Recent Research on the Fischer-Tropsch Synthesis Investigations on the Fischer-Tropsch process on a laboratory and semi-technical

scale have been in progress at the Fuel Research Station continuously since 1935. These investigations have been concerned with the factors which affect the activity and life of cobalt catalysts for the synthesis at atmospheric pressure, the synthesis at moderate pressures with cobalt and iron catalysts, the reaction mechanism, and the conversion of the primary products into secondary products, particularly high-grade lubricating oils and fatty acids. Owing to the interruption of the free dissemination of scientific information caused by the war, the results of many of the investigations have not been published, but it is hoped that this will be remedied in due course. In the present paper, it was considered that is would be of greater interest to report the results of some of the more recent research work. As investigation of the problems selected for discussion is still in progress this paper should be regarded as an “interim report.” Use of High Gas Throughputs In the Fischer-Tropsch process as employed in the industrial plants in Germany, France and Japan, a precipitated cobalt catalyst, supported on kieselguhr and containing thoria and magnesia as activators, was employed. This catalyst, in the form of small granules, was arranged in narrow spaces between water-cooled surfaces and was maintained at a temperature in the range 175°200°C. In order to achieve a 93-94 per cent conversion of the carbon monoxide in the synthesis gas, two or three stages were required and the overall gas space velocity was restricted to about 60 vol. per vol. catalyst space per hour. The space-time yield of the plants was therefore very small and did not, in fact, exceed 0.25 tons primary products per cu. m. of reaction space per day. If attempts were made to increase the space -time yield by increase in gas throughout, the conversion of the synthesis gas decreased, and if the temperature was increased to maintain conversion, the heat liberated by the reaction exceeded the heat-transfer limitations of the watercooled, fixed-bed system, the catalyst temperature rose rapidly and methane, carbon dioxide and carbon were produced. The products obtained comprised 40 to 60 per cent of low-grade petrol, 30 percent of high-grade Diesel oil and10 to 30 per cent of waxes. As a means of producing synthetic petrol, therefore, the German process suffers from two serious disadvantages. The space-time yield is low and the products contain a relatively small proportion of petrol of inferior quality. By employing an iron catalyst at temperatures in the range 300° to 330°C. and pressures of 250 to 350 lb. per sq. in., and carrying out the synthesis in a “fluid-catalyst” system, American technicians 1,2 claim that both these disadvantages can be overcome. Petrol of 80 octane number can be obtained as the major final product (80 percent of the total) and space-time yields “many times greater” than those obtained in Germany can be achieved.

By repressing the formation of carbon dioxide by water-gas-shift reaction and increasing the H2:CO utilization ratio it resulted in an increase in the proportion of carbon monoxide converted to hydrocarbons higher than methane from 60 to 80 percent. but the average carbon number was 3. 6 cm. and the average CO conversion. recirculation of residual gas. Before use for synthesis.1g. it was reduced at 450°C. This fraction of the products has not been analysed completely. with a catalyst capacity of 100 ml. and synthesis gas space velocity were studied in experiment 12/26 while adjusting the temperature to maintain a constant carbon monoxide conversion of about 95 per cent.000 vol. Iron Catalysts in Fixed Beds Although in commercial fixed-bed reaction vessels the space velocity cannot be increased much beyond 100 vol. It will be observed that at the high temperatures employed. per vol. per hour without overheating the catalyst it has been found that in small-scale laboratory reactors this limitation does not apply.. embedded in an electrically heated aluminium block. The general arrangement of the apparatus is shown in Fig. inert constituents and not more than o. had a marked beneficial effect. The average velocity over duration of the experiment (128 days of synthesis) was approximately 500 per hour. was employed as raw material. It will be observed that increase in pressure from 10 to 20 and from 20 to 25 atmos. 95 per cent.S.000 per hour. for 24 hours in pure hydrogen at a space velocity of 2. total sulphyr per 100 cu. The use of residual gas reciculation had a striking effect. catalyst per hour. synthetic-ammonia catalyst crushed and screened to 7/14 B.3 and the olefin content 75 per cent. 1 The catalyst employed was a commercial. The catalyst deteriorated in activity over the course of the experiment as indicated by the increase in temperature necessary to maintain conversion at a given space velocity. Synthesis gas (H2:CO=2:1) containing 5 per cent.It was clearly of importance not only to investigate these claims but to explore the implied possibilities of extending very materially the range of reaction conditions which can be employed in the synthesis process. The effects of pressure.m. Test Sieves.. . The reaction vessel employed in the experiments was a thick-walled steel tube. A summary of the conditions used and the results obtained is given in Table 1. in diameter. 10 mm internal diameter. rather more than half the higher hydrocarbons produced were in the range C2 to C4. fused-iron. as indicated by the reduction in temperature required to maintain conversion at a fixed space velocity and by the increase in space velocity permissible at fixed temperature without fall in conversion The CO conversion be maintained at about the 95 per cent level at space velocities up to 1.

