Study on the Nickel-based Catalysts and a Novel Reactor Model of Ethylbenzen Hydrogenation

摘要近年来，随着环境保护要求和标准的不断提高，必须深度降低燃料油中芳烃及硫的含量。目前，燃料油中芳烃和硫的脱除手段主要是加氢技术，所用催化剂多以镍（钴）及钼（钨）为主要组分。这类催化剂若以硫化态存在则加氢活性较低，若以金属态存在虽然加氢活性高，但容易被原料中的含硫组分毒化而失活。因此，研究和开发抗硫性金属催化剂和反应装置成为当前油品脱芳烃的重点之一。为了开发抗硫性金属催化剂，首先必须研究不同金属组分之间的相互作用规律以及催化剂制备方法对这种相互作用的影响。其次，载体与催化剂的整体性质和性能密切相关，也应予以重视。为此，本文第三章研究了Ni-Zr和Ni-W两大系列催化剂中金属组分间的相互作用及组...Abstract As the environmental requirement and regulations have become more and more stringent in recent years, the contents of both aromatics and sulfur-containing compounds in the fuel oil must be deceased greatly. At present, hydrogenation treatment is commonly considered to be the most efficient technology to remove sulfur and aromatic hydrocarbon from fuel oil. The main active composition...学位：工学博士院系专业：化学化工学院化学工程与生物工程系_工业催化学号：1912005140310

代数表示理论的若干研究成果

叙述了有限维代数的表示理论和李代数表示理论的若干研究成果.国家自然科学基

发挥精品课程示范作用提升教学质量

本文介绍了厦门大学高等代数课程组发挥国家精品课程示范作用,建设课程网站,组织福建省课程建设研讨,提升全省“高等代数“课程质量的思路与实践

A Novel Method for Preparation of Activated Alumina

[中文文摘]将结晶氯化铝与柠檬酸及淀粉等造孔剂混合,经直接干燥和焙烧制得了一种无定形活性氧化铝,并通过X射线粉末衍射、N2物理吸附及氨程序升温脱附等手段对活性氧化铝样品进行了表征,探讨了各组分对活性氧化铝样品性质所起的作用.与常规的活性氧化铝制备方法相比,这种制法省去了中和、老化、过滤和洗涤等步骤,缩短制备周期且过程容易控制.活性氧化铝具有适宜且可调节的比表面积和孔径分布,作为载体负载镍金属组分制成负载型催化剂后,对乙苯加氢饱和与加氢裂化表现出较高的催化活性.[英文文摘]A novel and simple method was developed to prepare alumina with suitable specific surface area and pore size distribution. First,AlCl3·6H2O and citric acid were heated without water in a water bath at 90 ℃ with stirring until a homogenous solution was obtained.Then starch was added into is solution.After the solution was dried at 110 ℃ and calcined at indicated temperature, activated alumina was obtained.The activated alumina was characterized by N2 adsorption,X-ray diffraction,and NH3 temperature-programmed desorption. Compared with the usual technology , this novel preparation did not include some steps such as aging , filtering , and washing. Moreover , the specific surface area and pore size distribution of the activated alumina could be controlled and modified by changing the preparation parameters. The supported Ni/ Al2O3 catalyst with the activated alumina as support showed higher activity for hydrogenation and hydrocracking of ethylbenzene.国家重点基础研究发展计划(973计,2004CB217805); 福建省“百千万人才工程”项目; 福建省自然科学基金(U0750016)

Reactor model with cross-flow for aromatics catalytic hydrogenation

[中文文摘]提出了一种抗硫中毒的芳烃加氢催化反应器模型,称之为交叉流反应器模型,把反应物料分为两股,其中含有噻吩的乙苯物料采用轴向连续流动方式由反应器进口进入催化剂床层,而氢气由铅直导管直接进入催化剂床层中,然后与乙苯物料混合。在氢气导管出口处形成含硫乙苯浓度低而氢气浓度高的特殊区域,因而硫对催化剂的中毒效应大幅度降低,整体上提高了乙苯加氢饱和反应效率。与传统轴向混合流反应器进行比较,在相同条件下交叉流反应器具有更好的整体加氢反应性能。分别建立了交叉流反应器与传统轴向混合流反应器模型,提出了两种反应器的催化反应转化率方程;利用此转化率方程,对实验数据进行处理,得到动力学参数,模型的计算结果与实验数据相吻合,也验证了在交叉流反应器中,硫的中毒效应明显减弱。[英文摘要]A novel reactor model named cross-flow reactor for aromatics catalytic hydrogenation was proposed.The reactants were divided into two flows:ethylbenzene with thiophene was introduced to the catalyst bed along the axial direction of the columnar reactor,while hydrogen was introduced into catalyst bed through a vertical pipe with openings.Because special areas with high H2 pressure and low H2S pressure were formed near these openings,the poisoning of catalyst by thiophene was substantially decreased,and consequently the reaction of et hylbenzene hydrogenation was improved as compared with the traditional reactor with mixed co-flow. Finally , kinetic models were established for this cross-flow reactor and the traditional reactor1And the conversion equations of these two reactors were given.By using these equations , the experiments data were fitted to obtain kinetics parameters. The calculation results agreed well with the experimental data. It was also demonst rated that sulfur poisoning in cross-flow reactor was weakened.国家重点基础研究发展计划项目(2004CB217805); 福建省“百千万人才工程”支持项目; 福建省自然科学基金项目(U0750016)

