|
|
FUNMAT research
activities on
Catalysis and Membranes
Contents • Short description of research
fields
• Relevant publications
•
Staff and laboratories
Short description of research fields
Catalysis is a key towards cheap, energy and environmental friendly chemical
processes for production or conversion of chemical components. In Norway such
research has received attention since the seventies, the main areas being
related to natural gas conversion, petrochemistry and refinery. The activities
focus on development of catalysts, catalyst design, characterisation and
testing, kinetics and mechanistic studies. Achievements in combinatorial
chemistry related to catalysts synthesis and evaluation have more recently
developed as a new important methodology.
Membrane technology has during some decades shifted focus from
concentrating on liquid filtration and water treatment, to become a field with
many possibilities owing to advances in materials synthesis, availability of
new materials, and design of nano- and microporous materials. Materials with
membrane and catalyst performance open for many new applications. Combinatorial
and High Throughput technology provides a new opportunity for discovery,
development and screening of new molecules and materials for targeted
applications. This new methodology provides powerful miniaturised automated
platforms that allow extensive mapping of parameter space.
The FUNMAT activities in catalysis and membranes have established
links to surface science, solid state chemistry and modelling, as well to
Norwegian and international industry. New catalysts have been designed and our
industrial partners have on that basis developed processes for
commercialisation; microporous SAPO-materials for MTO (methanol-to-olefin),
cobalt/rhenium supported alumina for Fischer-Tropsch and platinum/tin supported
hydrotalcite catalysts for dehydrogenation.
With respect to excellence and critical mass, FUNMAT will point at
the following fields (web-links will be established to the mentioned topics):
Porous Materials – oxides Microporous and mesoporous
materials are in focus, as are also pillared materials based on clays or other
layered crystal structures. Particular success has been achieved in
solvothermal synthesis of novel microporous materials, some having new
topologies, others being novel with respect to element or template
compositions. The ability to chemically modify known materials is important for
tuning their catalytic properties, as is the topology for separation and
selectivity. Research on Al, Si, P framework materials is complemented by solid
state chemistry activities on porous structures build by tetrahedral or
octahedral building units.
The porous materials are used as catalysts directly or as catalyst
supports. The activities have contributed to design and synthesis of active
catalysts within gas conversion and petrochemistry, such as the UOP/Norsk Hydro
MTO process. A mechanistic study of the MTO reaction and the proposed mechanism
is well recognised. The study of deactivation properties is another important
field.
The main focus is synthesis and modification of materials in order
to obtain desired performance. Characterisation such as unit cell or crystal
structure determination, surface measurements, pore size and volume
measurements, acidity characterisation, diffusion properties are equally
important. As a means to understand the crystallization processes in the gel
reactants and the role of templates or agents like fluoride, in-situ methods
XRD and NMR methods have been developed. Similar experiments are conducted for
following chemical changes in open framework structures during operational
(catalytic) conditions. The focus on materials synthesis/ design has triggered
development of new methodologies in combinatorial chemistry.
The use of
porous materials as adsorbents is another important focus area.
Porous materials – coordination polymers Recently, our
research on coordination polymers as absorbants and catalysts have in short
time led to discovery of many novel compounds. This new field will be
prioritised since hybrid frameworks provide additional chemical flexibility to
that of inorganic open framework structures. The research aims are inter alia
very open structures with huge internal surface areas, ability to functionalize
the organic linkers, construction of local coordination geometries resembling
that of catalytic active molecules, etc.
Supported catalysts and oxides Both low surface oxides (such
as silica and alumina) and porous materials are used as supports. Such oxides
are in addition used as catalysts alone. One has long experience with
impregnation/reaction of an active component onto a support, eventually
followed by activation. Crystal (surface) structure and degree/way of
dispersion of the active component are important aspects in addition to
testing, kinetics and mechanistic studies. Special competence is recognised on
processes like dehydrogenation of propane and Fischer-Tropsch. The research is
done in close collaboration with Statoil. Catalyst development and reactor
design for synthesis gas and hydrogen production is another area of importance.
Metal-organic complexes During the last decade focused
activities on metal-organic chemistry have been targeted towards
polymerisation, but also to activation of alkanes at lower temperatures.
Besides synthesis and characterisation of metal-organic complexes,
heterogenisation of metal-organic components on organic and inorganic surfaces
has been important. This also applies to mechanistic study in combination with
theoretical modelling of mechanism and energetic states.
