柴油绿色催化氧化脱硫的研究

发布时间：2018-10-10 09:59

【摘要】：燃油超深度脱硫已经成为世界范围内急需的一种环保技术。作为交通运输的主要燃料,柴油和汽油中的硫化物也是导致酸雨、雾霾和腐蚀的主要原因。氧化脱硫就包括了将含硫化合物氧化为相应的砜类物质并通过萃取或吸附将其除去的过程。在温和条件下使用一种新的氧化体系对模型柴油中的含硫化合物(BT,DBT,4,6-DMDBT)进行氧化脱硫。此体系,将Anderson型催化剂(C18H37)2N(CH3)2]3Co(OH)_6Mo_6O_(18)溶解在离子液体[Bpy]BF4中,对模型柴油进行催化氧化脱硫。以氧气为氧化剂。体系的循环性能相较于以前的报道有很大提升且对DBT脱除率可达100%。此体系可被循环五次且活性没有明显下降。此外,我们还根据一种新型的安德森型催化剂进行了催化氧化脱硫研究。新型的Anderson型杂多酸{[(CH3)3N(CH2)2OH]2}[H0.2K0.2Na2.6(H2O)6][IMo6O24]催化剂进是通过低共熔物进行合成的,而后对其进行XRD粉末衍射,傅里叶变换红外光谱(FTIR),热重分析使,循环伏安,ICP-AES表征。将此种杂多酸催化剂溶解到离子液体中对模型柴油进行催化氧化脱硫。这个催化体系包括过作为氧化剂的过氧化氢和1-辛基-3-甲基咪唑四氟硼酸盐离子液体,其表现出了可以在60℃下60分钟对DBT达到100%脱除率的高活性。此体系对柴油中几种常见硫化物脱硫活性顺序为DBT4,6-DMDBTBT。此脱硫体系表现出了良好的稳定性,其脱硫活性在20次循环实验中没有明显下降。另外,我们研究了一种以草酸和四丁基氯化铵以1/2摩尔比合成的草酸基低共熔剂催化模型柴油脱除DBT的过程。合成了此种草酸基低共熔剂并用IR,XRD,CV,EPR等方法对其进行表征并探究了其反应机理。作为催化剂和萃取剂,低共熔剂表现出了良好的活性。为了获得理想的低共熔剂,对低共熔剂的合成方法,氢键受体进行了一些列筛选,并确定了其合成的最优摩尔比。对反应过程中温度,氧硫比等影响进行了研究。这种草酸基低共熔剂在60℃条件下,180分钟可以达到对模型柴油中DBT的98%脱硫率。
[Abstract]:Ultra-deep desulfurization of fuel has become an urgent environmental protection technology all over the world. As the main fuel for transportation, sulfides in diesel and gasoline are also the main causes of acid rain, haze and corrosion. Oxidative desulfurization involves the oxidation of sulfur compounds to corresponding sulfones and their removal by extraction or adsorption. Sulfur compounds (BT,DBT,4,6-DMDBT) in model diesel oil were oxidized by a new oxidation system under mild conditions. In this system, the Anderson catalyst (C18H37) 2N (CH3) 2] 3Co (OH) was dissolved in the ionic liquid [Bpy] BF4, and the model diesel oil was desulfurized by catalytic oxidation. Oxygen is used as oxidant. Compared with previous reports, the cycle performance of the system has been greatly improved and the removal rate of DBT can be up to 100kW. The system can be recirculated five times and the activity does not decrease significantly. In addition, a new type of Anderson catalyst was used to study the catalytic oxidation desulfurization. A new type of Anderson heteropoly acid {[(CH3) 3N (CH2) 2OH] 2} [H0.2K0.2Na2.6 (H2O) 6] [IMo6O24] was synthesized by eutectic material, then was diffracted by XRD powder, characterized by Fourier transform infrared (FTIR) (FTIR), thermogravimetry, cyclic voltammetry ICP-AES. The catalytic oxidation desulfurization of model diesel oil was carried out by dissolving the heteropoly acid catalyst into ionic liquids. The catalytic system consists of hydrogen peroxide and 1-octyl -3-methylimidazolium tetrafluoroborate ionic liquids, which exhibit a high activity of 100% removal of DBT at 60 鈩，

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