Abstract
Literature about ZnAl2O4-supported iron Fischer-Tropsch to lower olefins (FTO) catalytic materials is sparse. Fe/K/spinel nanocomposites were synthesized by coprecipitation of Fe/Zn/Al nitrates with a precipitant as well as subsequent calcinations at 350 °C, followed by impregnation of potassium source. Materials were investigated by XRD, N2 sorption, FESEM, CO2-TPD as well as catalytic performance tests. Addition of potassium may remove the high-temperature desorption peak for strong basicity sites and increase both the strength and number of weak basicity sites on the surface of nanocomposites. Effects of reaction temperature, total pressure, space velocity as well as potassium content on catalytic performance of nanocomposites were systematically investigated. The ZnAl2O4 phase in support is able to remain a stable structure during the CO hydrogenation tests. The ZnAl2O4 phase may efficiently drive formed hydrocarbon molecules away from nanocomposite surface and thus can effectively hinder C–C coupling. Fe/K2O/ZnAl2O4·Al2O3 nanocomposites achieve very high short chain (C1-C4) hydrocarbon distribution value of 81.7–96.3% throughout their tested parameter range. At a condition of 0.5 MPa, 350 °C, and 1500 mL·g cat−1·h−1, the nanocomposite catalyst with a K2O content of 2%, which has a primary particle size of ca. 10 nm, achieves its maximum C2=-C4= hydrocarbon distribution of 53.4%, and, reaches a C2-C4 hydrocarbon distribution value of 61.7% which exceeds the ASF (Anderson-Schulz-Flory) limit value of 58%. These results indicate that novel supports and appropriate promoters own significant potential and are worthy of further investigations for iron-based FTO nanocomposite catalysts.
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References
Buyanov RA, Pakhomov NA (2001) Catalysts and processes for paraffin and olefin dehydrogenation. Kinet Catal 42:64–75
Chen W, Kimpel TF, Song Y, Chiang F-K, Zijlstra B, Pestman R, Wang P, Hensen EJM (2018) Influence of carbon deposits on the cobalt-catalyzed Fischer-Tropsch reaction: evidence of a two-site reaction model. ACS Catal 8:1580–1590
Collinge G, Kruse N, McEwen J-S (2017) Role of carbon monoxide in catalyst reconstruction for CO hydrogenation: first-principles study of the composition, structure, and stability of Cu/Co(1012) as a function of CO pressure. J Phys Chem C 121:2181–2191
Enger BC, Fossan Å-L, Borg Ø, Rytter E, Holmen A (2011) Modified alumina as catalyst support for cobalt in the Fischer-Tropsch synthesis. J Catal 284:9–22
Feyzi M, Khodaei MM, Shahmoradi J (2012) Effect of preparation and operation conditions on the catalytic performance of cobalt-based catalysts for light olefins production. Fuel Process Technol 93:90–98
Fronzo AD, Pirola C, Comazzi A, Galli F, Bianchi CL, Michele AD, Vivani R, Nocchetti M, Bastianini M, Boffito DC (2014) Co-based hydrotalcites as new catalysts for the Fischer-Tropsch synthesis process. Fuel 119:62–69
Galvis HMT, de Jong KP (2013) Catalysts for production of lower olefins from synthesis gas: a review. ACS Catal 3:2130–2149
Gupta M, Smith ML, Spivey JJ (2011) Heterogeneous catalytic conversion of dry syngas to ethanol and higher alcohols on Cu-based catalysts. ACS Catal 1:641–656
Jiao F, Li J, Pan X, Xiao J, Li H, Ma H, Wei M, Pan Y, Zhou Z, Li M, Miao S, Li J, Zhu Y, Xiao D, He T, Yang J, Qi F, Fu Q, Bao X (2016) Selective conversion of syngas to light olefins. Science 351:1065–1068
Jongsomjit B, Panpranot J, Goodwin JG (2001) Co-support compound formation in alumina-supported cobalt catalysts. J Catal 204:98–109
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
Liu Z, Xing Y, Xue Y, Wu D, Fang S (2015a) Synthesis, characterization, and Fischer-Tropsch performance of cobalt/zinc aluminate nanocomposites via a facile and corrosion-free coprecipitation route. J Nanopart Res 17. https://doi.org/10.1007/s11051-015-2899-3
Liu Z, Xue Y, Wu D, Xing Y, Fang S (2015b) Effects of water addition on CO hydrogenation over zinc-containing spinel-supported cobalt catalyst. Catal Lett 145:1941–1947
Liu Z, Wu D, Xing Y, Guo X, Fang S (2016) Effect of in-situ sulfur poisoning on zinc-containing spinel-supported cobalt CO hydrogenation catalyst. Appl Catal A Gen 514:164–172