Membranes Activities in liquid filtration and separation
cover the whole range from MF to NF/reverse osmosis. Main efforts relate to
membrane process development, but also new membranes have emerged from this
activity.
Research on gas separation is mainly directed to the development
of new membrane processes by developing new materials and characterisation of
their performance under relevant testing conditions. The activity covers a
broad range of materials from polymeric membranes for ethane/ethene separation
to inorganic membranes for CO2, H2 and O2 separation (microporous, mixed
conductors and Pd-based types). Currently, several industry projects are
running to develop new processes based on inorganic membranes in gas
separation, pervaporation and catalytic contactors. Recently a highly equipped
Membrane Process Laboratory was established where most of the activities on
inorganic membrane testing and process development are carried out.
For oxygen and hydrogen permeable membranes detailed structure
determination, and characterization of proton- and ion conductivities are
performed. Oxygen permeable membranes are furthermore studied in-situ by means
of XRD at working conditions.
Selection of relevant publications
Porous materials – oxides • I.M Dahl, S. Kolboe
”On the reaction mechanism for Hydrocarbon Formation from Methanol over
SAPO-34, Part 2 Isotopic Labeling Studies of the co-reaction of Popene and
Methanol.” J. Catal. 161(1996) 304-309
• Akporiaye, D. E.,
Fjellvåg, H.,Halvorsen, E. N., Hustveit, J., Karlsson, A. and Lillerud,
K. P. "The synthesis and structure solution of UiO-7, a new molecular sieve"
Chem. Comm. (1996) 601-602.
• Akporiaye, D. E., Fjellvåg,
H., Halvorsen, E. N., Haug, T., Karlsson, A. and Lillerud, K. P. "UiO-6: a
novel 12-ring AlPO4, made in an inorganic-organic cation system Chem. Commun.
(1996) 1553-1554.
• Kongshaug, K. O., Fjellvåg, H. and
Lillerud, K. P. ” The Synthesis and Crystal Structure of two Novel 3D Open
Framework Zinc Phosphates UiO-21 and UiO-22” Microporous Mesoporous
Mater. 39 (2000) 341-350.
• Christiansen, A. F., Fjellvåg,
H., Kjekshus, A. and Klewe, B. ”Synthesis and characterization of
molybdenum(VI)
oxide sulfates and crystal structure of two polymorphs of
MoO2(SO4)” J. Chem. Soc., Dalton Trans. 6 (2001) 806-
15.
• Vistad, Ø. B., Akporiaye, D. E. and Lillerud, K. P.
”Identification of a key precursor phase for synthesis of SAPO-
34 and
kinetics of formation investigated by in-situ X-ray diffraction, J. Phys. Chem.
B 105 (2001)12437-47
• P. Norby, F.I. Poshni, C.P. Grey, A.F.
Gualtieri and J.C. Hanson "Cation migration in zeolites; a combined in-situ
synchrotron X-ray powder diffraction and MAS NMR investigation of dehydration
of zeolite Cs(Na)-Y." J. Phys. Chem. B. 102 (1998) 839-856.
•
M.F. Ciraolo, J.C. Hanson, P. Norby and C.P. Grey “An In-situ X-ray Powder
Diffraction Study of the Adsorption of Hydrochlorofluorocarbons in
Zeolites” J. Phys. Chem. B 105 (2001) 2604-2611.
Porous materials – coordination polymers •
Kongshaug, K.O. and Fjellvåg, H. ”Coordination polymers constructed
from paddle-wheel building units”J. Solid State Chem. (2002)
• Kongshaug, K.O. and Fjellvåg, H., ”Synthesis and
characterization of CPO-1; three-dimensional coordination
polymers with
2,6-naphtalenedicarboxylate (ndc) ligands [M(ndc)(H2O)], M = Mn(II), Zn(II) and
Cd(II). Solid State Science (2002)
Supported catalysts and oxides • Nilsen, O., Kjekshus,
A. and Fjellvåg, H. ”Reconstruction and loss of platimun catalyst
during oxidation of ammonia” Appl. Catalysis A 207 (2001) 43-54.
• Åse Slagtern, Unni Olsbye, Richard Blom, Ivar M. Dahl, Helmer
Fjellvåg "Characterization of Ni on La modified Al2O3 catalysts during
CO2 reforming of methane" Appl. Catalysis A: 165 (1997) 379-390
Metallorganic complexes • R. Blom & I. M. Dahl
”On the sensitivity of metallocene catalysts toward molecular hydrogen
during ethylene polymerisation” Macromol. Chem. Phys., 200 (1999) 450.
