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CN101664694A - Catalyst for decomposition of N2O and preparation method and application thereof - Google Patents

Catalyst for decomposition of N2O and preparation method and application thereof Download PDF

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CN101664694A
CN101664694A CN 200810119339 CN200810119339A CN101664694A CN 101664694 A CN101664694 A CN 101664694A CN 200810119339 CN200810119339 CN 200810119339 CN 200810119339 A CN200810119339 A CN 200810119339A CN 101664694 A CN101664694 A CN 101664694A
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catalyst
molecular sieve
decomposes
metal oxide
temperature
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李翠清
王虹
宋永吉
王军利
迟姚玲
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Beijing Institute of Petrochemical Technology
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Beijing Institute of Petrochemical Technology
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/10Capture or disposal of greenhouse gases of nitrous oxide (N2O)

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Abstract

The invention relates to a catalyst for decomposition of N2O and a preparation method and application thereof. The catalyst contains a composite metal oxide and a ZRP, PSRY or beta molecular sieve carrier, wherein the composite metal oxide has a spinel structure and/or a perovskite-like structure, and the molecular general formula of the composite metal oxide is Co3-xMxO4 or La2-yMyBO4. The preparation method comprises the following steps: dissolving a corresponding metal salt and a corresponding organic complexing agent into water respectively, and mixing the components; putting the carrier into the aqueous solution for soaking; drying the mixture at a temperature of between 30 and 90 DEG C to obtain a catalyst precursor; and calcinating the catalyst precursor at a temperature of between500 and 1,000 DEG C for 2 to 10 hours to obtain the catalyst. The catalyst has the advantages and the effects of good activity and low decomposition temperature of N2O.

Description

A kind of N that is used for 2Catalyst and preparation method and purposes that O decomposes
Technical field
A kind of catalyst that the present invention relates to use in air pollution control technique is specifically related to a kind of N of being used for 2The catalyst that O decomposes.The invention still further relates to this Preparation of catalysts method and purposes.
Background technology
N 2O is a kind of important atmosphere pollution, and it is not only a kind of greenhouse gases, and ozone layer is had destruction.N 2The greenhouse effects of O are respectively CO 2310 times, CH 421 times (Ram í rez J P, Kapteijn F,
Figure A20081011933900031
Ffel K, et al.Formation and control of N 2O in nitricacid production.Where do we stand today? [J] .Appl.Catal.B, 2003,44:1).N 2Combustion process that derives from ocean, soil, agricultural, various fossil fuels and the chemical industry of O.The organic synthesis factory of nitric plant and employing nitric acid oxidation process (as producing adipic acid and glyoxal) is N 2The maximum emission source of O.Along with the continuous enhancing of people's environmental consciousness, N 2The improvement of O has caused the great attention of global various industrial production enterprise and environmental protection organization.
Have bibliographical information to adopt coprecipitation method to prepare cobalt cerium O composite metallic oxide catalyst, wherein cobalt is with Co 3O 4Form exists, and catalysis is at 10%O 2, 3%H 2O (percentage by volume) and 0.1%N is arranged 2Decomposing N during the O coexistence 2O's is active high, N in the time of 330 ℃ 2O just can decompose (Xue Li fully, Zhang Changbin, He Hong. nitrous oxide catalytic decomposition performance study on the cobalt cerium O composite metallic oxide catalyst. Chinese rare-earth journal, 2006,24 (special editions): 10 and Li Xue, Changbin Zhang, Hong He, Yasutake Teraoka.Catalyticdecomposition of N 2O over CeO 2Promoted Co 3O 4Spinel catalyst.AppliedCatalysis B:Environmental, 2007,75:157-164).
Report the Co that alkali metal K modifies in addition 3O 4Catalyst is at 0.5%N 2O, 2%O 2, 2.5%H 2Decomposing N under the O condition 2The activity of O, N 2The temperature that O decomposes fully is about 380 ℃ of (Kimihiro Asano, Chie Ohnishi, Shinji Iwamoto, Yasushi Shioya, Masashi Inoue.Potassium-doped Co 3O 4Catalyst for direct decomposition of N 2O.Applied Catalysis B:Environmental, 2008,78:242-249).
