CN113070097A - NO for ammonia selective catalytic reductionxCopper-based catalyst and preparation method thereof - Google Patents

NO for ammonia selective catalytic reductionxCopper-based catalyst and preparation method thereof Download PDF

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CN113070097A
CN113070097A CN202110334958.4A CN202110334958A CN113070097A CN 113070097 A CN113070097 A CN 113070097A CN 202110334958 A CN202110334958 A CN 202110334958A CN 113070097 A CN113070097 A CN 113070097A
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copper
molecular sieve
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aluminum
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贺泓
杜金鹏
单玉龙
刘忠其
余运波
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Research Center for Eco Environmental Sciences of CAS
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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    • B01J29/00—Catalysts comprising molecular sieves
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    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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Abstract

The invention provides a method for selective catalytic reduction of NO by ammoniaxThe copper-based catalyst comprises a molecular sieve with the silicon-aluminum ratio less than or equal to 8 and a copper active component loaded on the molecular sieve, wherein the pore diameter of the molecular sieve is
Figure DDA0002997074350000011
The molecular sieve has small pore size and can provide a large number of ion exchange sites and acidic sites, and is NOxAnd NH3Provides good active sites for NH3The rapid progress of the SCR reaction has important promoting effects, and the catalyst is applied to the selective catalytic reduction of NO by ammoniaxIn addition, the efficiency of catalytic reduction can be improved, the temperature window can be widened, and the application prospect is wideIs wide.

Description

NO for ammonia selective catalytic reductionxCopper-based catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for ammoniaSelective catalytic reduction of NOxThe copper-based catalyst and the preparation method thereof.
Background
Nitrogen Oxides (NO)x) Is an important pollutant in the atmosphere and has important contribution to a series of atmospheric pollution phenomena such as acid rain, dust haze, photochemical smog and the like. In the existing NOxIn the removal technique, NH3Selective reduction (NH)3SCR) is NO purificationxThe most widely and effectively technical means are applied. The core of this technology is NH3-an SCR catalyst. In order to meet the treatment conditions of different tail gases or flue gases, NH3The SCR catalyst needs to have a wide denitration temperature window, good low-temperature catalytic performance, excellent hydrothermal stability, and the like.
Zeolite molecular sieve catalysts, especially small pore structure zeolites, due to their excellent NH3SCR activity and hydrothermal stability, which are widely appreciated by researchers. At present, the copper-based small-pore zeolite molecular sieve is the catalyst which is the most widely researched and has the most application prospect. The molecular sieve framework comprises Si, Al and O. Wherein, the frameworks Si and Al are linked by O atoms and extend to the space to form a tetrahedral structure.
CN106111183A discloses a catalyst for selective catalytic reduction of nitrogen oxides and a preparation method thereof, wherein the catalyst comprises a molecular sieve and a transition metal loaded on the molecular sieve, is prepared from the molecular sieve and a transition metal precursor, and is dried to remove adsorbed moisture; mixing the metal precursor with water, stirring and dissolving to prepare a solution; the prepared solution and the pretreated molecular sieve are stirred and mixed, and the catalyst for selectively catalyzing and reducing nitrogen oxide is obtained after standing, drying, calcining and cooling to normal temperature, but the application temperature of the catalyst is narrow.
CN104437608A discloses a catalyst for selective catalytic reduction of nitrogen oxides by ammonia, which comprises an active component Fe, a rare earth element promoter (La, Ce or Sm) and a molecular sieve support (Beta or a mixture of Beta and ZSM-5), but the composition of the catalyst is more complicated.
Therefore, it is necessary to developCan be suitable for ammonia selective catalytic reduction of NOxCopper-based catalyst of (3) to effect NOxHigh efficiency catalytic reduction.
Disclosure of Invention
In view of the problems of the prior art, the present invention provides a method for ammonia-selective catalytic reduction of NOxIs a molecular sieve support having a small pore size and capable of providing a large number of ion exchange sites and acid sites, is NOxAnd NH3Provides good active sites for NH3The rapid progress of the SCR reaction has important promoting effects, and the catalyst is applied to the selective catalytic reduction of NO by ammoniaxIn addition, the catalytic reduction efficiency can be improved, the active temperature window can be widened, and the application prospect is wide.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for the selective catalytic reduction of NO by ammoniaxThe copper-based catalyst comprises a molecular sieve with the silicon-aluminum ratio less than or equal to 8 and a copper active component loaded on the molecular sieve; the pore diameter of the molecular sieve is
Figure BDA0002997074330000021
The invention provides a method for ammonia selective catalytic reduction of NOxThe copper-based catalyst adopts a molecular sieve with small aperture and selects an aluminum-rich molecular sieve, wherein the small-aperture silicon-aluminum molecular sieve has excellent NH3SCR activity and hydrothermal stability, the steric tetrahedral structure consisting of 3 electrons in the outermost Al atom and 4O centered on Al, requiring charge compensation due to lack of positive charge when it is H+When compensated, forms at that site
Figure BDA0002997074330000022
Acidic sites, also ion exchange sites; when transition metal ions are used for charge compensation, the site is usually used as an active site for chemical reaction, and more Al sites in the aluminum-rich molecular sieve can provide more acidic sites and ion exchange sites; furthermore, it is possible to provide a liquid crystal display device,the Al-rich zeolite contains a large number of adjacent para Al sites which can lead the transition metal Cu2+Form stronger bidentate structure (Cu) with molecular sieve2+2Z, Z representing the negative backbone charge), thus greatly improving the (hydro) thermal stability of the Cu species.
NO described in the present inventionxWherein x comprises 1, 2 or 2.5, etc., formula NOxRefers to a wide range of nitrogen oxides.
The molecular sieve of the present invention has a silica/alumina ratio of 8 or less, and may be, for example, 1, 1.8, 2.0, 2.6, 3.0, 3.4, 4.0, 4.2, 4.9, 5.0, 5.7, 6.0, 6.5, 7.0, 7.3 or 8, but is not limited to the values listed, and other values not listed in the range are also applicable.
