$ B
illio
ns
0
20
40
60
80
100
2010 2011 2012 2013 2018
Non energeticbioproducts
EnergeticBioproducts
Biorefinery Products: Global MarketsBCC Research, april 2014, EGY117A
A. Rodin, The thinker
Global Biorefinery Products market is accounted for $485.70 billion in 2015 and is expected to reach $1128.17 billion by 2022 growing at a CAGR of 12.57%
Stratistics MRC, october 2016
Spirits from marc511 aC
Pectines from fruit peels1934
Traditional valorization
Biogas production 1990
Oils and fats from food wastes
animal fats
acidic oils from refining of food grade
oils
Used cooking oils
Grape pomace
Tomato pomace
Pumpkin seeds
Rice bran
Spent coffee ground
Brewer spent grain
The problem of acidic oils
COO
COO
COO CH2
CH2
CH2
COOH
C18:2+
6-20 % for animal fats
60-80 % for FA from refining
Deacidification of acidic oils over SiO2- ZrO2
Oil Starting acidity Final acidity
1% oleic acid in rapeseed 0.98 0.16
3% oleic acid in rapeseed 3.33 0.27
Tobaccoseed 3.33 0.50
Raw fish oil 4.53 0.34
5% oleic acid in rapeseed 5.64 0.32
13% oleic acid in rapeseed 12.85 0.39
Chicken fat 18.60 2.51
20% oleic acid in rapeseed 19.60 0.59
30% oleic acid in rapeseed 29.06 1.59
1h, 180°C, MeOH/oil = 10/1
R. Psaro, N.Ravasio, F.Zaccheria, PCT/EP2008/062255 (2008); WO 2009037226 A1
Esterification+transesterificationwith MeOH over SiO2-ZrO2
0
10
20
30
40
50
60
70
80
90
100
1 2 3
%w
t
TG
FFA
DG
MG
FAME
0 1 h 6 h
B
iod
iese
l
Reduced Biodiesel and glycerine washingand purification steps
Transesterification + Esterification of Acidic Oils
0
20
40
60
80
100
1 2 3
% m
ol
TG
FFA
DG
MG
FAMEStarting material First run – 1 h Second run – 1 h
Transesterification + Esterification of Acidic Oils
0
20
40
60
80
100
1 2 3
% m
ol
TG
FFA
DG
MG
FAMEStarting material First run – 1 h Second run – 1 h
FFA FFA FAME MG DG TRI
53.7 7.4 79.8 16.6 0.9 1.6
7.4 1.2 97.2 0.7 0.5 0.5
B
iod
iese
l
Sugar esters
C. antarctica form B
Novozyme 435
HLB 6-8
Wetting agent, water in oilemulsifier
L (+) arabinose
O
O
O
O
7 7O
O 7
7
4
O
O
PolyurethanesEpoxy 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
Milling
Rice husk
Hulling
Whitening
Extr
act
ion
Rice bran oil
1 tonn
Rice bran
70 kg
200 kg
1. 35 tonn
WP2 Insulating materials for green-building
It. Pat. Apl. GE2012A000028 (07.03.2012),granted 05.09.2014, n. 0001410155
• Waste wool
• rice straw
Rice strawProduces CH4 when tilled back into the fiels
Open field burning phased out in many countries as it produces 23 Kg/ha PM10
Waste woolSPECIAL WASTE(Cat. 3 EC Regulation No 142/2011)
L.O.I. (Limiting Oxygen Ind.) > 25 %Contains ca. 3% of sulfur
Straw composites
Different behaviour in alkaliCNR-ISMAC BI
WP2
LantionineCistine
Alkali
Straw composites
- Partial hydrolisis of cheratine- Partial degradation of wool fiber forming an adhesiveproteic matrix- Formation of lantionine
CNR-ISMAC BI SEM 500x
WP2
A comparison
Polystyrene panels:
• Free-standing• Thermal Cond. (λ) ≈ 0.03 W/m
o
K• low cost• low density
• fossil based• Not recyclable• Very bad fire behaviour
Wool materials:
• Excellent fire behaviour• recyclable and compostable• produced from waste renewable materials• Thermal Cond (λ) ≈ 0.05 W/m
o
K
• Not free-standing• higher cost
Wool&Straw panels:
• Free standing!• Good fire behaviour• Highly perspirant• Suitable for anti-sismic building• reciclable and compostable• produced from waste renewable materials•Thermal Cond.(λ) ≈ 0.05 W/m
o
K
• higher cost
WP2
Silica from vegetables: Phytolits
Silica increases a tyre’s wet grip and cuts its rolling resistance by around 30%. That translates into a 5-7% reduction in fuel consumption.
Rice(MMT)
Bran(MMT)
Oil potential(MMT)
Oil actual(MMT)
China 131.186 9.18 1.84 0.090
India 89.178 6.24 1.25 0.820
Indonesia 42.954 3.01 0.60 --
Bangladesh 31.832 2.23 0.45 0.002
… … … … …
World 455.707 31.90 6.38 1.20
Source: www.fao.org/crop/statistics/en. Accessed 10 September 2012A. G. Gopala Krishna, INFORM 2013, 24(4), 260-265
Unexploited potential
Too Acidic !!! (Rancid)
Rice bran oil + glycerol
Esterification
Transesterification
SiO2-MOx
Catalyst Starting FFA StartingTG
FinalFFA
MG%
DG%
TG%
SiO2-TiO2 84 16 4.8 43.3 56.7 0
OCOR
OCOR
OCOR
+ RCOOH OCOR
OCOR
OH
+ OH
OCOR
OH
+OH
OH
OH
Zaccheria et al. Chem. Biol. Technol. Agric. (2015) 2, 23-30
HO
O
HO
O
HOOC
HOOC
+
Scheme 1 – Dimerisation reaction via Diels-Alder cyclisation
Nicoletta Ravasio
Fatty acid composition (%)
C16:0 C18:0 C18:1 C18:2 C18:3
16.8 1.6 40.2 39.5 1.9
Added value from the oilWP1
Gamma orizanol
• Anticholesterolemic• Cosmetic agents• UV filters• Antitumoral agents
Added value from the oilWP3
Plant waxes in oleogels
JAOCS 2009, 86, 1163RSC Advances 2015, 5, 50259
LWT - Food Sci. Techn. 2016, 68, 477
Organolectic
properties
Biological
properties
Infant formulas
Functional
properties
foaming, surfactant,
emulsifying action
Umami taste
Hydrolysed Vegetal Proteins - HVPs
Functional foods, cosmetics, taste enhancers
Oil
DFB
Xilanases, Phytases
Protein from defatted branWP4
0
1
2
3
4
5BITTER
SWEET
SOURSALT
UMAMI
MSG
UMAMIZYME TREATED
FLAVOURZYME TREATED
Protein from defatted branWP4
«Generally recognised as safe»
L. Bagnasco, V. M. Pappalardo, G. Speranza, et al. Food Res. Int., 2013, 50(1), 420-427.
α-1,3-L-arabinofuranose residues
linked on position O3 (mono-
substitution) and on position O2
and O3 (di-substitution)
β-(14)-linked D-xylopiranose chain
Arabinoxylan rice bran (MGN-3/Biobran) provides protection against whole-body γ-irradiationJournal of Radiation Research 2013, 54, 419–429
WP1 Rice Bran poly-saccharides
Parabenfood and cosmetics
oral care productssost. Triclosan
Antioxydants Antibacterial and antifungal agents
BHT E321
BHA E320
Metabolits potentially carcinogenics. Max 0,02% (FDA)
Poultry Sci, 2016, 95, 2435-2440