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The influence of different types of bisulfite cooking liquors on pine wood components
Karlstad University, Faculty of Health, Science and Technology (starting 2013), Department of Engineering and Chemical Sciences.ORCID iD: 0000-0003-4841-2568
Karlstad University, Faculty of Health, Science and Technology (starting 2013), Department of Engineering and Chemical Sciences. (Pulp technology)
MoRe Research, Örnsköldsvik, Sweden.
Domsjö Fabriker, Örnsköldsvik, Sweden.
2016 (English)In: BioResources, ISSN 1930-2126, E-ISSN 1930-2126, Vol. 11, no 3, 5961-5973 p.Article in journal (Refereed) Published
Abstract [en]

Single stage sodium bisulfite cooking of pine was carried out to study the initial phase of the bisulfite cook and the experiments were carried out using either a lab or a mill prepared cooking acid. The chemical consumption, the pH profile and the pulp yield with respect to cellulose, lignin, glucomannan, xylan and extractives were investigated. The pulp composition with respect to carbohydrates and lignin content was summarized in a kinetic model. The initial phase of the bisulfite cook was extended to 5 h cooking time down to a final pulp yield of about 60 %. The side reactions with respect to thiosulfate and sulfate formation were investigated continuously in all experiments. The cooking temperature used in these experiments was 154 °C.

Place, publisher, year, edition, pages
Raleigh: North Carolina State University , 2016. Vol. 11, no 3, 5961-5973 p.
Keyword [en]
Activation energy, bisulfite pulping, cellulose, extractives, glucomannan, lignin, pine, thiosulfate and xylan.
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
URN: urn:nbn:se:kau:diva-37304OAI: oai:DiVA.org:kau-37304DiVA: diva2:845060
Note

This paper was published as manuscript in the thesis and was then called "The Initial Phase of Sodium Bisulfite Pulping of Pine", Part II.

Available from: 2015-08-10 Created: 2015-08-06 Last updated: 2016-10-25Bibliographically approved
In thesis
1. The initial phase of the sodium bisulfite pulping of softwood dissolving pulp
Open this publication in new window or tab >>The initial phase of the sodium bisulfite pulping of softwood dissolving pulp
2015 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

The sulfite pulping process is today practised in only a small number of pulp mills around the globe and the number of sulfite mills that use sodium as the base (cation) is less than five. However, due to the increasing interest in the wood based biorefinery concept, the benefits of sulfite pulping and especially the sodium based variety, has recently gained a lot of interest. It was therefore considered to be of high importance to further study the sodium based sulfite process to investigate if its benefits could be better utilized in the future in the production of dissolving pulps. Of specific interest was to investigate how the pulping conditions in the initial part of the cook (≥ 60 % pulp yield) should be performed in the best way.

Thus, this thesis is focused on the initial phase of single stage sodium bisulfite cooking of either 100 % spruce or 100 % pine wood chips. The cooking experiments were carried out with either a lab prepared or a mill prepared cooking acid and the temperature and cooking time were varied. Activation energies for different wood components were investigated as well as side reactions concerning the formation of thiosulfate and sulfate.

Abstract [en]

Single stage sodium bisulfite cooking was carried out on either spruce or pine wood chips to investigate the influence of several process parameters in the initial phase of such a cook i.e. between 100 % and 60 % pulp yield. The cooking experiments were carried out with either a lab prepared or a mill prepared cooking acid and the temperature and time in the initial stage were varied. The influence of dissolved organics and inorganics components in the cooking liquor on the final pulp properties and side reactions were investigated. The impact of temperature and time on the pulp components were analyzed with respect to carbohydrates, lignin, extractives and thiosulfate. Kinetic equations were developed and the activation energies for delignification and carbohydrate dissolution were calculated using the Arrhenius equation.

It was found that if using a mill prepared cooking acid, this had a beneficial effect with respect to side reactions, better extractives removal and higher pH stability during the cook, compared to a corresponding cook with a lab prepared cooking acid. Cooking with mill prepared and lab prepared cooking acids showed the same behaviour with respect to delignification and carbohydrate degradation, but the lab acid experiments resulted in a higher thiosulfate formation during the cook. The cellulose yield was not affected at all during the initial phase of the sulfite cook verifying earlier results by other researchers. The temperature had an influence on both the delignification rate and the rate of hemicelluloses removal.  The corresponding activation energies were found to increase in the following order; cellulose, xylan, glucomannan and lignin.