2. The reaction tube and disengaging chamber were heated electrically.35:1. A central tube 0. Fig. which. 4.05 m. and the general arrangement of apparatus in the diagram Fig. external diameter served as a thermo-couple pocket and as a support for grids cut from steel gauze (4 mesh to the cm.5 by 7.000 g. Steady synthesis conditions were maintained continuously for 230 hours./sec. The use of these grids was found to be essential in order to obtain uniform fluidisation in long. that the catalyst was more active in the fluidized powder form than in the fixed bed. The complete elimination of carbon dioxide formation and the H2/CO utilization obtained are attributed to the use of a high recycle ratio. Almost complete carbon monoxide conversion was maintained at a constant temperature of 300+5°C. In order to obtain the linear velocity necessary to maintain the catalyst in a fluid condition (18 cm. in view of the absence of any of the usual cooling devices. disengaging chamber at the top to allow entrained catalyst to separate from the gas stream. internal diameter. 2. At the conclusion of the experiment. 3 and the photograph Fig.8 cm. is a striking illustration of the temperatureequalising effects of fluidisation. The synthesis gas used was of similar composition to that employed in the fixed-bed experiments.) without employing excessively high synthesis-gas rates recycle ratios considerably higher than those used in the fixed bed were employed. Iron Catalyst in a Fluid Bed It was clearly of considerable interest to determine the behaviour of the catalyst used in the above experiments in a fluidized state but under otherwise similar conditions to those employed in the fixed bed. The . and by comparison with the fixed-bed results.The boiling ranges and olefin contents of the liquid products obtained are shown in Table 2. the catalyst was still perfectly fluid and contained only 1 per cent of benzen-soluble organic matter (wax and resins).) which were made slightly convex to the gas flow and spaced at 5 cm. This indicates that the full activity of the catalyst was not being utilized. intervals up the tube. but this may be due to the higher H2:CO ratio employed. fitted with a conical gas inlet at the lower end and with a 30. of synthetic ammonia catalyst graded between 72 and 170 B.S. They did not seriously interfere with catalyst circulation.5 cm. It will be observed that the products were low-boiling and highly unsaturated and did not change markedly in composition with change in reaction conditions. Test Sieves and occupying a compacted volume of 400 ml. The results of an experiment in which 1.. The lower portion of the reaction tube is shown in the drawing. was employed for 305°C are recorded in Table 1.6 cm. no special heat-dissipating means (aluminium block or liquid jacket) being employed. Temperature explorations showed a maximum variation over the column of 4°C. but to minimize wax and carbon formation the H2:CO ration was increased to 2. despite increase in space velocity from 750 to 1. but the total amount of catalyst carried over with the gas stream during the experiment amounted to only 5 per cent of the whole.050 volumes per hour. narrow tubes. The reaction vessel employed consisted of a 3. No cyclone separators or filters were fitted to the reaction vessel. length of steel tube.

1. Using recirculation. Under non-recirculation conditions. For comparison with the performance of the synthetic ammonia catalyst. apart from the question of motorspirit quality which has not yet been investigated. the use of residual gas recirculation had little beneficial effect. the total yield of petrol will be of the order of 75 per cent of the final products. a . It is believed that these many be genuine and result from the hydrogenation of carbon dioxide. the iron catalyst gave an over-all superior performance to the cobalt. which brought about a big increase in methane formation. as the olefins can be polymerized to form high octane petrol. It was found possible to operate at a space velocity of 500 per hour with an 80 per cent carbon monoxide conversion by using a temperature of 220°C. although methane formation was higher. the cobalt catalyst gave higher yields of liquid hydrocarbons than iron at the same space velocity. the efficiency of utilization of the carbon monoxide was not much less than in the cobalt-catalyst process and the space-time yield of higher hydrocarbons was 15 times greater. The production of methane was reduced somewhat. Attempts to push the carbon monoxide conversion to the 95 percent level. Although the results reported at not regarded as the optimum obtainable. a rapid rise in temperature to 240°C. due to the low carbon dioxide formation. a reaction which might be expected to proceed under the conditions prevailing. Some of the results of the experiments are given in Table 1. was found to be necessary and no attempt was made to operate at higher velocities. some experiments were carried out with the normal cobalt-thoria-magnesia-kieselguhr catalyst at high space velocities in a fixed-bed apparatus similar to that shown in Fig. The composition of the liquid products obtained at similar temperatures in the fixed. were unsuccessful and merely resulted in an excessive production of methane and the formation of some carbon dioxide (see last column in Table 1). was employed. The normal synthesis gas. the results of the experiments in fixed and fluid beds are shown in comparison with those obtained in the German commercial plants. though not markedly inferior to those obtained in the fluid bed.. The figures show that. could not be reproduced on a commercial scale owing to heat transfer limitations which do not apply to the fluid catalyst system. negative values for carbon dioxide formation were recorded. but to maintain the conversion. and if this is done.. The high proportion of light hydrocarbons formed with the iron catalyst is not a disadvantage. H2:CO=2:1. (See Table 2) Comparative Results In Table 3. in the present experiments. but the production of C2 to C4 hydrocarbons was increased at the expense of the liquid products. The results obtained in the fixed bed. they afford confirmation of the claims made for the American process. At periods in the experiment. maintained in the experiments with the iron catalyst.latter is also believed to be responsible for the greatly increased proportion of C2-C4 hydrocarbons produced in the fluid bed. In contrast to the experience with the iron catalyst.

