J. Chem. Eng.

Data 2003, 48, 699-702 699

Liquid-Liquid Equilibria for the Binary Systems of

N-Formylmorpholine with Branched Cycloalkanes

MinSu Ko,† Sangyoup Na,† Soyoung Kwon,† Sungjin Lee,‡ and Hwayong Kim*,†

School of Chemical Engineering & Institute of Chemical Processes, Seoul National University,
Shinlim-dong, Kwanak-gu, Seoul 151-744, Korea, and School of General Education, Semyung University,
Sinwol-dong, Jechon, Chungbuk 390-711, Korea

Liquid-liquid equilibrium (LLE) data were measured for three binary systems containing N-formylmor-
pholine and branched cycloalkanes (methylcyclopentane, methylcyclohexane, and ethylcyclohexane) over
the temperature range around 300 K to close to the upper critical solution temperature (UCST) using
circulation type equipment with an equilibrium view cell. The compositions of both branched cycloalkane
rich and N-formylmorpholine rich phases were analyzed by on-line gas chromatography. The binary
liquid-liquid equilibrium data were correlated with the NRTL and UNIQUAC equations using
temperature-dependent parameters. Although clear deviation was observed in the vicinity of the UCST,
the NRTL and UNIQUAC equations fitted the experimental data well. The solubility of cycloalkane in
the N-formylmorpholine increases in the following order at the same temperature: methylcyclopentane,
methylcyclohexane, and ethylcyclohexane.

Introduction Table 1. Suppliers and Purity of the Used Chemicals

Many pairs of liquids of industrial importance have chemical supplier spec %a purity %b
limited mutual solubilities. Liquid-liquid equilibrium N-formylmorpholine ACROS >99.00 >99.99
(LLE) data are essential when considering separation methylcyclopentne ACROS >95.00 >99.15
processes. Recently, there have been ever-increasing de- methylcyclohexane Junsei Chemical >99.00 >99.89
Co., Inc.
mands for high-purity aromatic compounds as a feedstock
ethylcyclohexane ACROS >99.00 >99.94
for chemical synthesis. The aromatics are obtained by
separating out the reformates, which are the products of a The purity reported by the supplier. b The purity determined
catalytic reforming of naphtha. Extractive distillation and as area ratio by gas chromatography with a thermal conductivity
extraction processes are used to separate aromatics from detector after further purification.
hydrocarbon mixtures, especially to recover aromatics from
reformates. Also, many solvents such as sulfolane,1-5 measured in the temperature range from about 300 K to
N-methylpyrrolidone,6 glycol,7,8 and N-formylmorpholine9-11 the vicinity of the upper critical solution temperature
are used in these processes. The extractive distillation (UCST). Experimental data were correlated with the
process using N-formylmorpholine as a solvent is suitable nonrandom two-liquid (NRTL)14 and universal quasi-
for aromatics separation from reformates.12 This process chemical (UNIQUAC)15 models with the temperature-
minimizes aromatic content in gasoline and refines the dependent parameters.
extracted aromatics, which are used as raw materials for
petrochemical processes. Experimental Section
These days, commercial simulators are used for optimi-
zation of chemical processes. The optimum variable in the Chemicals. The chemicals were purchased and further
extractive distillation unit is a solvent-to-feed ratio. The purified with molecular sieves 13X. The suppliers and
operating cost and the initial equipment cost for the overall specification of the chemicals are listed in Table 1 together
plant can be reduced by optimizing the solvent-to-feed ratio. with the purities after purification, as determined using a
Binary LLE data containing N-formylmorpholine for wide HP 5890 gas chromatograph with a thermal conductivity
temperature ranges have become necessary because of the detector.
extractive distillation process to separate aromatics from Experimental Apparatus. Details of this apparatus
hydrocarbon mixtures.13 However, LLE data for these are given in our previous studies.16 The volume of the
mixtures are not available in the literature and the equilibrium cell was 240 cm3. The cell was made of
databank of simulators. stainless steel (SUS. 316) and placed inside the air bath.
The liquid-liquid equilibria for the N-formylmorpholine The air bath temperature was controlled by a PID tem-
and branched cycloalkane (methylcyclopentane, methylcy- perature controller to the desired temperature within (0.1
clohexane, and ethylcyclohexane) binary systems were K. And then, the fine control of the cell temperature within
(0.006 K was allowed by the flow rate of circulating-liquids
* To whom correspondence should be addressed. Fax: +82-2-888-6695. with the circulating minipump. The cell temperature was
E-mail: [email protected].
† Seoul National University. measured using a platinum resistance thermometer (1502A
‡ Semyung University. by Hart Scientific, Inc). Its uncertainty was estimated to
10.1021/je020208v CCC: $25.00 © 2003 American Chemical Society
Published on Web 03/21/2003
700 Journal of Chemical and Engineering Data, Vol. 48, No. 3, 2003

