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Aspects of optimizing pulp fibre properties for tissue and packaging materials
Mid Sweden University, Faculty of Science, Technology and Media, Department of Chemical Engineering.
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

To improve the competitive advantages of pulp fibre-based materials for tissue and packaging over fossil-based products, it is essential to increase knowledge of the selectivity of the cooking and the chemimechanical processes by optimizing the unit operations of impregnation, cooking and refining. A general goal in pulping processes is to achieve as efficient and even fibre separation as possible. A key to achieving this is to improve impregnation uniformity. In the case of chemical pulping, we need to study how a more even distribution of lignin at the fibre level via easily impregnated wood chips can be achieved using classic measures such as equalized hydroxide ion concentration, increased initial sulphide ion concentration, low sodium ion concentration and a low cooking temperature combined with an oxidative and reductive environment. In the case of chemithermomechanical pulp (CTMP) manufacturing, we need to achieve as even a degree of sulphonation as possible at the level of the individual fibres by means of improved sulphite ion distribution within the wood chips before they are pre-heated prior to entering the refiner. 

Firstly, we have studied selective cooking systems for sulphate pulp manufacturing in oxidative (polysulfide) and reductive (sodium borohydride) environments. The yield increased from 48% to a maximum of 53%, which resulted in faster dewatering when mimicking a tissue papermaking process. This could explain how the advantage of the increased yield (fewer fibres and a more open sheet structure) outweighs the negative effects of the higher hemicellulose content on the dewatering properties. Moreover, the increased proportion of hemicellulose in the fibre walls resulted in improved bonding and increased tensile index at a certain refining energy. 

Secondly, we have studied the uniformity of impregnation at the fibre level by developing an accurate way of measuring sulphur and sodium content in measuring points that are 5-10 µm in diameter with miniaturized X-ray-based technology. This technology is considered cheap and efficient enough to be introduced in industrial labs and/or in online equipment. Our newly built miniaturized energy dispersive X-ray fluorescence (ED-XRF) demonstrates the capability of imaging sulphur and possibly sodium distribution in wood chip fibres or individual fibres on a micro scale. 

In parallel, to the above research we have studied a new catalytic lignin-selective cooking method where a substantial portion of the dissolved lignin can be extracted as vanillin, creating significant value and opportunities for new cost-efficient wood biorefinery systems. 

Abstract [sv]

För att förbättra konkurrensfördelarna med massafiberbaserade material såsom mjukpapper och förpackningsmaterial, jämfört med fossilbaserade produkter, är det viktigt att förbättra kunskapen om massatillverknings-processers selektivitet genom att optimera enhetsprocesserna; impregnering, kokning och raffinering. Det övergripande målet för alla massatillverknings-processer är att erhålla så effektiv och jämn fiberseparation som möjligt. För att erhålla jämnare distribution av impregnering måste vi studera hur frisättning av lignin på fibernivå via lättimpregnerade träflis kan uppnås med klassiska åtgärder som; utjämnad hydroxidjonkoncentration, ökad initial sulfidjonkoncentration, låg natriumjonkoncentration och låg koktemperatur kombinerat med oxidativ och reduktiv miljö. Vid tillverkning av kemi­mekanisk massa (CTMP) behöver vi erhålla så jämn sulfoneringsgrad som möjligt ner till fibernivå. Här behöver vi förbättra fördelningen av sulfitjonerna i vedflisen innan förvärmningen före raffinören. 

Vi studerade först selektiva kokningssystem för tillverkning av sulfatmassa i oxidativ miljö, polysulfid, respektive i reduktiv miljö, natriumborhydrid. Utbytet ökade från 48% till i bästa fall 53%, vilket resulterade i snabbare avvattning vid betingelser som simulerar tillverkning av hygienprodukter. Vi kunde förklara det ökade utbytet med att den positiva inverkan av färre fibrer vid viss ytvikt och öppnare arkstruktur dominerar över den negativa inverkan av högre halt vattenabsorberande hemicellulosa på avvattnings­egenskaperna. Den högre halten hemicellulosa i fiberväggarna bidrog till förbättrade bindningsegenskaper och ökat dragindex vid en specifik raffineringsenergi. Därefter studerade vi sätt att utvärdera homogenitet i  impregnering på fibernivå genom att ta fram en metodik som kan mäta svavel- och natriuminnehåll i mätpunkter som är 5-10 µm i diameter. Mikroskopi baserad på röntgenfluorescens bedöms vara lämplig för detta ändamål samt tillräckligt billig och effektiv att framöver kunna användas i industrilaboratorier och/eller i online-utrustning. 

