CN102764643A - Vanadium-titanium oxide catalyst, and preparation method and application thereof - Google Patents

Vanadium-titanium oxide catalyst, and preparation method and application thereof Download PDF

Info

Publication number
CN102764643A
CN102764643A CN2012102457192A CN201210245719A CN102764643A CN 102764643 A CN102764643 A CN 102764643A CN 2012102457192 A CN2012102457192 A CN 2012102457192A CN 201210245719 A CN201210245719 A CN 201210245719A CN 102764643 A CN102764643 A CN 102764643A
Authority
CN
China
Prior art keywords
catalyst
presoma
vanadium
preferred
ammonium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2012102457192A
Other languages
Chinese (zh)
Inventor
贺泓
石晓燕
连志华
刘福东
谢利娟
丁世鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Research Center for Eco Environmental Sciences of CAS
Original Assignee
Research Center for Eco Environmental Sciences of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Research Center for Eco Environmental Sciences of CAS filed Critical Research Center for Eco Environmental Sciences of CAS
Priority to CN2012102457192A priority Critical patent/CN102764643A/en
Publication of CN102764643A publication Critical patent/CN102764643A/en
Pending legal-status Critical Current

Links

Landscapes

  • Catalysts (AREA)

Abstract

The invention relates to a vanadium-titanium oxide catalyst which can resist alkaline metal and alkaline earth metal poisoning. The catalyst is characterized in that the vanadium-titanium oxide catalyst is doped with an element Ce. The catalyst has fine resistance to alkaline metal poisoning, and above all, the doped cerium component has no influence on the activity of the SCR (selective catalytic reduction) catalyst while improving the resistance of the V2O5/(MoO3)x(WO3)1-x-TiO2 catalyst to alkaline metal poisoning. The preparation method of the catalyst is simple and easy to implement and has very excellent N2 generation selectivity; and meanwhile, the Ce is a non-poisonous component and can not do harm to human health and ecological environment.

