Lignin Modification Technologies to Phenolic Resins and ...¯a... · Global dispersing agent...
Transcript of Lignin Modification Technologies to Phenolic Resins and ...¯a... · Global dispersing agent...
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
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
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
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”