Abstract
Oxalic acid (OA), formed as an oxidation product in alkaline peroxide bleaching (P) of mechanical pulps, can form a sparingly soluble salt with calcium and cause severe scale deposit problems. The focus of this work was the question how much OA is formed from the different components of spruce (Picea abies (L.) Karst.), i.e., from cellulose, lignin, hemicelluloses, extractives, and bark, during the P-stage of bleaching. Isolated wood components and monosaccharides typical for spruce hemicelluloses and pectins were treated with chemicals of P-stage for 90 min at 73°C, and the released OA was analyzed by ion chromatography. Most OA was formed from galacturonic and glucuronic acids, xylans, and lignin. Taking into account the content of these substances in spruce wood, lignin can be regarded as the major source of oxalate. Untreated spruce bark was found to contain substantial amounts of oxalate, and an additional amount of oxalate was formed in the P-stage. It is evident that effective debarking is essential, not only for pulp brightness, but also for the control of calcium oxalate formation.
Acknowledgments
This work is part of the activities of the Process Chemistry Centre (PCC) at Åbo Akademi University. Jenni Rahikainen from VTT is acknowledged for supplying the EMAL lignin sample. Sappi Fine Paper Europe and Kemira are acknowledged for financing this work.
References
Agnemo, R., Gellerstedt, G. (1979) The reactions of lignin with alkaline hydrogen peroxide. Part II: Factors influencing the decomposition of phenolic structures. Acta Chem. Scand. B 33:337–342.10.3891/acta.chem.scand.33b-0337Search in Google Scholar
Alén, R. (2000) Structure and chemical composition of wood. In: Papermaking Science and Technology, Vol. 3 Forest Products Chemistry. Ed. Stenius, P. Fapet Oy, Helsinki. pp. 12–57.Search in Google Scholar
Auhorn, W., Melzer, J. (1979) Improved efficiency of wet end additives in closed wet end systems through elimination of detrimental substances. Tappi Ann. Meeting Proc., Tappi Press, Atlanta, USA. pp. 49–66.Search in Google Scholar
Bailey, C.W., Dence, C.W. (1969) Reactions of alkaline hydrogen peroxide with softwood lignin model compounds, spruce milled-groundwood lignin and spruce groundwood. Tappi J. 52:491–500.Search in Google Scholar
Björkman, A. (1956) Studies on finely divided wood, Part I. Extraction of lignin with neutral solvents. Svensk Papperstidning-Nordisk Cellulosa 59:477–485.Search in Google Scholar
Brännvall E. (2009) Wood handling. In: Pulping chemistry and technology. Eds. Ek, M., Gellerstedt, G., Henriksson, G. Walter de Gruyter GmbH & Co., Berlin. pp. 13–34.Search in Google Scholar
Buchert, J., Teleman, A., Harjunpää, V., Tenkanen, M., Viikari, L., Vuorinen, T. (1995) Effect of cooking and bleaching on the structure of xylan in conventional pine kraft pulp. Tappi J. 78:125–130.Search in Google Scholar
Doherty, W.O.S., Fellows, C.M., Gorjian, S., Senogles, E., Cheung, W.H. (2004) Inhibition of calcium oxalate monohydrate by poly(acrylic acid)s with different end groups. J. Appl. Polym. Sci. 91:2035–2041.Search in Google Scholar
Ek, M., Gierer, J., Jansbro, K., Reitberger, T. (1989) Study on the selectivity of bleaching with oxygen-containing species. Holzforschung 43:391–396.10.1515/hfsg.1989.43.6.391Search in Google Scholar
Elsander, A., Ek, M. Gellerstedt, G. (2000) Oxalic acid formation during ECF and TCF bleaching of kraft pulp. Tappi J. 83:73–77.Search in Google Scholar
Fengel, D., Wegener, G. (1989) Chemical composition and analysis of wood. In: Wood-Chemistry, Ultrastructure, Reactions. Walter de Gruyter, Berlin, Germany. pp. 26–59.Search in Google Scholar
Fiskari, J. (1999) Oxalic acid formation in oxygen chemical bleaching. Proceedings of the 1999 TAPPI Pulping Conference, Orlando, FL, USA, 31 Oct.–4 Nov. 1999, vol. 1, pp.7–10.Search in Google Scholar
Francheschi, V.R. (1987) Oxalic acid metabolism and calcium oxalate formation in Lemna minor L. Plant Cell Environm. 10:397–406.10.1111/j.1365-3040.1987.tb01816.xSearch in Google Scholar
