CN108251170A - 一种乙醇汽油生物添加剂 - Google Patents
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Abstract
一种乙醇汽油生物添加剂,由生物质汽油与复合改性剂混合配制成,以重量计,所述生物质汽油占乙醇汽油生物添加剂的比例为80~99.99%。将常规的烃类汽油与燃料乙醇混合,再加入本发明的乙醇汽油生物添加剂,调和成乙醇汽油。添加了该乙醇汽油生物添加剂的乙醇汽油,在燃烧性与稳定性上都有提升,尤其不易吸水分层。本发明将复合改性剂与生物质汽油配合使用,可以更好的提升乙醇汽油的使用性能。使用来源于可再生能源生物质的生物质汽油作为乙醇汽油生物添加剂的配方,不但绿色环保无污染,也为各种废弃生物质的加工再利用提供了思路。
Description
技术领域
本发明涉及一种乙醇汽油生物添加剂。
背景技术
2017年9月,国家发展改革委、国家能源局、财政部等十五部委联合印发了《关于扩大生物燃料乙醇生产和推广使用车用乙醇汽油的实施方案》。方案要求,到2020年,将在全国范围内推广使用车用乙醇汽油。其实早在2001年的时候,国家就已经开始在9个省份内推广使用乙醇汽油。相比于传统的烃类燃料,添加了燃料乙醇的汽油,可有效减少汽车尾气中的碳排放和PM2.5等细颗粒物以及其他有毒物质的污染。同时,由于乙醇属于可再生能源,往汽油里添加一定量的乙醇,既可以减少汽油这种不可再生能源的使用量,又能有效利用秸秆和大量过期变质的储备粮,将这些废料转变成可以利用的能源,可谓一举多得。但是,乙醇汽油也有弊端,首先,其燃烧性能较传统汽油差,数据显示,目前车用汽油的热值数据为43.03MJ/kg,而纯乙醇的热值仅为26MJ/kg,对于相同质量的汽油和乙醇来说,后者的热值几乎低了一半。另外,虽然乙醇汽油本身对发动机是不存在腐蚀性的,但是,乙醇汽油会溶解油路中原本存在的杂质,将其带入发动机,从而造成一定程度的损坏;另外,乙醇汽油在燃烧后会产生乙酸,乙酸具有腐蚀性。同时,乙醇容易吸水,会造成乙醇汽油分层。如果能改进乙醇汽油的燃烧性,并且降低其潜在的对机动车部件的腐蚀,将极大的推进乙醇汽油的使用范围与大众接受程度。
目前改进乙醇汽油性能的方法多集中在使用合理的添加剂,例如,CN103952195A公开了一种车用甲醇汽油复合添加剂的制备方法,包括缓蚀剂、燃料油性剂、清洁分散剂和助溶剂,使用添加剂后,甲醇汽油对汽车油箱、油泵、油表及供油管路腐蚀小,减少燃烧系统磨损,增强抗遇水分层能力,由于原理相同,可以类比到乙醇汽油。再例如,CN106833764A公开了一种汽油及制作方法,可以提高乙醇汽油的燃烧性能。还有CN101358151A,CN101792683A以及CN106398787A等,使用醇类、醛类、醚类与酯类作为乙醇汽油添加剂,来增强其稳定性。这些添加剂的使用目的都是增强乙醇汽油的燃烧性与稳定性,但还不够理想。
发明内容
本发明所要解决的技术问题是,针对目前乙醇汽油的缺点,提供一种乙醇汽油生物添加剂,将该添加剂加入到乙醇汽油中,可以提高乙醇汽油的燃烧性能和抗腐蚀性,同时防止乙醇汽油吸水分层。
本发明解决其技术问题所采用的技术方案是:一种乙醇汽油生物添加剂,是:由生物质汽油与复合改性剂混合配制而成。
