CN103170326A - Vanadium-cerium oxide catalyst as well as preparation method and purpose thereof - Google Patents
Vanadium-cerium oxide catalyst as well as preparation method and purpose thereof Download PDFInfo
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- CN103170326A CN103170326A CN2013101162028A CN201310116202A CN103170326A CN 103170326 A CN103170326 A CN 103170326A CN 2013101162028 A CN2013101162028 A CN 2013101162028A CN 201310116202 A CN201310116202 A CN 201310116202A CN 103170326 A CN103170326 A CN 103170326A
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Abstract
The invention relates to a vanadium-cerium oxide catalyst. The catalyst consists of the following chemical components: V2O5/CeO2, wherein the mass percentage of V2O5 in the vanadium-cerium oxide catalyst is 1%-10%. The invention further discloses a preparation method of the vanadium-cerium oxide catalyst. The vanadium-cerium oxide catalyst disclosed by the invention has NOx purification efficiency as high as 100% within 0-200 DEG C, has excellent SO2 intoxication resistance and can be operated within a wide temperature range.
Description
Technical field
The present invention relates to a kind of vanadium cerium oxide catalyst, preparation method and its usage, described catalyst is used for catalyzing and reducing nitrogen oxides.
Background technology
Nitrogen oxide (NO
x, comprise NO and NO
2) be one of Air Pollutants, it can cause acid rain, photochemical fog, forms higher ground level ozone concentration, also participates in forming airborne floating dust (PM2.5), also causes destruction and the greenhouse effects of ozone layer.。NO
xThe source can be divided into stationary source and moving source: stationary source is mainly the burning of Industrial Boiler and coal-burning power plant's fuel; Moving source mainly refers to the motor vehicles exhaust emissions.NO
xPollution to atmosphere is a global environmental problem, and it mainly contains NO to the impact of atmosphere
xDischarge capacity and atmosphere NO
xThe quick increase of concentration with making the variation of the character generation essence of China's atmosphere pollution, causes a series of city and regional environment problem, and health and ecological environment are consisted of grave danger.Therefore, how effectively to remove NO
xBecome the emphasis problem of current environmental protection.
At present with NH
3Be the reducing agent Selective Catalytic Reduction of NO
x(NH
3-catalyst system SCR) used mostly is V
2O
5-WO
3(MoO
3)/TiO
2And corresponding improved system, be widely used in the stationary source denitrating flue gas purification process such as coal-burning power plant, Industrial Boiler, have high NO in the higher temperature section
xPurification efficiency and anti-SO
2Poisoning performance.But catalyst system exists operating temperature window is narrower, N during high temperature
2The a large amount of generation of O caused N
2The shortcoming such as selective descend, high high-temp stability is poor.
The non-vanadium base NH that develops at present
3-SCR catalyst system mainly comprises molecular sieve catalyst and the oxide-based catalyst of load active component, though wherein Fe, Cu based molecular sieve catalyst superior performance, but still existing expensive, hydrothermal stability and the shortcoming such as sulfur resistance is relatively poor, Fe, Ce base oxide class catalyst exist that sulfur resistance is poor, the active shortcoming such as low.Therefore catalytic component based on vanadium is improved the satisfied needs of using and be still NH
3The important research content in-SCR field.
CN102909003A discloses a kind of vanadium cerium titanium catalyst of catalyzing and reducing nitrogen oxides, and this catalyst is take titanium dioxide as carrier, and vanadic anhydride is main active constituent, and ceria is the inferior active constituent of performance cooperative effect, and its composition is expressed as V
2O
5-CeO
2/ TiO
2, the content of vanadic anhydride is 0.1～1%, the mass content of ceria is 2～10%.But it is low in the catalytic activity of low temperature to invent disclosed catalyst, operating temperature window narrows, anti-SO
2Poisoning performance is relatively poor.
Summary of the invention
One of purpose of the present invention is to provide a kind of vanadium cerium oxide catalyst, and described catalyst exists〉have near the NO more than 100% in the temperature range of 200 ℃
xPurification efficiency has comparatively excellent anti-SO
2Poisoning performance, high high-temp stability is excellent, and the operating temperature window is wide.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1～10%.
Preferably, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1.5～8.5%, preferred 2～6%, further preferred 3%.
Described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is for example 1.8%, 2.5%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 9%, 9.5%.
