The alkylation of toluene with methanol to selective formation of p-xylene has been systematically studied. ZSM-12 （MTW）/ZSM-5 co-crystalline zeolite in 40：60 proportions have been synthesized by the same molar gel...The alkylation of toluene with methanol to selective formation of p-xylene has been systematically studied. ZSM-12 （MTW）/ZSM-5 co-crystalline zeolite in 40：60 proportions have been synthesized by the same molar gel composition, but at different temperatures and periods than that of ZSM-12 and ZSM-5, separately. All the prepared samples are characterized by XRD, SEM, BET, and XRF. The activity of toluene alkylation was investigated with a mixture of toluene and methanol as a feed over the ZSM-12, ZSM-12/ZSM-5 co-crystalline, ZSM-5, and physical mixture of ZSM-12/ZSM-5. From characterization, it is observed that the ZSM-12/ZSM-5 co-crystalline material is different from that of ZSM-12, ZSM-5, and their physical mixture. Further, the ZSM-12/ZSM-5 co-crystalline zeolite produces the highest content of xylene and has better selectivity for p-xylene than ZSM-12, ZSM-5, and their physical mixture.展开更多
A series of calcined HTLcs catalysts were prepared and modified with potassium phosphate by impregnation method to clarify the influence of catalyst alkalinity on the side chain alkylation of toluene with methanol for...A series of calcined HTLcs catalysts were prepared and modified with potassium phosphate by impregnation method to clarify the influence of catalyst alkalinity on the side chain alkylation of toluene with methanol for synthesis of ethylbenzene and styrene.The catalysts were characterized by X-ray diffraction(XRD),N_(2)physical adsorption-desorption,Fourier-transform infrared spectroscopy(FT-IR),Scanning electron microscopy(SEM),X-ray photoelectron spectrometry(XPS),NH_(3)temperature-programmed desorption(NH_(3)-TPD)and CO_(2)temperature-programmed desorption(CO_(2)-TPD).It was found that the selectivity of styrene was highest(39.25%)when the K_(3)PO_(4)loading was 7.5 wt%.And the total yield of styrene and ethylbenzene could reach 65.08%with 10 wt%K_(3)PO_(4)loading.This might due to the fact that the addition of K_(3)PO_(4)could adjust the acid and basic sites of catalysts.In addition,appropriate strength and amount of basic sites were favorable to producing more styrene.展开更多
The surface intermediate (C_2H_5^+ and CH_3C_6H_5^+) and the reactive pathway of nuclear alkylation of toluene with ethylene to para—ethyl toluene over Mg salt and phosphorus acid modified ZSM—5 zeolites have been s...The surface intermediate (C_2H_5^+ and CH_3C_6H_5^+) and the reactive pathway of nuclear alkylation of toluene with ethylene to para—ethyl toluene over Mg salt and phosphorus acid modified ZSM—5 zeolites have been studied by 1R and EPR methods.展开更多
Hierarchical nano-sized ZSM-5 aggregates were successfully synthesized via a seed-assisted method in the presence of cetyltrimethylammonium bromide(CTAB)through a facile one-step crystallization process.Commercial ZSM...Hierarchical nano-sized ZSM-5 aggregates were successfully synthesized via a seed-assisted method in the presence of cetyltrimethylammonium bromide(CTAB)through a facile one-step crystallization process.Commercial ZSM-5 zeolites with a SiO2/Al2O3 ratio comparable to that of ZSM-5 products were treated with alkali and used as the seed particles.The influences of crystallization conditions were investigated,and the possible synthesis mechanism was proposed.ZSM-5 zeolites with diff erent amounts of CTAB added were characterized using many techniques and evaluated in toluene alkylation with methanol.The results showed that a trace amount of CTAB signifi cantly promoted the crystallization of ZSM-5 zeolite,with the morphology changing from hexagonal-shape crystals to uniform spherical aggregates.CTAB may act as the structure-directing agent and assemble the primary crystallites to generate hierarchical ZSM-5 aggregates.The ZSM-5 zeolite with the smallest primary particles of 50-80 nm exhibited large specific surface area,abundant mesopores,and the greatest microporosity.The hierarchical nano-sized ZSM-5 aggregate showed higher toluene conversion and a longer lifetime without compromising the selectivity to xylene and p-xylene in toluene alkylation with methanol.展开更多
Core-shell structured ZSM-5@Silicalite-1 zeolite could effectively hinder the deactivation of catalyst surface. Currently, organic structure directing agents(OSDAs) are necessary in the conventional route for the synt...Core-shell structured ZSM-5@Silicalite-1 zeolite could effectively hinder the deactivation of catalyst surface. Currently, organic structure directing agents(OSDAs) are necessary in the conventional route for the synthesis of this core-shell zeolite under hydrothermal conditions, which is costly and environmental-unfriendly. In this research, a synthesis of the core-shell structured ZSM-5@Silicalite-1 zeolite with a strategy of alcohol filling and zeolite seeding without any organic template or solvent is exhibited. The obtained products are well characterized by X-ray powder diffractometer(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 sorption isotherms, solid magic angle spinning(MAS) NMR, temperature-programmed-desorption of ammonia(NH3-TPD), and X-ray photoelectron spectroscopy(XPS) techniques, in order to confirm the core-shell structure. More importantly, the core-shell structured ZSM-5@Silicalite-1 zeolite exhibits a long lifetime and a high p-xylene selectivity in the alkylation of toluene with methanol, compared with the conventional ZSM-5 catalyst.展开更多
文摘The alkylation of toluene with methanol to selective formation of p-xylene has been systematically studied. ZSM-12 （MTW）/ZSM-5 co-crystalline zeolite in 40：60 proportions have been synthesized by the same molar gel composition, but at different temperatures and periods than that of ZSM-12 and ZSM-5, separately. All the prepared samples are characterized by XRD, SEM, BET, and XRF. The activity of toluene alkylation was investigated with a mixture of toluene and methanol as a feed over the ZSM-12, ZSM-12/ZSM-5 co-crystalline, ZSM-5, and physical mixture of ZSM-12/ZSM-5. From characterization, it is observed that the ZSM-12/ZSM-5 co-crystalline material is different from that of ZSM-12, ZSM-5, and their physical mixture. Further, the ZSM-12/ZSM-5 co-crystalline zeolite produces the highest content of xylene and has better selectivity for p-xylene than ZSM-12, ZSM-5, and their physical mixture.
