‘The Anaiean Action of elem Genin Dlin ‘iN e(aerm 9), 505598 Ri, ae Petroleum Formation by Fischer-Tropsch Synthesis in Plate Tectonics’ PETER SZATMARY ABSTRACT Asomewhat speculative hypothesis of petroleum gene sisin the upper lithosphereis proposed, based on Fischer- ‘Tropsch synthesis. This hypothesis is distinct from both ‘the organic (biogenic) model and the inorganic model of hydrocarbon degassing from the Earth's interior. Fischer-Tropsch synthesis is a well-known industrial process whereby millions of tons of hydrocarbon oil resembling petroleum are produced annually from car- ‘bon monoxide or carbon dioxide and hydrogen gases, reacting on a metallic iron or iron-oxide catalyst. Like natural petroleum, this synthetic oil consists of gas, gaso- Tine, diesel oil, and wax fractions, all rich in saturated: phatic hydrocarbons and enriched in the light "C isotope. ‘The hypothesis presented in this paper proposes that petroleum liquids form by Fischer-Tropsch synthesis on magnetite and hematite catalysts when carbon dioxide (derived by massive metamorphic or igneous decarbona- tion of subducted sedimentary carbonates) reacts with hydrogen generated by the serpentinization (in the absence of air) of shallow-mantle lithosphere and ophio- lite thrust sheets. Oblique plate movements may favor hydrocarbon formation by creating deep faults that sid fluid flow and serpentinization. The world’s richest oil provinces, including those of the Middle East, may be tentatively interpreted to have formed by this mechs- nism. INTRODUCTION The origin of petroleum is generally attributed to the thermal breakdown of fossil organic matter or kerogen, (Hunt, 1979; Tissot and Welte, 1984). A small number of researchers attribute its origin to the degassing of hydro- carbons from the Earth’s interior (Gold, 1979, 1984). A third hypothesis is explored in this paper—petroleum formation in the lithosphere by Fischer-Tropsch synthe- sis. Like photosynthesis, Fischer-Tropsch synthesis pro- ‘duces organic compounds by the catalytic hydrogenation and reductive polymerization of carbon monoxide or ‘©Copyright 1909. The American Assocation of Paleum Geciogts ll ‘eases Manusstipecahed, March 2, 1908; cceptod, March 30, 699. 2peobras Research Coner(CENPES) Flo de Jane, raz! 21920 “The weer thanks Joacim Wericks and Daley. Aves fr hap discus sions and advo, Joba Maxwell ord two anonymous revewers fo eewing ‘he manuserp,and the management of he PETROBRAS Research Cantor {(CENPES) for encouragement and permission to publish carbon dioxide. At present, itis the only process for pro- ducing hydrocarbon oils resembling petroleum (com- posed of gas, gasoline, diesel oil, and wax fractions) synthetically on an industrial scale. During World War II, the process supplied Germany and its allies yearly with 1 million tons of synthetic hydrocarbon oil. In 1955, Fischer-Tropsch synthesis was introduced into South Africa, where Sasol’s present producing capacity is about 127,000 bbI/day (or 6 million tons/year) of syn- thetic oil (international Petroleum Encyclopedia, 1981). Soon after the start of industrial Fischer-Tropsch symthe- sis in South Africa, leading hydrocarbon chemists per- ceived its possible significance in petroleum genesis. Robinson (1963), past-president of the Royal Society of London, noted that the distribution of normal paraf- fins in crude oil is the same as that in hyéroformed oil produced by Fischer-Tropsch synthesis. He suggested ‘hat a primordial petroleum had formed perhaps 2 billion years ago by Fischer-Tropsch synthesis and subsequently underwent repeated hydroforming events while increas- ing amounts of biological material were added to it throughout the Earth’s history. Friedel and Sharkey (1963, 1968) found that the two parameters of the Fischer-Tropsch synthesis—the proba- bility of chain lengthening and that of chain branching— accurately predict the abundance of isomers in a Saudi Arabian oil, suggesting that it formed by Fischer- Tropsch synthesis and not by thermal breakdown of fos- sil organic matter. Elanskiy (1966), as quoted by Porfir'ev (1975), sug- szested that the serpentinization of iron-bearing olivine in the presence of CO; may form hematite and hydrocar- ‘bons such as ethane (Mendeleyev-Hess reaction). Studier et al (1965, 1968, 1972) demonstrated that the hydrocarbon composition of the Orgueil and Murray carbonaceous chondrite meteorites, in which benzene and toluene dominate at low carbon numbers and alipha- tic hydrocarbons dominate at high carbon numbers, can be reproduced experimentally by Fischer-Tropsch syn- thesis followed by reheating to cause partial transforma- tion of the alkanes to aromatics. Lancet and Anders (1970) showed that the large differ- ence in carbon isotope distribution observed between hydrocarbons (aromatic polymers and solvent- extractable bitumen) and carbonates (dolomite and breunnerite) in carbonaceous chondrites can also be reproduced by Fischer-Tropsch synthesis. They sug- gested that hydrocarbon synthesis took place during the accretion of these meteorites at 300-350 K (27°-77°C);, the synthesis was catalyzed by magnetite and hydrous sil- icates that formed, together with