Parallellt har också forskning utförts rörande en ny katalytisk lignin-selektiv kokningsmetod där en signifikant andel av ligninet kan lösas ut som värdefullt vanillin. Detta skapar framtida möjligheter att ta fram en kostnadseffektiv bioraffinaderimetodik där högt värde skapas både i form av väl separerade fibrer och i form av värdefulla naturliga kemikalier.

Place, publisher, year, edition, pages
Sundsvall: Mid Sweden University , 2021. , p. 76
Series
Mid Sweden University doctoral thesis, ISSN 1652-893X ; 348
National Category
Chemical Engineering Paper, Pulp and Fiber Technology
Identifiers
URN: urn:nbn:se:miun:diva-42090ISBN: 978-91-89341-15-9 (print)OAI: oai:DiVA.org:miun-42090DiVA, id: diva2:1556754
Public defence
2021-06-14, C312 och online via Zoom, Holmgatan 10, Sundsvall, 10:00 (English)
Opponent
Supervisors
Note

Vid tidpunkten för disputationen var följande delarbeten opublicerade: delarbete 3 inskickat, delarbete 4 & 5 manuskript.

At the time of the doctoral defence the following papers were unpublished: paper 3 submitted, paper 4 & 5 in manuscript.

Available from: 2021-05-24 Created: 2021-05-24 Last updated: 2023-01-18Bibliographically approved
List of papers
1. The effect of increased pulp yield using additives in the softwood kraft cook on the physical properties of low-grammage handsheets
Open this publication in new window or tab >>The effect of increased pulp yield using additives in the softwood kraft cook on the physical properties of low-grammage handsheets
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2017 (English)In: Nordic Pulp & Paper Research Journal, ISSN 0283-2631, E-ISSN 2000-0669, Vol. 32, no 3, p. 317-323Article in journal (Refereed) Published
Abstract [en]

The effect of increasing the pulp yield by the addition of sodium borohydride (NaBH4) or polysulfide (PS) in softwood kraft cooking, i.e. enhancing the retention of glucomannan, on the physical properties of low-grammage handsheets was studied. In addition to the yield improvement, an increase in tensile index was observed, especially at lower degrees of beating. These higher yield pulps showed an increase in pore volume, indicating an increased degree of swelling of the fibres. Presumably, the increased flexibility of the fibres affects the bonding strength and leads to the higher tensile index observed.

National Category
Chemical Engineering
Identifiers
urn:nbn:se:miun:diva-31895 (URN)10.3183/NPPRJ-2017-32-03-p317-323 (DOI)000411768200001 ()2-s2.0-85053279995 (Scopus ID)
Available from: 2017-10-18 Created: 2017-10-18 Last updated: 2021-05-24Bibliographically approved
2. Dewatering properties of low grammage handsheets softwood kraft pulps modified to minimize the need for refining
Open this publication in new window or tab >>Dewatering properties of low grammage handsheets softwood kraft pulps modified to minimize the need for refining
2018 (English)In: Nordic Pulp & Paper Research Journal, ISSN 0283-2631, E-ISSN 2000-0669, Vol. 33, no 3, p. 397-403Article in journal (Refereed) Published
Abstract [en]

Previous paper (Rahman et al. 2017) showed that the yield of softwood kraft pulp increased by the addition of either polysulfide or sodium borohydride because of higher hemicellulose retention. An increase in hemicellulose content can make dewatering more difficult as WRV of the pulp increases, but instead, an overall increase in pulp yield could improve dewatering as a sheet of a certain weight will contain fewer fibers, giving a more open sheet structure. It was therefore of interest to measure the dewatering properties of low grammage handsheets (20 g / m2) under conditions mimicking the tissue paper machine dewatering processes, and sheet strength properties, WRV, ° SR and fiber dimensions were also studied. The results showed that the positive influence of overall yield increase dominated the negative influence of an increase in hemicellulose content on the dewatering properties, particularly at lower refining energy levels. Furthermore, higher yield and higher hemicellulose content pulps had a higher tensile index at the same dryness. A given tensile index was achieved with less refining energy. The results indicate that increased yield and hemicellulose content by modifying the kraft pulping process will result in a pulp with a potential to improve tissue paper quality.

