Fuel 90 (2011) 536546

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Fuel
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Experimental apparatus for phase behavior study of solventbitumen systems: A critical review and design of a new apparatus
Mohammad Kariznovi, Hossein Nourozieh, Jalal Abedi
Department of Chemical and Petroleum Engineering, University of Calgary, Calgary, Canada

a r t i c l e

i n f o

a b s t r a c t
A new apparatus for studying the phase behavior of heavy oil and bitumen with different solvents has been tested. It has the capability of determining physical properties, such as density, viscosity, and compositions, of individual phases over a broad range of temperatures and pressures. One of the unique features of this apparatus is that the method of detecting presence of different phases is based on the values of density and viscosity of the phases rather than visual observation. Thus, the applicability of this apparatus is not restricted to uids that are transparent to visible light. In addition, this apparatus allows taking samples from each phase for further analysis. The other unique feature of the apparatus is that it is designed for an expeditious thermodynamic equilibration using a rocking cell with a free-rolling ball inside which allows the effective agitation. The success of this design relies upon coupling advanced apparatus construction techniques with accurate density and viscosity measurement for phase detection. The experimental apparatus was tested for vaporliquid, liquidliquid, and vaporliquidliquid equilibrium systems; and, the results are in good agreement with data published in the literature. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 3 June 2010 Received in revised form 10 October 2010 Accepted 13 October 2010 Available online 23 October 2010 Keywords: Experimental apparatus Phase behavior Solvent Bitumen

1. Introduction World production of heavy and extra-heavy oils, such as bitumen, has increased as the conventional light and medium crudes declined. In-situ bitumen recovery from oilsand formations has become economically successful over the past two decades in Canada. Inventions and developments of recovery processes, such as steam assisted gravity drainage (SAGD) and vapor extraction (VAPEX) have contributed to this success [13]. Numerous schemes to utilize solvent and heat have recently been invented and patented, in which the compound effects of solvents and heat on the bitumen viscosity would provide bitumen production rates that could be equivalent or even higher than those from the injection of steam or solvent alone [4,5]. However, the fact is the lack of basic data and mechanistic knowledge relevant to the solvent/heat-assisted-recovery processes. Even the most fundamental experimental data, such as the solubility of commonly used solvents in bitumen, are not available. The quantitative effects of solvent on bitumen viscosity, density, and phase behavior are also not well understood. Thus, to acquire basic knowledge for designing and optimizing such processes, it is crucial to nd out the phase behavior of the bitumen/solvent

Corresponding author. Address: 2500 University Dr., NW, Calgary, Alberta, Canada T2N 1N4. Tel.: +1 403 220 5594. E-mail address: jabedi@ucalgary.ca (J. Abedi).
0016-2361/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2010.10.019

system and its physical properties, such as density, viscosity, and composition of each phase. This study reviews the experimental setups that have been used for phase behavior study of bitumen/solvent systems. It is not the intention to only review the experimental setups, but also highlight their shortcomings and limitations. Table 1 summarized the apparatus which used for phase behavior study of bitumen/solvent system. The specications, capabilities, and limitations of each experimental setup are also provided. The application of the apparatus listed in Table 1 will be described in more details in Section 2. Considering the shortcomings and limitations of apparatuses that were used for bitumen/solvent phase behavior, it is essential to prepare, design, and construct an experimental apparatus for measuring vaporliquid, liquidliquid, and vaporliquidliquid systems or even one containing a solid phase. Most of the above-mentioned experimental apparatuses (Table 1) can be used only for vaporliquid system and do not have the capability of measuring the mole or weight fraction of feeding uids. However, the experimental and modeling studies by Mehrotra and Sverck [1216] and Sverck and Mehrotra [8,17] indicated that there is the possibility of formation of two liquid phases under certain conditions for bitumen/solvent system. For instance, they observed that, for a Cold Lake bitumen/carbon dioxide system at the lowest temperature (15 C) and high pressure, the solubility does not signicantly increase with increasing the pressure. In addition, there is crossover in the solubility measurement for

M. Kariznovi et al. / Fuel 90 (2011) 536546 Table 1 Capabilities and specications of different experimental apparatus. Experimental setup Equilibrium mechanism Visual observation Operation PVT study Jacobs et al. [6] Circulation U U U U L Fu et al. [7] Rocking 150 13.8 U U U V, L Svrcek and Mehrotra [8] Circulation 120 10 U U U U L >1200 Sayegh et al. [9] Circulation 140 13 U U U U L Abedi et al. [10] U 452 28 U U U U U U U 10175 Badamchi-Zadeh et al. [11] Magnetic mixer U 200 69 U U U U U U U 100 New Setup Rocking & ball 200 40 U U U U U U U U U 900

537

T, C P, MPa VL LL VLL Solubility Density Viscosity Volume Sampling S/B ratio Volume, cm3

