本文選題：選擇性加氫 + 雙金屬氧化物��； 參考：《山東農(nóng)業(yè)大學(xué)》2017年碩士論文

【摘要】：5-羥甲基糠醛作為最具潛力的生物質(zhì)基平臺(tái)分子之一,是聯(lián)系生物質(zhì)資源與石油基工業(yè)的橋梁和關(guān)鍵物質(zhì),它可以衍生出許多呋喃類化工產(chǎn)品通過(guò)催化加氫、氧化脫氫、酯化、鹵化等化學(xué)反應(yīng)。2.5-二甲基呋喃(DMF)是一種可比擬汽油的新型液體生物燃料,能解決乙醇作為生物質(zhì)燃料的諸多不足,可由5-羥甲基糠醛通過(guò)催化加氫制得,因此開(kāi)發(fā)一種高效轉(zhuǎn)化為DMF的催化劑是當(dāng)務(wù)之急。而尋找合適的載體是制備高選擇性催化劑的最有效的方法。雙金屬氧化物由于其酸堿度,穩(wěn)定性等特性在多相催化領(lǐng)域受到廣泛的關(guān)注。本文以金屬氧化物為載體,以Ru金屬為活性位點(diǎn)組裝催化劑,探究載體對(duì)Ru金屬催化5-羥甲基糠醛加氫性能的促進(jìn)作用。詳細(xì)內(nèi)容如下:1.CoFe類水滑石氧化物負(fù)載Ru對(duì)5-羥甲基糠醛加氫性能的研究本實(shí)驗(yàn)采用還原-沉淀法,將貴金屬Ru負(fù)載到MM-LDO(M=Co,Ni,Fe)表面,得到不同催化劑,并探究其對(duì)5-羥甲基糠醛的催化加氫性能。實(shí)驗(yàn)表明Ru/CoFe-LDO表現(xiàn)很高的催化活性。以Ru/CoFe-LDO為最優(yōu)催化劑,采用XRD、SEM、TEM、FT-IR、TGA、XPS等表征載體及催化劑的結(jié)構(gòu)特征,探究反應(yīng)溫度、反應(yīng)時(shí)間、反應(yīng)壓力、催化劑的量及煅燒溫度對(duì)催化性能的影響,并提出可能的反應(yīng)途徑。由于CoFe-LDO與貴金屬Ru的協(xié)同作用,進(jìn)一步促進(jìn)HMF轉(zhuǎn)化為DMF。2.Fe-Al金屬氧化物氣凝膠負(fù)載貴金屬Ru對(duì)5-羥甲基糠醛選擇性加氫性能的研究本實(shí)驗(yàn)采用恒pH-共沉淀法制備M-Al(M=Fe,Ni,Co,Cr,Mn)氫氧化物氣凝膠,通過(guò)超臨界乙醇干燥并煅燒得M-Al金屬氧化物氣凝膠。以M-Al金屬氧化物氣凝膠為載體的Ru基催化劑用于HMF的選擇性加氫反應(yīng),實(shí)驗(yàn)表明Ru/Fe-A表現(xiàn)出最好的活性及對(duì)DMF的選擇性。與類水滑石氧化物相比,金屬氧化物氣凝膠載體具有低密度,高比表面積,大孔和高熱穩(wěn)定等優(yōu)點(diǎn),具有較高的活性中心分散性和較好的傳質(zhì)性能。實(shí)驗(yàn)表明,Fe-A為載體表現(xiàn)出非常好的催化活性和對(duì)DMF的選擇性。通過(guò)重復(fù)性實(shí)驗(yàn)對(duì)催化劑進(jìn)行穩(wěn)定性測(cè)試,表明Ru/Fe-A具有很好的催化性能和穩(wěn)定性。3.ZIF模板化金屬氧化物負(fù)載貴金屬Ru對(duì)5-羥甲基糠醛選擇性加氫性能的研究本實(shí)驗(yàn)采用ZIF為模板制備中空結(jié)構(gòu)的ZnCo4O5復(fù)合氧化物,以其為載體采用傳統(tǒng)的浸漬-還原-沉淀法制備了 Ru基催化劑,并以此作為HMF選擇性加氫的催化劑。與類水滑石氧化物和金屬氧化物氣凝膠相比,中空結(jié)構(gòu)的ZnCo4O5復(fù)合氧化物載體具有十二面體結(jié)構(gòu),高比表面積,高熱穩(wěn)定等優(yōu)點(diǎn),具有較高的活性中心分散性和較好的傳質(zhì)性能,其中Ru的負(fù)載量為3%,DMF選擇性能達(dá)到95.3%,表明Ru/ZnCo4O5具有更好的催化活性。通過(guò)重復(fù)性實(shí)驗(yàn)對(duì)催化劑進(jìn)行穩(wěn)定性測(cè)試,表明Ru/Fe-A具有很好的催化性能和穩(wěn)定性。
[Abstract]:As one of the most promising biomass-based platform molecules, 5-hydroxymethyl furfural is a bridge and key substance between biomass resources and petroleum-based industry. It can derive many furan chemical products through catalytic hydrogenation, oxidative dehydrogenation and esterification. Halogenation and other chemical reactions .2.5- dimethylfuran (DMF) is a new liquid biofuel comparable to gasoline, which can solve many shortcomings of ethanol as biomass fuel and can be prepared by catalytic hydrogenation of 5-hydroxymethyl furfural. Therefore, it is urgent to develop a catalyst for high-efficiency conversion to DMF. Finding suitable support is the most effective method to prepare high selectivity catalyst. Bimetallic oxides have attracted much attention in heterogeneous catalysis due to their pH and stability. In this paper, metal oxide was used as the carrier and Ru metal as the active site to assemble the catalyst to explore the effect of the support on the hydrogenation of 