Fundamentals of Reservoir Fluids NORMAN J. CLARK MEMBER AIME Fundamentals of Reservoir F1uids--Introduction During the movement of oil and gas to the surface from the reservoir in which they are found, the temperatures and pressures to which they are subjected change significantly; as a result, their physical properties undergo many radical changes. The economic value of produced oil and gas is dependent upon these physical properties, and the operator finds it invaluable to be able to predict handling and producing techniques which will allow him to produce his reserves in a form that will provide a maximum profit. For many years, therefore, investigators have studied the phase behavior of hydrocarbon materials with the goal of fully developing methods for dctermining answers to problems concerning the physical behavior both of produced hydrocarbons and of those that are left in the reservoir. Written material'-' regarding the fundamental physical concepts governing hydrocarbon behavior and describing the methods employed in practically ap')lying these concepts to solving production problems is scattered throughout the literature. The purpose of this series, therefore, is to bring together these concepts and methods of their application in solving practical, day-to-day reservoir engineering problems. When production starts and pressure is reduced in a hydrocarbon reservoir, both liquid and gas are formed from what was at first only a liquid (as in an oil reservoir) or only a gas (as in a gas reservoir). One or the other of the two phases (liquid and gas) is produced differentially to some degree because of variations in permeability of the rock to gas and oil as saturations change. Therefore, the hydrocarbon analysis of the composite proOriginal manuscript received in Society of Petroleum Engineers office April 3, 1961. Revised manuscript received Nov. 17, 1961. lReferences given at end of paper. SPE 91 JANUARY, 1962 duced materials changes from that of the original material in place in the reservoirs. Obviously, then, the behavior of reservoir fluids during production operations becomes quite complex, and it is necessary to obtain laboratory analyses of the initial reservoir fluids for conditions of change where liquid and gas separate both differentially and under equilibrium conditions. With these data, production problems involving separation under various conditions can then be solved. The practical approach to the study of reservoir fluid behavior is to anticipate pressure and temperature changes to which the reservoir material will be SUbjected during production operations, both in the reservoir and at the surface; then the changes to reservoir fluid samples, which occur for each of these pressure and temperature conditions, are measured by laboratory tests. The study of oil and gas reservoir performance requires quantitative data on the composition, characteristics and behavior of the oil and gas in the reservoir under original conditions; in addition, similar data must be obtained for the oil and gas under all changing conditions of temperature and pressure-as the materials move to the wellbore, as they are produced to the surface, and as they are either gathered in the stock tank or piped to the consumer. The laws for perfect gases and perfect solutions do not apply, without modification, to the behavior of hydrocarbon mixtures. Although in recent years many investigators have made notable progress toward developing means for quantitatively evaluating hydrocarbon phase behavior, the industry still does not have a reliable theoretical method by which it can accurately and completely calculate the behavior of complex hydrocarbon mixtures under high pressures. Where the production problem deals with changes in the reservoir material under conditions approximating that of equilibrium conditions, such changes may be calculated with reasonable precision. For this purpose, the concept of K-values has been employed. A K-value is the ratio of the mole fraction of a component in the equilibrium gas phase to the mole fraction of the same component in the equilibrium liquid phase. In essence it is a measure of volatility, which is controlled by the balance between molecular forces at the condition of temperature and pressure to which the material is SUbjected. A complete description of equilibrium calculations, how they are made, their qualifications and application to reservoir engineering problems will be covered in this series. *** 11 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Editor's Note: The following paragraphs briefly introduce and summarize material to be found in a five-part series of Technical Articles which will be published in consecutive issues of JOURNAL OF PETROLEUM TECHNOLOGY. This series will cover the fundamentals of sampling, testing, adjusting and interpreting oil and gas sample data for use in reservoir studies. The first installment begins on page 12 of this issue. References, Tables and Figures will be numbered consecutively, but will be published only with the particular installment of the series in which they are first mentioned. NORMAN J. CLARK ENGINEERING DAllAS, TEX. Fundamentals of Reservoir Fluids, Part One FUNDAMENTALS OF RESERVOIR FLUIDS Sampling and Testing Oil Reservoir Samples NORMAN J. CLARK MEMBER AIME An oil-reservoir performance study depends upon a few direct laboratory measurements made on the reservoir oil sample. The following data usually are required: (l) original reservoir temperature and pressure; (2) pressurevolume relation at one or more temperatures, with one relation always being measured at reservoir temperature; (3) the effects of variation of separator pressure on the amounts of gas liberated and on the shrinkage of produced oil in the stock tank which results from such separation process; ( 4 ) differential gas liberation data; ( 5) the density or specific volume of reservoir fluid; (6) the relation of reservoir oil viscosity at reservoir temperature and at pressures ranging from reservoir pressure to atmospheric pressure with the viscosity of stock-tank oil; (7) a hydrocarbon analysis of the mixture as it existed originally in the reservoir; and (8) ASTM distillation analyses of residual oil. Complete and fairly accurate data on these various properties can be obtained with comparative ease and at moderate cost through a laboratory examination of a sample of reservoir oil. Extrac·ting Reservoir Oil Samples There are two general methods for obtaining a sample of reservoir oil for laboratory examination purposes-( 1 ) by means of subsurface samplers,"· and (2) by obtaining surface samples of separator liquid and gas. Several different types of subsurface samplers are used, the most notable of which are the Humble Oil & Refining Co. evacuated-chamber type" which has a valve only at the bottom of the sample chamber, the U. S. Bureau of Mines type,12 and the Gulf Oil Corp. type 13 which has valves on both the top and the bottom of the sample chamber. These instruments are run by wire line into the well to be sampled. Reservoir temperature and pressure are recorded either simultaneously or on separate runs made the same day as near the time of sampling as possible. Surface samples of oil and gas are obtained at the separator in separate containers and then recombined in the lab in proportion to the gas-oil ratio measured at the separator. Either method of obtaining the sample is suitable providing exacting procedures are followed to yield samples for laboratory tests that are truly representative of the 12 SPE 91 material as it exists at reservoir conditions of temperature and pressure. Local conditions and the experience of personnel usually determine which method is better to use." It is extremely important that experienced personnel plan and perform the sampling program; the manner in which the well is stabilized for sampling often completely controls the nature of the sample obtained and, therefore, the results of all subsequent studies utilizing the data. Laboratory Examination of the Oil Sample When a subsurface sampler is received in the lab, the saturation pressure of the oil sample at the measured reservoir temperature is determined and checked against the measured pressure at the time of sampling. Three subsurface samples usually are obtained from the well, the extra samples being used to check laboratory results (particularly in regard to the saturation pressure) and to conduct any repeat tests that might be required. Obtaining an accurate measurement of saturation pressure is very important because this value is utilized in many of the other tests performed on the sample. After this test, the sample is ready for further testing. When first received in the lab, separator oil and gas samples are recombined at reservoir temperature conditions, and the saturation pressure is determined. The re- (A) 8t /Bt.= (B) (E) (0) (C) ~~.~90~~C %.9959 Bt/Bt.= ;~:~~~~ =-1.0000 t.= ;~~3~~~CC 8t/ B =- 1.3532 8t/ Bta= ;~~j~~C~ =;(.0032 Bt/8,.", 227~·.~~~CcC =2.9681 Fig. I-Equilibrium liberation of gas from oil and gas mixture by removing mercury and reducing pressure (determination of PVT data at 134°F). JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Introduction NORMAN J. CLARK ENGINEERING DALLAS, TEX. sulting recombined sample of saturated oil then is used for subsequent tests in the same manner as the subsurface sample. (B) (A) (C) ~ GAS REMOVED CONSTANT PRESSURl "''' PSIG 1900 1900 1,037CC PSIG PSIG e,se ----"-GAS REMOVED CONSTAt<" PRESSlRE mcc o! S C 1600 1600 PSIG PSIG 7' Liberation of Dissolved Gas If liberated gas is permitted to stay in direct contact with a liquid sample (as shown by the equilibrium or flash process in Fig. 1), a different volume of gas will be liberated down to a given pressure than would be liberated if gas were removed from contact with the liquid as it is liberated. The remaining liquid is also different but in the opposite direction and, thus, shrinkage is different. Differential liberation is that process of gas liberation where the gas is removed as it is formed incident to a drop in pressure at constant temperature, as shown in Fig. 2. Fig. 3 compares equilibrium and differential shrinkages of a low-shrinkage oiP" under reservoir conditions as pressure drops. It shows that under equilibrium conditions a greater quantity of heavy components is progressively pulled into the gas by light gas components and, thus, shrinkage is greater. Under these conditions, the low shrinkage by differential liberation is caused by gas being removed as it is formed; this prevents the light gas molecules from being attracted to heavy liquid molecules, thereby minimizing the quantity of liquid pulled into the gas phase. Fig. 4 compares the equilibrium and differential shrinkages of a very high-shrinkage oil. In this case, the difference may be reversed from that of low-shrinkage oil (Fig. 3). A relatively greater volume of gas is formed in the highpressure range than is formed with low-shrinkage oil, a phenomenon caused by the large quantity of intermediates being pulled into the gas phase. These intermediates enter the gas phase because they have an inherently high kinetic energy and because they are strongly attracted to the light gas molecules which are densely spaced at the high-pressure condition. Once the intermediates are removed from the system by differential liberation, they have no further influence on gas liberation and oil shrinkage; therefore, oil shrinkage remains high through the lower pressure ranges. If the gas is not removed, as in the flash liberation process, intermediate molecules lose much of their tendency to vaporize. This is true for two reasons-( 1) a large quantity of intermediates is already present in the gas phase; and (2) the intermediates are attracted to the heavy liquid molecules, as well as to the light gas molecules. Obviously, then, shrinkage is less under equilibrium conditions than under the differential process. Differential Liberation Tests An oil sample is prepared for differential liberation testing by charging a quantity of saturated oil into a pressure-volume cell at original reservoir pressure and temperature. To perform the test, the pressure of the sample at constant reservoir temperature is reduced by withdrawing increments of mercury, as shown in Fig. 2. While the gas liberated during a pressure-reduction step JANUARY, 1962 H9 RETURNED Hg RETURNED CONSTANT PRESSURE CONSTANT PRESSURE Bo/Boa: :~:~:3 0 ,9664 Fig. 2-Differential liberation of gas from oil and gas mixture (determination of differential shrinkage and gas liberation data at 134°F). is withdrawn and metered, the reduced pressure on the oil sample is maintained constant by returning mercury to the cell. The cumulative volume of gas liberated by this differential liberation process, designated G r,,, is recorded for the corresponding pressures as cubic feet of gas at standard conditions of temperature and pressure (60°F and 14.7 psia) per barrel of oil saturated at the reservoir sampling conditions of temperature and pressure (134°F and 2,190 psig). The remaining volumes of saturated oil at the various pressure steps are recorded as the volume of saturated oil at reduced pressure and reservoir temperature per volume of saturated oil at sampling conditions of temperature and pressure. This is designated as the differential shrinkage factor B"/B,,,. Table 1 gives the differential liberation data for the oil sample to be used in the example problem. Note that the laboratory data are based on the sampling pressure, or the pressure existing in the wellbore at the time of sampling. In nearly all cases this is a lower pressure than that which existed at original conditions, and the value will require adjustment to a unity basis at initial reservoir pressure before it can be used in reservoir calculations. The adjustment procedure will be discussed later." Many calculations utilize differential liberation data in the form of a formation-volume-factor curve (or Bo curve) where units are expressed as barrels of oil at reservoir pressure and temperature per barrel of stock-tank oil. Commerical lab reports nearly always include calculated Bo data utilizing the residual oil volume, where all gas first was liberated at reservoir temperature and then brought up to standard conditions of temperature and pressure. A common mis-use is to apply this data directly to reservoir studies, utilizing production data as though the field production were separated similar to oil in the lab rather than at field separator conditions. The method for obtaining an adjusted Bo curve requires knowledge of either the initial flash BOit or its reciprocal, the initial flash oilshrinkage factor, which applies to the specific conditions of field separation by which the oil was produced. * * ''The method of adjusting differential liberation data will be discussed in the Feb., 1962 issue of Journal of Petroleum Technology. "*This method will be explained in the Feb., 1962 issue of J ourual of Petroleum Technology, following the section on adjustment of separator liberation data. 13 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Each type of liberation process is encountered to a certain degree at one time or another in the production of petroleum deposits; for a given oil sample, therefore, both processes must b<, investigated to provide data for any eventual reservoir study. ~h~~M~b~~RED GAS L'IBERATED LObr--~------------1 SEPARATED AT REDUCED PRESSURE .75 EOUILIBRIUMt-. _ ....-- LiJ LiJ 2 SEPARATED AT REDUCED PRESSURE 2: ::;) ..J 0.50 ~ ..J 0.50 > > ..J ..J o o SATURATED OIL AT ORIGINAL RESERVOIR PRESSURE - __ mw~ .25 SATURATED OIL AT ORIGINAL RESERVOIR PRESSURE --~ .25 OLW~~--_ _ _-~~~--------~~ PRESSURE PRESSURE - - - - - Fig. 4-Differential and equilihriUln shrinkage of a very high-shrinkage oil at reservoir temperature. Flash Liberation Tests to atmospheric pressure, and the volume and API gravity of the residual oil are measured. This complete process represents production to a separator, and then further production to the stock tank. Data determined from these tests are gas-oil ratios and shrinkage factors at various separator pressures. The gasoil ratios are determined as cubic feet of gas separated at standard conditions per barrel of residual stock-tank oil and, also, per barrel of initial reservoir oil. The shrinkage factor determined is the barrels of stock-tank oil per barrel of sample reservoir oil, and is designated 1IB o , , ' At least two separator pressures usually are selected for flash separation tests utilizing the burette-O psig and some pressure near 25 psig. Lab data from such tests on the sample oil are shown in Table 2. Note that this table does not show the volume of gas liberated from the oil in passing from the separator pressure to atmospheric pressure. Since measurements of this gas are subject to error due to the small volumes involved, the values usually are not recorded. The specific gravity of the gas liberated at the O-psig separator pressure is measured and recorded as shown in Table 6. A high-separator-pressure test is made between 100 and 200 psig utilizing a pressure-volume cell to withstand the high pressures, and similar data are obtained. Stock-tank gas-oil ratios usually are measured in conjunction with these tests because the greater volumes of gas liberated at the high pressures permit greater accuracy to be obtained. From the volumes and densities of the separator gas and residual oil separated at 0 psig, the specific volume of the initial oil is determined and recorded as shown in Table 6. The oil sample used in the example is saturated at sampling pressure and reservoir temperature. Two types of flash liberation tests are performed in the laboratory. 1. Separator tests are conducted to simulate the mechanism by which oil and its gas (which was dissolved at initial conditions but which is liberated in passing to separator conditions) are separated by the field separators. 2. Pressure-volume-temperature (PVT) tests are performed to determine, at constant reservoir temperature, the relation of total volume of oil and its gas with pressure. Although in a single-stage separation set-up oil is considered as being under flash equilibrium up to surface separation conditions, a degree of differential liberation is encountered if multistage separation exists. Although not usually the case, under some circumstances PVT measurements may require that oil and gas volumes be measured separately. Laboratory Separator Tests Separator data obtained from laboratory tests are particularly necessary in determining proper operation of field separators, and they serve as an important adjunct to proper reservoir control. Low-pressure separator tests are made in the laboratory by use of a Bunte burette into which a measured amount of saturated oil is bled from the quantity of sample oil. During a test, pressure is maintained in the burette at a constant pressure below 25 psig, and the volume of oil at the burette pressure is measured. The gas separated from the oil in the burette is measured by a wet-test meter. The burette pressure then is decreased TABLE I-DIFFERENTIAL LIBERATION DATA FOR SAM·PLE FLUID AT SAMPLE PRESSURE AND RESERVOIR TEMPERATURE p Pressure ~ p. =2190 1900 1600 1300 1000 700 400 195 o o 14 GL. Gas Liberated (scf/bbl Sat. Oil at p. and Tr) o 70 137 209 275 347 423 487 646 760 BO/Q08 IDifl'. Shrinkage Factor (bbl Sat. Oil/bbl TABLE 2-FLASH SEPARATION DATA ON SATURATED OIL SAM,PLE Oil at ps and T r ) 1.0000 .9664 .9355 .9034 .8731 .8405 .8029 .7750 .6850 .6650 (1) Separator Pressure (p,ig) (2) GOR Separator (,cf/STS) (3) GOR' Stock Tank (,cf/STB) (4) l/B o ./ fla,h Shrinkage Factor (STB/bbl ,ample oil) o 1190 0 0.602 20 1060 0.635 SO" 947 0.660 150 802 190 0.655 *Flashed from pressure in Col. (1) to 0 psi. ** Interpolated (6) GOR Separator (5) Gravity (OAPI) 42.9 45.0 45.7 45..4 (scf/bbl sample oil) Col. (2) X Col. (4) 717 675 625 525 from curve. JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Fig. 3-Differential and equilihriutn shrinka·ge of a lowshrinkage oil at reservoir tenIperature. 