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Extraction of essential oils from forestry wastes: a contribution to the sustainability of forest management? Catarina Nobre, Margarida Gonçalves, Benilde Mendes UBiA, Departamento de Ciências e Tecnologia da Biomassa Faculdade de Ciências e Tecnologia Erika Santos, Joana Pacheco, Inês Duarte, Domitília Marques CICAE, Instituto Superior Dom Afonso III Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Extraction of essential oils from forestry wastes: a contribution to the

sustainability of forest management?

Catarina Nobre, Margarida Gonçalves, Benilde Mendes UBiA, Departamento de Ciências e Tecnologia da Biomassa

Faculdade de Ciências e Tecnologia

Erika Santos, Joana Pacheco, Inês Duarte, Domitília Marques CICAE, Instituto Superior Dom Afonso III

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

Outline

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Bioenergy production in Europe

Forestry wastes – added value products

Essential Oils & Extraction methods

Hydrolats

Market for essential oils and hydrolats

Experimental procedure

Results

Concluding remarks

How much bioenergy can Europe produce without harming the environment?

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Source:

Valorisation of residual forestry biomass in order to:

• Improve economical viability of forestry activities

• Preserve biodiversity

• Improve forest management:

• Limit fire propagation

• Facilitate the mobility of forest

maintenance teams

Why forestry wastes?

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Type of forest Million ton / year

Forest 2,0

Wood tranformation 0,2

TOTAL 2,2

Type of residue Million ton / year

Bushes 5,0

Timber 0,5

Branches & Leaves 1,0

TOTAL 6,5

Why forestry wastes?

Source: Biomass Workgroup, Agriculture and Sea Comission June 2013

Forestry biomass production

Available forestry residues potential

Forestry biomass

Essential oil extraction

Essential Oil

Hydrolat

Biofuels Pellets

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Branches & leaves

Bushes Waste

timber

Why forestry wastes? Added-

value products

Energy production

Essential Oils

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Volatile, natural, complex compounds Strong odour

Aromatic plants’ secondary

metabolites

Antiseptic, bactericidal, antiviral and fungicidal properties

Essential Oils

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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• Essential oil’s major components determine their properties.

• These components include two groups of distinct biosynthesis.

Terpenes and terpenoids

Aromatic and aliphatic constituents

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Cistus ladanifer Oil • α-pinene (39%) (monoterpene hydrocarbon)

• viridiflorol (11,8%) (oxygenated sesquiterpene)

Pinus pinaster Oil

• β-caryophyllene (30,9%) (sesquiterpene hydrocarbon)

• β-selinene (13,45%) (sesquiterpene hydrocarbon)

• α-pinene (1,29%)

Essential Oils

• Bronchodilator

• Estrogen mimic

• Anti- inflammatory

Sources: Mariotti et al (1999), Mimoune et al (2013)

Monoterpene hydrocarbons 4,63 %

Oxygenated monoterpenes 2,98 %

Sesquiterpene hydrocarbons 75,43 %

Oxygenated sesquiterpenes 2,97 %

Oxygenated diterpenes 0,68 %

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Eucalyptus globulus Oil • 1,8-cineol (63,8%) (oxygenated monoterpene)

Lavandula spp. Oil • 1,8 – cineol (29,70%) • linalool (38,12%) (oxygenated sesquiterpene)

• camphor (16,11%) (oxygenated sesquiterpene)

Essential Oils

• Expectorant • Mouthwash • Insecticide • Baked goods • Beverages

Sources: Silvestre et al (1997), Smigielski et al (2013)

• Hygiene products • Cleaning agents • Chemical

intermediate (Vit. E)

• Anti-microbial • Plasticizer

Essential Oils - Extraction Methods

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Extraction Method

Solvent extraction

Expression

Steam

Distillation

Supercritical fluid

extraction

Microwave assisted

extraction

Enfleurage

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Essential Oils - Extraction Methods

Different essential oils extracted by: Steam distillation - 93% Other methods – 7%

Hydrodistillation: • Easily implemented • Low cost

• Quality oil

Hydrolats

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Isolation of volatile compounds

Hydrodistillation

Solvent extraction

Hydrolat • Subtle aromas • Biologically active

compouds • Antifugical and antibacterial

properties

Essential Oil

Hydrolat

Market for Essential Oils and Hydrolats

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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• Essential oils are extracted from over 3,000 plants.

