Biorefinery of Sustainable Biomass from Land and Sea

Transcription

1 Biorefinery of Sustainable Biomass from Land and Sea W.J.J. Huijgen J.W. van Hal November 2014 ECN-L

2 Biorefinery of Sustainable Biomass from Land and Sea Technology Development at ECN W.J.J. Huijgen & J.W. van Hal Maarssen November 5 th,

3 Energy research Centre of the Netherlands (ECN) What do we do: ECN develops market driven technology and know-how to enable a transition to a sustainable energy society Business units: Biomass & energy efficiency Solar energy Wind energy Policy studies Environment & energy engineering 5/11/2014 NPS 14 ECN Independent research institute ~600 employees Locations: - Petten (HQ) - Amsterdam - Eindhoven - Brussels - Beijing 2

4 Biomass waste wood (agricultural) residues energy corps aquatic biomass 5/11/2014 NPS 14 3

5 Lignocellulosic Biorefinery

6 Lignocellulose Pretreatment Several physical-chemical pretreatment routes to promote enzymatic cellulose hydrolysis under development. Main pretreatment routes (demo/commercial-scale): (Dilute) acid pre-treatment. Steam explosion. Routes effective for cellulose, however: Lignin ends up in residue (with unconverted sugars, process chemicals, ash, ). Residue generally only suitable for CHP. Alternative: Separation of lignin prior to enzymatic hydrolysis. Preserving native chemical functionalities of lignin. rganosolv Harmsen et al. (2010), Literature review of physical and chemical pretreatment processes for lignocellulosic biomass, report ECN-E /11/2014 NPS14 5

7 Lignocellulose Biorefinery Aims: Utilisation of >75wt% of biomass. Fractionation of all major constituents in a sufficient quality for valorisation. Lignocellulosic biomass Primary biorefinery Fractionation (organosolv) Paper & cellulosic materials Cellulose Hemicellulose (Enzymatic) hydrolysis Secondary biorefinery Fermentation Chemical conversion Ethanol Butanol Lactic acid... Furfural HMF Including extraction of high-quality lignin for production of materials/chemicals. Lignin Filler, adhesives,... Thermochemical depolymerisaton CHP Phenolics Fuel additives... Electricity Heat Reith et al. (2011) A step towards the development of a biorefinery, NPT procestechnologie, 18(1), /11/2014 NPS 14 6

8 rganosolv Process Solvent recycling Lignocellulose Solvent Water (+ catalyst) rganosolv Lignin separation Solvent separation Hemicellulose (derivatives) Cellulose (S) Lignin (S) ECN process: Solvents: aqueous ethanol, acetone, Typical process conditions: ºC, min, acid catalyst. ECN experience: Wide range of feedstocks: softwoods, hardwoods and herbaceous biomass. Know-how on optimum process parameters. Multiple process (& solvent) options depending on target products. J. Wildschut et al. (2013) Ethanol-based organosolv fractionation of wheat straw, Bioresource Technology, 135, /11/2014 NPS 14 7

9 Conversoin Cellulose to Glucose High enzymatic digestibility of organosolv cellulose pulps. Spin-off organosolv development: Cellulase Saver Method to reduce enzyme costs in production of sugars. Herbaceous biomass. Pretreatment technology independent. H 2 0 Biomass Protein extraction Pretreatment Enzymatic hydrolysis Glucose Dissolved proteins More information: Patent application W 2014/ Time (hrs) 5 FPU/gr 5 FPU/gr + extract 10 FPU/gr 20 FPU/gr 5/11/2014 NPS 14 8

10 Cellulose to Isosorbide ne-pot conversion of (ligno)cellulose to iso-sorbide. Low isosorbide yields from unpretreated lignocellulosic biomass. Pretreatment key to efficient one-pot conversions. High isosorbide yields attained (63%) when using a highly delignified organosolv pulp p de Beeck, B. et al., ChemSusChem 6(1) (2013) 199 5/11/2014 NPS 14 9

11 Cellulose to 2G Furan Derivatives Direct alcoholysis of cellulose to (intermediates for) HMF-ethers. Main product: ethylated-glucose (glucosides). ES-LT CATFUR Grisel, R.J.H. et al. (2014) Acid catalysed alcoholysis of lignocellulosic biomass: towards second generation furan-derivatives, Catalysis Today 223, /11/2014 NPS 14 10

