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org/jced Article

Measurement and Thermodynamic Modeling of Liquid−Liquid

Equilibrium Data for Ternary Systems (Water + Formaldehyde +
Methyl Isobutyl Ketone/Cyclohexanone) at Different Temperatures
Wenyang Fan, Qing Li, Dongmei Xu, Jun Gao, Huiwen Huang,* and Yinglong Wang
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ABSTRACT: To explore the separation of formaldehyde from its

aqueous solution, the liquid−liquid equilibrium data for the
systems (water + formaldehyde + methyl isobutyl ketone/
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cyclohexanone) were measured at 303.15, 313.15, and 323.15 K

in 101.3 kPa. The separation effect was judged by the separation
factor and the partition coefficient. The S values of methyl isobutyl
ketone and cyclohexanone are greater than unity, and the S and D
values of cyclohexanone are greater than methyl isobutyl ketone,
indicating that cyclohexanone is a suitable extractant compared
with methyl isobutyl ketone. The reliability of the measured data is
evaluated by Hand and Othmer−Tobias equations, and the R2
values of the two equations are close to unity. The universal quasi-chemical theory and nonrandom two-liquid theory models were
applied to fit the tie-line data of the investigated mixtures with a root mean square deviation lower than 0.01. Moreover, the binary
interaction parameters were validated using a topology of Gibbs energy of mixing surface analysis.

1. INTRODUCTION aldehyde, methanol, and methylal. However, there are only a

As a widely used chemical raw material, formaldehyde can be
used in many products such as synthetic resins, perfumes,
pharmaceutical products, and agrochemicals.1 Usually, form-
aldehyde is stored, transported, and industrially applied in the
form of an aqueous solution.2 However, the azeotropic3
formed by formaldehyde and water requires unique distillation
processes such as azeotropic distillation, extractive distillation,
and pressure swing distillation, which have the disadvantages of
high energy consumption and high cost.4−6 Therefore, low-
consumption processes such as extraction are more suitable for
separating formaldehyde in the water phase.
Liquid−liquid extraction, as an effective separation process,
can be used in industrial and economic applications.7,8 The
function parameters regressed by LLE data are of great
significance in the design of the extraction process. So far, there
have been many pieces of research on the ternary or
quaternary mixtures for formaldehyde, methanol, methylal,
and water in the literature. Niklas et al.9 studied the LLE
behavior of the mixtures (formaldehyde + water + PODE2)
and (formaldehyde + water + PODE3) at 280−340 K; Kuhnert
et al.10 investigated the vapor−liquid equilibrium (VLE) and
LLE for mixtures (formaldehyde + water/methylal + methylal)
and (formaldehyde + water + methanol + methylal) at
different temperatures under 101.3 kPa; Wang et al.11 studied
the LLE behavior for the mixtures (methylal + water + MIBC)
at 298.2 and 308.2 K under 101.3 kPa. At present, most
references have made reports on the separation of form-
few studies on LLE exploration of mixtures (formaldehyde +
water + solvents).
In the LLE experiment, the choice of solvent is an important
part. Suitable solvents must have not only good extraction
performance but also have appropriate properties.12 For
example, methyl isobutyl ketone (MIBK) and cyclohexanone
(CYC) have good extraction performance in an aqueous
system and were widely used in industry.13 In recent years,
many studies have been conducted on the literature with the
LLE data of MIBK and CYC in water systems. The LLE data
of the system (CYC + water + phenol) from 298.15 to 323.15
K in 101.3 kPa were explored by Cai et al.14 Dong et al.15
investigated the (water + furfuryl alcohol + MIBK) system at
298.2 K and 101.3 kPa. Wang et al.16 studied the extraction
behavior for the systems (water + n-propanol/isopropanol +
CYC) at 298.15 and 308.15 K. According to the above
literature, MIBK and CYC showed good extraction perform-
ance for aqueous systems. Therefore, MIBK and CYC were
used as solvents for separating formaldehyde from its aqueous
Received: February 26, 2022
Accepted: May 27, 2022

