Editing Frasch process

{{short description|Industrial method of sulfur extraction}}
{{infobox industrial process
| name           = Frasch process of Sulfur extraction
| image          = Frasch Process.png
| caption        = b
| type           = Superheated water
| sector         = [[Mining]]
| technologies   = 
| feedstock      =
| product        = [[Sulfur]]
| companies      =
| facility       =
| inventor       = [[Herman Frasch]]
| year           = 1894}}

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.<ref name = Ullmann/> 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%. <ref>[http://www.sulphurinstitute.org/learnmore/sulphur101.cfm The Sulphur Institute. "An Introduction to Sulphur."] {{Webarchive|url=https://web.archive.org/web/20160312131652/http://www.sulphurinstitute.org/learnmore/sulphur101.cfm |date=2016-03-12 }}, accessed 17 January 2011.</ref>

==History==
[[File:Frasch Process used on a salt dome.png|thumb|400px|Illustration that shows the structure of a sulfur-containing salt dome and the details of the Frasch pump used to extract the sulfur from underground formations. Superheated water is pumped into the formation to melt the sulfur. The molten sulfur is lifted to the surface with compressed air.<ref name=Ober/><ref name=Haynes/>]]

In 1867, miners discovered [[sulfur]] in the [[caprock]] of a [[salt dome]] in [[Calcasieu Parish, Louisiana]], but it was beneath [[quicksand]], 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.<ref>{{cite journal | title = Obituaries - Herman Frasch, Paul L. V. Héroult | journal = Industrial & Engineering Chemistry  | year = 1914 | volume = 6 | issue = 6 | pages = 505–507 | doi = 10.1021/ie50066a024}}</ref> 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]] oil field in Texas provided cheap fuel oil to the region.<ref>{{cite book | chapter-url = https://books.google.com/books?id=DsSmPKEOWDcC&pg=PA1512 | author = D'Arcy Shock | year = 1992 | chapter = Frasch sulfur mining | title = SME Mining Engineering Handbook | publisher = Society for Mining Metallurgy and Exploration | pages = 1512 | chapter-format = [[Google Books]] excerpt| isbn = 9780873351003 }}</ref>  The Frasch process began economic production at [[Sulphur, Louisiana|Sulphur Mines, Louisiana]] in 1903.<ref name=Ober/>

When Frasch's patent expired, the process was widely applied to similar salt-dome sulfur deposits along the [[Gulf Coast]] 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.<ref>[https://tshaonline.org/handbook/online/articles/dks04 Handbook of Texas Online: ''Sulfur industry''], accessed 20 February 2009.</ref>  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.<ref>[http://pubs.usgs.gov/of/2002/of02-298/of02-298.pdf Joyce A. Ober (2002) ''Materials Flow of Sulfur'', US Geological Survey, Open-File Report 02-298], p.12, PDF file, retrieved 20 February 2009.</ref> 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 [[permeability (earth sciences)|permeable]] rock layers trapped in between impermeable layers. Bacterial alteration of [[anhydrite]] or [[gypsum]], in the presence of hydrocarbons, produces limestone and [[hydrogen sulfide]] in the [[sulfur cycle]]. The hydrogen sulfide then oxidizes into sulfur, from percolating water, or through the action of anaerobic, sulfur-reducing bacteria <ref name=Ober>{{cite book |last1=Ober |first1=Joyce |title=MATERIALS FLOW OF SULFUR, USGS Open-File Report 02-298 |date=2002 |publisher=U.S. Dept. of the Interior, USGS |pages=12–13 |url=https://pubs.usgs.gov/of/2002/of02-298/of02-298.pdf}}</ref><ref name=Haynes>{{cite book |last1=Haynes |first1=Williams |title=Brimstone, The Stone that Burns |date=1959 |publisher=D. Van Nostrand Company, Inc. |location=Princeton |pages=4–5,54}}</ref>

In the Frasch process, three concentric tubes are introduced into the sulfur deposit. [[Superheated water]] (165&nbsp;°C, 2.5-3 MPa) is injected into the deposit via the outermost tube. Sulfur (m.p.&nbsp;115&nbsp;°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.<ref name = Ullmann/>

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.
<ref name =Ullmann>{{Ullmann | title = Sulfur | author = Wolfgang Nehb, Karel Vydra | doi = 10.1002/14356007.a25_507.pub2}}</ref>

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.<ref name = Ullmann/> A working demonstration model of the Frasch process suitable for the classroom has been described.<ref>{{cite journal | doi = 10.1021/ed008p1630 | journal = [[J. Chem. Educ.]] | title = A demonstration working model of the Frasch Process for mining sulfur | year = 1931 | last1 = Lebowitz | first1 = Samuel H. | volume = 8 | issue = 8 | pages = 1630|bibcode = 1931JChEd...8.1630L }}</ref>

