Production of Chemicals and Materials in Future Pulp Mill Biorefineries

Karin Lindgren, Innventia

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries2

INNVENTIA AB

Staff 270 Swedish R&D company Serving customers globally Pulp, paper, packaging, printing, new materials and biorefining

Lindgren Italic 4

Chemical pulping process

Source: Aker Kvaerner

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries4

Biorefinery – Simultaneous production of fibres, energy and chemicals

Increasing costs– Energy and wood

Decreasing trend prices on pulp Biorefinery is the solution

– Handling of large volumes of biomass– New pulp mill products– New efficient separation processes – Add “side” processes

Innventia approach– Kraft/soda pulp mill platform– Focus on the major components– Efficient separation process and mill integration

Lignin carbon fibres

Cellulose

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries6

Wood/plants- a mine for valuable polymersCellulose

Softwoods Hardwoods Agro/annual

Spruce Pine Birch Euca. glob.

Euca. urogr. Bagasse

Cellulose % 44 44 45 51 50 44

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries7

Cellulose Products

NanoCellulose

Kraft Pulp Fibres

Transparent Films

Fibre PLA Composite

Lignin from black liquor - LignoBoost

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries9

Carbohydrates

Extractives

Lignin

Black liquor

50% of the wood ends up in cooking liquor

Wood to kraft pulp mill

Pulp

Cellulose products

55-60 % of energy goes into the black liquor

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries10

Wood/plants – a mine for valuable polymers- lignin

Softwoods Hardwoods Agro/annual

Spruce Pine Euca. glob.

Euca. urogr. Hemp Bagasse

Lignin, % 27 28 24 29 25 22

Physical/chemical properties vary with species and process

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries11

The LignoBoost process

Lignin OUT

Recovery Boiler

Digester

Evaporation

BleachingWood Chips Pulp/Paper

Lignin IN Replacement of fossil fuel in lime kilns

50 L fuel oil ptp can be saved

Wood

Lime Kiln

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries12

The LignoBoost process

LigninBlack liquor

Precipitation Filtration Re-suspendingFiltration &

Displacement washing

CO2

H2SO4Wash liquor

Back to the evaporation plant

Back to the evaporation plant

LigninBlack liquor

Precipitation Filtration Re-suspendingFiltration &

Displacement washing

CO2

H2SO4Wash liquor

Back to the evaporation plant

Back to the evaporation plant

LigninBlack liquor

Precipitation Filtration Re-suspendingFiltration &

Displacement washing

CO2

H2SO4Wash liquor

Back to the evaporation plant

Back to the evaporation plant

LigninBlack liquor

Precipitation Filtration Re-suspendingFiltration &

Displacement washing

CO2

H2SO4Wash liquor

Back to the evaporation plant

Back to the evaporation plant

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries13

LignoBoost lignin – a new material

C 64 - 66 Na 0.05 - 0.4 Ash 0.3 - 1 S 1 - 3 N 0.1

Typical composition, %

OO

OH

OCH3

HO OCH3

HOHO

O

OH

OH

OOCH3

OHHO

OOH3CO

OHHOO

OH

OHO

OCH3

O

OHHO

HO

OCH3

OCH3

O

O

HO

HO

OCH3

HOO

OCH3

OH

OH

HOOCH3

OCH3

OCH3

OCH3

HO

HO

HO

HO

OH

OH

O

O

CHO

OCH3

OCH3

HO

O

OCH3

OOH3CO OCH3

HO O

HO

H3CO

OH

OHO

H3CO

O O

OH

OCH3

lignin

OHO

OHO

HO

HO

OCH3

O

OCH3

OH

O

HO

lignin

OCH3

HO

OH

HO

HO Kraft lignin Ligno-sulphonate

Solubility Alkali Water

Ash content 1% 25%

Sugar content 2% 10%

S 3% 5%

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries15

Metso filter in Innventias lignin demo plantVPA 104024 chambers1-1.2 t lignin/h

16Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries

Fossil fuel in pulp mill lime kilns

In Sweden ca 300.000 tonne oil/year

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Carbon fibres - High value application of lignin

Construction material in composites

Light Weight High Strength and Modulus High Resistans to Heat and Corrosion

Expensive

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries18

Oil or renewable

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries19

Manufacturing process of carbon fibres

Raw material

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries20

Carbon fibres from lignin

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Lignin can make difference

650 000 ton pulp/year

10% lignin extracted = 33 000 ton

… 16 000 ton carbon fibres

…can replace 40 % steel in 160.000 cars

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries22

Water and gas cleaning Main industrial source coal Physical and chemical activation Surface area up to 3000 m3/g

Activated carbon from lignin

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries23

Phenols from lignin

OH

R

Hemicellulose from black liquor, chips, saw dust and forestry residues

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries25

Wood/plants – a mine for valuable polymers- Hemicelluloses

Softwoods Hardwoods Agro/annual

Spruce Pine Birch Euca. glob.