15 TABLE 3-PRESSURE-VOLUME-TEMPERATURE RELATION AT RESERVOIR TEMPERATURE (BASED ON UNIT VOLUME OF SATURATED OIL AT SAMPLING PRESSURE) Pressure 8t/Bl8 In P-V Cell Volume Oil Or Oil and Gas -~ Pi ~ 3500 3000 2500 p,~2190 2130 2075 1970 1835 1680 1525 1380 1240 1120 1000 875 770 570 505 440 390 350 315 290 265 0.9824 0.9888 0.9959 1.0000 1.0090 1.0182 1.0397 1.0706 1.1173 1.1799 ,1.2586 1.3532 ,1.4639 1.5905 1.7809 2.0033 '2.6698 2.9881 3.4836 3.9614 4.4636 4.9415 5.4417 5.9194 PVT tests are performed by transferring a known volume of the saturated sample oil from the sampler to the pressure-volume cell, and then measuring the total volume at reservoir temperature and at pressures higher than sample saturation pressure. The sample is permitted to expand to pressures which are as low as practical, and the resulting volumes are recorded at various pressure points. The test process is shown in Fig. 1. Occasionally, the effect of temperature change on the sample is needed. In such a case, tests are repeated at two other temperatures, e.g., at atmospheric temperature and at some intermediate temperature between atmospheric and reservoir temperature. The data obtained are volume factors, designated B,jB,,, and are expressed as barrels of total oil and liberated dissolved gas at the pressure under consideration per barrel of saturated oil sample at sampling pressure. Table 3 gives laboratory pressure-volume data for the sample oil at a reservoir temperature of 134°F. Viscosity Relationships The viscosity of the reservoir oil sample usually is determined by a pressure or rolling-ball type of viscosimeter.",16 This apparatus is based upon the principle that oil viscosity determines the time required for a closefitted steel ball to roll down an inclined steel cylinder filled with oil. Time measurements are made at pressure intervals, and the viscosity is determined from the time data. Fig. 5, a plot of the laboratory viscosity data determined for the sample oil, shows that above the satura:tion pressure the viscosity increases with an increase in pressure; below the saturation pressure, viscosity increases with a decrease in pressure. The viscosity of residual or stock-tank oil is determined by an Ubbelohde'7 (or similar) viscosimeter at room temperature, at reservoir temperature and at some intermediate temperature. Hydrocarbon Analysis A hydrocarbon analysis is made of a portion of the saturated oil sample. Two types of apparatus are used in this analysis-(1) the Podbielniak (or pod column) for low-temperature distillation of the low-molecular-weight fractions, methane through hexane; and (2) a high-temperature apparatus for distilling heptane through nonane. JANUARY, 1962 08 r---r- -- --_.--f-. . - ~- f.\----+-----+---t------ f----- ------+-------i 061\ " 0.4 0.2 SAMPLE _ _++=-"-_±:__-__+jJSA-T-URr__AT-'O-N----t--=I ~_----+'~ r-- vi. _I-PRESSURE 2190 P$!G I----+-----+-----i---j-------r-,-----, 500 1000 1500 2000 2500 3000 3500 PRESSURE, PSIG Fig. 5-Viscosity of reservoir oil (temperature, 134°F). The residual is reported as the decane-plus fraction. In many cases, however, the sample is analyzed only through hexane, and the remainder is reported as a heptane-plus fraction. The accuracy and applicability of phase-behavior calculations for such things as optimum separator conditions will depend to a great degree upon the detail and accuracy of the hydrocarbon analysis in the range of the heavier components; therefore, accurate extended analyses through nonane should be obtained when practicable. In addition to the weight-per cent analysis obtained, the molecular weights and densities of the individual cuts are determined after volumetric measurements. The hydrocarbon analysis, molecular weight and density data for the sample oil are illustrated in Table 4. ASTM Distillation ASTM distillation test data may be used to extend the hydrocarbon analysis through the range of components heavier than hexane, in conjunction with more detailed phase-behavior calculations. In addition, the data serve as an index for evaluating crude because they indicate the boiling ranges of gasoline, kerosene and lube-stock constituents. ASTM distillation data for the oil sample are shown in Table 5. Orsat Gas Analyses An Orsat gas analysis is run on gas liberated from the oil to determine the amou·nts of components other than hydrocarbons which might be present-components such as oxygen, hydrogen sulfide and carbon dioxide. The nitrogen content may then be determined by difference calculations. TABLE 4-HYDROCARBON ANALYSIS OF OIL SAMPLE Density Component Methane Ethane Propane I-Butane N-Butane I·Pentane N-Pentane Hexane Heptane Octane Nonane Decone and Heavier Hexane and Heavier Weight (gm/cc Molecular Per Cent at 60'F) Weight 7.39 3.96 5.75 0.79 4.44 0.84 2.98 4.11 5.57 5.17 4.44 54.56 0.6826 0.7263 0.7430 0.7623 0.8472 86 99 ,110 123 285 0.8147 203 iOo.OO 15 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Pressure-Volume-Temperature Tests 10 TASLE 5-ASTM DISTILLATION OF RESIDUAL-OIL SAMPLE FLASHED TO 0 PSI AND 76°F Per Cent Over Temperature (OF) ISP 5 10 15 20 25 30 35 40 45 50 55 60 65 112 176 212 244 274 (l00 332 372 418 460 506 550 588 626 Maximum Temperature = 652°F Recovery, by Volume = 67 per cent Residue, by Volume = 31 per cent Loss, by Volume = 2 per cent Gravity of Overhead Product = 49.9 °API TABLE 6-MISCELLANEOUS OIL-SAMPLE DATA Specific Gravity of 0 psi Separator Gas @ 60°F _ Temperature, OF ___________ _ 76 105 1,865 Saturation Pressure, psi 2,040 0.02331 Specific Volume, cu ftjlb 0.02380 API Gravity, Residual Differential Liberation Oil _ Viscosity, cp: Saturated Oil, Residual Oil, Residual Oil, Residual Oil, 11. 12. Nomenclature 13. Tr = reservoir temperature, of 14. l/B o .! Bo/Bo. = = sampling pressure, psig gas liberated, scf/bbl saturated oil at p, and T,. two-phase flash formation volume factor, bbJ oil and gas/bbl saturated oil at p, and Tr flash shrinkage factor, STB/bbl sample oil differential shrinkage factor, bbl saturated oil! bbl oil at p, and Tr 15. 16. 17. ............. 134 2,190 0.02428 ~ ........ 45.4 . ... _ ............. 0.31 .... 2.92 1.99 1.48 Subsurface Sample of Oil and Gas", Oil and Gas Jour. (May 16, 1935). "Humble Subsurface Sample Equipment", Manual 0/ IT!structions, Engineering Laboratories, Inc., Tulsa, Okla. Lindsly, B. E.: "A Bureau of Mines Study of a BottomHole Sample from the Crescent Pool, Oklahoma", Pet. Eng. (Feb., Mar., Apr., 1936). Pirson, S. J.: Elements 0/ Oil Reservoir Engineering, McGrawHill Book Co., Inc., N. Y. (1950). Buckley, S. E.: Petrol,eum Conservation, AIME, Dallas (1951). Clark, N. J.: "It Pays to Know Your Petroleum", World Oil (April, 1953). Hocott, C. R. and Buckley, S. E.: "Measurements of the Viscosities of Oils Under Reservoir Conditions", Trans., AIME, (1941) 142, 131. Ubbelohde, L.: "The Simplest and Most Accurate Viscosimeter and Other Instruments with Suspended Level", Jour. of Inst. 0/ Pet. (1933) 19, 396. *** References 1. Lewis and Randall: Thermodynamics, McGraw-Hill Book Coo, Inc., N. Y. (1923). 2. Andrews: Trans., Roy. Soc. London (1869) 159. 3. Nielson, Ralph F.: "Molecular Explanation of Retrograde Condensation", Oil Weekly (Jan. 5, 1952). 4. van der Waals: Zeit. physik, Chem. (1890) 5, 133. 5. Sage, B. H. and Lacey, W. N.: Volumetric and Phase Be· havior of Hydrocarbons, Stanford U. Press, Stanford U., Calif. 6. Weinaug, C. F. and Bradley, H. A.: "The Phase Behavior of a Natural Hydrocarbon System", Trans., AIME (1951) 192, 233. 7. Allen, J. c.: "Factors Affecting Classification of Oil and Gas Wells", Paper presented at API Spring Meeting (1952) in Shreveport, La. 8. Kuenen: Zeit. physik, Chem., (1893) II, 38. 9. Clark, Norman J.: Elements of Petroleum Reservoirs, AIME, Dallas (1960). 10. Schilthuis, R. J.: "Techniques of Securing and Examining 16 NORMAN J. CLARK is the owner of Norman J. Clark Engineering Co., Dallas-based petroleum consulting firm. He organized the company in July, 1958, after resigning his position as assistant manager in charge of engineering and consulting work for Core Laboratories, Inc., Dallas. Before joining Core Labs in 1955, he had spent 14 years with Humble Oil & Refining Co. in Houston. He graduated from Southwest Texas State Teachers College with a BS degree in math and physics in 1937, and received a BS degree in petroleum engineering from The U. of Oklahoma in 1941. A frequent contributor to Society publications and to industry trade journals, he is the author of ELEMENTS OF PETROLEUM RESERVOIRS, a book published by the Society in 1960. JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 G L8 Bt/B t , = = = p, 2,190 psi and 134°F. 74°F 105° 134°F ~~ 1.096 Fundamentals of Reservoir Fluids, Part Two FUNDAMENTALS OF RESERVOIR FLUIDS Adjusting Oil Sample Data for Reservoir Studies NORMAN J. CLARK MEMBER AIME Introduction The presence of free gas in the form of a gas cap located above the oil zone in a reservoir usually indicates that equilibrium conditions exist between the gas and oil. Therefore, the oil at the gas-oil contact probably was saturated at initial reservoir conditions of pressure and temperature. Any reduction in this reservoir pressure as oil is produced causes gas to be released from solution in the oil. Oil samples taken from a reservoir after production has occurred, therefore, will contain less dissolved gas even though the oil was saturated at sampling pressure. If the reservoir is initially undersaturated and the sampling pressure is above saturation pressure, the sample will contain the same amount of dissolved gas as it did initially. If the sample has liberated some of its dissolved gas prior to sampling, the laboratory data must be adjusted to provide values comparable to those which would have been measured had the sample been taken at the initial reservoir pressure. It is necessary to have data on the oil sample at initial conditions of pressure and temperature because most reservoir calculations, particularly for reservoir behavior, utilize initial conditions as a basis. Amyx, Bass and Whiting'· have described the necessity of adjusting reservoir oil sample data. Adjustment Procedures Procedures for adjusting the various oil sample data are illustrated in detail in the following paragraphs, and then applied to the oil sample data of Tables 1 and 6. * In adjusting the example data used here, the following assumptions are made. 18References given at end of paper. ':'Tables 1 through 6 appeared with the first article in the Fundamentals af Reservoir Fluids series, published in the Jan., 1961. issue of Journal of Petroleum Technology. 1. In the reservoir from which the sample was taken, the oil was saturated at initial reservoir pressure. 2. As a result of the bottom-hole pressure traverses made at the time of sampling, the sampling pressure was found to be 2,190 psig. 3. Examinations of available information - such as early bottom-hole pressure measurements, drill-stem tests and other reservoir characteristics - revealed the initial reservoir pressure to be 2,500 psig. Therefore, the laboratory oil sample data will be adjusted to this pressure at a reservoir temperature of 134°P. Differential Liberation Data Corrective Gas Volume The relation for determining the corrective gas volume, or the amount of gas liberated from the sample oil between initial reservoir pressure and sampling pressure, is as follows. - p, X G CGV = Pi --L8(pS-p) p, - p where CGV • (1) = corrective gas volume, cu ft of gas/bbl of oil at p, and Tr, Pi = initial reservoir pressure, psig, p. = p sampling pressure, psig, = some low pressure on the straight-line portion of the gas liberation curve, psig, and GL,(ps-P) = gas liberated between p, and p, cu ft of gas/bbl of oil at p, and T, .. Utilizing the 400-psig-pressure data point for p, the value for the corrective gas volume is 2,500 - 2,190 CGV = 2,190 _ 400 X 423 = 73 cu ft. The corrective gas volume can also be determined graphically by plotting the differential gas liberation data and extrapolating the curve to the initial reservoir pressure. This technique, illustrated in Pig. 6, merely utilizes graphical means to obtain the results of Eg. 1. Corrective Oil Volume The next determination is the corrective oil volume; this is the volume of oil saturated at the initial reservoir pressure (2,500 psig) which, after the corrective gas volume of gas (73 cu ft) has been released, will result in SPE 91 FEBRUARY, 1962 143 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Editor's Note: This is the second of five Technical Articles in the Fundamentals of Reservoir Fluids series. The first, "Sampling and Testing Oil Reservoir Samples", appeared in the Jan., 1962, issue of JOURNAL OF PETROLEUM TECHNOLOGY. References, Tables and Figures are numbered consecutively, but are published only with the particular installment of the series in which they are first mentioned. NORMAN J. CLARK ENGINEERING DALLAS, TEX. 1 bbl of oil saturated at the sampling pressure (2,190 psig). The relation for obtaining the corrective oil volume is as follows. COV= (2) G L where G L - GL , + CGV COY (3) = adjusted value, scf of gas liberated to some reduced pressure/bbl of saturated oil at Pi and Tn and G", = value of unadjusted laboratory data, scf of gas liberated to some reduced pressure/bbl of saturated oil at p, and T,; and Bo Ho ' Bo/B" = COY Separator Liberation Data Laboratory separator liberation data, including gas-oilratio and shrinkage values, must be adjusted to the basis of initial saturated reservoir oil; since the amount of gas dissolved in the oil sample is a function of initial reservoir pressure, then the separator liberation data also are functions of that pressure. At the time of the reservoir study, it may be found that none of the laboratory separator tests on the sample were taken at the same pressure as that of the average separator pressure maintained in the field during its producing life. Therefore, laboratory separator results first are interpolated to obtain data on a basis of correct field separator pressure; the resulting data then are adjusted to a basis of correct initial reservoir pressure. The following paragraphs describe two methods by which this adjustment can be accomplished. The proper method to use should depend upon the data available or upon the data which the analyst considers more appropriate at the time he makes the adjustment. Generally, however, the first method presented will be the easier and the more straightforward of the two. Method 1 (4) where Bo/B" , = adjusted differential shrinkage factor, bbl of saturated oil at some reduced pressure/bbl of saturated oil at Pi and Tn and Fig. 8 shows the five steps to be followed in the first method. Step A-The laboratory separator data first are plotted graphically to obtain values which correspond to the 50-psig (or average) field trap pressure. These plots, shown in Fig. 9, indicate that 1 bbl of oil at p, and T, will be separated by a 50-psig trap into 0.660 STB of oil and 625 scf of gas. 700 I I I II 600 ,, II I 1\ I I i ! , i ii: J: (J) I :I! , .8000 1\ I '\ I, 1\ I I PRESSURE, PSIG Fig. 6-Laboratory differential-shrinkage and gas-liberation data, illustrating graphical method of determining corrective oil and gas voluDles in adjusting oil sample data to a basis of correct initial reservoir pressure (data from Table 1). 144 I 1\ ! I I I! i :! I I ! 1000 1500 i m 1 (J) -, I 0 <t .5000 "\ I 1 1\ , 2500 (5 is m ".6000~ ...J (5 I I 2000 I ! I i i= ~ ...J z ...,: I I ci IIJ <t a: (J) .7000 UJ U. ...J U. , i i I I I I I I I 500 , i I I ! I NOTE: CbRREtT. ~i' EST. TO BE 2,500 PSIG I I I I t I! I I I 1\.,1 I! 1• I,I I 100 I II i iI! Z <t <t .9000~ Ci ii j t-" IIJ 0 (!) i 1\ I I I ,.A a: ~ .oooo~ I-' «(J) .- ...J Om ~m 0 m JOOO PRESSURE PSIG Fig. 7-Adjusted differential liberation data to basis of correct initial reservoir pressure (data from Table 7). JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 where COY = corrective oil volume, bbl of oil at p, and Tr/bbl of oil at p, and T" and p = some low pressure on the straight-line portion of the differential liberation curve. The corrective oil volume may also be determined by the graphical method. Fig. 6 shows the corrective oil volume to be 1.035 bbl of oil at p, and T,.jbbl of oil at p, and T r • Adjusting the differential liberation data involves altering all of the data to a basis of 1 bbl of oil saturated at the initial reservoir pressure of 2,500 psig. This is accomplished by the following relations. Bo/B" = unadjusted laboratory shrinkage factor, bbl of saturated oil at some reduced pressure/bbl of saturated oil at p, and T ,. The laboratory differential liberation data of Table 1 are adjusted and the results of calculations are shown in Table 7. The adjusted differential liberation data then are plotted in the form of work curves for subsequent reservoir calculations, as shown by Fig. 7. SAT. OIL AT P. (2,190 PSIG) G AND T, (134 F) SAT. Oil AT p, (2,500 PSIG) AND T, (l34°F) STOCK.TANK OIL SEPTD. AT AVG. FiElD SEP. PRESSURE GAS, SCF 800 ~~ ~~700 ~~ I-~~II+ ~~ (!)'" ~ ~"""-'--'""-' Step {AI-flash liberation Data (Interpolated from laboratory Data). II .96bbl + / '00 a: « / /' III.J IDID ",ID .Jii:: 500 / / ·T - i"""-< :>....... j / ' !:;I~:::! ~ ;:.... 0.- UJO ~ T I I;; I/Bost- I-- I-- . GAS, SCF ~ ..... r- r-. 1 51PI GRAVITY -- SEP lOR - I ...... 