Membranes integrated in conversion processes as a way to process intensification
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1 Membranes integrated in conversion processes as a way to process intensification Ludo Diels, VITO, Belgium CPAC Satellite Workshop Rome, March 21 24, 2011
2 Membranes integrated in conversion processes as a way to process intensification» Introduction about process intensification and microreactor technology» The VITO approach» VITO demonstrators» Algae recovery» In situ Product Recovery» Catalyst immobilisation» Functionalised membranes» Catalytic Membrane Reactors» FMMC 27/03/2011 2
3 Green chemistry: Giving each molecule the same processing history Tank Reactor Tubular Reactor Batch process Continuous process 27/03/2011 3
4 Future challenges in MicroReactor Technology According to Norbert Kockmann (Lonza AG):» Scale up and robustness» Single and multiphase flow including solids;» Mixing, residence time, and plugging;» Heat transfer and reaction control;» Chemically stable and corrosion resistive.» Catalyst integration» Flexible and versatile;» Rapid screening and scale-up.» Cost efficient devices» Simple, robust, and combination with periphery.» Work-up steps and process design» Consistent and robust scale-up strategy» Complete plant integration; integration with separation & purification processes 27/03/2011 4
5 Potential energy Green chemistry: Maximizing effectiveness of intra- and intermolecular events Transition state CHALLENGE: the most efficient way of supplying energy (form and transfer mechanism) to let reactants molecules selectively overcome this barrier CHALLENGE: control of energy distribution amongst the reaction products Catalysis -Less energy - Higher specificity Reactants CHALLENGE: control of the geometry of approach and mutual orientation of molecules at the moment of collision Products Reaction coordinate 27/03/ Sustainable Chemistry 5
6 Maximizing synergistic effects from partial processes In situ product recovery 27/03/2011 6
7 Membranes integrated in conversion processes as a way to process intensification» Introduction about process intensification and microreactor technology» The VITO approach» VITO demonstrators» Algae recovery» In situ Product Recovery» Catalyst immobilisation» Functionalised membranes» Catalytic Membrane Reactors» FMMC 27/03/2011 7
8 Objective 1: Process intensification From batch to continuous + Integration of conversion and separation technology 27/03/ T. Van Gerven 8
9 Objective 2: From fossil-based to biomass-based chemistry Fossil resources Biomass Conversion Separation Chemicals Food ingredients CO 2 Separation Conversion Consumer Products 27/03/2011 9
10 From reaction + purification to integration of reaction and separation Substrate Chemical Reaction(s) Purification Manufacturing Product Substrate Fermentation Downstream processing Manufacturing Product Substrate Enzymatic process Downstream processing Manufacturing Product Substrate Reaction / conversion process Separation Manufacturing Product 27/03/
11 Membranes integrated in conversion processes as a way to process intensification» Introduction about process intensification and microreactor technology» The VITO approach» VITO demonstrators» Algae recovery» In situ Product Recovery» Catalyst immobilisation» Functionalised membranes» Catalytic Membrane Reactors» FMMC 27/03/
12 Algae production recovery with integrated water treatment» Continuous recovery of algae from production system by VITO membranes Better quality in production system Less energy needs for algae harvest Allows better water treatment 27/03/
13 CO 2 / NO x conversion in algae biomass: downstream processing drying CO 2 NO x water cultivation harvesting extraction purification O 2 Algae biomass Sc CO 2 extraction Cells Sc CO 2 Cell disruption - lipids - proteins - polysaccharides - dyes - chemicals - 27/03/
14 Purge Fermentation processes with In situ Product Recovery Integration of conversion and membrane separation to improve overall efficiency Bioreactor Separation Substrate Fermenter Broth + product Broth Product FEED PERMEATE VAPOUR (Δp) 27/03/
15 Orghanophilic pervaporation (OPV) membrane» Mixed matrix membranes for OPV at VITO PVDF or PAN support membrane on non-woven PE Thin layer of silica-filled PTMSP 27/03/
16 In situ alcohol recovery by organophilic pervaporation Integration of conversion and membrane separation to improve overall efficiency Pervaporation module Acidogenic fermentation Solventogenic fermentation 27/03/
17 In situ alcohol recovery by organophilic pervaporation» Continuous fermentation operational» Coupled to PV system continuous operation 27/03/
18 In situ alcohol recovery by organophilic pervaporation» Proof-of-concept for coupling of fermentation and pervaporation:»pervaporate concentration from g/l»productivity enhancement of 87%»Use of concentrated feedstocks α VITO PERVAP 4060 PERVATECH Organics/water »Direct future:»»use of in-house developed mixedmatrix composite PTMSP membrane»optimizing continuous conversion A/water E/water B/water B/E ,8 B/A ,36 A/E ,5 Flux (kg/m².h) /03/
