CN106732639A - Denitrating catalyst and preparation method thereof - Google Patents

Denitrating catalyst and preparation method thereof Download PDF

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Publication number
CN106732639A
CN106732639A CN201611217966.6A CN201611217966A CN106732639A CN 106732639 A CN106732639 A CN 106732639A CN 201611217966 A CN201611217966 A CN 201611217966A CN 106732639 A CN106732639 A CN 106732639A
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tio
catalyst
activated carbon
denitrating catalyst
composite
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吴道洪
宋敏洁
陈珊
王东方
王志军
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Beijing Shenwu Environmental and Energy Technology Co Ltd
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Beijing Shenwu Environmental and Energy Technology Co Ltd
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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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses denitrating catalyst and preparation method thereof, wherein, preparation method includes：Prepare the precipitation mixture of titanium hydroxide and aluminium hydroxide；Precipitation mixture is dried and is calcined, TiO is obtained2‑Al2O3Composite oxide carrier powder；By TiO2‑Al2O3Composite oxide carrier powder carries out extrusion molding, sizing and dries with active carbon powder, enamel powder and binding agent, obtains activated carbon/TiO2‑Al2O3Composite catalyst；Ammonium metatungstate, ammonium metavanadate are dissolved in oxalic acid, the first maceration extract is obtained；By activated carbon/TiO2‑Al2O3Composite catalyst is impregnated in the first maceration extract, obtains V2O5‑WO3/ activated carbon/TiO2‑Al2O3Composite catalyst；Prepare the second maceration extract；And by V2O5‑WO3/ activated carbon/TiO2‑Al2O3Composite catalyst is impregnated in the second maceration extract, obtains denitrating catalyst.The denitrating catalyst prepared using the method has denitration catalyst activity higher, and anti-wear performance and acid resistance are strong, active wide temperature region, and waste heat recovery can be carried out while denitration process are carried out to pending flue gas.

Description

Denitrating catalyst and preparation method thereof
Technical field
The present invention relates to chemical technology field, specifically, the present invention relates to denitrating catalyst and preparation method thereof.
Background technology
The NO of mankind's activity dischargexMore than 90% comes from fuel combustion process.It is various industrial furnaces, Civil energy-saving cooking stove, motor-driven During high temperature combustion of fuel in car and other internal combustion engines, the nitrogen substance oxidation generation NO in fuelx, in the air of participation burning N2And O2Also NO can be generatedx.From the point of view of energy resource structure, during the primary energy and power generation energy resource of China are constituted, coal is occupied definitely Leading position.And the coal of China more than 80% is directly burning, particularly for power station, Industrial Boiler and civil boiler In.Therefore, in considerably long period, the NO in flue gasXDischarge is to cause China air NOxOne principal element of pollution, how Reduce the NO of fixed source emissionXIt is an important topic of atmospheric environment improvement.
Denitrating flue gas belong to burning post-processing technology, and the smoke evacuation system of many developed countries all needs to install denitrating flue gas dress Put.Denitration method for flue gas is more, but obtains the only selective catalytic reduction and selectivity of a large amount of commercial Applications at present and non-urge Change reducing process.
China's coal-fired plant flue gas ash content is high, easily causes a series of problems, such as catalyst abrasion, blocking, poisoning, catalyst Blocking, poisoning can be by regenerating activity recovery, but catalyst abrasion is then the damage of catalyst physical structure, it is impossible to regenerate, mill Damage is the key factor of catalyst consumption.In addition, denitrating catalyst is contacted with acid strong corrosive medium aborning, cause catalysis The seriously corroded of agent, and also have elliptical gear phenomenon of the solid particle to catalyst while acid corrosion, long-term continuous Under applying working condition, catalyst is easy to damage.
Existing denitrating catalyst wear resistant technology is generally hardened using end face, and the resistance to of catalyst is improve to a certain extent Ash content is very high in mill performance, but China's ature of coal, and the only hardening of end face can't be fully solved the problem of catalyst abrasion, especially In the case of Flow Field Distribution inequality, catalyst can occur rupture because of wear-resisting insufficient strength, collapse under the washing away of ash flue gas high for it The non-renewable physical damage such as sunken.
Thus, current denitrating catalyst still has much room for improvement.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.Therefore, of the invention One purpose is to propose denitrating catalyst and preparation method thereof.The denitrating catalyst has denitration catalyst activity higher, resistance to Mill performance and acid resistance are strong, active wide temperature region, and waste heat can be carried out while denitration process are carried out to pending flue gas Reclaim, so as to reach the purpose of energy-conserving and environment-protective.
In the first aspect of the present invention, the present invention proposes a kind of method for preparing denitrating catalyst.It is of the invention Embodiment, the method includes：(1) titanium source reagent and silicon source reagent are configured to the titanium source aqueous solution and silicon source solution respectively, and will The titanium source aqueous solution and source of aluminium solution are co-precipitated, and are mixed with the precipitation of aluminium hydroxide to prepare titanium hydroxide Compound；(2) precipitation mixture is carried out into the first drying and the first roasting, to obtain TiO2-Al2O3Composite oxides are carried Body powder；(3) by the TiO2-Al2O3Composite oxide carrier powder is carried out with active carbon powder, enamel powder and binding agent Extrusion molding, sizing and drying, to obtain activated carbon/TiO2-Al2O3Composite catalyst；(4) by ammonium metatungstate, ammonium metavanadate It is dissolved in oxalic acid, to obtain the first maceration extract；(5) by the activated carbon/TiO2-Al2O3Composite catalyst is described first The first dipping is carried out in maceration extract, the second drying and the second roasting is carried out after completing first dipping, to obtain V2O5- WO3/ activated carbon/TiO2-Al2O3Composite catalyst；(6) iron chloride, lanthanum chloride are configured to mixed aqueous solution, to obtain Two maceration extracts；And (7) are by the V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst enters in second maceration extract Row second impregnates, and the 3rd drying and the 3rd roasting is carried out after completing second dipping, to obtain denitrating catalyst.
