由生物質(zhì)糖類一鍋法制備2，5二羥甲基四氫呋喃的研究
發(fā)布時(shí)間：2018-10-26 09:40
【摘要】：如今,許多發(fā)達(dá)國家,都在致力于研究開發(fā)和研究新型高效的和低污染乃至無污染的生物質(zhì)利用技術(shù),以達(dá)到替代或是緩解化石類不可再生能源的利用的目的,進(jìn)而為實(shí)現(xiàn)經(jīng)濟(jì)的可持續(xù)發(fā)展提供根本的保障。呋喃類衍生物是生物質(zhì)和可替代部分化石能源的化學(xué)品之間的橋梁,本篇文章中,就生物質(zhì)果糖的至2,5-二羥甲基四氫呋喃的轉(zhuǎn)化展開了研究:(1)首先對(duì)生物質(zhì)和可替代部分化石能源的化學(xué)品之間的橋梁—5-羥甲基糠醛(5-HMF)的加氫制備2,5-二羥甲基四氫呋喃(DHMTHF)的反應(yīng)進(jìn)行了研究。本章采用了傳統(tǒng)浸漬法制備得到Ru/SiO2 Aerogel催化劑,用于5-羥甲基糠醛到2,5-二羥甲基四氫呋喃的完全加氫反應(yīng)當(dāng)中,獲得了100%的5-HMF轉(zhuǎn)化率和98%的DHMTHF選擇性,該方法具有操作簡(jiǎn)單、高效的優(yōu)點(diǎn)。催與目前報(bào)道的文獻(xiàn)中釕催化劑相比,該催化劑在相對(duì)溫和的反應(yīng)條件下得到了很高的得率。(2)本章中我們選用非均相固體酸催化劑于果糖轉(zhuǎn)化制備5-羥甲基糠醛反應(yīng)體系,結(jié)合我們之前對(duì)于5-HMF下游轉(zhuǎn)化加氫制備2,5-二羥甲基四氫呋喃(DHMTHF)體系的研究,在水相和雙相體系中運(yùn)用目前已商品化的固體酸催化劑Amberlyst-15與金屬催化劑Ru/NH2CH3-MSNs一鍋法由果糖制備2,5-二羥甲基四氫呋喃。我們?cè)诘谝徊糠止ぷ鞯幕A(chǔ)上,提出利用胺基甲基雙修飾的介孔二氧化硅小球作NH2CH3-MSNs載體,浸漬法負(fù)載金屬釕,與固體酸催化劑Amberlyst-15機(jī)械混合用于果糖一鍋法制備2,5-二羥甲基四氫呋喃反應(yīng)當(dāng)中,在純水相和雙相體系中做了嘗試,分別得到20%和39.8%2,5-二羥甲基四氫呋喃得率。(3)本章我們?cè)O(shè)計(jì)制備了具有yolk-shell結(jié)構(gòu)的釕基負(fù)載型催化劑(Ru/CH3NH2-MNSs@SiO2-SO3H),用于果糖一步法制備2,5-二羥甲基四氫呋喃(DHMTHF)的研究。用該催化劑完成一鍋法果糖脫水加氫制備DHMTHF。該材料的外殼上嫁接磺酸基,用于果糖脫水制備5-羥甲基糠醛,進(jìn)而與材料中心核負(fù)載的金屬釕作用,用于5-羥甲基糠醛的加氫反應(yīng)。我們將Yolk-Shell雙功能催化劑用于果糖一步法制備2,5-二羥甲基四氫呋喃反應(yīng)當(dāng)中,在純水相體系中做了嘗試,得到了相對(duì)較高的HMF產(chǎn)率,但離我們預(yù)期目標(biāo)高產(chǎn)率的制備DHMTHF還有差距。
[Abstract]:Nowadays, many developed countries are devoting themselves to the research and development of new and efficient, low-pollution and even non-polluting biomass utilization technologies in order to replace or alleviate the use of fossil non-renewable energy. Furthermore, it provides the fundamental guarantee for realizing the sustainable development of the economy. Furan derivatives are a bridge between biomass and chemicals that can replace part of fossil energy. The conversion of biomass fructose to 2o 5- dihydroxymethyl tetrahydrofuran was studied. (1) the bridge between biomass and chemicals that can substitute some fossil energy, 5-hydroxymethyl furfural (5-HMF) was added. The synthesis of 2'5-dihydroxymethyl tetrahydrofuran (DHMTHF) from hydrogen was studied. In this chapter, Ru/SiO2 Aerogel catalyst was prepared by traditional impregnation method. The catalyst was used in the complete hydrogenation of 5-hydroxymethyl furfural to 2-dimethyl-5-methyl-tetrahydrofuran. The conversion of 5-HMF and the selectivity of DHMTHF were 100% and 98%, respectively. This method has the advantages of simple operation and high efficiency. Compared with the ruthenium catalyst reported in the literature, In this chapter, the heterogeneous solid acid catalyst was used to transform fructose to 5-hydroxymethylfurfural reaction system. In combination with our previous studies on the conversion and hydrogenation of 5-HMF downstream to the preparation of (DHMTHF) system of 2o 5- dihydroxymethyl tetrahydrofuran, In aqueous and biphasic systems, fructose was prepared from fructose by commercial solid acid catalyst Amberlyst-15 and metal catalyst Ru/NH2CH3-MSNs in one pot. On the basis of the first part of the work, we proposed to use the mesoporous silica pellets modified with aminomethyl methyl as the NH2CH3-MSNs carrier, and the impregnation method was used to support the metal ruthenium. Mechanical mixing with solid acid catalyst Amberlyst-15 was used in the one-pot reaction of fructose to prepare 2o 5- dihydroxymethyl tetrahydrofuran, which was attempted in pure water and biphasic systems. The yields of 20% and 39.8% of 2-dihydroxymethyl tetrahydrofuran were obtained respectively. (3) in this chapter, ruthenium supported catalysts (Ru/CH3NH2-MNSs@SiO2-SO3H) with yolk-shell structure were designed and prepared. A study on the preparation of (DHMTHF) by fructose one-step method was carried out. Preparation of DHMTHF. by one-pot dehydration and hydrogenation of fructose with this catalyst The sulfonic group was grafted onto the shell of the material for the dehydration of fructose to produce 5-hydroxymethylfurfural, which reacted with ruthenium supported on the core of the material and was used for the hydrogenation of 5-hydroxymethylfurfural. Yolk-Shell bifunctional catalyst was used in the one-step fructose synthesis of 2o 5- dihydroxymethyl tetrahydrofuran. In the pure water phase system, a relatively high yield of HMF was obtained. However, there is still a gap between the preparation of DHMTHF and its expected high yield.
