Hydrocarbons

    A hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons from which one hydrogen atom has been removed are functional groups, called hydrocarbyls. Aromatic hydrocarbons (arenes), alkanes, alkenes, cycloalkanes and alkyne-based compounds are different types of hydrocarbons. The majority of hydrocarbons found on earth naturally occur in crude oil, where decomposed organic matter provides an abundance of carbon and hydrogen which, when bonded, can catenate to form seemingly limitless chains.

    • In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons from which one hydrogen atom has been removed are functional groups, called hydrocarbyls. Aromatic hydrocarbons (arenes), alkanes, alkenes, cycloalkanes and alkyne-based compounds are different types of hydrocarbons.
    • The majority of hydrocarbons found on earth naturally occur in crude oil, where decomposed organic matter provides an abundance of carbon and hydrogen which, when bonded, can catenate to form seemingly limitless chains.
    • Extracted hydrocarbons in a liquid form are referred to as petroleum (literally “rock oil”) or mineral oil, whereas hydrocarbons in a gaseous form are referred to as natural gas. Petroleum and natural gas are found in the Earth’s subsurface with the tools of petroleum geology and are a significant source of fuel and raw materials for the production of organic chemicals.
    • The extraction of liquid hydrocarbon fuel from sedimentary basins is integral to modern energy development. Hydrocarbons are mined from tar sands and oil shale, and potentially extracted from sedimentary methane hydrates. These reserves require distillation and upgrading to produce synthetic crude and petroleum.
      Oil reserves in sedimentary rocks are the source of hydrocarbons for the energy, transport and petrochemical industry.
    • Hydrocarbons are economically important because major fossil fuels such as coal, petroleum and natural gas, and its derivatives such as plastics, paraffin, waxes, solvents and oils are hydrocarbons.

    SECTION ONE: TYPES OF HYDROCARBONS
    The classifications for hydrocarbons defined by IUPAC nomenclature of organic chemistry are as follows:

    • SATURATED HYDROCARBONS (alkanes): are the simplest of the hydrocarbon species and are composed entirely of single bonds and are saturated with hydrogen. The general formula for saturated hydrocarbons is CnH2n+2 (assuming non-cyclic structures). Saturated hydrocarbons are the basis of petroleum fuels and are found as either linear or branched species. Hydrocarbons with the same molecular formula but different structural formula are called structural isomers.

    • UNSATURATED HYDROCARBONS (alkenes, alkynes) have one or more double or triple bonds between carbon atoms. Those with double bond are called alkenes. Those with one double bond have the formula CnH2n (assuming non-cyclic structures). Those containing triple bonds are called alkynes, with general formula CnH2n-2.

    • CYCLOALKANES are hydrocarbons containing one or more carbon rings to which hydrogen atoms are attached. The general formula for a saturated hydrocarbon containing one ring is CnH2n.

    • AROMATIC HYDROCARBONS, also known as arenes, are hydrocarbons that have at least one aromatic ring.

    SECTION TWO: GENERAL PROPERTIES OF HYDROCARBONS

    • Because of differences in molecular structure, the empirical formula remains different between hydrocarbons; in linear, or “straight-run” alkanes, alkenes and alkynes, the amount of bonded hydrogen lessens in alkenes and alkynes due to the “self-bonding” or catenation of carbon preventing entire saturation of the hydrocarbon by the formation of double or triple bonds.
    • This inherent ability of hydrocarbons to bond to themselves is referred to as catenation, and allows hydrocarbon to form more complex molecules, such as cyclohexane, and in rarer cases, arenes such as benzene. This ability comes from the fact that the bond character between carbon atoms is entirely non-polar, in that the distribution of electrons between the two elements is somewhat even due to the same electronegativity values of the elements (~0.30), and does not result in the formation of an electrophile.
    • Generally, with catenation comes the loss of the total amount of bonded hydrocarbons and an increase in the amount of energy required for bond cleavage due to strain exerted upon the molecule;in molecules such as cyclohexane, this is referred to as ring strain, and occurs due to the “destabilized” spatial electron configuration of the atom.

