CN114015484A - 一种含有dmm1-3组分的汽油掺烧料及其清洁汽油 - Google Patents
一种含有dmm1-3组分的汽油掺烧料及其清洁汽油 Download PDFInfo
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- 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
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- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
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Abstract
本发明提供一种含有DMM1‑3组分的汽油掺烧料及其清洁汽油,所述汽油掺烧料按重量百分比计,包括以下组分:聚甲氧基二甲醚DMM1‑351%~60%;多氧化合物8~15%;多氮化合物10~16%;尿素或三聚氰胺5~15%;助溶剂10~12%;多氮化合物为邻苯二胺和亚硝酸钠在酸性条件下发生重氮化和酯化反应而得的产物;多氧化合物为过氧化叔丁酯;助溶剂为脂肪醇聚氧乙烯醚、乙醇胺和正戊醇按体积比2:1:1的混合物。本发明提供的汽油掺烧料及其清洁汽油能够高效实现发动机尾气中NOx、HC和CO的减排。该清洁汽油能够很好替代现有的汽油产品,还大大提高了聚甲氧基二甲醚DMM1‑3的添加量。
Description
技术领域
本发明属于一种清洁汽油,具体涉及一种含有DMM1-3组分的汽油掺烧料及其清洁汽油。
背景技术
当今世界,能源和环境已被确认为是影响全球经济社会可持续发展的主要因素,化石能源在人类生存和经济发展中仍起到极其重要的作用。化石能源如汽油和柴油等燃料的大量燃烧导致了大量的碳排放物(CO、HC)和氮氧化物(NOx)排放到空气中,严重污染空气质量,威胁着人类生存的环境和身体健康。
据数据统计,目前我国机动车保有量已达到2.9亿辆,并且每年都保持着20%以上的年增长率,日益庞大的车辆使用和增长率给我国化石能源的储备带来了极大的考验,如何减少化石能源的消耗,提供可替代性的可再生能源,成为我国能源和环保部门重点关注的问题。
随着我国压燃机排放法规愈加严格,法规中压燃机氮氧化物(NOx)、碳氢(HC)和CO的排放限值越来越低,人们迫切渴望提升燃油的品质,减少机动车尾气产生的有害气体,并很好达到国家相关排放标准。在寻找油品质量提升和替代品的过程中,虽然乙醇汽油可替代石化汽油进行使用,但是乙醇类燃料存在低温分层、遇水分层等缺点,在运输、储存和使用上有较大困难;且以醇类燃料替代石油燃料存在油品质量难以控制,无法解决尾气排放中有害气体排放量高、严重污染环境等问题。
另一方面,研究发现开展清洁燃油生产工艺和在汽车燃油中加入醚类清洁掺烧燃料能够大幅度改进燃油质量,减少机动车尾气中有害气体的排放。传统的醚类燃料如二甲醚,存在辛烷值低、常温常压下是气态等问题,应用受到较大限制;另外也有学者提出采用聚甲氧基二甲醚(DMMn,n=1~8)来作为清洁掺烧料,减少机动车尾气污染物的排放,但现有工艺方法往往是将DMM1~8混合使用,而无法将其很好分开,其中仅将DMM3-8组分作为柴油添加组分,而将DMM1-2组分作为汽油添加组分,这不仅浪费了DMM3的优良特性,且对于提升汽油的品质起到了限制作用。并且,由于DMM1-2的沸点较低,会导致调和后的汽油产品馏程改变,影响汽油的燃烧,出现爆燃等现象,反而增加了氮氧化物的排放。
对于汽油掺烧料而言,虽然已有报道公开了多种醚类添加燃料,但如何在现有技术的基础上,进一步提升油品品质,减少其污染物的排放,提供一种效果更佳的醚料掺烧料和清洁汽油,成为我国环境治理方面亟待解决的一个技术问题。
发明内容
本发明的目的就是为了解决机动车尾气排放的问题,从而提供一种含有DMM1-3组分的汽油掺烧料及其清洁汽油,本发明的汽油掺烧料能够高效实现发动机尾气中NOx、HC和CO的减排,大大减少机动车尾气中废气的排放对大气造成的污染,同时该清洁汽油能够很好替代现有的汽油产品,还大幅提高了聚甲氧基二甲醚DMM1-3的添加量,具备清洁环保的特点。
