In order to further improve the catalytic performance of zeolite catalyst for methanol to aromatics(MTA)technology, the double-tier SAPO-34/ZSM-5/quartz composite zeolite films were successfully synthesized via hydrot...In order to further improve the catalytic performance of zeolite catalyst for methanol to aromatics(MTA)technology, the double-tier SAPO-34/ZSM-5/quartz composite zeolite films were successfully synthesized via hydrothermal crystallization. The Si/Al ratio of SAPO-34 film was used as the only variable to study this material. The composite zeolite material with 0.6Si/Al ratio of SAPO-34 has the largest mesoporous specific surface area and the most suitable acid distribution. The catalytic performance for the MTA process showed that 0.6-SAPO-34/ZSM-5/quartz film has as high as 50.3% benzene-toluenexylene selectivity and 670 min lifetime. The MTA reaction is carried out through the path we designed to effectively avoid the hydrocarbon pool circulation of ZSM-5 zeolite, so as to improve the aromatics selectivity and inhibit the occurrence of deep side reactions to a great extent. The coke deposition behavior was monitored by thermogravimetric analysis and gas chromatograph/mass spectrometer, it is found that with the increase of Si/Al ratio, the active intermediates changed from low-substituted methylbenzene to high-substituted methylbenzene, which led to the rapid deactivation of the catalyst. This work provides a possibility to employ the synergy effect of composite zeolite film synthesizing anti-carbon deposition catalyst in MTA reaction.展开更多
In order to improve the activity and eliminate some impurities, pretreatment was used before hydrothermal synthesis. The fly ash was mixed with an aqueous NaOH solution, the alkali melted fly ash was also adopted, whi...In order to improve the activity and eliminate some impurities, pretreatment was used before hydrothermal synthesis. The fly ash was mixed with an aqueous NaOH solution, the alkali melted fly ash was also adopted, which is hydrothermally treated at about 104 ℃, and the liquid/solid ratio was controlled at 6：1. In order to control Si/Al molar ratio, SiO2 or Al2O3 powers were added to the fly ash. The results of XRD and SEM show that the alkali melted can activate fly ash and eliminate its quartz and mullite, along with the improvement of Si/Al molar ratio and alkalinity. In addition, zeolite Na-A changes into sodalite gradually, and nepheline is the synthesized intermediate product. Those results were discussed on the basis of a formation mechanism of zeolite from fly ash.展开更多
Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and but...Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and butene-1 and their mixtures on these catalysts at 300K and p=0—100kPa were measured using the intelligent gra- vimetric analyzer.The experimental results indicate that the presence of Al can significantly affect the adsorption of butene-1 than that of n-butane on ZSM-5 zeolites.Then,the double Langmuir(DL)model was applied to study the pure gas adsorption on ZSM-5 zeolites for pure n-butane and butene-1.By combining the DL model with the ideal adsorbed solution theory(IAST),the IAST-DL model was applied to model the butene-1(1)/n-butane(2)binary mixture adsorption on ZSM-5 zeolites with different Si/Al ratios.The calculated results are in good agreement with the experimental data,indicating that the IAST-DL model is effective for the present systems.Finally,the adsorp- tion over a wide range of variables was predicted at low pressure and 300K by the model proposed.It is found that the selectivity of butene-1 over n-butane increases linearly with the decrease of Si/Al ratio.A correlation between the selectivity and Si/Al ratio of the sample was proposed at 300K and p=0.08MPa.展开更多
A new Mg−10%Al−1%Zn−1%Si alloy with non-dendritic microstructure was prepared by strain induced melt activation(SIMA)process.The effect of compression ratio on the evolution of semisolid microstructure of the experime...A new Mg−10%Al−1%Zn−1%Si alloy with non-dendritic microstructure was prepared by strain induced melt activation(SIMA)process.The effect of compression ratio on the evolution of semisolid microstructure of the experimental alloy was investigated.The results indicate that the average size ofα-Mg grains decreases and spheroidizing tendency becomes more obvious with the compression ratios increasing from 0 to 40%.In addition,the eutectic Mg2Si phase in the Mg−10%Al−1%Zn−1%Si alloy transforms completely from the initial fishbone shape to globular shape by SIMA process.With the increasing of compression ratio,the morphology and average size of Mg2Si phases do not change obviously.The morphology modification mechanism of Mg2Si phase in Mg−10%Al−1%Zn−1%Si alloy by SIMA process was also studied.展开更多
