CN111173597B - 内燃机废气的后处理方法和内燃机 - Google Patents

内燃机废气的后处理方法和内燃机 Download PDF

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CN111173597B
CN111173597B CN201911099732.XA CN201911099732A CN111173597B CN 111173597 B CN111173597 B CN 111173597B CN 201911099732 A CN201911099732 A CN 201911099732A CN 111173597 B CN111173597 B CN 111173597B
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catalytic converter
internal combustion
oxidation catalytic
combustion engine
exhaust gas
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A.德林
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MAN Energy Solutions SE
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Abstract

燃烧气体燃料的内燃机(1)的废气的后处理方法，所述废气即以气体燃料操作模式操作的燃气发动机或双燃料发动机的废气，其中废气通过CH4‑氧化催化转化器(7)处理，CH4‑氧化催化转化器(7)包含烧绿石和/或β多晶型A‑型(BEA)沸石和/或钴‑镍氧化物用于CH4‑氧化并因此作为催化活性化合物，且其中要通过CH4‑氧化催化转化器处理的废气具有基于氮氧化物总比例为至少15%的NO2比例。

Description

内燃机废气的后处理方法和内燃机
技术领域
本发明的方法涉及燃烧气体燃料的内燃机的废气的后处理方法，所述废气即以气体燃料操作模式操作的燃气发动机或双燃料发动机的废气。本发明另外涉及内燃机，即燃气发动机或双燃料发动机。
背景技术
在气体燃料操作模式的燃气发动机和双燃料发动机中燃烧气体燃料，例如天然气。利用此类燃烧气体燃料的内燃机，由于气体燃料的不完全燃烧，会出现不希望的CH4(甲烷)排放。由于甲烷代表强温室气体，因此，使用燃烧气体燃料的内燃机，必须将向环境中的CH4排放保持为尽可能低。
从实践已知处理废气，废气通过CH4-氧化催化转化器离开燃烧气体燃料的内燃机的气缸，以在CH4-氧化催化转化器中将CH4置换。在从实践已知的内燃机中，特别是铂和/或钯在CH4-氧化催化转化器中用于CH4氧化，并因此作为具有铂族金属的催化活性化合物。通常，在从实践已知的内燃机中，用铂族金属装填CH4-氧化催化转化器通常达到超过7克铂和/或钯每升CH4-氧化催化转化器体积。
这是导致高成本的事物。另外，从实践已知的这种CH4-氧化催化转化器的操作时间相对较短，因为可进入CH4-氧化催化转化器区域的硫氧化物会使铂族金属的催化活性化合物失活。因此，用从实践已知的内燃机会限制减少CH4排放的可能性。
从DE 10 2015 001 495 A1已知一种用于操作内燃机的方法，其中燃烧气体燃料。废气通过CH4-氧化催化转化器处理，其中调节废气中的NO2比例，使得在CH4-氧化催化转化器的上游，废气中总氮氧化物中的NO2比例达到至少15%。
DE 10 2015 001 495 A1的CH4-氧化催化转化器优选包含Cer和/或钴和/或铜和/或铁作为活性组分用于CH4-氧化，它们优选嵌入结构 MOR、FER、PER、NFI、LTL、LAU、CHI或CHK的沸石基质中。
