CN109999825A - It is a kind of width window denitration without vanadium rare-earth base catalyst and preparation method thereof - Google Patents
It is a kind of width window denitration without vanadium rare-earth base catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of wide window denitrations without vanadium rare-earth base catalyst and preparation method thereof, in CeO2‑WO3‑TiO2On the basis of catalyst, by introducing chitosan, La2O3It is modified jointly with CuO, it was found that the use of chitosan, La2O3Synergistic effect between CuO and the oxide of Ce, the activity of catalyst when improving low temperature, medium temperature, high temperature, has widened the use temperature range of catalyst.Part TiO is replaced by introducing viscosity2, high temperature section catalyst activity is further increased, the ceiling temperature of catalyst activity window has been widened.
Description
Technical field
The present invention relates to a kind of denitrating catalysts more particularly to a kind of wide window denitration without vanadium rare-earth base catalyst and its system
Preparation Method.
Background technique
There are a large amount of industrial combustion boilers, including about 540,000 Industrial Boilers and nearly 200,000 Industrial Stoves (to burn in China
Knot machine, cement rotary kiln etc., glass furnace), biomass boiler, garbage burning boiler, fluidized bed furnace, NOxDischarge amount accounts for about NOx
The 30% of total release.Since the type of burning boiler is different, operating condition is changed greatly, and load adjustment is frequent, flue gas emission cigarette
Temperature degree is between 200~600 DEG C.Currently, the NH of industrial applications3SCR catalyst, mainly V2O5-TiO2Or V2O5-WO3
(MoO3)-TiO2, active window is 300-420 DEG C, so often will appear flue-gas temperature beyond catalyst effective active range
The case where.Although existing research has shown that the catalytic component based on vanadium in the presence of the SCR for widening active window, vanadium itself are violent in toxicity
The shortcomings that matter, is difficult to overcome, it is necessary to increase the relevant control measure of vanadium to prevent pollution of the vanadium in catalyst to environment, as a result,
Lead to cost increase.
China is the reserves of rare earth big country, especially light rare earth compared with horn of plenty, and the application for developing light rare earth helps to solve
Rare earth resources utilize unbalance problem.It is existing research shows that rare earth oxide is able to carry out SCR denitration reaction, applicant is based on
This, independent research is without vanadium rare earth based denitration catalyst (CN201510590915.7) and in multiple projects in early-stage study
It realizes industrial application, but finds that rare earth based denitration catalyst low temperature (200 DEG C~300 DEG C) denitration performance is compared in practice process
The performance of its medium temperature (300 DEG C~550 DEG C) denitration has considerable degree of decline, and high temperature (450~550 DEG C) denitration can newly be compared
There is the decline of lower degree with medium temperature (350 DEG C~450 DEG C) denitration performance, since flue-gas temperature often converts in practical application,
So that catalyst not uses at optimum conditions, so that denitration effect is unstable.Therefore, it is necessary to one kind in wide temperature range
Inside can also have superperformance without vanadium rare-earth base catalyst.
The formula and preparation method that there is catalyst the key of good catalyst effect to be catalyst, in applicant's early period
On the basis of work, by the adjustment to catalyst formulation and preparation method, obtain with good result without vanadium rare-earth base
Wide window denitrating catalyst.
Summary of the invention
The technical problems to be solved by the invention be provide it is a kind of with good denitration efficiency wide window (220 DEG C~
580 DEG C) SCR denitration and preparation method thereof, the catalyst is mainly in CeO2-WO3-TiO2Base catalyst on adopt
With a certain amount of chitosan, La2O3It is modified with CuO, finds use, the La of chitosan2O3With CuO and CeO2Between collaboration
Effect, so that catalyst performance has been under solving no vanadium rare-earth base catalyst catalytic performance decline being serious at low temperature and high temperature
The problem of decline.Further, the present invention has found that the introducing of clay can further increase by being studied addition clay
Denitrating catalyst widens the catalyst activity window temperature upper limit in the performance of high temperature section.
The present invention provide technical solution it is as follows: it is a kind of width window denitration without vanadium rare-earth base catalyst, formula includes: 70-100
Mass parts titanium dioxide, 100 mass parts deionizations, 10-20 mass parts chitosan, 8-10 mass parts cerium oxalate, 5-10 mass parts
Clay, 1-5 mass parts ammonium metatungstate, 2-4 mass parts lanthanum oxalate, 0.2-1 mass parts citric acid, 0.1-0.5 mass parts copper chloride,
0.1-0.5 mass parts dodecyl sodium sulfate, 0.1-0.5 mass parts ammonium hydroxide.
