CN114849767A - Oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides and preparation method and application thereof - Google Patents
Oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides and preparation method and application thereof Download PDFInfo
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- 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
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
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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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- 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
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7065—CHA-type, e.g. Chabazite, LZ-218
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides an oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane, and a preparation method and application thereof. The oxide molecular sieve composite catalyst comprises an active component and a carrier, wherein the active component is indium and cerium, the carrier is a silicon-aluminum molecular sieve, and the silicon-aluminum molecular sieve comprises a silicon-aluminum molecular sieve with an MFI structure, a silicon-aluminum molecular sieve with a BEA structure and a silicon-aluminum molecular sieve with a CHA structure. The catalyst has high catalytic activity, water resistance and high airspeed resistance, is simple and easy to operate in the preparation process, and is suitable for large-scale application in industrial production.
Description
Technical Field
The invention relates to the field of environmental catalysis, in particular to an oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane, a preparation method and application thereof.
Background
Nitrogen Oxides (NO) x ) One of the main air pollutants is NO, which is not only a significant cause of environmental pollution such as dust-haze, photochemical smog, acid rain, etc., but also respiratory diseases causing serious harm to human health x Emission reduction is particularly important. NO emitted by industry, traffic and energy sources x Account for more than 90 percent of the total amount of artificial emission, and need to be controlled intensively. At present, NO x Emission control technologies mainly include source control and end purification (including adsorption, absorption, or chemical reduction, etc.).
CN 104437608A discloses a catalyst for ammonia oxide ammonia selective catalytic reduction, which comprises Fe, rare earth element auxiliary agent and molecular sieve carrier Beta, ammonia is used as a reducing agent, and nitrogen oxides can be converted into harmless nitrogen under the condition of oxygen enrichment by using the catalyst. However, the selected rare earth element additive is expensive and high in production cost, and ammonia is used as a reducing agent, so that the defects of difficulty in storage, easiness in secondary pollution generation, high cost and the like exist.
CN 105396614A discloses a catalyst for removing ammonia oxide by ammonia selective catalytic reduction, and preparation and application thereof, wherein a Bate molecular sieve is used as a carrier, a copper salt is used as an active component precursor, an aqueous solution is prepared, a copper active component is introduced by a liquid phase ion exchange method, and the catalyst is obtained by drying, calcining and high-pressure extrusion molding.
In recent years, researchers have found that short-chain HC and oxygen-containing HC (directly linked C atoms are 2 or more) have excellent selective catalytic reduction of NO x Ability of (C) with methane (CH) 4 ) As an easily available reducing agent, has the advantages of large storage capacity, safety and the likeBy the advantages of convenient operation and NO environmental pollution after reaction, and the like, and is often accompanied by NO x Selective catalytic reduction of NO by methane present in combustion exhaust gases x (CH 4 SCR) can realize the cooperative control of two pollutants simultaneously, and has wide application prospect and economic value. Therefore, how to prepare an oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides is an important research direction in the field.
Disclosure of Invention
The invention aims to provide an oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the present invention is to provide an oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides, which comprises an active component and a carrier, wherein the active component is indium and cerium, the carrier is a silicon-aluminum molecular sieve, and the silicon-aluminum molecular sieve comprises a silicon-aluminum molecular sieve with a BEA structure, a silicon-aluminum molecular sieve with an MFI structure and a silicon-aluminum molecular sieve with a CHA structure.
The catalyst is used for methane selective reduction of nitrogen oxides, does not contain noble metals, takes a silicon-aluminum molecular sieve as a carrier, and enables the silicon-aluminum molecular sieve composite catalyst to be In CH under the synergistic action of active components of indium (In) and cerium (Ce) 4 The catalyst shows excellent catalytic activity, higher water resistance and high space velocity resistance in SCR reaction. The preparation process of the catalyst is simple and easy to operate, and is suitable for large-scale application in industrial production.
In a preferred embodiment of the present invention, the mass fraction of indium is 4 to 8%, the mass fraction of cerium is 8 to 32%, and the mass fraction of Beta molecular sieve is 60 to 88%, wherein the mass fraction of indium may be 4%, 5%, 6%, 7%, 8%, etc., the mass fraction of cerium may be 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, etc., and the mass fraction of silica-alumina molecular sieve may be 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, etc., based on 100% by mass of the catalyst, but the present invention is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.
Preferably, the silicon-aluminum molecular sieve with BEA structure is a low silicon-aluminum atomic ratio Beta molecular sieve.
Preferably, the silicon-aluminum atomic ratio of the low silicon-aluminum atomic ratio Beta molecular sieve is 1 to 30, wherein the silicon-aluminum atomic ratio can be 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 or 30, and the like, but is not limited to the recited values, and other unrecited values in the numerical range are also applicable.