Euca. urogr. Hemp Bagasse

Xylan, % 9 8 26 21 16 29 28

Glucomannan, % 19 18 3 4 3 2 2

• Glucomannan degrades in alkali

• Xylan is relatively stable in alkali

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries26

Chip leaching* for salt and hemicellulose removal

Chip kidney

Developed for pre-treatment prior to kraft pulpingLeaching liquor (acid or alkaline)

Polymeric hemicellulose and inorganic ions

Wood chips To processing• pulping• pelletizing• gasification

*Protected by patents: WO2004/050983, US2005/0034823, WO03/046276

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries27

Xylan from black liquor Industrial ultrafiltration trials with in-line ceramic membrane 2007 Laboratory membrane filtration unit at Innventia since 2003

White liquor

Toevaporation

White liquor

Retentate

UF-membraneFeed

Wood chips

Unbleached pulp

Principal outline of mill trial:

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries28

Polymeric Xylan from black liquor

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries29

Potential hemicellulose applications Gas barriers

Hydrogels

Fiber additives

Polymers (PLA) Xylitol, furfural Sugar acids Emulsifiers Carboxymethylation

Other applicationsO

HO

OH

O

HO

OH

O

O

HO

OH

O

O

OH

HO

HO

O

HO

OH

O

H O

OH

O

O

O

H O

O H

O

O

HO

OH

O

O

O H

OH

HO

H O

O

O

O

O H

O H

O H

O

O

O

H O

O

H O

O H

O

OH OH O

OO H

O H

O

O

H O O

O

OO H

O

O H

O

H O

O HH O O C

(Z )

SW fibre

4-5 times higher surface charge

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries30

Wood xylan feedstock for lactic acid and PLA

O

OHHOHO

OH

Acidic or enzyme hydrolysis

Pentoses and hexoses

Lactic acid

Fermentation or alkaline oxidation

Polymerization Polylactide (PLA)H3C

OH

O

OH

H3COH

O

OH

H3CO

O

OH

CH3

O

O CH3

O

O CH3

O

O CH3

O

O CH3

O

O CH3

O

O CH3

OH

O

O

OHHOHO

OH

HO

Hemicelluloses(glucomannan and/or xylan)

2G Ethanol from forestry residues

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries32

2G Ethanol

Acid/enzymatic pretreatment

OR Alkaline preteatment

– can handle all wood/forestry residues/annual plants – good separation of cellulose and lignin– established technology

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries33

Alkaline fractionation

Hydrolysis, Fermentation &

Distillation

Lignin Separation

Energy Recovery

Chemicals Recovery

Forestry Residues Ethanol

Sulphur-FreeLignin

Electric Power

Alkaline route from wood to ethanol

CO2

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries34

2G Ethanol- Alkaline Process Will it work in practice? Yes!

Tested in mill and pilot scale trials

70 t soda pulp produced 40 m3 pulp suspension used 700 litres of ethanol produced S-free lignin produced

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries35

Biofuels

Integrated Energy System

Fibre processing

Primary treat-ment

Pulpwood

Forestry/agri residues

Pulp &Cellulose

Chemicals and materials

The Future Wood/Agri Pulp Mill Biorefinery- many options available

Conver-sion

Conver-sion

Black liquor Heat & Power

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Possible time frame for commercialization

2- 5 years > 5 yearsLignin Fuel oil replacement

Pellet additive Dispersant Activated carbon

Benzene Phenol Carbon fibres

Xylan Gas barrier Fibre surface additive

Lactic acid, PLA Polyesters

Forestry residues

2G EtOH and S-free lignin High quality pellets

Syngas FT-diesel/DME

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries37

The pulp mill biorefinery

Lignin

Cellulose

Bark

Forestry residues

Hemi-cellulose

Extractives

Lignin

· Functional polymers· Bioactive compounds

· DME · Ethanol· FT-diesel · Biooil· Heat· Electricity· Solid fuel· Lignin

· Fiber additives· Barriers· Hydrogels

· Phenols· Carbon fiber· Binders· Dispersants· Activated carbon

Chemicals/MaterialsEnergy

Cellulose · Fibers· Derivatives· Nanocellulose

Thank you for the attention

Karin Lindgren, Production of Chemicals and Materials in Future Pulp Mill Biorefineries38