The vapor-liquid equilibrium of binary mixtures of propyl acetate, butyl acetate and isobutyl acetate with meth- anol has been determined at a constant pressure of 0.6 MPa. Results have been modeled with the Peng-Robi...The vapor-liquid equilibrium of binary mixtures of propyl acetate, butyl acetate and isobutyl acetate with meth- anol has been determined at a constant pressure of 0.6 MPa. Results have been modeled with the Peng-Robinson equation, a traditional cubic equation of state widely employed in chemical industries, as well as with the perturbed-chain statistical associating fluid PC-SAFT theory of Gross-Sadowski. By correlation of the binary inter- action parameters of these equations, the measured vapor-liquid equilibrium data can be accurately predicted. Thus, this work shows that these models are able to represent the experimental data for systems with associating comoounds via hydrogen bonding.展开更多
Two nonfoaming bubble separation techniques, air stripping and solvent sublation, are presented and discussed in order to recover butyl acetate (BA) from discharged wastewater after solvent extraction of penicillin. R...Two nonfoaming bubble separation techniques, air stripping and solvent sublation, are presented and discussed in order to recover butyl acetate (BA) from discharged wastewater after solvent extraction of penicillin. Results show air stripping is not suitable for the recovery of BA from the wastewater. Axial concentration of BA had a noted maximum point along the column. In contrast, solvent sublation is very effective to recover BA from the wastewater. In solvent sublation experiments, axial concentration of BA along the column first increased and then decreased from the bottom to the top because of two primary mass transport processes. One is the transport by adsorption or attachment to ascending bubbles, and the other is by dispersion at water-solvent interface and by water film in organic solvent layer. In order to elucidate the high removal efficiency in solvent sublation, the microstructure of the wastewater was studied with optic microscope, which was showed to be an emulsion of BA in water at large concentration of BA. Solvent sublation can be successfully used in the removal of BA from its emulsion in the wastewater. The surface tension of simulated solution composed of lysozyme and BA was studied to understand mutual effect of biological materials and BA. Results show that lysozyme affects the adsorption of BA at air-water interface and they may form a complex between BA and lysozyme molecules.展开更多
Speed of sound data for butyl acetate+benzene, or toluene, or o-xylene, or m-xylene, or p-xylene binary mixtures have been measured over the entire range of mole fraction at 308.15 K. The excess isentropic compressib...Speed of sound data for butyl acetate+benzene, or toluene, or o-xylene, or m-xylene, or p-xylene binary mixtures have been measured over the entire range of mole fraction at 308.15 K. The excess isentropic compressibilities ( Ks^E ) were computed from speed of sound and density data, derived from molar excess volume data. The Ks^E values were analyzed by using graph theoretical approach. The Ks^E values evaluated by graph theory compared reasonably well with their corresponding experimental values. The Ks^E data were also expressed in terms of Redlich-Kister polynomial equation to derive the coefficients and the standard deviation.展开更多
Mangenese oxides were synthesized using two new methods,a novel solvent‐free reaction and a reflux technique,that produced cryptomelane‐type products(K‐OMS‐2).Oxides were also synthesized using conventional method...Mangenese oxides were synthesized using two new methods,a novel solvent‐free reaction and a reflux technique,that produced cryptomelane‐type products(K‐OMS‐2).Oxides were also synthesized using conventional methods and all specimens were applied to the oxidation of ethyl acetate and butyl acetate,acting as models for the volatile organic compounds found in industrial emissions.The catalysts were also characterized using N2adsorption,X‐ray diffraction,scanning electron microscopy,temperature programmed reduction and X‐ray photoelectron spectroscopy.Each of the manganese oxides was found to be very active during the oxidation of both esters to CO2,and the synthesis methodology evidently had a significant impact on catalytic performance.The K‐OMS‐2nanorods synthesized by the solvent‐free method showed higher activity than K‐OMS‐2materials prepared by the reflux technique,and samples with cryptomelane were more active than those prepared by the conventional methods.The catalyst with the highest performance also exhibited good stability and allowed90%conversion of ethyl and butyl acetate to CO2at213and202°C,respectively.Significant differences in the catalyst performance were observed,clearly indicating that K‐OMS‐2nanorods prepared by the solvent‐free reaction were better catalysts for the selected VOC oxidations than the mixtures of manganese oxides traditionally obtained with conventional synthesis methods.The superior performance of the K‐OMS‐2catalysts might be related to the increased average oxidation state of the manganese in these structures.Significant correlations between the catalytic performance and the surface chemical properties were also identified,hig-hlighting the K‐OMS‐2properties associated with the enhanced catalytic performance of the materials.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
