本文選題：5-羥甲基糠醛(HMF) + 己糖　； 參考：《江南大學(xué)》2017年碩士論文

【摘要】：化石能源已經(jīng)無法滿足世界經(jīng)濟(jì)快速發(fā)展的需求,尋求和開發(fā)清潔可再生的綠色能源來替代傳統(tǒng)化石能源已經(jīng)迫在眉睫。生物質(zhì)作為一種儲量豐富、來源廣泛且可再生的能源已經(jīng)引起了人們的廣泛關(guān)注。碳水化合物作為生物質(zhì)能源的主要組成部分,開發(fā)利用其降解制備一些高附加值的平臺化合物具有重要的現(xiàn)實(shí)意義。其中5-羥甲基糠醛(HMF)作為連接生物質(zhì)和石油工業(yè)化學(xué)的紐帶,由碳水化合物脫水制備HMF具有十分深遠(yuǎn)的意義。本文主要研究席夫堿金屬配合物和改性MCM-41協(xié)同催化單糖脫水制備HMF的反應(yīng),以下是本文的主要研究內(nèi)容及成果:(1)首先合成了一種酸性功能化的離子液體1-(丙基-3-磺酸基)乙烯基咪唑硫酸氫鹽([(CH2)3SO3HVIm]HSO4,IL1),并將其固載到改性后的MCM-41上,得到一種固體酸催化劑MCM-41-IL1。將所制備的催化劑用于果糖脫水反應(yīng)制備HMF,發(fā)現(xiàn)具有較好的催化活性。以DMSO為溶劑,催化劑MCM-41-IL1用量為30 mg,在130℃下反應(yīng)3 h,催化果糖反應(yīng)活性最好,HMF產(chǎn)率可以達(dá)到86.3%。并對所制備的催化劑進(jìn)行了分析表征,發(fā)現(xiàn)固載離子液體后的MCM-41具有良好的穩(wěn)定性和較大的比表面積,可以作為良好的固體酸載體。(2)制備了席夫堿鉻金屬配合物并將其固載到不同基團(tuán)改性的MCM-41上,制備得到不同種類的非均相催化劑,并將其用于葡萄糖轉(zhuǎn)化制備HMF。考察了催化劑種類、反應(yīng)溫度、時(shí)間、催化劑用量和溶劑等因素對葡萄糖催化效果的影響。當(dāng)以DMSO為溶劑,在140℃下反應(yīng)4 h,催化劑Cr(Salten)-MCM-41-IL1的用量為50 mg時(shí),催化劑的催化活性最好,葡萄糖的轉(zhuǎn)化率為99.3%,HMF產(chǎn)率達(dá)到50.2%。當(dāng)以此催化劑催化果糖、蔗糖和菊粉其他反應(yīng)底物時(shí),仍然具有較高的催化活性。催化劑Cr(Salten)-MCM-41-IL1在循環(huán)使用5次后,催化葡萄糖轉(zhuǎn)化仍然保持較好的催化活性(HMF產(chǎn)率為42.2%)。(3)制備了一種氧鋯基席夫堿配合物,并將其固載到MCM-41上得到一種非均相催化劑,考察了其催化果糖制備HMF的效果。以Zr(IV)-salen-MCM-41為催化劑,探究了不同反應(yīng)因素對果糖轉(zhuǎn)化HMF產(chǎn)率的影響;發(fā)現(xiàn)以DMSO為溶劑,140℃下反應(yīng)4h,催化劑用量為50 mg時(shí),催化果糖轉(zhuǎn)化可以得到92.0%的HMF。將此催化劑用于催化其他反應(yīng)底物,發(fā)現(xiàn)催化蔗糖和菊粉時(shí)活性較好,HMF產(chǎn)率分別為77.4%和84.7%。對催化劑Zr(IV)-salen-MCM-41進(jìn)行了重復(fù)實(shí)驗(yàn),發(fā)現(xiàn)催化劑經(jīng)過4次循環(huán)使用仍然能保持較好的催化活性。
[Abstract]:Fossil energy has been unable to meet the rapid development of the world economy. It is urgent to seek and develop clean and renewable green energy to replace the traditional fossil energy. Biomass, as a kind of abundant and renewable energy, has attracted much attention. Carbohydrates are the main components of biomass energy. It is of great practical significance to develop and use carbohydrates to degrade and prepare some platform compounds with high added value. Among them, 5-hydroxymethylfurfural (HMF) is the link between biomass and petroleum industry chemistry. It is of great significance to prepare HMF from carbohydrate dehydration. The synthesis of HMF with Schiff base metal complexes and modified MCM-41 was studied in this paper. The main contents and achievements are as follows: (1) at first, a kind of acidic ionic liquid 1- (propyl-3-sulfonic acid) vinyl imidazole hydrogen sulfate ([(Ch _ 2) _ 3SO _ 3HVIm] HSO _ 4HSO _ 4I _ 1) was synthesized and immobilized on the modified MCM-41 to obtain a solid acid catalyst MCM-41-IL _ 1. The prepared catalyst was used in fructose dehydration to prepare HMF, and it was found that the catalyst had good catalytic activity. With DMSO as solvent, the amount of catalyst MCM-41-IL1 was 30 mg, and the reaction temperature was 130 鈩，

本文編號：2106756