CN115920876B - Preparation method and application of Nb-Ce-Zr denitration catalyst for SCR degradation - Google Patents
Preparation method and application of Nb-Ce-Zr denitration catalyst for SCR degradation Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 229910004625 Ce—Zr Inorganic materials 0.000 title claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 13
- 230000015556 catabolic process Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000001035 drying Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 4
- 229910009111 xH2 O Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims 3
- 238000000227 grinding Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 229910009112 xH2O Inorganic materials 0.000 abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 2
- 238000003915 air pollution Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000010955 niobium Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 1
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- 239000004480 active ingredient Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
本发明公开了一种用于NH3‑SCR降解NO的Nb‑Ce‑Zr/TiO2催化剂及其应用，属于大气污染治理和环保催化环境领域。该催化剂是以TiO2为载体，以Nb为主活性组分和金属Ce、Zr为助剂，采用浸渍法制备而成。首先称取计量比的C10H5NbO20·xH2O、Zr(NO3)4·5H2O和Ce(NO3)3·6H2O溶于去离子水中，并磁力搅拌溶解，之后在溶液中加入载体TiO2，70℃水浴磁力搅拌至水分蒸发完全。接着将制得的粉末置于干燥箱中过夜干燥，在500℃焙烧5h，自然冷却即制得用于SCR降解NO的Nb‑Ce‑Zr/TiO2催化剂。本发明的Nb‑Ce‑Zr/TiO2催化剂具备高的SCR降解NO能力。同时，助剂Ce、Zr与活性组分Nb之间能起到良好的协同催化作用，提高了催化剂的中低温活性，并拓宽催化剂的操作温度窗口。The invention discloses a Nb-Ce-Zr/ TiO2 catalyst for NH3 -SCR degradation of NO and its application, belonging to the field of air pollution control and environmental catalytic environment. The catalyst is prepared by an impregnation method with TiO2 as a carrier, Nb as a main active component and metal Ce and Zr as additives. First, weigh the stoichiometric ratio of C10H5NbO20 · xH2O , Zr( NO3 ) 4 · 5H2O and Ce( NO3 ) 3 · 6H2O and dissolve them in deionized water, stir them magnetically to dissolve, then add the carrier TiO2 to the solution, stir them magnetically in a 70°C water bath until the water evaporates completely. Then, the obtained powder is placed in a drying oven to dry overnight, roasted at 500°C for 5h, and naturally cooled to obtain a Nb-Ce-Zr/ TiO2 catalyst for SCR degradation of NO. The Nb-Ce-Zr/ TiO2 catalyst of the present invention has a high SCR NO degradation capability. At the same time, the additives Ce and Zr can play a good synergistic catalytic role with the active component Nb, thereby improving the medium and low temperature activity of the catalyst and widening the operating temperature window of the catalyst.
Description
Technical Field
The invention relates to a preparation method and application of a Nb-Ce-Zr catalyst for degrading NO by NH 3 -SCR, in particular to a catalyst for effectively degrading gas pollutants, belonging to the field of atmospheric pollution control and environmental protection catalytic environment.
Background
Nitrogen oxides NO X(NO、NO2 and N 2 O) are one of the main pollutants in the atmosphere and also one of the main factors in the generation of mist, where NO occupies more than 90%. NO X is harmful to human health, and secondary pollution such as photochemical smog and acid rain can be generated. Therefore, reducing NOx emissions and improving NOx removal efficiency has become one of the hot research directions in the current environmental catalytic field.
The SCR technology is a denitration technology applied commercially at present, and the technology is characterized in that a high-efficiency NO degradation catalyst is developed, and under the action of the catalyst, an external reducing agent (NH 3) is added to selectively reduce NO X into N 2, so that NO X in flue gas is degraded. Therefore, the development of a catalyst for SCR degradation of NO X is imperative.
The commercial V 2O5-WO3/TiO2 catalyst at home and abroad has poor low-temperature activity, the operation temperature window is narrow (350-400℃)(A remarkable catalyst combination to widen the operating temperature window of the selective catalytic reduction of NO by NH3.Chem Cat Chem,2014,6:2263-2269.),, and V 2O5 belongs to high-toxicity substances, the molecular sieve catalyst has poor water resistance and sulfur resistance, the noble metal catalyst has high preparation cost, is easy to be poisoned by sulfur, is easy to be sintered and deactivated at high temperature, cannot economically and environmentally remove NO x, and cannot meet the stricter emission standard of coal-fired power plants, so that development of an SCR catalyst with higher catalytic activity and wider operation temperature window is needed.