A Novel Method for Preparation of Activated Alumina

A novel and simple method was developed to prepare alumina with suitable specific surface area and pore size distribution. First, AlCl3 center dot 6H(2)O and citric acid were heated without water in a water bath at 90 degrees C with stirring until a homogenous solution was obtained. Then starch was added into is solution. After the solution was dried at 110 degrees C and calcined at indicated temperature, activated alumina was obtained. The activated alumina was characterized by N-2 adsorption, X-ray diffraction, and NH3 temperature-programmed desorption. Compared with the usual technology, this novel preparation did not include some steps such as aging, filtering, and washing. Moreover, the specific surface area and pore size distribution of the activated alumina could be controlled and modified by changing the preparation parameters. The supported Ni/Al2O3 catalyst with the activated alumina as support showed higher activity for hydrogenation and hydrocracking of ethylbenzene

Methods of Deriving a Reaction Mechanism from Its Rate Equation

将化学反应视为抽象的“化学流”,提出“完全速率方程”的概念,并阐述其物理意义,考察了完全速率方程的各种破缺形式及其所对应的反应历程的特性及自催化作用对速率方程的影响.通过举例说明,归纳总结了由速率方程推演反应历程所应遵循的原理和规则.Supposing that the concentrations of intermediates are invariable during the course of a chemical reaction,there will be a rate equation with full form called full rate equation:γ_(ful)=(F_f-F_b)/(F_(m-f)-F_(m-b)).The full rate equation,if a chemical reaction is regarded as chemical flow,has its physical meanings.F_f 、F_b、F_(m-f)、F_(m-b) can be called forward full-flow,backward full-flow,forward flow of decreasing intermediates and backward flow of decreasing intermediates respectively.F_f is defined as multiplication of the forward rate equation of every element reaction(ER) and the definitions of F_b、F_(m-f) and F_(m-b) are in analogy to F_f.The reaction mechanism(pathway) corresponding the full rate equation has three features:(1) every ER is reversible;(2) at least one molecule of reactants does not take part in first-step ER;(3) at least one molecule of products does not emerge in last-step ER.In most cases,the full rate equation appears as a certain kind of short forms.For example,if at least one of ERs is irreversible,then F_b=0.According to the physical meanings of rate equation and the understanding of the intermediates of the reaction concerned,we can easily derive the reaction pathway.Meanwhile the effects of autocatalysis on the form of the rate equation are also discussed

MVW-extensions of quaternionic classical groups

NSFC [10931006]We show that inside the real quaternionic symplectic group , every element is conjugate to its inverse. Similar result is proved for the real quaternionic orthogonal group . We also show that no similar result is possible in the p-adic case

Hydrogenation Performance of Unsupported Ni-Based Catalyst

采用固相反应法制备了nI-zr非负载型催化剂,通过bET、Xrd、H2-TPr和H2-TPd等手段对催化剂进行了表征,并评价了该系列催化剂的乙苯加氢活性。结果表明,相对纯nI催化剂,nI-zr非负载型催化剂具有较大的比表面积,提高了活性组分的利用率。同时由于nI、zr两组分的相互作用,使nI组分以游离nIO和难还原nIO两种相态存在;当二者比例适当时,nI-zr催化剂具有较强的吸附H2能力和较高的加氢活性。A series of unsupported Ni-Zr catalysts were prepared by solid-phase-reaction method,and characterized by using BET,XRD,H2-TPR and H2-TPD.Compared with pure Ni catalyst,the as-prepared Ni-Zr catalysts possessed relatively large surface area,being beneficial to the utility of active component.It is suggested that the introduction of Zr into Ni catalyst led to not only the occurrence of interaction between Ni and Zr,but also the considerable increase of the adsorption capacity for H2.The Ni-Zr catalyst with suitable interaction of Ni and Zr showed excellent ethylbenzene hydrogenation activity.国家重点基础研究发展计划“973”项目(2010CB226903); 国家自然科学基金项目(21073147)资