System 1-butanol Research Articles

Biobutanol extraction and dehydration with eucalyptus oil yielding linear and cyclic biofuel blends

AbstractThe biobutanol‐based biofuel fermentation is hindered by the challenge of inadequate fermentation broth concentration and the azeotropic systems of water. The application of eucalyptus oil in diesel fuel makes it a promising extractant for biobutanol extraction and dehydration, thus resulting in product recovery and the development of fuel blend technology. Eucalyptus oil‐derived 1,8‐cineole was applied to acetone‐butanol‐ethanol (ABE) and isobutanol systems to enhance the butanol recovery and dehydration. The recovery of n‐butanol and isobutanol reached 92% and 95%, respectively, while the water removal in a 2% butanol system exceeded 99%. These results demonstrated that 1,8‐cineole exhibited a high selectivity toward butanol, thus providing a robust theoretical foundation for the fermentation‐based biofuel recovery and the elimination of azeotropic systems. The introduction of high‐density diesel‐fuel‐like eucalyptus oil into low‐energy‐density biobutanol will increase the energy density of fermentation‐based alcohols, yielding linear and cyclic biofuel blends.

AP-x,y Equilibrium data of the binary systems of 1-Butanol and 2-Butanol with argon at 313.15 K and 333.15 K – Measurements and modeling

The equilibrium composition of two binary systems (argon–1-butanol and argon–2-butanol) was measured at 313.15 K and 333.15 K and at pressures up to 640 bar. A high-pressure optical view cell was used for the experiments, while theoretical calculations were based on the Peng-Robinson Equation of State with the Boston-Mathias alpha function. Different equilibrium compositions of argon in butanol isomers, as well as butanol isomer in argon were observed despite the similar molecular weight of isomers (M1-butanol = 74.121 g mol−1 and M2-butanol = 74.122 g mol−1) and a functional hydroxyl group. The difference in vapour pressure, dipole moment and solute-solute interactions lead to different solubility values. Nevertheless, the importance of data predicted by theoretical calculations is based on the possibility of obtaining an approximation to the thermodynamic behaviour of the real systems without the necessity of experimental data.

Experimental VLE Data of Binary Systems of Ester + Alcohol at 0.6 MPa. Verification using new Association Parameters for the Point– to–Point Test

Experimental data of vapor–liquid equilibria (VLE) are reported for the following binary systems: butyl acetate+ethanol, butyl acetate+1–propanol and butyl acetate+1–butanol at 0.6 MPa. No azeotrope was found in the butyl acetate+1–butanol system at 0.6 MPa. The thermodynamic consistency of the obtained data was analyzed using some equations of state (EOS) in the point–to–point test. The phase behavior was satisfactorily modelled using the Peng–Robinson EOS. The new association parameter of the Hayden–O’Connell method was determined from 144 pure substances and the influence of the second virial coefficient calculations in the point–to–point test was evaluated.

P-x,y Equilibrium Data of the Binary Systems of 2-Propanol, 1-Butanol and 2-Butanol with Carbon Dioxide at 313.15 K and 333.15 K

The ability to predict the behaviour of high-pressure mixtures of carbon dioxide and alcohol is important for industrial purposes. The equilibrium composition of three binary carbon dioxide-alcohol systems was measured at temperatures of 313.15 K and 333.15 K and at pressures of up to 100 bar for carbon dioxide-2-propanol, up to 160 bar for carbon dioxide-1-butanol and up to 150 bar for carbon dioxide-2-butanol. Different equilibrium compositions of carbon dioxide in alcohols were observed despite their similar molecular weight (M2-propanol = 60.100 g mol-1, M1-butanol = 74.121 g mol-1 and M2-butanol = 74.122 g mol-1) and place in the functional hydroxyl group (first or second carbon molecule). It is assumed that the differences in the phase equilibria are due to different vapor pressures, polarities and solute-solute interactions.