Measurement

Capability

two isotherms, which indicates that the measured solubility for carbon dioxide at 26 C and 10.6 MPa is slightly higher than at 15 C and 10.7 MPa. The possibility of the formation of a second liquid is increased as a heavier solvent, such as propane and butane, at a low temperature and high pressure, is used. Recently, the modeling study by Kariznovi et al. [18] conrms the possibility of a second liquid phase at a low temperature for carbon dioxide and ethane/bitumen systems. Thus, experimental data on phase behavior is required to determine the operating conditions that cause the formation of two liquid phases. Identication of the phases and measurement of their properties (viscosity and density) at conditions that have more than two phases are important for phase behavior study and evaluation of the performance of recovery processes. The main objective of this research is to propose an experimental apparatus to overcome the shortcomings associated with the apparatus used for bitumen/solvent phase behavior study. Thus, the proposed apparatus has no limitation for number of phases and has the capability of measuring the mole or weight fraction of feeding uids. It can handle temperatures (T) up to 200 C, which is the maximum operating temperature for the density measuring cell, and pressures (P) up to 40 MPa. The experimental setup has been veried using different simple binary and ternary systems. The validation of the apparatus has been made by using data from the literature for three different systems: vaporliquid, liquidliquid, and vaporliquidliquid systems. The results for these systems had been compared with published data; and, good agreement was obtained. In addition, the phase behavior of bitumen/propane mixture for vaporliquid and liquidliquid equilibrium were considered to validate the capability of the proposed apparatus for bitumen/solvent mixtures. The solubility as well as the saturated phase properties such as, density, viscosity, and volume of the phases, was presented. Section 3 describes the experimental apparatus and quality control tests that were conducted to validate the setup for phase behavior study.

2. Literature background The rst attempt to measure the properties of heavy oil and bitumen with solvents dates back to 1980 by Jacobs et al. [6] who measured the viscosity of gas-saturated Athabasca bitumen. Concurrently, Robinson et al. [19] and Robinson and Sim [20]

conducted phase behavior experiments on Athabasca bitumen saturated with carbon dioxide and ethane at high temperatures (up to 150 C) and Cold Lake bitumen saturated with carbon dioxide, respectively. In 1980, Jacobs et al. [6] used an experimental setup for measuring the effect of dissolved gases on the viscosity of bitumen. The experimental apparatus consisted of a gear pump, mixing cell, and viscometer, as shown in Fig. 1. To conduct an experiment, the mixing cell was charged with bitumen and then pressurized with desirable gases. A gas cylinder was connected to the mixing cell and kept the pressure constant during the experiment. The entire experimental setup was placed inside an insulated, electrically heated, uniform temperature air-bath. Bitumen with dissolved gas was pumped through the recycle and circulation lines. The recycle line took the bitumen to the top of the mixing cell. The density measuring cell and viscometer, which were installed on the circulation line, continuously measured the density and viscosity of the liquid phase. The division of ow in the circulation and recycle lines was controlled by means of a valve in the circulation line. A hemispherical screen at the top of mixing cell, which was designed to increase the contact surface between gas and liquid, speeded up the mixing process. The bitumen was circulated at a constant pressure and temperature, until no change in the viscosity of the liquid phase was observed. A constant viscosity for a considerable time indicated that liquid is saturated at the given temperature and pressure. Jacobs et al. [6] measured the effect of the dissolved gas (carbon dioxide, methane, and nitrogen) on the viscosity of Athabasca bitumen. In 1982, Mehrotra and Svrcek [1216] and Svrcek and Mehrotra [17] used the experimental setup of Jacobs et al. [6] to measure the effect of temperature and pressure on the solubility of methane, ethane, carbon monoxide, carbon dioxide, and nitrogen in four different Alberta bitumens (Athabasca, Cold Lake, Peace River, and Wabasca). The experimental setup was used to establish the equilibrium condition. To measure the solubility of gas in bitumen, they ashed the liquid phase at atmospheric condition. Addition to solubility, they measured the viscosity and density of the saturated phase for temperatures and pressures up to 110 C and 10 MPa, respectively. Mehrotra and Sverck concluded that the Jacobs et al. apparatus has the capability to operate in low temperature where bitumen has a viscosity in the order of one million centipoises. Fu et al. [7] designed an experimental apparatus for studying the vaporliquid equilibrium of carbon dioxide and nitrogen with

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Athabasca bitumen at the Alberta Research Council in 1985. They modied a Ruska rocking cell apparatus for conducting their experiments. Fig. 2 illustrates a schematic diagram of the apparatus. It consisted of a charging and discharging system, a rocking equilibration cell and a sampling and analysis system. The detailed shape of the equilibration cell and rocking system are shown in Figs. 3 and 4, respectively. The equilibration cell was placed in a constant temperature bath and was driven by a motor. To run an

experiment, the bitumen and gas were charged to the equilibration cell. Equilibrium was achieved by the rocking of the equilibrium cell and agitation. The pressure was measured during the experiment; and, when there was no pressure change, the system was stabilized for at least two days to ensure that the equilibrium condition has been reached. There was a piston inside the equilibrium cell (Fig. 3): this feature provided the capability of measuring the volume of liquid and vapor.

Fig. 1. Experimental setup designed by Jacobs et al. [6].

Fig. 2. Experimental setup designed by Fu et al. [7].

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Fig. 3. Equilibration cell designed by Fu et al. [7].

Fig. 4. Mixing and agitation mechanism in setup designed by Fu et al. [7].

