The Pd-promoted Ga/HZSM-5 catalyst was prepared by impregnation method and its catalytic activity for non-oxidative aromatization of C1 to C3 hydrocarbons was assessed using a microreactor-GC system operated with temp...The Pd-promoted Ga/HZSM-5 catalyst was prepared by impregnation method and its catalytic activity for non-oxidative aromatization of C1 to C3 hydrocarbons was assessed using a microreactor-GC system operated with temperature at 823 K and space velocity at 410 h-1. The catalyst is more catalytically active for methane conversion than Ga/HZSM-5. The mass spectroscopy analyses confirmed that 13CH4 was converted to aromatic products.展开更多
The non-oxidative aromatization of mixed CH4 with C3H8 over La-promoted Zn/HZSM-5 catalysts was studied in a fixed-bed reactor at 823 K with space velocity 600 h^-1 and CH4/C3H8(mol ratio)=5:l.The propane conversion a...The non-oxidative aromatization of mixed CH4 with C3H8 over La-promoted Zn/HZSM-5 catalysts was studied in a fixed-bed reactor at 823 K with space velocity 600 h^-1 and CH4/C3H8(mol ratio)=5:l.The propane conversion and the aromatic selectivities were up to 99%and 60%over the catalyst respectively,while methane conversion had an induction period with the highest conversion of 30%.The structure and surface acidity of the catalysts were characterized by XRD,NH3-TPD and TG-DTA.The influences of reaction and regenerative conditions on the activity and selectivity were also investigated.展开更多
Converting waste plastics directly into valuable aromatic chemicals is a promising,cost-effective recycling strategy.Traditional zeolite-catalyzed cracking of polyolefins to produce aromatics often needs high temperat...Converting waste plastics directly into valuable aromatic chemicals is a promising,cost-effective recycling strategy.Traditional zeolite-catalyzed cracking of polyolefins to produce aromatics often needs high temperatures and faces issues like low selectivity for liquid aromatics,separation difficulties,and rapid catalyst deactivation due to coking.To address this,a multifunctional Ni/HZSM-5 catalyst was developed to efficiently upgrade various polyolefins—including polyvinyl chloride—into gaseous alkanes(C_(1)–C_(5))and easily separable liquid aromatics(C_(6)–C_(12))at 400°C,without added solvents or hydrogen.Aromatic products make up 57.1 wt%of total output,with more than 97.8%selectivity for the liquid phase and a BTX(benzene,toluene,and xylene)selectivity of 76.1%.The high activity and selectivity for aromatics stem from synergistic interactions between Ni nanoparticles(NPs)and acid sites in the zeolite,which promote selective C–C bond breaking and control hydrogenolysis and aromatization pathways.This synergy allows precise control over the distribution of products by carbon number and favors the formation of separable aromatics.Notably,the catalyst also prevents coking by hydrogenolyzing and hydrogenating reactive intermediates before they form stable graphite-like deposits.Consequently,Ni/ZSM-5 catalyst demonstrates excellent stability,maintaining consistent aromatics yield over 13 consecutive cycles and processing over 30 times its weight in plastics without regeneration.After regeneration,the activity of the catalyst was fully restored,highlighting its potential for industrial use.This work offers valuable insights for designing durable,high-activity catalysts,providing a practical route to improve plastic recycling technologies.展开更多
The intrinsic reaction kinetics of methane aromatization under non-oxidative conditions over modified Mo/HZSM-5 catalysts was studied in the quartz pipe-reactor under ordinary pressure with the temperature ranging fro...The intrinsic reaction kinetics of methane aromatization under non-oxidative conditions over modified Mo/HZSM-5 catalysts was studied in the quartz pipe-reactor under ordinary pressure with the temperature ranging from 913.15 to 973.15 K and the space velocity from 700 to 2100 ml/（g·h）. The Langmuir-Hinshelwood model was chosen to describe the intrinsic kinetics while Levenberg-Marquardt method was selected to determine the parameters in the kinetic model. Statistical test and residual error distribution diagrams showed that experimental data were in good agreement with calculated data, and Langmuir-Hinshelwood model was suitable for the description of the intrinsic kinetics of methane aromatization under the reaction conditions discussed in this article.展开更多
The optimum Mo/[H^+] ratio per unit cell of the active precursors in Mo/HZSM-5 catalysts for methane dehydro-aromatization, measured by1H MAS NMR, was found to be about 1 when adjusting the acid sites by altering eith...The optimum Mo/[H^+] ratio per unit cell of the active precursors in Mo/HZSM-5 catalysts for methane dehydro-aromatization, measured by1H MAS NMR, was found to be about 1 when adjusting the acid sites by altering either the SiO2/Al2O3 ratios or the Mo loading. This implies that a concerted interaction between the Mo species and the Bronsted acid sites probably features the bifunctionality of the Mo/HZSM-5 catalyst. On the other hand, it was found that the driving force for Mo species to move into the HSZM-5 zeolite channels and the interaction between the Mo species and the Bronsted acid sites are closely and proportionably related with the amount of Bronsted acid sites per unit cell.展开更多
