Agro Resource Refining Concept (A2RC) applied to aromatic plants

Thierry TALOUThierry TALOU, Marjorie BERGOIN, Abraham ENDRIAS, Virginie MARECHAL, Marjorie BERGOIN, Abraham ENDRIAS, Virginie MARECHAL

AgroAgro--IndustrialIndustrial ChemistryChemistry LaboratoryLaboratorySENSORIC SENSORIC -- Key Centre in Key Centre in SensorySensory MetrologyMetrology

INP Toulouse / ENSIACETINP Toulouse / ENSIACET118 route de Narbonne 31077 TOULOUSE FRANCE118 route de Narbonne 31077 TOULOUSE FRANCE

Agro Resource Refining Concept

# BIOREFINERY

§ GREEN CHEMISTRY

@TOULOUSE since 1975

A2RC

Toulouse

Toulouse

Agro Resource Refining Concept (A2RC)

KEY WORDS:Sustainable agricultureRenewable resourcesAgro-resources ChemistryChemistry of « renewable carbon »Non Food Valorization aka « VANA »

DEFINITION:Sequential valorization of valuable components of raw plants or processed ones in order to generate by-products in additionto key product

Technical principle: Separation in extracts or raffinates of the different constituents of agro-resources

Economic principle: Transforming waste in by-products then co-products

PlantSeed

Petal

Leave

Stalk

Root

Traditionnal Extraction processes

Lipids

Sugars

Protéins

Secondary metabolites

Products Co-Products

Food Food & Non & Non FoodFoodBioBio--RaffineryRaffinery

SUNFLOWERHelianthus annus

2.0 T/ha

OIL

0.9 T/ha

ANIMALFEEDHIGH DENSITY

AGROMATERIAL

0.5 T/ha

2.5 T/haCARDBOARD

GELLINGAGENT

ESSENCE

LOW DENSITY AGROMATERIAL

1 HECTARE

2360 kg of STALK

BARK2100 kg

PITH260 kg

Agro-matérial3 m3

Paper paste1640 kg

500kgDRY CALYX

1 kg95 kg

Pectins

200 kgOrganicFertilizer

EssentialOil

1kg bulgarian rose absolute= 1,200 EUR1kg bulgarian rose essence = 6,000 EUR

1 kg centifolia rose absolute= 7,000 EUR

AROMATIC PLANTS

3 tons of roses petals hydrodistillated will give 1Kg of rose essence and… 2.999 ton of WASTE

Herbs&SpicesAromatic plants

DIRECT USE Product: 5-20%Waste: 80-95%

PROCESSING

HydrodistillationSolvent extraction

Product: 0.1-5%Waste: 95-99.9%

ConcreteOleoresinEssential Oil

Valorization of WASTE in CO-PRODUCTS

AGRICULTURAL VALORIZATION

Organic fertilizer

ENERGETIC VALORIZATION

Bio Fuel

CHEMICAL VALORIZATION

JASMINEJasminum officinale

1 ton of Jasmine petals = 8,000,000 petals = 1kg of absolute= 15,000 EUR (Grasse origin)= 1,500 EUR (Marocco origin)

Enfleurage Solvent extractionCis-jasmoneLinalolGeraniolBenzyl alcohol2-phenyl ethanolEugenolphytol

AROMATIC POMACE Petals ABSOLUTE1.0 Kg/T

Aromatic precursors

Non odorous aglycons

ExtractionResidue AROMATIC BY-PRODUCT

0.5 Kg/TCis-jasmoneGeraniolBenzyl alcohol2-phenyl ethanolEugenol

Enzymatic hydrolysisβ-glycosidase

Acetate buffer (0.2M, pH5)Enzymatic cocktail Rohament CW1 (1mg/mL)

