- CN114307634A CN114307634A CN202210005287.1A CN202210005287A CN114307634A CN 114307634 A CN114307634 A CN 114307634A CN 202210005287 A CN202210005287 A CN 202210005287A CN 114307634 A CN114307634 A CN 114307634A
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Abstract
The invention discloses a granular composite denitration agent and a preparation method and application thereof. The granular composite denitration agent comprises: a reducing agent, a non-supported manganese-cerium composite catalyst, a synergist and an organic binder. Weighing a reducing agent, a non-supported manganese-cerium composite catalyst and a synergist, mixing, conveying to a disc granulator or a rotary drum granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution onto the surface of a mixture, and performing rolling coating granulation; drying and sieving to obtain the granular composite denitration agent. The invention also discloses an unsupported manganese-cerium composite catalyst, which comprises manganese oxide and cerium oxide. The granular composite denitration agent has good fluidity, the denitration reaction temperature range is 100-1100 ℃, and the granular composite denitration agent can continuously play a denitration role in the subsequent flue gas full cooling process after being sprayed into the flue gas at 850-1100 ℃, so that the denitration efficiency is high, and the cost is low; meanwhile, the denitration agent has a catalytic deamination function and can reduce ammonia escape.
Description
Technical Field
The invention belongs to the technical field of incineration flue gas denitration, and particularly relates to a granular denitration agent and a preparation method and application thereof.
Background
Nitrogen Oxides (NO)x) Mainly comprising Nitric Oxide (NO) and nitrogen dioxide (NO)2) It is the main pollutant in the atmosphere. Coal and solid waste incineratorThe high temperature industrial process such as burning is NOxIs used as the primary emission source. To reduce NOxEnterprises such as industrial emission, coal-fired heat supply, coal-fired power generation, cement production and solid waste incineration generally adopt a selective non-catalytic reduction (SNCR) denitration technology or a Selective Catalytic Reduction (SCR) denitration technology. In the SNCR denitration process, reducing agent urea solution or ammonia water is atomized and sprayed into high-temperature flue gas at the temperature of 900-xReduction to N2. However, the SNCR technology alone has a low denitration efficiency, usually lower than 50%, and it is difficult to remove NOxThe emission level of (A) is continuously controlled at 100mg/Nm3In the following, increasing the amount of reducing agent urea and ammonia water results in increased ammonia slip. In the SCR denitration process, a catalyst module is usually arranged at the rear end of a flue gas facility, the reaction temperature is 180-400 ℃, and the commonly used reducing agent is ammonia water. In the SCR process, in order to prevent the catalyst from being deactivated, the flue gas needs to be subjected to a desulfurization treatment. The SCR denitration technology has high denitration efficiency which can reach more than 90 percent, but has large equipment investment and high operating cost. The development of high efficiency, low cost and low ammonia slip denitration technology is still an urgent need in the combustion/incineration field.
The recently developed denitration technology of the solid-state denitration agent shows higher denitration efficiency compared with the traditional SNCR technology. The technology is that a denitration agent in a powder state, a particle state or a particle powder mixed state is directly sprayed into the smoke with the temperature of 450-1050 ℃ by a pneumatic conveying device, and NO in the smoke can be removed by the SNCR principlex. The reducing agents in the solid denitrifying agents reported in the patent documents at present are all mixtures of various materials. The reported reductant components include: urea (CN 110639341A, CN 110270325A, CN 111672290A, CN 112403529A, CN 109316892A, CN 111001279A, CN 110026077 a), dicyandiamide (CN 113019118A, CN 109316892A), melamine (CN 108187490A, CN 111992035A), cyanuric acid (CN 107998852A, CN 108187490 a), ammonium hydrogen carbonate (CN 113019118A) and other organic amine-based compounds (CN 111686564A, CN 112915751 a); other additional ingredients reported include: manganese dioxide, titanium oxide, clay mineral, copper oxide, calcium magnesium acetate, potassium permanganate, sodium hydroxide, sodium bicarbonate, calcium carbonate and carboxymethyl celluloseA seed resin, and the like. The density and the grain diameter of the components of the materials are greatly different, so that the flow rates of different materials are obviously different during pneumatic conveying, and high-density materials are easy to deposit at a feed opening of feeding equipment or a bent part of a conveying pipeline and easily cause blockage; meanwhile, layering can occur between the granular materials and the powdery materials in the mixing process, so that the components in the mixed denitration agent are not uniformly distributed, and the denitration efficiency is unstable.
In order to solve the layering problem of the denitration agent containing the powdery substance, CN 111992035A reports a preparation method of the denitration agent for treating the flue gas of the high-efficiency energy-saving coal-fired boiler, and urea particles and supported Mn-TiO are mixed in the method2Ball milling, mixing with polyvinyl alcohol adhesive, and evaporating for granulation. In order to solve the problem of poor fluidity of the denitration agent containing powder substances, patent CN 111992035 a reports a preparation method of a high-fluidity and high-efficiency denitration agent, in which a denitration reducing agent, a binder and a powder synergist are mixed and stirred in water to form slurry, and then spray granulation is performed in a spray drying tower. The two granulation processes require additional heat sources and consume high energy.
Disclosure of Invention
The main purposes of the invention are as follows: aiming at the defects of the existing solid denitration agent, the granular denitration agent and the preparation method thereof are provided, the layering phenomenon of granular materials and powdery materials and the poor flowability phenomenon of high-density materials in the storage and use processes of the existing solid denitration agent are solved, low-cost coating granulation at normal temperature and normal pressure is realized, and meanwhile, the denitration efficiency is improved and the ammonia escape is reduced through screening and optimization of the components of the denitration agent. The invention also aims to provide an application method for flue gas denitration by using the granular denitration agent. The invention also aims to provide an unsupported manganese-cerium composite catalyst and application thereof in preparing a granular denitration agent for flue gas denitration.
