Misplaced Pages

#528471

107-446: In the usual implementation, carbon monoxide and hydrogen, the feedstocks for FT, are produced from coal , natural gas , or biomass in a process known as gasification . The process then converts these gases into synthetic lubrication oil and synthetic fuel . This process has received intermittent attention as a source of low-sulfur diesel fuel and to address the supply or cost of petroleum-derived hydrocarbons. Fischer–Tropsch process

214-512: A cyclothem . Cyclothems are thought to have their origin in glacial cycles that produced fluctuations in sea level , which alternately exposed and then flooded large areas of continental shelf. The woody tissue of plants is composed mainly of cellulose, hemicellulose, and lignin. Modern peat is mostly lignin, with a content of cellulose and hemicellulose ranging from 5% to 40%. Various other organic compounds, such as waxes and nitrogen- and sulfur-containing compounds, are also present. Lignin has

321-594: A syngas is converted to synthetic fuels. The steps for producing high-octane synthetic gasoline are as follows: With methane as the predominant target for GTL, much attention has focused on the three enzymes that process methane. These enzymes support the existence of methanotrophs , microorganisms that metabolize methane as their only source of carbon and energy. Aerobic methanotrophs harbor enzymes that oxygenate methane to methanol. The relevant enzymes are methane monooxygenases , which are found both in soluble and particulate (i.e. membrane-bound) varieties. They catalyze

428-600: A combination of landfill gas and pipeline natural gas. Starting as a biomass technology licensor In Summer of 2012 SGC Energia (SGCE) successfully commissioned a pilot multi tubular Fischer–Tropsch process unit and associated product upgrading units at the Pasadena, Tx Technology Center. The technology center focused on the development and operations of their XTLH solution which optimized processing of low value carbon waste streams into advanced fuels and wax products. This unit also serves as an operations training environment for

535-483: A continuous basis a new, larger scale full cycle Pilot Plant. It represents the second generation of INFRA's testing facility and is differentiated by a high degree of automation and extensive data gathering system. In 2015, INFRA built its own catalyst factory in Troitsk (Moscow, Russia). The catalyst factory has a capacity of over 15 tons per year, and produces the unique proprietary Fischer–Tropsch catalysts developed by

642-858: A factory in Bintulu , Malaysia . Another Shell GTL facility is the Pearl GTL plant in Qatar , the world's largest GTL facility. Sasol has recently built the Oryx GTL facility in Ras Laffan Industrial City , Qatar and together with Uzbekneftegaz and Petronas builds the Uzbekistan GTL plant. Chevron Corporation , in a joint venture with the Nigerian National Petroleum Corporation

749-434: A few of the building blocks of DNA and RNA within asteroids . Similarly, the hypothetical abiogenic petroleum formation requires some naturally occurring FT-like processes. Biological Fischer-Tropsch-type chemistry can be carried out by the enzyme nitrogenase at ambient conditions. Coal Coal is a combustible black or brownish-black sedimentary rock , formed as rock strata called coal seams . Coal

856-532: A mixture of H 2 and CO into aliphatic products is a multi-step reaction with several intermediate compounds. The growth of the hydrocarbon chain may be visualized as involving a repeated sequence in which hydrogen atoms are added to carbon and oxygen, the C–O bond is split and a new C–C bond is formed. For one –CH 2 – group produced by CO + 2 H 2 → (CH 2 ) + H 2 O, several reactions are necessary: The conversion of CO to alkanes involves hydrogenation of CO,

963-417: A process called carbonization . Carbonization proceeds primarily by dehydration , decarboxylation , and demethanation. Dehydration removes water molecules from the maturing coal via reactions such as Decarboxylation removes carbon dioxide from the maturing coal: while demethanation proceeds by reaction such as In these formulas, R represents the remainder of a cellulose or lignin molecule to which

1070-521: A rate of 140,000 barrels per day (22,000 m/d), with additional production of 120,000 barrels (19,000 m) of oil equivalent in natural gas liquids and ethane . Another plant in Ras Laffan, called Oryx GTL, has been commissioned in 2007 with a capacity of 34,000 barrels per day (5,400 m/d). The plant utilizes the Sasol slurry phase distillate process, which uses a cobalt catalyst. Oryx GTL

1177-409: A reactor must be desulfurized . Otherwise, sulfur-containing impurities deactivate (" poison ") the catalysts required for FT reactions. Several reactions are employed to adjust the H 2 :CO ratio. Most important is the water-gas shift reaction , which provides a source of hydrogen at the expense of carbon monoxide: For FT plants that use methane as the feedstock , another important reaction

SECTION 10

#1732772007529

1284-525: A series of three reactions: The methanol thus formed may be converted to gasoline by the Mobil process and methanol-to-olefins. In the early 1970s, Mobil developed an alternative procedure in which natural gas is converted to syngas, and then methanol . The methanol reacts in the presence of a zeolite catalyst to form various compounds. In the first step methanol is partially dehydrated to give dimethyl ether : The mixture of dimethyl ether and methanol

1391-540: A switch in fuels happened in London in the late sixteenth and early seventeenth centuries. Historian Ruth Goodman has traced the socioeconomic effects of that switch and its later spread throughout Britain and suggested that its importance in shaping the industrial adoption of coal has been previously underappreciated. The development of the Industrial Revolution led to the large-scale use of coal, as

