Dittmeyer, R.

Görke, O.

Kraut, M.

Pfeifer, P.

Schüler, N.

Thormann, J.

English

KITopen

Institute for Micro Process Engineering (IMVT)www.kit.eduKIT – University of the State of Baden-Wuerttemberg and National Research Center of the Helmholtz AssociationOpportunities and Challenges of Membrane Integration into Compact Microstructured ReactorsR. Dittmeyer, J. Thormann, O. Görke, P. Pfeifer, N. Schüler, M. KrautChinese-German Workshop on Inorganic Membranes, Guangzhou, March 21-25, 2010Institute for Micro Process Engineering 2 23.03.2010 Prof. R. DittmeyerWhat is KIT?Start: National Excellence Initiative 2006 - Success in all three funding lines Graduate Schools: Karlsruhe School of Optics and PhotonicsExcellence Clusters: DFG Center for Functional NanostructuresConcept for the Future: Merger of University and Research Center to form the Karlsruhe Institute of Technology (October 1, 2009)12 km, 20 Min. ,  i.Natural and Engineering Sciencest l  i i  i+Forschungszentrum Karlsruhe GmbHUniversität Karlsruhe (TH)10             Programs31             Institutes3690             Employees408 Mio € Budget11             Faculties118             Institutes4269             Employees299 Mio € Budget18353            StudentsNorth Campus South CampusInstitute for Micro Process Engineering 3 23.03.2010 Prof. R. DittmeyerKIT - Centers and FocusesKIT Centers:EnergyNano & Micro Science and TechnologyElementary Particle and AstroparticlePhysicsClimate and EnvironmentKIT Focuses:COMMputationMobility SystemsOptics and PhotonicsHumans and TechnologyApplied and New MaterialsInstitute for Micro ProcessEngineering (IMVT)North CampusInstitute for Micro Process Engineering 4 23.03.2010 Prof. R. DittmeyerIMVT - Mission StatementR&D for the manufacture of highly efficient microstructure devices for process engineering tasks in chemical, pharmaceutical and related industriesRenewing process engineering through “Process Intensification”Safe: Reduced reactive inventory, Quenching of reactions, Local production avoids transportEfficient: Energy and raw materials, Reduced heat and mass transport resistances and improved control on the process conditionsCompact: Higher space-time-yield, Integration of additional functions, CompartmentalizationCheap: Looking at investment plus operating costsFast: Standardized, well characterized equipmentPrinciples: Microstructuring of the reactor volume (thin fluid layers)Supply or removal of material and energy on the spot(hierarchical structures)Institute for Micro Process Engineering 5 23.03.2010 Prof. R. DittmeyerAdvantages:Excellent heat transfer(up to 20 kW pro cm3)Excellent mass transfer (channel to wall)High pressure resistanceInhibition or retardation of flames and explosions (depends)Challenges:Prone to pluggingProne to corrosionHigh pressure drop (depends)Key Features of Microstructure Devices100 µmCross flow metallic heat exchangerInstitute for Micro Process Engineering 6 23.03.2010 Prof. R. DittmeyerIMVT - CompetencesTestingSimulation(CFD)ManufacturingMicrostructuring(e.g., Micro Milling)Design (CAD-Software)AdaptationIMVTStackingJoining(e.g., Diffusion Bonding)Personnel 62 (5)Applications 26 (4)Administration 5 (1)Manufacturing 15Fundamentals 16Optional: coating with a functional layerInstitute for Micro Process Engineering 7 23.03.2010 Prof. R. DittmeyerWhy