LigniOx lignins - High performance concrete plasticizers and versatile dispersants - Anna Kalliola, Tapio Vehmas, Tiina Liitiä NWBC 2018, Helsinki
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LigniOx lignins – High performance concrete plasticizers and versatile dispersants Anna Kalliola, Tapio Vehmas, Tiina Liitiä NWBC 2018, Helsinki 1.2.2019 VTT – beyond the obvious
Content 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 1.2.2019 VTT – beyond the obvious
Markets for lignin based dispersants
x
End-uses similar to lignosulphonates and Dispersant market segmentation
synthetic polymers, e.g. polycarboxylates by application (2020)
Large market volumes – dispersants are
Pulp and paper
needed in many industrial processes and 7,9 8,7
9,7 Paints and coatings
products to improve flow properties, coloring 18,1 Construction
ability and stability Oil and gas
21,6
8-10 Mt/a plasticizer admixtures for cement/concrete 19,4 Automotive
5.5 Mt synthetic dispersants market expected by 2020 14,6 Detergents
Others
1.8 Mt dispersants for paints and coatings in 2017
Demand for sustainable and cost-efficient Global Dispersing agents market 2016-2020, Technavio.com
Global Dispersants Market, Research Report 2017, QYR
dispersants with high performance is Chemical & Material Research Center.
Frost&Sulivan (2007), European Coating Dispersant Markets,
increasing M120-39.
1.2.2019 VTT – beyond the obvious
LigniOx technology for high performance
dispersants O2
Lignin
Lignin conversion to water soluble anionic H2O
polyelectrolyte by alkali-O2 oxidation NaOH Ready-to-use
LigniOx solution
Safe and cost-efficient chemicals enabling pH
control
integration to biorefineries High lignin content, ≥ 15 w-%
Tinit. < 80 °C, t ~30 min
Adjustment of lignin properties by oxidation
conditions for wide range of applications
Applicable to various lignin side streams
Variable
Ox
FI20135986, US9676667 (granted) conditions
WO2015/049424 (pending)
WO2017/077198 A1 (pending)
Soda lignin Ref (SL)
Kalliola et al., Alkali-O2 oxidized lignin - A bio-based concrete
1.2.2019
plasticizer, Ind. – beyond
VTTCrops the2015
Prod, obvious
Reaction paths in alkali-O2 oxidation
PhOHs are starting point for Selection of the reaction path is pH
O2 oxidation under alkaline dependent!
conditions
pKa 10-11
Negative charge and molar Condensation
mass of LigniOx lignins can
be adjusted by selecting
oxidation conditions favoring
the preferred reaction path
Degradation
pKa 12-13
Adopted from Ji et al. (2009) & Chang and Gratzl (1980)
Softwood kraft lignin (KL)
Characteristics 100
KL
Anionic charge rising mainly from carboxylic
Precipitation yield, %
80 LigniOx-KL
acids in polymeric LigniOx lignins 60
Water-solubility of kraft and soda lignin can 40
be significantly improved (up to pH 4-6) 20
0
Different OH functionalities (31P NMR) in isolated lignins 2 3 4 5 6 7 8 9 10 11 12
pH
Carboxylic acid Aliphatic OH Phenolic OH Wheat straw soda lignin (SL)
4,0
100 SL
3,0 SL 15% ox
Precipitation yield (%)
80
mmol/g
SL 15% i.ox
2,0 60
SL 25% 1ox
SL 15% 2ox
SL constant pH ox
1,0 40
SL SL constant pH 2ox
20
0,0
SL LigniOx-SL KL LigniOx-KL 0
2 3 4 5 6 7 8
pH (-)
Tamminen et al., Improving the properties of technical lignins for material
1.2.2019 VTT – beyond the obvious
applications, 4th CIAB, 2018, Proceedings.
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
No plasticizer Superplasticizer, 0.2%
300
Super-
plasticizer LigniOx solutions
250
200
Slump (mm)
150
Lignosulfonate
100 Lignosulfonate, 0.4% LigniOx lignin, 0.4%
Soda
Lignin
50
0 Kalliola et al., Alkali-O2 oxidized lignin - A bio-based concrete
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 plasticizer, Ind. Crops Prod, 2015
1.2.2019 VTT – beyond the obvious
Plastizicer dosage (% on cement)
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 PAA Ligni PAA Ligni
Ox Ox
Oxidation conditions must be optimised to
specific end-uses and for each lignin type No notable effect on paste color when using
LigniOx lignin as substitute for commercial PAA
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.
