Corn rod-like WO<sub>3</sub> nanomaterials were successfully synthesized by a simple hydrothermal method. The morphology, structure and optical absorption properties of the prepared samples were characteri...Corn rod-like WO<sub>3</sub> nanomaterials were successfully synthesized by a simple hydrothermal method. The morphology, structure and optical absorption properties of the prepared samples were characterized by SEM, XRD, FTIR and UV-Vis-DRS. The WO<sub>3</sub> materials were corn rod-like morphology with about 800 nm for length and 150 nm for diameter, especially there were plenty of corn particles (about 20 nm) on the surface of corn rods. The X-ray diffraction peaks of the products corresponded with WO<sub>3</sub> standard card, and the characteristic peak of W-O bond was found in the infrared spectrum. The absorption band edge of the products was about 480 nm, indicating their potential visible-light-induced photocatalytic activity. In situ FTIR technology research showed that the prepared WO<sub>3</sub> nanomaterials had visible photocatalytic activity to gas-phase toluene. After a photocatalytic reaction for 8 hours toluene was effectively degraded, and carboxylic acid and aldehyde could be regarded as the intermediate products, and CO<sub>2</sub> was produced as the final product during the reaction process.展开更多
Catalytic methylation of toluene with methanol is an important alternative pathway for xylene production.Previous studies have indicated that methanol always undergoes several side reactions on acidic zeolites,resulti...Catalytic methylation of toluene with methanol is an important alternative pathway for xylene production.Previous studies have indicated that methanol always undergoes several side reactions on acidic zeolites,resulting in oxygencontaining byproducts such as dimethyl ethers,ketones,and carboxylic acids.Herein,the presence and distribution of the oxygenated compounds formed during toluene methylation were firstly examined by systematic chromatographic analysis.Plausible formation mechanisms for the various oxygenates are discussed.The most problematic byproduct is found to be acetic acid,which can lead to inferior product quality and damage downstream units.A feasible solution is presented for oxygenate removal after toluene methylation,in which acetic acid is eliminated by catalytic decomposition into low-boilingpoint acetone over a MgO catalyst.This process allows for all of the low-boiling-point oxygenates,including methanol,dimethyl ether,acetone,and butanone,to be removed from the aromatics phase,taking advantage of the temperature of the reaction effluent and standard distillation equipment.X-ray diffraction was used to characterize the crystal phase of the fresh and used MgO decarbonylation catalysts,while thermogravimetry/mass spectrometry and Fourier-transform infrared spectroscopy were applied to investigate the transformation mechanism of acetic acid over the decarbonylation catalyst.CO insertion and ketonization of acetic acid accounted for the formation and elimination of acetic acid,respectively.The combined methylation/decarbonylation process should enable the production of high-quality xylenes,an important industrial feedstock,by overcoming the main technical obstacles associated with the toluene methylation process.展开更多
It is crucial to efficiently separate and transport photo-induced charge carriers for the effective implementation of photocatalysis toward environmental remediation.A rational design strategy is proposed to validate ...It is crucial to efficiently separate and transport photo-induced charge carriers for the effective implementation of photocatalysis toward environmental remediation.A rational design strategy is proposed to validate such proposition through the construction of an interfacial structure in the form of LDH/Zn_(2)SnO_(4) heterostructures in this research.The interfacial charge transfer on LDH/Zn_(2)SnO_(4) is greatly promoted via the unique charge transfer pathway,as characterized by transient photocurrent responses,X-ray photoelectron spectroscopy,electron paramagnetic resonance spectrum,and photoluminescence analysis.As such,it contributes to the generation of reactive oxygen species(ROS)and the activation of reactants for the mineralization of toluene.According to the in situ DRIFTS spectra analysis,the accumulation of benzoic acid takes place possibly through the partial oxidation of the methyl group on toluene at the interface of the LDH/Zn 2 SnO 4 heterostructure.This process can greatly promote the photocatalytic oxidation of toluene with the enhanced ring-opening efficiency.The LDH/Zn 2 SnO 4 is thus demonstrated as superior photocatalyst against toluene(removal efficiency of 89.5%;mineralization of 83.1%;and quantum efficiency of 4.55×10^(−6) molecules/photon).As such,the performance of this composite far exceeds that of their individual components(e.g.,P25,pure Mg-Al LDH,or Zn_(2)SnO_(4)).This study is expected to offer a new path to the interfacial charge transfer mechanism based on the design of highly efficient photocatalysts for air purification.展开更多
Y zeolites have moderate microporous pore size, large specific surface area, and good hydrothermal stability, which were widely used in industrial adsorption of volatile organic compounds (VOCs), but the performance o...Y zeolites have moderate microporous pore size, large specific surface area, and good hydrothermal stability, which were widely used in industrial adsorption of volatile organic compounds (VOCs), but the performance of Y zeolites in adsorption of VOCs under high humidity conditions is terrible. In this paper, Y zeolites with different silica-alumina ratios were hydrophobically modified by organosilane and characterized by XRD, FTIR, SEM, BET, NMR. In the experiments of static and dynamic adsorption of VOCs by modified Y zeolites, it can be concluded that the static water adsorption capacity of Y zeolites with silica-aluminum ratio of 5 and 40 after silica modification decreased by 62 wt% and 53 wt%, under the conditions of high humidity, GHSV = 15,000 h<sup>-1</sup>, T = 35°C and initial concentration of toluene C<sub>0</sub> = 5000 mg·m<sup>-3</sup>. The saturation adsorption capacity of toluene was increased from 0.06 g·g<sup>-1</sup>, 0.09 g·g<sup>-1</sup> to 0.15 g·g<sup>-1</sup>, 0.21 g·g<sup>-1</sup>, the adsorption selectivity of Y zeolites for water was reduced and that for toluene was increased after Vapor phase silanization overlay modification. The present modification method might carry out targeted modification of zeolites surface, provide research ideas and guidance under high humidity conditions.展开更多