The molecular sieve of the invention has a pore diameter of
Figure BDA0002997074330000031
For example, can be
Figure BDA0002997074330000032
Figure BDA0002997074330000033
Or
Figure BDA0002997074330000034
And the like, but are not limited to the recited values, and other values not recited within the range are equally applicable.
Preferably, the configuration of the molecular sieve comprises any one of CHA, AEI, KFI, RTH, ERI, LTA, RHO, SFW or ITE, preferably CHA, AEI or KFI.
Preferably, the copper-based catalyst has a silicon to aluminum ratio of 2 to 8, and may be, for example, 2, 2.5, 2.9, 3.0, 3.4, 3.8, 4.0, 4.3, 4.7, 5.0, 5.2, 5.6, 6, 6.5, 6.8, 7, 7.2, 7.5 or 8, but not limited to the values recited, and other values not recited in this range are also applicable.
The silicon-aluminum ratio is preferably between 2 and 6, and the catalyst has better reaction activity and catalytic reaction effect.
Preferably, the copper-based catalyst has a copper loading of 0.1 to 10%, for example, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, but not limited to the recited values, and other values not recited in this range are also applicable.
In a second aspect, the present invention provides the method of the first aspect for ammonia-selective catalytic reduction of NOxWhen the configuration of the molecular sieve is CHA, the preparation method comprises the following steps:
(1) mixing an aluminum source and a copper source, sequentially adding a template agent, an alkali source and silica sol, and carrying out crystallization reaction at 100-140 ℃ to obtain a crystallized product;
(2) and sequentially carrying out primary roasting at 500-700 ℃, acid treatment and secondary roasting at 550-750 ℃ on the crystallized product to obtain the Cu-CHA molecular sieve.
The CHA-type molecular sieve is preferably synthesized by adopting the steps, so that one-step synthesis of copper and the molecular sieve is realized, copper can be more firmly loaded on the CHA-type molecular sieve, and the hydrothermal stability of the catalyst is more favorably improved.
In the present invention, the temperature of the crystallization reaction is 100 to 140 ℃, and may be, for example, 100 ℃, 105 ℃, 109 ℃, 114 ℃, 118 ℃, 123 ℃, 127 ℃, 132 ℃, 136 ℃, 140 ℃ or the like, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the molar ratio of copper in the copper source and aluminum in the aluminum source in step (1) is 0.2 to 1.0:1, and may be, for example, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1.0:1, but is not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, the molar ratio of the alkali source to the aluminum source is 1.0 to 2.0:1, and may be, for example, 1.0:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2.0:1, but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the alkali source is sodium hydroxide.
Preferably, the aluminum source is sodium metaaluminate.
Preferably, the molar ratio of the templating agent to the aluminum source is 0.2 to 1.0:1, for example, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, or 1.0:1, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the templating agent comprises tetraethylenepentamine.
Preferably, the mass ratio of the silica sol to the aluminum source is 0.05 to 0.5:1, and may be, for example, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1 or 0.5:1, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
Preferably, the silica sol is added as an aqueous silica sol solution.
Preferably, the silica sol aqueous solution contains 25 to 35 wt% of silica sol, for example, 25 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, etc., but not limited to the above-mentioned values, and other values not listed in this range are also applicable.
Preferably, step (1) comprises: dissolving an aluminum source in water, adding a copper source, stirring and mixing for the first time, then dropwise adding a template agent, then adding an alkali source, stirring and mixing for the second time, and then adding silica sol.
Preferably, the crystallization reaction is carried out for 1 to 10 days, for example, 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, or 10 days, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the crystallized product in the step (2) is washed and dried and then roasted again.
Preferably, the time period of the primary baking is 3 to 12 hours, for example, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the acid treated acid is nitric acid.
Preferably, the nitric acid concentration is 0.01 to 2mol/L, for example, 0.01mol/L, 0.05mol/L, 0.27mol/L, 0.49mol/L, 0.7mol/L, 0.92mol/L, 1.14mol/L, 1.35mol/L, 1.57mol/L, 1.79mol/L, or 2mol/L, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the acid-treated sample is washed and dried again and then subjected to secondary roasting.
Preferably, the time period of the secondary baking is 3 to 12 hours, for example, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
In a third aspect, the present invention provides the method of the first aspect for ammonia-selective catalytic reduction of NOxWhen the configuration of the molecular sieve is AEI, the preparation method comprises the following steps:
(1) mixing a Y-type molecular sieve and a template agent, stirring and mixing for the first time, adding an alkali source, stirring and mixing for the second time, and carrying out crystallization reaction at 100-160 ℃ to obtain a crystallized product;
(2) roasting the crystallized product for one time to obtain a roasted product;
(3) and carrying out primary reaction on the roasted product and an ammonia source solution, carrying out secondary reaction on a solid-phase product obtained by the primary reaction and a copper source solution, and roasting a secondary reaction product to obtain the Cu-AEI molecular sieve.
When the molecular sieve configuration of the catalyst is AEI, the steps are preferably adopted, the preparation of the AEI type molecular sieve is realized by taking the Y molecular sieve as a silicon source and an aluminum source and performing structural transformation, and the preparation of the Cu-AEI molecular sieve is realized by an ion exchange mode, wherein the AEI configuration has better reaction activity for ammonia catalytic reduction reaction.
