Beruflich Dokumente
Kultur Dokumente
J.D. Raal* and A.L. Muhlbauer' Deparfmenf of Chemical Engineering, Universdy of Natal, King George V Avenue, Durban 4001, SOUTH AFRICA
Accurate measurement of high pressure vapour-liquid equilibria is a most demanding task and has elicited much effort and ingenuity from researchers. The number and variety of approaches adopted attest to the exacting nature of the task offinding the most reliable, accurate and cost-effective approach. There is as yet no firm consensus of opinion as to which type of equipment is superior. Each type has its advantages and drawbacks and persuasive advocates. There are few areas of research in chemical engineering or physical chemistry in which so great a variety of equipment and techniques has been reported. The purpose of this publication is to summarize in some detail the equipment and procedures used to measure high pressure VLE and to comment on some of the difficulties common to several methods. In Part I we discuss dynamic measurement methods and refer to a new high-precision volumetric device we have developedfor gas chromatograph calibrationfor gas mixtures or for gas-liquid mixtures. In Part 11 we examine static methods for high pressure VLE measurement and present proposals for a new cell suitable for multiphase equilibrium and volumetric data measurement. A complete survey of the numerous types of equipment used and proposed is not feasible within reasonable length. Good reviews by Tsiklis[l] (1968) and Young[2] (1978) in particular are available, and our emphasis is on more recent developments. This review will be useful to those entering the field or those experiencing problem with a particular type of apparatu.
classified as a dynamic or flow method, othmise it is a static method. Sub-division of the static method depends on whether the phases are sampled or not. In a new development in our laboratories we have designed a static cell with internal circulation through the sampling valves, i.e. the design combines elements of the static and flow methods. The design and associated results will be published at a later
date.
OPTIC
NON-OPTIC
STATIC NON-ANALYTICAL
.c
T I
STATIC
STATIC
OMBINED
STATIC ANALYTICAL
E
OPTIC
NON-OPTIC
Dynamic and Static Analytical Methods Main features of the analytical method A schematic diagram of an apparatus in this category is shown in Figure 2. It consists of the following: (i) An equilibrium cell in which the vapour and liquid phases of the mixture are in equilibrium. (ii) An environment that controls the temperature of the equilibrium cell, e.g. airbath, oil or water bath, or a copper or aluminium jacket (Konrad et d.[4],Ng and Robinson [5]). (iii) A procedure for agitating and mixing the cell contents. Static methods use an internal stirrer whereas in dynamic methods the circulation of one or more phases fulfils this role. However, some vapour recirculation methods do have an additional internal stirrer. Rocking of the equilibrium cell assembly to attain equilibrium has also been used (Ashcroft et al. [ 6 ] ,Huang et al. [71)but this procedure is unnecessarily cumbersome.
70
(iv) A method for sampling the vapour and liquid phases. In the two-phase recirculation and single-pass vapour and liquid methods, sampling presents few problems since a representative portion of the flow is readily diverted for sampling. The vapour recirculation method requires some form of liquid sampling device. (v) A means for accurate analysis of the withdrawn samples. (vi) Pressure and temperature measuring devices.
PRESSURE AND TEMPERATURE MEASURING DEVICE
do
AG lTATl0N DEVICE
7 LIQUID SAMPLING A
SYSTEM
CONTROLLED ENVIRONMENT
It is recommended that several temperature sensors be installed in the walls of the equilibrium cell to test temperature homogeneity, which should be within 0.2K. There should be no conductive paths to or from the cell through fittings or attachments, and there should be no direct radiative energy exchange between the cell and the bath heaters. A copper lining on the interior of the constant temperature bath (if used) is recommended. Many authors have reported measurements of bath or cell temperature profiles, e.g. Rogers and Prausnitz [9], and Figuiere et al. [lo]. The attainment of equilibrium Since equilibrium requires a balance of all potentials that may cause change, a true state of equilibrium is probably never reached due to continuous small changes in the surroundings and to retarding resistances. Mechanical stining of the liquid phase produces fluid friction and its dissipation to the surroundings must produce some temperature gradient. Temperature,pressure, vapour and liquid composition,and in some cases stability of refractive index (Besserer and Robinson [ll]) are important indicators in judging whether equilibrium has been reached. Fredenslund [ 121 proposes, as a criterion, a change in pressure of less than 0.05% in 30 minutes. Repeated vapour and liquid sample composition analyses must give reproducible results within the limits of the analytical procedure. Disturbance of equilibrium during sampling Sampling of either the liquid or vapour phase may entail a change in the volume of the equilibrium cell with the size of the effect being inversely proportional to the cell volume. Pressure fluctuations of 0.1 and 0.01 bar due to sampling have been reported by Besserer and Robinson [ 113, and Wagner and Wichterle [ 131, respectively. In addition to the volume change due to sample removal, the sampling device itself (e.g. a sliding rod sampler) may produce interior cell-volume changes. A large cell-volume dampens these volumetric disturbances but the penalty in increased use of chemicals may be unattractive. Comparatively large cell volumes were used by Sagara et al.[14], Klink et al. [15], Aschroft et al. [6], and Reiff et al. [16], to counteract volume changes due to sampling. M o r e ingenious procedures, where the volume change is due only to the withdrawn samples, have been proposed. Rogers and Prausnitz [9] and Nakayama et al.[17] used sampling rods traversing the entire cell and sealed at both ends. In variable-volume cells, the pressure change due to sampling can be compensated by pressure adjustment (Nakayama et al. [17]). Phase compositions can also be analyzed in-situ by optical methods (Konrad et al. [4]) without disturbanceof the cell content.
