CN103816889A - Cerium and titanium supported vanadium catalyst, and preparation method and use thereof - Google Patents
Cerium and titanium supported vanadium catalyst, and preparation method and use thereof Download PDFInfo
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- CN103816889A CN103816889A CN201410061289.8A CN201410061289A CN103816889A CN 103816889 A CN103816889 A CN 103816889A CN 201410061289 A CN201410061289 A CN 201410061289A CN 103816889 A CN103816889 A CN 103816889A
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Abstract
The invention discloses a cerium titanium supported vanadium catalyst. The catalyst is composed of a CeaTibOx support and a V2O5 active component supported on the support, a ratio of a:b is 0.5:1-2:1, and the weight of the V2O5 active component accounts for 1-10% (except 3%) of the weight of the CeaTibOx support. The NOx purifying efficiency of the catalyst is close to above 100% at 200-400DEG C, and the catalyst has a very good NH3-SCR activity, a greatly widened operation temperature window and an excellent SO2 poisoning resistance, and can be used for catalyzing the NOx purification in an NH3-SCR process.
Description
Technical field
The present invention relates to a kind of cerium titanium load vanadium catalyst, preparation method and its usage.
Background technology
At present with NH
3for reducing agent Selective Catalytic Reduction of NO
x(NH
3-SCR) catalyst system used mostly is V
2o
5-WO
3(MoO
3)/TiO
2and corresponding improved system, be widely used in the stationary source such as coal-burning power plant, Industrial Boiler denitrating flue gas purification process, there is high NO in higher temperature section
xpurification efficiency and anti-SO
2poisoning performance.But catalyst system exists operating temperature window is narrower, N when high temperature
2the a large amount of generation of O caused N
2the shortcoming such as selective decline, high high-temp stability is poor.The non-vanadium base NH of exploitation 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 poor, Fe, Ce base oxide class catalyst exist poor, the active shortcoming such as low of sulfur resistance.Therefore catalytic component based on vanadium is improved and meets application needs and be still NH
3the important research content in-SCR field.
Paper (Lian Zhihua, Liu Fudong, Shi Xiaoyan, He Hong, V that the applicant formerly delivers
2o
5/ CeTiO
xcatalyst is for low temperature NH
3sCR, the 7th national Environmental Chemistry conference ,-25 days on the 22nd September in 2013) a kind of cerium titanium load vanadium catalyst is disclosed, by V
2o
5/ CeTiO
xcatalyst is for low temperature NH
3selective Catalytic Reduction of NO
x.But it has only realized the low temperature performance excellent of catalyst, and not mentioned anti-SO
2poisoning performance.
Summary of the invention
For the problem of prior art, one of object of the present invention is to provide a kind of cerium titanium load vanadium catalyst, and described catalyst, except having excellent cryogenic property, also has excellent anti-SO
2poisoning performance.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of cerium titanium load vanadium catalyst, described catalyst is by Ce
ati
bo
xcarrier and load on the V on this carrier
2o
5active component composition, described a:b is 0.5:1～2:1, with Ce
ati
bo
xthe quality of carrier is 100wt% meter, described V
2o
5the quality of active component is 1～10wt% and does not comprise 3wt%, i.e. described V
2o
5the quality of active component is Ce
ati
bo
x1～10wt% of the quality of carrier and do not comprise 3wt%, for example 1.5wt%, 2wt%, 2.5wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt% or 9.5wt%.
Described a:b is for example 0.5:1,0.6:1,0.7:1,0.8:1,0.9:1,1:1,1.1:1,1.2:1,1.3:1,1.4:1,1.5:1,1.6:1,1.7:1,1.8:1 or 1.9:1.
Preferably, with Ce
ati
bo
xthe quality of carrier is 100wt% meter, described V
2o
5the quality of active component is 1～3wt% and does not comprise 3wt%, preferably 2.8wt%.
The present invention is by selecting Ce
ati
bo
xas the V of carrier and appropriate amount
2o
5as active component, and the chemical composition of carrier has been carried out to concrete restriction, made the catalyst obtaining except having excellent cryogenic property, operating temperature window is significantly widened, and also has excellent anti-SO
2poisoning performance.
Two of object of the present invention is to provide a kind of preparation method of cerium titanium load vanadium catalyst as above, and described method is infusion process, comprises the steps:
(1) prepare Ce
ati
bo
xcarrier;
(2), under oxalic acid condition, preparation ammonium metavanadate solution, then by Ce
ati
bo
xcarrier impregnation, in solution, stirs, then evaporate to dryness, and dry, roasting under air atmosphere, obtains cerium titanium load vanadium catalyst.
