Oil Shale Processing
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Shale oil extraction is an industrial process for
unconventional oil Unconventional oil is petroleum produced or extracted using techniques other than the conventional method (oil well). Industry and governments across the globe are investing in unconventional oil sources due to the increasing scarcity of conventio ...
production. This process converts kerogen in oil shale into shale oil by pyrolysis, hydrogenation, or thermal dissolution. The resultant shale oil is used as
fuel oil Fuel oil is any of various fractions obtained from the distillation of petroleum (crude oil). Such oils include distillates (the lighter fractions) and residues (the heavier fractions). Fuel oils include heavy fuel oil, marine fuel oil (MFO), bun ...
or
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to meet refinery feedstock specifications by adding hydrogen and removing
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
and nitrogen impurities. Shale oil extraction is usually performed above ground (''ex situ'' processing) by mining the oil shale and then treating it in processing facilities. Other modern technologies perform the processing underground (on-site or '' in situ'' processing) by applying heat and extracting the oil via
oil well An oil well is a drillhole boring in Earth that is designed to bring petroleum oil hydrocarbons to the surface. Usually some natural gas is released as associated petroleum gas along with the oil. A well that is designed to produce only gas may ...
s. The earliest description of the process dates to the 10th century. In 1684, Great Britain granted the first formal extraction process patent. Extraction industries and innovations became widespread during the 19th century. The industry shrank in the mid-20th century following the discovery of large reserves of conventional oil, but high petroleum prices at the beginning of the 21st century have led to renewed interest, accompanied by the development and testing of newer technologies. As of 2010, major long-standing extraction industries are operating in Estonia, Brazil, and
China China, officially the People's Republic of China (PRC), is a country in East Asia. It is the world's most populous country, with a population exceeding 1.4 billion, slightly ahead of India. China spans the equivalent of five time zones and ...
. Its economic viability usually requires a lack of locally available crude oil. National energy security issues have also played a role in its development. Critics of shale oil extraction pose questions about
environmental management Environmental resource management is the management of the interaction and impact of human societies on the environment. It is not, as the phrase might suggest, the management of the environment itself. Environmental resources management aims ...
issues, such as waste disposal, extensive water use, waste water management, and air pollution.


History

In the 10th century, the Assyrian physician Masawaih al-Mardini (Mesue the Younger) wrote of his experiments in extracting oil from "some kind of bituminous shale". The first shale oil extraction patent was granted by the British Crown in 1684 to three people who had "found a way to extract and make great quantities of pitch, tarr, and oyle out of a sort of stone". Modern industrial extraction of shale oil originated in France with the implementation of a process invented by
Alexander Selligue Alexander François Selligue (1784-1845) was a French engineer. His name was in fact Alexandre François Gilles, but he used Selligue as an anagram of Gilles. In 1832, he together with David Blum patented an application of shale oil for direct il ...
in 1838, improved upon a decade later in Scotland using a process invented by James Young. During the late 19th century, plants were built in Australia, Brazil, Canada, and the United States. The 1894 invention of the
Pumpherston retort The Pumpherston retort (also known as the Bryson retort) was a type of oil-shale retort used in Scotland at the end of 19th and beginning of 20th century. It marked separation of the oil-shale industry from the coal industry as it was designed ...
, which was much less reliant on coal heat than its predecessors, marked the separation of the oil shale industry from the coal industry. China ( Manchuria), Estonia, New Zealand, South Africa, Spain,
Sweden Sweden, formally the Kingdom of Sweden,The United Nations Group of Experts on Geographical Names states that the country's formal name is the Kingdom of SwedenUNGEGN World Geographical Names, Sweden./ref> is a Nordic country located on ...
, and
Switzerland ). Swiss law does not designate a ''capital'' as such, but the federal parliament and government are installed in Bern, while other federal institutions, such as the federal courts, are in other cities (Bellinzona, Lausanne, Luzern, Neuchâtel ...
began extracting shale oil in the early 20th century. However, crude oil discoveries in Texas during the 1920s and in the Middle East in the mid 20th century brought most oil shale industries to a halt. In 1944, the US recommenced shale oil extraction as part of its
Synthetic Liquid Fuels Program The Synthetic Liquid Fuels Program was a program run by the United States Bureau of Mines to create the technology to produce synthetic fuel from coal and oil shale. It was initiated in 1944 during World War II. The Synthetic Liquid Fuels Act approv ...
. These industries continued until oil prices fell sharply in the 1980s. The last oil shale retort in the US, operated by Unocal Corporation, closed in 1991. The US program was restarted in 2003, followed by a commercial leasing program in 2005 permitting the extraction of oil shale and oil sands on federal lands in accordance with the
Energy Policy Act of 2005 The Energy Policy Act of 2005 () is a federal law signed by President George W. Bush on August 8, 2005, at Sandia National Laboratories in Albuquerque, New Mexico. The act, described by proponents as an attempt to combat growing energy problems ...
. , shale oil extraction is in operation in Estonia, Brazil, and China. In 2008, their industries produced about 930,000  tonnes (17,700
barrels A barrel or cask is a hollow cylindrical container with a bulging center, longer than it is wide. They are traditionally made of wooden staves and bound by wooden or metal hoops. The word vat is often used for large containers for liquids, u ...
per day) of shale oil. Australia, the US, and Canada have tested shale oil extraction techniques via demonstration projects and are planning commercial implementation; Morocco and Jordan have announced their intent to do the same. Only four processes are in commercial use:
Kiviter The Kiviter process is an above ground retorting technology for shale oil extraction. History The Kiviter process is based on the earlier vertical retort technology (Pintsch's generator). This technology underwent a long process of development ...
, Galoter, Fushun, and
Petrosix Petrosix is the world's largest surface oil shale pyrolysis retort with an diameter vertical shaft kiln, operational since 1992. It is located in São Mateus do Sul, Brazil, and it is owned and operated by the Brazil energy company Petrobras. Pet ...
.


