CN111375445B - Preparation method and application of molecular sieve supported manganese-based denitration catalyst - Google Patents
Preparation method and application of molecular sieve supported manganese-based denitration catalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The application discloses a preparation method of a molecular sieve supported manganese-based denitration catalyst, which comprises the steps of mixing a molecular sieve, a soluble aqueous solution of manganese salt and a ligand to form a mixed solution, enabling the electric properties of a complex formed by the molecular sieve, the manganese salt and the ligand to be opposite, carrying out electrostatic adsorption on the mixed solution, and the like. The molecular sieve supported manganese-based denitration catalyst prepared by the application has uniform particle size of active components and uniform distribution of the active components on the surface of a carrier, and is particularly suitable for removing nitrogen oxides.
Description
Technical Field
The application relates to a molecular sieve catalyst, in particular to a preparation method and application of a molecular sieve supported manganese-based denitration catalyst.
Background
NO as the consumption of Chinese coal and the keeping amount of motor vehicles are increased x The amount of emissions is rapidly rising, and environmental problems caused thereby are increasing. NO (NO) x The harm to human body and environment is huge: can harm the respiratory system of human body, form acid rain and photochemical smog, and also participate in destroying ozone layer. At present, NO is removed x The technique of (1) mainly comprises NO x Direct catalytic decomposition, NO x Storage-reduction catalytic cleaning (NSR), plasma technology, non-catalytic selective reduction (SNCR), selective Catalytic Reduction (SCR), etc.
Selective catalytic reduction for removal of NO x Can better remove NO x Is the mainstream technology successfully used in recent years, and the method uses NH 3 As a reducing agent, selectively convert NO x Reduction to N 2 . According to NO x Different sources, can remove NO by selective catalytic reduction x The technology of (2) is divided into a fixed source and a mobile source. The fixed source is mainly a coal-fired power plant, and the current commercially-used catalyst is V 2 O 5 +WO 3 /TiO 2 The catalyst has an activity temperature window of 300-400 ℃ and ash and SO 2 The catalyst is easy to deactivate in high environmental performance, and if the SCR device is placed in the dust removal desulfurization device, the temperature of the flue gas is reduced to below 200 ℃, so that the catalyst is difficult to function. The mobile source mainly refers to a motor vehicle, and with the gradual upgrade of emission regulations of the motor vehicle, the emission of the engine under the low-speed and low-load working conditions is more severe, which means that higher requirements are put on the low-temperature performance of the SCR catalyst.
To improve the removal of NO by catalytic reduction x The Chinese patent CN103157505B and CN103601211B report Cu-SSZ-13 molecular sieves, the ignition temperature of the catalyst is higher than 150 ℃, the temperature range of NOx conversion rate higher than 80% is up to 225-400 ℃, and the requirements of increasingly severe national emission standards cannot be completely met.
Therefore, it is necessary to remove NO by selective catalytic reduction x Further technical improvements are made to the catalyst of (a).
Disclosure of Invention
The inventor of the present application removes NO in selective catalytic reduction x The creatively found out in the catalyst research of the (2) is that the size and the distribution form of the active components in the molecular sieve supported manganese-based denitration catalyst have a critical influence on the ignition temperature, and if the particle size of the active components is uneven, the uneven distribution on the surface of the carrier can influence the activity and the ignition temperature of the molecular sieve supported manganese-based denitration catalyst.
The application aims to provide a preparation method of a molecular sieve supported manganese-based denitration catalyst, which comprises the following steps:
(1) Mixing a molecular sieve, a soluble aqueous solution of a manganese salt and a ligand to form a mixed solution, and making the molecular sieve and a complex formed by the manganese salt and the ligand opposite in electrical property;
(2) And carrying out electrostatic adsorption on the mixed solution, and washing, drying and roasting to obtain the molecular sieve supported manganese-based denitration catalyst.
The application also provides application of the molecular sieve supported manganese-based denitration catalyst, which is used for removing nitrogen oxides.
