CN106010632A - 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 PDF

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CN106010632A
CN106010632A CN201610379822.4A CN201610379822A CN106010632A CN 106010632 A CN106010632 A CN 106010632A CN 201610379822 A CN201610379822 A CN 201610379822A CN 106010632 A CN106010632 A CN 106010632A
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gasoline
tetrachloroethylene
lanthanum
catalytic oxidation
organic sulfur
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CN106010632B (zh
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杜荣斌
刘涛
夏宏宇
徐衡
王钧伟
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Anqing Normal University
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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

一种催化氧化萃取脱除汽油中有机硫的方法
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 (2)

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，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，汽油为原料，在双氧水-十二烷基磺酸镧的催化氧化作用下，在一定温度下反应一定时间，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。
2.根据权利要求1所述的脱除方法，其特征在于：脱除温度为30-75℃，反应时间为2～4小时，双氧水加入量为0.1-0.4mL，十二烷基磺酸镧加入量为0.0886-0.3544克，四氟乙烯加入量为4-6mL。
CN201610379822.4A 2016-05-26 2016-05-26 一种催化氧化萃取脱除汽油中有机硫的方法 Expired - Fee Related CN106010632B (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US20150252272A1 (en) * 2012-09-28 2015-09-10 Aditya Birla Science And Technology Company Limited Methods and compositions for desulfurization of compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US20150252272A1 (en) * 2012-09-28 2015-09-10 Aditya Birla Science And Technology Company Limited Methods and compositions for desulfurization of compositions

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