LigniOx lignins – Highperformance concreteplasticizers and versatiledispersants
Anna Kalliola, Tapio Vehmas, Tiina LiitiäNWBC 2018, Helsinki
7.11.2018 VTT – beyond the obvious
Market potential for lignin based dispersants
LigniOx technology for high performance dispersants
Characteristics & potential end-uses
LigniOx commercialisation
Oxidation of industrial lignin raw materials
Application studies
Mortar plasticizing
Dispersing special carbon black
Conclusions
7.11.2018 VTT – beyond the obvious
Content
7.11.2018 VTT – beyond the obvious
Markets for lignin based dispersants x
8,7
9,7
21,6
14,6
19,4
18,1
7,9
Dispersant market segmentation by application (2020)
Pulp and paper
Paints and coatings
Construction
Oil and gas
Automotive
Detergents
Others
Demand for sustainable and cost-efficient
dispersants with high performance is
increasing
Global Dispersing agents market 2016-2020, Technavio.com
Global Dispersants Market, Research Report 2017, QYR
Chemical & Material Research Center.
Frost&Sulivan (2007), European Coating Dispersant Markets,
M120-39.
End-uses similar to lignosulphonates and
synthetic polymers, e.g. polycarboxylates
Large market volumes – dispersants are
needed in many industrial processes and
products to improve flow properties, coloring
ability and stability
8-10 Mt/a plasticizer admixtures for cement/concrete
5.5 Mt synthetic dispersants market expected by 2020
1.8 Mt dispersants for paints and coatings in 2017
LigniOx technology for high performance dispersants
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
7.11.2018 VTT – beyond the obvious
Lignin conversion to water soluble anionic
polyelectrolyte by alkali-O2 oxidation
Lignin
NaOH
O2
H2O
pH
controlHigh 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
FI20135986, US9676667 (granted)
WO2015/049424 (pending)
WO2017/077198 A1 (pending)
Variable
Ox
conditions
Soda lignin Ref (SL)
Degradation
pKa 12-13
pKa 10-11
Selection of the reaction path is pH dependent!
Condensation
Reaction paths in alkali-O2 oxidation
PhOHs are starting point for
O2 oxidation under alkaline
conditions
Negative charge and molar
mass of LigniOx lignins can
be adjusted by selecting
oxidation conditions favoring
the preferred reaction path
Adopted from Ji et al. (2009) & Chang and Gratzl (1980)
7.11.2018 VTT – beyond the obvious
0
20
40
60
80
100
2 3 4 5 6 7 8 9 10 11 12
Pre
cip
itat
ion
yie
ld, %
pH
KL
LigniOx-KL
0
20
40
60
80
100
2 3 4 5 6 7 8
Pre
cip
itat
ion
yie
ld (
%)
pH (-)
SL
SL 15% ox
SL 15% i.ox
SL 25% 1ox
SL 15% 2ox
SL constant pH ox
SL constant pH 2oxSL
Wheat straw soda lignin (SL)
Softwood kraft lignin (KL)
Characteristics
0,0
1,0
2,0
3,0
4,0
SL LigniOx-SL KL LigniOx-KL
mm
ol/
g
Carboxylic acid Aliphatic OH Phenolic OH
Different OH functionalities (31P NMR) in isolated lignins
Tamminen et al., Improving the properties of technical lignins for material
applications, 4th CIAB, 2018, Proceedings.
Anionic charge rising mainly from carboxylic
acids in polymeric LigniOx lignins
Water-solubility of kraft and soda lignin can
be significantly improved (up to pH 4-6)
7.11.2018 VTT – beyond the obvious
End-use potential as concrete plasticizers
Better plasticization performance in coarse
concrete than with lignosulfonate admixture
Comparable plasticizing at higher dosage to
polycarboxylate based (PCE) superplasticizer
Equal compression strength with commercial
plasticizers 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
Superplasticizer, 0.2%
LigniOx lignin, 0.4%Lignosulfonate, 0.4%
No plasticizer
Kalliola et al., Alkali-O2 oxidized lignin - A bio-based concrete
plasticizer, Ind. Crops Prod, 2015
7.11.2018 VTT – beyond the obvious
End-use potential as versatile dispersants
In addition to cement, LigniOx lignins disperse
CaCO3, TiO2, and color pigments used e.g. in
paints and coatings
Better performance compared to lignosulfonate,
comparable to polyacrylic acid (PAA) based
dispersants at higher dosage
LigniOx lignins disperse acidic gypsum mix
leading to dense gypsum plaster
Performance to retardant gypsum hydration,
allowing longer working time of the material
Kalliola et al., Concrete Plasticizers and Versatile Dispersants
from LigniOx lignins. NWBC 2017, Proceedings.
