CN106010632B - 一种催化氧化萃取脱除汽油中有机硫的方法 - Google Patents
一种催化氧化萃取脱除汽油中有机硫的方法 Download PDFInfo
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Abstract
本发明的一种催化氧化萃取脱除汽油中有机硫的方法,包括以下步骤:在本发明所述的催化氧化萃取脱硫系统中,双氧水为氧化剂,十二烷基磺酸镧为催化剂,四氯乙烯为萃取剂,在容器中放入一定量的汽油、十二烷基磺酸镧、四氯乙烯和双氧水,搅拌,利用双氧水‑十二烷基磺酸镧的催化氧化作用,在一定的温度下反应一定时间,分离油相与含有有机硫氧化产物的四氯乙烯溶液,由此汽油中硫的脱除率高达95%,该方法能实现深度脱硫,工艺流程简单,设备投资低,环保节约。
Description
技术领域
本发明涉及一种催化氧化萃取工艺,尤其是涉及一种利用双氧水-十二烷基磺酸镧-四氯乙烯脱除汽油中有机硫所使用的催化氧化萃取工艺。
背景技术
随着环保法规的日益严格,世界范围内对车用燃料的质量要求更加苛刻,低硫“清洁燃料”的生产成为必然的趋势。尽管世界各国科研人员在燃油吸附脱硫和氧化脱硫领域有诸多成效,但吸附脱硫和氧化脱硫工作尚存在诸多亟待解决的问题。目前,车用燃油脱硫技术分为加氢脱硫和非加氢脱硫两大类。传统的催化加氧脱硫(HDS)工艺能够满足汽油的低硫要求,但存在投资大、操作条件苛刻、需要氢源,噻吩类硫化物难于脱除等问题。因此,研究和开发操作条件温和、投资少、效益高的非加氢脱硫技术,越来越受到国内外专家和学者的广泛重视。根据原油的产地不同,硫的含量也不一样,但其硫化物类型的分布差别不大,噻吩类化合物通常占总硫的60%~80%,硫醚占总硫量的25%左右。本发明在双氧水-十二烷基磺酸镧(分子式为La[C12H25SO3]3)的催化氧化作用下,以四氯乙烯为有机溶剂,利用四氯乙烯在温和的条件下有选择性地脱除有机硫的氧化产物,而其它烃类物质很少被萃取出来,一般小于汽油有机质的0.5%,且溶剂可以全部回收,是一种较有发展前途的脱硫工艺,工序简单。
发明内容
本发明的目的在于提供一种利用双氧水-十二烷基磺酸镧-四氯乙烯脱除汽油中有机硫的方法,可有效简化汽油中有机硫脱除程序,进一步提高汽油的品质。
本发明的方法是在一个三口烧瓶内,在双氧水-十二烷基磺酸镧的催化氧化作用下,利用四氯乙烯选择性地脱除汽油中有机硫的氧化产物。具体方法如下:
把一个三口烧瓶固定在油浴锅中,分别取4-6mL四氟乙烯,0.0886-0.3544克十二烷基磺酸镧(0.1-0.4mmol),0.1-0.4mL质量分数为30%的双氧水和汽油30mL,放入三口烧瓶中,加入搅拌,在30-75℃温度下反应2~4小时。经过2~4小时从上层油品中取样,用液相色谱测定硫含量。根据原始硫含量,计算出脱硫率(%)。用分液漏斗把上层的油相与下层的四氯乙烯溶液分离开,四氯乙烯中含有有机硫的氧化产物-砜或者亚砜,有机硫的萃取产物和双氧水等一些杂质。把四氯乙烯转移到150mL的锥形瓶中,加入适量的水摇晃,出现沉淀物,溶液变浑浊。把浑浊液过滤,滤走沉淀物,剩余的液体放到旋转蒸发仪旋转蒸发,得到的四氯乙烯循环使用。
本发明的原理反应如下:
利用双氧水-十二烷基磺酸镧的催化氧化作用将油品中的有机硫氧化,如烷基二苯并噻吩(分子式为R-DBT)、硫醚,使它们转化为相应的砜或者亚砜,用四氯乙烯萃取分离。
双氧水-十二烷基磺酸镧-四氯乙烯脱除汽油中有机硫的效果比较明显,反应条件温和(常压、中性、低于80℃),在较优的条件下有机硫脱除率最高可达95%,且脱硫后油品的结构基本未发生变化,有机质损失也较少,因而该法是一种效果好、安全、温和的脱除有机硫的方法,具有很好的发展前景。
本发明的特点是:
(1)能实现深度脱硫,产品硫含量可以达到10ppm以下。
(2)反应条件温和,温度<100℃,常压操作。
(3)无须氢源、耐压设备,工艺流程简单,设备投资低。
附图说明
图1为用于本发明的催化氧化萃取脱硫系统。
图2为用于本发明的脱硫反应装置。
具体实施方式
如附图2所示,把一个250mL三口烧瓶固定在油浴锅中,一个口连接冷凝管,通冷凝水。另两个口用胶塞封住,其中一个作为搅拌棒入口,另一个为温度计插入口。分别取4mL四氟乙烯,0.1772克十二烷基磺酸镧分子量(0.2mmol),0.2mL质量分数为30%的双氧水和汽油30mL,放入三口烧瓶中,搅拌,在50℃的恒定温度下反应3小时,从上层油品中取样分析,脱硫率达到为95%左右。用分液漏斗把上层的油相与下层的四氯乙烯溶液分离开,把四氯乙烯转移到150mL的锥形瓶中,加入30mL蒸馏水摇晃,溶液浑浊,过滤,滤走沉淀物,剩余的液体放到旋转蒸发仪在90℃下旋转蒸发4小时,得到的四氯乙烯循环使用。
Claims (1)
1.一种催化氧化萃取脱除汽油中有机硫的方法,其特征在于:在催化氧化萃取脱除系统中,加入0.1-0.4mL双氧水为氧化剂,加入0.0886-0.3544克十二烷基磺酸镧为催化剂,加入4-6mL四氯乙烯为萃取剂,30mL汽油为原料,在双氧水-十二烷基磺酸镧的催化氧化作用下,在30-75℃下,反应2~4小时,利用四氯乙烯有选择性脱除汽油中的有机硫的氧化产物,四氯乙烯经过后处理可循环使用。
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CN101270299A (zh) * | 2008-04-30 | 2008-09-24 | 武汉科技大学 | 一种轻质油品氧化脱硫的方法 |
CN101962567A (zh) * | 2010-09-30 | 2011-02-02 | 西安科技大学 | 一种油品中含硫化合物的催化氧化方法 |
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CN101962567A (zh) * | 2010-09-30 | 2011-02-02 | 西安科技大学 | 一种油品中含硫化合物的催化氧化方法 |
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