Quaternary, Ternary and Binary LLE Measurements for 2-Methoxy-2

Oct 31, 2016 - TAME(1) + Water(3) and Furfural(2) + Water(3). Binary Measurements from Thermal Conductivity Detector. Analysis as Mass Fractions, w, a...
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Quaternary, Ternary and Binary LLE Measurements for 2‑Methoxy-2-methylbutane + Furfural + Acetic Acid + Water at Temperatures between 298 and 341 K Mikael Man̈ nistö,‡ Juha-Pekka Pokki,*,‡ Hele Haapaniemi, and Ville Alopaeus Department of Biotechnology and Chemical Technology, Aalto University, P.O. Box 16100, FI-00076 Aalto, Finland ABSTRACT: Measured quaternary and ternary liquid−liquid equilibrium for 2-methoxy-2-methylbutane (tert-amyl methyl ether, TAME) with furfural, acetic acid, and water are presented in the temperature range between 298 and 341 K. In addition, binary pairs for TAME + water and furfural + water were measured in the range between 298 and 341 K. Results were modeled with UNIQUAC-HOC (Hayden−O’Connell) activity coefficient model and corresponding binary interaction parameters are presented along with measurement data. Solvent suitability for industrial use was assessed for 2-methoxy-2methylbutane and compared to 2-methoxy-2-methylpropane and other industrial solvents.

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INTRODUCTION Focus on biomass as a potential source of raw material for novel chemicals as well as a replacement source for current fossil fuel based chemicals is increasing. Furfural could be a possible source of industrial solvents, green chemicals and even a plausible source of traditional fuels.1 It is also being used as a solvent in lubrication oil production as well as a raw material in pharmaceutical processes. In addition to novel biomass refineries, old production paths like side streams in pulp and paper industry are also of interest in the studies due to their high content of components that could be further refined into furfural. Xylose is one such component that can be dehydrated to produce furfural.2−5 There are various studies to find a solvent for furfural extraction from water with high selectivity and low solubility to the aqueous phase. This work focuses on TAME as a solvent for the extraction of furfural. TAME has much smaller water solubility compared to other ethers such as MTBE studied in earlier work.6 Lower solubility makes TAME potentially interesting, as its loss to raffinate phase and wastewater streams is lower. It has also not been previously studied for such applications, and we aim to provide new data to use in modeling of extraction processes.

dried and distilled for the preparation of the standards to remove traces of water. Furfural (CAS: 98-01-1) had a reported purity of 99% and was distilled to obtain higher purity. Deionized water was prepared in-house using a Millipore Milli-Q system. The reported purities, analyzed purities, and refractive indexes of the compounds are shown in Table 1. Table 1. Used Chemicals and Their Reported and Measured GC Purities, in Wt %, and Refractive Indices, nD25, Measured at 101.3 kPaa chemical 2-methoxy-2methylbutane (TAME) TAME (distilled) furfural furfural (distilled) acetic acid acetic acid (dried distilled) deionized water analytical acetone

measured GC purity

nD25 measured

99

99 99.8+

nD25 from ref 7 1.3859

99.7 99.5 99.9 99.75 99.91

99.93

1.38541 1.52263

1.3859 1.52345 1.52345

1.33249 1.35553

1.3325 1.35596

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.

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EXPERIMENTAL SECTION Materials. All chemicals, except water and analytical acetone, were purchased from Sigma-Aldrich. Chemical purity was verified with gas chromatography (GC) and refractive index measurements with a Dr. Kernchen Abbemat digital automatic refractometer. Analytical acetone (CAS: 67-64-1) was used as an internal standard in the GC runs and was purchased from Merck. TAME (CAS: 994-05-8) had a reported purity of 99% and was distilled to further improve the purity. Acetic acid (HAc, CAS: 64-19-7) had a reported purity of 99.8%+ and was © XXXX American Chemical Society

reported GC purity

Mixtures were prepared gravimetrically using a Precisa 410AM-FR analytical balance, which was calibrated by TEOPAL, certified by FINAS (Finnish Accreditation Service). It had a reported uncertainty of u(m/g) = 0.002. Received: February 19, 2016 Accepted: October 17, 2016

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Table 2. Determined Response Factors, F, for the GC DetectorsThermal Conductivity Detector, TCD and Flame Ionizing Detector, FIDfor TAME + Furfural + Acetic Acid + Water Mixtures with Respect to Acetonea FID

TCD

component

TAME

furfural

HAc

TAME

furfural

HAc

water

F (response factor)

0.684

0.904

1.833

1.221

1.159

1.089

0.889

a

Standard uncertainties (u) are u(TAME, FID) = 0.013, u(furfural, FID) = 0.013, u(HAc, FID) = 0.032, u(TAME, TCD) = 0.021, u(furfural, TCD) = 0.016, u(HAc, TCD) = 0.012, u(water, TCD) = 0.011.