The content of vanadium is too low may cause active low, too high under the sulfur-bearing condition easy oxidation SO
2, and vanadium is poisonous.Simultaneously, in described catalyst, cerium oxide had both served as the carrier of vanadium, mutually promoted with vanadium again and improved activity.
Two of purpose of the present invention is to provide a kind of preparation method of vanadium cerium oxide catalyst as above, adopts the active high of vanadium cerium oxide catalyst that homogeneous precipitation method of the present invention obtains, has very excellent anti-SO
2Poisoning performance, high high-temp stability is excellent, and the operating temperature window is wide.
A kind of preparation method of vanadium cerium oxide catalyst, described method comprises the steps:
(1) preparation vanadium source and cerium source solution under the oxalic acid existence condition mix vanadium source and cerium source solution, obtain mixed solution;
(2) add excessive urea precipitating reagent in mixed solution, make vanadium and cerium ion precipitation fully, with the precipitated product suction filtration that obtains, washing, drying, roasting obtains described vanadium cerium oxide catalyst.
The present invention replaces ammoniacal liquor as precipitating reagent with urea, has prepared a series of vanadium cerium oxide catalyst with simple sluggish precipitation.
Described cerium source is selected from the mixture of any one or at least two kinds in cerous nitrate, ammonium ceric nitrate, cerous chlorate or cerous sulfate, preferred cerous nitrate.Described cerium source is selected from the mixture of cerous nitrate and ammonium ceric nitrate, the mixture of cerous nitrate and cerous chlorate, the mixture of cerous nitrate and cerous sulfate, the mixture of ammonium ceric nitrate and cerous chlorate, the mixture of ammonium ceric nitrate and cerous sulfate, the mixture of cerous chlorate and cerous sulfate, the mixture of cerous nitrate, ammonium ceric nitrate, cerous chlorate and cerous sulfate.
Described vanadium source is selected from the mixture of any one or at least two kinds in ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium vanadate or sodium pyrovanadate, described mixture is the mixture of sodium pyrovanadate and sodium vanadate for example, the mixture of potassium metavanadate and sodium metavanadate, the mixture of ammonium metavanadate and sodium pyrovanadate, the mixture of sodium vanadate and potassium metavanadate, the mixture of sodium metavanadate and ammonium metavanadate, the mixture of sodium pyrovanadate, sodium vanadate and potassium metavanadate, the mixture of sodium metavanadate, ammonium metavanadate and sodium vanadate, preferred ammonium metavanadate.
Preparation vanadium source and cerium source solution, vanadium source and cerium source solution mix, and control V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1～10%.
In sluggish precipitation, make precipitating reagent with urea, precipitate vanadium source (cerium source), can precipitate fully when the molar ratio in urea and vanadium source (cerium source) is 1:1 in theory, might there be the problem of incomplete hydrolysis due to urea, therefore need to adds excessive urea.Urea is hydrolyzed, it is a process that slowly discharges hydroxide ion and carbanion, the slow hydrolysis of urea makes vanadium ion in solution (cerium ion) reactant concentration on every side too large variation can not occur, with respect to other precipitating reagents such as ammoniacal liquor and carbonic hydroammonium etc., precipitate with more being conducive to the oxide precursor uniform particles.
Urea/(vanadium source+cerium source) mol ratio is 8～12:1, for example 8.2:1,8.4:1,8.6:1,8.8:1,9:1,9.2:1,9.4:1,9.6:1,9.8:1,10.2:1,10.6:1,10.8:1,11:1,11.4:1,11.8:1, preferred 10:1.
Urea/(vanadium source+cerium source) mol ratio is larger, hydrolysis of urea and corresponding the increasing of ammonia amount that discharge, and solution alkalescence strengthens, and sedimentary growing amount also increases thereupon, precipitate more fully, and productive rate is increase gradually also.Simultaneously, the degree of supersaturation of precipitation increases, and is theoretical according to Chemical Kinetics, and degree of supersaturation increases, and the generating rate of crystal grain is faster, makes nucleation rate apparently higher than the speed of growth of nucleus, is conducive to generate small size particle.Excessive when urea/(vanadium source+cerium source) mol ratio, sedimentary recruitment is not remarkable, and precipitation is close to fully, and excessive concentration, wastes raw material, and increases cost.