Processing principles

Shale oil extraction process decomposes oil shale and converts its kerogen into shale oil—a petroleum-like
synthetic crude Synthetic crude is the output from a bitumen/extra heavy oil upgrader facility used in connection with oil sand production. It may also refer to shale oil, an output from an oil shale pyrolysis. The properties of the synthetic crude depend on the ...
oil. The process is conducted by pyrolysis, hydrogenation, or thermal dissolution. The efficiencies of extraction processes are often evaluated by comparing their yields to the results of a Fischer Assay performed on a sample of the shale. The oldest and the most common extraction method involves pyrolysis (also known as ''retorting'' or destructive distillation). In this process, oil shale is heated in the absence of oxygen until its kerogen decomposes into condensable shale oil vapors and non-condensable combustible oil shale gas. Oil vapors and oil shale gas are then collected and cooled, causing the shale oil to condense. In addition, oil shale processing produces spent oil shale, which is a solid residue. Spent shale consists of
inorganic compound In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemist ...
s ( minerals) and
char Char may refer to: People *Char Fontane, American actress *Char Margolis, American spiritualist * René Char (1907–1988), French poet *The Char family of Colombia: ** Fuad Char, Colombian senator ** Alejandro Char Chaljub, mayor of Barranquilla ...
—a carbonaceous residue formed from kerogen. Burning the char off the spent shale produces oil shale ash. Spent shale and shale ash can be used as ingredients in cement or brick manufacture. The composition of the oil shale may lend added value to the extraction process through the recovery of by-products, including ammonia,
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
, aromatic compounds, pitch, asphalt, and waxes. Heating the oil shale to pyrolysis temperature and completing the endothermic kerogen decomposition reactions require a source of energy. Some technologies burn other
fossil fuel A fossil fuel is a hydrocarbon-containing material formed naturally in the Earth's crust from the remains of dead plants and animals that is extracted and burned as a fuel. The main fossil fuels are coal, oil, and natural gas. Fossil fuels m ...
s such as natural gas, oil, or coal to generate this heat and experimental methods have used electricity,
radio wave Radio waves are a type of electromagnetic radiation with the longest wavelengths in the electromagnetic spectrum, typically with frequencies of 300 gigahertz (GHz) and below. At 300 GHz, the corresponding wavelength is 1 mm (short ...
s, microwaves, or reactive fluids for this purpose. Two strategies are used to reduce, and even eliminate, external heat energy requirements: the oil shale gas and char by-products generated by pyrolysis may be burned as a source of energy, and the heat contained in hot spent oil shale and oil shale ash may be used to pre-heat the raw oil shale. For ''ex situ'' processing, oil shale is crushed into smaller pieces, increasing surface area for better extraction. The temperature at which decomposition of oil shale occurs depends on the time-scale of the process. In ''ex situ'' retorting processes, it begins at and proceeds more rapidly and completely at higher temperatures. The amount of oil produced is the highest when the temperature ranges between . The ratio of oil shale gas to shale oil generally increases along with retorting temperatures. For a modern ''in situ'' process, which might take several months of heating, decomposition may be conducted at temperatures as low as . Temperatures below are preferable, as this prevents the decomposition of limestone and
dolomite Dolomite may refer to: *Dolomite (mineral), a carbonate mineral *Dolomite (rock), also known as dolostone, a sedimentary carbonate rock *Dolomite, Alabama, United States, an unincorporated community *Dolomite, California, United States, an unincor ...
in the rock and thereby limits carbon dioxide emissions and energy consumption. Hydrogenation and thermal dissolution (reactive fluid processes) extract the oil using
hydrogen donor In chemistry, transfer hydrogenation is a chemical reaction involving the addition of hydrogen to a Chemical compound, compound from a source other than Diatomic molecule, molecular . It is applied in laboratory and industrial organic synthesis to ...
s, solvents, or a combination of these. Thermal dissolution involves the application of solvents at elevated temperatures and pressures, increasing oil output by cracking the dissolved organic matter. Different methods produce shale oil with different properties.


