MEMBRANE ASSISTED PROCESS INTENSIFICATION PAVES THE …
Transcript of MEMBRANE ASSISTED PROCESS INTENSIFICATION PAVES THE …
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MEMBRANE ASSISTED PROCESS INTENSIFICATION PAVES THE WAY FOR THE APPLICATION OF BIOCATALYSIS IN INDUSTRIAL PROCESSES.
Yamini Satyawali, Claudia Matassa, Wouter Van Hecke, Heleen De Wever, Marzio Monagheddu, Winnie [email protected]
7/02/2020
©VITO – Not for distribution 1
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VALUE CHAIN OF ENZYMATIC PROCESSES
7/02/2020
©VITO – Not for distribution 2Reference: Ferrer et al., 2015, Microbial biotechnology, 9, 22-34
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ESTERIFICATION CATALYZED BY LIPASE TO SYNTHESIZE FATTY ACID ESTERS
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Enzymatic Eco-friendly
• Solvent free
• Milder process conditions
Applications
• Food, cosmetics, personal care products, plasticizers, pharmaceuticals
Ref: Schumacher and Thum, Chem.Soc.Rev., 2013, 42, 6475
• Chemical catalyst• High temperature (150°C-
250°C (Unwanted) side reactions
resulting in intensive DSP
• Deodorization• Decoloring• Catalyst neutralization
(unstable product)• Distillation to purify product
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INDUSTRIALLY DRIVEN ESTER RESEARCH AT VITO: THE PROCESS
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• Technical aspects
• Sustainability analysis
• CO2 emission• Energy usage
ProcessConceptualization
Lipase selection
Process in mLscale
Processdevelopment (1-5 L scale)
Techno-economicevaluation
Pilot testing
▪ Free / Immobilized
▪ Reaction conditions
▪ Enzyme kinetics
▪ Pure & technical grade substrates
▪ Definitions of figures of merit▪ Yield▪ Productivity▪ Specific & total
productivity
▪ Process conditions
▪ Process intensification: In situ water removal
▪ Enzyme stability & Re-use
▪ Use of model to combine technical and economic data
▪ Identification of most influential parameter(s) on process economics
▪ At own or industrial site
▪ Mobile Pilot equipment
• Lipase used as biocatalyst for solvent free synthesis of esters using fatty acid and alcohol as substrates
• Infrastructure for batch and (semi) continuous processes (upscaling from 100 mL to approximately 5 L)
• Water removal approaches e.g. pervaporation for process intensification/zeolites
• Process up-scale to pilot scale with coupled hydrophilic pervaporation
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INDUSTRIALLY DRIVEN ESTER RESEARCH AT VITO: IN PICTURES
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Initial experiments in mL scale
Lab scale 3L reactor Lab scale PV set-up Pilot scale PV set-up
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1/ EMOLLIENTS: UPSCALED PROCESS WITH MEMBRANE ASSISTED WATER REMOVAL
Confidential 6
Solvent free Kg scale ester production process
Coupled with PV
Various Kg scale batches tested
Enzyme reusability and membrane stability
Product purification and application testing
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id c
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• High conversion with 99% fatty acid conversion
• <20 wt% residual alcohol (in the end product)
• 1-2 wt% residual acid (in the end product)
• No loss of substrates or products during water removal
• Very stable enzyme and membrane performance
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2/ MONO (DI)ACYLGLYCEROLS
Voettekst invulling 7
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id c
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Time (h)
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4234
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Lauric acid Monolaurin Dilaurin Trilaurin Glycerol
We
igh
t (%
)
65
32
3
65
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MAG DAG TAG
Sele
ctiv
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(%)
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3/POLYGLYCEROL ESTERS
Confidential 8
Polyglycerol + fatty acid → polyglycerol mono ester + water
Tests conducted at various polyglycerol-10: fatty acid weight ratios
Weight ratio(polyglycerol/fattyacid)
Finalconversion(%)
Acid value (mg KOH/g) Average degree ofesterification
1:1 99 0,64 3,73
1,5:1 99 0,43 3,09
2:1 99 0,5 2,82
3:1 100 0 2,78
Image source: whattech.comImage source:chemicalsinourlife.echa.europa.eu
Chem. Biochem. Eng. Q., 33 (4) 501–509 (2019)
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4/ ACETATE ESTERS
Many interesting acetate esters in flavour and fragrance industry
Figure 1: Acetate esters used as flavours and/or fragrances and investigated in VITO
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DETERMINATION OF REACTION KINETICS : CITRONELLYL ACETATE AS AN EXAMPLE …
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Experimentally determined methyl acetate (▲ ) and citronellol (■) concentrations and the corresponding model results (…).