Description

A kind of vanadium titanium oxide catalyst, Preparation Method And The Use
Technical field
The present invention relates to a kind of vanadium titanium oxide catalyst, be specifically related to the vanadium titanium oxide catalyst that a kind of cerium mixes, can be used for nitrogen oxide in the ammine selectivity catalytic reduction flue, belong to the environmental catalysis technical field.
Background technology
Contain SO in the flue gas of discharged from coal-fired boiler 2, NO xWith multiple oxious components such as dust, wherein nitrogen oxide (NO x) be one of pollutant of emphasis control.From the seventies in 20th century, developed countries such as Europe, U.S.A, day are in succession to coal-fired power station boiler NO xDischarging done restriction, and with technology and expanding economy, restriction is strict day by day.
Fuel combustion is NO xMain source (account for human total emission volumn 90%), China is to be main developing country with the fire coal, along with rapid economy development, the environmental pollution that fire coal causes is on the rise, particularly the NO in the coal-fired flue-gas x, the pollution of atmosphere has been become a major issue that can not be ignored, power plants boiler NO xAnnual emissions is increased to 271.3 ten thousand-300.7 ten thousand t in 2000 from 120.7 ten thousand-150.6 ten thousand t in 1987.In view of this, State Bureau of Environmental Protection is in the middle and later periods nineties 20th century, to coal-fired power station boiler NO xDischarging made restriction.
NO xThe improvement technology can be divided into three kinds of the post processings of improvement and burning of pre-treatment, the combustion system of burning.The NO that contains that the post processing of burning just produces burning xThe method handled of flue gas (tail gas), i.e. denitrating flue gas.
Under oxygen-containing atmosphere, NO in the preferential and waste gas of reducing agent xThe reaction catalytic process be called SCR (Selective Catalytic Reduction, SCR).With NH 3, urea [CO (NH 2) 2] wait as reducing agent V 2O 5-TiO 2Be catalyst, in suitable temperature range, the ammonia of gas phase or urea will be decomposed into free radical NH 3And NH 2Thereby, reach the NO that eliminates stationary source (like the thermal power plant) discharging xPurpose.
At present, the NH of industrial applications 3Selective Catalytic Reduction of NO xNH 3-SCR catalyst mainly is WO 3Or MoO 3Vanadium titanium catalyst (the V that mixes 2O 5/ TiO 2) system.NH 3-SCR catalyst system has been widely used in the stationary source denitrating flue gas.Vanadium titanium oxide catalyst, for example V 2O 5/ WO 3-TiO 2Or V 2O 5/ MoO 3-TiO 2Catalyst can receive the influence of alkali metal such as K that the cigarette flying dust brings, Na, Ca, Mg and alkaline-earth metal in carrying out the denitrating flue gas process, cause its catalytic activity significantly to reduce.Therefore, the poisoning of the alkali of vanadium titanium oxide catalyst (or alkaline earth) metallic element is its major issue in practical application.
To NH 3That-SCR catalyst activity has the greatest impact is K, Na, Ca, Mg, is example with the K element, 1%K 2O can make V 2O 5-WO 3/ TiO 2Catalyst is inactivation (The role of K almost completely 2O in the selective reduction of NO with NH 3Over a V 2O 5(WO 3)/TiO 2Commercial selective catalytic reduction catalyst, H.Kamata, K.Takahashi, C.U.Ingemar Odenbrand, Journal ofMolecular Catalysis A:Chemical, 139 (1999) 189-198).In addition, the vanadium titanium oxide catalyst is subject to that alkali metal is poisoned and inactivation has also limited him and is used for the higher denitrating flue gas of ash content alkali metal content, such as the high glass furnace of alkali metal content in the ash content.Therefore, improve the alkali resistant metal poisoning ability of catalytic component based on vanadium, especially vanadium titanium oxide catalyst, to prolonging the service life of catalyst, it is extremely important to widen its application.
Therefore, a kind of ammine selective catalyst with alkali resistant metal and alkaline-earth metal poisoning capability of exploitation is the problem demanding prompt solution in this area.
Summary of the invention
In order to solve catalytic component based on vanadium; Especially the vanadium titanium oxide catalyst is subject to the problem that alkali metal is poisoned to be influenced; The present invention has carried out doping vario-property to described catalytic component based on vanadium; Propose the catalytic component based on vanadium that a kind of Ce that possesses good alkali resistant metal poisoning performance mixes first, can be used as the stationary source denitrating flue gas.
Therefore, one of the object of the invention provides the catalytic component based on vanadium that a kind of cerium that is used for catalytic cleaning nitrogen oxide mixes.
Said catalyst is in the vanadium titanium oxide catalyst, to be doped with Elements C e, has the performance that good alkali resistant metal and alkaline-earth metal are poisoned.
In the catalytic component based on vanadium that said cerium mixes, the mol ratio of Elements C e and element V is preferably 0.1-10, for example 0.1-8,0.2-9,1-9,4-7,0.3,0.8,1.5,2.8,4.4,6.0,8.7,9.2,9.9 etc.
In the said catalyst, cerium (Ce) element exists with the oxidation states of matter, and the present invention finds that the oxide of said cerium (Ce) element and the oxide of each element in the catalytic component based on vanadium form solid solution in composite oxide catalysts.
The valence state of occurring in nature cerium (Ce) element is a lot, and the oxide of Ce of the present invention is CeO n, it is the oxide mixture of different valence state Ce, such as Ce 3+And Ce 4+Mixture.
Vanadium titanium oxide catalyst of the present invention is to comprise but be not limited to the catalyst of elemental vanadium and element titanyl compound; The oxide of transition metal such as for example all right containing element W and/or elements Mo; Described vanadium titanium oxide catalyst is a kind of catalyst well-known to those skilled in the art; The selection of its various elements all can be selected according to the professional knowledge of oneself grasping by those skilled in the art with the ratio of each element, and those skilled in the art should understand simultaneously, in the described various transition metal oxides; The valence state of metallic element can be selected, for example WO p, it is the oxide mixture of different valence state W, such as W 5+And W 6+Mixture; MoO q, it is the oxide mixture of different valence state Mo, such as Mo 5+And Mo 6+Mixture; FeO r, it is the oxide mixture of different valence state Fe, such as Fe 2+And Fe 3+Mixture, or the like.
Said catalytic component based on vanadium is the vanadium titanium oxide catalyst, and said vanadium titanium oxide catalyst preferably has general formula V 2O 5/ (MoO 3) x(WO 3) 1-x-TiO 2, wherein, x is selected from 0-1, and for example x is any 1 numerical value in 0.1,0.4,0.8,0.9, and preferred x is 0 or 1; X in the formula, y only are used for representing MoO in the said catalyst 3And WO 3Mol ratio, and do not represent V in the catalyst 2O 5, MoO 3, WO 3And TiO 2Between mass content, V in the catalyst 2O 5, MoO 3, WO 3And TiO 2Between mass content after described quality percentage composition limit.
For example, when x was 0.1,1-x was 0.9 in the catalyst, so MoO in the catalyst 3And WO 3Mol ratio be 1:9, then the structural formula of said catalyst is V 2O 5/ (MoO 3) 1(WO 3) 9-TiO 2When x was 0.5,1-x was 0.5 in the catalyst, so MoO in the catalyst 3And WO 3Mol ratio be 1:1, then the structural formula of said catalyst is V 2O 5/ (MoO 3) 1(WO 3) 1-TiO 2When x was 0,1-x was 1 in the catalyst, so MoO in the catalyst 3And WO 3Mol ratio be 1:0, then the structural formula of said catalyst is V 2O 5/ MoO 3-TiO 2X is 1 o'clock, and 1-x is 0 in the catalyst, so MoO in the catalyst 3And WO 3Mol ratio be 0:1, then the structural formula of said catalyst is V 2O 5/ WO 3-TiO 2
But in the catalytic component based on vanadium that described Ce mixes, V 2O 5, MoO 3, WO 3And TiO 2Between mass content be 100% all in the quality of metal oxide, wherein, V 2O 5Content be 0.5-5wt%, for example 0.5-4wt%, 0.8-5wt%, 1-3wt%, 0.6wt%, 1.1wt%, 1.7wt%, 2.3wt%, 3.5wt%, 4.6wt%, 4.9wt% etc.; WO 3Content be 0-10wt%, for example 0-8wt%, 1-10wt%, 3-6wt%, 0.1-10wt%, 0.3wt%, 0.9wt%, 1.7wt%, 2.5wt%, 4.1wt%, 4.9wt%, 6.7wt%, 8.8wt%, 9.5wt%, 9.8wt% etc.; MoO 3Content be 0-10wt%, for example 0-9wt%, 1-7wt%, 0-6wt%, 0.1-8wt%, 0.32wt%, 1.9wt%, 2.7wt%, 4.5wt%, 7.7wt%, 9.7wt% etc.
In the for example said catalytic component based on vanadium, metal oxide comprises as follows:
Figure BDA00001890806700041
But, WO 3And MoO 3Content can not be 0wt% simultaneously.
Said 0wt% does not contain corresponding material, for example WO in the catalyst 3Content be 0-10wt%, mean in the said catalyst, do not comprise metal oxide WO 3, or MoO 3Content be 0-10wt%, mean in the said catalyst, do not comprise metal oxide MoO 3
" comprising " of the present invention, mean it except that said component, can also comprise other components, these other components are given said catalyst different characteristic.For example can add scandium (Sc), titanium (Ti), chromium elements such as (Cr), in addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... form ".
Preferably, said catalyst obtains through immersion process for preparing.
Infusion process is one of method of making solid catalyst, is about to one or more active components and loads on the method on the carrier through impregnated carrier.Infusion process normally contacts with the aqueous solution of metallic salt with carrier, makes metallic salt solution absorption or is stored in the carrier, removes superfluous solution, makes catalyst through dry, calcining and activation again.
Preferably; The presoma of Ce is water-soluble Ce salt in the Preparation of catalysts process according to the invention; Valence state the present invention of said Elements C e does not do qualification; Can be+3 valencys ,+4 valencys etc., described water-soluble Ce salt is the disclosed any water-soluble Ce salt of prior art or new technology.
Preferably; The presoma of Ce according to the invention is selected from the combination of any a kind or at least 2 kinds in cerous chlorate, cerous nitrate, ammonium ceric nitrate or the cerous sulfate, and said combination is cerous chlorate/cerous nitrate, cerous nitrate/ammonium ceric nitrate, ammonium ceric nitrate/cerous sulfate, cerous nitrate/ammonium ceric nitrate/cerous sulfate etc. for example.
One of the object of the invention also is to provide the preparation method of the catalytic component based on vanadium that a kind of cerium mixes.The preparation method of the catalytic component based on vanadium that cerium of the present invention mixes is an infusion process, specifically comprises the steps:
(1) each precursor solution of preparation catalyst;
(2) in the solution that step (1) obtains, add the titanium tungsten powder, stirring load, drying, roasting get the vanadium titanium oxide catalyst that Ce mixes.
