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The initial phase of sodium sulfite pulping of softwood: A comparison of different pulping options
Karlstads universitet, Fakulteten för hälsa, natur- och teknikvetenskap (from 2013), Institutionen för ingenjörs- och kemivetenskaper (from 2013).ORCID-id: 0000-0003-4841-2568
2016 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Karlstad: Karlstads universitet, 2016. , s. 81
Serie
Karlstad University Studies, ISSN 1403-8099 ; 2016:43
Nyckelord [en]
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
Nationell ämneskategori
Kemiteknik
Forskningsämne
Kemiteknik
Identifikatorer
URN: urn:nbn:se:kau:diva-46929ISBN: 978-91-7063-726-1 (tryckt)OAI: oai:DiVA.org:kau-46929DiVA, id: diva2:1039534
Disputation
2016-12-15, Rejmersalen, 9C204, Karlstad University, Karlstad, Sweden, 13:00 (Engelska)
Opponent
Handledare
Forskningsfinansiär
KK-stiftelsenKempestiftelsernaMoRe ResearchDomsjö FabrikerKnut och Alice Wallenbergs Stiftelse
Anmärkning

Artikel 5 publicerad som manuskript i avhandlingen. 

Tillgänglig från: 2016-11-25 Skapad: 2016-10-24 Senast uppdaterad: 2019-10-28Bibliografiskt granskad
Delarbeten
1. The Initial Phase of Sodium Bisulfite Pulping of Spruce: Part 1
Öppna denna publikation i ny flik eller fönster >>The Initial Phase of Sodium Bisulfite Pulping of Spruce: Part 1
2016 (Engelska)Ingår i: Cellulose Chemistry and Technology, ISSN 0576-9787, Vol. 50, nr 2, s. 293-300Artikel i tidskrift (Refereegranskat) Published
Nyckelord
bisulphite cooking, cellulose, glucomannan, kinetics, lignin, spruce, thiosulphate and xylan
Nationell ämneskategori
Kemiteknik
Forskningsämne
Kemiteknik
Identifikatorer
urn:nbn:se:kau:diva-41142 (URN)000376835600015 ()
Tillgänglig från: 2016-03-29 Skapad: 2016-03-29 Senast uppdaterad: 2017-11-30Bibliografiskt granskad
2. The influence of the temperature on the initial phase of sodium bisulfite pulping of spruce
Öppna denna publikation i ny flik eller fönster >>The influence of the temperature on the initial phase of sodium bisulfite pulping of spruce
2015 (Engelska)Ingår i: O Papel, ISSN 0031-1057, Vol. 76, nr 4, s. 56-61Artikel i tidskrift (Refereegranskat) Published
Nyckelord
Bisulfite pulping, cellulose, glucomannan, kinetics, lignin, spruce, thiosulfate and xylan
Nationell ämneskategori
Kemiteknik
Forskningsämne
Kemiteknik
Identifikatorer
urn:nbn:se:kau:diva-36025 (URN)
Tillgänglig från: 2015-05-18 Skapad: 2015-05-18 Senast uppdaterad: 2016-10-24Bibliografiskt granskad
3. The influence of different types of bisulfite cooking liquors on pine wood components
Öppna denna publikation i ny flik eller fönster >>The influence of different types of bisulfite cooking liquors on pine wood components
2016 (Engelska)Ingår i: BioResources, ISSN 1930-2126, E-ISSN 1930-2126, Vol. 11, nr 3, s. 5961-5973Artikel i tidskrift (Refereegranskat) 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.

Ort, förlag, år, upplaga, sidor
Raleigh: North Carolina State University, 2016
Nyckelord
Activation energy, bisulfite pulping, cellulose, extractives, glucomannan, lignin, pine, thiosulfate and xylan.
Nationell ämneskategori
Kemiteknik
Forskningsämne
Kemiteknik
Identifikatorer
urn:nbn:se:kau:diva-37304 (URN)10.15376/biores.11.3.5961-5973 (DOI)000384922400025 ()
Anmärkning

