Seaweed Biorefinery in the Netherlands - TNO · Seaweed Biorefinery in the Netherlands J.W. van Hal...
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Seaweed Biorefinery in the
Netherlands
J.W. van Hal
October 2012
ECN-L--12-051
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www.ecn.nl
Seaweed Biorefinery in the
Netherlands
J.W. (Jaap) van Hal
Neeltje Jans
September 19, 2012
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2012-09-19
Pre-
cultivation
on Land
Planting at
SeaCultivation Harvesting Transport
Primary
Bio-
Refinery
Secondary
Bio-refinery
Products
and Energy
SBIR EOS LT
2 Seagriculture ECN
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The team:
Willem de Visser
Julia Wald
Willem Brandenburg
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© ECOFYS | |
Ecofys module
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5 2012-09-19
Aquatic Biomass
Seagriculture ECN
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Mission: ECN develops market driven technology and know-how to enable a transition to sustainable energy
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Locations
Petten (head office)
Amsterdam
Eindhoven
Beijing
Wieringerwerf
Brussels
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R&D fields
Energy
Efficiency &
CCS
Policy
Studies Energy
Engineering
Environment
Wind Energy
Solar Energy
Biomass
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www.ecn.nl
Biomass & Energy Efficiency
Neeltje Jans
2012
Your energy. Our passion.
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What we do
• Problem solving
Using our knowledge, technology, and facilities to solve our clients’ issues
• Technology development
Developing technology into prototypes and industrial application
• Studies & Policy support
Creating insights in energy technology and policy
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Biomass – a diverse energy source
waste wood (agricultural) residues energy corps aquatic biomass
Biomass = all organic material of non-fossil origin
meant for energy or chemicals/materials
production
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Biomass Pre-Treatment
Licensees, clients
• Torrefaction technology – Pilot plant under construction
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Biorefinery and processing
• Organosolv: fractionation technology – Conversion of lignocellulosic biomass into cellulose and pure
lignin
– Cellulose conversion to bio-ethanol
– Lignin: base materials for bio-chemicals
• Seaweed (macroalgae) as a bio-feedstock – Conversions to chemical intermediates
– Source of protein: alleviates land-use issues
• Synthesis processes – Catalytic conversion
– Separation processes
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Parts of seaweed plant
Holdfast
Stipe
Blade
Seagriculture ECN
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Does not compete with food
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No land use issues
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Bio-Offshore
• Seaweed cultivation area 5.000
km2 (<10 % of the NL area of the
North Sea @ 57.000 km2)
• Integration with off-shore wind
parks & (other) aquaculture
operations
• Energy potential up to 350 PJth (25
Mton dry biomass per year)
• ECN-C—05-008
Seagriculture ECN
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Potential Applications
• Furanics (carbohydrate conversion)
• Polyols for poly-urethanes (direct application)
• Butanol (fermentation)
• Bleach activators (derivatization)
• Phosphate recycling/fertilizers (Ash utilization)
• Fodder (protein fraction)
• …….
Seagriculture ECN
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Seaweed biorefinery process concept
Raw Seaweed
Processing Primary Biorefinery
Sugars
Proteins
Minerals
Fermentation
Chemical Conversion
Energy Carriers
Bulk Chemicals
Residues
Energy
Conversion
Seagriculture ECN
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Process synthesis
• To determine the maximum allowable raw material cost • Compare different biorefinery options • Identify profit drivers • Methodology
– Determine market value of potential products – Determine mass balance – Estimate CAPEX and OPEX – Estimate gross revenue per product – Evaluate market size vs plant output
Seagriculture ECN
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Several Cases Estimated
• Full biorefinery
• Alginate only
• Simplified biorefinery
• Sugar refinery
• Etc.
Seagriculture ECN
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Refined economic model
23
-200
0
200
400
600
800
1000
1 2 3 4 5 6
€/T
on
d.w
.
Scenario
Maximum RM Price
POT 2 years
POT 5 years
POT 10 years
2012-09-19 Seagriculture ECN
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2012-09-19
Saccharina latissima Laminaria digitata
Ulva sp.
Laminaria hyperborea
Alaria esculenta Palmaria palmata
24
Seaweed species native to the North Sea
Seagriculture ECN
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Palmaria (red seaweed)
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OO O
ROHO
OH
HOOH
OO
HO
OH
OR
Xylan (1,3 and 1,4 linkage)
O
HO OH
HO OH
OH
galactose
O
HO OH
HO OH
OH
glucose
Seagriculture ECN
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Total Carbohydrate compostion of Palmaria Palmata
0%
10%
20%
30%
40%
50%
60%
70%
Apr-98 May-98 Jun-98 Jul-98 Aug-98 Sep-98 Oct-98 Nov-98 Dec-98 Jan-99 Feb-99 Mar-99 Apr-99 May-99 Jun-99 Jul-99 Aug-99 Sep-99
Month
% S
ug
ar
Xylose Galactose Glucose total
Seagriculture ECN
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Differences between biomass
• Lignocellulosic biomass:
• Cellulose – Extremely recalcitrant
• Lignine – Heterogeneous polymer
– Species, source and time of harvesting dependent
• Hemicellulose – Easy to hydrolyse
• Ash – Low to high
• Overall composition reasonably stable
• Seaweed biomass • Carbohydrates
– Type dependent on species – Amount dependent on season and
location
• Proteins – Aminoacid composition dependent on
species – Amount dependent on season and
location
• Ash – Species dependent – Amount dependent on season an
location
• Extreme differences between seasons
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Rehydrated seaweed
Seagriculture ECN
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29 2012-09-19
Fractionation
Water + Seaweed
Optional Catalyst
Liquid
Solid
T: 120-160 °C t: 1-4 h Liquid:Solid=1:10 Cat: 0-1 M H2SO4
• After reaction, separation by centrifugation (10 min, 4000 rpm) and separation of the phases.
