CN1723340A - 压燃式内燃机的废气净化装置 - Google Patents
压燃式内燃机的废气净化装置 Download PDFInfo
- Publication number
- CN1723340A CN1723340A CNA2004800017416A CN200480001741A CN1723340A CN 1723340 A CN1723340 A CN 1723340A CN A2004800017416 A CNA2004800017416 A CN A2004800017416A CN 200480001741 A CN200480001741 A CN 200480001741A CN 1723340 A CN1723340 A CN 1723340A
- Authority
- CN
- China
- Prior art keywords
- waste gas
- catalyst
- capture
- fuel ratio
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9431—Processes characterised by a specific device
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0821—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with particulate filters
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
- F01N3/0842—Nitrogen oxides
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- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
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- 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
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- 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
- F01N3/2006—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating
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- F02D41/00—Electrical control of supply of combustible mixture or its constituents
- F02D41/02—Circuit arrangements for generating control signals
- F02D41/021—Introducing corrections for particular conditions exterior to the engine
- F02D41/0235—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus
- F02D41/024—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to increase temperature of the exhaust gas treating apparatus
- F02D41/0245—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to increase temperature of the exhaust gas treating apparatus by increasing temperature of the exhaust gas leaving the engine
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F02D41/00—Electrical control of supply of combustible mixture or its constituents
- F02D41/02—Circuit arrangements for generating control signals
- F02D41/021—Introducing corrections for particular conditions exterior to the engine
- F02D41/0235—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus
- F02D41/027—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to purge or regenerate the exhaust gas treating apparatus
- F02D41/0285—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to purge or regenerate the exhaust gas treating apparatus the exhaust gas treating apparatus being a SOx trap or adsorbent
