CN102553573A - Nitrogen oxide oxidizing catalyst and preparation method of nitrogen oxide oxidizing catalyst - Google Patents
Nitrogen oxide oxidizing catalyst and preparation method of nitrogen oxide oxidizing catalyst Download PDFInfo
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Abstract
The invention provides a catalyst for purifying nitrogen oxide. In the presence of oxygen, conversion from nitrogen oxide (such as NO, N2O and the like) to nitrogen dioxide can be realized at lower temperature. The catalyst is prepared by a coprecipitation method or a soaking method and the main active component of the catalyst is manganese oxide. The catalyst is suitable for catalytic oxidation of nitrogen monoxide in flue gas and then integrated control of desulfurization and denitrification is realized. The catalyst is applied to a purification test of simulated flue gas with NO concentration of 200ppm, the conversion from the NO to the NO2 can be realized at lower temperature, and the NO2 is fed into a desulfurizing tower for further reacting with a desulfurizing agent so as to realize removal of nitrogen oxides in flue gas. The catalyst has remarkable effect in flue gas denitrification of coal-fired industrial boilers, and has better practical value and economic benefit.
Description
Technical field
The present invention relates to nitrogen oxide removal method, particularly, the present invention relates to a kind of catalyst, its preparation method that is used for the oxidation removal nitrogen oxide, and uses thereof.
Background technology
Nitrogen oxide (NO
x) be one of major pollutants that cause atmosphere pollution, be mainly derived from the burning of fuel.NO
xCan participate in the formation of acid rain and photochemical fog, health and environment are all had great harm.Along with expanding economy, people's environmental protection and health perception strengthen gradually, and relevant laws and regulations are to NO
xEmission request also more and more stricter.Therefore, seek rational and effective NO
xControl technology have very important realistic meaning and economic benefit.NO
xControl device mainly contain control (novel burner design etc.) and burning back control (being gas denitrifying technology) in control (fuel denitride technology etc.), the combustion process before the burning.Burning back control technology comprises catalysis method, absorption process, absorption method, electrochemical process etc. again, and wherein catalysis method is one of more method of research at present.Catalysis method is divided into catalytic oxidation, catalytic reduction, catalytic decomposition again according to the difference of reaction principle.
As far as stationary source, nitric oxide (NO) accounts for flue gas NO
xMore than 90%, therefore, NO remove be control NO
xThe key of discharging.The research of catalysis method at present mainly concentrates on the SCR catalytic reduction, and is less relatively for the catalytic oxidation technical research.Catalytic oxidation is (like O at oxidant
2Deng) be NO under the condition that exists with part NO catalytic oxidation
2, absorb with wet method or semi-dry desulphurization absorbent again.This method can not cause secondary pollution owing to do not consume reducing agent, and desulphurization denitration when being expected to realize wet method or semidry method.Therefore, in recent years, NO catalytic oxidation technology has received extensive concern.
Patent CN 1317363A (2001) has announced a kind of NO of removing
xLiquid-phase catalyst, promptly utilize the oxygen in the flue to be oxidant, the complex compound Co (en of cobalt
2)
2+Be catalyst, in liquid phase, realize oxidation and the absorption of NO.It is the method for catalyst oxidation NO with the type ZSM 5 molecular sieve that patent CN 101259368A (2008) has announced a kind of, is 500ppmv in NO concentration, O
2Content is 20 (V) %, and general gas flow is 500mL/min, and relative humidity is 60%, and the time of staying is under the experiment condition of 1s, and NO is 76% at 20 ℃ conversion ratio.But because oxygen content is about 5-6% in the actual flue gas, well below 20%, and should the less (GHSV～3600h of experiment reaction velocity
-1), so this catalyst does not obtain widespread usage as yet.Patent CN 102188979A (2011) has announced the catalytic oxidation catalyst for denitrating flue gas, copper, vanadium load calcium cross-linked clay.At NO is 500ppm, O
2Be 10%, N
2Do balance gas, air speed is 12000h
-1, NO can reach 48% removal efficiency.
