Water Sampling

The goal of formation-water sampling is also one of obtaining a representative sample. The composition of formation water is not generally so dependent on the temperature and pressure changes, and sampling procedures are in most cases simpler than for oil and gas. Small volumes of formation water retrieved from a drill-stem test or formation tester can often be used for analysis of dissolved salts. Samples are more often taken from the separator or wellhead. Sampling Methods Drillstem tests are temporary completions of a productive interval; they allow short-term production of reservoir fluids for the measurement of pressure and collection of flow-rate data. During a drillstem test, or DST, fluids may or may not flow to the surface, depending on the reservoir pressure, the productivity of the formation, and the design of the test. If formation fluids flow to the surface, sampling may proceed just as in the case of a producing well test, as long as care is taken to produce all of the drilling mud filtrate that has invaded the pore space in the near wellbore area. This cleaning-up process may take some time, depending on how much filtrate loss or lost circulation occurred during drilling. DSTs are not generally reliable means of obtaining oil and gas samples, unless all the requirements for a representative sample are met. Water samples taken from DSTs are generally reliable if tests are made on site to ensure a representative sample. For example, when water samples that had been taken at intervals from the produced fluid column within the drillpipe on a well that did not flow to surface were analyzed, they showed how errors can be caused by incorrect sampling. In Table 1, below, we see an analysis of top, middle, and bottom samples taken from a 50 ft (15 m) column of fluid. These data show an increase in salinity with depth in the drillpipe, indicating that the first water was contaminated by mud filtrate (Noad 1962; Collins 1975). Only the bottom sample is representative. Constituent Top Sodium Calcium Magnesium Bicarbonate Sulfate Chloride Total dissolved solids 29,600 8,100 600 500 2,000 59,900 100,700 Concentration (mg/liter) Middle 43,500 13,100 900 500 1,300 91,800 151,100 Bottom 71,800 22,400 1,400 400 500 154,000 250,500

Table 1. Drillstem test recovery of Smackover Limestone formation water. Changes in ionic composition are apparent as produced water becomes more representative of formation fluid in the lower portion of the drillpipe (after Noad, 1962; courtesy of JPT) If it is desirable to measure the dissolved gas content of the formation water, the drillstem must be shut in to allow the pressure at the bottom of the well to build up. A sample of the formation water at formation conditions may then be taken with a subsurface sampler run through the drillpipe. Some DST tools also contain a subsurface sampling device within the tool assembly that catches a sample at bottomhole flowing conditions.

Sampling at the flow line is conducted in a manner similar to Method 3 for separator liquid. Figure 1 (Apparatus for sampling water at the flowline) illustrates how several volumes (at least ten) of water are allowed to flow upward through the sample container.

Figure 1

The sample container valves are then closed. If any air bubbles are present in the water, a new sample should be taken. Figure 2(An illustration of the two techniques for obtaining air-free water samples: (a)

Figure 2

overfilling sample container from the bottom up and (b) overfilling sample container within a larger container and capping under water) is an illustration of two methods of sampling water from the wellhead. In the first, a plastic or rubber tube is used to fill a sample bottle from the bottom. Several volumes of fluid are displaced before the tube is slowly removed and the container sealed. An alternative method is to place the sample container within a larger container, filling from the bottom of the inner one until the brine overflows both containers. The sample is then capped under water to prevent air contamination. At wellheads where oil and water are produced together, a simplified surge-tank separator can be assembled, as shown in Figure 3 (Apparatus for obtaining an oil-free sample at the wellhead).

Figure 3

The separation container is first rinsed with well fluid and then filled from the bottom. An oil-free sample is then withdrawn at the bottom of the separator. Sample Containers Containers that are used for water sampling are made from plastic, rubber, metal, and boro-silicate glass. Glass can absorb iron and manganese and may contribute boron or silica to the sample. Metal containers can yield abnormally high iron content values. Plastic or rubber containers may similarly contribute organic compounds to the water (Collins 1975). Probably the most satisfactory container, especially if the sample must be stored before use, is the polyethylene bottle. Because metal catalysts are used in plastics manufacturing, the metal content of the polyethylene should be obtained from the manufacturer. High-metal-content plastics are not suitable (Collins 1975). A pH determination should usually be made at the sampling point. The pH can be affected by the sampling technique and by handling in the laboratory. Changes in pH between source and laboratory can only be exposed by having testing data from the source. Soluble iron in the water can precipitate out unless care is taken to keep oxygen out of the sample or a solution of hydrochloric acid is added to the sample to "fix" the iron and keep it in solution until analysis (API RP 45 1981). Often two identical samples are

obtained in plastic containers one of which is acidified. Because glass containers can absorb heavy metals even if acid is used, plastic is preferable (Collins 1975). Each sample container should be clearly marked with all pertinent data.

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Reservoir Fluids Petroleum accumulations are defined as naturally occurring mixtures of organic compounds, primarily hydrocarbons, that are found within the earth. Beyond this shared definition, specimens of petroleum collected from various locations might appear to have very little in common. Petroleum samples can vary from clear liquids that look much like water to thicker, greenish or reddish-brown mixtures, or even highly viscous, semi-solid black substances. The odor of these hydrocarbons can range from a sweet, aromatic bouquet to the distinctly disagreeable smell of rotten eggs. Although the bulk of the chemical compounds that comprise crude oil are hydrocarbons, the fact that carbon atoms have the ability to form long branching and cyclic chains allows an almost limitless diversity in the molecular composition of petroleum accumulations. Different specialists involved in petroleum exploration and production have different reasons for wishing to examine and characterize the hydrocarbon fluids and water found together in petroleum reservoirs. For example, a chemical engineer may be interested in a crude oil's composition only as it relates to the amount of commercial products the oil will yield after refining. An exploration geochemist might have an interest in an oil or reservoir water's composition, insofar as it sheds light on the origin, maturation, and degradation of the oil or helps point the way toward a better geological interpretation. The petroleum engineer is particularly concerned with the analysis of hydrocarbons in order to determine their behavior under the varying conditions of pressure and temperature that occur in the reservoir and piping systems during the production process.