In order to achieve the purpose, the invention adopts the technical scheme that: the granular denitration agent is characterized by comprising the following components in percentage by mass based on 100% of the denitration agent: 5-20% of non-load manganese cerium composite catalyst, a proper amount of binder and the balance of reducing agent; based on 100% of the mass of the granular denitration agent, the content of manganese element in the non-supported manganese-cerium composite catalyst is not less than 1.4%, and the content of cerium element is not less than 0.04%. Preferably, the particulate composite denitration agent further comprises: 1-10% of synergist, namely the granular composite denitration agent comprises the following components in percentage by weight: 5-20% of non-load manganese cerium composite catalyst, 1-10% of synergist, a proper amount of binder and the balance of reducing agent. Preferably, the granular denitration agent comprises the following components by taking the total mass of the granular denitration agent as 100 percent: 6-18% or 9-18% of non-load type manganese cerium composite catalyst, 2-9% of synergist, a proper amount of binder and the balance of reducing agent.
The reducing agent comprises any one of urea, ammonium chloride and melamine or a mixture of two or more of the urea, the ammonium chloride and the melamine in any proportion, and is in a granular form. In high temperature flue gas, reducing agent reduces NOx to N2. The reducing agent is a main component of the particulate denitration agent, and usually accounts for 70% or more, such as 90% by mass.
After comparing various manganese-containing oxide catalysts, the inventors found that the unsupported manganese-cerium composite catalyst is particularly suitable for a particulate denitration agent. The unsupported manganese-cerium composite catalyst comprises a manganese oxide and cerium oxide. In the granular denitration agent, the non-supported manganese-cerium composite catalyst is adhered to the surface of the granular reducing agent through a binder. The manganese oxide can be manganese dioxide, manganese ore powder or a mixture of the manganese dioxide and the manganese ore powder in any proportion. The content of manganese element is not less than 1.4%, such as 1.4-12.5%, 3%, 6%, preferably not less than 1.5%, such as 1.5-12%, 1.5-9% by mass of the granular denitration agent as 100%; the cerium element content is not less than 0.04%, for example, 0.04 to 1.7%, 0.04 to 1.6%, preferably not less than 0.05% or not less than 0.1%, for example, 0.05 to 1.6%, 0.1 to 1.3%. The preferable scheme is that the content of manganese element is 1.5-12% by mass of the granular denitration agent as 100%; the content of cerium element is 0.05-1.6%. The preferred technical scheme is that the mass percent of the manganese oxide is 4.5-19.8% and the preferred range is 5-18% based on 100% of the mass of the granular denitration agent; the mass percent of cerium oxide is 0.05-2.0%, and the preferred range is 0.1-1.8%. The mass percentage of the cerium oxide is 1-10%, and the mass percentage of the manganese oxide is 90-99% based on 100% of the mass of the non-supported manganese-cerium composite catalyst. The preferable range is that the mass percent of cerium oxide is 2-9%, and the mass percent of manganese oxide is 91-98%; or the mass percent of cerium oxide is 3-8%, and the mass percent of manganese oxide is 92-97%; the mass percent of cerium oxide is 3-9%, and the mass percent of manganese oxide is 91-97%; the mass percent of cerium oxide is 3-10%, and the mass percent of manganese oxide is 90-97%.
The manganese oxide can be used for catalytically removing NO in flue gas in the temperature reduction stage of 600-100 DEG Cx. Manganese element in manganese oxide can adsorb NO and NH simultaneously3And promote electron transfer, thereby realizing efficient denitration. Manganese oxide in manganese oxide has strong adsorption of NH3Ability to convert NH in the absence of NO3And (3) oxidizing to realize high-efficiency catalytic deamination, so that ammonia escape can be reduced. Cerium oxide (Ce) supported on manganese oxide due to CeO2Has higher oxygen capacity and excellent catalytic reduction performance, and Ce is oxidized or reduced3+And Ce4+There is a rapid transition between to trap or release O atoms, promoting the conversion of NO to NO2Thereby enhancing the denitration ability of the manganese oxide. In order to ensure the denitration and deamination efficiency of the non-supported manganese-cerium composite catalyst, the particle size of the non-supported manganese-cerium composite catalyst is preferably 200 meshes or more.
And roasting and crushing the mixture of the cerium oxide and the manganese oxide to obtain the unsupported manganese-cerium composite catalyst, wherein the preferable mode is to treat the mixture of the cerium oxide and the manganese oxide by using dilute sulfuric acid before roasting. The preparation method specifically comprises the following steps: mixing cerium oxide, manganese dioxide or manganese ore powder in proportion at room temperature, stirring uniformly, adding a proper amount of water, mixing and stirring into slurry, drying (heating at 85-100 deg.C), and roasting at 300-500 deg.C for 3 hr or more; cooling, ball-milling and crushing to 200 meshes or above to obtain the non-supported manganese-cerium composite catalyst. The preparation method is preferably that cerium oxide, manganese dioxide or manganese ore powder is stirred and mixed evenly, then dilute sulphuric acid (such as 1mol/L) solution is added to be fully mixed and stirred into slurry, and the slurry is dried (the slurry can be heated properly such as 85 to 100 ℃) and roasted for 3 hours or more at the temperature of 300 ℃ and 500 ℃; cooling, ball-milling and crushing to 200 meshes or above to obtain the powdery non-supported manganese-cerium composite catalyst.
The patent also discloses the application of the non-supported manganese-cerium composite catalyst in preparing a granular denitration agent for flue gas denitration; the granular denitration agent comprises 5-20% of non-supported manganese-cerium composite catalyst, a binder and a reducing agent by taking the mass of the denitration agent as 100%; the reducing agent is particulate urea; the non-supported manganese-cerium composite catalyst comprises a manganese oxide and cerium oxide; based on 100% of the mass of the granular denitration agent, the content of manganese element in the non-supported manganese-cerium composite catalyst is not less than 1.4%, and the content of cerium element is not less than 0.04%; the non-supported manganese-cerium composite catalyst is adhered to the surface of the granular reducing agent through a binder; the binder is a water-soluble thermosetting resin having a decomposition temperature of 600 ℃ or lower, such as a water-soluble polyurethane resin or a water-soluble urea resin. Preferably, the content of manganese element in the non-supported manganese-cerium composite catalyst is not less than 1.5%, such as 1.5-12%; the content of cerium is not less than 0.05%, for example, 0.05 to 1.6%.
