【摘要】：隨著人類(lèi)社會(huì)、經(jīng)濟(jì)的不斷發(fā)展,全世界,尤其是以中國(guó)為代表的新興經(jīng)濟(jì)體對(duì)石油資源的需求日漸增加。然而,與此同時(shí),傳統(tǒng)石油資源卻正在日漸枯竭。油砂瀝青——作為世界儲(chǔ)量最大的一種非傳統(tǒng)化石能源之一,吸引著越來(lái)越多人的注意力。然而因?yàn)橛蜕盀r青粘度高、比重大、硫與氮以及重金屬雜質(zhì)含量高的特性,傳統(tǒng)沸石催化劑并不能很好的應(yīng)用于油砂瀝青的初改質(zhì)(催化減粘)過(guò)程中,而以MCM-41為代表的,有著比表面積大、孔道分布均勻、孔徑大等眾多優(yōu)點(diǎn)的有序介孔材料的出現(xiàn),為解決這一難題,提供了一種可能的催化轉(zhuǎn)化途徑。本論文的主要研究?jī)?nèi)容是通過(guò)以水熱穩(wěn)定性好,酸性強(qiáng)的斜發(fā)沸石(Clinoptilolite)為鋁源,在合適的條件下,合成出一種新型的具有Clin/MCM-41微-介孔復(fù)合結(jié)構(gòu)的催化劑,從而能夠更好的應(yīng)用于油砂瀝青的減粘改質(zhì)過(guò)程中。論文首先介紹了目前油砂工業(yè)的發(fā)展現(xiàn)狀、油砂瀝青催化改質(zhì)的機(jī)理以及天然沸石的催化性質(zhì),接著對(duì)有序介孔材料的性質(zhì)、合成方法以及在相關(guān)領(lǐng)域的應(yīng)用做了簡(jiǎn)要說(shuō)明,并對(duì)本實(shí)驗(yàn)所采用的以天然沸石為原料合成有序微介孔復(fù)合Clin/MCM-41的制備方法進(jìn)行了可行性分析。在實(shí)驗(yàn)部分,本論文首先采用單因素實(shí)驗(yàn),在不同合成條件下制得的多系列的微-介復(fù)合材料,接著運(yùn)用TEM、SEM、XRD、BET比表面積等分析技術(shù)對(duì)樣品進(jìn)行表征,從而找出最合適的合成路線(xiàn),并初步分析條件改變對(duì)材料結(jié)構(gòu)所產(chǎn)生影響的機(jī)理。經(jīng)過(guò)比對(duì),發(fā)現(xiàn)在反應(yīng)溫度為30℃、加入1g天然沸石原料、pH=10、120℃晶化溫度、48小時(shí)晶化時(shí)間的條件下,所得到的微-介孔復(fù)合Clin/MCM-41催化劑具有較大的比表面積、規(guī)整的介孔分布,并且制備過(guò)程相對(duì)合理、經(jīng)濟(jì)。接著在本實(shí)驗(yàn)中,作者將在優(yōu)化條件下所合成的微-介復(fù)合催化劑用于加拿大SAGD瀝青的催化減粘改質(zhì)反應(yīng)。研究發(fā)現(xiàn)：在30min,低溫水熱催化裂化的條件下,該新型微-介孔復(fù)合催化劑在減粘方面的表現(xiàn),比傳統(tǒng)改性催化劑有了很大的提升(減粘率達(dá)到81%,比同條件下改性沸石高30%)。同時(shí),以微-介復(fù)合材料為催化劑,生成物中飽和烴的含量更高,產(chǎn)物柴油餾分也高于傳統(tǒng)改性沸石。為了進(jìn)一步檢驗(yàn)催化劑的水熱裂化活性.本實(shí)驗(yàn)還以正十二烷為原料,在305～350℃的范圍內(nèi)進(jìn)行了水熱裂化.并分析了產(chǎn)物組分。最后,本論文還對(duì)整個(gè)改質(zhì)過(guò)程,進(jìn)行了初步的工藝過(guò)程能耗核算,結(jié)果顯示利用微介孔復(fù)合分子篩為催化劑的油砂瀝青改質(zhì)工藝的能量的消耗比傳統(tǒng)的露天開(kāi)采+溶劑抽提工藝+改質(zhì)工藝低30%以上。
[Abstract]:With the development of human society and economy, the demand for oil resources in the world, especially in the emerging economies represented by China, is increasing day by day. At the same time, however, traditional oil resources are drying up. Oil sand pitch, one of the largest unconventional fossil fuels in the world, is attracting more and more attention. However, because of its high viscosity, high specific gravity, high content of sulfur, nitrogen and heavy metal impurity, the traditional zeolite catalyst can not be used in the process of initial modification (catalytic viscosity reduction) of oil sand asphalt, as represented by MCM-41. The appearance of ordered mesoporous materials with many advantages, such as large specific surface area, uniform pore distribution and large pore size, provides a possible way for catalytic conversion to solve this problem. The main research content of this thesis is to synthesize a new type of catalyst with Clin/MCM-41 micro-mesoporous structure by using (Clinoptilolite) with good hydrothermal stability and strong acidity as aluminum source under suitable conditions. Thus, it can be better used in the process of viscosity reduction and upgrading of oil sand asphalt. This paper first introduces the development of oil sand industry, the mechanism of asphalt catalytic upgrading and the catalytic properties of natural zeolite. Then, the properties of ordered mesoporous materials, synthesis methods and their applications in related fields are briefly described. The preparation method of ordered micromesoporous Clin/MCM-41 using natural zeolite as raw material was analyzed. In the experiment part, the multi-series micro-dielectric composites were prepared by single-factor experiments under different synthetic conditions, and then the samples were characterized by TEM,SEM,XRD,BET specific surface area analysis. Thus the most suitable synthesis route is found and the mechanism of the influence of the change of the conditions on the structure of the material is analyzed preliminarily. After comparison, it was found that the micromesoporous composite Clin/MCM-41 catalyst had a large specific surface area under the conditions of 30 鈩，

本文編號(hào)：2336606