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Energy & Fuels 2009, 23, 23422358

Diesel Production from Fischer-Tropsch: The Past, the Present, and New Concepts
Dieter Leckel*
Fischer-Tropsch Renery Catalysis, Sasol Technology Research and DeVelopment, P.O. Box 1, Sasolburg 1947, South Africa ReceiVed January 22, 2009. ReVised Manuscript ReceiVed March 11, 2009

Fischer-Tropsch synthesis is technically classied into two categories, the high-temperature Fischer-Tropsch (HTFT) and the low-temperature Fischer-Tropsch (LTFT) processes. The criterion for this classication is the operating temperature of the synthesis, which ranges between 310-340 C for the HTFT process and 210-260 C for the LTFT process. A Fischer-Tropsch facility can be divided into roughly three sections, synthesis gas (syngas) generation, FT synthesis, and rening of the synthetic crude (syncrude). Fischer-Tropsch reneries differ regarding the product upgrading, and both transportation fuels and chemicals can be produced. Regarding the FT renery history, the conguration of each renery also reects the requirements of the fuel specication at that time. This paper gives a condensed overview of how Fischer-Tropsch facilities changed during the last 70 years and focuses in particular on the diesel fuel produced. Some conceptual ow schemes are additionally presented with emphasis on the combined upgrading of the high boiling part of the FT product spectrum with liquids derived from coal pyrolysis.

1. Introduction Commercialization of the Fischer-Tropsch (FT) technology began in 1934 when Ruhrchemie A.-G. undertook the industrial development of the Fischer-Tropsch process. Laboratory, pilotplant, and semicommercial investigations were followed by the construction of several commercial plants that used coal as syngas source and applying the low-temperature FT (LTFT) technology. The rst Fischer-Tropsch industrial plant went into operation in Germany in 1936, and in the 1940s over 1 million tons of FT liquids were produced yearly.1 A typical process scheme of those plants operating in Germany during the years 1939-1945 are presented together with representative diesel fuel characteristics of those facilities. Diesel oil was a byproduct of those plants, and high cetane numbers (>80) but low density were reported.1,2 The Carthage Hydrocol Fischer-Tropsch plant was an example of an earlier iron-based high-temperature (HTFT) process developed in the United States of America in the 1940-1950s.3,4 The processing scheme was laid out to maximize gasoline production based on natural gas, and the hydrogenated distillate byproduct had compared to a typical crude-derived distillate high cetane numbers (above 70). Construction of the rst coal-based Sasol FT plant (Sasol 1) at Sasolburg, South Africa, began in 1952, and the facility was highly complex, combining the two variants of the FischerTropsch process.5 The Sasol 1 renery consisted of four different reneries that were grouped together, namely, tar workup, HTFT oil workup, LTFT oil workup, and chemical workup. The design
* Phone: +27 16 960-3830. Fax: +27 11 522-3975. E-mail: dieter.leckel@ sasol.com. (1) Underwood, A. J. V. Ind. Eng. Chem 1940, 32 (4), 449454. (2) Weil, B. H.; Lane, J. C. The Technology of the Fischer-Tropsch Process; Constable: London, 1949. (3) Schulz, H. Appl. Catal., A 1999, 186, 312. (4) Keith, P. C. Oil Gas J. 1946, 102112. (5) Dry, M. E. Catal. Today 2002, 71, 227241.

had very little renery integration, apart from a common aqueous product workup and a transfer of the C3-C4 fraction from the LTFT oil workup to the HTFT oil workup section. The benet of the integration was more apparent in the gas loop and the blending opportunities of the unique characteristics of both types of Fischer-Tropsch products. The fuel specication during those years were not very demanding and the distillate produced needed little rening. The Sasol 1 plant design changed during the years, and the last change occurred in 2004 when coal gasication was replaced by natural gas reforming, transforming the site essentially into a gas-to-liquids (GTL) plant producing waxes and chemicals. The formation of OPEC and the oil crisis in the early 1970s prompted Sasol to construct another coal-based HTFT plant at Secunda, South Africa (Sasol 2); of which construction started in 1976.6 However, due to increases in oil price two plants were built, with Sasol 2 coming on stream in 1980 and the Sasol 3 plant being commissioned in 1983. The design of the Sasol 2 and Sasol 3 reneries were similar, except for the addition of a high pressure distillate hydrogenation section to the tar renery of Sasol 3, which processed gasication-derived coal pyrolysis liquids from both facilities. The original HTFT circulating uidized bed (CFB) synthesis reactors installed at Secunda were improved and scaled-up versions of those operating at Sasol 1, Sasolburg. These reactors were replaced in the late 1990s by Sasol Advanced Synthol (SAS) reactors. The Sasol 2 and 3 plants each consisted of four different reneries, namely tar workup, condensate workup, oil workup, and chemical workup. The two HTFT plants are, to date, so interlinked that the Sasol Secunda facility was renamed Sasol Synfuels. The facility produces 160 000 bpd of products that are mainly motorgasoline and diesel, but also includes chemicals. Another FT facility that is based on the Sasol iron-catalyzed HTFT Synthol technology is operated by PetroSA at Mossel
(6) Steynberg, A. Stud. Surf. Sci. Catal. 2004, 152, 1.

10.1021/ef900064c CCC: $40.75 2009 American Chemical Society Published on Web 04/16/2009

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Bay, South Africa, since 1993.7 This plant is supplied with natural gas and integrates the rening of natural gas liquids with that of the synthetic hydrocarbons from the HTFT synthesis. The process scheme is primarily designed to produce gasoline and smaller amounts of distillates. The rst commercial GTL facility based on cobalt-catalyzed FT synthesis started production in 1993 in Bintulu, Malaysia. On the basis of the Shell middle distillate synthesis (SMDS) technology, this plant typically produces a hydrocarbon spectrum that includes naphtha, kerosene, and distillates.8 Parafn and wax production is optional. The Sasol Oryx GTL plant using Sasol proprietary cobaltcatalyst-based LTFT technology was commissioned in 2006 in Las Raffan, Qatar.9 This technology uses the Sasol slurry phase distillate (Sasol SPD) process to produce mainly diesel fuel and naphtha as byproduct. First products were produced in 2007.10 The products from the 34 000 bpd Oryx GTL plant are similar to those from the SMDS process, since both use a similar rening concept to process a similar FT syncrude. The largest GTL facility (named Pearl) is being constructed by Shell in Las Raffan, Qatar, and will be based on the SMDS process using cobalt-based xed-bed LTFT technology to produce mainly distillate and base oils. Pearl will produce 140 000 barrels a day (bpd) of GTL products and 120 000 boe/d of condensate, liqueed petroleum gas and ethane. An annual output of 90 m barrel of combined products is estimated.11 In the following paragraphs the ow schemes of the abovementioned facilities are presented and, particularly, the distillate production and characteristics are discussed. Specic issues regarding conceptual Fischer-Tropsch fuels rening schemes12 for maximum diesel fuel production are considered; nally, renery concepts are presented that specically address the combined distillate rening of FT heavy ends and coal pyrolysis tar oil heavy ends. 2. Cobalt-based Low-Temperature Fischer-Tropsch (LTFT) Plants in Germany, 1935-1945 During World War II, Germany operated 12 high-pressure coal hydrogenation plants together with 9 LTFT plants to produce 4.5 million tons per annum of motor fuels, 90% of Germanys consumption at that time (Figure 1). The FT diesel was obtained by distillation of the light hydrocarbons from the FT reactors without further hydroprocessing, and as a consequence it contained olens and oxygenates. However, the FT process was at that time of secondary importance for the German fuel economy, producing 9.1% of the total German oil supply.13 The FT gasoline was of poor quality, which could not compete with gasoline derived from coal pyrolysis or coal hydrogenation processes. The outstanding good ignition and sulfur-free quality of the FT diesel oil was, in the German point of view, not
(7) (a) Terblanche, K. Hydroc. Eng. 1997, 2 (2), 24. (b) Steyn, C. The role of Mossgas in Southern Africa. 2nd Subsaharan Africa Catal Symp.; Swakopmund, Namibia, 2001. (8) (a) Sie, S. T. ReV. Chem. Eng 1998, 14 (2), 109. (b) Tim, P. J. A.; Van Wechem, H. M. H.; Senden, M. M. G. The Shell Middle Distillate Synthesis project - new opportunities for marketing natural gas; Alternate Energy 93 Conference, Colorado Springs, USA, April 27-30, 1993. (9) Daya, A. In vogue. Pet. Economist 2006, 73 (4), 27. (10) Anon, Oil Gas J 2007, 105 (5), 10. (11) Pearl GTL- a gem of a project, so long as it works. Pet. Economist; April 8-11, 2008. (12) De Klerk, A. Fischer-Tropsch Rening. Ph.D. Thesis, Dep. Chem. Eng., University of Pretoria, South Africa, February, 2008. (13) U.S. DOD. U.S. Naval Technical Mission in Europe Technical Report No. 248-45. The synthesis of hydrocarbons and chemicals from CO and H2 1945, p 8.

