the velica project - enea
TRANSCRIPT
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
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