CN100378206C - 烃燃料添加剂及相关方法 - Google Patents
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Abstract
本发明涉及用来提高效率和/或降低污染的烃燃料的燃料添加剂领域。燃料添加剂是可以分散在烃燃料或液体载体中的含磷组合物,其与燃料在燃烧区燃烧。
Description
相关申请
本专利申请要求2003年6月23日申请的系列号为No.60/480,701的美国临时专利申请的优先权,在这里将其全部引入作为参考。
发明的技术领域
本发明涉及燃料添加剂领域,尤其是涉及用于提高效率和/或降低污染的烃燃料添加剂。
发明背景
已经使用了许多烃燃料,其中每种都具有自己的优点和缺点。这些燃料的例子包括汽油、天然气、柴油、煤油、喷气式发动机燃料、LPG、重馏分、船用燃料、乙醇、煤、其它固体烃燃料等。在上一世纪,化合物已被用作燃料添加剂以改善各种燃料的各种参数,例如辛烷值。已知在很长时间内使用含铅汽油并随后被禁止。四乙基铅对辛烷值具有正效应而对环境有很大地负面影响。
除了四乙基铅以外,已知有几种元素在汽油或其它燃料中具有燃烧催化剂的特性。例如,除铅以外,有锰、铁、铜、铈、钙和钡。这些元素中的每一种在特定应用中都具有优点和缺点。某些铁化合物的缺点包括在汽油中有限的溶解度、毒性,并且作为添加剂是昂贵的。还可能与硫发生相互作用并产生硫化物沉淀,这是不期望的。
另一种经常用于汽油的添加剂是MTBE。虽然这种化合物使辛烷值显著增加,但该化合物被认为具有致癌性。还有,它易于与水混合,一旦泄漏就很危险。从加油站的地下储罐中泄漏的含MTBE汽油能潜在地溶入地下水并污染水井。由于MTBE对环境具有潜在的负面作用,乙醇也被考虑作为增加辛烷值的汽油添加剂。
除了提高燃烧效率这一工业目的,也要关注降低排烟量,特别是对于柴油燃料领域。工业上在降低烟气和颗粒物排放的燃料添加剂的发展上没有作出实质性的进步。
最后,调整燃烧参数尝试使其在降低CO和NOX排放方面的作用最大化。尽管这些尝试和这些尝试的组合试图使污染物最小化,然而就提高燃料效率和降低污染物而言,燃料燃烧仍然是一个关注的焦点。
包括燃烧催化剂的燃料添加剂在降低使用汽油燃料的公共汽车、卡车和汽车发动机的烟气和颗粒排放物方面是有利的。在柴油燃料应用中,提高效率和/或降低污染物的燃料添加剂也是有利的。在燃料应用中,降低烟气、颗粒和氮排放物是有利的。不会导致沉淀物形成的添加剂也是有利的。使产生的NOX含量降低的烃燃料添加剂也是有利的。最后,在燃烧过程中保持稳定的添加剂是有利的。
发明概述
本发明包括燃料添加剂和在烃燃料中使用该添加剂的方法。
本发明的燃料添加剂包括含[Y]XH2PO4、[Y]X+HPO4的含磷母液,其中Y是阳离子。在两种盐化合物中,Y不必是相同的阳离子。盐组分的阳离子部分可以是任何的阳离子,钾是优选的阳离子。在这种情况下,优选的化合物是KH2PO4、K2HPO4。这些盐至少部分地分散于水或其它适当的溶剂中以产生含磷母液。有利地,燃料添加剂的这个实施方案是无氨溶液。一种优选的实施方案包括在水存在下添加这些组分以产生作为含水母液的含磷母液。水做溶剂。其它优选的溶剂包括烃或醇。另一组优选的阳离子是碱金属或LA族元素。虽然NH4用作Y形成的燃料添加剂能提高燃料性能,但存在优选避免使用铵及氨的情况。
添加含磷母液或与载体流体混合。在烃燃料中,载体流体是用来将盐以至少部分分散的状态保持在载体流体中的流体,其是可混溶的,或能被保持在溶液中。在一个优选的实施方案中,通过热方式用载体流体从含磷母液中除去大部分溶剂,以产生燃料添加剂。当在燃烧区与燃料接触并燃烧时,燃料添加剂能增强燃烧。当与不含燃料添加剂的燃料相比较时,增强的燃烧意味着使燃料效率提高,或者使燃烧产生的废气中的污染物排放降低或这些效应的结合。典型的污染物可以包括烃燃料燃烧产生的NOX、颗粒物质、一氧化碳和其它公认的污染物。应当指出不同的地理区域根据空气特征集中力量使特定颗粒污染物最小化。降低目标污染物或组合污染物是非常有利的。或者,提高燃料效率导致污染物的总体积降低,还有经济优势。