In the present invention, when the molecular sieve configuration is AEI, the crystallization reaction temperature is 100 to 160 ℃, and may be, for example, 100 ℃, 107 ℃, 114 ℃, 120 ℃, 127 ℃, 134 ℃, 140 ℃, 147 ℃, 154 ℃, or 160 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the mass ratio of the template to the Y-type molecular sieve in step (1) is 0.1 to 1.0:1, and may be, for example, 0.1:1, 0.15:1, 0.19:1, 0.24:1, 0.28:1, 0.33:1, 0.37:1, 0.42:1, 0.46:1, 0.5:1, 0.6:1, 0.8:1, 0.9:1 or 1.0:1, but not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the mass ratio of the alkali source to the Y-type molecular sieve is 0.1 to 1.0:1, and may be, for example, 0.1:1, 0.15:1, 0.20:1, 0.24:1, 0.30:1, 0.42:1, 0.46:1, 0.5:1, 0.6:1, 0.8:1, 0.9:1, or 1.0:1, but is not limited to the above-mentioned values, and other values not specifically mentioned in this range are also applicable.
Preferably, the crystallization reaction is carried out for a period of time of 2h to 10 days, for example, 2h, 5h, 1 day, 1.5 days, 2.0 days, 3.0 days, 4.0 days, 5 days, 6 days, 7 days, 8 days, 9 days, or 10 days, etc., but not limited to the enumerated values, and other values not enumerated within this range are also applicable.
Preferably, the crystallized product in the step (2) is washed and dried and then roasted again.
Preferably, the temperature of the primary baking is 600 to 850 ℃, for example, 600 ℃, 660 ℃, 695 ℃, 700 ℃, 710 ℃, 740 ℃, 750 ℃, 800 ℃, 820 ℃, 850 ℃ and the like, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the time period of the primary baking is 1 to 20 hours, and for example, 1 hour, 3 hours, 4 hours, 6 hours, 7.4 hours, 8 hours, 9 hours, 10 hours, 12 hours, 15 hours, 18 hours or 20 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the concentration of the ammonia source solution in step (3) is 0.001-10 mol/L, for example, 0.001mol/L, 0.005mol/L, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.5mol/L, 0.6mol/L, 1.0mol/L, 2mol/L, 4mol/L, 5mol/L, 8mol/L or 10mol/L, etc., but not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the concentration of the copper source solution is 0.001 to 10mol/L, and may be, for example, 0.001mol/L, 0.02mol/L, 0.05mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 8mol/L or 10mol/L, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the temperature of the secondary baking is 400 to 800 ℃, for example, 400 ℃, 420 ℃, 450 ℃, 480 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 680 ℃, 700 ℃, 720 ℃, 750 ℃ or 800 ℃ and the like, but not limited to the recited values, and other values not recited in the range are also applicable.
In a fourth aspect, the present invention provides the method of the first aspect for ammonia-selective catalytic reduction of NOxWhen the configuration of the molecular sieve is KFI, the method comprises the following steps:
(1) mixing an aluminum source, an alkali source and potassium salt, sequentially adding silica sol and seed crystal, and carrying out crystallization reaction at 100-150 ℃ to obtain a crystallization product;
(2) and sequentially carrying out washing, ammonia source solution ion exchange and copper source solution ion exchange on the crystallized product, and roasting a solid-phase product after the copper source solution ion exchange to obtain the Cu-KFI molecular sieve.
When the configuration of the molecular sieve is KFI, the steps are adopted, so that the quantity of active sites of the molecular sieve is increased, and the catalytic activity is improved.
In the present invention, when the molecular sieve has a KFI configuration, the crystallization reaction temperature is 100 to 150 ℃, and for example, 100 ℃, 106 ℃, 112 ℃, 117 ℃, 123 ℃, 128 ℃, 134 ℃, 139 ℃, 145 ℃ or 150 ℃ may be used, but the present invention is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the molar ratio of the alkali source to the aluminum source in step (1) is 0.1 to 1:1, and may be, for example, 0.1:1, 0.12:1, 0.13:1, 0.14:1, 0.15:1, 0.2:1, 0.25:1, 0.4:1, 0.45:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1 or 1:1, but not limited to the above-mentioned values, and other values not listed in this range may be similarly applied.
Preferably, the molar ratio of the potassium salt to the aluminum source is 1 to 10:1, and may be, for example, 1:1, 2:1, 3:1, 4:1, 5.0:1, 6:1, 7:1, 8:1, 9:1, 9.5:1, or 10:1, but is not limited to the recited values, and other values not recited in this range are also applicable.
The mass ratio of the silica sol to the aluminum source is preferably 1 to 20:1, and may be, for example, 1:1, 5:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 15:1, 18:1 or 20:1, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the mass ratio of the seed crystal to the aluminum source is 0.001 to 1:1, and may be, for example, 0.001:1, 0.1:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.6:1, 0.8:1 or 1:1, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
Preferably, the mixing of step (1) comprises: mixing an aluminum source and an alkali source, stirring and mixing, adding a potassium salt, and stirring and mixing.
Preferably, the crystallization reaction is carried out for a period of time of 2h to 10 days, for example, 2h, 12h, 1 day, 1.5 days, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, or 10 days, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the molar concentration of the ammonia source solution is 0.001 to 10mol/L, and may be, for example, 0.001mol/L, 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.7mol/L, 0.8mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 8mol/L, or 10mol/L, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the molar concentration of the copper source solution is 0.001 to 10mol/L, and may be, for example, 0.001mol/L, 0.1mol/L, 0.15mol/L, 0.24mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 8mol/L, or 10mol/L, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the method also comprises the washing of solid-phase products after the ion exchange of the copper source solution between the ion exchange of the ammonia source solution and the ion exchange of the copper source solution.
