Lignin Modification Technologies to Phenolic Resins and Versatile

DispersantsTiina Liitiä,* Taina Ohra-aho, Heimo Kanerva, Hanne Wikberg,1 Juha Leppävuori,2

Anna Kalliola, Tapio Vehmas, Tarja Tamminen

VTT Technical Research Centre of Finland Ltd

* Tiina.Liitia@vtt.fi,

Current affiliations: 1Fortum, 2Neste

3

• Potential end-use applications for lignin with

high market volumes already in the short

term are

Phenol formaldehyde (PF) resins

Versatile dispersants

• Cost-efficient, environmentally friendly and

simple modification methods are still needed

to improve the lignin applicability

Towards lignin commercialisation

4

Techno-economically feasible lignin upgrading

technologies to tailor the lignin properties already at

the biorefineries towards the target end-uses

CatLignin: Highly reactive lignin for phenolic

resins

LigniOx: Water soluble polyelectrolytes for

concrete plasticizers and versatile dispersants

e.g. for paints, inks, coatings

Technologies for improved applicability to boost the lignin commercialisation

CatLignin - Highly

reactive lignin for resins

High-volume market with increasing demand

Global demand 6 Mt/a in 2013

7.2 Mt/a volumes expected by 2019

Main drivers for lignin use in phenolic resins

High phenol price fluctuating with oil price

Demand for non-toxic and environmentally

friendly products

Market potential for lignin based phenolic resins

Sources: CEH marketing research 2005 & MarketsandMarkets ”Phenolic Resins (Resols, Novolac and Others) Market for Wood-adhesives, Molding

Compounds, Laminates, Insulation and Other Applications: Global Industry Perspective, Comprehensive Analysis, and Forecast, 2014-2020

Wood adhesives

36.5%

Molding compounds

12.7%

Laminates 11.4%

Insulation 9.8%

Other applications

29.6%

Global phenolic resin demand by end use

Substitution of phenol with lignin in PF resins

Only part of phenol can be replaced with lignin in PF resins

due to lower reactivity

Methoxyl groups limit the reactivity - especially with

hardwood lignins

CatLignin – Highly reactive lignin by thermal treatment

Thermal treatment of black liquor activates lignin

already before separation and produces highly

reactive lignin for phenolic resins

Compatible with existing lignin separation processes

Dewatering properties, yield and purity comparable with

current commercial kraft lignins

VTT Patent Applications: WO2016207493, WO2018115592

Tailor-made properties by adjustment of heattreatment conditions

Activation demonstrated with

different industrial softwood (SW)

and hardwood (HW) black liquors

• Up to six fold increase of reactive

sites for PF resins with HW

• Activation by lignin demethylation

and demethoxylation

• Control by process conditions

• Proven in lab and pilot scale

Theoretical reactive sites based on 31P NMR: 1 x G-OH, 2 x p-H-OH, 3 x (Catechol-OH /2)

0 2 4 6 8

SW-Kraft Ref

SW-Cat1

SW-Cat2

SW-Cat3

HW-Kraft-Ref

HW-Cat1

HW-Cat2

HW-Cat3

Reactive sites, mmol/g

G-OH p-H-OH Catechol-OH

Controlled molar mass

• New phenolic functionalities

formed also by

depolymerisation

• In addition to the reactive

functionalities, also molar

mass can be adjusted

2

3

4

5

6

7

8

2000 2500 3000 3500 4000 4500 5000

Re

ac

tive

fu

nc

tio

na

liti

es

. m

mo

l/g

Molar mass, Mw

Phenolic OH Reactive sites

SW CatLignin

Higher reactivity in PF resin synthesis and curing

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

reference

• Faster curing enabling shorter reaction time or lower temperature – or higher phenol replacement

