CN1244671C - 锰从润滑剂源到燃料燃烧系统的转移 - Google Patents

锰从润滑剂源到燃料燃烧系统的转移 Download PDF

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CN1244671C
CN1244671C CNB031327737A CN03132773A CN1244671C CN 1244671 C CN1244671 C CN 1244671C CN B031327737 A CNB031327737 A CN B031327737A CN 03132773 A CN03132773 A CN 03132773A CN 1244671 C CN1244671 C CN 1244671C
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manganese
combustion
fuel
sulphur
lubricant
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CN1506614A (zh
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G·H·圭恩特
J·W·罗斯
V·J·加托
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Afton Chemical Intangibles LLC
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Ethyl Corp
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Abstract

本发明涉及一种将润滑剂源中的锰转移到燃料燃烧系统或燃烧系统产生的废气中的装置和方法。依据本发明,润滑剂中的锰将与燃烧产物中的磷、硫和/或铅相互作用。通过这一方式,锰可以将进入燃料或燃烧产物中、而且还会危害催化转化器、传感器和/或车载检测装置的有害物质清除或者使它们失去活性。本发明还将提高废气后处理系统的耐久性。

Description

锰从润滑剂源到燃料燃烧系统的转移
技术领域
本发明涉及一种将润滑剂源中的锰转移到燃料燃烧系统或燃烧系统产生的废气中的装置和方法。依据本发明,润滑剂中的锰将与燃烧产物中的磷、硫和/或铅相互作用。通过这一方式,锰可以将进入燃料或燃烧产物中的有害物质清除或者使它们失去活性,否则这些有害物质会危害催化转化器、传感器和/或车载检测装置。本发明还将提高废气后处理系统的耐久性。
背景技术
燃料燃烧系统存在的一个问题是,燃烧时燃料含有、或者获得、或者产生一种或多种金属(例如铅)、硫、和/或磷污染物,这些污染物将危害或恶化催化转化器、传感器或车载检测装置。
上述污染物导致的另一个问题是不合乎需要地增加了废气中的某些燃烧产物或副产物的含量。
还有一个问题就是上述污染物对后处理系统所产生的损害。这些污染物可能包括处在燃料或者空气中的元素磷、铅和硫,或者上述物质的化合物。污染物还可能从发动机或者燃烧系统的润滑剂中进入燃料、或者燃烧室、或者燃烧排出气流中,所说的润滑剂通常含有含磷和含硫的添加剂,以及与燃烧系统磨损有关的铅化合物。
众所周知的一个现象就是,车辆和其它燃烧系统消耗(即发动机燃烧)作为发动机或者燃烧系统运动部件的润滑剂的油类。润滑油进入燃烧系统和/或其排出气流中的途径也有很多种。很明显,润滑油中的多种组分或者添加剂也将被消耗或燃烧,而这些组分或者添加剂将对燃烧系统的催化剂、后处理系统和排放量产生不利的影响。
