Selective and durable fixed‐bed catalysts are highly desirable for developing eco‐efficient HPPO(hydrogen peroxide propylene oxide)process.The powder titanosilicate catalysts must be shaped before being applied in i...Selective and durable fixed‐bed catalysts are highly desirable for developing eco‐efficient HPPO(hydrogen peroxide propylene oxide)process.The powder titanosilicate catalysts must be shaped before being applied in industrial processes.As the essential additives for preparing formed catalysts,binders are usually the catalytically inert components,but they would cover the surface and pore mouth of zeolite,thereby declining the accessibility of active sites.By recrystallizing the binder(silica)/Ti‐MWW extrudates with the assistance of dual organic structure‐directing agents,the silica binder was converted into MWW zeolite phase to form a structured binder‐free Ti‐MWW zeolite with Si‐rich shell,which enhanced the diffusion efficiency and maintained the mechanical strength.Meanwhile,due to the partial dissolution of Si in the Ti‐MWW matrix,abundant silanol nests formed and part of framework TiO4 species were transferred into open TiO_(6)ones,improving the accumulation and activation ability of H_(2)O_(2)inside the monolith.Successive piperidine treatment and fluoridation of the binder‐free Ti‐MWW further enhanced the H_(2)O_(2)activation and oxygen transfer ability of the active Ti sites,and stabilized the Ti‐OOH intermediate through hydrogen bond formed between the end H in Ti‐OOH and the adjacent Si‐F species,thus achieving a more efficient epoxidation process.Additionally,the side reaction of PO hydrolysis was inhibited because the modification effectively quenched numerous Si‐OH groups.The lifetime of the modified binder‐free Ti‐MWW catalyst was 2400 h with the H_(2)O_(2)conversion and PO selectivity both above 99.5%.展开更多
A zeolitic titanosilicate with the composition of K_2TiSi_3O_9·H_2O, a structural analogue of natural mineral umbite K_2ZrSi_3O_9·H_2O, was hydrothermally synthesized in the SiO_2-TiO_2-K_2O-H_2O system and...A zeolitic titanosilicate with the composition of K_2TiSi_3O_9·H_2O, a structural analogue of natural mineral umbite K_2ZrSi_3O_9·H_2O, was hydrothermally synthesized in the SiO_2-TiO_2-K_2O-H_2O system and characterized by means of powder X-ray diffraction, SEM, IR and thermal analysis. The effects of TiO_2/SiO_2 and OH -/SiO_2 ratios on the crystallization of the umbite were discussed. The influence of the organic additives on the morphology of the crystal was also investigated and the crystals with different shapes were obtained.展开更多
A novel synthesis process for ETS-4 titanosilicate using commercial anatase as the titanium source in the absence of fluoride ions was studied. Fluoride ions and traced ETS-4 seeds have important roles in forming ETS-...A novel synthesis process for ETS-4 titanosilicate using commercial anatase as the titanium source in the absence of fluoride ions was studied. Fluoride ions and traced ETS-4 seeds have important roles in forming ETS-4 structures. However, the method using ETS-4 seeds instead of fluoride ions to improve product purity and productivity is environment-friendly. ETS-4, ETS-4（NS）, and ETS-4（NaF） were respectively synthesized using traced ETS-4 seeds, without seeds, and with fluoride ions. The as-synthesized samples were identified by X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis. Adsorption isotherms and adsorption heats of nitrogen and methane on the prepared ETS-4 were also measured. The results showed that ETS-4 samples could be prepared using anatase in the absence of fluoride ions, with good purity, comparable physicochemical properties, and excellent adsorption properties.展开更多
The mechanical properties of interfacial transition zones(ITZs)have traditionally been simplified by reducing the stiffness of cement in previous simulation methods.A novel approach based on the discrete element metho...The mechanical properties of interfacial transition zones(ITZs)have traditionally been simplified by reducing the stiffness of cement in previous simulation methods.A novel approach based on the discrete element method(DEM)has been developed for modeling concrete.This new approach efficiently simulates the meso-structure of ITZs,accurately capturing their heterogeneous properties.Validation against established uniaxial compression experiments confirms the precision of thismodel.The proposedmodel canmodel the process of damage evolution containing cracks initiation,propagation and penetration.Under increasing loads,cracks within ITZs progressively accumulate,culminating in macroscopic fractures that traverse themortarmatrix,forming the complex,serpentine path of cracks.This study reveals four distinct displacement patterns:tensile compliant,tensile opposite,mixed tensile-shear,and shear opposite patterns,each indicative of different stages in concrete’s damage evolution.The widening angle of these patterns delineates the progression of cracks,with the tensile compliant pattern signaling the initial crack appearance and the shear opposite pattern indicating the concrete model’s ultimate failure.展开更多