Described precipitation temperature is 80～100 ℃, for example 81 ℃, 83 ℃, 85 ℃, 87 ℃, 89 ℃, 91 ℃, 91.5 ℃, 92 ℃, 92.5 ℃, 93 ℃, 93.5 ℃, 94 ℃, 94.5 ℃, 95 ℃, 95.5 ℃, 96 ℃, 96.5 ℃, 97 ℃, 97.5 ℃, 98 ℃, 98.5 ℃, 99 ℃, 99.5 ℃, preferred 90 ℃.
The time of described precipitation is 8～15h, for example 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, preferred 9～13h, further preferred 12h.
The temperature of described drying is 90～110 ℃, for example 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, preferred 95～105 ℃, further preferred 100 ℃.
The time of described drying is 10～15h, for example 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, preferred 10～13h, further preferred 12h.
Described roasting is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, and for example 430 ℃, 460 ℃, 510 ℃, 540 ℃, 570 ℃, 580 ℃, 590 ℃, preferred 500～600 ℃, further preferred 500 ℃.
Described roasting time is 2～5h, for example 2.4h, 2.7h, 3.1h, 3.4h, 3.6h, 3.9h, 4.2h, 4.5h, 4.8h, preferably 3h.
A kind of preparation method of vanadium cerium oxide catalyst, described method comprises the steps:
(1 '), preparation cerous nitrate and ammonium metavanadate solution mixed cerous nitrate and ammonium metavanadate solution, obtain mixed solution, control V under the oxalic acid existence condition
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1～10%;
(2 ') adds excessive urea precipitating reagent in mixed solution, urea/(vanadium source+cerium source) mol ratio is 10:1, continuous stirring 12h under 90 ℃ of water bath condition makes vanadium and cerium ion precipitation fully, with the precipitated product suction filtration that obtains, washing, dry 12h in 100 ℃ of baking ovens is then in Muffle furnace, under air atmosphere, at 400 ℃, 500 ℃ or 600 ℃ of roasting 3h, obtain described vanadium cerium oxide catalyst.
Three of purpose of the present invention is to provide a kind of preparation method of vanadium cerium oxide catalyst as above, adopts of the present invention revolving to steam the active high of vanadium cerium oxide catalyst that dipping method obtains, has very excellent anti-SO
2Poisoning performance, high high-temp stability is excellent, and the operating temperature window is wide.
A kind of preparation method of vanadium cerium oxide catalyst, described method comprises the steps:
(1 ' ') under the oxalic acid existence condition, preparation vanadium source solution;
(2 ' ') takes CeO
2Impregnated in the solution of vanadium source, stir by the Rotary Evaporators evaporate to dryness, drying, roasting obtains vanadium cerium oxide catalyst.
Preparation vanadium source solution, and take CeO
2Impregnated in solution, control V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1～10%.
Described vanadium source is selected from the mixture of any one or at least two kinds in ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium vanadate or sodium pyrovanadate, described mixture is the mixture of sodium pyrovanadate and sodium vanadate for example, the mixture of potassium metavanadate and sodium metavanadate, the mixture of ammonium metavanadate and sodium pyrovanadate, the mixture of sodium vanadate and potassium metavanadate, the mixture of sodium metavanadate and ammonium metavanadate, the mixture of sodium pyrovanadate, sodium vanadate and potassium metavanadate, the mixture of sodium metavanadate, ammonium metavanadate and sodium vanadate, preferred ammonium metavanadate.
Described stirring is at room temperature carried out, and described room temperature is 25 ℃, and the time of stirring at room is 0.5～1.5 hour, and for example 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, preferred 1 hour.
The temperature of described Rotary Evaporators evaporate to dryness is 50～70 ℃, for example 52 ℃, 54 ℃, 56 ℃, 58 ℃, 61 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, and preferred 53～67 ℃, further preferred 60 ℃.
The temperature of described drying is 90～110 ℃, for example 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, preferred 95～105 ℃, further preferred 100 ℃.
The time of described drying is 10～15h, for example 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, preferred 10～13h, further preferred 12h.
Described roasting is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, and for example 430 ℃, 460 ℃, 510 ℃, 540 ℃, 570 ℃, 580 ℃, 590 ℃, preferred 500～600 ℃, further preferred 500 ℃.