Preferably, adopt sluggish precipitation to prepare Ce
ati
bo
xcarrier, comprises the steps:
(1 ') preparation Ce source and Ti solution, mix Ce source solution and Ti solution, obtains mixed solution;
(2 ') adds excessive urea precipitating reagent in mixed solution, stir so that Ce and the co-precipitation of Ti ion are complete, and by the precipitated product suction filtration obtaining, washing, dry, roasting under air atmosphere, obtains described Ce
ati
bo
xcarrier.
Preferably, described Ce 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, preferably cerous nitrate.
Preferably, described Ti source is selected from the mixture of any one or at least two kinds in titanium tetrachloride, titanium sulfate or butyl titanate, preferably sulfuric acid titanium.
Preferably, urea/(Ce source+Ti 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, preferably 10:1.
Urea/(Ce source+Ti 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 completely, and productive rate is increase gradually also.Meanwhile, the degree of supersaturation of precipitation increases, and according to Chemical Kinetics theory, degree of supersaturation increases, and the generating rate of crystal grain is faster, makes the speed of growth of nucleation rate apparently higher than nucleus, is conducive to generate small size particle.Excessive when urea/(Ce source+Ti source) mol ratio, sedimentary recruitment is not remarkable, and precipitation is close to completely, and excessive concentration, wastes raw material, and increases cost.
Preferably, 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 ℃, preferably 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, preferably 9～13h, further preferred 12h.
Preferably, described dry temperature is 90～110 ℃, for example 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, preferably 95～105 ℃, further preferably 100 ℃.
Preferably, the described dry time 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, preferably 9～13h, 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 ℃, preferably 500～600 ℃, further preferably 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.
Exemplary Ce
ati
bo
xcarrier preparation method comprises the steps: using cerous nitrate as Ce source, using titanium sulfate as Ti source, urea, as precipitating reagent, is made mixed solution by titanium sulfate and cerous nitrate, then adds wherein excessive urea precipitating reagent, continuous stirring 12h under 90 ℃ of water bath condition, make Ce and the co-precipitation of Ti ion complete, sediment is carried out to suction filtration and washing, afterwards filter cake is put in to 100 ℃ of oven drying 12h, finally in Muffle furnace, under air atmosphere in 400～600 ℃ of roasting 3h, obtain Ce
ati
bo
xcarrier.
Preferably, step (2) stirs at room temperature carries out, and mixing time is 0.5～3h, for example 0.7h, 0.9h, 1.1h, 1.3h, 1.5h, 1.7h, 1.9h, 2.1h, 2.3h, 2.5h, 2.7h or 2.9h.
Preferably, the described evaporate to dryness of step (2) adopts Rotary Evaporators to realize, and the temperature of evaporate to dryness is 40～80 ℃, for example 42 ℃, 44 ℃, 47 ℃, 50 ℃, 53 ℃, 56 ℃, 59 ℃, 62 ℃, 65 ℃, 68 ℃, 71 ℃, 74 ℃, 77 ℃ or 79 ℃.
Preferably, the described dry temperature of step (2) is 90～110 ℃, for example 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 106 ℃, 107 ℃, 108 ℃ or 109 ℃, preferably 95～105 ℃, further preferably 100 ℃.
Preferably, the described dry time of step (2) is 8～15h, for example 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h or 14.5h, preferably 9～13h, further preferred 12h.
Preferably, the described roasting of step (2) is carried out in air atmosphere, and described sintering temperature is 400～600 ℃, and for example 430 ℃, 460 ℃, 510 ℃, 540 ℃, 570 ℃, 580 ℃ or 590 ℃, preferably 500～600 ℃, further preferably 500 ℃.
Preferably, the described roasting time of step (2) is 2～5h, for example 2.4h, 2.7h, 3.1h, 3.4h, 3.6h, 3.9h, 4.2h, 4.5h or 4.8h, preferably 3h.
The preparation method of exemplary a kind of cerium titanium load vanadium catalyst, comprises the steps:
(a) using cerous nitrate as Ce source, using titanium sulfate as Ti source, urea, as precipitating reagent, is made mixed solution by titanium sulfate and cerous nitrate, then adds wherein excessive urea precipitating reagent, continuous stirring 12h under 90 ℃ of water bath condition, make Ce and the co-precipitation of Ti ion complete, sediment is carried out to suction filtration and washing, afterwards filter cake is put in to 100 ℃ of oven drying 12h, finally in Muffle furnace, under air atmosphere in 400～600 ℃ of roasting 3h, obtain Ce
ati
bo
xcarrier;
(a), under oxalic acid existence condition, preparation ammonium metavanadate solution, then by Ce
ati
bo
xcarrier impregnation in solution, stirring at room temperature 1h, 60 ℃ through Rotary Evaporators evaporate to dryness, 100 ℃ of oven drying 12h, finally under air atmosphere at 500 ℃ of roasting 3h, obtain cerium titanium load vanadium catalyst.
