In present work,liquid phase esterification of acetic acid with ethanol over dodecatungestophosphoric acid （DTPA） supported on K10 montmorillonite was systematically studied and optimization of process parameters wa...In present work,liquid phase esterification of acetic acid with ethanol over dodecatungestophosphoric acid （DTPA） supported on K10 montmorillonite was systematically studied and optimization of process parameters was carried out.The 20% m/m DTPA/K10 was found to be the optimum catalyst with 90% acetic acid conversion and 100% ethyl acetate selectivity.The study was also explored to see the feasibility of 20% m/m DTPA/K10 as a catalyst for the alkylation of acetic acid with other alcohols like methanol,iso-propanol and n-butanol.The 20% m/m DTPA/K10 has shown increased activity with the increase in carbon number,at the same alcohol reflux.The results are novel.展开更多
The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were i...The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were investigated in this study.The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst.The solid-phase reaction between alumina and BaO formed BaAl2O4,which re-constructed the alumina structure,resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering.The addition of barium was also beneficial for enhancing the catalytic activity,resulting from the changed catalytic reaction network.The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl,formate,and C=C functional groups on the catalyst surface,attributed to its relatively high ability to cause the gasification of these species.In addition,coking was considerably more significant over the Ba-Ni/Al2O3 catalyst.Moreover,the Ba-Ni/Al2O3 catalyst was more stable than the Ni/Al2O3catalyst,owing to the distinct forms of coke formed (carbon nanotube form over the Ba-Ni/Al2O3 catalyst,and the amorphous form over the Ni/Al2O3 catalyst).展开更多
The supported Pt catalysts(1 wt%)were prepared by the incipient impregnation method and analyzed using synchrotron-based X-ray diffraction,BET surface area,oxygen adsorption,CO pulse chemisorption,temperature-programm...The supported Pt catalysts(1 wt%)were prepared by the incipient impregnation method and analyzed using synchrotron-based X-ray diffraction,BET surface area,oxygen adsorption,CO pulse chemisorption,temperature-programmed desorption(TPD)of acetic acid,H2-TPD,NH3-TPD,O2-TPD,and H2-TPR.The reactivity of Pt-based catalysts was studied using a fixed bed reactor at 300 C and 4 MPa for hydrodeoxygenation of acetic acid,where Pt/TiO2 was very selective for ethane production.TPD experiments revealed that several conditions must be satisfied to achieve this high selectivity to ethane from acetic acid,such as Pt sites,moderate acidity,and medium metal-oxygen bond strength in the oxide support.This work provides insights in developing novel catalytic materials for hydrocarbon productions from various organics including bio-fuels.展开更多
The possibility of synthesizing acetic acid from CH4 and CO2 in the presence of O2 over a V2O5-PdCl2/Al2O3 catalyst has been explored. The result shows that it is feasible in catalyzing a direct conversion of CH4, CO2...The possibility of synthesizing acetic acid from CH4 and CO2 in the presence of O2 over a V2O5-PdCl2/Al2O3 catalyst has been explored. The result shows that it is feasible in catalyzing a direct conversion of CH4, CO2 and O2 to acetic acid. It is concluded that both CO2 and O2 are involved in the formation of acetic acid.展开更多
Considering energy shortage, large molecules in corn cob and easy separation of solid catalysts, nano oxides are used to transform corn cob into useful chemicals. Because of the microcrystals, nano oxides offer enough...Considering energy shortage, large molecules in corn cob and easy separation of solid catalysts, nano oxides are used to transform corn cob into useful chemicals. Because of the microcrystals, nano oxides offer enough accessible sites for cellulose, hemicellulose and monosaccharide from corn cob hydrolysis and oxidant. Chemical conversion of corn cob to organic acids is investigated over nano ceria, alumina, titania and zirconia under various atmospheres. Liquid products are mainly formic and acetic acids. A small amount of other compounds, such as D-xylose,D-glucose, arabinose and xylitol are also detected simultaneously. The yield of organic acids reaches 25%–29% over the nano oxide of ceria,zirconia and alumina with 3 h reaction time under 453 K and 1.2 MPa O2. The unique and fast conversion of corn cob is directly approached over the nano oxides. The results are comparative to those of biofermentation and offer an alternative method in chemically catalytic conversion of corn cob to useful chemicals in a one-pot chemical process.展开更多
An improved two-step process for converting carbohydrate biomass to acetic acid under hydrothermal conditions is proposed. The first step consists of the production of lactic acid from carbohydrate biomass, and the se...An improved two-step process for converting carbohydrate biomass to acetic acid under hydrothermal conditions is proposed. The first step consists of the production of lactic acid from carbohydrate biomass, and the second step consists of conversion of the lactic acid obtained in the first step to acetic acid using CuO as an oxidant. The results indicated that CuO as an oxidant in the second step can significantly improve the production of high-purity acetic acid from lactic acid, and the maximum yield of acetic acid was 61%, with a purity of 90%. The yield of acetic acid obtained using the improved two-step hydrothermal process from carbohydrate biomass, such as glucose, cellulose and starch, was greater than that obtained using traditional two-step process with H_2O_2 or O_2. In addition, a proposed pathway for the production of acetic acid from lactic acid in the second step with CuO was also discussed. The present study provides a useful two-step process for the production of acetic acid from carbohydrate biomass.展开更多
