A simple method for preparation of presulfided eggshell CoMoS/γ-Al2O3 catalysts with sharp boundary is developed, through which the eggshell thicknesses of Co and Mo could be easily regulated by controlling the impre...A simple method for preparation of presulfided eggshell CoMoS/γ-Al2O3 catalysts with sharp boundary is developed, through which the eggshell thicknesses of Co and Mo could be easily regulated by controlling the impregnation time. According to the results characterized by EDS, XRD, HRTEM and FT-IR of adsorbed CO, the active component structures, the nature and/or the amount of active sites on the eggshell catalyst are similar to these on the uniform catalyst. The evaluation results of the catalytic performance in selective hydrodesulfurization （HDS） of FCC gasoline show the presence of significant internal diffusion inhibition effect on HDS of S-compounds especially in the uniform catalyst. Compared with uniform catalyst, the eggshell catalyst could remarkably reduce such an internal diffusion inhibition effect due to a shortened diffusion path of the reactants, thus showing higher HDS activity and selectivity.展开更多
One of the main challenges in the design and operation of catalytic reactors for reactions with multiple paths/steps is the occurrence of undesirable reactions and products. In these cases, two main factors need to be...One of the main challenges in the design and operation of catalytic reactors for reactions with multiple paths/steps is the occurrence of undesirable reactions and products. In these cases, two main factors need to be considered in the reactor performance: the “conversion” of the feed and the “selectivity” of the process, which is the conversion split between the desired and the undesired products. In this work, a comprehensive model is developed and used to assess the impact of pore-size distribution (PSD) on both conversion and selectivity in series catalytic reactions. In particular, the evaluation considers the effects of various combinations of micro- and macro-porosity, the potential advantages of radial variation of the porosity in the catalyst pellets, and the effect of pellet size. Results show that, for series reactions, when the formation of the desired product is followed by an undesirable degradation reaction, higher porosity in pellets, particularly in the micro-range, gives higher overall conversion, but lowers selectivity towards the formation of the desired product. Selectivity in these pellets can be improved by using a non-uniform PSD that provides a radial gradient of effective diffusivity in pellets increasing from the center to the outer pellet surface. The pellet size also has a significant effect, and larger pellets show lower selectivity in most cases. In general, conversion and selectivity trends move in opposite directions with changes in PSD and the pore structural properties of pellets. Therefore, finding the optimum design of pellets is an optimization process that requires process modeling. Consequently, selecting the best catalyst properties involves optimization, and the needed tool is a comprehensive mathematical model that takes into account the details of mass transport and reaction kinetics in the catalyst pellets. Our primary objective has been the development of a flexible mathematical model that would be applicable to a wide range of conditions and can be used as a design tool and an optimization platform.展开更多
A comprehensive mathematical model is developed to simulate the interactions of the complex processes that take place in typical catalytic chemical reactors. This mathematical model includes correlations representing ...A comprehensive mathematical model is developed to simulate the interactions of the complex processes that take place in typical catalytic chemical reactors. This mathematical model includes correlations representing various modes of mass transport and chemical reactions. To illustrate the application and value of this approach for reactor optimizations, the model is applied to the case of series reactions with a desirable intermediate compound and the risk of degradation of this compound if the process conditions are not optimized. The modeling results show that in such cases, which are very common in practice, replacing the conventional uniform catalyst distribution with a novel non-uniform distribution will significantly improve the performance of the reactor and the production of the desirable compound. Various catalyst distribution options are compared, and a novel non-uniform loading of catalyst is identified that gives a much better performance compared to the conventional approach. The model is versatile and useful for both the design as well as the optimization of the catalytic fixed-bed reactors in a wide variety of reactor and reaction conditions.展开更多
基金supported by grants from the Major State Basic Research Development Program of China ("973" Program, 2010CB226905)the National Natural Science Foundation of China (Grant Nos. 21006128 and 21106185)+2 种基金the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20100133120007)the Shandong Provincial Natural Science Foundation of China (ZR2011BQ002)the Fundamental Research Funds for the Central Universities and the Graduate Innovation Project of China University of Petroleum (Grant No. CXZD11-06)
文摘A simple method for preparation of presulfided eggshell CoMoS/γ-Al2O3 catalysts with sharp boundary is developed, through which the eggshell thicknesses of Co and Mo could be easily regulated by controlling the impregnation time. According to the results characterized by EDS, XRD, HRTEM and FT-IR of adsorbed CO, the active component structures, the nature and/or the amount of active sites on the eggshell catalyst are similar to these on the uniform catalyst. The evaluation results of the catalytic performance in selective hydrodesulfurization （HDS） of FCC gasoline show the presence of significant internal diffusion inhibition effect on HDS of S-compounds especially in the uniform catalyst. Compared with uniform catalyst, the eggshell catalyst could remarkably reduce such an internal diffusion inhibition effect due to a shortened diffusion path of the reactants, thus showing higher HDS activity and selectivity.
文摘One of the main challenges in the design and operation of catalytic reactors for reactions with multiple paths/steps is the occurrence of undesirable reactions and products. In these cases, two main factors need to be considered in the reactor performance: the “conversion” of the feed and the “selectivity” of the process, which is the conversion split between the desired and the undesired products. In this work, a comprehensive model is developed and used to assess the impact of pore-size distribution (PSD) on both conversion and selectivity in series catalytic reactions. In particular, the evaluation considers the effects of various combinations of micro- and macro-porosity, the potential advantages of radial variation of the porosity in the catalyst pellets, and the effect of pellet size. Results show that, for series reactions, when the formation of the desired product is followed by an undesirable degradation reaction, higher porosity in pellets, particularly in the micro-range, gives higher overall conversion, but lowers selectivity towards the formation of the desired product. Selectivity in these pellets can be improved by using a non-uniform PSD that provides a radial gradient of effective diffusivity in pellets increasing from the center to the outer pellet surface. The pellet size also has a significant effect, and larger pellets show lower selectivity in most cases. In general, conversion and selectivity trends move in opposite directions with changes in PSD and the pore structural properties of pellets. Therefore, finding the optimum design of pellets is an optimization process that requires process modeling. Consequently, selecting the best catalyst properties involves optimization, and the needed tool is a comprehensive mathematical model that takes into account the details of mass transport and reaction kinetics in the catalyst pellets. Our primary objective has been the development of a flexible mathematical model that would be applicable to a wide range of conditions and can be used as a design tool and an optimization platform.
文摘A comprehensive mathematical model is developed to simulate the interactions of the complex processes that take place in typical catalytic chemical reactors. This mathematical model includes correlations representing various modes of mass transport and chemical reactions. To illustrate the application and value of this approach for reactor optimizations, the model is applied to the case of series reactions with a desirable intermediate compound and the risk of degradation of this compound if the process conditions are not optimized. The modeling results show that in such cases, which are very common in practice, replacing the conventional uniform catalyst distribution with a novel non-uniform distribution will significantly improve the performance of the reactor and the production of the desirable compound. Various catalyst distribution options are compared, and a novel non-uniform loading of catalyst is identified that gives a much better performance compared to the conventional approach. The model is versatile and useful for both the design as well as the optimization of the catalytic fixed-bed reactors in a wide variety of reactor and reaction conditions.