• About 300 are commonly traded

on the global market.

• These oils are used in different

industries such as cosmetics, pharmaceuticals, foods and households.

20%

20% 60%

Flavour Industry

PharmaceuticalIndustry

FragranceIndustry

Source: Promising EU markets for essential oils

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Market for Essential Oils and Hydrolats

Major EU producers are Mediterranean countries

• France • Italy • Spain • Portugal • Greece

213€/L 52€/L 79€/L 68€/L

Source: www.pronatural.com.pt

C. ladanifer Lavandula spp. E. globulus Pinus pinaster

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Eucalyptus globulus

Cistus ladanifer

Pinus pinaster

Lavandula spp.

Experimental procedure

Portuguese forestry wastes

Experimental procedure

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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1st set of experiments: • 30-70 g of biomass sample • 750 mL of water • 500 mL of collected distilate 2nd set of experiments: • 30 -70 g of biomass sample • 750 mL of water • 300 mL of collected distilate in 50 mL fractions 3rd set of experiments: • 120 - 200 g of biomass • 500 mL of water • 300 mL of collected distilate in 50 mL fractions

Experimental procedure

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Drying, evaporating, redissolving

Results - Hydrodistillation

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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0

500

1000

1500

2000

2500

3000

3500

Oil

Yie

ld

(mg

/g)

Extraction Yield - 1st set of experiments

Eucalyptus globulus 1

Eucalyptus globulus 2

Cistus ladanifer 1

Cistus ladanifer 2

Lavandula sp.1

Lavandula sp. 2

Pinus pinaster 1

Pinus pinaster 2

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Results - Hydrodistillation

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,16

0,18

0,2

0 50 100 150 200 250 300

Oil

Yie

ld (

% w

/w)

Distilled Water Volume (mL)

Cistus ladanifer

Cistus ladanifer 1(W/M Ratio = 7,59)

Cistus ladanifer 2(W/M Ratio = 5,57)

Cistus ladanifer 3(W/M = 1,90)

Cistus ladanifer 4(W/M = 1,50)

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Results - Hydrodistillation

0

0,1

0,2

0,3

0,4

0,5

0 50 100 150 200 250 300

Oil

Yie

ld (

% w

/w)

Distilled Water Volume (mL)

Eucalyptus globulus

Eucalyptus globulus 1(W/M Ratio = 10,60)

Eucalyptus globulus 2(W/M Ratio = 9,28)

Eucalyptus globulus 3(W/M Ratio = 2,19)

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Results - Hydrodistillation Sample

Sample Mass (g)

Distilled Water Volume (mL)

Oil Yield (% w/w) Water : Matrix

Ratio

Eucalyptus globulus

32,00 500 2,98 15,63

137,20 300 0,09 2,19

Cistus Ladanifer

58,83 300 0,67 5,57

200,00 300 0,03 1,50

Lavadula sp. 41,80 500 0,24 11,96

53,60 500 0,15 5,60

Pinus pinaster 54,50 300 0,62 5,50

112,63 500 0,09 4,44

Higher Water/Matrix

Ratio

Higher Oil Yield

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Results - Essential Oil Composition

Eucalyptus globulus cromatographic profile

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Results - Hydrolat Composition

Cistus ladanifer hydrolat cromatographic profile

Forestry wastes can be collected to produce secondary added-value

products.

This action may help to reduce branch density and promote biomass renovation.

In Portugal, forestry wastes have four main potential sources of essential oils and hydrolats: C. ladanifer, Lavandula spp., E. globulus and P. pinaster.

Concluding remarks

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Implementing this sort of procedure may help create more income for

forest owners;

Future work is needed in order to evaluate oil extraction from forestry

biomass mixes.

Concluding remarks

Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014

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Lignocellulosic Crops as Feedstock for Future Biorefineries, Lisbon 26-31 July 2014 27

Thank you for your attention!

E-mail: [email protected]

The authors would like to acknowledge the support of:

PROFORBIOMED

PROPELLET (QREN-INOVAÇÃO)

CMC Biomassa Lda