For the goal of sulfur recovery, most methods are aimed at the tail gas with high-concentration H2S, but few effective methods are used for low-concentration H2S. In this work, Low-concentration H2S could be purified ...For the goal of sulfur recovery, most methods are aimed at the tail gas with high-concentration H2S, but few effective methods are used for low-concentration H2S. In this work, Low-concentration H2S could be purified well by liquid phase catalytic oxidation (LCO), and the sulfur resource could also be recovered. The absorption solution was prepared by FeCl3 and sulfosalicylic acid. Under the experimental conditions, the conversion of H2S to S could be maintained above 94% at 60 ℃. In order to enhance the economical efficiency of LCO method, the absorption solution was modified by doping Ce, and a series of experiments were designed to investigate its performance. The results showed that the conversion of H2S had no obvious improvement, but above 98% conversion could be gained at 60 ℃, and the H2S conversion rate was enhanced. The optimum addition quality of Ce(NO3)3 was 0.08 g to 50 ml Fe3+ solution.展开更多
In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were...In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were obtained from a combination of experimental observation and hypothetical models. The results clearly showed that both the oxidation rate of toluene and generation rate of the aromatic product were proportional to the concentration of the substrate, the partial pressure of oxygen and the surface area of the catalyst. The energy barrier of toluene oxidation to benzyl alcohol was the highest(≈ 81 kJ mol^(-1)), while that of benzyl alcohol oxidation to benzaldehyde was the lowest(≈ 57 kJ mol^(-1)). Moreover, the activation energy of further oxidation of benzaldehyde in an acetic acid solvent was only slightly lower(≈ 1.9 kJ mol^(-1)) than that of toluene oxidation. Significantly, the transformation of benzyl alcohol indeed contributed to the generation of benzaldehyde and this step conformed to a first-order parallel-consecutive model. Increased reaction temperature and residence time favored the transformation of benzyl alcohol to benzaldehyde. In addition, doping with molybdenum at Mn/Mo = 3/1 enhanced the catalytic performance of the heterogeneous catalyst and was attributed to the presence of a synergetic effect between different metal cations. Regarding the microscopic kinetics, the LH-OS-ND mechanism(Langmuir–Hinshelwood adsorption of reagents on the same type of active sites and non-dissociative adsorption of oxygen) was verified as responsible for the heterogeneous oxidation of toluene. Oxygen and benzaldehyde were weakly adsorbed(Δ H_(ads,Oxy) ≈^(-1)5 kJ mol^(-1), Δ H _(ads)0,Bald) ≈-30 kJ mol^(-1)), but showed strong mobility(Δ S_(ads,Oxy) ≈-22 J mol^(-1) K^(-1)), Δ S_(ads,Bald) ≈-39 J mol^(-1) K^(-1)). The fundamental intrinsic rates were deduced based on the LH-OS-ND mechanism and showed great consistency with the macroscopic results.展开更多
Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a φ48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH...Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a φ48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH3COO)2.4H2O as catalyst.The Co2+ concentration [Co2+] was determined by extraction spectrophotometry and hereby the Co3+ concentration [Co3+] was obtained by mass balance.The results showed that [Co3+] reached the maximum at about 25-30min.[Co3+] increased with increasing Co catalyst amount at total Co concentration<150 mg.L-1 of toluene.The conversion of toluene,yield and selectivity of benzoic acid increased with the increasing [Co3+/Co2+] max.A high [Co3+] and a high [Co3+]/[Co2+] ratio are beneficial to the reaction.展开更多
