CN102319560A - Preparation method of manganese titanium catalysts - Google Patents
Preparation method of manganese titanium catalysts Download PDFInfo
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- CN102319560A CN102319560A CN201110139794A CN201110139794A CN102319560A CN 102319560 A CN102319560 A CN 102319560A CN 201110139794 A CN201110139794 A CN 201110139794A CN 201110139794 A CN201110139794 A CN 201110139794A CN 102319560 A CN102319560 A CN 102319560A
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Abstract
The invention discloses a preparation method of manganese titanium catalysts. Manganous nitrate and titanium dioxide are used as ingredients to be added into deionized water, the ultrasonic treatment is carried out after the mixing and the stirring, and then, the manganese titanium catalysts are obtained through drying and roasting, wherein the manganese titanium catalysts use the titanium oxides as carriers and use manganese oxides as active ingredients. The ingredient resources are rich, in addition, the pretreatment is not needed, and the preparation process is simple. Researches show that the application of ultrasonic waves in the catalyst preparation process generates important influence on the MnOx dispersion, the catalyst surface acid and the denitration reaction activity.
Description
Technical field
The invention belongs to coal steam-electric plant smoke denitration technology field, particularly a kind of preparation method of manganese titanium catalyst.
Background technology
Contain a large amount of Lattice Oxygen among the MnOx, help the carrying out of oxidation-reduction reaction, make it in the low-temperature SCR reaction, have very big activity.Therefore, many in recent years researchers are devoted to the research as the low-temperature SCR catalyst active component with MnOx.At present, low temperature MnOx/TiO
2Catalyst mainly is divided three classes, and one type is the support type manganese-based catalyst, mainly contains MnOx/TiO
2, MnOx/Al
2O
3, MnOx/USY (ultrastable Y-type zeolite) MnOx/AC, MnOx/ACF etc.; One type is the non-loading type manganese-based catalyst, the oxide catalyst that contains manganese that promptly directly obtains through certain presoma; Also have the manganese-based catalyst of one type of bimetallic oxide, such catalyst has added another kind of metal oxide in Mn oxide, utilize the synergy of two kinds of metal oxides, and it is active to obtain low-temperature SCR.
Make a general survey of a large amount of about MnOx/TiO
2The research of catalyst, the preparation method is conventional infusion process mostly, a small amount of reported literature coprecipitation and sol-gal process.The tradition infusion process because mass transfer force is less, causes activity component load quantity less (generally being no more than 10wt.%) in the dip loading process, otherwise unbodied MnOx can be in the crystallization of carrier table, thereby reduces activity of such catalysts.In addition, traditional catalyst prepared specific area is also smaller, and the higher catalyst activity that causes of light-off temperature is lower; Detitanium-ore-type TiO in the catalyst of coprecipitation preparation
2Very unstable, as easy as rolling off a log generation crystal transition causes the heat endurance of catalyst relatively poor; Sol-gal process can improve the dispersion of MnOx, therefore can the more a large amount of active component of load, thus obtain the catalyst of greater activity, but the optimum activity temperature of this type catalyst higher (＞150 ℃), the denitration efficiency below 120 ℃ is less than 90%.Therefore, developing highly active catalyst system is the key that realizes the low-temperature SCR process.
In recent years, the physics of ultrasonic cavitation and chemical effect in catalyst preparation process to the catalyst microscopic property (as active material grain size, catalyst aperture distribute and active component in the catalyst surface dispersity etc.) influence cause that people greatly pay close attention to.Chinese scholars has been carried out many researchs in the process of immersion process for preparing catalyst, introducing ultrasonic field; Research shows; In the preparation process, use ultrasonic wave can promote reactive metal on catalyst, evenly to disperse, can increase the active component permeability active component is fully contacted with carrier, improve the configuration of surface of catalyst; Specific surface area of catalyst is increased, finally improve the catalyst reaction activity.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of manganese titanium catalyst; Manganese titanium catalyst through this method preparation not only possesses very strong low-temperature catalytic activity; And temperature window is wide, and stability is high, apparently higher than other preparation methods' catalyst.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following:
A kind of preparation method of manganese titanium catalyst is a raw material with manganese nitrate and titanium dioxide, adds in the deionized water; Mix and stir the back ultrasonic Treatment, promptly get the manganese titanium catalyst through dry, roasting again, wherein; Described manganese titanium catalyst is carrier with the titanyl compound, is active component with the oxide of manganese.