Three of object of the present invention is to provide a kind of purposes of cerium titanium load vanadium catalyst as above, and described catalyst is for NH
3-SCR process catalytic purification NO
x.
Compared with the prior art, the present invention has following beneficial effect:
Catalyst of the present invention has the NO approaching more than 100% in the temperature range of 200～400 ℃
xpurification efficiency, has good NH
3-SCR activity, operating temperature window is significantly widened, and has excellent anti-SO
2poisoning performance.In addition, described catalyst floods after adopting the sluggish precipitation preparation take urea as precipitating reagent, simple, active component high degree of dispersion.
The specific embodiment
Further illustrate technical scheme of the present invention below by the specific embodiment.
Embodiment 1
A kind of cerium titanium load vanadium catalyst, described catalyst is by Ce
1ti
1o
xcarrier and load on the V on this carrier
2o
5active component composition, with Ce
1ti
1o
xthe quality of carrier is 100wt% meter, described V
2o
5the active component of active component is 2.8wt%.
The preparation method of catalyst as above comprises the steps:
(a) using cerous nitrate as Ce source, using titanium sulfate as Ti source, urea, as precipitating reagent, is made mixed solution by titanium sulfate and cerous nitrate, then adds wherein excessive urea precipitating reagent, continuous stirring 12h under 90 ℃ of water bath condition, make Ce and the co-precipitation of Ti ion complete, sediment is carried out to suction filtration and washing, afterwards filter cake is put in to 100 ℃ of oven drying 12h, finally in Muffle furnace, under air atmosphere in 400 ℃ of roasting 3h, obtain Ce
1ti
1o
xcarrier;
(a), under oxalic acid existence condition, preparation ammonium metavanadate solution, then by Ce
1ti
1o
xcarrier impregnation in solution, stirring at room temperature 1h, 60 ℃ through Rotary Evaporators evaporate to dryness, 100 ℃ of oven drying 12h, finally under air atmosphere at 500 ℃ of roasting 3h, obtain cerium titanium load vanadium catalyst.
Embodiment 2
Except step (1) sintering temperature is 500 ℃, all the other are identical with embodiment 1.
Embodiment 3
Except step (1) sintering temperature is 600 ℃, all the other are identical with embodiment 1.
Embodiment 4
A kind of cerium titanium load vanadium catalyst, described catalyst is by Ce
0.5ti
1o
xcarrier and load on the V on this carrier
2o
5active component composition, with Ce
0.5ti
1o
xthe quality of carrier is 100wt% meter, described V
2o
5the active component of active component is 1wt%.
The preparation method of catalyst as above comprises the steps:
(a) take cerous sulfate as Ce source, using butyl titanate as Ti source, urea, as precipitating reagent, is made mixed solution by titanium sulfate and cerous nitrate, then add wherein excessive urea precipitating reagent, urea/(Ce source+Ti source) mol ratio is 8:1, and continuous stirring 15h under 80 ℃ of water bath condition, makes Ce and the co-precipitation of Ti ion complete, sediment is carried out to suction filtration and washing, afterwards filter cake is put in to 90 ℃ of oven drying 15h, finally in Muffle furnace, under air atmosphere in 400 ℃ of roasting 5h, obtain Ce
0.5ti
1o
xcarrier;
(a), under oxalic acid existence condition, preparation ammonium metavanadate solution, then by Ce
0.5ti
1o
xcarrier impregnation in solution, stirring at room temperature 0.5h, 40 ℃ through Rotary Evaporators evaporate to dryness, 90 ℃ of oven drying 15h, finally under air atmosphere at 400 ℃ of roasting 5h, obtain cerium titanium load vanadium catalyst.
Embodiment 5
A kind of cerium titanium load vanadium catalyst, described catalyst is by Ce
2ti
1o
xcarrier and load on the V on this carrier
2o
5active component composition, with Ce
2ti
1o
xthe quality of carrier is 100wt% meter, described V
2o
5the active component of active component is 10wt%.
