Pergamon Chrmmd Enginrrring Science,Vol. 49, No. 11. pp. 1719-1727.

,994
Copyright Q 1994 ElscvierScienceLtd
Printed in Great Britain. All righasnsewcd
ooo9-2509/94 56.00 + 0.00
0909-2509(94,EOO4S-H

A NOVEL TECHNIQUE FOR RAPID LIQUID-VAPOUR

EQUILIBRIUM MEASUREMENT AND MODELLING

PH. VERNEAU and J. LIETOt

Laboratoire dAutomatique et de G&tie des Prockies, URA CNRS D1328, Universite Claude Bernard,
Lyon I, ITC-Lyon, 6 rue Jean Ma&, 69190 St-Fans, France

A. BOUDEHEN
Centre Technique ELF-ATOCHEM, Chemin de la Lone BP 32, 69310 Pierre-B&trite, France

and

J. BOUSQUET
SNEA, Tour ELF C%dex 45, 92078 Paris la Defense, France

Abatsct-The principles of an automated ebulliometer for fast binary vapour-liquid equilibrium data
measurement are presented. The system is made of a thermostated 0.5 1tank equipped wth a hollow shaft
and a self-inducing turbine to ensure fast equilibration, sampling and analysis systems, and a microcom-
puter for commanding the different valves and sensors, recording and analysing experimental data. The
automated feed system allows one to introduce successively in the tank, mixtures with known global
compositions. A given mixture is subjected to a temperature program consisting of symmetrical upward
and downward temperature paths. With a parameter estimation minimising a pressure criterion, the
(P, 7, x) technique associated with a mass balance leads to liquid-vapour equilibrium modelling. The tests
were performed with acetone-methanol and isopropanol-methanol mixtures. Good equilibrium data over
the full range of composition in broad P and T domains can be gathered in a short period of time.

JNTRODUCTION range 273-423 K and in the pressure range 0.1-2

Reliable vapour-liquid thermodynamic equilibrium
measurements are crucial for designing any distilla-
tion unit. The available ebulliometers which can be
used for obtaining these are based on two main tech-
niques. The dynamic technique implies forced convec-
tion of the two phases with eventual recirculation
(Othmer and Robert-Morley, 1947; Hala et al., 1967;
Berro et al., 1975) whereas with static techniques,
phases are strongly brought into contact and then left
without stirring until they reach equilibrium at con-
stant P and T (Gibbs and Van Ness, 1973; Slocum,
1975; Rousseaux et al., 1983; Kolbe and Gmehling,
1985; Reiff et al., 1987; Rarey and Gmehling, 1993).
If the available ebulliometers are well designed for
reaching equilibrium, they are not designed for
optimising the phase contact duration. Therefore, ob-
taining a complete set of thermodynamic data might
require as long as a month which, from an industrial
viewpoint, may sometimes be too long and/or too
costly. To reduce the data measurement duration sig-
nificantly, while obtaining a relevant thermodynamic
information, we applied the classical gas-liquid chem-
ical engineering concepts to the ebulliometric cell and
designed it as an efficient gas-liquid contractor.
MPa.
The experimental set-up is represented in Fig. 1. It
is made of an autoclave (the ebulliometric cell)
equipped with a jacket for circulation of heat transfer
fluids. The autoclave cover consists of four automated
valves, three thermocouples, one rupture disk, a pres-
sure sensor and an agitation system. The stirrer is
a self-inducing turbine entraining the gas phase into
the liquid through an hollow shaft. Four flanges are
placed in the autoclave to avoid any vortex formation.
The dimensions of the autoclave and its internals are
presented in Fig. 2. The two identical injection cir-
cuits are made of a tank, placed on a balance, from
which a liquid is pumped in a loop equipped with an
automated valve allowing the liquid discharge to the
autoclave. All the sensors are connected to a PC and
fully automated tests as well as manual ones can be
run. The gas phase can be analysed by an on-line gas
chromatograph. The analysis line must be carefully
insulated to avoid any condensation.
Automation
For automatic performance, a 386 Compaq com-
puter is used. The IO configuration is shown in Fig. 3.

EXPERIMENTAL APPARATUS Temperature and pressure measurements

General considerations The cell temperature is measured by an Engelhard
The apparatus can be applied in the temperature Pyrocontrole NB9-2722 thermometer (PT 100 sensor
pre-calibrated by Engelhard) set to f 0.05 K resolu-
Author to whom correspondence should be addressed tion. Stabilisation time < 5 s.

1719
1720 PH. VERNEAU
and J. LIETO
N2 low pressure NZ low pressure
I - Injection loop 1 N2 high pressure

The injection LOOP 2

is the same 11~ the 1
- Heating cord Carrier gas

Fig. 1. Experimental set-up for liquid-vapour thermodynamic equilibrium.