© XXXX American Chemical Society https://doi.org/10.1021/acs.jced.2c00121

A J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 1. Relevant Information of the Materials

a
The mass fraction of formaldehyde, MIBK, and CYC was analyzed by GC. Standard uncertainties u are u(T) = 0.06 K, u(p) = 0.52 kPa, and u(w)
= 0.0040.

solution, and the LLE exploration for the mixtures (form-

aldehyde + water + MIBK/CYC) has not been reported.
In this work, MIBK and CYC were selected as extractants to
separate formaldehyde from its aqueous solutions. The LLE
data of the systems (water + formaldehyde + MIBK/CYC)
were explored at 303.15, 313.15, and 323.15 K in 101.3 kPa.
The Hand and Othmer−Tobias equations checked the
reliability of the experimental contact line data. The effect of
separation was characterized by the separation factor (S) and
partition coefficient (D). The experimental tie-line data were
correlated by the universal quasi-chemical theory (UNI-
QUAC) and nonrandom two-liquid (NRTL) models. The
Gibbs energy topology of mixed surface analysis verified the
consistency of regression binary interaction parameters.
2. EXPERIMENTAL SECTION
2.1. Chemicals. The basic information of chemicals and
the mass fraction is shown in Table 1, while all the materials
were used without any additional treatment. Formaldehyde
aqueous solution was obtained by boiling paraformaldehyde in
high pH deionized water and filtering the turbid solution.10
The content of water in formaldehyde aqueous solution is
0.5910, which was determined by a gas chromatograph
(Agilent 7890a) with a thermal conductivity detector (TCD)
and a Porapak N column (3 mm × 3 m). The contents of
water in MIBK and CYC were determined by a Karl Fischer
moisture meter (ET08, METROHM), and the contents (mass
fraction) were 0.0020 and 0.0040, respectively. Deionized
water was prepared using an ultrapure water apparatus (CSR-
1D, Beijing Aisitaike Technology Development Co., Ltd.).
2.2. Experimental Procedures. The published literature
has listed devices and methods for liquid−liquid equilibrium
experiments.17−20 The LLE experiment was measured in a 50
mL self-designed equilibrium device, as shown in Figure 1.
First, water and solvents (MIBK or CYC) were added to the
device. Next, formaldehyde solution was added to the device
several times to determine different data points. The mass of
each sample was weighed by an analytical balance (METTLER
TOLEDO MS-TS, accuracy of ±0.0001 g). The temperature
in the device was regulated by a thermostatic water bath
(DKB-501S, Shanghai Jinghong Experimental Equipment Co.,
Ltd) and measured by a mercury thermometer with an
accuracy of ±0.1 K. The prepared mixture was fully stirred for
4 h at a given temperature. Afterward, the mixture was settled
for 8 h to achieve phase equilibrium. A series of LLE data were
measured by adjusting mixture composition and temper-
ature.21,22
B https://doi.org/10.1021/acs.jced.2c00121
Figure 1. Sketch map of the self-designed equilibrium glass: (1),
water inlet; (2), water outlet; (3), upper-layer sample; (4), lower-layer
sample; (5), magnetic stirrer.
2.3. Component Analysis. The contents (mass fraction)
of water, formaldehyde, MIBK, and CYC were measured
through the standard internal method (internal standard,
dioxane). The water phase and organic phase samples were
collected by a syringe and analyzed by an Agilent 7890A GC.
The detailed analytic conditions are provided in Table 2. The
same sample was analyzed not less than 3 times, and the
average results were used for the GUM Standard for
calculating standard uncertainty.23
Table 2. GC Analysis Conditions
name description of characteristic
column Porapak N column (3 mm × 3 m)
injector temp, 523.15 K
temperature initial temp, 323.15 K (2 min); heating rate, 10 K/
program min;final temp, 473.15 K
detector thermal conductivity detector (TCD); temp, 523.15 K
3. RESULTS AND DISCUSSION
3.1. LLE Experimental Results. The binary solubility data
for water + MIBK (or CYC) are plotted in Figures 2 and 3,
which were compared with the references.14,16,24−33 The
solubility of water and MIBK (or CYC) in this work agrees
well with the references. The experimental data for the two
mixtures (water + formaldehyde + MIBK) and (water +
formaldehyde + CYC) were measured at 303.15, 313.15, and
323.15 K in 101.3 kPa and are listed in Tables 3 and 4. The
subscripts 1, 2, and 3 refer to water, formaldehyde, and MIBK/
CYC, respectively. The LLE data are plotted in Figures 4−9.
The feed composition points for the two mixtures are shown in
Figures 4−9 and listed in Tables S1 and S2 in the Supporting
Information. The insoluble region in the phase diagram was
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Figure 2. Comparison of the binary solubility data with the references
for water + MIBK: (red solid circle), this work; (open square), from
ref 24; (open circle), from ref 25; (green open star), from ref 26;
(upside down blue open triangle), from ref 27; (open diamond), from
ref 28; (blue open triangle), from ref 29; (upside down open triangle),
from ref 30; (pink open diamond), from ref 31.
Figure 3. Comparison of the binary solubility data with the references
for water + CYC: (red solid circle), this work; (open square), from ref
24; (open circle), from ref 32; (green open star), from ref 14; (blue
open triangle), from ref 33; (pink open diamond), from ref 16.
obvious, indicating that MIBK and CYC could separate
formaldehyde from their aqueous solution. Figure S1 shows
the triangular diagrams of water + formaldehyde + MIBK/