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02D—CONTROLLING COMBUSTION ENGINES
- F02D41/00—Electrical control of supply of combustible mixture or its constituents
- F02D41/30—Controlling fuel injection
- F02D41/38—Controlling fuel injection of the high pressure type
- F02D41/40—Controlling fuel injection of the high pressure type with means for controlling injection timing or duration
- F02D41/402—Multiple injections
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F01N2240/18—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being an adsorber or absorber
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F01N2560/02—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics the means being an exhaust gas sensor
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F01N2610/00—Adding substances to exhaust gases
- F01N2610/03—Adding substances to exhaust gases the substance being hydrocarbons, e.g. engine fuel
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
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- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M26/00—Engine-pertinent apparatus for adding exhaust gases to combustion-air, main fuel or fuel-air mixture, e.g. by exhaust gas recirculation [EGR] systems
- F02M26/02—EGR systems specially adapted for supercharged engines
- F02M26/04—EGR systems specially adapted for supercharged engines with a single turbocharger
- F02M26/05—High pressure loops, i.e. wherein recirculated exhaust gas is taken out from the exhaust system upstream of the turbine and reintroduced into the intake system downstream of the compressor
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F02M26/00—Engine-pertinent apparatus for adding exhaust gases to combustion-air, main fuel or fuel-air mixture, e.g. by exhaust gas recirculation [EGR] systems
- F02M26/13—Arrangement or layout of EGR passages, e.g. in relation to specific engine parts or for incorporation of accessories
- F02M26/22—Arrangement or layout of EGR passages, e.g. in relation to specific engine parts or for incorporation of accessories with coolers in the recirculation passage
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F02M26/00—Engine-pertinent apparatus for adding exhaust gases to combustion-air, main fuel or fuel-air mixture, e.g. by exhaust gas recirculation [EGR] systems
