CN101250446A - 减少在燃烧含醇燃料的发动机中的沉积物的方法和组合物 - Google Patents
减少在燃烧含醇燃料的发动机中的沉积物的方法和组合物 Download PDFInfo
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- CN101250446A CN101250446A CNA2008100805467A CN200810080546A CN101250446A CN 101250446 A CN101250446 A CN 101250446A CN A2008100805467 A CNA2008100805467 A CN A2008100805467A CN 200810080546 A CN200810080546 A CN 200810080546A CN 101250446 A CN101250446 A CN 101250446A
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Abstract
本公开提供了用于减少在燃烧包含乙醇和腐蚀抑制剂的燃料的发动机中沉积物形成的组合物和方法。所述方法包括:(a)将该燃料与至少一种选自琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂和聚亚烷基胺分散剂的分散剂燃料添加剂相混合,和(b)在该发动机中燃烧该燃料和该至少一种分散剂燃料添加剂,其中与燃烧具有腐蚀抑制剂但不含该至少一种分散剂燃料添加剂的含醇燃料时发生的沉积物形成相比,减少了沉积物的形成。本公开还提供了用于减少在燃烧包含乙醇、腐蚀抑制剂和分散剂的发动机中沉积物形成的组合物和方法。
Description
相关申请
本申请要求2007年2月22日提出的美国临时申请号60/891,172的优先权。
技术领域
本公开涉及分散剂燃料添加剂在含醇和腐蚀抑制剂的燃料中的应用。该分散剂燃料添加剂提高了所形成的燃料的性能,并提高了在内燃机中使用不同量乙醇作为燃料对消费者和环境的益处。此外,本公开涉及十二烯基琥珀酸(DDSA)腐蚀抑制剂在含醇燃料中的应用。特别地,本公开提供了用于减少在燃烧包含醇(例如乙醇)和腐蚀抑制剂的燃料的发动机中的沉积物形成的组合物和方法。
背景技术
乙醇单独或在汽油混合物中的应用会在设计用于操作通常称为汽油的更非极性的烃类石油馏分的燃料装置方面产生新的问题。乙醇或含乙醇燃料的极性、腐蚀性、粘性、摩擦性质和可能的导电性会在燃料工业中产生新的问题和新的需求。
讨论的汽油和乙醇的通常混合物是15%汽油和85%乙醇,通常称作“E85”燃料(下文称作“E85”)。其它乙醇燃料可以包括例如10%乙醇(E10)和100%乙醇(E100)。
广泛采用设计用于防止人类消耗的添加剂处理商用乙醇。经过这种处理的乙醇称作变性醇(或变性乙醇),通常的变性剂包括汽油、汽油组分和煤油。在27 CFR 21.24中详细说明了其它用于使燃料乙醇不适于饮料用途的变性剂。
在汽油燃料中使用不同程度的乙醇会造成以下方面的问题,例如增加发动机沉积物、燃料稳定性、腐蚀、燃料经济性、燃料驱动性能、发光度、燃料经济性、反乳化性、点燃、驱动性能、抗氧化性、换油期限、达到CARB标准、达到Top-Tier汽车制造商标准、达到US EPA标准、溶解性、组分相容性、燃料管堵塞、发动机耐久性、发动机磨损和喷射器结垢,在燃料中添加某种燃料添加剂会将这些得以改善。
汽车制造商和其它部门的研究表明低pHe的乙醇(在E-85和E-10混合物中)会有助于使某种燃料系统部件加速腐蚀。尽管ASTM标准将总酸度(作为乙酸)限定为0.007质量%(56mg/L),但这一标准并不总是足以限定更腐蚀性的硫基酸。符合ASTM酸度标准的乙醇可以仍是低pHe的。这种加速腐蚀促使使用腐蚀抑制剂来缓冲乙醇并保护燃料分配系统的金属部件;然而,这些会造成不符合要求的发动机沉积物的形成。因此,通常需要缓冲剂。
DCI-11是一种在市场上可得到的腐蚀抑制剂和缓冲剂,由Innospec(以前的Associated Octel)销售,并用于燃料中。然而,包含这种和其它腐蚀抑制剂的含乙醇燃料的燃烧产生了发动机沉积物的问题。这些沉积与传统的由于燃料和润滑剂降解和/或燃烧形成的沉积物非常不同。
因此需要对在燃烧具有腐蚀抑制剂或汽油-乙醇腐蚀抑制剂混合物的含乙醇燃料的发动机中形成的这些新的和未预期的发动机沉积物的问题的解决方案。还需要保持DCI-11以缓冲在含乙醇燃料中存在的酸性组分(例如尤其是乙酸和/或硫基酸)但是同时克服该新的和未预期的沉积物形成的问题。
发明内容
此处所示的一种实施方式提供了用于减少或抑制在燃烧含乙醇燃料(包括但不局限于E100、E85、E50等直至E10,以及痕量乙醇在汽油中的混合物)的发动机(或发动机组件)中的源于腐蚀抑制剂的沉积物的燃料添加剂。
