CN1576353A - 改进燃烧和发动机清洁的馏出燃料组合物 - Google Patents
改进燃烧和发动机清洁的馏出燃料组合物 Download PDFInfo
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Abstract
本发明提供了一种馏出燃料添加剂组合物和一种燃料组合物,其含有馏出燃料、高碱性磺酸钙清净剂、琥珀酰亚胺分散剂和有机金属镁化合物。还提供一种改进柴油吸入体系清洁度的方法,该方法是在所述体系中燃烧含有燃料添加剂组合物的馏出燃料。
Description
技术领城
本发明涉及一种用于改进的馏出燃料添加剂组合物的高碱性磺酸钙清净剂和无灰琥珀酰亚胺分散剂之间的协同相互作用,除了金属去污剂和无灰分散剂以外,添加剂剂组合物还含有有机金属镁化合物。以该种添加剂组合物处理的馏出燃料的燃烧性能得以改进,这是因为清净剂和有机金属镁化合物,以及良好的燃料体系清洁度,该清洁度得益于清净剂/分散剂的相互作用。
背景技术
许多现有技术致力于配制馏出燃料添加剂组合物,以便燃烧时有利于环境,所述有利之处包括,例如,减少排放有毒污染物如氮氧化物和颗粒物,降低排放颗粒物的酸度和改善燃料经济性(每单位燃烧燃料数量排放更低的二氧化碳数量)。很少研究这些燃料对燃料体系清洁度的影响(例如在燃料喷射器上的积碳和漆膜)。
很需要有一种馏出燃料添加剂组合物,它能够同时改进燃烧性能、燃料和燃烧体系的清洁度,改善燃料经济性和减少污染物的产生。
发明内容
本发明的实施方案之一是提供了一种燃料添加剂组合物,其含有有机金属镁化合物,烷基取代的琥珀酰亚胺无灰分散剂和TBN高于200的高碱性磺酸钙清净剂。在另一实施方案中高碱性磺酸钙的TBN大约为300。
另一实施方案是提供了一种燃料,其含有较大量的中间馏份油和较少量的燃料添加剂组合物,所述燃料添加剂组合物含有有机金属镁化合物,烷基取代的琥珀酰亚胺无灰分散剂和TBN高于200的高碱性磺酸钙清净剂。
因此本发明一个实施方案还提供了一种改进燃料吸入体系清洁度的方法,其在燃料吸入体系中使用了含有燃料添加剂组合物的燃料,所述燃料添加剂组合物含有有机金属镁化合物,烷基取代的琥珀酰亚胺无灰分散剂和TBN大约为300的高碱性磺酸钙清净剂。
应该理解上述一般性说明和以下的详细说明仅仅是举例性的和解释性的,是为了对本发明和要求的权利提供进一步解释。
本发明的一个实施方案提供用于馏出燃料的馏出燃料添加剂组合物,以便可以提高燃料燃烧性能,同时也提供了优异的燃料吸入体系清洁度。本文中馏出燃料定义为沸点范围在140-360℃[284-680华氏度]的石油基烃类燃料,包括柴油和生物柴油,喷气燃料,海洋燃料和家庭用的加热燃油,含有本发明添加剂组合物的馏出燃料表现出燃烧性能的提高。
假如所述添加剂组合中的某个成份具有特定的比例,含有添加剂组合的燃料还表现出了优异的燃料喷射器清洁度,该清洁度是根据Cummins L 10柴油清净试验测定的。在Cummins L 10柴油清净实验中喷射级别至多为10.0时,测量了燃料喷射清洁度。
另一实施方案提供了一种添加剂组合物,一种含有添加剂组合物的馏出燃料和一种使用含有添加剂组合物的燃料以改进燃料吸入体系清洁度的方法。
在另一实施方案中,添加剂组合物含有至少一种有机金属镁配合物,高碱性磺酸钙清净剂和烷基取代的琥珀酰亚胺无灰分散剂,当该添加剂组合物溶解于馏出燃料中时,其满足以下关系:
-0.159x+0.243y-0.0143xy≤-8.4
其中
x=琥珀酰亚胺浓度(磅/千桶)
y=高碱性磺酸钙浓度(PTB)
同时有以下限定:
x=20-35,优选25-30和y=10-120,优选30-50。
有机金属镁化合物不影响喷射器清洁度,在一个实施方案中,有机金属镁化合物在燃料中的浓度最高约20PTB。
已知的用于改进燃烧性能的常规添加剂组合物以前认为不必要通过Cummins L 10柴油清净试验(其中“通过”的定义是平均喷射器级别为10.0或更低),为了辨别出影响喷射器级别的添加剂组合物中的组份,完成了试验设计,观察到高碱性磺酸钙清净剂和琥珀酰亚胺分散剂之间的协同作用(即非线性相互作用),惊奇地发现其结果是任何现有技术没有预料到的。
试验设计的结果被用于建立平均喷射器级别的模型,如下:
级别=-0.159x+0.243y-0.0143xy+8.4 (1)
其中
x=琥珀酰亚胺浓度(磅/千桶或PTB);
y=高碱性磺酸钙浓度(PTB)。
因为对于要通过CumminsL10柴油清净试验,平均喷射器级别必须是10.0或以下,计算式变为:
10.0≥-0.159x+0.243y-0.0143xy+18.4 (2)或
-0.159x+0.243y-0.0143xy≤-8.4 (3)
其中xy表示去污剂/分散剂的协同作用。
通过三个新的配方试验其满足以上计算式证实了该模型:
1.x=28PTB,y=32PTB
2.x=26PTB,y=40PTB
3.x=25PTB,y=48PTB
按照模型,三个配方全部给出平均喷射器级别低于10.0,当然计算式3中的x和y有无限个解,通常实际上解的实例在以下范围:
x=20-35,优选25-30;
y=10-120,优选30-50。
有机金属镁化合物的含量对于喷射器级别没有显著的不利影响,因此不受计算式3表示的模型的限制。仅作为经济方面的考虑,有机金属化合物镁的含量在一个实施方案中被限定为20PTB或更少。来自含有有机金属镁的组合物的利处并未直接与喷射器级别相关,但是其更多的优势在于减少排放颗粒,降低NOx和SOx,降低烃类,改进燃料经济性和燃烧性能。
甲基环戊二烯基镁三羰基(MMT)作为有机金属镁化合物,由850-2100MW PIBSA和类似四亚乙基五胺的聚烯烃聚胺制备的琥珀酰亚胺作为组合物中的无灰分散剂和TBN高达大约300的高碱性磺酸钙作为清净剂是特别有用的。MMT可以从Ethyl Corporation,Richmond,VA买到,用于CumminsL10研究的柴油燃料是高硫燃料(0.4wgt%硫),但是可以使用任何柴油燃料(包括低硫或超低硫燃料),单独的L10试验表明往含有本发明添加剂的燃料中加入2-乙基己基硝酸酯十六烷值提高剂不会降低清净作用。
具体实施方式
以下实施例进一步说明本发明的各方面,但是本发明不受其限制。
实施例
因为CumminsL10试验的设计是用来评估添加剂和在北美使用的公路燃料,所以HiTEC4080燃料被用于本实施例,这种添加剂是EthylCorporation’s的无抗泡沫剂的Greenburn公路柴油燃料添加剂组合物,以推荐的处理比率500ppm使用(w/w),配方列于表1。
组份 | %重量 | 500ppm总量中的组份(ppm) | 500ppm总量中的组份(PTB) |
HiTEC9645 | 15.34 | 76.7 | 22.8 |
2-乙基己醇 | 46.22 | 231.1 | 68.8 |
HiTEC611 | 32.16 | 160.8 | 47.9 |
HiTEC536 | 0.93 | 4.7 | 1.4 |
D-5021 | 0.97 | 4.9 | 1.5 |
HiTEC3062 | 4.38 | 21.9 | 6.6 |
表1.HiTEC4080组合物
对于该实施例的目的,使用北美组份Toland9310和50%的十二碳烯琥珀酸分别以相等重量代替European组份D-5021(抗乳化剂)和HiTEC536(防锈剂),每个试验中上述组份保持恒定的上述浓度。预期对CumminsL10级别有较大影响的组份是HiTEC9645(琥珀酰亚胺基分散剂),HiTEC611(高碱性磺酸钙)和HiTEC3062(芳香族溶剂中的62%MMT)。
得到的二水平三因子(23)设计表示于图1,轴上数字是PTB浓度。
所有试验使用同样的CumminsL10发动机和相同批次的高硫Cat1K燃料进行,试验次序是任意的,结果列于表2,
试验号 | PTB H-9645 | PTB H-611 | PTB H-3062 | 平均流动损失(%) | 平均CRC级别 |
D102-97-1 | 0 | 0 | 6.6 | 3.2 | 19.1 |
D102-98-1 | 23 | 0 | 0 | 4.2 | 14.7 |
D102-99-1 | 23 | 0 | 6.6 | 2.9 | 15.3 |
D102-100-1 | 23 | 48 | 0 | 2.3 | 9.9 |
D102-101-1 | 0 | 48 | 6.6 | 8.9 | 34.7 |
D102-102-1 | 11.5 | 24 | 3.3 | 4.1 | 16.8 |
D102-103-1 | 0 | 48 | 0 | 4.0 | 25.9 |
D102-104-1 | 23 | 48 | 6.6 | 3.1 | 11.9 |
D102-105-1 | 0 | 0 | 0 | 1.9 | 18.2 |
表2.H-4080试验设计的CumminsL10结果
表2中数据变化(AVONA)的分析指出,平均流动损失不依赖于所有的三个因素,对于CRC级别的AVONA表示如下。
对于CRC变化的分析:
来源 平方和 Df 平均平方 F-比率 P-值
A(H-9645) 265.651 1 265.651 29.81 0.0028
B(H-661) 28.5012 1 28.5012 3.20 0.1337
AB 124.031 1 124.031 13.92 0.0136
总误差 44.5563 5 8.91125
总量(corr.) 462.74 8
R-平方=90.3712%
R-平方(调整的d.f.)=84.5939%
Est的标准误差=2.98517
