本文關(guān)鍵詞：改性HMS分子篩的制備及催化氧化脫硫性能研究　出處：《青島科技大學(xué)》2017年碩士論文　論文類(lèi)型：學(xué)位論文

  更多相關(guān)文章： HMS分子篩 改性 汽油 噻吩 氧化脫硫

【摘要】：環(huán)保問(wèn)題是當(dāng)今社會(huì)關(guān)注的熱點(diǎn)問(wèn)題之一,汽油中硫化物燃燒后會(huì)造成嚴(yán)重的大氣污染,降低汽油中的硫含量,實(shí)現(xiàn)油品的深度脫硫刻不容緩。采用加氫脫硫技術(shù)深度脫除噻吩類(lèi)大分子硫化物必須在更加嚴(yán)苛的操作條件下進(jìn)行,生產(chǎn)成本也隨之提高。氧化脫硫是一種具有廣闊應(yīng)用前景的深度脫硫技術(shù),可以作為加氫脫硫的后續(xù)工藝來(lái)輔助脫硫。分子篩因其比表面積大、孔徑大小可調(diào)等優(yōu)勢(shì)成為一種被重點(diǎn)研究的氧化脫硫催化劑。本文以純硅HMS分子篩為研究對(duì)象,結(jié)合引入金屬雜原子、表面有機(jī)基團(tuán)功能化以及負(fù)載活性組分等方式對(duì)其進(jìn)行改性,制備了一系列氧化脫硫催化劑,采用XRD、FT-TR、SEM、TEM、N2吸附脫附、UV-Vis等手段對(duì)催化劑樣品進(jìn)行表征分析,并以模型油中噻吩的氧化脫除為探針?lè)磻?yīng)對(duì)催化劑的催化氧化脫硫性能進(jìn)行研究。主要內(nèi)容如下:(1)采用液相回流浸漬法對(duì)HMS分子篩進(jìn)行表面氨基改性,以改性后的分子篩為載體、磷鎢酸為活性組分制備了HPW-NH_2-HMS催化劑。表征結(jié)果顯示,催化劑保留了HMS分子篩的介孔結(jié)構(gòu)和磷鎢酸的Keggin結(jié)構(gòu)。將催化劑用于氧化脫硫反應(yīng),考察不同條件對(duì)催化劑氧化脫硫性能的影響。結(jié)果表明,在反應(yīng)溫度為60℃、n(H2O2)/n(S)=8、25%HPW-NH_2-HMS催化劑用量0.1 g·(10 mL)~(-1)、反應(yīng)時(shí)間120 min的條件下,噻吩的氧化脫除率可達(dá)93.89%。氧化脫硫反應(yīng)動(dòng)力學(xué)研究發(fā)現(xiàn),在以噻吩/正辛烷為模型油、30%(wt)雙氧水為氧化劑、25%HPW-NH_2-HMS為催化劑的反應(yīng)體系中,噻吩的氧化反應(yīng)為一級(jí)反應(yīng),反應(yīng)的活化能為31.9 KJ/mol。(2)采用超聲浸漬法對(duì)原位合成的Ti-HMS分子篩進(jìn)行負(fù)載金屬改性,制備了Fe/Ti-HMS、Cu/Ti-HMS和Zn/Ti-HMS催化劑。對(duì)催化劑的結(jié)構(gòu)和形貌進(jìn)行表征,結(jié)果顯示,Ti-HMS分子篩具有介孔孔道結(jié)構(gòu),金屬組分均勻的分散在分子篩的表面。氧化脫硫?qū)嶒?yàn)結(jié)果表明,金屬組分的存在可以有效地提高催化劑的催化活性,負(fù)載金屬組分的催化劑催化活性由大到小依次為Zn/Ti-HMS㧐Cu/Ti-HMS㧐Fe/Ti-HMS。(3)采用液相回流浸漬法對(duì)原位合成的Fe-HMS分子篩進(jìn)行表面氨基改性,通過(guò)表面接枝的氨基基團(tuán)來(lái)絡(luò)合固載Cu~(2+),制備了Cu~(2+)/Fe-HMS類(lèi)芬頓催化劑。Fe元素成功地進(jìn)入分子篩的骨架中,表面接枝氨基和絡(luò)合固載銅離子后催化劑的比表面積、孔體積和孔徑等參數(shù)均有所降低。將催化劑用于氧化脫硫反應(yīng),結(jié)果表明表面銅離子和骨架鐵表現(xiàn)出協(xié)同作用,銅離子對(duì)噻吩分子的選擇吸附性使其被優(yōu)先吸附到催化劑的表面,骨架鐵催化過(guò)氧化氫生成羥基自由基,兩種反應(yīng)物在催化劑表面不斷的積累,促進(jìn)了氧化反應(yīng)的進(jìn)行。
[Abstract]:Environmental protection is one of the hot issues in today's society. The combustion of sulfide in gasoline will cause serious air pollution and reduce sulfur content in gasoline, so it is urgent to achieve deep desulfurization of oil. The use of hydrodesulfurization technology to remove thiophene macromolecular sulfides must be carried out under more stringent operating conditions, and the cost of production is also increased. Oxidative desulfurization is a kind of deep desulfurization technology with broad application prospects, which can be used as a follow-up process for hydrodesulfurization to assist the desulfurization. Molecular sieves have become one of the most important catalysts for oxidative desulfurization because of their large specific surface area and adjustable pore size. The YISHION silicon HMS molecular sieve as the research object, modified by the combination of introducing metal atoms, surface organic functional groups and active component load, a series of oxidation desulfurization catalyst prepared by XRD, FT-TR, SEM, TEM, N2 adsorption desorption, UV-Vis catalyst samples were characterized by means of analysis and Study on properties of catalytic oxidation desulfurization catalyst to probe reaction to oxidative desulfurization of thiophene as