本文關(guān)鍵詞： 氧化脫硫 多相催化 POM/h-BN催化劑 h-BN H_2O_2　出處：《江蘇大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：近年來,隨著油品劣質(zhì)化的加重,燃油的含硫量也隨之增加。燃油燃燒產(chǎn)生的SOx會(huì)造成嚴(yán)重的環(huán)境污染,因此硫化物的脫除日益受到重視。燃油中的硫醇和硫醚可用簡單的物理或化學(xué)方法脫除,而噻吩類硫很難用傳統(tǒng)的加氫脫硫技術(shù)脫除。因此多種新型的脫硫方法應(yīng)運(yùn)而生,例如生物脫硫、吸附脫硫、萃取脫硫和氧化脫硫等。其中,氧化脫硫(ODS)因溫和的反應(yīng)條件和對(duì)芳香族硫化物的高活性已成為一種生產(chǎn)超低硫燃油的技術(shù)。ODS技術(shù)的關(guān)鍵是尋找一種高效穩(wěn)定的催化劑。本論文設(shè)計(jì)合成了一系列氮化硼負(fù)載雜多酸催化劑,并將其用于燃油深度脫硫的研究。首先,以類石墨烯型六方氮化硼(h-BN)作載體,利用溶劑熱法將磷鎢酸(HPW)負(fù)載到少層的h-BN中,成功制備了HPW/h-BN多相催化劑。通過掃描電鏡(SEM)、透射電鏡(TEM)、X射線衍射(XRD)等方法對(duì)催化劑進(jìn)行表征,結(jié)果表明HPW被成功限域到h-BN的微孔中,且負(fù)載后h-BN的結(jié)構(gòu)沒有發(fā)生變化。在ODS體系中,HPW/h-BN對(duì)二苯并噻吩(DBT)和4,6-二甲基二苯并噻吩(4,6-DMDBT)表現(xiàn)出極好的催化性。HPW/h-BN對(duì)DBT的脫除率能達(dá)到100%,且循環(huán)使用6次后催化劑的脫硫效率沒有明顯的降低。機(jī)理分析顯示,反應(yīng)過程中DBT和H_2O_2同時(shí)被吸附到催化劑表面,然后[PW12O40]3-接受H_2O_2的活性氧形成過氧物種W(O)2,最后DBT被W(O)2氧化成DBTO2,實(shí)現(xiàn)硫化物的脫除。采用浸漬法將硅鎢酸(HSiW)負(fù)載到h-BN中,成功制備了HSiW/h-BN多相催化劑。通過紅外光譜(FT-IR)、XRD、SEM、TEM等表征方法分析催化劑的形貌和結(jié)構(gòu),結(jié)果表明多相化后HSiW在h-BN上高度分散,且HSiW中的W元素會(huì)發(fā)生價(jià)態(tài)變化。HSiW/h-BN對(duì)DBT和4,6-DMDBT的脫除率均可達(dá)到100%,表現(xiàn)出良好的活性。循環(huán)實(shí)驗(yàn)研究表明使用9次后,HSiW/h-BN對(duì)DBT的脫除率仍然可以達(dá)到93%。分析認(rèn)為,HSi W的高度分散以及HSiW中W元素的價(jià)態(tài)變化均有利于催化反應(yīng)的進(jìn)行。以離子液體修飾的六方氮化硼(BN-IL)為載體負(fù)載磷鉬酸(HPMo),成功制備了HPMo/BN-IL多相催化劑。通過X射線光電子能譜(XPS)、拉曼(Raman)、XRD、TEM等表征方法對(duì)催化劑進(jìn)行分析,結(jié)果表明多相化后催化劑仍保持h-BN的層狀和介孔結(jié)構(gòu)�；钚詫�(shí)驗(yàn)研究表明,催化劑對(duì)4,6-DMDBT、DBT和3-MBT均表現(xiàn)出優(yōu)異的催化活性,且循環(huán)使用5次后催化劑對(duì)4,6-DMDBT的活性僅降低3.7%。分析認(rèn)為,IL的引入使得HPMo/BN-IL催化劑的活性中心不易脫落,從而提高了催化劑的穩(wěn)定性。干擾實(shí)驗(yàn)研究表明,催化劑在烯烴和芳香烴存在時(shí)表現(xiàn)出較好的對(duì)硫化物轉(zhuǎn)化選擇性。
[Abstract]:In recent years, with the deterioration of oil quality, the sulfur content of fuel increased. SOx produced by fuel combustion can cause serious environmental pollution. Therefore, more and more attention has been paid to the removal of sulfides. Mercaptan and sulfide in fuel oil can be removed by simple physical or chemical methods, while thiophene sulfur is difficult to be removed by traditional hydrodesulfurization technology. For example, biological desulfurization, adsorption desulfurization, extraction desulfurization, oxidation desulfurization, etc. Due to mild reaction conditions and high activity to aromatic sulfides, oxidative desulfurization (ODS) has become a key technology for the production of ultra-low sulfur fuel. ODS technology is to find a high efficient and stable catalyst. In this paper, a series of catalysts have been designed and synthesized. Boron nitride supported heteropoly acid catalyst, Firstly, the graphene type hexagonal boron nitride (h-BN) was used as the carrier, and the