Chemistry of Hydrocarbons
Despite the wide differences in the appearance of crude oils obtained from various localities, an ultimate analysis of these crudes for their weight percent of carbon, hydrogen, sulfur, nitrogen, and oxygen will show only minor differences. Table 1, below, gives the limits of these elements for nearly all crude oil samples. This phenomenon of consistency is due to the fact that hydrocarbon molecules have specific ratios of hydrogen and carbon atoms. This means that all hydrocarbons belong to one of a few series, although each series may have many thousand members. The differences in the properties of crude oils, therefore, may be explained by the relative amounts of each series present in the crude, although the relative amounts of carbon and hydrogen are not too different for each series. Hydrocarbons are classified as belonging to a particular series based on their molecular structure. Specifically, classification follows the arrangement of the carbon atoms (straight chains, branched chains, or cyclical), and the number of bonds between the carbon atoms (single, double, or triple). Element Carbon Hydrogen Weight % 84-87 11 - 14

Sulphur Nitrogen Oxygen Metals

0.06 - 8.00 0.02 - 1.70 0.08 - 1.82 0.00 - 0.14

Table 1. Element composition of crude oils (after Banks and King, 1984. courtesy of John Wiley and Sons) Hydrocarbons that are members of the paraffin oralkane series are common constituents of many crude oils. Alkane hydrocarbons are straight-chain or branched-chain configurations of carbon and hydrogen atoms that follow the general formula, C nH2n+2. The first member of the series (methane) has a formula CH4, the second member (ethane) is C2H6, and so on. The alkanes are saturated, that is, the carbon atoms are connected with single bonds. Figure 1(Models for methane and propane, showing the tetrahedral nature of the carbon-hydrogen configuration, after Burcik, 1979) shows the models used to visualize the structure of these hydrocarbons, and their "shorthand" formulas.

Figure 1

As longer chains are built, it becomes possible to arrange the carbon atoms in either linear or branched fashion without changing the relative number of carbon and hydrogen atoms. These different arrangements are called isomers and possess different physical

properties. For example, Table 2, below, gives the formulas and several physical properties for normal pentane, isopentane, and neopentane. Obviously, as the number of carbon atoms in a molecule increases, so does the number of possible isomers. Formula Name Molecular Boiling Critical weight point(F,14.7 press. psia) (psia) 72.151 72.151 96.92 82.12 488.6 490.4 Critical temp. (F) 385.7 369.03

CH3CH2 CH2 CH2 CH3

n-Pentane Isopentane

Neopentane 72.151

49.10

464.0

321.08

Table 2. Isomers of pentane showing the slight changes in physical constants due to the differences in structural formulas (from Engineering Data Book, 1972; reprinted by permission of NGP5A) All the straight-chain alkanes from CH4 (methane) to C40H82 (tetracontane) have been identified in crude oil. Typically, they amount to 15% to 20% of the oil. The possible isomers for these alkanes range from two for butane to about 6.2 1013 for tetracontane (Banks and King 1984). The alkanes are characterized by their chemical inertness, which probably accounts for their stability over long periods of geologic time. The first four members of this series (methane, ethane, propane, butane) exist as gases under standard conditions of pressure and temperature. Those from C 5H12 (pentane) to about C17H36 are liquids, and C18H38and higher are waxlike solids. "Paraffin" is a mixture of these solid members of the series. Saturated hydrocarbons that form closed rings rather than chains belong to the series known as cycloalkanes (also called naphthenesor cyclopraffins). These hydrocarbons follow the general formula CnH2n. Being saturated, these hydrocarbon compounds are relatively stable and possess chemical properties similar to those of the alkanes. Two very stable members of this series, cyclopentane and cyclohexane are shown in Figure 2 (Structure of several members of the cycloalkane series of hydrocarbons ).

Figure 2

Unsaturated hydrocarbons are compounds that contain a carbon-carbon double bond. That is, two valence electrons of each of two carbon atoms are involved in bonding the two carbons together. These compounds can add hydrogen to their structures under appropriate conditions, and are therefore said to be unsaturated (with hydrogen). One class of hydrocarbons that contains carbon-carbon double bonds is the arene (also called aromatic because many of them have fragrant odors) series. This group is made up of derivatives of benzene, whose formula is C6H6, and whose structure is shown in Figure 3 (Structure of several members of the arene, or aromatic, series.

Figure 3

The formula convention used here to represent benzene is called a Kekule structure. The compounds shown are common constituents of crude oil.) Although the benzene ring contains three double bonds, its unique structure allows it to be relatively stable and unreactive. The extra pairs of electrons are part of the overall ring structure and are not localized to one pair of carbon atoms. Some of the simpler members of this series consist of a benzene ring with one or more alkyl (CH3) groups attached as side chains in place of hydrogens. These compounds are common constituents of crude oil and include toluene and xylene. The arene hydrocarbons are either liquids or solids under standard conditions. Other unsaturated compounds are called alkenes orcycloalkenes, depending on their straight-chain or cyclic structures. They are known as olefins. Another series of unsaturated hydrocarbons is the acetylene series, which includes compounds having triple carbon-carbon bonds. Olefin compounds are very uncommon in crude oils and the acetylene series is virtually absent. This is undoubtedly due to the high degree of reactivity of these compounds, and their tendency to become saturated with hydrogen, forming alkanes (Banks and King 1984). Of the eighteen different possible hydrocarbon series, therefore, alkanes, cycloalkanes, and arenes are the common hydrocarbon constituents of most crude oils. One historical approach to the characterization of crude oils has been to classify them by base as either paraffinic, naphthenic, or intermediate. The term "naphthenic" is misleading here, for it is not directly related to the hydrocarbon series mentioned earlier, but simply indicates an oil that, upon distillation, forms a residue of asphaltic rather than waxy material (Banks and King 1984). The U.S. Bureau of Mines developed a classification system in which a crude sample is distilled and the key fractions recovered between specific temperatures tested for their specific gravity. This approach produces a range of nine possible classifications. These

groups can be further subdivided by the determination of the waxforming characteristics of the second (high boiling point) fraction. Crude oil Base API gravity of key fraction 1 40 or lighter API gravity of key fraction 2 30 or lighter UOP factor (average)