Alkaline earth metal （Mg,Ca,Sr and Ba）-doped Mo-V-Sb-O x catalysts,prepared by a dry-up method,have been investigated for their catalytic performance in the oxidation of propane under different reaction conditions.T...Alkaline earth metal （Mg,Ca,Sr and Ba）-doped Mo-V-Sb-O x catalysts,prepared by a dry-up method,have been investigated for their catalytic performance in the oxidation of propane under different reaction conditions.The catalysts have been characterized by N2 adsorption-desorption,temperature-programmed desorption （TPD） of NH3,SEM and XRD.Influence of water vapor on the catalytic performance,particularly on the selectivities to acetic acid and acrylic acid,has also been studied.The selectivity to acrylic acid was improved significantly by the doping of alkaline earth metals to Mo-V-Sb-O x catalysts.The surface acidic sites of the catalyst decreased with the doping of the catalyst with alkaline earth metals,which ultimately was found to be beneficial for obtaining high selectivity to acrylic acid.The catalytic activity and product selectivities were found to be influenced by the reaction temperature,C3H8/O2 ratio and space velocity.A significant improvement in the selectivity to acrylic acid has also been observed by the addition of water vapor in the feed of propane and oxygen in the oxidation of propane.展开更多
Synthesis of acetic acid by direct oxidation of ethylene on Pd-H4SiW12O40-based catalysts was studied in a fixed-bed integral reactor and a pulse differential reactor. From the performance of the catalysts with differ...Synthesis of acetic acid by direct oxidation of ethylene on Pd-H4SiW12O40-based catalysts was studied in a fixed-bed integral reactor and a pulse differential reactor. From the performance of the catalysts with different compositions and configurations, it is proposed that acetic acid is predominantly produced via an intermediate of acetaldehyde. This can be easily confirmed by comparing the product distributions in the integral and the differential reactors. The active sites for acetic acid formation are considered to exist mainly at the boundaries between the H4SiW12O40 and the Pd particles. The Pd-based catalysts reduced by H2/N2 have higher activities than those reduced by hydrazine, as explained by the degree of Pd dispersion obtained from the characteristics of hydrogen chemical adsorption. It was found that the Pd-Se-SiW12/SiO2 catalyst with selenium tetrachloride as a precursor was more active than that with potassium selenite, and that the acetic acid yield can be greatly increased by adding a suitable amount of dichloroethane (C2H4C12/C2H4 mole ratio=0.03) to the reactants.展开更多
In this article, phenyl acetate was synthesized from phenol and acetic anhydride over titanium silicalite-1, in which the organic structure-directing agents were immobilized(TS-1-U). The reaction conditions were speci...In this article, phenyl acetate was synthesized from phenol and acetic anhydride over titanium silicalite-1, in which the organic structure-directing agents were immobilized(TS-1-U). The reaction conditions were specified at a phenol to acetic anhydride molar ratio of 1:1.2, a catalyst dosage of 6 m%, and a reaction temperature of 70 ℃. A total of 96.5% of phenol was converted to phenyl acetate without producing any byproducts after 2.5 h of reaction. Besides, although the catalyst deactivation is inevitable, TS-1-U could be recycled for at least four times.展开更多
The aim of this paper is to use the microsatellites to evaluate acid-tolerance in Saccharomyces(S.) cerevisiae. Microsatellites have been widely used as the molecular marker to classify and identify S. cerevisiae stra...The aim of this paper is to use the microsatellites to evaluate acid-tolerance in Saccharomyces(S.) cerevisiae. Microsatellites have been widely used as the molecular marker to classify and identify S. cerevisiae strains, analyze genetic relationships among strains, and reveal genetic diversity of S. cerevisiae populations. In this paper, 25 key microsatellites of S. cerevisiae from 44 industrial yeast strains are investigated in the medium withconcentration gradients of acetic acid. Based on the analysis of correlations between the key microsatellite loci repeat numbers and acid-tolerance of the strains, the allele size of 4P14 a and 10P13 is positively related to acid-tolerance(p ? 0.05), the allele size of AT-X, 4P1 a and 10P8 are significantly negatively related to acid-tolerance(p ? 0.01). The above results provide informations on the molecular biodiversity of S. cerevisiae strains and can be a theoretical guidance for molecular marker assisted selection.展开更多
This work proposed to use the ionic liquid [EMIM][BF_4] as absorbent for the absorption of gaseous acetic acid. The feasibility of this technology was investigated from molecular level to industrial scale. The acetic ...This work proposed to use the ionic liquid [EMIM][BF_4] as absorbent for the absorption of gaseous acetic acid. The feasibility of this technology was investigated from molecular level to industrial scale. The acetic acid absorption experiment was carried out using [EMIM][BF_4],and the removal ratio of acetic acid in the gas product can achieve 88.6% at 20C under atmospheric pressure at the laboratory scale. Based on the experimental results, a reliable strict equilibrium phase model embedding the parameters of the UNIFAC model was established. On this basis, the conceptual process design and optimization of acetic acid removal by [EMIM][BF_4] at an industrial scale was done, and the most suitable design and operation parameters were obtained. For a further step, the binding energy between [EMIM][BF_4] and acetic acid was calculated to give some insights into the separation mechanism, and the results indicate that the interaction between acetic acid and IL is much stronger than that between nitrogen and IL. Moreover, hydrogen bond can be formed between the cation-acetic acid as well as the anion-acetic acid.展开更多