Seagriculture ECN
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Simultaneous extraction and
hydrolysis of Palmaria
• Tests with freeze-dried Palmaria at 2.5 and 25 gr dw scale.
• Hydrolysis of Palmaria to xylose proven.
• Optimum conditions: 0.1M acetic acid, 100C, 2hrs.
• Xylose concentration is dependent on the [H]+ concentration not on acid
Scale up and with fresh seaweeds. 0
0.05
0.1
0.15
0.2
0.25
0.3
0
2
4
6
8
10
12
14
16
18
0 20 40 60 80 100 120 140
Glu
cose
(g
./L
)
Xy
lose
(g
/L
)Time (minutes)
Palmaria Hydrolysis with 0.1 M Acetic Acid, 100 °C)
g xylose/L ron g xylose/L arjan g glucose/liter
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Palmaria hydrolysis
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0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
0 20 40 60 80 100 120 140
Co
nce
ntr
atio
n in
Liq
uid
(g
/L)
Time (minutes)
RT 50° 75° 100°C
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Palmaria hydrolysis as
function of acid
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0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
0 20 40 60 80 100 120 140
con
cen
tra
tio
n g
/L
time (min)
geen 0,05M H2SO4 0,10M CH3COOH 0,10M CF3COOH
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Fresh Palmaria tests (July
2012)
• Two tests in 20L autoclave (1 kg dw seaweed).
• >10 kg received, 5 kg wet per test.
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Test 1
• 0.1M acetic acid, 100C, 2h, 9 L/kg dw seaweed.
• Red seaweed turned into green ‘soup’.
• After centrifugation, ~6L viscous liquid, ~ 4kg solid product.
• pH ND, solids recovery 51.6% dw.
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Test 2
• 0.2M acetic acid, 100C, 2h, 9 L/kg dw seaweed. • Final pH 4.1! (pH 0.1M acetic acid 2.9)
– Acid neutralising capacity of seaweed
– Consumption of acetic acid?
– Acetic acid chosen because of integration possibilities with subsequent fermentation step. Another acid needed?
• Product looked similar.
• Solids recovery: 54.9% – Higher than test 1!
– Also observed for Laminaria! Reaction products of acetic acid? Less efficient extraction at lower pH?
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Yields sugars
• Yields based on amount of extract.
• Max. achievable yield based on liquor starting amount.
• Yield xylose: ~45%.
• Optimization of separation extracted Palmaria / extract might increase yield to max ~65%.
• Future work: optimisation of process conditions.
0
20
40
60
80
100
120
Dry, 0.1M Hac Wet, 0.1M Hac Wet, 0.2M Hac
Galactose Yield
Galactose Yield (max)
Glucose Yield
Glucose Yield (max)
Xylose Yield
Xylose Yield (max)
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After fractionation
• Convert chemically
• Convert biochemically
• Use the residues
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Digestion results
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0%
50%
100%
150%
200%
250%
300%
350%
400%
450%
Microalgae Seaweed low Seaweed high Cow manure Whole sugar beet
Normalized methane production
Normalized methane production
Seagriculture ECN
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Applicable to all seaweeds?
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Ulva (green seaweed)
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OO
OROHO
OH
OR
-O3SOOH
-OOC
OO
OROHO
OH
OR
-O3SOOH
OO
OROHO
-O3SO
OR
-O3SO OH
OO
-OOC
OR
OH
OH
OR
OH-O3SO
O
HO OH
HO OH
OH
glucose
HO
HO OH
HO OH
OH
mannitol
O
OHHO
OHHO
O
HO
glucuronic acid
O
HO OH
HO
OH
rhamnose
O
OH
HO
HO
OH
xylose
O
OH
HO
HO
OH
arabinose
Ulvans
Seagriculture ECN
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Ulva Lactuca carbohydrate seasonal composition changes
0%
5%
10%
15%
20%
25%
30%
Mannitol Glucuronic acid glucose arabinose xylose rhamnose
Carbohydrate
% c
arb
oh
yd
rate
(D
M %
ba
sis
)
Apr-71 Aug-71 Nov-71 Feb-72
Seagriculture ECN
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Question?
Further information
Jaap W. van Hal
The Energy Research Center of the Netherlands (ECN)
Biomass, Bio-Refinery and Processing
P.O. Box 1, 1755 ZG Petten
+31-(0)224-564297
http://seaweed.biorefinery.nl
http://www.noordzeeboerderij.nl
http://www.atsea-project.eu
http://www.mermaidproject.eu
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