CN100522317C - Composite Co-Ce oxide catalyst for direct low temperature catalytic decomposition of N2O - Google Patents
Composite Co-Ce oxide catalyst for direct low temperature catalytic decomposition of N2O Download PDFInfo
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- CN100522317C CN100522317C CNB2005101240323A CN200510124032A CN100522317C CN 100522317 C CN100522317 C CN 100522317C CN B2005101240323 A CNB2005101240323 A CN B2005101240323A CN 200510124032 A CN200510124032 A CN 200510124032A CN 100522317 C CN100522317 C CN 100522317C
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- Prior art keywords
- catalyst
- preparation
- cerium
- low temperature
- catalytic decomposition
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Abstract
The present invention discloses one kind of composite Co-Ce oxide catalyst for direct low temperature catalytic decomposition of N2O into N2 and O2. The catalyst has the main component Co3O4 and auxiliary component CeO2, with the molar ratio Ce/Co being 0-1. The catalyst is used in direct catalytic decomposition of N2O of concentration 1000 ppm into N2 and O2 in a fixed bed reactor at the conditions of normal pressure, 400 deg.c and space velocity of 0.048-0.2 g .s/cu cm. The catalyst is less affected by O2 and H2O, and has relatively high low temperature catalytic activity.
Description
Invention field
But the present invention relates to a kind of efficient catalytic N
2Cobalt and cerium compound oxide catalyst that O directly decomposes and preparation method thereof.
Technical background
For a long time, because nitrous oxide (N
2O) itself human body is not had overt toxicity, be not counted as a kind of dusty gas.But discovering in recent ten years, N
2O is that a kind of important atmosphere pollution-it is not only a kind of greenhouse gases, and ozone layer is had destruction.Because it is highly stable in stratosphere, average life span reaches 150 years, and its greenhouse effects are respectively CO
2310 times, CH
421 times [Applied Catalysis B:Environmental 44 (2003) 117-151].N
2O is NO in the stratosphere
xMain source, and NO
xOzone layer there is very big destruction [Science251 (1991) 932-934].At N
2In the two big emission sources of O, the discharging that mankind's activity caused is being the trend that rises year by year.Adipic acid production process, nitric acid production process, and the combustion process of various fossil fuels all can give off (comprising moving source and stationary source two parts) N of variable concentrations
2O[Applied Catalysis B:Environmental 9 (1996) 25-64].Though various countries do not formulate strict emission control standards except that Kyoto Protocol at present, some big adipic acid factories (as Du Pont, BASF etc.) have begun to take measures, and reduce the N in the tail gas
2The discharge capacity of O.
Catalyzing N
2O directly is decomposed into N
2And O
2Be to eliminate N
2The method that O is direct, the most most economical.The present elimination N that uses in adipic acid factory
2The method of O mainly is exactly the method for directly decomposing.But N in the adipic acid tail gas
2The concentration of O higher (about 30-50%), and N
2The O decomposition reaction is exothermic reaction, so cartalytic decomposition effect generally carries out under higher temperature, requires not high to the low temperature active of catalyst.Be lower than 400 ℃, N for other temperature
2The processing of the tail gas of O concentration about 0.1% as tail gas in the nitric acid production and vehicle exhaust etc., then requires catalyst at a lower temperature with regard to the energy catalyzing N
2O directly is decomposed into N
2And O
2, and require the O coexisted
2And H
2Influence such as O is little.
Noble metal Rh, Ru catalyst have better low temperature activity [Advances in Environmental Research4 (2000) 325-338, Applied Catalysis B:Environmental 13 (1997) 113-122] usually, but they are subjected to O
2And H
2The influence of O is bigger, and price is higher relatively, has limited their extensive use.US 5,407, and 652 disclose a series of houghite catabolite catalyst, and wherein with Co-Rh, Al-HT's is active best, can be at 450 ℃, 2.5%O
2And 2%H
2O exists down, reaches the N to 985ppm
2The elimination fully of O, catalytic performance that it is excellent and Rh are added with confidential relation.CN 03127927.9 discloses a kind of removing method of nitrous oxide, uses M
xCo
1-xCo
2O
4(M=Mg, Ni Zn) as catalyst, are decomposed into N at normal pressure, the 50-300 ℃ nitrous oxide with 1000ppm-30%
2And O
2
Brief summary of the invention
The present invention discloses a kind of low-temperature catalyzed N that is used for
2The preparation method of the cobalt and cerium compound oxide catalyst that O directly decomposes.
