發(fā)布時(shí)間：2018-11-06 19:21

【摘要】：隨著全球環(huán)境污染加劇,世界各國(guó)相繼實(shí)施了一系列更為嚴(yán)格的環(huán)境保護(hù)法規(guī),尤其是對(duì)油品中硫化物含量的要求日益嚴(yán)格。油品中的硫化物經(jīng)過(guò)燃燒以后產(chǎn)生的SOx會(huì)導(dǎo)致酸雨、溫室效應(yīng)和空氣污染,帶來(lái)嚴(yán)重的環(huán)境問(wèn)題,所以有效地脫除油品中的硫化物勢(shì)在必行。催化加氫方法可以有效除去油品中的硫醇、硫醚和二硫化物,但由于噻吩及其衍生物空間位阻效應(yīng),傳統(tǒng)催化加氫方法對(duì)其脫除效果不佳。鑒于離子液體和金屬離子都能與噻吩類硫化物發(fā)生相互作用,可以在較溫和條件下表現(xiàn)出較理想的脫硫效果,所以本文以SBA-15為載體,將離子液體和金屬離子共同負(fù)載于SBA-15上,在“雙活性中心”的作用下進(jìn)行油品的脫硫,這為吸附脫硫劑的設(shè)計(jì)與合成供了一個(gè)新的思路。本文首先合成離子液體1-乙氧基硅丙基-3-甲基咪唑氯鹽(IL),然后分別用溶膠凝膠法和分步法,將離子液體和金屬離子共同負(fù)載于介孔材料SBA-15上,合成金屬基離子液體負(fù)載化的SBA-15。將合成的一系列樣品使用紅外光譜(IR)、X-射線衍射(XRD)、N2吸附脫附、元素分析、掃描電鏡(SEM)、能譜分析(EDS)、X-射線熒光(XRF)、原子吸收(AAS)進(jìn)行表征,結(jié)果顯示離子液體和金屬離子可以共同負(fù)載到SBA-15上,并且在一定的比例范圍內(nèi),負(fù)載化的SBA-15仍保持二維六方介孔結(jié)構(gòu)。以溶膠凝膠法合成的一系列負(fù)載化SBA-15為吸附劑,對(duì)模擬油品進(jìn)行靜態(tài)脫硫,篩選最佳吸附劑。實(shí)驗(yàn)結(jié)果表明,3.2系列的負(fù)載化SBA-15對(duì)噻吩類硫化物脫除效率最高;對(duì)于不同硫化物的脫除效果為:DBTBTTS2-MTS;對(duì)于每種吸附劑而言,Zn-IL-SBA-15IL-SBA-15SBA-15。用3.2系列的吸附劑對(duì)含不同硫化物的模擬油品進(jìn)行靜態(tài)和動(dòng)態(tài)脫硫的實(shí)驗(yàn)考察。實(shí)驗(yàn)結(jié)果表明,在靜態(tài)脫硫?qū)嶒?yàn)中,時(shí)間、溫度、劑油比對(duì)脫硫效率均有一定的影響;動(dòng)態(tài)脫硫?qū)嶒?yàn)條件下,Zn-3.2IL-SBA-15對(duì)2-甲基噻吩、噻吩、苯并噻吩和二苯并噻吩的穿透時(shí)間分別為50min、110min、140min、160min,穿透硫容分別為0.362%、1.667%、2.070%、3.687%。回收實(shí)驗(yàn)顯示該吸附劑的回收次數(shù)不高,有待進(jìn)一步改進(jìn)。以溶膠凝膠法合成的Zn-3.2IL-SBA-15為吸附劑,進(jìn)行脫硫的吸附平衡實(shí)驗(yàn),探究其熱力學(xué)過(guò)程。Zn-3.2IL-SBA-15對(duì)噻吩、苯并噻吩的吸附等溫線用Henry、Langmuir、Freundlich三種方程進(jìn)行擬合,實(shí)驗(yàn)數(shù)據(jù)對(duì)Langmuir等溫方程的擬合效果最好,說(shuō)明噻吩和苯并噻吩傾向于單分子層吸附。熱力學(xué)計(jì)算結(jié)果表明,吸附劑Zn-3.2IL-SBA-15對(duì)噻吩和苯并噻吩的吸附過(guò)程是自發(fā)的、體系混亂度降低、放熱的物理過(guò)程,噻吩和苯并噻吩分子都屬于平行吸附。Zn-3.2IL-SBA-15和硫化物之間存在的π絡(luò)合、π-π絡(luò)合和靜電吸引力是該吸附劑脫除噻吩類硫化物的內(nèi)在機(jī)理。采用分步法合成金屬基離子液體負(fù)載化SBA-15,以提高兩種活性中心的負(fù)載率。實(shí)驗(yàn)結(jié)果表明,采用分步法雖然可以提高金屬離子或者離子液體的負(fù)載率,但是脫硫效果提升不高,且易造成SBA-15介孔結(jié)構(gòu)的破壞,其合適的比例,有待進(jìn)一步探究。
[Abstract]:With the increase of global environmental pollution, the countries of the world have successively implemented a series of more stringent environmental protection regulations, especially the demand for sulfide content in oil products. The SOx produced by the sulfide in the oil can lead to acid rain, greenhouse effect and air pollution, which brings serious environmental problems, so it is imperative to remove the sulfide in the oil effectively. the catalytic hydrogenation method can effectively remove the mercaptans, the thioethers and the disulfides in the oil products, but the traditional catalytic hydrogenation method is not good for the removal effect due to the steric hindrance effect of the alicyclic and the derivatives thereof. in that light of the interaction of the ionic liquid and the metal ion with the sulfur-like sulfide, the ideal desulfurization effect can be exhibited under mild conditions, so that the SBA-15 is used as a carrier, and the ionic liquid and the metal ion are co-loaded on the SBA-15, The desulfurization of oil is carried out under the action of the 鈥渄ouble active center鈥，

本文編號(hào)：2315228