平均绝对误差=1.55556
Durbin-Watson统计=2.10796
HiTHC3062和较高级别的AC,BC和ABC明显低于85%置信度水平,因此被排出,模型系数如下。
CRC的回归系数
常数 =-18.4375
A(H-9645) =-0.158696
B(H-611) =0.242708
AB =-0.0142663
回归系数表明HiTEC9645并未如期地降低了CRC响应(其为一种有利影响,因为较低的CRC级别意味着较少的喷射沉积),而HiTEC611则提高了级别。HiTEC9645和HiTEC611之间存在着显著的消极相互作用,也意味着在分散剂低浓度下HiTEC611对CRC的有害影响比在高浓度下分散剂所能抵销的更为多。换句话说当有大量HiTEC9645存在时HiTEC611提高了CRC级别,所述效应表示在图2的相互作用图中。通常0.3的p-值导致了将HiTHC611中单独从模型中被排出:该值指出仅在87%置信程度下该系数和0不同,但是假如模型包括HiTEC9645和HiTEC611之间相互作用,HiTEC611也被包括以便保持模型的等级。
改进的分散剂组合物以通过CumminsL10试验
根据上述提出的模型可以调节例如HiTEC4080中的各组份,以便达到所需的CRC目标。如上所述对于通过CumminsL10的最高的CRC级别是10.0,CRC的恒定响应曲线如图3所示,其中CRC为HiTEC9645和HiTEC611浓度(PTB)的函数。
根据上述CRC的模型,图3中对于10.0曲面(虚线)右侧的HiTEC9645和HiTEC611的任何组合均能够通过CumminsL10评估,在L10试验的9.0曲面上(实线)选择三个点,相应于这三个点的添加剂组合是:
1. 28PTB HiTEC9645+32PTB HiTEC611;
2. 26PTB HiTEC9645+40PTB HiTEC611;
3. 25PTB HiTEC9645+48PTB HiTEC611;
所有三个组合物也包括6.6PTB的Ethyl’s MMT作为如上述HiTEC3062的溶剂,抗乳化剂和防锈剂,得到的CumminsL10数据列于表3。
改进的组合 | 试验号 | 平均流动损失(%) | 平均CRC级别 |
1 | D102-107-2 | 2.0 | 8.6 |
2 | D102-107-1 | 3.1 | 8.5 |
3 | D102-109-1 | 3.3 | 9.9 |
表3.改进的HiTEC4080的CumminsL10结果
如上述模型和数据所预料,所有三个组合物都能够通过CumminsL10试验。
样品23试验设计确定了Greenburn柴油添加剂组合在CumminsL10试验中各组份的定量效果,发现琥珀酰亚胺分散剂(HiTEC9645)对于喷射器等级来说具有有益的效果,而高碱性磺酸钙清净剂(HiTEC611)则损害其效果。另外,还观察到了上述两个组份之间强烈的相互作用,其降低了清净剂的不期望的影响。MMT(HiTEC3062)对于喷射器的清洁度没有很大影响,从试验设计得到的模型被用于配制能够通过CumminsL10试验的改进的Greenburn类型组合物。
本发明的另一实施方案对于理解本发明公开的说明书和具体实例的本领域技术人员是明显的,如通常对说明书和权利要求的理解,“a”和“an”是指一个或一个以上。除非另外指出,在说明书和权利要求中用于表示成份,性能如分子量,百分比,比例,反应条件等等的所有数字在所有情况下均被理解为被术语“大约”修饰,因此除了有相反的说明以外,说明书和权利要求中出现的数字参数都有近似性,它们可以根据通过本发明以得到的所需性能而改变。至少并且不企图将申请限制到和权利要求范围等同的含义,每一数字参数至少是根据被报告的大量数字和通过使用普通完整技术形成的,尽管本发明中的宽范围出现的数字范围和参数是近似的,在具体实施例中出现的数值是尽可能准确的,但是任何数值本身都会包括由于在个别试验测定中出现的不可避免的标准偏差。也就是认为说明书和实施例仅是示范性的,本发明的确切范围和精神记载在以下的权利要求书中。
Claims (12)
1.一种馏出燃料添加剂组合物,其包括有机金属镁化合物,烷基取代的琥珀酰亚胺无灰分散剂和高碱性磺酸钙清净剂。
2.按照权利要求1所述的燃料添加剂组合物,其中有机金属镁化合物包括甲基环戊二烯基镁三羰基。
3.按照权利要求1所述的燃料添加组合物,其中琥珀酰亚胺是由聚异丁烯琥珀酸酐和聚烯烃聚胺制备的。
4.按照权利要求1所述的燃料添加组合物,其中琥珀酰亚胺是由聚异丁烯琥珀酸酐和四亚乙基五胺制备的。
5.按照权利要求1所述的燃料添加组合物,其中烷基取代的琥珀酰亚胺中的聚异丁烯是由分子量约850-2100的聚异丁烯制备的。
6.按照权利要求1所述的燃料添加组合物,其中烷基取代的琥珀酰亚胺中的聚异丁烯是由分子量约850-1300的聚异丁烯制备的。