    SECTION THREE: BURNING HYDROCARBONS: COMBUSTION
    Hydrocarbons are currently the main source of the world’s electric energy and heat sources (such as home heating) because of the energy produced when burnt. Often this energy is used directly as heat such as in home heaters, which use either petroleum or natural gas. The hydrocarbon is burnt and the heat is used to heat water, which is then circulated. A similar principle is used to create electric energy in power plants.
    Common properties of hydrocarbons are the facts that they produce steam, carbon dioxide and heat during combustion and that oxygen is required for combustion to take place. The simplest hydrocarbon, methane, burns as follows:
    CH4 + 2O2 → 2H2O + CO2 + Energy
    In inadequate supply of air, CO gas and water vapour are formed:
    2CH4 + 3O2 → 2CO + 4H2O
    Another example of this property is propane:
    C3H8 + 5O2 → 4H2O + 3 CO2 + Energy
    In general burning of hydrocarbons in air has the following chemical structure.
    CnH2n+2 + (3n+1)/2 O2 → (n+1) H2O + nCO2 + Energy
    Burning of hydrocarbons is an example of an exothermic chemical reaction.

    SECTION FOUR: PETROLEUM
    Petroleum is a naturally occurring flammable liquid consisting of a complex mixture of hydrocarbons of various molecular weights and other liquid organic compounds, that are found in geologic formations beneath the Earth’s surface. The name Petroleum covers both naturally occurring unprocessed crude oils and petroleum products that are made up of refined crude oil. A fossil fuel, it is formed when large quantities of dead organisms, usually zooplankton and algae, are buried underneath sedimentary rock and undergo intense heat and pressure.

    Petroleum is recovered mostly through oil drilling. This comes after the studies of structural geology (at the reservoir scale), sedimentary basin analysis, reservoir characterization (mainly in terms of porosity and permeable structures). It is refined and separated, most easily by boiling point, into a large number of consumer products, from gasoline and kerosene to asphalt and chemical reagents used to make plastics and pharmaceuticals. Petroleum is used in manufacturing a wide variety of materials, and it is estimated that the world consumes about 90 million barrels each day.

    In its strictest sense, petroleum includes only crude oil, but in common usage it includes all liquid, gaseous, and solid hydrocarbons. Under surface pressure and temperature conditions, lighter hydrocarbons methane, ethane, propane and butane occur as gases, while pentane and heavier ones are in the form of liquids or solids. However, in an underground oil reservoir the proportions of gas, liquid, and solid depend on subsurface conditions and on the phase diagram of the petroleum mixture.

    An oil well produces predominantly crude oil, with some natural gas dissolved in it. Because the pressure is lower at the surface than underground, some of the gas will come out of solution and be recovered (or burned) as associated gas or solution gas. A gas well produces predominantly natural gas. However, because the underground temperature and pressure are higher than at the surface, the gas may contain heavier hydrocarbons such as pentane, hexane, and heptane in the gaseous state. At surface conditions these will condense out of the gas to form natural gas condensate, often shortened to condensate. Condensate resembles gasoline in appearance and is similar in composition to some volatile light crude oils.

    The proportion of light hydrocarbons in the petroleum mixture varies greatly among different oil fields, ranging from as much as 97 percent by weight in the lighter oils to as little as 50 percent in the heavier oils and bitumens.

    The hydrocarbons in crude oil are mostly alkanes, cycloalkanes and various aromatic hydrocarbons while the other organic compounds contain nitrogen, oxygen and sulfur, and trace amounts of metals such as iron, nickel, copper and vanadium. The exact molecular composition varies widely from formation to formation but the proportion of chemical elements vary over fairly narrow limits.

    Crude oil varies greatly in appearance depending on its composition. It is usually black or dark brown (although it may be yellowish, reddish, or even greenish). In the reservoir it is usually found in association with natural gas, which being lighter forms a gas cap over the petroleum, and saline water which, being heavier than most forms of crude oil, generally sinks beneath it. Crude oil may also be found in semi-solid form mixed with sand and water, as in the Athabasca oil sands in Canada, where it is usually referred to as crude bitumen. In Canada, bitumen is considered a sticky, black, tar-like form of crude oil which is so thick and heavy that it must be heated or diluted before it will flow. Venezuela also has large amounts of oil in the Orinoco oil sands, although the hydrocarbons trapped in them are more fluid than in Canada and are usually called extra heavy oil. These oil sands resources are called unconventional oil to distinguish them from oil which can be extracted using traditional oil well methods. Between them, Canada and Venezuela contain an estimated 3.6 trillion barrels (570×109 m3) of bitumen and extra-heavy oil, about twice the volume of the world’s reserves of conventional oil.

