CN106150610A - Double fuel oxidation catalyst, double fuel SCR waste gas treatment mechanism, double-fuel diesel internal combustion engine and control method thereof - Google Patents
Double fuel oxidation catalyst, double fuel SCR waste gas treatment mechanism, double-fuel diesel internal combustion engine and control method thereof Download PDFInfo
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- CN106150610A CN106150610A CN201510580315.2A CN201510580315A CN106150610A CN 106150610 A CN106150610 A CN 106150610A CN 201510580315 A CN201510580315 A CN 201510580315A CN 106150610 A CN106150610 A CN 106150610A
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/30—Use of alternative fuels, e.g. biofuels
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Abstract
The present invention provides double fuel oxidation catalyst, double fuel SCR waste gas treatment mechanism, double-fuel diesel internal combustion engine and control method thereof, alleviates and can not obtain the NOx clean-up effect of SCR catalyst and black smoke removes the suffering of the PM clean-up effect brought that burns in filter.Double fuel oxidation catalyst is for processing the waste gas of internal combustion engine diesel fuel and gas fuel used as fuel, wherein, have concurrently and a contained nitric oxide production part in the burning waste gas of diesel fuel is converted into the function of nitrogen dioxide, with the function that methane oxidation contained in described waste gas is decomposed, when the inlet temperature flowing to double fuel oxidation catalyst of described burning waste gas is more than 200 DEG C less than 300 DEG C, described nitric oxide is less than more than 20% 60% to the conversion ratio of nitrogen dioxide, and when described inlet temperature is 380 DEG C, more than 80% oxidized decomposition of the methane in described waste gas.
Description
Technical field
The present invention relates to by general fuel used for diesel engine such as diesel fuel, i.e. light oil and natural
The burning waste gas of the internal combustion engine that gas (CNG or LNG) fuel uses as double fuel carries out contact process
Double fuel oxidation catalyst, possess this double fuel oxidation catalyst SCR catalyst mechanism,
Possess double-fuel diesel internal combustion engine and the control method thereof of this SCR catalyst mechanism.
Background technology
Natural gas is compared with petroleum fuel, for the carbon dioxide discharged in combustion and harmful discharge
(oxysulfide (SOx), nitrogen oxides are (hereinafter also referred to " NOx " for composition.), the particle shape thing of coal smoke type
Matter) few green fuel, and compared with petroleum fuel, resource also has superiority, therefore,
The most particularly application to cogeneration equipment receives much concern.
It addition, in for motor vehicle internal combustion engine, develop the special gas engine of spark ignition mode
And for practicality, but for the excellent existing diesel engine of the thermal efficiency as at existing diesel fuel
Research that is upper and that apply by the double fuel mode of natural gas is also carried out in trial.This is to make natural gas conduct
Auxiliary fuel sucks the combustor of electromotor from air inlet pipe, and the premixed gas generated by combustor is with light
Oil drop fire makes its technology burnt, and has the advantage that the transformation of internal combustion engine is little.
Here, natural gas is divided into the LPG (letter of Liquefied Petroleum Gas (liquefied petroleum gas)
Claim), LNG (abbreviation of Liquefied Natural Gas (liquefied natural gas)) and CNG (Compressed
The abbreviation of Natural Gas (compressed natural gas)) these 3 kinds.
LPG is the separator making under comfortable room temperature, normal pressure the natural gass such as propane in gas or butane
Or in the subtractive process of oil produce fuel i.e. gas liquefaction and with liquefaction storage material,
Used by gasification as required.
In its component of the unstrpped gas of LNG 85%～95% is methane, other ethane, propane,
The compositions such as butane are less.LNG is for carrying out carrying, store and being cooled to by such natural gas
Less than-162 DEG C made liquid, volume is compressed into about the 1/600 of gaseous state.For utilizing
Such LNG, need gas well, pipeline, be liquefied as complete equipment, LNG oil carrier, load bearing equipment,
Equipment for gasification etc. are referred to as a series of equipment of " LNG chain ".
CNG is that its gas component is identical with LNG, with methane with the natural gas of high pressure compression
For main body, methane accounts for 85%～95%, and other ethane, propane, butane etc. are less.Such CNG
Motor vehicle fuel as environmental protection receives much concern in recent years.
So, LNG and CNG natural gas is mainly made up of methane.Here, known methane and dioxy
Change carbon to compare, hard-decomposed height, accordingly, it is possible to promote greenhouse effects of the earth.
On the other hand, the internal combustion engine using diesel fuel the material discharged is by (following containing nitric oxide
Also referred to as " NO ".) gas shape composition and be commonly called microgranule particle-like substance constitute.
Wherein, microgranule is become " baking " state by injected fuel spray oil droplet generated because of heat during burning
Coal smoke (dry soot), the imperfect combustion combustion residue of the fuel brought and engine oil volatile ingredient
Sulfuration contained in the organic solvent soluble ingredient (Soluble Organic Fraction) constituted and fuel
These 3 kinds of compositions of the oxysulfide (sulfate) of compound burning are constituted.Coal smoke type in the present invention
Particle-like substance refers to that coal smoke (SOOT) is (hereinafter also referred to as " PM ".).
Here, as and by the exhaust-gas treatment of diesel fuel and the diesel engine of LNG fuel with urging
Agent, it is proposed that contain the catalyst (patent documentation of palladium and platinum with the mass ratio of 1:0.1～1:0.5
1)。
But, by technology disclosed in patent documentation 1, the burning of less than 300 DEG C more than 200 DEG C
EGT territory, nitric oxide is to nitrogen dioxide (hereinafter also referred to " NO2”.) additive reaction hardly
Carry out.Therefore, the downstream of catalyst described in patent documentation 1 it is configured at along exhaust gas flow direction
SCR catalyst (Selective Catalytic Reduction (Chemoselective reduction) catalyst；Below also
Referred to as " SCR ".) clean-up effect of nitrogen oxides and black smoke are removed filter (diesel particulate
Catcher/filter.Hereinafter also referred to " DPF ".The clean-up effect that the burning of the PM in) brings all may
Can not get.
Prior art literature
Patent documentation
Patent documentation 1: International Patent Publication WO2009/057961 publication
Summary of the invention
Invent problem to be solved
It is an object of the invention to, alleviate this double fuel oxidation catalyst in prior art and had
, the NOx clean-up effect that may can not get SCR catalyst and black smoke remove in filter and burn
The suffering of the PM clean-up effect brought.
For solving the technical scheme of problem
First aspect present invention provides a kind of double fuel oxidation catalyst, for processing diesel fuel and
The waste gas of the internal combustion engine that gas fuel uses as fuel, it is characterised in that have concurrently diesel fuel
Burning waste gas in a contained nitric oxide production part be converted into the function of nitrogen dioxide and by described
The function that methane oxidation contained in waste gas decomposes, the double fuel oxidation that flows at described burning waste gas is urged
When the inlet temperature of agent is more than 200 DEG C less than 300 DEG C, described nitric oxide is to nitrogen dioxide
Conversion ratio is less than more than 20% 60%, and when described inlet temperature is 380 DEG C, in described waste gas
More than 80% oxidized decomposition of methane.
The double fuel oxidation catalyst of the present invention can to using diesel fuel and gas fuel as double combustions
The burning waste gas of internal combustion engine that material uses carries out contact process, and it can have and comprises urging of metal-oxide
Agent carrier and be made up of palladium and platinum and supported in the catalytically-active metals of described catalyst carrier,
Wherein, about palladium and the mass ratio of platinum of described catalytically-active metals, when setting palladium as 1, platinum is more than
0.5 and less than 0.9.
