Terpènes, colophane et TOFA extraits du bois : une valeur ajoutée pour les usines de pâtes à papier F.BERTAUD, M. PETIT-CONIL Centre Technique du Papier - Grenoble Mercredi 10 Mai 2017, CTP, Grenoble Journée de valorisation du projet FUI POLYWOOD
Composés extractibles du bois composés autres que les constituants structuraux composés extraits par les solvants 25-35% 20-30% 40-45% 0.5-5% extractives 2-5% proteins <0.5% inorganics 0.1-1% «InTechFibres property do not divulgate» - Terpènes FB / 2017.05.10 2
Composés extractibles du bois composés extraits par solvants Extractives (%) Hardwood 3-8 1 birch 2-4 1 poplar 0.5-0.9 2 oak 0.2-0.25 3 eucalyptus 2.8-4.5 3 Softwood 10-25 1 pine 4-6 1 Black pine 2.8-4.3 2 Maritime pine 3-5 3 fir 0.6-2.6 2 larch 0.6-4.5 2 1 J. Gullichsen (1999) mg/g 3 F.Bertaud et al. (2008) 2 F.Bertaud et al. (2006) 3 F.Bertaud et al. (2008) fir larch B.pine M.pine Eu poplar oak «InTechFibres property do not divulgate» - Terpènes FB / 2017.05.10 3
Composés extractibles du bois Volatiles : monoterpenes (terpentine) pinene cymene limonene Fats and waxes : fatty acids & esters & alcohols, triglycerides Resins : resin acids and steroids abietic ac sitosterol Phenolics : stilbenes, lignans, tannins, flavonoids pinosylvin resveratrol isolariciresinol matairésinol taxifolin tannins miscellaneous compounds : sugars, alkaloids, coumarines, amino ac. «InTechFibres property do not divulgate» - Terpènes FB / 2017.05.10 4
Usines de pâtes chimiques (Kraft) Terpenes wood pulp Wood extractives are dissolved in Black Liquor reagents «InTechFibres property do not divulgate» - Terpènes FB / 2017.05.10 5
Usines de pâtes chimiques (Kraft) Terpenes wood pulp Wood extractives are dissolved in Black Liquor Dirty steams CONDENSER Turpentine Black Liquor condensate Crude sulphate turpentine 5 10 kg//t of kraft pulp, pine > spruce reagents CTO 30-50 kg / T pâte Kraft 50-70% of initial content Residual BL Soap recovering + acidification Crude Tall Oil (CTO) 6
Térébenthine (Turpentine) Térébenthine sulfonné Térébenthine de gemme (oleoresin) turpentine terpentine (natural oleoresin) composition of Nordic softwood kraft turpentine (%) a-pinene 60-83 b-pinene 2-7 D3-carene 11-28 others 2-6 J.Gullichsen and H.Lindberg (1999) Maritime pine wood chips Spruce wood chips F.Bertaud et al., Holzforschung in press (2017) «InTechFibres property do not divulgate» - Terpènes FB / 2017.05.10 7
Liqueur Noire CTO Hydrolysis of fats and waxes sodium and calcium soaps of Fatty acids and Resin acids (fatty acids completely hydrolysed, waxes more stable) Isomerisation of unsaturated fatty acids and resin acids levopimaric ac abietic ac Dissolution in Black liquor Tall oil soap + acidification CTO Rq : Sterol esters, waxes and free sterols do not form soluble soaps deposits (pitch) BL composition from Kraft pulping of birch (% by weight) Organics 78% degraded lignin 37.5% Isosaccharinic acids 22.6% Aliphatic acids 14.4% Resin and fatty acids 0.5% Polysaccharides 3% E.Vakkilainen (1999) TOC composition from Scandinavia E.Vakkilainen (1999) (% by weight) Resin acids 23% Fatty acids 57% Unsaponifiables 20% J. Gullichsen, H. Lindeberg (1999) «InTechFibres property do not divulgate» - Terpènes FB / 2017.05.10 8
Liqueur Noire CTO Hydrolysis of fats and waxes sodium and calcium soaps of Fatty acids and Resin acids (fatty acids completely hydrolysed, waxes more stable) Isomerisation of unsaturated fatty acids and resin acids levopimaric ac abietic ac Dissolution in Black liquor Tall oil soap + acidification CTO Rq : Sterol esters, waxes and free sterols do not form soluble soaps deposits (pitch) colophane TOFA BL composition from Kraft pulping of birch (% by weight) Organics 78% degraded lignin 37.5% Isosaccharinic acids 22.6% Aliphatic acids 14.4% Resin and fatty acids 0.5% Polysaccharides 3% E.Vakkilainen (1999) CTO composition from Scandinavia E.Vakkilainen (1999) (% by weight) Resin acids 23% Fatty acids 57% Unsaponifiables 20% J. Gullichsen, H. Lindeberg (1999) «InTechFibres property do not divulgate» - Terpènes FB / 2017.05.10 9
Marchés / Utilisations 20-40% 25-35% 25-35% «InTechFibres property do not divulgate» - Terpènes FB / 2017.05.10 10
Diagnostics des usines Expertises Terpènes volatiles et autres extractibles Mapping des emissions sur site Nouveaux marchés Terpènes solvants verts chimie de synthèse TallOil AG et Stérols Raffinage dans l usine : + valeurs ajoutées + Extraction des polyphénols des résidus/ bois avant cuisson «InTechFibres property do not divulgate» - PhenoLiq/ FB / 2017.05.10 11