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Saturday, July 6, 2019

Coal gasification

From Wikipedia, the free encyclopedia
 
Coal gasification is the process of producing syngas–a mixture consisting primarily of carbon monoxide (CO), hydrogen (H2), carbon dioxide (CO2), natural gas (CH4) , and water vapour (H2O)–from coal and water, air and/or oxygen.

Historically, coal was gasified to produce coal gas, also known as "town gas". Coal gas is combustible and was used for municipal lighting, and heating, before the advent of large scale production of natural gas from oil wells.

In current practice, large-scale coal gasification installations are primarily for electricity generation, or for production of chemical feedstocks. The hydrogen obtained from coal gasification can be used for various purposes such as making ammonia, powering a hydrogen economy, or upgrading fossil fuels.

Alternatively, coal-derived syngas can be converted into transportation fuels such as gasoline and diesel through additional treatment, or into methanol which itself can be used as transportation fuel or fuel additive, or which can be converted into gasoline.

Natural gas from coal gasification can be cooled until it liquifies for use as a fuel in the transport sector.

History

In the past, coal was converted to make coal gas, which was piped to customers to burn for illumination, heating, and cooking. High prices of oil and natural gas are leading to increased interest in "BTU Conversion" technologies such as gasification, methanation and liquefaction. The Synthetic Fuels Corporation was a U.S. government-funded corporation established in 1980 to create a market for alternatives to imported fossil fuels (such as coal gasification). The corporation was discontinued in 1985.

Early history of coal gas production by carbonization

Gas lighting in historical center of Wrocław, Poland
 
The Flemish scientist Jan Baptista van Helmont used the name "gas" in his Origins of Medicine (c. 1609) to describe his discovery of a "wild spirit" which escaped from heated wood and coal, and which "differed little from the chaos of the ancients". Similar experiments were carried out in 1681 by Johann Becker of Munich and in 1684 by John Clayton of Wigan, England. The latter called it "Spirit of the Coal". William Murdoch (later known as Murdock) discovered new ways of making, purifying and storing gas. Among others, he illuminated his house at Redruth and his cottage at Soho, Birmingham in 1792, the entrance to the Manchester Police Commissioners premises in 1797, the exterior of the factory of Boulton and Watt in Birmingham, and a large cotton mill in Salford, Lancashire in 1805.

Professor Jan Pieter Minckeleers lit his lecture room at the University of Louvain in 1783 and Lord Dundonald lit his house at Culross, Scotland, in 1787, the gas being carried in sealed vessels from the local tar works. In France, Philippe le Bon patented a gas fire in 1799 and demonstrated street lighting in 1801. Other demonstrations followed in France and in the United States, but, it is generally recognized that the first commercial gas works was built by the London and Westminster Gas Light and Coke Company in Great Peter Street in 1812 laying wooden pipes to illuminate Westminster Bridge with gas lights on New Year's Eve in 1813. In 1816, Rembrandt Peale and four others established the Gas Light Company of Baltimore, the first manufactured gas company in America. In 1821, natural gas was being used commercially in Fredonia, New York. The first German gas works was built in Hannover in 1825 and by 1870 there were 340 gas works in Germany making town gas from coal, wood, peat and other materials.

Working conditions in the Gas Light and Coke Company's Horseferry Road Works, London, in the 1830s were described by a French visitor, Flora Tristan, in her Promenades Dans Londres:
Two rows of furnaces on each side were fired up; the effect was not unlike the description of Vulcan's forge, except that the Cyclops were animated with a divine spark, whereas the dusky servants of the English furnaces were joyless, silent and benumbed.... The foreman told me that stokers were selected from among the strongest, but that nevertheless they all became consumptive after seven or eight years of toil and died of pulmonary consumption. That explained the sadness and apathy in the faces and every movement of the hapless men.
The first public piped gas supply was to 13 gas lamps, each with three glass globes along the length of Pall Mall, London in 1807. The credit for this goes to the inventor and entrepreneur Fredrick Winsor and the plumber Thomas Sugg, who made and laid the pipes. Digging up streets to lay pipes required legislation and this delayed the development of street lighting and gas for domestic use. Meanwhile, William Murdoch and his pupil Samuel Clegg were installing gas lighting in factories and work places, encountering no such impediments.

Early history of coal gas production by gasification

In the 1850s every small to medium-sized town and city had a gas plant to provide for street lighting. Subscribing customers could also have piped lines to their houses. By this era, gas lighting became accepted. Gaslight trickled down to the middle class and later came gas cookers and stoves.

The 1860s were the golden age of coal gas development. Scientists like Kekulé and Perkin cracked the secrets of organic chemistry to reveal how gas is made and its composition. From this came better gas plants and Perkin's purple dyes, such as Mauveine. In the 1850s, processes for making Producer gas and Water gas from coke were developed. Unenriched water gas may be described as Blue water gas (BWG). 

Mond gas, developed in the 1850s by Ludwig Mond, was producer gas made from coal instead of coke. It contained ammonia and coal tar and was processed to recover these valuable compounds. 

Blue water gas (BWG) burns with a non-luminous flame which makes it unsuitable for lighting purposes. Carburetted Water Gas (CWG), developed in the 1860s, is BWG enriched with gases obtained by spraying oil into a hot retort. It has a higher calorific value and burns with a luminous flame.