Figure 1. Typical process scheme of the FT plants in 1939-1945 Germany.13 Table 1. Quality of a World War II German FT Diesel14
property density @ 20 C cetane No. cloud point ash point bromine no. aniline point H C O ASTM D-158 distillation IBP 10% 50% 90% FBP units kg m-3 C C g Br2 /100 g C wt % wt % wt % C 193 218 248 291 311 value 768.1 80 0 78 6.9 86.5 15.0 84.9 0.14

Table 2. German WWII Diesel Fuel Specications16

Wehrmacht Sonder diesel diesel Luftwaffe Kriegsmarine Kraftstoff Kraftstoff K1 Treibstoff
810-865 45 -10 -30 55 1.0 810-865 45 -10 -30 21 1.0 810-865 50 -45 50 1.0 880 max none 55 1.0

specication
density @ 15 C, kg m-3 cetane No., min cloud point, C pour point, C, max ash point, C sulfur, wt %

incentive enough to develop an engine that could fully exploit the outstanding 90-100 cetane number. The diesel oil from the FT plants was used to upgrade the diesel fraction from coal tar with cetane numbers of 10-15 to diesel oil having cetane numbers ranging from 40-50. The product quality of a straight-run distillate produced by a cobaltbased FT catalyst is presented in Table 1.14 The diesel fuel was composed largely of linear parafns (88%), about 10% olens, and 2% polar compounds. The high cetane number of 80 is the result of the high n-parafn content of the fuel. The polar fraction contained mainly oxygenates such as carbonyls, alcohols and acids. Table 2 lists German WWII diesel fuel specications
(14) Dancuart, L. P.; de Haan, R.; de Klerk, A. Processing of Primary Fischer-Tropsch Products. In Studies in Surface Science and Catalysis 152; Steynberg, A., Dry, M. Eds.; Elsevier B.V: 2004; p 515. (15) Ward, C. C.; Schwartz, F. G.; Adams, N. G. Ind. Eng. Chem 1951, 43 (5), 11171119. (16) U.S. Navy Technical Mission in Europe, Technical Report No. 187-45, German Diesel Fuels, August 1945, p 3.

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Figure 2. Integration of natural gas in the Carthage Hydrocol HTFT renery (1950-1953). Table 3. Composition of Synthesis Product from the Hydrocol Process
fraction liquid petroleum gas, LPG naphtha (C5-204 C) distillate residue % olenicity 82 85-90 75-85 mass % 32 56 8 4 property
density @ 15 C, kg m-3 cetane No. pour point, C ash point, C (Pensky-Martens) bromine No., g Br2/100 g sulfur, g g-1 oxygen, wt % (by difference) Distillation 10% distilled 50% 90%

Table 4. Straight-run and Hydrogenated (20.7 MPa) Distillate Fuel Fractions by the Hydrocol FT Synthesis18
straight-run hydrogenated
787.9 56 (estd.) -9.4 806.3 71 (detd.) -1.1 71 2 80 0

iron-catalyst-based HTFT cobalt-catalyst-based LTFT straight-run

769.4 78 -1.1

that were achieved by blending fuel oil fractions obtained from the hydrogenation of coal, coke-oven tar or brown-coal tar oils.15 3. Iron-based High-Temperature Fischer-Tropsch (HTFT) Plants (USA) Hydrocarbon Research Inc. developed a HTFT process that was operated during the years 1951-1957, known as the Hydrocol process, which produced hydrocarbons mainly boiling in the petrol range.3,4 The octane rating of the straight-run gasoline was a RON of 62 with a MON of 68.17 By-products were high-grade diesel oil and oxygenated compounds such as alcohols. A 5000 bpsd FT plant operated briey in Brownsville, Texas. The processing scheme used natural gas, and the condensable natural gas was directly blended with the FTderived material (Figure 2). The xed uidized bed (FFB) reactors operated at about 2.1-4.5 MPa and 305-345 C, meaning the process applied was a HTFT process. The distillate fraction was not upgraded any further and reportedly18 had a cetane number of 45-50 and a pour point of less than -9 C. The products from the iron-based HTFT Hydrocol process consisted mainly of hydrocarbons boiling in the C5 to 204 C (naphtha) boiling range (Table 3).17 The hydrocarbons were rich in olens, specically R-olens, while lower amounts of oxygenates and aromatics were also part of the hydrocarbon products.
(17) Bruner, F. H. Ind. Eng. Chem 1949, 41 (11), 25112515. (18) Tilton, J. A.; Smith, W. M.; Hockberger, W. G. Ind. Eng. Chem 1948, 40 (7), 12691273.

47 200 0.30

204 232 304

227 260 327

221 249 288

Distillates from the HTFT Fluidized-bed Hydrocol Process. The hydrogenated liquid products were separated into naphtha, diesel fuel, and a bottoms product. The cut points were selected to give maximum diesel yield with a ash point above 66 C and a pour point of about -4 C. Light hydrocarbons boiling below 204 C were removed from the hydrogenated distillate, which resulted in a distillate density of 806.3 kg m-3 at 15 C (Table 4.) Hydrogenation of this distillate fraction reduced signicantly the olen and oxygenate content but increased the pour point. Nevertheless, a distillate with a high cetane number of 71 was obtained. It has to be noted that the cetane number of the hydrogenated iron-based HTFT distillate is well below that of the cobalt-based LTFT unhydrotreated distillate, which had a cetane value of 78 and indicated a high parafnicity of the latter distillate. 4. The Coal-based Sasol 1 Integrated HTFT-LTFT Plant The rst Fischer-Tropsch facility of Sasol at Sasolburg, South Africa, was, compared to the Hydrocol processing

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Figure 3. Sasol 1 integrated HTFT-LTFT plant in Sasolburg, South Africa (late 1950s).

scheme, more complex. It was the rst integrated plant that combined two variants of the Fischer-Tropsch process, the M.W. American Kellog Co. HTFT process, using circulating uidized bed (CFB) reactors at 2 MPa and 340 C and Germanys xed bed Arbeits-Gemeinschaft Lurgi and Ruhrchemie (ARGE) LTFT process, operating at 2.7 MPa and 230 C. Coal was gasied by Lurgi pressure gasiers using steam and oxygen, with the latter supplied by a Linde oxygen plant. The integration was done to maximize the benets of the unique characteristics of the FT products. Figure 3 shows the original

concept of the integrated nature and the products obtained from the facility operating in the late 1950s.19 Regarding the ARGE products, a rough separation of the FT synthesis product was effected between high- and low-boiling product fractions by partial or stepwise condensation of the reactor products. The reaction product consisted of hydrocarbons ranging from methane to extra-hard parafn waxes. The produced hydrocarbons condense as the temperature drops in the several units of
(19) Hoogendoorn, J. C.; Salomon, J. H. British Chem. Eng. 1957, 238244, 308-312, 368-373, 418-419.

