CN102091615A - Application of nano cerium dioxide supported nitrogen oxide storage-reduction catalyst in purifying lean-burn tail gases - Google Patents
Application of nano cerium dioxide supported nitrogen oxide storage-reduction catalyst in purifying lean-burn tail gases Download PDFInfo
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- CN102091615A CN102091615A CN 201010509440 CN201010509440A CN102091615A CN 102091615 A CN102091615 A CN 102091615A CN 201010509440 CN201010509440 CN 201010509440 CN 201010509440 A CN201010509440 A CN 201010509440A CN 102091615 A CN102091615 A CN 102091615A
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- platinum
- barium
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- cerium dioxide
- nitrogen oxide
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Abstract
The invention relates to application of a nano cerium dioxide supported nitrogen oxide storage-reduction catalyst in purifying lean-burn tail gases. The catalyst takes cerium dioxide nano-cube as a carrier and the nitrogen oxide storage component barium and the noble metal component platinum are supported on the cerium dioxide by a dipping method. The application is characterized in that the catalyst is formed by the noble metal platinum and the storage component barium which are supported on the cerium dioxide nano-cube; the content of platinum is 0.05-1.0% calculated according to the weight of the metal element and the platinum exists in the form of metal platinum or oxides of platinum; and the content of barium is 5-20% calculated according to the weight of the metal element and the barium exists in the form of barium oxide or barium carbonate. The catalyst prepared in the invention shows excellent NOx purifying property at the airspeed as high as 360,000h<-1> and the temperature of 200-400 DEG C, and the NOx average conversion efficiency is more than 97% and the highest conversion efficiency is more than 98% under the conditions that the lean-burn residence time is 60 seconds and the rich-burn residence time is 5 seconds.
Description
Technical field
The present invention is applied to environmental catalysis purification techniques field, relates to a kind of catalyst for nitrogen oxide storage and reduction that is used for the lean-combustion engine exhaust gas aftertreatment techniques.
Technical background
Along with the scarcity day by day of petroleum resources and the aggravation of global warming situation, lean-combustion engine (diesel engine and gasoline engine) has been subjected to extensive concern because of its higher fuel economy and lower greenhouse gas emissions, yet a large amount of nitrogen oxide (NOx) can not only cause outstanding environmental problems such as photochemical fog, acid rain in the tail gas, simultaneously human beings'health are had serious harm.Therefore, how effectively to remove the research focus that NOx in the lean-combustion engine tail gas becomes current environmental catalysis.A large amount of studies show that ammine selectivity catalytic reduction (NH
3-SCR), hydrocarbon SCR (HC-SCR) and NOx storage and reduction (NSR) be to be expected to be applied to the technical scheme that lean-combustion engine NOx purifies most.Wherein, NOx storage and reduction technology stores and injection apparatus because of not needing additional reducing agent, need not cloth and builds reducing agent interpolation station, has shown bigger advantage in the lean-combustion engine vent gas treatment.
Typical NSR catalyst is formed and is comprised noble metal (Pt, Rh, Pd), alkali metal or alkaline-earth metal, and the carrier of Large ratio surface (being generally aluminium oxide) (patent JP2600492, JP2003245550).Current is main flow research and application system with Pt/Ba/Al, and its effect in lean-burn tail gas NOx purifies can be divided into following a few step: under lean-burn was excess oxygen, NO was oxidized to NO under the effect of Pt
2, store by the form of basic component on the catalyst with nitrate; Under the dense combustion condition of adjusting to of engine cycle (oxygen deprivation), NOx is released, with the reduction components H that coexists in the tail gas
2, reactions such as CO, HC are converted into N
2The NSR technology is by after successfully integrating with the particle trapping technique, Demonstration Application on Japanese light diesel car, and energetically to the enforcement of this technology of Europe pursued.
