The Baeyer-Villiger(BV)oxidation of cyclohexanone is explored using IWV-type aluminosilicates with different Al sites as heterogeneous catalysts.The IWV framework exhibits a two-dimensional 12-membered ring(MR)pore sy...The Baeyer-Villiger(BV)oxidation of cyclohexanone is explored using IWV-type aluminosilicates with different Al sites as heterogeneous catalysts.The IWV framework exhibits a two-dimensional 12-membered ring(MR)pore system intersected by 14-MR supercages,resembling typical beta zeolite.To address the constraints associated with hydrothermal synthesis,IWV aluminosilicates were synthesized via interzeolite transformation of various FAU-type zeolites.HF-assisted transformation of dealuminated FAU zeolite resulted in the formation of a high-silica IWV aluminosilicate(Si/Al=54.6),whereas the incorporation of aluminum isopropoxide enables the tuning of Si/Al ratio down to 18.7.The alkaline conversion of protonated FAU zeolites,utilizing Na^(+)ions as mineralizing agents,produces high-Al content IWV derivatives in just four days.Catalytic evaluation demonstrates that the high-silica IWV catalyst exhibits a higher turnover number than the other IWV catalysts,along with enhancedε-caprolactone(CL)selectivity relative to that of high-silica beta zeolite.Facile modifications are performed to adjust Al sites,as characterized by pyridine-adsorbed infrared spectroscopy.Experimental evidence confirms that Al Brønsted acid sites improves the selective oxidation of cyclohexanone,while concurrently enhancing CL hydrolysis.展开更多
Low-cost adsorbents constituted by Fe-modified-aluminosilicates （laminar and zeolite type minerals） were developed and characterized to be used in the arsenic removal from groundwater. Iron activation was carried o...Low-cost adsorbents constituted by Fe-modified-aluminosilicates （laminar and zeolite type minerals） were developed and characterized to be used in the arsenic removal from groundwater. Iron activation was carried out ＂in situ＂ by the synthesis and deposition of mesoporous ferrihydrite. Natural iron-rich aluminosilicate was used as reference. All samples were characterized by X-ray diffraction, Raman spectroscopy, BET N2-adsorption, SEM-EDS microscopy and ICP chemical analysis. Experimental results of arsenic sorption showed that iron-poor raw materials were not active, unlike iron activated samples. The iron loading in all activated samples was below 5% （expressed as Fe203）, whereas the removal capacity of these samples reaches between 200-700 gg of As by g of adsorbent, after reusing between 17 cycles and 70 cycles up to adsorbent saturation. Differences can be associated to mineral structure and to the surface charge modification by iron deposition, affecting the attraction of the As-oxoanion. On the basis of low-cost raw materials, the easy chemical process for activation shows that these materials are potentially attractive for As（V） removal. Likewise, the activation of clay minerals, with natural high content of iron, seems to be a good strategy to enhance the arsenic adsorption ability and consequently the useful life of the adsorbent.展开更多
Well-ordered aluminosilicates(MAs)were prepared by in-situ assembly of pre-crystallized units of zeolite Y precursors at a commercial scale,and applied in an industrial fluid catalytic cracking unit for the first time...Well-ordered aluminosilicates(MAs)were prepared by in-situ assembly of pre-crystallized units of zeolite Y precursors at a commercial scale,and applied in an industrial fluid catalytic cracking unit for the first time.Compared with incumbent equilibrium catalyst,the surface area of trial equilibrium catalysts(30%inventory ratio)increased from 110 m^(2)g^(-1)to 120m^(2)g^(-1).Moreover,a significant increase of the mesoporous surfaceareaof trial equlibrium catalysts(30%inventoryrati)from 33 m g/to 40magi(22%increase).Furthermore,the equilibrium catalyst that contain 80%LPC-65 yields significantly lower heavy oil(0.23%)and higher total liquids(0.53%)compared with LDO-70.The industrial results demonstrated excellent hydrothermal stability and superior catalytic cracking properties,showing the promising futurein the industrial units.展开更多