24h@40°C

CHEMICAL VALORIZATION

HIBISCUSHibiscus sabdariffa

Enzymatic Infusion Solvent Extraction

ALICAMENT AROMATIC EXTRACTPetals

Leaves 1kg/100kg

Enzymatic Infusion Hydrodistillation

COSMETIC OILSeeds

Cold expression

C16:0 21%C18:0: 4%C18:1 37%C18:2 35%

25 kg/100kg

CHEMICAL VALORIZATION

SAFFRONCrocus sativus

1kg

160 000 petals waste : 360kg

Leaves : 1.500kg

+

Stigmas :SAFFRON SPICE

Hydrodistillation

Solvent extractionSolvent maceration

Flowers

Leaves

BulbsOxydation of aromatic precursorsvs Iris (Iridacea species) : ozon, peroxydes

Crocin :C20-caroténoïdRed color

Picrocrocin : No odorousBitter taste

Safranal :Typical flavor developpedduring drying process

O

H

HO

H

HO

OH

H

HH

OH

O

CHO

O

H

HO

H

HO

H

H

OHHOH

OH

+

CHO

O

H

HO

H

HO

H

H

OHHOH

OH

+

CHO

HO

H2O

H+

H+ ou OH-

Picrocrocine

Glucose

HTCC

Safranal

Glucose∆

β-glucosidase

H2O

H2O

4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00

50000

100000

150000

200000

250000

300000

350000

400000

450000

Time-->

Abundance

TIC: P1AM28B4.D

2.75

3.06 3.55 3.73

8.43 13.03 14.11

14.39

14.63 14.72

14.85

15.61

16.05 16.34

16.54

16.71

17.67

18.29 18.41 18.47 18.68

21.39

safranalAcetic acid + 2,3-butanedione

2-methylene-6,6-dimethylcyclohex-3-enal

isophorone

3-hydroxybutane-2-one

dihydroxophorone

cetoisophorone

2(5H)furanone

34 identified volatiles in saffron from Quercy8 main volatiles in saffron

Analytical Analytical profiles : GC/MSprofiles : GC/MS

Panel (10 persons) on 8 caracteristic samples

Aromagramme de l'échantillon 28B

0

1

2

3

4

5

6

7

8

9

10

0 5 10 15 20 25 30

temps de rétention

fréq

uenc

e de

dét

ectio

n

pic 1

pic 14

pic 12

pic 10pic 9

pic 8

pic 7

pic 6pic 5

pic 3pic 2

Aromagramme de l'échantillon 21A

0

1

2

3

4

5

6

7

8

9

10

0 5 10 15 20 25 30

temps de rétention

fréq

uenc

e de

dét

ectio

n

pic7

pic9

pic10

pic14pic13

dry saffrons few odors

least dry saffrons full of odors

Notes : FloralSpicyFattyPungent GreenBreadAnimalFruity

EarthyBluegrassCitrusSulfuratedMildWoodyRoastedIndetermined

Aromatic Aromatic profiles: GC/Oprofiles: GC/O

0

10

20

30

40

50

60Intensité globale

Epicé

Terreux

Renfermé

Grillé

FuméPiquant

Boisé

Sucré

Beurré

Foin/Herbe/Végétal

Iran H=14% Moy H<12% Moy H>18%

12 samples : 11 saffron from quercy1 iran

Global intensity

Spicy

Earthy

Musty

Roasted

Smoked

Woody

Pungent

Sweet

Buttery

Hay/Green

Sensory analysisSensory analysis

Oxydation of aromatic precursorsvs Iris (Iridacea species) : ozone, peroxydes

Solvent extractionSolvent maceration

HydrodistillationFlowers

Leaves

Bulbs

Aromatic products and dyes

Hydrodistillation Hydrodistillation ofof petalspetals

Essential Oil

Aromatic water

Compounds IR %area odours

unidentified 779 2,08

2-[5H]furanone 1036 15,07

2-ethyl-1-hexanol 1049 55,75 Mild sweet florale rosebenzeneacétaldehyde 1053 2,33 Powerful green pungent

phenylethylalcohol 1113 1,94 Mild rose honey

Safranal 1189 1,58 spicy

dihydrocarveol 1226 1,88 Sweet pepper spicy

L-carvone 1238 2,12 Herbaceous spicy

Solvent Maceration Solvent Maceration ofof petalspetals

Extraction :