Specific preparation process is as follows:
S1,100 mass parts deionized waters are injected into reaction kettle, opens stirring, temperature control after water temperature reaches 60-70 DEG C, is added
0.1-0.5 mass parts ammonium hydroxide stirs evenly；At such a temperature, and under agitation the 0.2-1 mass parts lemon into reaction kettle
Acid, 10-20 mass parts chitosan stir evenly；Sequentially add 1-5 mass parts ammonium metatungstate, 8-10 mass parts cerium oxalate, 2-4
Mass parts lanthanum oxalate, 0.1-0.5 mass parts copper chloride, stirs evenly；Add 0.1-0.5 mass parts dodecyl sodium sulfate,
50-70 mass parts titanium dioxide, stirs evenly；5-10 mass parts clay is added to stir evenly；Add 20-50 mass parts two
Titanium oxide stirs evenly, the slurry stirred evenly；
S2, reaction kettle stop stirring and heating, carry out aging to slurry；
S3, by the slurry after aging, continuous heating stirring makes liquid evaporation in evaporation tank, until slurry agglomerates, surface is opened
It splits, obtains dry agglomeration slurry；
S4, above-mentioned agglomeration slurry is packed into Muffle furnace and is calcined by temperature programming；Calcined agglomeration is starched again
Material carries out wet grinding grinding flour, finally dries, pulverizes, obtains wide window denitration without vanadium rare earth catalyst.
Further, in step S2 aging specific steps are as follows: natural aging 0.5-5 hours in a kettle.
Further, the condition of the temperature programming in step S4 are as follows: be warming up to 120 DEG C at room temperature, keep the temperature 0.5-5h；It rises again
Temperature keeps the temperature 1-6h to 380 DEG C；It is warming up to 620 DEG C again, keeps the temperature 1-6h；Then, cooled to room temperature.
Further, the condition of the wet grinding grinding in step S4 are as follows: time 0.5-2h reaches the powder diameter obtained
1.5 μm of D50 <, 3 μm of D90 <.
Further, the condition of the drying in step S4 are as follows: temperature is 100-105 DEG C, time 12-24h, until powder moisture
Less than 1%.
Further, the condition pulverized in step S4 are as follows: the powder of drying agglomeration is pulverized by disk crusher
Last shape.
The technical effect of the application are as follows:
(1) present invention obtains good catalyst effect by the research to catalyst formulation, is centainly contained by addition
Chitosan, the La of amount2O3With CuO to CeO2-WO3-TiO2Base catalyst be modified, improve catalyst low temperature and high temperature
Denitration performance.
(2) present invention further improves catalyst effect by the research to catalyst preparation step, is replaced with clay
Part TiO2, catalyst high temperature denitration performance is further improved, active window temperature upper limit is widened.
Specific embodiment
The specific embodiment of the invention is described below with reference to embodiment:
Embodiment 1
100 mass parts deionized waters are injected into reaction kettle, stirring, temperature control is opened after water temperature and, up to after 65 DEG C, 0.3g ammonia is added
Water stirs evenly；At such a temperature, and under agitation the 0.8g citric acid into reaction kettle, 10g chitosan stir evenly；Again
3g ammonium metatungstate, 9g cerium oxalate, 3g lanthanum oxalate are sequentially added, 0.3g copper chloride stirs evenly；Add 0.3g dodecyl sulphur
Sour sodium, 60g titanium dioxide, stir evenly；8g clay is added to stir evenly；It adds 30g titanium dioxide to stir evenly, obtain
The slurry stirred evenly；
Natural aging 3 hours in a kettle；
By the slurry after aging, continuous heating stirring makes liquid evaporation in evaporation tank, until slurry agglomerates, face checking,
Obtain dry agglomeration slurry；
Above-mentioned agglomeration slurry is packed into Muffle furnace, is warming up to 120 DEG C at room temperature, keeps the temperature 0.5-5h；It is warming up to 380 again
DEG C, keep the temperature 1-6h；It is warming up to 620 DEG C again, keeps the temperature 1-6h；Then, cooled to room temperature；Again by calcined agglomeration slurry into
Row wet grinding grinding flour grinds 1h, so that the powder diameter obtained is reached 1.5 μm of D50 <, 3 μm of D90 <, is finally in temperature
Dry 18h at 105 DEG C, to powder moisture less than 1%, the powder of drying agglomeration is ground into powder by disk crusher,
Low-temperature denitration is obtained without vanadium rare earth catalyst.
