CN107570205B - Preparation method of modified Beta molecular sieve catalyst - Google Patents
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Abstract
The invention provides a preparation method of a modified Beta molecular sieve based catalyst, and belongs to the technical field of catalysts. The method comprises the steps of preparing Beta molecular sieve raw powder, preparing a Mn-Co-Beta molecular sieve and preparing a Sn modified Mn-Co-Beta molecular sieve, wherein the molar ratio of Mn element to Co element is 5-8: 1, and the mass of Mn element accounts for 10-13% of the mass of the Mn-Co-Beta molecular sieve; the molar ratio of the Sn element to the manganese element is 1: 35-40. The catalyst prepared by the method can be applied to an automobile exhaust low-temperature SCR denitration system, and has better CO resistance on the premise of keeping a better temperature operation window2And SO2Poisoning ability, thereby ensuring better catalytic activity.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of catalysts, and in particular relates to a preparation method of a modified Beta molecular sieve catalyst.
[ background of the invention ]
Nitrogen oxides, which are common atmospheric pollutants, mainly from the combustion of fossil fuels, are not only the main cause of acid rain formation, but also react with hydrocarbons to form photochemical smog, and are now second only to the important atmospheric pollutants of inhalable particulate matter and sulfur dioxide. NO emitted from stationary source represented by flue gas of coal-fired power plant and mobile source represented by tail gas of diesel vehiclexOccupying about 60% of the emission share. Currently, Ammonia-selective catalytic Reduction (Ammonia-Selective catalytic Reduction of NO)xNH3-SCR) is the removal of stationary source NOxOne of the most efficient and widely used technical processes, the core of which is the catalyst, and currently the most widely used commercially is V2O5/TiO2Is a catalyst. The active temperature window of the catalyst is 300-450 ℃, and the SCR device needs to be arranged before dust removal and desulfurization, and the flue gas contains a large amount of fly ash, As and SO2And the like, which easily poison and deactivate the catalyst. Therefore, in order to reduce the catalyst poisoning and deactivation and prolong the service life of the catalyst, the SCR device needs to be placed after dust removal and desulfurization, and the flue gas temperature is lower than 200 ℃. On the other hand, since the catalyst contains heavy metal V and has biotoxicity, it is very important to develop an SCR denitration catalyst which is environmentally friendly and has excellent low-temperature SCR activity (particularly at 200 ℃ or lower).
Active components of the low-temperature SCR catalyst researched at present mainly comprise transition metals, mainly comprising V, Ce, Cu, Mn, Fe, Cr and the like. Form of catalystThe supported catalyst has a carrier of TiO, and the carrier of the supported catalyst is TiO2、ZrO2、Al2O3Molecular sieves and carbon materials, and the like. NO of molecular sieve type catalyst with excellent performancexThe conversion rate can basically reach more than 90 percent, however, under the actual working condition, a certain amount of SO exists in the tail gas of the motor vehicle2Hydrocarbons, CO2And H2O and the like, especially hydrocarbons compete to be adsorbed on the molecular sieve pore channels, side reactions and carbon deposition on the catalyst are caused, and the catalytic activity is further reduced, so that the prepared NH with low temperaturexCatalysts which are active in the SCR and hydrocarbon SCR reactions have a great practical significance.
[ summary of the invention ]
The invention aims to: aiming at the problems, the preparation method of the modified Beta molecular sieve catalyst is provided, and the catalyst prepared by the method can be applied to low-temperature and low-temperature NH (NH) of automobile exhaust3In an SCR denitration system, on the premise of keeping a better temperature operation window, the system has better SO resistance2、CO2And H2O poisoning capacity, thereby ensuring better catalytic activity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a modified Beta molecular sieve catalyst comprises the following steps:
(1) preparing Beta molecular sieve raw powder: SiO of the prepared Beta molecular sieve raw powder framework2/Al2O3The molar ratio is 25-40, the relative crystallinity is not less than 80%, and the specific surface area is 500-580 m2A pore volume of 0.25 to 0.50 cm/g3The mesoporous aperture is 4-15 nm;
(2) preparing the Mn-Co-Beta molecular sieve: the molar ratio of Mn element to Co element in the Mn-Co-Beta molecular sieve is 5-8: 1, and the mass of the Mn element accounts for 10-13% of that of the Mn-Co-Beta molecular sieve;
(3) preparing a Sn modified Mn-Co-Beta molecular sieve: and (3) soaking the Mn-Co-Beta molecular sieve prepared in the step (2) in a Sn salt solution in an equal volume, and drying and roasting to obtain the modified Beta molecular sieve catalyst, wherein the molar ratio of Sn element to Mn element is 1: 35-40.