CYC systems at different temperatures under 101.3 kPa in the
Supporting Information. For the system (water + form-
aldehyde + MIBK), the insoluble area did not change
significantly at different temperatures. For the system (water
+ formaldehyde + CYC), a similar result was observed.
Figure 10 shows the obtained triangular diagrams for the
systems (water + formaldehyde + MIBK/CYC) at 323.15 K,
compared with literature results that were determined by Song
et al.34 at 288.15 K under 101.3 kPa with another solvent
(dimethyl carbonate). As seen from Figure 10, the two-phase
area of the systems (water + formaldehyde + MIBK/CYC) is
larger than that of the system (water + formaldehyde +
dimethyl carbonate), indicating that MIBK and CYC have the
largest operating range among the three solvents. In addition,
C https://doi.org/10.1021/acs.jced.2c00121
pubs.acs.org/jced Article
the triangular diagrams for another system (water + methanol
+ biodiesel) determined by Santos et al.35 at 298.15 K under
101.3 kPa are plotted in Figure 10. Biodiesel is a mixture of
mono-alkyl esters (especially methyl or ethyl esters) and long-
chain aliphatic hydrocarbons (C14−C22), which are obtained
through a transesterification process. It can be seen from
Figure 10 that the two-phase area of the system (water +
methanol + biodiesel) is larger those that of the other three
systems, indicating that biodiesel as a suitable solvent has a
wide operating range in the process of extracting methanol
from its aqueous solution and can be a potential solvent for
separating formaldehyde.
3.2. Quality Test of Experimental Data. The mass
conservation of the experimental data corresponding to the tie-
line was checked by the method proposed by Marcilla et al.36
The contents of the water phase, organic phase, and feed
should meet the mass conservation law. The mass balance
equation is expressed as
M(w1) = MI(w1I) + MII(w1II) (1)
M(w2) = MI(w2I) + MII(w2II) (2)
M(w3) = MI(w3I) + MII(w3II) (3)
II I
where M, M , and M stand for the quality of the feed,
organic phase, and aqueous phase; wiII, wiI, and wi are the mass
fractions of component i in the organic phase, aqueous phase,
and feed, respectively.
1
N
|(MIwiI, n + MIIwiII, n) − Mwi , n|
δi(%) = × ∑ 100 ×
N n
Mwi , n
(4)
|(MI + MII) − M |
δ(%) = 100 ×
M (5)
where N indicates the sum of tie-line numbers; n refers to the
number of tie-lines.
According to the above equations, the value of M was
compared with the sum of M I and M II. The relative average
deviation (δi) and the deviation of each component’s mass
balance (δ) are calculated in eqs 4 and 5, respectively, which
indicate the difference between the sum of the masses of the
two phases and the feed. The values of δi and δ were no more
than 0.5%. Tables S1 and S2 list the values of δi and δ for the
two mixtures in the Supporting Information, which confirms
that the quality of the experimental data is relatively good.37
3.3. Reliability of the Tie-Line Data. Hand38 and
Othmer−Tobias39 evaluated the reliability of the measurement
data and gave the following results:
ln(w2II/w3II) = a + b ln(w2I/w1I) (6)
ln[(1 − w3II)/w3II] = c + d ln[(1 − w1I)/w1I] (7)
where a, b, c, and d are the equation parameters. wI1 and wI2
refer to the mass fractions of water and formaldehyde in the
raffinate layer, while wII2 and wII3 are the mass fractions of
formaldehyde and MIBK (or CYC) in the organic layer,
respectively. From Figures 11 and 12, the values of R2 for the
two equations are close to unity, indicating that the determined
LLE data are reliable.
3.4. Separation Factor and Partition Coefficient. The
separation factor (S) and partition coefficient (D) evaluated
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Table 3. Experimental Tie-Line Data (Mass Fraction) for Water (1) + Formaldehyde (2) + MIBK (3) at Different
Temperatures under 101.3 kPaa
the aqueous phase (raffinate phase) the organic phase (extract phase)
I I I II
T (K) w1 w2 w3 w1 w2II w3II D S
303.15 0.9844 0.0000 0.0156 0.0248 0.0000 0.9752
0.9449 0.0373 0.0178 0.0257 0.0018 0.9725 0.0483 1.7743
0.9104 0.0712 0.0184 0.0362 0.0047 0.9591 0.0660 1.6601
0.8696 0.1101 0.0203 0.0418 0.0084 0.9498 0.0763 1.5872
0.8283 0.1492 0.0225 0.0465 0.0120 0.9415 0.0804 1.4327
0.7836 0.1924 0.0240 0.0571 0.0186 0.9243 0.0967 1.3267
0.7464 0.2273 0.0263 0.0620 0.0252 0.9128 0.1109 1.3347
0.7102 0.2617 0.0281 0.0698 0.0311 0.8991 0.1188 1.2092
0.6739 0.2967 0.0294 0.0767 0.0384 0.8849 0.1294 1.1371
313.15 0.9852 0.0000 0.0148 0.0252 0.0000 0.9748
0.9493 0.0349 0.0158 0.0264 0.0018 0.9718 0.0516 1.8546
0.9123 0.0713 0.0164 0.0348 0.0049 0.9603 0.0687 1.8016
0.8709 0.1107 0.0184 0.0401 0.0088 0.9511 0.0795 1.7265
0.8306 0.1501 0.0193 0.0446 0.0126 0.9428 0.0839 1.5633
0.7895 0.1898 0.0207 0.0548 0.0201 0.9251 0.1059 1.5257
0.7505 0.2271 0.0224 0.0595 0.0265 0.9140 0.1167 1.4718
0.7165 0.2582 0.0253 0.0670 0.0327 0.9003 0.1266 1.3544
0.6846 0.2889 0.0265 0.0736 0.0403 0.8861 0.1395 1.2975
323.15 0.9865 0.0000 0.0135 0.0288 0.0000 0.9712
0.9386 0.0475 0.0139 0.0297 0.0036 0.9667 0.0758 2.3952
0.9131 0.0721 0.0148 0.0343 0.0062 0.9595 0.0860 2.2892
0.8751 0.1095 0.0154 0.0408 0.0103 0.9489 0.0941 2.0175
0.8387 0.1451 0.0162 0.0469 0.0166 0.9365 0.1144 2.0459
0.7976 0.1848 0.0176 0.0533 0.0221 0.9246 0.1196 1.7896
0.7593 0.2218 0.0189 0.0604 0.0287 0.9109 0.1294 1.6267
0.7164 0.2641 0.0195 0.0678 0.0356 0.8966 0.1348 1.4243
0.6841 0.2943 0.0216 0.0746 0.0431 0.8823 0.1464 1.3430
a
Standard uncertainties u are u(T) = 0.06 K, u(p) = 0.52 kPa, and u(w) = 0.0045.

