CN107353951B - 一种柴油十六烷值改进剂 - Google Patents
一种柴油十六烷值改进剂 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
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- C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
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Abstract
本发明涉及一种柴油十六烷值改进剂,其组分由2,2‑二硝基烷基酸酯、硝酸异辛酯及其他助剂组成。各组分重量份为:2,2‑二硝基烷基酸酯50~90;硝酸异辛酯10~40;助剂2~30;所述2,2‑二硝基烷基酸酯为短链烷基酸酯的二硝基化合物。所述助剂为溶剂、表面活性剂、清净分散剂中的一种或几种的混合物。本发明生产工艺简单,价格低廉,在柴油中添加0.5~4‰(重量百分比)后,可提高柴油十六烷值2~20个单位,可实现节油5~20%,可在降低柴油机油耗的同时有效降低尾气中有害物质的排放,使用效果良好。
Description
技术领域
本发明属于燃料添加剂领域,涉及一种柴油十六烷值改进剂配方,特别涉及一种2,2-二硝基烷基酸酯的新型柴油十六烷值改进剂组分的使用。
背景技术
近年来,随着柴油机的广泛使用,柴油的消耗量正逐年增长,而有限的柴油资源却日趋减少。同时由于柴油组分的烷烃分子量较大,在内燃机工作时柴油的燃烧率不够高,燃烧性能不够好,这不仅增大了耗油量,而且加深了排气对空气的污染程度。因此柴油的使用与环境保护等问题,受到人们的关注。国内外燃油科技产业界纷纷加大对柴油添加剂的研究开发力度,以改善发动机燃料的燃烧特性,达到节能和环保的目的。
我国第五阶段车用柴油国家标准要求,轻柴油的十六烷值不低于51。世界各国柴油十六烷值的主要因素是柴油调合的组分构成。直馏柴油的十六烷值比较高,因原油不同而异。馏程相同时,大庆直馏柴油十六烷值高达63,而辽河直馏柴油只有43。我国柴油的二次加工处理量占原油加工量的60-70wt%,二次加工柴油特别是重油催化裂化柴油的十六烷值很低,一般只有30-40。随着加工重质原油比例的增加,十六烷值整体水平将呈现下降的趋势。过去,我国轻柴油标准中规定柴油的十六烷值不低于45以及47,大部分炼油企业可以满足这个标准。但到2016年以后,我国实行了新的柴油规格标准,规定柴油的十六烷值应达到51以上,这样,许多炼油企业的柴油将达不到这个标准。因此,如何提高柴油十六烷值成了部分炼油企业所面临的比较迫切的问题。
柴油的十六烷值与柴油的化学组成有关:碳原子数相同或分子量相近的烃类中,正构烷烃的十六烷值最高,无侧链的芳香烃十六烷值最低,环烷烃和烯烃、异构烷烃居中。含有侧链的芳香烃和环烷烃,其链越长,分支越少,十六烷值就越高。提高柴油十六烷值的方法有三种:(1)将高十六烷值的直馏柴油与低十六烷值的二次加工柴油调配。但直馏柴油的产量有限,同时高十六烷值的直馏柴油被用作乙烯裂解原料,也会影响以直馏柴油为原料的乙烯的生产;(2)采用溶剂抽提和加氢处理、重整等工艺加以改善以提高其十六烷值,但是通过这些工艺的处理,加工成本是比较高的,对部分企业来说在经济上是不合算的;(3)添加十六烷值改进剂。这种方法具有工艺简单,成本低廉,灵活多样的特点。
国内外都对柴油十六烷值改进剂进行了广泛的研究,涉及到节油、降污、减少尾气烟度排放等方面,常见的十六烷值改进剂主要有烷基硝酸酯、过氧化物、醚、酯、胺等。存在的不足是添加量较少时,油品的十六烷值提高不够明显,添加较多量时 ,合格产品油的生产成本明显提高,经济型降低。
发明内容
本发明的目的在于提供一种生产工艺简单,价格低廉,性能较好、可降低柴油机油耗的柴油十六烷值改进剂。
本发明的技术方案包括2,2-二硝基烷基酸酯、硝酸异辛酯及其他助剂,各组分重量份为:
2,2-二硝基烷基酸酯 50~90;
硝酸异辛酯 10~40;
助剂 2~30。
本发明各组分优选重量份为:
2,2-二硝基烷基酸酯 60~80;
硝酸异辛酯 15~30;
助剂 5~20。
本发明所述2,2-二硝基烷基酸酯为C3~C8的烷基酸酯的二硝基化合物。
本发明所述2,2-二硝基烷基酸酯为2,2-二硝基烷基酸与碳原子个数为C1~C4脂肪醇的酯化合物。
本发明所述2,2-二硝基烷基酸酯为2,2-二硝基丙酸酯、2,2-二硝基丁酸酯、2,2-二硝基戊酸酯、2,2-二硝基异戊酸酯、2,2-二硝基烷基酸甲酯、2,2-二硝基烷基酸乙酯、2,2-二硝基烷基酸丙酯、2,2-二硝基烷基酸异丙酯。
本发明所述助剂为溶剂、表面活性剂、清净分散剂中的一种或几种的混合物。
本发明所述溶剂为航空煤油或柴油。
