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- Agnemo, Roland, 1944-
(författare)
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Ligniners reaktioner med alkalisk väteperoxid
- 1981
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Under alkaline conditions hydrogen peroxide can be used either as a 1ignin-degrading or a 1ignin-preserving bleaching agent. If heavy metal ions are present and/or silicate is absent in the reaction medium, hydrogen peroxide decomposes via hydroxyl radicals and superoxide ions to oxygen and water. These decomposition products are able to react for example with phenolic lignin structures and thereby cause a partial degradation of lignin. In such a system peroxide could act as a bleaching and delignifying agent at the same time and these properties can be utilized for the bleaching of chemical pulps.In order to elucidate the factors which influence the degradation of phenolic structures by oxidation with alkaline hydrogen peroxide the lignin model compounds-methylsyringyl alcohol was studied.By determining the first order reaction rate constants for the oxidation, the main results which were obtained indicate that phenolic lignin structures can be efficiently degraded especially if:A. The pH in the bleaching liquor is close to the pK -valueàfor hydrogen peroxide.B. The ionic strength in the bleaching medium is as high as possible.C. A fixed amount of heavy metal ions (manganese) is added to the bleaching liquor.In the presence of silicate and diethylentriaminepenta-acetic acid (DTPA) hydrogen peroxide is stabilized against decomposition. Under these conditions alkaline hydrogen peroxide is able to react only with lignin units containing conjugated carbonyl groups such as quinone, aryl-oe-carbonyl and cinnamaldehyd structures, leading to an elimination of the chromophoric structures without any substantial dissolution of lignin. In this part of work we have elucidated the kinetic behavior and the reaction products from lignin model compounds of the aryl-of- carbonyl and cinnamaldehyde types.1,2-Diarylpropan-1,3,-diol structures constitute an important building unit in native lignins. We have demonstrated that under hydrogen peroxide bleaching conditions the model compound 2,3--bis(4-hydroxy-3-methoxyphenyl)-3-ethoxy-propanol was converted to stilbenes, ûe. structures which when present in pulps may contribute to a rapid yellowing. The results obtained with model compounds under simulated lignin retaining bleaching conditions demonstrate that there are possibilities to improve the bleaching of mechanical pulps with hydrogen peroxide if:A. The remaining heavy metal ions complexed with DTPA are present in their lowest valence states.B. The concentration of hydroperoxy ions can be maintained at a high level at the lowest possible pH-value.
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| 2. |
- Antonsson, Stefan, 1979-
(författare)
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The Use of Lignin Derivatives to Improve Selected Paper Properties
- 2007
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
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| 7. |
- Friman, Linda, et al.
(författare)
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Tannin-iron impregnated thermomechanical pulp : Part II: Bleachability and brightness reversion
- 2004
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Ingår i: Nordic Pulp & Paper Research Journal. - 0283-2631 .- 2000-0669. ; 19:4, s. 525-531
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Tidskriftsartikel (refereegranskat)abstract
- Tannins are polymeric, phenolic constituents found in the bark of pine and spruce. When reacting with iron ions, tannins form strongly coloured complexes. Thus, the presence of bark in the mechanical pulping process leads to decreased brightness of the pulp. In order to evaluate the effects of the presence of iron on the properties of pulp, we have impregnated thermomechanical pulp (TMP) with 30 parts per million (ppm i.e. mg/kg) iron either as Fe3+ or as tannin-iron complexes and studied how such treatments affect bleachability and heat-induced brightness reversion. The bleaching agents studied are hydrogen peroxide and sodium dithionite. Treatment of the tannin-iron impregnated pulp with 1% by weight of diethylenetriaminepentaacetic acid (DTPA) before bleaching with 4% hydrogen peroxide almost eliminated the brightness loss caused by the impregnation. Such a treatment also removed all of the added iron from both the tannin-iron and FeCl3 impregnated pulps. Approximately 5% more of the added peroxide was required for oxidation of the tannins in the tannin-iron impregnated pulp. Contrary to what was observed with peroxide bleaching, dithionite bleaching did not reduce the amount of iron in the pulps. Instead, the added iron and tannin-iron negatively affected the dithionite bleaching, even if the pulps were extracted with DTPA before bleaching. It should therefore be advantageous to first bleach with peroxide, which removes most of the iron, and then with dithionite. Compared with dithionite, peroxide yields a more efficient bleaching. The reason for this is that the former reduces the light absorption coefficient, the k-value, more efficiently in the whole visible spectrum, whereas dithionite reduces it mainly at shorter wavelengths. In our experiments, the addition of tannin-iron or FeCl3 to the untreated pulp did not increase heat-induced brightness reversion. This is Supported by the fact that although extraction of the samples with DTPA before bleaching lowered the iron content slightly, it-did not affect the brightness reversion. The initial brightness reversion of the dithionite bleached pulps was larger than that observed for the peroxide bleached pulps.
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| 8. |
- Friman, Linda, et al.