the applicability of solvent MIBK and CYC, which were
defined as follows:40,41
S = (w2II/w2I)/(w1II/w1I)
D = w2II/w2I
where wI1and wI2
stand for the mass fractions of water and
formaldehyde in the aqueous layer; wII1 and wII2 indicate the
mass fractions of water and formaldehyde in the organic phase,
respectively.
The D and S values of the systems are shown in Tables 2
and 3. The relationship between the D and S values and the
mass fraction of formaldehyde in the MIBK (or CYC) layer is
shown in Figures 13 and 14. As shown in Tables 2 and 3, the S
values of the mixtures studied are far greater than unity,
indicating that the solvents can extract formaldehyde from its
aqueous solution. It can be seen from Figure 13 that, with the
increase in the formaldehyde content (extraction layer), the S
values gradually decrease. With the increase in system
temperature, the S values increased slightly. Compared to
MIBK, CYC has a higher S value at 323.15 K, suggesting that
CYC can be used as a suitable solvent and has a higher
molecular polarity of water is stronger than that of solvents
(MIBK/CYC). Therefore, the strong molecular polarity makes
(8) formaldehyde have significant solubility in the aqueous phase
(raffinate phase). Similar results and explanations have been
(9) shown in published papers.42,43
In addition, the values of S and D in this paper compared
with those of another extractant (dimethyl carbonate)
determined by Song et al.34 at 288.15 K under 101.3 kPa are
plotted in Figures 13 and 14. As seen from Figures 13 and 14,
the S and D of CYC are significantly better than dimethyl
carbonate. The S and D of CYC at 328.15 K are the better than
those of other systems. CYC has a significant advantage in
separating formaldehyde from its aqueous solution with the
high values of S and D.
3.5. Correlation of Experimental Tie-Line Data. The
determined LLE data for the ternary mixtures was correlated
using the UNIQUAC44 and NRTL45 models using Aspen Plus,
which were shown as follows:
NRTL model:

ij y
jjτ − ∑k xkτkjGkj zzz
temperature range to extract formaldehyde from its aqueous

jj ij z
∑k xkGkj zz
solution efficiently.
∑k Gkjxk j
∑j τjiGjixj xjGij

k {
As shown in Figure 14, the D values in each system were ln γi = + ∑
close to or less than unity, indicating that the formaldehyde ∑k Gkixk j
concentration in the extraction phase was close to or less than (10)
that in the extraction phase. This is due to the differences in
structure and polarity of these molecules. In this work, the UNIQUAC model:
D https://doi.org/10.1021/acs.jced.2c00121
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Table 4. Experimental Tie-Line Data (Mass Fraction) for the Water (1) + Formaldehyde (2) + CYC (3) System at Different
Temperatures under 101.3 kPaa
the aqueous phase (raffinate phase) the organic phase (extract phase)
I I I II
T (K) w1 w2 w3 w1 w2II w3II D S
303.15 0.9168 0.0000 0.0832 0.0613 0.0000 0.9387
0.8970 0.0189 0.0841 0.0792 0.0053 0.9155 0.2804 3.1760
0.8780 0.0355 0.0865 0.0956 0.0115 0.8929 0.3239 2.9751
0.8503 0.0595 0.0902 0.1115 0.0216 0.8669 0.3630 2.7684
0.8154 0.0921 0.0925 0.1270 0.0348 0.8382 0.3779 2.4260
0.7766 0.1279 0.0955 0.1418 0.0506 0.8076 0.3956 2.1667
0.7332 0.1619 0.1049 0.1579 0.0645 0.7776 0.3984 1.8499
0.6832 0.1963 0.1205 0.1723 0.0862 0.7415 0.4391 1.7412
0.6352 0.2267 0.1381 0.1873 0.1089 0.7038 0.4804 1.6291
313.15 0.9239 0.0000 0.0761 0.0678 0.0000 0.9322
0.8976 0.0168 0.0856 0.0807 0.0057 0.9136 0.3393 3.7738
0.8713 0.0343 0.0944 0.0975 0.0124 0.8901 0.3615 3.2307
0.8432 0.0583 0.0985 0.1137 0.0233 0.8630 0.3997 2.9639
0.8114 0.0870 0.1016 0.1295 0.0376 0.8329 0.4322 2.7079
0.7740 0.1161 0.1099 0.1446 0.0546 0.8008 0.4703 2.5173
0.7312 0.1409 0.1279 0.1611 0.0697 0.7692 0.4947 2.2452
0.6907 0.1611 0.1482 0.1757 0.0831 0.7412 0.5158 2.0278
0.6387 0.1936 0.1677 0.1910 0.1046 0.7044 0.5403 1.8067
323.15 0.9272 0.0000 0.0728 0.0703 0.0000 0.9297
0.8944 0.0142 0.0914 0.0925 0.0062 0.9013 0.4366 4.2218
0.8698 0.0307 0.0995 0.1138 0.0161 0.8701 0.5244 4.0083
0.8343 0.0521 0.1136 0.1305 0.0284 0.8411 0.5451 3.4849
0.8069 0.0746 0.1185 0.1472 0.0413 0.8115 0.5536 3.0348
0.7765 0.0973 0.1262 0.1664 0.0548 0.7788 0.5632 2.6282
0.7306 0.1243 0.1451 0.1899 0.0744 0.7357 0.5986 2.3028
0.6878 0.1463 0.1659 0.2058 0.0902 0.7040 0.6165 2.0605
0.6369 0.1721 0.1910 0.2247 0.1145 0.6608 0.6653 1.8858
a
Standard uncertainties u are u(T) = 0.06 K, u(p) = 0.52 kPa, and u(w) = 0.0045.