含磷母液的另一个优选的实施方案包括将[NH4]2HPO4加入[Y]XH2PO4、[Y]X+HPO4和水中。而另一个实施方案包括加入NH4C2H3O2,其中C2H3O2 -离子是醋酸根,这样溶液含有[Y]XH2PO4、[Y]X+HPO4、[NH4]2HPO4、NH4C2H3O2和水。当使用铵化合物制备燃料添加剂时,铵化合物定义为那些含有NHX基团的化合物,溶液中的氮基本上都以铵离子形式存在。至多存在可忽略数量的游离氨气。在一个优选的实施方案中,溶液的pH值为约6.0到8.0。
含磷母液的另一个优选的实施方案包括将[Y]XPO4加入[Y]XH2PO4和[Y]X+HPO4中。
虽然已经描述了正磷酸,也称作磷酸,但包括焦磷酸,它是正磷酸的缩合类似物。不同的是,通过使正磷酸缩合的方法,PO4 3-变成P2O7 2-或其它缩合的磷酸盐。因此,[Y]XH2PO4和[Y]X+HPO4是焦磷酸的前体。使用焦磷酸和其它缩合形式由此包含在正磷酸盐形式的定义内。
本发明一种实施方案的含磷母液可以用于任何类型的环境中,例如含水或亲水环境。在亲水环境的情况下,选择载体流体来进行适当的分散是有利的。在优选的实施方案中还包含在载体流体中促进分散以产生燃料添加剂的分散剂。对于液体烃燃料应用,至少一种载体流体可优选是与燃料高度混溶的亲水流体。
与没有燃料添加剂的燃料的燃烧相比,本发明的燃料添加剂可用于增强燃烧从而达到更充分的燃烧,使生成CO2和H2O的燃烧增加。结果是部分燃烧的产物以及NOX减少,从而提高了燃料效率。
通过将这种添加剂以足以使燃料效率提高或降低污染物的数量加入燃料中使用燃料添加剂。术语增强或增强燃烧是指这些效果中的任一个。使污染物降低的例子是使燃烧区产生的废气中的NOX降低。有利地是,通过添加本发明的燃料添加剂观察到了这两种效果。优选的实施方案包括通过燃料添加剂的添加将约50到150ppm磷加入到燃料中。增加磷的量也是有效的。应当指出可以用低重量百分比的磷制备非常划算的溶液。另一个优选目标是约1ppm的磷到150ppm的磷。低至0.25ppm的磷已经产生积极的试验结果。
本发明包括一种提高燃烧系统中烃燃料的燃料性能的方法,其中包括在烃燃料中加入有效提高烃燃料的燃料性能的量的燃料添加剂并使含有燃料添加剂的燃料燃烧的步骤。燃烧系统可以是本领域普通技术人员已知的用于燃烧烃的任何方式。燃烧系统可以包括一个或多个燃烧区。在一个优选的实施方案中,本方法使用液体烃燃料。类似地,添加剂可以和固体烃燃料一起使用。将添加剂加入烃燃料的结果是产生一种增强燃料,其具有大量适用于燃烧的烃燃料,和用来促进燃烧的一定数量的添加剂。优选地,与没有燃料添加剂的烃燃料的燃烧相比,增强燃料含有的磷的数量可以降低增强燃料燃烧时的排放物。更优选地,增强燃料含有约1到150ppm(重量)的磷。
本发明可选择的实施方案包括在燃烧系统中使烃燃料的燃料性能提高的方法,其中包括向烃燃料中加入有效量的化学添加组合物以提高燃料性能的步骤。通过生成中间溶液产生化学添加组合物,该中间溶液通过(i)在含水介质中混合活性NH2基源与下述中的一种得到:
(a)碱金属氢氧化物,以使中间溶液的pH值提高至12以上以形成铵/碱金属氢氧化物水溶液;或
(b)磷酸源,以使中间溶液的pH值降低至约0以形成酸性铵混合物。
下一个步骤包括将步骤(i.a.)的中间溶液与磷酸源混合;或者将(i.b.)的中间溶液以足以产生强放热反应的速率与氢氧化物混合。这导致在化学添加组合物形成期间,溶液中含有活性NH2基。将该化学添加组合物加入烃燃料。
本发明的母液或化学添加组合物可以被加入或包括燃烧燃料。再者,有利地是在烃基燃料中包含促进分散的分散剂。典型的燃料包括汽油和柴油燃料。