As discussed in the background section, SCR denitration technology is one of the denitration technologies commonly used in the prior art. The basic technical principle of the SCR is as follows: spraying reducing agent ammonia water into a low-temperature flue gas section (such as flue gas with the temperature of 180-420 ℃), and reacting NO under the action of a catalystxReduction to N2And H2And O. In the practical application of the SCR denitration process, the catalyst works in a module form, a catalyst module is formed by a plurality of flaky or blocky catalyst elements, and then a plurality of catalyst modules are combined together to form a catalytic denitration assembly. Wherein the catalyst applied comprises a manganese oxide containing catalyst. The manganese oxide catalyst has good low-temperature (150-250 ℃) denitration performance. Because the manganese oxide in the manganese oxide-containing catalyst can react with SO in the flue gas2Manganese sulfate is formed by reaction, resulting in manganese lossDe-catalysis of NH3The capability of removing NOx, namely the SCR catalytic denitration component containing manganese oxide needs to be arranged behind a flue gas desulfurization device. The temperature of the flue gas after the flue gas desulfurization device is usually lower than 200 ℃, and the manganese oxide-containing catalyst has catalytic denitration activity under the condition. In the SCR denitration catalyst module, the manganese oxide is usually supported on titanium dioxide (TO)2) TO form Mn-TO2And (3) compounding a catalyst. In order TO further improve the low-temperature denitration activity of the manganese-containing SCR denitration agent, cerium can be doped in manganese oxide and then loaded in TO2And forming the SCR denitration catalyst containing the manganese-cerium composite oxide. The preparation method of the manganese-cerium composite oxide for flue gas SCR denitration reported in literature comprises the following steps: dissolving cerium nitrate and manganese nitrate in water, then adding titanium oxide, evaporating to dryness, and roasting at 300-500 ℃ to prepare the manganese-cerium-containing composite oxide. Since cerium nitrate and manganese nitrate are expensive, the manganese-cerium composite oxide for the SCR denitration process is expensive to manufacture.
Different from the SCR denitration process, the denitration agent in the patent is injected into high-temperature flue gas at 850-1100 ℃, along with the gasification of a reducing agent and the progress of an SNCR reduction reaction, wherein the non-supported manganese-cerium composite catalyst is suspended in the flue gas in a particulate form, and the non-supported manganese-cerium composite catalyst and the residual reducing agent flow from a high-temperature section to a low-temperature section along with the flow of the flue gas. Under the condition that the temperature of flue gas is 100-600 ℃, the non-supported manganese-cerium composite catalyst continuously catalyzes NH3Reduction of NOxAnd the flue gas denitration of medium and low temperature sections is realized. The inventors have found that there is a slight degree of catalyst deactivation during the denitration process of the present invention. However, the sulfuric acid acidification treatment is carried out on the non-supported manganese-cerium composite catalyst, SO in the flue gas is well overcome2The problem of catalyst deactivation caused by the desulfurization can still play a role in high-efficiency catalytic denitration under the condition that the flue gas is not desulfurized.
The synergist comprises sodium bicarbonate and/or magnesium ore powder. The sodium bicarbonate can promote the generation of a large amount of OH active groups in the smoke at 850-1100 ℃, which is beneficial to NH3The reduction of NO can greatly improve the denitration reaction efficiency and widen the denitration reaction temperature window,by reaction of NH3The reactivity of the denitration by SNCR mode is reduced to 600 ℃. The magnesium oxide in the magnesium mineral powder has an oxygen defect structure surface, has strong catalytic capability on the dissociation of NO in incineration flue gas, and can promote NO to generate N2Thereby further increasing the denitration effect in the range of 100-300 ℃. In order to ensure high efficiency of catalytic denitration of the magnesium ore powder, the particle size of the magnesium ore powder is preferably 200 meshes or more. The sodium bicarbonate and the magnesium ore powder can be used independently or mixed according to any proportion, for example, the mass ratio of the sodium bicarbonate to the magnesium ore powder is 50: 50-20: 80, such as 30:70, 25:75, 35:65, 40:60 and the like. The synergist is not an essential component of the granular denitration agent, but the denitration effect is better when the synergist is added according to 0.1-10% of the total mass. The preferable proportion is 1-10% or 2-10% or 3-10% of the total mass of the granular denitration agent. The synergist is adhered to the surface of the granular reducing agent through a binder.
The binder according to the invention is preferably an organic binder, in particular a water-soluble thermosetting resin having a decomposition temperature of 600 ℃ or less, the amount of which can be determined experimentally in each case. The amount of the organic binder is usually 0.1 to 1.0%, such as 0.1 to 0.9%, 0.1 to 0.8%, etc., based on the total mass of the particulate denitration agent. Although various types of binders are disclosed in the prior art, repeated tests and comparisons show that the water-soluble thermosetting resins of the water-soluble polyurethane resin and the water-soluble urea-formaldehyde resin have extremely strong binding and balling capabilities, the mixture of the powdery non-supported manganese-cerium composite catalyst and the powdery denitration synergist can be firmly coated on the reducing agent urea particles, and when the granular denitration agent is sprayed into smoke at 850-. The binder can adopt one of water-soluble polyurethane resin and water-soluble urea-formaldehyde resin or a mixture of the two in any ratio.
Meanwhile, the invention also provides a preparation method of the granular denitration agent, which comprises the following steps:
the method comprises the following steps: uniformly mixing a granular reducing agent, a non-supported manganese-cerium composite catalyst and a synergist to obtain a mixture;
step two: preparing the organic binder into aqueous solution, spraying the aqueous solution on the mixture, and coating and granulating the mixture. For example, the coating can be carried out by a granulating apparatus such as a disk granulator or a drum granulator;
step three: and (3) drying the granules produced in the step two, sieving and screening the granules with the diameter of 1.0-4.0mm, preferably 1.5-3.5mm to prepare the granular denitration agent.
In the first step, when urea is used as the reducing agent, granular urea is generally available and is therefore a preferred reducing agent. If the reducing agent used is not in the form of particles, for example, commercial ammonium chloride and melamine are not in the form of particles, it is necessary to first pretreat the reducing agent to convert it to particles. It may be subjected to granulation pretreatment according to any known method. During granulation, granulation auxiliaries need to be added, which leads to a decrease in the overall reducing nitrogen content in the reducing agent. The mass percentage of the reduced nitrogen in the granular reducing agent is required to be not less than 25 percent.