The molecular sieve supported manganese-based denitration catalyst prepared by the preparation method provided by the application has the following advantages:
(1) The electrostatic adsorption is utilized to control the chargeability of the surface of the carrier and the coordination state in the manganese salt solution, and the directional adsorption of the synthesized manganese salt on the reducible oxide is designed, so that the single control of the acid site and the redox active site in the manganese-based catalyst is realized;
(2) The structure matching and the function cooperative matching of the acid site and the oxidation-reduction active site in the manganese-based catalyst are realized, and the service temperature of the molecular sieve supported manganese-based denitration catalyst can be reduced;
(3) The specific ligand and manganese salt are selected to be combined through coordination bonds by utilizing the specific isoelectric point of the oxide, and the high-stability high-dispersion low-temperature molecular sieve supported manganese-based denitration catalyst can be prepared by utilizing an electrostatic adsorption mode;
(4) In the molecular sieve supported manganese-based denitration catalyst, the particle size distribution of the manganese-containing compound of the active component is uniform, and the size distribution can be 0.5-1000 nm;
(5) When the molecular sieve supported manganese-based denitration catalyst is used for removing nitrogen oxides, the use temperature can be lower than 100 ℃, the NOx conversion rate can reach more than 80% when the reaction temperature is 95-465 ℃, and the NOx conversion rate can reach 100% when the reaction temperature is 150-465 ℃.
Drawings
FIG. 1 is a TEM spectrum of the finished catalyst Mn/SSZ-13 (5) -EA (en) prepared in example 1
FIG. 2 is a graph of the particle size distribution of Mn species in the finished catalyst Mn/SSZ-13 (5) -EA (en) prepared in example 1.
Fig. 3 is an XRD spectrum of the molecular sieve supported manganese-based catalyst prepared in examples 1 to 5.
Fig. 4 is a graph showing denitration performance of the molecular sieve-supported manganese-based catalysts prepared in examples 1 to 5.
Fig. 5 is a graph showing denitration performance of the molecular sieve-supported manganese-based catalysts prepared in examples 6 to 8.
FIG. 6 shows the denitration performance of Mn/SSZ-13 (10) -EA (en) as a catalyst after hydrothermal aging in example 10.
FIG. 7 shows denitration performance of the catalyst Mn/SSZ-13 (10) -EA (en) after hydrothermal aging in example 11
Fig. 8 is a graph showing denitration performance of the catalyst prepared in example 2 and the catalysts prepared in comparative examples 1 and 2.
FIG. 9 is H of the catalyst prepared in example 2 and the catalysts prepared in comparative examples 1 and 2 2 -TPR contrast plot.
Detailed Description
The application provides a preparation method of a molecular sieve supported manganese-based denitration catalyst, which is characterized in that when a molecular sieve, a soluble aqueous solution of manganese salt and a ligand are mixed to prepare a mixed solution, the molecular sieve and a complex formed by the manganese salt and the ligand are required to be opposite in electrical property. In order to make the electric property of the molecular sieve and the complex formed by the manganese salt and the ligand opposite, the method of adjusting the pH value of the mixed solution can be adopted. One embodiment is to adjust the pH of the mixture to be below the isoelectric point of the molecular sieve so that the complex formed by the manganese salt and the ligand is positively charged. In another embodiment, the pH of the mixture is adjusted to be above the isoelectric point of the molecular sieve, thereby negatively charging the complex formed by the manganese salt and the ligand.
The pH value of the mixed solution can be 1-14. Preferably, the pH of the mixed solution is 1 to 9.
The application provides a preparation method of a molecular sieve supported manganese-based denitration catalyst, wherein the framework configuration of the molecular sieve can be at least one selected from AEI, AFT, AFX, CHA, EAB, EMT, ERI, FAU, GME, JSR, KFI, LEV, LTL, LTN, MOZ, MSO, MWW, OFF, SAS, SAT, SAV, SBS, SBT, SFW, SSF, SZR, TSC, WEN and ZSM.
As a preferred mode, the molecular sieve has a framework configuration selected from at least one of AEI, CHA, FAU and ZSM.
As another preferred mode, the molecular sieve has a framework configuration selected from CHA.