A biodegradable polymer-assisted efficient and universal exfoliation route to a stable few layer dispersion of transition metal dichalcogenides

Quasi two-dimensional transition metal dichalcogenides (2D-TMDs) with 1–5 layers have been obtained by developing an effective and highly efficient bio-based polymer-solvent system by mild ultrasonication. The hydroxypropyl cellulose (HPC)/1-Butanol (BuOH) system was determined to be an universal polymer-solvent system to effectively exfoliate the bulk transition metal dichalcogenides (TMDs) MoS2, TiS2, WS2, NbS2 and MoSe2. The above process is significant as it is a room temperature liquid phase exfoliation method that leads to a stable dispersion of a few layer 2D-TMD having significant proportion (>50%) of exfoliated material which remains stable in suspension for several months.

Equilibrium Study and Analysis of Site Energy Distribution of Butanol Sorption on a Biosorbent

A biosorbent derived from oat hulls was employed to dehydrate butanol from water mixture to obtain a high-purity butanol product. As this process involves water and butanol binary sorption, it is important to investigate equilibrium of water and butanol sorption on the biosorbent. Previous studies investigated water sorption from a mixture of butanol and water. This work emphasizes the equilibrium of butanol sorption from pure butanol and butanol–water binary systems. The Dubinin–Polanyi models (applicable to micropore and large pore materials), which are equilibrium models derived from the adsorption potential theory of Polanyi, were applied to simulate the experimental data for butanol sorption on the aforementioned biosorbent. The models agreed with the experimental data. The parameter q0 (limiting mass for sorption) was estimated in the butanol–water binary as well as the pure butanol systems. The comparison of q0 from single and binary systems indicated that the competitive sorption occurred between butanol and water on the biosorbent. In order to analyze the energetics of the butanol sorption, the approximate site energy distribution of butanol sorption was further investigated. The results showed that water sorption had a higher value of weighted mean of site energy distribution than butanol sorption. This biosorbent had higher affinity to water and therefore had higher water sorption capacity. The dipole–dipole attraction, one kind of van der Waals force, could be one of the key mechanisms of butanol sorption by the biosorbent. Additionally, thermodynamic parameters were determined. The results indicated that the butanol sorption process was spontaneous and exothermic.

Vapor-liquid equilibria for binary and ternary systems composed of acetone, 1-butanol, and ethanol at atmospheric pressure

The experimental vapor-liquid equilibrium data for three binary systems of acetone + 1-butanol, ethanol + 1-butanol, acetone + ethanol and a ternary system of ethanol + acetone + 1-butanol at atmospheric pressure were measured using an ebulliometer. The binary experimental data were correlated using the Wilson, NRTL, and UNIQUAC models to obtain the binary interaction parameters of the models. These parameters were used to predict the ternary equilibrium data. The average absolute deviations of temperature (AAD T) between the experimental and correlation data of the three models are the same, 0.63, for the acetone + 1-butanol system, 0.72, 0.65, and 0.70, for the ethanol + 1-butanol system, and 0.15, 0.30, and 0.19, for the acetone + ethanol system, respectively. The AAD T values for the ternary system of ethanol + acetone + 1-butanol by comparing the experimental data with the data calculated using the three models were 0.28, 0.56, and 0.67, respectively.

Mechanism Analysis for Separation of Cyclohexane and tert-Butanol System via Ionic Liquids as Extractants and Process Optimization

Ionic liquids (ILs) are used in separation of organic substances in industry. In order to screen suitable ILs for industrial separation, the interaction between molecules is studied based on the ex...

Vapor–Liquid Equilibrium for Binary of 1-Butanol + N,N-Dimethylacetamide and Methyl Isobutyl Ketone + N,N-Dimethylacetamide at 101.3 kPa

Vapor–liquid equilibrium data for the binary systems of 1-butanol + N,N-dimethylacetamide and methyl isobutyl ketone + N,N-dimethylacetamide were measured at 101.3 kPa. The vapor–liquid equilibrium experiments of two systems were carried out in the modified Rose vapor recirculating-type equilibrium still. Van Ness and Herington tests were used to check the thermodynamic consistency of the experimental data. After meeting the thermodynamic consistency test, the nonrandom two-liquid, universal quasichemical, and Wilson models were used for correlation and regression of the experimental data. The binary interaction parameters of each model for the two binary systems were obtained. Comparing the equilibrium temperature and vapor-phase mole fraction for the experimental value and the calculated value, it shows that the two models had a good correlation with the experimental data.

