發(fā)布時(shí)間：2018-09-09 08:13

【摘要】：芳胺類物質(zhì)廣泛應(yīng)用于精細(xì)化工、燃料、醫(yī)藥等很多領(lǐng)域。通過硝芳基化合物催化加氫還原制備芳胺類物質(zhì)的過程,由于具有環(huán)境友好、易操作等優(yōu)點(diǎn),已經(jīng)成為目前生產(chǎn)芳胺類物質(zhì)最常用的方法。而在催化加氫過程中,高效的催化劑對(duì)于生產(chǎn)芳胺類化合物的生產(chǎn)成本和產(chǎn)品質(zhì)量具有重要影響。在本文中,主要制備了兩種負(fù)載型Pt基納米催化劑,用于4-硝基苯酚(4-NP)催化還原制備4-氨基苯酚(4-AP)的過程,研究納米催化劑在加氫反應(yīng)中的催化性能。主要包括:1、鉑修飾負(fù)載型鎳(NiPt)納米催化劑的制備首先,以葡萄糖碳化后的產(chǎn)物為還原劑,水滑石為載體制備得到了負(fù)載型鉑納米催化劑。其次再高溫煅燒得到鉑修飾負(fù)載型鎳納米催化劑。具體內(nèi)容為:采用類似成核/晶化隔離法制備得到鎳鋁水滑石(NiAl-LDH)前軀體,將NiAl-LDH前軀體與葡萄糖溶液混合,在晶化過程中,加入氯鉑酸,使晶化過程與還原過程同時(shí)進(jìn)行,從而制得高度分散的負(fù)載型鉑納米催化劑(Pt@LDH/C)。將Pt@LDH/C高溫煅燒得到鉑修飾負(fù)載型鎳納米催化劑(NiPt)。通過調(diào)變焙燒溫度考察了制備條件對(duì)納米催化劑形貌結(jié)構(gòu)的影響,最終確定出最優(yōu)的制備條件。2、納米催化劑的形貌和Pt的負(fù)載量對(duì)催化性能的影響在最佳的制備條件下,改變鉑的負(fù)載量,制備出一系列鉑負(fù)載量不同的NiPt納米催化劑,并對(duì)納米催化劑的結(jié)構(gòu)形貌等進(jìn)行了一系列的表征,考察了納米催化劑的催化性能。結(jié)果表明:當(dāng)鉑的理論負(fù)載量為0.6%時(shí),納米催化劑的活性最高。3、以生物質(zhì)為原料熔鹽法制備生物多孔炭(PC)催化劑載體在本研究中,生物質(zhì)通過一個(gè)簡(jiǎn)單的熔鹽合成過程轉(zhuǎn)化為多孔炭。通過這種方法碳化和活化過程能夠一步完成,并且由于熔鹽氯化鋅提供了一個(gè)較好的熔融環(huán)境,所以,碳化時(shí)間和溫度顯著的降低了。多孔炭的性質(zhì)通過XRD、TG-DSC、SEM、TEM、FT-IR和BET吸脫附等溫線表征。結(jié)果表明制備的多孔炭是無定形的,具有分級(jí)孔結(jié)構(gòu)并且比表面積高達(dá)1642 m2g-1,表面富含多種官能團(tuán)。這些官能團(tuán)能夠提供較多的吸附位點(diǎn)。4、二氧化錫與多孔炭復(fù)合物的制備及其對(duì)Pt納米催化劑的負(fù)載與催化性能研究首先,用溶劑熱法制備二氧化錫-多孔炭(SnO_2-PC)復(fù)合物。然后,再以乙二醇(EG)為還原劑,SnO_2-PC復(fù)合物為載體,制備得到了負(fù)載型鉑納米催化劑(Pt@SnO_2-PC)。具體內(nèi)容為:以氯化亞錫為錫源,堿性乙醇為還原劑和溶劑,在溶劑熱的條件下與多孔炭混合,制備出SnO_2-PC復(fù)合物。然后,再以此復(fù)合物為載體,以EG為還原劑,在乙二醇/水體系中,通過溶劑熱法制備Pt@SnO_2-PC。并對(duì)納米催化劑的結(jié)構(gòu)形貌等進(jìn)行了一系列的表征,考察了納米催化劑的催化性能。確定出氧化物對(duì)納米催化劑活性的影響。結(jié)果表明:SnO_2-PC對(duì)實(shí)驗(yàn)無催化作用;在相同Pt負(fù)載量的情況下,與Pt@PC相比,Pt@SnO_2-PC具有較高的活性。說明SnO_2對(duì)催化具有促進(jìn)作用。
[Abstract]:Aromatic amines are widely used in many fields, such as fine chemical industry, fuel, medicine and so on. The process of preparing aromatic amines by catalytic hydrogenation reduction of nitroaryl compounds has become the most commonly used method for the production of aromatic amines because of its environmental friendliness and ease of operation. In the process of catalytic hydrogenation, the efficient catalyst has an important effect on the production cost and product quality of aromatic amines. In this paper, two kinds of supported Pt based nanocatalysts were prepared for the catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). The main results are as follows: (1) Platinum modified supported nickel (NiPt) nanocatalysts were prepared. Firstly, supported platinum nanocatalysts were prepared by using glucose carbonized products as reducing agent and hydrotalcite as support. Secondly, platinum modified supported nickel nanocatalysts were obtained by calcining at high temperature. The main contents are as follows: the nickel aluminum hydrotalcite (NiAl-LDH) precursor was prepared by similar nucleation / crystallization isolation method. The NiAl-LDH precursor was mixed with glucose solution. In the process of crystallization, chloroplatinic acid was added, so that the crystallization process and the reduction process were carried out