Nowadays, extractive distillation is the main technique to produce 1,3-butadiene. This study simulated the 1,3-butadiene production process with DMF extractive distillation by Aspen Plus. The solvent ratio is the most...Nowadays, extractive distillation is the main technique to produce 1,3-butadiene. This study simulated the 1,3-butadiene production process with DMF extractive distillation by Aspen Plus. The solvent ratio is the most important parameter to the extractive distillation process. The article has given out the proper solvent ratios, reflux ratios, distillate ratios, and bottom product ratios of the columns. It also discusses the thermal loads of several columns. The results of simulation are consequently compared with the plant data, which shows good accordance with each other.展开更多
A series of bifunctional Zn Ce@SBA-15 catalysts with different Zn/Ce ratios were prepared by a solid-state grinding strategy and used in the conversion of ethanol to 1,3-butadiene(ETB).For the supported metal oxides,Z...A series of bifunctional Zn Ce@SBA-15 catalysts with different Zn/Ce ratios were prepared by a solid-state grinding strategy and used in the conversion of ethanol to 1,3-butadiene(ETB).For the supported metal oxides,Zn O serves as the active sites for the dehydrogenation of ethanol,and CeO_(2) promotes the aldolcondensation reaction.Based on the results of Py-FTIR and NH_(3)-TPD,it suggests that the yield of 1,3-butadiene is positively correlated with the number of weak Lewis acid sites on the catalyst surface,given their benefit for aldol-condensation reactions.The catalyst with an optimal Zn/Ce ratio of about 1:5 has the highest concentration of weak Lewis acid.Coupling with the Zn O sites,it contributes to a 98.4%conversion of ethanol and a 45.2%selective of 1,3-butadiene under relatively mild reaction conditions(375°C,101.325 k Pa,and 0.54 h^(-1)).展开更多
A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4...A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4 cut,is presented by coupling steady-state catalytic testing,in-depth characterization,kinetic evaluation,and density functional theory calculations.We reveal that:(i) 1,3-Butadiene hydrogenation on iridium is structure-sensitive with the optimal particle size of about 2 nm,and the H_(2) dissociation energy is a reliable activity descriptor;(ii) The nature of the NC hosts exerts a critical impact on the catalytic performance,and balanced nitrogen content and speciation seem key for the optimized performance;and (iii) Different deactivation mechanisms occur:fouling by coke deposition on the catalysts with a high N:C ratio (>1),and site blockage due to the competitive adsorption between 1-butene/cis-2-butene and 1,3-butadiene.These molecular insights provide valuable guidelines for the catalyst design in selective hydrogenations.展开更多
The surface species formed from the adsorption of 1,3-butadiene and 1,3-butadiene hydrogenation over the fresh Mo2C/γ-Al2O3 catalyst was studied by in situ IR spectroscopy. It is found that 1,3-butadiene adsorption o...The surface species formed from the adsorption of 1,3-butadiene and 1,3-butadiene hydrogenation over the fresh Mo2C/γ-Al2O3 catalyst was studied by in situ IR spectroscopy. It is found that 1,3-butadiene adsorption on the Mo2C/γ-Al2O3 catalyst mainly forms π-adsorbed butadiene(πs and πd) and σ-bonded surface species. These species are adsorbed mainly on the surface Moδ+(0<δ<2) sites as evidenced by co-adsorption of 1,3-butadiene and CO on the fresh Mo2C/γ-Al2O3 catalyst. The IR spectrometric analysis show that hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst produces mainly butane coupled with a small portion of butene. The selectivity of butene during the hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst might be explained by the adsorption mode of adsorbed 1,3-butadiene. Additionally, the active sites of the fresh Mo2C/γ-Al2O3 catalyst may be covered by coke during the hydrogenation reaction of 1,3-butadiene. The treatment with hydrogen at 673 K cannot remove the coke deposits from the surface of the Mo2C/γ-Al2O3 catalyst.展开更多
The forming limit diagram of Ti-15-3 alloy sheet was constituted at room temperature. The effects of different punch and rubber hardness on the limit principal strain distributions were investigated experimentally. Fi...The forming limit diagram of Ti-15-3 alloy sheet was constituted at room temperature. The effects of different punch and rubber hardness on the limit principal strain distributions were investigated experimentally. Finite element analysis models of the samples with dimensions of 180 mm×180 mm were established to analyze the friction coefficients of different interfaces. Effects of various friction coefficients on the strain distributions were studied in detail. Finally, the friction coefficients in the cold forming were determined by contrasting the strain results between the experimental data and the simulated ones.展开更多