Described roasting time is 2～5h, for example 2.4h, 2.7h, 3.1h, 3.4h, 3.6h, 3.9h, 4.2h, 4.5h, 4.8h, preferably 3h.
A kind of preparation method of vanadium cerium oxide catalyst, described method comprises the steps:
(1 ' ' ') under the oxalic acid existence condition, the preparation ammonium metavanadate solution;
(2 ' ' ') takes CeO
2Impregnated in ammonium metavanadate solution, stirring at room 1h is by 60 ℃ of Rotary Evaporators evaporates to dryness, and 100 ℃ of oven drying 12h in Muffle furnace, in 500 ℃ of roasting 3h, obtain vanadium cerium oxide catalyst under air atmosphere.
Four of purpose of the present invention is to provide a kind of preparation method of vanadium cerium oxide catalyst as above, adopts the active high of vanadium cerium oxide catalyst that just wet dipping method of the present invention obtains, has very excellent anti-SO
2Poisoning performance, high high-temp stability is excellent, and the operating temperature window is wide.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of preparation method of vanadium cerium oxide catalyst, described method are just wet infusion process, comprise the steps:
(1 ' ' ' ') is dissolved in the vanadium source in oxalic acid solution;
(2 ' ' ' ') takes CeO
2Impregnated in the solution that step (1 ' ' ' ') obtains, stir, ultrasonic, drying, roasting;
(3 ' ' ' ') and repeating step (2 ' ' ' '), to obtain V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1～10% vanadium cerium oxide catalyst.
The time of described stirring is 0.5～1.5 hour, for example 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, and preferred 0.5 hour.
The described ultrasonic time is 0.5～1.5 hour, for example 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, and preferred 1 hour.
The temperature of described drying is 90～110 ℃, for example 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, preferred 95～105 ℃, further preferred 100 ℃.
The time of described drying is 10～15h, for example 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, preferred 10～13h, further preferred 12h.
Described roasting is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, and for example 430 ℃, 460 ℃, 510 ℃, 540 ℃, 570 ℃, 580 ℃, 590 ℃, preferred 500～600 ℃, further preferred 500 ℃.
Described roasting time is 2～5h, for example 2.4h, 2.7h, 3.1h, 3.4h, 3.6h, 3.9h, 4.2h, 4.5h, 4.8h, preferably 3h.
A kind of preparation method of vanadium cerium oxide catalyst, described method are just wet infusion process, comprise the steps:
(1 ' ' ' ' ') ammonium metavanadate is dissolved in oxalic acid solution;
(2 ' ' ' ' ') takes CeO
2Impregnated in the solution that step (1 ' ' ' ' ') obtains, stirred 30 minutes, ultrasonic 1 hour, 100 ℃ of oven dryings 12 hours, in Muffle furnace, under air atmosphere in 500 ℃ of roasting 3h;
(3 ' ' ' ' ') and repeating step (2 ' ' ' ' '), obtain V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1～10% vanadium cerium oxide catalyst.
Five of purpose of the present invention is to provide a kind of preparation method of vanadium cerium oxide catalyst as above, adopts the active high of vanadium cerium oxide catalyst that the method for the invention obtains, has very excellent anti-SO
2Poisoning performance, high high-temp stability is excellent, and the operating temperature window is wide.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of preparation method of vanadium cerium oxide catalyst, described method is sol-gal process, comprises the steps:
(1 ' ' ' ' ' ') under the oxalic acid existence condition, the mixed solution of preparation ammonium metavanadate and cerous nitrate;
(2 ' ' ' ' ' ') slowly drips the organic acid aqueous solution in above-mentioned mixed solution, become transparent colloidal sol to mixed solution, and then stir and obtain gel, drying, roasting obtains vanadium cerium oxide catalyst.
Described organic acid is selected from the mixture of any one or at least two kinds in citric acid, adipic acid or succinic acid, optimization citric acid.
The temperature of described drying is 90～110 ℃, for example 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, preferred 95～105 ℃, further preferred 100 ℃.
The time of described drying is 10～15h, for example 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, preferred 10～13h, further preferred 12h.
Described roasting is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, and for example 430 ℃, 460 ℃, 510 ℃, 540 ℃, 570 ℃, 580 ℃, 590 ℃, preferred 500～600 ℃, further preferred 500 ℃.
