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Introduction
The world economy resource cycle:
Ancient time 2100 2000 1900
Biobased Biobased
Hydrocarbon
Chemurgy (W. J. Hale) 1934: hemp body & soybean car (Ford) WW2: corn, guayule, dandelion for rubber
Benefits of the Biobased economy
Non-renewable feedstock Process Product(s)
Waste
Conventional Fossil energy
Landfill or incineration
Renewable bioresource Bioprocess Bioproduct(s)
By-product(s)
Biobased Biomass
Recycle into bioresource
BioEconomy
Production – Trees
– Grasses
– Agricultural
Crops
– Agricultural
Residues
– Animal Wastes
– Municipal Solid
Waste
- Aquatic biomass
- Food byproducts
End-Uses Products – Plastics
– Functional Monomers
– Solvents
– Chemical Intermediates
– Phenolics
– Adhesives
– Hydraulic Fluids
– Fatty acids
– Carbon black
– Paints
– Dyes, Pigments, and Ink
– Detergents
– Paper
– Horticultural products
– Fiber boards
– Solvents
– Adhesives
– Plastic filler
– Abrasives
Fuel
Power
Processing - Acid/enzymatic
hydrolysis
- Fermentation
- Bioconversion
- Chemical Conversion
- Gasification
- Combustion
- Co-firing
Plant
Science – Genomics
– Enzymes
– Metabolism
– Composition
Year
2020FP1FP1
FP2FP2
Technology
Front today
Novel molecules
Bioprocesses
Modified Chemistry
Current chemistry
& technology
Waste & by-products
Existing crop plants
Dedicated crops
Modified plants
FP-1: the current and short-term developments in valorisation of existing crop parts and plant-based building blocks with existing or modified chemical and bio-processes
FP-2: longer-term perspective, requires a “quantum leap” for production of novel molecules by the integration of modified plants with new technologies
Integrated technology
Boeriu et al. 2005. Biomass valorisation for sustainable development. IWA Publishing
Sustainability criteria
Social sustainability
● Respecting human, land right and land use right
Economic sustainability
● Local development of the region
● Equitable profit sharing (owner, employees & local community)
Environmental sustainability
● Conservation of biodiversity
● Land preservation
● Water and soil preservation
Biomass – a sustainable resource
Critical points
Battle for acres
deforestation
Food vs. fuels & chemicals
Availability of this “unlimited” renewable resources
Occurrence and composition of biomass
Lignocellulosic biomass:
• 150 billion tonnes annually#
• Wood, chips, residues • Agricultural crops & residues • Grasses • Aquatic biomass • Vegetable oil plants (fatty acids) • Tannins (wood bark), lignans (seeds)
Proteins
Cellulose
Lignin
Hemicellulose
Terpenes #Balat and Ayar 2005 8
Chemicals from biomass
Biomass – a mixture of functionalised and non-
functionalised compounds that can be produced with
low enthalpy (H) losses
CxHzOy(OCHz)v
Oil / gas
lignin
protein
BiorefineryPetrochemical route
Biomass
CxHy
chemicals
nafta
CxHzOyN (S)v
CxHzNCxHzN
CxHzOy
carbohydrates
CxHzO
H
oils / fats
CxHyOz
CxHy
Boeriu et al. 2005. Biomass valorisation for sustainable development. IWA Publishing
Drivers for biobased chemicals & materials
Increased value of chemicals relative to fuels
Societal need to reduced dependency on feed stock supply
Potential for GHG savings
Economical potential for rural regions
Potential for more sustainable products
Declining reserves of easily accessible fossil feed stocks
Inexpensive natural gas and crude oil
(fracking and horizontal drilling technologies)
?
Chemicals and materials driven biorefineries
Increased profitability of 2nd generation biofuels production
Integrated with traditional starch, vegetable oil, sugar and paper producers
Diversification of agrifood industries non-food products
Increased supply of biomass (Mil. tons) for chemicals and materials due to The decline of paper and pulp industry
11
Biomass based chemicals
Biobased chemicals can have
● Same structure as fossil oil based chemicals
● Have a unique structure
Mandatory for development price effective biobased chemicals:
● Development of efficient set of toolboxes for conversion
technology
● Backwards integration with regard to feedstock
supply/refinery
● Forward integration with regard to
polymer/material/product development.
