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The Pulp-and-Paper BasedBiorefinery: Research Challenges
… and Market Opportunities
Carlos Pascoal Neto
RAIZ
• The biorefinery vs oil refinery
• The pulp-and-paper biorefinery
• Research challenges and market opportunities
• Cellulose
• Nanocellulose
• Hemicelluloses
• Sugars
• Lignin
• Extractives
A couple of examples from RAIZ – The Navigator CompanyBiorefinery R&D programme
Outline
The end of (cheap) oil
2
http://www.paulchefurka.ca/Population.html
The biorefiney vs oil refinery
3
An old concept for an old issue !
4
Source: Borregaard
The biorefiney vs oil refinery
The emerging bioeconomy
5
Bio chemical / fuels market trend
Silicon valley bank
6
The emerging bioeconomy
Lignocellulosics composition
7
Forest
Agricultural
Per Hoffmann, Oskar Faix and Ralph Lehnen
The pulp-and-paper biorefinery
8
Wood
Forest residues
Hemiceluloses Sugars
Biofuels (bioethanol …)BioplasticsBacterial cellulose …
Extractives(Triterpenes,
essential oils…)
Lignin
Cellulose fibres,
Nanocellulose
Electric energy, biofuels
Composites, textile fibres ….
Pulp-and-paper mill
PaperPulp
(~50% of initial wood material)
Biofuels(bioethanol …)
Hemiceluloses
AromaticsAdhesivesFoamsCarbon fibres …
BioactivecompoundsNutraceuticals …
BiopolymersFood additives …
Cellulose
9
Injection Moulding
Cellulose-basedcomposites for automotive industry
Cellulose
10
Wood Fibre Composites Market
Nanocellulose:Exploiting the nano scale of cellulose fibres
11
Nanocellulose
Nanocellulose
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Nanocellulose
13
Potencial Uses ofNanocellulose
Nanocellulose
14
Global Nanocellulose production capacities estimates for 2020
Conservative – 2500 tons /year. Optimistic – 5500 tons /year.
Hemicelluloses
15
Hemicelluloses
16
HEMICELLULOSES - XYLANS - POTENTIAL APPLICATIONS
furfural
xylitol
rheology modifiers
emulsifiers
gelling agents (prevent ice formation)
absorbents (increase water content bread)
food additives
adhesives
paper additives
medicine / pharmaceuticals
pentosan polysulfates PPS (Elmiron)
XOS - xiloologosaccharides
Hemicelluloses
17
GLOBAL MARKETS – XYLAN END PRODUCTS
Xylitol 2013 162 ktons - 670 M USD + 4 USD / kg
(corn cobs) 2020 242 ktons - 1 000 M USD
Furfural 2013 300 ktons + 1,8 USD / kg
(corn cobs) 2020 655 ktons - 1 200 M USD
Rheology modifiers
(organic & inorganic) 2020 5 600 M USD
XOS - xilooligosaccharides
(corn cobs) 10 – 25 USD / kg
Sugars
18
Sugar syrups
5 L beakers - RAIZ 50 L reactor - LNEG
Enzymatic hydrolysis – scale up
Sugars
Sugars
20
HO OH
OH
HO OH
O
Glycerol
3-Hydroxypropionic acid
HOOH
O
O
Succinic acid
HOOH
O
O
Fumaric acid
HOOH
O
O OH
Malic acid
O
HO
O
3-Hydroxybutirolactone
HOOH
O
O NH2
Aspartic acid
HO OH
OH
OH
OH
Xylitol/arabinitol
OH
O
O
Levulinic acid
OHHO
O
O
Itaconic acid
HO OH
O
NH2
O
Glutamic acid
O COOHHOOC
2,5-Furanedicarboxylic acid
HOOH
OH
OH
OH
OH
Sorbitol
HOOH
O
OH
OH
OH
OH
O
Glucaric acid
Biomass carbohydrates
C
C
C
C
C
B
B
B
B
BB
B
Platform chemicals from sugars
Sugars
21
Bacterial cellulose (Gluconacetobacter) Nanofibrils 10-100 nm width, 3D network
Wood fibers~20-40 mm width, ~1-3(>) mm length
Bacterial cellulose from wood/cellulose sugars
22
Sugars
Sugar based bio-products market
Sugars
23
Cellulosic bioethanol is emerging ≈ 17 billion L in 2022, 10% share
Bioethanol – a worldwide growing market
10% of bioethanol from lignocellulosics in 2022
24
H2SO4
Lignin
Lignin recovery from kraft black liquors
Lignin
25
Vanillin and Syringaldehyde
Glues for cork composites and stoppers
Vanillin and syringaldehydeobtained (2,5%) by eucalyptus globulus lignin oxidation
Lignin isolated and purified was used on the production ofglues, mixed with polymeric methylene diphenyldiisocyanate (pMDI).
26
Flexible polyurethane foams
Rigid polyurethane foams
Lignin polyols
• Lignin dried and submitted to oxypropylation reaction, using propylene oxide andKOH as catalyst.
• Lignin-based polyols led to the production of foams with lower densities andthermal conductivity, compared to the ones produced with the commercial material.
Lignin
Extractives
27
Triterpenic acids from Eucalyptus bark / biomass
Extractives
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Eucalyptus essential oils
For fragrances, cosmetics and pharmaceutical
products, a 1,5 billion € market
Forest biorefineries
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An option?
University of Aveiro
University of Beira Interior
University of Coimbra
University of Lisbon
University of Porto
Nova University of Lisbon
Bragança Polytechnic Institute
Biotrend
LNEG
PIEP
Acknowledgements
30
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