The main active component of catalyst of the present invention is Co
3O
4Spinelle, accessory constituent are CeO
2, the specific area of catalyst is 68-119m
2G
-1
Catalyst of the present invention adopts the coprecipitation preparation, it is characterized in that earlier cobalt nitrate and cerous nitrate are configured to the mixed solution of 0.5-0.8mol/l, stirs down at 10-40 ℃, drips 10-30%Na
2CO
3Or K
2CO
3The aqueous solution is as precipitating reagent, and regulating the pH value is 8.6-9.3, stirs 0-3 hour, leaves standstill 0-5 hour, and sediment is after suction filtration, washing, and dried overnight makes finished catalyst 400-500 ℃ of roasting at last.
In the Preparation of Catalyst among the present invention, with Ce/Co molar ratio computing CeO
2Addition be 0～1.
The prepared catalyst of the present invention is mainly used in normal pressure, (furnace temperature, down with) below 400 ℃, air speed W/F (W is a catalyst quality, and F is a gas flow, down with) are 0.2gscm
-3-0.048gscm
-3Under the operating condition, in the fixed bed reactors, 1000ppm and following N
2The cartalytic decomposition effect of O.At normal pressure, 0.2gscm
-3, under 250 ℃ of reaction conditions, can realize N to 1000ppm
2The complete catalytic decomposition of O; Add 10%O
2And 3%H
2Behind the O, can be 320 ℃ of realizations to 1000ppmN
2The complete catalytic decomposition of O.
The prepared catalyst of the present invention is subjected to O
2And H
2The influence of O is less, particularly is subjected to O
2Influence less, shown catalytic activity preferably.
The characteristics of catalyst of the present invention are: (1) Preparation of Catalyst is simple, is particularly suitable for large-scale production.(2) catalyst low-temperature activity is good, and O is coexisted
2And H
2The influence of O is little, and higher utility is arranged.
Instantiation
The Preparation of Catalyst example
Catalyst 1
With 7.28g Co (NO
3)
26H
2O is dissolved in the 40ml distilled water, forms clear solution, and room temperature and stirring drip 15wt%K down
2CO
3The aqueous solution, the pH value of regulator solution is 9.1, continue to stir 1 hour, leave standstill 3 hours after, suction filtration, washing, 100 ℃ of following dried overnight, 400 ℃ of following roastings 2 hours obtain finished catalyst at last.
Catalyst 2
With 7.28g Co (NO
3)
26H
2O and 0.63g Ce (NO
3)
36H
2O is dissolved in the 40ml distilled water, forms the mixed solution of clarification, and other Preparation of catalysts process is with catalyst 1.
Catalyst 3
With 7.28g Co (NO
3)
26H
2O and 5.45g Ce (NO
3)
36H
2O is dissolved in the 60ml distilled water, forms the mixed solution of clarification, and other Preparation of catalysts process is with catalyst 1.
Catalyst 4
With 7.28g Co (NO
3)
26H
2O and 8.66g Ce (NO
3)
36H
2O is dissolved in the 40ml distilled water, forms the mixed solution of clarification, and other Preparation of catalysts process is with catalyst 1.
Catalyst 5
Preparation process is substantially with catalyst 2, unique different be that control pH value is 8.6 when carrying out precipitation titration.
Catalyst 6
Preparation process is substantially with catalyst 2, unique different be after precipitation process is finished, the stirring of only having carried out 1 hour is aging.
Catalyzing N
2O decomposition reaction embodiment
Example 1
Getting 0.5g 40-60 order catalyst 1-6, to place internal diameter be the quartz tube reactor of 6mm, feeds N
2O concentration is the reacting gas of 1000ppm, and argon gas is a balance gas, and air speed is 0.2gscm
-3, under normal pressure,, the results are shown in table 1 by control heating furnace temperature programming successive reaction.
Catalyst N under the table 1 differential responses temperature
2The activity that O directly decomposes
A: conversion ratio reaches 100% actual furnace temperature
Example 2
Getting 0.5g 40-60 order catalyst 2, to place internal diameter be the quartz tube reactor of 6mm, feeds N
2O concentration is the reacting gas of 1000ppm, and argon gas is a balance gas, and the adjustment air speed is 0.2gscm
-3～0.048gscm
-3, under normal pressure,, the results are shown in table 2 by control heating furnace temperature programming successive reaction.
