CN1520455A - 燃料添加剂 - Google Patents
燃料添加剂 Download PDFInfo
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Abstract
公开了一种含有油酸链烷醇酰胺和烷氧基化油酸的燃料添加剂组合物。还公开了一种含有烃燃料和包含油酸链烷醇酰胺和烷氧基化油酸的燃料添加剂的燃料组合物,以及用本发明的燃料开动内燃机的方法。
Description
本发明涉及一种新型燃料添加剂,其制备方法和应用以及新型燃料配方。
表面活性剂已很长时间用作可影响燃料如汽油和柴油性能的添加剂。英国专利No 2217229公开了一种增溶的化合物作为燃料添加剂。具体地是公开了含有如下成分的组合物:
48份体积的脂肪醇乙氧基化物;
3-8份体积的月桂酸二乙醇酰胺;
3-8份体积的油酸二乙醇酰胺;和
1.5-4份体积的聚乙二醇醚和乙氧基化油酸。
这样的组成作为燃料添加剂是有效的并且能够增溶燃料中的水,因而减少了燃料的潜在腐蚀性作用。不过,这种组合物是有缺点的,特别在于它们要求高的添加剂/燃料比。此外,没有提及气体如CO,CO2和NOx的放出问题。
国际专利申请No WO 98/17745公开了另一种配方,它含有:
25%重量/重量的二乙醇酰胺;
50%重量/重量的乙氧基化醇;和
25%重量/重量的具有7个乙氧基基团的十四碳链脂肪酯。
WO‘745特别公开了包含特别是由脂肪酸二乙醇酰胺,脂肪醇乙氧基化物和脂肪酸的乙氧基化物组成的添加剂的燃料组合物,乙氧基化程度的选择要能够形成长期稳定的燃料组合物,特别是,其中通过仔细地选择乙氧基化程度可产生平衡的掺合物。
尽管这种添加剂提供了气体放出的明显减少和在低浓度下是可用的,但是仍需要能够减少气体放出,同时保持其性能水平的燃料组合物,并且可以更为经济有效地应用。
我们已令人惊异地发现,不使用乙氧基化醇可制备更为有利的添加剂。
因而按照本发明,我们提供了一种含有油酸链烷醇酰胺和烷氧基化油酸的燃料添加剂组合物。
如上所述的燃料添加剂组合物的特征特别在于醇,尤其是乙氧基化醇在该组合物中基本上是不存在的。因此我们提供的以上所述的燃料添加剂是实质上没有醇,特别是乙氧基化醇的。
油酸链烷醇酰胺优选是乙醇酰胺和更优选二乙醇酰胺。特别优选的是二乙醇酰胺和尤其是超二乙醇酰胺。
通常,有三种商业路线得到链烷醇酰胺:
酸十链烷醇胺=链烷醇酰胺+水
植物或动物油(甘油三酯)+链烷醇胺=链烷醇酰胺+甘油
甲基酯+链烷醇胺=链烷醇酰胺+甲醇
这些路线是按产品质量增加的顺序列出的。经由酸的路线通常应用过量的链烷醇胺,以得到此由用化学计量比的酸得到的产品更高酰胺量的产品;这些产品有时称为超酰胺。
油酸乙氧基化物可由全世界容易得到的各种原料产生。然而,在本发明的一个优选实施方案中油酸乙氧基化物可通过由动物脂肪如牛油或植物油如豆油等产生的酸的乙氧基化或酯化来制取。这样油酸母体可含有占优势,例如65-70%体积/体积的油酸,但也可含有亚油酸,例如10-12%体积/体积,还可包括少量硬脂酸,棕榈酸和/或肉豆蔻酸。
烷氧基化物可以是乙氧基化物或丙氧基化物或它们的混合物。乙氧基化的程度选定要使具有油酸二乙醇酰胺的掺合物性能最优化和可从0.5-20,但更优选从0.5-10,还更优选1-3。适合于这一范围内的产物例如可以是由1分子环氧乙烷加到1分子油酸中产生的。
油酸烷氧基化物与油酸链烷醇酰胺之比可以变化,且可以是从99∶1-1∶99体积/体积,优选3∶1-1∶1体积/体积和最优选1∶1体积/体积。
本发明的添加剂可以加到任何已知的烃燃料例如柴油,石油或醇如乙醇中,它可以含有水或不含水。本发明发现当加入到基于低馏分油的燃料中时效果特别好。
于是,按照本发明的进一步的特征,我们提供一种含有烃燃料的燃料组合物和如上文所述的燃料添加剂。
