Jereny Thompson Steven Farnival ECL Petroleum PVT Analysis Course March: 1991 Exploration Consultants Highlands Farm Greys Road Henley, Oxon, RGO 4PS, UK Tel. 0491 575980 Technologies € ! | !Why Study PVT? e Require Knowledge of Fluid Behaviour in Reservoir, Well and at surface ‘TRANSPORT ~ REFINING SURFACE SEPARATION GAS INJECTION © (RECYCLING) MULTLPHASE FLOW MISCIBLEAMMISICIBLE DISPLACEMENT SAMPLING ‘PRESSURE DECLINE a NEAR-WELLBORE BLOCKAGE e Over a Wide range of pressures, temperatures and compositionsContents CONTENTS 1. Gas Condensate Systems 1.1 Genesis 1.2 Composition 1.2.1 Paraffin Hydrocarbons. 1.2.2 Cycloparaffins 1.2.8 Aromatic Hydrocarbons 1.2.4 Polynuclear Hydrocarbons 1.2.5 Other Organic Components 1.2.6 Single Carbon Number Groups 2. Properties of Pure Substances 2.1 Laws and Definitions 2.1.1 Boyles’ Law 2.1.2 Charles’ Law 2.1.3 Avagadro’s Hypothesis 2.1.4 The Ideal Gas Law 2.2 Non Ideal Behaviour 2.3 Change of Phase 2.4 The Law of Corresponding States 2.5 Property Trends» 2.6 Characterisation PVT Course -i- March 1991 ECL Petroleum TechnologiesOo Contents 6. Equations of State 6.1 Ideal Gas Law 6.2 Phase Changes in EoS 6.3 Van der Waals’ EoS 6.4 Redlich-Kwong EoS 6.5 Soave-Redlich-Kwong EoS 6.6 Peng-Robinson EoS 6.1 Zudkevitch-Joffe EoS 6.8 Three Parameter EoS 6.9 Generalised BoS 6.10 EoS for Mixtures 7. Simulation of Experiments 7.1 Equilibrium Flash and Saturation Pressure Calculation 7.1.1 Flash Calculation 7.1.2 Bubble and Dew Point Calculations 7.2 Pressure Depletion Experiments 7.2.1 Constant Composition Expansion 7.2.2 Constant Volume Depletion 7.2.3 Differential Liberation 7.3 Lean Gas Injection 7.3.1 Swelling Test 7.3.2 Vapourisation Test 7.4 Multi-Stage Separators 7.5 Variation of Composition with Depth 7.6 Ternary Diagram PVT Course. iti ; March 1991 ECL Petroleum TechnologiesContents 8. Splitting and Grouping 8.1 Splitting 8.2 Grouping | | 9. Regression | 9.1 Prior to Regression 9.2 Rules for Regression 9.3 Variable Choice 9.4 Theoretical Model 10. PVT Data for Simulation 10.1 Blackoil Model 10.2 Pseudo-Compositional Model 10.3 Compositional Model References O PVT Course iv: March 1991 ECL Petroleum TechnologiesContents | | | APPENDICES A.1 Classical Thermodynamics | A.1.1 Conservation of Energy A.1.2 Measures of Energy | A.1.3 Fugacity and Fugacity Coefficient A.1.4 Multi-Component Mixtures A.15 Phase Equlibria A.1.6 Stability Analysis . A.1.7 Peneloux Volume Correction Method A.2 Viscosity Calculation A.2.1 Lohrenz, Bray and Clark A.2.2 Pedersen et al. | A.3 Pure Component Physical Properties A.4 Glossary of Terms and Definitions A.5 UKOOA Sampling Working Group - Guidlines for Sampling A.G Example PVT Report oO PVT Course ve March 1991 ECL Petroleam Technologies| Genesis ¢ Origin of Petroleum is organic material preserved in Sedimentary rock - plant and animal remains - oxygen deficient enviroment e Subject to temperature and burial history - pressure and (geological) time have little effect e Oil window: 5000 to 20000 ftGas Condensate Systems 1 GAS CONDENSATE SYSTEMS 1.1 Genesis Gas-condensates, in common with the other common forms of petroleum hydrocarbon systems, have as their origin organic matter which has been preserved in sedimentary rocks. This organic matter is invariably a mixture of both animal and plant remains which have avoided the normal fate of oxidation and decay. In the presence of an anoxic, or oxygen deficient environment, (such as a stagnant lagoon) dead plant and animal matter will accumulate along with silt to create an organi- cally rich sediment. This may later become a ‘black’ shale, a potential petroleum source rock. Whether or not this happens will depend on the subsequent burial and temperature history of the sediment. At relatively modest depths and temperatures, (less than 5000 Fect) anaerobic bacterial action forms kerogen from the remains, and it is the subsequent effect of temperature on the kerogen which determines the properties of the petroleum system which will ultimately result. Pressure and time have relatively little effect on the outcome. At temperatures above 120°F, kerogen begins to ercate crude oil, rich in asphaltenes. As the temperature is increased further, above 200°F, the system will begin to generate lighter hydrocarbons, and hence lighter oil. At around 350°F the amount of remaining C74 molecules in the system will be small, and it will have the properties of a gas condensate. A fur- ther increase in temperature will farther break down the intermediate paraffins to methane, which will be all that remains above 400°F. Under normal geothermal gradients therefore the so called ‘oil window’ will occur between the depths 5000- 21000 feet. Any organic material descending below 21000 feet is likely to produce only methane, and coal-like residues. ‘The properties of any gas-condensate system therefore depend, inter alia, on the nature of the organic source material, and the degree of ‘cooking’ to which it has. been subjected. However, the migration history is also critically important, as the reservoir rock in which the system is found may not necessarily be contiguous with the source material, and it may be that the constituents of the reservoir arrived at different times, or from separate sources. This may have important consequences on the initial conditions to be expected upon discovery, as certain migration conditions will pre-dispose a gas-condensate accumulation to be exactly at its dewpoint at initial reservoir conditions, even if there is little evidence of a liquid phase in the reservoir. PVT Course -l- March 1991 ECL Petroleum TechnologiesF Ambient T IMMATURE, a 100 200 300: FACIES OF ORGANIC METAMORPHISM Exposure - time assumed 50 my. Geothermal gradient 1.5°F/100ft - 2.7°C/100m. Yellow spores. & kerogen Biogenic gas Products oil Naphthenic |. CRACKING BEGINS? 90°F hd (60°C) MATURE Yellow to brown spores & kerogen Lean gas 140 Paratfinic oil, gas/ conflonsato| 400. 500. 