hydrogen and Mg-Fe carbonates, during serpentinization,990 Although Fischer-Tropsch synthesis has become widely accepted as an explanation for hydrocarbon syn- thesis in meteorites, it has hardly been considered as an alternative for the origin of petroleum—Hunt’s (1979) excellent textbook on petroleum geochemistry and geol- ‘ogy devotes only five lines of 612 pages to this process. Geologists have good reasons for their reluctance to apply Fischer-Tropsch synthesis to petroleum genesis. Until lately, no major geological source of hydrogen was known, although metallic iron—the chief Fischer- Tropsch catalyst—exists in very small amounts at low temperatures in the Earth and rapidly becomes poisoned by sulfide, sulfate, and chloride ions. ‘During the last few years, however, significant quanti- ties of hydrogen, formed by the reduction of water dur- ing serpentinization, have been observed on the surface in peridotites of the Oman ophiolites (Neal and Stanger, 1983), in the subsurface over the U.S. Mid-Continent gravity anomaly (Goebel et al, 1984; Coveney et al, 1987), and in experiments (Janecky and Seyfried, 1986). At the same time it has been shown that the iron oxides magnetite and hematite, widely present in geological environments, are also efficient catalysts for Fischer- ‘Tropsch synthesis and are much less susceptible to sulfur poisoning than metallic iron (Madon and Taylor, 1981). Finally, the advent of plate tectonics and the results from deep continental reflection profiling (Oliver, 1986) have created a geotectonic perspective fundamentally differ- ent from the one in which the organic model of petroleum genesis was born a century ago. Thus, these advances have led this writer to reexamine the role of Fischer- Tropsch synthesis in petroleum formation and to pro- ‘pose (Szatmari, 1986a, 1986b) that it may take place ona large scale during lithospheric plate interaction. ‘MECHANISM OF FISCHER-TROPSCH SYNTHESIS The basic reaction in Fischer-Tropsch synthesis (Anderson, 1984; Réper, 1983) is the highly exothermi ‘hydrogenation of carbon monoxide and the slightly endothermic hydrogenation of carbon dioxide. The lat- ter process takes place in two steps—carbon monoxide is formed first, and is then hydrogenated to hydrocarbons (Weatherbee and Bartholomew, 1984). To produce petroleum-type hydrocarbon mixtures by Fischer-Tropsch synthesis, the carbon-oxygen bond has to be broken first, and then it has to be replaced by a carbon-carbon or carbon-hydrogen bond. (In the some- what different Kolbel-Engelhardt synthesis, hydrocar- bbons are produced from carbon monoxide and water, so that the hydrogen-oxygen bond of the water molecule also has to be broken.) The catalyst is generally a Group VIII metal (iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum) or its oxide However, molybdenum, tungsten, and rhenium also adsorb carbon and hydrogen on surfaces and form tem- porary bonds. Each growing hydrocarbon chain either may react with ‘one or more carbon atoms or may terminate its growth by reacting only with hydrogen atoms. As a result of this Petroleum Formation by Fischer-Tropsch Synthesis 10 xit fF IMLET Ma/00=13 1B | chee + sev/war lise | “se x35) a4 | 93 257 oa | 86 oal vazg 35 | 76 _| INLET He/c0=0.67/ IF or VR | 12 | 79 4 . 203, oes | 59 € Z ool 4 S 8 [ 4 S 3 & ty 0.001} — am 4 3 L 3 4 0.0001} — 7 . coool Litr1rriiiiriy 23 5 7 9 11315 17 29 2123 25 27 CARBON NUMBER, n Figure 1—Schulz-Flory distribution of hydrocarbons formed. by Fischer-Tropsch synthesis on iron catalyst in slurry reactor at 249°C. Chain growth probability c is defined primarily by synthesis temperature and catalyst, and is not readily modified Dy changes in inlet H,/CO ratio, space velocity (V/V/AR = volume/volume/hour), or efficiency of conversion. (After Sat- {erfield and Huff, 1982.) wide range of probabilities, acomplex hydrocarbon mix- ture similar to petroleum is always produced instead of a single hydrocarbon compound. Hydrocarbons with short chains (especially methane) are the type most likely to be formed, so that methane and the lightest hydrocar- bon molecules are always the most abundant in number although not necessarily in weight. Within a given prod- uct, the ratio between the numbers of hydrocarbon mole- cules with successive carbon numbers is almost constant (C/G, = C/C, = C/C,) (Figure 1). This ratio is the probability of chain growth, and the resulting composi- tion is the Schulz-Flory distribution, Depending on this ratio, the mixture may range from pure methane if the ratio is 0, to predominantly liquid hydrocarbons if the ratio is 0.6-0.8, to predominantly solid waxes ifthe ratio is approximately 1. IRON OXIDE CATALYST The first iron catalyst used for hydrocarbon synthesis in 1923 by Fischer and Tropsch consisted of simple alka- lized iron filings. The catalyst is now made by either pre cipitating or fusing iron oxide and then reducingit at highPeter Szatmari temperature (230°-500°C) in pure hydrogen stream. Cat- alysts prepared by reduction in hydrogen stream at 500°C consist mostly of metallic iron and thus are highly sensitive to sulfur poisoning; those catalysts prepared by reduction at 230°C consist mostly