In this work, supramolecular fixation of three amines, including aniline, ethylenediamine, and diethylamine, using cobalt tetraphenylporphyrin （CoTPP） for SO2 removal was studied using UV-Vis and fluorescence measur...In this work, supramolecular fixation of three amines, including aniline, ethylenediamine, and diethylamine, using cobalt tetraphenylporphyrin （CoTPP） for SO2 removal was studied using UV-Vis and fluorescence measurements. The UV-Vis spectra showed that increasing amines concentrations resulted in bathochromic shift for CoTPP Soret absorption band （B band）. Once SO2 was introduced, it competed with CoTPP for aniline, ethylenediamine, and diethylamine, which eventually led to the release of CoTPP and the change of solution colour/absorption band. After that, the CoTPP was regenerated and got back to the first state. The fluorescence spectra offered that CoTPP interacted with aniline, ethylenediamine, and diethylamine to form 1：1 molecular adducts. The interactions of CoTPP with aniline, ethylenediamine, and diethylamine were entropy-driven. The interaction of CoTPP with aniline and diethylamine was endothermic, and that with ethylenediamine was exothermic. Ethylenediamine presented a stronger binding constant value for CoTPP, so it was considered as a potential agent for SO2 removal.展开更多
To study the mechanism of SO2 and Hg removal from flue gas, an experimental packed bed reactor was designed to simulate the dry FGD, where a mixture of lime and fly ash in ratio 1：3 w/w was used as the S02 and Hg sor...To study the mechanism of SO2 and Hg removal from flue gas, an experimental packed bed reactor was designed to simulate the dry FGD, where a mixture of lime and fly ash in ratio 1：3 w/w was used as the S02 and Hg sorbent, and steam at temperature of 100 ℃ was applied for activation of the sorbent, while the activation time set to 20 rain. The experimental factors including the SO2/Hg sorbent characteristics, 50% breakthrough time for SO2/Hg removal, sorbent packed bed depth and reaction temperature were investigated. The experimental results show that after steam activation, the BET specific surface area and specific pore volume increased from 37.8 to 45.5 m^2/g and from 0.42 to 0.51 cm^3/g, respectively. With activation of the sorbent by steam, the 50% breakthrough times of SO2 and Hg removal increased from 34 to 42 rain and from 23 to 45 rain, respectively. When the packed bed depth was increased from 5 to 25 ram. the 50% breakthrough times for Hg and S02 removal increased from 12 to 52 rain and from 6 to 47 rain, respectively. With the increase of the reaction temperature, the 50% breakthrough of SO2/Hg removal decreased accordingly. Steam activation can efficiently improve SO2/Hg removal simultaneously.展开更多
As special cylindrical briquettes of coal for long distance pipeline transportation and directly cleaned combustion the cleaned coal logs should possess two characteristics of transportation in pipeline and cleaned co...As special cylindrical briquettes of coal for long distance pipeline transportation and directly cleaned combustion the cleaned coal logs should possess two characteristics of transportation in pipeline and cleaned combustion. In order to make cleaned coal logs a rational technology for manufacturing, cleaned coal logs was designed and compound sulfur fixing binders with high effects of binding and sulfur-fixing was selected and combined. In addition, by means of characteristic experiments of strength, wear, waterproof and sulfur-fixing five different cleaned coal logs made with different compound sulfur fixing binders in different compaction conditions was tested and measured. Experimental results indicated that the manufacturing technology of cleaned coal logs was reasonable and the combination of compound sulfur fixing binders was scientific. Cleaned coal logs made up with the fourth group of coal mixture had high strength, good waterproof property, efficient sulfur-fixing, good characteristic of transportation, and achieved the performance requirement for pipeline transportation and sulfur fixing.展开更多
