EMERGING APPLICATION FOR NEW TYPES OF INDUSTRIAL LIGNINS

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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_at_cimv.fr
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RESSOURCES wood, straw, bagasses of sugar cane
sweet sorghum, hemp, flax, miscanthus
World availability of Lignocellulose from
agricuture and forestry gt 3 billions tons /
year Annual market for non foodstuff use lt 0,3
billions tons / year
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3,5 Billions tons of oil extracted /year
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BIOMASS OIL Competitiveness of the raw
material
1 ton of oil 400 1 ton of straw 80
1 ton of oil in petrochemistry 1,8 ton of
dry straw in agrichemistry
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THE PULP PRODUCTION TODAY
MECA
H OH-
WOOD
RAW PULP
COMMERCIAL PULP
BLEACHING
WASTES Sugars, Polysaccharides, Lignins, Modified
lignins, Résins, Organic oxidised molecules,
Minérals, Organic chlorine products...
RECYCLING minerals, energy
TREATMENTS
CONTINENTAL RIVERS
SOLID WASTES / DUMP
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LIGNOSULFONATES AND KRAFT LIGNINS

• Highly condensed materials with high sulfur
  content produced with the chemical pulps
• Industrial use
• - Fillers and low grade surfactants lt 5
• - Energy gt 95

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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.

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THE CIMV PROCESS
Straw, bagasses, wood Physical conditionning
Organic refining
Organic acid recycling
Organic acid recycling
Sugars Lignins Organic acid solution
Raw chemical pulp
H2O
Bleaching Peracides / H2O2 NaOH / H2O2
C5 sugars
Lignins
Commercial chemical pulp
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CIMV / KRAFT
DRY STRAW 80 / T
DRY WOOD 120 / T
Same investment / ton of product.
KRAFT
CIMV
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
0,4 to 0,5 T energy 70 / T
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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

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THE CIMV PRODUCTS the keys of the future
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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

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CIMV PAPER
PAPER Skoura printing paper 70 eucalyptus pulp / 30 softwood pulp Skoura printing paper 70 CIMV pulp / 30 softwood pulp
Schopper 21 40
Bulk 1,94 1,73
Bursting 1,35 1,33
Breaking length 2540 3218
Tear 72,1 40,1
Opacity 89,87 93,63
Porosity 134 38
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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 and new position 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

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• Additives for animal feeding
• Xylitol
• Surfactants
• Furfurol and derivatives
• Furanic polymers

XYLOSE
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PETROCHEMISTRY / AGROCHEMISTRY the convergent
point
The most prominent monomers of petrochemistry are

The CIMV process, following the agrichemistry
concept, can substitutes them by
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SOME FURANICS MONOMERS
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Bi-substitued furanic monomers
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Polycondensations
Polyester
Polyamide
Polyuréthane
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• Phenolic resins
• Polyuréthanes
• Polyesters
• Epoxy resins
• Adhesives

CIMV LIGNINS
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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
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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
  effect which 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.

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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
OH groups ( mmol/g of lignins) Formyl Acetyl Hydroxyl Total
OH aliphaticphenolic) 0.6 0.5 2.9 4
OH phenolic 0.2 0.05 0.85 1.1
OH aliphatic 0.4 0.45 2.05 2.9
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.
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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