Aromatization of alkanes represents an important process in the chemical industry,traditionally relying on noble metal catalysts.Developing a non-noble metal catalyst and a relevant new process offers significant pote...Aromatization of alkanes represents an important process in the chemical industry,traditionally relying on noble metal catalysts.Developing a non-noble metal catalyst and a relevant new process offers significant potential for promoting technologic progress in this field.Herein,we present Cu-ZSM-5 zeolite as a highly effective catalyst for alkane aromatization,achieving outstanding aromatics selectivity.In-situ Fourier transform infrared spectra of adsorbed nitric oxide,high-angle annular dark field scanning transmission electron microscopy,X-ray absorption spectroscopy,and electron paramagnetic resonance analyses reveal that the Cu^(2+)species act as the primary active centers for aromatics formation.During aromatization of alkanes,the reduction of Cu^(2+)to Cu^(+)species correlates with diminished aromatics selectivity.Notably,introducing CO_(2)into the reaction feed not only enhances aromatics selectivity by maintaining Cu^(2+)species in their active oxidation state under reducing conditions,but also improves catalytic stability by eliminating coke.Furthermore,CO_(2)is converted into CO and aromatic products during the reaction,offering a novel way for CO_(2)utilization through the coupling reaction of alkane and CO_(2).展开更多
Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in ...Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in shale gas.Owing to their thermodynamic resistance,converting CO_(2)and C_(3)H_(8) respectively remains difficult.Here,we achieve 60.2%aromatics selectivity and 48.8%propane conversion over H-ZSM-5-25 via a zeolite-catalyzing the coupling of CO_(2)and C_(3)H_(8).Operando dual-beam FTIR spectroscopy combined with ^(13)C-labeled CO_(2)tracing experiments revealed that CO_(2)is directly involved in the generation of aromatics,with its carbon atoms selectively embedded into the aromatic ring,bypassing the reverse water-gas shift pathway.Accordingly,a cooperative aromatization mechanism is proposed.Thereinto,lactones,produced from CO_(2)and olefins,are proven to be the key intermediate.This work not only provides an opportunity for simultaneous conversion of CO_(2)and C_(3)H_(8),but also expends coupling strategy designing of CO_(2)and alkanes over acidic zeolites.展开更多
Aromatization of light alkanes is a value-added process in both petrochemical and coal chemical industries.Here,single[Ga(OH)]^(2+)ion-exchanged mesoporous hollow-structured ZSM-5(Ga-MH-ZSM-5)material was prepared,and...Aromatization of light alkanes is a value-added process in both petrochemical and coal chemical industries.Here,single[Ga(OH)]^(2+)ion-exchanged mesoporous hollow-structured ZSM-5(Ga-MH-ZSM-5)material was prepared,and it shows unprecedented catalytic performance in light alkane aromatization,considering activity,product selectivity and catalytic stability.The average aromatics yields in ethane aromatization at 600℃and WHSV of 0.8 h^(-1) within 28 h and in propane aromatization at 580℃and WHSV of 1.1 h^(-1) within 20 h reach~18.4%and~70.8%with benzene,toluene and xylenes(BTX)accounting for~96%and~88%of aromatics,respectively.Ga-MH-ZSM-5-0.41 gave a TON for formation of aromatics(TON_(aromatics))from propane as high as 57479,whereas the reported catalysts maximally show a TON_(aromatics) of 5514.This also holds true for ethane aromatization;the TON_(aromatics) obtained on Ga-MH-ZSM-5-0.41 was³3845 in contrast to£392 on reported non-noble metal catalysts.The catalytic activity of Ga-MH-ZSM-5 highly depends on Ga species structures.[Ga(OH)]^(2+)ions are predominant species at Ga loading≤0.3 wt%,while more[Ga(OH)_(2)]^(+)and GaO_(x) oligomers are formed with increasing Ga content.Upon reduction with H_(2),[Ga(OH)]^(2+)and[Ga(OH)_(2)]^(+)are transformed into[GaH]^(2+)and[GaH_(2)]^(+)species,which show a propane dehydrogenation rate of 300 and 15 times of that of Brønsted acid sites respectively.The light alkanes are mainly dehydrogenated into light olefins on[GaH]^(2+)species,and then,oligomerized and cyclized into(alkyl)cycloalkanes on H^(+)sites,which is followed by possible ring expansion on H^(+)and sequential dehydrogenations into aromatics primarily on[GaH]^(2+).展开更多
Despite the widespread presence and frequent detection of polycyclic aromatic hydrocarbons(PAHs)in various aspects of life,there is limited research on their exposure levels in pregnant women and cumulative exposure f...Despite the widespread presence and frequent detection of polycyclic aromatic hydrocarbons(PAHs)in various aspects of life,there is limited research on their exposure levels in pregnant women and cumulative exposure from the living environment.This study included 1311 women in late pregnancy from the Zunyi birth cohort and measured the urinary concentrations of 10 hydroxylated PAH metabolites(OH-PAHs).Risk assessment was conducted based on the estimated daily intake to calculate the hazard quotient and hazard index(HI).A linear regression model was used to analyze the relationship between creatinine-adjusted OH-PAHs concentrations and living environment and lifestyle factors,while principal component analysis was applied to trace the sources of PAHs exposure.1-OHPYR was detected in all participants’urine,with naphthalene metabolites having the highest concentrations among creatinine-adjusted PAHs.OH-PAHs concentrations were associated with housing type,room number,cooking frequency,household size,exercise frequency,fuel type,distance from main road,and drinking water source.Pregnant women using traditional fuels and living in bungalows had higher health risks than those using clean energy and living in buildings.Those living within 100 m of a main road had higher HI than those farther away.Coal combustion was identified as the primary source of PAHs exposure.The study emphasizes the importance of reducing PAHs exposure,especially for pregnant women living in polluted environments.It recommends public health interventions such as improving indoor ventilation and providing clean energy to reduce related health risks.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