Two series of molybdenum-containing MCM-41 catalysts were prepared for oxidative desulfurization ofdibenzothiophene （DBT） using t-butylhydroperoxide （TBHP） as the oxidant. The electronic properties, pore dimension...Two series of molybdenum-containing MCM-41 catalysts were prepared for oxidative desulfurization ofdibenzothiophene （DBT） using t-butylhydroperoxide （TBHP） as the oxidant. The electronic properties, pore dimension and hydrophilic properties of the catalysts were studied by XRD, BET, and 1R spectrometry. The Mo-Al2O3 catalyst and TiMCM-3% were also studied for comparison. The two series of MCM-41 zeolite with MoO3 in the framework or impregnated on the surface exhibited considerable activities at low MoO3 content and both were faxbetter than the Mo-Al2O3 catalyst, but had lower activities as compared to the TiMCM-3% catalyst. The catalysts with the highest activity were evaluated in a fixed-bed reactor. The concentration of DBT in model diesel upon oxidative desulfurization was successfully reduced from 5000 ppm to less than 150 ppm, but the catalysts were deactivated very fast. The probable reason was the high affinity of DBTO2 to the MCM-41 skeleton, especially to MoO3. The catalysts could restore most of its original activity by treating with alcohol.展开更多
Producing methanol from coke oven gas(COG) is one of the important applications of COG. Removal of sulfur from COG is a key step of this process. Conversion and reaction kinetics over a commercial Fe-Mo/Al2O3 catalyst...Producing methanol from coke oven gas(COG) is one of the important applications of COG. Removal of sulfur from COG is a key step of this process. Conversion and reaction kinetics over a commercial Fe-Mo/Al2O3 catalyst(T-202) were studied in a continuous flow fixed bed reactor under pressures of 1.6-2.8 MPa, space time of 1.32-3.55 s and temperatures of 240-360 °C. Though the COG contains about 0.6 mol/mol H2, hydrogenation of CO and CO2 is not significant on this catalyst. The conversions of unsaturated hydrocarbons depend on their molecular structures. Diolefins and alkynes can be completely hydrogenated even at relatively low temperature and pressure. Olefins, in contrast, can only be progressively hydrogenated with increasing temperature and pressure. The hydrodesulfurization(HDS) of CS2 on this catalyst is easy. Complete conversion of CS2 was observed in the whole range of the conditions used in this work. The original COS in the COG can also be easily converted to a low level. However, its complete HDS is difficult due to the relatively high concentration of CO in the COG and due to the limitation of thermodynamics. H2 S can react with unsaturated hydrocarbons to form ethyl mercaptan and thiophene, which are then progressively hydrodesulfurized with increasing temperature and pressure. Based on the experimental observations, reaction kinetic models for the conversion of ethylene and sulfur-containing compounds were proposed; the values of the parameters in the models were obtained by regression of the experimental data.展开更多
The photochemical reaction of sulfur dioxide （802） with tetraphenylporphyrin magnesium （MgTPP） has been investigated in dichloromethane （CH2C12） solution at room temperature with illumination by visible light. C...The photochemical reaction of sulfur dioxide （802） with tetraphenylporphyrin magnesium （MgTPP） has been investigated in dichloromethane （CH2C12） solution at room temperature with illumination by visible light. Conventional fluorescence, UV-vis, and MS spectral analyses showed that under these conditions, SO2 was initially photochemically fixed by MgTPP to form a 1：1 molecular adduct. On continued irradiation and maintaining the flow of SO2, MS and XRD results showed that MgTPP is re- markably effective in the photochemical reduction of SO2 to sulfide （S2 ）. The kinetics of the photochemical reaction of MgTPP with SO2 was studied in a SO2-saturated solution. Under irradiation, the reaction follows pseudo first order kinetics for MgTPP, having a half-life decreasing from 106 to 57 min as the illumination intensity is increased from 350 to 600 Lm. This investigation of the photochemical fixation and reduction of SO2 by MgTPP is of key interest in elucidating fundamental pho- tochemical reaction mechanisms associated with porphyrins in the presence of SO2; furthermore, the analysis of the photo- chemical reaction may offer new opportunities for the fixation and reduction of SO2 to less harmful species.展开更多