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Figure 4. The LTFT ARGE separation and renery section of the original Sasol 1 integrated FT plant in 1957; the gure has been directly reproduced from ref. 12.

the cooling train of each reactor and are collected separately. By this way of partial condensation a rough separation in boiling ranges was achieved. From the reactor bottom and wax separator a hard wax, called reactor condensate, was obtained. The heat exchanger supplied the hot condensate medium-boiling hydrocarbons and the condenser supplied the cold condensate, the lighter hydrocarbon oils, reaction water, and water-soluble alcohols. Figure 4 shows the principal block ow diagram of the ARGE separation and renery section of the integrated facility, the process scheme of which included 8 separate units. The objective was to produce fuels such as petrol and diesel, but production of LPG and hydrogenated waxes was also included. The necessary synthetic naphtha quality was achieved by xed-bed rening at 400 C, thereby converting the oxygenates to parafns and shifting the double bond of the olens to the internal position. This improved fuel stability and octane number. The diesel was a blend of straight-run FT products and cracked stock from the thermal cracker, which diesel therefore contained olenic and oxygenated hydrocarbons. The wax streams were hydrogenated in xed-bed reactors over a nickel catalyst to saturate the small amounts of olens and oxygenates present. The Kellogg HTFT products recovery section can broadly be divided into two subsections, the hydrocarbon and the chemicals recovery section.19 The gasoline, distillate, and fuel oil fractions are obtained by essential ash distillations. Oxygenates and specically the acids were intermediately removed by routing the liquid streams boiling <343 C over a reactor containing silica-alumina beds, which at the same time achieved isomerization of the hydrocarbons and imparted a higher octane rating to the petrol portion. The heavy oil was essentially unaffected by this oil-treating process. During cooling of the gas from coal gasication, a large quantity of condensate separated out. This stream contains gas liquor, light aromatic oil, and tar. The ratio of water to tar in the condensate stream was high, and the composition was typically 98.3% water, 0.3% oil, and 1.4% tar. The gas liquor contained on average 0.85% ammonia and 0.15% tar acids. Those tar acids, after residual tar and oil were separated by gravity and sand ltration, were recovered by the phenolsolvan

process using a butyl acetate extraction.20 The tar and the light oil were worked up in a tar renery. The overheads, water and oil, from a rst atmospheric distillation unit (ADU) were separated, and the oil passed over a hydrogenation unit primarily to desulfurize the oil fraction. The bottoms of the ADU were routed to a vacuum tower that fractionated the ADU bottoms into an overhead and side stream of creosote and road tar prime, respectively, and a bottoms product of pitch. The creosote, tar, and pitch were sold as such. The aromatic-rich raw gas naphtha from the Rectisol gas purication, separated from the prewash methanol, was routed together with the overheads from the ADU from the tar renery to a naphtha hydrotreater. Gum-forming material and phenol, but also sulfur, were removed in this gas-phase hydrotreater. The hydrogenated naphtha was, after an alkali and water wash, fractionated in a petrol grade fraction, a fraction containing benzol, toluol, and xylenol, a neutral creosote fraction, and a heavy naphtha fraction; those latter fractions were sold as solvents (Figure 3). In the following years, the Kellogg HTFT process and the catalyst were improved by Sasol, which nally resulted in the Sasol HTFT Synthol process. Table 5 compares the straightrun FT products from the ARGE and Synthol process and highlights some properties of the fuel fractions.21,22 The olenicity of individual carbon numbers is much higher with regards to the HTFT product, and the carbon number distributions are also different. HTFT products are more branched and contain aromatics, whereas no aromatics are found in LTFT products. Because of the basic FT catalytic growth mechanism it is inevitable that a wide spectrum of carbon numbers is always obtained with the commercially applied FT synthesis. Straightrun distillate yield was ranging between 10 and 20 mass %, and in order to maximize the overall distillate yield, secondary processes were applied such as hydrocracking and C3/C4 olen oligomerization. The olen content of the FT synthesis product
(20) Hoogendoorn, J. C.; Salomon, J. H. British Chem. Eng. 1957, 368 373. (21) (a) Hoogendoorn, J. C.; Salomon, J. H. British Chem. Eng. 1957, 418419. (b) Jager, B.; Kelfkens, R. C.; Steynberg, A. P. A slurry bed reactor for low temperature Fischer-Tropsch. In: Natural Gas ConVersion II; Hyde, H. E., Howe, R. F. Eds.;Elsevier: 1994; 419-425. (22) Dry, M. E. Hydrocarbon Process. 1982, 121124.

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Table 5. Selectivity on Carbon Basis for Straight-run FT Products from the LTFT ARGE and HTFT Synthol Process21

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and Selected Properties of the Naphtha (C5-C10) and Diesel Cut (C11-C18)22
product fraction, mass % ARGE xed-bed, LTFT 4 4 4 18 19 48 3 32 60 (95) 0 7 0.6 0.4 25 65 (93) 0 6 <1 0.05 75

Sasol Synthol CFB, HTFT 7 24 6 36 12 9 6 65 14 (55) 10 6 6 2 73(60) 10 10 4 2 2 55

C1 C2-C4 olens C2-C4 parafns C5-C10 (naphtha) C11-C22 (diesel) C23+ (heavy oil and wax) water-soluble oxygenates Naphtha olens parafns (n-parafns) aromatics alcohols ketones acids Diesel olens parafns (n-parafns) aromatics alcohols ketones acids cetane No.

Table 6. Typical C5-C12 and C13-C18 Product Spectra (mass %) for LTFT (xed-bed, slurry) and HTFT (Synthol)12
xed-bed compounds parafns olens aromatic oxygenates n-parafns 53 40 0 7 95 65 28 0 7 93 29 64 0 7 96 slurry 44 50 0 6 95 13 70 5 12 55 HTFT 15 60 15 10 60 C5-C12 C13-C18 C5-C12 C13-C18 C5-C12 C13-C18

reported in the early 1980s.24,25 The straight-run diesel fuel from a LTFT operation (slurry and xed-bed) typically has a cetane number of 75-80, whereas the diesel hydrocracked from LTFT wax has a cetane number of about 70-75. Figure 5 depicts a process scheme26 that targets to maximize diesel fuel production based on LTFT synthesis. Almost two-thirds of the nal diesel comes from the wax hydrocracker distillate when the bottoms fraction is recycled to extinction. About one-third of the diesel would come from the fractionation of the hydrotreated LTFT condensate fraction. The inclusion of an oligomerization unit for the conversion of light olens to fuel boiling range hydrocarbons can add some 7% of distillate to a scheme where this option is excluded. The distillate derived from such oligomerization using, for example, C3-C6 olens is highly branched and consequently has a low cetane number. Advantageous is that all distillates are essentially free of nitrogen and sulfur and only small amounts of aromatics (<0.5 wt %) are present in the distillate from the wax hydrocracker. The nal diesel density is, however, low due to its high parafnicity and ranges between 760-780 kg m-3 at 15 C. The benet of the high cetane number of those FT distillates is that other low-quality diesel fuels can be blended into the diesel pool. The highly branched distillates produced from the shortchain olen oligomerization have low cetane numbers (about 30) and are therefore an ideal blending component for the FT distillates that have high cetane numbers of over 70. Those blends still maintain the advantage of being sulfur-, nitrogenand almost aromatic-free, having high cetane numbers (about 60-65) but lacking density, which is the only diesel fuel specication those blends will not achieve. 5. HTFT Plants and Diesel Producing Schemes, 1980 to Present Figure 6 shows the simplied ow scheme of the 2004 coalbased Sasol HTFT Synfuels plant in Secunda, South Africa, which was built in the late 1970s and early 1980s. Several major differences involve product separation and workup units. The tail gas is cryogenically separated into various components that enable C2 and C3 extraction. Unlike the original Sasol 1 plant at Sasolburg, where petrol was directly blended into petrol derived from crude oil, the Synfuels naphtha is reformed after removal of oxygenates and olens over a platformer for octane improvement. The Sasol Synfuels Secunda process scheme was conceived to maximize petrol production and includes a C3/C4 oligomerization unit to increase the petrol pool. After 1990, recovery of linear C6 to C8 R-olens was introduced. This was later followed by the extraction of heavier R-olens, which are puried for detergent alcohol production using the hydrofromylation reaction. Diesel production is part of the FT renery and is mainly achieved by hydroprocessing. Because FT syncrude products are free of sulfur and nitrogen, the main upgrading reactions involved are olen saturation, hydrodeoxygenation (HDO), and to a minor extent hydrodearomatization (HDA). As is shown in Figure 6, the coal-based HTFT Synfuels plant requires, in addition to the FT renery, a tar renery to process the pyrolysis products from the xedbed dry bottom (FBDB) gasication.
(24) Dry, M. E. The Sasol Fischer-Tropsch Processes. In: Applied Industrial Catalysis; Leech, B. E. Ed.; 1983; Vol. 2, Ch. 5, pp 167213. (25) Dry, M. E. ChemSA 1981, 286288. (26) Dancuart, L. P.; Steynberg, A. P. Fischer-Tropsch based GTL Technology: a New Process? In: Studies in Surface Science and Catalysis; Davis, B. H., Ocelli, M. L. Eds.; Elsevier: 2007, Vol. 163, pp 379-399.

