Abstract
In this work, we demonstrate an efficient and high-performance catalyst for the production of light olefins from synthesis gas employing manganese (Mn)-mediated graphene oxide. First the CO hydrogenation reaction was catalyzed using bimetallic alumina supported-cobalt-manganese catalysts with various ratio of cobalt to Mn (1:1, 1:2, 1:3, 2:1 and 3:1). After the determination of the effect of different ratios on C2–C4 light olefin production, the efficiency of nanoporous graphene and reduced graphene oxide as support at an optimum ratio of bimetallic Co–Mn/Al2O3 catalyst were evaluated. The catalysts were characterized by BET, TPR, FTIR, RAMAN, TGA, XRD, FESEM, ICP, and XPS measurements. The reactions carried out in a fixed bed reactor under the constant condition (320 °C, atmospheric pressure, H2/CO = 1). It was identified that light olefin selectivity of the catalysts varies with different ratios. By increasing of the amount of Mn up to 1, methane formation decreased and light olefin selectivity increased. Conversely, with the further increase of the amount of Mn, light olefin selectivity decreases. This phenomenon is attributed to varying the degrees of Mn incorporation in the Co3O4 particles, which causes different degrees of reduction limiting the available metallic Co surface area. Also, the advantages of reduced graphene oxide supported nanoparticles (NPs) included higher conversion and C2–C4 light olefin selectivity in comparison with the graphene supported catalyst. The obtained results from the TPR revealed that the NPs reducibility was higher for the RGO supported catalyst. An increase of selectivity and conversion of Co–Mn/RGO catalyst is likely due to altering the surface interactions of NPs with the functional groups on reduced graphene oxide which was confirmed with XPS, FTIR and Raman analyses.
Similar content being viewed by others
References
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
Chang CD (1983) Science and engineering hydrocarbons from methanol. Catal Rev Sci Eng 25:1–118
Galvis HMT, Jong KP (2013) Catalysts for production of lower olefins from synthesis gas: a review. ACS Catal 3:2130–2149
Dry ME (2002) The Fischer-Tropsch process: 1950–2000. Catal Today 71:227–241
Jong JOE, Bae W, Jun PKK (2009) Slurry-phase Fischer-Tropsch synthesis using Co/Al2O3, Co/SiO2 and Co/TiO2: effect of support on catalyst aggregation. Catal Lett 4:403–409
Xiong H, Jewell LL, Coville NJ (2015) Shaped carbons as supports for the catalytic conversion of syngas to clean fuels. ACS Catal 5:2640–2658
Chen X, Deng D, Pan X, Bao X (2015) Iron catalyst encapsulated in carbon nanotubes for CO hydrogenation to light olefins. J Catal 36:1631–1637
Moussa S, Panchakarla LS, Ho MQ, El-shall MS (2014) Graphene supported iron-based nanoparticles for catalytic production of liquid hydrocarbons from synthesis gas. ACS Catal 4:535–545
Vi F, Illas F (2015) Transition metal adatoms on graphene: a systematic density functional study. Carbon 95:525–534
Wang Y, Rong Z, Wang Y, Qu J (2016) Ruthenium nanoparticles loaded on functionalized graphene for liquid-phase hydrogenation of fine chemicals: comparison with carbon nanotube. J Catal 333:8–16
Luo M, Li H (2018) The effect of different solvents on graphene supported cobalt Fischer-Tropsch catalyst. React Kinet Mech Catal 124:279–291
Cheng Y (2016) Fischer-Tropsch synthesis to lower olefins over potassium-promoted reduced graphene oxide supported iron catalysts. ACS Catal 6:389–399
Wang Y (2018) Tailored synthesis of active reduced graphene oxides from waste graphite: structural defects and pollutant-dependent reactive radicals in aqueous organics decontamination. Appl Catal B Environ 229:71–80
Addad A, Siebe B (2017) Reduced graphene oxide decorated with Co3O4 nanoparticles nanocomposites: a reusable catalyst for highly efficient reduction of 4-nitrophenol, and Cr (VI) and dye removal from aqueous solutions. Chem Eng J 322:375–384
Cheng Y (2017) Mg and K dual-decorated Fe-on-reduced graphene oxide for selective catalyzing CO hydrogenation to light olefins with mitigated CO2 emission and enhanced activity. Appl Catal B Environ 204:475–485
Guo XN, Jiao ZF, Jin GQ, Guo XY (2015) Photocatalytic Fischer-Tropsch synthesis on graphene-supported worm-like ruthenium nanostructures. ACS Catal 5:3836–3840
Steen E, Prinsloo FF (2002) Comparison of preparation methods for carbon nanotubes supported iron Fischer-Tropsch catalysts. Catal Today 71:327–334
Guczi L (2006) CO hydrogenation over cobalt and iron catalysts supported over multiwall carbon nanotubes: effect of preparation. J Catal 244:24–32
Xiao J, Pan Y (2016) Selective conversion of syngas to light olefins. J Catal 351:1065–1068
Zhong L (2016) Cobalt carbide nanoprisms for direct production of lower olefins from syngas. Nat Publ Gr 538:84–87
Zhang Q, Kang J, Wang Y (2010) Development of novel catalysts for Fischer-Tropsch synthesis: tuning the product selectivity. Chem Cat Chem 2:1030–1058