Thus, embodiments in accordance with the present invention, the method prepares TiO by using titanium source reagent and silicon source reagent2- Al2O3Composite oxide carrier, and then be molded, shaped and dried with active component activated carbon and additive enamel, lived Property charcoal/TiO2-Al2O3Composite catalyst, activated carbon has flourishing pore structure and huge specific surface area, thus with strong Adsorptivity, meanwhile, activated carbon surface contains polynary oxygen-containing functional group, can adsorb the SO in pending flue gas2And vapor, from And improve the anti-SO of the denitrating catalyst for preparing2, vapour resistant poisoning performance, meanwhile, can be made by adding enamel The denitrating catalyst for preparing has hardness and wear-resisting, acid resistance higher；Further, by by activated carbon/TiO2- Al2O3Composite catalyst carries out the first dipping in the first maceration extract, can make active component alum and tungsten load activated carbon/ TiO2-Al2O3On composite catalyst, and then the second drying and the second roasting are carried out, obtain V2O5-WO3/ activated carbon/TiO2-Al2O3 Composite catalyst, thus, it is possible to make catalyst surface while adsorbing NH3With NO molecules, rich in oxidation activity position activated carbon And V2O5-WO3There is redox reaction in complex oxide surface, generate N2And H2O, reaches the purpose of removing NO；And then, will V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst carries out the second dipping in the second maceration extract, loads auxiliary agent iron and lanthanum In V2O5-WO3/ activated carbon/TiO2-Al2O3On composite catalyst, lived so as to significantly improve denitrating catalyst catalysis at low temperature Property.Thus, catalysis high can be effectively prepared using the method for preparing denitrating catalyst according to embodiments of the present invention to live Property, high abrasion, acid resistance, the denitrating catalyst of active wide temperature region.
In addition, the method for preparing denitrating catalyst according to the above embodiment of the present invention can also have following additional skill Art feature：
In some embodiments of the invention, in step (1), the titanium source aqueous solution is dense with the quality of source of aluminium solution Degree is than being 1:(0.01~2).
In some embodiments of the invention, in step (4), vanadium and the mol ratio of tungsten are 1 in first maceration extract: (0.1~5).Thus, it is possible to significantly improve the catalytic performance of the denitrating catalyst for preparing.
In some embodiments of the invention, in step (3), the sizing and drying are temperature at 95~115 degrees Celsius Carried out under degree.
In some embodiments of the invention, in step (3), the activated carbon/TiO that extrusion molding is obtained2-Al2O3It is multiple That closes catalyst is shaped as spherical, strip or honeycomb ceramics shape, preferably honeycomb ceramics shape.Thus, it is possible to significantly improve what is prepared The specific surface area of denitrating catalyst, so as to further improve the catalytic performance of the denitrating catalyst.
In some embodiments of the invention, in step (2), first roasting is carried out under 350~600 degrees Celsius Complete within 5~8 hours.
In some embodiments of the invention, in step (5), second roasting is carried out under 350~600 degrees Celsius Complete within 5~8 hours.
In some embodiments of the invention, in step (7), the 3rd roasting is carried out under 350~600 degrees Celsius Complete within 5~8 hours.
In some embodiments of the invention, the denitrating catalyst is with TiO2-Al2O3Composite oxides are carrier, with work Property charcoal be main active, with V2O5-WO3It is Supplementary active ingredients, using transition metal iron, rare-earth elements of lanthanum as auxiliary agent, with Enamel is used as additive；Wherein, based on the denitrating catalyst oeverall quality, the TiO2-Al2O3Composite oxide supported amount It is 10~60 mass %, the load capacity of the activated carbon is 10~50 mass %, the V2O5-WO3The load capacity of composite oxides Be 5~20 mass %, the transition metal iron load capacity be 0.1~10 mass %, the rare-earth elements of lanthanum load capacity be 0.1~ 10 mass %, the load capacity of the enamel is 1~10 mass %.Thus, the denitrating catalyst has denitration catalyst higher Activity, anti-wear performance and acid resistance are strong, active wide temperature region, and can enter while denitration process are carried out to pending flue gas Row waste heat recovery, so as to reach the purpose of energy-conserving and environment-protective.
In the second aspect of the present invention, the present invention proposes a kind of denitrating catalyst, and embodiments in accordance with the present invention are described Denitrating catalyst is prepared by the above-mentioned method for preparing denitrating catalyst according to embodiments of the present invention.
Thus, embodiments in accordance with the present invention, the denitrating catalyst has denitration catalyst activity higher, anti-wear performance Strong, the active wide temperature region with acid resistance, and waste heat recovery can be carried out while denitration process are carried out to pending flue gas, from And reach the purpose of energy-conserving and environment-protective.
In addition, denitrating catalyst according to the above embodiment of the present invention can also have following additional technical characteristic：
In some embodiments of the invention, the denitrating catalyst is with TiO2-Al2O3Composite oxides are carrier, with work Property charcoal be main active, with V2O5-WO3It is Supplementary active ingredients, using transition metal iron, rare-earth elements of lanthanum as auxiliary agent, with Enamel is used as additive；Wherein, based on the denitrating catalyst oeverall quality, the TiO2-Al2O3Composite oxide supported amount It is 10~60 mass %, the load capacity of the activated carbon is 10~50 mass %, the V2O5-WO3The load capacity of composite oxides Be 5~20 mass %, the transition metal iron load capacity be 0.1~10 mass %, the rare-earth elements of lanthanum load capacity be 0.1~ 10 mass %, the load capacity of the enamel is 1~10 mass %.Thus, the denitrating catalyst has denitration catalyst higher Activity, anti-wear performance and acid resistance are strong, active wide temperature region, and can enter while denitration process are carried out to pending flue gas Row waste heat recovery, so as to reach the purpose of energy-conserving and environment-protective.