Figure 4. Measured LLE data for water + formaldehyde + MIBK at Figure 5. Measured LLE data for water + formaldehyde + MIBK at
temperature 303.15 K: (open square), measured tie-line data; (red temperature 313.15 K: (open square), measured tie-line data; (red
open triangle), UNIQUAC model; (pink star), feed composition; open triangle), UNIQUAC model; (pink star), feed composition;
(blue open circle), NRTL model. (blue open circle), NRTL model.

Øi z θ Ø
ln γi = ln + qi ln i + li − i ∑ xjl j

ÄÅ ÉÑ
xi 2 Øi xi j where the non-randomness (αij) of the NRTL model was fixed
ÅÅ ij yz ÑÑ
ÅÅ j z ÑÑ
at 0.3; the UNIQUAC structure parameters (r and q) were
Å j z
+ qiÅÅ1 − lnjj∑ Øj τji zz − ∑ ÑÑ
ÅÅ jj zz ÑÑ
derived from the Aspen database and are listed in Table 5; xi is
ÑÑ
θτ
ÅÅÇ
j ij

k j { ÑÖ
the mole fraction of the component; θi and Øi are the area
j ∑ k
θ k τkj fraction and segment fraction, respectively; i, j, and k represent
(11)
the components.
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Figure 6. Measured LLE data for water + formaldehyde + MIBK at Figure 8. Measured LLE data for water + formaldehyde + CYC at
temperature 323.15 K: (open square), measured tie-line data; (red temperature 313.15 K: (open square), measured tie-line data; (red
open triangle), UNIQUAC model; (pink star), feed composition; open triangle), UNIQUAC model; (pink star), feed composition;
(blue open circle), NRTL model. (blue open circle), NRTL model.

Figure 7. Measured LLE data for water + formaldehyde + CYC at Figure 9. Measured LLE data for water + formaldehyde + CYC at
temperature 303.15 K: (open square), measured tie-line data; (red temperature 323.15 K: (open square), measured tie-line data; (red
open triangle), UNIQUAC model; (pink star), feed composition; open triangle), UNIQUAC model; (pink star), feed composition;
(blue open circle), NRTL model. (blue open circle), NRTL model.