Embodiment 2
100 mass parts deionized waters are injected into reaction kettle, stirring, temperature control is opened after water temperature and, up to after 65 DEG C, 0.3g ammonia is added
Water stirs evenly；At such a temperature, and under agitation the 0.8g citric acid into reaction kettle, 20g chitosan stir evenly；Again
3g ammonium metatungstate, 9g cerium oxalate, 2g lanthanum oxalate are sequentially added, 0.1g copper chloride stirs evenly；Add 0.3g dodecyl sulphur
Sour sodium, 60g titanium dioxide, stir evenly；8g clay is added to stir evenly；It adds 30g titanium dioxide to stir evenly, obtain
The slurry stirred evenly；
Other steps are same as Example 1.
Embodiment 3
100 mass parts deionized waters are injected into reaction kettle, stirring, temperature control is opened after water temperature and, up to after 65 DEG C, 0.3g ammonia is added
Water stirs evenly；At such a temperature, and under agitation the 0.8g citric acid into reaction kettle, 10g chitosan stir evenly；Again
3g ammonium metatungstate, 9g cerium oxalate, 4g lanthanum oxalate are sequentially added, 0.5g copper chloride stirs evenly；Add 0.3g dodecyl sulphur
Sour sodium, 60g titanium dioxide, stir evenly；8g clay is added to stir evenly；It adds 30g titanium dioxide to stir evenly, obtain
The slurry stirred evenly；
Other steps are same as Example 1.
Comparative example 1
Difference from Example 1 is to be not added with chitosan, lanthanum oxalate, copper chloride, and other conditions are identical.
Comparative example 2
Difference from Example 1 is to be not added with lanthanum oxalate, copper chloride, and other conditions are identical.
Comparative example 3
Difference from Example 1 is to be not added with chitosan, copper chloride, and other conditions are identical.
Comparative example 4
Difference from Example 1 is to be not added with chitosan, lanthanum oxalate, and other conditions are identical.
Comparative example 5
Difference from Example 1 is to be not added with chitosan, and other conditions are identical.
Comparative example 6
Difference from Example 1 is to be not added with lanthanum oxalate, and other conditions are identical.
Comparative example 7
Difference from Example 1 is being not added with copper chloride, and other conditions are identical.
Comparative example 8
Difference from Example 1 is clay replacing with TiO2, other conditions are identical.
Catalytic effect is investigated
The powder catalyst of embodiment and comparative example preparation is subjected to tabletting, is crushed and then is sieved acquisition 40- again
The catalyst of the particle of 60 mesh, the weighing above-mentioned beaded catalyst of 1g mixed with quartz sand reach 1mL be put into fixed bed 250
DEG C, 350 DEG C, 500 DEG C of temperature carry out SCR denitration reaction investigation.Although the present invention is the other reaction of laboratory level, can be anti-
The modified trend generated of base catalyst is coped with, provides guidance foundation for experiment is further amplified.
The group of reaction mixture gas becomes (volumetric concentration): the concentration of NO is 500ppm, NH3Concentration be 500ppm, SO2's
Concentration is 300ppm, O2Concentration be 5%, remaining is N2.Volume space velocity is 200000h-1。
There are uncertain fluctuations for catalytic effect of the catalyst before reaching stability, after reaching stable, catalysis
Agent effect is then highly stable within the quite a while, until causing catalytic performance to decline since level of deactivation is aggravated.This hair
Data when the bright conversion ratio by the 3h carried out in reaction acquisition NO is to guarantee that measured data are to stablize.Pass through monitor
Device measures the NO of reactor outlet, can obtain the conversion ratio of NO, the conversion ratio of NO reflects the denitration activity of catalyst.