In the first step, if the particle size of the unsupported manganese cerium composite catalyst and synergist is less than 200 meshes, pretreatment is also needed, and the particle size is reduced to 200 meshes or finer by crushing, such as ball milling. Thus, the unsupported manganese-cerium composite catalyst and the synergist can be uniformly adhered to the surface of the particulate reducing agent by the binder.
The granular denitration agent is sprayed into high-temperature flue gas such as 850-xAnd removing. The granular composite denitration agent is disintegrated by a reducing agent in high-temperature flue gas and releases NH3Removing NO in the smoke by SNCR methodx. And then, in the process of cooling the flue gas, the non-supported manganese-cerium composite catalyst is subjected to denitration by a Selective Catalytic Reduction (SCR) denitration principle, and simultaneously, residual ammonia in the flue gas is removed in a catalytic manner.
In conclusion, the granular denitration agent disclosed by the invention can continuously play a denitration role in the full cooling process after the flue gas is sprayed, so that the efficient denitration is realized and the ammonia escape is reduced. Compared with the prior art, the invention has the beneficial effects that: (1) the denitration agent has good fluidity and stable denitration effect; (2) the denitration reaction temperature window is wide, covers 100-; (3) the denitration method is widely applicable to denitration of industrial incineration flue gas of industrial coal-fired boilers, industrial kilns, municipal solid waste incineration, solid waste incineration and the like, and compared with an SCR denitration process, the denitration method is low in denitration cost and good in benefit.
Detailed Description
The objects, technical solutions and advantages of the present invention will be more clearly and completely described below with reference to examples and comparative examples. The description is illustrative in nature and is not intended to limit the scope of the claims. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention.
The single chemicals and raw materials required in the examples are purchased from commercial sources, and the brand and the production place are not limited.
Preparation of granular denitration agent
Example 1
A granular composite denitration agent comprises the following components: 90 parts by mass of a reducing agent, 8.9 parts by mass of an unsupported manganese-cerium composite catalyst, 1 part by mass of a denitration synergist and 0.1 part by mass of an organic binder. The reducing agent is granular urea, and the denitration synergist comprises the following components: 50 parts by mass of powdery sodium bicarbonate and 50 parts by mass of 200-mesh magnesium ore powder. The organic binder is water-soluble urea-formaldehyde resin.
The preparation method of the non-supported manganese-cerium composite catalyst comprises the following steps: stirring and uniformly mixing 10 parts by mass of cerium oxide and 90 parts by mass of manganese ore powder at room temperature, adding 1mol/L dilute sulfuric acid solution, mixing and stirring to obtain slurry, fully and uniformly mixing, drying at 85 ℃, and roasting at 500 ℃ for 3 hours; cooling, ball milling again and crushing to 200 meshes or above.
Weighing a granular reducing agent, a non-supported manganese-cerium composite catalyst and a denitration synergist, and mixing in a mixer; conveying the mixture to a disc granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution on the surface of the mixture, and carrying out rolling granulation; and naturally drying the produced particles, sieving the particles with the preferred diameter of 1.5-3.5mm, cooling and packaging.
The prepared granular composite denitration agent is used for denitration of flue gas of a coal-fired boiler and is sprayed into the flue gas at 900-1050 ℃ after being sprayed into a combustion chamber.
Example 2
A granular composite denitration agent comprises the following components: 85 parts by mass of a reducing agent, 11.7 parts by mass of an unsupported manganese-cerium composite catalyst, 3 parts by mass of a denitration synergist and 0.3 part by mass of an organic binder. The reducing agent is the mixture of urea and melamine to prepare particles, wherein the total content of the reducing nitrogen is 35 percent (by mass ratio). The organic binder is water-soluble polyurethane resin. The denitration synergist comprises the following components: 20 parts of powdery sodium bicarbonate and 80 parts of 200-mesh magnesium ore powder.
The preparation method of the non-supported manganese-cerium composite catalyst comprises the following steps: stirring and uniformly mixing 5 parts by mass of cerium oxide and 95 parts by mass of manganese dioxide at room temperature, then adding 1mol/L dilute sulfuric acid solution, mixing and stirring to obtain slurry, fully and uniformly mixing, drying at 90 ℃, and then roasting at 400 ℃ for 4 hours; cooling, ball milling again and crushing to 200 meshes or above.
Weighing a granular reducing agent, a non-supported manganese-cerium composite catalyst and a denitration synergist according to a mass ratio, and mixing in a mixer; conveying the mixture to a rotary drum granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution on the surface of the mixture, and carrying out rolling granulation; and conveying the produced granules to a drying cylinder for drying, sieving the granules with the preferred diameter of 1.5-3.5mm, cooling and packaging.
The prepared granular composite denitration agent is used for denitration of flue gas of a hazardous waste incinerator and is sprayed into the flue gas at 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 3
A granular composite denitration agent comprises the following components: 80 parts by mass of a reducing agent, 15 parts by mass of an unsupported manganese-cerium composite catalyst, 4.5 parts by mass of a denitration synergist and 0.5 part by mass of an organic binder. The reducing agent is a mixture of urea, ammonium chloride and melamine, and is prepared into particles, wherein the total content of reducing nitrogen is 25 percent (by mass). The organic binder comprises the following components: 50 parts by mass of a water-soluble urea-formaldehyde resin and 50 parts by mass of a water-soluble polyurethane resin. The denitration synergist comprises the following components: 30 parts by mass of powdery sodium bicarbonate and 70 parts by mass of 200-mesh magnesium ore powder.
The preparation method of the non-supported manganese-cerium composite catalyst comprises the following steps: stirring and uniformly mixing 8 parts by mass of cerium oxide and 92 parts by mass of manganese ore powder at room temperature, adding 1mol/L dilute sulfuric acid solution, mixing and stirring to obtain a slurry, fully and uniformly mixing, drying at 95 ℃, and roasting at 350 ℃ for 4 hours; cooling, ball milling again and crushing to 200 meshes or above.