'
Sample homogenization In liquid-phase sampling there is a tendency for the more volatile components t o flash preferentially, and thus to produce concentration gradients in the resultant vapour. Homogenizing this vapour mixture without recondensation is one of the more difficult problems in high pressure VLE measurement. Several procedures have been adopted in attempts to overcome this problem, for example: (i) the use of a stirred homogenization vessel in the sample line (Wagner and Wichterle [131);
(ii) circulation of the vapourized liquid sample with a pump through an evaporating chamber in a closed loop, before expelling the sample to a gas chromatograph (Nakayama et al. [ 171); (iii) expelling the liquid sample into an evacuated jet mixer (in which the swirling recirculation homogenizes the vapour, Miihlbauer and Fbal [18]). This device is remarkably simple but its size must be carefully calculated. A pressure uansducer flush-mounted in the wall of the jet mixer gives a reliable indication of the constancy of the liquid sample size.
Analysis of withdrawn samples Gas chromatography and spectroscopy are the most commonly used methods of analysis. Refractive index measurement in conjunction with GC analysis has also been reported (Besserer and Robinson [ll], and Kalra et al. [19]). A disadvantage of this procedure is that the high-pressure high-temperature equilibrium state differs considerably from that of the input to the gas chromatograph. In-situ phase composition analysis by spectroscopy (based on Beer's law) overcomes sample preparation difficulties. Konrad et al. (4) and Swaid [203report the use of infrared spectra (where the absorption bands are often well separated) to determine phase concentrations. Infrared, visual and ultraviolet spectroscopy or Raman scattering methods require more extensive calibration procedures than gas chromatography analysis, and the latter is used most frequently in VLE measurements. Visual and ultraviolet spectroscopy is largely restricted to aromatic or coloured compounds. Accurate gas chromatograph detector calibration (e.g. for thermal conductivity detectors) remains a considerable problem for gas mixtures or for gas-liquid mixtures when reliable commercial standards are not available. For many systems the response-factor ratios are not constant over the entire mole fraction range, and their variation with concentration must be determined. The precision volumehic calibration device developed in our laboratories (see Figure 3) fulfils this purpose (Raal[8]). The instrument is being developed commercially under international patent protection. The device is based on a novel principle in which a piston with an imbedded solenoid valve operates in a highly uniform cylinder. There is a shaft compensating mechanism so that the piston movement produces no change in the t o t a l interior volume, and displacement of a gas from the lower chamber to the upper chamber is exactly proportional to the piston Davel. The latter can be measured to 0.001 mm by counting steps of the stepper motor which drives the piston. For the calculation of volume/mole fractions, all equipment dimensions cancel and there is a single invariant equipment constant. In principle, no other volumetric or flow device or procedure can equal or surpass the accuracy of this instrument. A robust microdroplet dispenser with a volumetric discharge independent of fluid properties has been developed as an accessory for preparing standard gas-liquid mixtures, and can dispense volumes from 10 picolitres to 2 cm'. Temperature and pressure measurement Temperatures are easily measured with satisfactory accuracy using platinum resistance thermometers, thermocouples or thermistors. Highly stable thermistors with very steep temperature gradients are now available although such sensitivity is
7 3
not usually required. Bourdon-type pressure gauges and pressure transducers, some of the latter with temperature compensation over wide ranges, are favoured devices but may require calibration with a dead-weight piston gauge.
Degassing Degassing the non-volatile (liquid) component is necessary since dissolved gases will compete with the volatile component at low liquid-phase mole fractions. Degassing is especially important in systems where the two components have very s m a l l mutual solubilities, e.g. the propane-water system (Miihlbauer and Raal [18]).
PRESSURE
n
TEMPERATURE PROBE (Pt-loo1
PISTON
MAGNETIC COILS
IMPELLERS
SOLENOID VALVE /
-7
BEARtNG
STEPPER MOTOR
---a
74
The importance of degassing is stressed by Figuiere et al. [lo], Legret et al. 1211. Liquid degassing can be done in-situ in the cell or before sample introduction using equipment such as that of Van Ness and Abbott [22] or Battino et al. [23].