'I I / (.) III Step Un-Data from Adjusted Differential liberation Data. 10. II SEPARATOR PRESSURE, PSIG Fig. 9-Laboratory flash separator data vs separator pressure for sample oil (data from Table 2). +u== of gas in continuing to separator conditions, the total gas liberated to 50-psig separator conditions from 1 bbl of initial oil is 675 scf (or 604 + 70.5). The flash-shrinkage factor, adjusted for both initial reservoir pressure and field separator pressure, then is 0.6376 STB of oil/bbl of initial reservoir oil. Step E-The initial dissolved gas-oil ratio, adjusted for initial reservoir pressure and field separator pressure, is 1,059 scf (or 675/0.6376) of gas/STB of oil. Step (C)-From Data of Step {AI. I--~ Step (D)-Adjusted Shrinkage Factor =co. __ .6376 STB/bbllnitial Reservoir Oil. Method II Step (EI_Adjusted Initial Dissolved Gas-Oil Ratio = , ,059 cu ft/STB. Fig. 8-Graphic illustration of adjustment of flash shrinkage factor and dissolved gas-oil ratio to initial reservoir conditions using differential liberation data. Step B-The volume of gas which must be added to the volume measured in the laboratory so that the total volume will be consistent with an oil sample saturated at initial reservoir pressure is determined by the plot of adjusted differential data (Fig. 7 and Table 7). This amount is the corrective gas volume divided by the corrective oil volume and, in the case of the example problem, is 70.5 scf (or 73/1.035) of gas/bbl of oil at PI and Tr (or/0.966 bbl of oil at P. and Tr). Step C-Based on data from Step A, 0.966 bbl of oil at P. and Tr will separate through a 50-psig trap into 0.6376 STB (or 0.660 X 0.966) of oil and 604 scf (or 625 X 0.966) of gas. Step D-Since 1 bbl of oil at Pi and TT releases 70.5 scf of gas in going to the p s condition and then 604 scf The second method, illustrated in Fig. 10, utilizes flash separator data. Step A-The separator flash liberation data for a 150psig trap (Table 2) indicates that, for 1 bbl of oil at p., 0.655 STB of oil and 525 scf of gas will be separated through a 150-psig separator. Step B-The 150-psig separator data are used as a basis for preparing a gas-oil-ratio curve to determine the amount of gas liberated from oil when the pressure drops from Pi = 2,500 psig to the 2,190-psig sampling pressure. The assumption is made here that the gas liberation curve is a straight line between the highest (l50-psig) separator pressure and the sampling pressure, as shown by Fig. 11. Extrapolation of the curve indicates 80 scf of gas/bbl of oil at sampling pressure. Although this assumption is not exact, the existence of two partially compensating errors permits the approximation to be reasonable. These errors are as follows: (1) the line is a curve, which tends to decrease the gas volume required; and (2) the separation in the reservoir occurs at reser- TABLE 7-ADJUSTMENT OF DIFFERENTIAL LIBERATION DATA TO BASIS OF INITIAL RESERVOIR PRESSURE AND RESERVOIR TEMPERATURE (1) GLs Gas Librtd. (scf/bbl sat. oil at ps and TT} From Table 1 Adistd. Gas Liberated (scf/bbl sat. oil at pi and TT) Col. (2) + 73, .035*- (4) B./B •• Difl'. Shrinkage Factor (bbl sat. oil/ bbl sat. oil at p. and TT) From Table 1 -73* 0 70 137 209 275 347 423 487 646 0 70.5 138 203 272 336 406 479 1541 695 1.0350 1.0000 .9664 .9355 .9034 .8731 .8405 .8029 .7750 .6805 (2) (3) GL p pressure (psig) Pi = 2,500 p, = 2,190 1,900 1,600 1,300 1,000 VOO 1400 195 0 (5) B./B.I Adjstd. Difl'. Shrinkage Fador (bbl sat. oil/ bbl sat. oil at PI and TT) Col. (4)/1.035*' (6) B. Adjstd. Form. Volume Factor (bbl sat. oil/STB) Col. (5)/.6376*-- 1.0000 .9660 .9345 .9045 .8725 .8430 .8140 .7755 .7490 .6620 1.5684 1.5151 1.4657 1.4186 1.3684 1.3222 1.2767 ·1.2163 1.1747 1.0383 *Corrective gas volume. **Corrective oil yolu!11e. ***Adiusted flash shrinkage factor. FEBRUAUY, 1962 145 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 + 0 SAT. OIL AT P. (2,500 PSIG) SAT. Olt AT p,(2,190PS1Gl AND T, (13,f"f) AND T, (l34"F) ,---, ,---, STOCK.TANK OIL SEPTD. AT NOTED ,---, /'. II 150# Q-II = + .655 obi Pressure-Volume-Temperature Data Adjustment of the pressure-volume data B,/B" is necessary both to smooth and to extrapolate the data to the initial reservoir pressure. Smoothing the data may be accomplished by drawing a smooth curve through the points plotted as pressure vs volume; however, this manner of smoothing seldom is used because extrapolation of the curve through the laboratory data points in the range of the sampling pressure cannot be accomplished with satisfactory precision. The following empirical relation, however, usually will permit suitable smoothing and extrapolation of the relative-volume curve because the data BOO ii: o ~ I] Ibb' ~--- .301 .0431 .655.5T ?'" liberation 8bl Thermol Shrinkage from TemperatureCorreclion TolalGcr.liberaled -- 525 T c=1 Oil ~e~~~':1 ~ 0. "\ "\ (!) "\ 200 I-II + ~--Q--~~;,'''i + I}","" 11-. + ~ Q~63~;,''' II Step (E)-Determination of Adjusted Initial Dissolved Gas-Oil Ratio and Shrinkage factor, 50·psi Separator Pressure. • ~ Itl} + Slep (f)-Adjusted Shrinkage foctor .6363 STB/bbl Initial Reservoir Oil, Adiusted Initial Diss,olved Gas-Oil Ratio 680 cu ft/bbllnitiol Oil. 680,"" ~ 680/.6363 Step (G)-Adiusted Initial Dissolved Gas·Oil Ratio 1,068 cu ft/STB. Fig. IO-Graphic illustration of adjustment of Hash shrinkage factor and dissolved gas-oil ratio to initial reservoir conditions using Hash liberation data. w 0 0 III 0 ~ I "\ w t:c a:: - (f) Q. c Step (D)-Determinatian af Shrinkage from p, to p" 150-psi Separator Pressure. .L r-~ "\ l1...Cf) >- (!) "\ ~300 ....10 al 124= 649SCF Shrin~age per (U II GO! liberated = :3019/649 -' .000465 b~1 Shrinkage from p, ta p. and T, = 80 X .000465 .0372 bbl Shrlnkoge 146 111 STRAIGHT-LINE INTERPOLATION , I-I-. BETWEEN HIGHEST SEPARATOR .... f',. PRESSURE AND SAMPLE PRESSURE ::J....I en <{ '~f!,, __ ~r--+ ~~':~;.;Y:~} '" , ," S25(ult ,, :J:al al Step (C}-Determination of Shrinkage Due to Temperature Chonge and Gas liberation, J 50-psi Separator Pressure. 190 x .655 11- 500 M:l ~ 400 .655STB EXTRAPOLATED PORTION , ~ 8bl Shrinkage Due 1,,0 l, 600 ~ Step (B}-Dato from Plot of Flash Gas-Oil Ratio vs Pressure. 150#, FSEPARATOR DATA W tia:: "{ ,, , ,, , en Step (A)-Flash Liberation Data, l50-psi Separator Pressure. ------ II I I I I I I I I 700 tt ,---, r---. Oil Formation-Volume-Factor Curve The value of the adjusted flash separator shrinkage factor derived using Method I is considered to be the most accurate-that is, 0.6376 STB of oil (separated through a 50-psig separator at atmospheric temperature) /bbl of saturated oil at 2,500 psig and reservoir temperature. The formation-volume-factor curve, or differential liberation data, applicable to oil and gas separated in field separators is determined by dividing the differential oilshrinkage data by the adjusted flash-shrinkage factor. This is shown in Table 7 and plotted in Fig. 12. a:: GAS. SCF SEP.PRESSURE GAS, SCf Step F-At p, and Tn 1 bbl of oil will liberate 680 cu ft (either 603 + 77, or 705/1.0372) of gas; therefore, the adjusted initial shrinkage factor is 0.6363 STB (or 0.660/1.0372) of oil/bbl of oil at Pi and T,,,. Step G-The adjusted initial dissolved gas-oil ratio is 1,069 scf (or 680/0.6363) of gas/STB of oil. N N "c..- "• c. r: (f) ILl "\ 100 1"\ , "\ (II ::J \ en <{ , ,\ i', (!) : , , "\ 80CUFT ~ -100 500 1000 15M 2000 IIII 2500 3000 PRESSURE, PSIG Fig. II-Flash liberation data plotted vs pressure, illustrating method of estimating gas liberated between initial reservoir pressure and sample pressure per barrel of' saturated oil at sampling pressure. JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 voir temperature, which tends to increase the volume of gas required. The corrective gas volume can also be calculated algebraically by Eq. 1. Comparing this value with that of the corrective gas volume determined by differential liberation data reveals a difference of about 10 per cent. Since the value determined by the latter method is considered more accurate, it should be used if differential liberation data are available. Step C-The unknown volume of saturated oil required at PI and Tr to result in 1 bbl of saturated oil at P. and Tr must be determined. First, the thermal shrinkage for the oil in changing from 134 to 76°F is determined from the "National Standard Petroleum Oil Tables""; in the case of the example problem, this value is found to equal 0.0431 bbl of oil. The total shrinkage caused only by the liberation of total gas at both the 150-psig separator and the stock tank then equals 0.3019 bbl (or 1 - 0.6550 - 0.0431). Step D-The amount of shrinkage to the initial oil and the actual volume of the initial oil, before it changed from the Pi and Tr conditions to the conditions of P. and Tn are determined by first calculating an amount of shrinkage caused by the liberation of 1 cu ft of gas alone (without temperature effects). The value of this shrinkage equals 0.000465 bbl, or 0.3019/[525 + (190 X 0.655)], of sample oil. Therefore, the total shrinkage to the initial quantity of oil is .0372 bbl (or 0.000465 X 80), and the actual volume of initial oil is 1.0372 bbl (or 1 + 0.0372) saturated at P. and T •. Step E-Again from Fig. 9, the separator gas-oil ratio and shrinkage factor interpolated for a 50-psig trap pressure is 625 scf and 0.660 STB, respectively; for the same trap pressure, therefore, 1.0372 bbl of oil at Pi and T,,, will liberate 705 scf (or 625 + 80) of gas. 1.6 i ! / 1.5 / : 1-+I, I I cf'm I I >-" I ! :ri- __ ._, ~ I f~:~:i.:j a. I I-err- +- V : T ,_. --,-! I H-i+- 1,000 , I I )"i- ~tt , , l- -t+tt -tt -./::, '; :_ I{ fPRESSURE : I 1,.': ~O~~WV~~ ff , 2.5 •,'RESERVOIR INITIAL - LAST GOOD DATA POINT '~ I I I I I i-t , i ' I EXTRAPOLATED m ........ ~w / , ,/ I I I, 0 POINTS FROM LAB DATA I I 2,000 1,500 I I I 2,500 3,000 PRESSURE, PSIG Fig. 13-Procedure for adjusting PVT data. where Bt/B" 1000 1500 RESERVOIR 2000 2500 dissolved gas, volume at P and Tr/volume at Pi and T r • The relative-volume data for samples from undersaturated reservoirs with saturation pressures below sampling pressures do not require adjustment, but laboratory data usually must be smoothed by drawing the best curve through the data points. Calculations for adjusting the relative-volume data to initial reservoir conditions of 2,500 psig and 134°F are shown in Table 8, and the adjusted data are plotted in Fig. 14 as a work curve for reservoir study calculations. 3000 PRESSURE, PSIG Fig. 12-Formation-volume-factor curve adjusted to surface separation conditions (data from Table 7). usually plot either as a straight line or as one with only a gentle curve on co-ordinate paper." <I;; - p) 1 . p[-.-!...1 B,. (5) Specific Volume where Y = compressibility function of pressure, relative volume and saturation pressure for flash liberation data, p, = saturation pressure of sample, psia, P = any intermediate pressure, psia, and B,/B t , = relative volume of oil and its liberated dissolved gas, volume at P and Tr/volume at P, and T r • Values of the function Y are calculated from laboratory data and plotted vs pressure. The fact that a straight line usually can be drawn through the data points permits ease in extrapolating the curve to initial reservoir pressure. Fig. 13 illustrates this extrapolation. Calculation of the adjusted relative-volume data is accomplished by Eq. 5 in the following form. Bt/B" = 1 + Pi - P . The specific volume of saturated oil at Pi and Tr can be calculated by combining the volumes of shrunk oil and liberated gas determined from the flash gas-oil ratios; to this sum the corrective gas volume is added, with the assumption being made that all of such added gas is methane (molecular weight = 16). With high-shrinkage oils, where the first gas liberated may contain large proportions of heavy or intermediate components, this assumption may be quite erroneous; thus, precautions must be taken in estimating the molecular weight of the gas to be added. Hydrocarbon Analysis The hydrocarbon analysis data usually are adjusted only in cases where extreme accuracy is required. The adjustment procedure involves adding the corrective gas volume to the hydrocarbon analysis on a weight-per cent basis, with the assumption being made that all gas to be added (6) pY = relative volume of oil and its liberated TABLE 8-PROCEDURE FOR ADJUSTING PRESSURE·VOLUME-TEMPERATURE DATA TO BASIS OF 1 BBL OF OIL SATURATED AT INITIAL RESERVOIR PRESSURE Eq. 5, (1) (2) p p Pressure Pressure (psig) (psia) (3) St/S" ReI. Vol. From Table 3 ps - p Y = (p, - p)/{p[(Bt/B,,) - 1]} (5) (6) p[(S,/S .. ) - 1], [Col. (2)] X [Col. (3) - 1] Y Col. (4) (5) 5=01. = 2500 2515 tl415 2315 p, 1.0000 2205 2145 1.0090 1.0182 2090 1985 1.0397 1850 1.0706 1695 1.1173 1540 1.1799 1395 1.2586 1255 1.3532 1135 1.4639 1015 1.5905 1.7809 890 785 2.0033 585 2.6698 520 2.9881 455 3.4836 405 3.9614 *Values from smooth curve through data. Pi (4) = 2400 2300 2190 2130 2075 1970 1835 1680 1525 1380 1240 1120 1000 875 770 570 505 440 390 FEBRUARY, 1962 60 115 220 355 510 665 810 950 1070 1190 1315 1420 1620 1685 1750 1800 19.31 38.04 78.80 130.61 198.82 277.05 360.75 443.27 526.53 599.36 695.00 787.59 976.83 1033.81 1130.04 1199.37 3.1072 3.0232 2.7913 2.7179 2.5652 2.4000 2.2454 2.1430 2.0319 1.9855 1.8918 1.8029 1.6580 1.6300 1.5488 1.5024 (7) Y' 3.2270 3.1459 3.0638 2.9749 2.9275 2.8802 2.7913 2,6811 2.5546 2.4299 2.3121 2.1971 2.0985 2.0019 1.8976 1.8097 1.6502 1.5952 1.5411 1.5024 (8) Pi - 100 200 310 370 425 530 665 820 975 1120 1260 1380 1500 1625 1730 1930 1995 2060 2110 P (9) St/S .. Adiusted Col. (8) Cols. (2) X (7) + 1 1.0000 1.0132 1.0282 1.0473 1.0589 1.0706 1.0957 1.1341 1.1894 1.2606 1.3472 1.4570 1.5794 1.7382 1.9622 2.2178 2.9991 3.4051 3.9378 4.4677 147 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 500 ~ - I Ul a. 1.0 y 3.0 ~ / o t-t- 1- I r="1 I V V ! I is either methane (molecular weight = 16) or some mixture of components as deemed probable. This type of calculation is illustrated later under flash calculations. Limitations in Adjustment Procedures Correlations of Reservoir Oil Sample Data Various investigators have attempted to generalize oil sample data so that correlations could be made. They reasoned that by using these correlations they might eliminate the need for a great deal of expensive oil-reservoir sampling, testing and analysis. Since the reservoir-oil hydrocarbon analysis controls fluid data to a large extent, any accurate correlation of sample data must include some parameter of hydrocarbon analysis. This is impractical, however, because the hydrocarbon analysis may include anyone of an infinite number of combinations. Therefore, various correlations have limited value for precision reservoir calculation work, but they are extremely valuable for many practical, day-to.038 \\ \ .036 1\ .034 1.3000 \ .032 <D ..J ;:: .030 ::l \ w· 028 \ \/ ~ o ..J o w o z ~ x w ~ > .026 u u: u ~ .024 <I) /' .022 / H-1-t-+++++-t--t-+--i'1t~+- - i ,,\c-j- I-t~~~- n-f- ~ -f-t-+++--I-I-f---+-+-H-+ 1.0000 L...L-.L.LJL"L--I-L..l-LIO...Loo--'--...L-L...L,--1s00-L-LL..l-200LO...L-LL-lI...ll2500 1.0000 o PRESSURE, PSIG Fig. 14--Adjusted relative volume or PVT data (from Table 8). J.18 .020 .01 8 o ~ \ 3200 I~r--- / ~VfB~~; --< ""~ r / L I i_ ~ ~~BBLE OINT LOCUS ~~~ / ~OVII ~ -f' {>0,'0 ,0: ~ 1000 ~ / / i}o/(A) / \ SP ECIFIC VOLUMES LL ~ ·SURFACE GAS PER BARREL OF STOCK TANK OIL ~) (C) 3200 ~ 2000 f--" 3000 4000 --5000 6000 7000 PRESSURE (PSIA) Fig. 15-Pressure-volume relations of mixtures of oil and gas at 145 0 F (from J. C. Allen, Ref. 7). JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 The reservoir analyst must exercise caution when adjusting measurements made on either the subsurface sample or the recombined sample. In adjusting the example data used here, the assumption was made that the oil was saturated at initial reservoir pressure. If the reservoir oil had been saturated at some intermediate pressure between the sampling and initial reservoir pressures, however, the resulting adjusted data will be erroneous and all subsequent reservoir study calculations utilizing the erroneous data also will be in error. Espach21 has shown that in undersaturated reservoirs a great variance may exist in oil characteristics, including dissolved gas-oil ratios. If the reservoir is undersaturated, therefore, it usually is necessary to obtain more than one sample, depending upon the nature of the problem to be solved. Some naturally occurring crude oils exist at conditions very near to their critical temperatures and pressures. Because of the high-shrinkage behavior (or the behavior that may govern the change in physical state) of some crude oils during isothermal pressure changes at temperatures below but near the critical temperature, a thorough examination and study must be made not only of the data for such samples, but also of the reservoir conditions and characteristics; a study of this type is essential if the behavior of the oil sample is to be evaluated with the greatest precision. In Fig. 15 Allen' illustrates the basis for concern regarding interpretations of reservoir oil samples. This figure shows a sample of oil with four amounts of dissolved gas and, also, the flash liberation data from the resulting sample. Samples with oil-volume curves similiar to Curve A may be extrapolated to higher saturation pressures with reasonable precision. Samples with curves similiar to Curve B cannot be extrapolated with reasonable precision except over small pressure increments. This is explained by the fact that an oil having a shrinkage curve similiar to Curve C may exhibit a curve similar to Curve B after some of its initial dissolved gas has been liberated from solution. It is readily apparent, therefore, that conventional extrapolation of Curve B to the initial pressure will not provide the analyst with data which may be properly represented by Curve C. This is an exaggerated case, of course, because ranges of pressure change involved in extrapolation are usually small; however, it does illustrate the manner in which large errors may be encountered in the extrapolation process unless caution is exercised and unless a thorough investigation is made of all data associated with the oil sample. To illustrate the various shapes encountered, Fig. 16 shows differential shrinkage curves for five actual oil samples. 22 ,23 Curve E obviously represents an oil existing in the reservoir at conditions fairly near the critical state, and great care must be employed in adjusting its sample data. 1.0 50 0 45 0 W (J)W co:: ...J:::> u.m .9 0 :I: 00:: (!) Q. Zo:: Z it: ~o ,I- (f) 00:: olf ..J I-w m(J) u. < i= Z .7 30 o(!) >-u; III 0: ~o 0:: (!)t:( C 25 o ~t 0 o 0 0 ~ C m 0 ~ 0 ~ i-'<0 20 GOR 3950 BO/BOI~·271 SAT. PRESS.-4527 PSI' .5 15 0 1 2 3 4 5 6 7 VISCOSITY OF SAT. RESERVOIR OIL AT PI AND Tr , CP Fig. IS-Relation of API gravity to viscosity. .4 25 50 75 100 PRESSURE, PERCENT OF SATURATION PRESSURE Fi,g. 16-Comparison of differential shrinkage curves for different shrinkage oils. ,~ '--r-'--'--'--~-'--'-'--'--'--r---------o 1500 U-l---+--+--+------ __ 1--____I----tt!_:2-r20_0_C+U_F_T+-/B_B--j~1 r--f--+---+--+--+--+-+---+--+---+-----,4-+---+--+-----j I---t---+----+-+--+-+-_+_ +---+----+,-1I /-1 --t-----t-+-----l 1 1400 1300 ~ (J) Q. 1200 1---+---1---+--+--+----+--1--+--+--*1 1 I 7' ~~ ---+--+--J--- --- -+----+--+-----+--I--I--+-----i---+----+------j o 1100 - /, i I ~...J'''' I--~-~--T--r'~--+----+~~~~~.---+.---~-+~--+----+ 00 III :I:m 900 (J)I-BOO <(J) ii~700 ZO W (f) 600 :I: ~ , Ii, 400 e (' ,--j q , ! 1_ r-t-~,.- ~-fi 1-i~o:8,~fo "'o-l~_ ~i- T 'i' - r J__ 0:: o(!) r-i---t- 1---4t -- I-- ! ~",." .. - ~ ----I - -- '. ! ~ '" , i I i I I -,I--ii,-----+,-~.---yt---.f'-f-'+o SATURATED SAMPLE , , 0' ' " / 200 ,/ • i i UNDERSATURATED SAMPLE ! i I 092 0.88 0.84 I! I 0.80 0.76 D.n 0.66 I I 0.64 0.60 0.56 r -r I Y 0.96 I 0.52 0.46 044 0.40 1/80if WHEN FLASHED TO 0 PSIG Fig. 17-Relation of oil shrinkage to dissolved gas-oil ratio. day reservoir engineering calculations. Typical of these correlations are those presented by Standing" (GOR vs formation volume factor, bubble-point pressure and twophase formation volume factor) and by Beal24 (viscosities of air, water, natural gas, crude oil and associated gases). FEBRUARY, 19'62 Two of the most common correlations are shown in Figs. 17 and 18 for a large number of oil samples. Fig. 17 shows oil shrinkage at O-psig separator pressure plotted vs initial dissolved gas-oil ratio, and Fig. 18 shows the relation of stock-tank API gravity to the viscosity of initial reservoir oil. The close correlation between shrinkage and gas-oil ratio results from both parameters being volumetric and because of the small variation in vapor volumes of the various components. The good correlation between API gravity of stock-tank oil and the viscosity of initial oil is expected, since both have a functional relation to the molecular weight of the mixture and because a fairly uniform relation exists between the viscosities of initial oil and residual oil. In this respect, the residual oil is approximately two to four times as viscous as the initial saturated oil. References * 18. Amyx, 1. W., Bass, V. M., Jr. and Whiting, R. 1.: Petroleum Reservoir Engineering, McGraw-Hill Book Co., Inc., N. Y. (1960) . 19. "National Standard Petroleum Oil Tables", Circular C-41O (superceding C-154), U. S. Dept. of Commerce (1936). 20. Standing, M. B.: Volumetric and Phase Behavior 0/ Oil Field Hydrocarbon Systems, Reinhold Publishing Corp., N. Y. (1952) . 21. Espach, Ralph H.: "Variable Characteristics of Oil in the Tensleep Sandstone Reservoir, Elk Basin Field, Wyoming and Montana", Trans., AI ME (1950) 192,75. 22. Welsh, J. R., Simpson, R. E., Smith, 1. W. and Yust, C. S.: "A Study of Oil and Gas Conservation in the Pickton Field", Trans., AIME (1949) 186,55. 23. Crego, W. O. and Henegan, J. M.: "Report on the Mamou Field Pressure Maintenance Project", Trans., AIME (1951) 192, 263. 24. Beal, Carlton: "Viscosity of Air, Water, Natural Gas, Crude Oil and Its Associated Gases at Oil-field Temperatures and Pressures", Trans., AI ME (1946) 165, 194. *** "'For Refs. 1 through 17, see Jour. Pet. Tech. (Jan., 1962) 16. 149 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 ;3 .6 ...... eO oo~ I-Q. III U. U. 0 g 3S --II:-- ~c :I: o ~ o ~ .B 0 .j() ::!~ III ~ ~ Fundamentals of Reservoir Fluids, Part Three FUNDAMENTALS OF RESERVOIR FLUIDS Sampling and Testing Gas Reservoir Samples NORMAN J. CLARK MEMBER AIME An error has been noted in the second article of the series, "Adjusting Oil Sample Data for Reservoir Studies", which appeared in the Feb., 1962, issue of JOURNAL OF PETROLEUM TECHNOLOGY. On page 149, Fig. 16 shows a comparison of differential-shrinkage curves for five different-shrinkage oil samples. By each curve inside the figure, the symbol "B.IB • ." was incorrectly used to designate "adjusted flash shrinkage factor"; the correct symbol for "adjusted flash shrinkage factor" is "lIB.i'" For example, the data appearing by Curve (A) should read "1 lB." = .763" indicating the oil, from which this differential shrinkage curve was obtained, had a flash shrinkage factor of .763 STB oillbbl initial reservoir oil. Types of Gas Reserves Gas deposits are grouped into the following three broad classifications. 