CN104018918B - A kind of diesel engine exhaust gas purification device and preparation method thereof - Google Patents
A kind of diesel engine exhaust gas purification device and preparation method thereof Download PDFInfo
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- CN104018918B CN104018918B CN201410253764.1A CN201410253764A CN104018918B CN 104018918 B CN104018918 B CN 104018918B CN 201410253764 A CN201410253764 A CN 201410253764A CN 104018918 B CN104018918 B CN 104018918B
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- manganese
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Abstract
The invention discloses a kind of diesel engine exhaust gas purification device and preparation method thereof, this device includes the first purifying layer, the second purifying layer and the 3rd purifying layer；First purifying layer includes that the network structure being made up of resistance wire, described resistance wire area load have attapulgite；Second purifying layer includes titanyl compound and the oxide of the manganese as catalyst；3rd purifying layer includes matrix, carrier and the rare-earth oxide being carried on carrier, it is possible to the nitrogen oxides (NO in purification of diesel tail gas effectivelyx) and the pollutant such as soot particle (PM).
Description
Technical field
The present invention relates to diesel engine vent gas purified treatment field, particularly relate to a kind of diesel engine exhaust gas purification device and preparation thereof
Method.
Background technology
It is high that diesel engine has the thermal efficiency, fuel economy, and good dynamic property is sturdy and durable, the advantages such as maintenance cost is low, but
It is one of diesel engine vent gas major pollutants of having become as in air, the NO of more than 50% in airxPollute from motor-driven
Tail gas discharges, particularly exhaust emissions of diesel engine.It addition, city atmospheric environment quality-monitoring result also indicates that in recent years
Exhaust pollution of diesel engines has replaced gasoline engine tail gas pollution to become primary pollution source, and this trend is also continuing development.
Major pollutants in exhaust emissions of diesel engine thing have soot particle (PM) and nitrogen oxides (NOx), NOxIn an atmosphere
Can form ozone further, increase the ozone concentration in lower atmosphere, PM makes particle in air increase, contaminated air,
Affect visibility, also can be directly entered the respiratory system of people, health and environment are caused harm greatly.Due to bavin
In oil tail gas, oxygen content is high, and temperature is low, and usual way cannot the nitrogen oxides in purification of diesel tail gas effectively
(NOx) and the pollutant such as soot particle (PM).The processing method of pure Supported Honeycomb Ceramics noble metal catalyst is processing diesel oil
Tail gas is not ideal enough, and especially microgranule can be greatly improved PM2.5 air pollution index.
Summary of the invention
The present invention makes in view of the foregoing, it is an object of the present invention to provide a kind of diesel engine exhaust gas purification device and preparation thereof
Method, it is possible to the nitrogen oxides (NO in purification of diesel tail gas effectivelyx) and the pollutant such as soot particle (PM).
The present invention provides a kind of diesel engine exhaust gas purification device, and described device includes the first purification that tail gas starts to sequentially enter
Layer, the second purifying layer and the 3rd purifying layer.
First purifying layer includes that the network structure being made up of resistance wire, described resistance wire area load have attapulgite.
Second purifying layer includes that the filtration that titanyl compound and the oxide slurry as the manganese of catalyst load and be dried is coated with
Layer.
3rd purifying layer includes the mistake that matrix, carrier and the rare-earth oxide slurry being carried on carrier load and be dried
Filter coating.
Preferably, the thickness of the attapulgite of the resistance wire area load of described first purifying layer is 0.2mm to 0.5mm.
Preferably, the network structure in described first purifying layer has multiple, and spacing each other is 0.5cm to 1cm,
The thickness of described first purifying layer is 30cm to 40cm, described resistance wire composition cancellated thickness be 10cm extremely
15cm。
Preferably, the running voltage of described resistance wire is 220V, resistive heater keep the temperature of resistance wire to exist during work
Between 750 DEG C to 1000 DEG C.
