Reuse residues:Adding value to the food supply chain

Nicoletta Ravasio

Socio economic transitions

OCSE: 30% in 2030

$ 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

make use dispose

Linear economy

make use dispose

8 Milionstonn/year

1.900.000 tonn/year

900.000tonn/year

Agro-industry wastes

Spirits from marc511 aC

Pectines from fruit peels1934

Traditional valorization

Biogas production 1990

Cellulose

Proteins

Oil

Sterols

The green chemistry approach

Valorisationβ - glucan

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

MeOH +Sulfuric Acid

< 0.5% FFA

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

Oil Splitting

Esterification reactions

Lubricants

Monoglicerides

sterolesters

Sugar esters

Tannin esters

Non ionic surfactants from tannic acid and fattyacids

J. Surfact. Deterg. 16 (2013) 767

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

The integrated approach

All residues are valorized

Low and high added value products are obtained

RiceRes

RiceRes

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

Materials from husk

• husk + PLA or PHA• Silica + PLA or PHA• End of life

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)

Monoglycerides

Emulsifiers,

preservatives, additives in

food

cosmetics

pharmaceuticals

E 471

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

Sterols from gamma orizanolWP1

Plant waxes in oleogels

JAOCS 2009, 86, 1163RSC Advances 2015, 5, 50259

LWT - Food Sci. Techn. 2016, 68, 477

Rice Bran Oil

Defatted Bran

Waxes γ - orizanol

Proteins

polysaccharides

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

Oil

Defatted BSG Proteins

ArabinoXilans

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

Conclusions

• Socio-economic transitions push to re-think our rawmaterial pool

• Agro-industry wastes can play a significant role in thisscenario

but

• We have to use Green Chemistry tools

N. RavasioNicoletta Ravasio