Place, publisher, year, edition, pages
Karlstad: Karlstads universitet, 2015. 54 p.
Series
Karlstad University Studies, ISSN 1403-8099 ; 2015:34
Keyword
Activation energy, bisulfite pulping, cellulose, delignification, extractives, glucomannan, hemicelluloses, lignin, pine, spruce, thiosulfate, total SO2, xylan
National Category
Other Chemical Engineering Chemical Process Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kau:diva-36494 (URN)978-91-7063-652-3 (ISBN)
Presentation
2015-09-25, 9 C 203, Karlstad University, Karlstad, 13:00 (English)
Opponent
Supervisors
Funder
Knowledge Foundation
Note

Artikel 1: "The Initial Phase of Sodium Bisulfite Pulping of Spruce: Part 1" ingick i avhandlingen som manuskript. Nu publicerad.

Available from: 2015-09-04 Created: 2015-06-17 Last updated: 2016-03-31Bibliographically approved
2. The initial phase of sodium sulfite pulping of softwood: A comparison of different pulping options
Open this publication in new window or tab >>The initial phase of sodium sulfite pulping of softwood: A comparison of different pulping options
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Single stage and two-stage sodium sulfite cooking were carried out on either spruce, pine or pure pine heartwood chips to investigate the influence of several process parameters on the initial phase of such a cook down to about 60 % pulp yield. The cooking experiments were carried out in the laboratory with either a lab-prepared or a mill-prepared cooking acid and the temperature and time were varied. The influences of dissolved organic and inorganic components in the cooking liquor on the final pulp composition and on the extent of side reactions were investigated. Kinetic equations were developed and the activation energies for delignification and carbohydrate dissolution were calculated using the Arrhenius equation. A better understanding of the delignification mechanisms during bisulfite and acid sulfite cooking was obtained by analyzing the lignin carbohydrate complexes (LCC) present in the pulp when different cooking conditions were used. It was found that using a mill-prepared cooking acid beneficial effect with respect to side reactions, extractives removal and higher stability in pH during the cook were observed compared to a lab-prepared cooking acid. However, no significant difference in degrees of delignification or carbohydrate degradation was seen.

 The cellulose yield was not affected in the initial phase of the cook however; temperature had an influence on the rates of both delignification and hemicellulose removal. It was also found that the  corresponding activation energies increased in the order:  xylan, glucomannan, lignin and cellulose. The cooking temperature could thus be used to control the cook to a given carbohydrate composition in the final pulp. Lignin condensation reactions were observed during acid sulfite cooking, especially at higher temperatures. The LCC studies indicated the existence of covalent bonds between lignin and hemicellulose components with respect to xylan and glucomannan. LCC in native wood showed the presence of phenyl glycosides, ϒ-esters and α-ethers; whereas the α-ethers  were affected during sulfite pulping. The existence of covalent bonds between lignin and wood polysaccharides might be the rate-limiting factor in sulfite pulping.

Abstract [en]

The sulfite pulping process is today practised in only a small number of pulp mills around the globe and the number of sulfite mills that use sodium as the base (cation) is less than five. However, due to the increasing interest in the wood based biorefinery concept, the benefits of sulfite pulping and especially the sodium based variety, has recently gained a lot of interest. It was therefore considered to be of high importance to further study the sodium based sulfite process to investigate if its benefits could be better utilized in the future in the production of dissolving pulps. Of specific interest was to investigate how the pulping conditions in the initial part of the cook (≥ 60 % pulp yield) should be performed in the best way.

Thus, this thesis is focused on the initial phase of sodium based single stage bisulfite, acid sulfite and two-stage sulfite cooking of either 100 % spruce, 100 % pine or 100 % pine heartwood chips. The cooking experiments were carried out with either a lab prepared or a mill prepared cooking acid and the temperature and cooking time were varied. Activation energies for different wood components were investigated as well as side reactions concerning the formation of thiosulfate. LCC (Lignin carbohydrates complexes) studies were carried out to investigate the influence of different cooking conditions on lignin carbohydrate linkages.

Place, publisher, year, edition, pages
Karlstad: Karlstads universitet, 2016. 81 p.
Series
Karlstad University Studies, ISSN 1403-8099 ; 2016:43
Keyword
Activation energy, acid sulfite pulping, bisulfite pulping, cellulose, delignification, dissolving pulp, extractives, glucomannan, hemicelluloses, lignin, lignin condensation, lignin carbohydrate complexes, pine, spruce, thiosulfate, total SO2, xylan
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
urn:nbn:se:kau:diva-46929 (URN)978-91-7063-726-1 (ISBN)
Public defence
2016-12-15, Rejmersalen, 9C204, Karlstad University, Karlstad, Sweden, 13:00 (English)
Opponent
Supervisors
Funder
Knowledge FoundationThe Kempe FoundationsMoRe ResearchDomsjö FabrikerKnut and Alice Wallenberg Foundation
Available from: 2016-11-25 Created: 2016-10-24 Last updated: 2016-11-25Bibliographically approved

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