N 2The O decomposition reaction is a strong exothermal reaction, and reaction bed temperature raises significantly in course of reaction, and reaction bed temperature may reach 500-700 ℃.Though the catalyst of above-mentioned bibliographical information is better active, the sintering temperature of catalyst is on the low side, has only 400 ℃; N in the gas of Shi Yonging in addition 2The content of O has only 0.1-0.5%, N in the industrial smoke 2The concentration of O.Also there is a big difference apart from commercial Application to this shows it.
Patent documentation CN1440309A describes N in a kind of decomposition gas 2O catalyst, this catalyst comprise that 0.1-10mol% loads on the Co on the cerium oxide carrier 3-xM xO 4, wherein M is Fe and Al, x=0-2, catalyst and N 2O contacts under 500~1000 ℃ temperature and reacts.The embodiment of this patent shows, N 2O is at CoO 4/ CeO 2Or Co 2AlO 4/ CeO 2Decomposition temperature is higher on the catalyst, and decomposition temperature is more than 800 ℃ fully.
Patent documentation CN1324265A and CN1116411A mention N in a kind of Cu of containing catalyst decomposes gas 2O.It is M that this catalyst comprises a kind of general formula xAl 2O 4Compound, M is the mixture of Cu or Cu and Zn and/or Mg, x is 0.8~1.5.
Patent CN1214850C discloses N in a kind of decomposition gas 2O catalyst and technology, this catalyst are one or more years of iron zeolites, and the kind of zeolite is: MFI, BEA, FER, MOR and/or MEL; Carrying the iron zeolite is MFI, and zeolite is Fe-ZSM5, and iron is carried on the zeolite by ion-exchange.
Do not see in the above-mentioned document to have and be used for direct decomposing N with of the present invention 2The report of the Catalysts and its preparation method of O.
Summary of the invention
The purpose of this invention is to provide a kind of decomposing N that is used for 2The catalyst of O, it is that a kind of catalytic activity is good, N 2The catalyst that the decomposition temperature of O is low, it can be applicable to the direct decomposition of laughing gas, can make N in the industrial waste gas 2O concentration reduces, and reduces atmosphere pollution, the protection environment.
Another object of the present invention provides this Preparation of catalysts method.
A further object of the present invention provides the purposes of this catalyst.
The present invention realizes above-mentioned purpose by following technical proposal:
A kind of N that is used for 2The catalyst that O decomposes contains composite metal oxide and molecular sieve carrier,
Described composite metal oxide is spinel structure or perovskite-like structure, and general molecular formula is Co 3-xM xO 4Or La 2-yM yBO 4, M is one or both or the two or more combination that is selected from rare earth metal, transition metal, alkali metal or the alkaline-earth metal, B is one or more the combination that is selected from the transition metal, x=0~2.8, y=0~1.8.
Described molecular sieve carrier is ZRP, PSRY or beta-molecular sieve.
Described rare earth metal is La, Ce, Pr or Nd; Transition metal is Fe, Ni, Cu, Zn, Mn, Cr, V or Zr; Alkali metal is Na, K, Rb or Cs; Alkaline-earth metal is Mg, Ca, Sr or Ba.
Be used for N 2The Preparation of catalysts method that O decomposes, this method may further comprise the steps:
A) take by weighing corresponding metal salt and organic complexing agent, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent,
B) molecular sieve carrier is inserted in (a) aqueous solution and flood, and evaporating water obtains catalyst precursor under 30~90 ℃ of temperature, then catalyst precursor is placed 500~1000 ℃ of following roastings 2~10 hours, promptly obtains catalyst of the present invention.
Described metallic salt is nitrate or acetate, and organic complexing agent is citric acid, oxalic acid or acetic acid.