Preferably, the temperature of the baking is 500 to 800 ℃, for example, 500 ℃, 600 ℃, 623 ℃, 645 ℃, 667 ℃, 689 ℃, 712 ℃, 734 ℃, 756 ℃, 778 ℃ or 800 ℃ and the like, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the duration of the calcination is 1 to 20 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 10 hours, 15 hours or 20 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) according to the copper-based catalyst provided by the invention, copper has the function of the catalyst, and the molecular sieve contains a large number of active sites, so that the adsorption and oxidation effects on ammonia and nitrogen oxides are improved;
(2) the molecular sieve of the copper-based catalyst provided by the invention is a small-aperture molecular sieve, so that the hydrothermal stability of the catalyst is improved;
(3) the copper-based catalyst provided by the invention is applied to selective catalytic reduction of NO by ammoniaxWhen it is NO, itsxThe conversion rate of 200 ℃ can reach more than 90 percent, the catalyst has strong water-proof thermal property, and NO is treated by hydrothermal treatmentxThe conversion rate can still reach more than 85 percent at 200 ℃, the catalytic activity and the selectivity are high, and NO is generated by adopting a Cu-CHA catalystxThe conversion rate reaches more than 90 percent at 200 ℃, can reach more than 99 percent under better conditions, and NO is treated by hydrothermal treatmentxThe conversion rate can reach more than 95 percent at 200 ℃ under better conditions; NO when Cu-AEI catalyst is usedxThe conversion rate reaches more than 90 percent at 200 ℃, can reach more than 96 percent under better conditions, and NO is treated by hydrothermal treatmentxThe conversion rate can reach more than 93 percent at 200 ℃ under better conditions.
Drawings
FIG. 1 shows the use of a copper-based catalyst for NH in examples 1 to 3 of the present invention3-catalytic effect diagram of SCR reaction.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
First, an embodiment
Example 1
The embodiment provides a Cu-CHA catalyst, wherein a copper-based catalyst of the Cu-CHA comprises a CHA molecular sieve with a silicon-aluminum ratio of 4.2 and a copper active component loaded on the CHA molecular sieve; the pore diameter of the molecular sieve is
Figure BDA0002997074330000101
The loading of copper in the copper-based catalyst was 4.0 wt.%.
This embodiment also provides a preparation method of the Cu-CHA catalyst, the preparation method comprising the steps of:
(1) 1.542g NaAlO was first added2Completely dissolved in 14.166g H2To O, 2.298g of CuSO were then added4·5H2O, stirring for 1h, then adding TEPA 2.139g dropwise, then adding 1.1g NaOH, stirring for another 3h, then adding 10mL of silica sol (30 wt%); putting the completely mixed gel into a 100mL hydrothermal reaction kettle, and carrying out crystallization reaction at 120 ℃ for 5 days to obtain a crystallized product;
(2) carrying out suction filtration on the crystallized product by using deionized water, washing, then putting the crystallized product into a drying oven at 100 ℃ for drying for 12 hours, and then putting the product into a muffle furnace for roasting at 600 ℃ for 6 hours; in the post-treatment, the sample was placed in 0.1M HNO3And (3) treating the solution at 80 ℃ for 12h, carrying out suction filtration, washing and drying on the treated sample, and roasting the sample in a muffle furnace at 600 ℃ for 6h to obtain the Cu-CHA molecular sieve.
Example 2
The embodiment provides a Cu-AEI catalyst, wherein the Cu-AEI copper-based catalyst comprises an AEI molecular sieve with the silicon-aluminum ratio of 7.3 and a copper active component loaded on the AEI molecular sieve; the pore diameter of the molecular sieve is
Figure BDA0002997074330000111
The loading of copper in the copper-based catalyst was 2.8 wt.%.
The present embodiment also provides a preparation method of the Cu-AEI catalyst, which comprises the following steps:
(1) firstly, 3gY molecular sieve is dissolved in 25.5gH2To O, 4.5g1,1,3, 5-tetramethylpiperidine solution (20 wt.%) was then added, and after stirring for 3h, 0.75g NaOH was added, and stirring was continued for 5 h. Putting the completely mixed solution into a 100mL hydrothermal reaction kettle, and carrying out crystallization reaction at 140 ℃ for 3 days to obtain a crystallized product;
(2) performing suction filtration on the crystallized product by using deionized water, washing, then putting the crystallized product into a drying oven at 100 ℃ for drying for 12 hours, and then putting the product into a muffle furnace for roasting at 700 ℃ for 6 hours to obtain a roasted product;
(3) 1g of the calcined product was taken and dissolved in 100mL of 0.05M NH4Stirring in a water bath at 80 ℃ for 5 hours in a Cl solution to perform primary reaction, performing secondary reaction on the primary reaction, performing suction filtration, and drying to obtain NH4-SSZ-39 powder; then 1g of NH4-SSZ-39 powder dissolved in 100mL of 0.2M Cu (NO)3)2Stirring the solution at room temperature for 12 hours, filtering, drying, and roasting in a muffle furnace at 600 ℃ for 6 hours to obtain the Cu-AEI molecular sieve with the silicon-aluminum ratio of 7.3.
Example 3
The embodiment provides a Cu-KFI catalyst, wherein the Cu-based catalyst of the Cu-KFI comprises a KFI molecular sieve with a silicon-aluminum ratio of 4.2 and a copper active component loaded on the KFI molecular sieve; the pore diameter of the molecular sieve is
Figure BDA0002997074330000112
The loading of copper in the copper-based catalyst was 3.0 wt.%.
This example also provides a preparation method of the Cu-KFI catalyst, including the following steps:
(1) first 0.327g of sodium aluminate (NaAlO)2) Adding into 3.8g deionized water, stirring and mixing uniformly; adding 0.05g of sodium hydroxide (NaOH), and stirring for 1 hour; adding 2.5g potassium nitrate (KNO)3) Stirring for 1 hour; addition of 32g of silica sol, and stirring for 24 hours; 0.05g of seed crystals were added and stirred for 1 hour. Putting the obtained solution into a reaction kettle, and carrying out crystallization reaction for 3 days at 140 ℃ to obtain a crystallized product;
(2) the crystallized product was washed 6 times with deionized water and dried at 100 ℃ for 12h, the dried solid was ground with 0.5M ammonium chloride (NH)4Cl) carrying out ion exchange on the ammonia source solution for 5 hours at 80 ℃ for 4 times, washing the obtained solid with deionized water for more than 5 times, and drying at 100 ℃ for 12 hours;
the solid obtained by the ion exchange of the ammonia source solution is 0.2M Cu (NO)3)2Carrying out copper source ion exchange for 5h at 40 ℃ on the solution, washing the obtained solid-phase product with deionized water for more than 5 times, and drying for 12h at 100 ℃; and roasting the dried solid-phase product in a muffle furnace at 700 ℃ for 6h (the heating rate is 10 ℃/min) to obtain the Cu-KFI molecular sieve with the silicon-aluminum ratio of 4.2.
