CN102441327A - Operating methods for selective catalytic reduction of NOx - Google Patents

Operating methods for selective catalytic reduction of NOx Download PDF

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Publication number
CN102441327A
CN102441327A CN2011102966268A CN201110296626A CN102441327A CN 102441327 A CN102441327 A CN 102441327A CN 2011102966268 A CN2011102966268 A CN 2011102966268A CN 201110296626 A CN201110296626 A CN 201110296626A CN 102441327 A CN102441327 A CN 102441327A
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reducing agent
flow
agent material
catalyst
air
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CN2011102966268A
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CN102441327B (en
Inventor
T.M.斯隆
K.L.佩里
D.L.希尔登
N.D.布林克曼
J.H.李
M.B.维奥拉
S.J.施米格
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GM Global Technology Operations LLC
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GM Global Technology Operations LLC
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N9/00—Electrical control of exhaust gas treating apparatus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • F01N3/208—Control of selective catalytic reduction [SCR], e.g. dosing of reducing agent
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/03—Adding substances to exhaust gases the substance being hydrocarbons, e.g. engine fuel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/06—Adding substances to exhaust gases the substance being in the gaseous form
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2900/00—Details of electrical control or of the monitoring of the exhaust gas treating apparatus
    • F01N2900/06—Parameters used for exhaust control or diagnosing
    • F01N2900/18—Parameters used for exhaust control or diagnosing said parameters being related to the system for adding a substance into the exhaust
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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
    • 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
    • Y02T10/40—Engine management systems

Abstract

Where oxygenated hydrocarbons, such as ethanol, may be considered for use as a reductant to be added to diesel or gasoline engine exhaust for promoting the catalyzed reduction of NOx to N2, there is a need to continually adjust the amount of the reductant to be added as engine and catalyst operating conditions change. It is found that useful methods, to be practiced using a suitably programmed on-vehicle computer, can be based on a correlation for ethanol, or other specific reductant, with continually measured values of catalyst temperature, the oxygen and NOx contents of the exhaust, and the volumetric flow rate of the exhaust over a reduction catalyst, such as silver supported on alumina, selected for reduction of NOx to nitrogen. Effective amounts of the reductant for substantial reduction of NOx may be reliably determined using at least such parameters.

Description

The method of operating that is used for the SCR of nitrogen oxide
Technical field
The present invention relates to be used for managing nitrogen oxide and (most ofly be NO and NO from the discharge air-flow of Diesel engine or other lean-combustion engine 2, be generically and collectively referred to as NO X) the method for SCR.More specifically, the present invention relates to control and add the ethanol of suitable oxidizing hydrocarbons-for example in the discharge gas of preparation method, will discharge the NO in the air-flow with base metal, when selective reduction catalyst contacts thereby discharge gas flow with box lunch XReduce.
Background technology
Diesel engine, some gasoline engines and many HC fuel power-equipments turn round so that the fuel economy that is improved under the situation that is higher than stoichiometric air-fuel mass ratio.Yet this lean-combustion engine and other power sources produce oxygen, water and the nitrogen oxide (NO with relative high level X) hot type venting.With regard to Diesel engine, usually in about 200 ℃ to 400 ℃ scope, this temperature depends on the current ratio of the fuel consumption (load) of engine from the temperature of the discharge air-flow of the engine of preheating.Discharge representative, the exemplary composition of gas, by volume be approximately oxygen 10%, carbon dioxide 6%, carbon monoxide (CO) 0.1%, hydro carbons (HC) 180ppm, NO x235ppm, remainder are the nitrogen G&W basically.Discharge gas and often contain some very little rich carbon granules.And contain the situation of sulphur with regard to HC fuel, also possibly contain sulfur dioxide from the discharge gas of Combustion Source.Expectation handle the composition of this discharge gas so that denitrogenate, material that any outside carbon dioxide and the water is discharged into atmosphere is minimized.
NO XGas generally includes and has a small amount of nitrous oxide (N 2O) nitrogen oxide (NO) and nitrogen dioxide (NO 2) different mixtures, this NO XGas is difficult to be reduced to nitrogen (N 2), this is because hot type goes out air-flow high relatively oxygen (O is arranged 2) content (and water content).TWC Three Way Catalyst System successfully is used in the engine with about stoichiometric air-fuel ratio running, yet does not discharge in the gas NO at this oxygen enrichment effectively XBe reduced to acceptable level.
Thin NO XTrap can be removed NO effectively from discharge air-flow X, but said trap needs expensive noble metal and their long-term durability uncertain.People have considered selective catalytic reduction method, thus wherein lean-burn discharge gas oxidized accomplish unburned hydro carbons to the oxidation of carbon dioxide and water, carbon monoxide to the oxidation of carbon dioxide and some nitrogen oxide (NO) to nitrogen dioxide (NO 2) oxidation.With the NH of reducing agent material-for example 3Or NH 3Precursor (aqueous solution of urea) is ejected into the discharge air-flow of oxidation, and said discharge air-flow passes suitable catalyst with a large amount of NO XBe reduced to the nitrogen G&W.This practice is called as NO X" SCR " (SCR) because under not influencing the situation of discharging other oxides in the air-flow, realized this step.But urea SCR and ammonia SCR must be the additional reducing agent materials of storing on the car, and when during as reducing agent, avoiding the aqueous solution of urea when arctic weather, to freeze with urea.
