CN102380410A - Ferro-cobalt bimetallic catalyst for catalyzing nitrous oxide (N2O) decomposition - Google Patents
Ferro-cobalt bimetallic catalyst for catalyzing nitrous oxide (N2O) decomposition Download PDFInfo
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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)
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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
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- Y02P20/30—Improvements relating to adipic acid or caprolactam production
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Abstract
The invention provides a ferro-cobalt bimetallic load mordenite catalyst for catalyzing the nitrous oxide (N2O) decomposition and a preparation method. The catalyst can be used for decomposing most or all N2O in a pollution discharge system into N2 and O2 under the conditions that the space velocity is 30000h<-1>, the reaction temperature is 400 to 500 DEG C, the N2O concentration is 0.1 to 30 percent, and the H2O is 2 to 10 percent. In addition, the catalyst has high stability, and the activity of the catalyst is not decayed after 100h of the continuous nitric plant tail gas emission simulation. The catalyst has the advantages that the preparation process is simple, the cost is low, the catalyst is used for the catalytic N2O decomposition, the activity is high, and the stability is good. The technology has wide applicability, can be used for the N2O emission reduction process (such as processes of nitric acid production, adipate production and the like) of multiple industry sources and has wide application prospects.
Description
Technical field
The present invention relates to nitrous oxide (N
2O) catalytic decomposition catalyst and preparation thereof belong to heterogeneous catalysis technology and field of environment protection thereof, specifically are a kind of control atmosphere pollution, particularly administer the Catalysts and its preparation method of nitric plant and adipic acid factory tail gas pollution.
Background technology
N
2O is a kind of colourless, gas that faint sweet taste is arranged, and human body is not had overt toxicity.Suck the nervous excitation that makes the people on a small quantity, cause laugh (therefore being commonly called as laughing gas); Suction more then can make the people lose consciousness, sometimes with its anesthetic as slight operation.Present N
2O has been widely applied to electronics industry and medical domain, and fields such as semiconductor devices manufacturing, pressure packing and food industry.Because N
2The O stable in properties does not have obvious toxic action to human body, all is not counted as dusty gas for a long time, thereby does not obtain the attention of all circles.Naturally the N that produces in activity and the production process
2O generally all without stint enter atmosphere.Yet research in recent ten years shows, N
2O can not only the heavy damage ozone layer, and has very strong greenhouse effects.So far, N
2O has caused people's extensive attention to the harm of environment.N
2O is 6 kinds of greenhouse gases (CO of Kyoto Protocol regulation
2, N
2O, CH
4, HFC, PFC, SF
6One of).It is generally acknowledged, at present N in the atmosphere greenhouse gases composition
2O is only second to CO for the percentage contribution of global warming
2And CH
4And, N
2O is highly stable in the troposphere, and average life span is long, and its global warming potential is respectively CO
2310 times, CH
415 times.It is reported N
2The 270ppb of the background concn of O in atmosphere before by the industrial revolution is increased to 316ppb in 2000, annual rate increase with 0.2-0.3%.And discover that mankind's activity is to cause atmosphere N
2The main cause that O concentration increases is wherein discharged N
2The topmost industrial source of O comprises aliphatic acid production, production of chemical fertilizer such as nitric acid, adipic acid and uses the industrial process of nitric acid as oxidant.Therefore, research can efficiently remove in the production processes such as nitric acid and adipic acid and produce N
2Technology and the method for O have important practical significance.