Table 3. Optimized UNIQUAC-HOC Binary Interaction Parameters for Components Used component i

furfural

TAME

TAME

furfural

water

component j

water

water

furfural

HAc

HAc

HAc

Aij Aji Bij Bji Cij Cji Dij Dji

−4.0277 0.0267 68.5197 108.2790 0 0 0.0106 −0.0024

−0.4524 −1.931 −481.9 474.5 0 0 0 0

−0.5816 0.3131 −39.2688 −50.1292 0 0 0 0

−1.5780 1.2100 689.7579 −644.5795 0 0 0 0

0.0462 5.3635 235.4490 −2413.0124 0 0 0 0

−3.8465 0.7498 719.8953 14.1299 0 0 0 0

Table 4. TAME(1) + Water(3) and Furfural(2) + Water(3) Binary Measurements from Thermal Conductivity Detector Analysis as Mass Fractions, w, as a function of Temperature, T, at Pressure p = 101 kPaa organic phase

Table 5. continued organic phase

aqueous phase

Tcell/K

w1

w2

w3

w1

w2

w3

298.2 298.2 321.7 341.1 298.3 298.2 322.5 342.2

0.991 0.992 0.989 0.988 0 0 0 0

0 0 0 0 0.951 0.950 0.934 0.911

0.009 0.008 0.011 0.012 0.049 0.050 0.066 0.089

0.010 0.011 0.006 0.005 0 0 0 0

0 0 0 0 0.077 0.079 0.094 0.110

0.990 0.989 0.994 0.995 0.923 0.921 0.906 0.890

a

Standard uncertainties (u) are u(T/K) = 0.2, u(w1, organic) = 0.001, u(w2, organic) = 0.002, u(w3, organic) = 0.003, u(w1, aqueous) = 0.008, u(w2, aqueous) = 0.008, u(w3, aqueous) = 0.002, and u(p/kPa) = 1.

Table 5. TAME(1) + Furfural(2) + Water(3) Ternary Measurements from Thermal Conductivity Detector Analysis as Mass Fractions, w, as a Function of Temperature, T, at Pressure p = 101 kPaa organic phase

aqueous phase

Tcell/K

w1

w2

w3

w1

w2

w3

298.2 298.4 298.2 298.2 298.4 298.2 298.3 298.4 298.2 298.2 298.2 322.5 322.3 322.2 322.1

0.073 0.117 0.136 0.182 0.198 0.241 0.316 0.437 0.481 0.562 0.769 0.046 0.069 0.111 0.130

0.881 0.838 0.821 0.777 0.761 0.720 0.649 0.534 0.492 0.415 0.216 0.888 0.869 0.829 0.813

0.046 0.045 0.043 0.041 0.041 0.039 0.035 0.029 0.027 0.023 0.015 0.066 0.062 0.060 0.057

0.003 0.005 0.005 0.007 0.007 0.008 0.008 0.009 0.010 0.010 0.010 0.002 0.002 0.003 0.004

0.070 0.068 0.065 0.061 0.062 0.059 0.055 0.051 0.048 0.045 0.032 0.086 0.080 0.077 0.075

0.927 0.927 0.930 0.932 0.931 0.933 0.937 0.940 0.942 0.945 0.958 0.912 0.918 0.920 0.921

TAME

aqueous phase

Tcell/K

w1

w2

w3

w1

w2

w3

321.9 322.3 322.5 322.1 322.5 321.9 322.5 322.3 322.1 321.9 322.5 322.0 341.9 341.6 341.2 341.9 341.5 342.3 341.2 342.3 341.9 341.6 341.2 342.2 341.9 341.5

0.176 0.227 0.228 0.252 0.307 0.325 0.356 0.379 0.436 0.533 0.677 0.847 0.062 0.120 0.164 0.216 0.243 0.288 0.315 0.359 0.383 0.437 0.533 0.662 0.747 0.839

0.772 0.723 0.722 0.700 0.649 0.634 0.605 0.583 0.532 0.439 0.301 0.138 0.857 0.807 0.774 0.721 0.702 0.658 0.635 0.596 0.574 0.526 0.434 0.314 0.231 0.144

0.052 0.050 0.050 0.048 0.044 0.041 0.039 0.038 0.032 0.028 0.022 0.015 0.081 0.073 0.062 0.063 0.055 0.054 0.050 0.045 0.043 0.037 0.033 0.024 0.022 0.017

0.005 0.005 0.005 0.005 0.006 0.006 0.006 0.006 0.006 0.006 0.006 0.007 0.002 0.004 0.004 0.005 0.005 0.005 0.005 0.005 0.005 0.006 0.006 0.006 0.006 0.006

0.071 0.065 0.066 0.064 0.062 0.059 0.057 0.056 0.053 0.048 0.040 0.024 0.098 0.090 0.087 0.078 0.074 0.073 0.068 0.066 0.063 0.060 0.053 0.044 0.036 0.026

0.924 0.930 0.929 0.931 0.932 0.935 0.937 0.938 0.941 0.946 0.954 0.969 0.900 0.906 0.909 0.917 0.921 0.922 0.927 0.929 0.932 0.934 0.941 0.950 0.958 0.968

a Standard uncertainties (u) are u(T/K) = 0.2, u(w1,organic) = 0.007, u(w2,organic) = 0.007, u(w3,organic) = 0.002, u(w1,aqueous) = 0.001, u(w2,aqueous) = 0.002, u(w3,aqueous) = 0.003, and u(p/kPa) = 1.

Apparatus and Procedure. Quaternary and ternary liquid−liquid equilibrium (LLE) measurements for the quaternary and ternary systems with TAME were carried out in the temperature range from 298 to 341 K. The same static glass cell apparatus and measurement style used in earlier work6 was used in the measurements. Analysis of the equilibrium phases was done with an Agilent Technologies 6890N gas B

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Table 6. TAME(1) + Acetic Acid(2) + Water(3) Ternary Measurements from Thermal Conductivity Detector Analysis as Mass Fractions, w, as a Function of Temperature, T, at Pressure p = 101 kPaa organic phase

aqueous phase

Tcell/K

w1

w2

w3

w1

w2

w3

298.2 298.2 298.2 298.2 298.2 298.2 298.2 298.2 322.4 322.2 322.0 321.7 322.4 322.1 321.9 342.2 341.8 341.5 341.1 342.1 341.8 341.4