Nanocrystalline NH4ZrH(PO4)2·H2O was obtained by grinding ZrOC12·8H2O and (NH4)2HPO4 in the presence of surfactant PEG-400 via solid-state reaction at room temperature. The product NH4ZrH(PO4)2·H2...Nanocrystalline NH4ZrH(PO4)2·H2O was obtained by grinding ZrOC12·8H2O and (NH4)2HPO4 in the presence of surfactant PEG-400 via solid-state reaction at room temperature. The product NH4ZrH(PO4)2·H2O and its product of thermal decomposition were characterized using thermogravimetry and differential thermal analyses (TG/DTA), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), and transmission electron microscopy (TEM). Nanocrystalline NHaZrH(PO4)2·H2O with an average particle size of 17 nm was obtained when the product was kept at80℃ for 3 h. Its crystalline framework was stable at temperatures below 250℃. In addition, the catalytic performance of NH4ZrH(PO4)2·H2O in the synthesis of butyl acetate was investigated. The results show that NH4ZrH(PO4)2·H2O behaved as an excellent heterogeneous catalyst in the synthesis of butyl acetate.展开更多
Silica was used, as a catalyst carrier, to load cerous sulfate for catalyzing the synthesis of n-butyl acetate. The main purpose of this research was to explore the feasibility of silica in improving the decentrality ...Silica was used, as a catalyst carrier, to load cerous sulfate for catalyzing the synthesis of n-butyl acetate. The main purpose of this research was to explore the feasibility of silica in improving the decentrality and activity of the catalyst. The effects of molar ratio of butyl alcohol to acetic acid, the cerous sulfate loadings and the reaction time on the conversion of acetic acid were studied by single factor experiment method and orthogonal experiment method respectively. The refractive index (n20D) and molecular structure of the prepared n-butyl acetate were measured by Abbe Raefractometer and Fourier Transform Infrared spectroscope, respectively. The comparisons of the silica loaded and unloaded catalysts for catalyzing the synthesis of n-butyl acetate were made. The results showed that the suitable conditions for synthesizing n-butyl acetate were: molar ratio of butyl alcohol to acetic acid of 1.4∶1, use level of loaded cerous sulfate of 0.30 g and reaction time of 50 min, respectively. The maximum conversion of acetic acid for the silica loaded catalyst reached 98.62% which was 12.32% and 16.43% higher than those for the unloaded catalysts reported in literatures, but the use level of cerous sulfate for the former was much less than those for the latters under similar optimal technical conditions. The silica was proved to be a good catalyst carrier for enhancing decentrality and activity of the catalyst and increasing the conversion of acetic acid. The repentance of the silica loaded cerous sulfate was also investigated in the experiment.展开更多
Before proposing an innovative process for the coproduction of ethyl and butyl acetates, the individual syntheses of ethyl acetate and butyl acetate by two different routes were first studied. These syntheses involved...Before proposing an innovative process for the coproduction of ethyl and butyl acetates, the individual syntheses of ethyl acetate and butyl acetate by two different routes were first studied. These syntheses involved the reaction of ethanol or n-butanol with acetic acid or acetic anhydride in the presence of ion exchange resins: Amberlyst 15, Amberlyst 16, Amberlyst 36 and Dowex 50WX8. Kinetic and thermodynamic studies were performed with all resins. The lowest activation energy (Ea) value was obtained with Dowex 50WX8, which was identified as the best-performing resin, able to be reused at least in four runs without regeneration. The presence of water-azeotropes during the synthesis of ethyl acetate makes its purification difficult. A new strategy was adopted here, involving the use of ethanol and acetic anhydride as the starting material. In order to minimize acetic acid as co-product of this reaction, a novel two-step process for the coproduction of ethyl and butyl acetates was developed. The first step involves the production of ethyl acetate and its purification. Butyl acetate was produced in the second step: n-butanol was added to the mixture of acetic acid and the resin remaining after the first-step distillation. This process yields ethyl acetate and butyl acetate at high purity and shows an environmental benefit over the independent syntheses by green metrics calculation and life cycle assessment.展开更多