Wherein, the manganese nitrate quality accounts for 32.95% of titanium dioxide quality.Make that the quality that the oxide of manganese accounts for titanium dioxide is 10% in the manganese titanium catalyst that obtains after the roasting.
Wherein, described ultrasonic Treatment condition is 20～30kHz, 300～500W, and the processing time is 2～4h, preferred ultrasonic Treatment condition is 25kHz, 400W, the processing time is 2h.
Wherein, described drying condition is 100～120 ℃ of following dry 12～15h, preferred 110 ℃ of following dry 12h.
Wherein, described roasting condition is 250～500 ℃ of following roastings 2～4 hours.
Beneficial effect: the inventive method is introduced traditional immersion process for preparing MnOx/TiO with ultrasonic wave
2Adopt BET (Brunauer-Emmett-Teller specific area), XRD (X-ray diffraction), in situ FT-IR (In-situ Infrared), HRTEM characterization techniques such as (high-resolution-ration transmission electric-lens); And the activity rating that combines NO catalysis to eliminate; The use of system research ultrasonic wave in the preparation process is to the influence of microstructure, surface acid position and the NO catalytic activity of catalyst; And compare with traditional infusion process and sol-gal process, to have the higher low temperature active and the catalyst of heat endurance thereby optimize, for designing and developing economical and practical low-temperature SCR catalyst relevant basis reference is provided.The inventive method raw material sources are abundant, and need not to carry out preliminary treatment, and preparation technology is simple.
Description of drawings
Fig. 1 is the MnOx/TiO of the catalyst of distinct methods preparation
2The denitration performance comparison diagram.
Fig. 2 is carrier TiO
2XRD spectra with the catalyst of distinct methods preparation.
The HRTEM figure of two kinds of catalyst of Fig. 3.(1)Mn/TiO
2(UI，250℃，4h)；(2)％Mn/TiO
2(TI)。
The electron diffraction diagram of two kinds of catalyst of Fig. 4.(1)Mn/TiO
2(UI，250℃，4h)；(2)％Mn/TiO
2(TI)。
Fig. 5 absorbs saturated NH for two types of catalyst of ultrasonic immersing method and conventional immersion process for preparing down at 120 ℃
3Infared spectrum.
The specific embodiment
Based on following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, process conditions and result thereof only are used to explain the present invention, and the present invention that should also can not limit in claims to be described in detail.
Embodiment 1:
With manganese nitrate (Mn (NO
3)
26H
2O) and TiO
2(Degussa P25) is raw material.At first add the 50ml deionized water, stir adding 2g TiO with the back at the 100ml beaker
2And then add the manganese nitrate of 0.659g (P25).After mix stirring mixture is placed in the supersonic generator,,, take out at last the gained powder is changed in the Muffle furnace at 250 ℃ of following roasting 3h again at 110 ℃ of dry 12h with the ultrasonic Treatment 2h of 25kHz, 400W.Gained catalyst note is made Mn/TiO
2(UI, 250 ℃, 2h) (Mn/TiO
2(UI, 250 ℃, 2h) in, 250 ℃ the expression sintering temperatures, 2h representes ultrasonic treatment time).