We have developed an iron（III） phthalocyanine chloride‐catalyzed oxidation–aromatization ofα,β‐unsaturated ketones with hydrazine hydrate. Various 3,5‐disubstituted 1H‐pyrazoles were obtained in good to excel...We have developed an iron（III） phthalocyanine chloride‐catalyzed oxidation–aromatization ofα,β‐unsaturated ketones with hydrazine hydrate. Various 3,5‐disubstituted 1H‐pyrazoles were obtained in good to excellent yields. This method offers several advantages, including room‐tem‐perature conditions, short reaction time, high yields, simple work‐up procedure, and use of air as an oxidant. The catalyst can be recovered and reused five times without loss of activity.展开更多
The coking kinetics and reaction-regeneration on Zn/HZSM-5 （Zn/HZ） catalyst in the conversion of methanol to aromatics were investigated. The highest initial benzene, toluene and xylene （BTX） yield of ca. 67.7% wa...The coking kinetics and reaction-regeneration on Zn/HZSM-5 （Zn/HZ） catalyst in the conversion of methanol to aromatics were investigated. The highest initial benzene, toluene and xylene （BTX） yield of ca. 67.7% was obtained on fresh Zn/HZ catalyst, which showed the worst catalytic stability. The cycle of reaction-regeneration significantly modified the texture and acidity of Zn/HZ catalyst, which in turn affected its catalytic performance and coking behavior in methanol conversion to BTX. The residual carbon located on the surface of Zn/HZ catalyst led to the decrease of acid sites and the change on the acid sites distribution, which played an important roles on its activity and deactivation. It was found that the high B/L ratio and the low total acid sites concentration of the Zn/HZ catalyst favored to the high BTX yield and good catalytic stability in methanol conversion.展开更多
The influences of binder and molding method on the catalytic performance of methane aromatization in the absence of O2 over MoO3/ZSM-5 catalysts were investigated.SEM,NH3-TPD,FT-IR of adsorbed pyridine,N2 adsorption-d...The influences of binder and molding method on the catalytic performance of methane aromatization in the absence of O2 over MoO3/ZSM-5 catalysts were investigated.SEM,NH3-TPD,FT-IR of adsorbed pyridine,N2 adsorption-desorption,cyclohexane adsorption and XPS were employed to characterize the physical and chemical properties of the catalysts.It was found that SiO2 was a suitable binder for the catalyst due to its appropriate weak acidity.The laminar catalyst comprising of an inert spherical core and a MoO3/ZSM-5 laminar shell with 0.1 0.2 mm in thickness showed a better catalytic performance than the extruded catalyst.The improved activity of the laminar catalyst could be attributed to the easy carbonization of Mo species and the quick removal of reaction products from the catalyst surface.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
Zn/ZSM-5（NZ2） and Zn/Ni/ZSM-5（NZ3） as the catalysts for methanol to aromatics（MTA） were synthesized by a simple ultrasonic impregnation. The textural and acid properties of all catalysts were characterized using...Zn/ZSM-5（NZ2） and Zn/Ni/ZSM-5（NZ3） as the catalysts for methanol to aromatics（MTA） were synthesized by a simple ultrasonic impregnation. The textural and acid properties of all catalysts were characterized using XRD, HRTEM, NH;-TPD, Py-IR, XPS, XRF and TG techniques. The XRD and HRTEM results showed that the basic zeolite structures were not affected much with the incorporation of Zn and Ni species. However, great changes have taken place in acid properties. The Py-IR and XPS results indicated that the Zn-Lewis acid sites（ZnOH;species）, which have stronger interaction with the zeolite framework compared with ZnO species, were generated at the expense of B acid sites with the incorporation of zinc species. Moreover, the product analysis results showed that the incorporation of zinc species promoted the primary aromatization by enhancing the dehydroaromatization and suppressing the cracking and subsequent H-transfer reaction. Furthermore, the addition of Ni species well inhibited the loss of zinc species by converting partial ZnO species to ZnOH;species, and thus improved the aromatization activity and catalyst stability. The catalytic performance results showed that the NZ3 possess higher conversion of methanol in a longer time and lower average rate of coke formation compared with NZ2. In addition,the NZ3 also exhibited the highest yield of BTX as the reaction proceeds.展开更多
Platinum(Pt)supported on Zinc(Zn)modified silicalite-1(S-1)zeolite(denoted as Pt-Zn/S-1)was prepared by using a wetness-impregnation method and applied in the n-hexane aromatization reaction for the first time.Both Le...Platinum(Pt)supported on Zinc(Zn)modified silicalite-1(S-1)zeolite(denoted as Pt-Zn/S-1)was prepared by using a wetness-impregnation method and applied in the n-hexane aromatization reaction for the first time.Both Lewis and Bronsted acid sites were detected in Pt-Zn/S-1 catalyst by means of FT-IR adsorption of NH3 experiment,which were identified as mostly weak and medium ones.Besides,Pt and Zn species showed strong interaction,as revealed by the TPR(Temperature-programmed reduction)and XPS(X-ray photoelectron spectroscopy)experiments.Pt-Zn/S-1 catalyst exhibited excellent aromatization function rather than isomerization and cracking side reactions in the conversion of n-hexane.Pulse experimental study showed that 75.6%of n-hexane conversion and 76.8%of benzene selectivity were obtained over Pt0.1-Zn60/S-l catalyst at 550℃ and under atmospheric pressure.By spectroscopy tests and pulse experimental results,it was concluded that the n-hexane aromatization over Pt-Zn/S-1 catalyst follows a metal-acid bifunctional mechanism.Furthermore,with the assistance of Zn,the electron-deficient Pt species in Pt-Zn/S-1 showed good sulfur tolerance performance.展开更多