Citronellol
Confidential
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SUGAR ESTERS
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Time (h)
Glucose
Xylose
73
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Glucose Xylose
Sugar conversion
• Lauric acid as acyl donor equimolar• Lipozyme 435• 2-methyl 2-butanol as solvent• Solvent recycling
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7/02/2020
©VITO – Not for distribution 12
SOLVENT RECYCLING BY NF – NANOFILTRATION TESTS
Membrane Glucose Lauric acidGlucose
mono laurateGlucose di
laurate
Polymeric membrane 1
21 % 19 % 7 % 26 %
Ceramic membrane
72 % 64 % 70 % 77 %
Polymeric membrane 2
72 % 65 % 80 % 87 %
Polymeric membrane 3
100 % 82 % 95 % 92 %
Membrane rejections
Cross-flow velocity = 2 m/s (polymeric mem.), 0.3 m/s (ceramic mem.)Pressure = 20 bar (polymeric mem.), 10 bar (ceramic mem.)Temperature = room temp (22˚C)
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INnovative Chemoenzymatic InTEgrated processes – fosters competitiveness of the European green chemistry industry
A MULTI-STAKEHOLDERS PROJECT
3 universities and research organizations 2 SMEs 2 large
industries 1 innovation cluster
PROJECT DURATION:
48 months, from September 2019 to August 2023
INCITE aims to prompt a transition to a more flexible and sustainable chemistry by taking novel integrated upstream and downstream processing paths involving flow chemistry and membrane technology in two chemo-enzymatic processes to an industrial level
FOLLOW US
BUDGET:
Total cost: € 17.4 MEuropean Union’s Horizon 2020 Research and
Innovation Programme contribution: € 13.3 MOBJECTIVES
Contact: [email protected]
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ASYMMETRIC SYNTHESIS OF CHIRAL AMINES FROM ω-TRANSAMINASE
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• Pros:
• Ketones are readily available pro-chiral building blocks
• Very high regio & stereoselectivity of biocatalyst
• Engineered ω-transaminases are available (increasing substrate scope and stability)
• Cons:
• Unfavorable thermodynamic equilibrium →excess of the donor amine often required
• Product and co-product ketone inhibit the enzyme
• To achieve high yield in-situ product and/or co-product removal is often required
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APPLICATION OF HIGH MOLECULAR WEIGHT AMINE DONORS
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©VITO – Not for distribution 15
Development of an innovative process for chiral amine production and separation
NF Membrane
IPA
Jeffamine(400 & 600
g/mol)
HMW amine donors
Enzymatic reaction for chiral amine synthesiscombined with membrane ISPR for productrecovery and TD equilibrium shifting
Reaction optimization
Membrane filtration
ISPR proof of concept
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APPLICATION OF HIGH MOLECULAR WEIGHT AMINE DONORS
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©VITO – Not for distribution 16
HMW AD 6 (Jeffamine 600 g/mol) LMW AD 8
Filtration
Wild type
Reaction
Engineered
HMW AD 3 (Jeffamine 400 g/mol)
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APPLICATION OF HIGH MOLECULAR WEIGHT AMINE DONORS
7/02/2020
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• 25% additional conversion → ISPR proof of concept
• ~85% of HMW amino donors retained by NF
• Low product concentration • Membrane stability • Loss of unreacted ketone substrate
Process Biochemistry, Volume 80, 2019, Pages 17-25
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ENZYMATIC TRANSAMINATION IN ORGANIC SOLVENT/ SOLVENT-FREE MEDIUM AND MEMBRANE ASSISTED PRODUCT EXTRACTION
7/02/2020
©VITO – Not for distribution 18
N-heptane phase
Amine donor phase
BA
TA-v2
N-heptane phase
Amine donor phase
MPPA(BA)
Unreacted BAATA-v2(MPPA)
TA reaction
BA
Jeffamine ED-600
MPPA
TA in organic solvent
PIPI
Reaction Extraction
Heptane
Jeff amine ED-600 Enzyme
Aqueous extracting buffer pH 3
Membrane assisted product extraction
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MEMBRANE ASSISTED PRODUCT EXTRACTION IN ORGANIC SOLVENT
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Membrane contactor screening with synthetic solutions
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MP
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Puramem Selective
Puramem Performance
Hollow Fiber