is high, specically that of the HTFT process, which makes it obvious to apply olen oligomerization to increase the diesel pool. In the case of the LTFT process, waxes are the major product fraction, therefore wax hydrocracking is the appropriate process to maximize diesel yields. In addition to these two FT synthesis processes, slurry bed reactors systems can be applied. Kolbel et al.23 of the Technical University of Berlin did considerable work in this eld in the 1950s to the late 1970s. Sasols work on slurry started in the early 1980s, and in 1993 a slurry bed reactor (5 m nominal diameter) was commissioned using an iron-based catalyst that replaced the CFB units. The slurry bed reactor (SBR) is operated such that its product slate closely matches that of the xed-bed reactor; however, differences can be noted (Table 6). The composition is typical but not necessarily representative of process conditions optimal for conversion or wax selectivity or quality. However, Table 6 shows that the LTFT slurry synthesis product is much more olenic and contains less parafnic material than the xed-bed product. If a cobalt-based catalyst were used instead of the iron-based catalyst, then the olenicity of the product would be even lower. The process scheme changed once more in 2004 when coal gasication was changed by natural gas reforming, thus transforming the Sasol 1 plant at Sasolburg essentially into a GTL plant, producing waxes and chemicals rather then synthetic fuels. Maximum LTFT Diesel Fuel Production Schemes of the 1980s. Production schemes to maximize FT diesel fuel were
(23) Kolbel, H.; Ralek, M. Catal. ReV.-Sci. Eng. 1980, 21 (2), 225 174.

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Figure 5. Maximum LTFT diesel producing scheme.

As listed in Tables 5 and 6, the olen content of the HTFT syncrude is far higher compared to that of the LTFT synthesis; therefore, olen oligomerization plays a major role in a HTFT plant. The olens can be processed according to three processes: thermal polymerization via a free radical mechanism, acidcatalyzed processes using amorphous catalysts, and acidcatalyzed processes using zeolite-based catalysts. The thermal process produces a distillate that is fairly linear with cetane numbers around 50-60. However, compared to the catalytic processes, higher temperature and pressure and also a lower space velocity have to be applied. The distillate from a zeolite-based (i.e., ZSM-5 zeolite) oligomerization process has, despite being more branched, a cetane number of about 50.25,27 The molecules are mainly methyl-branched due to the catalysts pore structure, which results in a fairly high viscosity product (about 3.0 cSt at 40 C). Acid catalysts such as phosphoric acid on kieselguhr (CatPoly), originally developed by UOP, produce a highly branched distillate (C10-C14) with low cetane number values of about 30 (34 after hydrogenation) by recycling the gasoline back to the reactor. Overall distillate yield can be as high as 75%. This CatPoly distillate has, because of its highly branched nature, a low viscosity (1.8 cSt at 40 C), but its cold ow properties are outstanding. The amount of this diesel that can be blended to achieve a cetane number of, for example, 51, depends very much on the quality of the other distillate blend component. The FT process itself produces predominantly straight-chain products, therefore the quality of the distillate is high. The cetane number of the straight-run HTFT distillate is about 53. The Sasol HTFT Synfuels plant is geared to maximize petrol via short chain olen oligomerization rather than maximizing
(27) Dry, M. E. The Sasol Route to Chemicals and Fuels. In: Methane ConVersion; Bibby, D. M., Chang, C. D., Howe, R. F., Yurchak, S. Eds.;Elsevier B.V.: Amsterdam, 1988; pp 447-456.

distillates. This original HTFT plant design was the result of geopolitical- as well market-related circumstances. The dieselto-petrol ratio can vary in the range of 35/65 to 40/60. Fuel specications in the 1980s were not very demanding; therefore, the renery design does not reect the prevailing fuel specications. The complex CFP reactors were replaced in the 1990s by more energy efcient Sasol advanced Synthol (SAS) reactors developed by Sasol. Advantages over the CFB reactors are well documented.28 The product selectivities29 (Tables 7 and 8) from the SAS reactors are similar to those from the CFB reactors (Tables 1 and 2) due to the fact that the same catalyst composition is used. The more isothermal operation of the SAS reactors results in slightly lower methane selectivity. Although more and more olens are extracted at the HTFT Synfuels renery, most of the production volume to date still goes into fuels. The composition of the primary HTFT products (Table 7) highlights what is typical of HTFT rening. The oil product low in heteroatoms such as sulfur and nitrogen is rich in olens (predominantly R-olens); the oil is poor in aromatics and naphthenic hydrocarbons but contains percentage levels of oxygenates. The oil product is mainly linear and follows a Schulz-Flory distribution heavily weighted toward lighter hydrocarbons as opposed to a LTFT synthesis product. 6. Rening Fischer-Tropsch Syncrude Heavy Ends and Pyrolysis Tar Oil in a Coal-based HTFT Synfuels Plant FT Distillate Rening. The distillate (C11-C22) and residue (>360 C boiling material) fractions of the HTFT syncrude make up about 10% of the total products from the Fischer-Tropsch synthesis. The residue fraction is consequently quite small (3-4% of the total primary product), and an atmospheric
(28) Jager, B.; Dry, M. E.; Shingles, T.; Steynberg, A. P. Catal. Lett. 1990, 7, 293. (29) Steynberg, A. P.; Espinoza, R. L.; Jager, B.; Vosloo, A. C. Appl. Catal., A 1999, 186, 4154.

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Figure 6. Coal-based HTFT facility with xed-bed dry bottom (FBDB) gasication and separate FT and tar renery (Sasol Synfuels Renery 2004, Secunda, South Africa); CTN: coal tar naphtha, DHT: distillate hydrotreater, DU: distillation unit, HP: high pressure, HT: hydrotreater. Table 7. Selectivity on Carbon Basis for the SAS Reactors12
product methane C2-C4 olens C2-C4 parafns gasoline middle distillate heavy oils and waxes watersoluble oxygenates % 7 24 6 36 12 9 6

Table 8. Selectivity (Hydrocarbon Type) for the SAS Reactor12

product, % parafns olens aromatics oxygenates C5-C10 13 70 5 12 C11-C14 15 60 15 10

distillation unit (ADU) is all that is required for primary product separation. A separate vacuum distillation unit (VDU) is included in the renery design of the Sasol HTFT Synfuels facilities (Figures 6 and 7) to avoid potential problems that are associated with thermal cracking in the reboiler of the ADU.