Wrinkling is a common failure in the sheet metal forming of titanium owing to the relatively poor ability to shrink. It is important to predict wrinkling accurately in the sheet metal forming without costly trials. Th...Wrinkling is a common failure in the sheet metal forming of titanium owing to the relatively poor ability to shrink. It is important to predict wrinkling accurately in the sheet metal forming without costly trials. The ABAQUS/Explicit code was utilized to predict the wrinkling behavior in the sheet metal forming of Ti-15-3 alloy sheets. In terms of the comparison of wrinkling behavior between the simulation and experiment of the Fukui＇s conical cup tests at room temperature, the sensitivities of wrinkling simulation to various input parameters were evaluated comprehensively and quantitatively. Prediction of wrinkling and influence of rubber hardness on the winkling behavior in the rubber forming of convex flange were investigated quantitatively and validated by the rubber forming experiments. The excellent agreements between the simulations and the experiments conIirmed the accuracy of the prediction.展开更多
We have shown that some phenylethynylsilicon compounds are good cure crosslinkersof heat-curable silicone rubber(HCSR). In this paper the effects of 1, 1, 3, 3-tetramethyl-1, 3-diphenylethynyldisiloxane (TMDPDS) as a ...We have shown that some phenylethynylsilicon compounds are good cure crosslinkersof heat-curable silicone rubber(HCSR). In this paper the effects of 1, 1, 3, 3-tetramethyl-1, 3-diphenylethynyldisiloxane (TMDPDS) as a crosslinker on HCSR were studied. Thevulcanizates with fine mechanical properties could be obtained with suitable amounts ofTMDPDS. Sol fractions, and crosslinking density of vulcanizates and vulcanizationretardation effect of TMDPDS on hydrosilation curing silicone rubber were also discussed.展开更多
Natural rubber (NR) was reinforced in situ with nano CaCO3 that had been modified with methacrylic acid (MAA)(M-CaCO3).The structures and properties of the resulting composites were studied using attenuated total refl...Natural rubber (NR) was reinforced in situ with nano CaCO3 that had been modified with methacrylic acid (MAA)(M-CaCO3).The structures and properties of the resulting composites were studied using attenuated total reflection Fourier transform infrared spectroscopy(ATR-FTIR),scanning electron microscopy(SEM),and Mooney viscometer and mechanical tests.The results show that when NR is physically blended with CaCO3 and MAA,(Ca2+)-(–OOC) is formed in situ.When dicumyl peroxide (DCP) is added,the (Ca^2+)-(–OOC) self-homopolymerizes,and during the curing process poly-(Ca^2+)-(–OOC) is formed and grafts to the molecular chains of the NR via carbon-carbon double bonds.The NR/M-CaCO3 composites formed have close interfacial interaction and are well dispersed.Compared with the NR composites reinforced with unmodified nano CaCO3,the NR/M-CaCO3 composites have very different cure characteristics,rheological behavior,and mechanical properties,and these characteristics and properties show a significant relationship with the loading of M-CaCO3.展开更多
文摘Nowadays, extractive distillation is the main technique to produce 1,3-butadiene. This study simulated the 1,3-butadiene production process with DMF extractive distillation by Aspen Plus. The solvent ratio is the most important parameter to the extractive distillation process. The article has given out the proper solvent ratios, reflux ratios, distillate ratios, and bottom product ratios of the columns. It also discusses the thermal loads of several columns. The results of simulation are consequently compared with the plant data, which shows good accordance with each other.
基金National Natural Science Foundation of China for financial support(21878227)。
文摘A series of bifunctional Zn Ce@SBA-15 catalysts with different Zn/Ce ratios were prepared by a solid-state grinding strategy and used in the conversion of ethanol to 1,3-butadiene(ETB).For the supported metal oxides,Zn O serves as the active sites for the dehydrogenation of ethanol,and CeO_(2) promotes the aldolcondensation reaction.Based on the results of Py-FTIR and NH_(3)-TPD,it suggests that the yield of 1,3-butadiene is positively correlated with the number of weak Lewis acid sites on the catalyst surface,given their benefit for aldol-condensation reactions.The catalyst with an optimal Zn/Ce ratio of about 1:5 has the highest concentration of weak Lewis acid.Coupling with the Zn O sites,it contributes to a 98.4%conversion of ethanol and a 45.2%selective of 1,3-butadiene under relatively mild reaction conditions(375°C,101.325 k Pa,and 0.54 h^(-1)).
基金Zhejiang Normal University for providing the financial support (YS304320035, YS304320036, ZZ323205020521005039)Financial support from the National Natural Science Foundation of China (NSFC, 21606199)+1 种基金the Science and Technology Department of Zhejiang Province (LGG20B060004)the National Key Research and Development Program of China (2021YFA1501800, 2021YFA1501801, 2021YFA1501802) are also gratefully acknowledged。
文摘A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4 cut,is presented by coupling steady-state catalytic testing,in-depth characterization,kinetic evaluation,and density functional theory calculations.We reveal that:(i) 1,3-Butadiene hydrogenation on iridium is structure-sensitive with the optimal particle size of about 2 nm,and the H_(2) dissociation energy is a reliable activity descriptor;(ii) The nature of the NC hosts exerts a critical impact on the catalytic performance,and balanced nitrogen content and speciation seem key for the optimized performance;and (iii) Different deactivation mechanisms occur:fouling by coke deposition on the catalysts with a high N:C ratio (>1),and site blockage due to the competitive adsorption between 1-butene/cis-2-butene and 1,3-butadiene.These molecular insights provide valuable guidelines for the catalyst design in selective hydrogenations.
