CN100469859C - 一种乙醇改性剂及其应用 - Google Patents

一种乙醇改性剂及其应用 Download PDF

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CN100469859C
CN100469859C CNB2006101123076A CN200610112307A CN100469859C CN 100469859 C CN100469859 C CN 100469859C CN B2006101123076 A CNB2006101123076 A CN B2006101123076A CN 200610112307 A CN200610112307 A CN 200610112307A CN 100469859 C CN100469859 C CN 100469859C
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ethanol
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naphthenate
ethanol modifier
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侯金鹏
刘宝贵
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BEIJING ZHONGTIAN ALCOHOL ENERGY TECHNOLOGY Co Ltd
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Abstract

一种乙醇改性剂以及由改性剂制得的乙醇清洁汽油，其中乙醇改性剂是由如下重量配比的原料配制而成：除糖剂12-17、乳化剂2-5、抗氧剂2-6、防腐剂2-6、抗老化剂3-8、清洁剂1-3、抗磨剂7-10、助燃剂12-15、辛烷值改进剂22-28、相溶剂18-30。该乙醇改性剂各组分均为常规市售化学品，配料和制备方法简单；经该乙醇改性剂配置得到的乙醇清洁汽油优于国标93#汽油标准，并可达到欧IV排放标准。

Description

一种乙醇改性剂及其应用
技术领域
本发明属于将乙醇改性为清洁汽油的改性剂技术领域，尤其涉及一种能够使乙醇作为车用燃料的乙醇改性剂及其应用。
背景技术
随着石油需求量的不断增大和原油短缺问题的现实情况，我国正重点推广车用乙醇汽油，以解决日益严重的能源危机。乙醇是可再生的资源，燃烧过程中没有有害物质产生，是一种环保型清洁燃料。可用乙醇补充或替代日益紧张的石油能源，还可保护环境不受汽车尾气的危害。但乙醇燃料与石化燃料相比存在很多缺点：首先，乙醇是低碳醇，水溶性好，与汽油相比润滑性能差，直接作为汽车燃料使用会使汽缸内壁摩擦增大，温度急剧上升，甚至出现干烧现象，使发动机磨损加剧，影响发动机使用寿命；其次是我国的乙醇多是用发酵法生产，是在生物酶的作用下，将淀粉转化成糖，近而水解成乙醇的生产工艺。生产过程中，会有部分未水解的糖不能完全脱除而混杂于乙醇中。这些糖，遇高温会变成焦糖，燃烧过程中会在缸体内沉积，产生大量积碳；日久会影响发动机正常工作。再者，乙醇会对汽车中塑料、橡胶部件有一定腐蚀、融胀作用，乙醇燃烧后形成的乙酸也会对汽车发动机有一定的腐蚀作用；乙醇的闪点明显高于汽油，低温条件下不易点火。
目前存在各种各样的乙醇清洁燃料和用于在汽油中添加乙醇的改性剂，但这些乙醇清洁燃料和改性剂均不以乙醇作为车用燃料的主要成分，而是以石化汽油作为主要成分，添加10～30％左右的乙醇配制而成。该燃料尽管在燃烧过程中能够使汽车尾气排放的一氧化碳、碳氢化合物、酮类和苯类等有害物质减少，但没有根本改变对环境污染的影响，也没有改变对石油资源的依赖性，不能完全替代石化燃料作为车用燃料使用。
发明内容
本发明的目的在于提供一种能够使乙醇在不添加石化汽油的情况下可作为清洁燃料的乙醇改性剂及其应用，以及经过该乙醇改性剂改性后的乙醇清洁汽油。
本发明采用的技术方案如下：
一种乙醇改性剂，其特征在于它是由如下重量份数的原料配制而成：
除糖剂                 12-17
乳化剂                 2-5
抗氧剂                 2-6
防腐剂                 2-6
抗老化剂               3-8
清洁剂                 1-3
抗磨剂                 7-10
助燃剂               12-15
辛烷值改进剂         22-28
相溶剂               18-30
其中除糖剂为乙酸丁脂、乙酸异戊酯或乙酸乙酯中的一种或多种；乳化剂为烷基酚聚氧乙烯醚；抗氧剂为2，6—二叔丁基对甲酚；防腐剂为苯并三氮唑、苯并三唑衍生物或烷基氨基磷酸酯中的一种或多种；抗老化剂为苯基-α-萘胺、苯基-β-萘胺的一种或多种；清洁剂为环烷酸盐、石油磺酸盐或烷基苯磺酸钡中的一种或多种；抗磨剂为氯化石蜡；助燃剂为四氯乙烯或碳酸二甲酯中的一种或多种；辛烷值改进剂为甲基叔丁基醚、甲基叔戊基醚或异丙醚中的一种或多种；相溶剂为异丙醇、异丁醇、正丁醇或异辛醇中的一种或多种。
所述的环烷酸盐为环烷酸钡或环烷酸锰；所述的石油磺酸盐为石油磺酸钡或石油磺酸钠。
苯并三唑衍生物为苯并三唑脂肪胺盐或苯并三唑甲醛-胺缩合物(商品名称为T551)；烷基氨基磷酸酯中的烷基是辛烷或壬烷或二者的混合物。
其中除糖剂优选为乙酸乙酯，乳化剂优选为烷基酚聚氧乙烯醚；抗氧剂优选为2，6—二叔丁基对甲苯酚；防腐剂优选为苯并三氮唑，抗老化剂优选为苯基-α-萘胺，清洁剂优选为环烷酸钡，抗磨剂优选为氯化石蜡，助燃剂优选为四氯乙烯，辛烷值改进剂优选为甲基叔丁基醚，相溶剂优选为异丙醇、异丁醇1：1的混合液体。
所述的烷基酚聚氧乙烯醚为TX-4，TX-7或TX-10中的一种或多种，优选TX-4。
组成该乙醇改性剂的各组分全部采用市售化学品。
市售化工原料中没有氯化石蜡纯品，本发明中采用重量含量为52％的氯化石蜡。