In some embodiments of the invention, the TiO2-Al2O3The mol ratio of Ti and Al is 1 in composite oxides: (0.01~2), the V2O5-WO3The mol ratio of V and W is 1 in composite oxides:(0.1~5).Thus, it is possible to further improve The denitration catalyst activity of the denitrating catalyst.
Additional aspect of the invention and advantage will be set forth in part in the description, and will partly become from the following description Obtain substantially, or recognized by practice of the invention.
Brief description of the drawings
Of the invention above-mentioned and/or additional aspect and advantage will become from description of the accompanying drawings below to embodiment is combined Substantially and be readily appreciated that, wherein：
Fig. 1 is the method flow schematic diagram for preparing denitrating catalyst according to an embodiment of the invention.
Specific embodiment
Embodiments of the invention are described below in detail.The embodiments described below is exemplary, is only used for explaining this hair It is bright, and be not considered as limiting the invention.Unreceipted particular technique or condition in embodiment, according to text in the art Offer described technology or condition or carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument, For can by city available from conventional products.
In the description of the invention, it is to be understood that term " first ", " second " are only used for describing purpose, and can not It is interpreted as indicating or implying relative importance or the implicit quantity for indicating indicated technical characteristic.Thus, define " the One ", at least one this feature can be expressed or be implicitly included to the feature of " second ".
In the first aspect of the present invention, the present invention proposes a kind of method for preparing denitrating catalyst.It is of the invention Embodiment, the method includes：(1) titanium source reagent and silicon source reagent are configured to the titanium source aqueous solution and silicon source solution respectively, and will The titanium source aqueous solution and source of aluminium solution are co-precipitated, and are mixed with the precipitation of aluminium hydroxide to prepare titanium hydroxide Compound；(2) precipitation mixture is carried out into the first drying and the first roasting, to obtain TiO2-Al2O3Composite oxides are carried Body powder；(3) by the TiO2-Al2O3Composite oxide carrier powder is carried out with active carbon powder, enamel powder and binding agent Extrusion molding, sizing and drying, to obtain activated carbon/TiO2-Al2O3Composite catalyst；(4) by ammonium metatungstate, ammonium metavanadate It is dissolved in oxalic acid, to obtain the first maceration extract；(5) by the activated carbon/TiO2-Al2O3Composite catalyst is described first The first dipping is carried out in maceration extract, the second drying and the second roasting is carried out after completing first dipping, to obtain V2O5- WO3/ activated carbon/TiO2-Al2O3Composite catalyst；(6) iron chloride, lanthanum chloride are configured to mixed aqueous solution, to obtain Two maceration extracts；And (7) are by the V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst enters in second maceration extract Row second impregnates, and the 3rd drying and the 3rd roasting is carried out after completing second dipping, to obtain denitrating catalyst.
The method for preparing denitrating catalyst according to embodiments of the present invention is described in detail below, with reference to Fig. 1, the party Method includes：
S100：Prepare precipitation mixture
In the step, titanium source reagent and silicon source reagent are configured to the titanium source aqueous solution and silicon source solution respectively, and by titanium source The aqueous solution and silicon source solution are co-precipitated, to prepare the precipitation mixture of titanium hydroxide and aluminium hydroxide.Specifically, A certain amount of titanium source reagent of sulfuric acid oxygen titanium and silicon source reagent aluminium chloride can be taken, is dissolved separately in appropriate deionized water, stirred Mix uniform, to obtain the titanium source aqueous solution and silicon source solution；Further, by the titanium source aqueous solution, silicon source solution, ammoniacal liquor by simultaneously The mode of stream, is instilled by certain flow rate and is equipped with the reactor of a small amount of deionized water, and agitating device is provided with the reactor, it is ensured that Solution is well mixed, reaction is abundant, and the titanium source aqueous solution instills speed and can control the instillation speed of ammoniacal liquor with identical with silicon source solution Degree, the pH value of mixed liquor is controlled between 9~11, and co-precipitation obtains the precipitation mixture of titanium hydroxide and aluminium hydroxide.
Of the invention specifically to apply example, the titanium source aqueous solution and the mass concentration ratio of silicon source solution can be 1 in mixed liquor: (0.01~2), the precipitation mixture for thus preparing can be efficiently used for preparing TiO2-Al2O3Composite oxides are carried Body.
Embodiments in accordance with the present invention, the concentration of ammoniacal liquor is not particularly restricted, as long as can be used in the pH of mixed liquor Between 9~11, those skilled in the art can be selected according to actual needs for value control.
S200：Prepare TiO2-Al2O3Composite oxide carrier powder
In the step, precipitation mixture is carried out into the first drying and the first roasting, to obtain TiO2-Al2O3Combined oxidation Thing support powder.Specifically, precipitation mixture is carried out into filtering and washing for several times first, until filtrate pH value is 7 or so, Ran Houyi It is secondary to carry out the first drying and the first roasting, so that the Ti and Al in precipitation mixture are converted into TiO2-Al2O3Composite oxides Form.
Embodiments in accordance with the present invention, the first dry condition is not particularly restricted, and those skilled in the art can be with root Selected according to being actually needed, a specific embodiment of the invention, the first drying is carried out under 85~115 degrees Celsius Complete within 8~15 hours, it is possible thereby to effectively fully remove the moisture in precipitation mixture.
