The Frasch process is a method to extract sulfur from underground deposits by taking advantage of the low melting point of sulfur. It is the only industrial method of recovering sulfur from elemental deposits.
[ Most of the world's sulfur was obtained this way until the late 20th century, when sulfur recovered from petroleum and gas sources became more commonplace (see Claus process).
In the Frasch process, superheated water is pumped into the sulfur deposit; the sulfur melts and is extracted. The Frasch process is able to produce high-purity sulfur of about 99.5%.
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History
In 1867, miners discovered sulfur
Sulfur ( American spelling and the preferred IUPAC name) or sulphur ( Commonwealth spelling) is a chemical element; it has symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms ...
in the caprock Caprock or cap rock is a hard, resistant, and impermeable layer of rock that overlies and protects a reservoir of softer organic material, similar to the crust on a pie where the crust (caprock) prevents leakage of the soft filling (softer materia ...
of a salt dome
A salt dome is a type of structural dome formed when salt (or other evaporite minerals) intrudes into overlying rocks in a process known as diapirism. Salt domes can have unique surface and subsurface structures, and they can be discovered us ...
in Calcasieu Parish, Louisiana, but it was beneath quicksand
Quicksand (also known as sinking sand) is a colloid consisting of fine granular material (such as sand, silt or clay) and water. It forms in saturated loose sand when the sand is suddenly agitated. When water in the sand cannot escape, it crea ...
, which prevented mining. In 1894 the German-born American chemist, Herman Frasch (1852–1914), devised his Frasch method of sulfur removal using pipes to bypass the quicksand. This replaced the inefficient and polluting Sicilian method. The process proved successful, on December 24, 1894, when the first molten sulfur was brought to the surface. The Union Sulphur Company was incorporated in 1896 to utilize the process. However, the high cost of fuel needed to heat the water made the process uneconomic until the 1901 discovery of the Spindletop
Spindletop is an oil field located in the southern portion of Beaumont, Texas, in the United States. The Spindletop dome was derived from the Louann Salt evaporite layer of the Jurassic geologic period. On January 10, 1901, a well at Spindlet ...
oil field in Texas provided cheap fuel oil to the region. The Frasch process began economic production at Sulphur Mines, Louisiana in 1903.[
When Frasch's patent expired, the process was widely applied to similar salt-dome sulfur deposits along the ]Gulf Coast
The Gulf Coast of the United States, also known as the Gulf South or the South Coast, is the coastline along the Southern United States where they meet the Gulf of Mexico. The coastal states that have a shoreline on the Gulf of Mexico are Tex ...
of the United States. The second Frasch-process mine opened in 1912 in Brazoria County, Texas. The Gulf Coast came to dominate world sulfur production in the early and middle 20th century. However, starting in the 1970s, byproduct sulfur recovery from oil and natural gas lowered the price of sulfur and drove many Frasch-process mines out of business. The last United States Frasch sulfur mine closed in 2000. A Frasch mine in Iraq closed in 2003 due to the U.S. invasion of Iraq.
The Frasch process is still used to work sulfur deposits in Mexico, Ukraine and Poland.
Process
The Frasch sulfur process works best on either salt domes or bedded evaporite deposits, where sulfur is found in permeable rock layers trapped in between impermeable layers. Bacterial alteration of anhydrite or gypsum
Gypsum is a soft sulfate mineral composed of calcium sulfate Hydrate, dihydrate, with the chemical formula . It is widely mined and is used as a fertilizer and as the main constituent in many forms of plaster, drywall and blackboard or sidewalk ...
, in the presence of hydrocarbons, produces limestone and hydrogen sulfide
Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is toxic, corrosive, and flammable. Trace amounts in ambient atmosphere have a characteristic foul odor of rotten eggs. Swedish chemist ...
in the sulfur cycle
The sulfur cycle is a biogeochemical cycle in which the sulfur moves between rocks, waterways and living systems. It is important in geology as it affects many minerals and in life because sulfur is an essential element (CHNOPS), being a consti ...
. The hydrogen sulfide then oxidizes into sulfur, from percolating water, or through the action of anaerobic, sulfur-reducing bacteria
In the Frasch process, three concentric tubes are introduced into the sulfur deposit. Superheated water (165 °C, 2.5-3 MPa) is injected into the deposit via the outermost tube. Sulfur (m.p. 115 °C) melts and flows into the middle tube. Water pressure alone is unable to force the sulfur into the surface due to the molten sulfur's greater density, so hot air is introduced via the innermost tube to froth the sulfur, making it less dense, and pushing it to the surface.[
The sulfur obtained can be very pure (99.7 - 99.8%). In this form, it is light yellow in color. If contaminated by organic compounds, it can be dark-colored; further purification is not economic, and usually unnecessary. Using this method, the United States produced 3.89 million tons of sulfur in 1989, and Mexico produced 1.02 million tons of sulfur in 1991.
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The Frasch process can be used for deposits 50–800 meters deep. 3-38 cubic meters of superheated water are required to produce every tonne of sulfur, and the associated energy cost is significant.[ A working demonstration model of the Frasch process suitable for the classroom has been described.]
Economic Impact
List of Mines
Mexico
In 1955 Mexico became the world's second largest producer of sulfur behind the United States.
References
Further reading
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History of Sulphur (Sulphur, Louisiana)
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External links
*{{cite web , title = Strange mines tap sulphur , work = Popular Science , date = December 1942 , author = Alden P. Armagnac , publisher = Popular Science Publishing Co. , url = https://books.google.com/books?id=HCcDAAAAMBAJ&q=%22Frasch+process%22&pg=PA102 (Description of Frasch process)
Mineral processing
Sulfur mining