因此希望能抑止、减少或防止组分(例如来源于润滑剂源、空气或者燃料或者进入燃烧过程的其它物质中的磷、铅和/或硫)与燃烧排出气流之间的不利的相互作用,从而防止催化剂中毒、后处理系统故障和排放量增加。
发明内容
在一个实施方式中,本发明提供了一种方法来抑止、减少或防止组分(例如来源于润滑剂源、任何加工助剂或辅剂、燃料、燃料添加剂、空气或者进入燃烧过程的其它物质中的磷、铅和/或硫)与燃烧排出气流之间的不利的相互作用,从而防止催化剂中毒、后处理系统故障和/或排放量增加。
在另一个实施方式中,本发明提供了一种可以清除来自燃料或者燃料燃烧产物中的磷、铅和/或硫的系统。
而且,本发明还涉及一种可以提高燃烧系统后处理装置的耐久性的方法,该方法包括将烃类燃料的燃烧产物与含有锰的润滑剂接触,其中,润滑剂中的锰的量足以使锰和燃烧产物中的一种或多种选自磷、硫、铅或它们的化合物的污染物进行相互作用,并因此降低与后处理设备接触的一种或多种污染物的量。
本文中“锰”是指任何有机锰化合物或材料,包括但不局限于甲基环戊二烯基三羰基锰(MMT,购自Ethyl Corporation)、磺酸锰、石炭酸锰、水杨酸锰、烷基环戊二烯基三羰基锰、有机三羰基锰衍生物、烷基环戊二烯基锰衍生物、中性和高碱性的水杨酸锰、中性和高碱性的石炭酸锰、中性和高碱性的磺酸锰、羧酸锰,以及上述物质的组合物和混合物。锰优选以油溶性添加剂的形式存在于润滑剂中,其能够挥发并藉此进入燃烧室或排出气流中。它也可通过“大量”消耗的方式,也就是以通过阀导承或者围绕活塞环的方式进入燃烧室。在一个实施方式中,用少量的锰处理燃料或者其燃烧排出气,例如,在燃料或者燃烧排出气中锰的含量大约为20ppm或者更少。
本文中“基础油”是指可以选自下述物质的基础油:石蜡基础油、环烷基基础油、芳族基础油、聚α-烯烃、合成酯类和多羟基酯类,以及它们的混合物。在一个优选实施方式中,基础油含有少于或等于0.03wt%的硫,以及大于或等于90wt%的饱和物,其粘度指数大于或等于80并且小于或等于120。在另一个实施方式中,基础油含有小于或者等于0.03wt%的硫,以及大于或等于90wt%的饱和物,其粘度指数大于或等于120。而在一个更优选的实施方式中,基础油基本上不含硫。
本文中“清除”是指通过接触、结合、反应、掺混、化学键合、物理键合、粘附、聚结、附着、使失活、使惰性、消耗、合金化、收集、清洗、消耗或者任何其它方式或途径,使得第一种材料能使第二种材料不可利用或者利用性降低。
本文中“相互作用”是指清除。
本文中“使失去活性”是指清除。
本文中“烃类燃料”所指的烃类燃料例如,但不局限于柴油燃料、喷气式发动机燃料、醇类、醚类、煤油、低硫燃料、合成燃料(如Fischer-Tropsch燃料)、石油液化气、源自煤的燃料、基因工程生物燃料和农作物以及它们的提取物、天然气、丙烷、丁烷、发动机和航空无铅汽油、以及所谓的重整汽油(reformulated gasoline),其一般含有汽油沸程内的烃和可溶于燃料的氧化掺合剂,如醇、醚和其它合适的含氧有机化合物。适用于本发明的燃料的氧化剂包括甲醇、乙醇、异丙醇、叔丁醇、混合醇、甲基叔丁基醚、叔戊基甲基醚、乙基叔丁基醚和混合的醚类。使用时,重整汽油燃料中存在的氧化剂的量通常低于约25%(体积),其量优选可在总燃料中提供约0.5%~约5%(体积)的氧含量。这里,本文中“烃类燃料”或“燃料”也指汽油、船用燃料、煤(灰或浆)、原油、炼油“残渣”和副产物、原油提取物、危险废弃物、庭院修剪物和废弃物、木屑和锯末、农业废弃物、饲料、青贮饲料、塑料、和其它有机废品和/或副产物,以及上述物质的混合物,和它们在水、酒精和其它载流流体中的乳液、悬浮液和分散体。本文中“柴油燃料”是指选自以下物质的一种或多种燃料:柴油燃料、生物柴油、生物柴油衍生物燃料、合成柴油燃料,以及它们的混合物。烃类燃料优选基本上不含硫,这是指燃料中硫的含量平均不超过约30ppm。