Preferably, the silicoaluminophosphate molecular sieve having the MFI structure is a low silicoaluminophosphate ZSM-5 molecular sieve.
Preferably, the low silicon aluminum atomic ratio ZSM-5 molecular sieve has a silicon aluminum atomic ratio of 1-30, wherein the silicon aluminum atomic ratio may be 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 or 30, but is not limited to the recited values, and other unrecited values within the range of the recited values are also applicable.
Preferably, the silicoaluminophosphate molecular sieve having the CHA structure is a broad silicoaluminophosphate atomic ratio SSZ-13 molecular sieve.
Preferably, the wide silicon to aluminum atomic ratio SSZ-13 molecular sieve has a silicon to aluminum atomic ratio of 1 to 100, wherein the silicon to aluminum atomic ratio may be 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
The invention adopts a Beta molecular sieve and a ZSM-5 molecular sieve with low silicon-aluminum atomic ratio, wherein the low silicon-aluminum atomic ratio provides more acid sites to promote CH 4 And NO x Adsorption and conversion. The invention adopts the SSZ-13 molecular sieve with the wide silicon-aluminum ratio, wherein the wide silicon-aluminum atomic ratio brings the following beneficial effects: can be synthesized by various methods, and has wider application rangeAnd (4) universality.
The second purpose of the invention is to provide a preparation method of the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides, which comprises the following steps:
the method comprises the steps of soaking a silicon-aluminum molecular sieve in an aqueous solution containing cerium salt and indium salt after ammonium exchange, performing ion exchange after ultrasonic mixing to obtain a silicon-aluminum molecular sieve which completes ion exchange, loading active components containing cerium and indium on the surface of the silicon-aluminum molecular sieve which completes ion exchange, drying, and roasting to obtain the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides.
As a preferred embodiment of the present invention, the silico-aluminum molecular sieves include a silico-aluminum molecular sieve having a BEA structure, a silico-aluminum molecular sieve having an MFI structure, and a silico-aluminum molecular sieve having a CHA structure.
Preferably, the silicon-aluminum molecular sieve with BEA structure is a low silicon-aluminum atomic ratio Beta molecular sieve.
In the invention, the synthesis method of the Beta molecular sieve with low silicon-aluminum atomic ratio comprises the following steps: and synthesizing the Beta molecular sieve with the low silicon-aluminum atomic ratio by an organic template-free seed crystal method or an amino acid auxiliary template method.
Preferably, the silicoaluminophosphate molecular sieve having the MFI structure is a low silicon-to-aluminum atomic ratio ZSM-5 molecular sieve.
In the invention, the synthesis method of the ZSM-5 molecular sieve with low silicon-aluminum atomic ratio comprises the following steps: and urea, glucose or ammonium fluoride is adopted to assist in synthesizing the ZSM-5 molecular sieve with the low silicon-aluminum atomic ratio.
Preferably, the silicoaluminophosphate molecular sieve having the CHA structure is a broad silicoaluminophosphate atomic ratio SSZ-13 molecular sieve.
In the invention, the synthesis method of the SSZ-13 molecular sieve with the wide silicon-aluminum atomic ratio comprises the following steps: and synthesizing the SSZ-13 molecular sieve with the wide silicon-aluminum atomic ratio by a template method.
As a preferred embodiment of the present invention, the ammonium exchange method comprises: and (3) carrying out ion exchange on the low-silicon-aluminum atomic ratio Beta molecular sieve and an ammonium salt solution, and then filtering, washing and drying.
Preferably, the ammonium salt solution comprises ammonium nitrate and/or ammonium chloride.
Preferably, the ammonium exchange is repeated 2-3 times, wherein the repetition time can be 2 times or 3 times.
Preferably, the time for ammonium exchange is 2 to 8 hours, wherein the time can be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, and the like, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature of the ammonium exchange is 60 to 100 ℃, wherein the temperature can be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferred embodiment of the present invention, the cerium salt includes any one or a combination of at least two of nitrate, chloride, sulfate or acetate salts of cerium, wherein the combination is exemplified by, typically but not limited to: a combination of cerium nitrate and cerium chloride, a combination of cerium chloride and cerium sulfate, a combination of cerium sulfate and cerium acetate, and the like.
Preferably, the cerium salt is present in the aqueous solution at a concentration of 0.1 to 1M, wherein the concentration may be 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.6M, 0.7M, 0.8M, 0.9M or 1M, but is not limited to the recited values, and other values not recited within this range of values are equally applicable.
