TNO Science & Industry. Dr. Jean-Marie Bassett

Transcription

1 TNO Science & Industry Dr. Jean-Marie Bassett

2 TNO is the Netherlands-based Organisation for Applied Scientific Research. 76 years old, founded by Act of Parliament. About 4500 employees 12 Locations in NL Non-profit status 5 Core areas TNO Science & Industry 1000 employees Market : Government funding = 75:25

3 TNO is active in five core areas Quality of Life Defence, Security & Safety Built Environment & Geosciences Information & Communication Technology Science & Industry

4 PROCESS INTENSIFICATION FOCUS : THE CHEMICALS INDUSTRY MISSION : THE DEVELOPMENT OF LEADING EDGE SUSTAINABLE PROCESSES INNOVATION STRATEGY : TO BE KEY PLAYER IN THE CONVERSION OF BATCH PROCESSING TO SMALL CONTINUOUS PROCESSING

5 Portfolio of Process Intensification Technologies Membranes and membrane contactors Crystallisation & Precipitation Reactor Design & Development Hybrid Membrane Technology Absorption Adsorption Crystallisation Distillation Extraction Electrochemistry

6 Services Markets Served Consultancy Feasibility studies Process evaluation Oil & Gas Energy Chemicals Industry Pilot plant testing Conceptual engineering Demonstration Licensing

7 Market sector Chemicals Advanced reactors for integrated (bio) conversions, separations and/or heat exchange (incl. ISPR, mini & micro reactors). Product purification by melt-crystallisation and hydraulic wash columns. Particle engineering. Membrane-based technologies for enhanced contacting, efficient separations and novel product recovery.

8 Market sector Chemicals Dr. Mark Roelands Novel In Situ Product Removal Methods

9 Market sector Oil & Gas Gas treatment (a.o. H 2 O/ H 2 S/Hg/SO 2 /NH 3 ) for natural gas with e.g. high CO 2 content other industrial gases Oil treatment (a.o. H 2 O, sulphur, Hg) Treatment of production water CO 2 & sulphur mineralisation Upgrading of Bio-Oils from pyrolysis

10 Market sector Energy Post-combustion CO 2 capture - advanced fluegas scrubbing solvent development and characterisation TNO proprietary solvent CORAL performance testing up to level of industrial pilot compact membrane gas/liquid contactors Pre-combustion CO 2 capture syngas scrubbing solvent development and characterisation performance testing in laboratory mini-plant Modelling and assessing capture systems techno-economic modelling process modelling 0

11 Process Intensification: In-Situ Product Recovery from (bio)chemical processes ark Roelands, Dirk Verdoes, Jean-Marie Bassett

12 Contents Process Intensification at TNO In-Situ Product Recovery ISPR toolbox TNO Examples Conclusions 2

13 Process Development at TNO Good Ideas Proof-of -Principle Proof-of -Concept Pilot / Demo Full scale Does it work? How to operate? How to scale-up? laboratory scale bench scale pilot scale Central Theme = Processs Intensification: Continuous Intensified Contactors & Separations (CICS) Expertise: Membrane technology, Crystallisation, Extraction, Adsorption, Electrochemistry 3

14 TNO Separation Technology Process Intensification Purification of chemicals Crystallisation and wash column technology Intensified separations (cheaper, smarter, smaller) Membrane contactors (G-L and L-L) Hybrid Processes Innovative contactors In-Situ Product Recovery Helix Reactor (Catalytic) Membrane Reactors 4

15 Biotechnology: Draining or Fishing? OR 5

16 Product Recovery in (Fine)Chemical Processes Conventional current industrial practice Feed Modern academic studies Novel TNO development Feed Feed down stream processing TNO s aim: selective recovery 6

17 Advantages of ISPR Increased productivity Reduced costs Reduction of process steps From (fed-)batch to (semi-)continuous Better selectivity. Numerical example for combination fermentation-crystallisation Buque-Taboada, E.M. et al, Biotechnology and Bioengineering 86(7), 2004, p Continuous/(external) ISPR versus batch production/dsp Productivity increased by 50% Selectivity increased from 87% to 96% No crystallization in the fermenter 6-fold reduction in biocatalyst consumption per kg product 7