In the invention, preferably, the Beta molecular sieve raw powder is prepared by the following steps: firstly, the aluminum source NaAlO is added2Uniformly mixing and stirring template agents tetraethylammonium hydroxide, sodium hydroxide and deionized water, then adding silicon source silica sol into the mixed solution to form a uniform sol system, aging the sol system for 1-2 hours at the temperature of 60-80 ℃, then putting the sol system into a high-pressure reaction kettle, and heating to the temperature of 140-160 ℃ for crystallization for 36-72 hours; the molar composition of the synthetic raw material is SiO2：Al2O3: template agent: NaOH: h2O1.0: 0.025 to 0.04: 0.2-0.5: 0.2-0.4: 12-30, and filtering, washing and drying after hydrothermal crystallization to obtain the Beta molecular sieve raw powder.
In the invention, preferably, the Mn-Co-Beta molecular sieve is obtained by the following steps:
(1) performing ion exchange treatment on Beta molecular sieve raw powder by adopting an ammonium salt solution, and filtering, washing, drying and roasting to obtain the unammonium-removed Beta molecular sieve;
(2) soaking the deammoniated Beta molecular sieve in a manganese salt solution in an equal volume, adding an ammonium carbonate solution while stirring, stirring uniformly, and aging for 30-40 min; after filtering, drying and roasting, obtaining the manganese-loaded Beta molecular sieve;
(3) soaking the manganese-loaded Beta molecular sieve in a cobalt salt solution in an equal volume, adding an ammonium carbonate solution while stirring, stirring uniformly, and aging for 30-40 min; and filtering, drying and roasting to obtain the Mn-Co-Beta molecular sieve.
In the invention, preferably, in the step (3), the Mn-Co-Beta molecular sieve is immersed in a Sn salt solution in an equal volume for 2-8 hours, and the drying is carried out at 100-120 ℃ for 3-12 hours; the roasting condition is roasting for 3-5 hours at the temperature of 600-700 ℃.
In the invention, preferably, the ammonium salt used in the step (1) is one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium dihydrogen phosphate and ammonium citrate, the ion exchange temperature is 85-100 ℃, the exchange time is 2-10 h, the mass concentration of the ammonium salt is 6-12%, and the liquid-solid ratio is 1: 1-10: 1.
Preferably, the drying condition in the step (1) is drying for 5-20 hours at the temperature of 60-100 ℃; the roasting condition is roasting for 3-5 hours at the temperature of 500-600 ℃.
Preferably, in the step (2), the same volume of manganese salt solution is adopted to impregnate the deaminized Beta molecular sieve for 2-8 hours, and the drying condition is that the Beta molecular sieve is dried for 3-12 hours at the temperature of 100-120 ℃; the roasting condition is roasting for 3-5 hours at the temperature of 600-700 ℃.
Preferably, in the step (3), the cobalt salt solution is used for soaking the manganese-loaded Beta molecular sieve for 2-8 hours in an equal volume, and the drying condition is that the drying is carried out at the temperature of 100-120 ℃ for 3-12 hours; the roasting condition is roasting for 3-5 hours at the temperature of 600-700 ℃.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the invention, two metals of Mn and Co are loaded on a Beta molecular sieve and then modified by Sn, the active potentials are mutually influenced by controlling the proportion of 3 active components of Mn, Co and Sn, the number of active sites on the surface of the catalyst, the oxygen hole concentration and the acidic sites of B acid and L acid are effectively increased, the prepared catalyst can be applied to an automobile tail gas low-temperature SCR (Selective catalytic reduction) denitration system, the catalyst has excellent catalytic activity within the temperature range of 150-600 ℃, the conversion rate of NOx is more than 90%, and the catalyst can also be used for the toxic component SO coexisting in diesel vehicle tail gas2、CO2、H2O and C3H6The catalytic reaction is generated, so that the catalyst has better anti-poisoning capability and better catalytic activity is ensured.