燃料组合物中该添加剂的浓度可以不同,特别是取决于燃料的特征,不过该浓度可以是很低的,一般为0.5∶1000-50∶1000体积/体积数量级,优选1∶1000-50∶1000体积/体积,更优选1∶100-5∶100体积/体积。
烃燃料可包含任何已知的烃燃料或它们的混合物,因此这些燃料包括但应不限于柴油,例如石油柴油,生物柴油,汽油,航空燃料,醇等。
在本发明的一个燃料组合物实施方案中,烃燃料是石油柴油燃料。这种燃料一般可从石油的蒸馏得到,其效力可用十六烷值测定。适合用于本发明的柴油燃料一般具有的十六烷值为35-60,优选40-50。基于燃料使用量的总体积,为了形成本发明的燃料组合物混合的柴油燃料的量可为60%体积/体积-95%体积/体积。该柴油燃料可以包括石油柴油,生物柴油或生物柴油与石油柴油以99∶1-1∶99的任何比例混合。
优选,当本发明的燃料是生物柴油和石油柴油的混合物时,这可含有至多50%体积/体积的生物柴油,例如1~50%体积/体积,优选5-30%体积/体积,更优选10-20%体积/体积。
在本发明的另一个特征中,烃燃料如柴油或汽油可包括一定量的充氧剂,例如醇,一种链烷醇,如乙醇。当有醇存在时,醇的量可以变化,特别是取决于燃料的特性,且可以是1-50%体积/体积的量,优选5-20%体积/体积。
用作燃料的乙醇可从矿物燃料原料或通过得自谷物或其他生物原料的糖的发酵产生。因此,适合于本发明的燃料组合物应用的乙醇可以是得自酵母或微生物发酵的淀粉基糖的燃料级乙醇。这种淀粉基糖可以从玉米,甘蔗,木薯淀粉和制糖甜菜中提取。另外,燃料级乙醇可由特定的生物原料通过已知的稀和/或浓酸和/或酶促水解产生,例如从废工业源包括城市废物的纤维素部分,废纸,纸淤渣,锯末产生。生物量材料也可从农业残余物包括例如米壳和造纸场淤渣收集。
适合用于本发明的燃料级乙醇可不含或仅含少量的水。此外,适用于本发明的燃料级乙醇可含较高量的水,直达5%重量/重量(含水乙醇)。
以前乙醇与柴油燃料结合使用造成一些问题,其中乙醇/柴油燃料混合物会令人不快地分离成两个截然不同的相,特别是当有水存在时,并使该混合物不适于用作易燃的燃料。使用本发明的燃料添加剂可使含水乙醇与传统的柴油燃料令人满意地混合而不会产生两相。使用本发明的混合燃料级乙醇,能够给予总燃料组合物一些理想的燃料特性,如改进的燃料稳定性,较低的烟尘和颗粒物,较低的CO和NOx的放出,改进的抗曝震特性,和/或改进的防冻特性。
在说明本发明的燃料组合物时,燃料添加剂中不存在醇不应理解为在燃料组合物中不存在醇,例如乙醇。
本发明添加剂的存在保证了燃料组合物形成一种始终稳定的均匀组合物和同时产生一个单层,其结果导致更完全的燃料,从而减少了污染和增加了每加仑英里数。
结果,混合燃料,特别是醇基的混合燃料能够用较冷燃料时更精确地烧尽,以减少醛过酸和过氧化物反应中产生的铁-甲酸盐,它们是造成发动机破坏的原因。
在本发明的另一个方面,我们提供一种如含有液体烃燃料和上文所述表面活性剂组合物的燃料组合物。
在本发明的燃料组合物中,烃燃料可以是任何通常已知的燃料,例如汽油,柴油,生物柴油等。此外,本发明的燃料可任何地包括一种充氧剂,该充氧剂可以是醇,例如乙醇。当像乙醇这样的充氧器存在时,燃料中乙醇的量可以不同,并可以是从0-25%体积/体积乙醇,优选1-10%体积/体积乙醇。
我们进一步提供一种开动内燃机和方法,其包括使用本发明的燃料组合物。
国际专利申请No.WO 99/35215,Wenzel,描述了一种用于易燃燃料的添加剂,其包括一个氮源,如尿素。尽管该添加剂被说成是减少NOx,但该组合物是很复杂的,并包括许多成分,其中包括:
水溶性醇,
C6-C12醇,
C6-C18乙氧基化醇,
C10-C24脂肪酸,和
一个氮源。
我们现在令人惊奇地发现前述的添加剂与含氮化合物如尿素结合时适合于以很低的燃料:添加剂比例应用。
因此按照本发明,我们提供一种包含如上文所述的油酸链烷醇酰胺,烷氧基化的油酸和含氮化合物的燃料添加剂组合物。
