Shape-selective catalysts for the disproportionation of toluene were prepared by the modification of the cylinder-shaped ZSM-5 zeolite extrudates with chemical liquid deposition with TEOS (tetraethyl orthosilicate)....Shape-selective catalysts for the disproportionation of toluene were prepared by the modification of the cylinder-shaped ZSM-5 zeolite extrudates with chemical liquid deposition with TEOS (tetraethyl orthosilicate).Various parameters for preparing catalysts were changed to investigate the suitable conditions.The resulting cata-lysts were tested in a pressured fixed bed reactor and characterized by SEM (scanning electron microscopy).The conversion of toluene and para-xylene selectivity were influenced remarkably by the n(SiO2)/n(Al2O3) ratio of ZSM-5 zeolite,the type and amount of deposition agent,acid and solvent used,and the time and cycle of deposition treatment.TEOS was proved to be a more efficient agent than the conventional polysiloxanes when the deposition amount was low.The catalyst prepared at the suitable conditions exhibited a high para-xylene selectivity of 91.1% with considerable high conversion of 25.6%.SEM analyses confirmed the formation of a layer of amorphous silica on the external surface of ZSM-5 zeolie crystals,which was responsible for the highly enhanced shape-selectivity.展开更多
Exo-tetrahydrodicyclopentadiene (exo-TCD) is an important high-energy fuel. Silicotungstic acid (SiW) immobilized on H-type β zeolite (Hβ) at room temperature were used to prepare the Hβ zeolite catalysts wit...Exo-tetrahydrodicyclopentadiene (exo-TCD) is an important high-energy fuel. Silicotungstic acid (SiW) immobilized on H-type β zeolite (Hβ) at room temperature were used to prepare the Hβ zeolite catalysts with different SiW contents. Catalytic performances of the catalysts were investigated during the preparation of exo-TCD via isomerization of endo-tetrahydrodicyclopentadiene (endo-TCD). The properties of catalysts were characterized by XRD, temperature pro- grammed desorption of ammonia (NHa-TPD), FT-IR, and N2-adsorption techniques. SiW was highly dispersed on the surface of Hβ zeolite, and the 10% SiW/Hβ zeolite catalyst had the highest amount of weak acidity among all SiW/Hβ zeolite catalysts. The influence of different factors on isomerization reaction was investigated. At a reaction temperature of 240 ℃, a n(cyclohexane) / n(endo-TCD) ratio of 10, a m(catalyst)/m(endo-TCD) ratio of 0.3, an initial pressure of 1.0 MPa, and a reaction time of 1.5 h in the presence of 10% SiW/Hβ catalyst calcined at 400 ℃, the conversion of endo-TCD reached up to 92.0%, with the yield of exo-TCD equating to 51.0%.展开更多
The mesoporous Al-SBA-15 zeolite was obtained via impregnation of pure silica-based SBA-15 zeolite with aluminum nitrate.The Al-SBA-15 sample was calcined in air at 800 ℃ for 6 h and hydrothermally treated at near 1...The mesoporous Al-SBA-15 zeolite was obtained via impregnation of pure silica-based SBA-15 zeolite with aluminum nitrate.The Al-SBA-15 sample was calcined in air at 800 ℃ for 6 h and hydrothermally treated at near 100 ℃ for 120 h,respectively,and then the thermal and hydrothermal stability of Al-SBA-15 sample was investigated by X-ray diffractometry (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM) and nitrogen adsorption and desorption techniques.The Al-SBA-15 sample was also studied by 27 Al nuclear magnetic resonance (27 Al NMR) and ammonia temperature programmed desorption (NH 3-TPD) techniques.In addition,the catalytic activity of Al-SBA-15 zeolite was investigated by the Friedel-Crafts reactions of 2,4-di-tert-butylphenol with cinnamyl alcohol.The test results showed that the thermal and hydrothermal stability of Al-SBA-15 zeolite was better than that of SBA-15 zeo-lite.The Al-SBA-15 zeolite sample prepared by impregnation method exhibits more framework aluminum species and Al-O-Si units.Therefore,the number of the surface hydroxyl groups was reduced,resulting in the stabilization of framework structure ofAl-SBA-15 zeolite.The aluminum species can form weak and medium-strong acid sites with catalytic activity.展开更多
A comparison of the adsorption of benzoic acid and p-nitrobenzoic acid on the new hypercrosslinked polymeric adsorbent AM-1, with that by macroporous Amberlite XAD-4, including the equilibrium adsorption isotherms, th...A comparison of the adsorption of benzoic acid and p-nitrobenzoic acid on the new hypercrosslinked polymeric adsorbent AM-1, with that by macroporous Amberlite XAD-4, including the equilibrium adsorption isotherms, the dynamic adsorption behaviors through column and the adsorption thermodynamics were studied. Results show that Freundlich equation gives a fitting adsorption isotherm. The specific surface of AM-1 is only 67% of that of Amberlite XAD-4, but the adsorption capacities on AM-1 are much higher about 125%~166% than that on Amberlite XAD-4, which is contributed to the micropore mechanism and polarity. The negative values of the adsorption enthalpy are indicative of an exothermic process. Enthalpy and free energy changes of adsorption both manifest a physic-sorption process. The negative values of the adsorption entropy indicate that the adsorption is well consistent with the restricted mobilities and the configurations of the adsorbed benzoic acid molecules on the surface of studied adsorbents with superficial heterogeneity. Both adsorbents were used in mini-column experiments for adsorbing benzoic acid expecting to elucidate the higher breakthrough adsorption capacity of the new hypercrosslinked polymeric adsorbent AM-1 as compared with that of Amberlite XAD-4.展开更多
基金Supported by the Key Natural Science Foundation for Universities of Jiangsu Province(06KJA53012) the National Natural Science Foundation of China(20776069 20976084)
文摘Shape-selective catalysts for the disproportionation of toluene were prepared by the modification of the cylinder-shaped ZSM-5 zeolite extrudates with chemical liquid deposition with TEOS (tetraethyl orthosilicate).Various parameters for preparing catalysts were changed to investigate the suitable conditions.The resulting cata-lysts were tested in a pressured fixed bed reactor and characterized by SEM (scanning electron microscopy).The conversion of toluene and para-xylene selectivity were influenced remarkably by the n(SiO2)/n(Al2O3) ratio of ZSM-5 zeolite,the type and amount of deposition agent,acid and solvent used,and the time and cycle of deposition treatment.TEOS was proved to be a more efficient agent than the conventional polysiloxanes when the deposition amount was low.The catalyst prepared at the suitable conditions exhibited a high para-xylene selectivity of 91.1% with considerable high conversion of 25.6%.SEM analyses confirmed the formation of a layer of amorphous silica on the external surface of ZSM-5 zeolie crystals,which was responsible for the highly enhanced shape-selectivity.