2. When the Beta molecular sieve raw powder is prepared, the sol system is aged for 1-2 hours at the temperature of 60-80 ℃, then crystallization reaction is carried out, the crystallization degree of the Beta molecular sieve can be over 85 percent, and the Beta molecular sieve with rich micropores and stable framework structure can be obtained by controlling the proportion of each component in the sol system.
3. In the preparation process of the Mn-Co-Beta molecular sieve, firstly, the Beta molecular sieve after deammoniation is impregnated by soluble manganese salt and cobalt salt, so that manganese ions and cobalt ions enter the pore channels of the molecular sieve, then ammonium carbonate is added as a precipitator, the mixture is filtered and roasted, the manganese carbonate and the manganese cobaltate are decomposed, and a large amount of generated gas enables active substances in the pore channels to have smaller particle size and higher surface energy, so that the catalytic reaction activity is improved.
[ detailed description ] embodiments
In order that the invention may be more clearly expressed, the invention will now be further described by way of specific examples.
Example 1
A preparation method of a modified Beta molecular sieve catalyst comprises the following steps:
(1) preparing Beta molecular sieve raw powder: firstly, mixing and stirring uniformly 2.05g of aluminum source NaAlO2, 29.45g of template agent tetraethylammonium hydroxide, 8g of sodium hydroxide and 216g of deionized water, then adding 60.08g of silicon source silica sol into the mixed solution to form a uniform sol system, aging the sol system for 2 hours at 60 ℃, then placing the sol system into a high-pressure reaction kettle, and heating to 160 ℃ for crystallization for 36 hours; after hydrothermal crystallization, filtering, washing and drying, the Beta molecular sieve raw powder is obtained. The Beta molecular sieve raw powder has the relative crystallinity of not less than 80 percent and the specific surface area of 500-580 m2A pore volume of 0.25 to 0.50 cm/g3The mesoporous aperture is 4-15 nm;
(2) preparing the Mn-Co-Beta molecular sieve:
ion exchange treatment is carried out on Beta molecular sieve raw powder for 10 hours by adopting ammonium chloride with the mass concentration of 6% at the temperature of 85 ℃, and the liquid-solid ratio is 1: 1. Filtering, washing with water, and drying at 60 deg.C for 5 hr; then roasting for 5 hours at the temperature of 500 ℃ to obtain the deammoniated Beta molecular sieve;
weighing 3.19g of manganese nitrate, fully dissolving in deionized water to obtain a manganese nitrate solution, soaking the deammoniated Beta molecular sieve in the manganese nitrate solution for 2 hours in an equal volume, adding 2g of 0.05 mol/L ammonium carbonate solution while stirring, stirring uniformly, aging for 30min, filtering, drying at 100 ℃ for 12 hours, roasting at 600 ℃ for 5 hours, filtering, drying and roasting to obtain the manganese-loaded Beta molecular sieve;
weighing 1.036g of cobalt nitrate, fully dissolving the cobalt nitrate in deionized water to obtain a cobalt nitrate solution, soaking the manganese-loaded Beta molecular sieve in the cobalt nitrate solution for 2 hours in an equal volume, adding 1.5g of 0.03 mol/L ammonium carbonate solution while stirring, stirring uniformly, aging for 30min, filtering, drying at 100 ℃ for 12 hours, and roasting at 600 ℃ for 5 hours to obtain the Mn-Co-Beta molecular sieve.
(3) Preparing a Sn modified Mn-Co-Beta molecular sieve: and (3) fully dissolving 0.199g of tin nitrate in deionized water to obtain a tin nitrate solution, soaking the Mn-Co-Beta molecular sieve prepared in the step (2) in the tin nitrate solution in an equal volume for 2 hours, filtering, drying at the temperature of 100 ℃ for 3 hours, and roasting at the temperature of 600 ℃ for 5 hours.