Sourdough starters for making traditional steamed bread are rich in microbes.Studies have shown that,in addition to yeast and lactic acid bacteria(LAB),acetic acid bacteria(AAB)are other functional species in sourdoug...Sourdough starters for making traditional steamed bread are rich in microbes.Studies have shown that,in addition to yeast and lactic acid bacteria(LAB),acetic acid bacteria(AAB)are other functional species in sourdough,but the influences of AAB on the properties of sourdough and steamed bread were rarely reported.This study aimed to assess the effects of a selected strain of acetic acid bacterium on the properties of sourdough and steamed bread.Sourdoughs and steamed breads were prepared from five different starter cultures,marked as CK(control check,with no starters),Y(only yeast),YL(yeast+LAB),YA(yeast+AAB)and YLA(yeast+LAB+AAB),and their properties were determined.The results of sour dough properties showed that the YLA sourdough had the highest total titratable acid of 14.6 mL and the lowest pH of 3.87 compared with the other groups after fermentation to 8 h;and the YLA sourdough had the greatest elasticity and viscosity.The results of quality properties of steamed bread revealed that the L*value(88.40±0.09)of the YA steamed bread was significantly higher than those of the YLA and YL steamed breads;the YLA steamed bread had the highest specific volume and the highest sensory score of 89.6±3.31 in comparison to those of the other groups;the hardness and chewiness of YLA and YA steamed breads were significantly lower than those of the other groups.Volatile compounds in the steamed breads were also determined by SPME-GC-MS.A total of 42 flavor substances were detected,including 3 kinds of alcohols,8 kinds of aldehydes,7 kinds of ketones,2 kinds of acids,15 kinds of esters,1 furan,and 6 kinds of other types of compounds,mainly alkanes and esters,followed by alcohols and aldehydes.The YLA steamed bread was richer in esters,aldehydes,and acids than those from the other treatment groups.By contrast,alkanes and aldehydes were dominant in the Y and YL steamed breads.Therefore,the flavor and quality of the steamed bread made from the YLA sourdough could be improved obviously.These results could provide references for the application of AAB in dough fermentation and the improvement of new kinds of starters.展开更多
In this study, mixed metal oxides developed with a perovskite-type structure that show great potential for use in catalysis. Perovskite oxide catalysts with the composition LaMoxV1-xOn （x = 0.1, 0.3, 0.5, 0.7, and 0....In this study, mixed metal oxides developed with a perovskite-type structure that show great potential for use in catalysis. Perovskite oxide catalysts with the composition LaMoxV1-xOn （x = 0.1, 0.3, 0.5, 0.7, and 0.9） have been synthesized by the sol-gel method and then used in the ethane dry reforming reaction for the direct synthesis of acetic acid. The influence of the nature of the metallic source （metal, nitrate, acetylacetonate, and ammonium） on gel formation has been studied by Fourier-transform infrared spectroscopy （FT-IR） and thermogravimetric analysis （TGA-DTA）. After calcination, the obtained perovskites were characterized by X-ray diffraction （XRD） and energy-dispersive X-ray spectrometry （EDS） coupled with scanning electron microscopy （SEM）. The catalysts were then subjected to thermo-programmed reduction （TPR）. The surface area （BET） was found to increase from 2.6 m^2/g （x = 0.1） to 5.1 m2/g （x = 1.0） with increasing molybdenum content following calcinations at 750 °C, and pure LaMoxV1-xOn perovskite was obtained with good homogeneity. The catalysts have been characterized by XRD, SEM, EDS, and carbon analysis （CA）. The results indicate that through this synthesis it is possible to obtain highly crystalline, homogeneous and pure solids, with well-defined structures. The direct synthesis of acetic acid from ethane over the perovskite catalysts was studied at temperatures between 450 and 850 °C and elevated pressures between 1 and 8 bar. It was found that the yield of acetic acid and the selectivity of its formation could be increased by incorporating more molybdenum into the perovskite structure. The experimental studies have shown that the calcination temperature and the molybdenum content have a significant influence on the catalytic activity. Amongst the catalysts tested, LaMo0.7V0.3O4.2 exhibited the best activity and stability.展开更多
In September 2009 a commercial unit for manufacture of acetic acid by low-pressure oxo-synthesis at the Guizhou Crystal Group had come on stream,which also symbolized the termination of the existing acetic acid produc...In September 2009 a commercial unit for manufacture of acetic acid by low-pressure oxo-synthesis at the Guizhou Crystal Group had come on stream,which also symbolized the termination of the existing acetic acid production process by the mercury method characteristic of heavy pollution at the Guizhou Crystal Group.This project covers展开更多
A study was conducted on the isolation of poplar （Populusxeurarnaricana （Dode） Guineir cv. I -72/58） wood components with aqueous acetic acid （AcOH） containing small amounts of sulfuric acid. The reaction time, ...A study was conducted on the isolation of poplar （Populusxeurarnaricana （Dode） Guineir cv. I -72/58） wood components with aqueous acetic acid （AcOH） containing small amounts of sulfuric acid. The reaction time, concentration of acetic acid, ratio of liquor to wood, and concentration of acid catalyst were investigated to examine their effects on the fractionation of wood components. The three main separated components were characterized. The results showed that the optimum conditions for fractionation of poplar wood components were： 0.3% H2SO4 in reaction solution, ratio of liquor to wood 6, reflux time 3 h, and 90% AcOH. The residues were mainly composed of a-Cellulose and hemicellulose, The water insoluble precipitate （acetic acid lignin, AcL） had a low weight-average molecular weight range from 341 to 253 （Mw） and a narrow molecular weight distribution from 1.1 to 1.2. The sugar analysis revealed the solubilized products resulted mainly from hemicellulose and exited as monosaccharides.展开更多
