玛瑞常压渣油反应前后重质组分含硫结构变化研究
发布时间：2018-12-07 16:39
【摘要】：在渣油加工过程中,渣油分子中不同含硫官能团由于其化学结构和周围环境不同,在反应过程中转化行为不同,因此,研究不同反应前后渣油中含硫结构的形态和含量变化,可以指导渣油加工工艺优化和硫元素的有效脱除。为了确证沥青质中+6价硫的形态,利用浓盐酸或者乙醇萃取的方法对玛瑞常压渣油临氮反应产物、加氢反应产物和沙轻减渣加氢反应产物进行处理,采用氯化钡滴定的方法检验洗出的溶液中是否含有硫酸盐,结果表明玛瑞常渣临氮反应的胶质和沥青质中均观测不到硫酸盐,即所研究沥青质中+6价硫为有机硫。以玛瑞常压渣油(MRAR)为原料,在395℃下进行临氮热反应,反应时间分别为30 min、60 min、90 min、120 min、150 min,对不同反应时间的产物进行SARA四组分分离,分别测定组分偶极矩以表征极性,利用1H-NMR表征各组分分子平均结构参数、分析分子的缔合性质,利用X射线吸收近边结构谱(XANES)分析胶质和沥青质中不同含硫结构的形态和相对含量,分析结果表明,胶质和沥青质中含硫结构的主要存在形式为还原态的噻吩,此外,以中间态的亚砜、砜和氧化态的硫酸酯形式存在;含硫结构的形态和含量与重质组分的极性、缔合性关系不大;对重质组分的极性和体系的胶体稳定性进行研究,结果表明,胶质和沥青质的偶极矩差异越大,二者的胶溶能力越差,体系的胶体稳定性也越差;此外,体系中四组分含量和重质组分的分子结构参数也对胶体稳定性有影响。对玛瑞常压渣油和沙轻减压渣油加氢反应样品进行分析,加氢后样品胶质的缩合度增大,不同渣油样品沥青质的变化情况不一致。加氢反应样品中各含硫结构的相对含量略有变化,绝对含量均减小,表明组分发生了加氢脱硫反应,但脱硫选择性不明显。玛瑞常渣临氮反应与加氢反应中各含硫结构的变化规律明显不一致,表明渣油临氮反应和加氢反应中虽然都发生了脱硫反应,但含硫结构发生的反应不同。
[Abstract]:In the process of residue processing, different sulfur functional groups in residue molecules have different transformation behaviors in the reaction process because of their different chemical structure and surrounding environment. Therefore, the morphology and content changes of sulfur containing structures in residue before and after different reactions are studied. It can guide the optimization of residue processing process and the effective removal of sulfur elements. In order to confirm the form of hexavalent sulfur in asphaltene, concentrated hydrochloric acid or ethanol extraction was used to treat the products of atmospheric residue nitrogen reaction, hydrogenation reaction products and sand light slags hydrogenation products. The method of barium chloride titration was used to test whether there was sulfate in the washed solution. The results showed that sulfate was not observed in the colloid and asphaltene of the reaction of Mari constant residue, that is, the hexavalent sulfur in the asphaltene was organic sulfur. Under the condition of 395 鈩，
本文编号：2367475
[Abstract]:In the process of residue processing, different sulfur functional groups in residue molecules have different transformation behaviors in the reaction process because of their different chemical structure and surrounding environment. Therefore, the morphology and content changes of sulfur containing structures in residue before and after different reactions are studied. It can guide the optimization of residue processing process and the effective removal of sulfur elements. In order to confirm the form of hexavalent sulfur in asphaltene, concentrated hydrochloric acid or ethanol extraction was used to treat the products of atmospheric residue nitrogen reaction, hydrogenation reaction products and sand light slags hydrogenation products. The method of barium chloride titration was used to test whether there was sulfate in the washed solution. The results showed that sulfate was not observed in the colloid and asphaltene of the reaction of Mari constant residue, that is, the hexavalent sulfur in the asphaltene was organic sulfur. Under the condition of 395 鈩，
本文编号：2367475
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