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

Copyright Q 1994 ElscvierScienceLtd
Printed in Great Britain. All righasnsewcd
ooo9-2509/94 56.00 + 0.00


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

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


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


cell (inlet valve opened). 273-328 K) with pneumatic command. 233473 K). H EXPERIMENTAL PROCEDURE ==iG The entire system is pressure proofed with Nz or Fig. VERNEAU and J. Heating cord Carrier gas Fig. 273-523 K) and cooled with an Haake cryostat (F3-K. Valves on the tank: we used gate valves by Grayel France (range of operating conditions * +/YJ_+$! O-6 MPa. (3) The desired amount of liquid is pumped into the tion were used (C&6 kg). Liquid injection U Q Two stainless-steel membrane pumps by Lewa (FClV and FCMi) were used. 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. 233423 K). A 4 D 1 Valves Valves on lines: we used Whitey valves (range of z operating conditions: &20 MPa. Experimental set-up for liquid-vapour thermodynamic equilibrium. The repeatability and ing procedure: hysteresis of this sensor are approximately 0. and the cell is kept under vacuum prior to liquid introduction.1720 PH. Stabilisation time < 0. thermostat (F3-S. Injection loop 1 N2 high pressure The injection LOOP 2 is the same 11~ the 1 .05% of full scale. I d Electrovalves with pneumatic command O-220 V/&l MPa by Lucifer were used. Two Mettler balances (PM 6000) with 0. vacuum.1 g resolu. They are placed in tanks 1 and 2. LIETO N2 low pressure NZ low pressure I . the loop is filled with liquid up to the inlet valve. Ebulliometric cell dimensions. Heat and cold production T The autoclave jacket was heated with an Haake <. Weight measurements (2) The feed tank weight is recorded. Liquids are degassed and purified by distillation.3 ms. (1) Prior to the experiment. 1. 2. .

T(t)and z (initial global composition) are position. It is clear that any thermodynamic compositions evenly distributed between 0 and 1 (x. We selected simple thermo- another global composition by adding a given dynamic models which represent the experimental amount of one of the liquids. Gas-phase analysis can be performed for modelling validation purposes. z. RESULTS AND DISCUSSION Traditional liquid-vapour equilibrium measure- MODELLINC ments are made with stabilised temperature and com- P(r). P is calculated with thermodyn- tain the exact amount injected. We propose to change T with time (i. A saw-tooth shape temperature profile is established. (4) The feed tank weight is recorded again to ob.1. Thermodynamics parameters are in. Nine or ten global data very well. the global composition of equation for the liquid phase). 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). A novel technique for rapid liquid-vapour equilibrium measurement and modelling 1721 Mettler Balance PM6ooo IPressure I Display WIKA VT%340 0. measured.e. ideal fluids. phases is established. Figure 4 illustrates the experi- This sequence is repeated many times as desired for mental data modelling. The resulting T(t) and P(t) are recorded. equation can be used for representing strongly non- liquid mole fraction) are necessary for optimal results. 3. is known. is a gradient method. When this information amic models (virial equation for the gas and Wilson is known for the two liquids. IO configuration of the controlling computer. The parameter estima- the mixture.6 MPa %Srnpliq En&hart Tamp liq TI . Engelbart Temp Vap TI Engel hart Electrovalves Fig. tion technique minimising (5) Stirring and temperature control are started. The equilibrium pressure .

S.S. Pressure evolution during upward (. LIETO Tknnodynamicmc& E. I I3 Au Fig. From this P(T) representation. -) and downward( + ) temperaturepaths for methanol-acetone. AP. ing to increasing and decreasing temperature. i. Parameters of the Riedel equation were estimated must be between the P(t) measurements correspond.. P(T) was represented by the Riedel vapour equation LnP=A-_+fLnT+DT’. we proceeded as follows.I722 PH. The diflerence are from the equilibrium pressure. how large is the between the two computed pressures is characteristic . To obtain a better estimation of AP. VERNEAU and J. Figure 5 rep- resents P(T) for the two temperature profiles.5. activity c&f. Fig.O. applied to the methanol-acetone binary. Flow diagram for experimental data modelling. To answer this question. we conclude that AP is very small and that our measurements are very close to the equilibrium pressure.e. The Pressure can be calculated from the two parameter question is to know how close our P measurements sets and common temperature data. E. 4. with increasing and decreasing P(t) paths separately.O. we treated separately the increasing and decreasing temperature subprograms.

