Department of Forest Biomaterials and Technology From forest to biomaterials, Extraction of valuable chemicals

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1 Department of Forest Biomaterials and Technology From forest to biomaterials, Extraction of valuable chemicals MEHRDAD ARSHADI, 25 th of MAY 2017, GELA, ITALY

2 Sweden & SLU Sweden 66 % of the land area covered by forest, Umeå Faculty of Forest Sciences Foresters Wild life ecologists Uppsala Faculty of Natural Resources and Agricultural Sciences Agronomists Chemists Biologists Faculty of Veterinary Medicine and Animal Science Vets Alnarp Faculty of Landscape Planning, Horticulture and Agricultural Science Landscape architects

3 The wood components Wood Low-molecular-weight substances Macromolecular substances Organic matter Inorganic matter Polysacharides Lignin Extractives Ash Cellulose Hemicellulose

4 Extractives Group of non-structural components in wood Consists of both hydrophilic and lipophilic compounds Dissolves in either water or organic solvents Different amounts and distribution of extractives from tree to tree, dependent on: - wood species - growing site (latitude, altitude, wind exposure etc) - position within the tree - genetic factors

5 Extractives Gives the colour and odour to the trees Protects the tree from microbic and insect attacks The energy stock of the living cells of trees The heartwood of pine is filled with extractives Terpenes, fatty/resin acids, alcoholes, triterpenoids and stereoids, stilbenes

6 National Projects: Fatty/resin acids in PC & PS ( ) TALLRAFF project, ( ), Bo Rydin, SCA Cooperation: Lund University, SLU CETEX project ( ), FORMAS Cooperation: York University, SLU

7 Wood Chemistry Research Collaborations SLU: Mehrdad Arshadi (Asso. Prof, Org. Chem) Urban Bergsten (Professor,Silviculture) Paul Geladi (Professor, Chemometric) Calle Nilsson (EM Professor, Analyt. Chem.) Rashmi Kataria (Ph D in Carbo. Chem.) Thomas Ulvcrona (Ph D, Forest Matr.) Daniel Ericsson (Ph D, Forest Matr.) Carina Jonsson (Research Eng.) Tommy Mörling (Ph D) Natalia Bukhanko (Ph D, Chemistry) Ingegerd Backlund (Ph D Forest science) Anteneh Assefa (Ph D, Chemistry) York University: James Clark (Professor, Head) Andrew Hunt (Ph D., Scientific Leader ) Vitaliy Budarin (Ph D, Microwave Tech.) Tom Attard (Ph D, Supercritical ext.) Mohammed Chowdhury (Ph D Student) Lund University: Gunnar Lidèn (Professor) Mats Galbe (Asso. Professor, Carbohydrates) Sara Johansson (Ph D Student) Karin Carlqvist (Ph D student)

8 30-year old lodgepole pine (Pinus contorta) stand in northern Sweden. FATTY AND RESIN ACID CONTENT IN DIFFERENT WOOD TISSUES OF PINUS CONTORTA AND PINUS SYLVESTRIS PROJECT PC & PC

9 Pinus Contorta (Lodgepole pine) Not a domestic species in Sweden, introduced from British Columbia and Yukon, Canada. Produces about 30% more stem volume than the domestic pine species, Scots pine Most stands planted in the 70s and 80s

10 Aim Examine the fatty and resin acids contents in different fractions of lodgepole pine and Scots pine from various geographic sites in Sweden. PINUS CONTORTA (lodgepole pine) = PC PINUS SYLVESTRIS (Scots pine) = PS

11 Sampling method in forest Totally 60 trees (30 PS and 30 PC) selected From five different sites 5 mm increment cores were taken from each sampled tree at a height of 1.3 m Site index (height in m at age of 100 year) Table 1 Stand data for the five sites Lat. Altitude, Year of Site index, m, H100 Number Site N m, a. s. l. planting Ps Pc of pairs S1 (Öjebyn) S2 (Lillögda) S3 (Korseleberget) S4 (Toböle) S5 (Öd) 63, Ps- Pinus sylvestris Pc- Pinus contorta Drill cores of stemwood

12 Separation of sapwood and heartwood Different color Dyed with a 50/50 blend of saturated sulphanilic acid (C 6 H 7 NO 3 S) and 10% sodium nitrite (NaNO 2 ) Different moisture content Sapwood Heartwood

13 Isolation/detection of extractives Soxhlet extraction: Petroleum ether (bp 40 to 60 C) and acetone (90:10 v/v)

14 Results 21 fatty and 10 resin acids were identified. Total amount of fatty and resin acids in Scots pine varied between 0.24% and 4.1% of dry material. Total amount of fatty and resin acids in lodgepole pine varied between 0.23% and 2.6 % of dry material. Resin acids were associated with heartwood and fatty acids with sapwood. The two species show differences in hexadecanoic and heptadecanoic acid contents.

