Design and Manufacturing of Catalytic Membrane Reactors by Developing New Nano-architectured Catalytic and Selective Membrane Materials This project is supported by the European Community s Seventh Framework Programme Grant Agreement Nº NMP3-LA-2011-262840 Duration: 4 years. Starting date: 01-July-2011 Contact: joseluis.viviente@tecnalia.com Then present document reflects only the author s views and the Union is not liable for any use that may be made of the information contained therein. 05-08-2013 / Page 1
DEMCAMER s Aim (I) To develop innovative multifunctional Catalytic Membrane Reactors (CMR) Based on: new nano-architectured catalysts and selective membranes materials To improve the CMRs : performance durability cost effectiveness sustainability: lower environmental impact lower use of raw materials Set up and validate pilot prototypes 05-08-2013 / Page 2
DEMCAMER s Aim (II) CMRs to be used for selected chemical processes: Autothermal Reforming (ATR) Fischer-Tropsch Synthesis (FTS) Water Gas Shift (WGS) Oxidative Coupling of Methane (OCM) For the production of: pure hydrogen liquid hydrocarbons ethylene 05-08-2013 / Page 3
DEMCAMER Partnership This research is carried out by a multidisciplinary and complementary team consisting of 17 top level European organisations from 10 countries: 8 research institutes and universities working together with representative top industries in different sectors (from raw materials suppliers to chemical end-users). 05-08-2013 / Page 4 University of Calabria
Consortium Composition 1. TECNALIA, Spain 2. VITO, Belgium 3. UNICAL, Italy 4. TU/e, The Netherlands 5. ICP-CSIC, Spain 6. FhG-IKTS, Germany 7. BIC, Russian Federation 8. INERIS, France 9. RKV, German 10. CERPOTECH, Norway 11. HYBRID, The Netherlands 12. HYGEAR, The Netherlands 13. ABNT, Spain 14. QUANTIS, Switzerland 15. HÖGANÄS, Sweden 16. TOTAL RC, Belgium 17. TOTAL EP, France University of Calabria 05-08-2013 / Page 5
Project Structure Development of novel catalyst materials Development of innovative membranes Novel catalytic membrane reactors designed: on the basis of novel catalysts and membranes using new reactor configurations supported by simulation Modelling and simulation at different levels: materials (membranes and catalysts) reactor prototypes control system Lab scale and prototype reactors testing and validation Life Cycle Analysis, industrial risk assessment study 05-08-2013 / Page 6
Partnership Synergies 05-08-2013 / Page 7
Overview of the Work Structure WP2. Industrial specifications [HYGEAR] WP11. Scientific coordination [TU/e] WP10. Dissemination and Exploitation [UNICAL] WP1. Management [TECNALIA] WP3. Catalysts development [CSIC] Catalyst preparation Catalyst characterisation Activity test Scale up WP5. Lab scale reactors [TU/e] Integration in CMRs Testing of CMRs WP6. Pilot prototype [HYGEAR] Design of Pilot Set up WP4. Membrane development [VITO] Material for membranes Membranes support Membranes development and characterization WP7. Testing and Validation [ABNT] FAT Testing and validation WP8. Modeling and Simulation [UNICAL] Ab initio calculations Transport in membranes CMR simulations Process simulations Pilot scale simulation WP9. LCA and Safety issues [INERIS] 05-08-2013 / Page 8
Scientific and Technical Objectives (I) New membrane materials and nano-architectured catalysts improved properties long durability reduced cost Better understanding of fundamental physicochemical mechanisms relationship between structure/property/performance manufacturing process of membranes and catalysts Achieving radical improvements in membrane reactors design modelling efficiency of configurations 05-08-2013 / Page 9
Scientific and Technical Objectives (II) Validating reactor configurations at semi-industrial prototype level in all four selected chemical process (ATR, WGS, OCM, FTS) for pure hydrogen, liquid hydrocarbons and ethylene production Improving cost efficiency of reactors by increasing their performance decreasing raw materials consumption decreasing associated energy losses Use of new raw materials (i.e. convert non-reactive raw materials) Assessment of the four CMR developed processes health and safety environmental impact a complete LCA of the developed technologies 05-08-2013 / Page 10