7.按照权利要求1所述的燃料添加组合物,其中烷基取代的琥珀酰亚胺中的聚异丁烯是由分子量约950的聚异丁烯制备的。
8.按照权利要求1所述的燃料添加组合物,其中的组合物包括有机金属镁配合物,高碱性磺酸钙清净剂和无灰烷基取代的琥珀酰亚胺分散剂,当添加剂组合物溶解于馏出燃料中时,要满足以下关系:
-0.159x+0.243y-0.0143xy≤-8.4
其中x=琥珀酰亚胺浓度(磅/千桶)
y=高碱性磺酸钙浓度(PTB)
同时有以下限定:
x=20-35和y=10-120。
9.按照权利要求1所述的燃料添加组合物,其中高碱性磺酸钙的TBN约为200以上。
10.按照权利要求1所述的燃料添加组合物,其中高碱性磺酸钙的TBN约为300。
11.一种燃料,其含有较大量中间馏份油和少量的燃料添加剂组合物,所述燃料添加剂组合物其含有有机金属镁化合物,烷基取代的琥珀酰亚胺无灰分散剂和TBN约为300的高碱性磺酸钙清净剂。
12.一种改进燃料吸入体系清洁度的方法,其在燃料吸入体系中使用含有馏出燃料添加剂组合物的燃料,所述馏出燃料添加剂组合物中包括有机金属镁化合物,烷基取代的琥珀酰亚胺无灰分散剂和TBN约为300的高碱性磺酸钙清净剂。
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US10/614,771 US20050005506A1 (en) | 2003-07-08 | 2003-07-08 | Distillate fuel compositions for improved combustion and engine cleanliness |
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KR20070055386A (ko) * | 2005-11-25 | 2007-05-30 | 인피늄 인터내셔날 리미티드 | 선박용 또는 정치식 디젤 엔진의 작동 방법 |
EP1790710A1 (en) | 2005-11-25 | 2007-05-30 | Infineum International Limited | A Method of Operating a Marine or Stationary Diesel Engine |
US8883865B2 (en) | 2006-09-05 | 2014-11-11 | Cerion Technology, Inc. | Cerium-containing nanoparticles |
EP2064153B1 (en) | 2006-09-05 | 2016-06-29 | Cerion LLC | Method of preparing cerium dioxide nanoparticles |
US10435639B2 (en) | 2006-09-05 | 2019-10-08 | Cerion, Llc | Fuel additive containing lattice engineered cerium dioxide nanoparticles |
CA2782212A1 (en) * | 2009-11-30 | 2011-06-03 | The Lubrizol Corporation | Methods of controlling sulfur trioxide levels in internal combustion engines |
CN103205288B (zh) * | 2013-03-06 | 2016-01-20 | 陕西明瑞资源再生有限公司 | 一种清洁合成柴油及其合成工艺 |
WO2015058037A1 (en) | 2013-10-17 | 2015-04-23 | Cerion, Llc | Malic acid stabilized nanoceria particles |
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US3883320A (en) * | 1972-12-07 | 1975-05-13 | Standard Oil Co | Reducing deposits and smoke from jet fuels with additives incorporating an ammonium salt |
US4247301A (en) * | 1978-06-19 | 1981-01-27 | Chevron Research Company | Deposit control and dispersant additives |
