Hierarchical beta zeolites with SiO2/Al2O3 molar ratios of 16 to 25 were obtained by alkaline treatment in NaOH solution. The effects of treatment temperature on crystallinity, textural properties and chemical composi...Hierarchical beta zeolites with SiO2/Al2O3 molar ratios of 16 to 25 were obtained by alkaline treatment in NaOH solution. The effects of treatment temperature on crystallinity, textural properties and chemical composites were studied by XRD, N2 sorption, FT-IR and XRF techniques. The desulfurization performance of parent and alkaline-treated beta zeolites was investigated by static absorption in four model fuels, containing four sulfur compounds of different molecular sizes like thiophene (TP), 3-methylthiophene (3-MT), benzothiophene (BT) and dibenzothiophene (DBT), respectively. The crystallinity was observed to be successfully maintained when the treatment temperature was below 50 ℃. Mesoporosity of beta zeolite was evidently developed with alkaline treatment. The formation of mesopore remarkably improved the desulfurization performance for TP, 3-MT, BT and DBT, especially for DBT with larger molecular diameter. Though the addition of toluene in the model fuels resulted in a significant drop of the desulfurization performance of mesoporous beta zeolite, the introduction of cerium ions to some extent mitigated the effect of toluene, which means that both the adsorbent’s porous structure and the adsorption mode are responsible for the desulfurization performance. The adsorbent of cerium ion-exchanged mesoporous beta showed about 80% recovery of desulfurization after the first regeneration.展开更多
Zeolites NaY and Ce(IV)Y were employed as adsorbents to remove organic sulfur compounds from model gasoline (MG) solutions with and without toluene in static adsorption experiments at room temperature (RT) and a...Zeolites NaY and Ce(IV)Y were employed as adsorbents to remove organic sulfur compounds from model gasoline (MG) solutions with and without toluene in static adsorption experiments at room temperature (RT) and atmospheric pressure. The adsorbents were characterized by XRD, XRF and pyridine infrared spectrum (IR). The adsorption experiments show that the desulfurization performance of Ce(IV)Y is much better than that of NaY. The sulfur removal over both NaY and Ce(IV)Y decreases with the increase of toluene concentration in MG, however, the decline tendency on Ce(IV)Y is smooth, and it is steep on NaY. FT-IR spectra of thiophene adsorption indicate that thiophene molecules are mainly adsorbed on NaY via π electron interaction, but on Ce(IV)Y, in addition to the π electron interaction, both Ce^4+-S direct interaction and protonation of thiophene also play important roles. Toluene molecules are adsorbed on NaY also via π electron interaction. Although the amount of Bronsted acid sites is increased due to the introduction of Ce^4+ ions into NaY zeolite, it is not found to influence the adsorption mode of toluene over Ce(IV)Y. Compared with NaY zeolite, the improved desulfurization performance over Ce(IV)Y for removing organic sulfur compounds from MG solution, especially those containing large amount of aromatics, may be ascribed to the direct Ce(IV)-S interaction, which is much resistant to the influence resulted from toluene adsorption.展开更多
The adsorption removal of indole and quinoline in octane with and without toluene over zeolites NaY and Yttrium Ion-exchanged Y(YY)using batch adsorption experiments was studied at 25℃and 0.1 MPa.YY was prepared by t...The adsorption removal of indole and quinoline in octane with and without toluene over zeolites NaY and Yttrium Ion-exchanged Y(YY)using batch adsorption experiments was studied at 25℃and 0.1 MPa.YY was prepared by treating NaY with Y(NO3)3 solution twice via liquid ion-exchange method.NaY and YY were both characterized by XRD,SEM,N2 adsorption,XRF,NH3-TPD,and pyridine-FTIR techniques.Adsorption isotherms of indole,quinoline and toluene in octane were conducted at 25.0℃to explain the influence of toluene on nitrogen removal over NaY and YY.The partial destruct of the crystalline structure of NaY was observed after the introduction of yttrium ion,which led to an