1498-561: A tenth. Indonesia and Australia export the most, followed by Russia . The word originally took the form col in Old English , from reconstructed Proto-Germanic * kula ( n ), from Proto-Indo-European root * g ( e ) u-lo- "live coal". Germanic cognates include the Old Frisian kole , Middle Dutch cole , Dutch kool , Old High German chol , German Kohle and Old Norse kol . Irish gual

1605-403: A weight basis. This composition reflects partly the composition of the precursor plants. The second main fraction of coal is ash, an undesirable, noncombustable mixture of inorganic minerals. The composition of ash is often discussed in terms of oxides obtained after combustion in air: Of particular interest is the sulfur content of coal, which can vary from less than 1% to as much as 4%. Most of

1712-406: A weight composition of about 54% carbon, 6% hydrogen, and 30% oxygen, while cellulose has a weight composition of about 44% carbon, 6% hydrogen, and 49% oxygen. Bituminous coal has a composition of about 84.4% carbon, 5.4% hydrogen, 6.7% oxygen, 1.7% nitrogen, and 1.8% sulfur, on a weight basis. The low oxygen content of coal shows that coalification removed most of the oxygen and much of the hydrogen

1819-462: Is dry reforming , which converts the methane into CO and H 2 : Generally, the Fischer–Tropsch process is operated in the temperature range of 150–300 °C (302–572 °F). Higher temperatures lead to faster reactions and higher conversion rates but also tend to favor methane production. For this reason, the temperature is usually maintained at the low to middle part of the range. Increasing

1926-422: Is 12,000 barrels per day (1,900 m/d). Construction is underway for Velocys' commercial reference plant incorporating its microchannel Fischer–Tropsch technology; ENVIA Energy's Oklahoma City GTL project being built adjacent to Waste Management's East Oak landfill site. The project is being financed by a joint venture between Waste Management, NRG Energy, Ventech and Velocys. The feedstock for this plant will be

2033-514: Is a joint venture between QatarEnergy and Sasol . The world's largest scale implementation of Fischer–Tropsch technology is a series of plants operated by Sasol in South Africa , a country with large coal reserves, but little oil. With a capacity of 165000 Bpd at its Secunda plant. The first commercial plant opened in 1952. Sasol uses coal and natural gas as feedstocks and produces a variety of synthetic petroleum products, including most of

2140-636: Is also a cognate via the Indo-European root. The conversion of dead vegetation into coal is called coalification . At various times in the geologic past, the Earth had dense forests in low-lying areas. In these wetlands, the process of coalification began when dead plant matter was protected from oxidation , usually by mud or acidic water, and was converted into peat . The resulting peat bogs , which trapped immense amounts of carbon, were eventually deeply buried by sediments. Then, over millions of years,

2247-457: Is best known for being used in the first integrated GTL-plant operated and built by Shell in Bintulu , Malaysia. In addition to the active metal (usually Fe or Co), two other components comprise the catalyst: promoters and the catalyst support . Promoters are additives that enhance the behavior of the catalyst. For F-T catalysts, typical promoters including potassium and copper, which are usually added as salts. The choice of promoters depends on

SECTION 20

#1732772007529

2354-429: Is burned in a turbine). Hot exhaust gases from the turbine are used to raise steam in a heat recovery steam generator which powers a supplemental steam turbine . The overall plant efficiency when used to provide combined heat and power can reach as much as 94%. IGCC power plants emit less local pollution than conventional pulverized coal-fueled plants. Other ways to use coal are as coal-water slurry fuel (CWS), which

2461-425: Is called gasification . Synthesis gas ("syngas") is obtained from biomass/coal gasification is a mixture of hydrogen and carbon monoxide. The H 2 :CO ratio is adjusted using the water-gas shift reaction . Coal-based FT plants produce varying amounts of CO 2 , depending upon the energy source of the gasification process. However, most coal-based plants rely on the feed coal to supply all the energy requirements of

2568-1191: Is commissioning the Escravos GTL in Nigeria , which uses Sasol technology. PetroSA , South Africa's national oil company, owns and operates a 22,000 barrels/day (capacity) GTL plant in Mossel Bay , using Sasol GTL technology. New generation of GTL technology is being pursued for the conversion of unconventional, remote and problem gas into valuable liquid fuels. GTL plants based on innovative Fischer–Tropsch catalysts have been built by INFRA Technology . Other mainly U.S. companies include Velocys, ENVIA Energy, Waste Management, NRG Energy, ThyssenKrupp Industrial Solutions, Liberty GTL, Petrobras , Greenway Innovative Energy, Primus Green Energy, Compact GTL, and Petronas. Several of these processes have proven themselves with demonstration flights using their jet fuels. Another proposed solution to stranded gas involves use of novel FPSO for offshore conversion of gas to liquids such as methanol , diesel , petrol , synthetic crude , and naphtha . GTL using natural gas

2675-627: Is discussed as a step of producing carbon-neutral liquid hydrocarbon fuels from CO 2 and hydrogen. The process was first developed by Franz Fischer and Hans Tropsch at the Kaiser Wilhelm Institute for Coal Research in Mülheim an der Ruhr , Germany, in 1925. The Fischer–Tropsch process involves a series of chemical reactions that produce a variety of hydrocarbons, ideally having the formula (C n H 2 n +2 ). The more useful reactions produce alkanes as follows: where n

