An effective route to improve the catalytic performance of SAPO-34 in the methanol-to-olefin reaction by simple oxalic acid treatment was investigated. The samples were characterized by XRD, SEM, N2 adsorption-desorpt...An effective route to improve the catalytic performance of SAPO-34 in the methanol-to-olefin reaction by simple oxalic acid treatment was investigated. The samples were characterized by XRD, SEM, N2 adsorption-desorption, XRF, TG, 29Si MAS NMR and NH3-TPD techniques. The results indicated that the external surface acidity of SAPO-34 was finely tuned by oxalic acid treatment, and the selectivity to C2H4 on SAPO-34 and the catalyst lifetime in the methanol-to-olefin reaction were greatly improved.展开更多
近些年,我国成功开发了以煤为原料的甲醇制烯烃(Methanol to Olefins,MTO)生产工艺和技术,带动煤制烯烃产业的快速发展,保障了国家能源安全。流化床式反应器是MTO工业生产的核心反应装置,通过计算流体力学(Computational Fluid Dynamics...近些年,我国成功开发了以煤为原料的甲醇制烯烃(Methanol to Olefins,MTO)生产工艺和技术,带动煤制烯烃产业的快速发展,保障了国家能源安全。流化床式反应器是MTO工业生产的核心反应装置,通过计算流体力学(Computational Fluid Dynamics,CFD)方法深入认知MTO流化床内的流化特性规律具有重要的意义,它可以从理论上更加准确地指导MTO流化床的优化与放大。本工作采用基于宏观-亚网格层次的气泡EMMS曳力和传统TFM耦合计算的多尺度CFD方法,对工业尺度MTO流化床内的多相流化行为进行了三维数值模拟。模拟结果表明,该多尺度CFD方法考虑了气泡结构对气-固相间曳力的影响,能较准确地预测MTO流化床内轴向颗粒浓度的"S-型"分布规律,且得到实验数据的验证;所预测的径向颗粒浓度分布呈现出经典的"环-核"分布规律,气体/颗粒的轴向时均速度在径向上的分布也与实际情况相互佐证,表明该多尺度CFD方法显著改善了基于均匀曳力的传统TFM对于宏观流场的预测能力。下一步工作将多尺度CFD方法拓展应用于MTO流化床优化放大及反应特性的研究。展开更多
The methanol-to-olefin （MTO） process has attracted much attention and many problems including lifetime and selectivity of light olefins have all been connected to the diffusion problems in zeolite crystals. However,...The methanol-to-olefin （MTO） process has attracted much attention and many problems including lifetime and selectivity of light olefins have all been connected to the diffusion problems in zeolite crystals. However, a quantitative study of diffusion problems in SAPO-34 zeolites is lacking. In this paper, we performed a high-precision diffusion measurement of the diffusion behavior of ethane and propane, which represent ethylene and propylene respectively, over SAPO-34. The diffusions of ethane and propane over fresh and coked SAPO-34 zeolites with different crystal sizes were carefully studied. Ethane and propane show different diffusion behavior in SAPO-34. The diffusion of ethane is almost not influenced by the crystal size and coke percentage, whereas that of propane is strongly affected. A slower diffusion velocity was observed in bigger crystals, and the diffusion velocity decline signifcantly with the coke percentage increasing. The diffusion coefficient was calculated with both the internal and surface diffusion models, and the results show that the surface diffusion plays a key role in the diffusion process of both ethane and propane. We believe that this work would be helpful for understanding the diffusion of different molecules in SAPO-34 zeolites, and may lay the foundation of MTO research.展开更多
The methanol-to-olefin induction reaction over the SAPO-34 was performed using a fluidized-bed system.We found that the whole induction period could be divided into three reaction stages.Further investigation of the r...The methanol-to-olefin induction reaction over the SAPO-34 was performed using a fluidized-bed system.We found that the whole induction period could be divided into three reaction stages.Further investigation of the reaction kinetics revealed that this induction reaction behavior was different from that over H-ZSM-5 catalyst.Compared with the H-ZSM-5,the generation of initial active centers is easier over SAPO-34 because of its limited diffusivity and the spatial confinement effect of the cages.However,the autocatalysis reaction stage is difficult over SAPO-34 because of the continuous formation of inactive methyladamantanes.展开更多
文摘An effective route to improve the catalytic performance of SAPO-34 in the methanol-to-olefin reaction by simple oxalic acid treatment was investigated. The samples were characterized by XRD, SEM, N2 adsorption-desorption, XRF, TG, 29Si MAS NMR and NH3-TPD techniques. The results indicated that the external surface acidity of SAPO-34 was finely tuned by oxalic acid treatment, and the selectivity to C2H4 on SAPO-34 and the catalyst lifetime in the methanol-to-olefin reaction were greatly improved.
文摘近些年,我国成功开发了以煤为原料的甲醇制烯烃(Methanol to Olefins,MTO)生产工艺和技术,带动煤制烯烃产业的快速发展,保障了国家能源安全。流化床式反应器是MTO工业生产的核心反应装置,通过计算流体力学(Computational Fluid Dynamics,CFD)方法深入认知MTO流化床内的流化特性规律具有重要的意义,它可以从理论上更加准确地指导MTO流化床的优化与放大。本工作采用基于宏观-亚网格层次的气泡EMMS曳力和传统TFM耦合计算的多尺度CFD方法,对工业尺度MTO流化床内的多相流化行为进行了三维数值模拟。模拟结果表明,该多尺度CFD方法考虑了气泡结构对气-固相间曳力的影响,能较准确地预测MTO流化床内轴向颗粒浓度的"S-型"分布规律,且得到实验数据的验证;所预测的径向颗粒浓度分布呈现出经典的"环-核"分布规律,气体/颗粒的轴向时均速度在径向上的分布也与实际情况相互佐证,表明该多尺度CFD方法显著改善了基于均匀曳力的传统TFM对于宏观流场的预测能力。下一步工作将多尺度CFD方法拓展应用于MTO流化床优化放大及反应特性的研究。
文摘The methanol-to-olefin （MTO） process has attracted much attention and many problems including lifetime and selectivity of light olefins have all been connected to the diffusion problems in zeolite crystals. However, a quantitative study of diffusion problems in SAPO-34 zeolites is lacking. In this paper, we performed a high-precision diffusion measurement of the diffusion behavior of ethane and propane, which represent ethylene and propylene respectively, over SAPO-34. The diffusions of ethane and propane over fresh and coked SAPO-34 zeolites with different crystal sizes were carefully studied. Ethane and propane show different diffusion behavior in SAPO-34. The diffusion of ethane is almost not influenced by the crystal size and coke percentage, whereas that of propane is strongly affected. A slower diffusion velocity was observed in bigger crystals, and the diffusion velocity decline signifcantly with the coke percentage increasing. The diffusion coefficient was calculated with both the internal and surface diffusion models, and the results show that the surface diffusion plays a key role in the diffusion process of both ethane and propane. We believe that this work would be helpful for understanding the diffusion of different molecules in SAPO-34 zeolites, and may lay the foundation of MTO research.
文摘The methanol-to-olefin induction reaction over the SAPO-34 was performed using a fluidized-bed system.We found that the whole induction period could be divided into three reaction stages.Further investigation of the reaction kinetics revealed that this induction reaction behavior was different from that over H-ZSM-5 catalyst.Compared with the H-ZSM-5,the generation of initial active centers is easier over SAPO-34 because of its limited diffusivity and the spatial confinement effect of the cages.However,the autocatalysis reaction stage is difficult over SAPO-34 because of the continuous formation of inactive methyladamantanes.