Understanding water interactions with organic surfaces: environmental molecular beam and molecular dynamics studies of the water-butanol system.

The interactions between water molecules and condensed n-butanol surfaces are investigated at temperatures from 160 to 240 K using the environmental molecular beam experimental method and complementary molecular dynamics (MD) simulations. In the experiments hyperthermal water molecules are directed onto a condensed n-butanol layer and the flux from the surface is detected in different directions. A small fraction of the water molecules scatters inelastically from the surface while losing 60-90% of their initial kinetic energy in collisions, and the angular distributions of these molecules are broad for both solid and liquid surfaces. The majority of the impinging water molecules are thermalized and trapped on the surface, while subsequent desorption is governed by two different processes: one where molecules bind briefly to the surface (residence time τ < 10 μs), and another where the molecules trap for a longer time τ = 0.8-2.0 ms before desorbing. Water molecules trapped on a liquid n-butanol surface are substantially less likely to escape from the surface compared to a solid layer. The MD calculations provide detialed insight into surface melting, adsorption, absorption and desorption processes. Calculated angular distributions and kinetic energy of emitted water molecules agree well with the experimental data. In spite of its hydrophobic tail and enhanced surface organization below the melting temperature, butanol's hydrophilic functional groups are concluded to be surprisingly accessible to adsorbed water molecules; a finding that may be explained by rapid diffusion of water away from hydrophobic surface structures towards more strongly bound conformational structures.

A systematic study on volumetric and transport properties of binary systems 1-propanol + n-hexadecane, 1-butanol + n-hexadecane and 1-propanol + ethyl oleate at different temperatures: Experimental and modeling

Densities (ρ), viscosities (η), speed of sounds (u) and refractive indices (nD) at temperature range (293.15–343.15) K with 5 K interval, for three binary mixtures (1-propanol + n-hexadecane, 1-butanol + n-hexadecane and 1-propanol + ethyl oleate), were measured at atmospheric pressure. Based on the corresponding experimental data, excess molar volume (VE), viscosity deviation (Δη) and deviation in refractive index (ΔnD) have been calculated. Beside these properties, molar excess Gibbs free energies of activation of viscous flow (Δ*GE) and deviation in isentropic compressibility (Δκs) were calculated from measured density, viscosity and speed of sound data. The excess/deviation functions have been fitted by Redlich-Kister equation and discussed in terms of molecular interactions existing in the mixtures. Viscosity modeling was performed using four models: UNIFAC-VISCO, ASOG-VISCO, Teja-Rice and McAllister. Experimental viscosity data have been used to determine new binary UNIFAC-VISCO and ASOG-VISCO interaction parameters and the interaction parameters for correlation models by applying some optimization technique. For all systems, positive deviations were observed for the excess molar volumes in the whole concentration range. A negative deviation and an inversion sign for the excess dynamic viscosity were observed in the systems of 1-butanol + n-hexadecane and 1-propanol + n-hexadecane, respectively, while positive deviation was observed for 1-propanol + ethyl oleate mixture. The results of viscosity modeling showed that four-body McAllister models are suitable to describe viscosities for all systems and temperatures with maximum percentage deviations (PDmax) less than 0.5%.