model oil. The main contents are as follows: (1) liquid phase reflux impregnation method was used to modify the surface of HMS zeolite, and the HPW-NH_2-HMS catalyst was prepared by using modified molecular sieve as carrier and phosphotungstic acid as active component. The characterization results showed that the catalyst retained the mesoporous structure of HMS molecular sieve and the Keggin structure of phosphotungstic acid. The effect of different conditions on the oxidation desulfurization performance of the catalyst was investigated by using the catalyst for oxidation desulfurization. The results showed that the oxidation removal rate of thiophene could reach 93.89% at the reaction temperature of 60, n (H2O2) /n (S) =8, 25%HPW-NH_2-HMS catalyst dosage 0.1 g ~ (10 mL) ~ (-1) and reaction time 120 min. Kinetic studies on oxidative desulfurization showed that thiophene oxidation reaction was first order reaction in the reaction system of thiophene / octane as model oil, 30% (WT) hydrogen peroxide as oxidant and 25%HPW-NH_2-HMS as catalyst, and the activation energy of reaction was 31.9 KJ/mol. (2) Ti-HMS molecular sieves in situ synthesized by ultrasonic impregnation are modified by metal loading, and the catalysts of Fe/Ti-HMS, Cu/Ti-HMS and Zn/Ti-HMS are prepared. The structure and morphology of the catalyst were characterized. The results showed that the Ti-HMS molecular sieve had mesoporous pore structure and the metal component was dispersed evenly on the surface of the molecular sieve. The results of oxidative desulfurization experiments show that the presence of metal components can effectively improve the catalytic activity of the catalysts. The catalytic activity of supported metal components is Zn/Ti-HMS to Cu/Ti-HMS Fe/Ti-HMS from large to small. (3) liquid phase reflux impregnation method was used to modify the surface of Fe-HMS zeolite synthesized in situ. The Cu~ (2+) /Fe-HMS Fenton like catalyst was prepared by complexing Cu~ (2+) with surface grafting amino group. The Fe element successfully entered the skeleton of the zeolite. The surface area, pore volume and pore size of the catalyst decreased after grafting with amino groups and complexing with copper ions. The catalyst for oxidative desulfurization reaction, the results showed that the surface of copper ion and iron skeleton showed synergistic effect of selective adsorption of copper ions on the thiophene molecules to be preferentially adsorbed to the surface of the catalyst skeleton iron catalyzed hydrogen peroxide generation of hydroxyl radicals, two kinds of reactants on the catalyst surface and the accumulation promoted oxidation reaction the.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：TE624.9

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 陳煥章,李永丹,趙地順,王春芳;汽油和柴油氧化脫硫技術(shù)進(jìn)展[J];化工進(jìn)展;2004年09期

2 郭永剛;李元春;;柴油氧化脫硫技術(shù)的研究進(jìn)展[J];當(dāng)代石油石化;2006年03期

3 劉淑芝;孫蘭蘭;張曉麗;王寶輝;崔寶臣;;柴油氧化脫硫技術(shù)研究進(jìn)展[J];化工進(jìn)展;2007年02期

4 宗立遠(yuǎn);;柴油氧化脫硫技術(shù)的研究進(jìn)展[J];河北工業(yè)科技;2007年03期

5 李林;唐曉東;鄒雯p，

本文編號(hào)：1342829