==Economic Impact==

{| class="wikitable defaultright"
|+ World Production of Sulphur (1900-1929) (long tons)<ref>{{cite report |title=Information Circular 6329: Sulphur, General Information |date=August 1930 |publisher=Bureau of Mines |page=22 |url=https://archive.org/details/pub_usgov-bmines-information-circular_6329/page/n25/mode/1up}}</ref>
! Year !! United States !! Italy !! Japan !! Chile !! Spain !! Total{{efn|Not including other scattered production throughout the world}}
|-
| 1900 || 3,147 || 535,525 || 14,211 || 1,661 || 738 || 555,282
|-
| 1901 || 6,867 || 554,203 || 16,287 || 2,037 || 600 || 597,994
|-
| 1902 || 7,446 || 530,913 || 17,996 || 2,594 || 443 || 559,394
|-
| 1903 || 35,097 || 545,005 || 22,513 || 3,504 || 1,653 || 607,772
|-
| 1904 || 85,000 || 519,231 || 25,165 || 3,538 || 595 || 633,529
|-
| 1905 || 220,000 || 559,942 || 24,264 || 3,417 || 600 || 808,223
|-
| 1906 || 295,123 || 491,920 || 27,885 || 4,525 || 689 || 820,142
|-
| 1907 || 188,878 || 420,229 || 32,803 || 2,859 || 3,555 || 648,324
|-
| 1908 || 364,444 || 438,279 || 32,891 || 2,662 || 2,941 || 841,217
|-
| 1909 || 273,983 || 428,189 || 36,317 || 4,437 || 3,375 || 746,301
|-
| 1910 || 247,060 || 423,563 || 43,154 || 3,762 || 3,773 || 721,312
|-
| 1911 || 205,066 || 407,620 || 49,481 || 4,380 || 6,476 || 673,023
|-
| 1912 || 787,735 || 383,300 || 53,692 || 4,361 || 4,519 || 1,233,607
|-
| 1913 || 491,080 || 380,209 || 58,509 || 6,542 || 7,381 || 943,721
|-
| 1914 || 417,690 || 371,875 || 72,944 || 9,850 || 7,933 || 880,292
|-
| 1915 || 520,582 || 352,451 || 71,066 || 9,615 || 9,517 || 963,231
|-
| 1916 || 649,683 || 265,120 || 104,707 || 14,644 || 10,461 || 1,044,515
|-
| 1917 || 1,134,412 || 208,501 || 116,224 || 17,787 || 12,681 || 1,489,605
|-
| 1918 || 1,353,525 || 230,596 || 63,748 || 19,248 || 12,537 || 1,679,654
|-
| 1919 || 1,190,575 || 222,555 || 49,831 || 18,611 || 11,263 || 1,492,835
|-
| 1920 || 1,255,249 || 259,440 || 38,975 || 13,129 || 12,200 || 1,578,993
|-
| 1921 || 1,879,150 || 269,547 || 36,013 || 9,517 || 5,170 || 2,199,397
|-
| 1922 || 1,830,942 || 154,696 || 34,095 || 12,057 || 13,028 || 2,054,818
|-
| 1923 || 2,036,097 || 252,293 || 36,825 || 11,200 || 8,382 || 2,344,797
|-
| 1924 || 1,220,561 || 290,241 || 46,133 || 9,611 || 9,388 || 1,575,934
|-
| 1925 || 1,409,262 || 259,428 || 46,962 || 8,929 || 7,859 || 1,732,440
|-
| 1926 || 1,890,027 || 267,107 || 47,020 || 8,787 || 9,351 || 2,222,292
|-
| 1927 || 2,111,618 || 300,888 || 60,371 || 12,303 || 10,065 || 2,495,245
|-
| 1928 || 1,981,873 || 291,430 || 68,956 || 15,423 || 10,199 || 2,367,881
|-
| 1929 || 2,362,389 || 323,000{{efn|name=est|estimate}} || 58,718 || 16,000{{efn|name=est}} || 10,000{{efn|name=est}} || 2,770,107
|}