98 0. is very small and the measured pressures are closely The data reported in Table 1 show that the differ.04 0.1362 . 0. x) mass transfer between phases.0023 .13 0.0909 0.0053 CES 49:11-C .oOl7 392. If heat transfer is the information might not be sufficient. 0.22 0. The experiments implying ature evolution with time induces a competition be.0000 0. 0.3408 . 0. 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.0023 . 0. the pressure difference between up.0.69 0. 0. 0.0031 386.0104 357.0003 0.0035 339. o. The during the temperature profile evolution.0009 . t for acetone = 0.11 0.3192 .0044 34 1.0000 335.1116 .0006 . 0. 0. However.08 0.0023 .0035 394.71 0.1539 0. 0.0971 0. 0. 0.1871 0. 0.0913 . However. Pd.0564 0.0066 380. 0.0022 .0095 351.ooo7 .0107 363. 0. We observed that very often.0002 0. 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.0083 376. AP is negative: the experimental error associated with pressure mass transfer is the limiting process.0013 .1891 . Pressure deviation induced by upward and downward temperature paths for methanol-acetone..72 0.2280 0.126 p “P P down DP = Pu. If methanol-acetone binary.5075 0.19 0.0019 .84 0.0025 337.2136 0.64 0. 0. an on-line gas chromatograph.86 0.1642 0.0014 .4429 0.oQO4 .02 0.0694 0.78 0. 0.0798 .1659 ~ 0. 0.0854 ~ o.3620 0. 0.003 1 331.4429 0. or is of the order of magnitude of the obtained simultaneously during the same experi- experimental pressure error.62 0.ooo3 _ 0.4734 0. If we suppose that the The gas-phase composition can be obtained from cell is perfectly mixed-a reasonable hypothesis be.0605 o.0021 .0017 .3636 .1555 .2601 0.3389 0.1349 0. 0.2436 0.0044 384. This information is cause of the cell and stirrer design-there is a com.65 0.0077 378. 0.0021 ~ 0.0000 0. 0.83 0.0062 343.0017 388.0851 0. the pressure 1%.1192 . 0.2459 . 0.0024 .0016 .1107 0.2992 .0020 _ 0. o. 0. 0.0002 .1440 0. The parameters estimation results were expressed sensor dynamic can be neglected with respect to the as y =f(x) curves.0101 369.2158 .0092 374.4148 .2803 .0023 .0650 0.3874 0.0001 0.0012 .0105 365.1044 . 6. 0.0. 0.0018 0.0094 371.2625 .0097 355. 1975). o.20 0.14 0.50 0. 0.58 0.0076 349.4141 0.a302 0.53 0.ooo9 .0096 353.0796 0. 0.0007 . . representative of the thermodynamic equilibrium.1772 .0056 382.0695 0.0014 333. WPa) (MPa) (MPa) DPjP up 396.1037 0. T. We conclude that the ments.2969 0.1262 0.1753 0. 0.77 0. 0.87 0. 0. 0.0104 359.0648 0. 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.4742 0.1274 .0108 361.96 0.10 0.49 0.0607 0. 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.0567 0.68 0.2303 .2780 0.0103 367. limiting process. temperature sensor dynamic.0012 . 0. 0.52 0. 0. We exemplify the use of isothermal data with the ward and downward P(t) paths must be positive. scribed (Hirata et al.0081 347. 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.1183 0.3171 0.0744 0.92 0.0000 390. the two binaries were reproducible within less than tween heat and mass transfer.5057 0.1454 . 0. 0.0068 345.26 0.67 0. 0.0033 329.3886 . The comparison between Table 1.0019 .28 0.0008 O. The temper. 0. the AP must be decreasing temperature and is to be compared with negative.0744 0. 0.1999 0.0977 .2020 .0016 . the AP measurements.

0 x & y mol. .0 0. + 330 - z )I 325 0. LIETO time time Fig. With 318K < T < 365K. 8. 7.1975) for methanol-acetone isothermal data for 318 K < T < 365 K at P = 0.5- F 't 330 .. 6.-) and published experimental data ( + ) (Hirata et al. Isothermal and isobaric data obtention from dynamic database..0 0 c) 0 0 a 335 - iz c) :0. acetone x mol.0 0.5 1. . acetone Fig.0 0.1013 MPa. 340 (D cl. our model represents the litera. l-l-C!C.0 0. experimental data is made in Figs 7 and 8 corres.005. Comparison between our model (. acetone x mol. 323 K -C T-c 383K. With with the published experimental data. Prac. acetone Fig.0 0. Therefore. VERNEAU and J..1724 PH. frac. The use of isobaric data is exemplified with a non- ture experimental data with a AT difference less than degassed isopropanol-methanol binary.0 0. our data (and the associated model) and published 1% and a mole fraction difference less than 0. 1975) for methaol acetone isothermal data for 323 K c T < 383 K at P = 0. 340 335 .5 1.1013 MPa. - z 7 325 11 0. Comparison between our model (...-) and published experimental data ( + ) (Hirata et al.. Prac..5 1. our model fits perfectly pond@ to two temperature domains.5 1.0 x i% y mol. 0.