本发明所述表面活性剂为烷基酚聚氧乙烯醚或脂肪醇聚氧乙烯醚。
本发明所述清净剂分散剂为聚异丁烯丁二酰亚胺或丁二酰亚胺。
本发明中2,2-二硝基烷基酸酯为主要和最重要的组分。所述2,2-二硝基烷基酸酯类化合物是硝基烷烃酯的衍生物。是一种同时含硝基和酯基的含能化合物,其分子内含有2个硝基基团和1个酯基团,其结构如下式所示。由于其分子结构中存在含能基团,在较低的能量(热能)刺激下就会迅速分解,产生大量的自由基,放出大量的热能,有助于引发柴油中烃类化合物的燃烧分解。
本发明的柴油十六烷值改进剂的制备方法为:将上述组分按照所述比例直接搅拌混合均匀即可。
为了表明本发明的效果,以市售国IV柴油作为对照,当本发明添加量为0.8‰时,柴油十六烷值由49提高60,使用依维柯柴油动力车进行道路实验,结果表明,使用本发明的柴油十六烷值改进剂后,节油12%,并且在柴油燃烧过程中没有黑烟;在船用柴油机上进行测试,节油率最大可达8%,氮氧化物NOx排放降低10~20%,一氧化碳CO排放降低10~25%,碳氢化合物CH排放降低20~30%。
2,2-二硝基烷基酸酯类化合物是硝基烷烃酯的衍生物,硝基醇的应用最为广泛。硝基醇适宜用作各种纤维酯、聚丙烯腈及它们的共聚物、改性氨基塑料的溶剂,还可用作乳化剂和高分子化合物的增塑剂。偕二硝基能量高,安定性适宜,而且单个分子中具有两个硝基,属于多硝基化合物,在分解时可以产生更多的RO·和NO2·自由基来引发燃烧过程中所需要的链氧化反应。因此多硝酸酯的十六烷值改进效果要好于单硝酸酯,多硝基酯提高十六烷值的效率通常是单硝酸酯的2-5倍,而用量约为单硝酸酯用量的1/5-1/2。目前2,2-二硝基烷基酸主要作为含能粘合剂的单体使用,有成熟和低成本的合成方法和路线,在与脂肪醇反应后,就可低成本的合成2,2-二硝基烷基酸酯类化合物,因此是一种更吸引人的高效十六烷值改进剂 。
与现有技术相比,本发明的有益效果是:生产工艺简单,价格低廉,在柴油中添加0.5‰~4‰(重量百分比)后,可提高柴油十六烷值2~20个单位,可实现节油5~20%,并可在降低柴油机油耗的同时有效降低尾气中有害物质的排放,使用效果良好。
下面结合具体实施方式对本发明作进一步说明(以下各组分均为重量份)。
具体实施方式
实施例1
2,2-二硝基丙酸丁酯80份,硝酸异辛酯15份,航空煤油5份。将2,2-二硝基丙酸甲酯和硝酸异辛酯直接混合,再加入航空煤油,常温、常压下进行搅拌,混合均匀即可。
实施例2
2,2-二硝基丁酸丙酯70份,硝酸异辛酯20份,聚异丁烯丁二酰亚胺5份,脂肪醇聚氧乙烯醚3份,柴油2份。将2,2-二硝基丁酸乙酯、硝酸异辛酯,聚异丁烯丁二酰亚胺和脂肪醇聚氧乙烯醚直接加入到柴油中,常温常压下进行搅拌,混合均匀即可。
实施例3
2,2-二硝基戊酸甲酯65份,硝酸异辛酯15份,丁二酰亚胺5份,烷基酚聚氧乙烯醚2份,航空煤油13份。将2,2-二硝基戊酸甲酯、硝酸异辛酯、丁二酰亚胺和烷基酚聚氧乙烯醚直接加入到航空煤油中,常温、常压直接混合搅拌均匀即可。
实施例4
2,2-二硝基异戊酸乙酯60份,硝酸异辛酯30份,丁二酰亚胺5份,烷基酚聚氧乙烯醚5份。将2,2-二硝基异戊酸乙酯、烷基酚聚氧乙烯醚和丁二酰亚胺直接加入到硝酸异辛酯中,常温、常压下进行搅拌,混合均匀即可。
Claims (8)
1.一种柴油十六烷值改进剂,其特征在于:各组分重量份为:
2,2-二硝基烷基酸酯 50~90;
硝酸异辛酯 10~40;
助剂 2~30;
所述助剂为溶剂、表面活性剂、清净分散剂中的一种或几种的混合物。
2.根据权利要求1所述的柴油十六烷值改进剂,其特征在于:各组分优选重量份为:
2,2-二硝基烷基酸酯 60~80;
硝酸异辛酯 15~30;
助剂 5~20。
3.根据权利要求1所述的柴油十六烷值改进剂,其特征在于:所述2,2-二硝基烷基酸酯为C3~C8的烷基酸酯的二硝基化合物。
4.根据权利要求1或2所述的柴油十六烷值改进剂,其特征在于:所述2,2-二硝基烷基酸酯为2,2-二硝基烷基酸与碳原子个数为C1~C4脂肪醇的酯化合物。
5.根据权利要求1所述的柴油十六烷值改进剂,其特征在于:所述2,2-二硝基烷基酸酯为2,2-二硝基丙酸酯、2,2-二硝基丁酸酯、2,2-二硝基戊酸酯、2,2-二硝基异戊酸酯、2,2-二硝基烷基酸甲酯、2,2-二硝基烷基酸乙酯、2,2-二硝基烷基酸丙酯、2,2-二硝基烷基酸异丙酯。
6.根据权利要求1所述的柴油十六烷值改进剂,其特征在于:所述溶剂为航空煤油或柴油。
7.根据权利要求1所述的柴油十六烷值改进剂,其特征在于:所述表面活性剂为烷基酚聚氧乙烯醚或脂肪醇聚氧乙烯醚。
8.根据权利要求1所述的柴油十六烷值改进剂,其特征在于:所述清净剂分散剂为聚异丁烯丁二酰亚胺或丁二酰亚胺。
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