+ Furfural + Water between 298 and - American Chemical Society

Article pubs.acs.org/jced

Ternary and Binary LLE Measurements for Solvent (4-Methyl-2pentanone and 2‑Methyl-2-butanol) + Furfural + Water between 298 and 401 K Mikael Man̈ nistö,†,∥ Juha-Pekka Pokki,*,†,∥ Arianna Creati,†,‡ Arthur Voisin,†,§ Anna Zaitseva,† and Ville Alopaeus† †

Department of Biotechnology and Chemical Technology, School of Chemical Technology, Aalto University, P.O. Box 16100, 00076 Aalto, Finland ‡ Department of Applied Science and Technology, Politecnico di Torino, Corso Duca degli Abruzzi, 24, 10129 Torino, Italy § Département Chimie Fine et Ingénierie, INSA de ROUEN, 76801 Saint Etienne du Rouvray Cedex, France ABSTRACT: Two solvents, 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK) and 2-methyl-2-butanol (tertpentanol, TAA), were tested and compared according to their performance in furfural extraction from aqueous solutions. Two new experimental apparatus were built and novel liquid−liquid equilibrium of ternary systems consisting of solvent, furfural, and water were measured between 298 and 401 K having boiling point pressure up to 4 bar. In addition, liquid−liquid equilibrium of binary systems were measured between 298 and 352 K at atmospheric pressure. Measurements were modeled with UNIQUAC activity coefficient model and its binary interaction parameters were presented together with the measured data. The suitability of solvent for industrial use was discussed with selectivity and distribution factors.

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INTRODUCTION Growing interest in biomass as a source of both traditional and novel chemicals motivates developing processing methods of biomass. Furfural is one such product that can be obtained from xylose through dehydration and as a byproduct from production and storage of fruit juices and wines.1−3 It can also be obtained from biomass through treatment with steam and sulfuric acid4 or as a side product in lignocellulose processes.5 Furfural is used as an extraction solvent for different lubricating oil manufacturing processes,6 as a raw material for pharmaceuticals and phenolic resins as well as an intermediate in many processes.2 This compound is currently separated from the product solution of a biorefinery with three main methods: distillation, adsorption, and liquid−liquid extraction.7 Separation of furfural from aqueous mixtures by distillation is not efficient due to water−furfural azeotrope and high energy consumption.8 Issues related to handling and regeneration of adsorbents such as charcoal or wood chips in furfural adsorption process make these processes commercially challenging. Studies in membrane technology using hydrophobic polyurethanurea membranes have also received some interest lately.1 Consequently, liquid−liquid extraction of furfural appears as the most convenient choice for furfural upgrading at the moment. In order to develop processes for liquid−liquid extraction, phase equilibria of the components is crucial. Measurements are of interest when evaluating suitable solvents within such processes, as all LLE extraction processes are based on © XXXX American Chemical Society

component distribution between different phases. To facilitate development of furfural extraction units, many different solvents have been studied for their ternary liquid−liquid equilibria with water and furfural.7,9 In this work, liquid−liquid equilibrium (LLE) of methyl isobutyl ketone (MIBK) and 2methyl-2-butanol (TAA) as solvents in ternary solvent− furfural−water mixtures were studied. The work introduces novel high temperature liquid−liquid equilibria data for both mixtures under solution vapor pressure (up to 400 kPa in 400 K) for use in development of LLE processes. High temperature LLE data are useful when designing for example biphasic reactors10,11 for furfural production. Additionally, two new apparatuses for liquid−liquid equilibria measurements are introduced, one for atmospheric pressure and one that withstands higher boiling point pressure caused by higher temperatures.

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EXPERIMENTAL SECTION

Materials. All chemicals, except water, were purchased from Sigma-Aldrich. Gas chromatography (GC) runs and refractive index measurements were carried out for all components to verify their purity. Analytical acetone (CAS: 67-64-1) was used as an internal standard in the GC runs; it was purchased from Merck. Two bottles of MIBK (CAS: 108-10-1) were purchased

Received: August 31, 2015 Accepted: January 19, 2016

A

DOI: 10.1021/acs.jced.5b00738 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Used Chemicalsa

chemical 4-methyl-2pentanone, (MIBK) (First bottle) 4-methyl-2pentanone, (MIBK) (Second bottle) furfural (purchased) furfural (distilled) 2-methyl-2-butanol (TAA) deionized water analytical acetone

nD25 measured at 101.3 kPa

nD25 ref 12 at 101.3 kPa

reported GC purity [wt %]

measured GC purity [wt %]

99.5+

99.76

99.5+

99.6

1.39327

1.3933

99

99.5 99.9 99.87

1.52263 1.40219

1.52345 1.52345 1.40238

99.93

1.33249 1.35553

1.3325 1.35596

99

1.3933

Figure 4. Stainless steel cell and air bath.

a

Refractive indices measured in atmospheric pressure and room temperature, standard uncertainty (u) reported by the refractometer manufacturer u(nD) = 0.0005 and u(T/K) = 0.03. Determined uncertainties are u(w) = 0.05, u(p/kPa) = 2.7.

