本文關鍵詞： 甲醇水蒸氣重整制氫 Ni基催化劑 Cu基催化劑 Pr Sm　出處：《昆明理工大學》2017年碩士論文　論文類型：學位論文

【摘要】：甲醇是最簡單的醇類,來源廣泛,含氫量高,含硫量低(5ppm)。因為甲醇不含C-C鍵,所以在甲醇水蒸氣重整制氫(SMR)過程中所需反應溫度低(200-350℃),產生的副產物少。甲醇水蒸氣重整制氫能夠為燃料電池提供高純度低CO的氫氣,被認為是極具應用前景的制氫技術。Ni能促進C-C鍵、O-H鍵和C-H鍵的斷裂因此被應用于甲醇水蒸氣重整制氫當中,但Ni基催化劑的催化反應需要的反應溫度較高。Cu基催化劑因其高活性和對氫氣的高選擇性而被廣泛的應用于甲醇水蒸氣重整制氫,但是Cu的金屬穩(wěn)定性低,極易燒結致使催化劑失活,因此,選取Ni和Cu改性。本論文研究了稀土金屬Pr和Sm負載到Ni基和Cu基催化劑當中對甲醇水蒸氣重整制氫催化性能的影響,著重考察了稀土負載量對催化劑性能的影響,并且通過XRD、H2-TPR、XPS、Raman、TGA、O2-TPO、TEM和HAADF/STEM等表征手段深入研究了稀土金屬對催化劑結構特性的影響與催化活性之間的相互關系。主要研究結果如下:(1)探究了 Pr負載到Ni/Al2O3催化劑上對催化活性的影響。采用等體積浸漬法制備了不同Pr負載量的Ni/Al2O3催化劑,結果表明,Pr負載量低于12.5%時,催化劑的在甲醇水蒸氣重整制氫中催化活性得到提高,Pr的最佳負載量為10%;Pr使得Ni/Al203催化劑當中NiO從NiAl204中脫離,催化劑還原后形成了Pr6O11@Ni/NiO超級結構,得到更多的活性金屬Ni,提高了催化劑的催化性能;Ni/Al2O3催化劑在本試驗條件中僅有少量活性炭形成,Pr的存在可以減少催化劑表面的活性炭并且提高催化劑的催化穩(wěn)定性。(2)考察了 Sm的添加對Cu/Al203催化劑催化活性的影響。將Sm負載到Cu/A1203催化劑中,催化劑在甲醇水蒸氣重整制氫中的催化活性隨Sm負載量增加而降低;Sm的添加抑制了 Cu/Al2O3中CuO的還原,不利于CuO的形成;Sm使得Cu在催化劑表面形成團聚,使得其顆粒增大,減少了 Cu的總表面積,使得催化劑催化活性顯著降低。(3)研究了 Sm負載量與Ni/Al203催化劑催化活性的關系。Sm的負載量在5-10%之間時,催化活性隨Sm負載量增加而提升,最佳負載量為10%;Sm與Pr一樣,也能夠使NiO從NiAl204中脫離,但是稀土金屬負載量達到12.5%以上時,負載Sm的Ni/Al203催化劑催化性能低于負載相同含量Pr的Ni/Al203催化劑;浸漬時間為12h時所得催化劑催化性能高于浸漬時間為Oh和24h的催化劑,干燥時間為24h時,催化劑性能高于干燥時間為4h的催化劑。
[Abstract]:Methanol is one of the most simple alcohols, wide source, high hydrogen content, low sulfur content (5ppm). Because methanol does not contain C-C key, so in the methanol steam reforming (SMR) reaction temperature required in the process of low (200-350 DEG C), byproducts. The steam reforming of methanol and hydrogen can provide the hydrogen with high purity and low CO for fuel cell is considered to be promising hydrogen production technology of.Ni can promote the C-C bond cleavage of the O-H bond and C-H bond are therefore used in methanol steam reforming for hydrogen production, but the required reaction temperature catalytic reaction of Ni based catalysts with high.Cu catalyst for its high activity and the hydrogen selectivity and is widely used in the methanol steam reforming for hydrogen production, but the metal stability of Cu is low, easy to cause the sintering deactivation of the catalyst, therefore, selected Ni and Cu modified. This paper studies the rare earth metals Pr and Sm load to the Ni based and Cu based catalysts Effect of methanol steam reforming for hydrogen production by catalytic performance, focuses on the influence of loading on the catalytic performance of rare earth, and through XRD, H2-TPR, XPS, Raman, TGA, O2-TPO, TEM and HAADF/STEM were used to study the relationship between the effect of rare earth metal on properties of the catalyst structure and catalytic activity. The main results are as follows: (1) to explore the Pr load to the Ni/Al2O3 catalyst on the catalytic activity. The effects of the Ni/Al2O3 catalysts with different Pr loadings prepared by impregnation method. The results show that the Pr load is lower than 12.5%, the catalyst in methanol steam reforming for hydrogen production in catalytic activity was improved and the optimal loading Pr 10%; Pr NiO NiAl204 from the Ni/Al203 catalyst in the catalyst formed from Pr6O11@Ni/NiO super structure, obtained more active metal Ni, improved catalyst The catalytic performance of Ni/Al2O3 catalyst; only a small amount of activated carbon is formed in the condition of this experiment, the presence of Pr can reduce the activated carbon on the catalyst surface and improve the catalytic stability of the catalyst. (2) investigated the effect of Sm addition on the catalytic activity of Cu/Al203 catalyst. The load will Sm to the Cu/A1203 catalyst, the catalyst in the methanol steam reforming catalyst the activity of hydrogen production with the loading amount of Sm increased; the addition of Sm inhibited the reduction of Cu/Al2O3 in CuO, is not conducive to the formation of CuO; Sm makes Cu agglomeration on the catalyst surface, the particle size, reduce the total surface area of Cu, the catalytic activity decreased significantly. (3) the research on load the amount of.Sm Sm load Ni/Al203 catalyst catalytic activity and the catalytic activity in 5-10%, as Sm loading increased, the best load was 10%; Sm and Pr, also can make NiO from The NiAl204 detachment, but rare earth metal loading reached more than 12.5%, the catalytic properties of Sm supported Ni/Al203 is lower than that of the catalyst Ni/Al203 the same content of Pr; the soaking time was 12h higher than that of the catalytic performance of catalyst impregnation time as catalyst Oh and 24h, the drying time is 24h, the catalyst performance is higher than that of dry time is 4H the catalyst.

【學位授予單位】：昆明理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36;TQ116.2

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