Ammonia (NH<sub>3</sub>) dissociation and oxidation in a cylindrical quartz reactor has been experimentally studied for various inlet NH<sub>3</sub> concentrations (5%, 10%, and 15%) and reacto...Ammonia (NH<sub>3</sub>) dissociation and oxidation in a cylindrical quartz reactor has been experimentally studied for various inlet NH<sub>3</sub> concentrations (5%, 10%, and 15%) and reactor temperatures between 700 K and 1000 K. The thermal effects during both NH<sub>3</sub> dissociation (endothermic) and oxidation (exothermic) were observed using a bundle of thermocouples positioned along the central axis of the quartz reactor, while the corresponding NH<sub>3</sub> conversions and nitrogen oxides emissions were determined by analysing the gas composition of the reactor exit stream. A stronger endothermic effect, as indicated by a greater temperature drop during NH<sub>3</sub> dissociation, was observed as the NH<sub>3</sub> feed concentration and reactor temperature increased. During NH<sub>3</sub> oxidation, a predominantly greater exothermic effect with increasing NH<sub>3</sub> feed concentration and reactor temperature was also evident;however, it was apparent that NH<sub>3</sub> dissociation occurred near the reactor inlet, preceding the downstream NH<sub>3</sub> and H<sub>2</sub> oxidation. For both NH<sub>3</sub> dissociation and oxidation, NH<sub>3</sub> conversion increased with increasing temperature and decreasing initial NH<sub>3</sub> concentration. Significant levels of NO<sub>X</sub> emissions were observed during NH<sub>3</sub> oxidation, which increased with increasing temperature. From the experimental results, it is speculated that the stainless-steel in the thermocouple bundle may have catalysed NH<sub>3</sub> dissociation and thus changed the reaction chemistry during NH<sub>3</sub> oxidation.展开更多
A significant reaction in the synthesis of biomass-based chemicals is the catalyst-based and targeted oxidation of monosaccharides into valuable sugar acids.In this study,an activated carbon supported gold catalyst wa...A significant reaction in the synthesis of biomass-based chemicals is the catalyst-based and targeted oxidation of monosaccharides into valuable sugar acids.In this study,an activated carbon supported gold catalyst was used to oxidize glucose and xylose to gluconic acid and xylonic acid under neutral condition.Optimization of reaction conditions for the catalysts was performed using both a batch reactor and a flow-through reactor.In a batch reactor,the yields of gluconic and xylonic acid reached 93%and 92%,respectively,at 90℃ within 180 min.In a flow reactor,both reactions reached a similar yield at 80℃ with the weight hourly space velocity of 47.1 h^(-1).The reaction kinetics were explored in the flow reactor.The oxidation of glucose and xylose to gluconic and xylonic acid followed a first-order kinetics and the turnover frequency was 0.195 and 0.161 s^(-1),respectively.The activation energy was evaluated to be 60.58 and 59.30 kJ·mol^(-1),respectively.This study presents an environmentally friendly and feasible method for the selective oxidation of monosaccharides using an activated carbon supported gold catalyst,benefiting the high-value application of carbohydrates.展开更多
The oxidation reactor plays a key role in producing rutile titanium dioxide （TiO2） from vapor-phase titanium tetrachloride （TiCl4） by employing a swirling flow operation for enhanced gas mixing. This work aims to ...The oxidation reactor plays a key role in producing rutile titanium dioxide （TiO2） from vapor-phase titanium tetrachloride （TiCl4） by employing a swirling flow operation for enhanced gas mixing. This work aims to understand the effect of reactor configuration on the 3-D swirling flow field using computational fluid dynamics （CFD） simulation. Considering the anisotropic turbulence involved, the Reynolds stress model is applied to describe the complex swirling flow together with the cross-flow mixing of gases. The results show significant effect of the flow angle between the wall jet of air stream （representing TiCl4 in practice） and the axial direction on the initial flow field of cross-flow mixing, where 60° gives smooth profiles of axial velocity development while 90° may provide the fastest mixing between the jet and the axial bulk flow. The pipe shape for the reaction and developing zone, i.e., straight, expanding and shrinking, shows slight influence on the hydrodynamics.展开更多
The reactions of cationic zirconium oxide clusters （ZrxOy^＋） with ethylene （C2H4） were investigated by using a time-of-flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source. S...The reactions of cationic zirconium oxide clusters （ZrxOy^＋） with ethylene （C2H4） were investigated by using a time-of-flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source. Some hydrogen containing products （ZrO2）xH^＋（x=-1-4） were observed after the reaction. The density functional theory calculations indicate that apart from the common oxygen transfer reaction channel, the hydrogen abstraction channel can also occur in （ZrO2）x^＋＋C2H4, which supports that the observed （ZrO2）xH^＋ may be due to （ZrO2）x^＋＋C2H4→（ZrO2）xH^＋＋C2H3. The rate constants of different reaction channels were also calculated by Rice-Rarnsberger-Kassel-Marcus theory.展开更多