当适用于燃烧的大量燃料与一定数量的含磷母液或化学添加组分合物相混合时产生增强燃料,该含磷母液或化学添加组合物的数量足以使增强燃料燃烧的排放物降低或效率提高。在某些环境下,载体流体是一定数量的目标流体,即含有理想燃料的流体。
美国专利No.5,540,788中已经披露了磷酸、碱金属氢氧化物和活性NH2基源的组合物,该组合物用于产生转化表面,该专利的公开内容在这里引用作为参考。本发明包括转化表面组合物作为燃料添加剂的用途。在一个实施方案中,燃料添加剂是用于烃燃料增强的化学添加组合物,其中所述化学添加组合物具有美国专利No.5,540,788公开的组成。该实施方案在活性NH2基源的使用方面是独特的,其在某些环境条件下是有利的。虽然包括活性NH2基的化学组合物具有某些优点,但其能导致游离氨存在。本发明的燃料添加剂的各种其它实施方案避免游离氨和相关问题的产生。
发明详述
在本方法中,本发明的燃料添加剂据信是实施烃燃料的气相转化,以实现更充分地燃烧成CO2和H2O。优选地,燃料添加剂作为载体流体中分散体提供。制备优选包括形成乳化的含水母液并随后加入基础油中。通过应用乳化剂和分散剂可以帮助分散。在一个优选的实施方案中,使用基于无油基的总基数为30到160的分散剂。使用红外和其它试验技术进行试验确定具有本发明燃料添加剂的烃燃料燃烧排放的废气中的CO降低。
这里公开的新组合物和前述的Defalco组合物都可以用来产生增强的燃料性能。
本发明包括燃料添加剂在发动机燃烧室中的用途。对于用于柴油发动机,这被认为是特别有价值的。用于发动机为燃烧提供使颗粒物和其它排放物降低的好处。本发明的方法在燃烧过程中产生的高温下是有效的,从而在发动机在燃烧过程中产生的热量导致的高温下运行时,燃料添加剂能与金属部件接触。
试验显示,由于发动机热被降低,在燃料中使用燃料添加剂提供了保护。假定这是绝缘作用的结果。还有,氧自由基增加。观察到效率提高。该效率提高可能是燃烧期间催化作用的结果。
本发明优选配方的一个例子包括以下比率:1.597摩尔KH2PO4、0.693摩尔K2HPO4、0.315摩尔[NH4]2HPO4和水。通过调节这些组分的比率可以控制溶液的pH值。通过调节产生的H2PO4 -和HPO4 2-离子的比率,溶液可以产生优选的约6.0到约8.0的pH值。
在一个优选的实施方案中,KH2PO4,K2HPO4,[NH4]2HPO4和水产生含磷母液,将该母液加入载体流体,例如精制油载体流体,并与分散剂混合。典型的分散剂包括Chevron的TFA 4690C、聚链烯基琥珀酰亚胺、和Oronite ODA 78012或Ethyl Corporation,Richmond Va的Ethyl Hitec 646。典型的载体流体包括聚氧丙烯单醇和多醇、聚氧丁烯单醇和多醇,Bayer,Pittsburg,Pa等的ActaclearND17,等等。以约10wt%的比例将含磷母液加入精制油载体流体。加热除去大部分数量的溶剂,在这种情况下是水。这时的混合物可以描述为胶体。当将获得的溶液混入燃料中时,溶液中有效量的磷被稀释。优选实施方案的一个例子是溶液中含0.3wt%磷。一旦添加到燃料中,磷含量可以为5-100ppb并且仍是有效的。优选地,在燃料中使用1-250ppm磷。较高的量也是有效的。更优选地,含有燃料添加剂的燃料中有1-150ppm(重量)磷。
可选择实施方案的实施例中,用于燃料的含磷母液包括将约2.6摩尔(M)的碱金属和铵阳离子正磷酸盐混合,获得的含水母液在环境温度下的pH值为7。测定体积的该含水母液悬浮于精制油载体流体和分散剂的混合物中,加热除去含水母液中的大部分水,并稀释至约0.3wt%P。这个混合物,进一步稀释,作为燃料添加剂。优选用相同的精制油载体流体实现稀释。II类基础油是优选的。其它优选的载体流体包括轻质烃、汽油、聚合汽油、煤油、柴油、轻石脑油,API定义的I、III、IV、V或VI类基础油、芳香族油、聚丁烯、聚二醇、重油或它们的混合物。当以这种方式制备的含水母液加入到燃料中时,其作用在于在常规的发动机操作条件下使污染物分子的排放降低。可选择实施方案的实施例包括在水中的磷酸、氢氧化钾、氢氧化铵的用途。也可以添加醋酸。可以调整组分的数量以达到预期的pH值。