Furthermore, it became possible to take a sample from both the liquid and vapor at equilibrium. During sampling, the Ruska pump maintained a constant pressure by means of the piston. Liquid and vapor samples could be collected for further analysis. The setup was tested for a temperature and pressure of 150 C and 13.8 MPa, respectively. This apparatus could not measure the density and viscosity of saturated phase, but it could be used for vaporliquid phase equilibrium. Fu et al. [21] ran same experiments for Cold Lake bitumen with methane and ethane at the Alberta Research Council in 1988. In 1989, Svrcek and Mehrotra [8] designed a new apparatus for measuring the solubility and viscosity and density of gas saturated bitumen, and they conducted some experiments with Peace River bitumen. The experimental apparatus, which is illustrated in Fig. 5, consisted of a Haake Rotovisco RV2 viscometer, Anton Paar DP 2000 density measuring cell, Lewa diaphragm pump, and

mixing cell with some necessary instrumentation. The entire setup was placed in a Blue M oven to control the temperature. To run the experiment for specic temperature, bitumen was charged into the mixing cell; and, gas was then introduced into the cell. To measure the solubility, the pressure was increased stepwise and the experiment started with the lowest experiment pressure, and the gas was dissolved into the bitumen through repeated circulation. The pump drew bitumen from the bottom of the mixing cell to either discharge it into the top of the mixing cell for further circulation or to transfer it through the density measuring cell and sampling cell. Bitumen owed through the micro lter of differential pressure (DP) cell, which monitored the pressure drop across it. This feature provided the capability of detecting solid formation. Any sharp increase in the pressure drop indicated the formation of solid phase. The viscosity of the liquid phase was measured during the experiments, and the equilibrium condition was determined by constant viscosity. When equilibrium was achieved, a liquid sample was taken for solubility measurement, and the system pressure was increased for the next pressure step. This procedure was repeated up to a maximum pressure of 10 MPa. Sayegh et al. [9] designed an experimental setup (Fig. 6) for measuring the phase behavior and physical properties of heavy oil/carbon dioxide mixtures and generated the data for Lindbergh heavy oil. The experimental setup was used for saturating crude oil with carbon dioxide and also the measurement of the saturated phases composition, density, and viscosity. The apparatus consisted of two cells with oating pistons. One of cells had two windows for visual observation, and the other was a blind cell. The two cells were connected by a gear pump for uid circulation and mixing. The top of the cells were connected through two capillary viscometers for low and high range viscosity measurements and a digital density measuring cell. The bypass loop allowed the measurement of either the viscosity or density of the liquid phase from the top or bottom of both cells. To initialize the experiment, half of the window cell was lled with bitumen and the rest lled with solvent (carbon dioxide). The uids were drawn from the bottom of the window cell by the gear pump and allowed to ow through the blind cell, viscometer, and density measuring cell, followed by spraying at the top of the window cell. This procedure was used to mix the uids in the

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Fig. 5. Experimental setup designed by Svrcek and Mehrotra [8].

Fig. 6. Experimental setup designed by Sayegh et al. [9].

system and saturate the bitumen with carbon dioxide. If the initial amount of carbon dioxide was not sufcient to saturate the oil, further carbon dioxide was introduced into system.

When the pressure remained constant, it was assumed that equilibrium was achieved. Excess carbon dioxide was purged out at a constant pressure, and the system was left for at least 12 h.

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The viscosity and density of the saturated phase at the top and bottom portions of the blind cell were measured. The saturated bitumen sample could be taken from either the top or bottom of the cells by using the sampling valve. Abedi et al. [10] used an indirect approach for phase behavior study using X-ray imaging. They developed an X-ray view cell apparatus for studying the phase behavior of complex organic uids. Use of this apparatus provided the ability of determining individual phase densities and compositions, without sampling, over a broad range of temperatures and pressures. This apparatus utilized transmitted X-rays, instead of visible light, as the basis for phase detection. Thus, it was not restricted to uids that were transparent to visible light, and it could operate over a broader temperature range than the classic technique. Another feature of the cell was that gas could be added continually. This new apparatus had extended the temperature and pressure range of the classic technique to 452 C and 28 MPa, respectively. The schematic diagram of the apparatus is shown in Fig. 7. It had three key elements: a polychromatic X-ray source, the variable

volume view cell, and the image capture, processing, and viewing system. The entire setup, except the image processing and viewing components, was placed in a lead-lined cabinet. The X-rays emitted by the tungsten source and transmitted through the walls of the view cell were focused with an image intensier, converted to visible light using a uorescent screen and visualized by a high-resolution video camera. The number of phases present, other than dispersed solid phases, was determined visually, and the image analysis measurements were performed automatically on portions of the images selected manually. In a recent study, Badamchi-Zadeh et al. [11] used DB Robinson Jefri PVT Cell to measure the solubility of Athabasca bitumen with propane and carbon dioxide, as shown in Fig. 8. The heart of apparatus was transparent equilibration cell which surrounded in pressurized hydraulic uid. Magnetic mixer provided an efcient agitation and oating piston allowed to adjust the equilibrium volume. The volume of cell could be measured using calibrated cathetometer positioned through the cell window. The

Digital Store Computer Control Signal ADC

Lead Cabinet

Pressure Gauge

X-ray Image Intensifier View Cell

Camera

Philips mcn-167 x-ray Generator

Digital to ntsc Converter Vga Monitor Heater Control Panel Video Typewriter Video Recorder Colour Monitor

Fig. 7. Experimental setup designed by Abedi et al. [10].

Fig. 8. DB Robinson Jefri PVT cell used by Badamchi-Zadeh et al. [11].