In order to investigate catalyst activity window, after the present invention makes catalyst runs 3h reach stable with catalyst at 200 DEG C,
Reaction temperature is promoted for interval with 5 DEG C, is catalyst activity window in the temperature that the conversion ratio of NO meets or exceeds 95% for the first time
Lower limit temperature, since catalyst activity curve is similar parabolic shape, the conversion ratio for being continuously heating to NO declines for the first time
Temperature extremely or lower than 95% is catalyst activity window upper limit temperature.Thereby, it is possible to reflect the active window width of catalyst.
See Table 1 for details for catalytic result
A reaction temperature is 250 DEG C；B reaction temperature is 350 DEG C；C reaction temperature is 500 DEG C；
Comparative example 1 is the catalyst of the applicant's early-stage study: CeO2-WO3-TiO2, the basis as this research is urged
Agent.The conversion ratio of NO of catalyst under conditions of 250 DEG C is to reach 95%, the conversion of NO under conditions of 380 DEG C
Rate is more than 99%, and the conversion ratio of NO under conditions of 500 DEG C is 98% or more.Usual denitrating catalyst activity curve is similar
Parabolic shape, until reaching lower window edge temperature, catalyst activity before catalyst reaches Process window lower limit temperature
Increase rapidly, once during reaction temperature enters catalyst activity window, then slowly growth is up to parallel for catalyst activity, then
Slowly decline, when reaction temperature is more than catalyst activity window upper limit, catalyst activity then declines significantly.Generally, it is considered that NO with
NH3When being reacted, SO2Also due to oxidation generates SO3, but NO reduction reaction carry out it is more sensitive to temperature, so improve temperature
Degree is conducive to the progress of SCR denitration, but the lasting raising of temperature can impact the structure of catalyst, therefore, not temperature
Higher more advantageous to SCR denitration, therefore, for catalyst, there are reactivity windows.The base catalyst is in middle height
The conversion ratio with good NO of temperature section, but cause catalyst activity to reduce more bright due to the reduction of temperature in low-temperature zone
It is aobvious, and the activity of high temperature section also occurs reducing relative to middle-temperature section.Therefore, it is necessary to improve catalyst with can
It is enough that also there is better catalytic performance in low-temperature zone, and widen its active window.
Comparative example 2-4 is respectively that chitosan, La are used alone on the basis of comparative example 12O3Or CuO is modified.For
The modification of chitosan in comparative example 2, the addition of usual chitosan can be improved the dispersibility of active component, and in calcination process
Middle chitosan before decomposition, in decomposable process, after even decomposing may remaining carbon hinder the reunion of active component, after decomposition
Possible remaining carbon also produces influence to the valence state of active component.It can be seen that the addition of chitosan from the result of comparative example 2
So that catalyst all increases in the activity of low high temperature, this may with the raising of catalyst dispersity and reduce catalyst
Agglomeration is related.But the modification of chitosan fails to widen the active window of catalyst.For La in comparative example 32O3Modification,
In general, La2O3It keeps auxiliary agent to use as the structure in catalyst, is able to maintain the structure and valence state of catalyst activity component.From right
The result of ratio 3, which can be seen that, is added La2O3Afterwards, the activity of catalyst low-temperature zone is substantially reduced, and middle-temperature section activity has slightly
It reduces, may show the oxide of active component Ce by part La with catalyst2O3Instead of related, and catalyst is in high temperature section
Performance but only slightly decline, may be with La2O3Valence state and structure to the oxide of Ce have good holding related.
La2O3The upper limit of catalyst activity window has been widened, but has also improved the lower limit of catalyst activity window simultaneously.For comparative example 4
The modification of middle CuO, usual CuO itself can realize SCR reaction as catalyst at low temperature, but activity decline is aobvious at high temperature
It writes, the introducing of CuO also will affect the valence state of the oxide of Ce.The addition that can be seen that CuO from the result of comparative example 4 significantly mentions
High denitration activity of the catalyst in low temperature, also has a little activity to be promoted, but apparent activity decline occurs in high temperature section in medium temperature.
CuO has widened the lower limit of catalyst activity window, but also reduces the upper limit of catalyst activity window simultaneously.