Classification of extraction technologies

Industry analysts have created several classifications of the technologies used to extract shale oil from oil shale. ''By process principles'': Based on the treatment of raw oil shale by heat and solvents the methods are classified as pyrolysis, hydrogenation, or thermal dissolution. ''By location'': A frequently used distinction considers whether processing is done above or below ground, and classifies the technologies broadly as ''ex situ'' (displaced) or ''in situ'' (in place). In ''ex situ'' processing, also known as above-ground retorting, the oil shale is mined either
underground Underground most commonly refers to: * Subterranea (geography), the regions beneath the surface of the Earth Underground may also refer to: Places * The Underground (Boston), a music club in the Allston neighborhood of Boston * The Underground (S ...
or at the surface and then transported to a processing facility. In contrast, ''in situ'' processing converts the kerogen while it is still in the form of an oil shale deposit, following which it is then extracted via
oil well An oil well is a drillhole boring in Earth that is designed to bring petroleum oil hydrocarbons to the surface. Usually some natural gas is released as associated petroleum gas along with the oil. A well that is designed to produce only gas may ...
s, where it rises in the same way as conventional crude oil. Unlike ''ex situ'' processing, it does not involve mining or spent oil shale disposal aboveground as spent oil shale stays underground. ''By heating method'': The method of transferring heat from combustion products to the oil shale may be classified as direct or indirect. While methods that allow combustion products to contact the oil shale within the
retort In a chemistry laboratory, a retort is a device used for distillation or dry distillation of substances. It consists of a spherical vessel with a long downward-pointing neck. The liquid to be distilled is placed in the vessel and heated. The n ...
are classified as ''direct'', methods that burn materials external to the retort to heat another material that contacts the oil shale are described as ''indirect'' ''By heat carrier'': Based on the material used to deliver heat energy to the oil shale, processing technologies have been classified into gas heat carrier, solid heat carrier, wall conduction, reactive fluid, and volumetric heating methods. Heat carrier methods can be sub-classified as direct or indirect. The following table shows extraction technologies classified by heating method, heat carrier and location (''in situ'' or ''ex situ''). ''By raw oil shale particle size'': The various ''ex situ'' processing technologies may be differentiated by the size of the oil shale particles that are fed into the retorts. As a rule, gas heat carrier technologies process oil shale lumps varying in diameter from , while solid heat carrier and wall conduction technologies process fines which are particles less than in diameter. ''By retort orientation'': "Ex-situ" technologies are sometimes classified as vertical or horizontal. Vertical retorts are usually shaft kilns where a bed of shale moves from top to bottom by gravity. Horizontal retorts are usually horizontal rotating drums or screws where shale moves from one end to the other. As a general rule, vertical retorts process lumps using a gas heat carrier, while horizontal retorts process fines using solid heat carrier. ''By complexity of technology'': ''In situ'' technologies are usually classified either as ''true in situ'' processes or ''modified in situ'' processes. ''True in situ'' processes do not involve mining or crushing the oil shale. ''Modified in situ'' processes involve drilling and fracturing the target oil shale deposit to create voids in the deposit. The voids enable a better flow of gases and fluids through the deposit, thereby increasing the volume and quality of the shale oil produced.


''Ex situ'' technologies


Internal combustion

Internal combustion technologies burn materials (typically char and oil shale gas) within a vertical shaft retort to supply heat for pyrolysis. Typically raw oil shale particles between and in size are fed into the top of the retort and are heated by the rising hot gases, which pass through the descending oil shale, thereby causing decomposition of the kerogen at about . Shale oil mist, evolved gases and cooled combustion gases are removed from the top of the retort then moved to separation equipment. Condensed shale oil is collected, while non-condensable gas is recycled and used to carry heat up the retort. In the lower part of the retort, air is injected for the combustion which heats the spent oil shale and gases to between and . Cold recycled gas may enter the bottom of the retort to cool the shale ash. The Union A and Superior Direct processes depart from this pattern. In the Union A process, oil shale is fed through the bottom of the retort and a pump moves it upward. In the Superior Direct process, oil shale is processed in a horizontal, segmented, doughnut-shaped traveling-grate retort. Internal combustion technologies such as the Paraho Direct are thermally efficient, since combustion of char on the spent shale and heat recovered from the shale ash and evolved gases can provide all the heat requirements of the retort. These technologies can achieve 80–90% of Fischer assay yield. Two well-established shale oil industries use internal combustion technologies: Kiviter process facilities have been operated continuously in Estonia since the 1920s, and a number of Chinese companies operate Fushun process facilities. Common drawbacks of internal combustion technologies are that the combustible oil shale gas is diluted by combustion gases and particles smaller than can not be processed. Uneven distribution of gas across the retort can result in blockages when hot spots cause particles to fuse or disintegrate.


Hot recycled solids

Hot recycled solids technologies deliver heat to the oil shale by recycling hot solid particles—typically oil shale ash. These technologies usually employ rotating kiln or fluidized bed retorts, fed by fine oil shale particles generally having a diameter of less than ; some technologies use particles even smaller than . The recycled particles are heated in a separate chamber or vessel to about and then mixed with the raw oil shale to cause the shale to decompose at about . Oil vapour and shale oil gas are separated from the solids and cooled to condense and collect the oil. Heat recovered from the combustion gases and shale ash may be used to dry and preheat the raw oil shale before it is mixed with the hot recycle solids. In the Galoter and Enefit processes, the spent oil shale is burnt in a separate furnace and the resulting hot ash is separated from the combustion gas and mixed with oil shale particles in a rotating kiln. Combustion gases from the furnace are used to dry the oil shale in a dryer before mixing with hot ash. The
TOSCO II process The TOSCO II process is an above ground retorting technology for shale oil extraction, which uses fine particles of oil shale that are heated in a rotating kiln. The particularity of this process is that it use hot ceramic balls for the heat tran ...
uses ceramic balls instead of shale ash as the hot recycled solids. The distinguishing feature of the Alberta Taciuk Process (ATP) is that the entire process occurs in a single rotating multi–chamber horizontal vessel. Because the hot recycle solids are heated in a separate furnace, the oil shale gas from these technologies is not diluted with combustion exhaust gas. Another advantage is that there is no limit on the smallest particles that the retort can process, thus allowing all the crushed feed to be used. One disadvantage is that more water is used to handle the resulting finer shale ash.