The NOx storage and reduction is one to relate to that NO oxidation, NOx store, discharge, the cascade reaction of reduction, have only and possess above excellent properties simultaneously, could realize the efficient purification to NOx, this design to each component units of NSR catalyst, integration and coupling are had higher requirement.In the NSR catalyst, the performance of carrier such as specific area, pore volume pass through the degree of scatter of influence and modulation noble metal and basic component, thereby influence the performance of NSR catalyst; Carrier plays an important role in the NOx adsorption process simultaneously.Ceria (CeO
2) sill has been widely used in catalyzing manufacturing of hydrogen and purifying, three-way catalyst and other catalytic process (Esch F, Fabris S, Zhou L, Montini T, Africh C, Fornasiero P, Comelli G, Rosei R, Science, 2005,309,752).Studies show that CeO
2The size of particle, pattern, Local Structure can obviously influence the catalytic performance (Zhou K, Wang X, Sun X, Peng Q, Li Y, J.Catal.2005,299,206) of cerium oxide base material; In the last few years, material synthesized the especially rise of nano material controlledly synthesis technology, made that accurately the size and the pattern of control synthetic material become possible (Bell A.T, Science, 2003,299,1688 on nanoscale; Xia Y.N, Yang P.D, Sun Y.G, Wu Y, MarersB, Gates B, Yin Y. D, Kim F, Yan H.Q, Adv.Mater.2003,15,353), the new way of high performance material/Catalyst Design that Open from This Side.
Summary of the invention
Based on above-mentioned thinking, the invention provides a kind of is the Pt/Ba/CeO of carrier with the cerium dioxide nano cubic body
2Storage and reduction catalyst, this catalyst is a carrier with the cerium dioxide nano cubic body, with infusion process basic component, noble metal is assembled, for NO oxidation, storage, constructing of restoring function unit provide the high activity of controllable size crystal face; Utilize the redox property of this metal oxide excellence simultaneously, dispersion and the grappling effect good to noble metal component are to promote the performance of each functional unit, the NOx storage and reduction catalyst of design performance excellence.
Catalyst of the present invention is a kind of catalyst that is used for purifying lean-combustion engine tail gas NOx, it is characterized in that this catalyst is by loading on CeO
2Noble metal platinum on the nanocube and basic component barium constitute, it is 0.05～1.0wt.% that the content of platinum converts by the metal element wt, oxide formation with metal platinum or platinum exists, it is 5～20wt.% that the content of barium converts by the metal element wt, exists with the form of barium monoxide or brium carbonate.
The Preparation of catalysts method is an infusion process among the present invention, and its key step is:
With the cerium dioxide nano cubic body is carrier, and a certain amount of soluble barium salt is mixed with the aqueous solution, impregnated on the carrier, removes moisture through the decompression rotary evaporation, and oven dry is spent the night, and roasting 3～6h makes Ba/CeO in air atmosphere
2Composite oxides;
A certain amount of solubility platinum salt is mixed with the aqueous solution, is impregnated into the Ba/CeO of above-mentioned preparation
2On, through the decompression rotary evaporation, oven dry is spent the night, and roasting 3～6h promptly makes Pt/Ba/CeO in air atmosphere
2Catalyst.
Described preparation method is characterized in that:
The pattern of described carrier ceria material is a nanocube;
The soluble barium salt is at least a in barium nitrate or barium chloride or the barium acetate, and its concentration is 0.01～1mol/L;
Solubility platinum salt is at least a in platinum nitrate or platinum chloride or chloroplatinic acid or ammonium chloroplatinate or the potassium chloroplatinate, and its concentration is 0.001～0.2mol/L;
Described preparation method removes moisture in the mode of decompression rotary evaporation under 30～90 ℃;
Described preparation method, bake out temperature is 60～120 ℃;
Described preparation method, sintering temperature is 500～1000 ℃.
The catalyst of the present invention preparation in air speed up to 360,000h
-1Shown excellent NOx purifying property in 200～400 ℃ of scopes are equal: in the lean-burn time of staying is 60 seconds, average conversion to NOx under 5 seconds the condition of dense combustion reaches more than 97%, and the highest transformation efficiency reaches more than 98%, shows excellent high-speed characteristic and high activity.
The catalyst that this method makes also can carry out slurrying according to actual needs, is coated on pottery or the metal beehive carrier, is prepared into integer catalyzer and uses.