According to above-mentioned experimental result, the applicant attempts to introduce chitosan, La2O3Or two kinds of elements carry out catalyst in CuO
Performance.Comparative example 5 introduces La2O3It is modified with CuO, the conversion ratio of the NO of low high temperature is being introduced separately into La2O3
Or between the catalyst of CuO, the high conversion rate of NO when low medium temperature is in being not introduced into La2O3With the base catalyst of CuO, when high temperature
NO conversion ratio lower than being not introduced into La2O3With the base catalyst of CuO, the window temperature of catalyst is in bound relative to base
Plinth catalyst is widened, but expanded width is both less than introduced separately into La2O3Or the catalyst of CuO.It shows La2O3Change with CuO
Interaction between property agent is smaller, may more play respective modifying function.Comparative example 6 introduce chitosan and CuO into
Row is modified, and the high conversion rate of NO when low temperature in the catalyst for being introduced separately into chitosan and CuO and is not introduced into chitosan and CuO
Base catalyst, the conversion ratio of NO is being introduced separately between chitosan and the catalyst of CuO when medium temperature, higher than being not introduced into shell
The base catalyst of glycan and CuO, the conversion ratio of NO is being introduced separately between chitosan and the catalyst of CuO when high temperature, with
The base catalyst for being not introduced into chitosan and CuO maintains an equal level, which further widens.Chitosan and
CuO modifying agent further increases the conversion ratio of NO when catalyst low temperature, may use due to chitosan and CuO
Introducing causes the oxide of catalyst surface Ce and CuO that can further disperse, and produces interaction.Comparative example 7 introduces
Chitosan and La2O3It is modified, the conversion ratio of the NO of low temperature is being introduced separately into chitosan and La2O3Catalyst between,
Lower than being not introduced into chitosan and La2O3Base catalyst, the conversion ratio of the NO of medium temperature is being introduced separately into chitosan and La2O3
Catalyst between, higher than being not introduced into chitosan and La2O3Base catalyst, the high conversion rate of high temperature NO is in being introduced separately into
Chitosan and La2O3Catalyst and be not introduced into chitosan and La2O3Base catalyst, catalyst activity window temperature is not
It is able to achieve and further widens.Chitosan and La2O3Modifying agent further increases the conversion ratio of NO when catalyst low temperature,
It may use due to chitosan and La2O3Introducing lead to the oxide and La of catalyst surface Ce2O3Can further it divide
It dissipates, and produces interaction.
It is analyzed according to above content, so that the case where catalyst performance can further increase occurs all to draw with chitosan
Enter it is related, may be due to chitosan peptizaiton, prevent agglomeration and may remaining carbon effect.Then, Shen
It asks someone chitosan, La further2O3It is collectively incorporated into catalyst with CuO to be modified, embodiment 1-3 shows that being collectively incorporated into shell gathers
Sugar, La2O3It, may remaining carbon, La when with CuO2O3Unexpected synergistic effect has occurred with the oxide of CuO and Ce,
Obvious further promotion is all obtained in the conversion ratio of the NO of low middle high three temperature sections, the bound of activation window is obvious
Further expand.It may be to improve La in catalyst surface2O3On the basis of the dispersibility of the oxide of CuO and Ce,
La2O3Interaction is more prone to produce between CuO and the oxide of Ce, possible remaining carbon and CuO jointly can be to the oxygen of Ce
The valence state of compound has an impact, may remaining carbon and La2O3Influence is produced on the holding of catalyst structure jointly, and then is made
The synergistic effect of each component can preferably be played in low high temperature by obtaining catalyst, improved catalyst performance comprehensively and widened
The active window of catalyst.The collaboration that modification may promote favorable factor jointly of above-mentioned three kinds of substances improves, and has converted not
Therefore there is the General Promotion of catalyst performance in sharp factor.Above-mentioned experimental study shows that embodiment 1-3 can be for good
The wide window of good catalytic effect provides meaningful guidance without vanadium rare earth based denitration catalyst.
On the basis of investigating catalyst formulation, applicant has also investigated influence of the addition to catalyst performance of clay,
By comparative example 8 as can be seen that the introducing of clay does not generate materially affect to the conversion ratio of the NO of low medium temperature, and make high temperature NO
Conversion ratio promoted, and catalyst activity window upper limit is widened, may be to sticky related, viscosity of clay
It is advantageously possible for catalyst and keeps structure temperature at high temperature.It provides guidance further to widen catalyst activity window.
Many other changes and remodeling can be made by not departing from the spirit and scope of the present invention.It should be appreciated that the present invention is not
It is limited to specific embodiment, the scope of the present invention is defined by the following claims.