Described roasting time is 2～5h, for example 2.4h, 2.7h, 3.1h, 3.4h, 3.6h, 3.9h, 4.2h, 4.5h, 4.8h, preferably 3h.
A kind of preparation method of vanadium cerium oxide catalyst, described method is sol-gal process, comprises the steps:
(1 ' ' ' ' ' ' ') under the oxalic acid existence condition, the mixed solution of preparation ammonium metavanadate and cerous nitrate;
(2 ' ' ' ' ' ' ') in the situation that stir, slowly drip the lemon aqueous acid in above-mentioned mixed solution, become transparent colloidal sol to mixed solution, then stir and obtain gel, 100 ℃ of oven dryings 12 hours, in Muffle furnace, in 500 ℃ of roasting 3h, obtain vanadium cerium oxide catalyst under air atmosphere.
Six of purpose of the present invention is to provide a kind of purposes of vanadium cerium oxide catalyst as above, and described vanadium cerium oxide catalyst is used for catalyzing and reducing nitrogen oxides.
Compared with prior art, the present invention has following beneficial effect:
(1) V that adopts the method for the invention to prepare
2O
5/ CeO
2Catalyst all has good NH
3-SCR is active, the NH of the catalyst of sluggish precipitation preparation
3-SCR activity is the most excellent, and has good anti-sulfur poisonous performance;
(2) V
2O
5/ CeO
2Catalyst adopts the sluggish precipitation preparation take urea as precipitating reagent, and is simple, the active component high degree of dispersion;
(3) vanadium cerium oxide catalyst of the present invention〉have near the NO more than 100% in the temperature range of 200 ℃
xPurification efficiency has comparatively excellent anti-SO
2Poisoning performance, and the operating temperature window is wide.
The specific embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 3%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) preparation cerous nitrate and ammonium metavanadate solution mix cerous nitrate and ammonium metavanadate solution, obtain mixed solution, control V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 3%;
(2) add excessive urea precipitating reagent in mixed solution, urea/(vanadium source+cerium source) mol ratio is 10:1, continuous stirring 12h under 90 ℃ of water bath condition makes vanadium and cerium ion precipitation fully, with the precipitated product suction filtration that obtains, washing, dry 12h in 100 ℃ of baking ovens is then in Muffle furnace, under air atmosphere, at 500 ℃ of roasting 3h, obtain described vanadium cerium oxide catalyst.
Embodiment 2
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 3%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) under the oxalic acid existence condition, preparation vanadium source solution;
(2) take CeO
2Impregnated in the solution of vanadium source, stirring at room 1h is by 60 ℃ of Rotary Evaporators evaporates to dryness, and 100 ℃ of oven drying 12h in Muffle furnace, in 500 ℃ of roasting 3h, obtain vanadium cerium oxide catalyst under air atmosphere.
Embodiment 3
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 3%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) the vanadium source is dissolved in oxalic acid solution;
(2) take CeO
2Impregnated in the solution that step (1) obtains, stirred 30 minutes, ultrasonic 1 hour, 100 ℃ of oven dryings 12 hours, in Muffle furnace, under air atmosphere in 500 ℃ of roasting 3h;
(3) repeating step (2), obtain V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 3% vanadium cerium oxide catalyst.
Embodiment 4
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 3%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) under the oxalic acid existence condition, the mixed solution in preparation vanadium source and cerium source;
(2) in the situation that stir, slowly drip the lemon aqueous acid in above-mentioned mixed solution, become transparent colloidal sol to mixed solution, then stir and obtain gel, 100 ℃ of oven dryings 12 hours are in Muffle furnace, in 500 ℃ of roasting 3h, obtain vanadium cerium oxide catalyst under air atmosphere.
Get the 3%V of embodiment 1-4 distinct methods preparation
2O
5/ CeO
2Catalyst, catalyst volume 0.6mL, the 40-60 order is put into the catalyst activity evaluating apparatus, and activity rating carries out in fixed bed reactors.Simulated flue gas consists of (500ppm NH
3, 500ppm NO, 5%O
2), N
2Be Balance Air, total flow is 500mL/min, and reaction velocity is 50000h
-1
Made catalyst (3%V
2O
5/ CeO
2-sluggish precipitation) exist have near the NO more than 100% in the temperature range of 200 ℃
xPurification efficiency has comparatively excellent anti-SO
2Poisoning performance, and the operating temperature window is wide.Concrete activity data sees the following form.