Use has more cheaply, method realizes the NO from the discharge air-flow of lean-combustion engine more easily XReduction will be useful.
Summary of the invention
The invention provides a kind of method of using and adding that is used for managing methyl alcohol, propyl alcohol, butanols or the aldehyde of ethanol or other suitable these type of alcohol of low-molecular-weight oxidizing hydrocarbons (OHC)-for example, the hydro carbons (OHC) of ethanol or said other suitable low-molecular-weight oxidations is as the oxidizing hydrocarbons reducing agent in the OHC-SCR process and be used as and contain oxygen and moisture lean-burn is discharged the NO in the gas XCatalytic reduction reactor.According to some condition and characteristic of discharging air-flow and the following characteristic of the reducing catalyst of sign in this manual, continue to monitor and regulate the amount of adding the oxidizing hydrocarbons of discharging air-flow to.The target that sustainable management OHC adds is the demand of avoiding the discharge gas of the ammonia that is used for the OHC-SCR reactor downstream with post processing.The further target of a large amount of use oxidizing hydrocarbons is that the total fuel consumption of vehicle motor and gas extraction system thereof is minimized.
The existing vehicle motor of great majority uses the power source of the burning of HC fuel and air as them.Said engine comprises a plurality of cylinders, and each cylinder all has the powertrain system that is connected to the propelling that is used for vehicle and the reciprocating piston of bent axle.The present invention provides in order to air and fuel computer control ground, sequentially, periodically be presented to the method for each cylinder.Along with piston moves back and forth in their corresponding cylinder, controlled air-and-fuel mixture sequentially gets into corresponding cylinder, and wherein combustible mixture is compressed and lights.Combustion driven piston in power stroke in each cylinder then is that exhaust stroke-combustion by-products is drained into the exhaust manifold from cylinder in this exhaust stroke, is drained into then in the discharge gas conduit of vehicle.Produce stable discharge air-flow in composition in the background technology part of this specification shown in the continuous running in the above of this lean-combustion engine and the temperature range.For example, said fuel can be the mixture or the similar fuel of diesel oil, gasoline, natural gas, liquefied petroleum gas (major part is a propane), dimethyl ether, ethanol, ethanol and gasoline.Hydrogen also can be used as fuel.
Contain oxygen and moisture discharge gas and at first can be directed to oxidation conversion device that air-flow passes, that contain catalyst, to be used for the oxidation of carbon monoxide and imperfect combustion HC fuel component.Said oxidation conversion device also can promote the oxidation of some nitrogen oxide to nitrogen dioxide to prepare to discharge air-flow; Make this discharge air-flow in scr reactor, carry out downstream, the gas extraction system that this scr reactor is used for leaving vehicle at the discharge air-flow is before with NO 2With other NO XComponent is reduced to nitrogen.According to the present invention, oxidizing hydrocarbons is added into the discharge air-flow in the appropriate location at the scr reactor upper reaches.The example that is used for suitable oxidizing hydrocarbons SCR (OHC-SCR) catalyst of practice of the present invention is the granular materials of the silver (or silver oxide) that comprises nano-scale, and this material is deposited and is supported on the alumina particle of micron-scale.For example, supported silver catalyst particle can suitably be deposited as the shallow layer on the wall of the passage aisle that a plurality of air-flows that extrude, the ceramic honeycomb material all in one piece pass.
According to the embodiment of the present invention, ethanol (or other suitable oxidizing hydrocarbons) is sprayed into the discharge gas at (or otherwise inserting) OHC-SCR catalyst upper reaches.In order more effectively to influence NO with tight contact of OHC-SCR catalyst along with discharging air-flow XThe reduction of component; Confirm at this as the inventor; Continue to monitor the OHC-SCR catalyst with discharge gas some continue parameter of changing, and based on the parameter value of confirming continue to regulate add the oxidizing hydrocarbons of discharging air-flow to amount so that make it consistent with predetermined policy.
Further according to the method for the invention the diagram of example, below the interpolation that continued to obtain and be used to manage oxidizing hydrocarbons with the in good time time interval of every kind measured value or determined value in four kinds of (at least) parameters: (ⅰ) temperature of OHC-SCR catalyst, NO in the discharge gas at the OHC-SCR catalyst upper reaches just in time XThe typical value (ⅲ) of amount of typical value (ⅱ) and oxygen of amount, and (ⅳ) through or pass the measured value of the discharge gas flow speed of catalyst.Just discharge flow rate of gas, can measure or definite measured value-gas hourly space velocity (SV, h for example -1) or equivalence value.For example, when confirming the space velocity of particular moment, use the current unit volume of gas and the ratio of the fixed volume of the OHC-SCR catalyst of being scheduled to of per hour discharging under the standard conditions of temperature and pressure.In practice of the present invention, obtain the typical value of the accurate and reliable oxygen content in the discharge gas at the OHC-SCR catalyst upper reaches confirm it is important at every turn for what add to the OHC that discharges gas.