该氮化合物可以选自氨,肼,烷基肼,二烷基肼,尿素,乙醇胺,单烷基乙醇胺,和二烷基乙醇胺,其中的烷基独立地选自甲基、乙基、正丙基或异丙基。尿素是优选的。该含氮化合物可以是无水的化合物或含水的化合物,例如一种水溶液,和可以是高达5%重量/重量的水溶液。
按照本发明的再一个特征,我们提供一种增溶燃料组合物中的含氮化合物的方法,该方法包括混合如上文所述的烃燃料、氮化合物和燃料添加剂。本发明的方法可任选地包括加入一种醇如乙醇或水,如上文所述。
我们还提供在制造本发明的燃料添加剂时使用氮化合物。我们特别提供在制造本发明的燃料添加剂时使用尿素。
我们还提供一种含有烃燃料,如前文所述的添加剂和氮的化合物的燃料组合物。
在本发明的这种燃料组合物中,含氮化合物可通过掺入燃料添加剂中的方式加入,或可以单独地加入。
此外,含氮化合物可以以水溶液的形式加入。
本发明超过现有技术的特别优点是可以制成实质上无水的燃料组合物,除了痕量的水沾污外。术语痕量水沾污我们一般意指0.1%重量/重量的水或更少。
于是,按照本发明的另一方面,我们提供在制造如前所述的燃料组合物时使用尿素。
本发明的燃料添加剂或燃料组合物也可任选地包含十六烷值助促进剂,其量按混合物体积计为0.1%体积/体积-10%体积/体积。当十六烷值助促进剂包括在本发明的燃料组合物中时,它可以作为本发明添加剂的一部分加入,或可单独加入。
适用于该混合物的十六烷值助促进剂选自硝酸2-乙基己基酯,叔丁基过氧化物,二甘醇甲基醚,环己醇和它们的混合物。该混合物中十六烷值助促进剂存在的量随特定的柴油燃料的十六烷值和特定燃料组合物中存在的乙醇量而变化。通常柴油燃料的十六烷值愈低,十六烷值助促进剂的量愈高。类似地,由于乙醇通常起着十六烷值抑制剂的作用,所以溶液中乙醇的浓度愈高,就会需要混合物中有更多的十六烷值助促进剂。
本发明的燃料添加剂的优点尤其在于它们在产生微乳状液方面比现有技术的添加剂更有效。因此甚至在水的存在下它们能够与烃燃料,例如柴油/乙醇更有效地产生稳定、清亮和均匀的溶液。因此,按照本发明的另一个方面,我们提供如上文所述的一种燃料组合物,它任选地包括一定量的水,和该燃料是由基本上稳定,基本上清亮,基本上均匀的溶液构成。
此外,本发明的燃料添加剂或燃料组合物也可任选地包括一种破乳剂,其量按混合物的体积计少于5%体积/体积和优选少于1%体积/体积。
燃料组合物处于或接近其浊点时的量度是根据该燃料的电导率测定的。例如水的电导率为100mS cm-1和醇,例如乙醇的电导率为20-30mS cm-1。燃料,如汽油或柴油是非极性的,其电导率实际上是0。此外,我们发现燃料,例如如前所述汽油或柴油,任选地包括醇如乙醇的非均匀混合物可具有较高的电导率读数,而当均匀性趋近时,电导率将减小,而且当该组合物是清亮均匀的溶液时,电导率达到最小值。
按照本发明的另一个方面,我们提供一种测定燃料组合物均匀性的方法,该方法包括测量该组合物的电导率。
电导率可在不同的温度下测定。然而,我们发现在实际上为环境温度的情况下测量是优选的,和尤其是在25.1℃。下面给出的电导率值都涉及在25.1℃测定的这种值。此外,由于已知电导率可随温度的不同而不同,所以于不同温度取得的任何电导率值均应按在25.1℃测量的值进行校准。
我们特别提供一种测定燃料组合物均匀性的方法,该组合物含有一种燃料和一种充氧剂。
本发明的优选添加剂是非离子型表面活性剂,优选某些表面活性剂的混合物。本发明的一个优选的方面是,根据其特性和使用中的浓度选择表面活性剂,将添加剂(以及任何存在的水和非燃料液体)在燃料内增溶。为此目的,方便的是考虑表面活性剂的亲水亲油平衡值(HLB),该值按下式计算。
这些值将取决于亲水链,通常是乙氧基化链的长度。这种链的长度可增加增溶作用的程度,因为其具有较大的增溶能力。
本发明具有统一任何液体燃料的HLB要求的能力,而这又能用于C5以上碳链的任何燃料的某一用量。好处是处理的量直接与共溶能力相关。
