PTRL 1010 and PTRL 5015

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UNIT 3

The School of Petroleum Engineering FACULTY OF ENGINEERING THE UNIVERSITY OF NEW SOUTH WALES PROGRAM 3045

PTRL1010
Introduction to the Petroleum Industry and

PTRL 5015
Overview of the Petroleum Industry

UNIT 3
Presenter: Henry A Salisch

The Origin of Oil and Gas Generation and Migration

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3.1 Theories
Various theories and suppositions have been published in the course of time about the origin of hydrocarbons and their accumulation. It was a big step forward when it became a general opinion that origin and accumulation were two completely different things that have nothing to do with one another, neither in time nor in location. Petroleum and natural gases in smallest droplets or bubbles may be carried from source rocks by flowing ground water over enormous distances within the pore spaces of sandstones or porous limestones. Nobody has ever found a dependable way to determine the location or even the formation where this or that type of oil or gas comes from. Modern techniques of isotope analysis only enable specialists to date whether a particular gas originates from petroleum or from coal by their difference in C12/C13 ratio. There are two main groups of theories about the origin of these substances, the inorganic and the organic one.

3.1.1 Inorganic Theories

These, in general, are the older ones. They simply say that petroleum hydrocarbons originate from inorganic sources, such as volcanoes, carbides of metals, or simply from the reaction of carbon dioxide, water and catalysts with sunlight. In most of these theories the evidence is provided by methane which is found in volcanic gases, within the atmosphere of stars, in metamorphic rock and in other places where nobody would expect it to occur. Granite or other crystalline rocks in deeper layers of the earth may contain carbides which can create methane or similar gases by their reaction with water but, in general, these theories have little to do with real petroleum hydrocarbons. Methane is a gas that may originate from a large number of organic and inorganic processes and thus it is not good evidence for theories of inorganic origin. Other arguments came from countries where oil, asphalt and tars occur in regions where no sediments but only metamorphic rocks occur, such as in central Sweden. Isotopic analyses of these oil tars, however, showed that they are of mesozoic age (65 to 225 million years ago) and must come from mesozoic sediments that were lying above earlier mesozoic rocks. Since then they have been eroded, leaving behind them only these rare drops and patches of bitumen.

3.2.2 Organic Theories

Source rock analysts and geochemists are not in complete agreement on the types of organic material from which hydrocarbons are generated. Some suggest that only plant material is involved. Others conclude that animal and plant material contribute to petroleum generation. Plant and animal remains contain abundant carbon and hydrogen, which are the fundamental elements in petroleum and gas. Of those who are partial to plant material, some differentiate between fibrous, structured plants (trees, shrub and grass) to generate coal and non-fibrous, unstructured algae to generate oil Others, however, indicate that some coal generative environments can form significant amounts of oil as well as gas. Figure 3.1

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Figure 3.1 Chemical relations between petroleum hydrocarbons and other natural hydrocarbons (Beckmann)

Most organic theories try to prove that the so-called petrobitumina originate mostly from planctonic organisms of the sea, of brackish waters and also from lakes. These organisms live in such waters in enormous quantities and contain fatty acids and amino acids which are basic ingredients for the generation of oil. Most of this plankton production occurs on the shelf around the continents and in waters not deeper than about one thousand metres (3,300 feet). Figure 3.2 Such organisms need phosphoric and nitric salts in order to live. These salts come from onshore and nearshore sediments and are swept into the sea by rivers and estuaries. Some of the organisms are plants, mostly algae, and contain chlorophyll. This chemical compound belongs to the group of porphyrins and enables plants to build up complicated hydrocarbons from carbon dioxide and the energy of sunlight. Fragments of such porphyrin rings, derived from chlorophyll, are found in all types of crude oil besides fragments of haemoglobin and other similar compounds coming from the remains of animals, such as foraminifers, minute crustaceans and small worms. Iron oxides, copper and vanadium are also found regularly in crudes.