此处所示的另一实施方式提供了一种用于减少或抑制在燃烧含腐蚀抑制剂和乙醇的燃料(包括但不局限于E100、E85、E50等直至E10,以及痕量乙醇在汽油中的混合物)的发动机(或发动机组件)中的沉积物的分散剂燃料添加剂。适合的分散剂燃料添加剂包括琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂、聚亚烷基胺分散剂和聚亚异丁基胺分散剂。
在另一实施方式中,观察到该分散剂或其混合物在减少或阻止在燃烧含乙醇且进一步包含用作腐蚀抑制剂的至少一种有机酸和至少一种胺或其盐的组合的燃料的发动机中形成的发动机沉积物的产生。
在此处的一种实施方式中,该燃料组合物中的乙醇含量为约74~约85%。在另一实施方式中,该燃料为100%乙醇,在另一实施方式中,该燃料组合物中的乙醇含量约为50%,或约50%~约74%。
另一实施方式提供了一种用于改善腐蚀抑制和/或用于减少在内燃机中的发动机沉积物的形成的方法,所述方法包括在所述发动机中燃烧一种包含汽油、乙醇和至少一种分散剂燃料添加剂的燃料组合物。此处所用的分散剂燃料添加剂能够有效防止或最小化在内燃机中与含乙醇和腐蚀抑制剂的燃料接触的金属表面和某些塑料或合成部件或表面的腐蚀和/或其上的沉积物。例如燃料泵、阀门、衬垫、浮筒装置、继电器或信号装置、量器、筛网、过滤器、进气阀、活塞及其它的部件都会遭受一定程度的腐蚀和/或沉积。该腐蚀和/或沉积会取决于暴露的类型和时间、暴露表面的化学性质、和乙醇和腐蚀抑制剂在燃料中的浓度而变化。通过本公开,用于含乙醇燃料的燃料添加剂包或浓缩物可以设计用于减少在这些发动机中的腐蚀和沉积物的形成。此处的燃料添加剂浓缩物可以包括一种或多种腐蚀抑制剂、分散剂和稀释剂,该稀释剂可以为油、燃料、汽油、乙醇、溶剂、载液、或其它能在汽油发动机中燃烧的物质。
此处提供了一种用于含乙醇燃料的燃料添加剂包或浓缩物,所述浓缩物包括一种或多种此处所述的腐蚀抑制剂和稀释剂,该稀释剂可以为油、燃料、汽油、乙醇、溶剂、载液、或其它能在汽油发动机中燃烧的液体物质。
因此,在此处的一种实施方式中,提供了一种包含乙醇和分散剂的燃料添加剂浓缩物,用于包含此处所限定的腐蚀抑制剂的汽油中,腐蚀抑制剂包括但不局限于具有由有机酸或二酸和胺、二胺或多胺结合而成的产物的那些物质。
因此,在此处的另一实施例中,提供了一种用于减少在燃烧含乙醇燃料的内燃机中的腐蚀和/或由腐蚀抑制剂产生的沉积物的组合物,所述组合物包含汽油、乙醇和一种或多种选自以下的物质:琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂、聚亚烷基胺分散剂和聚亚异丁基胺分散剂。
在另一实施方式中,一种用于减少在燃烧含醇燃料组合物的内燃机中沉积物的形成的方法,可以包括将该燃料与十二烯基琥珀酸(DDSA)腐蚀抑制剂混合,和在该发动机中燃烧该燃料和DDSA腐蚀抑制剂。与燃烧具有基本不合DDSA腐蚀抑制剂的腐蚀抑制剂的含醇燃料组合物时发生的沉积物形成相比,可以减少沉积物的形成。
在另一实施方式中,一种用于减少在燃烧含醇燃料的内燃机中沉积物形成的组合物可以包括DDSA腐蚀抑制剂和醇。
在另一实施方式中,一种燃料可以包含一种或多种醇、汽油和DDSA腐蚀抑制剂。
本发明包括以下方面:
1.一种用于减少在燃烧包含腐蚀抑制剂的含醇燃料组合物的内燃机中沉积物形成的方法,所述方法包括:
(a)将该燃料与至少一种选自琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂和聚亚烷基胺分散剂的分散剂燃料添加剂相混合,和
(b)在该发动机中燃烧该燃料和该至少一种分散剂燃料添加剂,
其中与燃烧具有腐蚀抑制剂但不含该至少一种分散剂燃料添加剂的含醇燃料时发生的沉积物形成相比,减少了沉积物的形成。
2.方面1的方法,其中该燃料进一步包含汽油。
3.方面1的方法,其中该醇选自甲醇、乙醇、丙醇、丁醇及其任意组合的混合物。
4.方面1的方法,其中该醇是乙醇。
5.方面4的方法,其中该燃料组合物中的乙醇含量为约10重量%~约100重量%。
6.方面4的方法,其中该燃料组合物中的乙醇含量为约15重量%~约85重量%。
7.方面4的方法,其中该燃料组合物中的乙醇含量为约74重量%~约85重量%。
8.方面1的方法,其中该腐蚀抑制剂包含十二烯基琥珀酸(DDSA)。
9.方面1的方法,其中该腐蚀抑制剂选自具有结构NH2(CH2)n-NH-(CH2)m-O-C8-10的那些物质,其中n和m独立地为1~约10。
10.方面1的方法,其中该腐蚀抑制剂选自具有结构NH2(CH2)n-NH-C8-10的那些物质,其中n为1~约10。
11.方面1的方法,其中该腐蚀抑制剂包含将羧酸或二酸与胺、二胺或多胺混合的产物。
12.方面1的方法,其中该腐蚀抑制剂具有小于700的分子量,选自单胺、二胺、三胺、多胺、醚胺、亚胺、咪唑啉、噻二唑、一元羧酸、二元羧酸、对-亚苯基二胺、二环己基胺、烷基取代的琥珀酸酐和酸、及其混合物和反应产物和其盐。
13.方面1的方法,其中该聚亚烷基胺分散剂包括聚亚异丁基胺分散剂。
14.方面1的方法,其中该方法进一步包括:
将该燃料与至少一种选自以下的燃料添加剂混合:酚;受阻酚;聚烯烃胺;芳基胺;二苯基胺;一元羧酸;二元羧酸;多元羧酸;氧化烷基酚树脂;甲醛与4-(1,1-二甲基乙基)苯酚、甲基环氧乙烷和环氧乙烷的聚合物;选自四乙基铅、甲基环戊二烯基三羰基锰、叠氮化物、过氧化物和硝酸烷基酯的辛烷值增强剂;单酯;二酯;醚;酮;二醚;聚醚;甘醇二甲醚;二元醇;环氧乙烷;C1-C8脂肪族烃;环氧丁烷;环氧丙烷;环氧乙烷;环氧化物;丁烷;戊烷;二甲苯;一氧化二氮;硝基甲烷;苯酚盐;水杨酸盐;磺酸盐;壬基苯酚乙氧化物;可溶于燃料的碱金属洗涤剂;和含碱土金属的洗涤剂。
15.一种用于减少在燃烧含醇燃料的内燃机中沉积物形成的组合物,所述组合物包含:
(a)腐蚀抑制剂,
(b)醇,和
(c)琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂和聚亚烷基胺分散剂中的至少一种。
16.方面15的组合物,其中该腐蚀抑制剂包含十二烯基琥珀酸(DDSA)。
17.方面15的组合物,其中该醇选自甲醇、乙醇、丙醇、丁醇及其任意组合的混合物。
18.方面15的组合物,其中该醇是乙醇。
19.方面18的组合物,其中该燃料组合物中的乙醇含量为约10重量%~约100重量%。
20.方面18的组合物,其中该燃料组合物中的乙醇含量为约15重量%~约85重量%。
21.方面18的组合物,其中该燃料组合物中的乙醇含量为约74重量%~约85重量%。
22.方面15的组合物,其中该聚亚烷基胺分散剂包含聚亚异丁基胺分散剂。
23.方面15的组合物,其中该燃料进一步包含汽油。
24.一种用于燃烧包含腐蚀抑制剂的含醇燃料的汽油发动机的燃料添加剂浓缩物,所述浓缩物包括:
(a)一种或多种腐蚀抑制剂,
(b)琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂和聚亚烷基胺分散剂中的至少一种,和
(c)选自油、燃料、汽油、醇、溶剂、载液和其它可在汽油发动机中燃烧的液体物质的稀释剂。
25.一种燃料添加剂浓缩物,包含醇,和琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂和聚亚烷基胺分散剂中的至少一种。
26.方面25的燃料添加剂,其中该醇是乙醇。
27.方面26的燃料添加剂,其中该燃料组合物中的乙醇含量为约10重量%~约100重量%。
28.方面26的燃料添加剂,其中该燃料组合物中的乙醇含量为约15重量%~约85重量%。
29.方面26的燃料添加剂,其中该燃料组合物中的乙醇含量为约74重量%~约85重量%。
30.方面25的燃料添加剂,其中该聚亚烷基胺分散剂包含聚亚异丁基胺分散剂。
31.一种燃料,包含:
(a)醇,
(b)汽油,
(c)燃料添加剂,包含琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂、聚亚烷基胺分散剂和聚亚异丁基胺分散剂中的至少一种,和
(d)腐蚀抑制剂,选自Innospec DCI-11腐蚀抑制剂、Petrolite Tolad3222腐蚀抑制剂、Petrolite Tolad 3224腐蚀抑制剂、Nalco 5403腐蚀抑制剂、ENDCOR FE-9730腐蚀抑制剂、MidContinental MCC5011E腐蚀抑制剂、MidContinental MCC5011EW腐蚀抑制剂、CorrPro 654腐蚀抑制剂、NALCO 5403腐蚀抑制剂、ENDCOR FE 9730腐蚀抑制剂和BetzACN 13腐蚀抑制剂和十二烯基琥珀酸腐蚀抑制剂。
32.方面31的燃料组合物,其中该醇是乙醇。
33.方面32的燃料组合物,其中该燃料组合物中的乙醇含量为约10重量%~约100重量%。
34.方面32的燃料组合物,其中该燃料组合物中的乙醇含量为约15重量%~约85重量%。
35.方面32的燃料组合物,其中该燃料组合物中的乙醇含量为约74重量%~约85重量%。
36.方面31的燃料组合物,其中该DCI-11腐蚀抑制剂包括有机酸和胺或二胺的反应产物。
37.方面31的燃料组合物,其中该DCI-11腐蚀抑制剂包括NH2(CH2)n-NH-C8-10结构,其中n为1~约10。
38.方面31的燃料组合物,其中Petrolite Tolad 3222腐蚀抑制剂和Petrolite Tolad 3224腐蚀抑制剂均独立包含结构NH2(CH2)n-NH-(CH2)mO-C8-10,其中n和m独立地为1~约10。
39.方面31的燃料,其中该聚亚烷基胺分散剂包含聚亚异丁基胺分散剂。
40.一种用于减少在燃烧含醇燃料组合物的内燃机中的沉积物形成的方法,所述方法包括:
(a)将该燃料与十二烯基琥珀酸腐蚀抑制剂混合,和
(b)在该发动机中燃烧该燃料和该十二烯基琥珀酸腐蚀抑制剂,
其中与燃烧具有腐蚀抑制剂但基本不含十二烯基琥珀酸腐蚀抑制剂的含醇燃料时发生的沉积物形成相比,减少了沉积物的形成。
41.方面40的方法,其中该燃料进一步包含汽油。
42.方面40的方法,其中该醇选自甲醇、乙醇、丙醇、丁醇及其任意组合的混合物。
43.方面40的方法,其中该醇是乙醇。
44.方面43的方法,其中该燃料组合物中的乙醇含量为约10重量%~约100重量%。
