Synthesis of ethyl acetate by esterification of acetic acid with ethanol over a heteropolyacid on montmorillonite K10

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.

Tailoring Ni based catalysts by indium for the dehydrogenative coupling of ethanol into ethyl acetate

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.

Production of Bio-gasoline by Co-cracking of Acetic Acid in Bio-oil and Ethanol

Abstract Acetic acid was selected as the model compound representing the carboxylic acids present in bio-oil. This work focuses the co-cracking of acetic acid with ethanol for bio-gasoline production. The influences of reaction temperature and pressure on the conversion of reactants as well as the selectivity and Conaposition of the crudegasoline phase were investigated. It was found that increasing reaction temperature benefited the conversion of reactants and pressurized cracking produced a higher crude gasoline yield. At 400 ℃ and 1 MPa, the conversion of the reactants reached over 99% and the selectivity of the gasoline phase reached 42.79% （by mass）. The gasoline phase shows outstanding quality, with a hydrocarbon content of 100%.

Pressure Swing Distillation for Separation of Ethyl Acetate and Ethanol in Sub-plateau Region

The pressure swing distillation(PSD)process for separation of ethyl acetate and ethanol mixture in subplateau region was simulated.The pressure of low-pressure column was set at 0.086 MPa,which is in accordance with the atmospheric pressure in the Yunnan-Guizhou region,while the pressure of high-pressure column was determined as 0.304 MPa.Various design parameters,including the plate number,the reflux ratio,and the feeding positions,were optimized,while taking into consideration the total annual cost(TAC).Furthermore,based on the general PSD,the partially heatintegrated pressure swing distillation(PHIPSD)process and the fully heat-integrated pressure swing distillation(FHIPSD)process were also studied.The processes with heat integration showed lower capital cost and lower energy cost,and TACs of the PHIPSD and FHIPSD decreased to 377.21×103$/a and 371.66×103$/a,respectively.Compared with the non-heat integrated process,TACs of the PHIPSD and FHIPSD could be reduced by 27.82%and 28.89%,respectively.The results showed that the FHIPSD process could effectively separate the ethyl acetate-ethanol mixture,and it was more economical and reasonable.This work can provide some technical references for the separation of such azeotropes in the sub-plateau region.

Thermoresistant, Ethanol-Resistant and Acid-Resistant Properties of Acetic Acid Bacteria Isolated from Fermented Mango Alcohol

Vinegar production is seriously affected by the sensitivity of acetic acid bacteria (AAB) to high temperature, high ethanol concentrations, and high acetic acid concentrations. The aim of this study was to investigate the thermo-ethanol-acid tolerance characters of five AAB strains (VMA1, VMA5, VMA7, VMAM, VMAO) previously isolated from fermented mango alcohol and belonging to Gluconoacetobacter genera. As result, the five AAB strains exhibited good growth and acid production at temperatures up to 45°C;they could tolerate and produce acetic acid at ethanol concentrations up to 20% (v/v). In addition, the studied strains showed growth at acetic acid concentrations up to 4.5% (w/v). Strains VMA7 and VMAO showed the highest resistance properties: they demonstrated acid production at 50°C and VMAO could even grow at 60°C;they tolerated and produced acetic acid at 25% (v/v) ethanol concentration;they showed resistance to acetic acid concentrations up to 6% (w/v). Considering all these properties, the use of these strains would seriously contribute to improving the quality of the vinegar produced and help to reduce the cooling water feeds in vinegar production especially in hot countries in the context of global warming.

Acetic acid-and furfural-based adaptive evolution of Saccharomyces cerevisiae strains for improving stress tolerance and lignocellulosic ethanol production