本发明的目的之一是提供一种含有DMM1-3组分的汽油掺烧料,其特征在于,所述汽油掺烧料按重量百分比计,包括以下组分:
所述多氮化合物为邻苯二胺和亚硝酸钠在酸性条件下发生重氮化和酯化反应而得的产物;
所述多氧化合物为以苯甲酰氯和70%(v/v)叔丁基过氧化氢为原料,在添加盐水和氢氧化钠的条件下发生反应制得的98%(v/v)过氧化叔丁酯;
所述助溶剂为脂肪醇聚氧乙烯醚、乙醇胺和正戊醇按体积比2:1:1的混合物。
本发明提供的上述汽油掺烧料配方,最关键的发明点是通过配方的合理研发,能够在汽油中将DMM3组分作为掺烧料,且DMM1-3的添加量提升到50%以上,而本发明的发明人通过文献调研发现,现有报道几乎没有将DMM3组分作为汽油掺烧料,而是选择作为柴油掺烧料,同时DMM作为掺烧料的添加量无法超过50%。本发明不仅提高了DMM1-3的添加量,同时还大幅减少了多氧化合物和多氮化合物的用量,并在一定程度上减少了尿素或三聚氰胺的用量,其掺烧料成本更低。
由于聚甲氧基二甲醚组分DMM1和DMM2的闪点低,氧含量相比偏低,因此本发明选择加入DMM3组分来提高其闪点,解决聚甲氧基二甲醚DMM1-2作为汽油掺烧料时存在的以上弊端。本发明还将多氧化合物与DMM1-3进行复配,其中多氧化合物是以70%叔丁基过氧化氢、苯甲酰氯为原料,在添加盐水和氢氧化钠的条件下发生反应制得的98%过氧化叔丁酯,该化合物的含氧量高,能够很好解决聚甲氧基二甲醚中组分DMM1和DMM2的问题,二者进行复配,能够提供充足的氧支持燃油燃烧,起到了相互促进、协同增效的作用,对于机动车尾排的减排效果显著。
本发明的掺烧料配方中选择尿素或三聚氰胺与多氮化合物复配,应用于发动机中能够起到很好的脱硝作用,大大减少了机动车尾气的氮氧化物排放量。尿素将汽油机排气中的NOx还原为N2和水,但是其也存在NOx低温转化效率低下,排气管路产生沉积物及氨泄漏等缺陷,而采用多氮化合物进行复配,能够很好解决这一缺陷。同时采用多氧化合物与DMM1-3组成节能减排剂,能够更高效地使燃油在发动机内充分燃烧,实现全面的节能减排。
理论上,本发明的掺烧料中,DMM1、DMM2、DMM3的比例可以根据需要调整,但建议的较佳质量比为DMM1:DMM2:DMM3=1:2:3。
进一步的是,所述叔丁基过氧化氢与苯甲酰氯的摩尔比为1:1。
进一步的是,所述盐水的浓度为2g/L,所述氢氧化钠的浓度为5mol/L。
进一步的是,所述邻苯二胺的纯度为99.5%(m/m)以上,所述亚硝酸钠的纯度为99m/m%以上。
进一步的是,所述邻苯二胺与亚硝酸钠的摩尔比为1.2~1.5:1。
进一步的是,所述酸为浓硫酸,其质量分数为98%,浓硫酸的用量为邻苯二胺摩尔量的2.5倍。
进一步的是,所述多氮化合物的反应温度为75~82℃,所述多氧化合物的反应温度为50~60℃。
本发明的目的之二是提供一种如上所述含有DMM1-3组分的汽油掺烧料的清洁汽油,包括如下组分:
汽油掺烧料:15%~20%;
汽油组份:80%~85%;
其中,所述汽油组份包括国标汽油和非国标汽油,
进一步的是,所述国标汽油为市售国标92号、95号或98号汽油;所述非国标汽油的研究法辛烷值≥85,硫含量≤70ppm。
与现有技术相比,本发明的有益效果如下:
本发明提供的含有DMM1-3组分的汽油掺烧料及其清洁汽油,是通过多种高含氮组分的复配以及高含氧组分的复配,再与汽油组分进行混合调配,充分考虑燃油在发动机内燃烧的特性,从根本出发改变燃油燃烧过程不充分导致产生大量有害气体的缺陷。同时本发明首次将DMM3组分与DMM1-2联用作为汽油掺烧料组分,不仅很好解决了DMM1和DMM2组分闪点低,作为燃料不稳定的问题,还大幅提高了其添加量,减少了其它成分的添加量。本发明各种组分的复配能够起到在燃烧过程中补充所需氧环境,并高效阻止氮氧化和高效催化氮还原的功能,相互促进,增强了两者协同效果,更加有效地减少了燃烧不充分和爆燃引起的机动车尾气中有害气体排放的问题。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例对本发明进行具体描述,有必要指出的是,以下实施例仅用于对本发明进行解释和说明,并不用于限定本发明。本领域技术人员根据上述发明内容所做出的一些非本质的改进和调整,仍属于本发明的保护范围。