Preferably, the indium salt comprises any one of nitrate, chloride, sulphate or acetate salts of indium or a combination of at least two thereof, wherein typical but non-limiting examples are: a combination of indium nitrate and indium chloride, a combination of indium chloride and indium sulfate, a combination of indium sulfate and indium acetate, and the like.
Preferably, the concentration of the indium salt in the aqueous solution is 0.1 to 1M, wherein the concentration may be 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.6M, 0.7M, 0.8M, 0.9M, 1M, etc., but is not limited to the recited values, and other values not recited in the range of values are also applicable.
In a preferred embodiment of the present invention, the ultrasonic mixing is performed for 10 to 60min, wherein the ultrasonic mixing may be performed for 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, or 60min, but the ultrasonic mixing is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
Preferably, the ultrasonic mixing is performed at a frequency of 10 to 100HZ, wherein the frequency may be 10HZ, 20HZ, 30HZ, 40HZ, 50HZ, 60HZ, 70HZ, 80HZ, 90HZ, 100HZ, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the stirring time of the ion exchange is 6-12 h, wherein the stirring time can be 6h, 7h, 8h, 9h, 10h, 11h or 12h, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the stirring temperature of the ion exchange is 60 to 100 ℃, wherein the stirring temperature can be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the method of loading comprises dipping and oil bath heating cladding.
Preferably, the impregnation comprises: and (3) impregnating active components containing cerium and indium in the residual solution on the surface of the silicon-aluminum molecular sieve which completes ion exchange.
Preferably, the temperature of the impregnation is 60 to 80 ℃, wherein the temperature can be 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃ or 80 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time for the immersion is 20-60 min, wherein the time can be 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the oil bath heating cladding comprises: and (3) placing the silicon-aluminum molecular sieve subjected to ion exchange in a mixed solution, stirring, adding active component salt and urotropine, and heating in an oil bath to complete coating.
Preferably, the mixed solution comprises ethanol and water, and the volume ratio of the ethanol to the water is 1: (0.5 to 1.5), wherein the volume ratio may be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1:1.5, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the stirring time is 0.5 to 2 hours, wherein the time can be 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1.0 hour, 1.1 hour, 1.2 hour, 1.3 hour, 1.4 hour, 1.5 hour, 1.6 hour, 1.7 hour, 1.8 hour, 1.9 hour or 2 hours, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the active component salts include cerium salts and indium salts.
Preferably, the cerium salt comprises any one of, or a combination of at least two of, nitrate, chloride, sulfate or acetate salts of cerium, with typical but non-limiting examples being: a combination of cerium nitrate and cerium chloride, a combination of cerium chloride and cerium sulfate, a combination of cerium sulfate and cerium acetate, and the like.
Preferably, the cerium salt is present in the mixed solution at a concentration of 0.1 to 1M, wherein the concentration may be 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.6M, 0.7M, 0.8M, 0.9M, or 1M, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the indium salt comprises any one of nitrate, chloride, sulphate or acetate salts of indium or a combination of at least two thereof, wherein typical but non-limiting examples are: a combination of indium nitrate and indium chloride, a combination of indium chloride and indium sulfate, a combination of indium sulfate and indium acetate, and the like.
Preferably, the concentration of the indium salt in the mixed solution is 0.1 to 1M, wherein the concentration may be 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.6M, 0.7M, 0.8M, 0.9M, 1M, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the molar ratio of the active ingredient salt to the urotropin is 0.05 to 0.5, wherein the molar ratio may be 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5, etc., but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the temperature of the oil bath is 60 to 100 ℃, wherein the temperature can be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the oil bath is carried out for 1 to 4 hours, wherein the time can be 1 hour, 2 hours, 3 hours, 4 hours and the like, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
In a preferred embodiment of the present invention, the drying temperature is 80 to 150 ℃, wherein the temperature may be 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying time is 4-12 h, wherein the drying time can be 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature of the baking is 400 to 700 ℃, wherein the temperature may be 400 ℃, 120 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, 620 ℃, 640 ℃, 660 ℃, 680 ℃ or 700 ℃, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the baking time is 4 to 8 hours, wherein the time can be 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours, 6 hours, 6.2 hours, 6.4 hours, 6.6 hours, 6.8 hours, 7.0 hours, 7.2 hours, 7.4 hours, 7.6 hours, 7.8 hours or 8 hours, etc., but not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
As a preferred technical solution of the present invention, the preparation method comprises:
the method comprises the steps of performing ammonium ion exchange on a silicon-aluminum molecular sieve, then soaking the silicon-aluminum molecular sieve in an aqueous solution containing cerium salt and indium salt, performing ultrasonic mixing for 10-60 min, then performing ion exchange at the stirring temperature of 60-100 ℃ for 6-12 h to obtain the silicon-aluminum molecular sieve for completing ion exchange, loading active components containing cerium and indium on the surface of the silicon-aluminum molecular sieve for completing ion exchange, drying at the temperature of 80-150 ℃ for 4-12 h, and then roasting at the temperature of 400-700 ℃ for 4-8 h to obtain the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane.