Weighing a granular reducing agent, a non-supported manganese-cerium composite catalyst and a denitration synergist according to a mass ratio, and mixing in a mixer; conveying the mixture to a disc granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution on the surface of the mixture, and carrying out rolling granulation; and conveying the produced granules to a drying cylinder for drying, sieving the granules with the preferred diameter of 1.5-3.5mm, cooling and packaging.
The prepared granular composite denitration agent is used for denitration of coal-fired boiler flue gas, and is sprayed into the flue gas with the temperature of 850-950 ℃ after being sprayed into a combustion chamber.
Example 4
A granular composite denitration agent comprises the following components: 75 parts by mass of a reducing agent, 14.4 parts by mass of an unsupported manganese-cerium composite catalyst, 10 parts by mass of a denitration synergist and 0.6 part by mass of an organic binder. The reducing agent is granular urea. The organic binder is water-soluble urea-formaldehyde resin. The denitration synergist comprises the following components: 25 parts by mass of powdery sodium bicarbonate and 75 parts by mass of 200-mesh magnesium ore powder.
The preparation method of the non-supported manganese-cerium composite catalyst comprises the following steps: stirring and uniformly mixing 6 parts by mass of cerium oxide and 94 parts by mass of manganese dioxide at room temperature, then adding 1mol/L dilute sulfuric acid solution, mixing and stirring to obtain slurry, fully and uniformly mixing, drying at 100 ℃, and then roasting at 300 ℃ for 5 hours; cooling, ball milling again and crushing to 200 meshes or above.
Weighing a granular reducing agent, a non-supported manganese-cerium composite catalyst and a denitration synergist according to a mass ratio, and mixing in a mixer; conveying the mixture to a rotary drum granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution on the surface of the mixture, and carrying out rolling granulation; and naturally drying the produced particles, sieving the particles with the preferred diameter of 1.5-3.5mm, cooling and packaging.
The prepared granular composite denitration agent is used for denitration of flue gas of an urban domestic garbage incinerator and is sprayed into the flue gas at 950-1000 ℃ after being sprayed into a combustion chamber.
Comparative example 1
The granular composite denitration agent is prepared according to the same formula and steps of example 4, but the preparation process of the unsupported manganese-cerium composite catalyst is not carried out with dilute sulfuric acid acidification treatment.
Example 5
A granular composite denitration agent comprises the following components: 70 parts by mass of a reducing agent, 20 parts by mass of an unsupported manganese-cerium composite catalyst, 9.2 parts by mass of a denitration synergist and 0.8 part by mass of an organic binder. The reducing agent is granular urea. The organic binder comprises the following components: 80 parts by mass of water-soluble urea-formaldehyde resin and 20 parts by mass of water-soluble polyurethane resin. The denitration synergist comprises the following components: 35 parts by mass of powdery sodium bicarbonate and 65 parts by mass of 200-mesh magnesium ore powder.
The preparation method of the non-supported manganese-cerium composite catalyst comprises the following steps: stirring and uniformly mixing 1 part by mass of cerium oxide and 99 parts by mass of manganese ore powder at room temperature, adding 1mol/L of dilute sulfuric acid solution, mixing and stirring to obtain a slurry, fully and uniformly mixing, drying at 90 ℃, and roasting at 450 ℃ for 3.5 hours; cooling, ball milling again and crushing to 200 meshes or above.
Weighing a granular reducing agent, a non-supported manganese-cerium composite catalyst and a denitration synergist according to a mass ratio, and mixing in a mixer; conveying the mixture to a disc granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution on the surface of the mixture, and carrying out rolling granulation; and conveying the produced granules to a drying cylinder for drying, sieving the granules with the preferred diameter of 1.5-3.5mm, cooling and packaging.
The prepared granular composite denitration agent is used for denitration of flue gas of an urban domestic garbage incinerator and is sprayed into the flue gas at 950-1000 ℃ after being sprayed into a combustion chamber.
Comparative example 2
The granular composite denitration agent is prepared according to the same formula and steps of example 5, but the preparation process of the unsupported manganese-cerium composite catalyst is not carried out with dilute sulfuric acid acidification treatment.
Example 6
A granular composite denitration agent comprises the following components: 85 parts by mass of a reducing agent, 5 parts by mass of an unsupported manganese-cerium composite catalyst, 9 parts by mass of a denitration synergist and 1 part by mass of an organic binder. The reducing agent is granular urea. The organic binder comprises the following components: 20 parts by mass of water-soluble urea-formaldehyde resin and 80 parts by mass of water-soluble polyurethane resin. The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the non-supported manganese-cerium composite catalyst comprises the following steps: stirring and uniformly mixing 7.5 parts by mass of cerium oxide and 92.5 parts by mass of manganese ore powder at room temperature, adding 1mol/L dilute sulfuric acid solution, mixing and stirring to obtain a slurry, fully and uniformly mixing, drying at 90 ℃, and roasting at 400 ℃ for 3.5 hours; cooling, ball milling again and crushing to 200 meshes or above.
Weighing a granular reducing agent, a non-supported manganese-cerium composite catalyst and a denitration synergist according to a mass ratio, and mixing in a mixer; conveying the mixture to a rotary drum granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution on the surface of the mixture, and carrying out rolling granulation; and conveying the produced granules to a drying cylinder for drying, sieving the granules with the preferred diameter of 1.5-3.5mm, cooling and packaging.
The prepared granular composite denitration agent is used for denitration of coal-fired boiler flue gas, and is sprayed into the flue gas with the temperature of 1000-1100 ℃ after being sprayed into a combustion chamber.
Comparative example 3
The granular composite denitration agent is prepared according to the same formula and steps of example 6, but the preparation process of the unsupported manganese-cerium composite catalyst is not carried out with dilute sulfuric acid acidification treatment.
Comparative examples
Comparative example 1
Mn-TiO to be used in conventional SCR denitration module2The supported catalyst is transferred to a granular denitration agent. Mn-TiO2The preparation method of the catalyst comprises the following steps: dispersing 80 parts by mass of nano titanium dioxide in 100 parts by mass of water, uniformly stirring, adding 90 parts by mass of manganese nitrate into the nano titanium dioxide dispersion, drying in an oven, roasting at 500 ℃ for 6 hours, cooling, and ball-milling and crushing to 200 meshes or more. The prepared Mn-TiO2The catalyst was used in place of the unsupported manganese cerium composite catalyst described in example 1, and then a particulate composite denitration agent was prepared according to the same procedure.