【學(xué)位授予單位】：上海師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O626.11
本文編號(hào)：2295309
[Abstract]:Nowadays, many developed countries are devoting themselves to the research and development of new and efficient, low-pollution and even non-polluting biomass utilization technologies in order to replace or alleviate the use of fossil non-renewable energy. Furthermore, it provides the fundamental guarantee for realizing the sustainable development of the economy. Furan derivatives are a bridge between biomass and chemicals that can replace part of fossil energy. The conversion of biomass fructose to 2o 5- dihydroxymethyl tetrahydrofuran was studied. (1) the bridge between biomass and chemicals that can substitute some fossil energy, 5-hydroxymethyl furfural (5-HMF) was added. The synthesis of 2'5-dihydroxymethyl tetrahydrofuran (DHMTHF) from hydrogen was studied. In this chapter, Ru/SiO2 Aerogel catalyst was prepared by traditional impregnation method. The catalyst was used in the complete hydrogenation of 5-hydroxymethyl furfural to 2-dimethyl-5-methyl-tetrahydrofuran. The conversion of 5-HMF and the selectivity of DHMTHF were 100% and 98%, respectively. This method has the advantages of simple operation and high efficiency. Compared with the ruthenium catalyst reported in the literature, In this chapter, the heterogeneous solid acid catalyst was used to transform fructose to 5-hydroxymethylfurfural reaction system. In combination with our previous studies on the conversion and hydrogenation of 5-HMF downstream to the preparation of (DHMTHF) system of 2o 5- dihydroxymethyl tetrahydrofuran, In aqueous and biphasic systems, fructose was prepared from fructose by commercial solid acid catalyst Amberlyst-15 and metal catalyst Ru/NH2CH3-MSNs in one pot. On the basis of the first part of the work, we proposed to use the mesoporous silica pellets modified with aminomethyl methyl as the NH2CH3-MSNs carrier, and the impregnation method was used to support the metal ruthenium. Mechanical mixing with solid acid catalyst Amberlyst-15 was used in the one-pot reaction of fructose to prepare 2o 5- dihydroxymethyl tetrahydrofuran, which was attempted in pure water and biphasic systems. The yields of 20% and 39.8% of 2-dihydroxymethyl tetrahydrofuran were obtained respectively. (3) in this chapter, ruthenium supported catalysts (Ru/CH3NH2-MNSs@SiO2-SO3H) with yolk-shell structure were designed and prepared. A study on the preparation of (DHMTHF) by fructose one-step method was carried out. Preparation of DHMTHF. by one-pot dehydration and hydrogenation of fructose with this catalyst The sulfonic group was grafted onto the shell of the material for the dehydration of fructose to produce 5-hydroxymethylfurfural, which reacted with ruthenium supported on the core of the material and was used for the hydrogenation of 5-hydroxymethylfurfural. Yolk-Shell bifunctional catalyst was used in the one-step fructose synthesis of 2o 5- dihydroxymethyl tetrahydrofuran. In the pure water phase system, a relatively high yield of HMF was obtained. However, there is still a gap between the preparation of DHMTHF and its expected high yield.
【學(xué)位授予單位】：上海師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O626.11
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