Catalytic activity and selectivity of prepared catalysts (Fe2O3/ and Fe2O3/AC(KOH)) were investigated for liquid phase aerobic oxidation of primary and secondary alcohols, in a batch reactor, using solvent free condit...Catalytic activity and selectivity of prepared catalysts (Fe2O3/ and Fe2O3/AC(KOH)) were investigated for liquid phase aerobic oxidation of primary and secondary alcohols, in a batch reactor, using solvent free condition and/or eco-friendly solvents. The catalysts were characterized by SEM, EDX, XRD, FTIR, TGA/DTA, and surface area and pore size analysis. Experimental data revealed that Fe2O3/AC(KOH) was an efficient catalyst for the oxidation (dehydrogenation) of alcohol while was found to show catalytic activity for both dehydration and dehydrogenation of alcohols. The catalysts were recycled by simple filtration, and used several times without any loss of catalytic activity.展开更多
Hydrogen sulfide in rural biogas was removed with liquid-phase catalytic oxidation.By using rare earth as catalyst,and sulfosalicylic acid as stabilizer,H2S purification efficiency could increase as high as 96%,and su...Hydrogen sulfide in rural biogas was removed with liquid-phase catalytic oxidation.By using rare earth as catalyst,and sulfosalicylic acid as stabilizer,H2S purification efficiency could increase as high as 96%,and sulfur capacity of the composite solution was about 3 g/L.The results show that purification efficiency was affected by catalyst addition,pH,experimental temperature,and sulfur capacity.The parameters effects on catalytic oxidation were studied,and the optimized conditions were that Fe3+ concentration 0.08 mg/L,reaction temperature 70°C,pH 9.0,with a absorption solution volume of 50 mL,a gas flow rate 200 mL/min,and H2S mass concentration of 1.58-2.02 mg/m3.展开更多
In this paper, two microwave irradiation methods：（i） liquid-phase microwave irradiation（MWI） reduction of graphite oxide suspension dissolved in de-ionized water and N, N-dimethylformamide, respectively, and（ii...In this paper, two microwave irradiation methods：（i） liquid-phase microwave irradiation（MWI） reduction of graphite oxide suspension dissolved in de-ionized water and N, N-dimethylformamide, respectively, and（ii） solid-phase MWI reduction of graphite oxide powder have been successfully carried out to reduce graphite oxide. The reduced graphene oxide products are thoroughly characterized by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectral analysis, Raman spectroscopy, UV-Vis absorption spectral analysis,and four-point probe conductivity measurements. The results show that both methods can efficiently remove the oxygencontaining functional groups attached to the graphite layers, though the solid-phase MWI reduction method can obtain far more efficiently a higher quality-reduced graphene oxide with fewer defects. The I（D）/I（G） ratio of the solid-phase MWI sample is as low as 0.46, which is only half of that of the liquid-phase MWI samples. The electrical conductivity of the reduced graphene oxide by the solid method reaches 747.9 S/m, which is about 25 times higher than that made by the liquid-phase method.展开更多
Iron oxide nanoparticles were synthesized by precipitation method and supported on activated carbon. The catalyst thus obtained was characterized by various physicochemical techniques, and used for the liquid phase de...Iron oxide nanoparticles were synthesized by precipitation method and supported on activated carbon. The catalyst thus obtained was characterized by various physicochemical techniques, and used for the liquid phase dehydrogenation/oxidation of octanol in a batch reactor at various temperatures in the range 30 °C - 60 °C. Maximum conversion of octanol to octanal was attained at 60°C in 30 min. However, with longer reaction time, the selectivity of the catalyst was found to change in favor of octene as a product. The catalyst could be recovered and reused multiple times without any decline in its catalytic performance.展开更多
为提升钒电池负极侧电极的电化学活性,采用液相氧化法对碳纳米管进行改性,并将其引入石墨毡表面制备复合电极。首先对碳纳米管与石墨毡的电化学性能进行对比,再通过液相氧化改性对碳纳米管的电化学活性进一步优化,最后制备了碳纳米管石...为提升钒电池负极侧电极的电化学活性,采用液相氧化法对碳纳米管进行改性,并将其引入石墨毡表面制备复合电极。首先对碳纳米管与石墨毡的电化学性能进行对比,再通过液相氧化改性对碳纳米管的电化学活性进一步优化,最后制备了碳纳米管石墨毡复合电极,并采用充放电测试考察其性能表现。结果表明:在浓H_(2)SO_(4)与浓HNO_(3)体积比为1∶3,温度80℃,改性时间2 h条件下得到的碳纳米管电化学活性最佳。在120 mA cm 2的电流密度下,以复合电极为负极的电池电压效率和能量效率分别为87.96%、83.47%,分别比石墨毡(82.08%、77.31%)提高了5.88和6.16个百分点,具有良好的倍率性能。展开更多
