Synthesis Of In-situ Crystalline Catalytic Material And Its Applied Research On Catalytic Process Of Hydrocracking

This dissertation focus on the research and development of an in-situ synthesis catalytic material which is important in the field of petroleum cracking. Such special material is featured for which a famous FAU zeolite, Y type zeolite, crystallized in hydrothermal condition and directly grows on the surface of a kind of matrix. Referring to characteristic of traditional in-situ synthesis FCC catalyst and concerning about the shortcomings of present in-situ synthesis technology while basing on the requirements of hydrocracking catalyst, this research presents a series of modified schemes or novel methods according innovative in-situ synthesis concept. Firstly, while a low-cost industrial in-situ Y zeolite can be produced by the use of various cheap coal series kaolin matrix, a fast in-situ synthesis technology by optimizing preparation condition or parameters can be realized with crystallization time declining from present about 30h to less 12h or even more 6h. Secondly, by combining zeolite synthesis with expanding in-situ concept, a series of new multi-component zeolites can be prepared by in-situ compounding referring to not only solid synthesis process using porous amorphous material as feed but also in-situ recombination of electrical or structure auxiliaries such as titanium, zinc and rare earth, etc., which, for example, a zinc-incorporate in-situ Y zeolite has crystallinity 56% with as high as 3.5m% zinc content. Moreover, by the new concept of in-situ crystal self-transformation, different modified in-situ synthesis methods are developed related to free-of silica source or solid silica present and kinds of zeolie are attained with different appearance or granular-size, which, for example, a micro screw-form or nanometer sphere-form mesoporous zeolite was assembleded and then a new crystal self-transformation (3 zeolite with 60% more pore volume than traditionalβ zeolite was also synthesized by the use of these mesoporous materials.Depending on the new in-situ synthesis given by our research, a series of novel in-situ synthesis catalytic materials are prepared, whose characteristics differ from traditional material as they show super-micro crystal granular with 100-200 nm size, high B/L acidity ratio and concentrated mesoporous pore distribution in the range of 4-20nm with 40% or more than 60% ration. Furthermore, this dissertation and related research does much more effort on catalytic application of new in-situ synthesis. Getting rid of limitation of in-situ concept in the scope of FCC catalyst, much more works have been done on dual-function catalyst design, recipe optimization, hydrocracking process evaluation, hydrocracing operating way and product-cut scheme in order to coordinate properties of new in-situ material with requirement of hydrocracking process and its catalyst. It is demonstrated that, in one aspect, in-situ zeolite has more effective catalytic capability based on unit active site, in another aspect, it has excellent ring-open activity as so called in-situ type hydrocracking catalyst can produce tail oil with generally 2-3 unit lower than traditional hydrocracking catalyst on BMCI index. While low BMCI index tail oil is high quality ethylene feed, refineries have to treat more and more inferior feeds with high aromatic content. Thus, in-situ catalytic material or zeolite will provide a new material application reservoir and give hydrocracking catalyst R&D more space on selection and change. Also, a new opportunity for advancement for hydrocracking technology is presented.