The said presoma of step (1) is the presoma of contained element in the said catalyst, and said presoma comprises vanadium presoma, tungsten presoma, molybdenum presoma and cerium precursor, perhaps can also comprise iron presoma, scandium presoma, titanium precursor body, chromium presoma etc.Preferably, said presoma all can be water-soluble.
Preferably, said cerium precursor is selected from the combination of any a kind or at least 2 kinds in cerous chlorate, cerous nitrate, ammonium ceric nitrate or the cerous sulfate.
Preferably, said vanadium presoma is selected from the combination of any a kind or at least 2 kinds in sodium metavanadate, ammonium metavanadate, the potassium metavanadate, and said combination is sodium metavanadate/ammonium metavanadate, potassium metavanadate/sodium metavanadate, sodium metavanadate/ammonium metavanadate/potassium metavanadate etc. for example.
Preferably; Said tungsten presoma is selected from water-soluble tungsten salt or tungstates; The preferably combination of any a kind or at least 2 kinds in ammonium tungstate, ammonium paratungstate, nitric acid tungsten, tungsten chloride, sulfuric acid tungsten, said combination is ammonium tungstate/ammonium paratungstate, tungsten chloride/nitric acid tungsten, sulfuric acid tungsten/nitric acid tungsten/ammonium tungstate etc. for example.
Preferably; Said molybdenum presoma is selected from water-soluble molybdenum salt or molybdate; The preferably combination of any a kind or at least 2 kinds in ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, nitric acid molybdenum, molybdenum chloride, molybdenum trisulfate, said combination is ammonium molybdate/ammonium tetramolybdate, nitric acid molybdenum/ammonium molybdate, ammonium tetramolybdate/molybdenum trisulfate/molybdenum chloride etc. for example.
Preferably, in the said precursor solution, the mol ratio of Ce element and V element is 0.1-10, preferred 1-10, for example preferred 2-6,3-5,2-7,4.0,9.3,7.8 etc., further preferred 2-7.
After preparing the precursor solution of an element in the said catalyst, need said presoma be loaded on the carrier, obtain the catalyst that needs after oven dry, the roasting.Carrier of the present invention is a titanium dioxide; Said titanium dioxide is to add with the form of anatase titanium dioxide and/or titanium tungsten powder, and the ratio of the precursor solution that the addition of anatase titanium dioxide and/or titanium tungsten powder and step (1) obtain is (0.5-5g)/10mL.
Preferably; The adding quality of said anatase titanium dioxide of step (2) and/or titanium tungsten powder is (0.5-5) g/10mL precursor solution; The amount of the titanium tungsten powder that adds in for example every 10mL precursor solution is 0.5-4.8g, 0.7-4.2g, 1-3g2-3g, 0.6g, 2.1g, 3.3g, 4.1g, 4.8g etc.; Preferred 0.8-3g/10mL precursor solution, further preferred 1g/10mL precursor solution.
Preferably, the temperature of the said stirring load of step (2) is 20-50 ℃, for example 20-30 ℃, 30-50 ℃, 22 ℃, 26 ℃, 31 ℃, 36 ℃, 44 ℃, 48 ℃ etc., further preferred 25 ℃.
Preferably, the time of the said stirring load of step (2) is 1-5h, for example 1.2-5h, 2-5h, 1-4.7h, 3.5-4.7h, 1.3h, 2.5h, 3.5h, 4.9h etc., preferably 1-2h, most preferably 2h.
Drying is operation well-known to those skilled in the art, and the disclosed drying means of any prior art or new technology all can be used for the present invention, typical case but non-limiting instance has forced air drying, infra-red drying, microwave drying, air dry etc.
Preferably, the said drying of step of the present invention (2) is selected from heat drying or air dry, preferred heat drying, and further preferred convection oven is dry, in infra-red drying or the microwave drying any a kind.
Preferably, the said drying of step (2) is a heat drying, and baking temperature is 100-150 ℃, for example 100-120 ℃, 120-150 ℃, 115 ℃, 125 ℃, 130 ℃, 142 ℃, 148 ℃ etc., preferred 100-120 ℃, most preferably 110 ℃; Baking temperature is low excessively, and drying is not thorough, and the time cost that is spent is high; Baking temperature is too high, causes the change of the character of filter cake to be dried easily.
Preferably, step (2) is preferably 5-36h said drying time, for example 5-35h, 5-27h, 6-33h, 9-25h, 7h, 16h, 24h, 31h, 35h etc., further preferred 7-24h, preferred especially 9-12h, most preferably 10h.
Roasting (Roasting) is that the course of reaction of carrying out under the condition of fusion does not take place at high temperature solid material, and oxidation, pyrolysis, reduction, halogenation etc. can be arranged, and is technology well-known to those skilled in the art.
Preferably, the said sintering temperature of step (2) is 300-800 ℃, for example 310-750 ℃, 400-800 ℃, 500-700 ℃, 307 ℃, 450 ℃, 520 ℃, 680 ℃, 780 ℃ etc., and preferred 400-500 ℃, further preferred 500 ℃.
Preferably, the preferred 3-24h of the said roasting time of step (2), for example 3-20h, 4-23h, 5-17h, 6h, 13h, 21h etc., further preferred 4-8h, most preferably 5h.
Those skilled in the art can be selected from roasting apparatus according to actual conditions, and preferably, the said roasting of step (2) is carried out in Muffle furnace.
One of the object of the invention also is to provide a kind of method of selective catalyst reduction of nitrogen oxides; The method of said selective catalyst reduction of nitrogen oxides is used vanadium titanium oxide catalyst provided by the invention; Promptly be doped with the vanadium titanium oxide catalyst of Ce element, specifically comprise the steps:
(1) supported catalyst;
(2) tail gas is carried out SCR.
The said supported catalyst of step (1) is the vanadium titanium oxide catalyst of doped Ce of the present invention; The load of said catalyst is that the form with coating is coated on the wall surface of tail gas stream circulation passage; The wall surface of said tail gas stream circulation passage preferably can fixed catalyst at its surperficial material; For example has cavernous material; Typical case but non-limiting instance have porous resin, many hollow fibers, pottery or have the metallic article etc. of honeycomb, preferably have pottery or metal honeycomb.
In the actual conditions; If being fixed on the wall surface of tail gas stream circulation passage, catalyst has difficult installation; For example the wall surface of passage does not have the cellular material, and so, catalyst provided by the present invention can be processed the spherical or tabular exhaust gas channel that places; When treating that tail gas stream is crossed the catalyst that places exhaust gas channel, can react with the reducibility gas that exists.
The SCR denitration reaction is to depend on ammonia (NH 3) as reducing agent and NO xChemical reaction takes place, and to reach the purpose of denitration, therefore, ammonia is exactly the direct reducing agent of denitration reaction.Obtaining of ammonia be that those skilled in the art can obtain according to prior art or new technology, and the acquisition methods of present existing ammonia mainly contains two kinds: urea method prepares ammonia and liquid ammonia process for caustic soda purification prepares ammonia.Described urea method prepares ammonia can comprise that hydrolyze urea or pyrolysis urea obtain ammonia; Described liquid ammonia process for caustic soda purification prepares ammonia for liquefied ammonia is evaporated to ammonia.Those skilled in the art should understand, and the acquisition methods of ammonia of the present invention is not limited to above-mentioned two kinds of methods, and the method for the disclosed acquisition ammonia of any prior art and new technology all can be used for the present invention.
Preferably, step (2) is said carries out selective reduction for spray into reducing agent at the upper reaches of catalyst to tail gas, and reducing agent and tail gas carry out reduction reaction after mixing; Said reducing agent adopts ammonia or urea.
Preferably, said tail gas is moving source nitrogen-containing oxide gas, for example exhaust gas from diesel vehicle, or stationary source nitrogen-containing oxide gas, coal-fired plant flue gas for example, Industrial Stoves flue gas.
Catalyst of the present invention is the vanadium titanium oxide catalyst that the Ce of alkali resistant metal and the alkaline-earth metal poisoning capability of a kind of raising vanadium titanium catalyst of being used for ammine selectivity catalytic reduction nitrous oxides mixes.Catalyst of the present invention improves vanadium titanium catalyst alkali resistant metal and alkaline-earth metal ability; Specifically be through Ce being added in the vanadium titanium catalyst; Thereby improved the ability that its alkali resistant metal and alkaline-earth metal are poisoned, and do not influenced the denitration activity and the selectivity of vanadium titanium catalyst.The present invention adds the method for Ce in the vanadium titanium oxide catalyst simple, improves the anti-poisoning performance of vanadium titanium catalyst, prolongs it and be used for the coal-fired plant flue gas service life when being the stationary source catalytic purification of nitroxide of representative.
Compared with prior art, the present invention has following beneficial effect:
(1) the vanadium titanium oxide catalyst of said cerium doping has the performance of good alkali resistant metal and alkaline-earth metal poisoning, and the cerium component of especially mixing is improving V 2O 5/ (MoO 3) x(WO 3) 1-x-TiO 2In the time of catalyst alkali resistant metal and alkaline-earth metal poisoning performance, its SCR catalyst activity there is not influence;
(2) preparation method is simple, does not change the production technology of catalytic component based on vanadium;
(3) has very excellent N 2Generate selectivity;
(4) the new Ce that adds is nontoxic component, can not work the mischief to health and ecological environment.
The specific embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1
Be cerium salt, vanadic salts with six nitric hydrate ceriums, ammonium metavanadate respectively, the V that preparation Ce mixes 2O 5/ WO 3-TiO 2Catalyst, wherein V 2O 5Load capacity is 1%, and the mol ratio of Ce/V is 4.After each presoma salt is dissolved as the aqueous solution and mixes, in this solution, add commercial titanium tungsten powder powder (WO again 3Content 5wt%); Liquor capacity and titanium tungsten powder mass ratio are 10:1 (mL/g), at 30 ℃ of following continuous stirring 2h, behind the rotary evaporation; The catalyst that obtains is put into baking oven spend the night, after Muffle furnace roasting 5h in 500 ℃ of air makes powder catalyst in 100 ℃ of oven dry.The catalyst that makes is ground, sieves, and it is subsequent use to get the 40-60 order, is called catalyst Ce4VWTi.
Comparative Examples 1
Identical with the experiment condition of embodiment 1, but do not add the presoma of Ce, the 1%V of Ce is not added in preparation 2O 5/ WO 3-TiO 2Catalyst is called VWTi.
Embodiment 2