Comparative example 2
Mn-TiO to be used in conventional SCR denitration module2The supported catalyst is transferred to a granular denitration agent. Mn-TiO2The preparation method of the catalyst comprises the following steps: dispersing 80 parts by mass of nano titanium dioxide in 100 parts by mass of water, uniformly stirring, adding 40 parts by mass of manganese nitrate into the nano titanium dioxide dispersion liquid, drying in an oven, roasting at 500 ℃ for 6 hours, cooling, and ball-milling and crushing to 200 meshes or more. The prepared Mn-TiO2The catalyst was used in place of the unsupported manganese cerium composite catalyst described in example 1, and then a particulate composite denitration agent was prepared according to the same procedure.
Comparative example 3
The supported manganese-cerium composite oxide catalyst used in the traditional SCR denitration module is transferred into a granular denitration agent. The preparation method of the manganese-cerium composite oxide catalyst comprises the following steps: fully dissolving 10 parts by mass of cerium nitrate and 90 parts by mass of manganese nitrate in water, adding 100 parts by mass of titanium oxide sieved by a 200-mesh sieve, uniformly stirring, drying in an oven, roasting for 6 hours at 450 ℃, cooling, and ball-milling and crushing to 200 meshes or more. The prepared supported manganese-cerium composite oxide catalyst was used in place of the unsupported cerium-manganese composite catalyst described in example 1, and then the particulate composite denitration agent was prepared according to the same procedure.
Comparative example 4
The supported manganese-cerium composite oxide catalyst used in the traditional SCR denitration module is transferred into a granular denitration agent. The preparation method of the manganese-cerium composite oxide catalyst comprises the following steps: fully dissolving 5 parts by mass of cerium nitrate and 95 parts by mass of manganese nitrate in water, adding 100 parts by mass of titanium oxide sieved by a 200-mesh sieve, uniformly stirring, drying in an oven, roasting for 6 hours at 450 ℃, cooling, and ball-milling and crushing to 200 meshes or more. The prepared supported manganese-cerium composite oxide catalyst was used in place of the unsupported manganese-cerium composite catalyst described in example 1, and then the particulate composite denitration agent was prepared according to the same procedure.
Comparative example 5
The supported manganese-cerium composite oxide catalyst used in the traditional SCR denitration module is transferred into a granular denitration agent. The preparation method of the manganese-cerium composite oxide catalyst comprises the following steps: fully dissolving 2 parts by mass of cerium nitrate and 98 parts by mass of manganese nitrate in water, adding 100 parts by mass of titanium oxide sieved by a 200-mesh sieve, uniformly stirring, drying in an oven, roasting for 5 hours at 500 ℃, cooling, and ball-milling and crushing to 200 meshes or more. The prepared supported manganese-cerium composite oxide catalyst was used in place of the unsupported manganese-cerium composite catalyst described in example 1, and then the particulate composite denitration agent was prepared according to the same procedure.
The mass percentages of cerium and manganese in the particulate composite denitration agents of examples 1 to 6 and comparative examples 1 to 3 with respect to the particulate denitration agent are shown in table 1.
TABLE 1
Evaluation of denitration Effect
The flue gas full-temperature denitration agents prepared in the embodiments 1-6, the comparison examples 1-3 and the comparison examples 1-5 are used in an industrial field in real timeOnline monitoring of NO in chimney gas of incineration facilityxAnd NH3Concentration change of NO in chimney gas without using granular composite denitration agentxThe hour-average concentration of the flue gas is the initial concentration, and NO in the flue gas is used when the flue gas full-temperature denitration agent is usedxThe hourly mean concentration of (a) is the concentration after treatment, and the denitration effect of the prepared granular composite denitration agent is evaluated, and the results are shown in tables 2 to 3.
As can be seen from the using effect data of the examples 1 to 6 in the table 2, the granular composite denitration agent prepared by the examples 1 to 6 in the patent can ensure that the hourly mean concentration of NOx in the discharged flue gas is 80mg/Nm3The hourly mean ammonia slip concentration was controlled to 8mg/Nm3Hereinafter, the denitration efficiency is more than 75%.
As can be seen from the data of the use effects of comparative examples 1 to 3 in Table 3, compared with the use effects of the particulate denitration agents prepared in examples 4 to 6, the unsupported manganese cerium composite catalyst in the particulate denitration agent is used without dilute sulfuric acid acidification treatment, and the same NO is used in the same processxUnder the conditions of initial concentration and the same using amount of the particulate denitration agent, the hour-average concentration of NOx in the flue gas rises by about 10-34%, and the hour-average concentration of ammonia escaping rises by 23-38%, which shows that the SO in the flue gas can be effectively reduced or avoided by using the non-supported manganese-cerium composite catalyst subjected to dilute sulfuric acid acidification treatment2The catalyst deactivation caused by the method enhances the catalytic denitration and catalytic deamination effects of the catalyst.
As can be seen from the use effect data of comparative examples 1-5 in Table 4, compared with the use effect of example 1, the supported Mn-TiO used in the traditional SCR denitration module2The granular denitration agent prepared by transferring the catalyst and the manganese-cerium composite oxide catalyst into the granular denitration agent cannot fully ensure that the hourly mean concentration of NOx in the discharged flue gas is 80mg/Nm3The hourly mean concentration of ammonia slip was difficult to control at 8mg/Nm3Hereinafter, the denitration efficiency is significantly decreased.
The above are only preferred embodiments of the present invention. It should be noted that the above-mentioned preferred embodiments should not be considered as limiting the invention, whose scope shall be governed by the scope defined by the claims. It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention, and such changes and modifications should be considered as within the scope of the invention.
Claims (20)
1. The granular denitration agent is characterized by comprising the following components by mass percent of 100 percent: 5-20% of non-load manganese cerium composite catalyst, a proper amount of binder and the balance of reducing agent;
wherein the reducing agent is urea, ammonium chloride or melamine or a mixture of any two or three of the urea, the ammonium chloride or the melamine in any proportion, and the reducing agent is in a granular form;
the non-supported manganese-cerium composite catalyst comprises a manganese oxide and cerium oxide; based on 100% of the mass of the granular denitration agent, the content of manganese element in the non-supported manganese-cerium composite catalyst is not less than 1.4%, and the content of cerium element is not less than 0.04%; the non-supported manganese-cerium composite catalyst is adhered to the surface of the granular reducing agent through a binder;
the binder is a water-soluble thermosetting resin having a decomposition temperature of 600 ℃ or lower.
