Title: EMERGING APPLICATION FOR NEW TYPES OF INDUSTRIAL LIGNINS
1EMERGING 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
2RESSOURCES 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
33,5 Billions tons of oil extracted /year
4BIOMASS 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
5THE 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
6LIGNOSULFONATES 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
7A 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.
8THE 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
9CIMV / 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
10CIMV 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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12THE CIMV PRODUCTS the keys of the future
13THE 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
14CIMV PAPER
15CIMV 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
16- Additives for animal feeding
- Xylitol
- Surfactants
- Furfurol and derivatives
- Furanic polymers
XYLOSE
17PETROCHEMISTRY / 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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19SOME FURANICS MONOMERS
20Bi-substitued furanic monomers
21Polycondensations
Polyester
Polyamide
Polyuréthane
22- Phenolic resins
- Polyuréthanes
- Polyesters
- Epoxy resins
- Adhesives
CIMV LIGNINS
23A.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
24CIMV 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.
25CIMV 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.
26CIMV 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
27CIMV LIGNINS
28CIMV LIGNINS
APPI-QqToF-MS of extracted wheat straw lignin
29CIMV LIGNINS
30CIMV LIGNINS
31CIMV LIGNINS
32CIMV LIGNINS
33CIMV LIGNINS
34CIMV LIGNINS
35CIMV LIGNINS
36CIMV LIGNINS
37CIMV LIGNINS
38CIMV LIGNINS
39Tentative 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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42CIMV LIGNINS
Negative ion APPI-QqToF-MS of the Wheat Straw
Lignin in Dioxane
43CIMV LIGNINS
44CIMV LIGNINS
45CIMV LIGNINS
46CIMV LIGNINS
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48Negative oligomer ions
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50CIMV LIGNINS
51THE FIRST FACTORY
52CIMV / 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
53THE 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
54SUSTAINABLE 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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5640 km - 127 330 T
40 to 50 km - 184 530 T
50 to 60 km - 240 097 T
harvesting 1/3 years
57Straw, bagasses, wood
Organic refining
Hydro-Organic refining
Lignins
C5 Sugars
Cellulose
Agrichemistry
Paper
Polymeric materials
Monomers