The catalysts obtained in examples 1 to 3 were used as examples, and they were applied to NH3-SCR test, test conditions: [ NO ]]＝[NH3]＝500ppm，[O2]＝[H2O]＝5％,N2Balance, volume airspeed 200000h-1. The catalytic efficiency at different temperatures is shown in FIG. 1, and it can be seen from FIG. 1 that the catalysts provided in examples 1 to 3 can achieve 90% NO at 250 ℃xThe conversion rate is high, and the Cu-CHA molecular sieve and the Cu-AEI molecular sieve can reach 90 percent of NO at 200 DEG CxThe conversion rate and the denitration temperature window are further widened.
Example 4
The embodiment provides a Cu-CHA catalyst, wherein a copper-based catalyst of the Cu-CHA comprises a CHA molecular sieve with a silicon-aluminum ratio of 4.2 and a copper active component loaded on the CHA molecular sieve; the pore diameter of the molecular sieve is
Figure BDA0002997074330000121
The loading of copper in the copper-based catalyst was 3.8 wt.%.
This embodiment also provides a preparation method of the Cu-CHA catalyst, the preparation method comprising the steps of:
(1) 0.8242g NaAlO was first added2Completely dissolved in 12.234g H2To O, 2.2723g of CuSO were then added4·5H2O, stirring for 2h, then adding TEPA0.5326g dropwise, then adding 0.8g NaOH, stirring for another 6h, then adding 9mL of silica sol (25 wt%); putting the completely mixed gel into a 90mL hydrothermal reaction kettle, and carrying out crystallization reaction at 100 ℃ for 7 days to obtain a crystallized product;
(2) carrying out suction filtration on the crystallized product by using deionized water, washing, then putting the crystallized product into a 90 ℃ oven for drying for 8h, and then putting the product into a muffle furnace for roasting for 3h at 700 ℃; in the post-treatment, the sample was placed in 0.05M HNO3And (3) treating the solution at 60 ℃ for 24h, carrying out suction filtration, washing and drying on the treated sample, and roasting the sample in a muffle furnace at 750 ℃ for 3h to obtain the Cu-CHA molecular sieve.
Example 5
The embodiment provides a Cu-CHA catalyst, wherein a copper-based catalyst of the Cu-CHA comprises a CHA molecular sieve with a silicon-aluminum ratio of 5.2 and a copper active component loaded on the CHA molecular sieve; the pore diameter of the molecular sieve is
Figure BDA0002997074330000131
The loading of copper in the copper-based catalyst was 3.0 wt.%.
This embodiment also provides a preparation method of the Cu-CHA catalyst, the preparation method comprising the steps of:
(1) 1.2385g NaAlO was first added2Completely dissolved in 12.3568g H2To O, 2.272g of CuSO were then added4·5H2O, stirring for 2.3h, then adding TEPA2.7632g dropwise, then adding 0.63g NaOH, stirring for 2.5h, then adding 12mL of silica sol (35 wt%); putting the completely mixed gel into a 100mL hydrothermal reaction kettle, and carrying out crystallization reaction at 140 ℃ for 3 days to obtain a crystallized product;
(2) carrying out suction filtration on the crystallized product by using deionized water, washing, then putting the crystallized product into a 110 ℃ drying oven for drying for 10h, and then putting the product into a muffle furnace for roasting for 12h at 500 ℃; in the post-treatment, the sample was placed in 2M HNO3And (3) treating the solution at 90 ℃ for 6h, carrying out suction filtration, washing and drying on the treated sample, and roasting the sample in a muffle furnace at 550 ℃ for 12h to obtain the Cu-CHA molecular sieve.
Example 6
The embodiment provides a Cu-AEI catalyst, wherein the Cu-AEI copper-based catalyst comprises an AEI molecular sieve with a silicon-aluminum ratio of 4.2 and a copper active component loaded on the AEI molecular sieve; the pore diameter of the molecular sieve is
Figure BDA0002997074330000141
The loading of copper in the copper-based catalyst was 3.3 wt.%.
The present embodiment also provides a preparation method of the Cu-AEI catalyst, which comprises the following steps:
(1) firstly, 3gY molecular sieve is dissolved in 20.6g H2To O, 1.5g of 1,1,3, 5-tetramethylpiperidine solution (25 wt.%) was then added and stirred for 1h, followed by addition of 0.3g NaOH and stirring continued for 10 h. Putting the completely mixed solution into a 100mL hydrothermal reaction kettle, and carrying out crystallization reaction at 160 ℃ for 1 day to obtain a crystallized product;
(2) carrying out suction filtration on the crystallized product by using deionized water, washing, then putting the crystallized product into a 90 ℃ oven for drying for 14h, and then putting the product into a muffle furnace for roasting at 750 ℃ for 4h to obtain a roasted product;
(3) 1g of the calcined product was taken and dissolved in 80mL of 0.09M NH4Stirring in a water bath at 90 ℃ for 2h in a Cl solution to perform a primary reaction, performing the primary reaction twice, performing suction filtration, and drying to obtain NH4-SSZ-39 powder; then 1g of NH4-SSZ-39 powder dissolved in 120mL of 0.1M Cu (NO)3)2Stirring the solution for 24 hours at room temperature (22 ℃), filtering, drying, and roasting in a muffle furnace for 4 hours at 650 ℃ to obtain the Cu-AEI molecular sieve.