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Figure 3.2 Sources of organic material

(Clark)

Even in well-aerated waters, however, dead plankton on the bottom may be preserved from oxidation by sediments falling on top of it and blocking it off from oxygen. Thus, the probability of conservation is fairly high in all regions with active sedimentation, where organic material on the bottom is rapidly covered by sediment, saving it from oxidation. Generally, in all sediments deposited in water there is a constant lack of oxygen. The amount of burial is a function of how much sediment is discharged by streams and rivers into lakes and the sea, as well as the time involved in the depositional process. Thick accumulation of silt, clay and organic material (material of low permeability to stop the circulation of oxygen-bearing water) can produce large volumes of petroleum if there is enough time for the alteration process to occur. The production of plankton in the world is prodigious. Within the Black Sea every year 2.7 thousand million tons of plankton are produced, containing on the average 1%-3% of fatty acids and 4%-16% of amino acids. These plankton organisms mostly live only a very short time. When they die, they are eaten by other organisms, or they sink to the bottom, where they become prey to microbes which destroy their bodies and modify the chemical compounds contained in their tissues. In waters rich in oxygen all material which could be important for the generation of oil is likely to be oxidised and get lost. Thus, the preservation of oil and a high oxygen presence are incompatible.

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Some research indicates that terrestrial organic materials can generate coal and gas, and that marine organic material forms oil. There are positive indications that the coal-forming environment of the Upper Cretaceous-Eocene fluvio-deltaic Latrobe Group generates oil in the important Australian Gippsland basin (Bass Strait fields). Distance from terrestrial sediment and organic sources may also have significance as to the type of petroleum. The conversion from organic material is assisted by pressure caused by burial, temperature and thermal alteration and degradation. These factors result from depth, some bacterial action in a closed non-oxidising chemical system, radioactivity and catalysis. It is well documented that shales and some carbonates contain organic material that bears hydrocarbons of types similar to those in petroleum. These shales and carbonates are called source beds. The hydrocarbons are of the same type as those found in living plants and animals and consist of asphalt and kerogen. Variations in the compositions of different crude oils are probably due to chemical variations in the compositions of the organic material that produced them. Crude oil high in asphalt probably came from organic material that was high in protein. Paraffin oil, on the other hand, was probably derived from fatty organic material. Normal heat flow within the earths crust produces an average geothermal gradient of about 1.5F/100 feet (approx. 2.73C/100m). Maturation studies on various crude types indicate that temperatures required to produce oil occur between approximate depths of 5,000 feet and 20,000 feet (1,500m-6,000m approx.) under average heat flow conditions. Temperatures below 6,000 metres are excessive for oil generation and most often produce gas. Above 1,500 metres the crust is too cool to generate oil or gas. The best source rocks are considered to be organically rich, black-coloured shales deposited in a non-oxidising, quiet marine environment. Shale thickness is probably an important factor in the amount of petroleum generated. Organic matter in shale averages approximately 1% of the shale rock volume. Clay mineral constituents comprise the remaining 99%. Figure 3.3 Kerogen, derived from marine and lacustrine organic matter, will produce both oil and gas on maturation, whereas organic matter derived from terrestrial plant material is believed to yield primarily gas. Kerogen is an insoluble, high molecular weight, polymeric compound which comprises about 90% of the organic material in shale. The remaining 10% contains bitumen of varying composition which, according to some researchers, is thermally altered kerogen. Kerogen, as the major organic constituent in source rocks, is a primary factor in forming bitumen that migrates to accumulate as crude oil. Thermal conversion of kerogen to bitumen is the important process of crude oil formation. Thermal alteration increases the carbon content of the migratable hydrocarbons, which leave the unmigratable residual kerogen components behind. Organic matter in sediments undergoes a series of reactions (maturation) which alter the chemical structure of the compounds to produce hydrocarbons. The rate of these reactions depends predominantly on time and temperature and, hence, the burial history of the basin. The atomic H/C ratio of kerogen tends to decrease with maturation.