The third purpose of the invention is to provide the application of the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides, which is used in the field of environmental catalysis.
The oxide molecular sieve composite catalyst can be applied to the co-elimination of nitrogen oxides and methane in the fields of flue gas, waste gas, natural gas, automobile tail gas and the like.
Compared with the prior art, the invention has the following beneficial effects:
the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxide by methane provided by the invention has excellent catalytic activity, higher water resistance and high space velocity resistance, the preparation method of the catalyst is simple, no noble metal is contained, the cost is lower, and the catalyst can be applied to industrial large-scale production.
Drawings
Fig. 1 is an XRD pattern of the oxide molecular sieve composite catalyst of example 1 of the present invention.
Figure 2 is a graph of the nitrogen oxide conversion of an oxidic molecular sieve composite catalyst under first test conditions in example 1, example 2, example 4 and example 6 of the present invention.
FIG. 3 is a graph of the nitrogen oxide conversion of an oxidic molecular sieve composite catalyst under anti-water tolerance test conditions in examples 1, 2, 4 and 6 of the present invention.
Figure 4 is a graph of the nitrogen oxide conversion of an oxide molecular sieve composite catalyst under second test conditions in example 3 of the invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The embodiment provides an oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides and a preparation method thereof:
the oxide molecular sieve composite catalyst consists of 6 percent of indium (In), 16 percent of cerium (Ce) active component and Beta molecular sieve carrier with silicon-aluminum atomic ratio of 14.
The preparation method comprises the following steps: adding indium nitrate with the indium (In) content of 6% and cerium nitrate with the cerium (Ce) content of 16% into 100mL of water, adding a Beta molecular sieve with the content of 78% and completing the exchange with ammonium nitrate, performing ultrasonic dispersion for 20 minutes, stirring for 10 hours In an oil bath at 60 ℃ to complete the ion exchange, performing rotary evaporation at 80 ℃ to impregnate active components containing indium and cerium on the surface of the Beta molecular sieve, drying for 8 hours at 100 ℃, transferring the obtained Beta molecular sieve containing metal active components into a muffle furnace under the air condition, and roasting for 6 hours at 600 ℃ to obtain the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane.
The XRD patterns of the catalysts in this example are shown in fig. 1, and the conversion of nitrogen oxides is shown in fig. 2 and 3.
Example 2
The embodiment provides an oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides and a preparation method thereof:
the oxide molecular sieve composite catalyst consists of 5.5 percent of indium (In), 27 percent of active component of cerium (Ce) and Beta molecular sieve carrier with the silicon-aluminum atomic ratio of 14.
The preparation method comprises the following steps: adding indium nitrate with the indium (In) content of 5.5% and cerium nitrate with the cerium (Ce) content of 27% into 200mL of water, adding Beta molecular sieve with the indium (In) content of 67.5% and completing the exchange with ammonium nitrate, performing ultrasonic treatment for 10 minutes, stirring for 8 hours at 80 ℃ In an oil bath, completing the ion exchange, performing rotary evaporation at 80 ℃ to impregnate active components containing indium and cerium on the surface of the Beta molecular sieve, drying for 8 hours at 120 ℃, transferring the obtained Beta molecular sieve containing metal active components into a muffle furnace under the air condition, and roasting for 6 hours at 600 ℃ to obtain the oxide/molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane.
The conversion rate of nitrogen oxide in the application of the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxide in this example is shown in fig. 2 and fig. 3.
Example 3
The embodiment provides an oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides and a preparation method thereof:
the oxide molecular sieve composite catalyst consists of 4 percent of indium (In), 4 percent of active component of cerium (Ce) and Beta molecular sieve carrier with silicon-aluminum atomic ratio of 6.
The preparation method comprises the following steps: adding indium nitrate with the indium (In) content of 4% and cerium nitrate with the cerium (Ce) content of 4% into 100mL of water, adding Beta molecular sieve with the content of 70% and used for finishing first ion exchange with ammonium nitrate, performing ultrasonic treatment for 60 minutes, stirring for 9 hours under an oil bath at 85 ℃ to finish ion exchange, performing rotary evaporation at 70 ℃ to impregnate active components containing indium and cerium on the surface of the Beta molecular sieve, drying for 12 hours at 120 ℃, transferring the obtained Beta molecular sieve containing metal active components into a muffle furnace under the air condition, and roasting for 6 hours at 500 ℃ to obtain the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane.