Aromatization of methanol over co-impregnated La/Zn/HZSM-5 zeolite catalyst was studied.The selectivity of aromatics and BTX(benzene,toluene,and xylene)reached 64.0%and 56.6%,respectively,using La/Zn/HZSM-5 at 437...Aromatization of methanol over co-impregnated La/Zn/HZSM-5 zeolite catalyst was studied.The selectivity of aromatics and BTX(benzene,toluene,and xylene)reached 64.0%and 56.6%,respectively,using La/Zn/HZSM-5 at 437°C,0.1 MPa and methanol WHSV(weight hourly space velocity)=0.8 h-1.Catalytic results showed that the La species was a very good promoter,increased selectivity of aromatics,and prolonged the catalyst lifetime on stream.The effects of the SiO2/Al2O3 ratio in zeolite,Zn and La loading,WHSV,reaction temperature, water content in the feed and H2 pretreatment of catalysts on the catalytic performance were studied in detail. Characterizations of the catalysts by thermogravimetric analysis(TGA),NH3-TPD(temperature programmed desorption),SEM(scanning electron micrograph),N2 adsorption-desorption,XRD(X-ray diffraction)and XRF (X-ray fluorescence),were carried out to understand the structure and discuss the aromatization performance of La/Zn/HZSM-5 zeolite catalyst.展开更多
In this work, nickel metal supported on different supports(SiO_2, Al_2O_3, ZSM-5) were prepared by spraying nickel nitrate on the supports and calcined at 873 K. Then, they were characterized by XRD, XRF, N_2 adsorpt...In this work, nickel metal supported on different supports(SiO_2, Al_2O_3, ZSM-5) were prepared by spraying nickel nitrate on the supports and calcined at 873 K. Then, they were characterized by XRD, XRF, N_2 adsorption–desorption, NH_3-TPD, MCH-TPD, H_2-TPR, and pyridine-FTIR,and tested as catalysts for the dehydrogenation aromatization and isomerization of methylcyclohexane(MCH) under the conditions of S-Zorb catalytic adsorption desulfurization(T ? 673 K, P ? 1.5 MPa, WHSV ? 5 h^(-1)). The H2-TPR results showed that the interaction of NiO with support decreased in the order of NiO/ZSM-5-Fe < NiO/ZSM-5 < NiO/Al_2O_3< NiO/SiO2. The decrease of the interaction appeared to facilitate the reduction of Ni and therefore to promote the dehydrogenation aromatization of MCH.It was found that a direct correlation existed between the gasoline components yields, cracking activity and the total number of different supports acid sites measured by NH_3-TPD tests. Higher total acidity of ZSM-5 resulted in gasoline loss because of higher cracking activity of MCH. The number of total acid sites of NiO/ZSM-5-Fe decreased and the medium strong Br€onsted acid sites necessary for MCH isomerization increased after the modification of ZSM-5 by iron metal. So, NiO/ZSM-5-Fe exhibited enhanced MCH conversion, aromatic and isomerization yields when compared to NiO/ZSM-5 and other Ni-based catalysts. This study shows that NiO/ZSM-5-Fe catalyst may be possible to be integrated into the S-Zorb system achieving the recovery of the octane number of gasoline.展开更多
The conversion of methane to olefins,aromatics,and hydrogen(MTOAH)can be used to stably obtain hydrocarbons when the effect of the catalytic surface is optimized from the reaction engineering perspective.In this study...The conversion of methane to olefins,aromatics,and hydrogen(MTOAH)can be used to stably obtain hydrocarbons when the effect of the catalytic surface is optimized from the reaction engineering perspective.In this study,Fe/Si C catalysts were packed into a quartz tube reactor.The catalytic surfaces of Si C and the impregnated Fe species decreased the apparent activation energies(E_a)of methane consumption in the blank reactor between 965 and 1020℃.Consequently,the hydrocarbon yield increased by 2.4times at 1020℃.Based on the model reactions of ethane,ethylene,and acetylene mixed with hydrogen in the range of 500-1020℃,an excess amount of Fe in the reactor favored the C-C coupling reaction over the selective hydrogenation of acetylene;consequently,coke formation was favored over the hydrogenation reaction.The gas-phase reactions and catalyst properties were optimized to increase hydrocarbon yields while reducing coke selectivity.The 0.2Fe catalyst-packed reactor(0.26 wt%Fe)resulted in a hydrocarbon yield of 7.1%and a coke selectivity of<2%when the ratio of the void space of the postcatalyst zone to the catalyst space was adjusted to be≥2.Based on these findings,the facile approach of decoupling the reaction zone between the catalyst surface and the gas-phase reaction can provide insights into catalytic reactor design,thereby facilitating the scale-up from the laboratory to the commercial scale.展开更多
1,3,5-Trisubstituted pyrazolines are rapidly and conveniently oxidized to their corresponding pyrazoles by 1,3-dichloro-5,5- dimethylhydantoin（DCH） in solution and solvent-free conditions under microwave irradiation...1,3,5-Trisubstituted pyrazolines are rapidly and conveniently oxidized to their corresponding pyrazoles by 1,3-dichloro-5,5- dimethylhydantoin（DCH） in solution and solvent-free conditions under microwave irradiation.The presence of silica gel as a supporting agent is shown to be effective in reducing the reaction times and increasing the yields.展开更多
基金the National Natural Science Foundation of China （No. 20343002, 20433030） from PetroChina are gratefully acknowledged.
