發(fā)布時(shí)間：2018-04-16 14:21

  本文選題：糠醛 + HMF��； 參考：《天津工業(yè)大學(xué)》2017年碩士論文

【摘要】：生物質(zhì)作為唯一可再生的有機(jī)碳資源,具有來源豐富,價(jià)格低廉,綠色環(huán)保以及可再生等優(yōu)點(diǎn),是替代石油生產(chǎn)燃料和化學(xué)品的理想選擇。其中,糠醛和5-輕甲基糠醛(HMF)是兩種重要的生物質(zhì)基平臺(tái)分子,可以通過不同的基元反應(yīng)制備具有高附加值的平臺(tái)分子下游化學(xué)品,例如:糠偶姻、糠偶酰、5,5'-二羥甲基糠偶姻(DHMF),5,5'-二羥甲基糠偶酰(BHMF)等。但是目前這些轉(zhuǎn)化還存在反應(yīng)條件苛刻、產(chǎn)物選擇性差、催化體系過于復(fù)雜以及催化劑難以回收重復(fù)利用等問題。因此,發(fā)展更多高效溫和催化體系來解決上述問題,為這些基元反應(yīng)提供新的方法和思路顯的尤為重要。本文主要分為以下幾個(gè)部分:第一章主要介紹了生物質(zhì)和平臺(tái)分子的概念以及目前生物質(zhì)轉(zhuǎn)化制備燃料的發(fā)展?fàn)顩r;接著詳細(xì)介紹了平臺(tái)分子糠醛和HMF的制備以及各自轉(zhuǎn)化成為化學(xué)品或者燃料分子的最具代表性的研究進(jìn)展;最后,簡單介紹了本文所應(yīng)用的催化體系及研究進(jìn)展。第二章介紹了平臺(tái)分子糠醛和HMF通過自身碳-碳偶聯(lián)反應(yīng)制備C10和C12糠偶姻的方法。反應(yīng)使用蒙脫土負(fù)載的噻唑類離子液體和堿結(jié)合形成的卡賓為催化劑,實(shí)現(xiàn)了糠醛和HMF的自身增碳偶聯(lián),獲得了最高99%的C10糠偶姻產(chǎn)率以及98%的C12糠偶姻產(chǎn)率�？疾炝瞬煌�溶劑對反應(yīng)的影響,發(fā)現(xiàn)在無溶劑條件下該反應(yīng)依然可以得到很高的收率。同時(shí),研究了不同噻唑類離子液體對反應(yīng)產(chǎn)率的影響,發(fā)現(xiàn)噻唑環(huán)上帶有給電子基團(tuán)的離子液體比帶有吸電子基團(tuán)的具有更高的催化活性。最后研究了負(fù)載催化劑的重復(fù)利用性能,發(fā)現(xiàn)該催化體系重復(fù)利用四次以后產(chǎn)率并沒有明顯的減少。第三章介紹了C10和C12糠偶姻選擇性氧化制備α-呋喃基二酮的方法。合成了具有典型Keggin型結(jié)構(gòu)的八鉬酸季銨鹽和十鎢酸季銨鹽催化劑,在較為溫和的條件下,獲得了100%的糠偶酰收率和94%的BHMF收率。提出了八鉬酸季銨鹽催化該反應(yīng)可能的反應(yīng)機(jī)理,發(fā)現(xiàn)與八鉬酸季銨鹽催化劑相比,十鎢酸季銨鹽催化劑在C10和C12糠偶姻選擇性氧化反應(yīng)中的催化活性較低。與傳統(tǒng)方法相比,該方法具有操作簡單、環(huán)境友好、催化劑可以回收利用等特點(diǎn)。第四章對全文進(jìn)行了總結(jié)。綜上所述,本文主要以平臺(tái)分子糠醛和HMF為研究對象,發(fā)展了蒙脫土負(fù)載的卡賓催化體系以及具有典型Keggin型結(jié)構(gòu)的八鉬酸季銨鹽和十鎢酸季銨鹽催化體系,實(shí)現(xiàn)了平臺(tái)分子到不同化學(xué)品的綠色轉(zhuǎn)化過程,研究了不同催化劑對反應(yīng)活性和選擇性的影響規(guī)律,拓展了生物質(zhì)基平臺(tái)分子的轉(zhuǎn)化和應(yīng)用。
[Abstract]:Biomass, as the only renewable organic carbon resource, has the advantages of rich sources, low price, green environment and renewable. It is an ideal alternative to oil to produce fuels and chemicals.Among them, furfural and 5-light methylfurfural (HMF) are two important biomass-based platform molecules, which can be used to prepare high value-added downstream chemicals, such as furfural, furfural and 5-methylfurfural, such as furfural and 5-methylfurfural.BHMFs, DHMFN, DHMFN, DHMFN, DHMFN, DHMF5, DHMF5, BHMFs, and BHMFs, and so on.However, at present, there are still some problems such as harsh reaction conditions, poor selectivity of products, complex catalytic system and the difficulty of catalyst recovery and reuse.Therefore, it is very important to develop more efficient and moderate catalytic systems to solve the above problems and provide new methods and ideas for these elementary reactions.This paper is divided into the following parts: the first chapter mainly introduces the concept of biomass and platform molecules and the current development of biomass conversion to fuel;Then, the preparation of furfural and HMF and the most representative research progress of their conversion to chemical or fuel molecules are introduced in detail. Finally, the catalytic system and research progress in this paper are briefly introduced.In chapter 2, the method of preparing C _ 10 and C _ 12 furfural with HMF by self-carbon-carbon coupling reaction was introduced.Using montmorillonite supported thiazole ionic liquid and carbene formed by alkali as catalyst, the coupling of furfural and HMF was realized. The highest yield of C10 furfurin and 98% C12 furfural was obtained.The effects of different solvents on the reaction were investigated. It was found that the yield of the reaction was still high under the condition of no solvent.At the same time, the effect of different thiazole ionic liquids on the yield of the reaction was studied. It was found that the ionic liquids with electron donating groups on the thiazole ring had higher catalytic activity than those with electron absorbing groups.Finally, the reutilization performance of the supported catalyst was studied, and it was found that the yield of the catalyst was not significantly reduced after the reuse of the catalyst system for four times.In chapter 3, the method of selective oxidation of C _ 10 and C _ 12 furanyl diketones was introduced.Quaternary ammonium octamolybdate and quaternary ammonium decatungstate catalysts with typical Keggin structure were synthesized. Under mild conditions, 100% furfuryl yield and 94% BHMF yield were obtained.The possible reaction mechanism of quaternary ammonium octamolybdate was proposed. It was found that the catalytic activity of quaternary ammonium decatungstate catalyst was lower than that of quaternary ammonium octamolybdate catalyst in the selective oxidation of C 10 and C 12 furfurin.Compared with the traditional method, this method has the advantages of simple operation, friendly environment and recyclable catalyst.Chapter four summarizes the full text.To sum up, in this paper, the montmorillonite supported carbene catalytic system and the quaternary ammonium octamolybdate and decatungstate quaternary ammonium salt with typical Keggin structure were developed with the platform molecule furfural and HMF as the research objects.The green conversion process from platform molecules to different chemicals was realized. The effects of different catalysts on the activity and selectivity of the reaction were studied. The conversion and application of biomass based platform molecules were expanded.
【學(xué)位授予單位】：天津工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.251