When the framework configuration of the molecular sieve is CHA, the CHA-configured molecular sieve may be at least one selected from the group consisting of SAPO-34, SAPO-44, SAPO-47, LZ-218, LZ-235, LZ-236, SSZ-13, SSZ-62, ZK-14, ZYT-6, linde D, and Linde R.
As a preferred mode, the CHA-configured molecular sieve is selected from at least one of SSZ-13 molecular sieve and SAPO-34 molecular sieve.
As another preferred mode, in the CHA configuration molecular sieve, the silicon-aluminum ratio is 5 to 60.
The application provides a preparation method of a molecular sieve supported manganese-based denitration catalyst, and the manganese salt used in the preparation method can be soluble manganese salt commonly used in the field. As a preferred mode, the manganese salt is selected from at least one of manganese nitrate, manganese chloride, manganese carbonate, manganese sulfate, manganese oxalate and disodium salt of ethylenediamine tetraacetic acid.
The application provides a preparation method of a molecular sieve supported manganese-based denitration catalyst, and the ligand used can be a ligand capable of forming a complex with manganese salt. As a preferred mode, the ligand is at least one selected from the group consisting of diethylamine, triethylamine, diphenylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pyridine, 2-methyl-8-hydroxyquinoline, salicylic acid, sulfosalicylic acid, glycine, oxalic acid, acetic acid, disodium edetate, tartaric acid, succinic acid, lactic acid, acetylacetone and ammonia. As a further preferred mode, the ligand is selected from at least one of ammonia, ethylenediamine, acetic acid, oxalic acid, salicylic acid and acetylacetone.
The ratio between the manganese salt and the ligand should be such that the manganese salt and the ligand form a complex and such that the molecular sieve is electrically opposite to the complex formed by the manganese salt and the ligand in the mixed solution. Preferably, the molar ratio between the manganese salt and the ligand is 1:0.5-20.
The application provides a preparation method of a molecular sieve supported manganese-based denitration catalyst, which comprises the following steps of (2) carrying out electrostatic adsorption and washing on a mixed solution, and then drying. The drying temperature may be a temperature commonly used in the art. Preferably, the drying temperature is 80 to 200 ℃.
The application provides a preparation method of a molecular sieve supported manganese-based denitration catalyst, which comprises the following steps of (2) carrying out electrostatic adsorption, washing and drying on a mixed solution, and then roasting. The firing temperature may be a temperature commonly used in the art. Preferably, the firing temperature is 300 to 800 ℃.
The molecular sieve supported manganese-based denitration catalyst prepared by the preparation method provided by the application has the advantages that the manganese loading amount is preferably 1-10wt%, and the particle size distribution of the manganese-containing compound is preferably 0.5-1000 nm.
The molecular sieve supported manganese-based denitration catalyst prepared by the preparation method provided by the application is suitable for removing nitrogen oxides, and is particularly suitable for removing nitrogen oxides in tail gas discharged by diesel vehicles and/or low-temperature flue gas discharged by coal-fired power plants.
When the molecular sieve supported manganese-based denitration catalyst prepared by the application is used for removing nitrogen oxides, the reaction temperature can be more than 95 ℃. Preferably, the reaction temperature is 95 to 465 ℃. It is further preferable that the reaction temperature is 150 to 465 ℃.
The application will be further illustrated with reference to the following specific examples, without limiting the application to these specific embodiments. It will be appreciated by those skilled in the art that the application encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1: catalyst preparation
Dispersing 1g of SSZ-13 molecular sieve with a silicon-aluminum ratio of 5 in 100mL of water, sequentially adding manganese nitrate and ligand ethylenediamine under intense stirring, stirring for 1h, slowly dropwise adding dilute nitric acid, and controlling the pH to be about 7. After electrostatic adsorption for 24h, the solution was suction filtered and the resulting solid powder was washed with deionized water. Three washes with 100mL deionized water each time. After washing, the product is dried for 12 hours at 110 ℃ in a blast oven, then transferred to a muffle furnace, heated to 550 ℃ at 1 ℃/min and kept at constant temperature for 6 hours to obtain a catalyst finished product, which is marked as Mn/SSZ-13 (5) -EA (en).
