CN102229823A - 一种萜烯碳酸异丙酯汽油抗爆剂 - Google Patents

一种萜烯碳酸异丙酯汽油抗爆剂 Download PDF

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CN102229823A
CN102229823A CN2011101554754A CN201110155475A CN102229823A CN 102229823 A CN102229823 A CN 102229823A CN 2011101554754 A CN2011101554754 A CN 2011101554754A CN 201110155475 A CN201110155475 A CN 201110155475A CN 102229823 A CN102229823 A CN 102229823A
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刘立强
孟文斌
钱佐阵
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Xi'an Wonder Science & Technology Co ltd
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Abstract

本发明涉及抗爆剂技术领域，具体涉及一种萜烯碳酸异丙酯汽油抗爆剂。本发明汽油抗爆剂具有独特的性能和用途，可以作为新型功能性化合物使用，用量少即可提高汽油的辛烷值，即提高汽油的防爆效果。本发明包括以下重量份的原料：四乙基溴化胺0.1～3.0份、α-蒎烯60～100份、异丙醇20～40份。

Description

一种萜烯碳酸异丙酯汽油抗爆剂
一、技术领域：
本发明涉及抗爆剂技术领域，具体涉及一种萜烯碳酸异丙酯汽油抗爆剂。
二、背景技术：
汽油是汽车发动机的主要动力燃料，随着汽车的发展和技术进步，对汽油的要求越来越高，提高汽油的质量是必然趋势，加入汽油抗爆剂是提高汽油辛烷值的方法之一，汽油抗爆剂是一类能够改善汽油燃烧状况，提高汽油辛烷值的化学物质，而汽油辛烷值是反应汽油质量的关键之一，对汽油来说，只须向油中添加少量的抗爆剂便能够有效地提高汽油辛烷值，这对炼油厂增产汽油、节能、 提高生产灵活性和经济效益来说，是一种既简便而又有效的办法，因而国际上大的石油公司都十分重视新型高效廉价的汽油抗爆剂的研究和产品开发。
辛烷值是车用汽油最重要的质量指标，它综合反映一个国家炼油工业水平和车辆设计水平，采用抗爆剂是提高车用汽油辛烷值的重要手段。四乙基铅是1921年发现的，1923年开始在车用汽油中使用，直至1959年被人们唯一使用的辛烷值改进剂，1960年四甲基铅进入抗爆剂市场，催化重整工艺的发展使其使用量迅速增加，烷基铅抗爆剂具有工艺简单、成本低廉、效果突出的优势，所以一直是效率很高的辛烷值改进剂，自1970年日本东京新宿区发生铅中毒事件后，由烷基铅抗爆剂造成的铅污染引起了人们的广泛重视。研究结果表明，烷基铅本身和它燃烧后的产物都有毒，对环境和人体的危害大，1980年以来美国和西欧逐步禁止TEL在汽油中添加，我国已于2000年7月在全国停止销售和使用含铅汽油，这就导致了优质无铅汽油的需求量也日益增加，促使各国都去努力探索高效而经济的途径来提高汽油的辛烷值。人们对非铅抗爆剂的探索一直在不懈努力。几十年来国内外所研发的无铅汽油抗爆剂种类繁多。
金属类抗爆剂典型化合物是甲基环戊二烯三羰基锰([MnCH3C5H5(CO)3])。MMT不易蒸发损失、不溶于水、性质稳定、能够与油品进行很好的兼容，有效地改善汽油品质。但作为金属抗爆剂也存在不少缺点，MMT的燃烧排放物会沉积在燃烧室、进气阀和火花塞表面，缩短进气阀寿命，使火花阻塞不能正常点火，影响发动机正常工作，并对汽车尾气净化剂有中毒现象。鉴于MMT的种种缺点，欧洲共同体国家和日本已禁止使用MMT作为汽油添加剂，1999年6月我国家环保局也批准MMT限量使用，我国颁布的汽油标准GB17930-1999(车用无铅汽油标准)没有明确禁止使用锰类抗爆剂，但是允许MMT的加入量为18mg/L。
由于金属类抗爆剂产生的颗粒物污染和对三元催化器的损害等问题，对其研究处于相对停滞阶段。各国对抗爆剂的研究重点放在了非金属类，非金属类抗爆剂主要有醚、醇、酯类等。 
甲基叔丁基醚，简称MTBE，作为汽油添加剂已经在全世界范围内普遍使用。它不仅能有效提高汽油辛烷值，而且还能改善汽车性能，降低排气中CO含量，同时降低汽油生产成本。MTBE应用至今，需求量、消费量一直处于高增长状态，其生产技术也日趋成熟。但最近，美国加州以污染水质为由，禁止使用MTBE，美国国家环境保护部门也有类似动作。这表明，美国已开始限制MTBE生产及应用。美国是MTBE消费大国，这一演变将使MTBE产业受到威胁。
