提高USY型FCC催化剂硫转移和催化裂化活性的研究

采用镁、铈、镧和磷对USY型FCC催化剂进行改性，采用FT IR分析方法对改性催化剂的表面酸性进行了表征，研究了硫转移活性组分对催化剂的硫转移和催化裂化活性的影响。结果表明，多次氧化 还原循环后，改性催化剂仍保持较好的硫转移活性，可以达到60%以上。镁的引入会减少基质和分子筛表面强酸的数量，少量镁的引入对催化裂化活性影响不大，铈和镧的引入会使分子筛和基质的表面酸量得到显著增加，提高催化裂化活性，但同时会引起焦炭的增加，磷改性可改善基质和分子筛表面酸性，抑制焦炭的产生，保持催化裂化活性的同时使汽油中的烯烃质量分数下降6%。     

ZSM－5（核）／AlPO4－5（壳）双结构分子筛的合成与催化裂化性能

 采用X射线衍射、扫描电镜、X射线能量散射谱、红外光谱和核磁共振等多种物化方法对合成的ZSM－5（核）／AlPO4－5（壳）双结构分子筛进行了表征，证明这种材料具有以ZSM－5为核层、以AlPO4－5为壳层的双结构特征．考察了合成条件对ZSM－5（核）／AlPO4－5（壳）分子筛形貌的影响，发现ZSM－5分子筛的加入方式对产物的形貌有较大影响．重油裂化反应结果表明，ZSM－5（核）／AlPO4－5（壳）双结构分子筛的催化性能比ZSM－5和ZSM－5／AlPO4－5机械混合分子筛样品好，表现为原油转化率和低碳烯烃、汽油及柴油收率提高．     

Studies on the cracking ofn-hexane over H-ZSM-48

The influence of various reaction parameters such as temperature, WHSV and H₂ ton-C₆ molar ratio onn-hexane cracking at atmospheric pressure over ZSM-48 has been studied. The influence of SiO₂/Al₂O₃ variations and isomorphous substitution by Ga and Fe has also been investigated. A linear relationship between the specific catalytic activity for the cracking ofn-hexane and the concentration of strong acid sites has been found.     

USY型分子筛与高岭土的水热热压固化及固化体性能研究

应用水热热压技术制备了各种USY型分子筛-高岭土的固化成型体,并对其进行物相分析、表面酸性以及对正十五烷裂解的催化性能测定。实验结果表明:USY型分子筛与高岭土的固化体具有较强的B酸中心,而几乎没有L酸中心。135℃下得到的固化体对n-十五烷的裂解活性及汽油转化率都高于未经处理的样品。水热热压固化温度是影响固化体性能的重要条件,可以利用固化体组分的改变及固化条件的控制来调节固化体表面酸性及其催化性能。     

纳米硅铝介孔分子筛的合成及其催化裂化性能

采用低温晶化法一步合成了纳米硅铝介孔分子筛( 记为Z-1),并通过XRD、BET、N2吸/脱附曲线和TEM等手段对其结构性质进行了表征.结果表明:所合成的分子筛具有类似MCM-41的六方结构,较好的介孔特征,孔分布狭窄,纳米级晶粒( 40～50 nm ).用氨气程序升温脱附（NH3-TPD）法测试了其酸强度;并采用脉冲法,以异丙苯和1,3,5-三异丙苯的催化裂化为探针反应,考察了该分子筛的催化裂化性能和水热稳定性.Z-1与后嫁接法制得的AlMCM-41相比,呈现出较高的催化活性、选择性和蒸气稳定性.     

SDY型沸石的浸取处理及其对催化性能的影响

分别用Ｎａ２Ｈ２ＥＤＴＡ、Ｈ４ＥＤＴＡ和Ｈｃｌ对ＳＤＹ型沸石的非骨架铝进行了浸取处理，并应用化学分析、ＸＲＤ、高真空苯吸附、低温Ｎ２吸附、ＮＨ３－ＴＰＤ和正庚烷裂解脉冲微型反应等物理和化学实验技术对浸取前后样品的结构、酸性和催化性能进行了研究。发现Ｎａ２Ｈ２ＥＤＴＡ能选择地浸取沉积于沸石微孔和二次孔中的非骨架铝碎片，且不损伤沸石骨架，浸取出部分非骨架铝后的样品，其正庚烷裂解和抗氮性能均有所提高。     

Analysis of Acidic Properties of Zeolitic and Non-Zeolitic Solid Acid Catalysts Using Temperature-Programmed Desorption of Ammonia

A method of ammonia temperature-programmed desorption (TPD) for analysis of acidic property of a solid was improved by introduction of a water vapor treatment method and development of a theory for calculation of ammonia adsorption heat from the TPD profile. The improved method was applied to various solid acid catalysts to establish relationships between the acidic properties and catalytic performances for various acid-catalyzed reactions. Here, examples of the applications to some important acid catalysts are reviewed. The exact analysis of acidic property of Y zeolite and its change by such modifications as steaming and ethylenediaminetetraacetic acid (EDTA) treatment gave a new interpretation on the generation of alkane (paraffin) cracking activity on an ultra stable Y (USY) zeolite. The surface density and strength of acid sites on WO₃/ZrO₂ and SO₄ ^2–/ZrO₂ catalysts were determined, and their relations with catalytic activities for Friedel–Crafts type alkylation and skeletal isomerization of alkane were found.     

Catalytic cracking of C5+ gasoline over hy zeolite

The catalytic conversion of a C5+ natural gasoline over the HY zeolite has been studied. The results show the formation of C2, C3 and C4 hydrocarbons with an apparent activation energy of ca. 39 kJ mol^-1. This revised version was published online in June 2006 with corrections to the Cover Date.     

The Application of Composite Energy Methods to n-butyl Radical β-scission Reaction Kinetic Estimations

Hydrocarbon cracking reactions are key steps in petroleum refinery processes and understanding reaction kinetics has very important applications in the petroleum industry. In this work, G3 and complete basis set (CBS) composite energy methods were applied to investigate butyl radical β-scission reaction kinetics and energetics. Experimental thermodynamic and kinetic data were employed to evaluate the accuracy of these calculations. The CBS compound model proved to have excellent agreement with the experimental data, indicating that it is a reliable method for studying other large hydrocarbon cracking reactions. Furthermore, a reaction kinetic model with pressure and temperature effects was proposed. For P ≤ P ₀, k = 2.04 × 10⁹ × P ^0.51 × e^(-9745.70/T); for P > P ₀, k = 9.43 × 10¹³ × e^{(-15135.70/T)}, where k is the reaction rate constant in units of s⁻¹; P is pressure in units of kPa, T is temperature in units of Kelvin, and the switching pressure is P ₀ = 1.53 × 10⁹ × e^{(-10610.24/T)}. This model can be easily applied to different reaction conditions without performing additional expensive and complicated calculations.     

表面活性剂改性的铝交联累托土的表征及催化性能

用ＸＲＤ，低温Ｎ２吸附／脱附，骨架振动红外光谱等手段对以聚乙烯醇为支撑前体合成的一类新型的表面活性剂改性的铝交联累托土进行了表征，同时对它们进行了柴油催化转化为汽油的微反活性测试，结果表明其热稳定性与催化活性比以传统制备方法合成的铝交联累托土都有明显提高。