- F02M26/13—Arrangement or layout of EGR passages, e.g. in relation to specific engine parts or for incorporation of accessories
- F02M26/22—Arrangement or layout of EGR passages, e.g. in relation to specific engine parts or for incorporation of accessories with coolers in the recirculation passage
- F02M26/23—Layout, e.g. schematics
- F02M26/28—Layout, e.g. schematics with liquid-cooled heat exchangers
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
一种能够捕获被包含在废气中的SOX的SOX捕获催化剂(11),在发动机排气通道中布置在NOX存储催化剂(12)的上游。当SOX捕获催化剂(11)的SOX捕获率降低时,流入SOX捕获催化剂(11)内的废气的空燃比保持为稀,并在该状态下升高SOX捕获催化剂(11)的温度。此时所捕获的SOX在SOX捕获催化剂(11)内散布,由此恢复SOX捕获率。
Description
发明领域
本发明涉及一种压燃式内燃机的废气净化装置。
背景技术
现有技术中公知的是这样一种内燃机,其具有布置在发动机排气通道中的NOX存储催化剂,当流入废气中的空燃比稀时,该NOX存储催化剂存储被包含在废气中的NOX,当流入废气中的空燃比变成化学计量空燃比或浓时,该NOX存储催化剂释放所存储的NOX。在该内燃机中,当在低空燃比状态下燃烧燃料时所产生的NOX被存储在NOX存储催化剂中。另一方面,当NOX存储催化剂的NOX存储能力达到饱和时,废气的空燃比临时变浓,并由此使NOX从NOX存储催化剂中释放出来并减少。
然而,燃料和润滑油都含有硫磺。所以,废气中含有SOX。该SOX与NOX一起存储在NOX存储催化剂中。但是,仅仅通过将废气的空燃比变浓不会使该SOX从NOX存储催化剂释放出来。所以,存储在NOX存储催化剂中的SOX的量逐渐增加。结果,可被存储的NOX的量最终会逐渐减少。
所以,本领域公知的是这样一种内燃机,其具有在发动机排气通道中布置在NOX存储催化剂上游的SOX吸收剂,从而防止SOX被送至NOX存储催化剂(见日本未审专利,公开号为NO.2000-145436)。在该内燃机中,SOX吸收剂吸收被包含在废气中的SOX。因此,防止了SOX流入NOX存储催化剂中。结果,由于SOX的存储可防止NOX的存储能力降低。
但是,当利用这种SOX吸收剂时,如果SOX吸收剂的SOX吸收能力最终饱和,SOX将最终流入NOX存储催化剂中。然而,对于该SOX吸收剂,如果SOX吸收剂的温度升高并使流入SOX吸收剂的废气的空燃比变浓,就可从SOX吸收剂释放所吸收的SOX,并由此可恢复SOX吸收剂。但是,以这种方式从SOX吸收剂释放SOX,所释放的SOX将最终存储于NOX存储催化剂中。所以,在这种内燃机中,设置绕过NOX存储催化剂的旁路通道。当从SOX吸收剂释放SOX时,所释放的SOX经由该旁路通道排入大气。
在上述的SOX吸收剂中,通过升高SOX吸收剂的温度并以这种方式使流入SOX吸收剂的废气的空燃比变浓,SOX可从SOX吸收剂释放出来。然而,这样,SOX仅从SOX吸收剂逐渐地释放出来。所以,为了使所有的所吸收的SOX从SOX吸收剂释放出来,空燃比必须长时间为浓的,因此就有需要大量燃料或还原剂的问题。而且,从SOX吸收剂所释放的SOX排入大气。这也是不可取的。
这样,当使用SOX吸收剂时,如果SOX的释放不受控制,SOX的吸收能力就会出现极限。所以,当使用SOX吸收剂时,SOX的释放必须受控。然而,如果SOX的释放受控,即只要使SOX从SOX吸收剂释放,上述问题就会出现。
发明内容
本发明的一个目的是提供一种压燃式内燃机的废气净化装置,该废气净化装置能够抑制SOX从SOX捕获催化剂的释放作用,同时保持NOX存储催化剂的高NOX存储能力。
根据本发明,提供一种用于压燃式内燃机的废气净化装置,其具有布置在发动机排气通道中并能够捕获包含在废气中的SOX的SOX捕获催化剂、和在排气通道中布置在SOX捕获催化剂的下游的NOX存储催化剂,当流入废气的空燃比稀时该NOX存储催化剂存储被包含于废气中的NOX,当流入废气的空燃比变成化学计量空燃比或变浓时释放所存储的NOX,其中当流入SOX捕获催化剂内的废气的空燃比稀时,所述的SOX捕获催化剂捕获被包含于废气中的SOX,其特性是当SOX捕获催化剂的温度在废气的稀空燃比状态下被升高时使所捕获的SOX逐渐在SOX捕获催化剂内扩散,并且如果SOX捕获催化剂的温度为SOX捕获温度或更高、当流入SOX捕获催化剂的废气的空燃比变浓时就释放所捕获的SOX;所述装置具有空燃比控制部件和估算部件,在发动机操作过程中该空燃比控制部件使流入SOX捕获催化剂内的废气的空燃比继续保持为稀的而不允许其变浓,该估算部件用于估算SOX捕获率,而该SOX捕获率表示由SOX捕获催化剂所捕获的SOX在废气包含的SOX中所占比率;当SOX捕获率降至预定比率之下时,所述装置使得SOX捕获催化剂的温度在废气的稀空燃比状态下升高从而由此恢复SOX捕获率。
附图的简要说明
图1为压燃式内燃机的概图;
图2为压燃式内燃机的另一实施例的概图;
图3为压燃式内燃机的再一个实施例的概图;
图4A和4B为颗粒过滤器的结构的视图;
图5为NOX存储催化剂的催化剂载体的表面部分的剖视图;
图6为SOX捕获催化剂的催化剂载体的表面部分的剖视图;
图7为SOX捕获率的视图;
图8说明了温度升高控制;
图9所示为喷射正时;