Preferably, described second purifying layer slurry also include the oxide of at least two variable valency metal as catalyst promoter,
Described metal includes ferrum, copper, vanadium, cerium, at least one in nobelium, and the quality accounting of the oxide of described manganese (accounts for entirety
The ratio of catalyst) between 5% to 15% quality, the mol ratio of manganese and variable valency metal is between 0.1 to 3.
Preferably, the rare-earth oxide in described 3rd purifying layer is cerium, in the oxide of lanthanum and/or praseodymium at least
One, between described rare-earth oxide quality accounting in described carrier is 1% to 10%, the oxide of described cerium
Between quality accounting in described rare-earth oxide is 45% to 95%.
Especially it is carried on ceramic honey comb (being dried after mixture paste dipping).
Optionally, it is equipped with diesel particulate filter between described first purifying layer and the second purifying layer.
Further, the preparation method of the resistance wire of described first purifying layer includes step:
Step S101, takes attapulgite and is uniformly mixed in aqueous solution, stir and form serosity.
Step S102, takes resistance wire and is dipped in described serosity 10 minutes to 15 minutes.
Step S103, takes out resistance wire, is dried 0.5 hour to 1.5 hours at a temperature of 50 DEG C to 120 DEG C.
Step S104, repeats step S101 and obtains the resistance wire of area load attapulgite to step S103 for tri-times to six times.
Further, the preparation method of described second purifying layer includes step:
Step S201 takes titanium and the nitrate of manganese and acetate is uniformly mixed in aqueous solution, and is stirred, wherein manganese
Oxide mass accounting between 5% to 15%.
Step S202, adds at least two variable valency metal ferrum, copper, vanadium, cerium or the nitrate of nobelium and acetate, wherein manganese
And the mol ratio of variable valency metal is between 0.1 to 3.
Step S203, will stand 1 hour to 3 hours after said mixture high-speed stirred 0.5 hour.
Step S204, takes blank ceramic honey comb and is dipped in taking-up after 5 minutes to 10 minutes in described mixture, be centrifuged and go
Except additional size, after drying completely at 50 DEG C to 120 DEG C, obtain described second at 400 DEG C to 600 DEG C of roasting 3h to 4
Purifying layer.
Further, the preparation method of described 3rd purifying layer includes step:
Step S301, the nitrate or the chlorate that take attapulgite and cerium, lanthanum and/or praseodymium be uniformly mixed in aqueous solution,
Wherein metal-oxide quality accounting in the carrier is between 1% to 10%, the oxide of cerium matter in metal-oxide
Amount accounting is between 45% to 95%.
Step S302, will stand 1 hour to 2 hours after said mixture high-speed stirred 0.5 hour.
Step S303, takes blank ceramic honey comb and is dipped in described mixture and takes out after 7 minutes to 15 minutes, centrifugal segregation
Additional size, after drying completely at 50 DEG C to 120 DEG C, obtained institute to 4 hours in 3 hours 400 DEG C to 600 DEG C roastings
State the 3rd purifying layer.
Beneficial effects of the present invention: can the nitrogen oxides (NO in purification of diesel tail gas effectivelyx) and soot particle (PM)
Deng pollutant.
Accompanying drawing explanation
Fig. 1 is the structural representation of a kind of diesel engine exhaust gas purification device of the present invention；
Fig. 2 is the network structure schematic diagram of the resistance wire composition of first purifying layer of the present invention；
Fig. 3 is the preparation method flow chart of the resistance wire of first purifying layer of the present invention；
Fig. 4 is the preparation method flow chart of second purifying layer of the present invention；.
Fig. 5 is the preparation method flow chart of the 3rd purifying layer of the present invention.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention of greater clarity, below in conjunction with detailed description of the invention reference
Accompanying drawing, the present invention is described in more detail.It should be understood that these describe the most exemplary, and it is not intended to limit this
The scope of invention.Additionally, in the following description, the description to known features and technology is eliminated, to avoid unnecessarily
Obscure idea of the invention.
The present invention provides a kind of diesel engine exhaust gas purification device and preparation method thereof, and this device can purification diesel engine effectively
Nitrogen oxides (NO in tail gasx) and the pollutant such as soot particle (PM).
