1. 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 1LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG

2.  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 2 LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG

3. Quality & safety of products Green Chemistry And Process Technology Refining Nutrition, metabolism & Health Industrial environment And Safety - Analytical Controls - Production, made-to-order refining - Research & Development - Audit - Watch & Information - Professional Training A synergy of competences Services provided 3 LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG

4. Challenges of green chemistry LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 4 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 and an opportuny of agricultural development To propose opportunity of innovation with completely new products

5. 5 CEDOP plateform A European Research and Development Centre for the industrial-scale production of bioproducts and green chemistry processes (8,8 M€) LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG

6. Seeds Crude oils Refined oils Bioproducts Oilseed crushing REFINING CEDOP PLATEFORM Bioproduits Raw materials to bioproducts 6 LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG

7. 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 7 LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG

8. Biosolvents Biosurfactants Biolubricants Biopolymers Cosmetics GMP dedicated technology Markets 8 Biocides & innifuges LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG

9. LUBRICANTS LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 9 5 Milions tons 95% 30% 2006 80% PME

10. 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 » LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 10 BIOLUBRICANTS

11. Soaps Glycerol Free FA "Partial" glycerides Glycerol CH 2 - O - C - R 1 O CH 2 - O - C - R 3 O R 2 - C - O - CH O Fatty acid (-COOH) + Alcool (-CH 2 OH)  Ester (-COOC-) + H 2 O 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 11

12. Fats and Oils main components Fatty acids 12 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 BUT, "double bounds" 0 1 2 or 3 AND "acid function" Double bounds and acid functions chemically mean reactivity

13. 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. LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 13 BIOLUBRICANTS : REQUIREMENTS

14. 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 14 LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG VOSOLUB PROJECT : OBJECTIVES

15. 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 LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 15 VOSOLUB PROJECT : PREVIOUS EXPERIENCE

16. VOSOLUB PROJECT: PARTNERS LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 16

17. 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) LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 17 Obtention of VHOSO for lubricant application

18. 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 LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 18 Soft Refining of VHOSO Aim of the refining of vegetable oils The objective of the refining is to remove « objectionable components »

19. Free fatty acid< 0,05% 0,1% AO Moisture< 0,05% 0,1% Insoluble matterMax 0,01% absent Peroxide value (meq 02/kg)< 1 ……. < 0,5 Phosphorus1 ppm max / 5 ppm max TasteNeutral / no taste Color1,5r / 15y (Lobibon 5p 1/4) Soap< 10 ppm < 5 ppm LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 19 Typical refined oil quality sheet general specifications

20. IronMax 400 ppb / 100 ppb CopperMax 50 ppb / 10 ppb PesticidesNon detectable WaxesCold test negative PAH total25 ppb max Heavy PAH5 ppb max Benzo a pyreneMax 1 ppb LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 20 Typical refined oil quality sheet contaminants

21. 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 sheet OTHER SPECIFICATIONS

22. Chemical Refining LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 22 Reactives used Phospholipides Free fatty acid (soapstocks), phospholipides, H 3 PO 4, métal traces, some pigments, oxidation products some contaminants H 3 PO 4 (H 2 O) Phosphoric acid NaOH Caustic soda water Crude oil Water degumming Acid conditioning Neutralization Reactives used Removed compounds

23. Chemical refining LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 23 REFINED OIL Filtration Dewaxing (sunflower) Washing water (soapstocks, phospholipides) Washing water (soapstocks, phospholipides) water Flavors, tasty compounds,pesticides Vapor, vacuum High temperature BlanketingNitrogen Coloured pigments, soap traces, phospholipides traces, Polar oxidation products Coloured pigments, soap traces, phospholipides traces, Polar oxidation products Activated bleaching clays Drying (vacuum) Washings Centrifugation Bleaching Deodorization

24. 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 LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 24 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%)

25. Composition and characteristics (Vosolub – WP2 & 4 specification and evaluation- V. Bouillon BfB Oil Research 28/03/12) TestsUnitMethods Specification requirements Fatty acids content & composition % (m/m)ISO 5508/5509Min 88% oleic acid Tocopherols composition and contents Mg/kgISO 9936> 600 Triglycerides polymers composition and content % (m/m)ISO 16931Max 3 Peroxide valueMéq02/kgISO 3960Max 1,5 Metals by ICP-OESPpmASTM D 5185 Expected P, other metals < 5 Acid numberMeg KOH/gASTM D 664Max 2 Water content% (m/m)Karl FisherMax 0,1 LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 25 Specification requirements on soft refined oil

26. Analysis results VOSO E4009 crude oil VOSO SR3 E4009 15/01/08 VOSO SR3 E4009 07/03/08 FFA (%)0,520,530,56 PV (meq 02/kg)2,610,5 Tocopherols (ppm)719713700 Rancimat 100°C, 20L/h (h)-22,224,4 Phosphorus content (ppm)31< 34 Fe (ppm)--4 Cu (ppm)--0,007 LUBMAT – 6/8th June 2012 – BILBAO – X. PAGES - ITERG 26 Production of large quantity of mild refined raw material

27. Specification Requirements on Base oil

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