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The behavior of kraft lignin during thermal treatment
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
2010 (English)In: Journal of Analytical and Applied Pyrolysis, ISSN 0165-2370, E-ISSN 1873-250X, Vol. 87, no 1, 70-77 p.Article in journal (Refereed) Published
Abstract [en]

Purified kraft lignin fractions from technical pulping liquors of softwood and hardwood have been subjected to step-wise analytical pyrolysis in the temperature interval 200-900 degrees C. The heterogenic structure of kraft lignin was revealed by the formation of pyrolysis products throughout the entire temperature interval although the majority of products were formed at 500-600 degrees C. Beyond 700 degrees C, no further pyrolysis products could be detected but a substantial portion of the lignin was shown to be converted into thermally stable products (char) not accessible by analytical pyrolysis. With pre-oxidation of the lignin with air at 250 degrees C prior to pyrolysis, a shift towards higher pyrolysis temperature was observed with a concomitant change in product composition. Thermal gravimetric analysis on such lignins also showed an improved stability against degradation. Methylation of the lignin prior to pyrolysis did not induce any significant changes in behavior, except for much lower T-g values.

Place, publisher, year, edition, pages
2010. Vol. 87, no 1, 70-77 p.
Keyword [en]
Analytical pyrolysis, Dimethyl carbonate, Kraft lignin, Methylation, Oxidation, Thermal gravimetric analysis
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-19180DOI: 10.1016/j.jaap.2009.10.005ISI: 000274277200011Scopus ID: 2-s2.0-77949303526OAI: oai:DiVA.org:kth-19180DiVA: diva2:337227
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Chemical Properties and Thermal Behaviour of Kraft Lignins
Open this publication in new window or tab >>Chemical Properties and Thermal Behaviour of Kraft Lignins
2009 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

Research concerning lignin has increased during the last years due to its renewability and ready availability in black liquor at pulp mills. Today, the kraft lignin found in black liquor is used as a fuel to gain energy in the recovery boiler at the mill. However, a new isolation concept, LignoBoost®, has enabled isolation of part of the lignin while allowing the use of black liquor as a fuel. This isolated lignin can be utilised as a fuel in, for example, thermal power stations or further upgraded to more value-added products. In this context, the most interesting value-added product is carbon fibre. The demand for carbon fibre has increased, but the biggest obstacle for a more extended use is the high production cost. About half of the production cost is related to the raw material.

In this work, the possibility of using kraft lignin as a precursor for carbon fibre production has been investigated through fundamental studies. Kraft lignins originating from birch, Eucalyptus globulus, softwoods and softwoods from liner production have been studied. By separating the lignin while still in solution in the black liquor, unwanted large particles such as carbohydrates can easily be removed. After isolation according to the LignoBoost process and purification with the use of an ion-exchanger, the lignins have been both chemically and thermally characterised. Identification of the released compounds at different temperatures has been performed because only 40% of carbon relative to original lignin remains, down from theoretical 60% after thermal treatment up to 1000°C. The main released compounds were phenols, as revealed by pyrolysis-GC/MS. Additionally, a pre-oxidation was done in order to try to stabilise the lignins. It was shown that an oxidation prior to the thermal treatment increases the yield by more than 10% and that the main release of compounds takes place between 400°C and 600°C. Fractionated lignin is better qualified as raw material for carbon fibre production because it is purer and its softening temperature can be detected. Fractionated kraft lignins from all investigated wood sources have high possibilities to act as precursors for the manufacture of carbon fibre.

Place, publisher, year, edition, pages
Stockholm: KTH, 2009. ix, 47 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2009:47
National Category
Analytical Chemistry
Identifiers
urn:nbn:se:kth:diva-11010 (URN)978-91-7415-406-1 (ISBN)
Presentation
STFI-salen, Innventia, Drottning Kristinas väg 61, 114 86 Stockholm (Swedish)
Opponent
Supervisors
Available from: 2009-09-10 Created: 2009-09-07 Last updated: 2010-11-03Bibliographically approved
2. Carbon Fibres from Kraft Lignin
Open this publication in new window or tab >>Carbon Fibres from Kraft Lignin
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Alternative title[sv]
Kolfiber från sulfatlignin
Abstract [en]

Kraft lignin has a high potential for use in more valuable applications than its current use as fuel in pulp mills and integrated pulp and paper mills. The possibility of using kraft lignin, a green material with a carbon content of more than 60 %, for the manufacturing of carbon fibres was investigated in this thesis. The strong and lightweight carbon fibre material has many potential application areas, e.g. in cars; the main obstacle limiting its demand is the high production cost, with the raw material (petroleum pitch and polyactrylonitrile) and fibre spinning constituting approximately 50 % of the cost.