Embodiment 2:
With manganese nitrate (Mn (NO
3)
26H
2O) and TiO
2(Degussa P25) is raw material.At first add the 50ml deionized water, stir adding 2gTiO with the back at the 100ml beaker
2And then add the manganese nitrate of 0.659g (P25).After mix stirring mixture is placed in the supersonic generator,,, take out at last the gained powder is changed in the Muffle furnace at 250 ℃ of following roasting 3h again at 110 ℃ of dry 12h with the ultrasonic Treatment 4h of 25kHz, 400W.Gained catalyst note is made Mn/TiO
2(UI, 250 ℃, 4h) (Mn/TiO
2(UI, 250 ℃, 4h) in, 250 ℃ the expression sintering temperatures, 4h representes ultrasonic treatment time).
Embodiment 3:
With manganese nitrate (Mn (NO
3)
26H
2O) and TiO
2(Degussa P25) is raw material.At first add the 50ml deionized water, stir adding 2gTiO with the back at the 100ml beaker
2And then add the manganese nitrate of 0.659g (P25).After mix stirring mixture is placed in the supersonic generator,,, take out at last the gained powder is changed in the Muffle furnace at 500 ℃ of following roasting 3h again at 110 ℃ of dry 12h with the ultrasonic Treatment 2h of 25kHz, 400W.Gained catalyst note is made Mn/TiO
2(UI, 500 ℃, 2h).(Mn/TiO
2(UI, 500 ℃, 2h) in, 500 ℃ the expression sintering temperatures, 2h representes ultrasonic treatment time).
Embodiment 4:
In the 50ml deionized water, add 2g TiO
2(P25), add the manganese nitrate of 0.659g, replace ultrasonic wave with mechanical agitation, 20 ℃ are stirred down and are stirred to moisture under the 2h, 85 ℃ and evaporate basically, and 250 ℃ of following roasting 3h through 110 ℃ of dry 12h after, gained catalyst remember and make Mn/TiO
2(TI).
Embodiment 5:
The manganese nitrate of tetrabutyl titanate (1mol), ethanol (1mol), water (0.05-0.5mol), acetate (0.01-0.5mol) and 0.659g is at room temperature mixed, and solution is converted into vitreosol behind the vigorous stirring 30min.After at room temperature leaving standstill a few days, colloidal sol is converted into the grey black gel.Gel at 110 ℃ of dry 12h, is obtained porosu solid, 500 ℃ of roasting 3h, gained catalyst note is made Mn/TiO
2(SG).
Embodiment 6: the test of catalyst denitration activity
Test condition:
Said catalyst carries out the denitration test under fixed bed simulated flue gas condition: the denitrating catalyst after getting said modification, place the reaction tube isothermal region, and flue gas gets into reaction tube, in reaction tube, carries out selective-catalytic-reduction denitrified reaction through catalyst action.
Come simulated flue gas to form in the flue gas with the steel gas cylinder and comprise NO, O
2, N
2, NH
3, flue gas consists of volume fraction Φ (NO)=Φ (NH3)=0.08%, and Φ (O2)=5% is with N
2Be balance gas.Air speed is than nSV=2.4 * 10
4h
-1, total flue gas flow is 100ml/min.Each pipeline gas gets into reactor again after mass flowmenter (all flowmeters are all through the soap-foam flowmeter calibration) gets into the gas mixer mixed equilibrium.Adopt German Testo 330-2 LL flue gas analyzer measuring N O, NO
2, O
2Concentration.Calculate the NO removal efficiency in view of the above.In order to guarantee data stability and accuracy, each operating mode was stablized 30 minutes at least.
Test result:
Other low temperature manganese titanium catalysts provided by the invention; Be to adopt traditional infusion process, Prepared by Sol Gel Method, and the ultrasonic wave catalyst prepared not only possess very strong low-temperature catalyzed work; 120 ℃ of NO removal efficiencies reach nearly 100%; And temperature window is wide, and stability is high, apparently higher than the catalyst of prepared by other.Like Fig. 1.