In the finished catalyst Mn/SSZ-13 (5) -EA (en), SSZ-13 (5) represents an SSZ-13 molecular sieve with a silicon-aluminum ratio of 5, and the suffix en represents that a ligand complexed with manganese in the electrostatic adsorption process is ethylenediamine (ethylene diamine)
The Mn loading in the finished catalyst Mn/SSZ-13 (5) -EA (en) was 1.3wt% by ICP analysis.
The prepared catalyst finished product Mn/SSZ-13 (5) -EA (en) has a TEM spectrum shown in figure 1 and the manganese species particle size distribution shown in figure 2. As can be seen from FIGS. 1 and 2, the particle size distribution of the manganese species is relatively narrow, with particles in the range of 3-5 nm accounting for about 95%.
The XRD spectrum of the prepared catalyst finished product Mn/SSZ-13 (5) -EA (en) is shown in figure 3. As can be seen from fig. 3, the XRD spectrum of the catalyst after loading manganese did not show diffraction peaks of manganese species, indicating that the manganese species were in a highly dispersed state.
Example 2: preparation of the catalyst
The silica-alumina ratio of the SSZ-13 molecular sieve was adjusted to 10, and the catalyst was prepared under the same operation conditions as in claim 1, and the obtained catalyst was designated Mn/SSZ-13 (10) -EA (en).
The XRD spectrum of the prepared catalyst finished product Mn/SSZ-13 (10) -EA (en) is shown in figure 3. As can be seen from fig. 3, the XRD spectrum of the catalyst after loading manganese did not show diffraction peaks of manganese species, indicating that the manganese species were in a highly dispersed state.
Example 3: preparation of the catalyst
The silica-alumina ratio of the SSZ-13 molecular sieve was adjusted to 20, and the catalyst was prepared under the same operation conditions as in claim 1, and the obtained catalyst was designated Mn/SSZ-13 (20) -EA (en).
The XRD spectrum of the prepared catalyst finished product Mn/SSZ-13 (20) -EA (en) is shown in figure 3. As can be seen from fig. 3, the XRD spectrum of the catalyst after loading manganese did not show diffraction peaks of manganese species, indicating that the manganese species were in a highly dispersed state.
Example 4: preparation of the catalyst
The silica-alumina ratio of the SSZ-13 molecular sieve was adjusted to 30, and the catalyst was prepared under the same operation conditions as in claim 1, and the obtained catalyst was designated Mn/SSZ-13 (30) -EA (en).
The XRD spectrum of the prepared catalyst finished product Mn/SSZ-13 (30) -EA (en) is shown in figure 3. As can be seen from fig. 3, the XRD spectrum of the catalyst after loading manganese did not show diffraction peaks of manganese species, indicating that the manganese species were in a highly dispersed state.
Example 5: preparation of the catalyst
The catalyst was prepared by changing SSZ-13 molecular sieve to SAPO-34 molecular sieve having a silica-alumina ratio of 40, and the remainder was prepared according to the same operating conditions as in claim 1, and the obtained catalyst was designated as Mn/SAPO-34 (40) -EA (en).
The XRD spectrum of the prepared catalyst finished product Mn/SAPO-34 (40) -EA (en) is shown in figure 3. As can be seen from fig. 3, the XRD spectrum of the catalyst after loading manganese did not show diffraction peaks of manganese species, indicating that the manganese species were in a highly dispersed state.
Example 6: preparation of the catalyst
The ligand is changed from ethylenediamine to oxalic acid (oxalic acid), and the catalyst is prepared under the same operation conditions as in claim 2, and the obtained catalyst is designated as Mn/SSZ-13 (10) -EA (oa).
Example 7: preparation of the catalyst
The ligand was changed from ethylenediamine to acetylacetone (acetyl acetone), and the catalyst was prepared under the same operation conditions as in claim 2, and the obtained catalyst was designated as Mn/SSZ-13 (10) -EA (acac).