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maximum volume of cell was 100 cm3 and its maximum operational pressure and temperature were 69 MPa and 200 C. The inline viscometer (Viscopro2000 Cambridge) and density measuring cell (Anton Paar DMA 5000) measured the density and viscosity of saturated phase which was displaced from PVT cell. A pycnometer was used to take liquid sample for solubility measurement and further analysis. To conduct an experiment, a specic mass of solvent and bitumen were charged into PVT cell. The mass fraction was calculated based on volume and density measurement. The solvent and bitumen were mixed at liquid phase to expedite mixing process and reduce the equilibration time. They measured the PVT cell volume from pump displacement and cathetometer reading. For a given composition, Badamchi-Zadeh et al. [11] measured the saturation pressure in two steps. The rst step was to estimate the saturation pressure while more accurate pressure measurements were obtained in the second step. The pressure of the PVT cell was decreased by gradual expansion of cell volume. They measured the pressure and volume of cell at constant time intervals. Then, by plotting pressure versus specic volume, the bubble point was estimated from the change in slope of pressurevolume plot. This method gave the approximate saturation pressure; because, the system was not at equilibrium during the volume expansion. In the second step, the system was compressed and equilibrium was established. Then, the pressure was decreased step wise and after each step, the system was allowed to reach the equilibrium and the pressure became stable. Addition to saturation pressure, they measured the density and viscosity of saturated phase during their experiments. The apparatuses of Abedi et al. [10] and Badamchi-Zadeh et al. [11] were the only ones that could detect more than one liquid phase; whereas, the other setups explained here had no capability of identifying second liquids. The Abedi et al. apparatus detected the number of phases; however, it could not measure the physical properties, such as viscosity and composition, of the different

phases. In Badamchi-Zadeh et al. apparatus, the equilibration cell volume was less than 100 cm3. Hence, if more than one liquid phase exists, the volumes of the phases were relatively small to measure the phase properties. In addition, if there is more than two phases at the equilibrium condition, the solvent to bitumen (S/B) ratio in the feed affects the nal phase properties. Most of above-mentioned experimental apparatuses did not have the capability of measuring the mole or weight fraction of feeding uids. 3. Experimental apparatus The composition, density, and viscosity of the each phase in a saturated bitumen/solvent system are the basic data for phase behavior study. The apparatus has been designed to acquire the experimental data of the following information for various solvent/bitumen systems at a wide range of temperatures and pressures: (1) Solubility of solvents in bitumen. (2) Number of phases, volume ratios and compositions of each phase (gas chromatography, GC, of evolved gas; B.P. distribution; and, saturates, aromatics, resins and asphaltenes, SARA, characteristics of the evaporation residue) at equilibrium. (3) Viscosity and density of the saturated phases. The schematic diagram of the apparatus is shown in Fig. 9. It consists of feeding cells, an equilibration cell, four sampling cells, a density measuring cell, a viscometer, and two Quizix automated pressure activated pumps. The Quizix pumps charge and discharge water to displace the uids or keeping the pressure constant. The equilibration, sampling, and feeding cells are equipped with the pistons to prevent the contamination of the mixture with water. The pistons are sealed with the Viton o-rings supported by the Teon backup rings.
2 4 1 5

3
835 cp

0.835 gr/cc

4 7 8 6

12

10 11 11

13 1. 2. 3. 4. 5. 6. 7. 8. Blue M Oven Evaluation Unit (mPDS 2000 v3) Evaluation Unit (ViscoPro 2000) Connect to Computer Density Measuring Cell Viscometer Pressure Transducer Sample Port 9. Sampling Cell 10. Equilibrium Cell 11. Feeding Cell 12. Heater 13. Temperature Controller 14. Quizix Pump 15. Computer 14 14
70 oC

15

Fig. 9. The proposed apparatus for the phase behavior study of bitumen/solvent systems.

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The equilibration and sampling cells, density measuring cell, and viscometer are placed in a temperature-controlled Blue M oven. The two pumps (Quizix pumps) control system pressure. The rocking action of the equilibration cell with the rolling ball expedites the mixing of solvent and bitumen and reaching equilibrium condition. Hu [22] used free rolling ball to investigate the equilibrium properties of aqueous solution. His study conrmed that the addition of the free-rolling ball can signicantly decrease the equilibration time. The density measuring cell and viscometer are used for phase detection, which shows a clear separation of the phases and allows for accurate phase volume measurements. The density measuring cell can detect any phases which passing through it; this feature allows us to detect the phases even with very small volume. However, if the volume of phase be less than 10 cm3, it is not possible to take a phase sample. In this case, the experiment is repeated with the same initial composition but higher initial volume of bitumen and solvent. Commercial PVT systems require a subjective visual observation for phase detection; whereas, this apparatus does not. Data is produced directly and does not require subjective evaluation. The rocking equilibration cell has a maximum volume of about 900 cm3, which allows sufcient saturated phase volume for measurement of physical properties, such as density and viscosity. In addition, it provides ease of phase detection and enough phase volumes for their further analyses. The Quizix pumps charge and discharge the uids with an accuracy of 0.001 cm3. The density measuring cell and viscometer are installed in series to improve the phase detection. Their in-line measurements provide data of higher accuracy than sending very small samples to the viscometer and density measuring cell separately. In case of solid formation [23,24] such as asphaltene or wax, the solid precipitates around the rocking ball. When the cell is placed in upward position, the solid settles down at the bottom of rocking cell. After each experiment, the rocking cell is opened to check for asphaltene precipitation. The sample uid is discharged from the top of the rocking cell through the viscometer and density measuring cell, while maintaining the temperature and pressure constant. In this design, the sample volume is enough large so that a visual evaluation of phases is not required. This methodology allows the detection of the phase variation within the system as the data is collected from the viscometer and/or density measuring cell. The density measuring cell and viscometer have the capability of detecting small changes in density and viscosity over a wide range of pressures and temperatures. The Anton Paar custom density measuring cell has been used, and it can measure the uid density in the range of 03 g/cm3 with an error of 0.0010.0001 g/cm3 (dependent on the measuring conditions) in a temperature and pressure range of 10 to +200 C and 070 MPa (010,000 psi), respectively. The density measuring cell was calibrated using nitrogen and water for pressures from 0 to 13.79 MPa (02000 psi g) and temperatures between 40 and 190 C. The data for the densities of nitrogen and water at specic temperature and pressure were taken from National Institute of Standards and Technology (NIST) database. The calibration can be extended to higher pressures (40 MPa). The accuracy of density measurements were examined with pure hydrocarbons and standard uids. The density measurements are precise to 0.0005 g/cm3. The Cambridge viscometer has the capability to measure viscosity in the range of 0.210,000 cp with an accuracy of 1.0% of full scale and temperature and pressure up to 315 C and 140.6 MPa (20,000 psi), respectively. It was factory calibrated; the accuracy of measurements was tested with pure hydrocarbons and standard uids. The average error for the measurements was less than 5%.