Interpretation of result:
Shown in Figure 1 for adopting the MnOx/TiO of different preparation method's preparations
2Activity of such catalysts.Can find out obviously that more than 150 ℃, the NO removal efficiency that various preparation methods obtain is all near 100%, activity difference is little, and very big difference is arranged at low temperatures.Mn/TiO
2(UI) catalyst series denitration efficiency in the time of 80 ℃ can reach about 70% Mn/TiO
2(SG) also shown reactivity preferably, yet, Mn/TiO
2(TI) will reach that identical NO removal efficiency is temperature required will be more than 150 ℃.Along with the rising of reaction temperature, various catalyst activities strengthen rapidly, still, and Mn/TiO
2(SG) and Mn/TiO
2(UI) activity difference increases, two kinds of Mn/TiO
2(UI) removal efficiency of catalyst NO in the time of 120 ℃ is near 100%, and Mn/TiO
2(SG) catalyst n O removal efficiency is only about 85%.Clearly can find out, adopt the catalyst series of ultrasonic immersing method preparation to show stronger low-temperature reactivity (≤150 ℃).
In addition, we have also investigated the influence to catalyst activity of dip time and calcining heat.As shown in Figure 1, the differing greatly of the catalyst low-temperature activity that 250 ℃ of dippings 2h and 4h obtain, denitration efficiency has reached 65% during 80 ℃ of the latter; Along with the rising of reaction temperature, catalyst activity strengthens rapidly, and both activities difference diminishes.Under the equal dip time, along with the increase of calcining heat, the catalyst reaction activity change is little, has proved absolutely that the ultrasonic immersing time is bigger to the activity of such catalysts influence.
Embodiment 7: relevant characterization.
Catalyst B ET specific area and pore size determination carry out on the gold dust spectrum F-Sorb 3400 specific surface area analysis appearance of Beijing, and sample vacuumizes preliminary treatment 2h under 200 ℃, with N
2Be adsorbate, under-196 ℃, measure.
XRD-2 type X-ray diffraction analyzer, tube voltage 35kV, tube current 20mA are adopted in the analysis of catalyst phase structure; 0.02 °/s of step-length, X ray wavelength are 1.5406A, the Cu target; 2 θ/θ coupling continuous sweep, scanning angle is 10 °～70 °, catalyst sample needs fully to grind before test; Get an amount of powder filled also pressing on glass carrier, the about 1mm of sample powder thickness.
Adopt the microtexture of JEOL JEM-2100 high-resolution projection electron microscopy study catalyst.At first need carry out preliminary treatment to sample before the test: the sample that takes a morsel is immersed in the ethanol, drips to after stirring on the copper slide glass, and then 110 ℃ are dried to ethanol and evaporate fully.
With NH
3Molecule is made probe and is adopted Nicolet 5700 in-situ ft-ir appearance to obtain information such as catalyst surface acid position, active component dispersiveness, sweep limits 4000～400cm
-1, resolution ratio 4cm
-1, catalyst sample is pressed into thin slice.
Characterization result:
Characterization result is seen table 1 and Fig. 2～5.
The specific area of loaded catalyst all is higher than carrier, shows like table 1.In addition, the specific area of a series of catalyst that the ultrasonic wave immersion process for preparing obtains is all greater than conventional infusion process, wherein Mn/TiO
2(UI, 250 ℃, specific area 4h) is maximum, reaches 60.2m
2/ g, this makes the Mn element get into TiO because " ultrasonic cavitation " effect of in dipping process, being produced of ultrasonic wave spreads active component in the darker duct, top layer of carrier
2Lattice in, with TiO
2Between interact, and active component is evenly distributed, prepare the catalyst of high degree of dispersion high-specific surface area, this XRD and HTREM analysis result with hereinafter is consistent.Comparatively speaking, the Mn/TiO of Prepared by Sol Gel Method
2(SG) specific surface area of catalyst is maximum, is 64.2m
2/ g.Reason is that change in reaction conditions comparatively relaxes in the conversion process of sol-gel, and the reaction precursor body contacts more abundant in colloid, more helps the dispersion of metal oxide, thereby forms bigger specific area.The active testing result but shows Mn/TiO
2(UI, 250 ℃, activity 4h) is the highest, and the specific surface of this explanation catalyst is not unique decisive factor of activity of such catalysts.In addition, the ultrasonic wave dip time increases, and the dispersion that utilizes Mn oxide is more arranged, and therefore, the specific area of catalyst enlarges markedly.Calcining heat increases to 500 ℃, and too obvious variation does not take place specific surface area of catalyst, but the aperture significantly increases.In general, the ultrasonic wave dip time is bigger to the specific surface and the aperture influence of catalyst, and the influence of calcination time is less.