In the double fuel oxidation catalyst of the present invention, about described mass ratio, when setting palladium as 1, platinum
Can be less than more than 0.55 0.88.
The described double fuel oxidation catalyst of the present invention can be possibly together with as the second active catalyst gold
The iridium belonged to.
For the double fuel oxidation catalyst of the present invention, described catalyst carrier can be by gamma oxidation
Aluminum constitutes and contains the catalyst carrier of lanthana.
The present invention provides a kind of SCR waste gas treatment mechanism, makees by diesel fuel and gas fuel
For double fuel use internal combustion engine, particle-like substance containing nitric oxide, methane and coal smoke type
Burning waste gas carries out purified treatment, it is characterised in that move the upstream side in direction from described burner exhaust stream
Possess successively towards downstream: above-mentioned arbitrary double fuel oxidation catalyst；Existence at nitrogen dioxide
Under make at least some of burning of particle-like substance of described coal smoke type and the black smoke that is removed removes
Filter and/or, the supply source of reducing agent that is made up of carbamide and/or ammonia and selective contact reduction
(SCR) catalyst.
The present invention provides a kind of double-fuel diesel internal combustion engine, it is characterised in that possess above-mentioned SCR
Waste gas treatment mechanism.
The present invention provides the control method of a kind of double-fuel diesel internal combustion engine, controls above-mentioned double fuel bavin
Oil internal combustion engine, it is characterised in that at the entrance flowing to described double fuel oxidation catalyst of burning waste gas
When temperature is more than 380 DEG C, described natural gas is sucked from air inlet pipe the combustor of Diesel engine.
It addition, the present invention provides the control method of a kind of double-fuel diesel internal combustion engine, control above-mentioned double
Fuel diesel internal combustion engine, it is characterised in that calculate with volume ratio, make to be inhaled into diesel oil from air inlet pipe and send out
The quantity delivered of the natural gas of the combustor of motivation relative to the quantity delivered of described diesel fuel be 30% with
Upper less than 75%.
It addition, the present invention provides the control method of a kind of double-fuel diesel internal combustion engine, control above-mentioned double
Fuel diesel internal combustion engine, it is characterised in that burning waste gas flow to described double fuel oxidation catalyst
Inlet temperature when being more than 380 DEG C, described natural gas is sucked from air inlet pipe the combustion of Diesel engine
Burn room, and, calculate with volume ratio, make the air inlet pipe from Diesel engine be inhaled into Diesel engine
The quantity delivered of the natural gas of combustor is more than 30% 75% relative to the quantity delivered of described diesel fuel
Below.
Invention effect
The double fuel oxidation catalyst of the present invention for process using diesel fuel and gas fuel as
The waste gas of the internal combustion engine that fuel uses, has concurrently nitric oxide contained in the burning waste gas of diesel fuel
A part be converted into the function of nitrogen dioxide and methane oxidation contained in described waste gas decomposed
Function, the inlet temperature flowing to double fuel oxidation catalyst at described burning waste gas is more than 200 DEG C
When less than 300 DEG C, described nitric oxide is less than more than 20% 60% to the conversion ratio of nitrogen dioxide,
And when described inlet temperature is 380 DEG C, more than 80% oxidized decomposition of the methane in described waste gas,
Thus, it is possible to alleviate that double fuel oxidation catalyst of the prior art is had, may can not get
The NOx clean-up effect of SCR catalyst and black smoke remove the PM brought that burns in filter and purify effect
The suffering of fruit.
Accompanying drawing explanation
Fig. 1 be the double fuel oxidation catalyst representing and being configured with the present invention in order (hereinafter also referred to
“DOC”.) and the illustraton of model of configuration example of double fuel SCR mechanism of the present invention of SCR；
Fig. 2 is the double fuel SCR representing the present invention being configured with DOC, DPF and SCR in order
The illustraton of model of the configuration example of mechanism；
Fig. 3 is to represent that to be configured with DOC, DPF, SCR and ammoxidation catalyst in order (following
Also referred to as " AMOx ".) the illustraton of model of configuration example of double fuel SCR mechanism of the present invention；
Fig. 4 is the double of the present invention that represents and be configured with DOC, DPF, DOC and SCR in order
The illustraton of model of the configuration example of fuel SCR mechanism；
Fig. 5 is the basis representing and being configured with DOC, DPF, DOC, SCR and AMOx in order
The illustraton of model of the configuration example of the double fuel SCR mechanism of invention；
Fig. 6 is the present invention representing and being configured with DOC and SCR/DPF mono-body catalyst in order
The illustraton of model of the configuration example of double fuel SCR mechanism；
Fig. 7 represents and is configured with DOC, SCR/DPF mono-body catalyst and AMOx in order
The illustraton of model of the configuration example of the double fuel SCR mechanism of the present invention；
Fig. 8 is the illustraton of model of the configuration example of the double-fuel diesel internal combustion engine representing the present invention.
Symbol description
1 electromotor (diesel fuel and the dual fuel engine of gas fuel)
2 double fuel oxidation catalysts (DOC:Diesel Oxidation Catalyst)
3 black smokes remove filter (DPF:Diesel Particulate Filter)
4 selective reduction catalysts (SCR:Selective Catalytic Reduction)
5 ammoxidation catalysts (AMOx:Ammonia Oxidation Catalyst)
The 6 one-piece type catalyst of SCR/DPF
7 reducing agent injectors
8 DOC inlet temperature sensors
The ejector of 9 gas fuels
The ejector of 10 diesel fuels
The supply pipeline of 11 gas fuels
The supply pipeline of 12 diesel fuels
The supply pipeline of 13 reducing agents
14 coolers for recycled exhaust gas
21 engine main bodies
22 combustor
23 pistons
25 air inlet pipe
26 exhaustors
Detailed description of the invention
The double fuel oxidation catalyst of the present invention is used for processing use gas fuel and diesel fuel is made
For the waste gas of the internal combustion engine of fuel, have concurrently contained nitric oxide production in the burning waste gas of diesel fuel
A part is converted into the merit of methane contained in the function of nitrogen dioxide and the above-mentioned waste gas of oxidation Decomposition
Can, the inlet temperature flowing to double fuel oxidation catalyst at above-mentioned burning waste gas is more than 200 DEG C
When less than 300 DEG C, above-mentioned nitric oxide it is less than more than 20% 60% to the conversion ratio of nitrogen dioxide,
And when above-mentioned inlet temperature is 380 DEG C, more than 80% oxidized decomposition of the methane in above-mentioned waste gas.
＜ natural gas ＞
The gas fuel used in the present invention is in above-mentioned 3 kinds of natural gass, CNG or LNG.
Here, from infrastructure, conveying machinery material and operate cheap and easy this point, preferably make
Use CNG.Additionally, from the viewpoint of equipment, CNG and LNG is generally not capable of and use, but the present invention
In can be used together, even if in the case of being recited as " CNG or LNG ", also comprise them and use
Situation.
＜ metal-oxide ＞
In the double fuel oxidation catalyst of the present invention, as the metal-oxide as catalyst carrier,
The catalysis as usual oxidation catalyst such as aluminium oxide, zirconium oxide, titanium dioxide, cerium oxide can be enumerated
The oxide that agent carrier uses, wherein, is up to 50～300m from specific surface area2/ g, the available initial stage is alive
Property this point set out, preferably γ type aluminium oxide is (following also referred to as " gama-alumina ".) and anatase titanium dioxide dioxy
Change titanium.It should be noted that can also suitably use heat durability lasting: zirconium oxide, rutile
Type titanium dioxide and cerium oxide.