Liquid injection
U Q Two stainless-steel membrane pumps by Lewa
(FClV and FCMi) were used.
A 4
D
1 Valves
Valves on lines: we used Whitey valves (range of
z operating conditions: &20 MPa, 273-328 K)
with pneumatic command.
Valves on the tank: we used gate valves by
Grayel France (range of operating conditions
* +/YJ_+$! O-6 MPa, 233473 K).
I
d Electrovalves with pneumatic command O-220
V/&l MPa by Lucifer were used.

Heat and cold production

T The autoclave jacket was heated with an Haake
<- thermostat (F3-S, 273-523 K) and cooled with an
Haake cryostat (F3-K, 233423 K).

H EXPERIMENTAL PROCEDURE
==iG The entire system is pressure proofed with Nz or
Fig. 2. Ebulliometric cell dimensions. vacuum, and the cell is kept under vacuum prior to
liquid introduction. Liquids are degassed and purified
by distillation. They are placed in tanks 1 and 2.
Pressure measurement is performed using a Wika The cell is fed with liquids A and B through two
pressure sensor (model 891-10-500) with nominal parallel and identical circuits according to the follow-
O-1 MPa (10 bar) full reading. The repeatability and ing procedure:
hysteresis of this sensor are approximately 0.05% of
full scale. Stabilisation time < 0.3 ms. (1) Prior to the experiment, the loop is filled with
liquid up to the inlet valve.
Weight measurements (2) The feed tank weight is recorded.
Two Mettler balances (PM 6000) with 0.1 g resolu- (3) The desired amount of liquid is pumped into the
tion were used (C&6 kg). cell (inlet valve opened).
 A novel technique for rapid liquid-vapour equilibrium measurement and modelling 1721

Mettler
Balance
PM6ooo

IPressure I
Display WIKA
VT%340 0.1.6 MPa

%Srnpliq
En&hart

Tamp liq
TI
- Engelbart

Temp
Vap TI
Engel hart

Electrovalves

Fig. 3. IO configuration of the controlling computer.

(4) The feed tank weight is recorded again to ob- phases is established. P is calculated with thermodyn-
tain the exact amount injected. When this information amic models (virial equation for the gas and Wilson
is known for the two liquids, the global composition of equation for the liquid phase). The parameter estima-
the mixture, z, is known. tion technique minimising
(5) Stirring and temperature control are started.
A saw-tooth shape temperature profile is established.
The resulting T(t) and P(t) are recorded.
is a gradient method. Figure 4 illustrates the experi-
This sequence is repeated many times as desired for mental data modelling. We selected simple thermo-
another global composition by adding a given dynamic models which represent the experimental
amount of one of the liquids. Nine or ten global data very well. It is clear that any thermodynamic
compositions evenly distributed between 0 and 1 (x, equation can be used for representing strongly non-
liquid mole fraction) are necessary for optimal results. ideal fluids.
Gas-phase analysis can be performed for modelling
validation purposes. RESULTS AND DISCUSSION