文摘The Pd-promoted Ga/HZSM-5 catalyst was prepared by impregnation method and its catalytic activity for non-oxidative aromatization of C1 to C3 hydrocarbons was assessed using a microreactor-GC system operated with temperature at 823 K and space velocity at 410 h-1. The catalyst is more catalytically active for methane conversion than Ga/HZSM-5. The mass spectroscopy analyses confirmed that 13CH4 was converted to aromatic products.
基金This work is supported by the National Science Foundation of China(Grant Nos 2034300220433030)and PetroChina.
文摘The non-oxidative aromatization of mixed CH4 with C3H8 over La-promoted Zn/HZSM-5 catalysts was studied in a fixed-bed reactor at 823 K with space velocity 600 h^-1 and CH4/C3H8(mol ratio)=5:l.The propane conversion and the aromatic selectivities were up to 99%and 60%over the catalyst respectively,while methane conversion had an induction period with the highest conversion of 30%.The structure and surface acidity of the catalysts were characterized by XRD,NH3-TPD and TG-DTA.The influences of reaction and regenerative conditions on the activity and selectivity were also investigated.
基金supported by the National Key R&D Program of China(2021YFA1501700)the National Natural Science Foundation of China(22272114)+2 种基金the Funding for Hundred Talent Program(20822041E4079)the Fundamental Research Funds from Sichuan University(2022SCUNL103)This work has also been supported by SINOPEC Research Institute of Petroleum Processing Co.,Ltd.via collaborative project No.36800000-24-ZC0607-0175.
文摘Converting waste plastics directly into valuable aromatic chemicals is a promising,cost-effective recycling strategy.Traditional zeolite-catalyzed cracking of polyolefins to produce aromatics often needs high temperatures and faces issues like low selectivity for liquid aromatics,separation difficulties,and rapid catalyst deactivation due to coking.To address this,a multifunctional Ni/HZSM-5 catalyst was developed to efficiently upgrade various polyolefins—including polyvinyl chloride—into gaseous alkanes(C_(1)–C_(5))and easily separable liquid aromatics(C_(6)–C_(12))at 400°C,without added solvents or hydrogen.Aromatic products make up 57.1 wt%of total output,with more than 97.8%selectivity for the liquid phase and a BTX(benzene,toluene,and xylene)selectivity of 76.1%.The high activity and selectivity for aromatics stem from synergistic interactions between Ni nanoparticles(NPs)and acid sites in the zeolite,which promote selective C–C bond breaking and control hydrogenolysis and aromatization pathways.This synergy allows precise control over the distribution of products by carbon number and favors the formation of separable aromatics.Notably,the catalyst also prevents coking by hydrogenolyzing and hydrogenating reactive intermediates before they form stable graphite-like deposits.Consequently,Ni/ZSM-5 catalyst demonstrates excellent stability,maintaining consistent aromatics yield over 13 consecutive cycles and processing over 30 times its weight in plastics without regeneration.After regeneration,the activity of the catalyst was fully restored,highlighting its potential for industrial use.This work offers valuable insights for designing durable,high-activity catalysts,providing a practical route to improve plastic recycling technologies.
文摘The intrinsic reaction kinetics of methane aromatization under non-oxidative conditions over modified Mo/HZSM-5 catalysts was studied in the quartz pipe-reactor under ordinary pressure with the temperature ranging from 913.15 to 973.15 K and the space velocity from 700 to 2100 ml/（g·h）. The Langmuir-Hinshelwood model was chosen to describe the intrinsic kinetics while Levenberg-Marquardt method was selected to determine the parameters in the kinetic model. Statistical test and residual error distribution diagrams showed that experimental data were in good agreement with calculated data, and Langmuir-Hinshelwood model was suitable for the description of the intrinsic kinetics of methane aromatization under the reaction conditions discussed in this article.
文摘The optimum Mo/[H^+] ratio per unit cell of the active precursors in Mo/HZSM-5 catalysts for methane dehydro-aromatization, measured by1H MAS NMR, was found to be about 1 when adjusting the acid sites by altering either the SiO2/Al2O3 ratios or the Mo loading. This implies that a concerted interaction between the Mo species and the Bronsted acid sites probably features the bifunctionality of the Mo/HZSM-5 catalyst. On the other hand, it was found that the driving force for Mo species to move into the HSZM-5 zeolite channels and the interaction between the Mo species and the Bronsted acid sites are closely and proportionably related with the amount of Bronsted acid sites per unit cell.