Gierer, J., Imsgard, F. (1977) The reactions of lignins with oxygen and hydrogen peroxide in alkaline media. Svensk Papperstidn. 80:510–518.Search in Google Scholar
Hudgins, J.W., Krekling, T., Francheschi, V.R. (2003) Distribution of calcium oxalate crystals in the secondary phloem of conifers: a constitiutive defense mechanism? New Phytol. 159:677–690.10.1046/j.1469-8137.2003.00839.xSearch in Google Scholar PubMed
Johnson, D. (1998) Removing beerstone: a look at alternative cleaning methods. Modern Brew. Age 49(March 23):37.Search in Google Scholar
Kempf, A.W., Dence, C.W. The reactions of hardwood lignin models with alkaline hydrogen peroxide. Chemisty of Delignification with Oxygen, Ozone and Peroxides, Uni Publishers Co., Tokyo, 1980, pp. 207–216.Search in Google Scholar
Kiss, J. (1974) β-eliminative degradation of carbohydrates containing uronic acid residues. Adv. Carbohydr. Chem. Biochem. 29:229–303.Search in Google Scholar
Košíková, B., Joniak, D., Polčin, J. (1984) Behaviour of lignin-saccharidic spruce wood complex in thermal mechanical pulping. I. TMP process. Cellulose Chem. Technol. 18:63–71.Search in Google Scholar
Kostinen, K. (2000) Wood handling application. In: Papermaking Science and Technology, Vol. 6A Chemical Pulping. Eds. Gullichsen, J., Fogelholm, C.-J. Fapet Oy, Helsinki. pp. 331–340.Search in Google Scholar
Krasowski, J.A., Marton, J. (1983) The formation of oxalic acid during bleaching of kraft pulp. J. Wood Chem. Technol. 3:445–458.Search in Google Scholar
Krogell, J., Holmbom, B., Pranovich, A., Hemming, J., Willför, S. (2012) Extraction and chemical characterization of Norway spruce inner and outer bark. Nord. Pulp Paper Res. J. 27:6–17.Search in Google Scholar
Nilvebrant, N.-O., Reimann, A. (1996) Xylan as a source for oxalic acid during ozone bleaching. Proceedings of the 4th EWLP Conference, Stresa, Italy. pp. 485–491.Search in Google Scholar
Omori, S., Dence, C.W. (1981) The reactions of alkaline hydrogen peroxide with lignin model dimers. Wood Sci. Technol. 15:113–123.Search in Google Scholar
Örså, F., Holmbom, B. (1994) A convenient method for the determination of wood extractives in papermaking process waters and effluents. J. Pulp Paper Sci. 20:361–365.Search in Google Scholar
Pranovich, A., Sundberg, K., Holmbom, B. (2003) Chemical changes in thermomechanical pulp at alkaline conditions. J. Wood Chem. Tech. 23:89–112.Search in Google Scholar
Rahikainen, J.L., Martin-Sampedro, R., Heikkinen, H., Rovio, S., Marjamaa, K., Tamminen, T., Rojas, O.J., Kruus, K. (2013) Inhibitory effect of lignin during cellulose bioconversion: The effect of lignin chemistry on non-productive enzyme adsorption. Bioresource Technol. 133:270–278.10.1016/j.biortech.2013.01.075Search in Google Scholar PubMed
Sjöde, A. Chemical Characterization in the Biorefinery of Lignocellulose. Formation and Management of Oxalic Acid and Analysis of Feedstocks for Bioethanol Production. Ph.D. thesis. Karlstad University, Faculty of Technology and Science, Sweden, 2008.Search in Google Scholar
Sjöde, A., Jönsson, L.J., Nilvebrant N.-O. (2005) Oxalic acid in bleaching processes-formation and control. Appita Annual Conference. 13th ISWFPC 2:303–309.Search in Google Scholar
Sjöström, E. Wood Chemistry – Fundamentals and Applications. 2nd edn., Academic Press, San Diego, CA, 1993, 49–108, 208.Search in Google Scholar
Sjöström, J. (1990) Fractionation and characterization of organic substances dissolved in water during groundwood pulping of spruce. Nord. Pulp Pap. Res. J. 5:9–15.Search in Google Scholar
Song, T., Pranovich, A., Holmbom, B. (2013) Separation of polymeric galactoglucomannans from hot-water extract of spruce wood. Bioresource Technol. 130:198–203.10.1016/j.biortech.2012.11.149Search in Google Scholar PubMed
Terelius, H., Nilsson, M., Blomberg, T. (2001) Calcium oxalate in mechanical pulp. Proceedings of the IMP Conference 2001. pp.125–132.Search in Google Scholar
Thornton, J., Ekman, R., Holmbom, B., Örså, F. (1994) Polysaccharides dissolved from Norway spruce in thermomechanical pulping and peroxide bleaching. J. Wood Chem. Technol. 14:159–175.Search in Google Scholar