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Figure 3.3 Percentages of mineral, organic material, bitumen, kerogen and rock

(Barker)

Figure 3.4 Oils aint oils

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Figure 3.5 Microscopic section of oil-bearing rock

Figure 3.6 Boiling is a simple, single-word explanation of how crude oil is separated into its eight basic parts

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3.2 Source Rocks for Oil and Gas

Shales with well-preserved organic material are the most important potential source rocks for hydrocarbons. They are not, however, reservoirs unless they can act as such when they are fractured since they are not naturally permeable. Shales constitute good seals for porous reservoir rocks and can thus provide good hydrocarbon traps. The organic material, if sufficiently mature, can be extracted by distillation when the rocks are very close to surface; or it can be produced commercially by more conventional means if an existing system of extensive fractures can be accessed by well bores. Shales do not constitute reservoir rocks

3.3 Oil and Gas Migration

As mentioned in the previous chapter, hydrocarbons are generated in fine-grained source rocks, but they accumulate in, and are produced from, more permeable reservoir rocks. The movement of hydrocarbons from source rocks to reservoir rocks is known as migration. The concept of migration is now universally accepted, notwithstanding limited agreement about mechanism and distances. When petroleum moves from source beds to reservoir beds, it does so by primary migration. When it moves within the reservoir after it has accumulated, it does it by secondary migration. It is not known, at present, whether petroleum in the form of oil or gas moved over great or only short distances before accumulating into deposits as we know them today. Depending on circumstances either case is possible. It is probable that some small amounts of petroleum generate within the reservoir rocks in which they accumulate. However, the bulk of it probably comes from source beds external to the reservoir. It is also not known whether petroleum components were dissolved in the water of the rock or existed as free hydrocarbon mixtures side-by-side with the water in the source rock pore space. It is accepted, however, that petroleum compounds originated in muds and silts, and that rock compaction squeezed them from these source beds into the pore spaces of the layers of sands and carbonates where deposits of oil and gas are located today. It is believed that the primary migration of oil and gas took place in some kind of solution in compaction or pore water, in clay dehydration water, in meteoric water or in gas moving towards the reservoir where it established a position of equilibrium for the given hydrodynamic and structural conditions. Being lighter than the adjacent water, the oil and gas floated upward through the tiny tortuous pore channels in the sand until stopped by overlying dense rock layers. Movement of cementing solutions through a reservoir can similarly displace oil and gas to other locations as the initial pore space is occupied by mineral material. All pores, caverns and cavities in rocks or sediments below the water table are filled with some liquid or gas, more than 99% with water. The rest, restricted to very rare cases, may contain oil or gas. All these pore fillings are affected by a system of static and dynamic pressures which are the main reason for the migration and the eventual trapping of petroleum hydrocarbons in reservoirs. Most obvious is the pressure caused by the weight of overlying sediments, called overburden pressure. Sediments, on an average, have a specific weight of 2.5 to 3.0 g/cc. At a depth of, for instance, 1,000 metres (approx. 3,300ft) a sandstone is compressed by a weight of rocks of 2.5 to 3.0 tons per square metre. All sediments have to support this overburden pressure. Mudstones become compacted, losing a large part of their water content and becoming solid claystones. Sandstones with an initial pore space of more than 40% lose part of their porosity, remaining with 20% and less. The water squeezed out of the pore space moves towards higher zones with lower pressure. This compaction will cease only when the sandstone or claystone is able to carry the weight of the overlying sediment by its internal stability. Then the internal tension or

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pressure of the solid framework equals the overburden pressure. If the pore space were empty, it would be under constant atmospheric pressure only. In reality, the weight of the pore filling mostly salt water gives rise to the so-called formation pressure. Usually this formation pressure may be calculated in kg/cm2/m by multiplying the depth, in metres, by a factor of 0.107 (or in the case of feet, in psi/ft, by multiplying the depth in feet, by a factor of 0.465/ft). Regions with very young and unconsolidated sediments mostly show higher pressure gradients. Other factors affecting the contents of pore space are surface tensions between the surfaces of the sand grains, water content, oil droplets and gas bubbles. During compaction the water surplus of the sediments will be expelled and move to zones of lower pressure, carrying with it droplets of oil and bubbles of gas. Under normal conditions water shows higher affinity for the rock surface; the pore space then is water wet and will always retain a fine film of water covering the surface of the rock. Compaction of source sediments in a basin which is sinking will remain a permanent process over geologic times. The squeezed out water is kept moving for the same time and even longer, and the path of its migration may cover hundreds of kilometres, always within the narrow pore space and at a very low, hardly measurable, speed. Many of these migration paths may lead into the open and the oil droplets will be lost by oxidation. Others will end when reaching so called traps which may constitute reservoirs and which form the essence of oil and gas fields. But before one can speak of a reservoir, oil droplet will have required millions of years to join to form bigger drops, and gas bubbles will have to form gas caps. Even if it has taken millions of years to fill a reservoir with oil and gas, it may only take a few dozen years to retrieve most of the commercially recoverable hydrocarbons from the reservoir.