Membranes in Microstructure Devices ?Two systems:Membrane reactor for hydrogen production: (1) reforming of natural gas / biogas, (2) dehydrogenation of methylcyclohexaneGravity-insensitive gas/liquid separation or contactingMicrostructure devices dooffer a large surface to volume ratio and can serve as hierarchical supports for very thin membranes,provide excellent indirect heat transfer,allow to supply reactants or withdraw products along the flow path through the channel walls,enable an influence on multiphase flow through the wetting properties of the channel walls.Institute for Micro Process Engineering 8 23.03.2010 Prof. R. DittmeyerMembrane Reactor for Hydrogen ProductionInstitute for Micro Process Engineering 9 23.03.2010 Prof. R. Dittmeyer1) Membrane Steam Reformer for Natural GasIdea dates back more than 20 years (Oertel et al., 1987, TH Aachen)>> 100 research papers; many patents; several industry-led consortia (Japan, US/Canada, Europe)Yasuda et al., ICCMR-7, 2005Institute for Micro Process Engineering 10 23.03.2010 Prof. R. Dittmeyer1) Membrane Steam Reformer for Natural GasIdea dates back more than 20 years (Oertel et al., 1987, TH Aachen)>> 100 research papers; many patents; several industry-led consortia (Japan, US/Canada, Europe)Fewer steps / more compact unitLower temperature due to synergy between reaction and separationHigher efficiency / lower cost Yasuda et al., ICCMR-7, 2005Institute for Micro Process Engineering 11 23.03.2010 Prof. R. DittmeyerTokyo Gas System – Membranes Yasuda et al., ICCMR-7, 2005R. Dittmeyer, J. Caro, in: G. Ertl et al. (Eds.), Handbook of Heterogeneous Catalysis, 2nd Ed., Wiley-VCH, Weinheim, 2008, Ch. 10.7 Membrane:Cold-rolled Pd alloy foil with <20 µm thickness hot-pressed on a porous stainless-steel structural support using a porous blanket for protection against intermetallic diffusion.Single tube hydrogen flux:4.2 mN3·m2·h-1 at 550°C, Feed: Syngas with S/C = 3 at 9 bar, Permeate: Steam as sweep gas at 0.4 barInstitute for Micro Process Engineering 12 23.03.2010 Prof. R. DittmeyerTokyo Gas System – Reactor DesignNatural gas+SteamHydrogenOff gasFurnaceBurnerDistribution plateExhaustgasReactor tubeMembranemodulePrimary catalyst bedJacketHeaderReactor Size:1.2 m × 0.75 m × 1.35 m (with thermal insulation)2 (Elements/Tube) × 7 (Tubes/Module) × 16 (Modules) = 224 Elements (membrane area: 10.3 m2)Yasuda et al., ICCMR-7, 2005Institute for Micro Process Engineering 13 23.03.2010 Prof. R. DittmeyerTechnical ChallengesMembrane and catalyst performanceIntegration of catalyst and membraneMinimization of the mass transfer resistances for hydrogen in the whole system Supply of the heat for the endothermic reaction on the spotReactor designthin membrane; active catalystHeat demand (550°C):molkJHCOHOHCH R 1.186428232224 =Δ+⇔+molkJHOHOH R 6.2465.0823222 −=Δ⇔+18.9% of the H2 had to be burnt to provide the reaction heatHeat release by burning of H2:Institute for Micro Process Engineering 14 23.03.2010 Prof. R. DittmeyerThin Membranes1)  Magnetron sputtering of a thin film on a perfect surface (e.g. Si wafer)Jansen et al., Energy Procedia 1, 2009, 253R. Bredesen, ForuM Workshop, SINTEF, Oslo, Nov. 2002Pd/Ag-TargetAr2)  Application of the film on a supporting structurePerfect surface allows growth of a perfect filmGood control of the compositionMultiple