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 閆少康;孫紹暉;馬春松;孫培勤;陳俊武;;生物質(zhì)基含氧化合物化學(xué)催化法制備長鏈烷烴的研究進(jìn)展[J];化工進(jìn)展;2016年05期

2 歐陽洪生;肖竹錢;蔣成君;方晟;毛建衛(wèi);;生物質(zhì)基平臺(tái)化合物糠醛的研究進(jìn)展[J];應(yīng)用化工;2014年10期

3 Gabriel Morales;Juan A.Melero;Marta Paniagua;Jose Iglesias;Blanca Hernandez;Maria Sanza;;磺酸多相催化劑用于二甲基亞砜中C_6-單糖脫水制5-羥甲基糠醛(英)[J];催化學(xué)報(bào);2014年05期

4 路瑤;魏賢勇;宗志敏;陸永超;趙煒;曹景沛;;木質(zhì)素的結(jié)構(gòu)研究與應(yīng)用[J];化學(xué)進(jìn)展;2013年05期

5 張家榮;李軍;王普光;董曉麗;高爽;;八鉬酸季銨鹽催化H_2O_2氧化醇制備醛酮[J];大連工業(yè)大學(xué)學(xué)報(bào);2012年04期

6 于建榮;陳大明;江洪波;;能源作物發(fā)展現(xiàn)狀和商業(yè)化前景[J];生物產(chǎn)業(yè)技術(shù);2009年05期

7 陳紅;丁運(yùn)生;查敏;張效敏;;蒙脫土負(fù)載[C_(14)mim]~+有機(jī)陽離子催化合成檸檬酸三丁酯[J];工業(yè)催化;2007年09期

8 陳文明;王君;陳明功;邵群;陳明強(qiáng);;分子篩催化木糖制備糠醛的研究[J];化學(xué)與生物工程;2007年01期

9 王輝,曾和平;超聲波催化糠偶姻縮合的研究[J];化學(xué)試劑;2003年03期

10 溫輝梁,劉崇波,黃紹華,鄧國榮;相轉(zhuǎn)移催化Wulff-Kischner反應(yīng)制備2-甲基呋喃[J];南昌大學(xué)學(xué)報(bào)(理科版);1999年04期

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