图10A-10C所示为所存储的SOX量ΣSOX1和所存储的SOX量SO(n)之间的关系,其用于升温控制等;
图11为所存储的SOX量ΣSOX1等变化的时间图;
图12为实施SOX稳定处理第一实施例的流程图;
图13为实施SOX稳定处理第二实施例的流程图;
图14为SOX稳定处理的时间图;
图15为颗粒过滤器的升温控制的时间图;
图16为SOX释放控制的时间图;
图17A和17B为所存储的NOX量NOXA的图等;
图18为执行NOX存储催化剂处理的流程图;
最佳实施方式
图1所示为压燃式内燃机的概图。
参照图1,1表示发动机主体,2表示每个气缸的燃烧室,3表示用于将燃料喷入每个燃烧室2内的电控燃料喷射器,4表示进气歧管,5表示排气歧管。进气歧管4经由进气道6与废气涡轮增压器7的压缩机7a的出口相连。压缩机7a的入口与空气滤清器8相连。布置在进气管6内的节流阀9由步进电机驱动。而且,进气管6周围设置的是冷却装置(中间冷却器)10,用于冷却流经进气管6内的进气。在图1所示的实施例中,发动机冷却水被引入冷却装置10内。发动机冷却水将进气冷却。另一方面,排气歧管5与废气涡轮增压器7的废气涡轮7b的入口相连,同时废气涡轮7b的出口与SOX捕获催化剂11的入口相连。此外,SOX捕获催化剂11的出口经由排气管13与NOX存储催化剂12相连。排气管13具有还原剂供给阀14,用于把由例如碳氢化合物组成的还原剂提供到流经排气管13内部的废气中。
排气歧管5和进气歧管4经由废气再循环(以下称为“EGR”)通道15互连。EGR通道15具有电控EGR控制阀16。此外,EGR通道15周围布置有冷却装置17,用于冷却流经EGR通道15内的EGR气体。在图1所示的实施例中,发动机冷却水被导入冷却装置17内。发动机冷却水将EGR气体冷却。另一方面,每个燃料喷射器3经由燃料供给管18与共轨19相连。从电控可变排量燃料泵20向该共轨19供给燃料。供入共轨19的燃料经由每个燃料供给管18供至燃料喷射器3。
电控单元30由数字计算机组成,该数字计算机具有只读存储器(ROM)32、随机存储器(RAM)33、微处理器(CPU)34、输入口35、和输出口36,它们都通过双向总线31彼此相连。SOX捕获催化剂11具有温度传感器21,用于检测该SOX捕获催化剂11的温度。NOX存储催化剂12具有温度传感器22,用于检测该NOX存储催化剂12的温度。温度传感器21和22的输出信号经由相应的AD转换器37输入至输入口35。而且,NOX存储催化剂12具有压差传感器23,用于检测NOX存储催化剂12之前和之后的压差。压差传感器23的输出信号经由相应的AD转换器37输入至输入口35。
加速踏板40具有负载传感器41并与其相连,该负载传感器41产生与加速踏板40的压低量L成比例的输出电压。负载传感器41的输出电压经由相应的AD转换器37输入至输入口35。此外,输入口35连有曲柄转角传感器42,每次曲柄转动例如15度该曲柄转角传感器42就产生输出脉冲。另一方面,输出口36经由相应的驱动电路38与燃料喷射器3、节流阀9步进电机、还原剂供给阀14、EGR控制阀16、和燃料泵20相连。
图2示出了压燃式内燃机的另一实施例。在该实施例中,除了还原剂供给阀14连至排气管13以外,排气歧管5中例如第1气缸的歧管5a具有碳氢化合物供给阀24,用于供给例如碳氢化合物。
另一方面,图3示出了压燃式内燃机的再一个实施例。在该实施例中,排气管13具有SOX传感器25,用于检测从SOX捕获催化剂11流出的废气中的SOX浓度。
首先,解释图1至图3所示的NOX存储催化剂12,NOX存储催化剂12置于三维网状结构的整体载体或小球状载体上,或者置于蜂窝结构的颗粒过滤器上。这样,NOX存储催化剂12可以置于各种类型的载体上,但在下文,将描述NOX存储催化剂12置于颗粒过滤器上的情况。
图4A和4B示出了携带NOX存储催化剂12的颗粒过滤器12a的结构。注意,图4A为颗粒过滤器12a的前视图,而图4B为颗粒过滤器12a的侧剖视图。如图4A和4B所示,颗粒过滤器12a形成蜂窝结构并具有多个互相平行延伸的排气通道60和61。这些排气通道由废气流入通道60和废气流出通道61组成,其中废气流入通道60的下游端由栓塞62密封,废气流出通道61的上游端由栓塞63密封。要注意的是,图4A中的阴影部表示栓塞63。所以,废气流入通道60和废气流出通道61经由薄分隔壁64交替布置。换句话说,废气流入通道60和废气流出通道61布置成使每个废气流入通道60由四个废气流出通道61包围、每个废气流出通道61由四个废气流入通道60包围。
颗粒过滤器12a由诸如堇青石之类的多孔材料形成。所以,流入废气流入通道60内的废气经由周围的分隔壁64流出并到达邻接的废气流出通道61内,如图4B的箭头所示。
当NOX存储催化剂12以这种方式置于颗粒过滤器12a上时,废气流入通道60和废气流出通道61的周围的壁,也即,分隔壁64的两侧的表面和分隔壁64的细孔的内壁负载由氧化铝组成的催化剂载体。图5示意性地示出了这种催化剂载体45的表面部的剖面。如图5所示,催化剂载体45负载被散布在其表面的贵金属催化剂46。此外,催化剂载体45由其表面上的一层NOX吸收剂47组成。
在本发明的这个实施例中,铂Pt用作贵金属催化剂46。作为形成NOX吸收剂47的成分,例如,可使用至少其中一种选自钾K、钠Na、铯Cs或其它碱金属,钡Ba、钙Ca或其它碱土,镧La、钇Y或其它稀土金属的元素。
如果供至发动机进气通道、燃烧室2、和NOX存储催化剂12排气通道上游的空气和燃料(碳氢化合物)的比率称为“废气的空燃比”,那么吸收剂47进行NOX吸收和释放作用,当废气的空燃比稀时存储NOX,当废气中的氧浓度降低时释放所存储的NOX。