Conduction through a wall

These technologies transfer heat to the oil shale by conducting it through the retort wall. The shale feed usually consists of fine particles. Their advantage lies in the fact that retort vapors are not combined with combustion exhaust. The
Combustion Resources Combustion Resources, Inc. was a consulting company based in Provo, Utah, United States. It provided consulting services in the fields of fuel and combustion, such as testing of flow and mixing systems, reactor design, gas and particle sampling, g ...
process uses a hydrogen–fired rotating kiln, where hot gas is circulated through an outer
annulus Annulus (or anulus) or annular indicates a ring- or donut-shaped area or structure. It may refer to: Human anatomy * ''Anulus fibrosus disci intervertebralis'', spinal structure * Annulus of Zinn, a.k.a. annular tendon or ''anulus tendineus com ...
. The Oil-Tech staged electrically heated retort consists of individual inter-connected heating chambers, stacked atop each other. Its principal advantage lies in its
modular design Modular design, or modularity in design, is a design principle that subdivides a system into smaller parts called ''modules'' (such as modular process skids), which can be independently created, modified, replaced, or exchanged with other modules ...
, which enhances its portability and adaptability. The
Red Leaf Resources Red Leaf Resources, Inc, doing business as Green Leaf Carbon Technologies, is an oil-shale technology company based in Salt Lake City, Utah, United States. It is the developer of the shale oil extraction technology HCCO® (Homogeneous Charged Con ...
EcoShale In-Capsule Process combines surface mining with a lower-temperature heating method similar to ''in situ'' processes by operating within the confines of an earthen structure. A hot gas circulated through parallel pipes heats the oil shale rubble. An installation within the empty space created by mining would permit rapid reclamation of the topography. A general drawback of conduction through a wall technologies is that the retorts are more costly when scaled-up due to the resulting large amount of heat conducting walls made of high-temperature alloys.


Externally generated hot gas

In general, externally generated hot gas technologies are similar to internal combustion technologies in that they also process oil shale lumps in vertical shaft kilns. Significantly, though, the heat in these technologies is delivered by gases heated outside the retort vessel, and therefore the retort vapors are not diluted with combustion exhaust. The
Petrosix Petrosix is the world's largest surface oil shale pyrolysis retort with an diameter vertical shaft kiln, operational since 1992. It is located in São Mateus do Sul, Brazil, and it is owned and operated by the Brazil energy company Petrobras. Pet ...
and Paraho Indirect employ this technology. In addition to not accepting fine particles as feed, these technologies do not utilize the potential heat of combusting the char on the spent shale and thus must burn more valuable fuels. However, due to the lack of combustion of the spent shale, the oil shale does not exceed and significant carbonate mineral decomposition and subsequent CO2 generation can be avoided for some oil shales. Also, these technologies tend to be the more stable and easier to control than internal combustion or hot solid recycle technologies.


Reactive fluids

Kerogen is tightly bound to the shale and resists dissolution by most solvents. Despite this constraint, extraction using especially reactive fluids has been tested, including those in a supercritical state. Reactive fluid technologies are suitable for processing oil shales with a low hydrogen content. In these technologies, hydrogen gas (H2) or hydrogen donors (chemicals that donate hydrogen during chemical reactions) react with coke
precursors Precursor or Precursors may refer to: * Precursor (religion), a forerunner, predecessor ** The Precursor, John the Baptist Science and technology * Precursor (bird), a hypothesized genus of fossil birds that was composed of fossilized parts of un ...
(chemical structures in the oil shale that are prone to form char during retorting but have not yet done so). Reactive fluid technologies include the IGT Hytort (high-pressure H2) process, donor solvent processes, and the Chattanooga fluidized bed reactor. In the IGT Hytort oil shale is processed in a high-pressure hydrogen environment. The Chattanooga process uses a fluidized bed reactor and an associated hydrogen-fired heater for oil shale thermal cracking and hydrogenation. Laboratory results indicate that these technologies can often obtain significantly higher oil yields than pyrolysis processes. Drawbacks are the additional cost and complexity of hydrogen production and high-pressure retort vessels.


Plasma gasification

Several experimental tests have been conducted for the oil-shale gasification by using
plasma Plasma or plasm may refer to: Science * Plasma (physics), one of the four fundamental states of matter * Plasma (mineral), a green translucent silica mineral * Quark–gluon plasma, a state of matter in quantum chromodynamics Biology * Blood pla ...
technologies. In these technologies, oil shale is bombarded by
radicals Radical may refer to: Politics and ideology Politics *Radical politics, the political intent of fundamental societal change *Radicalism (historical), the Radical Movement that began in late 18th century Britain and spread to continental Europe and ...
( ions). The radicals crack kerogen molecules forming
synthetic gas Syngas, or synthesis gas, is a mixture of hydrogen and carbon monoxide, in various ratios. The gas often contains some carbon dioxide and methane. It is principly used for producing ammonia or methanol. Syngas is combustible and can be used as ...
and oil. Air, hydrogen or nitrogen are used as plasma gas and processes may operate in an
arc ARC may refer to: Business * Aircraft Radio Corporation, a major avionics manufacturer from the 1920s to the '50s * Airlines Reporting Corporation, an airline-owned company that provides ticket distribution, reporting, and settlement services * ...
,
plasma arc A plasma torch (also known as a plasma arc, plasma gun, plasma cutter, or plasmatron) is a device for generating a directed flow of plasma. The plasma jet can be used for applications including plasma cutting, plasma arc welding, plasma spraying ...
, or plasma electrolysis mode. The main benefit of these technologies is processing without using water.