Acetic acid and furfural are known as prevalent inhibitors deriving from pretreatment during lignocellulosic ethanol production.They negatively impact cell growth,glucose uptake and ethanol biosynthesis of Saccharomyces cerevisiae strains.Development of industrial S.cerevisiae strains with high tolerance towards these inhibitors is thus critical for efficient lignocellulosic ethanol production.In this study,the acetic acid or furfural tolerance of different S.cerevisiae strains could be significantly enhanced after adaptive evolution via serial cultivation for 40 generations under stress conditions.The acetic acid-based adaptive strain SPSC01-TA9 produced 30.5 g·L^(-1)ethanol with a yield of 0.46 g·g^(-1)in the presence of 9 g·L^(-1)acetic acid,while the acetic acid/furfural-based adaptive strain SPSC01-TAF94 produced more ethanol of 36.2 g·L^(-1)with increased yield up to 0.49 g·g^(-1)in the presence of both 9 g·L^(-1)acetic acid and 4 g·L^(-1)furfural.Significant improvements were also observed during non-detoxified corn stover hydrolysate culture by SPSC01-TAF94,which achieved ethanol production and yield of 29.1 g·L^(-1)and 0.49 g·g^(-1),respectively,the growth and fermentation efficiency of acetic acid/furfural-based adaptive strain in hydrolysate was 95%higher than those of wildtype strains,indicating the acetic acid-and furfural-based adaptive evolution strategy could be an effective approach for improving lignocellulosic ethanol production.The adapted strains developed in this study with enhanced tolerance against acetic acid and furfural could be potentially contribute to economically feasible and sustainable lignocellulosic biorefinery.

Formation mechanisms of ethyl acetate and organic acids in Kluyveromyces marxianus L1-1 in Chinese acid rice soup

This study aims to explore the formation mechanism of ethyl acetate and organic acids in acid rice soup(rice-acid soup)inoculated with Kluyveromyces marxianus L1-1 through the complementary analysis of transcriptome and proteome.The quantity of K.marxianus L1-1 varied significantly in the fermentation process of rice-acid soup and the first and third days were the two key turning points in the growth phase of K.marxianus L1-1.Importantly,the concentrations of ethyl acetate,ethanol,acetic acid,and L-lactic acid increased from day 1 to day 3.At least 4231 genes and 2937 proteins were identified and 610 differentially expressed proteins were annotated to 30 Kyoto Encyclopedia of Genes and Genomes(KEGG)pathways based on the analysis results of transcriptome and proteome.The key genes and proteins including up-regulated alcohol dehydrogenase family,alcohol O-acetyltransferase,acetyl-CoA C-acetyltransferase,acyl-coenzyme A thioester hydrolase,and down-regulated aldehyde dehydrogenase family were involved in glycolysis/gluconeogenesis pathways,starch and sucrose metabolism pathways,amino sugar and nucleotide sugar metabolism pathways,tricarboxylic acid(TCA)cycle,and pyruvate metabolism pathways,thus promoting the formation of ethyl acetate,organic acids,alcohols,and other esters.Our results revealed the formation mechanisms of ethyl acetate and organic acids in rice-acid soup inoculated with K.marxianus L1-1.

A Comparative Study of Ultrasound-Guided Intratumoral Acetic Acid and Ethanol Injection Therapy for Liver Tumors in Rats

To compare the therapeutic efficacy of USguided intratumoral injection of acetic acid and ethanol in 77 rats with transplanted Walker256 carcinosarcoma. The rats were divided into three groups: intratumoral acetic acid injection (IAI), intratumoral ethanol injection (IEI), and control group receiving intratumoral saline injection (ISI). Tumor growth rates were measured. Pathologic changes were chronologically observed, and tumor necrosis was quantified as a percentage of the tumor volume using a semiquantitative method. Results: Tumor growth rates were -(37±23)% in the IAI group, (210±174)% in the IEI group and (1 303±473)% in the ISI group (P<0.05). Tumor necrosis rates were (97.4±3.7)%, (79.4±10.9)% and (27.2±10.3)% respectively (P<0.01). In addition, the pathologic results showed that necrosis was more complete and repair of the peripheral tissue of tumor was faster in the IAI group as compared with the IEI group. Conclusion: IAI is more effective than IEI in the local therapy for liver tumors.

