MCM-41 zeolite and Iron (Ⅱ) -Phen/MCM-41 zeolite have been preparedand characterized by XRD,IR, NH3-TPD, BET and UV-Vis. The Iron(Ⅱ)-Phen/MCM-41 zeolite+30% H2O2 system is capable for catalyzing hydroxylation of Phe...MCM-41 zeolite and Iron (Ⅱ) -Phen/MCM-41 zeolite have been preparedand characterized by XRD,IR, NH3-TPD, BET and UV-Vis. The Iron(Ⅱ)-Phen/MCM-41 zeolite+30% H2O2 system is capable for catalyzing hydroxylation of Phenol.展开更多
In this study,various ZSM-5/MCM-41 micro/mesoporous zeolite composites have been prepared by alkalidesilication and surfactant-directed recrystallization of ZSM-5.The effects of particle size and Si/Al ratio of initia...In this study,various ZSM-5/MCM-41 micro/mesoporous zeolite composites have been prepared by alkalidesilication and surfactant-directed recrystallization of ZSM-5.The effects of particle size and Si/Al ratio of initial ZSM-5 zeolites on the structure and catalytic performance of ZSM-5/MCM-41 composites are studied.The results of XRD,TEM N_2-adsorption-desorption,NH_3-TPD and in situ FT-IR revealed that ordered hexagonal MCM-41 mesopores with 3-4 nm pore size were formed around ZSM-5 crystals,and the specific surface area and mesopore volume of composites increased with increasing the Si/Al ratio of initial ZSM-5.Catalytic cracking of n-dodecane(550℃,4 MPa) showed that the ZSM-5/MCM-41 composites obtained from the high Si/Al ratio and nano-sized initial ZSM-5 zeolites exhibited superior catalytic performance,with the improvement higher than 87%in the catalytic activities and 21%in the deactivation rate compared with untreated zeolites.This could be ascribed to their suitable pore structure,which enhanced the diffusion of reactant molecules in pores of catalysts.展开更多
The reaction mechanism for alkylation of benzene with propylene over the β zeolite and the MCM-22 zeolite were investigated respectively by in-situ IR spectrometry. Three types of experiments were carried out. （1） ...The reaction mechanism for alkylation of benzene with propylene over the β zeolite and the MCM-22 zeolite were investigated respectively by in-situ IR spectrometry. Three types of experiments were carried out. （1） IR spectra of the gas-phase propylene, benzene and isopropyl benzene were recorded. （2） IR spectra of the above-mentioned substances as adsorbates that have combined with the zeolite wafer were recorded. （3） IR spectra of the reaction modes were recorded. The test results showed that the alkytation reaction over the zeolite β was ascribed to the mechanism of carbonium ions, whereas the alkylation reaction over the zeolite MCM-22 was ascribed to the synchronous reaction mechanism.展开更多
The performance of MCM-22 zeolite for catalytic isomerization of 1-hexene has been studied. At a n(H2)/n(1-hexene) ratio of 8, the influence of steam treatment temperature, reaction temperature and reaction pressure o...The performance of MCM-22 zeolite for catalytic isomerization of 1-hexene has been studied. At a n(H2)/n(1-hexene) ratio of 8, the influence of steam treatment temperature, reaction temperature and reaction pressure on the performance of MCM-22 zeolite for catalytic skeletal isomerization of 1-hexene was examined. The experimental results showed that at a steam treatment temperature of 500℃, a reaction temperature of 270℃, a space velocity of 1.0 h-1 and a reaction pressure of 0.2 MPa, the MCM-22 zeolite exhibited excellent performance for catalytic skeletal isomerization of 1-hexene with the i-hexene yield reaching 66.15%. Compared with other commonly used molecular sieve catalysts, the MCM-22 zeolite catalyst exhibited better catalytic performance for skeletal isomerization of 1-hexene.展开更多
ITQ-2 zeolites were prepared by sequential alkali-swelling and ultrasonic-delamination of precursor MCM-22 and characterized by X-ray powder diffraction, scanning electron microscopy, nitrogen adsorption-desorption, a...ITQ-2 zeolites were prepared by sequential alkali-swelling and ultrasonic-delamination of precursor MCM-22 and characterized by X-ray powder diffraction, scanning electron microscopy, nitrogen adsorption-desorption, ammonia temperature-programmed desorption and in-situ Fourier-transform infrared spectroscopy. The delamination induced a change in the morphology of ITQ-2 zeolites from aggregated thin platelets to scattered platelets, together with a significant increase in external specific surface area, which reached a plateau at the ultrasonic treatment time of 3 h. The catalytic cracking of n-dodecane over ITQ-2 zeolites was evaluated with ITQ-2 coated on the inside wall of a tubular reactor at 550 ℃ and 4 MPa. The sample obtained by ultrasonic treatment of 3 h （ITQ-2-3） gave the highest initial conversion of n-dodecane, whereas those of 5 h and I h gave the conversion even lower than MCM-22, which was in agreement with the trend of the ratio of strong Lewis acid to the total acid amount. Although the amount of cokes deposited on ITQ-2-3 was larger than that on MCM-22, the former deactivated slowly, suggesting that a large external specific surface area benefits the stability of zeolite coatings,展开更多