Embodiments in accordance with the present invention, the condition of the first roasting is not particularly restricted, and those skilled in the art can be with root Selected according to being actually needed, a specific embodiment of the invention, the first roasting is entered under 350~600 degrees Celsius What row was completed for 5~8 hours, it is possible thereby to the Ti and Al in precipitation mixture effectively are converted into TiO2-Al2O3Combined oxidation The form of thing, and then TiO can be significantly improved2-Al2O3The load capacity of activated carbon on composite oxide carrier.
S300：Prepare activated carbon/TiO2-Al2O3Composite catalyst
In the step, by TiO2-Al2O3Composite oxide carrier powder enters with active carbon powder, enamel powder and binding agent Row extrusion molding, sizing and drying, to obtain activated carbon/TiO2-Al2O3Composite catalyst.Embodiments in accordance with the present invention, Activated carbon has flourishing pore structure and huge specific surface area, thus with strong adsorptivity, meanwhile, activated carbon surface contains Polynary oxygen-containing functional group, can adsorb the SO in pending flue gas2And vapor, so as to improve the denitration catalyst for preparing The anti-SO of agent2, vapour resistant poisoning performance, meanwhile, embodiments in accordance with the present invention can make to prepare by adding enamel Denitrating catalyst have hardness and wear-resisting, acid resistance higher.
Embodiments in accordance with the present invention, the species of binding agent is not particularly restricted, and those skilled in the art can basis It is actually needed and is selected, a specific embodiment of the invention, binding agent can be glycerine, it is possible thereby to effectively will TiO2-Al2O3Composite oxide carrier powder is bonded with active carbon powder, enamel powder.
Embodiments in accordance with the present invention, activated carbon/TiO2-Al2O3The shape of composite catalyst is not particularly restricted, this Art personnel can be selected according to actual needs, according to a particular embodiment of the invention, the work that extrusion molding is obtained Property charcoal/TiO2-Al2O3The shape of composite catalyst can be spherical, strip or honeycomb ceramics shape, if catalyst is spherical, catalyst Diameter can be 3~6mm；If catalyst is strip, catalyst can be cylindrical shape, and diameter can be 3~6mm, length Can be 10~60mm；If catalyst is cellular, cross section can be cuboid, square, or circular, fan-shaped, Ellipse etc., size can for 150mm × 150mm × 150mm, 250mm × 200mm × 150mm etc., aperture can for 10mm × 10mm, 15mm × 15mm etc., profile, size, aperture determine after being considered according to composite factors such as specific operating mode, use environments. According to a preferred embodiment of the invention, activated carbon/TiO2-Al2O3Composite catalyst can be honeycomb ceramics shape, and inventor is by big Amount experiment it was unexpectedly observed that the specific surface area of the honeycomb ceramics shape catalyst catalyst of comparing other shapes is big, catalyst and reaction The contact surface of medium is bigger, and catalytic reaction is in hgher efficiency, and when catalyst is honeycomb ceramics shape, the specific surface area of catalyst exists 300m2/m3More than, mechanical strength is more than 2MPa, and the catalysis activity of nitrogen oxides reduction may be up to more than 98%.
Embodiments in accordance with the present invention, sizing and dry condition are not particularly restricted, and those skilled in the art can be with Selected according to actual needs, a specific embodiment of the invention, sizing and drying are at 95~115 degrees Celsius At a temperature of carry out, thus, it is possible to effectively to the activated carbon/TiO of extrusion molding2-Al2O3Composite catalyst is shaped, and Fully remove moisture therein.
S400：Prepare the first maceration extract
In the step, ammonium metatungstate, ammonium metavanadate are dissolved in oxalic acid, to obtain the first maceration extract.
According to a particular embodiment of the invention, vanadium and the mol ratio of tungsten are 1 in the first maceration extract:(0.1~5).Thus, may be used To significantly improve the load capacity of V and W in the denitrating catalyst for preparing, so as to improve the denitration performance of denitrating catalyst.
S500：Prepare V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst
In the step, by activated carbon/TiO2-Al2O3Composite catalyst carries out the first dipping in the first maceration extract, completes The second drying and the second roasting are carried out after dipping, to obtain V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst.Specifically Ground, dipping can carry out completing for 5~8 hours at normal temperatures, it is possible thereby to effectively make V and W be supported on activated carbon/TiO2- Al2O3On composite catalyst, after the completion of the first dipping, will be loaded with 85~115 degrees Celsius first the activated carbon of V and W/ TiO2-Al2O3Composite catalyst is dried 8~15 hours, so that moisture therein is fully removed, then carries out the second roasting.Root According to embodiments of the invention, inventor is had found, activated carbon/TiO is supported on by by active component V and W2-Al2O3Composite catalyzing In agent, catalyst surface can be made while adsorbing NH3With NO molecules, rich in oxidation activity position activated carbon and V2O5-WO3 There is redox reaction in complex oxide surface, generate N2And H2O, reaches the purpose of removing NO.
Embodiments in accordance with the present invention, the condition of the second roasting is not particularly restricted, and those skilled in the art can be with root Selected according to being actually needed, a specific embodiment of the invention, the second roasting is entered under 350~600 degrees Celsius What row was completed for 5~8 hours, it is possible thereby to effectively make V and W with V2O5-WO3The form of composite oxides be supported on activated carbon/ TiO2-Al2O3The surface of composite catalyst, such that it is able to significantly improve the denitration performance of denitrating catalyst.
S600：Prepare the second maceration extract
In the step, iron chloride, lanthanum chloride are configured to mixed aqueous solution, to obtain the second maceration extract.
Embodiments in accordance with the present invention, iron is not particularly restricted with the concentration of lanthanum in mixed aqueous solution, as long as can have Effect ground makes iron be supported on V with lanthanum2O5-WO3/ activated carbon/TiO2-Al2O3On composite catalyst, those skilled in the art can be with Selected according to actual needs.