With the catalyst is weight basis, and composite metal oxide is preferably 0.1~50% in the load capacity of molecular sieve carrier.
Catalyst of the present invention also can contain other component, binder component for example, and described binding agent is aluminium oxide, Ludox for example.
A further object of the present invention provides the purposes of this catalyst.This catalyst can be used for the N of any concentration in the decomposition gas 2O, the O in the gas 2, NOx, CO 2The existence that reaches gas components such as CO does not influence the use of described catalyst.Be the temperature rise of control beds, use N in the gas of described catalyst treatment 2The concentration of O is preferably less than 20v%.
Adopt the N that is used for of the present invention 2The catalyst that O decomposes, its catalytic activity is good, N 2The decomposition temperature of O is low.Its application can make N in the industrial waste gas 2O concentration reduces, and reduces atmosphere pollution, the protection environment.
The specific embodiment
By the following examples technical scheme of the present invention is further described.
In each embodiment, adopt following experimental facilities and analytical method: adopt fixed-bed micro-reactor to estimate catalyst provided by the invention at N 2Catalytic activity in the O decomposition reaction.Reactor adopts the quartz ampoule of internal diameter 8mm, the temperature reaction of automatic temperature control instrument control program, and programming rate is 5 ℃/min.The catalyst particles granularity is the 20-40 order, takes by weighing the sample of 0.4g, is filled in the constant temperature zone of reaction tube, prepares reacting gas on request in advance, and gas composition is the N of 12v% 2O, the O of 16.8v% 2, all the other are N 2, gas flow is 80ml/min, reaction end gas adopts gas-chromatography and the online detection of NOx analyzer.Use remaining N in Paropak Q chromatographic column and the TCD detector detection reaction tail gas 2O, the NO that forms in the NOx analyzer detection reaction.Use T 10And T 95Expression N 2The O conversion ratio is 10% and the reaction temperature of 95% o'clock correspondence, T 10Be N 2The O temperature of initial decomposition, T 95Be N 2The complete decomposition temperature of O, this temperature is low more, and catalyst activity is good more.
Adopt the crystal structure of Japanese XRD-7000 type X-ray diffractometer test sample.Experiment condition is Cu K αTarget, voltage 40KV, electric current 30mA, 4 °/min of sweep speed, 5 ° 80 ° of sweep limits.
In following examples, the activity of such catalysts appreciation condition is not described, all adopt above-mentioned experiment condition.
Embodiment 1
Take by weighing cobalt nitrate (Co (NO 3) 26H 2O) 402.87g and citric acid (C 6H 8O 7H 2O) 296.26g, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent, molecular sieve carrier ZRP 1500g inserted in the aqueous solution flood, and drying obtains catalyst precursor under 30 ℃ of temperature, and it is 10% Co that above-mentioned presoma was promptly obtained load capacity of the present invention in 10 hours 500 ℃ of roastings 3O 4/ ZRP catalyst.The XRD analysis result shows that composite metal oxide has spinel structure.
This catalyst is used for N 2The decomposition of O, gas composition is: the N of 0.65v% 2O, the O of 0.88v% 2, all the other are N 2Condition under, N 2The decomposition temperature T of O 10Be 310 ℃, T 95It is 470 ℃.
Embodiment 2
Take by weighing cobalt nitrate (C 6H 8O 7H 2O) 1282.68g, lanthanum nitrate (La (NO 3) 36H 2O) 146.81g, potassium nitrate (KNO 3) 34.28g and citric acid 1069.97g, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent, molecular sieve carrier ZRP 500 gram and beta-molecular sieve 500g inserted in the aqueous solution flood, and drying obtains catalyst precursor under 30 ℃ of temperature, and it is 30% La that above-mentioned presoma was promptly obtained load capacity in 4 hours 800 ℃ of roastings 0.2K 0.2Co 2.6O 4/ (ZRP+ β) catalyst.The XRD analysis result shows that composite metal oxide has spinel structure.
