Difference between revisions of "Petroleum"

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Petroleum (L. petroleum, from Latin: petra rock + oleum oil^[1]) or crude oil is a naturally occurring, toxic, flammable liquid consisting of a complex mixture of hydrocarbons of various molecular weights, and other organic compounds, that are found in geologic formations beneath the Earth's surface. Petroleum is recovered mostly through oil drilling. It is refined and separated, most easily by boiling point, into a large number of consumer products, from petrol and kerosene to asphalt and chemical reagents used to make plastics and pharmaceuticals.^[2] The term petroleum was first used in the treatise De Natura Fossilium, published in 1546 by the German mineralogist Georg Bauer, also known as Georgius Agricola.^[3]

Composition

In its strictest sense, petroleum includes only crude oil, but in common usage it includes both crude oil and natural gas. Both crude oil and natural gas are predominantly a mixture of hydrocarbons. Under surface pressure and temperature conditions, the lighter hydrocarbons methane, ethane, propane and butane occur as gases, while the heavier ones from pentane and up are in the form of liquids or solids. However, in the underground oil reservoir the proportion which is gas or liquid varies depending on the subsurface conditions, and on the phase diagram of the petroleum mixture.^[4]

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 predominately 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. Under surface conditions these will condense out of the gas and form natural gas condensate, often shortened to condensate. Condensate resembles petrol in appearance and is similar in composition to some volatile light crude oils.

The proportion of light hydrocarbons in the petroleum mixture is highly variable between different oil fields and ranges from as much as 97% by weight in the lighter oils to as little as 50% 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 as follows:^[5]

Four different types of hydrocarbon molecules appear in crude oil. The relative percentage of each varies from oil to oil, determining the properties of each oil.^[4]

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, tar-like form of crude oil which is so thick and heavy that it must be heated or diluted before it will flow.^[7] 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 (570×10^⁹ m³) of bitumen and extra-heavy oil, about twice the volume of the world's reserves of conventional oil.^[8]

Petroleum is used mostly, by volume, for producing fuel oil and petrol, both important "primary energy" sources.^[9] 84% by volume of the hydrocarbons present in petroleum is converted into energy-rich fuels (petroleum-based fuels), including petrol, diesel, jet, heating, and other fuel oils, and liquefied petroleum gas.^[10] 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% 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,^[11] or 595 km³ (3.74 trillion barrels) with oil sands.^[12] Consumption is currently around 84 million barrels (13.4×10^⁶ m³) per day, or 4.9 km³ per year.

Chemistry

Petroleum is a mixture of a very large number of different hydrocarbons; the most commonly found molecules are alkanes (linear or branched), cycloalkanes, 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 C_nH_2n+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 petrol, the ones from nonane (C₉H₂₀) to hexadecane (C₁₆H₃₄) into diesel fuel and kerosene (primary component of many types of jet fuel), and the ones from hexadecane upwards 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 butane's 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 C_nH_2n. 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 C_nH_n. 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. For example, 2,2,4-trimethylpentane (isooctane), widely used in petrol, has a chemical formula of C₈H₁₈ and it reacts with oxygen exothermically:^[13]

2 C₈H₁₈(l) + 25 O₂(g) → 16 CO₂(g) + 18 H₂O(g) + 10.86 MJ/mol (of octane)

The amount of various molecules in an oil sample can be determined in laboratory. The molecules are typically extracted in a solvent, then separated in a gas chromatograph, and finally determined with a suitable detector, such as a flame ionization detector or a mass spectrometer.^[14]

Incomplete combustion of petroleum or petrol results in production of toxic byproducts. Too little oxygen results in carbon monoxide. Due to the high temperatures and high pressures involved, exhaust gases from petrol combustion in car engines usually include nitrogen oxides which are responsible for creation of photochemical smog.

Empirical equations for the thermal properties of petroleum products

Heat of combustion

At a constant volume the heat of combustion of a petroleum product can be approximated as follows:

<math>Q_v = 12,400 - 2,100d^2</math>

where <math>Q_v</math> is measured in cal/gram and d is the specific gravity at 60 °F (16 °C).

