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ENZYMATIC CONVERSION OF RENEWABLE BIOMASS INTO GREEN HIGH VALUE PRODUCTS
K. Vanbroekhoven & W. Dejonghe, VITOEuropean workshop: Inclusion of primary production in biobased value chainsBrussels, 20/02/2020
19/02/2020
©VITO – Not for distribution 1
ESTERS
SYNTHESIS ORGANIC ESTERS FROM AGRICULTURAL COMPOUNDS AVAILABLE IN EUROPE
19/02/2020
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▪ Agricultural compounds used in ester synthesis
Vegetable oilAnimal fat
Long chain fatty acids: > C12
ESTERS
VEGETABLE OILS PRODUCED IN EUROPE
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2017: EU36 Mton seed → 12 Mton oil
Seeds Rape and turnip rape Sunflower Soya
https://ec.europa.eu/eurostat/statistical-atlas/gis/viewer/?year=&chapter=12&mids=BKGCNT,BKGNT22016,C12M04&o=1,1,1&ch=AGF,AGR¢er=49.50449,27.3328,3&lcis=C12M04&Kumar et al.? 2016, dx.doi.org/10,1016/B978-0-12-802980-0,00019-5
M = million
200 Mton
Coconut oil: C12
BUT: - 80 % food + 15 % biodiesel- C18: Oleic + linoleic acid, no C16 + C12
ANIMAL FAT PRODUCED IN EUROPE
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Total production of different categories of animal fats in EU
Destination of edible and Cat 3 fat in 2014 in EU.
1,5 Mton animal fat/yearBeef, pig and poultryPalmitic, oleic, stearic acid
0,6 Mton animal fat/year used in oleochemical industry (40 %) to make:
- fatty acids- fatty alcohols- glycerol
Source: EFPRA
M = million
ESTERS
SYNTHESIS ORGANIC ESTERS FROM AGRICULTURAL COMPOUNDS AVAILABLE IN EUROPE
19/02/2020
©VITO – Not for distribution 6
▪ Agricultural compounds used in ester synthesis
Long chain FA
Acrylic acidMethacrylic acid
Short chain FA
ESTERS
SYNTHESIS ORGANIC ESTERS FROM AGRICULTURAL COMPOUNDS AVAILABLE IN EUROPE
19/02/2020
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▪ Biomass used in ester synthesis
Short chain FALong chain FA(metha)crylic acid
Natural Petrochemical
Alcohol
(Poly)Glycerol
Sugar
ESTERS
SYNTHESIS ORGANIC ESTERS FROM AGRICULTURAL COMPOUNDS AVAILABLE IN EUROPE
19/02/2020
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▪ Agricultural compounds used in ester synthesis
AlcoholGlycerol: 2,2 Mton from biodiesel + FASugar
Natural Petrochemical
Short chain FALong chain FA(metha)crylic acid
M = million
ESTERS
SUGAR PRODUCTION IN EUROPE
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Cereals2017: 310 Mtons217 Mtons starch (70%)
Sugar beet2018: 120 Mtons18 Mtons sucrose (15%)
Potatoes2018: 52 Mtons8 Mtons starch (15%)
https://ec.europa.eu/eurostat/statistics-explained/index.php/Agricultural_production_-_crops#Potatoes_and_sugar_beet
https://ec.europa.eu/eurostat/statistical-atlas/gis/viewer/?year=&chapter=12&mids=BKGCNT,BKGNT22016,C12M03&o=1,1,1&ch=AGF,AGR¢er=49.50449,27.3328,3&lcis=BKGNT22016&
M = million
Sugar mainly used in food14 kTon sucrose esters/2015
ESTERS
SYNTHESIS ORGANIC ESTERS FROM AGRICULTURAL COMPOUNDS AVAILABLE IN EUROPE
19/02/2020
©VITO – Not for distribution 10
▪ Agricultural compounds used in ester synthesis
AlcoholGlycerolSugar
Natural Petrochemical
Short chain FALong chain FA(metha)crylic acid
Short chainLong chain > C6
ESTERS
SYNTHESIS ORGANIC ESTERS FROM AGRICULTURAL COMPOUNDS AVAILABLE IN EUROPE
19/02/2020
©VITO – Not for distribution 11
▪ Agricultural compounds used in ester synthesis
AlcoholGlycerolSugar
Natural Petrochemical
Short chain FALong chain FA(metha)crylic acid
Short chainLong chain > C6
ESTERS
SYNTHESIS ORGANIC ESTERS FROM AGRICULTURAL COMPOUNDS AVAILABLE IN EUROPE
19/02/2020
©VITO – Not for distribution 12
▪ Agricultural compounds used in ester synthesis
AlcoholGlycerolSugar
Natural Petrochemical
Short chain FALong chain FA(metha)crylic acid
Short chainLong chain > C6
CAN AN ALTERNATIVE PROCESS BE DEVELOPED FOR ESTER SYNTHESIS?