VWTi catalyst fines in Ce4VWTi among the embodiment 1 and the Comparative Examples 1 is carried out the K element poisons.KNO 3Be dissolved in the aqueous solution, according to KNO 3Liquor capacity and catalyst fines mass ratio are that 2:1 floods, and the K addition is that the mol ratio of K/V is 4.Catalyst fines impregnated in KNO 3Behind the solution 12h, in 100 ℃ of oven dry, roasting 3h in 500 ℃ of air makes Powdered poisoned catalyst through Muffle furnace in baking oven.The poisoned catalyst that makes is ground, sieves, and it is subsequent use to get the 40-60 order, is called catalyst K-Ce4VWTi and K-VWTi.
Embodiment 3
VWTi catalyst fines in Ce4VWTi among the embodiment 1 and the Comparative Examples 1 is carried out the Ca element poisons.With Ca (NO 3) 24H 2O is dissolved in the aqueous solution, is that 2:1 floods according to calcium nitrate solution volume and catalyst fines mass ratio, and the Ca addition is that the mol ratio of Ca/V is 8.After catalyst fines impregnated in calcium nitrate solution 12h, in 100 ℃ of oven dry, roasting 5h in 500 ℃ of air made Powdered poisoned catalyst through Muffle furnace in baking oven.The poisoned catalyst that makes is ground, sieves, and it is subsequent use to get the 40-60 order, is called catalyst Ca-Ce4VWTi and Ca-VWTi.
Embodiment 4
VWTi catalyst fines in Ce4VWTi among the embodiment 1 and the Comparative Examples 1 is carried out the Mg element poisons.With Mg (NO 3) 26H 2O is dissolved in the aqueous solution, is that 2:1 floods according to calcium nitrate solution volume and catalyst fines mass ratio, and the Mg addition is that the mol ratio of Mg/V is 8.After catalyst fines impregnated in calcium nitrate solution 12h, in 100 ℃ of oven dry, roasting 5h in 50 ℃ of air made Powdered poisoned catalyst through Muffle furnace in baking oven.The poisoned catalyst that makes is ground, sieves, and it is subsequent use to get the 40-60 order, is called catalyst Mg-Ce4VWTi and Mg-VWTi.
Embodiment 5
VWTi catalyst fines in Ce4VWTi among the embodiment 1 and the Comparative Examples 1 is carried out the Na element poisons.With NaNO 3Being dissolved in the aqueous solution, is that 2:1 floods according to calcium nitrate solution volume and catalyst fines mass ratio, and the Na addition is that the mol ratio of Na/V is 4.After catalyst fines impregnated in calcium nitrate solution 12h, in 10 ℃ of oven dry, roasting 3h in 500 ℃ of air made Powdered poisoned catalyst through Muffle furnace in baking oven.The poisoned catalyst that makes is ground, sieves, and it is subsequent use to get the 40-60 order, is called catalyst n a-Ce4VWTi and Na-VWTi.
Embodiment 6
With the fresh and poisoned catalyst VWTi that embodiment 1-2 and Comparative Examples 1 make, C4VWTi, K-VWTi and K-C4VWTi carry out NH on homemade micro fixed-bed reactor 3Selective Catalytic Reduction of NO xThe investigation of reactivity.The use amount of catalyst is 0.12mL, the consisting of of reaction mixture gas: [NO]=[NH 3]=500ppm, [O 2]=5%, N 2Make balance gas, total gas flow rate is 500mL/min, and air speed is 100,000h -1, reaction temperature 275-450 ℃.NO and NH 3And accessory substance N 2O, NO 2All utilize the infrared-gas pond to measure.Reaction result is as shown in table 1.
Table 1 catalyst activity evaluation result and anti-K poisoning result
The data of table 1 show; The doping of Ce does not influence the VWTi activity of such catalysts basically, has also improved the low temperature active of VWTi catalyst, and is under 4 the toxic dose in the K/V mol ratio; The active basic forfeiture of VWTi, and K-C4VWTi still can keep higher NO in the reaction temperature interval xConversion ratio.
Embodiment 7
Use embodiment 3-5 interpolation alkaline-earth metal and alkali metal Ca, Mg, Ce4VWTi among the embodiment 1 of Na and the VWTi in the Comparative Examples 1 investigate the influence of reaction velocity to catalyst activity on homemade micro fixed-bed reactor.The use amount of catalyst is 0.3mL, the consisting of of reaction mixture gas: [NO]=[NH 3]=500ppm, [O 2]=5%, N 2Make balance gas, total gas flow rate is 500mL/min, and corresponding air speed is 100,000h -1, reaction temperature 275-450 ℃.NO and NH 3And accessory substance N 2O, NO 2All utilize the infrared-gas pond to measure.Reaction result is as shown in table 2.
The anti-Ca of table 2 catalyst, Mg, Na poisoning evaluation result
Figure BDA00001890806700122
Figure BDA00001890806700131
Can find out by table 2; Under identical alkaline-earth metal Ca, the Mg situation identical with the Alkali-Metal Na additive capacity; Its NOx conversion ratio of VWTi catalyst of Ce of having mixed all is superior to the VWTi catalyst, explains that the VWTi catalyst of the Ce that mixed has the performance of very excellent alkali resistant metal and alkaline-earth metal poisoning.
Embodiment 8
Be cerium salt, vanadic salts with six nitric hydrate ceriums, ammonium metavanadate respectively, the different 0.6%V of content of vanadium that preparation Ce mixes 2O 5/ WO 3-TiO 2Catalyst, the mol ratio of Ce/V is 7, is called Ce-V0.6WTi.Identical with embodiment 1, after each presoma salt is dissolved as the aqueous solution and mixes, in this solution, add commercial titanium tungsten powder powder (WO again 3Content 5wt%); Liquor capacity and titanium tungsten powder mass ratio are 10:1 (mL/g), and continuous stirring 2h at ambient temperature is behind the rotary evaporation; The catalyst that obtains is put into baking oven spend the night, after Muffle furnace roasting 5h in 500 ℃ of air makes powder catalyst in 100 ℃ of oven dry.The catalyst that makes is ground, sieves, and it is subsequent use to get the 40-60 order, is called catalyst Ce4VWTi.
Comparative Examples 2
Identical with the experiment condition of embodiment 8, but do not add the presoma of Ce, the 0.6%V of Ce is not added in preparation 2O 5/ WO 3-TiO 2Catalyst is called V0.6WTi.
Embodiment 9
V0.6WTi catalyst fines in Ce-V0.6WTi among the embodiment 8 and the Comparative Examples 2 and the Ce4VWTi among the embodiment 1 and Comparative Examples 1VWTi are carried out the K element to poison.KNO 3Be dissolved in the aqueous solution, according to KNO 3Liquor capacity and catalyst fines mass ratio are that 2:1 floods, K addition from 0.1% to 1.8%.Catalyst fines impregnated in KNO 3Behind the solution 12h, in 100 ℃ of oven dry, roasting 3h in 500 ℃ of air makes Powdered poisoned catalyst through Muffle furnace in baking oven.The poisoned catalyst that makes is ground, sieves, and it is subsequent use to get the 40-60 order.
Embodiment 10
The VWTi that uses the serial K among the embodiment 9 to poison, Ce4VWTi, V0.6WTi, CeV0.6WTi investigates the influence of reaction velocity to catalyst activity on the self-control micro fixed-bed reactor.The use amount of catalyst is 0.3mL, the consisting of of reaction mixture gas: [NO]=[NH 3]=500ppm, [O 2]=5%, N 2Make balance gas, total gas flow rate is 500mL/min, and corresponding air speed is 100,000h -1, 325 ℃ of reaction temperatures.NO and NH 3And accessory substance N 2O, NO 2All utilize the infrared-gas pond to measure.Reaction result is as shown in table 3.
Table 3 catalyst is along with the variation of the K addition activity rating result at 325 ℃
Figure BDA00001890806700141
Can find out by table 3; Along with the increase of K addition, VWTi and V0.6WTi rapid catalyst deactivation, but VWTi and the V0.6WTi catalyst of the Ce that mixed then shown the ability that excellent anti-K poisons; Addition at K is not higher than at 0.86% o'clock, the NO in the time of 325 ℃ xConversion ratio is still near 100%; Even when the toxic dose 1.72% of VWTi and the basic inactivation of V0.6WTi; CeV0.6WTi and Ce4VWTi catalyst still have 72% and 87% conversion ratio, explain that the doping of Ce effectively improves the alkali resistant metal poisoning ability of VWTi catalyst.
Embodiment 11
Be respectively cerium precursor with the cerous chlorate, potassium metavanadate is the vanadium presoma, and ammonium molybdate is the molybdenum presoma, the V that preparation Ce mixes 2O 5/ MoO 3-TiO 2Catalyst, wherein V 2O 5Account for the 0.5wt% of metal oxide, MoO 3Account for the 10wt% of metal oxide, the mol ratio of Ce/V is 10, after each presoma salt is dissolved as the aqueous solution and mixes, in this solution, adds commercial Detitanium-ore-type TiO again 2Powder, liquor capacity and TiO 2The powder quality ratio is 10:5 (mL/g), at 50 ℃ of following continuous stirring 1h, behind the rotary evaporation, the catalyst that obtains is put into infrared blast dry oven in 100 ℃ of oven dry 36h, after Muffle furnace roasting 24h in 300 ℃ of air makes powder catalyst.The catalyst that makes is ground, sieves, and it is subsequent use to get the 40-60 order, makes the V that elemental cerium is mixed 2O 5/ MoO 3-TiO 2Catalyst is called CeV0.5MoTi.
Comparative Examples 3
Identical with the experiment condition of embodiment 11, but do not add the presoma of Ce, the 0.5%V of Ce is not added in preparation 2O 5/ MoO 3-TiO 2Catalyst is called V0.5MoTi.
Embodiment 12
Ce-V0.5MoTi among the embodiment 11 and V0.5MoTi catalyst fines are carried out the poisoning of K element.KNO 3Be dissolved in the aqueous solution, according to KNO 3Liquor capacity and catalyst fines mass ratio are that 2:1 floods, and the K addition is 0.5wt.%.Catalyst fines impregnated in KNO 3Behind the solution 12h, in 100 ℃ of oven dry, roasting 3h in 500 ℃ of air makes Powdered poisoned catalyst through Muffle furnace in baking oven.The poisoned catalyst that makes is ground, sieves, and it is subsequent use to get the 40-60 order.Be called K-CeV0.5MoTi and K-V0.5MoTi.
Embodiment 13
Use the CeV0.5MoTi of embodiment 11-12 and Comparative Examples 3, V0.5MoTi, K-CeV0.5MoTi and K-V0.5MoTi investigate the influence of reaction velocity to catalyst activity on homemade micro fixed-bed reactor.The use amount of catalyst is 0.3mL, the consisting of of reaction mixture gas: [NO]=[NH 3]=500ppm, [O 2]=5%, N 2Make balance gas, total gas flow rate is 500mL/min, and corresponding air speed is 100,000h -1, reaction temperature 250-450 ℃.NO and NH 3And accessory substance N 2O, NO 2All utilize the infrared-gas pond to measure.Reaction result is as shown in table 4.
The anti-Ca of table 4 catalyst, Mg, Na poisoning evaluation result
Figure BDA00001890806700161
Embodiment 14
Be respectively cerium precursor with the cerous chlorate, potassium metavanadate is the vanadium presoma, and ammonium paratungstate is the tungsten presoma, and ammonium dimolybdate is present body, the V that preparation Ce mixes 2O 5/ (MoO 3) x(WO 3) 1-x-TiO 2Catalyst, wherein, x is selected from 0-1, and the amount and the reaction condition of each presoma of interpolation are relevant in the selection numerical value of concrete x and the experiment, wherein V 2O 5Account for the 5wt% of metal oxide, the mol ratio of Ce/V is 0.1, after each presoma salt is dissolved as the aqueous solution and mixes; In this solution, add commercial titanium tungsten powder powder again; Liquor capacity and titanium tungsten powder mass ratio are 10:0.5 (mL/g), at 20 ℃ of following continuous stirring 5h, behind the rotary evaporation; The catalyst that obtains is put into infrared blast dry oven in 150 ℃ of oven dry 5h, after Muffle furnace roasting 3h in 800 ℃ of air makes powder catalyst.The catalyst that makes is ground, sieves, and it is subsequent use to get the 40-60 order, makes the V that elemental cerium is mixed 2O 5/ (MoO 3) x(WO 3) y-TiO 2Catalyst.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technological process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.