497°C) DEGENERATIONZ 30°F, Li METAMORPHIC Dark brown to Ce kerogen Dry gas carbon : Dry gas 10,000 20,000 600. BARREN: 00°} 00" Low - Grade Mineral Metamorphism From Fuller, After Evans & StaplinGas Condensate Systems 1.2 Composition Because of the organic nature of their source, all petroleum accumulations, including gas condensates, have hydrocarbons as their predominant constituents However, there are many instances of accumulations containing significant percent. ages of inorganic components, the most common being the so called “acid” gases, carbon dioxide and hydrogen sulphide. Systems containing acid gases are also re. ferred to as being “sour”. The hydrocarbon constituents of petroleum systems are classified into the following categories, most of which describe series (known as homologous series) of compounds having a common basic characteristic or structure, and differing only in the number of structural carbon atoms. (And hence molecular weight) 1 Paraffin Hydrocarbons 2 Cycloparaffins 3 Aromatic Hydrocarbons 4 Polynuclear Hydrocarbons 5 Categories 1-4 above containing additional atoms as follows: a) Sulphur b) Nitrogen c) Oxygen @) Metals-most commonly Iron, Vanadium, Nickel. The main properties and characteristics of these categories are described overleaf, with specific reference, where appropriate, to the importance of these prop- erties in determining phase behaviour. PVT Course -2- March 1991 ECL Petroleum TechnologiesPARAFFIN HYDROCARBONS & H | METHANE H—C—H H ETHANE : CH,CH, PROPANE ' CH,CH,CH, n-BUTANE CH,CH,CH,CH, i-BUTANE Gia CH, n-PENTANE CH,CH,CH,CH,CH, i-PENTANE CH.GHCH,CH, oH a CH, neo-PENTANEO O Gas Condensate Systems 1.2.1 Paraffin Hydrocarbons These compounds, also known as aliphatic hydrocarbons, and generically referred to as “alkanes”, are the simplest and often the most abundant constituents of petroleum systems. They are stable and unreactive, and all have the general chemical formula C, H2n+2- Methane, CH; is the first member of the series, having n=1. The next few members of the series are as follows: n Alkane Formula 2 Ethane CHe 3 Propane CoHe 4 Butane Csi 5 Pentane CF 6 Hexane CoH 7 Heptane Cris 8 Octane Celie 9 Nonane CoH ~and so on— Carbon always exhibits a valency of 4, and hence all the carbon- carbon bonds in paraffin hydrocarbons are single bonds. In chemical nomenclature this condition is referred to as saturation and is in no way related to the meaning of saturation as related to the PVT behaviour of oil and gas systems. For n=4, (Butane) and above, the molecules may have different possible structures despite having the same formula and molecular weight. In addition to having a straight chain structure, a particular formula may also represent molecules which are branched, and the potential number of variants increases rapidly with n. The straight chain molecules are referred to as normal paraffins, and the branched molecules are generically grouped as iso paraffins. The physical properties of the iso paraffins (such as boiling point, liquid density and critical properties) may differ substantially from those of the normal paraffin having the same molecular weight, and these variations impact the phase behaviour of mixtures containing them. All potential variants having the same formula (even those belonging to a different ho- mologous series) are referred to as isomers. At low values of n, the isomers of a given paraffin can be distinguished by gas chromatography analysis, as it is at low n values that the physical property differences between isomers is greatest. As n increases, so the differences diminish, and the paraffins themselves become much PVT Course -3- March 1991 ECL Petroleum TechnologiesCYCLOPARAFFINS CYCLOPROPANE CYCLOBUTANE CYCLOPENTANE ae i ’ CH CH, NZ CYCLOHEXANE METHYLCYCLOHEXANE CH, CHGas Condensate Systems less volatile, and therefore more difficult to resolve using GC. Systems containing significant amounts of high molecular weight paraffins will be waxy, and will pre- cipitate out wax as temperature decreases. Rather than exhibiting a continuous reduction in viscosity with temperature, such systems will have a tendency to ‘set” at. a given temperature. Appendix A.2 details the physical properties of the common constituents of hydrocarbon systems. PVT Course 4 “March 1991 ECL Petroleum TechnologiesAROMATIC HYDROCARBONS & BENZENE TOLUENE XYLENEGas Condensate Systems 1.2.2 Cycloparaffins These are compounds where the chain structures of normal paraffins have been formed into rings, but all the carbon-carbon bonds are still single, and they are therefore, from a chemical nomenclature viewpoint, saturated. It is possible to form a ring paraffin from three or more carbon atoms, the first member of the series being cyclopropane, C3 Hs. Alll the simple cycloparaffins have the chemical formula C,, Hn, which is the same generic form as the olefins, or alkenes. These compounds are characterised by having one or more carbon-carbon double bonds, the simplest olefin being ethylene. Olefins are not naturally occurring, but the have considerable importance in the downstream petroleum business. At low carbon numbers cycloparaffins are significantly less stable than their normal paraffin counterparts (i.e molecules having the same carbon number) and are therefore present in much smaller amounts. However, in gas/condensate systems in particular, reactive species can have a significant effect on phase behaviour even in relatively small amounts. As the molecular weight of cycloparaffins increase they form collections of contiguous rings of five or six carbons atoms per ring, rather than single rings of ever increasing size. These are collectively known as naphthenes, and are equally as stable as their chain paraffin counterparts. PVT Course 5. : March 1991 ECL Petroleum TechnologiesPOLYNUCLEAR HYDROCARBON: NAPHTHALENE PHENANTHRENE INDANOo © Gas Condensate Systems 1.2.3 Aromatic Hydrocarbons Aromatic hydrocarbons are compounds containing one or more benzene tings, these being stable ring compounds with the formula CeHe, and are normally represented by the structural formula shown on the facing page. This representa tion credits the benzene molecule with three double carbon-carbon bonds and the molecule is therefore unsaturated, and hence a more reactive species than paraffins having similar carbon numbers. The basic benzene ring can be attached to paraffin based chains, the most common derivatives, being toluene and xylene. In the case of xylene, it can be seen that there can be three possible structural forms of this molecule, the one illustrated being the meta form. The other two are the ortho and para forms which all have slightly different properties from one another. Benzene tings also coalesce into multi-ring structures as molecular weight increases, The aromatic content of a gas-condensate has a significant effect on its phase behaviour. PVT Course 6 : March 1991 ECL Petroleum TechnologiesPYRIDINE PHENOL OH ETHYL MERCAPTAN — CH,CH,SH METHYLTHIAZOLE cH, — N ) SsGas Condensate Systems 1.2.4 Polynuclear Hydrocarbons These are compounds, such as asphaltenes and high molecular weight ey- cloparaffins, having a number of carbon ring structures attached together. Com- binations of aromatic and eycloparaffin rings are not infrequent, an example being the molecule of indan. 