(författare)
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Tannin-iron impregnated thermomechanical pulp : Part I: Effects of extractions and heat on brightness
- 2004
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Ingår i: Nordic Pulp & Paper Research Journal. - 0283-2631 .- 2000-0669. ; 19:2, s. 229-236
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Tidskriftsartikel (refereegranskat)abstract
- Tannins are polyphenolic compounds found mainly in bark. When reacting with iron, they form strongly coloured complexes, which through contamination from the bark may induce a brightness decrease of mechanical pulps. Wood itself contains phenolic compounds, which can form coloured complexes with iron. We have investigated gallotannin as a model for metal-binding sites in the pulp. The behaviour of tannin-iron complexes in solution and in pulp has been studied. In aqueous solution, the tannin-iron complexes can be decolourised by the addition of diethylenetriaminepentaacetic acid (DTPA). The colour of the tannin-iron complexes was very pH-dependent. Thus in solution, these were decolourised at low pH and at high pH the spectral characteristics were changed substantially. We have studied the effects on brightness and heatinduced brightness loss of the impregnation of thermomechanical pulp (TMP) with 30 parts per million iron (ppm i.e. mg/kg) either as iron or tannin-iron as well as the possibility to decrease such effects by using various solvent extractions. The tannin-iron impregnation causes a decrease in ISO-brightness of approximately 3% and an increase in the light absorption coefficient (k) by approximately 2 m(2)/kg at the tannin-iron absorbance maximum. 565 run. These effects are approximately ten times higher than those observed for the Pulp only impregnated with iron. Extraction with 1% by weight of DTPA provides a way to reduce the brightness decrease induced by the tanniniron complexes and the observed decrease can be attributed to removal of iron from the pulp. Acid extraction was the most efficient way to reduce the iron content in the pulps and to decoulorise the tannin-iron impregnated pulp. However, after acid extraction of iron impregnated Pulps, new chromophores were evidently formed. Addition of the reducing agent, sulphite, to extractions had no effect on the iron removal or the brightness of the impregnated pulps. The heat-induced brightness loss is not influenced by the addition of tannin-iron or iron. The brightness loss caused by heat was lower for pulps extracted with DTPA.
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| 9. |
- Karlsson, Anette, et al.
(författare)
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High consistency hydrogen peroxide bleaching of mechanical pulps with varying amounts of fines
- 2010
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Ingår i: Nordic Pulp & Paper Research Journal. - 0283-2631 .- 2000-0669. ; 25:3, s. 256-268
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Tidskriftsartikel (refereegranskat)abstract
- Hydrogen peroxide is a widely used bleaching chemical for mechanical pulps and is particularly useful when high brightness levels are required. The objective of this work was to study fines as a limiting factor for reaching higher brightness levels in high consistency hydrogen peroxide bleaching of Norway spruce (Picea abies) thermomechanical (TMP) and stone groundwood (SGW) pulps. The hydrogen peroxide bleaching efficiency (i.e. light absorption coefficient reduction) was studied as a function of temperature, alkali charge and fines content using an experimental design based on MODDE software (Umetrics AB).It is known that all types of fines contain more lignin, hemicelluloses, pectins, metals and less cellulose than long fibres. The light absorption coefficient was greater for unbleached TMP than for unbleached SGW pulp and an increased quantity of fines increased the light absorption coefficient for both pulp types. The increase was, however, most pronounced for the TMP. Furthermore, the data suggests that both the fibre fraction and the fines fraction are more coloured in the thermomechanical pulp. In most cases, increased amounts of fines in the pulp had a negative impact on the bleached pulp brightness in spite of the improved light scattering ability accompanying the addition of fines. A level of fines exceeding 50% was especially detrimental resulting in lower pulp brightness due to a higher light absorption coefficient.Increasing the bleaching temperature did not improve the bleaching efficiency. The optimal bleaching temperature at a hydrogen peroxide charge of 4.5% was found to be 70°C within the tested interval of 70-110°C. For a fines content of 25%, the stone groundwood pulp displayed a brightness of 83% whereas the thermomechanical pulp achieved a brightness of 79%.
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| 10. |
- Logenius, Louise, et al.
(författare)
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A study of the formation and elimination of chromophores in wood under mechanical pulping conditions using spectroscopy
- 2010
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Ingår i: Paperi ja puu - Paper and timber. - 0031-1243. ; 92:5, s. 35-39
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Tidskriftsartikel (refereegranskat)abstract
- Thin sections of wood, i.e., shavings, were used in spectroscopic measurements studying the formation and elimination of chromophores under mechanical pulping conditions. Light absorption coefficients, light scattering coefficients, and brightness were monitored.The method was applied to study how temperature in the absence of mechanical energy affects wood brightness. An increase in absorption coefficient at 420 nm indicates formation of ortho-quinone structures. By applying mechanical pulp processing conditions, the light absorption coefficient increased in the 400-500-nm wavelength region, probably due to the formation of chromophores in the lignin. Comparison of heat treated wood shavings with mechanical pulps indicated that additional chromophores were created during the mechanical pulping processes.The method was also used in studying how high-temperature hydrogen peroxide bleaching of the wood shavings affects the light absorption coefficients. The light absorption spectra reveal information about chromophore elimination in wood chemical components during hydrogen peroxide bleaching at slightly pressurized conditions. This is relevant to processes, such as the alkaline peroxide mechanical pulp process, in which the wood chips are impregnated with bleaching chemicals before refining. The easy penetration of chemicals into the wood shavings ensures rapid and even distribution of the treatment chemicals. A change in light absorption coefficient at shorter wavelengths (400-500 nm) was observed.
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