Be used to measure the Current Temperatures of selective reduction catalyst and be used for confirming that the proper sensors of the useful value of discharge gas flow speed is available.Similarly, be used for providing constantly or the definite oxygen percentage of total discharge gas (for example, with) and NO XThe sensor of the useful instantaneous concentration of (for example, to discharge a few millionths of gas componant) also is available.By pre-programmed suitably, computer based control system can be used for receiving these type of data from corresponding sensor; And can be used for using this type of data available so that continue and analyze these parameters apace, these parameters are used for confirming to add the amount of discharging the oxidizing hydrocarbons reducing agent in the air-flow in each running of vehicle motor.This based on sensor and system for computer can be used as engine control system part work or with said engine control system cooperation, said engine control system is used for-for example measures, confirms and is controlled to the air of engine and interpolation and other engine runnings of fuel.
According to preferred implementation of the present invention; And through illustrative example; The control system of suitable interpolation OHC-SCR reducing agent can consider the currency of the discharge gas/OHC-SCR parameter of top appointment, and confirms to add to the amount (quality or volume) of the reducing agent of discharging air-flow.For example, said control system can be programmed to every mole of NO XComponent is added the reducing agent (like ethanol) of 1 mole of numerical value, confirms or estimate to discharge every mole of NO in the gas based on the combination of the currency of said four parameters then XComponent.As will be in greater detail in the following specification, be expected at the reducing agent that the concrete OHC-SCR system that is used for specific engines and vehicle uses for any (or each), but the form of predefined parameter combination and corresponding reducing agent interpolation value.Can said form stores be used for managing ongoing memory to the vehicle computer control system that the reducing agent of discharging air-flow adds.Will be appreciated that the same engine in the different vehicle can use different reducing agents, different mechanism or device in order to add reducing agent to discharging air-flow and the parameter combinations different forms with corresponding reducing agent interpolation value.The main target that management OHC adds is to realize NO XEfficient reduction to nitrogen makes the formation of the ammonia in the reduction reactor minimize simultaneously, and the reducing agent interpolation is minimized the influence of total fuel economy of engine vehicle system.
In other embodiments of the present invention, the currency of four parameters can be used in the vehicle computer system so that be used for calculating current reduction dosage based on the data or the making of calculation procedure of storing.
Oxidizing hydrocarbons reducing agent material will be carried in the suitable holder on the vehicle, and be transferred so that add engine to or discharge air-flow through suitable conduit.Preferably, the reducing agent material is an ethanol, and ethanol certainly is the fuel or the fuel element of vehicle.For example, when fuel be that the mixture of ethanol and diesel fuel or the mixture of ethanol and gasoline-for example oxidizing hydrocarbons/hydrocarbon mixture can be used as additional OHC-SCR reduction additive.
Through to the consulting of the detailed description of the specific embodiment of practice of the present invention, it is clear that other purposes and advantage will become, and practice of the present invention below will provide (as nonrestrictive explanation) in this manual.
Description of drawings
Fig. 1 is the sketch map that flows from the exhaust manifold of Diesel engine (or other lean-combustion engines or power-equipment) the discharge air-flow through discharging the gas conduit system, and said discharge gas conduit system comprises oxidation catalysis reactor and OHC-SCR catalytic reactor.The explanation of sensing station and reducing agent point of addition is also shown in this figure.
Fig. 2 is the sketch map of OHC-SCR reactor.In this embodiment, the particle of silver-aluminium oxide catalyst is applied to the circulation passage of the cellular body of cordierite material all in one piece as coating material.The material all in one piece that contains this silver-aluminium oxide catalyst is had the proper metal housings close of the entrance and exit of discharging air-flow.
Embodiment
It is a kind of with ethanol and the operation strategy of other suitable oxidizing hydrocarbons as the OHC-SCR reducing agent in the discharge gas of lean-combustion engine that the present invention provides.Under the situation of using silver-aluminium oxide catalyst, ethanol is to NO XBe suitable and preferred reducing agent, in the diesel oil of broad and petrol engine operating condition scope, produce the NO of 70%-99% XTransformation efficiency.Oxidizing hydrocarbons and NO XPlacing the reaction formation of catalyst place nitrogen, carbon dioxide and water with oxygen.NO thus XTherefore be converted into the suitable major part of reducing agent and discharge the material that the environment of discharging gas is allowed.