layers and continuous manufacture possibleInstitute for Micro Process Engineering 15 23.03.2010 Prof. R. DittmeyerTube-Based Reactor Design Optionsmembrane tubeburner tubeCatalyst in shell BoxCatalyst in annulusJansen et al., Energy Procedia 1, 2009, 253Institute for Micro Process Engineering 16 23.03.2010 Prof. R. DittmeyerThe Microsystems Technology ApproachAlumina Sealing PlatePalladiumSilicon WaferSiO2Si3N4Pt-Heating ElementCross SectionTop ViewPd-MembraneH2 Flux ~ 360 m3/m2h at 500°C and 0.1 barα(H2/N2) ~ 1800Franz et al., IEEE MEMS, 1999, 382Palladium membrane microsystem for hydrogen separationInstitute for Micro Process Engineering 17 23.03.2010 Prof. R. DittmeyerKarnik et al., Proc. IMRET 5, Strasbourg, May 27-30, 2001T = 250 °C WGS-ReactorT = 280 °CΔP = 0.68 bar5.5 µmSEM(spin-on-glass)Microsystem for Methanol ReformingInstitute for Micro Process Engineering 18 23.03.2010 Prof. R. DittmeyerPalladium Membrane Microsystems – StatusMore recent work by several research groups - MESA+ Institute for Nanotechnology, Twente University, NL- MIT, Cambridge/MA, USA- AIST, Ibaraki and Sendai, JP- SINTEF, Oslo, NO- IMTEK, Freiburg/DE…But reactor size and design options are very limited when relying on silicon-based microfabrication technologiesPd microsystems are focused on portable hydrogen generation (Holladay et al., Chem. Rev. 104, 2004, 4767-4790)Institute for Micro Process Engineering 19 23.03.2010 Prof. R. DittmeyerSystems Based on Micromachining of MetalsStacked design using diffusion bonding of thin Pd foils and micro-structured metal sheetsOperating temperature is limited (interdiffusion of metals) Coating of sheets and foils with lower melting metals possible (soldering) H2H2CH4/H2OCH4/H2OPd-MembraneReforming CatalystOxidation CatalystOptions for heatingAlternating layers for H2 removal and oxidationCH4 + O2Alternating channels (in each layer) for H2 removal and oxidationInstitute for Micro Process Engineering 20 23.03.2010 Prof. R. DittmeyerCatalyst Coating of Microstructured Metal SheetsSol-Gel WashcoatCatalyst coating can be applied before or after stacking/joining of the sheets depending on the joining methodInstitute for Micro Process Engineering 21 23.03.2010 Prof. R. DittmeyerDiffusion Bonding of Pd foils to Stainless SteelFirst attempts at IMVT for bonding of 5 µm thick Pd foils (CETH, Marcoussis/FR) to micro-structured stainless steel sheets (1.4404)Micro-structured sheetPd foilSupport (solid frame, porous interior)Bonding with IMVT standard conditions for stainless steel:T ↓T ↓PittingNo damage visibleInstitute for Micro Process Engineering 22 23.03.2010 Prof. R. DittmeyerLaser Welding of Pd foils to Stainless SteelFirst attempt at IMVT with laser welding of thin Pd foils to microstructuredstainless steel sheets5 µm thick Pd foil between two micro-structured stainless steel sheetsCoplanar sheets with burr-free microstructurePerformed with a multi-purpose pulsed laser Leak-free integration achievedca. 