所述乙醇改性剂的制备方法，将相溶剂按比例投入到搅拌设备内，再将抗氧剂与防腐剂的固体粘稠料投入设备，以80～1000转/分的速率搅拌，使之溶解、稀释成均一液体。
再将改性剂中的其它各原料投入到搅拌设备内，以200～1000转/分的搅拌速率进行搅拌混合，直到各组分混合均匀，得到乙醇改性剂。
一种乙醇清洁汽油，其由乙醇改性剂和乙醇配置而成，其中乙醇改性剂与乙醇的重量配比为1∶4～1：15.6，所述乙醇的重量浓度为95％-100％。
所述乙醇清洁汽油的制备方法为，按重量配比将乙醇改性剂和乙醇加入搅拌罐，并在常温常压下进行搅拌，搅拌速率为200～1000转/分，直至二组分完全混合，即得乙醇清洁汽油。
在乙醇清洁汽油中，除糖剂能够消除乙醇所含糖类物质在燃烧过程中产生积碳的问题，并能改善乙醇的燃烧性能；抗氧剂对甲苯酚，能提高乙醇的抗氧化性能和稳定性；防腐剂能减弱乙醇汽油对铜、铁和铝等金属件的腐蚀；防老化剂，其能够有效地减少乙醇汽油对橡胶件的溶胀、老化作用，保证各部件的密封性能良好；助燃剂能有效地改善乙醇汽油的低温燃烧性能，抗磨剂氯化石蜡既能使各种组分充分互溶，还可以增加乙醇汽油的油性，增加润滑能力，减少汽车发动机的运行噪声；辛烷值改进剂可有效地提高乙醇汽油的辛烷值，避免爆震，使得乙醇汽油顺利地燃烧，动力增加；相溶剂为高碳醇类的混合物，以提高各组分混合的均匀程度；乳化剂选用表面活性剂具有良好的油溶性和乳化性能，能消除乙醇中所含的大颗粒水分对乙醇燃烧性能的影响。作为乙醇改性清洁汽油的主体成分—乙醇，其纯度要求必须在95％以上(重量比)。
该乙醇改性剂可以将乙醇改性为性能优良的车用燃料—乙醇改性清洁汽油，并可达到欧IV排放标准。一吨乙醇清洁汽油中，乙醇最大量为840～940kg。使用该乙醇改性剂配制乙醇清洁汽油所需的设备简单，只需将乙醇改性剂各组分混合搅拌均匀，然后投入到乙醇中，经过搅拌装置进行剪切搅拌混合，使乙醇和乙醇改性剂各组分充分混合即可。
本发明的有益效果在于，该乙醇改性剂各组分均为常规市售化学品，配料和制备方法简单，不需添加汽油就能够将乙醇改性为车用清洁燃油，并且改性的乙醇汽油性能优于国标93#汽油标准。该乙醇改性剂可作为工业乙醇和生物乙醇配车用清洁燃料的添加剂得到广泛的应用。
具体实施方式
下面结合实施例对本发明作进一步的阐述。
实施例1：
按如下重量配比取乙醇改性剂各组分：
乙酸丁脂                               15   重量份
烷基酚聚氧乙烯醚TX—4                  3    重量份
2，6-二叔丁基对甲苯酚                  3    重量份
苯并三氮唑                             3    重量份
苯基-1-萘胺                            3    重量份
环烷酸钡                               2    重量份
四氯乙烯                               14   重量份
氯化石蜡                               8    重量份
甲基叔丁基醚                           26   重量份
异丙醇、异丁醇混合物                   23   重量份
其中异丙醇、异丁醇混合物中异丙醇与异丁醇的体积比为1：1；
将异丙醇、异丁醇按比例混合，投入搅拌设备，再将二叔丁基对甲酚、苯并三氮唑的固体粘稠料投入设备，以200转/分的速率搅拌，使之溶解、稀释成均一液体。
将改性剂中其它各原料投入到搅拌混合设备内，以800转/分的搅拌速率下进行搅拌混合，直到各组分混合均匀，得到乙醇改性剂。
将实施例1制备的乙醇改性剂160kg和840kg浓度为95重％的乙醇投放到搅拌器内，在600转/分的转速下进行搅拌混合，进行搅拌混合，得到改性乙醇清洁汽油。对该乙醇清洁汽油进行各项性能检测，并将检测数据与93#汽油国家标准进行对比的情况见表1。
      表1 乙醇清洁燃料与93#汽油的各项性能指标对比情况
Figure C200610112307D00061
由上表可以看出，经过该乙醇改性剂进行改性的乙醇清洁汽油的各项性能指标均达到或优于93#汽油的国标标准。
排放监测结果如下：
监测样车：
车牌号：鲁A—M4068东风雪铁龙DC7163SX轿车，
        发动机编号：0179242
        累计行程：174186km
排放CO、HC浓度检测结果
Figure C200610112307D00071
实施例2
按重量比取下列组分配制改性剂：
乙酸乙酯                       6重量份
乙酸丁酯                       8重量份
2，6-二叔丁基对甲苯酚          2.5重量份
烷基酚聚氧乙烯醚TX—7          2.5重量份
苯并三氮唑                     3.5重量份
苯基-1-萘胺                    2重量份
苯基-2-萘胺                    2重量份
环烷酸锰                       2.5重量份
四氯乙烯                       15重量份
氯化石蜡                       7重量份
甲基叔丁基醚                   23重量份
正丁醇、辛醇混合液             26重量份
其中正丁醇、辛醇混合液中正丁醇与辛醇体积比为7：3。
将辛醇、丁醇按比例混合，投入搅拌设备，再将二叔丁基对甲酚、苯丙三氮唑的固体粘稠料投入设备，以200转/分的速率搅拌，使之溶解、稀释成均一液体。
将上述其他各原料投入到搅拌混合设备内，以800转/分的搅拌速率进行搅拌混合，直到各组分混合均匀，得到乙醇改性剂。
将实例2制备的改性剂200公斤，95重％乙醇800公斤放入搅拌罐，充分搅拌均匀，即成乙醇含量82～～85％的高清洁乙醇汽油。
此例乙醇汽油的特点是低温启动效果好，动力强劲，抗氧化能力强，能长时间保存。
表2 实施例2乙醇清洁燃料的检测指标
 
