Development of a

Lignocellulose Biorefinery
Concept based on
Organosolv Pretreatment
W.J.J. Huijgen
R. van der Linden
J.H. Reith
H. den Uil

April 2013
ECN-L--13-011
Development of a Lignocellulose
Biorefinery Concept based on
Organosolv Pretreatment
W.J.J. Huijgen, R. van der Linden, J.H. Reith & H. den Uil
2nd Iberoamerican Congress on Biorefineries
Jaen, Spain
11th April 2013

www.ecn.nl
Contents
• ECN

• Biomass pretreatment
– Biorefinery & lignocellulosic biomass
– Cellulose saccharification
– ECN organosolv process

• Experimental results
– Optimisation process conditions
– Lignin isolation, characterisation & application

• Process evaluation
– Mass and energy balances
– Cost evaluation

• Conclusions & current research 2

Energy research Centre of the
Netherlands (ECN)
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– With and for the market, we develop knowledge and
technology that enable a transition to a sustainable
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3
Biorefining /
Biomass Pretreatment
Biorefinery
”The sustainable processing of biomass into a spectrum of marketable
products (food, feed, materials, chemicals) and energy (fuels, power, heat)”

(definition IEA Bioenergy task 42)

Various types of biorefineries depending on type of biomass:

 lignocellulosic biomass.

5
Lignocellulosic Biomass
• Lignocellulosic biomass:
– Hardwood: poplar, willow, ...
– Softwood: spruce, pine, ...
– Herbaceous: miscanthus, wheat straw, …

• Available in form of:

– (Forestry / agricultural) residues.
– Energy crops.

• Advantages compared to other types of biomass:

– Wide range of low cost feedstocks.
– No direct competition with food production.
– High CO2 reduction of derived fuels and products.

6
Lignocellulose Constituents
• Sugar polymers:
– Cellulose, linear polymer of glucose.
– Hemicellulose, branched copolymer of C5
and C6 sugars.

• Lignin:
– Polymer of aromatic compounds.

• Factors influencing composition:

– Plant species.
– Part of plant (bark, stem, …).
– Location of cultivation, ….
Source: University of North Dakota.

7
Saccharification Cellulose
• Hydrolysis of cellulose into glucose: enzymatic or chemocatalytic.
– Benefit enzymatic hydrolysis: selectivity to glucose.

• Direct enzymatic saccharification of lignocellulose not feasible:

– Structural components linked (physically & chemically).
– Cellulose protected against decay by lignin.
– Crystallinity cellulose.

• Pretreatment: overcoming biomass

‘recalcitrance’ by e.g.:
– Removing hemicellulose and lignin to improve
accessibility for hydrolytic enzymes.
– Removing / altering lignin to reduce non-productive
cellulase binding.
Source: USDA Agricultural Research Service.
– Reducing crystallinity of cellulose.
8
Pre-treatment
• Several physical-chemical pre-treatment routes under development.

• Main pretreatment routes (pilot-scale)1:

– (Dilute) acid pre-treatment
– Steam explosion

• Routes effective for cellulose, however:

– Lignin ends up in residue (with unconverted sugars, process chemicals, ash, etc).
– Residue generally only suitable for CHP.

• Alternative:
– Separation of lignin prior to enzymatic hydrolysis.
– Preserving chemical structure of lignin & enabling higher value applications.
 Organosolv.
1 Harmsen et al. (2010), Literature review of physical and chemical pretreatment processes for lignocellulosic biomass, report ECN-E--10-013. 9
ECN Organosolv Process
Lignocellulose Biorefinery
• Why organosolv?
– Fractionation of all major constituents in a sufficient quality for valorisation.
– Including extraction of high-quality lignin for production of chemicals.

Primary biorefinery Paper & Secondary biorefinery

cellulosic
materials Ethanol
Butanol
Fermentation
Lactic acid
...
(Enzymatic)
hydrolysis
Cellulose
Furfural
Lignocellulosic Chemical
biomass HMF
conversion
Fractionation Hemicellulose …
(organosolv)

Phenolics
Lignin Thermochemical
Fuel additives
depolymerisaton
...

Electricity
Filler, CHP
adhesives, Heat
...

11
 Organosolv Process
Solvent recycling

Lignocellulose
Lignin Solvent Hemicellulose
Solvent Organosolv
separation separation (derivatives)
Water (+ catalyst)

Cellulose (S) Lignin (S)

(to enzymatic hydrolysis)

• Solvents: aqueous ethanol, acetone, …

• Catalyst: H2SO4, ...
• Typical process conditions: 160-200 ºC, 30-120 min.