The conversion of nitrogen oxides in the application of the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides described in this example is shown in fig. 4.
Example 4
The embodiment provides an oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides and a preparation method thereof:
the oxide molecular sieve composite catalyst consists of 6 percent of indium (In), 16 percent of active component of cerium (Ce) and Beta molecular sieve carrier with silicon-aluminum atomic ratio of 6.
The preparation method comprises the following steps: adding indium nitrate with the indium (In) content of 6% and cerium nitrate with the cerium (Ce) content of 16% into 100mL of water, adding a Beta molecular sieve with the content of 78% and completing the exchange with ammonium nitrate, performing ultrasonic treatment for 30 minutes, stirring for 9 hours at 85 ℃ In an oil bath to complete ion exchange, performing rotary evaporation at 70 ℃ to dip active components containing indium and cerium on the surface of the Beta molecular sieve, and then drying for 12 hours at 80 ℃; and transferring the obtained Beta molecular sieve containing the metal active component into a muffle furnace under an air condition, and roasting at 600 ℃ for 8 hours to obtain the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane.
The conversion rate of nitrogen oxide in the application of the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxide in this example is shown in fig. 2 and fig. 3.
Example 5
The embodiment provides an oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides and a preparation method thereof:
the oxide molecular sieve composite catalyst consists of 8 percent of indium (In), 20 percent of active component of cerium (Ce) and SSZ-13 molecular sieve carrier with the silicon-aluminum atomic ratio of 10.
The preparation method comprises the following steps: adding indium nitrate with the indium (In) content of 8% and cerium nitrate with the cerium (Ce) content of 20% into 150mL of water, adding SSZ-13 molecular sieve with the indium (In) content of 72% and completing ammonium nitrate exchange, performing ultrasonic treatment for 30 minutes, stirring for 8 hours under an oil bath at 85 ℃ to complete ion exchange, performing rotary evaporation at 80 ℃ to impregnate active components containing indium and cerium on the surface of the SSZ-13 molecular sieve, drying for 4 hours at 100 ℃, transferring the obtained SSZ-13 molecular sieve containing metal active components into a muffle furnace under the air condition, and roasting for 8 hours at 600 ℃ to obtain the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane.
Example 6
The embodiment provides an oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides and a preparation method thereof:
the oxide molecular sieve composite catalyst consists of 5.5 percent of indium (In), 27 percent of active component of cerium (Ce) and Beta molecular sieve carrier with silicon-aluminum atomic ratio of 6.
The preparation method comprises the following steps: adding indium nitrate with the indium (In) content of 5.5% and cerium nitrate with the cerium (Ce) content of 27% into 200mL of water, adding Beta molecular sieve with the indium (In) content of 67.5% and completing the exchange with ammonium nitrate, performing ultrasonic treatment for 10 minutes, stirring for 8 hours at 80 ℃ In an oil bath, completing the ion exchange, performing rotary evaporation at 80 ℃ to impregnate active components containing indium and cerium on the surface of the Beta molecular sieve, drying for 8 hours at 120 ℃, transferring the obtained Beta molecular sieve containing metal active components into a muffle furnace under the air condition, and roasting for 6 hours at 600 ℃ to obtain the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane.
The conversion rate of nitrogen oxide in the application of the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxide in this example is shown in fig. 2 and 3.
Example 7
The embodiment provides an oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides and a preparation method thereof:
the oxide molecular sieve composite catalyst consists of 6 percent of indium (In), 16 percent of active component of cerium (Ce) and Beta molecular sieve carrier with silicon-aluminum atomic ratio of 6.
The preparation method comprises the following steps: adding indium nitrate with the indium (In) content of 6% and cerium nitrate with the cerium (Ce) content of 16% into 100mL of water, adding a Beta molecular sieve with the content of 78%, performing ultrasonic treatment for 30 minutes, stirring for 1 hour at room temperature, performing rotary evaporation at 70 ℃, drying for 12 hours at 80 ℃, transferring the obtained Beta molecular sieve containing the metal active component into a muffle furnace under the air condition, and roasting for 8 hours at 600 ℃ to obtain the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane.
Example 8
This example was carried out under the same conditions as in example 1 except that the Beta zeolite having a silicon/aluminum atomic ratio of 14 was replaced with the Beta zeolite having a silicon/aluminum atomic ratio of 250.
Comparative example 1
The comparative example provides an oxide molecular sieve composite catalyst for selective reduction of nitrogen oxides by methane and a preparation method thereof:
the oxide molecular sieve composite catalyst consists of an active component of 6 percent indium (In) and a Beta molecular sieve carrier with the silicon-aluminum atomic ratio of 14.