Embodiment 5
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) under the oxalic acid existence condition, preparation cerous sulfate and sodium metavanadate solution mix cerous sulfate and sodium metavanadate solution, obtain mixed solution, control V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1%;
(2) add excessive urea precipitating reagent in mixed solution, urea/(cerous sulfate+sodium metavanadate) mol ratio is 8:1, continuous stirring 15h under 80 ℃ of water bath condition makes vanadium and cerium ion precipitation fully, with the precipitated product suction filtration that obtains, washing, dry 15h in 90 ℃ of baking ovens is then in Muffle furnace, under air atmosphere, at 400 ℃ of roasting 5h, obtain described vanadium cerium oxide catalyst.
Embodiment 6
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 10%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) preparation cerous nitrate and ammonium metavanadate solution mix cerous nitrate and ammonium metavanadate solution, obtain mixed solution, control V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 10%;
(2) under the oxalic acid existence condition, add excessive urea precipitating reagent in mixed solution, urea/(vanadium source+cerium source) mol ratio is 12:1, continuous stirring 15h under 100 ℃ of water bath condition, make vanadium and cerium ion precipitation fully, with the precipitated product suction filtration that obtains, washing, dry 10h in 110 ℃ of baking ovens, then in Muffle furnace, under air atmosphere, at 600 ℃ of roasting 2h, obtain described vanadium cerium oxide catalyst.
Embodiment 7
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) under the oxalic acid existence condition, preparation cerous sulfate solution;
(2) take CeO
2Impregnated in cerous sulfate solution, stirring at room 0.5h is by 50 ℃ of Rotary Evaporators evaporates to dryness, and 90 ℃ of oven drying 15h in Muffle furnace, in 400 ℃ of roasting 5h, obtain vanadium cerium oxide catalyst under air atmosphere.
Embodiment 8
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 10%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) under the oxalic acid existence condition, preparation sodium metavanadate solution;
(2) take CeO
2Impregnated in sodium metavanadate solution, stirring at room 1.5h is by 70 ℃ of Rotary Evaporators evaporates to dryness, and 110 ℃ of oven drying 10h in Muffle furnace, in 600 ℃ of roasting 2h, obtain vanadium cerium oxide catalyst under air atmosphere.
Embodiment 9
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) sodium metavanadate is dissolved in oxalic acid solution;
(2) take CeO
2Impregnated in the solution that step (1) obtains, stirred 90 minutes, ultrasonic 0.5 hour, 90 ℃ of oven dryings 15 hours, in Muffle furnace, under air atmosphere in 400 ℃ of roasting 5h;
(3) repeating step (2), obtain V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1% vanadium cerium oxide catalyst.
Embodiment 10
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 10%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) ammonium metavanadate is dissolved in oxalic acid solution;
(2) take CeO
2Impregnated in the solution that step (1) obtains, stirred 60 minutes, ultrasonic 1.5 hours, 110 ℃ of oven dryings 10 hours, in Muffle furnace, under air atmosphere in 600 ℃ of roasting 2h;
(3) repeating step (2), obtain V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 10% vanadium cerium oxide catalyst.
Embodiment 11
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) under the oxalic acid existence condition, the mixed solution of preparation cerous sulfate and ammonium metavanadate;
(2) in the situation that stir, slowly drip the aqueous solution of adipic acid in above-mentioned mixed solution, become transparent colloidal sol to mixed solution, then stir and obtain gel, 110 ℃ of oven dryings 10 hours are in Muffle furnace, in 600 ℃ of roasting 2h, obtain vanadium cerium oxide catalyst under air atmosphere.
Embodiment 12
A kind of vanadium cerium oxide catalyst, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 10%.
The preparation method of described vanadium cerium oxide catalyst comprises the steps:
(1) under the oxalic acid existence condition, the mixed solution of preparation cerous sulfate and ammonium metavanadate;
(2) in the situation that stir, slowly drip the aqueous solution of succinic acid in above-mentioned mixed solution, become transparent colloidal sol to mixed solution, then stir and obtain gel, 90 ℃ of oven dryings 15 hours are in Muffle furnace, in 400 ℃ of roasting 5h, obtain vanadium cerium oxide catalyst under air atmosphere.