Development of <i>α</i>-Amino Acid Detection with Peroxyoxalate Chemiluminescence by Using Water-Acetonitrile-Ethyl Acetate Mixed Solution

Peroxyoxalate chemiluminescence was, for the first time, examined by using ternary mixed solutions of water-hydrophilic/hydrophobic organic solvent. Eosin Y as a model fluorescence compound was dissolved with the ternary solutions of water (1.0 mM carbonate buffer, pH 9.0)-acetonitrile-ethyl acetate, water-rich of 15:3:2 volume ratio and organic solvent-rich of 3:8:4 volume ratio, to which bis(2,4,6-trichlorophenyl) oxalate and hydrogen peroxide chemiluminescence reagent were added. The chemiluminescence observed with the ternary solutions, especially the organic solvent-rich solution, showed a larger signal than that observed with the water only solution or water-acetonitrile mixed solution. Chemiluminescence in the presence of twenty types of α-amino acid was similarly examined by using the ternary organic solvent-rich solution. The chemiluminescence of three α-amino acids with fluorescence properties was enhanced with the ternary solution. The data reported here may contribute to development of a new, sensitive peroxyoxalate chemiluminescence detection system.

Catalytic upgrading biomass-derived ethanol and acetic acid into C4 chemicals

Synthesis of value-added chemicals from biomass is an essential strategy to mitigate the global dependency on fossil resources and achieve the aim of carbon neutrality. Thereinto, ethanol and acetic acid are crucial biomass-derived platform molecules.Recently, catalytic upgrading ethanol and acetic acid into C4 energy-intensive fuels and chemicals via the elongation of carbon backbone has received widespread attention. The primary focus of this review is to systematically describe the recent breakthrough in the conversion of ethanol or acetic acid to C4 chemicals including 1,3-butadiene, n-butenes, isobutene or n-butanol.Special attentions will be given to heterogeneous catalyst design strategies, reaction parameters on the catalytic performance along with the relevant mechanism investigations, as well as their future challenges and opportunities. The present review will provide the detailed insights into the synthesis of C4 chemicals from biomass-derived ethanol and acetic acid and shed a light on the development of highly efficient catalysts.

Transformation of Ethanol to Ethyl Acetate over Cu/SiO2 Catalysts Modified by ZrO2

Direct transformation of ethanol to ethyl acetate was investigated on a series of Cu（ZrO2）/SiO2 catalysts. Inductively coupled plasma（ICP）, surface area analysis, X-ray diffraction（XRD）, H2-temperature programmed reduc- tion（H2-TPR）, X-ray photoelectron spectroscopy（XPS）, NH3-temperature programmed desorption（NH3-TPD） and Fourier transform-infrared spectroscopy（FTIR） techniques were used to characterize the catalysts. The results reveal that ZrO2 can improve the dispersion of copper species and increase the acidity of the Cu（ZrO2）/SiO2 catalysts. The Cu0 is responsible for ethanol dehydrogenation to acetaldehyde, and both the Lewis acid and Bronsted acid sites were in favor of the selectivity to ethyl acetate. The synergistic effect of Cu0 and an appropriate amount of acidic sites played an important role in the production of ethyl acetate.

Effects of pomegranate ethyl acetate extract on rat islet cells

Objective The present study investigated the effects of pomegranate ethyl acetate extract(PEE)on cell viability of primary rat islet cells.Methods PEE was extracted by using 95% ethanol and a series of organic solvents.Primary isolated islet cells of rat were cultured in high glucose and/or high fat conditions with or without PEE.Cell viability was determined by MTT assay.Insulin secretion was assessed by using radioimmunoassay.Results Insulin levels were significantly higher in cells treated with high glucose+PEE,palmitic acid+PEE,and olein acid+PEE compared to the cells treated with high glucose,palmitic acid,or oleic acid alone,in which the insulin levels were markedly less than that of the normal control group.Conclusion PEE promotes islet cell growth and insulin secretion,which is suggested that PEE can protect islet cell function in both high glucose and high fatty acid environments.

Towards Biorefinery Production of Microalgal Biofuels and Bioproducts: Production of Acetic Acid from the Fermentation of <i>Chlorella</i>sp. and <i>Tetraselmis suecica</i>Hydrolysates