In this paper, (2H- methyl) toluene was prepared by catalysed halogen- tritium substitution method from benzyl bromide, then it was nitrated to produce (8H- methyl) trinitrotoluene. The tritiated product was purified ...In this paper, (2H- methyl) toluene was prepared by catalysed halogen- tritium substitution method from benzyl bromide, then it was nitrated to produce (8H- methyl) trinitrotoluene. The tritiated product was purified by thin- layer chromatography. At last, the pure 3H- TNT was obtained with specific radioactivity of 3.77 GBq/mmol. Radiochemical purity was over 98% and the ultraviolet absorption spectrum of tritiated TNT was conformed with that of standard sample. Using 3H- TNT as a tracer, its toxicokinetics was sudied in rats. The results showed that the toxicokinetics characteristics of TNT were quickly absorbed into the blood, Vd】2L/kg.h, long T1/2β and fixed accumulation with four routes of administration, TNT and its metabolites were mainly excreted by the urine. The half- life of TNT in the urine were 1,1- 24h. A trace of radioactivity of 3H- TNT and its metabolites could be detected in the urine on 7th day after administration (9.25×106Bq/kg).展开更多
With the shape selective zeolite catalyst,toluene alkylation with methanol to para-xylene(MTPX)technology could produce highly pure para-xylene(PX)in one step.The lower feedstock cost and less energy consumption in pr...With the shape selective zeolite catalyst,toluene alkylation with methanol to para-xylene(MTPX)technology could produce highly pure para-xylene(PX)in one step.The lower feedstock cost and less energy consumption in products separation make it more competitive compared to the current toluene disproportionation route.Thus,MTPX is regarded as the most reasonable production route for PX production.This article reviews the strategies that applied to the preparation of high-performance catalysts for MTPX,with special focus on the precise control of pore dimension and acid sites distribution in zeolite to achieve the highest selectivity to PX.The outlook of the MTPX catalyst is also proposed to guide the catalyst development in the field.展开更多
Two novel washcoats Ce0.8Zr0.15La0.05Oδ and Ce0.8Zr0.2O2 was prepared by an impregnation method, which acted as a host for the active Pd component to prepare Pd/Ce0.8Zr0.15La0.05Oδ/substrate and Pd/Ce0.8Zr0.2O2/subs...Two novel washcoats Ce0.8Zr0.15La0.05Oδ and Ce0.8Zr0.2O2 was prepared by an impregnation method, which acted as a host for the active Pd component to prepare Pd/Ce0.8Zr0.15La0.05Oδ/substrate and Pd/Ce0.8Zr0.2O2/substrate monolithic catalysts for toluene combustion. The washcoats was characterized by X-ray diffraction (XRD), Raman spectroscopy, Brunauner-Emmett-Teller (BET), and H2-temperature-programmed reduction (H2-TPR). The result indicated that both the washcoats had strong vibration-shock resistance according to ultrasonic test. Doping La3+ into CeO2-ZrO2 solid solution could generate more oxygen vacancies, and could inhibit the sinter of CeO2-ZrO2 solid solution when calcined at high temperatures (800, 900 and 1000 °C). The washcoat Ce0.8Zr0.15La0.05Oδ had much better redox properties. The reductive temperature of Ce4+ species shifted to low temperature by 60 °C when the washcoats calcined at high temperatures (800, 900 and 1000 °C). The Pd/Ce0.8Zr0.15La0.05Oδ/substrate monolithic catalyst calcination at 500 °C had the best catalytic activity and the 95% toluene conversion at a temperature as low as 190 °C. When calcined at low temperature (500 and 700 °C), the catalytic activity has little improvement, however, when calcined at high temperature, the catalytic activity of Pd/Ce0.8Zr0.15La0.05Oδ/substrate monolithic catalysts had significant improvement. As catalyst washcoat, the Ce0.8Zr0.15La0.05Oδ had better thermal stability than the washcoat Ce0.8Zr0.2O2, the developed Pd/Ce0.8Zr0.15La0.05Oδ/ substrate monolithic catalyst in this work was promising for eliminating Volatile organic compounds.展开更多
A series of calcined HTLcs catalysts were prepared and modified with potassium phosphate by impregnation method to clarify the influence of catalyst alkalinity on the side chain alkylation of toluene with methanol for...A series of calcined HTLcs catalysts were prepared and modified with potassium phosphate by impregnation method to clarify the influence of catalyst alkalinity on the side chain alkylation of toluene with methanol for synthesis of ethylbenzene and styrene.The catalysts were characterized by X-ray diffraction(XRD),N_(2)physical adsorption-desorption,Fourier-transform infrared spectroscopy(FT-IR),Scanning electron microscopy(SEM),X-ray photoelectron spectrometry(XPS),NH_(3)temperature-programmed desorption(NH_(3)-TPD)and CO_(2)temperature-programmed desorption(CO_(2)-TPD).It was found that the selectivity of styrene was highest(39.25%)when the K_(3)PO_(4)loading was 7.5 wt%.And the total yield of styrene and ethylbenzene could reach 65.08%with 10 wt%K_(3)PO_(4)loading.This might due to the fact that the addition of K_(3)PO_(4)could adjust the acid and basic sites of catalysts.In addition,appropriate strength and amount of basic sites were favorable to producing more styrene.展开更多
A new method was introduced to detect the concentration of OH radical in dielectric barrier discharge(DBD)reaction.A film, which was impregnated with salicylic acid,was used to detect OH radical in plasma reaction at ...A new method was introduced to detect the concentration of OH radical in dielectric barrier discharge(DBD)reaction.A film, which was impregnated with salicylic acid,was used to detect OH radical in plasma reaction at room temperature and atmospheric pressure.Salicylic acid reacts with OH radical and produces 2,5-dihydroxybenzoic acid(2,5-DHBA).Then,a high performance liquid chromatography(HPLC)was carried out to detect the concentration of 2,5-DHBA.Therefore,OH radical in nonthermal plasma reaction could be calculated.In this plasma reaction,the applied voltage was controlled at 10 kV,the initial concentration of toluene was 400 mg/m3,and the gas flow rate was 300 ml/min.It was observed that when the film was placed away from the plasma area,2,5-DHBA could not be detected by HPLC,although the sampling time lasted for 48 h.On the other hand,when the film was placed in the plasma area and the sampling time being too long(>4 h),the concentration of 2,5-DHBA was also below detection limit,and it could not be detected by HPLC.However,when the film was placed in the plasma reaction field with the sampling time being 3 h,the concentration of OH radical was calculated to be 10.54×1012 cm-3.In addition,concentration of OH radical was investigated under different humidity,such as 0.2%,0.4%,0.6%,0.8%,and 1.0%.The results showed that the amount of OH radical stayed at order of magnitude of 1012 cm-3 and increased with the increase of humidity.展开更多
The adsorption performance of toluene on ultra-stable Y zeolite (USY) was studied via dynamic adsorption. The eff ects of bed temperature, initial concentration, and feed fl ow rate on adsorption were investigated. Th...The adsorption performance of toluene on ultra-stable Y zeolite (USY) was studied via dynamic adsorption. The eff ects of bed temperature, initial concentration, and feed fl ow rate on adsorption were investigated. The Yoon-Nelson model was used to fi t the toluene breakthrough curves. The length of mass transfer zone was calculated based on breakthrough curves. The Langmuir-Freundlich model fi t the adsorption isotherms of toluene on USY, which indicated that the surface of USY was heterogeneous. The adsorption isosteric heat calculated from adsorption isotherms ranged from 54.3 to 69.8 kJ/mol, indicating physical adsorption. The combined technique of temperature swing adsorption with vacuum swing adsorption (TVSA) exhibited excellent desorption performance, which was attributed to the low desorption activation energy. Under optimized TVSA conditions, the desorption rate of toluene reached 90.6% within 10 min. The long-term cyclic utilization results indicated that the adsorption capacity of USY was stable.展开更多
