Naturalresources

7.9.2018

Tarja TamminenTainise V. LourençonAnna KalliolaTiina Liitiä

POTENTIAL OF LATINAMERICA IN THEPRODUCTION OF

LIGNIN

Lignocellulosicfeedstock

Pulp for paperand board

Cellulosefraction for bio-

ethanol

Other bio-basedproducts

Lignin side-stream Technical lignin

Isolation

Lignocellulosic bio-refinery

Lignin is the major by-product of chemical pulpingand emerging biorefineries

~55 Mt/a kraft lignin* produced by chemicalpulping, of which ~150 kt/a recoveredcurrently**~1.8Mt/a lignosulphonates recovered**Substantial amount of lignin estimated tooriginate from the 2nd generation bioethanolproduction

Most of the lignin is burned for energy, and onlysmall fraction is utilised in high-value products

* Gellerstedt et al (2013)** Calculated based on several public sources

Lignin by-products from lignocellulosicbiorefinery

Kraft lignin recovery today

Stora Enso (2015)50,000 tons

Suzano (2018)20,000 tons

MeadWestvaco (1942)30,000 - 60,000 tons

Domtar (2013)27,000 tons

West Fraser (2017)10,000 tons

Courtesy of Klaus Niemelä, VTT

ChinaUnknown

132 million t/a chemical pulpproduced globally 55 million t/alignin extracted 11 million t/acould be recovered

Emerging lignin market

Emergingprocesses willincrease lignin

availability in themarket

High valueor

high volume?

Only fractionof lignin

production isutilized in high

valueapplications

Higher Value from Lignin

LIGNIN• Kraft• Soda• Organosolv• Hydrolysis residue

Phenolic resins forwood products

Rubber andplastic products

Carbonised materials

Thermoplastic materials

• CatLignin technology forhighly reactive lignin

• Solvent fractionation• Biotechnical activation

Surface active agents• LigniOx technology for versatile dispersants• Concrete and gypsum plasticizers• Dispersant for inorganic fillers/pigments

Food & feed• Structure modifier• Functional additive• Edible films

• Reinforcement fillers• Antioxidants• Fire retardants

• Thermoplastic matrix polymer for composites• Tackifier for hot melt adhesives• Coatings

• Carbon black by HTC• Activated carbon

Fuels &chemicals• HTL• Pyrolysis• Solvolysis

Schematicrepresentationof nativesoftwood ligninstructure

(Brunow et al., 1998)

Building blocks of lignin

p-Coumarylalcohol

Coniferylalcohol

Sinapylalcohol

Phenolic lignin is valuable renewable rawmaterial for the chemicals, fuels andmaterials to replace the present oil basedproducts

Lignin accounts for 15–30% of thebiomass

Wood structure(Copyright University of Canterbury, 1996,

www.nzwood.co.nz)

Lignin in plants

• Sulphonated & water soluble• High molar mass• Low content of phenolic units• Low thermal stability

Lignosulphonates

• Water insoluble• Low to medium molar mass• High content of phenolic units• High lignin purity• Soda & organosolv lignins sulphur-free unlike kraft lignin

Spent liquor lignins(kraft, soda, organosolv)

• Polysaccharide and protein impurities• Limited solubility• Rather native non-depolymerised structure• Low phenol content, high aliphatic hydroxyl content• Sulphur-free

Hydrolysis lignins Bio

mat

eria

ls,c

hem

ical

san

dfu

els

Key features of industrially produced lignins

• Reactivity: High phenol & low methoxyl content• Alkali solubilityPhenol

formaldehyde(PF) resins

Phenolformaldehyde

(PF) resins

• Reactivity: Aliphatic hydroxyl functionalities• Dispersion stability / solubility in polyol formulation• Viscosity control: Low molar mass

Polyurethanes(PU)

Polyurethanes(PU)

• Thermally moldable: Low softening temperature• Strength: High molar mass, linearity (native structure)• Thermal stability, non-odorous