Zhang X, Liu Y, Liu G, Tao K, Meng F (2010) One-step preparation of bimodal Fe–Mn–K/SiO2 catalyst and its catalytic performance of slurry phase Fischer-Tropsch synthesis. Catal Lett 2:7–16
Al-dossary M, Ismail AA, Fierro JLG, Bouzid H, Al-sayari SA (2015) Effect of Mn loading onto MnFeO nanocomposites for the CO2 hydrogenation reaction. Appl Catal B Environ 165:651–660
Tristantini D, Borg Q, Ilver L, Ja S (2009) Hydrocarbon production via Fischer-Tropsch synthesis from H2 -poor syngas over different Fe-Co/Al2O3 bimetallic catalysts. Appl Catal B Environ 89:167–182
Mirzaei AA, Faizi M, Habibpour R (2006) Effect of preparation conditions on the catalytic performance of cobalt manganese oxide catalysts for conversion of synthesis gas to light olefins. Appl Catal A Gen 306:98–107
Khodaei MM, Feyzi M, Shahmoradi J, Joshaghani M (2014) The sol-gel derived Co-Mn/TiO2 catalysts for light olefins production. Chem Cat Chem 42:2–8
Werner S, Johnson GR, Bell AT (2014) Synthesis and characterization of supported cobalt–manganese nanoparticles as model catalysts for Fischer-Tropsch synthesis. ChemCatChem 6:2881–2888
Zakeri M, Samimi A, Khorram M, Atashi H, Mirzaei A (2010) Effect of forming on selectivity and attrition of co-precipitated Co-Mn Fischer-Tropsch catalysts. Powder Technol 200:164–170
Colley S, Copperthwaite RG, Hutchings GJ, Van der Riet M (1988) Carbon monoxide hydrogenation using cobalt manganese oxide catalysts: initial catalyst optimization studies. Ind Eng Chem Res 27:1339–1344
Li X, Zhong B, Peng S, Wang Q (1994) Fischer-Tropsch synthesis on Fe-Mn ultrafine catalysts. Catal Lett 23:245–250
Chua CK, Pumera M (2015) The reduction of graphene oxide with hydrazine: elucidating its reductive capability based on a reaction-model approach. Chem Commun 52:72–75
Zafari R, Abdouss M, Zamani Y (2019) Application of response surface methodology for the optimization of light olefins production from CO hydrogenation using an efficient catalyst. Fuel 237:1262–1273
Dinse A, Aigner M, Ulbrich M, Johnson GR, Bell AT (2012) Effects of Mn promotion on the activity and selectivity of Co/SiO2 for Fischer-Tropsch synthesis. J Catal 288:104–114
Gregg SJ, Sing KSW (1982) Adsorption, surface area and porosity. J Electrochem Soc 114:279
Rønning M (2010) Combined XRD and XANES studies of a Re-promoted Co/γ-Al2O3catalyst at Fischer-Tropsch synthesis conditions. Catal Today 155:289–295
Feyzi M, Hassankhani A (2013) TiO2 supported cobalt-manganese nano catalysts for light olefins production from syngas. J Energy Chem 22:645–652
Zafari R, Abdouss M, Zamani Y, Tavasoli A (2017) An efficient catalyst for light olefins production from CO hydrogenation: synergistic effect of Zn and Ce promoters on performance of Co–Mn/SiO2 catalyst. Catal Lett 147:2475–2486
Krishnamoorthy K, Veerapandian M, Yun K, Kim S (2012) The chemical and structural analysis of graphene oxide with different degrees of oxidation. Carbon 53:38–49
Liang Q, Chen K, Hou W, Yan Q (1998) CO hydrogenation over nanometer spinel-type Co/Mn complex oxides prepared by sol-gel method. Appl Catal A Gen 166:191–199
Pedersen E, Svenum IH, Blekkan EA (2018) Mn promoted Co catalysts for Fischer-Tropsch production of light olefins—an experimental and theoretical study. J Catal 361:23–32
Johnson GR, Werner S, Bell AT (2015) An investigation into the effects of Mn promotion on the activity and selectivity of Co/SiO2 for Fischer-Tropsch synthesis: evidence for enhanced CO adsorption and dissociation. ACS Catal 5:5888–5903
Ma J, Wang L, Mu X, Cao Y (2015) Enhanced electrocatalytic activity of Pt nanoparticles supported on functionalized graphene for methanol oxidation and oxygen reduction. J Colloid Interface Sci 457:102–107
Park S (2011) Hydrazine-reduction of graphite- and graphene oxide. Carbon 49:3019–3023
Wang WX (2012) The study of interaction between graphene and metals by Raman spectroscopy. J Appl Phys 109:501–503
Hosseini A, Salari D (2011) Chemical-physical properties of spinel CoMn2O4 nano-powders and catalytic activity in the 2-propanol and toluene combustion: effect of preparation method. J Environ Sci Heal A 46:291–297
Sun L, Zhou L, Yang C, Yuan Y (2017) oxide as an efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions. Int J Hydrog Energy 42:15140–15148
Bezemer GL (2006) Investigation of promoter effects of manganese oxide on carbon nanofiber-supported cobalt catalysts for Fischer-Tropsch synthesis. J Catal 237:152–161
Acknowledgements
The authors gratefully acknowledge Research Institute of Petroleum Industry and Amirkabir University of Technology for funding support of this research. We are also thankful for XPS laboratory at University of Laval (Canada).
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Zafari, R., Abdouss, M. & Zamani, Y. Effect of Mn and reduced graphene oxide for the Fischer–Tropsch reaction: an efficient catalyst for the production of light olefins from syngas. Reac Kinet Mech Cat 129, 707–724 (2020). https://doi.org/10.1007/s11144-020-01742-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11144-020-01742-7