The hydrophilic ZSM-5 zeolite membranes are applied to separate the inorganic acid solutions and inorganic acid/inorganic salt mixtures by pervaporation,and the membrane presents good stability,dehydration,and desalin...The hydrophilic ZSM-5 zeolite membranes are applied to separate the inorganic acid solutions and inorganic acid/inorganic salt mixtures by pervaporation,and the membrane presents good stability,dehydration,and desalination performance.Influences of inorganic acid type(H_(2)SO_(4),H_(3)PO_(4),HNO_(3),and HCl),H_(2)SO_(4)concentration(1-6 mol·L^(-1)),test temperature(60-90℃)and inorganic acid/inorganic salt type(2 mol·L^(-1)H_(2)SO_(4)and sulfate,2 mol·L^(-1)H3PO4 and phosphate)on the pervaporation performance are investigated in this work.Either for concentrating 3%(mass)H_(2)SO_(4)solution or consecutive dehydrating 20%(mass)H_(2)SO_(4)solution,the hydrophilic ZSM-5 zeolite membrane has a good dehydration performance and stability.Even though the H_(2)SO_(4)concentration and test temperature are increased to 6 M and 90℃,only H_(2)O molecules could pass through the membrane and pH value of the permeation is kept neutral.Besides,the membrane has good dehydration and desalination performance for H_(2)SO_(4)/sulfates and H_(3)PO_(4)/phosphate mixtures,and the rejection of natrium salt,molysite,and magnesium is almost 100%.展开更多
Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were invest...Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were investigated by static adsorption experiments.The morphologies,structural features,and physicochemical properties of the adsorbents were characterized by X-ray diffraction,Brunauer-Emmett-Teller analysis,NH3 temperature-programmed desorption,scanning electron microscopy,transmission electron microscopy,and pyridine adsorption infrared spectroscopy.The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance.The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface.A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite.Furthermore,the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions.The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic,spontaneous,disordered,and primarily involved physical adsorption.展开更多
The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 ...The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 adsorption-desorption,X-ray fluorescence spectroscopy,scanning electron microscopy,X-ray diffraction,magic angle spinning nuclear magnetic resonance,temperature-programmed desorption of ammonia,and infrared spectroscopy of pyridine adsorption.The results suggest that the BET surface area and SiO2/Al2O3 ratio of these samples are similar,while the snowflake-shaped ZSM-5 zeolite possesses more of the(101) face,and distortion,dislocation,and asymmetry in the framework,resulting in a larger number of acid sites than the conventional samples.Catalysts for the methanol to olefin(MTO) reaction were prepared by loading Ca on the samples.The snowflake-shaped Ca/ZSM-5 zeolite exhibited excellent selectivity for total light olefin(72%) and propene(39%) in MTO.The catalytic performance influenced by the morphology can be mainly attributed to the snowflake-shaped ZSM-5 zeolite possessing distortion,dislocation,and asymmetry in the framework,and lower diffusion limitation than the conventional samples.展开更多
The promoting effect of introducing Zn into nano-ZSM-5 zeolites by conventional impregnation method and isomorphous substitution on the performance of 1-hexene aromatization was investigated. The nano-ZSM-5 zeolite wa...The promoting effect of introducing Zn into nano-ZSM-5 zeolites by conventional impregnation method and isomorphous substitution on the performance of 1-hexene aromatization was investigated. The nano-ZSM-5 zeolite was synthesized by a seed-induced method without organic templates. The Zn-modified nano-ZSM-5 zeolite catalysts, xZ n/HNZ5 and y Zn/Al-HNZ5, were prepared by the conventional impregnation method and isomorphous substitution, respectively. The structure, chemical composition and acidity of the catalysts were characterized by XRD, XRF, N2 adsorption, SEM, NH3-TPD and Py-IR, while the catalytic properties were evaluated at 480 °C and a weight hourly space velocity(WHSV) of 2.0 h-1 in the aromatization procedure of 1-hexene. Compared with xZ n/HNZ5, y Zn/Al-HNZ5 exhibited smaller particles and higher dispersion of Zn species, which led to greater intergranular mesopore and homogeneous acidity distribution. Experimental results indicated that the synergy effect between the Brnsted and Lewis acid sites of the isomorphously substituted nano-ZSM-5 zeolites could significantly increase aromatics yield and improve catalytic stability in the 1-hexene aromatization.展开更多