The design concept of the catalyst is that firstly, metal active components with good NO removal effect and low cost and low toxicity are screened out, and the addition of the auxiliary agent can promote the high dispersion of the active components and strengthen the interaction between the auxiliary agent, the active components and the carrier, so that the low-temperature denitration activity and the stability of the catalyst are improved. Therefore, according to the classification and structural characteristics of metals, the Nb element is found to have similar properties to V because of being in the same family as V, the toxicity is weaker than V, and the niobium-based material is used as a solid acid catalyst, so that the acidity of the catalyst can be remarkably improved. Thus we explored the content of the active component Nb and found that 10% of the active component Nb had some high temperature activity but poor low temperature activity. It is reported In the literature that Cu, la, fe, co and In promoters are incorporated to increase the low temperature activity of the catalyst, but that both Fe, cu, la, co and In promoters do not perform well at low temperatures. The metal composite oxide structure with Cu, la, fe, co and In auxiliary agent has the capability of oxygen storage and oxygen release, and has the capability of improving low-temperature activity and stability, but cannot be shown.
Disclosure of Invention
The invention aims to provide a preparation method and application of a Nb-Ce-Zr catalyst for degrading NO by SCR, and the method has the advantages of simple process, easy operation and low cost. The Nb-Ce-Zr catalyst prepared by the method obviously improves the denitration activity of the catalyst and widens the operating temperature window. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the Nb-Ce-Zr catalyst for degrading NO by SCR comprises the following steps:
(a) The metered amounts of C 10H5NbO20.xH2O、Zr(NO3)4.5H2 O and Ce (NO 3)3·6H2 O were dissolved in deionized water and stirred to dissolve;
(b) Adding a metered TiO 2 carrier into the solution (a), heating the solution in a magnetic stirrer at a constant temperature of 70 ℃, and drying in water bath;
(c) Placing the sample in step (b) in a 110 ℃ oven, and drying for 12 hours;
(d) And (3) placing the sample obtained in the step (C) in a muffle furnace at 500 ℃ and roasting for 5 hours to obtain the Nb-Ce-Zr/TiO 2 catalyst.
According to the scheme, the mass of the carrier is 100%, and the addition amount of the active component Nb is 3% -15%.
According to the scheme, the addition amount of the auxiliary agent Ce is 1% -9% based on 100% of the mass of the carrier.
According to the scheme, the addition amount of the auxiliary agent Zr is 0.5% -3% based on 100% of the mass of the carrier.
The invention also provides an application of the Nb-Ce-Zr catalyst machine for SCR prepared by the preparation method in the technical scheme in a flue gas SCR NO degradation reaction.
Compared with the prior art, the invention has the following advantages:
(1) The Nb-Ce-Zr catalyst for the SCR degradation NO reaction has higher catalytic activity and wider operating temperature window, the NO conversion rate under the condition of 200 ℃ is 80%, the highest NO conversion rate 100% reaction temperature is T top =250-450 ℃, and the operating temperature window T 80 is 210-500 ℃.
(2) The preparation method has simple process and easy control of preparation conditions, and is suitable for industrial production.
Drawings
FIG. 1 is a graph showing the catalytic activity of the catalysts prepared in examples 1,2, 3, 4 and 5.
FIG. 2 is a graph showing the catalytic activity of the catalysts prepared in examples 1, 5, 6, 7, 8, 9 and 10.
FIG. 3 is a graph showing the catalytic activity test of the catalysts prepared in examples 1, 11, 12, 13, 14 and 15.
FIG. 4 is a graph showing the catalytic activity of the catalysts prepared in examples 1, 9 and 12.
Fig. 5 is an XRD spectrum of the catalyst prepared in example 1, example 9 and example 12.
Detailed Description
The preparation method of the Nb-Ce-Zr catalyst for degrading NO by SCR comprises the following steps:
(a) The metered amounts of C 10H5NbO20.xH2O、Ce(NO3)3·6H2 O and Zr (NO 3)4.5H2 O were dissolved in deionized water and stirred to dissolve;
(b) Adding a metered TiO 2 carrier into the solution (a), heating the solution in a magnetic stirrer at a constant temperature of 70 ℃, and drying in water bath;
(c) Placing the sample in step (b) in a 110 ℃ oven, and drying for 12 hours;
(d) And (C) placing the sample obtained in the step (C) in a muffle furnace at 500 ℃, roasting for 5 hours, and naturally cooling to room temperature to obtain the Nb-Ce-Zr/TiO 2 catalyst.
According to the scheme, the mass of the carrier is 100%, and the addition amount of the active component Nb is 3% -15%.
According to the scheme, the addition amount of the auxiliary agent Ce is 1% -9% based on 100% of the mass of the carrier.