Traditional liquid-vapour equilibrium measure-

MODELLINC ments are made with stabilised temperature and com-
P(r), T(t)and z (initial global composition) are position. We propose to change T with time (i.e.
measured. Thermodynamics parameters are in- impose a T(t) prdile) for a global mixture composi-
itialised and a flash mass balance between the two tion and to record P(t). The equilibrium pressure
I722 PH. VERNEAU and J. LIETO
Tknnodynamicmc&
E.O.S. E.O.S.
activity c&f.
I
Fig. 4. Flow diagram for experimental
Fig.5. Pressure evolution during upward (- - -) and
downward( + ) temperaturepaths for methanol-acetone.
must be between the P(t) measurements correspond-
ing to increasing and decreasing temperature. The
question is to know how close our P measurements
are from the equilibrium pressure, i.e. how large is the
I3 Au
data modelling.
AP. To answer this question, we treated separately the
increasing and decreasing temperature subprograms,
applied to the methanol-acetone binary. Figure 5 rep-
resents P(T) for the two temperature profiles. From
this P(T) representation, we conclude that AP is very
small and that our measurements are very close to the
equilibrium pressure.
To obtain a better estimation of AP, we proceeded
as follows. P(T) was represented by the Riedel vapour
equation
LnP=A-_+fLnT+DT.
Parameters of the Riedel equation were estimated
with increasing and decreasing P(t) paths separately.
Pressure can be calculated from the two parameter
sets and common temperature data. The diflerence
between the two computed pressures is characteristic
 A novel technique for rapid liquid-vapour equilibrium measurement and modelling 1723
of the hysteresis associated with the increasing and mass transfer is the limiting process, the AP must be
decreasing temperature and is to be compared with negative. We observed that very often, AP is negative:
the experimental error associated with pressure mass transfer is the limiting process. However, the AP
measurements. is very small and the measured pressures are closely
The data reported in Table 1 show that the differ- representative of the thermodynamic equilibrium. The
ence between the computed pressures is generally proposed technique is particularly well suited to the
smaller than the average residual difference obtained automatic modelling of isothermal and isobaric data
after estimation, or is of the order of magnitude of the obtained simultaneously during the same experi-
experimental pressure error. We conclude that the ments. Isothermal and isobaric data can be extracted
thermodynamic equilibrium is established at any time from the T(t) and P(c) data as shown in Fig. 6. The
during the temperature profile evolution. acetone-methanol and methanol-isopropanol binaries
Our ebulliometric cell was designed as a gas-liquid were selected to test our equipment because their
reactor and therefore we were able to enhance mass liquid-phase thermodynamic equilibrium are well de-
and heat transfers rates between phases. The temper- scribed (Hirata et al., 1975). The experiments implying
ature evolution with time induces a competition be- the two binaries were reproducible within less than
tween heat and mass transfer. However, the pressure 1%. The parameters estimation results were expressed
sensor dynamic can be neglected with respect to the as y =f(x) curves.
temperature sensor dynamic. If we suppose that the The gas-phase composition can be obtained from
cell is perfectly mixed-a reasonable hypothesis be- an on-line gas chromatograph. This information is
cause of the cell and stirrer design-there is a com- important for the model validation and crucial for
petition between the heat transfer to the sensor and some strongly non-ideal cases for which the (P, T, x)
mass transfer between phases. If heat transfer is the information might not be sufficient.
limiting process, the pressure difference between up- We exemplify the use of isothermal data with the
ward and downward P(t) paths must be positive. If methanol-acetone binary. The comparison between

Table 1. Pressure deviation induced by upward and downward temperature

paths for methanol-acetone, t for acetone = 0.126

p P P down DP = Pu. - Pd.

WPa) (MPa) (MPa) DPjP up

396.28 0.5075 0.5057 0.0018 0.0035

394.26 0.4742 0.4734 0.0008 O.oOl7
392.22 0.4429 0.4429 0.0000 0.0000
390.20 0.4141 0.4148 - o.ooo7 - 0.0017
388.19 0.3874 0.3886 - 0.0012 - 0.0031
386.14 0.3620 0.3636 - 0.0016 - 0.0044
384.13 0.3389 0.3408 - 0.0019 - 0.0056
382.11 0.3171 0.3192 - 0.0021 - 0.0066
380.10 0.2969 0.2992 - 0.0023 - 0.0077
378.08 0.2780 0.2803 - 0.0023 - 0.0083
376.04 0.2601 0.2625 - 0.0024 - 0.0092
374.02 0.2436 0.2459 - 0.0023 - 0.0094
371.98 0.2280 0.2303 - 0.0023 - 0.0101
369.96 0.2136 0.2158 - 0.0022 - 0.0103
367.92 0.1999 0.2020 - 0.0021 ~ 0.0105
365.87 0.1871 0.1891 - 0.0020 _ 0.0107
363.86 0.1753 0.1772 - 0.0019 - 0.0108
361.84 0.1642 0.1659 ~ 0.0017 - 0.0104
359.83 0.1539 0.1555 - 0.0016 - 0.0104
357.78 0.1440 0.1454 - 0.0014 - 0.0097
355.77 0.1349 0.1362 - 0.0013 - 0.0096
353.72 0.1262 0.1274 - 0.0012 - 0.0095
351.71 0.1183 0.1192 - o.ooo9 - 0.0076
349.69 0.1107 0.1116 - 0.0009 - 0.0081
347.68 0.1037 0.1044 - 0.0007 - 0.0068
345.67 0.0971 0.0977 - 0.0006 - 0.0062
343.65 0.0909 0.0913 - o.oQO4 - 0.0044
34 1.64 0.0851 0.0854 ~ o.ooo3 _ 0.0035
339.62 0.0796 0.0798 - 0.0002 - 0.0025
337.58 0.0744 0.0744 0.0000 0.0000
335.53 0.0695 0.0694 0.0001 0.0014
333.52 0.0650 0.0648 0.0002 0.003 1
331.50 0.0607 0.0605 o.a302 0.0033
329.49 0.0567 0.0564 0.0003 0.0053

CES 49:11-C
1724 PH. VERNEAU and J. LIETO

time

time
Fig. 6. Isothermal and isobaric data obtention from dynamic database.

340

335
;;

+
330 -
z
)I

325 0.
0.0 0.5 1.0 0.0 0.5 1.0
x & y mol. frac. acetone x mol. Prac. acetone

Fig. 7. Comparison between our model (- - - -) and published experimental data ( + ) (Hirata et al., 1975)
for methaol acetone isothermal data for 323 K c T < 383 K at P = 0.1013 MPa.

