EMERGING APPLICATION FOR NEW TYPES OF INDUSTRIAL LIGNINS

1. EMERGING APPLICATION FOR NEW TYPES OF INDUSTRIAL LIGNINS UNIVERSITY OF TOULOUSE Prof. Dr. Michel DELMAS 134-142, Rue Danton 92593 Levallois Perret Cedex, France  +33 (0)1 41 34 28 50 -  +33 (0)1 41 34 28 60 www.cimv.fr – contact@cimv.fr

2. RESSOURCES : wood, straw, bagasses of sugar cane & sweet sorghum, hemp, flax, miscanthus… World availability of Lignocellulose from agricuture and forestry > 3 billions tons / year Annual market for non foodstuff use < 0,3 billions tons / year

3. 3,5 Billions tons of oil extracted /year

4. BIOMASS & OIL : Competitiveness of the raw material 1 ton of oil in petrochemistry ≈ 1,8 ton of dry straw in agrichemistry 1 ton of oil ≈ 400 € 1 ton of straw ≈ 80 €

5. THE PULP PRODUCTION TODAY MECA WOOD H+ OH- RAW PULP BLEACHING COMMERCIAL PULP WASTES Sugars, Polysaccharides, Lignins, Modified lignins, Résins, Organic oxidised molecules, Minérals, Organic chlorine products... RECYCLING : minerals, energy TREATMENTS SOLID WASTES / DUMP CONTINENTAL RIVERS

6. LIGNOSULFONATES AND KRAFT LIGNINS • Highly condensed materials with high sulfur content produced with the chemical pulps • Industrial use : - Fillers and low grade surfactants < 5 % - Energy > 95 %

7. A TECHNICAL REVOLUTION : THE CIMV PROCESS • The first worldwide refinery on the oil refinery model • The first technology which allows the separation of the three main bio polymèrs naturels without degradation at atmospheric pressure. • Industrial property : 3 internationals patents + 3 new patents in current registration • Complete use of the vegetal matter. 3 commodities produced for a huge worldwide market . • The scaling up from the pilot plant to the factory meets sustainable development requirements.

8. THE CIMV PROCESS Straw, bagasses, wood : Physical conditionning Organic refining Organic acid recycling Organic acid recycling Raw chemical pulp Sugars + Lignins Organic acid solution H2O Bleaching: Peracides / H2O2 NaOH / H2O2 Lignins C5 sugars Commercial chemical pulp

9. CIMV / KRAFT DRY STRAW 80 € / T DRY WOOD 120 € / T Same investment / ton of product. CIMV KRAFT 0,4 to 0,5 T energy 70 € / T 0,4 to 0,5 T of chemical pulp 500 € / T 0,4 to 0,5 T Monomers & polymers 700 € / T 0,4 to 0,5 T of chemical pulp 500 € / T

10. CIMV PILOT PLANT • Localisation of the pilot plant on the site of POMACLE, near REIMS • The pilot plant program has been financed by CIMV (6 M€) with the participation of OSEO-ANVAR, The Regional Council of Champagnes Ardennes and the GIE Céréales Recherches et Développement • Industrial process validated in 2006

12. THE CIMV PRODUCTS : the keys of the future

13. THE CIMV CELLULOSE • Physical and pulping properties close to hardwood commercial pulp set up by the Centre Technique du Papier –Grenoble • A unique position in the market • Due to a production in exemplary economical and environnemental production  0 déforestation, 0 chlorine, small quantity of water, no pollution. • Due to the use of annual plant(straw, sugar cane and sweet sorghum bagasses, miscanthus etc…)which can help to solve the fibers supply regarding the increase of the pulp demand worldwide

14. CIMV PAPER

15. CIMV XYLOSE • Xylose is the most abundent product on earth after glucose but has today very small market : xylitol # 40 000 T/year, furfurol and furfurylic alcool # 200 000 T/year • An unique andnewposition on the market for the CIMV xylose due to a production in exemplary economical and environnemental conditions • furfurol and furfurylic alcool are in our concept key stones of the Agrichemistry