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CIMV LIGNINS
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CIMV LIGNINS
APPI-QqToF-MS of extracted wheat straw lignin
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CIMV LIGNINS
Characteristic Ions Cpd Calculated m/z Observed m/z Abundance Difference (ppm)
C19H17O4 1 309.1127 309.11 7.69 8.7
C18H19O6 2 331.1182 331.1172 84.6 3
C19H17O6 3 341.1025 341.0999 63.5 7.6
C19H19O6 4 343.1182 343.1166 100.00a 4.6
C20H15O6 5 351.0869 351.0859 9.87a 2.8
C20H17O6 6 353.1025 353.1019. 9.21a 1.7
C18H20O8. 7 364.1158 364.1149 62.44 2.4
C21H21O6 8 369.1338 369.1329 100 2.4
C21H23O8 9 403.1393 403.1363 50.06 7.4
C25H21O7 10 433.1287 433.1282 17.38 -1.1
C28H27O8 11 491.1706 491.1709 63.33a -0.6
C28H29O8 12 493.1862 493.1861 18.18a 0.2
C28H29O9 13 509.189 509.1881 68.18a 1.8
C29H29O9 14 521.1812 521.1811 16.66a 0.2
C29H31O9 15 523.1968 523.1967 22.11 0.2
C29H31O10 16 539.1917 539.1916 13.63 0.2
C30H31O10 17 551.1917 551.1909 22.72a 1.5
C30H33O10 18 553.2074 553.2068 4.91 1.1
C31H31O11 19 579.1866 579.1859 9.16 1.2
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CIMV LIGNINS
Characteristic Ions Cpd Calculated m/z Observed m/z Abundance Difference (ppm)
C31H33O11 20 581.2023 581.2022 4.62a 0.2
C37H35O8 21 607.2332 607.2322 12.5 1.6
C37H33O10 22 637.2074 637.2066 9.86 1.2
C38H39O10 23 655.2543 655.2418 5.92 1.9
C38H37O12 24 685.2285 685.2271 9.25 2
C39H39O13 25 715.2547 715.2545 24.23b 0.3
C40H41O13 26 729.2848 729.2847 26.32b 0.1
C41H41O14 27 757.2496 757.2495 9.42b 0.1
C46H45O12 28 789.2911 789.2898 16.45b 1.6
C47H43O14 29 831.2653 831.2651 22.41b 0.2
C49H49O14 30 861.3122 861.312 16.92b 0.2
C49H49O15 31 877.3071 877.3059 18.92b 1.4
C50H51O15 32 891.3228 891.3226 11.14b 0.2
C53H47O14 33 907.2966 907.2965 10.12b 0.1
C55H51O15 34 951.3228 951.3226 10.11b 0.2
C57H49O15 35 973.3071 973.3069 12.11b 2
C59H52O14 36 984.3357 984.3355 15.16b 0.2
C64H59O16 37 1083.3803 1083.38 9.98b 0.3
C64H59O17 38 1099.3752 1099.375 8.12b 0.3
C65H61O17 39 1113.3909 1113.391 10.17b 0.2
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CIMV LIGNINS
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CIMV LIGNINS
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CIMV LIGNINS
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CIMV LIGNINS
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CIMV LIGNINS
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CIMV LIGNINS
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CIMV LIGNINS
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CIMV LIGNINS
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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.
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CIMV LIGNINS
Negative ion APPI-QqToF-MS of the Wheat Straw
Lignin in Dioxane
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CIMV LIGNINS
Characteristic Ions Cpd Calculated m/z Observed m/z Abundance Difference (ppm)
C10H9O4- 41 193.0501 193.051 72.14a -4.1
C16H13O4- 42 269.0814 269.08 51.61a 5.5
C17H15O5- 43 299.0919 299.092 48.28a -0.3
C18H15O5- 44 311.0919 311.092 61.12a -0.3
C19H17O5- 45 325.1076 325.108 50.12a 0.3
C18H17O6- 2 329.1025 329.102 100.00a 1.5
C20H19O5- 46 339.1232 339.123 14.90a -0.3
C19H17O6- 47 341.1025 341.101 40.62a 3.5
C19H19O6- 48 343.1182 343.118 45.71a 0.29
C21H19O7- 49 383.1131 383.113 50 0.3
C21H21O7- 50 385.1076 385.108 64.52 0.3
C21H21O8- 51 401.1236 401.124 38.77 0.2
C26H29O7- 52 453.1913 453.191 21.4 -0.2
C27H30O8- 53 482.1941 482.194 12.91 0.2
C28H25O8- 54 489.1549 489.155 35.82 0.2
C28H27O8- 55 491.1706 491.171 36.73 0
C28H27O9- 13 507.1655 507.165 67.34 0.2
C29H29O9- 15 521.1812 521.181 36.15 0.2
C30H32O9- 56 536.2046 536.205 22.5 0.2
C30H29O10- 17 549.1761 549.176 26.63 0.2
C30H31O11- 57 567.1865 567.186 15.12 0.2
C38H35O12- 24 683.2493 683.249 30.12b 0
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CIMV LIGNINS
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CIMV LIGNINS
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CIMV LIGNINS
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Negative oligomer ions
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CIMV LIGNINS
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THE FIRST FACTORY
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CIMV / CHAMPAGNE

• CIMV-CHAMPAGNE ARDENNES is a subsidiary of CIMV
  and CHAMPAGNE CEREALES
• This joint venture 65/35 makes the straw supply
  feel secure.
• The factory will refine 140 000 T of straw/year
  and will create 130 jobs
• We set up an industrial and commercial strategy
  for a worldwilde extrapolation

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THE CONSTRUCTION OF THE FACTORY

• CIMV carries out the basic engineering.
• The industrial production line is built with
  standard equipments well known in sugar, oil,
  vegetal oil and chemical industry.
• We work with
• Organic refining pulp separation DE SMET
• Evaporation / désolvantation GEA KESNER
• Hydro-organic refining pulp operations
  ANDRITZ, CTP
• Liquid / Liquid extraction ROBATEL, KHUNI
• Inter-blocks connections PONTICELLI
• Detailed engineering and construction CITEX
  TECHNIP, THEBAULT INGENIERIE
• The production will start in october 2009

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SUSTAINABLE DEVELOPMENT

• Organic acids recycled no pollution
• Bleaching, partly in organic media, reduces the
  water consumption dramatically ( gt 80).
• No green house effect with straw used for energy.
• A CIMV factory substitutes in a year the
  deforestation of 2500 hectares of forest by 140
  000 T of straw.

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40 km - 127 330 T
40 to 50 km - 184 530 T
50 to 60 km - 240 097 T
harvesting 1/3 years
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Straw, bagasses, wood
Organic refining
Hydro-Organic refining
Lignins
C5 Sugars
Cellulose
Agrichemistry
Paper
Polymeric materials
Monomers