基金supported by the National Natural Science Foundation of China(Grant Nos.22288101,22472016)the National Key Research and Development Program of the Ministry of Science and Technology(No.2022YFE0116000)+1 种基金the Chinese Academy of Sciences Strategy Leading Technology Project(No.XDA29000000)the Youth Innovation Promotion Association CAS(No.2021182)。
文摘Aromatization of alkanes represents an important process in the chemical industry,traditionally relying on noble metal catalysts.Developing a non-noble metal catalyst and a relevant new process offers significant potential for promoting technologic progress in this field.Herein,we present Cu-ZSM-5 zeolite as a highly effective catalyst for alkane aromatization,achieving outstanding aromatics selectivity.In-situ Fourier transform infrared spectra of adsorbed nitric oxide,high-angle annular dark field scanning transmission electron microscopy,X-ray absorption spectroscopy,and electron paramagnetic resonance analyses reveal that the Cu^(2+)species act as the primary active centers for aromatics formation.During aromatization of alkanes,the reduction of Cu^(2+)to Cu^(+)species correlates with diminished aromatics selectivity.Notably,introducing CO_(2)into the reaction feed not only enhances aromatics selectivity by maintaining Cu^(2+)species in their active oxidation state under reducing conditions,but also improves catalytic stability by eliminating coke.Furthermore,CO_(2)is converted into CO and aromatic products during the reaction,offering a novel way for CO_(2)utilization through the coupling reaction of alkane and CO_(2).
文摘Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in shale gas.Owing to their thermodynamic resistance,converting CO_(2)and C_(3)H_(8) respectively remains difficult.Here,we achieve 60.2%aromatics selectivity and 48.8%propane conversion over H-ZSM-5-25 via a zeolite-catalyzing the coupling of CO_(2)and C_(3)H_(8).Operando dual-beam FTIR spectroscopy combined with ^(13)C-labeled CO_(2)tracing experiments revealed that CO_(2)is directly involved in the generation of aromatics,with its carbon atoms selectively embedded into the aromatic ring,bypassing the reverse water-gas shift pathway.Accordingly,a cooperative aromatization mechanism is proposed.Thereinto,lactones,produced from CO_(2)and olefins,are proven to be the key intermediate.This work not only provides an opportunity for simultaneous conversion of CO_(2)and C_(3)H_(8),but also expends coupling strategy designing of CO_(2)and alkanes over acidic zeolites.
文摘Aromatization of light alkanes is a value-added process in both petrochemical and coal chemical industries.Here,single[Ga(OH)]^(2+)ion-exchanged mesoporous hollow-structured ZSM-5(Ga-MH-ZSM-5)material was prepared,and it shows unprecedented catalytic performance in light alkane aromatization,considering activity,product selectivity and catalytic stability.The average aromatics yields in ethane aromatization at 600℃and WHSV of 0.8 h^(-1) within 28 h and in propane aromatization at 580℃and WHSV of 1.1 h^(-1) within 20 h reach~18.4%and~70.8%with benzene,toluene and xylenes(BTX)accounting for~96%and~88%of aromatics,respectively.Ga-MH-ZSM-5-0.41 gave a TON for formation of aromatics(TON_(aromatics))from propane as high as 57479,whereas the reported catalysts maximally show a TON_(aromatics) of 5514.This also holds true for ethane aromatization;the TON_(aromatics) obtained on Ga-MH-ZSM-5-0.41 was³3845 in contrast to£392 on reported non-noble metal catalysts.The catalytic activity of Ga-MH-ZSM-5 highly depends on Ga species structures.[Ga(OH)]^(2+)ions are predominant species at Ga loading≤0.3 wt%,while more[Ga(OH)_(2)]^(+)and GaO_(x) oligomers are formed with increasing Ga content.Upon reduction with H_(2),[Ga(OH)]^(2+)and[Ga(OH)_(2)]^(+)are transformed into[GaH]^(2+)and[GaH_(2)]^(+)species,which show a propane dehydrogenation rate of 300 and 15 times of that of Brønsted acid sites respectively.The light alkanes are mainly dehydrogenated into light olefins on[GaH]^(2+)species,and then,oligomerized and cyclized into(alkyl)cycloalkanes on H^(+)sites,which is followed by possible ring expansion on H^(+)and sequential dehydrogenations into aromatics primarily on[GaH]^(2+).
基金supported by the National Key R&D Program of China(Nos.2018YFC1004300 and 2018YFC1004302)the Science&Technology Program of Guizhou Province(Nos.QKHHBZ[2020]3002,QKHPTRC-GCC[2022]039-1 and QKHPTRCCXTD[2022]014)the Scientific Research Program of Guizhou Provincial Department of Education(No.QJJ[2023]019).
文摘Despite the widespread presence and frequent detection of polycyclic aromatic hydrocarbons(PAHs)in various aspects of life,there is limited research on their exposure levels in pregnant women and cumulative exposure from the living environment.This study included 1311 women in late pregnancy from the Zunyi birth cohort and measured the urinary concentrations of 10 hydroxylated PAH metabolites(OH-PAHs).Risk assessment was conducted based on the estimated daily intake to calculate the hazard quotient and hazard index(HI).A linear regression model was used to analyze the relationship between creatinine-adjusted OH-PAHs concentrations and living environment and lifestyle factors,while principal component analysis was applied to trace the sources of PAHs exposure.1-OHPYR was detected in all participants’urine,with naphthalene metabolites having the highest concentrations among creatinine-adjusted PAHs.OH-PAHs concentrations were associated with housing type,room number,cooking frequency,household size,exercise frequency,fuel type,distance from main road,and drinking water source.Pregnant women using traditional fuels and living in bungalows had higher health risks than those using clean energy and living in buildings.Those living within 100 m of a main road had higher HI than those farther away.Coal combustion was identified as the primary source of PAHs exposure.The study emphasizes the importance of reducing PAHs exposure,especially for pregnant women living in polluted environments.It recommends public health interventions such as improving indoor ventilation and providing clean energy to reduce related health risks.