Keywords
dwell time, hemicellulose, refining, solid content, suction box dewatering, tensile index, thermoporosimetry, water retention value
National Category
Chemical Engineering
Identifiers
urn:nbn:se:miun:diva-32836 (URN)10.1515/npprj-2018-3037 (DOI)000450923900005 ()2-s2.0-85052642839 (Scopus ID)
Available from: 2018-02-12 Created: 2018-02-12 Last updated: 2021-05-24Bibliographically approved
3. On-Site X-ray Fluorescence Spectrometry Measurement Strategy for Assessing the Sulfonation to Improve Chemimechanical Pulping Processes
Open this publication in new window or tab >>On-Site X-ray Fluorescence Spectrometry Measurement Strategy for Assessing the Sulfonation to Improve Chemimechanical Pulping Processes
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2022 (English)In: ACS Omega, E-ISSN 2470-1343, Vol. 7, no 51, p. 48555-48563Article in journal (Refereed) Published
Abstract [en]

Minimizing the fiber property distribution would have the potential to improve the pulp properties and the process efficiency of chemimechanical pulp. To achieve this, it is essential to improve the level of knowledge of how evenly distributed the sulfonate concentration is between the individual chemimechanical pulp fibers. Due to the variation in quality between pulpwood and sawmill chips, as well as the on-chip screening method, it is difficult to develop an impregnation system that ensures the even distribution of sodium sulfite (Na2SO3) impregnation liquid. It is, therefore, crucial to measure the distribution of sulfonate groups within wood chips and fibers on a microscale. Typically, the degree of unevenness, i.e., the amount of fiber sulfonation and softening prior to defibration, is unknown on a microlevel due to excessively robust or complex processing methods. The degree of sulfonation at the fiber level can be determined by measuring the distribution of elemental sulfur and counterions of sulfonate groups, such as sodium or calcium. A miniaturized energy-dispersive X-ray fluorescence (ED-XRF) method has been developed to address this issue, enabling the analysis of sulfur distributions. It is effective enough to be applied to industrial laboratories for further development, i.e., improved image resolution and measurement time. 

National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:miun:diva-46771 (URN)10.1021/acsomega.2c07086 (DOI)000903289800001 ()2-s2.0-85144530016 (Scopus ID)
Available from: 2023-01-09 Created: 2023-01-09 Last updated: 2023-01-26Bibliographically approved
4.
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5. Improve the competitive advantages of pulp fiber-based products over fossil-based materials
Open this publication in new window or tab >>Improve the competitive advantages of pulp fiber-based products over fossil-based materials
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2021 (English)In: Accelerating the progress towards the 2030 SDGs in times of crisis / [ed] Catrin Johansson, Volker Mauerhofer, Östersund: Mid Sweden University , 2021, p. 2133-2145Conference paper, Published paper (Refereed)
Abstract [en]

To improve the competitive advantages of pulp fibre based materials such as tissue and packaging products over the fossil-based products, it is of key importance to improve the knowledge of the selectivity of the cooking process. There is also demand to expand the fundamental scientific understanding of pulp and paper manufacturing systems because of growing demand for replacing plastics. However, it is challenged to improve the selectivity of the cooking process by optimizing unit operation such as impregnation, cooking and refining. For pulp production based on chips regardless of chemical (kraft or sulphite) or high-yield (chemimechanical or semi-chemical pulp) pulping process, the efficiency of the impregnation is always crucial. To improve impregnation uniformity, we need to study how even distribution of lignin releases down to fibre level via easily impregnated wood chips. It can be achieved, using classic measures such as; equalized hydroxide ion concentration, increased initial sulphide ion concentration, low sodium ion concentration and low boiling temperature combined with the oxidative and reductive environment to understand how the chemicals quickly enter and distribute in the chips. However, we have studied the uniformity of impregnation at fibre level by the possibility of accurately measuring S and Na content by collimating the X-ray beam into a ~200 µm spot in diameter using energy-dispersive X-ray fluorescence (ED-XRF) spectrometry. In addition, we have also studied improved impregnation by selective cooking systems for sulphate pulp in oxidative (polysulfide) and reductive (sodium borohydride, NaBH4) environments. Our aim is to develop standard measurement methods to improve the smoothness of fibre properties for tissue and packaging products to reach the sustainable development goal (SDG) stated by the UN at target 9.5 “Enhance research and upgrade industrial technologies”.

Place, publisher, year, edition, pages
Östersund: Mid Sweden University, 2021
Keywords
CTMP, ED-XRF, Hemicellulose, Impregnation, polysulfide
National Category
Chemical Engineering
Identifiers
urn:nbn:se:miun:diva-43614 (URN)978-91-89341-17-3 (ISBN)
Conference
27th International Sustainable Development Research Society Conference, Östersund, Sweden, July 13 – 15, 2021.
Available from: 2021-11-05 Created: 2021-11-05 Last updated: 2023-01-18Bibliographically approved

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Rahman, Hafizur

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