0.992 0.963 0.926 0.878 0.789 0.733 0.666 0.392 0.990 0.963 0.929 0.886 0.815 0.766 0.710 0.989 0.961 0.928 0.886 0.824 0.778 0.717

0.000 0.025 0.056 0.095 0.167 0.210 0.259 0.344 0.000 0.023 0.052 0.088 0.148 0.186 0.228 0.000 0.023 0.051 0.086 0.139 0.176 0.221

0.008 0.012 0.018 0.027 0.044 0.057 0.075 0.264 0.010 0.014 0.019 0.026 0.037 0.048 0.062 0.011 0.016 0.021 0.028 0.037 0.046 0.062

0.010 0.012 0.014 0.018 0.025 0.033 0.045 0.066 0.006 0.008 0.011 0.014 0.022 0.030 0.041 0.005 0.007 0.010 0.014 0.022 0.030 0.042

0.000 0.057 0.114 0.173 0.257 0.303 0.348 0.394 0.000 0.058 0.117 0.178 0.264 0.311 0.354 0.000 0.061 0.122 0.184 0.269 0.315 0.359

0.990 0.931 0.872 0.809 0.718 0.664 0.607 0.540 0.994 0.934 0.872 0.808 0.714 0.659 0.605 0.995 0.932 0.868 0.802 0.709 0.655 0.599

Figure 1. Furfural mass fractions in extract and raffinate phase for TAME (1) + furfural (2) + water (3) (left) and Othmer−Tobias plot (right) as calculated from data presented in Table 5: ◆, measured at 298 K; ▲, measured at 322 K; ○, measured at 341 K.

Figure 2. Acetic acid mass fractions in extract and raffinate phase for TAME (1) + acetic acid (2) + water (3) (left) and Othmer−Tobias plot (right) as calculated from data presented in Table 6: ◆, measured at 298 K; ▲, measured at 322 K; ○, measured at 341 K.

chromatograph equipped with two detectors and two columns. The setup was explained in further in detail in earlier work.6,8 Analysis of Samples. Method for response factor development was discussed in earlier work6 along with uncertainty

a

Standard uncertainties (u) are u(T/K) = 0.2, u(w1,organic) = 0.005, u(w2,organic) = 0.004, u(w3,organic) = 0.002, u(w1,aqueous) = 0.001, u(w2,aqueous) = 0.006, u(w3,aqueous) = 0.006, and u(p/kPa) = 1.

Table 7. TAME(1) + Furfural(2) + Acetic acid(3) + Water(4) Quaternary Measurements from Thermal Conductivity Detector Analysis as Mass Fractions, w, as a Function of Temperature, T, at Pressure p = 101 kPaa organic phase

aqueous phase

Tcell/K

w1

w2

w3

w4

w1

w2

w3

w4

298.4 298.4 298.3 298.4 298.3 298.2 298.2 298.2 298.2 298.2 298.2 298.2 321.9 322.2 322.4 322.2 322.0 321.7 321.7 322.4 321.9 321.9 322.2 322.2 341.8

0.415 0.488 0.563 0.565 0.579 0.622 0.633 0.636 0.691 0.699 0.749 0.770 0.468 0.492 0.601 0.609 0.624 0.645 0.649 0.669 0.699 0.701 0.750 0.769 0.624

0.285 0.235 0.236 0.185 0.251 0.135 0.191 0.122 0.087 0.072 0.038 0.032 0.259 0.218 0.165 0.210 0.224 0.122 0.110 0.168 0.065 0.080 0.036 0.029 0.109

0.152 0.169 0.109 0.172 0.078 0.185 0.108 0.189 0.183 0.195 0.189 0.177 0.147 0.153 0.165 0.102 0.074 0.179 0.183 0.100 0.191 0.181 0.188 0.179 0.198

0.148 0.108 0.092 0.078 0.092 0.058 0.068 0.053 0.039 0.034 0.024 0.021 0.126 0.137 0.069 0.079 0.078 0.054 0.058 0.063 0.045 0.038 0.026 0.023 0.069

0.074 0.043 0.041 0.029 0.045 0.021 0.029 0.019 0.016 0.014 0.013 0.012 0.069 0.044 0.029 0.040 0.044 0.020 0.017 0.027 0.012 0.014 0.009 0.009 0.018

0.320 0.275 0.290 0.226 0.311 0.177 0.245 0.160 0.122 0.102 0.059 0.051 0.325 0.281 0.234 0.292 0.318 0.184 0.164 0.251 0.105 0.128 0.062 0.053 0.170

0.079 0.067 0.045 0.054 0.035 0.048 0.038 0.047 0.040 0.040 0.034 0.033 0.082 0.074 0.062 0.048 0.038 0.054 0.050 0.041 0.043 0.044 0.037 0.035 0.060

0.527 0.615 0.624 0.691 0.609 0.754 0.688 0.774 0.822 0.844 0.894 0.904 0.524 0.601 0.675 0.620 0.600 0.742 0.769 0.681 0.840 0.814 0.892 0.903 0.752

