發(fā)布時(shí)間：2018-06-12 11:29

  本文選題：固體雜多酸 + 多孔載體��； 參考：《山東大學(xué)》2017年碩士論文

【摘要】：燃油中硫的燃燒能形成SO_x,是酸塵降(霧、雨、雪等)形成的主要因素,其中危害最大的當(dāng)屬酸雨,不僅腐蝕建筑物、樹木,惡化生態(tài)環(huán)境,而且會(huì)導(dǎo)致水質(zhì)酸化、土壤品質(zhì)、糧食大量減產(chǎn),給經(jīng)濟(jì)帶來巨大損失。近年來隨著人民環(huán)保理念逐漸加強(qiáng),世界各主要國家紛紛頒布法令限定油中的硫含量,2017年1月1日,我國開始全面實(shí)行國五排放標(biāo)準(zhǔn),當(dāng)務(wù)之急是如何高效脫除燃料油中的難溶含硫化物。氧化脫硫操作條件溫和,對(duì)噻吩等雜環(huán)類有機(jī)硫化物脫除效率高,且不需要消耗氫氣,是替代加氫脫硫最有希望的深度脫硫技術(shù)之一。Keggin結(jié)構(gòu)雜多酸具有脫硫活性高、酸性可調(diào)節(jié)、操作條件溫和等優(yōu)勢而得到廣泛應(yīng)用。鑒于雜多酸以上諸多優(yōu)勢,本文主要將活性組分固體雜多酸咪唑磷鎢酸負(fù)載在多孔載體上,并考察催化劑對(duì)油品脫硫效果。研究內(nèi)容如下:首先,采用共沉淀、機(jī)械混合、溶膠-凝膠法負(fù)載活性組分1-丁基-3甲基咪唑磷鎢酸鹽([BMIM]_3HPW)并考察了對(duì)DBT(二苯并噻吩)的脫硫性能。結(jié)果表明,最佳反應(yīng)條件是以共沉淀法負(fù)載的30wt%[BMIM]_3HPW/介孔SiO_2為催化劑,催化劑與油質(zhì)量比0.22%,O/S=6,75℃下攪拌反應(yīng)120min,反應(yīng)完成后水洗,DBT脫除率達(dá)到99%以上。對(duì)反應(yīng)后的催化劑進(jìn)行重復(fù)再利用,共沉淀及溶膠凝膠法負(fù)載的[BMIM]_3HPW/SiO_2催化劑具備良好的再生活性,且[BMIM]_3HPW/介孔 SiO_2 的穩(wěn)定性要高于[BMIM]_3HPW/SiO_2。其次,分別采用共沉淀和機(jī)械混合法將[Bmim]_3PW_(12)O_(40)負(fù)載在H_2O、HC_1、HNO_3、NaOH處理過的活性炭上,并探究上述催化劑對(duì)DBT的催化性能。實(shí)驗(yàn)結(jié)果表明,最佳反應(yīng)條件為以HNO_3-C作為載體,O:S=10:1,DMF與模擬油體積比 1:5,60℃下反應(yīng) 2h,[Bmim]_3PW_(12)O_(40)/HNO_3-C 負(fù)載量為 50wt%時(shí),DBT脫除率最高,達(dá)到了 86.95%,表明該催化劑催化活性高,工業(yè)應(yīng)用前景廣闊。再次,主要研究了[Bmim]_3PW_(12)O_(40)/SiO_2、[Bmim]_3PW_(12)O_(40)/C、[Bmim]_3PW_(12)O_(40)/SiO_2、[Bmim]_3PW_(12)O_(40)/C幾種催化劑對(duì)200#溶劑油的脫硫性能。通過以上研究得出,最佳反應(yīng)條件為O:S=14:1,DMF與200#體積比1:2,催化劑占油品質(zhì)量的0.263%,70 ℃下反應(yīng)2h,不加乙酸時(shí),以30wt%[Bmim]_3PW_(12)O_(40)/SiO_2作為催化劑,200#脫硫率可達(dá)到82.5%,加入乙酸后,以30wt%[Bmim]_3PW_(12)O_(40)/介孔SiO_2作為催化劑時(shí),200#脫硫率達(dá)到了 98.5%,可滿足工業(yè)生產(chǎn)需要,并證實(shí)了前言中猜測催化劑對(duì)于輕質(zhì)油品如200#溶劑油應(yīng)同樣具有高的催化活性的正確性。最后,鑒于工程碩士需要實(shí)習(xí)一年,總結(jié)了專業(yè)實(shí)踐一年的主要實(shí)習(xí)內(nèi)容,實(shí)習(xí)心得及初步具備的工程思想,為科學(xué)研究轉(zhuǎn)化成工業(yè)生產(chǎn)力做了鋪墊。
[Abstract]:The combustion of sulfur in fuel oil can form SOS x, which is the main factor of acid dust falling (fog, rain, snow, etc.). The most harmful factor is acid rain, which not only corrodes buildings, trees, and deteriorates the ecological environment, but also leads to water quality acidification and soil quality. A large reduction in grain production has brought huge losses to the economy. In recent years, as the people's concept of environmental protection has gradually strengthened, major countries in the world have promulgated laws to limit the sulfur content in oil. On January 1, 2017, China began to implement the national five emission standards. The urgent task is how to efficiently remove insoluble sulfides from fuel oil. The oxidation desulfurization has the advantages of mild operating conditions, high removal efficiency for thiophene and other heterocyclic organic sulfides, and no need for hydrogen consumption. It is one of the most promising deep desulfurization technologies for hydrodesulfurization. Keggin structure heteropoly acids have high desulfurization activity. Acid adjustable, mild operating conditions and other advantages and widely used. In view of the advantages of heteropoly acids, solid heteropoly acid imidazophos tungstic acid was supported on porous carrier and the desulfurization effect of catalyst on oil was investigated. The main contents are as follows: firstly, coprecipitation, mechanical mixing and sol-gel method were used to support the active component 1- Ding Ji-3 methyl imidazophos tungstate ([BMIM] 3H PWC) and the desulfurization performance of p-DBT (dibenzothiophene) was investigated. The results show that the optimum reaction conditions are as follows: 30wt% [BMIM] / mesoporous SiO-2 as catalyst supported by coprecipitation method, and the ratio of catalyst to oil is 0.22o / Sn 675 鈩，

本文編號(hào)：2009513