There are (for example below 300 ℃) active relatively poor, problems such as energy consumption is high, cost is high, complicated operation under the low temperature in existing oxidation and denitration catalyst, needs the novel oxidation and denitration catalyst of research and development badly.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide a kind of nitrogen oxide oxide catalyst, can be with nitrogen oxide (for example NO, N under the condition that oxygen exists
2O etc.) catalytic oxidation is a nitrogen dioxide, absorbs with wet method or semi-dry desulphurization absorbent again, has characteristics such as economical and efficient, non-secondary pollution.
Said nitrogen oxide oxide catalyst is the manganese-base oxide catalyst; Said catalyst activity component is a manganese oxide; Said manganese oxide load is on inorganic carrier, or in manganese oxide and cobalt oxide, cerium oxide, the cupric oxide a kind or at least 2 kinds is formed O composite metallic oxide catalysts.
Preferably, said carrier is an inorganic oxide carrier, preferred silica, alundum (Al, titanium dioxide or its mixture, preferred alundum (Al or titanium dioxide, more preferably titanium dioxide.
Preferably, when said manganese oxide load was on carrier, manganese oxide content was effective dose; Preferably account for the 1wt%～30wt% of total catalyst weight; For example 1.01%, 1.1%, 1.2%, 19%, 21%, 25%, 29%, 29.9% etc., further be preferably 5wt%～25wt%, more preferably 7wt%～15wt%; Be preferably 8wt%～12wt% especially, most preferably 10wt%.
Said O composite metallic oxide catalyst typical case but non-limiting instance have: manganese oxide/cobalt oxide/cerium oxide, manganese oxide/cobalt oxide/cupric oxide, manganese oxide/cerium oxide/cupric oxide, manganese oxide/cobalt oxide/cerium oxide/cupric oxide etc.
Preferably; Said O composite metallic oxide catalyst is formed by a kind in manganese oxide and cobalt oxide, cerium oxide, the cupric oxide; For example manganese oxide/cobalt oxide, manganese oxide/cerium oxide, manganese oxide/cupric oxide etc., further preferred, form by a kind in manganese oxide and cobalt oxide, the cerium oxide; Preferred especially, form by manganese oxide and cerium oxide.
Preferably, the mol ratio of manganese element and other metallic elements is 1: 4～4: 1 in the said O composite metallic oxide catalyst, further is preferably 1: 3～3: 1, more preferably 1: 2～2: 1, is preferably 1: 1 especially.
One of the object of the invention also is to provide a kind of co-precipitation preparation method of said nitrogen oxide oxide catalyst; Said method comprises: by the formulated metal salt solution, regulate the pH value of metal salt solution, make precipitation by metallic ion; Wear out successively then; Filter, roasting obtains the nitrogen oxide oxide catalyst.
Preferably, grind after the roasting, compressing tablet, screening obtain the nitrogen oxide oxide catalyst, further preferably chooses 20～90 order catalyst, more preferably chooses 30～70 orders, especially preferably chooses 40～60 orders.
Said slaine is the salt of manganese salt and other metallic elements of forming O composite metallic oxide catalyst; Be a kind or at least 2 kinds combination in manganese salt and cobalt salt, cerium salt, the mantoquita, said combination typical case but non-limiting instance have: the combination of manganese salt and cobalt salt, the combination of manganese salt and mantoquita; The combination of manganese salt, cobalt salt, cerium salt; The combination of manganese salt, cerium salt, mantoquita, the combinations of manganese salt, cobalt salt, cerium salt, mantoquita etc. are preferably a kind combination in manganese salt and cobalt salt, cerium salt, the mantoquita; Further be preferably a kind combination in manganese salt and cobalt salt, the cerium salt, be preferably the combination of manganese salt and cerium salt especially; Preferred said slaine is a water soluble salt, further is preferably nitrate or acetate, is preferably nitrate especially.