As green solvents,ionic liquids(ILs)are quite suitable for the absorption of volatile organic compounds(VOCs)such as benzene and its homologues.However,solvent selection is the key to the VOC absorption process.In the...As green solvents,ionic liquids(ILs)are quite suitable for the absorption of volatile organic compounds(VOCs)such as benzene and its homologues.However,solvent selection is the key to the VOC absorption process.In the present study,a rapid solvent screening tool,Conductor-like Screening Model for Real Solvents(COSMO-RS),was used to predict the solubility of toluene in 816 ILs.The effects of four structure characters,namely,the type and alkyl chain length of the cations and anions on the solubility of toluene were discussed.The following conclusions were drawn from the results:(1)ILs with pyrrolidinium-based cations showed better solubility than pyridinium-and imidazoliumbased ones.(2)The solubility of toluene in PF6-based ILs increased with the increasing alkyl chain length,while its solubility in Ac-based ILs exhibited the opposite trend.(3)Toluene showed greater solubility in Cl-based ILs than those based on other anions.(4)The solubility of toluene increased with the anion alkyl chain length.Ac-based ILs were chosen as the most promising potential solvents,and further studied to determine the relationship between various interaction energy parameters and toluene solubility.The results showed that the misfit energy played a dominant role during the absorption process.Furthermore,several ILs were selected for experimental verification of the predicted solubility behavior using liquid and gaseous toluene.The results demonstrated that COSMO-RS could be used to semi-quantitatively and qualitatively predict the solubility of toluene,and this model had promising prospects in screening ILs for VOCs absorption.In summary,this study provided a fundamental basis and practical data for the control and treatment of VOCs.展开更多
An experimental system for measuring the VLE of polymer solutions based on the staticvapor-pressure method has been established,VLE data for mixtures of toluene and polystyrene withdifferent molecular weight covering ...An experimental system for measuring the VLE of polymer solutions based on the staticvapor-pressure method has been established,VLE data for mixtures of toluene and polystyrene withdifferent molecular weight covering a wide range from 2.98×10~3 to 3.84×10~6 were obtained at 35℃.The reduced pressure p/p°versus weight fraction W plot is found to be independent on the molecularweight of the polymer within the experimental error.Calculated activity coefficients are also independenton the molecular weight.However,for the Flory-Huggins interaction parameter x,not only a strongconcentration dependence is observed,but also the molecular weight of the polymer exerts definiteinfluence.Generally,the parameter x slightly increases as the molecular weight of the polymer decreasesespecially when the molecular weight is low.The dependence of the parameter x on the molecularweight can be neglected when the molecular weight of polymer is greater than 1.00×10~4.展开更多
The hierarchical nanostructured N-doped TiO2 immobilized activated carbon fiber(N-TiO2/ACF)porous composites are fabricated to removal dynamic toluene gas.The results show that nitrogen ions doping and ACF modificatio...The hierarchical nanostructured N-doped TiO2 immobilized activated carbon fiber(N-TiO2/ACF)porous composites are fabricated to removal dynamic toluene gas.The results show that nitrogen ions doping and ACF modification can decrease the band gap of TiO2,leading to red shift toward visible light region.Interestingly,N-TiO2/ACF exhibits strongly synergistic effect owing to high surface area,good crystallinity,enhanced bandgap structure and light harvesting.The toluene removal rate of N-TiO2/ACF composites is 2.29 times higher than that of TiO2.The N-TiO2/ACF for toluene degradation followed the Langmuir-Hinshelwood kinetic model,and the rate constant is enhanced 8 times compared with TiO2.The possible photodegradation pathway and mechanisms are proposed.展开更多
An efficient toluene removal in air using a plasma photocatalytic system(PPS)not only needs favorable surface reactions over photocatalysts under the action of plasma,but also requires the photocatalysts to efficientl...An efficient toluene removal in air using a plasma photocatalytic system(PPS)not only needs favorable surface reactions over photocatalysts under the action of plasma,but also requires the photocatalysts to efficiently absorb light emitted from the discharge for driving the photocatalytic reactions.We report here that the PPS constructed by integrating a black titania(B-TiO2)photocatalyst with a dielectric barrier discharge(DBD)can effectively remove toluene with above 70%CO2 selectivity and remarkably reduced the concentration of secondary pollutants of ozone and nitrogen oxides at a specific energy input of 1500 J-I-1,while exhibiting good stability.Photocatalyst characterizations suggest that the B-TiO2 provides a high concentration of oxygen vacancies for the surface oxidation of toluene in DBD,and efficiently absorbs ultraviolet-visible light emitted from the discharge to induce plasma photocatalytic oxidation of toluene.The presence of B-TiO2 in the plasma region also results in a high discharge efficiency,facilitating the generation of large numbers of reactive species and thus the oxidation of toluene towards CO2.The greatly enhanced performance of the PPS integrated with B-TiO2 in toluene removal offers a promising approach to efficiently remove refractory volatile organic compounds from air at low temperatures.展开更多
Biochar supported nickel(Ni/BC)has been widely studied as a cheap and easy-to-prepare catalyst with potential applications in tar reforming during the gasification of low-rank fuels,such as brown coal and biomass.Howe...Biochar supported nickel(Ni/BC)has been widely studied as a cheap and easy-to-prepare catalyst with potential applications in tar reforming during the gasification of low-rank fuels,such as brown coal and biomass.However,the role and behaviors of inherent K species,especially their interactions with Ni particles and the biochar support,are not well understood yet.In this work,three Ni/BC catalysts with varying K amount were prepared from raw,water-washed,and acid-washed biomass.They were used in steam reforming of toluene as a tar model compound to elucidate the effects of inherent K on the catalytic activity and stability.Detailed characterization indicated that K enhanced water adsorption due to its hydroscopicity and lowered the condensation and graphitization degrees of biochar,but the alteration to the electronic state of Ni was not observed.These effects together led to a temperature-dependent role of K.That is,at relatively low temperatures of 450 and 500℃,toluene conversion was increased in the presence of K,due to the increased concentration of adsorbed water around Ni particles.By contrast,at relatively higher temperatures of 550 and 600℃,although initial high activity was achieved,Ni/BC with K deactivated rapidly because of the accelerated consumption of the biochar support.展开更多
