Sassari, 5 maggio 2015

Fiber plants based biorefineries:

The VeLiCa project

“From ancient crops

materials and products for the future”

VeLiCa

www.velica.org

02/2011-07/2013

Varietal selection

scrutching

pressing

Oil

Fiber

Biofuels

Lubricants

polyols

ω-3, ω-6

Varietal selection

Protein hydrolisates

scrutching

Biomass

Oligomers and sugars

Pressing

Oil

Fiber

Green building materials

Flax

Hemp

Linoal Carmagnola

Valoal Carmagnola Sel.

Kaolin Fibranova

Solal Futura

Festival Felina

Merlin Fedora

Natural Ferimon

Flax and hemp in Lombardy

Up to 2,30 tonn/ha Up to 0,55 tonn/ha

Up to 15 tonn/ha (biomass)

monoics

Linoleic acid (18:2n-6)

(LA)

α-Linolenic acid (18:3n-3)

(ALA)

V. M. Pappalardo, D. Ubiali et al. “Preparation of PUFA concentrates as acylglycerols via enzymatic hydrolysis of hempseed oil”, Eur. J .Lip. Sci. Techn., 2014, 116, 1496-1504

ForumAlpinum 2014

The oil

O

O

O

O

7 7O

O 7

7

4

Selective hydrogenation

Increases oxidative stability Preserves cold properties

The issue of polyunsaturation

F. Zaccheria, R. Psaro, N. Ravasio, Green Chemistry, 11 (2009) 462

Cu cat Ni cat

Hempseed methylesters

t min

C18:3 C18:2 C18:1 C18:0 C16:0 CN* IV # Pp§ (°C)

Initial composition 17.3 57 13.2 2.8 6.4 43 164 -20

After Hydrogenation 100’ - 40 50 2.9 6.3 51 118 -13

Flaxseed methylesters

t

min

C18:3 C18:2 C18:1 C18:0 C16:0 CN* IV # Pp §

(°C)

Initial composition 58.2 16.7 16.3 3.4 5.4 36 186 -23

After Hydrogenation 30’ - 27 63 4.2 5.3 53 112 -11

*CN (Cetane number) – is an indicator of the combustion speed of diesel fuel. According to EN14214 should be > 51 # IV ( Iodine value) – The lower the IV the higher the oxidative stability. EN14214 ≤ 120 § Pp (Pour point ) – Low Pp stands for good cold properties.

F.Zaccheria, N.Ravasio, P.Bondioli, Eur.J.Lip.Sci.Techn. 114 (2012) 24-30

Idrogenazione selettiva: il lino e la canapa Stabilization of the oil: Biodiesel

CH2OH

CH2OH

CH2OHH3CH2C +Acid Catalyst

+ 3 H2O

Triester, TEFatty acid

HO

O

n

CH2O

H3CH2C

CH2O

CH2O

O

13

O

13

O13

TMP

Catalysts t (h) Alcohol Conv. %

SiO2-ZrO2 6 TMP 99

SiO2-TiO2 8 TMP 97

SiO2-Al2O3 8 TMP 96

SiO2-ZrO2 6 NPG 91

SiO2-ZrO2 6 PE 99

S. Brini, R. Psaro, M. N. Ravasio, F. Zaccheria, PCT Int. Appl. (2014), WO 2014006595 A1 20140109.

Solid acid catalysts for the esterification of fatty acids with polyols

Biolubricants

Sel. to triesters up to 95 %

Modified Sturm Test OECD 303A, ISO 11733 (CONFIRMATORY TEST)