Thermal conductivity

The thermal conductivity of petroleum based liquids can be modeled as follows:

<math>K = \frac{0.813}{d}[1-0.0203(t-32)]</math>,

where K is measured in BTU · hr⁻¹ft⁻² , t is measured in °F and d is the specific gravity at 60 °F (16 °C).

Specific heat

The specific heat of a petroleum oils can be modeled as follows:

<math>c = \frac{1}{\sqrt{d}} [0.388+0.00045t]</math>,

where c is measured in BTU/lbm-°F, t is the temperature in Fahrenheit and d is the specific gravity at 60 °F (16 °C).

In units of kcal/(kg·°C), the formula is:

<math>\frac{1}{\sqrt{d}} [0.402+0.00081t]</math>,

where the temperature t is in Celsius and d is the specific gravity at 15 °C.

Latent heat of vaporization

The latent heat of vaporization can be modeled under atmospheric conditions as follows:

<math>L = \frac{1}{d}[110.9 - 0.09t]</math>,

where L is measured in BTU/lbm, t is measured in °F and d is the specific gravity at 60 °F (16 °C).

In units of kcal/kg, the formula is:

<math>L = \frac{1}{d}[194.4 - 0.162t]</math>,

where the temperature t is in Celsius and d is the specific gravity at 15 °C.^[15]

Formation

According to generally accepted theory, petroleum is derived from ancient biomass.^[16] It is a fossil fuel derived from ancient fossilized organic materials. The theory was initially based on the isolation of molecules from petroleum that closely resemble known biomolecules.

More specifically, crude oil and natural gas are products of heating of ancient organic materials (i.e. kerogen) over geological time. Formation of petroleum occurs from hydrocarbon pyrolysis, in a variety of mostly endothermic reactions at high temperature and/or pressure.^[17] Today's oil formed from the preserved remains of prehistoric zooplankton and algae, which had settled to a sea or lake bottom in large quantities under anoxic conditions (the remains of prehistoric terrestrial plants, on the other hand, tended to form coal). Over geological time the organic matter mixed with mud, and was buried under heavy layers of sediment resulting in high levels of heat and pressure (diagenesis). This process caused the organic matter to change, first into a waxy material known as kerogen, which is found in various oil shales around the world, and then with more heat into liquid and gaseous hydrocarbons via a process known as catagenesis.

There were certain warm nutrient-rich environments such as the Gulf of Mexico and the ancient Tethys Sea where the large amounts of organic material falling to the ocean floor exceeded the rate at which it could decompose. This resulted in large masses of organic material being buried under subsequent deposits such as shale formed from mud. This massive organic deposit later became heated and transformed under pressure into oil.^[18]

Geologists often refer to the temperature range in which oil forms as an "oil window"^[19]—below the minimum temperature oil remains trapped in the form of kerogen, and above the maximum temperature the oil is converted to natural gas through the process of thermal cracking. Sometimes, oil which is formed at extreme depths may migrate and become trapped at much shallower depths than where it was formed. The Athabasca Oil Sands is one example of this.

Abiogenic origin

A small number of geologists adhere to the abiogenic petroleum origin hypothesis and maintain that hydrocarbons of purely inorganic origin exist within Earth's interior. Chemists Marcellin Berthelot and Dmitri Mendeleev, as well as astronomer Thomas Gold championed the theory in the Western world by supporting the work done by Nikolai Kudryavtsev and Vladimir Porfiriev in the 1950s. It is currently supported primarily by Jack F. Kenney, Vladilen Krayushkin, and Vladimir Kutcherov.^[20][21]

The abiogenic origin hypothesis has not yet been ruled out, but it has little support among modern petroleum geologists.^[22] Its advocates consider that it is "still an open question"^[23] Extensive research into the chemical structure of kerogen has identified algae as the primary source of oil. The abiogenic origin hypothesis fails to explain the presence of these markers in kerogen and oil, as well as failing to explain how inorganic origin could be achieved at temperatures and pressures sufficient to convert kerogen to graphite. It has not been successfully used in uncovering oil deposits by geologists, as the hypothesis lacks any mechanism for determining where the process may occur.^[24] More recently scientists at the Carnegie Institution for Science have found that ethane and heavier hydrocarbons can be synthesized under conditions of the upper mantle.^[25]