Thermoplasticcomposites

Thermoplasticcomposites

All afterplastization (and

purification ofhydrolysis lignin)

Spent liquor lignins& purified

hydrolysis lignin

Spent liquorlignins of SW and

annual plants> >

Main product requirements and lignin applicabilitybased on inherent structural features 1/2

• Water solubility: hydrophilic functionalities (-SO3H, -COOH)

• Hydrophilic/hydrophobic balance and molar massapplication dependent

Surface activeagents

Surface activeagents

• Less sensitive for purity or chemical structure in mostcases

• High quality demands for carbon fibers: high purity,adjustable thermal properties, spinnability, high molarmass, linearity

Carbonisedmaterials

Carbonisedmaterials

• Native structure with easily degradable aryl etherlinkages

• Sulphur free for some catalytic conversion

Fuels andchemicals

Fuels andchemicals

Lignosulphonates assuch

& All other afterfunctionalisation

For mostapplications all

lignins, alsohydrolysis lignin as

such

Hydrolysis lignin(after purification)

probably best

Main product requirements and lignin applicabilitybased on inherent structural features 2/2

Higher Value from Lignin

LIGNIN• Kraft• Soda• Organosolv• Hydrolysis residue

Phenolic resins forwood products

Rubber andplastic products

Carbonised materials

Thermoplastic materials

• CatLignin technology forhighly reactive lignin

• Solvent fractionation• Biotechnical activation

Surface active agents• LigniOx technology for versatile dispersants• Concrete and gypsum plasticizers• Dispersant for inorganic fillers/pigments

Food & feed• Structure modifier• Functional additive• Edible films

• Reinforcement fillers• Antioxidants• Fire retardants

• Thermoplastic matrix polymer for composites• Tackifier for hot melt adhesives• Coatings

• Carbon black by HTC• Activated carbon

Fuels &chemicals• HTL• Pyrolysis• Solvolysis

Lignin for phenol formaldehyde (PF) resins

High-volume market with increasing demandGlobal demand 6 Mt/a in 2013

7.2 Mt/a volumes expected by 2019

Main drivers for lignin use in phenolic resinsHigh phenol price fluctuating with oil price

Demand for non-toxic and environmentallyfriendly products

Market potential for lignin based phenolic resins

Sources: CEH marketing research 2005 & MarketsandMarkets ”Phenolic Resins (Resols, Novolac and Others) Market for Wood-adhesives, MoldingCompounds, Laminates, Insulation and Other Applications: Global Industry Perspective, Comprehensive Analysis, and Forecast, 2014-2020

Woodadhesives

36.5%

Moldingcompounds

12.7%Laminates

11.4%

Insulation9.8%

Otherapplications …

Global phenolic resin demandby end use

Low reactivity of lignin limits the use inPF resin applications

Only 20 - 40% phenol can bereplaced with lignin in PFresinsMethoxyl groups limit thereactivity, especially forhardwood lignin. However, inpractice it has been shownthat even HW lignin can beconsidered as a potential rawmaterial for PF resins.

Simultaneous activation and precipitation of lignin fromblack liquor results in highly reactive lignin with up to fivetimes more reactive sites for PF resins than currentcommercial lignins*

• Reactive CatLignin (Catechol enriched Lignin) enables high phenolreplacement levels - even with HW lignins

• Yield and purity comparable with present lignin separation technologies• Integration to existing lignin separation processes possible

CatLignin - new reactive lignin for highphenol replacement

VTT Patent Applications: WO2016207493, WO2018115592

Higher reactivity in PF resin synthesis and curing

• Three times higher formaldehyde consumption with SW CatLignin compared to the commercialreference