evident decline in BET surface area and pore volume of YY.Strong Br?nsted acidity and medium Lewis acidity were introduced by yttrium ion-exchange.Though the specific surface area and pore volume of YY were much lower than those of NaY,YY exhibited equivalent adsorption capacities for indole and quinoline as NaY in model fuels without toluene.In the presence of 20 vol%toluene,however,YY exhibited much higher adsorption capacities for indole and quinoline than NaY,especially in the case of quinoline.The improved toluene-tolerant of YY was ascribed to the strong acid–base interaction between YY and quinoline and the decreased adsorption strength between YY and toluene.展开更多
This work presented the synthesis of Ni-based metal-organic framework material with a paddle-wheel structure Ni3(BTC)2 (Ni-BTC) and its application in thiophene (TP) adsorption from gasoline distillate by batch method...This work presented the synthesis of Ni-based metal-organic framework material with a paddle-wheel structure Ni3(BTC)2 (Ni-BTC) and its application in thiophene (TP) adsorption from gasoline distillate by batch method. Adsorption isotherms of TP, cyclohexene, and toluene in cyclohexane onto Ni-BTC were conducted at 298-308 K to interpret the different effect of cyclohexene and toluene on TP adsorption. The results showed that, compared w让h cyclohexene, toluene addition in model gasoline led to a more evident decline in sulfur capacity of Ni-BTC, which is opposite to isostructural HKUST-1. The adsorption isotherms of TP, cyclohexene and toluene fit Langmuir model, S-type model and Temkin model well, respectively, indicating that the adsorption mechanisms of TP and the two competitors are different from one another The adsorption capacities on Ni-BTC followed the order of cyclohexene < toluene < TP at the same equilibrium concentrations, implying the order of the adsorption affinities, which is in good agreement with the different extent of influence by the two competitors. The enthalpy of TP adsorption on Ni-BTC was estimated to be -80.01 kj/mol, almost twice that on HKUST-1. The poor reusability of Ni-BTC in batch experiment, which is owing to its sensitivity to the air, can be prevented from regenerating used Ni-BTC in fixed-bed reactor by N2 flow. The difference between Ni-BTC and HKUST-1 in maximum adsorption capacity (q0),△H of TP adsorption, and stability demonstrates that the central metal in isostructural MOFs plays a key role in adjusting the desulfurization performance, which may open up a potential avenue for the development of MOF-based adsorbents with superior desulfurization performance.展开更多
The key to improve the performance of heteroatom catalysts is to ensure the orderliness of catalysts and the good dispersion of heteroatoms.The alkalinity plays the indispensable role in synthetic process of V-MCM-41 ...The key to improve the performance of heteroatom catalysts is to ensure the orderliness of catalysts and the good dispersion of heteroatoms.The alkalinity plays the indispensable role in synthetic process of V-MCM-41 catalyst.The excessive alkalinity of synthetic system will make the MCM-41 difficult to crystallize,even to dissolve.It is easy to accumulate for heteroatomic species in the system of low alkalinity.Herein,the highly ordered VMCM-41 with high vanadic content in framework is synthesized in the condition of excessive NH3·H2 O in this paper.A series of characterization results prove the good dispersion of vanadium species,and most of vanadium gets into the framework of MCM-41 with the states of tetravalence and pentavalence.Furthermore,the modified MCM-41 by other transition metals is successful synthesized by the method of V-MCM-41 in this paper.The VMCM-41 shows well catalytic activity for the selective oxidation of benzyl alcohol,which up to 74.83%for the conversion of benzyl alcohol and 96.20%for selectivity of benzaldehyde when initial V/Si=0.10.The paper provides the possibility for industrial application of V-MCM-41 in the oxidation of benzyl alcohol for benzaldehyde.Besides,the work provides a significant idea for the synthesis of modified MCM-41 by well-dispersed transition metals.展开更多