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supported by the Industrial Research Project of Shaanxi Science and Technology Department(2014K08-29)Science and Technology Plan Project of Xi’an(CXY1511(7))Scientific Research Foundation of Northwest University~~
文摘We have developed an iron（III） phthalocyanine chloride‐catalyzed oxidation–aromatization ofα,β‐unsaturated ketones with hydrazine hydrate. Various 3,5‐disubstituted 1H‐pyrazoles were obtained in good to excellent yields. This method offers several advantages, including room‐tem‐perature conditions, short reaction time, high yields, simple work‐up procedure, and use of air as an oxidant. The catalyst can be recovered and reused five times without loss of activity.
基金supported by the National Ministry of Education(NCET-10-878)Shaanxi"13115"Innovation Project(2009ZDKJ-70)Shaanxi Key Innovation Project(2011ZKC4-08)
文摘The coking kinetics and reaction-regeneration on Zn/HZSM-5 （Zn/HZ） catalyst in the conversion of methanol to aromatics were investigated. The highest initial benzene, toluene and xylene （BTX） yield of ca. 67.7% was obtained on fresh Zn/HZ catalyst, which showed the worst catalytic stability. The cycle of reaction-regeneration significantly modified the texture and acidity of Zn/HZ catalyst, which in turn affected its catalytic performance and coking behavior in methanol conversion to BTX. The residual carbon located on the surface of Zn/HZ catalyst led to the decrease of acid sites and the change on the acid sites distribution, which played an important roles on its activity and deactivation. It was found that the high B/L ratio and the low total acid sites concentration of the Zn/HZ catalyst favored to the high BTX yield and good catalytic stability in methanol conversion.
基金supported by the National Basic Research Program of China(Grant 2005CB 221405)
文摘The influences of binder and molding method on the catalytic performance of methane aromatization in the absence of O2 over MoO3/ZSM-5 catalysts were investigated.SEM,NH3-TPD,FT-IR of adsorbed pyridine,N2 adsorption-desorption,cyclohexane adsorption and XPS were employed to characterize the physical and chemical properties of the catalysts.It was found that SiO2 was a suitable binder for the catalyst due to its appropriate weak acidity.The laminar catalyst comprising of an inert spherical core and a MoO3/ZSM-5 laminar shell with 0.1 0.2 mm in thickness showed a better catalytic performance than the extruded catalyst.The improved activity of the laminar catalyst could be attributed to the easy carbonization of Mo species and the quick removal of reaction products from the catalyst surface.
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entrusted by the Project of "utilization of low rank coal" strategic leading special fundstrategic leading special fund of CAS (XDA-07070800 and XDA-07070400)the Opening Foundation of State Key Laboratory of Coal Conversion (J16-17-602)
文摘Zn/ZSM-5（NZ2） and Zn/Ni/ZSM-5（NZ3） as the catalysts for methanol to aromatics（MTA） were synthesized by a simple ultrasonic impregnation. The textural and acid properties of all catalysts were characterized using XRD, HRTEM, NH;-TPD, Py-IR, XPS, XRF and TG techniques. The XRD and HRTEM results showed that the basic zeolite structures were not affected much with the incorporation of Zn and Ni species. However, great changes have taken place in acid properties. The Py-IR and XPS results indicated that the Zn-Lewis acid sites（ZnOH;species）, which have stronger interaction with the zeolite framework compared with ZnO species, were generated at the expense of B acid sites with the incorporation of zinc species. Moreover, the product analysis results showed that the incorporation of zinc species promoted the primary aromatization by enhancing the dehydroaromatization and suppressing the cracking and subsequent H-transfer reaction. Furthermore, the addition of Ni species well inhibited the loss of zinc species by converting partial ZnO species to ZnOH;species, and thus improved the aromatization activity and catalyst stability. The catalytic performance results showed that the NZ3 possess higher conversion of methanol in a longer time and lower average rate of coke formation compared with NZ2. In addition,the NZ3 also exhibited the highest yield of BTX as the reaction proceeds.
基金financially supported by the National Natural Science Foundation of China (21603023)
文摘Platinum(Pt)supported on Zinc(Zn)modified silicalite-1(S-1)zeolite(denoted as Pt-Zn/S-1)was prepared by using a wetness-impregnation method and applied in the n-hexane aromatization reaction for the first time.Both Lewis and Bronsted acid sites were detected in Pt-Zn/S-1 catalyst by means of FT-IR adsorption of NH3 experiment,which were identified as mostly weak and medium ones.Besides,Pt and Zn species showed strong interaction,as revealed by the TPR(Temperature-programmed reduction)and XPS(X-ray photoelectron spectroscopy)experiments.Pt-Zn/S-1 catalyst exhibited excellent aromatization function rather than isomerization and cracking side reactions in the conversion of n-hexane.Pulse experimental study showed that 75.6%of n-hexane conversion and 76.8%of benzene selectivity were obtained over Pt0.1-Zn60/S-l catalyst at 550℃ and under atmospheric pressure.By spectroscopy tests and pulse experimental results,it was concluded that the n-hexane aromatization over Pt-Zn/S-1 catalyst follows a metal-acid bifunctional mechanism.Furthermore,with the assistance of Zn,the electron-deficient Pt species in Pt-Zn/S-1 showed good sulfur tolerance performance.