1. Dissolved gas deposits, as the name implies, refer to gas which is dissolved in the oil in place in the reservoir and which will be liberated as pressure drops when oil is produced. 2. Associated gas deposits identify caps of gas which are located above and in equilibrium with oil zones in the reservoir. 3. Nonassociated gas deposits are free gas deposits which are located away from and not in equilibrium with oil deposits in the reservoir. Thornton" has classified free gas deposits into three types, according to the phase behavior of the gas as temperature, pressure, or both, decline. Any of these three types-(l) retrograde gas condensate, (2) wet gas and (3) dry gas-may apply to either associated or nonassociated gas deposits. The type of gas data most frequently needed for reservoir studies depends, of course, on the types of gas being considered and the nature of the problem. For instance, if the problem involves gas containing heavy components which will condense in the form of retrograde condensate as pressure drops in the reservoir, the information needed may be very complex and may require that numerous tests 266 and measurements be made to obtain it. If the problem involves wet gas where no retrograde condensation occurs but where liquid is recovered in separators or if it involves dry gas where no liquid is condensed in either the reservoir or separator, then the information needed may be somewhat less complex. However, the gas-behavior information normally required for oil-reservoir studies includes hydrocarbon-analysis data, pressure-volume-temperature (PVT) relationships and viscosity relationships; these data may be required either for gas in the form of free gas saturation in the oil zones of an oil reservoir or gas-cap gas in equilibrium with an oil rim. If the oil reservoir has high-shrinkage oil in place or if the reservoir temperature is near the critical temperature of the mixture, the gas hydrocarbon-analysis and PVT data may be highly changeable as reservoir pressure decreases. Obviously, therefore, the tests conducted for these properties may become complex. Both dry-gas and wet-gas reservoir studies usually require hydrocarbon-analysis data and PVT relationships. In addition, wet-gas reservoir studies also require data necessary to determine phase-behavior characteristics under conditions of surface separation. Most free gas deposits, especially the deep high-pressure reservoirs, fall into the gas-condensate classification because of the retrograde condensation of liquid which occurs in the reservoir as pressure drops. Testing the gas from these reservoirs involves gathering sufficient data to indicate characteristics and phase behavior of the reservoir fluid at reservoir temperature, plus data which describe these same properties under surface separation conditions. To prevent losing substantial amounts of retrograde liquid in wet-gas reservoirs, it is important that enough tests be conducted on the produced gas to positively identify it as not being retrograde material. Extracting Gas Samples A representative sample of gas as it exists in the reservoir must be obtained for laboratory analysis. In the past, bottom-hole gas samples have been extracted with a special subsurface sampling container" which, when lowered to the bottom of the gas well, permitted samples to be obtained without first losing some condensable material through a loss in pressure. Using this subsurface sampler to extract gas samples has several disadvantages, however, "References given at end of paper. SPE 91 JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Editor's Note: This is the third of five Technical Articles in the Fundamentals of Reservoir Fluids series. References, Tables and Figures are numbered consecutively, but are published only with the particular installment of the series in which they are first mentioned. NORMAN J. CLARK ENGINEERING DAllAS, TEX. Laboratory Examination of Gas Samples Hydrocarbon Analysis The laboratory procedure for examining the components of the gas sample essentially consists of (1) analyzing the gas sample for methane, ethane and propane, (2) distilling the components from the charcoal sampler and obtaining a hydrocarbon analysis of the butane-plus in that mixture and (3) obtaining a hydrocarbon analysis of the separator liquid. The hydrocarbon analysis of the material from the charcoal sampler is mathematically combined with the methane, ethane and propane analyses of the gas sample on the basis of the volume of gas passed through the charcoal sampler. Finally, the hydrocarbon analysis of the original reservoir material is obtained by mathematically combining the previously combined gas and charcoal liquid analysis with the analysis of the separator liquid on the basis of the measured separator gasliquid ratio. Distillation Test practice, published data such as that of Katz, et ai,'" and Carr, Kobayashi and Burrows"' usually can be utilized. Calculations of Gas PVT Relationships Theoretically, a "perfect gas" is one in which the molecules are so small and far apart that they never come close enough together to be influenced by attractive forces. Furthermore, the volume occupied by the molecules themselves is infinitesimally small compared to the space within which the molecules are free to move. The pressure-volume-temperature behavior of this so-called "perfect gas" conforms to that predicted by the following well-known laws of Boyle and Charles. pV = nRT (7) where p = pressure, psia, V = volume, cu ft, n = number of lb moles, R = gas constant = 10.71, and T = temperature, oR (460 + OF). A gram molecular weight of any actual gas (for example, methane = 16 gm) occupies only 23.6 liters of space; within this space, however, there are 6.06 X 10" molecules. In view of this, it is readily apparent that practically all actual gases experience some degree of molecular attraction or interference and, thus, deviate somewhat from the so-called "perfect-gas" laws. A compressibility factor Z is incorporated in the ideal gas law equation (Eq. 7) to make the relation applicable to hydrocarbon gases. The term Z corrects for the nonconformance of the actual gas to the ideal relation, i.e., for the difference in pressure caused by the added molecular attraction or internal pressure, and for the difference in total volume occupied by the molecules brought about by the reduction of the volume of the molecules themselves. The resulting relation is pV = ZnRT . where Z = compressibility factor, dimensionless. The numerical value for the compressibility factor may be obtained from experimental data or it may be approximated by a method of correlation by Kay" called the "pseudocritical" method. This latter method, involving use of the hydrocarbon analysis of the reservoir gas, is explained in detail in the following paragraphs. For the example calculations which follow, the hydrocarbon analysis of a gas-cap gas will be used, and compressibility factors will be calculated through the pressure range up to the original pressure of the reservoir from which the oil sample was taken. As shown in Table 9, the pseudocritical temperature of the gas is found by summing all the products of mol TABLE 9-CAlCUlATION OF PSEUDOCRITICAl TEMPERATURE AND PRESSURE FOR GAS·CAP HYDROCARBON MIXTURE (1) (2) (3) A high-temperature or Hypercal distillation test is run on the stock-tank sample to obtain data from which the hydrocarbon analysis can be mathematically extended with better precision through a wide range of heavy components. Crit. Temp. (OR) NGSMA Gas-Cap Gas Data Book Component (mol frac.) Viscosity Methane Occasionally, gas viscosity measurements are needed for certain reservoir behavior calculations involving fluidflow problems, and these measurements are difficult to make. Fortunately, however, viscosity values do not vary greatly between the different natural gases so that, in Propane MARCH, 1962 (8) (4) .(5) (6) pc Mix. Pseudo- Camp. Mix. erit. PseudoPress. erit. (psia) Temp. (OR) NGSMA (CoL 2) (CoL 3) Data Book To Compo Hydrocarbon Analysis of Ethane Butane Pentane Hexane Heptane+ .8087 .0976 .0520 .0215 .0073 .0038 .0091 344 550 672 750' 839' 914 972 278.2 53.7 34.9 16.1 6.1 3.5 8.8 To = 401.3 1.0000 *Average of critical values for iso-and nor-components. crit. IPress. (psia) (Col. 2) ,(Col. 3) 673 709 643 537' 485' 435 396 544.3 69.2 33.4 11.5 3.5 1.7 3.6 pc = 667.2 267 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 the most notable one being that the size of the obtained sample is too small to permit an accurate analysis of the heavier components. Another drawback is that troublesome condensation occurs within the sampler when the temperature of the sampler is reduced. For these reasons, therefore, gas reservoirs are nearly always sampled at the surface, even though both pressure and temperature are reduced on the produced material at the surface and some of the gas will have condensed to form a liquid. Obviously, then, all gas-sampling techniques require that careful procedures be followed if the analyst is to be provided a material for laboratory testing which truly represents the material existing in the reservoir. There are two general methods for sampling gas wells. os The first utilizes the full-scale field separator, and the second method utilizes a tubing head or line probe which diverts a portion of the produced material to a small-scale portable separator called a "test car". Normally used when detailed testing is required, the latter method will be described in a later section dealing with the sampling of gas-condensate reservoirs. In sampling gas reservoirs for the purpose of determining only the hydrocarbon analysis of the original reservoir material, the method utilizing the full-scale field separator is usually employed as follows. First, the separator and gas measuring equipment are calibrated, and the gas-oil ratio is measured accurately. Samples of the separator gas, the separator liquid and the stock-tank liquid then are taken and forwarded to the laboratory for subseqent testing. A charcoal sample" of the butanes and heavier components in the separator gas sometimes is taken, but this practice has been minimized if not obviated by the recent development of the chromatograph for obtaining accurate hydrocarbon analyses of these heavy fractions in gas samples. TABLE 10-CALCULATION OF COMPRESSIBILITY FACTOR FOR GAS·CAP GAS AT 134 OF (1) (2) (3) (4) (5) redcd. Press. (Col. 1) (Col. 3) (6) Tr Mix. Pseudo· ceded. Temp. (Col. 2) (Col. 4) 3.77 3.47 \3.17 2.87 2.57 2.27 1.97 1.67 1.37 1.07 0.77 1.48 1.48 1.48 1.48 1.48 1.48 1.48 1.48 1.48 1.48 1.48 Pi Mix. Ta pc Pseudo- Mix. Mix. Pseudocrit. Pseudo· erit. Press. Temp. (OR) (psia) C'R or 460 + OF) Table 9 Table 9 T Temp. p Pressure (psia) 594 594 594 594 594 594 594 594 594 594 594 2515 2315 2115 1915 1715 1515 1315 1115 915 715 515 401 401 401 401 401 401 401 401 401 401 401 667 667 667 667 667 667 667 667 667 667 667 (7) Z Compressibility factor (Fig. 20) .780 .780 .784 .790 .800 .815 .832 .855 .875 .900 .925 with the temperature the same in both cases. For convenience, therefore, it is customary to use the compressibility data in terms of these relations as follows. V = 1,000 Vb Pb Tr Zr _ 1,000 B (9) 5.615 pr Tb Zb - 5.615 g where V = volume of gas, in bbl at P and Tr/Mscf gas, Vb = volume of gas, in Mscf, Pb = base pressure from which volume is being converted, psia, Tb = atmospheric temperature, 460 + OF, .95 1 : I '">- 0 .,. I ~ i: :i !!i I , ~I-' i '""8'" r-~ I-eH- ~--L f-- -f - e- e- I .80 f-- i~ 'I.. r-c- e. e- -f-f-- .75 e-~-~ "e- - 1+-4- f -; -iT ;-!- I ~+- f- - - -H--- - c-r- i i I tt I .85 w N ,1 ! 1,\ - - -- e-- - - - f-=- I.5no 1,000 f- =li- 2,000 2,500 PRESSURE, PSIG Fig. 20-Calculated compressibility-factor curve for gascap gas (Table 10). 700 1.0 -.. 1_ Cf) 'CM""""' U"C .6 0.' V ~ TR 680 r-. ).~ r"_ 1.. 0.8 " 0.7 ..JCf) «m o « '1.3 0.' .. 380 t=Cf) a:: -,." II 0.' o a:: " 1.~' ,,1..'0. ~RITICAL TEMPERA~~~..L o 1.0 2.0 PSEUDO·REDUCED PRESSURE 3.0 4.0 '.0 '.0 1.1.1 Cf) a. 7.0 =MOLECULARAB;~~~:~E P~:I~I~~~ -I--" 620 0:: o o t= i."'" ::JI.I.I T R- MOLECULAR AV[RAGE 0.3 ..J « o ./ 340 8.0 PRESSURE Fig. 19-Compressibility of natural gases (after Brown, Ref. 30). a:: a. 640 O(!) ABSOLUTE TEMPERATURE 0.4 Il V ~ 660 1.:::-:,...- ./ 1.1.1 01.1.1 '1.2 268 1.1.1 ./ .lA N a:: :J Cf) Cf) ./ "I--, 10' ~I~ « a. W '~':"M.ocn"cm o 0 ::J 300 O.S 0.6 0.7 O.B 600 0.9 1.0 SPECIFIC GRAVITY OF GAS: tAIR=I.O) 1.1.1 Cf) a. Fig. 21-Approximate pseudocritical temperature and pressure in relation to gas gravity; air = 1.0 (after Brown, Ref. 30). JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 fraction times critical temperature, which have been computed for each of the individual components, while the pseudocritical pressure is calculated by adding the individual-component products of mol fraction times critical pressure. The pseudoreduced temperature is the ratio of the pseudocritical temperature to the absolute temperature under consideration; similarly, the pseudoreduced pressure is the ratio of the pseudocritical pressure to the absolute pressure. A classic correlation by Brown'· gives Z factors plotted against pseudoreduced pressures for various pseudoreduced temperatures, as shown in Fig. 19. The Z-factor curve for the sample gas is then obtained by determining the pseudoreduced temperature for the gas, which is (460° + 134°F/401°R, or 1.48. Since the compressibility curve is to be based on the gas at reservoir temperature for the pressure range between atmospheric and the original reservoir pressure of 2,515 psia, various pressure points throughout the range are chosen and the corresponding reduced pressures calculated. With the reduced temperature and pressure data, the corresponding Z factors are obtained from Fig. 19. These determinations are illustrated in Table 10, and the Z-factor curve is plotted in Fig. 20. In case a hydrocarbon analysis of a particular gas is not available, a similar procedure may be utilized to determine compressibility relations, provided the specific gravity of the gas is known. This process utilizes correlations by Brown'· of pseudocritical temperature and pressure with gas specific gravity, as shown in Fig. 21. If the density of the gas changes as pressure changes, this must be taken into consideration and Z factors must be calculated at each point corresponding to the proper density value. In oil-production operations, volumes of produced free or gas-cap gas are metered at the surface and referred to some base temperature and pressure. It is necessary in reservoir calculations, therefore, particularly in volumetricbalance calculations, to refer these volumes back to various reservoir pressures. These relative gas volumes are calculated utilizing the compressibility factors as barrels of gas at the reservoir pressure and temperature per thousand cubic feet of gas at standard conditions. In addition, it is necessary to refer volumes of gas at original reservoir conditions to various reservoir pressures below the original pressure as barrels of gas at reduced reservoir pressure per barrel of gas at original reservoir pressure, Zb Pr T,. = compressibility factor at atmospheric pressure, = reservoir pressure at reservoir conditions, psia, = temperature to which volume is being con- V = where C = (10) Sampling and Testing Retrograde Gas-Condensate Reservoirs The problems involved in the study of gas-condensate reservoir materials are many and complex if complete phase-behavior analyses are to be made so that operations yielding maximum economic recovery may be followed. The basis for the complexity of the problem lies in the change of composition of produced material brought about by the retrograde condensation in the reservoir of the heavier hydrocarbon components as reservoir pressure drops. This retrogade condensation drastically affects desirable operations because the condensate material provides a large portion of the income from the produced gas (or, conversely, would provide the loss of income if allowed to condense in the reservoir to form a liquid saturation). Because this liquid saturation constitutes only a small per cent of the entire reservoir pore volume, displacement of it from most areas of the reservoir other than adjacent to wellbores cannot be accomplished mechanically by producing the reservoir gas. The problem of surface separation is involved in gas production, whether the produced gas is at original reserTABLE ll-PRESSURE-VOLUME RElATION OF GAS CAP AT 134 0 F = C~ = C = 178.1 By. 1,000 Pb Vb T . 5.615 ZlJ Til p Data, C = ·1,000 X 14.65 ~< 1 X 594 = 2,980. 5.615 X 1 X 520 (2) (3) z Compressp p Pressure (psig) Pressure 2500 2300 2100 1900 1700 1500 1300 1100 900 700 500 2515 2315 2115 1915 1715 1515 1315 1115 915 715 515 MARCH, 1962 {psia) . 2 "" '.0 Q. ~ en 1\ , •• 0 « (!) ...J en en 1\ 3.0 I\. . at CD 2.0 r..... a; Vj =.9242,..., ~ ,.0 a:: o > RESERVOIR 1,000 1,500 PRESSURE: 2,000 2.500 PSIG Fig. 22-V-curve (pressure volume) for gas-cap gas at 134°F (Table II). 1,000 Pb Vb T,. 5.615 Zb Tb . (1) en 500 C~ p,. Equation, V (,) ibility Factor (Fig. 20) .780 .780 .784 .790 .800 .815 .832 .855 .875 .900 .925 (4) V or 178.1 By (bbl gas at p/Mscf gas) 2980 (Col. 3) (Col. 2) Vi = .9242 1.0041 1.1046 1.2293 1.3901 1.6031 1.8854 r2.2851 2.8497 3.7510 5.3524 (5) By/Byi (bbl gas at p/bbl gas at pi) 1.0000 1.0864 ,1.1952 1.3301 1.5041 1.7346 2.0400 2.4725 3.0834 4.0586 5.7913 voir pressure or at some reduced pressure. It is necessary, therefore, to establish proper separation conditions if a maximum amount of liquid is to be recovered in the separator. After reservoir pressure drops and liquid drops out in the reservoir to form a hydrocarbon saturation, the hydrocarbon analysis of the composite material produced to the surface will have changed considerably, depending upon the amount of material condensing in the reservoir due to retrograde effects. The produced material is leaner, the heavy components of the original material being the first to drop out in the reservoir as pressure drops. Conditions of one- and two-stage separation still will exist where maximum stock-tank liquid will be separated at the surface; however, these separator conditions may have changed substantially from the corresponding conditions where original reservoir material is being produced from the reservoir. The reservoir may be produced by pressure depletion or by cycling operations. In straight pressure-depletion operations, the liquids that condense by retrograde are lost. To eliminate some of the retrograde loss in cycling operations, the dry gas is returned to the reservoir to displace the condensate gas at high reservoir pressure. Cycling may be carried out at anyone or a combination of changing reservoir-pressure conditions during the producing life of the reservoir. Selecting the better method for a specific reservoir, however, depends upon the economics and other factors involved. In making studies of condensate-gas reservoirs, it is necessary to know the quantity and quality of the material recoverable under both types of operations. Complete phase-behavior data of the reservoir fluid under conditions of pressure depletion generally will provide the information needed to evaluate both methods of operations; therefore, field and laboratory tests are designed to provide such information. This information includes the following: (1) the quantity, hydrocarbon analysis and specific volume of original material in the reservoir; (2) the quantities of vapor and condensed liquid in the reservoir at subsequent reduced reservoir pressures; and (3) the complete surface separation history as reservoir 269 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 verted, 460 + of, Zr = compressibility factor at reservoir conditions, and By = volume of gas at reservoir conditions per volume of gas at standard conditions. Complete calculations of a V-curve for example gas analysis are shown in Table II, and results are plotted in Fig. 22. The relation of barrels of gas at reduced reservoir pressures per barrel of gas at initial conditions of pressure and temperature is determined by dividing the value for V at the pressure in question by the value for V, at initial conditions. When plotted, the relation is called the By/By, curve. Complete calculations of the curve from the example gas analysis are shown in Table 11. This curve closely parallels the V-curve and, therefore, is not illustrated. For convenience in calculating values for V and By/By" Eq. 9 is rearranged and all constant factors are grouped together as one constant, as follows. 