Example 8: preparation of the catalyst
The ligand is changed from ethylenediamine to salicylic acid (Salicylic acid), and the catalyst is prepared under the same operation conditions as in claim 2, and the obtained catalyst is named Mn/SSZ-13 (10) -EA (sa).
Example 9: denitration performance test
The catalysts prepared in examples 1 to 8 were subjected to SCR activity evaluation. The evaluation method is as follows:
a100 mg sample of the catalyst was taken and placed in a fixed bed reactor, and the catalyst was tested for its denitration activity in the range of 65 to 465 ℃. The denitration performance test conditions of the molecular sieve supported manganese-based SCR low-temperature denitration catalyst are as follows: space velocity 40000h -1 Simulating smoke components: 500ppm NO, 500ppm NH 3 ,、5％H 2 O，5％O 2 Ar is balance gas.
The denitration performance of the catalysts prepared in examples 1 to 8 is shown in fig. 1 and fig. 2.
Example 10: steam resistance test
The catalyst Mn/SSZ-13 (10) -EA (en) prepared in example 2 was subjected to hydrothermal aging and then to NH 3 -SCR activity evaluation.
Hydrothermal aging conditions: space velocity 30000h -1 The temperature is 670 ℃, the water vapor concentration is 10 percent, the air is balance gas, and the aging time is 64 hours.
After the completion of the hydrothermal aging, the catalyst Mn/SSZ-13 (10) -EA (en) after the hydrothermal aging was tested for its denitration performance under the conditions of example 9, as shown in FIG. 6.
Example 11: sulfur resistance test
The catalyst prepared in example 2 was sulfur aged and then NH was performed 3 -SCR activity evaluation:
sulfur aging conditions: space velocity 30000h -1 At a temperature of 250 ℃, SO 2 The concentration is 112ppm, the concentration of water vapor is 10%, air is balance gas, and the aging time is 16h.
After the completion of the sulfur aging, the catalyst Mn/SSZ-13 (10) -EA (en) after hydrothermal aging was tested for its denitration performance under the conditions of example 9, as shown in FIG. 7.
Comparative example 1 impregnation method for preparing catalyst
By contrast, 1g of the SSZ-13 molecular sieve in example 2 was immersed in an equal amount of an aqueous solution of manganese nitrate by an isovolumetric immersion method, immersed for 24 hours at room temperature, dried at 110℃for 12 hours after removal of the solvent by a rotary evaporator, then placed in a muffle furnace, heated to 550℃at 1℃per minute, and kept at a constant temperature for 6 hours to obtain a catalyst finished product, designated Mn/SSZ-13 (10) -Imp.
Comparative example 2 preparation of catalyst by ion exchange method
By contrast, 1g of the SSZ-13 molecular sieve of example 2 was taken and added to 100mL of a 0.1mol/L manganese nitrate solution, stirred for 4h, and washed three times with 100mL of deionized water. Drying in a blast oven for 12 hours after washing, then placing in a muffle furnace, heating to 550 ℃ at 1 ℃/min, and keeping the temperature for 6 hours to obtain a catalyst finished product, which is marked as Mn/SSZ-13 (10) -IE.
The catalyst of example 2 was tested for denitration performance with the catalysts prepared in comparative examples 1 and 2, as shown in fig. 8.
H of the catalyst prepared in example 2 and the catalysts prepared in comparative examples 1 and 2 2 -a TPR comparison graph, as shown in fig. 9.
As can be seen from the above examples and comparative examples, the molecular sieve-supported manganese-based catalyst prepared by the preparation method provided by the present application:
(1) The particle size distribution is narrower, the dispersity is higher, and compared with the catalyst prepared by the impregnation method and the ion exchange method, the denitration activity is higher;
(2) The reduction temperature is lower than that of the impregnation method and the ion exchange method, which shows that the reduction temperature is higher, and the reduction temperature is more favorable for the NH3-SCR reaction, thereby improving the denitration activity of the catalyst.