The preparation method comprises the following steps: adding indium nitrate with the indium (In) content of 6% into 100mL of water, adding a Beta molecular sieve with the content of 94% and completing the exchange with ammonium nitrate, performing ultrasonic treatment for 20 minutes, stirring for 10 hours under an oil bath at 60 ℃, completing ion exchange, performing rotary evaporation at 80 ℃ to impregnate an active component containing indium on the surface of the Beta molecular sieve, then drying for 8 hours at 100 ℃, transferring the obtained Beta molecular sieve containing a metal active component into a muffle furnace under the air condition, and roasting for 6 hours at 600 ℃ to obtain the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane.
The oxide molecular sieve composite catalysts for methane selective reduction of nitrogen oxides in examples 1 to 8 and comparative example 1 were tested for catalytic activity and water resistance, and the test results are shown in table 1:
the method for testing the catalytic activity is divided into a first test condition, a second test condition and a water resistance test condition.
First test conditions: 0.2g of catalyst is placed in a fixed bed reactor with the inner diameter of 5mm, nitrogen is used as a balancer, and the airspeed is 16000h -1 On the contraryContinuously introducing reaction gas into a fixed bed reactor, wherein the concentration of reaction gas methane is 2000ppm, the concentration of nitric oxide is 1200ppm, and the oxygen content is 3.8%; under the test conditions, the test results of the oxide/molecular sieve composite catalyst for methane selective reduction of nitrogen oxides provided in example 1, example 2, example 4 and example 6 are shown in fig. 2, and the time for the nitrogen oxide conversion rate to reach 90% in examples 1, 2, 4 to 8 and comparative example 1 is shown in table 1;
test method for water repellency: placing 0.2g of catalyst in a fixed bed reactor with an inner diameter of 5mm, using nitrogen as a balancer, and setting the airspeed at 16000h -1 The reaction gas was continuously fed into the fixed bed reactor, the reaction gas had a methane concentration of 2000ppm, a nitric oxide concentration of 1200ppm, an oxygen content of 3.8% and a water content of 10%, under the test conditions, the test results of the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides provided in examples 1, 2, 4 and 6 are shown in fig. 3, and the time for the nitrogen oxide conversion rate to reach 90% in examples 1 to 8 and comparative example 1 is shown in table 1;
second test conditions: placing 0.2g of catalyst in a fixed bed reactor with an inner diameter of 5mm, using nitrogen as a balancer, and keeping the space velocity of 70000h -1 The reaction gas is continuously introduced into the fixed bed reactor, the concentration of the reaction gas methane is 2000ppm, the concentration of nitric oxide is 1200ppm, and the oxygen content is 3.8%; under the test conditions, the test results of the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides provided in example 3 are shown in fig. 4, and the time for the nitrogen oxide conversion rate to reach 90% in example 3 is shown in table 1.
TABLE 1
From the above table it can be found that: the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane provided by the invention comprises active components In and Ce and a silicon-aluminum molecular sieve carrier, the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane has higher catalytic performance at the temperature of 400-600 ℃, and the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane does not contain noble metals and toxic active components, so that the cost of the catalyst is greatly saved, the catalyst is environment-friendly, and meanwhile, the catalyst has good water resistance, the preparation method is simple, and the industrial large-scale production is easy.
It can be known from the combination of examples 1 to 6 that the oxide molecular sieve composite catalyst for selective reduction of nitrogen oxides by methane provided in examples 1 to 6 still has high catalytic activity at a water content of 10%, and the conversion rate of nitrogen oxides reaches more than 90% at a temperature of more than 450 ℃.
Combining with example 3, the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxide has excellent space velocity resistance performance at 70000h -1 The catalyst still has higher catalytic performance at space velocity, and the conversion rate of nitrogen oxides reaches more than 90 percent at the temperature of more than 410 ℃.
In combination with example 7, it can be seen that the oxide molecular sieve composite catalyst for selective reduction of nitrogen oxides by methane must undergo two ion exchanges during the synthesis process, and that simple impregnation has a certain inhibiting effect on the catalytic performance of the catalyst.
In combination with example 8, it can be seen that the silica-alumina ratio has an important influence on the acidity of the catalyst, and the Beta molecular sieve support with a high silica-alumina ratio has an inhibiting effect on the catalytic performance of the catalyst.
Combining example 1 and comparative example 1, it can be known that In and Ce as active components are absent, and the addition of Ce can greatly improve the catalytic performance and water resistance of the catalyst.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by using methane comprises an active component and a carrier, wherein the active component is indium and cerium, the carrier is a silicon-aluminum molecular sieve, and the silicon-aluminum molecular sieve comprises a silicon-aluminum molecular sieve with a BEA structure, a silicon-aluminum molecular sieve with an MFI structure and a silicon-aluminum molecular sieve with a CHA structure.