16. Additives for animal feeding • Xylitol • Surfactants • Furfurol and derivatives • Furanic polymers • … XYLOSE

17. PETROCHEMISTRY / AGROCHEMISTRY : the convergent point The most prominent monomers of petrochemistry are : The CIMV process, following the agrichemistry concept, can substitutes them by:

19. SOME FURANICS MONOMERS

20. Bi-substitued furanic monomers

21. Polycondensations Polyester Polyamide Polyuréthane

22. Phenolic resins • Polyuréthanes • Polyesters • Epoxy resins • Adhesives • … CIMV LIGNINS

23. A.Gardziella, L.A. Pilato and A.Knop in the 2nd edition(2000) of their reference book ,” Phenolic Resins” write page 527 and 528 : “ On the basis of its structure, lignins may be considered a kind of phenolic condensate in the broadest sense of the term, making it logical to use it in production of phenolic resins. Pertinent tests involving the use of lignin in various areas have been carried out in the last few years, and some have been successful. At present, it is necessary to wait and see whether the cellulose and paper industry can further develop sulfur-free digestion processes and bring these into large-scale production, since a basic requirement for the use of lignin is generally the availability of sulfur-free, low molecular mass lignins. Such materials are basically available by way of organosolv process. However, the organosolv process, involving organic wood digestion, is currently only used to a limited extent on an industrial scale.”  CIMV will be the first society to give an answer

24. CIMV LIGNINS • Perfect substitutes for phenolic and more widely hydroxyl monomers and oligomers for thermosetting and thermoplastic polymers towards a green plastic industry • A unique position on the market due to a production in exemplary economical and environnemental conditions • New materials without influence on the greenhouse effectwhich can reduce the oil dependence of this industrial sector • As we know the structure and the functionnality of ours lignins, the market price is close to the market price of the corresponding monomers and oiligomers from oil origin.

25. CIMV LIGNINS The molar mass distribution curves of lignin, obtained by Size Exclusion Chromatography show a molecular weights comprised between 1000 and 1500 g/mol. The formyl, acetyl and hydroxyl groups The presence of formyl and acetyl groups comes from the conditions of extraction (acetic acid / formic acid media). The amount of carboxylic groups is about 1,00 mmol/g of lignin.

26. CIMV LIGNINS We have published a complete mass spectrometry analysis on the wheat straw lignins extracted with our technology : • Structural elucidation of the wheat straw polymer by atmospheric pressure chemical ionisation tandem mass spectrometry and matrix assisted laser desorption /ionisation time of flight mass spectrometry; Joseph H. BANOUB and Michel DELMAS Journal of Mass Spectrometry, 2003, 38, 900-903 • Elucidation of the complex molecular structure of wheat straw lignins by atmospheric pressure photoionization quadrupole time-of-flight tandem mass spectrometry ; Joseph H. BANOUB, Bouchra BENJELLOUN-MLAYAH, Fabio ZIARELLI, Nicolas JOLY and Michel DELMAS Rapid Communications in Mass Spectrometry, 2007,21, 2867-2888