75
2 cT
=!
m s
I SAMPLE
SAMPLE
Table 1 Shale Phase Reckculstlon Aooarutus Aenorted in the Utersture Operating Range Claimed Equilibration time min Cell Measurement Device Sample Size VaP Liq
Cell Volume
Ref.
Date
cma
fl
! a ! Q u
RT RT RT RT DWP B B
r"
1201180
3.5 SOQOO
3.5
15 168 230 50 56 100 304 Stainless steel Austenitic steel Chromium-nickel steel Stainless steel Stainless steel Hastelloy C-276
RT
DWP DWP
B B 501200
Recirculation Fredenslund Dorau Weber Meister Meister Freitag Chou Shah 3251500 137 423 316 Stainess steel 83 Sapphire TC TC RT
30 60 5/10
m
10
Recirculation
Kim
(36) 1989
100
TC
25
0.5
I
-
(1I Due t o space limitations only first author mentioned. ( 2 ) Material of construction of equilibrium cell. (3) TC = thermocouple; RT = Platinum Resistance Thermometer (Pt 100 0). (4) B = Bourdon pressure gauge; PT = Ressure transducer; DWP = Dead weight piston Qauge.
Two-Phase Rockc
Operating Ranus
in the Utararure
I
Volume
Equilibration time
Sample Size
Temp
R S S S
Press
VSP
Liq
Ref.
Date
cm3
bar
(2)
1 3 1
(4)
min TC TS
RT TC
fl
B B
( 2 5 1 1965 Muirbrook (261 1983 K i n 0 (27) 1983 Kubota 128) 1984 Radosz (291 1985 Moms Yorizane (30) 1986 Takishima (31)1986 (32) 1990 lnomata 133134) 1988 D'Souza Adams (35)1988 Kim (36)1989 (37)1989 Shibata Jennings (38)1989 Weber (40) 1989 (41)1990 (42) 1990
200 300 106 60 100 160
700
1250 403 Stainless steel 500 Stainless steel 800 304 Stainless steel 350 146-109 90 304 Stainless steel
8
PT PT B B PT
11 600
134700
120 15 10115 60 1 6 1 80 250 422 100 1 9 0 1 103 250 3 16 Stainless steel Stainless steel Sapphire
QT TC RT
1 0 0 201250
100 03
750 100
1 50
100
40 65 60
suzuw
PT
60 3 16 Stainless steal
Stainless steel
3 001
lo00
m
DWP
m
300 Stainless steel
Hastelloy C
m
RT
RT
DWP PT
B 8
10 30145
100
480
TC
FT
Fink
1 20
10000
0 . 2 1 750
(1)Due to space limitations only first author mentioned. (2)Material of construction of equilibrium cell. (3)TC = thermocouple; RT = Platinum Resistance Thermometer If? 100 n).TS = Thermistor, QT = Quartz Thermometer (4) B = Bourdon pressure gauge; PT = Presswe transducer; D W = Dead weight piston gauge.
I t
from the cell. In the liquid phase and two-phase recirculation methods the liquid phase can be sampled by isolating a quantity of the circulating phase, e.g. by diversion through the external loops of commercially available liquid or vapour chromatography valves. The use of Rheodyne or Valco valves was reported by DSouza and Teja [331, DSouza et al. [34], Adams et al. [351, Jennings and Teja [38], Kim et al. [36], and Fink and Hershey [42]. This feature makes liquid sampling relatively easy and sfmightforward when compared to the static method, for example. This simplicity of sampling in the two-phase recirculation method is, however, somewhat negated by the added complexity of a liquid recirculation loop. Another reason for the popularity of these methods is the increasing availability of commercially manufactured (usually magnetically driven) pumps. Muirbrook and husnitz[25] and Fleck and hausnitz[49] had to design and construct their own pumps which they describe in detail. One of the earliest examples of this type of apparatus was that used by Muirbrook and Prausnitz[25] to measure the ternary system nitrogen-oxygen-carbon dioxide. The circulation of the phases provided sufficient agitation to ensure equilibration of the phases, and no additional liquid phase agitation was required. Samples for analysis were obtained by blocking off sections of the circulation line. Calibration of these sample spaces permitted the determination of phase molar volumes. Liquid entrainment in the vapour stream was prevented by a simple baffle. The authors reported using a liquid level indicator. The vapour recirculation apparatus of Fredenslund et al. [12] has a unique sampling device. Its principle subsequently formed the basis of the liquid sampling devices of Meister [50], and those developed for the static equilibrium cells of Bae et al. [51], Ng and Robinson [5], and Muhlbauer and Raal[18]. It had a 5 mm diameter rod with a 3.5 pl hole drilled near its tip. The latter was totally immersed in the n withdrawal of the liquid phase upon insertion of the rod into the equilibrium cell. O sampling rod the hole came into alignment with sample ports drilled into the cell wall. Carrier gas then flushed the sample to a gas chromatograph for composition analysis. Freitag and Robinson [24] extracted liquid samples directly from the equilibrium cell through a 90 cm capillary tube, at the end of which was located the liquid sampling valve. The arrangement provided for the acquisition of a lowpressure vapour sample of the same composition as the high-pressure liquid in the cell. All of the sample was captured as it flashed while flowing through the capillary tube and needle valve. The low pressure sample was circulated to ensure homogeneity before being analyzed. Dorau et al. [52] extracted both the vapour and liquid samples directly from the equilibrium cell through capillary tubes. These capillaries led to evacuated flasks attached by rapid connection couplings. In order to obtain representative liquid samples the authors reported that the flask volume had to be greater than the inventory of the capillary tubing. The experimental method of Chou et al. [53] was somewhat similar. The equilibrium cell had separate sampling ports for the vapour and liquid phases respectively. A specially designed detachable microcell, similar in principle to the ones used by Legret et al. [21], was attached to each sampling port. The microcell collected an equilibrium phase sample from the sample analysis system (enclosed in a separate air bath) for composition analysis. In the sample analysis system, the microcell was attached to a variable-volume bellows assembly