The oligomerization of light olefins is an alternative for generating clean liquid fuels.In this study,the MCM-22 zeolite featuring a partially disordered layered structure with framework combined 10 membered ring(10 ...The oligomerization of light olefins is an alternative for generating clean liquid fuels.In this study,the MCM-22 zeolite featuring a partially disordered layered structure with framework combined 10 membered ring(10 MR)was discussed for 1-hexene oligomerization.MCM-22 and Y zeolite were compared to investigate the influences of the framework and acidity strength on the activity and yield in the 1-hexene oligomerization.The results indicated that the MCM-22 zeolite was an efficient catalyst for oligomerization compared to Y zeolite.The MCM-22 zeolite was characterized in detail by NMR,Py-FTIR,and TG analyses.The catalytic performance and deactivation properties of MCM-22 zeolite in the oligomerization reaction of 1-hexene were investigated.Structure-activity relationships were established through the kinetic study.Although the density of strong acid sites was essential for the oligomerization of 1-hexene,the presence of low pressure was also necessary for the formation of dimers.Thus,MCM-22 zeolite demonstrates a substantial improvement in initial conversion and catalyst lifespan for 1-hexene oligomerization.展开更多
Adsorption of xenon in zeolite MCM-22, a zeolite containing two separate pore systems, has been investigated in detail by variable temperature (VT) 129Xe NMR spectroscopy. NMR results suggest that Xe atoms are prefere...Adsorption of xenon in zeolite MCM-22, a zeolite containing two separate pore systems, has been investigated in detail by variable temperature (VT) 129Xe NMR spectroscopy. NMR results suggest that Xe atoms are preferentially adsorbed in the supercages of the zeolite at low Xe pressure (less than a few atmosphere), while Xe atoms can penetrate into the two-dimensional sinusoidal channels at high Xe pressure. Exchange of xenon at the different adsorption sites in the same supercage, i.e. xenon atoms in the two pockets and those in the central part of the supercage, was confirmed at 145 K by two-dimensional (2D) 129Xe NMR exchange spectroscopy. The time scale for the exchange is about several milliseconds.展开更多
Mesoporous aluminosilicate MCM-48 containing zeolite secondary building units in the pore wall has been synthesized in alkaline media with a two-step procedure.The aluminosilicate precursors comprising zeolite seconda...Mesoporous aluminosilicate MCM-48 containing zeolite secondary building units in the pore wall has been synthesized in alkaline media with a two-step procedure.The aluminosilicate precursors comprising zeolite secondary building units were first synthesized by carefully controlling reaction conditions and then were assembled using co-templates of gemini surfactant[C18H37N(CH3)2(CH2)3-N(CH3)2C18H37]2+(18-3-18)and triethanolamine(TEA).X-ray Diffraction(XRD)patterns of the as-made samples indicated that highly ordered mesostructured MCM-48 was formed.Transmission Electron Microscopy(TEM)images further verified the formation of MCM-48 with uniform cubic pore channel system having the pore opening diameter of about 25Å.Compared with the conventionally synthesized MCM-48,the as-synthesized MCM-48 sample showed an adsorption band at 520–600 cm-1 in its FT-IR spectrum,which was assigned to five-membered ring vibration from zeolite structure.This suggested the presence of zeolite building units in the pore wall.N2 adsorption data showed that the material had a much higher specific surface area(1200 m2/g)than the conventional MCM-48(1100 m2/g).Finally,the cat-alytic performance of the as-made MCM-48 was evaluated by hydrogenation dealkylation reaction of heavy aromatic hydrocarbons.Catalytic results showed that the as-made MCM-48 catalyst exhibited higher conversion than the con-ventional MCM-48 catalyst.The as-made mesostructured MCM-48 may have a potential catalytic application in the conversion of bulky molecules.展开更多
The benzene alkylation process for the production of ethylbenzene has undergone significant improvements during recent decades.Various environmentally benign zeolite-catalyzed ethylbenzene processes,including ZSM-5-ze...The benzene alkylation process for the production of ethylbenzene has undergone significant improvements during recent decades.Various environmentally benign zeolite-catalyzed ethylbenzene processes,including ZSM-5-zeolite-based vapor-phase ethylbenzene processes and Y-,β-,and MCM-22-zeolite-based liquid-phase processes,have been developed and commercialized.Pure ethylene,ethanol,and dilute ethylene have been used as ethylation agents.Here,the development and industrial application of alkylation catalysts and benzene ethylation techniques are summarized,and some other promising innovations are discussed.Recent advances in benzene alkylation over hierarchical zeolites with improved access to active sites and molecular transport are also covered.Zeolites with short diffusion lengths are promising candidates as better alkylation catalysts.The key point is how to obtain such materials easily and economically.The structure-activity relationships of commercial zeolites in these processes are discussed.Liquid-phase processes catalyzed by β and MCM-22 are more profitable than vapor-phase processes catalyzed by ZSM-5.展开更多
文摘MCM-41 zeolite and Iron (Ⅱ) -Phen/MCM-41 zeolite have been preparedand characterized by XRD,IR, NH3-TPD, BET and UV-Vis. The Iron(Ⅱ)-Phen/MCM-41 zeolite+30% H2O2 system is capable for catalyzing hydroxylation of Phenol.