＜ effect composition ＞
If above-mentioned double fuel oxidation catalyst contains oxysulfide, chlorine and chlorinated compound, lanthana
As effect composition, then can suppress crystal transition during high temperature, be derived from the burning waste gas of diesel fuel
Oxysulfide (SO contained by2) suppression etc. of catalyst poisoning can be realized, the most preferably.
That is, oxysulfide, chlorine and chlorine compound has oxysulfide (SO2) catalyst poisoning brought presses down
Effect processed, on the other hand, lanthana gama-alumina and anatase titanium dioxide to becoming the reason that thermostability reduces
The crystalline transition of titanium dioxide lanthanum has inhibition.
Such effect composition is by being dissolved in ion exchange water the raw material i.e. metal oxygen with carrier
It is dried after compound is mixing, burns till, can be contained in catalyst carrier.Above-mentioned for fully obtaining
Effect, preferably makes such effect composition be contained in catalyst carrier with the scope of 0.3～5 mass %.
＜ granularity ＞
The mean diameter of the catalyst carrier used in the double fuel oxidation catalyst of the present invention is (by laser
Diffraction-type hondrometer measures, and the volume being equivalent to particle diameter distribution adds up the particle diameter (D50) of 50%) it is preferably
0.5～15 μm.If too small, then the viscosity of the slurry being applied in honeycomb ceramics becomes high viscosity, easily draws
Rise blocking and bad, if excessive, then honeycomb ceramics support film strength reduce, may be because of vibration
Peel off.
Granularity adjusts and known method can be used to carry out.That is, can be by using pulverizer and/or grader
Adjust.
As pulverizer, ball mill pulverizer, attritor mill pulverizer, sand milling pulverizer, pearl can be enumerated
Grinding machine, draw point grinding and crushing machine, sledge mill pulverizer, grinding pulverizer, jet pulverizer etc..
On the other hand, as grader, vibrating screen classifier, ultrasonic vibration screening machine can be used, shake
Dynamic screening machine, whirlpool formula grader, gas flow sizing machine (pyramid type, sharp turn jet) etc..
＜ metal oxide carrier is to the loading method ＞ of catalyst matrix
The method making catalyst matrix carrying metal oxide carrier and catalytically-active metals can use
Known method, but owing to high supporting of catalytically-active metals can be suppressed to lose and be recycled into
This, it is therefore preferable that adopt with the following method: first, make the catalyst being made up of above-mentioned metal-oxide
Supported carrier is in carrier matrix, then, carries on a shoulder pole on the catalyst matrix be supported with this catalyst carrier
Carry catalytically-active metals.
Use honeycomb monolith carrier as catalyst matrix in the case of, preferably make catalyst matrix with
At least mode supported catalyst agent carrier of more than 50g/L (liter).If that is, the supporting of catalyst carrier
Measure very few, then can not increase the loading of catalytically-active metals, now may not obtain the cleanest
Change effect.More preferably catalyst carrier 50～200g/L scope.
＜ catalyst matrix ＞
As catalyst matrix, in order to can carry out gas stream by processing, it is possible to use known
The catalyst matrix of honeycomb circulation type.As the material of this catalyst matrix, can be from pottery, nothing
Organic fiber and metal select.Here, as preferred Porous honeycomb circulation monolithic substrate, permissible
Use cordierite, Alpha-alumina, carborundum, aluminium titanates, silicon nitride, zirconium dioxide, mullite,
The base material of the known ceramic material such as spodumene, alumina-silica magnesia or Zirconium orthosilicate..
Catalyst matrix as inorfil, it is possible to use by silicon dioxide fibre, aluminium oxide fibre
The ceramic fibre of the compositions such as the oxide of dimension and silicon, titanium or zirconium.
It addition, as metal catalyst matrix, it is possible to use titanium system, stainless steel or contain
The matrix of the alloy of more than 2 in nickel, chromium and aluminum.
As catalyst matrix, the most particularly becoming present aspect favourable, it is advantageous to use honeycomb stream
The catalyst matrix of the cordierite of logical monolithic.
＜ binding agent ＞
As suitable to the binding agent supporting process supporting carrier of catalyst matrix, oxygen can be enumerated
Change aluminum and silicon dioxide, they are not limited.As alumina adhesive, can enumerate aluminium oxide,
Aluminium hydroxide and aluminic acid hydroxide.Alternatively, it is also possible to use aluminium salt and the oxidation of colloid mode
Aluminum.As silica binder, including the silicon dioxide (SiO comprising cabosil2) various
Mode.And, as binding agent, can be used alone them, or by zirconium dioxide, aluminium oxide,
And the proper combination such as silicon dioxide uses.
＜ catalytically-active metals support ＞
The double fuel oxidation catalyst of the present invention such as can obtain as follows: at catalyst matrix
On by and with inorganic bond in the way of support the catalyst carrier comprising metal-oxide, and do
Dry, heat treatment, impregnated in the catalyst matrix being supported with catalyst carrier obtained containing palladium ion
(live as second with the catalytically-active metals aqueous solution of platinum ion or containing palladium ion and platinum ion and iridium
Property catalyst metals iridium) ion catalytically-active metals aqueous solution in keep 12～24 hours, make this
A little compositions are co-precipitated in catalyst carrier and are dried, heat treatment.
＜ catalytically-active metals ＞
In the double fuel oxidation catalyst of the present invention, in order to have concurrently catalyst temperature (generally with to catalyst
The temperature of the burning waste gas of supply is equal) it is that methane oxidation when more than 380 DEG C decomposes the methane brought
Clean-up effect and the oxidation of NO when less than 300 DEG C bring to NO2Changing effect, need to contain
There are palladium and platinum and then the most also can contain iridium, and the mass ratio of palladium and platinum is when setting palladium as 1, platinum
Need in the scope more than 0.5 and less than 0.9.As the preferred scope of mass ratio, platinum is 0.55
Above less than 0.88.That is, if the amount of platinum is very few, then the NO that the oxidation of NO is brought2Life
Become few, the NOx that the PM flammability being difficult to obtain in the DPF in downstream and SCR catalyst are brought
Purifying property, if too much, then the purifying property of the hydro carbons containing methane is easily reduced.Additionally, it is above-mentioned
Mass ratio more preferably in the range of less than more than 0.55 0.8.
It addition, using iridium as the second active catalytic metals and with in the case of preferred quality compare model
It is less than more than 0.2 0.9 when being trapped among the quality setting palladium as 1.If the amount of iridium is very few, then can not get
The mutually auxiliary effect of palladium catalyst that the interpolation of iridium catalyst is brought, the purifying property of the hydro carbons containing methane and
NO2Growing amount can not get increasing, thus the PM flammability in the DPF in downstream and SCR catalyst
The raising advantage of the NOx purifying property brought is few.If too much, then wasting high catalyst,
Shortcoming practicality.More preferably in the range of less than more than 0.28 0.86.
＜ contains the water soluble compound ＞ of catalytically-active metals
As the water soluble compound containing platinum, chlorination platinic acid, four ammino platinum nitrates, two Asias can be enumerated
Nitro diamino platinum etc..Wherein, from noble metal support (co-precipitation) property height from the viewpoint of, be preferably
Dinitroso diammonia platinum.As the water soluble compound containing palladium, can enumerate Palladous nitrate., Palladous chloride.,
Dinitroso diamino palladium, palladium etc..