2782-603: Is entirely vertical; however, metamorphism may cause lateral changes of rank, irrespective of depth. For example, some of the coal seams of the Madrid, New Mexico coal field were partially converted to anthracite by contact metamorphism from an igneous sill while the remainder of the seams remained as bituminous coal. The earliest recognized use is from the Shenyang area of China where by 4000 BC Neolithic inhabitants had begun carving ornaments from black lignite. Coal from

2889-534: Is followed by diverse methods to convert the hydrogen-carbon monoxide mixtures to liquids. Direct partial combustion has been demonstrated in nature but not replicated commercially. Technologies reliant on partial combustion have been commercialized mainly in regions where natural gas is inexpensive. The motivation for GTL is to produce liquid fuels, which are more readily transported than methane. Methane must be cooled below its critical temperature of -82.3 °C in order to be liquified under pressure. Because of

2996-455: Is made when metallurgical coal (also known as coking coal ) is baked in an oven without oxygen at temperatures as high as 1,000 °C, driving off the volatile constituents and fusing together the fixed carbon and residual ash. Metallurgical coke is used as a fuel and as a reducing agent in smelting iron ore in a blast furnace . The carbon monoxide produced by its combustion reduces hematite (an iron oxide ) to iron. Pig iron , which

3103-409: Is more abundant, and anthracite. The % carbon in coal follows the order anthracite > bituminous > lignite > brown coal. The fuel value of coal varies in the same order. Some anthracite deposits contain pure carbon in the form of graphite . For bituminous coal, the elemental composition on a dry, ash-free basis of 84.4% carbon, 5.4% hydrogen, 6.7% oxygen, 1.7% nitrogen, and 1.8% sulfur, on

3210-418: Is more economical when there is wide gap between the prevailing natural gas price and crude oil price on a Barrel of oil equivalent (BOE) basis. A coefficient of 0.1724 results in full oil parity . GTL is a mechanism to bring down the diesel/gasoline/crude oil international prices at par with the natural gas price in an expanding global natural gas production at cheaper than crude oil price. When natural gas

3317-432: Is mostly carbon with variable amounts of other elements , chiefly hydrogen , sulfur , oxygen , and nitrogen . Coal is a type of fossil fuel , formed when dead plant matter decays into peat which is converted into coal by the heat and pressure of deep burial over millions of years. Vast deposits of coal originate in former wetlands called coal forests that covered much of the Earth's tropical land areas during

Fischer–Tropsch process - Misplaced Pages Continue

3424-604: Is then further dehydrated over a zeolite catalyst such as ZSM-5 , and in practice is polymerized and hydrogenated to give a gasoline with hydrocarbons of five or more carbon atoms making up 80% of the fuel by weight. The Mobil MTG process is practiced from coal-derived methanol in China by JAMG . A more modern implementation of MTG is the Topsøe improved gasoline synthesis (TiGAS). Methanol can be converted to olefins using zeolite and SAPO-based heterogeneous catalysts . Depending on

3531-515: Is too rich in dissolved carbon, is also produced. Gas to liquids Gas to liquids ( GTL ) is a refinery process to convert natural gas or other gaseous hydrocarbons into longer-chain hydrocarbons, such as gasoline or diesel fuel . Methane -rich gases are converted into liquid synthetic fuels . Two general strategies exist: (i) direct partial combustion of methane to methanol and (ii) Fischer–Tropsch -like processes that convert carbon monoxide and hydrogen into hydrocarbons. Strategy ii

3638-426: Is typically 10–20. The formation of methane ( n = 1) is unwanted. Most of the alkanes produced tend to be straight-chain, suitable as diesel fuel . In addition to alkane formation, competing reactions give small amounts of alkenes , as well as alcohols and other oxygenated hydrocarbons. The reaction is a highly exothermic reaction due to a standard reaction enthalpy (ΔH) of −165 kJ/mol CO combined. Converting

3745-452: Is used as fuel. 27.6% of world energy was supplied by coal in 2017 and Asia used almost three-quarters of it. Other large-scale applications also exist. The energy density of coal is roughly 24 megajoules per kilogram (approximately 6.7 kilowatt-hours per kg). For a coal power plant with a 40% efficiency, it takes an estimated 325 kg (717 lb) of coal to power a 100 W lightbulb for one year. In 2022, 68% of global coal use

3852-715: The Bronze Age (3000–2000 BC), where it formed part of funeral pyres . In Roman Britain , with the exception of two modern fields, "the Romans were exploiting coals in all the major coalfields in England and Wales by the end of the second century AD". Evidence of trade in coal, dated to about AD 200, has been found at the Roman settlement at Heronbridge , near Chester ; and in the Fenlands of East Anglia , where coal from

3959-521: The Fushun mine in northeastern China was used to smelt copper as early as 1000 BC. Marco Polo , the Italian who traveled to China in the 13th century, described coal as "black stones ... which burn like logs", and said coal was so plentiful, people could take three hot baths a week. In Europe, the earliest reference to the use of coal as fuel is from the geological treatise On Stones (Lap. 16) by

4066-550: The Kaiser-Wilhelm-Institut for Chemistry in 1926. They filed a number of patents, e.g. , U.S. patent 1,746,464 , applied 1926, published 1930. It was commercialized by Brabag in Germany in 1936. Being petroleum-poor but coal-rich, Germany used the process during World War II to produce ersatz (replacement) fuels. FT production accounted for an estimated 9% of German war production of fuels and 25% of

