Sulfur Frasch process

The majority of elementary sulfur is produced as a by-product of petroleum and natural gas processing and only 4% comes from native sources [mainly native mined elemental sulfur from China and extracted sulfur (Frasch process) from underground deposits in Poland]. 

Sulfur is commercially recovered from wells sunk into the salt domes along the Gulf Goast of the U.S. Using the Frasch process heated water is forced into the wells to melt the sulfur, which is then brought to the surface. 

Fluid deposits are defined as those which can be recovered in fluid form by pumping, in solution, or as particles in a slurry. Petroleum products and Frasch process sulfur are special cases. At this time no vaUd distinction is made between resources on the continental shelf and in the deep oceans. However, deep seabed deposits of minerals which can be separated by differential solution are expected to be amenable to fluid mining methods in either environment. 

Sulfur is produced from a variety of sources using many different techniques in many countries around the world. Worldwide changes have affected not only the sources of sulfur, but also the amounts consumed. Sulfur sources in the United States underwent significant changes during the 1980s. Voluntary sulfur from the Frasch process (mines) suppHed only 25% of the sulfur in the United States in 1995, compared to about 53% in 1980, whereas recovered or involuntary sulfur suppHed 63% of the sulfur in the United States in 1995, compared to 34% in 1980. About 12% is suppHed from other forms, primarily by metallurgy (21,33). 

Sulfuric acid is the most important sulfur-containing intermediate product. More than 85% of the sulfur consumed in the world is either converted to sulfuric acid or produced direcdy as such (see Sulfuric acid and sulfur trioxide). Worldwide, well over half of the sulfuric acid is used in the manufacture of phosphatic fertilizers and ammonium sulfate for fertilizers. The sulfur source may be voluntary elemental, such as from the Frasch process recovered elemental from natural gas or petroleum or sulfur dioxide from smelter operations. 

The sulfiu can be piped long distances in liquid form or transported molten in ships, barges or rail cars. Alternatively it can be prilled or bandied as nuggets or chunks. Despite the vast bulk of liquid sulfur mined by the Frasch process it is obtained in very pure form. There is virtually no selenium, tellurium or arsenic impurity, and the product is usually 99.5-99.9% pure. ... 

The Frasch process, developed in 1894, produces sulfur from underground deposits. 

Frasch process for mining sulfur. Superheatad watar at 165°C is sent down through the outer pipe to form a pool of molten sulfur (mp = 119°C) at the base. Compressed air, pumped down the inner pipe, brings the sulfur to the surface. Sulfur deposits are often 100 m or more beneath the earth s surface, covered with quicksand and rock. 

Frasch process The process used to extract native sulfur from underground deposits, 558... 

Sulfur is widely distributed as sulfide ores, which include galena, PbS cinnabar, HgS iron pyrite, FeS, and sphalerite, ZnS (Fig. 15.11). Because these ores are so common, sulfur is a by-product of the extraction of a number of metals, especially copper. Sulfur is also found as deposits of the native element (called brimstone), which are formed by bacterial action on H,S. The low melting point of sulfur (115°C) is utilized in the Frasch process, in which superheated water is used to melt solid sulfur underground and compressed air pushes the resulting slurry to the surface. Sulfur is also commonly found in petroleum, and extracting it chemically has been made inexpensive and safe by the use of heterogeneous catalysts, particularly zeolites (see Section 13.14). One method used to remove sulfur in the form of H2S from petroleum and natural gas is the Claus process, in which some of the H2S is first oxidized to sulfur dioxide ... 

Frasch process A process for mining sulfur that uses superheated water to melt the sulfur and compressed air to force it to the surface, free energy See Gibbs free energy. free expansion Expansion against zero opposing pressure. 

The origin of the small Sy content of all commercial sulfur samples is the following. Elemental sulfur is produced either by the Frasch process (mining of sulfur deposits) or by the Claus process (partial oxidation of HyS) [62]. In each case liquid sulfur is produced (at ca. 140 °C) which at this temperature consists of 95% Ss and ca. 5% other sulfur homocycles of which Sy is the main component. On slow cooling and crystalhzation most of the non-Ss species convert to the more stable Ss and to polymeric sulfur but traces of Sy are built into the crystal lattice of Ss as sohd state defects. In some commercial samples traces of Ss or Sg were detected in addition. The Sy defects survive for years if not forever at 20 °C. The composition of the commercial samples depends mainly on the coohng rate and on other experimental conditions. Only recrystalhzation from organic solvents removes Sy and, of course, the insoluble polymeric sulfur and produces pure a-Ss [59]. 