In this study the characterization of an aluminosilicate synthesized from commercial Al2(SO4)3 and colloidal SiO2 is presented, as well as its capacity for the removal of copper from aqueous solution. Characterization...In this study the characterization of an aluminosilicate synthesized from commercial Al2(SO4)3 and colloidal SiO2 is presented, as well as its capacity for the removal of copper from aqueous solution. Characterization of the synthesized material was performed using X-ray diffraction, BET nitrogen adsorption-desorption, mass titration and the Boehm method. In order to obtain stable agglomeration and enhance its surface area (165 - 243 m2/g) and solid adsorbing capabilities, the molar ratio SiO2:Al2O3 (1:3, 1:1 and 3:1) was studied, the solubility of the preparation material, synthesis-procedure time and solution pH function were also examined. The maximum capacity to remove copper ions from an aqueous solution by synthesized aluminosilicate was 16 mg/g at pH 4 and 25℃. The Langmuir model fitted better to the copper adsorption experimental data.展开更多
Currently,the Al_(2)O_(3)content in the high-alumina slag systems within blast furnaces is generally limited to 16wt%–18.5wt%,making it challenging to overcome this limitation.Unlike most studies that concentrated on...Currently,the Al_(2)O_(3)content in the high-alumina slag systems within blast furnaces is generally limited to 16wt%–18.5wt%,making it challenging to overcome this limitation.Unlike most studies that concentrated on managing the MgO/Al_(2)O_(3)ratio or basicity,this paper explored the effect of equimolar substitution of MgO for CaO on the viscosity and structure of a high-alumina CaO-MgO-Al_(2)O_(3)-SiO_(2)slag system,providing theoretical guidance and data to facilitate the application of high-alumina ores.The results revealed that the viscosity first decreased and then increased with higher MgO substitution,reaching a minimum at 15mol%MgO concentration.Fourier transform infrared spectroscopy(FTIR)results found that the depths of the troughs representing[SiO_(4)]tetrahedra,[AlO_(4)]tetrahedra,and Si-O-Al bending became progressively deeper with increased MgO substitution.Deconvolution of the Raman spectra showed that the average number of bridging oxygens per Si atom and the X_(Q^(3))/X_(Q^(2))(X_(Q^(i))is the molar fraction of Q^(i) unit,and i is the number of bridging oxygens in a[SiO_(4)]tetrahedral unit)ratio increased from 2.30 and 1.02 to 2.52 and 2.14,respectively,indicating a progressive polymerization of the silicate structure.X-ray photoelectron spectroscopy(XPS)results highlighted that non-bridging oxygen content decreased from 77.97mol% to 63.41mol% with increasing MgO concentration,whereas bridging oxygen and free oxygen contents increased.Structural analysis demonstrated a gradual increase in the polymerization degree of the tetrahedral structure with the increase in MgO substitution.However,bond strength is another important factor affecting the slag viscosity.The occurrence of a viscosity minimum can be attributed to the complex evolution of bond strengths of non-bridging oxygens generated during depolymerization of the[SiO_(4)]and[AlO_(4)]tetrahedral structures by CaO and MgO.展开更多
China has abundant resources of high-alumina coal(HAC).However,its application as a raw gasification material is limited owing to high ash-fusion characteristics.For overcoming the limitation,this study employed Xinji...China has abundant resources of high-alumina coal(HAC).However,its application as a raw gasification material is limited owing to high ash-fusion characteristics.For overcoming the limitation,this study employed Xinjiang coal(XJ),having a low ash fusion temperature,to improve the ash fusibility and viscosity of high-alumina Jungar coal(JG).The evolution of Al-containing phases and structures during mixed ash melting were investigated based on XRD,XPS,27Al NMR,high-temperature stage microscopy(HTSM),and thermodynamic simulations.An increase in the XJ mass ratio resulted in the transformation of gehlenite to anorthite and mullite,producing more amorphous materials at high temperature.These phenomena were manifested at a microscopic imaging as an increase in the number of reaction/melting sites and their area expansion rate,as well as a decrease in ash area shrinkage and melting temperature.Moreover,the introduction of XJ altered the alumina-oxygen network,reducing the binding to the silicaoxygen network and converting some[AlO_(6)]^(9-)to[AlO_(4)]^(5-)as the relative concentration of O_(2)-and O-increases.Consequently,the decrease in the stability of the aluminate structure improves the AFT and viscosity.Based on these results,a mechanism to improve the ash fusion characteristics of HAC based on coal blending is proposed.展开更多
ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a signifi...ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a significant synthetic challenge.Herein,we demonstrate the possibility to control the Al distribution in ITR zeolites using zeolite A as an aluminum source(A-ITR).The A-ITR exhibited similar crystallinity,nanosheet morphology,textual parameters,and acidic concentration with those of conventional ITR made zeolites using aluminum isopropoxide as an aluminum source(C-ITR).Characterizations of the zeolite product with^(27)Al MQ.MAS NMR spectra,^(27)Al MAS NMR spectra,and 1-hexene cracking reveal that the A-ITR zeolites have more Al species distributed in T6 and T8 sites located in relatively smaller micropores of the framework than C-ITR.As a result,the A-ITR gave enhanced catalyst lifetime and propylene selectivity due to the suppression of the aromatic cycle in the MTP reaction,compared with the C-ITR.This work provides an alternative approach to prepare efficient ITR zeolites for MTP reaction.展开更多
The effects of different Al_(2)O_(3)/SiO_(2)(Al/Si)ratios on the structure and tensile strength of Na_(2)O-CaO-MgO-Al_(2)O_(3)-SiO_(2)glass fiber were investigated by Raman,tensile strength tests and molecular dynamic...The effects of different Al_(2)O_(3)/SiO_(2)(Al/Si)ratios on the structure and tensile strength of Na_(2)O-CaO-MgO-Al_(2)O_(3)-SiO_(2)glass fiber were investigated by Raman,tensile strength tests and molecular dynamics simulation.The results showed that Al^(3+)mainly existed in the form of[AlO_(4)]within the glass network.With the increase of Al/Si ratio,the Si-O-Al linkage gradually became the main connection mode of glass network.The increase of bridging oxygen content and variation of Q^(n) indicated that a higher degree of network polymerization was formed.The tensile strength of the glass fibers obtained through experiments increased from 2653.56 to 2856.83 MPa,which was confirmed by the corresponding molecular dynamics simulation.During the stretching process,the Si-O bonds in the Si-O-Al linkage tended to break regardless of the compositional changes,and the increase of fractured Si-O-Al and Al-O-Al linkage absorbed more energy to resist the destroy.展开更多
基金supported by the National Natural Science Foundation of China(No.22302116)the Fundamental Research Program of Shanxi Province(No.202203021212412)Qingchuang Technology Support Program of the University in Shandong Province(No.2023KJ246).
文摘The Baeyer-Villiger(BV)oxidation of cyclohexanone is explored using IWV-type aluminosilicates with different Al sites as heterogeneous catalysts.The IWV framework exhibits a two-dimensional 12-membered ring(MR)pore system intersected by 14-MR supercages,resembling typical beta zeolite.To address the constraints associated with hydrothermal synthesis,IWV aluminosilicates were synthesized via interzeolite transformation of various FAU-type zeolites.HF-assisted transformation of dealuminated FAU zeolite resulted in the formation of a high-silica IWV aluminosilicate(Si/Al=54.6),whereas the incorporation of aluminum isopropoxide enables the tuning of Si/Al ratio down to 18.7.The alkaline conversion of protonated FAU zeolites,utilizing Na^(+)ions as mineralizing agents,produces high-Al content IWV derivatives in just four days.Catalytic evaluation demonstrates that the high-silica IWV catalyst exhibits a higher turnover number than the other IWV catalysts,along with enhancedε-caprolactone(CL)selectivity relative to that of high-silica beta zeolite.Facile modifications are performed to adjust Al sites,as characterized by pyridine-adsorbed infrared spectroscopy.Experimental evidence confirms that Al Brønsted acid sites improves the selective oxidation of cyclohexanone,while concurrently enhancing CL hydrolysis.
文摘Low-cost adsorbents constituted by Fe-modified-aluminosilicates （laminar and zeolite type minerals） were developed and characterized to be used in the arsenic removal from groundwater. Iron activation was carried out ＂in situ＂ by the synthesis and deposition of mesoporous ferrihydrite. Natural iron-rich aluminosilicate was used as reference. All samples were characterized by X-ray diffraction, Raman spectroscopy, BET N2-adsorption, SEM-EDS microscopy and ICP chemical analysis. Experimental results of arsenic sorption showed that iron-poor raw materials were not active, unlike iron activated samples. The iron loading in all activated samples was below 5% （expressed as Fe203）, whereas the removal capacity of these samples reaches between 200-700 gg of As by g of adsorbent, after reusing between 17 cycles and 70 cycles up to adsorbent saturation. Differences can be associated to mineral structure and to the surface charge modification by iron deposition, affecting the attraction of the As-oxoanion. On the basis of low-cost raw materials, the easy chemical process for activation shows that these materials are potentially attractive for As（V） removal. Likewise, the activation of clay minerals, with natural high content of iron, seems to be a good strategy to enhance the arsenic adsorption ability and consequently the useful life of the adsorbent.
