本文選題：介孔材料　切入點：離子液體　出處：《江南大學(xué)》2017年碩士論文

【摘要】：生物柴油是一種環(huán)境友好且可再生的生物質(zhì)能源,可作為替代石油質(zhì)能源的燃料,具有良好的市場前景。而生物柴油工業(yè)化生產(chǎn)的關(guān)鍵在于高效非均相催化劑的制備。目前催化合成生物柴油所用的非均相催化劑種類較多,其中固載型離子液體因綠色環(huán)保性受到廣泛的關(guān)注。本研究旨在設(shè)計、制備系列酸性介孔材料,并進行酸性離子液體的固載,得到擁有雙酸位特性的固載型離子液體催化劑;以大豆油和甲醇酯交換合成生物柴油的反應(yīng)為探針,考察所制備的雙酸位特性的固載型離子液體的催化性能。首先,采用一步水解共縮合并結(jié)合水熱技術(shù),制備了一系列酸性雜化介孔材料SO_4~(2-)-x/ZrO_2-SiO_2-y。利用傅里葉紅外光譜、固體核磁(29Si MAS NMR)以及X射線光電子能譜對雜化材料的組成和結(jié)構(gòu)進行表征,三者共同驗證了雜化材料的合成;通過廣角X射線衍射分析以及N2物理吸附測定,對雜化材料的孔結(jié)構(gòu)性質(zhì)進行表征,發(fā)現(xiàn)所合成雜化材料都具有優(yōu)良的介孔結(jié)構(gòu);利用酸堿滴定法對雜化材料表面的酸量進行測定,結(jié)果表明,雜化材料表面的Br?nsted酸容量主要由其活性組分SO_4~(2-)的量決定。其次,采用表面嫁接法將酸性離子液體—磺酸功能化咪唑硫酸氫鹽([Ps-im]HSO4)固載到雜化介孔材料SO_4~(2-)-x/ZrO_2-SiO_2-y上,制備了系列固載型離子液體SO_4~(2-)-x/ZrO_2-SiO_2-y-IL。該系列催化劑擁有優(yōu)良的結(jié)構(gòu)特性以及獨特的雙酸位性質(zhì),其催化活性不僅比均相催化劑高,更優(yōu)于單酸性位的固載型離子液體SBA-15-IL。運用傅里葉紅外光譜、X射線衍射、N2物理吸附、透射電鏡和熱重等表征手段,對催化劑的結(jié)構(gòu)、組成進行分析。此外,還以SO_4~(2-)-1.2/ZrO_2-SiO_2-1.0-IL為例,對酯交換反應(yīng)的工藝參數(shù)進行單因素優(yōu)化,得到適宜的工藝為:140℃的反應(yīng)溫度,4 h的反應(yīng)時間,30:1的醇油摩爾比以及5 wt%的催化劑用量(基于大豆油質(zhì)量的百分比),在此條件下,所得生物柴油的收率超過96%;但在重復(fù)利用的過程中,催化劑的活性逐漸降低,其原因可能是由親水性載體對甘油的吸附導(dǎo)致的。最后,為了增強雜化材料的疏水性,從而提高固載型離子液體的重復(fù)利用性,因此在雜化材料的合成過程中,采用有機硅((CH3CH2O)3Si-Et-Si(OCH2CH3)3,BTEE)取代無機硅(正硅酸四乙酯,TEOS),即對無機雜化材料進行有機改性,合成有機-無機雜化材料SO_4~(2-)/ZrO_2-SiO_2(Et),并進行不同離子液體用量的固載。采用傅里葉紅外光譜、固體核磁、X射線光電子能譜、X射線衍射、透射電鏡、N2物理吸附測試及熱重等表征方法,對有機-無機雜化材料及其固載型離子液體的組成、孔洞結(jié)構(gòu)、熱穩(wěn)定性和酸性位點類型等性質(zhì)進行了分析;此外,還通過接觸角測試儀對載體的疏水性改性效果進行了表征。以固載型離子液體為酯交換反應(yīng)的催化劑,采用單因素和響應(yīng)面分析法對反應(yīng)工藝參數(shù)進行優(yōu)化。結(jié)果表明:在離子液體固載量為2.50 mmol·g~(-1),催化劑用量(基于大豆油質(zhì)量的百分比)為5.0 wt%,反應(yīng)溫度為151.0℃,反應(yīng)時間為3.5 h,醇油摩爾比為21:1時,生物柴油的收率達(dá)99.02%。此外,該催化劑表現(xiàn)出優(yōu)良的重復(fù)利用性。
[Abstract]:Biodiesel is a kind of environmental friendly and renewable biomass energy, can be used as a substitute for petroleum energy fuels, with good market prospects. And the key to produce biodiesel is a highly efficient heterogeneous catalyst preparation. Currently used in catalytic synthesis of biodiesel heterogeneous catalyst supported more species, which the ionic liquid due to environmental protection has been widely concerned. The purpose of this study is to design and prepare a series of acidic mesoporous materials, and acidic ionic liquid immobilized, get double acid properties of supported ionic liquid catalyst; transesterification of soybean oil and methanol to biodiesel synthesis reaction as a probe, double acid characteristics on the preparation of supported ionic liquid catalysis. Firstly, using one step hydrolysis co condensation and combination of hydrothermal technique, a series of acid hybrid mesoporous materials were synthesized by using SO_4~ (2-) -x/ ZrO_2-SiO_2-y. by Fourier transform infrared spectroscopy, NMR (29Si MAS NMR) and X ray photoelectron spectroscopy were used to characterize the composition and structure of hybrid materials, the three together to verify the synthesis of hybrid materials; through the analysis of wide angle X ray diffraction and N2 physical adsorption were determined to characterize the pore structure properties of the hybrid materials, find the synthesis