45.方面43的方法,其中该燃料组合物中的乙醇含量为约15重量%~约85重量%。
46.方面43的方法,其中该燃料组合物中的乙醇含量为约74重量%~约85重量%。
47.方面40的方法,其中所述方法基本由以下组成:
(a)将该燃料与十二烯基琥珀酸腐蚀抑制剂混合,和
(b)在该发动机中燃烧该燃料和该十二烯基琥珀酸腐蚀抑制剂。
48.一种用于减少在燃烧含醇燃料的内燃机中沉积物形成的组合物,所述组合物包含:
(a)十二烯基琥珀酸腐蚀抑制剂,和
(b)醇。
49.方面48的组合物,其中该醇选自甲醇、乙醇、丙醇、丁醇及其任意组合的混合物。
50.方面48的组合物,其中该醇是乙醇。
51.方面48的组合物,其中该燃料进一步包含汽油。
52.方面48的组合物,其中该组合物基本由(a)十二烯基琥珀酸腐蚀抑制剂,和(b)醇组成。
53.一种燃料添加剂浓缩物,包含醇和十二烯基琥珀酸(DDSA)腐蚀抑制剂。
54.一种燃料,包含:
(a)一种或多种醇,
(b)汽油,和
(c)十二烯基琥珀酸(DDSA)腐蚀抑制剂。
55.方面54的燃料,其中该一种或多种醇包括乙醇。
56.方面55的燃料,其中该燃料组合物中的乙醇含量为约10重量%~约100重量%。
57.方面55的燃料,其中该燃料组合物中的乙醇含量为约15重量%~约85重量%。
58.方面55的燃料,其中该燃料组合物中的乙醇含量为约74重量%~约85重量%。
应当理解前述概述和以下详述都仅为示例性和解释性的,并用于对要求保护的本公开进行进一步的解释。
实施方式详述
此处的“腐蚀”是指由于暴露于含乙醇的燃料而使发动机表面或发动机的一部分或部件或发动机组分或部件的任意降解、生锈、弱化、恶化、软化等。
此处的“PEA”和“聚醚胺”是指具有一个或多个胺氮原子和一个或多个含氧醚键的有机化合物。因此,前缀“聚”在此并不限定需要两个或多个,而是本领域的普通术语,在一种实施方式中,如果其分子量和溶解性能够防止沉积形成,其可以包括具有一个胺氮原子和一个含氧醚键的有机化合物。醚部分可以来自例如环氧乙烷、环氧丙烷、环氧丁烷及其混合物。在一种特定的实施方式中,PEA可以为二胺和/或可以具有大于700的分子量。在另一实施方式中,该聚醚胺的分子量可以为700~3000,特别为900~1500。更特别地,适用于本公开的PEA也可以包括氨基甲酸酯、氨基氨基甲酸酯、单和二硫代氨基甲酸酯、氨基烷基、和酰氨基链烷醇胺,所有这些都是本领域技术人员已知的。本公开的性能的关键在于对该洗涤剂在含乙醇的燃料中的溶解性需要要求的极性比常规(非极性的)聚亚异丁基洗涤剂所存在的极性更高。
此处的“腐蚀抑制”或“减少腐蚀”是指在最小化、减少、消除或防止腐蚀方面的任何改进。
此处的“沉积物”或“发动机沉积物”是指在发动机内积累的固体物质,其中该沉积物可以源自燃烧前的燃料、未燃烧的燃料和燃烧副产物,或来自添加到乙醇或乙醇-汽油混合物中的腐蚀抑制剂。该沉积物也可以包括在进气阀上的物质(已知的进气阀沉积物或IVD)或燃烧腔沉积物(已知的CCD)或燃烧喷射器沉积物。此处的“沉积物”可以存在于与包含乙醇和腐蚀抑制剂的燃料接触的燃烧发动机中的金属表面和某些塑料或合成部件或表面的内部或上面。例如燃料泵、阀门、衬垫、浮筒装置、继电器或信号装置、量器、筛网、过滤器、进气阀、燃烧腔、端口喷射器、活塞及其它的部件都会遭受一定程度的来自乙醇燃料中所述的腐蚀抑制剂的沉积物。
此处的“乙醇”是指乙醇,化合物C2H5OH。其可以以多种质量或等级存在或提供,例如商用或燃料等级,以及纯的或试剂等级的乙醇,可以来自任何来源,例如但不局限于石油精炼物流、蒸馏馏分和生物来源(例如来自玉米或其它农作物的生物乙醇)。在一些实施方式中,乙醇的含量可以为基于总燃料组合物的约10~约100wt%。在另一实施方式中,乙醇的含量可以为基于总燃料组合物的约15~约85wt%。在甚至更进一步的实施方式中,乙醇的含量可以为基于总燃料组合物的约74~约85wt%。
此处的“New Energy乙醇”是指由称作New Energy的公司制备或为其制备的乙醇,已知该乙醇具有约0.9PTB或更少的Innospec DCI-11腐蚀抑制剂。
此处的“ADM乙醇”是指由Archer Daniels Midland Corporation制备或为其制备的乙醇,已知其具有约32PTB的Innospec DCI-11腐蚀抑制剂。
此处的“腐蚀抑制剂”是指以下中的至少一种:低分子量(即<700)的胺(单胺、二胺、三胺和多胺)、胺、醚胺、亚胺、咪唑啉、噻二唑、一元羧酸、二元羧酸、对-亚苯基二胺和二环己基胺、烷基取代的琥珀酸酐和酸及其混合物和其盐。适用于此处的腐蚀抑制剂也可以包括或包含四丙链烯基琥珀酸或其酸酐及其聚合物。这些可以包括商业产品,例如已知为Pettolite Tolad 3222和Petrolite Tolad 3224的那些,这些被认为一般地具有结构NH2(CH2)n-NH-(CH2)m-O-C8-10,其中n和m分别为1~约10。此处作为“腐蚀抑制剂”的还包括Innospec(以前的AssociatedOctel)产品DCI-11TM,认为其含有有机酸和胺或二胺例如DuomineTM(具有结构NH2(CH2)n-NH-C8-10,其中n为1~约10)的反应产物。DCI-11产品被认为是低分子量(<500)的羧酸的胺盐。另一适合的腐蚀抑制剂是十二烯基琥珀酸(DDSA)。