More specifically, in heavily loaded federal test program (Heavy-Duty Federal Test Procedure schedule) step, realized 81% average N O XTransformation efficiency, said heavily loaded federal test program spray under the situation of discharging air-flow at ethanol and on 6.6 liters of Diesel engines, move.Ethanol is a kind of reducing agent of OHC-SCR especially efficiently, allows NO XThe catalytic temperature of reduction can be low to moderate 250 ℃.The partial oxidation products of ethanol-for example acetaldehyde, and other alcohol also is OHC-SCR reducing agent on an equal basis efficiently.Through the combination of experiment and mathematical modeling, developed operation strategy and during engine running, used ethanol from discharge gas, to remove NO efficiently as the OHC-SCR reducing agent XOnly need the operation strategy that disclosed reducing agent in this specification adds is done change slightly, be applicable to that other oxidizing hydrocarbons (or mixture of oxidizing hydrocarbons and hydro carbons) of OHC-SCR also can be used.
The practice of the method that the control reducing agent adds can be better understood after the running to Diesel engine (or other lean-combustion engines) and its discharge gas system describes, and said discharge gas system is included in to discharge in the gas path and is used for NO XThe reactor that contains catalyst of the reduction of component.
Fig. 1 is the NO that is used to discharge gas XExemplary diesel engine that the OHC-SCR of content handles and the schematic functional block diagram of discharging gas system.
Consult Fig. 1 at present, the schematic functional block diagram of exemplary engine discharge gas system 10 has been shown among the figure.For example, engine 12 can be the engine of gasolene type internal combustion engine, diesel-type explosive motor, hybrid power engine and/or other suitable types.Engine 12 produces moment of torsion through the cylinder 14 internal combustion air/fuel mixtures at engine 12.Engine 12 can comprise the cylinder 14 of the cylinder of any right quantity-for example.For example, engine 12 can comprise 2,3,4,5,6,8,10 or 12 cylinders.
Through inlet manifold 13, air is sucked each cylinder 14 of engine 12 by order.By electronic throttle controller (ETC) 13 ' ' 'The air throttle 13 that activates 〃The air that control gets into each cylinder 14 of engine 12 flows.Air with from the fuel mix of one or more fuel injectors 15 to form the mixture of air and fuel; With regard to the sky combustion mass ratio that Diesel engine and this mixture of other lean-combustion engines have the stoichiometric proportion that significantly is higher than fuel, this sky combustion mass ratio of diesel fuel and gasoline is approximately 14.7.Thereby the air/fuel mixture in each cylinder 14 is lighted by order and is burnt to produce the moment of torsion propelled vehicles.And the burning of air/fuel mixture produces discharges gas, and said discharge gas enters the exhaust manifold 17 from each cylinder 14.Discharge the lasting stream of air-flow conduct and during engine running, flow out, and flow into discharge gas system 16 from exhaust manifold 17.
Discharge gas system 16 and comprise processing catalyst, sensor, computer control module etc., said parts cooperatively interact and discharge nitrogen oxide (NO in the gas to reduce X) amount.Discharge gas system 16 and generally include oxidation catalyst 20, reducing agent injection of material device 22 and OHC-SCR catalyst 24.Said OHC-SCR catalyst 24 is carried in the OHC-SCR reaction vessel usually, and the example of said OHC-SCR reactor is shown in Fig. 2.In Fig. 1, cross first from the discharge air communication of exhaust manifold 17 and discharge gas conduit part 21 arrival oxidation catalysts 20.Oxidized discharge air communication is crossed second and is discharged gas conduit part 23 arrival OHC-SCR catalyst 24, then through the 3rd duct portion 25.Discharging gas can flow out from discharging gas system through the 3rd duct portion 25.Discharge gas system 16 and can comprise that also other install-for example are used for removing the filter or the trap (not shown) of carbonaceous particles material from discharging air-flow.
In this example, reducing agent injection of material device 22 with oxidizing hydrocarbons reducing agent material (for example, ethanol) spray into second discharge gas conduit part 23, OHC-SCR catalyst 24 the upper reaches.OHC-SCR catalyst 24 can absorb ethanol or other oxidizing hydrocarbons reducing agents, and promotes the NO in reducing agent and the discharge air-flow that flows XThe reduction reaction of component and oxygen is with NO XComponent is reduced to nitrogen.OHC-SCR catalyst 24 preferably is supported on the catalyst of the silver particles on the alumina particle.OHC-SCR catalyst 24 can use with the diesel particulate filter combination or use with any other suitable tectonic association.
Pass through NO XReact the NO that from discharge gas, removes with the oxidizing hydrocarbons reducing agent XPercentage be called as transformation efficiency or NO XConversion ratio.According to the present invention, NO XHow much being closely related of the reducing agent of conversion ratio and the discharge air-flow that continues to confirm to add to OHC-SCR catalyst 24 upper reaches.
One group of sensor that can be considered as the parts of discharging gas system 16 has been used in the practice that is used herein to the reduction dosage of confirming to add to OHC-SCR catalyst 24.Discharge gas system 16 and can comprise NO XSensor 28 and 30 and temperature sensor (often being thermocouple) 32,34 and 36.Discharge gas system 16 and also comprise lambda sensor 38, this lambda sensor 38 also plays an important role in practice of the present invention.A NO XSensor 28 is positioned at the upper reaches of oxidation catalyst 20, and another NO XSensor 30 is positioned the downstream of OHC-SCR catalyst 24.In other embodiments, NO XSensor 28 is positioned between oxidation catalyst 20 and the OHC-SCR catalyst 24.Temperature sensor also can be positioned on the inboard of OHC-SCR catalyst 24 or near.In some practice of the present invention, the 3rd duct portion 25, OHC-SCR catalyst 24 other components of downstream sensing-for example the existence of ammonia also possibly be useful.