The olens and oxygenates present in the HTFT syncrude are susceptible to thermal decomposition when the reboiler temperature exceeds 300-320 C. The distillate and residue fractions are contained in two streams from the HTFT synthesis, namely the stabilized light oil (SLO) and the decanted oil (DO). The DO is the heaviest fraction, and it consists mainly of residue material and some catalyst nes that have not been removed by the cyclones in

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Figure 7. Operation of the HTFT heavy-end syncrude conversion and separation units in the Sasol Synfuels facilities at Secunda, South Africa (2008). The vacuum gas oil, in practice, comprises of two fractions, a light vacuum gas oil (LVGO) and a heavy vacuum gas oil (HVGO) that are combined for further hydroprocessing.

the Fischer-Tropsch synthesis reactors. This product is knocked out after the feed-product heat exchanger of the synthesis reactors, which partially condenses some of the heavier products. The SLO is recovered after further cooling and contains distillate and residue. The SLO and DO fractions are both ash separations and should be viewed as rough splits that result from the design of Fischer-Tropsch product cooling, rather than intentional product separation steps. The HTFT distillate and residue cuts are different in composition from the predominantly linear parafns and waxes that are found in the equivalent LTFT cuts. It contains a signicant amount of aromatics (but little polynuclear aromatics), oxygenates, and olens, but as in the LTFT syncrude, it is almost sulfur and nitrogen-free. In the case of HTFT distillate, it is olens and oxygenates that are the major compound classes to be saturated. Less severe hydrotreating conditions are required, although olens and oxygenates are capable of highly exothermic reactions. An important consideration in HTFT distillate rening is the product density, which is too low, on account of the low aromatic content of HTFT distillate. These and other important aspects will be highlighted during the further discussions. The HTFT residue fraction is comparatively clean, apart from some iron that is present as iron carboxylates. The HTFT residue can be hydrocracked to distillate and naphtha, or it can be dewaxed to produce base oils;30 however, hydro-dewaxing is the preferred process in the present HTFT Secunda Synfuels facility. Because the HTFT distillates have an inherently low density, preservation of aromatics in the Synfuels facility for inclusion in the nal diesel pool is highly desirable. Rening of FBDB Gasication Derived Pyrolysis Tar Oil. The feed to the tar distillation unit (Figure 8) consists of phenolic pitch, after phenol extraction in a phenosolvan unit, crude tar oil from a coal tar ltration unit and the recycle stream (residue oil) from the coal tar naphtha hydrogenation. A typical product distribution from tar distillation consisted of six fractions, namely, light naphtha (10%), heavy naphtha (8%), medium creosote (25%), heavy creosote, (13%), residue oil (5%), and pitch (39%). The light naphtha, heavy naphtha, and Rectisol naphtha from the Rectisol unit are combined to serve as feed for the coal tar naphtha (CTN) hydrogenation unit. In this unit the feed is
(30) Leckel, D. Energy Fuels 2009, 23, 3845.

preheated and ashed to separate the naphtha range material from the heavier boiling material at around 210 C. The heavier material, called residue oil, is recycled to the tar distillation unit, while the naphtha vapor is hydrotreated at 5 MPa pressure. The hydrogenated naphtha consists of mainly parafns and aromatics, but with low octane number (typically around 80), and it is used as a fuel-blending component. The medium creosote, heavy creosote, and residue oil from the tar distillation unit are combined and hydrogenated at high pressure (18.5 MPa) in a creosote hydrotreater that consists of four reactors in series. The product is a mixture of hydrogenated naphtha and distillate. The creosote distillate is an important blending component, since it is the main source of diesel density in the HTFT Synfuels renery.29 The pyrolysis liquids have a low hydrogen-to-carbon ratio and high nitrogen, oxygen, and polynuclear aromatic concentrations. Similar compositions are found in liquids derived from direct coal pyrolysis.31 Due to the high levels of nitrogen, phenolic compounds, and polynuclear aromatics, severe hydroprocessing conditions are necessary, and consequently, hydrogen consumption in these coal tar naphtha and creosote hydrogenation units is typically high. The high hydrogen pressures and low space velocities applied for the hydroprocessing of the distillate boiling coal pyrolysis liquids favor heteroatom removal.32 Nitrogen (<15 ppm), sulfur (<1 ppm), and phenolics levels (<100 ppm) obtained in the nal tar oil distillate of the Sasol HTFT Synfuels plant are low; however, density remains relatively high (870-880 kg m-3).32 Properties of Hydrotreated HTFT and Pyrolysis Tar Oil Distillates. The hydroprocessing of straight-run HTFT distillate over sulded NiMo/Al2O3 catalysts yields product characteristics that are shown in Table 9. The moderate pressures of 5.0 MPa does not favor monoaromatic saturation and more severe process conditions are required, specically higher operating pressures and temperatures combined with low space velocities to achieve the hydrogenation of monoaromatics.33 The products from HTFT straight-run distillate hydrotreating are naphtha and mainly diesel. The naphtha product results from the hydrodeoxygenation reaction, which shifts the oxygenates
(31) Teo, K. C.; Watkinson, A. P. Fuel 1990, 69 (10), 12111218. (32) (a) Leckel, D. Energy Fuels. 2006, 20, 17611766. (b) Leckel, D. Energy Fuels. 2008, 22, 231236. (33) (a) Cooper, B. H.; Donnis, B. B. L. Appl. Catal., A 1996, 137, 203. (b) Girgis, M. J.; Gates, B. C. Ind. Eng. Chem. Res. 1991, 30, 2021.

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Figure 8. Tar workup section at Sasols HTFT Synfuels plant at Secunda, South Africa. Table 9. Selected Properties of HTFT Distillate Hydrotreated over a NiMo/Al2O3 Catalyst at 5.0 MPa30
hydrotreated HTFT distillate 63 804.1 2.29 546 74 -1 -2 378 381 0.004 1.18 <1 <1 22.44 22.20 0.24 not detected EN590-Euro 4 diesel fuel specication 51 min 820-845 2.0-4.5 460 max 62 min
a a

Table 10. Comparison of Properties of Hydrotreated Pyrolysis Tar Oil Distillate and HTFT Distillate30
property density at 15 C, kg m-3 viscosity at 40 C, cSt HPLC-aromatics, mass % monoaromatics diaromatics polycondensed aromatics cetane number CFPP, C cloud point, C phenolics, mg kg-1 nitrogen, mg kg-1 sulfur, mg kg-1 pyrolysis tar oil distillate 887.3 2.33 25.50 24.0 1.20 0.30 38 -7 -2 58 6 <1 HTFT distillate 804.1 2.23 22.45 22.2 0.24 <0.01 63 -2 -1 <1 <1 <1

properties cetane No. density at 15 C (kg m-3) viscosity at 40 C (cSt) lubricity, HFRR (m) ash point (C) cloud point (C) cold lter plugging point (C) T95 distillation point (C) nal boiling point (C) acid content (mg KOH/g) olen content (g Br2/100 g) N (g g-1) S (g g-1) total aromatic by HPLC (mass %) mononuclear dinuclear polynuclear
a

360 max

10 max

11 max

Dependent on climate.

initially boiling in the distillate range into the naphtha range. The naphtha with a nal boiling point below 190 C has a RON in the range of 35-40 and has therefore to be further upgraded, typically by catalytic reforming. The hydrotreated HTFT distillate has a cetane number in the range of 55-65, mainly as a result of its high linear parafn content and low concentration of polycyclic aromatics. The bulk of aromatics are predominantly long chain alkylbenzenes that, due to their high parafnicity, also have a high cetane number. HTFT distillates are clean fuels, low in sulfur and nitrogen (<1 ppm), but due to its parafnicity lack density compared to crudeoil-derived diesel.