此处的“分散剂”、“分散剂添加剂”或“分散剂燃料添加剂”是指包含两个或多个相同或不同类型的分散剂的分散剂、分散剂-洗涤剂或分散剂组合物。适合的分散剂包括但不局限于琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂、聚亚烷基胺分散剂和聚亚异丁基胺分散剂。
适用于此处公开的组合物中的燃料添加剂也可以包括以下中的一种或多种:酚;受阻酚;聚烯烃胺;芳基胺;二苯基胺;一元羧酸;二元羧酸;多元羧酸;氧化烷基酚树脂;甲醛与4-(1,1-二甲基乙基)苯酚、甲基环氧乙烷和环氧乙烷的聚合物;选自四乙基铅、甲基环戊二烯基三羰基锰、叠氮化物、过氧化物和硝酸烷基酯的辛烷值增强剂;单酯;二酯;醚;酮;二醚;聚醚;甘醇二甲醚;二元醇;环氧乙烷;C1-C8脂肪族烃;环氧丁烷;环氧丙烷;环氧乙烷;环氧化物;丁烷;戊烷;二甲苯;一氧化二氮;硝基甲烷;苯酚盐;水杨酸盐;磺酸盐;壬基苯酚乙氧化物;可溶于燃料的碱金属洗涤剂;含碱土金属的洗涤剂。
Petrolite Tolad 357是一种适用于此处的腐蚀抑制剂,被认为是一种具有约700或更低的分子量的包含(1)链烯基琥珀酸或酸酐(ASAA)和(2)ASAA和三烷醇胺(例如三乙醇胺(TEA))的反应产物(其中将ASAA(3摩尔)与TEA(1摩尔)反应产生酰胺和/或胺盐)的组合物。
在另一实施方式中,该腐蚀抑制剂是将有机酸或二酸与胺、二胺或多胺以约5∶1的比例混合的产物。
在此处的另一实施方式中,提供了一种燃料组合物,其可以为或可以包含1.0~100体积%的一种或多种醇和0~99%的汽油和腐蚀抑制剂,所述抑制剂包含(a)约35wt%~70wt%的至少一种单或二链烯基琥珀酸,其中该链烯基具有8~18个碳原子;和(b)约30wt%~65wt%的包含2~12个碳原子的脂肪族或脂环族胺、二胺或多胺。在一种实施方式中,可以将该腐蚀抑制剂溶解在烃溶剂中,该烃溶剂由芳香族烃、含1~4个碳原子的醇或其混合物构成,烃溶剂与(a)和(b)的总和之比为约15∶85~50∶50,其中该腐蚀抑制剂在该燃料组合物中的含量低于约1000ppm。
在此处的另一实施方式中,该腐蚀抑制剂可以为或包含这样的组合物:具有(a)约75wt%~95wt%的至少一种聚合不饱和脂肪族一元羧酸,所述不饱和酸每分子具有16~18个碳原子,和(b)约5wt%~25wt%的至少一种其中链烯基具有8~18个碳原子的单链烯基琥珀酸。
在另一实施方式中,该腐蚀抑制剂可以包含十二烯基琥珀酸(DDSA)。
该腐蚀抑制剂可以混合到乙醇或汽油或乙醇/汽油混合物中,或与其混合。
此处的腐蚀抑制剂可以包括但不局限于以下商业产品及其衍生物和化学等价产物:
Octel DCI-11,通常以例如约20PTB用于燃料乙醇中
Petrolite Tolad 3222,通常以例如约20PTB用于燃料乙醇中
Petrolite Tolad 3224,通常以例如约13PTB用于燃料乙醇中
Petrolite Tolad 357,通常以例如约15PTB用于燃料乙醇中
Nalco 5403,通常以例如约30PTB用于燃料乙醇中
ENDCOR FE-9730(以前的BetzACN 13),通常以例如约20PTB用于燃料乙醇中
MidContinental MCC5011E,通常以例如约20PTB用于燃料乙醇中
MidContinental MCC5011EW,通常以例如约27PTB用于燃料乙醇中
CorrPro 654,通常以例如约13PTB用于燃料乙醇中
Afton Chemical的HiTEC6455,以例如约32PTB
此处的“PTB”是指在燃料添加剂工业中通用的专业术语“磅/千桶”。PTB略等于约4ppm。
因此,在此处的一种实施方式中,提供了一种用于减少在内燃机中形成的沉积物的方法,所述方法包括在所述发动机中燃烧一种燃料组合物,该燃料组合物包含汽油、醇、腐蚀抑制剂和至少一种分散剂燃料添加剂,由此与当燃烧包含腐蚀抑制剂但不包含至少一种分散剂燃料添加剂的含醇燃料组合物时在发动机中产生的沉积物相比,防止或减少了发动机中的沉积物。在此处的一种实施方式中,该醇是乙醇,在另一种实施方式中,其是甲醇、丙醇、丁醇和/或包含其任意组合的混合物。
而且已经发现过量的酸性组分(例如乙酸和含硫酸性组分)有助于在发动机中和/或在阀门或其它发动机部件上的沉积物累积。此处分散剂的使用通过缓冲该乙酸和/或含硫酸性组分有助于略微提高pH值,由此减少或防止促进沉积物的反应产物的形成。此处的分散剂的使用还有利于缓冲该酸性腐蚀抑制剂。因此,本公开提供了一种以用于含乙醇的燃料中的分散剂的形式的腐蚀抑制剂缓冲剂。
此处还提供了一种燃料,其包含(a)选自甲醇、乙醇、丙醇和丁醇及其混合物的醇,(b)汽油,(c)将有机羧酸或二酸和胺、二胺或多胺合并的产物,和(d)分散剂,包含以下中的一种或多种:琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂、聚亚烷基胺分散剂、聚亚异丁基胺分散剂。