Objective This study was designed to conduct a retrospective and systematic occupational health risk assessment(OHRA)of enterprises that used benzene,toluene,and xylene(BTX)in Shanghai,China.Methods All data for the s...Objective This study was designed to conduct a retrospective and systematic occupational health risk assessment(OHRA)of enterprises that used benzene,toluene,and xylene(BTX)in Shanghai,China.Methods All data for the study were obtained from 1,705 occupational health examination and evaluation reports from 2013 to 2017,and a semiquantitative model following Chinese OHRA guidelines(GBZ/T 298-2017)was applied for the assessment.Results The selected enterprises using BTX were mainly involved in manufacturing of products.Using the exposure level method,health risk levels associated with exposure to BTX were classified as medium,negligible,or low.However,the risk levels associated with benzene and toluene were significantly different according to job types,with gluers and inkers exhibiting greater health risks.For the same job type,the health risk levels assessed using the comprehensive index method were higher than those using the exposure level method.Conclusion Our OHRA reveals that workers who are exposed to BTX still face excessive health risk.Additionally,the risk level varied depending on job categories and exposure to specific chemicals.Therefore,additional control measures recommended by OHRA guidelines are essential to reduce worker exposure levels.展开更多
Five kinds of polyimides were synthesized using five dianhydrides (including 2,2-bis[4-(3,4-dicarboxyphenoxy)- phenyl] propane dianhydride (BPADA),3,3',4,4'-diphenylsulfone-tetracarboxylic dianhydride (DSDA),4...Five kinds of polyimides were synthesized using five dianhydrides (including 2,2-bis[4-(3,4-dicarboxyphenoxy)- phenyl] propane dianhydride (BPADA),3,3',4,4'-diphenylsulfone-tetracarboxylic dianhydride (DSDA),4,4'- (hexafluoroisopropylidene)-diphthalic anhydride (6FDA),1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA), and 4,4'-oxydiphthlic dianhydride (ODPA)) and 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane (BDAF) via the two- step method that included polyaddition to form the polyamic aci...展开更多
Regenerated activated carbon(RAC)samples were prepared by carbon activation using waste activated carbon from solid waste resources as the carbon source precursor coupled with adding alkaline additives,and then were f...Regenerated activated carbon(RAC)samples were prepared by carbon activation using waste activated carbon from solid waste resources as the carbon source precursor coupled with adding alkaline additives,and then were further modified by potassium ferrate to finally prepare high-performance carbon for VOCs adsorption.At the same time,the samples before and after modification were systematically studied through characterization techniques such as SEM,Raman spectrometry,FT-IR,XPS,and dynamic/static adsorption.The results showed that the specific surface area and pore volume of the RAC after modification by the strong oxidant potassium ferrate increased by 1.4 times;the degree of defects was enhanced and the content of oxygen-containing functional groups on the surface increased significantly.Among them,the sample modified with potassium ferrate for 24 h had the best dynamic toluene adsorption performance(375.5 mg/g),and the dynamic adsorption capacity was twice that of the original sample(192.8 mg/g).The static adsorption test found that the maximum adsorption capacity of RAC-6%K_(2)FeO_(4)+H_(2)SO_(4)-24h was 796 mg/g,which indicated that the potassium ferrate modification treatment could significantly increase the VOCs adsorption performance of RAC.In addition,through consecutive toluene adsorption-desorption cycle tests,it was found that the RAC-6%K_(2)FeO_(4)+H_(2)SO_(4)-24h sample still retained 91%of adsorption activity after the fifth regeneration cycle.This indicates that RAC-6%K_(2)FeO_(4)+H_(2)SO_(4)-24h has good cycle stability and great application value for the efficient purification of industrial waste VOCs gas.展开更多
MFI molecular sieve with high specific surface area,adjustable pore size and low production cost have been recognized as an effective adsorbent for VOCs removal.In this paper,NaOH solution was used to etch ZSM-5 to in...MFI molecular sieve with high specific surface area,adjustable pore size and low production cost have been recognized as an effective adsorbent for VOCs removal.In this paper,NaOH solution was used to etch ZSM-5 to increase specific surface area and micro-mesoporous content.Graphene oxide(GO)was loaded on ZSM-5 by ultrasonic-assisted heating immersion method,and largeπ-bond structure and oxygen-containing functional groups were added to ZSM-5 for improving the composite adsorption performance.In addition,the properties of OH-ZSM-5 and ZSM-5@GO composites for toluene adsorption under different factors were also studied.It was positively correlated with initial concentration and adsorbent mass,but was negatively correlated with temperature.Meanwhile,the results showed that the saturated adsorption capacity of OH-ZSM-5(107.3 mg/g)was 1.34 times higher than that of ZG-15%(80.2 mg/g).The pseudo-first-order and pseudo-second-order kinetic model can well describe the adsorption behavior of toluene on the OH-ZSM-5 and ZG-15%,respectively.The adsorption mechanism of OH-ZSM-5 was mainly pore-filled adsorption.However,the adsorption mechanisms of ZSM-5@GO composite were pore-filled adsorption,π-πinteraction,and H-bond interaction.This study will help to design a new strategy for enhancing the performance of traditional adsorbent ZSM-5 in VOCs removal.展开更多
文摘Corn rod-like WO<sub>3</sub> nanomaterials were successfully synthesized by a simple hydrothermal method. The morphology, structure and optical absorption properties of the prepared samples were characterized by SEM, XRD, FTIR and UV-Vis-DRS. The WO<sub>3</sub> materials were corn rod-like morphology with about 800 nm for length and 150 nm for diameter, especially there were plenty of corn particles (about 20 nm) on the surface of corn rods. The X-ray diffraction peaks of the products corresponded with WO<sub>3</sub> standard card, and the characteristic peak of W-O bond was found in the infrared spectrum. The absorption band edge of the products was about 480 nm, indicating their potential visible-light-induced photocatalytic activity. In situ FTIR technology research showed that the prepared WO<sub>3</sub> nanomaterials had visible photocatalytic activity to gas-phase toluene. After a photocatalytic reaction for 8 hours toluene was effectively degraded, and carboxylic acid and aldehyde could be regarded as the intermediate products, and CO<sub>2</sub> was produced as the final product during the reaction process.
