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  本文選題：檸檬醛加氫 + 碳化鉬��； 參考：《華東理工大學》2017年碩士論文

【摘要】：α,β-不飽和醛/酮及其加氫產(chǎn)物為農(nóng)化、醫(yī)藥、精細化工、食品工業(yè)等領(lǐng)域提供了豐富的化工原料及中間體。近年來,對于該類有機物合成的探索日益增多,現(xiàn)有研究主要集中在貴金屬催化劑,較高的商業(yè)成本和性能的不理想是此類催化劑在該反應(yīng)中實現(xiàn)工業(yè)化的瓶頸。碳化鉬作為催化材料具有與鉑、鈀等貴金屬相近的催化加氫效能,而被譽為"類鉑催化劑",利用過渡金屬碳化物對貴金屬催化劑作為替代是一個解決貴金屬資源緊張和降低使用成本的有效途徑,有利于豐富碳化鉬種類完善制備理論和工藝,對該類催化材料應(yīng)用范圍的拓寬具備實踐意義。本論文工作以鉬酸銨和有機胺(苯胺、十二胺、乙二胺、吡啶和四乙烯五胺等)為原料,通過有機-無機雜化法利用共沉淀首先得到特定形貌(納米線、層狀、長方體及片層堆積)的M_oO_x/amine前軀體,再采用程序升溫反應(yīng)法在氮氣中高溫熱解前軀體進行滲碳反應(yīng),制備出多種碳化鉬催化劑。嘗試以1,6-己二胺、1,2-丙二胺為客體在前軀體合成時加入氧化劑APS,得到了形貌了枝狀前軀體和暴露(101)晶面的介孔M_oC材料。同時,引入CTAB、SDS、PEG-1500等考察表面活性劑對所合成前軀體形貌的影響,探索其影響機制及規(guī)律。采用SEM、TEM、XRD、TGA等表征手段對樣品進行物性分析,比較不同制備過程對樣品造成的性質(zhì)差異,總結(jié)調(diào)控規(guī)律。以非貴金屬催化劑檸檬醛選擇性加氫制備橙花醇/香葉醇的反應(yīng),對碳化鉬樣品的選擇性加氫效能能進行考察,提出將碳化鉬作為精細化工中選擇性加氫反應(yīng)催化劑的新思路。研究結(jié)果表明:在水溶液中通過改變雜化前軀體中有機胺的種類可得到形貌和晶面可調(diào)的體相碳化鉬,并達到增大比表面積的效果。雜化過程中引入表面活性劑對晶粒形貌和分散性都有不同程度的改善。采用有機-無機雜化法制備的體相碳化鉬對檸檬醛催化加氫的轉(zhuǎn)化率可達88%,選擇性受暴露晶面的不同而體現(xiàn)較大差異性。
[Abstract]:偽, 尾 -unsaturated aldehydes / ketones and their hydrogenation products provide abundant chemical raw materials and intermediates for agrochemical, pharmaceutical, fine chemical, food industry and so on.In recent years, more and more researches have been made on the synthesis of this kind of organic compounds. The existing researches mainly focus on noble metal catalysts. The high commercial cost and unsatisfactory performance are the bottleneck of industrialization of this kind of catalysts.Molybdenum carbide as a catalytic material has similar catalytic hydrogenation performance to platinum, palladium and other precious metals.The transition metal carbide is an effective way to solve the shortage of precious metal resources and reduce the cost of use. It is beneficial to enrich the preparation theory and technology of molybdenum carbide.It is of practical significance to widen the scope of application of this kind of catalytic materials.In this paper, ammonium molybdate and organic amines (aniline, dodecylamine, ethylenediamine, pyridine and tetraethylenepentylamine) were used as raw materials.The M_oO_x/amine precursor of cuboid and lamellar) was prepared by using programmed temperature reaction method to carburize the precursor body at high temperature in nitrogen to prepare various molybdenum carbide catalysts.A mesoporous M_oC material with dendritic precursor and exposed crystal plane was obtained by adding oxidizer APSs in the synthesis of prosomas by using 1Hexanediamine as the guest.At the same time, the influence of surfactant on the morphology of the precursor was investigated by introducing CTABX SDS- PEG-1500, and the mechanism and regularity of the influence were explored.The physical properties of the samples were analyzed by means of SEMTEMX XRDGA, and the properties of different preparation processes were compared, and the regulation rules were summarized.Selective hydrogenation of citral to hesperol / geraniol was carried out on a non-noble metal catalyst. The performance of selective hydrogenation of molybdenum carbide samples was investigated. A new idea of using molybdenum carbide as a catalyst for selective hydrogenation in fine chemical industry was put forward.The results show that molybdenum carbide with adjustable morphology and crystal plane can be obtained by changing the kinds of organic amines in the hybrid body in aqueous solution, and the effect of increasing the specific surface area can be achieved.The addition of surfactants in the hybrid process improves the grain morphology and dispersity in varying degrees.The conversion of molybdenum carbide prepared by organic-inorganic hybrid method for catalytic hydrogenation of citral can reach 88%.
【學位授予單位】：華東理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36

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