而且已经发现使用十二烯基琥珀酸(DDSA)腐蚀抑制剂减少了在内燃机中形成的沉积物。在一种实施方式中,DDSA适用于代替常规的DCI-11腐蚀抑制剂。此外,在另一实施方式中,DDSA腐蚀抑制剂可以与分散剂燃料添加剂一起使用,或不与其一起使用。
以下实施例进一步描述了本公开的一些方面,但并不限制本公开内容。
实施例
测试方法-Chevrolet Impala FFV测试-在20063.5升6-气缸Flexible Fuel Vehicle(FFV)Chevrolet Impala上进行5000英里进气阀沉积物测试。FFV是指能够以高达85%乙醇和15%烃(例如无铅汽油)的混合物运转的车辆。该测试由多级100分钟循环构成,该多级100分钟循环由加速和以25MPH、40MPH和65MPH稳定驱动的混合构成。在开始里程累计之前和在5000英里测试之后称重该发动机的六个进气阀。进气阀沉积物(IVD)之差的平均值作为平均进气阀沉积物重量报道。
表I
5,000英里Cbevrolet Impala PPV沉积物测试结果 | |||||||||
实施例 | 乙醇来源 | 乙醇,% | RUL汽油,% | H-6400PEA,PTB | H-6560,曼尼希碱分散剂,PTB | H-6455,DDSAPTB | DCI-11,PTB | 硫酸钠,ppm vol. | 平均IVDmg/阀 |
1 | none | 0 | 100 | 0 | 0 | 429 | |||
2 | A | 84 | 16 | 0 | 32 | 227 | |||
3 | B | 84 | 16 | 0 | 0 | 99 | |||
4 | B | 84 | 16 | 0 | 32 | 230 | |||
5 | B | 84 | 16 | 4 | 96 | ||||
6 | A | 84 | 16 | 500 | 32 | 4 | |||
7 | A | 84 | 16 | 85 | 32 | 11 | |||
8 | A | 84 | 16 | 85 | 32 | 14 | |||
9 | A | 84 | 16 | 42.5 | 42.5 | 32 | 16 | ||
10 | B | 84 | 16 | 32 | 81 |
在该表中,乙醇来源A是指包含4ppm硫酸盐和32PTB InnospecDCI-11腐蚀抑制剂的ADM变性乙醇。该32PTB Innospec DCI-11示于表中。在任何实施例中在乙醇来源A中不再添加额外的DCI-11。乙醇来源B是指包含少于1ppm硫酸盐和0.9PTB腐蚀抑制剂的New Energy变性乙醇。
实施例1-在20063.5L Flexible Fuel(FFV)Chevrolet Impala中运行无添加剂的常规合格无铅(RUL)汽油5000英里,运行改性的Quad 4循环。429mg/阀的沉积物量是这种燃料和测试循环所预期的典型数据。
实施例2-通过混合84%乙醇来源A和16%的常规合格无铅汽油制备燃料。提供的乙醇来源A包含32PTB的Innospec DCI-11腐蚀抑制剂。这示于表1中。在该混合物中不添加另外的DCI-11。当在ChevroletImpala FFV测试中,实施例2产生了令人惊奇的高水平的进气系统沉积物。纯乙醇清洁燃烧,产生非常少的沉积物,因此人们将预期既然只有15%~20%的E-85燃料由该无铅汽油构成,那么实施例2会产生少于100mg/阀的沉积物或为100%汽油观察到的沉积物的仅15~20%。但是,实施例2给出了令人惊奇的高水平平均IVD值,为227mg/阀,其大于预测值的两倍。
实施例3-由包含少于1PTB腐蚀抑制剂的84%乙醇样品B制备燃料。当在Chevrolet Impala FFV测试中测试该燃料时,其产生99mg/阀的平均进气阀沉积物。这大于在84%清洁燃烧乙醇和16%合格无铅汽油的混合物上进行的测试的预期值。
实施例4-通过混合84%的包含非常少腐蚀抑制剂的乙醇样品B和16%的合格无铅汽油和32PTB的Innospec DCI-11腐蚀抑制剂制备燃料。当在Chevrolet Impala FFV测试中测试该燃料时,其产生与实施例2中测试的燃料基本相同的沉积物水平,230mg/阀。这些结果显示Innospec腐蚀抑制剂DCI-11令人惊奇地有助于进气阀沉积物的质量。
实施例5-通过混合84%的包含非常少硫酸盐的乙醇样品B和16%的合格无铅汽油和4ppm的硫酸钠制备燃料。结果的平均IVD值为96mg/阀,这表明乙醇样品A的硫酸盐含量不会明显有助于实施例2中的高平均IVD值。
实施例6-该燃料包含与实施例2中相同的组成加上500PTB的Afton Chemical的HiTEC6400聚醚胺(PEA)。当在Chevrolet ImpalaFFV测试中测试该燃料时,其产生平均IVD仅为4mg/阀的进气阀沉积物,尽管其包含提供的32PTB的Innospec DCI-11腐蚀抑制剂。