实施例1
1、制备磷酸/醋酸溶液[H3PO4/HOAC溶液]。对于这个实施例,H3PO4/HOAC溶液为约90%摩尔H3PO4和10%摩尔HOAC。
2、制备用于反应的去离子水
3、将2,736.39lbs氢氧化钾加入水中
4、向该水溶液中加入1315.14lbs氢氧化铵(29%)
5、向获得的溶液中添加H3PO4/HOAC溶液,并允许反应。
6、反应后,用醋酸将pH值调整至约7.0。该反应获得的产品可用作化学添加组分以增强烃燃料。
实施例2:
在精制油载体流体中的KH2PO4、K2HPO4、[NH4]2HPO4燃料添加剂作为添加剂加入柴油燃料,采用这种燃料添加剂的实验室试验显示,其在燃料效率方面有较大改进。也对钠用作这种配方中的阳离子进行了评价。LA族金属也是优选的阳离子。涉及阳离子选择的因素包括商业费用和耐蚀性。
实施例3:
与没有燃料添加剂的柴油相比,实施例2中描述的燃料添加剂的应用使低硫柴油燃料产生的燃料废气中排放的CO降低74%、SO2降低34%和颗粒物降低55%。
实施例4:
与没有燃料添加剂的天然气的燃烧相比,上述燃料添加剂的应用使天然气中燃烧形成的一氧化碳降低87%和NOX降低18%。
实施例5:
组分 | lbs | 单位比率重量 |
磷酸氢氧化钾氢氧化铵醋酸去离子水 | 2,5832,7361,3156723,105 | 0.250.260.130.060.30 |
总含磷母液 | 10,411 | 1.00 |
实施例6:
组分 | 投入lbs | 单位比率重量 |
Star4基础油煤油ODA 78012Hitec 646Actaclear ND 17含磷母液(实施例5) | 8,5441,28220520585273 | 0.790.120.020.020.010.03 |
总计 | 10,748 | 1.00 |
用基础油进一步稀释以将燃料添加剂调整至预期的磷浓度。将溶剂从溶液中除去以产生燃料添加剂。在这种情况下,溶剂是水并通过加热脱水。
可选择的实施方案包括[NH4]H2PO4、[NH4]2HPO4和水的用途。
在一个优选的实施方案中,通过溶剂中盐的溶解度或分散性以及溶剂的挥发度限定溶剂。例如,优选将盐分散在全部溶剂中,但是溶剂具有这样的挥发度,即能沸腾出溶液并优选能回收再利用而对获得的产品没有影响。
虽然只显示或描述了本发明的一些形式,但对本领域技术人员来说很明显本发明并不只限于此,不脱离本发明的范围可以容易得到各种变化。例如,加入燃料或载体流体中的盐可以通过快速剪切混合实现而不用产生中间溶液以及随后热脱除溶剂。至于盐,[Y]XH2PO4、[Y]X+HPO4还包含[Y]X[H2PO4]Z、[Y]X+[HPO4]Z,这里x、z是可变的整数。
Claims (11)
1.一种燃料添加剂,其包括盐的混合物和载体流体,该盐的混合物包括
[Y]XH2PO4;和
[Y]X+HPO4,其中[Y]是阳离子,该载体流体可以将盐以至少部分分散的状态保持在载体流体内部,当在燃烧区内与燃料接触并燃烧时,燃料添加剂可以增强燃烧,增强的燃烧可通过提高的燃料效率或燃料和燃料添加剂燃烧产生的废气中降低的污染物排放来测定,其中通过调节所述组分的比率控制溶液的pH值,通过调节产生的H2PO4 -和HPO4 2-离子的比率,溶液产生6.0到8.0的pH值。
2.权利要求1的燃料添加剂,进一步包括[NH4]2HPO4。
3.权利要求2的燃料添加剂,进一步包括NH4C2H3O2,其中C2H3O2是醋酸根。