现在参考随后的实施例说明本发明,但决不是限制本发明。
实施例1
组合物的制备
通过混合各组分构成添加剂组合物,油酸超二乙醇酰胺,乙氧基化油酸的比例为1∶1。将1%的这种组合物加到7.7%乙醇/92.3%柴油混合物,包括鉴定的柴油,US No 1柴油,10%含0.1%十六烷值增进剂的芳族柴油中,产生光学透明和稳定的微乳状液燃料。将这些燃料作为机动车燃料在1991底特律柴油系列60发动机上用EPA(美国环境保护局)重型发动机鉴定试验进行测试(如联邦管理法规(Code ofFederal Regulations)标题(Title)40,部分(Part)86,亚部分N(Subpart N)中所述)。
测量有毒废气遗漏并与基本无添加剂(unadditised)的柴油的有毒废气遗漏比较。得到有毒气体CO,CO2,NOx和颗粒物的显著减少,结果示于表I-III。
实施例2
试验方案
用柴油,无水乙醇和浓度最高达5%体积/体积的水构成混合物。然后用添加剂滴定浑浊的混合物,直至形成透明、稳定的微乳状液,将微乳化柴油/乙醇/水混合物所需的添加剂体积对水含量绘图,并示于图1中,使用该试验方案可以比较添加剂的相对效率。
图1表明包含油酸二乙醇胺和乙氧基化油酸1∶1比例的添加剂与现有技术的含脂肪酸乙氧基化物,二乙醇胺和乙氧基化醇的比例为1∶1∶2的添加剂的性能比较。
实施例3
石油柴油/生物柴油/乙醇混合物
混合物由鉴定的柴油,生物柴油和乙醇构成,用实施例1中所述表面活性剂添加剂稳定。与基本柴油相比,放出试验表明CO,NOx和颗粒物减少。
实施例4
石油柴油/乙醇/尿素混合物
实施例A 0.25%尿素在乙醇中的溶液与US No 1柴油以7.7∶92.3的比例混合,加入1.0%实施例1中所述的添加剂,产生透明的微乳状液机动车燃料。用该混合物进行试验表明有毒气体的放出比基本柴油又降低,尿素对得到的这种减少做出了贡献。
实施例5
汽油/乙醇混合物
由EPA和CARB汽油与不同量的乙醇构成混合物,例如典型的混合物含有90%体积/体积汽油和10%乙醇。将少量,一般为1%体积/体积的本发明添加剂加到该汽油/乙醇混合物中,所得到的这种燃料作为机动车燃料进行试验,并把废气的放出与基本汽油的废气放出做比较。结果证实乙醇/汽油混合物燃烧产生较低水平的有毒气体放出。
表I
表II
表III
Claims (45)
1.一种含有油酸链烷醇酰胺和烷氧基化油酸的燃料添加剂组合物。
2.权利要求1的燃料添加剂组合物,其特征在于该添加剂基本上是没有乙氧基化醇的。
3.权利要求1的燃料添加剂,其特征在于油酸链烷醇酰胺是乙醇酰胺。
4.权利要求3的燃料添加剂组合物,其特征在于油酸乙醇酰胺是二乙醇酰胺。
5.权利要求1的燃料添加剂组合物,其特征在于烷氧基化油酸是乙氧基化的油酸,丙氧基化的油酸或它们的混合物。
6.权利要求5的燃料添加剂,其特征在于烷氧基化油酸是乙氧基化的油酸。
7.权利要求5的燃料添加剂组合物,其特征在于烷氧基化的程度是每摩尔油酸0.5-10摩尔烷氧基化物。
8.权利要求7的燃料添加剂组合物,其特征在于烷氧基化的程度是每摩尔油酸1摩尔烷氧基化物。
9.权利要求1的燃料添加剂组合物,其特征在于烷氧基化油酸的母体含有65-70%体积/体积油酸。
10.权利要求9的燃料添加剂组合物,其特征在于烷氧基化油酸母体含有其他的酸,这些酸选自一种或多种亚油酸,硬脂酸,棕榈酸和肉豆蔻酸。
11.权利要求1的燃料添加剂组合物,其特征是油酸二乙醇酰胺与乙氧基化油酸的比例为99∶1-1∶99体积/体积。
12.权利要求11的燃料添加剂,其特征为油酸二乙醇酰胺与乙氧基化油酸之比是1∶1。
13.一种含有烃燃料和权利要求1的燃料添加剂的燃料组合物。
14.权利要求13的燃料组合物,其特征在于烃燃料是选自一种或多种柴油,例如石油柴油或生物柴油,汽油,航空燃料和醇。