79
(1)Equilibrium Cell; (2) windows,' (3)sample charging pump; (4) liquid sample; (5) pressure transducer; (6)sampler; (7) magnetic pwnp; (8)magnetic stirrer; (9)jlash tank; (10) temperature controller: (11) vacuum pump: (12) NH, sample cylinder; (13)N2gas cylinder: (14)NH3 gas cylinder: (15)He gas cylinder; (16)air bath: (I 7 ) gas chromatograph. (Reprinted with permission from J.Chem.Eng.(Japan); Copyright 1986, American Chemical Society)
that acted both as a flash vessel and pump. The bellows assembly circulated the flashed sample through the gas chromatographic sampling valve until a homogeneous sample suitable for composition analysis was obtained. p o r tvalve which (with The experimental apparatus of Kubota et al. [27]used a 6 the appropriate setting) allowed the high pressure pump to circulate either the vapour o r liquid phase. Representative samples of the vapour and liquid phases were trapped in the 4-port valve and subsequently released into a low pressure line. The sample was circulated until it was homogenized before analysis by gas chromatography. The authors claimed that equilibration of the phases required approximately 2 hours. In recent years the most popular method of sampling the circulatingphases is by using a commercial sampling valve located in the circulation lines. Shibata and Sander [37] used a more elaborate method of trapping vapour and liquid samples in sample bombs and transfemng these to a gas chromatograph for analysis. The latter is very similar to the vapour recirculation methods used by Dorou et al. [521 and Chou et al. [53]. Yorizane et al. [30]describe an unusual method of cell content agitation. The apparatus consisted of two equilibrium cells which were connected to each other at
both the top and bottom ends by means of flexible stainless steel tubes. One cell was fixed while the other was moved slowly up and down by means of a mechanical device. This motion produced a pressure merit which induced liquid- and vapour phase-flows in opposite directions to equalize the pressure. For recirculation methods in general, vapourization and condensation of the circulating liquid and vapour streams must be avoided. This has been overcome in a number of ways, for example: (a) Having three separately controlled temperature zones, one for the equilibrium cell and another for the vapour recirculation loop in which the temperature was slightly greater than the equilibrium temperature. The third zone for the liquid recirculation loop was maintained at a temperature slightly lower than the equilibrium temperature. A good example is the equipment of Takishima et al. [31] and Inomata et al. [32]. Both have similar circulation loops and sampling h r e e different temperature zones (see Figure 6). systems housed in t (b) Sampling the phases directly from the equilibrium cell, which partially negates the advantages of a recirculation method. (c) Removing samples from the equilibrium cell by some device, and transferring these samples to an analysis device (Dorou et al. [52]; Shibata and Sandler [37]; Chou et al. [53]). It is interesting to note that Kubota et al. [27], King et al. [26], Takishima et al. [31], Inomata et al. [32] and Suzuki and Sue [41], all report the use of internal stirrers to aid in the equilibration process. Difficultiesencountered in the recirculation methods are: (i) Maintaining an adequate liquid level in the equilibrium cell. The only authors who mentioned the use of a liquid-level measuring device were Muirbrook and Prausnitz [25] and Simnick et al. [43]. All other authors appear to rely on visual observation to maintain the desired liquid level. (ii) Prevention of droplet entrainment in the effluent vapour stream. The only specific reference to a demisting device was by Muirbrook and Prausnitz [25].
a
LIQUID FEED
I
8
PREHEATER
MIXER
,$LOURFEED
TIM0 3
Temp
Cell
(2)
Measurement Device
Hold up time
Sample size
C m
Date
1977 1980 1986 1986 1986 1990 90
K
703
710 710 623 673
sec
(43)
3 16 Stainless Steel
316 Stainless steel 316 Stainless steel 3 16 Stainless steel 450 Stainless steel
10
30 250 10-50
I
pt
50012 000
1320/1 860
18-36
I I
= 100 n
NA
NA
(1 Due to space limitations only first author mentioned (2) Material of construction of equilibrium cell (3) TC = thermocouple; RT = Ratinurn Resistance Thermometer, (41 B = Bourdon pressure gauge.