As an essential part of the grassland ecological system,study on the carbon storage has great significances to the carbon reduction in grassland ecological system.The carbon storage in biomass,carbon storage in soil a...As an essential part of the grassland ecological system,study on the carbon storage has great significances to the carbon reduction in grassland ecological system.The carbon storage in biomass,carbon storage in soil and soil respiration are summarized in this paper to provide scientific reference for the evaluation of carbon storage in artificial grassland.展开更多
The liquid phase selective hydrogenation of cinnamaldehyde has been investigated over the catalysts Co-C-T(T=400-700℃),which were derived from the carbonization of the MOF precursor Co-BTC at different temperatures i...The liquid phase selective hydrogenation of cinnamaldehyde has been investigated over the catalysts Co-C-T(T=400-700℃),which were derived from the carbonization of the MOF precursor Co-BTC at different temperatures in inert atmosphere.Co-C-500 exhibited a higher conversion(85.3%)than those carbonized at other temperatures,with 51.5%selectivity to cinnamyl alcohol,under a mild condition(90℃,4 h,2 MPa H_(2),solvent:9 ml ethanol and 1 ml water).The high catalytic activity of Co-C-500 can be ascribed to the large specific surface area of the catalyst,the uniformly dispersed metallic cobalt nanoparticles,and the more defect sites on the carbon support.Moreover,Co-C-500 showed excellent reusability in 5 successive cycles,mainly related to the uniformly dispersed cobalt nanoparticles embedded in carbon support.展开更多
A series of Ni/HZSM-5 and Ni/HIM-5 bi-functional catalysts were synthesized and applied to the aqueous-phase hydrodeoxygenation(HDO)of phenol.The Ni dispersibility and particle sizes were shown to be directly related ...A series of Ni/HZSM-5 and Ni/HIM-5 bi-functional catalysts were synthesized and applied to the aqueous-phase hydrodeoxygenation(HDO)of phenol.The Ni dispersibility and particle sizes were shown to be directly related to the porosity and crystal sizes of the parent zeolites,which further influenced the catalytic performances.The large pores and small crystal sizes of the parent zeolites were beneficial for dispersing Ni and forming small Ni particles,and the corresponding Ni/zeolite catalyst exhibited a higher phenol conversion and selectivity towards hydrocarbons.Importantly,the Ni/HIM-5 bi-functional catalyst exhibited a high activity(98.3%)and high selectivity for hydrocarbons(98.8%)when heated at 220°C for 1 h and is thus a new potential catalyst for the HDO of phenolics to form hydrocarbons in the aqueous phase.展开更多
基金supported by the Fundamental Research Funds for the Central Universities(No.DUT10LK25)the Natural Science Foundation of China(No.21106014)
文摘Hierarchical beta zeolites with SiO2/Al2O3 molar ratios of 16 to 25 were obtained by alkaline treatment in NaOH solution. The effects of treatment temperature on crystallinity, textural properties and chemical composites were studied by XRD, N2 sorption, FT-IR and XRF techniques. The desulfurization performance of parent and alkaline-treated beta zeolites was investigated by static absorption in four model fuels, containing four sulfur compounds of different molecular sizes like thiophene (TP), 3-methylthiophene (3-MT), benzothiophene (BT) and dibenzothiophene (DBT), respectively. The crystallinity was observed to be successfully maintained when the treatment temperature was below 50 ℃. Mesoporosity of beta zeolite was evidently developed with alkaline treatment. The formation of mesopore remarkably improved the desulfurization performance for TP, 3-MT, BT and DBT, especially for DBT with larger molecular diameter. Though the addition of toluene in the model fuels resulted in a significant drop of the desulfurization performance of mesoporous beta zeolite, the introduction of cerium ions to some extent mitigated the effect of toluene, which means that both the adsorbent’s porous structure and the adsorption mode are responsible for the desulfurization performance. The adsorbent of cerium ion-exchanged mesoporous beta showed about 80% recovery of desulfurization after the first regeneration.