基金We gratefully acknowledge the support from the National 973 Program of China(Grant No.2003CB615800).
文摘Catalytic methylation of toluene with methanol is an important alternative pathway for xylene production.Previous studies have indicated that methanol always undergoes several side reactions on acidic zeolites,resulting in oxygencontaining byproducts such as dimethyl ethers,ketones,and carboxylic acids.Herein,the presence and distribution of the oxygenated compounds formed during toluene methylation were firstly examined by systematic chromatographic analysis.Plausible formation mechanisms for the various oxygenates are discussed.The most problematic byproduct is found to be acetic acid,which can lead to inferior product quality and damage downstream units.A feasible solution is presented for oxygenate removal after toluene methylation,in which acetic acid is eliminated by catalytic decomposition into low-boilingpoint acetone over a MgO catalyst.This process allows for all of the low-boiling-point oxygenates,including methanol,dimethyl ether,acetone,and butanone,to be removed from the aromatics phase,taking advantage of the temperature of the reaction effluent and standard distillation equipment.X-ray diffraction was used to characterize the crystal phase of the fresh and used MgO decarbonylation catalysts,while thermogravimetry/mass spectrometry and Fourier-transform infrared spectroscopy were applied to investigate the transformation mechanism of acetic acid over the decarbonylation catalyst.CO insertion and ketonization of acetic acid accounted for the formation and elimination of acetic acid,respectively.The combined methylation/decarbonylation process should enable the production of high-quality xylenes,an important industrial feedstock,by overcoming the main technical obstacles associated with the toluene methylation process.
基金This work was supported by the National Natural Science Foundation of China(21822601,22176029,22172019)the Sichuan Natural Science Foundation for Distinguished Scholars(2021JDJQ0006)+2 种基金the 111 Project(B20030)the Funda-mental Research Funds for the Central Universities(ZYGX2019Z021)KHK acknowledges support made by a grant from the National Research Foundation of Korea(NRF)funded by the Ministry Of Science And ITC(MSIT)Of The Kor-ean Government(Grant No:2021R1A3B1068304).
文摘It is crucial to efficiently separate and transport photo-induced charge carriers for the effective implementation of photocatalysis toward environmental remediation.A rational design strategy is proposed to validate such proposition through the construction of an interfacial structure in the form of LDH/Zn_(2)SnO_(4) heterostructures in this research.The interfacial charge transfer on LDH/Zn_(2)SnO_(4) is greatly promoted via the unique charge transfer pathway,as characterized by transient photocurrent responses,X-ray photoelectron spectroscopy,electron paramagnetic resonance spectrum,and photoluminescence analysis.As such,it contributes to the generation of reactive oxygen species(ROS)and the activation of reactants for the mineralization of toluene.According to the in situ DRIFTS spectra analysis,the accumulation of benzoic acid takes place possibly through the partial oxidation of the methyl group on toluene at the interface of the LDH/Zn 2 SnO 4 heterostructure.This process can greatly promote the photocatalytic oxidation of toluene with the enhanced ring-opening efficiency.The LDH/Zn 2 SnO 4 is thus demonstrated as superior photocatalyst against toluene(removal efficiency of 89.5%;mineralization of 83.1%;and quantum efficiency of 4.55×10^(−6) molecules/photon).As such,the performance of this composite far exceeds that of their individual components(e.g.,P25,pure Mg-Al LDH,or Zn_(2)SnO_(4)).This study is expected to offer a new path to the interfacial charge transfer mechanism based on the design of highly efficient photocatalysts for air purification.
文摘Y zeolites have moderate microporous pore size, large specific surface area, and good hydrothermal stability, which were widely used in industrial adsorption of volatile organic compounds (VOCs), but the performance of Y zeolites in adsorption of VOCs under high humidity conditions is terrible. In this paper, Y zeolites with different silica-alumina ratios were hydrophobically modified by organosilane and characterized by XRD, FTIR, SEM, BET, NMR. In the experiments of static and dynamic adsorption of VOCs by modified Y zeolites, it can be concluded that the static water adsorption capacity of Y zeolites with silica-aluminum ratio of 5 and 40 after silica modification decreased by 62 wt% and 53 wt%, under the conditions of high humidity, GHSV = 15,000 h<sup>-1</sup>, T = 35°C and initial concentration of toluene C<sub>0</sub> = 5000 mg·m<sup>-3</sup>. The saturation adsorption capacity of toluene was increased from 0.06 g·g<sup>-1</sup>, 0.09 g·g<sup>-1</sup> to 0.15 g·g<sup>-1</sup>, 0.21 g·g<sup>-1</sup>, the adsorption selectivity of Y zeolites for water was reduced and that for toluene was increased after Vapor phase silanization overlay modification. The present modification method might carry out targeted modification of zeolites surface, provide research ideas and guidance under high humidity conditions.