基金the Natural Science Foundation of Yunnan Province (2001E0011Q)the Science Foundation of The Education Department of Yunnan Province (0142111 and 07Z11402)
文摘For the goal of sulfur recovery, most methods are aimed at the tail gas with high-concentration H2S, but few effective methods are used for low-concentration H2S. In this work, Low-concentration H2S could be purified well by liquid phase catalytic oxidation (LCO), and the sulfur resource could also be recovered. The absorption solution was prepared by FeCl3 and sulfosalicylic acid. Under the experimental conditions, the conversion of H2S to S could be maintained above 94% at 60 ℃. In order to enhance the economical efficiency of LCO method, the absorption solution was modified by doping Ce, and a series of experiments were designed to investigate its performance. The results showed that the conversion of H2S had no obvious improvement, but above 98% conversion could be gained at 60 ℃, and the H2S conversion rate was enhanced. The optimum addition quality of Ce(NO3)3 was 0.08 g to 50 ml Fe3+ solution.
基金supported by the National Natural Science Foundation of China (No. 21376163)
文摘In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reactor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were obtained from a combination of experimental observation and hypothetical models. The results clearly showed that both the oxidation rate of toluene and generation rate of the aromatic product were proportional to the concentration of the substrate, the partial pressure of oxygen and the surface area of the catalyst. The energy barrier of toluene oxidation to benzyl alcohol was the highest(≈ 81 kJ mol^(-1)), while that of benzyl alcohol oxidation to benzaldehyde was the lowest(≈ 57 kJ mol^(-1)). Moreover, the activation energy of further oxidation of benzaldehyde in an acetic acid solvent was only slightly lower(≈ 1.9 kJ mol^(-1)) than that of toluene oxidation. Significantly, the transformation of benzyl alcohol indeed contributed to the generation of benzaldehyde and this step conformed to a first-order parallel-consecutive model. Increased reaction temperature and residence time favored the transformation of benzyl alcohol to benzaldehyde. In addition, doping with molybdenum at Mn/Mo = 3/1 enhanced the catalytic performance of the heterogeneous catalyst and was attributed to the presence of a synergetic effect between different metal cations. Regarding the microscopic kinetics, the LH-OS-ND mechanism(Langmuir–Hinshelwood adsorption of reagents on the same type of active sites and non-dissociative adsorption of oxygen) was verified as responsible for the heterogeneous oxidation of toluene. Oxygen and benzaldehyde were weakly adsorbed(Δ H_(ads,Oxy) ≈^(-1)5 kJ mol^(-1), Δ H _(ads)0,Bald) ≈-30 kJ mol^(-1)), but showed strong mobility(Δ S_(ads,Oxy) ≈-22 J mol^(-1) K^(-1)), Δ S_(ads,Bald) ≈-39 J mol^(-1) K^(-1)). The fundamental intrinsic rates were deduced based on the LH-OS-ND mechanism and showed great consistency with the macroscopic results.
基金Supported by the National Natural Science Foundation of China （20576081, 20736009） and the Ph.D. Programs Foundation of Ministry of Education of China （20070610128）.
文摘Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a φ48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH3COO)2.4H2O as catalyst.The Co2+ concentration [Co2+] was determined by extraction spectrophotometry and hereby the Co3+ concentration [Co3+] was obtained by mass balance.The results showed that [Co3+] reached the maximum at about 25-30min.[Co3+] increased with increasing Co catalyst amount at total Co concentration<150 mg.L-1 of toluene.The conversion of toluene,yield and selectivity of benzoic acid increased with the increasing [Co3+/Co2+] max.A high [Co3+] and a high [Co3+]/[Co2+] ratio are beneficial to the reaction.