也即,如果以把钡Ba用作形成NOX吸收剂47的成分的情况为例对此进行解释,则当废气的空燃比稀时、也即当废气中的氧浓度高时,含在废气中的NO在铂Pt 46上像在图5所示的那样被氧化成NO2,然后被吸入NOX吸收剂47中,并在NOX吸收剂47中以硝酸离子NO3 -的形式扩散同时与氧化钡BaO结合。这样,NOX被吸入NOX吸收剂47中。只要废气中的氧浓度高,NO2就会在铂Pt 46的表面上产生。只要NOX吸收剂47的NOX吸收能力没有饱和,NO2就会被吸收于NOX吸收剂47中并且产生硝酸离子NO3 -。
与此相反,通过从还原剂供给阀14供给还原剂从而使废气的空燃比变浓或变为化学计量空燃比,由于废气中的氧气浓度降低,反应沿着相反方向(NO3 -→NO2)进行,所以NOX吸收剂47中的硝酸离子NO3 -以NO2的形式从NOX吸收剂47释放出来。接着,所释放的NOX通过包含在废气中的未燃的碳氢化合物或CO而还原。
这样,当废气的空燃比稀时,也即,当在稀空燃比的状态下燃烧燃料时,废气中的NOX被吸入NOX吸收剂47中。然而,如果持续在稀空燃比的状态下燃烧燃料,则在该时间过程中,NOX吸收剂47的NOX吸收能力变得饱和,所以NOX将不再能够被NOX吸收剂47所吸收。因此,在NOX吸收剂47的吸收能力变得饱和之前,从还原剂供给阀14供给还原剂从而临时地使废气的空燃比变浓并由此从NOX吸收剂47释放NOX。
但是,废气含有SOX,也即SO2。当该SO2流入NOX存储催化剂12时,该SO2在铂Pt 46上被氧化并变成SO3。接着,该SO2被吸入NOX吸收剂47中并与氧化钡BaO结合,同时以硫酸根离子SO4 2-的形式扩散于NOX吸收剂47中从而形成稳定的硫酸盐BaSO4。然而,NOX吸收剂47具有较强的碱度,因此该硫酸盐BaSO4稳定且难以分解。如果仅仅使废气的空燃比变浓,该硫酸盐BaSO4将保持而不被分解。所以,在NOX吸收剂47中,硫酸盐BaSO4将随着时间的流逝而增加,因此NOX吸收剂47可吸收的NOX的量随着时间的流逝而减少。
然而,在这种情况下,像开始所描述的那样,如果将NOX存储催化剂11的温度升高至SOX释放温度600℃或更高,并且在那种状态下使流入NOX存储催化剂12的废气的空燃比浓,SOX将从NOX吸收剂47释放出来。但是,在这种情况下,SOX每次仅从NOX吸收剂47释放少许。因此,为了从NOX吸收剂47释放所有的所吸收的SOX,空燃比必须长时间为浓,由此出现了需要大量燃料或还原剂的问题。此外,从NOX吸收剂47所释放的SOX被排入大气中。这也是不可取的。
所以,在本发明中,将SOX捕获催化剂布置在NOX存储催化剂12的上游,该SOX捕获催化剂11用于捕获包含在废气中的SOX,由此防止SOX流入NOX存储催化剂12中。接下来,解释该SOX捕获催化剂11。
SOX捕获催化剂11由例如蜂窝结构的整体催化剂组成,并具有许多废气通孔,该通孔沿SOX捕获催化剂11的轴向直线延伸。当由蜂窝结构的整体催化剂以这种方式形成SOX捕获催化剂11时,废气通孔的内部周壁负载例如由氧化铝组成的催化剂载体。图6示意性地示出了该催化剂载体50的表面部的剖面。如图6所示,催化剂载体50的表面上形成有涂层51。而且,涂层51的表面上负载所散布的贵金属催化剂52。
在本发明的这个实施例中,铂Pt用作贵金属催化剂52。作为形成涂层51的成分,例如,可使用至少其中一种选自钾K、钠Na、铯Cs或其它碱金属,钡Ba、钙Ca或其它碱土,镧La、钇Y或其它稀土金属的元素。也即,SOX捕获催化剂11的涂层51呈现较强的碱性。
所以,包含在废气中的SOX、也即SO2如图6所示地在铂52上被氧化,然后被捕获于涂层51中。也即,SO2以硫酸根离子SO4 2-的形式散布在涂层51中以形成硫酸盐。注意,如上所述,涂层51呈现较强的碱度。所以,包含在废气中的部分SO2如图5所示地被直接捕获于涂层51中。
在图6中,涂层51中的浓度表示所捕获的SOX的浓度。从图6可以理解的是,涂层51中的SOX浓度在该涂层51的表面附近最高,并且离该涂层表面越深、SOX浓度越逐渐变低。如果涂层51表面附近的SOX浓度变高,涂层51表面的碱度就越弱,SOX捕获能力越弱。所以,如果SOX捕获催化剂11捕获的SOX在被包含于废气的SOX中所占的百分比称为“SOX捕获率”,则该SOX捕获率随着涂层51表面的碱度变弱而降低。
图7示出了SOX捕获率随着时间的变化。如图7所示,SOX捕获率最初接近于100%,但随着时间的流逝迅速降低。因此,在本发明中,如图8所示,当SOX捕获率降至预定比之下时,进行升温控制以在废气的稀空燃比状态下使SOX捕获催化剂11的温度升高并由此恢复SOX捕获率。
也即,如果在废气的稀空燃比状态下升高SOX捕获催化剂11的温度,则集中在涂层51表面附近的SOX朝着涂层51的深部扩散,这样涂层51中的SOX浓度变得均匀。也即,涂层51中所产生的硫酸盐从集中在涂层51表面附近的不稳定状态转变成均匀扩散于涂层51整个内部的稳定状态。如果涂层51表面附近的SOX朝着涂层51的深部分散,那么涂层51表面附近的SOX的浓度将降低。所以,当SOX捕获催化剂11的升温控制完成时,SOX捕获率将如图8所示地恢复。
当执行SOX捕获催化剂11的升温控制时,如果使SOX捕获催化剂11的温度基本约为450℃,涂层51表面附近的SOX就会扩散至涂层51中。如果使SOX捕获催化剂11的温度升至约600℃,涂层51中的SOX浓度就会变得相当均匀。因此,在进行SOX捕获催化剂的升温控制的时候,优选的是在废气的稀空燃比状态下将SOX捕获催化剂11的温度升高至约600℃。
注意,当升高SOX捕获催化剂11的温度时,如果废气的空燃比变浓,SOX将从SOX捕获催化剂11释放出来。所以,当升高SOX捕获催化剂11的温度时,废气的空燃比不得变浓。而且,当涂层51表面附近的SOX的浓度变高,即使不升高SOX捕获催化剂11的温度,如果使废气的空燃比变浓,SOX将从SOX捕获催化剂11释放出来。所以,在本发明中,当SOX捕获催化剂11的温度为SOX释放温度或更高时,防止流入SOX捕获催化剂11的废气的空燃比变浓。