phosphotungstate HPWs were loaded into the less layer h-BN by solvothermal method. HPW/h-BN multiphase catalysts were successfully prepared and characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results showed that HPW was successfully confined to the micropores of h-BN. The structure of h-BN has not changed after loading. In ODS system, the catalytic activity of HPW-h-BN p-dibenzothiophene (DBT) and 4-dimethyldimethyldibenzothiophene (4-dimethyldibenzothiophene 44-DMDBT) is excellent. The removal rate of DBT by HPW-h-BN can reach 100%, and the catalyst can be recycled for 6 times. The mechanism analysis shows that, During the reaction, DBT and H _ 2O _ 2 were adsorbed on the surface of the catalyst at the same time, then [PW12O40] _ 3- reactive oxygen species received by H _ 2O _ 2 to form the superoxide species WO _ (2). Finally, DBT was oxidized to DBTO2 by WKO _ (2) to realize the removal of sulfides. HSiW (silicotungstic acid) was loaded into h-BN by impregnation method. HSiW/h-BN multiphase catalyst was successfully prepared. The morphology and structure of the catalyst were analyzed by FTIR and TEM. The results showed that HSiW was highly dispersed on h-BN. The valence of W element in HSiW will change. The removal rate of DBT and 4HSiW / h-BN can reach 100, showing good activity. The cyclic experiment shows that the removal rate of HSiW / h-BN can still reach 93% after 9 times of use of HSiW / h-BN. It is concluded that the removal rate of HSiW / h-BN can reach 93.The results show that the removal rate of HSiW / h-BN can still reach 93% after 9 times of use of HSiW / h-BN. The high dispersion of HPMo/BN-IL and the change of valence state of W element in HSiW were all beneficial to the catalytic reaction. HPMo/BN-IL multiphase catalyst was successfully prepared by using boron nitride (BN-ILL) modified with ionic liquid as the carrier to support HPMoO _ 4. The catalysts were characterized by means of electron spectroscopy (EDS) and Raman Raman spectroscopy (Ram) and X-ray diffraction (XRD) TEM. The results showed that the layered and mesoporous structure of h-BN remained after heterogeneous reaction, and the catalytic activity of the catalyst for 46-DMDBT DBT and 3-MBT was excellent. The activity of the catalyst to 4N 6-DMDBT was only decreased by 3.7% after 5 cycles. It is considered that the introduction of IL makes the active center of HPMo/BN-IL catalyst not easy to fall off, thus improving the stability of the catalyst. In the presence of alkenes and aromatic hydrocarbons, the catalyst exhibited good conversion selectivity to sulfides.
【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TE624.9

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