Synthesis of ZSM-5 zeolite typically utilizes small molecule polyamines or quaternary ammonium salts as organic structure guiding agent(OSDA).By contrast,the OSDA-free hydrothermal synthesis system eliminates the use ...Synthesis of ZSM-5 zeolite typically utilizes small molecule polyamines or quaternary ammonium salts as organic structure guiding agent(OSDA).By contrast,the OSDA-free hydrothermal synthesis system eliminates the use of organic templates and the subsequent calcination procedure.This not only reduces the cost of synthesis,but also prevents environmental pollution from the combustion of organic templates,representing an eco-friendly approach.Despite this,literature suggests that even so-called template-free synthesis systems often involve trace amount of organic substances like alcohol.In the present work,a calcined commercial ZSM-5 zeolite was served as seed,with sodium aluminate as aluminum source and silica sol as silicon source,ensuring an entirely template-free synthesis system.Polycrystalline ZSM-5 aggregates consisted of rod-like nanocrystals were successfully prepared in the completely OSDA-free system.Effects of the Si/Al ratio in ZSM-5 seed,dosage and crystallization conditions such as crystallization temperature and crystallization time on ZSM-5 synthesis were investigated.The results show that a highly crystallinity ZSM-5 aggregate consisting of primary nano-sized crystals less than 100 nm is produced from a gel precursor with 5.6%(in mass)seed after hydrothermal treatment for 48 h.Furthermore,the Si/Al ratio in ZSM-5 seed has little effect on the topological structure and pore structure of the synthesized samples.However,the seeds with a low Si/Al ratio facilitate faster crystallization of zeolite and enhance the acidity,especially the strong acid centers,of the catalyst.The catalytic performance of the synthesized polycrystalline ZSM-5 was evaluated during dehydration of methanol and compared with a commercial reference ZSM-5r.The results exhibit that as compared with the reference catalyst,the fabricated sample has a longer catalytic lifetime(16 h vs 8 h)attributed to its hierarchical pores derived from the loosely packed primary nanoparticles.Additionally,the prepared polycrystalline catalyst also exhibits a higher aromatics selectivity(28.1%-29.8%vs 26.5%).展开更多
To analyze the effect of single grain deformation behaviors on microforming process, a crystal plasticity model was developed considering grains at free surface layer as single grains. Based on the rate-dependent crys...To analyze the effect of single grain deformation behaviors on microforming process, a crystal plasticity model was developed considering grains at free surface layer as single grains. Based on the rate-dependent crystal plasticity theory, the analysis of the scale effect mechanism on upsetting deformation of micro rods was performed with respect to specimen dimension, original grain orientation and its distribution. The results show that flow stress decreases significantly with the scaling down of the specimen. The distribution of the grain orientation has an evident effect on flow stress of the micro specimen, and the effect becomes smaller with the progress of plastic deformation. For the anisotropy of single grains, inhomogeneous deformation occurs at the surface layer, which leads to the increase of surface roughness, especially for small specimens. The effect of grain anisotropy on the surface topography can be decreased by the transition grains. The simulation results are validated by upsetting deformation experiments. This indicates that the developed model is suitable for the analysis of microforming processes with characteristics, such as scale dependency, scatter of flow stress and inhomogeneous deformation.展开更多
基金National Natural Science Foundation of China(U19B2003,21706177,21975174)Foundation Supported by China Petroleum&Chemical Corporation(121014-2)。
文摘Synthesis of ZSM-5 zeolite typically utilizes small molecule polyamines or quaternary ammonium salts as organic structure guiding agent(OSDA).By contrast,the OSDA-free hydrothermal synthesis system eliminates the use of organic templates and the subsequent calcination procedure.This not only reduces the cost of synthesis,but also prevents environmental pollution from the combustion of organic templates,representing an eco-friendly approach.Despite this,literature suggests that even so-called template-free synthesis systems often involve trace amount of organic substances like alcohol.In the present work,a calcined commercial ZSM-5 zeolite was served as seed,with sodium aluminate as aluminum source and silica sol as silicon source,ensuring an entirely template-free synthesis system.Polycrystalline ZSM-5 aggregates consisted of rod-like nanocrystals were successfully prepared in the completely OSDA-free system.Effects of the Si/Al ratio in ZSM-5 seed,dosage and crystallization conditions such as crystallization temperature and crystallization time on ZSM-5 synthesis were investigated.The results show that a highly crystallinity ZSM-5 aggregate consisting of primary nano-sized crystals less than 100 nm is produced from a gel precursor with 5.6%(in mass)seed after hydrothermal treatment for 48 h.Furthermore,the Si/Al ratio in ZSM-5 seed has little effect on the topological structure and pore structure of the synthesized samples.However,the seeds with a low Si/Al ratio facilitate faster crystallization of zeolite and enhance the acidity,especially the strong acid centers,of the catalyst.The catalytic performance of the synthesized polycrystalline ZSM-5 was evaluated during dehydration of methanol and compared with a commercial reference ZSM-5r.The results exhibit that as compared with the reference catalyst,the fabricated sample has a longer catalytic lifetime(16 h vs 8 h)attributed to its hierarchical pores derived from the loosely packed primary nanoparticles.Additionally,the prepared polycrystalline catalyst also exhibits a higher aromatics selectivity(28.1%-29.8%vs 26.5%).
基金Project (50835002) supported by the National Natural Science Foundation of ChinaProject (QC08C55) supported by the Natural Science Foundation of Heilongjiang Province, China Project (200802131031) supported by the PhD. Programs Foundation of Ministry of Education of China for Young Scholars
文摘To analyze the effect of single grain deformation behaviors on microforming process, a crystal plasticity model was developed considering grains at free surface layer as single grains. Based on the rate-dependent crystal plasticity theory, the analysis of the scale effect mechanism on upsetting deformation of micro rods was performed with respect to specimen dimension, original grain orientation and its distribution. The results show that flow stress decreases significantly with the scaling down of the specimen. The distribution of the grain orientation has an evident effect on flow stress of the micro specimen, and the effect becomes smaller with the progress of plastic deformation. For the anisotropy of single grains, inhomogeneous deformation occurs at the surface layer, which leads to the increase of surface roughness, especially for small specimens. The effect of grain anisotropy on the surface topography can be decreased by the transition grains. The simulation results are validated by upsetting deformation experiments. This indicates that the developed model is suitable for the analysis of microforming processes with characteristics, such as scale dependency, scatter of flow stress and inhomogeneous deformation.