Liu Z, Wu D, Guo X, Fang S, Wang L, Xing Y, Suib SL (2017) Robust macroscopic 3D sponges of manganese oxide molecular sieves. Chem Eur J 23:16213–16218
Luk HT, Mondelli C, Perez-Ramirez J, Ferre DC, Stewart JA (2017) Status and prospects in higher alcohols synthesis from syngas. Chem Soc Rev 46:1358–1426
Madikizela-Mnqanqeni NN, Coville NJ (2005) The effect of cobalt and zinc precursors on Co (10%)/Zn (x%)/TiO2 (x=0, 5) Fischer-Tropsch catalysts. J Mol Catal A Chem 225:137–142
Maitlis PM, de Klerk A (2013) Greener Fischer-Tropsch processes for fuels and feedstocks. Wiley-VCH Verlag & Co. KGaA, Weinheim, pp 237–265
Maitlis PM, Zanotti V (2008) Organometallic models for metal surface reactions: chain growth involving electrophilic methylidynes in the Fischer-Tropsch reaction. Catal Lett 122:80–83
Maitlis PM, Zanotti V (2009) The role of electrophilic species in the Fischer-Tropsch reaction. Chem Commun 1619–1634
Marin RP, Kondrat SA, Davies TE, Morgan DJ, Enache DI, Combes GB, Taylor SH, Bartley JK, Hutchings GJ (2014) Novel cobalt zinc oxide Fischer-Tropsch catalysts synthesised using supercritical anti-solvent precipitation. Catal Sci Technol 4:1970–1978
Mo X, Tsai Y-T, Gao J, Mao D, Goodwin JGJ (2012) Effect of component interaction on the activity of Co/CuZnO for CO hydrogenation. J Catal 285:208–215
Pan Z, Bukur DB (2011) Fischer-Tropsch synthesis on Co/ZnO catalyst-effect of pretreatment procedure. Appl Catal A Gen 404:74–80
Pan Z, Parvari M, Bukur DB (2014) Fischer-Tropsch synthesis on Co/ZnO - two step activation procedure for improved performance. Appl Catal A Gen 480:79–85
Paredes-Nunez A, Lorito D, Burel L, Motta-Meira D, Agostini G, Guilhaume N, Schuurman Y, Meunier F (2018) CO hydrogenation on cobalt-based catalysts: tin poisoning unravels CO in hollow sites as a main surface intermediate. Angew Chem Int Ed 57:547–550
Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Simmieniewska T (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (recommendations 1984). Pure Appl Chem 57:603–619
Tihay F, Pourroy G, Roger AC, Kiennemann A (1998) Selective synthesis of C2-C4 olefins on Fe-Co based metal/oxide composite materials. Stud Surf Sci Catal 119:143–148
Torres Galvis HM, Bitter JH, Ruitenbeek M, de Jong KP (2012) Supported iron nanoparticles as catalysts for sustainable production of lower olefins. Science 335:835–838
Torres Galvis HM, Koeken ACJ, Bitter JH, Davidian T, Ruitenbeek M, Dugulan AI, de Jong KP (2013) Effects of sodium and sulfur on catalytic performance of supported iron catalysts for the Fischer-Tropsch synthesis of lower olefins. J Catal 303:22–30
Wan H, Wu B, Zhang C, Teng B, Zhu Y, Xiang H, Li Y (2006) Effect of Al2O3/SiO2 ratio on iron-based catalysts for Fischer-Tropsch synthesis. Fuel 85:1371–1377
Wang X, Ning W, Hu L, Li Y (2012) Influences of Al2O3 on the structure and reactive performance of Co/ZnO catalyst. Catal Commun 24:61–64
Xing Y, Liu Z, Xue Y, Wu D, Fang S (2016) Variation trends of CO hydrogenation performance of (Al)-O-(Zn) supported cobalt nanocomposites: effects of gradual doping with Zn-O Lewis base. Catal Lett 146:682–691
Xue Y, Ge H, Chen Z, Zhai Y, Zhang J, Sun J, Abbas M, Lin K, Zhao W, Chen J (2018) Effect of strain on the performance of iron-based catalyst in Fischer-Tropsch synthesis. J Catal 358:237–242
Yang W, Gao H, Xiang H, Yin D, Yang Y, Yang J, Xu Y, Li Y (2001) Cobalt supported mesoporous silica catalyst for Fischer-Tropsch synthesis. Acta Chim Sin 59:1870–1877
Zhong L, Yu F, An Y, Zhao Y, Sun Y, Li Z, Lin T, Lin Y, Qi X, Dai Y, Gu L, Hu J, Jin S, Shen Q, Wang H (2016) Cobalt carbide nanoprisms for direct production of lower olefins from syngas. Nature 538:84–87
Zhukhovitskiy AV, Kobylianskii IJ, Wu C-Y, Toste FD (2018) Migratory insertion of carbenes into Au(III)-C bonds. J Am Chem Soc 140:466–474
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We thank the National Natural Science Foundation of China (NSFC, No. 21571161) for financial support.
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Xing, Y., Zhao, C., Jia, G. et al. Coprecipitated Fe/K/spinel nanocomposites for Fischer-Tropsch to lower olefins. J Nanopart Res 20, 202 (2018). https://doi.org/10.1007/s11051-018-4304-5
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DOI: https://doi.org/10.1007/s11051-018-4304-5