15.权利要求13的燃料组合物,其特征在于组合物包括一定量的水,和燃料由基本稳定,基本透明和基本均匀的溶液组成。
16.权利要求13的燃料组合物,其特征在于添加剂与燃料之比为0.5-50∶1000体积/体积。
17.权利要求16的燃料组合物,其特征在于添加剂与燃料之比为1∶1000-50∶1000体积/体积。
18.权利要求17的燃料组合物,其特征在于添加剂与燃之比为1-5∶100体积/体积。
19.权利要求13的燃料组合物,其特征在于燃料是柴油燃料。
20.权利要求19的燃料组合物,其特征在于柴油燃料是石油柴油。
21.权利要求20的燃料组合物,其特征在于柴油燃料是石油柴油和生物柴油的混合物。
22.权利要求20的燃料组合物,其特征在于柴油燃料是生物柴油。
23.权利要求19的燃料组合物,其特征在于燃料是柴油和醇的混合物。
24.权利要求23的燃料组合物,其特征在于醇是乙醇。
25.权利要求23的燃料组合物,其特征在于燃料是含水乙醇/柴油混合物。
26.权利要求25的燃料组合物,其特征在于添加剂与燃料之比最高可达5%体积/体积。
27.权利要求23的燃料组合物,其特征在于燃料是无水乙醇/柴油混合物。
28.权利要求13的燃料组合物,其特征在于燃料是汽油。
29.权利要求28的燃料组合物,其特征在于燃料是汽油/乙醇混合物。
30.权利要求29的燃料组合物,其特征在于添加剂与燃料之比最高可达5%体积/体积。
31.权利要求13的燃料组合物,其特征在于还有含氮的化合物存在。
32.权利要求31的燃料组合物,其特征在于含氮的化合物选自氨,肼,烷基肼,二烷基肼,尿素,乙醇胺,单烷基乙醇胺,二烷基乙醇胺,其中烷基独立地选自甲基,乙基,正丙基或异丙基。
33.权利要求32的燃料组合物,其特征在于含氮的化合物是尿素。
34.一种增溶燃料组合物中含氮的化合物的方法,其包括混合烃燃料,含氮的化合物和权利要求1的燃料添加剂组合物。
35.含氮化合物在制备权利要求31的燃料组合物中的用途。
36.权利要求35的用途,其特征在于含氮的化合物是尿素。
37.权利要求1的燃料添加剂,其特征在于该添加剂还包含十六烷值助促进剂,其量为0.1%体积/体积至10%体积/体积。
38.权利要求13的燃料组合物,其特征在于该燃料组合物还含有十六烷值助促进剂,其量为0.1%体积/体积至1%体积/体积。
39.权利要求1的燃料添加剂,其特征在于该添加剂还包含一种破乳剂,其量少于5%体积/体积。
40.权利要求13的燃料组合物,其特征在于该燃料组合物还含有破乳剂,其量少于5%体积/体积。
41.油酸链烷醇酰胺在制备权利要求1的燃料添加剂中的用途。
42.烷氧基化油酸在制备权利要求1的燃料添加剂组合物中的用途。
43.一种开动内燃机的方法,该方法包括使用权利要求13的燃料。
44.权利要求43的方法,其特征在于从该发动机排放的废气的毒性减少。
45.实质上如说明书实施例所描述的燃料添加剂或燃料组合物。
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GB0110354.8 | 2001-04-27 | ||
GBGB0110354.8A GB0110354D0 (en) | 2001-04-27 | 2001-04-27 | Fuel additives |
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CN1229474C CN1229474C (zh) | 2005-11-30 |
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US (1) | US7172635B2 (zh) |
EP (1) | EP1390451A2 (zh) |
JP (1) | JP2004528453A (zh) |
