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J. Caro Tool Box Ceramic membranes for
catalysis
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Lighthouse projects (in preparation)
German Competence Network Catalysis

• Automotive Emission Control
• Innovative Methods of Catalyst Characterisation
• Multiphase Catalysis
• Membranes / Membrane Reactors

Funding budget approx. 12 Mio. (for 3 years)
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German Competence Network Catalysis ConNeCat

• Target
• Lighthouse Project
•  Tool-Box Ceramic Membranes for Catalysis
•  
• meets the necessary requirements of ConNeCat
•  
• Project is interdisciplinary, field overlapping
  
• Catalysis, Chemical Engineering, Theory and
  Modelling,
• Materials Science, Physical Chemistry
•  
• Network Co-operation 10 partners
• Þ  Membrane Producer, Chemical Industry, Process
  Developing Industry,
• Apparatus Developing Industry
• Þ  Universities, Research Institutes
•  
• Project is pre-competitive, high risc...
•  
• Aim of the project
• A Development of a Tool-Box filled with (i)
  membranes, (ii) modules,

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• Tool-Box
• A) Development of a Tool-Box of membranes,
  modules, application
• software, reactor know-how for the
  membrane-supported catalysis
• O2-permeable hollow fibres and capillaries with
  an oxygen-flux ? 0.5 m3/m2 h bar
• High-temperature module up to 900C housing
  oxygen-permeable membranes of 0.1 m2 area
• Full-ceramic module with 1 m2 microporous and
  catalytically active membrane area
• Technologies for the catalytic coating of
  membranes/modules
• Software for modeling of the different types of
  membrane reactors, modeling of the combined mass
  and heat transfer

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• Testing
• Testing of the Tool-Box in membrane-supported
  praxis-relevant catalytic model reactions in
  different types of membrane reactors
•  
• Membrane Flow-Through Reactor
• Selective hydrogenations
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• Permselective Membrane Reactor
• Selektive oxidations
•  
•  
• Membrane Contactor/Diffusor
• Selective hydrogenations
• Dimerizations

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• Reactor Principle 1 Membrane Flow-Through
  Reactor

• Problem of Packed Bed Reactor
• Different influences of mass transport reduce
  selectivity
• Solution Membrane Reactor!
• Controlled mass transport in porous catalytic
  membrane layer
• Suppression of pore diffusion by forced fluid
  flow
• Maximum selectivity due to the micro-kinetics
  can be reached
• Selective hydrogenation
• ?-methylstyrene ? cumene
• 1,3-cyclooctadien ? cycloocten

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Reactor Principle 2 Permselective Membrane
Reactor

• Main path Natural gas ? liquid products
  FiTro-synthesis
• Costs Linde-plant 40 of capital costs of a
  syngas plant
• Selective oxidation of CH4 ? syngas in membrane
  reactor with O2 which iscontinously separated
  from air

• Problems
• Material problems in sandwich-arrangement
• Stability of the oxidic O2- -transporting layer
• Low membrane surface to module volume ratio

• Solutions
• Monophase perovskite materials
  extruded/spuncapillaries/fibres
• Protecting coatings Sm-doted CeO2
• Use of capillaries/fibres with 1.5 m2/l

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• Reactor Principle 3 Catalytic Diffusor/Contactor
  Reactor (esp. for gas/liquid reactions)

Problem Selectivity of heterogeneously catalysed
gas/liquid reactions

• Solution
• Use of a porous catalytic membrane Reaction zone
  in the porous catalyst layer can be shifted by
  gas pressure
• Porous membrane is the carrier of a catalytic
  ionic liquid

• Selective hydrogenation
• ?-methylstyrene ? cumene
• 1,3-cyclooctadien ? cycloocten
•  
• Olefin dimerization
• propene ? hexene