VOSOLUB PROJECT

New formulations of sunflower-based bio-lubricants with high oleic acid content

XAVIER PAGES-XATART-PARES, ITERG ‘S Technical Manager

x.pages@iterg.com

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CTI for producers and transformers of fats and oils

Authority : French Ministry for Finance, Economy and Employment

2012 Budget : 6.3 M € Staff : 78 ISO 9001: 2000 certification

ITERG: French CTI (Technical Industrial Centre)

Le Réseau

de l’Excellence Technologique

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Quality & safetyof products

Green ChemistryAnd Process

Technology Refining

Nutrition, metabolism& Health

Industrial environmentAnd Safety - Analytical Controls

- Production, made-to-order refining

- Research & Development

- Audit

- Watch & Information

- Professional Training

A synergy of competences Services provided

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Challenges of green chemistry

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To save fossil resources

To participate efficiently to the reduction of greenhouse gas emission

To offer to chemical industry opportunity of developing more respectful processes of the environment and often

less expensive (REACH)

To offer an additional outlet to the field of crops andan opportuny of agricultural development

To propose opportunity of innovation with completely new products

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CEDOP plateform

A European Research and Development Centre for the industrial-scale production of bioproducts and green chemistry processes (8,8 M€)

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Seeds

Crude oils

Refined oils

Bioproducts

Oilseed crushing

REFINING

CEDOP PLATEFORM

Bioproduits

Raw materials to bioproducts

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Customized production of finished products for niche industries

Transferring processes from laboratory-scale to pilot-scale production, scale-up and process

validation including economical and environmental evaluation

Coordinating and implementing Research & Development programmes aimed at developing

new processes and bioproducts

Industrial pre-production models for wide-scale and/or test market formulation testing

Our services

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Biosolvents

BiosurfactantsBiolubricants

Biopolymers

CosmeticsGMP dedicated

technology

Markets

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Biocides & innifuges

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LUBRICANTS

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5 Milions tons

95%

30%

2006

80% PME

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Plant based lubricants have a number or inherents qualities that give them advantages over petroleum oils :

reduce impact on human health and environment use of renewable resources

But , first of all : Technical performances are needed for the wide range of

applications COST has to be under control ! fats and oils have to be managed,…… « differently »

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BIOLUBRICANTS

SoapsGlycerol

Free FA"Partial" glyceridesGlycerol

CH2 - O - C - R1

O

CH2 - O - C - R3

O

R2 - C - O - CH

O

Fatty acid (-COOH) + Alcool (-CH2OH) Ester (-COOC-) + H2O

ester bound

Fats and Oils main components areTriglycerides

The acid function of 3 fatty acids will react with the 3 alcohol functions of glycerol, building triglycerides out of a new kind of bound called “ester“

Glycerol

Fatty acids

Under certain conditions, the ester bound may be

disrupted by

hydrolysis

saponification

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Fats and Oils main componentsFatty acids

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A fatty acid is composed of carbon (C), hydrogen (H) and oxygen (O) atoms, organised in long hydrocarbonated chains:

The majority of fats and oils contain fatty acids with 16 and 18 C atoms

Stearic acid

18 C & 0 double boundOleic acid

18 C & 1 double bound

Linoleic acid

18 C & 2 double bounds

- Linolenic acid

18 C & 3 double bounds

BUT,"double bounds"

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2 or 3

AND"acid

function"

Double bounds and acid functions chemically mean reactivity

One of the most important barriers to the adoption of biolubricants onto the market is their higher price compared to mineral oil based lubricants. In order to improve the market penetration of biolubricants, it is therefore necessary to decrease their purchase cost. The formulations tested in VOSOLUB project use new bases (developed in the framework of IBIOLAB project) that are obtained from:

A new variety of oil seeds: very high oleic sunflower seeds give an oil with a very good resistance to oxidation and good flow properties.