In order to recover the SiO_2 contained in the mother liquor in the course ofNaY zeolite synthesis to minimize pollution, the influence of various preparation conditions on thefiltering velocity of gel slurry was stud...In order to recover the SiO_2 contained in the mother liquor in the course ofNaY zeolite synthesis to minimize pollution, the influence of various preparation conditions on thefiltering velocity of gel slurry was studied using the SiO_2/Al_2O_3 gel recovered from the NaYmother liquor in the laboratory. The results of study had shown that at a SiO_2/Al_2O_3 ratio in thefeed equating to 9∶1 the SiO_2 recovery rate and Al_2O_3 utilization rate were high with a fasterflow velocity of the filtrate. The pH value of the system had great impact on the flow velocity offiltrate. Between the two methods for regulating the pH value, the one for formation ofsilica/alumina gel slurry by addition of sulfuric acid prior to adding aluminium sulfate in thesolution could secure a faster filtration velocity. The filtration velocity was decreased in tandemwith increasing SiO_2 concentration in mother liquor, meanwhile an increase in dry filter cakeyield.展开更多
A series of as-synthesized HZSM-5 zeolites with different Si/Al ratios(25,90,120,240 and 400)were post-treated by ultrasonication for an optimum time of 60 min.The morphology,acidity and textural properties of HZSM-5 ...A series of as-synthesized HZSM-5 zeolites with different Si/Al ratios(25,90,120,240 and 400)were post-treated by ultrasonication for an optimum time of 60 min.The morphology,acidity and textural properties of HZSM-5 were characterized with XRD,SEM,N_2 adsorption and NH3-TPD techniques.The catalytic performance was evaluated by dehydration of methanol to dimethyl ether(DME),which is a promising gaseous automotive fuel in future.It was found that the Si/Al ratio of HZSM-5 had considerable impacts on its catalytic performance for dehydration of methanol to DME.Its activity increased with decreasing Si/Al ratio from 400 to 25.Ultrasonication of HZSM-5 could significantly improve its catalytic performance.展开更多
基金supported by the National Natural Science Foundation of China (51974312, 51974308)the National Key Research & Development Program of China (2019YFE0100100)。
文摘In order to further improve the catalytic performance of zeolite catalyst for methanol to aromatics(MTA)technology, the double-tier SAPO-34/ZSM-5/quartz composite zeolite films were successfully synthesized via hydrothermal crystallization. The Si/Al ratio of SAPO-34 film was used as the only variable to study this material. The composite zeolite material with 0.6Si/Al ratio of SAPO-34 has the largest mesoporous specific surface area and the most suitable acid distribution. The catalytic performance for the MTA process showed that 0.6-SAPO-34/ZSM-5/quartz film has as high as 50.3% benzene-toluenexylene selectivity and 670 min lifetime. The MTA reaction is carried out through the path we designed to effectively avoid the hydrocarbon pool circulation of ZSM-5 zeolite, so as to improve the aromatics selectivity and inhibit the occurrence of deep side reactions to a great extent. The coke deposition behavior was monitored by thermogravimetric analysis and gas chromatograph/mass spectrometer, it is found that with the increase of Si/Al ratio, the active intermediates changed from low-substituted methylbenzene to high-substituted methylbenzene, which led to the rapid deactivation of the catalyst. This work provides a possibility to employ the synergy effect of composite zeolite film synthesizing anti-carbon deposition catalyst in MTA reaction.
基金Supported by the Henan Outstanding Youth Science Fund (0612002400)
文摘In order to improve the activity and eliminate some impurities, pretreatment was used before hydrothermal synthesis. The fly ash was mixed with an aqueous NaOH solution, the alkali melted fly ash was also adopted, which is hydrothermally treated at about 104 ℃, and the liquid/solid ratio was controlled at 6：1. In order to control Si/Al molar ratio, SiO2 or Al2O3 powers were added to the fly ash. The results of XRD and SEM show that the alkali melted can activate fly ash and eliminate its quartz and mullite, along with the improvement of Si/Al molar ratio and alkalinity. In addition, zeolite Na-A changes into sodalite gradually, and nepheline is the synthesized intermediate product. Those results were discussed on the basis of a formation mechanism of zeolite from fly ash.