According to the scheme, the addition amount of the auxiliary agent Zr is 0.5% -3% based on 100% of the mass of the carrier.
The following describes the invention in more detail with reference to a few examples, but is not intended to limit the invention to the examples described.
EXAMPLE 1 Synthesis of 10% Nb/TiO 2 catalyst
Weighing 0.810g of C 10H5NbO20.xH2 O, dissolving in 30ml of deionized water, mixing and stirring until the C 10H5NbO20.xH2 O is dissolved, adding 2g of TiO 2, then heating the mixture at a constant temperature of 70 ℃ for water bath drying in a magnetic stirrer, then placing the dried sample in a 110 ℃ drying box for drying for 12 hours, finally roasting the dried sample in a 550 ℃ muffle furnace for 5 hours, tabletting and crushing the roasted powder to 20-40 meshes under the pressure of 10Mpa by a tablet press, and thus obtaining the 10% Nb/TiO 2 catalyst.
Evaluation of catalyst
The activity evaluation of the catalyst was carried out in a self-made continuous flow fixed bed reactor. The reaction tube is a quartz tube with an inner diameter of 6mm and a length of 33cm, the reaction temperature is measured by a thermocouple arranged in the middle of the reaction tube, and the reaction temperature is controlled by a temperature programming controller. The gas flow is controlled by a mass flowmeter, the reaction raw material gas comprises 400ppm NH 3、400ppm NO、3％O2 and balance gas Ar, the catalyst dosage in the experiment is 0.2g, the reaction temperature is 150-500 ℃, and the reaction temperature is sampled every 50 ℃. The conversion of NO was calculated by detection with a smoke analyzer (MRU, VARIO PLUS). The conversion curves of the catalyst to NO at different temperature points are shown in FIGS. 1, 2, 3 and 4, and the NO conversion rate and the operating temperature window of the catalyst at 200 ℃ and the optimal activity temperature are shown in Table 1.
Examples 2 to 5
Compared with example 1, only the content of Nb in the catalyst active component is different, and the other processes are the same as those of example 1, namely, the Nb/TiO 2 catalyst with different Nb contents is prepared. The catalyst compositions of examples 2 to 5 are shown in table 1.
Evaluation of catalyst
The graph of the catalyst versus NO conversion at various temperature points is shown in fig. 1, following the evaluation method of example 1. The NO conversion at 200 ℃, the optimum activity temperature and the operating temperature window are shown in table 2.
Examples 6 to 10
The process is the same as that of example 1, except that the auxiliary agent Ce is added and the content of the auxiliary agent Ce is different, and the process is the same as that of example 1, and concretely comprises the steps of weighing 0.810g C10H5NbO20.xH2O、0.025g～0.454g Ce(NO3)2·6H2O、30ml deionized water, mixing and stirring until the deionized water is dissolved, adding 2g TiO2, heating a magnetic stirrer at a constant temperature of 70 ℃ for water bath drying, placing the dried sample in a 110 ℃ drying box for drying for 12 hours, finally roasting in a 550 ℃ muffle furnace for 5 hours, tabletting and crushing the roasted powder to 20-40 meshes under the pressure of 10Mpa by a tablet press, and obtaining the Nb-Ce/TiO 2 catalyst with different Ce auxiliary agent contents. The catalyst compositions of examples 6 to 11 are shown in Table 1.
Evaluation of catalyst
The graph of the catalyst versus NO conversion at various temperature points is shown in fig. 1, following the evaluation method of example 1. The NO conversion at 200 ℃, the optimum activity temperature and the operating temperature window are shown in table 2.
Examples 11 to 15
The process is the same as that of example 1 except that the auxiliary agent Zr is added and the content of the auxiliary agent Zr is different, and the process is the same as that of example 1, and specifically comprises the steps of weighing 0.810g C10H5NbO20.xH2O、0.353g Ce(NO3)2·6H2O、0.035g～0.209g Zr(NO3)4.5H2O 30ml deionized water, mixing and stirring until the deionized water is dissolved, adding 2g of TiO 2, heating a magnetic stirrer at a constant temperature of 70 ℃ for water bath drying, placing the dried sample in a 110 ℃ drying box for drying for 12 hours, roasting in a 550 ℃ muffle furnace for 5 hours, tabletting and crushing the roasted powder to 20-40 meshes under the pressure of 10Mpa by a tablet press, and obtaining the Nb-Ce-Zr/TiO 2 catalyst with different Ce auxiliary agent contents. The catalyst compositions of examples 12 to 16 are shown in Table 1
Evaluation of catalyst
The graph of the catalyst versus NO conversion at various temperature points is shown in fig. 1, following the evaluation method of example 1. The NO conversion at 200 ℃, the optimum activity temperature and the operating temperature window are shown in table 2.