Example 3
Getting 0.5g 40-60 order catalyst 1 and 2, to place internal diameter be the quartz tube reactor of 6mm, feeds 1000ppm N
2O gas, 0 or 10%O
2, 0 or 3% water vapour, argon gas are balance gas, air speed is 0.2gscm
-3, under normal pressure,, the results are shown in table 3 and table 4 by control heating furnace temperature programming successive reaction.
Catalyst 2 catalyzing Ns under the table 2 differential responses temperature
2The activity that O directly decomposes
A: conversion ratio reaches 100% actual furnace temperature
Catalyst 1 catalyzing N under the table 3 differential responses temperature
2The activity that O directly decomposes
Catalyst 2 catalyzing Ns under the table 4 differential responses temperature
2The activity that O directly decomposes
A: conversion ratio reaches 100% actual furnace temperature
Claims (7)
1. low-temperature catalyzed N
2O directly is decomposed into N
2And O
2Cobalt and cerium compound oxide catalyst, it is characterized in that: the main active component of catalyst is Co
3O
4, accessory constituent is CeO
2, the cerium constituent content is counted (〉 0 with total metallic element)-5.48mol%, the specific area of catalyst is 68-119m
2/ g.
2. Preparation of catalysts method as claimed in claim 1, it is characterized in that adopting the method for co-precipitation, cobalt salt and cerium salt are configured to the 0.5-0.8mol/l mixed solution, under 10-40 ℃, add precipitating reagent and under pH=8.6-9.3, precipitate, after wearing out, filtration, washing, drying, last roasting obtains catalyst, and the cerium constituent content is counted (〉 0 with total metallic element in the catalyst)-5.48mol%.
3. preparation method as claimed in claim 2 is characterized in that described cobalt salt and cerium salt are the nitrate of 0-6 the crystallization water of band.
4. preparation method as claimed in claim 2 is characterized in that precipitating reagent is the Na of 10-30wt%
2CO
3Or K
2CO
3The aqueous solution.
5. preparation method as claimed in claim 2 is characterized in that burin-in process comprises leaving standstill of 0-3 hour stirring and 0-5 hour.
6. preparation method as claimed in claim 2 is characterized in that precipitation process carries out at 10-40 ℃.
7. preparation method as claimed in claim 2 is characterized in that sintering temperature is 400-500 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101240323A CN100522317C (en) | 2005-11-28 | 2005-11-28 | Composite Co-Ce oxide catalyst for direct low temperature catalytic decomposition of N2O |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101240323A CN100522317C (en) | 2005-11-28 | 2005-11-28 | Composite Co-Ce oxide catalyst for direct low temperature catalytic decomposition of N2O |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1973961A CN1973961A (en) | 2007-06-06 |
| CN100522317C true CN100522317C (en) | 2009-08-05 |
Family
ID=38124482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101240323A Active CN100522317C (en) | 2005-11-28 | 2005-11-28 | Composite Co-Ce oxide catalyst for direct low temperature catalytic decomposition of N2O |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376107B (en) * | 2008-09-25 | 2011-08-31 | 烟台大学 | Cobalt aluminum composite oxide supported gold catalyst for decomposing dinitrogen monoxide and preparation method thereof |
| CN114643055B (en) * | 2022-04-08 | 2023-07-07 | 浙江大学 | Nano-gold-loaded nano cerium oxide for catalyzing direct decomposition of nitrogen oxides and preparation method thereof |
| CN116371413A (en) * | 2023-03-02 | 2023-07-04 | 上海交通大学 | Modified cobalt-based catalyst for low-temperature high-efficiency decomposition of nitrous oxide and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219445A (en) * | 1998-11-16 | 1999-06-16 | 天津大学 | New synthetic copper methoxide series catalysts and their preparation method |
| CN1440309A (en) * | 2000-07-05 | 2003-09-03 | 挪威海德罗公开有限公司 | Catalyst for decomposing nitrous oxide and method for performing processes comprising formation of nitrous oxide |
| CN1557546A (en) * | 2004-01-16 | 2004-12-29 | 复旦大学 | Composite oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof |
-
2005
- 2005-11-28 CN CNB2005101240323A patent/CN100522317C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219445A (en) * | 1998-11-16 | 1999-06-16 | 天津大学 | New synthetic copper methoxide series catalysts and their preparation method |
| CN1440309A (en) * | 2000-07-05 | 2003-09-03 | 挪威海德罗公开有限公司 | Catalyst for decomposing nitrous oxide and method for performing processes comprising formation of nitrous oxide |
| CN1557546A (en) * | 2004-01-16 | 2004-12-29 | 复旦大学 | Composite oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof |
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| CN1973961A (en) | 2007-06-06 |
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