本文選題：鈀金屬催化劑 + 二氧化鈦��； 參考：《南京大學(xué)》2015年博士論文

【摘要】：雙烯烴和炔烴選擇性加氫是重要的石油化工和精細化工過程。本工作用微型催化反應(yīng)評價和工業(yè)側(cè)線反應(yīng)評價結(jié)合X-射線粉末衍射(XRD)、比表面積和孔結(jié)構(gòu)測試、CO吸附、熱重-差熱分析(TG-DTA)等多種物理化學(xué)手段研究了納米Ti02為載體的負載型納米鈀金屬催化劑長鏈正構(gòu)雙烯選擇性加氫反應(yīng)性能,系統(tǒng)和深入地探討了納米Pd/TiO2催化劑成型工藝、載體孔結(jié)構(gòu)、催化劑幾何形狀、Pd金屬在成型后的Ti02載體上的分布對催化劑長鏈正構(gòu)雙烯烴選擇性加氫反應(yīng)性能的影響,初步探討了納米碳管(CNTs)為載體的負載型納米鈀金屬催化劑乙炔選擇性加氫反應(yīng)性能,為開發(fā)雙烯烴和炔烴高選擇性加氫實用新型納米催化劑提供了重要參考信息。主要研究結(jié)果如下：1.發(fā)明了一種負載型納米Pd/TiO2催化劑成型新方法。將Pd/TiO2粉末催化劑先經(jīng)氫還原處理,再以A1203為粘結(jié)劑擠出成型,在高純氮氣保護下進行熱處理。所制備的納米Pd/TiO2成型催化劑具有優(yōu)良機械強度和長鏈正構(gòu)雙烯選擇性加氫反應(yīng)性能。系統(tǒng)地研究了不同造孔劑對成型后納米Ti02載體孔結(jié)構(gòu)以及Pd/TiO2和催化劑長鏈正構(gòu)雙烯選擇性加氫反應(yīng)的影響,發(fā)現(xiàn)以硬脂酸鋁為造孔劑的Pd/TiO2催化劑具有優(yōu)良的長鏈正構(gòu)雙烯選擇性加氫性能。2.發(fā)現(xiàn)成型的負載型納米Pd/TiO2催化劑幾何形狀以及活性組份Pd金屬在Ti02載體上分布方式對催化劑長鏈正構(gòu)雙烯選擇性加氫反應(yīng)性能有一定影響。三葉草形Pd/TiO2催化劑比圓柱形Pd/TiO2催化劑具有更優(yōu)良的長鏈正構(gòu)雙烯選擇性加氫反應(yīng)性能�；钚越M份Pd金屬在三葉草形TiO2載體上呈非均勻的殼型分布的催化劑比均勻分布的催化劑具有更高的長鏈正構(gòu)雙烯加氫選擇性。3.研制了不含其它粘結(jié)劑的純Ti02三葉草形載體,以其負載的Pd金屬催化劑經(jīng)工業(yè)側(cè)線反應(yīng)評價,結(jié)果表明其長鏈正構(gòu)雙烯選擇性加氫反應(yīng)性能優(yōu)良、運行穩(wěn)定。4.發(fā)現(xiàn)碳納米管(CNTs)為載體的負載型鈀金屬催化劑活性金屬Pd在管內(nèi)外表面的分布狀態(tài)以及載體管徑大小對催化劑乙炔選擇性加氫反應(yīng)性能有很大影響。Pd金屬分布在CNTs管外表面比分布在內(nèi)表面具有更高的生成乙烯選擇性,這是因為位于管外的Pd與CNTs載體發(fā)生電子相互作用導(dǎo)致Pd金屬具有更高的電荷密度；Pd金屬分布在CNTs管外表面的催化劑,管徑減小乙炔轉(zhuǎn)化率降低,這是由于管徑較小的CNTs外表面電荷密度較大,與管外的Pd金屬電子相互作用更強。
[Abstract]:Selective hydrogenation of diolefins and alkynes is an important petrochemical and fine chemical process. In this work, micro-catalytic reaction evaluation and industrial side-line reaction evaluation combined with X- ray powder diffraction (XRDX), specific surface area and pore structure were used to test CO adsorption. Various physical and chemical methods, such as thermogravimetric differential thermal analysis (TG-DTA), were used to study the selective hydrogenation of long chain n-diene over supported nano-palladium metal catalyst (Ti02). The forming process of nanocrystalline Pd/TiO2 catalyst was systematically and deeply discussed. The effect of pore structure and geometry of catalyst on the selective hydrogenation of long chain diolefin on Ti02 carrier was investigated. The selective hydrogenation of acetylene over supported nano-palladium metal catalyst supported on carbon nanotubes (CNTs) was preliminarily discussed, which provided important reference information for the development of high selectivity hydrogenation of diolefin and alkynes. The main results are as follows: 1. A new forming method of supported nano Pd/TiO2 catalyst was invented. Pd/TiO2 powder catalyst was treated by hydrogen reduction, then extruded with A1203 as binder, and then heat treated under the protection of high purity nitrogen. The nanocrystalline Pd/TiO2 catalyst has excellent mechanical strength and long chain diene selective hydrogenation performance. The effects of different pore-making agents on the pore structure of nano-scale Ti02 carrier and the selective hydrogenation of Pd/TiO2 and catalyst were studied. It was found that the Pd/TiO2 catalyst with aluminum stearate as pore-making agent had excellent selective hydrogenation performance of long chain n-diene. It was found that the geometry of the Pd/TiO2 catalyst and the distribution of PD metal on the Ti02 support had a certain effect on the selective hydrogenation of long chain n-diene. Clover Pd/TiO2 catalyst has better performance in selective hydrogenation of long chain normal diene than cylindrical Pd/TiO2 catalyst. The hydrogenation selectivity of the active component PD metal on the clover TiO2 support is higher than that of the homogeneous catalyst with a long chain diene hydrogenation. A pure Ti02 clover carrier without other binders was prepared. Its supported PD metal catalyst was evaluated by industrial side-line reaction. The results showed that the long chain n-diene selective hydrogenation reaction was excellent and the operation was stable .4. It is found that the distribution of active metal PD on the surface of the supported palladium metal catalyst and the diameter of the support tube have great influence on the catalytic performance of selective hydrogenation of acetylene. The outer surface of CNTs tube has higher ethylene selectivity than that of distributed inner surface. This is due to the electron interaction between PD and CNTs support outside the tube, which results in higher charge density of PD metal and lower acetylene conversion due to the distribution of PD metal on the outer surface of CNTs tube. This is due to the larger charge density on the outer surface of CNTs with smaller tube diameter and stronger interaction with PD metal electrons outside the tube.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：O643.36;TB383.1

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