Claims (9)
1. The preparation method of the molecular sieve supported manganese-based denitration catalyst is characterized by comprising the following steps of:
(1) Mixing a molecular sieve, a soluble aqueous solution of manganese salt and a ligand to form a mixed solution, adjusting the pH value of the mixed solution to 7, and making the electric properties of a complex formed by the molecular sieve, the manganese salt and the ligand opposite; the framework configuration of the molecular sieve is CHA, and the silicon-aluminum ratio is 5-60;
the manganese salt is at least one selected from manganese nitrate, manganese chloride, manganese carbonate, manganese sulfate, manganese oxalate and disodium salt of ethylenediamine tetraacetic acid;
the ligand is at least one of ammonia, ethylenediamine, acetic acid, oxalic acid, salicylic acid and acetylacetone;
the molar ratio between the manganese salt and the ligand is 1:0.5-20;
(2) Carrying out electrostatic adsorption on the mixed solution, and washing, drying and roasting to obtain a molecular sieve supported manganese-based denitration catalyst; in the molecular sieve supported manganese-based denitration catalyst, the particle size distribution of the manganese-containing compound is 0.5-1000 nm.
2. The method for preparing a molecular sieve supported manganese-based denitration catalyst according to claim 1, wherein the CHA-configuration molecular sieve is selected from at least one of SAPO-34, SAPO-44, SAPO-47, LZ-218, LZ-235, LZ-236, SSZ-13, SSZ-62, ZK-14, ZYT-6, linde D and Linde R.
3. The method for preparing a molecular sieve supported manganese-based denitration catalyst according to claim 2, wherein the CHA-configuration molecular sieve is at least one selected from the group consisting of SSZ-13 molecular sieve and SAPO-34 molecular sieve.
4. The method for preparing a molecular sieve supported manganese-based denitration catalyst according to claim 1, wherein in the step (2), the drying temperature is 80 to 200 ℃ and the calcination temperature is 300 to 800 ℃.
5. The method for preparing the molecular sieve supported manganese-based denitration catalyst according to claim 1, which is characterized by comprising the following steps of:
in the molecular sieve supported manganese-based denitration catalyst, the manganese loading amount is 1-10wt%.
6. Use of the molecular sieve supported manganese-based denitration catalyst as claimed in claim 1, characterized in that the molecular sieve supported manganese-based denitration catalyst is used for removal of nitrogen oxides.
7. The use of the molecular sieve supported manganese-based denitration catalyst as claimed in claim 6, which is characterized in that the molecular sieve supported manganese-based denitration catalyst is used for removing nitrogen oxides in tail gas discharged by diesel vehicles and/or low-temperature flue gas discharged by coal-fired power plants.
8. The use of the molecular sieve supported manganese-based denitration catalyst as claimed in claim 6, wherein when the molecular sieve supported manganese-based denitration catalyst is used for removing nitrogen oxides, the reaction temperature is 95-465 ℃.
9. The use of the molecular sieve supported manganese-based denitration catalyst as claimed in claim 8, wherein when the molecular sieve supported manganese-based denitration catalyst is used for removing nitrogen oxides, the reaction temperature is 150-465 ℃.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101596454A (en) * | 2009-07-22 | 2009-12-09 | 南开大学 | Clay load palladium catalyst and preparation method thereof |
| CN102179263A (en) * | 2011-03-10 | 2011-09-14 | 天津大学 | Manganese modified molecular sieve type selective catalytic reduction catalyst for diesel engine |
| CN102500358A (en) * | 2011-11-23 | 2012-06-20 | 浙江大学 | Denitration catalyst with excellent alkali metal and alkaline-earth metal poisoning resistance |
