CN101301627B - 仿生催化氧气氧化噻吩类化合物的方法 - Google Patents
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Abstract
本发明属于催化氧化脱硫技术领域，公开了一种仿生催化氧化噻吩类化合物的方法。其特征是仿生催化剂的结构如通式I、II所示：
其中：M＝Fe、Co或Mn；R1＝NO2、NH2、Cl、F、SOH3或H；R2＝NO2、NH2、Cl、F、SOH3或H；R3＝NO2、NH2、Cl、F、SOH3或H；R4＝NO2、NH2、Cl、F、SOH3或H；R5＝NO2、NH2、Cl、F、SOH3或H。本发明的效果和益处是以金属酞菁类和金属卟啉类化合物为催化剂，可以实现在温和条件下高选择性地传递、活化氧分子，催化氧化有机物。此反应体系不需要加入共氧剂，不腐蚀油品且对环境友好，催化剂用量小，可回收利用，使成本降低，反应温度和反应压力不高，而且可实现油品的深度脱硫。
Description
技术领域
本发明属于催化氧化脱硫技术领域，涉及一种仿生催化氧气氧化噻吩类化合物的方法。
背景技术
加氢脱硫是目前较成熟的工艺，容易脱除油品中的硫醇、硫醚。但对二苯并噻吩，特别是4位或4、6位取代的二苯并噻吩加氢困难。氧化脱硫的反应条件温和、不耗费氢气，能够有效脱除二苯并噻吩和烷基取代二苯并噻吩系列硫化物，工艺投资和操作费用较低，操作条件比加氢脱硫更容易，应用前景广阔。
氧化脱硫中的关键步骤是对硫化物的氧化反应。早期使用氧气进行氧化脱硫的技术是对活泼硫醇的氧化，反应以四磺基酞菁钴为催化剂，在常温常压下，硫醇形成二硫醚，可以脱除硫醇的气味，但达不到真正脱硫的目的(Brouwer MW，Piet P，German L A.Autoxidation of thiols with cobalt(II)phthalocyaninetetrasodiunm sulfonate attached to poly(vinylamine)II.Kinetic measurements.Journal Molecular Catalysis，1985，29，347-361；Sorokin A，Meunier B.Oxidation ofpolycyclic aromatic hydrocarbons catalyzed by iron tetrasulfophthalocyanine FePcS：inverse isotope effects and oxygen，labeling studies.Eur.J.Inorg.Chem.1998，1269-1281.)。以氧气为氧化剂对噻吩类物质的氧化反应主要采用共氧剂的方法，氧气首先氧化共氧剂，使共氧剂成为液相氧化剂，达到与硫化物传质加快，间接氧化噻吩类化合物的目的，Murata等(Murata S，Murata K，Kidena K et al.ANovel Oxidative desulfurization system for diesel fuels with molecular oxygen in thepresence of cobalt catalysts and aldehydes.Energy & Fuels，2004，18(1)：116-121.)考察了用O2作为氧化剂，辛醛为共氧剂，在钴盐的作用下对模拟油品和柴油的氧化脱硫。反应首先把苯、DBT、辛醛和钴盐的混合物稳定在40℃，然后通入常压的O2，大约经过15min后，DBT几乎定量的转化为砜类，通过硅土或氧化铝吸附除掉。同样，苯甲硫醚、二苯硫化物、BT和4，6-DMDBT等也可以被定量的氧化成相应的砜类。对于柴油氧化反应后发现硫含量从193μg/g降低到低于5μg/g。类似，H.Lu(Lu H Y，Gao J B，Jiang Z X et al.Oxidative desulfurization ofdibenzothiophene with molecular oxygen using emulsion catalysis.Chem.Commun.2007，150-152.)也用O2作为氧化剂，醛为共氧剂，在杂多酸催化剂/表面活性剂(C18H37N(CH3)3/PV2Mo10O40)的共同作用下，通过乳液氧化，将DBT氧化成DBTO2，继而萃取分离。该氧化反应中实际对硫化物物进行氧化的物质是过氧辛酸，反应后残留部分会使油品的酸值增加。X.Ma等(Ma X，Zhou A，Song C.Anovel method for oxidative desulfurization of liquid hydrocarbon fuels based oncatalytic oxidation using molecular oxygen coupled with selective adsorption.Catalysis Today，2007，123：276-284.)用O2，以Fe(III)盐为催化剂，对模拟和实际航空燃油进行氧化反应，反应后用活性炭进行吸附过滤。在25℃和常压的温和条件下，反应时间2h，模型BTs全部转化为相应的亚砜和砜。硫化物的活性顺序为：2-甲基苯并噻吩(2-methylbenzothiophene，2-MBT)＞5-甲基苯并噻吩(5-methylbenzothiophene，5-MBT)＞BT＞＞DBT。此项研究对BTs效果较好，对于难以处理的DBT不理想，反应后仍有大部分DBT保留。然而该类反应需消耗大量醛等共氧剂，成本也比较高。
发明内容
本发明要解决的技术问题是提供一种仿生催化氧气氧化噻吩类化合物的方法。