Distillates derived from HTFT synthesis have a lower density compared to gasication-tar-derived distillate despite the same level of total aromatics (Table 10). The cetane number of the pyrolysis tar oil distillate is low compared to the FT distillate.33 The FT distillate is mainly parafnic with the aromatics in the distillate being predominantly monoaromatics. Those aromatics structures are particularly alkylated benzenes carrying a long alkyl side chain and hydroaromatics in the form of indans and tetralins. The levels of naphthalenes or anthracenes in a hydrotreated HTFT distillate are generally below 0.50 mass %. The hydrotreated pyrolysis tar oil distillate is mainly naphthenic (hydroaromatics). Blending Opportunity of HTFT and Pyrolysis Tar Oil Distillates. The complementary nature of the properties of the hydrotreated HTFT and FBDB gasication-derived tar distillates is advantageous. The tar distillate redresses adequately the main shortcoming of the HTFT distillate, namely density (Figure 9). Figure 9 illustrates the blending of a HTFT distillate with a gasication-tar-derived distillate, both distillates hydroprocessed

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Figure 9. Blending a HTFT distillate with density of 804.1 kg m-3 with a FBDB gasication-derived tar oil distillate having a density of 887 kg m-3. EN590-Euro 4 minimum diesel density specication at 15 C is achieved at a blend ratio of 20% tar oil to 80% HTFT distillate. Table 11. Selected Fuel Properties of a Typical Final Synfuels HTFT Diesel Blend Commercially Marketed by Sasol in South Africa30
analysis units method ASTM D4052 ASTM D86 commercial nal diesel 829 178 200 240 361 374 70 2.23 -1 <1 53 0.4 567 307 42.8 35.3 36.8

density @ 15 C kg m-3 distillation IBP C T10 C T50 C T95 C FBP C ash point C viscosity @ 40 C cSt CFPP C sulfur mg kg-1 cetane No. oxidation stability mg (100 mL)-1 HFRR WSD m HFRR WSD @ 250 g/g m lubricity improver net heating value MJ kg-1 MJ l-1 total aromatics mass %

gas coming from an off-shore gas eld. There are two main renery sections, the oil workup section taking care of the all hydrocarbons and the aqueous phase workup section rening the water-soluble oxygenates. Integration features of the plant are the combined upgrading of the natural gas liquid derived naphtha with the synthetic FT naphtha and the combined rening of the natural gas condensates with the synthetic FT distillates (Figure 10).12,26 A key unit for distillate production in the renery is the oligomerization unit that uses the conversion of olens to distillate (COD) process that was specically developed for the upgrading of FT olens to diesel. The process was designed in South Africa by the Central Energy Fund (CEF) and Sud-Chemie using a ZSM-5 zeolite catalyst (Sud-Chemie COD 9).34 The mixture of olens is converted in three reactors. One reactor can be taken off-line for in situ catalyst regeneration by controlled carbon burnoff. Distillate of high quality (cetane numbers of 48-54) but low density (800 kg m-3 at 15 C) is produced.28,35 The distillate hydrotreater (DHT) hydrogenates the COD distillate together with the distillate of the SLO distillation to produce diesel and kerosene. The straight-run distillate from the NGL recovery is combined with the hydrotreated product to produce a nal diesel. The PetroSA diesel fuel formulations have CFPP values typically in the range of -20 C and lower due to the large portion of iso-parafns present. Aromatic content generally is less than 18%, with the bulk of the aromatics being single ring monoaromatics. 8. The Shell LTFT Gas-to-Liquids Plant (Bintulu, Malayia) Shells rst commercial GTL facility based on the Shell middle distillate synthesis (SMDS) technology was the 12 500 bpd plant commissioned in Bintulu, Sarawak, Malaysia in 1993. It was partly destroyed by an explosion in the air separation unit in December 1997. A new air separation unit was constructed, and the plant was recommissioned in May 2000. It has been in operation without problems since then. Shell developed its LTFT technology based on the SMDS process. The process consists of three major steps, namely, the synthesis gas generation from natural gas, heavy parafn synthesis (HPS) using the generated syngas, and heavy parafn conversion (HPC) to middle distillates.36 Maximum distillate production is achieved by rst using the Fischer-Tropsch reaction to produce heavier products (high R-value), which then is selectively cracked to the desired carbon number range. The Shell Co LTFT catalyst development resulted in a catalyst producing an R-value of around 0.90 and higher, while synthesis gas conversion between 80-95% with a C5+ product selectivity in the range 85-95% have been reported.37-39 A simplied ow scheme of the SMDS plant in Bintulu is shown in Figure 11. It is a two-stage process converting synthesis gas into middle distillates. The hydrocracker in the HPC step is operated in the range of 300-350 C and 3-5 MPa with a Shell proprietary noble metal hydrocracking catalyst.38 In the HPC stage the olens and oxygenates are removed by hydrogenation, and the resulting parafnic hydro(34) Minnie, O. R.; Petersen, F. W.; Samadi, F. R. The effect of 1-hexene extraction on the COD process conVersion of olens to distillates. South African Chem. Eng. Congr.: Sun City, South Africa, 2003. (35) Knottenbelt, C. Catal. Today 2002, 71, 437. (36) Sie, S. T.; Senden, M. M. G.; Van Wechem, M. M. M. Catal. Today 1991, 8, 371394. (37) Dry, M. E.; Steynberg, A. Stud. Surf. Sci. Catal. 2004, 152, 406. (38) Smith, R.; Asaro, M. Fuels of the future. Technology Intelligence for Gas to Liquids Strategies; SRI: Menlo Park, CA, 2005.

ASTM ASTM IP 309 ASTM ASTM ASTM ASTM

D93 D445 D5453 D613 D2274 D6079

ASTM D240 ASTM D6591

at the Sasol Synfuels renery at Secunda, South Africa. This example shows that a HTFT distillate of 804 kg m-3 density can be blended with about 20 vol % of a gasication tar derived distillate with a density of 887 kg m-3 to achieve the EN590Euro 4 minimum density diesel fuel specication. Table 11 shows typical properties of a nal HTFT Synfuels diesel blend commercially marketed by Sasol in South Africa, which includes 71 vol % of a HTFT light distillate fraction, 25 vol % of a gasication-tar-derived distillate, and 4 vol % of a HTFT heavy distillate fraction.30 The nal blended diesel fuel properties comply with the EN590-Euro 4 diesel fuel specications meeting a summer grade B cold lter plugging point (CFPP). The integration, therefore, of a tar renery into an FT plant creates opportunities for fuel processing and in downstream fuel blending. 7. The PetroSA HTFT Gas-to-Liquids Plant The PetroSA facility at Mossel Bay, South Africa, is based on the HTFT Synthol technology developed by Sasol and has been in operation since 1993. This plant is supplied with natural gas (NG) and integrates the rening of natural gas liquids (NGL) with that of the synthetic hydrocarbons from the HTFT synthesis. The process scheme is primarily designed to produce gasoline and smaller amounts of distillates. The syngas for the FT synthesis using a fused iron catalyst is produced from natural

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Figure 10. Oil work-up at PetroSA renery, Mosselbay, South Africa.

Figure 11. Simplied ow scheme of the Shell LTFT GTL plant at Bintulu, Malaysia.

carbons are hydroisomerized and hydrocracked into the desired boiling range. The product is fractionated and the unconverted wax-fraction can either be sold as a wax or recycled to the hydrocracker. The product selectivity can be inuenced by varying the single-pass conversion.39 Depending on the hydrocracking severity, the product composition can be varied from 15% lights and naphtha, 25% kerosene, and 60% gas oil (distillate) in gas oil mode, to 25% lights and naphtha, 50% kerosene, and 25% gas oil in kerosene mode. Some typical product properties are given in Table 12.40,41 Although the wax, parafns, and LPG can be sold as nal products, the marketing of the fuel products

depend on Shells ability to blend it with the products from their crude oil reneries to meet fuel specications. 9. The Sasol Oryx LTFT Gas-to-Liquids Plant in Qatar The 34 000 bpd Oryx GTL plant at Las Raffan, Qatar, uses LTFT technology that is based on the Sasol SPD process. The SPD process uses a Co-based Sasol proprietary catalyst typically operating at 230 C and 2.5 MPa. The basic renery design (Figure 12) is very similar to that of the Shell Bintulu renery. The renery section receives two feed streams, namely wax and condensate that are combined to serve as feed to the hydrocracker. The hydrocracker uses

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Table 13. Typical Properties of a Hydrocracked Distillate of the Sasol SPD Process
property G100 779 310 (at 90%) 1.4 75 (cetane No.) 0.0003 43.6 density @ 15 C, kg m-3 boiling range, C cetane No. CFPP ash point, C total aromatics, wt % viscosity @ 40 C, cSt lubricity, HFRR WSD, m sulfur, mg kg-1 Net heating value, MJ kg-1(MJ L-1) distillate 769 151-334 73 -19 58 0.1 2.0 617 <1 43.79 (33.65)

Table 12. Typical Kerosene and Gas Oil Properties of the Shell LTFT GTL Plant in Malaysia40,41 and Properties of a GTL Test