基金financially supported by the National Natural Science Foundation of China(No.20903054)Liaoning Provincial Natural Science Foundation(No.2014020107)+1 种基金Program for Liaoning excellent talents in university(No.LJQ2014041)sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry(SRF for ROCS,SEM)
文摘The surface species formed from the adsorption of 1,3-butadiene and 1,3-butadiene hydrogenation over the fresh Mo2C/γ-Al2O3 catalyst was studied by in situ IR spectroscopy. It is found that 1,3-butadiene adsorption on the Mo2C/γ-Al2O3 catalyst mainly forms π-adsorbed butadiene(πs and πd) and σ-bonded surface species. These species are adsorbed mainly on the surface Moδ+(0<δ<2) sites as evidenced by co-adsorption of 1,3-butadiene and CO on the fresh Mo2C/γ-Al2O3 catalyst. The IR spectrometric analysis show that hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst produces mainly butane coupled with a small portion of butene. The selectivity of butene during the hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst might be explained by the adsorption mode of adsorbed 1,3-butadiene. Additionally, the active sites of the fresh Mo2C/γ-Al2O3 catalyst may be covered by coke during the hydrogenation reaction of 1,3-butadiene. The treatment with hydrogen at 673 K cannot remove the coke deposits from the surface of the Mo2C/γ-Al2O3 catalyst.
文摘The forming limit diagram of Ti-15-3 alloy sheet was constituted at room temperature. The effects of different punch and rubber hardness on the limit principal strain distributions were investigated experimentally. Finite element analysis models of the samples with dimensions of 180 mm×180 mm were established to analyze the friction coefficients of different interfaces. Effects of various friction coefficients on the strain distributions were studied in detail. Finally, the friction coefficients in the cold forming were determined by contrasting the strain results between the experimental data and the simulated ones.
文摘Wrinkling is a common failure in the sheet metal forming of titanium owing to the relatively poor ability to shrink. It is important to predict wrinkling accurately in the sheet metal forming without costly trials. The ABAQUS/Explicit code was utilized to predict the wrinkling behavior in the sheet metal forming of Ti-15-3 alloy sheets. In terms of the comparison of wrinkling behavior between the simulation and experiment of the Fukui＇s conical cup tests at room temperature, the sensitivities of wrinkling simulation to various input parameters were evaluated comprehensively and quantitatively. Prediction of wrinkling and influence of rubber hardness on the winkling behavior in the rubber forming of convex flange were investigated quantitatively and validated by the rubber forming experiments. The excellent agreements between the simulations and the experiments conIirmed the accuracy of the prediction.
文摘We have shown that some phenylethynylsilicon compounds are good cure crosslinkersof heat-curable silicone rubber(HCSR). In this paper the effects of 1, 1, 3, 3-tetramethyl-1, 3-diphenylethynyldisiloxane (TMDPDS) as a crosslinker on HCSR were studied. Thevulcanizates with fine mechanical properties could be obtained with suitable amounts ofTMDPDS. Sol fractions, and crosslinking density of vulcanizates and vulcanizationretardation effect of TMDPDS on hydrosilation curing silicone rubber were also discussed.
基金Funded by National Natural Science Foundation of China(No.50763006)the Central Public Interest Scientific Institution Basal Research Fund for the Chinese Academy of Tropical Agricultural Sciences(No.1630122018005)。
文摘Natural rubber (NR) was reinforced in situ with nano CaCO3 that had been modified with methacrylic acid (MAA)(M-CaCO3).The structures and properties of the resulting composites were studied using attenuated total reflection Fourier transform infrared spectroscopy(ATR-FTIR),scanning electron microscopy(SEM),and Mooney viscometer and mechanical tests.The results show that when NR is physically blended with CaCO3 and MAA,(Ca2+)-(–OOC) is formed in situ.When dicumyl peroxide (DCP) is added,the (Ca^2+)-(–OOC) self-homopolymerizes,and during the curing process poly-(Ca^2+)-(–OOC) is formed and grafts to the molecular chains of the NR via carbon-carbon double bonds.The NR/M-CaCO3 composites formed have close interfacial interaction and are well dispersed.Compared with the NR composites reinforced with unmodified nano CaCO3,the NR/M-CaCO3 composites have very different cure characteristics,rheological behavior,and mechanical properties,and these characteristics and properties show a significant relationship with the loading of M-CaCO3.