The carburetted water gas process was improved by Thaddeus S. C. Lowe in 1875. The gas oil was fixed into the BWG via thermocracking in the carburettor and superheater of the CWG generating set. CWG was the dominant technology in the US from the 1880s until the 1950s, replacing coal gasification. CWG has a CV of 20 MJ/m3 i.e. slightly more than half that of natural gas.

Development of the coal gas industry in the UK

The advent of incandescent gas lighting in factories, homes and in the streets, replacing oil lamps and candles with steady clear light, almost matching daylight in its colour, turned night into day for many—making night shift work possible in industries where light was all important—in spinning, weaving and making up garments etc. The social significance of this change is difficult for generations brought up with lighting after dark available at the touch of a switch to appreciate. Not only was industrial production accelerated, but streets were made safe, social intercourse facilitated and reading and writing made more widespread. Gas works were built in almost every town, main streets were brightly illuminated and gas was piped in the streets to the majority of urban households. The invention of the gas meter and the pre-payment meter in the late 1880s played an important role in selling town gas to domestic and commercial customers. 

1934 gas cooker in England
 
The education and training of the large workforce, the attempts to standardise manufacturing and commercial practices and the moderating of commercial rivalry between supply companies prompted the founding of associations of gas managers, first in Scotland in 1861. A British Association of Gas Managers was formed in 1863 in Manchester and this, after a turbulent history, became the foundation of the Institute of Gas Engineers (IGE). In 1903, the reconstructed Institution of Civil Engineers (ICE) initiated courses for students of gas manufacture in the City and Guilds of London Institute. The IGE was granted the Royal Charter in 1929. Universities were slow to respond to the needs of the industry and it was not until 1908 that the first Professorship of Coal Gas and Fuel Industries was founded at the University of Leeds. In 1926, the Gas Light and Coke Company opened Watson House adjacent to Nine Elms Gas Works. At first, this was a scientific laboratory. Later it included a centre for training apprentices but its major contribution to the industry was its gas appliance testing facilities, which were made available to the whole industry, including gas appliance manufacturers. Using this facility, the industry established not only safety but also performance standards for both the manufacture of gas appliances and their servicing in customers' homes and commercial premises. 

During World War I, the gas industry's by-products, phenol, toluene and ammonia and sulphurous compounds were valuable ingredients for explosives. Much coal for the gas works was shipped by sea and was vulnerable to enemy attack. The gas industry was a large employer of clerks, mainly male before the war. But the advent of the typewriter and the female typist made another important social change that was, unlike the employment of women in war-time industry, to have long-lasting effects. 

The inter-war years were marked by the development of the continuous vertical retort which replaced many of the batch fed horizontal retorts. There were improvements in storage, especially the waterless gas holder, and distribution with the advent of 2–4 inch steel pipes to convey gas at up to 50 psi (340 kPa) as feeder mains compared to the traditional cast iron pipes working at an average of 2–3 inches water gauge (500–750 Pa). Benzole as a vehicle fuel and coal tar as the main feedstock for the emerging organic chemical industry provided the gas industry with substantial revenues. Petroleum supplanted coal tar as the primary feedstock of the organic chemical industry after World War II and the loss of this market contributed to the economic problems of the gas industry after the war. 

A wide variety of appliances and uses for gas developed over the years. Gas fires, gas cookers, refrigerators, washing machines, hand irons, pokers for lighting coal fires, gas-heated baths, remotely controlled clusters of gas lights, gas engines of various types and, in later years, gas warm air and hot water central heating and air conditioning, all of which made immense contributions to the improvement of the quality of life in cities and towns worldwide. The evolution of electric lighting made available from public supply extinguished the gas light, except where colour matching was practised as in haberdashery shops.

Process

Scheme of a Lurgi gasifier
 
During gasification, the coal is blown through with oxygen and steam (water vapor) while also being heated (and in some cases pressurized). If the coal is heated by external heat sources the process is called "allothermal", while "autothermal" process assumes heating of the coal via exothermal chemical reactions occurring inside the gasifier itself. It is essential that the oxidizer supplied is insufficient for complete oxidizing (combustion) of the fuel. During the reactions mentioned, oxygen and water molecules oxidize the coal and produce a gaseous mixture of carbon dioxide (CO2), carbon monoxide (CO), water vapour (H2O), and molecular hydrogen (H2). (Some by-products like tar, phenols, etc. are also possible end products, depending on the specific gasification technology utilized.) This process has been conducted in-situ within natural coal seams (referred to as underground coal gasification) and in coal refineries. The desired end product is usually syngas (i.e., a combination of H2 + CO), but the produced coal gas may also be further refined to produce additional quantities of H2:
3C (i.e., coal) + O2 + H2O → H2 + 3CO
If the refiner wants to produce alkanes (i.e., hydrocarbons present in natural gas, gasoline, and diesel fuel), the coal gas is collected at this state and routed to a Fischer-Tropsch reactor. If, however, hydrogen is the desired end-product, the coal gas (primarily the CO product) undergoes the water gas shift reaction where more hydrogen is produced by additional reaction with water vapor:
CO + H2O → CO2 + H2
Although other technologies for coal gasification currently exist, all employ, in general, the same chemical processes. For low-grade coals (i.e., "brown coals") which contain significant amounts of water, there are technologies in which no steam is required during the reaction, with coal (carbon) and oxygen being the only reactants. As well, some coal gasification technologies do not require high pressures. Some utilize pulverized coal as fuel while others work with relatively large fractions of coal. Gasification technologies also vary in the way the blowing is supplied. 

