Liquid-liquid equilibria for methyl isobutyl ketone + cresols + water at 333.15 K, 343.15 K and 353.15 K: Experimental results and data correlation

doi:10.1016/j.fluid.2016.07.023

Fluid Phase Equilibria

Volume 427, 15 November 2016, Pages 291-296

https://doi.org/10.1016/j.fluid.2016.07.023 Get rights and content

Abstract

In this work, the liquid-liquid equilibrium (LLE) data for ternary systems, methyl isobutyl ketone + o, m or p-cresol + water were measured at 333.15 K, 343.15 K and 353.15 K under 101.3 kPa. The nonrandom (NRTL) and universal quasichemical (UNIQUAC) models were used to correlate the experimental data, and the results indicated that, both models predicted LLE data quite accurately, with root mean square deviations (RMSD) less than 2.5%. The binary interaction parameters calculated from these two models were also reported. Distribution coefficient and selectivity were calculated to assess the extraction performance of methyl isobutyl ketone.

Introduction

Coal gasification or distillation produces wastewater with highly concentrated phenols, which contains volatile phenols such as phenol and cresols, nonvolatile phenols such as hydroquinone and polyphenols, ammonia, organic acids and other substances. Among these pollutants, cresols are harmful to organism at concentration higher than 250 mg L⁻¹ [1], and may bring long-term adverse effects to the aquatic environment. Cresols are extremely toxic, even more toxic than phenol: e.g. the LD50 (rats oral) of o-, m-, p-cresol and phenol are 121, 242, 207 and 317 mg/kg respectively. They also have higher bio-accumulation potential than phenol as indicated by the octanol-water partition coefficient: e.g. log Kow of o-, m-, p-cresol and phenol are 1.95, 1.96, 1.95 and 1.46 respectively [2]. Thus it is necessary to remove cresols from waste waters before discharging them [3].

Solvent extraction is a frequently used method to treat phenols containing waste water with a range of advantages such as ease of implement, high throughput, versatility and economical efficiency [4]. This method has being used in China [5], South Africa [1], United states [1], [6], etc., for quite a few decades, and the process simulation, operation cost and industrial implementation has been studied thoroughly [7], [8]. Liquid-liquid equilibria (LLE) data are essential for designing or optimizing an extraction process [9], [10], [11]. Some LLE data of the ternary solvent-cresol-water systems have been published in recent years. The experimental data for (toluene + o-, m-, p-cresol + water), (ethylbenzene + o-, m-, p-cresol + water), (heptane + o-, m-, p-cresol + water) and (octane + o-, m-, p-cresol + water) systems were measured by Martin et al. [12], [13]. Kupatkin et al. [14] studied the ternary systems, (trimethylcarbinol + o-cresol + water) and (trimethylcarbinol + m-cresol + water) at 298.2 and 323.2 K. The system (methyl butyl ketone + o-, m-, p-cresol + water) at 298.2 and 313.2 K was investigated by Lv et al. [15]. The LLE data of the systems, (2-methoxy-2-methylpropane + o-, m-, p-cresol + water) at 298.15 and 313.15 K were reported by Luo et al. [16], [17], [18].

Methyl isobutyl ketone (MIBK) is considered to be an excellent extraction solvent to separate cresols from water with high distribution coefficients, and has been used to treat phenolic waste water in industry [5], [7]. It also has attracted the interest of researchers, with tie line data for the systems, (methyl isobutyl ketone + o- or p-cresol + water), measured at 303.2 K by Telkikar et al. [19]. However, recovering phenols from waste water in industry are usually performed at temperatures above 333 K to avoid clogging the extraction installation by paraffin wax (melting point between 328.15 and 335.15 K) in the industrial efflux [20], while corresponding LLE data in such temperature range remain unknown. Hence it is critical to study solvent extraction of cresols with MIBK above 333 K for designing or optimizing wastewater treatment process in industry.