Crude oil

Crude oil reservoirs

Three conditions must be present for oil reservoirs to form: a source rock rich in hydrocarbon material buried deep enough for subterranean heat to cook it into oil; a porous and permeable reservoir rock for it to accumulate in; and a cap rock (seal) or other mechanism that prevents it from escaping to the surface. Within these reservoirs, fluids will typically organize themselves like a three-layer cake with a layer of water below the oil layer and a layer of gas above it, although the different layers vary in size between reservoirs. Because most hydrocarbons are lighter than rock or water, they often migrate upward through adjacent rock layers until either reaching the surface or becoming trapped within porous rocks (known as reservoirs) by impermeable rocks above. However, the process is influenced by underground water flows, causing oil to migrate hundreds of kilometres horizontally or even short distances downward before becoming trapped in a reservoir. When hydrocarbons are concentrated in a trap, an oil field forms, from which the liquid can be extracted by drilling and pumping.

The reactions that produce oil and natural gas are often modeled as first order breakdown reactions, where hydrocarbons are broken down to oil and natural gas by a set of parallel reactions, and oil eventually breaks down to natural gas by another set of reactions. The latter set is regularly used in petrochemical plants and oil refineries.

Wells are drilled into oil reservoirs to extract the crude oil. "Natural lift" production methods that rely on the natural reservoir pressure to force the oil to the surface are usually sufficient for a while after reservoirs are first tapped. In some reservoirs, such as in the Middle East, the natural pressure is sufficient over a long time. The natural pressure in many reservoirs, however, eventually dissipates. Then the oil must be pumped out using “artificial lift” created by mechanical pumps powered by gas or electricity. Over time, these "primary" methods become less effective and "secondary" production methods may be used. A common secondary method is “waterflood” or injection of water into the reservoir to increase pressure and force the oil to the drilled shaft or "wellbore." Eventually "tertiary" or "enhanced" oil recovery methods may be used to increase the oil's flow characteristics by injecting steam, carbon dioxide and other gases or chemicals into the reservoir. In the United States, primary production methods account for less than 40% of the oil produced on a daily basis, secondary methods account for about half, and tertiary recovery the remaining 10%. Extracting oil (or “bitumen”) from oil/tar sand and oil shale deposits requires mining the sand or shale and heating it in a vessel or retort, or using “in-situ” methods of injecting heated liquids into the deposit and then pumping out the oil-saturated liquid.

Unconventional oil reservoirs

Oil-eating bacteria biodegrades oil that has escaped to the surface. Oil sands are reservoirs of partially biodegraded oil still in the process of escaping and being biodegraded, but they contain so much migrating oil that, although most of it has escaped, vast amounts are still present—more than can be found in conventional oil reservoirs. The lighter fractions of the crude oil are destroyed first, resulting in reservoirs containing an extremely heavy form of crude oil, called crude bitumen in Canada, or extra-heavy crude oil in Venezuela. These two countries have the world's largest deposits of oil sands.

On the other hand, oil shales are source rocks that have not been exposed to heat or pressure long enough to convert their trapped hydrocarbons into crude oil. Technically speaking, oil shales are not really shales and do not really contain oil, but are usually relatively hard rocks called marls containing a waxy substance called kerogen. The kerogen trapped in the rock can be converted into crude oil using heat and pressure to simulate natural processes. The method has been known for centuries and was patented in 1694 under British Crown Patent No. 330 covering, "A way to extract and make great quantityes of pitch, tarr, and oyle out of a sort of stone." Although oil shales are found in many countries, the United States has the world's largest deposits.^[26]

Classification

The petroleum industry generally classifies crude oil by the geographic location it is produced in (e.g. West Texas Intermediate, Brent, or Oman), its API gravity (an oil industry measure of density), and by its sulfur content. Crude oil may be considered light if it has low density or heavy if it has high density; and it may be referred to as sweet if it contains relatively little sulfur or sour if it contains substantial amounts of sulfur.