基金supported by the Fundamental Research Funds for the Key Universities (Grant No. DUT10LK25)the National Natural Science Foundation of China (Grant No. 21106014)
文摘Zeolites NaY and Ce(IV)Y were employed as adsorbents to remove organic sulfur compounds from model gasoline (MG) solutions with and without toluene in static adsorption experiments at room temperature (RT) and atmospheric pressure. The adsorbents were characterized by XRD, XRF and pyridine infrared spectrum (IR). The adsorption experiments show that the desulfurization performance of Ce(IV)Y is much better than that of NaY. The sulfur removal over both NaY and Ce(IV)Y decreases with the increase of toluene concentration in MG, however, the decline tendency on Ce(IV)Y is smooth, and it is steep on NaY. FT-IR spectra of thiophene adsorption indicate that thiophene molecules are mainly adsorbed on NaY via π electron interaction, but on Ce(IV)Y, in addition to the π electron interaction, both Ce^4+-S direct interaction and protonation of thiophene also play important roles. Toluene molecules are adsorbed on NaY also via π electron interaction. Although the amount of Bronsted acid sites is increased due to the introduction of Ce^4+ ions into NaY zeolite, it is not found to influence the adsorption mode of toluene over Ce(IV)Y. Compared with NaY zeolite, the improved desulfurization performance over Ce(IV)Y for removing organic sulfur compounds from MG solution, especially those containing large amount of aromatics, may be ascribed to the direct Ce(IV)-S interaction, which is much resistant to the influence resulted from toluene adsorption.
基金the financial support from Natural Science Foundation of China-Liaoning United Funds(U1508205)Fundamental Research Funds for the Central Universities(DUT15ZD113)the Key Laboratory of Applied Surface and Colloid Chemistry(Shanxi Normal University).
文摘The adsorption removal of indole and quinoline in octane with and without toluene over zeolites NaY and Yttrium Ion-exchanged Y(YY)using batch adsorption experiments was studied at 25℃and 0.1 MPa.YY was prepared by treating NaY with Y(NO3)3 solution twice via liquid ion-exchange method.NaY and YY were both characterized by XRD,SEM,N2 adsorption,XRF,NH3-TPD,and pyridine-FTIR techniques.Adsorption isotherms of indole,quinoline and toluene in octane were conducted at 25.0℃to explain the influence of toluene on nitrogen removal over NaY and YY.The partial destruct of the crystalline structure of NaY was observed after the introduction of yttrium ion,which led to an evident decline in BET surface area and pore volume of YY.Strong Br?nsted acidity and medium Lewis acidity were introduced by yttrium ion-exchange.Though the specific surface area and pore volume of YY were much lower than those of NaY,YY exhibited equivalent adsorption capacities for indole and quinoline as NaY in model fuels without toluene.In the presence of 20 vol%toluene,however,YY exhibited much higher adsorption capacities for indole and quinoline than NaY,especially in the case of quinoline.The improved toluene-tolerant of YY was ascribed to the strong acid–base interaction between YY and quinoline and the decreased adsorption strength between YY and toluene.
基金financial supports from the Natural Science Foundation of China-Liaoning United Funds(grant no.U1508205)the Fundamental Research Funds for the Central Universities(grant no.DUT15ZD113)the Key Laboratory of Applied Surface and Colloid Chemistry(Shanxi Normal University)
文摘This work presented the synthesis of Ni-based metal-organic framework material with a paddle-wheel structure Ni3(BTC)2 (Ni-BTC) and its application in thiophene (TP) adsorption from gasoline distillate by batch method. Adsorption isotherms of TP, cyclohexene, and toluene in cyclohexane onto Ni-BTC were conducted at 298-308 K to interpret the different effect of cyclohexene and toluene on TP adsorption. The results showed that, compared w让h cyclohexene, toluene addition in model gasoline led to a more evident decline in sulfur capacity of Ni-BTC, which is opposite to isostructural HKUST-1. The adsorption isotherms of TP, cyclohexene and toluene fit Langmuir model, S-type model and Temkin model well, respectively, indicating that the adsorption mechanisms of TP and the two competitors are different from one another The adsorption capacities on Ni-BTC followed the order of cyclohexene < toluene < TP at the same equilibrium concentrations, implying the order of the adsorption affinities, which is in good agreement with the different extent of influence by the two competitors. The enthalpy of TP adsorption on Ni-BTC was estimated to be -80.01 kj/mol, almost twice that on HKUST-1. The poor reusability of Ni-BTC in batch experiment, which is owing to its sensitivity to the air, can be prevented from regenerating used Ni-BTC in fixed-bed reactor by N2 flow. The difference between Ni-BTC and HKUST-1 in maximum adsorption capacity (q0),△H of TP adsorption, and stability demonstrates that the central metal in isostructural MOFs plays a key role in adjusting the desulfurization performance, which may open up a potential avenue for the development of MOF-based adsorbents with superior desulfurization performance.