萜烯类(terpenes)物质是一类具有较强化学活性的天然烃类化合物，在自然界广泛分布，到1991年，人类发现的萜烯类化合物已经超过22000种。德国的奥托·瓦拉赫因研究萜类化合物具有创造性成果，于1910年成为诺贝尔化学奖获得者。萜烯类物质作为一类非常重要的化合物引起了全世界的瞩目。萜类化合物多具较强的香气和生物活性。CN101144041介绍了一种车用汽油抗爆剂混合物，属汽油抗爆剂领域，以环戊二烯三羰基锰(CMT)抗爆剂，替代现有的甲基环戊二烯三羰基锰(MMT)抗爆剂，达到提升汽油组分油品辛烷值，特别是提升低标号汽油组分油品辛烷值的目的。
三、发明内容：
本发明的目的在于提供一种萜烯碳酸异丙酯汽油抗爆剂,其添加少量就可
提高汽油的防爆效果。
本发明本发明采用的技术方案为 ：一种萜烯碳酸异丙酯汽油抗爆剂，包括以下重量份的原料为：四乙基溴化胺0.1～3.0份、α-蒎烯60～100份、 异丙醇20～40份。
包括以下重量份的原料为：四乙基溴化胺0.1～2份、α-蒎烯70～85份、 异丙醇28～32份。
一种萜烯碳酸异丙酯汽油抗爆剂的制备方法为：在带有电动搅拌器和热电偶探头的500mL的高压反应釜中加入60～100克的α-蒎烯与28～32克异丙醇和1克的四乙基溴化胺催化剂，搅拌升温至50℃～150℃，从引导管加入二氧化碳，使反应釜达的压力达到3～20 Mpa，反应过程中，控制二氧化碳的压力在4～12MPa之间维持在6小时，并充分搅拌反应物，然后降低反应釜温度至40℃，将多余的二氧化碳通过引导管放空，从反应釜底部放出物料浅黄透明的液体，得到萜烯碳酸异丙酯。
与现有技术相比，本发明具有的优点和效果如下：本发明汽油抗爆剂具有独特的性能和用途，可以作为新型功能性化合物使用，用量少即可提高汽油的辛烷值，即提高汽油的防爆效果。
四、具体实施方式：
实施例1
在500mL高压反应釜中加入70克α-蒎烯，30克异丙醇，和0.1克四乙基溴化胺催化剂，搅拌升温至120℃。从引导管加入二氧化碳，使反应釜压力达到4MPa，开动搅拌。反应过程中，控制二氧化碳压力在4MPa±0.02MPa之间，反应时间为6小时。然后降低反应釜温度至40℃，将多余二氧化碳通过引导管放空。从反应釜底部放出物料，得浅黄色透明的液体A—萜烯碳酸异丙酯。
实施例2
在500mL高压反应釜中加入84克α-蒎烯，30克异丙醇，和0.2克四乙基溴化胺催化剂，搅拌升温至80℃。从引导管加入二氧化碳，使反应釜压力达到6MPa，开动搅拌。反应过程中，控制二氧化碳压力在6MPa±0.02MPa之间，反应时间6小时。然后降低反应釜温度至40℃，将多余二氧化碳通过引导管放空。从反应釜底部放出物料，得浅黄色透明的液体B—萜烯碳酸异丙酯。
实施例3
在500mL高压反应釜中加入70克α-蒎烯，30克异丙醇，和0.5克四乙基溴化胺催化剂，搅拌升温至60℃。从引导管加入二氧化碳，使反应釜压力达到8MPa，开动搅拌。反应过程中，控制二氧化碳压力在8MPa±0.02MPa之间，反应时间6小时。然后降低反应釜温度至40℃，将多余二氧化碳通过引导管放空。从反应釜底部放出物料，得浅黄色透明的液体C—萜烯碳酸异丙酯。
实施例4
在500mL高压反应釜中加入70克α-蒎烯，30克异丙醇，和1.0克四乙基溴化胺催化剂，搅拌升温至90℃。从引导管加入二氧化碳，使反应釜压力达到10MPa，开动搅拌。反应过程中，控制二氧化碳压力在10MPa±0.02MPa之间，反应时间6小时。然后降低反应釜温度至40℃，将多余二氧化碳通过引导管放空。从反应釜底部放出物料，得浅黄色透明的液体D—萜烯碳酸异丙酯。
实施例5
在500mL高压反应釜中加入70克α-蒎烯，30克异丙醇，和2.0克四乙基溴化胺催化剂，搅拌升温至90℃。从引导管加入二氧化碳，使反应釜压力达到12MPa，开动搅拌。反应过程中，控制二氧化碳压力在12MPa±0.02MPa之间，反应时间6小时。然后降低反应釜温度至40℃，将多余二氧化碳通过引导管放空。从反应釜底部放出物料，得浅黄色透明的液体E—萜烯碳酸异丙酯。
合成化合物的收率汇总见表1。
Figure 2011101554754100002DEST_PATH_IMAGE001
发明的效果
本发明的效果通过实施例6至实施例20来说明。
实施例6至实施例10列出了萜烯碳酸异丙酯在汽油A中使用效果。取1000mL汽油A，将萜烯碳酸异丙酯按照3%比例加入到汽油A中，混合均匀后，测定汽油A的辛烷值。其辛烷值数据见表2。
Figure 2011101554754100002DEST_PATH_IMAGE002
实施例11至实施例15列出了萜烯碳酸异丙酯D在汽油A中使用效果。取1000mL汽油A，将萜烯碳酸异丙酯D按照一定比例加入到汽油A中，混合均匀后，测定汽油A的辛烷值。其辛烷值数据见表3。
Figure 2011101554754100002DEST_PATH_IMAGE003
实施例16至实施例20列出了萜烯碳酸异丙酯D在汽油B～汽油F中使用效果。取1000mL汽油，将萜烯碳酸异丙酯D按照3%的比例加入到汽油中，混合均匀后，测定汽油的辛烷值。其辛烷值数据见表4。
Figure 2011101554754100002DEST_PATH_IMAGE004
表2数据说明萜烯碳酸异丙酯A～萜烯碳酸异丙酯E在汽油A中的效果是一致的。从表3和表4的数据可以看出，萜烯碳酸异丙酯在汽油中具有较好的使用效果，可以提高汽油的辛烷值。同时，在不同的汽油中也有很好的使用效果。
测定用的汽油性质见表5～表10。
 