levels

0

1

2

3

4

5

6

7

8

0 50 100 150

Vis

co

sit

y, P

Reaction time, min

LignoBoost

CatLignin

SW Kraft Ref

SW CatLignin

0

5

10

15

20

25

30

35

40

45

0

0,5

1

1,5

2

2,5

SW-Kraft Ref SW-CatLignin

Ge

lti

me

(50%

ph

en

ol

rep

lac

em

en

t), m

in

Fo

rma

lde

hyd

e c

on

su

mp

tio

n

(100

% lig

nin

), m

mo

l/g

Series1 Series2

50% phenol

substitution, 80°C

Formaldehyde

consumptionGel time

Improved bonding strength in Birch plywood

Nearly 20% increase in birch plywood strength at 50% phenol substitution level with SW CatLignin

compared to commercial reference kraft lignin

Significantly improved wood failure also after boiling test

Birch plywood, resins and tests (EN 314-1) by an industrial partner

Leppävuori et al. International Symposium on Wood, Fibre and Pulping Chemistry, 2017

Conclusions on CatLignin

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

• Up to six times more reactive sites

• Properties can be controlled by conditions

• Applicable to SW and HW kraft lignin

• Faster curing & improved plywood bonding qualityenabling higher replacement levels

• High number of phenolic functionalities beneficialalso for other end-uses, e.g. improvedantioxidative properties shown

LigniOx

for dispersants

Markets for lignin based surface active agents

8-10 Mt/a plasticizer admixtures for cement/concrete

5.5 Mt/a dispersant market expected by 2020

1.8 Mt/a dispersants for paints and coatings in 2017

Large market volumes – dispersants, emulsifiers, detergents, and

foaming agents are needed in many industrial processes and

consumer products

Demand for sustainable and cost-efficient surface active agents

with high performance is increasing

End-use applications similar to lignosulphonates and

synthetic polyelectrolytes, e.g. polycarboxylates

Global dispersing agent markets 2016-2017, Technavio.com

Global dispersants market, Research report 2017, QYR Chemical & Material Research Center.

Frost& Sulivan (2007), European Coating Dispersant Markets, M120-39.

Variable

Ox

conditions

Lignin

NaOH

O2

H2O

pH

control

High lignin content, ≥ 15 w-%

Tinit. < 80 °C, t = 30 min

Ready-to-use

LigniOx solution

Kalliola et al., Alkali-O2 oxidized lignin - A bio-based

concrete plasticizer, Ind. Crops Prod, 2015

Soda lignin Ref (SL)

Lignin conversion to water soluble anionic

polyelectrolyte by alkali-O2 oxidation

Safe and cost-efficient chemicals enabling integration to

biorefineries

Adjustment of lignin properties by oxidation conditions for

wide range of applications

Applicable to various lignin side streams

FI20135986, US9676667 (granted)

WO2015/049424 (pending)

WO2017/077198 A1 (pending)

LigniOx technology for high performance lignindispersants

High performance concrete plasticizers

• Plasticizers (cement dispersants) improve the

workability of fresh concrete at low water contents

leading to strong concrete

• Currently used plasticizers:

Lignosulphonates and sulphonated kraft lignin:

Bio-based, low cost, low performance

Sulphonated melamine and naphthalene

condensates: Low performance, high cost,

synthetic

Polycarboxylate ethers (PCE): High performance

superplasticizers, high cost, synthetic

Demand for cost competitive biobased alternatives with

high performance

Better performance in coarse concrete than with

commercial lignosulfonate admixture

Comparable plasticizing performance at higher

dosage to polycarboxylate based superplasticizer

Equal compression strength with synthetic

superplasticizer in matured concrete

0

50

100

150

200

250

300

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

Slu

mp

(mm

)

Plastizicer dosage (% on cement)

LigniOx solutions

Lignosulfonate

Super-

plasticizer

Soda

Lignin

Kalliola et al., Alkali-O2 oxidized lignin - A bio-based concrete

plasticizer, Ind. Crops Prod, 2015

Superplasticizer, 0.2%

LigniOx lignin, 0.4%Lignosulfonate, 0.4%

No plasticizer

Soda lignin based LigniOx concrete plasticizers

Plasticizing performance of oxidised kraft lignin in mortar

• Oxidised softwood kraft lignin provides better plasticizing performance in mortar also compared to

commercial synthetic products

• Improved performance by optimising the oxidation conditions, meeting also the requirements of

industrial processes

300 mm, table

100 mm

100120140160180200220240260280300

Haegerm

ann f

low

table

, m

m

Mortar (CEM I 52,5N Megasementti by Finnsementti)0.60 % dosage with TBF, no consolidation