appeared to be worth further investigation.. acids.. Rôle of Alcohols In the synthesis with cobalt catalysts at temperatures in the range 180° to 200°C. (1) the OXO reaction always gives a mixture of normal and iso-alcohols. however. that alcohols are the true primary products of the Fischer-Tropsch synthesis.) and with a high gas velocity. Primary Products When a synthetic ammonia iron catalyst is employed at high temperatures (280° to 300°C. and it has been suggested that these substances arise as the result of side reaction (e. in fact. and pressures from atmospheric to 10 atmos. moreover. The olefin content of the liquid products was very much lower than that of the iron catalyst products and it is clear that the products as a whole were very much less suitable as a source of high quality motor fuel than those obtained with the iron catalyst. the products. synthesis gas per hour with an 80 percent.7. appreciable amounts of alcohols are produced. They were very similar to the products obtained in the normal atmospheric pressure. in the Synol process of the I. are almost entirely hydrocarbon in nature. Thus. pressure. therefore. it was of importance to determine whether any evidence could be obtained that alcohols might be intermediate compounds in the synthesis with cobalt catalyst. in which a synthetic ammonia iron catalyst is used at relatively low temperatures (190° to 220°C. suggested by early workers in the field 6. In the first place. The liquid products (see Table 2) were similar in boiling range to those obtained with iron but contained a higher proportion of middle contained a higher proportion of middle oil. the OXO reaction) and play no part in the main reaction mechanism.g.) as in the experiments reported in the preceding section of this paper. (2) the OXO reaction only proceeds at a reasonable rate at pressures above 50 atmos. etc. as employed in the German commercial plants. as was. The possibility.5. although it is possible in the laboratory to employ the normal type of cobalt catalyst at space velocities up to 500 vol. When iron catalysts are used in the synthesis at 10 or 20 atmos. the performance is inferior and cannot be sustained without excessive production of methane. straight chain primary alcohols constitute 60 per cent of the liquid products. which could be maintained for prolonged periods without a rapid rise in reaction temperature.performance. cobalt catalyst process. carbon monoxide conversions and obtain somewhat similar results to those obtained with a synthetic ammonia iron catalyst. The total oxygen containing substances (alcohols. (3) iron catalyst are of low activity for the OXO reaction.4. The C2 to C4 fraction had an average carbon number of 3:1 and contained 50 per cent of olefins.. Thus. the alcohol content of the products is low but the olefin content very high. It seems unlikely that these alcohols can have been produced from olefins by the OXO reaction because. apart from water.G.) do not amount to more than about 1 per cent of the whole. ketones. and it has now . aldehydes.