＜ contains the water soluble compound ＞ of the second catalytically-active metals
In the present invention, the metal beyond the palladium removing of catalytically-active metals and platinum is referred to as the second catalysis activity
Metal, as the water soluble compound containing iridium, can enumerate nitric acid iridium, sulphuric acid iridium, iridium chloride, six
Ammino iridium chloride etc..
At the water soluble compound of above-mentioned active noble metals and the second catalytically-active metals relative to water
Dissolubility is low and can not get expecting in the case of concentration, for improving dissolubility, it is also possible to add nitric acid or
Hydrochloric acid etc..
The double fuel oxidation catalyst ＞ of the ＜ present invention
The double fuel oxidation catalyst of the present invention has concurrently and is divided by the unburned methane oxidation of gas fuel
Solve function and a part of the NO from diesel combustion waste gas is converted into NO efficiently2Merit
Energy.
That is, high vehicle speeds is exceeded when the inlet temperature of the double fuel oxidation catalyst flowing to the present invention
During time (high load capacity) 350 DEG C, can purified natural gas fuel and being derived from during diesel fuel mixed combustion
The hard-decomposed composition namely for methane of natural gas, on the other hand, when inlet temperature is that vehicle travels in city
During time (underload) less than 300 DEG C, an oxygen can be carried out for the situation of only diesel fueled combustion
Change carbon (hereinafter also referred to " CO ".), hydro carbons (hereinafter referred to as " HC ".) and SOF (unburned fuel or unburned
Lubricating oil) purification and nitric oxide (NO) to nitrogen dioxide (NO2) conversion.
Therefore, when using the double fuel oxidation catalyst of the present invention, preferably in the combustion of catalyst inlet
Burning EGT is to use double fuel, if comparing in the range of usual more than 350 DEG C and less than 600 DEG C
More than temperature province that is 200 DEG C that this temperature field is low less than 300 DEG C, the most only carry out diesel fuel
Burning.The scope using the preferred temperature of dual-fuel to be more than 380 DEG C less than 450 DEG C.This
Although having in terms of the oxidation removing of the methane that the double fuel oxidation catalyst of invention is in burning waste gas
High activity, but in the case of burning exhaust-gas treatment temperature is too low, activity reduces, and may can not get institute
Desired methane removal rate.On the other hand, in the feelings that the burnt gas temperature territory of catalyst inlet is too high
Under condition, the durability of catalyst may deteriorate.
According to such reason, in the double-fuel diesel of double fuel oxidation catalyst possessing the present invention
In combustion engine, it is preferably as follows and is controlled, it may be assumed that use the double fuel oxidation catalyst of the present invention, at place
When the catalyst inlet temperature of reason object gas is more than 350 DEG C, diesel fuel and natural gas are mixed to
Combustor spray, and with oxidation catalyst to burning waste gas in residual fuel composition namely for methane at
Reason.Additionally, condition beyond above-mentioned condition can in a known manner on the basis of.
Such as, for the performance, burning exhaust gas properties, combustion characteristics of dual-fuel diesel engine, when making
Natural gas (CNG or LNG) supply heat changes relative to total ratio (Qg/Qt) putting into heat
Time, with the increase of natural gas supply ratio, Smoke concentration, i.e. black smoke density can significantly reduce.
Operating here, known compared to diesel oil, the ignition timing of double fuel operating is slower.In addition, it is known that sky
So gas supply ratio (CNG or LNG in the total volume of CNG or LNG and diesel fuel
Volume.Hereinafter also referred to " CNG supplies ratio ".) be in less than 75% scope time, can obtain
To high BTHE equal with the operating of common diesel oil, if but CNG supply ratio be more than
75%, then can cause being increased dramatically of Combustion fluctuation, igniting can be unstable, and BTHE can be significantly
Reduce.In the present invention, for CNG supply ratio, the pistons work brought due to firing delay
Amount loss is few, can highly keep BTHE, it is advantageous to be set to less than 75%.Here, it is excellent
Selecting CNG supply ratio is more than 30%.That is, if less than 30%, then Smoke concentration is high,
Less than using dual-fuel advantage.Additionally, Qg/Qt=0% represents situation about only operating with diesel fuel.
The double fuel SCR waste gas treatment mechanism ＞ of the ＜ present invention
The double fuel SCR waste gas treatment mechanism of the present invention is to using diesel fuel and gas fuel work
For dual-fuel internal combustion engine, particle-like substance containing nitric oxide, methane and coal smoke type burning
Waste gas carries out purified treatment, and moves the upstream side in direction towards downstream from burner exhaust stream, in order
Possess: the double fuel oxidation catalyst of the invention described above；Above-mentioned coal smoke is made in the presence of nitrogen dioxide
At least some of burning of the particle-like substance of type and the black smoke that is removed remove filter and/or,
The supply source of the reducing agent being made up of carbamide and/or ammonia and selective contact reduction (SCR) catalyst.
Fig. 1 represents an example of the double fuel SCR waste gas treatment mechanism of the present invention.In this example, by bavin
The internal combustion engine i.e. waste gas of electromotor 1 that oil fuel and gas fuel use as double fuel passes through this
Bright double fuel oxidation catalyst (DOC), NO is converted into NO2, CO, HC, SOF quilt simultaneously
Remove, and, methane the most oxidized and remove after, be mixed into from reducing agent injector 7
The reducing agent being made up of carbamide and/or ammonia is (hereinafter also referred to " reducing agent ".), it is then supplied to select
Property contact reducing catalyst (" SCR " or " SCR catalyst "), NOx is by selectivity contact reduction,
Discharge purified waste gas eventually.
Here, the reaction mechanism of selective contact reducing catalyst is illustrated.Using reducing agent
(carbamide, ammonia (hereinafter also referred to " NH3”.) etc.) and selective contact reduction (SCR) system in, can send out
Raw several chemical reactions, all these chemical reactions generally represent and NOx are reduced to element shape nitrogen
Reaction.Overriding reaction mechanism is represented by chemical formula (1).
[changing 1] 4NO+4NH3+O2→4N2+6H2O·····(1)
The non-selective reaction that carries out of oxygen with competition forms by-product sometimes or unproductive disappears
Consumption NH3.As such non-selective reaction, such as, can enumerate the NH shown in chemical formula (2)3's
Complete oxidation.
[changing 2] 4NH3+5NO2→4NO+6H2O·····(2)
And then, NOxPresent in NO2With NH3Reaction be considered by shown in chemical formula (3)
Reaction is carried out.
[changing 3] 3NO2+4NH3→(7/2)N2+6H2O·····(3)
And, NH3With NO and NO2Between reaction by shown in chemical formula (4) reaction show.
[changing 4] NO+NO2+2NH3→2N2+3H2O·····(4)
The response speed of the reaction shown in chemical formula (1), (3) and (4) is according to reaction temperature and is used
The kind of catalyst and significantly different, the speed of the reaction shown in chemical formula (4) is typically up to chemical formula (1)
And 2～10 times of the speed of the reaction shown in (3).
Therefore, for improving the NOx clean-up effect of SCR catalyst, preferably by NO and NO2Appearance
Long-pending ratio is set to 1:0.5～1:1.5, and this will be appreciated that.
Fig. 2 represents other example of the double fuel SCR waste gas treatment mechanism of the present invention.In this example, Fig. 1
Example in the burning waste gas discharged from DOC before reducing agent injector 7 adds reducing agent, first
Filter is removed (following by least one of black smoke of the particle-like substance in order to remove coal smoke type
Also referred to as " DPF ".)3.
