Reaction Rates of Lignin and Hexenuronic Acids with Chlorine Dioxide, Ozone, and Sulfuric Acid
Keywords:
Eucalyptus, kraft pulp, lignin, hexenuronic acids, ozone, chlorine dioxide, sulfuric acid, reaction ratesAbstract
The reaction rates of lignin and hexenuronic acids (HexA) with chlorine dioxide, ozone, and sulfuric acid were investigated. In unbleached and oxygen-delignified eucalyptus kraft pulps containing both lignin and HexA, only HexA, or only lignin reacted with chlorine dioxide, ozone, and sulfuric acid under typical bleaching conditions. The maximum reaction rates of chlorine dioxide with lignin and HexA were 57.2 and 26 mmol/kg/min, respectively, for unbleached pulp, and 26.7 and 13 mmol/kg/min, respectively, for oxygen-delignified pulp. The maximum reaction rates of ozone with lignin and HexA were 58.6 and 132 mmol/kg/min, respectively, for unbleached pulp, and 56.8 and 134 mmol/kg/min, respectively, for oxygen-delignified pulp. The maximum reaction rates of sulfuric acid with lignin, and HexA were 1.11 and 0.93 mmol/kg/min, respectively, for unbleached pulp, and 1.95 and 0.80 mmol/kg/min, respectively, for oxygen-delignified pulp. Chlorine dioxide reacts faster with HexA in the presence of the residual lignin. The kinetic results suggest that pulp treatment with ozone, when justifiable, should follow but not precede chlorine dioxide oxidation. Unbleached pulp residual lignin and HexA react twice as fast with chlorine dioxide than the lignin and HexA present in oxygen-delignified pulp, while the pulp type has no significant effect on lignin and HexA reactivity toward ozone. HexA reactions with sulfuric acid and ozone can be described by two-phase pseudo first-order reaction rates.References
Barroca MJM, Simões RMS, Castro JA (2001) Kinetics of chlorine dioxide delignification of a hardwood kraft pulp. Appita J 54(2):190-195.nChandranupap P, Nguyen KL (2000) Effect of pH on kinetics and bleaching efficiency of chlorine dioxide delignification. Appita J 53(2):108-110.nChapman AA, Nguyen KL, Cook RA (1998) Instantaneous effectiveness of ozone bleaching at high consistency. Appita J 51(1):57-61.nCosta MM (2001) The effect of hexenuronic acids on eucalyptus kraft pulp bleachability. PhD Thesis. Federal University of Viçosa. 182 pp.nCosta MM, Colodette JL (2007) The impact of kappa number composition on eucalyptus kraft pulp bleachability. Braz J Chem Eng 24(1):61-71.nDevenyns J, Chauveheid E (1997) Uronic acid and metals control. International Symposium On Wood And Pulping Chemistry, Montreal, Canada. V1: M5-1-M5-4.nEiras KM, Colodette JL (2003) Eucalyptus kraft pulp bleaching with chlorine dioxide at high temperature. J Pulp Pap Sci 29(2):64-69.nHenricson K (1997) AHL-Stage-A new bleaching stage for kappa reduction and metal profile control. International Emerging Technologies Conference and Exhibition, Orlando, FL.nJiang ZH, Bouchard J, Berry R (2006) Evidence for the formation of lignin-hexenuronic acid-xylan complexes during modified kraft pulping processes. Holzforschung 60:137-142.nJiang ZH, Lierop BV, Berry R (2000) Hexenuronic acid groups in pulping and bleaching chemistry. Tappi J 83(1):167-175.nLachenal D, Chirat C (2000) High temperature ClO2 bleaching of hardwood kraft pulp. Tappi J 83(8):96.nReeve DW (1996) Chlorine dioxide in delignification. Pages 261-286 in C. W. Dence and D. W. Reeve, eds. Pulp bleaching-principles and practice. Tappi Press, Atlanta, GA.nPryke D, Reeve DW (1997) A survey of ClO2 delignification practices in Canada. Tappi J 80(5):153-161.nTappi Standard Procedures and Useful Methods (1998) Tappi Press. Atlanta, GA.nTessier P, Savoie M (2000) Chlorine dioxide bleaching kinetics of hardwood kraft pulp. Tappi J 83(6):50-55.nTörngren A (2002) Hexenuronic acid reactions in chlorine dioxide bleaching-aspects on in situ formation of molecular chlorine. Nord Pulp Pap Res 17(2):179-182.nToven K, Gellerstedt G, Kleppe P, Moe S (2002) Use of chlorine dioxide and ozone in combination in pre-bleaching. J Pulp Pap Sci 28(9):305-310.nTran AV (2006) High-consistency ozonation of hardwood kraft pulp. Holzforschung 60(6):685-690.nVuorinen T, Burchert J, Teleman A, Tenkanen M, Fagerstrom P (1996) Selective hydrolysis of hexenuronic acid groups and its application in ECF and TCF bleaching of kraft pulps. International Pulp Bleaching Conference, Washington, DC.n
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