The excited-state double-proton transfer （ESDPT） mechanism of 2-amino-3-methoxypyridine and acetic acid com- plex is studied by the density functional theory （DFT） and time-dependent DFT with CAM-B3LYP functional....The excited-state double-proton transfer （ESDPT） mechanism of 2-amino-3-methoxypyridine and acetic acid com- plex is studied by the density functional theory （DFT） and time-dependent DFT with CAM-B3LYP functional. The complex is connected through two different types of inter-molecular hydrogen bonds. After photo-excitation, both hydrogen bonds get strengthened, which can facilitate the ESDPT reaction. The scanned potential energy curve along the proton transfer coordinate indicates that the ESDPT reaction proceeds in a stepwise pattern.展开更多
Exploring stable and robust catalysts to replace the current toxic CuCr based catalysts for dehydrogenative coupling of ethanol to ethyl acetate is a challenging but promising task.Herein,novel NiIn based catalysts we...Exploring stable and robust catalysts to replace the current toxic CuCr based catalysts for dehydrogenative coupling of ethanol to ethyl acetate is a challenging but promising task.Herein,novel NiIn based catalysts were developed by tailoring Ni catalysts with Indium(In)for this reaction.Over the optimal Ni0.1Zn0.7Al0.3InOx catalyst,the ethyl acetate selectivity reached 90.1%at 46.2%ethanol conversion under the conditions of 548 K and a weight hourly space velocity of 1.9 h^(-1)in the 370 h time on stream.Moreover,the ethyl acetate productivity surpassed 1.1 g_(ethyl acetate)g_(catalyst)^(-1)h^(-1),,one of the best performance in current works.According to catalyst characterizations and conditional experiments,the active sites for dehydrogenative coupling of ethanol to ethyl acetate were proved to be Ni4In alloys.The presence of In tailored the chemical properties of Ni,and subsequently inhibited the C-C cracking and/or condensation reactions during ethanol conversions.Over Ni4In alloy sites,ethanol was dehydrogenated into acetaldehyde,and then transformed into acetyl species with the removal of H atoms.Finally,the coupling between acetyl species and surface-abundant ethoxyde species into ethyl acetate was achieved,affording a high ethyl acetate selectivity and catalyst stability.展开更多
The conversion of waste polylactic acid(PLA)plastics into high-value-added chemicals through electrochemical methods is a promising and sustainable approach.However,developing efficient and highly selective catalysts ...The conversion of waste polylactic acid(PLA)plastics into high-value-added chemicals through electrochemical methods is a promising and sustainable approach.However,developing efficient and highly selective catalysts for lactic acid oxidation reaction(LAOR)and understanding the reaction process are challenging.Here,we report the electrooxidation of waste PLA to acetate at a high current density of 100 mA cm-2 with high Faraday efficiency(~95%)and excellent stability(>100 h)over a nickel selenide nanosheet catalyst.In addition,a total Faraday efficiency of up to 190%was achieved for carboxylic acids,including acetic acid and formic acid,by coupling with the cathodic CO_(2) reduction reaction.In situ experimental results and theoretical simulations revealed that the catalytic activity center of LAOR was dynamically formed NiOOH species,and the surface-adsorbed SeO_(x) species accelerated the formation of Ni~(3+)species,thus promoting catalytic activity.The mechanism of lactic acid electrooxidation was further elucidated.Lactic acid was dehydrogenated to produce pyruvate first and then formed CH_3CO due to preferential C-C bond cleavage,resulting in the presence of acetate.This work demonstrated a sustainable method for recycling waste PLA and CO_(2) into high-value-added products.展开更多
The acetic acid-water binary system is a classical hydroxy-carboxy mixed system, while new and interesting phenomena appear under stimulated Raman scattering(SRS).Compared with the weaker signal of the acetic acid-wat...The acetic acid-water binary system is a classical hydroxy-carboxy mixed system, while new and interesting phenomena appear under stimulated Raman scattering(SRS).Compared with the weaker signal of the acetic acid-water binary system obtained in spontaneous Raman scattering, SRS provides a finer band and a relatively distinct structural transition point.The structural transformation points are respectively at 30% and 80% by volume ratio under the condition of spontaneous Raman spectroscopy, while they are respectively at 15% and 25% under the condition of SRS.This phenomenon is attributed to the generation of laser induced plasma and shockwave induced dynamic high pressure environment during SRS.展开更多
文摘In present work,liquid phase esterification of acetic acid with ethanol over dodecatungestophosphoric acid （DTPA） supported on K10 montmorillonite was systematically studied and optimization of process parameters was carried out.The 20% m/m DTPA/K10 was found to be the optimum catalyst with 90% acetic acid conversion and 100% ethyl acetate selectivity.The study was also explored to see the feasibility of 20% m/m DTPA/K10 as a catalyst for the alkylation of acetic acid with other alcohols like methanol,iso-propanol and n-butanol.The 20% m/m DTPA/K10 has shown increased activity with the increase in carbon number,at the same alcohol reflux.The results are novel.