Can in this wise the present invention double fuel oxidation catalyst burner exhaust stream downstream arrange
There is the DPF3 of coal smoke type particulate material capture trap function.Now, by the double fuel oxygen of the present invention
Change catalyst, from NO to NO2Efficient Conversion function, can be at NO2In the presence of make coal smoke
The particulate material of type burns efficiently with relatively low temperature.It is not as a result, it is possible to cause closing of DPF3
Plug and the problem of negative pressure and purifying combustion waste gas, and reduce a part of NOx simultaneously.DPF is special
It is preferably the most commercially available DPF being commonly called wall-flow filter type manufactured by pottery, but
Comprise and weave cotton cloth or the other type of DPF of thermostability cloth of non-woven fabrics can also use as DPF.
In other example of the double fuel SCR waste gas treatment mechanism of the present invention shown in Fig. 3, at Fig. 2
In the burner exhaust stream downstream of SCR4 be provided with ammoxidation catalyst (AMOx) 5.By this
AMOx5, can remove the residual ammonia oxidation in burning waste gas.
In other example of the double fuel SCR waste gas treatment mechanism of the present invention shown in Fig. 4, at Fig. 2
The burner exhaust stream downstream of the DPF3 of shown example and the upstream side of reducing agent injector 7 also configure that
There is DOC2.By this structure, compared with the double fuel SCR waste gas treatment mechanism shown in Fig. 2, can
Together to supply NO2 to DPF3 and SCR2, such that it is able to improve DPF3 PM flammability and
The NOx purifying property of SCR2.
In other example of the double fuel SCR waste gas treatment mechanism of the present invention shown in Fig. 5, at Fig. 4
The burner exhaust stream downstream of the SCR4 of the double fuel SCR waste gas treatment mechanism example of the shown present invention
It is configured with AMOx5.By this structure, the double fuel SCR waste gas treatment mechanism shown in Fig. 4 is arranged
The residual ammonia gone out removes.
In other example of the double fuel SCR waste gas treatment mechanism of the present invention shown in Fig. 6, electromotor 1
Burning waste gas purified by DOC2 after, reducing agent injector 7 add reducing agent, then pass through
The one-piece type catalyst of SCR/DPF 6, i.e. SCR and DPF catalyst integrally.According to this knot
Structure, single honeycomb catalyst body just can have the function that PM purifies and NOx purifies, Ke Yishi
Existing miniaturization.
Fig. 7 represents the downstream configuration of the one-piece type catalyst of SCR/DPF 6 in the example shown in Fig. 6
There is the example of AMOx5.
The double-fuel diesel internal combustion engine of the present invention such as possesses the double fuel SCR shown in Fig. 1～Fig. 7 and gives up
Gas disposal mechanism.
In Fig. 8, as an example of the double-fuel diesel internal combustion engine of the present invention, it is shown that possess Fig. 2 institute
The illustraton of model of the double-fuel diesel internal combustion engine of the double fuel SCR waste gas treatment mechanism of the type shown.
Diesel engine shown here is exhaust recirculation type, in the air inlet pipe of engine main body 21
Having cooler for recycled exhaust gas 14 between 25 and exhaustor 26, one of waste gas by cooler for recycled exhaust gas 14
After cooling, from air inlet pipe 25 to the circulation supply of the combustor 22 of engine main body 21.In air inlet pipe
25, it is provided with the ejector 9 of the gas fuel that the supply pipeline 11 with gas fuel is connected, natural
Gas fuel is inhaled in combustor when the air inlet of engine main body 21 circulates.At engine main body 21
Combustor 22, be provided with the ejector 10 of the diesel fuel that the supply pipeline 12 with diesel fuel is connected,
Diesel fuel can be supplied to combustor 22.On exhaustor 26, move direction from burner exhaust stream
Upstream is provided with in order towards downstream: for measuring the temperature of the burning waste gas being directed to DOC2
The reducing agent spray that DOC inlet temperature sensor 8, DOC2 are connected with the supply pipeline 13 of reducing agent
Emitter 7 and SCR4.Additionally, in figure, label symbol 23 represents the piston of engine main body 21.
In this double-fuel diesel internal combustion engine of the present invention, measure combustion by DOC inlet temperature sensor 8
Burn the temperature of waste gas, and when this temperature is more than 350 DEG C, carry out the ejector 9 from gas fuel
The control of supply gas fuel.
Above, enumerate and preferred embodiment illustrate the present invention, but the oxidation of the double fuel of the present invention
Catalyst, SCR waste gas treatment mechanism, double-fuel diesel internal combustion engine and double-fuel diesel internal combustion engine
Control method is not limited to the formation scheme of above-mentioned embodiment.
Those skilled in the art, according to existing known opinion, can suitably change the double fuel oxidation of the present invention
Catalyst, SCR waste gas treatment mechanism, double-fuel diesel internal combustion engine and double-fuel diesel internal combustion engine
Control method.Even if carrying out such change, if its possess the present invention double fuel oxidation catalyst,
SCR waste gas treatment mechanism, double-fuel diesel internal combustion engine and the control method of double-fuel diesel internal combustion engine
Scheme, then would naturally fall within scope of the invention.
Embodiment
Below, it is shown that embodiment illustrates in greater detail the present invention, but the invention is not restricted to these and implement
Example.
＜ embodiment 1 ＞
Make double fuel oxidation catalyst as follows, in this double fuel oxidation catalyst, cladding
There are lanthana and the gamma-aluminium oxide carrier containing the gama-alumina as metal-oxide expensive with as activity
The palladium of metallic catalyst and the mass ratio of platinum are 1:0.6.
First, gama-alumina (GB-13, water chemistry society system) is pulverized, exchange to ion in advance
Water 750g dissolves Lanthanum (III) nitrate 6 hydrate (La (NO3)3·6H2O) (with Guang Chun medicine society system) 9.36g and
In the lanthanum nitrate aqueous solution of preparation, stir and put into mean diameter (D50) in batches and be adjusted
It is that the gama-alumina powder 300g of 5 μm mixes.Afterwards, from lanthanum nitrate aqueous solution, γ-oxygen is taken out
Changing aluminium powder, the container moving to floor space big is the driest, then, uses electric furnace to carry out with 500 DEG C
The heat treatment (burning till) of 2 hours.Afterwards, crush with magnetic mortar, make mean diameter (D50) become
It is 5 μm, obtains being made up of the gama-alumina of 1 mass % and containing the catalyst carrier of lanthana.
Secondly, use magnetic ball grinding machine, this catalyst carrier 25g of lanthana, oxidation will be coated with
Alumina gel (Nissan Chemical society system, AS200) 9.3g, colloidal silica (Nissan Chemical society system, ス ノ
テ ッ Network O) 15.5g together mixes with ion exchange water 75g, obtains washcoat coating (WC)
Use slurry.This slurry is coated cordierite honeycomb ceramics (diameter 21mm, length 20mm, #
300cpsi), after drying, carry out the heat treatment of 2 hours with 500 DEG C, obtain being coated with catalyst carrier
Honeycomb structure.The catalyst carrier painting amount of this honeycomb structure is relative to the hair body of honeycomb structure
Amass as 100g/L (L: rise).
Then, Palladous chloride. (PdCl has been prepared2) (palladium is (hereinafter also referred to for hydrochloric acid 3.6 mass % aqueous solution
“Pd”.) be 100g/L) and dinitroso diammonia platinum (Pt (NO2)2(NH3)2) (platinum is (the most also for aqueous solution
It is referred to as " Pt ".) be 8.5 mass %).