Biomass based chemicals preferably should result from waste streams or crops avoiding food vs. non–food use competition
Chemicals and materials driven biorefineries
Renewable chemicals
Global market $ 3.6 billion (2013)
Estimated $ 12 billion (2020)
Biobased aromatics
www.chemweek.com; august 2013
Biobased chemicals: developments
Lab scale Glycolic acid Butadiene Glucaric acid Adipic acid HMDA p-Xylene
Pilot, demonstration Acetic acid Acrylic acid 3-OH-acrylic acid 2,5-FDCA Aromatics
Commercial Ethylene Ethylene glycol Propylene* Propylene glycol 1,3-propandiol Epichlorohydrin Lactic acid Acetone Isobutene Succinic acid 1,4-Butandiol Isoprene 2,5-FDCA* Sebacic acid Dodecanoic acid
www.chemweek.com; august 2013
SMEs Multinationals
Trends: Circular economy
industrial economy producing no waste and pollution
material flows:
● biological nutrients
● technical nutrients
Needs:
● Business process innovation
● Business model innovation
● Enabling technologies
Some examples: • Cyrculating on the fly
• Plastic recycling
• Deconstruction Disassembling & rebuilding China: leading National development strategy 12th Five year plan 2011-1
The circular economy, Nature, March 2016
Wageningen UR Food & Biobased Research
Contract research organisation, part of Wageningen UR
About 100 scientists committed to biobased chemicals,
materials, and biorefinery technology
Developing chemical and biotechnological conversion routes to
biobased drop-in solutions and functional replacement
polymers
Network throughout the value chain
17
Wageningen UR Food & Biobased Research
Biofuels & bio-energy
Bio-based materials
Bio-based chemicals
Bio-based Products
Biomass
Provide added value for our customers
by creating sustainable and functional solutions
Biorefinery &
Sustainable value chains
Bioconversion
Sustainable Chemistry
Industrial Biotechnology
Process engineering -> efficient and sustainable processes
New markets and new products
Biobased Chemicals Programme (WUR-FBR)
Focus areas:
● Carbohydrate based chemicals:
● Furan platform
● Isohexide platform
● Sugar biotech platform
● Lignin based chemicals
● Oil based chemicals
● Protein derived chemicals
Alternative renewable feedstocks (WUR-FBR)
Alternative vegetable sources:
● Algae, Algicoat project (oils, FA)
● Dandelion, EU-Pearls (latex)
● Seaweeds (biorefinery)
Laminaria
digitata
Ulva sp.
(green)
Alaria
esculenta Palmaria
palmata
Alternative renewable feedstocks (WUR-FBR)
Chitin – 2nd most available resource
The Chit4Value project
Olefins Biofuels
Polycarbonates
Alternative feedstocks: CO2 capture (WUR-FBR)
Immobilized Enzymes
CO2
CH3OH
Gasoline
substitute DME &
biodiesel
Raw material for
chemicals & materials
Immobilized Enzymes
CO2
CH3OH
Gasoline
substitute DME &
biodiesel
Raw material for
chemicals & materials
(Bio)catalysts HCOOH
The BioCoMet project
Polyamides: present and future (WUR-FBR)
Commercial polyamides (petro-
based)
Nylons Aramids
Polyaldaramides
(Glylons)
Polyglutamic acid
Furanic polyamides
-Caprolactam
Valerolactam
1,4-butandiamine
Adipic acid
Terephtalic acid
Sebacic acid
Bio-based polyamides
Drop-in New
polyamides
Health, cosmetics
Food
Biobased ε-caprolactam (WUR-FBR)
OH
NH2 NH2
O
Potato-based Lysine
HC COOH
NH2
H2N(CH2)4lysine oxidase
lysine
C COOH
O
H2N(CH2)4
2-keto-6-aminocaproic acidisolated from plants
i. reductionii. dehydrationiii. hydrogenation H2
C COOHH2N(CH2)4
N
O
H
caprolactam6-aminocaproic acid
In plant Enzymatic/chemical steps
N
e.g. NOCl/horHNO3/-H2O
e.g. hydroxylamine
sulphate/-H2O
Beckmann rearrangement oleum
or ammonia
NOH
O
O
H
NH2(CH2)4CH2COOH
CNH2(CH2)4
NH2(CH2)4CH
L-lysine oxidase
COOH
O
NH2
COOH
Existing process Proposed biosynthetic route
a)
b)oraminotransferase
1. reduction (chemical or enzymatic)2. dehydration
3. hydrogenation
Fossil resources Biomass/sugars
A novel bio-synthetic cascade to synthesise -caprolactam utilising intermediates (lysine) synthesised in planta
Project ECHO-Lysine
Efficient route to 5-aminovaleric acid (WUR-FBR)
Immobilization of L-lysine oxidase
Pukin et al, 2010, J. Mol. Cat. B. Enzymatic
Oxidation of L-lysine in 120 mM Lys/Lys.HCl, pH 7.4, 37 C, 3 U LysOx (immob), 50 ml
95% yield 5-aminovaleric acid
reuse of the biocatalyst for several cycles
Polyaldaramides: green biopolymers (WUR-FBR)
C6, C5 sugars Uronic acids
Amino acids
Aldaric acids/esters
,-alkyldiamines
Polyaldaramides
T, Cat (E) T, Cat (E)
T, Cat (E) T, Cat (E)
T, Cat (E)
Project BioProduction
Markets:
Food
Cosmetics
Polymers
Pharma
Polyesters
Substrates for:
Macrolactones
Estolides
Oil based chemicals (WUR-FBR)
Applications: Flavours Emulsifiers
Hydrolysis
Strategic project ValOil
Lignin conversion (WUR-FBR)
Binders/resins
Ocobinders
Ocobinders
Polymerisation Depolymerisation
Composites Coatings Surfactants
Monomeric chemicals Chemical/ Enzymatic upgrading
(Bio-)catalysis
Fractionation Oligomeric fragments
Confidential 31 31
Biobased performance materials (WUR-FBR)
Expanded PLA – 3D foamed structures
● Good cell structure
● Density <30 g/l
Renewable polyamides & Non-isocyanate polyurethanes
Intended application area:
(Car refinish) Coatings
Potential spin off application:
Insulation materials,
construction materials