基金partially supported by the National Natural Science Foundation of China(Grant Nos.21601026,21771030)Fundamental Research Funds for the Central Universities(DUT16RC(4)10,DUT18RC(6)008)。
文摘The key to improve the performance of heteroatom catalysts is to ensure the orderliness of catalysts and the good dispersion of heteroatoms.The alkalinity plays the indispensable role in synthetic process of V-MCM-41 catalyst.The excessive alkalinity of synthetic system will make the MCM-41 difficult to crystallize,even to dissolve.It is easy to accumulate for heteroatomic species in the system of low alkalinity.Herein,the highly ordered VMCM-41 with high vanadic content in framework is synthesized in the condition of excessive NH3·H2 O in this paper.A series of characterization results prove the good dispersion of vanadium species,and most of vanadium gets into the framework of MCM-41 with the states of tetravalence and pentavalence.Furthermore,the modified MCM-41 by other transition metals is successful synthesized by the method of V-MCM-41 in this paper.The VMCM-41 shows well catalytic activity for the selective oxidation of benzyl alcohol,which up to 74.83%for the conversion of benzyl alcohol and 96.20%for selectivity of benzaldehyde when initial V/Si=0.10.The paper provides the possibility for industrial application of V-MCM-41 in the oxidation of benzyl alcohol for benzaldehyde.Besides,the work provides a significant idea for the synthesis of modified MCM-41 by well-dispersed transition metals.
基金Supported by National Basic Research Program of China(2010CB951502)Scientific Research Program of Public Welfare for Agriculture(201203006)+1 种基金The Planning Subject of 12th Five-Year Plan in National Science and Technology for the Rural Development in China(2012BAD13B07)The Central Public Research Institutes for Basic Research Funds Projects(BRF1610322012009)
文摘As an essential part of the grassland ecological system,study on the carbon storage has great significances to the carbon reduction in grassland ecological system.The carbon storage in biomass,carbon storage in soil and soil respiration are summarized in this paper to provide scientific reference for the evaluation of carbon storage in artificial grassland.
基金financial support from the National Natural Science Foundation of China(22272016).
文摘The liquid phase selective hydrogenation of cinnamaldehyde has been investigated over the catalysts Co-C-T(T=400-700℃),which were derived from the carbonization of the MOF precursor Co-BTC at different temperatures in inert atmosphere.Co-C-500 exhibited a higher conversion(85.3%)than those carbonized at other temperatures,with 51.5%selectivity to cinnamyl alcohol,under a mild condition(90℃,4 h,2 MPa H_(2),solvent:9 ml ethanol and 1 ml water).The high catalytic activity of Co-C-500 can be ascribed to the large specific surface area of the catalyst,the uniformly dispersed metallic cobalt nanoparticles,and the more defect sites on the carbon support.Moreover,Co-C-500 showed excellent reusability in 5 successive cycles,mainly related to the uniformly dispersed cobalt nanoparticles embedded in carbon support.
基金This work was supported by the National Natural Science Foundation of China(Grant No.21908225)the National Key Research and Development Program of China(Grant No.2016YFB0600505)Youth Innovation Promotion Association,CAS(2014037).
文摘A series of Ni/HZSM-5 and Ni/HIM-5 bi-functional catalysts were synthesized and applied to the aqueous-phase hydrodeoxygenation(HDO)of phenol.The Ni dispersibility and particle sizes were shown to be directly related to the porosity and crystal sizes of the parent zeolites,which further influenced the catalytic performances.The large pores and small crystal sizes of the parent zeolites were beneficial for dispersing Ni and forming small Ni particles,and the corresponding Ni/zeolite catalyst exhibited a higher phenol conversion and selectivity towards hydrocarbons.Importantly,the Ni/HIM-5 bi-functional catalyst exhibited a high activity(98.3%)and high selectivity for hydrocarbons(98.8%)when heated at 220°C for 1 h and is thus a new potential catalyst for the HDO of phenolics to form hydrocarbons in the aqueous phase.