13
Ref: Schumacher and Thum, Chem.Soc.Rev., 2013, 42, 6475
Green & sustainable process
Natural & organic products
Esterification catalyzed by Lipase to synthesize fatty acid esters
INDUSTRIALLY DRIVEN ESTER RESEARCH AT VITO: THE PROCESS
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• Model based assessment
• Techno –economical assessment
• 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
INDUSTRIALLY DRIVEN ESTER RESEARCH AT VITO: IN PICTURES & KG SCALE
15
Initial experiments in mL scale
Lab scale 3L reactor Lab scale PV set-up Pilot scale PV set-up
1/ EMOLLIENTS: UPSCALED PROCESS WITH MEMBRANE ASSISTED WATER REMOVAL
Confidential 16
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
0
0,5
1
1,5
2
2,5
3
Wat
er (
%)
• High conversion of fatty acids• Solvent free: High product yields• No loss of substrates or products during
water removal• Very stable enzyme and membrane
performance
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]
MONO (DI)ACYLGLYCEROLS AND POLYGLYCEROLS
Voettekst invulling 18
Image source:chemicalsinourlife.echa.europa.eu Image source: whattech.com
Mono (di)acylglycerol
Polyglycerol ester
Organic compoundResource instead of feed additive
SUGAR ESTERS
19
Advantage enzymatic process:- Mild process: DSP- Regioselectivity: Degree esterification- Green solvent: sustainable + re-usable
Use of mono-, oligosaccharides and agricultural side stream
ESTERS
SYNTHESIS ORGANIC ESTERS FROM CHEMICALS PRODUCED IN EUROPE
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▪ Primary substrates used in ester synthesis
Fatty acidVegetable oilAnimal fat
AlcoholGlycerolSugar
Natural Petrochemical
Powered by: TNO & VITO
2/19/2020 21
Horizons Feedstock Conversion Technology Bio-Aromatics Applications
Sugar to Bio-Aromatics
C5 Sugars/Furfural
Biomass residues &Recycle streams
Specialty€€€
Lignin to Bio-Aromatics
Thermochemical Conversion of
Biomass to Bio-Aromatics
Diels-Alder
Catalytic Depolymerization
Pyrolysis
Gasification Bulk€
Lignin
ESTERIFICATION OF PHENOL ALIKES FROM LIGNIN DEPOLYMERIZATION
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OH
OH
O
O
OH
O
OH
OH
O
O
OH
O
O
OH
O
S lignin, R1 = OMe, R2 = -OMe
H lignin, R1 = H, R2 = -H
G lignin, R1 = H, R2 = -OMe
OH
OH
R1
R2
a)
biosynthesis
OH
O
OH
OH
O
OH
O O
dimeric
monolignol
derivatives
oligomeric
monolignol
derivatives
OH
O O
OH
PG DCA
PS DSA
hydroboration/
oxidationreduction
catalytic
hydrogenation
LIGNIN OIL
OH
R1
R2
O
OH
OR
1
R2
OH
OR2
OH
O R1
OOH
OHO
R1
R2
OH
lignin
OR
1R
2
OHOH
OH
R2
O
O
O
R1
R2
OH
O
R1
R2
OH
OH
O
R1
R2
OH
O
R1
R2
OH
OH
OH
O
R1
R2
OHlignin
O
R1
OH
lignin
b)LIGNIN
catalytic
hydrogenationDCA
CHEMICAL SYNTHESIS
OH
O
CH3
OH
OH
O
CH3
O
O
CH2
R
FRP (AIBN)
OH O
CH3
O
O
R1
R2
Rn
Novozyme 435
5A MS, Methyl Methacrylate
polymerization
Enzymatic conversion
23
ESTERS OF ALCOHOL DERIVATIVES FROM C5 SUGARS
4-methoxybenzyl alcohol
Furfuryl alcohol
Tetrahydrofurfuryl alcohol
ESTERS OF MONOTERPENE ALCOHOLS
a-pinene
b-pinene
Pine forest
Geraniol
Citronellol
Linalool
Flavor & Fragrance
Acetate esters
Figure 1: Acetate esters used as flavours and/or fragrances and investigated in VITO
Figure 1: Acetate esters used as flavours and/or fragrances and investigated in VITO
(meth)acrylate esters
OLIGOSACCHARIDES
BIOMASS DERIVED POLYSACCHARIDES INTO HIGH-PERFORMANCE FUNCTIONALINGREDIENTS
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Properties:▪ Prebiotic (FOS, GOS, POS, MOS)
▪ Antioxidant (XOS)
▪ Antimicrobial (COS)
▪ Anti-coagulant (COS)
▪ Plant elicitors (POS, COS,
carrageenan)
▪ Plant biostimulant (COS,
carrageenan)
Oligo’s from algae
POS
COS
ChitinChitosan
StarchUlvan, carrageenan, laminarin, fucoidan
Lactose
Mannan
MOS
Confidential
Investigatedby VITO
XOS
GOS
OLIGOCAR
MOOV - MOBILISATION AND OPTIMISATION OF VALUE CHAINS
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OPTIMISED VALUE CHAINS
INTERACTIVE DASHBOARDS
TAKE HOME MESSAGE
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▪ European agricultural feedstocks in the synthesis of biobased esters
▪ Biobased short chain alcohols and fatty acids result in 100 % biobased esters
▪ The interest in the market of enzymatically produced biobased esters ↑
▪ VITO developed a sustainable enzymatically based technology to produce a
portfolio of esters & can optimize the value chain
▪ Call for participation in our developments:
▪ Your feedstocks for our enzymatic ester synthesis
▪ Screening functionality of esters in your application
COLLEAGUES
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MOOV teamEnzyme team
Y. Satyawali W. Van Hecke L. Cauwenberghs H. Elslander A. De Meyer R. Guisson
Thanks for your attention!
M. Martinez Garcia