Examples molecular sieve catalysts composition table:
Specific examples catalyst compositions are shown in table 1:
Results of activity evaluation:
The specific activity evaluation results are shown in table 2:
XRD characterization
In fig. 5, the three catalysts all show characteristic diffraction peaks of anatase and rutile phase TiO 2, mainly based on anatase TiO 2 crystal structure, and the three catalysts can not detect characteristic diffraction peaks of metal oxides such as Nb 2O5,ZrO2, which indicate that the substances may exist in amorphous or poor crystal phases or are highly dispersed on the surface of the catalyst, or the size of the microcrystals may be lower than the detection limit of XRD, and in addition, the 10% Nb-7% Ce/TiO 2 and 10% Nb-7% Ce-0.7% Zr/TiO 2 catalysts show weak characteristic diffraction peaks of cubic CeO 2 crystal forms, and the characteristic diffraction peak intensity of TiO 2 is reduced, which indicates that the addition of the auxiliary agent is beneficial to reducing the crystallinity of the catalyst. The size of the anatase phase TiO 2 (101) crystal grain is calculated by adopting a Scherrer formula, the crystal grain size of the catalyst is almost unchanged after the addition agent Ce is introduced, and the crystal grain size of the 10 percent Nb-7 percent Ce/TiO 2 catalyst is reduced from 15.8nm to 15.6nm after the addition agent Zr is introduced. This is probably due to the fact that after the catalyst has introduced the promoter Zr, the interaction between the active ingredient Nb, the promoter and the support TiO 2 is enhanced, causing the crystallite size to decrease to a different extent.
Claims (3)
1. The preparation method of the Nb-Ce-Zr denitration catalyst for NH 3 -SCR degradation is characterized by comprising the following steps:
(1) Weighing active components C 10H5NbO20.xH2 O, an auxiliary agent Zr (NO 3)4.5H2 O and an auxiliary agent Ce (NO 3)3·6H2 O), adding 30ml of deionized water, and stirring until the active components C 10H5NbO20.xH2 O, the auxiliary agent Zr and the auxiliary agent Ce are completely dissolved to obtain a transparent solution;
(2) Adding the metered TiO 2 carrier into the transparent solution obtained in the step (1) to obtain mixed slurry;
(3) Adding a magnetic stirrer into the mixed slurry obtained in the step (2), heating the mixed slurry at a constant temperature of 70 ℃ in the magnetic stirrer, and drying in water bath;
(4) Placing the sample obtained in the step (3) in an oven, and drying overnight;
(5) Grinding the sample obtained in the step (4) into fine powder, placing the fine powder in a muffle furnace, roasting, and naturally cooling to room temperature to obtain the SCR degradation NO catalyst;
Taking the mass of the carrier as 100%, wherein the adding amount of the active component Nb is 3% -15%;
the mass percentage of the auxiliary agent Ce is 0.5% -9% by taking the mass of the carrier as 100%;
the mass percentage of the auxiliary agent Zr is 0.5% -3% by taking the mass of the carrier as 100%.
2. The method for preparing the Nb-Ce-Zr denitration catalyst for NH 3 -SCR degradation according to claim 1, wherein,
The drying temperature is 110 ℃;
the drying time is 12 hours;
The roasting temperature is 500 ℃;
the roasting time is 5 hours.
3. Use of a Nb-Ce-Zr denitration catalyst for NH 3 -SCR degradation according to claim 1 or 2 in tail gas denitration.
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| CN104368329A (en) * | 2014-09-19 | 2015-02-25 | 中国科学院生态环境研究中心 | Cerium-niobium-zirconium composite oxide catalyst, preparation method and uses thereof |
| CN105879858A (en) * | 2016-04-15 | 2016-08-24 | 中国建筑材料科学研究总院 | Denitrification catalyst and preparation method thereof |
| CN106423139A (en) * | 2016-11-14 | 2017-02-22 | 包头稀土研究院 | Rare-earth-based SCR denitration catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104368329A (en) * | 2014-09-19 | 2015-02-25 | 中国科学院生态环境研究中心 | Cerium-niobium-zirconium composite oxide catalyst, preparation method and uses thereof |
| CN105879858A (en) * | 2016-04-15 | 2016-08-24 | 中国建筑材料科学研究总院 | Denitrification catalyst and preparation method thereof |
| CN106423139A (en) * | 2016-11-14 | 2017-02-22 | 包头稀土研究院 | Rare-earth-based SCR denitration catalyst and preparation method thereof |
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