Catalysts for ATR - WGS - OCM - FTS Reactions Development of catalytic materials Physicochemical characterisation Activity tests Scale-up and confirmation 05-08-2013 / Page 11
Membranes ATR - WGS - OCM - FTS Reactions Development of novel materials and membranes for application in CMRs MIEC membranes Hollow fibres (H 2 and O 2 permeation) Coatings (O 2 permeation) Metallic membranes (H 2 permeation) Zeolite membranes (H 2 permeation and water removal) 05-08-2013 / Page 12
Development of Materials for Novel Membranes Perovskite powders for MIEC membranes Selection and manufacture of a wide range of feedstock powders for the development of hollow fibres for O 2 and H 2 permeation Materials for inter-diffusion layers of metal based membranes Manufacture of Al 2 O 3 and YSZ based powders for development of layers by thermal spraying Optimisation of morphology by freeze granulation process before granulation after granulation 05-08-2013 / Page 13
Development of Materials for Zeolites Nanocrystals having FAU-Y topology with uniform particles size distribution have been prepared in high yield through an organic-template-free hydrothermal synthesis by using a FAU membrane as structure directing agents. Advantages: The membrane used as structure directing agent can be readily removed at the end of the reaction, thus avoiding challenging purification procedures. The method is simple, eco-friendly and highly reproducible. The method could be favourably extended to other microporous alumino-silicate of different topologies. 05-08-2013 / Page 14
Development of High-Quality Metallic Supports for MIEC, Zeolite and Metal-Based Membranes Materials for metallic membrane supports Different powder morphologies, finer particle sizes Metal powders for surface layers in gradient structures Metallic membrane supports Planar porous metallic supports for H 2 permeation membranes Gradient and homogenous structures with different strengths and porosities Planar compacted metallic porous supports for O 2 permeation membranes Porous tubes 05-08-2013 / Page 15
MIEC Membranes for H 2 and O 2 Permeation Development of perovskite membranes by spinning and phase inversion methods Permeation measurements A-site B-site O 2- Structural characterisation: XRD and SEM analyses Intensity a.u. 2θ 05-08-2013 / Page 16
Zeolite Membranes for H 2 and Water Separation Improvement of FAU membrane layer by anchoring of the zeolite seeds onto support Structural characterisation: XRD and SEM analyses Permeation tests: single and mixed gas (dry and humidified) 4000 3000 Intensity, a.u. 2000 1000 0 4 10 16 22 28 34 40 46 52 58 64 70 2 theta University of Calabria 05-08-2013 / Page 17
Development of Lab-Scale CMRs Selection of Catalytic Membranes Reactors components: catalysts membranes materials supports sealings Integration of these elements into lab-scale reactors specifically designed for ATR, WGS, OCM and FTS Validation of the performance of lab-scale reactors Identification of best designs for pilot prototypes 05-08-2013 / Page 18
Reactor Configurations - ATR Reverse flow CMR concept for combined high-temperature O 2 separation and autothermal reforming of methane 05-08-2013 / Page 19
Reactor Configurations - WGS WGS reaction and hydrogen separation coupled in one single unit CO + H 2 O CO 2 + H 2 0 H 222 = -41.09 kj/mol Micro-structured CMR concept maximisation of membrane area complete process integration unique mass and heat transfer capabilities maximal energy and mass transfer efficiency 05-08-2013 / Page 20
WGS in a Fixed-Bed Membrane Reactor in Permeate Pure H 2 Pd-Ag membrane Catalytic bed Feed Retentate H 2 CO CO 2 MFC CO, CO 2, H 2, H 2 O (Retentate) Permeate GC 6890 Agilent H 2 CO, CO 2, H 2 H 2 O Furnace Membrane reactor scheme Experimental laboratory-scale plant MR TR Temperature, C 350-400 Feed Pressure, bar 7-9 7.5 Permeate Pressure, bar 1 - H 2 O /CO feed molar ratio 1 GHSV (gas hourly space velocity) 8,000; 14,700; 36,700 h -1 Feed composition (dry), % CO:H 2 :CO 2 :N 2 = 46:48:5:1 No sweep gas was used University of Calabria 05-08-2013 / Page 21