18 Starting situation for ISPR in (Fine) Chemicals: Produces a great variety of molecules Often complex and dilute media Consequences for ISPR Need for highly selective separation principles Suited for In-Situ and/or In-Stream Recovery Conclusion There will be no single generic ISPRmethod, but we need a TOOLBOX with a number of separation techniques, which are multi-application and which can quickly be tailored for specific molecules 8

19 Molecular properties versus separation principles Vapour pressure Solubility Partition coefficient Size exclusion Charge/surface interaction Distillation/ Stripping X Extraction X X Crystallisation Template Crystal. X Adsorption/IX SIRs Chromatography X X Membrane technology Pervaporation Pertraction X X Electroseparation Crystel BeXtel Electrodialysis TNO has a broad portfolio in separation technology Extra opportunities for combinations of separation techniques 9

20 TNO Focal Area for ISPR: (Fine) Chemicals Examples of target classes of molecules and their properties to hook up separation (Fine) chemicals (the fish) Terpenes Fatty acids Alcohols Amino acids Esters Sugars Proteins Fats Aldehydes/Ketones Properties (the bait/food) Hydrophobic interaction Charge/hydrophobic interaction Vapour pressure/hydrophilic interaction Charge/solubility Hydrophobic interaction/vapour pressure Solubility/hydrophilic interaction Charge/solubility/molecular size/shape Hydrofobic interaction Vapour pressure/hydrophobic interaction 0

21 ISPR at TNO our approach A. Feasibility study technical/economical Selection separation technique - physical properties / models Determination process parameters - experimental screening - process models Demonstration - proof-of-principle B. Scale-up - pilot / demo / full-scale 1

22 TNO s ISPR-Toolbox Characteristics of TNO s portfolio Expertise in development and application of innovative separation processes Multi-applicable tools to hook specific molecular properties 6 patents pending on specific ISPR-techniques Use of hybrid separation techniques to develop new fishing rods ractical examples from the Toolbox ) SIRs = extraction/adsorption particles ) Pertraction = membrane contactor and extraction ) CRYSTEL = crystallisation and electrochemistry ) Template Induced Crystallisation ) Electro Dialysis (provisional) 2

23 How Solvent Impregnated Resins work Start End 3

24 Conceptual process with SIRs SIRs = Extraction(/adsorption) + flotation Microstructure of a typical macroporous polymer Recycle liquid phase Filter Status Principle proven Patent pending SIR Reactor Recycle SIRS Product Example: recovery of phenol from fermentation with Pseudomonas Putida 4

25 Solvent selection criteria for phenol Able to form hydrogen bridges with phenol C=O C-OH C=N, etc Extractant should not dissolve in H2O Nice to have: π-π interactions with aromatic ring of phenol Ideal extractant... H-bond π-π interactions Hydrophobic tail 5

26 Equipment for Medium-Throughput Screening Characteristics Parallel reactors Robotics for dosing / sampling / diluting On-line HPLC analysis ISPR-Applications Screening of extractants Screening of adsorbents Screening of templates Additional Applications Solubility measurements Effect of additives Reactions 6

27 he most SIR-ious extractant at the moment... haracteristics SIR-ious extractant Extractant is not toxic for Pseudomonas Putida Ionic Liquid low water solubility Good hydrogen bond acceptor due to phosphate-group Partition coefficient for phenol of about 600 between Extractant and H 2 O compared to a partition coefficient of 31 for octanol : H 2 O 7

28 Proof of principle for SIRs Conditions fed-batch fermentations Phenol producing Pseudomonas Putida S12 strain Starting volume = 1.5 L, end volume = L Total volume fermentor = 2.5 L Nitrogen limited, glycerol as C- source 3 fermentations to validate ISPR Control + 50 g Adsorbent (XAD-4) + 50 g SIRs (XAD-4 with extractant) 8

29 . putida Fed-batch fermentation: reference Phenol in aqueous phase (mm) Control Time (hr) 9