Table 2. Response Factors for the GC Detectors with MIBK + Furfural + Water Mixtures with Respect to Acetonea FID

TCD

component

MIBK

furfural

MIBK

furfural

water

F (response factor)

0.688

0.999

1.190

1.268

0.886

a

Standard uncertainties (u) are u(MIBK, FID) = 0.011, u(furfural, FID) = 0.016, u(MIBK, TCD) = 0.017, u(furfural, TCD) = 0.018, u(water, TCD) = 0.011.

Table 3. Response Factors for the GC Detectors with TAA + Furfural + Water Mixtures with Respect to Acetonea

Figure 1. Glass cells in mixing position.

FID

TCD

component

TAA

furfural

TAA

furfural

water

F (response factor)

0.660

1.002

1.216

1.274

0.897

a

Standard uncertainties (u) are u(TAA, FID) = 0.008, u(furfural, FID) = 0.014, u(TAA, TCD) = 0.014, u(furfural, TCD) = 0.014, u(water, TCD) = 0.012.

Figure 2. Experimental setup with all glass cells in decanting position.

Figure 5. GC setup.

Deionized water was prepared in-house using a Millipore MilliQ system. Refractive indexes were measured with a Dr. Kernchen Abbemat digital automatic refractometer. The reported purities, analyzed purities and refractive indexes of the compounds are shown in Table 1. Mixtures were prepared gravimetrically using a Precisa 410AM-FR analytical balance. It was calibrated by TEOPAL with a reported uncertainty of u(m/g) = 0.002. Apparatus and Procedure. Liquid−liquid equilibrium (LLE) measurements for the ternary systems were carried out between 298 and 401 K with two static apparatuses. The

Figure 3. Schematic of the mixing system.

from Sigma-Aldrich and both were tested for their purity with GC and found to meet the minimum purity requirement. TAA (CAS: 75-85-4) and furfural (CAS: 98-01-1) were purchased from Sigma-Aldrich and both had reported purities of 99%. Furfural was distilled in vacuum to obtain higher purity. B



Article

Table 4. Optimized UNIQUAC Parameters component i component j Aij Aji Bij Bji Cij Cji Dij Dji

furfural water −4.02768 0.02669 68.51970 108.27900 0 0 0.01062 −0.00243

TAA water 0.60866 −2.14146 −199.38564 515.83626 0 0 0.00011 −0.00004

TAA furfural −0.10606 0.86010 −171.47340 −249.36674 0 0 0 0

MIBK furfural 0.04808 −0.12154 28.89310 −84.09120 0 0 0 0

MIBK water 1.56395 −1.68715 −882.08360 372.45320 0 0 −0.00041 0.00055

function of inlet and outlet temperatures was developed based on separate measurements with water in the cells. Calibrated temperature probes were used during development of the correlation. Stainless Steel Cell. Ternary mixtures of solvent + water + furfural were measured with the stainless steel apparatus at a temperature range from 371 to 401 K. The cell was equipped with a Teflon coated magnetic stirrer and the sampling was made using stainless steel tubes (dead volume in tubes ∼0.5 mL) immersed into the equilibrium phases. The samples were pushed out by the solution vapor pressure inside the cell, which was in all cases higher than atmospheric pressure. The cell was located inside a JEFRI DBR air circulation oven. Windows of the oven and the windows of the cell made the observation of liquid phase split possible. The setup for the cell is illustrated in Figure 4. The apparatus makes it possible to measure high temperature LLE and accurately determine the plait points of different mixtures as a function of temperature. The cell consist of a stainless steel block, two windows, a stainless steel lid, temperature and pressure sensors, and sampling lines. Sampling line valves and the first part of the line after the oven is not thermostated and flashing can therefore occur in the line. To prevent this, the sampling lines were cooled to ∼20 °C to facilitate condensation of the sample prior to drawing it to a 20 mL container. Samples were also taken directly into cooled acetone solution within the container, through a septum, to efficiently capture the volatile components of the samples. The control system of temperature of the air bath was adjusted according to signal of the Pt-100 sensor (ΔT = ±0.2 K) located inside the air circulation bath. Temperature for the liquid within the cell was measured using a Pt-100 probe (ΔT = ±0.2 K) and a Nokeval display unit. The pressure was measured using a Rosemount pressure gauge (300s series) equipped with a Lyth hydraulic pressure transducer. The 4−20 mA signal of Rosemount was read with a Nokeval display unit. This pressure measurement system was calibrated at five temperatures (25, 50, 70, 100, and 130 °C) ΔP was found by calibration to be less than 12 kPa. The mixture was prepared gravimetrically prior to feeding it into the cell. The cell was vacuumed to feed the mixture into the cell via the sampling line and after feeding the liquid it was roughly vacuumed to remove air entering the cell during the filling. At equilibrium temperatures above 370 K, the vapor pressure of the solution inside the cell exceeded the atmospheric pressure (over 1 bar). This overpressure was used to draw the samples. First, approximately 3−5 mL of solution was drained slowly and then sample taken. This was to remove any dead volume within the transfer line for more representative sampling. Temperature of the cell and air bath