4173-607: The Midlands was transported via the Car Dyke for use in drying grain. Coal cinders have been found in the hearths of villas and Roman forts , particularly in Northumberland , dated to around AD 400. In the west of England, contemporary writers described the wonder of a permanent brazier of coal on the altar of Minerva at Aquae Sulis (modern day Bath ), although in fact easily accessible surface coal from what became

4280-728: The Somerset coalfield was in common use in quite lowly dwellings locally. Evidence of coal's use for iron -working in the city during the Roman period has been found. In Eschweiler , Rhineland , deposits of bituminous coal were used by the Romans for the smelting of iron ore . No evidence exists of coal being of great importance in Britain before about AD 1000, the High Middle Ages . Coal came to be referred to as "seacoal" in

4387-640: The United States Department of Energy and the United States Department of Transportation . Syntroleum has worked to develop a synthetic jet fuel blend that will help the Air Force to reduce its dependence on imported petroleum. The Air Force, which is the United States military's largest user of fuel, began exploring alternative fuel sources in 1999. On December 15, 2006, a B-52 took off from Edwards Air Force Base , California for

Fischer–Tropsch process - Misplaced Pages Continue

4494-491: The coal gap in the Permian–Triassic extinction event , where coal is rare. Favorable geography alone does not explain the extensive Carboniferous coal beds. Other factors contributing to rapid coal deposition were high oxygen levels, above 30%, that promoted intense wildfires and formation of charcoal that was all but indigestible by decomposing organisms; high carbon dioxide levels that promoted plant growth; and

4601-538: The hydrogenolysis (cleavage with H 2 ) of C–O bonds, and the formation of C–C bonds. Such reactions are assumed to proceed via initial formation of surface-bound metal carbonyls . The CO ligand is speculated to undergo dissociation, possibly into oxide and carbide ligands. Other potential intermediates are various C 1 fragments including formyl (CHO) , hydroxycarbene (HCOH), hydroxymethyl (CH 2 OH), methyl (CH 3 ), methylene (CH 2 ), methylidyne (CH), and hydroxymethylidyne (COH). Furthermore, and critical to

4708-447: The steam engine took over from the water wheel . In 1700, five-sixths of the world's coal was mined in Britain. Britain would have run out of suitable sites for watermills by the 1830s if coal had not been available as a source of energy. In 1947 there were some 750,000 miners in Britain, but the last deep coal mine in the UK closed in 2015. A grade between bituminous coal and anthracite

4815-400: The water gas shift reaction . Removing impurities, particularly nitrogen, carbon dioxide and water, from the raw synthesis gas mixture yields pure synthesis gas (syngas). The pure syngas is routed into the Fischer–Tropsch process, where the syngas reacts over an iron or cobalt catalyst to produce synthetic hydrocarbons, including alcohols. Methanol is made from methane (natural gas) in

4922-472: The 1100 BPD Juniper GTL facility constructed in Westlake, LA. In October 2006, Finnish paper and pulp manufacturer UPM announced its plans to produce biodiesel by the Fischer–Tropsch process alongside the manufacturing processes at its European paper and pulp plants, using waste biomass resulting from paper and pulp manufacturing processes as source material. A demonstration-scale Fischer–Tropsch plant

5029-407: The 13th century; the wharf where the material arrived in London was known as Seacoal Lane, so identified in a charter of King Henry III granted in 1253. Initially, the name was given because much coal was found on the shore, having fallen from the exposed coal seams on cliffs above or washed out of underwater coal outcrops, but by the time of Henry VIII , it was understood to derive from the way it

5136-596: The Carboniferous, and suggested that climatic and tectonic factors were a more plausible explanation, reconstruction of ancestral enzymes by phylogenetic analysis corroborated a hypothesis that lignin degrading enzymes appeared in fungi approximately 200 MYa. One likely tectonic factor was the Central Pangean Mountains , an enormous range running along the equator that reached its greatest elevation near this time. Climate modeling suggests that

5243-598: The Central Pangean Mountains contributed to the deposition of vast quantities of coal in the late Carboniferous. The mountains created an area of year-round heavy precipitation, with no dry season typical of a monsoon climate. This is necessary for the preservation of peat in coal swamps. Coal is known from Precambrian strata, which predate land plants. This coal is presumed to have originated from residues of algae. Sometimes coal seams (also known as coal beds) are interbedded with other sediments in

5350-515: The FT products. In order to avoid this, some researchers have proposed using zeolites or other catalyst substrates with fixed sized pores that can restrict the formation of hydrocarbons longer than some characteristic size (usually n  < 10). This way they can drive the reaction so as to minimize methane formation without producing many long-chained hydrocarbons. Such efforts have had only limited success. Four metals are active as catalysts for

5457-399: The Fischer–Tropsch process using natural gas and coal at its demonstration plant near Tulsa, Oklahoma . Syntroleum is working to commercialize its licensed Fischer–Tropsch technology via coal-to-liquid plants in the United States, China, and Germany, as well as gas-to-liquid plants internationally. Using natural gas as a feedstock, the ultra-clean, low sulfur fuel has been tested extensively by

SECTION 50

#1732772007529

5564-453: The Fischer–Tropsch process: iron, cobalt, nickel, and ruthenium. Since FT process typically transforms inexpensive precursors into complex mixtures that require further refining, FT catalysts are based on inexpensive metals, especially iron and cobalt. Nickel generates too much methane, so it is not used. Typically, such heterogeneous catalysts are obtained through precipitation from iron nitrate solutions. Such solutions can be used to deposit

