CN104368329A - Cerium-niobium-zirconium composite oxide catalyst, preparation method and uses thereof - Google Patents
Cerium-niobium-zirconium composite oxide catalyst, preparation method and uses thereof Download PDFInfo
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- CN104368329A CN104368329A CN201410482869.4A CN201410482869A CN104368329A CN 104368329 A CN104368329 A CN 104368329A CN 201410482869 A CN201410482869 A CN 201410482869A CN 104368329 A CN104368329 A CN 104368329A
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Abstract
The present invention relates to a cerium-niobium-zirconium composite oxide catalyst, a preparation method and uses thereof. The catalyst has the following chemical composition: CeNbaZr2Ox, wherein a is 0-1.0 and does not include 0. The method comprises: (1) preparing a mixed aqueous solution comprising a cerium source and a zirconium source; (2) adding a niobium source aqueous solution and an excess urea precipitation agent to the mixed solution in the step (1) to completely precipitate cerium, niobium and zirconium; (3) carrying out suction filtration and washing on the obtained precipitated product to obtain the filter cake; and (4) drying and calcining the filter cake to obtain the cerium-niobium-zirconium composite oxide catalyst, wherein the catalyst has characteristics of excellent low-temperature activity, wide operation temperature window, high N2 selectivity and high NOx conversion rate, and can be used for the NH3-SCR reaction.
Description
Technical field
The present invention relates to a kind of cerium niobium zirconium mixed oxide catalyst, preparation method and its usage.
Background technology
NH
3selective Catalytic Reduction of NO
x(NH
3-SCR) be the exhaust gas from diesel vehicle NO of at present practical application
xcontrol technology, the catalyst of use mostly is V
2o
5-WO
3(MoO
3)/TiO
2.But this system remains in problems, such as operating temperature window narrows, TiO
2easy generation crystal transfer and active component V
2o
5there is bio-toxicity etc.Therefore efficient and eco-friendly NH is developed
3-SCR catalyst is used for exhaust gas from diesel vehicle NO
xcontrol has very important Significance for Environment.
CeO
2be often used as NH
3the auxiliary agent of-SCR catalyst or carrier, but easily sinter when high temperature, thus reduce active.Research finds to CeO
2the cerium Zirconium oxide stability that doping Zr is formed is apparently higher than CeO
2, there is certain NH simultaneously
3-SCR activity.But the temperature window of this oxide is narrower, and low temperature active is poor, in order to by NO in its practical application exhaust gas from diesel vehicle
xefficient removal, further must optimize and modification it.
Summary of the invention
For the problem of prior art, the object of the present invention is to provide a kind of cerium niobium zirconium mixed oxide catalyst, the low temperature active of described catalyst is excellent, operating temperature window is wide, N
2selective and NO
xconversion ratio is high.
In order to achieve the above object, present invention employs following technical scheme:
A kind of cerium niobium zirconium mixed oxide catalyst, described catalyst has following chemical composition: CeNb
azr
2o
x, wherein a is 0 ~ 1.0 and does not comprise 0, such as 0.1,0.15,0.2,0.25,0.3,0.35,0.4,0.45,0.5,0.55,0.6,0.65,0.7,0.75,0.8,0.85,0.9 or 0.95.
In catalyst of the present invention, the mol ratio of Ce and Zr is the mol ratio of 1:2, Nb and Ce is a.
The present invention by the oxide of composite niobium, to significantly improve low-temperature catalytic activity, the N of catalyst
2selective and NO
xconversion ratio.
Two of object of the present invention is the preparation method providing a kind of cerium niobium zirconium mixed oxide catalyst as above, and it is sluggish precipitation, comprises the following steps:
(1) mixed aqueous solution in cerium source and zirconium source is prepared;
(2) in the mixed solution of step (1), add the aqueous solution in niobium source and excessive urea precipitation agent, make cerium, niobium and zirconium precipitate completely;
(3) precipitated product obtained is carried out suction filtration and washing, obtain filter cake;
(4) filter cake is dried and roasting, obtain described cerium niobium zirconium mixed oxide catalyst.