Claims (10)

1. alkali resistant metal and the alkaline-earth metal vanadium titanium oxide catalyst of poisoning is characterized in that said catalyst is doped with Elements C e in the vanadium titanium oxide catalyst.
2. catalyst as claimed in claim 1 is characterized in that, in the said catalyst, the mol ratio of Elements C e and element V is preferably 0.1-10;
Preferably, said vanadium titanium oxide catalyst is V 2O 5/ (MoO 3) x(WO 3) 1-x-TiO 2, wherein, x is selected from 0-1, and preferred x is selected from 0 or 1;
Preferably, be 100% in the quality of metal oxide, in the vanadium titanium catalyst that Ce mixes, V 2O 5Content be 0.5-5wt%, WO 3Content be 0-10wt%, MoO 3Content be 0-10wt%.
3. according to claim 1 or claim 2 catalyst is characterized in that said catalyst obtains through immersion process for preparing;
Preferably, the presoma of Ce is selected from water-soluble Ce salt in the said Preparation of catalysts process, preferably the combination of any a kind or at least 2 kinds in cerous chlorate, cerous nitrate, ammonium ceric nitrate or cerous sulfate.
4. one kind like the described Preparation of catalysts method of one of claim 1-3, it is characterized in that said method comprises the steps:
(1) each precursor solution of preparation catalyst;
(2) in the solution that step (1) obtains, add anatase titanium dioxide and/or titanium tungsten powder, stirring load, drying, roasting get the vanadium titanium oxide catalyst that Ce mixes.
5. method as claimed in claim 4 is characterized in that, said each presoma all can be water-soluble; Said presoma comprises vanadium presoma and cerium precursor, also comprises tungsten presoma and/or molybdenum presoma;
Preferably, said cerium precursor is selected from the combination of any a kind or at least 2 kinds in cerous chlorate, cerous nitrate, ammonium ceric nitrate or the cerous sulfate;
Preferably, said vanadium presoma is selected from the combination of any a kind or at least 2 kinds in sodium metavanadate, ammonium metavanadate, the potassium metavanadate; Said tungsten presoma is selected from water-soluble tungsten salt or tungstates, preferably the combination of any a kind or at least 2 kinds in ammonium tungstate, ammonium paratungstate, nitric acid tungsten, tungsten chloride, sulfuric acid tungsten; Said molybdenum presoma is selected from water-soluble molybdenum salt or molybdate, preferably the combination of any a kind or at least 2 kinds in ammonium molybdate, ammonium dimolybdate, ammonium tetramolybdate, nitric acid molybdenum, molybdenum chloride, molybdenum trisulfate;
Preferably, in the said precursor solution, the mol ratio of Ce element and V element is 0.1-10, preferred 1-10, further preferred 2-7.
6. like claim 4 or 5 described methods; It is characterized in that; The adding quality of the said titanium tungsten powder of step (2) is (0.5-5) g/10mL precursor solution; The adding quality of preferred titanium tungsten powder is (0.8-3g)/10mL precursor solution, and the adding quality of further preferred titanium tungsten powder is the 1g/10mL precursor solution;
Preferably, the temperature of the said stirring load of step (2) is 20-50 ℃, preferred 20-30 ℃, and further preferred 25 ℃;
Preferably, the time of the said stirring load of step (2) is 1-5h, preferred 1-2h, most preferably 2h.
7. like the described method of one of claim 4-6, it is characterized in that the said drying of step (2) is selected from heat drying or air dry, preferred heat drying, further preferred convection oven is dry, in infra-red drying or the microwave drying any a kind;
Preferably, the said drying of step (2) is a heat drying, and baking temperature is 100-150 ℃, preferred 100-120 ℃, and most preferably 110 ℃; Be preferably 5-36h drying time, further preferred 7-24h, preferred especially 9-12h, most preferably 10h;
Preferably, the said sintering temperature of step (2) is 300-800 ℃, preferred 400-500 ℃, and further preferred 500 ℃; The preferred 3-24h of said roasting time, further preferred 4-8h, most preferably 5h;
Preferably, the said roasting of step (2) is carried out in Muffle furnace.
8. the method for a selective catalyst reduction of nitrogen oxides is characterized in that, said method is used like the described vanadium titanium oxide catalyst of one of claim 1-3.
9. method as claimed in claim 8 is characterized in that said method comprises the steps:
(1) supported catalyst;
(2) tail gas is carried out SCR.
10. method as claimed in claim 9; It is characterized in that; The said supported catalyst of step (1) is the vanadium titanium oxide catalyst with one of claim 1-3 described doped Ce; Form with coating is coated on the wall surface of tail gas stream circulation passage, and the wall surface of said tail gas stream circulation passage preferably has pottery or metal honeycomb;
Or the said supported catalyst of step (1) is for to process the spherical or tabular exhaust gas channel that places with catalyst;
Preferably, step (2) is said carries out selective reduction for spray into reducing agent at the upper reaches of catalyst to tail gas, and reducing agent and tail gas carry out reduction reaction after mixing; Said reducing agent adopts ammonia or urea;
Preferably, said tail gas is moving source nitrogen-containing oxide gas, for example exhaust gas from diesel vehicle, or stationary source nitrogen-containing oxide gas, coal-fired plant flue gas for example, Industrial Stoves flue gas.
CN2012102457192A 2012-07-16 2012-07-16 Vanadium-titanium oxide catalyst, and preparation method and application thereof Pending CN102764643A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2012102457192A CN102764643A (en) 2012-07-16 2012-07-16 Vanadium-titanium oxide catalyst, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2012102457192A CN102764643A (en) 2012-07-16 2012-07-16 Vanadium-titanium oxide catalyst, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN102764643A true CN102764643A (en) 2012-11-07

