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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 BirchEuca. 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
H2SO4
Wash liquor
Back to the evaporation plant
Back to the evaporation plant
LigninBlack liquor
Precipitation Filtration Re-suspendingFiltration &
Displacement washing
CO2
H2SO4
Wash liquor
Back to the evaporation plant
Back to the evaporation plant
LigninBlack liquor
Precipitation Filtration Re-suspendingFiltration &
Displacement washing
CO2
H2SO4
Wash liquor
Back to the evaporation plant
Back to the evaporation plant
LigninBlack liquor
Precipitation Filtration Re-suspendingFiltration &
Displacement washing
CO2
H2SO4
Wash 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
O
OH3CO
OHHO
O
OH
OHO
OCH3
O
OH
HO
HO
OCH3
OCH3
O
O
HO
HO
OCH3
HOO
OCH3
OH
OH
HO
OCH3
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
17
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
21
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 BirchEuca. 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 pulping
Leaching 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-membrane
Feed
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
HO
OH
O
O
O
HO
O H
O
O
HO
O H
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
O
O HO H
O
O
H O O
O
O
O 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
OHHO
HO
OH
Acidic or enzyme hydrolysis
Pentoses and hexoses
Lactic acid
Fermentation or alkaline oxidation
Polymerization Polylactide (PLA)H3C
OH
O
OH
H3C
OH
O
OH
H3C
O
O
OH
CH3
O
O CH3
O
O CH3
O
O CH3
O
O CH3
O
O CH3
O
O CH3
OH
O
O
OHHO
HO
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 ResiduesEthanol
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
36
Possible time frame for commercialization
2- 5 years > 5 years
Lignin 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