Adsorption rates of n-hexane on the 5A zeolite at 100 to 300 ℃ and 0.01 to 10 kPa are determined by an intelligent gravimetric analyzer (IGA-100), and the adsorption diffusion performance of n-hexane on 5A zeolite ...Adsorption rates of n-hexane on the 5A zeolite at 100 to 300 ℃ and 0.01 to 10 kPa are determined by an intelligent gravimetric analyzer (IGA-100), and the adsorption diffusion performance of n-hexane on 5A zeolite pellets with different secondary pore distributions is analyzed. The results indicate that 5A-1 and 5A-6 zeolites have similar micropore and mesopore size distribution, while the 5A-6 zeolite has a larger secondary pore volume when the pore diameter is between 0.1 and 1 μm and more secondary pores when the pore diameter is less than 0.01 μm. The effective diffusion coefficient of nhexane on the 5A-6 zeolite pellet is 10 ^-6 to 10 4 cm^2/s, about 2 to 5 times higher than that on the 5A-1 zeolite. The effective diffusion coefficient of n-hexane on the 5A-1 zeolite pellet improves from 5 × 10^-7 to 2 × 10 6cm^2/s when the temperature increases from 100 to 300 ~C. However, the effective diffusion coefficient of n-hexane on the 5A-6 zeolite remains almost unchanged at different temperatures. The molecular average free path of n-hexane decreases from 627.15-963.28 to 0.63-0, 96 Ixm with the adsorption pressure increasing from 0.01 to 10 kPa. Such a flee path is close to the secondary pore diameter, resulting in significant Knudsen diffusion in the secondary pores. Thus, the effective diffusion coefficient of n-hexane on the 5A zeolite pellets increases before 1 kPa and decreases after 1 kPa.展开更多
Various ZSM-5 zeolites modified with alkali metals (Li, Na, K, Rb, and Cs) were prepared using ion exchange. The catalysts were used to enhance the catalytic dehydration of lactic acid (LA) to acrylic acid (AA)....Various ZSM-5 zeolites modified with alkali metals (Li, Na, K, Rb, and Cs) were prepared using ion exchange. The catalysts were used to enhance the catalytic dehydration of lactic acid (LA) to acrylic acid (AA). The effects of cationic species on the structures and surface acid-base distributions of the ZSM-5 zeolites were investigated. The important factors that affect the catalytic performance were also identified. The modified ZSM-5 catalysts were characterized using X-ray diffraction, tempera- ture-programmed desorptions of NH3 and CO2, pyridine adsorption spectroscopy, and N2 adsorption to determine the crystal phase structures, surface acidities and basicities, nature of acid sites, specific surface areas, and pore volumes. The results show that the acid-base sites that are adjusted by alkali-metal species, particularly weak acid-base sites, are mainly responsible for the formation of AA. The KZSM-5 catalyst, in particular, significantly improved LA conversion and AA selectivity because of the synergistic effect of weak acid-base sites. The reaction was conducted at different reaction temperatures and liquid hourly space velocities (LHSVs) to understand the catalyst selectivity for AA and trends in byproduct formation. Approximately 98% LA conversion and 77% AA selectivity were achieved using the KZSM-5 catalyst under the optimum conditions (40 wt% LA aqueous solution, 365 ℃, and LHSV 2 h-1).展开更多
The effects of rare earth(RE)on the structure,acidity,and catalytic performance of HZSM-5 zeolite were investigated.A series of RE/HZSM-5 catalysts,containing 7.54% RE(RE=La,Ce,Pr,Nd,Sm,Eu or Gd),were prepared by ...The effects of rare earth(RE)on the structure,acidity,and catalytic performance of HZSM-5 zeolite were investigated.A series of RE/HZSM-5 catalysts,containing 7.54% RE(RE=La,Ce,Pr,Nd,Sm,Eu or Gd),were prepared by the impregnation of the ZSM-5 type zeolites(Si/Al=64:1)with the corresponding RE nitrate aqueous solutions.The catalysts were characterized by means of FT-IR,UV-Vis,NH3-TPD,and IR spectroscopy of adsorbed pyridine.The catalytic performances of the RE/HZSM-5 for the catalytic cracking of mixed butane to light olefins were also measured with a fixed bed microreactor.The results revealed that the addition of light rare earth metal on the HZSM-5 catalyst greatly enhanced the selectivity to olefins,especially to propylene,thus increasing the total yield of olefins in the catalytic cracking of butane.Among the RE-modified HZSM-5 samples,Ce/HZSM-5 gave the highest yield of total olefins,and Nd/HZSM-5 gave the highest yield of propene at a reaction temperature of 600℃.The presence of rare earth metal on the HZSM-5 sample,not only modified the acidic properties of HZSM-5 including the amount of acid sites and acid type,that is,the ratio of L/B(Lewis acid/Brnsted acid),but also altered the basic properties of it,which in turn promoted the catalytic performance of HZSM-5 for the catalytic cracking of butane.展开更多
Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of...Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of 1-hexene was investigated. The results indicate that isomorphous substitution promotes the incorporation of Ga heteroatoms into the framework along with the formation of extra-framework GaO;species([GaO;]a) that have stronger interactions with the negative potential of the framework. In addition, based on the Py-IR results and catalytic performance, the [GaO;]aspecies with stronger Lewis acid sites produced a better synergism with moderate Br?nsted acid sites and thus improved the selectivity to aromatic compounds. However, the impregnation results in the formation of Ga;O;phase and small amounts of GaO;species that are mainly located on the external surface([GaO;];), which contribute to weaker Lewis acid sites due to weaker interactions with the zeolite framework. During 1-hexene aromatization, the nanosized Ga isomorphously substituted ZSM-5 zeolite samples(Gax-NZ5) exhibited better catalytic performance compared to the impregnated samples, and the highest aromatic yield(i.e.,65.4 wt%) was achieved over the Ga4.2-NZ5 sample, which contained with the highest Ga content.展开更多
HZSM-5 zeolites with the micro-mesopore hierarchical porosity have been prepared by the post-synthesis of alkali-treatment, and their thermal and hydrothermal stabilities were studied using DTA, XRD, and NH3-TPD chara...HZSM-5 zeolites with the micro-mesopore hierarchical porosity have been prepared by the post-synthesis of alkali-treatment, and their thermal and hydrothermal stabilities were studied using DTA, XRD, and NH3-TPD characterization techniques. Compared to the unmodified zeolite, the thermal and hydrothermal stabilities of the alkali-treated ZSM-5 zeolites were slightly deteriorated because of the introduction of mesopores caused by the desilication. Nevertheless, the alkali-treated zeolite framework could be maintained until the temperature increased to 1175 ℃.展开更多
The adsorption behavior of benzene and propylene in zeolite ZSM-5 was studied by Grand Canonical Monte Carlo(GCMC) simulations. It could be found that benzene and propylene molecules showed different adsorption beha...The adsorption behavior of benzene and propylene in zeolite ZSM-5 was studied by Grand Canonical Monte Carlo(GCMC) simulations. It could be found that benzene and propylene molecules showed different adsorption behavior in the zeolite cavities. The loadings of propylene were significantly larger than those of benzene at 100 kPa. From the figures of potential energy distribution, the potential energy of benzene/zeolite was more negative than that of propylene/zeolite, so benzene could be adsorbed more stably than propylene. When the temperature was in- creased from 298 to 443 K at 100 kPa, the loading ofpropylene was reduced from 99 to 82 molecules, whereas that of benzene changed little. When benzene and propylene were adsorbed in zeolite simultaneously, the competitive adsorption of them occurred; therefore, the potential energy distribution could be changed significantly. Besides, the adsorption isotherms of benzene and propylene in ZSM-5 at 298 and 443 K were simulated. The results exhibit that the different factors influenced the molecular adsorption at various temperatures and pressures, leading to the diffe- rent rules for the adsorption of benzene and propylene molecules in the zeolite. At a low pressure, the unfavorable energy of propylene/zeolite and the "commensurate freezing" phenomenon of benzene would make the loadings of itself higher than those of propylene. When pressure was higher than 5 kPa, the adsorption of benzene in ZSM-5 would nearly reach saturation.展开更多
The most prestigious catalyst applied in natural gas (methane) non-oxidative conversion to petrochemicals is 6%Mo/H-ZSM-5. Chromium, molybdenum and tungsten are the group VI metals. Hence, in this work, 6%Mo/H-ZSM-5...The most prestigious catalyst applied in natural gas (methane) non-oxidative conversion to petrochemicals is 6%Mo/H-ZSM-5. Chromium, molybdenum and tungsten are the group VI metals. Hence, in this work, 6%Mo/H-ZSM-5 was correlated with 3%Cr+3%Mo/H-ZSM-5 and 3%W+3%Mo/H-ZSM-5 as catalysts to examine their promoting or inhibiting effects on the various reactions taking place during methane conversion. The catalytic activities of these catalysts were tested in a continuous flow fixed bed reactor at 700℃ and a GHSV of 1500 ml·g^-1·h^-1 Characterization of the catalysts using XRD, TGA and TPD were investigated. XRD and NH3-TPD showed greater interaction between the W-phase and the Bronsted acid sites in the channels of the zeolite than between Cr-phase and the acid sites in the zeolite.展开更多