Effective mixing, through agitation by rocking, results in a reduction in the time required to reach equilibrium. Conducting experiments in a signicantly reduced time provides the opportunity to undertake parallel experiments in phase equilibration, phase sampling, and measurements of phase density and viscosity. 3.1. Experimental procedure Prior to each experiment, the entire system is thoroughly cleaned to remove any contaminant, such as oil and solid particles. Toluene, acetone, and similar solvents are used to clean and remove bitumen, water, and any contaminants from the cells. To clean inside of the cells, it is possible to easily disassemble the cells and remove them completely. Then, to ensure no contaminants are left inside the system, cells and lines are successively evacuated and ushed with dry helium. Bitumen is charged into the equilibration cell using the two Quizix pumps. By measuring the volume and density of bitumen at a constant temperature and pressure, the mass of the bitumen inside the equilibration cell is obtained. The solvent is then charged into the cell with the same procedure. Thus, the mass fraction of the injected uids is known. To measure the solubility at a specic temperature and pressure, the experimental pressure and temperature are xed: the Quizix pump keeps a constant pressure with an error of less than 5 kPa. The equilibration cell is rocked to achieve effective mixing and reach the equilibrium condition for the bitumen/solvent system. The required equilibration time depends on the experimental conditions, such as pressure and temperature, as well as solvent and bitumen properties. Bitumen viscosity is the key factor for the equilibrium time. For instance, at a high temperature (>80 C), the equilibration time is much less than a low-temperature condition. This is due to the high bitumen viscosity, which is lower at higher temperatures, allowing for easier and more effective mixing. During the mixing period, the volume of water, which is charged or discharged to keep a constant pressure in the equilibration cell, is recorded. When there is no change in the cumulative volume of water, equilibrium is achieved. To discharge the saturated bitumen from the top of the rocking cell, the equilibration cell is rst kept in an upright position (vertical position) for a few hours to obtain single bulk volume of each phase vertically segregated in the order of phase density. Then, all the lines connecting the sampling cells to the equilibration cell are lled with helium gas at equilibrium pressure (helium, as a carrying gas, has no effect on G.C. analyses). Helium and equilibrium uid are in contact in the line not in the cell; therefore, due to small contact area (tube area $0.012 cm2) the helium gas has no significant effect on the equilibrium properties. In addition, to have no sample phase contamination with helium, about 1015 cm3 of each phase is purged before phase sampling. Now, the equilibrium uids are discharged through the density measuring cell and viscometer, while maintaining a constant temperature and pressure. The pressure is measured by both the in-line and the Quizix pump pressure transducers. The pressure difference exerted by the friction of the pistons was found to less than 70 kPa (10 psi). The value reported by the in-line pressure transducer, which is the exact system pressure, is reported as equilibrium pressure. The phase samples are collected with steady readings of the viscometer and the density measuring cell; any change in density and viscosity indicates a passage of a phase boundary through the measuring instruments. Liquids and vapor phases are transferred into sampling cells 13, and the last sampling cell is used to purge the phase boundary portion and clean the transition between the phases. The heavier phase can completely displace the lighter phase, which vertically segregated in the order of phase density, results in clean samples with sharp density variation. The volume

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of each phase is measured by monitoring the volume of water charged to the equilibration cell. Saturated samples can be collected through the sampling port for compositional analysis or further studies. To measure the solubility of the saturated liquid(s), the collected samples are ashed at atmospheric pressure. The volume of the evolved gas is measured by the Chandler Engineering Gasometer (Model 2331) with 0.2% accuracy of the reading. Then, the solubility is calculated using two methods: volumetric and mass conservation. The former method is on the basis of the volume measured by the Gasometer. Having the density of the gas at atmospheric condition, the mass of solvent (evolved gas) is calculated. The latter is on the basis of the weighting the sample before and after evolving the solvent.