在本发明中,基本上,假定SOX捕获催化剂11在从购买车辆的时刻至其寿命终止时没有更换地使用。近年来,特别是包含在燃料中的硫黄的量已经减少。所以,如果使SOX捕获催化剂11的能力大至某一程度,SOX捕获催化剂11就可以不更换地使用至该车辆的寿命终止时。例如,如果车辆的潜在运行距离为500,000km,就使SOX捕获催化剂11的捕获能力能够在约250,000km以前不进行升温控制的情况下,以高SOX捕获率继续捕获SOX。在这种情况下,最初的升温控制约在250,000km时执行。
接着,将参照图9解释升高SOX捕获催化剂11温度的方法。
升高SOX捕获催化剂11温度的其中一个有效方法就是,延迟燃料喷射正时直至压缩上止点之后。也即,一般地,在图9中,主要燃料Qm在接近(I)中所示的压缩上止点时喷射。在这种情况下,如图9的(II)所示,如果主要燃料Qm的喷散正时延迟,后燃期将会变得更长,所以废气温度就升高。如果废气温度升高,SOX捕获催化剂11的温度将随之升高。
此外,为了升高SOX捕获催化剂11的温度,如图9的(III)所示,除了主要燃料Qm以外,还可以在进气上止点附近喷射增补燃料QV。如果以这种方式另外喷射增补燃料QV,被燃烧的燃料增加的量正好为增补燃料QV的量,因此废气温度升高,SOX捕获催化剂11的温度也由此升高。
另一方面,如果以这种方式在进气上止点附近喷射增补燃料QV,由于压缩冲程的压缩热,从该增补燃料QV产生醛、酮、过氧化物、一氧化碳、和其它中间产物。这些中间产物加速了主要燃料Qm的反应。所以,在这种情况下,如图9的(III)所示,即使主要燃料Qm的喷散正时大大延迟,也会实现良好的燃烧而不会点火不良。也即,主要燃料Qm的喷射正时可以大大延迟,因此废气温度将变得相当高,SOX捕获催化剂11的温度也因此迅速升高。
而且,为了升高SOX捕获催化剂11的温度,如图9的(IV)所示,除了主要燃料Qm以外,在膨胀冲程或排气冲程中还可以喷射增补燃料Qp。也即,在这种情况下,增补燃料Qp的主要部分不燃烧并以未燃的碳氢化合物的形式排入排气通道内。该未燃的碳氢化合物被SOX捕获催化剂11上的过量氧气氧化。此时发生的氧化反应的热量使SOX捕获催化剂11的温度升高。
另一方面,在图2所示的内燃机中,也可以从碳氢化合物供给阀24供给碳氢化合物并将采用氢化合物的氧化反应产生的热量来升高SOX捕获催化剂11的温度。此外,可以执行图9的(II)至(IV)所示的任一喷射控制程序并从碳氢化合物供给阀24供给碳氢化合物。注意,无论使用哪种方法来升高温度,流入SOX捕获催化剂11的废气的空燃比不要浓,而是保持稀。
接下来,参照图10A至12解释在SOX捕获催化剂11上进行SOX稳定处理的第一实施例。
在该第一实施例中,估算SOX捕获催化剂11所捕获的SOX的量。当SOX捕获催化剂11所捕获的SOX的量超过预定量时,判定SOX捕获率已经降至预定比之下。这时,为了恢复SOX捕获率,在升温度控制中在废气的稀空燃比状态下升高SOX捕获催化剂11的温度。
换句话说,燃料含有一定比率的硫磺。所以,包含在废气中的SOX的量、也即由SOX捕获催化剂11所捕获的SOX的量与燃料喷射量成比例。燃料喷射量为所需扭距和发动机速度的函数。所以,由SOX捕获催化剂11所捕获的SOX的量也变成所需扭矩和发动机速度的函数。在本发明的这个实施例中,将单位时间内被捕获于SOX捕获催化剂11中的SOX量SOXA,作为所需扭矩TQ和发动机速度N的函数按如图10A所示的图谱(map)形式预先存储于ROM32中。
进一步,润滑油含有一定比率的硫磺。燃烧室2中所燃烧的润滑油的量,更确切地说,包含在废气中并被SOX捕获催化剂所捕获的SOX的量,变成所需扭矩和发动机速度的函数。在本发明的该实施例中,包含在润滑油中并在单位时间内被捕获于SOX捕获催化剂11中的SOX量SOXB,作为所需扭矩TQ和发动机速度N的函数按如图10B所示的图谱形式预先存储于ROM32中。通过累积相加SOX量SOXA和SOX量SOXB,计算在SOX捕获催化剂11中所捕获的SOX总量ΣSOX1。
而且,在本发明的这个实施例中,如图10C所示,预先存储SOX捕获催化剂11的温度升高时的SOX总量ΣSOX1与预定的SOX量SO(n)之间的关系。当SOX总量ΣSOX1超过预定的SOX量SO(n)(n=1,2,3,...)时,执行SOX捕获催化剂11的升温控制。注意,在图10C中,n表示升温处理的次数。从图10C可以理解的是,当用于恢复SOX捕获率的升温处理的次数n增加时,预定量SO(n)增加。处理的次数n越大,预定量SO(n)增加的比率越少。也即,SO(d)对SO(2)的增加比率比SO(2)对SO(1)的增加比率小。
也即,如图11的时间图所示,由SOX捕获催化剂11所捕获的SOX总量ΣSOX1随着时间的流逝继续增加到容许值MAX为止。注意在图11中,当ΣSOX1=MAX时的时间为运行距离约为500,000km的时间。
另一方面,在图11中,SOX浓度表示SOX捕获催化剂11表面附近的SOX的浓度。从图11可以理解的是,当SOX捕获催化剂11表面附近的SOX的浓度超过容许值SOZ时,在升温控制中在废气的稀空燃比A/F状态下升高SOX捕获催化剂11的温度T。当执行升温控制时,SOX捕获催化剂11表面附近的SOX的浓度降低,但SOX浓度的降低量随着每个升温控制程序而变得更小。所以,从执行其中一个升温控制程序到执行下一个升温控制的间隔随着每个升温控制程序而变得更短。
注意,如图11所示,所捕获的SOX总量ΣSOX1达到SO(1),SO(2),...意味着SOX捕获催化剂11表面附近的SOX的浓度达到了容许值SOZ。