Example 2
A preparation method of a modified Beta molecular sieve catalyst comprises the following steps:
(1) preparing Beta molecular sieve raw powder: firstly, mixing and stirring uniformly 2.97g of aluminum source NaAlO2, 51.54g of template agent tetraethylammonium hydroxide, 12g of sodium hydroxide and 378g of deionized water, then adding 60.08g of silicon source silica sol into the mixed solution to form a uniform sol system, aging the sol system for 1.5 hours at 70 ℃, then placing the sol system into a high-pressure reaction kettle, and heating to 150 ℃ for crystallization for 60 hours; after hydrothermal crystallization, filtering, washing and drying, the Beta molecular sieve raw powder is obtained. The Beta molecular sieve has a relative crystallinity of not less than 80% and a specific surface area of 500-580 m2A pore volume of 0.25 to 0.50 cm/g3The mesoporous aperture is 4-15 nm;
(2) preparing the Mn-Co-Beta molecular sieve:
performing ion exchange treatment on Beta molecular sieve raw powder for 6 hours by adopting ammonium sulfate with the mass concentration of 10% at the temperature of 90 ℃, wherein the liquid-solid ratio is 5: 1. Filtering, washing with water, and drying at 80 deg.C for 15 hr; then roasting for 4 hours at the temperature of 550 ℃ to obtain the deammoniated Beta molecular sieve;
weighing 3.67g of manganese nitrate, fully dissolving in deionized water to obtain a manganese nitrate solution, soaking the deammoniated Beta molecular sieve in the manganese nitrate solution for 6 hours in an equal volume, adding 2g of 0.06 mol/L ammonium carbonate solution under stirring, stirring uniformly, aging for 35min, filtering, drying at 110 ℃ for 6 hours, roasting at 650 ℃ for 4 hours, filtering, drying and roasting to obtain the manganese-loaded Beta molecular sieve;
weighing 1.19g of cobalt nitrate, fully dissolving the cobalt nitrate in deionized water to obtain a cobalt nitrate solution, soaking the manganese-loaded Beta molecular sieve in the cobalt nitrate solution for 6 hours in an equal volume, adding 1.5g of 0.04 mol/L ammonium carbonate solution while stirring, stirring uniformly, aging for 35 minutes, filtering, drying at the temperature of 110 ℃ for 8 hours, and roasting at the temperature of 650 ℃ for 4 hours to obtain the Mn-Co-Beta molecular sieve.
(3) Preparing a Sn modified Mn-Co-Beta molecular sieve: and (3) fully dissolving 0.22g of tin nitrate in deionized water to obtain a tin nitrate solution, soaking the Mn-Co-Beta molecular sieve prepared in the step (2) in the tin nitrate solution in an equal volume manner for 6 hours, filtering, drying at the temperature of 110 ℃ for 10 hours, and roasting at the temperature of 650 ℃ for 4 hours.