需要进一步改善废气中CH4的分解，以减少使用气体燃料操作的内燃机的CH4排放。
发明内容
由此出发，本发明基于以下目的：建立燃烧气体燃料的内燃机的废气的新型后处理方法和相应的内燃机。
这个目的通过根据本申请的方法解决。
根据本发明，废气通过CH4-氧化催化转化器处理，CH4-氧化催化转化器包含烧绿石和/或β多晶型A-型(BEA)沸石和/或钴-镍氧化物，用于CH4-氧化并因此作为催化活性化合物。
根据本发明，要通过CH4-氧化催化转化器处理的废气具有基于氮氧化物总比例为至少15%的NO2比例。
利用在此提出的本发明，为了减少CH4排放，其中燃烧气体燃料的内燃机的废气以限定的NO2比例通过CH4-氧化催化转化器处理，CH4-氧化催化转化器包含烧绿石和/或BEA沸石和/或钴-镍氧化物用于CH4-氧化并因此作为催化活性化合物。在此，本发明基于这样的认识：利用这种CH4-氧化催化转化器，可用至少一种以上催化活性化合物最佳地分解CH4，即，特别是在要通过CH4-氧化催化转化器处理(即，在CH4-氧化催化转化器的上游)的废气中的NO2比例基于氮氧化物总比例达到至少15%时。
根据有利的进一步研发，CH4-氧化催化转化器因此包含烧绿石作为催化活性化合物用于CH4-氧化。优选烧绿石包含选自下组的至少一种烧绿石：Sm2Zr2O7、Sm2Mo2O7、La2Ti2O7、La2CoxSn2-xO7-δ、La2CoxZr2-xO7-δ、Mn2CoxZr2-xO7-δ、Pr2Ru2O7、ZrTiGd2O7、Pr2Co2O7和Pr2CoxZr2-xO7-δ，其中0≤δ≤2。这种CH4-氧化催化转化器，与在CH4-氧化催化转化器上游以限定的方式调节的废气中的NO2比例相结合，实现CH4的最佳分解。
根据有利的进一步研发，烧绿石和/或β多晶型A-型(BEA)沸石的元素由稀土金属和/或铁和/或钴和/或镍和/或铜取代。这也对在CH4-氧化催化转化器中CH4最佳地分解起作用。
根据有利的进一步研发，CH4-氧化催化转化器包含钴-镍化合物CoxNiy，优选作为氧化物，用于CH4-氧化并因此作为催化活性化合物，其中1≤x≤10，优选1≤x≤4，其中0≤y≤9，优选1≤y≤4，并且优选x+y≤10，优选x+y≤8，特别优选x+y≤6。在CH4-氧化催化转化器中用这种钴-镍氧化物作为催化活性化合物，CH4也可最佳地分解，即，特别是在CH4-氧化催化转化器上游的废气中的NO2比例基于氮氧化物总比例达到至少15%时。
根据有利的进一步研发，通过燃烧气体燃料的内燃机的至少一个燃烧参数和/或在CH4-氧化催化转化器的上游通过NO-氧化催化转化器来调节废气中的NO2比例。由此，可特别有利地在CH4-氧化催化转化器的上游调节废气中的NO2比例。
根据有利的进一步研发，在CH4-氧化催化转化器上游的废气通过SCR催化转化器处理，其中在CH4-氧化催化转化器下游和SCR催化转化器上游将NH3或NH3前体物质引入废气。经由SCR催化转化器，在已通过CH4-氧化催化转化器处理的废气中，氮氧化物比例可随后减小。
根据本发明的内燃机在本申请中限定。
本发明优选的进一步研发可自以下描述得出。
附图说明
本发明的示例性实施方案通过附图更详细地说明，但不限于此。其中显示：
图1为根据本发明的内燃机的高度概略显示的视图，用于说明根据本发明的内燃机废气的后处理方法。
具体实施方案
本发明涉及一种内燃机，在所述内燃机中燃烧气体燃料。另外，本发明涉及燃烧气体燃料的内燃机的废气的后处理方法。
图1显示根据本发明的内燃机1的高度概略显示的图。内燃机1包含至少一个具有气缸3的气缸体2。在内燃机1的气缸3中燃烧气体燃料，例如天然气。内燃机1是以气体燃料操作模式操作的燃气发动机或双燃料发动机。