2. The particulate denitrifier according to claim 1, wherein the denitrifier contains manganese in an amount of not less than 1.5%, for example, 1.5 to 12%, based on 100% by mass of the denitrifier; the content of cerium is not less than 0.05%, for example, 0.05 to 1.6%.
3. The granular denitration agent according to claim 1, wherein the granular composite denitration agent further comprises 1-10% of synergist, preferably 2-10% or 3-10%, and the synergist is sodium bicarbonate or magnesium ore powder or a mixture of the sodium bicarbonate and the magnesium ore powder in any proportion; the synergist is adhered to the surface of the granular reducing agent through a binder.
4. The particulate denitration agent according to claim 3, wherein the particulate composite denitration agent comprises the following components: 5-20% of unsupported manganese cerium composite catalyst, such as 6-18% or 9-18%, 1-10% of synergist, proper amount of binder and the balance of reducing agent.
5. The granular denitration agent as claimed in claim 1, wherein the binder is one of water-soluble polyurethane resin and water-soluble urea-formaldehyde resin or a mixture of the two at any ratio.
6. The granular denitration agent according to claim 1, wherein the mass percentage of the manganese oxide is 4.5-19.8%, and the preferable range is 5-18% based on 100% of the granular denitration agent; the mass percentage of the cerium oxide is 0.05-2.0 percent, and the preferred range is 0.1-1.8 percent, based on 100 percent of the mass of the granular denitration agent.
7. The granular denitration agent according to claim 1, wherein the manganese oxide is manganese dioxide, manganese ore powder or a mixture of the manganese dioxide and the manganese ore powder in any proportion.
8. The particulate denitration agent according to any one of claims 1 to 7, wherein the reducing agent is particulate urea; the non-supported manganese-cerium composite catalyst comprises manganese ore powder; the binder is water-soluble polyurethane resin or water-soluble urea-formaldehyde resin.
9. The particulate denitration agent according to claim 1, wherein the unsupported manganese-cerium composite catalyst is prepared by a method comprising: calcining the mixture of cerium oxide and manganese oxide, and pulverizing, such as ball milling to 200 mesh or finer; preferably, the cerium oxide and manganese oxide mixture is treated with dilute sulfuric acid before being calcined.
10. The particulate denitrifier according to claim 1, wherein the particulate denitrifier has a diameter of 1.0 to 4.0mm, preferably 1.5 to 3.5 mm.
11. The method for preparing the particulate denitration agent according to claim 1, comprising the steps of:
the method comprises the following steps: uniformly mixing a granular reducing agent, a non-supported manganese-cerium composite catalyst and a synergist to obtain a mixture;
step two: preparing an organic binder into an aqueous solution, spraying the aqueous solution onto the mixture, and coating and granulating the mixture;
step three: and (4) drying the granules produced in the step two, and sieving and screening the granules with the diameter of 1.0-4.0mm, preferably 1.5-3.5mm to obtain the granular denitration agent.
12. The use of the particulate denitrifier of claim 1 in the denitration of flue gas, wherein: the granular denitration agent is injected into high-temperature flue gas at 850-.
13. An unsupported manganese-cerium composite catalyst is characterized by comprising manganese oxide and cerium oxide; based on the mass of the composite catalyst as 100%, the mass percent of cerium oxide is 1-10%, and the mass percent of manganese oxide is 90-99%.
14. The unsupported manganese-cerium composite catalyst according to claim 13, wherein the manganese oxide is manganese dioxide, manganese ore powder or a mixture of the two in any proportion.
15. The unsupported manganese-cerium composite catalyst according to claim 13 or 14, wherein the mass percent of cerium oxide is 2-9%, and the mass percent of manganese oxide is 91-98%; or the mass percent of cerium oxide is 3-8%, and the mass percent of manganese oxide is 92-97%; the mass percent of cerium oxide is 3-9%, and the mass percent of manganese oxide is 91-97%; the mass percent of cerium oxide is 3-10%, and the mass percent of manganese oxide is 90-97%; the particle size of the non-supported manganese-cerium composite catalyst is 200 meshes or finer.
16. The unsupported manganese-cerium composite catalyst according to claim 13, prepared by a process comprising: and roasting and crushing the mixture of cerium oxide and manganese oxide to obtain the non-supported manganese-cerium composite catalyst.
17. The unsupported manganese-cerium composite catalyst according to claim 13, prepared by a process comprising: mixing cerium oxide and manganese oxide in proportion; roasting at the temperature of 300-500 ℃ after treatment by dilute sulfuric acid; cooling and crushing to obtain the non-supported manganese cerium composite catalyst.
18. Use of the unsupported manganese-cerium composite catalyst according to any one of claims 13 to 17 for the preparation of a particulate denitrifier for flue gas denitration.
19. The use of the unsupported manganese-cerium composite catalyst according to claim 18 in the preparation of a particulate denitration agent for flue gas denitration, wherein the particulate denitration agent comprises 5-20% of the unsupported manganese-cerium composite catalyst, a binder and a reducing agent, based on 100% by mass of the denitration agent; the reducing agent is particulate urea; the content of manganese element in the non-supported manganese-cerium composite catalyst is not less than 1.4 percent, and the content of cerium element in the non-supported manganese-cerium composite catalyst is not less than 0.04 percent; the non-supported manganese-cerium composite catalyst is adhered to the surface of the granular reducing agent through a binder; the binder is a water-soluble thermosetting resin having a decomposition temperature of 600 ℃ or lower, such as a water-soluble polyurethane resin or a water-soluble urea resin.