进一步,以重量计,所述生物质汽油占乙醇汽油生物添加剂的比例为80~99.99%,优选85~99%。
进一步,所述生物质汽油来源于热解生物质油高压加氢;所述热解生物质油是由玉米秸秆、果壳果核、树皮树根等生物质被研磨成颗粒后,在隔绝空气的条件下,迅速被加热到一定温度(600~1000℃),后又迅速冷凝,生成的一种棕黑色液体;所述热解生物质油一般包括酚类、酮类、酸类、醇类、醚类、呋喃类等含氧有机物;所述热解生物质油经过高压加氢后,其中的含氧有机物脱氧转化为烃类;所述高压加氢的条件,一般选用280~400℃,2~20 MPa的氢气压力,优选350~400℃,10~15MPa,以过渡金属化合物为催化剂。加氢后的热解生物质油经过过滤除去杂质,静置分层除去水相,再将油相蒸馏,收集馏程在70~205℃之间的有机物,即为生物质汽油。研究实践表明,由热解生物质油加氢得到的生物质汽油与燃料乙醇和传统烃类原料均有良好的互溶性,并且可以对燃料乙醇的吸水效应有一定的抑制作用。
进一步,所述复合改性剂的配制方法如下:以重量计,防蚀剂1~5份,优选1~2份,助稳剂1~7份,优选2~3份,增燃剂1~10份,优选6~10份。
进一步,所述防蚀剂由防蚀剂A和防蚀剂B混合制成,所述防蚀剂A是苯丙三唑,巯基苯丙三唑,甲基苯丙三唑中的一种或几种,所述防蚀剂B是由硬脂酸甲酯,硬脂酸乙酯中的一种或两种,所述防蚀剂A和防蚀剂B按以下的重量份数进行配制:防蚀剂A 1~10份,优选1~5份,防蚀剂B 1~3份。
进一步,所述助稳剂由助稳剂A和助稳剂B混合制成,所述助稳剂A是六偏磷酸钠,六偏磷酸钾中的一种或两种,所述助稳剂B是叔丁基邻苯二酚、二叔丁基苯酚中的一种或两种,所述助稳剂A和助稳剂B按以下的重量份数进行配制:助稳剂A 1~5份,优选1~2份,助稳剂B 5~9份(优选7~9份)。
进一步,所述增燃剂由增燃剂A和增燃剂B混合制成,所述增燃剂A是碳6到碳10芳烃中的一种或几种,所述增燃剂B是碳6到碳11烷烃中的一种或几种,所述增燃剂A和增燃剂B按以下的重量份数进行配制:增燃剂A 1~5份(优选1~2份),增燃剂B 1~20份(优选15~20份)。
将烃类汽油与燃料乙醇混合,配制成乙醇汽油,以体积计,燃料乙醇/乙醇汽油为0~100%(优选1~15%)。所述烃类汽油包括但不限于由馏程在70~205℃之间的链烷烃、环烷烃、烯烃、芳烃组成的混合烃类或单一烃类物质。将本发明的乙醇汽油生物添加剂加入到乙醇汽油中,以重量计,乙醇汽油生物添加剂占乙醇汽油的比例为5~30%。
本发明的复合改性剂也可作为乙醇汽油添加剂,直接加入乙醇汽油中,对乙醇汽油的燃烧性和稳定性也有一定的提高。但是,研究实践表明,复合改性剂与生物质汽油混合配制的添加剂加入到乙醇汽油中,对乙醇汽油各方面的性质,尤其是稳定性,有更明显的改进。这是由于,首先生物质汽油中的烃类与传统汽油中的烃类完全可以互溶,其次,生物质汽油源于热解生物质油加氢,即源于含氧有机物加氢,所以其与含氧有机物乙醇也有很好的相容性。生物质汽油的极性介于燃料乙醇与烃类汽油之间,是两者良好的稳定剂。而当生物质汽油与复合改性剂配合使用时,生物质汽油中的加氢不完全的活泼中间体可以与复合改性剂中的有效组分发挥协同效应,使乙醇汽油的燃烧性能增加,并防止其吸水分层。同时,生物质汽油源于热解生物质油,目前用于制作热解生物质油的生物质一般都为废弃生物质。这部分生物质或者作为燃料烧掉,或者作为农业废物被处理掉,浪费了大量的资源,同时也污染了环境。而本发明将其制作成为高附加值的添加剂,为玉米秸秆、果壳果核、树皮树根等废弃生物质找到了加工再利用的方法。
