Seaweed Biorefinery in the Netherlands

Transcription

1 Seaweed Biorefinery in the Netherlands J.W. van Hal October 2012 ECN-L

2 Seaweed Biorefinery in the Netherlands J.W. (Jaap) van Hal Neeltje Jans September 19,

3 SBIR EOS LT Precultivation on Land Planting at Sea Cultivation Harvesting Transport Primary Bio- Refinery Secondary Bio-refinery Products and Energy Seagriculture ECN 2

4 The team: Willem de Visser Julia Wald Willem Brandenburg

5 Ecofys module ECOFYS

6 Aquatic Biomass Seagriculture ECN 5

7 Mission: ECN develops market driven technology and knowhow to enable a transition to sustainable energy Seagriculture ECN 6

8 Locations Petten (head office) Wieringerwerf Amsterdam Eindhoven Brussels Beijing Seagriculture ECN 7

9 R&D fields Policy Studies Energy Engineering Environment Wind Energy Solar Energy Biomass Energy Efficiency & CCS Seagriculture ECN 8

10 Biomass & Energy Efficiency Your energy. Our passion. Neeltje Jans

11 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 Seagriculture ECN 10

12 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 Seagriculture ECN 11

13 Biomass Pre-Treatment Licensees, clients Torrefaction technology Pilot plant under construction Seagriculture ECN 12

14 Biomass Gasification: Milena, Olga & Tara

15 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 Seagriculture ECN 14

16 Parts of seaweed plant Blade Stipe Holdfast Seagriculture ECN 15

17 Does not compete with food Seagriculture ECN 16

18 No land use issues Seagriculture ECN 17

19 Bio-Offshore Seaweed cultivation area km 2 (<10 % of the NL area of the North 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 Seagriculture ECN 18

20 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 19

21 Seaweed biorefinery process concept Sugars Fermentation Energy Carriers Raw Seaweed Processing Primary Biorefinery Proteins Chemical Conversion Bulk Chemicals Residues Minerals Energy Conversion Seagriculture ECN 20

22 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 21

23 Several Cases Estimated Full biorefinery Alginate only Simplified biorefinery Sugar refinery Etc Seagriculture ECN 22

24 /Ton d.w. Refined economic model 1000 Maximum RM Price POT 2 years POT 5 years POT 10 years Scenario Seagriculture ECN 23

25 Seaweed species native to the North Sea Saccharina latissima Laminaria digitata Laminaria hyperborea Ulva sp Alaria esculenta Seagriculture ECN Palmaria palmata 24

26 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 Seagriculture ECN 25

27 % 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 Xylose Galactose Glucose total Seagriculture ECN 26

28 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 Seagriculture ECN 27

29 Rehydrated seaweed Seagriculture ECN 28

30 Fractionation Water + Seaweed T: 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 Seagriculture ECN 29

31 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 Palmaria Hydrolysis with 0.1 M Acetic Acid, 100 C) Scale up and with fresh seaweeds Time (minutes) g xylose/l ron g xylose/l arjan g glucose/liter Seagriculture ECN 30

32 Concentration in Liquid (g/l) Palmaria hydrolysis Time (minutes) RT C Seagriculture ECN 31

33 concentration g/l Palmaria hydrolysis as function of acid time (min) geen 0,05M H2SO4 0,10M CH3COOH 0,10M CF3COOH Seagriculture ECN 32

34 Fresh Palmaria tests (July 2012) Two tests in 20L autoclave (1 kg dw seaweed). >10 kg received, 5 kg wet per test Seagriculture ECN 33

35 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 Seagriculture ECN 34

36 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? Seagriculture ECN 35

37 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 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) Seagriculture ECN 36

38 After fractionation Convert chemically Convert biochemically Use the residues Seagriculture ECN 37

39 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 Seagriculture ECN 38

40 Applicable to all seaweeds?

41 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 Seagriculture ECN 40

42 % carbohydrate (DM % basis) Ulva Lactuca carbohydrate seasonal composition changes 30% 25% 20% 15% 10% 5% 0% Mannitol Glucuronic acid glucose arabinose xylose rhamnose Carbohydrate Apr-71 Aug-71 Nov-71 Feb-72 Seagriculture ECN 41

43 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) Seagriculture ECN 42