2. The oxide molecular sieve composite catalyst of claim 1, wherein the mass fraction of indium is 4 to 8%, the mass fraction of cerium is 8 to 32%, and the mass fraction of the silicon-aluminum molecular sieve is 60 to 88%, based on 100% by mass of the catalyst;
preferably, the silicon-aluminum molecular sieve with BEA structure is a low silicon-aluminum atomic ratio Beta molecular sieve;
preferably, the silicon-aluminum atomic ratio of the low silicon-aluminum atomic ratio Beta molecular sieve is 1-30;
preferably, the silicoaluminophosphate molecular sieve having the MFI structure is a low silicoaluminophosphate ZSM-5 molecular sieve;
preferably, the silicon-aluminum atomic ratio of the low silicon-aluminum atomic ratio ZSM-5 molecular sieve is 1-30;
preferably, the silicoaluminophosphate molecular sieve having the CHA structure is a wide silicon-aluminum atomic ratio SSZ-13 molecular sieve;
preferably, the silicon-aluminum atomic ratio of the wide silicon-aluminum atomic ratio SSZ-13 molecular sieve is 1-100.
3. A method for preparing the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides according to claim 1 or 2, comprising:
the method comprises the steps of soaking a silicon-aluminum molecular sieve in an aqueous solution containing cerium salt and indium salt after ammonium exchange, performing ion exchange after ultrasonic mixing to obtain a silicon-aluminum molecular sieve which completes ion exchange, loading active components containing cerium and indium on the surface of the silicon-aluminum molecular sieve which completes ion exchange, drying, and roasting to obtain the oxide molecular sieve composite catalyst for methane selective reduction of nitrogen oxides.
4. The production method according to claim 3, wherein the silicoaluminophosphate molecular sieves include a silicoaluminophosphate molecular sieve having an MFI structure, a silicoaluminophosphate molecular sieve having a BEA structure and a silicoaluminophosphate molecular sieve having a CHA structure;
preferably, the silicon-aluminum molecular sieve with BEA structure is a low silicon-aluminum atomic ratio Beta molecular sieve;
preferably, the silicoaluminophosphate molecular sieve having the MFI structure is a low silicoaluminophosphate ZSM-5 molecular sieve;
preferably, the silicoaluminophosphate molecular sieve having the CHA structure is a broad silicoaluminophosphate atomic ratio SSZ-13 molecular sieve.
5. The method of claim 3 or 4, wherein the ammonium exchange process comprises: carrying out ion exchange on the Beta molecular sieve with low silicon-aluminum atomic ratio and an ammonium salt solution, and then filtering, washing and drying;
preferably, the ammonium salt solution comprises ammonium nitrate and/or ammonium chloride;
preferably, the ammonium exchange is repeated for 2-3 times;
preferably, the ammonium exchange time is 2-8 h;
preferably, the temperature of the ammonium exchange is 60-100 ℃.
6. The production method according to any one of claims 3 to 5, wherein the cerium salt comprises any one of or a combination of at least two of nitrate, chloride, sulfate, or acetate salts of cerium;
preferably, the concentration of the cerium salt in the aqueous solution is 0.1-1M;
preferably, the indium salt comprises any one of nitrate, chloride, sulphate or acetate salts of indium or a combination of at least two thereof;
preferably, the concentration of the indium salt in the aqueous solution is 0.1-1M.
7. The method according to any one of claims 3 to 6, wherein the ultrasonic mixing is performed for 10 to 60 min;
preferably, the frequency of the ultrasonic mixing is 10-100 HZ;
preferably, the stirring time of the ion exchange is 6-12 h;
preferably, the stirring temperature of the ion exchange is 60-100 ℃;
preferably, the method of loading comprises dipping and oil bath heating cladding;
preferably, the impregnation comprises: impregnating active components containing cerium and indium in the residual solution on the surface of the silicon-aluminum molecular sieve which completes ion exchange;
preferably, the dipping temperature is 60-80 ℃;
preferably, the dipping time is 20-120 min;
preferably, the oil bath heating cladding comprises: placing the silicon-aluminum molecular sieve subjected to ion exchange in a mixed solution, stirring, adding active component salt and urotropine, and heating in an oil bath to complete coating;
preferably, the mixed solution comprises ethanol and water, and the volume ratio of the ethanol to the water is 1: (0.5 to 1.5);
preferably, the stirring time is 0.5-2 h;
preferably, the active component salts include cerium salts and indium salts;
preferably, the cerium salt comprises any one or a combination of at least two of nitrate, chloride, sulfate or acetate salts of cerium;
preferably, the concentration of the cerium salt in the mixed solution is 0.1-1M;
preferably, the indium salt comprises any one of nitrate, chloride, sulphate or acetate salts of indium or a combination of at least two thereof;
preferably, the concentration of the indium salt in the mixed solution is 0.1-1M;
preferably, the molar ratio of the active component salt to the urotropine is 0.05-0.5;
preferably, the temperature of the oil bath is 60-100 ℃;
preferably, the oil bath time is 1-4 h.
