Integration of membrane based separation processes in white ... - NBV

Integration of membrane based separation processes in white ... - NBV

Integration of membrane basedseparation processes in whitebiotechnologyMark RoelandsNBV-NMG 2009.06.11

Introduction Mark RoelandsMark RoelandsSenior Research ScientistTNO Separation Technology – Apeldoorn /DelftMSc Chemical EngineeringPhD Separation Technology, promotor Peter JansensProcess & Energy LaboratoryDelft University of Technology - DelftProcess researcherAkzo Nobel Chemicals Research - Arnhem2

Contents• Introduction- Membrane Technology at TNO- Bioprocess Technology at TNO• Membrane based bioprocesses- Solvent Impregnated Resins / Pertraction- (Thermo)Pervaporation- Membrane Slurry Reactor• SummaryNBV-NMG 2009.06.11

Membrane Technology at TNOChemicals : Process IntensificationMembrane-based separations (Thermo) Pervaporation PertractionMembrane reactors Membrane slurry reactor Catalytic membrane reactorOil & Gas / Energy : CO 2capture Membrane gas absorption MemfracWater : Decentral Water Treatment Memstill Pertraction MAC/FACT MAAS Catalytic Membrane ContactorMaterials surface modificationNBV-NMG 2009.06.11

Process & Equipment Development ChainGoodIdeasProof-of-PrincipleProof-of-ConceptPilot /DemoProventechnologyDoes it work? How to construct?Performance?How to scale-up?How to implement?laboratory scalebench scalepilot scaledemo/full scale9

Pilot installations Process Intensification TNOProcessIndustrieGalvano, Food,Energy, PaperEmulsion pertraction-1 & 2FACT-1CO2-Catcher EONZeolite dryer2000 2002 2004 2006 2008 2010Pertraction-1 NH3-MGA-1 HELIX NH3-MGA-2 HWC-1 HWC-2 Pertraction-2ChemicalsWater2000 2002 2004 2006 2008 2010NBV-NMG 2009.06.11FACT-2 Memstill-1 Memstill-2 Memstill-3

Ref: Laane NBV-NMG 2009.06.11

Bio-process development at TNO• Chemicals: transition from fossil to renewables- feedstock pretreatment- integrated reactor with separationto improve volumetric productivity• Oil & Gas: transition from fossil to renewables- thermal conversion of biomass- upgrading of biogas• Energy: CO 2 utilisation- algae cultures• Water: decentral water treatment- MBR / FBR flux increasement- Denutritor prevention of biofoulingNBV-NMG 2009.06.11

Bio-based chemicals by means of solventresistant micro organism (Pseudomonas P.)External compoundEfflux systemFine / bulkchemicalExternal compoundFine/bulkchemicalSugarCentral metabolite(overproduced)PhenylalanineMicro organisms are the almost perfect chemical plants: multi-stepprocess, H 2 O as solvent, high selectivity, catalysed, low p & T, but ….unfortunately the piping for the product outlet is not connected

Product inhibitionProduct inhibition is a generic problem inchemicals production in fermentationsPhenol was chosen as model compound:- typical example of hydroxylated aromatics- could already be produced by P. Putida S12 1- inhibits the production at >2 mM for P. putida- very hydrophilic (solubility ~ 0.9 mol/l)- high boiling point (182 o C),- low vapour pressure (31 Pa at 20 o C)NBV-NMG 2009.06.111Wierckx et al., 2005

Product Recovery in (Bio)Chemical ProcessesConventionalModernNovelFeedFeedFeeddownstreamprocessingAim: selective recoveryNBV-NMG 2009.06.11

Starting situation for ISPR in (Bio)Chemicals:• Produces a great variety of molecules• Often complex and dilute mediaConsequences for ISPR• Need for highly selective separation principles• Suited for In-Situ and/or In-Stream RecoveryConclusionThere will be no single generic ISPRmethod,but we need a TOOLBOX with anumber of separation techniques, whichare multi-application and which canquickly be tailored for specific moleculesNBV-NMG 2009.06.11

Bioproduct separation technology classificationMolecular familiy (example) (novel) separation technology auxiliary• Polar + volatile (thermo)-pervaporation membraneEtOH, BuOH• Polar + non-volatile Solvent Impregnated Resins solventphenol, p-hydroxystyrene pertraction (membrane)• Charged + low solubility Template Crystallization templatecarboxylic acids, amino acids Crystelcinnamic acid, fumaric acid,l-Tyrosine, L-Glutamic acid• Charged + high solubility Electro-electro-dialysis membranecarboxylic acids, amineslactic acidNBV-NMG 2009.06.11