Ulmgren, P., Rådeström, R. (2000) On the formation of oxalate in bleach plant filtrates on hot storage. Nord. Pulp Paper Res. J. 15:128–132.Search in Google Scholar
Varhimo, A. (2009) Wood raw materials. In: Papermaking Science and Technology, Vol. 5 Mechanical Pulping. Ed. Lönnberg, B. Paperi ja Puu Oy, Helsinki. pp. 70–115.Search in Google Scholar
Vuorinen, T., Fagerström, P., Räsänen, E., Vikkula, A., Henricson, K., Teleman, A. (1997) Selective hydrolysis of hexenuronic acid groups opens new possibilities for development of bleaching processes. ISWPC 1997, M4-1-M4-4.Search in Google Scholar
Yu, L., Ni, Y. (2005) Oxalate formation during peroxide bleaching of mechanical pulps. Appita J. 58:138–142, 148.Search in Google Scholar
Zhang, J.X., Yu, E., Ni, Y., Zhou, Y., Joliette, D. (2002) Calcium oxalate in Tembec maple BCTMP line. APPW 2002, Durban.Search in Google Scholar
Zhang, J.X., Yu, L., Ni, Y., Zhou, Y., Joliette, D. (2006) Calcium oxalate related scaling in a BCTMP line. Pulp Paper Can. 107:52–55.Search in Google Scholar
©2014 by Walter de Gruyter Berlin/Boston
Articles in the same Issue
- Frontmatter
- Review
- Effects of induced drought and tilting on biomass allocation, wood properties, compression wood formation and chemical composition of young Pinus radiata genotypes (clones)
- Original Articles
- Multi-step degradation method for β-O-4 linkages in lignins: α-TSA method. Part 1: Reaction of non-phenolic dimeric β-O-4 model compound
- Pulp delignification with oxygen and copper(II)-polyimine complexes
- Enzyme pretreatment of dissolving pulp as a way to improve the following dissolution in NaOH/ZnO
- Formation of oxalic acid in alkaline peroxide treatment of different wood components
- Pretreatment of hardwood chips via autohydrolysis supported by acetic and formic acid
- Synthesis and physicochemical properties of hydroxypropyl tannins from maritime pine bark (Pinus pinaster Ait.)
- Analysis of lignin and extractives in the oak wood of the 17th century warship Vasa
- Esterification of wood with citric acid: The catalytic effects of sodium hypophosphite (SHP)
- Bio-based epoxy resins with low molecular weight kraft lignin and pyrogallol
- Influence of toasting treatment on permeability of six wood species for enological use
- Experimental study of wood acoustic absorption characteristics
- Appearance, corrosion properties, and leach resistance of spruce and pine wood treated with Mea modified micronized copper preservative (MCu)
- DNA barcoding for identification of the endangered species Aquilaria sinensis: comparison of data from heated or aged wood samples
- Meetings
- Meetings
Articles in the same Issue
- Frontmatter
- Review
- Effects of induced drought and tilting on biomass allocation, wood properties, compression wood formation and chemical composition of young Pinus radiata genotypes (clones)
- Original Articles
- Multi-step degradation method for β-O-4 linkages in lignins: α-TSA method. Part 1: Reaction of non-phenolic dimeric β-O-4 model compound
- Pulp delignification with oxygen and copper(II)-polyimine complexes
- Enzyme pretreatment of dissolving pulp as a way to improve the following dissolution in NaOH/ZnO
- Formation of oxalic acid in alkaline peroxide treatment of different wood components
- Pretreatment of hardwood chips via autohydrolysis supported by acetic and formic acid
- Synthesis and physicochemical properties of hydroxypropyl tannins from maritime pine bark (Pinus pinaster Ait.)
- Analysis of lignin and extractives in the oak wood of the 17th century warship Vasa
- Esterification of wood with citric acid: The catalytic effects of sodium hypophosphite (SHP)
- Bio-based epoxy resins with low molecular weight kraft lignin and pyrogallol
- Influence of toasting treatment on permeability of six wood species for enological use
- Experimental study of wood acoustic absorption characteristics
- Appearance, corrosion properties, and leach resistance of spruce and pine wood treated with Mea modified micronized copper preservative (MCu)
- DNA barcoding for identification of the endangered species Aquilaria sinensis: comparison of data from heated or aged wood samples
- Meetings
- Meetings