基金Supported by the National Natural Science Foundation of China(U123213421306132)the Doctoral Program of Higher Education(20120032120008)
文摘In this study,various ZSM-5/MCM-41 micro/mesoporous zeolite composites have been prepared by alkalidesilication and surfactant-directed recrystallization of ZSM-5.The effects of particle size and Si/Al ratio of initial ZSM-5 zeolites on the structure and catalytic performance of ZSM-5/MCM-41 composites are studied.The results of XRD,TEM N_2-adsorption-desorption,NH_3-TPD and in situ FT-IR revealed that ordered hexagonal MCM-41 mesopores with 3-4 nm pore size were formed around ZSM-5 crystals,and the specific surface area and mesopore volume of composites increased with increasing the Si/Al ratio of initial ZSM-5.Catalytic cracking of n-dodecane(550℃,4 MPa) showed that the ZSM-5/MCM-41 composites obtained from the high Si/Al ratio and nano-sized initial ZSM-5 zeolites exhibited superior catalytic performance,with the improvement higher than 87%in the catalytic activities and 21%in the deactivation rate compared with untreated zeolites.This could be ascribed to their suitable pore structure,which enhanced the diffusion of reactant molecules in pores of catalysts.
文摘The reaction mechanism for alkylation of benzene with propylene over the β zeolite and the MCM-22 zeolite were investigated respectively by in-situ IR spectrometry. Three types of experiments were carried out. （1） IR spectra of the gas-phase propylene, benzene and isopropyl benzene were recorded. （2） IR spectra of the above-mentioned substances as adsorbates that have combined with the zeolite wafer were recorded. （3） IR spectra of the reaction modes were recorded. The test results showed that the alkytation reaction over the zeolite β was ascribed to the mechanism of carbonium ions, whereas the alkylation reaction over the zeolite MCM-22 was ascribed to the synchronous reaction mechanism.
文摘The performance of MCM-22 zeolite for catalytic isomerization of 1-hexene has been studied. At a n(H2)/n(1-hexene) ratio of 8, the influence of steam treatment temperature, reaction temperature and reaction pressure on the performance of MCM-22 zeolite for catalytic skeletal isomerization of 1-hexene was examined. The experimental results showed that at a steam treatment temperature of 500℃, a reaction temperature of 270℃, a space velocity of 1.0 h-1 and a reaction pressure of 0.2 MPa, the MCM-22 zeolite exhibited excellent performance for catalytic skeletal isomerization of 1-hexene with the i-hexene yield reaching 66.15%. Compared with other commonly used molecular sieve catalysts, the MCM-22 zeolite catalyst exhibited better catalytic performance for skeletal isomerization of 1-hexene.
文摘ITQ-2 zeolites were prepared by sequential alkali-swelling and ultrasonic-delamination of precursor MCM-22 and characterized by X-ray powder diffraction, scanning electron microscopy, nitrogen adsorption-desorption, ammonia temperature-programmed desorption and in-situ Fourier-transform infrared spectroscopy. The delamination induced a change in the morphology of ITQ-2 zeolites from aggregated thin platelets to scattered platelets, together with a significant increase in external specific surface area, which reached a plateau at the ultrasonic treatment time of 3 h. The catalytic cracking of n-dodecane over ITQ-2 zeolites was evaluated with ITQ-2 coated on the inside wall of a tubular reactor at 550 ℃ and 4 MPa. The sample obtained by ultrasonic treatment of 3 h （ITQ-2-3） gave the highest initial conversion of n-dodecane, whereas those of 5 h and I h gave the conversion even lower than MCM-22, which was in agreement with the trend of the ratio of strong Lewis acid to the total acid amount. Although the amount of cokes deposited on ITQ-2-3 was larger than that on MCM-22, the former deactivated slowly, suggesting that a large external specific surface area benefits the stability of zeolite coatings,
基金Financial support from the Natural Science Foundation of China(21706177 and U19B2003)Guangxi Key Laboratory of Green Chemical Materials and Safety Technology,Beibu Gulf University(2022SYSZZ04)China Petroleum&Chemical Corporation(121014-2).