A new refining process: a soft refining process is used instead of complete and classical refining (reduction of the processing costs due to the tailoring of refining to oils and elimination of useless steps).

The new variety of oil seeds in combination with the soft refining process allow to obtain base oils with high stability, with a low impact on the environment and at a lower cost compared to polyolesters.

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BIOLUBRICANTS : REQUIREMENTS

Creating an active European SMEs network specialized in biolubricants production ensuring the supply of the very high oleic sunflower base oil at a competitive market price.

Testing under real operating conditions formulations of sunflower-based biolubricants with high oleic acid content. These formulations (including hydraulic fluids, greases, and neat oil metal-working fluids) will be tested in three European demonstrating sites).

Evaluating and comparing the technical performance and environmental impacts of the sun-flower-based formulations with the corresponding mineral ones.

Fostering the transfer of the VOSOLUB results at the European scale through a dissemination plan relying on an information campaign promoting the use of bio-lubricants

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VOSOLUB PROJECT : OBJECTIVES

The formulations that will be evaluated in VOSOLUB have been previously developed in the framework of IBIOLAB project (Improvement of BIolubricant Manufacturing and Development thanks to the Obtaining of EcoLABels in a wide Range of Industrial Sectors , FP6). This collective research project brought together 22 partners who represented the whole spectrum of the biolubricant sector – SMEs, R&D performers and associations -from seven countries.

This project has been selected as excellent project and sucess story

2 new formulations (hydraulic fluids and grease) of sunflower based bio lubricants are already eco-labelled Ibiolab project has been done to reach the necessary specifications to obtain European ecolabel for lubricants

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VOSOLUB PROJECT : PREVIOUS EXPERIENCE

VOSOLUB PROJECT: PARTNERS

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it is important to target very high quality crude oil, high in c18 :1, high in tocopherols and adapted to mild refining,

The High Oleic variety sunflower seed comes from special breeding by specialized planting seed breeding companies (without the use of genetic modification). Because of its low content of polyunsaturated fatty acids (linoleic) while its high content in monounsaturated fatty acids (oleic), the oil from high oleic sunflower seeds has an enhanced fluidity (even at low temperatures) and a better stability (even at high temperatures). The cold flow properties are also further sustained by the low presence of stearic and palmitic acids.

This variety is provided by ARTERRIS with quality control allowing to obtain good quality seeds (low in FFA)

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Obtention of VHOSO for lubricant application

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For the consumer (edible use)• to provide “good

quality” oil satisfying its actual wishes (colorless, limpid, no odour, no taste,...)

For Industrials • to provide good

quality oil with high shelflife and characteristics conform to specifications

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Soft Refining of VHOSOAim of the refining of vegetable oils

The objective of the refining is to remove « objectionable components »

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Free fatty acid < 0,05% 0,1% AO

Moisture < 0,05% 0,1%

Insoluble matter Max 0,01% absent

Peroxide value (meq 02/kg) < 1 ……. < 0,5

Phosphorus 1 ppm max / 5 ppm max

Taste Neutral / no taste

Color 1,5r / 15y (Lobibon 5p 1/4)

Soap < 10 ppm < 5 ppm

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Typical refined oil quality sheetgeneral specifications

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Iron Max 400 ppb / 100 ppb

Copper Max 50 ppb / 10 ppb

Pesticides Non detectable

Waxes Cold test negative

PAH total 25 ppb max

Heavy PAH 5 ppb max

Benzo a pyrene Max 1 ppb

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Typical refined oil quality sheetcontaminants

Sometimes found in industrial quality sheets Metal traces : nickel, cadmium, lead arsenic, mercury

(max 0.1 to 0.02 ppm)

Microbiological characteristics • total viable count (<1000 per gram) ,entero bacteria, • moulds, yeasts, lypolytic bacteria (<10 per gram)

and also PRODUCT SPECIFICATIONS IV, fatty acid composition, melting point,

N20, rancimat,…...