Hollow fiber (HF) contactor with modified housing and the flat sheet (FS) membrane contactor
High product
purity (>97%)
PIPI
Reaction Extraction
Heptane
Jeff amine ED-600 Enzyme
Aqueous extracting buffer pH 3
4-fold higher product yieldJ Chem Technol Biotechnol 2020; 95: 604–613
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SPINNING THREE-LIQUID-PHASE REACTOR
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Configuration 1 Configuration 2
M
A
B
C
M
A
B
CBA
N-heptane phase
Amine donor phase
MPPA(BA)
Unreacted BAATA-v2(MPPA)
• Feasibility test with synthetic solutions • Enzymatic reaction with product recovery
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SPINNING THREE-LIQUID-PHASE REACTOR
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pH
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Buffer heptane Jeffamine ED-600 pH
• After 5h operation • 71% MPPA extracted • 9,7% AD loss• No BA detected
150 rpm 200 rpm
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ENZYMATIC PRODUCTION OF OLIGOSACCHARIDES FROM POLYSACCHARIDES
CONFIDENTIAL 22
Oligo’s from algae
POS
COS
ChitinChitosan
Starch
Ulvan, carrageenan, laminarin, fucoidan, β-glucan
Lactose
Mannan
MOS
XOS
GOS
i
i
Studiedby VITO
• Properties▪ Prebiotic (FOS, GOS, POS, MOS)▪ Antioxidant (XOS)▪ Antimicrobial (COS) ▪ Anti-coagulant (COS)▪ Plant elicitors (POS, COS,
carrageenan)▪ Plant biostimulant (COS,
carrageenan)
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ENZYMATIC PRODUCTION OF OLIGOSACCHARIDES FROM POLYSACCHARIDES
Short term research
Offline fractionation by cascade of membranesConventional batch process
CONFIDENTIAL
• Disadvantages:• Steered by reaction time:▪ Products with broad range of dp▪ Monosaccharides
• Enzyme inhibition
• Continuous processing:• Enzyme membrane reactor• combining hydrolysis with
separation
Longer term research
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ENZYMATIC PRODUCTION OF CARRAGEENAN OLIGOSACCHARIDES
OLIGOCAR
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• Polysaccharide found in red seaweed• Structure▪ Linear sulfated polysaccharide (> 100-
1000 kDa)▪ Repeating D-Galactose and 3,6
anhydrogalactose units▪ Different types but mainly κ, ι, and λ
carrageenan with▪ 1, 2 or 3 ester sulphate groups
• Thickener in food
D-galactose
3,6 anhydrogalactose
Hydrolysed by carrageenase
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Cloning and production of carrageenase
enzymes
Enzymatic and chemical
hydrolysis of carrageenan
Functionality testing:
Plant elicitor
Plant biostimulant
Prebiotic
OLIGOCAR
CARRAGEENAN HYDROLYSIS AND BIOACTIVITY OLIGOSACCHARIDES
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pBACT5.0: Syngulon expression vector
0 h: starting kappa carrageenan in all 3 bottles has an Mn of approx. 440 kDa
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BIOWOOD
ENZYMATIC PRODUCTION OF XYLAN AND MANNAN OLIGOSACCHARIDES FROM HEMICELLULOSE
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▪ Structure hemicellulose: difference hard- and softwood
Poplar
Birch
Pauly et al., 2008; Malgas et al., 2015; Bajpai, 2016
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ENZYMATIC PRODUCTION OF XYLAN OLIGOSACCHARIDES FROM XYLAN BIRCHWOOD
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xylose XOS2 XOS3 XOS4 XOS5 XOS6 glucose
suga
r [m
g/L]
Xylan (7%) + Viscozyme (12 U/g)
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suga
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Xylan (7%) + CellicCTec2 (12 U/g)
0 h 1 h 2 h 4 h 6 h 24 h
Mainly glucose producedLow conversion xylan
Less glucose producedHigher conversion xylanMainly xylose and DP2 produced
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PRODUCTS
CONTINUOUS ENZYMATIC PRODUCTION OF XYLAN AND MANNAN OLIGOSACCHARIDES IN EMR
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▪ Enzymatic hydrolysis of xylan and mannan: Continuous enzyme membrane reactor
• Control degree of polymerization OS• Decrease enzyme inhibition • Enzymes can be recycled and re-used:▪ Cost for hydrolysis▪ Total productivity (g product/g enzyme)
OS = oligosaccharide
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HEALTH
MATERIALS
ENERGY
CHEMISTRY
LAND USE
New value chainsfrom alternative
feedstock
Biomass
CO2
Sustainableindustrialprocesses
ProcessIntensification
New synthesisroutes
Reuse/valorisation
process streams
FROM SCENCETO APPLICATION