4.一种在具有燃烧区的燃烧系统中提高烃燃料的燃料性能的方法,其中包括向燃烧区以有效提高燃料性能的量提供权利要求1的燃料添加剂,并使含有燃料添加剂的烃燃料燃烧,一旦将所述燃料添加剂添加到燃料中,燃料中的磷含量为1-250ppm磷。
5.权利要求4的提高燃料性能的方法,其中烃燃料是液体烃燃料。
6.权利要求4的提高燃料性能的方法,其中烃燃料是固体烃燃料。
7.一种增强燃料,其包括
适用于燃烧的大量烃燃料,和可以增强燃烧的一定数量的权利要求1的燃料添加剂,一旦将所述燃料添加剂添加到燃料中,燃料中的磷含量为1-250ppm磷。
8.权利要求7的增强燃料,其中磷以1到150ppm重量的量存在于烃燃料中。
9.一种生产用于燃烧系统的增强烃燃料的方法,其包括如下步骤:在烃燃料中加入有效量的化学添加组合物以提高燃料性能,该化学添加组合物包括混合磷酸源、碱金属氢氧化物、氢氧化铵和水的反应产物,一旦将所述化学添加组合物添加到燃料中,燃料中的磷含量为1-250ppm磷。
10.权利要求9的生产用于燃烧系统的增强烃燃料的方法,其中化学添加组合物进一步包括醋酸。
11.一种生产根据权利要求1的用于增强烃燃料燃烧的燃料添加剂的方法,该方法包括如下步骤:
将盐[Y]XH2PO4和[Y]X+HPO4混入溶剂中,其中[Y]是阳离子,使该盐至少部分地分散在溶剂中以生产含磷母液;
将含磷母液和载体流体混合,以使含磷母液基本上分散于载体流体中;
通过热方式从含磷母液和载体流体的混合物中除去大部分溶剂以产生燃料添加剂,当在烃燃料的存在下将该燃料添加剂加入燃烧区并燃烧时,该添加剂可以增强燃烧。
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US3644106A (en) * | 1966-08-24 | 1972-02-22 | Victor C E Burnop | Colloidal dispersions |
US5540788A (en) * | 1995-02-24 | 1996-07-30 | Mdechem, Inc. | Method of preparing iron-phosphate conversion surfaces |
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KR20060081658A (ko) | 2006-07-13 |
PL379422A1 (pl) | 2006-09-04 |
AR046386A1 (es) | 2005-12-07 |
CA2529645A1 (en) | 2005-01-06 |
JP2007521365A (ja) | 2007-08-02 |
IL172607A0 (en) | 2006-04-10 |
CN1809626A (zh) | 2006-07-26 |
WO2005001004A2 (en) | 2005-01-06 |
US20100024289A1 (en) | 2010-02-04 |
US20050028434A1 (en) | 2005-02-10 |
MXPA06000066A (es) | 2006-04-07 |
EA200600080A1 (ru) | 2006-08-25 |
WO2005001004A3 (en) | 2005-04-14 |
US7604672B2 (en) | 2009-10-20 |
EA008844B1 (ru) | 2007-08-31 |
EP1644466A2 (en) | 2006-04-12 |
BRPI0411883A (pt) | 2006-08-29 |
CR8210A (es) | 2006-08-09 |
ZA200600052B (en) | 2007-12-27 |
AU2004252550A1 (en) | 2005-01-06 |
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