图12示出了用于实施SOX稳定处理的第一实施例的程序。
参照图12,首先,在步骤100中,从图10A和图10B读取单位时间内所捕获的SOX的量SOXA和SOXB。接下来,在步骤101中,将这些SOXA和SOXB的和加入SOX总量ΣSOX1中。接着,在步骤102中,判断SOX总量ΣSOX1是否已经达到图10C所示的预定量SO(n)(n=1,2,3,...)。当SOX总量ΣSOX1已经达到预定量SO(n)时,程序进入步骤103,在该步骤103中执行升温控制。
如图13和14示出了SOX稳定处理的第二实施例。在该实施例中,如图3所示,SOX传感器25布置在SOX捕获催化剂11的下游。该SOX传感器25检测从SOX捕获催化剂11流出的废气中的SOX的浓度。也即,在第二实施例中,如图14所示,当SOX传感器25所检测的废气中的SOX的浓度超过预定浓度SOY时,断定SOX捕获率已经降至预定比之下。此时,为了恢复SOX捕获率,在升温控制中在废气的稀空燃比A/F状态下升高SOX捕获催化剂11的温度T。
图13示出了用于实施第二实施例的程序。
参照图13,首先,在步骤110中,读取SOX传感器25的输出信号,例如输出电压V。接下来,在步骤111中,判断SOX传感器25的电源电压V是否已经超过设定值VX,也即,判断废气中的SOX浓度是否已经超过预定浓度SOY。当V>VX时,也即,当废气中的SOX浓度已经超过预定浓度SOY时,程度进入步骤112,在该步骤112中执行升温控制。
接下来,参照图15-18描述用于NOX存储催化剂12的处理。
在本发明的这个实施例中,将单位时间内存储于NOX存储催化剂12中的NOX的量NOXA作为所需转矩TQ和发动机速度N的函数按如图17A所示的图谱形式预先存储在ROM32中。通过累积相加该NOX量NOXA,计算存储在NOX存储催化剂11中的NOX总量ΣNOX。在本发明的这个实施例中,如图15所示,每次NOX总量ΣNOX达到容许值NX,流入NOX存储催化剂12内的废气的空燃比A/F临时变浓,由此NOX从NOX存储催化剂12释放出来。
注意,当流入NOX存储催化剂12内的废气的空燃比A/F变浓时,流入SOX捕获催化剂11内的废气的空燃比A/F必须保持为稀的。所以,在本发明的该实施例中,还原剂供给装置,例如图1至图3所示的还原剂供给阀14布置在SOX捕获催化剂11与NOX存储催化剂12之间的排气通道中。当NOX应该从NOX存储催化剂12释放出来时,通过从还原剂供给阀14向排气通道供给还原剂,流入NOX存储催化剂12内的废气的空燃比临时变浓。
另一方面,包含在废气中的颗粒物在载有NOX存储催化剂12的颗粒过滤器12a上被捕获、接着被氧化。然而,如果所捕获的颗粒物的量比所氧化的颗粒物的量大,则颗粒物将逐渐沉积在颗粒过滤器12a上。在这种情况下,如果颗粒物的沉积增加,就必须除去所沉积的颗粒物。在这种情况下,如果在空气过量的情况下将颗粒过滤器12a的温度升高至约600℃,则所沉积的颗粒物就被氧化和去除。
因此,在本发明的这个实施例中,当沉积在颗粒过滤器12a上的颗粒物的量超过容许量时,在废气的稀空燃比状态下升高颗粒过滤器12a的温度,并由此通过氧化将所沉积的颗粒物除去。具体地说,在本发明的这个实施例中,如图15所示,当由压差传感器23所检测的颗粒过滤器12a之前和之后的压差ΔP超过容许值PX时,则断定所沉积的颗粒物的量已经超过容许量。此时,流入颗粒过滤器12a内的废气的空燃比保持为稀的,颗粒过滤器12a的温度T在升温控制中被升高。注意,如果颗粒过滤器12a的温度T变高,所捕获的NOX总量ΣNOX由于NOX从NOX存储催化剂12释放出来而降低。
当颗粒过滤器12a的温度应该升高时,SOX捕获催化剂11的温度不必升高。所以,当颗粒过滤器12a的温度升高时,从还原剂供给阀14供给还原剂,供给范围为可将废气的空燃比保持为稀的,并且将还原剂氧化反应的所产生的热量用来升高颗粒过滤器12a的温度T。
另一方面,当SOX捕获催化剂11的SOX捕获率为100%时,SOX一点也不流入NOX存储催化剂12内。所以,在这种情况下,绝对没有SOX被存储于NOX存储催化剂12的危险。与此相反,当SOX捕获率不是100%时,即使SOX捕获率接近100%,SOX也会被存储于NOX存储催化剂12中。然而,在该情况下,单位时间内存储于NOX存储催化剂12中的SOX的量极小。这可以说,如果经过很长时间,则大量的SOX将会存储在NOX存储催化剂12。如果存储大量的SOX,所储存的SOX就不得不被释放。
如上所述,为了使SOX从NOX存储催化剂12释放出来,必须使NOX存储催化剂12的温度升至SOX释放温度并使流入NOX存储催化剂12的废气空燃比变浓。因此,在本发明的这个实施例中,如图16所示,当存储在NOX存储催化剂12中的SOX的量ΣSOX2达到容许值SOX2时,将NOX存储催化剂12的温度T升高至NOX释放温度TX,并且使流入NOX存储催化剂12的废气的空燃比变浓。注意,将单位时间内存储在NOX存储催化剂12中的SOX的量SOXZ作为所需转矩TQ和发动机速度N的函数按如图17B的图谱所示形式预先存储在ROM32中。通过累积相加该SOX的量SOXZ,计算所存储的SOX总量ΣSOX2。
当从NOX存储催化剂12释放SOX时,如果使流入SOX捕获催化剂11的废气的空燃比变浓,则被捕获于SOX捕获催化剂11中的SOX将会从SOX捕获催化剂11释放,所释放的SOX将会被存储在NOX存储催化剂12中。所以,当从NOX存储催化剂12释放SOX时,不能使流入SOX捕获催化剂11的废气的空燃比变浓。相应地,在本发明的这个实施例中,当SOX应该从NOX存储催化剂12释放出来时,首先,使流入SOX捕获催化剂11和NOX存储催化剂12内的废气的空燃比保持为稀,并从还原剂供给阀14供给还原剂以将NOX存储催化剂12的温度T升高至NOX释放温度TX,然后,使流入SOX捕获催化剂11内的废气的空燃比保持为稀,并且增加从还原剂供给阀14供给的还原剂的供给量,从而使得流入NOX存储催化剂12内的废气的空燃比变浓。注意,在这种情况下,可选择地,还可以将流入NOX存储催化剂12内的废气的空燃比在浓和稀之间进行转换。