measurements at atmospheric pressure were done with a thermostated glass cell apparatus, from which samples were taken using Hamilton sample−lock syringes. High pressure measurements were done with a stainless steel cell apparatus similar to that used by Bo et al.13 The solution was mixed for approximately 30 min after reaching the required temperature and allowed to settle for approximately 30 min after mixing. The time varied depending on density difference of the phases, but it was possible to visually identify when the phases had mixed and separated properly from both apparatuses. Contents of the equilibrium phases were analyzed with an Agilent Technologies 6890N gas chromatograph equipped with two detectors and two columns. After the inlet, there was 1 m inert transfer line to a quartz y splitter that divided the sample to a 28 m DBWaxETR column, connected to the Thermal Conductivity Detector (TCD) and a 30 m HP-5 column, connected to the Flame Ionization Detector (FID). Glass Cell. Binary systems of solvent + water and ternary systems of solvent + water + furfural were investigated with the glass apparatus between 298 and 352 K. There are four identical cells in the device, each approximately 25 mL. Each individual cell is closed from atmosphere and the material of the cells limits the temperatures to a maximum of 353 K. Higher temperatures would increase the solution vapor pressure inside the cells and potentially break them. The cells are filled with the solutions independently and the use of four cells in series makes it possible to study of four different mixtures at the same time. Cells can be operated independently if needed. The cell type is similar to those used by Mardani et al.14 The apparatus allows fast simultaneous measurement of multiple different compositions. Temperatures can be stabilized on a range from 298 to 358 K with the current water bath setup. Higher boiling point heating media would allow for higher temperature but the vapor pressure of the solution would limit the usability range. Such a cell is shown in Figure 1 and the setup in Figure 2. The temperature of the cells was controlled with a Lauda E200 water bath. Mixing of the cells was done with Teflon coated magnetic stirrer that was freely moving within the cell. The four cells were attached to a plate, which was attached to a pivot point. An electric motor connected to a rotating eccentric wheel rocks the plate and the magnetic stirrer moves freely and mixes the liquids together. The schematic of the mixing style is shown in Figure 3. The samples were taken through the septum sampling points visible in Figure 1 using Hamilton Gastight #1001-series syringes with sample lock. Temperature for the heating liquid was measured at the inlet of cell 1 and outlet of cell 4. Correlation for the temperatures inside all the cells as a C



Article

used for water, it has a lower detection limit for the organic components and was used for critical comparison with respect to TCD measurements. The ratio of organic components in FID was compared to their ratio in TCD. The primary analysis technique was TCD, as it can also detect water. Response factors were calculated with

and the pressure within the cell were all logged when taking samples. Due to the incomplete degassing of the solution, the vapor pressure is not accurate and therefore only approximation is reported. The nitrogen line was used to push out any solution left in the cell after measurements and assist in drying and cleaning of the cell between runs. Analysis of Samples. Binary standards for the components were made gravimetrically with an analytical balance into 10 mL volumetric flasks. In the standards, two components were used to see if they affect the response factors (furfural + water, furfural + solvent, solvent + water). Although FID could not be

ΔFi =

Fi = Fstd ·

A std mi · Ai mstd

and their uncertainties with

⎛ ∂Fi ⎞2 ⎛ ∂Fi ⎞2 ⎛ ∂Fi ⎞2 ⎛ ∂Fi ⎞2 ·ΔAi ⎟ + ⎜ ·ΔA std ⎟ + ⎜ ·Δmbalance⎟ + ⎜ ·Δmbalance⎟ ⎜ ⎝ ∂Ai ⎠ ⎝ ∂A std ⎠ ⎝ ∂mi ⎠ ⎝ ∂mstd ⎠