The preparation method of catalyst as above comprises the steps:
(a) using cerous nitrate as Ce source, using titanium tetrachloride as Ti source, urea, as precipitating reagent, is made mixed solution by titanium sulfate and cerous nitrate, then add wherein excessive urea precipitating reagent, urea/(Ce source+Ti source) mol ratio is 12:1, and continuous stirring 8h under 100 ℃ of water bath condition, makes Ce and the co-precipitation of Ti ion complete, sediment is carried out to suction filtration and washing, afterwards filter cake is put in to 110 ℃ of oven drying 8h, finally in Muffle furnace, under air atmosphere in 600 ℃ of roasting 2h, obtain Ce
2ti
1o
xcarrier;
(a), under oxalic acid existence condition, preparation ammonium metavanadate solution, then by Ce
2ti
1o
xcarrier impregnation in solution, stirring at room temperature 3h, 80 ℃ through Rotary Evaporators evaporate to dryness, 110 ℃ of oven drying 8h, finally under air atmosphere at 600 ℃ of roasting 2h, obtain cerium titanium load vanadium catalyst.
Embodiment 6
A kind of cerium titanium load vanadium catalyst, described catalyst is by Ce
0.8ti
1o
xcarrier and load on the V on this carrier
2o
5active component composition, with Ce
0.8ti
1o
xthe quality of carrier is 100wt% meter, described V
2o
5the active component of active component is 6wt%.
The preparation method of catalyst as above comprises the steps:
(a) using cerous nitrate as Ce source, using titanium sulfate as Ti source, urea, as precipitating reagent, is made mixed solution by titanium sulfate and cerous nitrate, then add wherein excessive urea precipitating reagent, urea/(Ce source+Ti source) mol ratio is 10:1, and continuous stirring 12h under 100 ℃ of water bath condition, makes Ce and the co-precipitation of Ti ion complete, sediment is carried out to suction filtration and washing, afterwards filter cake is put in to 100 ℃ of oven drying 12h, finally in Muffle furnace, under air atmosphere in 400 ℃ of roasting 3h, obtain Ce
0.8ti
1o
xcarrier;
(a), under oxalic acid existence condition, preparation ammonium metavanadate solution, then by Ce
0.8ti
1o
xcarrier impregnation in solution, stirring at room temperature 2h, 60 ℃ through Rotary Evaporators evaporate to dryness, 100 ℃ of oven drying 12h, finally under air atmosphere at 500 ℃ of roasting 3h, obtain cerium titanium load vanadium catalyst.
Comparative example 1
Preparing carrier is CeO
2, active component is V
2o
5catalyst.
Comparative example 2
Preparing carrier is TiO
2, active component is V
2o
5catalyst.
Get the catalyst that embodiment 1～4 and comparative example 1～2 prepare, catalyst volume 0.6mL, 40-60 order, puts into 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
2for Balance Air, total flow is 500mL/min, and reaction velocity is 50000h
-1.Test result is as shown in table 1.
Table 1
The anti-SO of table 2
2poisoning performance test
Applicant's statement, the present invention illustrates detailed method of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed method, does not mean that the present invention must rely on above-mentioned detailed method and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a cerium titanium load vanadium catalyst, is characterized in that, described catalyst is by Ce
ati
bo
xcarrier and load on the V on this carrier
2o
5active component composition, described a:b is 0.5:1～2:1, with Ce
ati
bo
xthe quality of carrier is 100wt% meter, described V
2o
5the quality of active component is 1～10wt% and does not comprise 3wt%.
2. catalyst as claimed in claim 1, is characterized in that, with Ce
ati
bo
xthe quality of carrier is 100wt% meter, described V
2o
5the quality of active component is 1～3wt% and does not comprise 3wt%, preferably 2.8wt%.
3. a preparation method for cerium titanium load vanadium catalyst as claimed in claim 1 or 2, is characterized in that, described method comprises the steps:
(1) prepare Ce
ati
bo
xcarrier;
(2), under oxalic acid condition, preparation ammonium metavanadate solution, then by Ce
ati
bo
xcarrier impregnation, in solution, stirs, then evaporate to dryness, and dry, roasting under air atmosphere, obtains cerium titanium load vanadium catalyst.
4. method as claimed in claim 3, is characterized in that, step (1) adopts sluggish precipitation to prepare Ce
ati
bo
xcarrier, comprises the steps:
(1 ') preparation Ce source and Ti solution, mix Ce source solution and Ti solution, obtains mixed solution;
(2 ') adds excessive urea precipitating reagent in mixed solution, stir so that Ce and the co-precipitation of Ti ion are complete, and by the precipitated product suction filtration obtaining, washing, dry, roasting under air atmosphere, obtains described Ce
ati
bo
xcarrier.
5. method as claimed in claim 4, is characterized in that, the described Ce of step (1 ') 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, preferably cerous nitrate;
Preferably, the described Ti of step (1 ') source is selected from the mixture of any one or at least two kinds in titanium tetrachloride, titanium sulfate or butyl titanate, preferably sulfuric acid titanium;
Preferably, urea/(Ce source+Ti source) mol ratio is 8～12:1, preferably 10:1.