基金supported by the National Natural Science Foundation of China(No.51876080)the Strategic International Scientific and Technological Innovation Cooperation Special Funds of National Key Research and Development Program of China(No.2016YFE0204000)+3 种基金the Program for Taishan Scholars of Shandong Province Governmentthe Recruitment Program of Global Experts(Thousand Youth Talents Plan)the Natural Science Foundation of Shandong Province(ZR2017BB002)the Key Research and Development Program of Shandong Province(2018GSF116014)。
文摘The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were investigated in this study.The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst.The solid-phase reaction between alumina and BaO formed BaAl2O4,which re-constructed the alumina structure,resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering.The addition of barium was also beneficial for enhancing the catalytic activity,resulting from the changed catalytic reaction network.The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl,formate,and C=C functional groups on the catalyst surface,attributed to its relatively high ability to cause the gasification of these species.In addition,coking was considerably more significant over the Ba-Ni/Al2O3 catalyst.Moreover,the Ba-Ni/Al2O3 catalyst was more stable than the Ni/Al2O3catalyst,owing to the distinct forms of coke formed (carbon nanotube form over the Ba-Ni/Al2O3 catalyst,and the amorphous form over the Ni/Al2O3 catalyst).
文摘The supported Pt catalysts(1 wt%)were prepared by the incipient impregnation method and analyzed using synchrotron-based X-ray diffraction,BET surface area,oxygen adsorption,CO pulse chemisorption,temperature-programmed desorption(TPD)of acetic acid,H2-TPD,NH3-TPD,O2-TPD,and H2-TPR.The reactivity of Pt-based catalysts was studied using a fixed bed reactor at 300 C and 4 MPa for hydrodeoxygenation of acetic acid,where Pt/TiO2 was very selective for ethane production.TPD experiments revealed that several conditions must be satisfied to achieve this high selectivity to ethane from acetic acid,such as Pt sites,moderate acidity,and medium metal-oxygen bond strength in the oxide support.This work provides insights in developing novel catalytic materials for hydrocarbon productions from various organics including bio-fuels.
基金support of both the Foundation of National Science(No.20001016)the Research Foundation for Returned Scholars of Shanxi Province,China.
文摘The possibility of synthesizing acetic acid from CH4 and CO2 in the presence of O2 over a V2O5-PdCl2/Al2O3 catalyst has been explored. The result shows that it is feasible in catalyzing a direct conversion of CH4, CO2 and O2 to acetic acid. It is concluded that both CO2 and O2 are involved in the formation of acetic acid.
基金supported by the Doctoral Fund of the Ministry of Education of China(Grant No.20100091120035)NSF of China(21103087)
文摘Considering energy shortage, large molecules in corn cob and easy separation of solid catalysts, nano oxides are used to transform corn cob into useful chemicals. Because of the microcrystals, nano oxides offer enough accessible sites for cellulose, hemicellulose and monosaccharide from corn cob hydrolysis and oxidant. Chemical conversion of corn cob to organic acids is investigated over nano ceria, alumina, titania and zirconia under various atmospheres. Liquid products are mainly formic and acetic acids. A small amount of other compounds, such as D-xylose,D-glucose, arabinose and xylitol are also detected simultaneously. The yield of organic acids reaches 25%–29% over the nano oxide of ceria,zirconia and alumina with 3 h reaction time under 453 K and 1.2 MPa O2. The unique and fast conversion of corn cob is directly approached over the nano oxides. The results are comparative to those of biofermentation and offer an alternative method in chemically catalytic conversion of corn cob to useful chemicals in a one-pot chemical process.