具体实施方式
以下结合实施例对本发明作进一步说明。
实施例1
生物质汽油来源于热解树皮生物质油加氢,加氢条件为350℃,15MPa氢气压力,以MoS2为催化剂,加氢后经过过滤除去杂质,静置分层除去水相,并收集馏程在70~205℃之间有机物为生物质汽油。复合改性剂中(以重量计)防蚀剂3份,助稳剂5份,增燃剂7份。其中,防蚀剂的配制方法为,以重量计,防蚀剂A 5份,防蚀剂B 2份,防蚀剂A由苯丙三唑和甲基苯丙三唑组成,两者比例(以重量计)为1/1,防蚀剂B由硬脂酸甲酯和硬脂酸乙酯组成,两者比例(以重量计)为3/1。助稳剂的配制方法为,以重量计,助稳剂A 3份,助稳剂B 5份,助稳剂A为六偏磷酸钠,助稳剂B由叔丁基邻苯二酚和二叔丁基苯酚组成,两者比例(以重量计)为1/3。增燃剂的配制方法为,以重量计,增燃剂A 2份,增燃剂B 13份,增燃剂A由甲苯和二甲苯组成,两者比例(以重量计)为1/1,增燃剂B由异构碳9和异构碳10链烷烃组成,两者比例(以重量计)为2/3。烃类汽油为燕山直馏汽油。
将生物质汽油与复合改性剂在常温常压下按一定比例进行混合,配制成乙醇汽油生物添加剂,以重量计,生物质汽油/乙醇汽油生物添加剂为90%。将烃类汽油与燃料乙醇在常温常压下混合,配制成乙醇汽油,以体积计,燃料乙醇/乙醇汽油为10%。将乙醇汽油生物添加剂加入到乙醇汽油中,以重量计,乙醇汽油生物添加剂占乙醇汽油的8%,配制成乙醇汽油1。
实施例2
生物质汽油同实施例1,烃类汽油同实施例1,复合改性剂同实施例1。将生物质汽油与复合改性剂在常温常压下按一定比例进行混合,配制成乙醇汽油生物添加剂,以重量计,生物质汽油/乙醇汽油生物添加剂为80%。将烃类汽油与燃料乙醇在常温常压下混合,配制成乙醇汽油,以体积计,燃料乙醇/乙醇汽油为10%。将乙醇汽油生物添加剂加入到乙醇汽油中,以重量计,乙醇汽油生物添加剂占乙醇汽油的8%,配制成乙醇汽油2。
实施例3
生物质汽油同实施例1,烃类汽油同实施例1,复合改性剂同实施例1。将生物质汽油与复合改性剂在常温常压下按一定比例进行混合,配制成乙醇汽油生物添加剂,以重量计,生物质汽油/乙醇汽油生物添加剂为90%。将烃类汽油与燃料乙醇在常温常压下混合,配制成乙醇汽油,以体积计,燃料乙醇/乙醇汽油为10%。将乙醇汽油生物添加剂加入到乙醇汽油,以重量计,乙醇汽油生物添加剂占乙醇汽油的20%,配制成乙醇汽油3。
实施例4
生物质汽油同实施例1,烃类汽油同实施例1。复合改性剂中(以重量计)防蚀剂5份,助稳剂5份,增燃剂3份。其中,防蚀剂的配制方法为,以重量计,防蚀剂A 7份,防蚀剂B2份,防蚀剂A为甲基苯丙三唑,防蚀剂B由硬脂酸甲酯和硬脂酸乙酯组成,两者比例(以重量计)为5/2。助稳剂的配制方法为,以重量计,助稳剂A 5份,助稳剂B 8份,助稳剂A为六偏磷酸钾,助稳剂B为叔丁基邻苯二酚。增燃剂的配制方法为,以重量计,增燃剂A 1份,增燃剂B 4份,增燃剂A为各种结构的碳9芳烃,增燃剂B由各种结构的碳8~10烷烃组成。
