【摘要】：為了減緩燃料油給環(huán)境造成的污染,各國政府對燃料油中硫含量進(jìn)行嚴(yán)格的限制,燃料油中以噻吩類化合物及其衍生物形式存在的有機(jī)硫化物在加氫脫硫工藝中比較難以脫除,致使生產(chǎn)成本增加。氧化脫硫工藝條件緩和,脫硫成本低,關(guān)鍵是開發(fā)既能夠深度脫硫又高效經(jīng)濟(jì)的催化劑。本文將過渡金屬Fe/V摻雜到HMS和MCM-41中,制得負(fù)載型Fe-V-HMS和V-MCM-41催化劑,研究了兩種催化劑對DBT的氧化脫除效果,并通過NH3-TPD、XRD、H2-TPR、FT-IR以及SEM等表征手段對催化劑進(jìn)行分析,考察催化劑活性組分的負(fù)載方法、負(fù)載量、溶液pH值以及焙燒溫度對催化性能影響;研究了氧化脫硫反應(yīng)動(dòng)力學(xué);通過正交實(shí)驗(yàn)確定了氧化脫硫反應(yīng)最佳工藝條件。研究表明,采用一步合成法制備的Fe-V-HMS催化劑氧化脫硫性能優(yōu)于等體積浸漬法,在合成溶液pH值為10、焙燒溫度為550℃、Si/(Fe+V)摩爾比為14.8、V/Fe摩爾比為1:2條件下制備的Fe-V-HMS催化劑脫硫效果最好;在反應(yīng)溫度60℃,反應(yīng)時(shí)間45min,O/S摩爾比為4.5,催化劑用量8g/L(oil)的條件下,脫硫率可達(dá)99%以上;DBT氧化生成的DBTO2吸附在Fe-V-HMS催化劑表面,Fe-V-HMS在氧化脫硫反應(yīng)過程中同時(shí)具有催化和吸附作用;Fe-V-HMS催化氧化脫硫反應(yīng)屬于一級反應(yīng),其表觀活化能為Ea=38.79kJ/mol、指前因子k0=1.33×105。采用水熱法制得的V-MCM-41催化劑在Si/V(摩爾比)=50、pH為10.5條件下,V-MCM-41催化劑脫硫效果最好,V-MCM-41催化劑經(jīng)過正交試驗(yàn)的優(yōu)化,在O/S為4.5,反應(yīng)溫度70℃,催化劑用量3g/L(oil),反應(yīng)時(shí)間60min的條件下催化劑的脫硫率達(dá)到98%以上。以V-MCM-41為催化劑的氧化脫硫反應(yīng)屬于一級反應(yīng),其表觀活化能為Ea=52.48kJ/mol、指前因子k0=8.04×106min-1。
文內(nèi)圖片：
圖片說明：HMS(a、b)和：Fe-V-HMS(c、d)的掃描電鏡（SEM）圖譜
[Abstract]:In order to slow down the environmental pollution caused by fuel oil, governments of various countries strictly limit the sulfur content in fuel oil. The organic sulfides in the form of thiophene compounds and their derivatives in fuel oil are difficult to be removed in hydrodesulfurization process, which leads to the increase of production cost. The process conditions of oxidative desulfurization are relaxed and the cost of desulphurization is low. the key is to develop catalysts which can both deep desulphurization and high efficiency and economy. In this paper, supported Fe-V-HMS and V-MCM-41 catalysts were prepared by doping transition metal Fe/V into HMS and MCM-41. The oxidative removal effects of the two catalysts on DBT were studied. The catalysts were characterized by NH3-TPD,XRD,H2-TPR,FT-IR and SEM. The effects of loading method, loading amount, pH value of solution and calcination temperature on the catalytic performance were investigated. The kinetics of oxidative desulfurization was studied, and the optimum technological conditions of oxidative desulfurization were determined by orthogonal experiment. The results show that the oxidative desulfurization performance of Fe-V-HMS catalyst prepared by one-step synthesis method is better than that of equal volume impregnation method. When the pH value of synthesis solution is 10, the calcination temperature is 550 鈩，

本文編號：2510139