Preferably, use the pH value of the mixed liquor adjusting metal salt solution of highly basic and weak base, the further preferred Na that uses
2CO
3The pH value of regulating metal salt solution with the mixed liquor of NaOH.
Preferably, the said deposition fully that is precipitated as, the said precipitation by metallic ion that can think more than 99% that precipitates fully, or definite by the those skilled in the art according to the professional knowledge of its grasp.
Preferably, said being deposited under the stirring carried out.
Preferably, the said sedimentation time is more than the 2h, and for example 2.1h, 3h, 4h, 6h, 9h, 10h, 15h, 20h etc. further are preferably more than the 5h, more preferably more than the 8h, are preferably more than the 12h especially.
Preferably, said ageing time is more than the 8h, and for example 8.1h, 8.2h, 8.5h, 9h, 25h, 29h, 31h, 31.5h, 31.9h etc. further are preferably 10～32h, and more preferably 11～28h is preferably 12～24h especially.
Preferably, filter back washing gained sediment, further preferably adopt the deionized water washing.
Preferably, before the roasting gained sediment is carried out drying; Preferred said baking temperature is more than 90 ℃; For example 90.5 ℃, 91 ℃, 92 ℃, 101 ℃, 109 ℃, 130 ℃, 140 ℃, 145 ℃, 149 ℃, 149.9 ℃, 160 ℃ etc.; Further be preferably 100 ℃～150 ℃, more preferably 110 ℃～120 ℃, be preferably 110 ℃ especially; Be more than the 8h preferred said drying time, and for example 8.1h, 8.2h, 8.5h, 9h, 25h, 29h, 31h, 31.5h, 31.9h etc. further are preferably 10～32h, and more preferably 11～28h is preferably 12h especially.
Preferably, said roasting is carried out under air atmosphere.
Preferably, said sintering temperature is 200～700 ℃, for example: 201 ℃, 202 ℃, 205 ℃, 499 ℃, 599 ℃, 650 ℃, 690 ℃, 695 ℃, 699 ℃ etc., further be preferably 300～600 ℃, be preferably 300～500 ℃ especially.
Preferably; Said roasting time is more than the 2h, for example: 2.01h, 2.02h, 2.05h, 2.1h, 2.2h, 2.5h, 4h, 6h, 8h, 15h, 18h, 19h, 25h, 30h etc. further are preferably 2～20h; More preferably 2～10h is preferably 2～5h especially.
Adopt the nitrogen oxide oxide catalyst of coprecipitation preparation method preparation of said nitrogen oxide oxide catalyst active high down, the conversion ratio to nitrogen oxide in the time of 200 ℃ can reach 77%, can reach 96% at 250 ℃, has active preferably.
One of the object of the invention also is to provide a kind of immersion process for preparation method of said nitrogen oxide oxide catalyst, and said method comprises: by the formulated manganese salt solution, add carrier; Stir; Evaporation, oven dry, roasting; Grinding successively, compressing tablet, screening then makes the nitrogen oxide oxide catalyst.
Preferably, said manganese salt is water-soluble manganese salt, further is preferably manganese nitrate or manganese acetate.
Preferably, said manganese salt solution is the aqueous solution of manganese salt, and special preferred solvent is a deionized water.
Preferably, said carrier is an inorganic oxide carrier, preferred silica, alundum (Al, titanium dioxide or its mixture, preferred alundum (Al or titanium dioxide, more preferably titanium dioxide.
Preferably, said mixing time is more than the 2h, and for example 2.1h, 3h, 4h, 6h, 9h, 10h, 15h, 20h etc. further are preferably more than the 5h, more preferably more than the 8h, are preferably more than the 12h especially.
Preferably, the rotary evaporation mode is adopted in said evaporation.
Preferably, said evaporating temperature is more than 30 ℃, for example: 31 ℃, 32 ℃, 51 ℃, 52 ℃, 80 ℃, 90 ℃, 95 ℃, 99 ℃, 110 ℃ etc., further be preferably more than 50 ℃, and more preferably 60 ℃～100 ℃, be preferably 70 ℃ especially.
