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