Such as Fig. 1, shown in Fig. 2, a kind of diesel engine exhaust gas purification device, including the first purifying layer 1, the second purifying layer 2
With the 3rd purifying layer 3.First purifying layer 1 is substantially carried out preparation and the NO of reducing agent COxSNCR reduction reaction,
Two purifying layers 2 are substantially carried out NOxSCR reduction reaction, the 3rd purifying layer 3 is substantially carried out NOxAbsorption.
First purifying layer 1 includes that the network structure being made up of resistance wire 4, resistance wire 4 area load have attapulgite, structure
Become SNCR denitration system.The thickness of the attapulgite of resistance wire 4 area load of the first purifying layer 1 is 0.2mm to 0.5mm.
Network structure in first purifying layer 1 has multiple, and spacing each other is 0.5cm to 1cm, the first purifying layer 1
Thickness is 30cm to 40cm, and the cancellated thickness of resistance wire 4 composition is 10cm to 15cm.The work of resistance wire 4
It is 220V as voltage, resistive heater 4 keep the temperature of resistance wire 4 between 750 DEG C to 1000 DEG C during work, make
Carbon soot particles (PM) generates CO, utilizes the reproducibility of CO to remove NO under high temperature and low temperature simultaneouslyx.Absorption is at attapulgite
The reactional equation of the carbon soot particles on soil surface is:
2C+O2 2CO,
C+O2——CO2。
CO can be with the NO in diesel engine vent gas under 750 DEG C to 1000 DEG C environmentxReaction, its reactional equation is as follows:
2NO+2CO——N2+2CO2,
2NO2+4CO——N2+4CO2。
In first purifying layer 1 in addition to the network structure of resistance wire 4 composition, remaining 20cm to 25cm part is empty
Heart pipeline, on the one hand can ensure CO and NOxFully react in this hollow pipe, on the other hand exhaust temperature can be made to reduce,
Meet the reaction temperature requirement of the second purifying layer.
It is equipped with diesel particulate filter 5 between first purifying layer 1 and the second purifying layer 2, is used for filtering unreacted carbon
Cigarette microgranule (PM), protects the catalyst in the second purifying layer, reduces the temperature of tail gas the most further.
Second purifying layer 2 includes titanyl compound and the oxide of the manganese as catalyst, constitutes SCR denitration system.The
Two purifying layers 2 also include the oxide of at least two variable valency metal as catalyst promoter, described metal includes ferrum, copper,
Vanadium, cerium, at least one in nobelium, the quality accounting of the oxide of described manganese between 5% to 15% quality, manganese with appraise at the current rate
The mol ratio of metal is between 0.1 to 3.
After diesel engine vent gas flows through hollow pipe and the diesel particulate filter 5 of the first purifying layer 1, temperature is down to 300 DEG C
To 400 DEG C, meeting the SCR reaction condition of the second purifying layer 2, its reactional equation is as follows:
2NO+2CO catalyst n2+ 2CO2,
2NO2+ 4CO catalyst n2+4CO2,
HC+NO2Catalyst n2+H2O+CO2。
3rd purifying layer 3 includes matrix, carrier and the rare-earth oxide being carried on carrier.In 3rd purifying layer 3
The oxide that rare-earth oxide is cerium, lanthanum and/or praseodymium at least one, described rare-earth oxide is in institute
State the quality accounting in carrier between 1% to 10%, the oxide of described cerium quality in described rare-earth oxide
Accounting is between 50% to 95%.(unification is once)
Diesel engine vent gas is through the first purifying layer 1 and the second purifying layer 2, a part of NOx, CO, HC there is reduction reaction,
Remaining NOx, CO, HC enter the 3rd purifying layer 3, attapulgite in the 3rd purifying layer 3 absorbs the NO in tail gasx、
The oxide of cerium not by electronics occupied orbital or unpaired electron track and NO in CO, HC, and carrierxHad
Electron orbit can form binding molecule sub-track, can keep for a long time at normal temperatures, can release when high temperature (400 DEG C)
Put.It is clean that the composite oxides that the oxide of lanthanum and/or praseodymium and the oxide of cerium form make NOx be easier to be saved in the 3rd
Change in layer 3.When the 3rd purifying layer 3 absorption reaches saturated, the 3rd purifying layer 3 is heated to 400 DEG C, absorption can be made
NOxRelease, simultaneously as the oxide of cerium has the feature of storage oxygen, therefore, the NO when being heated to 400 DEG CxWill be with NO2
Form release.