Preferably; Said bake out temperature is more than 80 ℃, for example: 80.1 ℃, 80.5 ℃, 81 ℃, 82 ℃, 85 ℃, 91 ℃, 140 ℃, 145 ℃, 149 ℃, 160 ℃ etc., further be preferably more than 90 ℃; More preferably 100 ℃～150 ℃, be preferably 110 ℃ especially.
Preferably, said drying time is more than the 8h, and for example 8.1h, 8.2h, 8.5h, 9h, 25h, 29h, 31h, 31.5h, 31.9h etc. further are preferably 10～32h, and more preferably 11～28h is preferably 12h especially.
Preferably, said sintering temperature is 200～700 ℃, for example: 201 ℃, 202 ℃, 205 ℃, 499 ℃, 599 ℃, 650 ℃, 690 ℃, 695 ℃, 699 ℃ etc., further be preferably 300～600 ℃, be preferably 400～500 ℃ especially.
Preferably; Said roasting time is more than the 2h, for example: 2.01h, 2.02h, 2.05h, 2.1h, 2.2h, 2.5h, 4h, 6h, 8h, 15h, 18h, 19h, 25h, 30h etc. further are preferably 2～20h; More preferably 2～10h is preferably 3～5h especially.
Preferably, 20～90 order catalyst are chosen in said screening, more preferably choose 30～70 order catalyst, especially preferably choose 40～60 order catalyst.
Adopt nitrogen oxide oxide catalyst conversion ratio to nitrogen oxide in the time of 250 ℃ of the immersion process for preparation method preparation of said nitrogen oxide oxide catalyst can reach 65%, can reach 82%, have active preferably at 300 ℃.
One of the object of the invention also is to provide the purposes of said nitrogen oxide oxide catalyst.
Said nitrogen oxide oxide catalyst can be applicable to removing of nitrogen oxide in the coal-burned industrial boiler flue gas or desulfurization and denitrification integral technology.
Nitrogen oxide oxide catalyst according to the invention can use separately, also can be used with other catalyst.
Manganese oxide according to the invention is manganese dioxide (MnO
2).
The invention provides a kind of gating catalytic oxidation nitrogen oxide catalyst; Said catalyst (for example below 300 ℃) at low temperatures has very high conversion ratio to nitrogen oxide; Need not add any fuel in its use; Utilize directly that oxygen is oxidant in the air, energy consumption is low, simple to operate, reaction condition is gentle, can reduce advantages such as secondary pollution and continuous operation but have.
Simultaneously, the present invention also provides the preparation method of two kinds of gating catalytic oxidation nitrogen oxide catalysts.It is simple that said method prepares process, easy to operate, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is that instance 1 preparation catalyst is to NO catalytic oxidation activity evaluation result figure
Fig. 2 is that instance 2 preparation catalyst are to NO catalytic oxidation activity evaluation result figure
Fig. 3 is that instance 2 preparation catalyst 4 prepare catalyst to NO catalytic oxidation activity evaluation result figure with instance 3.
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.
Used manganese acetate, 50% manganese nitrate solution, cerous nitrate, cobalt nitrate, the copper nitrate of preparation catalyst is Guangdong Xilong Chemical Co., Ltd's production in the embodiment of the invention; Analyze pure; Only be to help to understand the present invention, should be regarded as concrete restriction of the present invention.
Embodiment 1
Take by weighing the aqueous solution that obtains manganese after 2.22g four hydration manganese acetates dissolve, take by weighing 5.00g titanium dioxide (TiO
2) add wherein, continue to stir 5h, 70 ℃ of rotary evaporations, 110 ℃ of dried over night, 400 ℃ of roasting 5h, cooling back grinding, compressing tablet, screening, it is subsequent use to choose 40-60 order catalyst, is designated as catalyst 1.The quality that changes four hydration manganese acetates is 0.22g, 4.46g, and the consumption of titanium dioxide is constant, and the impregnated sample that obtains different manganese load capacity under the kindred circumstances is designated as catalyst 2 and catalyst 3 respectively.