3.3.1 Primary Migration

This involves the generation of hydrocarbons in the source rock, their movement within it and their expulsion into the reservoir rock or into carrier beds. These are the porous and permeable rocks that carry the petroleum to the reservoir. Primary migration is the direct result of hydrocarbon generation, although the exact process is not well understood. Hydrocarbons do not move through the source rock by solution in water because the volumes of water required are not available. Furthermore, they do not migrate as a separate oil phase because oil droplets may be too large to pass through the narrow pore throats of the source rock. However, some thermal expansion may cause an overpressuring of the pore fluids and force them along. One of the most widely accepted theories of primary migration suggests that fluid generation occurs in sealed, confined systems and source rocks perform much like pressure cookers. The generation of hydrocarbons leads to a decrease in kerogen volume (an increase in pore space), but an overpressuring occurs as this space is filled by hydrocarbons. The overpressuring causes the opening of safety valves in the system (partings and microfractures), which allow the fluids to migrate in and out of the source rock. Figure 3.7 The expulsion of the petroleum causes a drop in pressure, and the system reseals until the overpressuring is built up again by generation. Cycles continue until generation ceases. As mentioned, an important process involved in expelling the newly formed hydrocarbons from their source sediments is the compaction of clay rocks. The actual agency responsible for taking the hydrocarbons out of the source rocks and making them available for primary migration is presumably related to the properties of the source sediments. The most obvious and measurable of these properties are those of the individual clay minerals.

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Associated methods of expulsion from a source rock into a carrier bed or reservoir rock include migration into silty stringers within the source rock, vertical migration along fault planes and diffusion both above and below the source rock.

Figure 3.7 Schematic diagram showing hydrocarbon expulsion and primary migration from source rock to carrier beds (Cornford)

3.4 Technical Properties and Commercial Value of Petroleum and Natural Gas
Petroleum, oil and gas do not have uniform compositions and characteristics worldwide. They vary from one area to another, depending on the temperatures and pressures under which they were generated and modifications that may have occurred during migration to and into the reservoirs where they will eventually accumulate. Figure 3.4 shows different types of oils, from very light to heavy. Figure 3.5 is a cross-section of a rock that shows where oil or gas are located within a reservoir rock The subproducts of oil and gas are the commercially important aspects of hydrocarbons. The subproducts of oil are basically obtained by boiling. Different subproducts are obtained at different temperatures as shown in Figure 3.6. A well-site geologist has no possibility of making any real analysis of the oil or gas coming from an open-hole test or from the first production of a newly drilled well, but he/she should know, as early as possible, the quality of the hydrocarbon and the price the company will get for it. There are some simple tests which may show what type of petroleum has been found and the technical term used to describe it. The technical term is directly related to the commercial value of the crude or gas.