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Table 7. continued organic phase

aqueous phase

Tcell/K

w1

w2

w3

w4

w1

w2

w3

w4

341.5 341.1 341.5 341.8 342.2 342.1 341.5 342.1 341.8 341.8

0.637 0.650 0.657 0.663 0.674 0.688 0.700 0.724 0.742 0.750

0.214 0.117 0.205 0.185 0.066 0.156 0.077 0.145 0.030 0.034

0.073 0.177 0.067 0.085 0.211 0.097 0.181 0.082 0.193 0.186

0.076 0.056 0.071 0.067 0.049 0.059 0.042 0.049 0.035 0.030

0.046 0.020 0.042 0.036 0.012 0.038 0.014 0.025 0.008 0.009

0.323 0.189 0.314 0.288 0.113 0.253 0.132 0.246 0.057 0.064

0.040 0.061 0.035 0.042 0.054 0.043 0.050 0.035 0.042 0.040

0.591 0.730 0.609 0.634 0.821 0.666 0.804 0.694 0.893 0.887

a Standard uncertainties (u) are u(T/K) = 0.2, u(w1,organic) = 0.005, u(w2,organic) = 0.007, u(w3,organic) = 0.004, u(w4,organic) = 0.002, u(w1,aqueous) = 0.001, u(w2,aqueous) = 0.007, u(w3,aqueous) = 0.006, u(w4,aqueous) = 0.006, and u(p/kPa) = 1.

estimation. For TAME measurements, the following mixtures, all diluted with known amount of acetone, were made for the response factor determination: furfural + water, furfural + TAME, TAME + water, HAc + water, HAc + furfural, and HAc + TAME; five separate samples of each mixture were prepared with different compositions. Response factors were calculated with eq 1 and their uncertainties with eq 2

ΔFi =

A Fi = Fstd × std × Ai

mi g mstd g

(1)

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

(2)

Response factors for TAME, furfural, HAc, and water along with their calculated uncertainty are visible in Table 2. Modeling. Measured data points for the binary systems were modeled with available literature data for LLE9−14 and VLE15−21 using UNIQUAC-HOC activity coefficient model. Regression was done using Aspen Plus 8.6 data regression system. All the used VLE data for furfural + water binary was found to pass the Herington test and all the used VLE data for HAc + water was found to pass either Herington test (Calvar,16 Bernatova,17 and Ping19) or Van Ness test (Arich,15 Bernatova,17 Luo,18 and Ping19). The fit of the parameters regressed using binary data was tested against the ternary and quaternary measurements. The regressed UNIQUAC parameters are shown in Table 3. Pure component properties were retrieved with Aspen Plus from NIST ThermoData Engine database. Hayden− O’Connell eta parameters for TAME were missing but set equal to parameters of diethyl ether (CAS: 60-29-7) based on the similarity of chemical structure.

Figure 3. Comparison of our measured TAME(1) + Water(2) binary data (Table 4) to literature data. Left figure represents the aqueous phase and right figure the organic phase. The line represents the model; ○, this work; *, literature data by Linek et al.;9 + , literature data by Stephenson et al.;10 ▲, literature data by Arce et al.12

Figure 4. Regressed models for TAME(1) + furfural(2) + water(3) with UNIQUAC-HOC, shown with our measurements (Table 5). Left figure is the water phase enlarged. − , modeled; ◆, measured. D

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phase indicated the success of sampling. These graphs both provide a trend that follows mass fraction of furfural in one phase. Although the graphs do not directly provide an analytical method for determining errors in measurements, the deviation from a clear trend shown by the plots for the Othmer−Tobias, furfural mass fractions or the LLE diagrams were taken as an indication of unsuccessful sampling and these points were rejected. Plots for TAME(1) + furfural(2) + water(3) are available in Figure 1 and plots for TAME(1) + acetic acid(2) + water(3) are available in Figure 2. In total, both rejection methods resulted in 12 rejected data points for the furfural ternary and none for the acetic acid ternary and the quaternary system. To validate our measurements further, the measured binary TAME + water data was compared to literature in Figure 3. The regressed UNIQUAC parameters and the model for TAME + furfural + water and for TAME + acetic acid + water were compared to our measured data in Figures 4 and 5. Figure 6 represents the quaternary system with the model. In addition to graphical analysis, a RMSD value for all the data sets was calculated and the values are reported in Table 8. To analyze efficiency of the solvent, we calculated both the selectivity and distribution factor for furfural and for acetic acid with the selected solvent mixtures. The distribution coefficient was calculated with eq 3 and selectivity calculated with eq 4 wfurfural,extract K= wfurfural,raffinate (3) Figure 5. Regressed parameters for TAME(1) + acetic acid(2) + water(3) with UNIQUAC-HOC, shown with our measurements (Table 6). Left figure is the water phase enlarged. − , modeled; ◆, measured.

S=

■

wfurfural,extract wfurfural,raffinate

×

wwater,raffinate wwater,extract

(4)

The calculated distribution coefficients and selectivities are presented in Tables 9 and 10. Plots for the selectivity of furfural and acetic acid in the extraction as well as the distribution factors for TAME(1) + furfural(2) + water(3) are shown in Figure 7 and with TAME(1) + acetic acid(2) + water(3) in Figure 8. When furfural selectivity and distribution between phases is compared to for example tert-amyl alcohol (TAA) or methyl isobutyl ketone (MIBK) studied earlier,8 it can be observed that the distribution coefficients lie between those of TAA and MIBK. MIBK has a higher selectivity toward furfural than TAME does; however, both have considerably higher selectivity than that of TAA. MIBK is generally considered as a good solvent for process industry and as TAME has in our studies shown similar efficiency, it is a good potential subject for further analysis. In Figure 9, we have presented the measured data within this work and the earlier work conducted on MIBK and TAA. In case of acetic acid, MIBK has been studied earlier by Saien23 and TAA by Fahim and Al-Muhtaseb.24 Their measured