The LLE data of ternary systems, (methyl isobutyl ketone + o-, m-, p-cresol + water) at (333.15, 343.15 and 353.15) K under 101.3 kPa were measured in this work. The experimental data were correlated by NRTL [21] and UNIQUAC [22] activity coefficient to yield binary interaction parameters.

Section snippets

Materials

The purity and source of chemical reagents in this work are listed in Table 1. These chemicals were used without further purification since their purity had been verified with analysis methods listed in Table 1. Distilled water was used throughout all experiments.

Apparatus and procedure

The experimental LLE data for the ternary systems, MIBK + o, m or p-cresol + water were measured at 333.15 K, 343.15 K and 353.15 K under 101.3 kPa. Certain amounts of MIBK, o, m or p-cresol, and water were loaded into a 100 mL glass

Experimental LLE data

Table 2, Table 3, Table 4 show the LLE data of ternary systems, MIBK + cresols + water at (333.15, 343.15 and 353.15) K under 101.3 kPa. All concentrations are expressed in mole fraction. The tie-lines data for the studied systems at were plotted in the triangular diagrams as shown in Fig. 1, Fig. 2, Fig. 3.

To estimate the capacity of MIBK to separate cresols from wastewater, the distribution coefficient (D) and separation factor (S) are calculated as follow $D = \frac{x_{21}}{x_{23}}$ $S = D \frac{x_{33}}{x_{31}}$ where x₂₁ and x₂₃

Conclusions

The LLE data for the ternary systems, MIBK + o-, m-, p-cresol + water, were measured at 333.15 K, 343.15 K and 353.15 K under 101.3 kPa. These LLE data indicates MIBK extracts cresols from water with rather high distribution coefficients and selectivities. In addition, MIBK shows better physical properties than other extractants such as MBK (e.g. lower solubility and lower boiling point). All the results indicate MIBK is a very promising extractant to recovery cresols from water above 333 K.

Acknowledgments

Financial support from the Fundamental Research Funds for the Central Universities, SCUT (2014ZZ0057) and SCUT (2015ZM046), the Project of the Science & Technology New Star of Pearl River in Guangzhou (2011J2200056), the Guangdong Science Foundation (2014A030310260) and National Science Foundation of China (20906028 and 21506066) are gratefully acknowledged.

References (26)

Q.H. Ji et al.
J. Clean. Prod.
(2016)
C.F. Yang et al.
Chem. Eng. J.
(2006)
G. Busca et al.
J. Hazard. Mater
(2008)
C.F. Yang et al.
Fluid Phase Equilib.
(2007)
L.J. Luo et al.
Fluid Phase Equilib.
(2015)
R. Lv et al.
Fluid Phase Equilib.
(2015)
L.J. Luo et al.
Chin. J. Chem. Eng.
(2016)
H. Fiege et al.
Ullmann's Encycl. Ind. Chem.
(2012)
C.H. Wei et al.
J. Environ. Sci-China
(2006)
V.S. Kislik
Solvent Extraction: Classical and Novel Approzches
(2012)

C.F. Yang et al.

Ind. Eng. Chem. Res.

(2013)

Z.J. Yu et al.

Ind. Eng. Chem. Res.

(2010)

Y. Chen et al.

J. Chem. Eng. Data

(2014)

Cited by (30)