The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total ...The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total acid amounts, their density and the amount of B-type acid of HZSM-5 catalysts rapidly decreased, while the amounts of L-type acid had almost no change and thus the ratio of L/B was obviously enhanced with the increase of calcination temperature (excluding 800 ℃). The catalytic performances of modified HZSM-5 catalysts for the cracking of n-butane were also investigated. The main properties of these catalysts were characterized by means of XRD, N2 adsorption at low temperature, NH3-TPD, FTIR of pyridine adsorption and BET surface area measurements. The results showed that HZSM-5 zeolite pretreated at 800 ℃ had very low catalytic activity for n-butane cracking. In the calcination temperature range of 500-700 ℃, the total selectivity to olefins, propylene and butene were increased with the increase of calcination temperature, while, the selectivity for arene decreased with the calcination temperature. The HZSM-5 zeolite calcined at 700 ℃ produced light olefins with high yield, at the reaction temperature of 650 ℃ the yields of total olefins and ethylene were 52.8% and 29.4%, respectively. Besides, the more important role is that high calcination temperature treatment improved the duration stability of HZSM-5 zeolites. The effect of calcination temperature on the physico-chemical properties and catalytic performance of HZSM-5 for cracking of n-butane was explored. It was found that the calcination temperature had large effects on the surface area, crystallinity and acid properties of HZSM-5 catalyst, which further affected the catalytic performance for n-butane cracking.展开更多
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
基金supported by the National Natural Science Foundation of China(21868012 and 22368025)Jiangxi Provincial Department of Science and Technology(20171BCB24005 and 20202BAB203011).
文摘The hydrophilic ZSM-5 zeolite membranes are applied to separate the inorganic acid solutions and inorganic acid/inorganic salt mixtures by pervaporation,and the membrane presents good stability,dehydration,and desalination performance.Influences of inorganic acid type(H_(2)SO_(4),H_(3)PO_(4),HNO_(3),and HCl),H_(2)SO_(4)concentration(1-6 mol·L^(-1)),test temperature(60-90℃)and inorganic acid/inorganic salt type(2 mol·L^(-1)H_(2)SO_(4)and sulfate,2 mol·L^(-1)H3PO4 and phosphate)on the pervaporation performance are investigated in this work.Either for concentrating 3%(mass)H_(2)SO_(4)solution or consecutive dehydrating 20%(mass)H_(2)SO_(4)solution,the hydrophilic ZSM-5 zeolite membrane has a good dehydration performance and stability.Even though the H_(2)SO_(4)concentration and test temperature are increased to 6 M and 90℃,only H_(2)O molecules could pass through the membrane and pH value of the permeation is kept neutral.Besides,the membrane has good dehydration and desalination performance for H_(2)SO_(4)/sulfates and H_(3)PO_(4)/phosphate mixtures,and the rejection of natrium salt,molysite,and magnesium is almost 100%.
基金This work was financially supported by the Natural Science Foundation of Shandong Province(ZR2021MB134 and ZR2022MB019)the National Natural Science Foundation of China(22008131)+1 种基金the Talent Fund for Province and Ministry Co-construction Collaborative Innovation Center of Eco-chemical Engineering(STHGYX2220)the Opening Fund of State Key Laboratory of Heavy Oil Processing(SKLOP202002002).
文摘Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were investigated by static adsorption experiments.The morphologies,structural features,and physicochemical properties of the adsorbents were characterized by X-ray diffraction,Brunauer-Emmett-Teller analysis,NH3 temperature-programmed desorption,scanning electron microscopy,transmission electron microscopy,and pyridine adsorption infrared spectroscopy.The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance.The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface.A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite.Furthermore,the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions.The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic,spontaneous,disordered,and primarily involved physical adsorption.