Family

ID=47092349

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2012102457192A Pending CN102764643A (en) 2012-07-16 2012-07-16 Vanadium-titanium oxide catalyst, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN102764643A (en)

Cited By (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103252232A (en) * 2013-05-30 2013-08-21 中国科学院生态环境研究中心 Zirconium-doped vanadium-based oxide catalyst, and preparation method and application thereof
CN104815707A (en) * 2015-05-07 2015-08-05 中国华能集团清洁能源技术研究院有限公司 Inactivated vanadium-titanium-based honeycomb-like denitration catalyst low-temperature modifying regeneration liquid and preparation method thereof
CN105222199A (en) * 2015-11-14 2016-01-06 无锡清杨机械制造有限公司 A kind of smoke exhaust ventilator with air-cleaning function
CN105219248A (en) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 A kind of coating preventing and treating haze
CN105214406A (en) * 2015-11-13 2016-01-06 朱忠良 A kind of automobile eliminates the unusual smell method
CN105214240A (en) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 A kind of possess the breathing mask filtered with purification function
CN105214481A (en) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 A kind of flue gas purifying technique
CN105214482A (en) * 2015-11-14 2016-01-06 华玉叶 A kind of domestic briquet stove flue gas purifying method
CN105214489A (en) * 2015-11-14 2016-01-06 华玉叶 A kind of domestic briquet stove flue gas purifying method
CN105214395A (en) * 2015-11-14 2016-01-06 无锡清杨机械制造有限公司 A kind of screen pack preventing and treating haze
CN105214661A (en) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 A kind of catalyst preventing and treating haze
CN105214479A (en) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 A kind of flue gas purifying technique
CN105233580A (en) * 2015-11-13 2016-01-13 无锡桥阳机械制造有限公司 Air purifier for preventing and treating haze
CN105233675A (en) * 2015-11-13 2016-01-13 无锡桥阳机械制造有限公司 Filter screen for preventing and controlling haze
CN105238251A (en) * 2015-11-13 2016-01-13 无锡桥阳机械制造有限公司 Coating for preventing and controlling haze
CN105233680A (en) * 2015-11-13 2016-01-13 无锡桥阳机械制造有限公司 Air-conditioning filter capable of controlling haze
CN105233591A (en) * 2015-11-13 2016-01-13 朱忠良 Abnormal odor removing method for automobile
CN105233581A (en) * 2015-11-13 2016-01-13 无锡清杨机械制造有限公司 Filter screen capable of controlling haze
CN105233676A (en) * 2015-11-13 2016-01-13 无锡桥阳机械制造有限公司 Filter screen for preventing and controlling haze
CN105251352A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Smoke purification technology
CN105249561A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Mask for preventing and treating haze
CN105258256A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Method for purifying air in building with central air-conditioning
CN105251349A (en) * 2015-11-14 2016-01-20 华玉叶 Method for purifying indoor air by means of domestic heating radiator
CN105251343A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Method for purifying indoor air by means of fan
CN105251346A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Filter screen for preventing and treating haze
CN105251273A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Filter screen for preventing and treating haze
CN105251291A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Method for purifying indoor air by means of fan
CN105255346A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Paint for prevention and treatment of haze
CN105251344A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Flue gas scrubbing technology
CN105251342A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Air conditioner filter for preventing and treating haze
CN105251294A (en) * 2015-11-13 2016-01-20 无锡清杨机械制造有限公司 Air conditioner filter for preventing and treating haze
CN105251345A (en) * 2015-11-13 2016-01-20 朱忠良 Air conditioner filter for preventing and treating haze
CN105258224A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Air purifier for preventing and treating haze
CN105276701A (en) * 2015-11-14 2016-01-27 无锡清杨机械制造有限公司 Window type air purifier
CN105276719A (en) * 2015-11-13 2016-01-27 无锡桥阳机械制造有限公司 Central air conditioner with purification function
CN105289128A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Filter screen used for preventing and controlling fog and haze
CN105298936A (en) * 2015-11-14 2016-02-03 无锡清杨机械制造有限公司 Bathroom exhaust fan with purifying function
CN105289719A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Composition used for preventing and controlling fog and haze
CN105289127A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Filter screen used for preventing and controlling fog and haze
CN105289183A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Air filter
CN105298938A (en) * 2015-11-14 2016-02-03 无锡清杨机械制造有限公司 Bathroom exhaust fan with purification function
CN105289285A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Fan with purifying function
CN105299774A (en) * 2015-11-14 2016-02-03 无锡清杨机械制造有限公司 Window type air purifier
CN105288888A (en) * 2015-11-14 2016-02-03 无锡清杨机械制造有限公司 Respiratory mask with filtering and purification functions
CN105298939A (en) * 2015-11-14 2016-02-03 无锡清杨机械制造有限公司 Bathroom exhaust fan with purification function
CN105299791A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Air purification method for buildings with central air-conditionings
CN105299792A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Central air conditioner with purification function
CN105327618A (en) * 2015-12-03 2016-02-17 华玉叶 Household coal stove flue gas purification method
CN105344239A (en) * 2015-11-14 2016-02-24 华玉叶 A method of purifying indoor air by utilization of a household heating radiator
CN105381709A (en) * 2015-11-13 2016-03-09 无锡桥阳机械制造有限公司 Canister used for gas mask
CN105381712A (en) * 2015-11-14 2016-03-09 无锡清杨机械制造有限公司 Air conditioner filter for preventing and treating haze
CN105396232A (en) * 2015-11-13 2016-03-16 无锡桥阳机械制造有限公司 Canister for gas mask
CN105413451A (en) * 2015-11-13 2016-03-23 无锡桥阳机械制造有限公司 Air conditioner filter for preventing and controlling haze
CN105423461A (en) * 2015-11-13 2016-03-23 无锡桥阳机械制造有限公司 Central air conditioner with purifying function
CN105413323A (en) * 2015-11-13 2016-03-23 无锡桥阳机械制造有限公司 Air conditioner filter for preventing and controlling haze
CN105413078A (en) * 2015-11-14 2016-03-23 无锡清杨机械制造有限公司 Breathing mask with filtering and purifying functions
CN105413077A (en) * 2015-11-13 2016-03-23 朱忠良 Breathing mask suitable for high-pollution weather
CN105413076A (en) * 2015-11-13 2016-03-23 无锡桥阳机械制造有限公司 Breathing mask with filtering and purifying functions
CN105435631A (en) * 2015-11-14 2016-03-30 华玉叶 Method for purifying indoor air by use of domestic finned radiator
CN105435541A (en) * 2015-11-13 2016-03-30 无锡桥阳机械制造有限公司 Filtering mesh capable of preventing and controlling haze
CN105457411A (en) * 2015-11-13 2016-04-06 无锡桥阳机械制造有限公司 Air-conditioning filter for control of haze
CN105457624A (en) * 2015-11-17 2016-04-06 安徽省元琛环保科技有限公司 Composite metal oxide catalyst for low temperature denitration and preparation method thereof
CN105457485A (en) * 2015-11-13 2016-04-06 无锡桥阳机械制造有限公司 Method for purifying indoor air by fan
CN105605675A (en) * 2015-11-13 2016-05-25 无锡桥阳机械制造有限公司 Air purifier for preventing and treating haze
CN105597522A (en) * 2015-11-14 2016-05-25 华玉叶 Household coal stove flue gas purification method
CN105817218A (en) * 2016-03-23 2016-08-03 清华大学 Vanadium-titanium catalyst for removing UPOPs in exhaust gas
CN105964244A (en) * 2016-05-09 2016-09-28 大唐南京环保科技有限责任公司 Vanadium-titanium powder suitable for denitration catalyst with multitime regeneration as well as preparation method and application thereof
CN106179323A (en) * 2016-07-01 2016-12-07 中国科学院城市环境研究所 A kind of vanadium tungsten titanium oxide catalyst and its production and use
CN106268779A (en) * 2016-08-11 2017-01-04 重庆大学 A kind of middle high temperature SCR denitration with alkali resistant metal poisoning and preparation method thereof
CN106732505A (en) * 2016-11-17 2017-05-31 中国建筑材料科学研究总院 Denitrating catalyst and its preparation method and application
CN107670675A (en) * 2017-10-12 2018-02-09 王玉红 A kind of automobile-used zinc sulphide tail-gas catalyst and preparation method thereof
CN108236943A (en) * 2016-12-23 2018-07-03 中国科学院宁波城市环境观测研究站 A kind of preparation method of vanadium oxide catalyst
CN109012684A (en) * 2018-10-10 2018-12-18 大连中威海跃科技有限公司 Catalyst for denitrating flue gas and its preparation method and application
CN110508273A (en) * 2019-07-26 2019-11-29 华侨大学 A kind of low temperature vanadium titanium-based SCR denitration and preparation method thereof
CN110721701A (en) * 2019-10-16 2020-01-24 山东大学 Cobalt-chromium modified catalyst and preparation method and application thereof
CN114192158A (en) * 2021-12-30 2022-03-18 山东大学 Preparation method of CO and NOx synergistic removal catalyst
CN114515568A (en) * 2022-01-28 2022-05-20 中国科学院城市环境研究所 Modified denitration catalyst and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101396655A (en) * 2008-10-23 2009-04-01 清华大学 Titanium-base multi-component catalyst for power plant flue-gas SCR denitration and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101396655A (en) * 2008-10-23 2009-04-01 清华大学 Titanium-base multi-component catalyst for power plant flue-gas SCR denitration and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
邹鹏等: "钒钛SCR脱硝催化剂低温研究进展", 《电力科技与环保》, vol. 27, no. 5, 31 October 2011 (2011-10-31) *