    Petroleum is used mostly, by volume, for producing fuel oil and gasoline, both important “primary energy” sources. 84 percent by volume of the hydrocarbons present in petroleum is converted into energy-rich fuels (petroleum-based fuels), including gasoline, diesel, jet, heating, and other fuel oils, and liquefied petroleum gas.The lighter grades of crude oil produce the best yields of these products, but as the world’s reserves of light and medium oil are depleted, oil refineries are increasingly having to process heavy oil and bitumen, and use more complex and expensive methods to produce the products required. Because heavier crude oils have too much carbon and not enough hydrogen, these processes generally involve removing carbon from or adding hydrogen to the molecules, and using fluid catalytic cracking to convert the longer, more complex molecules in the oil to the shorter, simpler ones in the fuels.

    Due to its high energy density, easy transportability and relative abundance, oil has become the world’s most important source of energy since the mid-1950s. Petroleum is also the raw material for many chemical products, including pharmaceuticals, solvents, fertilizers, pesticides, and plastics; the 16 percent not used for energy production is converted into these other materials. Petroleum is found in porous rock formations in the upper strata of some areas of the Earth’s crust. There is also petroleum in oil sands (tar sands). Known oil reserves are typically estimated at around 190 km3 (1.2 trillion (short scale) barrels) without oil sands, or 595 km3 (3.74 trillion barrels) with oil sands. Consumption is currently around 84 million barrels (13.4×106 m3) per day, or 4.9 km3 per year. Which in turn yields a remaining oil supply of only about 120 years, if current demand remain static.

    Petroleum is a mixture of a very large number of different hydrocarbons; the most commonly found molecules are alkanes (paraffins), cycloalkanes (naphthenes), aromatic hydrocarbons, or more complicated chemicals like asphaltenes. Each petroleum variety has a unique mix of molecules, which define its physical and chemical properties, like color and viscosity.

    The alkanes, also known as paraffins, are saturated hydrocarbons with straight or branched chains which contain only carbon and hydrogen and have the general formula CnH2n+2. They generally have from 5 to 40 carbon atoms per molecule, although trace amounts of shorter or longer molecules may be present in the mixture.

    The alkanes from pentane (C5H12) to octane (C8H18) are refined into gasoline, the ones from nonane (C9H20) to hexadecane (C16H34) into diesel fuel, kerosene and jet fuel. Alkanes with more than 16 carbon atoms can be refined into fuel oil and lubricating oil.

    At the heavier end of the range, paraffin wax is an alkane with approximately 25 carbon atoms, while asphalt has 35 and up, although these are usually cracked by modern refineries into more valuable products.

    The shortest molecules, those with four or fewer carbon atoms, are in a gaseous state at room temperature. They are the petroleum gases. Depending on demand and the cost of recovery, these gases are either flared off, sold as liquified petroleum gas under pressure, or used to power the refinery’s own burners. During the winter, butane (C4H10), is blended into the petrol pool at high rates, because its high vapor pressure assists with cold starts. Liquified under pressure slightly above atmospheric, it is best known for powering cigarette lighters, but it is also a main fuel source for many developing countries. Propane can be liquified under modest pressure, and is consumed for just about every application relying on petroleum for energy, from cooking to heating to transportation.

    The cycloalkanes, also known as naphthenes, are saturated hydrocarbons which have one or more carbon rings to which hydrogen atoms are attached according to the formula CnH2n. Cycloalkanes have similar properties to alkanes but have higher boiling points.

    The aromatic hydrocarbons are unsaturated hydrocarbons which have one or more planar six-carbon rings called benzene rings, to which hydrogen atoms are attached with the formula CnHn. They tend to burn with a sooty flame, and many have a sweet aroma. Some are carcinogenic.

    These different molecules are separated by fractional distillation at an oil refinery to produce petrol, jet fuel, kerosene, and other hydrocarbons.