Claims (7)
1. a kind of width window denitration is without vanadium rare-earth base catalyst, which is characterized in that
Formula includes: 70-100 mass parts titanium dioxide, 100 mass parts deionizations, 10-20 mass parts chitosan, 8-10 mass
Part cerium oxalate, 5-10 mass parts clay, 1-5 mass parts ammonium metatungstate, 2-4 mass parts lanthanum oxalate, 0.2-1 mass parts citric acid,
0.1-0.5 mass parts copper chloride, 0.1-0.5 mass parts dodecyl sodium sulfate, 0.1-0.5 mass parts ammonium hydroxide.
2. a kind of preparation method of the width window denitration without vanadium rare-earth base catalyst, which is characterized in that
It is prepared by following steps:
S1,100 mass parts deionized waters are injected into reaction kettle, opens stirring, temperature control after water temperature reaches 60-70 DEG C, 0.1- is added
0.5 mass parts ammonium hydroxide stirs evenly；At such a temperature, and under agitation the 0.2-1 mass parts citric acid into reaction kettle,
10-20 mass parts chitosan stirs evenly；Sequentially add 1-5 mass parts ammonium metatungstate, 8-10 mass parts cerium oxalate, 2-4 matter
Part lanthanum oxalate is measured, 0.1-0.5 mass parts copper chloride stirs evenly；Add 0.1-0.5 mass parts dodecyl sodium sulfate, 50-
70 mass parts titanium dioxide, stir evenly；5-10 mass parts clay is added to stir evenly；Add 20-50 mass parts dioxy
Change titanium to stir evenly, the slurry stirred evenly；
S2, reaction kettle stop stirring and heating, carry out aging to slurry；
S3, by the slurry after aging, continuous heating stirring makes liquid evaporation in evaporation tank, until slurry agglomerates, face checking,
Obtain dry agglomeration slurry；
S4, above-mentioned agglomeration slurry is packed into Muffle furnace and is calcined by temperature programming；Again by calcined agglomeration slurry into
Row wet grinding grinding flour, finally dries, pulverizes, and obtains wide window denitration without vanadium rare earth catalyst.
3. preparation method of the width window denitration without vanadium rare-earth base catalyst according to claim 2, which is characterized in that step
The specific steps of aging in S2 are as follows: natural aging 0.5-5 hours in a kettle.
4. preparation method of the width window denitration without vanadium rare-earth base catalyst according to claim 2, which is characterized in that step
The condition of temperature programming in S4 are as follows: be warming up to 120 DEG C at room temperature, keep the temperature 0.5-5h；It is warming up to 380 DEG C again, keeps the temperature 1-6h；
It is warming up to 620 DEG C again, keeps the temperature 1-6h；Then, cooled to room temperature.
5. preparation method of the width window denitration without vanadium rare-earth base catalyst according to claim 2, which is characterized in that step
The condition of wet grinding grinding in S4 are as follows: time 0.5-2h makes the powder diameter obtained reach 1.5 μm of D50 <, 3 μm of D90 <.
6. preparation method of the width window denitration without vanadium rare-earth base catalyst according to claim 2, which is characterized in that step
The condition of drying in S4 are as follows: temperature is 100-105 DEG C, time 12-24h, until powder moisture is less than 1%.
7. preparation method of the width window denitration without vanadium rare-earth base catalyst according to claim 2, which is characterized in that step
The condition pulverized in S4 are as follows: the powder of drying agglomeration is ground into powder by disk crusher.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479299A (en) * | 2019-09-06 | 2019-11-22 | 山东科技大学 | A kind of low temperature flue qi exhaustion denox catalyst and preparation method thereof |
| CN112337475A (en) * | 2020-11-26 | 2021-02-09 | 西安科技大学 | Preparation method of rare earth-based SCR denitration catalyst used under high-arsenic condition |
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| CN112371109A (en) * | 2020-11-26 | 2021-02-19 | 西安建筑科技大学 | Preparation method of aged vanadium-based catalyst and rare earth regenerated denitration catalyst |
| CN112473688A (en) * | 2020-11-26 | 2021-03-12 | 西安科技大学 | Preparation method of rare earth chelated vanadium low-cost wide-temperature-window denitration catalyst |
| CN117839563A (en) * | 2024-03-07 | 2024-04-09 | 江苏泰禾金属工业有限公司 | Hollow spherical cuprous oxide soft template method drying and roasting preparation device |
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