6.0 lL pressure decreases, which includes optimum separation data together with hydrocarbon analyses of separator gas, separator liquid, stock-tank gas and liquid. Test Car Method t From Well From Field Separator 10.000 Crosby # 10,000 # Heise Trap ~ f";-1 LJ Healer Field Separator Method The test car method of testing condensate-gas material, whereby complete phase behavior is determined, is quite time-consuming and expensive because it involves a great deal of laboratory work. To simplify the testing procedure 150 5 \ 0 ~C4+ Ind 5 ~ o/-_ .... ____ ~ IN PROOUCED ~OTAL c4 + ~ROGRADE V ~ ~ LIQUID FRACTION LIQUID IN I ' 1000 1500 PRESSURE, PSIA AT roOF Fig. 23-Flow diagram of portable apparatus for gas-condensate testing (from Hoffman, Crump and Hocott, Ref. 32). 270 500 ~ $A~ 5 0 / \ \ Heater 2000 , ~ 2500 3()00 Fig. 24-Retrograde liquid condensation and C4 + fraction in produced gas resulting from depletion of a condensatebearing reservoir (from Standing, Lindblad and Parsons, Ref. 34). JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Gathering the afore-mentioned data is best accomplished by using a test car, where all data are obtained by actual measurements or where some data are calculated with some actual measurements used as control data. The test car method of sampling condensate-gas reservoirs is described in detail by Flaitz and Parks" and by Hoffman, Crump and Hocott." A flow diagram of a portable apparatus given in Ref. 32 is shown in Fig. 23. Katz and Brown" have pointed out that this method requires accurate calibration of field separation equipment and a determination of proper sampling rates and conditions in order to divert aliquot portions of the produced stream into the small-scale separators of the test car. The aliquot portion of the produced stream is heated and compressed to reservoir temperature and original reservoir pressure, and then produced to one- and two-stage productionseparator (test car) systems at varying controlled pressures. Separated materials are sampled and sent to the laboratory where their hydrocarbon analyses are determined. The hydrocarbon analysis of the original reservoir material is found from these tests, from which the amount of hydrocarbons originally in place in a unit volume of pore space may be determined; a compressibility factor then can be determined by pseudocritical calculations. In addition, this compressibility-factor value may be checked in the laboratory by using a pressure-volume cell. Also from these tests, the optimum conditions of one- and two-stage separator systems are determined for conditions where the reservoir material is produced while the reservoir is at original pressure. The aliquot material is produced to the test car and flashed at various pressures below original reservoir pre~­ sure in the high-pressure retrograde separator at reservo~r temperature. At each of these high-pressure tests, quantIties of liquid and gas formed and their hydrocar.bon analyses are determined from the samples so obtamed. Data from these tests are used to indicate the severity of retrograde condensation by plots such as those of Standing, Lindblad and Parsons" shown in Fig. 24. T~e analyses of the gas usually are determined by dIfferences between the analyses of the original material and those of the produced liquid because some difficulty exists in determining accurate gas analyses at the high temperature and pressure. Plots of liquid content and hydrocarbon analyses of the gas produced during the depletion of the reservoir are illustrated in Figs. 24 and 25. The change in hydrocarbon analysis of retrograde liquid during the depletion of the reservoir is illustrated in Fig. 26. Gas from the retrograde separator is produced to the production separators (test car), and optimum surface separation conditions are determined for one- and twostage separator systems at various pressure conditions of the retrograde separator. Data from these tests show the changes in field separator conditions that must be made as reservoir pressure drops in order to obtain maximum separator recovery. Samples of separator gas, separator liquid, stock-tank gas (test car) and residual liquid are taken and sent to the laboratory where hydrocarbon analyses are obtained. Shrinkage factors on the condensate and data on liquid content of separated gas are obtained from this information. The tests just outlined may be limited in number to the extent that optimum separator conditions are found for gas at original reservoir pressure only; therefore, fill-in data on such items as shrinkage, gas-oil ratios, gravity of stock-tank liquid and density of separated gas may be calculated by means of phase-behavior calculations. The K-values in such instances may be obtained from various published correlations, from experimental data on the sample, or by further elaborate testing of the sample. so that reservoir behavior can be studied quickly and economically, laboratory procedures may have been developed to simulate test car work. Although the procedure may vary between companies because of the difference in thinking between the individuals involved, the basic information desired is the same and the procedures are v -- O. 8 o. 6 - c, O. 5 z O. 4 l3 O. 3 0 C( a:: O. 2 II.. oJ 0 . 0.1 5 ~ ~ O. I -- ~ 0.06 ~ 0.05 , .... en 0 C2 '\ r-- 0.04 ~ 0.03 '. ,', 0.02 V CrY ......... C4 .h " ""'- ............... 0.01 5 1 L CJ '~ ~ \ - 1000 500 ISOO PRESSURE 5!~ 2000 t?' 2500 3000 PSIA Fig. 2S-Composition change of produced material from gas-condensate reservoir described by Fig. 24. (from Standing, Lindblad and Parsons, Ref. 34). ;CONDENSATE 1 1.0 0.8 A .... O. 6 " o5 ............... 0.4 z o ~a:: 0.2 o "'""'"- --- ~ o i= O. I ~ o _~ , 0.08 en 00D6 a.. o , I V ~ ~ GAS IN CELL AT ORIGINAL RESERVOIR PRESSURE 'TEMPERATURE MERCURY REMOVED PRESSURE REDUCED RETROGRADE CONDENSATE FORMED MERCURY REMOVED CONnlUATION OF STEP 8 Fig. 27-EquiIibrium retrograde condensation of liquid from gas. lLF--r-~ c. / ,1 I t-- t-- lr" , 0.05 0.0J /' .'t. 00.04 o :5 C,,,, 0.3 II.. oJ 0.1 5 Z ~ / t-.. 19 ~ / I ::J 0.02 0.015 I MO 500 I~ ~ PRESSURE 2~ 2500 ~ PSIA Fig. 26-Composition change of reservoir liquid phase for gas-condensate reservoir described by Fig. 24 (from Standing, 'Lindblad and Parsons, Ref. 34). MARCH, 1962 A GAS IN CELL AT ORIGINAL RESERVOIR PRESSURE &TEMPERATURE B GAS REIIOVED PRESSURE REDUCED RETROGRADE CONDENSATE C CONTINUATION OF STEP B ~nRM~n Fig. 23-Differential retrograde conden,ation of liquid from gas. 271 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 i= 0.0 8 basically similar. With this method, a recombined sample is obtained using the field separator method of sampling (described earlier), and then charged into a pressurevolume cell for laboratory testing. If pressure is dropped on a gas sample by increasing the volume without withdrawing gas, a different volume of liquid will drop out by retrograde condensation than will occur if the pressure is dropped by removing gas without changing the volume of the remainder of the sample. The first process (illustrated by Fig. 27) is termed equilibrium, or flash, condensation. The latter process (Fig. 28) is termed differential condensation and is analogous to production from a closed reservoir. A comparison of equilibrium and differential condensation of a retrograde gas measured in the laboratory is presented in Fig. 29. More liquid condenses under equilibrium conditions than under differential conditions because a greater quantity of gas remains in the system from which heavy components may condense as pressure drops . Sloan"·3G describes flash condensation tests performed by step-wise increases in the volume of the material. At several reduced pressure conditions, small subsamples of material are obtained for hydrocarbon analyses and data similar to those of Figs. 24, 25 and 26 are obtained. The 1.00 ~ .75 ~ SATURATED lAS AT OmlKAlRESm PRESSURE_ -I o >.50 EQUILIBRIUM // /"'--,",",~....--"~" /~~ DIFFERENTIAL Fig. 30--.:Condensate lost by retrograde effects. a L---P-=REc-=-S.....,..S-U=R=E--=---=---:~~-=--=--=--=--=---:;..-Fig. 29-Differential and equilibriuDl condensation of liquid froDl retrograde gas. General Retrograde-Condensate-Gas ProbleDls Two main problems face an operator as he attempts to economically produce gas and condensate from a retrograde-gas-condensate reservoir: (l) determining the proper reservoir operating conditions to provide minimum retrograde condensation of liquid from the gas in the reservoir rock; and (2) adjusting separator conditions to provide maximum condensation of condensate from the gas in the stock tank. The following example calculations illustrate the solutions to these two problems. Problem No. I-Retrograde Condensation (Fig. 30) Assumptions: 1. Original Reservoir Volume-lO billion scf of gas. 2. Total Original Gas Recovered-80 per cent. 3. Abandonment Conditions-(a) fast-pressure-depletion, low-abandonment-pressure operations, retrograde = 19 bbl of condensate/MMcf of gas; and (b) slowproducing-rate water-drive operations with high abandonment pressure, retrograde = 10 bbl of condensate/MMcf of gas. Solution: Condensate Lost under 3 (a) = 10,000 X 0.8 X 19 = 152,000 bbl. Condensate Lost under 3(b) = 10,000 X 0.8 X 10 = 80,000 bbl. Difference Lost by 3 (a) over 3 (b) = 72,000 bbl of condensate. It should be recognized that the displacement aspects involved in this type of problem are so influential that they can easily reverse the outcome of the answer. In this regard, the operator may find that more total liquid can be obtained under conditions where the time or reservoir-heterogeneity factor will act to permit more original gas to be produced by pressure depletion. Problem No.2-Separator Recovery (Fig. 31) Assumptions: 1. Original Reservoir Volume-lO billion scf of gas. 2. Total Original Gas Produced to Surface-80 per cent. 3. Separator Producing Conditions-(a) average recovery under 350-psig trap pressure = 95 bbl/MMcf of 272 Fig. 31-Recovery of condensate in separation equipDlent. original gas; and (b) average recovery under 100-psig trap pressure = 90 bbl/MMcf of original gas. Solution: Condensate Recovered under 3(a) = 10,000 X 0.8 X 95 = 760,000 STB. Condensate Recovered under 3(b) = 10,000 X 0.8 X 90 = 720,000 STB. Difference in Recovery of 3(a) over 3(b) = 40,000 STB of condensate. References 25. Thornton, O. F.: "Gas-Condensate Reservoirs-A Review", Pet. Eng. Riel. Annual (1947) 124. 26. Lewis, J. 0.: "Interpretation Well Test Data in Gas Condensate Fields", Pet. Eng. (Sept., 1947). 27. Bulletin T. S. 351, California Nat. Gasoline Assn. 28. Katz, D. L, et al: Handbook of Natural Gas Engineering, McGraw-Hill Book Co., Inc., N. Y. (1959). 29. Kay, W. B.: "Density of Hydrocarbon Gases and Vapors", Ind. Eng. ekem. (1936) 28, 1014. 30. Brown, G. G.: "The Compressibility of Gases", Pet. Eng. (Jan., Feb., March, April, 1940). 31. Flaitz, J. M. and Parks, A. S.: "Sampling Gas-Condensate Wells", Trans., AIME (1942) 146, 13. 32. Hoffman, A. E., Crump, J. S. and Hocott, C. R.: "Equilibrium Constants for a Gas-Condensate System", Paper 219-G presented at AIME Petroleum Branch Fall Meeting (1952). 33. Katz, D. L and Brown, G. G,.: "Sampling Two-Phase Streams from High Pressure Condensate Wells", Pet. Eng. (March, April, 1947). 34. Standing, M. B., Lindblad, E. N. and Parsons, R. L: "Calculated Recoveries by Cycling from a Retrograde Reservoir of Variable Permeability", Trans., AIME (1948) 174, 165. 35. Sloan, J. P.: "Laboratory Studies and Their Relation to Cycling Problems", Oil and Gas Jour. (March 25, 1948). 36. Sloan, J. P.: "Phase Behavior of Natural Gas and Condensate 'Systems", Pet. Eng. (Feb., 1950). 37. Carr, Norman L, Kobayashi, Riki and Burrows, David B.: "Viscosity of Hydrocarhon Gases Under Pressure", Trans., AIME (1954) 201,264. *** JOURNAl. OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 disadvantage of this method is the possibility that some loss in accuracy may result because of the small size of the subsample involved; this possibility is more probable when determining the subsample's hydrocarbon analyses at various reservoir pressures. However, inaccuracies now can be minimized by using the chromatograph. Fundamentals of Reservoir Fluids, Part Four FUNDAMENTALS OF RESERVOIR FLUIDS Theoretical Aspects of Oil and Gas Equilibrium Calculations NORMAN J. CLARK MEMBER AIME Introduction The economic value of produced oil and gas is dependent upon their physical properties. It is of great importance to the operator, therefore, to be able to predict means of producing and handling his reserves which will permit production of materials in such form as to provide a maximum profit. Unfortunately, precise calculations of such are extremely difficult to make. There have been made available in the literature, however, certain generalized data and data on specific hydrocarbon systems that permit the development of methods whereby physical changes occurring to hydrocarbon mixtures can be approximated with a fair degree of precision. Burcik 19 has described in considerable detail various properties and physical changes occurring to hydrocarbon systems, and one method of predicting changes is developed by Buckley." This system may be utilized and calculated results may be correlated with laboratory equilibrium data obtained on the oil sample under controlled conditions in order to obtain more complete and exact results than usually is possible through use of laboratory data alone. Equilibrium calculations for produced hydrocarbon mixtures permit the analyst to determine how particular operating conditions and techniques will affect ( 1 ) gas-oil ratios, (2) composition and gasoline content of liberated gas, (3) composition and gravity of liberated oil, (4) amount and composition of the gas liberated upon flashing the oil from the separator to the stock tank and (5) shrinkage of oil in passing from the reservoir to the stock tank. The Ideal Gas Laws The laws of Dalton and Raoult governing the behavior of ideal gases and solutions were applied by early investigators in calculating the behavior of hydrocarbon mix4VReferences given at end of article. APRIL, 196:! SPE 91 tures (e.g., see Huntington'"). The ideal solution follows the laws of additive volumes. DaMon's law indicates that in a mixture of gases the total pressure is equal to the sum of the partial pressures. From this law, the following relation may be obtained. Partial Pressure of a Gas Component = 7Ty ( 11 ) where 7T = total pressure on the system, psia, and y = mol fraction of the component in the vapor. Raoult's law indicates that the partial vapor pressure of a component in a liquid mixture depends upon the amount of the component in the liquid and the vapor pressure of the pure component. From this law, the following relation is obtained. Partial Vapor Pressure (12) of a Liquid Component = px where p = vapor pressure of the same component in the pure state, and x = mol fraction of the same component in the liquid. When the liquid-gas system is in equilibrium, the total pressure on the system is equal to the vapor pressure of the liquid, and the partial pressure of a component in the gas is equal to the partial vapor pressure of the same component in the liquid. This is shown in the following relation. 7Ty = px (13 ) A rearrangement of this equation to y p -=--= X K , (14) 7T where K = equilibrium or volatility constant, formed the basis for hydrocarbon behavior calculations used by earlier investigators. This relation was found to be a fairly good approximation at temperatures and pressures approaching atmospheric, where molecules are far apart and have little attraction for each other. At high pressures and at temperatures approaching the critical, however, deviations from the behavior of ideal gases and the effects of total pressure on the vapor pressure of the mixture have such pronounced effects on the equilibrium condition that Dalton's and Raoult's laws have been found completely inapplicable." Many past investigations into the estimation and use of critical temperatures, critical pressures and convergence pressures have been employed in an attempt to more precisely ;{73 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Editor's Note: This is the fourth of five Technical Articles in the Fundamentals of Reservoir Fluids series. References, Tables, Figures and Equations are numbered consecutively, but are published only with the particular installment of the series in which they are first mentioned. NORMAN J. CLARK ENGINEERING DALLAS, TEXAS evaluate the relation of K at higher pressures and temperatures."'" K -Values in Equilibrium Calculations When dealing with surface separation problems, the pressures and temperatures usually encountered are low, that is, below 500 psig and 100°F, respectively; in such cases, the published correlations mentioned previously will provide reasonably good approximations. This is especially true if theoretical behavior calculations are made only after calculated data are found to match data obtained in laboratory separation tests (to be described later). Only when dealing with unusual hydrocarbon mixtures will such correlations not be applicable, in which case the analyst may find that, after proper checks are made. only the detailed laboratory data will apply. When dealing with problems in subsurface separation at high pressures and temperatures, a considerable amount of laboratory data must always be obtained if precise calculations are to be made. The significance of Eq. 14 stems from the following. MOL FRAC Cj HYDROCARBON ANALYSIS One use of this relation would be in estimating the analysis of a gas cap in equilibrium with an oil zonea calculation which can be made if the K-values for the significant components are known; in a problem of this type, the components involved may include those that are much heavier than those normally dealt with individually at low temperatures and pressures. The difficulty, however, lies in recognizing the significant components and in knowing the K-values for these components at the elevated pressure and temperature existing in the reservoir. 3H C3 1.0000 EQUILIBRIUM AT ~~~4;;;;';';;"'~ ~TEMP. AND PRESS. MOL FRAC (1 HYDROCARBON C2 C3 ANALYSIS [ .3572 === CN - --r:oooo- Y(C j f,ac) .9287 K(fo, Cj)" - - - = = 2./fJ X(C 1f,ac) .3572 Fig. 32-Hydrocarbon vapor and liquid in equilibrium, illustrating basis of K-values. If accurate composItion analyses of the oil and gas equilibrium phases are to be made, it may become necessary to employ some correlation procedure to smooth out the scatter of laboratory data points and to develop from the data some mutually consistent equilibrium constants. One such procedure, developed by Buckley and published in detail by Hoffman, Crump and Hocott," utilizes plots of log KP (the equilibrium constant times the absolute pressure) vs a function b (~ _. Til ~), T where b is a constant characteristic of the particular hydrocarbon, To is its boiling point in OR and T is the temperature in OR. These plots are reasonably straight lines which permit K-values to be correlated, and they can be extrapolated and interpolated with reasonable precision to determine consistent K -values of other components. The value for the constant b for each component is determined by the following relation. If the qnalyst knows the hydrocarbon analysis of one phase of the material in equilibrium with the other phase and if he has at his disposal the applicable equilibrium constants for all components in the mixture, he can then calculate the hydrocarbon composition of the other phase of the material. In Fig. 32, which illustrates the relation y = Kx of Eq. 14, the mol fraction of methane in the liquid phase is 0.3572 and the value for the equilibrium constant for methane at 2,190 psig and 134°F is 2.60, The value for y, or the mol fraction of methane in the equilibrium vapor, is then 0.9287 (or 2.60 X 0.3572), .9287 C2 b= (logp,. - log 14.7) (15 ) (-~~ -- T~) where p, = critical pressure, psi a, and T, = critical temperature, OR. Values for h for the various pure components through decane are given in Table 12. The example problem shown in Table 13 utilizes Eq. 14 to calculate an analysis for a gas-cap gas in equilibrium with the example oil used earlier. For purposes of these calculations, K-values were obtained from Buckley" for methane, and from Katz and Hachmuth'6 for ethane TABLE 12-VALUES FOR b FUNCTION FOR PURE HYDROCARBON COMPONENTS Component ---Methane Ethane Propane I-Butane N-Butane I-Pentane Value 808 .. 