Example 7
The embodiment provides a Cu-AEI catalyst, wherein the Cu-AEI copper-based catalyst comprises an AEI molecular sieve with the silicon-aluminum ratio of 5.6 and a copper active component loaded on the AEI molecular sieve; the pore diameter of the molecular sieve is
Figure BDA0002997074330000142
The loading of copper in the copper-based catalyst was 2.8 wt.%.
The present embodiment also provides a preparation method of the Cu-AEI catalyst, which comprises the following steps:
(1) firstly, 3gY molecular sieve is dissolved in 12.8g H2To O, 4.5g of 1,1,3, 5-tetramethylpiperidine solution (30 wt%) was added, and after stirring for 5 hours, 1.5g of NaOH was added and stirring was continued for 3 hours. Putting the completely mixed solution into a 90mL hydrothermal reaction kettle, and carrying out crystallization reaction at 100 ℃ for 5 days to obtain a crystallized product;
(2) performing suction filtration on the crystallized product by using deionized water, washing, then putting the crystallized product into a 120 ℃ drying oven for drying for 8h, and then putting the product into a muffle furnace for roasting at 650 ℃ for 10h to obtain a roasted product;
(3) taking 1g of the roasted product, dissolving in 120mL of 0.02M NH4Stirring in a water bath at 60 ℃ for 10 hours in a Cl solution to perform primary reaction, performing secondary reaction on the primary reaction, performing suction filtration, and drying to obtain NH4-SSZ-39 powder; then 1g of NH4-SSZ-39 powder dissolved in 120mL of 0.5M Cu (NO)3)2Stirring the solution at room temperature (35 ℃) for 9 hours, filtering, drying, and roasting the solution in a muffle furnace at 550 ℃ for 4 hours to obtain the Cu-AEI molecular sieve.
Example 8
The embodiment provides a Cu-KFI catalyst, wherein the Cu-based catalyst of the Cu-KFI comprises a KFI molecular sieve with a silicon-aluminum ratio of 5.2 and a copper active component loaded on the KFI molecular sieve; the pore diameter of the molecular sieve is
Figure BDA0002997074330000151
The loading of copper in the copper-based catalyst was 2.8 wt.%.
This example also provides a preparation method of the Cu-KFI catalyst, including the following steps:
(1) first 0.327g of sodium aluminate (NaAlO)2) Adding into 4.0g deionized water, stirring to mix well; adding 0.02g of sodium hydroxide (NaOH), and stirring for 2 hours; 3.9g potassium nitrate (KNO) was added3) Stirring for 6 hours; adding 2.6g of silica sol, and stirring for 12 hours; 0.04g of seed crystal was added thereto, and the mixture was stirred for 3 hours. Putting the obtained solution into a reaction kettle, and carrying out crystallization reaction for 1 day at 150 ℃ to obtain a crystallized product;
(2) the crystallized product was washed 8 times with deionized water and thenDrying at 110 deg.C for 10h, grinding the dried solid, and adding 1M ammonium chloride (NH)4Cl) performing ion exchange on the ammonia source solution for 7 times at 90 ℃ for 8h, washing the obtained solid with deionized water for 10 times, and drying for 16h at 90 ℃;
the solid obtained by the ion exchange of the ammonia source solution is 0.5M Cu (NO)3)2Carrying out copper source ion exchange for 7h at 50 ℃ on the solution, washing the obtained solid-phase product for 6 times by using deionized water, and drying for 8h at 120 ℃; and (3) roasting the dried solid-phase product in a muffle furnace at 800 ℃ for 3h (the heating rate is 12 ℃/min) to obtain the Cu-KFI molecular sieve.
Example 9
The embodiment provides a Cu-KFI catalyst, wherein the Cu-based catalyst of the Cu-KFI comprises a KFI molecular sieve with a silicon-aluminum ratio of 4.7 and a copper active component loaded on the KFI molecular sieve; the pore diameter of the molecular sieve is
Figure BDA0002997074330000161
The loading of copper in the copper-based catalyst was 3.0 wt.%.
This example also provides a preparation method of the Cu-KFI catalyst, including the following steps:
(1) first 0.327g of sodium aluminate (NaAlO)2) Adding into 3.5g deionized water, stirring and mixing uniformly; adding 0.07g of sodium hydroxide (NaOH), and stirring for 1 hour; adding 2.1g potassium nitrate (KNO)3) Stirring for 1 hour; adding 3.8g of silica sol, and stirring for 28 hours; 0.16g of seed crystals were added and stirred for 0.5 h. Putting the obtained solution into a reaction kettle, and carrying out crystallization reaction for 5 days at 100 ℃ to obtain a crystallized product;
(2) the crystallized product was washed 5 times with deionized water and dried at 100 ℃ for 12h, the dried solid was ground with 0.5M ammonium chloride (NH)4Cl) carrying out ion exchange on the ammonia source solution for 5h at 60 ℃ for 4 times, washing the obtained solid with deionized water for 9 times, and drying at 100 ℃ for 12 h;
the solid obtained by the ion exchange of the ammonia source solution is 0.2M Cu (NO)3)2Carrying out copper source ion exchange for 5h at 40 ℃ on the solution, washing the obtained solid-phase product with deionized water for more than 5 times, and drying for 12h at 100 ℃; dried solid phaseAnd roasting the product in a muffle furnace at 700 ℃ for 6h (the heating rate is 10 ℃/min), thus obtaining the Cu-KFI molecular sieve with the silicon-aluminum ratio of 4.2.
Example 10
This example provides a Cu-CHA catalyst, which is the same as example 1 except that the Cu-CHA copper-based catalyst comprises a CHA molecular sieve having a Si/Al ratio of 7.6, and is prepared in a manner similar to example 1.
Example 11
This example provides a Cu-AEI catalyst, which is the same as example 2 except that the Cu-AEI copper-based catalyst comprises an AEI molecular sieve having a Si/Al ratio of 7.9, and is prepared in a manner similar to example 1.