The specific embodiment
The present invention enumerate following examples in order more clearly to illustrate, but it there is not any restriction to scope of the present invention.
The Preparation of Catalyst example
Embodiment 1: take by weighing 0.6 gram Ba (CH
3COO)
2, the Ba (CH of preparation 0.1mol/L
3COO)
2Solution joins 5g cerium dioxide nano cubic body in the above-mentioned solution, and dipping 2h at 30～90 ℃ of following decompression rotary evaporations, with the moisture evaporate to dryness, 120 ℃ of following dried overnight, through Muffle furnace roasting 4h in 500 ℃ of air, obtains Ba/CeO with the sample that obtains
2Sample;
Take by weighing 0.029 gram PtCl
4, the PtCl of preparation 0.07mol/L
4Solution is with the Ba/CeO of above-mentioned preparation
2Sample joins PtCl
4In the solution, dipping 2h, other operation and Ba/CeO
2Sample preparation is identical, gets catalyst 1, and grinding is sieved, and it is standby to get 40～60 orders.
Embodiment 2: take by weighing 2.1 gram Ba (CH
3COO)
2, the Ba (CH of preparation 0.35mol/L
3COO)
2Solution joins 5g cerium dioxide nano cubic body in the above-mentioned solution, and dipping 2h at 30～90 ℃ of following decompression rotary evaporations, with the moisture evaporate to dryness, 120 ℃ of following dried overnight, through Muffle furnace roasting 4h in 500 ℃ of air, obtains Ba/CeO with the sample that obtains
2Sample;
Take by weighing 0.029 gram PtCl
4, the PtCl of preparation 0.07mol/L
4Solution is with the Ba/CeO of above-mentioned preparation
2Sample joins PtCl
4In the solution, dipping 2h, other operation and Ba/CeO
2Sample preparation is identical, gets catalyst 2, and grinding is sieved, and it is standby to get 40～60 orders.
The catalytic activity test case
Embodiment 3: the catalyst 1 with embodiment 1 preparation carries out the experiment of NOx storage and reduction on micro fixed-bed reactor.The use amount of catalyst is 100mg, the consisting of of reaction mixture gas: lean-burn [NO]=500ppm, [O
2]=8%, N
2Balance, the time of staying is 67s; Dense combustion [NO]=500ppm, [H
2]=0.5%, the time of staying is 33s.Reaction velocity is 360,000h
-1, experimental temperature is 200～400 ℃, at each temperature spot, carries out 20 lean-burns-dense combustion dynamic circulation, asks for its mean value to investigate the removal effect of NSR catalyst to NOx, the result is as shown in table 1.
Pt/Ba/CeO under table 1. different temperatures
2NOx storage and reduction average conversion (%)
| Catalyst | 200℃ | 300℃ | 400℃ |
| Catalyst 1 | 96.6％ | 98.7％ | 98.0％ |
| Catalyst 2 | 97.5％ | 98.8％ | 97.6％ |
Embodiment 4: the catalyst 2 with embodiment 2 preparations carries out the experiment of NOx storage and reduction on micro fixed-bed reactor.The use amount of catalyst is 100mg, the consisting of of reaction mixture gas: lean-burn [NO]=500ppm, [O
2]=8%, N
2Balance, the time of staying is 60s; Dense combustion [NO]=500ppm, [H
2]=3.0%, the time of staying is 5s.Reaction velocity is 360,000h
-1, experimental temperature is 200～400 ℃, at each temperature spot, carries out 20 lean-burns-dense combustion dynamic circulation, asks for its mean value to investigate the NSR catalyst to NO
xRemoval effect, the result is as shown in table 1.
Claims (3)
1. the application of nano ceric oxide support type catalyst for nitrogen oxide storage and reduction in purifying lean-burn tail gas, it is characterized in that this catalyst for nitrogen oxide storage and reduction is barium salt and platinum salt to be carried on the carrier ceria by infusion process obtain, wherein carrier is the cerium dioxide nano cubic body, it is 0.05～1.0wt.% that the content of platinum converts by the metal element wt, oxide formation with metal platinum or platinum exists, it is 5～20wt.% that the content of barium converts by the metal element wt, exists with the form of barium monoxide or brium carbonate.