Pennsylvania, Paraffinic USA Mid Continent Intermediate USA Gulf Coast, USA Leduc, CAN Lloydminster, CAN Kuwait Abqaiq, SAU.AR. North Sea Naphthenic Intermediate Naphthenic Paraffinicintermediate Paraffinicintermediate Intermediate

12.2 - 12.5

33 - 40 33 or heavier 33 - 40 33+ 40 or lighter 40 or lighter

20 - 30 20 or heavier 20 - 30 20+ 20 - 30 20 - 30

11.8 - 12.0 11.0 - 11.8 11.84 11.35 11.93 12.00

33-40

20-30

11.84-11.98

Table 3. Classification of crude oil by base and UOP characterization factors. High UOP factors indicate more paraffinic composition, low UOP factors indicate a greater percentage of naphthene and aromatic compounds (after Buthod, 1962; courtesy of SPE/AIME) An attempt to establish a single index number that would provide a correlation for the base of a crude oil resulted in the U.O.P. characterization factor (Universal Oil Products Co.). This number is based on the average boiling point and specific gravity of a sample: values between 12.5 and 13.0 are found for paraffinic hydrocarbons; between 11.0 and 12.0 for naphfhenic hydrocarbons; and between 9.0 and 12.0 for aromatics. Table 3, above, shows the base and U.O.P. factors for several typical crude oils. These classification systems are mentioned here primarily because of their wide coverage, and because practically all known crude oils have been analyzed and classified by these methods and references to them are still common. In general, these classification methods serve as a guide to the ultimate commercial value of refined products obtained from a given crude. Modern crude oil classification commonly is based on a division of the hydrocarbons present into three main groups: alkanes, naphthenes, and aromatics, in combination with nitrogen, sulfur, and oxygen compounds (called resins and asphaltenes). This system can be depicted with a ternary diagram, as shown in Figure 4(Ternary diagram showing the composition of the six classes of crude oils according to Tissot and Welte.

Figure 4

Samples are shown from 541 oil fields-- from Tissot and Welte, 1978, reprinted by permission of Springer-Verlag). Here we see 541 oils plotted according to the percentage of these three groups in their composition. There are few oils with more than 50% naphthenic content. Paraffinic-naphthenic, paraffinic, and aromatic-intermediate oils are most common (Tissot and Welte 1978). Natural gas is composed primarily of the lighter (low carbon) members of the paraffin series. Methane and ethane frequently comprise 80% to 90% by volume of a natural gas (Amyx, Bass, and Whiting 1960). A natural gas with a greater percentage of high carbon constituents will typically yield larger amounts of natural gasoline or other liquids. All hydrocarbon mixtures, whether natural gas or crude oil, contain various amounts of nonhydrocarbon substances. Crude oils typically contain organic compounds which incorporate various combinations of sulfur, nitrogen, and oxygen atoms. Some organic compounds also contain metallic elements, particularly vanadium and nickel. While these components are distributed throughout the whole distillation range of a crude oil, they tend to be concentrated in the heavier components. The color and odor of crude oil stems mainly from the nitrogen, sulfur, and oxygen compounds concentrated in the C 26 C40+ fractions (Banks and King 1984). Sulfur is the most common nonhydrocarbon constituent, and the average sulfur content of crude oil is 0.65% by weight (Banks and King 1984). Carbon dioxide, nitrogen, hydrogen sulfide, helium, and hydrogen are the more common impurities found in natural gas hydrocarbon mixtures. For our purposes, these impurities are important because they can cause deviations from typical hydrocarbon behavior if they are present in sufficient quantities. In addition, impurities

such as hydrogen sulfide and carbon dioxide can also cause severe corrosion and handling problems for a production engineer. Sulfur contamination can also lead to serious refining problems for chemical and process engineers. Detailed analytical separation of crude oil or natural gas samples into components far beyond C6H14 (the hexanes) is expensive and not commonly done for most oilfield applications. As we shall see in later sections of this module, laboratory measurements of physical behavior or correlations based on easily measured properties are sufficient for most petroleum engineering purposes.

Classification of Reservoir Fluids

Common oilfield classifications of oil and natural gas rely on observed producing characteristics and easily measured specific gravity. The gas-oil ratio (GOR), gas gravity, and oil gravity are used to categorize reservoir hydrocarbons. Gas-oil ratio in this case refers to the cubic feet of gas produced per barrel of liquid (or cubic meters per cubic meter), with both volumes measured at standard conditions of temperature and pressure. As we shall see, the pressure and temperature of surface separators, and the number of separation stages, control the gas-oil ratio for a given system. Specific gravity, of course, is the ratio of the density of a substance to the density of some reference substance. For gases, the standard reference is dry air at the same temperature and pressure as the gas in question. These conditions should be specified. Specific gravity is also equal to the ratio of the molecular weight of the gas to the molecular weight of air (28.97). For liquids, the reference is pure water at 60 F (289 K) and one atmosphere (14.7 psia or 101 kPa). For hydrocarbon liquids, the API gravity (American Petroleum Institute) scale is most commonly used in the oil industry. A similar scale is the European Baume gravity scale. These two oil gravity scales expand and invert e range of numerical values for oil specific gravity. For example, a very heavy oil might have a specific gravity of 0.96, while a light distillate might be 0.78. Expressed in degrees API, these same gravities would range from 160 (heavy) to 500 (light). Baume gravity values are very close to API gravity over the general oil range. These scales allow gravity measuring hydrometers to be easily calibrated with a linear scale, and values are often correlated with other oil properties. Water has an API and Baume gravity of 10.0. The relationship between API gravity and specific gravity is given as:

Reservoir fluid Surface appearance Dry gas Wet gas colorless gas Colorless gas with small amount of clear or strawcolored liquid

GOR range Essentially Greater than 100 MSCF/bbl

Gas specific gravity 0.60 -0.65 no liquids 0.65 - 0.85

API gravity

60 - 70

Condensate

Colorless gas 3 to 100 with significant MSCF/bbl amounts of (900-18000

0.65 - 0.85

50 - 70

lightcolored liquid "Volatile" or high shrinkage oil "Black" or low shrinkage oil Heavy oil Tar Brown liquid with various yellow, red, or green hues Dark brown to black viscous liquid Black, very viscous liquid Black substance

m3/m3) About 3000 SCF/bbl (500 m3/m3) 100 - 2500 SCF/bbl Essentially no gas in solution Viscosity >10,000 cp 0.65-0.85 40 -50

(20 - 450 m3m3)

30 - 40

10 - 25 <10

Typical composition, mole % C1 Dry gas Wet gas Condensate "Volatile" or high shrinkage oil "Black" or low shrinkage oil Heavy oil Tar 20 3.0 2.0 2.0 2.0 71 90+ 49 2.8 1.9 1.6 1.2 43.5 87 64 4.4 7.5 2.3 4.7 1.7 4.1 .8 3.0 3.8 16.7 96 C2 2.7 C3 0.3 C4 0.5 C5 0.1 C6+ .4

Table 1. General categories of reservoir hydrocarbons. There are no definite boundaries between these classifications and usage may vary depending on location. Gravities and GOR are also dependent on separation conditions Table 1. shows the classifications of reservoir fluids, based on GOR and fluid gravities. A typical composition is also given, showing the mole percent of the lighter paraffin constituents relative to the heavier hydrocarbons. Remember that a mole is one molecular weight unit of any substance. Thus, a pound-mole is an amount of a substance equal to ifs molecular weight in pounds. The molecular weight of methane is 16.04, and one pound-mole of methane is equivalent to 16.04 pounds of methane. Similarly, one gram-mole is 16.04 grams of methane. It so happens that in the case of ideal gases, moles of any two gases occupy equivalent volumes and contain equivalent numbers of molecules at equivalent temperatures and pressures. So in this sense a mole can be thought of as a discrete number of molecules. For a mixture, the mole percent of a component in the total volume is the fraction of molecules in the mixture that are that component.

The categories in Table 1 are not rigorously defined. In general, low GOR, low APIgravity oils have lesser amounts of the light paraffinic hydrocarbons, while dry gases are composed almost entirely of these compounds. As we shall see, sampling and analyzing the behavior of dry gas or black oil systems are relatively straightforward procedures. Condensate and volatile oil systems, on the other hand, can be much more complex in terms of their physical chemistry.

Characteristics of Formation Water

In addition to liquid and gaseous hydrocarbons, petroleum reservoirs always contain a third fluid, water. Formation water is termedconnate water if it is believed to be a remnant of the original water in which the sediment was deposited. Meteoric water refers to formation waters that originate as rainfall and are carried into the ground via outcrops, fractures, or permeable sediments. Interstitialwater is the preferred term for the formation water that shares the pore space of the hydrocarbon reservoir with oil and gas, regardless of origin. Interstitial water saturations in petroleum reservoirs usually range from 10% to 50% of the pore space, and water saturations can vary throughout a reservoir, depending on the pore structure of the rock (Levorsen 1967). Formation waters are most commonly distinguished by their varying degrees of salinity, that is, the amount of dissolved ions present in the water. The ionic composition of formation water is usually measured in milligrams per liter and expressed in milligrams per liter (mg/I) or parts per million (ppm). A unit volume of solution is taken to have a million parts of weight, and the number of parts of weight contributed to the solution by a given ionic component is the parts by weight per million. Parts per million is only equivalent to milligrams per liter at a solution density equal to that of pure water. Since most formation waters have densities close to this value, the difference between numerical values in mg/I and ppm is not great. However, for an extremely salty water the difference could be as great as 20%. Composition, parts per million Common Chemical ions name Seawater Cretaceous,sandstone Miocene Burgan Field Kuwait formation Lagunilla Fields Venezuela L. Cretaceous limestone Rodessa Field, Texas-La.

Cations Na+ and K+ Ca++ Mg++ Anions ClSO4= CO3= HCO3Chloride Sulfate Carbonate 19,350 2,690 150 95,275 198 360 154,388 89 120 5,263 7,548 73 225,749 140,063 284 Sodium and 11,000 potassium Calcium Magnesium 420 1,300 46,191 10,158 2,206 2,003 10 63 61,538 20,917 2,874

Bicarbonate Total ppm 34,910

Other common ions include: barium (Ba++), lithium (Li++), iron (Fe+), Nitrate (NO3- ), bromide (Br-), iodide (I-), sulfide (S=) and strontium (Sr++). Table 5. Composition of typical formation waters. The composition of seawater is given for comparison (after Levorsen, 1987; courtesy of W.H. Freeman Co.) Table 5 shows some typical formation water compositional analyses. The total of all ionic components is often termed "total dissolved solids," and used as a reference index in comparison of formation waters. More informative techniques for categorizing formation waters involve the plotting of ionic composition on diagrams, as shown in Figure 1 (Formation water composition diagrams.

