CN107812517A - A kind of cerium tungsten tantalum denitrating catalyst and preparation method thereof - Google Patents

A kind of cerium tungsten tantalum denitrating catalyst and preparation method thereof Download PDF

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CN107812517A
CN107812517A CN201610820706.1A CN201610820706A CN107812517A CN 107812517 A CN107812517 A CN 107812517A CN 201610820706 A CN201610820706 A CN 201610820706A CN 107812517 A CN107812517 A CN 107812517A
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tantalum
cerium
catalyst
tungsten
source
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陈勇
胡建锋
吴晓东
吴新谦
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Longyan Cercis Innovation Research Institute
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Longyan Cercis Innovation Research Institute
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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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—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
    • 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
    • B01D53/90—Injecting reactants
    • 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

Abstract

The present invention provides a kind of cerium tungsten tantalum denitrating catalyst, and elemental cerium, elemental tungsten, the mol ratio of element tantalum are 2~5 in the catalyst：1~4：1~4.The preparation method of above-mentioned cerium tungsten tantalum denitrating catalyst, comprises the following steps：1) first by cerium source and tungsten source mixed dissolution in water, tantalum source is then added, obtains mixed solution；2) use weak caustic solution regulating step 1) gained mixed solution pH so that pH value reaches 9~11；3) mixing liquid obtained by step 2) is filtered successively, dried, ground, active component is made；4) active component and carrier powder, auxiliary agent and water obtained by step 3) is taken to be mixed and stirred for uniformly, obtaining paste pug；5) paste pug obtained by step 4) is subjected to extrusion molding, obtains preformed catalyst；6) take preformed catalyst obtained by step 5) to be dried, obtain dried preformed catalyst；7) dried preformed catalyst obtained by step 6) is calcined, obtains cerium tungsten tantalum denitrating catalyst finished product.Denitrating catalyst nonhazardous prepared by the present invention, activity are high, service life length.