The interaction parameters for the ternary mixture were

calculated by the objective function (OF).46
M 2 3
OF = ∑ ∑ ∑ (wijkexp − wijkcal)2
k=1 j=1 i=1 (12)

where wcal and wexp stand for the calculated and experimental
composition of components, respectively; the subscripts j, k,
and i denote the order numbers of phases, tie-lines, and Figure 10. Comparison of triangular diagrams for this work and
components, respectively; M means the number of tie-lines. references: (red open square), water + formaldehyde + MIBK at
The optimized binary parameters of the two models are 323.15 K, this work; (blue open square), water + formaldehyde +
CYC at 323.15 K, this work; (open triangle), water + formaldehyde +
added in Table 6. The LLE data calculated by the two models
dimethyl carbonate measured at 288.15 K by Song et al., from ref 34;
are shown in Tables S3−S6 of the Supporting Information. (open circle), water + methanol + biodiesel measured at 298.15 K by
Figures 4−9 show the results of two systems using UNIQUAC Santos et al., from ref 35.
and NRTL models. The root mean square deviation (RMSD)
is as follows:47
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Figure 11. Hand plots for water + formaldehyde + MIBK (or CYC)
at 303.15, 313.15, and 323.15 K under 101.3 kPa: MIBK, (open
square), 303.15 K; (red open circle), 313.15 K; (blue open triangle),
323.15 K; CYC, (solid square), 303.15 K; (red solid circle), 313.15 K;
(blue solid triangle), 323.15 K.
Figure 13. Separation factor (S) vs mass fraction of formaldehyde in
the MIBK (or CYC) layer under 101.3 kPa: MIBK, (open square),
303.15 K; (red open circle), 313.15 K; (blue open triangle), 323.15 K;
CYC, (solid square), 303.15 K; (red solid circle), 313.15 K; (blue
solid triangle), 323.15 K; (upside down open triangle), dimethyl
carbonate, from ref 34.

Figure 12. Othmer−Tobias plots for water + formaldehyde + MIBK

(or CYC) at 303.15, 313.15, and 323.15 K under 101.3 kPa: MIBK, Figure 14. Partition coefficient (D) vs mass fraction of formaldehyde
(open square), 303.15 K; (red open circle), 313.15 K; (blue open in the MIBK (or CYC) layer under 101.3 kPa: MIBK, (open square),
triangle), 323.15 K; CYC, (solid square), 303.15 K; (red solid circle), 303.15 K; (red open circle), 313.15 K; (blue open triangle), 323.15 K;
CYC, (solid square), 303.15 K; (red solid circle), 313.15 K; (blue

ÄÅ M É
313.15 K; (blue solid triangle), 323.15 K.

ÅÅ ∑ ∑2 ∑3 (w exp − w cal)2 ÑÑÑ1/2

solid triangle), 323.15 K; (upside down open triangle), dimethyl

ÅÅ k = 1 j = 1 k = 1 ijk ÑÑ
RMSD = ÅÅÅ ÑÑ
carbonate, from ref 34.

ÅÅ ÑÑ
ÅÅÇ ÑÑ
ijk

ÑÖ
Table 5. r and q for Pure Components
6 M
(13)
component r q
It can be seen from Table 6 that the RMSD values are all less water 0.9200 1.4000
than 0.01, indicating that the calculated values are consistent formaldehyde 1.1496 1.2030
with the determined tie-line values. Otherwise, Figures 4−9 MIBK 3.9520 4.5959
show that the calculated values agree with the experimental CYC 3.1120 4.0679
data. The RMSD values of the NRTL model (0.004 and 0.005)
are slightly smaller than those of the UNIQUAC model (0.006
and 0.007), indicating that the NRTL model has better separating formaldehyde, and the NRTL model shows better
correlation performance for the ternary system in this work. relevance to the system in this work. So, we took the system
3.6. Evaluatin of Interaction Parameters. To verify the water + formaldehyde + CYC at 323.15 K as an example to test
consistency of the binary parameters of the NRTL and the optimized binary parameters of the NRTL model. Figure
UNIQUAC models, the graphical user interface (GUI) tool in 15 shows the GM/RT surfaces using the NRTL model of the
MATLAB in Reyes-Labarta’s work (Gibbs energy topology tie-line data for the system water + formaldehyde + CYC at
analysis of mixed surfaces) was involved in the verification.48 In 323.15 K under 101.3 kPa. As shown in Figure 15a,b, the LLE
this work, CYC has a significant extraction performance in junction estimated by the NRTL model is tangent to the GM/
G https://doi.org/10.1021/acs.jced.2c00121
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
 Journal of Chemical & Engineering Data pubs.acs.org/jced Article