15 Fatty acid content (microgram/gram) Ankarskatan n= Korseleberget n=5 Lillögda n= Toböle n=6 Öd n= P. contorta heartwood P.contorta sapwood P. sylvestris heartwood P. sylvestris sapwood

16 Resin acid content (microgram/gram) Ankarskatan n=8 Korseleberget n=5 Lillögda n= Toböle n=6 Öd n= P. contorta heartwood P.contorta sapwood P. sylvestris heartwood P. sylvestris sapwood

17 Multivariate modelling Extracted out relevant information from large data matrix p1 + X Model components p2 Correlating to -age of samples -moisture content -tree species noise + E Fatty- & resin acids t1 t2

18 Fatty/resin acids composition in heartwood and sapwood parts of Scots pine and in lodgepole pine Mehrdad Arshadi, Ingegerd Backlund, Paul Geladi, Urban Bergsten,Comparison of fatty and resin acid composition in boreal lodgepolepine and Scots pine for biorefinery applications, Industrial Crops and products, 49, 2013,

19 Conclusions Significant higher extractive concentrations in heartwood than in sapwood A typical mature lodgepole pine stand (100 and 140 tons of dry weight biomass/ha): 150 kg fatty acids/ha 1 ton resin acids/ha In addition, other substances such as waxes and aromatics can be derived. Fractionation of different part of trees are essential for optimal utilization of biorefinery feedstock.

20 Practical implications This study implies that heartwood from Scots pine is suitable for resin extraction while lodgepole pine presents a better option for general fatty- and resin acid extraction because of the extractives evenly distribution between wood types and the faster growth rate of lodgepole pine. Fractionation and selection of heartwood and sapwood may optimize the industrial applications (e.g. biodiesel production) of each fraction and add value to the overall economy of pine silviculture.

21 Example of wood-based biodiesel SunPine, a company in Sweden: (2010) producing m 3 crude tall oil diesel per year from pine an associated plant for an annual production of tons of resins. UPM-Kymmene Corporation in Finland: (2015) Annual renewable diesel production: 100,000 tonnes/120 million litres

22 TALLRAFF Project Characterization and selection of tree and wood fractions for biorefinery applications

23 Aim of TALLRAFF project The objective of the project is to prepare for an optimal allocation of fractions for future sugar and lignin platform applications.

24 Chemical Characterization Needles SLU/LU LU Assessment of pretreatment, sugar yields in hydrolysis and inhibitory properties for fermentation, SLU Wood samples (from stands) Branches Juvenile wood Heartwood Reaction wood Pretreatment (to enable hydrolysis to recover sugars ) Solid fraction liquid fraction SLU Model predictions Allocation strategies Hydrolysis Monosaccharides, Extractives, Lignin

25 Clear-cut stand (slow growth, 1-3) Thinning stand (fast growth, 4-6) Parameter Tree 1 Tree 2 Tree 3 Tree 4 Tree 5 Tree 6 Tree age (an. rings at 1.3m) Tree height (m) Green crown proportion (%) Stem diameter at 1.3m (cm) Stem volume on bark (m 3 o.b.) Dry weights (kg) -Tree (total) -Branches -Bark -Needles -Branch whorls -Sapwood -Heartwood -Pulpwood -Timber

26 Several tree fractions Needles Branches Sapwood 1.3 m, 50%, 75% Heartwood 1.3 m, 50% Knot wood Bark Needles Knot wood Sapwood Heartwood Branches Bark Batches at the freeze house

27 Raw material composition

28 Total fatty and resin acids concentration Total fatty acids and resin acid conentration (ug/g biomass) branches needle bark sap wood 1,3m heart wood 1,3m sap wood 50% Different fractions of tree Tree 1 Tree 5 Tree 4 heart wood 50% sap wood 75% knots

