Product selectivity and reaction pathway are highly dependent on surface structure of heterogeneous catalysts.For vapor-phase hydrogenation of dimethyl oxalate(DMO),"EG route"(DMO→methyl glycolate(MG)ethyle...Product selectivity and reaction pathway are highly dependent on surface structure of heterogeneous catalysts.For vapor-phase hydrogenation of dimethyl oxalate(DMO),"EG route"(DMO→methyl glycolate(MG)ethylene glycol(EG)→ethanol(ET))and"MA route"(DMO→MG→methyl acetate(MA))were proposed over traditional Cu based catalysts and Mo-based or Fe-based catalysts,respectively.Herein,tunable yield of ET(93.7%)and MA(72.1%)were obtained through different reaction routes over WO_(x) modified Cu/SiO_(2) catalysts,and the corresponding reaction route was further proved by kinetic study and in-situ DRIFTS technology.Mechanistic studies demonstrated that H_(2) activation ability,acid density and Cu-WO_(x) interaction on the catalysts were tuned by regulating the surface W density,which resulted in the different reaction pathway and product selectivity.What's more,high yield of MA produced from DMO hydrogenation was firstly reported with the H_(2) pressure as low as 0.5 MPa.展开更多
Zirconium-based MOFs of the UiO family have attracted considerable attention due to their high thermal,chemical and mechanical stability. With the aim of further exploring the applications of zirconium-based UiO-66 in...Zirconium-based MOFs of the UiO family have attracted considerable attention due to their high thermal,chemical and mechanical stability. With the aim of further exploring the applications of zirconium-based UiO-66 in acid-catalyzed reactions and elucidating the effects of the defects in UiO-66 materials on their catalytic performances, in this work, a series of zirconium-containing UiO-66 samples were synthesized by varying the synthesis temperatures and BDC/Zr(terephthalic acid/ZrCl) ratios in the synthesis system.The synthesized UiO-66 samples were characterized by X-ray diffraction(XRD), Nadsorption-desorption,scanning electron microscopy(SEM), thermogravimetrical analysis(TGA), temperature-programmed desorption of NH(NH-TPD). Their catalytic performances were investigated in transesterification of tributyrin and soybean oil with methanol. The results showed that UiO-66 samples with different amounts of defects could be successfully prepared by varying the synthesis temperatures and/or the BDC/Zr ratios used in the synthesis system. The catalytic activities of the UiO-66 materials greatly depended on their linker defects and enhanced with the increase of the defect amount. The UiO-66 was an efficient catalyst for transesterification of tributyrin and soybean oil with methanol under mild reaction conditions and its catalytic activity was comparable to other solid acid catalysts reported in the literatures. The UiO-66 catalyst was relatively stable and could be reused.展开更多
The South Yellow Sea basin is filled with Mesozoic-Cenozoic continental sediments overlying pre-Palaeozoic and Mesozoic-Palaeozoic marine sediments.Conventional multi-channel seismic data cannot describe the velocity ...The South Yellow Sea basin is filled with Mesozoic-Cenozoic continental sediments overlying pre-Palaeozoic and Mesozoic-Palaeozoic marine sediments.Conventional multi-channel seismic data cannot describe the velocity structure of the marine residual basin in detail,leading to the lack of a deeper understanding of the distribution and lithology owing to strong energy shielding on the top interface of marine sediments.In this study,we present seismic tomography data from ocean bottom seismographs that describe the NEE-trending velocity distributions of the basin.The results indicate that strong velocity variations occur at shallow crustal levels.Horizontal velocity bodies show good correlation with surface geological features,and multi-layer features exist in the vertical velocity framework(depth:0–10 km).The analyses of the velocity model,gravity data,magnetic data,multichannel seismic profiles,and drilling data showed that high-velocity anomalies(>6.5 km/s)of small(thickness:1–2 km)and large(thickness:>5 km)scales were caused by igneous complexes in the multi-layer structure,which were active during the Palaeogene.Possible locations of good Mesozoic and Palaeozoic marine strata are limited to the Central Uplift and the western part of the Northern Depression along the wide-angle ocean bottom seismograph array.Following the Indosinian movement,a strong compression existed in the Northern Depression during the extensional phase that caused the formation of folds in the middle of the survey line.This study is useful for reconstructing the regional tectonic evolution and delineating the distribution of the marine residual basin in the South Yellow Sea basin.展开更多