N
2The direct decomposition technique of O catalysis is with N
2O directly is decomposed into N under the effect of catalyst
2And O
2Because this method is simple, expense is low, need not add reducing agent, is considered to eliminate N
2The Perfected process of O.Present catalyzing N
2The catalyst that O decomposes mainly comprises metal oxide catalyst, like MnO
x/ MgO etc. (US 5705136); The hydrotalcite composite oxides of deriving are like Rh
0.01Mg
0.71Al
0.28O
1.145(EP 1262224B1) etc.; The spinel structure composite oxides are like CuAl
2O
4(US6723295B1) etc.; Modified molecular sieve catalyst is like Co-ZSM-5 (US 5171553).Wherein ion-exchange cobalt molecular sieve catalyst is because its high N
2O degrading activity and anti-toxic (NO, O
2, H
2Advantage such as O) is at the N that administers production processes dischargings such as nitric acid or adipic acid
2O tail gas aspect has very high using value and Research Significance.Especially mordenite molecular sieve (Co-MOR) catalyst of in author's research in early stage, finding the cobalt load of ion-exchange preparation has very high catalyzing N
2O degrading activity (being higher than Co-ZSM-5), and activity still keeps very high in the presence of other gases.But Co-MOR catalyst ion exchange degree still can not reach 100%, and residual hydroxyl proton can cause catalyst that inactivation in the presence of the water is being arranged, and stability needs further to improve.On the other hand, the Fe molecular sieve is owing to have very high anti-poisoning (SO
2And H
2O etc.) and excellent stability, also be widely used in N
2The O cartalytic decomposition effect; But its activity is lower than the Co molecular sieve.Therefore the present invention is through two step ion-exchanges; Successively Co and two kinds of metals of Fe are incorporated into molecular sieve; In conjunction with Fe ion high stability and Co ion advantage of high activity, prepared and had high catalytic activity more and the Co of stability, the MOR molecular sieve catalyst of Fe bimetallic load.
Summary of the invention
The object of the present invention is to provide a kind of mordenite molecular sieve catalyst (CoFe-MOR) that is used for the ferro-cobalt bimetallic load that industrial source discharging nitrous oxide eliminates and preparation method thereof.
The present invention utilizes the CoFe-MOR catalyst, and under experimental condition, air speed is 30,000h
-1, temperature is 400-500 ℃, N
2O concentration is 0.1-30%, O
2Be 5-10%, NO is 0.1-1%, H
2When O is 2-10%, can be with most or all of N in the system
2O is decomposed into N
2And O
2And have very high stability, after carrying out 100 hours continuously under the simulation nitric acid tail gas condition, activity of such catalysts is obviously decay not.
For realizing above-mentioned purpose, the N that is used for provided by the invention
2The CoFe-MOR catalyst that O decomposes is to be the source molecular sieve with the modenite, prepares through two step ion-exchanges successively load C o and Fe active component.Described active component Co and the Fe load capacity in the MOR molecular sieve is respectively 1-10% and 0.1-5%.Exchange sequence with first Co after Fe be the best, concrete preparation method is following:
1) under certain pH value (is 2-9 like the pH value) is with the Co that contains of 0.01-2mol/L
2+The aqueous solution and modenite (MOR) room temperature under exchange 24-48 hour, repeats 1-5 time, dried 15-25 hour for 80-100 ℃ time, be warming up to then in 500 ℃ of air constant temperature calcining 4-6 hour, obtain cobalt loaded mordenite (Co-MOR);
2) under certain pH value (is 2-9 like the pH value) is with the Fe that contains of 0.01-2mol/L
3+The aqueous solution and Co-MOR exchange 24-48 hour, repeats 1-5 time, dried 15-25 hour for 80-100 ℃ time, be warming up to then in 500 ℃ of air constant temperature calcining 4-6 hour, obtain ferro-cobalt loaded mordenite (CoFe-MOR) catalyst.
Catalyst preparation process of the present invention is simple, and is with low cost, and it is active high to be used for the nitrous oxide catalytic decomposition, good stability.Be applicable to the N of nitric acid production factory
2The reduction of discharging process of O, application prospect is very wide.The present invention also can be applied to other industrial source, like N such as adipic acid factories
2The reduction of discharging process of O.
Description of drawings
N under Fig. 1: CoFe-MOR, FeCo-MOR, Co-MOR and the Fe-MOR catalyst different temperatures
2(air speed is 30 to the O degrading activity, 000h
-1, N
2O concentration is 0.5%).
Fig. 2: CoFe-MOR is N under different atmosphere
2(air speed is 30 to the O degrading activity, 000h
-1, N
2O concentration is 0.5%, N
2O is 0.5%, O
2Be 5%, NO is 0.1%, H
2O is 2%).
Fig. 3: N under the CoFe-MOR catalyst simulating pollution atmosphere
2(air speed is 30 to the test of O stability of factorization, 000h
-1, N
2O concentration is 0.5%, O
2Be 5%, NO is 0.1%, H
2O is 2%).