NO XSensor occurs with different forms with lambda sensor, and form that can be different is used.They often are electrochemical devices, and this electrochemical device will be discharged air-flow and air or other with reference to material relatively.Their signal is received by engine control module or other computer based modules and uses.And can be through using from NO with the control module of other sensor signals-for example quality air flow sensor combination XThe signal of sensor or lambda sensor is to obtain the current NO that discharges in the air-flow XThe useful value of concentration or oxygen concentration.
NO thus X Sensor 28 and 30 is respectively applied for the NO of the upstream and downstream that obtains OHC-SCR catalyst 24 XThe measured value of concentration.In other words, NO XSensor 28 and 30 is used to obtain the NO that flows into and flow out OHC-SCR catalyst 24 XMeasured value or numerical value.Said NO XSensor 28 and 30 produces corresponding to the NO of correspondence position at them XThe signal of the numerical value of concentration (ppm), said signal is called NOX respectively InAnd NOX Out
Temperature sensor 32,34 and 36 is positioned to spread all over all places of discharging gas system 16.For example, as shown in Figure 1, temperature sensor 34 is positioned the downstream of oxidation catalyst 20 and the upper reaches of OHC-SCR catalyst 24, and temperature sensor 36 is positioned the downstream of OHC-SCR catalyst 24.Temperature sensor 32 is positioned the upper reaches of oxidation catalyst 20.In the temperature sensor 32,34 and 36 each all measured the temperature at the discharge gas of their corresponding positions, and exports one corresponding to the signal of measuring temperature.Said signal is exported through temperature sensor 32,34 and 36, and in Fig. 1, is called T respectively A, T BAnd T C
The moment of torsion output of engine control module (ECM) 40 control engines 12.In this function; ECM40 can receive the signal from one or more sensors, the sensor that said sensor comprises MAPS (MAP), quality air flow sensor (MAF), TPS (TPS), intake air temperature sensor (IAS) and is used for other engine running parameters of engine running control.In practice of the present invention, ECM40 comprises that also reducing agent adds control module 42, and said reducing agent adds the mass flowrate of control module 42 controls by the oxidizing hydrocarbons reducing agent of reducing agent injection of material device 22 injections.By this way, reducing agent adds the amount that control module 42 controls are conducted to the reducing agent material of OHC-SCR catalyst 24.It is principle pre-programmed according to the present invention computer components with the interpolation of management reducing agent material that reducing agent adds control module 42, and said reducing agent material is used for the NO with the OHC-SCR catalyst 24 mobile discharge air-flows that contact XThe reduction of component.For example, the reducing agent material can be stored in fuel tank or other the suitable holders, and is delivered to reducing agent injection of material device 22 through the conduit (not shown).
As schematically illustrated in Fig. 1, reducing agent adds control module 42 and receives from temperature sensor, one or more NO XThe signal of component sensor and at least one lambda sensor.Except temperature sensor and discharge gas composition sensors; Also be provided with and detect the sensor of discharging the gaseous mass flow rate at the upper reaches of OHC-SCR catalyst 24; Said sensor is used for discharging continue confirming of gas volume flow rate through module 42, thus the calculating of the space velocity (or similarly discharging gas volume) of the discharge gas that is used for contacting with OHC-SCR catalyst 24.For example, In some embodiments of the present invention, reducing agent adds control module and can use the data that quality air flows and fuel flows that get into engine to confirm or to estimate current discharge specific gas flow rate.
In Fig. 1, reducing agent is sent to the discharge air-flow through reducing agent is realized to discharging air-flow in OHC-SCR catalyst injected upstream.The additive method that reducing agent transmits comprises: the cylinder that 2) sprays into igniting in the later stage of expansion stroke; 3) deactivated cylinder that is ejected into not igniting and does not add combustion fuel; 4) before closing the intake & exhaust valves cylinder deactivation, being ejected in the cylinder, then in follow-up circulation, open air bleeding valve, discharge gas system so that allow any product of reducing agent and reducing agent to get into.In practice, oxidizing hydrocarbons adds through vehicle motor, thereby preferably can reduce or exempt the use of discharging oxidation reactor in the air-flow.
Continue to confirm to add to discharge air-flow in description for use in NO XThe method of reducing agent of suitable quality of effective reduction before, explanation earlier is used to contain NO XAnd contain reducing agent discharge gas pass and said gas is helpful with the example of effective reactor that contacts (or container) of OHC-SCR reducing catalyst 24 in being placed on catalytic reactor.Fig. 2 shows OHC-SCR reactor 60.