1.2.5 Other Organic Components Although animal and plant matter consists of complex organic molecules containing appreciable amounts of oxygen and nitrogen, (e.g. proteins) these molecules lack Jong term stability, and relatively few oxygen and nitrogen con- taining compounds survive the petroleum formation processes. Those that do are predominantly eyclic compounds in the case of nitrogen, (e.g. pyridine) and aro- matic alcohols, aldchydes, and carboxylic acids in the case of oxygen. Sulphur compounds are relatively common, these being formed by the action of hydrogen sulphide on organic molecules, especially the more reactive species. ‘The hydrogen sulphide can be sourced either biologically, by the action of sulphate reducing bacteria, or by inorganic reactions involving metal sulphides. ‘The most. common organo-sulphur compounds in petroleum systems are mercaptans, which cun be regarded as esters of hydrogen sulphide. They are reactive, and therefore strongly influence phase behaviour when present even in relatively modest amounts. Organo-metallic compounds do not have a significant effect on phase be- haviour, usually because they are present in only trace amounts. Their importance stems from the adverse effects they can have on refinery processes, which is why they often feature in extended compositional analyses and petroleum fluid assays, PVT Course -T- : March 1991 ECL Petroleum TechnologiesSCN Groups e Proliferation of isomers with increasing Carbon number makes individual identification impossible «Introduce Single Carbon Number (SCN) Groups eSCN group a: all hydrocarbons with Ti(nCn_) < T, < Th(Ch) -ie. Benzene (C¢H¢) is usually found in SCN group 7.Gas Condensate Systems 1.2.6 Single Carbon Number Groups It can be seen from the previous sections that there is a considerable di- versity of components present in natural hydrocarbon fluids. The organic source material, the burial and temperature history, and the action of microbes all affect the ultimate composition of the fluid, and the relative amounts of the different com- ponents. For the lower molecular weights, modern analytical methods can identify individual components, and isomers of these basic components. However as the molecular weights of the hydrocarbon components rise, it becomes less easy to dis- criminate them using routine analytical methods. The most usual compromise is to report the composition of the higher molecular weight residues in terms of boil- ing point fractions, which are the amounts of fluid which distil over between two specified temperatures. The temperature intervals are often chosen so as to be between the boiling points of each member of the series of normal paraffins, and the fractions are referred to by the number of carbon atoms in the relevent normal paraffin, Thus, the fraction which is referred to as the C9 fraction includes com- pounds which may have less than 9 carbon atoms, but have a higher boiling point thau the normal paraffin with the same number of carbon atoms. In, for example, the C7 boiling point fraction, benzene, which has only 6 carbon atoms, would be included. Similarly, toluene would be included in the C8 group. These groups are often referred to as single carbon number (SCN) groups, which is therefore mislead- ing. It is important to recognise that only in the case ‘of an extremely paraffinic fluid would the reported single carbon number groupings have the properties of the corresponding normal paraffin, such as molecular weight or critical tempera- ture and pressure. In most cases such an assumption will lead to difficulties in predicting fluid behaviour. For carbon numbers above which analysis for individ- ual components becomes impractical, (around C10-+) it is important to know the relative amounts of paraffinic, naphthenic, and aromatic compounds in each of the single carbon number groupings, in order that better estimates of group properties can be made. If true distillations are performed, as against simulated distillations using gas chromatography, this can be partially achieved by measuring the molec- ular weight and specific gravity of each true boiling point (TBP) fraction. A true paraffin, naphthene, and aromatic (PNA) breakdown has to be performed via mass spectrometry methods for the heavier fractions, and this is not a routine procedure. PVT Course 8 March 1991 ECL Petroleum TechnologiesBoyle's Law 1 Pressure For a fixed mass of gas at constant temperature : pV = Constant 1/Volume —> Charles’ Law 1 Temperature For a fixed mass of gas at constant | pressure V/T = ConstantOo O Properties of Pure Substances 2 PROPERTIES OF PURE SUBSTANCES From the previous section, we have seen that most hydrocarbons can be grouped into “series”. As might be expected, the physical properties of members of such series tend to vary in some prescribed way. We shall use these trends to develop mathematical relationships to model the behaviour of hydrocarbon fluids across ranges of pressures, volumes and temperatures. However, firstly, we need to identify the key physical properties of components and discuss how the vary. 2.1 Laws and Definitions The basic information needed to apply thermodynamics to the behaviour of fluids are pressure, volume, temperature and composition. The inter-relationship of these quantities will form the basis for the development and use of Equations of state (EoS). 2.1.1: Boyle’s Law Boyle's Law is based on observations made around 1660, that for a fixed 's of gas at a fixed temperature, the product of pressure and volume is a constant, pV = constant () 2.1.2: Charles’ Law Over a century later (1787) it was observed that for a fixed mass of gas at constant pressure, the volume varies linearly with temperature, ie. if the gas had a volume Vo at 0°C, at a temperature T: V=V(1 +a) 2) The gradient, a, is found to have the value 1/273 and, as a consequence, when T = ~273°C the gas volume will become zero. By re-specifying a temperature seale T" with the same spacing of degrees as the centigrade scale, but starting with 0 ut 273°C the volume/temperature relationship becomes: Vo aw Vv 373 T (3) PVT Course -9- “March 1991 ECL Petroleum TechnologiesAvagadro’s Hypothesis e Equal volumes of gas at the same conditions of temperature and pressure contain the same number of molecules e One mole of any gas at standard conditions will occupy a fixed volume e 1 gram mole weight of a substance occupies a volume of 22400 cm? at a pressure of 760 mm Hg and o°C e 1 pound mole weight of a substance occupies 379.484 f23 at a pressure of 14.7 psia and 60°FProperties of Pure Substances i The scale is the absolute temperature scale, measured in degrees kelvin (K), jrhere | K=C4+273 (4) The Fahrenheit equivalent is the Rankine scale, R, where | | R= F +460 (5) | -1.3: Avagadro’s Hypothesis Advanced as a hypothesis in 1811, it is now sufficiently validated to be Jevated to a physical law. It states that the number of molecules in a gas of specified volume, temperature and pressure is the same for all gases, and is independent of he nature of the gas. It follows from this that the ratios of masses of two different ses of the same volume, pressure and temperature must be the ratio of the weight of the molecules of the gases, given that the same number of molecules are being ompared. Expressed another way, a molecular weight of gas (eg. 2 mass units of hydrogen, 32 mass units of oxygen, 16 mass units of methane ete.) will contain a known number of molecules and occupy a predictable volume. Such a quantity is bbreviated to a mole, and can be expressed in any mass units required. ie. 1 gramme mole occupies a volume of 22400 cc at a pressure of 760 mm mercury and 0°C, and contains 6.06 x 10? molecules. In oil field units the appropriate mass unit is the pound, and the standard conditions are shifted slightly. ‘The resulting definition is: 1 Ib mole occupies a volume of 379.484 cubic feet at a pressure of 14.7 psia and a temperature of 60°F. | Therefore 2lbs of hydrogen, 32 Ib of oxygen and 16 Ib of methane will all ccupy 379.484 cubic feet at the specified conditions: assuming they behave ideally! VT Course -10- March 1991 ECL Petroleum TechnologiesIdeal Gas Law © Boyle’s Law: fixed mass of gas at constant temperature | pV =constant ¢ Charles’ Law: fixed mass of gas at constant pressure “ stant = = constan T «Combining — Ideal Gas Law pV = NRT - R= 10.732 psia/ ft? /lbmole - R= 0.0821 barsa/m3/kgmoleC Properties of Pure Substances 2.1.4: The Ideal Gas Law | Combining Boyle’s Law with Charles’s Law, and a similar observation con- \ccrning the variation of pressure with temperature at constant volume, yields the ideal gas law: PV =RT (6) which is an equation of state for ideal gases. The constant, R, is defined using |Avagadro’s hypothesis, and in oilfield nits is: | psia 0.13255 ole If 1 lb-mole is involved, at a pressure of 14.7 psia and temperature of 60°F, the volume occupied will be : 10.732 x (60+ 400) 4, 14.7 = 379.5cu. ft. If N Ib-moles are involved then the relationship is simply: PV=NRT (7) All the foregoing assumed that we are dealing with an ideal gas, which most gases are not, certainly not over the range of conditions encountered in oil fe applications. However, many gases (including mixtures such as air) exhibit pchaviour approximating closely to ideal at and around standard conditions. Ideal behaviour pre-supposes two properties of a gas, neither of which are rue, namely: . (i) The molecules are infinitely small (ii) There are no inter-molecular forces. Condition (i) is imposed by Charles’ Law, in that all volume must vanish at IT =0. For condition (ii) to hold would mean that no gaseous element or compound could ever change state into a liquid or a solid. PVT Course -ll- : March 1991 ECL Pctroleum TechnologiesAssumptions and Limitations e Assumptions of the Ideal Gas Law pV = NRT - Molecules are point-like, ie. zero volume - No inter-molecular forces e but - Gases are not infinitely compressible - No account of change of phase| Properties of Pure Substances | 2.2 Non-Ideal Behaviour Various attempts were made in the latter half of the 19th Century to modify the ideal gas equation of state to account for departures from ideal behaviour, one if the more famous being the * Van der Waals equation: | a | (p+ FY — 0) = RE (8) | | Where the 6 term can be loosely interpreted as a correction for the finite size df the molecules and a/V? as an “internal pressure” correction for the existence of intermolecular forces. Several others were published afterwards, notably by Clausius (1880) Berthelot (1878) and Dieterici (1899). i a : (p+ Rveopy =b)=RT Clausius (9) | (p+ pV —b)=RT Berthelot (10) | p(V-b)= Reepl-s7pp) Dicterict (41) | | As with the Van der Waals equation, the constants a and b are specific to the as. For applications where the prediction of changes of state are unimportant, such s relating the volume of a real gas at one set of temperature and pressure conditions Jo another set, the problem is overcome via the use of Z-factors or compressibility factors. These are functions both of temperature and pressure, and the gas involved, and the method is applicable to gas mixtures also. | The problem of relating the gas in state (i) to state (ii) is thus: PiVi _ p2Ve Th ~ Ti (2) The Z-factors neéd to be known for each state, although often the Z factor At standard conditions (60°F, 14.7 psia) is equated to 1. They can be calculated or measured, the calculation method for mixtures lying on the validity of the law of corresponding states, which is discussed later. * This equation will be analysed in some detail in the section on Equations of State VT Course -12- March 1991 ECL Petroleum TechnologiesTHE p-V-T RELATION OF A PURE SUBSTANCE From Adkins “Equilibrium Thermodynamics”THE TWO MOST USEFUL PROJECTIONS OF THE p-V-T SURFACE From Adkins “Equilibrium Thermodynamics”Critical Point VAPOUR Triple Point TemperatureoO I Properties of Pure Substances los Change of Phase | One obvious observation of non-ideal behaviour is that gases do become liquids, and vice versa, and that the properties of the two phases are quite differ- ent. For any pure substance a diagram can be constructed (from observations and experiments) which will illustrate the behaviour of a fixed mass of the substance under all conditions of temperature and pressure. Such a diagram is a phase dia- |gram, and a typical example is shown on the facing page. By definition, since it relates pressure, volume and temperature it is a 3-dimensional plot, which contains too much information to be quantitatively useful, and it is therefore most usual to examine projections and slices through the plot, either in the P-V plane or the P-T plane. A projection of the diagram onto the P-T plane is shown overleaf. Since, for a given temperature, liquification and solidification proceed at constant pressure, the mixed phase regions project into lines on the P-T plane. At one temperature, the triple point, all three phases can co-exist. Unusually, the diagram for water has a negative slope to the solid line, which is why isothermal compression of ice causes it to melt. The liquid/vapour line comes to an abrupt end at the coordinate p, and Ty known as the critical point. For temperatures above T., the critical temperature, liquification cannot be achieved by isothermal compression. At the critical point one nuole of substance occupies a critical volume V,. These three critical constants for any gas are not related by the gas law. Indeed the quantity (RT.)