The mesoscopic failure mechanism and the macro-mechanical characteristics of soil-rock mixture(S-RM) under external load are largely controlled by S-RM's meso-structural features. The objective of this work is to ...The mesoscopic failure mechanism and the macro-mechanical characteristics of soil-rock mixture(S-RM) under external load are largely controlled by S-RM's meso-structural features. The objective of this work is to improve the three-dimensional technology for the generation of the random meso-structural models of S-RM, for randomly generating irregular rock blocks in S-RM with different shapes, sizes, and distributions according to the characteristics of the rock blocks' size distribution. Based on the new improved technology, a software system named as R-SRM3 D for generation and visualization of S-RM is developed. Using R-SRM3 D, a three-dimensional meso-structural model of S-RM is generated and used to study the meso-mechanical behavior through a series of true-triaxial numerical tests. From the numerical tests, the following conclusions are obtained. The meso-stress field of S-RM is influenced by the distribution of the internal rock blocks, and the macro-mechanical characteristics of S-RM are anisotropic in 3D; the intermediate principal stress and the soil-rock interface properties have significant influence on the macro strength of S-RM.展开更多
Outwash deposit is a unique type of geological materials, and its features such as heterogeneity, discontinuity and nonlinearity determine the complexity of mechanical characteristics and failure mechanism. In this wo...Outwash deposit is a unique type of geological materials, and its features such as heterogeneity, discontinuity and nonlinearity determine the complexity of mechanical characteristics and failure mechanism. In this work, random meso-structure of outwash deposits was constructed by the technique of computer random simulation based on characteristics of its meso-structure in the statistical sense and some simplifications, and a series of large direct shear tests on numerical samples of outwash deposits with stone contents of 15%, 30%, 45% and 60% were conducted using the discrete element method to further investigate its mechanical characteristics and failure mechanism under external load. The results show that the deformation characteristics and shear strength of outwash deposits are to some extent improved with the increase of stone content, and the shear stress–shear displacement curves of outwash deposits show great differences at the post-peak stage due to the random spatial distribution and content of stones. From the mesoscopic view, normal directions of contacts between "soil" and "stone" particles undergo apparent deflection as the shear displacement continues during the shearing process, accompanying redistribution of the magnitude of contact forces during the shearing process. For outwash deposits, the shear zone formed after shear failure is an irregular stripe due to the movements of stones near the shear zone, and it expands gradually with the increase of stone content. In addition, there is an approximately linear relation between the mean increment of internal friction angle and the stone content lying between 30% and 60%, and a concave nonlinear relation between the mean increment of cohesion and stone content, which are in good agreement with the existing research results.展开更多
1-Butylene epoxidation was catalyzed by microporous titanosilicate molecular sieves TS-1 synthesized by different methods and mesoporous titanosilicate molecular sieves Ti-HMS, using dilute hydrogen peroxide solution ...1-Butylene epoxidation was catalyzed by microporous titanosilicate molecular sieves TS-1 synthesized by different methods and mesoporous titanosilicate molecular sieves Ti-HMS, using dilute hydrogen peroxide solution as oxidant. The effect of the Si/Ti molar ratio of the catalyst TS-1 and Ti-HMS on their performance was investigated. Conventional TS-1 has smaller crystal size and higher activity than that of TS-1 synthesized by using TPABr as template or the method of gas-solid phase. The TS-1 synthesized by using TPABr as template exhibits the highest selectivity to 1, 2-epoxybutane （BO）. With the increase of Ti content in molecular sieves, the conversion of H2O2 increases. The catalytic activity of mesoporous Ti-HMS is lower than that of TS-1, and large amount of H2O2 is decomposed in 1-butylene epoxidation. The primary reason for low activity of Ti-HMS in 1-butylene epoxidation is that Ti-HMS has poorer hydrophobicity property than TS-1.展开更多