This catalyst is used for N 2The decomposition of O, N 2The decomposition temperature T of O 10Be 350 ℃, T 95It is 520 ℃.
Embodiment 3
Take by weighing cobalt nitrate 638.84g, cerous nitrate (Ce (NO 3) 36H 2O) 953.17g, ferric nitrate (Fe (NO 3) 29H 2O) 886.79g and citric acid 1385.54g, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent, molecular sieve carrier beta-molecular sieve 700g inserted in the aqueous solution flood, and drying obtains catalyst precursor under 60 ℃ of temperature, and it is 50% CoCeFeO that above-mentioned presoma was promptly obtained load capacity of the present invention in 6 hours 700 ℃ of roastings 4/ beta catalyst.The XRD analysis result shows that composite metal oxide has spinel structure.
This catalyst is used for N 2The decomposition of O, N 2The decomposition temperature T of O 10Be 360 ℃, T 95It is 530 ℃.
Embodiment 4
Take by weighing cobalt nitrate 1968.89g and barium nitrate (Ba (NO 3) 2) 649.92g and citric acid 1941.01g, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent, molecular sieve carrier ZRP 400g inserted in the aqueous solution flood, and drying obtains catalyst precursor under 90 ℃ of temperature, and it is 70% Co that above-mentioned presoma was promptly got load capacity of the present invention in 4 hours 600 ℃ of roastings 2.2Ba 0.8O 4/ ZRP catalyst.The XRD analysis result shows that composite metal oxide has spinel structure.
This catalyst is used for N 2The decomposition of O, gas composition is: the N of 0.65v% 2O, all the other are N 2Condition under, N 2The decomposition temperature T of O 10Be 340 ℃, T 95It is 470 ℃.
Embodiment 5
Take by weighing cobalt nitrate 1235.33g, 50% manganese nitrate solution 506.39g, lanthanum nitrate 1531.70g, magnesium nitrate 362.79g, citric acid 2232.71g, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent, molecular sieve carrier beta-molecular sieve 120g inserted in the aqueous solution flood, and vacuum drying obtains catalyst precursor under 80 ℃ of temperature, and it is 90% LaCo that above-mentioned presoma was promptly got load capacity of the present invention in 2 hours 1000 ℃ of roastings 1.2Mn 0.4Mg 0.4O 4/ beta catalyst.XRD analysis detects spinel structure and perovskite-like structure.
This catalyst is used for N 2The decomposition of O, N 2The decomposition temperature T of O 10Be 385 ℃, T 95It is 510 ℃.
Embodiment 6
Take by weighing cobalt nitrate 39.77g, calcium nitrate 161.35g, lanthanum nitrate 532.55g, oxalic acid 258.41g, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent, molecular sieve carrier beta-molecular sieve 1000g inserted in the aqueous solution flood, and drying obtains catalyst precursor under 70 ℃ of temperature, and it is 20% La that above-mentioned presoma was promptly got load capacity of the present invention in 6 hours 600 ℃ of roastings 1.8Co 0.2CaO 4/ beta catalyst.The XRD analysis result shows that composite metal oxide has perovskite-like structure.
This catalyst is used for N 2The decomposition of O, N 2The decomposition temperature T of O 10Be 450 ℃, T 95It is 650 ℃.
Embodiment 7
Take by weighing cobalt acetate 8.13g, Schweinfurt green 3.26g and acetic acid 2.94g, they are soluble in water respectively, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent, molecular sieve carrier PSRY molecular sieve 4000g inserted in the aqueous solution flood, and drying obtains catalyst precursor under 70 ℃ of temperature, and it is 0.1% Co that above-mentioned presoma was promptly got load capacity of the present invention in 4 hours 800 ℃ of roastings 2CuO 4/ PSRY catalyst, the XRD analysis result shows that composite metal oxide has spinel structure.
This catalyst is used for N 2The decomposition of O, N 2The decomposition temperature T of O 10Be 450 ℃, T 95It is 650 ℃.