US4240801A (en) * | 1979-05-31 | 1980-12-23 | Ethyl Corporation | Diesel fuel composition |
US4482356A (en) * | 1983-12-30 | 1984-11-13 | Ethyl Corporation | Diesel fuel containing alkenyl succinimide |
US4659338A (en) * | 1985-08-16 | 1987-04-21 | The Lubrizol Corporation | Fuel compositions for lessening valve seat recession |
US4781730A (en) * | 1987-06-05 | 1988-11-01 | The Lubrizol Corporation | Fuel additive comprising a hydrocarbon soluble alkali or alkaline earth metal compound and a demulsifier |
US5944858A (en) * | 1990-09-20 | 1999-08-31 | Ethyl Petroleum Additives, Ltd. | Hydrocarbonaceous fuel compositions and additives therefor |
EP0476196B1 (en) * | 1990-09-20 | 1993-11-18 | Ethyl Petroleum Additives Limited | Hydrocarbonaceous fuel compositions and additives therefor |
DE69006029T2 (de) * | 1990-09-20 | 1994-05-05 | Ethyl Petroleum Additives Ltd | Kohlenwasserkraftstoffzusammensetzungen und Zusätze dazu. |
AU668151B2 (en) * | 1992-05-06 | 1996-04-26 | Afton Chemical Corporation | Composition for control of induction system deposits |
GB2285057B (en) * | 1993-12-23 | 1997-12-10 | Ethyl Petroleum Additives Ltd | Evaporative burner fuels and additives therefor |
US5454843A (en) * | 1994-03-02 | 1995-10-03 | Ethyl Corporation | Reducing deposit formation in gasoline engines |
GB2289287A (en) * | 1994-05-04 | 1995-11-15 | Ethyl Petroleum Additives Ltd | Fuel foam control additive |
CA2205143C (en) * | 1996-05-14 | 2003-07-15 | Ethyl Corporation | Enhanced combustion of hydrocarbonaceous burner fuels |
GB2321906A (en) * | 1997-02-07 | 1998-08-12 | Ethyl Petroleum Additives Ltd | Fuel additive for reducing engine emissions |
GB2322138A (en) * | 1997-02-17 | 1998-08-19 | Ethyl Petroleum Additives Ltd | Foam reducing fuel additive |
GB9714828D0 (en) * | 1997-07-15 | 1997-09-17 | Exxon Chemical Patents Inc | Improved fuel oil compositions |
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- 2004-07-07 CN CNB200410063711XA patent/CN100506955C/zh not_active Expired - Fee Related
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