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Lignin release during oxygen delignification – kinetics, structure and potential
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology.ORCID iD: 0009-0006-6182-1031
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Oxygen delignification is a critical stage in modern kraft pulp production, enabling significant reductions in chlorine-based bleaching chemicals and environmental emissions while maintaining fiber quality. The process remains limited by challenges in efficiency and selectivity, governed jointly by chemical reactions and mass transport constraints. This thesis investigates the interplay between these mechanisms and explores the properties and valorisation potential of oxidized lignin (oxlignin) extracted from oxygen-stage wash liquors. Experimental results demonstrate that lignin removal during oxygen delignification is driven by a combination of rapid early-stage oxidative reactions and diffusion-controlled leaching. High oxygen pressure and sufficient alkalinity promote lignin depolymerization and oxidation, improving selectivity, while insufficient chemical conditions lead to lignin redeposition and cellulose degradation. Upstream factors such as brownstock washing efficiency and storage conditions significantly influenced lignin leaching and pulp quality, highlighting the importance of integrated process control. Oxlignin, isolated from industrial filtrates, differed markedly from conventional kraft lignin, exhibiting higher carboxylic acid content, improved water solubility, and a narrower molecular weight distribution. These properties suggest potential applications as dispersants or additives in biopolymer formulations. Ultrafiltration proved to be a viable approach for fractionating oxlignin. By connecting process optimization with resource valorisation, this work contributes to more sustainable kraft pulp production and supports the development of new lignin-based value streams in future biorefineries.

Abstract [sv]

Syrgasdelignifiering är ett viktigt steg i modern sulfatmassaproduktion och möjliggör en betydande minskning av klorbaserade blekkemikalier och miljöutsläpp samtidigt som fiberkvaliteten bibehålls. Trots att processen är väl etablerad finns begränsningar i effektivitet och selektivitet, vilka påverkas av både kemiska reaktioner och masstransportfenomen. Denna avhandling undersöker samspelet mellan dessa faktorer samt utforskar egenskaperna och värdepotentialen hos oxiderat lignin (oxlignin) som extraherats från tvättvätskor i syrgassteget. Studierna visar att ligninavlägsnandet styrs av en kombination av oxidativa reaktioner och diffusionsbegränsningar. Faktorer uppströms, såsom massatvätt och lagringsförhållanden, påverkar lakning av lignin och massakvalitet, vilket understryker vikten av integrerad processkontroll. Oxlignin, isolerat från industriella tvättvätskor, uppvisade tydliga skillnader jämfört med konventionella svartlutslignin, högre halt av karboxylsyror, förbättrad vattenlöslighet och mer homogen molekylviktsfördelning. Dessa egenskaper innebär potential för användning som till exempel dispergeringsmedel. Ultrafiltrering visades vara en möjlig metod för fraktionering av oxlignin. Genom att koppla processoptimering till resursvärdering bidrar detta arbete till en mer hållbar massaproduktion och utveckling av nya värdeflöden i bioraffinaderier.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2025. , p. 61
Series
TRITA-CBH-FOU ; 2025-40
Keywords [en]
Oxygen delignification, lignin valorization, oxlignin, mass transport, kraft pulp, ultrafiltration
Keywords [sv]
Syreblekning, ligninvärdering, oxlignin, masstransport, sulfatmassa, ultrafiltrering
National Category
Paper, Pulp and Fiber Technology
Research subject
Fibre and Polymer Science
Identifiers
URN: urn:nbn:se:kth:diva-374258ISBN: 978-91-8106-505-3 (print)OAI: oai:DiVA.org:kth-374258DiVA, id: diva2:2022310
Public defence
2026-01-23, F3 Lindstedtvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Vinnova
Note

QC 20251216

Available from: 2025-12-16 Created: 2025-12-16 Last updated: 2026-01-12Bibliographically approved
List of papers
1. On the nature of the selectivity of oxygen delignification
Open this publication in new window or tab >>On the nature of the selectivity of oxygen delignification
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2025 (English)In: Nordic Pulp & Paper Research Journal, ISSN 0283-2631, E-ISSN 2000-0669, Vol. 40, no 1, p. 61-69Article in journal (Refereed) Published
Abstract [en]

This work has focused on oxygen's role in the delignification process within the context of pulp production. We have investigated the role of oxygen in a complex set of chemical reactions taking place during this process, including both oxidative and non-oxidative reactions. This study explores the impact of pH changes during the oxygen delignification process and the characteristics of the resulting pulps. Additionally, this research examines the effect of oxygen, by comparing conventional oxygen delignification with trials using air and nitrogen. Industrial softwood kraft pulps with a kappa number of 35 were subjected to delignification for 20-120 min under alkaline conditions. The resulting pulps were assessed for kappa number, intrinsic viscosity, fiber charge, and ISO brightness. An important observation from this research is the reduction in lignin molecular weight upon exposure to oxygen and air, suggesting depolymerization reactions facilitated by oxygen species, whereas nitrogen exposure results in less pronounced changes. This finding underscores the impact of oxygen in altering lignin structure, thus informing the selectivity and effectiveness of the delignification process.