文摘Exo-tetrahydrodicyclopentadiene (exo-TCD) is an important high-energy fuel. Silicotungstic acid (SiW) immobilized on H-type β zeolite (Hβ) at room temperature were used to prepare the Hβ zeolite catalysts with different SiW contents. Catalytic performances of the catalysts were investigated during the preparation of exo-TCD via isomerization of endo-tetrahydrodicyclopentadiene (endo-TCD). The properties of catalysts were characterized by XRD, temperature pro- grammed desorption of ammonia (NHa-TPD), FT-IR, and N2-adsorption techniques. SiW was highly dispersed on the surface of Hβ zeolite, and the 10% SiW/Hβ zeolite catalyst had the highest amount of weak acidity among all SiW/Hβ zeolite catalysts. The influence of different factors on isomerization reaction was investigated. At a reaction temperature of 240 ℃, a n(cyclohexane) / n(endo-TCD) ratio of 10, a m(catalyst)/m(endo-TCD) ratio of 0.3, an initial pressure of 1.0 MPa, and a reaction time of 1.5 h in the presence of 10% SiW/Hβ catalyst calcined at 400 ℃, the conversion of endo-TCD reached up to 92.0%, with the yield of exo-TCD equating to 51.0%.
文摘The mesoporous Al-SBA-15 zeolite was obtained via impregnation of pure silica-based SBA-15 zeolite with aluminum nitrate.The Al-SBA-15 sample was calcined in air at 800 ℃ for 6 h and hydrothermally treated at near 100 ℃ for 120 h,respectively,and then the thermal and hydrothermal stability of Al-SBA-15 sample was investigated by X-ray diffractometry (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM) and nitrogen adsorption and desorption techniques.The Al-SBA-15 sample was also studied by 27 Al nuclear magnetic resonance (27 Al NMR) and ammonia temperature programmed desorption (NH 3-TPD) techniques.In addition,the catalytic activity of Al-SBA-15 zeolite was investigated by the Friedel-Crafts reactions of 2,4-di-tert-butylphenol with cinnamyl alcohol.The test results showed that the thermal and hydrothermal stability of Al-SBA-15 zeolite was better than that of SBA-15 zeo-lite.The Al-SBA-15 zeolite sample prepared by impregnation method exhibits more framework aluminum species and Al-O-Si units.Therefore,the number of the surface hydroxyl groups was reduced,resulting in the stabilization of framework structure ofAl-SBA-15 zeolite.The aluminum species can form weak and medium-strong acid sites with catalytic activity.
基金Educational Committee of Jiangsu Province. (01KJD150004)
文摘A comparison of the adsorption of benzoic acid and p-nitrobenzoic acid on the new hypercrosslinked polymeric adsorbent AM-1, with that by macroporous Amberlite XAD-4, including the equilibrium adsorption isotherms, the dynamic adsorption behaviors through column and the adsorption thermodynamics were studied. Results show that Freundlich equation gives a fitting adsorption isotherm. The specific surface of AM-1 is only 67% of that of Amberlite XAD-4, but the adsorption capacities on AM-1 are much higher about 125%~166% than that on Amberlite XAD-4, which is contributed to the micropore mechanism and polarity. The negative values of the adsorption enthalpy are indicative of an exothermic process. Enthalpy and free energy changes of adsorption both manifest a physic-sorption process. The negative values of the adsorption entropy indicate that the adsorption is well consistent with the restricted mobilities and the configurations of the adsorbed benzoic acid molecules on the surface of studied adsorbents with superficial heterogeneity. Both adsorbents were used in mini-column experiments for adsorbing benzoic acid expecting to elucidate the higher breakthrough adsorption capacity of the new hypercrosslinked polymeric adsorbent AM-1 as compared with that of Amberlite XAD-4.