Analysis of degradation products in rayon spinning baths
-
Eva Liftinger
,
Gabriele Schild
Abstract
An analytical method for the determination and quantification of the main organic degradation products of viscose spinning baths was outlined herein and successfully applied. Samples were ethoximated and silylated for GC-MS analysis. The main challenge in the analysis was the quantification of the degradation products because standard compounds are often not commercially available. Analyte recovery was optimized with regard to pH and lyophilization conditions. Given that the spinning bath analytes showed a very broad range of volatility, internal standardization by the degradation product of uniformly 13C-labeled glucose in alkaline media was used. This approach allowed for the first time for the accounting of a major part of the organic components in the viscose spinning baths. On average, 57% of total organic carbon was characterized by quantifying 21 individual substances. The methodology opens new perspectives of keeping track of the formation and origin of organic degradation products. It is a prerequisite to all further efforts to avoid contamination of the spinning bath and achieve a higher product quality and a better closure of process cycles. Furthermore, it can be easily applied to other highly complex industrial process streams involving polysaccharide degradation products as they are emerging, for instance, in biorefineries.
Acknowledgments
Financial support was provided by the Austrian government, the provinces of Lower Austria, Upper Austria and Carinthia, as well as by the Lenzing AG. We also express our gratitude to the Johannes Kepler University, Linz, the University of Natural Resources and Life Sciences Vienna (BOKU), and the Lenzing AG for their in-kind contributions.
References
Andrews, M.A. (1989) Capillary gas-chromatographic analysis of monosaccharides: improvements and comparisons using trifluoroacetylation and trimethylsilylation of sugar O-benzyl- and O-methyl-oximes. Carbohydr. Res. 194:1–19.10.1016/0008-6215(89)85001-3Suche in Google Scholar
Aspinall, G.O., Greenwood, C.T., Sturgeon, R.J. (1961) The degradation of xylans by alkali. J. Chem. Soc. 712:3667–3674.10.1039/jr9610003667Suche in Google Scholar
Becker, M., Liebner, F., Rosenau, T., Potthast, A. (2013a) Ethoximation-silylation approach for mono- and disaccharide analysis and characterization of their identification parameters by GC/MS. Talanta 115:642–651.10.1016/j.talanta.2013.05.052Suche in Google Scholar
Becker, M., Zweckmair, T., Forneck, A., Rosenau, T., Potthast, A., Liebner, F. (2013b) Evaluation of different derivatisation approaches for gas chromatographic-mass spectrometric analysis of carbohydrates in complex matrices of biological and synthetic origin. J. Chromatogr. A 1281:115–126.10.1016/j.chroma.2013.01.053Suche in Google Scholar
Bogolitsyna, A., Becker, M., Borgards, A., Liebner, F., Rosenau, T., Potthast, A. (2012) Degradation products of lignocellulosics in pulp mill effluents: comparison and evaluation of different gas chromatographic techniques for a comprehensive analysis. Holzforschung 66:917–925.10.1515/hf-2012-0008Suche in Google Scholar
Coleman, J.E., Ricciuti, C., Swern, D. (1956) Improved preparation of 9(10),10(9)-ketohydroxystearic acids by oxidation of oleic acid with potassium permanganate in neutral solution. J. Am. Chem. Soc. 78:5342–5345.10.1021/ja01601a050Suche in Google Scholar
DIN-32645. Chemische Analytik – Nachweis-, Erfassungs- und Bestimmungsgrenze unter Wiederholbedingungen DIN 32645, 2011.Suche in Google Scholar
Knill, C.J., Kennedy, J.F. (2003) Determination of the degradation products present in a cellulose alkaline hydrolysate. Cell. Chem. Technol. 37:19–33.Suche in Google Scholar
Matsunaga, S., Kawamura, K. (2000) Determination of alpha- and beta-hydroxycarbonyls and dicarbonyls in snow and rain samples by GC/FID and GC/MS employing benzyl hydroxyl oxime derivatization. Anal. Chem. 72:4742–4746.10.1021/ac000267gSuche in Google Scholar
Mizuno, T., Weiss, A.H. (1974) Synthesis and utilization of formose sugars. In: Advances in Carbohydrate Chemistry and Biochemistry. Eds. Tipson, R.S., Horton, D. Academic Press, New York. pp. 173–227.10.1016/S0065-2318(08)60250-4Suche in Google Scholar
Mozdyniewicz, D.J., Schild, G., Sixta, H. (2014) Alkaline steeping of dissolving pulp. Part II: soluble compounds in the press lye. Cellulose 21:2889–2900.10.1007/s10570-014-0291-6Suche in Google Scholar
Niemelä, K. (1988) Gas-liquid chromatography-mass spectrometry studies on pine kraft black liquors. III. The liberation of carboxylic acids in the initial phase of pulping. J. Chromatogr. A 446:247–252.10.1016/S0021-9673(00)94439-XSuche in Google Scholar
Niemelä, K. (1990) Conversion of xylan, starch, and chitin into carboxylic acids by treatment with alkali. Carbohydr. Res. 204:37–49.10.1016/0008-6215(90)84019-QSuche in Google Scholar
Niemelä, K., Sjöström, E. (1986) The conversion of cellulose into carboxylic cids by drastic alkali treatment. Biomass 11:215–221.10.1016/0144-4565(86)90068-5Suche in Google Scholar