The specific embodiment
Embodiment 1:CoFe-MOR catalyst, air speed are 30,000h
-1, N
2O concentration is 0.5%, N under the different temperatures
2The O decomposition reaction is active.Reacting initial temperature is 280 ℃, and full conversion temperature is 430 ℃.
The preparation of CoFe-MOR: be under 6 conditions 1), with the Co that contains of 0.1mol/L at pH
2+The aqueous solution and MOR exchange 24 hours, repeats 3 times, dried 24 hours down for 80 ℃, be warming up in 500 ℃ of air constant temperature calcining then 4 hours, obtain Co-MOR;
2) be under 6 conditions in the pH value, with the Fe that contains of 0.1mol/L
3+The aqueous solution and Co-MOR exchange 24 hours, repeats 3 times, dried 24 hours down for 80 ℃, be warming up in 500 ℃ of air constant temperature calcining then 4 hours, obtain the CoFe-MOR catalyst.
Catalytic reaction adopts fixed bed continuous-flow reaction evaluating device, at N
2The O initial concentration is 0.5%, and air speed is 30,000h
-1, N when temperature is 280 ℃
2O begins to transform, and 355 ℃ of conversion ratios reach 50%, 430 ℃ of full conversion.
Embodiment 2: iron cobalt loaded mordenite (FeCo-MOR) catalyst of different exchange sequence preparations, air speed is 30,000h
-1, N
2O concentration is 0.5%, N under the different temperatures
2The O degrading activity.Reacting initial temperature is 325 ℃, and full conversion temperature is 525 ℃.
The preparation of FeCo-MOR: be under 6 conditions 1), with the Fe that contains of 0.1mol/L at pH
3+The aqueous solution and MOR exchange 24 hours, repeats 3 times, dried 24 hours down for 80 ℃, be warming up in 500 ℃ of air constant temperature calcining then 4 hours, obtain iron loaded mordenite (Fe-MOR);
2) be under 6 conditions at pH, with the Co that contains of 0.1mol/L
2+The aqueous solution and Fe-MOR exchange 24 hours, repeats 3 times, dried 24 hours down for 80 ℃, be warming up in 500 ℃ of air constant temperature calcining then 4 hours, obtain the FeCo-MOR catalyst.
Catalytic reaction adopts fixed bed continuous-flow reaction evaluating device, at N
2The O initial concentration is 0.5%, and air speed is 30,000h
-1, N when temperature is 350 ℃
2O begins to transform, and 455 ℃ of conversion ratios reach 50%, 575 ℃ of full conversion.
Embodiment 3:CoFe-MOR catalyst, air speed are 30,000h
-1, N
2O concentration is 0.5%, (NO, O under the different interference atmosphere
2, H
2O), different temperatures N
2The degrading activity of O.The result is illustrated in NO, O
2, H
2When O exists separately and jointly respectively, N
250% conversion temperature of O is respectively 355,350,375 and 380 ℃.
Catalyst is the CoFe-MOR catalyst in the instance 1, estimates on the device in instance 1 and carries out.Catalyst amount is 0.1g, and air speed is 30,000h
-1, adjustment all gases flow and balance gas He throughput make initial concentration N
2O is 0.5%, O
2Be 5%, NO is 0.1%, H
2O is 2%.From 200-600 ℃ of temperature programming, investigate N
2The O conversion ratio.The result is illustrated in NO, O
2, H
2When O exists separately and jointly respectively, N
250% conversion temperature of O is respectively 355,350,375 and 380 ℃.
Embodiment 4:CoFe-MOR catalyst activity estimation of stability.Identical with instance 3 catalyst system therefors with evaluating apparatus.Air speed is 30,000h
-1, N
2O concentration is 0.5%, N
2O is 0.5%, O
2Be 5%, NO is 0.1%, H
2O is 2%.N in the time of 375 ℃
2N when the O conversion ratio is 71%, 400 ℃
2N when the O conversion ratio is 92%, 425 ℃
2The O conversion ratio is 100%; And after reaction was carried out 100 hours continuously, activity of such catalysts is obviously decay not.