检测项目 93#汽油参数    检测结果 单项结论
辛烷值(RON) ≥93 94 合格范围
实际胶质mg/100ml  ≤5 1 合格范围
硫含量％(M/M) ≤0.08 0.04 合格范围
铜片腐蚀(50℃3h)           ≤1 1a 合格范围
实施例3
改性剂按下列组分购成：
乙酸丁酯                15       重量份
四氯乙烯                14       重量份
氯化石蜡                8        重量份
二叔丁基对甲酚          4        重量份
苯并三氮唑              4        重量份
苯基-1-萘胺             4        重量份
异丙醇、正丁醇混合物    20       重量份
甲基叔丁基醚            26       重量份
烷基酚聚氧乙烯醚TX-10   3        重量份
环烷酸锰                2        重量份
其中异丙醇、正丁醇混合物中异丙醇与正丁醇的体积比为1：1。
将异丙醇、正丁醇按比例混合，投入搅拌设备，将二叔丁基对甲酚、苯并三氮唑等固体、粘稠料投入设备，以200转/分的速率搅拌，使之溶解、稀释成均一液体。
将上述其他各原料投入到搅拌混合设备内，以800转/分的搅拌速率下进行搅拌混合，直到各组分混合均匀，得到乙醇改性剂。
取上述改性剂210公斤，95重％乙醇790公斤，加入搅拌罐以600～800分/转的速度逐渐加速搅拌10～15分钟，混合均匀后，静置15分钟，得乙醇清洁汽油。
该实例所得清洁燃料性能优越，辛烷值高，动力性能好，低温启动性能良好，排放污染小。
表3 实施例3乙醇清洁燃料的检测指标
 