5-hydroxymethyl furfural catalyzed by Ru. The hydrogenation properties of 5-hydroxymethylfurfural supported on Cofe hydrotalcite oxides were studied. In this experiment, the noble metal Ru was loaded on the surface of MM-LDO (MM-LDO) MCoCoNiFe) by reduction-precipitation method, and different catalysts were obtained. The catalytic hydrogenation of 5-hydroxymethyl furfural was investigated. The experimental results show that Ru/CoFe-LDO exhibits high catalytic activity. Using Ru/CoFe-LDO as the optimal catalyst, the structure characteristics of the support and catalyst were characterized by XRDX SEMMET TGA XPS. The effects of reaction temperature, reaction time, reaction pressure, amount of catalyst and calcination temperature on the catalytic performance were investigated, and the possible reaction paths were proposed. Due to the synergistic effect of CoFe-LDO and noble metal Ru, the conversion of HMF to DMF.2.Fe-Al metal oxide aerogel loaded with noble metal Ru for selective hydrogenation of 5-hydroxymethyl furfural was further promoted. M-Al metal oxide aerogels were prepared by drying and calcining with supercritical ethanol. Ru based catalyst supported on M-Al metal oxide aerogel was used for selective hydrogenation of HMF. The results showed that Ru/Fe-A exhibited the best activity and selectivity to DMF. Compared with hydrotalcite-like oxides, metal oxide aerogel carriers have the advantages of low density, high specific surface area, large pore size and high thermal stability. The experimental results show that Fe-A as the carrier has very good catalytic activity and selectivity to DMF. The stability of the catalyst was tested by repeated experiments. The results showed that Ru/Fe-A had good catalytic performance and stability. 3. The selective hydrogenation of 5-hydroxymethylfurfural with metal oxides supported on Ru was studied. In this experiment, hollow ZnCo4O5 composite oxides were prepared by using ZIF as template. Ru based catalysts were prepared by traditional impregnation-reduction-precipitation method and used as catalysts for selective hydrogenation of HMF. Compared with hydrotalcite-like oxides and metal oxide aerogels, hollow ZnCo4O5 composite oxide carriers have the advantages of dodecahedron structure, high specific surface area, high thermal stability, high dispersion of active centers and better mass transfer properties. The selectivity of Ru to DMF is 95.3, which indicates that Ru/ZnCo4O5 has better catalytic activity. The stability of the catalyst was tested by repeated experiments. The results show that Ru/Fe-A has good catalytic performance and stability.
【學(xué)位授予單位】：山東農(nóng)業(yè)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

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本文編號(hào)：1809445