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The Use of Lignin Derivatives to Improve Selected Paper Properties
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
2007 (English)Licentiate thesis, comprehensive summary (Other scientific)
Abstract [sv]

Ved består huvudsakligen av tre typer av polymerer, cellulosa, hemicellulosa och lignin. Lignin bildas i naturen genom enzymatiskt initierad oxidativ koppling av tre olika typer av fenylpropan-enheter. Dessa bygger genom olika kol-kol- och kol-syre-bindningar upp en amorf tredimensionell polymer. När kemisk massa tillverkas bryts lignin ner och löses ut i kokluten. Luten innehåller de förbrukade kokkemikalierna och bränns generellt i en sodapanna för att regenerera kemikalierna och producera ånga. Sodapannan är emellertid dyr. Därför har den blivit produktionsbegränsande på många massabruk. Att avlägsna en del av ligninet från avluten vore därför önskvärt och att finna ekonomiskt intressanta produkter baserade på lignin från svartlut är därför ett viktigt forskningsområde .

Ett lämpligt område för ligninprodukter vore som tillsatts i oblekt massa. Oblekt massa används till stor del för tillverkning av kraftliner, topp- och bottenskikten på wellpapp. När lådor av wellpapp lagras i containrar som färdas över haven, förändras den relativa luftfuktigheten. Detta gör att lådorna kollapsar lättare än om de skulle ha lagrats vid konstant luftfuktighet, även en hög sådan. Detta är på grund av det så kallade mekanosorptiva- eller accelererade krypfenomenet. Genom tillsatts av våtstyrkemedel till kraftliner eller behandla den med hydrofoba ämnen, finns indikatoner på att mekanosorptiva effekten skulle kunna minska.

För att försöka minska den effekten har ett lågmolekylärt kraftlignin, som utvunnits med hjälp av tvärsflödesfiltrering av svartlut och svavelsyrafällning, använts. Genom derivatisering av detta lignin med linolja erhölls ett hydrofobt ligninderivat som uppvisar strukturella likheter med biopolymeren suberin. När detta suberinlika ligninderivat tillsätts till massa verkar det mekanosorptiva krypet minska. När lågmolekylärt lignin används tillsammans med ligninradikalinitiatorerna lackas eller mangan(III) i kraftlinermassa erhålls dessutom en våtstyrka på ca 5% av torrstyrkan. Efter aminering av detta lignin gav en tillsatts till kraftlinermassan en våtstyrka på upp till 10% av torrstyrkan. Det finns indikationer på att det mekanosorptiva krypet samtidigt minskar när dessa behandlingar görs som ger upphov till ökad våtstyrka.

Abstract [en]

Wood consists mainly of three types of polymers; cellulose, hemi cellulose and lignin. Lignin is formed in nature through enzymatic initiated oxidative coupling of three different kinds of phenyl propane units. These form by various carbon-carbon and carbon-oxygen bonds, an amorphous three-dimensional polymer. As chemical pulp is produced, lignin is degraded and dissolved into pulping liquors. These liquors contain the spent cooking chemicals and are generally burnt in a recovery boiler to regenerate cooking chemicals and produce steam. However, the recovery boiler is expensive. Hence, it has become the bottleneck for production in many pulp mills. Removal of some lignin from the spent cooking liquor would, for that reason, be desired and valuable products based on lignin from cooking liquors are searched for.

One suitable area for lignin products would be as additive in unbleached pulp. A major product from unbleached pulp is kraftliner, the top and bottom layers of corrugated board. When boxes of corrugated board are stored in containers travelling overseas the relative humidity is varying. This makes the boxes collapse more easily than if they were stored at constant humidity, even a high one. This is due to the so called mechano-sorptive or accelerated creep phenomenon. By addition of wet strength additive to kraftliner or treating it with hydrophobic compounds there are indications on that the mechano-sorptive effect would decrease.