(iii) Ensuring that the pumps used do not contaminate the equilibrium mixture or create stagnant spaces. The former problem has largely been overcome by the use of magnetically coupled pumps. (iv) Avoiding the possibility of partial condensation and vaporisation of the circulating vapour and liquid streams respectively. (v) Avoiding undesirable pressure gradients across the equilibrium cell caused by the circulating pump. In principle this is a weakness of the circulation method since flow cannot be produced without a pressure gradient. In practice data from circulation methods compare well with those from static type cells. In a new development in our laboratories (Raal [54]), the liquid stirrer itself provides a small recirculating flow through a liquid sampling valve mounted in the cell wall.
The Single-Vapour and Liquid Pass M e t h o d This is a relatively recent development of the dynamic method and was developed principally for high-temperature and high-pressure vapour-liquid equilibrium measurements, where thermal degradation of a hydrocarbon could occur. The features of a typical single vapour-liquid pass method are shown in Figure 7, and a description of the method follows. Separate streams of vapour and liquid components are contacted co-currently at a controlled temperature and pressure in a mixing unit. The combined stream passes into an equilibrium cell where the mixture separates into vapour and liquid phases. The two phases exit from the equilibrium cell separately and sampling is achieved by the diversion of the effluent streams. A summary of some of the apparatus described in the literature is given in Table 3. Single Vapour-Liquid Pass Apparatus in the Literature The apparatus used by Inomata et al. [46] for a variety of hydrocarbon systems shows the essential features common to all flow apparatus of this kind. The gaseous component at its critical pressure was supplied from a buffer tank. The gaseous and liquid components were contacted co-currently before entering the preheater. The preheater consisted of a tube which was initially heated by an electric line heater and finally by an air bath. The air bath was used to adjust the mixture to the desired equilibrium temperature. The static mixer produced homogenization and rapid equilibration. The cell design incorporated features to minimise fluid entrainment, a problem with this type of apparatus. The inlet nozzle was inclined so as to minimise liquid entrainment in the vapour phase and as an additional measure a demister was fitted at the vapour outlet. To avoid entrainment of the liquid withdrawn from the cell and to maintain a steady liquid level, the cell was fitted with an overflow-type level-control system and back-pressure regulator. The liquid level could be detected by a capacitor sensor, and according to the authors proved a useful aid in achieving steady-state operation. Simnick et al. [43] combined the final heater and static mixer features into one unit. They fitted a notched twisted ribbon inside the entire length of their heater/mixer. This unit brought the final temperature of the mixture to within 1C of the equilibrium temperature. The apparatus of Sebastian et al. [443 was essentially the same as that of Simnick et al. [43]. However, the equilibrium cell used by Lin et al.[45] was different as they found the capacitor level-indicator of Simnick et al.[43]
83
J.D.Raal and A L . M W b a w r
to be unsuitable for the system being measured, and they designed an optical cell.
The sapphire window created a sealing problem as no organic elastomer could seal at the temperatures of interest. The problem was solved by using a gold O-ring with a copper shim. This seal was nevertheless considered to be the factor limiting the operating pressures and temperatures. The auxiliary apparatus of Niesen et al. [47] was essentially the same as that of Lin et al. [45] but their equilibrium cell differed. Severe corrosion problems were experienced which ruled out the use of a liquid-level measuring device and necessitated the use of a view cell. Simnick et al. [43], Sebastian et al. [44], Lin et al. [45], and Inomata et a1 [46] indicated that the measured compositions of the vapour and liquid phases were independent of the feed flow rates tested, confirming that equilibrium had indeed been reached. Sebastian et al. [44]and Inomata et al. [46] found thermal decompositions to be negligibly small. Roebers and Theis [48] describe a well-designed equilibrium cell which theoretically has superior temperature and pressure operating ranges to other equilibrium cells. Experimental results using this cell were in press at the time of writing and unavailable for comment. Difficulties encountered by this method are : (i) E n s u r i n g that equilibrium has been reached in one pass. (ii) Ensuring complete phase separation in the equilibrium cell. (iii) Achieving a steady liquid level in the equilibrium cell. (iv) Prevention of droplet entrainment in the effluent stream. (v) Ensuring the pumps do not contaminate the equilibrium mixture. (vi) Minimizingthe effect of undesirablepressure gradients across the equilibrium cell. In addition, the designer faces materials selection problems due to the very reason these apparatus were designed, namely high temperatures.
