CN1246070C - Rarefied-burning automobile exhaust gas catalyzing and purifying method and apparatus - Google Patents
Rarefied-burning automobile exhaust gas catalyzing and purifying method and apparatus Download PDFInfo
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- CN1246070C CN1246070C CNB021170843A CN02117084A CN1246070C CN 1246070 C CN1246070 C CN 1246070C CN B021170843 A CNB021170843 A CN B021170843A CN 02117084 A CN02117084 A CN 02117084A CN 1246070 C CN1246070 C CN 1246070C
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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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Abstract
The present invention relates to a thin combustion type automobile tail gas catalyzing and purifying method and a device thereof, which relates to the automobile tail gas purifying technique. In the present invention, an engine exhaust pipe is provided with two catalytic reaction beds; an additional reducing agent nozzle is arranged between the two reaction beds; the first reaction bed uses hydrocarbons in tail gas to reduce nitrous oxides and simultaneously causes hydrocarbons and carbon monoxide in tail gas to be converted into carbon dioxide and water; the second reaction bed uses additional oxygenous hydrocarbon reducers to reduce nitrous oxides and simultaneously causes the additional reducers to be converted into carbon dioxide and water. Compared with the prior art, the present invention can widen active temperature range, enhance the purification efficiency of nitrous oxides, utilize the nitrous oxide reducing function of hydrocarbons in the tail gas of engines and additional oxygenous hydrocarbons in a coordinating mode, reduce the consumption of the additional reducers and convert hydrocarbons and carbon monoxide into carbon dioxide and water with high efficiency.
Description
Technical field
Lean burn is meant the burning of carrying out under the air excess condition.The present invention relates to a kind of Rarefied-burning automobile exhaust gas catalyzing and purifying method and device; belong to field of environment protection; more particularly, relate to and a kind ofly make nitrogen oxide (NOx), hydrocarbon (HC) and carbon monoxide (CO) in lean burn type vehicle gasoline engine and the diesel engine vent gas be converted into nitrogen (N
2), water (H
2O) and carbon dioxide (CO
2) method and apparatus.
Background technology
Lean burn can improve fuel economy, reduces pollutant discharge amount, thereby along with the growing to even greater heights of energy savings and protection environment cry, the market prospects of lean burn type vehicular engine are boundless.Yet the tail gas that lean burn engines is discharged contains a large amount of oxygen, and now business-like three-way catalyst can not purify NOx wherein effectively.At present, the NOx waste gas that contains oxygen for the discharge of coal-burning boiler and nitric acid production and so on stationary source, adopt ammonia selective catalytic reduction method to purify mostly, yet, leak and to cause secondary pollution problems because of existing ammonia to carry inconvenience and excess ammonia, so this method is suitable for the catalytic purification processing of lean burn type vehicle exhaust.
Round the catalytic purification of lean burn type vehicle exhaust, academia and industrial circle have been made extensive work closely during the last ten years, and how these work mainly are conceived to is harmless object with conversion of nitrogen oxides.Based on considering from the thermodynamics angle, decompose nitrogen oxides is that nitrogen and oxygen are possible, people attempt at first by direct catalytic decomposition purifying nitrogen oxide, yet, oxygen has very strong depression effect to the catalytic decomposition of nitrogen oxide, thereby can not be applied to the catalytic purification of lean burn type vehicle exhaust.The nitrogen oxide (Catalysis today, 1991,10:57～71) of discovery in the last hydrocarbon of Cu/ZSM-5 (zeolite catalyst of Copper Ion Exchange) can reduce oxygen-containing atmosphere such as early 1990s Japan scholar Iwamoto.Subsequently, the hydrocarbon selective catalyst reduction of nitrogen oxides becomes the research focus of environmental catalysis circle, and this method is considered to the Rarefied-burning automobile exhaust gas catalyzing and purifying method of tool actual application prospect.Up to the present, the catalyst of studying comprises the zeolite and supported non-noble metal oxide three classes of carried noble metal, metal ion exchanged, hydrocarbon as reducing agent mainly is low-carbon alkene, alkane, oxygen-bearing hydrocarbon (as low-carbon alcohols, ether or ketone), and contained mixing hydrocarbon (the Catalysis Surveys from Japan of vehicle exhaust itself, 1999,3:139-146).