==List of Mines==

{{table alignment}}
{| class="wikitable col4right col5right col6right"
|+ Frasch Sulphur mines in the United States (1895-1966)<ref>{{cite book |title=The Economics of the Sulphur Industry |date=1970 |page=204 |isbn=978-1-317-35392-8 |url=https://books.google.com/books?id=nLDOCwAAQBAJ&pg=PT204 |last1=Hazleton |first1=Jared E. |publisher=Routledge }}</ref><ref name="mindat_pelto">{{cite web |title=(no title) |url=https://www.mindat.org/feature-4336801.html |archive-date=2025-04-23 |archive-url=https://web.archive.org/web/20250423140154/https://www.mindat.org/feature-4336801.html}}</ref>
! Dome !! State !! Company !! From !! Until !! Total long tons !! {{font color|#00ff00|Dry land}}<br/>{{font color|#ffd500|marsh/swamp/lake}}<br/>{{font color|#0000ff|offshore}}
|-
| Sulphur Mine || La || [[Union Sulphur Company|Union]] || Dec 27, 1894 || Dec 23, 1924 || 9,412,165
|-
| [[Freeport Sulphur Company#Bryan Mound|Bryan Mound]] || Tx || [[Freeport Sulphur Company|Freeport]] || Nov 12, 1912 || Sep 30, 1935 || 5,001,068 || style="background: #00ff00" | {{coord|28.918|-95.377|name=Bryan Mound sulphur mine}}
|-
| Big Hill || Tx || [[Texas Gulf Sulphur Company|Texas Gulf]] || Mar 19, 1919 || Aug 10, 1936 || 12,349,597
|-
| [[Freeport Sulphur Company#Hoskins Mound|Hoskins Mound]] || Tx || Freeport || Mar 31, 1923 || May 26, 1955 || 10,895,090 || style="background: #00ff00" | {{coord|29.136|-95.231|name=Hoskins Mound sulphur mine}}
|-
| Big Creek || Tx || Union || Mar 6, 1925 || Feb 24, 1926 || 1,450
|-
| Palangana || Tx || Duval || Oct 27, 1928 || Mar 10, 1935 || 236,662
|-
| Boling || Tx || Union || Nov 14, 1928 || Aug 30, 1929 || 9,164
|-
| Boling || Tx || Texas Gulf || Mar 19, 1929 || || >61,118,065
|-
| Long Point || Tx || Texas Gulf || Mar 19, 1930 || Oct 19, 1938 || 402,105
|-
| Lake Peigneur || La || Jefferson Lake || Oct 20, 1932 || Jun 7, 1936 || 430,811 || {{coord|29|59|19|N|91|58|59|W}}
|-
| Grand Ecaille || La || Freeport || Dec 8, 1933 || || >30,885,243 || style="background: #ffd500" | {{coord|29.38|-89.78}}
|-
| Boling || Tx || Duval || Mar 23, 1935 || Apr 25, 1940 || 571,123
|-
| Boling || Tx || Baker-Williams || Jun 2, 1935 || Dec 18, 1935 || 1,435
|-
| Clemens || Tx || Jefferson Lake || May 3, 1937 || Dec 14, 1960 || 2,975,828
|-
| Orchard<ref>{{cite news |newspaper=Chemical Markets |volume=44 |issue=5 |date=May 1939 |title=Sulfur in 1938 |page=504 |url=https://archive.org/details/sim_chemical-week_1939-05_44_5/page/504/mode/1up?q=%22orchard%20dome%22}}</ref> || Tx || Duval || 1938
|-
| Orchard || Tx || Jefferson Lake || Jun 7, 1946 || || >4,551,472
|-
| Moss Bluff || Tx || Texas Gulf || Jun 24, 1948 || || >5,081,343
|-
| Starks Dome || La || Jefferson Lake || Jun 15, 1951 || Dec 13, 1960 || 840,249
|-
| Spindletop Mine || Tx || Texas Lake || May 12, 1952 || || >6,310,721
|-
| [[Freeport Sulphur Company#Bay Ste. Elaine|Bay Ste. Elaine]] || La || Freeport || Nov 19, 1952 || Dec 29, 1959 || 1,131,204 || style="background: #ffd500" | {{coord|29|10|47|N|90|39|35|W}}
|-
| Damon || Tx || Standard Sulphur || Nov 11, 1953 || Apr 20, 1957 || 139,618
|-
| [[Freeport Sulphur Company#Garden Island Bay|Garden Island Bay]] || La || Freeport || Nov 19, 1953 || 1991<ref name="myb_1991_v1"/> || >7,006,991 || style="background: #ffd500 | {{coord|29.093|-89.193}}<ref>{{cite web |title=The Freeport Sulphur Mine near Garden Island Bay |date=6 March 2014 |url=https://www.louisianasportsman.com/fishing/the-freeport-sulphur-mine-near-garden-island-bay/ |archive-url=https://web.archive.org/web/20250422234446/https://www.louisianasportsman.com/fishing/the-freeport-sulphur-mine-near-garden-island-bay/ |archive-date=2025-04-22}}</ref>
|-
| [[Freeport Sulphur Company#Nash|Nash]] || Tx || Freeport || Feb 3, 1954 || Nov 23, 1956 || 153,115 || style="background: #00ff00" | {{coord|29.308|-95.655}}<ref>{{cite web |title=mindat: Nash Dome Mine |url=https://www.mindat.org/loc-274186.html}}</ref>
|-
| [[Freeport Sulphur Company#Chacahoula|Chacahoula]] || La || Freeport || Feb 25, 1955 || Sep 28, 1962 || 1,199,015 || style="background: #00ff00" | {{coord|29|45|0|N|90|55|48|W}}
|-
| Fannett || Tx || Texas Gulf || May 6, 1958 || || >1,773,737
|-
| High Island || Tx || United States || Mar 25, 1960 || Feb 8, 1962 || 36,708
|-
| [[Freeport Sulphur Company#Grand Isle|Grand Isle]] || La || Freeport || Apr 17, 1960 || 1991<ref name="myb_1991_v1">{{cite book |url=https://archive.org/details/pub_usgov-minerals-yearbook_1991_1/page/1544/mode/1up?q=%22grand+isle%22 |page=1544 |title=Minerals Yearbook 1991 Vol 1 Metals and Minerals|date=1991 }}</ref> || >4,466,021 || style="background: #0000ff" | {{coord|29.193|-89.892}}<ref>{{cite web |title=What are Grand Isle's offshore hotspots |date=28 January 2008 |url=https://www.louisianasportsman.com/fishing/what-are-grand-isles-offshore-hotspots/ |archive-date=2025-04-22 |archive-url=https://web.archive.org/web/20250422111818/https://www.louisianasportsman.com/fishing/what-are-grand-isles-offshore-hotspots/}}</ref>
|-
| [[Freeport Sulphur Company#Lake Pelto|Lake Pelto]] || La || Freeport || Nov 26, 1960 || || >2,474,693 || style="background: #ffd500" | {{coord|29.1|-90.677}}
|-
| Big Hill || Tx || Texas Gulf || Oct 8, 1965 || || >107,830
|-
| Sulphur Mine || La || Allied Chemical || Sep 18, 1966 || || >1,447
|-
| Nash || Tx || Phelan Sulphur || Nov 7, 1966 || || >622
|}