Typical refined oil quality sheetOTHER SPECIFICATIONS

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Chemical Refining

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Reactives used

Phospholipides

Free fatty acid (soapstocks), phospholipides, H3PO4, métal traces, some pigments, oxidation products some contaminants

H3PO4 (H2O)

Phosphoric acid

NaOH

Caustic soda

water

Crude oil

Water degumming

Acid conditioning

Neutralization

Reactives used Removed compounds

Chemical refining

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REFINED OIL

Filtration

Dewaxing(sunflower)

Washing water(soapstocks, phospholipides)

water

Flavors, tasty compounds,pesticides

Vapor, vacuum

High temperature

BlanketingNitrogen

Coloured pigments , soap traces, phospholipides traces,Polar oxidation products

Activated bleaching clays

Drying (vacuum)

WashingsCentrifugation

Bleaching

Deodorization

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SOFT REFINING a process of purification of the chosen raw materials adapted to each targeted application,

allowing to obtain oils with high stability , high tocopherols content

presenting the lowest impact on the environment and a reduced cost

No washings, no centrifugal separation,

No waste water, 20% solid residu , -25/30 % energy

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Soft refining of VHOSO

Soft deodorisation :

under vacuum, vapour, 160°C, 2h

Trisyl treatement :

addition of water (0,3%) and trisyl (0,5%), under vacuum, 70°C, 30 mn

Drying :

under vacuum, 80°C, 10 mn

Acid conditioning :

80°C, 45 mn, 0,2% citric acid (concentration = 50%)

Composition and characteristics(Vosolub – WP2 & 4 specification and evaluation- V. Bouillon BfB Oil Research 28/03/12)

Tests Unit Methods Specification requirements

Fatty acids content & composition % (m/m) ISO 5508/5509 Min 88% oleic acid

Tocopherols composition and contents Mg/kg ISO 9936 > 600

Triglycerides polymers composition and content % (m/m) ISO 16931 Max 3

Peroxide value Méq02/kg ISO 3960 Max 1,5

Metals by ICP-OES Ppm ASTM D 5185 Expected P, other metals < 5

Acid number Meg KOH/g ASTM D 664 Max 2

Water content % (m/m) Karl Fisher Max 0,1

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Specification requirements on soft refined oil

Specification Requirements on Base oil

Properties Tests Unit Methods Specification requirementsFatty acids composition and content % (m/m) ISO 5508 / 5509 min 88 % oleic acid

Tocopherols composition and content mg/Kg ISO 9936 > 600

Triglycerides polymers composition and content % (m/m) ISO 16931 Max 3

Iodine value cg I2 / g ISO 3961 Max 100

Peroxide value méqO2/kg ISO 3960 Max 1,5

Metals by ICP-OES mg/kg ASTM D 5185 Exepted P, other metals < 3

Acid number mg KOH/g ASTM D 664 Max 1,2

Water content % (m/m) Karl Fisher Max 0,1

Kinematic viscosity at 0°C mm²/s ISO 3104 Convenient for formulated products

Kinematic viscosity at 40°C mm²/s ISO 3104 Convenient for formulated products

Kinematic viscosity at 100°C mm²/s ISO 3104 Convenient for formulated products

Viscosity Index ASTM D 2270 min 190

Cloud point °C ASTM D 2500 min -10

Pour point °C ISO 3016 min -15 (Better -20°C)

Low temperature stability 7 days at -10°CViscosity change (%)

ASTM D 2532 Initial viscosity ± 10%

PMCC flash point °C ASTM D 93 min 200

COC flash point °C ASTM D 92 min 220

Fire point °C ASTM D 92 min 250

Autoignition point °C ASTM E 659 min 350

Noack volatility loss at 150°C %(m/m) ASTM D 5800 mod Max 2

Composition and characteristics

Viscosity

Cold properties

Hot Properties

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THANK YOUFOR YOUR ATTENTION