基金support through the research programs(Grant Nos.DQzX-KY-21-008,KYWX-21-023,and KYWX-21-022).
文摘Well-ordered aluminosilicates(MAs)were prepared by in-situ assembly of pre-crystallized units of zeolite Y precursors at a commercial scale,and applied in an industrial fluid catalytic cracking unit for the first time.Compared with incumbent equilibrium catalyst,the surface area of trial equilibrium catalysts(30%inventory ratio)increased from 110 m^(2)g^(-1)to 120m^(2)g^(-1).Moreover,a significant increase of the mesoporous surfaceareaof trial equlibrium catalysts(30%inventoryrati)from 33 m g/to 40magi(22%increase).Furthermore,the equilibrium catalyst that contain 80%LPC-65 yields significantly lower heavy oil(0.23%)and higher total liquids(0.53%)compared with LDO-70.The industrial results demonstrated excellent hydrothermal stability and superior catalytic cracking properties,showing the promising futurein the industrial units.
文摘In this study the characterization of an aluminosilicate synthesized from commercial Al2(SO4)3 and colloidal SiO2 is presented, as well as its capacity for the removal of copper from aqueous solution. Characterization of the synthesized material was performed using X-ray diffraction, BET nitrogen adsorption-desorption, mass titration and the Boehm method. In order to obtain stable agglomeration and enhance its surface area (165 - 243 m2/g) and solid adsorbing capabilities, the molar ratio SiO2:Al2O3 (1:3, 1:1 and 3:1) was studied, the solubility of the preparation material, synthesis-procedure time and solution pH function were also examined. The maximum capacity to remove copper ions from an aqueous solution by synthesized aluminosilicate was 16 mg/g at pH 4 and 25℃. The Langmuir model fitted better to the copper adsorption experimental data.
基金financially supported by the National Natural Science Foundation of China(Nos.52425408 and 52304345)the Fundamental Research Funds for the Central Universities,China(No.2023CDJXY-016)the Postdoctoral Science Foundation of Chongqing(No.CSTB2023NSCQ-BHX0174)。
文摘Currently,the Al_(2)O_(3)content in the high-alumina slag systems within blast furnaces is generally limited to 16wt%–18.5wt%,making it challenging to overcome this limitation.Unlike most studies that concentrated on managing the MgO/Al_(2)O_(3)ratio or basicity,this paper explored the effect of equimolar substitution of MgO for CaO on the viscosity and structure of a high-alumina CaO-MgO-Al_(2)O_(3)-SiO_(2)slag system,providing theoretical guidance and data to facilitate the application of high-alumina ores.The results revealed that the viscosity first decreased and then increased with higher MgO substitution,reaching a minimum at 15mol%MgO concentration.Fourier transform infrared spectroscopy(FTIR)results found that the depths of the troughs representing[SiO_(4)]tetrahedra,[AlO_(4)]tetrahedra,and Si-O-Al bending became progressively deeper with increased MgO substitution.Deconvolution of the Raman spectra showed that the average number of bridging oxygens per Si atom and the X_(Q^(3))/X_(Q^(2))(X_(Q^(i))is the molar fraction of Q^(i) unit,and i is the number of bridging oxygens in a[SiO_(4)]tetrahedral unit)ratio increased from 2.30 and 1.02 to 2.52 and 2.14,respectively,indicating a progressive polymerization of the silicate structure.X-ray photoelectron spectroscopy(XPS)results highlighted that non-bridging oxygen content decreased from 77.97mol% to 63.41mol% with increasing MgO concentration,whereas bridging oxygen and free oxygen contents increased.Structural analysis demonstrated a gradual increase in the polymerization degree of the tetrahedral structure with the increase in MgO substitution.However,bond strength is another important factor affecting the slag viscosity.The occurrence of a viscosity minimum can be attributed to the complex evolution of bond strengths of non-bridging oxygens generated during depolymerization of the[SiO_(4)]and[AlO_(4)]tetrahedral structures by CaO and MgO.