340 (D
cl.0
0
c)
0
0
a
335 -
iz c)
:0.5-
F 't
330 - .
-
z
7

325 11
0.0 0.5 1.0 0.0 0.5 1.0
x i% y mol. Prac. acetone x mol. l-l-C!C. acetone

Fig. 8. Comparison between our model (- - - -) and published experimental data ( + ) (Hirata et al.,1975)
for methanol-acetone isothermal data for 318 K < T < 365 K at P = 0.1013 MPa.

our data (and the associated model) and published 1% and a mole fraction difference less than 0.005.
experimental data is made in Figs 7 and 8 corres- With 318K < T < 365K, our model fits perfectly
pond@ to two temperature domains. With with the published experimental data.
323 K -C T-c 383K, our model represents the litera- The use of isobaric data is exemplified with a non-
ture experimental data with a AT difference less than degassed isopropanol-methanol binary. Therefore,
 A novel technique for rapid liquid-vapour equilibrium measurement and modelling 1725
isobaric data were strongly affected by solubilised inducing turbine, equipped with automatic constitu-
gases in the binary constituents. ent injection systems, an on-line gas chromatograph,
As illustrated in Figs 9 and 10, our estimation pre- and connected to a PC. P, T, .z are automatically
dicts a positive azeotrope because of solubilised gases registered and the analytical system gives y. Phase
which are desorbing in the cell and increase the pres- modelling implies the virial equation for the gas and
sure. As expected, this pressure change is stronger in Wilson equation for the liquid, but any other thermo-
the weak pressure domain, Even with poorly prepared dynamic equation can be used. The (P, T, x) technique
solvents, the estimation predicts the literature experi- associated with a flash mass balance leads to a model
mental data within 1%. computing P and using a gradient technique for the
Experiments with the isopropanol-methanol bi- parameters estimation.
nary were performed at two stirring speeds: 13.7 Hz The stirring system induces an efficient gas-liquid
(no gas recirculation) and 27.7 Hz (gas recirculation). contact which allows a very rapid thermodynamic
Figures 11 and 12 illustrate the stirring effect on the equilibrium settling. Therefore, dynamic T(t) paths
modelling based on isobaric data at P = 0.1013MPa. can be imposed for a global composition. We can
The stirring speed affects the residual pressure dif- gather several hundreds of P, T data for one composi-
ference as shown in Table 2. tion. The experiment duration (2 days) is definitely
shorter than the classical ebulliometric technique
CONCLUSION duration for the same information content. The re-
We designed and constructed an ebulliometric sults are obtained with a 1% precision. We applied
cell-a thermostated autoclave-stirred with a self- our technique to industrially relevant binaries and

-
360

;; 350

I-- 345

340

_ -
d-0 0.5 1.0 0.0 0.5 1.0
x & y mol. frec. methanol x mol. Prac. me thano I

Fig. 9. Comparison between our model (- -- -) and published experimental data ( + ) (Hirata er al., 1975)
for isopropanol-methanol isobaric data, P = 0.085 MPa.

360

2 350 0

F0.5
I- 345 G

340

0.0 0.5 1.0

x & y mol. frac. methanol

Fig. 10. Comparison between our model (- - - -) and published experimental data ( -+ ) (Hirata et al.,
1975) for isopropanol-methaol isobaric data, P = 0.15 MPa.
1726 PH. VERNEAU and J. LIETO

360

340

0.0 0.5 1.0

Ol x mo I . frsc. methanol

Fig. Il. Stirring speed effect. Comparison between our model (- - - -) +nd publishedexperimental data
( + ) (Hiram et al., 1975) for isopropanol-methanol isobaric at P = 0.1013 MPa and 13.7 Hz (no gas
recirculation).

360

355

.
~3350
:0.5
+345 :
.
-
340 i?

335
0.0 0.5 1.0
x mol. frac. me then o I

Fig. 12. Stirring speed effect. Comparison between our model (- - - -) and published experimental data
( + ) (Hirata et al., 1975) for isopropanol-methanol isobaric data at P = 0.1013 MPa and 27.7 Hz (gas
recirculation).

Table 2. Stirring speed influence on x liquid molar fraction of the volatile

residual pressure difference
Y vapour molar fraction of the volatile
AP (%)
.I! global molar fraction of the volatile
N (Hz)
13.7 2.5 Greek letters
27.1 1.8 A difference

Subscripts
cal calculated
were able to obtain y = f(x) curves. The model valida- exp experimental
tion was obtained through the comparison between
computed and analysed gas-phase molar fractions REFERENCES
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iquilibres liquideevapeur des solutions. le binaire
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