0 0.5 1.0 0. We applied cell-a thermostated autoclave-stirred with a self. methanol x mol. Prac. 360 2 350 0 F0. dynamic T(t) paths modelling based on isobaric data at P = 0. associated with a flash mass balance leads to a model mental data within 1%.15 MPa. 10. Comparison between our model (. contact which allows a very rapid thermodynamic Figures 11 and 12 illustrate the stirring effect on the equilibrium settling.7 Hz The stirring system induces an efficient gas-liquid (no gas recirculation) and 27. f’rec. We can The stirring speed affects the residual pressure dif. frac. can be imposed for a global composition. Even with poorly prepared dynamic equation can be used. this pressure change is stronger in Wilson equation for the liquid. ent injection systems.. computing P and using a gradient technique for the Experiments with the isopropanol-methanol bi.0 0.. 1975) for isopropanol-methanol isobaric data. P. 350 I-. .. T. As expected. nary were performed at two stirring speeds: 13.5 1. our estimation pre. P = 0.5 1. T data for one composi- ference as shown in Table 2.-. modelling implies the virial equation for the gas and sure. . The re- We designed and constructed an ebulliometric sults are obtained with a 1% precision.z are automatically dicts a positive azeotrope because of solubilised gases registered and the analytical system gives y. 9. gather several hundreds of P.345 340 _ - d-0 0. T. parameters estimation.085 MPa. our technique to industrially relevant binaries and - 360 ...-) and published experimental data ( -+ ) (Hirata et al. A novel technique for rapid liquid-vapour equilibrium measurement and modelling 1725 isobaric data were strongly affected by solubilised inducing turbine.5 I. P = 0.1013MPa. As illustrated in Figs 9 and 10.0 x & y mol. The experiment duration (2 days) is definitely shorter than the classical ebulliometric technique CONCLUSION duration for the same information content. tion. x) technique solvents. -) and published experimental data ( + ) (Hirata er al. The (P. the estimation predicts the literature experi.345 G 340 0. 1975) for isopropanol-methaol isobaric data. but any other thermo- the weak pressure domain. an on-line gas chromatograph.0 x & y mol. and connected to a PC.7 Hz (gas recirculation). Comparison between our model (. Phase which are desorbing in the cell and increase the pres. Therefore. me thano I Fig. methanol Fig. equipped with automatic constitu- gases in the binary constituents.

I! global molar fraction of the volatile N (Hz) 13. VERNEAU and J. and Van Ness. C. Vapor-liquid equilibria t time from total pressure measurements. Comparison between our model (. K Engng Chem. C.1013 MPa and 27...0 Ol x mo I .7 Hz (gas recirculation). 12.-) +nd publishedexperimental data ( + ) (Hiram et al. methanol Fig.7 Hz (no gas recirculation). exp experimental tion was obtained through the comparison between computed and analysed gas-phase molar fractions REFERENCES and the small values of the average residual pressure Berro. - 340 i? 335 0.0 x mol. J.0 0. Stirring speed influence on x liquid molar fraction of the volatile residual pressure difference Y vapour molar fraction of the volatile AP (%) . 1118-1123.0 0. liomttre pour la d&termination rapide et prkcise des iquilibres liquideevapeur des solutions. 11(3). frsc. le binaire NOTATION m&hanol-1 propanol g 60.. 41ck-413. . 1975. Comparison between our model (. Fundam. 360 355 . R...5 Greek letters 27. The model valida. 72(10). 1975) for isopropanol-methanol isobaric at P = 0.5 1.8 A difference Subscripts cal calculated were able to obtain y = f(x) curves. LIETO 360 340 0. Un ebul- difference induced by the temperature programming. them.1013 MPa and 13. H. P pressure.OZ”C. Phys. Stirring speed effect. R. A new apparatus. Deyrieux. Table 2.-) and published experimental data ( + ) (Hirata et al. Pa Gibbs. and Peneloux. frac.5 +345 : .1 1. A... ~3350 :0.1726 PH.. T temperature. Il..5 1. Stirring speed effect. Ind.7 2. 1975) for isopropanol-methanol isobaric data at P = 0. E. me then o I Fig.

126128. Fried. ties of ethanol + water. and Robert-Morley. Results for (methane + n-pentane).. A static Aided Data Book of Vapor Liquid Equilibria.. 1946. and Gemhling.. P. Ind. Kolbe. Pick. A static Phase Equilibria 23. and Vilim. 38(7). Vapour po-liquid equilibrium data. method for determination of vapour liquid equilibria and Othmer. J. Computer Reiff. 7Twmodyn. B. 153-168. and Lucas. 1985. V. and-Magahama. I _ measurements at high temperatures and -msults pressures.. Peters-Gerth. 14(2). W. A novel technique for rapid liquid&vapour equilibrium measurement and modelling 1727 Hala. J. I.. Elsevier.. Fluid Phase Equilibria 83. Hiraia. R. Multipurpose high-pressure phase-equilib- Rarey. and Renon.. 1975. them. S. atures using a new variable-volume cell. Peraamon Press. 0. Composition of satured liquid molar volume at high pressures and temper- vapors from boiling binary solutions apparatus for deter. Engng Chem. J. Liauid Eauilibrium. .. J. Engng Chem. differential static apparatus for the measurements of va.. and Gmehling. Fluid Rousseaux.* Ohe. equilibrium apparatus for (vapour + liquid) equilibrium Amsterdam.. Vapour-liquid equilibria meas.. S. Slocum. K. E. 1993. Fundam. 279-287. libria 11. Thermodynamic proper. 19. P.. 751-757.467477. urements from 90 to 150°C by the static method. M.. F. 1967. E. Richon. F. H. K. D. 213-226. D. Ind. E. Fluid Phase Equi- minations under pressure. 1983. Computer-operated rium apparatus. 1975. Oxford. 1987.