Successful commercialization of microalgal bio-industry requires the design of an integrated microalgal biorefinery system that facilitates the co-production of biofuels, high-value products and industrial chemicals from the biomass. In this study, we investigated the use of sugar hydrolysate obtained from enzymatic saccharification of microalgal biomass (Chlorella sp. and T. suecica) as fermentation feedstock to produce industrially important chemicals, in particular acetic acid and butyric acid. By using hydrolysate with low sugar content as substrate for the anaerobic fermentation (1.5 - 2.4 g/L), we were able to prevent the bacterium C. saccharoperbutylacetonicum from activating its solventogenesis pathway. As a result, the fermentation process generated a product stream that was dominated by organic acids (acetic acid and butyric acid) rather than solvents (butanol, ethanol and acetone). Acetic acid constituted up to 92 wt% of Chlorella’s fermentation products and 80 wt% of T. suecica’s fermentation products. For T. suecica, the fermentation consumed almost all of the sugar available in the hydrolysate (up to 92% of initial sugar) and produced a reasonable yield of fermentation products (0.08 g fermentation products/g sugar). The Gompertz equation was successfully used to predict the formation kinetics of acetic acid and other fermentation products across both species. The results in the study demonstrate the production of industrially important chemicals, such as acetic acid and butyric acid, from the fermentation of microalgal sugar. The process described in the study can potentially be used as a value-adding step to generate biochemicals from cell debris in an integrated microalgal biorefinery system.

Catalytic Hydrogenation of Acetic Acid to Acetaldehyde: Synergistic Effect of Bifunctional Co/Ce-Fe Oxide Solid Solution Catalysts

The large-scale industrial production of acetic acid (HAc) from carbonylation of methanol has enabled intense research interest from direct hydrogenation of HAc to acetaldehyde (AA).Herein,a series of cerium-iron oxide solid solution supported metallic cobalt catalysts were prepared by modified sol-gel method and were applied in gas-phase hydrogenation of HAc to AA.A synergistic effect between the hydrogenation metal cobalt and Ce-Fe oxide solid solution is revealed.Specifically,oxygen vacancies provide the active sites for adsorption of HAc,while highly uniformly dispersed metallic Co adsorbs H2 and activates the reduction of HAc into AA.Moreover,the metallic Co can also assist the cyclical conversion between Fe3+/Fe2+ and Ce3+/Ce4+ on the surface of Ce1.xFexO2-δ supports.The unique effect substantially enhances the ability of the support material to rapidly capture oxygen atoms from HAc.It is found that the catalyst of 5% Co/Ce0.8Fe0.2O2-δ with the highest concentration of oxygen vacancy presents the best catalytic performance (i.e.acetaldehyde yield reaches 49.9%) under the optimal reaction conditions (i.e.623 K and H2 flow rate =10 mL/min).This work indicates that the Co/Ce-Fe oxide solid solution catalyst can be potentially used for the selective hydrogenation from HAc to AA.The synergy between the metallic Co and Ce1-xFexO2-δ revealed can be extended to the design of other composite catalysts.

A Computational Study on Iridium-Catalyzed Production of Acetic Acid from Ethanol and Water Solution

The mechanism for the production of acetic acid from ethanol and water mixture catalyzed by iridium catalyst has been theoretically investigated.The cooperation of the iridium center and bpyO ligand is highlighted,which plays an important role in the catalytic activity.The hydrogen release from the iridium center is the rate-determining step,with an energy barrier of 22.5 kcal/mol.The electronic structure analysis suggests electron-donating substituents could decrease the energy barrier.

Therapeutic potential of ethyl acetate fraction of Tephrosia purpurea Linn.leaves in a rat model of gout

Objective: The present study is to determine the potential treatment effects of ethyl acetate fraction of Tephrosia purpurea Linn. leaves(EATP) against gout.Methods: Gout in experimental rats was induced with potassium oxonate at the dose of 250 mg/kg(intraperitoneal injection) for 7 consecutive days;EATP was administered 1 h after administration of the potassium oxonate on each day of experiment. Potassium oxonate was discontinued on the 8 th day;thereafter allopurinol(10 mg/kg, p.o.) and EATP(200 and 400 mg/kg, p.o.) were continued until day 14. The uric acid level was measured from serum and urine during the experiment. Other biochemical parameters were assessed, including blood and urine creatinine, erythrocyte sedimentation rate, and total protein. Blood urea nitrogen, serum aspartate aminotransferase serum alanine aminotransferase and alkaline phosphatase were also measured. The blood was analyzed for levels of malondialdehyde and the antioxidant enzymes such as superoxide dismutase, catalase and glutathione peroxidase.Histopathological and radiological changes in the ankle of rats were observed after completion of the experiment.Results: EATP was able to decrease serum uric acid and creatinine level;it also reduced inflammation,oxidative stress and lysosomal enzyme level, which has a role in acute inflammation. EATP increased uric acid excretion through urine due to its uricosuric effect.Conclusion: EATP lowered the serum uric acid level and increased the urine uric acid level through excretion, which is useful in the treatment of gout. Hence the EATP was found to be helpful in the treatment of gout.