/(p.V.), the critical coefficient, is normally between the values of 3 and 3.5 (ideal gas behaviour would make it equal to 1) for simple gases, but can rise above 5 for reactive, polyatomic compounds. PVT Course -13- ‘i March 1991 ECL Petroleum TechnologiesBEHAVIOR OF OIL FIELD HYDROCARBON SYSTEMS PSEUDO REDUCED PRESSURE & z 5 e g E a 5 3 g i o xv COMPRESSIBILITY FACTOR estien SEPARA cust © W 2 3 14 PSEUDO REDUCED PRESSURE Comprensiisty Factors for Natural Gates (After Sunding and Kate, Trans. AIME, 1942)| Properties of Pure Substances I \2-4 The Law of Cor ondin ites | Nevertheless, it was found (by Van der Weals, 1873) that diverse real gases appear to have much more PVT behaviour in common, when their equations of state are expressed in reduced form, that is that the pressures, temperatures and ‘volumes are all expressed as a ratio of the critical properties for the gas in question, ire Te and Vc, This implies that the P-V slices through the phase diagrams of different gases will all appear the same if scaled using 'reduced’ pressures volumes ‘and temperatures (ie. as functions of p/p., V/V; and T/T.). For simple, single ‘component gases, this conclusion, referred to as the law of corresponding states, holds quite well, but fails progressively for more complex, polar species. When applied to the gaseous region in the phase diagram, the law of corre- sponding states means that the same real gas compressibility factors (or Z-Factors) Ireferred to earlier can be applied to different gases when they are in the same reduced conditions. ie. Z is unique to a given p/p., T/Te. It was not until 1936 that experimental work by Kay, and correlations lbased on his data, proved the extension of the Law of corresponding states to the Itreatment of gaseous mixtures, specifically hydrocarbon gas mixtures. Based on the omposition of the gas mixture, a set of critical constants can be calculated for the mixture from mole fraction weighted critical value for the individual components of the mixture. The resulting values are called pseudo-criticals, denoted Pre The and Vpe and are used in exactly the same way as pe, and T, in the determination f Z-factors. This can be done from the now famous chart generated by M.B. tanding in 1942, shown opposite. Various numerical methods also exist, among he more popular being the Yarborough-Hall method , ref.(1) , which forms the hei of calculation of the HP-41-C fluids pack. | Naturally occurring oil and gas mixtures are usually too complex for a omplete classification of all constituent components. Standard laboratory analyses sually only identify three non-hydrocarbons, namely Nz, H2S, CO» and the hydro- arbons C;,C2,Cs,iC4,nC4,iCs,nCs and components called Ce, hexanes, ete. As has been noted, the number of isomers increases rapidly for carbon number 6 and eee It has been estimated that there are between 1 x 10° and 3 x 10° isomers of ‘so! ! | | | | | pr Course, -14- March 1991 | ECL Petroleum Technologies | | |Property Trends e For Hydrocarbon Groups, Properties increasing with increasing mole weight - I. : Critical Temperature | -,: Normal Boiling Point - - Vz: Critical Volume -w : Acentric Factor eel i. - po: Normal Liquid Density | - Pa: Parachor Decreasing with Increasing Mole Weight | -pe: Critical Pressure - Z,: Critical Z-Factori | | Properties of Pure Substances 2.5 Property Trend: For the hydrocarbon series such as the Alkunes, most physical properties | such as the critical pressures and temperatures, normal boiling point temperatures, | * acentric factor, etc., are found to either increase or decrease monotonically with increasing Carbon number (and hence molecular weight). This variation is used as the basis for the characterisation of “unknown” components, as will be seen in the next section. | Most laboratory p-V-T reports consist the indentification of the three non- hydrocarbons: 1. Carbon Dioxide 2. Nitrogen 3. Hydrogen Sulphide and occasionally traces of Helium and Carbon Monoxide, Next the specific hydro- carbon components, Methane, Ethane, Propane and the two isomers of Butane and Pentane, the iso- and normal-alkanes (Pentane contains a third isomer, neo-Pentane which rarely occurs in natural Petroleum but if it does it is “lumped” into the iso- Pentane). After this, the number of isomers increases rapidly and so we generally |switch to the SCN description. The components called hexanes, heptanes, etc., are usually referred to as Single Carbon Number (SCN) groups and are defined, ie. hexanes, as all hydro- carbons that boil between the normal boiling of nCs and nCe, etc. Tables of the properties of SCN groups for “typical” fluids are widely available, see Whit- |son (1983), but ideally the density and mole weight of such “lumped” components should always be reported in a laboratory analysis, but rarely are. i All p-V-T reports should have a component analysis up to some upper icarbon number to be specified by the owner of the fluid, say 6, 11 or 19. The residual hydrocarbon fluid is usually referred to as the plus fraction, ie. Cr, Ciz4 ‘or Czo4. For such a component, only a limited set of information will be made available, usually the mole weight My4 and the specific gravity yy.4. For use in lan EoS model, it is necessary to calculate the EoS parameters, such a8 Ts, pey lete., via correlations depending on My and 4. ee | * See Glossary, Appendix A.4 | pvr Course -15- - March 1991 ECL Petroleum TechnologiesCharacterisation e Plus fraction properties reported: | Mn++ - y+ May have to be estimated from SCN tables |e EoS requires T,,p.,w, etc. e Correlations such as | Riazi-Daubert 6 = aTpy - (a,b,c) are tabulated coefficients (see Whitson, 1983).oO Properties of Pure Substances (2.6 Characterisation | Several authors have generated correlations for calculating the EoS param- icters Te, Pe, w, etc., from mole weight and specific gravity, such as Kesler-Lee: | Pe = 8.3634 — = | — (0.24244 + 2.20804 + 24 ourx 10-7, | vse 28 107772 — (0.42019 + a) x 10-978 (12) | T. = 341.7 4 811.0y + (0.20444 oatt4y)T | (0.4669 — 3.2623) x 10° OOO eee Ts (Inpyr ~ 5.92714 + $9848 + 1,28862InT4,, — 0.169347 Tf,) (15.2518 — = ais 472UnTy,» + 0.43577TP,) (Thr < 0.8) (14) w = ~7.904 + 0.1352Ky — 0.007465K2, + 8.359T;,, (18) w= | (Th,r > 0.8) (15) where T, and T, are the normal boiling point and critical temperatures, in degrees Rankine, respectively, 7 is the 60/60 specific gravity (density of the fraction at latmospheric pressure and 60°F divided by the density of water in g/cm® at the same conditions), p, is the critical pressure in psia, Ky is the Watson characterisation factor, Ky = T;!