3. Conclusions
Several synthetic and analytical procedures and many different types of dynamic equipment for high pressure VLE measurement have been surveyed. The problems common to most methods were reviewed, including the attainment of equilibrium, sampling from a high-pressure space, sample homogenization, and accurate sample analysis. Calibration of gas chromatograph detectors for gas mixtures or gas-liquid mixtures will be facilitated with a new high-precision volumetric device capable of producing binary or multicomponent mixtures from ppm values up to 50 mole%. In Part I1 static procedures used for high pressure VLE measurement are reviewed.
References
1. Tsiklis, D.S. 1968. Handbook of Techniques i n High Pressure Research Engineering. New
York: Plenum Press. 2. Young,C.L. 1978. An Experimental Method for Studying Phase Behaviour of Mixtures at High Temperatures and Pressures. In McGlaston, M.L. (senior reporter) A S p e c i a l i s t Periodical Report, V01.2: Chemical Thermodynamics: 71-104. London. The Chemical Society. 3. biters, U.K. & Schneider, G.M. 1986. High Pressure Phase Equilibria: Experimental
84
Methods. Fluid Phase Equilibria, 29,145-160. 4. Konrad R., Swaid 1. & Schneider. G.M., 1983. High-Pressure Phase Studies on Fluid Mixtures of Low-Volatile Organic Substances with Supercritical Carbon Dioxide. Fluid Phase Equilibria, 10,307-314. 5. Ng, H.J. & Robinson, DB. 1978. Equilibrium Phase Properties of the Toluene-Carbon Dioxide System. J. Chem. Eng. Data, 23(4), 325-327. 6. Ashcroft. S.J.. Shean. R.B. & Williams C.J.J.. 1983. A Visual Equilibrium Cell for Multiphase Systems at Pressures up to 690 Bar. Chem. Eng. Res. Des.. 61.51-55.7. 7. Huang, S.S.S., Leu. A.D., Ng. H.J. & Robinson, DB. 1985. The Phase Behaviour of Two Mixtures of Methane. Carbon Dioxide, Hydrogen Sulphide and Water. Fluid Phase Equilibria, 19,21-32. 8. Raal, J.D. 1992. A New Device for the Calibration of Gas Chromatographs for Gas Mixtures. Pitcon 92, New Orleans, USA. 9. Rogers, B.L. and Prausnitz, J.M. 1970. Sample-Extraction Apparatus for High Pressure Vapour-Liquid Equilibria. Ind. Eng. Chem. Fundam.. 9(1). 174-177. . , Renon, H., Richon, D. & Szwarc, H. 1980. Vapour10. Figuiere. P., Hom, J.F., Laugier, S liquid Equilibria up to 40 OOO kPa and 400OC: A New Static Method. AlChE J.. 26(5). 872-875. 11. Besserer, G.J. and Robinson, D.B. 1971. A High Pressure Autocollimating Refractometer for Determining Coexisting Liquid and Vapour Phase Densities. Can. J. Chem. Eng., 49, 651-656. 12. Fredenslund, Aa., Mollerup, J. and Christensen, L.J. 1973. An Apparatus for Accurate Determination of Vapour-Liquid Equilibrium Properties and Gas PVT Properties. Cryogenics, 13,414419. 13. Wagner, 2. and Wichterle, I. 1987. High-Pressure Vapour-Liquid Equilibrium in Systems Containing Carbon Dioxide, 1-hexene and n-hexane. Fluid Phase Equilibria, 33,109-123. 14. Sagara, H., Arai. Y. and Saito, S. 1972. Vapour-Liquid Equilibria of Binary and Ternary Systems Containing Hydrogen and Light Hydrocarbons. J. Chem. Eng. (Japan), 54,339348. 15. Klink, A.E., Cheh, H.Y. and Amich (Jr), E.H. 1975. The Vapour-Liquid Equilibrium of Hydrogen-n-Butane System at Elevated Pressures. AlChE J.. 21(6), 1142-1148. 16. Reiff, W.E., Peters-Gerth. P. and Lucas. K. 1987. A Static Equilibrium Apparatus for (Vapour + Liquid) Equilibrium Measurements at High Temperatures and Pressures. Results for (methane + n-pentane). I., Chem. Thermodynamics, 19,467477. 17. Nakayama, T., Sagara, H., Arai. K. and Saito, S. 1987. High Pressure Liquid-Liquid Equilibria for the System of Water, Ethanol and 1.1-Difluoroethane at 323.2 K. Fluid Phase Equilibria, 38, 109-127. 18. Miihlbauer, A.L. and Raal, J.D. 1991. Measurement and Thermodynamic Interpretation of Vapour-Liquid Equilibria in the Toluene-C02 System. Fluid Phase Equilibria, 64.213236. 19. Kalra, H., Kubota, H., Robinson, D.B. and Ng,H.J. 1978. Equilibrium Phase Properties of the Carbon Dioxide-n-HeptaneSystem. J. Chem. Eng. Data, 23(4). 317-321. 20. Swaid I. 1983. Dissertation, University of Bochum. 21. Legret, D. Richon, D. and Renon. H. 1980. Static Still for Measuring Vapour-Liquid Equilibria up to 50 bar. Ind. Eng. Chem. Fundam.. 19,122-126. 22. Van Ness, H.C. and Abbott, MM. 1978. A Procedure for Rapid Degassing of Liquids. Ind. Eng. Chem. Fundam.. 17,66-67.