hybrid materials have excellent mesoporous structure; using acid-base titration of the hybrid material surface acidity were measured. The results show that the hybrid materials on the surface of Br? Nsted Acid capacity is mainly composed of the active component SO_4~ (2-) the amount of decision. Secondly, the surface grafting method of acidic ionic liquids - SO3 h-functionalized hydrogen sulfate ([Ps-im]HSO4) immobilized to hybrid mesoporous materials SO_4~ (2-) -x/ZrO_2-SiO_2-y, a series of supported ionic liquid to prepare SO_4~ (2-) -x/ ZrO_2-SiO_2-y-IL. catalyst of the series. The structure characteristics of excellent and unique double acid properties, its catalytic activity than the homogeneous catalyst is high, more than a single acid supported ionic liquid SBA-15-IL. by Fourier transform infrared spectroscopy, X ray diffraction, N2 physical adsorption, TEM and TGA characterization means, the structure of the catalysts, composition were analyzed. In addition, the SO_4~ (2-) -1.2/ZrO_2-SiO_2-1.0-IL as an example, the single factor optimization of process parameters on the transesterification were obtained, the appropriate process is: reaction temperature 140 C, reaction time 4 h, methanol to oil molar ratio 30:1, catalyst 5 wt% dosage (percentage based on the quality of soybean oil), under these conditions, the biodiesel yield was over 96%; but in the process of repeated use, the catalyst activity gradually decreased, the reason may be caused by a hydrophilic carrier adsorption of glycerol. Finally, in order to enhance the clutter The hydrophobic material, so as to improve the reusability of the immobilized ionic liquids, the synthesis process of the hybrid materials, by using silicone ((CH3CH2O) 3Si-Et-Si (OCH2CH3) 3, BTEE) to replace the inorganic silicon (four ethyl orthosilicate, TEOS), that of inorganic hybrid materials for organic modification the synthesis of organic inorganic hybrid materials of SO_4~ (2-) /ZrO_2-SiO_2 (Et), and different amount of ionic liquid supported by Fourier transform infrared spectroscopy, 1H NMR, X ray photoelectron spectroscopy, X ray diffraction, transmission electron microscopy, N2 adsorption test and thermogravimetric characterization methods of organic-inorganic hybrid materials and supported ionic liquid composition, pore structure, thermal stability and acid site types are analyzed; in addition, the contact angle measurement instrument of hydrophobic carrier modification effect were investigated. The ionic liquid immobilized for transesterification reaction The catalyst, using single factor and response surface analysis on the reaction parameters were optimized. The results showed that: in the ionic liquid loading is 2.50 mmol - g~ (-1), the amount of catalyst (percentage based on the quality of soybean oil) was 5 wt%, the reaction temperature is 151 DEG C, the reaction time is 3.5 h, the molar ratio of methanol to oil for 21:1, the biodiesel yield was 99.02%. in addition, the catalyst exhibited excellent reusability.

【學(xué)位授予單位】：江南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36;TE667

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