Characterization of tree and wood fractions for biorefinery applications SARA JOHANSSON COST FP0901 TURKU SEPTEMBER 18, 2013

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Characterization of tree and wood fractions for biorefinery applications SARA JOHANSSON COST FP0901 TURKU SEPTEMBER 18, 2013

To characterize differences in raw material composition and processability of well defined tree and wood fractions Department of Forest Biomaterials and Technology Department of Chemical Engineering

2 trees from SLU field trials Scots pine (Pinus sylvestris) Tree 1 From clearcut stand Dense population in youth Slow growth Tree 5 From thinned stand Extremely sparse population in youth Fast growth

Each tree divided into 9 fractions 75% 50% 1.3 m Branches Needles Knotwood Bark Sapwood Heartwood Needles Branches Sapwood 1.3 m, 50%, 75% Heartwood 1.3 m, 50% Knotwood Bark

Objectives of the work in Lund Raw material analysis Moisture and ash content Total extractives content Structural carbohydrates and lignin Pretreatment Solid fraction Carbohydrates and lignin Liquid fraction Mono and oligosacharides Furans and acetic acid Yields and recoveries Enzymatic hydrolysis Carbohydrates and lignin Overall glucose yield

Raw material

Moisture content ~50% ~20% Heartwood is considerably drier than other fractions

The composition of pine Percent dry weight composition Glucan Mannan Xylan Lignin 46 12 9 30 Handbook on Bioethanol, ed. Wyman C.E. Cellulose Arabinoglucuronoxylan Galactoglucomannan Lignin Pulp and Paper Chemistry and Technology, ed. Ek, Gellerstedt, Henriksson

Raw material analysis 2 step acid hydrolysis strong acid 30 C, 60 min dilute acid 120 C, 60 min Klason and acid soluble lignin HPLC used for sugar analysis 2 step acid hydrolysis Milled and dried raw material

Carbohydrates ~20% more glucan in Tree 5 Bigger difference between the trees than within the trees (glu and xyl) 10 25% difference within the trees 5 25% more mannan in Tree 5 25 40% more xylan in Tree 5

Lignin content The faster grown tree (5) has a sligthly higher lignin content than the slower grown tree n.d.

Extraction Soxhlet extraction Water Ethanol Extraction before raw material analysis To assess extractives content Extractives may disturb results

Extractives Heartwood richer in extractives than sapwood Top has more extractives than bottom Hydrophilic Salts Sugars Lignans Fenols fungicides Hydrophobic Fats and fatty acids Waxes Terpenes pine smell

Summary Raw material The faster grown tree richer in carbohydrates than the slower grown tree Heartwood richer in extractives than sapwood Top has more extractives than bottom (of the trunk)

Pretreatment Steam pretreatment 2.5% SO 2 (based on moisture content) 210 C 5 minutes

Yields of mono and oligosacharides after pretreatment 100% higher yield Sapwood 1.3 m Tree 5 (fast growth) Highest glucose yield Lowest mannose and xylose yields Heartwood 1.3 m Tree 1 (slow growth) Lowest glucose yield Highest mannose and xylose yields 60% higher yield 90% higher yield

Recovery of carbohydrates after pretreatment Less sugars recovered from the faster grown tree > pretreatment acted more severely Hemicellulose more easily hydrolyzed than cellulose > lower recoveries of mannan and xylan compared to glucan Heartwood has somewhat higher recoveries of hemicellulose than other fractions

Hydrolysis of lignocellulose Palmqvist, E.; Hahn Hägerdal, B., 1999

Yields of furans and acetic acid after pretreatment The faster grown tree yielded more furans and acetic acid from sapwood and heartwood fractions Knotwood had similar yields for both trees Heartwood had lower yields than other fractions

Summary Pretreatment All hemicellulose solubilized at the conditions used Glucan was recovered in fiber as well as in liquid fraction of the pretreated slurry Mannan and xylan only recovered in the liquid fraction The pretreatment acted harsher on the faster grown tree Lower carbohydrate recoveries than the slow grown tree Higher yields of furans from sapwood and heartwood knotwood had similar yields from the two trees Lower WIS content than the slower grown tree Heartwood withstood the pretreatment better than other fractions Higher recoveries of carbohydates Lower yields of furans

Enzymatic hydrolysis Conv. E.H (%) 1 Overall yield (%) 2 UW 0.1 40 60 UW 0.2 76 87 W 0.1 56 71 W 0.2 86 92 1 Final conversion, based on glucan content in pretreated material 2 Overall glucose yield after pretreatment and enzymatic hydrolysis, based on glucan content in the raw material Sapwood (1.3 m) from slowgrown tree Washed and unwashed material 2 different enzyme dosages 10 FPU/g WIS 20 FPU/g WIS

Outlook Pretreatments at different conditions optimization Enzymatic hydrolysis of more pretreated material

Tommy Möhrling Paul Geladi Thomas Ulvcrona Mehrdad Arshadi Gunnar Lidén Mats Galbe Thank you for your attention! This work was financed by a grant from the Bo Rydin foundation