1.2.2019 VTT – beyond the obvious
LigniOx commercialization
LigniOx BBI Innovation Action Main activities
Lignin oxidation technology for versatile Oxidation concepts for various technical lignins
lignin dispersants, 05/2017 – 04/2021, 5.6 M€
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
1.2.2019 VTT – beyond the obvious
Oxidation of industrial lignin raw materials 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 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 1.2.2019 VTT – beyond the obvious
Plasticizing mortar
Oxidised KL and OSL providing better plasticizing performance compared to commercial
synthetic products, oxidized HL also showing rather good performance
Mortar: Sand, CEM I 52,5N, H2O
Improved performance by optimising the conditions Dosing: 0,6% on cem, + defoamer
300
Haegermann flow table, mm
280
260 PCE Refs Naphtalene
240 based Ref
1 00 mm
220
200 300 mm, table
180
160 Lignosulphonate
140 Refs
120
100
References: dosing based on informed d.m.
LigniOx: dosingVTT
1.2.2019 – beyond
based on lignin content
the obviousLigniOx adsorption on cement
Working mechanism to achieve full dispersion? Cement paste: CEM I 52,5N, w/c 0.4
In-house method:
LigniOx-KL reach the max. adsorption already with dosing of 0,5% 1) Separation of water phase by
centrifugation
Working mechanism rather similar to the commercial plasticizers 2) Quantification of the un-adsorbed
amount of plasticizer by UV
0,60%
Adsorbed on cement, %
SNF
0,50%
LS 2
0,40%
LigniOx-KL 2
0,30% LigniOx-KL 5
0,20%
0,10%
0,00%
0,00% 0,25% 0,50% 0,75% 1,00% 1,25%
Dosed on cement, %
Sippola, J. 2018. Adsorption of plasticizers on ordinary
Portland cement surface, Bachelor thesis.
1.2.2019 VTT – beyond the obviousDispersing special carbon black
Special Carbon Black is widely used e.g. in paint Special black (Orion Engineered Carbons): 10% in H2O
Dispersant dose: 2,5…0,25%
pigmenting, conductive coating, water based inks, Commercial dispersant products: Polyacrylic acid
textile printing pastes, UV-filters and aqueous graphite (PAA), Lignosulfonate (LS)
dispersions Mixing: Omni mixer Sorvall, OCI intruments
Viscosity: AR-G2 rheometer, Texas Instruments, @25C
Polyacrylic acid dispersants, lignosulfonates Microscopy imaging and particle analysis
Oxidized lignins tested
LigniOx-KL 3 kDa & 7 kDa
LIgniOx-OSL 7 kDa
LigniOx-HL 20 kDa
1.2.2019 VTT – beyond the obviousDispersing special carbon black
Rheology
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
100,000 100,000
-
2,5 % dosing PAA 0,75% dosing
10,000 LS 10,000
LigniOx-HL, 20 kDa
Viscosity, Pa.s
1,000 LigniOx-KL, 3 kDa 1,000
LigniOx-KL, 7 kDa
LigniOx-OSL, 7 kDa
0,100 0,100
0,010 0,010
0,001 0,001
1 10 100 1000 1 10 100 1000
1.2.2019 Share rate, 1/s
VTT – beyond the obvious Share rate, 1/sDispersing special carbon black
Microscopy, particle size analysis
Better dispersing performance of LigniOx lignins over No dispersant - (pH 3,5) Synthetic dispersant
synthetic commercial reference supported also by
microscopy and particle size analyses
3500
- (pH 3,5)
Number of particles
3000
Sythetic dispersant
2500
LigniOx-KL 3 kDa
2000 Lignosulfonate LigniOx-KL 7 kDa
LigniOx-KL 7 kDa
1500
1000
500
0
5-1000 1000-10000 10000-50000 50000-200000
Particle size, µm2
1.2.2019 VTT – beyond the obviousConclusions 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. 1.2.2019 VTT – beyond the obvious
Acknowledgements
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
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”
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