"Direct blowing" assumes the coal and the oxidizer being supplied towards each other from the opposite sides of the reactor channel. In this case the oxidizer passes through coke and (more likely) ashes to the reaction zone where it interacts with coal. The hot gas produced then passes fresh fuel and heats it while absorbing some products of thermal destruction of the fuel, such as tars and phenols. Thus, the gas requires significant refining before being used in the Fischer-Tropsch reaction. Products of the refinement are highly toxic and require special facilities for their utilization. As a result, the plant utilizing the described technologies has to be very large to be economically efficient. One of such plants called SASOL is situated in the Republic of South Africa (RSA). It was built due to embargo applied to the country preventing it from importing oil and natural gas. RSA is rich in Bituminous coal and Anthracite and was able to arrange the use of the well known high pressure "Lurgi" gasification process developed in Germany in the first half of 20th century. 

"Reversed blowing" (as compared to the previous type described which was invented first) assumes the coal and the oxidizer being supplied from the same side of the reactor. In this case there is no chemical interaction between coal and oxidizer before the reaction zone. The gas produced in the reaction zone passes solid products of gasification (coke and ashes), and CO2 and H2O contained in the gas are additionally chemically restored to CO and H2. As compared to the "direct blowing" technology, no toxic by-products are present in the gas: those are disabled in the reaction zone. This type of gasification has been developed in the first half of 20th century, along with the "direct blowing", but the rate of gas production in it is significantly lower than that in "direct blowing" and there were no further efforts of developing the "reversed blowing" processes until 1980-s when a Soviet research facility KATEKNIIUgol' (R&D Institute for developing Kansk-Achinsk coal field) began R&D activities to produce the technology now known as "TERMOKOKS-S" process. The reason for reviving the interest in this type of gasification process is that it is ecologically clean and able to produce two types of useful products (simultaneously or separately): gas (either combustible or syngas) and middle-temperature coke. The former may be used as a fuel for gas boilers and diesel-generators or as syngas for producing gasoline, etc., the latter - as a technological fuel in metallurgy, as a chemical absorbent or as raw material for household fuel briquettes. Combustion of the product gas in gas boilers is ecologically cleaner than combustion of initial coal. Thus, a plant utilizing gasification technology with the "reversed blowing" is able to produce two valuable products of which one has relatively zero production cost since the latter is covered by competitive market price of the other. As the Soviet Union and its KATEKNIIUgol' ceased to exist, the technology was adopted by the individual scientists who originally developed it and is now being further researched in Russia and commercially distributed worldwide. Industrial plants utilizing it are now known to function in Ulaan-Baatar (Mongolia) and Krasnoyarsk (Russia). 

Pressurized airflow bed gasification technology created through the joint development between Wison Group and Shell (Hybrid). For example: Hybrid is an advanced pulverized coal gasification technology, this technology combined with the existing advantages of Shell SCGP waste heat boiler, includes more than just a conveying system, pulverized coal pressurized gasification burner arrangement, lateral jet burner membrane type water wall, and the intermittent discharge has been fully validated in the existing SCGP plant such as mature and reliable technology, at the same time, it removed the existing process complications and in the syngas cooler (waste pan) and [fly ash] filters which easily failed, and combined the current existing gasification technology that is widely used in synthetic gas quench process. It not only retains the original Shell SCGP waste heat boiler of coal characteristics of strong adaptability, and ability to scale up easily, but also absorb the advantages of the existing quench technology.

Underground coal gasification

Underground coal gasification (UCG) is an industrial gasification process, which is carried out in non-mined coal seams. It involves injection of a gaseous oxidizing agent, usually oxygen or air, and bringing the resulting product gas to the surface through production wells drilled from the surface. The product gas can be used as a chemical feedstock or as fuel for power generation. The technique can be applied to resources that are otherwise not economical to extract. It also offers an alternative to conventional coal mining methods. Compared to traditional coal mining and gasification, UCG has less environmental and social impact, though environmental concerns exist, including the potential for aquifer contamination.

Carbon capture technology

Carbon capture, utilization, and sequestration (or storage) is increasingly being utilized in modern coal gasification projects to address the greenhouse gas emissions concern associated with the use of coal and carbonaceous fuels. In this respect, gasification has a significant advantage over conventional combustion of mined coal, in which CO2 resulting from combustion is considerably diluted by nitrogen and residual oxygen in the near-ambient pressure combustion exhaust, making it relatively difficult, energy-intensive, and expensive to capture the CO2 (this is known as “post-combustion” CO2 capture).