实施例7-该燃料包含与实施例2中相同的组成加上85PTB的HiTEC6400PEA。当在Chevrolet Impala FFV测试中测试该燃料时,其产生的平均IVD仅为11mg/阀,尽管其包含32PTB的Innospec DCI-11腐蚀抑制剂。
实施例8-该燃料包含与实施例2中相同的组成加上85PTB的包含曼尼希分散剂的Afton Chemical的HiTEC6560添加剂包。当在Chevrolet Impala FFV中测试该燃料时,其产生14mg/阀的平均IVD,尽管其包含32PTB的Innospec DCI-11腐蚀抑制剂。
实施例9-该燃料包含与实施例2中相同的组成加上85PTB的包含曼尼希分散剂的Afton Chemical的HiTEC6560添加剂包。当在Chevrolet Impala FFV中测试该燃料时,其产生14mg/阀的平均IVD,尽管其包含32PTB的Innospec DCI-11腐蚀抑制剂。
实施例10-该燃料包含与实施例3中相同的组成加上32PTB的Afton Chemical的腐蚀抑制剂HiTEC6455十二烯基琥珀酸(DDSA)。当在Chevrolet Impala FFV测试中测试该燃料时,其产生81mg/阀的平均IVD。该结果低于由实施例4中的Innospec DCI-11腐蚀抑制剂产生的230mg/阀的平均IVD值。
通常,大多数进气阀沉积物是由进气阀上的燃料组分分解形成的,设计添加剂用于去除这些沉积物类型。这些实施例显示大多数由乙醇-汽油燃料混合物形成的沉积物可来自腐蚀抑制剂的使用,其会产生不同类型的进气阀沉积物。已经发现分散剂添加剂可以有效去除由燃料形成的常规沉积物,而且也能够有效去除由在乙醇-汽油燃料混合物中使用腐蚀抑制剂造成的沉积物。
下表II提供了各种含乙醇燃料的一些适合的添加剂组合由此可以控制或减少在燃烧含乙醇燃料的发动机中的腐蚀的示例。
表II
燃料 | A | B | C | D | E | F | G | H | I | J |
E85E85E85E85E85E85E85E85E85 | 40-20040-20040-20040-20040-20040-20040-20040-20040-200 | 120 | 80 | 100 | 120 | 140 | 160 | 100 | 120 | 100 |
其中含量以最终燃料中ppm计:
A=HiTEC6400PEA,包括曼尼希分散剂的HiTEC6560添加剂包,或其它适当的分散剂,例如琥珀酰亚胺、琥珀酰胺、聚亚烷基胺、聚亚异丁基胺,和酰胺
B=DCI-11腐蚀抑制剂
C=Petrolite Tolad 3222腐蚀抑制剂
D=Petrolite Tolad 3224腐蚀抑制剂
E=Petrolite Tolad 357腐蚀抑制剂
F=MidContinental MCC5011E腐蚀抑制剂
G=MidContinental MCC5011EW腐蚀抑制剂
H=CorrPro 654腐蚀抑制剂
I=Nalco 5403腐蚀抑制剂
J=ENDCOR FE 9730腐蚀抑制剂
表II示出了腐蚀抑制剂可以如何与一种或多种分散剂燃料添加剂相混合由此结果减少或防止燃烧E85燃料的发动机中的进气沉积物的实施例。
因此,在此处的一种实施方式中,提供了一种包含乙醇、汽油、一种或多种分散剂燃料添加剂和选自Octel DCI-11腐蚀抑制剂、PetroliteTolad 3222腐蚀抑制剂、Petrolite Tolad 3224腐蚀抑制剂、Nalco 5403腐蚀抑制剂、ENDCOR FE-9730腐蚀抑制剂、MidContinental MCC5011E腐蚀抑制剂、MidContinental MCC5011EW腐蚀抑制剂、CorrPro 654腐蚀抑制剂、NALCO 5403腐蚀抑制剂、ENDCOR FE 9730腐蚀抑制剂和BetzACN 13腐蚀抑制剂或其化学等价物的腐蚀抑制剂的燃料。在一种实施方式中,该燃料是E85汽油-乙醇混合物。
在此处的一种实施方式中,腐蚀抑制剂与分散剂燃料添加剂的比例可以为约1∶20~约20∶1。在另一实施方式中,腐蚀抑制剂与分散剂燃料添加剂的比例可以为约1∶10~约10∶1。在另一实施方式中,腐蚀抑制剂与分散剂燃料添加剂的比例可以为约1∶5~约5∶1。
在此处的另一实施方式中,腐蚀抑制剂(例如DCI-11)的最小含量为约5PTB,在另一实施方式中,其在最终燃料中的含量为约10PTB~约30PTB。此外,在一种实施方式中,该燃料可以包含30~60PTB的分散剂燃料添加剂。
考虑到本说明书和此处所公开的公开内容的实施,本公开的其它实施方式对于本领域的技术人员将是显而易见的。在该说明书和权利要求书全文中所用的“一个”和/或“一种”可以表示一个(种)或多于一个(种)。除非另外指出,所有在本说明书和权利要求书中使用的表示试剂、性质(例如分子量、百分比、比例、反应条件等)的数量的数值都应当理解为在所有情况下可用术语“约”修饰。因此,除非相反指出,在说明书和权利要求书中提出的数值参数都是可以取决于通过本公开得到的所需性质而变化的近似值。最低限度地,且并不用于试图限定等价于权利要求的范围的原则的应用,各数值参数至少应当根据所报道的有效数字和应用常规取舍技术进行解释。尽管描述本公开较宽范围的数值范围和参数都是近似值,也尽可能精确地报道在特别实施例中所提出的数值。然而,由于在各自测试方式中存在的标准偏差,任何数值本身都必然包含某些误差。希望将该说明书和实施例仅理解为示例性的,下述权利要求指出了该公开的真正范围和精神。