• H.Heiberg, O. Swang, O.B.Ryan, O. Gropen ”C-H Activation at a
Cationic Platinum (II) Center: A Quantum Chemical Investigation” J. Phys.
Chem. A, 103(1999) 10004-10008
• Richard Blom, Ole Swang, Richard
H. Heyn, "Semi-Batch Polymerisations of Ethylene with Metallocene Catalysts in
the Presence of Hydrogen, 3. Correlation Between Hydrogen Sensitivity and
Molecular Parameters", Macromol. Chem. Phys. 203, 381-387 (No. 2, 2002)
• Richard Blom, Ole Swang, "Dynamic Behaviour of
Tris(2-methylallyl)chromium - NMR and DFT Results", Eur. J. Inorg. Chem. 2002,
411-415.
• E. W. Hansen, R. Blom, P. O. Kvernberg, "Diffusion of
Methylaluminoxane (MAO) in Toluene Probed by 1H-NMR Spin-Lattice Relaxation
Time", Macromol. Chem. Phys. 202, 2880-2889 (No. 14, 2001).
• R.
Blom, I.M. Dahl, O. Swang, "Methyl side chain formation on the CrCp2/SiO2
catalyst during poly-merisation of ethylene: Spectroscopic analyses and
theoretical modelling", J. Catal. 2000, 194, 352-363
Membranes • Helmer Fjellvåg, Bjørn C.
Hauback and Rune Bredesen. "Crystal Structure of the Mixed Conductor
Sr4Fe4Co2O13". Journal of Materials Chemistry 7 (12) 1997, 2415-2419.
• Christian Simon, Rune Bredesen and Christelle Denonville.
“Characterisation of surface modified alumina membranes”. In the
Proceedings of the International Conference on Inorganic Membranes, June 22-26,
1998, Nagoya, Japan, p. 416-419.
• Rune Bredesen,
Frédéric Mertins and Truls Norby. “Measurements of surface
exchange kinetics and chemical diffusion in dense oxygen selective
membranes”. Catalysis Today, 56 (2000) 315-324.
• Rune
Bredesen, Truls Norby, Asgeir Bardal and Vibeke Lynum. “Phase relations,
chemical diffusion and electrical conductivity in pure and doped Sr4Fe6O13
mixed conductor materials”. Solid State Ionics, 135 (2000) 687-97.
• Arian Nijmeijer, Henk Kruidhof, Rune Bredesen and Henk Verweij.
”Preparation and properties of hydrothermally stable ?-alumina
membranes”. J. Am Ceram. Soc. 84 ?1? (2001) 136-140.
•
Asgeir Bardal and Rune Bredesen. “Intergrowth of (Sr1-yLay)4Fe6O13?? and
(Sr1-xLax)FeO13-? in mixed conductor membrane materials”. J. Materials
Sci. 36 ?22? (2001) 5357-5367.
Combinatorial methods • D.E. Akporiaye, I.M. Dahl, A.
Karlsson and R. Wendelboe ”Combinatorial Approach to the Hydrothermal
Synthesis of Zeolites” Angew. Chem. Internat. Ed. 37 (5) (1998)
609-611
• D. Akporiaye, I. Dahl, A. Karlsson, M. Plassen, R.
Wendelbo, D.S. Bem, R. W. Broach, G. J. Lewis, M. Miller, J. Moscoso,
“Combinatorial Chemistry – The emperor’s new clothes?”,
Micro. Meso. Materials, (2001).
• WO9836826 Multiautoclave for
combinatorial synthesis of zeolites and other materials
•
WO0102089 Multi-test assembly for evaluating, detecting and monitoring
processes at elevated pressure
• WO0144801 Process for
simultaneously evaluating a plurality of catalyst
Staff and laboratories
Permanent staff (professors, associate professors,
scientists) • Catalysis
• Combinatorial chemistry
•
Metalorganic chemistry
• Solid state chemistry
• Membrane
technology
• Surface science
Post docs • Catalysis
• Combinatorial
chemistry
• Metalorganic chemistry
• Solid state
chemistry
• Membrane technology
• Surface science
Phd-students • Catalysis
• Combinatorial
chemistry
• Metalorganic chemistry
• Solid state
chemistry
• Membrane technology
• Surface science
in
addition to foreign guest scientists and master-students
|
|