基金financial support from the National Key Technology Research&Development Program(Grant No.2013BAC14B04)the National Natural Science Foundation of China(Grant No.21336006)+1 种基金the Shanxi Province Key Research&Development Program(international cooperation,Grant No.201803D421099)Supported by Shanxi Scholarship Council of China(Grant No.2017-035)。
文摘A series of calcined HTLcs catalysts were prepared and modified with potassium phosphate by impregnation method to clarify the influence of catalyst alkalinity on the side chain alkylation of toluene with methanol for synthesis of ethylbenzene and styrene.The catalysts were characterized by X-ray diffraction(XRD),N_(2)physical adsorption-desorption,Fourier-transform infrared spectroscopy(FT-IR),Scanning electron microscopy(SEM),X-ray photoelectron spectrometry(XPS),NH_(3)temperature-programmed desorption(NH_(3)-TPD)and CO_(2)temperature-programmed desorption(CO_(2)-TPD).It was found that the selectivity of styrene was highest(39.25%)when the K_(3)PO_(4)loading was 7.5 wt%.And the total yield of styrene and ethylbenzene could reach 65.08%with 10 wt%K_(3)PO_(4)loading.This might due to the fact that the addition of K_(3)PO_(4)could adjust the acid and basic sites of catalysts.In addition,appropriate strength and amount of basic sites were favorable to producing more styrene.
文摘The surface intermediate (C_2H_5^+ and CH_3C_6H_5^+) and the reactive pathway of nuclear alkylation of toluene with ethylene to para—ethyl toluene over Mg salt and phosphorus acid modified ZSM—5 zeolites have been studied by 1R and EPR methods.
基金supported by the National Natural Science Foundation of China(No.21276183).
文摘Hierarchical nano-sized ZSM-5 aggregates were successfully synthesized via a seed-assisted method in the presence of cetyltrimethylammonium bromide(CTAB)through a facile one-step crystallization process.Commercial ZSM-5 zeolites with a SiO2/Al2O3 ratio comparable to that of ZSM-5 products were treated with alkali and used as the seed particles.The influences of crystallization conditions were investigated,and the possible synthesis mechanism was proposed.ZSM-5 zeolites with diff erent amounts of CTAB added were characterized using many techniques and evaluated in toluene alkylation with methanol.The results showed that a trace amount of CTAB signifi cantly promoted the crystallization of ZSM-5 zeolite,with the morphology changing from hexagonal-shape crystals to uniform spherical aggregates.CTAB may act as the structure-directing agent and assemble the primary crystallites to generate hierarchical ZSM-5 aggregates.The ZSM-5 zeolite with the smallest primary particles of 50-80 nm exhibited large specific surface area,abundant mesopores,and the greatest microporosity.The hierarchical nano-sized ZSM-5 aggregate showed higher toluene conversion and a longer lifetime without compromising the selectivity to xylene and p-xylene in toluene alkylation with methanol.
基金This work was supported by the National Key Research and Development Program of China(No.2017YFB0702803)the Fundamental Research Funds for the Central Universities,China(No.2021QNA4028)the National Natural Science Foundation of China(Nos.21802121,2217020097,21720102001).
文摘Core-shell structured ZSM-5@Silicalite-1 zeolite could effectively hinder the deactivation of catalyst surface. Currently, organic structure directing agents(OSDAs) are necessary in the conventional route for the synthesis of this core-shell zeolite under hydrothermal conditions, which is costly and environmental-unfriendly. In this research, a synthesis of the core-shell structured ZSM-5@Silicalite-1 zeolite with a strategy of alcohol filling and zeolite seeding without any organic template or solvent is exhibited. The obtained products are well characterized by X-ray powder diffractometer(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 sorption isotherms, solid magic angle spinning(MAS) NMR, temperature-programmed-desorption of ammonia(NH3-TPD), and X-ray photoelectron spectroscopy(XPS) techniques, in order to confirm the core-shell structure. More importantly, the core-shell structured ZSM-5@Silicalite-1 zeolite exhibits a long lifetime and a high p-xylene selectivity in the alkylation of toluene with methanol, compared with the conventional ZSM-5 catalyst.