Consult Fig. 2; OHC-SCR reactor 60 can comprise stainless pipe body 62; Said stainless pipe body 62 is used for tight seal-that for example extrude, columned, favose cordierite catalyst support 64, and said supporter 64 is visible in the section window of pipe body 62 sides.Supporter 64 can be formed by other known suitable pottery or metal materials.In this embodiment, cordierite supporter 64 is formed by a plurality of discharge gas communication passages that the discharge gas access face 65 from the upper reaches-catalyst support extends to the discharge gas vent face (invisible among Fig. 2) of downstream-catalyst support.These small circulation passages are represented as cross spider in the diagram of discharging gas access face 65.For example, during the extruding of ceramic body, form 400 circulation passages per square inch usually at inlet face.The beaded catalyst that covers silver on the aluminium oxide is on the wall of each passage that is coated in honeycomb of the form with coating.Steel body 62 is bigger than the upstream and downstream of discharging gas conduit with the diameter of the money base reducing catalyst supporter 64 of sealing, so that when the discharge air-flow occupies the inlet face 65 of catalyst support 64 and flows through the coating passage, reduce the resistance of discharging air-flow.Discharge air-flow is guided the OHC-SCR catalyst that supports on the conduit wall with supporter 64 and contacts thereby supporter 64 is sealed in the steel body 62.
As as can be seen from Figure 2, the upstream extremity of steel obturator 62 (as discharging shown in the airflow direction arrow 66) is discharged 68 sealings of gas access part by the stainless steel of expansion.Discharge gas access 70 sizes of intake section 68 are set to and are suitable for reception from the discharge air-flow of discharging gas conduit 23 (Fig. 1).Discharge gas access part 68 and be soldered to steel obturator 62.With similar method; The downstream of steel obturator 62 (discharge airflow direction arrow 72) is shunk by mobile section, steel is discharged 74 sealings of gas part, and said steel is discharged gas part 74 and had and be suitable for being soldered to the discharge gas vent 76 that downstream row goes out the gas conduit part.
Temperature sensor (not shown in Fig. 2) can be positioned in the steel obturator 62.For example, this sensor can be positioned on the upper reaches 65 and/or the downstream of catalyst support 64.
According to practice of the present invention, must obtain through covering the NO that contains of silver-colored selective reduction catalyst on the aluminium oxide XDischarge the measured value of the volume flow rate of air-flow.As shown in Figure 2, discharge air-flow and be separated at the inlet face 65 of catalyst support 64, flow through a plurality of very little passages then, and the silver catalyst of coating granule form has been applied to said passage.In this embodiment, often preferably use the volume of the volume outside, the surface of supporter 64 as catalyst.Thus, contain NO XThe discharge air-flow can be with respect to the useful measured value of space velocity coating, the multichannel supporter through confirming divided by the per hour volumetric flow rate of discharge gas with the external volume that contains the cordierite bodies of discharging gas channel.For example, volumetric flow rate can be confirmed under the standard temperature and pressure (STP) of the actual temperature of discharging gas and pressure or discharge gas.
Be used for the oxidizing hydrocarbons reducing agent is added into the operation strategy of discharging air-flow at these, an important control variables is the reductant concentration and the NO at the OHC-SCR catalyst upper reaches XThe ratio of concentration.As shown in Figure 1, sensor is used for measuring N O under given operating condition XConcentration, and with an amount of reducing agent introducing discharge gas.Reductant concentration is represented with the carbon particulate concentrations with respect to the concentration of nitrogen oxide that is included in the reducing agent, and will be designated C1 (reducing agent)/NO XRatio.Therefore, when ethanol is used as the reducing agent material, at C1/NO XIn the ratio, 1 mole of ethanol provides 2 moles of C1 reducing agents.
Be used for the random process modeling of the reducing agent interpolation of OHC-SCR
The inventor has used random process modeling (SPM) that the quantitative relation of discharging between gas parameter and the silver catalyst temperature is provided at this, contains NO so that management is added into XThe oxidizing hydrocarbons of discharge air-flow.The random process modeling is advanced experience modeling method, and it carries out interpolation operation between data point after adjusting is present in the noise of the data that are used for tectonic model.Employed SPM instrument obtains from Ricardo based on Matlab and through power engineering experimental design (DEPE) group.
In an example using this modeling, during two different known diesel engines operation cycle, based on NO takes place XThe running engine data mining random process model that transforms: heavily loaded federal test program (HDFTP) and auxiliary emission test (SET), it also is the United States Federal's test program.Confirm to be catalyst inlet temperature, catalyst inlet NO from the input data that experiment obtains X, each concentration and the gas hourly space velocity that passes catalyst in C1 hydro carbons (ethanol) and the oxygen.Output variable is NO XConversion ratio or relevant back OHC-SCR NO XConcentration.