检测项目 93#汽油参数    检测结果 单项结论
辛烷值(RON) ≥93 95 合格范围
实际胶质mg/100ml  ≤5 1 合格范围
硫含量％(M/M) ≤0.08 0.04 合格范围
铜片腐蚀(50℃3h)           ≤1 1a 合格范围
实施例4
按下列成分取原料构成乙醇改性剂：
乙酸丁酯                  14      重量份
四氯乙烯                  12      重量份
氯化石蜡                  9       重量份
二叔丁基对甲苯酚          5       重量份
苯并三氮唑脂肪胺盐        3       重量份
苯基-1-萘胺               3       重量份
异丙醇、辛醇混合物        22      重量份
甲基叔丁基醚              25      重量份
壬基酚聚氧乙烯醚          4       重量份
环烷酸钡                  3       重量份
其中异丙醇、辛醇混合物中异丙醇与辛醇的体积比为6：4。
将异丙醇、辛醇按比例混合，投入搅拌设备，将二叔丁基对甲酚、苯并三氮唑脂肪胺盐等固体、粘稠料投入设备，以200转/分的速率搅拌，使之溶解、稀释成均一液体。
将上述其他各原料投入到搅拌混合设备内，以800转/分的搅拌速率下进行搅拌混合，直到各组分混合均匀，静置15分钟，滤除沉淀杂质，得清洁燃料乙醇改性剂。
将本例制得的改性剂200公斤，95重％乙醇800公斤置入开口罐中，用搅拌器、静态混合器搅混均匀，即得燃料乙醇。此例中乙醇约占81％。
此例燃料乙醇的特点是：起动性能良好，燃料燃烧充分，动力强劲，加速性能良好，适用于高压缩比的车辆使用。而且尾气排放良好，污染物极少，堪称清洁燃料。
表4 实施例4乙醇清洁燃料的检测指标
 