图1显示有进料4，该气体燃料被送到内燃机的气缸3，特别是增压空气和燃气(gas)的混合物。排放5显示，在燃烧期间产生的废气从气缸3排放，并通过内燃机1的废气后处理系统6进行处理。
废气后处理系统6包含CH4-氧化催化转化器7。CH4-氧化催化转化器包含烧绿石和/或β多晶型A-型(BEA)沸石和/或钴-镍氧化物，用于CH4-氧化并因此作为催化活性化合物。
要通过CH4-氧化催化转化器7处理的废气包含基于废气中氮氧化物总比例为至少15%的NO2比例，优选至少30%，特别优选至少50%。
在所示的示例性实施方案中，废气后处理系统6包含在CH4-氧化催化转化器7上游的NO-氧化催化转化器8，以便首先通过NO-氧化催化转化器8处理离开内燃机1的气缸3的废气，并借助于NO-氧化催化转化器8，将基于废气中氮氧化物总比例的废气中NO2的比例调节到至少15%，优选到至少30%，特别优选到至少50%。
作为对NO-氧化催化转化器8的替代或补充，也可通过燃烧气体燃料的内燃机1的燃烧参数来调节废气中的NO2比例。
根据本发明的有利的进一步研发，CH4-氧化催化转化器至少包含烧绿石用于CH4-氧化。
在此，烧绿石至少包含选自下组的烧绿石：
Sm2Zr2O7,
Sm2Mo2O7,
La2Ti2O7,
La2CoxSn2-xO7-δ,
La2CoxZr2-xO7-δ,
Mn2CoxZr2-xO7-δ,
Pr2Ru2O7,
ZrTiGd2O7,
Pr2Co2O7和
Pr2CoxZr2-xO7-δ
其中0≤δ≤2 。
根据本发明的有利的进一步研发，CH4-氧化催化转化器包含β多晶型A-型(BEA)沸石，作为对烧绿石的补充或替代。
特别是在CH4-氧化催化转化器包含烧绿石和/或BEA沸石用于CH4-氧化并因此作为催化活性化合物时，烧绿石和/或BEA沸石的元素优选由稀土金属和/或用铁和/或用钴和/或用镍和/或用铜取代。另外，烧绿石和/或BEA沸石可富含Rh、Ru、Ir、Os、Bi、Zn、Gd，因为在烧绿石和/或BEA沸石中使用这些元素。
另外，通过加入碱金属和碱土金属，可提高CH4-氧化催化转化器7的热稳定性。因此，除了烧绿石和/或BEA沸石外，CH4-氧化催化转化器7也可包含碱金属和碱土金属。
根据本发明的有利的进一步研发，CH4-氧化催化转化器7包含钴-镍化合物CoxNiy，用于CH4-氧化并因此作为催化活性化合物，其中已证明氧化形式是有利的。
以下适用于钴-镍化合物CoxNiy：
1 ≤ x ≤ 10，优选1 ≤ x ≤ 4，
0 ≤ y ≤ 9，优选1 ≤ y ≤ 4，
X + y ≤ 10，优选x + y ≤ 8，特别优选x + y ≤ 6 。
可存在钴-镍化合物 CoxNiy，特别是其氧化物，作为对烧绿石和/或β多晶型A-型(BEA)沸石的替代或补充。
作为上述催化活性组分的基质，单独或组合的Al2O3、TiO2、SiO2和WO3是可能的。
在该示例性实施方案中，在CH4-氧化催化转化器的下游布置SCR催化转化器9，通过它处理离开CH4-氧化催化转化器7的废气，用于减小废气中的氮氧化物比例。在此，在CH4-氧化催化转化器7下游和SCR催化转化器9上游的废气的流动方向上可见布置用于将NH3或NH3前体物质引入废气的引入装置10，以有效去除或减少在SCR催化转化器9区域中的废气中的氮氧化物。
利用在此提出的本发明，在燃烧气体燃料的内燃机的废气中CH4的有效分解是可能的，即，在CH4-氧化催化转化器的区域中不必使用铂族金属的金属，例如铂和/或钯。
在用于分解CH4的催化活性组分中，在每种情况下，铂和钯的比例分别小于5%，优选小于3%，最优选小于1%。根据有利的进一步研发，用于CH4分解的活性组分中铂和钯的总和的比例小于5%，有利地小于3%，最有利地小于1%。
参考数字列表
1 内燃机
2 气缸体
3 气缸
4 进料
5 排放
6 废气后处理系统
7 CH4-氧化催化转化器
8 NO-氧化催化转化器
9 SCR催化转化器
10 引入装置。