Take by weighing the 14.32g mass fraction and be 50% manganese nitrate (Mn (NO
3)
2) solution adds deionized water and obtain Mn (NO
3)
2Solution takes by weighing 11.65g cobalt nitrate (Co (NO
3)
2) be dissolved in the deionized water Co (NO that obtains
3)
2Solution is 1: 1 mixed according to cobalt manganese mol ratio, in above-mentioned mixed liquor, adds the sodium carbonate (Na of 0.5mol/L
2CO
3) and mixed liquor (the mol ratio Na of NaOH (NaOH)
2CO
3/ NaOH=1: 2),, make Mn until pH=10
2+And Co
2+Metal ion precipitates fully, continues to stir suspension 5h, and aging 12h filters out the gained sediment; Spend deionised water, 110 ℃ of dried overnight, 300 ℃ of roasting 5h under air atmosphere; Grinding, compressing tablet, screening, it is subsequent use to choose 40-60 order catalyst, is designated as catalyst 4.Substitute cobalt (Co) as second active component with cerium (Ce), copper (Cu), make catalyst 5, catalyst 6 respectively with quadrat method.
Embodiment 3
Take by weighing the 14.32g mass fraction and be 50% manganese nitrate (Mn (NO
3)
2) solution adds deionized water and obtain Mn (NO
3)
2Solution takes by weighing 23.30g cobalt nitrate (Co (NO
3)
2) be dissolved in the deionized water Co (NO that obtains
3)
2Solution is 2: 1 mixed according to cobalt manganese mol ratio, in above-mentioned mixed liquor, adds the sodium carbonate (Na of 0.5mol/L
2CO
3) and mixed liquor (the mol ratio Na of NaOH (NaOH)
2CO
3/ NaOH=1: 2),, make Mn until pH=8
2+And Co
2+Metal ion precipitates fully, continues to stir suspension 10h, and aging 24h filters out the gained sediment; Spend deionised water, 110 ℃ of dried overnight, 500 ℃ of roasting 3h under air atmosphere; Grinding, compressing tablet, screening, it is subsequent use to choose 40-60 order catalyst, is designated as catalyst 7.Change the consumption of cobalt nitrate, weighing 5.83g cobalt nitrate, the manganese nitrate consumption is constant.Obtain the catalyst that cobalt manganese mol ratio was respectively 1: 2 under the kindred circumstances, be designated as catalyst 8.
Instance 4
1-3 is positioned in the fixed bed reactors with the 200mg catalyst, and experiment condition is following: NO:200ppm, O
2: 6%, N
2Be balance gas, total gas flow rate is 500mL/min, and reaction velocity is 100000h
-1-80000h
-1The reaction temperature interval is from 100 ℃ to 400 ℃, NO and product NO
2, accessory substance N
2O etc. all utilize the infrared-gas pond to detect.
Fig. 1 is that instance 1 preparation catalyst is to NO catalytic oxidation activity evaluation result figure; Data show that catalyst 1 and catalyst 3 samples have catalytic oxidation performance preferably to NO among the figure; Locate at 200 ℃, catalyst 1, catalyst 3 samples are respectively 22%, 22% to the conversion ratio of NO; The conversion ratio of two samples is respectively 63%, 65% all above 50% in the time of 250 ℃; Two sample conversion ratios then reach 82%, 80% in the time of 300 ℃.
Instance 5
4-6 is positioned in the fixed bed reactors with the 200mg catalyst, and experiment condition is following: NO:200ppm, O
2: 6%, N
2Be balance gas, total gas flow rate is 500mL/min, and reaction velocity is 100000h
-1-80000h
-1The reaction temperature interval is from 100 ℃ to 400 ℃, NO and product NO
2, accessory substance N
2O etc. all utilize the infrared-gas pond to detect.