5671-577: The Greek scientist Theophrastus (c. 371–287 BC): Among the materials that are dug because they are useful, those known as anthrakes [coals] are made of earth, and, once set on fire, they burn like charcoal [anthrakes]. They are found in Liguria ;... and in Elis as one approaches Olympia by the mountain road; and they are used by those who work in metals. Outcrop coal was used in Britain during

5778-568: The Shell FT process structure. The company went bankrupt in 2011 due to impracticalities in the process. Biomass gasification (BG) and Fischer–Tropsch (FT) synthesis can in principle be combined to produce renewable transportation fuels ( biofuels ). In partnership with Sunfire, Audi produces E-diesel in small scale with two steps, the second one being FT. Syntroleum , a publicly traded United States company, has produced over 400,000 U.S. gallons (1,500,000 L) of diesel and jet fuel from

5885-484: The United States and India, some coal-producing states have invested in Fischer–Tropsch plants. In Pennsylvania, Waste Management and Processors, Inc. was funded by the state to implement FT technology licensed from Shell and Sasol to convert so-called waste coal (leftovers from the mining process) into low-sulfur diesel fuel. Choren Industries has built a plant in Germany that converts biomass to syngas and fuels using

5992-490: The United States' gas consumption or 30% of the European Union's annual gas consumption, a resource that could be useful using GTL. Gas-to-liquids processes may also be used for the economic extraction of gas deposits in locations where it is not economical to build a pipeline. This process will be increasingly significant as crude oil resources are depleted . Royal Dutch Shell produces a diesel from natural gas in

6099-466: The associated cryogenic apparatus, LNG tankers are used for transport. Methanol is a conveniently handled combustible liquid, but its energy density is half of that of gasoline. A GtL process may be established via the Fischer–Tropsch process which comprises several chemical reactions that convert a mixture of carbon monoxide (CO) and hydrogen (H 2 ) into long chained hydrocarbons. These hydrocarbons are typically liquid or semi-liquid and ideally have

6206-559: The automobile fuel. Many refinements and adjustments have been made to the process since Fischer and Tropsch's time. The United States Bureau of Mines , in a program initiated by the Synthetic Liquid Fuels Act , employed seven Operation Paperclip synthetic fuel scientists in a Fischer–Tropsch plant in Louisiana, Missouri in 1946. In Britain, Alfred August Aicher obtained several patents for improvements to

6313-585: The catalyst and the specific process conditions. Examination of the above equation reveals that methane will always be the largest single product so long as α is less than 0.5; however, by increasing α close to one, the total amount of methane formed can be minimized compared to the sum of all of the various long-chained products. Increasing α increases the formation of long-chained hydrocarbons. The very long-chained hydrocarbons are waxes, which are solid at room temperature. Therefore, for production of liquid transportation fuels it may be necessary to crack some of

6420-485: The catalyst pore size, this process can afford either C2 or C3 products, which are important monomers. A third gas-to-liquids process builds on the MTG technology by converting natural gas-derived syngas into drop-in gasoline and jet fuel via a thermochemical single-loop process. The STG+ process follows four principal steps in one continuous process loop. This process consists of four fixed bed reactors in series in which

6527-550: The catalyst's support, ceria functions as a reverse water-gas shift catalyst, further increasing the yield of the reaction. The short-chain hydrocarbons were upgraded to liquid fuels over solid acid catalysts, such as zeolites . Using conventional FT technology the process ranges in carbon efficiency from 25 to 50 percent and a thermal efficiency of about 50% for CTL facilities idealised at 60% with GTL facilities at about 60% efficiency idealised to 80% efficiency. A Fischer–Tropsch-type process has also been suggested to have produced

SECTION 60

#1732772007529

6634-525: The company's R&D division. In 2016, INFRA designed and built a modular, transportable GTL (gas-to-liquid) M100 plant for processing natural and associated gas into synthetic crude oil in Wharton (Texas, USA). The M100 plant is operating as a technology demonstration unit, R&D platform for catalyst refinement, and economic model to scale the Infra GTL process into larger and more efficient plants. In

6741-519: The country's diesel fuel . PetroSA , another South African company, operates a refinery with a 36,000 barrels a day plant that completed semi-commercial demonstration in 2011, paving the way to begin commercial preparation. The technology can be used to convert natural gas, biomass or coal into synthetic fuels. One of the largest implementations of Fischer–Tropsch technology is in Bintulu , Malaysia. This Shell facility converts natural gas into low- sulfur Diesel fuels and food-grade wax. The scale

6848-571: The environment , causing premature death and illness, and it is the largest anthropogenic source of carbon dioxide contributing to climate change . Fourteen billion tonnes of carbon dioxide were emitted by burning coal in 2020, which is 40% of total fossil fuel emissions and over 25% of total global greenhouse gas emissions . As part of worldwide energy transition , many countries have reduced or eliminated their use of coal power . The United Nations Secretary General asked governments to stop building new coal plants by 2020. Global coal use

6955-430: The evolution of the first trees . But bacteria and fungi did not immediately evolve the ability to decompose lignin, so the wood did not fully decay but became buried under sediment, eventually turning into coal. About 300 million years ago, mushrooms and other fungi developed this ability, ending the main coal-formation period of earth's history. Although some authors pointed at some evidence of lignin degradation during

