CN101548075B - 内燃机的排气净化装置 - Google Patents
内燃机的排气净化装置 Download PDFInfo
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- CN101548075B CN101548075B CN2008800010152A CN200880001015A CN101548075B CN 101548075 B CN101548075 B CN 101548075B CN 2008800010152 A CN2008800010152 A CN 2008800010152A CN 200880001015 A CN200880001015 A CN 200880001015A CN 101548075 B CN101548075 B CN 101548075B
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- 238000002485 combustion reaction Methods 0.000 title claims abstract description 23
- 238000000746 purification Methods 0.000 title claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000446 fuel Substances 0.000 claims abstract description 39
- 238000001514 detection method Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000005864 Sulphur Substances 0.000 claims description 42
- 229910000765 intermetallic Inorganic materials 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 42
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 11
- 229910052788 barium Inorganic materials 0.000 description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- JQUCWIWWWKZNCS-LESHARBVSA-N C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F Chemical compound C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F JQUCWIWWWKZNCS-LESHARBVSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical group [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OMBVEVHRIQULKW-DNQXCXABSA-M (3r,5r)-7-[3-(4-fluorophenyl)-8-oxo-7-phenyl-1-propan-2-yl-5,6-dihydro-4h-pyrrolo[2,3-c]azepin-2-yl]-3,5-dihydroxyheptanoate Chemical compound O=C1C=2N(C(C)C)C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C(C=3C=CC(F)=CC=3)C=2CCCN1C1=CC=CC=C1 OMBVEVHRIQULKW-DNQXCXABSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229940126540 compound 41 Drugs 0.000 description 2
- 239000002828 fuel tank Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- WGFNXGPBPIJYLI-UHFFFAOYSA-N 2,6-difluoro-3-[(3-fluorophenyl)sulfonylamino]-n-(3-methoxy-1h-pyrazolo[3,4-b]pyridin-5-yl)benzamide Chemical compound C1=C2C(OC)=NNC2=NC=C1NC(=O)C(C=1F)=C(F)C=CC=1NS(=O)(=O)C1=CC=CC(F)=C1 WGFNXGPBPIJYLI-UHFFFAOYSA-N 0.000 description 1