本文中“燃烧系统”和“装置”是指,例如但不局限于,任何柴油-电力混合动力汽车、汽油-电力混合动力汽车、两冲程发动机、任何和所有燃烧器或燃烧装置,例如包括但不限于静态燃烧器、垃圾焚化炉、柴油燃料燃烧器、柴油燃料发动机、汽车柴油发动机、汽油燃料燃烧器、汽油燃料发动机、电厂发电机等。可能从本发明中获得益处的烃类燃料燃烧系统包括所有的燃烧装置、系统、设备和/或燃烧燃料的发动机。本文中“燃烧系统”也是指所有内部和外部燃烧设备、机器、发动机、涡轮发动机、喷气式发动机、焚化炉、锅炉、蒸发燃烧器、等离子燃烧系统、等离子弧、静态燃烧器等可以燃烧烃类燃料或烃类燃料可以在其中燃烧的装置。
本文中“接触”是指接触、使聚集、反应、络合、配合、结合、掺合、混合等的可以使两种或者更多种材料之间发生联系的方式,无论该方式是否发生物理或者化学反应或变化。
本文中“基本上不含磷和磷的化合物”是指元素磷或者磷的化合物在润滑剂中的含量小于约10ppm。磷的这种低含量在很多现有的润滑剂配方中是理想的,而且可以预料到,更低磷含量的润滑剂将是我们不断寻求的,或许是我们需要的。润滑剂中磷的含量优选介于1ppm和约1500ppm之间。润滑剂中更优选的磷含量介于500ppm和1200ppm之间。
本文中“后处理系统”或者“后处理装置”是指设计为对燃烧产物进行氧化、还原或其它方式的处理来接触来自燃烧室的燃烧产物的任何装置或系统。这种后处理系统例如但不局限于是汽车三元催化转化器、贫NOx捕捉器,催化柴油颗粒过滤器和连续再生技术柴油颗粒过滤器。“后处理系统”也包括象O2传感器和NOx传感器这样的辅助传感器。类似的汽油燃烧后处理系统是已知的,而且由于从本发明中获得了益处而被包含在上述的“后处理系统”中。
应该理解的是,前面的概述以及下面的详述都只是示例性和解释性的,其目的都是对本发明所要求保护的内容提供更进一步的解释。
附图说明
图1表示排出气中含或不含锰对催化剂上沉积的磷量的影响。
图2表示排出气中存在或不存在锰时,突围的烃、一氧化碳和NOx排放物的百分含量。
图3表示燃烧含锰汽油与燃烧不含锰的燃料的汽车相比的CO和NOx排放量。
具体实施方式
在一个更具体的实施方式中,本发明提供了一种方法来减少至少一种污染物的含量或者降低其有害影响,这些污染物选自磷、铅、硫及它们的化合物,它们存在于用润滑剂润滑的燃烧系统中烃类燃料燃烧时所产生的排出气流中。该方法包括如下步骤:(a)用润滑剂润滑燃烧系统,该润滑剂含有大量的、具有润滑粘度的基础油,和少量的一种或几种添加剂,所述的添加剂含有:(i)至少一种有机硫化合物,或者至少一种有机磷化合物,或者此二者,和(ii)至少一种锰源,(b)在燃烧系统中燃烧烃类燃料以产生燃烧产物,所述燃烧产物中含有至少一种选自硫、铅、磷和它们的化合物的物质;和(c)将锰与燃烧产物中的硫、铅、磷和它们的化合物进行接触,从而使锰与硫、铅、磷和/或它们的化合物发生相互作用。而正是锰与硫、铅、磷及它们的化合物之间的相互作用导致了污染物质被清除,并因此获得了很多有益效果。通过清除污染物获得的有益效果包括:保持了催化转化器、传感器、LNT以及DPF的性能。
如果汽车在燃料中含有锰的情况下行驶,例如汽油中加入了MMT燃料添加剂的情况,发现有较少的磷沉积到汽车的催化转化器上(参见图1)。图1中的图表显示,当燃料中的锰被燃烧时催化剂上沉积的磷较少。更具体地说,图1说明,当排出气中含有锰时,催化剂上沉积的磷的量减少了50%以上(从略小于4wt%到约1.5wt%)。这与前面的数据是一致的,表明锰在燃烧或排出气流中与磷结合形成了不会在催化剂上形成不渗透性釉层的、稳定的锰-磷或者硫酸锰类物质。催化剂上的磷越少,“突围”(即以未被转化的排放物形式通过)的排放物就越少。因此在排出气流中含有锰是我们所期望的。
