【摘要】：在渣油加工過程中,渣油分子中不同含硫官能團(tuán)由于其化學(xué)結(jié)構(gòu)和周圍環(huán)境不同,在反應(yīng)過程中轉(zhuǎn)化行為不同,因此,研究不同反應(yīng)前后渣油中含硫結(jié)構(gòu)的形態(tài)和含量變化,可以指導(dǎo)渣油加工工藝優(yōu)化和硫元素的有效脫除。為了確證瀝青質(zhì)中+6價(jià)硫的形態(tài),利用濃鹽酸或者乙醇萃取的方法對(duì)瑪瑞常壓渣油臨氮反應(yīng)產(chǎn)物、加氫反應(yīng)產(chǎn)物和沙輕減渣加氫反應(yīng)產(chǎn)物進(jìn)行處理,采用氯化鋇滴定的方法檢驗(yàn)洗出的溶液中是否含有硫酸鹽,結(jié)果表明瑪瑞常渣臨氮反應(yīng)的膠質(zhì)和瀝青質(zhì)中均觀測(cè)不到硫酸鹽,即所研究瀝青質(zhì)中+6價(jià)硫?yàn)橛袡C(jī)硫。以瑪瑞常壓渣油(MRAR)為原料,在395℃下進(jìn)行臨氮熱反應(yīng),反應(yīng)時(shí)間分別為30 min、60 min、90 min、120 min、150 min,對(duì)不同反應(yīng)時(shí)間的產(chǎn)物進(jìn)行SARA四組分分離,分別測(cè)定組分偶極矩以表征極性,利用1H-NMR表征各組分分子平均結(jié)構(gòu)參數(shù)、分析分子的締合性質(zhì),利用X射線吸收近邊結(jié)構(gòu)譜(XANES)分析膠質(zhì)和瀝青質(zhì)中不同含硫結(jié)構(gòu)的形態(tài)和相對(duì)含量,分析結(jié)果表明,膠質(zhì)和瀝青質(zhì)中含硫結(jié)構(gòu)的主要存在形式為還原態(tài)的噻吩,此外,以中間態(tài)的亞砜、砜和氧化態(tài)的硫酸酯形式存在;含硫結(jié)構(gòu)的形態(tài)和含量與重質(zhì)組分的極性、締合性關(guān)系不大;對(duì)重質(zhì)組分的極性和體系的膠體穩(wěn)定性進(jìn)行研究,結(jié)果表明,膠質(zhì)和瀝青質(zhì)的偶極矩差異越大,二者的膠溶能力越差,體系的膠體穩(wěn)定性也越差;此外,體系中四組分含量和重質(zhì)組分的分子結(jié)構(gòu)參數(shù)也對(duì)膠體穩(wěn)定性有影響。對(duì)瑪瑞常壓渣油和沙輕減壓渣油加氫反應(yīng)樣品進(jìn)行分析,加氫后樣品膠質(zhì)的縮合度增大,不同渣油樣品瀝青質(zhì)的變化情況不一致。加氫反應(yīng)樣品中各含硫結(jié)構(gòu)的相對(duì)含量略有變化,絕對(duì)含量均減小,表明組分發(fā)生了加氫脫硫反應(yīng),但脫硫選擇性不明顯�，斎鸪ＴR氮反應(yīng)與加氫反應(yīng)中各含硫結(jié)構(gòu)的變化規(guī)律明顯不一致,表明渣油臨氮反應(yīng)和加氫反應(yīng)中雖然都發(fā)生了脫硫反應(yīng),但含硫結(jié)構(gòu)發(fā)生的反應(yīng)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，

本文編號(hào)：2367475