where Ai denotes peak area for component i, Astd for acetone as the internal standard and mi and mstd the masses weighed in grams for component i and the standard, respectively. Fstd was set to 1. Uncertainties for the individual component areas in TCD were determined by injection of the samples used to calculate response factors through GC five times consecutively and calculating the relative standard deviation of the peaks. Consequently, the relative uncertainty was used to calculate the estimated uncertainties for each measurement. Mass uncertainty was estimated to be 3 times the reported uncertainty of the analytical balance (0.006 g), as there were three weighing per each sample. Response factors for MIBK + furfural + water and their calculated uncertainties are visible in Table 2 and for TAA + furfural + water in Table 3. Samples from the glass cells were taken by first weighing the clean Hamilton syringe, then drawing the sample from the glass cell, weighing the syringe, adding the internal standard and weighing the syringe again. Then the sample was injected into a 2 mL GC vial and closed with the aluminum crimp septa for analysis. The samples from the stainless steel cell were taken, so that an empty 20 mL headspace GC vial was sealed with a septum cap and weighed. Next, acetone was added to the vial as an internal standard while keeping it open to atmosphere by puncturing it with a needle, and the vial was weighed again. After this, the sample was pushed from the cell into the vial with the needle keeping it open to the atmosphere. The vial was shaken and then samples were taken from the vial in to standard 2 mL GC vials for analysis. The method of GC analysis was having a constant temperature at 80 °C for 2 min and then ramped the temperature up to 105 °C at 50 °C/min, held constant temperature for 3 min and then ramped the temperature up to 150 °C at 60 °C/min. This temperature was held for 5 min and then ramped to 200 °C at the 60 °C/min and held there for 3 min. The inlet pressure was kept at 62 kPa, temperature at 250 °C and helium carrier gas flow at 82.1 mL/min. The column pressure was the same as the inlet, the flow was 1.6 mL/min and the average velocity was 29 cm/sec between the inlet and the quartz y splitter. The exact ratio of gas flow in HP-5 (FID) and DBWaxETR (TCD) column was not known but separate response factors for the detectors takes it into account. Figure 5 shows the GC analysis setup. Modeling. The measured data points and literature data4,15−26 were modeled using UNIQUAC-HOC (Hayden−

O’Connell), where UNIQUAC is the model for liquid activity coefficients and HOC is the model for vapor phase fugacities. An in-house modeling software27 and Aspen Plus version 8.6 were used to regress the parameters of UNIQUAC with HOC. The binary interaction parameters were optimized based on the binary mixtures of the components. The parameters were tested in Aspen Plus version 8.6 with the measured ternary systems and were found to estimate the data more accurately than parameters available in the Aspen Plus database. The optimized UNIQUAC parameters are shown in Table 4. All pure component properties and required parameters were retrieved with the Aspen Plus from NIST ThermoData Engine database. Hayden−O’Connell eta parameters for TAA were missing but set equal to parameter of t-BuOH based on the similarity of their chemical structure.

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RESULTS AND DISCUSSION Mass for each component in the sample was calculated based on the recorded GC peak areas and the response factors discussed earlier

Figure 6. Furfural mass fractions in extract and raffinate phase for TAA (1) + furfural (2) + water (3) (left) and Othmer−Tobias plot (right): ◆, measured at 298 K; , measured at 322 K; ▲, measured at 341 K; ■, measured at 371 K; ●, measured at 401 K; × , literature values from Croker and Bowrey25 at 303 K; *, literature values from Conway and Philip26 at 298 K.

mi =

Fi ·Ai ·mstd Fstd·A std

Difference between the sum of calculated component masses using the weighted standard mass and the peak areas and the weighted mass of sample was compared and it served as the first indication of success of sampling and GC analysis. The D



Article

Table 7. TAA(1) + Furfural(2) + Water(3) Ternary Measurements for Mass Fractions in Glass Cells from Thermal Conductivity Detector Analysis at Pressure p = 101 kPaa organic phase

Figure 7. Furfural mass fractions in extract and raffinate phases for MIBK (1) + furfural (2) + water (3) (left) and Othmer−Tobias plot (right): ◆, measured at 303 K; , measured at 322 K; ▲, measured at 341 K; ■, measured at 371 K; ●, measured at 401 K; × , literature values from Croker and Bowrey25 at 303 K; *, literature values from Conway and Philip26 at 298 K.