A Simple Method for Quantifying Polycarbonate and Polyethylene Terephthalate Microplastics in Environmental Samples by Liquid Chromatography–Tandem Mass Spectrometry

Microplastics (MPs) have frequently been found in the environment. However, studies of the quantification methods for MPs are still needed. Plastics are polymers with different degrees of polymerization. In this study, alkali-assisted thermal hydrolysis was applied to depolymerize two plastics containing ester groups, polycarbonate (PC) and polyethylene terephthalate (PET), in a pentanol or butanol system. By determining the concentrations of the depolymerized building block compounds, i.e., bisphenol A and p-phthalic acid, we quantified the amounts of PC and PET MPs in environmental samples. Recoveries of 87.2–97.1% were obtained for the PC and PET plastic particles spiked in the landfill sludge. The method was successfully applied to determine the occurrence of PC and PET MPs in samples of sludge, marine sediments, indoor dust, digestive residues in mussel and clam, and sea salt and rock salt. High concentrations of 246 and 430 mg/kg were determined for PC and PET type MPs, respectively, in an indoor du...

Thermophysical properties of 1,2,4-trimethylbenzene in admixtures with 1-butanol or 2-butanol at high pressures

The systems of 1-butanol or 2-butanol+1,2,4-trimethylbenzene were characterized measuring densities and isobaric heat capacities at high pressures. Densities of 2-butanol and 1,2,4-trimethylbenzene and the binary systems 1-butanol or 2-butanol+1,2,4-trimethylbenzene were measured at the ranges p=(0.1–140)MPa and T=(273.15–333.15)K. For these measurements, a high-pressure vibrating tube densimeter was used and data were successfully correlated with the empirical Tammann-Tait equation. In order to complete the characterization, isobaric heat capacities were measured over the range of (0.1–25)MPa at two different temperatures (293.15 and 313.15)K for the same pure compounds and binary mixtures. These measurements were performed in a high-pressure automated flow calorimeter. Excess molar heat capacities were evaluated for the mixtures and a positive deviation from the ideality was obtained for both systems.

Effect of Phase-Equilibrium Uncertainties on the Separation of Heterogeneous Azeotropes—Application to the Water + 1-Butanol System

This paper extends application of the Margules-based phase-equilibrium uncertainty method to a system exhibiting a heterogeneous azeotrope. The author developed the method in order to provide pract...

Viscosities of binary liquid systems: Prediction and correlation

The viscosity of binary liquid systems of 1-Butanol, C 4 H 9 OH with Hexadecane, C 16 H 34 and Squalane, C 30 H 62 , were determined theoretically over the complete concentration range, at 298.15, 303.15, 308.15 K and at atmospheric pressure. Hinds relation and modified Kendall-Monroe method is employed in the calculation. Deviation in viscosity is calculated and the obtained results were analysed in terms of the applied approach, the structure of the investigated system, the nature of components of the binary liquid systems and the interactions in the system.

Extraction of Lactic Acid in Mixed Solvent Electrolyte System Containing Water, 1-Butanol and Ammonium Sulfate

Abstract Extraction of lactic acid from its aqueous solution was carried out at 30.0°C in a mixed solvent electrolyte system containing water, 1-butanol and ammonium sulfate ((NH4)2SO4). The salt appeared to reduce mutual solubility between water and 1-butanol leading to an enlarged two-phase region of the mixture. The effect was more pronounced at high salt concentration. In view of extraction, ternary mixture containing water, 1-butanol and lactic acid, (NH4)2SO4 effectively salted-out 1-butanol and lactic acid leading to a reduced concentration of these two components in the aqueous phase. Distribution coefficient and degree of lactic acid extraction were significantly improved with increasing concentration of the salt. Additionally, (NH4)2SO4 helped lessen the transfer of one solvent into the other, which is the problem normally encountered in extraction when partially miscible solvents are employed. It also advantageously allowed the extraction to be carried out at a high solvent-to-aqueous phase volume ratio, where large recovery of the acid was achieved. Extraction of lactic acid in this mixed solvent electrolyte system could be further improved by operating it in a stage-wise mode rather than a batch one.