A novel strategy for efficient immobilization of electroactive Thionine(Th)on the gold(Au)electrode surface based on calcium carbonate-gold nanoparticles(CaCO3-AuNPs)inorganic hybrid composite was proposed and conduct...A novel strategy for efficient immobilization of electroactive Thionine(Th)on the gold(Au)electrode surface based on calcium carbonate-gold nanoparticles(CaCO3-AuNPs)inorganic hybrid composite was proposed and conducted by the strong electrostatic interaction between positively charged Th and negatively charged CaCO3-AuNPs composite.The hybrid composite was obtained by the adsorption of AuNPs onto the surface of CaCO3 microspheres through electrostatic interaction.Due to the microporous architecture,large surface area,and good biocompatibility of CaCO3-AuNPs composite,the amount and stability of the immobilized Th were highly strengthened.The application of the resulting Th modified electrode in the hydrogen peroxide(H2O2)sensor was also investigated.It exhibited rapid response to H2O2 within 3 s.The linear calibration ranged from 8.00×107to 1.06×10 -3mol/L with a detection limit of 2.00×10 -7mol/L.展开更多
文摘In this work, supramolecular fixation of three amines, including aniline, ethylenediamine, and diethylamine, using cobalt tetraphenylporphyrin （CoTPP） for SO2 removal was studied using UV-Vis and fluorescence measurements. The UV-Vis spectra showed that increasing amines concentrations resulted in bathochromic shift for CoTPP Soret absorption band （B band）. Once SO2 was introduced, it competed with CoTPP for aniline, ethylenediamine, and diethylamine, which eventually led to the release of CoTPP and the change of solution colour/absorption band. After that, the CoTPP was regenerated and got back to the first state. The fluorescence spectra offered that CoTPP interacted with aniline, ethylenediamine, and diethylamine to form 1：1 molecular adducts. The interactions of CoTPP with aniline, ethylenediamine, and diethylamine were entropy-driven. The interaction of CoTPP with aniline and diethylamine was endothermic, and that with ethylenediamine was exothermic. Ethylenediamine presented a stronger binding constant value for CoTPP, so it was considered as a potential agent for SO2 removal.
基金supported by the National High-Tech R&D Program of China (No. 2008AA06Z318)the Ministry of Environmental Protection of China (Nos. 201009048 and 200909025)
文摘To study the mechanism of SO2 and Hg removal from flue gas, an experimental packed bed reactor was designed to simulate the dry FGD, where a mixture of lime and fly ash in ratio 1：3 w/w was used as the S02 and Hg sorbent, and steam at temperature of 100 ℃ was applied for activation of the sorbent, while the activation time set to 20 rain. The experimental factors including the SO2/Hg sorbent characteristics, 50% breakthrough time for SO2/Hg removal, sorbent packed bed depth and reaction temperature were investigated. The experimental results show that after steam activation, the BET specific surface area and specific pore volume increased from 37.8 to 45.5 m^2/g and from 0.42 to 0.51 cm^3/g, respectively. With activation of the sorbent by steam, the 50% breakthrough times of SO2 and Hg removal increased from 34 to 42 rain and from 23 to 45 rain, respectively. When the packed bed depth was increased from 5 to 25 ram. the 50% breakthrough times for Hg and S02 removal increased from 12 to 52 rain and from 6 to 47 rain, respectively. With the increase of the reaction temperature, the 50% breakthrough of SO2/Hg removal decreased accordingly. Steam activation can efficiently improve SO2/Hg removal simultaneously.
基金Supported by the National Natural Science Foundation of China (50364003)
文摘As special cylindrical briquettes of coal for long distance pipeline transportation and directly cleaned combustion the cleaned coal logs should possess two characteristics of transportation in pipeline and cleaned combustion. In order to make cleaned coal logs a rational technology for manufacturing, cleaned coal logs was designed and compound sulfur fixing binders with high effects of binding and sulfur-fixing was selected and combined. In addition, by means of characteristic experiments of strength, wear, waterproof and sulfur-fixing five different cleaned coal logs made with different compound sulfur fixing binders in different compaction conditions was tested and measured. Experimental results indicated that the manufacturing technology of cleaned coal logs was reasonable and the combination of compound sulfur fixing binders was scientific. Cleaned coal logs made up with the fourth group of coal mixture had high strength, good waterproof property, efficient sulfur-fixing, good characteristic of transportation, and achieved the performance requirement for pipeline transportation and sulfur fixing.