Trying to decrease this effect, low molecular weight kraft lignin has been used. It was obtained by cross-flow filtration of black liquor and precipitation by sulphuric acid. By derivatisation of this lignin by linseed oil, a hydrophobic lignin derivative was obtained, similar in structure to units in the biopolymer suberin. As this suberin-like lignin-derivative was added to pulp the mechano-sorptive creep seemed to be lowered. Furthermore, when the low molecular weight lignin was used together with the lignin radical initiators laccase or manganese(III) in kraftliner pulp, a wet strength of about 5% of dry strength was obtained. An amination treatment of this lignin and addition to kraftliner pulp resulted in a wet strength of up to 10% of dry strength. There are indications of that the mechano-sorptive creep also decreases as these treatments, resulting in increased wet strength, are made.

Place, publisher, year, edition, pages
Stockholm: KTH , 2007. , 28 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2007:56
Keyword [en]
kraft lignin, black liquor, cross-flow filtration, lignin derivative, kraftliner, oxidative coupling, laccase, manganese, linseed oil, mechano-sorptive creep
Keyword [sv]
kraftlignin, svartlut, tvärsflödesfiltrering, ligninderivat, kraftliner, oxidativ koppling, lackas, mangan, linolja, mekanosorptivt kryp
National Category
Paper, Pulp and Fiber Technology
Identifiers
URN: urn:nbn:se:kth:diva-4503ISBN: 978-91-7178-745-3 (print)OAI: oai:DiVA.org:kth-4503DiVA: diva2:12585
Presentation
2007-10-05, Q31, Osquldas väg 6, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20101103Available from: 2007-10-01 Created: 2007-10-01 Last updated: 2010-11-03Bibliographically approved
List of papers
1. Low Mw-lignin fractions together with vegetable oils as available oligomers for novel paper-coating applications as hydrophobic barrier
Open this publication in new window or tab >>Low Mw-lignin fractions together with vegetable oils as available oligomers for novel paper-coating applications as hydrophobic barrier
2008 (English)In: Industrial crops and products (Print), ISSN 0926-6690, Vol. 27, no 1, 98-103 p.Article in journal (Refereed) Published
Abstract [en]

Lignin residues are available in large amounts as kraft lignin from chemical pulping processes. This lignin is mainly incinerated in recovery boilers. The recovery boilers are often the bottle-necks in the overall pulping process when pulp production increases are desired. Through cross-flow nano-filtration of the black liquor from kraft pulping, a low-molecular weight lignin fraction can be removed thus decreasing the organic load on the recovery boilers. The low-molecular weight lignin fraction furthermore exhibit different characteristics compared to other commercial kraft lignins and represents a new raw material source in novel applications.

The low-molecular weight lignin was used together with a vegetable oil to produce a new hydrophobic lignin derivative similar to suberin. The lignin and the lignin derivative was analysed with FT-IR, UV-vis and SEC. The ability of the product to make paper surfaces hydrophobic was also evaluated.

The results demonstrate the possibility to make a suberin-like lignin derivative that is potentially of interest in paper-coating applications due to its capability to interact well with wood fibres and make paper hydrophobic.

Keyword
lignin; black liquor; nano-filtration; hydrophobization; linseed oil; suberin
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-9708 (URN)10.1016/j.indcrop.2007.08.006 (DOI)000252909500016 ()2-s2.0-36448982818 (Scopus ID)
Note
QC 20100622Available from: 2008-12-01 Created: 2008-12-01 Last updated: 2010-06-29Bibliographically approved
2. Laccase-initiated cross-linking of lignocellulose fibres using a ultra-filtered lignin isolated from kraft black liquor
Open this publication in new window or tab >>Laccase-initiated cross-linking of lignocellulose fibres using a ultra-filtered lignin isolated from kraft black liquor
Show others...
2007 (English)In: Applied Microbiology and Biotechnology, ISSN 0175-7598, E-ISSN 1432-0614, Vol. 77, no 4, 809-817 p.Article in journal (Refereed) Published
Abstract [en]