20. The use of the unsupported manganese-cerium composite catalyst according to claim 19 in the preparation of a particulate denitration agent for flue gas denitration, wherein the content of manganese element in the unsupported manganese-cerium composite catalyst is not less than 1.5%, for example 1.5-12%; the content of cerium is not less than 0.05%, for example, 0.05 to 1.6%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114768868A (en) * | 2022-05-06 | 2022-07-22 | 无锡卓能环境科技有限公司 | Preparation method of urea suitable for flue gas denitration of biomass boilers such as waste incineration |
| CN114870828A (en) * | 2022-05-20 | 2022-08-09 | 安徽中环环保科技股份有限公司 | Honeycomb stone cerium-loaded composite denitration agent and preparation method and application thereof |
| CN115414777A (en) * | 2022-08-12 | 2022-12-02 | 太原钢铁(集团)有限公司 | Composite denitration agent for lime rotary kiln tail flue gas denitration and preparation process thereof |
| CN116272334A (en) * | 2022-12-26 | 2023-06-23 | 杭州尚善若水环保科技有限公司 | Coupling desulfurization and denitrification medicament, preparation method and use method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0909583A1 (en) * | 1997-10-17 | 1999-04-21 | Nikki-Universal Co., Ltd. | Supported catalysts,preparation and use thereof |
| JP2003038143A (en) * | 2001-07-26 | 2003-02-12 | Mitsubishi Gas Chem Co Inc | Deoxidization agent composition |
| CN101952023A (en) * | 2007-10-08 | 2011-01-19 | 巴斯夫欧洲公司 | Use of moulded bodies with catalytic properties as reactor fittings |
| CN102078753A (en) * | 2010-12-31 | 2011-06-01 | 华东理工大学 | Cellular activated carbon-based denitration catalyst as well as preparation and application thereof |
| CN105050711A (en) * | 2013-03-14 | 2015-11-11 | 庄信万丰股份有限公司 | Cerium-modified manganese octahedral molecular sieves as catalysts for selective catalytic reduction |
| CN105289586A (en) * | 2015-11-29 | 2016-02-03 | 北京化工大学 | Spherical cerium-manganese composite oxide low-temperature denitration catalyst, and preparation method and application thereof |
| CN111282569A (en) * | 2020-03-11 | 2020-06-16 | 浙江大学 | Mixed synergistic enhanced low-temperature SCR denitration catalyst and preparation method thereof |
| CN111467880A (en) * | 2020-06-24 | 2020-07-31 | 苏州中材非金属矿工业设计研究院有限公司 | Multifunctional air filtering material and preparation method thereof |
| CN113522287A (en) * | 2021-06-24 | 2021-10-22 | 中科合成油技术有限公司 | Carbon-supported metal catalyst with hierarchical pore structure, preparation method and application thereof |
| CN113713607A (en) * | 2021-08-25 | 2021-11-30 | 同碧(上海)环保科技有限公司 | Granular ICR (intensive Care reactor) denitration agent and preparation method thereof |
| CN113769547A (en) * | 2021-08-31 | 2021-12-10 | 嘉兴沃特泰科环保科技股份有限公司 | Granular composite denitration agent and preparation method thereof |
-
2022
- 2022-01-05 CN CN202210005287.1A patent/CN114307634A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0909583A1 (en) * | 1997-10-17 | 1999-04-21 | Nikki-Universal Co., Ltd. | Supported catalysts,preparation and use thereof |
| JP2003038143A (en) * | 2001-07-26 | 2003-02-12 | Mitsubishi Gas Chem Co Inc | Deoxidization agent composition |
| CN101952023A (en) * | 2007-10-08 | 2011-01-19 | 巴斯夫欧洲公司 | Use of moulded bodies with catalytic properties as reactor fittings |
| CN102078753A (en) * | 2010-12-31 | 2011-06-01 | 华东理工大学 | Cellular activated carbon-based denitration catalyst as well as preparation and application thereof |
| CN105050711A (en) * | 2013-03-14 | 2015-11-11 | 庄信万丰股份有限公司 | Cerium-modified manganese octahedral molecular sieves as catalysts for selective catalytic reduction |
| US20160346770A1 (en) * | 2013-03-14 | 2016-12-01 | Johnson Matthey Public Limited Company | Cerium-modified manganese octahedral molecular sieves as catalysts for selective catalytic reduction |
| CN105289586A (en) * | 2015-11-29 | 2016-02-03 | 北京化工大学 | Spherical cerium-manganese composite oxide low-temperature denitration catalyst, and preparation method and application thereof |
| CN111282569A (en) * | 2020-03-11 | 2020-06-16 | 浙江大学 | Mixed synergistic enhanced low-temperature SCR denitration catalyst and preparation method thereof |
| CN111467880A (en) * | 2020-06-24 | 2020-07-31 | 苏州中材非金属矿工业设计研究院有限公司 | Multifunctional air filtering material and preparation method thereof |
| CN113522287A (en) * | 2021-06-24 | 2021-10-22 | 中科合成油技术有限公司 | Carbon-supported metal catalyst with hierarchical pore structure, preparation method and application thereof |
| CN113713607A (en) * | 2021-08-25 | 2021-11-30 | 同碧(上海)环保科技有限公司 | Granular ICR (intensive Care reactor) denitration agent and preparation method thereof |
| CN113769547A (en) * | 2021-08-31 | 2021-12-10 | 嘉兴沃特泰科环保科技股份有限公司 | Granular composite denitration agent and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114768868A (en) * | 2022-05-06 | 2022-07-22 | 无锡卓能环境科技有限公司 | Preparation method of urea suitable for flue gas denitration of biomass boilers such as waste incineration |
| CN114870828A (en) * | 2022-05-20 | 2022-08-09 | 安徽中环环保科技股份有限公司 | Honeycomb stone cerium-loaded composite denitration agent and preparation method and application thereof |
| CN115414777A (en) * | 2022-08-12 | 2022-12-02 | 太原钢铁(集团)有限公司 | Composite denitration agent for lime rotary kiln tail flue gas denitration and preparation process thereof |
| CN116272334A (en) * | 2022-12-26 | 2023-06-23 | 杭州尚善若水环保科技有限公司 | Coupling desulfurization and denitrification medicament, preparation method and use method thereof |
| CN116272334B (en) * | 2022-12-26 | 2023-08-15 | 杭州尚善若水环保科技有限公司 | Coupling desulfurization and denitrification medicament, preparation method and use method thereof |
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