将生物质汽油与复合改性剂在常温常压下按一定比例进行混合,配制成乙醇汽油生物添加剂,以重量计,生物质汽油/乙醇汽油生物添加剂为90%。将烃类汽油与燃料乙醇在常温常压下混合,配制成乙醇汽油,以体积计,燃料乙醇/乙醇汽油为10%。将乙醇汽油生物添加剂加入到乙醇汽油中,以重量计,乙醇汽油生物添加剂占乙醇汽油的8%,配制成乙醇汽油4。
对比例1,烃类汽油同实施例1,将烃类汽油直接与燃料乙醇混合,以体积计,燃料乙醇/乙醇汽油为10%,配制成乙醇汽油5。
对比例2,生物质汽油同实施例1,烃类汽油同实施例1,将烃类汽油与燃料乙醇在常温常压下混合,配制成乙醇汽油,以体积计,燃料乙醇/乙醇汽油为10%。将生物质汽油作为乙醇汽油生物添加剂加入到乙醇汽油中,以重量计,乙醇汽油生物添加剂占乙醇汽油的8%,配制成乙醇汽油6。
对比例3,烃类汽油同实施例1,复合改性剂同实施例1,将烃类汽油与燃料乙醇在常温常压下混合,配制成乙醇汽油,以体积计,燃料乙醇/乙醇汽油为10%。将复合改性剂加入到乙醇汽油中,以重量计,复合改性剂占乙醇汽油的8%,配制成乙醇汽油7。
测试乙醇汽油1~7的性质,如表1所示。
表1 乙醇汽油1~7的性质
Claims (8)
1.一种乙醇汽油生物添加剂,其特征在于:由生物质汽油与复合改性剂混合配制而成。
2.根据权利要求1所述的乙醇汽油生物添加剂,其特征在于:所述生物质汽油占乙醇汽油生物添加剂的比例为80~99.99%。
3.根据权利要求1或2所述的乙醇汽油生物添加剂,其特征在于:所述生物质汽油来源于热解生物质油高压加氢;所述热解生物质油是由生物质被研磨成颗粒后,在隔绝空气的条件下,迅速被加热到一定温度,后又迅速冷凝,生成的一种棕黑色液体;所述高压加氢的条件,选用280~400℃,2~20MPa氢气压力,以过渡金属化合物为催化剂;加氢后的热解生物质油经过过滤除去杂质,静置分层除去水相,再将油相蒸馏,收集馏程在70~205 ℃之间的有机物,即为生物质汽油。
4.根据权利要求3所述的乙醇汽油生物添加剂,其特征在于:所述生物质为玉米秸秆、果壳果核或树皮树根。
5.根据权利要求1或2所述的乙醇汽油生物添加剂,其特征在于:所述复合改性剂的配制方法如下:以重量计,防蚀剂1~5份,助稳剂1~7份,增燃剂1~10份。
6.根据权利要求5所述的乙醇汽油生物添加剂,其特征在于:所述防蚀剂由防蚀剂A和防蚀剂B混合制成,所述防蚀剂A是苯丙三唑,巯基苯丙三唑,甲基苯丙三唑中的一种或几种,所述防蚀剂B是由硬脂酸甲酯,硬脂酸乙酯中的一种或两种,所述防蚀剂A和防蚀剂B按以下的重量份数进行配制:防蚀剂A 1~10份,防蚀剂B 1~3份。
7.根据权利要求5所述的乙醇汽油生物添加剂,其特征在于:所述助稳剂由助稳剂A和助稳剂B混合制成,所述助稳剂A是六偏磷酸钠,六偏磷酸钾中的一种或两种,所述助稳剂B是叔丁基邻苯二酚、二叔丁基苯酚中的一种或两种,所述助稳剂A和助稳剂B按以下的重量份数进行配制:助稳剂A 1~5份,助稳剂B 5~9份。
8.根据权利要求5所述的乙醇汽油生物添加剂,其特征在于:所述增燃剂由增燃剂A和增燃剂B混合制成,所述增燃剂A是碳6到碳10芳烃中的一种或几种,所述增燃剂B是碳6到碳11烷烃中的一种或几种,所述增燃剂A和增燃剂B按以下的重量份数进行配制:增燃剂A 1~5份,增燃剂B 1~20份。
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