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Natural gases may be called sweet or sour, dry or wet. Sweet gases show a neutral reaction to a wet strip of pH paper. They consist of hydrocarbon gases, mostly of methane and, perhaps, of inert gases such as nitrogen. They will not attack steel pipes, are handy for transport and are always more valuable than sour gases. The gas itself may differ considerably in quality and composition. The component found in the highest percentage is always methane, the lightest hydrocarbon gas. Heavier hydrocarbon gases like ethane, propane, butane and pentane usually have less or no methane. Gas fields that contain considerable percentages of sulphuric gases like hydrogen sulphide (H2S) are called sour, the pure ones are called sweet. Sulphuric gases are very disagreeable for drilling, production and marketing. They must be stripped or washed out by chemical or physio-chemical processes and converted to pure sulphur. Other disagreeable components are carbon dioxide (CO2) and nitrogen. CO2 may come from volcanic processes in the neighbourhood and it is disagreeable because it attacks the steel of the pipes in and close to the well and it also diminished the calorific value of the gas. It must be stripped off before selling the gas. Sour gases show some acidity when tested with a moist strip of pH paper and they may contain carbonic acid (H2CO3) and/or hydrogen sulphide (H2S). The latter, when present in a relatively high percentage, is the worst possible component. It is very poisonous for all living beings; it will destroy all steel and iron pipes and has to be stripped chemically before transport. There is an overproduction of sulphur worldwide, because so many gas fields produce sulphur from sour gas and in enormous quantities. Sulphur gases, therefore, have low commercial value. H2CO3 or rather gases with CO2 occur near volcanic regions or over coal fields. If the gas is not completely dry, it will attack steel pipe. Thus, if in large quantities, it may reduce the commercial value of the gas. Dry gases are those which do not contain condensate, while wet gases contain considerable amounts of condensate gases like propane, butane, pentane and even hexane. These heavier hydrocarbon gases turn to the liquid state at low temperature and at high pressure, and may form liquid drops in pipelines in winter or cause difficulties in underground storage facilities. They are highly valued hydrocarbons as feed stocks for refineries. In principle, all newly found gas-bearing structures have a commercial handicap: Gas can be sold only when the size of the structure and its gas content are known, because the diameter of the pipe lines, the size of the installation and the quantity to be sold per day or year must be known before a selling contract can be signed. That means that a large amount of money, paid for drilling, installations, etc will not bring any income or interest for years until the commercial production can start. Crude oils usually are classified by their gravity, their pour point, their flame point and their sulphur content. Gravity is one of the most valuable tests, and it has a direct relation to the price. It can be tested easily by an aerometer. In the U.S.A. and most other oil producing areas, gravity is measured in API-grades. Water would have a gravity of 10API. Crudes heavier than water have a lower API gravity. Some very heavy crudes are known to have gravities of 4API. Light crudes can have gravities above 40API. They contain a high amount of low-boiling components and will give high percentages of petrol (gasoline). They are sold at higher prices, especially if they are sulphur-free. Low gravity API oils bring low amounts of petrol and special cracking processes

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have to be applied to increase the amount of higher paying refining products. On the bother hand, they will supply a high percentage of heating oils and lubricants. The Pour Point of crude oils is most important for treating, transportation handling and refining. Pour Point means the temperature at which a liquid crude becomes a stiff smear which may block tanks, pipelines and installations. A pour point of less than 10 centigrade means behaviour similar to water. High pour points make it necessary to heat the oil during pipeline transport, and heater treaters have to be used for the separation of gas and water. There are crudes with pour points of more than 20 centigrade, which become stiff even on cold summer days in temperate climates. Paraffin compounds cause high pour points by forming solid needles and increasing the viscosity of the crude. They are sold at a lower price. The flame point of crudes varies between 80 and less than 0 centigrade. Low flame points show that a crude contains high amounts of low-boiling hydrocarbons such as benzene. They are sold at a higher price. The sulphur content of crudes may go up to more than 10%, usually with low API gravity, high viscosity and high flame point types of oil. Such high sulphur content usually occurs near salt domes or in a series containing gypsum or anhydrite. The sulphur may occur in solid state, or it may be dissolved within the oil. Sulphur must be removed by chemical means. It constitutes one of the worst factors in air pollution. Sulphur content reduces the price of crudes significantly.

3.2.1 A Unit of Measurement to Remember

Specific gravity is one of the most important hydrocarbon parameters. Although the unit of grams/cubic centimetre (g/cc) is being used in the decimal system, it is customary in the oil industry to use the term hydrocarbon gravity and express it in units of degrees API or API. (The term API stands for American Petroleum Institute). To convert from g/cc to units of degrees API, the following relation is being used:

oAPI = (141.5/Specific Gravity 60/60F) 131.5

where Specific Gravity 60/60F means specific gravity of oil at 60oF referred to water at 60oF. Thus, water will have a Specific Gravity of 10oAPI (its density is 1.0g/cc). A type of oil that has a density of 0.85 g/cc, will have a Specific Gravity of 35oAPI

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