基金supported by the National Natural Science Foundation of China(No.21277091)the State Key Program of National Natural Science Foundation of China(No.21436007)+2 种基金key Basic Research Projects of Science and Technology Commission of Shanghai(14JC1403100)the Program for Professor of Special Appointment(Eastern Scholar) at Shanghai Institutions of Higher Learning(ZXDF160002)the Project-sponsored by SRF for ROCS,SEM(BG1600002)
文摘An improved two-step process for converting carbohydrate biomass to acetic acid under hydrothermal conditions is proposed. The first step consists of the production of lactic acid from carbohydrate biomass, and the second step consists of conversion of the lactic acid obtained in the first step to acetic acid using CuO as an oxidant. The results indicated that CuO as an oxidant in the second step can significantly improve the production of high-purity acetic acid from lactic acid, and the maximum yield of acetic acid was 61%, with a purity of 90%. The yield of acetic acid obtained using the improved two-step hydrothermal process from carbohydrate biomass, such as glucose, cellulose and starch, was greater than that obtained using traditional two-step process with H_2O_2 or O_2. In addition, a proposed pathway for the production of acetic acid from lactic acid in the second step with CuO was also discussed. The present study provides a useful two-step process for the production of acetic acid from carbohydrate biomass.
文摘Alkaline earth metal （Mg,Ca,Sr and Ba）-doped Mo-V-Sb-O x catalysts,prepared by a dry-up method,have been investigated for their catalytic performance in the oxidation of propane under different reaction conditions.The catalysts have been characterized by N2 adsorption-desorption,temperature-programmed desorption （TPD） of NH3,SEM and XRD.Influence of water vapor on the catalytic performance,particularly on the selectivities to acetic acid and acrylic acid,has also been studied.The selectivity to acrylic acid was improved significantly by the doping of alkaline earth metals to Mo-V-Sb-O x catalysts.The surface acidic sites of the catalyst decreased with the doping of the catalyst with alkaline earth metals,which ultimately was found to be beneficial for obtaining high selectivity to acrylic acid.The catalytic activity and product selectivities were found to be influenced by the reaction temperature,C3H8/O2 ratio and space velocity.A significant improvement in the selectivity to acrylic acid has also been observed by the addition of water vapor in the feed of propane and oxygen in the oxidation of propane.
文摘Synthesis of acetic acid by direct oxidation of ethylene on Pd-H4SiW12O40-based catalysts was studied in a fixed-bed integral reactor and a pulse differential reactor. From the performance of the catalysts with different compositions and configurations, it is proposed that acetic acid is predominantly produced via an intermediate of acetaldehyde. This can be easily confirmed by comparing the product distributions in the integral and the differential reactors. The active sites for acetic acid formation are considered to exist mainly at the boundaries between the H4SiW12O40 and the Pd particles. The Pd-based catalysts reduced by H2/N2 have higher activities than those reduced by hydrazine, as explained by the degree of Pd dispersion obtained from the characteristics of hydrogen chemical adsorption. It was found that the Pd-Se-SiW12/SiO2 catalyst with selenium tetrachloride as a precursor was more active than that with potassium selenite, and that the acetic acid yield can be greatly increased by adding a suitable amount of dichloroethane (C2H4C12/C2H4 mole ratio=0.03) to the reactants.
基金financially supported by the SINOPEC(Contact No.S413025)
文摘In this article, phenyl acetate was synthesized from phenol and acetic anhydride over titanium silicalite-1, in which the organic structure-directing agents were immobilized(TS-1-U). The reaction conditions were specified at a phenol to acetic anhydride molar ratio of 1:1.2, a catalyst dosage of 6 m%, and a reaction temperature of 70 ℃. A total of 96.5% of phenol was converted to phenyl acetate without producing any byproducts after 2.5 h of reaction. Besides, although the catalyst deactivation is inevitable, TS-1-U could be recycled for at least four times.
基金Funded by Open Project Program of the Key Laboratory of Industrial Biotechnology,Ministry of Education,China(KLIBKF201102)the Fok Ying-Tong Education Foundation of China(No.131020)+2 种基金the program for New Century Excellent Talents in University(NCET-11-0665)the Fundamental Research Funds for the Central Universities(JUSRP51313B)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘The aim of this paper is to use the microsatellites to evaluate acid-tolerance in Saccharomyces(S.) cerevisiae. Microsatellites have been widely used as the molecular marker to classify and identify S. cerevisiae strains, analyze genetic relationships among strains, and reveal genetic diversity of S. cerevisiae populations. In this paper, 25 key microsatellites of S. cerevisiae from 44 industrial yeast strains are investigated in the medium withconcentration gradients of acetic acid. Based on the analysis of correlations between the key microsatellite loci repeat numbers and acid-tolerance of the strains, the allele size of 4P14 a and 10P13 is positively related to acid-tolerance(p ? 0.05), the allele size of AT-X, 4P1 a and 10P8 are significantly negatively related to acid-tolerance(p ? 0.01). The above results provide informations on the molecular biodiversity of S. cerevisiae strains and can be a theoretical guidance for molecular marker assisted selection.
基金financially supported by the National Natural Science Foundation of China(No.U1862103)
文摘This work proposed to use the ionic liquid [EMIM][BF_4] as absorbent for the absorption of gaseous acetic acid. The feasibility of this technology was investigated from molecular level to industrial scale. The acetic acid absorption experiment was carried out using [EMIM][BF_4],and the removal ratio of acetic acid in the gas product can achieve 88.6% at 20C under atmospheric pressure at the laboratory scale. Based on the experimental results, a reliable strict equilibrium phase model embedding the parameters of the UNIFAC model was established. On this basis, the conceptual process design and optimization of acetic acid removal by [EMIM][BF_4] at an industrial scale was done, and the most suitable design and operation parameters were obtained. For a further step, the binding energy between [EMIM][BF_4] and acetic acid was calculated to give some insights into the separation mechanism, and the results indicate that the interaction between acetic acid and IL is much stronger than that between nitrogen and IL. Moreover, hydrogen bond can be formed between the cation-acetic acid as well as the anion-acetic acid.