Description

A kind of cerium tungsten tantalum denitrating catalyst and preparation method thereof
Technical field
The present invention relates to a kind of selective catalyst reduction of nitrogen oxides (NOx) catalyst and preparation method thereof, especially relate to A kind of and cerium tungsten tantalum denitrating catalyst and preparation method thereof.
Background technology
In recent years, problem of environmental pollution is more and more prominent, and the haze weather of continuation occurs in north of China large area region, So that people focus more on the improvement of air environmental pollution, NOxOne of main reason as haze, is arranged by environmental administration The atmosphere pollution administered for emphasis, various purification NOxDenitration technology greatly developed and applied.
SCR technology (SCR) is current efficiency highest denitration technology, and its denitration efficiency can reach More than 80%, its technical principle is：In reducing agent NH3Under the conditions of existing, contain NOxFlue gas by catalyst, in a constant temperature Surface in the range of degree in catalyst chemically reacts so that NOxWith NH3Reaction changes into harmless N2And H2O.SCR technology The characteristics of be NO in the presence of catalystxAnd NH3Can just it be reacted between about 300 DEG C to 400 DEG C, at present, country row Put NOxStationary source be coal-burning boiler, what discharged from coal-fired boiler came out contains NOxFlue gas substantially all in this temperature Section, therefore, as long as to catalyst can SCR reactions directly occur for boiler emission smoke contacts, SCR technology is big so as to obtain Sizable application.
The core of SCR denitration technology is denitrating catalyst, at present, V2O5-WO3/TiO2It is wide Deng catalytic component based on vanadium General is used for business denitrating catalyst, and it, with good activity, while has good anti-when between 300 DEG C to 400 DEG C Hydrothermal stability and sulfur poisoning-resistant.But main active vfanadium compound is a kind of noxious material, in the use of catalyst During, it can be distributed in surrounding environment, so as to produce harm to health and ecological environment.Meanwhile discarded vanadium base The problem of processing of denitrating catalyst also receives much concern as one.
Existing SCR denitration has a drawback to be can be by NOxThe influence of middle sulfur dioxide and easily lose work Property, and then reduce the service life of denitrating catalyst.
For this reason, it may be necessary to provide a kind of nonhazardous, high activity, the denitrating catalyst of service life length, and the catalyst is used In Selective Catalytic Reduction of NOx。
The content of the invention
Denitrating catalyst grown the invention reside in a kind of nonhazardous of offer, high activity, service life and preparation method thereof.
What the present invention was realized in：
A kind of cerium tungsten tantalum denitrating catalyst, elemental cerium, elemental tungsten, the mol ratio of element tantalum are 2~5 in the catalyst：1~ 4：1~4.
In cerium tungsten tantalum denitrating catalyst, when the mol ratio of these three elements is in this scope, its catalytic activity is best.
A kind of preparation method of cerium tungsten tantalum denitrating catalyst as described above, comprises the following steps：
1) first by cerium source and tungsten source mixed dissolution in water, tantalum source is then added, obtains mixed solution；
The cerium source includes the one or more of cerous nitrate, cerous acetate, cerous carbonate, cerous sulfate or cerous cerium hydroxide；
The tungsten source includes ammonium paratungstate, the one or more of ammonium metatungstate；
The tantalum source includes the one or more of ethanol tantalum, tantalic chloride, tantalum hydroxide or tantalum pentoxide；
Cerium source, the preferred above-mentioned substance in tungsten source and tantalum source, it is every other to be dissolved in water and containing the change of cerium, tungsten and tantalum element Compound can regard cerium source, tungsten source and tantalum source.
Because cerium source, tungsten source and tantalum source are substantially powder granule thing, if directly mixed, it is difficult to well mixed.Cerium source, The purpose that tungsten source and tantalum source are dissolved in the water is that the amount that water is added in order that it is well mixed at least should ensure that and be enough to dissolve cerium Source, tungsten source and tantalum source.It is to allow these three active components to be uniformly dispersed that cerium source, tungsten source are well mixed with tantalum source, is so made The catalyst activity obtained is more preferable.
Cerium source and tungsten source are first mixed, then add tantalum source, this is done to allow Ce first together with W precipitations, shape Viability preferably Ce-W systems；Then Ta is introduced, Ta is incorporated in the surface of Ce-W systems, due to Ta2O5Property it is stable, can To cause the resistance to SO_2 of the component of whole activity to improve, and then extend the service life of catalyst.
2) use weak caustic solution regulating step 1) gained mixed solution pH so that pH value reaches 9~11；
With the pH of weak base regulation solution, be on the one hand advantageous to the regulation of pH value, another aspect weak base will not be to active component Activity have an impact.When solution ph reaches 9~11, active component can than being more completely precipitated out from solution, So the purpose for adjusting pH with weak caustic solution is in order to allow active component to be precipitated out as far as possible, in case filtering uses in next step.
3) mixing liquid obtained by step 2) is filtered, obtains pug；The pug for filtering gained is dried, obtained Block；The block of gained after drying is ground, obtains powder, gained powder is active component；