Although under desirable reaction condition, hydrocarbon nitrogen oxides reduction effectively on above-mentioned catalyst,, the clean-up effect under the actual working conditions is not good.The main cause that this situation occurs is, existing catalyzing and reducing nitrogen oxides method adopts single catalyst-reducing agent combined system, a catalytic reduction reaction bed promptly only is set, this reaction bed contains one or more compounds that can be used as catalyst, and the reduction of nitrogen oxide is carried out in a reaction bed.The deficiency of this method is: 1) the nitrogen oxide reduction efficiency is not high enough; 2) the active temperature scope is narrower, its reason is that the efficient of hydrocarbon oxidation catalyst nitrogen oxides reduction is the volcano type with the reaction temperature variation, promptly there is a suitable active temperature interval, temperature is too high or too low all to be unfavorable for the nitrogen oxide reduction, and single catalyst-reducing agent combination only has higher activity in a narrow temperature range; 3) lean burn type vehicle exhaust hydrocarbons content is lower, for nitrogen oxides reduction effectively, needs the external carbon hydrogen compound to make reducing agent.Yet, the prior art scheme is difficult to accomplish to make vehicle exhaust institute hydrocarbon-containiproducts own and external carbon hydrogen compound all to can be effectively used to nitrogen oxides reduction, and guarantee that hydrocarbon can be converted into carbon dioxide and water efficiently, prevents the exhaust hydrocarbon concentration over-standard; 4) the prior art scheme is not investigated the purification efficiency of carbon monoxide specially.
Summary of the invention:
The objective of the invention is to propose a kind of Rarefied-burning automobile exhaust gas catalyzing and purifying method and device, more particularly, be that proposition is a kind of suitable with lean burn type vehicle exhaust, the efficient nitrogen oxides reduction of energy in wider temperature range, and make hydrocarbon and carbon monoxide be oxidized to the method and apparatus of carbon dioxide and water efficiently.
The objective of the invention is to be achieved through the following technical solutions:
A kind of Rarefied-burning automobile exhaust gas catalyzing and purifying method, this method is carried out as follows:
(1) tail gas of discharging from engine is introduced into first catalytic bed, in this reaction bed to load on Al
2O
3On the oxide of Ag, Ga, Co, Sn or In make catalyst, with the contained hydrocarbon nitrogen oxides reduction of tail gas itself, make contained hydrocarbon of tail gas itself and carbon monoxide be converted into carbon dioxide and water simultaneously;
(2) from the first catalytic bed tail gas discharged with after the oxygen-bearing hydrocarbon reducing agent that adds evenly mixes, enter second catalytic bed, in this reaction bed, utilize Al
2O
3Or load on Al
2O
3On the oxide of Ag, Ga, Co, Sn or In make catalyst, nitrogen oxides reduction makes the reducing agent that adds be converted into carbon dioxide and water simultaneously.
The oxygen-bearing hydrocarbon reducing agent that adds described in this method can adopt methyl alcohol or ethanol.
A kind of device of implementing above-mentioned Rarefied-burning automobile exhaust gas catalyzing and purifying method, this device comprises two two catalytic bed that active temperature is different, first catalytic bed is arranged on exhaust pipe of engine leading portion, second catalytic bed is arranged on blast pipe stage casing or back segment, is provided with between two catalytic bed and adds oxygen-bearing hydrocarbon reducing agent nozzle.