Table 6. Optimized Interaction Parameters for Water (1) + Formaldehyde (2) + Solvent (3)a
NRTL parameters UNIQUAC parameters
i-j aij aji bij/K bji/K RMSD aij aji bij (K) bji (K) RMSD
rmaldehyde (2) + MIBK (3)
1-2 0.49 0.56 1116.85 −1010.57 0.0037 1.03 −1.15 −1206.71 901.47 0.0062
1-3 8.026 3.23 −857.83 −548.68 0.85 2.17 −609.37 −831.61
2-3 11.61 0.45 −1778.51 −140.64 −19.07 −10.13 −5756.75 3231.41
ormaldehyde (2) + CYC (3)
1-2 5.26 1.96 1707.83 −25.36 0.0055 1.25 −2.35 −1366.71 851.47 0.0075
1-3 2.62 −0.12 399.79 160.52 1.58 −1.01 −535.10 187.36
2-3 5.81 −7.73 725.38 1281.22 −4.02 4.61 1247.24 −2526.22
a
NRTL: τij = aij + bij/T; UNIQUAC: τij = exp(aij + bij/T).

Figure 15. Evaluation of the model parameter for the water + formaldehyde + CYC at 323.15 K: (a) GM/RT surface and (b) the cut along with
experimental ternary tie-line #4.

RT surface, indicating that the mixed Gibbs free energy value is
in the minimum state. Through the verification of each system,
the experimental data and the data calculated by the two
models are in the minimum state of mixed Gibbs free energy.
Therefore, the regression binary parameters of the two models
satisfy the coherence consistency.
4. CONCLUSIONS
The LLE data for (water + formaldehyde + MIBK/CYC) were
studied at 303.15, 313.15, and 323.15 K under 101.3 kPa. The
relative error of the feed mass and the total masses of the
conjugated phases are less than 0.5%. The Hand and Othmer−
Tobias equations checked the reliability of the experimental
contact line data, and the values of R2 for the two equations are
close to unity. The D and S were used to evaluate the
extraction performance of MIBK and CYC to formaldehyde
from its aqueous solution. The values of S are greater than
unity, which demonstrates that cyclohexanone was a suitable
extractant compared to methyl isobutyl ketone. The
UNIQUAC and NRTL models were used to correlate with
the data of the experiment with the RMSD values lower than
0.01. Compared with the UNIQUAC model, the NRTL model
has better correlation performance for the ternary systems in
this work. In addition, the topology of Gibbs energy of mixing
H https://doi.org/10.1021/acs.jced.2c00121
surface analysis verified the consistency of the binary
interaction parameters.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jced.2c00121.
Additional figures and tables showing the feed
composition and quality test, comparison of ternary
phase diagrams at different temperatures, and correlation
of experimental tie-line data (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Huiwen Huang − College of Chemical and Biological
Engineering, Shandong University of Science and Technology,
Qingdao 266590, China; orcid.org/0000-0003-1711-
9449; Email: hwsdust@163.com
Authors
Wenyang Fan − College of Chemical and Biological
Engineering, Shandong University of Science and Technology,
Qingdao 266590, China; orcid.org/0000-0002-6881-
9106
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Qing Li − College of Chemical and Biological Engineering,
Shandong University of Science and Technology, Qingdao
266590, China
Dongmei Xu − College of Chemical and Biological
Engineering, Shandong University of Science and Technology,
Qingdao 266590, China; orcid.org/0000-0002-5770-
0513
Jun Gao − College of Chemical and Biological Engineering,
Shandong University of Science and Technology, Qingdao
266590, China; orcid.org/0000-0003-1145-9565
Yinglong Wang − College of Chemical Engineering, Qingdao
University of Science and Technology, Qingdao 266590,
China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jced.2c00121
Funding
This work was financially supported by the Postdoctoral
Research Project of Qingdao (nos. 01020240112 and
01020240113).
Notes
The authors declare no competing financial interest.
■
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