Figure 1

Shown here are the (a) Tickell method and the (b) Stiff method for seawater ). These graphs are useful in making quick visual comparisons of formation water from different formations. The Tickell method (Tickell 1921) uses the reaction value of the various ions as a value for graphing. The reaction value is equal to the mg/l concentration times the valence, divided by the atomic weight. Thus 420 mg/l calcium is equal to a reaction value of 420 2 40.08 = 20.9. If the reaction values for all ions are added together, a particular ion's reaction value may be expressed as a percentage of the total. Reaction values are also called equivalents per million,or milliequivalents per liter. The Stiff method (Stiff 1951) also uses milliequivalents per liter, but the scale is horizontal, resulting in a "butterfly" pattern. Usually the sodium and chloride scales are graduated in scale units of

100 milliequivalents, and the other ionic scales in units of 10, although the scales can be varied for any group of diagrams under comparison. Salinity is the most important characteristic that can be measured for a formation water sample. The ways in which formation water and hydrocarbon mixtures change with pressure and temperature depend upon the degree of salinity. For example, the solubility of natural gas in a formation water with 150,000 ppm total dissolved solids is only about half the solubility in pure water. However, even in pure water, the solubility of natural gas is not great; it is only about 10 to 30 SCF/ bbl (2 to 5 m3/m3) under most reservoir conditions. Determination of the formation water salinity is more important for correct interpretation of electric well logs. The resistivity of a formation water is related to its salinity, and a value of formation water resistivity is necessary for the quantitative evaluation of resistivity logs. Although this value can be estimated from log data and correlations, the best results are obtained when a sample of formation water is retrieved and analyzed. Applications of Reservoir Fluid Data Before we discuss the behavior of reservoir fluids, and the techniques for analyzing that behavior, we should briefly review our reasons for acquiring this information. As we shall see, there are a variety of correlations available for estimating fluid properties based on a few easily obtained measurements. These methods are, of course, somewhat less precise than a complete laboratory analysis of a reservoir fluid. However, correlations are valuable aids in the design of our ultimate sampling and analysis procedure, and are often the only data available for preliminary calculations, proposals, and estimates. Figure 1 (Applications of reservoir fluid property data in different areas ) is a generalized matrix showing the application of fluid property estimates and analyses in different areas of the exploration and production process.

Figure 1

While reservoir engineers generally have the greatest claim on such data, reservoir fluid analyses are also quite valuable to geologists and production specialists. Often the process of applying fluid data is one of revision and improvement. For example, a geologist may use correlations along with an oil or gas gravity measurement from a nearby well for help in obtaining an estimate of the potential reserves to be found in an exploration prospect. After the exploration well is drilled (and successfull), a well test may allow those same correlations to be used with the known gravity, GOR, and pressure data from the discovery well. In an ideal situation, a fluid sample may be recovered from the discovery well for analysis. This more precise information on the properties of the hydrocarbon accumulation may be used by geologists and engineers to justify further development drilling. One or several of the development wells may then be completed and reservoir fluid samples retrieved. The laboratory analysis of such samples provides the more accurate information needed to help plan the development of the field, design production facilities, determine the size and cost of equipment, and thereby make economic decisions. After production has been established, further sampling and analysis may be requested by the engineer to evaluate potential improved recovery projects. If such a project is implemented, routine sampling may even become a necessary part of the project's maintenance. All of this points toward a general increase in the amount of reservoir fluid sampling and in the accuracy of the overall interpretation of reservoir behavior, as the development of a field or reservoir progresses. However, the degree of accuracy required in engineering calculations is usually directly related to the cost of the proposed project. In the past,

unless an expensive enhanced recovery project was being considered, the cost of obtaining good reservoir fluid samples for reservoir analysis was often difficult to justify. However, the costs of development in today's industry, particularly in the offshore areas, are making early routine fluid sampling much more commonplace. The value of the data obtained from a sampling procedure, however, is only as good as the procedure itself. It is vitally important that the proper procedure be followed in obtaining a reservoir fluid sample, or the data will be no better than that estimated from correlations, and perhaps worse (and a good deal more expensive).

Hydrocarbon Sampling Procedures After conditioning, reservoir fluid samples may be taken with a subsurface sampling device, or individual samples of oil and gas may be taken at the surface and recombined to obtain a representative sample. The choice of sampling technique is influenced by: the volume of sample required; the type of reservoir fluid to be sampled; the degree of reservoir depletion; the surface and subsurface equipment. Subsurface sampling is the trapping of a volume of fluid in a pressurized container suspended on a wireline inside the well to the productive interval. This method is often used when: only a small volume of fluid is required; the oil to be sampled is not so viscous that it impairs sampler operation; the flowing bottomhole pressure is known to be greater than the reservoir oil saturation pressure;

the subsurface equipment will not prevent the sampler from reaching the appropriate depth or make its retrieval difficult. Surface sampling involves the taking of samples of separator oil and gas, along with accurate measurements of their relative rates, and reconstructing a representative sample in the laboratory. This method is often used when: a large volume of both oil and gas are required for analysis (as in the case of gas condensate fluids); the facilities for separating oil and gas and measuring their rates are in excellent condition and operated by thoroughly competent people; the fluid at the bottom of the well is not representative of the reservoir fluid (i.e., gas condensate reservoirs and oil reservoirs producing large quantities of water). Generally, a subsurface sample is preferred if gas and oil surface measurement capabilities are in question. However, if they are reliable, the surface sampling technique can give a statistically valid value of GOR measured over a long period of time. Subsurface Sampling The specific procedure to follow for subsurface sampling includes the following steps: 1. Condition the well to insure that a single-phase, representative fluid is flowing at the productive interval 2. Either shut in the well or allow it to continue flowing at a very low rate 3. Run pressure and temperature surveys to determine fluid levels and pressures 4. Select the sampling point and run the bottomhole fluid sampler to depth 5. Actuate the sampler and retrieve the sample 6. Repeat the sampling operation to obtain duplicate samples (at least two, preferably three samples should be retrieved) 7. Perform a quality check on the samples at the surface 8. Transfer the samples to a storage container for transport to the laboratory Let us briefly consider each of these steps. The decision to shut the well in or produce during sampling is dependent on flowing conditions. If the maximum flowing bottomhole pressure is less than or close to the reservoir fluid's bubble point, shutting in the well will allow the pressure to build up in the wellbore; ideally, this will redissolve the gas that