文摘Selective and durable fixed‐bed catalysts are highly desirable for developing eco‐efficient HPPO(hydrogen peroxide propylene oxide)process.The powder titanosilicate catalysts must be shaped before being applied in industrial processes.As the essential additives for preparing formed catalysts,binders are usually the catalytically inert components,but they would cover the surface and pore mouth of zeolite,thereby declining the accessibility of active sites.By recrystallizing the binder(silica)/Ti‐MWW extrudates with the assistance of dual organic structure‐directing agents,the silica binder was converted into MWW zeolite phase to form a structured binder‐free Ti‐MWW zeolite with Si‐rich shell,which enhanced the diffusion efficiency and maintained the mechanical strength.Meanwhile,due to the partial dissolution of Si in the Ti‐MWW matrix,abundant silanol nests formed and part of framework TiO4 species were transferred into open TiO_(6)ones,improving the accumulation and activation ability of H_(2)O_(2)inside the monolith.Successive piperidine treatment and fluoridation of the binder‐free Ti‐MWW further enhanced the H_(2)O_(2)activation and oxygen transfer ability of the active Ti sites,and stabilized the Ti‐OOH intermediate through hydrogen bond formed between the end H in Ti‐OOH and the adjacent Si‐F species,thus achieving a more efficient epoxidation process.Additionally,the side reaction of PO hydrolysis was inhibited because the modification effectively quenched numerous Si‐OH groups.The lifetime of the modified binder‐free Ti‐MWW catalyst was 2400 h with the H_(2)O_(2)conversion and PO selectivity both above 99.5%.
基金Supported by the National Natural Science Foundation of China and the state key laboratory of Inorganic Synthesi
文摘A zeolitic titanosilicate with the composition of K_2TiSi_3O_9·H_2O, a structural analogue of natural mineral umbite K_2ZrSi_3O_9·H_2O, was hydrothermally synthesized in the SiO_2-TiO_2-K_2O-H_2O system and characterized by means of powder X-ray diffraction, SEM, IR and thermal analysis. The effects of TiO_2/SiO_2 and OH -/SiO_2 ratios on the crystallization of the umbite were discussed. The influence of the organic additives on the morphology of the crystal was also investigated and the crystals with different shapes were obtained.
基金supported by the National Natural Science Foundation of China (No. 51074205)
文摘A novel synthesis process for ETS-4 titanosilicate using commercial anatase as the titanium source in the absence of fluoride ions was studied. Fluoride ions and traced ETS-4 seeds have important roles in forming ETS-4 structures. However, the method using ETS-4 seeds instead of fluoride ions to improve product purity and productivity is environment-friendly. ETS-4, ETS-4（NS）, and ETS-4（NaF） were respectively synthesized using traced ETS-4 seeds, without seeds, and with fluoride ions. The as-synthesized samples were identified by X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis. Adsorption isotherms and adsorption heats of nitrogen and methane on the prepared ETS-4 were also measured. The results showed that ETS-4 samples could be prepared using anatase in the absence of fluoride ions, with good purity, comparable physicochemical properties, and excellent adsorption properties.
基金funded by the Research Project Supported by Shanxi Scholarship Council of China(2022-067)the Opening Project of State Key Laboratory of Explosion Science and Technology(Beijing Institute of Technology)(KFJJ22-14M).
文摘The mechanical properties of interfacial transition zones(ITZs)have traditionally been simplified by reducing the stiffness of cement in previous simulation methods.A novel approach based on the discrete element method(DEM)has been developed for modeling concrete.This new approach efficiently simulates the meso-structure of ITZs,accurately capturing their heterogeneous properties.Validation against established uniaxial compression experiments confirms the precision of thismodel.The proposedmodel canmodel the process of damage evolution containing cracks initiation,propagation and penetration.Under increasing loads,cracks within ITZs progressively accumulate,culminating in macroscopic fractures that traverse themortarmatrix,forming the complex,serpentine path of cracks.This study reveals four distinct displacement patterns:tensile compliant,tensile opposite,mixed tensile-shear,and shear opposite patterns,each indicative of different stages in concrete’s damage evolution.The widening angle of these patterns delineates the progression of cracks,with the tensile compliant pattern signaling the initial crack appearance and the shear opposite pattern indicating the concrete model’s ultimate failure.