CN (1) | CN1229474C (zh) |
BR (1) | BR0209209A (zh) |
CA (1) | CA2445419A1 (zh) |
GB (1) | GB0110354D0 (zh) |
MX (1) | MXPA03009843A (zh) |
PL (1) | PL364380A1 (zh) |
RU (1) | RU2003134365A (zh) |
WO (1) | WO2002088280A2 (zh) |
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- 2002-04-26 PL PL02364380A patent/PL364380A1/xx unknown
- 2002-04-26 CA CA002445419A patent/CA2445419A1/en not_active Abandoned
- 2002-04-26 CN CNB028127498A patent/CN1229474C/zh not_active Expired - Fee Related
- 2002-04-26 JP JP2002585564A patent/JP2004528453A/ja active Pending
- 2002-04-26 EP EP02766652A patent/EP1390451A2/en not_active Withdrawn
- 2002-04-26 WO PCT/GB2002/001867 patent/WO2002088280A2/en not_active Application Discontinuation
- 2002-04-26 BR BR0209209-3A patent/BR0209209A/pt not_active IP Right Cessation
- 2002-04-26 RU RU2003134365/04A patent/RU2003134365A/ru not_active Application Discontinuation
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CN101469284B (zh) * | 2007-12-27 | 2012-09-12 | 中国石油化工股份有限公司 | 一种柴油十六烷值改进剂组合物及含有该组合物的柴油 |
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Also Published As
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JP2004528453A (ja) | 2004-09-16 |
WO2002088280A3 (en) | 2002-12-27 |
EP1390451A2 (en) | 2004-02-25 |
MXPA03009843A (es) | 2004-12-06 |
GB0110354D0 (en) | 2001-06-20 |
CN1229474C (zh) | 2005-11-30 |
PL364380A1 (en) | 2004-12-13 |
WO2002088280A2 (en) | 2002-11-07 |
US20040200137A1 (en) | 2004-10-14 |
US7172635B2 (en) | 2007-02-06 |
BR0209209A (pt) | 2004-07-06 |
RU2003134365A (ru) | 2005-06-10 |
CA2445419A1 (en) | 2002-11-07 |
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