Claims (20)

1.燃烧气体燃料的内燃机(1)的废气的后处理方法，所述废气即以气体燃料操作模式操作的燃气发动机或双燃料发动机的废气，
其中废气通过CH4-氧化催化转化器(7)处理，CH4-氧化催化转化器(7)包含烧绿石、β多晶型A-型沸石和钴-镍化合物用于CH4-氧化并因此作为催化活性化合物，
其中要通过CH4-氧化催化转化器处理的废气具有基于氮氧化物总比例为至少15％的NO2比例，
其中烧绿石用于CH4-氧化并且至少包含选自下组的烧绿石：
Sm2Zr2O7、Sm2Mo2O7、La2Ti2O7、La2CoxSn2-xO7-δ、La2CoxZr2-xO7-δ、Mn2CoxZr2-xO7-δ、Pr2Ru2O7、ZrTiGd2O7、Pr2Co2O7和Pr2CoxZr2-xO7-δ，其中0≤δ≤2，
其中钴-镍化合物是COxNiy，
其中1≤x≤10，
其中0≤y≤9，
其中x+y≤10和
其中在用于分解CH4的催化活性组分中，铂和钯的比例小于5％。
2.根据权利要求1所述的方法，其中1≤x≤4。
3.根据权利要求1所述的方法，其中1≤y≤4。
4.根据权利要求1所述的方法，其中钴-镍化合物是COxNiy的氧化形式。
5.根据权利要求1所述的方法，其特征在于，在CH4-氧化催化转化器(7)的上游，要通过CH4-氧化催化转化器(7)处理的废气具有基于氮氧化物总比例为至少30％的NO2比例。
6.根据权利要求1所述的方法，其特征在于，在CH4-氧化催化转化器(7)的上游，要通过CH4-氧化催化转化器(7)处理的废气具有基于氮氧化物总比例为至少50％的NO2比例。
7.根据权利要求1至6中任一项所述的方法，其特征在于，烧绿石和/或β多晶型A-型沸石的元素由稀土金属和/或铁和/或钴和/或镍和/或铜取代。
8.根据权利要求1所述的方法，其特征在于，x+y≤8。
9.根据权利要求1所述的方法，其特征在于，x+y≤6。
10.根据权利要求1至6中任一项所述的方法，其特征在于，
通过燃烧气体燃料的内燃机(1)的至少一个燃烧参数来调节废气中的NO2比例，和/或通过NO-氧化催化转化器(8)调节CH4-氧化催化转化器(7)上游的废气中的NO2比例。
11.根据权利要求1至6中任一项所述的方法，其特征在于，在CH4-氧化催化转化器(7)下游的废气通过SCR催化转化器(9)处理，其中在CH4-氧化催化转化器(7)下游和SCR催化转化器(9)上游将NH3或NH3前体物质引入废气。
12.一种内燃机(1)，即燃气发动机或双燃料发动机，
具有气缸(3)，其中气体燃料可燃，
具有CH4-氧化催化转化器(7)，废气通过它可处理，CH4-氧化催化转化器(7)包含烧绿石、β多晶型A-型沸石和钴-镍化合物用于CH4-氧化并因此作为催化活性化合物，
其中，内燃机和/或在CH4-氧化催化转化器(7)上游的NO-氧化催化转化器(8)在要通过CH4-氧化催化转化器(7)处理的废气中调节基于氮氧化物总比例的NO2比例为至少15％，
其中烧绿石用于CH4-氧化并且至少包含选自下组的烧绿石：
Sm2Zr2O7、Sm2Mo2O7、La2Ti2O7、La2CoxSn2-xO7-δ、La2CoxZr2-xO7-δ、Mn2CoxZr2-xO7-δ、Pr2Ru2O7、ZrTiGd2O7、Pr2Co2O7和Pr2CoxZr2-xO7-δ，其中0≤δ≤2，
其中钴-镍化合物是COxNiy，
其中1≤x≤10，
其中0≤y≤9，
其中x+y≤10和
其中在用于分解CH4的催化活性组分中，铂和钯的比例小于5％。
13.根据权利要求12所述的内燃机，其中1≤x≤4。
14.根据权利要求12所述的内燃机，其中1≤y≤4。
15.根据权利要求12所述的内燃机，其中钴-镍化合物是COxNiy的氧化形式。
16.根据权利要求12所述的内燃机，其中x+y≤8。
17.根据权利要求16所述的内燃机，其中钴-镍化合物是COxNiy的氧化形式。
18.根据权利要求16所述的内燃机，其中x+y≤6。
19.根据权利要求12至18中任一项所述的内燃机，其特征在于，烧绿石和/或β多晶型A-型沸石的元素由稀土金属和/或铁和/或钴和/或镍和/或铜取代。
20.根据权利要求12至18中任一项所述的内燃机，其特征在于，
在CH4-氧化催化转化器(7)的下游布置SCR催化转化器(9)，
在CH4-氧化催化转化器(7)的下游和SCR催化转化器(9)的上游布置引入装置(10)，用于将NH3或NH3前体物质引入废气。
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