has formed near the well. The shut-in time may vary from 2 to 3 hours for a highproductivity well to as much as 72 hours for a low-productivity well (Amyx, Bass, and Whiting 1960). If the flowing bottomhole pressure is well above the bubble point, the low-flow-rate technique provides additional assurance that the fluid in the wellbore is representative of the reservoir fluid. A pressure-temperature survey is run to determine the location of the gas-oil and wateroil interfaces where the well is shut in. These contacts can be determined by plotting the measured pressure versus depth, and noting the points of slope change ( Figure 1 , Typical wellbore gradient plot showing location of gas-oil and oil-water contacts within wellbore).

Figure 1

The best place to sample is at the lowest point in the wellbore passed by all the fluid entering the well, and where the static pressure is above the estimated bubble-point pressure. When water is present, the sample may be collected just above the oil-water contact, if the pressure at that point is at least equal to the bubble-point pressure. If not, the water level may be lowered by bailing. If the water cannot be removed, or if an obstruction prevents the wireline sampler from reaching the required depth, another well should be considered.

The bottomhole sampler is next run to the sampling point and actuated. A variety of commercially available samplers differ primarily in the following ways: The actuation mechanism (jar-operated, clock-operated, or electronic) The size of sample obtained (usually 500 to 1000 cm3, with larger sizes available on request) The working pressure (usually up to 10,000 psi, with higher pressure devices available on request) The type of construction (normal or corrosive, H2S service) Figure 2 (Schematic of a typical bottomhole sampler showing (a) sampler open while going in hole, and (b) sampler closed after reaching sampling point) is a schematic of a typical bottomhole sampling device.

Figure 2

It is representative of the two principal types of samplers, the Wofford and the Leutert. The sampler shown is about 6 ft (2 m) in length and about 1 1/2 in (4 cm) in diameter. The actuator, which releases the springs and closes the sampler valves, may be mechanically operated by jarring the tool so as to shear the pins holding the sampler open, or may have a clock-driven mechanism designed to close the sampler after perhaps 2 1/2, 5, or 10 hours. Electronic triggering devices are also available. These devices are run on an electric line and allow subsurface pressure and temperature conditions to be monitored at the surface via the electronic cable. When the pressure conditions are considered appropriate, the sampler can be activated electronically from the surface. If run in conjunction with a casing collar locator, precise control of sampling depth is maintained. This approach can be useful in eliminating the need to run a pressure/temperature survey prior to running conventional sampling equipment. The sampler should be run with the chamber open, at speeds between 100 to 200 ft/min (30 to 60 m/min). Just before reaching sampling depth, speed should be reduced. With the sample at the proper depth, upward and downward movements should be made over a 20 to 30 ft (6 to 8 m) interval to ensure the sampler ports are clear. If a clockactuation mechanism is used, the sampler should be at the sampling depth about 30 minutes before closing and removed about 15 minutes later (Flopetrol 1973). At least two or three samples should be obtained. This allows comparison to determine if the samples are truly representative; it also provides a backup sample if leakage or loss occurs on the way to the laboratory. Usually, two complete sampling devices are available on location in case of malfunctions. A check on the quality of the sample should be done on each oil sample when the sampler has been retrieved to the surface. This check estimates the bubble-point pressure of the fluid in the sampler, allowing its value to be compared with that estimated by correlations. If the measured and estimated values are close, one can feel relatively sure that the sample is good. Also, if multiple samples have measured bubblepoint pressures that are similar (within 2%), the samples can be assumed to be representative. The bubble-point pressure measured at the surface should be slightly less than the bubble-point pressure at the point where the sample was taken, simply because the pressure in the sampler has fallen slightly as the temperature has been reduced in bringing the sampler to the surface. If the measured bubble-point pressure is greater than the sampling pressure, it is an indication that the sampler has either collected free gas or leaked oil. The check is done by removing the actuator from the sample chamber and attaching a head that allows the injection of mercury into the chamber. A calibrated mercury pump is hooked up to the sampler head and mercury is pumped under pressure, opening the sampler valve and allowing mercury to enter the chamber. Small volumes of mercury are pumped and the chamber is agitated until the pressure observed at the pump stabilizes. The pressure and pump readings are recorded. This is repeated until the response from the mercury injection becomes very large. The pump reading versus pressure is plotted, as shown in Figure 3 (Plot of mercury pump reading versus chamber pressure indicating bubble-point pressure of oil samples).

Figure 3

A significant change in slope will occur at the saturation pressure. The sample is then transferred to a container suitable for transportation, again using the mercury pump. Figure 4 (Apparatus for transferring bottomhole sample into storage container for shipment to laboratory using mercury pump pressure) shows how this apparatus is constructed.