Industrial pharmaceutical wastewater usually contains butyl acetate(BA)with a concentration of 1 wt%-7 wt%,and the traditional method for BA recovery is distillation with high energy consumption.Adsorption method is d...Industrial pharmaceutical wastewater usually contains butyl acetate(BA)with a concentration of 1 wt%-7 wt%,and the traditional method for BA recovery is distillation with high energy consumption.Adsorption method is developed to recover BA with low concentration for the high efficiency and low energy consumption.Medium polar polyacrylate resins with macroporous structure of 233.1 nm and average particle size of about 526.5μm are successfully synthesized by suspension polymerization and used for the BA adsorption and desorption.The maximum adsorption capacity reaches 171.1 mg g^(-1)with relative standard deviation(RSD)value of 0.2%,which is more than twice the results in the literature.The BA desorption rate is 97.0%at 100℃with RSD value of 0.4%,and the resins are beneficial to the reuse in the adsorption-desorption cycle.The adsorption thermodynamics and kinetics are investigated,and the BA adsorption is a spontaneous and endothermic process with the increase of disorder degree.This process is mainly contributed by physical absorption and agree well with Freundlich model and pseudo-first-order adsorption kinetic model.The adsorption method avoids boiling a large amount of wastewater and hopefully provides a novel alternative technology for the BA recovery.展开更多
Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation...Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence (XRF), HE temperature programmed reduction (H2-TPR), and NH3 temperature programmed desorption (NH3-TPD). Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.展开更多
The compatibility and dynamics of latex bidirectional/nterpenetrating polymer networks (LBIPNs) and latex IPN(LIPN) of poly(vinyl acetate)(PVAc) and poly (butyl acrylate )(PBA) are investigated by means of dynamic mec...The compatibility and dynamics of latex bidirectional/nterpenetrating polymer networks (LBIPNs) and latex IPN(LIPN) of poly(vinyl acetate)(PVAc) and poly (butyl acrylate )(PBA) are investigated by means of dynamic mechanical spectroscopy (DMS) and nuclear magnetic resonance (NMR) techniques. The results of DMS show that the compatibility of the LBIPNs is much better than that of the corresponding LIPN and depends to, a large extent on the distribution of PVAc both in the core and in the shell. The results of NMR measurements indicate that the rotational correlation times of the side- groups of PBA in the LBIPN are longer than those in the LIPN. The relation between the ^(13)C linewidths of PBA and temperature is also discussed.展开更多
文摘The vapor-liquid equilibrium of binary mixtures of propyl acetate, butyl acetate and isobutyl acetate with meth- anol has been determined at a constant pressure of 0.6 MPa. Results have been modeled with the Peng-Robinson equation, a traditional cubic equation of state widely employed in chemical industries, as well as with the perturbed-chain statistical associating fluid PC-SAFT theory of Gross-Sadowski. By correlation of the binary inter- action parameters of these equations, the measured vapor-liquid equilibrium data can be accurately predicted. Thus, this work shows that these models are able to represent the experimental data for systems with associating comoounds via hydrogen bonding.
基金Supported by the National Natural Science Foundation of China (No. 20406021, No. 20236050 and No. 20221603).
文摘Two nonfoaming bubble separation techniques, air stripping and solvent sublation, are presented and discussed in order to recover butyl acetate (BA) from discharged wastewater after solvent extraction of penicillin. Results show air stripping is not suitable for the recovery of BA from the wastewater. Axial concentration of BA had a noted maximum point along the column. In contrast, solvent sublation is very effective to recover BA from the wastewater. In solvent sublation experiments, axial concentration of BA along the column first increased and then decreased from the bottom to the top because of two primary mass transport processes. One is the transport by adsorption or attachment to ascending bubbles, and the other is by dispersion at water-solvent interface and by water film in organic solvent layer. In order to elucidate the high removal efficiency in solvent sublation, the microstructure of the wastewater was studied with optic microscope, which was showed to be an emulsion of BA in water at large concentration of BA. Solvent sublation can be successfully used in the removal of BA from its emulsion in the wastewater. The surface tension of simulated solution composed of lysozyme and BA was studied to understand mutual effect of biological materials and BA. Results show that lysozyme affects the adsorption of BA at air-water interface and they may form a complex between BA and lysozyme molecules.