Fig. 2 is that instance 2 preparation catalyst are to NO catalytic oxidation activity evaluation result figure; Data show that catalyst 5 samples are best to the catalytic oxidation effect of NO among the figure; Catalyst 4 takes second place; Catalyst 6 is relatively poor, and wherein catalyst 5, catalyst 4,6 three samples of catalyst are followed successively by 28%, 26%, 0.6% to NO Catalytic Oxygen conversion ratio under 150 ℃ of reaction temperatures; 200 ℃ are followed successively by 77%, 43%, 33%; Be followed successively by 96%, 72%, 61% under 250 ℃ of reaction temperatures; Wherein catalyst 5 samples all show catalytic performance preferably to the NO catalytic oxidation in whole temperature range, and oxidation has catalytic effect preferably to catalyst 4 samples to NO＜200 ℃ low-temperature zone.
Instance 6
Fig. 3 is a catalyst 7 and 8 pairs of NO catalytic oxidation activities of catalyst evaluation result figure in catalyst 4 catalyst and the instance 3 in the instance 2, and the transformation efficiency to the NO oxidation of catalyst 6, catalyst 7, catalyst 8 three samples correspondence under 150 ℃ of temperature conditions is followed successively by 26.1%, 26.6%, 17%; Transformation efficiency corresponding under 200 ℃ of temperature conditions is followed successively by 43.6%, 47.4%, 38.5%; The transformation efficiency that three samples are corresponding under 250 ℃ of temperature conditions is followed successively by 72%, 76%, 70% all above 50%.
Can know that by above embodiment nitrogen oxide oxide catalyst according to the invention effect aspect denitrating flue gas is remarkable, has good practical values and economic benefit.
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. nitrogen oxide oxide catalyst; Said catalyst is the manganese-base oxide catalyst; It is characterized in that; Said catalyst activity component is a manganese oxide, and said manganese oxide load is on inorganic carrier, or in manganese oxide and cobalt oxide, cerium oxide, the cupric oxide a kind or at least 2 kinds is formed O composite metallic oxide catalysts.
2. catalyst as claimed in claim 1 is characterized in that, said carrier is an inorganic oxide carrier, preferred silica, alundum (Al, titanium dioxide or its mixture, preferred alundum (Al or titanium dioxide, more preferably titanium dioxide;
Preferably, when said manganese oxide load was on carrier, manganese oxide content was effective dose; Preferably account for the 1wt%～30wt% of total catalyst weight, further be preferably 5wt%～25wt%, more preferably 7wt%～15wt%; Be preferably 8wt%～12wt% especially, most preferably 10wt%.
3. according to claim 1 or claim 2 catalyst; It is characterized in that; Said O composite metallic oxide catalyst is preferably formed by a kind in manganese oxide and cobalt oxide, cerium oxide, the cupric oxide, and is further preferred, forms by a kind in manganese oxide and cobalt oxide, the cerium oxide; Preferred especially, form by manganese oxide and cerium oxide;
Preferably, the mol ratio of manganese element and other metallic elements is 1: 4～4: 1 in the said O composite metallic oxide catalyst, further is preferably 1: 3～3: 1, more preferably 1: 2～2: 1, is preferably 1: 1 especially.
4. the co-precipitation preparation method of each said nitrogen oxide oxide catalyst of claim 1-3 is characterized in that, said method comprises: by the formulated metal salt solution; Regulate the pH value of metal salt solution; Make precipitation by metallic ion, wear out successively then, filter; Roasting obtains the nitrogen oxide oxide catalyst.
