本文選題：鈣鈦礦載體 + 甲烷重整制氫�。� 參考：《南昌大學》2017年碩士論文

【摘要】：甲烷重整反應可充分利用天然氣資源,緩解溫室效應,同時能產(chǎn)生高效、潔凈的二次能源氫氣,因而受到世界各國研究學者的廣泛關注。鎳基催化劑活性相對較高,且價格低廉、資源豐富,是理想的甲烷重整催化劑。但是鎳基催化劑存在活性組分容易燒結聚集,高溫反應條件下積炭嚴重等缺點,導致催化劑中毒失活。鎳基催化劑需要解決的核心問題是,如何提高Ni~0活性組分的分散度以及如何阻止Ni晶粒在高溫重整反應中聚集。本文從理解甲烷重整制氫機理入手,深入研究了Ni活性組分與載體的相互作用、催化劑結構、以及如何有效控制Ni晶粒尺寸等方面出發(fā),設計合成了幾種高效抗積炭重整催化劑。1、采用甘氨酸燃燒法(GNC)、溶膠凝膠法(SG)、共沉淀法(CP)設計合成了三種La FeO_3載體;負載Ni活性組分后結合DBD等離子體技術處理得到催化劑用于甲烷水蒸氣重整反應。研究結果表明,GNC和SG法比CP法制備的催化劑表現(xiàn)出更好的催化活性。雖然使用CP法制備的催化劑載體比表面積最大,但是負載Ni后催化劑活性最差且最不穩(wěn)定;使用SG法制備催化劑載體比表面積最小,綜合催化活性和催化穩(wěn)定性兩者因素,其催化性能最佳。經(jīng)過DBD等離子處理后,H2-TPR結果表明,催化劑活性中心Ni與LaFeO_3載體相互作用增強,從而使活性金屬Ni~0在載體表面的分散度增強。SEM和TGA-DSC結果證實,使用等離子處理能有效抑制Ni/LaFeO_3-CP-P催化劑表面積炭生成。2、研究了LaNiO_3@SiO_2核殼型催化劑用于甲烷干氣重整反應。以水熱法制備立方形貌的LaNiO_3,使用正硅酸四乙酯TEOS為硅源,CTAB陽離子表面活性劑作模板劑,制備了一系列不同殼層厚度的核殼型催化劑用于甲烷干氣重整反應。研究結果表明,采用SiO_2殼層包裹的核殼La NiO_3催化劑,表現(xiàn)良好的催化劑活性和優(yōu)越的抗積炭性能。這歸因于SiO_2殼層的保護作用,有效控制了金屬Ni的納米顆粒尺寸防止其在高溫下燒結和聚集,并且使積炭缺少物理生長空間,這可能是提高催化劑活性和抗積炭性能的本質原因。
[Abstract]:Methane reforming can make full use of natural gas resources, alleviate Greenhouse Effect and produce high efficiency and clean secondary energy hydrogen, so it has been paid more and more attention by researchers all over the world. Nickel based catalyst is an ideal catalyst for methane reforming because of its relatively high activity, low price and abundant resources. However, nickel based catalysts have some disadvantages such as easy sintering and aggregation of active components and serious deposition of carbon under high temperature reaction conditions, which lead to deactivation of catalyst poisoning. The key problems to be solved for nickel based catalysts are how to improve the dispersion of active components of Ni~0 and how to prevent Ni grains from aggregating in high temperature reforming reaction. Based on understanding the mechanism of methane reforming hydrogen production, the interaction of Ni active component with support, the structure of catalyst and how to effectively control the grain size of Ni were studied. Three kinds of La FeO_3 carriers were designed and synthesized by using glycine combustion method, sol-gel method and co-precipitation method. After supported Ni active component was treated by DBD plasma technique, the catalyst was used for methane steam reforming. The results showed that the catalyst prepared by GNC and SG showed better catalytic activity than that prepared by CP method. Although the specific surface area of the catalyst prepared by CP method was the largest, the catalyst activity was the worst and the most unstable after Ni loading, and the catalyst support prepared by SG method had the smallest specific surface area, which combined the catalytic activity and catalytic stability factors. Its catalytic performance is the best. After DBD plasma treatment, the results of H2-TPR show that the interaction between Ni, the active center of the catalyst, and the support of LaFeO_3 is enhanced, thus the dispersion of the active metal Ni~0 on the surface of the support is enhanced. Plasma treatment can effectively inhibit the formation of carbon deposition on the surface of Ni/LaFeO_3-CP-P catalyst. The LaNiO_3@SiO_2 core-shell catalyst was used in dry gas reforming of methane. A series of core-shell catalysts with different shell thickness were prepared by hydrothermal method for methane dry gas reforming using tetraethyl orthosilicate (TEOS) as the template of CTAB cationic surfactants. The results show that the core-shell La NiO_3 catalyst coated with SiO_2 has good catalytic activity and excellent resistance to coke deposition. This is attributed to the protective effect of the SiO_2 shell, which effectively controls the size of the metal Ni nanoparticles to prevent them from sintering and aggregating at high temperature, and makes the carbon deposition lack of physical growth space. This may be the essential reason for the improvement of catalyst activity and resistance to carbon deposition.
【學位授予單位】：南昌大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36;TQ116.2

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