發(fā)布時(shí)間：2018-03-09 22:32

  本文選題：Rochow反應(yīng)　切入點(diǎn)：M2　出處：《中國科學(xué)院大學(xué)(中國科學(xué)院過程工程研究所)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：甲基氯硅烷是最重要也是用量最大的有機(jī)硅單體,是整個(gè)有機(jī)硅工業(yè)的基礎(chǔ)和支柱。工業(yè)生產(chǎn)中,其主要是采用直接法(即Rochow反應(yīng))來合成。采用固態(tài)的硅粉(Si)在銅基催化作用下與氣態(tài)的一氯甲烷(MeC1)接觸反應(yīng),目標(biāo)產(chǎn)物為二甲基二氯硅烷(M2,Me2SiCl2)。銅基催化劑是該反應(yīng)的經(jīng)典催化劑,然而,目前的研究主要集中于微米尺度銅催化劑的開發(fā),且催化性能即M2選擇性和Si轉(zhuǎn)化率仍然有待進(jìn)一步提高。因此,開發(fā)新型高效催化體系及探索其催化機(jī)理仍然是一項(xiàng)具有理論和實(shí)際應(yīng)用價(jià)值的研究課題�；诖�,本論文開展了以下研究工作:(1)在采用液相還原法制備金屬Cu納米線基礎(chǔ)上,通過調(diào)控溫度和時(shí)間氧化制備了一系列含有不同Cu、Cu_2O和CuO組分的納米線和納米管材料,并將其用于Rochow反應(yīng)中。相較于一元和二元組分催化劑,三元Cu-Cu_2O-CuO多壁核殼納米線表現(xiàn)出更加優(yōu)異的M2選擇性和Si轉(zhuǎn)化率。這歸因于三元層狀異質(zhì)結(jié)構(gòu)及不同組元間的協(xié)同作用。(2)采用六面體、八面體和菱形十二面體三種Cu_2O納米晶作為模型催化體系研究了晶面對(duì)Rochow反應(yīng)催化性能的影響。實(shí)驗(yàn)結(jié)果表明暴露{100}晶面的Cu_2O六面體M2的催化選擇性最優(yōu),這歸因于其表面結(jié)構(gòu)對(duì)MeC1的解離吸附最強(qiáng)。在此基礎(chǔ)上將ZnO納米粒子負(fù)載在不同晶面的Cu_2O納米晶上得到5%ZnO/Cu_2O異質(zhì)結(jié)納米晶,催化性能顯示負(fù)載于六面體Cu_2O的異質(zhì)結(jié)納米晶表現(xiàn)出更加優(yōu)異的M2選擇性和Si轉(zhuǎn)化率,證實(shí)其形成的P-N異質(zhì)結(jié)構(gòu)對(duì)催化性能具有促進(jìn)作用。(3)采用硬模板法制備了一種多孔CuO-ZnO納米復(fù)合物,并將其回用于Rochow反應(yīng)中。本方法是以回收的有機(jī)硅單體合成反應(yīng)中的廢觸體為原料。質(zhì)量占比67wt%的炭黑制備的CZ80/20復(fù)合物與商業(yè)催化劑的催化性能基本相當(dāng),這得益于二元組分比例及二者的協(xié)同作用。本方法對(duì)循環(huán)工藝的發(fā)展進(jìn)行了有益的探索。
[Abstract]:Methyl chlorosilane is the most important and the largest amount of silicone monomer. It is the foundation and pillar of the whole organosilicon industry. It is mainly synthesized by direct method (i.e. Rochow reaction). The solid silica fume is used to react with gaseous methylene chloride (MeC1) under the catalysis of copper. The target product is dimethyl dichlorosilane M _ 2N _ 2M _ 2i _ 2SiCl _ 2H _ 2O. Cu-based catalyst is the classic catalyst for this reaction. However, the current research is mainly focused on the development of micron scale copper catalyst. The selectivity of M2 and the conversion of Si still need to be further improved. Therefore, it is still a research topic with theoretical and practical application value to develop a new type of highly efficient catalytic system and explore its catalytic mechanism. In this paper, the following research work was carried out: (1) A series of nanowires and nanotube materials containing different Cu 2O and CuO components were prepared by controlling the temperature and time of oxidation on the basis of liquid phase reduction method to prepare Cu nanowires. And used in Rochow reaction. Compared with monolithic and binary catalyst, Ternary Cu-Cu_2O-CuO multiwalled core-shell nanowires exhibit better M2 selectivity and Si conversion due to ternary layered heterostructures and synergistic effects between different components. The effects of octahedron and rhombohedral 12 Cu_2O nanocrystals on the catalytic performance of Cu_2O hexahedron M2 exposed to {100} plane were investigated as model catalysts. The results showed that the selectivity of Cu_2O hexahedron M2 exposed to {100} faces was optimal. This is attributed to the strongest dissociation and adsorption of MeC1 on its surface structure. On this basis, 5ZnO / Cu _ 2O heterojunction nanocrystals were obtained by loading ZnO nanoparticles onto Cu_2O nanocrystals with different faces. The catalytic properties showed that the heterojunction nanocrystals supported on hexahedron Cu_2O exhibited better M2 selectivity and Si conversion. It is confirmed that the P-N heterostructure has a catalytic effect on the catalytic performance. (3) A porous CuO-ZnO nanocomposite was prepared by hard template method. In this method, the waste thixodes in the synthesis of organic silicon monomers were used as raw materials. The catalytic properties of the CZ80/20 complexes prepared from carbon black with 67 wt% mass ratio were basically equal to those of commercial catalysts. This method is beneficial to the development of recycling process.
【學(xué)位授予單位】：中國科學(xué)院大學(xué)(中國科學(xué)院過程工程研究所)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36

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