Example 3
A preparation method of a modified Beta molecular sieve catalyst comprises the following steps:
(1) preparing Beta molecular sieve raw powder: firstly 3.28g of NaAlO as an aluminium source273.63g of template agent tetraethylammonium hydroxide, 16g of sodium hydroxide and 540g of deionized water are mixed and stirred uniformly, then 60.08g of silicon source silica sol is added into the mixed solution to form a uniform sol system, the sol system is aged for 2 hours at 80 ℃, then the sol system is put into a high-pressure reaction kettle, and the temperature is raised to 160 ℃ for crystallization for 36 hours; after hydrothermal crystallization, filtering, washing and drying, the Beta molecular sieve raw powder is obtained. The Beta molecular sieve raw powder has the relative crystallinity of not less than 80 percent and the specific surface area of 500-580 m2A pore volume of 0.25 to 0.50 cm/g3The mesoporous aperture is 4-15 nm;
(2) preparing the Mn-Co-Beta molecular sieve:
performing ion exchange treatment on Beta molecular sieve raw powder for 2 hours at the temperature of 100 ℃ by adopting ammonium nitrate with the mass concentration of 12%, wherein the liquid-solid ratio is 10: 1. Filtering, washing with water, and drying at 100 deg.C for 20 hr; then roasting for 5 hours at the temperature of 600 ℃ to obtain the deammoniated Beta molecular sieve;
weighing 4.15g of manganese nitrate, fully dissolving the manganese nitrate in deionized water to obtain a manganese nitrate solution, soaking the deammoniated Beta molecular sieve in the manganese nitrate solution for 8 hours in an equal volume, adding 2g of 0.08 mol/L ammonium carbonate solution while stirring, stirring uniformly, aging for 40min, filtering, drying at 120 ℃ for 3 hours, roasting at 700 ℃ for 3 hours, filtering, drying and roasting to obtain the manganese-loaded Beta molecular sieve;
weighing 1.344g of cobalt nitrate, fully dissolving the cobalt nitrate in deionized water to obtain a cobalt nitrate solution, soaking the manganese-loaded Beta molecular sieve in the cobalt nitrate solution for 8 hours in an equal volume, adding 1.5g of 0.05 mol/L ammonium carbonate solution while stirring, stirring uniformly, aging for 40min, filtering, drying at 120 ℃ for 3 hours, and roasting at 700 ℃ for 3 hours to obtain the Mn-Co-Beta molecular sieve.
(3) Preparing a Sn modified Mn-Co-Beta molecular sieve: and (3) fully dissolving 0.241g of tin nitrate in deionized water to obtain a tin nitrate solution, soaking the Mn-Co-Beta molecular sieve prepared in the step (2) in the tin nitrate solution in an equal volume manner for 8 hours, filtering, drying at the temperature of 120 ℃ for 3 hours, and roasting at the temperature of 700 ℃ for 3 hours.
Comparative example 1
This comparative example differs from example 2 in that no Sn modification step is employed and a Mn-Co-Beta molecular sieve is obtained.
Comparative example 2
This comparative example differs from example 2 in that the Beta molecular sieve raw powder used was obtained commercially.
Comparative example 3
This comparative example is different from example 2 in that the preparation of the Mn-Co-Beta molecular sieve was carried out without adding an ammonium carbonate solution and aging.
First, the catalytic performance test of the catalyst synthesized by the invention on SCR of NOx
And (3) carrying out activity test on the modified Beta molecular sieve catalyst prepared by the method on a catalyst activity evaluation device, wherein the test conditions are as follows: the temperature is 150 ℃ and 600 ℃, the reaction gas is simulated motor vehicle tail gas,wherein NO and NH3500ppm, 10% O2,10％H2O,N2In order to balance the gas, as a result, the reaction space velocity is 50000h-1The results are shown in Table 1.
Table 1 NOx conversion at different temperatures for the catalysts prepared in the examples and comparative examples
| Group of | 150℃ | 200℃ | 300℃ | 350℃ | 400℃ | 450℃ | 500℃ | 550℃ | 600℃ |
| Example 1 | 52 | 64 | 86 | 98 | 95 | 93 | 91 | 90 | 86 |
| Example 2 | 47 | 57 | 89 | 99 | 96 | 92 | 90 | 88 | 84 |
| Example 3 | 50 | 58 | 90 | 99 | 96 | 92 | 91 | 89 | 85 |
| Comparative example 1 | 20 | 29 | 56 | 88 | 92 | 90 | 86 | 71 | 62 |
| Comparative example 2 | 31 | 41 | 70 | 72 | 78 | 90 | 85 | 72 | 65 |
| Comparative example 3 | 44 | 52 | 80 | 89 | 90 | 89 | 89 | 80 | 71 |
As can be seen from the results in Table 1, the catalysts prepared in the examples of the present invention have better NOx conversion rate in the range of 150 ℃ and 600 ℃, while the comparative examples have narrower activity windows, which indicates that the catalysts prepared in the examples of the present invention have excellent catalytic activity by modification.