Cited By (82)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103252232A (en) * 2013-05-30 2013-08-21 中国科学院生态环境研究中心 Zirconium-doped vanadium-based oxide catalyst, and preparation method and application thereof
CN103252232B (en) * 2013-05-30 2015-09-30 中国科学院生态环境研究中心 A kind of vanadium oxide catalyst, preparation method and its usage of zirconium doping
CN104815707A (en) * 2015-05-07 2015-08-05 中国华能集团清洁能源技术研究院有限公司 Inactivated vanadium-titanium-based honeycomb-like denitration catalyst low-temperature modifying regeneration liquid and preparation method thereof
CN104815707B (en) * 2015-05-07 2017-12-08 中国华能集团清洁能源技术研究院有限公司 One kind inactivation vanadium titanium-based Faveolate denitration catalyst low temperature modification regenerated liquid and preparation method thereof
CN105289183A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Air filter
CN105289719A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Composition used for preventing and controlling fog and haze
CN105214240A (en) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 A kind of possess the breathing mask filtered with purification function
CN105214481A (en) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 A kind of flue gas purifying technique
CN105605675A (en) * 2015-11-13 2016-05-25 无锡桥阳机械制造有限公司 Air purifier for preventing and treating haze
CN105457485A (en) * 2015-11-13 2016-04-06 无锡桥阳机械制造有限公司 Method for purifying indoor air by fan
CN105457411A (en) * 2015-11-13 2016-04-06 无锡桥阳机械制造有限公司 Air-conditioning filter for control of haze
CN105214661A (en) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 A kind of catalyst preventing and treating haze
CN105214479A (en) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 A kind of flue gas purifying technique
CN105233580A (en) * 2015-11-13 2016-01-13 无锡桥阳机械制造有限公司 Air purifier for preventing and treating haze
CN105233675A (en) * 2015-11-13 2016-01-13 无锡桥阳机械制造有限公司 Filter screen for preventing and controlling haze
CN105238251A (en) * 2015-11-13 2016-01-13 无锡桥阳机械制造有限公司 Coating for preventing and controlling haze
CN105233680A (en) * 2015-11-13 2016-01-13 无锡桥阳机械制造有限公司 Air-conditioning filter capable of controlling haze
CN105233591A (en) * 2015-11-13 2016-01-13 朱忠良 Abnormal odor removing method for automobile
CN105233581A (en) * 2015-11-13 2016-01-13 无锡清杨机械制造有限公司 Filter screen capable of controlling haze
CN105233676A (en) * 2015-11-13 2016-01-13 无锡桥阳机械制造有限公司 Filter screen for preventing and controlling haze
CN105251352A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Smoke purification technology
CN105249561A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Mask for preventing and treating haze
CN105258256A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Method for purifying air in building with central air-conditioning
CN105435541A (en) * 2015-11-13 2016-03-30 无锡桥阳机械制造有限公司 Filtering mesh capable of preventing and controlling haze
CN105251343A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Method for purifying indoor air by means of fan
CN105251346A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Filter screen for preventing and treating haze
CN105251273A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Filter screen for preventing and treating haze
CN105251291A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Method for purifying indoor air by means of fan
CN105255346A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Paint for prevention and treatment of haze
CN105251344A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Flue gas scrubbing technology
CN105251342A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Air conditioner filter for preventing and treating haze
CN105251294A (en) * 2015-11-13 2016-01-20 无锡清杨机械制造有限公司 Air conditioner filter for preventing and treating haze
CN105251345A (en) * 2015-11-13 2016-01-20 朱忠良 Air conditioner filter for preventing and treating haze
CN105289285A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Fan with purifying function
CN105413076A (en) * 2015-11-13 2016-03-23 无锡桥阳机械制造有限公司 Breathing mask with filtering and purifying functions
CN105276719A (en) * 2015-11-13 2016-01-27 无锡桥阳机械制造有限公司 Central air conditioner with purification function
CN105289128A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Filter screen used for preventing and controlling fog and haze
CN105413077A (en) * 2015-11-13 2016-03-23 朱忠良 Breathing mask suitable for high-pollution weather
CN105413323A (en) * 2015-11-13 2016-03-23 无锡桥阳机械制造有限公司 Air conditioner filter for preventing and controlling haze
CN105289127A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Filter screen used for preventing and controlling fog and haze
CN105219248A (en) * 2015-11-13 2016-01-06 无锡桥阳机械制造有限公司 A kind of coating preventing and treating haze
CN105423461A (en) * 2015-11-13 2016-03-23 无锡桥阳机械制造有限公司 Central air conditioner with purifying function
CN105258224A (en) * 2015-11-13 2016-01-20 无锡桥阳机械制造有限公司 Air purifier for preventing and treating haze
CN105413451A (en) * 2015-11-13 2016-03-23 无锡桥阳机械制造有限公司 Air conditioner filter for preventing and controlling haze
CN105214406A (en) * 2015-11-13 2016-01-06 朱忠良 A kind of automobile eliminates the unusual smell method
CN105396232A (en) * 2015-11-13 2016-03-16 无锡桥阳机械制造有限公司 Canister for gas mask
CN105299791A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Air purification method for buildings with central air-conditionings
CN105299792A (en) * 2015-11-13 2016-02-03 无锡桥阳机械制造有限公司 Central air conditioner with purification function
CN105381709A (en) * 2015-11-13 2016-03-09 无锡桥阳机械制造有限公司 Canister used for gas mask
CN105344239A (en) * 2015-11-14 2016-02-24 华玉叶 A method of purifying indoor air by utilization of a household heating radiator
CN105381712A (en) * 2015-11-14 2016-03-09 无锡清杨机械制造有限公司 Air conditioner filter for preventing and treating haze
CN105276701A (en) * 2015-11-14 2016-01-27 无锡清杨机械制造有限公司 Window type air purifier
CN105435631A (en) * 2015-11-14 2016-03-30 华玉叶 Method for purifying indoor air by use of domestic finned radiator
CN105222199A (en) * 2015-11-14 2016-01-06 无锡清杨机械制造有限公司 A kind of smoke exhaust ventilator with air-cleaning function
CN105298938A (en) * 2015-11-14 2016-02-03 无锡清杨机械制造有限公司 Bathroom exhaust fan with purification function
CN105597522A (en) * 2015-11-14 2016-05-25 华玉叶 Household coal stove flue gas purification method
CN105413078A (en) * 2015-11-14 2016-03-23 无锡清杨机械制造有限公司 Breathing mask with filtering and purifying functions
CN105298936A (en) * 2015-11-14 2016-02-03 无锡清杨机械制造有限公司 Bathroom exhaust fan with purifying function
CN105299774A (en) * 2015-11-14 2016-02-03 无锡清杨机械制造有限公司 Window type air purifier
CN105214482A (en) * 2015-11-14 2016-01-06 华玉叶 A kind of domestic briquet stove flue gas purifying method
CN105251349A (en) * 2015-11-14 2016-01-20 华玉叶 Method for purifying indoor air by means of domestic heating radiator
CN105214395A (en) * 2015-11-14 2016-01-06 无锡清杨机械制造有限公司 A kind of screen pack preventing and treating haze
CN105288888A (en) * 2015-11-14 2016-02-03 无锡清杨机械制造有限公司 Respiratory mask with filtering and purification functions
CN105214489A (en) * 2015-11-14 2016-01-06 华玉叶 A kind of domestic briquet stove flue gas purifying method
CN105298939A (en) * 2015-11-14 2016-02-03 无锡清杨机械制造有限公司 Bathroom exhaust fan with purification function
CN105457624A (en) * 2015-11-17 2016-04-06 安徽省元琛环保科技有限公司 Composite metal oxide catalyst for low temperature denitration and preparation method thereof
CN105327618A (en) * 2015-12-03 2016-02-17 华玉叶 Household coal stove flue gas purification method
CN105817218A (en) * 2016-03-23 2016-08-03 清华大学 Vanadium-titanium catalyst for removing UPOPs in exhaust gas
CN105964244B (en) * 2016-05-09 2018-11-09 大唐南京环保科技有限责任公司 A kind of vanadium titanium valve and the preparation method and application thereof being suitable for repeatedly regeneration denitrating catalyst
CN105964244A (en) * 2016-05-09 2016-09-28 大唐南京环保科技有限责任公司 Vanadium-titanium powder suitable for denitration catalyst with multitime regeneration as well as preparation method and application thereof
CN106179323A (en) * 2016-07-01 2016-12-07 中国科学院城市环境研究所 A kind of vanadium tungsten titanium oxide catalyst and its production and use
CN106268779A (en) * 2016-08-11 2017-01-04 重庆大学 A kind of middle high temperature SCR denitration with alkali resistant metal poisoning and preparation method thereof
CN106732505A (en) * 2016-11-17 2017-05-31 中国建筑材料科学研究总院 Denitrating catalyst and its preparation method and application
CN108236943A (en) * 2016-12-23 2018-07-03 中国科学院宁波城市环境观测研究站 A kind of preparation method of vanadium oxide catalyst
CN107670675A (en) * 2017-10-12 2018-02-09 王玉红 A kind of automobile-used zinc sulphide tail-gas catalyst and preparation method thereof
CN109012684A (en) * 2018-10-10 2018-12-18 大连中威海跃科技有限公司 Catalyst for denitrating flue gas and its preparation method and application
CN109012684B (en) * 2018-10-10 2021-09-10 大连中威海跃科技有限公司 Flue gas denitration catalyst and preparation method and application thereof
CN110508273A (en) * 2019-07-26 2019-11-29 华侨大学 A kind of low temperature vanadium titanium-based SCR denitration and preparation method thereof
CN110721701A (en) * 2019-10-16 2020-01-24 山东大学 Cobalt-chromium modified catalyst and preparation method and application thereof
CN110721701B (en) * 2019-10-16 2020-08-18 山东大学 Cobalt-chromium modified catalyst and preparation method and application thereof
CN114192158A (en) * 2021-12-30 2022-03-18 山东大学 Preparation method of CO and NOx synergistic removal catalyst
CN114515568A (en) * 2022-01-28 2022-05-20 中国科学院城市环境研究所 Modified denitration catalyst and preparation method thereof