The sphalerite oxidative kinetics under hypergene condition was simulated and studied by means of a mixed flow reactor over a pH range of 1.0 7.8,and at dissolution temperatures from 20 to 55℃,ferric ion concentratio...The sphalerite oxidative kinetics under hypergene condition was simulated and studied by means of a mixed flow reactor over a pH range of 1.0 7.8,and at dissolution temperatures from 20 to 55℃,ferric ion concentrations from 1.0×10-5 to 1.0×10-2 mol/L,O 2 flux of 0.5 L/min,and oxidants of ferric ion and O 2.It is indicated that with ferric ion as oxidant,the oxidation rate of sphalerite increases with increasing ferric ion concentration,temperature and decreasing pH value,and under the studied conditions,the dissolution rates of Zn and Cd are approximately identical,with the values of activation energy being 41.75 and 42.51 kJ·mol-1,respectively,suggesting that the oxidation rate of sphalerite is controlled by chemical reactions on mineral surface.However,with O 2 as oxidant,the oxidation mechanism of sphalerite varies with pH value.Oxidation rate decreases with increasing pH value when pH is lower than 5.95,whereas the increase of pH value results in an increase in oxidation rate when pH value is higher than 7.The oxidation rate of sphalerite can be expressed as:R Zn =10 1.1663 [Fe3+] 0 0.154 ·[H+] 0.2659 ·e-41.75/RT or R Cd =10 1.7292 [Fe3+] 0 0.170 ·[H+] 0.2637 ·e-42.展开更多
文摘Ammonia (NH<sub>3</sub>) dissociation and oxidation in a cylindrical quartz reactor has been experimentally studied for various inlet NH<sub>3</sub> concentrations (5%, 10%, and 15%) and reactor temperatures between 700 K and 1000 K. The thermal effects during both NH<sub>3</sub> dissociation (endothermic) and oxidation (exothermic) were observed using a bundle of thermocouples positioned along the central axis of the quartz reactor, while the corresponding NH<sub>3</sub> conversions and nitrogen oxides emissions were determined by analysing the gas composition of the reactor exit stream. A stronger endothermic effect, as indicated by a greater temperature drop during NH<sub>3</sub> dissociation, was observed as the NH<sub>3</sub> feed concentration and reactor temperature increased. During NH<sub>3</sub> oxidation, a predominantly greater exothermic effect with increasing NH<sub>3</sub> feed concentration and reactor temperature was also evident;however, it was apparent that NH<sub>3</sub> dissociation occurred near the reactor inlet, preceding the downstream NH<sub>3</sub> and H<sub>2</sub> oxidation. For both NH<sub>3</sub> dissociation and oxidation, NH<sub>3</sub> conversion increased with increasing temperature and decreasing initial NH<sub>3</sub> concentration. Significant levels of NO<sub>X</sub> emissions were observed during NH<sub>3</sub> oxidation, which increased with increasing temperature. From the experimental results, it is speculated that the stainless-steel in the thermocouple bundle may have catalysed NH<sub>3</sub> dissociation and thus changed the reaction chemistry during NH<sub>3</sub> oxidation.
基金support from the National Key Research and Development Program of China(Grant No.2021YFC2101604)the National Natural Science Foundation of China(Grant No.22108088)the Natural Science Foundation of Guangdong,China(Grant No.2023A1515012740)。
文摘A significant reaction in the synthesis of biomass-based chemicals is the catalyst-based and targeted oxidation of monosaccharides into valuable sugar acids.In this study,an activated carbon supported gold catalyst was used to oxidize glucose and xylose to gluconic acid and xylonic acid under neutral condition.Optimization of reaction conditions for the catalysts was performed using both a batch reactor and a flow-through reactor.In a batch reactor,the yields of gluconic and xylonic acid reached 93%and 92%,respectively,at 90℃ within 180 min.In a flow reactor,both reactions reached a similar yield at 80℃ with the weight hourly space velocity of 47.1 h^(-1).The reaction kinetics were explored in the flow reactor.The oxidation of glucose and xylose to gluconic and xylonic acid followed a first-order kinetics and the turnover frequency was 0.195 and 0.161 s^(-1),respectively.The activation energy was evaluated to be 60.58 and 59.30 kJ·mol^(-1),respectively.This study presents an environmentally friendly and feasible method for the selective oxidation of monosaccharides using an activated carbon supported gold catalyst,benefiting the high-value application of carbohydrates.