文摘Catalytic activity and selectivity of prepared catalysts (Fe2O3/ and Fe2O3/AC(KOH)) were investigated for liquid phase aerobic oxidation of primary and secondary alcohols, in a batch reactor, using solvent free condition and/or eco-friendly solvents. The catalysts were characterized by SEM, EDX, XRD, FTIR, TGA/DTA, and surface area and pore size analysis. Experimental data revealed that Fe2O3/AC(KOH) was an efficient catalyst for the oxidation (dehydrogenation) of alcohol while was found to show catalytic activity for both dehydration and dehydrogenation of alcohols. The catalysts were recycled by simple filtration, and used several times without any loss of catalytic activity.
基金Project(2008ZX07105-002) supported by the Erhai Lake Project of National Science and Technology Major Project in the 11th Five years Plan of China
文摘Hydrogen sulfide in rural biogas was removed with liquid-phase catalytic oxidation.By using rare earth as catalyst,and sulfosalicylic acid as stabilizer,H2S purification efficiency could increase as high as 96%,and sulfur capacity of the composite solution was about 3 g/L.The results show that purification efficiency was affected by catalyst addition,pH,experimental temperature,and sulfur capacity.The parameters effects on catalytic oxidation were studied,and the optimized conditions were that Fe3+ concentration 0.08 mg/L,reaction temperature 70°C,pH 9.0,with a absorption solution volume of 50 mL,a gas flow rate 200 mL/min,and H2S mass concentration of 1.58-2.02 mg/m3.
基金Project supported by the National Natural Science Foundation of China(Grant No.61176090)the National Science and Technology Project 02,China(Grant No.2013ZX02303-004)
文摘In this paper, two microwave irradiation methods：（i） liquid-phase microwave irradiation（MWI） reduction of graphite oxide suspension dissolved in de-ionized water and N, N-dimethylformamide, respectively, and（ii） solid-phase MWI reduction of graphite oxide powder have been successfully carried out to reduce graphite oxide. The reduced graphene oxide products are thoroughly characterized by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectral analysis, Raman spectroscopy, UV-Vis absorption spectral analysis,and four-point probe conductivity measurements. The results show that both methods can efficiently remove the oxygencontaining functional groups attached to the graphite layers, though the solid-phase MWI reduction method can obtain far more efficiently a higher quality-reduced graphene oxide with fewer defects. The I（D）/I（G） ratio of the solid-phase MWI sample is as low as 0.46, which is only half of that of the liquid-phase MWI samples. The electrical conductivity of the reduced graphene oxide by the solid method reaches 747.9 S/m, which is about 25 times higher than that made by the liquid-phase method.
文摘Iron oxide nanoparticles were synthesized by precipitation method and supported on activated carbon. The catalyst thus obtained was characterized by various physicochemical techniques, and used for the liquid phase dehydrogenation/oxidation of octanol in a batch reactor at various temperatures in the range 30 °C - 60 °C. Maximum conversion of octanol to octanal was attained at 60°C in 30 min. However, with longer reaction time, the selectivity of the catalyst was found to change in favor of octene as a product. The catalyst could be recovered and reused multiple times without any decline in its catalytic performance.
文摘为提升钒电池负极侧电极的电化学活性,采用液相氧化法对碳纳米管进行改性,并将其引入石墨毡表面制备复合电极。首先对碳纳米管与石墨毡的电化学性能进行对比,再通过液相氧化改性对碳纳米管的电化学活性进一步优化,最后制备了碳纳米管石墨毡复合电极,并采用充放电测试考察其性能表现。结果表明:在浓H_(2)SO_(4)与浓HNO_(3)体积比为1∶3,温度80℃,改性时间2 h条件下得到的碳纳米管电化学活性最佳。在120 mA cm 2的电流密度下,以复合电极为负极的电池电压效率和能量效率分别为87.96%、83.47%,分别比石墨毡(82.08%、77.31%)提高了5.88和6.16个百分点,具有良好的倍率性能。