Fuel G100 (Shell Int. Gas Ltd.)42

property density @ 15 , kg m-3 boiling range, C (ASTM D86) total aromatics, wt % cetane index sulfur, wt % lower heating value, MJ kg-1 smoke point, mm ash point, C freezing point, C kerosene 738 155-191 <0.1 58 >50 42 -47 gas oil 776 184-357 <0.05 76

ChevronTexaco isocracking technology with a Chevron proprietary hydrocracking catalyst, which is a commercially available sulded base metal catalyst on an acidic support. Typical operating conditions are 350 C and 7 MPa, with the temperature being adjusted to maintain a per pass conversion of around 60%. The product from hydrocracking is distilled to produce LPG (3-7%), naphtha (20-30%), and distillate (65-75%), with the unconverted >360 C waxy product being recycled back to the hydrocracker.43 The reaction water is separated by distillation into an alcohol-rich overheads product that is incinerated and a carboxylic-acid-containing water product that is biologically degraded to purify the water. No oxygenates are recovered from the reaction water. The distillate is sold as transportation fuel blend stock, whereas the naphtha can be marketed as steam cracker feed since it has a poor octane value RON (50-55).44 Typical properties of a Sasol SPD distillate are listed in Table 13.45 The distillates contain virtually no heteroatoms and have an almost zero aromatic hydrocarbon content. This results in a high cetane number (above 70) but a low density, which is the major reason that LTFT-derived distillate is not able to meet diesel fuel specications. These excellent fuel properties contribute to the clean combustion of the LTFT diesel but to the loss of volumetric heating value. The distillate can exhibit a range of cold ow properties, depending on the hydrocracking severity. Lubricating properties are poor, but with addition of

lubricity improvers an acceptable level of lubricity performance can be achieved. 10. Conceptual Fischer-Tropsch Renery Designs Some conceptual FT renery designs to maximize diesel fuel production were developed by A. de Klerk.12 Both hightemperature and low-temperature Fischer-Tropsch technology were considered. Distillates from HTFT and LTFT are essentially sulfur-free and have a low aromatic content and a high straight-run cetane number.39,46,47 It was demonstrated that LTFT or GTL diesel compared to CARB or Swedish EC1 diesel produced the lowest regulated and unregulated exhaust emissions.48 The excellent fuel properties of a LTFT diesel contribute to a clean combustion but also to a loss of volumetric heating value.49 There is, however, the one diesel fuel specication that is not easily met by FT diesel, and that is density (820-845 kg m-3 at 15 C). The density of a hydrocracked LTFT distillate typically ranges between 760 and 780 kg m-3 due to only negligible amounts of aromatics and high parafnicity.45 A hydrotreated HTFT distillate30 contains, on the other hand, some aromatics, mainly monoaromatics, which results in a density between 804 and 813 kg m-3. With regards to maximum diesel production in a LTFT facility, cetane number (>70) or volume (due to the high R-value

Figure 12. Simplied process ow diagram of the Sasol Oryx GTL plant at Las Raffan, Qatar.

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Figure 13. Coal-based HTFT plant with FBDB gasication and integrated FT and tar heavy end rening; SDA: solvent deasphalting.

in the FT synthesis step) is not the issue but rather density. The constraint in a HTFT facility targeting maximum diesel production is the volume (due to the lower R-value in the FT synthesis step) rather than density or cetane. The distillate fraction in the straight-run HTFT syncrude is about 8%. This property relationship regarding the LTFT and the HTFT distillate is referred to by De Klerk in his thesis12 as the densitycetane-yield triangle. It is possible to meet any two of the mentioned three properties without too much rening effort, but meeting all three is very difcult. The conceptual FT renery studies conrmed that it is possible to produce on-specication motor-gasoline and jet fuel in a Fischer-Tropsch renery, but that Fischer-Tropsch syncrude is not suited for the production of on-specication diesel fuel. It was concluded by de Klerk that HTFT and LTFT syncrude is on a molecular level unsuited for maximizing Euro 4 type diesel fuel production, but is best achieved by blending the syncrude-derived distillate with material form other sources such as coal pyrolysis products or crude oil.
(39) Eilers, J.; Posthuma, S. A.; Sie, S. T. Catal. Lett. 1990, 7, 253. (40) Tijm, P. J. A. Prepr. Pap.-Am. Chem. Soc., DiV. Fuel Chem 1994, 39 (4), 1146.

11. Integrated Rening of FT and FBDB Gasication-Derived Heavy Fractions Revisiting the complexity of a Sasol HTFT Synfuels facility it is obvious that reducing the number of processing units could reduce complexity and could also reduce capital costs of an alternative type of Synfuels renery design. Instead of rening FT and gasication-derived pyrolysis tar oil heavy ends separately, the combined upgrading of those heavy ends was
(41) Schrauwen, F. J. M. Shell Middle Distillate Synthesis (SMDS) process. In: Handbook of Petroleum Rening Processes; Meyers, R. A. Ed.; Mc-Graw-Hill: New York, 2004; pp 15-25. (42) Wu, T.; Huang, Z.; Zhang, W.-G.; fang, J.-H.; Yin, Q. Energy Fuels 2007, 21 (4), 19081914. (43) Dancuart, L. P.; De Haan, R.; De Klerk, A. Stud. Surf. Sci. Catal. 2004, 152, 482. (44) Dancuart, L. P.; Mayer, J. F.; Tallman, M. J.; Adams, J. Prepr. Pap.-Am. Chem. Soc., DiV. Pet. Chem 2003, 48 (2), 132. (45) Lamprecht, D.; Dancuart, L. P.; Harrilall, K. Energy Fuels 2007, 21 (5), 2862852. (46) Ward, C. C.; Schwartz, F. G.; Adams, N. G. Ind. Eng. Chem. Res. 1951, 43 (5), 11171119. (47) Cookson, D. J.; Smith, B. E. Energy Fuels 1992, 6 (5), 581585. (48) Fanick, E. R.; Schubert, P. F.; Russell, B. J.; Freeks, R. L. Comparison of emission characteristics of convetional and, hydrotreated and Fischer-Tropsch diesel fuels in a heavy duty diesel engine; SAE Tech. Pap. Ser. 2001, 2001-01-3519.

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Figure 14. Coal-based LTFT plant with FBDB gasication and integrated FT and tar heavy end rening; HC: hydrocracker.

considered. This processing scheme is, to date, not commercially practiced but could potentially be incorporated in future FT plants producing on-specication diesel fuels. Figure 13 is a proposal of such a less complex renery scheme. Since heavy ends from the HTFT synthesis and gasication derived pyrolysis tar oils might potentially contain solids from the FT synthesis catalyst and the coal gasication process (i.e., ash or char), the heavy end upgrading unit of those proposed FT facilities would typically employ an ebullated or slurry bed hydrocracker. Slurry bed hydrocracking studies to convert the heavy coal pyrolysis fraction boiling above 360 C into liquid fuel fractions were conducted at Sasol in the years 1984 to 1987 at Sasols research and development pilot plant facilities at Sasolburg. It was established that those heavy fractions could successfully be converted to liquid fuel fractions such as naphtha and distillates using the spent iron-based Sasol HTFT catalyst. The fuel fractions (C4-400 C) had to be further hydroprocessed in dedicated naphtha and diesel hydrotreaters to adjust the heteroatom content to targeted fuel specications.
(49) Schaberg, P. W.; Myburgh, I. S.; Botha, J. J.; Roets, P. N.; Viljoen, C. L.; Dancuart, L. P.; Starr, M. E. Diesel exhaust emissions using Sasol Slurry Phase Distillate Process Fuels. SAE Tech. Pap. Ser. 1997, 972898.