基金Supported by the Fundamental Research Funds for the Central Universities,HUST(Z2009008)the National Natural Science Foundation of China(20973068)
文摘Aromatization of methanol over co-impregnated La/Zn/HZSM-5 zeolite catalyst was studied.The selectivity of aromatics and BTX(benzene,toluene,and xylene)reached 64.0%and 56.6%,respectively,using La/Zn/HZSM-5 at 437°C,0.1 MPa and methanol WHSV(weight hourly space velocity)=0.8 h-1.Catalytic results showed that the La species was a very good promoter,increased selectivity of aromatics,and prolonged the catalyst lifetime on stream.The effects of the SiO2/Al2O3 ratio in zeolite,Zn and La loading,WHSV,reaction temperature, water content in the feed and H2 pretreatment of catalysts on the catalytic performance were studied in detail. Characterizations of the catalysts by thermogravimetric analysis(TGA),NH3-TPD(temperature programmed desorption),SEM(scanning electron micrograph),N2 adsorption-desorption,XRD(X-ray diffraction)and XRF (X-ray fluorescence),were carried out to understand the structure and discuss the aromatization performance of La/Zn/HZSM-5 zeolite catalyst.
基金financial support from the National Natural Science Foundation of China(21433001,21406251 and 21403265)Science and Technology Development Projects of SINOPEC,China(No.113138,112008 and 110099)The Young Taishan Scholars Program of Shandong Province(tsqn20161052)
文摘In this work, nickel metal supported on different supports(SiO_2, Al_2O_3, ZSM-5) were prepared by spraying nickel nitrate on the supports and calcined at 873 K. Then, they were characterized by XRD, XRF, N_2 adsorption–desorption, NH_3-TPD, MCH-TPD, H_2-TPR, and pyridine-FTIR,and tested as catalysts for the dehydrogenation aromatization and isomerization of methylcyclohexane(MCH) under the conditions of S-Zorb catalytic adsorption desulfurization(T ? 673 K, P ? 1.5 MPa, WHSV ? 5 h^(-1)). The H2-TPR results showed that the interaction of NiO with support decreased in the order of NiO/ZSM-5-Fe < NiO/ZSM-5 < NiO/Al_2O_3< NiO/SiO2. The decrease of the interaction appeared to facilitate the reduction of Ni and therefore to promote the dehydrogenation aromatization of MCH.It was found that a direct correlation existed between the gasoline components yields, cracking activity and the total number of different supports acid sites measured by NH_3-TPD tests. Higher total acidity of ZSM-5 resulted in gasoline loss because of higher cracking activity of MCH. The number of total acid sites of NiO/ZSM-5-Fe decreased and the medium strong Br€onsted acid sites necessary for MCH isomerization increased after the modification of ZSM-5 by iron metal. So, NiO/ZSM-5-Fe exhibited enhanced MCH conversion, aromatic and isomerization yields when compared to NiO/ZSM-5 and other Ni-based catalysts. This study shows that NiO/ZSM-5-Fe catalyst may be possible to be integrated into the S-Zorb system achieving the recovery of the octane number of gasoline.
基金supported by the C1 Gas Refinery Program through the National Research Foundation of Korea (NRF)funded by the Ministry of Science,ICT&Future Planning (NRF2017M3D3A1A01037001)supported by the Ministry of Trade,Industry and Energy (MOTIE),Korea Institute for Advancement of Technology (KIAT)through the Virtual Engineering Platform Program (P0022334)。
文摘The conversion of methane to olefins,aromatics,and hydrogen(MTOAH)can be used to stably obtain hydrocarbons when the effect of the catalytic surface is optimized from the reaction engineering perspective.In this study,Fe/Si C catalysts were packed into a quartz tube reactor.The catalytic surfaces of Si C and the impregnated Fe species decreased the apparent activation energies(E_a)of methane consumption in the blank reactor between 965 and 1020℃.Consequently,the hydrocarbon yield increased by 2.4times at 1020℃.Based on the model reactions of ethane,ethylene,and acetylene mixed with hydrogen in the range of 500-1020℃,an excess amount of Fe in the reactor favored the C-C coupling reaction over the selective hydrogenation of acetylene;consequently,coke formation was favored over the hydrogenation reaction.The gas-phase reactions and catalyst properties were optimized to increase hydrocarbon yields while reducing coke selectivity.The 0.2Fe catalyst-packed reactor(0.26 wt%Fe)resulted in a hydrocarbon yield of 7.1%and a coke selectivity of<2%when the ratio of the void space of the postcatalyst zone to the catalyst space was adjusted to be≥2.Based on these findings,the facile approach of decoupling the reaction zone between the catalyst surface and the gas-phase reaction can provide insights into catalytic reactor design,thereby facilitating the scale-up from the laboratory to the commercial scale.
文摘1,3,5-Trisubstituted pyrazolines are rapidly and conveniently oxidized to their corresponding pyrazoles by 1,3-dichloro-5,5- dimethylhydantoin（DCH） in solution and solvent-free conditions under microwave irradiation.The presence of silica gel as a supporting agent is shown to be effective in reducing the reaction times and increasing the yields.