S700：Obtain denitrating catalyst
In the step, by V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst carries out the second leaching in the second maceration extract Stain, carries out the 3rd drying and the 3rd roasting, to obtain denitrating catalyst after completing the second dipping.Specifically, can be by V2O5- WO3/ activated carbon/TiO2-Al2O3Composite catalyst incipient impregnation is in the second maceration extract, and dipping 5~8 is small at normal temperatures When, thus, it is possible to effectively make iron be supported on V with lanthanum2O5-WO3/ activated carbon/TiO2-Al2O3On composite catalyst, the second dipping After the completion of, the V of iron and lanthanum will be loaded with 85~115 degrees Celsius first2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyzing Agent is dried 8~15 hours, so that moisture therein is fully removed, then carries out the 3rd roasting.Embodiments in accordance with the present invention, Inventor's discovery, V is supported on by making transition metal iron and rare-earth elements of lanthanum2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyzing In agent, the denitrating catalyst for preparing catalysis activity under cryogenic can be significantly improved.
Embodiments in accordance with the present invention, the condition of the 3rd roasting is not particularly restricted, and those skilled in the art can be with root Selected according to being actually needed, a specific embodiment of the invention, the 3rd roasting is entered under 350~600 degrees Celsius What row was completed for 5~8 hours, thus, it is possible to effectively make iron be supported on V with lanthanum2O5-WO3/ activated carbon/TiO2-Al2O3It is compound to urge In agent, and then improve the denitrating catalyst for preparing catalysis activity at low temperature.
According to a particular embodiment of the invention, denitrating catalyst is with TiO2-Al2O3Composite oxides are carrier, with activated carbon It is main active, with V2O5-WO3It is Supplementary active ingredients, using transition metal iron, rare-earth elements of lanthanum as auxiliary agent, with enamel As additive；Wherein, based on denitrating catalyst oeverall quality, TiO2-Al2O3Composite oxide supported amount is 10~60 matter Amount %, the load capacity of activated carbon is 10~50 mass %, V2O5-WO3The load capacity of composite oxides is 5~20 mass %, transition Metallic iron load capacity is that 0.1~10 mass %, rare-earth elements of lanthanum load capacity are 0.1~10 mass %, the load capacity of enamel for 1~ 10 mass %.Thus, the denitrating catalyst has denitration catalyst activity higher, and anti-wear performance and acid resistance are strong, activity temperature Qu Kuan, and waste heat recovery can be carried out while denitration process are carried out to pending flue gas, so as to reach the mesh of energy-conserving and environment-protective 's.
Thus, embodiments in accordance with the present invention, the method prepares TiO by using titanium source reagent and silicon source reagent2- Al2O3Composite oxide carrier, and then be molded, shaped and dried with active component activated carbon and additive enamel, lived Property charcoal/TiO2-Al2O3Composite catalyst, activated carbon has flourishing pore structure and huge specific surface area, thus with strong Adsorptivity, meanwhile, activated carbon surface contains polynary oxygen-containing functional group, can adsorb the SO in pending flue gas2And vapor, from And improve the anti-SO of the denitrating catalyst for preparing2, vapour resistant poisoning performance, meanwhile, can be made by adding enamel The denitrating catalyst for preparing has hardness and wear-resisting, acid resistance higher；Further, by by activated carbon/TiO2- Al2O3Composite catalyst carries out the first dipping in the first maceration extract, can make active component alum and tungsten load activated carbon/ TiO2-Al2O3On composite catalyst, and then the second drying and the second roasting are carried out, obtain V2O5-WO3/ activated carbon/TiO2-Al2O3 Composite catalyst, thus, it is possible to make catalyst surface while adsorbing NH3With NO molecules, rich in oxidation activity position activated carbon And V2O5-WO3There is redox reaction in complex oxide surface, generate N2And H2O, reaches the purpose of removing NO；And then, will V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst carries out the second dipping in the second maceration extract, loads auxiliary agent iron and lanthanum In V2O5-WO3/ activated carbon/TiO2-Al2O3On composite catalyst, lived so as to significantly improve denitrating catalyst catalysis at low temperature Property.Thus, catalysis high can be effectively prepared using the method for preparing denitrating catalyst according to embodiments of the present invention to live Property, high abrasion, acid resistance, active wide temperature region and with function of recovering waste heat denitrating catalyst.
In the second aspect of the present invention, the present invention proposes a kind of denitrating catalyst, embodiments in accordance with the present invention, and this takes off Denox catalyst is prepared by the above-mentioned method for preparing denitrating catalyst according to embodiments of the present invention.
Embodiments in accordance with the present invention, the denitrating catalyst is with TiO2-Al2O3Composite oxides are carrier, are with activated carbon Main active, with V2O5-WO3It is Supplementary active ingredients, using transition metal iron, rare-earth elements of lanthanum as auxiliary agent, is made with enamel It is additive；Wherein, based on denitrating catalyst oeverall quality, TiO2-Al2O3Composite oxide supported amount is 10~60 mass %, The load capacity of activated carbon is 10~50 mass %, V2O5-WO3The load capacity of composite oxides is 5~20 mass %, transition metal Iron load capacity is 0.1~10 mass %, rare-earth elements of lanthanum load capacity is 0.1~10 mass %, and the load capacity of enamel is 1~10 matter Amount %.Thus, the denitrating catalyst has denitration catalyst activity higher, and anti-wear performance and acid resistance are strong, active wide temperature region, And waste heat recovery can be carried out while denitration process are carried out to pending flue gas, so as to reach the purpose of energy-conserving and environment-protective.
Embodiments in accordance with the present invention, TiO2-Al2O3The mol ratio of Ti and Al can be 1 in composite oxides:(0.01~ 2), it is possible thereby to significantly improve activated carbon in TiO2-Al2O3Load capacity on composite oxides, so as to improve prepare de- The catalysis activity of denox catalyst.