图18所示为NOX存储催化剂12的处理程序。
参照图18,首先,在步骤120中,根据图17A所示的图谱计算单位时间内被吸收的NOX的量NOXA。接着,在步骤121中,将该NOXA加至被存储在NOX存储催化剂12中的NOX总量ΣNOX中。接下来,在步骤122中,判断所存储的NOX总量ΣNOX是否已经超过容许值NX。当ΣNOX>NX,程序进入步骤123,在该步骤123中执行变浓处理,通过从还原剂供给阀14供给还原剂,把流入NOX存储催化剂12内的废气的空燃比临时地从稀改变成浓,并清除ΣNOX。
接着,在步骤124中,压差传感器23用来检测颗粒过滤器12a之前和之后的压差ΔP。下一步,在步骤125中,判断压差ΔP是否已经超过容许值PX。当ΔP>PX,程序进入步骤126,在该步骤126中执行颗粒过滤器12a的升温控制。通过将流入颗粒过滤器12a的废气的空燃比保持为稀并从还原剂供给阀14供给还原剂,执行颗粒过滤器12a的升温控制。
接下来,在步骤127中,根据图17B所示的图谱计算单位时间内所存储的SOX量SOXZ。下一步,在步骤128中,判断所存储的SOX总量ΣSOX2是否已经超过容许值SX2。当ΣSOX>SX2时,程序进入步骤130,在该步骤130中使流入NOX存储催化剂12内的废气的空燃比保持为稀并从还原剂供给阀14供给还原剂,从而在升温控制中将NOX存储催化剂12的温度T升高至SOX释放温度TX。接着,在步骤131中,在变浓处理中将从还原剂供给阀14供给的还原剂用来保持流入NOX存储催化剂12的废气的空燃比为富,并且清除ΣSOX2。
Claims (10)
1.一种用于压燃式内燃机的废气净化装置,该内燃机具有布置在发动机排气通道中并能够捕获包含在废气中的SOX的SOX捕获催化剂、和在排气通道中布置在SOX捕获催化剂的下游的NOX存储催化剂,当流入废气的空燃比稀时该NOX存储催化剂存储被包含于废气中的NOX,当流入废气的空燃比变成化学计量空燃比或变浓时释放所存储的NOX,其中当流入SOX捕获催化剂内的废气的空燃比稀时,所述的SOX捕获催化剂捕获被包含于废气中的SOX,其特性是当SOX捕获催化剂的温度在废气的稀空燃比状态下被升高时使所捕获的SOX在SOX捕获催化剂内逐渐扩散,并且如果SOX捕获催化剂的温度为SOX释放温度或更高、则当流入SOX捕获催化剂的废气的空燃比变浓时就释放所捕获的SOX;所述装置具有空燃比控制部件和估算部件,在发动机操作过程中该空燃比控制部件使流入SOX捕获催化剂内的废气的空燃比连续保持为稀而不允许其变浓,该估算部件用于估算SOX捕获率,而该SOX捕获率表示由SOX捕获催化剂所捕获的SOX在废气包含的SOX中的比率;当SOX捕获率降至预定比之下,所述装置使得SOX捕获催化剂的温度在废气的稀空燃比状态下升高从而由此恢复SOX捕获率。
2.根据权利要求1所述的废气净化装置,其特征在于,所述SOX捕获催化剂由形成于催化剂载体上的涂层和保持在该涂层上的贵金属催化剂组成,该涂层含有被散布在其中的碱金属、碱土金属、或稀土金属。
3.根据权利要求1所述的废气净化装置,其特征在于,估算被捕获在所述SOX捕获催化剂中的SOX的量,当被捕获于SOX捕获催化剂中的SOX的量超过预定量时,断定SOX捕获率已经降至预定比之下,此时通过在废气的稀空燃比状态下升高SOX捕获催化剂的温度而恢复该SOX捕获率。
4.根据权利要求3所述的废气净化装置,其特征在于,所述预定量随着恢复SOX捕获率的处理次数的增加而增加,处理次数越大、预定量的增加比率越小。
5.根据权利要求1所述的废气净化装置,在排气通道中在SOX捕获催化剂的下游布置有能够检测废气中的SOX浓度的SOX传感器,根据所述SOX传感器的输出信号计算SOX捕获率。
6.根据权利要求5所述的废气净化装置,其特征在于,当SOX传感器所检测的废气中的SOX浓度超过预定浓度时,断定该SOX捕获率已经降至预定比之下,此时通过在废气的稀空燃比状态下升高SOX捕获催化剂的温度来恢复该SOX捕获率。
7.根据权利要求1所述的废气净化装置,其特征在于,在SOX捕获催化剂和NOX存储催化剂之间的排气通道中布置有还原剂供给装置,当NOX应该从NOX存储催化剂释放出来时,从该还原剂供给装置将还原剂供至排气通道内从而临时使流入NOX存储催化剂内的废气的空燃比变浓。
8.根据权利要求1所述的废气净化装置,其特征在于,NOX存储催化剂置于颗粒过滤器上,该颗粒过滤器用于捕获并氧化被包含在废气中的颗粒物。
9.根据权利要求8所述的废气净化装置,当沉积在颗粒过滤器上的颗粒物的量超过容许量时,使颗粒过滤器的温度在废气的稀空燃比状态下被升高,从而通过氧化除去所沉积的颗粒物。
10.根据权利要求7所述的废气净化装置,其特征在于,当SOX存储在NOX存储催化剂中时,NOX存储催化剂的温度被升高至SOX释放温度,并从还原剂供给装置将还原剂供至排气通道内从而使流入NOX存储催化剂内的废气的空燃比变浓。
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ES2282917T3 (es) | 2007-10-16 |
US20060064969A1 (en) | 2006-03-30 |
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