of magnetite and are not as sensitive to sulfur poisoning (Madon and Taylor, 1981). During the synthesis, metallic iron catalysts gradually are converted into magnetite with various amounts of iron carbides, and their surface becomes deactivated by the deposition of graphitic carbon. The oxidation of metallic iron catalysts into magnetite does not alter their activity, showing that iron oxides ae just as effective cat- alysts as metallic iron (McCartney et al, 1953). ‘Oxidation of the catalyst prior to synthesis may actu. ally increase its activity. Thus, Dwyer and Somorjai (1978) showed that the amount of methane formed over a preoxidized iron foil increased ten times relative to the amount formed over a clean reduced foil. They noted a similar, fivefold increase when, instead of carbon mon- oxide, they hydrogenated carbon dioxide, which oxi- dized the surface of the iron catalyst (Joyner, 1977). Placing silica-supported hematite in a stream of syn- thesis gas (CO+H,), Wang and Ekerdt (1983) found that its catalytic activity rose for 150 hours and then became relatively constant as the hematite was converted to mag- netite with very litle iron carbide. After 56 days of use, mostly between 200°-240°C, part of the catalyst was con- verted to iron carbides. The catalytic activity of iron oxides during hydrocar- bon synthesis was studied in detail by Reymond et al (4982) and Pommier et al (1985). They found that unheated magnetite or hematite catalyst precursors are only very slightly active, and they do not become signifi- cantly active after treatment with the synthesis gas itself. Heating at 250°C also results in little improvement. High activities of 1 kg of hydrocarbons per 1 kg of catalyst per hour are obtained, however, if the silica- or alumi supported hematite is formed by heating the iron catalyst to 500°C in an oxidizing atmosphere; these activities fur- ther increase as the hematite is converted to magnetite during synthesis. Chain growth probability « is also higher for the preoxidized than for the prereduced cata- lyst, and when the former is spent, no inactive carbon or iron carbide is observed on its surface (Figure 2) (Pom- tier et al, 1985). These observations suggested to Pommier et al (1985) that ionic (oxidic)ironis just as active in Fischer-Tropsch synthesis as metallic iron. During synthesis, surface mag- netite is continuously oxidized to hematite by dissocia- tion of CO and is again reduced to magnetite by hydrogen, The fact that magnetite or hematite precursors show litte catalytic activity even if heated to 250°C, whereas hematite obtained from them at 500°C is very active and lastingly so, indicated to Pommier et al (1988) that at such temperatures the iron oxide may exchange cations with its silica or alumina support, so that iron ions move into more stable positions in the silica or alu- ‘mina lattice. This, in turn, indicates that iron silicates may also be active catalysts for Fischer-Tropsch synthe- sis 991 Sie 10181201 is 4000 7,300] a = | 3000 2 209 é 2000 zg 2 wo 1000 Time (h) Figure 2—Etfeets of reducing and oxidizing pretreatments on efficiency of iron oxide catalyst precursor in Fischer-Tropsch synthesis. (1) Transformed fo magnetite by heating in helium for 1 hr at 250°C. (2) Transformed to magnetite by heating in hhydrogen for 15 hr at 250°C. (3) Reduced to metalic iron by hheating in hydrogen for 15 brat 500 °C. (4) Oxidized to hematite by heating in oxygen for 2 hr at $00°C. (5) First reduced to ‘metallic iron asin 3, then oxidized to hematite as in 4. Arrows point toward scale to be used. (After Pommier et al, 1985.) Carbon Dioxide Source: Decarbonation of Sediments On Earth, in contrast to the other terrestrial planets, most of the carbon dioxide was withdrawn from the atmosphere early to form sedimentary carbonates. The carbon dioxide content of these rocks is 10,000 times ‘more than that of the atmosphere to which it is contin- ually recycled by metamorphic and igneous decarbona- tion (Berner et al, 1983; Berner and Barron, 1984). ‘Metamorphic decarbonation of magnesite or dolomite in the presence of silica and water is considerable, even at low temperatures (300°-500°C) (Figure 3)—dolomites rich in quartz or clay minerals, as well as dolomitic cement in sandstones and shales, are transformed first into hydrous and then into anhydrous Ca-Mg silicates and calcite while releasing CO,. With increasing temper- atures during metamorphic decarbonization, talc, trem- olite, diopside, and forsterite form in quartz-tich dolomites, and oisite/clinozoisite, margarite, grossu- larite, and anorthite form in marls (Winkler, 1976). Mg- bearing fluids issuing from serpentinizing peridotites ‘may dolomitize limestones and thereby lower their decar- bonation temperature, Decarbonation temperatures may be reached as a result of subduction, igneous intrusion, ot rifting, the latter affecting mostly prerift sequences. Although much of the CO, degassed from subducted. sedimentary carbonates rises to the surface in volcanic ares, a significant portion also rises where there are no volcanoes—in accretionary prisms, in backarc basins, and in subduction zones without significant volcanic