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LIGNIN - Isolation, thermal degradation and application in bioplastics
Aleš Ház, Radovan Tiňo, Štefan Šutý, Michal Jablonský, Igor Šurina
EFPRO – CEPI 3th Early Stage Researchers Workshop 25th November 2014, Brussels
Department of Wood, Pulp and Paper Institute of Natural and Synthetic Polymers Slovak University of Technology in Bratislava Radlinskeho 9 Bratislava, 812 37 mail: [email protected]
Possibilities • The future of the papermaking industry is in its
transformation into modern LCF biorefineries (Lignocellulose Feedstock Biorefinery).
• It is assumed, that in these biorefineries will be the cellulose and lignin fractions processed into large variety of products with added value.
• Nowadays, the lignin fraction is used mostly as a source of energy in pulp and paper business. On the other hand it represents a huge asset using its potential as a raw material for chemical industry.
By-product of Cellpap’s industry
• Production of lignin from papermaking industry and industry that creates LC waste is more than 50 mil. tones of lignin per year
• Lignin is the most important source of aromatic compounds which belongs to renewable sources with high potential of sustainability
• Replacement of fossil sources by lignin as a source of energy and valuable chemicals
Increasing value of the lignin
• The key solution for increasing value of the lignin is in the fractionation and isolation of lignin
We focused our research on finding the efficient methods of lignin isolation from black liquor of annual plants, softwood and hardwood by using inorganic and organic acids, CO2 and various polyelectrolytes.
• The obtained fractions of isolated lignins were characterized by TGA, DSC, FTIR, py-GC / MS, GPC, UV-Vis.
• isolation of lignin from the black liquor with high yield
• thermal degradation and decomposition of lignin pyrolysis mechanisms at selected temperatures
• identification of its degradation products
• Explanation of pyrolysis mechanism at selected temperatures
Fig. 1 Comparison of thermal stability [1]
Main areas of interest
Fig. 3 Identification of kraft lignin pyrolysis products of annual plants black liquor isolated by ultrafiltration
Fig. 2 Dependence of products creating by all selected temperatures of pyrolysis (precipitated lignin from beech wood lignin)
Temperature [°C]
Res
po
nse
fac
tor
Fig. 4 Suggested mechanism of structures formation in kraft lignin pyrolysis
Utilization of lignin in rubber blends
NEW PRODUCTS
In the area of bio-composite polymers we have focused our research on application of lignins in elastomeric mixtures on the basis of natural rubber.
The addition of the plasticized lignin acts not as reinforcing filler, but it retains excellent elastic properties of vulcanizers, increases the thermal stability and partially improves tensile strength.
Types of ligninosulfonates Mw (g.mol-1) Calcium content (%) Sulfur content (%)
Calcium lignosulfonate CA 120 24 000 5 6
Calcium lignosulfonate DP 624 30 000 5 7
Calcium lignosulfonate DP 625 6 000 5 5
Calcium lignosulfonate DP 850 6 400 1,8 6
Calcium lignosulfonate DP 990 64 000 7,1 7
Natrium lignosulfonate DP 991 6 100 0,01 7
Lignin isolated from black liquor obtained from annual plants (OP Papirna Ltd., Olsany, Czech Republic)
Lignin 1 1900 - 0,5
Lignin isolated from kraft black liquor of beech wood (Bukoza Holding Inc., Hencovce, Slovak Republic)
Lignin 2 1700 - 4
LIG
NO
SULF
ON
ATE
LI
GN
IN
The influence of lignosulfonate content on the adhession the rubber blend to polyester cord determened by PEEL TEST
Application of Ca lignosulfonate as a promotor of adhession in real blends
Samples Elemental analysis (%wt)
H/C O/C
N C H S O
Lignin 1 1,18 63,64 5,93 0,49 28,34 0,093 0,445
Lignin 2 0,28 55,68 4,62 3,91 31,65 0,083 0,568
Borrement CA 120 0,14 46,63 5,35 5,62 28,96 0,115 0,621
Compounds
Non-conjugated
phenolic structures
(I+III)
Conjugated phenolic
structures (II+IV)
Total amount of
phenolic hydroxyl
groups
mmol/g mmol/g mmol/g
Lignin 1 2,238 0,312 2,550
Lignin 2 3,129 0,393 3,521
Borrement CA 120 1,437 0,129 1,565
Lignins characterisation
Influence of different lignin samples on retention of elongation at break
Without stabilizer 1 phr IPPD 1 phr Lignin 1
1 phr Lignin 2
1 phr CA 120
IPP
D
Lig
nin
2
* PHG – phenolic hydroxyl groups
Without stabilizer
1 phr IPPD + 1 phr Lignin1
1 phr IPPD + 1 phr Lignin2
1 phr IPPD + 1 phr CA 120
Influence of two-component stabilizers on retention of tensile strength at break
50
60
70
80
90
100
110
120
0 72 168
Perc
en
t re
ten
tio
n o
f T
Sb
(%
)
Ageing time (hours)
Results in bioplastics
• Lignin acts as a filler which is suitable replacement
of carbon black in quite wide range of
concentrations in rubber blend - the highest
reinforcing effect was observed in case of lignin
• Lignin improves rubber-to-metal and rubber-to-
polyesters adhesion
• Lignin and lignosulfonates has a great potential as
antioxidant of rubber blends
Conclusions
• Modifications of lignins isolation techniques results in structures that are more suitable for final applications.
• Kinetic parameters of thermal degradation can help to determine the appropriate conditions for obtaining valuable lignin degradation products.
• By proper characterization of lignins is easy to find optimal conditions for processing lignins in industry.
• One of many examples is application of lignin in rubber as filler with valuable additional value – stabilizer, adhesion improver and antioxidant.
Conclusion
Thank you for your attention
Department of Wood, Pulp and Paper Institute of Natural and Synthetic Polymers Radlinskeho 9 Bratislava, 812 37
mail: [email protected] This work was supported by the Slovak Research and Development Agency, Slovakia, under the contract No. APVV-0850-11 and APVV-0694-12.
