Symposium on Advances in Fischer-Tropsch Chemistry Presented Before the Division of Petroleum Chemistry, Inc. 219th National Meeting, American Chemical Society San Francisco, CA, March 26-31, 2000 i Comparative Study of Fischer-Tropsch Synthesis with Carbon Monoxide/ Hydrogen and Carbon Monoxide/ Hydrogen/Nitrogen Mixtures Paul J. Collier, Meleri Johns and Graham J. Hutchings Department of Chemistry University of Cardiff P.O. Box 912 CF1037B, UK INTRODUCTION Recently there has been a resurgence of interest in the Fischer-Tropsch Synthesis reaction. Partly, this has been the result of the commercialization of the Shell SMDS (Shell Middle Distillate Synthesis) process in Malaysia in 1995 (1). This is a two-stage process involving Fischer-Tropsch synthesis, using a promoted cobalt catalyst, and with subsequent hydrocracking (2). A similar approach had been previously commercialized by Sasol in South Africa based on a promoted iron catalyst (3). There is much current interest in the use of air blown methane partial oxidation technology for the produc- tion of synthesis gas (4), with the ultimate goal of eliminating the need for Pure oxygen, which requires an expensive air separation plant, thereby reducing capital expenditure costs. An exciting recent development in Fis- cher Tropsch technology has been the development of F-T processes, by Syntroleum and others, able to utilize the nitrogen rich syngas feeds, whi result from using air in the syngas production step. Iis fair to say that world produc- tion of crude oil has reached its zenith and is expected to decline during the next century, eventually making ex- ploitation increasingly commercially non-viable. Since the major world economies are heavily dependent on the availability of inexpensive oil, this realization of the finite nature of World oil reserves has spurred the Pace of development of new tech- Tologies that can utilize natural gas ot coal as feedstocks for the produc- ‘ion of synthetic fuels. An additional impetus to find alternatives to oil- based technologies has been given by the extensive reserves of natural gas discovered in the last two decades in remote locations (5). The develop- ment of efficient alternative routes of- fers exceptional business opportun- ities as the global energy market re- acts to declining oil reserves. One such technology is the Fischer- ‘Tropsch (F-T) reaction, which trans- forms mixtures of carbon monoxide and hydrogen (syngas) in to a wide range of products including hydro- 199 carbons and oxygenates (6). The F-T reaction was developed in the early part of the century (7), and has seen continued development since then, particularly with the SMDS process (2). Figure 1 illustrates how interest in FT technology has varied with the level of hydrocarbon reserves (oiland gs) as measured by academic pub- lishing and patent activity. Proven re- serves are defined as oil or gas which geological and engineering informa- tion indicates with reasonable cer- tainty can be recovered in the future from known reservoirs under exist- ing operating conditions. It is clear that the level of crude oil reserves has been a major factor in determining interest in the F-T synthesis, but, in addition, the increasing reserves of natural gas throughout the 1980's and 1990's has also stimulated F-T research, Recently a 70 bpd pilot plant has been commissioned (8), which uses Nz/H2/CO feeds derived from autothermal methane oxidation which contain high nitrogen dilution levels (45-50%) for an F-T based gas to liquids process. The overall proc- ess is envisaged to comprise three parts: syngas generation, E-T synthe- sis, and a fractionation unit for prod- uct separation (9). In addition, Jess and co-workers have examined the use of nitrogen rich syngas (pro- duced by catalytic partial oxidation of methane with ait) asa feed foracom- mercial precipitated iron based F-T catalyst (10). The present paper briefly considers this renewed inter- fest in the Fischer-Tropsch process and discusses data for a Co- Zr0p/SiOz catalyst investigated un- der conditions with varying levels of nitrogen dilution in the feed.Ty Ta goo a2 os cou ow 5001 EDD HEE Fig 1 Veron nF Tepe rest wt row ol ards rsenes ‘Figure 2. Scher (1976-1806 (12). EXPERIMENTAL A Co-Zr02/SiOz catalyst was prepared by consecutive impregna ation of Grace silica (BET surface area 20 m?g'}) with Zr(OCHzCH2CHs)4 and Co(NO3)26H20, by a route ‘Snalogous to that reported by Shell (11). After each addition of zirconium precursor the carrier ‘was dried at doped carrier was then impregnated swith aliquots of a Co(NO3)2.6F420 so- lution and dried atroom temperature and calcined in air for two hours at ‘minal Co” loading of 10 nominal Zt” loading of ‘The catalyst was tested for Fis- cher-Tropsch synthesis in a fixed bed gnicroreactor (Figure 2). The inlet gas flow rate and composition were de~ termined by two Brooks mass flow ‘controllers and the catalyst bed tem perature controlled by PID tempera. fare control in conjunction with a thermocouple situated in the middle of the bed. Condensable products ‘were collected in a vessel located downstream of the reactor, which ‘was periodically emptied to enable the determination of mass balances and hydrocarbon selectivities. The Gown stream pressure in the rig was ~ controlled by a back pressure regula tor and the reactor effiuent gas fed to adport valve connected to an on-line GC to allow