General information: Reith et al. (2011) A step towards the development of a Biorefinery, NPT procestechnologie, 18(1), 26-28

12
Experimental Results
 Experimental Set-up Organosolv
Milling Analysis
composition
Washing Enzymatic hydrolysis
Lignocellulose Solid residue
Analysis sugars
Solvent / H2O Filtration (monomeric +
oligomeric)
Filtrate
Analysis other
Optional: compounds
catalyst
Volume: 0.5 / 2 / 20 ltr Lignin separation &
Stirring analysis
Temperature ↑
T reactor
T jacket
p

p
T

0 t
t
14
Lignocellulosic Feedstocks
• Effectiveness organosolv dependent on type of lignocellulosic biomass:
– Large variety of feedstocks tested.
– Optimum pretreatment conditions feedstock dependent.
– Organosolv less suitable for softwoods and dense hardwoods.
– Best results obtained for specific annual plants (straw) and hardwoods (willow, birch).

 ECN: primary focus on agricultural residues, like wheat straw.

Feedstock Pretreated Feedstock Pretreated

Straw

Willow
15
Example Comparison Feedstocks

• Ease of pulping:
– Birch >> wheat straw ~ poplar > rice straw.

• Differences between feedstocks: 70

– Acid neutralisation capacity. 60

 Different dose of acid needed. 50

Pulp yield (%)

– But also, structural differences. 40

30 wheat straw
(mol H +/ kg dw) pH 4 rice straw
20
Rice straw 0.40 poplar
10 birch
Poplar 0.08
0
Wheat straw 0.31 1 2 3 4 5 6
Birch 0.04 pH (-)

Huijgen et al. (2012) Progress in organosolv fractionation…, 8th Int. Conf. on Renewable Resources & Biorefineries, Toulouse, France. 16
Process Parameters

Wheat straw
• Parametric optimisation studies:
– Feedstocks: wheat straw & willow.
– Solvents: ethanol & acetone.
– Studied variables:
– Particle size
– Pretreatment severity:
– Temperature
– Reaction time

After organosolv
– Acid catalysts such as H2SO4
– Solvent mixture : solid ratio (L/S)
– Solvent-water ratio
– Stirring rate

17
Process-Product Scheme
Input Output Parameters

Pulp

Wheat straw Pulp yield:

Cellulose
T↓, [H2SO4]↓, t↓, EtOH↑
Cellulose Hemi- Glucan content:
cellulose T↑, [H2SO4]↑, t↑, EtOH↓
Hemi-
cellulose Enzymatic digestibility:
Lignin
T↑, [H2SO4]↑, t↑, EtOH↓
Lignin
Xyloses & Yield:
derivatives T↓, [H2SO4]↓, t↓, EtOH↓

Yield:
Lignin
T↑, [H2SO4]↑, t↑, EtOH↑

Wildschut et al. (2013) Ethanol-based organosolv fractionation of wheat straw…, Bioresource Technology (in press).
18
 Optimisation
• Optimisation towards different products possible.
• Example from published results: enzymatic digestibility.

Enzymatic
Feedstock T (°C) Solvent (% w/w) Catalyst
digestibility (%)
Wheat straw 1 205 50% acetone Auto 80
Wheat straw 4 210 50% EtOH Auto 86
Olive tree 2 210 43% EtOH Auto 90
Wheat straw 3 190 60% EtOH HCl (20 mM) 99
Wheat straw 4 190 60% EtOH H2SO4 (30 mM) 89
Willow 3 190 60% EtOH H2SO4 (10 mM) 87
Wheat straw 5 175 & 220 H2O & 60% EtOH Auto 93

1 Huijgen et al. (2010) Pretreatment and fractionation of wheat straw..., Ind Eng Chem Res, 49(20), 10132-10140.
2 Diaz et al. (2011) Organosolv pretreatment of olive tree biomass for fermentable sugars, Holzforschung, 65(2), 177-183.
3 Huijgen et al. (2011) Catalytic organosolv fractionation of willow wood and wheat straw..., J Chem Technol Biotechnol, 86(11), 1428-1438.
4 Wildschut et al. (2013) Ethanol-based organosolv fractionation of wheat straw…, Bioresource Technology (in press).
5 Huijgen et al. (2012) Fractionation of wheat straw by prehydrolysis, organosolv delignification and… , Bioresource Technology, 114, 389-398.
19
Reduction Enzyme Dose
• Enzyme use major cost factor. 100
20
– Analytical lab protocol: high dose of 15
20 FPU/gr substrate. 80 10
– Reduction required. 5

Glucose yield (%)

60

• Example wheat straw pulp. 40

– Organosolv: 190°C, 60min, 60:40%

20
w/w EtOH:H2O, 30mM H2SO4.
– 25% reduction enzyme use possible 0
with similar glucose yield. 0 24 48 72
time (hrs)

• Reduction to 10 FPU/gr demonstrated with complete enzymatic hydrolysis.