In gasification, on the other hand, oxygen is normally supplied to the gasifiers and just enough fuel is combusted to provide the heat to gasify the rest; moreover, gasification is often performed at elevated pressure. The resulting syngas is typically at higher pressure and not diluted by nitrogen, allowing for much easier, efficient, and less costly removal of CO2. Gasification and integrated gasification combined cycle’s unique ability to easily remove CO2 from the syngas prior to its combustion in a gas turbine (called "pre-combustion" CO2 capture) or its use in fuels or chemicals synthesis is one of its significant advantages over conventional coal utilization systems.

CO2 capture technology options

All coal gasification-based conversion processes require removal of hydrogen sulfide (H2S; an acid gas) from the syngas as part of the overall plant configuration. Typical acid gas removal (AGR) processes employed for gasification design are either a chemical solvent system (e.g., amine gas treating systems based on MDEA, for example) or a physical solvent system (e.g., Rectisol or Selexol). Process selection is mostly dependent on the syngas cleanup requirement and costs. Conventional chemical/physical AGR processes using MDEA, Rectisol or Selexol are commercially proven technologies and can be designed for selective removal of CO2 in addition to H2S from a syngas stream. For significant capture of CO2 from a gasification plant (e.g. > 80%) the CO in the syngas must first be converted to CO2 and hydrogen (H2) via a water-gas-shift (WGS) step upstream of the AGR plant. 

For gasification applications, or Integrated Gasification Combined Cycle (IGCC), the plant modifications required to add the ability to capture CO2 are minimal. The syngas produced by the gasifiers needs to be treated through various processes for the removal of impurities already in the gas stream, so all that is required to remove CO2 is to add the necessary equipment, an absorber and regenerator, to this process train. 

In combustion applications, modifications must be made to the exhaust stack and because of the lower concentrations of CO2 present in the exhaust, much larger volumes of total gas require processing, necessitating larger and more expensive equipment.

IGCC (Integrated Gasification Combined Cycle) based projects in the United States with CO2 capture and use/storage

Mississippi Power’s Kemper Project is in late stages of construction. It will be a lignite-fuel IGCC plant, generating a net 524 MW of power from syngas, while capturing over 65% of CO2 generated using the Selexol process. The technology at the Kemper facility, Transport-Integrated Gasification (TRIG), was developed and is licensed by KBR. The CO2 will be sent by pipeline to depleted oil fields in Mississippi for enhanced oil recovery operations. 

Hydrogen Energy California (HECA) will be a 300MW net, coal and petroleum coke-fueled IGCC polygeneration plant (producing hydrogen for both power generation and fertilizer manufacture). Ninety percent of the CO2 produced will be captured (using Rectisol) and transported to Elk Hills Oil Field for EOR, enabling recovery of 5 million additional barrels of domestic oil per year. 

Summit’s Texas Clean Energy Project (TCEP) will be a coal-fueled, IGCC-based 400MW power/polygeneration project (also producing urea fertilizer), which will capture 90% of its CO2 in pre-combustion using the Rectisol process. The CO2 not used in fertilizer manufacture will be used for enhanced oil recovery in the West Texas Permian Basin. 

Plants such as the Texas Clean Energy Project which employ carbon capture and storage have been touted as a partial, or interim, solution to climate change issues if they can be made economically viable by improved design and mass production. There has been opposition from utility regulators and ratepayers due to increased cost; and from environmentalists such as Bill McKibben, who view any continued use of fossil fuels as counterproductive.

By-products

The by-products of coal gas manufacture included coke, coal tar, sulfur and ammonia; all useful products. Dyes, medicines, including sulfa drugs, saccharin and many organic compounds are therefore derived from coal gas. 

Coke is used as a smokeless fuel and for the manufacture of water gas and producer gas. Coal tar is subjected to fractional distillation to recover various products, including
Sulfur is used in the manufacture of sulfuric acid and ammonia is used in the manufacture of fertilisers.

Commercialization

According to the Gasification and Syngas Technologies Council, a trade association, there are globally 272 operating gasification plants with 686 gasifiers and 74 plants with 238 gasifiers under construction. Most of them use coal as feedstock.

As of 2017 large scale expansion of the coal gasification industry was occurring only in China where local governments and energy companies promote the industry to provide jobs and a market for coal. For the most part, the plants are located in remote, coal-rich areas. 

The central government is aware of the conflicts with environmental goals: in addition to producing a great deal of carbon dioxide, the plants use a great deal of water in areas where water is scarce.

Environmental impact

Environmental impact of manufactured coal gas industry

From its original development until the wide-scale adoption of natural gas, more than 50,000 manufactured gas plants were in existence in the United States alone. The process of manufacturing gas usually produced a number of by-products that contaminated the soil and groundwater in and around the manufacturing plant, so many former town gas plants are a serious environmental concern, and cleanup and remediation costs are often high. Manufactured gas plants (MGPs) were typically sited near or adjacent to waterways that were used to transport in coal and for the discharge of wastewater contaminated with tar, ammonia and/or drip oils, as well as outright waste tars and tar-water emulsions. 