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

Tillgänglig från: 2015-08-10 Skapad: 2015-08-06 Senast uppdaterad: 2017-11-02Bibliografiskt granskad
4. Some process aspects on single-stage bisulfite pulping of pine
Öppna denna publikation i ny flik eller fönster >>Some process aspects on single-stage bisulfite pulping of pine
2016 (Engelska)Ingår i: Nordic Pulp & Paper Research Journal, ISSN 0283-2631, E-ISSN 2000-0669, Vol. 31, nr 3, s. 379-385Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Sulfite pulping of pine is well-known to be a risky process because problematic lignin conden-sation reactions can occur resulting in poor pulp quality. However, sulfite pulping of pine is interesting of economic reasons as pine wood is cheaper than spruce. Therefore it has become interesting to investigate sulfite pulping again to determine if old data are still valid. Thus sodium bisulfite pulping of pine was carried out to investigate the influence of time, temperature and cooking acid quality. A small comparison of spruce pulping was also included. By using different cooking temperatures the activation energies for delignification and for degradation of cellulose and hemicelluloses could be determined. The results showed no lignin condensation reactions, thus it was not problematic to carry out these pine cooking experiments. It was found that glucomannan had higher activation energy than xylan and the activation energies of these hemicelluloses were lower than the corresponding value for the lignin degradation. It was found that the activation energy for bisulfite pulping of pine was slightly lower than the activation energy for bisulfite pulping of spruce.

Ort, förlag, år, upplaga, sidor
AB SVENSK PAPPERSTIDNING, 2016
Nyckelord
Activation energy, Bisulfite pulping, Cellulose, Extractives, Glucomannans, Lignin, Pine, Spruce, Thiosulfate, Xylans
Nationell ämneskategori
Kemiteknik
Forskningsämne
Kemiteknik
Identifikatorer
urn:nbn:se:kau:diva-47275 (URN)10.3183/NPPRJ-2016-31-03-p379-385 (DOI)000387974700001 ()
Tillgänglig från: 2016-11-24 Skapad: 2016-11-24 Senast uppdaterad: 2019-11-21Bibliografiskt granskad
5. Some process aspects on acid sulphite pulping of softwood
Öppna denna publikation i ny flik eller fönster >>Some process aspects on acid sulphite pulping of softwood
2016 (Engelska)Ingår i: Journal of Science & Technology for Forest Products and Processes, ISSN 1927-6311, E-ISSN 1927-632X, Vol. 6, nr 2, s. 48-54Artikel i tidskrift (Refereegranskat) Published
Ort, förlag, år, upplaga, sidor
Montreal: Pulp and Paper Technical Association of Canada, 2016
Nationell ämneskategori
Kemiteknik
Forskningsämne
Kemiteknik
Identifikatorer
urn:nbn:se:kau:diva-48304 (URN)000402538300004 ()
Tillgänglig från: 2017-04-11 Skapad: 2017-04-11 Senast uppdaterad: 2019-11-21Bibliografiskt granskad
6. The Reactivity of Lignin Carbohydrate Complex (LCC) During Manufacture of Dissolving Sulphite Pulp from Softwood
Öppna denna publikation i ny flik eller fönster >>The Reactivity of Lignin Carbohydrate Complex (LCC) During Manufacture of Dissolving Sulphite Pulp from Softwood
Visa övriga...
2018 (Engelska)Ingår i: Industrial crops and products (Print), ISSN 0926-6690, E-ISSN 1872-633X, s. 315-322Artikel i tidskrift (Refereegranskat) Published
Ort, förlag, år, upplaga, sidor
Elsevier, 2018
Nyckelord
Lignin carbohydrate complexes, pine heartwood, acid sulfite pulping, two-stage sulfite pulping, covalent bonds
Nationell ämneskategori
Kemiteknik
Forskningsämne
Kemi; Kemiteknik
Identifikatorer
urn:nbn:se:kau:diva-46925 (URN)10.1016/j.indcrop.2018.02.038 (DOI)000428824100037 ()
Forskningsfinansiär
Domsjö FabrikerKK-stiftelsenMoRe ResearchKnut och Alice Wallenbergs StiftelseKempestiftelserna
Tillgänglig från: 2016-10-24 Skapad: 2016-10-24 Senast uppdaterad: 2018-09-06Bibliografiskt granskad

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