Abstract
The hydrogenation of CO to hydrocarbons is investigated over zirconia iron-based catalysts prepared by co-precipitation. These catalysts, in which the Fe-content varied between 0 and 100 %, were tested in the CO hydrogenation reaction under fixed reaction conditions (H2/CO = 2, T = 250 °C, P = 20 bar, GHSV = 0.0083 L/g.s.). The resulting activity data indicated that CO conversion is strongly dependent on the iron contents of the catalysts. The lowest CO conversion (<5 %) was obtained using Zr-rich catalysts (15Fe and 5Fe), and the highest CO conversion was obtained using Zr-free (100Fe) catalysts. For this catalyst, the CO conversion level reaches 38.5 %, with selectivities for the C2–C4 and C5+ hydrocarbons of 49.7 and 27.7 %, respectively. However, the activity profile of this catalyst slightly decreases with the time on-stream, indicating that it is progressively deactivated. If the activity is normalized to the iron content, the 95Fe and 85Fe catalysts display slightly better performances and are relatively stable for on stream periods of at least 48 h.
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Pour AN, Shahri SMK, Zamani Y, Zamanian A (2010) Promoter effect on the CO2-H2O formation during Fischer–Tropsch synthesis on iron-based catalysts. J Nat Gas Chem 19:193–197
Lohitharn N, Goodwin JG Jr (2009) An investigation using SSITKA of chain growth on Fe and FeMnK Fischer–Tropsch synthesis catalysts. Catal Commun 10:758–762
Khodakov AY, Chu W, Fongarland P (2007) Advances in the development of novel cobalt Fischer–Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels. Chem Rev 107:1692–1744
Herranz T, Rojas S, Pérez-Alonso FJ, Ojeda M, Terreros P, Fierro JLG (2006) Hydrogenation of carbon oxides over promoted Fe-Mn catalysts prepared by the microemulsion methodology. Appl Catal A 311:66–75
Feyzi M, Mirzaei AA (2010) Performance and characterization of iron-nickel catalysts for light olefin production. J Nat Gas Chem 19:422–430
Ma X, Sun Q, Cao F, Ying W, Fang D (2006) Effects of the different supports on the activity and selectivity of iron-cobalt bimetallic catalyst for Fischer–Tropsch synthesis. J Nat Gas Chem 15:335–339
Panpranot J, Goodwin JG Jr, Sayari A (2002) CO hydrogenation on Ru-promoted Co/MCM-41 catalysts. J Catal 211:530–539
Dutta P, Elbashir NO, Manivannan A, Seehra MS, Roberts CB (2004) Characterization of Fischer–Tropsch cobalt-based catalytic systems (Co/SiO2 and Co/Al2O3) by X-ray diffraction and magnetic measurements. Catal Lett 98:203–210
Sun S, Fujimoto K, Zhang Y, Tsubaki N (2003) A highly active and stable Fischer–Tropsch synthesis cobalt/silica catalyst with bimodal cobalt particle distribution. Catal Commun 4:361–364
Wu B, Tian L, Xiang H, Zhang Z, Li Y-W (2005) Novel precipitated iron Fischer–Tropsch catalysts with Fe3O4 coexisting with α-Fe2O3. Catal Lett 102:211–218
Xu J, Bartholomew C, Sudweeks J, Eggett D (2003) Design, synthesis, and catalytic properties of silica-supported, Pt-promoted iron Fischer–Tropsch catalysts. Top Catal 26:55–71
Curtis V, Nicolaides CP, Coville NJ, Hildebrandt D, Glasser D (1999) The effect of sulfur on supported cobalt Fischer–Tropsch catalysts. Catal Today 49:33–40