7062-475: The facility of C–O bond scission. Using C-labelled ethylene and propene over cobalt catalysts results in incorporation of these olefins into the growing chain. Chain growth reaction thus appears to involve both 'olefin insertion' as well as 'CO-insertion'. Fischer–Tropsch plants associated with biomass or coal or related solid feedstocks (sources of carbon) must first convert the solid fuel into gases. These gases include CO, H 2 , and alkanes. This conversion

7169-519: The factors involved in coalification, temperature is much more important than either pressure or time of burial. Subbituminous coal can form at temperatures as low as 35 to 80 °C (95 to 176 °F) while anthracite requires a temperature of at least 180 to 245 °C (356 to 473 °F). Although coal is known from most geologic periods , 90% of all coal beds were deposited in the Carboniferous and Permian periods. Paradoxically, this

7276-516: The first time powered solely by a 50–50 blend of JP-8 and Syntroleum's FT fuel. The seven-hour flight test was considered a success. The goal of the flight test program is to qualify the fuel blend for fleet use on the service's B-52s, and then flight test and qualification on other aircraft. The test program concluded in 2007. This program is part of the Department of Defense Assured Fuel Initiative, an effort to develop secure domestic sources for

7383-498: The form of iron pyrite (FeS 2 ). Being a dense mineral, it can be removed from coal by mechanical means, e.g. by froth flotation . Some sulfate occurs in coal, especially weathered samples. It is not volatilized and can be removed by washing. Minor components include: As minerals, Hg, As, and Se are not problematic to the environment, especially since they are only trace components. They become however mobile (volatile or water-soluble) when these minerals are combusted. Most coal

7490-449: The formula (C n H 2 n +2 ). In order to obtain the mixture of CO and H 2 required for the Fischer–Tropsch process, methane (main component of natural gas) may be subjected to partial oxidation which yields a raw synthesis gas mixture of mostly carbon dioxide , carbon monoxide , hydrogen gas (and sometimes water and nitrogen). The ratio of carbon monoxide to hydrogen in the raw synthesis gas mixture can be adjusted e.g. using

7597-475: The heat and pressure of deep burial caused the loss of water, methane and carbon dioxide and increased the proportion of carbon. The grade of coal produced depended on the maximum pressure and temperature reached, with lignite (also called "brown coal") produced under relatively mild conditions, and sub-bituminous coal , bituminous coal , or anthracite coal (also called "hard coal" or "black coal") produced in turn with increasing temperature and pressure. Of

7704-431: The increasing tendency of the anthracite to break with a conchoidal fracture , similar to the way thick glass breaks. As geological processes apply pressure to dead biotic material over time, under suitable conditions, its metamorphic grade or rank increases successively into: There are several international standards for coal. The classification of coal is generally based on the content of volatiles . However

7811-518: The late Carboniferous ( Pennsylvanian ) and Permian times. Coal is used primarily as a fuel. While coal has been known and used for thousands of years, its usage was limited until the Industrial Revolution . With the invention of the steam engine , coal consumption increased. In 2020, coal supplied about a quarter of the world's primary energy and over a third of its electricity . Some iron and steel -making and other industrial processes burn coal. The extraction and burning of coal damages

7918-409: The lowest reaction temperatures and produces higher molecular weight hydrocarbons. Ruthenium catalysts consist of the metal, without any promoters, thus providing relatively simple system suitable for mechanistic analysis. Its high price preclude industrial applications. Cobalt catalysts are more active for FT synthesis when the feedstock is natural gas. Natural gas has a high hydrogen to carbon ratio, so

8025-444: The metal salt onto the catalyst support (see below). Such treated materials transform into active catalysts by heating under CO, H 2 or with the feedstock to be treated, i.e., the catalysts are generated in situ. Owing to the multistep nature of the FT process, analysis of the catalytically active species is challenging. Furthermore, as is known for iron catalysts, a number of phases may coexist and may participate in diverse steps in

8132-533: The microbes Moorella thermoacetica and Yarrowia lipolytica . This process is known as biological gas-to-liquids. Using gas-to-liquids processes, refineries can convert some of their gaseous waste products ( flare gas ) into valuable fuel oils , which can be sold as is or blended only with diesel fuel . The World Bank estimates that over 150 billion cubic metres (5.3 × 10 ^  cu ft) of natural gas are flared or vented annually, an amount worth approximately $ 30.6 billion, equivalent to 25% of

8239-424: The military energy needs. The Pentagon hopes to reduce its use of crude oil from foreign producers and obtain about half of its aviation fuel from alternative sources by 2016. Carbon dioxide is not a typical feedstock for FT catalysis. Hydrogen and carbon dioxide react over a cobalt-based catalyst, producing methane. With iron-based catalysts unsaturated short-chain hydrocarbons are also produced. Upon introduction to

8346-453: The morphology and some properties of the original plant. In many coals, individual macerals can be identified visually. Some macerals include: In coalification huminite is replaced by vitreous (shiny) vitrinite . Maturation of bituminous coal is characterized by bitumenization , in which part of the coal is converted to bitumen , a hydrocarbon-rich gel. Maturation to anthracite is characterized by debitumenization (from demethanation) and

8453-405: The most important distinction is between thermal coal (also known as steam coal), which is burnt to generate electricity via steam; and metallurgical coal (also known as coking coal), which is burnt at high temperature to make steel . Hilt's law is a geological observation that (within a small area) the deeper the coal is found, the higher its rank (or grade). It applies if the thermal gradient