0.5 mmca. 5 cmInstitute for Micro Process Engineering 23 23.03.2010 Prof. R. DittmeyerTechnical ChallengesHigh geometrical precision and subtle control of the energy input per unit length requiredHigh aspect ratio of the weld seam needed for joining of multiple layers / stacks from the topHigh power, high speed continuous wave laser system with precise control (positioning, laser power, linear velocity, dynamic control)Stainless steelStainless steel5 µm100 µm200 µmInstitute for Micro Process Engineering 24 23.03.2010 Prof. R. DittmeyerWeld Seam Geometry for Different Energy InputLinear velocity determines energy input per unit length Material: Hastelloy C-22Fiber and spot: d = 150 µmOptics: F=200 mm; FP = -1 mm6 m/min 8 m/min 10 m/min 14 m/min 18 m/minVelocity:1 kW continuous wave CO2 fiber laser (Rofin-Sinar Laser GmbH, Hamburg/Germany)Institute for Micro Process Engineering 25 23.03.2010 Prof. R. DittmeyerVelocity versus Depth for Different Laser PowerMaterial: Standard construction steelDepth (mm)Linear velocity (m/min)Focusing optics: CFO50Spot diameter: 0.2 mmFocal point: -2 mmContinuous wave YAG disk laser (Trumpf Laser Technology, Schramberg/Germany)60 Sheetswith 0.1 mmInstitute for Micro Process Engineering 26 23.03.2010 Prof. R. DittmeyerAlternative to Pd Foils – Coating of Porous SubstratesPorous interiorPorous supportPd alloy coating (various methods: e.g., ELP)Porous intermediate layer (metal interdiffusionbarrier)Not compatible with diffusion bonding due to ceramic interdiffusionbarrierCeramic membrane coatings applicable (comparable to metal supported SOFCs)Solid frameHigh precision laser welding for joining of stacksInstitute for Micro Process Engineering 27 23.03.2010 Prof. R. DittmeyerGravity-insensitive Gas/Liquid SystemsInstitute for Micro Process Engineering 28 23.03.2010 Prof. R. DittmeyerWhy Gas/Liquid-Separation in Microstructures ?For processes fully based on compact „intensified“ microstructure equipment often phase separation is a bottleneckGas-Liquid separation is important in many multiphase reactions (e.g., liquid-phase hydrogenation or oxidation)Application: Development of a „Micro“-DMFC supported universal battery charging systemPure MeOHTankAnode sideMicromixerCO2-SeparatorCathode sideAirH+H2OMeOHMeOH solution (depleted)−+ ++→+ eHCOOHOHCH 66223OHeHO 22 3665.1 →++−+ H2O-RecoveryCO2Air (depleted)Institute for Micro Process Engineering 29 23.03.2010 Prof. R. DittmeyerPreliminary Work on G/L-Separation at IMVTCyclone separator combined with a fine-porous metallic membraneTargets: high recovery of the gas; low pressure drop Tested with CO2 in waterPermeateRetentateGas and LiquidMembraneLiquidInstitute for Micro Process Engineering 30 23.03.2010 Prof. R. DittmeyerCyclone/Membrane Separator – DesignL(out) CycloneInletFeed“Membrane“ (on top)30 µm2 µmMetallic superalloy membranes prepared be electrochemical etching at TU Braunschweig2 µm 2 µmJ. Rösler, D. Mukherji, Adv. Eng. Mat. 5, 2003, 916-918Bottom plateN2H2O, CO2CyclonesCover plateMem-branePermeate collector Cover plateØ = 7.6 mmH = 5 mmInstitute for Micro Process Engineering 31 23.03.2010 Prof. R. DittmeyerCyclone/Membrane Separator – Results1101001000100001 1,2 1,4 1,6 1,8 2Retentate pressure [bar]Separation factor0%6%12%18%24%YieldSeparation factor αYieldFPVVY &&=FOHCOPOHCOwwww⎟⎟⎠⎞⎜⎜⎝⎛⎟⎟⎠⎞⎜⎜⎝⎛=2222 /α Permeate yield:Separation factor:Conditions:T = 26 +/-2 °C3 ml/min H2O6 ml/min CO2Institute for Micro Process Engineering 32 23.03.2010 Prof. R. DittmeyerSeparation Based on Wetting Properties of WallDemonstrated for liquid-liquid systems in capillariesTwo-phase flowDemonstrated also for liquid-liquid as well as gas-liquid systems in porous membrane contactors (pertraction, degassing)Aqueous phaseOrganic phaseHydrophobic wallsHydrophilic wallHydrophobic asymmetric porous membranes (hollow fibers or sheets)Materials: Polymers (PTFE, PP, etc.)SilicaCarbonInstitute for Micro Process Engineering 33 23.03.2010 Prof. R. DittmeyerBasics of MicrosievesGehrke and Keuter, EuroNanoForum, 02.