本文關(guān)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(xué)》2017年碩士論文　論文類型：學(xué)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?yàn)榧状疾缓珻-C鍵,所以在甲醇水蒸氣重整制氫(SMR)過程中所需反應(yīng)溫度低(200-350℃),產(chǎn)生的副產(chǎn)物少。甲醇水蒸氣重整制氫能夠?yàn)槿剂想姵靥峁└呒兌鹊虲O的氫氣,被認(rèn)為是極具應(yīng)用前景的制氫技術(shù)。Ni能促進(jìn)C-C鍵、O-H鍵和C-H鍵的斷裂因此被應(yīng)用于甲醇水蒸氣重整制氫當(dāng)中,但Ni基催化劑的催化反應(yīng)需要的反應(yīng)溫度較高。Cu基催化劑因其高活性和對(duì)氫氣的高選擇性而被廣泛的應(yīng)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(jié)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(fù)載到Ni基和Cu基催化劑當(dāng)中對(duì)甲醇水蒸氣重整制氫催化性能的影響,著重考察了稀土負(fù)載量對(duì)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(duì)催化劑結(jié)構(gòu)特性的影響與催化活性之間的相互關(guān)系。主要研究結(jié)果如下:(1)探究了 Pr負(fù)載到Ni/Al2O3催化劑上對(duì)催化活性的影響。采用等體積浸漬法制備了不同Pr負(fù)載量的Ni/Al2O3催化劑,結(jié)果表明,Pr負(fù)載量低于12.5%時(shí),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(fù)載量為10%;Pr使得Ni/Al203催化劑當(dāng)中NiO從NiAl204中脫離,催化劑還原后形成了Pr6O11@Ni/NiO超級(jí)結(jié)構(gòu),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(yàn)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(duì)Cu/Al203催化劑催化活性的影響。將Sm負(fù)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(fù)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(tuán)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(fù)載量與Ni/Al203催化劑催化活性的關(guān)系。Sm的負(fù)載量在5-10%之間時(shí),催化活性隨Sm負(fù)載量增加而提升,最佳負(fù)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(fù)載量達(dá)到12.5%以上時(shí),負(fù)載Sm的Ni/Al203催化劑催化性能低于負(fù)載相同含量Pr的Ni/Al203催化劑;浸漬時(shí)間為12h時(shí)所得催化劑催化性能高于浸漬時(shí)間為Oh和24h的催化劑,干燥時(shí)間為24h時(shí),催化劑性能高于干燥時(shí)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(xué)位授予單位】：昆明理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;TQ116.2

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