19 Biomass chemicals - energy Electricity Carbohydrates Fats Proteins Sugars Fatty acids Amino acids Alcohols Carbonic acids MFC H2, CO NH3 H2, Acetic acid CO2 CH4 CO2 Liquor Hydrolysis Acidogenesis Acetogenesis Methanogenesis Biohydrogenation + E-donor Alcohols Acids Nutrients 27/03/ 27/03/
20 Wastewater + waste transformation into chemicals 27/03/
21 Functionalized membranes: reactive membranes» Nano Activated membranes (NAM)» Ag, TiO 2 (desinfection)» Pt, Pd, Fe, Au (catalysis, oxidation-reduction)» Biocatalyst Activated membranes (BAM)» Enzyme immobilisation» Bioplasma (Patent)» Zirfon (Patent)» Co-factor immobilisation? Reagentia Membraan Reactor Permeaat Retentaat Geïmmobiliseerd enzyme Covalent ~ 100ng/cm² 27/03/
22 Immobilization of enzymes on membranes 27/03/
23 Membrane electrode assemblies» (Bio)chemical reactions by» Catalysts (inorganic, enzymes, bacteria) on electrodes» Linked to a membrane (MEA)» Where the electrochemical voltage improves the efficiency of the reaction» Whereas simultaneous electron transfer is transformed into electric current via an external cirquit» E.g. acetate oxidation by Geobacter» E.g. CO2 reduction to formic acid, butyric acid» E.g. Hydrogenation of NO to NH2OH» E.g. Dehydrogenation of nitrobenzene to aniline 27/03/
24 (Bio)electrochemical cells» VITOs highlights» Microbial fuel cell working on acetate» Enriched microbial community» PTFE layered carbon electrode with current collector» Zirfon (ion permeable membrane) coated on carbon electrode (thin; less O2 permeability, less biofouling potential than Nafion or Fumasep (PEM)» Separator and fuel cell expertise» Electrochemical expertise» Porous gas electrode development» Future stack development» 1600 mw/m² (Pt-electrode Penn State)» 1220 mw/m² (VITO-electrode Penn State )» 2720 mw/m² (Pt-electrode best ever) 27/03/
25 Affinity separations in OSN OSN is more complicated than filtration in water Potential for affinity separation with functionalised/grafted membranes ~ 1 nm 27/03/2011 Hydrofobic or functional group 25
26 Membrane functionalization at VITO/UA Post-modification based on organometal chemistry : grignard reaction (patent) M R direct, covalent bond highly stable Compatible with a wide variety of functional groups Opens path to :» affinity separations» membranes tailored to separation Status : reproducible hydrophobic membrane at lab-scale 2011 : optimization hydrophobization + 1st functionalization 27/03/
27 Catalyst recovery» Homogeneous catalyst modfication and membrane modification in order to recover catalysts from reaction mixtures» Pharmaceuticals» Fine chemicals» Biomolecules» Polymers» Removal of impurities, reaction compounds, cata + Membrane Increase of selectivity cata + Modified membrane R 27/03/
28 Catalytic Membrane Reactors Dehydrogenation of ethane H H 3 C 2 C CH 2 CH 3 sweep + H + H 3 C sweep + H 2 CH 3 Legend HF membrane wall Cat layer or bed Approximate temperature window for Useful T - window Membrane material ion conductivity Reaction thermodynamics Catalyst operation Temperature ( C) 27/03/
29 Concept of MIEC hollow fiber membrane reactor for dehydrogenation reactions sweep sweep + H 2 H 2 H 2 H 2 H 2 H 2 C 2 H 6 CH 3 -CH 3 CH 2 =CH 2 + H 2 C 2 H 4 H 2 H 2 H 2 H 2 H 2 H 2 = 2 H e - high ph 2 (reaction side) V H H + e- h + low ph 2 2 H e - = H 2010, 2 VITO NV 27/03/ (sweep side) MIEC material catalyst
30 Concept of MIEC hollow fiber membrane reactor for oxidative coupling of methane air O 2 depleted air O 2 O 2 O 2 O 2 O 2 CH 4 CH 4 + O 2 CH 2 =CH 2 + H 2 O CH 4, CH x C 2, H 2 O O 2 O 2 O 2 O 2 O 2 2 O 2- = O e - Low po 2 (reaction side) O 2- e - V O h + O e - = 2 O 2- High po 2 (air) 27/03/ MIEC material catalyst
31 Concept of MIEC hollow fiber membrane reactor for dehydrogenation/cracking reactions sweep sweep + H 2 H 2 H 2 H 2 H 2 H 2 C 4 H 10 C 4 H 10 2 CH 2 =CH 2 + H 2 C 2 H 4 H 2 H 2 H 2 H 2 H 2 H 2 = 2 H e - high ph 2 (reaction side) V H H + e- h + low ph 2 2 H e - = 2010, H(sweep 2 VITO NV side) MIEC material catalyst 27/03/
32 How do we operate? Individual integrated approach R&D National and European research projects Strategic co-operation and partnerships Own developments (new products, concepts) 27/03/
33 Our references 27/03/
34 More info on 27/03/
35 Membranes integrated in conversion processes as a way to process intensification» Introduction about process intensification and microreactor technology» The VITO approach» VITO demonstrators» Algae recovery» In situ Product Recovery» Catalyst immobilisation» Functionalised membranes» Catalytic Membrane Reactors» FMMC 27/03/
36 A government funded initiative to stimulate the development and integration of microfluidic applications in Flemish industry by knowledge diffusion and partner matching 27/03/
37 Project leaders: Funding: In line with: Flanders Initative for Sustainable CHemistry 27/03/
38 A government funded initiative to stimulate the development and integration of microfluidic applications in Flemish industry by knowledge diffusion and partner matching Activities: - Competention-inventorisation - partnermatching starting innovative projects between members - informing proactively through newsletters and website - Organizing seminars, workshops and bilateral contacts 27/03/
39 FMMC after 8 months > 20 members from Flemish industry & Academia R I C
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