Should be noted that and understand, in the situation that do not break away from the desired the spirit and scope of the present invention of accompanying claim, can make to the present invention of foregoing detailed description various modifications and improvement.Therefore, the scope of claimed technical scheme is not subjected to the restriction of given any specific exemplary teachings.
Applicant's statement, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not mean that namely the present invention must rely on above-mentioned method detailed and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention is 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., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a vanadium cerium oxide catalyst, is characterized in that, described catalyst has following chemical composition: V
2O
5/ CeO
2, described V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1～10%.
2. the preparation method of a vanadium cerium oxide catalyst as claimed in claim 1, is characterized in that, described method is sluggish precipitation, comprises the steps:
(1) preparation vanadium source and cerium source solution under the oxalic acid existence condition mix vanadium source and cerium source solution, obtain mixed solution;
(2) add excessive urea precipitating reagent in mixed solution, make vanadium and cerium ion precipitation fully, with the precipitated product suction filtration that obtains, washing, drying, roasting obtains described vanadium cerium oxide catalyst.
3. method as claimed in claim 2, is characterized in that, described cerium source is selected from the mixture of any one or at least two kinds in cerous nitrate, ammonium ceric nitrate, cerous chlorate or cerous sulfate, preferred cerous nitrate;
Preferably, described vanadium source is selected from the mixture of any one or at least two kinds in ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium vanadate or sodium pyrovanadate, preferred ammonium metavanadate;
Preferably, urea/(vanadium source+cerium source) mol ratio is 8～12:1, preferred 10:1;
Preferably, described precipitation temperature is 80～100 ℃, preferred 90 ℃;
Preferably, the time of described precipitation is 8～15h, preferred 9～13h, further preferred 12h;
Preferably, the temperature of described drying is 90～110 ℃, preferred 95～105 ℃, and further preferred 100 ℃;
Preferably, the time of described drying is 10～15h, preferred 10～13h, further preferred 12h;
Preferably, described roasting is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, and preferred 500～600 ℃, further preferred 500 ℃;
Preferably, described roasting time is 2～5h, preferred 3h;
Preferably, a kind of preparation method of vanadium cerium oxide catalyst, described method comprises the steps:
(1 '), preparation cerous nitrate and ammonium metavanadate solution mixed cerous nitrate and ammonium metavanadate solution, obtain mixed solution, control V under the oxalic acid existence condition
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1～10%;
(2 ') adds excessive urea precipitating reagent in mixed solution, urea/(vanadium source+cerium source) mol ratio is 10:1, continuous stirring 12h under 90 ℃ of water bath condition makes vanadium and cerium ion precipitation fully, with the precipitated product suction filtration that obtains, washing, dry 12h in 100 ℃ of baking ovens is then in Muffle furnace, under air atmosphere, at 400 ℃, 500 ℃ or 600 ℃ of roasting 3h, obtain described vanadium cerium oxide catalyst.
4. the preparation method of a vanadium cerium oxide catalyst as claimed in claim 1, is characterized in that, described method comprises the steps: for revolving the steaming infusion process
(1 ' ') under the oxalic acid existence condition, preparation vanadium source solution;
(2 ' ') takes CeO
2Impregnated in the solution of vanadium source, stir by the Rotary Evaporators evaporate to dryness, drying, roasting obtains vanadium cerium oxide catalyst.
5. method as claimed in claim 4, is characterized in that, described vanadium source is selected from the mixture of any one or at least two kinds in ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium vanadate or sodium pyrovanadate, preferred ammonium metavanadate;
Preferably, described stirring is at room temperature carried out, and the time of stirring at room is 0.5～1.5 hour, preferred 1 hour;
Preferably, the temperature of described Rotary Evaporators evaporate to dryness is 50～70 ℃, preferred 53～67 ℃, and further preferred 60 ℃;
Preferably, the temperature of described drying is 90～110 ℃, preferred 95～105 ℃, and further preferred 100 ℃;
Preferably, the time of described drying is 10～15h, preferred 10～13h, further preferred 12h;
Preferably, described roasting is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, and preferred 500～600 ℃, further preferred 500 ℃;
Preferably, described roasting time is 2～5h, preferred 3h;
Preferably, a kind of preparation method of vanadium cerium oxide catalyst, described method comprises the steps:
(1 ' ' ') under the oxalic acid existence condition, the preparation ammonium metavanadate solution;
(2 ' ' ') takes CeO
2Impregnated in ammonium metavanadate solution, stirring at room 1h is by 60 ℃ of Rotary Evaporators evaporates to dryness, and 100 ℃ of oven drying 12h in Muffle furnace, in 500 ℃ of roasting 3h, obtain vanadium cerium oxide catalyst under air atmosphere.