Figure 4

A container whose capacity should be at least 10% greater than the sampler chamber is filled with mercury while in the laboratory. At the site, the sampler is connected to the system via the transfer head. With valves 4, 5, and 8 open, mercury is pumped until it appears at a loosened connection at valve 6. This purges the connecting lines and head. The connection at valve 6 is tightened and valves 5, 6, 9 are closed, while 4 and 8 are open. Mercury is pumped until the sampler opens. The pressure is recorded, and mercury is pumped again until the pressure is at least 500 psi (3450 kPa) above the sampling point pressure. The sampler should be gently rocked and pressured with mercury until the pressure response to mercury injection shows that the sampler is liquid full. When this occurs, first valve 5 and then valve 6 are slowly opened while pumping mercury to maintain pressure. Valve 9 is then opened slightly and mercury is allowed to drain into a calibrated receiver while pump pressure is maintained. When the volume of mercury withdrawn from the storage container exceeds the volume of the sampler, valve 9 is closed, followed by valve 6. Container pressure and temperature are recorded. A small amount of mercury should be withdrawn (about 10% of sampler volume) to allow a vapor phase to form in the storage container. (Under no circumstances should any hydrocarbon fluid be withdrawn.) This volume should be recorded, and the container tagged and checked for leaks before shipment. Transfer of the bottomhole sampler fluid may also be carried out using gravity and the density differences of oil and mercury.

Figure 5 (Apparatus for transferring bottomhole sample into storage container, using gravity drainage) shows the apparatus for this method.

Figure 5

Air is purged from the lines and sight glass by pumping mercury through them and out through loosened connections. With all connections tightened, valves 6 and 7 are closed and mercury is pumped into the system until the pressure exceeds the pressure in the sampler. Valve 6 is opened and the sample is pressured into a single-liquid phase by alternately injecting mercury and gently rocking the sampler. Valve 7 is opened, allowing mercury to flow by gravity from the container into the sampler and displace the sample into the container. The sampler is tilted to enable the mercury to flow gently downhill without mixing with the oil. At this point, valve 4 may be closed, and the mercury pump removed for other use. The sight glass will be filled with mercury when the transfer is complete, if the container has a larger capacity than the sampler. The valves on the container are then closed and the container detached from the system. A vapor space should be created in the container by releasing a portion of the remaining mercury before the container is tagged for shipment. The API Recommended Practice No. 44 details additional transfer systems when sampling equipment is slightly different in configuration. The measurement of the sample bubble-point pressure may be done after transfer to the storage container rather than before, depending on the preference of the sampling

company. The vapor space in the storage container allows for thermal expansion without danger of bursting or leakage.

Surface Sampling
The procedure for surface sampling includes the following steps: 1. Condition the well to insure that a single-phase representative fluid is flowing into the wellbore 2. Maintain the final conditioning flow rate 3. Accurately measure and record the GOR 4. Sample the gas and oil streams at the primary or first stage separator and at separator pressure 5. Accurately record sample data and tag for shipment to laboratory After conditioning the well, the final conditioning flow rate should insure a stable GOR. Generally, the low stabilized rate will not exceed 100 bbl/day (16 m 3/day) for an oil well, or 1 MMSCF/day (30 Mm3/day) for a gas well, unless the reservoir has high deliverability. (Moderate deliverability oil wells completed with large diameter tubing can experience heading at low rates, so this must be considered a rough rule of thumb.) It is essential that the gas and oil rates be accurately measured and that the resulting GOR not fluctuate. Every effort should be made to employ experienced personnel for this critical operation. When multistage separation is used, both the samples should be taken from the highestpressure separator within one hour of each other. Multiple gas and oil samples should be collected, as with subsurface sampling. Figure 1(Schematic of surface production facilities with sampling points noted.

Figure 1

Difference in conditions between separator and stock tank require adjustment of GOR ) shows a schematic of a basic single separator surface production facility with surface sampling points noted. Because the oil is collected at separator pressure and temperature, and the producing gas-oil ratio often is measured relative to the stock tank barrel, an adjustment may be necessary to determine the actual ratio in which the samples should be recombined. The measured gas-oil ratio must be multiplied by a shrinkage factor from separator to stock tank conditions. This factor is usually determined in the laboratory by "flashing" a small volume of separator oil to stock tank conditions. If the oil rate is measured within the separator, or by a positive volume meter associated with the separator, the GOR adjustment is not necessary. If multiple stage separation takes place and significant stock tank vapors are recovered, the true GOR will be the sum of the gas volumes collected at the various stages divided by the stock tank liquid volume. If the surface gas and oil samples are taken at the highest pressure separator, the recombination GOR should be determined from the relative amounts of gas and oil at the high pressure separator's conditions.

Surface Gas Sampling

There are three basic methods for sampling the gas stream. Method 1. Filling an evacuated container. Method 2. Filling an air-filled container after purging it with separator gas.

Method 3. Filling a liquid-filled container by displacement with separator gas. For a GOR of less than 1500 scf/bbl, two cylinders of 20-liter capacity should be obtained. Between 1500 and 3000 scf/bbl, three cylinders are required, and above 3000 scf/bbl, four cylinders are necessary. Method 1 requires that the connecting line between the separator and sample container be purged with gas, and that the gas then be allowed to flow into the container until the desired pressure is reached. Although this method requires that an evacuated container be available on location, it is the recommended method for gas sampling. Pressure on the container should be checked prior to sampling to ensure that a vacuum exists. Method 2 requires that the container be filled and emptied with separator gas several times in order to purge the container of air. The number of recommended successive purge cycles is inversely proportional to the separator's maximum gas pressure, as shown in Table 1, below. Method 3 requires that a two-valve sample container be filled with a liquid, preferably mercury or salt water (but glycol or water may be used). The container is kept vertical while the upper valve is connected to the separator and the lower valve is opened to withdraw the liquid. When all the liquid is displaced, the valves are closed and the container is removed for shipment. Maximum container pressure psig 10-14 15-19 20-29 30 - 59 60 - 84 85 - 149 150 - 450 450+ (kPa) (70-100) (100-150) (150-200) (200-400) (400-600) (600-1000) (1000-3100) (3100+) 16 13 10 8 5 4 3 2 Minimum purge cycles

Table 1. Recommended gas sample container purging cycles for surface separator sampling (from API RP44. 1966; reprinted by permission of API). Several problems may be encountered during gas sampling, including: entrained oil in the gas stream; corrosive gases in the gas stream; condensation of hydrocarbons within the container. Entrained oil can be eliminated by being certain to sample downstream of a correctly functioning mist extractor. If a mist extractor is not available, a filter should be installed in the line connecting the sample container to the source.