文摘Speed of sound data for butyl acetate+benzene, or toluene, or o-xylene, or m-xylene, or p-xylene binary mixtures have been measured over the entire range of mole fraction at 308.15 K. The excess isentropic compressibilities ( Ks^E ) were computed from speed of sound and density data, derived from molar excess volume data. The Ks^E values were analyzed by using graph theoretical approach. The Ks^E values evaluated by graph theory compared reasonably well with their corresponding experimental values. The Ks^E data were also expressed in terms of Redlich-Kister polynomial equation to derive the coefficients and the standard deviation.
基金This work was supported by project “AIProcMat@N2020‐Advanced Industrial Processes and Materials for a Sustainable Northern Region of Portugal 2020”, with the reference NORTE‐01‐0145‐FEDER‐000006, supported by Norte Portugal Regional Operational Programme
文摘Mangenese oxides were synthesized using two new methods,a novel solvent‐free reaction and a reflux technique,that produced cryptomelane‐type products(K‐OMS‐2).Oxides were also synthesized using conventional methods and all specimens were applied to the oxidation of ethyl acetate and butyl acetate,acting as models for the volatile organic compounds found in industrial emissions.The catalysts were also characterized using N2adsorption,X‐ray diffraction,scanning electron microscopy,temperature programmed reduction and X‐ray photoelectron spectroscopy.Each of the manganese oxides was found to be very active during the oxidation of both esters to CO2,and the synthesis methodology evidently had a significant impact on catalytic performance.The K‐OMS‐2nanorods synthesized by the solvent‐free method showed higher activity than K‐OMS‐2materials prepared by the reflux technique,and samples with cryptomelane were more active than those prepared by the conventional methods.The catalyst with the highest performance also exhibited good stability and allowed90%conversion of ethyl and butyl acetate to CO2at213and202°C,respectively.Significant differences in the catalyst performance were observed,clearly indicating that K‐OMS‐2nanorods prepared by the solvent‐free reaction were better catalysts for the selected VOC oxidations than the mixtures of manganese oxides traditionally obtained with conventional synthesis methods.The superior performance of the K‐OMS‐2catalysts might be related to the increased average oxidation state of the manganese in these structures.Significant correlations between the catalytic performance and the surface chemical properties were also identified,hig-hlighting the K‐OMS‐2properties associated with the enhanced catalytic performance of the materials.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
基金the Natural Science Foundation of Guangxi Province, China (No. 0640009)
文摘Nanocrystalline NH4ZrH(PO4)2·H2O was obtained by grinding ZrOC12·8H2O and (NH4)2HPO4 in the presence of surfactant PEG-400 via solid-state reaction at room temperature. The product NH4ZrH(PO4)2·H2O and its product of thermal decomposition were characterized using thermogravimetry and differential thermal analyses (TG/DTA), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), and transmission electron microscopy (TEM). Nanocrystalline NHaZrH(PO4)2·H2O with an average particle size of 17 nm was obtained when the product was kept at80℃ for 3 h. Its crystalline framework was stable at temperatures below 250℃. In addition, the catalytic performance of NH4ZrH(PO4)2·H2O in the synthesis of butyl acetate was investigated. The results show that NH4ZrH(PO4)2·H2O behaved as an excellent heterogeneous catalyst in the synthesis of butyl acetate.
基金Jiangxi Programs for Science and Technology Development (2005)
文摘Silica was used, as a catalyst carrier, to load cerous sulfate for catalyzing the synthesis of n-butyl acetate. The main purpose of this research was to explore the feasibility of silica in improving the decentrality and activity of the catalyst. The effects of molar ratio of butyl alcohol to acetic acid, the cerous sulfate loadings and the reaction time on the conversion of acetic acid were studied by single factor experiment method and orthogonal experiment method respectively. The refractive index (n20D) and molecular structure of the prepared n-butyl acetate were measured by Abbe Raefractometer and Fourier Transform Infrared spectroscope, respectively. The comparisons of the silica loaded and unloaded catalysts for catalyzing the synthesis of n-butyl acetate were made. The results showed that the suitable conditions for synthesizing n-butyl acetate were: molar ratio of butyl alcohol to acetic acid of 1.4∶1, use level of loaded cerous sulfate of 0.30 g and reaction time of 50 min, respectively. The maximum conversion of acetic acid for the silica loaded catalyst reached 98.62% which was 12.32% and 16.43% higher than those for the unloaded catalysts reported in literatures, but the use level of cerous sulfate for the former was much less than those for the latters under similar optimal technical conditions. The silica was proved to be a good catalyst carrier for enhancing decentrality and activity of the catalyst and increasing the conversion of acetic acid. The repentance of the silica loaded cerous sulfate was also investigated in the experiment.