Table 2. Experimental and Calculated LLE Data for the Table 4. Experimental and Calculated LLE Data for the
Methylcyclopentane (1) + N-Formylmorpholine (2) Ethylcyclohexane (1) + N-Formylmorpholine (2) System
System
ethylcyclohexane NFM
methylcyclopentane NFM rich phase, x11 rich phase, x12
rich phase, x11 rich phase, x12
T/K exp NRTL UNIQUAC exp NRTL UNIQUAC
T/K exp NRTL UNIQUAC exp NRTL UNIQUAC
297.85 0.9797 0.9773 0.9776 0.0274 0.0263 0.0273
300.27 0.9835 0.9829 0.9828 0.0673 0.0687 0.0689 311.01 0.9756 0.9760 0.9764 0.0347 0.0357 0.0358
311.55 0.9751 0.9771 0.9771 0.0806 0.0773 0.0772 319.70 0.9714 0.9742 0.9745 0.0417 0.0432 0.0428
319.28 0.9712 0.9721 0.9722 0.0880 0.0848 0.0847 329.05 0.9679 0.9712 0.9714 0.0494 0.0528 0.0519
328.84 0.9669 0.9646 0.9647 0.0942 0.0965 0.0964 338.63 0.9655 0.9669 0.9668 0.0628 0.0644 0.0632
338.80 0.9561 0.9548 0.9549 0.1057 0.1122 0.1122 348.67 0.9619 0.9605 0.9601 0.0802 0.0791 0.0777
348.93 0.9447 0.9419 0.9420 0.1329 0.1330 0.1331 358.01 0.9537 0.9521 0.9514 0.1031 0.0957 0.0944
358.33 0.9253 0.9264 0.9264 0.1539 0.1581 0.1583 362.87 0.9502 0.9464 0.9456 0.1123 0.1058 0.1047
368.06 0.8991 0.9051 0.9051 0.1903 0.1923 0.1925 368.63 0.9390 0.9383 0.9373 0.1299 0.1194 0.1186
373.19 0.8896 0.8908 0.8907 0.2217 0.2149 0.2151 372.44 0.9316 0.9319 0.9308 0.1395 0.1295 0.1291
378.18 0.8751 0.8741 0.8740 0.2544 0.2409 0.2410 378.41 0.9210 0.9196 0.9184 0.1489 0.1477 0.1479
383.12 0.8562 0.8538 0.8536 0.2789 0.2717 0.2717 383.34 0.9078 0.9068 0.9057 0.1589 0.1655 0.1662
387.07 0.8323 0.8337 0.8336 0.3073 0.3012 0.3010 387.97 0.8937 0.8920 0.8910 0.1763 0.1851 0.1864
390.95 0.8114 0.8094 0.8094 0.3340 0.3358 0.3355 392.81 0.8716 0.8724 0.8719 0.1951 0.2096 0.2116
395.44 0.7693 0.7720 0.7721 0.3816 0.3866 0.3866 397.46 0.8518 0.8483 0.8485 0.2261 0.2383 0.2410
398.73 0.7344 0.7332 0.7327 0.4210 0.4363 0.4363 403.13 0.8220 0.8076 0.8097 0.2652 0.2842 0.2875
407.64 0.7737 0.7604 0.7651 0.3214 0.3357 0.3385
Table 3. Experimental and Calculated LLE Data for the 408.62 0.7306 0.7471 0.7527 0.3629 0.3497 0.3526
Methylcyclohexane (1) + N- Formylmorpholine (2) 409.63 0.6944 0.7319 0.7385 0.3966 0.3658 0.3680
System
methylcyclohexane NFM analyzed at least three times, and the average values were
rich phase, x11 rich phase, x12 used. The average error of duplicating sample analysis is
T/K exp NRTL UNIQUAC exp NRTL UNIQUAC 0.1%.
301.24 0.9784 0.9782 0.9784 0.0626 0.0609 0.0629
309.04 0.9787 0.9776 0.9778 0.0672 0.0677 0.0686 Results and Discussion
323.96 0.9758 0.9744 0.9744 0.0797 0.0831 0.0822
The measurement for the three systems methylcyclo-
335.97 0.9679 0.9712 0.9693 0.0984 0.0984 0.0966
345.80 0.9590 0.9631 0.9628 0.1086 0.1137 0.1115 pentane (1) + N-formylmorpholine (2), methylcyclohexane
352.48 0.9521 0.9572 0.9568 0.1268 0.1261 0.1237 (1) + N-formylmorpholine (2), and ethylcyclohexane (1) +
362.06 0.9484 0.9453 0.9447 0.1511 0.1477 0.1456 N-formylmorpholine (2) were performed within the range
372.11 0.9362 0.9262 0.9256 0.1850 0.1776 0.1765 of about 300 K to the vicinity of the upper critical solution
376.82 0.9247 0.9136 0.9131 0.2083 0.1955 0.1951 temperature (UCST). The experimental data are given in
381.88 0.9067 0.8962 0.8958 0.2292 0.2189 0.2193 Tables 2-4.
387.54 0.8713 0.8697 0.8698 0.2539 0.2519 0.2537
392.81 0.8285 0.8345 0.8354 0.2860 0.2933 0.2965 The binary liquid-liquid equilibrium data were cor-
398.53 0.7584 0.7743 0.7771 0.3382 0.3597 0.3650 related using the NRTL and UNIQUAC models. NRTL and
401.17 0.7096 0.7304 0.7347 0.3978 0.4065 0.4127 UNIQUAC models could not correlate the binary LLE data
402.28 0.6905 0.7054 0.7104 0.4205 0.4319 0.4387 in the vicinity of the critical temperature because of the
nonanalytical behavior with the flat slopes of the two
be within (0.006 K. The cell and the quartz window were branches of the coexistence curve near the critical region.
sealed with PTFE (Teflon) gaskets. The magnetic stirrer Therefore, these models were modified to use the binary
promoted the mixing. The cell temperature is controlled interaction parameters with temperature dependency. Dif-
using the two methods. The thermometer was calibrated ferent expressions for describing the temperature depen-
at the ice point and by comparison to standard platinum dency of the binary interaction parameter of these models
thermometers (SPRTs) calibrated on the basis of the are found in the literature and commercial software.17-21
international temperature scale of 1990 (ITS-90). The In this work, temperature-dependent binary interaction
sampling system was connected to a gas chromatograph parameters suggested by Aspen Technology Inc. were
(Hewlett-Packard 5890 Series II) with a thermal conduc- chosen.21 The excess Gibbs energy for the binary systems
tivity detector (TCD) and a 1.828 m × 0.003 175 m column of NRTL and UNIQUAC models is expressed by the
packed with Chromosorb WHP 100/120 coated with OV- following equations
101.
Experimental Procedure. The mixture was fed into the NRTL model:

( )
equilibrium cell that was initially evacuated. The mixture
was stirred for at least 1 h with the magnetic stirrer and gE τ21G21 τ12G12
) x1x2 + (1)
then left to settle for at least 2 h. Each phase was circulated RT x1 + x2G21 x2 + x1G12
with recirculation pumps for 1 h. The sampling was made
when the cell temperature change was within (0.02 K for G12 ) exp(-R12τ12), R12 ) R21 (2)
10 min. The samples were analyzed by gas chromatogra-
phy. The temperatures of the injector and the detector were τ12 ) a12 + b12/T + c12 ln T (3)
maintained at 523.15 K. After 1 min holding at 353.15 K,
the column temperature was raised to the final tempera- where x is the mole fraction, R12 ()R21) is the nonrandom-
ture of 423.15 K at the rate of 25 K‚min-1. Helium was ness parameter, and τ12 (*τ21) is the interaction parameter.
used as the carrier gas at the rate of 23 cm3‚min-1. Single- For a binary mixture, the NRTL model contains seven
phase samples of known composition were used to calibrate parameters. In this work, the nonrandomness parameter
the gas chromatograph in the composition range of interest. is fixed as 0.3 and the six binary interaction parameters
The samples of each phase at the same temperature were are optimized.
 Journal of Chemical and Engineering Data, Vol. 48, No. 3, 2003 701