Preferably, described cerium source is selected from the mixture of any one or at least two kinds in cerous chlorate, cerous nitrate, ammonium ceric nitrate or cerous sulfate, the mixture of described mixture such as cerous chlorate and cerous nitrate, the mixture of ammonium ceric nitrate and cerous sulfate, the mixture of cerous chlorate, cerous nitrate and ammonium ceric nitrate, the mixture of cerous sulfate, cerous chlorate, cerous nitrate and ammonium ceric nitrate, preferred cerous nitrate.
Preferably, described zirconium source is selected from the mixture of any one or at least two kinds in protochloride zirconium, zirconium nitrate or zirconium sulfate, the mixture of described mixture such as protochloride zirconium and zirconium nitrate, the mixture of protochloride zirconium and zirconium sulfate, the mixture of zirconium nitrate and zirconium sulfate, the mixture of protochloride zirconium, zirconium nitrate and zirconium sulfate, preferred zirconium nitrate.
Preferably, described niobium source is that columbium pentachloride is or/and niobium oxalate.
In sluggish precipitation, make precipitating reagent with urea, precipitation cerium source, zirconium source or niobium source, because urea likely exists the problem of not exclusively hydrolysis, therefore need to add excess urea.Urea is hydrolyzed, it is the process of a slow releasing hydroxide ion and carbanion, the slow hydrolysis of urea makes the reactant concentration around cerium ion in solution, zirconium ion or niobium ion that too large change can not occur, relative to other precipitating reagents as ammoniacal liquor and carbonic hydroammonium etc., precipitate with being more conducive to oxide precursor uniform particles.
Urea/(cerium source+niobium source+zirconium source) mol ratio is 8 ~ 12:1, such as 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/(cerium source+niobium source+zirconium source) mol ratio is larger, hydrolysis of urea and the ammonia amount that discharges is corresponding increases, and solution alkaline strengthens, and sedimentary growing amount also increases thereupon, and precipitation is more complete, and productive rate also increases gradually.Meanwhile, the degree of supersaturation of precipitation increases, 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 generating small size particle.When urea/(cerium source+niobium source+zirconium source) mol ratio is excessive, sedimentary recruitment is not remarkable, and precipitation is close to completely, and excessive concentration, waste raw material, increase cost.
Preferably, described precipitation is carried out under agitation, and described mixing time is 0.5 ~ 24h, such as 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 18h or 22h, preferably 1 ~ 15h, and example is preferred 12h further.
Preferably, the temperature of described precipitation is 60 ~ 100 DEG C, such as 65 DEG C, 72 DEG C, 75 DEG C, 78 DEG C, 83 DEG C, 88 DEG C, 92 DEG C, 95 DEG C, 98 DEG C, preferably 70 ~ 98 DEG C, preferably 90 DEG C further.
Preferably, the temperature of described oven dry is 80 ~ 120 DEG C, and drying time is 1 ~ 36h.
Preferably, described bake out temperature is 100 DEG C, and drying time is 12h.
The temperature of described oven dry is such as 84 DEG C, 88 DEG C, 92 DEG C, 96 DEG C, 100 DEG C, 104 DEG C, 108 DEG C, 112 DEG C or 116 DEG C.The time of described oven dry is such as 2h, 4h, 8h, 12h, 16h, 20h, 24h, 28h, 30h or 34h.
Preferably, described roasting is carried out in air atmosphere, and described sintering temperature is 400 ~ 600 DEG C, and roasting time is 2 ~ 5h.
Preferably, described sintering temperature is 500 DEG C, and roasting time is 3h.
Described sintering temperature is such as 420 DEG C, 440 DEG C, 460 DEG C, 480 DEG C, 500 DEG C, 520 DEG C, 540 DEG C, 560 DEG C or 580 DEG C.Described roasting time is such as 2.3h, 2.6h, 2.9h, 3.2h, 3.5h, 3.8h, 4.1h, 4.4h or 4.7h.
As the preferred technical solution of the present invention, one consists of CeNbZr
2the preparation method of the cerium niobium zirconium mixed oxide catalyst of Ox, it is sluggish precipitation, comprises the following steps:
(1) mixed aqueous solution of cerous nitrate and zirconium nitrate is prepared;
(2) in the mixed solution of step (1), the aqueous solution of columbium pentachloride and excessive urea precipitation agent is added, wherein, urea/(cerous nitrate+zirconium nitrate+columbium pentachloride) mol ratio is 10, at 90 DEG C, stir 12h, makes cerium, niobium and zirconium precipitate completely;
(3) precipitated product obtained is carried out suction filtration and washing extremely neutrality, obtain filter cake;
(4) filter cake 100 DEG C is dried 12h, then in air atmosphere, at 500 DEG C of roasting 3h, obtain described cerium niobium zirconium mixed oxide catalyst.
