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”