Embodiments in accordance with the present invention, V2O5-WO3The mol ratio of V and W is 1 in composite oxides:(0.1~5).Thus, The denitration catalyst activity of denitrating catalyst can further be improved.
Thus, embodiments in accordance with the present invention, the denitrating catalyst has a denitration catalyst activity higher, anti-wear performance and Acid resistance is strong, active wide temperature region, and waste heat recovery can be carried out while denitration process are carried out to pending flue gas, so that Reach the purpose of energy-conserving and environment-protective.
Below with reference to specific embodiment, present invention is described, it is necessary to explanation, these embodiments are only description Property, and the present invention is limited never in any form.
Embodiment 1
1st, carrier is prepared
The titanyl sulfate of 43.96g and the aluminium chloride of 36.64g are taken, is dissolved separately in appropriate deionized water, stirring is equal Even, it is 1 that the ratio between titanium source solution and silicon source solution, both concentration are obtained respectively:1.Titanium source solution, silicon source solution, the ammonia that will be obtained Water by way of cocurrent, by certain flow rate instill reactor in, be provided with agitating device in the reactor.Titanium source solution and silicon source Solution instillation speed is identical, controls the instillation speed of ammoniacal liquor, and by the pH value control of reaction solution 10, co-precipitation obtains titanium hydroxide With the precipitation mixture of aluminium hydroxide.By the sediment suction filtration, washing, it is repeated several times, until filtrate pH value is to 7 or so.Then After drying 12h under the conditions of 105 DEG C of baking oven, the solid that will be obtained is placed in Muffle furnace, and 350 are warming up to the speed of 5 DEG C/min DEG C, constant temperature 1.5h, constant temperature 3h, obtains TiO after being then warming up to 500 DEG C with the speed of 5 DEG C/min again2-Al2O3Composite oxides Carrier.
2nd, active component load
33.5g active components active carbon powder, 9.31g enamel powder are mixed with the support powder that above-mentioned steps are obtained It is even, after adding additive enamel, binding agent glycerine to stir, carry out being extruded into strip.Then by this part carry out microwave sizing, Dried process, obtains activated carbon/TiO after treatment2-Al2O3Composite catalyst.
Then the ammonium metavanadate reagent of the ammonium metatungstate of 11g, 5.07g is dissolved in appropriate oxalic acid, by previous step Activated carbon/the TiO for obtaining2-Al2O3Composite catalyst is dipped in isometric solution, and dipping temperature is normal temperature, dip time 6h, after drying 12h under the conditions of 105 DEG C after the completion of dipping, the solid that will be obtained is placed in Muffle furnace, with the speed of 5 DEG C/min It is warming up to 350 DEG C, constant temperature 1.5h, constant temperature 3h, obtains V after being then warming up to 500 DEG C with the speed of 5 DEG C/min again2O5-WO3/ living Property charcoal/TiO2-Al2O3Composite catalyst.
3rd, auxiliary agent load
By the iron chloride (FeCl of 9.18g3·6H2O), 5.04g lanthanum chlorides (LaCl3·7H2O) be dissolved in it is appropriate go from In sub- water, and catalyst precursor obtained above is dipped in isometric solution, dipping temperature is normal temperature, dip time 6h, after drying 12h under the conditions of 105 DEG C after the completion of dipping, the solid that will be obtained is placed in Muffle furnace, with the speed of 5 DEG C/min 350 DEG C are warming up to, constant temperature 1.5h, constant temperature 3h after being then warming up to 500 DEG C with the speed of 5 DEG C/min again obtain enamel to add The denitrating catalyst finished product of agent.
4th, measuring mechanical property
The above-mentioned strip catalyst (section is 5mm × 5mm circular) that length is 50mm is taken, is surveyed by detector for strength of particles It is 2.5MPa to obtain catalyst axial direction mechanical strength.
5th, catalyst activity evaluation
Obtained catalyst carries out activity rating, air speed 5000h by fixed bed catalyst evaluating apparatus-1, in flue gas NH3/ NO is 1, and controlling reaction temperature is 200~250 DEG C, and the denitration activity of catalyst is up to 99%.Reaction temperature is 400 DEG C When, the denitration activity of catalyst is up to more than 89%.
Embodiment 2
1st, carrier is prepared
The titanyl sulfate of 72.77g and the aluminium chloride of 30.33g are taken, is dissolved separately in appropriate deionized water, stirring is equal Even, it is 1 that the ratio between titanium source solution and silicon source solution, both concentration are obtained respectively:0.5.The titanium source solution that to obtain, silicon source solution, Ammoniacal liquor by way of cocurrent, by certain flow rate instill reactor in, be provided with agitating device in the reactor.Titanium source solution and aluminium Source solution instillation speed is identical, controls the instillation speed of ammoniacal liquor, and by the pH value control of reaction solution 10, co-precipitation obtains hydroxide The precipitation mixture of titanium and aluminium hydroxide.By the sediment suction filtration, washing, it is repeated several times, until filtrate pH value is to 7 or so.So After drying 12h under the conditions of 110 DEG C of baking oven afterwards, the solid that will be obtained is placed in Muffle furnace, is warming up to the speed of 10 DEG C/min 350 DEG C, constant temperature 2h, constant temperature 2h, obtains TiO after being then warming up to 500 DEG C with the speed of 5 DEG C/min again2-Al2O3Composite oxides Carrier.
2nd, active component load
27g active components active carbon powder, 4.79g enamel powder are mixed with the support powder that above-mentioned steps are obtained It is even, after adding additive enamel, binding agent glycerine to stir, carry out being extruded into honeycomb shaped.Then this part is carried out micro- Ripple sizing, dried process, obtain activated carbon/TiO after treatment2-Al2O3Composite catalyst.
