Measurements and correlation of liquid-liquid equilibrium data for the ternary (3-heptanone + phenol + water) system

https://doi.org/10.1016/j.jct.2016.11.004Get rights and content

Highlights

  • The liquid-liquid equilibrium data for 3-heptanone + phenol + water were measured.

  • The distribution coefficient of phenol and selectivity for solvent extraction efficiency were calculated.

  • The NRTL model (two regression methods) and UNIQUAC model were used to correlate the experimental data with good results.

  • The physical meaning of the regressed binary parameters was explained by intermolecular attractive energy.

  • The activity coefficient of phenol and enthalpy change in extraction process were investigated.

Abstract

Liquid-liquid equilibrium (LLE) for the ternary (3-heptanone + phenol + water) system has been determined under atmospheric pressure at 298.15 K, 303.15 K, 318.15 K and 323.15 K. The NRTL and UNIQUAC models were used to correlate the experimental results. The corresponding binary parameters were obtained and their physical meaning is explained by intermolecular attractive energy. The results from the two models agree well with experimental values. The NRTL model was more accurate than that of the UNIQUAC model. Meanwhile, the NRTL model was used to regress all the experimental values at different temperatures simultaneously, which is defined as total-regression. Compared with the individual regression by the NRTL model, the total regression by the NRTL model has fewer parameters and covers a wider interpolated range from 298.15 K to 323.15 K. The distribution coefficient for phenol changes with temperature. The phenol concentration can be expressed as a function of activity coefficient of phenol in both phases. The effect of temperature on the extraction performance of 3-heptanone was also investigated. The phenol extraction process by 3-heptanone is exothermic. The increase of temperature is not a benefit to phenol extraction.

Introduction

Phenol is one of the most prevalent forms of organic pollutants which commonly exists in waste water from petroleum, petrochemical, coal conversion, phenol-production, and phenolic resin industries [1]. The concentrations of phenol in effluents change from 0.1 to 17 × 103 mg L−1, which contribute (40–80)% of the total chemical oxygen demand (COD) [2]. The phenol compounds are very harmful to living organisms even at low concentration due to their toxicity and carcinogenic properties [3]. Due to the safety and environmental problems, it is essential to collect and remove phenol from waste water of various production units. Liquid–liquid extraction is one of the most explored methods for removal or separation of phenol from aqueous solution. This method is regarded as the best choice for treating waste water containing phenol with high concentrations (>1000 mg·L−1), because the phenol in waste water can be effectively recovered. In the past, volatile or water-soluble organic solvents such as benzene, toluene, heptane, methyl-isobutyl ketone, isopropyl ether, and isopropyl acetate were used for the phenol extraction. However its application is limited due to the high energy consumption. Meanwhile, these materials used for extraction are usually hydrophilic, which would lead to more solvent loss and secondary environmental pollution [4], [5]. So developing a more efficient solvent is crucial to improve such processes. Everson and Parker [6] reported that 3-heptanone might be a possible alternative to MIBK, the former is less soluble in water than the latter. The MIBK is 4.5 times more soluble in the aqueous phase than 3-heptanone at 298.15 K. Compared to the conventional physical extraction solvent, 3-heptanone has relatively strong phenol extraction ability as MIBK, lower mass loss in water, and also the 3-heptanone does not form an azeotrope with water.

The liquid-liquid equilibrium (LLE) data for various (solvent + phenol + water) ternary systems have been obtained because of their importance for phenol extraction. Xu and Ju et al. [7], [8], [9] reported the LLE values for (isopropyl ether + phenol + water) and (isobutanal + phenol + water) systems. Yang et al. [10] determined the experimental values for the (methyl isobutyl ketone + phenol + water) system. Martin et al. [11], [12], [13] reported experimental results for the {aromatic hydrocarbons (toluene or ethylbenzene) + phenols + water} systems, {aliphatic hydrocarbons (heptane or octane) + phenols + water} systems and {(1-butanol or 2-butanol or tert-butanol) + phenol + water} systems. Hwang et al. [14] researched the LLE for the (dimethyl carbonate + phenol + water) and (diphenyl carbonate + phenol + water) systems. Lei et al. [15] studied the extraction of phenol with 2-methoxy-2-methylpropane. Chasib et al. [16] reported values for five solvents {ethylene glycol, diethylene glycol, poly (ethylene glycol) (2 0 0), dimethyl sulfoxide and tetramethylene sulfolane (sulfolane)] + phenol + water} systems. Gilani et al. [17] studied four different solvents {(1-octanol or cyclohexanone or 2-ethyl-1-hexanol or isobutyl acetate) + phenol + water} systems. Park et al. [18] studied the (methyl phenyl carbonate + phenol + water) system. Chen et al. [19] determined experimental values for (methyl butyl ketone + phenol + water) system. Liu et al. [20] studied the LLE for the (methyl tert-butyl ketone + phenol + water) system. Gai et al. [21] reported the findings from measurement and correlation of LLE for the (mesityl oxide + phenol + water) ternary system. However, the LLE of the (3-heptanone + phenol + water) ternary system has not been reported in the available literature.

To obtain reliable data for simulating phenol recovery from the waste water, in this work, the LLE data were determined for the ternary system (3-heptanone + phenol + water) at 298.15 K, 303.15 K, 318.15 K and 323.15 K under atmosphere pressure. The LLE results were correlated using the non-random two-liquid (NRTL) [22] and the universal quasi-chemical (UNIQUAC) [23] activity coefficient models to obtain the binary parameters of these components.

Section snippets

Chemicals

The supplier and the purity grades (expressed as mass fraction) of the chemical reagents used in this work are shown in Table 1. The purity of the materials was checked with gas chromatography by suppliers. All of the chemicals in the study were used without further purification. Deionised and distilled water was used in all experiments.

Apparatus and procedure

The LLE was measured by using a 50 mL glass equilibrium cell consisting of a heating jacket to keep the temperature constant. The cell temperature was controlled

The distribution coefficient and selectivity

To estimate the ability of 3-heptanone to separate phenol from waste water, the distribution coefficient (D) and the selectivity (S) are calculated asD=w2Ow2WS=(w2/w3)O(w2/w3)W

Here D represents the distribution coefficient of phenol in mass fraction. The distribution coefficient and selectivity for phenol at each temperature were also calculated and are presented in Table 5. The results show that 3-heptanone provides a high phenol distribution coefficient and high selectivity factor. Meanwhile,

Conclusions

LLE for the ternary system (3-heptanone + phenol + water) was measured at 298.15 K, 303.15 K, 318.15 K, and 323.15 K at atmosphere pressure. The distribution coefficient and selectivity reflect that 3-heptanone is an efficient solvent to remove phenol from waste water. The Hand and Bachman equations were used to check the reliability of the experimental tie-line values. The experimental results were correlated with the NRTL and UNIQUAC models, and the binary parameters were obtained. Both models give a

Acknowledgements

The acknowledge financial support from The National Science Fund for Distinguished Young Scholars of China (Grant No. 51425405) and the Science and Technology Project of Hunan Province (Grant No. 2014SK3173) are gratefully acknowledged.

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