Corrosive gases such as H2S or CO2are easily absorbed by water and will react with steel containers. If such gases are present, the liquid-displacement method should not utilize water, brine, or glycol. Additionally, the gas should be dried by passing it over a suitable drying agent (such as anhydrous calcium sulfate). Nonmetal cylinders should be used if gas is suspected to contain H2S or CO2. Recommended sizes for gas-dehydration tubes are listed in API HP 44. Measurement of H2S and CO2 content should be performed at the well site if significant amounts of these components are present. Absorption/adsorption of these components during transportation and storage prior to laboratory analysis can render an otherwise "sour" sample "sweet." Condensation of hydrocarbons within the sample container can be a problem, especially when the separator temperature is significantly higher than the sample container. This problem can result in a non-representative sample being obtained, especially when Methods 2 or 3 are used for sampling. Use of an evacuated container (Method 1) will not eliminate the condensation, but will make its effect less serious. Other steps include warming the sampling container and maintaining it in a vertical position during purging to allow condensation to drain out.

Surface Liquid Sampling

There are three basic methods for liquid sampling: Method 1. Displacement of a liquid-filled sample container (mercury, brine, glycol, and water are suitable). Method 2. Displacement of a gas-filled sample container (separator gas is used). Method 3. Purging the container with separator oil. All of these methods have the objective of obtaining a sample of separator oil with no loss of dissolved gas and with no contamination by extraneous gases or liquids. All connections used to conduct fluid from the separator to the sample container must be purged with separator oil to avoid contamination. Method 1 requires that a sample container, with a capacity of about 600 cm3, be filled with a liquid (mercury, brine, glycol, or water) and connected to the separator as shown in Figure 1 (Sampling apparatus for obtaining separator oil sample by the displacement of a liquid from a prefilled sample container). After purging the sampling line, valve 5 is opened to allow the container to come to separator pressure.

Figure 1

Then valve 6 is slowly opened to allow the oil to flow into the container and displace the resident liquid with minimum pressure reduction. When the desired sample volume is collected, valve 6 is closed, followed by valve 5. A vapor space is left in the container by withdrawing an additional 10% of the displacement fluid. It is critical that absolutely no amount of hydrocarbon sample be withdrawn during this procedure. The container is disconnected, checked for leaks, and tagged for shipment. Method 2 requires that the container first be filled with separator gas at separator pressure. Method 2 for obtaining gas samples should be followed for filling the container. With a pressure gauge installed on the top of the container, the bottom of the container is connected through a purged line to the separator. The sample is taken by opening the bottom valve and bleeding off the gas through the top valve, adjusting the rate so that no appreciable pressure drop occurs in the container. A pressure drop will cause part of the oil to vaporize, resulting in a nonrepresentative sample. When oil flows from the top valve, both valves are closed and the container is disconnected. A vapor space may be provided for by displacing a portion (10% of sample container) of the oil with separator gas, at the constant container pressure, from top to bottom. Another technique is, with the container in a vertical position, to release 10% of the sample contents from the bottom valve. This technique should only be used if the earlier methods cannot be followed. It is very important that the technique used for providing a vapor space be noted on the sampling records. Laboratory personnel must remove the displacing gas before using the oil for recombination.

Method 3 for liquid sampling requires that separator oil be flowed from bottom to top through the sample container at a pressure equal to the separator pressure. After several container volumes have flowed through the container, the valves are closed. A portion (10%) of the container volume is quickly released from the bottom valve with the container in a vertical position. This method requires considerable care to ensure that dissolved gas is not released into the container during flow. Methods 1 and 2 are preferable. The loss of sample in Method 3 can result in questionable results, and this technique should only be followed as a last resort. Several problems can occur during oil sampling, including these possibilities: Separator temperature may be lower than that of the sample container, causing vaporization within the container H2S or CO2 can react with water and attack the container walls The sample container should be cooled to separator temperature or below. If the oil vaporizes within the container, an insufficient volume of oil may be recovered. Also, if flashed vapors are lost, a nonrepresentative sample will result. H2S and CO2 corrosion can be minimized by taking care to obtain a water-free sample from the separator. A calcium sulfate drying tube can be used if emulsified water is unavoidable. Dry gas wells and oil wells that flow undersaturated liquid at the surface may be sampled at the wellhead using these surface sampling techniques, provided the pressure rating of the sample containers is sufficient to permit such a procedure. Split-stream sampling is another surface sampling technique that has been utilized, particularly for gas condensate wells. A small-diameter tube is inserted into the middle of the flow stream, usually in the center of the flow stream, 8 to 10 ft (2-3 m) below the wellhead, or just upstream of the separator. The velocity of the fluid in the flow tube should be the same as that in the flow line or tubing. The flow is diverted into sampling bottles or into a small, temperature-control led separator, from which recombination samples may be taken, thereby averaging out any small fluctuations in the instantaneous GOR. The split-stream method loses accuracy with very high liquid content gases where much of the liquid is flowing close to the walls of the tubing, and a sample from the tubing center is not representative (Amyx, Bass, and Whiting 1960). For this reason split-stream sampling is not recommended and its use is discouraged for any sampling involving multiphase flow.