基金supported by Young Key Teachers Training Program of Henan University of Technology and Young Key Teachers Cultivation Plan in Colleges and Universities of Henan province (2019GGJS-088)sponsored by Natural Science Foundation of Henan(202300410113)
文摘Sourdough starters for making traditional steamed bread are rich in microbes.Studies have shown that,in addition to yeast and lactic acid bacteria(LAB),acetic acid bacteria(AAB)are other functional species in sourdough,but the influences of AAB on the properties of sourdough and steamed bread were rarely reported.This study aimed to assess the effects of a selected strain of acetic acid bacterium on the properties of sourdough and steamed bread.Sourdoughs and steamed breads were prepared from five different starter cultures,marked as CK(control check,with no starters),Y(only yeast),YL(yeast+LAB),YA(yeast+AAB)and YLA(yeast+LAB+AAB),and their properties were determined.The results of sour dough properties showed that the YLA sourdough had the highest total titratable acid of 14.6 mL and the lowest pH of 3.87 compared with the other groups after fermentation to 8 h;and the YLA sourdough had the greatest elasticity and viscosity.The results of quality properties of steamed bread revealed that the L*value(88.40±0.09)of the YA steamed bread was significantly higher than those of the YLA and YL steamed breads;the YLA steamed bread had the highest specific volume and the highest sensory score of 89.6±3.31 in comparison to those of the other groups;the hardness and chewiness of YLA and YA steamed breads were significantly lower than those of the other groups.Volatile compounds in the steamed breads were also determined by SPME-GC-MS.A total of 42 flavor substances were detected,including 3 kinds of alcohols,8 kinds of aldehydes,7 kinds of ketones,2 kinds of acids,15 kinds of esters,1 furan,and 6 kinds of other types of compounds,mainly alkanes and esters,followed by alcohols and aldehydes.The YLA steamed bread was richer in esters,aldehydes,and acids than those from the other treatment groups.By contrast,alkanes and aldehydes were dominant in the Y and YL steamed breads.Therefore,the flavor and quality of the steamed bread made from the YLA sourdough could be improved obviously.These results could provide references for the application of AAB in dough fermentation and the improvement of new kinds of starters.
文摘In this study, mixed metal oxides developed with a perovskite-type structure that show great potential for use in catalysis. Perovskite oxide catalysts with the composition LaMoxV1-xOn （x = 0.1, 0.3, 0.5, 0.7, and 0.9） have been synthesized by the sol-gel method and then used in the ethane dry reforming reaction for the direct synthesis of acetic acid. The influence of the nature of the metallic source （metal, nitrate, acetylacetonate, and ammonium） on gel formation has been studied by Fourier-transform infrared spectroscopy （FT-IR） and thermogravimetric analysis （TGA-DTA）. After calcination, the obtained perovskites were characterized by X-ray diffraction （XRD） and energy-dispersive X-ray spectrometry （EDS） coupled with scanning electron microscopy （SEM）. The catalysts were then subjected to thermo-programmed reduction （TPR）. The surface area （BET） was found to increase from 2.6 m^2/g （x = 0.1） to 5.1 m2/g （x = 1.0） with increasing molybdenum content following calcinations at 750 °C, and pure LaMoxV1-xOn perovskite was obtained with good homogeneity. The catalysts have been characterized by XRD, SEM, EDS, and carbon analysis （CA）. The results indicate that through this synthesis it is possible to obtain highly crystalline, homogeneous and pure solids, with well-defined structures. The direct synthesis of acetic acid from ethane over the perovskite catalysts was studied at temperatures between 450 and 850 °C and elevated pressures between 1 and 8 bar. It was found that the yield of acetic acid and the selectivity of its formation could be increased by incorporating more molybdenum into the perovskite structure. The experimental studies have shown that the calcination temperature and the molybdenum content have a significant influence on the catalytic activity. Amongst the catalysts tested, LaMo0.7V0.3O4.2 exhibited the best activity and stability.
文摘In September 2009 a commercial unit for manufacture of acetic acid by low-pressure oxo-synthesis at the Guizhou Crystal Group had come on stream,which also symbolized the termination of the existing acetic acid production process by the mercury method characteristic of heavy pollution at the Guizhou Crystal Group.This project covers
文摘A study was conducted on the isolation of poplar （Populusxeurarnaricana （Dode） Guineir cv. I -72/58） wood components with aqueous acetic acid （AcOH） containing small amounts of sulfuric acid. The reaction time, concentration of acetic acid, ratio of liquor to wood, and concentration of acid catalyst were investigated to examine their effects on the fractionation of wood components. The three main separated components were characterized. The results showed that the optimum conditions for fractionation of poplar wood components were： 0.3% H2SO4 in reaction solution, ratio of liquor to wood 6, reflux time 3 h, and 90% AcOH. The residues were mainly composed of a-Cellulose and hemicellulose, The water insoluble precipitate （acetic acid lignin, AcL） had a low weight-average molecular weight range from 341 to 253 （Mw） and a narrow molecular weight distribution from 1.1 to 1.2. The sugar analysis revealed the solubilized products resulted mainly from hemicellulose and exited as monosaccharides.