Claims (2)
1. the catalyst that decomposes of the inferior nitrogen of a catalytic oxidation is characterized in that being is carrier with modenite (MOR) molecular sieve, and load bimetallic Co and Fe are active component.The developed by molecule formula is: CoFe-MOR, each constituent content is: Co is that 1-10%, Fe are that 0.1-5%, MOR are 80-98%.
2. Preparation of catalysts method as claimed in claim 1 is characterized in that catalyst passes through the two step load C o of aqueous solution ion-exchange elder generation, and back loading Fe active component prepares to the MOR molecular sieve, and concrete steps are following:
1) be 2-9 in the pH value, with the Co that contains of 0.01-2mol/L
2+The aqueous solution and MOR at room temperature exchange 24-48 hour, repeat 1-5 time, 80-100 ℃ of down oven dry 15-25 hour in 500 ℃ of air constant temperature calcining 4-6 hour then, obtains the MOR (Co-MOR) of cobalt load;
2) be 2-9 in the pH value, with the Fe that contains of 0.01-2mol/L
3+The aqueous solution and Co-MOR at room temperature exchange 24-48 hour, repeat 1-5 time, 80-100 ℃ of down oven dry 15-25 hour in 500 ℃ of air constant temperature calcining 4-6 hour then, obtains above-mentioned catalyst.
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|---|---|---|---|
| CN2011102403893A CN102380410A (en) | 2011-08-19 | 2011-08-19 | Ferro-cobalt bimetallic catalyst for catalyzing nitrous oxide (N2O) decomposition |
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|---|---|---|---|
| CN2011102403893A CN102380410A (en) | 2011-08-19 | 2011-08-19 | Ferro-cobalt bimetallic catalyst for catalyzing nitrous oxide (N2O) decomposition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007998A (en) * | 2012-05-30 | 2013-04-03 | 中国科学院生态环境研究中心 | Method for preparing molecular sieve based catalyst for catalytic decomposition and reduction of nitrous oxide |
| CN105749959A (en) * | 2016-02-18 | 2016-07-13 | 中国科学院上海高等研究院 | High-silica molecular sieve catalyst used for nitrous oxide decomposition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2258030C2 (en) * | 2000-02-11 | 2005-08-10 | Уде Гмбх | N2o decomposition catalyst, use and a method for preparation thereof |
| CN101204665A (en) * | 2006-12-21 | 2008-06-25 | 中国科学院生态环境研究中心 | Integral type catalyst decomposing nitrous oxide and preparation method thereof |
-
2011
- 2011-08-19 CN CN2011102403893A patent/CN102380410A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2258030C2 (en) * | 2000-02-11 | 2005-08-10 | Уде Гмбх | N2o decomposition catalyst, use and a method for preparation thereof |
| CN101204665A (en) * | 2006-12-21 | 2008-06-25 | 中国科学院生态环境研究中心 | Integral type catalyst decomposing nitrous oxide and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LAN DONG LI，ET AL: "Fe-USY Zeolite Catalyst for Effective Decomposition of Nitrous Oxide", 《ENVIRON. SCI. TECHNO》, vol. 41, 31 December 2007 (2007-12-31), pages 7901 - 7906 * |
| XINYAN ZHANG，ET AL: "CoMOR zeolite catalyst prepared by buffered ion exchange for effective decomposition of nitrous oxide", 《JOURNAL OF HAZARDOUS MATERIALS》, vol. 192, 8 July 2011 (2011-07-08), pages 1756 - 1765, XP028275930, DOI: doi:10.1016/j.jhazmat.2011.07.001 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007998A (en) * | 2012-05-30 | 2013-04-03 | 中国科学院生态环境研究中心 | Method for preparing molecular sieve based catalyst for catalytic decomposition and reduction of nitrous oxide |
| CN105749959A (en) * | 2016-02-18 | 2016-07-13 | 中国科学院上海高等研究院 | High-silica molecular sieve catalyst used for nitrous oxide decomposition |
| CN105749959B (en) * | 2016-02-18 | 2018-05-15 | 中国科学院上海高等研究院 | A kind of high-silica zeolite catalyst for nitrous oxide |
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Application publication date: 20120321 |