30 Effect of an adsorbent in a batch fermentation 10 Phenol in aqueous phase (mm) Control +50g XAD-4 Addition of XAD-4 Product release Time (hr) 0

31 Phenol in aqueous phase (mm) Pseudomonas Putida: Thank you SIR Addition of SIRs +50g +50g XAD-4 XAD-4 +50g +50g SIR SIR Control Product release Time (hr) phenol concentration in aqueous phase remains low! 1

32 omparison 3 different fed-batch fermentations Phenol produced (mmol) Productivity (µmol/l/h) Yield P/S (mol%) Control g XAD g SIR Conclusions SIR Proof of Principle for SIR-technology is delivered Phenol production, productivity and yield increase 2

33 Pertraction: model compound and solvent Phenol as model compound 1-octanol as model solvent Previous research in combination with P. putida fermentations 3

34 In-situ pertraction set-up Feed Membrane Reactor (aq) 1-Octanol 1 M NaOH Purification In-situ pertraction 4

35 In-situ pertraction [1] + = 5

36 In-situ pertraction [2] 6

37 Pertraction: Proven Technology/Process Innovation Main technical & economical features Low investment Pertraction has great Compact Equipment potential for In-Situ Product Stable and large interface Removal in (fine) chemical Flexible operation production processes Pertraction unit Invista Vlissingen (NL) waste water Bioreactor 15 m 3 /h aromatics process since 1999 feed stoc k 7 Simplified Process Flow Diagram Industrial Pertraction installation

38 In-situ crystallisation Model compounds: Charged molecules with low solubility for neutral species: carboxylic acids, amino acids Techniques: Electrochemically induced crystallisation (Crystel) - localized driving force Template induced crystallisation (TIC) - requires suitable templates - but also driving force 8

39 CRYSTEL: CRYSTallization with ELectrochemistry Principle: Carboxylates are very soluble around ph 7, but solubility decreases significantly with decreasing ph Idea: Affect the local ph to induce crystallization without affecting the bulk ph CRYSTEL Method: Water electrolysis in fermentation broth At anode: H 2 O 2 H + + ½ O e - At cathode: 2 H 2 O + 2 e - 2 OH - + H 2 9

40 Results Crystel Lab Scale Tests (1) Example: fermentative production of Cinnamic acid 0 pk A = 4.44 Cinnamate is dominant species in fermentation broth Solubility sodium cinnamate = 90 g/l (cold water) Solubility cinnamic acid = 0.55 g/l (25 C) Na-cinnamate (mm) Na-cinnamate Na-cinnamate Na-cinnamate current current current ph ph Time (minutes) ph No re-dissolution of precipitated cinnamic acid during product recovery ph, I (A)

41 Results Crystel Lab Scale Tests (2) Depending on electrolysis conditions, cinnamic acid is precipitated as a solid on the anode, or as flocks in the vicinity of the anode. Product removal by scraping, flottation, filtration, current reversal, etc. 1

42 Conclusions CRYSTEL Method for in-situ removal of fermentation products by local ph control. Maintaining constant product concentration in fermentation broth. Avoiding inhibition or poisoning of fermentation process Electricity as reagent. No additional consumption of chemicals and thus no inorganic byproduct from ph-switch reaction (e.g. gypsum). 2

43 Template Induced Crystallization Templates are heterogeneous seeds promoting crystallization Templates do not dissolve in undersaturated solution Templates act as carrier material for the crystallized product Separation of the product from broth simplified TIC principle is generic, but compound-specific Template Screening Methodology is required 3

44 Template Screening Methodology Cinnamic acid is the model compound Induction time measurements to examine suitability of templates for TIC Using ph-track methodology Induction time is calculated using Inflection Point calculations Methodology is implemented in robotized equipment Statistical analysis of data 4

45 Model compound Model compound: Cinnamic acid (aromatic carboxylic acid) Driving force: ph shift crystallization CAH CA + H ( aq) ( aq) ( aq) + Low solubility High solubility ph 5