• Faster curing enabling shorter reaction time or lower temperature

0

1

2

3

4

5

6

7

8

0 50 100 150

Visc

osity

,PReaction time, min

LignoBoost

CatLignin

SW Kraft Ref

SW CatLignin

051015202530354045

0

0,5

1

1,5

2

2,5

SW-Kraft Ref SW-CatLignin

Gelt

ime

(50%

phen

olre

plac

emen

t),

min

Form

alde

hyde

cons

umpt

ion

(100

%lig

nin)

,mm

ol/g

Series1 Series2

50% phenolsubstitution, 80°C

Formaldehydeconsumption

Gel time

Thermal treatment of black liquor demethylatesand demethoxylates kraft lignin resulting in highlyreactive lignin for PF resins

• Up to six times more reactive sites for PF resins• Properties can be controlled by conditions• Applicable to SW and HW kraft lignin• Faster curing & improved plywood bonding

quality enabling higher replacement levels• High number of phenolic functionalities beneficial

also for other end-uses, e.g. improvedantioxidative properties shown

Summary of the potential of theCatLignin technology

Lignin as surface active agent

Markets for lignin based surface active agents

Up to 15 Mt/a plasticizer admixtures for cement/concrete(worldwide)400 kt/a dispersants for paints (worldwide)100 kt/a dispersants for coatings (Europe)

Large market volumes – dispersants, emulsifiers, detergents,and foaming agents are needed in many industrial processesand consumer products

Demand for sustainable and cost-efficient surfaceactive agents with high performance is increasing

End-use applications similar to lignosulphonates and syntheticpolyelectrolytes, e.g. polycarboxylates

High performance concrete plasticizers

• Plasticizers (cement dispersants) improve the workabilityof fresh concrete at low water contents leading to strongconcrete

• Currently used plasticizers:Lignosulphonates and sulphonated kraft lignin:Bio-based, low cost, low performanceSulphonated melamine and naphthalenecondensates: Low performance, high cost,syntheticPolycarboxylate ethers (PCE): High performancesuperplasticizers, high cost, synthetic

Demand for cost competitive biobasedalternatives with high performance

VariableOx

conditions

Lignin

NaOH

O2

H2O

pH control

High lignin content, 15 w-%Tinit. < 80 °C, t = 30 min

Ready-to-useLigniOx solution

Kalliola et al., Alkali-O2 oxidized lignin - A bio-basedconcrete plasticizer, Ind. Crops Prod, 2015

Soda lignin Ref (SL)

Lignin conversion to water soluble anionicpolyelectrolyte by alkali-O2 oxidation

Safe and cost-efficient chemicals enabling integration tobiorefineriesAdjustment of lignin properties by oxidation conditionsfor wide range of applicationsApplicable to various lignin side streams

FI20135986, US9676667 (granted)WO2015/049424 (pending)

WO2017/077198 A1 (pending)

LigniOx technology for high performance lignindispersants

LigniOx lignins (kraft, soda) perform as dispersants for pigments, fillers and other inorganic particles

• Better dispersants for TiO2, CaCO3 and kaolin than lignosulfonate ref or unmodified lignins

• Comparable to polyacrylic acid (PAA) based dispersant at higher dosage without notable effect onpigment paste color

LigniOx dispersants for pigments and fillers

0

20

40

60

80

100

120

140

160

0 300 600 900 1200

Shea

rstr

ess(

Pa)

Shear rate (1/s)

TiO2

0 300 600 900 1200

Shear rate (1/s)

CaCO3

SL, 0.06%

LigniOx-SL 0.06%

PAA 0.05% LigniOx-KL 1.0%

PAA 0.5%

Lignosulfonate & SL, 1.0%

KL, 1.0%

LigniOx-SL 0.05%

CaCO3TiO2

TiO2 Color pigment

PAA LigniOx

PAA LigniOx

Dispersant for Carbon blackSoda and Kraft LigniOx lignins are potential dispersants alsofor carbon black

Equal performance to commercial lignosulfonatedispersantBetter than commercial polyacrylic acid based product

No change in stability after storing (7 days, 1½ m)