Vapor–Liquid Equilibria, Density, Speed of Sound, and Viscosity for the Poly(ethylene glycol) 400 + 1-Propanol and 1-Butanol Systems

By using the improved isopiestic method, solvent activity measurements have been performed on the systems poly(ethylene glycol) 400 (PEG 400) + 1-propanol and 1-butanol at 298.15 K. Calcium chloride was used as the isopiestic standard for the calculation of activities. The obtained solvent activity data were correlated with the original Flory–Huggins model. The strength of interaction between different alcohols and the polymer was discussed on the basis of the obtained Flory–Huggins interaction parameters. Measurement of the density, speed of sound, and viscosity data were also performed at T = (288.15 to 328.15) K for the PEG 400 + 1-propanol and 1-butanol systems. The excess molar volume, VE, isentropic compression deviation, ΔKs, and viscosity deviation, Δη, have been calculated for each composition from the experimental data and fitted to the Redlich–Kister equation.

Liquid–Liquid Equilibria of Water + 1-Butanol + Amino Acid (Glycine or dl-Alanine or l-Leucine) at 313.15 K

Amino acids play an important role both in animal metabolism and in industrial processes. Since they are rarely found in nature in a free form, they must be obtained by biosynthesis or protein hydrolysis, often resulting in aqueous mixtures containing various solutes including several types of amino acids. As a consequence, the cost of the separation processes and concentration of amino acids can be as high as 90 % of their total manufacturing cost. In this way, the design of such processes requires knowledge of the partitioning behavior in two-phase systems and thermodynamic models should support this optimization procedure. However, both the complexity of biomolecules, due to their multiple functional groups, and the crucial role of water make the standard available thermodynamic models unattractive for the computation of phase behavior. Therefore, new thermodynamic models for the description of the phase behavior of systems containing biomolecules are required. In this work, liquid–liquid equilibrium data of the ternary systems 1-butanol + water + amino acid (glycine, dl-alanine or l-leucine) were measured at 313.15 K. The experimental results were correlated and interaction parameters were estimated for the modified-NRTL, UNIFAC and UNIFAC-Campinas models. The modified-NRTL model was able to describe the data better than the UNIFAC and UNIFAC-Campinas models.

Densities, Viscosities, and Refractive Indices of the Ternary Mixture Dimethyladipate + 2-Butanone + 1-Butanol at T = (288.15 to 323.15) K

Excess molar volumes VE, refractive index deviations ΔnD, and viscosity deviations Δη of the ternary dimethyladipate + 2-butanone + 1-butanol and binary 2-butanone + 1-butanol systems are determined from the measured densities ρ, refractive indices nD, and viscosities η. Viscosities and viscosity deviations of the binary dimethyladipate + 2-butanone system are also presented. Measurements are carried out at eight temperatures from (288.15 to 323.15) K and at an ambient pressure of 0.1 MPa. Instruments from Anton Paar were utilized: a digital vibrating tube densimeter type DMA 5000, RXA 156 refractometer, and SVM 3000/G2 digital Stabinger viscometer. Excess properties of the binary system were fitted to the Redlich–Kister polynomial equation, whereas for the ternary system, the Nagata–Tamura equation was applied. To try to comprehend the nature of the interactions between compounds that cause nonideal behavior in mixtures, FT-IR spectra of the binary constituents were collected at T = 298.15 K. VE data of ...

Isobaric Vapor-Liquid-Liquid Equilibria for 1-Butanol + Water + 2,3-Butanediol at 101.3 kPa

Vapor-liquid-liquid equilibria (VLLE) data were determined for the ternary system 1-butanol + water + 2,3-butanediol at 101.3 kPa. A binary heterogeneous minimum boiling azeotrope was found at 365.95 K with mass fractions of 0.526 and 0.474 for 1-butanol and water, respectively. A modified UNIQUAC model was used to predict VLLE by using experimental data, including VLE of 1-butanol + 2,3-butanediol, VLE of water + 2,3-butanediol, LLE of 1-butanol + water, and one LLE tie-line of 1-butanol + water + 2,3-butanediol. The experimental data were compared with the calculated values. The absolute average relative deviations (AARD) are 1.65%, 1.72%, and 2.22% for organic liquid phase, aqueous liquid phase, and vapor phase, respectively. It demonstrates an appropriate fit of the modified UNIQUAC model.