Synthol

Synthetic waxes Synthine process Synthoil Synthol... 

Fischer-Tropsch Process. The Hterature on the hydrogenation of carbon monoxide dates back to 1902 when the synthesis of methane from synthesis gas over a nickel catalyst was reported (17). In 1923, F. Fischer and H. Tropsch reported the formation of a mixture of organic compounds they called synthol by reaction of synthesis gas over alkalized iron turnings at 10—15 MPa (99—150 atm) and 400—450°C (18). This mixture contained mostly oxygenated compounds, but also contained a small amount of alkanes and alkenes. Further study of the reaction at 0.7 MPa (6.9 atm) revealed that low pressure favored olefinic and paraffinic hydrocarbons and minimized oxygenates, but at this pressure the reaction rate was very low. Because of their pioneering work on catalytic hydrocarbon synthesis, this class of reactions became known as the Fischer-Tropsch (FT) synthesis. 

Sasol produces synthetic fuels and chemicals from coal-derived synthesis gas. Two significant variations of this technology have been commercialized, and new process variations are continually under development. Sasol One used both the fixed-bed (Arge) process, operated at about 240°C, as weU as a circulating fluidized-bed (Synthol) system operating at 340°C. Each ET reactor type has a characteristic product distribution that includes coproducts isolated for use in the chemical industry. Paraffin wax is one of the principal coproducts of the low temperature Arge process. Alcohols, ketones, and lower paraffins are among the valuable coproducts obtained from the Synthol process. 

Recent advances in Eischer-Tropsch technology at Sasol include the demonstration of the slurry-bed Eischer-Tropsch process and the new generation Sasol Advanced Synthol (SAS) Reactor, which is a classical fluidized-bed reactor design. The slurry-bed reactor is considered a superior alternative to the Arge tubular fixed-bed reactor. Commercial implementation of a slurry-bed design requires development of efficient catalyst separation techniques. Sasol has developed proprietary technology that provides satisfactory separation of wax and soHd catalyst, and a commercial-scale reactor is being commissioned in the first half of 1993. 

A number of chemical products are derived from Sasol s synthetic fuel operations based on the Fischer-Tropsch synthesis including paraffin waxes from the Arge process and several polar and nonpolar hydrocarbon mixtures from the Synthol process. Products suitable for use as hot melt adhesives, PVC lubricants, cormgated cardboard coating emulsions, and poHshes have been developed from Arge waxes. Wax blends containing medium and hard wax fractions are useful for making candles, and over 20,000 t/yr of wax are sold for this appHcation. 

Synthol coproducts include alcohols, ketones, and lower paraffins. They are used mainly as solvents in the paint and printing industries, although some alcohols are blended into fuels. In 1992 Sasol began producing 17,500 t/yr 1-butanol [71-36-3] from 5-07-acetaldehyde [75-07-0] and plaimed to start a plant to produce high purity ethanol [64-17-5] in 1993. Acetone [67-64-1] and methyl ethyl ketone [78-93-3] are two ketone coproducts sold as solvents. 

Table 1. Product Selectivities for Commercial Fixed-Bed and Synthol Units ...

The second reaction is called the Fischer-Tropsch synthesis of hydrocarbons. Depending on the conditions and catalysts, a wide range of hydrocarbons from very light materials up to heavy waxes can be produced. Catalysts for the Fischer-Tropsch reaction iaclude iron, cobalt, nickel, and mthenium. Reaction temperatures range from about 150 to 350°C reaction pressures range from 0.1 to tens of MPa (1 to several hundred atm) (77). The Fischer-Tropsch process was developed iadustriaHy under the designation of the Synthol process by the M. W. Kellogg Co. from 1940 to 1960 (83). 

The purified raw gas goes to a Synthol (Eischer-Tropsch) unit for catalytic conversion of CO and H2 to Hquid fuels. The tars and oils obtained from quenching the raw gas from the gasifiers go to a Phenosolvan plant to provide tar products for the refinery and ammonia for fertilizer. The Synthol plant has seven reactors, each with 1.9 x 10 m /h (1.6 x 10 ft /d) gas feed. Annual plant production is 1.5 x 10 t motor fuels, 185 x 10 t ethylene,... 

Sasol Fischer-Tropsch Process. 1-Propanol is one of the products from Sasol s Fischer-Tropsch process (7). Coal (qv) is gasified ia Lurgi reactors to produce synthesis gas (H2/CO). After separation from gas Hquids and purification, the synthesis gas is fed iato the Sasol Synthol plant where it is entrained with a powdered iron-based catalyst within the fluid-bed reactors. The exothermic Fischer-Tropsch reaction produces a mixture of hydrocarbons (qv) and oxygenates. The condensation products from the process consist of hydrocarbon Hquids and an aqueous stream that contains a mixture of ketones (qv) and alcohols. The ketones and alcohols are recovered and most of the alcohols are used for the blending of high octane gasoline. Some of the alcohol streams are further purified by distillation to yield pure 1-propanol and ethanol ia a multiunit plant, which has a total capacity of 25,000-30,000 t/yr (see Coal conversion processes, gasification). 

Sasol uses both fixed-bed reactors and transported fluidized-bed reactors to convert synthesis gas to hydrocarbons. The multitubular, water-cooled fixed-bed reactors were designed by Lurgi and Ruhrchemie, whereas the newer fluidized-bed reactors scaled up from a pilot unit by Kellogg are now known as Sasol Synthol reactors. The two reactor types use different iron-based catalysts and give different product distributions. 