Industrial kraft lignins originating from both softwood (spruce/pine) and hardwood (birch/aspen) were isolated with the LignoBoost technique and then purified and characterized to determine the best suitable lignin for the production of carbon fibre. Using ultrafiltration of the black liquor before isolation using the LignoBoost technique, a kraft lignin with satisfactory high purity was obtained. The fractionated kraft lignin can be used either as such or as a softening agent during melt spinning to obtain continuously spun kraft lignin fibres.

The behaviour during thermal treatment was found to differ depending on the type of kraft lignin used. After oxidative stabilisation, the studied lignins became more stable, and thus, the final yield after carbonisation was increased by 10-20 % in comparison to stabilisation in absence of oxygen. The identified products indicate that the main reactions during oxidative stabilisation are radical, oxidation, condensation and rearrangement reactions.

The structural differences between softwood and hardwood kraft lignins facilitated the stabilisation of the softwood lignin fibre as compared with the hardwood lignin fibres. Thermal stabilisation in an inert atmosphere using only heat was successfully achieved for the softwood kraft lignin fibres. Stabilisation and carbonisation was successfully performed in a one-step operation on softwood kraft lignin fibres. Thus, it seems possible that the separate stabilisation step can be omitted, which may reduce the processing costs of softwood kraft lignin-based carbon fibres.

Abstract [sv]

Sulfatlignin har hög potential för att kunna användas i mer värdefulla applikationer jämfört med idag då det främst används som bränsle i massabruk och integrerade massa/pappersbruk. I egenskap av ett grönt material med en kolhalt på mer än 60 %, har möjligheterna att använda kraftlignin vid kolfibertillverkning undersöks i den här avhandlingen. Kolfiber är lätt och starkt med många olika potentiella användningsområden. Det som idag huvudsakligen begränsar efterfrågan är den höga produktionskostnaden, där råmaterialet (petroleum pitch och polyakrylonitril) och fiberspinningen står för ca 50 % av kostnaden.

Industriella sulfatligniner från både barrved (gran/tall) och lövved (björk/asp) har framställts enligt LignoBoost-processen och har därefter renats och karaktäriserats med syfte att hitta det mest lämpliga råmaterialet för tillverkning av kolfiber. Genom att använda ultrafiltrering av svartlut innan isolering med LignoBoost-tekniken, kan man få ett kraftlignin som är tillräckligt rent. Det fraktionerade kraftligninet kan användas antingen rent eller som mjukgörare under smältspinning, för att få fram kontinuerligt spunna sulfatligninfibrer.

Sulfatligniner från olika vedslag beter sig olika under termisk behandling. Efter oxidativ stabilisering blir ligninerna mer stabila jämfört med stabilisering i frånvaro av syre, vilket medför ett högre utbyte med 10-20 % av den slutgiltiga kolfibern efter karbonisering. De viktigaste reaktionerna som sker under oxidativ stabilisering av fibrer från sulfatlignin är radikal-, oxiderings- och omlagringsreaktioner.

De strukturella skillnaderna mellan sulfatlignin från barrved och lövved gör det möjligt att stabilisera barrvedslignin mycket fortare. Termisk stabilisering i inert atmosfär med endast värme har lyckats med sulfatligninfibrer från barrved. Vidare har även stabilisering och karbonisering i ett enda steg lyckats med sulfatligninfibrer från barrved. Detta kan göra det möjligt att utesluta stabiliseringssteget, vilket förhoppningsvis kan reducera processkostnaderna för kolfiber från barrvedssulfatlignin.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. xvii, 52 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:13
National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-92256 (URN)978-91-7501-283-4 (ISBN)
Public defence
2012-04-20, STFI-salen, Drottning Kristinas väg 61, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20120330Available from: 2012-03-30 Created: 2012-03-30 Last updated: 2012-03-30Bibliographically approved

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