The geographic location is important because it affects transportation costs to the refinery. Light crude oil is more desirable than heavy oil since it produces a higher yield of petrol, while sweet oil commands a higher price than sour oil because it has fewer environmental problems and requires less refining to meet sulfur standards imposed on fuels in consuming countries. Each crude oil has unique molecular characteristics which are understood by the use of crude oil assay analysis in petroleum laboratories.

Barrels from an area in which the crude oil's molecular characteristics have been determined and the oil has been classified are used as pricing references throughout the world. Some of the common reference crudes are:

• West Texas Intermediate (WTI), a very high-quality, sweet, light oil delivered at Cushing, Oklahoma for North American oil
• Brent Blend, comprising 15 oils from fields in the Brent and Ninian systems in the East Shetland Basin of the North Sea. The oil is landed at Sullom Voe terminal in Shetland. Oil production from Europe, Africa and Middle Eastern oil flowing West tends to be priced off this oil, which forms a benchmark
• Dubai-Oman, used as benchmark for Middle East sour crude oil flowing to the Asia-Pacific region
• Tapis (from Malaysia, used as a reference for light Far East oil)
• Minas (from Indonesia, used as a reference for heavy Far East oil)
• The OPEC Reference Basket, a weighted average of oil blends from various OPEC (The Organization of the Petroleum Exporting Countries) countries
• Midway Sunset Heavy, by which heavy oil in California is priced ^[27]

There are declining amounts of these benchmark oils being produced each year, so other oils are more commonly what is actually delivered. While the reference price may be for West Texas Intermediate delivered at Cushing, the actual oil being traded may be a discounted Canadian heavy oil delivered at Hardisty, Alberta, and for a Brent Blend delivered at Shetland, it may be a Russian Export Blend delivered at the port of Primorsk.^[28]

Petroleum industry

The petroleum industry is involved in the global processes of exploration, extraction, refining, transporting (often with oil tankers and pipelines), and marketing petroleum products. The largest volume products of the industry are fuel oil and petrol . Petroleum is also the raw material for many chemical products, including pharmaceuticals, solvents, fertilizers, pesticides, and plastics. The industry is usually divided into three major components: upstream, midstream and downstream. Midstream operations are usually included in the downstream category.

Petroleum is vital to many industries, and is of importance to the maintenance of industrialized civilization itself, and thus is critical concern to many nations. Oil accounts for a large percentage of the world's energy consumption, ranging from a low of 32% for Europe and Asia, up to a high of 53% for the Middle East. Other geographic regions' consumption patterns are as follows: South and Central America (44%), Africa (41%), and North America (40%). The world at large consumes 30 billion barrels (4.8 km³) of oil per year, and the top oil consumers largely consist of developed nations. In fact, 24% of the oil consumed in 2004 went to the United States alone,^[29] though by 2007 this had dropped to 21% of world oil consumed.^[30]

In the US, in the states of Arizona, California, Hawaii, Nevada, Oregon and Washington, the Western States Petroleum Association (WSPA) represents companies responsible for producing, distributing, refining, transporting and marketing petroleum. This non-profit trade association was founded in 1907, and is the oldest petroleum trade association in the United States.^[31]

History

Petroleum, in one form or another, has been used since ancient times, and is now important across society, including in economy, politics and technology. The rise in importance was mostly due to the invention of the internal combustion engine, the rise in commercial aviation and the increasing use of plastic.

More than 4000 years ago, according to Herodotus and Diodorus Siculus, asphalt was used in the construction of the walls and towers of Babylon; there were oil pits near Ardericca (near Babylon), and a pitch spring on Zacynthus.^[32] Great quantities of it were found on the banks of the river Issus, one of the tributaries of the Euphrates. Ancient Persian tablets indicate the medicinal and lighting uses of petroleum in the upper levels of their society.

In the 1850s, the process to distill kerosene from petroleum was invented by Ignacy Łukasiewicz, providing a cheaper alternative to whale oil. The demand for the petroleum as a fuel for lighting in North America and around the world quickly grew.^[33] The world's first commercial oil well was drilled in Poland in 1853. Oil exploration developed in many parts of the world with the Russian Empire, particularly the Branobel company in Azerbaijan, taking the lead in production by the end of the 19th century.^[34] Oil exploration in North America during the early 20th century later led to the U.S. becoming the leading producer by the mid 1900s. As petroleum production in the U.S. peaked during the 1960s, however, Saudi Arabia and Russia surpassed the U.S.