After mixed liquor cooling obtained by step 2) active component is had to be precipitated out, using the method for filtering collect activity into Point, obtain block.Block grind into powder is easy to be well mixed with support powder, auxiliary agent and water in step 4).
4) active component and carrier powder, auxiliary agent and water obtained by step 3) is taken to be mixed and stirred for uniformly, obtaining paste pug；
The effect for adding carrier is load active component, allows active component to be dispersed in carrier surface, allows active component Fully haptoreaction thing, catalytic reaction thing it can be reacted.
Add auxiliary agent and be advantageous to catalyst machine-shaping.
Preferably matched on the basis of support powder quality, between each component as follows：Active component and carrier powder quality Than for 1:7 to 1:11, auxiliary agent is 1 with support powder mass ratio:9 to 1:18, water is 1 with support powder mass ratio:2 to 1:4.
5) paste pug obtained by step 4) is subjected to extrusion molding, obtains preformed catalyst；
Extrusion molding is carried out with extrusion forming device, required shape can be extruded according to being actually needed.
6) take preformed catalyst obtained by step 5) to be dried, obtain dried preformed catalyst；
7) dried preformed catalyst obtained by step 6) is calcined, obtains cerium tungsten tantalum denitrating catalyst finished product.
Preferably, after mixing cerium source and tungsten source in step 1), 6 hours~12 hours are stood, 6 are stood again after adding tantalum source Hour~12 hours.
The purpose stood for the first time be in order to form active preferably Ce-W systems, stand for second be in order that Ta is suitable Profit combines the surface of Ce-W systems.
Preferably, weak caustic solution includes urea liquid or ammonia spirit in step 2).
Ammonia spirit preferred mass fraction is 20%~30% ammonia spirit.While add weak caustic solution, while testing molten Liquid pH, until pH value of solution reaches 9~11, then stopping adds alkali lye.
Preferably, step 2) also includes heating and whipping step；Heating-up temperature is 50 DEG C~120 DEG C, and mixing time is 8 small When~12 hours.
Heating and stirring purpose be in order that active component mixing it is more uniform.
Preferably, drying condition is in 100 DEG C~120 DEG C dryings 8 hours~16 hours in step 3).
Preferably, support powder includes TiO in step 4)2Powder, SiO2Powder, Al2O3The one or more of powder.
Carrier can be the mixture of single carrier or several carriers.
Preferably, it is adjuvant used including structural promoter, bonding agent, acid solution, alkali lye in step 4)；Wherein, structural promoter bag Glass fibre, paper pulp cotton or stearic one or more are included, bonding agent includes carboxymethyl cellulose or polyoxyethylene, acid solution bag Lactic acid is included, alkali lye includes ammonia spirit or urea liquid.
Preferably, preformed catalyst is cellular square body or cellular cylinder in step 5).
Preferably, calcination condition is to be calcined 3 hours~8 hours at 300 DEG C~700 DEG C in step 7).
Heating rate can not be too fast in calcination process, and decomposition reaction is not abundant enough in the too fast then catalyst of heating rate, system The catalyst performance obtained is bad, and the heating rate in experiment is generally less than 10 DEG C/min.
The invention has the advantages that：
Tungsten is a kind of good solid acid modifying agent, due to its good activity and stability, in high temperature stationary source flue gas Denitration field, tungsten have the potentiality for substituting vanadium.
A kind of cerium LREE higher as content, price is relatively low, has the condition of large-scale application, CeO2 With good oxygen migration performance and storage put oxygen performance, therefore, CeO2It can be used for Selective Catalytic Reduction of NOx。CeO2And transition Metal oxide combines the redox property that will be helpful to improve catalyst.
Tantalum is a kind of stable chemical element of property, and Ta oxide is a kind of solid acid oxide of good performance, tool There is good catalytic performance, meanwhile, the property of Ta oxides is relatively stable.
Containing cerium, tungsten, three kinds of elements of tantalum material denitrating catalyst, not only without the toxic action of vanadium, and have Higher catalytic activity and preferable resistance to SO_2.
Cerium source and tungsten source are first mixed, then add tantalum source, this is done to allow Ce first together with W precipitations, shape Viability preferably Ce-W systems；Then Ta is introduced, Ta is incorporated in the surface of Ce-W systems, due to Ta2O5Property it is stable, can To cause the resistance to SO_2 of the component of whole activity to improve, and then extend the service life of catalyst.
Brief description of the drawings
Fig. 1 is the catalytic efficiency curve map of catalyst at different temperatures；
Fig. 2 is resistance to SO_2 curve map of the catalyst within a period of time.
Embodiment
To describe the technology contents of the present invention, construction feature, the objects and the effects in detail, below in conjunction with embodiment And accompanying drawing is coordinated to be explained in detail.
Embodiment 1
A kind of cerium tungsten tantalum denitrating catalyst, elemental cerium, elemental tungsten, the mol ratio of element tantalum are 2 in the catalyst：4：1.
The preparation method of above-mentioned cerium tungsten tantalum denitrating catalyst, comprises the following steps：
1) first by cerium source and tungsten source mixed dissolution in water, 6 hours are stood；Then add tantalum source and stand 10 hours again, Obtain mixed solution；Cerium source, tungsten source, the sampling in tantalum source are as shown in the table：
Cerium source Molecular weight Weigh quality/g
