【摘要】：氧化脫硫(Oxidative desulfurization ODS)是一種有效的石油脫硫工藝。但是該工藝中所需的催化劑存在制備耗能大,水溶性氧化劑無法與硫化物完全反應(yīng)的缺點。本研究將采用浸漬法制備新型催化劑,添加溶油性氧化劑,解決了氧化脫硫中的兩大缺陷,同時對催化劑制備條件、表征、反應(yīng)條件、重復(fù)使用性、反應(yīng)動力學(xué)、機理等方面進行詳細(xì)研究。該催化劑能將硫含量從400 mg?kg-1降到3.52mg?kg-1,且能重復(fù)使用7次。本研究采用浸漬法將鎢負(fù)載在丙烯酸系弱酸性陽離子交換樹脂D152上,制成了催化劑W/D152。實驗研究了浸漬鎢溶液p H值、溫度、濃度等制備條件對催化氧化去除二苯并噻吩(DBT)活性的影響,并確定了催化劑最佳制備條件。運用紅外光譜(FTIR)和環(huán)境電鏡掃描(SEM)對W/D152的微觀面貌進行了觀察和分析。結(jié)果表明,在p H值為2.5,溫度為30℃,質(zhì)量體積濃度為2.5%的含鎢溶液條件下制備的催化劑脫硫效果最佳;初始溶液含硫濃度為400 mg?kg-1,最高去除率達到99.1%,處理后的樣品含硫量約3.52 mg?kg-1,達到了總含硫量要求小于10 mg?kg-1的歐五標(biāo)準(zhǔn)。對新制備的催化劑進行表征。采用環(huán)境電鏡掃描(SEM)和紅外。催化劑表征結(jié)果表明,鎢成功負(fù)載在樹脂上,并形成一層薄層。以二苯并噻吩為目標(biāo)處理物,以過氧化環(huán)己酮(CYHPO)為氧化劑分別對反應(yīng)溫度、反應(yīng)時間、氧化劑用量、催化劑用量四個反應(yīng)因素進行考察,選擇最佳催化氧化條件。實驗結(jié)果表明:在反應(yīng)溫度為100℃、反應(yīng)時間為40min,模擬油與催化劑的質(zhì)量比為100,氧化劑與含硫量摩爾比為2.5時,反應(yīng)條件最佳。在最佳反應(yīng)條件下,將初始含硫量為400 mg?kg-1減低到含硫量約3.52 mg?kg-1,最高去除率達到99.1%。催化劑的重復(fù)使用次數(shù)是衡量一種催化劑可靠性的一個重要指標(biāo)。在相同反應(yīng)條件下,重復(fù)使用該催化劑,實驗結(jié)果表明:該催化劑循環(huán)使用7次后,仍可達到歐五標(biāo)準(zhǔn),具備良好的重復(fù)使用效能。對本實驗的反應(yīng)動力學(xué)進行模擬,模擬結(jié)果表明:該催化劑催化氧化二苯并噻吩的反應(yīng)符合一級動力學(xué)模型,速率常數(shù)為0.1091 min-1,對比沒添加催化劑的反應(yīng)動力學(xué),反應(yīng)時間達到40 min后,脫硫率只有45.3%。此外,本催化氧化的反應(yīng)機理也進行了研究。采用真實汽油對新制備的催化劑進行脫硫效果驗證。實驗結(jié)果表明:該催化劑在于模擬實驗相同反應(yīng)條件下,脫硫率為97%,具備一定的工業(yè)使用價值。
[Abstract]:Oxidative desulfurization (Oxidative desulfurization ODS) is an effective process for petroleum desulfurization. However, the catalyst needed in this process has the disadvantages of high energy consumption and water soluble oxidants can not completely react with sulfides. In this study, a new type of catalyst was prepared by impregnation, and dissolved oxidant was added to solve the two major defects in oxidative desulfurization. At the same time, the preparation conditions, characterization, reaction conditions, reusability and kinetics of the catalyst were studied. The mechanism is studied in detail. The catalyst can reduce sulfur content from 400 mg?kg-1 to 3.52 mg / kg -1 and can be reused for 7 times. In this paper, W / D 152 catalyst was prepared by impregnating tungsten onto acrylic acid weak acid cation exchange resin D152. The effects of preparation conditions such as pH value, temperature and concentration of impregnated tungsten solution on the catalytic oxidation of dibenzothiophene (DBT) were studied and the optimum preparation conditions were determined. The microstructure of W/D152 was observed and analyzed by infrared (FTIR) and scanning (SEM). The results showed that the desulfurization effect of the catalyst was the best under the conditions of pH 2.5, temperature 30 鈩，

本文編號：2218532