Place, publisher, year, edition, pages
Walter de Gruyter GmbH, 2025
Keywords
alkaline extraction, alkaline leaching, kraft pulp, oxygen delignification, selectivity, viscosity
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-363103 (URN)10.1515/npprj-2024-0026 (DOI)001359220200001 ()2-s2.0-105003286446 (Scopus ID)
Note

QC 20250506

Available from: 2025-05-06 Created: 2025-05-06 Last updated: 2025-12-16Bibliographically approved
2. Oxlignin: A Novel Type of Technical Lignin from Kraft Pulp Mills
Open this publication in new window or tab >>Oxlignin: A Novel Type of Technical Lignin from Kraft Pulp Mills
2025 (English)In: ACS Omega, E-ISSN 2470-1343, Vol. 10, no 18, p. 18784-18792Article in journal (Refereed) Published
Abstract [en]

Lignin, a bio-originated polymer, is being explored as an alternative to nonrenewable fossil resources. It is obtained from biomass during pulping and is mostly burned for energy. In most kraft pulp lines, residual lignin in the pulp is oxidized and solubilized during an oxygen delignification step. This study proposes an isolation method for lignin solubilized during oxygen delignification, which we refer to as "oxlignin", and explores its structural characteristics and properties. The study found acid precipitation to be an effective method for partially isolating oxlignin from the oxygen delignification step. Various analytical methods were employed, including UV-vis absorption analysis, 31P NMR spectroscopy, FT-IR spectroscopy, SEC, and TGA. In addition, the solubility of the lignin was studied in four different solvents and compared to the commercial kraft lignins. The study found that oxlignin is a promising substitute for lignosulfonates in certain applications due to its hydrophilicity and high solubility in water, methanol, and ethanol. Compared to kraft lignins, oxlignin has a lower phenolic group content but higher carboxylic acid content.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2025
National Category
Paper, Pulp and Fiber Technology Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-365288 (URN)10.1021/acsomega.5c00434 (DOI)001478739200001 ()40385208 (PubMedID)2-s2.0-105003767951 (Scopus ID)
Note

QC 20250619

Available from: 2025-06-19 Created: 2025-06-19 Last updated: 2025-12-16Bibliographically approved
3. Effect of storage conditions on the brownstock washing and oxygen delignification of kraft pulps
Open this publication in new window or tab >>Effect of storage conditions on the brownstock washing and oxygen delignification of kraft pulps
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2025 (English)In: Cellulose, ISSN 0969-0239, E-ISSN 1572-882X, Vol. 32, no 4, p. 2567-2579Article in journal (Refereed) Published
Abstract [en]

A long-term goal of the pulping industry is to optimize process parameters for efficiently removing degraded and soluble lignin during the fiber line processes such as kraft pulping, brownstock washing, and bleaching. This study investigates how pulp storage affects the efficiency of brownstock washing and oxygen delignification. Three pulp groups were rinsed with warm and cold water at 40 °C and 5 °C, respectively, and then stored under varying conditions (1 day, 1 week at temperatures of 5 °C and 60 °C. Our findings indicate that after one week of storage at 60 °C, more lignin was extracted, highlighting the influence of storage temperature and time on Kappa reduction (lignin removal) during storage. Additionally, larger lignin fragments were removed with increased storage temperature and time, suggesting that degraded lignin molecules trapped within the fibers can leach out during storage and be subsequently removed in washing. The different storage conditions had only a slight effect on oxygen delignification performance. We conclude that storage conditions, particularly temperature and time, significantly impact lignin removal efficiency and can enhance the pulp washing process. This study also provides valuable insights into lignin mass transfer during storage, offering guidance for industrial applications. The study also revealed that pulp quality after oxygen delignification is influenced by pH and lignin agglomeration and retention in the fibers during preceding washing and storage operations, emphasizing the need for careful control of the latter conditions to minimize cellulose degradation.

Place, publisher, year, edition, pages
Springer Nature, 2025
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-374256 (URN)10.1007/s10570-025-06396-z (DOI)001410203900001 ()2-s2.0-105001086485 (Scopus ID)
Funder
Vinnova, 2021-02089Vinnova, 2021-02087KTH Royal Institute of Technology
Note

QC 20251219

Available from: 2025-12-16 Created: 2025-12-16 Last updated: 2026-01-21Bibliographically approved
4. Ultrafiltration for molecular-weight-based separation of lignin from oxygen delignification process streams
Open this publication in new window or tab >>Ultrafiltration for molecular-weight-based separation of lignin from oxygen delignification process streams
(English)Manuscript (preprint) (Other academic)
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-374255 (URN)
Note

QC 20251219

Available from: 2025-12-16 Created: 2025-12-16 Last updated: 2025-12-19Bibliographically approved
5. Oxygen transfer and lignin diffusion studied through staged delignification and turbulent mixing
Open this publication in new window or tab >>Oxygen transfer and lignin diffusion studied through staged delignification and turbulent mixing
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(English)Manuscript (preprint) (Other academic)
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-374253 (URN)
Note

QC 20251219

Available from: 2025-12-16 Created: 2025-12-16 Last updated: 2026-01-21Bibliographically approved

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