Ce(NO3)3·6H2O 434.12
Ce(AC)3·5H2O 407.28
Ce2(CO3)3·5H2O 550.33 550.33
Ce(SO4)2·4H2O 404.30
Ce(OH)3 191.14
Tungsten source Molecular weight Weigh quality/g
(NH4)5W12O38.5H2O 3133.37 1044.46
(NH4)6W7O24.6H2O 1887.26
Tantalum source Molecular weight Weigh quality/g
C10H25O5Ta 406.29 406.29
TaCl5 358.21
Ta(OH)5 266
Ta2O5 441.89
2) use urea liquid regulating step 1) gained mixed solution pH so that pH value reaches 9；Heat and stir；Heating Temperature is 50 DEG C, and mixing time is 12 hours.
3) mixing liquid obtained by step 2) is filtered, obtains pug；The pug for filtering gained is dried 8 at 120 DEG C Hour is dried, and obtains block；The block of gained after drying is ground, obtains powder, gained powder is activearm Point；
4) active component and carrier powder, auxiliary agent and water obtained by step 3) is taken to be mixed and stirred for uniformly, obtaining paste pug； The sampling of active component and carrier powder, auxiliary agent and water is as shown in the table：
5) paste pug obtained by step 4) is subjected to extrusion molding, preformed catalyst is cellular cylinder, is molded Catalyst；
6) take preformed catalyst obtained by step 5) to be dried, obtain dried preformed catalyst；
7) dried preformed catalyst obtained by step 6) to be calcined, calcination condition is to be calcined 8 hours at 300 DEG C, Obtain cerium tungsten tantalum denitrating catalyst finished product.
Embodiment 2
A kind of cerium tungsten tantalum denitrating catalyst, elemental cerium, elemental tungsten, the mol ratio of element tantalum are 5 in the catalyst：1：4.
The preparation method of above-mentioned cerium tungsten tantalum denitrating catalyst, comprises the following steps：
1) first by cerium source and tungsten source mixed dissolution in water, 12 hours are stood；Then add tantalum source and stand 8 hours again, Obtain mixed solution；Cerium source, tungsten source, the sampling in tantalum source are as shown in the table：
Cerium source Molecular weight Weigh quality/g
Ce(NO3)3·6H2O 434.12 434.12
Ce(AC)3·5H2O 407.28 407.28
Ce2(CO3)3·5H2O 550.33 550.33
Ce(SO4)2·4H2O 404.30 404.30
Ce(OH)3 191.14
Tungsten source Molecular weight Weigh quality/g
(NH4)5W12O38.5H2O 3133.37
(NH4)6W7O24.6H2O 1887.26 269.61
Tantalum source Molecular weight Weigh quality/g
C10H25O5Ta 406.29 1432.84
TaCl5 358.21
Ta(OH)5 266
Ta2O5 441.89
2) use ammonia spirit regulating step 1) gained mixed solution pH so that pH value reaches 10；Heat and stir；Heating Temperature is 120 DEG C, and mixing time is 8 hours.
3) mixing liquid obtained by step 2) is filtered, obtains pug；The pug for filtering gained is dried 16 at 100 DEG C Hour is dried, and obtains block；The block of gained after drying is ground, obtains powder, gained powder is activearm Point；
4) active component and carrier powder, auxiliary agent and water obtained by step 3) is taken to be mixed and stirred for uniformly, obtaining paste pug； The sampling of active component and carrier powder, auxiliary agent and water is as shown in the table：
5) paste pug obtained by step 4) is subjected to extrusion molding, preformed catalyst is cellular square body, is molded Catalyst；
6) take preformed catalyst obtained by step 5) to be dried, obtain dried preformed catalyst；
7) dried preformed catalyst obtained by step 6) to be calcined, calcination condition is to be calcined 3 hours at 700 DEG C, Obtain cerium tungsten tantalum denitrating catalyst finished product.
Embodiment 3
A kind of cerium tungsten tantalum denitrating catalyst, elemental cerium, elemental tungsten, the mol ratio of element tantalum are 3 in the catalyst：2：3.
The preparation method of above-mentioned cerium tungsten tantalum denitrating catalyst, comprises the following steps：
1) first by cerium source and tungsten source mixed dissolution in water, 7 hours are stood；Then add tantalum source and stand 11 hours again, Obtain mixed solution；Cerium source, tungsten source, the sampling in tantalum source are as shown in the table：
2) use urea liquid regulating step 1) gained mixed solution pH so that pH value reaches 11；Heat and stir；Heating Temperature is 60 DEG C, and mixing time is 11 hours.
3) mixing liquid obtained by step 2) is filtered, obtains pug；The pug for filtering gained is dried 9 at 115 DEG C Hour is dried, and obtains block；The block of gained after drying is ground, obtains powder, gained powder is activearm Point；
4) active component and carrier powder, auxiliary agent and water obtained by step 3) is taken to be mixed and stirred for uniformly, obtaining paste pug； The sampling of active component and carrier powder, auxiliary agent and water is as shown in the table：
5) paste pug obtained by step 4) is subjected to extrusion molding, preformed catalyst is cellular cylinder, is molded Catalyst；
6) take preformed catalyst obtained by step 5) to be dried, obtain dried preformed catalyst；
7) dried preformed catalyst obtained by step 6) to be calcined, calcination condition is to be calcined 7 hours at 400 DEG C, Obtain cerium tungsten tantalum denitrating catalyst finished product.
Embodiment 4
A kind of cerium tungsten tantalum denitrating catalyst, elemental cerium, elemental tungsten, the mol ratio of element tantalum are 4 in the catalyst：3：2.
The preparation method of above-mentioned cerium tungsten tantalum denitrating catalyst, comprises the following steps：
1) first by cerium source and tungsten source mixed dissolution in water, 11 hours are stood；Then add tantalum source and stand 7 hours again, Obtain mixed solution；Cerium source, tungsten source, the sampling in tantalum source are as shown in the table：
2) use ammonia spirit regulating step 1) gained mixed solution pH so that pH value reaches 11；Heat and stir；Heating Temperature is 105 DEG C, and mixing time is 9 hours.
3) mixing liquid obtained by step 2) is filtered, obtains pug；The pug for filtering gained is dried 14 at 105 DEG C Hour is dried, and obtains block；The block of gained after drying is ground, obtains powder, gained powder is activearm Point；