29 Total fatty/resin acid in extract Tree fractions Total Fatty acid and Resin acids in extract (%) Tree 1 Tree 5 Tree 4 Branches Needle Bark Sap wood 1,3 m Heart wood 1,3 m Sap wood 50 % Heart wood 50 % Sap wood 75 % Knots

30 Total fatty/resin acids in different fractions Total Fatty and Resin acid (µg/g of biomass) Branches Needle Bark Sap wood 1,3 m Heart wood 1,3 m Sap wood 50 % Heart wood 50 % Sap wood 75 % Knots Tree 1 Tree 2 Tree 3 Tree 4 Tree 5 Tree 6

31 Conclusions In Branches, heart wood (1.3m) and knots high concentration of total fatty and resin acids High fatty and resin acid in extract in heart wood (1.3m) from tree 1 and 4 Optimization or more biomass needed

32 CETEX Project Cost-Effective Tailored EXtraction of high-value chemicals from low-cost conifer biomaterials

33 Aim of CETEX project to develop green and efficient processes for isolation of chemicals from tree/wood fractions for production of sustainable bio-based chemicals. quantitative analysis of chemical compounds in different fractions (stump heartwood, cones, branches, bark, and needles)

34 Supercritical and microwave extraction

35 Extraction yields (%) from supercritical CO 2 -extraction of lodgepole pine Cones Needles Branches Bark Stem top Stem base Tree no 1, CO Tree no 1 = small tree, mountainous region Tree no 1, CO2+EtOH Tree no 2, CO Tree no 2 = big tree, mountainous region Tree no 2, CO2+EtOH Tree no 3, CO2 no Tree no 3 = small tree, lower region Tree no 3, CO2+EtOH no Tree no 4, CO2 no Tree no 4 = big tree, lower region Tree no 4, CO2+EtOH no Extraction yields (%) from hexane extraction of lodgepole pine Cones Needles Branches Bark Stem top Stem base Tree no Tree no 1 = small tree, mountainous region Tree no Tree no 2 = big tree, mountainous region Tree no Tree no 3 = small tree, lower region Tree no Tree no 4 = big tree, lower region

36 Extraction yield Cones Branches Needles Bark Stump heartwood * - Bark, from logs with large diameter ** - Bark, from logs with small diameter

37 Content of extractives in cones

38 Terpenes and derivatives

39 Resin acids

40 Content of extractives in needles

41 Content of extractives in bark

42 Biplot of fatty/resin acids

43 Carbohydrates Cellulose % Lignin% 10 0 Cones Branches Needles Bark large diameter Bark small diameter Stump heartwood

44 Relevant publications Arshadi, M., Hunt, A.J. and Clark, J.H Supercritical fluid extraction (SFE) as an effective tool in reducing auto-oxidation of dried pine sawdust for power generation. RSC Advances, 2 (5), Arshadi, M., Backlund, I., Geladi, P. and Bergsten, U Comparison of fatty and resin acid composition in boreal lodgepole pine and Scots pine for biorefinery applications. Industrial Crops and Products, 49, Backlund, I., Arshadi, M., Hunt, A.J., McElroy, C.R., Attard, T.M. and Bergsten, U Extractive profiles of different lodgepole pine (Pinus contorta) fractions grown under a direct seeding-based silvic.ultural regime. Industrial Crops and Products, 58, Sara Johansson, Karin Carlqvist, Rashmi Kataria, Thomas Ulvcrona, Urban Bergsten, Mehrdad Arshadi, Mats Galbe, Gunnar Lidén, Implications of differences in chemical properties of stem fractions of Scots pine for use in biorefineries, Wood Sci Technol (2015) 49: Thomas M. Attard, Mehrdad Arshadi, Andrew J. Hunt, Calle Nilsson, Vitaliy L. Budarin, Elizabeth Valencia-Reyes, and James H. Clark. Impact of supercritical extraction on solid fuel wood pellet properties and off-gassing during storage, 2016, Green Chemistry, page 1-9. DOI: /c5gc02479j Ingegerd Backlund, Cost-effective cultivation of lodgepole pine for biorefinery application. Doctoral Thesis, 2013:81.

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