This project has received funding from the Bio-Based Industries Joint Undertaking under the European Union’s Horizon 2020 research and innovation programmeunder grant agreement No 745246.

LigniOx process concept for hydrolysis lignin –

Converting lignin into dispersants and carbohydrate-rich residue to

ethanol

Minna Yamamoto1, Anna Kalliola2, Tom Granström1, Tiina Liitiä2

St1 Oy1 and VTT2, Finland

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St1 home market

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Kajaani, Finland, 2016

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LigniOx commercialization – main activities: Oxidation concepts for various technical lignins

Scale-up and construction of mobile LigniOx pilot unit

Integration to biorefineries

Product formulation & prototype for concrete plasticizers

Demonstration of process and product performance at industrial conditions

Techno-economic & environmental assessments, and regulatory issues for market uptake

LigniOx BBI Innovation ActionLignin oxidation technology for versatile lignin dispersants 05/2017 – 04/2021, 6.6 M€

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• Safe and cost-efficient chemicals enabling integration to biorefineries

• Applicable to various lignin side streams

• Adjustment of lignin properties by oxidation conditions for wide range of applications

FI20135986, US9676667, ZL201480054352.3 (granted) WO2015/049424 (pending)

WO2017/077198 A1 (pending)

LigniOx technology for high-performance dispersants

Lignin

NaOH

O2

H2O

pH

controlHigh lignin content, Tinit. < 80 °C

LigniOx solution

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

concrete plasticizer, Ind. Crops Prod, 2015

Lignin conversion to water soluble anionic polyelectrolyte by alkali-O2 oxidation

Dispersing performance of oxidized kraftand soda lignins demonstrated for several inorganic pigments and end-uses

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100

120

140

160

180

200

220

240

260

280

300

Hae

germ

ann

flo

w, m

m

Plasticization in mortar

300 mm, table

1 00 mm

Naphtalene

based Ref

Polycarboxylate

Ether Refs

Lignosulphonate

Refs

Mortar: Sand, CEM I 52,5N, H2O (w/c 0,4)Plasticizer: 0,60% on cem, delayed dosingFlow value: berofe consolidation

• Oxidised KL and OSL have demonstrated high plasticizing performance, oxidized HL also showing good cement dispersing effect compared to commercial plasticizer products

• Better plasticization performance after optimising the lignin quality as well as oxidation

Results 2018 - NWBC, Helsinki

100

120

140

160

180

200

220

240

260

280

300

Hae

germ

ann

flo

w, m

mMortar: Sand, CEM I 52,5N, H2O (w/c 0,5)Plasticizer: 0,30% on cem, pre-dosingFlow value: after consolidation

Naphtalene

based Ref

Results 2019

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LigniOx integration to Cellunolix® bioethanol process

Pretreatment

Enzymatic

Hydrolysis

Solid-Liquid

Separation

Fermentation DistillationBioethanol

Energy Production

Sawdust

Hydrolysis Lignin

Hydrolysate

Lignin

Oxidation

Solid-Liquid

Separation LigniOx productConcentration

Solids for energy

production

Cellulose rich solid residueLigniOx product

• OPTION 1: Cellulose rich LigniOx insolubles to the enzymatic hydrolysis

• OPTION 2: LigniOx product as additive/surfactant to the enzymatic hydrolysis

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Enzymatic hydrolysis - Cellunolix® substratesupplemented with 20% oxidation residue

• 20% of the substrate could be replaced withoxidation residue

• Insolubles treated with higher alkali (HA) released more glucose

• Cost-benefit from higher ethanol yield and reduced use of pH control control chemicals

• Drawbacks: slower filtration stage, sodium loadto process150

200

250

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400

0 20 40 60 80

Fe

rme

nta

ble

su

ga

rs

(g/k

g s

ub

str

ate

DM

)

Hydrolysis time (h)

100% Cellunolix REF

80% REF, theoretical yield

80% REF+20% LigniOx HA

80% REF+20% LigniOx LA

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10,0

12,0

14,0

16,0

18,0

20,0

22,0

24,0

26,0

28,0

0 10 20 30 40 50

Glu

cose (

g/k

g)

Hydrolysis time (h)

0% LigniOx

2,5% LigniOx (HL)

5% LigniOx (HL)

2,5% LigniOx (Kraft)

5% LigniOx (Kraft)

Enzymatic hydrolysis - LigniOx product as additive in Cellunolix® hydrolysis

• LigniOx product based on kraft and hydrolysislignin (HL) improved the glucose yield

• Max 16% yield improvements observed

• Higher than 2.5% dosage impaired the filtration

• Ongoing study

• Comparison with commercial additives

• The effect of LigniOx product on fermentation

16%

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Summary

• LigniOx process converts technical lignins into versatile dispersants

• Application tests show competitive plasticizing performance with conventional products

• Pilot scale oxidation trials ongoing

• Process integration to Cellunolix® bioethanol plant is studied

• Solid residue from LigniOx oxidation could be directed back to ethanol process

• The improved yield is due to the glucose released from solids and the surfactant effect of the LigniOx solution

• Cost reduction through higher ethanol yield and reduced use of pH control chemical

• Slow filtration and sodium load to the bioethanol process are the main drawbacks

• LigniOx product improves the enzymatic hydrolysis yield

• Mechanism of the yield improvement to be revealed

• Comparison to commercial surfactants and lignosulfonates ongoing

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Acknowledgements

• Bio Based Industries Joint Undertaking (BBI JU) under the European Union‘s Horizon 2020 Researchand Innovation program is acknowledged for funding the project LigniOx (Lignin oxidationtechnology for versatile lignin dispersants) under grant agreement No 745246.

Thank you!

minna.yamamoto@st1.fi

www.st1.eu

ILS Poster 45:

Conversion of lignin side-streams from novel biorefineries into

high-performance dispersants by LigniOx technology(VTT Tech. Res. Centre., Finland1, Fortum, Finland2) Anna Kalliola1, Tapio Vehmas1,

Patrik Borenius2, Hanne Wikberg2, Tiina Liitiä1