4) active component and carrier powder, auxiliary agent and water obtained by step 3) is taken to be mixed and stirred for uniformly, obtaining paste pug； The sampling of active component and carrier powder, auxiliary agent and water is as shown in the table：
5) paste pug obtained by step 4) is subjected to extrusion molding, preformed catalyst is cellular square body, is molded Catalyst；
6) take preformed catalyst obtained by step 5) to be dried, obtain dried preformed catalyst；
7) dried preformed catalyst obtained by step 6) to be calcined, calcination condition is to be calcined 4 hours at 600 DEG C, Obtain cerium tungsten tantalum denitrating catalyst finished product.
Embodiment 5
A kind of cerium tungsten tantalum denitrating catalyst, elemental cerium, elemental tungsten, the mol ratio of element tantalum are 5 in the catalyst：4：4.
The preparation method of above-mentioned cerium tungsten tantalum denitrating catalyst, comprises the following steps：
1) first by cerium source and tungsten source mixed dissolution in water, 8 hours are stood；Then add tantalum source and stand 12 hours again, Obtain mixed solution；Cerium source, tungsten source, the sampling in tantalum source are as shown in the table：
Cerium source Molecular weight Weigh quality/g
Ce(NO3)3·6H2O 434.12 434.12
Ce(AC)3·5H2O 407.28
Ce2(CO3)3·5H2O 550.33 550.33
Ce(SO4)2·4H2O 404.30 404.30
Ce(OH)3 191.14 191.14
Tungsten source Molecular weight Weigh quality/g
(NH4)5W12O38.5H2O 3133.37 1044.46
(NH4)6W7O24.6H2O 1887.26
Tantalum source Molecular weight Weigh quality/g
C10H25O5Ta 406.29
TaCl5 358.21 358.21
Ta(OH)5 266 266
Ta2O5 441.89 441.89
2) use urea liquid regulating step 1) gained mixed solution pH so that pH value reaches 10；Heat and stir；Heating Temperature is 75 DEG C, and mixing time is 10 hours.
3) mixing liquid obtained by step 2) is filtered, obtains pug；The pug for filtering gained is dried 11 at 110 DEG C Hour is dried, and obtains block；The block of gained after drying is ground, obtains powder, gained powder is activearm Point；
4) active component and carrier powder, auxiliary agent and water obtained by step 3) is taken to be mixed and stirred for uniformly, obtaining paste pug； The sampling of active component and carrier powder, auxiliary agent and water is as shown in the table：
5) paste pug obtained by step 4) is subjected to extrusion molding, preformed catalyst is cellular cylinder, is molded Catalyst；
6) take preformed catalyst obtained by step 5) to be dried, obtain dried preformed catalyst；
7) dried preformed catalyst obtained by step 6) to be calcined, calcination condition is to be calcined 5 hours at 500 DEG C, Obtain cerium tungsten tantalum denitrating catalyst finished product.
Embodiment 6
A kind of cerium tungsten tantalum denitrating catalyst, elemental cerium, elemental tungsten, the mol ratio of element tantalum are 2 in the catalyst：1：1.
The preparation method of above-mentioned cerium tungsten tantalum denitrating catalyst, comprises the following steps：
1) first by cerium source and tungsten source mixed dissolution in water, 10 hours are stood；Then add tantalum source and stand 6 hours again, Obtain mixed solution；Cerium source, tungsten source, the sampling in tantalum source are as shown in the table：
2) use ammonia spirit regulating step 1) gained mixed solution pH so that pH value reaches 9；Heat and stir；Heating Temperature is 95 DEG C, and mixing time is 10 hours.
3) mixing liquid obtained by step 2) is filtered, obtains pug；The pug for filtering gained is dried 12 at 110 DEG C Hour is dried, and obtains block；The block of gained after drying is ground, obtains powder, gained powder is activearm Point；
4) active component and carrier powder, auxiliary agent and water obtained by step 3) is taken to be mixed and stirred for uniformly, obtaining paste pug； The sampling of active component and carrier powder, auxiliary agent and water is as shown in the table：
5) paste pug obtained by step 4) is subjected to extrusion molding, preformed catalyst is cellular square body, is molded Catalyst；
6) take preformed catalyst obtained by step 5) to be dried, obtain dried preformed catalyst；
7) dried preformed catalyst obtained by step 6) to be calcined, calcination condition is to be calcined 6 hours at 500 DEG C, Obtain cerium tungsten tantalum denitrating catalyst finished product.
Catalyst performance is tested：In continuously flowing fixed bed device, under normal pressure, reaction velocity 5000h-1, prepare mould Intend flue gas includes NO, SO by catalyst, simulated flue gas2(SO2Concentration is 250ppm), NH3And H2O, N2As Balance Air, use The NO of flue gas analyzer detection reactor inlet and outletxConcentration, calculate the catalytic efficiency of catalyst.
Fig. 1 is the catalytic efficiency curve map of catalyst at different temperatures prepared by embodiment 6.Can from figure Go out, when reaction temperature reaches more than 305 DEG C, the efficiency of catalyst can reach more than 90%, and reaction temperature rises to 490 DEG C When, the efficiency of catalyst still maintains more than 90%.
Fig. 2 is resistance to SO_2 curve map of the catalyst within a period of time prepared by embodiment 6.The sulfur poisoning-resistant of catalyst Property is tested, and works as SO2When concentration is 250ppm and test temperature is 300 DEG C, every test in 30 minutes once.The catalyst After 24 hours, denitration efficiency can maintain 87% or so.
Embodiments of the invention are the foregoing is only, not thereby limit the scope of patent protection of the present invention, every utilization The equivalent structure or equivalent flow conversion that description of the invention and accompanying drawing content are made, or directly or indirectly it is used in other correlations Technical field, be included within the scope of the present invention.