基金Synfuels China Co.Ltd.for the financial and equipments support
文摘The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 adsorption-desorption,X-ray fluorescence spectroscopy,scanning electron microscopy,X-ray diffraction,magic angle spinning nuclear magnetic resonance,temperature-programmed desorption of ammonia,and infrared spectroscopy of pyridine adsorption.The results suggest that the BET surface area and SiO2/Al2O3 ratio of these samples are similar,while the snowflake-shaped ZSM-5 zeolite possesses more of the(101) face,and distortion,dislocation,and asymmetry in the framework,resulting in a larger number of acid sites than the conventional samples.Catalysts for the methanol to olefin(MTO) reaction were prepared by loading Ca on the samples.The snowflake-shaped Ca/ZSM-5 zeolite exhibited excellent selectivity for total light olefin(72%) and propene(39%) in MTO.The catalytic performance influenced by the morphology can be mainly attributed to the snowflake-shaped ZSM-5 zeolite possessing distortion,dislocation,and asymmetry in the framework,and lower diffusion limitation than the conventional samples.
基金Project(21276067)supported by the National Natural Science Foundation of China
文摘The promoting effect of introducing Zn into nano-ZSM-5 zeolites by conventional impregnation method and isomorphous substitution on the performance of 1-hexene aromatization was investigated. The nano-ZSM-5 zeolite was synthesized by a seed-induced method without organic templates. The Zn-modified nano-ZSM-5 zeolite catalysts, xZ n/HNZ5 and y Zn/Al-HNZ5, were prepared by the conventional impregnation method and isomorphous substitution, respectively. The structure, chemical composition and acidity of the catalysts were characterized by XRD, XRF, N2 adsorption, SEM, NH3-TPD and Py-IR, while the catalytic properties were evaluated at 480 °C and a weight hourly space velocity(WHSV) of 2.0 h-1 in the aromatization procedure of 1-hexene. Compared with xZ n/HNZ5, y Zn/Al-HNZ5 exhibited smaller particles and higher dispersion of Zn species, which led to greater intergranular mesopore and homogeneous acidity distribution. Experimental results indicated that the synergy effect between the Brnsted and Lewis acid sites of the isomorphously substituted nano-ZSM-5 zeolites could significantly increase aromatics yield and improve catalytic stability in the 1-hexene aromatization.
基金The National Natural Science Foundation of China ( No.20876074)
文摘Adsorption rates of n-hexane on the 5A zeolite at 100 to 300 ℃ and 0.01 to 10 kPa are determined by an intelligent gravimetric analyzer (IGA-100), and the adsorption diffusion performance of n-hexane on 5A zeolite pellets with different secondary pore distributions is analyzed. The results indicate that 5A-1 and 5A-6 zeolites have similar micropore and mesopore size distribution, while the 5A-6 zeolite has a larger secondary pore volume when the pore diameter is between 0.1 and 1 μm and more secondary pores when the pore diameter is less than 0.01 μm. The effective diffusion coefficient of nhexane on the 5A-6 zeolite pellet is 10 ^-6 to 10 4 cm^2/s, about 2 to 5 times higher than that on the 5A-1 zeolite. The effective diffusion coefficient of n-hexane on the 5A-1 zeolite pellet improves from 5 × 10^-7 to 2 × 10 6cm^2/s when the temperature increases from 100 to 300 ~C. However, the effective diffusion coefficient of n-hexane on the 5A-6 zeolite remains almost unchanged at different temperatures. The molecular average free path of n-hexane decreases from 627.15-963.28 to 0.63-0, 96 Ixm with the adsorption pressure increasing from 0.01 to 10 kPa. Such a flee path is close to the secondary pore diameter, resulting in significant Knudsen diffusion in the secondary pores. Thus, the effective diffusion coefficient of n-hexane on the 5A zeolite pellets increases before 1 kPa and decreases after 1 kPa.