''In situ'' technologies

'' In situ'' technologies heat oil shale underground by injecting hot fluids into the rock formation, or by using linear or planar heating sources followed by
thermal conduction Conduction is the process by which heat is transferred from the hotter end to the colder end of an object. The ability of the object to conduct heat is known as its ''thermal conductivity'', and is denoted . Heat spontaneously flows along a tem ...
and convection to distribute heat through the target area. Shale oil is then recovered through vertical wells drilled into the formation. These technologies are potentially able to extract more shale oil from a given area of land than conventional ''
ex situ Svalbard GLOBAL SEED BANK, an ''ex situ'' conservation. ''Ex situ'' conservation literally means, "off-site conservation". It is the process of protecting an endangered species, variety or breed, of plant or animal outside its natural habitat; ...
'' processing technologies, as the wells can reach greater depths than surface mines. They present an opportunity to recover shale oil from low-grade deposits that traditional mining techniques could not extract. John Fell experimented with ''in situ'' extraction, at
Newnes Newnes (), an abandoned oil shale mining site of the Wolgan Valley, is located in the Central Tablelands region of New South Wales, Australia. The site that was operational in the early 20th century is now partly surrounded by Wollemi Nationa ...
, In Australia, during 1921, with some success, but his ambitions were well ahead of technologies available at the time. During World War II a modified ''in situ'' extraction process was implemented without significant success in Germany. One of the earliest successful ''in situ'' processes was underground gasification by electrical energy (
Ljungström Ljungström is a Swedish family originating from Jönköping County, Småland, through the bailiff Johan ''Liungström'' (''floruit'' 1716, died circa 1730). Members in selection * Johan Patrik Ljungström (1784–1859), jeweler * Jonas Patrik ...
method)—a process exploited between 1940 and 1966 for shale oil extraction at Kvarntorp in Sweden. Prior to the 1980s, many variations of the ''in situ'' process were explored in the United States. The first modified ''in situ'' oil shale experiment in the United States was conducted by
Occidental Petroleum Occidental Petroleum Corporation (often abbreviated Oxy in reference to its ticker symbol and logo) is an American company engaged in hydrocarbon exploration in the United States, and the Middle East as well as petrochemical manufacturing in the ...
in 1972 at Logan Wash, Colorado. Newer technologies are being explored that use a variety of heat sources and heat delivery systems.


Wall conduction

Wall conduction ''in situ'' technologies use heating elements or heating pipes placed within the oil shale formation. The
Shell in situ conversion process The Shell ''in situ'' conversion process (Shell ICP) is an ''in situ'' shale oil extraction technology to convert kerogen in oil shale to shale oil. It is developed by the Shell Oil Company. History Shell's ''in situ'' conversion process has been ...
(Shell ICP) uses electrical heating elements for heating the oil shale layer to between over a period of approximately four years. The processing area is isolated from surrounding groundwater by a freeze wall consisting of wells filled with a circulating super-chilled fluid. Disadvantages of this process are large electrical power consumption, extensive water use, and the risk of groundwater pollution. The process was tested since the early 1980s at the Mahogany test site in the Piceance Basin. of oil were extracted in 2004 at a testing area. In the CCR Process proposed by American Shale Oil,
superheated steam Superheated steam is steam at a temperature higher than its vaporization point at the absolute pressure where the temperature is measured. Superheated steam can therefore cool (lose internal energy) by some amount, resulting in a lowering of its ...
or another heat transfer medium is circulated through a series of pipes placed below the oil shale layer to be extracted. The system combines horizontal wells, through which steam is passed, and vertical wells, which provide both vertical heat transfer through refluxing of converted shale oil and a means to collect the produced hydrocarbons. Heat is supplied by combustion of natural gas or
propane Propane () is a three-carbon alkane with the molecular formula . It is a gas at standard temperature and pressure, but compressible to a transportable liquid. A by-product of natural gas processing and petroleum refining, it is commonly used a ...
in the initial phase and by oil shale gas at a later stage. The Geothermic Fuels Cells Process (IEP GFC) proposed by
Independent Energy Partners Independent Energy Partners, Inc. (IEP) is an oil shale resources company based in Parker, Colorado, the United States. It is a developer of the Geothermic Fuels Cells Process, an '' in-situ'' shale oil extraction process. CEO of the company i ...
extracts shale oil by exploiting a high-temperature stack of
fuel cell A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most batteries in requ ...
s. The cells, placed in the oil shale formation, are fueled by natural gas during a warm-up period and afterward by oil shale gas generated by its own waste heat.


Externally generated hot gas

Externally generated hot gas ''in situ'' technologies use hot gases heated above-ground and then injected into the oil shale formation. The
Chevron CRUSH Chevron CRUSH is an experimental ''in situ'' shale oil extraction technology to convert kerogen in oil shale to shale oil. The name stands for Chevron's Technology for the Recovery and Upgrading of Oil from Shale. It is developed jointly by Chevro ...
process, which was researched by
Chevron Corporation Chevron Corporation is an American multinational energy corporation. The second-largest direct descendant of Standard Oil, and originally known as the Standard Oil Company of California (shortened to Socal or CalSo), it is headquartered in S ...
in partnership with Los Alamos National Laboratory, injects heated carbon dioxide into the formation via drilled wells and to heat the formation through a series of horizontal fractures through which the gas is circulated. General Synfuels International has proposed the
Omnishale process Omnishale process (also known as the ''Petro Probe process'') is an ''in situ'' shale oil extraction technology to convert kerogen in oil shale to shale oil. This process is classified as an externally generated hot gas technology. The technology ...
involving injection of super-heated air into the oil shale formation.
Mountain West Energy Mountain West Energy, LLC is an American unconventional oil recovery technology research and development company based in Orem, Utah. It is a developer of the In-situ Vapor Extraction Technology, an '' in-situ'' shale oil extraction technology. The ...
's In Situ Vapor Extraction process uses similar principles of injection of high-temperature gas.