The present invention compared with prior art, have the following advantages and beneficial effect: 1) by two different catalytic bed of active temperature are set, can widen nitrogen oxide reducing activity temperature range, simultaneously, make full use of the ability of engine exhaust institute's hydrocarbon-containiproducts and additional reducing agent nitrogen oxides reduction; 2) it is higher to be arranged on the reaction bed temperature of first catalytic bed of exhaust pipe of engine leading portion, can utilize the contained hydrocarbon partial reduction nitrogen oxide of engine exhaust.Simultaneously, make hydrocarbon and carbon monoxide in the exhaust be converted into carbon dioxide and water; 3) in second catalytic bed of blast pipe stage casing or back segment, utilize the active temperature catalyst-reducing agent lower to make up further nitrogen oxides reduction than first reaction bed, can guarantee efficient purifying nitrogen oxide, and owing to utilize the institute of engine hydrocarbon-containiproducts own to reduce the part nitrogen oxide at first reaction bed, so can reduce the consumption of additional reducing agent.In sum, can draw, compare with the prior art scheme, the present invention can widen the active temperature scope, improve purification of nitrogen oxides efficient, coordination utilizes engine exhaust institute hydrocarbon-containiproducts and adds the effect of oxygen-bearing hydrocarbon nitrogen oxides reduction, reduces the consumption of additional reducing agent, and efficiently transforms hydrocarbon and carbon monoxide is carbon dioxide and water.
Description of drawings
Fig. 1 is the structural principle schematic diagram of Rarefied-burning automobile exhaust gas catalyzing and purifying device.
Among the figure: 1 is enmgine exhaust; 2 is first catalytic bed; 3 spray into mouth for additional reducing agent; 4 is second catalytic bed.
The specific embodiment
This method and apparatus is selected nitrogen oxides reduction activity that existing research filters out catalyst preferably for use, as Al
2O
3Or load on Al
2O
3On the oxide of metals such as Ag, Ga, Co, Sn or In make catalyst.Unlike the prior art, Rarefied-burning automobile exhaust gas catalyzing and purifying method that the present invention proposes and device are based on the dual catalyst with different activities temperature-reducing agent combined system, specifically, two catalytic bed are set on the exhaust pipe of engine exactly, first catalytic bed 2 is arranged on the leading portion of the exhaust pipe of engine, promptly near the exhaust manifold 1; Second catalytic bed 4 is arranged on blast pipe stage casing or back segment, is provided with between two catalytic bed and adds oxygen-bearing hydrocarbon reducing agent nozzle 3, as shown in Figure 1.Wherein, the reaction temperature of first catalytic bed is higher, between 400～600 ℃; The reaction temperature of second catalytic bed is lower, between 300～450 ℃.
The tail gas of discharging from engine enters first catalytic bed 2 behind exhaust manifold 1, in this reaction bed, utilize the contained hydrocarbon oxidation catalyst nitrogen oxides reduction of engine exhaust, simultaneously, makes hydrocarbon and carbon monoxide be oxidized to carbon dioxide and water.From first catalytic bed gas of discharging and the oxygen-bearing hydrocarbon reducing agent that adds, after methyl alcohol or the even mixing of ethanol, enter second catalytic bed 4, in this reaction bed, utilize the additional reducing agent catalyzing and reducing nitrogen oxides, simultaneously, make additional reducing agent be oxidized to carbon dioxide and water.
Experiment shows, with nitric oxide (NO), propylene (C
3H
6), oxygen (O
2), carbon monoxide (CO), sulfur dioxide (SO
2), water (H
2O) and nitrogen (N
2) the mist simulation lean burn type vehicle exhaust formed.Propylene in the first catalytic bed utilization simulation gas etc. is made reducing agent, and second catalytic bed adopts the oxygen-bearing hydrocarbon that adds to make reducing agent.With Al
2O
3Or load on Al
2O
3On the oxide of metals such as Ag, Co, Ga, In or Sn make catalyst.When air speed is 42,000h
-1～100,000h
-1The volume ratio of the oxygen-bearing hydrocarbon/nitrogen oxide of second reaction bed is 1～4, the first catalytic reaction bed tempertaure is 400～600 ℃, when the second catalytic reaction bed tempertaure is 300～450 ℃, purification of nitrogen oxides efficient can reach more than 60%, and hydrocarbon and carbon monoxide purification efficiency are higher than 80%.