图2中的排放数据表示的是废气中存在锰或不存在锰时,突围的烃、一氧化碳和NOx排放物的百分含量。随着磷危害的减少,催化剂的活性增加,突围出催化剂的污染物的量减少,从而导致排放量降低。图2清楚地表明,在含锰燃料燃烧所产生的排出气流中,不良排放量明显降低了。
图1和图2所示的试验是1993 Toyota Camry汽车靠基础燃料或是靠基础燃料加8.3mg Mn/L行驶100,000英里的试验。在累计行驶100,000英里之后拆开催化转化器并进行分析,以确定其长度方向各离散点上磷的重量。同时,也通过测量未转化的突围排放物的百分含量来对催化剂进行分析,以确定催化剂的效率。燃料中有锰(源自MMT)的汽车的催化转化器上沉积的磷较少,从而也导致未经转化的突围排放物较少。
从Ethyl Corporation进行的1992/1993 EPA Waiver Fleet测试中,可以得到更进一步的证据来表明在含锰润滑剂的燃烧产物中存在锰可以防磷和降低排放量。在该测试中,燃烧含锰汽油(锰来自8.3mg Mn/L的MMT燃料添加剂)的汽车与燃烧不含MMT锰源的基线燃料的汽车相比,其CO和NOx的排放量更低。(参见图3,其中使用:22辆汽车(成对);1993 Ford Escort TLEV,1993Toyota Camry,1992 Crown Victoria,1993 Honda Civic TLEV;汽车的选择是基于Automotive Company和EPA的评价,Public Docket A-9241,1993年11月9日;里程表计量燃料-300ppm S-使用汽油洁净剂-喷溅混入MMT;所有汽车用相同的检定燃料完成排放量检测)。转化器中催化剂的表面不能区分锰是源自燃料还是源自润滑剂,因为这两种材料同时在远离催化剂的上游燃烧。
在另一个测验中,两辆Ford Taurus汽车按照EPA通用动力试验驱动序列(Universal Dynamometer Driving Sequence,UDDS)进行了7个循环以上的行驶,之后分别收集全部的悬浮颗粒状(TSP)排出气颗粒排放物,并在LawrenceLivermore国家实验室用X射线吸收光谱(XAS)对过滤器进行分析,以确定排出气中存在的锰的种类。表1的数据表明了分析结果,其中主要的锰种类是磷酸盐和硫酸盐,这表明锰是与发动机润滑剂和燃料中的磷和硫相结合的。
     表1 由XAS测得的锰的种类(在排出气颗粒物中的wt%)
         汽车                  磷酸盐+硫酸盐
          1                         84
          2                         82
表1中的质量分析的置信度为95%+/-5%。
应该理解的是,那些依据本发明被润滑剂中的锰清除掉的污染物质可能来源于烃类燃料燃烧时使用的空气。在另一个实施方式中,那些依据本发明被锰清除掉的污染物可能来源于烃类燃料。而在本发明的另外一个实施方式中,被锰清除掉的污染物可能来源于用以润滑燃烧系统的润滑剂。
在一个具体实施方式中,用以清除污染物的润滑剂担载的锰可以通过放入、“漏入”、流入、渗入、推入或压入、抽入、浸入,或者吸入,或者其它有意或无意的方式而进入燃烧系统的燃烧室。在这一实施方式中,污染物在燃烧过程中间或者燃烧过程之后与锰相遇并发生相互作用,从而使污染物被清除。因此,当含锰的润滑剂在燃烧系统中的阀门周围溢出时,也就完成了本发明的方法的这一实施方式,其中阀门例如可以是,但不局限于汽车发动机的进气阀或排气阀。通过这种方式,锰与污染物相遇并相互作用,从而将污染物清除。
在另一个实施方式中,使锰有意或者无意地在含有污染物的燃烧产物离开燃烧室的途中与之相遇,通过这一方式可使得清除过程发生在燃烧系统的燃烧室外部。