Diethylether (yield 0.20%-0.30%)Hexane (yield 0.15%-0.20%)

15min, 30min, 60minSolvent

Flowers

To remove waxes using absolute ethanol

Solvent evaporation Concrete

Absolute

0

5

10

15

20

25

30

35

Green

Peanut

Mushroom

Burned

Floral Honey

Pungent Honey

Fresh Honey

Pungent Green

Bread

Animal

Roasted

Fruity

Aromatic productsAromatic productsDiethylether

Hexane

t=60min

t=15 min

t=30minPhenylethyl alcohol

4-hydroxybenzene ethanol

Undecane2-phenylethylester formic acid

05

1015202530354045Green

Peanut

Mushroom

Burned

Floral Honey

Pungent Honey

Fresh Honey

Pungent Green

Bread

Animal

Roasted

Fruity

Dying products Dying products

lypohilic extraction (cyclohexane) yellow – red colors

analysis by HPLC/UV/MS λ=450nm

carotenoids : M= 568, C40H56O2

Esterified Lutein or zeaxanthin

Hydrodistillation Hydrodistillation of of leavesleaves

Essential Oil

Aromatic water

Compounds IR odours %area8h

%area16h

furfural 827 Spicy, groove 1,03

2-hexenal 848 Powerful, green 3,93

2-[5H]-furanone 916 6,58 5,81unidentified 1346 1,32

2,2,6,7-tetramethylbicyclo-[4,3,0]nona-4,9-[1]dien-8-ol

1381 1,15

Dodecanoic acid 1578 Fatty 2,98 1,21

Tetradecanoic acid 1767 1,66 1,48

SolvantLeaves

Extraction :

Diethylether (0.35%-0.70%)Hexane ( 0.20%-0.35%)

3, 5, 7 days

Solvent evaporation Concrete

Solvent Maceration Solvent Maceration ofof leavesleaves

dichloromethanesamples

0,00

1,00

2,00

3,00

4,00

5,00

6,00

5,20 5,35 5,55 6,70 7,67 9,55 9,75 10,15 10,87 11,48 12,06 13,56 14,12 14,62 16,54 19,21 20,70 24,19

I moy 7j I moy 5j I moy 3j

peanut

peanut/animal

peanut

mushroom/earthy

burned

honey pungent

honey

honey

green f loral

honey

floral honey

citrus

citrus honey f loral

hay

green hay hay

citrus

2-[5H]-furanone

nonanal (fatty floral)

phenyl ethyl alcohol (mild honey)

octanoique acide (oily, mild)

alpha terpinéol (mild honey lilac)

coumaran

beta-ionone (woody)

2-hydroxy-beta-ionone

Ether

0,00

1,00

2,00

3,00

4,00

5,00

6,00

Imoy7j

Imoy5j

Imoy3j

peanut

2-[5H]-furanone

peanut

mushroom/earthy

honey f loral

honey pungent green

honey green

honey green

honey hay

honey

roasted hayhay

hay hay

phenylacétaldehyde (powerful green floral)

phenylethyl alcohol (mild rose honey)

dihydro-4-hydroxy-2-[3H]-furanone

coumaran

benzene acetique acide

orcinol

hexane

ether

Aromatic productsAromatic products

Dying products Dying products

lypohilic extraction (cyclohexane) yellow -green

analysis by HPLC/UV/MS λ=450nm

carotenoids : M= 568, C40H56O2 et M=600, C40H56O4 + chlorophyll

Lutein, zeaxanthin and neoxanthin

Industrial FeasabilityIndustrial Feasability::Petals and leavesPetals and leaves@pilot @pilot scale scale 300L 300L

Leaves Petals

Cyclohexane

Petals extractedleaves Cyclohexane

Leaves Petals

0.3kg/100kg 0.2kg/100kg

Leaves

Cyclohexane

extractedleaves

Petals

Cyclohexane

Petals

INDUSTRIAL APPLICATION

1kg

Petals co-product: 0.7kgLeaves co-product : 4.5kg

+

Thank you Thank you for for your your attention!attention!

A2RC