Ion exchange water 25g adds above-mentioned Palladous chloride. hydrochloric acid solution 0.118mL (milliliter) and on
State dinitroso diammonia platinum aqueous solution 0.08g, make active noble metals and support aqueous solution.This activity is expensive
The mass ratio of Pt, Pd and Pt that metal supports Pd and 6.8mg in aqueous solution containing 11.8mg is
1:0.58.
Above-mentioned active noble metals is supported aqueous solution and adds glass container, be impregnated with wherein and seal coating
There is the honeycomb structure of said catalyst carrier (hereinafter also referred to as " catalyst carrier ".).At this shape
Use drying machine to heat 24 hours with 50 DEG C under state, make palladium and platinum be co-precipitated in catalyst carrier
Support, then take out catalyst carrier.After drying, carry out the heat treatment process of 2 hours with 500 DEG C,
Obtain the double fuel oxidation catalyst of embodiment 1.Analysis active noble metals supports the residual liquid of aqueous solution
Result is, for active noble metals supports dose rate, it is 99 mass % that Pd supports dose rate, and Pt supports
Dose rate is 100 mass %.
＜ active noble metals supports dose rate ＞
Above-mentioned active noble metals supports dose rate and investigates as follows.That is, for active noble metals
Support the residual liquid supported after process of aqueous solution, use inductively coupled plasma ICP Atomic Emission Spectrophotometer dress
Put (ICP-AES:Inductively Coupled Plasma-Atomic Emission Spectrometry) to enter
The quantitative analysis of row activity, and ask for active noble metals with following formula (1) and support dose rate.
[several 1]
(the 1-amount of Pd, Pt, Ir in rear solution (active noble metals support)/(active noble metals supports
The amount of Pd, Pt, Ir in front aqueous solution)) × 100% ... (1)
＜ embodiment 2 ＞
It is set to 1 except above-mentioned active noble metals being supported contained, the mass ratio of Pd and Pt in aqueous solution:
Beyond 0.85, implement similarly to Example 1, obtain the double fuel oxidation catalyst of embodiment 2.
Make catalyst carrier i.e., similarly to Example 1, afterwards, in ion exchange water 25g
Add above-mentioned palladium chloride aqueous solution 0.080mL, above-mentioned dinitroso diammonia platinum aqueous solution 0.08g, system
Catalytically-active metals is become to support aqueous solution.Above-mentioned active noble metals supports in aqueous solution containing 8.0mg's
The mass ratio of Pt, Pd and the Pt of Pd and 6.8mg is 1:0.85.Afterwards, still with embodiment 1
Similarly implement, obtain the double fuel oxidation catalyst of embodiment 2.Active noble metals load the most now
For carrying capacity rate, it is 100 mass % that Pd supports dose rate, and it is 100 mass % that Pt supports dose rate.
＜ embodiment 3 ＞
Except adding further on the basis of Pd and Pt that above-mentioned active noble metals supports contained by aqueous solution
Iridium is (hereinafter also referred to " Ir ".Beyond), implement similarly to Example 1, obtain the double fuel of the present invention
Oxidation catalyst.
Make catalyst carrier i.e., similarly to Example 1, add in ion exchange water 25g
State palladium chloride aqueous solution 0.118mL, above-mentioned dinitroso diammonia platinum aqueous solution 0.08g, nitric acid iridium
(Ir(NO3)4) aqueous solution (Ir is 100g/L) 0.034mL, make active noble metals and support aqueous solution.Should
Active noble metals support the Ir of Pt, 3.4mg of Pd, 6.8mg that aqueous solution contains 11.8mg, Pd,
The mass ratio of Pt and Ir is 1:0.58:0.29.Afterwards, implement similarly to Example 1, obtain
The double fuel oxidation catalyst of embodiment 3.For active noble metals with regard to now supports dose rate, Pd
Supporting dose rate is 99 mass %, and it is 100 mass % that Pt supports dose rate, and it is 97 mass % that Ir supports dose rate.
＜ embodiment 4 ＞
Except adding further on the basis of Pd and Pt that above-mentioned active noble metals supports contained by aqueous solution
Beyond Ir, implement similarly to Example 1, obtain the double fuel oxidation catalyst of the present invention.
Make catalyst carrier i.e., similarly to Example 1, add in ion exchange water 25g
State palladium chloride aqueous solution 0.118mL, above-mentioned dinitroso diammonia platinum aqueous solution 0.08g, nitric acid iridium molten
Liquid (Ir is 100g/L) 0.102mL, makes active noble metals and supports aqueous solution.This active noble metals is carried on a shoulder pole
Carry the Ir of Pt, 10.2mg of Pd, 6.8mg of containing 11.8mg in aqueous solution, Pd, Pt and Ir
Mass ratio be 1:0.58:0.86.Afterwards, implement similarly to Example 1, obtain embodiment 4
Double fuel oxidation catalyst.For active noble metals with regard to now supports dose rate, Pd supports dose rate and is
98 mass %, it is 99 mass % that Pt supports dose rate, and it is 95 mass % that Ir supports dose rate.
＜ embodiment 5 ＞
Palladous nitrate. (Pd (NO is used in the same manner as patent documentation 13)2) and chlorination platinic acid (H2PtCl6), by upper
State active noble metals to support in aqueous solution the mass ratio of contained Pd and Pt and be adjusted to 1:0.55, remove
Beyond this, implement similarly to Example 1, obtain the double fuel oxidation catalyst of the present invention.
Make catalyst carrier i.e., similarly to Example 1, afterwards, in ion exchange water 25g
(Pt is 8.5 matter to add above-mentioned palladium nitrate aqueous solution 0.123mL and platinum chloride aqueous acid
Amount %) 0.08g, makes catalytically-active metals and supports aqueous solution.This active noble metals supports in aqueous solution
The mass ratio of Pt, Pd and the Pt of Pd, 6.8mg containing 12.3mg is 1:0.55.Afterwards, with
Embodiment 1 is similarly implemented, and obtains the double fuel oxidation catalyst of embodiment 5.Activity the most now
For noble metal loadings rate, it is 93 mass % that Pd supports dose rate, and it is 98 mass % that Pt supports dose rate.
＜ embodiment 6 ＞
Except the palladium chloride aqueous solution of embodiment 1 being replaced with Palladous nitrate. (Pd (NO3)2) (Pd is aqueous solution
Beyond 100g/L), implement similarly to Example 1, obtain the double fuel oxidation catalyst of embodiment 6.
Make catalyst carrier i.e., similarly to Example 1, afterwards, in ion exchange water 25g
Add above-mentioned palladium nitrate aqueous solution 0.118mL, above-mentioned dinitroso diammonia platinum aqueous solution 0.08g, system
Catalytically-active metals is become to support aqueous solution.Above-mentioned active noble metals supports in aqueous solution containing 11.8mg
The mass ratio of Pt, Pd and Pt of Pd, 6.8mg be 1:0.58.Afterwards, still with embodiment
1 similarly implements, and obtains the double fuel oxidation catalyst of embodiment 6.Active noble metals the most now
For supporting dose rate, it is 100 mass % that Pd supports dose rate, and it is 100 mass % that Pt supports dose rate.
＜ embodiment 7 ＞
It is set to 1 except above-mentioned active noble metals being supported contained, the mass ratio of Pd and Pt in aqueous solution:
Beyond 0.75, implement similarly to Example 1, obtain the double fuel oxidation catalyst of embodiment 7.