Embodiment:
Embodiment 1
Simulation lean burn type vehicle exhaust is by 1100ppm NO, 600ppm C
3H
6, 3000ppm CO, 5%O
2, 10%H
2O and 80ppm SO
2, all the other are N
2Form.Two Ag/Al that catalytic bed all prepares with sol-gel process
2O
3(content of Ag is 5%) makes catalyst.Between first and second catalytic bed, spray into methyl alcohol (CH
3OH), after the first reaction bed exit gas mixed, methanol concentration was 2500ppm.When air speed is 42,000h
-1, the temperature of first catalytic bed is 450～550 ℃, when the temperature of second catalytic bed is 300～400 ℃.The NOx purification efficiency is 75%～85%, and the hydrocarbon purification efficiency is 89%～98%, and the carbon monoxide purification efficiency is 88%～99%.
Simulation lean burn type vehicle exhaust is by 1100ppm NO, 1100ppm C
3H
6, 3000ppm CO, 5%O
2, 10%H
2O and 80ppm SO
2, all the other are N
2Form.The first catalytic bed Ga
2O
3/ Al
2O
3Make catalyst (Ga
2O
3Content be 27%), second catalytic bed is with the Co/Al of immersion process for preparing
2O
3(content of Co is 2%) makes catalyst.Between first and second catalytic bed, spray into methyl alcohol (CH
3OH), after the first reaction bed exit gas mixed, methanol concentration was 2500ppm.When air speed is 100,000h
-1, the temperature of first catalytic bed is 470～570 ℃, when the temperature of second catalytic bed is 320～420 ℃.The NOx purification efficiency is 60%～69%, and the hydrocarbon purification efficiency is 80%～89%, and the carbon monoxide purification efficiency is 83%～94%.
Simulation lean burn type vehicle exhaust is by 1000ppm NO, 1000ppm C
3H
6, 3000ppm CO, 8%O
2, 10%H
2O and 80ppm SO
2, all the other are N
2Form the Ga that first catalytic bed prepares with sol-gel process
2O
3/ Al
2O
3(Ga
2O
3Content be 27%) make catalyst, second catalytic bed is with the Ag/Al of sol-gel process preparation
2O
3(Ag content is 5%) makes catalyst.Between first and second catalytic bed, spray into ethanol (C
2H
5OH), after the first reaction bed exit gas mixed, concentration of alcohol was 2000ppm.When air speed is 60,000h
-1, the reaction temperature of first catalytic bed is 470～570 ℃, when the second catalytic bed reaction temperature is 350～450 ℃.The NOx purification efficiency is 74%～87%, and the hydrocarbon purification efficiency is 83%～95%, and the carbon monoxide purification efficiency is 87%～96%.
Embodiment 4
Simulation lean burn type vehicle exhaust is by 1000ppm NO, 1000ppm C
3H
6, 3000ppm CO, 8%O
2, 10%H
2O and 80ppm SO
2, all the other are N
2Form the SnO that first catalytic bed prepares with sol-gel process
2/ Al
2O
3(SnO
2Content be 10%) make catalyst, second catalytic bed is with the Ag/Al of immersion process for preparing
2O
3(Ag content is 2%) makes catalyst.Between first and second catalytic bed, spray into ethanol (C
2H
5OH), after the first reaction bed exit gas mixed, concentration of alcohol was 2000ppm.When air speed is 50,000h
-1, the reaction temperature of first catalytic bed is 450～530 ℃, when the second catalytic bed reaction temperature is 350～450 ℃.The NOx purification efficiency is 64%～86%, and the hydrocarbon purification efficiency is 81%～91%, and the carbon monoxide purification efficiency is 83%～97%.
Embodiment 5
Simulation lean burn type vehicle exhaust is by 1000ppm NO, 1000ppm C
3H
6, 3000ppm CO, 8%O
2, 10%H
2O and 80ppm SO
2, all the other are N
2Form first catalytic bed In/Al of immersion process for preparing
2O
3(content of In is 3%) makes catalyst, the Al that second catalytic bed prepares with sol-gel process
2O
3Make catalyst.Between first and second catalytic bed, spray into methyl alcohol (CH
3OH), after the first reaction bed exit gas mixed, methanol concentration was 2000ppm.When air speed is 70,000h
-1, the reaction temperature of first catalytic bed is 450～550 ℃, when the second catalytic bed reaction temperature is 300～400 ℃.The NOx purification efficiency is 60%～84%, and the hydrocarbon purification efficiency is 84%～93%, and the carbon monoxide purification efficiency is 85%～98%.