Example 12
This example provides a Cu-CHA catalyst, which is the same as example 1 except that the Cu-CHA copper-based catalyst comprises a CHA molecular sieve having a Si/Al ratio of 7.8, and is prepared in a manner similar to example 1.
Second, comparative example
Comparative example 1
This comparative example provides a Cu-CHA catalyst, which is the same as example 1 except that the Cu-AEI copper-based catalyst comprises a CHA molecular sieve having a silica to alumina ratio of 9.0, and which was prepared in a manner similar to example 1.
Comparative example 2
This comparative example provides a Cu-CHA catalyst, which is the same as example 2 except that the Cu-AEI copper-based catalyst comprises an AEI molecular sieve having a silicon to aluminum ratio of 8.3, and is prepared in a manner similar to example 2.
Comparative example 3
This comparative example provides a Cu-CHA catalyst, which is the same as example 3 except that the Cu-KFI copper-based catalyst comprises a KFI molecular sieve having a silicon to aluminum ratio of 9.2, and is prepared in a manner similar to example 3.
Third, test and results
The test method comprises the following steps: the catalysts of the above examples and comparative examples were used to apply them to NH3-SCR test, test conditions: [ NO ]]＝[NH3]＝500ppm，[O2]＝[H2O]＝5％，N2Balance, volume airspeed 200000h-1. No at different temperaturesxThe catalytic efficiency of (a) is shown in table 1.
The copper-based catalysts of the above examples and comparative examples were subjected to hydrothermal treatment at 750 ℃ for 16 hours, and then the catalytic effects thereof were tested in the above manner, and the results are shown in table 1.
TABLE 1
Figure BDA0002997074330000171
Figure BDA0002997074330000181
From table 1, the following points can be seen:
(1) it can be seen from the comprehensive examples 1 to 12 that the copper-based catalyst provided by the invention has small pore diameter, can provide a large amount of ion exchange sites and acid sites, and is NOxAnd NH3Provides good active sites for adsorption of NOxThe conversion rate of 200 ℃ can reach more than 90 percent, the catalyst has strong water-proof thermal property, and NO is treated by hydrothermal treatmentxThe conversion rate can still reach more than 85 percent at 200 ℃;
(2) by combining example 1 with comparative example 1, it can be seen that the CHA molecular sieve with a Si/Al ratio of 4.2 in example 1 has NO in example 1 compared to the CHA molecular sieve with a Si/Al ratio of 9.0 in comparative example 1xThe conversion rate can reach 99% at 200 ℃, and NO is treated by hydrothermal treatmentxThe conversion rate of 200 ℃ can reach 98 percent, compared with NO in comparative example 1xThe conversion rate is only 70 percent at 200 ℃, and NO is treated by hydrothermal treatmentxThe conversion rate of 200 ℃ is reduced to 68%, and the results of integrating example 2 and comparative example 2, and integrating example 3 and comparative example 3 have similar data, thereby showing that the invention remarkably improves NO by controlling the silicon-aluminum ratio of the molecular sieve in a specific rangexConversion rate and broadens the temperature window;
(3) as can be seen by combining example 1, example 10 and example 12, the silica to alumina ratio of the molecular sieve in example 1 is 4.2, phaseNO in example 1 compared to 7.6 and 7.8 for the molecular sieves in examples 10 and 12, respectivelyxThe conversion rate can reach 99% at 200 ℃, and NO is treated by hydrothermal treatmentxThe conversion rate of 200 ℃ can reach 98 percent, while the NO in example 10 and example 12xThe conversion rate is 90 percent at 200 ℃, and NO is treated by hydrothermal treatmentxThe conversion rate of 200 ℃ is reduced to 88%, and the results of integrating the example 2 and the example 11 also have similar data, thereby showing that the invention further improves NO by further controlling the silicon-aluminum ratio of the molecular sieve within a specific rangexConversion rate and broadens the temperature window.
In conclusion, the catalyst is used for the selective catalytic reduction of NO by ammoniaxThe copper-based catalyst can be NOxAnd NH3Provides good active sites for adsorption of NOxThe conversion rate of 200 ℃ can reach more than 90 percent, the catalyst has strong water-proof thermal property, and NO is treated by hydrothermal treatmentxThe conversion rate can still reach more than 85 percent at 200 ℃, the conversion rate is high, and the temperature window is wide.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. NO for ammonia selective catalytic reductionxThe copper-based catalyst is characterized by comprising a molecular sieve with the silicon-aluminum ratio less than or equal to 8 and a copper active component loaded on the molecular sieve;
the pore diameter of the molecular sieve is
Figure FDA0002997074320000011
2. Copper-based catalyst according to claim 1, characterized in that the configuration of the molecular sieve comprises any of CHA, AEI, KFI, RTH, ERI, LTA, RHO, SFW or ITE;
preferably, the silicon-aluminum ratio of the copper-based catalyst is 2-8;
preferably, the loading amount of copper in the copper-based catalyst is 0.1-10%.
3. The process of claim 1 or 2 for ammonia-selective catalytic reduction of NOxThe preparation method of the copper-based catalyst is characterized in that when the configuration of the molecular sieve is CHA, the preparation method comprises the following steps:
(1) mixing an aluminum source and a copper source, sequentially adding a template agent, an alkali source and silica sol, and carrying out crystallization reaction at 100-140 ℃ to obtain a crystallized product;
(2) and sequentially carrying out primary roasting at 500-700 ℃, acid treatment and secondary roasting at 550-750 ℃ on the crystallized product to obtain the Cu-CHA molecular sieve.