The texture property of table 1 catalyst and carrier
Fig. 2 has compared carrier TiO
2XRD spectra with the catalyst of distinct methods preparation.For TiO
2Carrier is 27.5,38.3,48.5,54.2,62.5,68.7,70.3,75.1 ° of diffraction maximums of locating to occur anatase crystal through analyzing at 2.For Mn/TiO
2(TI), carrier TiO
2Diffraction peak intensity obviously reduce, show TiO
2Degree of crystallization reduce, and MnO does not appear
XDiffraction maximum, explain that Mn oxide exists with dispersed or amorphous state.With Mn/TiO
2(TI) compare catalyst Mn/TiO
2(SG), Mn/TiO
2(UI, 250 ℃, 4h) and Mn/TiO
2(UI, 500 ℃, TiO 2h)
2Diffraction peak intensity obviously reduces, and MnO also do not occur
XDiffraction maximum, and TiO
2The angle of diffraction also slightly the skew.The The above results explanation, Mn has dispersion preferably at carrier surface, and the interpolation of Mn oxide has reduced carrier TiO
2Degree of crystallinity, possibly exist comparatively strong interaction between Mn and the Ti.
The HRTEM figure of the catalyst that Fig. 3 obtains for different preparation methods.HRTEM is used to study the microstructure and the crystalline condition of catalyst sample.Mn/TiO among Fig. 3 (1)
2(UI) crystal grain edge is irregular, and particle size and the crystal face of two kinds of different crystalline lattice spacings occurs greatly about about 10nm, and the spacing of lattice of a is 0.268nm, is slightly less than that crystal face is the TiO of (112) in the anatase crystal
2Spacing of lattice (0.283nm), the spacing of lattice of b is 0.312nm, is slightly less than the spacing of lattice (0.323nm) for (201) of crystal face in the Mn oxide; And two crystal faces have lap, have explained that Mn oxide is dispersed in carrier surface, and certain interaction is arranged between the two.Mn/TiO among Fig. 3 (2)
2(TI) crystal grain edge comparison rule, about about 20nm, its particle is bigger greatly for particle size, shows that sintering of catalyst causes particle agglomeration; And the crystal face of two kinds of different crystalline lattice spacings appears, wherein the spacing of lattice of c is 0.418nm, with MnO
2Crystal face conform to, the spacing of lattice of d is 0.352nm, with crystal face in the anatase crystal be the TiO of (101)
2Crystal face conforms to, and some is overlapping for two kinds of crystal faces, and explaining also has interaction between the two.From HRTEM figure, can find out catalyst Mn/TiO
2(UI) Mn oxide and anatase crystal TiO in
2Degree of crystallinity little because the variation of spacing of lattice, so interaction between the two is than catalyst Mn/TiO
2(TI) big.
Fig. 4 has done electron diffraction analysis for these two kinds of catalyst granules.The electron diffraction diagram of general monocrystal is the spot of regular distribution, and the electron diffraction diagram of polycrystalline is a series of concentric circles, and the electron diffraction diagram of amorphous substance is the concentric circles of a series of disperses.Mostly what in two figure, observe is diffraction pattern, is illustrated as the monocrystal electronic diffraction, infers that these tiny particles are MnO
XCrystallite.But Fig. 4 has also formed diffraction halation in (1), has explained that a certain amount of amorphous substance exists, and draws in conjunction with the phenetic analysis of front, and the ultrasonic wave infusion process has strengthened Mn oxide and loaded on the dispersiveness on the carrier.