12 Lignin Applications low volume - high value market /t specialty chemicals for food, fragrance and pharmaceuticals bio-plastics bio-resins for woodadhesives additives for flooring material alkylphenols bio-fuel for CHP high volume - low value market 100 /t fuel-additives bio-bitumen for green asphalt bio-char for soil improvement activated carbon, carbon-fibres and carbon-black P.J. de Wild et al. (2014) Lignin pyrolysis for profitable lignocellulosic biorefineries, Biofuels, Bioproducts & Biorefining (biofpr) 8(5), catechols guaiacols syringols 11

13 Phenol-Formaldehyde Resins Successful replacement of phenol by lignin in PF resins. Substitution up to 50% w/w (hardwood lignin). Papadopoulou et al. (2012) Thermosetting adhesives with renewable raw materials for wood-based products, UBICHEM-III, Thessaloniki, Greece. 5/11/2014 NPS 14 12

14 Seaweed Biorefinery

15 Seaweed Biorefinery Development of biorefinery technologies for cultivated seaweeds to produce 3 rd generation biofuels & chemicals. Large difference in composition between main classes of seaweed (brown, red and green). Need to develop specific biorefinery schemes for various types of seaweeds. Seaweeds still expensive feedstock coproduction of high-value specialty chemicals and commodity carbohydrates. Blade Stipe Holdfast 5/11/2014 NPS 14 14

16 Seaweed Species from the North Sea Saccharina lattisima Laminaria digitata Laminaria hyperborea Ulva sp. 5/11/2014 Alaria esculenta NPS 14 Palmaria palmata 15

17 Why Seaweeds or Macroalgae? Do not compete with food Do not compete with any other land use Grow in cold seawater The fastest growing biomass at our latitude (Kelps) Composition complementary for fuel/chemicals production to lignocellulosic biomass & micro-algae. Mainly composed of (specialty) carbohydrates, protein and minerals, e.g.: Brown seaweeds (Kelps): mannitol (sugar alcohol) & alginic acid (thickening & gelling agent). Green seaweeds: ulvans (bioactives) & rhamnose. Red seaweeds: xylans & carrageenan (thickening & gelling agent). J.W. van Hal et al. (2014) pportunities and challenges for seaweed in the biobased economy, Trends in Biotechnology, 32(5), /11/2014 NPS 14 16

18 Seaweed Biorefinery Concept Sugars Fermentation Energy Carriers Raw Seaweed Processing Primary Biorefinery Proteins Chemical Conversion Bulk Chemicals Residues Minerals Energy Conversion 5/11/2014 NPS 14 17

19 Example: Biorefinery of Kelps? Hot water Mild acid Laminaria Alginate FDCA WUR Protein Laminarin Mannitol Fuoidan UF Laminarin Mannitol Patent filed on mannitol extraction from brown seaweed. J. van Hal & W.J.J. Huijgen, Process for mannitol extraction from seaweed, patent application NL /11/2014 NPS 14 18

20 Saccharina tests Harvest June 2013, Galway, Ireland. Huge leaves cut to ~5 cm pieces for experiments. Moisture: 82-85%. Isolation of mannitol & laminarin by extraction with fresh water (1:1). T ( C) ph Solids (dw%) RT /11/2014 NPS 14 19

21 From Seaweed to Isomannide Crude carbohydrates Mannitol Purification Conversion into iso-mannide 5/11/2014 NPS 14 20

22 Applications of Isomannide Isomer of isosorbide Interconvertable into other isomers Separation based on boiling point possible Intermediate for Plasticizers Fuel additives PET replacements Epoxy resins PUR 5/11/2014 NPS 14 21

23 Summary Seaweed Biorefinery Cost analysis biorefinery of Kelps: Need to valorize multiple components from seaweed Seaweed to only biofuels not as attractive biorefinery Profit driver is isomannide Based on pay-back time of 2 years, seaweed may cost up to 1000/ton (dry matter) Challenges ahead: Increasing volumetric through-put (seaweeds ~20% dw, diluted streams). Early stage of development scale-up & efficiency improvement. Development reliable cultivation & supply chain of seaweeds. 5/11/2014 NPS 14 22

24 Question? Further information Jaap W. van Hal Innovation Manager Biorefinery Energy Research Centre of the Netherlands (ECN) Biomass and Energy Efficiency P.. Box 1, 1755 ZG Petten +31-(0) /11/2014 NPS 14 23

25 ECN Westerduinweg 3 P.. Box LE Petten 1755 LG Petten The Netherlands The Netherlands T F info@ ecn.nl 8