实施例1
一种含有DMM1-3组分的汽油掺烧料,按如下表1中的原料配方组成:
表1
其中,助溶剂为脂肪醇聚氧乙烯醚、乙醇胺和正戊醇按体积比2:1:1的混合物。DMM1:DMM2:DMM3=1:2:3m/m/m。
其中,多氧化合物为以70v/v%叔丁基过氧化氢、苯甲酰氯为原料(摩尔比1:1),在添加盐水(浓度为2g/L)和氢氧化钠(浓度为5mol/L)的条件下与80~90℃发生反应制得的98v/v%过氧化叔丁酯。
多氮化合物的制备方法如下:
在反应釜中先加入由邻苯二胺(99.5%)与98%浓硫酸配成的悬浮液(邻苯二胺与浓硫酸的摩尔比为1:2.5),搅拌均匀,控制瓶内温度为75~82℃,然后经漏斗缓慢滴加由亚硝酸钠(99%)与水制成的溶液,并使之剧烈机械搅拌,滴加时间为1.5h(邻苯二胺的用量为亚硝酸钠摩尔量的1.2~1.5倍),滴加完毕后继续搅拌反应20min,将所得沉淀物趁热抽滤,并依次用工业乙醇和乙醚洗涤后,真空干燥一段时间,得到产物,产率90%以上。
制备过程中涉及的主要反应式如下(酯化反应为副反应,产物很少,可忽略):
清洁汽油配方按如下表2配置:
表2
其中,非国标汽油的研究法辛烷值为86,硫含量为64ppm。
对比例1
一种清洁汽油,将其中的助溶剂改为脂肪醇聚氧乙烯醚和乙醇胺按体积比2:1的混合物。
对比例2
一种清洁汽油,将其中的助溶剂改为乙醇胺和正丁醇按体积比1:1的混合物。
对比例3
一种清洁汽油,将其中的助溶剂改为脂肪醇聚氧乙烯醚、乙醇胺和正戊醇按体积比2:2:1的混合物。
实验例1
将表2(清洁汽油1-5)以及对比例1-3中配制的清洁汽油用于汽油发动机的台架试验,以未添加掺烧料的原汽油样的排放量作为参照,分别添加到DA468汽油发动机燃烧室内燃烧,进行污染物排放等性能检测,测试方法如下:按照汽油车怠速下尾气中污染物的排放量进行检测,分别检测怠速下尾气中NOx的排放量、HC的排放量和CO的排放量。
表3
从表3可以看出,采用本发明的清洁汽油后,汽油发动机尾气中各废气物的排放量均得到了较大幅度的下降,且对比例的效果要显著低于本发明。
Claims (10)
2.根据权利要求1所述的含有DMM1-3组分的汽油掺烧料,其特征在于,所述叔丁基过氧化氢与苯甲酰氯的摩尔比为1:1。
3.根据权利要求1所述的含有DMM1-3组分的汽油掺烧料,其特征在于,所述盐水的浓度为2g/L,所述氢氧化钠的浓度为5mol/L。
4.根据权利要求1所述的含有DMM1-3组分的汽油掺烧料,其特征在于,所述邻苯二胺的纯度为99.5m/m%以上,所述亚硝酸钠的纯度为99%m/m以上。
5.根据权利要求1所述的含有DMM1-3组分的汽油掺烧料,其特征在于,所述邻苯二胺与亚硝酸钠的摩尔比为1.2~1.5:1。
6.根据权利要求1所述的含有DMM1-3组分的汽油掺烧料,其特征在于,所述酸为浓硫酸,其质量分数为98%,浓硫酸的用量为邻苯二胺摩尔量的2.5倍。
7.根据权利要求1所述的含有DMM1-3组分的汽油掺烧料,其特征在于,所述多氮化合物的反应温度为75~82℃,所述多氧化合物的反应温度为50~60℃。
8.一种如权利要求1-7任一项所述含有DMM1-3组分的汽油掺烧料的清洁汽油,其特征在于,包括如下组分:
汽油掺烧料15%~20%;
汽油组份:80%~85%;
其中,所述汽油组份包括国标汽油和非国标汽油。
9.根据权利要求8所述的清洁汽油,其特征在于,所述国标汽油为市售国标92号、95号或98号汽油。
10.根据权利要求8所述的清洁汽油,其特征在于,所述非国标汽油的研究法辛烷值≥85,硫含量≤70ppm。
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