Carbon Black (Special black): 10%Dispersant dose: 15%Efficient mixing procedure: Sorvall

0,001

0,010

0,100

1,000

10,000

100,000

1000,000

0 1 10 100 1000

Visc

osity

,Pa

(@25

C)

Share rate, 1/s

- (pH 3,5)

- (pH 9,5)

Synthetic dispersant

Lignosulfonate

LigniOx-SL

LigniOx-KL

LigniOx technology is a simple and cost-efficient way to convert lignin into a high-performance concrete plasticizerHigher performance compared to lignosulfonates and most synthetic admixturesMore sustainable and economic alternative to current synthetic superplasticizersTechnology can be readily integrated into biorefineries or applied by chemicalproducersApplicable for different technical lignin typesProperties of LigniOx lignins can be adjusted in a controlled manner by theoxidation conditionsLigniOx enables production of ready-to-use dispersants for versatile applicationareas with high market volumesIn addition to cement LigniOx lignins can disperse several pigments: carbon black,TiO2, CaCO3, kaolin, and gypsum

Summary of the potential of theLigniOx technology

Lignin for composites and coatings

Why thermoplastic lignin ?

Thermoplastic properties are needed inseveral end-products, such as

Plastic compositesCoatingsCarbon fibersHot melt adhesivesAsphalt

Lignin can provide cost savings withadditional functionality, e.g.

• Antioxidativity• UV-protection• Fire retardance

Improving lignin properties by aqueoussolvent fractionationHomogeneous fractions with variable propertiesusing simple, green and inexpensive solvents fordiffetent target products

Solventfractionation

Solventfractionation

Lignin Phenolic OH Carb SulphurxCOOH

INS PREC SOL

References:Jääskeläinen, A.-S., Liitiä, T., Mikkelson, A., Tamminen, T., Industrial Crops and Products 103(2017), 51-58.Jääskeläinen, A.-S., Willberg-Keyriläinen, P., Liitiä, T., Tamminen, T., Nordic Pulp and Paper Research Journal, accepted.Dominguez-Robles, J., Tamminen, T., Liitiä, T., Peresin, M.S., Rodriguez, A., Jääskeläinen, A.-S., accepted

Antioxidative properties against UV light(PP composites)

No effect on initial mechanical propertiesBetter performance compared to commercial AOsNo need for secondary AOs with ligninThe performance of all studied lignins equally good.

05001000150020002500

05

101520253035

Mod

ulus

(MPa

)and

Stra

inat

brea

k(%

)

Tens

ilest

reng

th(M

Pa) Tensile strength Modulus

• AO-free PP with 0.9 w-% lignin• Commercial AO references:

0.9w% Irganox 1010 (Prim. AO)0 or 0.5% w-% Irgafos 168 (Sec. AO)

UV ageing: Cycles of UV-A irradiation at 50°C for 22 hand 2 h condensation at 38°C. for 500h (ASTM G154)

Lignin samples without Sec.AO

01020304050

OIT

,min

Thermal stability (PP composites)Better performance than with commercial AOs against thermal oxidationImproved properties with high amount of free phenolic hydroxyl groups

• Catechol rich CatLignin better than conventional kraft lignin

• Fractionation improved antioxidative properties of kraft lignin

• SOL & PREC comparable with CatLignin

Co-use of secondary AO beneficial with best performing ligninsOxidative induction time (OIT)

Lignin can be converted tothermoplastic and moldable

Externally with additives: simple,cost efficient, but migration ofplasticizers possible

Internally by chemicalmodification: no migration,although more expensive

Lignin thermoplasticization

Hot melt adhesives (HMA)Increasing demand for safe solvent free adhesives due tostringent environmental regulations

Thermoplastic adhesives applied as liquid when hot, glueseam formed by solidification when cooled downNo release of volatile compoundsPackaging industry is the biggest user of HMAs,Main constituents of HMAs• Cohesive polymer providing the strength properties• Tackifier providing adhesion and compatibility• Softeners to adjust the melt flow properties