As it is shown on figure 3, the preparation method of the resistance wire of the first purifying layer includes step:
Step S101, takes attapulgite and is uniformly mixed in aqueous solution, stir and form serosity.
Step S102, takes resistance wire and is dipped in described serosity 10 minutes to 15 minutes.
Step S103, takes out resistance wire, is dried 0.5 hour to 1.5 hours at a temperature of 50 DEG C to 120 DEG C.
Step S104, repeats step S101 and obtains the resistance wire of area load attapulgite to step S103 for tri-times to six times.
As shown in Figure 4, the preparation method of the second purifying layer includes step:
Step S201 takes titanium and the nitrate of manganese and acetate is uniformly mixed in aqueous solution, and is stirred, wherein manganese
Oxide mass accounting between 5% to 15%.
Step S202, adds at least two variable valency metal ferrum, copper, vanadium, cerium or the nitrate of nobelium and acetate, wherein manganese
And the mol ratio of variable valency metal is between 0.1 to 3.
Step S203, will stand 1 hour to 3 hours after said mixture high-speed stirred 0.5 hour.
Step S204, takes blank ceramic honey comb and is dipped in taking-up after 5 minutes to 10 minutes in described mixture, be centrifuged and go
Except additional size, after drying completely at 50 DEG C to 120 DEG C, within 3 hours, obtained to 4 hours 400 DEG C to 600 DEG C roastings
Described second purifying layer.
As it is shown in figure 5, the preparation method of the 3rd purifying layer includes step:
Step S301, the nitrate or the chlorate that take attapulgite and cerium, lanthanum and/or praseodymium be uniformly mixed in aqueous solution,
Wherein metal-oxide quality accounting in the carrier is between 1% to 10%, the oxide of cerium matter in metal-oxide
Amount accounting is between 45% to 95%.
Step S302, will stand 1 hour to 2 hours after said mixture high-speed stirred 0.5 hour.
Step S303, takes blank ceramic honey comb and is dipped in described mixture and takes out after 7 minutes to 15 minutes, centrifugal segregation
Additional size, after drying completely at 50 DEG C to 120 DEG C, obtained institute to 4 hours in 3 hours 400 DEG C to 600 DEG C roastings
State the 3rd purifying layer.
Embodiment 1
Taking attapulgite uniformly to mix with aqueous solution, stirring forms serosity.
Take resistance wire to be dipped in above-mentioned solution 10 minutes.
Take out resistance wire, be dried 1 hour at a temperature of 100 DEG C.
Repeat above step and obtain the resistance wire of area load attapulgite for 4 times.
Embodiment 2
Taking attapulgite uniformly to mix with aqueous solution, stirring forms serosity.
Take resistance wire to be dipped in above-mentioned solution 15 minutes.
Take out resistance wire, be dried 0.5 hour at a temperature of 120 DEG C.
Repeat above step and obtain the resistance wire of area load attapulgite for 5 times.
Embodiment 3
Weigh certain mass titanium and the nitrate of manganese and acetate uniformly mixes and stirring in aqueous solution, the wherein oxide of manganese
Reduced mass is between 10%.
Weigh the variable valency metal ferrum of certain mass, copper, vanadium, cerium, the nitrate of nobelium and acetate, manganese and variable valency metal
Mol ratio is 2.
2 hours will be stood after said mixture high-speed stirred half an hour.
Take blank ceramic honey comb to be dipped in described mixture paste 7 minutes.
Take out and centrifugal segregation additional size, after drying completely at 70 DEG C, 500 DEG C of roastings 5 hours, obtain second clean
Change layer.