Experimentize with 6.6 liters of turbocharging type Diesel engines.Forming the discharge gas system by the diesel oxidation catalyst in exhaust manifold downstream, then is 10 liters of Ag/Al 2O 3The OHC-SCR catalyst.When the effluent air temp at the spray site place of measuring is higher than 220 ℃, ethanol is sprayed into the discharge gas system between oxidation catalyst and the silver catalyst bed.To discharge the measured value of gaseous matter with Fast Fourier Transform (FFT) infrared spectroscopy (FTIR) photometer, and all can produce this measured value at each engine cycle period per second.
Along with engine running in two federal test circulations, the test of engine produces several thousand data points.Use 164 data points to be configured to the satisfactory model of HDFTP; This model is successfully by the random process modeling analysis of in engine control module, implementing, thereby along with Diesel engine running and the ethanol that is controlled to concrete Diesel engine adds in or the circulation that overlap similar with test loop.Yet,, selected performance variable scope at random is divided into high temperature type and low temperature type for the summary of the exemplary operation parameter in this test is provided.
Be used for illustration purpose, the value of these performance variables is divided into low scope and high scope.The low scope of these variablees is as follows:
< 300 ℃ of temperature
NO XConcentration<200ppm
O 2Concentration<11%
Space velocity<50000hr -1
The high scope of these variablees is meant the value of these upper limits that surpass low scope.This grouping causes producing 16 exemplary operating conditions, constitutes the low value of 4 performance variables and 16 various combinations of high value.Because each exemplary operating condition is represented the scope of a variate-value, so realize maximum NO XTransform required C1 (reducing agent)/NO XRatio also can be a scope.Show in 16 exemplary operating conditions each and realize maximum NO XTransform required C1 (reducing agent)/NO XThe scope of ratio.Confirmed this scope through the random process modeling of the engine data that in HDFTP and auxiliary emission test (SET), obtains.With ethanol as reducing agent, shown in form 1:
Form 1 is with the operation strategy of ethanol as the HC-OHC-SCR reducing agent
Temperature NO X Space velocity O 2 C1 (ethanol)/NO X
Low Low Low Low 2
Low Low Low High 2-40
Low Low High Low 2-3
Low Low High High 2
Low High Low Low 2-37
Low High Low High 1-2
Low High High Low 1-2
Low High High High 1-14
High Low Low Low 3-32
High Low Low High 1-40
High Low High Low 2-31
High Low High High 6-72
High High Low Low 9-12
High High Low High 7-23
High High High Low 4-26
High High High High 6-10
If engine data is enough comprehensive, then the modeling of engine data valued random all can provide the C1/NO of expectation under any desired engine operation condition XRatio.Under 3 to 5 concrete engine condition of each in satisfying height-substandard, top form is configured to use the C1/NO of expectation XThe stochastic modeling of ratio prediction (through engine data is carried out interpolation), Here it is provides the reason of scope.In the practice of reality, the quantity that is used for the concrete engine condition of particle test program will be used based on the random process model of the engine data that is used for this particle test program and confirm.
In other words, engine calibration will be used than 16 much more points of point and limit the controllable engine condition under the federal test program for example, or other engine runnings selected, expectation circulate.But in case develop random process model from about 100-200 the appropriate Engine Block Test service condition of selecting that is used for the particle test program, during test program, this model all can be used for predicting the C1/NO of expectation under any operating condition so XRatio.The quantity of the needs prediction operating condition that the particle test program is required will be based on the NO of needs XThe amount of reducing agent is confirmed, is avoided simultaneously storing a large amount of reducing agents onboard, and can not surpass acceptable effective fuel economy penalty owing to the consumption of ethanol.
Thus, for the real engine alignment purpose, will be at each confirm preferred C1 (ethanol)/NO under big and different operating conditions right quantity XRatio.Confirm preferred C1 (ethanol)/NO XThe factor that ratio will be considered except four variablees that limit operating condition, flows out the NO of OHC-SCR catalyst in addition XThe ammonia of mass flowrate, discharge gas componant that other are not supposed to-for example mass flowrate and through adding ethanol to discharging the equivalent fuel economy loss that gas causes, said discharge gas componant possibly be the accessory substance that the OHC-SCR catalyst is operated.In this embodiment, ethanol is vehicle-mounted and is stored in the container of vehicle that said container is independent of the normal fuel case, and in discharging gas system, uses as required.Also can use other devices of the reducing agent of supply needs according to following description.The engine fuel that uses can be diesel oil, gasoline, hydrogen, natural gas, LPG, dimethylether or other suitable lean-combustion engine fuel.
The random process modeling also has been applied to from the NO in the exhaust of four-cylinder gasoline fuel, lean-burn operation, spark-ignition direct-injection (SIDI) engine XOHC-SCR.The mixture of ethanol and 85% ethanol, 15% gasoline (by volume, this fuel is called E85) is as OHC reduction additive.When engine was in the warming up pattern, engine drove cycle with new Europe, in said warming up pattern, discharged gas and was in the temperature that is suitable for effective silver catalyst function.Test and data acquisition are carried out with reference to Diesel engine as described above.Obtain several thousand data points and be used for the engine running circulation.Equally; The appropriate model that is used to drive circulation with the exploitation of hundreds of data points; This hundreds of data points is by the random process modeling analysis of in engine control module, implementing, be used for when petrol engine during with or the cycle that overlap similar with test loop control ethanol to concrete petrolic interpolation.