Polar + non-volatile: pertraction& Solvent Impregnated Resins• Model compound = phenol• Pertraction with octanol• Solvent Impregnated Resins withionic liquidNBV-NMG 2009.06.11

How solvent impregnated resins work…StartEndWhy consider solvent impregnated resins?- No emulsification problems with solvent- No phase toxicityNBV-NMG 2009.06.11

P. putida Fed-batch fermentation - [phenol] as f(time)NBV-NMG 2009.06.11

P. putida Fed-batch fermentations with XAD4Product releaseAddition of adsorbentNBV-NMG 2009.06.11

P. putida Fed-batch fermentations - SIRsProduct releaseAddition of SIRsconcentration in aqueousphase remains low!NBV-NMG 2009.06.11

Comparison of three different fed-batch fermentationsPhenolproducedProductivityYield P/SControl 1 1 150g XAD-4 2.5 1.2 1.250g SIR 4.3 1.7 1.7NBV-NMG 2009.06.11

In-situ pertraction [1]+ =NBV-NMG 2009.06.11

In-situ pertraction [2]NBV-NMG 2009.06.11

From extraction to in-situ pertractionFeedFeedFeed1-OctanolMembrane1-OctanolReactor (aq)Reactor (aq)1 M NaOHIn-situ 2nd phase Membrane extractionReactor (aq)1-OctanolIn-stream pertraction1 M NaOHPurificationIn-situ pertractionNBV-NMG 2009.06.11

Example of product inhibitionNBV-NMG 2009.06.11

Fed-batch pertractie12,0[biomass] (g/L); [phenol] (mM); Ph/BM (-)10,08,06,04,02,0BiomassPhenol (aq)Phenol (oct)Phenol (total)Ph/BM0,00 20 40 60 80 100Time (h)NBV-NMG 2009.06.11

Charged + low solubility: crystel Depending on electrolysis conditions, cinnamic acid is precipitated as asolid on the anode, or as flocks in the vicinity of the anode. Product removal by scraping, flottation, filtration, current reversal, etc.NBV-NMG 2009.06.11

Charged + high solubility:Electro-Electro-Dialysis (EED)Recovery of highly solubleorganic bases and acids fromits salt.e.g. a carboxylic acidTypical process parameters:feedEnergy consumption:1 – 5 kWh/kgRecovery:30 – 50 wt%NBV-NMG 2009.06.11

Conclusions TNO ISPR portfolio• Bioproducts often toxic or inhibiting to micro-organism• ISPR improves productivity, reduces steps in DSP• Tailor-made by use of auxiliaries• TNO develops toolbox of ISPR techniques:- polar volatile: thermoPV- polar non-volatile: pertraction & SIRs- charged low-soluble: TIC & Crystel- charged high-soluble: EED• Deliverables:- proof-of-principles- models and methods for screening auxiliaries- experimental techniques for mass-transfer- process models for technical-economical evaluationNBV-NMG 2009.06.11

Polar + volatile:ThermoPervaporation• Selective evaporation ofeither organic or water bychoice of membrane• Temperature difference,provides driving force• Heat contained in thepermeate vapour directlyheats the feed streamNBV-NMG 2009.06.11

ThermoPV test unitMembranesSulzer A (organophilic)• Removal of volatile organics fromwater• Tested with the system(s)• Ethanol – waterSulzer B (hydrophilic)• Permeation of water from volatileneutral organics and their mixtures• Tested with the system(s)• Ethanol – water• Ethylene glycol - water• Butanol - waterNBV-NMG 2009.06.11

Thermo pervaporation - experimentalLaboratory scale studyMixture ethanol – waterconcentrations from 10%v/v to 30%v/vNBV-NMG 2009.06.11

Thermo Pervaporation - resultsPerformanceInternal heat recovery[%]25%20%15%10%5%0%00 10 20 30 40 500,70,60,50,40,30,20,1Permeate Flux[kg/m 2 h]Permeate Ethanol concentration[%w/w]70%60%50%40%30%20%10%0%0 10 20 30 40 50∆T [ºC]∆T [ºC]Internal heat recovery (76ºC)Internal heat recovery (57ºC)Permeate flux (76ºC)Permeate Flux (56ºC)76ºC57ºCNBV-NMG 2009.06.11

Potential applications of Thermo PV (I)Ethanol separation fromfermentation broth• Continuous ethanol removal fromfermentation broth• Possibility of increasing fermentationproductivity• Potential energy savings compared toconventional pervaporation• Possibility of using low grade heat orwaste heat• Modular design• Easy to scale up• Small foot print and weightEnergy estimation for ethanol recoveryDesign parametersEthanol feed concentrationEthanol permeate concentrationInitial Feed TemperatureFinal retentate TemperatureRecovery of ethanolSeparation factorInternal heat recoveryEnergy usageFactors for developmentValueUnits10% [%w/w]52% [%w/w]20 ºC66 ºC84% [-]7 [molar basis]90% [-]3,1 [MJ/kgEtOH]• Single-stage process: Focus onmembrane selectivity and thermal stability• Multi-stage process: Focus onmembrane fluxNBV-NMG 2009.06.11