Embodiment 4
Weigh certain mass titanium and the nitrate of manganese and acetate uniformly mixes and stirring in aqueous solution, the wherein oxide of manganese
Reduced mass is between 11%.
Weigh the variable valency metal ferrum of certain mass, copper, vanadium, cerium, the nitrate of nobelium and acetate；Manganese and variable valency metal
Mol ratio is 1.5.
2 hours will be stood after said mixture high-speed stirred half an hour.
Take blank ceramic honey comb to be dipped in described mixture 10 minutes.
Take out and centrifugal segregation additional size, after drying completely at 80 DEG C, 450 DEG C of roastings 4 hours, obtain second clean
Change layer.
Embodiment 5
Weigh the attapulgite of certain mass and the nitrate of cerium, lanthanum and/or praseodymium or chlorate uniformly mix with in aqueous solution,
Wherein the oxide of cerium, lanthanum and/or praseodymium accounts for the 7% of carrier quality, and cerium oxide accounts for the 60% of whole oxide mass.
2 hours will be stood after said mixture high-speed stirred half an hour.
Take blank ceramic honey comb to be dipped in described mixture 8 minutes.
Take out and centrifugal segregation additional size, after drying completely at 100 DEG C, 500 DEG C of roastings 3.5 hours, obtain the
Three purifying layers.
Embodiment 6
Weigh the attapulgite of certain mass and the nitrate of cerium, lanthanum and/or praseodymium or chlorate uniformly mix with in aqueous solution,
Wherein the oxide of cerium, lanthanum and/or praseodymium accounts for the 5% of carrier quality, and cerium oxide accounts for the 70% of whole oxide mass.
2 hours will be stood after said mixture high-speed stirred half an hour.
Take blank ceramic honey comb to be dipped in described mixture 10 minutes.
Take out and centrifugal segregation additional size, after drying completely at 110 DEG C, 450 DEG C of roastings 4 hours, obtain the 3rd
Purifying layer.
It should be appreciated that the above-mentioned detailed description of the invention of the present invention is used only for exemplary illustration or explains that the present invention's is former
Reason, and be not construed as limiting the invention.Therefore, that is done in the case of without departing from the spirit and scope of the present invention appoints
What amendment, equivalent, improvement etc., should be included within the scope of the present invention.Additionally, the appended power of the present invention
It is complete that profit requires to be intended to fall in the equivalents on scope and border or this scope and border
Portion changes and modifications example.
Claims (6)
1. a diesel engine exhaust gas purification device, it is characterised in that described device exhaust starts the first purifying layer sequentially entered, the second purifying layer and the 3rd purifying layer；
First purifying layer includes that the network structure being made up of resistance wire, described resistance wire area load have attapulgite；
Second purifying layer includes the filtering coatings that titanyl compound and the oxide slurry as the manganese of catalyst load；
3rd purifying layer includes the filtering coatings that matrix, carrier and the rare-earth oxide slurry being carried on carrier load；
The thickness of the attapulgite of the resistance wire area load of described first purifying layer is 0.2mm to 0.5mm；
Network structure in described first purifying layer has multiple, and spacing each other is 0.5cm to 1cm, and the thickness of described first purifying layer is 30cm to 40cm, and the cancellated thickness of described resistance wire composition is 10cm to 15cm；
The running voltage of described resistance wire is 220V, resistive heater keep the temperature of resistance wire between 750 DEG C to 1000 DEG C during work；
Described second purifying layer slurry also includes that the oxide of at least two variable valency metal is as catalyst promoter, described metal includes ferrum, copper, vanadium, cerium, at least one in nobelium, the quality accounting of the oxide of described manganese i.e. accounts for the ratio of integer catalyzer between 5% to 15%, the mol ratio of manganese and variable valency metal is between 0.1 to 3, and the second purifying layer slurry is carried on ceramic honey comb and is dried.