文摘The oligomerization of light olefins is an alternative for generating clean liquid fuels.In this study,the MCM-22 zeolite featuring a partially disordered layered structure with framework combined 10 membered ring(10 MR)was discussed for 1-hexene oligomerization.MCM-22 and Y zeolite were compared to investigate the influences of the framework and acidity strength on the activity and yield in the 1-hexene oligomerization.The results indicated that the MCM-22 zeolite was an efficient catalyst for oligomerization compared to Y zeolite.The MCM-22 zeolite was characterized in detail by NMR,Py-FTIR,and TG analyses.The catalytic performance and deactivation properties of MCM-22 zeolite in the oligomerization reaction of 1-hexene were investigated.Structure-activity relationships were established through the kinetic study.Although the density of strong acid sites was essential for the oligomerization of 1-hexene,the presence of low pressure was also necessary for the formation of dimers.Thus,MCM-22 zeolite demonstrates a substantial improvement in initial conversion and catalyst lifespan for 1-hexene oligomerization.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 29873065).
文摘Adsorption of xenon in zeolite MCM-22, a zeolite containing two separate pore systems, has been investigated in detail by variable temperature (VT) 129Xe NMR spectroscopy. NMR results suggest that Xe atoms are preferentially adsorbed in the supercages of the zeolite at low Xe pressure (less than a few atmosphere), while Xe atoms can penetrate into the two-dimensional sinusoidal channels at high Xe pressure. Exchange of xenon at the different adsorption sites in the same supercage, i.e. xenon atoms in the two pockets and those in the central part of the supercage, was confirmed at 145 K by two-dimensional (2D) 129Xe NMR exchange spectroscopy. The time scale for the exchange is about several milliseconds.
基金supported by National Basic Research Program of China(Grant No.2004CB217806)National Natural Science Foundation of China(Grant No.20476060)。
文摘Mesoporous aluminosilicate MCM-48 containing zeolite secondary building units in the pore wall has been synthesized in alkaline media with a two-step procedure.The aluminosilicate precursors comprising zeolite secondary building units were first synthesized by carefully controlling reaction conditions and then were assembled using co-templates of gemini surfactant[C18H37N(CH3)2(CH2)3-N(CH3)2C18H37]2+(18-3-18)and triethanolamine(TEA).X-ray Diffraction(XRD)patterns of the as-made samples indicated that highly ordered mesostructured MCM-48 was formed.Transmission Electron Microscopy(TEM)images further verified the formation of MCM-48 with uniform cubic pore channel system having the pore opening diameter of about 25Å.Compared with the conventionally synthesized MCM-48,the as-synthesized MCM-48 sample showed an adsorption band at 520–600 cm-1 in its FT-IR spectrum,which was assigned to five-membered ring vibration from zeolite structure.This suggested the presence of zeolite building units in the pore wall.N2 adsorption data showed that the material had a much higher specific surface area(1200 m2/g)than the conventional MCM-48(1100 m2/g).Finally,the cat-alytic performance of the as-made MCM-48 was evaluated by hydrogenation dealkylation reaction of heavy aromatic hydrocarbons.Catalytic results showed that the as-made MCM-48 catalyst exhibited higher conversion than the con-ventional MCM-48 catalyst.The as-made mesostructured MCM-48 may have a potential catalytic application in the conversion of bulky molecules.
文摘The benzene alkylation process for the production of ethylbenzene has undergone significant improvements during recent decades.Various environmentally benign zeolite-catalyzed ethylbenzene processes,including ZSM-5-zeolite-based vapor-phase ethylbenzene processes and Y-,β-,and MCM-22-zeolite-based liquid-phase processes,have been developed and commercialized.Pure ethylene,ethanol,and dilute ethylene have been used as ethylation agents.Here,the development and industrial application of alkylation catalysts and benzene ethylation techniques are summarized,and some other promising innovations are discussed.Recent advances in benzene alkylation over hierarchical zeolites with improved access to active sites and molecular transport are also covered.Zeolites with short diffusion lengths are promising candidates as better alkylation catalysts.The key point is how to obtain such materials easily and economically.The structure-activity relationships of commercial zeolites in these processes are discussed.Liquid-phase processes catalyzed by β and MCM-22 are more profitable than vapor-phase processes catalyzed by ZSM-5.