RESULTS AND DISCUSSION Samples were analyzed with the GC and the mass fractions calculated based on the response factors. Component masses in the samples were calculated based on GC peak areas for components and standard and response factors for each component. The method for calculating the masses and mass fractions of each of the components were presented in detail in earlier work,6 as were the methods for the calculation of uncertainties for each composition. The measured data for the quaternary, ternary and binary mixtures TAME and other components are presented in tables below. Binary mixtures for TAME + Water and Furfural + Water in Table 4. The ternary mixtures in Table 5 for TAME + furfural + water and in Table 6 for TAME + HAc + water. The quaternary mixtures of TAME + furfural + HAc + water are presented in Table 7. Othmer−Tobias plot22 and a plot of furfural mass fraction in TAME phase as a function of furfural mass fraction in aqueous

Figure 6. Regressed parameters for TAME(1) + furfural(2) + acetic acid(3) + water(4) with UNIQUAC-HOC, shown with our measurements (Table 7). The spheres represent measured data points and the surface represents the model. Temperatures from left to right are 298 K, 322 K, 341 K. E

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Table 8. Calculated RMSD for the Regressed Models for TAME(1) + Furfural(2) + Acetic Acid (3) and Water(4) Presented with Measurement Temperature, T, the Data Type and Reference to the Table in Which the Data Can Be Found Tcell/K

data type

table

∼298 ∼322 ∼341 ∼298 ∼322 ∼341 ∼298 ∼322 ∼341 298−341 298−341

quaternary quaternary quaternary ternary ternary ternary ternary ternary ternary binary binary

Table Table Table Table Table Table Table Table Table Table Table

RMSDTAME

RMSDFurfural

RMSDHAc

RMSDWater

0.01424 0.01366 0.02016 0.00828 0.00601 0.00568 0.00050 0.00070 0.00138 0.00482

0.01790 0.01846 0.01803

0.01872 0.02268 0.02083 0.02119 0.02503 0.02005

0.04433 0.05093 0.05237 0.01480 0.02357 0.02079 0.00698 0.00774 0.01077 0.00482 0.00467

7 7 7 6 6 6 5 5 5 4 4

0.00714 0.00777 0.01089 0.00467

Table 9. Calculated Distribution Coefficients, K, and Selectivities, S, of the Mixture TAME(1) + Furfural(2) + Water(3) Presented with Measurement Temperature, T, and Furfural Mass Fraction, w, from the Data Presented in Table 5a

Table 9. continued Tcell/K

wfurfural,extract

wfurfural,raffinate

Kfurfural

Sfurfural

341.6 341.9

0.807 0.858

0.090 0.098

8.95 8.79

111.85 98.08

a

Tcell/K

wfurfural,extract

wfurfural,raffinate

Kfurfural

Sfurfural

298.2 298.2 298.2 298.4 298.3 298.2 298.4 298.2 298.2 298.4 298.2 322.0 322.5 321.9 322.1 322.3 322.5 321.9 322.5 322.1 322.5 322.3 321.9 322.1 322.2 322.3 322.5 341.5 341.9 342.2 341.2 341.6 341.9 342.3 341.2 342.3 341.5 341.9 341.2

0.216 0.415 0.492 0.535 0.649 0.720 0.761 0.778 0.821 0.838 0.881 0.138 0.301 0.439 0.532 0.583 0.605 0.634 0.649 0.700 0.722 0.723 0.772 0.813 0.829 0.869 0.888 0.144 0.231 0.314 0.434 0.526 0.574 0.596 0.635 0.658 0.702 0.721 0.774

0.032 0.045 0.048 0.050 0.055 0.059 0.062 0.061 0.065 0.068 0.069 0.024 0.040 0.048 0.053 0.056 0.058 0.059 0.062 0.064 0.066 0.065 0.071 0.075 0.077 0.080 0.086 0.026 0.036 0.044 0.053 0.060 0.063 0.066 0.068 0.073 0.074 0.078 0.087

6.78 9.25 10.23 10.62 11.79 12.23 12.26 12.70 12.72 12.33 12.69 5.67 7.56 9.14 10.01 10.43 10.52 10.74 10.45 10.94 11.00 11.07 10.80 10.82 10.76 10.87 10.37 5.52 6.35 7.06 8.13 8.74 9.07 9.00 9.39 9.00 9.53 9.21 8.94

420.15 384.33 360.81 348.70 315.31 295.56 281.36 290.95 275.03 255.95 254.14 368.75 331.11 303.86 290.70 262.00 251.56 241.35 220.33 214.11 203.52 203.88 192.47 175.24 165.97 160.59 144.57 314.11 283.35 279.84 232.81 221.49 196.46 185.77 175.52 154.02 158.01 134.99 131.37

Standard uncertainties (u) are u(T/K) = 0.2, u(wfurfural,extract) = 0.007, u(wfurfural,aqueous) = 0.002, u(K) = 1.32, u(S) = 27.10.

Table 10. Calculated Distribution Coefficients, K, and Selectivities, S, of the mixture TAME(1) + Acetic Acid(2) + Water(3) Presented with Measurement Temperature, T, and Furfural Mass Fraction, w, from the Data Presented in Table 6a Tcell/K

wHAc,extract

wHAc,raffinate

KHAc

SHAc

298.2 298.2 298.2 298.2 298.2 298.2 298.2 322.2 322.0 321.7 322.4 322.1 321.9 341.8 341.5 341.1 342.1 341.8 341.4

0.0245 0.0563 0.0954 0.1669 0.2103 0.2586 0.3438 0.0233 0.0523 0.0880 0.1479 0.1860 0.2281 0.0231 0.0514 0.0858 0.1391 0.1762 0.2205

0.0566 0.1139 0.1731 0.2568 0.3035 0.3478 0.3938 0.0583 0.1172 0.1784 0.2640 0.3115 0.3540 0.0611 0.1220 0.1843 0.2693 0.3153 0.3584

0.43 0.49 0.55 0.65 0.69 0.74 0.87 0.40 0.45 0.49 0.56 0.60 0.64 0.38 0.42 0.47 0.52 0.56 0.62

32.66 23.92 16.61 10.51 8.14 6.01 1.78 26.98 20.53 15.19 10.72 8.20 6.27 22.41 17.46 13.44 10.00 7.92 5.91

a

Standard uncertainties (u) are u(T/K) = 0.2, u(wfurfural,extract) = 0.004, u(wfurfural,aqueous) = 0.006, u(K) = 0.05, u(S) = 2.97.