Device the most according to claim 1, it is characterized in that, rare-earth oxide in described 3rd purifying layer is cerium, at least one in the oxide of lanthanum and/or praseodymium, between described rare-earth oxide quality accounting in described carrier is 1% to 10%, between the oxide of described cerium quality accounting in described rare-earth oxide is 45% to 95%.
Device the most according to claim 1, it is characterised in that be equipped with diesel particulate filter between described first purifying layer and the second purifying layer.
The preparation method of device the most according to claim 1, it is characterised in that step prepared by the resistance wire of described first purifying layer:
Step S101, takes attapulgite and is uniformly mixed in aqueous solution, stir and form serosity；
Step S102, takes resistance wire and is dipped in described serosity 10 minutes to 15 minutes；
Step S103, takes out resistance wire, is dried 0.5 hour to 1.5 hours at a temperature of 50 DEG C to 120 DEG C;
Step S104, repeats step S101 and obtains the resistance wire of area load attapulgite to step S103 for tri-times to six times.
Preparation method the most according to claim 4, it is characterised in that the preparation method of described second purifying layer includes step:
Step S201 takes titanium and the nitrate of manganese and acetate is uniformly mixed in aqueous solution, and is stirred, and wherein the oxide mass accounting of manganese is between 5% to 15%；
Step S202, adds at least two variable valency metal ferrum, and copper, vanadium, cerium or the nitrate of nobelium and acetate, wherein the mol ratio of manganese and variable valency metal is between 0.1 to 3；
Step S203, will stand 1 hour to 3 hours after said mixture high-speed stirred 0.5 hour；
Step S204, takes blank ceramic honey comb and is dipped in taking-up after 5 minutes to 10 minutes in described mixture, centrifugal segregation additional size, after drying completely at 50 DEG C to 120 DEG C, within 3 to 4 hours, obtain described second purifying layer 400 DEG C to 600 DEG C roastings.
Preparation method the most according to claim 4, it is characterised in that the preparation method of described 3rd purifying layer includes step:
Step S301, take attapulgite and cerium, lanthanum and/or the nitrate of praseodymium or chlorate are uniformly mixed in aqueous solution, and wherein metal-oxide quality accounting in the carrier is between 1% to 10%, and the oxide of cerium quality accounting in metal-oxide is between 45% to 95%;
Step S302, will stand 1 hour to 2 hours after said mixture high-speed stirred 0.5 hour；
Step S303, takes blank ceramic honey comb and is dipped in taking-up after 7 minutes to 15 minutes in described mixture, centrifugal segregation additional size, after drying completely at 50 DEG C to 120 DEG C, within 3 hours to 4 hours, obtain described 3rd purifying layer 400 DEG C to 600 DEG C roastings.
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| CN201410253764.1A CN104018918B (en) | 2014-06-09 | 2014-06-09 | A kind of diesel engine exhaust gas purification device and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070770A (en) * | 2006-03-24 | 2007-11-14 | 通用汽车环球科技运作公司 | Diesel particulate filter regeneration via resistive surface heating |
| CN101564646A (en) * | 2008-04-22 | 2009-10-28 | 赫多特普索化工设备公司 | Method for purification of an exhaust gas from a diesel engine |
| CN102387851A (en) * | 2009-04-03 | 2012-03-21 | 巴斯夫公司 | Emissions treatment system with ammonia-generating and SCR catalysts |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030198579A1 (en) * | 2002-04-22 | 2003-10-23 | Labarge William J. | Exhaust emission treatment device with a sulfur-free catalyst composition |
| JP5844672B2 (en) * | 2012-03-28 | 2016-01-20 | 日本碍子株式会社 | Honeycomb structure |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070770A (en) * | 2006-03-24 | 2007-11-14 | 通用汽车环球科技运作公司 | Diesel particulate filter regeneration via resistive surface heating |
| CN101564646A (en) * | 2008-04-22 | 2009-10-28 | 赫多特普索化工设备公司 | Method for purification of an exhaust gas from a diesel engine |
| CN102387851A (en) * | 2009-04-03 | 2012-03-21 | 巴斯夫公司 | Emissions treatment system with ammonia-generating and SCR catalysts |
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