In the earliest days of MGP operations, coal tar was considered a waste and often disposed into the environment in and around the plant locations. While uses for coal tar developed by the late-19th century, the market for tar varied and plants that could not sell tar at a given time could store tar for future use, attempt to burn it as boiler fuel, or dump the tar as waste. Commonly, waste tars were disposed of in old gas holders, adits or even mine shafts (if present). Over time, the waste tars degrade with phenols, benzene (and other mono-aromatics – BTEX) and polycyclic aromatic hydrocarbons released as pollutant plumes that can escape into the surrounding environment. Other wastes included "blue billy", which is a ferroferricyanide compound—the blue colour is from Prussian blue, which was commercially used as a dye. Blue billy is typically a granular material and was sometimes sold locally with the strap line "guaranteed weed free drives". The presence of blue billy can give gas works waste a characteristic musty/bitter almonds or marzipan smell which is associated with cyanide gas. 

The shift to the Carburetted Water Gas process initially resulted in a reduced output of water gas tar as compared to the volume of coal tars. The advent of automobiles reduced the availability of naphtha for carburetion oil, as that fraction was desirable as motor fuel. MGPs that shifted to heavier grades of oil often experienced problems with the production of tar-water emulsions, which were difficult, time consuming, and costly to break. (The cause of tar change water emulsions is complex and was related to several factors, including free carbon in the carburetion oil and the substitution of bituminous coal as a feedstock instead of coke.) The production of large volumes of tar-water emulsions quickly filled up available storage capacity at MGPs and plant management often dumped the emulsions in pits, from which they may or may not have been later reclaimed. Even if the emulsions were reclaimed, the environmental damage from placing tars in unlined pits remained. The dumping of emulsions (and other tarry residues such as tar sludges, tank bottoms, and off-spec tars) into the soil and waters around MGPs is a significant factor in the pollution found at former manufactured gas plants (known as "FMGPs" in environmental remediation) today.

Contaminants commonly associated with FMGPs include:
  • BTEX
    • Diffused out from deposits of coal/gas tars
    • Leaks of carburetting oil/light oil
    • Leaks from drip pots, that collected condensible hydrocarbons from the gas
  • Coal tar waste/sludge
    • Typically found in sumps of gas holders and decanting ponds.
    • Coal tar sludge has no resale value and so was always dumped.
  • Volatile organic compounds
  • Polycyclic aromatic hydrocarbons (PAHs)
    • Present in coal tar, gas tar, and pitch at significant concentrations.
  • Heavy metals
    • Leaded solder for gas mains, lead piping, coal ashes.
  • Cyanide
    • Purifier waste has large amounts of complex ferrocyanides in it.
  • Lampblack
    • Only found where crude oil was used as gasification feedstock.
  • Tar emulsions
Coal tar and coal tar sludges are frequently denser than water and are present in the environment as a dense non-aqueous phase liquid

In the UK, a number of former gasworks sites have been redeveloped for residential and other uses (including the Millennium Dome), being seen as prime developable land within the confines of city boundaries. Such development opportunities are now leading to problems associated with planning and the Contaminated Land Regime and have recently been debated in the House of Commons.

Environmental impact of modern coal gasification

Coal gasification processes require controls and pollution prevention measures to mitigate pollutant emissions. Pollutants or emissions of concern in the context of coal gasification include primarily:
  • Ash & slag
Non-slagging gasifiers produce dry ash similar to that produced by conventional coal combustion, which can be an environmental liability if the ash (typically containing heavy metals) is leachable or caustic, and if the ash must be stored in ash ponds. Slagging gasifiers, which are utilized at many of the major coal gasification applications worldwide, have considerable advantage in that ash components are fused into a glassy slag, capturing trace heavy metals in the non-leachable glassy matrix, rendering the material non-toxic. This non-hazardous slag has multiple beneficial uses such as aggregate in concrete, aggregate in asphalt for road construction, grit in abrasive blasting, roofing granules, etc.
  • Carbon dioxide (CO2)
CO2 is of paramount importance in global climate change.
  • Mercury
  • Arsenic
  • Particulate matter (PM)
Ash is formed in gasification from inorganic impurities in the coal. Some of these impurities react to form microscopic solids which can be suspended in the syngas produced by gasification.
  • Sulfur dioxide (SO2)
Typically coal contains anywhere from 0.2 to 5 percent sulfur by dry weight, which converts to H2S and COS in the gasifiers due to the high temperatures and low oxygen levels. These "acid gases" are removed from the syngas produced by the gasifiers by acid gas removal equipment prior to the syngas being burned in the gas turbine to produce electricity, or prior to its use in fuels synthesis.
  • Nitrogen oxides (NOx)
(NOx) refers to nitric oxide (NO) and nitrogen dioxide (NO2). Coal usually contains between 0.5 and 3 percent nitrogen on a dry weight basis, most of which converts to harmless nitrogen gas. Small levels of ammonia and hydrogen cyanide are produced, and must be removed during the syngas cooling process. In the case of power generation, NOx also can be formed downstream by the combustion of syngas in turbines.

Fischer–Tropsch process

From Wikipedia, the free encyclopedia

The Fischer–Tropsch process is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen into liquid hydrocarbons. These reactions occur in the presence of metal catalysts, typically at temperatures of 150–300 °C (302–572 °F) and pressures of one to several tens of atmospheres. The process was first developed by Franz Fischer and Hans Tropsch at the Kaiser-Wilhelm-Institut für Kohlenforschung in Mülheim an der Ruhr, Germany, in 1925.
 