compositional analysis indicated that the evolved gas was pure propane (more than 99.5%). Hence, the mass of dissolved gas could be measured from the volumetric data. Table 2 summarizes the propane composition in the liquid phase. The experimental data by Reamer and Sage [25] for this binary system is also shown for comparison. 3.2.2. Liquidliquid The liquidliquid mixing experiment was performed to investigate the capability of the experimental setup in identifying two liquids. Alcohol/hydrocarbon and alcohol/water systems were used for measuring purposes. The measured density was compared with literature data. 3.2.2.1. 1-Butanol/water system. A specic volume of 1-butanol and water was mixed at a temperature of 25 C and atmospheric pressure. After equilibration, all lines were lled with nitrogen, and the mixture was then displaced through the density measuring cell, with the density being continuously measured. Fig. 11 illustrates the experimental results for the density measurement during the sampling. As depicted in the gure, at the start of the sampling, nitrogen owed though the density measuring cell, and its density was close to zero; then the rst liquid passed through the density measuring cell, there was a sharp change in density. There was a second jump for the second liquid. The measured densities for both liquids were compared with results reported by Hill and Malisof [26] and are summarized in Table 3. The change in density from liquid 1 to liquid 2 was not very sharp. This was an indication that the vertical segregation between them was not complete. The data suggested that ne droplets of the upper liquid were still suspended in the densest lower liquid. This situation could be alle-

3.2. Experimental results 3.2.1. Vaporliquid The binary system of propane and n-decane was selected for the vaporliquid system. The saturation pressure and phase composition were measured at different temperatures. The results were compared with the experimental data reported by Reamer and Sage [25] at three different conditions. The experiment was conducted based on the experimental procedure previously discussed. When equilibrium was achieved, the equilibration cell was placed in a vertical position for phase alignment. While the equilibrium uid was discharged from the equilibration cell, its density was measured continuously. Fig. 10 shows the density measurement during the sampling. The density in early time was about 0.003 g/cm3, which shows the density of helium inside the lines. The ow rate to push the uids was too low (0.1 3 cm3/min) to keep the cylinder at equilibrium. This ow rate was obtained by trial and error. This was the maximum rate in which the uids were displaced at constant pressure. It depends on the equilibrium uid properties and apparatus specication such as o-ring and line diameter. After about 20 min, the gas phase was detected at the density measuring cell. There was a sharp change in density from $0.003 to $0.05 g/cm3 which shows the density of a vapor mixture containing mostly propane. The density measuring cell detected the two different gases with a small density difference. Discharging was continued to detect the other phase, which was liquid. The sharp increases in density from $0.05 to $0.5 g/cm3 conrmed the liquid phase. Vapor phase composition was measured using gas chromatography and it was propane (for all experiments, more than 99.8% propane). To obtain the composition of propane in liquid phase, the saturated liquid was ashed at atmospheric condition. The

Table 2 Propane composition (mole fraction) in saturated liquid phase for propane/n-decane system. Propane mole fraction in liquid Reamer and Sage [25] This study T = 71.1 C P = 1.379 MPa 0.5899 0.580 T = 104.4 C P = 2.758 MPa 0.7003 0.699 T = 137.8 C P = 4.137 MPa 0.7023 0.707

Density , gr/cm3 a

0.8 0.6 0.4 0.2 0

0.5

Density , gr/cm3 a

0.4 0.3 0.2 0.1 0 0 1 2 3 Time, hr 4 5

Table 3 Density measurement for 1-butanol/water system at 25 C and 0.101325 MPa. Phase density Alcohol phase Water phase Hill and Malisof [26] (g/cm3) 0.8450 0.9865 This study (g/cm3) 0.835 0.981

10 Time, min

20

30

Fig. 11. Density measurement for liquidliquid equlibria: 1-butanol/water system.

Fig. 10. Density measurements for vaporliquid equilibria: propane/n-decane system.

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Density , gr/cm3 a

0.8 0.6 0.4 0.2 0 0 5 10 Time, min 15 20

Fig. 12. Density measurement for liquidliquid equlibria: methanol/n-decane system.

viated by leaving the equilibration cell at vertical position for longer time. 3.2.2.2. Methanol/n-decane. A specic volume of methanol and ndecane was mixed at a temperature of 25 C and atmospheric pressure. As before, all lines were lled with nitrogen; and, the mixture was then displaced through the density measuring cell, while the density was measured. Fig. 12 shows the density variation for this case. As the gure shows, at rst, nitrogen owed through the density measuring cell, and its density is close to zero. When rst liquid passed through the density measuring cell, there was a sharp change in density. The density became stable when the nitrogen was displaced by rst liquid. A second jump occurs when liquid 2 reached the density measuring cell. 3.2.3. Vaporliquidliquid The ternary system of ethane, n-decane, and methanol was selected, and the number of phases was measured at a specic temperature and pressure. The experimental results for the temperature of 37 C and pressure of 1.207 MPa are presented. Table 4 summarizes the feeding properties of three components and the composition of each component in the mixture.