*/y and Th, is the reduced boiling point temperature, Thy, = n/t. Other correlations are available due to Cavett for pe, Te and Edmister for w. The correlations of Riazi-Daubert are particularly attractive since they are of Ithe form: | 6=alpy (16) where the set of properties @ that can be estimated are mole weight My, critical temperature and pressure T., pe, molar volume and density Vm, p. The values for {the three coefficients in (5), (a,2,c) are given in Whitson (1983). pvr Course -16- March 1991 ECL Petroleum Technologies_fs0u06 -foseu0b Fesoue6 resoueb reseus6 _feseued revues ebuny $5001 Begg) 9991-0 cag owey jb Loree 96500 riot 2Melt DL mow Firvornbesti Ay IPT, Nae A7B, p, 16Se ‘TABLE 1—GENERALIZED PROPERTIES OF PETROLEUM HEXANE PLUS GROUPS Average Hydrocarbon Boiling Range Boling Foi! Density Molecular Group Comme aa (g/ml) “Weight Ge 36510 692 “97 810 1867 0.685 84 68.210 989 1567102101 o7ee 35 989101264 210.110258.1 74s 107 1251101813 259.110.3044 o7es 32h 1813101748 304.410.3464 0778 134 1746101964 3464103055, 0789 447, 196.4102168 3855104222 208: 0800161 2168102359 422.2104887 227. ost 175 2359102538 456.7 104092 os 190, 2539102711 468.210520 oBs2 206 271.410287.3 520 tos47 oes 222 267 10303" 547. 10877 ose 237 303 10317 577 10603 ogse 251 317 10331 603 10628 0887 203, 331 10344 628 106s oes2 275 344 10357 852 10675 0867 ° 291 357 10369 675 10696 c872 505 369 10981 696 0717 os77 318 981 10382 717 10737 ost at 392 10402 737 10756 ess 345, 402 10413 75510775 oss 359 413 10423775 10793 0893374 423 10432 793 10.810 rc) 432 10441 810 10.826 oes = 402, 441 10450 828 10842 92 416 450 10459 B42 10.857 0.908 430, 459 10468 857 10874 0909 aaa 468 874 0888 osi2 458 476 888 10901 ose 472 483 901 10915 0917 486 ose 500 ose 514 ose 528 0926 542 oss 556 030 © 570 oes! 5Be 0933598 oss gia 0837626 JOURNAL OF FETROLEUM TECHNOLOGY4 690 aanyojedwes bv 60 OO OSE COS OGZ COZ OSL ODL OS AO Sree sate IZ eidwos JULIO }09: 0060 oo8'0 004°0 009°0 oos'o = mapa P>>>>0Properties of Mixtures 3 PROPERTIES OF MIXTURES Generally, when dealing with hydrocarbon fluids we are not considering single pure component fluids but mixtures of thousands, if not millions, of differ. ent molecular species. Thus we need to study the effect of multi-component fluid mixtures. 3.1 Phase Behaviour The phase behaviour of gaseous mixtures is best illustrated by the contrast between the P-T projections of a pure substance and that of a typical binary hy- drocarbon mixture. The liquid- vapour line of the pure substances now becomes ‘an envelope, defining a P-T area in which both vapour and liquid can coexist, and the shape and position of the envelope will vary markedly and the properties of the two components or the binary mixture are varied, Also, there is no longer a critical point defining the maximum temperature and pressure beyond which liquification \becomes impossible by isothermal compression alone, but rather a cricondentherm and cricondenbar which define the extremes of the phase envelope but do not inter- sect on it. There is a point however which is commonly called the critical point, and which defines the point at which the intensive properties of the liquid and the vapour are equal. (Intensive properties, in contrast to extensive properties are independent of the amount of substance present. e.g. Density, pressure, surface tension, refractive index, specific heat ete). If the phase envelope is encountered from the single phase region via an isothermal pressure reduction, the behaviour of the system will depend upon which side of the critical point the isotherm intersects he envelope. To the left, the envelope defines bubble points, that is the system will Ppcar as a liquid and begin to liberate gas as the pressure is reduced isothermally ‘thin the envelope. To the right of the critical point the system will appear as a ‘ondensing vapour under these circumstances. Within the envelope exists a series of loci called quality lines, emanating from the critical point, and these define the volume percentage of liquid in equilibrium with the vapour at any point. However hese lines do not give any indication of the composition of either the liquid or the apour. It can be seen that for certain isothermal pressure.reductions, between the ritical point and the cricondentherm, retrograde condensation will occur, reach a fnaximum volume, and with further pressure reduction some of the condensed liquid vill re-vaporise. This is retrograde condensation behaviour and is a feature of most ret gas systems. VT Course -17- March 1991 ECL Petroleum TechnologiesPHASE DIAGRAMS OF ETHANE-n-DECANE MIXTURES 20:80 40:60 x Critical pointGe Properties of Mixtures The shape of the phase envelope is a function of the amount and type of components in the mixture, a phase envelope being unique to a given system composition. If, in the binary mixture example shown, the initial composition is varied from 100% pure A to 100% pure B, a continuous family of phase envelopes may be drawn, starting from the pure component line of A and ending with the pure component line of B. If B is the heavier component of the two (ie decane in an cthane-decane mixture) the phase envelopes described by mixtures containing very high proportions of B will show bubble point behaviour, that is the critical point lies on or very close to the cricondentherm, and any isothermal decompression will encounter the phase envelope to, the left of the critical point. By contrast, niixtures rich in the lighter component will provide opportunities for isothermal decompression to take place to the right of the critical point and allow retrograde condensation behaviour to occur. The critical points of all the family of envelopes will define a curve known as the eritical point locus, and this definition also applies to multiple component mixtures, The phase envelope, indicating the quality lines, can be measured from experiments for any mixture, but the procedure is both time consuming and expen- sive, and it is the purpose of equation of state matching to enable the attributes of a phase diagram to be computed on the basis of a relatively modest experimental data set. Not only is the shape of the envelope, the position of the ericonden- therm, cricondenbar and plait point important to ascertain, but also the position and shape of the quality lines, as these are necessary for separator condition op- timisation, and depletion performance predictions for retrograde reservoirs. The prediction of vapour-liquid equilibrium