Sulfur for commercial purposes is derived mainly from native elemental sulfur mined by the Frasch process. Large quantities of sulfur are also recovered from the roasting of metal sulfides and the refining of crude oil, i.e., from the sulfur by-products of purified sour natural gas and petroleum (the designation sour is generally associated with high-sulfur petroleum products). Reserves of elemental sulfur in evaporite and volcanic deposits and of sulfur associated with natural gas,... 

Frank-Wen flickering cluster model, of liquid water, 26 15, 16 Frascati Manual, 21 610 Frasch sulfur extraction process, 23 564, 570-573... 

Sulfur is mined by the recovery method known as the Frasch process, which was invented by Herman Frasch in Germany in the early 1900s. This process forces superheated water, under pressure, into deep underground sulfur deposits. Compressed air then forces the molten sulfur to the surface, where it is cooled. There are other methods for mining sulfur, but the Frasch process is the most important and most economical. 

Elemental sulfur is recovered from its ore deposits found throughout the world. It is obtained commercially by the Frasch process, recovery from wells sunk into salt domes. Heated water under pressure is forced into the underground deposits to melt sulfur. Liquid sulfur is then brought to the surface. Sulfur is recovered by distillation. Often the ore is concentrated by froth flotation. 

Elemental sulfur1-4 occurs naturally in association with volcanic vents and, in Texas and Louisiana, as underground deposits. The latter are mined by injecting air and superheated water, which melts the sulfur and carries it to the surface in the return flow (the Frasch process). Most of the sulfur used in industry, however, comes as a by-product of the desulfurization of fossil fuels. For example, Albertan sour natural gas, which often contains over 30% (90%, in some cases) hydrogen sulfide (H2S), as well as hydrocarbons (mainly methane) and small amounts of C02, carbonyl sulfide (COS), and water, is sweetened by scrubbing out the H2S and then converting it to elemental S in the Claus process.5 The Claus process is applicable in any industrial operation that produces H2S (see Section 8.5) it converts this highly toxic gas to nontoxic, relatively unreactive, and easily transportable solid sulfur. 

Fig. 1. The Frasch process (a) initial heating (b) movement of Hquid sulfur and (c) result of pumping compressed air. The thinner arrows indicate the...

Pyrite is the most abundant of the metal sulfides. For many years, until the Frasch process was developed, pyrite was the main source of sulfur and, for much of the first half of the twentieth century, comprised over 50% of world sulfur production. Pyrite reserves are distributed throughout the world and known deposits have been mined in about 30 countries. Possibly the largest pyrite reserves in the world are located in southern Spain, Portugal, and the CIS. Large deposits are also in Canada, Cyprus, Finland, Italy, Japan, Norway, South Africa, Sweden, Turkey, the United States, and Yugoslavia. However, the three main regional producers of pyrites continue to be Western Europe Eastern Europe, including the CIS and China. 

Sulfur is a very important industrial chemical. Current consumption ranks sulfur with the top five inorganic and organic chemicals produced in the U.S. The U.S. is the largest producer and consumer of sulfur in the world. The U.S. position in sulfur production resulted from the development of the Frasch process toward the end of the 19th century for mining the large sulfur deposits associated with salt domes in Texas and Louisiana. 

Sulfur is a, relatively abundant element, occurring as an impurity in many metal ores and fossil fuels. It also occurs in relatively pure form from which it can be mined via the Frasch process. Until recently Frasch mining was the major source of supply in the world with the largest producers being the U.S., Mexico and Poland. In the late 1960 s, recovery of sulfur as a by-product from "cleaning" operations began to accelerate rapidly. Sulfur recovery from... 

Aside from the U.S., Mexico is one of the few countries in the world that produces sulfur by the Frasch process. Its output of Frasch sulfur has been on a general decline in recent years. 

FRASCH PROCESS. A process by which much of the world s sulfur is obtained. Developed about 1900 by Herman Frasch, the process involves melting sulfur underground by introducing superheated water through a pipe under pressure and forcing the molten sulfur to the surface by compressed air... 

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