Fig. 5 absorbs saturated NH for two types of catalyst of ultrasonic immersing method and conventional immersion process for preparing down at 120 ℃
3Infared spectrum.Can find out, can observe NH at three kinds of catalyst surfaces
4 +Ion and complex bound NH
3Molecule.For Mn/TiO
2(TI), can observe 1640cm
-1And 1460cm
-1Stronger NH
3Absworption peak, 1195
-1And 3700cm
-1Poor absorption peak and 3000-3500cm
-1Between a broad peak.For Mn/TiO
2(UI, 250 ℃, 4h), in addition 1330 and 1540cm
-1Observed faint NH
3Absworption peak.By comparison, Mn/TiO
2(UI, 500 ℃, 2h) at 1750cm
-1Stronger absworption peak has appearred, in addition, and 1195cm
-1Absworption peak moved on to low band 1095cm
-1, 1540cm
-1Moved on to 1510cm
-1, and 1330cm
-1Absworption peak disappear.1460 and 1640cm
-1The absworption peak at place belongs to NH respectively
3At catalyst surface
The NH that forms on the acid sites
4 +Asymmetric and the symmetric curvature vibration of middle N-H key is at 1195cm
-1The peak at place belongs to NH
3The coordination attitude NH that on catalyst surface Lewis acid sites, forms
3The symmetric curvature vibration of middle N-H key, 1330cm
-1The peak at place belongs to the coordination attitude NH that forms on the Lewis acid sites
3, 3200-3450cm
-1Absworption peak be the stretching vibration of O-H and N-H key, can think NH
3The coordination absorption that between the oxygen atom of catalyst surface, forms with hydrogen atom and metal oxide.1540cm
-1And 1510cm
-1Absworption peak belongs to NH
2Species.Generally believe SCR reaction at first the starting from NH on the support type manganese-based catalyst
3Absorption, dehydrogenation forms active intermediate product NH then
2, follow NH
2And react between the NO, generate N at last
2And H
2O.The NH of ADSORPTION STATE
3The NH that oxidative dehydrogenation forms
2It is the necessary pilot process of reaction.
Above-mentioned analysis can draw such conclusion: the ultrasonic wave catalyst prepared, and corresponding conventional infusion process, more NH has appearred in its surface
3Absorb sour site, especially more Lewis acid position, and formed intermediate product NH
2, therefore help the carrying out that low-temperature SCR reacts.Wherein, Mn/TiO
2(UI, 250 ℃, 4h) catalyst surface acid position is (two kinds at most
Acid, two kinds of Lewis acid), it is active that this is indicating that also this catalyst has higher denitration reaction.
Characterization result is analyzed:
1) XRD, BET and HRTEM characterization result show, " ultrasonic cavitation " effect that ultrasonic wave is produced in the catalyst soakage process spreads active component in the darker duct, top layer of carrier, and the Mn element gets into TiO
2Lattice in, with TiO
2Between interact, and active component is evenly distributed, the catalyst that therefore obtains has bigger specific surface, MnOx is in fully decentralized amorphous state.
2) NH
3The In situ FT-IR infrared analysis of absorption shows Mn/TiO
2(UI) catalyst surface has more NH
3Absorb the acid position, especially Lewis acid, and SCR intermediate product NH has appearred
2, be more conducive to the carrying out of SCR denitration reaction.
Claims (5)
1. the preparation method of a manganese titanium catalyst; It is characterized in that with manganese nitrate and titanium dioxide be raw material, add in the deionized water, mix and stir the back ultrasonic Treatment; Promptly get the manganese titanium catalyst through dry, roasting again; Wherein, described manganese titanium catalyst is carrier with the titanyl compound, is active component with the oxide of manganese.
2. the preparation method of manganese titanium catalyst according to claim 1 is characterized in that the manganese nitrate quality accounts for 32.95% of titanium dioxide quality.