within the confines of a phase envelope re- lics upon a correct adaptation of the laws governing ideal solutions. | : PVT Course -18- March 1991 ECL Petroleum TechnologiesRAOULT'S LAW IDEAL SOLUTION BEHAVIOUR Vapour Pressure of Pure A “a Mixiure Vapour Pressure Vapour Pressure of Pure B wy ae Partial Pressure Due toA Partial Pressure Due to B { 100 50 0 Mole Percent of Component A in the Liquid Ke 5 a a 2 a 5 3 a o > Py = Xx Pat Xe PaProperties of Mixtures 3.1.1 Raoult’s Law Raoult’s Law is based on observations and experiments performed around 1886, and states that for a liquid mixture in equilibrium with its vapour, the partial Pressure in the vapour due to a given component (i) is the product of its mole fraction in the liquid and its (pure component) vapour pressure, ie: Pi = ZiPoi rve pi is the partial pressure in the vapour due to component i, 2; is the mole tion of component i in the liquid mixture and po; is the pure component vapour pressure of component i at the prevailing conditions. 3.1.2 Dalton’s Law Dalton’s Law of partial pressures states that the partial pressure due to a gas within a mixture of gases is the same pressure as would be measured if it alone were present under the same conditions as the mixture. If perfect gas properties are assumed, then: N;RT Pi Vp and _ NrRT Pr= Vp where p; is the partial pressure in the gas mixture due to component i, N is the number of moles of component i in the gas mixture, Vris the total volume oecupied by the gas mixture, Nz is the total number of moles in the mixture and R and T are the gas constant and absolute temperature respectively. PVT Course -19- ft March 1991 ECL Petroleum TechnologiesRAOULT'S LAW NON-IDEAL SOLUTION BEHAVIOUR | Vapour Pressure of Pure A ze Liquid Composition & Vapour Pressure of Pure B Vapour Pressure 100 50 0 Mole Percent of Component AProperties of Mixtures It can be sven therefore that pi/pr = Ni/Np = y; where yj is the mole fraction of component i in the gas. Combining this with Raoults? Law gives: ZiPoi = Pi or a PT The term y;/2i, which is the ratio of the mole fraction of component i in ont, to its'mole fraction in the liquid is known as the equilibrium constant ue. It can be seen that if these laws are obeyed, then the mole fraction of a given component in either phase of a mixture is known, and the vapour pressure of the pure component under the prevailing conditions is also known, then for any given pressure the mole fraction in the other phase can be calculated. Oo: PVT Course -20- "March 1991 ECL Petroleum TechnologiesPRESSURE, PSIA — 304 80g ya git Ty Soo Ys ay 108 o Soe eee PRESSURE, PSIA — n-BUTANE 18-18 CONV. PRESS. 800 PSIAProperties of Mixtures 3.1.3 K-values The combination of Raoult’s Law and Dalton’s Law gives the direction iu which the solution to vapour-liquid equilibrium problems in real hydrocarbon systems is to be found. However, the actual calculation of K-values is not quite so ight forward, for the following reasons: a) The vapour mixture is assumed to be a perfect gas. this is only approxi- mately true over a limited range of low pressures. }) Raoult’s Law only applies to ideal solutions, and most solutions depart from ideal behaviour, unless the components of the mixture are very closely re- lated in chemical structure and physical properties. This is partial for hydrocarbons from the same homologous series, and also for very di- lute solutions where there is a large contrast between the vapour pressures of the solvent. and the solute, This forms the basis of molecular weight dctermination by boiling point elevation or freezing point depression ¢) For many of the gascous pure components in naturally occurring mixtures are well above the critical point, and therefore a true pure component vapour pressure does not exist. These difficulties are overcome, in part via the use of other more complex (hermodynannic functions (fugacity - see appendix A1, section A.1.3 ) to account for the non-ideal behaviour of gases and solutions, such that the equations retain their basic form, For example, both Dalton’s Law and Raoult’s Law can be re-written in terins of fugacities, thus allowing the original formulations to be used and yet taking account of the non ideal behaviour. Prior to the advent of widely available computing power, attempts were made to incorporate as much experimental work as possible on the liquid-vapour equilibrium properties of hydrocarbon systems, into a comprehensive set of charts. These charts, from the natural gas Producers Association in North America, were widely used throughout the 1950's, 60’s and 70's for calculations predicting the compositions of liquids and vapours, especially for © processing applications. The procedure is a tedious, iterative one which has now been superceded by EoS methods and is mentioned for historical completness. Any of the contemporary NGPA handbooks will describe the method in detail. The K-value itself however, is readily calculated from laboratory analysis data, und at less severe conditions of temperature and pressure, ie < 1000 psi and < 200°F various methods exist for using these measured data to perform valuable validity checks on P-V-T sample information. PVT Course. -21- March 1991 ECL Petroleum TechnologiesPHASE ENVELOPES FOR RESERVOIR FLUIDS. CIS CRITICAL POINT Tres, Pres ° GAS CONDENSATE VOLATILE OIL t w c =: Q a Ww c a BLACK OIL TEMPERATURE ———>Properties of Mixtures 3.2 Fluid Types The “nature” or “type” of a fiuid is best defined by using the phase envelope and the local pressure and temperatures, ie: a. Dry Gas b. Gas Condensate c. Volatile Oil d. Crude Oil as in the diagram opposite. The phase envelope is unique for each particular composition of hydro- carbons and non-hydrocarbons. The proximity of the critical temperature to the reservoir or surface temperature defines the fluid type. Note that Dry Gas and Crude Oil systems can essentially be described by non-Equation of State approaches using suitable correlations provided that they are only subject to pressure and temperature changes. Although many authors have generated correlations to describe particular “volatile” fluids, ie Gas Condensates and Volatile Oils, none of these is general and Equation of State methods must be used, This having been said, the use of Equations of State to describe Dry Gases and Crnde Oils is usually very easy because both systems are dominated by only a fow very similar components. PVT Course -22- March 1991 ECL Pctroleum Technologies- a hole samplers e Surface samplin g - Wellhead - Separator Fluid Sampling e = sampling C e Often Competes with Well Testing ObjectivesSampling of Gas Condensate