Novotny, O., Cejpek, K., Velisek, J. (2008) Formation of carboxylic acids during degradation of monosaccharides. Czech J. Food Sci. 26:117–131.10.17221/2465-CJFSSuche in Google Scholar
Richards, G.N., Sephton, H.H. (1957) The alkaline degradation of polysaccharides. Part I. Soluble products of the action of sodium hydroxide on cellulose. J. Chem. Soc. 4492–4499.10.1039/jr9570004492Suche in Google Scholar
Shaw, P.B., Robinson, G.F., Rice, C.R., Humphreys, P.N., Laws, A.P. (2012) A robust method for the synthesis and isolation of β-gluco-isosaccharinic acid ((2R,4S)-2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid) from cellulose and measurement of its aqueous pKa. Carbohydr. Res. 349:6–11.10.1016/j.carres.2011.11.022Suche in Google Scholar
Yaylayan, V.A., Huyghues-Despointes, A. (1996) Identification of per-O-(trimethylsilyl) derivatives of aldoses generated from thermal decomposition of N-(1-deoxy-D-fructopyrano s-1-yl)proline: reversibility of the Amadori rearrangement. Carbohydr. Res. 286:179–187.10.1016/0008-6215(96)00046-8Suche in Google Scholar
©2015 by De Gruyter
Artikel in diesem Heft
- Frontmatter
- Effect of hydroxide and sulfite ion concentration in alkaline sulfite anthraquinone (ASA) pulping – a comparative study
- Novel insight in carbohydrate degradation during alkaline treatment
- Activated hydrogen peroxide decolorization of a model azo dye-colored pulp
- Effects of inorganic salts on the degradation of 2,5-dihydroxy-[1,4]-benzoquinone as a key chromophore in pulps by hydrogen peroxide under basic conditions
- Analysis of degradation products in rayon spinning baths
- Effect of cellulase-assisted refining on the thermal degradation of bleached high-density paper
- Synthesis and characterization of functionalized 4-O-methylglucuronoxylan derivatives
- Hydrophobic materials based on cotton linter cellulose and an epoxy-activated polyester derived from a suberin monomer
- Depolymerization of cellulose during cold acidic chlorite treatment
- Enhanced stability of PVA electrospun fibers in water by adding cellulose nanocrystals
- Micro-nanoparticle gels obtained from bark for their use alone and with chitosan and Na-CMC in paper coatings
- Conversion of sulfur-free black liquor into fuel gas by supercritical water gasification
- Modification of acid hydrolysis lignin for value-added applications by micronization followed by hydrothermal alkaline treatment
- Preparation of lignin-containing porous microspheres through the copolymerization of lignin acrylate derivatives with styrene and divinylbenzene
- Wood-based activated carbons for supercapacitors with organic electrolyte
- Functionality and physico-chemical characteristics of wheat straw lignin, Biolignin™, derivatives formed in the oxypropylation process
- Antioxidant activity of various lignins and lignin-related phenylpropanoid units with high and low molecular weight
- Characterization of technical lignins by NMR spectroscopy: optimization of functional group analysis by 31P NMR spectroscopy
- Chemical composition of volatiles extracted from indigenous tree species of Uganda: composition of bark extracts from Psorospermum febrifugum and Milicia excelsa
Artikel in diesem Heft
- Frontmatter
- Effect of hydroxide and sulfite ion concentration in alkaline sulfite anthraquinone (ASA) pulping – a comparative study
- Novel insight in carbohydrate degradation during alkaline treatment
- Activated hydrogen peroxide decolorization of a model azo dye-colored pulp
- Effects of inorganic salts on the degradation of 2,5-dihydroxy-[1,4]-benzoquinone as a key chromophore in pulps by hydrogen peroxide under basic conditions
- Analysis of degradation products in rayon spinning baths
- Effect of cellulase-assisted refining on the thermal degradation of bleached high-density paper
- Synthesis and characterization of functionalized 4-O-methylglucuronoxylan derivatives
- Hydrophobic materials based on cotton linter cellulose and an epoxy-activated polyester derived from a suberin monomer
- Depolymerization of cellulose during cold acidic chlorite treatment
- Enhanced stability of PVA electrospun fibers in water by adding cellulose nanocrystals
- Micro-nanoparticle gels obtained from bark for their use alone and with chitosan and Na-CMC in paper coatings
- Conversion of sulfur-free black liquor into fuel gas by supercritical water gasification
- Modification of acid hydrolysis lignin for value-added applications by micronization followed by hydrothermal alkaline treatment
- Preparation of lignin-containing porous microspheres through the copolymerization of lignin acrylate derivatives with styrene and divinylbenzene
- Wood-based activated carbons for supercapacitors with organic electrolyte
- Functionality and physico-chemical characteristics of wheat straw lignin, Biolignin™, derivatives formed in the oxypropylation process
- Antioxidant activity of various lignins and lignin-related phenylpropanoid units with high and low molecular weight
- Characterization of technical lignins by NMR spectroscopy: optimization of functional group analysis by 31P NMR spectroscopy
- Chemical composition of volatiles extracted from indigenous tree species of Uganda: composition of bark extracts from Psorospermum febrifugum and Milicia excelsa