Waste heat recovery from hot steel slag was determined in a granular bed through the combination of numerical simulation and an industrial test method.First,the effective thermal conductivity of the granular bed was c...Waste heat recovery from hot steel slag was determined in a granular bed through the combination of numerical simulation and an industrial test method.First,the effective thermal conductivity of the granular bed was calculated.Then,the unsteady-state model was used to simulate the heat recovery under three different flow fields(O-type,S-type,and nonshielding type(Nontype)).Second,the simulation results were validated by in-situ industrial experiments.The two methods confirmed that the heat recovery efficiencies of the flow fields from high to low followed the order of Nontype,S-type,and O-type.Finally,heat recovery was carried out under the Nontype flow field in an industrial test.The heat recovery efficiency increased from~76%and~78%to~81%when the steel slag thickness decreased from 400 and 300 to 200 mm,corresponding to reductions in the steel slag mass from 3.96 and 2.97 to 1.98 t with a blower air volume of 14687 m^(3)/h.Therefore,the research results showed that numerical simulation can not only guide experiments on waste heat recovery but also optimize the flow field.Most importantly,the method proposed in this paper has achieved higher waste heat recovery from hot steel slag in industrial scale.展开更多
基金supported by National Natural Science Foundation of China (No.22102147 and 22002151)State Key Laboratory of Chemical Engineering (No.SKL-ChE-22A02)+2 种基金Zhejiang Provincial Natural Science Foundation of China under Grant No.LQ21B030009the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDA29050300)Qinchuang Yuan high-level innovation and entrepreneurship talents implementing project (No.QCYRCXM-2022-177)。
文摘Product selectivity and reaction pathway are highly dependent on surface structure of heterogeneous catalysts.For vapor-phase hydrogenation of dimethyl oxalate(DMO),"EG route"(DMO→methyl glycolate(MG)ethylene glycol(EG)→ethanol(ET))and"MA route"(DMO→MG→methyl acetate(MA))were proposed over traditional Cu based catalysts and Mo-based or Fe-based catalysts,respectively.Herein,tunable yield of ET(93.7%)and MA(72.1%)were obtained through different reaction routes over WO_(x) modified Cu/SiO_(2) catalysts,and the corresponding reaction route was further proved by kinetic study and in-situ DRIFTS technology.Mechanistic studies demonstrated that H_(2) activation ability,acid density and Cu-WO_(x) interaction on the catalysts were tuned by regulating the surface W density,which resulted in the different reaction pathway and product selectivity.What's more,high yield of MA produced from DMO hydrogenation was firstly reported with the H_(2) pressure as low as 0.5 MPa.
基金supported by the National Science Foundation of China (Nos. 20971095 and 21576177)Research Project Supported by Shanxi Scholarship Council of China (2013-047)
文摘Zirconium-based MOFs of the UiO family have attracted considerable attention due to their high thermal,chemical and mechanical stability. With the aim of further exploring the applications of zirconium-based UiO-66 in acid-catalyzed reactions and elucidating the effects of the defects in UiO-66 materials on their catalytic performances, in this work, a series of zirconium-containing UiO-66 samples were synthesized by varying the synthesis temperatures and BDC/Zr(terephthalic acid/ZrCl) ratios in the synthesis system.The synthesized UiO-66 samples were characterized by X-ray diffraction(XRD), Nadsorption-desorption,scanning electron microscopy(SEM), thermogravimetrical analysis(TGA), temperature-programmed desorption of NH(NH-TPD). Their catalytic performances were investigated in transesterification of tributyrin and soybean oil with methanol. The results showed that UiO-66 samples with different amounts of defects could be successfully prepared by varying the synthesis temperatures and/or the BDC/Zr ratios used in the synthesis system. The catalytic activities of the UiO-66 materials greatly depended on their linker defects and enhanced with the increase of the defect amount. The UiO-66 was an efficient catalyst for transesterification of tributyrin and soybean oil with methanol under mild reaction conditions and its catalytic activity was comparable to other solid acid catalysts reported in the literatures. The UiO-66 catalyst was relatively stable and could be reused.