The uids were injected in a liquid state into the equilibration cell, and the injected volume and corresponding composition were measured. The volume and composition of each component is given in Table 4. Nitrogen was used to pressurize the line and discharge the system at a constant pressure (1.207 MPa). Fig. 13 illustrates the density measurement for this system. The density in early time was about 0.013 g/cm3 which shows the density of nitrogen inside the lines. The ow rate to push the uids was kept constant (3 cm3/ min) to maintain the system at equilibrium. After about 5 min, the gas phase (mostly ethane) was detected at the density measuring cell. There was a sharp change in density from 0.013 to 0.015 g/ cm3, which shows the density of a mixture which was almost all ethane. Fig. 13b shows that the transition from nitrogen to the vapor phase (ethane) was clearly detected by density measuring cell. This result conrmed that the density measuring cell can accurately detect two different gases with very small density differences. Fig. 13a shows the density measurement for the entire experiment. The two liquid densities were 0.682 and 0.735 g/cm3, respectively. There was a sharp transition in the density measurement, which can be used to identify the two liquids, as well as two vapor phases. 3.2.4. Solubility of propane in bitumen To examine the capability of apparatus for bitumen/solvent phase behavior study, the solubility of propane in bitumen at different conditions were measured. The propane (99.5 wt.% purity) used in these measurements was supplied by Praxair. The density and viscosity of the bitumen at 50 C was measured by an Anton Paar density measuring cell and Cambridge viscometer, respectively. The measured density and viscosity were 0.992 g/cm3 and 9845.9 mPa s, respectively. The procedure to charge the equilibration cell was described in Section 3.2. The bitumen was preheated and transferred directly to the density measuring cell and viscometer. The properties of the bitumen were measured to calculate the mass of bitumen charged into the equilibration cell. The bitumen and solvent were displaced at constant pressure and temperature to have accurate amount of the components. The experiments at pressure of 4 MPa and three different temperatures, 50, 100, and 150 C, were conducted. The procedure for equilibration and discharging the equilibrium uids were described in Section 3.2. It was found that at 100 C and 150 C, vaporliquid equilibrium exists while at 50 C, the liquid liquid was observed. The properties of the saturated phases as well as the solubility are summarized in Table 5. The phase detection during the displacement of the equilibrium phases were done on the basis of the density measurements. Fig. 14 illustrates the phase change during the discharging of the equilibrium uids at 100.5 C and 4 MPa. The total composition of the propane in the mixture at initial stage was 40% weight.

Table 4 Initial composition and properties of each component for vaporliquidliquid system. Component Ethane n-Decane Methanol Volume (cm3) 53.6 195.9 81.0 Pressure (MPa) 4.924 0.101 0.101 Density (g/cm3) 0.3366 0.7265 0.7918 Mole 0.6 1 2 Molecular weight (g/mol) 30.07 142.29 32.05

a
Density , gr/cm3 a

1 0.8 0.6 0.4 0.2 0 0 50 100 Time, min 150

b
Density , gr/cm3 a

0.02 0.015 0.01 0.005 0 0 5 10 Time, min 15 20

Fig. 13. Density measurement for vaporliquidliquid system: (a) entire experiment and (b) vapor transition.

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Table 5 Initial bitumen/propane ratio and corresponding equilibrium properties for bitumen/ propane system. Temperature (C) S/B ratio* Solubility (wt.% C3) Phase 1 Phase 2 Saturated phase properties Viscosity (mPa s) Bitumen rich (phase 2) 50.9 100.5 149.8
*

Density (g/cm3) Phase 1 0.586 0.105 0.065 Phase 2 0.860 0.775 0.849

1/1 2/3 1/4

62.5 Pure C3 Pure C3

21.5 22.9 8.7

127.0 2.7 5.4

S/B ratio: solvent to bitumen ratio wt/wt.