27. CIMV LIGNINS

28. CIMV LIGNINS APPI-QqToF-MS of extracted wheat straw lignin

29. CIMV LIGNINS

30. CIMV LIGNINS

31. CIMV LIGNINS

32. CIMV LIGNINS

33. CIMV LIGNINS

34. CIMV LIGNINS

35. CIMV LIGNINS

36. CIMV LIGNINS

37. CIMV LIGNINS

38. CIMV LIGNINS

39. C H + + R C H O H H C R 2 2 2 H C O H + H O O H R R 1 1 O C H O C H H O C H 3 3 3 O H O O O O H C H 2 O C H O C H O C H 3 3 3 O H O O H O O H O O H + O O H + [ C H O ] 2 + [ C H O ] : R = C H O H ; R = H 3 : R = C H O ; R = C H 2 0 1 5 6 [ C H O ] 1 8 1 9 6 1 2 2 1 2 2 . 1 9 1 7 6 + [ C H O ] + 5 + 4 1 8 2 0 8 [ C H O ] : R = C H O ; R = C H + R 6 [ C H O ] 1 9 1 9 6 1 2 3 : R = C H O ; R = C H = C H 2 2 0 1 7 6 1 2 . 7 + 9 : R = C H O H ; R = C H - C H O H - C H O [ C H O ] 1 2 2 2 2 1 2 3 8 + 8 [ C H O ] : R = C H O ; R = C H = C H - C H 2 2 1 1 6 1 2 2 R 1 R 3 C H 2 + O H + O H O H H O H C 2 O O C H 3 O O O H O H O O C H + H 3 O C H 3 O O O H O C H 3 O C H 3 O O H O O H + [ C H O ] 2 5 2 1 7 + [ C H O ] 1 0 2 2 8 8 9 1 1 + 1 2 [ C H O ] : R = C H O H ; R = C H ; R = H 2 8 2 9 8 1 2 2 3 3 + 1 3 : R = C H O H ; R = H ; R = O C H [ C H O ] 1 2 2 3 3 2 8 2 9 9 + 1 7 [ C H O ] : R = C H O H ; R = C H C H O ; R = O C H 3 0 3 1 1 0 1 2 2 2 3 3 + 1 8 [ C H O ] : R = C H O H ; R = C H O H - C H ; R = O C H 3 0 3 3 1 0 3 1 2 2 3 3 + 1 9 [ C H O ] : R = C H O H ; R = C H = C H - C O O H ; R = O C H 3 1 3 1 1 1 1 2 2 3 3 + 2 0 [ C H O ] : R = C H O H ; R = C H - C H - C O O H ; R = O C H 3 1 3 3 1 1 1 2 2 2 2 3 3 Tentative molecular structures of the isolated 57 different specific ions obtained from the wheat straw lignin, recorded in the positive and negative modes APPI-QqToF-MS.

40. R + 2 R R 1 3 O R + 2 H O R 3 R 4 O R 1 O R H O 4 O C H H O 3 O O + H O H O H R 5 O O C H 3 O + H O C H 3 O C H O O H 3 O O H O H C O H O O C H 3 O O C H H O 3 O O H O C H 3 O O C H 3 O O H + [ C H O ] 4 7 4 3 1 4 2 9 + 2 8 [ C H O ] : R = C H ; R = R = R = H 4 6 4 5 1 2 1 3 2 3 4 + + 3 2 [ C H O ] [ C H O ] 2 1 : R = C H ; R = C H = C H ; R = R = R = H : R = C H O H ; R = C H = C H ; R = R = O C H 5 0 5 1 1 5 3 7 3 5 8 1 3 2 2 3 4 5 1 2 2 2 3 4 3 + 2 2 [ C H O ] : R = H ; R = C O C H = C H ; R = R = H ; R = O H 3 7 3 3 1 0 1 2 2 3 4 5 + 2 3 : R = C H O ; R = C H ; R = R = O C H [ C H O ] 1 2 3 3 4 3 3 8 3 9 1 0 + [ C H O ] 2 4 : R = C H O H ; R = C H O ; R = H ; R = R = O C H 3 8 3 7 1 2 1 2 2 3 4 5 3 + : R = C H O H ; R = C H O ; R = R = R = O C H 2 5 [ C H O ] 1 2 2 3 4 5 3 3 9 3 9 1 3 + 2 6 : R = C H O H ; R = C H - C H O ; R = R = R = O C H [ C H O ] 1 2 2 2 3 4 5 3 4 0 4 1 1 3 + 2 7 [ C H O ] : R = C H O H ; R = C H = C H - C O O H ; R = R = R = O C H 4 1 4 1 1 4 1 2 2 3 4 5 3

42. CIMV LIGNINS Negative ion APPI-QqToF-MS of the Wheat Straw Lignin in Dioxane

43. CIMV LIGNINS

44. CIMV LIGNINS

45. CIMV LIGNINS

46. CIMV LIGNINS

48. Negative oligomer ions

50. CIMV LIGNINS