基金The National Natural Science Foundation of China under contract No.41806048the Open Fund of the Hubei Key Laboratory of Marine Geological Resources under contract No.MGR202009+2 种基金the Fund from the Key Laboratory of Deep-Earth Dynamics of Ministry of Natural Resource,Institute of Geology,Chinese Academy of Geological Sciences under contract No.J1901-16the Aoshan Science and Technology Innovation Project of Pilot National Laboratory for Marine Science and Technology(Qingdao)under contract No.2015ASKJ03-Seabed Resourcesthe Fund from the Korea Institute of Ocean Science and Technology(KIOST)under contract No.PE99741.
文摘The South Yellow Sea basin is filled with Mesozoic-Cenozoic continental sediments overlying pre-Palaeozoic and Mesozoic-Palaeozoic marine sediments.Conventional multi-channel seismic data cannot describe the velocity structure of the marine residual basin in detail,leading to the lack of a deeper understanding of the distribution and lithology owing to strong energy shielding on the top interface of marine sediments.In this study,we present seismic tomography data from ocean bottom seismographs that describe the NEE-trending velocity distributions of the basin.The results indicate that strong velocity variations occur at shallow crustal levels.Horizontal velocity bodies show good correlation with surface geological features,and multi-layer features exist in the vertical velocity framework(depth:0–10 km).The analyses of the velocity model,gravity data,magnetic data,multichannel seismic profiles,and drilling data showed that high-velocity anomalies(>6.5 km/s)of small(thickness:1–2 km)and large(thickness:>5 km)scales were caused by igneous complexes in the multi-layer structure,which were active during the Palaeogene.Possible locations of good Mesozoic and Palaeozoic marine strata are limited to the Central Uplift and the western part of the Northern Depression along the wide-angle ocean bottom seismograph array.Following the Indosinian movement,a strong compression existed in the Northern Depression during the extensional phase that caused the formation of folds in the middle of the survey line.This study is useful for reconstructing the regional tectonic evolution and delineating the distribution of the marine residual basin in the South Yellow Sea basin.
基金financially supported by the National Natural Science Foundation of China(No.51972019)the National Key Research and Development Program of China(No.2019YFC1905702)。
文摘Waste heat recovery from hot steel slag was determined in a granular bed through the combination of numerical simulation and an industrial test method.First,the effective thermal conductivity of the granular bed was calculated.Then,the unsteady-state model was used to simulate the heat recovery under three different flow fields(O-type,S-type,and nonshielding type(Nontype)).Second,the simulation results were validated by in-situ industrial experiments.The two methods confirmed that the heat recovery efficiencies of the flow fields from high to low followed the order of Nontype,S-type,and O-type.Finally,heat recovery was carried out under the Nontype flow field in an industrial test.The heat recovery efficiency increased from~76%and~78%to~81%when the steel slag thickness decreased from 400 and 300 to 200 mm,corresponding to reductions in the steel slag mass from 3.96 and 2.97 to 1.98 t with a blower air volume of 14687 m^(3)/h.Therefore,the research results showed that numerical simulation can not only guide experiments on waste heat recovery but also optimize the flow field.Most importantly,the method proposed in this paper has achieved higher waste heat recovery from hot steel slag in industrial scale.