Make catalyst carrier i.e., similarly to Example 1, afterwards, in ion exchange water 25g
Add above-mentioned palladium chloride aqueous solution 0.091mL, above-mentioned dinitroso diammonia platinum aqueous solution 0.08g, system
Catalytically-active metals is become to support aqueous solution.Above-mentioned active noble metals supports in aqueous solution containing 9.1mg's
The mass ratio of Pt, Pd and the Pt of Pd, 6.8mg is 1:0.75.Afterwards, still same with embodiment 1
Sample ground is implemented, and obtains the double fuel oxidation catalyst of embodiment 7.Active noble metals the most now supports
For dose rate, it is 99 mass % that Pd supports dose rate, and it is 100 mass % that Pt supports dose rate.
＜ comparative example 1 ＞
Implement in the same manner as the embodiment 4 of patent documentation 1, obtain above-mentioned active noble metals and support water-soluble
The double fuel oxidation catalyst that mass ratio is 1:0.20 of Pd and Pt contained in liquid.
That is, using Palladous nitrate. and chlorination platinic acid, having made Pd is 34.0mg and Pt is 6.8mg's
The aqueous solution 25g of catalytically-active metals.The mass ratio of Pd and Pt is 1:0.20.Afterwards, with enforcement
Example 1 is similarly implemented, and obtains the double fuel oxidation catalyst of comparative example 1.The expensive gold of activity the most now
Belonging to for supporting dose rate, it is 85 mass % that Pd supports dose rate, and it is 98 mass % that Pt supports dose rate.
＜ comparative example 2 ＞
Implement in the same manner as the embodiment 3 of patent documentation 1, obtain above-mentioned active noble metals and support water-soluble
The double fuel oxidation catalyst that mass ratio is 1:0.46 of Pd and Pt contained in liquid.
Make catalyst carrier i.e., similarly to Example 1, then, use Palladous nitrate. and platinum chloride
Acid, has made the aqueous solution 25g of the catalytically-active metals that Pd is 14.8mg and Pt is 6.8mg.This
Time, the mass ratio of Pd and Pt is 1:0.46.Afterwards, implement similarly to Example 1, compared
The double fuel oxidation catalyst of relatively example 2.For active noble metals with regard to now supports dose rate, Pd supports
Dose rate is 92 mass %, and it is 98 mass % that Pt supports dose rate.
＜ comparative example 3 ＞
It is set to 1 except above-mentioned active noble metals being supported contained, the mass ratio of Pd and Pt in aqueous solution:
Beyond 0.93, implement similarly to Example 1, obtain the double fuel oxidation catalyst of the present invention.
Make catalyst carrier and palladium chloride aqueous solution and dinitroso two i.e., similarly to Example 1
Ammonia platinum aqueous solution.Afterwards, add in ion exchange water 25g above-mentioned palladium chloride aqueous solution 0.073mL,
With dinitroso diammonia platinum aqueous solution 0.08g, make active noble metals and support aqueous solution.This activity is expensive
The mass ratio of Pt, Pd and Pt that metal supports Pd, the 6.8mg in aqueous solution containing 7.3mg is 1:
0.93.Afterwards, implement similarly to Example 1, obtain the double fuel oxidation catalyst of comparative example 3.
For active noble metals with regard to now supports dose rate, it is 100 mass % that Pd supports dose rate, Pt loading
Rate is 100 mass %.
＜ comparative example 4 ＞
Implement similarly to Example 1, obtain above-mentioned active noble metals and support Pd contained in aqueous solution
The double fuel oxidation catalyst that mass ratio is 1:0.47 with Pt.
Make catalyst carrier i.e., similarly to Example 1, afterwards, in ion exchange water 25g
Add above-mentioned palladium chloride aqueous solution 0.146mL, dinitroso diammonia platinum aqueous solution 0.08g, make and urge
Change active metal and support aqueous solution.Above-mentioned active noble metals support in aqueous solution containing 14.6mg Pd,
The mass ratio of Pt, Pd and the Pt of 6.8mg is 1:0.47.Afterwards, implement similarly to Example 1,
Obtain the double fuel oxidation catalyst of comparative example 4.For active noble metals with regard to now supports dose rate,
It is 97 mass % that Pd supports dose rate, and it is 99 mass % that Pt supports dose rate.
By these embodiments 1～7 and the double fuel oxidation catalyst of comparative example 1～4 be summarized in table 1.
[table 1]
Characteristic ＞ of ＜ double fuel oxidation catalyst
＜ purifying property test ＞
For the test gas made with the mixing condition shown in table 2, with the space velocity shown in table 2
The condition evaluating purifying property of above-mentioned double fuel oxidation catalyst bodies.Relative to now, catalyst
Burner exhaust stream move the concentration of upstream side in direction, by online FT-IR assay downstream
Concentration, try to achieve by NO to NO2Conversion ratio and methane, ethane, propane, carbon monoxide
Cut rate.Table 3～table 7 represent its result.
[table 2]
＜ test gas and experimental condition ＞
[table 3]
＜ by NO to NO2Conversion ratio ＞
| 200℃ | 250℃ | 300℃ | |
| Embodiment 1 | 20% | 35% | 28% |
| Embodiment 2 | 26% | 46% | 37% |
| Embodiment 3 | 32% | 55% | 43% |
| Embodiment 4 | 37% | 60% | 48% |
| Embodiment 5 | 20% | 35% | 27% |
| Embodiment 6 | 21% | 37% | 29% |
| Embodiment 7 | 23% | 40% | 33% |
| Comparative example 1 | 5% | 8% | 3% |
| Comparative example 2 | 10% | 17% | 9% |
| Comparative example 3 | 30% | 60% | 44% |
| Comparative example 4 | 10% | 18% | 10% |
[table 4]
＜ methane cut rate ＞
| 380℃ | 400℃ | 420℃ | |
| Embodiment 1 | 90% | 98% | 100% |
| Embodiment 2 | 80% | 98% | 100% |
| Embodiment 3 | 93% | 99% | 100% |
| Embodiment 4 | 97% | 100% | 100% |
| Embodiment 5 | 90% | 97% | 100% |
| Embodiment 6 | 92% | 99% | 100% |
| Embodiment 7 | 87% | 98% | 100% |
| Comparative example 1 | 97% | 98% | 100% |
| Comparative example 2 | 92% | 98% | 100% |
| Comparative example 3 | 14% | 18% | 28% |
| Comparative example 4 | 91% | 98% | 100% |
[table 5]
Cut rate ＞ of ＜ ethane
| 380℃ | 400℃ | 420℃ | |
| Embodiment 1 | 94% | 99% | 100% |
| Embodiment 2 | 83% | 99% | 100% |
| Embodiment 3 | 97% | 99% | 100% |
| Embodiment 4 | 99% | 100% | 100% |
| Embodiment 5 | 94% | 98% | 100% |
| Embodiment 6 | 95% | 99% | 100% |
| Embodiment 7 | 90% | 99% | 100% |
| Comparative example 1 | 99% | 99% | 100% |
| Comparative example 2 | 96% | 99% | 100% |
| Comparative example 3 | 43% | 51% | 60% |
| Comparative example 4 | 95% | 99% | 100% |
[table 6]
Cut rate ＞ of ＜ propane
| 380℃ | 400℃ | 420℃ | |
| Embodiment 1 | 100% | 100% | 100% |
| Embodiment 2 | 100% | 100% | 100% |
| Embodiment 3 | 100% | 100% | 100% |
| Embodiment 4 | 100% | 100% | 100% |
| Embodiment 5 | 100% | 100% | 100% |
| Embodiment 6 | 100% | 100% | 100% |
| Embodiment 7 | 100% | 100% | 100% |
| Comparative example 1 | 100% | 100% | 100% |
| Comparative example 2 | 100% | 100% | 100% |
| Comparative example 3 | 66% | 73% | 81% |
| Comparative example 4 | 100% | 100% | 100% |
[table 7]
Cut rate ＞ of ＜ carbon monoxide
| 200℃ | 250℃ | 300℃ | |
| Embodiment 1 | 98% | 100% | 100% |
| Embodiment 2 | 97% | 100% | 100% |
| Embodiment 3 | 98% | 100% | 100% |
| Embodiment 4 | 98% | 100% | 100% |
| Embodiment 5 | 97% | 100% | 100% |
| Embodiment 6 | 98% | 100% | 100% |
| Embodiment 7 | 98% | 100% | 100% |
| Comparative example 1 | 100% | 100% | 100% |
| Comparative example 2 | 99% | 100% | 100% |
| Comparative example 3 | 95% | 100% | 100% |
| Comparative example 4 | 99% | 100% | 100% |
Distinguishing according to these tables 3～7, the double fuel oxidation catalyst of embodiment 1～7 is contemplated
Run at a low speed in city and only with the catalyst inlet temperature in the case of diesel fuel be 200 DEG C with
In the usage range of upper less than 300 DEG C, by NO to NO2Conversion ratio be 20%～60%, meet make
For DPF or the function of SCR catalyst.Particularly, the double fuel oxygen of embodiment 3 and embodiment 4
Change the NO that catalyst brings2Conversion ratio is up to more than 50%, by comparison, and comparative example 1, comparative example
2 and the double fuel oxidation catalyst of comparative example 4 bring by NO to NO2Conversion ratio be
2%～18%, its activity can not be said to be abundant.