Figure 7. Distribution coefficient and selectivity for the mixture of TAME(1) + furfural(2) + water(3) for furfural as a function of furfural mass fraction in raffinate: ◆, measured at 298 K; ▲, measured at 322 K; ○, measured at 341 K. F

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and MTBE in the quaternary solvent (1) + furfural (2) + acetic acid (3) + water (4) mixtures. When the distribution coefficients for furfural are drawn as a function of furfural mass fraction in raffinate phase for the quaternary mixtures, we can see that for both cases, the behavior quickly changes from the behavior of the ternary furfural mixture. The effect is faster with MTBE, but TAME does not keep the furfural behavior for long either. The behavior can be seen in the quaternary graphs Figures 11 and 13 as a function of both acetic acid and furfural mass fractions. The effect is further presented in a comparison of the ternary and the quaternary mixtures in Figures 12 and 14. These figures illustrate clearly the effect acetic acid has on the distribution and further suggest that in an industrial process acetic acid should be removed prior to furfural. In the light of these results, however, it seems that TAME is the most suitable solvent out of the ones our group has been working with so far.

Figure 8. Distribution coefficient and selectivity for the mixture of TAME(1) + HAc(2) + water(3) for acetic acid as a function of acetic acid mass fraction in raffinate: ◆, measured at 298 K; ▲, measured at 322 K; ○, measured at 341 K.

data can be used to calculate distribution coefficient and selectivity of the solvent for acetic acid. The data measured by us provides distribution coefficients and selectivities for TAME that can be compared to our earlier measured data for MTBE6 as well as measurements by others. These are presented in Figure 10. From the ternary figures it would seem that TAME would be a suitable and effective solvent to extract furfural from an aqueous mixture, this is also backed up by the quaternary measurements. In Tables 11 and 12, we present the distribution coefficients and selectivites for both components with TAME

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CONCLUSIONS This work presents new liquid−liquid equilibria data for binary, ternary, and quaternary systems with TAME as a solvent. Systems consist of solvent + furfural + acetic acid + water in different compositions. Measured experimental data along with literature data was used to regress the parameters for UNIQUAC thermodynamic model combined with a Hayden O’Connell gas

Figure 9. Distribution coefficient and selectivity for the mixture of solvent(1) + furfural(2) + water(3) for furfural as a function of furfural mass fraction in raffinate: ◇, MIBK;8 *, MTBE6 at 298 K; △, MTBE6 at 308 K; □, TAME; ○, TAA.8 G

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Figure 10. Distribution coefficient and selectivity for the mixture of solvent(1) + acetic acid(2) + water(3) for acetic acid as a function of acetic acid mass fraction in raffinate: ◇, MIBK;23 *, MTBE6 at 298 K; △, MTBE6 at 308 K; □, TAME; ○, TAA.24

Table 11. Distribution Coefficients and Selectivities of Furfural and Acetic Acid in Quaternary Mixtures with TAME (1) + Furfural (2) + Acetic Acid (3) + Water (4) Tcell/K

w2,ext

w3,ext

K2

K3

S2

S3

298.2 298.2 298.2 298.2 298.2 298.2 298.4 298.2 298.4 298.3 298.3 298.4 322.2 322.2 321.9 321.9 321.7 321.7 322.4 322.4 322.2 322.2

0.0293 0.0355 0.0672 0.0811 0.1142 0.1269 0.1744 0.1809 0.2223 0.2244 0.2390 0.2702 0.0275 0.0332 0.0608 0.0750 0.1029 0.1151 0.1556 0.1588 0.1997 0.2058

0.1865 0.1987 0.2054 0.1932 0.2000 0.1955 0.1822 0.1151 0.1803 0.1161 0.0837 0.1627 0.1882 0.1975 0.2008 0.1905 0.1937 0.1889 0.1747 0.1067 0.1088 0.1632

5.38 5.48 4.87 4.54 4.01 3.85 3.14 2.86 2.51 2.39 2.20 1.91 5.12 5.10 4.36 4.02 3.59 3.26 2.65 2.45 2.13 2.06

0.61 0.64 0.69 0.70 0.75 0.75 0.81 0.77 0.85 0.81 0.80 0.88 0.55 0.57 0.61 0.62 0.66 0.66 0.70 0.66 0.71 0.77

229.76 203.28 121.21 97.10 58.78 51.11 28.20 28.96 14.41 16.31 14.62 6.83 205.74 174.02 81.44 85.84 47.86 45.43 26.11 26.69 16.93 9.14

26.08 23.60 17.29 14.99 11.06 10.01 7.27 7.85 4.88 5.54 5.34 3.16 22.00 19.30 11.41 13.24 8.85 9.22 6.88 7.22 5.68 3.39

Table 11. continued Tcell/K

w2,ext

w3,ext

K2

K3

S2

S3

322.0 321.9 341.8 341.8 342.2 341.5 341.8 341.1 342.1 342.1 342.1 341.8 341.8 341.5 341.5 341.5