Reference 20% vegetable oil 20% hydrogenated oil

S. Dworakowska, D. Bogdal, N.Ravasio, F.Zaccheria, Catalysis Today, 2014, 223, 148– 156

Polyurethane foams

O

O

O

O

7 7O

O 7

7

4

O

O

Polyurethanes

Epoxy resins

Acrilic resins

Exploit the presence of polyunsaturation

Exploit the presence of polyunsaturation

O

OR

OR

O

O

RO

RO

O

O

RO

RO

O

Higher reticulation, thermosetting resins, polyurethanes………………

O

OR

OR

O

Hydrolysed Vegetal Proteins - HVPs

Functional foods, cosmetics, taste enhancers

Organolectic

properties

Biological

properties

Antioxidants,

antinfiammatori,

anti ipertensivi

Functional

properties

foaming, surfactant,

emulsifying action

Umami taste

Oil

cake

Enzymatic hydrolisis

Protein fraction from the meal

0,0

1,0

2,0

3,0

4,0BITTER

SWEET

SOURSALTY

UMAMI Umamizyme 1 h

Umamizyme 5 h

Umamizyme 11 h

Umamizyme 24 h

0

1

2

3

4BITTER

SWEET

SOURSALTY

UMAMI Flavourzyme 1 h

Flavourzyme 5 h

Flavourzyme 11 h

Flavourzyme 24 h

Protein fraction of the meal

Mucilage is a typical constituent of secondary cell wall of plants

Polysaccharide components: neutral (arabinose, xylose, galactose)

acidic (rhamnose, fucose, galactose, galacturonic acid)

Polysaccharides from the meal

Water extraction from the meal (after mechanical pressing) is the best method to obtain sample with high swelling abilities.

G. Speranza et al., Food Chemistry 148 (2014) 60–69

scrutching

Fiber

Oil

pressing

Technical fiber from the plant grown up till maturity and macerated on the field.

Unsuitable to produce textiles

Waste wool SPECIAL WASTE (Cat. 3 EC Regulation No 142/2011) L.O.I. (Limiting Oxygen Ind.) > 25 % Contains ca. 3% of sulfur

Green building materials

Different behaviour in alkali CNR-ISMAC BI

Lantionine Cistine

Alkali

Green building materials

- Partial hydrolisis of cheratine - Partial degradation of wool fiber forming an adhesive proteic matrix - Formation of lantionine

CNR-ISMAC BI SEM 500x

Green building materials

CNR-ISMAC BI

M. Bianchetto Songia, A. Patrucco, M.N. Ravasio, C.Tonin

“Composite of natural origin and method for its preparation” Italian Pat. Appl. GE2012A000028 (07.03.2012), Granted 05.09.2014 n. 0001410155

PARAGONIAMO….

Polystyrene panels: • Free-standing • Thermal Cond. (λ) ≈ 0.03 W/m

o

K • low cost • low density • fossil based • Not reciclable • Very bad fire behaviour

Wool materials: • Excellent fire behaviour • reciclable and compostable • produced from waste renewable materials • Not free-standing • Thermal Cond (λ) ≈ 0.05 W/m

o

K • higher cost

Wool&Hemp panels: • Free standing! • Good fire behaviour • reciclable and compostable • produced from waste renewable materials • Thermal Cond.(λ) ≈ 0.05 W/m

o

K • higher cost

CNR-ISMAC BI

New combinations….

A path to green L-(+)-lactic acid production

Bacillus coagulans

XZL4 US 20130143286

Total recovery 0.42 g/ghemp hurds

ee >99%

Productivity C5 1.08 g/Lh

C6 1.79 g/Lh

PolyLacticAcid

G. Ottolina, S.Riva et al., ChemSusChem 2014, 7, 1991

Bioresource Technology, 2015 in the press

C6 0.99 g/g

C5 0.95 g/g

The final residue…..

The VeLiCa biorefinery ……

…resulted in the creation of a portfolio of bio-based products

cutting across many market sectors as well as of a portfolio of

innovative processes for the exploitation of all the parts of the plant

…demonstrated that it is possible to obtain new, high added-value

products from residues thus making again profitable the cultivation of

hemp and flax

…catalyzed the creation of a network of scientists with

complementary expertises

…allowed to grow up young researchers with “tailor-made” profiles

to work in this field.

The VeLiCa biorefinery ……

2 patents

5 research contracts

2 “son” projects:

1300 ha of hemp sown in 2014

Giovanna Speranza

UniMi Daniela Ubiali

UniPv Claudio Tonin

ISMAC Bi

Tella Galasso

IBBA Gianluca Ottolina

ICRM

The dream team