3. the preparation method of manganese titanium catalyst according to claim 1 is characterized in that described ultrasonic Treatment condition is 20～30kHz, 300～500W, and the processing time is 2～4h.
4. the preparation method of manganese titanium catalyst according to claim 1 is characterized in that described drying condition is 100～120 ℃ of down dry 12～15h.
5. the preparation method of manganese titanium catalyst according to claim 1 is characterized in that described roasting condition is 250～500 ℃ of following roasting 2～4h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106902813A (en) * | 2017-03-16 | 2017-06-30 | 山东师范大学 | A kind of samarium doped, the manganese based denitration catalyst of zirconium and preparation method |
| CN109675612A (en) * | 2018-12-31 | 2019-04-26 | 萍乡市华星环保工程技术有限公司 | A kind of molecular sieve catalyst and its production method of middle low-temperature denitration |
| CN109876799A (en) * | 2019-04-08 | 2019-06-14 | 国电环境保护研究院有限公司 | Ultralow temperature SCR denitration and preparation method thereof |
| CN113000045A (en) * | 2019-12-20 | 2021-06-22 | 北京市劳动保护科学研究所 | Manganese-based catalyst and preparation method and application thereof |
| CN113522274A (en) * | 2021-08-06 | 2021-10-22 | 上海环境卫生工程设计院有限公司 | Alkali metal poisoning-resistant low-temperature manganese-based SCR denitration catalyst and preparation method thereof |
| CN116037102A (en) * | 2023-01-30 | 2023-05-02 | 东南大学 | Three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst and preparation and application thereof |
-
2011
- 2011-05-27 CN CN201110139794A patent/CN102319560A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 《Journal of Colloid and Interface Science》 20110517 Yaping Zhang et al. Novel ultrasonic-modified MnOx/TiO2 for low-temperature selective catalytic reduction (SCR) of NO with ammonia 第213页第2节及第214页表1 1-5 第361卷, * |
| YAPING ZHANG ET AL.: "Novel ultrasonic–modified MnOx/TiO2 for low-temperature selective catalytic reduction (SCR) of NO with ammonia", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106902813A (en) * | 2017-03-16 | 2017-06-30 | 山东师范大学 | A kind of samarium doped, the manganese based denitration catalyst of zirconium and preparation method |
| CN106902813B (en) * | 2017-03-16 | 2019-09-24 | 山东师范大学 | The manganese based denitration catalyst and preparation method of a kind of samarium doped, zirconium |
| CN109675612A (en) * | 2018-12-31 | 2019-04-26 | 萍乡市华星环保工程技术有限公司 | A kind of molecular sieve catalyst and its production method of middle low-temperature denitration |
| CN109876799A (en) * | 2019-04-08 | 2019-06-14 | 国电环境保护研究院有限公司 | Ultralow temperature SCR denitration and preparation method thereof |
| CN113000045A (en) * | 2019-12-20 | 2021-06-22 | 北京市劳动保护科学研究所 | Manganese-based catalyst and preparation method and application thereof |
| CN113000045B (en) * | 2019-12-20 | 2023-05-23 | 北京市劳动保护科学研究所 | Manganese-based catalyst and preparation method and application thereof |
| CN113522274A (en) * | 2021-08-06 | 2021-10-22 | 上海环境卫生工程设计院有限公司 | Alkali metal poisoning-resistant low-temperature manganese-based SCR denitration catalyst and preparation method thereof |
| CN113522274B (en) * | 2021-08-06 | 2023-09-01 | 上海环境卫生工程设计院有限公司 | Alkali metal poisoning resistant low-temperature manganese-based SCR denitration catalyst and preparation method thereof |
| CN116037102A (en) * | 2023-01-30 | 2023-05-02 | 东南大学 | Three-dimensional ordered macroporous ultralow Wen Tuoxiao water-resistant catalyst and preparation and application thereof |
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