Reactor Configurations - OCM CMR with packed-bed configuration (modified from Caro et al., 2010) 2CH 4 + O 2 C 2 H 4 + 2H 2 O 0 H 298 = -141 kj/mol CH 4 optimising operating parameters (CH 4 /O 2 feed ratio, T) to achieve enhanced CH 4 conversion, best C 2 selectivity and C 2 product yield 05-08-2013 / Page 22
Reactor Configurations - FTS packed bed membrane reactor distributed feeding HC s + H 2 O in-situ water removal HC s Shell Catalyst particles P 1 P 2 Cross-section View: PBMR Membrane Shell Permeate Catalyst Side: particles H 2 O P 2 P 1 Permeate Side: H 2 O + Gas sweep Permeate Side: H 2 O HC s Cross-section View: PBMR Membrane Reaction Compartment (CO Feeding) H 2 Feeding Membranes for the distributed feeding of H 2 P 1 > P 2 Catalyst Particles H 2 CO Reaction Compartment Reaction Compartment (Syngas Feeding) Membranes for the selective H 2 O removal P 1 > P 2 Catalyst Particles Permeate Side: H 2 O Reaction Compartment catalytic membrane milli-reactor in-situ water removal Shell Permeate Catalyst P 1 P 1 Side: particles H 2 O P 2 Permeate Side: H 2 O + Gas sweep HC s Permeate Side: H 2 O Cross-section View: CMM HC s Membrane Reaction Compartment (Syngas Feeding) Membranes for the selective H 2 O removal P 1 > P 2 Permeate Side: H 2 O Catalyst Layer Reaction Channel 05-08-2013 / Page 23
Modelling and Simulation (I) For membranes: Study of zeolite membranes properties by means of molecular modelling and quantum chemical calculations: Identification of structure-function relationships at molecular level Identification of the optimal procedure for evaluating the selectivity Identification selectivity of gases Comparative analysis between the fundamental transport properties of Pd and Pd-based alloys and the corresponding properties of new (non-pd) alloys formed from different metals For catalysts: Search for the optimal catalyst s structure for ATR, WGS, OCM, FTS by correlation between their morphological and structural properties and their catalytic performance 05-08-2013 / Page 24
Modelling and Simulation (II) For ATR: Develop a reliable dynamic model in a reverse-flow membrane reactor For WGS: Develop a phenomenological model for fluidised-bed membrane microreactors Develop a reliable 2D model for membrane micro-reactors Compare fluidised bed and packed-bed membrane micro-reactors Analyse 1D or 2D dimensionless models for fixed-bed membrane reactor For OCM: Develop a reliable 1D detailed model for the study of hollow fibre MIEC membranes reactors with packed-bed configuration For FTS: 2D simulations of a fixed-bed catalytic membrane reactor 05-08-2013 / Page 25
Modelling and Simulation (III) Evaluation of the membrane separation properties: Mathematical models describing the permeation in metal and zeolite membranes Identification of elementary steps affecting the permeation through the membrane and their influence on mass transport properties Processes: Design of new processes integrated with catalytic membrane reactors Analysis of the performance of the integrated processes as function of the operating conditions assuring the best performance of the whole integrated process Pilot scale: Modelling of the pilot scale reactors for ATR, WGS, OCM and FTS Definition and modelling of control strategies and control routines for the pilot scale reactors 05-08-2013 / Page 26
Modelling Example (I) Transport in Metal-Based Membranes Model based on a multicomponent approach Physical system Feed Side Pd-based layer Porous support Permeate Side 1 2 3 4 Gaseous Film Pd-based layer Layer 1 Porous support Layer n Gaseous Film Membrane layers Pd-based layer Porous support Multicomponent Mass Transfer Adsorption Surface-to-Bulk Bulk Diffusion Bulk-to-Surface Desorption Layer 1 Mass transfer in the pores Layer n Multicomponent Mass Transfer Mass transfer mechanisms Mathematical description University of Calabria 05-08-2013 / Page 27