Then the ammonium metavanadate reagent of the ammonium metatungstate of 9.2g, 8.48g is dissolved in appropriate oxalic acid, by previous step Activated carbon/the TiO for obtaining2-Al2O3Composite catalyst is dipped in isometric solution, and dipping temperature is normal temperature, dip time 6h, after drying 10h under the conditions of 110 DEG C after the completion of dipping, the solid that will be obtained is placed in Muffle furnace, with the speed of 10 DEG C/min It is warming up to 350 DEG C, constant temperature 2h, constant temperature 2h, obtains V after being then warming up to 500 DEG C with the speed of 5 DEG C/min again2O5-WO3/ activity Charcoal/TiO2-Al2O3Composite catalyst.
3rd, auxiliary agent load
By the iron chloride (FeCl of 3.39g3·6H2O), 6.38g lanthanum chlorides (LaCl3·7H2O) be dissolved in it is appropriate go from In sub- water, and catalyst precursor obtained above is dipped in isometric solution, dipping temperature is normal temperature, dip time 8h, after drying 12h under the conditions of 110 DEG C after the completion of dipping, the solid that will be obtained is placed in Muffle furnace, with the speed of 10 DEG C/min 350 DEG C are warming up to, constant temperature 1.5h, constant temperature 3h after being then warming up to 500 DEG C with the speed of 5 DEG C/min again obtain enamel to add The denitrating catalyst finished product of agent.
4th, measuring mechanical property
The above-mentioned honeycomb ceramics shape catalyst (section is 5mm × 5mm squares) that length is 50mm is taken, is surveyed by granule strength Determine instrument to measure catalyst axial direction mechanical strength is 2.9MPa.
5th, catalyst activity evaluation
Obtained catalyst carries out activity rating, air speed 5000h by fixed bed catalyst evaluating apparatus-1, in flue gas NH3/ NO is 1, and controlling reaction temperature is 200~250 DEG C, and the denitration activity of catalyst is up to 100%.Reaction temperature is 400 DEG C When, the denitration activity of catalyst is up to more than 92%.
Embodiment 3
1st, carrier is prepared
The titanyl sulfate of 37.79g and the aluminium chloride of 63.01g are taken, is dissolved separately in appropriate deionized water, stirring is equal Even, it is 1 that the ratio between titanium source solution and silicon source solution, both concentration are obtained respectively:2.Titanium source solution, silicon source solution, the ammonia that will be obtained Water by way of cocurrent, by certain flow rate instill reactor in, be provided with agitating device in the reactor.Titanium source solution and silicon source Solution instillation speed is identical, controls the instillation speed of ammoniacal liquor, and by the pH value control of reaction solution 10, co-precipitation obtains titanium hydroxide With the precipitation mixture of aluminium hydroxide.By the sediment suction filtration, washing, it is repeated several times, until filtrate pH value is to 7 or so.Then After drying 8h under the conditions of 115 DEG C of baking oven, the solid that will be obtained is placed in Muffle furnace, and 350 are warming up to the speed of 10 DEG C/min DEG C, constant temperature 2h, constant temperature 2h, obtains TiO after being then warming up to 500 DEG C with the speed of 5 DEG C/min again2-Al2O3Composite oxides are carried Body.
2nd, active component load
28g active components active carbon powder, 6.79g enamel powder are mixed with the support powder that above-mentioned steps are obtained It is even, after adding additive enamel, binding agent glycerine to stir, carry out being extruded into honeycomb shaped.Then this part is carried out micro- Ripple sizing, dried process, obtain activated carbon/TiO after treatment2-Al2O3Composite catalyst.
Then the ammonium metavanadate reagent of the ammonium metatungstate of 16.45g, 2.53g is dissolved in appropriate oxalic acid, by previous step Rapid activated carbon/the TiO for obtaining2-Al2O3Composite catalyst is dipped in isometric solution, and dipping temperature is normal temperature, during dipping Between 6h, after drying 8h under the conditions of 115 DEG C after the completion of dipping, the solid that will be obtained is placed in Muffle furnace, with the speed of 10 DEG C/min Degree is warming up to 350 DEG C, constant temperature 2h, and constant temperature 2h, obtains V after being then warming up to 500 DEG C with the speed of 5 DEG C/min again2O5-WO3/ living Property charcoal/TiO2-Al2O3Composite catalyst.
3rd, auxiliary agent load
By the iron chloride (FeCl of 5.42g3·6H2O), 6.38g lanthanum chlorides (LaCl3·7H2O) be dissolved in it is appropriate go from In sub- water, and catalyst precursor obtained above is dipped in isometric solution, dipping temperature is normal temperature, dip time 5h, after drying 8h under the conditions of 115 DEG C after the completion of dipping, the solid that will be obtained is placed in Muffle furnace, with the speed of 10 DEG C/min 350 DEG C are warming up to, constant temperature 1.5h, constant temperature 3h after being then warming up to 600 DEG C with the speed of 5 DEG C/min again obtain enamel to add The denitrating catalyst finished product of agent.
4th, measuring mechanical property
The above-mentioned honeycomb ceramics shape catalyst (section is 5mm × 5mm squares) that length is 50mm is taken, is surveyed by granule strength Determine instrument to measure catalyst axial direction mechanical strength is 2.2MPa.
5th, catalyst activity evaluation
Obtained catalyst carries out activity rating, air speed 5000h by fixed bed catalyst evaluating apparatus-1, in flue gas NH3/ NO is 1, and controlling reaction temperature is 200~250 DEG C, and the denitration activity of catalyst is up to 96%.Reaction temperature is 400 DEG C When, the denitration activity of catalyst is up to more than 83%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office Combined in an appropriate manner in one or more embodiments or example.Additionally, in the case of not conflicting, the skill of this area Art personnel can be tied the feature of the different embodiments or example described in this specification and different embodiments or example Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned Embodiment is changed, changes, replacing and modification.