1415 .......... 1792 2045 ..... 2129 2375 Component N-Pentone Hexane Heptane Octane Nonane Decane Value 2473 .. 2780 3061 .. 3333 .. 3602 3B47 .1 () (. II '\ A L () F PET 1I0LEl1!1t TEI:H" OLO(; y Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 The idea of using the equilibrium constant K in phase behavior calculations is sound, requiring only that appropriate K-values be known for components of the material within the range of temperatures and pressures covered by the particular investigation. However, the difficulty in obtaining the proper K-values for these individual components arises from the fact that the values vary not only with temperature and pressure changes, but also with changes in the composition of the mixture; thus, a K-value for a given component actually changes each time the mixture in which the component exists changes. Obviously, therefore, K-values must be chosen with knowledgeable care. The analyst can obtain hydrocarbon K-values for solving his production problems from two general sources: (1) from published general correlations such as those appearing in the Natural Gasoline Supply Men's Assn.-NGAA Engineering Data Book," and (2) from expensive and time-consuming laboratory measurements made on samples extracted from the specific hydrocarbon system under consideration. Examples of the first source include the K -values for carbon dioxide, oxygen and nitrogen reported by Sage, Lacey and Hicks," and those for water reported by Poettmann and Dean." TABLE 13-CALCULATION OF HYDROCARBON ANALYSIS OF GAS·CAP GAS IN EQUILIBRIUM WITH RESERVOIR OIL AT RESERVOIR TEMPERATURE PRESSURE = 2,190 PSIG; y = Kx (1) (2) (4) (5) x K* EquiJib. Constant at 2·,190 psig, 134"F (2205)(Col. 3) 2.600 .864 .562 .343 .149 .158 5,733 1,906 1,240 756 469 349 From Table 14-r .3572 .1021 .1011 .0697 .0411 .0370 .0436 .0364 .0280 .1838 1.0000 Methane Ethane Butane Propane Pentane Hexane Heptane Octane -+ (6) (7) (8) KP Hydrocarb. Anal. of liquid Xo (Mol Fmc.) Component Nonane Decone (3) From Correlation KP Curve of b(-i- -- +) 61 vs b Function (Col. 2205 5,733 2,420 1,300 780 450 265 172** 110** 2.600 1.098 .590 .354 .204 .120 .078 .050 73** 50** .023 KP 2.650 -1.873 1.291 .830 .328 - .167 - .574 - .968 -1.345 -1.699 Calc. Hydroearb. Anal. of Vapor (Mol Frae.) (Col. 7)(Col. 2) Y Aditd. Hydroearb. Anal. of Vapor (Mol Frae.) (Col. 8) (1: Col.8!. .9287 .1121 .0597 .0247 .0084 .0044 .0034 .0018 .0009 .0042 1.1483 .BOB7 .0976 .0520 .0215 .0073 .0038 .0030 .0016 .0008 .0037 1.0000 y K (9) .033 tTable 14 will appear in May, 1962 issue of Journal of Petroleum Technology. C2 -C6 inclusive, Katz and Hochmuth (interpolated for temperature of 134°F). "''''Extrapolated values. *Dato as follows: c I , Buckley; 3.0 C,II I 1 1 c 1.0 U L- r-- J-' 2 ~ I. c , -" ).-' ~ J.,ool--' 0.1 "'" ~~ C4 ,,,.1. The Material-Ba,lance Calculation I 11 I--'I--' Y' .... r-- will be consistent with each other and (2) extrapolate to determine K-values for components heavier than hexane. These calculations are shown in Table 13, and the correlation is illustrated in Fig. 34. An excellent set of K-values now generally available for use with production problems appears in the Natural Gasoline Supply Men's Assn.-NGAA Engineering Data Book." These charts cover a range of convergence pressures between 600 and 20,000 psia. The proper convergence pressure for a particular hydrocarbon system can be calculated by using a method described by Lenoir and White." With the convergence pressure of the system determined, the proper K-values for the components are obtained either directly or by interpolation from the charts. In many cases, the analyst must determine the equilibrium conditions existing between two phases of hydrocarbon materials at a specific set of temperature and pressure conditions, but the only analysis he knows is that of the original single-phase material from which the two phases were derived; further, this known analysis is valid only for the temperature and pressure conditions under which the single-phase material existed. A material-balance I 2.0 b-function plot to (1) smooth the values so that they >f _.-4.. ,.,i, 1,..-1--' .... 1--' ".I.~ 1,..-..... , .... ,,,.1. C6 J.,oo I"'" ++r l t±ttili Ii 100 I LEGEND o X CI 0.01 ITiil'ITIill .,i, 100 150 TEMPERATURE: OF ~~.7 200 Fig. 33-Correlation of K-values at 2,190 psig vs temperature to obtaiu K-values at 134°F. APRIl.., 1962 1+++++-H--J,.rn· c, I I I 1 I c~ I ~i .~cs~ j.- -l-i--W--i-W++-I-l ++1 r~+ H+Ji _1+ ill I ' c, U)';;, Ii 1--" I I I c. 11111' : "co -+I-.,..:-~~4-~l-Il-,:-,I_H-H-+-+-+r-r_ J-, t t;., .I- ·liil. i 1r i I • H i LEGEND x Calculat.d Points Adluat.d Point. t- _ . 1- ( t-+ IT ~'~'iffi~fir .lillI1~~~1~Trr~ C DATA POINTS INTERPOLATED POINTS BUCKLEY'S DATA I--'t 40 50 m iii 1 1 i 1++++++++' . ! !, I I ~ 1,000.__ _ -1 tm1 l J..+.t+++++++++++ i -+++-J i -1.5 EXTRAPOLAI£D -1.00 0.00 1.00 b( 2.00 3.00 ~_~) T. T Fig. 34-Correlation of KP vs b-function to determine K-values for heavier components at 2,190 psig and 134°F. 375 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 through hexane. In this example problem, the assumption is made that no reliable data could be found for octane and heavier components for a pressure of 2,190 psig and a temperature of 134°F; thus, the methanethrough-hexane data must be extrapolated to obtain the proper K-values for components heavier than hexane. Further assume that K-values for methane through heptane could not be found in the literature for a temperature of 134°F; therefore, as shown in Fig. 33, the analyst must plot curves of K vs temperature and then interpolate to find the values of K at 134°F. If there is considerable curvature to the correlations, a better method would be to plot KP vs the reciprocal of absolute temperature-a correlation which, according to Buckley and Lightfoot," usually plots as a straight line. After determining these K-values, each of which is consistent within itself, the analyst must utilize a KP vs calculation which permits the analyst to solve problems of this type is developed in the following paragraphs. Suppose that a given quantity of a single-phase hydrocarbon material (such as a liquid mixture) existing at some elevated temperature and pressure has its temperature and pressure reduced; if none of the original material is lost and if a combination of liquid and vapor results, the following relation will hold. Xo =V, + L, . (16) whereXo = original single-phase material, Ib-mol, V, = vapor at altered conditions of temperature and pressure, Ib-mol, and L, = liquid at altered conditions of temperature and pressure, Ib-mol. The original single-phase material is. composed of all components; i.e., ANAL YSI~ ', .,,,, (2 [ (3 HYDROCARBON ANALYSIS -~­ - -- CN~ ORIGINAL LIQUID HYDROCARBON ANALYSIS (1 .3572 (2 --- CJ } MOL fRAC --- eN - - _ (:: J l.OOOoI LB. MOL X .35n MOL FRAC =.60185 LB MOL X .$.497 MOL FRAC + .3515 La MOL x .0025 /,()L FRA~_ .3571 LB MOL (1 '" .Jsn _oo~,~ . 1.0000 LB MOL C 1 Fig. 35-Material balance of methane in original singlephase liquid with methane in vapor and liquid separated from the original liquid. y, KxXo (22) = -=-=-=--:--::KV,+L, Then, substituting Xo - V, from Eq. 16 in Eq. 22 for L, results in y, = KV, + X o - V, (23) If the relation is based on lib-mol of original material, the following simplified equation results. y, = V,(K - 1) + 1 (24) = y/K, A material balance on anyone component is, therefore, And, since x xo_c,Xo = x,_c,L, + Y,-C,V, . (20) xo_c,Xo = amount of methane in the original material, lb-mol, x,_o,L, = amount of methane in the resulting liquid L" lb-mol, and Y'-C1 V, = amount of methane in the resulting vapor V" lb-mol. The significance and utility of the material balance of Eq. 20 will be illustrated with data of the example oil sample and answers from more complete, subsequent calculations. The value for xo_c, of the oil sample at reservoir conditions is 0.3572 from the hydrocarbon analysis. The value of x,-o, of the L, or separator liquid separated at 0 psig and 70°F separator conditions was found to be 0.0025. The value of Y,-c, of the V, or separator vapor was found to be 0.5497. In addition, L, was found to be 0.3515 lb-mol and V, was found to be 0.6485 lb-mol. Thus, a check by Eq. 20 shows the relationship of these values as illustrated by Fig. 35 to be (1 X 0.3572) = (0.6485 X 0.5497) + (0.3515 X 0.0025), or 0.3572 lb-mol = 0.3564 lb-mol + 0.0008 lb-mol. (25) x, = V,(K - 1) + 1 Problems of flash separation are then solved by a trialand-error calculation utilizing Eq. 24, in which a value for V, is assumed for the amount of equilibrium vapor. The correct value for V, is chosen when the sum of all the calculated mol fractions of the components in either equilibrium phase equals unity. where The values for V, and L, used here, as well as the hydrocarbon analysis of the newly formed vapor and liquid, were calculated by the material-balance equation that incorporates both the volumes and compositions of the two phases, as follows. The fraction y/K from Eq. 14 is substituted for x in Eq. 20, resulting in y,L, (21) xaXo = K + y,V, , and 376 Reference~ 38. Buckley, S. E.: "Calculation of Equilibria in Hydrocarbon Mixtures", Trans., AIME (1938) 127, 178. .39. Huntington, R. L.: "Elements of Vaporization and Condensa· tion", Refiner and Natural Gasoline Manufacturer (March, 1940). 40. Brown, G. G.: "The Compressibility of Gases", Pet. Engl. (May, June, 1940). 41. Smith, K. A. and Smith, R. B.: Pet. Processing (Dec., 19491 4, 1355. 42. Liquid-Vapor Equilibrium in Mixtures oj Light Hydrocarbons. The M. W. Kellogg Co. (1950). 43. Engin,eering Data Book, Seventh Ed., Natural Gasoline Supply Men's Assn. and NGAA (l9571. 44. Sage, B. H., Hicks, B. L. and Lacey, W. N.: Drill. and Prod. Prac., API (1938) 386. 45. Poettmann, F. H. and Dean: Pet. Refiner (Dec., 1948) 25, No. 12. 46. Katz. D. L. and Hachmuth, K. H.: "Vaporization Equilibrium Constants in a Crude OiLNatural Gas System", Ind. and Engr. Chem. (Sept., 1937) 29, No.9. 47. Buckley, S. E. and Lightfoot, J. H.: "Effects of Pressure and Temperature on Condensation of Distillate from Natural Gas", Trans., AIME (1941) 142, 232. 48. Lenoir, J. M. and White, G. A.: "Predicting Convergence Pressure", Pet. Refiner (March, 1958) 37, No.3. 49. Burcik, E. J.: Properties 0/ Reservoir Fluids, John Wiley & Sons, Inc., N. Y. (1957). *** JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Xo = xo-c, + XO-C2 + XO-03 + .... + xo-on ' (17) where xo-o, is the amount of methane in the original singlephase material in Ib-mol. Similarly, the separated phases of the original material are composed of all the components. V, = Y,-c, + Y'-C2 + Y'-03 + .... + Y,-c n (18) and L, = x,-o, + X'-C2 + X'-03 + .... + x,-on (19) where Y,-c, = amount of methane in the V, vapor, mol fraction, and x,_c, = amount of methane in the L, liquid, mol fraction. HYDROCARBON Fundamentals of Reservoir Fluids, Part Five FUNDAMENTALS OF RESERVOIR FLUIDS Practical Application of Oil and Gas Equilibrium Calculations NORMAN J. CLARK Editor's Note: This is the fifth and last Technical Article in the Fundamentals of Reservoir Fluids series. References. Tables, Figures and Equations have been numbered consecutively, but were published only with the particular installment of the series in which they were first mentioned. Introduction When hydrocarbon materials are subjected to changing conditions of pressure and temperature, their physical properties change. By utilizing methods to predict these changes, the operator can determine the one set of pressure-temperature conditions that will provide the hydrocarbon materials in a form offering the maximum economic advantage. He then can purchase and install equipment designed to provide these optimum separator conditions, thus eliminating time-consuming field experimentation and costly equipment modifications and replacements. The utility of the equilibrium equations in determining optimum field separation conditions can perhaps best be presented through a complete series of calculations. Optimum field separation conditions will be determined by flash calculations for both single-stage and two-stage separator systems. Preliminary Calculations The hydrocarbon analysis of original reservoir oil is recorded on the basis of weight per cent, as shown by the lab data of Table 4. * This analysis must first be converted to a mol per cent basis for use in all subsequent calculations. This conversion is shown in Table 14. The values for molecular weights of components methane through pentanes are for paraffin series from published literature. The molecular weights for hexane and heavier components are experimental values determined in the laboratory. In addition, the gallons of liquid per mol and the vapor equivalent, in cubic feet of vapor per gallon of liquid, must be obtained for each component. Published data are used for normal paraffin components for methane through pentane, and laboratory data are used to determine the MAY, 1962 values for the heavier components. Calculations for the example oil are shown by Table 14. Verification of Calculations and [(-Values Used Before a series of calculations can be considered reliable, especially if K-valves are used which were obtained from the literature or from some correlation procedure, a trial flash calculation must be made for a case in which corresponding laboratory data are available. Thus, laboratory data can be checked against the calculated results, the differences studied, and the causes for variation eliminated before long, tedious behavior calculations are subsequently made. The best check calculations are based on the O-psig flash separator test because it is considered the easiest to control and, thus, the most reliable of the laboratory separator tests. The first calculation involves determining the hydrocarbon analyses of residual-liquid and separated-gas phases, and the quantity of liquid and gas formed at 0 psig and 70 P separation conditions resulting from 1 mol of original sampled oil at 2,190 psig and 134°P. It is significant that 1 mol of the original oil is used as a basis and its original conditions of temperateure and pressure are not considered in the flash calculation. Pirst, a value for the quantity of gas formed V" (some fraction of a mol of stock-tank vapor formed from 1 mol of original singlephase material) is estimated. This will be some value between 0 and 1.0 if the change of state in the original material results in two phases. If by Eq. 24** the sum of the component hydrocarbon analyses for the gas formed is calculated to be 1.00, the assumed value for V" is correct; if not, new values for V" are chosen and the calculations are repeated until a V" is found which will result in the component analyses' summing to equal unity. Table 15 illustrates this procedure. After the hydrocarbon analysis of the equilibrium gas is found, the hydrocarbon analysis of the residual oil is calculated by Eq. 14. * * The next step is the calculation of molecular weight and GPM of the various saleable components of the equilibrium gas formed, and the gallons per mol and pounds per mol of the equilibrium liquid formed. These data, calculated in Table 16, are based on the preliminary data 0 Optimum Field Separation Conditions ':'Jour. Pet. Tech. (Jan., 1962) 15. NORMAN J. CLARK ENGINEERING DALLAS, TEXAS SPE 91 '·"\Jour. Pet. Tech. (April. 1%2) 373. 491 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 MEMBER AIME tABLE 14 (I) (2) HYDROCARBON ANALYSIS AND DATA OF SUBSURFACE OIL SAMPLE (3) (4) (5) (6) (7) (8) Density (gm/cc at 60° F) Lab. Data Density (Ib/gal at 60° F) 8.345 (Col. 6) Gal/Mol, Published Data or (Col. 3)/(Col. 7) (9) Vapor Equivalent (cu ft vapor/ gal liquid at 60° F) 379/(Col. 8) 5.696 6.061 6.200 6.361 7.149 7.05 9.0 10.37 12.34 11.92 13.84 13.69 15.098 16.334 17.742 19.337 32.172 53.S 42.0 36.6 30.8 31.8 27.4 27.7 25.10 23.20 21.36 19.60 11.78 Xo Companent Weight Per Cent (From Table4) Molecular Weight Source as Noted Mol/100 Ib Sat. Material (Col. 2)/(Col. 3) Hydrocarbon Analysis of Sample Oil Xo (mol frac) (Col. 4)/~ (Col. 4) Methane Ethane Propane I-Butane N-Butane I-Pentane N-Pentane Hexane Heptane Octane Nonane Decane + 7.39 3.96 5.75 0.79 4.44 0.84 2.98 4.11 5.57 5.17 4.44 54.56 16.03t 30.05t 44.06t 58.08t 58.08t 72.09t 72.09t 86. tt 99. tt 110. tt 123. tt 230.* tt .4610 .1318 .1305 .0136 .0764 .0117 .0413 .0478 .0563 .0470 .0361 .2372 .3572 .1021 .1011 .0105 .0592 .0091 .0320 .0370 .0436 .0364 .0280 .1838 1.2907 1.0000 100.00 .6826 .7263 .7430 .7623 .8567* * Adjusted values to permit matching calculated with laboratory separation data. t From publ i shed literature. t t From lab data. ATMOSPHERIC SEPARATION FLASH CALCULATIONS-SUBSURFACE OIL TO STOCK TANK (CHECK OF LABORATORY RESULTS AND FLASH CALCULATIONS)* Equations: Conditions of Flash: Estimated (1) K Xo Yst Liquid Xo V st (3) (2) = Vst(K-1) + 1; +; Y t Xst= Xo = V st +L st ' From 2,190 psig and 134° F = .6485 , Lst (4) To 0 psig and 70° F • = .3515. (5) (7) (8) Yst Xst Hydrocarbon Analysis of Stock-Tank Vapor V st (mol frac), (Col. 4)/(Col. 6) Hydrocarbon Analysis of Stock-Tank Liquid Lst (mol frac), (Col. 7)/(Col. 3) (6) xo Com~onent Hydrocarbon Analysis of Original Reservoir Oil Xo (mol frac from Table 14) Methane Ethane Propane I-Butane N-Butane I-Pentane N-Pentane Hexane Heptane Octane Nonane Decane+ K Equi I ibrium Constant at opsig and 70° F K xo' K - 1, Vst(K - 1) + 1, (Col. 2)(Col. 3) (Cal. 3) - 1 V st (Col. 5) + 1 221.10 32.99 8.299 3.197 2.180 .898 .6463 .2177 .0701 .0223 .0066 78.97692 3.36828 .83903 .03357 .12906 .00817 .02068 .00805 .00306 .00081 .00018 .3572 .1021 .1011 .0105 .0592 .0091 .0320 .0370 .0436 .0364 .0280 .1838 220.10 31.99 7.299 2.197 1.180 .1020 .3537 .7823 .9299 .9777 .9934 -1.0000 143.73485 21.74552 5.73340 2.42475 1.76523 .93385 .77063 .49268 .39696 .36596 .35578 .35150 1.0000 .5497 .1549 .1463 .0138 .0731 .0087 .0268 .0163 .0077 .0022 .0005 .0025 .0047 .0176 .0043 .0335 .0097 .0415 .0751 .1098 .0995 .0787 .5231 1.0000 1.0000 * Subscripts 0, 1, 2 and st denote conditions at reservoir, first-stage separator, second-stage separator and stock-tank, respectively. TABLE 16 - ATMOSPHERIC SEPARATION, CALCULATION OF FLUID DATA FROM RESULTS OF FLASH CALCULATIONS (CHECK OF LABORATORY RESULTS AND FLASH CALCULATIONS) (9) (8) (6) (7) (2) (3) (4) (5) (1) Yst Component Methane Ethane Propane I-Butane N-Butane I-Pentane N-Pentane Hexane Heptane Octane Nonane Decane+ Hydrocarbon Hydrocarbon GPM* Vapor Analysis of Analysis of Stock-Tank Mol Wt. Gal/Mol Lb/Mol Stock-Tank Stock -Tank Mol Wt.of Equivalent, Gal/Mol of VaporVst Stock - Tank Stock- Tank Vapor Vst Liquid Lst Components Components (cu ft vapor/ Stock -Tank 1,000(Col.2) (mol frac from (mol frac from (from (from gal component, Vapor Vst Liquid Lst Liquid Lst (Col.6) (Col. 3)(Col. 5) (Col. 3)(Col. 4) Table 15) Table 15) Table 14) Table 14) from Table 14) (Col. 2)(Col. 4) .5497 .1549 .1463 .0138 .0731 .0087 .0268 .0163 .0077 .0022 .0005 1.0000 *GPM 492 Cg (10) Xst 3.997, C4 .0025 .0047 .0176 .0043 .0335 .0097 .0415 .0751 .1098 .0995 .0787 .5231 16.03 30.05 44.06 58.08 58.08 72.09 72.09 86 99 110 123 230 1.0000 7.05 9.00 10.37 12.34 11.92 13.84 13.69 15.098 16.334 17.742 19.337 32.172 53.80 42.00 36.60 30.80 31.80 27.40 27.70 25.10 23.20 21.36 19.60 11.78 8.8117 4.6547 6.4460 .8015 4.2456 .6272 1.9320 1.4018 .7623 .2420 .0615 3.997 .448 2.299 .318 .968 .649 .332 .103 .026 29.9864 9.140 .0176 .0423 .1825 .0531 .3993 .1342 .5681 1.1339 1.7935 1.7653 1.5218 16.8292 .0401 .1412 .7755 .2497 1.9457 .6993 2.9917 6.4586 10.8702 10.9450 9.6801 120.3130 24.4409 165.1101 2.747, C5 + = 2.396. JOURNAL OF l'ETROUWM TECHNO.LOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 TABLE 15 - tween these two measurements so that, when only one is known, the other can he determined for purposes of evaluating the vapor equivalent for a component. This relation is given by the following equation. 