Second, anti-poisoning ability test
The modified Beta molecular sieve catalyst prepared by the method is subjected to activity test on a catalyst activity evaluation device under simulated flue gas conditions, wherein the flue gas conditions are NO and O2The volume fractions of (A) and (B) are respectively 0.1% and 5%, the ammonia-nitrogen ratio is 1:1, and CO is2Is 0.03% by volume, SO2Is 0.01% by volume, H2The volume fraction of O is 10%, N2The reaction space velocity is 50000h-1. The test results are shown in Table 2.
Table 2 NOx conversion over time for the catalysts prepared in the examples and comparative examples
As can be seen from the results in Table 2, the catalysts obtained in examples 1 to 3 contained CO2、H2O、SO2Still has better NH in the atmosphere3SCR catalytic performance, comparative example 1 is not modified by adding Sn, and the anti-toxicity performance is poor, so that the catalytic activity of the catalyst in the environment is influenced.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (8)
1. A preparation method of a modified Beta molecular sieve catalyst is characterized by comprising the following steps:
(1) preparing Beta molecular sieve raw powder: SiO of the prepared Beta molecular sieve raw powder framework2/Al2O3The molar ratio is 25-40, the relative crystallinity is not less than 80%, and the specific surface area is 500-580 m2A pore volume of 0.25 to 0.50 cm/g3The mesoporous aperture is 4-15 nm; the Beta molecular sieve raw powder is prepared by the following steps: firstly, the aluminum source NaAlO is added2Uniformly mixing and stirring template agents tetraethylammonium hydroxide, sodium hydroxide and deionized water, then adding silicon source silica sol into the mixed solution to form a uniform sol system, aging the sol system for 1-2 hours at the temperature of 60-80 ℃, then putting the sol system into a high-pressure reaction kettle, and heating to the temperature of 140-160 ℃ for crystallization for 36-72 hours; the molar composition of the synthetic raw material is SiO2：Al2O3: template agent: NaOH: h2O = 1.0: 0.025 to 0.04: 0.2-0.5: 0.2-0.4: 12-30, filtering, washing and drying after hydrothermal crystallization to obtain Beta molecular sieve raw powder;
(2) preparing a Mn-Co-Beta molecular sieve, wherein the molar ratio of Mn element to Co element in the Mn-Co-Beta molecular sieve is 5-8: 1, the mass of Mn element accounts for 10-13% of the mass of the Mn-Co-Beta molecular sieve, and the preparation method comprises the following specific steps of ① carrying out ion exchange treatment on Beta molecular sieve raw powder by adopting an ammonium salt solution, filtering, washing with water, drying and roasting to obtain a de-ammonium Beta molecular sieve, ② impregnating the de-ammonium Beta molecular sieve by adopting a manganese salt solution in an equal volume manner, then adding an ammonium carbonate solution under stirring, stirring uniformly, aging for 30-40 min, filtering, drying and roasting to obtain a manganese-loaded Beta molecular sieve, ③ impregnating the manganese-loaded Beta molecular sieve by adopting a cobalt salt solution in an equal volume manner, then adding an ammonium carbonate solution under stirring, aging for 30-40 min, filtering, drying and roasting to obtain the Mn-Co-Beta molecular sieve;
(3) preparing a Sn modified Mn-Co-Beta molecular sieve: and (3) soaking the Mn-Co-Beta molecular sieve prepared in the step (2) in a Sn salt solution in an equal volume, and drying and roasting to obtain the modified Beta molecular sieve catalyst, wherein the molar ratio of Sn element to manganese element is 1: 35-40.
2. The method of claim 1, wherein: in the step (3), soaking the Mn-Co-Beta molecular sieve in a Sn salt solution in an equal volume for 2-8 hours, wherein the drying condition is drying at 100-120 ℃ for 3-12 hours; the roasting condition is roasting for 3-5 hours at the temperature of 600-700 ℃.
3. The preparation method according to claim 1, wherein the ammonium salt used in the step ① is one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium dihydrogen phosphate and ammonium citrate, the ion exchange temperature is 85-100 ℃, the exchange time is 2-10 h, the mass concentration of the ammonium salt is 6-12%, and the liquid-solid ratio is 1: 1-10: 1.
4. The method according to claim 1, wherein the drying in step ① is performed at 60-100 ℃ for 5-20 hours, and the baking is performed at 500-600 ℃ for 3-5 hours.
