發(fā)布時(shí)間：2018-05-08 21:20

  本文選題：生物質(zhì)資源 + 高值化利用�。� 參考：《江西師范大學(xué)》2017年碩士論文

【摘要】：隨著化石能源的日益枯竭以及環(huán)境問(wèn)題的愈加嚴(yán)重,松節(jié)油、纖維素和半纖維素等可再生生物質(zhì)資源的高值化利用近年來(lái)受到了研究者的廣泛關(guān)注。然而由于現(xiàn)有工藝技術(shù)大多采用傳統(tǒng)無(wú)機(jī)質(zhì)子酸催化劑,導(dǎo)致這類(lèi)資源的深加工利用率較低,三廢矛盾較為突出,造成了極大的資源浪費(fèi)和環(huán)境污染問(wèn)題,亟需開(kāi)發(fā)綠色高效的酸催化劑以實(shí)現(xiàn)生物質(zhì)資源的高值化利用。作為綠色化學(xué)最為典型的代表,離子液體因其具有許多獨(dú)特的物化性質(zhì),為生物質(zhì)資源的高值化利用提供了新的發(fā)展契機(jī)。因此,本論文通過(guò)調(diào)控離子液體的酸度,根據(jù)不同反應(yīng)類(lèi)型“量身定制”出一系列高催化活性的酸功能化離子液體,替代傳統(tǒng)酸催化劑用于綠色合成萜烯酯與高效水解半纖維素,從而實(shí)現(xiàn)生物質(zhì)資源的高值化利用。本論文的主要研究工作如下:第一部分:設(shè)計(jì)合成了六種不同酸度的磺酸功能化離子液體,并用于催化萜烯醇與乙酸酐反應(yīng)合成萜烯酯香料,探究了離子液體的酸度與其催化活性之間的構(gòu)效關(guān)系。研究結(jié)果表明,離子液體的酸度可顯著影響目標(biāo)產(chǎn)物萜烯酯的產(chǎn)率,調(diào)節(jié)離子液體催化劑的pH值在1~2范圍,萜烯醇轉(zhuǎn)化率和萜烯酯選擇性均可達(dá)到最優(yōu)。反應(yīng)完成后,離子液體催化劑[Ps2TMEDA][BF4]2可自動(dòng)沉淀析出,經(jīng)簡(jiǎn)單過(guò)濾即可實(shí)現(xiàn)催化劑的回收套用,且催化劑重復(fù)使用五次以上活性無(wú)明顯變化。此外,本論文還詳細(xì)考察了合成萜烯酯的酯化反應(yīng)動(dòng)力學(xué),并建立擬均相動(dòng)力學(xué)模型,回歸得到離子液體催化酯化體系的動(dòng)力學(xué)參數(shù),為實(shí)現(xiàn)離子液體催化合成萜烯酯過(guò)程提供可靠的基礎(chǔ)數(shù)據(jù)和設(shè)計(jì)依據(jù)。第二部分:設(shè)計(jì)合成了三種強(qiáng)酸性膽堿離子液體催化劑,并用于催化半纖維素高效水解制備糠醛。研究結(jié)果發(fā)現(xiàn),離子液體的催化活性與其酸強(qiáng)度密切相關(guān),酸強(qiáng)度越大,其催化性能越好。離子液體[N111C2OSO3H][CF3SO3]催化半纖維素水解制備糠醛,在1,4-二氧六環(huán)為溶劑、催化劑用量0.1g、反應(yīng)溫度120°C、反應(yīng)時(shí)間6 h的優(yōu)化反應(yīng)條件下,糠醛產(chǎn)率高達(dá)82.0%,進(jìn)一步將該催化劑用于木糖脫水制備糠醛,木糖轉(zhuǎn)化率和糠醛產(chǎn)率均在95%以上,同樣表現(xiàn)出很好的催化性能,催化劑循環(huán)使用五次,催化活性無(wú)明顯下降。
[Abstract]:With the increasingly depletion of fossil energy and the increasingly serious environmental problems, the high value utilization of renewable biomass resources such as turpentine, cellulose and hemicellulose has been widely concerned by researchers in recent years. However, due to the traditional inorganic proton acid catalyst used in the existing technology, the utilization rate of this kind of resources is low, and the contradiction between the three wastes is more prominent, resulting in a great waste of resources and environmental pollution. It is urgent to develop green and efficient acid catalyst to realize high value utilization of biomass resources. As the most typical representative of green chemistry, ionic liquids have many unique physicochemical properties, which provide a new opportunity for the development of high value utilization of biomass resources. Therefore, by regulating the acidity of ionic liquids, a series of acid-functionalized ionic liquids with high catalytic activity were developed according to different reaction types. Instead of traditional acid catalysts, terpenes were synthesized green and hemicellulose was hydrolyzed in order to realize high value utilization of biomass resources. The main work of this thesis is as follows: in the first part, six kinds of sulfonic acid functionalized ionic liquids with different acidity were designed and synthesized, which were used to catalyze the reaction of terpene alcohol with acetic anhydride to synthesize terpene esters. The relationship between acidity and catalytic activity of ionic liquids was investigated. The results showed that the acidity of ionic liquid could significantly affect the yield of terpene ester, and the conversion of terpene alcohol and the selectivity of terpene ester could be optimized by adjusting the pH value of ionic liquid catalyst in the range of 1 ~ 2. After the reaction, the ionic liquid catalyst [Ps2TMEDA] [BF4] 2 can precipitate and precipitate automatically. After simple filtration, the catalyst can be recovered and applied, and the activity of the catalyst has no obvious change after repeated use for more than five times. In addition, the kinetics of esterification of synthetic terpene esters was investigated in detail, and a pseudo-homogeneous kinetic model was established, and the kinetic parameters of ionic liquid catalyzed esterification system were obtained by regression analysis. It provides reliable basic data and design basis for the synthesis of terpene esters catalyzed by ionic liquids. In the second part, three kinds of strong acidic choline ionic liquid catalysts were designed and synthesized, which were used to catalyze the hydrolysis of hemicellulose to furfural. The results show that the catalytic activity of ionic liquids is closely related to their acid strength, and the higher the acid strength, the better the catalytic activity of ionic liquids. Ionic liquid [N111C2OSO3H] [CF3SO3] catalyzes the hydrolysis of hemicellulose to furfural under the optimum conditions of 1: 4- dioxane as solvent, the amount of catalyst 0.1 g, the reaction temperature 120 擄C, the reaction time 6 h. The yield of furfural was up to 82.0. The catalyst was further used in xylose dehydration to produce furfural. The conversion rate of xylose and the yield of furfural were above 95%, which also showed good catalytic performance. The catalytic activity did not decrease obviously when the catalyst was reused for five times.
【學(xué)位授予單位】：江西師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O643.36

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