379 X 8.345 X D (26) Vapor Equivalent MW where Vapor Equivalent = cu ft (at 60°F)/gal of liquid, 379 = cu ft of gas/lb-mol of gas, 8.345 = weight of water, lb/gal, D = density of component, gm/cc, and MW = molecular weight, or lb/lb-mol. Fig. 36 is a correlation of molecular weight and density for pure paraffin components and for hydrocarbon mixtures obtained from residual fluids of reservoir-oil samples and gas-condensate samples. This correlation, made with data from several thousand measurements, is used to determine or verify one parameter when the other is known. Adjustments in the molecular weight and density of the heavy fraction may be considered as changes which compensate for inaccuracies in the K-values used. To minimize the amount of this required adjustment, the best K-value for the heavy fraction is obtained by a plot of b vs K-values on semilog paper for the various components at the temperature and pressure under consideration. The best K-values obtainable for the light components, together with their b-values from Table 12, * * are first plotted as shown on Fig. 37. The line is extrapolated to a b-value calculated by Eq. 15** for the heavy fraction or fractions, utilizing values for critical pressure, critical temperature and average boiling point for the heavy frac':"'J our. Pet. Tech. (April, 19'62) 374. 500 I 450 400 ~ LEGEND: CURVE A PURE COMPONENTS CURVE B COMPONENT CUTS BY HYPERCAL DISTILLATION OF CONDENSATE SAMPLES CURVE C "Jour. Pet. Tech. (Jan .. 1962) 16. I ~~tlbuA:~ F~81t M~~1~R~\L °rAMPLES 350 TABLE 17 - ATMOSPHERIC SEPARATION, CALCULATION OF FLUID DATA FROM RESULTS OF FLASH CALCULATION (CHECK ON VALIDITY OF LABORATORY DATA AND FLASH CALCULATIONS) 300 Ib 165.1101 Ib/mol gal/mol = g.;r = 24.4409 6.756 ;: 42.9° AP I Stock-Tank Gas-Oil Ratia: Vst (cu ft/mol)(gal/bbl) _ .6485 x 379 x 42 .3515 x 24.• 4409 Lst (gal/mal) 250 Aj 1202 sef gas/STB 200 Flash Shrinkage Factor: 24.4409 (gal/mal)(mal/bbl) Lst 1/B 0: f = :::...----=-'----'----'::..: (gal/bbl) .602 STB oillbbl orig. sample oil. x 2.9431 x .3515 150 42 v 100 Specific Gravity of Separator Gas: SG = MW gas MWair = 29.9864 = 1.0351 28.97 (mol/100 Ib)(cu ft/bbl) mol/bbl = (100)(cu ft/lb) = C B/ /~ 1/ V ./ 50 Mals per Barrel Original Reservoir Oil: 30 1.2907 x 5.615 100 x .024625* =2. 9431 * Adjusted to cause agreement in calculated and lab-measured shrinkage-factar data. MAY, 19j'il I I Gravity of Stock Tank Oil: I III 0.4 0.5 0.6 0.7 0.8 0.9 1.0 DENSITY Fig. 36-Molecular weight vs density for pure hydrocarbon cmnponents and hydrocarbon mixtures obtained from residual fluids of subsurface oil samples and condensate samples. 493 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 calculated in Table 14 and the hydrocarbon analyses of the equilibrium materials calculated in Table 15. With these calculated data, it is then possible to calculate the (1) gravity of stock-tank oil, (2) gas-oil ratio, (3) shrinkage factor and (4) specific gravity of gas. These calculations are made with units explained in Table 17. The calculated values, however, were found to vary slightly from the corresponding laboratory values; therefore, certain adjustments of calculated data which were within laboratory accuracy were made to permit complete agreement within allowable precision. Adjustments can be made on the molecular weight and/or density of the C lO + fraction in the original material (Table 14) and the specific volume of the original material (Table 6*). These quantities are difficult to measure in the laboratory, and the allowable adjustment in values may be up to as much as 20 and 10 per cent, respectively. Any change made in the value for molecular weight of the Co + fraction will require (1) recalculation of the hydrocarbon analysis on a mol fraction basis in Table 14, (2) new volumetric factors for the C,o + fraction in Table 14 and (3) re-evaluation of the mols-per-barrel factor in Table 17. From a study of the tabular calculations, increasing the molecular weight will increase the gallons-per-mol factor, which increases API gravity, decreases gas-oil ratio, decreases shrinkage (Le., increases the shrinkage factor) and increases the specific gravity of gas. Increasing the value for density will have an opposite effect on these calculated values. Increasing the specific volume of reservoir oil will result in decreasing the mols-per-barrel value, thus increasing shrinkage (decreasing the shrinkage factor). A final and reasonable check for the example calculation was made when the molecular weight of the C IO + fraction was changed from 285 to 230; the density of the C,o + fraction changed from 0.8472 to 0.8567 gm/cc, and the specific volume of the original material changed from 0.02428 to 0.024625 cu ft/lb. The process of adjusting molecular weights and densities often requires a knowledge of the general relationship be- 5000 - ~ :::::: CURVE EXTRAPOLATED TO b-VALUE 4618 TO FIND K-VALUE FOR C6 + FRACTION OF.0003 4500 -.. 4000 --------- / -~.----- --.- - .- -------"- ---------- 1--- - " .. - / -_.- - - - ---'---, - -- 3500 3000 / / 2500 -- -- -- -- --- -- -- / I I _.------+ ------7,4.. -----. / ~ -- -- / I I I X""""'- X:;-X/;':C5 (2473) ~x '-C (2375) ~X_ N-C 4(218 ) x I-C 4 (2045) C 3 (i792) I I 3 2000 / 1500 I I I I ~XC2(i415) 1000 ~X'6;(8f8) I I I I 500 o 1000 -.-----.--- --_ .. - I I I 10.0 100 1.0 0.1 0.00001 0.0001 0.001 CONSTANT K Fig. 37-Plot of b·values vs K-values of hydrocarbon components to determine K-value for. residual mixtures tion or fractions from Figs. 38, 39 and 40, respectively. The following example illustrates this calculation for the case where a K-value is obtained for the entire Co + fraction utilizing the data of Table 4 for 0 psig and 70°F conditions. Given: C, + fraction having SG = .8147, MW = 203. Then: gravity = 42.2° API; p" critical pressure = 276 psia, from Fig. 38; To, critical temperature = 795°F, from Fig. 39, = 795 + 460 = 1,255° R; T b , boiling point = 472°F, from Fig. 40, = 472 + 460 = 932° R; log 276 - log 14.65 and b 1 1 ------_.932 1,255 2.441 - 1.166 .0010729 - .0007968 = 4,618. The curve of Fig. 37 is extrapolated to a b-value of 4,618, and the K-value of .00033 is thus determined for the Co + fraction. In this case, all the heavy components in the Co + fraction are handled together. More accurate equilibrium calculations will be accomplished when each of the heavy-component cuts is handled separately so that b-values and K-values are obtained for each. 100 leo 140 160 leo 200 a.. <f) UJ Q: Il- .J 5 180200 -1:+ - "" . _+ ~ j,j De ... => -< '''' ------ ." --- De W 0.. ...'" W .J « o ;:: it' o -- -- f-- 1100 - ! - 1-- r- , ~ I ,-I-!-. ;- -, I I .,.~ '0" I I_+~'. -l I i 1 i \-t- 'I I : I ,-'" -- k:~V:;::::~ ~ -·-~.Irr·· lo~ , V I--"" V ...... 1- ,f-""" 'J.....- .,0- --..... ~ V I--"" f' ...... V I- W ...... L-- :..r-:v v I ...... I- .- ...... L-- L-- ...... 1--"" -~ '''''' , 1- -- • '0f-""" !1"~;6: .~'" I - I ~ i;:::::;:: "':"- /;" :::.;.--:: ....... ;:::: ~ ~~~~~ '" ." ." I 1--- - - ." I ~~ - I I r--f· 1-- - l - I- "'" I- -I-- '" 1- 000 ! • :-- f- ,- I -r-- -- -- --- -- "----I- I ,--- ,- ---1--- ." MOLECULAR WEIGHT Fig. 39-Critical temperature of petroleum fractions vs molecular weight. (Courtesy Petrocon Engineering Co., Compton, Calif.) MOLAL BOILING POINT, OF ... iii ui Q: => <f) A second and third set of check calculations may be made to determine the match between the calculated data and the lab separation data for the two remaining conditions of laboratory separator pressures listed in Table 2- 220 « (Co +)' $00 I (!) iii ~ ." Q: « .J => 0 40~ UJ .J E Q: 0 ~ 0 MOLECULAR WEIGHT Fig. 38-Critical pressure of petroleum fractions vs molecular weight. (Courtesy Petroeon Engineering Co., Compton, Calif.) 494 MOLAL BOILING POINT, OF Fig. 40-Molecular weight of petroleum fractions vs molal boiling point. (Courtesy Petrocon Engineering Co., Compton, Calif.) JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 EQUILIBRIUM 0.01 to insure applicability of the equilibrium constants used. These check calculations are made in a similar m:umer to the single-stage separation calculation presente6 in the following paragraphs and, therefore, will not be shown here. Instead, for this series of example calculations, it is assumed that the data providing a match with the O-psig flash will also provide a suitable match for the other labOI"atory separator conditions. Single-Stage Separation Single-stage separation, illustrated in Fig. 41, is defined as the process wherein original reservoir oil Xo (single phase) is produced to a separator where vapor V, and liquid L, are separated while at equilibrium conditions; the liquid L, (single phase) is then produced to the stock tank where vapor V", and liquid L." are separated while at equilibrium conditions. The separator conditions of pressure and temperature chosen to illustrate the method of calculating single-stage Fig. 41-Schematic diagram showing flash separation of original reservoir liquid through one separator stage and stock tank. Equations: (1) Component Methane Ethane Propane I-Butane N-Butane I·Pentane N·Pentane Hexane Heptane Octane Nonane Decane + Y, = K Xo V, (K - 1) + 1 x, ; Conditions of Flash: Liquid Xo From Estimated V, = .5052 L, = .4948 (2) (4) (3) Xo Hydrocarbon K Analysis of Original Res· Equilibrium ervoir Oil Xo Constant ,t K xo 100 psig and (mol frac from (Col. 2)(Col. 3) Table 14) 70° F .3572 .1021 .1011 .0105 .0592 .0091 .0320 .0370 .0436 .0364 .0280 .1838 28.6399 4.3679 1.0985 .4294 .3043 .1238 .0933 .0329 .0121 .0042 .0013 10.23017 .44596 .11106 .00451 .01801 .00113 .00299 .00122 .00053 .00015 .00004 Y, XO = V, + L, . =- ; K 2,190 psig and 134° F To (6) (7) V,(K - 1) + 1 V, (Col.5) + 1 Y, Hydrocarbon Analysis of First.Stage Vapor V, (mol frac), (Col. 4)/(Col. 6) (5) K - 1 (Col. 3) - 27.6399 3.3679 0.0985 - .5706 - .6957 - .8762 - .9067 - .9671 - .9879 - .9958 - .9987 -1.0000 100 ps ig and 70° F 14.96368 2.70146 1.04976 .71173 .64853 .55734 .54194 .51142 .50091 .49692 .49546 .49480 1.0000 TABLE 19 - K Conditions of Flash: Component Estimated (2) x, Hydrocarbon Analysis of F irst·Stage Sep. Liquid L,(mol frac from Table 14) Methane Ethane Propane I·Butane N·Butane I·Pentane N·Pentane Hexane Heptane Octane Nonane Decane+ .0239 .0378 .0963 .0148 .0913 .0163 .0590 .0723 .0870 .0733 .0565 .3715 1.0000 MA Y. 1962 .6836 .1651 .1058 .0063 .0278 .0020 .0055 .0024 .0011 .0003 .0001 .0239 .0378 .0963 .0148 .0913 .0163 .0590 .0723 .0870 .0733 .0565 .3715 1.0000 1.0000 SINGLE-STAGE SEPARATION FLASH CALCULATIONS-FIRST-STAGE LIQUID TO STOCK TANK Equations: (1) (8) x, Hydrocarbon Analysisof F irst.Stage Liquid L, (mol frac), (Col. 7)/(Col. 3) x, Yst K Liquid L, V st = .1507 , Lst (3) From 100 psig and 70° F .8493. (4) K Equilibrium Constant at o psig and 70° F K x, (Col. 2)(Col. 3) 217.0068 31.3946 7.6667 2.9184 1.9796 .7993 .5755 .1918 .0602 .0188 .0056 5.18646 1.18672 .73830 .04319 .18074 .01303 .03395 .01387 .00524 .00138 .00032 (5) K- 1 (Col. 3) - 216.0068 30.3946 6.6667 1.9184 0.9796 .2007 .4245 .8082 .9398 .9812 .9944 -1.0000 o psig To (6) Vst(K - 1) + 1 Vst (Col.5) + 1 33.55222 5.58047 2.00467 1.28910 1.14763 .96975 .93603 .87820 .85837 .85213 .85014 .84930 and 70° F • (7) Yst Hydrocarbon Analysis of Stock· Tank Vapor Vst (mol frac), (Col. 4)/(Col. 6) (8) Xst Hydrocarbon Analysis of Stock-Tank liquid Lst (mol frac), (Col. 7)/(Col. 3) .1546 .2127 .3681 .0335 .1575 .0134 .0363 .0158 .0061 .0016 .0004 .0007 .0068 .0480 .0115 .0796 .0168 .0630 .0823 .1014 .0860 .0665 .4374 1.0000 1.0000 495 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 TABLE 18 _. SINGLE-STAGE SEPARATION FLASH CALCULATIONS-SUBSURFACE OIL SAMPLE TO FIRST-STAGE SEPARATOR TABLE 20 _ SINGLE·STAGE SEPARATION, CALCULATION OF FLUID DATA FROM RESULTS OF FLASH CALCULATION ( 11) (10) (8) (9) (7) (6) (5) (3) (4) (2) (1) y, x, y., Hydrocarb. Hydrocarb. Hydrocarb. Hydrocarb. Anal. of Anal. of Anol. of Anal. of L,(mol Ls,(mol V, (mol Vsdmol Component Methane Ethane Propane I-Butane N-Butane I-Pentane N"Pentane Hexane Heptane Octane Nenana Decane frac from frac from frac from frac from Table 18) Table 18) Table 19) Table 19) .6836 .1651 .1058 .0063 .0278 .0020 .0055 .0024 .0011 .0003 .0001 .0239 .0378 .0963 .0148 .0913 .0163 .0590 .0723 .0870 .0733 .0565 .3715 1.0000 .1546 .2127 .3681 .0335 .1575 .0134 .0363 .0158 .0061 .0016 .0004 .0007 .0068 .0480 .0115 .0796 .0168 .0630 .0823 .1014 .0860 .0665 .4374 1.0000 1.0000 * GPM first-stage vapor: ** GPM stock-tank vapor: 1.0000 C a = 2.891, Ca = 10.057, C 4 = 1.079, C4 = 6.041 , (12) Vapor X~,;.t Equiv. (cu Mol Wt.of Gal/Mol of Components Components ft vapor! gal comp.) (from Table 14) (from Table 14) Table 14 16.03 30.05 44.06 58.08 58.08 72.09 72.09 86 99 110 123 230 7.050 9.000 10.370 12.340 11.920 13.840 13.690 15.098 16.334 17.742 19.337 32.172 53.80 42.00 36.60 30.80 31.80 27.40 27.70 25.10 23.20 21.36 19.60 11.78 from GPM" GPM' V st , V" Lb/Molof GollMol of 1,000(Col.2) 1,OOO(Col.4) LsI Ls' (Col.8) (Col.8) (Col.5)(Col.7) (Col.5)(Col.6) 2.891 .205 .874 .073 .199 .096 .047 .014 .005 10.057 1.088 4.953 .489 1.310 .629 .263 .075 .020 4.404 18.884 .0049 .0612 .4978 .1419 .9488 .2325 .8625 1.2426 1.6563 1.5258 1.2859 14.0720 22.5322 .0112 .2043 2.1149 .6679 4.6232 1.2111 4.5417 7.0778 10.0386 9.4600 8.1795 100.6020 148.7322 C s + = .434. Cs + = 2.786 • Two-Sta·ge Separation Two-stage separation, illustrated in Fig. 45, is defined as the process wherein original reservoir oil Xo (single phase) is produced to the first-stage (or high-pressure) separator where vapor V, and liquid L, are separated while at equilibrium conditions; the liquid L, (single phase) is produced from the first-stage separator into the secondstage (or low-pressure) separator where vapor V, and liquid L, are separated while at equilibrium conditions; finally, the liquid L2 (single phase) is produced from the second-stage separator into the stock tank at atmospheric pressure where vapor V" and liquid L" are separated while at equilibrium conditions. The separator conditions of pressure and temperature chosen to illustrate the method of calculating two-stage separation are 100 psig and 70°F for the first-stage separator, and 10 psig and 70° F for the second-stage separator. The K-values used are pertinent to their respective components at these conditions of pressure and temperature. The hydrocarbon analyses of the first-stage separator vapor V, and liquid L, are calculated as shown in Table 18 under the single-stage separation example. The hydrocarbon analyses of the second-stage vapor V, and liquid L, are calculated as shown in Table 22 based on material of a hydrocarbon analysis of the first-stage separator liquid from Table 18. The values for V, and L, were found by trial and error to be 0.09684 and 0.90316, respectively. The hydrocarbon analyses of the stock-tank vapor V" and liquid L" are calculated as shown in Table 23 based on material of a hydrocarbon analysis of the second-stage liquid from Table 22. The values for V" and L" were found by trial and error to be 0.0325 and 0.9675, respectively. The hydrocarbon analyses of the second-stage vapor TABLE 21 - SINGLE-STAGE SEPARATION, CALCULATION OF FLUID DATA FROM RESULTS OF FLASH CALCULATIONS Gravity of Stock- Tank Oil: Ib/mol Ib 148.7322 gal/mal gal 22.5322 6.6009 ;: 47° API Separator Gas-Oi I Ratio: V, (cu ft/mol){gal/bbl} L, x Lst (gal/mol) .5052 x 379 x 42 .4948 x .8493 x 22.5322 849 scf gas/STB oil. Stock-Tank Gas·Oi I Ratio: Vs! (cu ft/mol}{gal/bbl) = .1507 x 379 x 42 Lst (gal/mol) .8493 x 22.5322 125 scf gas/STB oil. Flash Shrinkage Factor: lIBoil = (gal/mol}{mollbbl) L, x Lst (gal/bbl) 22.5322 x 2.9431 x .4948 x .8493 42 0.6635 STB oilibbl orig. sample oil. JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 separation are 100 psig and 70°F, respectively The Kvalues used are assumed to be pertinent to their respective components at these conditions of pressure and temperature. The hydrocarbon analyses of the single-stage separator liquid and gas are calculated by Table 18. The values for V, and L, were found by trial and error to be 0.5052 and 0.4948, respectively. The 100-psig separator liquid is then considered as original material, and flash calculations are made on its composition at O-psig and 70°F stock-tank conditions. The hydrocarbon-analysis calculations for the gas and liquid material are shown in Table 19. The values for V" and L" were found by trial and error to be 0.1507 and 0.8493, respectively. The trial-and-error calculation is performed by assuming a value for V and calculating for the summation of y, repeating the calculations until the value of the summation for y equals unity. The hydrocarbon analysis of the liquid and gas separated at the 100-psig separator (from Table 18) and the hydrocarbon analysis of the liquid and gas separated in the O-psig stock tank (from Table 19) are combined with the preliminary data in Table 14 to <:alculate the GPM of both separator and stock-tank gas, and the gallons per mol and pounds per mol of stock-tank liquid. These calculations are shown in Table 20. The final calculations of (1) stock-tank oil gravity, (2) separator gas-oil ratio, (3) stock-tank gas-oil ratio and (4) shrinkage factor are shown in Table 21. These data are determined by means of similar calculations utilizing appropriate K-values at other chosen separator pressures, and the results of all the calculations are plotted in the form of curves. These curves (illustrated by Figs. 42, 43 and 44) then permit interpolation of optimum single-stage separator pressure conditions. Note that the O-psig conditions for the single-stage separator are the same as the check calculations; those points are plotted in Figs. 42, 43 and 44. /" " 45 44 - , .- - -- >-- A are 200 psig for the first-stage separator and 20 psig for the second-stage separator. The shrinkage factor for optimum two-stage separation is seen to be 0.6765 STB oiljbbl of reservoir oil (from Fig. 49) and for optimum single-stage separation is seen to be 0.664 STB oiljbbl of reservoir oil (from Fig. 42) . Therefore, two-stage separation provides 0.0125 bbl more oil in the stock-tank per barrel of reservoir oil produced than does optimum single-stage separation. For a given reserve, therefore, the economics of the problem will involve: (1) additional stock-tank oil recovered and its price (if allowables are not changed by the operations, the added income will be deferred); (2) an increase in income from increase in gravity, if such is the case; (3) a decrease in gas volume resulting from increases in oil volume and its price, if gas is being sold; and (4) additional 11 ~ 10 '" .... '"0.. / 9 V '" o'" ..J ..J -< .;.; ~ -< ) ,I <!I 7 ...-<fil w '" !!! II 43 6 ..J / .,so ...z.u V B o ." 3 '"~ - ~ I U 17 0 ...... .. .. . c5< ..... -- -- --- ._-- -.._.- -- _ ---- v:". ,, ......... , ; 2 / C 1-·-3 1- .. _ C - I-- 4•• J --( o .62 ., rr ...z ./ / c4 - ~ I ..... ...... ..... LL o 0 ~ / <!I I -- v o 2C 40 60 !I:l 100 .... Cs.+;. I- - - 120 140 160 180 200 SEPARATOR PRESSURE: PSIG 10 Fig. 44-Effects of separator pressure on GPM content of liberated gases, single-stage separation at 70°F (solid lines represent stock-tank gas; dashed lines represent separator gas). .600 SEPARATOR PRESSURE: PSIG Fig. 42-Effects of separator pressure on .gravity and volume of stock-tank oil (singlestage separation at 70°F)-(A) residual oil gravity, API at 60°F; and (B) l/B'i residual oil volume, STB/bbl saturated oil. 0 ~ '>m ....... t- .1<10 lL ::;) o .... 0: ... o ~\ \ I I ~ SEPARATOR RATIO -It 1', ..... (!) 0:"" o tt,., 0: ~~ l&J en ./ V t? ~~ .........V " .. 00 StPARATOR rt V /'" / t--.so r--STOCK-TANK 1'--.- 1<, - R,(I~IO '00 '00 PRESSURE: PSIG 1--- '00 o ~ Z so .,. 