沸石基微—介孔复合催化剂用于沥青减粘改质过程的研究
发布时间：2018-11-16 20:47
【摘要】：随着人类社会、经济的不断发展,全世界,尤其是以中国为代表的新兴经济体对石油资源的需求日渐增加。然而,与此同时,传统石油资源却正在日渐枯竭。油砂沥青——作为世界储量最大的一种非传统化石能源之一,吸引着越来越多人的注意力。然而因为油砂沥青粘度高、比重大、硫与氮以及重金属杂质含量高的特性,传统沸石催化剂并不能很好的应用于油砂沥青的初改质(催化减粘)过程中,而以MCM-41为代表的,有着比表面积大、孔道分布均匀、孔径大等众多优点的有序介孔材料的出现,为解决这一难题,提供了一种可能的催化转化途径。本论文的主要研究内容是通过以水热稳定性好,酸性强的斜发沸石(Clinoptilolite)为铝源,在合适的条件下,合成出一种新型的具有Clin/MCM-41微-介孔复合结构的催化剂,从而能够更好的应用于油砂沥青的减粘改质过程中。论文首先介绍了目前油砂工业的发展现状、油砂沥青催化改质的机理以及天然沸石的催化性质,接着对有序介孔材料的性质、合成方法以及在相关领域的应用做了简要说明,并对本实验所采用的以天然沸石为原料合成有序微介孔复合Clin/MCM-41的制备方法进行了可行性分析。在实验部分,本论文首先采用单因素实验,在不同合成条件下制得的多系列的微-介复合材料,接着运用TEM、SEM、XRD、BET比表面积等分析技术对样品进行表征,从而找出最合适的合成路线,并初步分析条件改变对材料结构所产生影响的机理。经过比对,发现在反应温度为30℃、加入1g天然沸石原料、pH=10、120℃晶化温度、48小时晶化时间的条件下,所得到的微-介孔复合Clin/MCM-41催化剂具有较大的比表面积、规整的介孔分布,并且制备过程相对合理、经济。接着在本实验中,作者将在优化条件下所合成的微-介复合催化剂用于加拿大SAGD沥青的催化减粘改质反应。研究发现：在30min,低温水热催化裂化的条件下,该新型微-介孔复合催化剂在减粘方面的表现,比传统改性催化剂有了很大的提升(减粘率达到81%,比同条件下改性沸石高30%)。同时,以微-介复合材料为催化剂,生成物中饱和烃的含量更高,产物柴油馏分也高于传统改性沸石。为了进一步检验催化剂的水热裂化活性.本实验还以正十二烷为原料,在305～350℃的范围内进行了水热裂化.并分析了产物组分。最后,本论文还对整个改质过程,进行了初步的工艺过程能耗核算,结果显示利用微介孔复合分子筛为催化剂的油砂沥青改质工艺的能量的消耗比传统的露天开采+溶剂抽提工艺+改质工艺低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，
本文编号：2336606
[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，
本文编号：2336606
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