===Mexico===

In 1955 Mexico became the world's second largest producer of sulfur behind the United States.

{{table alignment}}
{| class="wikitable defaultright"
|+ Native Sulfur production in Mexico (long tons)<ref>{{cite book |title=Minerals Yearbook 1957 Vol 1 Metals and Minerals Except Fuels |date=1957 |page=1126 |url=https://archive.org/details/pub_usgov-minerals-yearbook_1957_1/page/1126/mode/2up?q=%22azufre+veracruz%22}}</ref>
! !! 1948-1952 (avg) !! 1953 !! 1954 !! 1955 !! 1956 !! 1957
|-
| Total || 8,452 || 5,900 || 52,407 || 475,487 || 758,415 || 1,007,915
|-
| Frasch || colspan=5 | || 990,122
|}

==References==
<references/>
{{notelist}}

==Further reading==
*{{cite journal
| author = Herman Frasch
| title = The Perkin's Medal Award - Address of Acceptance
| journal = Industrial & Engineering Chemistry 
| year = 1912
| volume = 4
| issue = 2
| pages = 134–140
| doi = 10.1021/ie50038a016| url = https://zenodo.org/record/1428716
}}
*{{cite journal
| author = Herman Frasch
| title = Unveiling of the Portrait of Herman Frasch
| journal = Industrial & Engineering Chemistry 
| year = 1918
| volume = 10
| issue = 4
| pages = 326–327
| doi = 10.1021/ie50100a038}}
*[https://web.archive.org/web/20070630202909/http://www.sulphur.org/history.htm History of Sulphur (Sulphur, Louisiana) ]
*{{cite journal
| author =Stuart Bruchey
| title = Brimstone, The Stone That Burns: The Story of the Frasch Sulphur Industry'' by Williams Haynes''
| journal = Journal of Economic History
| year = 1960
| volume = 20
| issue = 2
| pages = 326–327
| jstor=2114864}}
*{{cite journal
| author = Walter Botsch
| title = Chemiker, Techniker, Unternehmer: Zum 150. Geburtstag von Hermann Frasch
| journal = Chemie in unserer Zeit
| year = 2001
| volume = 35
| issue = 5
| pages = 324–331
| doi = 10.1002/1521-3781(200110)35:5<324::AID-CIUZ324>3.0.CO;2-9 }}

==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)

[[Category:Mineral processing]]
[[Category:Sulfur mining]]