5. The preparation method according to claim 1, wherein in the step ②, the equal-volume impregnation of the deammoniated Beta molecular sieve with a manganese salt solution is carried out for 2-8 hours, the drying is carried out at 100-120 ℃ for 3-12 hours, and the roasting is carried out at 600-700 ℃ for 3-5 hours.
6. The preparation method of claim 1, wherein in the step ③, the manganese-loaded Beta molecular sieve is impregnated with a cobalt salt solution in an equal volume for 2-8 hours under the drying condition of drying at 100-120 ℃ for 3-12 hours and under the roasting condition of roasting at 600-700 ℃ for 3-5 hours.
7. A modified Beta molecular sieve catalyst prepared by the preparation method of any one of claims 1-6.
8. The modified Beta molecular sieve catalyst prepared by the preparation method of any one of claims 1 to 6 and used for preparing a catalyst at low temperature NH3-use in SCR.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101992116A (en) * | 2009-08-10 | 2011-03-30 | 北京石油化工学院 | MnMe/molecular sieve series catalysts and preparation and application thereof |
| CN103386322A (en) * | 2012-05-08 | 2013-11-13 | 南京理工大学 | Fe-ZSM-5 catalyst used in NOx selective catalytic reduction, and preparation method thereof |
| CN103752352A (en) * | 2014-01-02 | 2014-04-30 | 上海大学 | Method for preparing denitrified catalyst through cobalt-manganese double-exchange molecular sieve |
| CN104190464A (en) * | 2014-08-04 | 2014-12-10 | 南昌大学 | Preparation method of Sn-based micropore molecular sieve NOx-SCR (selective catalytic reduction) catalyst |
| CN104229818A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Synthetic method of beta molecular sieve |
| CN104437604A (en) * | 2014-10-29 | 2015-03-25 | 复旦大学 | Mn-Ce-ZSM-11 catalyst as well as preparation method and application of Mn-Ce-ZSM-11 catalyst |
| CN105854932A (en) * | 2016-04-20 | 2016-08-17 | 东南大学 | Cu-Mn bimetallic composite type low-temperature denitration catalyst and preparation method thereof |
| CN106732755A (en) * | 2016-12-23 | 2017-05-31 | 中节能万润股份有限公司 | A kind of preparation method of the compound integral extruding type denitrating catalyst of molecular sieve multivariant oxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101294098B1 (en) * | 2010-03-11 | 2013-08-08 | 존슨 맛쎄이 퍼블릭 리미티드 컴파니 | DISORDERED MOLECULAR SIEVE SUPPORTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NOx |
-
2017
- 2017-10-23 CN CN201711004438.7A patent/CN107570205B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101992116A (en) * | 2009-08-10 | 2011-03-30 | 北京石油化工学院 | MnMe/molecular sieve series catalysts and preparation and application thereof |
| CN103386322A (en) * | 2012-05-08 | 2013-11-13 | 南京理工大学 | Fe-ZSM-5 catalyst used in NOx selective catalytic reduction, and preparation method thereof |
| CN104229818A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Synthetic method of beta molecular sieve |
| CN103752352A (en) * | 2014-01-02 | 2014-04-30 | 上海大学 | Method for preparing denitrified catalyst through cobalt-manganese double-exchange molecular sieve |
| CN104190464A (en) * | 2014-08-04 | 2014-12-10 | 南昌大学 | Preparation method of Sn-based micropore molecular sieve NOx-SCR (selective catalytic reduction) catalyst |
| CN104437604A (en) * | 2014-10-29 | 2015-03-25 | 复旦大学 | Mn-Ce-ZSM-11 catalyst as well as preparation method and application of Mn-Ce-ZSM-11 catalyst |
| CN105854932A (en) * | 2016-04-20 | 2016-08-17 | 东南大学 | Cu-Mn bimetallic composite type low-temperature denitration catalyst and preparation method thereof |
| CN106732755A (en) * | 2016-12-23 | 2017-05-31 | 中节能万润股份有限公司 | A kind of preparation method of the compound integral extruding type denitrating catalyst of molecular sieve multivariant oxide |
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