文摘In this paper, (2H- methyl) toluene was prepared by catalysed halogen- tritium substitution method from benzyl bromide, then it was nitrated to produce (8H- methyl) trinitrotoluene. The tritiated product was purified by thin- layer chromatography. At last, the pure 3H- TNT was obtained with specific radioactivity of 3.77 GBq/mmol. Radiochemical purity was over 98% and the ultraviolet absorption spectrum of tritiated TNT was conformed with that of standard sample. Using 3H- TNT as a tracer, its toxicokinetics was sudied in rats. The results showed that the toxicokinetics characteristics of TNT were quickly absorbed into the blood, Vd】2L/kg.h, long T1/2β and fixed accumulation with four routes of administration, TNT and its metabolites were mainly excreted by the urine. The half- life of TNT in the urine were 1,1- 24h. A trace of radioactivity of 3H- TNT and its metabolites could be detected in the urine on 7th day after administration (9.25×106Bq/kg).
基金the funding support(Project No.:CF9300172922)from National Institute of Clean-and-low-carbon Energy.
文摘With the shape selective zeolite catalyst,toluene alkylation with methanol to para-xylene(MTPX)technology could produce highly pure para-xylene(PX)in one step.The lower feedstock cost and less energy consumption in products separation make it more competitive compared to the current toluene disproportionation route.Thus,MTPX is regarded as the most reasonable production route for PX production.This article reviews the strategies that applied to the preparation of high-performance catalysts for MTPX,with special focus on the precise control of pore dimension and acid sites distribution in zeolite to achieve the highest selectivity to PX.The outlook of the MTPX catalyst is also proposed to guide the catalyst development in the field.
基金Project supported by Zhejiang Provincial Natural Science Foundation of China (203147)the National Natural Science Foundation of China (20473075)
文摘Two novel washcoats Ce0.8Zr0.15La0.05Oδ and Ce0.8Zr0.2O2 was prepared by an impregnation method, which acted as a host for the active Pd component to prepare Pd/Ce0.8Zr0.15La0.05Oδ/substrate and Pd/Ce0.8Zr0.2O2/substrate monolithic catalysts for toluene combustion. The washcoats was characterized by X-ray diffraction (XRD), Raman spectroscopy, Brunauner-Emmett-Teller (BET), and H2-temperature-programmed reduction (H2-TPR). The result indicated that both the washcoats had strong vibration-shock resistance according to ultrasonic test. Doping La3+ into CeO2-ZrO2 solid solution could generate more oxygen vacancies, and could inhibit the sinter of CeO2-ZrO2 solid solution when calcined at high temperatures (800, 900 and 1000 °C). The washcoat Ce0.8Zr0.15La0.05Oδ had much better redox properties. The reductive temperature of Ce4+ species shifted to low temperature by 60 °C when the washcoats calcined at high temperatures (800, 900 and 1000 °C). The Pd/Ce0.8Zr0.15La0.05Oδ/substrate monolithic catalyst calcination at 500 °C had the best catalytic activity and the 95% toluene conversion at a temperature as low as 190 °C. When calcined at low temperature (500 and 700 °C), the catalytic activity has little improvement, however, when calcined at high temperature, the catalytic activity of Pd/Ce0.8Zr0.15La0.05Oδ/substrate monolithic catalysts had significant improvement. As catalyst washcoat, the Ce0.8Zr0.15La0.05Oδ had better thermal stability than the washcoat Ce0.8Zr0.2O2, the developed Pd/Ce0.8Zr0.15La0.05Oδ/ substrate monolithic catalyst in this work was promising for eliminating Volatile organic compounds.
基金financial support from the National Key Technology Research&Development Program(Grant No.2013BAC14B04)the National Natural Science Foundation of China(Grant No.21336006)+1 种基金the Shanxi Province Key Research&Development Program(international cooperation,Grant No.201803D421099)Supported by Shanxi Scholarship Council of China(Grant No.2017-035)。
文摘A series of calcined HTLcs catalysts were prepared and modified with potassium phosphate by impregnation method to clarify the influence of catalyst alkalinity on the side chain alkylation of toluene with methanol for synthesis of ethylbenzene and styrene.The catalysts were characterized by X-ray diffraction(XRD),N_(2)physical adsorption-desorption,Fourier-transform infrared spectroscopy(FT-IR),Scanning electron microscopy(SEM),X-ray photoelectron spectrometry(XPS),NH_(3)temperature-programmed desorption(NH_(3)-TPD)and CO_(2)temperature-programmed desorption(CO_(2)-TPD).It was found that the selectivity of styrene was highest(39.25%)when the K_(3)PO_(4)loading was 7.5 wt%.And the total yield of styrene and ethylbenzene could reach 65.08%with 10 wt%K_(3)PO_(4)loading.This might due to the fact that the addition of K_(3)PO_(4)could adjust the acid and basic sites of catalysts.In addition,appropriate strength and amount of basic sites were favorable to producing more styrene.
基金supported by the National Natural Sci-ence Foundation of China(No.50708021)the GuangzhouUniversity Xinmiao Project(No.gyf1-1001)the Guangzhou University Scientific Research Start-up Project(No.gyf1-1002)
文摘A new method was introduced to detect the concentration of OH radical in dielectric barrier discharge(DBD)reaction.A film, which was impregnated with salicylic acid,was used to detect OH radical in plasma reaction at room temperature and atmospheric pressure.Salicylic acid reacts with OH radical and produces 2,5-dihydroxybenzoic acid(2,5-DHBA).Then,a high performance liquid chromatography(HPLC)was carried out to detect the concentration of 2,5-DHBA.Therefore,OH radical in nonthermal plasma reaction could be calculated.In this plasma reaction,the applied voltage was controlled at 10 kV,the initial concentration of toluene was 400 mg/m3,and the gas flow rate was 300 ml/min.It was observed that when the film was placed away from the plasma area,2,5-DHBA could not be detected by HPLC,although the sampling time lasted for 48 h.On the other hand,when the film was placed in the plasma area and the sampling time being too long(>4 h),the concentration of 2,5-DHBA was also below detection limit,and it could not be detected by HPLC.However,when the film was placed in the plasma reaction field with the sampling time being 3 h,the concentration of OH radical was calculated to be 10.54×1012 cm-3.In addition,concentration of OH radical was investigated under different humidity,such as 0.2%,0.4%,0.6%,0.8%,and 1.0%.The results showed that the amount of OH radical stayed at order of magnitude of 1012 cm-3 and increased with the increase of humidity.