ExxonMobil Electrofrac

ExxonMobil ExxonMobil Corporation (commonly shortened to Exxon) is an American multinational oil and gas corporation headquartered in Irving, Texas. It is the largest direct descendant of John D. Rockefeller's Standard Oil, and was formed on November 30, ...
's ''in situ'' technology (
ExxonMobil Electrofrac ExxonMobil Electrofrac is an ''in situ'' shale oil extraction technology proposed by ExxonMobil for converting kerogen in oil shale to shale oil. Technology ExxonMobil Electrofrac uses a series of fractures created in the oil shale formation. Pre ...
) uses electrical heating with elements of both wall conduction and volumetric heating methods. It injects an electrically conductive material such as
calcined petroleum coke Petroleum coke, abbreviated coke or petcoke, is a final carbon-rich solid material that derives from oil refining, and is one type of the group of fuels referred to as cokes. Petcoke is the coke that, in particular, derives from a final cracki ...
into the hydraulic fractures created in the oil shale formation which then forms a heating element. Heating wells are placed in a parallel row with a second horizontal well intersecting them at their toe. This allows opposing electrical charges to be applied at either end.


Volumetric heating

The Illinois Institute of Technology developed the concept of oil shale volumetric heating using radio waves (radio frequency processing) during the late 1970s. This technology was further developed by
Lawrence Livermore National Laboratory Lawrence Livermore National Laboratory (LLNL) is a federal research facility in Livermore, California, United States. The lab was originally established as the University of California Radiation Laboratory, Livermore Branch in 1952 in response ...
. Oil shale is heated by vertical electrode arrays. Deeper volumes could be processed at slower heating rates by installations spaced at tens of meters. The concept presumes a radio frequency at which the skin depth is many tens of meters, thereby overcoming the thermal diffusion times needed for conductive heating. Its drawbacks include intensive electrical demand and the possibility that groundwater or char would absorb undue amounts of the energy. Radio frequency processing in conjunction with critical fluids is being developed by Raytheon together with CF Technologies and tested by
Schlumberger Schlumberger Limited (), doing business as SLB, is an oilfield services company. Schlumberger has four principal executive offices located in Paris, Houston, London, and The Hague. Schlumberger is the world's largest offshore drilling compa ...
. Microwave heating technologies are based on the same principles as radio wave heating, although it is believed that radio wave heating is an improvement over microwave heating because its energy can penetrate farther into the oil shale formation. The microwave heating process was tested by
Global Resource Corporation Global means of or referring to a globe and may also refer to: Entertainment * ''Global'' (Paul van Dyk album), 2003 * ''Global'' (Bunji Garlin album), 2007 * ''Global'' (Humanoid album), 1989 * ''Global'' (Todd Rundgren album), 2015 * Bruno ...
. Electro-Petroleum proposes electrically
enhanced oil recovery Enhanced oil recovery (abbreviated EOR), also called tertiary recovery, is the extraction of crude oil from an oil field that cannot be extracted otherwise. EOR can extract 30% to 60% or more of a reservoir's oil, compared to 20% to 40% using ...
by the passage of direct current between cathodes in producing wells and anodes located either at the surface or at depth in other wells. The passage of the current through the oil shale formation results in resistive
Joule heating Joule heating, also known as resistive, resistance, or Ohmic heating, is the process by which the passage of an electric current through a conductor (material), conductor produces heat. Joule's first law (also just Joule's law), also known in c ...
.


Shale oil

The properties of raw shale oil vary depending on the composition of the parent oil shale and the extraction technology used. Like conventional oil, shale oil is a complex mixture of hydrocarbons, and it is characterized using bulk properties of the oil. Shale oil usually contains large quantities of
olefin In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond. Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic, an ...
ic and aromatic hydrocarbons. Shale oil can also contain significant quantities of heteroatoms. A typical shale oil composition includes 0.5–1% of oxygen, 1.5–2% of nitrogen and 0.15–1% of
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
, and some deposits contain more heteroatoms. Mineral particles and metals are often present as well. Generally, the oil is less fluid than crude oil, becoming pourable at temperatures between , while conventional crude oil is pourable at temperatures between ; this property affects shale oil's ability to be transported in existing pipelines. Shale oil contains polycyclic aromatic hydrocarbons which are carcinogenic. It has been described that raw shale oil has a mild carcinogenic potential which is comparable to some intermediate refinery products, while upgraded shale oil has lower carcinogenic potential as most of the polycyclic aromatics are believed to broken down by hydrogenation. Although raw shale oil can be immediately burnt as a fuel oil, many of its applications require that it be upgraded. The differing properties of the raw oils call for correspondingly various pre-treatments before it can be sent to a conventional oil refinery. Particulates in the raw oil clog downstream processes;
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
and nitrogen create air pollution. Sulfur and nitrogen, along with the arsenic and iron that may be present, also destroy the catalysts used in refining.
Olefin In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond. Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic, an ...
s form insoluble sediments and cause instability. The oxygen within the oil, present at higher levels than in
crude oil Petroleum, also known as crude oil, or simply oil, is a naturally occurring yellowish-black liquid mixture of mainly hydrocarbons, and is found in geological formations. The name ''petroleum'' covers both naturally occurring unprocessed crude ...
, lends itself to the formation of destructive free radicals.
Hydrodesulfurization Hydrodesulfurization (HDS) is a catalytic chemical process widely used to remove sulfur (S) from natural gas and from refined petroleum products, such as gasoline or petrol, jet fuel, kerosene, diesel fuel, and fuel oils. The purpose of remov ...
and
hydrodenitrogenation Hydrodenitrogenation (HDN) is an industrial process for the removal of nitrogen from petroleum. Organonitrogen compounds, even though they occur at low levels, are undesirable because they cause poisoning of downstream catalysts. Furthermore, up ...
can address these problems and result in a product comparable to benchmark crude oil. Phenols can be first be removed by water extraction. Upgrading shale oil into transport fuels requires adjusting hydrogen–carbon ratios by adding hydrogen (
hydrocracking In petrochemistry, petroleum geology and organic chemistry, cracking is the process whereby complex organic molecules such as kerogens or long-chain hydrocarbons are broken down into simpler molecules such as light hydrocarbons, by the breaking of ...
) or removing carbon (
coking Coking is the heating of coal in the absence of oxygen to a temperature above 600 °C to drive off the volatile components of the raw coal, leaving a hard, strong, porous material of high carbon content called coke. Coke consists almost ent ...
). Before World War II, most shale oil was upgraded for use as transport fuels. Afterwards, it was used as a raw material for chemical intermediates, pure chemicals and industrial resins, and as a railroad wood preservative. As of 2008, it is primarily used as a heating oil and marine fuel, and to a lesser extent in the production of various chemicals. Shale oil's concentration of high-boiling point compounds is suited for the production of middle distillates such as kerosene,
jet fuel Jet fuel or aviation turbine fuel (ATF, also abbreviated avtur) is a type of aviation fuel designed for use in aircraft powered by gas-turbine engines. It is colorless to straw-colored in appearance. The most commonly used fuels for commercial a ...
and diesel fuel. Additional cracking can create the lighter hydrocarbons used in gasoline.