Claims (10)

  1. A kind of 1. cerium tungsten tantalum denitrating catalyst, it is characterised in that：Elemental cerium, elemental tungsten, the mol ratio of element tantalum in the catalyst For 2~5：1~4：1~4.
  2. 2. a kind of preparation method of cerium tungsten tantalum denitrating catalyst as claimed in claim 1, comprises the following steps：
    1) first by cerium source and tungsten source mixed dissolution in water, tantalum source is then added, obtains mixed solution；
    The cerium source includes the one or more of cerous nitrate, cerous acetate, cerous carbonate, cerous sulfate or cerous cerium hydroxide；
    The tungsten source includes ammonium paratungstate, the one or more of ammonium metatungstate；
    The tantalum source includes the one or more of ethanol tantalum, tantalic chloride, tantalum hydroxide or tantalum pentoxide；
    2) use weak caustic solution regulating step 1) gained mixed solution pH so that pH value reaches 9~11；
    3) mixing liquid obtained by step 2) is filtered, obtains pug；The pug for filtering gained is dried, obtains bulk Thing；The block of gained after drying is ground, obtains powder, gained powder is active component；
    4) active component and carrier powder, auxiliary agent and water obtained by step 3) is taken to be mixed and stirred for uniformly, obtaining paste pug；
    5) paste pug obtained by step 4) is subjected to extrusion molding, obtains preformed catalyst；
    6) take preformed catalyst obtained by step 5) to be dried, obtain dried preformed catalyst；
    7) dried preformed catalyst obtained by step 6) is calcined, obtains cerium tungsten tantalum denitrating catalyst finished product.
  3. 3. the preparation method of cerium tungsten tantalum denitrating catalyst as claimed in claim 2, it is characterised in that in step 1) by cerium source and After the mixing of tungsten source, 6 hours~12 hours are stood, 6 hours~12 hours are stood again after adding tantalum source.
  4. 4. the preparation method of cerium tungsten tantalum denitrating catalyst as claimed in claim 2, it is characterised in that weak caustic solution in step 2) Including urea liquid or ammonia spirit.
  5. 5. the preparation method of cerium tungsten tantalum denitrating catalyst as claimed in claim 2, it is characterised in that step 2) also includes heating And whipping step；Heating-up temperature is 50 DEG C~120 DEG C, and mixing time is 8 hours~12 hours.
  6. 6. the preparation method of cerium tungsten tantalum denitrating catalyst as claimed in claim 2, it is characterised in that drying condition in step 3) For in 100 DEG C~120 DEG C dryings 8 hours~16 hours.
  7. 7. the preparation method of cerium tungsten tantalum denitrating catalyst as claimed in claim 2, it is characterised in that support powder in step 4) Including TiO2Powder, SiO2Powder, Al2O3The one or more of powder.
  8. 8. the preparation method of cerium tungsten tantalum denitrating catalyst as claimed in claim 2, it is characterised in that adjuvant used in step 4) Including structural promoter, bonding agent, acid solution, alkali lye；Wherein, structural promoter includes glass fibre, paper pulp cotton or stearic one kind Or it is several, bonding agent includes carboxymethyl cellulose or polyoxyethylene, and acid solution includes lactic acid, and alkali lye includes ammonia spirit or urea is molten Liquid.
  9. 9. the preparation method of cerium tungsten tantalum denitrating catalyst as claimed in claim 2, it is characterised in that shaped catalyst in step 5) Agent is cellular square body or cellular cylinder.
  10. 10. the preparation method of cerium tungsten tantalum denitrating catalyst as claimed in claim 2, it is characterised in that calcining bar in step 7) Part is to be calcined 3 hours~8 hours at 300 DEG C~700 DEG C.
CN201610820706.1A 2016-09-13 2016-09-13 A kind of cerium tungsten tantalum denitrating catalyst and preparation method thereof Pending CN107812517A (en)