Adopt the CeNbZr that above-mentioned optimal technical scheme obtains
2ox catalyst in temperature under the condition of 200 ~ 450 DEG C, NO
xpurification efficiency is all more than 80%, and its low temperature active significantly improves, and operating temperature window is wide.
Three of object of the present invention is the purposes providing the catalysis of a kind of cerium niobium zirconium mixed oxide as above, and it is for NH
3-SCR reacts.
Compared with the prior art, the present invention has following beneficial effect:
(1) CeNbZr prepared by Nb is added
2o
xcatalyst low-temperature activity significantly improves, and simultaneous temperature window is also obviously widened;
(2) interpolation of Nb facilitates the interaction between Nb, Ce and Zr, catalyst redox process has been more prone to, thus improves NO
xremoval efficiency;
(3) take urea as the sluggish precipitation of precipitating reagent, preparation process is simple, with low cost, easily realizes industrialization.
Detailed description of the invention
Technical scheme of the present invention is further illustrated below by detailed description of the invention.
Embodiment 1
A certain amount of cerous nitrate and zirconium nitrate are dissolved in a certain amount of deionized water completely, then add the NbCl fully dissolved
5the aqueous solution and excessive urea precipitation agent, wherein urea/(cerous nitrate+zirconium nitrate+columbium pentachloride) mol ratio is 10:1, and it is 250ml that the most backward above mixed solution adds deionized water to cumulative volume, and stirs 12h continuously under 90 DEG C of water bath condition.After above-mentioned mixed liquor is cooled to room temperature, by deionized water, abundant suction filtration and washing extremely neutrality is carried out to gained sediment, then sediment is placed in 100 DEG C of oven for drying 12h, in air atmosphere, at 500 DEG C of roasting 3h, obtains consisting of CeNb finally
azr
2o
xcerium niobium zirconium mixed oxide catalyst, wherein a is 0.1.
Embodiment 2
All the other conditions with embodiment 1, except control a is except 0.5.
Embodiment 3
All the other conditions with embodiment 1, except control a is except 1.
Comparative example 1
All the other conditions with embodiment 1, except control a is except 0.
NH is carried out with the catalyst that embodiment 1-3 and comparative example 1 obtain
3selective Catalytic Reduction of NO
xthe investigation of reactivity.
Test condition simulated flue gas consists of, and the concentration of each component is NH
3=500ppm, NO=500ppm, O
2=5%, N
2for Balance Air, total flow=500mL/min, reaction velocity is 50,000h
-1, reaction temperature 150 ~ 500 DEG C.NO and NH
3and accessory substance N
2o, NO
2infrared-gas pond is all utilized to measure.Test result is as shown in the table:
Embodiment 4
A certain amount of cerous nitrate and zirconium nitrate are dissolved in a certain amount of deionized water completely, then add the NbCl fully dissolved
5the aqueous solution and excessive urea precipitation agent, wherein urea/(cerous nitrate+zirconium nitrate+columbium pentachloride) mol ratio is 8:1, and it is 250ml that the most backward above mixed solution adds deionized water to cumulative volume, and stirs 24h continuously under 60 DEG C of water bath condition.After above-mentioned mixed liquor is cooled to room temperature, by deionized water, abundant suction filtration and washing extremely neutrality is carried out to gained sediment, then sediment is placed in 80 DEG C of oven for drying 36h, in air atmosphere, at 400 DEG C of roasting 5h, obtains consisting of CeNb finally
azr
2o
xcerium niobium zirconium mixed oxide catalyst, wherein a is 1.0.
Embodiment 5
A certain amount of cerous nitrate and zirconium nitrate are dissolved in a certain amount of deionized water completely, then add the NbCl fully dissolved
5the aqueous solution and excessive urea precipitation agent, wherein urea/(cerous nitrate+zirconium nitrate+columbium pentachloride) mol ratio is 12:1, it is 250ml that the most backward above mixed solution adds deionized water to cumulative volume, and stirs 0.5h continuously under 100 DEG C of water bath condition.After above-mentioned mixed liquor is cooled to room temperature, by deionized water, abundant suction filtration and washing extremely neutrality is carried out to gained sediment, then sediment is placed in 120 DEG C of oven for drying 1h, in air atmosphere, at 600 DEG C of roasting 2h, obtains consisting of CeNb finally
azr
2o
xcerium niobium zirconium mixed oxide catalyst, wherein a is 1.0.