Table 5. TAA (1) + Furfural(2) + Water(3) Binary Measurements for Mass Fractions from Thermal Conductivity Detector Analysis at Pressure p = 101 kPaa organic phase

aqueous phase

Tcell/K

w1

w2

w3

w1

w2

w3

298.3 298.2 302.9 321.4 350.2 298.2 298.3 303.0 322.4 370.7 370.7 401.0 401.0

0 0 0 0 0 0.781 0.782 0.786 0.808 0.812 0.815 0.805 0.805

0.953 0.952 0.946 0.927 0.899 0 0 0 0 0 0 0 0

0.047 0.048 0.054 0.073 0.101 0.219 0.218 0.214 0.192 0.188 0.185 0.195 0.195

0 0 0 0 0 0.108 0.109 0.094 0.073 0.060 0.060 0.066 0.066

0.081 0.084 0.089 0.098 0.141 0 0 0 0 0 0 0 0

0.919 0.916 0.911 0.902 0.859 0.892 0.891 0.906 0.927 0.940 0.940 0.934 0.934

Standard uncertainties (u) are u(T/K) = 0.2, u(w1, organic) = 0.006, u(w2, organic) = 0.006, u(w3, organic) = 0.005, u(w1, aqueous) = 0.002, u(w2, aqueous) = 0.003, u(w3, aqueous) = 0.004, and u(p/kPa) = 1.

aqueous phase

w1

w2

w3

w1

w2

w3

302.8 303.1 303.2 322.6 342.2 303.1 302.8 322.4 401.0 401.0

0 0 0 0 0 0.981 0.981 0.975 0.941 0.941

0.950 0.950 0.949 0.935 0.898 0 0 0 0 0

0.050 0.050 0.051 0.065 0.102 0.019 0.019 0.025 0.059 0.059

0 0 0 0 0 0.016 0.016 0.014 0.018 0.019

0.085 0.087 0.087 0.101 0.120 0 0 0 0 0

0.915 0.913 0.913 0.899 0.880 0.984 0.984 0.986 0.982 0.981

w2

w3

w1

w2

w3

298.2 298.1 298.1 298.2 298.2 298.2 298.2 298.2 303.1 302.9 302.8 302.7 321.7 322.2 321.4 321.7 322 322.1 322.4 321.6 322 342.3 341.8 341.4 340.9 350.9 352.2 351.6

0.158 0.233 0.329 0.351 0.430 0.515 0.517 0.644 0.079 0.243 0.422 0.642 0.169 0.250 0.270 0.369 0.449 0.450 0.545 0.666 0.674 0.082 0.249 0.439 0.675 0.163 0.556 0.679

0.743 0.634 0.487 0.464 0.352 0.245 0.240 0.114 0.844 0.621 0.370 0.126 0.703 0.601 0.571 0.448 0.349 0.349 0.245 0.129 0.118 0.809 0.583 0.368 0.131 0.676 0.243 0.126

0.099 0.133 0.184 0.185 0.218 0.240 0.243 0.242 0.077 0.136 0.208 0.232 0.128 0.149 0.159 0.183 0.202 0.201 0.210 0.205 0.208 0.109 0.168 0.193 0.194 0.161 0.201 0.195

0.048 0.061 0.078 0.081 0.094 0.103 0.101 0.111 0.025 0.057 0.084 0.100 0.034 0.046 0.049 0.065 0.071 0.072 0.074 0.074 0.074 0.016 0.042 0.057 0.064 0.027 0.060 0.064

0.084 0.084 0.081 0.077 0.069 0.052 0.051 0.027 0.089 0.083 0.067 0.030 0.091 0.089 0.088 0.081 0.068 0.066 0.046 0.027 0.024 0.121 0.100 0.067 0.026 0.114 0.049 0.026

0.868 0.855 0.841 0.842 0.837 0.845 0.848 0.862 0.886 0.860 0.849 0.870 0.875 0.865 0.863 0.854 0.861 0.862 0.880 0.899 0.902 0.863 0.858 0.876 0.910 0.859 0.891 0.910

the sampled points. Mass fraction of each component was calculated from the masses based on the peak areas. mi wi = mi + mj + mk

Table 6. MIBK(1) + Furfural(2) + Water(3) Binary Measurements for Mass Fractions from Thermal Conductivity Detector Analysis at Pressure p = 101 kPaa Tcell/K

w1

a Standard uncertainties (u) are u(T/K) = 0.2, u(w1, organic) = 0.006, u(w2, organic) = 0.006, u(w3, organic) = 0.005, u(w1, aqueous) = 0.002, u(w2, aqueous) = 0.003, u(w3, aqueous) = 0.004, and u(p/kPa) = 1.

a

organic phase

aqueous phase

Tcell/K

The uncertainty for each composition was determined with Δwi =

⎞2 ⎛ ∂w ⎛ ∂wi ⎞2 ⎛ ∂wi ⎞2 i ⎜ ⎟ ·Δmi⎟ + ⎜ ·Δmj⎟ + ⎜ ·Δmk ⎟ ⎜ ⎝ ∂mi ⎠ ⎝ ∂mk ⎠ ⎝ ∂mj ⎠