Resinous tackifiers :• Low Mw• Tg > RT• Interactions between

polymer and substrate e.g.via hydrogen bonds

Novel sustainable hot melt adhesive formulationse.g. for packages using wood based components

Lignin tackifierCellulose based cohesive polymer

Biobased hot melt adhesives

Best formulations provided comparable or higherbond strength compared to commercial HMAreference

All studied lignins potential tackifiers for HMAs andPSAsProperties can be adjusted by lignin type,formulation, and chemical modificationTOFA-esterification of lignin enables formulationswithout any softenersUnmodified lignins to be used with softeners

Patent application: FI20175001 Biobased hot-melt adhesive including lignin as component

HMA Ref: Sitomelt 745/5

Ref

Lignin

050

100150200250300350400

Max

load

/wei

ght(

N/g

)

Debonding strength

Adjustment of lignin thermoplasticity bychemical modification

Materials Substituentchain length

DS%

Tg°C

SW Kraft (KL) - 0 145-155Acetic-KL C2 100 110-130Octanoic-KL * C8 20 ~ 125

30 ~ 10040 ~ 7560 ~ 60

100 ~ 45TOFA-L ** C18 mix 90 10-20

100 Broad, starts < 0

Acetylated lignin

Tofa-esterified lignin

Lignin thermoplasticity can be increased, e.g. by esterificationAdjustment of Tg possible using variable substituent chain length

and degree of substitution (DS)

Tall oil fatty acid (TOFA), mainlycomposed of unsaturated fatty acids• C18:1 oleic acid 24.9%• C18:2 linoleic acid 52.4%• C18:3 linolenic acid 9.0%

* Koivu et al. 13th EWLP, 2014** VTT Patent: Functionalized lignin and method of producing the same. FI2012/050965

Lignin based barrier material for packaging applications

TOFA-Lignin coating provides improved barrier propertiesin fiber based packages with good film formation

Reduced water vapour transmission rate – Comparable to PLAReduced oxygen transmission rate (OTR)Medium aroma barrier propertiesImproved grease barrier

Sample WVTR g/m2/24hNormalized to a coat weight of 10 g/m2

Paperboard 480 (+/- 28)

TOFA-HW lignin 73 (+/- 11)

TOFA-SW lignin 66 (+/- 4)

PLA 68-84

Water Vapour Transmission Rate (WVTR)

VTT Patent: FI2012/050965Hult et al. Industrial Crops and Products 50 (2013) 694– 700, Holzforschung 67:8 (2013)899 – 905.

Paperboard as such and paperboard coatedwith thermoplastic TOFA-lignin

Measured at 25 °C at 50 % RH using a desiccant in the cup (ASTM E95)

Lignin can be plasticized externally or internally by chemical modificationwhich offers several application possibilities

Chemical modification offers versatile tool for adjustment of thermal propertiesof lignin

• No need of additional plasticizers and risk of migration

• TOFA, a side-stream of pulping industry, is potential biobased raw material forlignin plasticization

The intrinsic properties of lignin can provide additional benefits in thermoplasticmaterials

• Antioxidativity, UV protection, fire resistance

Summary of the potential of the lignin forthermoplastic applications

35VTT 2018

Finnish Funding Agency for Innovation (Tekes)• TUTL CatLignin – Reactive lignin for phenolic resins• ProLignin under the Wood Wisdom EraNet 2 program

Biobased industries Joint Undertaking (BBI JU)• LigniOx - Lignin oxidation technology for versatile lignin

dispersants (grant agreement No 745246)

Acknowledgements

This project has received funding from the Bio-Based Industries Joint Undertaking under the European Union’sHorizon 2020 research and innovation programme under grant agreement n° 745246. Programme: H2020 BBI-2016-D03: Valorization of lignin and other side-streams to increase efficiency of biorefineries and increasesustainability of the whole value chain”