Decanted oil, the heaviest fraction of the HTFT synthesis, contains mostly long-chain linear parafns and the major part of the aromatics produced by the HTFT synthesis reaction. Those aromatics are typically alkylated benzenes and tetralins and contain smaller portions of alkylated naphthalenes. Initial tests in batch autoclaves at Sasol have shown that the heavy fraction of pyrolysis tar oils can be hydroprocessed together with the heavy end from the HTFT synthesis. This work indicated that a scheme as provided in Figure 13 could present a viable alternative option of a CTL facility applying FBDB gasication and FT synthesis. The FT synthesis could either be based on the high-temperature but also on the low-temperature technology, which would then result in a ow scheme as pictured in Figure 14. The LTFT heavy ends are in this case upgraded together with the FBDB gasication-derived pyrolysis heavy fraction in a dedicated hydrocracker. 12. Recent Global Fischer-Tropsch CTL Developments The International Energy Agency (IEA) foresees that fossil fuels will continue to dominate energy supplies in 2030 with the transportation sector expected to account for two-thirds of the growth, and global daily oil demand will possibly reach

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Table 14. Selected Indirect FT Coal-to-Liquids Plants under Consideration in the United States
project lead project partner none cited GE, Haldor Topsoe, NACC, ExxonMobil Rentech, GE ANRTL,CPC Sasol, Shell, DOE N/A Adams County Baard Energy NACC, GRE, Falkirk location Oakland, IL Ascensuion, Parish, LA Medicine Bow, WY Cook Inlet, AK Gilberton, PA Southern IL, Soutwest IN, Western KY Natches, MS Wellsville, OH AZ status feasibility feasibility design (2011) feasibility design feasibility feasibility feasibility feasibility capacity, bpd 25 000 N/A 13 000 80 000 5000 1800 35 000 10-50 000 40 000 cost N/A $5 billion $1.4 billion $5-8 billion $612 million N/A $650-750 million $4 billion N/A

American Clean Coal Fuels Synfuels Inc. DKRW Advanced Fuels AIDA WMPI Rentech/Peabody Rentech Rentech Headwaters

115 million barrels per day in 2030.50 The currently known reserves of coal exceed those of crude oil by a factor of 25, with the United States, Russia, and China having the largest coal reserves in the world.5 China and India together account for almost three-quarters of the recent increase in coal demand in developing countries and two-thirds of the increase in world coal demand. As the United States seeks out solutions toward energy independence, liquefaction technologies such as the FischerTropsch process, that can produce liquid fuels from coal, are becoming more and more attractive, specically at high oil prices. Concepts consist of independent, stand-alone CTL facilities but also CTL options involving cositing of a CTL facility with an integrated gasication combined cycle (IGCC) power plant, where syngas from the IGCC is routed to the FT plant. Both concepts produce distillate and naphtha. The only commercial-scale indirect coal liquefaction (ICL) processes producing liquid synthetic fuels and currently in operation are those operated by Sasol in South Africa. These plants currently produce about 37% of South Africas transportation fuel requirements. The United States has two commercial facilities that convert coal to fuels and chemicals by indirect liquefaction. The Great Plains Synfuels Plant, located in Beulah, North Dakota, produces synthetic natural gas (SNG) from North Dakota lignite by Lurgi FBDB gasication and methanation. Operated by the Dakota Gasication Company (DGC), the plant converts lignite to pipeline quality gas in 14 Lurgi gasiers. Indirect coal liquefaction projects are currently being studied or planned in China, Philippines, Germany, Netherlands, India, Indonesia, Australia, Mongolia, Pakistan, and Canada. In the United States, indirect coal liquefaction projects are being considered in Alaska, Arizona, Colorado, Illinois, Indiana, Kentucky, Louisiana, Mississippi, Montana, North Dakota, Ohio, Pennsylvania, Texas, West Virginia and Wyoming. Table 14 lists51 in more detail various FT CTL projects under consideration in the United States of America. The prospects for a commercial FT CTL industry in the United States remain presently unclear with three major hurdles blocking the way forward, namely, the uncertainty about the costs and performance of CTL plants, the uncertainty about the future course of world oil prices, and the signicance of greenhouse gas emissions (CO2) reduction from such CTL plants. CTL plants with carbon dioxide capture and sequestration can produce fuels with life-cycle greenhouse gas emission proles that are as good or better than that of petroleum-derived
(50) Lloyd Wright, T. Hydrocarbon Process. 2007, (Supplement), 4. (51) Smith, R.; Asaro, M.; Naqvi, S. Fuels of the Future. Technology Intelligence for Coal to Liquids Strategies; CRI Consulting: July 2008.

production; however, the technical and overall challenge is to reduce the immense CO2 emissions. 13. Conclusions A brief overview was given on the development of Fischer-Tropsch plants and their renery ow schemes, spanning from the rst commercial Fischer-Tropsch plant in 1930s Germany until the newest conceptual studies. Special emphasis was placed on the distillate upgrading and the relevant fuel properties. The oldest Fischer-Tropsch facility still in operation is Sasol 1, which is now over 50 years old, although not producing fuels anymore. Sasol Synfuels at Secunda, South Africa, previously Sasol 2 and 3, is still producing predominantly fuels but is now also coproducing chemicals. The Fischer-Tropsch syncrude composition and its distillate yields are mainly determined by the FT catalyst type, iron- or cobalt-based, and the reaction conditions. The carbon number distribution of a HTFT and a LTFT synthesis product is different. HTFT syncrude has a high naphtha yield and low contents of material boiling above 360 C, wheres a synthesis product from the LTFT process consists of a considerable amount of higher boiling hydrocarbons. The nal distillate yield is substantially larger in case of the LTFT process. Fuel specications and environmental legislations have changed during the decades and affected the reneries, which had to alternate their processing schemes to meet the new product specications and the required emission standards. These changes are most of the time accompanied by large capital investments. The HTFT facilities are, with regards to the renery ow schemes, far more complex than the LTFT facilities. The latter ow schemes are simple and consist mainly of a hydroprocessing step and a fractionation step to produce naphtha and middle distillate. The drawback of LTFT reneries is that they are not able to produce nal fuels rather than fuel blending stocks. The HTFT syncrude is better suited to diesel fuel production than LTFT syncrude since the distillate boiling range material contains aromatics, hydroaromatics, and naphthenes, resulting in a diesel density that is closer to the required diesel specication. Blending with coal pyrolysis products or crude-oil-derived distillates or otherwise distillates derived from direct coal liquefaction are ways to produce a nal diesel complying with fuel specication. Alternative ways for production of onspecication diesel fuel, as highlighted in the provided conceptual ow schemes, could be the combined hydroprocessing of heavy boiling fractions derived from FT synthesis and coal pyrolysis or liquefaction. Important diesel fuel properties are cetane number, density, sulfur, polycyclic aromatic content, viscosity, cold ow, lubric-

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ity, ash point, and distillation range. The cetane number, the main quality criterion for a diesel fuel, is a measure of ignition and combustion ability of the diesel fuel, and the higher the number the better the fuel quality. Cetane numbers for FT diesel are generally exceeding the required diesel fuel specications, since Fischer-Tropsch molecules are mainly linear. Density is an important factor for fuel consumption, whereas the other properties mentioned have an effect on emissions. Although density is not a problem for aromatic-containing HTFT diesel, LTFT diesel contains virtually no aromatics and the resulting density of 770-780 kg m-3 poses a rening challenge. However, synthetic LTFT distillate is increasingly blended into top quality diesel fuels to reduce emissions in modern highperformance diesel engines. Fischer-Tropsch syncrude, be it HTFT or LTFT syncrude derived, has unique properties and lends itself to a rening that

is different from upgrading crude-oil-derived material. FischerTropsch specic rening technologies or catalysts have not been developed in the past, and the FT reners therefore adopted technologies that were commercially offered for crude oil rening. There are, however, exceptions, and Axens is now offering the Gasel technology (a Eni/IFP/Axens combined development) within their technology portfolio, which provides XTL LTFT technology with integrated product upgrading by hydrocracking.52
Acknowledgment. The author appreciates the permission of Sasol Technology to publish this work.
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(52) (a) Fedou, S.; Douziech, D.; Caprani, E. J. PetroTech Soc. 2008, 2631. (b) Caprani, E. Gasel: the XTL technology suite for the conVersion of syngas to diesel; OAPEC-IFP Joint Seminar, June 18, 2008.