基金Key Research and Development Plan of Shaanxi Province(2023-YBGY-290)Research Project of Shaanxi Yanchang Petroleum(Group)Co.,Ltd.(No.ycsy2023ky-B-81)。
文摘Various ZSM-5 zeolites modified with alkali metals (Li, Na, K, Rb, and Cs) were prepared using ion exchange. The catalysts were used to enhance the catalytic dehydration of lactic acid (LA) to acrylic acid (AA). The effects of cationic species on the structures and surface acid-base distributions of the ZSM-5 zeolites were investigated. The important factors that affect the catalytic performance were also identified. The modified ZSM-5 catalysts were characterized using X-ray diffraction, tempera- ture-programmed desorptions of NH3 and CO2, pyridine adsorption spectroscopy, and N2 adsorption to determine the crystal phase structures, surface acidities and basicities, nature of acid sites, specific surface areas, and pore volumes. The results show that the acid-base sites that are adjusted by alkali-metal species, particularly weak acid-base sites, are mainly responsible for the formation of AA. The KZSM-5 catalyst, in particular, significantly improved LA conversion and AA selectivity because of the synergistic effect of weak acid-base sites. The reaction was conducted at different reaction temperatures and liquid hourly space velocities (LHSVs) to understand the catalyst selectivity for AA and trends in byproduct formation. Approximately 98% LA conversion and 77% AA selectivity were achieved using the KZSM-5 catalyst under the optimum conditions (40 wt% LA aqueous solution, 365 ℃, and LHSV 2 h-1).
基金Project supported by the National Basic Research Program of China(2004CB2178062005CB221402)+1 种基金the National NaturalScience Foundation of China(20373043)Young Scientists Innovation Foundation of CNPC(04E7025)
文摘The effects of rare earth(RE)on the structure,acidity,and catalytic performance of HZSM-5 zeolite were investigated.A series of RE/HZSM-5 catalysts,containing 7.54% RE(RE=La,Ce,Pr,Nd,Sm,Eu or Gd),were prepared by the impregnation of the ZSM-5 type zeolites(Si/Al=64:1)with the corresponding RE nitrate aqueous solutions.The catalysts were characterized by means of FT-IR,UV-Vis,NH3-TPD,and IR spectroscopy of adsorbed pyridine.The catalytic performances of the RE/HZSM-5 for the catalytic cracking of mixed butane to light olefins were also measured with a fixed bed microreactor.The results revealed that the addition of light rare earth metal on the HZSM-5 catalyst greatly enhanced the selectivity to olefins,especially to propylene,thus increasing the total yield of olefins in the catalytic cracking of butane.Among the RE-modified HZSM-5 samples,Ce/HZSM-5 gave the highest yield of total olefins,and Nd/HZSM-5 gave the highest yield of propene at a reaction temperature of 600℃.The presence of rare earth metal on the HZSM-5 sample,not only modified the acidic properties of HZSM-5 including the amount of acid sites and acid type,that is,the ratio of L/B(Lewis acid/Brnsted acid),but also altered the basic properties of it,which in turn promoted the catalytic performance of HZSM-5 for the catalytic cracking of butane.
基金supported by the National Natural Science Foundation of China(Nos.21276067 and 21676074)Programs of International S&T cooperation(No.2014DFR41110)
文摘Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of 1-hexene was investigated. The results indicate that isomorphous substitution promotes the incorporation of Ga heteroatoms into the framework along with the formation of extra-framework GaO;species([GaO;]a) that have stronger interactions with the negative potential of the framework. In addition, based on the Py-IR results and catalytic performance, the [GaO;]aspecies with stronger Lewis acid sites produced a better synergism with moderate Br?nsted acid sites and thus improved the selectivity to aromatic compounds. However, the impregnation results in the formation of Ga;O;phase and small amounts of GaO;species that are mainly located on the external surface([GaO;];), which contribute to weaker Lewis acid sites due to weaker interactions with the zeolite framework. During 1-hexene aromatization, the nanosized Ga isomorphously substituted ZSM-5 zeolite samples(Gax-NZ5) exhibited better catalytic performance compared to the impregnated samples, and the highest aromatic yield(i.e.,65.4 wt%) was achieved over the Ga4.2-NZ5 sample, which contained with the highest Ga content.