检测项目 93#汽油参数    检测结果 单项结论
辛烷值(RON) ≥93 95 合格范围
实际胶质mg/100ml  ≤5 1 合格范围
硫含量％(M/M) ≤0.08 0.04 合格范围
铜片腐蚀(50℃3h)           ≤1 1a 合格范围
10％蒸发温度/℃ ≤70 61 合格范围
50％蒸发温度℃ ≤120 74 合格范围
90％蒸发温度℃ ≤190 156 合格范围
终馏点℃ ≤210 180 合格范围

Claims (7)

1.一种乙醇改性剂，其特征在于它是由如下重量份数的原料配制而成：
除糖剂                       12-17
乳化剂                       2-5
抗氧剂                       2-6
防腐剂                       2-6
抗老化剂                     3-8
清洁剂                       1-3
抗磨剂                       7-10
助燃剂                       12-15
辛烷值改进剂                 22-28
相溶剂                       18-30
其中除糖剂为乙酸丁酯、乙酸异戊酯或乙酸乙酯中的一种或多种；乳化剂为烷基酚聚氧乙烯醚；抗氧剂为2，6—二叔丁基对甲酚；防腐剂为苯并三氮唑、苯并三唑衍生物或烷基氨基磷酸酯中的一种或多种；抗老化剂为苯基-α-萘胺、苯基-β-萘胺中的一种或两种；清洁剂为环烷酸盐、石油磺酸盐或烷基苯磺酸钡中的一种或多种；抗磨剂为氯化石蜡；助燃剂为四氯乙烯或碳酸二甲酯中的一种或两种；辛烷值改进剂为甲基叔丁基醚、甲基叔戊基醚或异丙醚中的一种或多种；相溶剂为异丙醇、异丁醇、正丁醇或异辛醇中的一种或多种。
2.权利要求1所述的一种乙醇改性剂，其中所述的环烷酸盐为环烷酸钡或环烷酸锰；所述的石油磺酸盐为石油磺酸钡或石油磺酸钠。
3、权利要求1所述的一种乙醇改性剂，其中所述的除糖剂为乙酸乙酯，乳化剂为烷基酚聚氧乙烯醚，抗氧剂为2，6—二叔丁基对甲酚，防腐剂为苯并三氮唑，抗老化剂为苯基-α-萘胺，清洁剂为环烷酸钡，抗磨剂为氯化石蜡，助燃剂为四氯乙烯，辛烷值改进剂为甲基叔丁基醚。
4、权利要求1-3中任一项所述的一种乙醇改性剂，其中所述的烷基酚聚氧乙烯醚为TX-4，TX-7或TX-10中的一种或多种。
5、权利要求1-3中任一项所述的乙醇改性剂的制备方法，将相溶剂按比例投入到搅拌设备内，再将抗氧剂与防腐剂的固体粘稠料投入设备，以80～1000转/分的速率搅拌，使之溶解、稀释成均一液体；
再将改性剂中的其它各原料投入到搅拌设备内，以200～1000转/分的搅拌速率进行搅拌混合，直到各组分混合均匀，得到乙醇改性剂。
6、一种乙醇清洁汽油，其由权利要求1-3中任一项所述的乙醇改性剂和乙醇配制而成，其中乙醇改性剂与乙醇的重量配比为1∶4～1：15.6，所述乙醇的重量浓度为95％-100％。
7、权利要求6所述的乙醇清洁汽油的制备方法，按重量配比将乙醇改性剂和乙醇加入搅拌罐，并在常温常压下进行搅拌，搅拌速率为200～1000转/分，直至二组分完全混合，即得乙醇清洁汽油。
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