Economics

The dominant question for shale oil production is under what conditions shale oil is economically viable. According to the United States Department of Energy, the capital costs of a ''ex-situ'' processing complex are $3–10 billion. The various attempts to develop oil shale deposits have succeeded only when the shale-oil production cost in a given region is lower than the price of petroleum or its other substitutes. According to a survey conducted by the
RAND Corporation The RAND Corporation (from the phrase "research and development") is an American nonprofit global policy think tank created in 1948 by Douglas Aircraft Company to offer research and analysis to the United States Armed Forces. It is financed ...
, the cost of producing shale oil at a hypothetical surface retorting complex in the United States (comprising a mine, retorting plant, upgrading plant, supporting utilities, and spent oil shale reclamation), would be in a range of $70–95 per barrel ($440–600/m3), adjusted to 2005 values. Assuming a gradual increase in output after the start of commercial production, the analysis projects a gradual reduction in processing costs to $30–40 per barrel ($190–250/m3) after achieving the milestone of . The United States Department of Energy estimates that the ''ex-situ'' processing would be economic at sustained average world oil prices above $54 per barrel and ''in-situ'' processing would be economic at prices above $35 per barrel. These estimates assume a return rate of 15%. Royal Dutch Shell announced in 2006 that its Shell ICP technology would realize a profit when crude oil prices are higher than $30 per barrel ($190/m3), while some technologies at full-scale production assert profitability at oil prices even lower than $20 per barrel ($130/m3). To increase the efficiency of oil shale retorting and by this the viability of the shale oil production, researchers have proposed and tested several co-pyrolysis processes, in which other materials such as
biomass Biomass is plant-based material used as a fuel for heat or electricity production. It can be in the form of wood, wood residues, energy crops, agricultural residues, and waste from industry, farms, and households. Some people use the terms bi ...
, peat, waste
bitumen Asphalt, also known as bitumen (, ), is a sticky, black, highly viscous liquid or semi-solid form of petroleum. It may be found in natural deposits or may be a refined product, and is classed as a pitch. Before the 20th century, the term a ...
, or rubber and plastic wastes are retorted along with the oil shale. Some modified technologies propose combining a fluidized bed retort with a circulated fluidized bed furnace for burning the by-products of pyrolysis (char and oil shale gas) and thereby improving oil yield, increasing throughput, and decreasing retorting time. Other ways of improving the economics of shale oil extraction could be to increase the size of the operation to achieve economies of scale, use oil shale that is a by-product of coal mining such as at Fushun China, produce specialty chemicals as by
Viru Keemia Grupp Viru Keemia Grupp (VKG) is an Estonian holding group of oil shale industry, power generation, and public utility companies. History After Estonia gained independence, the state owned oil shale enterprise, Riigi Põlevkivitööstus ( en, Eston ...
in Estonia, co-generate electricity from the waste heat and process high grade oil shale that yields more oil per shale processed. A possible measure of the viability of oil shale as an energy source lies in the ratio of the energy in the extracted oil to the energy used in its mining and processing (Energy Returned on Energy Invested, or EROEI). A 1984 study estimated the EROEI of the various known oil shale deposits as varying between 0.7–13.3; Some companies and newer technologies assert an EROEI between 3 and 10. According to the World Energy Outlook 2010, the EROEI of ''ex-situ'' processing is typically 4 to 5 while of ''in-situ'' processing it may be even as low as 2. To increase the EROEI, several combined technologies were proposed. These include the usage of process waste heat, e.g.
gasification Gasification is a process that converts biomass- or fossil fuel-based carbonaceous materials into gases, including as the largest fractions: nitrogen (N2), carbon monoxide (CO), hydrogen (H2), and carbon dioxide (). This is achieved by reacting ...
or combustion of the residual carbon (char), and the usage of waste heat from other industrial processes, such as
coal gasification Coal gasification is the process of producing syngas—a mixture consisting primarily of carbon monoxide (CO), hydrogen (H2), carbon dioxide (CO2), methane (CH4), and water vapour (H2O)—from coal and water, air and/or oxygen. Historically, coal ...
and nuclear power generation. The water requirements of extraction processes are an additional economic consideration in regions where water is a scarce resource.