8560-407: The nature of Carboniferous forests, which included lycophyte trees whose determinate growth meant that carbon was not tied up in heartwood of living trees for long periods. One theory suggested that about 360 million years ago, some plants evolved the ability to produce lignin , a complex polymer that made their cellulose stems much harder and more woody. The ability to produce lignin led to

8667-455: The number of double bonds between carbon). As carbonization proceeds, aliphatic compounds convert to aromatic compounds . Similarly, aromatic rings fuse into polyaromatic compounds (linked rings of carbon atoms). The structure increasingly resembles graphene , the structural element of graphite. Chemical changes are accompanied by physical changes, such as decrease in average pore size. The macerals are coalified plant parts that retain

8774-514: The optimal H 2 :CO ratio is around 1.8–2.1. Iron-based catalysts can tolerate lower ratios, due to the intrinsic water-gas shift reaction activity of the iron catalyst. This reactivity can be important for synthesis gas derived from coal or biomass, which tend to have relatively low H 2 :CO ratios (< 1). Efficient removal of heat from the reactor is the basic need of FT reactors since these reactions are characterized by high exothermicity. Four types of reactors are discussed: In general

8881-434: The oxygenation according to the following stoichiometry: Anaerobic methanotrophs rely on the bioconversion of methane using the enzymes called methyl-coenzyme M reductases . These organisms effect reverse methanogenesis . Strenuous efforts have been made to elucidate the mechanisms of these methane-converting enzymes, which would enable their catalysis to be replicated in vitro. Biodiesel can be made from CO 2 using

8988-456: The pre-combustion treatment, turbine technology (e.g. supercritical steam generator ) and the age of the plant. A few integrated gasification combined cycle (IGCC) power plants have been built, which burn coal more efficiently. Instead of pulverizing the coal and burning it directly as fuel in the steam-generating boiler, the coal is gasified to create syngas , which is burned in a gas turbine to produce electricity (just like natural gas

9095-479: The pressure leads to higher conversion rates and also favors the formation of long-chained alkanes , both of which are desirable. Typical pressures range from one to several tens of atmospheres. Even higher pressures would be favorable, but the benefits may not justify the additional costs of high-pressure equipment, and higher pressures can lead to catalyst deactivation via coke formation. A variety of synthesis-gas compositions can be used. For cobalt-based catalysts

9202-430: The primary metal, i.e., iron vs cobalt. While group 1 alkali metals (e.g., potassium), help iron catalysts, they poison cobalt catalysts. Catalysts are supported on high-surface-area binders/supports such as silica , alumina , or zeolites . The F-T process attracted attention as a means of Nazi Germany to produce liquid hydrocarbons. The original process was developed by Franz Fischer and Hans Tropsch , working at

9309-484: The primary metal, iron vs cobalt. Iron catalysts need alkali promotion to attain high activity and stability (e.g. 0.5 wt% K 2 O ). Potassium-doped α-Fe 2 O 3 are synthesized under variable calcination temperatures (400–800 °C). Addition of Cu for reduction promotion, addition of SiO 2 , Al 2 O 3 for structural promotion and maybe some manganese can be applied for selectivity control (e.g. high olefinicity). The choice of promoters depends on

9416-605: The process in the 1930s and 1940s. Aicher's company was named Synthetic Oils Ltd (not related to a company of the same name in Canada). Around the 1930s and 1940s, Arthur Imhausen developed and implemented an industrial process for producing edible fats from these synthetic oils through oxidation . The products were fractionally distilled and the edible fats were obtained from the C 9 - C 16 fraction which were reacted with glycerol such as that synthesized from propylene. "Coal butter" margarine made from synthetic oils

9523-457: The process. Carbon monoxide for FT catalysis is derived from hydrocarbons. In gas to liquids (GTL) technology, the hydrocarbons are low molecular weight materials that often would be discarded or flared. Stranded gas provides relatively cheap gas. For GTL to be commercially viable, gas must remain relatively cheaper than oil. Several reactions are required to obtain the gaseous reactants required for FT catalysis . First, reactant gases entering

9630-406: The product distribution of hydrocarbons formed during the Fischer–Tropsch process follows an Anderson–Schulz–Flory distribution , which can be expressed as: where W n is the weight fraction of hydrocarbons containing n carbon atoms, and α is the chain growth probability or the probability that a molecule will continue reacting to form a longer chain. In general, α is largely determined by

9737-403: The production of liquid fuels, are reactions that form C–C bonds, such as migratory insertion . Many related stoichiometric reactions have been simulated on discrete metal clusters , but homogeneous Fischer–Tropsch catalysts are of no commercial importance. Addition of isotopically labelled alcohol to the feed stream results in incorporation of alcohols into product. This observation establishes

9844-483: The proposed commercial facilities. In 2010, INFRA built a compact Pilot Plant for conversion of natural gas into synthetic oil. The plant modeled the full cycle of the GTL chemical process including the intake of pipeline gas, sulfur removal, steam methane reforming, syngas conditioning, and Fischer–Tropsch synthesis. In 2013 the first pilot plant was acquired by VNIIGAZ Gazprom LLC. In 2014 INFRA commissioned and operated on

9951-427: The reacting groups are attached. Dehydration and decarboxylation take place early in coalification, while demethanation begins only after the coal has already reached bituminous rank. The effect of decarboxylation is to reduce the percentage of oxygen, while demethanation reduces the percentage of hydrogen. Dehydration does both, and (together with demethanation) reduces the saturation of the carbon backbone (increasing