Today, about 90% of vehicular fuel needs are met by oil. Petroleum also makes up 40% of total energy consumption in the United States, but is responsible for only 2% of electricity generation. Petroleum's worth as a portable, dense energy source powering the vast majority of vehicles and as the base of many industrial chemicals makes it one of the world's most important commodities.

The top three oil producing countries are Saudi Arabia, Russia, and the United States.^[35] About 80% of the world's readily accessible reserves are located in the Middle East, with 62.5% coming from the Arab 5: Saudi Arabia, UAE, Iraq, Qatar and Kuwait. A large portion of the world's total oil exists as unconventional sources, such as bitumen in Canada and Venezuela and oil shale. While significant volumes of oil are extracted from oil sands, particularly in Canada, logistical and technical hurdles remain, and Canada's oil sands are not expected to provide more than a few million barrels per day in the foreseeable future.

Price

After the collapse of the OPEC-administered pricing system in 1985, and a short lived experiment with netback pricing, oil-exporting countries adopted a market-linked pricing mechanism.^[36] First adopted by PEMEX in 1986, market-linked pricing was widely accepted, and by 1988 became and still is the main method for pricing crude oil in international trade.^[36] The current reference, or pricing markers, are Brent, WTI, and Dubai/Oman.^[36]

Uses

The chemical structure of petroleum is heterogeneous, composed of hydrocarbon chains of different lengths. Because of this, petroleum may be taken to oil refineries and the hydrocarbon chemicals separated by distillation and treated by other chemical processes, to be used for a variety of purposes. See Petroleum products.

Fuels

The most common distillations of petroleum are fuels. Fuels include (by increasing molecular masses):

• Liquefied petroleum gas (LPG)
• Ethane and other short-chain alkanes
• Gasoline (Petrol)
• Diesel fuel (petrodiesel)
• Kerosene
• Jet fuel
• Fuel oils

Other derivatives

Certain types of resultant hydrocarbons may be mixed with other non-hydrocarbons, to create other end products:

• Alkenes (olefins) which can be manufactured into plastics or other compounds
• Lubricants (produces light machine oils, motor oils, and greases, adding viscosity stabilizers as required).
• Wax, used in the packaging of frozen foods, among others.
• Sulfur or Sulfuric acid. These are a useful industrial materials. Sulfuric acid is usually prepared as the acid precursor oleum, a byproduct of sulfur removal from fuels.
• Bulk tar.
• Asphalt
• Petroleum coke, used in speciality carbon products or as solid fuel.
• Paraffin wax
• Aromatic petrochemicals to be used as precursors in other chemical production.

Petroleum by country

Consumption statistics

• Global Carbon Emissions.svg

  Global fossil carbon emissions, an indicator of consumption, for 1800–2007. Total is black, Oil is in blue.

• EIA IEO2006.jpg

  World energy consumption, 1980–2030. Source: International Energy Outlook 2006.

• Oil consumption per day by region from 1980 to 2006.svg

  daily oil consumption from 1980 to 2006

• Oil consumption per day by region from 1980 to 2006 solid3.svg

  oil consumption by percentage of total per region from 1980 to 2006: red=USA, blue=Europe, yellow=Asia+Oceania

Consumption

This table orders the amount of petroleum consumed in 2008 in thousand barrels (bbl) per day and in thousand cubic metres (m³) per day:^[37][38][39]

Source: US Energy Information Administration

Population Data:^[40]

¹ peak production of oil already passed in this state

² This country is not a major oil producer

Production

In petroleum industry parlance, production refers to the quantity of crude extracted from reserves, not the literal creation of the product.

Source: U.S. Energy Information Administration

¹ Peak production of conventional oil already passed in this state

² Although Canadian conventional oil production is declining, total oil production is increasing as oil sands production grows. If oil sands are included, it has the world's second largest oil reserves after Saudi Arabia.

³ Though still a member, Iraq has not been included in production figures since 1998