Claims (2)
1, a kind of Rarefied-burning automobile exhaust gas catalyzing and purifying method is characterized in that: comprise the steps:
(1) the engine tail gas of discharging is introduced into first catalytic bed, in this reaction bed to load on Al
2O
3On the oxide of Ag, Ga, Co, Sn or In make catalyst, the hydrocarbon oxidation catalyst nitrogen oxides reduction that contains with tail gas itself, make contained hydrocarbon of tail gas itself and carbon monoxide be converted into carbon dioxide and water simultaneously, its reaction temperature is between 400～600 ℃
(2) from the first catalytic bed tail gas discharged with after the oxygen-bearing hydrocarbon reducing agent that adds evenly mixes, enter second catalytic bed, in this reaction bed, utilize Al
2O
3Or load on Al
2O
3On the oxide of Ag, Ga, Co, Sn or In make catalyst, nitrogen oxides reduction, make the oxygen-bearing hydrocarbon reducing agent that adds be converted into carbon dioxide and water simultaneously, its reaction temperature is between 300～450 ℃, and the reaction temperature of second catalytic bed is lower than the reaction temperature of first catalytic bed; The described oxygen-bearing hydrocarbon reducing agent that adds is methyl alcohol or ethanol.
2, implement the device of Rarefied-burning automobile exhaust gas catalyzing and purifying method according to claim 1, it is characterized in that: this device is by first catalytic bed, second catalytic bed and be arranged on two oxygen-bearing hydrocarbon reducing agent nozzles between the reaction bed and form, and described first catalytic bed is to load on Al
2O
3On the oxide of Ag, Ga, Co, Sn or In make catalyst, second catalytic bed is utilized Al
2O
3Or load on Al
2O
3On the oxide of Ag, Ga, Co, Sn or In make catalyst, press the flow direction of vehicle exhaust, described first catalytic bed is arranged on the leading portion of the exhaust pipe of engine, second catalytic bed is arranged on the stage casing or the back segment of blast pipe.
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| CNB021170843A CN1246070C (en) | 2002-04-29 | 2002-04-29 | Rarefied-burning automobile exhaust gas catalyzing and purifying method and apparatus |
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|---|---|---|---|
| CNB021170843A CN1246070C (en) | 2002-04-29 | 2002-04-29 | Rarefied-burning automobile exhaust gas catalyzing and purifying method and apparatus |
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|---|---|
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| CN1246070C true CN1246070C (en) | 2006-03-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102791972A (en) * | 2010-05-12 | 2012-11-21 | 丰田自动车株式会社 | Exhaust purification device for internal combustion engine |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3938187B2 (en) * | 2005-05-17 | 2007-06-27 | いすゞ自動車株式会社 | Exhaust gas purification method and exhaust gas purification system |
| JP4703260B2 (en) * | 2005-05-17 | 2011-06-15 | Ｕｄトラックス株式会社 | Engine exhaust purification device and exhaust pipe structure used therefor |
| CN101024147B (en) * | 2006-02-17 | 2011-12-28 | 陈妙生 | Wast gas purifier |
| US8635855B2 (en) | 2009-06-17 | 2014-01-28 | GM Global Technology Operations LLC | Exhaust gas treatment system including a lean NOx trap and two-way catalyst and method of using the same |
| CN115715981A (en) * | 2022-11-04 | 2023-02-28 | 安徽华塑股份有限公司 | Preparation method of catalyst for preparing ethanol by carbon dioxide hydrogenation |
-
2002
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102791972A (en) * | 2010-05-12 | 2012-11-21 | 丰田自动车株式会社 | Exhaust purification device for internal combustion engine |
| CN102791972B (en) * | 2010-05-12 | 2013-10-23 | 丰田自动车株式会社 | Exhaust purification device for internal combustion engine |
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| Publication number | Publication date |
|---|---|
| CN1454701A (en) | 2003-11-12 |
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