Δmi = ⎞2 ⎞2 ⎛ ∂mi ⎞2 ⎛ ∂m ⎞2 ⎛ ∂mi ⎛ ∂mi ·ΔAi ⎟ + ⎜ ·ΔA std ⎟ + ⎜ i ·ΔFi ⎟ + ⎜ ·Δmstd ⎟ ⎜ ⎠ ⎝ ∂mstd ⎠ ⎝ ∂Fi ⎠ ⎝ ∂A std ⎠ ⎝ ∂Ai

Othmer−Tobias plot28 and a plot of furfural mass fraction in solvent phase as a function of furfural mass fraction in aqueous phase were used as the second and third indication of the success of sampling. Points out of the trend visible in the figures and clear outliers in the LLE diagrams were rejected. Plots for TAA are available in Figure 6 and for MIBK in Figure 7. The Othmer−Tobias28 plots show clear trends that are similar to those reported to other solvents in the original article. In addition, the measurements at temperature close to room


following requirement was chosen: Absolute relative difference higher than 10% was not acceptable and caused the rejection of E



Article

Table 8. MIBK(1) + Furfural (2) + Water (3) Ternary Measurements for Mass Fractions in Glass Cells from Thermal Conductivity Detector Analysis at Pressure p = 101 kPaa organic phase

Table 9. TAA (1) + Furfural (2) + Water (3) Ternary Measurements for Mass Fractions in Stainless Steel Cell from Thermal Conductivity Detector Analysis at Pressure p ∼ 150 kPa for 371 K and p ∼ 400 kPa for 400 Ka

aqueous phase

organic phase

aqueous phase

Tcell/K

w1

w2

w3

w1

w2

w3

Tcell/K

w1

w2

w3

w1

w2

w3

302.3 303.1 303.1 303.0 302.0 302.0 302.0 302.3 302.3 302.6 302.3 302.6 302.6 302.9 302.9 321.3 322.8 322.6 320.9 322.9 320.6 321.3 322.7 321.8 321.2 322.6 321.8 321.7 322.2 322.2 341.9 340.2 339.6 340.8 341.4 342.0

0.144 0.187 0.200 0.286 0.414 0.424 0.562 0.579 0.607 0.664 0.691 0.780 0.788 0.881 0.884 0.142 0.182 0.397 0.404 0.506 0.560 0.576 0.619 0.660 0.688 0.711 0.775 0.838 0.874 0.879 0.393 0.405 0.417 0.565 0.773 0.875

0.809 0.770 0.757 0.675 0.549 0.541 0.408 0.391 0.362 0.306 0.281 0.196 0.187 0.097 0.095 0.799 0.763 0.560 0.545 0.456 0.407 0.388 0.347 0.302 0.279 0.258 0.194 0.136 0.097 0.093 0.536 0.542 0.533 0.383 0.191 0.092

0.047 0.043 0.043 0.039 0.037 0.035 0.030 0.030 0.031 0.030 0.028 0.024 0.025 0.022 0.021 0.059 0.055 0.043 0.051 0.038 0.033 0.036 0.034 0.038 0.033 0.031 0.031 0.026 0.029 0.028 0.071 0.053 0.050 0.052 0.036 0.033

0.005 0.005 0.006 0.008 0.010 0.011 0.012 0.012 0.013 0.013 0.014 0.014 0.014 0.014 0.015 0.005 0.005 0.010 0.010 0.010 0.010 0.011 0.011 0.014 0.012 0.011 0.012 0.013 0.014 0.013 0.009 0.011 0.009 0.013 0.014 0.013

0.066 0.064 0.064 0.055 0.047 0.045 0.034 0.034 0.031 0.027 0.025 0.017 0.017 0.009 0.008 0.074 0.073 0.052 0.050 0.040 0.037 0.037 0.031 0.029 0.025 0.023 0.018 0.013 0.009 0.009 0.057 0.059 0.056 0.042 0.021 0.010

0.929 0.931 0.930 0.937 0.943 0.944 0.954 0.954 0.956 0.960 0.961 0.969 0.969 0.977 0.977 0.921 0.922 0.938 0.940 0.950 0.953 0.952 0.958 0.957 0.963 0.966 0.970 0.974 0.977 0.978 0.934 0.930 0.935 0.945 0.965 0.977

371.3 371.3 371.3 371.5 371.5 371.5 371.5 371.6 371.6 371.6 371.6 400 400 401.2 401.1 401.1 401.2 401.1 401.1

0.22 0.22 0.22 0.455 0.456 0.62 0.621 0.621 0.622 0.722 0.723 0.184 0.184 0.445 0.445 0.445 0.446 0.608 0.609