Systems 4 SAMPLING OF GAS CONDENSATE SYSTEMS In order to gain an insight into the phase behaviour of gas- condensate or volatile oil systems, valid samples of the systems must be available for laboratory analysis and experimentation, However, the very characteristics of these systems, which warrant such thorough investigations, ensure that they are also the most difficult to sample accurately. Much can be done by way of proper preparation for testing and sampling, in order to ensure that the maximum opportunity is offered for the securing of valid samples. Included as Appendix 3 are the proceedings of a UKOOA committee charged with investigating the state of hydrocarbon sampling, and recommending sampling practices with particular reference to gas-condensate systems. This is particularly relevant to the planning of testing and sampling campaigns. By the very nature of such events however, well tests and the associated sampling campaigns tend to be unique, especially on discovery /appraisal wells, and rarely go completely to plan. Many opportunities arise for things to go wrong, and some combinations of circumstances ensure that valid samples cannot be obtained. What follows is a discussion of sampling from the point of view of it already having been carried out, and the resulting samples analysed and reported. By being aware of the operational circumstances susroundings the sampling, the validity of the sample(s) data for use in further detailed studies such as EOS matching, can be commented on. Certain events can disqualify samples from further study immediately - others may merely alter the weight given to a particular set of data, Given the sensitivity of the phase behaviour of a gas- condensate systems to composition and contamination, this is especially important. PVT Course -23- March 1991 ECL Petroleum TechnologiesEFFECT OF PRESSURE DRAWDOWN" ON SAMPLE QUALITY Static Reservoir Pressure Dew 7 Point Locus Bubble Point Locus Pressure Flowing well has pressure drop of Ap in near wellbore region. Samples taken at points 1& 4 - Single phase 2&3 - Two phaseSampling of Gas Condensate Systems 4.1 Sampling Methods Samples of fluid may be taken from a well either on surface or ut the bottom of the hole close to, or at, the hydrocarbon bearing horizon. With the exception of RFT samples, which can be taken as part of the wireline logging programme, sampling is part of a well test programme. Although RFT samples may give a good indication of fluid type and properties, and be quite adequate for geochemi- cal studies, risks of contamination from mud additives, and difficulties of properly transferring samples, mean that they are rarely used for full PVT analysis, un- less nothing else is available. In wells drilled using oil based drilling fluids it is most unlikely that any useful quantitatve information will be obtained from RFT hydrocarbon samples. PVT Course -24- March 1991 ECL Petroleum TechnologiesBottom Hole Samplers e RFT _ - Contamination with mud | filtrate a Transfer difficulties - Drawdown not controllable - Sampling pressure unknown e Specialised Tool - Assumption of monophasic flow at sample depth - Leakage during retrieval - Incomplete transfer of heavy ends at surface - Adsorption of acid gases by samplerSampling of Gas Condensate Systems 4.1.1 Downhole Sampling Downhole samplers are slim chambers, which are positioned close to the producing zone of interest by means of wireline, either slick line or electric line. The chambers are equipped with valves which are operated either via time delay devices, or by surface signals in the case of electric line. The chambers, when sealed ly valve closure, are retrieved to surface, and the contents transferred to more casily handled pressure containers for shipment to the PVT laboratory. A sample size of 600ce is typical. They can either be of the "flow through” type, or the more recently developed positive displacement type, a schematic diagram of which is shown opposite. The advantage of this type of sampler is that samples can be transferred from the sampler without the need to use mercury to displace the fluid. Mercury has the double disadvantage of being highly toxic, and highly corrosive to aluminium and aluminium alloys, which is why any vessels containing mercury are forbidden from transport by helicopter. Sampling normally takes place with the well flowing, in order that fresh wellstream is passing the samplers during the process. Static samples, particularly in gas condensate systems are to be avoided due to the continual enrichment of the downbole fluid resulting from condensate segregation and dropout in the tubing. Nevertheless, attempts are made to avoid excessive drawdowns due to the likeli- hood of dropping the downhole Suid below its dewpoint. If the flowing fluid is already 2-phase at the downhole sample point, it is highly likely that the correct amounts of each phase will not be ttapped together in the samples, and the sample properties will therefore be unrepresentative of the reservoir fluid. For reservoirs whose fiuids are already at dewpoint at reservoir conditions, two phase wellstream flow is obviously unavoidable. Apart from the drawdown problem, which is purely a function of the particular reservoir properties (and therefore beyond the control of testing administration), the other potential problems associated with downhole sampling arc as follows:- (i) Leakage from sample chambers during retrieval. Modern downhole sam- plers are much Jess prone to this occurrance, but it has in the past been a significant problem. The lighter components would be the ones most prone to escape, and in doing so would distort the composition and phase be- haviour of the sample. Consistency of surface measured chamber pressures between companion samples should highlight any major problems. Just ap- plying the gas laws to the fluid should give a rough guide as to the expected pressure in a sampler at surface. (ii) Contamination with mud additives. This is only likely to be a problem if the well has not been allowed to clean up sufficiently prior to sampling. In situations where it is known that the fluid exists at, or close to, its dewpoint PVT Course -25- March 1991 ECL Petroleum Technologies} : BOTTOM HOLE SAMPLER wa POSITIVE DISPLACEMENT TYPE pee Electric Line or Slickline Valve Triggering Assembly Electrical Initiation by wireline or mechanical by clock delay Air chamber Valve eae Choke e |__— Sample chamber t+ Water eeeecee eect Floating piston C Se ee wi mh ! Valve |__—— Sample inflow port Typical Specifications Sample size 600cc Totallength 10 feet Tool diameter <2 inches Max pressure 10000 PSI