0.2134 0.2460 0.0277 0.0316 0.0617 0.0718 0.1021 0.1095 0.1371 0.1458 0.1479 0.1747 0.1873 0.1944 0.2034 0.2603

0.0788 0.1566 0.2031 0.1956 0.2223 0.1909 0.2089 0.1876 0.0871 0.1708 0.1035 0.0909 0.1692 0.0712 0.0775 0.1409

1.94 1.77 4.61 4.61 3.88 3.59 3.27 2.89 2.29 2.36 2.22 2.03 1.92 1.87 1.81 1.53

0.70 0.79 0.51 0.52 0.58 0.57 0.63 0.61 0.58 0.64 0.61 0.63 0.68 0.65 0.66 0.83

14.97 7.39 119.31 137.63 66.02 70.03 36.21 38.07 32.33 24.70 25.45 19.24 12.69 16.10 14.10 3.62

5.42 3.31 13.24 15.52 9.83 11.15 7.02 8.03 8.26 6.68 7.06 6.02 4.52 5.56 5.12 1.97

a Standard uncertainties (u) are u(T/K) = 0.2, u(w2,organic) = 0.007, u(w3,organic) = 0.004, u(K2) = 0.37, u(K3) = 0.05, u(S2) = 7.69, u(S3) = 1.12.

phase model. Models can be seen to describe the systems accurately. The models over predict the amount of solvent in aqueous phase slightly. TAME was compared to a previously studied solvent, MTBE, and both of the solvents show low H

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Table 12. Distribution Coefficients and Selectivities of Furfural and Acetic Acid in Quaternary Mixtures with MTBE (1) + Furfural (2) + Acetic Acid (3) + Water (4).6 Tcell/K

w2,ext

w3,ext

K2

K3

S2

S3

298.2 298.2 298.2 298.2 298.2 298.3 298.2 298.4 298.2 298.2 298.2 298.4 298.2 298.2 307.6 307.6 307.8 307.8 307.5 307.8 307.7 307.8 307.7 307.7

0.2030 0.2561 0.2586 0.2064 0.1777 0.2474 0.1899 0.2711 0.1768 0.1355 0.1449 0.2348 0.1616 0.1413 0.1777 0.2486 0.2712 0.1783 0.1359 0.1466 0.2363 0.1622 0.1424 0.1324

0.0409 0.0428 0.0823 0.0873 0.0873 0.1299 0.1374 0.1680 0.1788 0.1936 0.1945 0.2188 0.2342 0.2367 0.0851 0.1277 0.1645 0.1750 0.1897 0.1901 0.2162 0.2290 0.2325 0.2704

6.69 7.22 6.33 5.86 5.62 5.11 4.81 4.12 4.03 3.64 3.66 2.57 2.77 2.72 5.49 4.91 3.89 3.85 3.54 3.52 2.49 2.69 2.68 1.60

1.04 1.08 1.11 1.09 1.08 1.13 1.12 1.13 1.13 1.11 1.11 1.09 1.11 1.10 1.01 1.08 1.08 1.07 1.06 1.06 1.06 1.07 1.06 1.04

135.16 125.00 72.89 72.76 74.19 38.61 37.76 21.04 23.88 20.58 19.95 7.35 9.55 9.52 74.35 38.32 20.20 23.73 21.00 20.34 7.30 9.74 9.88 2.92

21.02 18.66 12.81 13.55 14.20 8.56 8.79 5.76 6.69 6.26 6.06 3.13 3.83 3.85 13.70 8.44 5.58 6.61 6.29 6.10 3.11 3.86 3.91 1.89

Figure 13. Distribution coefficient of furfural for the mixture of MTBE(1) + furfural(2) + acetic acid(3) + water(4) in a x−y projection (left graph) and in a ternary plot (right graph) as a function of furfural mass fraction in raffinate:6 ◇, 298 K; ○, 308 K.

Figure 14. Distribution coefficient of furfural for the mixture of MTBE(1) + furfural(2) + water(3) (left graph) and for the mixture of MTBE(1) + furfural(2) + acetic acid(3) + water(4) (right graph) as a function of acetic acid mass fraction in raffinate:6 ◇, 298 K; ○, 308 K.

solubility to aqueous phase and high selectivity toward extraction of furfural. Further study on such solvents would be advisable, as it would seem that though TAME has relatively high selectivity, the distribution coefficient at low furfural mass fractions is relatively low. This would suggest large amounts of TAME to be needed for the extraction at similar mass fractions of furfural when compared with MIBK, (methyl isobutyl ketone), which is one industrially common solvent. Despite the higher amounts needed, both the distribution coefficient and the selectivity toward acetic acid in ternary mixtures is considerably lower than with MIBK.

a Standard uncertainties (u) are u(T/K) = 0.2, u(w2,organic) = 0.003, u(w3,organic) = 0.003, u(K2) = 0.42, u(K3) = 0.05, u(S2) = 4.39, u(S3) = 0.73.

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AUTHOR INFORMATION

Corresponding Author

Figure 11. Distribution coefficient of furfural for the mixture of TAME(1) + furfural(2) + acetic acid(3) + water(4) in an x−y projection (left graph) and in a ternary plot (right graph) as a function of furfural mass fraction in raffinate: ◇, 298 K; △, 323 K; ○, 343 K.

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

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

Funding

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

The authors declare no competing financial interest.

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REFERENCES

(1) Addepally, U.; Thulluri, C. Recent progress in production of fuel range liquid hydrocarbons from biomass-derived furanics via strategic catalytic routes. Fuel 2015, 159, 935−942. (2) Cabezas, J. L.; Barcena, L. A.; Coca, J.; Cockrem, M. Extraction of furfural from aqueous solutions using alcohols. J. Chem. Eng. Data 1988, 33, 435−437.