基金supported by the European Union’s Seventh Framework Program for research,technological development and demonstration(FP7/2007-2013)[Grant Agreement No.605215]CONACyT for providing funding through PhD scholarship no.383910.
文摘Before proposing an innovative process for the coproduction of ethyl and butyl acetates, the individual syntheses of ethyl acetate and butyl acetate by two different routes were first studied. These syntheses involved the reaction of ethanol or n-butanol with acetic acid or acetic anhydride in the presence of ion exchange resins: Amberlyst 15, Amberlyst 16, Amberlyst 36 and Dowex 50WX8. Kinetic and thermodynamic studies were performed with all resins. The lowest activation energy (Ea) value was obtained with Dowex 50WX8, which was identified as the best-performing resin, able to be reused at least in four runs without regeneration. The presence of water-azeotropes during the synthesis of ethyl acetate makes its purification difficult. A new strategy was adopted here, involving the use of ethanol and acetic anhydride as the starting material. In order to minimize acetic acid as co-product of this reaction, a novel two-step process for the coproduction of ethyl and butyl acetates was developed. The first step involves the production of ethyl acetate and its purification. Butyl acetate was produced in the second step: n-butanol was added to the mixture of acetic acid and the resin remaining after the first-step distillation. This process yields ethyl acetate and butyl acetate at high purity and shows an environmental benefit over the independent syntheses by green metrics calculation and life cycle assessment.
基金the supports of National Key R&D Program of China(No.2021YFC2101000)Research and Application Service Platform Project of API Manufacturing Environmental Protection and Safety Technology in China(No.2020-0107-3-1)+1 种基金National Natural Science Foundation of China(No.22008138)Key R&D Program of Petro-China(No.2021ZZ01)on this work
文摘Industrial pharmaceutical wastewater usually contains butyl acetate(BA)with a concentration of 1 wt%-7 wt%,and the traditional method for BA recovery is distillation with high energy consumption.Adsorption method is developed to recover BA with low concentration for the high efficiency and low energy consumption.Medium polar polyacrylate resins with macroporous structure of 233.1 nm and average particle size of about 526.5μm are successfully synthesized by suspension polymerization and used for the BA adsorption and desorption.The maximum adsorption capacity reaches 171.1 mg g^(-1)with relative standard deviation(RSD)value of 0.2%,which is more than twice the results in the literature.The BA desorption rate is 97.0%at 100℃with RSD value of 0.4%,and the resins are beneficial to the reuse in the adsorption-desorption cycle.The adsorption thermodynamics and kinetics are investigated,and the BA adsorption is a spontaneous and endothermic process with the increase of disorder degree.This process is mainly contributed by physical absorption and agree well with Freundlich model and pseudo-first-order adsorption kinetic model.The adsorption method avoids boiling a large amount of wastewater and hopefully provides a novel alternative technology for the BA recovery.
基金supported by the National High Technology Research and Development Program of China(No.2012AA063101)the National Basic Research Program of China(No.2010CB732300)the"Strategic Priority Research Program"of the Chinese Academy of Sciences(No.XDB05050200)
文摘Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence (XRF), HE temperature programmed reduction (H2-TPR), and NH3 temperature programmed desorption (NH3-TPD). Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.
文摘The compatibility and dynamics of latex bidirectional/nterpenetrating polymer networks (LBIPNs) and latex IPN(LIPN) of poly(vinyl acetate)(PVAc) and poly (butyl acrylate )(PBA) are investigated by means of dynamic mechanical spectroscopy (DMS) and nuclear magnetic resonance (NMR) techniques. The results of DMS show that the compatibility of the LBIPNs is much better than that of the corresponding LIPN and depends to, a large extent on the distribution of PVAc both in the core and in the shell. The results of NMR measurements indicate that the rotational correlation times of the side- groups of PBA in the LBIPN are longer than those in the LIPN. The relation between the ^(13)C linewidths of PBA and temperature is also discussed.