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Alkaline steeping of dissolving pulp. Part I: cellulose degradation kinetics

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Abstract

The production of cellulosic man made fibres by the viscose process has been known for more than 120 years now, but still some aspects are not sufficiently understood in detail. The carbohydrates in the pulp are exposed to varying conditions during the manufacturing process. In the first production step of steeping, the strong alkaline treatment leads to undesirable loss reactions of the cellulose. In this study, a comprehensive kinetic model was developed for process simulation of cellulose degradation for the fist time comprising primary and secondary peeling, stopping and alkaline hydrolysis. A total chlorine free bleached beech sulfite pulp was treated with 18 % sodium hydroxide at 40, 50 and 60 °C for time periods up to 80 h. The corresponding reaction rates, activation energies and frequency factors for all reaction steps were calculated. The peeling-off reaction was of great significance for the cellulose yield loss, due to a contribution of the secondary peeling after random chain scission. The moderate decrease of the intrinsic viscosity and the changes in molar mass distribution indicated the validity of the assumption. Further, a reduction of the carbonyl and an increase of the carboxyl groups in the cellulose were observed due to the formation of the stable metasaccharinic acid at the reducing ends of the molecules. The fibre morphology was investigated by SEM measurements. Already short alkaline treatment times favored the dissolution of fibril fragments from the fibre surface leading to a smooth fibre surface.

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Abbreviations

BAR:

Benzilic acid rearrangement

CCOA:

Carbazole-9-carbonyloxyamine

D :

Overall carbohydrate yield loss

DMAc:

N,N-Dimethylacetamide

DP:

Degree of polymerisation

FDAM:

9H-fluoren-2-yl-diazomethane

FE-SEM:

Scanning electron microscope

H :

Material degraded by hydrolysis

HPLC:

High performance liquid chromatography

ISA:

Isosaccharinic acid

k h :

Rate constant of the alkaline hydrolysis

k p :

Rate constant of the peeling reaction

k s :

Rate constant of the stopping reaction

MALLS:

Multi-angle laser light scattering

MSA:

Metasaccharinic acid

MB:

Methylene blue

MMD:

Molar mass distribution

Mn:

Number-average molecular weight

Mw:

Weight-average molecular weight

Odp:

Oven dried pulp

P :

Mole fraction of peeled-off material

PAD:

Pulsed amperometric detection

PDI:

Polydispersity index

R :

Amount of reducing end groups

R 0 :

Initial reducing end group mole fraction

REG:

Reducing end group

SEC:

Size exclusion chromatography

TCF:

Total chlorine free

WRV:

Water retention value

Γ0 :

Initial amount of the carbohydrates

η:

Intrinsic viscosity

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Acknowledgments

Financial support was provided by the Austrian government, the provinces of lower Austria, upper Austria, and Carinthia as well as by Lenzing AG. We also express our gratitude to the Johannes Kepler University, Linz, the University of Natural Resources and Applied Life Sciences, Vienna, and Lenzing AG for their in-kind contributions

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Authors and Affiliations

  1. Kompetenzzentrum Holz GmbH, Altenberger Strasse 69, 4040, Linz, Austria

    Danuta Joanna Mozdyniewicz

  2. Department of Forest Products Technology, Aalto University School of Science and Technology, Vuorimiehentie 1, P.O. Box 16300, Espoo, Finland

    Kaarlo Nieminen & Herbert Sixta

Authors
  1. Danuta Joanna Mozdyniewicz
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  2. Kaarlo Nieminen
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  3. Herbert Sixta
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Correspondence to Herbert Sixta.

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Mozdyniewicz, D.J., Nieminen, K. & Sixta, H. Alkaline steeping of dissolving pulp. Part I: cellulose degradation kinetics. Cellulose 20, 1437–1451 (2013). https://doi.org/10.1007/s10570-013-9926-2

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  • DOI: https://doi.org/10.1007/s10570-013-9926-2

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