文摘The oxidation reactor plays a key role in producing rutile titanium dioxide （TiO2） from vapor-phase titanium tetrachloride （TiCl4） by employing a swirling flow operation for enhanced gas mixing. This work aims to understand the effect of reactor configuration on the 3-D swirling flow field using computational fluid dynamics （CFD） simulation. Considering the anisotropic turbulence involved, the Reynolds stress model is applied to describe the complex swirling flow together with the cross-flow mixing of gases. The results show significant effect of the flow angle between the wall jet of air stream （representing TiCl4 in practice） and the axial direction on the initial flow field of cross-flow mixing, where 60° gives smooth profiles of axial velocity development while 90° may provide the fastest mixing between the jet and the axial bulk flow. The pipe shape for the reaction and developing zone, i.e., straight, expanding and shrinking, shows slight influence on the hydrodynamics.
基金VI. ACKNOWLEDGEMENTS This work was supported by the Hundred Talents fund of The Chinese Academy of Sciences, the National Natural Science Foundation of China （No.20703048, No.20803083, and No.20933008）, the Center for Molecular Science Foundation of Institute of Chemistry, Chinese Academy of Sciences （No.CMS-CX200803）, and the National Basic Research Programs of China （No.2006CB932100 and No.2006CB806200）.
文摘The reactions of cationic zirconium oxide clusters （ZrxOy^＋） with ethylene （C2H4） were investigated by using a time-of-flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source. Some hydrogen containing products （ZrO2）xH^＋（x=-1-4） were observed after the reaction. The density functional theory calculations indicate that apart from the common oxygen transfer reaction channel, the hydrogen abstraction channel can also occur in （ZrO2）x^＋＋C2H4, which supports that the observed （ZrO2）xH^＋ may be due to （ZrO2）x^＋＋C2H4→（ZrO2）xH^＋＋C2H3. The rate constants of different reaction channels were also calculated by Rice-Rarnsberger-Kassel-Marcus theory.
基金supported jointly by the National Natural Science Foundation of China (Grant No. 40930425)the Science and Technology Foundation of Guizhou Province [Grant No. (2010)2229]the Geological Science Foundation of the Bureau of Geology and Mineral Exploration and Development of Guizhou Province [Grant No. (2009)18]
文摘The sphalerite oxidative kinetics under hypergene condition was simulated and studied by means of a mixed flow reactor over a pH range of 1.0 7.8,and at dissolution temperatures from 20 to 55℃,ferric ion concentrations from 1.0×10-5 to 1.0×10-2 mol/L,O 2 flux of 0.5 L/min,and oxidants of ferric ion and O 2.It is indicated that with ferric ion as oxidant,the oxidation rate of sphalerite increases with increasing ferric ion concentration,temperature and decreasing pH value,and under the studied conditions,the dissolution rates of Zn and Cd are approximately identical,with the values of activation energy being 41.75 and 42.51 kJ·mol-1,respectively,suggesting that the oxidation rate of sphalerite is controlled by chemical reactions on mineral surface.However,with O 2 as oxidant,the oxidation mechanism of sphalerite varies with pH value.Oxidation rate decreases with increasing pH value when pH is lower than 5.95,whereas the increase of pH value results in an increase in oxidation rate when pH value is higher than 7.The oxidation rate of sphalerite can be expressed as:R Zn =10 1.1663 [Fe3+] 0 0.154 ·[H+] 0.2659 ·e-41.75/RT or R Cd =10 1.7292 [Fe3+] 0 0.170 ·[H+] 0.2637 ·e-42.
基金supported by National Natural Science Foundation of China(U2003123,22172184)Weiqiao-UCAS Special Projects on Low-Carbon Technology Development(GYY-DTFZ-2022-015)+1 种基金Fundamental Research Project of ICC-CAS(SCJC-DT-2022-04)Open Fund of State Key Laboratory of Coal and CBM Co-mining(2022KF23)。