0.562 0.561 0.56 0.324 0.324 0.172 0.172 0.175 0.174 0.081 0.081 0.514 0.513 0.356 0.349 0.349 0.355 0.174 0.173

0.218 0.219 0.22 0.221 0.22 0.208 0.207 0.204 0.204 0.197 0.196 0.302 0.303 0.199 0.206 0.206 0.199 0.218 0.218

0.047 0.047 0.047 0.062 0.062 0.062 0.062 0.062 0.063 0.059 0.06 0.051 0.05 0.056 0.057 0.057 0.056 0.054 0.055

0.142 0.142 0.142 0.074 0.074 0.036 0.037 0.037 0.037 0.017 0.017 0.193 0.194 0.088 0.087 0.087 0.087 0.041 0.041

0.811 0.811 0.811 0.864 0.864 0.902 0.901 0.901 0.9 0.924 0.923 0.756 0.756 0.856 0.856 0.856 0.857 0.905 0.904


LLE area as a function of temperature for both of the systems are shown in Figures 12 and 13. As can be seen from the figures for both solvents with water, the literature data agrees well with our measurements. Our regressed UNIQUAC parameters also provide a binary model that agrees with both our data and the literature values below 370 K. Our measurements indicate the possibility of the upper solution critical point as temperature exceeds 401 K but temperature is not reaching it and the literature values are missing. The model for MIBK + furfural + water predicts the measured values very well on other temperatures than 401 K. However, the proximity of the plait point temperature is expected to cause inaccuracy in the model. The parameters still predict the plait point behavior correctly. For TAA + furfural + water the model slightly overpredicts the values on the organic phase. This can lead to issues in the use of the model in process design and further optimization should be done. Suitability of the solvent for industrial application was analyzed using the distribution factor calculated by wfurfural,extract K= wfurfural,raffinate

a

Standard uncertainties (u) are u(T/K) = 0.2, u(w1, organic) = 0.006, u(w2, organic) = 0.007, u(w3, organic) = 0.002, u(w1, aqueous) = 0.001, u(w2, aqueous) = 0.002, u(w3, aqueous) = 0.002, and u(p/kPa) = 1.

temperature show good agreement with literature data for both of the solvents. Measurements for both the glass cell apparatus and the stainless steel apparatus are in the following tables. The results for binary mixtures are shown in Table 5 (TAA) and Table 6 (MIBK). The ternary mixtures in lower temperature range (from 298 to 341 K) are shown in Table 7 for TAA and in Table 8 for MIBK and the results for higher temperature range (from 371 to 401 K) ternary measurements done in the stainless steel apparatus are available in Table 9 for TAA and in Table 10 for MIBK. Binary MIBK + water and TAA + water data are compared to available literature in Figures 8 and 9. The regressed parameters for UNIQUAC models for MIBK + furfural + water and TAA + furfural + water are compared to our measured and available literature data in Figures 10 and 11. Schematic drawings of the

and selectivity calculated by

S=

( ) ( ) wfurfural wsolvent

wfurfural wsolvent

extract

raffinate

−1

( ) ·( ) ·

wwater wsolvent

wwater wsolvent

extract −1 raffinate

Plots for the distribution coefficient and selectivity of furfural within TAA (1) + furfural (2) + water (3) mixtures are shown F



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Table 10. MIBK(1) + Furfural(2) + Water(3) Ternary Measurements for Mass Fractions in Stainless Steel Cell from Thermal Conductivity Detector Analysis at Pressure p ∼ 150 kPa for 371 K and p ∼ 400 kPa for 400 Ka organic phase

aqueous phase

Tcell/K

w1

w2

w3

w1

w2

w3

371.9 371.9 371.8 371.8 371.6 371.6 371.6 371.5 371.5 371.6 371.5 371.5 401.5 401.5 401.2 401.2 401.1 401.1 401.2 401.2 401.0 401.1 401.1 401.0

0.142 0.142 0.142 0.143 0.408 0.409 0.410 0.573 0.573 0.746 0.763 0.762 0.130 0.130 0.166 0.165 0.326 0.327 0.403 0.404 0.541 0.582 0.582 0.720

0.746 0.745 0.749 0.747 0.517 0.517 0.515 0.364 0.365 0.211 0.189 0.190 0.671 0.670 0.655 0.655 0.550 0.548 0.494 0.497 0.371 0.326 0.326 0.202

0.112 0.113 0.109 0.110 0.075 0.074 0.075 0.063 0.062 0.043 0.048 0.048 0.199 0.200 0.179 0.180 0.124 0.125 0.103 0.099 0.088 0.092 0.092 0.078

