High value chemicals from spruce (Picea abies) extracts losses in the supply chain
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1 High value chemicals from spruce (Picea abies) extracts losses in the supply chain Eelis Halmemies, Ms.Sc Hanna Brännström, Ph.D. Kokkola Material Week,
2 Routes to valuable bioactive extractives Tall oil Sitosterol CLAs Stem wood Pulping Papermaking Stump-root system Foliage Tannins Flavonoids Knots Bark Lignans Flavonoids Stilbenes Stilbenes Betulin Tannins Lignans Stilbenes
3 Effect of supply chain to extractives Harvesting method o How damaging is it to e.g. wood bark? Transportation o How and how quickly is the material transported to storage site? Storage o Covered or uncovered? Tree species o Unique extractives in different wood species. E.g. betulin in birch bark Physical form of the wood o Typically smaller size means greater loss of extractives Weather o Rainfall can extract hydrophilic extractives Season o Certain hydrophobic extractives accumulate during winter Other environmental conditions
4 Chemical changes during wood storage After felling the tree, the content of extractives starts immediately to decrease causing alteration in the chemical composition of this fraction The major chemical changes in the resin during wood storage are: 1. Evaporation of volatile terpenoids 2. Rapid hydrolysis of triglycerides accompanied by slower hydrolysis of waxes, especially steryl esters 3. Oxidation/degradation/polymerization of resin acids, unsaturated fatty acids and to some extent other unsaturated compounds
5 BioHub WP4: Feedstock characterization and fractioning BioHub project develops methods and business models for forest terminals. Aim: to create new feedstock delivery regimes for the refining industries based on property changes during terminal and logistical operations i.e. "right material for right industry". Experimental set-up: storage studies for forestry side-streams incl. spruce bark, logging residues, stumps
6 BioHub WP4: Feedstock characterization and fractioning Chemical analysis: main focus is on extractives analysis: Lipophilic and hydrophilic extractives: o Extractives groups (GC/FID), individual extractives compounds (both free and esterified) (GC/MSD and GC/FID) Emphasis on phenolic extractives: o Folin-Ciocalteu assay and other UV-Vis methods. Structural characterization (LC/MS, possibly NMR and/or Py-GC/MS). Main focus is on analysis of tannins and lignans. Change in the antioxidant properties of phenolic compounds o DPPH method
7 Materials for analyses Un-covered pile of spruce bark (450 m 3 ) Snow-covered pile of spruce bark (450 m 3 ) Un-debarked single stems (spruce sawlogs)
8 Construction of the non-covered pile
9 Total dissolved solids (TDS) 40,00 Gravimetric extractives (% of dry matter) 35,00 30,00 25,00 20,00 15,00 10,00 5,00 0,00 P(0) P(4) P(12) TK(0) TK(4)Y TK(4)R TK(4)K TK(12)Y TK(12)R TK(12)K TK(24)Y TK(24)R TK(24)K
10 Total dissolved solids (TDS) 40,00 35,00 Gravimetric extractives (% of dry matter) It seems that hydrophilic extractives are best preserved in the middle of the pile. The loss of extractives is most substantial where the exposure to external influences (weather, UVradiation etc.) is the greatest. 30,00 25,00 20,00 15,00 10,00 5,00 0,
11 Focus on stilbenes
12 Focus on stilbenes
13 mg/g of dry matter Focus on stilbenes Change in the amount of stilbenes during storage LOG (0) LOG (4) LOG (12) SPRUCE BARK PILE (0) SPRUCE BARK PILE (4)
14 Extractives from hot water extraction (ASE) SPRUCE BARK PILE (0-SAMPLE) HYDROPHILIC EXTRACTIVES resin acids 4 % other 2 % flavonoids 2 % fatty acids 1 % Stilbenes 13 % sugars 39 % alcohols 19 % organic acids 20 % timescale (weeks)
15 Extractives from hot water extraction (ASE) SPRUCE BARK PILE (4 WEEK-SAMPLE) HYDROPHILIC EXTRACTIVES flavonoids 2 % other 0 % resin acids 0 % alcohols 22 % sugars 50 % organic acids 25 % timescale (weeks)
16 Extractives from hot water extraction (ASE) SPRUCE BARK PILE (12 WEEK-SAMPLE) HYDROPHILIC EXTRACTIVES alcohols 7 % resin acids 1 % flavonoids 1 % other 0 % organic acids 31 % sugars 60 % timescale (weeks)
17 Conclusions The effect of the way of storage and the physical form of the wood on the chemical composition of its extractives is substantial. This kind of information could be utilized to improve the logistics of the wood supply chain to get the right kind of material to right customer at the right time. In order to maximize the potential value of the forestry side streams, and to make correct decisions about handling of the material, more comprehensive research is still needed
18 Thank you!
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