Figure 2011101554754100002DEST_PATH_IMAGE006
Figure 2011101554754100002DEST_PATH_IMAGE007
Figure 2011101554754100002DEST_PATH_IMAGE008
Figure 2011101554754100002DEST_PATH_IMAGE009
Figure 2011101554754100002DEST_PATH_IMAGE010

Claims (3)

1.一种萜烯碳酸异丙酯汽油抗爆剂，其特征在于：包括以下重量份的原料为：四乙基溴化胺0.1～3.0份、α-蒎烯60～100份、 异丙醇20～40份。
2.根据权利要求1所述的一种萜烯碳酸异丙酯汽油抗爆剂，其特征在于：包括以下重量份的原料为：四乙基溴化胺0.1～2份、α-蒎烯70～85份、 异丙醇28～32份。
3.根据权利要求1所述的一种萜烯碳酸异丙酯汽油抗爆剂的制备方法，其特征在于：所述的抗爆剂的制备方法为：在带有电动搅拌器和热电偶探头的500mL的高压反应釜中加入60～100克的α-蒎烯与28～32克异丙醇和1克的四乙基溴化胺催化剂，搅拌升温至50℃～150℃，从引导管加入二氧化碳，使反应釜达的压力达到3～20 Mpa，反应过程中，控制二氧化碳的压力在4～12MPa之间维持在6小时，并充分搅拌反应物，然后降低反应釜温度至40℃，将多余的二氧化碳通过引导管放空，从反应釜底部放出物料浅黄透明的液体，得到萜烯碳酸异丙酯。
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