10058-453: The reaction. Such phases include various oxides and carbides as well as polymorphs of the metals. Control of these constituents may be relevant to product distributions. Aside from iron and cobalt, nickel and ruthenium are active for converting the CO/H 2 mixture to hydrocarbons. Although expensive, ruthenium is the most active of the Fischer–Tropsch catalysts in the sense that It works at

10165-399: The sulfur and most of the nitrogen is incorporated into the organic fraction in the form of organosulfur compounds and organonitrogen compounds . This sulfur and nitrogen are strongly bound within the hydrocarbon matrix. These elements are released as SO 2 and NO x upon combustion. They cannot be removed, economically at least, otherwise. Some coals contain inorganic sulfur, mainly in

10272-458: The water-gas shift is not needed for cobalt catalysts. Cobalt-based catalysts are more sensitive than their iron counterparts. Illustrative of real world catalyst selection, high-temperature Fischer–Tropsch (HTFT), which operates at 330–350 °C, uses an iron-based catalyst. This process was used extensively by Sasol in their coal-to-liquid plants (CTL). Low-temperature Fischer–Tropsch (LTFT) uses an iron- or cobalt-based catalyst. This process

10379-415: The world's coal-generated electricity. Efforts around the world to reduce the use of coal have led some regions to switch to natural gas and renewable energy . In 2018 coal-fired power station capacity factor averaged 51%, that is they operated for about half their available operating hours. Coke is a solid carbonaceous residue that is used in manufacturing steel and other iron-containing products. Coke

10486-590: Was 8.3 billion tonnes in 2022, and is set to remain at record levels in 2023. To meet the Paris Agreement target of keeping global warming below 2 °C (3.6 °F) coal use needs to halve from 2020 to 2030, and "phasing down" coal was agreed upon in the Glasgow Climate Pact . The largest consumer and importer of coal in 2020 was China , which accounts for almost half the world's annual coal production, followed by India with about

10593-574: Was based on the trading of this commodity. Coal continues to arrive on beaches around the world from both natural erosion of exposed coal seams and windswept spills from cargo ships. Many homes in such areas gather this coal as a significant, and sometimes primary, source of home heating fuel. Coal consists mainly of a black mixture of diverse organic compounds and polymers. Of course, several kinds of coals exist, with variable dark colors and variable compositions. Young coals (brown coal, lignite) are not black. The two main black coals are bituminous, which

10700-549: Was built and operated by Rentech, Inc., in partnership with ClearFuels, a company specializing in biomass gasification. Located in Commerce City, Colorado, the facility produces about 10 barrels per day (1.6 m/d) of fuels from natural gas. Commercial-scale facilities were planned for Rialto, California ; Natchez, Mississippi ; Port St. Joe, Florida ; and White River, Ontario . Rentech closed down their pilot plant in 2013, and abandoned work on their FT process as well as

10807-510: Was carried to London by sea. In 1257–1259, coal from Newcastle upon Tyne was shipped to London for the smiths and lime -burners building Westminster Abbey . Seacoal Lane and Newcastle Lane, where coal was unloaded at wharves along the River Fleet , still exist. These easily accessible sources had largely become exhausted (or could not meet the growing demand) by the 13th century, when underground extraction by shaft mining or adits

10914-612: Was developed in the Soviet Union , or in an MHD topping cycle . However these are not widely used due to lack of profit. In 2017 38% of the world's electricity came from coal, the same percentage as 30 years previously. In 2018 global installed capacity was 2 TW (of which 1TW is in China) which was 30% of total electricity generation capacity. The most dependent major country is South Africa, with over 80% of its electricity generated by coal; but China alone generates more than half of

11021-408: Was developed. The alternative name was "pitcoal", because it came from mines. Cooking and home heating with coal (in addition to firewood or instead of it) has been done in various times and places throughout human history, especially in times and places where ground-surface coal was available and firewood was scarce, but a widespread reliance on coal for home hearths probably never existed until such

11128-497: Was during the Late Paleozoic icehouse , a time of global glaciation . However, the drop in global sea level accompanying the glaciation exposed continental shelves that had previously been submerged, and to these were added wide river deltas produced by increased erosion due to the drop in base level . These widespread areas of wetlands provided ideal conditions for coal formation. The rapid formation of coal ended with

11235-504: Was found to be nutritious and of agreeable taste, and it was incorporated into diets contributing as much as 700 calories per day. The process required at least 60 kg of coal per kg of synthetic butter. The LTFT facility Pearl GTL at Ras Laffan , Qatar, is the second largest FT plant in the world after Sasol's Secunda plant in South Africa. It uses cobalt catalysts at 230 °C, converting natural gas to petroleum liquids at

11342-564: Was once known as "steam coal" as it was widely used as a fuel for steam locomotives . In this specialized use, it is sometimes known as "sea coal" in the United States. Small "steam coal", also called dry small steam nuts (DSSN), was used as a fuel for domestic water heating . Coal played an important role in industry in the 19th and 20th century. The predecessor of the European Union , the European Coal and Steel Community ,

11449-430: Was used for electricity generation. Coal burnt in coal power stations to generate electricity is called thermal coal . It is usually pulverized and then burned in a furnace with a boiler . The furnace heat converts boiler water to steam , which is then used to spin turbines which turn generators and create electricity. The thermodynamic efficiency of this process varies between about 25% and 50% depending on

#528471