Process design, simulation and experimental studies of heteroazeotropic batch distillation for phenol dehydration
2023, Chemical Engineering Research and Design
Phenolic compounds are important groups of chemicals with many applications. Due to the strong affinity between phenols and water, the dehydration of phenolic compounds is often necessary and inevitable. The conventional method for phenol dehydration is the direct distillation without entrainers, leading to high phenol concentration (2–5 wt%) in wastewater and significant difficulty in subsequent wastewater treatment. In this work, heteroazeotropic batch distillation was studied by simulations and experiments to remove water from water-bearing phenols. By simulation, effects of entrainer type, operating pressure, number of theoretical stages, entrainer amount and decanter hold-up on dehydration efficiency were studied in detail. The results showed that the heteroazeotropic batch distillation using ethylbenzene as the entrainer yielded desirable dehydration results with many advantages. The wastewater generated in the dehydration process showed a much lower content of phenolic compounds than the direct distillation, greatly reducing the cost and difficulty of wastewater treatment. The energy consumption of heteroazeotropic distillation was also lower than the direct distillation. Batch distillation experiments were performed to validate the reliability of simulation results. The experimental results were in high agreement with simulations. The produced phenol products showed a water content of 470 ppm, and the content of phenolic compounds in wastewater was reduced to as low as 5.0 ppm. The heteroazeotropic batch distillation proposed in this study suggested an ideal strategy for phenol dehydration which is economically feasible and environmental-friendly.
Extracting phenolic compounds from aqueous solutions by cyclohexanone, a highly efficient extractant
2022, Journal of Industrial and Engineering Chemistry
Citation Excerpt :
Researchers [7,8] stated that compared to other methods, it has the advantages of high economic efficiency, high degree of automation, highly-effective treatment of high-concentration phenolic wastewater, and good-suitability for large-scale applications. According to the extraction mechanisms, the extraction of phenolic compounds can be physical or chemical processes [9,10]. Due to the difficulty in recovering extractants for chemical extraction processes, physical extraction processes are generally used for phenolic wastewater treatment and at present, the commonly used extractants are DIPE and MIBK [11–15].
Methyl isobutyl ketone (MIBK) and diisopropyl ether (DIPE) are two commonly used extractants in industry, but their efficiency in extracting phenols, especially polyhydroxyphenols, is low. In the work, a highly-efficient extractant was proposed to extract phenolic compounds, including polyhydroxyphenols. The interactions between three extractants, cyclohexanone (CYC), MIBK and DIPE, and phenols were analyzed by the COSMO-RS method and CYC shows stronger interactions with phenols than MIBK and DIPE. The results of Fourier-transform infrared spectroscopy (FTIR) show that strong hydrogen bonds are formed between CYC and phenolic compounds, in agreement with the results of the COSMO-RS method. The effects of concentration, temperature and pH values on the extractant performance were studied. Results showed that the performance of CYC is the best, followed by MIBK and DIPE, whose performance is the worst. As CYC was used as the extractant, the distribution coefficients of the three phenolic compounds, phenol, resorcinol and phloroglucinol, are 96.7, 47.8, 13.0, respectively. These values are 35%, 263%, and 160% larger than those of phenol, resorcinol and phloroglucinol, respectively, corresponding to MIBK. CYC is a highly-efficient extractant for the extraction of phenolic compounds, including polyhydroxyphenol.
Exploration of liquid-liquid equilibrium and interaction between guaiacol and water extracted by four ester solvents
2022, Journal of Chemical Thermodynamics
Citation Excerpt :
The guaiacol is oxidized through the electron transfer of the complex. In treating phenol wastewater, the extraction method can be used as a green method [11–13]. Charlie et al. [14] investigated the LLE behavior for the water + guaiacol + isopropyl acetate in 298.2 and 323.2 K under 101.3 kPa.