20
Increase Consistency
• Consistency:
– Analytical lab protocol: 3% w/v.
– Industrial: 15-20% w/v required.

Conversion glucan to glucose (%)

100

• Test: 80

– Two EtOH organosolv pulps from wheat straw. 60

– Enzyme: Accelerase TRIO (10FPU/g pulp). Pulp A - 15% w/v
40 Pulp B - 15% w/v
Pulp A - 3% w/v

• Results: 20 Pulp B - 3% w/v

– No significant influence product inhibition. 0

0 24 48 72
– Potential to lower enzyme doses larger at low time (hrs)
consistency.
– Glucose concentrations from ~20 to ~110 g/L.

21
Lignin Isolation & Characterisation
• Lignin isolation:
– Insoluble in H2O, soluble in ethanol & acetone.
– Precipitation lignin from organosolv liquor.
– Lignin isolation efficiency >90%.

• Lignin characteristics:
– Light brown to black (compacted) powder.
– High purity (>>90 wt%).
– Main contaminant oligomeric xylose (hemicellulose).
– Lignin sulphur and ash free (max 0.1 wt% S).
– Molecular weight (relative to other types of lignins):
– Low average (2000-3500 g/mol).
– Narrow distribution.

 Organosolv lignin promising properties for valorisation

(next presentation Paul de Wild).

22
 Phenol Formaldehyde Resins
• Successful replacement of phenol by lignin in phenol-formaldehyde resins.
• Substitution up to 20% w/w (limited by amount of lignin available).
• Additional tests with higher substitution degrees this year.

Testing according to the EN314.1 standard

Sample PF std PFL10 PFL20

Immersion in water of 20°C for 24h

Shear strength, N/mm2 1.04 1.16 1.33
4h boiling - 16h drying at 60°C- 4h in boiling water -
1h in cool water
Shear strength, N/mm2 0.82 0.96 1.07
Formaldehyde emissions
(test method: JIS A 1460), 0.075 0.059 0.088
mg/L

Papadopoulou et al. (2012) Thermosetting adhesives with renewable raw materials for wood-based products, UBIOCHEM-III, Thessaloniki, Greece. 23
Process Evaluation

24
Organosolv Process
• Process design in ASPEN:
– Feedstock: wheat straw.
– Products: cellulose pulp, lignin, and furfural.
– Fractionation input based on experimental results.

Van der Linden et al. (2012) Ethanol-based Organosolv Biorefineries… , Nordic Wood Biorefinery Conference, Helsinki (FIN). 25
Mass & Energy Balances
• Straw to products: 67% wt.

• Heat integration essential: Products (kg dw/kg dw straw)

– Decrease heat duty by 81% after Pinch analysis.
Cellulose (pulp) 0.46
Furfural 0.04
• Energy consumption: ~20% of LHV of straw
Lignin 0.18
(excl. electricity).
Others (incl
1.31
waste water)
• Options for reduction energy consumption: Sum 1.99
– Anaerobic digestion aqueous waste stream.
– Combustion of residues e.g. from crusher.

26
Economic Evaluation - I
• Scale: Price (€/ton) M€/yr
– 150 kton/yr straw (dw) Cellulose 350 24.0
– Straw from a 50 km radius Furfural 625 3.8
– 8000 hrs of operation / yr Lignin 750 19.9
– Price index: 2011 Income 47.7
– Location: EU
– General surcharge factors used. Straw 70 10.5
Ethanol 750 0.4
Utilities 7.5
• Recycling solvent essential for
Maintenance 6.2
economy.
Other 11.3
OPEX 35.9

Total fixed capital (M€) 82.0

Pay-back time (yr) 7.0
27
Economic Evaluation - II
• Largest uncertainty in cost evaluation of investment (organosolv reactor).
• Economy strongly dependent on feedstock price and product values.

Cellulose (€/ton) Payback time (yr)

Low 300 9.9
Base case 350 7.0
High 400 5.4

• Comparison steam explosion vs organosolv:

– Additional revenues lignin > extra costs organosolv.
– Lower pay-back time biorefinery due to valorisation all three major fractions.

28
Conclusions
• Experimental:
– Process optimisation performed for hardwoods and straws.
– Enzymatic hydrolysis cellulose improved substantially (up to ~90%).
– Successful isolation of lignin with high purity (>>90%).

• Process evaluation:
– Recycling organic solvent crucial (conceptually and energetically feasible).
– Product and feedstock prices crucial for economy of organosolv biorefinery.

29
Ongoing and Future Work
• Lignin application tests with industrial partners.
• Construction bench-scale continuous organosolv reactor.
• Partnering for further technology development & commercialisation.
2007 2010 2013

0.1 L

20 L

Continuous biomass 30
0.5 & 2 L pretreatment reactor
Thank you for your attention

More information:

huijgen@ecn.nl

This work has been funded by the Dutch ministry of Economic Affairs and the European
Commission in the context of the various national and European projects.

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F +31 224 56 44 80 www.ecn.nl

31
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