Potential applications of Thermo PV (II)Dehydration of Isopropanol• Energy for water evaporation 2.28 MJ/kg• System very suited for water concentrations above 5%wtEnergy estimation for isopropanoldehydration: 80% savingsEnergy estimation for isopropanoldehydration: 31% savingsNBV-NMG 2009.06.11

Potential applications of Thermo PV (III)Water separation from ethanoland butanolWater separation from othersolvents• Technology proven for the dehydrationof ethanol and butanol with high watercontent• 30-50% energy savings compared toconventional pervaporation• Markets: biofuels• Technology proven for the dehydrationof ethelene glycol with high watercontent• Energy savings compared toconventional pervaporation• Markets: Biodiesel production(purification of glycerol), organicsolvent purificationNBV-NMG 2009.06.11

Thermo Pervaporation - summary• Applications:- evaporation of organics from broth- dewatering of organics• Advantages of Thermo PVOperational50% energy savingscompared toconventionalpervaporationMechanicalSmall, light weightequipmentPossibility of usinglow grade heatModular designNBV-NMG 2009.06.11

Membrane Slurry Reactor: integration ofheterogeneous catalysis, reaction and separationPrincipleProduct can pass membrane, while (bio)catalyst particles are retained in reactorLab scale MSRAdvantages• Suited as add-on to batch reactors• Continuous operation• Low hold up of catalyst in system• Mild mechanical treatment of catalyst• Suited for chemical and bio-catalysisand for relatively small particles• Increased activity catalystNBV-NMG 2009.06.11

Demonstration of MSR-CLEA:hydrolysis of Penicillin GReactionPenicillin acylase CLEAAPA-MSR Precipitationwith 5% CLEAsMSREnzymatic conversion of Penicillin G into Phenylacetic acid and 6-aminopenicillanic acid (6-APA)NBV-NMG 2009.06.11

Installation for demonstration of MSR-CLEAhydrolysis of Penicillin GPenGfeedAPA-PrecipitationMSRConditions Feed: 10% K-Pen G [CLEA]: 5, 7.5 & 10 % Conversion: 65, 75 & 82% V reactor = 400 ml τ = 70 min T=20°C, pH=8.0 1M NaOH to maintain pH 100 mM Phosphate buffer Precipitation of 6-APA atpH=4.3NBV-NMG 2009.06.11

NBV-NMG 2009.06.11Demonstration MSR-CLEA (1)Batch hydrolysis of Penicillin G

Demonstration MSR-CLEA (2)Continuous hydrolysis of Penicillin GNBV-NMG 2009.06.11

CONCLUSION• Membrane Slurry Reactor is a concept for a continuousprocess which combines heterogeneous catalysis, reactionand separation• Low hold-up of catalyst in MSR and no pumping/externalhandling needed• Membrane Slurry Reactor is suited as add on for batchreactor• CLEAs are interesting biocatalysts which are suited for usein Membrane Slurry Reactor• Proof of Principle delivered for hydrolysis of Penicillin byCLEA in Membrane Slurry ReactorNBV-NMG 2009.06.11

Summary• TNO develops membrane based processes integrated with whitebiotechnology• Proof-of-principles• From ISPR portfolio:- pertraction – polar compounds- solvent impregnated resins – polar compounds• (Thermo)-pervaporation :- volatile compounds- dehydration• Membrane slurry reactor – enzymatic conversion=> Next step proof-of-conceptNBV-NMG 2009.06.11

Business opportunities Portfolio of advanced membrane technologies- Membrane contactors: MGA, pertraction, memstill- Process intensification: integration of reaction and separation Access to innovative technology, research teams, and TNO's intellectualproperty (IP) portfolio- Licensing and colloboration More informationDr. Jean-Marie Bassett ( Oil and gasChemicalsEnergyAlbert Jansen ( WaterNBV-NMG 2009.06.11

AcknowledgementsLouise Heerema, Corjan van den Berg, Jan-HarmUrbanus, Peter van den Broeke, Eva Sanchez, DirkVerdoes, Albert Jansen, Paul Bussmann, FrankVercauterenThis project is financially supported by the Netherlands Ministry ofEconomic Affairs and the B-Basic partner organizations ( B-Basic, a public-private NWO-ACTS programme (ACTS =Advanced Chemical Technologies for Sustainability).NBV-NMG 2009.06.11

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