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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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
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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
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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!
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