基金the National Key Project for Basic Research of China(973 Project)(No.2005CB221403)the Knowledge Innovation Program of the Chinese Academy of Sciences(Grant:DICP K2007D3)
文摘HZSM-5 zeolites with the micro-mesopore hierarchical porosity have been prepared by the post-synthesis of alkali-treatment, and their thermal and hydrothermal stabilities were studied using DTA, XRD, and NH3-TPD characterization techniques. Compared to the unmodified zeolite, the thermal and hydrothermal stabilities of the alkali-treated ZSM-5 zeolites were slightly deteriorated because of the introduction of mesopores caused by the desilication. Nevertheless, the alkali-treated zeolite framework could be maintained until the temperature increased to 1175 ℃.
基金Supported by the National Natural Science Foundation of China(Nos.20576012 and 20625621)
文摘The adsorption behavior of benzene and propylene in zeolite ZSM-5 was studied by Grand Canonical Monte Carlo(GCMC) simulations. It could be found that benzene and propylene molecules showed different adsorption behavior in the zeolite cavities. The loadings of propylene were significantly larger than those of benzene at 100 kPa. From the figures of potential energy distribution, the potential energy of benzene/zeolite was more negative than that of propylene/zeolite, so benzene could be adsorbed more stably than propylene. When the temperature was in- creased from 298 to 443 K at 100 kPa, the loading ofpropylene was reduced from 99 to 82 molecules, whereas that of benzene changed little. When benzene and propylene were adsorbed in zeolite simultaneously, the competitive adsorption of them occurred; therefore, the potential energy distribution could be changed significantly. Besides, the adsorption isotherms of benzene and propylene in ZSM-5 at 298 and 443 K were simulated. The results exhibit that the different factors influenced the molecular adsorption at various temperatures and pressures, leading to the diffe- rent rules for the adsorption of benzene and propylene molecules in the zeolite. At a low pressure, the unfavorable energy of propylene/zeolite and the "commensurate freezing" phenomenon of benzene would make the loadings of itself higher than those of propylene. When pressure was higher than 5 kPa, the adsorption of benzene in ZSM-5 would nearly reach saturation.
文摘The most prestigious catalyst applied in natural gas (methane) non-oxidative conversion to petrochemicals is 6%Mo/H-ZSM-5. Chromium, molybdenum and tungsten are the group VI metals. Hence, in this work, 6%Mo/H-ZSM-5 was correlated with 3%Cr+3%Mo/H-ZSM-5 and 3%W+3%Mo/H-ZSM-5 as catalysts to examine their promoting or inhibiting effects on the various reactions taking place during methane conversion. The catalytic activities of these catalysts were tested in a continuous flow fixed bed reactor at 700℃ and a GHSV of 1500 ml·g^-1·h^-1 Characterization of the catalysts using XRD, TGA and TPD were investigated. XRD and NH3-TPD showed greater interaction between the W-phase and the Bronsted acid sites in the channels of the zeolite than between Cr-phase and the acid sites in the zeolite.
基金The authors would like to thank the financial support from the National Basic Research Program of China fgrant No.2004CB 217806)the National Natural Science Foundation of China (Grant No.20373043) the Scientific Research Key Foundation for the Returned Overseas Chinese Scholars of State Education Ministry.
文摘The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total acid amounts, their density and the amount of B-type acid of HZSM-5 catalysts rapidly decreased, while the amounts of L-type acid had almost no change and thus the ratio of L/B was obviously enhanced with the increase of calcination temperature (excluding 800 ℃). The catalytic performances of modified HZSM-5 catalysts for the cracking of n-butane were also investigated. The main properties of these catalysts were characterized by means of XRD, N2 adsorption at low temperature, NH3-TPD, FTIR of pyridine adsorption and BET surface area measurements. The results showed that HZSM-5 zeolite pretreated at 800 ℃ had very low catalytic activity for n-butane cracking. In the calcination temperature range of 500-700 ℃, the total selectivity to olefins, propylene and butene were increased with the increase of calcination temperature, while, the selectivity for arene decreased with the calcination temperature. The HZSM-5 zeolite calcined at 700 ℃ produced light olefins with high yield, at the reaction temperature of 650 ℃ the yields of total olefins and ethylene were 52.8% and 29.4%, respectively. Besides, the more important role is that high calcination temperature treatment improved the duration stability of HZSM-5 zeolites. The effect of calcination temperature on the physico-chemical properties and catalytic performance of HZSM-5 for cracking of n-butane was explored. It was found that the calcination temperature had large effects on the surface area, crystallinity and acid properties of HZSM-5 catalyst, which further affected the catalytic performance for n-butane cracking.
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.