本发明采用的技术方案是：选用具有通式(I)结构的金属酞菁或通式(II)结构的金属卟啉中的任何一种作为催化剂；通式(I)、(II)中，M为过渡金属，M＝Fe、Co或Mn；R1＝NO2、NH2、Cl、F、SOH3或H；R2＝NO2、NH2、Cl、F、SOH3或H；R3＝NO2、NH2、Cl、F、SOH3或H；R4＝NO2、NH2、Cl、F、SOH3或H；R5＝NO2、NH2、Cl、F、SOH3或H；催化剂的用量与反应体系总重量百分比的0.01％～1％，以C6～C20烃类化合物为溶剂，通入0.1MPa～5MPa的氧气，控制反应温度为80℃～180℃，反应时间为1h～12h。
本发明可以选用具有通式(I)结构的金属酞菁作催化剂，其中M＝Fe或Co，R1＝R3＝R4＝R5＝H，R2＝NO2；或者选用具有通式(II)结构的金属卟啉作催化剂，其中M＝Mn。
本发明的效果和益处是以金属酞菁类和金属卟啉类化合物为催化剂，可以实现在温和条件下高选择性地传递、活化氧分子，催化氧化有机物。此反应体系不需要加入共氧剂，不腐蚀油品且对环境友好，催化剂用量小，可回收利用，使成本降低，反应温度和反应压力不高，而且可实现油品的深度脱硫。
具体实施方式
以下结合技术方案详细叙述本发明的具体实施例。
实施例1
称取0.015g四-(邻氯苯基)锰卟啉(即通式(II)中R1＝Cl，R2＝R3＝R4＝R5＝H，M＝Mn)，15g含500μg/g二苯并噻吩的十氢化萘溶液，装入100ml高压釜中，通入氧气，压力为0.5MPa，油浴控温100℃，反应3h。经过减压抽滤实现催化剂和液相的分离。所得产品用气相色谱分析检测，得到二苯并噻吩的转化率为99.8％。反应产物由GC-MS认证。
实施例2
称取0.15g四-硝基铁酞菁(即通式(I)中R2＝NO2，R1＝R3＝R4＝R5＝H，M＝Fe)，15g含500μg/g二苯并噻吩的十氢化萘溶液，装入100ml高压釜中，通入氧气，压力为0.3MPa，油浴控温100℃，反应2h。处理步骤同实施例1。所得产品用气相色谱分析检测，得到二苯并噻吩的转化率为98.7％。反应产物由GC-MS认证。
实施例3
称取0.0015g十六氯酞菁铁(即通式(I)中R1＝R2＝R3＝R4＝R5＝Cl，M＝Fe)，15g含500μg/g二苯并噻吩的十氢化萘溶液装入100ml高压釜中，通入氧气，压力为0.5MPa，油浴控温80℃，反应5h。处理步骤同实施例1。所得产品用气相色谱分析检测，得到二苯并噻吩的转化率为32.7％。反应产物由GC-MS认证。
实施例4
称取0.075g四-硝基酞菁铁(即通式(I)中R2＝NO2，R1＝R3＝R4＝R5＝H，M＝Fe)，15g含500μg/g二苯并噻吩的十氢化萘溶液装入100ml高压釜中，通入氧气，压力为1.0MPa，油浴控温120℃，反应3h。处理步骤同实施例1。所得产品用气相色谱分析检测，得到二苯并噻吩的转化率为93.7％。反应产物由GC-MS认证。
实施例5
称取0.15g四-硝基铁酞菁(即通式(I)中R2＝NO2，M＝Fe)，15g含500μg/g4，6-二甲基二苯并噻吩的十氢化萘溶液，装入100ml高压釜中，通入氧气，压力为0.3MPa，油浴控温100℃，反应2h。处理步骤同实施例1。所得产品用气相色谱分析检测，得到二苯并噻吩的转化率为99.8％。反应产物由GC-MS认证。
Claims (3)
1.一种仿生催化氧气氧化噻吩类化合物的方法，其特征是选用具有通式(I)结构的金属酞菁或通式(II)结构的金属卟啉作为催化剂；
通式(I)中，M为过渡金属，M＝Fe、Co或Mn；R1＝NO2、NH2、Cl、F、SOH3或H；R2＝NO2、NH2、Cl、F、SOH3或H；R3＝NO2、NH2、Cl、F、SOH3或H；R4＝NO2、NH2、Cl、F、SOH3或H；R5＝NO2、NH2、Cl、F、SOH3或H；通式(II)中M＝Fe、Co或Mn；R1＝Cl或H；R2＝Cl或H；R3＝Cl或H；R4＝Cl或H；R5＝Cl或H；催化剂的用量与反应体系总重量的百分比为0.01％～1％，以C6～C20烃化合物为溶剂，通入0.1MPa～5MPa的氧气，反应温度为80℃～180℃，反应时间为1h～12h。
2.根据权利要求1所述的仿生催化氧气氧化噻吩类化合物的方法，其特征是具有通式(I)结构的金属酞菁作催化剂，其中M＝Fe或Co，R1＝R3＝R4＝R5＝H，R2＝NO2。
3.根据权利要求1所述的仿生催化氧气氧化噻吩类化合物的方法，其特征是具有通式(II)结构的金属卟啉作催化剂，其中M＝Mn。
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| CN103922903B (zh) * | 2014-04-01 | 2016-03-30 | 湖南大学 | 用共轭聚合金属卟啉催化氧化烷烃和环烷烃的方法 |
| CN104277870B (zh) * | 2014-10-16 | 2017-04-12 | 大连理工大学 | 一种用于氧化脱硫的苯并噻吩类化合物光解反应方法 |
| CN105419853B (zh) * | 2015-12-16 | 2017-07-28 | 中国科学院山西煤炭化学研究所 | 一种离子液体中燃油仿生氧化脱硫的方法 |
| CN106083867B (zh) * | 2016-07-16 | 2018-07-20 | 中国科学院山西煤炭化学研究所 | 一种改性金属卟啉的制备方法及其催化氧化脱硫的应用 |
| CN109503328B (zh) * | 2018-12-21 | 2020-09-29 | 大连理工大学 | 在常温下制备2-苯基-2-丙醇的方法 |
| CN110564447A (zh) * | 2019-07-26 | 2019-12-13 | 大连理工大学 | 二苯并噻吩类化合物催化氧化生成2-(2-羟基苯基)-苯亚磺酸及其盐的氧化脱硫方法 |
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