在本发明的另一个实施方式中,锰从润滑剂中挥发出来,并被转移到含有燃料的燃烧室内。
在另一个实施方式中,燃烧系统采用了一个精密的再循环过程,曲轴箱中的蒸汽再循环进入燃烧室的多个进气歧管之一。以这种方式,使含有硫、磷和/或铅污染物的任何润滑剂在燃烧时或者在废气中与锰相遇并发生相互作用。
这样,在另一个测试中,一辆1997 Ford Taurus汽车按照EPA UDDS行驶了7个以上的循环,测验时使用的燃料含有8.3mg Mn/L,曲轴箱使用的发动机油含有1,000ppm的磷,通过质量平衡称量测试中消耗的磷和锰的总质量。收集废气排放物的TSP并进行分析,以确定过滤器上存在的锰和磷的质量。由此确定,在TSP过滤器上存在的磷与锰的摩尔比与二者在燃料和油中消耗的质量相等或相当。表2说明了计算出的消耗的P∶Mn摩尔比和过滤器上收集到的质量。
            表2 汽车行驶,油料消耗,锰消耗和摩尔比
          P∶Mn摩尔比            过滤器上测得的P∶Mn
             0.27                        0.32
本发明的另一个实施方式中提供了一种装置,用以实施一种能使排出气中存在的至少一种选自磷、铅、硫和它们的化合物的污染物的含量降低,或者能减少这些污染物质的有害作用的方法,其中该装置含有:(a)适于燃烧烃类燃料的燃烧室;(b)将烃类燃料引入燃烧室的装置;(c)将燃烧产物移出燃烧室的装置;和(d)一种润滑剂,含有大量具有润滑粘度的基础油和少量的一种或几种添加剂,其中添加剂含有:(i)至少一种有机硫化合物,或者至少一种有机磷化合物,或者此二者,和(ii)至少一种锰源。该装置还可含有一个后处理装置或系统。
依据本发明的一个实施方式,润滑剂中的有机硫化合物可以选自硫化烯烃,硫化的脂肪和植物油,硫化的不饱和酯和酰胺,无灰且含金属的二硫代氨基甲酸盐,取代的噻二唑,硫化的位阻酚,硫化烷基酚,中性含金属磺酸盐洗涤剂,高碱性含金属磺酸盐洗涤剂,中性含金属石炭酸盐洗涤剂,和高碱性含金属石炭酸盐洗涤剂,或者上述物质的结合物和混合物。
依据本发明的另一个实施方式,润滑剂中的有机磷化合物可以选自中性和高碱性的伯、仲及芳基二烷基二硫代磷酸锌(ZDDP),三烷基-及三芳基亚磷酸盐,混合烷基/芳基亚磷酸盐,烷基和芳基偶磷硫羟硫代硫酸盐,以及烷基和芳基偶磷硫代硫酸盐,以及上述物质的结合物或混合物。
已经发现,当燃烧系统的排出气流中存在源自甲基环戊二烯基三羰基锰的锰时,在催化剂之类的部件上检测到的磷可以大幅度减少。具体地说,本发明可以使后处理设备上检测到的这些污染物的量减少20%(重量)以上,更优选可减少60%到80%(重量)。这就使上述后处理设备或系统的耐久性能获得巨大的、非常令人满意的提高。
附图1、2和3是对本发明的多个方面的进一步说明,而并非对发明的限制。
通过研究本文所公开的本发明的说明书、附图和实施例,本发明的其它实施方式对于本领域的熟练技术人员而言是显而易见的。我们的意图是仅将说明书和附图认为是示范性的,而本发明的实际范围和精神由所附的权利要求来限定。

Claims (34)

1.一种减少烃类燃料在由润滑剂进行润滑的燃烧系统中燃烧时所产生的排出气流中至少一种选自磷、铅、硫及它们的化合物的污染物的危害作用的方法,该方法包括如下步骤:
(a)用润滑剂润滑燃烧系统,该润滑剂含有大量具有润滑粘度的基础油和少量的一种或几种添加剂,所述的添加剂含有:(i)至少一种有机硫化合物,或者至少一种有机磷化合物,或者此二者,和(ii)至少一种锰源;
(b)在燃烧系统中燃烧烃类燃料和润滑剂以产生燃烧产物,所述燃烧产物中含有锰和至少一种选自硫、铅、磷和它们的化合物的物质;
(c)将锰与燃烧产物中的硫、铅、磷和它们的化合物进行接触,
由此使锰与硫、铅、磷及它们的化合物发生相互作用。
