本文選題：二甲醚 + 部分氧化　； 參考：《遼寧工業(yè)大學(xué)》2015年碩士論文

【摘要】：二甲醚（DME）穩(wěn)定，無毒，無腐蝕性，且具有較高的含氫量，是一種理想的氫載體。二甲醚的生產(chǎn)技術(shù)已逐步成熟，所以由二甲醚制氫有其可行性。前人的研究多集中于催化劑的篩選與反應(yīng)條件的優(yōu)化上，針對(duì)二甲醚部分氧化重整制氫催化劑的優(yōu)化的工作卻比較少。 本文在針對(duì)二甲醚部分氧化重整制氫反應(yīng)過程與催化劑作用研究基礎(chǔ)上，對(duì)該反應(yīng)的催化劑體系中的重整催化劑進(jìn)行優(yōu)化。主要以堿土金屬對(duì)重整催化劑Ni/Al2O3進(jìn)行改性，并考察了不同Ce:Zr比例的Ni/Ce-Zr-Ox催化劑和Ni基介孔載體催化劑的反應(yīng)性能，比較了催化劑優(yōu)化效果。 以堿土金屬（Mg、Ca、Sr、Ba）對(duì)重整催化劑Ni/Al2O3進(jìn)行改性， MgO的加入會(huì)提高NiAl2O4的結(jié)晶度與穩(wěn)定性，在催化劑還原過程中生成的Ni含量較少，且趨于納米粒子，因而活性高，穩(wěn)定性好，催化劑性能優(yōu)于未改性的催化劑；而Ca、Sr、Ba改性的催化劑沒有促進(jìn)NiAl2O4的結(jié)晶，在低溫下即被還原，其性能不如未改性的。 Mg加入量改性的研究表明，7.5%MgO、10%MgO改性均能夠提高Ni/Al2O3的催化活性，但7.5%MgO改性的催化劑中NiAl2O4穩(wěn)定性適宜，，能夠在還原時(shí)形成適量的Ni活性中心，所以7.5%MgO改性的催化劑效果更明顯。 不同Ce:Zr比例的Ni/Ce-Zr-Ox催化劑的反應(yīng)性能均優(yōu)于Ni/Al2O3的反應(yīng)性能，其中Ce:Zr比為1:4的催化劑效果最優(yōu)，因?yàn)樵贑e:Zr=1:4的載體中形成結(jié)晶度適宜的鈰鋯固溶體，在固溶體的影響下NiO顆粒較小，同時(shí)鈰鋯固溶體因其獨(dú)特的氧化還原性質(zhì)提高活性組分NiO的分散度，使得催化劑活性及穩(wěn)定性均有所提升。 三種Ni基介孔載體催化劑（Ni/介孔Al2O3、介孔Ni-7.5%MgO-Al2O3與Ni/介孔7.5%MgO-Al2O3）都在較低溫度下，即會(huì)有較大量Ni被還原出來而形成多原子活性中心，無論是氫氣收率還是含碳產(chǎn)物選擇性均不如Ni/Al2O3催化劑的催化性能。最后對(duì)比發(fā)現(xiàn)，7.5%MgO改性的Ni/Al2O3催化劑優(yōu)于的Ni/Ce-Zr-Ox(Ce:Zr=1:4)催化劑。
[Abstract]:DMEs are stable, non-toxic, non-corrosive, and have high hydrogen content, which is an ideal hydrogen carrier. The production technology of dimethyl ether has matured gradually, so it is feasible to produce hydrogen from dimethyl ether. Previous studies have focused on the selection of catalysts and optimization of reaction conditions, but less work has been done on the optimization of catalysts for partial oxidative reforming of dimethyl ether for hydrogen production. Based on the study of the reaction process of partial oxidative reforming of dimethyl ether for hydrogen production and the reaction of catalyst, the reforming catalyst in the catalyst system of this reaction was optimized. The Ni / Al _ 2O _ 3 reforming catalyst was modified by alkali earth metal, and the reaction performance of Ni / Ce-Zr-Ox catalyst with different ce: Zr ratio and Ni / Ce-Zr-Ox catalyst was investigated, and the optimum performance of the catalyst was compared. The Ni / Al _ 2O _ 3 reforming catalyst was modified by alkaline earth metal (MgO). The addition of MgO can improve the crystallinity and stability of NiAl _ 2O _ 4. The Ni content produced in the reduction process of the catalyst is less and tends to nanometer particles, so it has high activity and good stability. The catalytic performance of the catalyst was better than that of the unmodified catalyst, while the catalyst modified by CaOSR-Ba did not promote the crystallization of NiAl _ 2O _ 4 and was reduced at low temperature. The results of mg addition showed that the modified Ni / Al _ 2O _ 3 catalyst could improve the catalytic activity of Ni / Al _ 2O _ 3, but the Ni _ (Al _ 2O _ 4) _ 4 catalyst modified by 7.5MgO was suitable for the stability of Ni _ (Al _ 2O _ 4) and formed a proper amount of Ni _ 2O _ 3 active center during the reduction. So the effect of 7.5 MgO modified catalyst is more obvious. The reaction performance of Ni / Ce-Zr-Ox catalyst with different ce: Zr ratio is better than that of Ni / Al _ 2O _ 3. The catalyst with ce: Zr ratio of 1:4 is the best, because the cerium-zirconium solid solution with suitable crystallinity is formed in the support of ce: Zr-1: 4, and the nio particle is smaller under the influence of solid solution. At the same time, the cerium zirconium solid solution increased the dispersion of nio because of its unique redox property, which improved the activity and stability of the catalyst. The Ni / Al _ 2O _ 3, Ni _ (7.5) Al _ 2O _ 3 and Ni / Al _ 2O _ 3 / Ni / Ni / Al _ 2O _ 3 mesoporous catalysts were reduced to form polyatomic active centers at lower temperatures, and the Ni / Al _ 2O _ 3 / Ni / Al _ 2O _ 3 mesoporous catalysts were reduced to form polyatomic active centers. Both hydrogen yield and selectivity of carbon-containing products were not as good as that of Ni / Al _ 2O _ 3 catalyst. Finally, it is found that the Ni / Al _ 2O _ 3 catalyst modified by 7.5MgO is superior to the Ni / Ce-Zr-Ox-Cew: Zr1: 4 catalyst.
【學(xué)位授予單位】：遼寧工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TQ116.2;O643.36

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