As a premier example of C1 chemistry, the Fischer–Tropsch process is an important reaction in both coal liquefaction and gas to liquids technology for producing liquid hydrocarbons. 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 Fischer–Tropsch process then converts these gases into a synthetic lubrication oil and synthetic fuel. The Fischer–Tropsch process has received intermittent attention as a source of low-sulfur diesel fuel and to address the supply or cost of petroleum-derived hydrocarbons.

Reaction mechanism

The Fischer–Tropsch process involves a series of chemical reactions that produce a variety of hydrocarbons, ideally having the formula (CnH2n+2). The more useful reactions produce alkanes as follows:
(2n + 1) H2 + n CO → CnH2n+2 + n H2O
where n 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.

Fischer–Tropsch intermediates and elemental reactions

Converting a mixture of H2 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 –CH2– group produced by CO + 2 H2 → (CH2) + H2O, several reactions are necessary:
  • Associative adsorption of CO
  • Splitting of the C–O bond
  • Dissociative adsorption of 2 H2
  • Transfer of 2 H to the oxygen to yield H2O
  • Desorption of H2O
  • Transfer of 2 H to the carbon to yield CH2
The conversion of CO to alkanes involves hydrogenation of CO, the hydrogenolysis (cleavage with H2) 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 C1 fragments including formyl (CHO), hydroxycarbene (HCOH), hydroxymethyl (CH2OH), methyl (CH3), methylene (CH2), methylidyne (CH), and hydroxymethylidyne (COH). Furthermore, and critical to 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 poorly developed and of no commercial importance. 

Addition of isotopically labelled alcohol to the feed stream results in incorporation of alcohols into product. This observation establishes the facility of C–O bond scission. Using 14C-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’.

Feedstocks: gasification

Fischer–Tropsch plants associated with coal or related solid feedstocks (sources of carbon) must first convert the solid fuel into gaseous reactants, i.e., CO, H2, and alkanes. This conversion is called gasification and the product is called synthesis gas ("syngas"). Synthesis gas obtained from coal gasification tends to have a H2:CO ratio of ~0.7 compared to the ideal ratio of ~2. This ratio is adjusted via the water-gas shift reaction. Coal-based Fischer–Tropsch plants produce varying amounts of CO2, 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 the Fischer–Tropsch process.

Feedstocks: GTL

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. GTL is viable provided gas remains relatively cheaper than oil. 

Several reactions are required to obtain the gaseous reactants required for Fischer–Tropsch catalysis. First, reactant gases entering a Fischer–Tropsch reactor must be desulfurized. Otherwise, sulfur-containing impurities deactivate ("poison") the catalysts required for Fischer–Tropsch reactions.

Several reactions are employed to adjust the H2:CO ratio. Most important is the water-gas shift reaction, which provides a source of hydrogen at the expense of carbon monoxide:
H2O + CO → H2 + CO2
For Fischer–Tropsch plants that use methane as the feedstock, another important reaction is steam reforming, which converts the methane into CO and H2:
H2O + CH4 → CO + 3 H2

Process conditions

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 the pressure leads to higher conversion rates and also favors 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 the optimal H2:CO ratio is around 1.8–2.1. Iron-based catalysts can tolerate lower ratios, due to 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 H2:CO ratios (< 1).

Design of the Fischer–Tropsch process reactor

Efficient removal of heat from the reactor is the basic need of Fischer–Tropsch reactors since these reactions are characterized by high exothermicity. Four types of reactors are discussed:

Multi tubular fixed-bed reactor

This type of reactor contains a number of tubes with small diameter. These tubes contain catalyst and are surrounded by boiling water which removes the heat of reaction. A fixed-bed reactor is suitable for operation at low temperatures and has an upper temperature limit of 257 °C (530 K). Excess temperature leads to carbon deposition and hence blockage of the reactor. Since large amounts of the products formed are in liquid state, this type of reactor can also be referred to as a trickle flow reactor system.

Entrained flow reactor

An important requirement of the reactor for the Fischer–Tropsch process is to remove the heat of the reaction. This type of reactor contains two banks of heat exchangers which remove heat; the remainder of which is removed by the products and recycled in the system. The formation of heavy waxes should be avoided, since they condense on the catalyst and form agglomerations. This leads to fluidization. Hence, risers are operated over 297 °C (570 K).

Slurry reactors

Heat removal is done by internal cooling coils. The synthesis gas is bubbled through the waxy products and finely-divided catalyst which is suspended in the liquid medium. This also provides agitation of the contents of the reactor. The catalyst particle size reduces diffusional heat and mass transfer limitations. A lower temperature in the reactor leads to a more viscous product and a higher temperature (> 297 °C, 570 K) gives an undesirable product spectrum. Also, separation of the product from the catalyst is a problem.