As the reducing agent of OHC-SCR, the advantage of ethanol or other effective oxides can realize in the discharge gas of engine that said engine is designed to any fuel-alcohol mixture or any fuel-oxide mixture operation.Under one situation of back, reducing agent can use the source of the contents of fuel tank as the OHC-SCR reducing agent easily.The concentration of the effective oxide in the fuel is big more, attainable NO XThe improvement of conversion ratio is just big more.If desired, spray into discharge gas before oxide can separate with fuel so that its concentration is improved and makes the reducing agent that sprays into more effective.The available film realization of this separation, water or the extraction of other suitable chemical substance realize or use other appropriate method to realize.With as stated similarly program can be used for developing the operation strategy that is used for any engine fuel-oxide mixture.

Claims (10)

1. the method for the addition of a definite oxidizing hydrocarbons reducing agent material, said reducing agent material are used for coming the NO of the discharge gas of the vehicle that free lean-combustion engine drives XThe catalyst of component promotes reduction; Said vehicle motor comprises a plurality of combustion cylinders and the exhaust manifold that is connected to said cylinder; Fuel and air are mixed and light so that drive the reciprocating piston in the cylinder in said combustion cylinders, in said exhaust manifold, are combined into from the combustion product of cylinder to comprise oxygen, water, nitrogen and NO XThe continuous part of discharge air-flow; And said vehicle comprises the discharge gas conduit, and said discharge gas conduit is used for discharging flow conductance to reactor so that contact with silver/aluminium oxide catalyst in being included in said reactor, thereby makes NO through reacting with the oxidizing hydrocarbons reducing agent that is added XComponent generation electronation; When vehicle operation and generation discharge air-flow, said method comprises:
Air-flow get into contain the reactor of reducing catalyst before, test constantly (a) discharge air-flow a part oxygen content and (b) discharge the NO of the part of air-flow XContent;
Test constantly (c) contains the temperature of the reducing catalyst in the reactor of reducing catalyst;
The flow gas hourly space velocity of the discharge air-flow that contacts of test constantly (d) and reducing catalyst; And use four measuring value (a-d) at least:
Continue to confirm the amount of reducing agent material, so that pass through the NO of silver catalyst reduction XAmount maximization, said reducing agent material are added to the forward part of work as of discharging air-flow before getting into reduction reactor discharging air-flow, said definite use pre-programmed, car-mounted computer and the current at least four measuring value of use carry out; And
Discharging air current flow, add current definite amount of reducing agent to the discharge air-flow to before reducing catalyst contacts.
2. the method for the addition of definite oxidizing hydrocarbons reducing agent material as claimed in claim 1, wherein the reducing agent material comprises the alcohol of from the set that following each item is formed, selecting: methyl alcohol, ethanol, propyl alcohol, butanols or this type of pure aldehyde.
3. the method for the addition of definite oxidizing hydrocarbons reducing agent material as claimed in claim 1, wherein the reducing agent material comprises ethanol.
4. the method for the addition of definite oxidizing hydrocarbons reducing agent material as claimed in claim 1, wherein reducing catalyst comprises the silver-colored particle that is supported on the alumina particle.
5. the method for the addition of definite oxidizing hydrocarbons reducing agent material as claimed in claim 1 is wherein carried out in the discharge gas conduit that is added on the reducing catalyst upper reaches of reducing agent material.
6. the method for the addition of definite oxidizing hydrocarbons reducing agent material as claimed in claim 1, wherein adding the reducing agent material is that it is spurted in the combustion product in the cylinder, it gets into exhaust manifold and discharges gas conduit then.
7. the method for the addition of definite oxidizing hydrocarbons reducing agent material as claimed in claim 1, wherein the reducing agent material is added in the cylinder, and under the situation of reducing agent material that need not to burn, enters the exhaust manifold from cylinder.
8. the method for the addition of definite oxidizing hydrocarbons reducing agent material as claimed in claim 1; Wherein the fuel of vehicle motor is one or more materials of from the set that following each item is formed, selecting: diesel oil, gasoline, hydrogen, natural gas, liquefied petroleum gas, ethanol, methyl alcohol and ethane.
9. the method for the addition of definite oxidizing hydrocarbons reducing agent material as claimed in claim 1, wherein add to the reducing agent material of discharging air-flow amount continue confirm to comprise through car-mounted computer and come to table look-up with reference to the predetermined of addition of the selected reducing agent material of the selected scope that is used for the four measuring value.
10. the method for the addition of definite oxidizing hydrocarbons reducing agent material as claimed in claim 9; Wherein the reducing agent material is an ethanol, and add to the ethanol of discharging air-flow amount continue confirm to comprise through car-mounted computer and come to table look-up with reference to the predetermined of addition of the ethanol of the selected scope that is used for the four measuring value.
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