Seaweed Biorefinery in the Netherlands J.W. van Hal October 2012 ECN-L--12-051
Seaweed Biorefinery in the Netherlands J.W. (Jaap) van Hal Neeltje Jans September 19, 2012 www.ecn.nl
SBIR EOS LT Precultivation on Land Planting at Sea Cultivation Harvesting Transport Primary Bio- Refinery Secondary Bio-refinery Products and Energy 2012-09-19 Seagriculture ECN 2
The team: Willem de Visser Julia Wald Willem Brandenburg
Ecofys module ECOFYS
Aquatic Biomass 2012-09-19 Seagriculture ECN 5
Mission: ECN develops market driven technology and knowhow to enable a transition to sustainable energy 2012-09-19 Seagriculture ECN 6
Locations Petten (head office) Wieringerwerf Amsterdam Eindhoven Brussels Beijing 2012-09-19 Seagriculture ECN 7
R&D fields Policy Studies Energy Engineering Environment Wind Energy Solar Energy Biomass Energy Efficiency & CCS 2012-09-19 Seagriculture ECN 8
Biomass & Energy Efficiency Your energy. Our passion. Neeltje Jans 2012 www.ecn.nl
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 2012-09-19 Seagriculture ECN 10
Biomass a diverse energy source Biomass = all organic material of non-fossil origin meant for energy or chemicals/materials production waste wood (agricultural) residues energy corps aquatic biomass 2012-09-19 Seagriculture ECN 11
Biomass Pre-Treatment Licensees, clients Torrefaction technology Pilot plant under construction 2012-09-19 Seagriculture ECN 12
Biomass Gasification: Milena, Olga & Tara
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 2012-09-19 Seagriculture ECN 14
Parts of seaweed plant Blade Stipe Holdfast 2012-09-19 Seagriculture ECN 15
Does not compete with food 2012-09-19 Seagriculture ECN 16
No land use issues 2012-09-19 Seagriculture ECN 17
Bio-Offshore Seaweed cultivation area 5.000 km 2 (<10 % of the NL area of the North Sea @ 57.000 km 2 ) 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 2012-09-19 Seagriculture ECN 18
Potential Applications Furanics (carbohydrate conversion) Polyols for poly-urethanes (direct application) Butanol (fermentation) Bleach activators (derivatization) Phosphate recycling/fertilizers (Ash utilization) Fodder (protein fraction). 2012-09-19 Seagriculture ECN 19
Seaweed biorefinery process concept Sugars Fermentation Energy Carriers Raw Seaweed Processing Primary Biorefinery Proteins Chemical Conversion Bulk Chemicals Residues Minerals Energy Conversion 2012-09-19 Seagriculture ECN 20
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 2012-09-19 Seagriculture ECN 21
Several Cases Estimated Full biorefinery Alginate only Simplified biorefinery Sugar refinery Etc. 2012-09-19 Seagriculture ECN 22
/Ton d.w. Refined economic model 1000 Maximum RM Price 800 600 400 200 POT 2 years POT 5 years POT 10 years 0-200 1 2 3 4 5 6 Scenario 2012-09-19 Seagriculture ECN 23
Seaweed species native to the North Sea Saccharina latissima Laminaria digitata Laminaria hyperborea Ulva sp. 2012-09-19 Alaria esculenta Seagriculture ECN Palmaria palmata 24
Palmaria (red seaweed) RO HO OH O HO O O O OH HO OH O OR Xylan (1,3 and 1,4 linkage) HO O OH HO OH OH HO O OH HO OH OH galactose glucose 2012-09-19 Seagriculture ECN 25
% Sugar Total Carbohydrate compostion of Palmaria Palmata 70% 60% 50% 40% 30% 20% 10% 0% 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 2012-09-19 Xylose Galactose Glucose total Seagriculture ECN 26
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 2012-09-19 Seagriculture ECN 27
Rehydrated seaweed 2012-09-19 Seagriculture ECN 28
Fractionation Water + Seaweed T: 120-160 C t: 1-4 h Liquid:Solid=1:10 Cat: 0-1 M H 2 SO 4 Optional Catalyst Liquid Solid After reaction, separation by centrifugation (10 min, 4000 rpm) and separation of the phases. 2012-09-19 Seagriculture ECN 29
Xylose (g/l) Glucose (g./l) 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 18 16 14 12 10 8 6 4 2 Palmaria Hydrolysis with 0.1 M Acetic Acid, 100 C) 0.3 0.25 0.2 0.15 0.1 0.05 Scale up and with fresh seaweeds. 0 0 0 20 40 60 80 100 120 140 Time (minutes) g xylose/l ron g xylose/l arjan g glucose/liter 2012-09-19 Seagriculture ECN 30
Concentration in Liquid (g/l) Palmaria hydrolysis 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0 20 40 60 80 100 120 140 Time (minutes) RT 50 75 100 C 2012-09-19 Seagriculture ECN 31
concentration g/l Palmaria hydrolysis as function of acid 16.0 14.0 12.0 10.0 8.0 6.0 4.0 2.0 0.0 0 20 40 60 80 100 120 140 time (min) geen 0,05M H2SO4 0,10M CH3COOH 0,10M CF3COOH 2012-09-19 Seagriculture ECN 32
Fresh Palmaria tests (July 2012) Two tests in 20L autoclave (1 kg dw seaweed). >10 kg received, 5 kg wet per test. 2012-09-19 Seagriculture ECN 33
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. 2012-09-19 Seagriculture ECN 34
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? 2012-09-19 Seagriculture ECN 35
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. 120 100 80 60 40 20 0 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) 2012-09-19 Seagriculture ECN 36
After fractionation Convert chemically Convert biochemically Use the residues 2012-09-19 Seagriculture ECN 37
Digestion results 450% Normalized methane production 400% 350% 300% 250% 200% 150% 100% 50% 0% Microalgae Seaweed low Seaweed high Cow manure Whole sugar beet Normalized methane production 2012-09-19 Seagriculture ECN 38
Applicable to all seaweeds?
Ulva (green seaweed) HO OH OH HO HO OH mannitol HO OH OH HO O O HO OH HO OH OH glucose xylose HO OH HO O O HO HO OH O HO OH OH glucuronic acid arabinose Ulvans - OR OOC RO O O HO O OH - O 3 SO OH OR RO O O HO O OH - O 3 SO OH OR O O O HO OH OH O HO rhamnose RO HO - O 3 SO - OOC OR OH O OH - O 3 SO OH OR O - O 3 SO OH 2012-09-19 Seagriculture ECN 40
% carbohydrate (DM % basis) Ulva Lactuca carbohydrate seasonal composition changes 30% 25% 20% 15% 10% 5% 0% Mannitol Glucuronic acid glucose arabinose xylose rhamnose Carbohydrate 2012-09-19 Apr-71 Aug-71 Nov-71 Feb-72 Seagriculture ECN 41
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 vanhal@ecn.nl http://seaweed.biorefinery.nl http://www.noordzeeboerderij.nl http://www.atsea-project.eu http://www.mermaidproject.eu 2012-09-19 Seagriculture ECN 42