Embodiment 8
Take by weighing ferric nitrate (Fe (NO 3) 29H 2O) 179.28g, lanthanum nitrate 384.32g and citric acid 280.11g, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent, molecular sieve carrier ZRP 1000g inserted in the aqueous solution flood, and drying obtains catalyst precursor under 70 ℃ of temperature, and it is 15% La that above-mentioned presoma was promptly obtained load capacity in 4 hours 800 ℃ of roastings 2FeO 4/ ZRP catalyst.The XRD analysis result shows that composite metal oxide has perovskite-like structure.
This catalyst is used for N 2The decomposition of O, N 2The decomposition temperature T of O 10Be 420 ℃, T 95It is 540 ℃.
Embodiment 9
Take by weighing cobalt nitrate 875.67g, zinc nitrate (Zn (NO 3) 26H 2O) 642.92g and citric acid 638.22g, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent, molecular sieve carrier β 1000g inserted in the aqueous solution flood, and drying obtains catalyst precursor under 60 ℃ of temperature, and it is 20% ZnCo that above-mentioned presoma was promptly obtained load capacity in 4 hours 600 ℃ of roastings 2O 4/ beta catalyst.The XRD analysis result shows that composite metal oxide has spinel structure.
This catalyst is used for N 2The decomposition of O, N 2The decomposition temperature T of O 10Be 360 ℃, T 95It is 500 ℃.
Embodiment 10
Take by weighing cobalt nitrate 315.29g and citric acid 227.94g, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent, molecular sieve carrier β 1000g inserted in the aqueous solution flood, and drying obtains catalyst precursor under 70 ℃ of temperature, and it is 8% Co that above-mentioned presoma was promptly obtained load capacity in 4 hours 800 ℃ of roastings 3O 4/ beta catalyst.The XRD analysis result shows that composite metal oxide has spinel structure.
This catalyst is used for N 2The decomposition of O, N 2The decomposition temperature T of O 10Be 340 ℃, T 95It is 450 ℃.
Embodiment 11
Take by weighing cobalt nitrate 559.47g, cerous nitrate 30.99g and citric acid 433.36g, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent, molecular sieve carrier ZRP 1000g inserted in the aqueous solution flood, and drying obtains catalyst precursor under 70 ℃ of temperature, and it is 15% Co that above-mentioned presoma was promptly obtained load capacity in 6 hours 800 ℃ of roastings 2.8Ce 0.2O 4/ ZRP catalyst.The XRD analysis result shows that composite metal oxide has spinel structure.
This catalyst is used for N 2The decomposition of O, N 2The decomposition temperature T of O 10Be 349 ℃, T 95It is 455 ℃.

Claims (7)

1, a kind of N that is used for 2The catalyst that O decomposes contains composite metal oxide and molecular sieve carrier, it is characterized in that:
Described composite metal oxide has spinel structure and/or perovskite-like structure, and general molecular formula is Co 3-xM xO 4Or La 2-yM yBO 4, M is one or both or the two or more combination that is selected from rare earth metal, transition metal, alkali metal or the alkaline-earth metal, B is one or more the combination that is selected from the transition metal, and x=0~2.8, y=0~1.8,
Described molecular sieve carrier is ZRP, PSRY or beta-molecular sieve.
2, the N that is used for according to claim 1 2The catalyst that O decomposes, it is characterized in that: described rare earth metal is La, Ce, Pr or Nd; Transition metal is Fe, Ni, Cu, Zn, Mn, Cr, V or Zr; Alkali metal is Na, K, Rb or Cs; Alkaline-earth metal is Mg, Ca, Sr or Ba.
3, the N that is used for according to claim 1 2The catalyst that O decomposes, it is characterized in that: be benchmark with the catalyst weight, composite metal oxide is 0.1~90% in the load capacity of molecular sieve carrier, and the preferred negative carrying capacity is 0.1~50%.