基金Supported by the National Natural Science Foundation of China （Nos.20236010,20476004） and China Petroleum ＆ Chemical Corporation （No.X504023）.
文摘Four ZSM-5 zeolite catalysts with different Si/Al ratios for the catalytic cracking of C4 fractions to produce ethylene and propylene were prepared in this study.First,the adsorption isotherms of pure n-butane and butene-1 and their mixtures on these catalysts at 300K and p=0—100kPa were measured using the intelligent gra- vimetric analyzer.The experimental results indicate that the presence of Al can significantly affect the adsorption of butene-1 than that of n-butane on ZSM-5 zeolites.Then,the double Langmuir(DL)model was applied to study the pure gas adsorption on ZSM-5 zeolites for pure n-butane and butene-1.By combining the DL model with the ideal adsorbed solution theory(IAST),the IAST-DL model was applied to model the butene-1(1)/n-butane(2)binary mixture adsorption on ZSM-5 zeolites with different Si/Al ratios.The calculated results are in good agreement with the experimental data,indicating that the IAST-DL model is effective for the present systems.Finally,the adsorp- tion over a wide range of variables was predicted at low pressure and 300K by the model proposed.It is found that the selectivity of butene-1 over n-butane increases linearly with the decrease of Si/Al ratio.A correlation between the selectivity and Si/Al ratio of the sample was proposed at 300K and p=0.08MPa.
基金The authors are grateful for the financial supports from the National Natural Science Foundation of China(Nos.41807235,50674038).
文摘A new Mg−10%Al−1%Zn−1%Si alloy with non-dendritic microstructure was prepared by strain induced melt activation(SIMA)process.The effect of compression ratio on the evolution of semisolid microstructure of the experimental alloy was investigated.The results indicate that the average size ofα-Mg grains decreases and spheroidizing tendency becomes more obvious with the compression ratios increasing from 0 to 40%.In addition,the eutectic Mg2Si phase in the Mg−10%Al−1%Zn−1%Si alloy transforms completely from the initial fishbone shape to globular shape by SIMA process.With the increasing of compression ratio,the morphology and average size of Mg2Si phases do not change obviously.The morphology modification mechanism of Mg2Si phase in Mg−10%Al−1%Zn−1%Si alloy by SIMA process was also studied.
文摘In order to recover the SiO_2 contained in the mother liquor in the course ofNaY zeolite synthesis to minimize pollution, the influence of various preparation conditions on thefiltering velocity of gel slurry was studied using the SiO_2/Al_2O_3 gel recovered from the NaYmother liquor in the laboratory. The results of study had shown that at a SiO_2/Al_2O_3 ratio in thefeed equating to 9∶1 the SiO_2 recovery rate and Al_2O_3 utilization rate were high with a fasterflow velocity of the filtrate. The pH value of the system had great impact on the flow velocity offiltrate. Between the two methods for regulating the pH value, the one for formation ofsilica/alumina gel slurry by addition of sulfuric acid prior to adding aluminium sulfate in thesolution could secure a faster filtration velocity. The filtration velocity was decreased in tandemwith increasing SiO_2 concentration in mother liquor, meanwhile an increase in dry filter cakeyield.
文摘A series of as-synthesized HZSM-5 zeolites with different Si/Al ratios(25,90,120,240 and 400)were post-treated by ultrasonication for an optimum time of 60 min.The morphology,acidity and textural properties of HZSM-5 were characterized with XRD,SEM,N_2 adsorption and NH3-TPD techniques.The catalytic performance was evaluated by dehydration of methanol to dimethyl ether(DME),which is a promising gaseous automotive fuel in future.It was found that the Si/Al ratio of HZSM-5 had considerable impacts on its catalytic performance for dehydration of methanol to DME.Its activity increased with decreasing Si/Al ratio from 400 to 25.Ultrasonication of HZSM-5 could significantly improve its catalytic performance.