5. method as claimed in claim 4; It is characterized in that, preferably grind after the said roasting, compressing tablet, screening obtain the nitrogen oxide oxide catalyst, further preferably chooses 20～90 order catalyst; More preferably choose 30～70 orders, especially preferably choose 40～60 orders;
Said slaine is the salt of manganese salt and other metallic elements of forming O composite metallic oxide catalyst; Be a kind or at least 2 kinds combination in manganese salt and cobalt salt, cerium salt, the mantoquita; Be preferably a kind combination in manganese salt and cobalt salt, cerium salt, the mantoquita; Further be preferably a kind combination in manganese salt and cobalt salt, the cerium salt, be preferably the combination of manganese salt and cerium salt especially; Preferred said slaine is a water soluble salt, further is preferably nitrate or acetate, is preferably nitrate especially;
Preferably, use the pH value of the mixed liquor adjusting metal salt solution of highly basic and weak base, the further preferred Na that uses
2CO
3The pH value of regulating metal salt solution with the mixed liquor of NaOH;
Preferably, the said deposition fully that is precipitated as;
Preferably, said being deposited under the stirring carried out;
Preferably, the said sedimentation time is more than the 2h, further is preferably more than the 5h, more preferably more than the 8h, is preferably more than the 12h especially;
Preferably, said ageing time is more than the 8h, further is preferably 10～32h, and more preferably 11～28h is preferably 12～24h especially;
Preferably, filter back washing gained sediment, further preferably adopt the deionized water washing.
6. like claim 4 or 5 described methods, it is characterized in that, preferably the gained sediment is carried out drying before the roasting; Preferred said baking temperature is more than 90 ℃, further is preferably 100 ℃～150 ℃, more preferably 110 ℃～120 ℃, is preferably 110 ℃ especially; Be more than the 8h preferred said drying time, further is preferably 10～32h, and more preferably 11～28h is preferably 12h especially;
Preferably, said roasting is carried out under air atmosphere;
Preferably, said sintering temperature is 200～700 ℃, further is preferably 300～600 ℃, is preferably 300～500 ℃ especially;
Preferably, said roasting time is more than the 2h, further is preferably 2～20h, and more preferably 2～10h is preferably 2～5h especially.
7. the immersion process for preparation method of each said nitrogen oxide oxide catalyst of claim 1-3 is characterized in that, said method comprises: by the formulated manganese salt solution; Add carrier, stir, evaporation; Oven dry; Roasting, grinding successively, compressing tablet, screening then makes the nitrogen oxide oxide catalyst.
8. method as claimed in claim 7 is characterized in that, said manganese salt is preferably water-soluble manganese salt, further is preferably manganese nitrate or manganese acetate;
Preferably, said manganese salt solution is the aqueous solution of manganese salt, and special preferred solvent is a deionized water;
Preferably, said carrier is an inorganic oxide carrier, preferred silica, alundum (Al, titanium dioxide or its mixture, preferred alundum (Al or titanium dioxide, more preferably titanium dioxide;
Preferably, said mixing time is more than the 2h, further is preferably more than the 5h, more preferably more than the 8h, is preferably more than the 12h especially;
Preferably, the rotary evaporation mode is adopted in said evaporation;
Preferably, said evaporating temperature is more than 30 ℃, further is preferably more than 50 ℃, more preferably 60 ℃～100 ℃, is preferably 70 ℃ especially.
9. like claim 7 or 8 described methods, it is characterized in that said bake out temperature is preferably more than 80 ℃, further be preferably more than 90 ℃, more preferably 100 ℃～150 ℃, be preferably 110 ℃ especially;
Preferably, said drying time is more than the 8h, further is preferably 10～32h, and more preferably 11～28h is preferably 12h especially;
Preferably, said sintering temperature is 200～700 ℃, further is preferably 300～600 ℃, is preferably 400～500 ℃ especially;
Preferably, said roasting time is more than the 2h, further is preferably 2～20h, and more preferably 2～10h is preferably 3～5h especially;
Preferably, 20～90 order catalyst are chosen in said screening, more preferably choose 30～70 order catalyst, especially preferably choose 40～60 order catalyst.
10. like the purposes of each said nitrogen oxide oxide catalyst of claim 1-3, it is characterized in that said nitrogen oxide oxide catalyst can be applicable to removing of nitrogen oxide in the coal-burned industrial boiler flue gas or desulfurization and denitrification integral technology.
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