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Cited By (1)

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CN114392635A (en) * 2022-02-28 2022-04-26 稀美资源(广东)有限公司 Tantalum ethoxide automatic constant-temperature collecting and subpackaging device

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Publication number Priority date Publication date Assignee Title
CN101721992A (en) * 2009-12-16 2010-06-09 清华大学 Ceria-based denitration catalyst and preparation method thereof
CN104437463A (en) * 2014-11-20 2015-03-25 清华大学 Cerium tantalum composite oxide denitration catalyst and preparation method and application of cerium tantalum composite oxide denitration catalyst
CN105618077A (en) * 2015-07-30 2016-06-01 盐城工学院 Preparation method for denitration ceramic cellular catalyst and catalyst prepared by preparation method

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Publication number Priority date Publication date Assignee Title
CN101721992A (en) * 2009-12-16 2010-06-09 清华大学 Ceria-based denitration catalyst and preparation method thereof
CN104437463A (en) * 2014-11-20 2015-03-25 清华大学 Cerium tantalum composite oxide denitration catalyst and preparation method and application of cerium tantalum composite oxide denitration catalyst
CN105618077A (en) * 2015-07-30 2016-06-01 盐城工学院 Preparation method for denitration ceramic cellular catalyst and catalyst prepared by preparation method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114392635A (en) * 2022-02-28 2022-04-26 稀美资源(广东)有限公司 Tantalum ethoxide automatic constant-temperature collecting and subpackaging device

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