simultaneously. A highly dispersed supported platinum nanocatalyst (Pt@LDH/C) was prepared. Preparation of Platinum modified Nickel Nano-catalyst (NiPt). By calcining Pt@LDH/C at High temperature The effects of preparation conditions on the morphology and structure of nano-catalysts were investigated by changing the calcination temperature, and the optimum preparation conditions were determined. The effects of the morphology of nano-catalysts and the amount of Pt loading on the catalytic performance were obtained under the optimum preparation conditions. A series of NiPt nanocatalysts with different platinum loading were prepared by changing the loading amount of platinum. The structure and morphology of the nanocrystalline catalysts were characterized and the catalytic properties of the nanocrystalline catalysts were investigated. The results showed that when the theoretical loading amount of platinum was 0.6, the activity of nanometer catalyst was the highest. The bioporous carbon (PC) catalyst carrier was prepared by using biomass as raw material and molten salt as raw material in this study. Biomass is converted into porous carbon through a simple molten salt synthesis process. The carbonation and activation process can be completed in one step by this method, and the carbonation time and temperature are significantly reduced because the molten salt zinc chloride provides a better melting environment. The properties of porous carbon were characterized by XRD,TG-DSC,SEM,TEM,FT-IR and BET adsorption isotherms. The results show that the prepared porous carbon is amorphous, with a graded pore structure and a specific surface area of 1642 m2g-1.The surface is rich in various functional groups. These functional groups can provide more adsorption sites. 4. Preparation of Sno _ 2 / porous carbon complexes and their support and catalytic performance on Pt nanocatalysts. Firstly, solvothermal synthesis of tin dioxide / porous carbon (SnO_2-PC) complexes is studied. Then the supported platinum nanocatalyst (Pt@SnO_2-PC) was prepared by using ethylene glycol (EG) as the reductant Sno _ 2-PC complex as the carrier. The main contents are as follows: using stannous chloride as tin source, alkaline ethanol as reducing agent and solvent, the SnO_2-PC complex was prepared by mixing with porous carbon under solvothermal conditions. Then, using this complex as carrier and EG as reducing agent, Pt@SnO_2-PC. was prepared by solvothermal method in ethylene glycol / water system. The structure and morphology of the nanocatalysts were characterized and the catalytic properties of the nanocrystalline catalysts were investigated. The effect of oxide on the activity of nanometer catalyst was determined. The results show that: SnO2-PC has no catalytic effect on the experiment, and PtSn-SnO2-PC has higher activity than Pt@PC under the same Pt loading. The results show that SnO_2 can promote the catalysis.
【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O643.36;TQ243.1

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