Effect of thermal pretreatment on the surface structure of PtSn/SiO2 catalyst and its performance in acetic acid hydrogenation

The effect of thermal pretreatment on the active sites and catalytic performances of PtSn/SiO2 catalyst in acetic acid （AcOH） hydrogenation was investigated in this article. The catalysts were characterized by N2 physical adsorption, X-ray diffraction, transmission electron microscopy, pyridine Fourier-transform infrared spectra, and H2-O2 titration on its physicochemical properties. The results showed that Pt species were formed primarily in crystalline structure and no PtSnx alloy was observed. Meanwhile, with the increment of thermal pretreatrnent temperature, Pt dispersion showed a decreas- ing trend due to the aggregation of Pt particles. Simultaneously, the amount of Lewis acid sites was remarkably influenced by such thermal pretreatment owning to the consequent physicochemical property variation of Sn species. Interestingly, the catalytic activity showed the similar variation trend with that of Lewis acid sites, confirming the important roles of Lewis acid sites in AcOH hydrogenation. Moreover, a balancing effect between exposed Pt and Lewis acid sites was obtained, resulting in the superior catalytic performance in AcOH hydrogenation.

The cooperation effect of Ni and Pt in the hydrogenation of acetic acid

The catalytic hydrogenation of carboxylic acid to alcohols is one of the important strategies for the conversion of biomass.Herein,a series of Ni-doped PtSn catalysts were prepared,characterized and studied in the hydrogenation of acetic acid.The Ni dopant has a strong interaction with Pt,which promotes the hydrogen adsorption,providing an activated hydrogen-rich environment for the hydrogenation.Meanwhile,the presence of Ni also improves the Pt dispersion,giving more accessible active sites for hydrogen activation.The cooperation of Pt and Ni significantly promotes the catalytic activity of the hydrogenation of acetic acid to ethanol.As a result,the catalyst with 0.1%Ni exhibits the best reaction activity,and its space time yield is twice as that of the PtSn/SiO2 catalyst.It provides a meaningful instruction on the catalyst design for the carboxylic acid hydrogenation.

Impact of Ionic Liquid 1-Ethyl-3-Methylimidazolium Acetate Mediated Extraction on Lignin Features

This study aims at investigating the impact of ionic liquid extraction on lignin structure by studying the mechanism of lignin depolymerization in 1-ethyl-3-methylimidazolium acetate EMIM[OAc]) and comparing it with that of organosolv and milled wood methods. Ionic liquid mediated lignin (ILL) using EMIM[OAc]), ethanol organosolv lignin (EOL) and milled wood lignin (MWL) were isolated from Typha capensis (TC) and subjected to several analytical characterizations. Experimental data shows that ILL exhibited a relatively lower degree of condensation, lower aromatic C-C structures and a higher aliphatic OH with values of 0.42/Ar, 1.94/Ar and 1.33/Ar moieties compared with EOL values of 0.92/Ar, 2.22/Ar and 0.51/Ar moieties respectively. The ILL was depolymerized under mild conditions giving relatively higher β-aryl ether linkages content, higher molecular mass, and exhibited closer structures and reactivity to native lignin than EOL. These insights on TC lignin depolymerization in EMIM[OAc]) acetate may contribute to better value-addition of lignocellulosic biomass.

Synthesis, Spectroscopic and Crystal Structure Studies on Ethyl 5,7-Dimethyl Coumarin-4-Acetate

Ethyl ester of 5,7-dimethyl coumarin-4-acetic acid has been synthesized from 3,5-Xylenol in a two step sequence of reaction involving Pechmann cyclisation and acid catalyzed esterification. The title compound 2 crystallizes in Monoclinic form, space group P 1 21/c 1, with a = 8.6248(4) ?, b = 18.9103(8) , c = 8.4204(4)?, β = 101.241(2)?, V = 1347.00(11) ?, D cal = 1.283 Mg/cm3, Z = 4. The molecule is stabilized by intermolecular C-H … O bonds.