基金support from the National Natural Science Foundation of China(22408004)the Scientific Research Foundation for the Introduction of Talent,Anhui University of Science and Technology(2023yjrc90)+1 种基金the Fundamental Research Funds of the AUST(2024JBQN0015)the Open Research Fund Program of Anhui Provincial Institute of Modern Coal Processing Technology,Anhui University of Science and Technology(MTY202302).
文摘China has abundant resources of high-alumina coal(HAC).However,its application as a raw gasification material is limited owing to high ash-fusion characteristics.For overcoming the limitation,this study employed Xinjiang coal(XJ),having a low ash fusion temperature,to improve the ash fusibility and viscosity of high-alumina Jungar coal(JG).The evolution of Al-containing phases and structures during mixed ash melting were investigated based on XRD,XPS,27Al NMR,high-temperature stage microscopy(HTSM),and thermodynamic simulations.An increase in the XJ mass ratio resulted in the transformation of gehlenite to anorthite and mullite,producing more amorphous materials at high temperature.These phenomena were manifested at a microscopic imaging as an increase in the number of reaction/melting sites and their area expansion rate,as well as a decrease in ash area shrinkage and melting temperature.Moreover,the introduction of XJ altered the alumina-oxygen network,reducing the binding to the silicaoxygen network and converting some[AlO_(6)]^(9-)to[AlO_(4)]^(5-)as the relative concentration of O_(2)-and O-increases.Consequently,the decrease in the stability of the aluminate structure improves the AFT and viscosity.Based on these results,a mechanism to improve the ash fusion characteristics of HAC based on coal blending is proposed.
基金supported by the National Key Research and Development Program of China(2022YFA1503602)the National Natural Science Foundation of China(22288101,U21B20101 and 22172141)+1 种基金the BASF International Network of Centers of Excellence projectthe Zhejiang Provincial Natural Science Foundation of China(LR24B030001)。
文摘ITR zeolite could be potentially used as catalysts in methanol to propylene(MTP),where their performance is strongly related to its Al distribution.However,the control of Al distribution in ITR zeolite poses a significant synthetic challenge.Herein,we demonstrate the possibility to control the Al distribution in ITR zeolites using zeolite A as an aluminum source(A-ITR).The A-ITR exhibited similar crystallinity,nanosheet morphology,textual parameters,and acidic concentration with those of conventional ITR made zeolites using aluminum isopropoxide as an aluminum source(C-ITR).Characterizations of the zeolite product with^(27)Al MQ.MAS NMR spectra,^(27)Al MAS NMR spectra,and 1-hexene cracking reveal that the A-ITR zeolites have more Al species distributed in T6 and T8 sites located in relatively smaller micropores of the framework than C-ITR.As a result,the A-ITR gave enhanced catalyst lifetime and propylene selectivity due to the suppression of the aromatic cycle in the MTP reaction,compared with the C-ITR.This work provides an alternative approach to prepare efficient ITR zeolites for MTP reaction.
基金Funded by National Natural Science Foundation of China(No.52172019)Shandong Provincial Youth Innovation Team Development Plan of Colleges and Universities(No.2022KJ100)。
文摘The effects of different Al_(2)O_(3)/SiO_(2)(Al/Si)ratios on the structure and tensile strength of Na_(2)O-CaO-MgO-Al_(2)O_(3)-SiO_(2)glass fiber were investigated by Raman,tensile strength tests and molecular dynamics simulation.The results showed that Al^(3+)mainly existed in the form of[AlO_(4)]within the glass network.With the increase of Al/Si ratio,the Si-O-Al linkage gradually became the main connection mode of glass network.The increase of bridging oxygen content and variation of Q^(n) indicated that a higher degree of network polymerization was formed.The tensile strength of the glass fibers obtained through experiments increased from 2653.56 to 2856.83 MPa,which was confirmed by the corresponding molecular dynamics simulation.During the stretching process,the Si-O bonds in the Si-O-Al linkage tended to break regardless of the compositional changes,and the increase of fractured Si-O-Al and Al-O-Al linkage absorbed more energy to resist the destroy.