0: (!) t! ~ ,0 .. ~ Fig. 43-Effects of separator pressure on gas-oil ratio (single-stage separation at 70°F). MAY, 1962 SECONDSTACE FIRST STAGE SEPARA,TlON '.J SEPARATION l, ! = v, I + L, ,_~ QUANT'n ,"p"R.no ".PO ... NOCIQ!.HO PH.'" Fig. 45-Schematic diagram showing flash separation of original reservoir liquid through two separator stages and stock tank. 497 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 and liquid from Table 22 and the stock-tank vapor and liquid from Table 23, together with preliminary data from Table 14, are used to calculate GPM content of secondstage and stock-tank vapor, and gallons per mol and pounds per mol of stock-tank liquid. These calculations are shown in Table 24. . Table 25 shows the final calculations of (1) stock-tank oil gravity, (2) 100-psig separator gas-oil ratio, (3) 10psig separator gas-oil ratio, (4) stock-tank gas-oil ratio and (5) shrinkage factor. These calculations are performed for various two-stage pressures while holding the first-stage pressure constant, and the optimum second-stage pressure is determined for the listed data. Curves representing plots of these data are shown in Figs. 46 through 49, with the sample calculated data points shown. To determine the optimum first- and second-stage pressures, it is necessary to repeat the series of calculations for other first-stage pressures. Plots of API gravity and liB" data for stock-tank oil calculated for first-stage pressures of 75, 100, 150, 200 and 250 psig are shown in Figs. 48 and 49, respectively. From these plots it is seen that, if high stock-tank oil gravity and low shrinkage are desired, the optimum separator conditions cost of two-stage separation equipment over one-stage separation equipment. Should the gas separated at the surface be rich in condensate content (as the gas from this example indicates) and if reserves of reservoir fluid from which gas is produced are fairly large, the operator may wish to determine the economic feasibility of installing a natural-gasoline plant to strip the condensate from the gas for sale. A problem of this nature may consider several plans with varying degrees of decreasing the stock-tank oil recovery and increasing the condensate content of the gas, the economics of which involve such things as (1) the market value of natural gasoline compared to the market value of stocktank oil, (2) the cost of the gasoline plant installation and (3) the added revenue from the recovered natural gasoline. Other problems of a similar nature are involved when pressure maintenance operations are invoked to increase recovery by more efficient reservoir displacement or vapor· ization. SECOND-STAGE SEPARATOR PRESSURE: Fig. 46-Effects· of separator pressure on gas-oil ratio (two-stage separation at 70°F, first-stage separator pressure 100 psig). There are certain types of problems involved in the manipulation of hydrocarbon analyses with which the analyst must be able to cope in order to perform some phase-behavior calculations. One general type involves altering the original hydrocarbon analysis by adding volumes of other hydrocarbons, and this problem is solved by adding the hydrocarbons on a mol fraction basis. A typical example is involved with the example oil sample used here. If precision calculations of phase behavior had been mandatory, it would have required adding the 73 cu ft of gas to the barrel of sample oil at sampling temperature and pressure on a mol basis, and the hydrocarbon analysis of the original oil so obtained would have been used in the calculations of flash separation. It was assumed, however, that the example calculations did not warrant such precise treatment. In addition, the analysis of the 73 cu ft of gas was unknown, and an estimation would have been required. Pure methane is usually assumed in such cases. This same type of calculation, however, is illustrated in a gas-lift problem; the addition of gas-lift gas to the gaslifted produced oil has a hydrocarbon analysis of the sample oil, and the gas used for gas-lift has th'; analysis of TABLE 22-TWO·STAGE SEPARATION FLASH CALCULATIONS-FIRST·STAGE LIQUID TO SECOND·STAGE SEPARATOR TABLE 23-TWO·STAGE SEPARATION flASH CAlCULATIONS-SECOND·STAGE LIQUID TO STOCK TANK '"', E"""ltons: Condittons01 Fla1h: E.timated Yz - .09684. (2) -, ~ Ethane P,op"",, j.8ul" .... N.B"t .. " .. I.P.nt" .. e N.P e """,.. H"xone Heptane 0<;10"" Nona .... 0""0"" ' Estimaled .90316. (4) (6) 1" , (C"I.2)(C"I.3) (Co!.3)- I V2 (Col.5),1 129.3522 18.7449 4.6356 1.7773 1.2267 .4960 .3522 .1182 .0388 .0123 .0033 3.09152 .70856 .44641 .02630 .11200 .00808 .02078 .00855 .00338 .00090 .00019 128.3522 17.7449 3.6356 0.7773 0.2267 -.5040 -.6478 -.8818 -.9612 -.9877 -.9967 -1.0000 13.42963 2.71842 1.35207 1.07527 1.02195 .95119 .93727 .91461 .90692 .90435 .90348 .90316 '" , , V 2 (K (8, (7) EqUlhb"uIh Conslanl at 10 P~'9 and 70"F .0239 .0378 .0963 .0148 .0913 .0163 .0590 .0723 .0870 .0733 .0565 .3715. Methone Candllion. of Flosh: T"lOpsiIlQnd70"F. IOOp"'l0nd70°F ~ L2 (3) Hyd.oca.bon Anoly.is of FltSI.Stog. S.p.Liq.L, (mol /'0" from _(ompo",,'" U""idL, ", , -, Hydrocarbon Anoly.i,,,1 " Hydrocarbon ~.cond·SlO1I. s....::ond.St0'l. Vapor V2 (mollrac), (Col. 4)/(Col. 6) Liqu.dl z (Cot.7)/(Col.3) ~ .0712 .0093 .0037 .0010 .0002 .0119 ,0138 .0893 .0171 .0629 .0791 .0959 .0811 .0625 -~ 1.0000 101'''9 ond 70° f To Op",gond70'f. L" '" 13) '",,, K Equ,lib"um Cansl"n' o' Op.igand Compan.nl ~ ~ (Cot. 2)(Col, 3) (Col.]) - 1 I), I V,,(Col,51+ I M.than. E,hon. P<opane I.Bulan. N·Bulan. I.P.nlane N.Penlan" H"xan. H"pl"n" Oclan .. Nonan .. D.can .. + .0018 .0139 .0712 .013B .0B93 .0171 .0629 .0791 .0959 .0811 .0625 217.0068 31.3946 7.6667 2.9184 1.9796 .7993 .5755 .191Q .0602 .DI88 .0056 ,39061 .43638 .54587 .04027 .17678 .01361 .03620 .01517 .00507 .00152 .(l(l035 216.0068 30.3946 6.6667 1.9184 0.9196 -.2007 -.4245 -.8082 _.9398 .9812 -,9944 -1.0000 8.02022 1.98782 1.21667 1.06235 1.031B4 .9934B .98620 .97373 .96946 .96811 ,96768 .96750 (mol froc). .3301 .024,5 .1096 .0085 12' -, V", - .0325, From Hydroca,b<>n AnalysIs 01 5",,<>nd·5Io 9" Sep.L'q.L 2 (m<>1 f'a" Irom "n"ly.is,,1 .2302 .2607 .0222 ii' L,qu,d L2 1.0000 ~ '" , , '''',,(I( Hydrocarbon Anolys .. of SI<>ck·Tonk Vap'" V~, (mol f,,,c), (C"I.4l/(C<>I.6) .0487 .2195 .4485 .0379 .1713 .0138 .0367 .0156 .00" .0016 .0004 '-.," Hyd.oca,b"" Analy~i~ of Slack-Tank Liquid L s ' (mol (.DC), (Col.7l/(eol.!! .0002 .0070 .0585 .0130 .0865 .0112 .0638 .0812 .0989 .0838 .0646 .:.~ 1.0000 TABLE 24 - ComE:onent Methane Ethane Propane I-Butane N-Butane I-Pentane N-Pentane Hexane Heptane Octane Nonane Decane+ * GPM TWO-STAGE SEPARATION, CALCULATION OF FLUID DATA FROM RESULTS OF FLASH CALCULATIONS (8) ( 11) (7) (9) (12) (4) (5) (6) (10) Vapor X2 xsI Y2 Yst Equiv. (cu Hydrocarb. Hydrocarb. Hydrocarb. Hydrocarb. GPM** GPM* It/gal Anal. of Anal. of Anal.of Anal.of Mol Wt.of .Gal/Molof V2 , Vst, Gal/Mol of Lb/Molof comp.) V2 (mol L2 (mol Lst (mol Components Components Vst (mol l,OOO(Col.2) l,OOO(Col.4) Lst Lst from (from frae from frae from frae from (from fraefrom (Col.8) (Col.5)(Col.?) (Col.5)(Col.6) Table 14) Table 14 (Col.8) Table 22) Table 22) Table 23) Table 23) Table 14) (2) (1) .2302 .2607 .3301 .0245 .1096 .0085 .0222 .0093 .0037 .0010 .0002 .0018 .0139 .0712 .0138 .0893 .0171 .0629 .0791 .0959 .0811 .0625 .4114 .0487 .2195 .4485 .0379 .1713 .0138 .0367 .0156 .0060 .0016 .0004 1.0000 1.0000 1.0000 second"stage vapor: ** GPM stock-tank vapor: ·1911 (3) Ca 9.019 Ca = 12.254 , .0002 .0070 .0585 .0130 .0865 .0172 .0638 .0812 .0989 .0838 .0646 .4253 16.03 30.05 44.06 58.08 58.08 72.09 72.09 86 99 110 123 230 1.0000 C 4 = 4.242 C 4 =6.618, 7.050 9.000 10.370 12.340 11.920 13.840 13.690 15.098 16.334 17.742 19.337 32.172 53.80 42.00 36.60 30.80 31.80 27.40 27.70 25.10 23.20 21.36 19.60 11.78 9.019 .?95 3.447 .310 .801 .371 .159 .047 .010 12.254 1.231 5.387 .504 1.325 .622 .259 .075 .020 14.959 21.677 .0014 .0630 .6066 • 1604 1.0311 .2380 .8734 1.2260 1.6154 1.4868 1.2492 13.6828 .0032 .2104 2.5775 .7550 5.0239 1.2399 4.5993 6.9832 9.7911 9.2180 7.9458 97.8190 22.2341 146.1664 Cs = 1.698. C s = 2.805 • JOl·H.'.\/. OF PETHOLEl ~ TECH:\OI.OI;\ Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Calculating an Adjusted Hydrocarbon Analysis PS~ th~ produced material as reservoir pressure drops and retrograde condensation occurs in the reservoir; thus, the condensate study must be guided by premises based on such changes. Extending the Hydrocarbon Analysis A problem which often confronts the analyst is that of extending the hydrocarbon analysis from one which groups all heavy components together, such as hexane-plus components, to one which breaks the heavy group into individual heavy components. The hydrocarbon analysis of the I / 48 ~-... ~-~ ------- - ~ ----~. /"-" IL .., <> ..... 47 Il/" I II I I I I a: ~ ,:: ;; ~ -~~ r-- ~~;; .::::"~ ........ ------ ~ --- ----;- 20 PS1G ~ OPTIMUM SECOND SEPARA7R PRESSUY ~ STAGE C> (5 ! c---' .. '" I- ..J I V ;~A;t~;p~:r~~RM :~~~~URE 46 I LEGiND FIRST-STAGE SEPARATOR PRESSURES ::i::::> A _ _ _ _ 75 PSIG ~ t----- W '" E - 45 - B - 1 0 0 PSIG C _ - 1 5 0 PSIG D - - - 200 PSIG m - __ 250 PSIG 1 m I I • ~ • ~ ro SECOND-STAGE SEPARATOR PRESSURE: PSIG Fig. 48-Effects of separator pressure on gravity of stocktank oil (two-stage separation at 70°F). 14 -- - 13 12 / u. ~11 LEGEND, ..J _ ___ FIRST·STAGE SEPARATOR GAS SECOND-STAGE SEPARATOR GAS _ _ STOCK·TANK GAS ............. 0 0 r--.. --.. ..J 9 ~ .. 8 "" " ..'" o 7 w I- W 6 !E ..J go; 5 IZ \': 4 z o u '" 3 "C) en ", ~ "'t - -< 10 .... ~ ::l (5 .... 1' ~~ ",:0 = PSIG OPTIMUM SECOND STAGE SEPARATOR 7ESSURE D LEGEND, FIRST-STAGE SEPARATOR PRESSURES A ____ oJ -- -- ---- --- - - - 30 7S PSIG B 100 PSIG C _ _ 150 PSIG o -- __ 200 PSIG E - - __ 250 PSIG .650 <t _ _ c, 40 ~ 50 ::l 0 c, 60 en ILJ Cst C,+ 70 80 90 100 Fig. 47-Effects of separator pressure on GPM of liberated gases (two-stage separation at 70°F; first-stage separator pressure 100 psig). 1962 A'"' C,+ ....... -- LOCUS OF OPTIMUM FIRST STAGE SEPARATOR PRESSURES > c, C " " I ..J 0 'C, SECOND·STAGE SEPARATOR PRESSURE: PSIG MAY, .6W "'. oJ ~~ 20 iLl I i'- \, ~ II c, ....... - .-- .......-:: E III I ..:. t- " I' t\ I 200 PSIG = OPTIMUM FIRST STAGE SEPARATOR PRESSURE III III .670 ..... \. __.L "r-..:::, • Art.4.. ..J \ C) ~ -S'o+ .... £.~ .. -~~ - -- ---.~ .... t/~I~ .... ...... .............. ~ ~ en ~ 10 Vi ~ -"".l2 a:: ::l z o I ~ c, '""-w ::i .680 ILJ a:: o !e .640 10 m SECOND-STAGE 30 ~ • 70 SEPARATOR PRESSURE: PSIG Fig. 49--Effects of separator pressure on residual oil volume (two-stage separation at 70°F). 499 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 gas-cap gas in equilibrium with the oil at sampling conditions of reservoir temperature and pressure, as calculated in Table 13. It will also be assumed that the gas-lift ratio is 3 Mcf/bbl of reservoir oil. The calculation of the hydrocarbon analysis of the combined mixture is shown in Table 26. The 3 Mcf gas/bbl of reservoir oil ratio is equivalent to 2.9425 mols gas/mol of reservoir oil. In oil reservoirs where pressure drops substantially, such as is typically the case with dissolved-gas-drive reservoirs, the average produced GOR becomes very high compared to the dissolved GOR of the original reservoir oil. The combined material thus produced is substantially altered in composition from that of the original reservoir oil. This is true because of the large amounts of methane and ethane which comprise the gas that has evolved incident to pressure drop in the reservoir. While the surface separation calculations illustrated here apply to the original oil mixture being produced to the surface, they do not apply to a higher-GOR oil and gas produced later in the life of such a reservoir because the oil that was originally combined with a substantial portion of the subsequently produced gas remains behind at reservoir conditions. Oils that later deviate to a troublesome degree from the calculated behavior of early reservoir life generally are those which have reservoir temperatures near the critical and which contain a high percentage of intermediate components such as propane, butanes and pentanes. Therefore, additional study and laboratory data may be required to analyze such a reservoir material properly. However, the practice has been to treat such oils as unusual cases, using the techniques developed herein which apply to the bulk of the oils normally encountered in practice. The' general premise does not apply to condensate materials because drastic changes occur to the composition of the TABLE 25 - TWO-STAGE SEPARATION CALCULATION OF FLUID DATA FROM RESULTS OF FLASH CALCULATIONS 70Q Gravity af Stack-Tank Oil: Ib/mol _ 146.1664 _ 65740 = 477° API gal/mol - 22.2341 - . -. 100-psig Separator Gas-Oil Ratio: V, (cu ft/mol)(gal/bbl) L, x L2 x Lst (gal/mol) 600 36.95 CC of C 19+ (.5052)(379) (42) 500 (.4948) (.90316) (.9675) (22.2341) 837 cu ft/STB oil. 10-psig Separator Gas-Oi I Ratio: V 2 (cu ft/mol)(gal/bbl) ou. W 400 (.09684) (379) (42) L2 x Lst (gal/mol) ::> '">< w '" ""'"w >- (.90316) (.9675) (22.2341) 79 cu ft/STB oil. Stoc\,c-Tank Gas-Oil Ratio: V st (cu ft/mol)(gal/bbl) (.03250)(379)(42) (.9675)(22.2341) Lst (gal/mal) = 24 cu ft/STB 300 oil 200 LEGEND 100 • (22.2341) (2.9431) (.4948) (.90316) (.9675) ASH. . DISTILLATION DATA + 42 BOILING POINT 0.6736 STB oil/bbl orig. sample oil. 10 sample oil is assumed for purposes of illustration; the hexane-plus fraction is grouped together and is equal to 0.3288, as shown in Table 27. The heavy fraction is broken down into individual components up to C 19 +. The breakdown is made on the basis of the ASTM distillation curve shown in Fig. 50, plotted from the ASTM data of Table 5. * The process involves determining the volume of each component per 100 cc of charge stock of residual oil. The component volumes are determined based on the known mid-boiling points of the components from published data. With the volume of each component and its specific gravity known, the weight of each component is determined; with the molecular weight of each component known, the mol per cent of each component in the hexane- 26-CALCULATION Data: OF ORIGINAL Combining GOR (2) 60 70 80 90 100 cc In many cases, it is necessary to heat oils to break wateroil emulsions. Volatile materials may be lost to such a considerable extent that the gravity of the stock-tank oil is severely reduced. This is particularly true if the heating is done before separation. The effect of such operations ANALYSIS OF A GAS-LIFT 3 Mef 3000/(cu ft/mol) bbl reservoir oil 5.615 (mol/l00 Ib)/100 (cu ft/lb) (3) 50 Effects of Using Heat to Break Emulsions 2.9425 SYSTEM mols gas-lift gas mol reservoir oil (4) Component Reservoir Oi I (mol frac)** Gas-L ift Gas (Mol frac)*** Mols Gas Camponent/ MoiOil, 2.9425(Col.3) Methane Ethane Propane I-Butane N-Butane I-Pentane N-Pentane Hexane Heptane Octane Nonane Decane + .3572 .1021 .1011 .0105 .0592 .0091 .0320 .0370 .0436 .0364 .0280 .1838 .8087 .0976 .0520 2.3795 .2872 .1530 .0215 .0633 .0073 .0038 .0030 .0016 .0008 .0037 1.0000 1.0000 --- 40 plus fraction can then be calculated. The extended hydrocarbon analysis is then obtained by combining the hydrocarbon analysis of the hexane-plus fraction on the basis of 0.3288 fraction of the total. Complete calculations illustrating the method are shown in Table 27. HYDROCARBON 3000/379 5.615 x 1.2907/100(.02463)* (l) 30 Fig. 50-ASTM distillation curve of residual oil showing mid-boiling points and volumes of hydrocarbons in mixture. *Jour. Pet. Tech. (Jan., 1962) 16. TABLE 20 PERCENT DISTILLED, CC PER 100 (5) (6) Mol Component/ 3.9425 Mols Hydrocarbon Analysis Combined Mixture, Mixture, (Col. 2) + (Col.4) (Col. 5)/£ (Col. 5) .0215 .0112 .0088 .0047 .0024 .0109 2.7367 .3893 .2541 .0105 .1225 .0091 .0535 .0482 .0524 .0411 .0304 .1947 .6941 .0987 .0645 .0027 .0311 .0023 .0136 .0122 .0119 .0104 .0077 .0494 2.9425 3.9425 1.0000 * Adjusted value. See Table 14. ** Assumed analysis of sample reservoir oil. *** Assumed calculated value of original equilibrium gas-cap gas. 500 JOURNAL OF PETROLEUM TECHNOLOGY Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Flash Shrinkage Factor: (gal/mol) (mol/bbl) L, x L2 x Lst 1/ Boi! = (gal/bbl) TABLE 27-EXTENSION OF HYDROCARBON ANALYSIS BY USE OF ASTM DISTILLATION DATA (1) Component (2) Hydrocarbon Analysis Sample Oil, Xo(mol frae) Lab Data .3572 .1021 .1011 .0105 .0592 .0091 .0320 .3288* Vol/l00 cc C6+ Frae. (from ASTM and Fig. 50) 6.25 7.30 7.90 7.20 5.30 4.20 4.05 3.95 3.90 3.35 3.50 3.55 2.60 36.95 (4) Specific Gravity (from Published Data) (5) gm/l00cc C6 + Frae., (Col. 3)(Col. 4) (.999)*** .6640 .6880 .7070 .7220 .7340 .7471 .7560 .7630 .7690 .7760 .7780 .7820 .7860 .7896** 4.146 5.017 5.580 5.193 3.886 3.135 3.059 3.011 2.996 2.597 2.720 2.773 2.042 29.147 * C 6 + fraction. (6) Mol Wt. (from Published Data) 86.2 100.2 114.2 128.3 142.3 156.3 170.3 184.4 198.4 212.4 226.4 240.5 254.5 268.5 (7) (8) Mol/l00 ce (Col. 5)/(Col. 6) Hydrocarbon Analysis (mal fro c), (Col. 7)/I(Col. 7) (9) Extended Hydrocarbon Analysis (mol frae), (.3288)(Col.8) .0672 .0501 .0489 .0405 .0273 .0201 .0180 .0163 .0151 .0122 .0120 .0115 .0080 .1086 .1474 .1099 .1073 .0889 .0599 .0441 .0395 .0358 .0331 .0268 .0263 .0252 .0176 .2382 .3572 .1021 .1011 .0105 .0592 .0091 .0320 .0485 .0361 .0353 .0292 .0197 .0145 .0130 .0118 .0109 .0088 .0086 .0083 .0058 .0783 = .4558 1.0000 1.0000 ** C 19 + data for normal C19' *** 1 ee water weighs .999 gm at 60° F. can be calculated using flash calculations, the only requirement being that the analyst know the hydrocarbon analysis of the mixture being heated and the temperature and pressure of the material when separated. General Oil-Shrinkage Problems The operator encounters two main problems regarding the economic production of oil reservoirs-( 1) the problem of determining proper reservoir operating conditions to provide minimum shrinkage of oil in the reservoir, and (2) the problem of adjusting separator conditions to provide minimum stock-tank shrinkage of produced oil. The following two sample calculations illustrate these two proplems in a general way. Reservoir Shrinkage Problem Assumptions: 1. Reservoir Volume = 10 million bbl original oil-filled pore space. 2. Abandonment Conditions-(a)low-pressure primary operations, 50 per cent of oil-filled pore space remains with differential oil shrinkage Bo/Bai = 0.75; and (b) highpressure gas or water-injection operations, 50 per cent of oil-filled pore space remains with differential oil shrinkage Bo/Boi = 0.95. 3. Surface Separator Shrinkage l/B u;, = 0.664. Solution: Recovery under 2 (a) = [ 10,000,000 - 5,000,000] .75 X 0.664 = 2,200,000 STB oil, Recovery under 2 (b) = 5,000,000] .95 [ 10,000,000 X 0.664 MAY, 1962 = 3,140,000 STB oil, Difference in Recovery = 940,000 STB more oil from 2(b) than 2(a). Separator Shrinkage Problem Assumptions: 1. Same reservoir as in "Reservoir Shrinkage" problem. 2. Separator Producing Conditions-(a) O-psig trappressure operations permit stock-tank oil shrinkage l/Bai! of 0.603 to occur; and (b) optimum separator pressure operations permit stock-tank oil shrinkage ljBo" of 0.664 to occur. 3. Reservoir displacement under both operations results in 50 per cent of oil-filled pore space remaining with .95 shrinkage to reservoir oil. Solution: 5,000,000] Recovery under 2 (a) = [ 10,000,000 .95 X 0.603 = 2,850,000 STB oil, Recovery under 2 (b) = [ J 0,000,000 5,0~g;000 1 X 0.664 3,140,000 STB oil, Difference in Recovery = 290,000 STB more oil from 2(b) than 2(a). It is important to note that the economic justification for operation under optimum conditions may be somewhat reduced or reversed if the separated gas is delivered to a gasoline plant where the remaining liquefiable hydrocarbons will be recovered. Acknowledgment The author wishes to thank his associates, J. D. Lindner and T. G. Roberts, for their advise and assistance during the preparation of the five Technical Articles in the Fundamentals of Reservoir Fluids series. *** 501 Downloaded from http://onepetro.org/jpt/article-pdf/14/01/11/2214317/spe-91-pa.pdf by guest on 05 May 2022 Methane Ethane Propane I-Butane N-Butane I-Pentane N-Pentane Hexane Cut C 7 Cs C9 Cl0 Cn C12 C13 C14 C 15 C 16 Cn C1S C 19 + (3)