85
23. Battino. R., Banzhof, M., Bogan. M. and Wilhelm. E. 1971. Apparatus for Rapid Degassing of Liquids, Part 1 1 1. Analytical Chemisay, 4 3 ( 6 ) , 806-807. 24. Freitag, N.P. and Robinson, D.B. 1986. Equilibrium Phase Properties of HydrogenMethane-Carbon Dioxide, HydrogenCarbon Dioxide-n-Pentane and Hydrogen-n-Pentane Systems. Fluid Phase Equilibrii 31,183-201. 25. Muirbrook. N.K. and Prausnitz, JM. 1965. Multicomponent Vapour-Liquid Equilibria at High Pressures: Part 1. Experimental Study of the Nitrogen-Oxygen-Carbon Dioxide System at O O C . AlChE J.. 1 1 ( 6 ) , 1092-1096. 26. King, MB.. Alderson, D.A., Fallah, F.H.. Kassim, KM., Sheldon, J.R. andMahmud, R.S. 1983.Some Vapour-Liquid and Vapour-Solid Equilibrium Measurements of Relevance for Supercritical Extraction Operations and their Correlation. In Paulaitis. M.E., Penninger. J.M.L., Gray, R.D. and Davidson. P. (eds). Chemical Engineering at Supercritical Fluid Conditions. Ann Arbor: The Butterworth Group: pp.31-80. 27.Kubota, H.. Inotome. H.. Tanka, Y. and Makita, T. 1983.Vapour-Liquid Equilibria of the Ethylene-PropyleneSystem under High Pressure. J. Chem.Eng. (Japan), 1 6 ( 2 ) , 99-103. 28.Radosz. M. 1984. Variable-Volume Circulation Apparatus for Measuring High-Pressure Fluid Phase Equilibria. Ber. Bensenges. Phys. Chem., 88.859-862. 29.Morris, W.O. and Donohue. M.D. 1985. Vapour-Liquid Equilibrium in Mixtures Containing Carbon Dioxide, Toluene, and I-methylnaphthalene. J. Chem. Eng. Data, 30,
259-263. 30.Yorizane, M., Yoshmura, S . . Masuoka, H.. Miyano. Y. and Kakimoto, Y. 1985.New Procedure for Vapour-Liquid Equilibria. Nitrogen + Carbon Dioxide, Methane + Freon 2 2 , and Methane +Freon 12.J. Chem. Eng. Data., 30.174-176. 31.Takishima, S., Saiki, K., Arai., K. Saito. s. 1986.Phase Equilibria for CO, - C2HflH - H20 System. J. Chem. Eng. (Japan), 1 9 ( 1 ) , 48-56. 32.Inomata, H., Ihawa, N.. Arai, K. and Saito. S. 1988. Vapour-Liquid Equilibria for the Ammonia-Methanol-Water System. J. Chem. Eng. Data, 33,2629. 33. DSouza, R. and Teja, AS. 1988.High Pressure Phase Equilibria in the System Glucose + Fructose + Water + Ethanol + Carbon Dioxide. Fluid Phase Equilibria, 39,211-224. 3 4 .DSouza, R., Patrick, J.R. and Teja, AS. 1988.High Pressure Phase Equilibrium in the Carbon Dioxide-n-Hexadecane and Carbon Dioxide-Water System. Can. J. Chem. Eng.. 66,319-323. 35. Adams, W.R., Zollweg. J.A.. Street, W.B. and Rizvi, S.S. 1988.New Apparatus for Measurement of Supercritical Fluid-Liquid Phase Equilibria AlChE J.. 3 4 ( 8 ) , 1387-1391. 36. Kim,C.H., Clark, A.B., Vimalchand, P. and Donohue, M.D. 1989. High Pressure Binary Phase Equilibria of Aromatic Hydrocarbons with CO, and C2H6.J. Chem. Eng. Data, 34, 391-395. 37.Shibata, S.K. and Sandler S.I. 1989. High Pressure Vapour-Liquid Equilibria Involving Mixtures of Nimogen, Carbon-Dioxide and Cyclohexane. J. Chem. Eng. Data. 3 4 ,291298. 38.Jennings, D.W. and Teja, AS. 1989.Vapour-Liquid Equilibria in the Carbon-Dioxide-1Hexene and Carbon Dioxide-1-Hexyne Systems. J. Chem. Eng. Data, 34.305-309. 39.Weber. W., Zeck, S. and Knapp. H. 1984.Gas Solubilities in Liquid Solvents at High
Pressures. Apparatus and Results for Binary and Ternary Systems of N , CO, and CH50H. Fluid Phase Equilibria, 18,253-278.