文摘Two series of molybdenum-containing MCM-41 catalysts were prepared for oxidative desulfurization ofdibenzothiophene （DBT） using t-butylhydroperoxide （TBHP） as the oxidant. The electronic properties, pore dimension and hydrophilic properties of the catalysts were studied by XRD, BET, and 1R spectrometry. The Mo-Al2O3 catalyst and TiMCM-3% were also studied for comparison. The two series of MCM-41 zeolite with MoO3 in the framework or impregnated on the surface exhibited considerable activities at low MoO3 content and both were faxbetter than the Mo-Al2O3 catalyst, but had lower activities as compared to the TiMCM-3% catalyst. The catalysts with the highest activity were evaluated in a fixed-bed reactor. The concentration of DBT in model diesel upon oxidative desulfurization was successfully reduced from 5000 ppm to less than 150 ppm, but the catalysts were deactivated very fast. The probable reason was the high affinity of DBTO2 to the MCM-41 skeleton, especially to MoO3. The catalysts could restore most of its original activity by treating with alcohol.
文摘Producing methanol from coke oven gas(COG) is one of the important applications of COG. Removal of sulfur from COG is a key step of this process. Conversion and reaction kinetics over a commercial Fe-Mo/Al2O3 catalyst(T-202) were studied in a continuous flow fixed bed reactor under pressures of 1.6-2.8 MPa, space time of 1.32-3.55 s and temperatures of 240-360 °C. Though the COG contains about 0.6 mol/mol H2, hydrogenation of CO and CO2 is not significant on this catalyst. The conversions of unsaturated hydrocarbons depend on their molecular structures. Diolefins and alkynes can be completely hydrogenated even at relatively low temperature and pressure. Olefins, in contrast, can only be progressively hydrogenated with increasing temperature and pressure. The hydrodesulfurization(HDS) of CS2 on this catalyst is easy. Complete conversion of CS2 was observed in the whole range of the conditions used in this work. The original COS in the COG can also be easily converted to a low level. However, its complete HDS is difficult due to the relatively high concentration of CO in the COG and due to the limitation of thermodynamics. H2 S can react with unsaturated hydrocarbons to form ethyl mercaptan and thiophene, which are then progressively hydrodesulfurized with increasing temperature and pressure. Based on the experimental observations, reaction kinetic models for the conversion of ethylene and sulfur-containing compounds were proposed; the values of the parameters in the models were obtained by regression of the experimental data.
基金supported by the Foundation of Inner Mongolia Autonomous Region’s Educational Commission(NJZZ11068)the School Scientific Research Fund (ZD201004,Inner Mongolia University of Technology,China)Yongfeng Boyuan Industry Co.,Ltd. (Jiangxi Province,China)
文摘The photochemical reaction of sulfur dioxide （802） with tetraphenylporphyrin magnesium （MgTPP） has been investigated in dichloromethane （CH2C12） solution at room temperature with illumination by visible light. Conventional fluorescence, UV-vis, and MS spectral analyses showed that under these conditions, SO2 was initially photochemically fixed by MgTPP to form a 1：1 molecular adduct. On continued irradiation and maintaining the flow of SO2, MS and XRD results showed that MgTPP is re- markably effective in the photochemical reduction of SO2 to sulfide （S2 ）. The kinetics of the photochemical reaction of MgTPP with SO2 was studied in a SO2-saturated solution. Under irradiation, the reaction follows pseudo first order kinetics for MgTPP, having a half-life decreasing from 106 to 57 min as the illumination intensity is increased from 350 to 600 Lm. This investigation of the photochemical fixation and reduction of SO2 by MgTPP is of key interest in elucidating fundamental pho- tochemical reaction mechanisms associated with porphyrins in the presence of SO2; furthermore, the analysis of the photo- chemical reaction may offer new opportunities for the fixation and reduction of SO2 to less harmful species.
基金supported by the National Natural Science Foundation of China(20775039)
文摘A novel strategy for efficient immobilization of electroactive Thionine(Th)on the gold(Au)electrode surface based on calcium carbonate-gold nanoparticles(CaCO3-AuNPs)inorganic hybrid composite was proposed and conducted by the strong electrostatic interaction between positively charged Th and negatively charged CaCO3-AuNPs composite.The hybrid composite was obtained by the adsorption of AuNPs onto the surface of CaCO3 microspheres through electrostatic interaction.Due to the microporous architecture,large surface area,and good biocompatibility of CaCO3-AuNPs composite,the amount and stability of the immobilized Th were highly strengthened.The application of the resulting Th modified electrode in the hydrogen peroxide(H2O2)sensor was also investigated.It exhibited rapid response to H2O2 within 3 s.The linear calibration ranged from 8.00×107to 1.06×10 -3mol/L with a detection limit of 2.00×10 -7mol/L.