apparatus. This has provided a stepping stone to the further advancement achieved in this study. The authors wish to express their appreciation for the nancial support of all member companies of the SHARP consortium: Alberta Innovates Energy and Environment Solutions, Athabasca Oil Sands Co., Chevron Energy Technology Co., Computer Modeling Group Ltd., ConocoPhillips Canada, Devon Canada Co., Foundation CMG, Husky Energy, Japan Canada Oil Sands Ltd., Laricina Energy Ltd., Nexen Inc., OSUM Oil Sands Co., Penn West Energy, Statoil, Suncor Energy, and Total E&P Canada. The authors also thank professors Gordon R. Moore, Raj Mehta, and Mehran Pooladi-Darvish and the technical support of Kees Van Fraassen and Dan Marentette. References
[1] Butler RM, Stephens DJ. The gravity drainage of steam-heated oil to parallel horizontal wells. J Can Petrol Technol 1981;20(2):906. [2] Butler RM. A new approach to the modelling of steam-assisted gravity drainage. J Can Petrol Technol 1985;24(3):4251. [3] Butler RM, Mokrys IJ. Solvent analogy model of steam-assisted gravity drainage. AOSTRA J Res 1989;5(1):1731. [4] Mokrys IJ. The rise of interfering solvent chambers: solvent analog model of SAGD. M.Sc. Thesis, Calgary, AB: University of Calgary; 1989. [5] Butler RM, Mokrys IJ. A new process (VAPEX) for recovering heavy oils using hot water and hydrocarbon vapour. J Can Petrol Technol 1991;30(1):97106. [6] Jacobs FA, Donnelly JK, Stanislav J, Svrcek WY. Viscosity of gas saturated bitumen. J Can Petrol Technol 1980;19(4):4650. [7] Fu CT, Puttagunta VR, Vilcsak G. Vapour liquid equilibrium properties for pseudo-binary mixtures of CO2 Athabasca bitumen and N2 Athabasca bitumen. AOSTRA J Res 1985;2(2):7381. [8] Svrcek WY, Mehrotra AK. Properties of Peace River bitumen saturated with eld gas mixtures. J Can Petrol Technol 1989;28(2):506. [9] Sayegh SG, Rao DN, Kokal S, Najman J. Phase behaviour and physical properties of lindbergh heavy oil/CO2 mixtures. J Can Petrol Technol 1990;29(6): 319. [10] Abedi SJ, Cai HY, Seyfaie S, Shaw JM. Simultaneous phase behaviour, elemental composition and density measurement using X-ray imaging. Fluid Phase Equilib 1999;158160:77581. [11] Badamchi-Zadeh A, Yarranton HW, Svrcek WY, Maini BB. Phase behaviour and physical property measurement for VAPEX solvents: part I. Propane and Athabasca bitumen. J Can Petrol Technol 2009;8(1):5461. [12] Mehrotra AK, Svrcek WY. Measurement and correlation of viscosity, density and gas solubility for Marguerite Lake bitumen saturated with carbon dioxide. AOSTRA J Res 1984;1(1):5162. [13] Mehrotra AK, Svrcek WY. Viscosity, density and gas solubility data for oil sand bitumens. Part I: Athabasca bitumen saturated with CO and C2H6. AOSTRA J Res 1985;1(4):2638. [14] Mehrotra AK, Svrcek WY. Viscosity, density and gas solubility data for oil sand bitumens. Part II: Peace River bitumen saturated with N2, CO, CH4, CO2 and C2H6. AOSTRA J Res 1985;1(4):26979. [15] Mehrotra AK, Svrcek WY. Viscosity, density and gas solubility data for oil sand bitumens. Part III: Wabasca bitumen saturated with N2, CO, CH4, CO2 and C2H6. AOSTRA J Res 1985;2(2):8393. [16] Mehrotra AK, Svrcek WY. Properties of Cold Lake bitumen saturated with pure gases and gas mixtures. Can J Chem Eng 1988;66(4):65665. [17] Svrcek WY, Mehrotra AK. Gas solubility, viscosity and density measurements for Athabasca bitumen. J Can Petrol Technol 1982;21(4):318. [18] Kariznovi M, Nourozieh H, Abedi J. Bitumen characterization and pseudocomponents determination for equation of state modeling. Energy Fuels 2010;24(1):62433. [19] Robinson DB, Kalra H, Sim SK. Behavior of bitumenwatergas systems. Final Report on AOSTRA Research Agreement 43. Edmonton, AB: University of Alberta; 1980. [20] Robinson DB, Sim SK. The behavior of bitumen mixture during in-situ recovery. A Progress Report on Agreement 184. Edmonton, AB: University of Alberta; 1981. [21] Fu CT, Puttagunta VR, Vilcsak G. Gas solubility of methane and ethane in Cold Lake bitumen at in situ conditions. J Can Petrol Technol 1988;27(4):7985. [22] Hu YF. Solubility of mannitol in aqueous sodium chloride by the isopiestic method. J Solut Chem 1998;27(3):25560. [23] Mousavi-Dehghani SA, Riazi MR, Vafaie-Sefti M, Mansoori GA. An analysis of methods for determination of onsets of asphaltene phase separations. J Petrol Sci Eng 2004;42(2-4):14556. [24] Vazquez D, Mansoori GA. Identication and measurement of petroleum precipitates. J Petrol Sci Eng 2000;26(14):4955. [25] Reamer HH, Sage BH. Phase equilibria in hydrocarbon systems. Volumetric and phase behavior of the propane-n-decane system. J Chem Eng Data 1966;11(1):1724. [26] Hill AE, Malisoff WM. The mutual solubility of liquids. III. The mutual solubility of phenol and water. IV. The mutual solubility of normal butyl alcohol and water. J Am Chem Soc 1926;48(4):91827.

Density, gr/cm 3 a

0.8 0.6 0.4 0.2 0 0 100 200 Volume, cm3 300

Fig. 14. Density versus volume for bitumen/propane system at 100.5 C and 4 MPa.

The total volume of mixture before mixing was 334.18 cm3 and the equilibrium volume was 255.03 cm3 (at equilibrium temperature and pressure). As depicted in Fig. 14, the volume of each phase and corresponding density were measured during the experiment. 4. Conclusion A new experimental apparatus for heavy oil and bitumen has been tested for the study of vaporliquid, liquidliquid, and vaporliquidliquid equilibria. The technique and apparatus described here have already provided, and continue to generate, data of value that are unattainable in other ways and offer much promise for the future. The density measurement is an accurate method for phase detection; and, if it is coupled with the viscosity measurement, it will provide a unique method for phase behavior study. The preliminary tests show the experimental setup has the capability of detecting of the separate phases, as well as generating reliable data for phase behavior, of different vaporliquid, liquid liquid, and vaporliquidliquid systems. The unique feature of the new setup in measuring the accurate volume of feeding uids and equilibrium phases provides the ability to not only acquire the volumetric data for equilibrium phases, but also obtain the effect of the solvent/bitumen feeding ratio on the composition and volume of the phases and other properties. Acknowledgment This work has been carried out as a part of the SHARP (Solvent/ Heat-Assisted Recovery Processes) research consortium executed at the University of Calgary. The consortium was initiated by Dr. Tadahiro Okazawa, a retired Senior Research Advisor of Imperial Oil Resources Ltd., he had been keenly aware of the serious lack of physical data which could otherwise augment effective applications of these recovery processes. Dr. Okazawa is acknowledged for his being responsible for drawing the blue prints of this research consortium including the original design of the unique experimental