Jothimurugesan K, Goodwin JG Jr, Gangwal SK, Spivey JJ (2000) Development of Fe Fischer–Tropsch catalysts for slurry bubble column reactors. Catal Today 58:335–344
Dry ME (2002) The Fischer–Tropsch process: 1950–2000. Catal Today 71:227–241
De Smit E, Weckhuysen BM (2008) The renaissance of iron-based Fischer–Tropsch synthesis: on the multifaceted catalyst deactivation behaviour. Chem Soc Rev 37:2758–2781
Davis BH (2003) Fischer–Tropsch synthesis: relationship between iron catalyst composition and process variables. Catal Today 84:83–98
Bukur DB, Lang X, Mukesh D, Zimmerman WH, Rosynek MP, Li C (1990) Binder/support effects on the activity and selectivity of iron catalysts in the Fischer–Tropsch synthesis. Ind Eng Chem Res 29:1588–1599
Wang H, Yang Y, Xu J, Wang H, Ding M, Li Y (2010) Study of bimetallic interactions and promoter effects of FeZn, FeMn and FeCr Fischer–Tropsch synthesis catalysts. J Mol Catal A 326:29–40
Lohitharn N, Goodwin JG Jr (2008) Impact of Cr, Mn and Zr addition on Fe Fischer–Tropsch synthesis catalysis: investigation at the active site level using SSITKA. J Catal 257:142–151
Al-Dossary M, Fierro JLG, Spivey JJ (2014) Cu-promoted Fe2O3/MgO-based Fischer–Tropsch catalysts of biomass-derived syngas. Ind Eng Chem Res 54:911–921
Campos A, Lohitharn N, Roy A, Lotero E, Goodwin JG Jr, Spivey JJ (2010) An activity and XANES study of Mn-promoted, Fe-based Fischer–Tropsch catalysts. Appl Catal A 375:12–16
Li S, Meitzner GD, Iglesia E (2001) Structure and site evolution of iron oxide catalyst precursors during the Fischer–Tropsch synthesis. Journal of Physical Chemistry B 105:5743–5750
Zhang H, Yang X, Zhou L, Su Y, Liu Z (2009) Conversion of syngas to higher alcohols over Cu-Fe-Zr catalysts induced by ethanol. J Nat Gas Chem 18:337–340
Lohitharn N, Goodwin JG Jr, Lotero E (2008) Fe-based Fischer–Tropsch synthesis catalysts containing carbide-forming transition metal promoters. J Catal 255:104–113
Qing M, Yang Y, Wu B, Xu J, Zhang C, Gao P, Li Y (2011) Modification of Fe–SiO2 interaction with zirconia for iron-based Fischer–Tropsch catalysts. J Catal 279:111–122
All S, Chen B, Goodwin JG (1995) Zr promotion of Co/SiO2 for Fischer–Tropsch synthesis. J Catal 157:35–41
Hong J, Chu W, Chernavskii PA, Khodakov AY (2010) Effects of zirconia promotion on the structure and performance of smaller and larger pore silica-supported cobalt catalysts for Fischer–Tropsch synthesis. Appl Catal A 382:28–35
Jongsomjit B, Kittiruangrayub S, Praserthdam P (2007) Study of cobalt dispersion onto the mixed nano-SiO2–ZrO2 supports and its application as a catalytic phase. Mater Chem Phys 105:14–19
Moradi GR, Basir MM, Taeb A, Kiennemann A (2003) Promotion of Co/SiO2 Fischer–Tropsch catalysts with zirconium. Catal Commun 4:27–32
Ma X, Sun Q, Ying W, Fang D (2009) Effects of promoters on catalytic performance of Fe-Co/SiO2 catalyst for Fischer–Tropsch synthesis. J Nat Gas Chem 18:354–358
Yang J, Sun Y, Tang Y, Liu Y, Wang H, Tian L, Wang H, Zhang Z, Xiang H, Li Y (2006) Effect of magnesium promoter on iron-based catalyst for Fischer–Tropsch synthesis. J Mol Catal A 245:26–36
Herranz T, Rojas S, Pérez-Alonso FJ, Ojeda M, Terreros P, Fierro JLG (2006) Carbon oxide hydrogenation over silica-supported iron-based catalysts: influence of the preparation route. Appl Catal A 308:19–30