No notable effect on paste color when using
LigniOx lignin as substitute for commercial PAA
PAA LigniOx
PAA LigniOx
Oxidation conditions must be optimised to specific end-uses and for each lignin type
7.11.2018 VTT – beyond the obvious
LigniOx commercialization
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-economy & LCA
Regulatory issues for market uptake
LigniOx BBI Innovation ActionLignin oxidation technology for versatile
lignin dispersants, 05/2017 – 04/2021, 5.6 M€
Lignin Origin Characteristics Coding
Kraft Softwood Rich in PhOH, low carbohydrate content KL
Organosolv Wheat straw Relatively rich in PhOH OSL
Hydrolysis Softwood Low PhOH, high carbohydrate content HL
7.11.2018 VTT – beyond the obvious
Oxidation of industrial lignin raw materials
Oxidation technology is optimized for the different lignins
Minimization of NaOH consumption
Safe operation with O2
Industrially feasible concepts
Evaluation of LigniOx products in mortar and
concrete in comparison to commercial plasticizers
7.11.2018 VTT – beyond the obvious
Oxidised KL and OSL providing better plasticizing performance compared to commercial
synthetic products, oxidized HL also showing rather good performance
Improved performance by optimising the conditions
Plasticizing mortar
300 mm, table
100 mm
100
120
140
160
180
200
220
240
260
280
300
Hae
ge
rma
nn
flow
tab
le, m
m
Naphtalene
based RefPCE Refs
Lignosulphonate
Refs
References: dosing based on informed d.m.
LigniOx: dosing based on lignin content
Mortar: Sand, CEM I 52,5N, H2O
Dosing: 0,6% on cem, + defoamer
0,00%
0,10%
0,20%
0,30%
0,40%
0,50%
0,60%
0,00% 0,25% 0,50% 0,75% 1,00% 1,25%
Ad
so
rbe
do
n c
em
en
t, %
Dosed on cement, %
SNF
LS 2
LigniOx-KL 2
LigniOx-KL 5
7.11.2018 VTT – beyond the obvious
Working mechanism to achieve full dispersion?
LigniOx-KL reach the max. adsorption already with dosing of 0,5%
Working mechanism rather similar to the commercial plasticizers
LigniOx adsorption on cement
Cement paste: CEM I 52,5N, w/c 0.4
In-house method:
1) Separation of water phase by
centrifugation
2) Quantification of the un-adsorbed
amount of plasticizer by UV
Sippola, J. 2018. Adsorption of plasticizers on ordinary
Portland cement surface, Bachelor thesis.
7.11.2018 VTT – beyond the obvious
Special black (Orion Engineered Carbons): 10% in H2O
Dispersant dose: 2,5…0,25%
Commercial dispersant products: Polyacrylic acid
(PAA), Lignosulfonate (LS)
Mixing: Omni mixer Sorvall, OCI intruments
Viscosity: AR-G2 rheometer, Texas Instruments, @25C
Microscopy imaging and particle analysis
Dispersing special carbon black
Special Carbon Black is widely used e.g. in paint
pigmenting, conductive coating, water based inks,
textile printing pastes, UV-filters and aqueous graphite
dispersions
Polyacrylic acid dispersants, lignosulfonates
Oxidized lignins tested
LigniOx-KL 3 kDa & 7 kDa
LIgniOx-OSL 7 kDa
LigniOx-HL 20 kDa
7.11.2018 VTT – beyond the obvious
Dispersing special carbon blackRheology
0,001
0,010
0,100
1,000
10,000
100,000
1 10 100 1000
Share rate, 1/s
0,75% dosing
0,001
0,010
0,100
1,000
10,000
100,000
1 10 100 1000
Vis
cosi
ty, P
a.s
Share rate, 1/s
2,5 % dosing -
PAA
LS
LigniOx-HL, 20 kDa
LigniOx-KL, 3 kDa
LigniOx-KL, 7 kDa
LigniOx-OSL, 7 kDa
LigniOx lignins show high dispersing performance in special carbon black, 2,5% dosing
No changes in viscosity after 7d storage
LigniOx-KL 7 kDa still showing high performance with decreased dosing
7.11.2018 VTT – beyond the obvious
No dispersant - (pH 3,5) Synthetic dispersant
LigniOx-KL 7 kDaLignosulfonate
Dispersing special carbon blackMicroscopy, particle size analysis
0
500
1000
1500
2000
2500
3000
3500
5-1000 1000-10000 10000-50000 50000-200000
Nu
mb
er o
f p
arti
cles
Particle size, µm2
- (pH 3,5)
Sythetic dispersant
LigniOx-KL 3 kDa
LigniOx-KL 7 kDa
Better dispersing performance of LigniOx lignins over
synthetic commercial reference supported also by
microscopy and particle size analyses
7.11.2018 VTT – beyond the obvious
Conclusions
LigniOx technology converts various industrial lignins to
high-performing plasticizers and versatile dispersant.
In addition to kraft lignin, organosolv and hydrolysis
lignin based LigniOx solutions show high dispersing in
cementitious material.
LigniOx lignins also efficiently disperse special carbon
black in water, opening new application possibilities.
LigniOx is cost-efficient and environmentally friendly
technology that can be integrated into biorefineries.
Biobased industries Joint Undertaking (BBI JU)
LigniOx - Lignin oxidation technology for versatile
lignin dispersants (grant agreement No 745246)
Juha Kaunisto, Jaakko Sippola and Ritva Heinonen
are thanked for performing the oxidations and
application testing
7.11.2018 VTT – beyond the obvious
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”