Claims (9)
1.一种用于减少在燃烧包含腐蚀抑制剂的含醇燃料组合物的内燃机中沉积物形成的方法,所述方法包括:
(a)将该燃料与至少一种选自琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂和聚亚烷基胺分散剂的分散剂燃料添加剂相混合,和
(b)在该发动机中燃烧该燃料和该至少一种分散剂燃料添加剂,
其中与燃烧具有腐蚀抑制剂但不含该至少一种分散剂燃料添加剂的含醇燃料时发生的沉积物形成相比,减少了沉积物的形成。
2.一种用于减少在燃烧含醇燃料的内燃机中沉积物形成的组合物,所述组合物包含:
(a)腐蚀抑制剂,
(b)醇,和
(c)琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂和聚亚烷基胺分散剂中的至少一种。
3.一种用于燃烧包含腐蚀抑制剂的含醇燃料的汽油发动机的燃料添加剂浓缩物,所述浓缩物包括:
(a)一种或多种腐蚀抑制剂,
(b)琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂和聚亚烷基胺分散剂中的至少一种,和
(c)选自油、燃料、汽油、醇、溶剂、载液和其它可在汽油发动机中燃烧的液体物质的稀释剂。
4.一种燃料添加剂浓缩物,包含醇,和琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂和聚亚烷基胺分散剂中的至少一种。
5.一种燃料,包含:
(a)醇,
(b)汽油,
(c)燃料添加剂,包含琥珀酰亚胺分散剂、琥珀酰胺分散剂、酰胺、曼尼希碱分散剂、聚亚烷基胺分散剂和聚亚异丁基胺分散剂中的至少一种,和
(d)腐蚀抑制剂,选自Innospec DCI-11腐蚀抑制剂、Petrolite Tolad3222腐蚀抑制剂、Petrolite Tolad 3224腐蚀抑制剂、Nalco 5403腐蚀抑制剂、ENDCOR FE-9730腐蚀抑制剂、MidContinental MCC5011E腐蚀抑制剂、MidContinental MCC5011EW腐蚀抑制剂、CorrPro 654腐蚀抑制剂、NALCO 5403腐蚀抑制剂、ENDCOR FE 9730腐蚀抑制剂和BetzACN 13腐蚀抑制剂和十二烯基琥珀酸腐蚀抑制剂。
6.一种用于减少在燃烧含醇燃料组合物的内燃机中的沉积物形成的方法,所述方法包括:
(a)将该燃料与十二烯基琥珀酸腐蚀抑制剂混合,和
(b)在该发动机中燃烧该燃料和该十二烯基琥珀酸腐蚀抑制剂,
其中与燃烧具有腐蚀抑制剂但基本不合十二烯基琥珀酸腐蚀抑制剂的含醇燃料时发生的沉积物形成相比,减少了沉积物的形成。
7.一种用于减少在燃烧含醇燃料的内燃机中沉积物形成的组合物,所述组合物包含:
(a)十二烯基琥珀酸腐蚀抑制剂,和
(b)醇。
8.一种燃料添加剂浓缩物,包含醇和十二烯基琥珀酸(DDSA)腐蚀抑制剂。
9.一种燃料,包含:
(a)一种或多种醇,
(b)汽油,和
(c)十二烯基琥珀酸(DDSA)腐蚀抑制剂。
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CN103666564B (zh) * | 2012-09-26 | 2015-07-01 | 中国石油化工股份有限公司 | 一种阻垢组合物及其用途 |
CN105008496A (zh) * | 2013-03-07 | 2015-10-28 | 路博润公司 | 耐离子腐蚀抑制剂和用于燃料的抑制剂组合 |
CN105765039A (zh) * | 2013-10-24 | 2016-07-13 | 巴斯夫欧洲公司 | 复合酯在燃料中的用途 |
CN105765039B (zh) * | 2013-10-24 | 2019-02-12 | 巴斯夫欧洲公司 | 复合酯在燃料中的用途 |
CN107880953A (zh) * | 2017-11-03 | 2018-04-06 | 深圳市广昌达石油添加剂有限公司 | 腐蚀抑制剂及其制备方法和应用 |
CN107880953B (zh) * | 2017-11-03 | 2019-11-29 | 深圳市广昌达石油添加剂有限公司 | 腐蚀抑制剂及其制备方法和应用 |
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US20080202561A1 (en) | 2008-08-28 |
BRPI0705107B1 (pt) | 2017-04-04 |
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