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40.Weber. L.A. 1989. Simple Apparatus for Vapour-Liquid Equilibrium Measurements with Data for the Binary Systems of Carbon Dioxide with n-Butane and n-hexane. Fluid Phase Equilibria, 3(4), 171-175. 41. Suzuki, K. and Sue. H. 1990. Isothermal Vapour-Liquid Equilibrium Data for Binary Systems at High Pressures. Carbon Dioxide-ethanol, Carbon Dioxide-1-1 -propanol, Ethene-Ethanol,and Ethane-1-Propanol Systems. J. Chem. Eng. Data, 35.63-66. 42. Fink, S.D. and Hershey. H.C. 1990. Modelling the Vapour-Liquid Equilibria of 1.1.1Trichloroethane + Carbon Dioxide and Toluene + Carbon Dioxide at 308.323 and 353 K. Ind. Eng. Chem. Res., 29.295-306. 43. Simnick, J.J., Lawson, C.C., Lm, H.M. and Chao. K.C. 1977. Vapour-Liquid Equilibrium of Hydrogefletralin System at Elevated Temperatures and Pressures. AlChE J.. 23(4), 469476. 4 4 . Sebastian. HM., Simmick. J.J., Lin, HM. and Chao, K.C. 1980. Gas-Liquid Equilibrium in Mixtures of Carbon Dioxide + Toluene and Carbon Dioxide + m-Xylene. J. Chem. Eng. Data, 25,246-248. 45. Lm. H.M.. Kim C.H., Let, W.A. and Chao. K.C. 1985. New Vapour-Liquid Equilibrium Apparatus for Elevated Temperatures and Pressures. Ind. Eng. Chem. Fundam., 24, 260262. 46. Inomata, H., Tuchiya. K., Atai. K. and Saito. S. 1986. Measurement of Vapour-Liquid Equilibria at Elevated Temperatures and Pressures using a Flow-Type Apparatus. J. Chem. Eng. (Japan), 19(5). 386-391. 47. Niesen. V.. Palvara, A., Kidnay, A.J. and Esavage. 1986. An apparatus for Vapour-Liquid Equilibrium at Elevated Temperatures and Pressures and Selected Results for the WaterEthanol and Methanol-Ethanol Systems. Fluid Phase Equilibria, 31,283-298. 48. Roebers. J.R. and Theis, M.C. 1990. An equilibrium View Cell for Measuring Phase Equilibria at Elevated Temperatures and Pressures. Ind Eng. Chem. Re.. 29,1568-1570. 49. Fleck, R.N. and Prausnitz J.M. 1968. Apparatus for Determination of Liquid-Liquid-Gas Equilibria at Advanced Pressures. Ind. Eng. Chem. Fundam.. 7(1), 174-176. 50. Meister, K.H. 1985. Apparatuses for the Determination of High-Pressure Vapour-Liquid Equilibrium Data. Lmde Reports on Science and Technology, 39.23-29.42 51. Bae, H.K.. Nagahama, K. and Hirata, M. 1981. Measurement and Correlation of High Pressure Vapour-Liquid Equilibria for the Systems Ethylene-1-Butene and EthylenePropylene. J. Chem. Eng. (Japan), 14(1). 1-6. 52. Dorau, W:. Kremer, H.W. and Knapp, H. 1983. An apparatus for the Investigation of Low-Temperature, High-Pressure, Vapour-Liquid and Vapour-Liquid-Liquid Equilibria. Fluid Phase Equilibria, 11.83-89. 53. Chou, C.F.. Forbert, R.R. and Prausnitz, J.M. 1990. High Pressure Vapour-Liquid Equilibria for COJn-Decane, COfletralin and Cob-Decanereealin at 71.1 and 104,4"C. J. Chem. Eng. Data, 35.26-29. 54. Raal, J.D. 1993. Unpublished work, contact author. 55. Shah, N.N., Pozo de Fernandes, M.E., Zollweg, J.A. and Streett, WB. 1990. VapourLiquid Equilibrium in the System Carbon Dioxide + 2.2-Dimethylpropane from 262 to 424 K at Pressures to 8.4 MPa. J. Chem. Eng. Data, 35,278-283.
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