Similar Documents

Publication Publication Date Title
CN102764643A (en) Vanadium-titanium oxide catalyst, and preparation method and application thereof
CN105148928B (en) Water resistant sulfur resistive type denitrating flue gas powder catalyst, preparation method and its usage
CN105214679B (en) A kind of water resistant sulfur resistive type denitrating flue gas powder catalyst, preparation method and its usage
CN101920213B (en) Low temperature SCR denitration catalyst taking organic metal framework as carrier and preparation method thereof
CN105056923B (en) A kind of water resistant sulfur resistive type denitrating catalyst, preparation method and its usage
CN102658161B (en) Supported iron-based composite oxide catalyst and preparation method thereof
CN105080566A (en) Flue gas denitrification powder catalyst as well as preparation method and application thereof
CN109569587A (en) A kind of manganese-based low-temperature catalyst for denitrating flue gas and preparation method thereof
CN104525216B (en) Denitrating catalyst under the conditions of wide temperature window high-sulfur and preparation method thereof
CN102764645B (en) SCR (selective catalytic reduction) nitrogen oxide catalyst, and preparation method and application thereof
CN106582606B (en) Non-vanadium low-temperature denitration catalyst and preparation method thereof
CN101411984A (en) Other transitional metals doped ferrotitanium composite oxides catalyst for selectively reducing nitrous oxides by ammonia
CN105771961B (en) A kind of CeO2Nanotube supported denitrating catalyst and preparation method thereof
CN105148927B (en) A kind of water resistant sulfur resistive type denitrating flue gas powder catalyst, preparation method and its usage
CN101396656A (en) Power plant flue-gas SCR denitration catalyst capable of preventing sulfur trioxide poisoning and preparation method thereof
CN112742413B (en) Low-temperature SCR denitration catalyst and preparation method and application thereof
CN105833901A (en) PrOx-MnOx/SAPO-34 low-temperature SCR smoke denitration catalyst and preparation method and application thereof
CN104741114A (en) Flat-plate type high-temperature SCR (Selective Catalytic Reduction) denitration catalyst and preparation method thereof
CN106582874A (en) High temperature resistant phosphotungstic acid adsorbed iron-based oxide catalyst and preparation method thereof
CN110586073A (en) Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof
CN102513095B (en) Medium temperature denitration catalyst with carbon-based material loaded with cerium tungsten and preparation method of medium temperature denitration catalyst
CN105618029A (en) SCR (Selective Catalytic Reduction) denitration catalyst coated with rare earth and preparation method thereof
CN113398952A (en) Flue gas wide-temperature SCR denitration catalyst and production process thereof
CN106513005A (en) A preparing method of an iron-based composite oxide catalyst
CN106362733A (en) High-temperature resistant manganite catalyst and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20121107