Environmental considerations

Mining oil shale involves a number of environmental impacts, more pronounced in surface mining than in underground mining. These include acid drainage induced by the sudden rapid exposure and subsequent oxidation of formerly buried materials, the introduction of metals including
mercury Mercury commonly refers to: * Mercury (planet), the nearest planet to the Sun * Mercury (element), a metallic chemical element with the symbol Hg * Mercury (mythology), a Roman god Mercury or The Mercury may also refer to: Companies * Merc ...
into surface-water and groundwater, increased erosion, sulfur-gas emissions, and air pollution caused by the production of particulates during processing, transport, and support activities. In 2002, about 97% of air pollution, 86% of total waste and 23% of water pollution in Estonia came from the power industry, which uses oil shale as the main resource for its power production. Oil-shale extraction can damage the biological and recreational value of land and the ecosystem in the mining area. Combustion and thermal processing generate waste material. In addition, the atmospheric emissions from oil shale processing and combustion include carbon dioxide, a
greenhouse gas A greenhouse gas (GHG or GhG) is a gas that Absorption (electromagnetic radiation), absorbs and Emission (electromagnetic radiation), emits radiant energy within the thermal infrared range, causing the greenhouse effect. The primary greenhouse ...
. Environmentalists oppose production and usage of oil shale, as it creates even more greenhouse gases than conventional fossil fuels. Experimental ''in situ'' conversion processes and carbon capture and storage technologies may reduce some of these concerns in the future, but at the same time they may cause other problems, including groundwater pollution. Among the water contaminants commonly associated with oil shale processing are oxygen and nitrogen heterocyclic hydrocarbons. Commonly detected examples include quinoline derivatives, pyridine, and various alkyl homologues of pyridine ( picoline,
lutidine Lutidine is the trivial name used to describe the chemical compounds which are dimethyl derivatives of pyridine Pyridine is a basic heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one met ...
). Water concerns are sensitive issues in arid regions, such as the western US and Israel's
Negev Desert The Negev or Negeb (; he, הַנֶּגֶב, hanNegév; ar, ٱلنَّقَب, an-Naqab) is a desert and semidesert region of southern Israel. The region's largest city and administrative capital is Beersheba (pop. ), in the north. At its southe ...
, where plans exist to expand oil-shale extraction despite a
water shortage Water scarcity (closely related to water stress or water crisis) is the lack of fresh water resources to meet the standard water demand. There are two types of water scarcity: physical or economic water scarcity. Physical water scarcity is where ...
. Depending on technology, above-ground retorting uses between one and five barrels of water per barrel of produced shale-oil. A 2008 programmatic environmental impact statement issued by the US
Bureau of Land Management The Bureau of Land Management (BLM) is an agency within the United States Department of the Interior responsible for administering federal lands. Headquartered in Washington DC, and with oversight over , it governs one eighth of the country's la ...
stated that surface mining and retort operations produce of waste water per of processed oil shale. ''In situ'' processing, according to one estimate, uses about one-tenth as much water.
Environmental A biophysical environment is a biotic and abiotic surrounding of an organism or population, and consequently includes the factors that have an influence in their survival, development, and evolution. A biophysical environment can vary in scale f ...
activists, including members of
Greenpeace Greenpeace is an independent global campaigning network, founded in Canada in 1971 by Irving Stowe and Dorothy Stowe, immigrant environmental activists from the United States. Greenpeace states its goal is to "ensure the ability of the Earth t ...
, have organized strong protests against the oil shale industry. In one result,
Queensland Energy Resources Queensland Energy Resources Limited (QERL) is an Australian oil shale mining and shale oil extraction company with the headquarters in Brisbane. It is the developer of the Stuart (Yarwun) and McFarlane oil shale projects. History Queensland En ...
put the proposed
Stuart Oil Shale Project The Stuart Oil Shale Project is an oil shale development project in Yarwun near Gladstone, Queensland, Australia. It is Australia's first major attempt since the 1950s to restart commercial use of oil shale. The project was originally developed ...
in Australia on hold in 2004.


See also

*
Oil shale in China Oil shale in China is an important source of unconventional oil. A total Chinese oil shale resource amounts of 720 billion tonnes, located in 80 deposits of 47 oil shale basins. This is equal to 48 billion tonnes of shale oil ...
* Oil shale in Estonia *
Oil shale in Jordan Oil shale in Jordan represents a significant resource. Oil shale deposits in Jordan underlie more than 60% of Jordanian territory. The total resources amounts to 31 billion tonnes of oil shale. The deposits include a high quality marinite oil s ...
*
Oil shale geology Oil shale geology is a branch of geologic sciences which studies the formation and composition of oil shales–fine-grained sedimentary rocks containing significant amounts of kerogen, and belonging to the group of sapropel fuels. Oil shale f ...
*
Oil shale reserves Oil shale reserves refers to oil shale resources that are economically recoverable under current economic conditions and technological abilities. Oil shale deposits range from small presently economically unrecoverable to large potentially recovera ...


References


External links


Oil Shale. A Scientific-Technical Journal
()
Oil Shale and Tar Sands Programmatic Environmental Impact Statement (EIS) Information Center.
Concerning potential leases of Federal oil sands lands in Utah and oil shale lands in Utah, Wyoming, and Colorado.
The United States National Oil Shale Association (NOSA)
{{DEFAULTSORT:Shale Oil Extraction Petroleum production Arab inventions