文摘The adsorption performance of toluene on ultra-stable Y zeolite (USY) was studied via dynamic adsorption. The eff ects of bed temperature, initial concentration, and feed fl ow rate on adsorption were investigated. The Yoon-Nelson model was used to fi t the toluene breakthrough curves. The length of mass transfer zone was calculated based on breakthrough curves. The Langmuir-Freundlich model fi t the adsorption isotherms of toluene on USY, which indicated that the surface of USY was heterogeneous. The adsorption isosteric heat calculated from adsorption isotherms ranged from 54.3 to 69.8 kJ/mol, indicating physical adsorption. The combined technique of temperature swing adsorption with vacuum swing adsorption (TVSA) exhibited excellent desorption performance, which was attributed to the low desorption activation energy. Under optimized TVSA conditions, the desorption rate of toluene reached 90.6% within 10 min. The long-term cyclic utilization results indicated that the adsorption capacity of USY was stable.
基金supported by the National Natural Science Foundation of China(51474146,21806102)Graduate Program Funding of Shanghai Polytechnic University(A01GY18F022-d04,EGD18YJ0004)Gaoyuan Discipline of Shanghai–Environmental Science and Engineering(Resource Recycling Science and Engineering)
文摘As green solvents,ionic liquids(ILs)are quite suitable for the absorption of volatile organic compounds(VOCs)such as benzene and its homologues.However,solvent selection is the key to the VOC absorption process.In the present study,a rapid solvent screening tool,Conductor-like Screening Model for Real Solvents(COSMO-RS),was used to predict the solubility of toluene in 816 ILs.The effects of four structure characters,namely,the type and alkyl chain length of the cations and anions on the solubility of toluene were discussed.The following conclusions were drawn from the results:(1)ILs with pyrrolidinium-based cations showed better solubility than pyridinium-and imidazoliumbased ones.(2)The solubility of toluene in PF6-based ILs increased with the increasing alkyl chain length,while its solubility in Ac-based ILs exhibited the opposite trend.(3)Toluene showed greater solubility in Cl-based ILs than those based on other anions.(4)The solubility of toluene increased with the anion alkyl chain length.Ac-based ILs were chosen as the most promising potential solvents,and further studied to determine the relationship between various interaction energy parameters and toluene solubility.The results showed that the misfit energy played a dominant role during the absorption process.Furthermore,several ILs were selected for experimental verification of the predicted solubility behavior using liquid and gaseous toluene.The results demonstrated that COSMO-RS could be used to semi-quantitatively and qualitatively predict the solubility of toluene,and this model had promising prospects in screening ILs for VOCs absorption.In summary,this study provided a fundamental basis and practical data for the control and treatment of VOCs.
文摘An experimental system for measuring the VLE of polymer solutions based on the staticvapor-pressure method has been established,VLE data for mixtures of toluene and polystyrene withdifferent molecular weight covering a wide range from 2.98×10~3 to 3.84×10~6 were obtained at 35℃.The reduced pressure p/p°versus weight fraction W plot is found to be independent on the molecularweight of the polymer within the experimental error.Calculated activity coefficients are also independenton the molecular weight.However,for the Flory-Huggins interaction parameter x,not only a strongconcentration dependence is observed,but also the molecular weight of the polymer exerts definiteinfluence.Generally,the parameter x slightly increases as the molecular weight of the polymer decreasesespecially when the molecular weight is low.The dependence of the parameter x on the molecularweight can be neglected when the molecular weight of polymer is greater than 1.00×10~4.
基金This study was supported by the CNPC Research Institute of Safety and Environmental Protection Technology(No.PPCIP2017005).
文摘The hierarchical nanostructured N-doped TiO2 immobilized activated carbon fiber(N-TiO2/ACF)porous composites are fabricated to removal dynamic toluene gas.The results show that nitrogen ions doping and ACF modification can decrease the band gap of TiO2,leading to red shift toward visible light region.Interestingly,N-TiO2/ACF exhibits strongly synergistic effect owing to high surface area,good crystallinity,enhanced bandgap structure and light harvesting.The toluene removal rate of N-TiO2/ACF composites is 2.29 times higher than that of TiO2.The N-TiO2/ACF for toluene degradation followed the Langmuir-Hinshelwood kinetic model,and the rate constant is enhanced 8 times compared with TiO2.The possible photodegradation pathway and mechanisms are proposed.
基金supported by National Natural Science Foundation of China (No. 21808024)Fundamental Research Funds for the Central Universities (DMU 3132018175)
文摘An efficient toluene removal in air using a plasma photocatalytic system(PPS)not only needs favorable surface reactions over photocatalysts under the action of plasma,but also requires the photocatalysts to efficiently absorb light emitted from the discharge for driving the photocatalytic reactions.We report here that the PPS constructed by integrating a black titania(B-TiO2)photocatalyst with a dielectric barrier discharge(DBD)can effectively remove toluene with above 70%CO2 selectivity and remarkably reduced the concentration of secondary pollutants of ozone and nitrogen oxides at a specific energy input of 1500 J-I-1,while exhibiting good stability.Photocatalyst characterizations suggest that the B-TiO2 provides a high concentration of oxygen vacancies for the surface oxidation of toluene in DBD,and efficiently absorbs ultraviolet-visible light emitted from the discharge to induce plasma photocatalytic oxidation of toluene.The presence of B-TiO2 in the plasma region also results in a high discharge efficiency,facilitating the generation of large numbers of reactive species and thus the oxidation of toluene towards CO2.The greatly enhanced performance of the PPS integrated with B-TiO2 in toluene removal offers a promising approach to efficiently remove refractory volatile organic compounds from air at low temperatures.