Claims (10)

1. a kind of method for preparing denitrating catalyst, it is characterised in that including：
(1) titanium source reagent and silicon source reagent are configured to the titanium source aqueous solution and silicon source solution respectively, and by the titanium source aqueous solution It is co-precipitated with source of aluminium solution, to prepare the precipitation mixture of titanium hydroxide and aluminium hydroxide；
(2) precipitation mixture is carried out into the first drying and the first roasting, to obtain TiO2-Al2O3Composite oxide carrier Powder；
(3) by the TiO2-Al2O3Composite oxide carrier powder is extruded with active carbon powder, enamel powder and binding agent It is molded, shapes and dries, to obtain activated carbon/TiO2-Al2O3Composite catalyst；
(4) ammonium metatungstate, ammonium metavanadate are dissolved in oxalic acid, to obtain the first maceration extract；
(5) by the activated carbon/TiO2-Al2O3Composite catalyst carries out the first dipping in first maceration extract, completes institute The second drying and the second roasting are carried out after stating the first dipping, to obtain V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyzing Agent；
(6) iron chloride, lanthanum chloride are configured to mixed aqueous solution, to obtain the second maceration extract；And
(7) by the V2O5-WO3/ activated carbon/TiO2-Al2O3Composite catalyst carries out the second leaching in second maceration extract Stain, carries out the 3rd drying and the 3rd roasting, to obtain denitrating catalyst after completing second dipping.
2. the method for preparing denitrating catalyst according to claim 1, it is characterised in that in step (1), the titanium source water Solution is 1 with the mass concentration ratio of source of aluminium solution:(0.01~2).
3. the method for preparing denitrating catalyst according to claim 1, it is characterised in that in step (4), first leaching Vanadium and the mol ratio of tungsten are 1 in stain liquid:(0.1~5).
4. the method for preparing denitrating catalyst according to claim 1, it is characterised in that in step (3), the sizing and Drying is carried out at a temperature of 95~115 degrees Celsius.
5. the method for preparing denitrating catalyst according to claim 1, it is characterised in that in step (3), extrusion molding is obtained Activated carbon/the TiO for arriving2-Al2O3Being shaped as composite catalyst is spherical, strip or honeycomb ceramics shape,
It is preferred that honeycomb ceramics shape.
6. the method for preparing denitrating catalyst according to claim 1, it is characterised in that in step (2), first roasting Burning is to carry out completing for 5~8 hours under 350~600 degrees Celsius,
Optionally, in step (5), second roasting is to carry out completing for 5~8 hours under 350~600 degrees Celsius,
Optionally, in step (7), the 3rd roasting is to carry out completing for 5~8 hours under 350~600 degrees Celsius.
7. the method for preparing denitrating catalyst according to claim 1, it is characterised in that the denitrating catalyst is with TiO2- Al2O3Composite oxides are carrier, with activated carbon as main active, with V2O5-WO3It is Supplementary active ingredients, with transition gold Category iron, rare-earth elements of lanthanum as auxiliary agent, using enamel as additive；
Wherein, based on the denitrating catalyst oeverall quality, the TiO2-Al2O3Composite oxide supported amount is 10~60 matter Amount %, the load capacity of the activated carbon is 10~50 mass %, the V2O5-WO3The load capacity of composite oxides is 5~20 matter Amount %, the transition metal iron load capacity is 0.1~10 mass %, the rare-earth elements of lanthanum load capacity is 0.1~10 mass %, The load capacity of the enamel is 1~10 mass %.
8. a kind of denitrating catalyst, it is characterised in that the denitrating catalyst is by claim 1~7 any one methods described Prepare.
9. denitrating catalyst according to claim 8, it is characterised in that the denitrating catalyst is with TiO2-Al2O3It is compound Oxide is carrier, with activated carbon as main active, with V2O5-WO3Composite oxides are Supplementary active ingredients, with transition Metallic iron, rare-earth elements of lanthanum as auxiliary agent, using enamel as additive；
Wherein, based on the denitrating catalyst oeverall quality, the TiO2-Al2O3Composite oxide supported amount is 10~60 matter Amount %, the load capacity of the activated carbon is 10~50 mass %, the V2O5-WO3The load capacity of composite oxides is 5~20 matter Amount %, the transition metal iron load capacity is 0.1~10 mass %, the rare-earth elements of lanthanum load capacity is 0.1~10 mass %, The load capacity of the enamel is 1~10 mass %.
10. denitrating catalyst according to claim 9, it is characterised in that the TiO2-Al2O3In composite oxides Ti with The mol ratio of Al is 1:(0.01~2), the V2O5-WO3The mol ratio of V and W is 1 in composite oxides:(0.1~5).
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CN115990491A (en) * 2021-10-20 2023-04-21 中国石油天然气股份有限公司 Denitration catalyst and preparation method and application thereof
CN114247447A (en) * 2021-11-23 2022-03-29 中海油天津化工研究设计院有限公司 Low-temperature denitration catalyst with modified carbon material as carrier and preparation method thereof
CN114247447B (en) * 2021-11-23 2024-02-13 中海油天津化工研究设计院有限公司 Low-temperature denitration catalyst taking modified carbon material as carrier and preparation method thereof
CN114931943A (en) * 2022-05-18 2022-08-23 山东亮剑环保新材料有限公司 SCR denitration catalyst and production method thereof
CN115920900A (en) * 2022-11-24 2023-04-07 大唐南京环保科技有限责任公司 Supermolecule low-temperature honeycomb denitration catalyst with ball-like structure and preparation method thereof
CN116116451A (en) * 2022-11-25 2023-05-16 光大环境科技（中国）有限公司 Preparation method of low-temperature synergistic denitration and dioxin removal composite catalyst

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