Feed Modelling Example (II) WGS Fixed-Bed Membrane Reactor Retentate 1 Pd-Ag membrane Catalytic bed Permeate Pure H 2 1500 Pd-Ag MR Traditional reactor CO Conversion, - 0.5 TR Temperature Feed pressure Feed mixture composition 300-450 C 500, 1000;1500; 3000 kpa CO: H 2 O: CO 2 : H 2 : N 2 = 31.25:31.3:25.5:33:1, % molar 0 10000 h -1 300 400 500 Temperature, C H 2 O/CO feed molar ratio 1 GHSV 10000-40000 h -1 University of Calabria 05-08-2013 / Page 28
Modelling Example (III) WGS Process Simulation Traditional Process H 2 (high purity) WGS HT WGS LT CO 2 separation H 2 purification CO 2 NATURAL GAS Steam Methane Reforming Membrane Integrated Process H 2 WGS (high purity) MR H 2 (high purity) CO 2 separation H 2 purification University of Calabria 05-08-2013 / Page 29 CO 2
WGS Membrane Reactor Integration Permeate (H 2 highly pure) Modelling Example (III) cont d Alternative downstream post-treatments WGS MR H 2 H 2 CO 2 separation H 2 purification NG REFORMING water WGS MR Retentate stream CO 2 separation H 2 purification H 2 CO 2 compression and storage University of Calabria 05-08-2013 / Page 30
Pilot Scale Prototypes Design and setup of the pilot scale catalytic membrane reactors Pilot reactors for ATR, WGS, OCM and FTS processes Depending on the working pressure all reactors will be designed and manufactured according the Pressure Equipment Directive of the EC (97/23/EEC) Overall system controls for the different reactor types will be designed and constructed to ensure automatic operation of the systems and safety aspects and control strategies developed according to Pilot scale modelling All system components will be mounted into an enclosure and will undergo a Factory Acceptance Test (FAT) before being set into operation for validation and testing. 05-08-2013 / Page 31
Pilot Prototypes Testing and Validation Testing and validation of the pilot scale prototype reactors For testing and validating of the pilots, corresponding test plans and protocols will be defined including parameters and/or values that have to be derived from the tests, such as system efficiency, etc. Results will be compared to the requirements and specifications Test results will be used in Modelling and Simulation to validate and improve the pilot scale models and the system control strategies, as well as for the LCA and the accidental industrial risk assessment 05-08-2013 / Page 32
Life Cycle Assessment and Safety Issues Assessment of socio-economic sustainability of the proposed technologies from an environmental and safety perspective. Environmental Life Cycle Assessment analysis of the CMR process Identification and evaluation of key safety parameters and risk analysis Proposal of recommendations for the safe operation of the CMR technology Socio-economic analysis to evaluate the sustainability and feasibility of the CMR technology (process performance, environmental and safety constraints) compared to currently available technologies Process Performance Constraints Environmental Constraints Safety Constraints Socio-Economic Analysis 05-08-2013 / Page 33
Environmental Life Cycle Assessment Objectives of the Life Cycle Assessment DEMCAMER will perform a robust environmental Life Cycle Assessment (LCA) of the new technologies to be developed (CMR) compared with the reference technologies (baseline) Within DEMCAMER, the LCA focuses on the following environmental impact categories over the entire life cycle of the processes: Greenhouse gas (GHG) emissions (climate change) Non-renewable primary energy use Direct and indirect impacts on human health Direct and indirect impact on ecosystems Water use (incl. water impact assessment) 05-08-2013 / Page 34
Environmental Life Cycle Assessment Objectives of the Life Cycle Assessment Example of ATR-CMR Reference technology (baseline) CMR technology compared with 05-08-2013 / Page 35
Thank you for your attention 05-08-2013 / Page 36