8. The method according to any one of claims 3 to 7, wherein the drying temperature is 80 to 150 ℃;
preferably, the drying time is 4-12 h;
preferably, the roasting temperature is 400-700 ℃;
preferably, the roasting time is 4-8 h.
9. The production method according to any one of claims 3 to 8, characterized by comprising:
the method comprises the steps of performing ammonium exchange on a silicon-aluminum molecular sieve, then soaking the silicon-aluminum molecular sieve in an aqueous solution containing cerium salt and indium salt, performing ultrasonic mixing for 10-60 min, then performing ion exchange at the stirring temperature of 60-100 ℃ for 6-12 h to obtain the silicon-aluminum molecular sieve for completing ion exchange, loading active components containing cerium and indium on the surface of the silicon-aluminum molecular sieve for completing ion exchange, drying at the temperature of 80-150 ℃ for 4-12 h, and then roasting at the temperature of 400-700 ℃ for 4-8 h to obtain the oxide molecular sieve composite catalyst for selectively reducing nitrogen oxides by methane.
10. Use of the oxidic molecular sieve composite catalyst for methane selective reduction of nitrogen oxides according to claim 1 or 2, wherein the oxidic molecular sieve composite catalyst is used in the field of environmental catalysis.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1314476A1 (en) * | 2001-11-26 | 2003-05-28 | Technische Universiteit Delft | Zeolite catalysts and their use in selective catalytic reduction of NOx |
| CN102029178A (en) * | 2010-10-18 | 2011-04-27 | 清华大学 | Copper-based molecular sieve catalyst and preparation method thereof |
| CN102869427A (en) * | 2010-03-11 | 2013-01-09 | 约翰逊马西有限公司 | Disordered molecular sieve supports for the selective catalytic reduction of nox |
| 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 |
| CN107029781A (en) * | 2016-02-04 | 2017-08-11 | 中触媒新材料股份有限公司 | Iron and cerium modified beta-molecular sieve selective reduction catalyst and preparation method and application |
| CN111957342A (en) * | 2020-07-08 | 2020-11-20 | 华南理工大学 | Small pore molecular sieve loaded bimetallic material for removing nitrogen oxides in tail gas of diesel vehicles at low temperature and preparation method and application thereof |
| WO2021104264A1 (en) * | 2019-11-25 | 2021-06-03 | Basf Se | Rare earth element containing zeolitic material having the aei framework type and coated monolith substrate |
| CN113713851A (en) * | 2021-09-28 | 2021-11-30 | 哈尔滨工业大学（深圳） | Preparation method of In/H-beta catalyst for improving sulfur resistance and water resistance |
-
2022
- 2022-04-18 CN CN202210405785.5A patent/CN114849767A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1314476A1 (en) * | 2001-11-26 | 2003-05-28 | Technische Universiteit Delft | Zeolite catalysts and their use in selective catalytic reduction of NOx |
| CN102869427A (en) * | 2010-03-11 | 2013-01-09 | 约翰逊马西有限公司 | Disordered molecular sieve supports for the selective catalytic reduction of nox |
| CN102029178A (en) * | 2010-10-18 | 2011-04-27 | 清华大学 | Copper-based molecular sieve catalyst and preparation method thereof |
| CN107029781A (en) * | 2016-02-04 | 2017-08-11 | 中触媒新材料股份有限公司 | Iron and cerium modified beta-molecular sieve selective reduction catalyst and preparation method and application |
| 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 |
| WO2021104264A1 (en) * | 2019-11-25 | 2021-06-03 | Basf Se | Rare earth element containing zeolitic material having the aei framework type and coated monolith substrate |
| CN111957342A (en) * | 2020-07-08 | 2020-11-20 | 华南理工大学 | Small pore molecular sieve loaded bimetallic material for removing nitrogen oxides in tail gas of diesel vehicles at low temperature and preparation method and application thereof |
| CN113713851A (en) * | 2021-09-28 | 2021-11-30 | 哈尔滨工业大学（深圳） | Preparation method of In/H-beta catalyst for improving sulfur resistance and water resistance |
Non-Patent Citations (1)
| Title |
|---|
| H. BERNDT ET.AL: "Selective catalytic reduction of NO under lean conditions by methane and propane over indium/cerium-promoted zeolites" * |
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