appreciable amounts of alcohols appear in the reaction products. i. per cent by weight of fraction 30°-200°C 19. An increase in gas rate (decrease in time of contact) also leads to a small.) and of the total non-aqueous products of the reaction. catalyst per hour. per 70 ml. It will be noted that with the cobalt catalyst at the normal synthesis temperatures and with hydrogen or nitrogen as carrier gas. The results of some experiments with n-propyl and n-octyl alcohols are summarized in Table 5. The reaction products have not yet been completely examined. was necessary to effect an 80 percent dehydration of npropyl alcohol in an atmosphere of hydrogen.9 200°-300°C 27. the main products are water and the corresponding olefin and paraffin.0 19.. the alcohols were passed over the reduced catalyst at a rate similar to that at which products are produced in the Fischer-Tropsch process. In the presence of an iron catalyst a temperature of 260°C.p. pressure but did not vary markedly with change in reaction conditions. but in the presence of water gas.3 and 1.5 10. including methane and the wax deposited on the catalyst.. This view is given support by the behaviour of pure alcohols in the presence of Fischer-Tropsch catalysts at temperatures in the usual synthesis range. At temperatures below the synthesis range. gaseous hydrocarbons were produced from octyl alcohol and the liquid . The experimental results obtained using a cobalt thoria magnesia kieselguhr catalyst and normal synthesis gas (H2:CO-2:1) are shown in Table 4.7 14. approximately 1 g. the alcohols were completely decomposed. At higher temperatures.5 per cent of the total products at 10 atmos. pressure:-Reaction Temperature °C 160 167 173 Alcohols. The alcohol content of the reaction water amounted to between 1. Distribution of alcohols The alcohols were distributed throughout the liquid products as shown by the following data for synthesis at 10 atmos. 30° to 300°C. pressure than at atmospheric pressure. The alcohol contents are appreciably higher at 10 atmos. The alcohol and olefin contents are expressed both as percentages of the liquid products (b.5 The results given in Table 4 are consistent with the view that alcohols are the initial synthesis products and that they become dehydrated to olefins which undergo hydrogenation to the paraffins to a degree dependent on the reaction conditions. but significant increase in alcohol content.e. but from preliminary examination it seems that at 150°C. n-propyl alcohol was only converted to the extent of 30 to50 per cent.1 19. some alcohol remained unchanged.been established that if the temperature is reduced materially below the normal synthesis range.

G. 45. Oil Gas J. D. J. In the work on the synthesis process at high space velocities..products had an extended boiling range. Hall. the author was assisted by Mr. References 1. O. Much more experimental work will be required in order to establish clearly the role of alcohols in the Fischer-Tropsch synthesis. Rennie and Dr. Acknowledgments The work described in this paper forms part of the programme of the Fuel Research Board of the Department of Scientific and Industrial Research and this account is published by permission of the Director of Fuel Research. therefore. that methyl alcohol cannot be an intermediate product in the Fischer synthesis..I. but by dehydration of the alcohols followed by reduction and hydrogenation cracking to form lower hydrocarbons. 102.” B. 46. P. but the preliminary results reported above. Oil Gas J. J.. In the present experiments with higher alcohols in a nitrogen atmosphere. The fact that the iron catalyst was very much less active than the cobalt for alcohol dehydration is in conformity with the observation that Fischer products obtained with iron catalyst always posses an appreciably higher alcohol content than those obtained with cobalt. S.. Eidus8 studied the behaviour of methyl alcohol over cobalt catalysts at 180°C. It is hoped as a result of further work to build up a picture of the reaction mechanism into which the whole range of syntheses based on carbon monoxide and hydrogen (methane synthesis. S. Final Report No.. It is concluded is this case. At 150°C some higher-boiling products were produced from propyl alcohol.. by Mr.S.C. Keith. D. 1947.J. G. 2. The illustrations are Crown copyright and are reproduced by permission of the Controller of H. He concluded. and by condensation reactions to form more complex substances. The effluent gas in his experiments contained 31 per cent carbon monoxide and 67 per cent hydrogen (on a nitrogen-free basis) and he deduced that the hydrocarbons were formed by synthesis from the gaseous decomposition products of the alcohol. and in the study of reaction mechanism. and obtained a range of gaseous and liquid hydrocarbons resembling those obtained in the /Fischer synthesis. 1946. synthesis of higher alcohols and higher hydrocarbons) can be fitted. 139. . therefore. Gall. 447. that the products are derived not by synthesis from carbon monoxide and hydrogen. E. and Phinney. A. Gibson. “Interrogation of Ruhrchemie A. and Eidus’ contention that this compound does not function as an intermediate is not disputed. methanol synthesis. and Gall.M. 3. methyl alcohol is only present in very small amounts when the synthesis is carried out under alcohol producing conditions.C. Roberts. R. Stationery Office.1 per cent. Mr. the maximum carbon monoxide content of the effluent gases (on a nitrogen-free basis) was 2. Craxford. Smith. strongly suggest that formation of alcohols is a stage in the main reaction mechanism and not the result of an independent side reaction. 72. L. C.

1926. 1943.O. 1930. Eidus..” C. Bull... 6. 118. Amer.S.. 52. C.G. 107. “The synthesis of Hydrocarbons and Chemicals fromCO and Hydrocarbon: B. 60. O. Ya. I.S. E. P. Chem.. Soc. D. and Nash.L.C.3. R. Smith. (U.R. 5.. . Report File No. T.I. Hawk.W. Holroyd. Reichl.O.. and Golden.G. Naval Technical Mission in Europe). A. “I. 8. Miscellaneous Report No. Leuna.154.. Farbenindustrie A.S.I. 65. F.221. Sci.S. 7.S..4. Acad. H. Nature. Elvins. XXXII. U. O.

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