Table 5. Temperature Dependence of the Parameters of the NRTL Equation with r12 ) 0.3 for the Branched
Cycloalkanes (1) + N-Formylmorpholine (2) Binary Systems
binary interaction parameters
system a12 a21 b12/K b21/K c12 c21
methylcyclopentane + NFM -14.616 82.929 2413.9 -3071.7 1.7193 -12.407
methylcyclohexane + NFM 254.71 29.701 -11370 -371.47 -37.485 -4.6313
ethylcyclohexane + NFM 194.08 -8.3869 -8527.4 2036.1 -28.539 0.75341

Table 6. Temperature Dependence of the Parameters of the UNIQUAC Equation for the Branched Cycloalkanes (1) +
N-Formylmorpholine (2) Binary Systems
binary interaction parameters
system a12 a21 b12/K b21/K c12 c21
methylcyclopentane + NFM 19.367 -42.600 -1388.3 1985.5 -2.6934 6.2238
methylcyclohexane + NFM -86.992 23.740 4063.3 -1376.3 12.760 -3.4167
ethylcyclohexane + NFM -70.549 27.740 3435.6 -1770.8 10.256 -3.9047

UNIQUAC model:
gE ) gEcombinatorial + gEresidual (4)

gEcombinatorial Φ1 Φ2
) x1 ln + x2 ln +
RT x1 x2

2
z
(
q1x1 ln
θ1
Φ1
+ q2x2 ln
θ2
Φ2
(5) )
gEresidual
) -q1x1 ln[θ1 + θ2τ21] - q2x2 ln[θ2 + θ1τ12] (6)
RT
x1r1 x1q1
Φ1 ) θ1 ) (7)
x1r1 + x2r2 x1q1 + x2q2
τ12 ) exp(a12 + b12/T + c12 ln T) (8)

Figure 1. Experimental and calculated liquid-liquid equilibrium

where Φ is the segment fraction, θ is the area fraction, r
data for the methylcyclopentane (1) + N-formylmorpholine (2)
and q are pure component relative volume and surface area mixture: points, experimental results; black solid line, NRTL with
parameters, respectively, and τ12 (*τ21) is the interaction R ) 0.3.
parameter. The r and q values of N-formylmorpholine,
methylcylopentane, methylcyclohexane, and ethylcyclohex-
ane were estimated by the Bondi method. These values are
(4.8642, 4.052), (3.9664, 3008), (4.6447, 3.548), and (5.3191,
4.088), respectively. The coordination number, z, was set
to 10.
The parameters in both models were found by minimiz-
ing the objective function

{( Tcalc
)
- Tkexp
( )}
2
N 2 2 xcalc - xijexp 2

∑ ∑∑
k ij
OF ) + (9)
k)1 σTk i)1 j)1 σxijk

where N is the number of experimental data in each group

k and σk is the standard deviation of group k. The
superscripts calc and exp present calculated properties and
experimental properties, respectively. The binary param-
eters for these models were evaluated by a nonlinear
Figure 2. Experimental and calculated liquid-liquid equilibrium
regression method based on the maximum likelihood. The data for the methylcyclohexane (1) + N-formylmorpholine (2)
temperature-dependent binary parameters of these models mixture: points, experimental results; black solid line, NRTL with
are given in Tables 5 and 6. R ) 0.3.
Figures 1-3 show graphical representations of the
experimental data and the calculated data in the form of The percent absolute average deviations (AAD%) of the
T, x′, x′′ diagrams, whereby the calculated values have composition in both phases over the considered tempera-
been obtained by means of the NRTL equation. The NRTL ture range for the NRTL and UNIQUAC equations are
and UNIQUAC models predict similar coexistence curves listed in Table 7. Both the NRTL and UNIQUAC models
over a wide temperature range. The UCSTs and critical predict the experimental data for the branched cycloal-
compositions calculated by these models were reported in kanes rich phase with an AAD of 0.8%, while the deviation
Table 8. is 3% for the N-formylmorpholine rich phase. The NRTL
702 Journal of Chemical and Engineering Data, Vol. 48, No. 3, 2003

measured data were correlated with the temperature-

dependent interaction parameters of the NRTL and
UNIQUAC models.

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Conclusions Received for review November 18, 2002. Accepted February 17,
2003. This work was supported by the Brain Korea 21 Program
Liquid-liquid equilibrium data for three binary branched supported by the Ministry of Education and LG-Caltex Research
cycloalkanes + N-formylmorpholine systems were mea- and by the National Research Laboratory (NRL) Program supported
by Korea Institute of S&T Evaluation and Planning.
sured in the temperature range from around 300 K to the
near upper critical solution temperature (UCST). The JE020208V