Fluid-bed and circulating catalyst (riser) reactors

These are used for high-temperature Fischer–Tropsch synthesis (nearly 340 °C) to produce low-molecular-weight unsaturated hydrocarbons on alkalized fused iron catalysts. The fluid-bed technology (as adapted from the catalytic cracking of heavy petroleum distillates) was introduced by Hydrocarbon Research in 1946–50 and named the 'Hydrocol' process. A large scale Fischer–Tropsch Hydrocol plant (350,000 tons per annum) operated during 1951–57 in Brownsville, Texas. Due to technical problems, and lacking economy due to increasing petroleum availability, this development was discontinued. Fluid-bed Fischer–Tropsch synthesis has recently been very successfully reinvestigated by Sasol. One reactor with a capacity of 500,000 tons per annum is now in operation and even larger ones are being built (nearly 850,000 tons per annum). The process is now used mainly for C2 and C7 alkene production. This new development can be regarded as an important progress in Fischer–Tropsch technology. A high-temperature process with a circulating iron catalyst ('circulating fluid bed', 'riser reactor', 'entrained catalyst process') was introduced by the Kellogg Company and a respective plant built at Sasol in 1956. It was improved by Sasol for successful operation. At Secunda, South Africa, Sasol operated 16 advanced reactors of this type with a capacity of approximately 330,000 tons per annum each. Now the circulating catalyst process is being replaced by the superior Sasol-advanced fluid-bed technology. Early experiments with cobalt catalyst particles suspended in oil have been performed by Fischer. The bubble column reactor with a powdered iron slurry catalyst and a CO-rich syngas was particularly developed to pilot plant scale by Kölbel at the Rheinpreuben Company in 1953. Recently (since 1990) low-temperature Fischer–Tropsch slurry processes are under investigation for the use of iron and cobalt catalysts, particularly for the production of a hydrocarbon wax, or to be hydrocracked and isomerised to produce diesel fuel, by Exxon and Sasol. Today slurry-phase (bubble column) low-temperature Fischer–Tropsch synthesis is regarded by many authors as the most efficient process for Fischer–Tropsch clean diesel production. This Fischer–Tropsch technology is also under development by the Statoil Company (Norway) for use on a vessel to convert associated gas at offshore oil fields into a hydrocarbon liquid.

Product distribution

In general the product distribution of hydrocarbons formed during the Fischer–Tropsch process follows an Anderson–Schulz–Flory distribution, which can be expressed as:
Wn/n = (1 − α)2αn−1
where Wn 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 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 the Fischer–Tropsch 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 lots of long-chained hydrocarbons. Such efforts have had only limited success.

Catalysts

A variety of catalysts can be used for the Fischer–Tropsch process, the most common are the transition metals cobalt, iron, and ruthenium. Nickel can also be used, but tends to favor methane formation (“methanation”).

Cobalt

Cobalt-based catalysts are highly active, although iron may be more suitable for certain applications. Cobalt catalysts are more active for Fischer–Tropsch synthesis when the feedstock is natural gas. Natural gas has a high hydrogen to carbon ratio, so the water-gas shift is not needed for cobalt catalysts. Iron catalysts are preferred for lower quality feedstocks such as coal or biomass. Synthesis gases derived from these hydrogen-poor feedstocks has a low-hydrogen-content and require the water-gas shift reaction. Unlike the other metals used for this process (Co, Ni, Ru), which remain in the metallic state during synthesis, iron catalysts tend to form a number of phases, including various oxides and carbides during the reaction. Control of these phase transformations can be important in maintaining catalytic activity and preventing breakdown of the catalyst particles.

Methylidynetricobaltnonacarbonyl is a molecule that illustrates the kind of reduced carbon species speculated to occur in the Fischer–Tropsch process.
 
In addition to the active metal the catalysts typically contain a number of "promoters," including potassium and copper. Group 1 alkali metals, including potassium, are a poison for cobalt catalysts but are promoters for iron catalysts. Catalysts are supported on high-surface-area binders/supports such as silica, alumina, or zeolites. Promotors also have an important influence on activity. Alkali metal oxides and copper are common promotors, but the formulation depends on the primary metal, iron vs cobalt. Alkali oxides on cobalt catalysts generally cause activity to drop severely even with very low alkali loadings. C≥5 and CO2 selectivity increase while methane and C2–C4 selectivity decrease. In addition, the alkene to alkane ratio increases.

Fischer–Tropsch catalysts are sensitive to poisoning by sulfur-containing compounds. Cobalt-based catalysts are more sensitive than their iron counterparts.

Iron

Fischer–Tropsch iron catalysts need alkali promotion to attain high activity and stability (e.g. 0.5 wt% K
2
O
). 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 working catalyst is only obtained when—after reduction with hydrogen—in the initial period of synthesis several iron carbide phases and elemental carbon are formed whereas iron oxides are still present in addition to some metallic iron. With iron catalysts two directions of selectivity have been pursued. One direction has aimed at a low-molecular-weight olefinic hydrocarbon mixture to be produced in an entrained phase or fluid bed process (Sasol–Synthol process). Due to the relatively high reaction temperature (approx. 340 °C), the average molecular weight of the product is so low that no liquid product phase occurs under reaction conditions. The catalyst particles moving around in the reactor are small (particle diameter 100 µm) and carbon deposition on the catalyst does not disturb reactor operation. Thus a low catalyst porosity with small pore diameters as obtained from fused magnetite (plus promoters) after reduction with hydrogen is appropriate. For maximising the overall gasoline yield, C3 and C4 alkenes have been oligomerized at Sasol. However, recovering the olefins for use as chemicals in, e.g., polymerization processes is advantageous today. The second direction of iron catalyst development has aimed at highest catalyst activity to be used at low reaction temperature where most of the hydrocarbon product is in the liquid phase under reaction conditions. Typically, such catalysts are obtained through precipitation from nitrate solutions. A high content of a carrier provides mechanical strength and wide pores for easy mass transfer of the reactants in the liquid product filling the pores. The main product fraction then is a paraffin wax, which is refined to marketable wax materials at Sasol; however, it also can be very selectively hydrocracked to a high quality diesel fuel. Thus, iron catalysts are very flexible.