- QOVYHDHLFPKQQG-NDEPHWFRSA-N N[C@@H](CCC(=O)N1CCC(CC1)NC1=C2C=CC=CC2=NC(NCC2=CN(CCCNCCCNC3CCCCC3)N=N2)=N1)C(O)=O Chemical compound N[C@@H](CCC(=O)N1CCC(CC1)NC1=C2C=CC=CC2=NC(NCC2=CN(CCCNCCCNC3CCCCC3)N=N2)=N1)C(O)=O QOVYHDHLFPKQQG-NDEPHWFRSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001552 barium Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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Abstract
在内燃机中，利用比供给到燃烧室(2)内的燃料量少的量的、与该燃料量成比例的燃料，在样品气体生成室(14)内生成检测硫用的样品气体。设置有具有捕获样品气体中含有的硫的传感部，并且可由传感部的物性变化检测被该传感部捕获的硫的量的SOx传感器(16)，由该SOx传感器(16)的输出值推定流入到催化剂(8)中的SOx量。
Description
技术领域
本发明涉及内燃机的排气净化装置。
背景技术
以往人们就知道为了检测排气中的SOx浓度而在内燃机排气通路内配置的SOx浓度传感器，这些公知的SOx浓度传感器，通常使用固体电解质，测量通过SOx变成硫酸离子而产生的电动势，从而检测排气中的SOx浓度(例如参照日本特开2004-239706号公报)。
然而，使用这样的SOx浓度传感器的现有的SOx检测装置，存在只在高温下工作、装置规模大、特别是在SOx浓度低时不能检测出SOx浓度的大问题。像这种SOx浓度传感器过去只因为瞬时地直接检测排气中的SOx浓度才引人注目，这样一来，只要想瞬时地直接检测排气中的SOx浓度，就必然地产生如上所述的种种问题。
于是，本发明者转换想法，不是检测瞬时的SOx浓度，而是着眼于检测经过长期间的硫(S)的累计量。并且判明，若进行这样的想法的转换，则即使不直接检测排气中的SOx浓度，也能够容易地推定排气中的SOx量。
发明内容
本发明的目的在于提供能够容易地检测流入到催化剂中的SOx量的内燃机的排气净化装置。
根据本发明，提供一种内燃机的排气净化装置，所述内燃机在内燃机排气通路内配置有排气净化用催化剂，所述的内燃机的排气净化装置具备SOx传感器，由该SOx传感器的输出值推定流入到催化剂中的SOx量，所述SOx传感器具有传感部，并且可由传感部的物性变化检测被传感部捕获的硫的量，所述传感部利用比供给到燃烧室内的燃料量少的量的、且与该燃料量成比例的燃料生成检测硫用的样品气体，并捕获该样品气体中含有的硫。
附图说明
图1表示压缩点火式内燃机的总体图；
图2是用于说明硫的检测原理的图；
图3是用于说明硫的检测方法的图；
图4是用于说明硫的检测方法的图；
图5是用于说明硫的检测方法的图；
图6是表示另一实施例的SOx传感器的传感部周围的侧面剖面图；
图7是用于检测SOx中毒量的流程图。
具体实施方式
图1表示压缩点火式内燃机的总体图。
参照图1，各符号分别表示如下：1-内燃机主体、2-各气缸的燃烧室、3-用于向各燃烧室2内分别喷射燃料的电子控制式燃料喷射阀、4-吸气歧管、5-排气歧管、6-燃料箱。排气歧管5通过排气管7与排气净化用催化剂8连接。在图1表示的实施例中，该催化剂8包括捕获排气中含有的SOx以使SOx不流入到配置于催化剂8的下游的催化剂中的SOx捕集催化剂。
在燃料箱6上安装有燃料供给泵9，从燃料供给泵9排出的燃料在燃料分流器10中被分流成喷射用燃料和样品用燃料。喷射用燃料通过燃料供给管11与用于向各燃料喷射阀3分配燃料的共轨12连接，样品用燃料通过燃料供给管13与在排气管7的周围形成的样品气体生成室14连接。被供给到该样品气体生成室14内的样品燃料，相比于供给到燃烧室2内的喷射用燃料为极少量，并且与喷射量燃料成比例。
如图1所示，设置有用于向样品气体生成室14内供给空气的空气泵15，利用由燃料供给管13供给的燃料和由空气泵15供给的空气在样品气体生成室14内生成检测硫用的样品气体。另外，在样品气体生成室14内配置有用于检测样品气体中的硫的SOx传感器16。
电子控制单元20包括数字计算机，具备利用双向性总线21相互连接的ROM(只读存储器)22、RAM(随机存储器)23、CPU(微处理器)24、输入端口25和输出端口26。SOx传感器16的输出在检测电路29中被校正，已校正的输出通过相对应的AD转换器27输入至输入端口25。另外，在油门踏板30上连接有发生与油门踏板30的踏下量L成比例的输出电压的负荷传感器31，负荷传感器31的输出电压通过相对应的AD转换器27输入至输入端口25。此外，在输入端口25上连接有每当曲轴旋转例如15°就发生输出脉冲的曲轴转角传感器32。另一方面，输出端口26通过相对应的驱动电路28与燃料喷射阀3、燃料供给泵9和空气泵15连接。