In this work, the effect of Trametes pubescens laccase (TpL) used in combination with a low-molecular-weight ultra-filtered lignin (UFL) to improve mechanical properties of kraft liner pulp and chemi-thermo-mechanical pulp was studied. UFL was isolated by ultra-filtration from the kraft cooking black liquor obtained from softwood pulping. This by-product from the pulp industry contains an oligomeric lignin with almost twice the amount of free phenolic moieties than residual kraft pulp lignin. The reactivity of TpL on UFL and kraft pulp was studied by nuclear magnetic resonance spectroscopy and size exclusion chromatography. Laccase was shown to polymerise UFL and residual kraft pulp lignin in the fibres, seen by the increase in their average molecular weight and in the case of UFL as a decrease in the amount of phenolic hydroxyls. The laccase initiated cross-linking of lignin, mediated by UFL, which gives rise to more than a twofold increase in wet strength of kraft liner pulp handsheets without loosing other critical mechanical properties. Hence, this could be an interesting path to decrease mechano-sorptive creep that has been reported to lessen in extent as wet strength is given to papers. The laccase/2,2'azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) mediator system showed a greater increase in wet tensile strength of the resulting pulp sheets than the laccase/UFL system. However, other mechanical properties such as dry tensile strength, compression strength and Scott Bond internal strength were negatively affected by the laccase/ABTS system.

Keyword
laccase; oxidation; ultra-filtered lignin; mediator; wet strength; biorefinery; kraft pulp; fibre bonding; MEDIATOR SYSTEM; PULP FIBERS; OXIDATION; PAPER; BIODEGRADATION; DEGRADATION; MECHANISMS; ACIDS
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-9709 (URN)10.1007/s00253-007-1203-6 (DOI)000251090900008 ()2-s2.0-36348971163 (Scopus ID)
Note
QC 20100629Available from: 2008-12-01 Created: 2008-12-01 Last updated: 2010-06-29Bibliographically approved
3. Adding lignin derivatives to decrease the effect of mechano-sorptive creep in linerboard
Open this publication in new window or tab >>Adding lignin derivatives to decrease the effect of mechano-sorptive creep in linerboard
2008 (English)In: Appita journal, ISSN 1038-6807, Vol. 61, no 6, 468-471 p.Article in journal (Refereed) Published
Abstract [en]

When load is applied to any type of paper while varying the relative humidity, the paper will creep more than if the same load is applied at constant humidity. This behaviour is called mechano-sorptive creep or accelerated creep, and the reasons for its occurrence in paper are still not fully understood. However, wet strength and the addition of apolar (hydrophobic) compounds to sheets have previously been suggested as factors improving the mechano-sorptive creep performance.

This work evaluates a method for improving wet strength and tests the addition of a hydrophobic compound, with particular reference to mechano-sorptive creep stiffness. Wet strength was improved by subjecting kraft liner pulp to low-molecular-weight lignin, obtained by cross-flow filtration, and to the radical initiator manganese(III). The hydrophobic compound added was a suberin-like lignin derivative. Adding the suberin-like lignin derivative significantly increased the mechano-sorptive creep stiffness, even though the stiffness at 90% rh decreased in the tested samples. This was probably because of the decrease in hygroexpansion caused by this hydrophobic additive.

Even though it is possible significantly to increase the wet strength of kraft liner pulp by adding manganese(III) and cross-flow-filtered lignin, doing so has no significant effect on mechano-sorptive creep stiffness.

Keyword
lignin derivatives; mechano-sorptive creep; wet strength; kraft liner; hygroexpansion; oxidative coupling; CROSS-LINKING; BLACK LIQUOR; PAPER
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-9710 (URN)000261303200021 ()2-s2.0-56649114226 (Scopus ID)
Note
Uppdaterad från manuskript till artikel: 20101103. QC 20100629Available from: 2008-12-01 Created: 2008-12-01 Last updated: 2010-11-03Bibliographically approved

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