-05.06.09, PragueInstitute for Micro Process Engineering 34 23.03.2010 Prof. R. DittmeyerSilicon-based MicrosievesPore size 1-2 µmS. Kuiper, R. Brink, W. Nijdam, G.J.M. Krijnen, M.C. Elwenspoek, J. Membr. Sci. 196,2002, 149-157Pore size 500 nmJuaz et al., J. Membr. Sci. 323, 2008, 347-351Institute for Micro Process Engineering 35 23.03.2010 Prof. R. DittmeyerMetal-based MicrosievesLaser ablation with a femtosecond laserM.J. Geerken, M.N.W. Groenendijk, R.G.H. Lammertink, M. Wessling, J. Membr. Sci. 310, 2008, 374-383Inlet Exit50 µm thick stainless steel foilInstitute for Micro Process Engineering 36 23.03.2010 Prof. R. DittmeyerMetal-based Microsieves – OptionsElectron beam lithography followed by galvanic deposition of Ni or other metals (LIGA process) (KIT, Karlsruhe/Germany)Track etching of polymers followed by galvanic deposition of Ni or other metals (GSI, Darmstadt/Germany)Micro galvanics and laser ablation (Fraunhofer IUSE, Oberhausen/Germany)dfP ασ cos≤ΔStable G/L-Interface: f = 4 for circular poresState of the art (IUSE):  d = 0.5 - 1 µmInstitute for Micro Process Engineering 37 23.03.2010 Prof. R. DittmeyerSummary/OutlookMembrane integration in microstructures is on the agenda Unit design and fabrication technology is (at least) equally important as membrane and catalyst development if working devices are targetedMicrosystems are not in the focus at IMVTCurrent targetsCompact hydrogen production systems (Pd alloy membranes)Gas/liquid separation based on porous membranes (metal-based microsieves)Water removal from organic reaction mixtures via selective membranesIntegrated oxygen-separation from air for high-temperature oxidation reaction with ceramic membranes on metallic substrates is being consideredInstitute for Micro Process Engineering 38 23.03.2010 Prof. R. DittmeyerBackup – IMVTInstitute for Micro Process Engineering 39 23.03.2010 Prof. R. DittmeyerMillingEmbossing300 µmEtchingTurning50 µmEroding10 µmLaser DrillingMicrostructuringInstitute for Micro Process Engineering 40 23.03.2010 Prof. R. DittmeyerFDiffusion BondingElectron Beam WeldingLaser Welding HT-SolderingJoiningInstitute for Micro Process Engineering 41 23.03.2010 Prof. R. DittmeyerMicrostructured Reactor for 1500 kg/h Fast exothermic liquid-phase reaction in hot concentrated sulfuric acidMaterial: Hastelloy C-22 Institute for Micro Process Engineering 42 23.03.2010 Prof. R. DittmeyerIMVT - PersonnelMechanical µ-Structuring and Manufacturing Development (MF) [15]L. Bohn, R. Dürrschnabel, M. Hofheinz, A. Hüll, H. Lambach, G. Rabsch, D. Scherhaufer, M. Schmidt, M. Schöffler, C. Schorle, J. Schwab, S. Schweikert-Joß, V. Toth, T. Wunsch, J. DörflingerMaterials for µ-PE (WMF) [6]Th. Gietzelt, A. Dubbe, L. Eichhorn, U. Gerhards, F. Messerschmidt, M. ZürkerModelling and Simulation (MSM) [5]A. Wenka, W. Benzinger, C. Fräulin, F. Özkan, U. SchygullaIn situ Analytics and Sensors (ASM) [5]G. Rinke, A. Ewinger, S. Heidecker, S. Kerschbaum, A. UrbanThermal µ-PE (TMV) [12]J. Brandner, E. Anurjew, F. Brighenti, J. Bucko, C. Grehl, E. Hansjosten, M. Jäger, N. Kamaruzaman, S. Maikowske, H. Maria Joseph, A. Vitoriosi, W. WibelChemical µ-PE – Gas Phase / Multi Phase (CMV1) [12]P. Pfeifer, O. Görke, K. Hecht, H. Kreuder, P. Piermartini, C. Spiegel, S. Tauro, J. Thormann, G. Straczewski, N.N., N.N., N.N.Chemical µ-PE – Liquid Phase (CMV2) [6]M. Kraut, K. Haas-Santo, A. Hensel, A. Kölbl, N. Schüler, N.N.Direction (2)R. Dittmeyer, A. KarcherAdministration (4)W. Ratajczak, M. Götz, A. Schäfer, W. SchneckInstitute for Micro Process Engineering 43 23.03.2010 Prof. R. DittmeyerBackup – Hydrogen ProductionInstitute for Micro Process Engineering 44 23.03.2010 Prof. R. Dittmeyer2) Methylcyclohexane DehydrogenationBackground: storage of excess electricity or heat (nuclear, renewable) Chemical storage of hydrogen produced by electrolysis Capacity: 6.1 wt.-% or 43 kg H2 / m3Heat demand (300°C):molkJHHHCHC R 3.2153573287147 =Δ+⇔molkJHOHOH R 5.2445.0573222 −=Δ⇔+Heat release by burning of H2:29.4% of the H2 had to be burnt to provide the reaction heatHeat storage for solarthermal power plants Capacity: 215 kJ/mol or 2194 kJ/kg For comparison: heat capacity of molten NaNO3: 1.83 kJ/kg·KInstitute for Micro Process Engineering 45 23.03.2010 Prof. R. DittmeyerPd Membrane Microsystems (not exhaustive)F.C. Gielens, H.D. Tong, C.J.M. van Rijn, M.A.G. Vorstman, J.T.F. Keurentjies, High-flux palladium-silver alloy membranes fabricated by microsystem technology, Desalination 147, 2002, 417-423H.D. Tong, F.C. Gielens, J.G.E. Gardeniers, H.V. Jansen, C.J.M. van Rijn, M.C. Elwenspoek, W. Nijdam, Microfabricated Palladium-Silver Alloy Membranes and Their Application in Hydrogen Separation, Ind. Eng. Chem. Res. 43, 2004, 4182-4187B.A. Wilhite, M.A. Schmidt, K.F. Jensen, Palladium-Based Membranes for Hydrogen Separation: Device Performance and Chemical Stability, Ind. Eng. Chem. Res. 43, 2004, 7083-7091J.D. Holladay, Y. Wang. E. Jones, Review of Developments in Portable Hydrogen Production Using Microreactor Technology, Chem. Rev. 104, 2004, 4767-4790S.-Y. Ye, S. Tanaka, M. Esashi, S. Hamakawa, T. Hanaoka, F. Mizukami, Thin palladium membrane microreactors with oxidized porous silicon support and their application, JMM 15, 2005, 2011-2018Y. Zhang, J. Gwak, Y. Murakoshi, T. Ikehara, R. Maeda, C. Nishimura, Hydrogen permeation characteristics of thin Pd membrane prepared by microfabrication technology, J. Membr. Sci. 277, 2006, 203-209F.C. Gielens, R.J.J. Knibbeler, P.F.J. Duysinx, H.D. Tong, M.A.G. Vorstman, J.T.F. Keurentjes, Influence of steam and carbon dioxide on the hydrogen flux through thin Pd/Ag and Pd membranes, J. Membr. Sci. 279, 2006, 176-185F.C. Gielens, H.D. Tong, M.A.G. Vorstman, J.T.F. Keurentjes, Measurement and modeling of hydrogen transport through high-flux Pd membranes, J. Membr. Sci. 289, 2007, 15-25 L.S. McLeod F.L. Degertekin, A.G. Fedorov, Determination of the rate-limiting mechanism for permeation of hydrogen through microfabricated palladium-silver alloy membranes, J. Membr. Sci. 341, 2009, 225-232

Opportunities and challenges of membrane integration into compact microstructure reactors

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Opportunities and challenges of membrane integration into compact microstructure reactors

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