由生物质糖类一锅法制备2，5二羟甲基四氢呋喃的研究
发布时间：2018-10-26 09:40
【摘要】：如今,许多发达国家,都在致力于研究开发和研究新型高效的和低污染乃至无污染的生物质利用技术,以达到替代或是缓解化石类不可再生能源的利用的目的,进而为实现经济的可持续发展提供根本的保障。呋喃类衍生物是生物质和可替代部分化石能源的化学品之间的桥梁,本篇文章中,就生物质果糖的至2,5-二羟甲基四氢呋喃的转化展开了研究:(1)首先对生物质和可替代部分化石能源的化学品之间的桥梁—5-羟甲基糠醛(5-HMF)的加氢制备2,5-二羟甲基四氢呋喃(DHMTHF)的反应进行了研究。本章采用了传统浸渍法制备得到Ru/SiO2 Aerogel催化剂,用于5-羟甲基糠醛到2,5-二羟甲基四氢呋喃的完全加氢反应当中,获得了100%的5-HMF转化率和98%的DHMTHF选择性,该方法具有操作简单、高效的优点。催与目前报道的文献中钌催化剂相比,该催化剂在相对温和的反应条件下得到了很高的得率。(2)本章中我们选用非均相固体酸催化剂于果糖转化制备5-羟甲基糠醛反应体系,结合我们之前对于5-HMF下游转化加氢制备2,5-二羟甲基四氢呋喃(DHMTHF)体系的研究,在水相和双相体系中运用目前已商品化的固体酸催化剂Amberlyst-15与金属催化剂Ru/NH2CH3-MSNs一锅法由果糖制备2,5-二羟甲基四氢呋喃。我们在第一部分工作的基础上,提出利用胺基甲基双修饰的介孔二氧化硅小球作NH2CH3-MSNs载体,浸渍法负载金属钌,与固体酸催化剂Amberlyst-15机械混合用于果糖一锅法制备2,5-二羟甲基四氢呋喃反应当中,在纯水相和双相体系中做了尝试,分别得到20%和39.8%2,5-二羟甲基四氢呋喃得率。(3)本章我们设计制备了具有yolk-shell结构的钌基负载型催化剂(Ru/CH3NH2-MNSs@SiO2-SO3H),用于果糖一步法制备2,5-二羟甲基四氢呋喃(DHMTHF)的研究。用该催化剂完成一锅法果糖脱水加氢制备DHMTHF。该材料的外壳上嫁接磺酸基,用于果糖脱水制备5-羟甲基糠醛,进而与材料中心核负载的金属钌作用,用于5-羟甲基糠醛的加氢反应。我们将Yolk-Shell双功能催化剂用于果糖一步法制备2,5-二羟甲基四氢呋喃反应当中,在纯水相体系中做了尝试,得到了相对较高的HMF产率,但离我们预期目标高产率的制备DHMTHF还有差距。
[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.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626.11
本文编号：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.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626.11
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