Pérez-Alonso FJ, Granados ML, Ojeda M, Herranz T, Rojas S, Terreros P, Fierro JLG, Gracia M, Gancedo JR (2006) Relevance in the Fischer–Tropsch synthesis of the formation of Fe-O-Ce interactions on iron-cerium mixed oxide systems. J Phys Chem B 110:23870–23880
Fischer F, Tropsch H (1930) Über die Entwicklung unserer Benzinsynthese aus Kohlenoxyd und Wasserstoff bei gewöhnlichem Druck. Brennstoff—Chemie 11:489
Cornell RM, Schwertmann U (1996) The iron oxides: structures, properties, reactions and uses. VCH Publishers, New York
Fischer F, Tropsch H (1923) Über die Herstellung synthetischer Ölgemische (Synthol) durch Aufbau aus Kohlenoxyd und Wasserstoff. Brennstoff—Chemie 4:276
Fischer F, Tropsch H (1926) The synthesis of petroleum at atmospheric pressures from gasification products of coal. Brennstoff—Chemie 7:97
Briggs D, Seah MP (1990) Practical surface analysis. In: Briggs D, Seah MP (eds) Auger and X-ray photoelectron spectroscopy. John Wiley & Sons, Chichester
Wagner CD, Davis LE, Zeller MV, Taylor JA, Raymond RH, Gale LH (1981) Empirical atomic sensitivity factors for quantitative analysis by electron spectroscopy for chemical analysis. Surf Interface Anal 3:211–225
Park J-Y, Lee Y-J, Khanna PK, Jun K-W, Bae JW, Kim YH (2010) Alumina-supported iron oxide nanoparticles as Fischer–Tropsch catalysts: effect of particle size of iron oxide. J Mol Catal A 323:84–90
Gallegos NG, Alvarez AM, Cagnoli MV, Bengoa JF, Marchetti SG, Mercader RC, Yeramian AA (1996) Selectivity to olefins of Fe/SiO2–MgO catalysts in the Fischer–Tropsch reaction. J Catal 161:132–142
Den Breejen JP, Radstake PB, Bezemer GL, Bitter JH, Frøseth V, Holmen A, De Jong KP (2009) On the origin of the cobalt particle size effects in Fischer–Tropsch catalysis. J Am Chem Soc 131:7197–7203
Bezemer GL, Bitter JH, Kuipers HPCE, Oosterbeek H, Holewijn JE, Xu X, Kapteijn F, Van Diilen AJ, De Jong KP (2006) Cobalt particle size effects in the Fischer–Tropsch reaction studied with carbon nanofiber supported catalysts. J Am Chem Soc 128:3956–3964
Li S, Li A, Krishnamoorthy S, Iglesia E (2001) Effects of Zn, Cu, and K promoters on the structure and on the reduction, carburization, and catalytic behavior of iron-based Fischer–Tropsch synthesis catalysts. Catal Lett 77:197–205
Zhang H, Ma H, Zhang H, Ying W, Fang D (2012) Effects of Zr and K promoters on precipitated iron-based catalysts for Fischer–Tropsch synthesis. Catal Lett 142:131–137
Torres Galvis HM, Bitter JH, Davidian T, Ruitenbeek M, Dugulan AI, De Jong KP (2012) Iron particle size effects for direct production of lower olefins from synthesis gas. J Am Chem Soc 134:16207–16215
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M. Al-Dossary gratefully acknowledges financial support from SABIC-Saudi Arabia for PhD program.
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Al-Dossary, M., Ojeda, M. & Fierro, J.L.G. Syngas Conversion to Hydrocarbons on Zirconia-Supported Iron Catalysts. Catal Lett 145, 1126–1137 (2015). https://doi.org/10.1007/s10562-015-1504-9
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DOI: https://doi.org/10.1007/s10562-015-1504-9