46 Model compound 6

47 ph-track: Experimental setup & principle HCl CA + H + CAH ph T CA - HCl 7

48 ph-track: Inflection Point calculations 4,1 4,05 t 0 ph [-] 4 τ ind t PI 1 st derivative 3 rd derivative t PI t max 3,95 DATA FIT y = , Time [min] 8

49 ph-track: Typical result (blanc & TiO 2 template) 9

50 Statistical analysis of induction times Statistical test to qualify templates as promoting crystallization Calculation of probability distributions of blank and template experiments 0

51 Results blank and ZrO 2 experiments 1

52 Conclusions TIC Screening methodology to evaluate templates is proved* Likely generic for all charged molecules affected by ph Driving force for in-situ crystallization can be induced Combination of induced driving force and templated crystallization is solution to yield low soluble components with high purity *J. Urbanus, C.P.M. Roelands, J.H. ter Horst, D. Verdoes, P.J. Jansens, Screening for templates that promote crystallization, Food and Bioproducts Processing 86(2), ,

53 Conclusions TNO ISPR (fine)chemicals produced by fermentation Products often toxic or inhibiting to microorganism ISPR improves productivity Multi-applicable techniques required Tailor-made by use of auxiliairies TNO developing toolbox of ISPR techniques Feasibility study first, followed by scaling-up 3

54 Acknowledgements TNO: Louise Heerema, Corjan van den Berg, Jan-Harm Urbanus,Tahmineh Nasrollahnejad, Robert de Bruyn, Joost van Erkel, Roel Bisselink, Dirk Verdoes, Paul Bussmann Delft University of Technology: Luuk van der Wielen, Peter Jansens, Joop ter Horst TU/e: Jos Keurentjens This project is financially supported by the Netherlands Ministry of Economic Affairs and the B-Basic partner organizations ( through B-Basic, a public-private NWO-ACTS programme (ACTS = Advanced Chemical Technologies for Sustainability). 4

55 Message With the proper fishing rods and baits it will be possible to catch the (gold)fish 5

56 TNO Quality of Life / Bioconversion Renewable feedstock: focus on lignocellulose hydrolysate R Products: focus on substituted (hydroxy-)aromates 6

57 Substituted (hydroxy-)aromates many & diverse applications, e.g. in plastics (LCP s), resins, fibers petroleum-based often difficult to synthesize chemically R Alternative: bio-based production no petroleum dependency / green production prices may go down to < $ 5 / kg Challenge: TOXIC to most microorganisms: solvent tolerant host mandatory Pseudomonas putida S12 7

58 Electrodialysis as a separation technique Electro-electrodialysis EED Conventional Electrodialysis CED Electrodialysis using Bipolar Membranes ED Recovery of the organic acid/base from its salt Concentrating of organic acids/bases or salts Recovery of the organic acid/base from its salt Typical energy consumption: 0,2 5 kwh/kg 8

59 Recovery of an organic base from its salt by electro-electrodialysis Product recovery enabling continuous operation: n 2 2 t = 0 Feedstock O 2 /air micro-org. Fermentor (4 - n) wt% R-NH 3 + Separation unit ~40 wt% R-NH 2 ~4 wt% R-NH Energy consumption: 1 2 kwh/kg

60 Electro-electrodialysis To fermentor for ph-adjustment MEA-product (Na 2 SO 4?) CEM AEM To fermentor CEM O 2 H 2 H + Cl - OH - H + H + MEAH + Electrolyte (H 2 SO 4 ) Electrolyte (HCl) Diluate (MEA-Cl) Concentrate (Na 2 SO 4 ) from fermentor 0

61 Laboratory electro-electrodialysis set-up 1

62 ISPR at TNO our approach molecular affinity mass transfer proof-of -principle process concepts process models proof-of -concept creening solvents templates Mass transfer - coefficients - growth rates Exp lab - increase productivity Configuration -In-Situ or In-Stream? - batch or continuous? Cost per unit product vs base case ISPR next step 2

63 Process configuration TIC feed Crystallized product Template solvent product 3

64 Conceptual integrated process for in-situ ph-shift crystallization of amino acids localized on electrodes Substrate carboxylic acid broth 4