The use of a fluidized-bed reactor is possible only when the reactants are essentiaUy in the gaseous phase. Eluidized-beds are not suitable for middle distiUate synthesis, where a heavy wax is formed. Eor gasoline synthesis processes like the MobU MTG process and the Synthol process, such reactors are especiaUy suitable when frequent or continuous regeneration of the catalyst is required. Slurry reactors and ebuUiating-bed reactors comprising a three-phase system with very fine catalyst are, in principle, suitable for middle distiUate and wax synthesis, but have not been appHed on a commercial scale. 

Status of Indirect Liquefaction Technology The only commercial indirect coal liquefaction plants for the production of transportation fuels are operated by SASOL in South Africa. Construction of the original plant was begun in 1950, and operations began in 1955. This plant employs both fixed-bed (Arge) and entrained-bed (Synthol) reactors. Two additional plants were later constructed with start-ups in 1980 and 1983. These latter plants employ dry-ash Lurgi Mark IV coal gasifiers and entrained-bed (Synthol) reactors for synthesis gas conversion. These plants currently produce 45 percent of South Africa s transportation fuel requirements, and, in addition, they produce more than 120 other products from coal. 

SASOL has pursued the development of alternative reactors to overcome specific operational difficulties encountered with the fixed-bed and entrained-bed reactors. After several years of attempts to overcome the high catalyst circulation rates and consequent abrasion in the Synthol reactors, a bubbling fluidized-bed reactor 1 m (3.3 ft) in diameter was constructed in 1983. Following successflil testing, SASOL designed and construc ted a full-scale commercial reac tor 5 m (16.4 ft) in diameter. The reactor was successfully commissioned in 1989 and remains in operation. 

The largest Fischer-Tropsch facility based on natural gas is the Mossgas plant located in Mossel Bay, South Africa. Natural gas is converted to synthesis gas in a two-stage reformer and subsequently converted to hydrocarbons by SASOL s Synthol technology. The plant, commissioned in 1992, has a capacity of 7155 mVd (45,000 bbFd). 

Fischer Tropsch technology is best exemplified by the SASOL projects in South Africa. After coal is gasified to a synthesis gas mixture, it is purified in a rectisol unit. The purified gas mixture is reacted in a synthol unit over an iron-based catalyst. The main products are gasoline, diesel fuel, and jet fuels. By-products are ethylene, propylene, alpha olefins, sulfur, phenol, and ammonia which are used for the production of downstream chemicals. 

One discouraging problem is the decrease in reactor or combustor performance when a pilot plant is scaled up to a larger commercial plant. These problems can be related to poor gas flow patterns, undesirable solid mixing patterns and physical operating problems (Matsen, 1985). In the synthol CFB reactors constructed in South Africa, first scale-up from the pilot plant increased the gas throughput by a factor of 500. Shingles and McDonald (1988) describe the severe problems initially encountered and their resolution. 

Shingles, T., and McDonald, A. F., Commercial Experience with Synthol CFB Reactors, in Circulating Fluidized Bed Technol. II, (P. Basu, and B. P. Large, eds.), Peigamon Press, Oxford (1988)... 

Kellogg Synthol Fused Fe Circulating fluidized bed 1955 Sasol 1, Sasolburg, South Africa... 

Sasol Advanced Synthol Fused Fe Fixed fluidized bed 1995 Synfuels, Secunda, South Africa... 

The Sasol 2 and 3 facilities (presently known as Sasol Synfuels) were constructed in Secunda, South Africa, in response to the 1973 oil crisis. Syncrude was produced by Fe-HTFT synthesis in improved Sasol Synthol circulating fluidized bed reactors36. The syncrude composition was similar to the Kellogg Fe-HTFT syncrude of Sasol 1 (Table 18.8). There was limited integration between the two facilities, which had a combined nameplate capacity of 120,000 barrels per day oil equivalent. 

Change occurred in high-temperature Fischer-Tropsch reactor technology. The circulating fluidized bed Sasol Synthol reactors were replaced by fixed fluidized bed Sasol Advanced Synthol (SAS) reactors.44 This did not meaningfully affect the Fe-HTFT syncrude composition, but it reduced the operating cost of HTFT synthesis. 

Fischer-Tropsch A process for converting synthesis gas (a mixture of carbon monoxide and hydrogen) to liquid fuels. Modified versions were known as the Synol and Synthol processes. The process is operated under pressure at 200 to 350°C, over a catalyst. Several different catalyst systems have been used at different periods, notably iron-zinc oxide, nickel-thoria on kieselgtihr, cobalt-thoria on kieselgiihr, and cemented iron oxide. The main products are C5-Cn aliphatic hydrocarbons the aromatics content can be varied by varying the process conditions. The basic reaction was discovered in 1923 by F. Fischer and... 

SASOL [Suid-Afrikaans Sintetiese Olie] Not a process but a large coal gasification complex in South Africa, operated by the South African Oil and Gas Corporation. It first operated in 1955 but took several years to be fully commissioned. A Lurgi fixed-bed gasification unit is used for the primary process. Downstream processes include the following ones, described under their respective names Aige, Fischer-Tropsch, Rectisol, Sulfohn, Synthol. 

Synthol A version of the Fischer-Tropsch process, for making liquid fuels and organic chemicals from syngas. Developed by Pullman Kellogg between 1940 and 1960. First operated at the SASOL plant in South Africa in 1955. The name was used also for the product from the original Fischer-Tropsch process, developed in the 1920s. See also Synol. Hydrocarbon Process., 1963, 42(11), 225. 

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