SW kraft lignin oxidised in

variable conditions

Lignosulphonate

Refs

PCE Refs

Naphtalene

based Ref

References: dosing based on informed (active) d.m. content

LigniOx: dosing based on lignin content

VTT 2018

• In paint, coating and ink formulations the solid pigments

and fillers (e.g. TiO2, CaCO3, carbon black) are

stabilized by dispersants

Improved flow properties

Easier processing at higher pigment loads

Consistent color, quality and durability

• 1.8 Mt/a dispersants used 2017 for paints and coatings

• Currently mainly synthetic dispersants and surface

active agents (e.g. acrylates) are used

Dispersant for paints, inks and coatings

Increasing demand towards more cost-efficient and environmental-friendly

aqueous dispersants, e.g. in the growing water-borne paints and coatings

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 on

pigment paste color

LigniOx dispersants for pigments and fillers

0

20

40

60

80

100

120

140

160

0 300 600 900 1200

She

ar s

tre

ss (

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

Kalliola et al., Nordic Wood Biorefinery

Conference, 2017

Dispersant for Carbon black• Soda and Kraft LigniOx lignins are potential dispersants also for

carbon black

Equal performance to commercial lignosulfonate dispersant

Better 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

Vis

cosi

ty, P

a (@

25

C)

Share rate, 1/s

Day 0

- (pH 3,5)

- (pH 9,5)

Synthetic dispersant

Lignosulfonate

LigniOx-SL

LigniOx-KL

0,001

0,010

0,100

1,000

10,000

100,000

1000,000

0 1 10 100 1000

Vis

cosi

ty, P

a (@

25

C)

Share rate, 1/s

Day 7

- (pH 3,5)

- (pH 9,5)

Synthetic dispersant

Lignosulfonate

LigniOx-SL

LigniOx-KL

Dispersing Carbon blackMicroscopy, particle size analysis

• Better dispersing performance of Soda and Kraft LigniOx

lignins over synthetic commercial reference supported

also by microscopy and particle size analyses

• Oxidised kraft lignin slightly better than oxidised soda

lignin

No dispersant - (pH 3,5)

Synthetic dispersant LigniOx-SL

Lignosulfonate

LigniOx technology is a simple and cost-efficient way to convert lignin into a high-performance concrete plasticizer

• Higher performance compared to lignosulfonates and most synthetic admixtures

• More sustainable and economic alternative to current synthetic superplasticizers

• Technology can be readily integrated into biorefineries or applied by chemical producers

• Applicable for different technical lignin types

Properties of LigniOx lignins can be adjusted in a controlled manner by the oxidation conditions

LigniOx enables production of ready-to-use dispersants for versatile application areas with high market volumes

• In addition to cement LigniOx lignins can disperse several pigments (carbon black, TiO2, CaCO3, kaolin, and gypsum)

Conclusions on LigniOx

28www.ligniox.eu 02/10/2018

Main activities :

Oxidation concepts for various technical lignins

Scale-up and construction of mobile pilot unit

Integration to biorefineries

Product formulation & prototype for concrete

plasticizers

Demonstration of process and product

performance at industrial conditions

Techno-economic and environmental

assessments

Regulatory issues for market uptake

LigniOx BBI Innovation Action (05/2017 – 04/2021, 5.6 M€)

LigniOx commercialisation

29www.ligniox.eu 02/10/2018

Expected results and impacts

AFTER THE PROJECT

1-3 YEARS AFTER THE PROJECT

Sustainable and cost-competitive lignin based high-performance concrete plasticizer on the market

Versatile high-

performance LigniOx

dispersants for wide

range of applications

Techno-economically

viable & environmentally

friendly lignin upgrading

technology ready for

commercial scale

installations

30VTT 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’s

Horizon 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 increase

sustainability of the whole value chain”