4, the described N that is used for of claim 1 2The Preparation of catalysts method that O decomposes, it is characterized in that: this method may further comprise the steps:
A) with corresponding metal salt and organic complexing agent, be dissolved in the water respectively and measure compounding and close solution, obtain the aqueous solution of metalline and organic complexing agent,
B) molecular sieve carrier is inserted in (a) aqueous solution and flood, and drying obtains catalyst precursor under 30~90 ℃ of temperature, then catalyst precursor is placed 500~1000 ℃ of following roastings 2~10 hours, promptly obtains catalyst of the present invention.
5, according to claim 1,3,4 described Preparation of catalysts methods, it is characterized in that: described metallic salt is nitrate or acetate, and organic complexing agent is citric acid, oxalic acid or acetic acid.
6, according to the described N that is used for of claim 3 2The Preparation of catalysts method that O decomposes, it is characterized in that: be benchmark with the catalyst weight, composite metal oxide is 0.1~90% in the load capacity of molecular sieve carrier, and the preferred negative carrying capacity is 0.1~50%.
7, the described catalyst of claim 1 is used for flue gas or industrial waste gas N 2The purposes that O decomposes.
CN 200810119339 2008-09-04 2008-09-04 Catalyst for decomposition of N2O and preparation method and application thereof Pending CN101664694A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101934227A (en) * 2010-09-09 2011-01-05 复旦大学 Catalyst for selective reduction of NOx with NH3 and preparation method thereof
CN102698581A (en) * 2012-05-28 2012-10-03 成都信息工程学院 Method for producing sodium sulfate and sodium nitrate by simultaneous desulfurization and denitrification by soda-citric acid cobalt (II)
CN103861597A (en) * 2012-12-18 2014-06-18 中国科学院大连化学物理研究所 Supported spinel compound and preparation and application thereof
CN106994341A (en) * 2017-04-20 2017-08-01 北京石油化工学院 For photocatalysis Decomposition N2O catalyst and its production and use
CZ307189B6 (en) * 2017-01-30 2018-03-07 Ústav fyzikální chemie J. Heyrovského AV ČR, v. v. i. A method of production of catalysts of a perovskite structure, catalysts perovskite structure and their use for high temperature decomposition of N2O
CN115779916A (en) * 2022-12-06 2023-03-14 北京石油化工学院 Catalyst, method for reducing nitrogen oxides and application of catalyst

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101934227A (en) * 2010-09-09 2011-01-05 复旦大学 Catalyst for selective reduction of NOx with NH3 and preparation method thereof
CN101934227B (en) * 2010-09-09 2012-10-17 复旦大学 Catalyst for selective reduction of NOx with NH3 and preparation method thereof
CN102698581A (en) * 2012-05-28 2012-10-03 成都信息工程学院 Method for producing sodium sulfate and sodium nitrate by simultaneous desulfurization and denitrification by soda-citric acid cobalt (II)
CN103861597A (en) * 2012-12-18 2014-06-18 中国科学院大连化学物理研究所 Supported spinel compound and preparation and application thereof
CN103861597B (en) * 2012-12-18 2017-04-05 中国科学院大连化学物理研究所 A kind of support type catalytic removal of nox and its preparation and application
CZ307189B6 (en) * 2017-01-30 2018-03-07 Ústav fyzikální chemie J. Heyrovského AV ČR, v. v. i. A method of production of catalysts of a perovskite structure, catalysts perovskite structure and their use for high temperature decomposition of N2O
CN106994341A (en) * 2017-04-20 2017-08-01 北京石油化工学院 For photocatalysis Decomposition N2O catalyst and its production and use
CN106994341B (en) * 2017-04-20 2020-07-03 北京石油化工学院 For photocatalytic decomposition of N2Catalyst of O and preparation method and application thereof
CN115779916A (en) * 2022-12-06 2023-03-14 北京石油化工学院 Catalyst, method for reducing nitrogen oxides and application of catalyst

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Application publication date: 20100310