基金Project(51109117)supported by the National Natural Science Foundation of ChinaProject(20111081125)supported by the Independent Research Plan of Tsinghua University,ChinaProject(2013-KY-4)supported by the State Key Laboratory of Hydroscience and Engineering Project,China
文摘The mesoscopic failure mechanism and the macro-mechanical characteristics of soil-rock mixture(S-RM) under external load are largely controlled by S-RM's meso-structural features. The objective of this work is to improve the three-dimensional technology for the generation of the random meso-structural models of S-RM, for randomly generating irregular rock blocks in S-RM with different shapes, sizes, and distributions according to the characteristics of the rock blocks' size distribution. Based on the new improved technology, a software system named as R-SRM3 D for generation and visualization of S-RM is developed. Using R-SRM3 D, a three-dimensional meso-structural model of S-RM is generated and used to study the meso-mechanical behavior through a series of true-triaxial numerical tests. From the numerical tests, the following conclusions are obtained. The meso-stress field of S-RM is influenced by the distribution of the internal rock blocks, and the macro-mechanical characteristics of S-RM are anisotropic in 3D; the intermediate principal stress and the soil-rock interface properties have significant influence on the macro strength of S-RM.
基金Project(2011CB013504) supported by the National Basic Research Program(973 Program)of ChinaProject(2013BAB06B01) supported by the National Science&Technology Pillar Program during the Twelfth Five-year Plan Period+2 种基金Projects(11772118,51479049,51709282) supported by the National Natural Science Foundation of ChinaProject(2017M620838) supported by the Postdoctoral Science Foundation of ChinaProject(487237) supported by the Natural Sciences and Engineering Research Council of Canada
文摘Outwash deposit is a unique type of geological materials, and its features such as heterogeneity, discontinuity and nonlinearity determine the complexity of mechanical characteristics and failure mechanism. In this work, random meso-structure of outwash deposits was constructed by the technique of computer random simulation based on characteristics of its meso-structure in the statistical sense and some simplifications, and a series of large direct shear tests on numerical samples of outwash deposits with stone contents of 15%, 30%, 45% and 60% were conducted using the discrete element method to further investigate its mechanical characteristics and failure mechanism under external load. The results show that the deformation characteristics and shear strength of outwash deposits are to some extent improved with the increase of stone content, and the shear stress–shear displacement curves of outwash deposits show great differences at the post-peak stage due to the random spatial distribution and content of stones. From the mesoscopic view, normal directions of contacts between "soil" and "stone" particles undergo apparent deflection as the shear displacement continues during the shearing process, accompanying redistribution of the magnitude of contact forces during the shearing process. For outwash deposits, the shear zone formed after shear failure is an irregular stripe due to the movements of stones near the shear zone, and it expands gradually with the increase of stone content. In addition, there is an approximately linear relation between the mean increment of internal friction angle and the stone content lying between 30% and 60%, and a concave nonlinear relation between the mean increment of cohesion and stone content, which are in good agreement with the existing research results.
基金supported by the National Natural Science Foundation of China (21277009)the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality(PHR201107104)~~
文摘1-Butylene epoxidation was catalyzed by microporous titanosilicate molecular sieves TS-1 synthesized by different methods and mesoporous titanosilicate molecular sieves Ti-HMS, using dilute hydrogen peroxide solution as oxidant. The effect of the Si/Ti molar ratio of the catalyst TS-1 and Ti-HMS on their performance was investigated. Conventional TS-1 has smaller crystal size and higher activity than that of TS-1 synthesized by using TPABr as template or the method of gas-solid phase. The TS-1 synthesized by using TPABr as template exhibits the highest selectivity to 1, 2-epoxybutane （BO）. With the increase of Ti content in molecular sieves, the conversion of H2O2 increases. The catalytic activity of mesoporous Ti-HMS is lower than that of TS-1, and large amount of H2O2 is decomposed in 1-butylene epoxidation. The primary reason for low activity of Ti-HMS in 1-butylene epoxidation is that Ti-HMS has poorer hydrophobicity property than TS-1.