6. the preparation method of a vanadium cerium oxide catalyst as claimed in claim 1, is characterized in that, described method is just wet infusion process, comprises the steps:
(1 ' ' ' ') is dissolved in the vanadium source in oxalic acid solution;
(2 ' ' ' ') takes CeO
2Impregnated in the solution that step (1 ' ' ' ') obtains, stir, ultrasonic, drying, roasting;
(3 ' ' ' ') and repeating step (2 ' ' ' '), to obtain V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1～10% vanadium cerium oxide catalyst.
7. method as claimed in claim 6, is characterized in that, the time of described stirring is 0.5～1.5 hour, preferred 0.5 hour;
Preferably, the described ultrasonic time is 0.5～1.5 hour, preferred 1 hour;
Preferably, the temperature of described drying is 90～110 ℃, preferred 95～105 ℃, and further preferred 100 ℃;
Preferably, the time of described drying is 10～15h, preferred 10～13h, further preferred 12h;
Preferably, described roasting is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, and preferred 500～600 ℃, further preferred 500 ℃;
Preferably, described roasting time is 2～5h, preferred 3h;
Preferably, a kind of preparation method of vanadium cerium oxide catalyst comprises the steps:
(1 ' ' ' ' ') ammonium metavanadate is dissolved in oxalic acid solution;
(2 ' ' ' ' ') takes CeO
2Impregnated in the solution that step (1 ' ' ' ' ') obtains, stirred 30 minutes, ultrasonic 1 hour, 100 ℃ of oven dryings 12 hours, in Muffle furnace, under air atmosphere in 500 ℃ of roasting 3h;
(3 ' ' ' ' ') and repeating step (2 ' ' ' ' '), obtain V
2O
5The mass percent that accounts for described vanadium cerium oxide catalyst is 1～10% vanadium cerium oxide catalyst.
8. the preparation method of a vanadium cerium oxide catalyst as claimed in claim 1, is characterized in that, described method is sol-gal process, comprises the steps:
(1 ' ' ' ' ' ') under the oxalic acid existence condition, the mixed solution in preparation vanadium source and cerium source;
(2 ' ' ' ' ' ') slowly drips the organic acid aqueous solution in above-mentioned mixed solution, become transparent colloidal sol to mixed solution, and then stir and obtain gel, drying, roasting obtains vanadium cerium oxide catalyst.
9. method as claimed in claim 8, is characterized in that, described organic acid is selected from the mixture of any one or at least two kinds in citric acid, adipic acid or succinic acid, optimization citric acid;
Preferably, the temperature of described drying is 90～110 ℃, preferred 95～105 ℃, and further preferred 100 ℃;
Preferably, the time of described drying is 10～15h, preferred 10～13h, further preferred 12h;
Preferably, described roasting is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, and preferred 500～600 ℃, further preferred 500 ℃;
Preferably, described roasting time is 2～5h, preferred 3h;
Preferably, a kind of preparation method of vanadium cerium oxide catalyst comprises the steps:
(1 ' ' ' ' ' ' ') under the oxalic acid existence condition, the mixed solution of preparation ammonium metavanadate and cerous nitrate;
(2 ' ' ' ' ' ' ') in the situation that stir, slowly drip the lemon aqueous acid in above-mentioned mixed solution, become transparent colloidal sol to mixed solution, then stir and obtain gel, 100 ℃ of oven dryings 12 hours, in Muffle furnace, in 500 ℃ of roasting 3h, obtain vanadium cerium oxide catalyst under air atmosphere.
10. the purposes of a vanadium cerium oxide catalyst as claimed in claim 1, is characterized in that, described vanadium cerium oxide catalyst is used for catalyzing and reducing nitrogen oxides.
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| CN110354839A (en) * | 2019-08-20 | 2019-10-22 | 北京晨晰环保工程有限公司 | A kind of cerium based composite metal oxidate nanometer floral material and the preparation method and application thereof |
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