Binary Liquid–Liquid Equilibria of γ-Valerolactone with Some Hydrocarbons

Abstract

Liquid−liquid equilibrium data in binary systems γ-valerolactone + hydrocarbon (n-heptane, n-decane, n-dodecane, cyclohexane, and 2,4,4-trimethyl-1-penetene) were determined by direct analytical and cloud-point methods. The experimental data were smoothed by the extended scaling law equation which respects nonclassical behavior of fluid mixtures in critical loci. The nonrandom two-liquid equation's parameters were evaluated from the data obtained, as well. Since the molecule of γ-valerolactone retains a quite high dipole moment, the acquired experimental data on liquid−liquid equilibrium were used for the testing of predictive capabilities of the perturbed-chain polar SAFT equation of state (PCP-SAFT) in comparison to the original PC-SAFT model. Vapor pressures of γ-valerolactone in the temperature range from 264 K to 313 K and its liquid densities at temperatures from 288 K to 363 K were measured and utilized for evaluation of the PCP-SAFT and PC-SAFT parameters. It was found that prediction of liquid−liquid equilibrium performed by the polar PCP-SAFT equation with pure component parameters can be classified as relatively successful. ■ INTRODUCTIONγ-Valerolactone (GVL) is a natural compound which can be found for example in fruits. Recently this compound has gained attention as a versatile sustainable liquid which can be efficiently produced from biomass, preferentially from lignocellulose. The versatility of GVL is very wide. GVL can be utilized as liquid fuel, green solvent, and food additive or as an organic intermediate in the syntheses of other chemicals. To produce GVL from biomass, different technologies are studied. A pioneering technology suggested by Horvath et. al 1 involves a high pressure hydrogenation step which is rather costly for large-scale production of GVL. Romań et al. 2 devised a less expensive method to synthesize the key biofuel component, which could make its industrial production much more costeffective. From this point of view the utilization of GVL as fuel, fuel additive, or fuel precursor seems to be very promising. GVL can be converted to lower molecular weight valerate esters (methyl-, ethyl-, and propyl valerate) suitable for use as a gasoline additive and higher esters (butyl and pentyl valerate) that could be used directly as a diesel fuel or as a diesel additive. 3 Alternatively GVL can be converted to butane molecules which can be further combined to yield longer hydrocarbon chains for diesel or jet fuels. 4 A comparison of GVL with absolute ethanol as a gasoline additive was done by Horvath et al. 5 It was found that most of the data for GVL are comparable with that of ethanol. The lower vapor pressure of GVL even leads to improved performance. According to experiments carried out by Bereczky et al., 6 the addition of GVL to diesel fuels had relatively little effect on engine performance and NO x emission, but it significantly reduced the exhaust concentration of CO, unburned fuel, and smoke. The use of GVL as direct additive to gasoline can be restricted however because of t...

Vapor Pressures, Densities, and PC-SAFT Parameters for 11 Bio-compounds

“…We found the literature data from 11 other sources, and we compared these different data sets in Fig. 3 [56,[65][66][67][68][69][70][71][72][73][74]. Most of the data fall within a few percentage points of each other, but there is one point from Havasi et al [69] that is about 40 % lower than the other data.…”

“…3 Comparison of vapor pressure data for gamma-valerolactone from different sources. This work, [65], [66], [67], [68], [69], [70], [56], [71], [72], [73], [74]…”

“…For some of the compounds in this article PC-SAFT parameters have already been presented in the literature (2-methylfuran, [50,51]; 2-pentanone [37,52]; cyclopentyl methyl ether [53]; furfural [37,54]; tetrahydrofuran [37,55] and γ-valerolactone [56]. We have refit parameters for these compounds because we had more data to include in the regression, including the new data measured in this article.…”

Isobaric Vapor–Liquid Equilibria of Binary Mixtures of γ-Valerolactone + Acetone and Ethyl Acetate

“…22 Ruzǐcǩa measured the enthalpy of vaporization and fusion as well as condensed phase heat capacity of GVL. 21 R ̌ehaḱ studied the binary liquid−liquid equilibria of GVL with selected hydrocarbons referring to its biofuel applications 24 and determined its thermal and volumetric properties. 25 Ceriani's group reported liquid−liquid equilibria data for three n-tetradecane-based ternary mixtures of GVL.…”

Liquid–Liquid Equilibria of Ternary Mixtures (1-Heptanol, Propanone, 2-Butanone or 2-Heptanone + γ-Valerolactone + n-Tetradecane)

“…Nonetheless, the interest in GVL for industrial applications is quite recent so the compound is still not produced at commercial scale and little is known about its interactions with other chemicals. Accordingly, the few studies available on this subject are related to the liquid–liquid equilibria of GVL + hydrocarbon, − GVL + toluene + hydrocarbon, , GVL + n -tetradecane + carboxylic acids, and GVL + n -tetradecane + esters and the vapor–liquid equilibria of GVL + alcohols, , GVL + water, ,, and GVL + formic acid. , …”