    SECTION FIVE: CHARACTERIZING CRUDE OILS
    Assessing the refining value of a crude oil requires a full description of the crude oil and its components, involving scores of properties. However, two properties are especially useful for quickly classifying and comparing crude oils: API gravity (a measure of density) and sulfur content.
    PART ONE: API GRAVITY (Density)
    The density of a crude oil indicates how light or heavy it is, as a whole. Lighter crudes contain higher proportions of small molecules, which the refinery can process into gasoline, jet fuel, and diesel (for which demand is growing). Heavier crudes contain higher proportions of large molecules, which the refinery can either (1) use in heavy industrial fuels, asphalt, and other heavy products (for which the markets are less dynamic and in some cases shrinking) or (2) process into smaller molecules that can go into the transportation fuels products.
    In the refining industry, the density of an oil is usually expressed in terms of API gravity, a parameter whose units are degrees (o API) – e.g., 35oAPI. API gravity varies inversely with density (i.e., the lighter the material, the higher its API gravity). By definition, water has API gravity of 10o.
    Exhibit 2 indicates the quality of a typical light crude (35°API) and a typical heavy crude (25°API), in terms of their natural yields of light gases, gasoline components, distillate (mainly jet fuel and diesel) components, and heavy oils. The exhibit also shows the average demand profile for these product categories in the developed countries.

    The natural yields of the heavy oils from both the light and the heavy crudes exceed the demand for heavy refined products, and the natural yield of heavy oil from the heavy crude is more than twice that of the light crude. These general characteristics of crude oils imply that (1) refineries must be capable of converting at least some, and perhaps most, of theheavy oil into light products, and (2) the heavier the crude, the more of this conversion capacity is required to produce any given product slate.
    3.2.2 Sulfur Content
    Of all the hetero-elements in crude oil, sulfur has the most important effects on refining.
    ♦ Sufficiently high sulfur levels in refinery streams can (1) deactivate (“poison”) the catalysts that promote desired chemical reactions in certain refining processes, (2) cause corrosion in refinery equipment, and (3) lead to air emissions of sulfur compounds, which are undesirable and may be subject to stringent regulatory controls.
    ♦ Sulfur in vehicle fuels leads to undesirable vehicle emissions of sulfur compounds and interferes with vehicle emission control systems that are directed at regulated emissions such as volatile organic compounds, nitrogen oxides, and particulates.
    Consequently, refineries must have the capability to remove sulfur from crude oil and refinery streams to the extent needed to mitigate these unwanted effects. The higher the sulfur content of the crude, the greater the required degree of sulfur control and the higher the associated cost.
    The sulfur content of crude oil and refinery streams is usually expressed in weight percent (wt%) or parts per million by weight (ppmw). In the refining industry, crude oil is called sweet (low sulfur) if its sulfur level is less than a threshold value (e.g., 0.5 wt% (5,000 ppmw)) and sour (high sulfur) if its sulfur level is above a higher threshold. Most sour crudes have sulfur levels in the range of 1.0–2.0 wt%, but some have sulfur levels > 4 wt%.
    Within any given crude oil, sulfur concentration tends to increase progressively with increasing carbon number. Thus, crude fractions in the fuel oil and asphalt boiling range have higher sulfur content than those in the jet and diesel boiling range, which in turn have higher sulfur content than those in the gasoline boiling range. Similarly, the heavier components in, say, the gasoline boiling range have higher sulfur content than the lighter components in that boiling range.
    3.2.3 Classifying Crude Oils by API Gravity and Sulfur Content
    Exhibit 3 shows a widely-used scheme for classifying crude oils on the basis of their API gravity and sulfur content. Each crude class is defined by a range of API gravity and a range of sulfur content; the names of the categories indicate these ranges in qualitative terms.
    Exhibit 4 lists some important crude oils in the world oil trade and indicates the API gravity/sulfur classification for each of these crudes.

    2.1 Exploration
    In the past, surface features such as tar seeps or gas pockmarks provided initial clues to the location of shallow hydrocarbon deposits. Today, a series of surveys, starting with broad geological mapping through increasingly advanced methods such as passive seismic, reflective seismic, magnetic and gravity surveys give data to sophisticated analysis tools that identify potential hydrocarbon bearing rock as “prospects.” Chart: Norwegian Petroleum Directorate (Barents Sea)
    An offshore well typically costs $30 million, with most falling in the $10-$100 million range. Rig leases are typically $200,000 – $700,000 per day. The average US onshore well costs about $4 million, as many have much lower production capacity. Smaller companies exploring marginal onshore fields may drill a shallow well for as little as $100,000.
    This means that oil companies spend much time on analysis models of good exploration data, and will only drill when models give a good indication of source rock and probability of finding oil or gas. The first wells in a region are called wildcats because little may be known about potential dangers, such as the downhole pressures that will be encountered, and therefore require particular care and attention to safety equipment.
    If a find (strike, penetration) is made, additional reservoir characterization such as production testing, appraisal wells, etc., are needed to determine the size and production apacity of the reservoir in order to justify a development
    decision.