图2表示利用SOx传感器16的硫的检测原理。SOx传感器16的传感部，由能够捕获样品气体中硫的金属或金属化合物形成，图2(A)用符号40模式地表示形成SOx传感器16的传感部的该金属或金属化合物。图2(A)所表示的金属或金属化合物40包括不含硫的金属或金属化合物。在本发明的实施例中，该金属或金属化合物40包括碱金属、碱土类金属、稀土类金属、贵金属或这些金属的化合物。
以下，以作为该金属或金属化合物40使用作为碱土类金属的一种的钡(Ba)或其化合物的情况为例对硫的检测方法进行说明。
钡(Ba)在大气中变为氧化钡(BaO)。该氧化钡(BaO)被置于排气中时，利用排气中所含有的CO、CO2而立即变成碳酸钡(BaCO3)。而且，该碳酸钡(BaCO3)，利用排气中含有的NOx变成硝酸钡(Ba(NO3)2)。
即，在使用钡(Ba)的情况下，图2(A)所示的金属或金属化合物40是氧化钡(BaO)、碳酸钡(BaCO3)或硝酸钡(Ba(NO3)2)，在该金属或金属化合物40被置于排气中的情况下，变成硝酸钡(Ba(NO3)2)。在本发明的实施例中，图2(A)所示的金属或金属化合物40由氧化钡(BaO)构成。
另一方面，在燃料内含有硫，因此样品气体中含有硫，该硫(S)以SOx的形式被金属或金属化合物40捕获而变成图2(A)所示的含有硫的金属化合物41。在使用钡(Ba)的情况下，该含有硫的金属化合物41是硫酸钡(BaSO4)。因此，在金属或金属化合物40被置于样品气体中的情况下，如图2(B)所示，由氧化钡(BaO)构成的金属化合物40的一部分的氧化钡(BaO)变成硫酸钡(BaSO4)。一般地表现的话，氧化物的一部分变成硫酸盐。该场合下，金属化合物41中的硫酸盐的情况是，随着时间经过，即被捕获的硫的量越增大就越高。
再者，当样品气体的空燃比为稀，即样品气体中存在充分的氧，样品气体的温度比300℃左右高时，样品气体中的硫容易以SOx的形式被金属或金属化合物40，即SOx传感器16的传感部捕获。因此，在图1所示的实施例中，控制空气泵15使得样品气体的空燃比为稀，为了为使SOx传感器16的传感部的温度达到容易以SOx的形式捕获硫的温度而提高样品气体温度，在排气管7的周围形成有样品气体生成室14。当然，为了提高样品气体的温度，也可以使用电加热器等的其他的升温装置。
另一方面，图2(C)表示金属或金属化合物40由贵金属或其化合物构成的情况。作为该贵金属，可以使用钯(Pb)、铑(Ph)或铂(Pt)，图2(C)表示作为一例使用钯(Pb)的情况。该情况下，若硫被捕获，则金属氧化物(PdO)变成硫化物(PdS)。
当氧化物变成硫酸盐时，或者金属氧化物变成硫化物时，物性发生变化，因此，可以由该物性的变化检测被捕获的硫的量。另一方面，如前所述，被供给到样品气体生成室14中的燃料量，与被供给到燃烧室2内的燃料喷射量成比例，因此，若知道样品气体中的硫的量，就可知道排气中的硫的量，即流入到催化剂8中的SOx量。
因此，在本发明中，设置SOx传感器16，由该SOx传感器16的输出值推定流入到催化剂8中的SOx量，所述SOx传感器16具有捕获样品气体中所含有的硫的传感部，并且可由传感部的物性变化检测被传感部捕获的硫的量。
接着，一边参照图3～图6，一边对应该测量的物性、和与应该测量的物性相应的检测方法的代表例进行说明。再者，对于所述图3～图6，以如图2(B)所示的氧化物变成硫酸盐的情况为例进行说明。
图3表示被测量的物性为电物性，被测量的电物性为电阻的情况。
图3(A)表示硫(S)的捕获量与电阻值R的关系。如图3(A)所示，硫(S)的捕获量越增大，即从氧化物向硫酸盐的变化量越多，电阻值R越增大。因此，可以由电阻值R求出硫(S)的捕获量，即流入到催化剂8中的SOx量的累积值。
图3(B)表示图1所示的SOx传感器16的检测部。如图3(B)所示，配置于样品气体生成室14内的SOx传感器16的检测部，由检测用传感部51和参照用传感部53构成，所述检测用传感部51由被一对端子50支撑的金属化合物片形成，所述参照用传感部53由被一对端子52支撑的金属化合物片形成。检测用传感部51由氧化物形成，参照用传感部53由硫酸盐形成。当样品气体流通时，参照用传感部53不变化，但检测用传感部51的氧化物一点一点地变成硫酸盐。这样一来，检测用传感部51的电阻值R便逐渐增大。
检测用传感部51的电阻值R在周围的温度变高时变高。因此，为了除去这样的温度变化给电阻值R带来的影响，设置有参照用传感部53，例如，使用包括如图3(C)所示的惠斯登电桥的检测电路29(图1)，由检测用传感部51的电阻值与参照用传感部53的电阻值之差求出硫(S)的捕获量。在使用如图3(C)所示的惠斯登电桥时，电压计54所显现的电压V，如图3(D)所示，随着硫(S)的捕集量增大而降低。该电压V通过AD转换器27输入至输入端口25。