for the analysis of two F-T reaction systems by a single GC. Condensed products were analyzed by off-line GC analysis and mass bal- ances were typically 95-100 (see Table y. ‘The catalyst was mixed with 2 mam glass beads (inactive in blank re- dction) to dilute the bed and reduced jn situ prior to reaction in 50 ml/min fofahyarogen/nitrogen mix (10% Ha) by heating at 1°C/min from room sture to 400°C, holding for 12 hours, followed by cooling to ambi- tent temperature. After the reduction the reactor was pressured to 322 psig with feed gas at ambient tex, peratureand the catalystoven heated Fo 150°C at 5*C/min and held at 350°C to thermally stabilize before continued heating to 206°C at a rate of 5'C/min. The reaction was per formed ly at 206°C with a fixed GHSV of 2000 he. In practice this inevitably means that the partial pressure of CO and He changes s the Fitrogen dilution level is altered. The catalyst was tested forapproximately $50 hours and was brought on line Tasing a feed of 40% Nz, 21% CO and 39% Ha. After about 460 hours of 0p teration the feed was switched to 35% CO and 65% Ha (ie. nitrogen dilution removed). Four analysis periods ‘were used to determine the CO con Sumption and hydrocarbon selectiv: ity CHable 1). Test periods 1 and 2 are hen nitrogen dilutions presentand test periods 3 and 4 cover the period When nitrogen dilution was Te moved. RESULTS AND DISCUSSION Powder X-ray diffraction (XRD) analysis of the 10% Co-Z:02/SiOz satalyst prior to reaction gave a fairly Svea diffraction pattern, although “fraction lines attributable to cubic CosOa and. hexagonal Coz0s were Getected. Temperature Programmed Reduction (TPR) analysis ofthe cata Iyets prior to reaction show broad re YEcton peaks attributable to the Seduction of CogOs to CoO and COO te Co. XRD analysis of the ex-reactor Gatalyst at the end of the reaction showed the presence of Vary SHON Giftractions at 4.13 and 3.73 A, which were also observed in a powder XRD Uiffraction pattern of asample of wax ecovered from the collection trap during one of the F-T experiments In addition, lines indexed to hep cobalt 2.023 A) were ob- Served in the ex-reactor catalysts, al- though no diffraction lines were SSbeerved for ecp cobalt metal in the ex reactor samples.Molar conversion (as expressed as number of moles CO consumed per hour per g of catalyst) increased ‘upon changing the reactant feed from. 40% nitrogen dilution to no nitrogen. dilution. This is a consequence of the fact that the reaction was performed with fixed GHSV leading to an in- crease in hydrogen and carbon mon- oxide partial pressures when the nitrogen dilution was removed. It is well known that for cobalt catalysts the F-T reaction is approximately first order in hydrogen, although this of course is dependent on the exact ex- perimental conditions and higher or- ders in Hz have also been reported (2). This means that when switching from 40% Nz to no nitrogen diluent the hydrogen partial pressure in- creases from 125.6 to 209.3 psig thus bringing about an increase in the rate of CO conversion. Table 1 shows that the carbon number selectivity is broadly unaf- fected by changing the feed composi- fion. Schulz Flory analysis (only Cs+ hydrocarbon selectivity data in- cluded in analysis) of the hydrocar- bon selectivity data give a values of Tablet Effect of Nitrogen Dilution Level on Molar Conversion of CO and Hydrocarbon Selectivity on a 10% Co(Zr02- SiOz Catalyst SE] a] aS rae SSS ee oe a afer — he par Pape ta a ee TTA “extn ee rate “eh gauge eG 0.82, 0.90, 0.82 and 0.85 for the four test periods respectively. This is typi- cal for a cobalt catalyst and demon- strates that the presence of nitrogen dilution in the feed does not alter the surface polymerization kinetics for this catalyst. ‘The experimental data obtained with the 10% Co-Z102/SiO2 catalyst shows that the use of nitrogen diluted synthesis gas feeds is not detrimental to the operation of Fischer-Tropsch processes. This is in agreement with Jess and co-workers who have exam- ined the use of nitrogen diluted feeds but with a commercial iron catalyst (11). Incontrast to the cobalt-zirconia catalysis reported here the iron based catalysttested by Jess and co-workers gave significant levels of carbon diox- ide (up to 25%). LITERATURE CITED (1) Wender, 1, Fuel Proc. Techn., 48, 238-257 (1996). @) Eilers, J, Posthuma, 5. A., Sie, S.T, Catalysis Letters, Z, 253- 270 (1990).. 201 @) @ ® 9) 0) q@) a2) see Espinoza, R. L., Steynberg, A.P, Jager, B., Volosoo, A. C, Appl. Catal. A: General, 186, 13 (1999), for recent develop- ‘ments in this area. Taylor, M. R, "Catalytic Partial (Oxidation for Syngas Produc- tion’, Presented at "Remote Gas Utilisation” 3rd December 1997, London, IBC Confer- ences Ltd. Agee, M. A, Stud. Surf. Sci Catal, 119, 981 (1998). Hindermann, J. P, Hutchings, G.J. and Kiennemann, A. Catal. Rev.Sci. Eng,, 35, 1 2993). Anderson, R.B,, in Catalysis, vol. 4, Ed. P. H. Emmett (Rhein- hold, New York 1956) p 29-255. "Business Briefs", Chemistry in Industry, September 1999. Agee, K. L,, US, 4833170, 1989 assigned to GTG Inc, Agee, K.L, US. 4973453, 1990 as- signed to GTG Inc. Jess, A., Popp, R., Hedden, K., ‘Appl. Catal. A: General, 186, 321-342 (1999), and references therein. EP 110 449 assigned to Shell, EP 0 127 220 assigned to Shell. Data source: BP Chemicals (Oil and Gas reserves data 1997), US. Patent Office and IST BIDS (University of Bath, UK).