Figure 12. Distribution coefficient of furfural for the mixture of TAME(1) + furfural(2) + water(3) (left graph) and for the mixture of TAME(1) + furfural(2) + acetic acid(3) + water(4) (right graph) as a function of furfural mass fraction in raffinate: ◇, 298 K; △, 323 K; ○, 343 K. I

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(3) Sahu, A. K.; Srivastava, V. C.; Mall, I. D.; Lataye, D. H. Adsorption of Furfural from Aqueous Solution onto Activated Carbon: Kinetic, Equilibrium and Thermodynamic Study. Sep. Sci. Technol. 2008, 43, 1239−1259. (4) Pei, Y.; Wu, K.; Wang, J.; Fan, J. Recovery of Furfural from Aqueous Solution by Ionic Liquid Based Liquid−Liquid Extraction. Sep. Sci. Technol. 2008, 43, 2090−2102. (5) Lamminpäa,̈ K.; Ahola, J.; Tanskanen, J. Acid-catalysed xylose dehydration into furfural in the presence of kraft lignin. Bioresour. Technol. 2015, 177, 94−101. (6) Männistö, M.; Pokki, J.-P.; Haapaniemi, H.; Alopaeus, V. Quaternary, Ternary, and Binary LLE Measurements for 2-Methoxy-2methylpropane + Furfural + Acetic Acid + Water at Temperatures between 298 and 307 K. J. Chem. Eng. Data 2016, 61, 2458−2466. (7) Design Institute for Physical Properties DIPPR Project 801 (Full Version), 2014. http://aiche.org/dippr (accessed February, 2016). (8) Männistö, M.; Pokki, J.-P.; Creati, A.; Voisin, A.; Zaitseva, A.; Alopaeus, V. Ternary and Binary LLE Measurements for Solvent (4Methyl-2-pentanone and 2-Methyl-2-butanol) + Furfural + Water between 298 and 401 K. J. Chem. Eng. Data 2016, 61, 903−911. (9) Linek, J.; Bernatova, S. Liquid-Liquid Equilibria in the System Methanol-Water-Tert-Amyl Methyl Ether. Collect. Czech. Chem. Commun. 1986, 51, 188. (10) Stephenson, R. M. Mutual solubilities: water-ketones, waterethers, and water-gasoline-alcohols. J. Chem. Eng. Data 1992, 37, 80− 95. (11) Stephenson, R. M. Mutual solubility of water and aldehydes. J. Chem. Eng. Data 1993, 38, 630−633. (12) Arce, A.; Blanco, M.; Riveiro, R.; Vidal, I. Liquid-liquid equilibria of (MTBE or TAME) + ethanol + water mixtures. Can. J. Chem. Eng. 1996, 74, 419−422. (13) Liu, D.; Li, Q.; Chen, Z. Determination of mutual solubility data for four binary systems by the cloud point-equilibrium stillheterothermic methods. Tianranqi Huagong 1994, 19, 52−58. (14) Park, S.; Hwang, I.; Kwak, H. Binary Liquid−Liquid Equilibrium (LLE) for Dibutyl Ether (DBE) + Water from (288.15 to 318.15) K and Ternary LLE for Systems of DBE + C1 ∼ C4 Alcohols + Water at 298.15 K. J. Chem. Eng. Data 2008, 53, 2089−2094. (15) Arich, G.; Tagliavini, G. Liquid-vapor equilibrium isotherms for the water-acetic acid system. Ric. Sci. 1958, 28, 2493. (16) Calvar, N.; Domínguez, A.; Tojo, J. Vapor−liquid equilibria for the quaternary reactive system ethyl acetate + ethanol + water + acetic acid and some of the constituent binary systems at 101.3 kPa. Fluid Phase Equilib. 2005, 235, 215−222. (17) Bernatová, S.; Aim, K.; Wichterle, I. Isothermal vapour−liquid equilibrium with chemical reaction in the quaternary water + methanol + acetic acid + methyl acetate system, and in five binary subsystems. Fluid Phase Equilib. 2006, 247, 96−101. (18) Luo, J.; Wu, S.; Sun, Y. Vapor-Liquid Equilibrium of Acetic Acid-Water System Under Magnetic Field. Tianjin Daxue Xuebao 2007, 40, 1300. (19) Ping, L.; Peng, Y.; Mao, J. Vapor-Liquid Equilibria of Acetic Acid-Water-N-Methylpyrrolidone System at 26.67 kPa. J. Chem. Eng. Chin. Univ. 2011, 25, 554−558. (20) Tsirlin, Y. A. Liquid-vapour equilibrium in the furfural - water system at reduced pressures. Zh. Fiz. Khim. 1962, 36, 1673. (21) Ni, X.; Wang, Z. Studies on VLE of Carbinol-Furfural-WaterAcetic acid. Chemical Engineering (China) 1987, 3, 50. (22) Othmer, D. F.; Tobias, P. E. Liquid-Liquid Extraction Data The Line Correlation. Ind. Eng. Chem. 1942, 34, 693−696. (23) Saien, J.; Daliri, S.; Norouzi, M. Liquid-liquid equilibria for the system water + 4-methylpentan-2-one + acetic acid at several temperatures. J. Chem. Eng. Data 2012, 57, 2553−2559. (24) Fahim, M. A.; Al-Muhtaseb, S. A. Liquid-liquid equilibria of the ternary system water + acetic acid + 2-methyl-2-butanol. J. Chem. Eng. Data 1996, 41, 1311−1314.

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