4. The production method according to claim 3, wherein the molar ratio of copper in the copper source and aluminum in the aluminum source in step (1) is 0.2 to 1.0: 1;
preferably, the molar ratio of the alkali source to the aluminum source is 1.0-2.0: 1;
preferably, the alkali source is sodium hydroxide;
preferably, the aluminum source is sodium metaaluminate;
preferably, the molar ratio of the template to the aluminum source is 0.2-1.0: 1;
preferably, the templating agent comprises tetraethylenepentamine;
preferably, the mass ratio of the silica sol to the aluminum source is 0.05-0.5: 1;
preferably, the silica sol is added as an aqueous silica sol solution;
preferably, the mass percentage of the silica sol in the silica sol aqueous solution is 25-35 wt%;
preferably, step (1) comprises: dissolving an aluminum source in water, adding a copper source, stirring and mixing for the first time, then dropwise adding a template agent, then adding an alkali source, stirring and mixing for the second time, and then adding silica sol;
preferably, the crystallization reaction time is 1-10 days.
5. The method according to claim 3 or 4, wherein the crystallized product is washed and dried in the step (2) and then calcined again;
preferably, the time length of the primary roasting is 3-12 h;
preferably, the acid-treated acid is nitric acid;
preferably, the acid-treated sample is washed and dried again and then is subjected to secondary roasting;
preferably, the secondary roasting time is 3-12 h.
6. The process of claim 1 or 2 for ammonia-selective catalytic reduction of NOxThe preparation method of the copper-based catalyst is characterized in that when the configuration of the molecular sieve is AEI, the preparation method comprises the following steps:
(1) mixing a Y-type molecular sieve and a template agent, stirring and mixing for the first time, adding an alkali source, stirring and mixing for the second time, and carrying out crystallization reaction at 100-160 ℃ to obtain a crystallized product;
(2) roasting the crystallized product for one time to obtain a roasted product;
(3) and carrying out primary reaction on the roasted product and an ammonia source solution, carrying out secondary reaction on a solid-phase product obtained by the primary reaction and a copper source solution, and roasting a secondary reaction product to obtain the Cu-AEI molecular sieve.
7. The preparation method according to claim 6, wherein the mass ratio of the template to the Y-type molecular sieve in the step (1) is 0.1-1.0: 1;
preferably, the mass ratio of the alkali source to the Y-type molecular sieve is 0.1-1.0: 1;
preferably, the crystallization reaction time is 2 h-10 days;
preferably, the crystallized product in the step (2) is washed and dried and then is roasted again;
preferably, the temperature of the primary roasting is 600-850 ℃;
preferably, the time length of the primary roasting is 1-20 hours.
8. The method according to claim 6 or 7, wherein the concentration of the ammonia source solution in the step (3) is 0.001 to 10 mol/L;
preferably, the concentration of the copper source solution is 0.001-10 mol/L;
preferably, the temperature of the secondary roasting is 400-800 ℃.
9. The process of claim 1 or 2 for ammonia-selective catalytic reduction of NOxThe preparation method of the copper-based catalyst is characterized in that when the configuration of the molecular sieve is KFI, the method comprises the following steps:
(1) mixing an aluminum source, an alkali source and potassium salt, sequentially adding silica sol and seed crystal, and carrying out crystallization reaction at 100-150 ℃ to obtain a crystallization product;
(2) and sequentially carrying out washing, ammonia source solution ion exchange and copper source solution ion exchange on the crystallized product, and roasting a solid-phase product after the copper source solution ion exchange to obtain the Cu-KFI molecular sieve.
10. The preparation method according to claim 9, wherein the molar ratio of the alkali source to the aluminum source in the step (1) is 0.1 to 1: 1;
preferably, the molar ratio of the potassium salt to the aluminum source is 1-10: 1;
preferably, the mass ratio of the silica sol to the aluminum source is 1-20: 1;
preferably, the mass ratio of the seed crystal to the aluminum source is 0.001-1: 1;
preferably, the crystallization reaction time is 2 h-10 days;
preferably, the molar concentration of the ammonia source solution is 0.001-10 mol/L;
preferably, the molar concentration of the copper source solution is 0.001-10 mol/L;
preferably, the roasting temperature is 500-800 ℃;
preferably, the roasting time is 1-20 h.
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CN111315482A (en) * 2017-09-07 2020-06-19 巴斯夫公司 Zeolites with reduced extra-framework aluminum
CN108097301A (en) * 2017-12-14 2018-06-01 中国科学院生态环境研究中心 One kind is used for NH3Composite catalyst of-SCR reactions and its preparation method and application
CN109399664A (en) * 2018-09-26 2019-03-01 山东国瓷功能材料股份有限公司 A kind of preparation method and applications of the AEI molecular sieve of controlled grain
CN110510635A (en) * 2019-09-20 2019-11-29 中国科学院生态环境研究中心 A kind of Cu-SSZ-39 molecular sieve and its preparation method and application
CN111266132A (en) * 2020-02-05 2020-06-12 浙江大学 Preparation method of Cu-KFI catalyst for ammonia selective catalytic reduction reaction
CN112473730A (en) * 2020-12-14 2021-03-12 大连海事大学 Copper-based CHA-type silicon-aluminum molecular sieve catalyst and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
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CN114870887A (en) * 2022-04-28 2022-08-09 中化学科学技术研究有限公司 Cu-SSZ-39 molecular sieve, preparation method thereof and DeNOx catalyst
CN115672265A (en) * 2022-04-28 2023-02-03 中国科学院过程工程研究所 Copper-loaded FAU type molecular sieve and preparation method and application thereof
CN115672265B (en) * 2022-04-28 2023-12-08 中国科学院过程工程研究所 Copper-loaded FAU type molecular sieve and preparation method and application thereof
CN114870887B (en) * 2022-04-28 2024-05-14 中化学科学技术研究有限公司 Cu-SSZ-39 molecular sieve, preparation method thereof and DeNOx catalyst
CN114733563A (en) * 2022-05-10 2022-07-12 中国科学院生态环境研究中心 Cu-CHA and H-AEI composite catalyst and preparation method and application thereof

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Application publication date: 20210706