Ruthenium

Ruthenium is the most active of the FT catalysts. It works at the lowest reaction temperatures, and it produces the highest molecular weight hydrocarbons. It acts as a Fischer–Tropsch catalyst as the pure metal, without any promotors, thus providing the simplest catalytic system of Fischer–Tropsch synthesis, where mechanistic conclusions should be the easiest—e.g., much easier than with iron as the catalyst. Like with nickel, the selectivity changes to mainly methane at elevated temperature. Its high price and limited world resources exclude industrial application. Systematic Fischer–Tropsch studies with ruthenium catalysts should contribute substantially to the further exploration of the fundamentals of Fischer–Tropsch synthesis. There is an interesting question to consider: what features have the metals nickel, iron, cobalt, and ruthenium in common to let them—and only them—be Fischer–Tropsch catalysts, converting the CO/H2 mixture to aliphatic (long chain) hydrocarbons in a ‘one step reaction’. The term ‘one step reaction’ means that reaction intermediates are not desorbed from the catalyst surface. In particular, it is amazing that the much carbided alkalized iron catalyst gives a similar reaction as the just metallic ruthenium catalyst.

HTFT and LTFT

High-Temperature Fischer–Tropsch (or HTFT) is operated at temperatures of 330–350 °C and uses an iron-based catalyst. This process was used extensively by Sasol in their coal-to-liquid plants (CTL). Low-Temperature Fischer–Tropsch (LTFT) is operated at lower temperatures and uses an iron or cobalt-based catalyst. This process is best known for being used in the first integrated GTL-plant operated and built by Shell in Bintulu, Malaysia.

History

Max Planck Institute for Coal Research at Mülheim an der Ruhr, Germany.
 
Since the invention of the original process by Fischer and Tropsch, working at the Kaiser-Wilhelm-Institut for Chemistry in the 1920s, many refinements and adjustments were made. Fischer and Tropsch 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 Fischer–Tropsch process during World War II to produce ersatz (replacement) fuels. Fischer–Tropsch production accounted for an estimated 9% of German war production of fuels and 25% of the automobile fuel.

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 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).

Commercialization

Fluidized bed gasification with FT-pilot in Güssing, Burgenland, Austria

Ras Laffan, Qatar

ORYX GTL Plant – Qatar

The LTFT facility Pearl GTL at Ras Laffan, Qatar, is the largest FT plant. It uses cobalt catalysts at 230 °C, converting natural gas to petroleum liquids at a rate of 140,000 barrels per day (22,000 m3/d), with additional production of 120,000 barrels (19,000 m3) of oil equivalent in natural gas liquids and ethane. The plant in Ras Laffan was commissioned in 2007, called Oryx GTL, has a capacity of 34,000 barrels per day (5,400 m3/d). The plant utilizes the Sasol slurry phase distillate process, which uses a cobalt catalyst. Oryx GTL is a joint venture between Qatar Petroleum and Sasol.

Sasol

A SASOL garage in Gauteng

Another large 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. The first commercial plant opened in 1952. Sasol uses coal and now natural gas as feedstocks and produces a variety of synthetic petroleum products, including most of the country's diesel fuel.

Sasol scrapped plans to build the GTL plant in Westlake, Louisiana.

PetroSA

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.

Shell middle distillate synthesis

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 is 12,000 barrels per day (1,900 m3/d).

Velocys

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 a combination of landfill gas and pipeline natural gas.

UPM (Finland)

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.

Rentech

A demonstration-scale Fischer–Tropsch plant 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 m3/d) of fuels from natural gas. Commercial-scale facilities are 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 the proposed commercial facilities.

INFRA GTL Technology

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 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 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.

Other

In 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 Fischer–Tropsch technology licensed from Shell and Sasol to convert so-called waste coal (leftovers from the mining process) into low-sulfur diesel fuel.

Research developments

Choren Industries has built a plant in Germany that converts biomass to syngas and fuels using the Shell Fischer–Tropsch 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).

U.S. Air Force certification

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 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 the United States Department of Energy (DOE) and the United States Department of Transportation (DOT). Most recently, Syntroleum has been working with the United States Air Force 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 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 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. With the B-52 now approved to use the FT blend, the C-17 Globemaster III, the B-1B, and eventually every airframe in its inventory to use the fuel by 2011.

Carbon dioxide reuse

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 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.

Process efficiency

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.

Fischer–Tropsch in nature

A Fischer–Tropsch-type process has also been suggested to have produced 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.

Hydrogen-like atom

From Wikipedia, the free encyclopedia https://en.wikipedia.org/wiki/Hydrogen-like_atom ...