The catalyst obtained by embodiment 4 and 5 carries out NH
3selective Catalytic Reduction of NO
xthe investigation of reactivity.
Test condition simulated flue gas consists of, and the concentration of each component is NH
3=500ppm, NO=500ppm, O
2=5%, N
2for Balance Air, total flow=500mL/min, reaction velocity is 50,000h
-1, reaction temperature 150 ~ 500 DEG C.NO and NH
3and accessory substance N
2o, NO
2infrared-gas pond is all utilized to measure.Test result is as shown in the table:
Applicant states, 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 namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a cerium niobium zirconium mixed oxide catalyst, is characterized in that, described catalyst has following chemical composition: CeNb
azr
2o
x, wherein a is 0 ~ 1.0 and does not comprise 0.
2. a preparation method for cerium niobium zirconium mixed oxide catalyst as claimed in claim 1, is characterized in that, said method comprising the steps of:
(1) mixed aqueous solution in cerium source and zirconium source is prepared;
(2) in the mixed solution of step (1), add the aqueous solution in niobium source and excessive urea precipitation agent, make cerium, niobium and zirconium precipitate completely;
(3) precipitated product obtained is carried out suction filtration and washing, obtain filter cake;
(4) filter cake is dried and roasting, obtain described cerium niobium zirconium mixed 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 chlorate, cerous nitrate, ammonium ceric nitrate or cerous sulfate, preferred cerous nitrate;
Preferably, described zirconium source is selected from the mixture of any one or at least two kinds in protochloride zirconium, zirconium nitrate or zirconium sulfate, preferred zirconium nitrate;
Preferably, described niobium source is that columbium pentachloride is or/and niobium oxalate.
4. method as claimed in claim 2 or claim 3, it is characterized in that, urea/(cerium source+niobium source+zirconium source) mol ratio is 8 ~ 12:1, preferred 10:1.
5. the method as described in one of claim 2-4, is characterized in that, described precipitation is carried out under agitation, and described mixing time is 0.5 ~ 24h, preferably 1 ~ 15h, further preferred 12h;
Preferably, the temperature of described precipitation is 60 ~ 100 DEG C, preferably 70 ~ 98 DEG C, preferably 90 DEG C further.
6. the method as described in one of claim 2-5, is characterized in that, the temperature of described oven dry is 80 ~ 120 DEG C, and drying time is 1 ~ 36h;
Preferably, described bake out temperature is 100 DEG C, and drying time is 12h.
7. the method as described in one of claim 2-6, is characterized in that, described roasting is carried out in air atmosphere, and described sintering temperature is 400 ~ 600 DEG C, and roasting time is 2 ~ 5h.
8. the method as described in one of claim 2-7, is characterized in that, described sintering temperature is 500 DEG C, and roasting time is 3h.
9. the method as described in one of claim 2-8, is characterized in that, said method comprising the steps of:
(1) mixed aqueous solution of cerous nitrate and zirconium nitrate is prepared;
(2) in the mixed solution of step (1), the aqueous solution of columbium pentachloride and excessive urea precipitation agent is added, wherein, urea/(cerous nitrate+zirconium nitrate+columbium pentachloride) mol ratio is 10, at 90 DEG C, stir 12h, makes cerium, niobium and zirconium precipitate completely;
(3) precipitated product obtained is carried out suction filtration and washing extremely neutrality, obtain filter cake;
(4) filter cake 100 DEG C is dried 12h, then in air atmosphere, at 500 DEG C of roasting 3h, obtain cerium niobium zirconium mixed oxide catalyst.
10. a purposes for cerium niobium zirconium mixed oxide as claimed in claim 1 catalysis, it is characterized in that, it is for NH
3-SCR reacts.
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| CN115920876A (en) * | 2021-09-23 | 2023-04-07 | 重庆理工大学 | Preparation method and application of Nb-Ce-Zr denitration catalyst for SCR degradation |
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