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

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http://www.paulchefurka.ca/Population.html

The biorefiney vs oil refinery

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An old concept for an old issue !

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Source: Borregaard

The biorefiney vs oil refinery

The emerging bioeconomy

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Bio chemical / fuels market trend

Silicon valley bank

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The emerging bioeconomy

Lignocellulosics composition

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Forest

Agricultural

Per Hoffmann, Oskar Faix and Ralph Lehnen

The pulp-and-paper biorefinery

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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

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Injection Moulding

Cellulose-basedcomposites for automotive industry

Cellulose

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Wood Fibre Composites Market

Nanocellulose:Exploiting the nano scale of cellulose fibres

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Nanocellulose

Nanocellulose

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Nanocellulose

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Potencial Uses ofNanocellulose

Nanocellulose

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Global Nanocellulose production capacities estimates for 2020

Conservative – 2500 tons /year. Optimistic – 5500 tons /year.

Hemicelluloses

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Hemicelluloses

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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

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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

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Sugar syrups

5 L beakers - RAIZ 50 L reactor - LNEG

Enzymatic hydrolysis – scale up

Sugars

Sugars

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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

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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

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Sugars

Sugar based bio-products market

Sugars

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Cellulosic bioethanol is emerging ≈ 17 billion L in 2022, 10% share

Bioethanol – a worldwide growing market

10% of bioethanol from lignocellulosics in 2022

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H2SO4

Lignin

Lignin recovery from kraft black liquors

Lignin

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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).

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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

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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

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