2. catalyst according to claim 1, it is characterized in that, barium salt in the catalyst precursor is at least a in barium nitrate or barium chloride or the barium acetate, and the platinum salt in the catalyst precursor is at least a in platinum nitrate or platinum chloride or chloroplatinic acid or ammonium chloroplatinate or the potassium chloroplatinate.
3. catalyst according to claim 1 is characterized in that, can be prepared into integer catalyzer by coating molding in application process.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127933A (en) * | 2013-02-06 | 2013-06-05 | 中国科学院生态环境研究中心 | Nano cerium oxide silver-loaded catalyst, manufacturing method and purpose thereof |
| CN105289596A (en) * | 2015-10-27 | 2016-02-03 | 中国科学院生态环境研究中心 | Cerium dioxide nanorod supported nitrogen oxide storage catalyst and preparation method and application thereof |
| CN105363441A (en) * | 2014-08-08 | 2016-03-02 | 丰田自动车株式会社 | NOx STORAGE REDUCTION CATALYST AND PRODUCTION METHOD THEREOF |
| CN108212152A (en) * | 2016-12-22 | 2018-06-29 | 中国科学院宁波城市环境观测研究站 | A kind of oxide carried type NO of low temperature cerium zirconiumxCatalyst and its application |
| CN108212151A (en) * | 2016-12-22 | 2018-06-29 | 中国科学院宁波城市环境观测研究站 | A kind of oxide carried type NO of low temperature cerium zirconiumxThe preparation method of catalyst |
| CN108686640A (en) * | 2017-03-31 | 2018-10-23 | 丰田自动车株式会社 | Exhaust gas purifying catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762585A (en) * | 2005-09-30 | 2006-04-26 | 清华大学 | Preparation process of selective reduction catalyst for lean-burn gasoline motor car exhausted gas nitrogen oxide |
-
2010
- 2010-10-15 CN CN 201010509440 patent/CN102091615A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762585A (en) * | 2005-09-30 | 2006-04-26 | 清华大学 | Preparation process of selective reduction catalyst for lean-burn gasoline motor car exhausted gas nitrogen oxide |
Non-Patent Citations (1)
| Title |
|---|
| 《Applied Catalysis B:Environmental》 20061122 M. Piacentini, et al NOx storage-reduction behavior of Pt-Ba/MO2(MO2 = SiO2, CeO2, ZrO2) catalysts 105-117 1 第72卷, * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127933A (en) * | 2013-02-06 | 2013-06-05 | 中国科学院生态环境研究中心 | Nano cerium oxide silver-loaded catalyst, manufacturing method and purpose thereof |
| CN105363441A (en) * | 2014-08-08 | 2016-03-02 | 丰田自动车株式会社 | NOx STORAGE REDUCTION CATALYST AND PRODUCTION METHOD THEREOF |
| CN105289596A (en) * | 2015-10-27 | 2016-02-03 | 中国科学院生态环境研究中心 | Cerium dioxide nanorod supported nitrogen oxide storage catalyst and preparation method and application thereof |
| CN105289596B (en) * | 2015-10-27 | 2018-07-13 | 中国科学院生态环境研究中心 | A kind of ceric oxide nanorod supported nitrogen oxide storage catalyst and its preparation method and application |
| CN108212152A (en) * | 2016-12-22 | 2018-06-29 | 中国科学院宁波城市环境观测研究站 | A kind of oxide carried type NO of low temperature cerium zirconiumxCatalyst and its application |
| CN108212151A (en) * | 2016-12-22 | 2018-06-29 | 中国科学院宁波城市环境观测研究站 | A kind of oxide carried type NO of low temperature cerium zirconiumxThe preparation method of catalyst |
| CN108686640A (en) * | 2017-03-31 | 2018-10-23 | 丰田自动车株式会社 | Exhaust gas purifying catalyst |
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Application publication date: 20110615 |