0.008 0.008 0.009 0.009 0.012 0.013 0.013 0.013 0.013 0.014 0.014 0.014 0.019 0.019 0.019 0.019 0.021 0.020 0.021 0.021 0.019 0.021 0.020 0.020

0.134 0.134 0.137 0.136 0.073 0.074 0.072 0.048 0.048 0.027 0.025 0.025 0.223 0.223 0.188 0.187 0.122 0.122 0.101 0.100 0.067 0.060 0.060 0.034

0.858 0.858 0.854 0.855 0.915 0.913 0.915 0.939 0.939 0.959 0.961 0.961 0.758 0.758 0.793 0.794 0.857 0.858 0.878 0.879 0.914 0.919 0.920 0.946

Figure 9. Comparison of our measured TAA (1) + water (2) binary data to literature data. The left figure represents the aqueous phase and the right the organic phase: ●, this work; , literature values by Stephenson et al.;17 + , literature values by Chiou and Chen.;9 ◆, literature values by Ginnings and Baum;33 *, literature values by Pai and Chen.34


Figure 10. Regressed model for MIBK (1) + furfural (2) + water (3) with UNIQUAC, shown with our measurements and literature data: ◆, measured; , modeled; + , literature values from Conway and Philip26 at 298 K; × , literature values from Croker and Bowrey25 at 303 K.

Figure 8. Comparison of our measured MIBK (1) + water (2) binary data to literature data. The left figure represents the aqueous phase and the right the organic phase: line represents the model; ●, this work; , literature values by Ginnings et al;29 ◆, literature values by Yang et al.;30 ▲, literature values by Fang et al.;31 × , literature values by Stephenson et al.32

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CONCLUSIONS New liquid−liquid equilibrium data was measured for the ternary systems of TAA + furfural + water and MIBK + furfural + water. Both MIBK and TAA are suitable solvents for furfural extraction in an aqueous system. MIBK showed a larger LLE area than TAA. There is also a clear correlation on the size of the LLE area and temperature. As the temperature of the solution increases, the LLE area decreases. At the highest temperatures measured in this work, the shape of the ternary LLE curve changes due to the binary system of furfural and water becomes soluble to each other. MIBK was less soluble in raffinate and more efficient in transferring furfural in extract

in Figure 14 and within MIBK (1) + furfural (2) + water (3) mixtures in Figure 15. Distribution coefficient K and selectivity S plots for TAA show that when temperature is kept low, the solvent behaves effectively; however, as temperature goes up, selectivity and distribution factors both deteriorate fast. The same can be seen happening for MIBK; however, the effect is not as drastic for selectivity. G



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Figure 13. Schematic figure of TAA (1) + furfural (2) + water (3) two phase region behavior as a function of temperature (models as in Figure 11, the smaller the area, the higher the temperature).

Figure 14. Plots for the distribution coefficient (left figure) and selectivity of furfural (right figure) within TAA (1) + furfural (2) + water (3) mixtures as a function of furfural mass fraction in raffinate: ◆, measured at 298 K; , measured at 322 K; ▲, measured at 341 K; ■, measured at 371 K; ●, measured at 401 K. Figure 11. Regressed model for TAA (1) + furfural (2) + water (3) with UNIQUAC, shown with our measurements and literature data: ◆, measured; , modeled; × , literature values from Cabezas et al.4 at 298 K.

Figure 15. Plots for the distribution coefficient (left figure) and selectivity of furfural (right figure) within MIBK (1) + furfural (2) + water (3) mixtures as a function of furfural mass fraction in raffinate: ◆, measured at 303 K; , measured at 322 K; ▲, measured at 341 K; ■, measured at 371 K; ●, measured at 401 K.

■

Figure 12. Schematic figure of MIBK (1) + furfural (2) + water (3) two phase region behavior as a function of temperature (models as in Figure 10, the smaller the area, the higher the temperature).

AUTHOR INFORMATION

Corresponding Author

*E-mail: juha-pekka.pokki@aalto.fi. Author Contributions ∥

These authors contributed equally. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

than TAA as seen in Figures 14 and 15. This leads to lower solvent losses and more efficient recycling of solvent. These factors affect the economics of the separation process. It can therefore be said that MIBK is the more suitable solvent out of these two for furfural extraction. The measured LLE of this work and literature LLE, VLE and excess enthalpy data for the ternary systems and their binary subsystems were used in the optimization of the parameters of the UNIQUAC activity coefficient model. Model described the phase behavior well over the large temperature range.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors would like to acknowledge the Academy of Finland (Suomen Akatemia) for its financial support (decision number 253336). H



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Article

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+ Furfural + Water between 298 and - American Chemical Society

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