基金supported by the National Key Research and Development Program of China(2018YFB1501403)the National Natural Science Foundation of China(51776134 and 51406129)the Technology Foundation for Selected Overseas Chinese Scholars,Ministry of Human Resources and Social Security of China(2016)。
文摘Biochar supported nickel(Ni/BC)has been widely studied as a cheap and easy-to-prepare catalyst with potential applications in tar reforming during the gasification of low-rank fuels,such as brown coal and biomass.However,the role and behaviors of inherent K species,especially their interactions with Ni particles and the biochar support,are not well understood yet.In this work,three Ni/BC catalysts with varying K amount were prepared from raw,water-washed,and acid-washed biomass.They were used in steam reforming of toluene as a tar model compound to elucidate the effects of inherent K on the catalytic activity and stability.Detailed characterization indicated that K enhanced water adsorption due to its hydroscopicity and lowered the condensation and graphitization degrees of biochar,but the alteration to the electronic state of Ni was not observed.These effects together led to a temperature-dependent role of K.That is,at relatively low temperatures of 450 and 500℃,toluene conversion was increased in the presence of K,due to the increased concentration of adsorbed water around Ni particles.By contrast,at relatively higher temperatures of 550 and 600℃,although initial high activity was achieved,Ni/BC with K deactivated rapidly because of the accelerated consumption of the biochar support.
基金supported by research grants from the National Natural Science Foundation of China[No.81474929]。
文摘Objective This study was designed to conduct a retrospective and systematic occupational health risk assessment(OHRA)of enterprises that used benzene,toluene,and xylene(BTX)in Shanghai,China.Methods All data for the study were obtained from 1,705 occupational health examination and evaluation reports from 2013 to 2017,and a semiquantitative model following Chinese OHRA guidelines(GBZ/T 298-2017)was applied for the assessment.Results The selected enterprises using BTX were mainly involved in manufacturing of products.Using the exposure level method,health risk levels associated with exposure to BTX were classified as medium,negligible,or low.However,the risk levels associated with benzene and toluene were significantly different according to job types,with gluers and inkers exhibiting greater health risks.For the same job type,the health risk levels assessed using the comprehensive index method were higher than those using the exposure level method.Conclusion Our OHRA reveals that workers who are exposed to BTX still face excessive health risk.Additionally,the risk level varied depending on job categories and exposure to specific chemicals.Therefore,additional control measures recommended by OHRA guidelines are essential to reduce worker exposure levels.
基金supported by the Major State Basic Research Program of China (No.2003CB615701 )National Natural Science Foundation of China (Nos.20736003,20676067)+2 种基金National High Technology Research and Development Program of China (No.2007AA06Z317)Foundation of Ministry of Education of China (No.20070003130)SINOPEC Foundation (No.X505002).
文摘Five kinds of polyimides were synthesized using five dianhydrides (including 2,2-bis[4-(3,4-dicarboxyphenoxy)- phenyl] propane dianhydride (BPADA),3,3',4,4'-diphenylsulfone-tetracarboxylic dianhydride (DSDA),4,4'- (hexafluoroisopropylidene)-diphthalic anhydride (6FDA),1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA), and 4,4'-oxydiphthlic dianhydride (ODPA)) and 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane (BDAF) via the two- step method that included polyaddition to form the polyamic aci...
基金financialy supported by the National Natural Science Foundation of China (No.21936005,52070114,21876093)the Postdoctoral Science Program of China (No.2019M660061)
文摘Regenerated activated carbon(RAC)samples were prepared by carbon activation using waste activated carbon from solid waste resources as the carbon source precursor coupled with adding alkaline additives,and then were further modified by potassium ferrate to finally prepare high-performance carbon for VOCs adsorption.At the same time,the samples before and after modification were systematically studied through characterization techniques such as SEM,Raman spectrometry,FT-IR,XPS,and dynamic/static adsorption.The results showed that the specific surface area and pore volume of the RAC after modification by the strong oxidant potassium ferrate increased by 1.4 times;the degree of defects was enhanced and the content of oxygen-containing functional groups on the surface increased significantly.Among them,the sample modified with potassium ferrate for 24 h had the best dynamic toluene adsorption performance(375.5 mg/g),and the dynamic adsorption capacity was twice that of the original sample(192.8 mg/g).The static adsorption test found that the maximum adsorption capacity of RAC-6%K_(2)FeO_(4)+H_(2)SO_(4)-24h was 796 mg/g,which indicated that the potassium ferrate modification treatment could significantly increase the VOCs adsorption performance of RAC.In addition,through consecutive toluene adsorption-desorption cycle tests,it was found that the RAC-6%K_(2)FeO_(4)+H_(2)SO_(4)-24h sample still retained 91%of adsorption activity after the fifth regeneration cycle.This indicates that RAC-6%K_(2)FeO_(4)+H_(2)SO_(4)-24h has good cycle stability and great application value for the efficient purification of industrial waste VOCs gas.
基金This research is financially supported by the Open Project Program of State Key Laboratory of Petroleum Pollution Control(No.PPCIP2017005).
文摘MFI molecular sieve with high specific surface area,adjustable pore size and low production cost have been recognized as an effective adsorbent for VOCs removal.In this paper,NaOH solution was used to etch ZSM-5 to increase specific surface area and micro-mesoporous content.Graphene oxide(GO)was loaded on ZSM-5 by ultrasonic-assisted heating immersion method,and largeπ-bond structure and oxygen-containing functional groups were added to ZSM-5 for improving the composite adsorption performance.In addition,the properties of OH-ZSM-5 and ZSM-5@GO composites for toluene adsorption under different factors were also studied.It was positively correlated with initial concentration and adsorbent mass,but was negatively correlated with temperature.Meanwhile,the results showed that the saturated adsorption capacity of OH-ZSM-5(107.3 mg/g)was 1.34 times higher than that of ZG-15%(80.2 mg/g).The pseudo-first-order and pseudo-second-order kinetic model can well describe the adsorption behavior of toluene on the OH-ZSM-5 and ZG-15%,respectively.The adsorption mechanism of OH-ZSM-5 was mainly pore-filled adsorption.However,the adsorption mechanisms of ZSM-5@GO composite were pore-filled adsorption,π-πinteraction,and H-bond interaction.This study will help to design a new strategy for enhancing the performance of traditional adsorbent ZSM-5 in VOCs removal.