Four ester solvents were selected as extractants and compared to explore the separation process of recovering guaiacol from an aqueous solution. The liquid-liquid equilibrium (LLE) data for water + guaiacol+ {methyl acetate, ethyl acetate, n-propyl acetate or n-butyl acetate} were measured in 303.2 K and 101.3 kPa. The separate performance in the four extractants was compared and evaluated by the distribution coefficient (D) and the separation factor (S). The NRTL and UNIQUAC models were correlated and fitted to experimental data to obtain regression parameters. Furthermore, the hybrid surface analysis based on Gibbs energy topology verified that the binary interaction parameters are consistent with the measured data. The root mean square deviation (RMSD) of the NRTL and UNIQUAC model does not exceed 0.0076 and 0.0086, respectively, indicating that the above models are suitable for studying the correlation of the system. In addition, the interaction and interaction energy between component molecules were studied through the DMol3 module.
Oilfield produced water treatment by liquid-liquid extraction: A review
2021, Journal of Petroleum Science and Engineering
Oilfield produced water treatment represent a global challenge due to the presence of several contaminants such as heavy metals and dissolved organic compounds. They cannot be removed by conventional equipment and may threat the environment when discarded. Hence, oil industry has the challenge of manage the produced water according to the disposal standards set by environmental agencies and, at the same time, overcome weight and space limitations in the platforms. Choosing the best technology involves the understanding of the process, construction and operational cost, along with the maintenance and management of the removed pollutants. In addition, different oilfield produced water composition and volume also lead to different options for its management. In this context, the study of technological routes such as liquid-liquid extraction is of great interest to the petroleum industry due to the variety of solvents and the different approaches available to accomplish the produced water treatment decontamination. Despite the extensive liquid-liquid extraction application for analysis and remediation of complex mixtures, there is no literature review on this topic. Thus, this paper presents a review of soluble organic compounds removal from oilfield produced water by the liquid-liquid extraction process. The novelty of each extraction method was highlighted and possible applications in the oil industry were identified.
Investigation of liquid–liquid equilibrium of the ternary system (water + 1,6-diaminohexane + 2-methyl-1-propanol or 3-methyl-1-butanol) at different temperatures
2020, Chinese Journal of Chemical Engineering
In this study, the LLE data of ternary system (water + 1,6-diaminohexane + 2-methyl-1-propanol) and (water + 1,6-diaminohexane + 3-methyl-1-butanol) were measured at 293.15, 303.15 and 313.15 K under atmospheric pressure. Reliability of the experimental tie-line data was checked by empirical Hand, Othmer − Tobias and Bachman equations. Distribution coefficient (D) and selectivity (S) were calculated in order to investigate capability of the studied organic solvents for 1,6-diaminohexane extraction. The high values of separation factors demonstrated that 2-methyl-1-propanol and 3-methyl-1-butanol were applicable for this purpose. The experimental data were correlated by nonrandom two-liquid (NRTL) and universal quasi-chemical (UNIQUAC) models. The percent-root-mean-square deviation (RMSD) values for NRTL and UNIQUAC models were less than 0.15, which indicated that the experimental data have been sufficiently correlated.
Experimental measurement, correlation and COSMO-SAC prediction of liquid-liquid equilibrium for MIPK + dimethylphenols + water mixtures
2020, Journal of Chemical Thermodynamics
Liquid-liquid equilibrium (LLE) data for ternary systems of methyl isopropyl ketone (MIPK) + 2,3-/3,4-/3,5-dimethylphenol + water was determined from 298.15 K to 338.15 K under 101.3 kPa in this work. Distribution coefficient and selectivity were calculated to investigate solvent extraction efficiency of dimethylphenol from water and their high values indicated that MIPK could extract dimethylphenols well. The NRTL and UNIQUAC models were applied to correlate experimental LLE data and related root-mean square deviations (RMSDs) were less than 0.5%. Additionally, the experimental data was predicted by COSMO-SAC model, and the corresponding RMSD values demonstrated that COSMO-SAC model can be applied as a predictive tool to calculate LLE data of the investigated ternary systems.

View all citing articles on Scopus

View full text

Liquid-liquid equilibria for methyl isobutyl ketone + cresols + water at 333.15 K, 343.15 K and 353.15 K: Experimental results and data correlation

Abstract

Introduction

Section snippets

Materials

Apparatus and procedure

Experimental LLE data

Conclusions

Acknowledgments

J. Clean. Prod.

Chem. Eng. J.

J. Hazard. Mater

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

Chin. J. Chem. Eng.

Ullmann's Encycl. Ind. Chem.

J. Environ. Sci-China

Solvent Extraction: Classical and Novel Approzches

Ind. Eng. Chem. Res.

Ind. Eng. Chem. Res.

J. Chem. Eng. Data