图4～图6表示被测量的物性为热物性，被测量的热物性为热容量和导热性的情况。
如图4(A)所示，硫(S)的捕获量越增大，由金属化合物片形成的传感部的热容量越减少。因此如图4(B)所示，在传感部周围的温度上升时，硫(S)的捕获量越增大则传感部的中心温度的上升率越增高。
图5(A)表示SOx传感器16的检测部。在图5(A)所示的例子中，设置有具有一对引线60的热敏电阻元件61、和具有一对引线62的热敏电阻元件63。而且，在该例子中，通过利用金属化合物64包围热敏电阻元件61的周围而形成有检测用传感部65，通过利用金属化合物66包围热敏电阻元件63的周围而形成有参照用传感部67。
在该例中，可由检测用传感部65周围的温度变化时的热敏电阻元件61的电阻值的变化的应答性推定金属化合物64的热容量，由参照用传感部67周围的温度变化时的热敏电阻元件63的电阻值的变化的应答性推定金属化合物63的热容量，由这些热容量之差求出硫(S)的捕集量。
即，具体地讲，使用如图5(B)所示的惠斯登电桥，以电压的形式求得热敏电阻元件61的电阻值与热敏电阻元件63的电阻值之差。该情况下，显现该电阻值之差的电压计68的电压V，如图5(C)所示，被检测用传感部65捕获的硫(S)越增大则越降低。
在图6所示的例子中，设置有用于将检测用传感部65和参照用传感部67分别加热的加热器69、70。在该例中，即使是周围的温度不变化的情况下，也可以通过使这些加热器69、70发热，来求得金属化合物64与金属化合物66的热容量之差。
另外，当使检测用传感部65为高温时，由金属化合物64捕获的SOx放出，检测用传感部65被再生。因此，在该例中，通过使加热器69发热，而使检测用传感部65的温度上升，由此能够将检测用的传感部65再生。再者，该场合下，即使使样品气体的空燃比暂时为浓也能够将检测用传感部65再生。
在图1表示的实施例中，流入到SOx捕集催化剂8中的SOx被SOx捕集催化剂8捕获。因此，能够由SOx传感器16的输出值推定SOx捕集催化剂8的SOx中毒量。图7表示用于检测SOx捕集催化剂8的SOx中毒量的程序。
参照图7，首先，在步骤80中读出根据内燃机的运转状态算出的燃料喷射量。由该燃料喷射量可知被供给到样品气体生成室14内的燃料量。接着，在步骤81中算出使样品气体的空燃比为目标稀空燃比所需的目标空气供给量。接着，在步骤82中，控制空气泵15使得供给到样品气体生成室14内的空气量为该目标空气供给量。接着，在步骤83中读出例如在图3(D)中由V表示的SOx传感器16的输出值，在步骤84中由该输出值V推定SOx捕集催化剂8的SOx中毒量。
Claims (8)
1.一种内燃机的排气净化装置，所述内燃机在内燃机排气通路内配置有排气净化用催化剂，所述的内燃机的排气净化装置具备SOx传感器，由该SOx传感器的输出值推定流入到所述催化剂中的SOx量，所述SOx传感器具有传感部，并且可由该传感部的物性变化检测被该传感部捕获的硫的量，所述传感部利用比供给到燃烧室内的燃料量少的量的、且与该燃料量成比例的燃料生成检测硫用的样品气体，并捕获该样品气体中含有的硫。
2.根据权利要求1所述的内燃机的排气净化装置，其中，该样品气体的空燃比被维持为稀。
3.根据权利要求1所述的内燃机的排气净化装置，其中，为了使所述传感部的温度为容易以SOx的形式捕获硫的温度，样品气体的温度被提高。
4.根据权利要求1所述的内燃机的排气净化装置，其中，所述传感部由在捕获到硫时变成硫酸盐的金属化合物形成。
5.根据权利要求4所述的内燃机的排气净化装置，其中，所述金属化合物包括碱金属、碱土类金属、稀土类金属或贵金属的化合物。
6.根据权利要求1所述的内燃机的排气净化装置，其中，根据被捕获的硫的量而变化的所述传感部的物性，是由电阻所代表的电物性或由热容量和导热性所代表的热物性。
7.根据权利要求1所述的内燃机的排气净化装置，其中，所述传感部包括在捕获到硫时变成硫酸盐的检测用传感部、和本来就为硫酸盐的参照用传感部。
8.根据权利要求1所述的内燃机的排气净化装置，其中，由所述SOx传感器的输出值推定所述催化剂的SOx中毒量。
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| US8047063B2 (en) | 2011-11-01 |
| JP2008286002A (ja) | 2008-11-27 |
| WO2008143273A1 (ja) | 2008-11-27 |
| US20090320450A1 (en) | 2009-12-31 |
| CN101548075A (zh) | 2009-09-30 |
| EP2148051A1 (en) | 2010-01-27 |
| JP4710871B2 (ja) | 2011-06-29 |
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