6. the method as described in claim 4 or 5, is characterized in that, the described precipitation temperature of step (2 ') is 80～100 ℃, preferably 90 ℃;
Preferably, the time of the described precipitation of step (2 ') is 8～15h, preferably 9～13h, further preferred 12h;
Preferably, the described dry temperature of step (2 ') is 90～110 ℃, preferably 95～105 ℃, and further preferably 100 ℃;
Preferably, the described dry time of step (2 ') is 8～15h, preferably 9～13h, further preferred 12h;
Preferably, the described sintering temperature of step (2 ') is 400～600 ℃, preferably 500～600 ℃, and further preferably 500 ℃;
Preferably, the described roasting time of step (2 ') is 2～5h, preferably 3h.
7. the method as described in one of claim 3-6, is characterized in that, step (2) stirs at room temperature carries out, and mixing time is 0.5～3h, preferably 1h;
Preferably, the described evaporate to dryness of step (2) adopts Rotary Evaporators to realize, and the temperature of evaporate to dryness is 40～80 ℃, preferably 60 ℃;
Preferably, the described dry temperature of step (2) is 90～110 ℃, preferably 95～105 ℃, and further preferably 100 ℃;
Preferably, the described dry time of step (2) is 8～15h, preferably 9～13h, further preferred 12h.
8. the method as described in one of claim 3-7, is characterized in that, the described sintering temperature of step (2) is 400～600 ℃, preferably 500～600 ℃, and further preferably 500 ℃;
Preferably, the described roasting time of step (2) is 2～5h, preferably 3h.
9. the method as described in one of claim 3-8, is characterized in that, described method comprises the steps:
(a) using cerous nitrate as Ce source, using titanium sulfate as Ti source, urea, as precipitating reagent, is made mixed solution by titanium sulfate and cerous nitrate, then adds wherein excessive urea precipitating reagent, continuous stirring 12h under 90 ℃ of water bath condition, make Ce and the co-precipitation of Ti ion complete, sediment is carried out to suction filtration and washing, afterwards filter cake is put in to 100 ℃ of oven drying 12h, finally in Muffle furnace, under air atmosphere in 400～600 ℃ of roasting 3h, obtain Ce
ati
bo
xcarrier;
(b), under oxalic acid existence condition, preparation ammonium metavanadate solution, then by Ce
ati
bo
xcarrier impregnation in solution, stirring at room temperature 1h, 60 ℃ through Rotary Evaporators evaporate to dryness, 100 ℃ of oven drying 12h, finally under air atmosphere at 500 ℃ of roasting 3h, obtain cerium titanium load vanadium catalyst.
10. a purposes for cerium titanium load vanadium catalyst as claimed in claim 1 or 2, is characterized in that, described catalyst is for NH
3-SCR process catalytic purification NO
x.
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| CN105214642A (en) * | 2015-09-21 | 2016-01-06 | 安徽迪诺环保新材料科技有限公司 | A kind of preparation method of low-temperature SCR catalyst for denitrating flue gas raw material and application thereof |
| CN105688888A (en) * | 2016-01-14 | 2016-06-22 | 济南大学 | High-performance vanadium, cerium and titanium composite oxide catalyst for flue gas denitration and preparation method thereof |
| CN107670658A (en) * | 2017-11-09 | 2018-02-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Catalyst for chlorobenzene low-temperature catalytic burning 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 |
| CN108236944A (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 vanadium oxide catalyst and its application |
| CN110833827A (en) * | 2018-08-15 | 2020-02-25 | 南京理工大学 | High nitrogen selectivity vanadium-based oxide catalyst and preparation method thereof |
| CN115990524A (en) * | 2022-12-02 | 2023-04-21 | 中国科学院城市环境研究所 | Low-vanadium catalyst and preparation method and application thereof |
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| CN107670658A (en) * | 2017-11-09 | 2018-02-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Catalyst for chlorobenzene low-temperature catalytic burning and its preparation method and application |
| CN110833827A (en) * | 2018-08-15 | 2020-02-25 | 南京理工大学 | High nitrogen selectivity vanadium-based oxide catalyst and preparation method thereof |
| CN110833827B (en) * | 2018-08-15 | 2022-11-04 | 南京理工大学 | High nitrogen selectivity vanadium-based oxide catalyst and preparation method thereof |
| CN115990524A (en) * | 2022-12-02 | 2023-04-21 | 中国科学院城市环境研究所 | Low-vanadium catalyst and preparation method and application thereof |
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