文摘The excited-state double-proton transfer （ESDPT） mechanism of 2-amino-3-methoxypyridine and acetic acid com- plex is studied by the density functional theory （DFT） and time-dependent DFT with CAM-B3LYP functional. The complex is connected through two different types of inter-molecular hydrogen bonds. After photo-excitation, both hydrogen bonds get strengthened, which can facilitate the ESDPT reaction. The scanned potential energy curve along the proton transfer coordinate indicates that the ESDPT reaction proceeds in a stepwise pattern.
基金supported by the National Science Foundation of China(21776268,21721004,22108274 and 22378383)“Transformational Technologies for Clean Energy and Demonstration”,Strategic Priority Research Program of the Chinese Academy of Sciences,(XDA 21060200)support provided by Shanxi Yanchang Petroleum(Group)Co.,Ltd.(yc-hw-2022ky-02).
文摘Exploring stable and robust catalysts to replace the current toxic CuCr based catalysts for dehydrogenative coupling of ethanol to ethyl acetate is a challenging but promising task.Herein,novel NiIn based catalysts were developed by tailoring Ni catalysts with Indium(In)for this reaction.Over the optimal Ni0.1Zn0.7Al0.3InOx catalyst,the ethyl acetate selectivity reached 90.1%at 46.2%ethanol conversion under the conditions of 548 K and a weight hourly space velocity of 1.9 h^(-1)in the 370 h time on stream.Moreover,the ethyl acetate productivity surpassed 1.1 g_(ethyl acetate)g_(catalyst)^(-1)h^(-1),,one of the best performance in current works.According to catalyst characterizations and conditional experiments,the active sites for dehydrogenative coupling of ethanol to ethyl acetate were proved to be Ni4In alloys.The presence of In tailored the chemical properties of Ni,and subsequently inhibited the C-C cracking and/or condensation reactions during ethanol conversions.Over Ni4In alloy sites,ethanol was dehydrogenated into acetaldehyde,and then transformed into acetyl species with the removal of H atoms.Finally,the coupling between acetyl species and surface-abundant ethoxyde species into ethyl acetate was achieved,affording a high ethyl acetate selectivity and catalyst stability.
基金financially supported by the National Key R&D Program of China (2021YFA1501700)the National Science Foundation of China (22272114)+4 种基金the Fundamental Research Funds from Sichuan University (2022SCUNL103)the Funding for Hundred Talent Program of Sichuan University (20822041E4079)the NSFC (22102018 and 52171201)the Huzhou Science and Technology Bureau (2022GZ45)the Hefei National Research Center for Physical Sciences at the Microscale (KF2021005)。
文摘The conversion of waste polylactic acid(PLA)plastics into high-value-added chemicals through electrochemical methods is a promising and sustainable approach.However,developing efficient and highly selective catalysts for lactic acid oxidation reaction(LAOR)and understanding the reaction process are challenging.Here,we report the electrooxidation of waste PLA to acetate at a high current density of 100 mA cm-2 with high Faraday efficiency(~95%)and excellent stability(>100 h)over a nickel selenide nanosheet catalyst.In addition,a total Faraday efficiency of up to 190%was achieved for carboxylic acids,including acetic acid and formic acid,by coupling with the cathodic CO_(2) reduction reaction.In situ experimental results and theoretical simulations revealed that the catalytic activity center of LAOR was dynamically formed NiOOH species,and the surface-adsorbed SeO_(x) species accelerated the formation of Ni~(3+)species,thus promoting catalytic activity.The mechanism of lactic acid electrooxidation was further elucidated.Lactic acid was dehydrogenated to produce pyruvate first and then formed CH_3CO due to preferential C-C bond cleavage,resulting in the presence of acetate.This work demonstrated a sustainable method for recycling waste PLA and CO_(2) into high-value-added products.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11574113,11374123,and 11104106)Science and Technology Planning Project of Jilin Province,China(Grant Nos.20180101238JC,20170204076GX,20180101006JC,20190103041JH,and 20190201260JC)Post-Doctoral Innovative Talent Support Program,China(Grant Nos.BX20180127 and 2019M651192)
文摘The acetic acid-water binary system is a classical hydroxy-carboxy mixed system, while new and interesting phenomena appear under stimulated Raman scattering(SRS).Compared with the weaker signal of the acetic acid-water binary system obtained in spontaneous Raman scattering, SRS provides a finer band and a relatively distinct structural transition point.The structural transformation points are respectively at 30% and 80% by volume ratio under the condition of spontaneous Raman spectroscopy, while they are respectively at 15% and 25% under the condition of SRS.This phenomenon is attributed to the generation of laser induced plasma and shockwave induced dynamic high pressure environment during SRS.
