The HybSi membrane: from research to industrial demonstration Jaap Vente
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1 The HybSi membrane: from research to industrial demonstration Jaap Vente Presented at the NMG-Matchmaking Event, November 22 nd, Arnhem, The Netherlands ECN-L November 2010
2 The HybSi membrane: from research to industrial demonstration Jaap Vente
3 HybSi Characteristics Pervaporation membrane with unrivalled stability: Higher temperatures Acid conditions Aggressive solvents Hybrid material with: Si O Si Si CH 2 CH 2 Si bonds 2
4 Value for the manufacturer Market size: 5,000 20,000 m 2 /yr; 12, ,000 tubes / yr 3
5 Application Bio-ethanol Value for the end-user Conventional process Distillation + mol sieve Energy savings Costs savings 30% 20% (2-3 ct/l lower EtOH production cost) Pay back period 3 years Acetone Distillation 40% 25% 2 years Esterification reactions Methanol from toluene Distillation (batch process) Extraction + distillation 50% 30% ± 1 year 50% 30% ± 1 year
6 Pervaporation Selective evaporation via a membrane Much higher energy efficiency than distillation Feed Membrane Permeation Permeate Evaporation 5
7 Prime applications Separation of azeotropes Capacity increase through debottlenecking 6
8 The opposition Commercially available pervaporation membranes Polymers - PVA (Sulzer Chemtech) - Polyimide (Vaperma) Ceramics - Zeolite A (Mitsui, Mitsubishi, Inocermic, Zeolite Solutions) - SiO 2 (Pervatech) 7
9 Towards a generally accepted technology Limitations currently perceived by the end-user - Limited stability - High risk option - Predictability has to improve (where is the predictive tool?) - Application window too small Current challenges - Higher application temperatures - Higher resistance against acids and alkalines - Higher stability in aggressive solvents - Larger application window w.r.t. water content - Effective methanol removal - Resistance against condensation 8
10 From infancy to maturity 9
11 Where did we start? Status
12 Looking back Ideation First attempts (UT) First publication: hot article First membrane tubes + testing (UT & ECN) HybSi day HybSi the movie Patent 1 filed Patent 2 filed Patent 3 filed
13 Long term performance 150 C 3% H 2 O in BuOH Measurement stopped after 1000 days 12
14 Acid resistance (HAc in EtOH) Various levels of HAc in EtOH 70 C 5% H 2 O in EtOH 13
15 High temperature performance Ethanol dehydration 5 or 10% H 2 O in Ethanol Temperature o C 14
16 HybSi advantages over commercial products Higher application temperatures C Higher resistance against acids and alkalines - ~ 2 < ph < ~8 Higher stability in aggressive solvents - NMP, MEK Larger application window w.r.t. water content - Measurement up 30% performed Effective methanol removal - Feasibility shown Resistance against condensation - All liquid feed no issue 15
17 HybSi advantages over commercial products High temperature operation Suitability for vapour permeation Resistance to aprotic solvents Acid compatability 0 High flux isothermal modules Selectivity MeOH vs. organics Selectivity H 2 O vs. Low investment costs Polymeric HybSi organics Zeolite A 16
18 Implementation trajectory Formation of value chain - end-user - system builder - membrane manufacture - Knowledge provider Three letter of interest system builders: interest ranges from 300 m 2 /yr to several 1000m 2 /yr Running actions for external parties: - Delivery of lab modules - In house application tests - On site pilot testing 17
19 Industrial pilot test Consortium: - Trion Partners, Air Products, Sulzer Chemtech, and Deltalinqs 30m 3 of end of pipe fuel from 30-35% to ~2% water 1m 2 membrane area Winter 2011 Lab result promising! 18
20 What has ECN to offer? Non-exclusive license on Broad patent portfolio: - Materials on various HybSi membranes - Hollow fibres, multichannel, external surface tubes, (especially for production > 200 m 2 /yr) - Sealing technology & module concept Know-how - Coating technology - Sol-gel procedures The names and logos - HybSi - ECN technology inside 19
21 What more has ECN to offer? Contract research - Fine tuning membranes - Process testing - Process simulations and design Technological website - (>50 unique visits per week) Large industrial network Parties with proven commercial interest Existing distribution list 20
22 Industrial involvement Commitment from end users - Tests & module sales - Process analyses - Letters of Intent to come to actual utilisation Interest from OEM - Letters of interests - Active participation Contract with manufacturers - First licence granted to Pervatech 21
23 Acknowledgements Industrial collaborators & clients - Sabic - Huntsman - Air Products - DSM - Sulzer Chemtec - Pervatech - Trion partners Knowledge network University of Twente University of Amsterdam TNO Financial support - STW - AgentschapNL - DSTI Membrane Technology Group /memtech 22
24 HybSi ready for take off Scientific Papers Chem. Commun., 2008, 1103 J. Mater. Chem., 2008, 18, 2150 J. Sol-Gel Sci Techn, 2008, 48, J. Mem. Sci., 2008, 319, ChemSusChem, 2009, 2, J. Sol-Gel Sci Techn, 2010, accepted Patents WO/2007/ ; WO/2010/008283; WO/01/62371; WO/01/
25
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