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MOF mediated synthesis of Co catalysts for production of liquid fuels 

Depletion of petroleum and environmental concerns have driven a worldwide research on alternative processes for the production of energy carriers. Among the various possibilities and chemical conversion routes, syngas (a mixture of CO and H2) production followed by Fischer–Tropsch synthesis (FTS) holds promises for extensive implementation in the near future [1].

Transition metals are used in FTS process due to their considerable activity. Among them Co, Fe and Ru present the highest activity. Cobalt is preferred because of its higher activity for FTS, selectivity toward linear products, more stability, low activity towards water-gas shift (WGS) reaction and low price [2].

Last years, much effort has been put to tune the FT product selectivity of Co-based catalysts, which is dictated by the ASF polymerization model. In this respect, adding an acid functionality to the FTS catalyst formulation increases the product yields toward the C5–C11 cut [3]. However,  the strong Co–zeolite interaction results in a higher selectivity toward methane due to increased activity for hydrogenation and hydrocarbon hydrogenolysis reactions [4].

Recently, Metal Organic Frameworks (MOFs) have emerged as promising precursors for the synthesis of nanomaterials, because of their unique structure, atomic metal dispersion and textural properties. Namely, via pyrolysis of the commercial MOF Basolite® F300, highly dispersed iron carbides embedded in a matrix of porous carbon were obtained for the FTS [5].

Accordingly, this project aims at developing highly active and stable cobalt catalysts for the FTS via MOF pyrolysis, the first step being the selection, preparation and characterization of different cobalt MOFs, followed by the study of the pyrolysis conditions to finally proceed with the catalytic testing for the FTS in a six-flow fixed-bed microreactor setup [6].

  1. S. Sartipi, M. Makkee, F. Kapteijn, J. Gascon, Catalysis engineering of bifunctional solids for the one-step synthesis of liquid fuels from syngas: a review, Catal. Sci. Technol., 4 (2014) 893-907
  2. M. Davari, S. Karimi, A. Tavasoli, A. Karimi, Enhancement of activity, selectivity and stability of CNTs-supported cobalt catalyst in Fischer–Tropsch via CNTs functionalization, Applied Catalysis A: General. 485 (2014) 133-142.
  3.  B. Sun, M. Qiao, K. Fan, J. Ulrich, F. Tao, Fischer–Tropsch Synthesis over Molecular Sieve Supported Catalysts. ChemCatChem 3 (2011) 542–550
  4. S. Sartipi, K. Parashar, M.J. Valero-Romero, V.P. Santos, B. van der Linden, M. Makkee, F. Kapteijn, J. Gascon, Hierarchical H-ZSM-5-supported cobalt for the direct synthesis of gasoline-range hydrocarbons from syngas: Advantages, limitations, and mechanistic insight, Journal of Catalysis. 305 (2013) 179-190
  5.  V.P. Santos,  T.A. Wezendonk, J.J.D. Jaén,  A.I. Dugulan,  M.A. Nasalevich,  H-U. Islam, A. Chojecki, S. Sartipi, X. Sun, A.A. Hakeem, A.C.J. Koeken, M. Ruitenbeek, T. Davidian, G.R. Meima, G. Sankar, F. Kapteijn,  M. Makkee, J. Gascon, Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts.  Nature Communications 6 (2015) 
  6. S. Sartipi, H. Jansma, D. Bosma, B. Boshuizen, M. Makkee, J. Gascon, F. Kapteijn, F.Six-flow operations for catalyst development in Fischer-Tropsch synthesis: Bridging the gap between high-throughput experimentation and extensive product evaluation,  Rev Sci Instrum. 84  (2013) 124101.

Synthesis of DDR zeolite membranes for gas separation

For years, gas separation through a membrane has been hoped to be an environmentally benign and simple process in refinery, chemical and petrochemical industries since distillation, extraction, and absorption processes are generally energy consuming and/or require complicated facilities [1]. 

Zeolites have attracted much attention in this field due to their exceptional thermal and chemical stability as well as their uniform system of subnanometer-sized pores [2]. In contrast to the ‘‘8-ring’’ zeolites (with effective pore diameters from about 0.35 to 0.45 nm) such as natural chabazite and zeolite A which have been commonly applied as host systems in kinetic separation processes, all silica DDR-type zeolites are free of cations. The decreased hydrophilicity and catalytic activity make DDR zeolites promising adsorbents for practical applications, such as, separation of CO2/CH4 and olefin/paraffin mixtures [3]

However, several decades after the first zeolitic membrane was reported [4] it is fair to admit that synthesis reproducibility is still the main drawback. As zeolites cannot be prepared as self-supported membranes in a practical way, porous supports commonly of alumina or stainless steel are used to grow the zeolite membranes on [5].

Consequently, this project focuses on the development of a reproducible preparation method of a DDR type zeolite membrane, denoted Sigma1 with SiO2/Al2O3=400, by addressing the support seeding (which reduces the influence of the support in the flux and selectivity properties of the resulting zeolite membrane) by means of secondary growth method on Al2O3 supports.

  1. T. Binder, C. Chmelik, J. Kärger, A. Martinez-Joaristi, J. Gascon, F. Kapteijn, D. Ruthven, A diffusion study of small hydrocarbons in DDR zeolites by micro-imaging, Microporous and Mesoporous Materials. 180 (2013) 219-228.
  2. N. Kosinov, C. Auffret, G.J. Borghuis, V.G.P. Sripathi, E.J.M. Hensen, Influence of the Si/Al ratio on the separation properties of SSZ-13 zeolite membranes, J. Membr. Sci. 484 (2015) 140-145.
  3.  T. Tomita, K. Nakayama, H. Sakai, Gas separation characteristics of DDR type zeolite membrane, Microporous and Mesoporous Materials. 68 (2004) 71-75
  4. A. Ishikawa, T. H. Chiang, F. Toda, Separation of water–alcohol mixtures by permeation through a zeolite membrane on porous glass, J. Chem. Soc., Chem. Commun., 12 (1989) 764−765.
  5. Practical Approach to Zeolitic Membranes and Coatings: State of the Art, Opportunities, Barriers, and Future Perspectives, J. Gascon, F. Kapteijn, B. Zornoza, V. Sebastián, C. Casado,  J. Coronas, Chem. Mater. 25 (2012) 2829−2844


The Basque Government Ministery for Education, Language Policy and Culture is gratefully acknowledged for financial support.