| CN102950008A (en) * | 2011-08-29 | 2013-03-06 | 中国石油化工股份有限公司 | Composite smoke SCR (selective catalytic reduction) denitrification catalyst and preparation method thereof |
| CN103599813A (en) * | 2013-12-04 | 2014-02-26 | 北京化工大学 | Molecular sieve based catalyst used for low-temperature SCR denitration and its preparation method |
| CN104128200A (en) * | 2014-07-22 | 2014-11-05 | 清华大学苏州汽车研究院（吴江） | Copper-based SCR catalyst and preparation method thereof |
| CN104785302A (en) * | 2015-04-21 | 2015-07-22 | 北京大学包头创新研究院 | Selective catalytic reduction denitration catalyst, preparation method and application thereof |
| WO2016078292A1 (en) * | 2014-11-18 | 2016-05-26 | 福州大学 | Sulfur dioxide-resistant low temperature manganese-iron oxide denitrification catalyst and preparation method thereof |
| CN105749973A (en) * | 2014-12-15 | 2016-07-13 | 中国科学院大连化学物理研究所 | Immobilization method for assembling metal complex in meso-porous material |
| CN106423193A (en) * | 2016-09-21 | 2017-02-22 | 中国建筑材料科学研究总院 | Honeycomb manganese denitration catalyst and preparation method thereof |
| CN106799255A (en) * | 2017-02-23 | 2017-06-06 | 华中科技大学 | The preparation method and applications of the molecular sieve catalysts of one-step synthesis method Cu SSZ 39 |
| CN107362807A (en) * | 2017-07-31 | 2017-11-21 | 华南理工大学 | A kind of Mn/Co bases low temperature SCO catalyst and preparation method thereof |
| CN108620070A (en) * | 2018-04-13 | 2018-10-09 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method thereof for synthesis gas C2 oxygenatedchemicals |
-
2018
- 2018-12-29 CN CN201811637619.8A patent/CN111375445B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101596454A (en) * | 2009-07-22 | 2009-12-09 | 南开大学 | Clay load palladium catalyst and preparation method thereof |
| CN102179263A (en) * | 2011-03-10 | 2011-09-14 | 天津大学 | Manganese modified molecular sieve type selective catalytic reduction catalyst for diesel engine |
| CN102950008A (en) * | 2011-08-29 | 2013-03-06 | 中国石油化工股份有限公司 | Composite smoke SCR (selective catalytic reduction) denitrification catalyst and preparation method thereof |
| CN102500358A (en) * | 2011-11-23 | 2012-06-20 | 浙江大学 | Denitration catalyst with excellent alkali metal and alkaline-earth metal poisoning resistance |
| CN103599813A (en) * | 2013-12-04 | 2014-02-26 | 北京化工大学 | Molecular sieve based catalyst used for low-temperature SCR denitration and its preparation method |
| CN104128200A (en) * | 2014-07-22 | 2014-11-05 | 清华大学苏州汽车研究院（吴江） | Copper-based SCR catalyst and preparation method thereof |
| WO2016078292A1 (en) * | 2014-11-18 | 2016-05-26 | 福州大学 | Sulfur dioxide-resistant low temperature manganese-iron oxide denitrification catalyst and preparation method thereof |
| CN105749973A (en) * | 2014-12-15 | 2016-07-13 | 中国科学院大连化学物理研究所 | Immobilization method for assembling metal complex in meso-porous material |
| CN104785302A (en) * | 2015-04-21 | 2015-07-22 | 北京大学包头创新研究院 | Selective catalytic reduction denitration catalyst, preparation method and application thereof |
| CN106423193A (en) * | 2016-09-21 | 2017-02-22 | 中国建筑材料科学研究总院 | Honeycomb manganese denitration catalyst and preparation method thereof |
| CN106799255A (en) * | 2017-02-23 | 2017-06-06 | 华中科技大学 | The preparation method and applications of the molecular sieve catalysts of one-step synthesis method Cu SSZ 39 |
| CN107362807A (en) * | 2017-07-31 | 2017-11-21 | 华南理工大学 | A kind of Mn/Co bases low temperature SCO catalyst and preparation method thereof |
| CN108620070A (en) * | 2018-04-13 | 2018-10-09 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method thereof for synthesis gas C2 oxygenatedchemicals |
Non-Patent Citations (1)
| Title |
|---|
| Hongli Wu et al..Solvent-Free Aerobic Oxidation of Alcohols Catalyzed by an Efficient and Recyclable Palladium Heterogeneous Catalyst.《Adv. Synth. Catal.》.2005,第347卷第1356-1360页. * |
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