On the other hand, the double fuel oxidation catalyst of embodiment 1 and embodiment 2 is in contemplated high speed
When travelling (high load capacity), in diesel fuel be mixed with volume ratio 30%～60% the feelings of natural gas
Under condition, when catalyst inlet temperature is 380 DEG C, can be by hard-decomposed methane abatement more than 80%.
By comparison, the double fuel oxidation catalyst of comparative example 3 when catalyst inlet temperature is 380 DEG C,
For the rate of cutting extremely low 14% methane purifying rate.
It addition, by the double fuel oxidation catalysis of embodiment 2 that the mass ratio of Pd and Pt is 1:0.85
When the double fuel oxidation catalyst of agent and embodiment 2 that mass ratio is 1:0.75 compares, the latter
Cutting excellence in terms of rate by what methane cut rate and ethane, its performance and mass ratio are other of 1:0.58
The double fuel oxidation catalyst of embodiment is identical level.
The catalyst inlet temperature of diesel fuel when travelling in city be more than 200 DEG C 300 DEG C with
Under scope in, the double fuel oxidation catalyst of the present invention makes NO to NO2Conversion ratio high, help
In use the SCR mechanism of DPF or SCR catalyst to bituminous coal particulate material and the purification of NOx,
And the method passing through the present invention of mixed gas in diesel fuel when running at high speed (high load capacity),
Can be with the hard-decomposed methane of high purification.
Claims (10)
1. a double fuel oxidation catalyst, for process using diesel fuel and gas fuel as
The waste gas of the internal combustion engine that fuel uses, it is characterised in that
Have concurrently and a contained nitric oxide production part in the burning waste gas of diesel fuel is converted into dioxy
The function changing nitrogen and the function that methane oxidation contained in described waste gas is decomposed,
The inlet temperature flowing to double fuel oxidation catalyst at described burning waste gas is more than 200 DEG C
When less than 300 DEG C, described nitric oxide is less than more than 20% 60% to the conversion ratio of nitrogen dioxide,
And when described inlet temperature is 380 DEG C, more than 80% oxidized decomposition of the methane in described waste gas.
Double fuel oxidation catalyst the most according to claim 1, it is characterised in that
There is the catalyst carrier comprising metal-oxide and be made up of palladium and platinum and supported in described
The catalytically-active metals of catalyst carrier,
About palladium and the mass ratio of platinum of described catalytically-active metals, when setting palladium as 1, platinum is more than 0.5
And less than 0.9.
Double fuel oxidation catalyst the most according to claim 1 and 2, it is characterised in that
About described mass ratio, when setting palladium as 1, platinum is less than more than 0.55 0.88.
4., according to the double fuel oxidation catalyst according to any one of claims 1 to 3, its feature exists
In,
Described double fuel oxidation catalyst is possibly together with the iridium as the second active catalytic metals.
5., according to the double fuel oxidation catalyst according to any one of Claims 1 to 4, its feature exists
In,
Described catalyst carrier is the catalyst carrier being made up of and containing lanthana gama-alumina.
6. a double fuel SCR waste gas treatment mechanism, to using diesel fuel and gas fuel as
The internal combustion engine that double fuel uses, particle-like substance containing nitric oxide, methane and coal smoke type combustion
Burn waste gas and carry out purified treatment, it is characterised in that
The upstream side moving direction from described burner exhaust stream possesses successively towards downstream:
Double fuel oxidation catalyst according to any one of Claims 1 to 5；
At least some of burning of the particle-like substance of described coal smoke type is made in the presence of nitrogen dioxide
And the black smoke that is removed remove filter and/or, the confession of reducing agent that is made up of carbamide and/or ammonia
To source and selective contact reducing catalyst.
7. a double-fuel diesel internal combustion engine, it is characterised in that there is on exhaustor claim 6
Described SCR waste gas treatment mechanism.
8. a control method for double-fuel diesel internal combustion engine, controls the double combustions described in claim 6
Material diesel engine, it is characterised in that
The inlet temperature flowing to described double fuel oxidation catalyst at burning waste gas is more than 380 DEG C
Time, described natural gas is sucked from air inlet pipe the combustor of Diesel engine.
9. a control method for double-fuel diesel internal combustion engine, controls the double combustions described in claim 6
Material diesel engine, it is characterised in that
Calculate with volume ratio, make to be inhaled into from air inlet pipe the confession of the natural gas of the combustor of Diesel engine
Giving amount is less than more than 30% 75% relative to the quantity delivered of described diesel fuel.
10. a control method for double-fuel diesel internal combustion engine, controls the double combustions described in claim 6
Material diesel engine, it is characterised in that
The inlet temperature flowing to described double fuel oxidation catalyst at burning waste gas is more than 380 DEG C
Time, described natural gas is sucked from air inlet pipe the combustor of Diesel engine, and,
Calculate with volume ratio, make the air inlet pipe from Diesel engine be inhaled into the combustor of Diesel engine
The quantity delivered of natural gas be less than more than 30% 75% relative to the quantity delivered of described diesel fuel.
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| CN108714370A (en) * | 2018-08-24 | 2018-10-30 | 重庆康明斯发动机有限公司 | A kind of exhaust treatment system |
| CN108714360A (en) * | 2018-08-24 | 2018-10-30 | 重庆康明斯发动机有限公司 | A kind of exhaust treatment system |
| CN109653853A (en) * | 2019-01-28 | 2019-04-19 | 江苏大学 | Diesel engine vent gas joint processing system and control method |
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| JP6501115B2 (en) | 2019-04-17 |
| JP2016215091A (en) | 2016-12-22 |
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