2.如权利要求1所述的方法,其中燃烧产物中的硫、铅、磷及它们的化合物源自燃料。
3.如权利要求1所述的方法,其中燃烧产物中的硫、铅、磷及它们的化合物源自燃料燃烧时所用的空气。
4.如权利要求1所述的方法,其中燃烧产物中的硫、铅、磷及它们的化合物源自润滑剂。
5.如权利要求1所述的方法,其中的排出气流基本上不含磷及其化合物。
6.如权利要求1所述的方法,其中的燃烧系统还包括后处理系统。
7.如权利要求6所述的方法,其中后处理系统选自催化柴油颗粒过滤器和连续再生技术柴油颗粒过滤器。
8.如权利要求1所述的方法,其中的燃烧系统选自任何一种柴油-电力混合动力汽车、汽油-电力混合动力汽车、两冲程发动机、任何一种燃烧器或燃烧装置、静态燃烧器、垃圾焚化炉、柴油燃料燃烧器、柴油燃料发动机、汽车柴油发动机、汽油燃料燃烧器、汽油燃料发动机、电厂发电机、任何一种内部和外设的燃烧设备、机器、发动机、涡轮发动机、喷气式发动机、锅炉、焚化炉、蒸发燃烧器、等离子燃烧系统、等离子弧、静态燃烧器以及可以燃烧烃类燃料或者烃类燃料在其中被燃烧的装置。
9.如权利要求1所述的方法,其中的烃类燃料选自柴油燃料、生物柴油、生物柴油衍生物燃料、合成柴油燃料、喷气式发动机燃料、醇类、醚类、煤油、低硫燃料、合成燃料、费托燃料、液化石油气、源自煤的燃料、基因工程生物燃料和农作物以及它们的提取物、天然气、丙烷、丁烷、无铅发动机和航空汽油、含有汽油沸程内的烃和燃料可溶性的氧化掺和剂的重整汽油、汽油、船用燃料、煤(灰或浆)、原油、炼油“残渣”和副产物、原油提取物、危险废弃物、庭院修剪物和废弃物、木屑和锯末、农业废弃物、饲料、青贮饲料、塑料、有机废品,和上述物质的混合物,以及它们在水、酒精和其它载流流体中的乳液、悬浮液和分散体。
10.一种用以实施如权利要求1所述方法的装置,该装置包括:
(a)适于燃烧烃类燃料的燃烧室;
(b)将烃类燃料引入燃烧室的装置;
(c)将燃烧产物移出燃烧室的装置;和
(d)一种润滑剂,含有大量具有润滑粘度的基础油和少量的一种或几种添加剂,其中添加剂含有:(i)至少一种有机硫化合物,或者至少一种有机磷化合物,或者此二者,和(ii)至少一种锰源。
11.如权利要求10所述的装置,还包括后处理系统。
12.如权利要求11所述的装置,其中的后处理系统选自催化柴油颗粒过滤器和连续式再生技术柴油颗粒过滤器。
13.如权利要求10所述的装置,其中该装置选自任何一种柴油-电力混合动力汽车、汽油-电力混合动力汽车、两冲程发动机、任何一种燃烧器或燃烧装置、静态燃烧器、垃圾焚化炉、柴油燃料燃烧器、柴油燃料发动机、汽车柴油发动机、汽油燃料燃烧器、汽油燃料发动机、电厂发电机、任何一种内部和外设的燃烧设备、机器、发动机、涡轮发动机、喷气式发动机、锅炉、焚化炉、蒸发燃烧器、等离子燃烧系统、等离子弧、静态燃烧器以及可以燃烧烃类燃料或者烃类燃料在其中被燃烧的装置。
14.一种提高燃烧系统的后处理装置的耐久性的方法,该方法包括将烃类燃料和润滑剂在燃烧系统中燃烧的产物与含有足够量的锰的润滑剂接触,其中,润滑剂中的锰的量足以使锰和燃烧产物中的一种或多种选自磷、硫、铅或它们的化合物的污染物进行相互作用,从而降低与后处理设备接触的一种或多种污染物的量。
15.如权利要求14所述的方法,其中后处理装置上检测到的磷的量,与润滑剂中不含锰时检测到的磷量相比,减少了20重量%到80重量%。
16.如权利要求14所述的方法,其中后处理装置上检测到的硫的量,与润滑剂中不含锰时检测到的硫量相比,减少了20重量%到80重量%。
17.如权利要求14所述的方法,其中后处理装置上检测到的铅的量,与润滑剂中不含锰时检测到的铅量相比,减少了20重量%到80重量%。
18.如权利要求1所述的方法,其中润滑剂中的有机硫化合物选自硫化烯烃,硫化的脂肪和植物油,硫化的不饱和酯和酰胺,无灰且含金属的二硫代氨基甲酸盐,取代的噻二唑,硫化的位阻酚,硫化烷基酚,中性含金属的磺酸盐洗涤剂,高碱性含金属磺酸盐洗涤剂,中性含金属石炭酸盐洗涤剂,和高碱性含金属石炭酸盐洗涤剂,或者上述物质的结合物和混合物。
19.如权利要求1所述的方法,其中润滑剂中的有机磷化合物选自中性和高碱性的伯、仲和芳基二烷基二硫代磷酸锌(ZDDP),三烷基-和三芳基亚磷酸盐,混合烷基/芳基亚磷酸盐,烷基和芳基偶磷硫羟硫代硫酸盐,以及烷基和芳基偶磷硫代硫酸盐,以及上述物质的结合物或混合物。
20.如权利要求1所述的方法,其中润滑剂中的锰源选自甲基环戊二烯基三羰基锰,烷基环戊二烯基三羰基锰,有机三羰基锰的衍生物,烷基环戊二烯基锰的衍生物,中性和高碱性的水杨酸锰,中性和高碱性的石炭酸锰,中性和高碱性磺酸锰,羧酸锰,以及上述物质的结合物和混合物。
21.如权利要求1所述的方法,其中,基础油选自石蜡基础油、环烷基础油、芳族基础油、聚α-烯烃、合成酯类和多羟基酯类,以及它们的混合物。
22.如权利要求1所述的方法,其中,基础油含有小于或等于0.03wt%的硫,以及大于或等于90wt%的饱和物,其粘度指数大于或等于80并且小于或等于120。
23.如权利要求1所述的方法,其中,基础油含有小于或等于0.03wt%的硫,以及大于或等于9wt%的饱和物,其粘度指数大于或等于120。
24.如权利要求1所述的方法,其中,基础油基本上不含硫。
25.如权利要求1所述的方法,其中,烃类燃料含有少量的硫。
26.如权利要求1所述的方法,其中,烃类燃料基本上不含硫。
27.如权利要求1所述的方法,其中,烃类燃料含有少量的硫,并且进一步用氧化剂进行了处理。
28.如权利要求1所述的方法,其中,烃类燃料基本上不含硫,并且进一步用氧化剂进行了处理。
29.如权利要求1所述的方法,其中,烃类燃料含有少量的硫,并且进一步用少量的锰进行了处理。
30.如权利要求1所述的方法,其中,烃类燃料基本上不含硫,并且进一步用少量的锰进行了处理。
31.一种减少存烃类燃料在由润滑剂润滑的燃烧系统中燃烧时所产生的排出气流中至少一种选自磷、铅、硫及它们的化合物中的污染物的有害影响的方法,该方法包括如下步骤:
(a)用润滑剂润滑燃烧系统,该润滑剂含有大量具有润滑粘度的基础油和少量的一种或几种添加剂,所述的添加剂含有:(i)至少一种有机硫化合物,或者至少一种有机磷化合物,或者此二者,和(ii)至少一种锰源;其中锰从润滑剂中挥发并被携带进入所述燃烧系统的燃烧室中;
(b)在燃烧系统中燃烧烃类燃料以产生燃烧产物,所述燃烧产物中含有至少一种选自硫、铅、磷和它们的化合物的物质;
(c)将锰与燃烧产物中的硫、铅、磷和它们的化合物进行接触,从而使锰与硫、铅、磷和它们的化合物发生相互作用。
32.一种减少烃类燃料在由润滑剂润滑的燃烧系统中燃烧时所产生的排出气流中至少一种选自磷、铅、硫及它们的化合物中的污染物的有害影响的方法,该方法包括如下步骤:
(a)用润滑剂润滑燃烧系统,该润滑剂含有大量具有润滑粘度的基础油和少量的一种或几种添加剂,所述的添加剂含有:(i)至少一种有机硫化合物,或者至少一种有机磷化合物,或者此二者,和(ii)至少一种锰源;其中锰通过大量消耗而进入所述燃烧系统的燃烧室中;
(b)在燃烧系统中燃烧烃类燃料以产生燃烧产物,所述燃烧产物中含有至少一种选自硫、铅、磷和它们的化合物的物质;
(c)将锰与燃烧产物中的硫、铅、磷和它们的化合物进行接触,从而使锰与硫、铅、磷和它们的化合物发生相互作用。
33.权利要求1的方法,其中燃烧系统利用精密循环工艺,从而使曲轴箱中的蒸气循环进入进气歧管或燃烧室中。
34.权利要求6的方法,其中减少了所述至少一种污染物对后处理系统的有害影响。
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