Pre-treatment of the paper pulp in the bleaching process using biodegradable chelating agents

  • I. S. S. Pinto
  • O. S. Ascenso
  • M. T. Barros
  • H. M. V. M. Soares
Original Paper


The aim of this work was to study the application of two biodegradable chelating agents, pyridine-2,6-dicarboxylic acid (PDA) and methylglycinediacetic acid (MGDA), in the treatment of the pulp, prior to hydrogen peroxide bleaching. Such compounds must remove transition metals (Mn, Fe and Cu) from pulp, that catalyze the degradation of hydrogen peroxide, and Ca, which is also problematic due to the formation of precipitates that accumulate in the equipment. Computer simulations were first performed to study the best conditions for metal complexation, and optimum pH was defined as 5–5.5 for PDA and 6.5–7 for MGDA. Metals removal from the pulp, as well as the subsequent bleaching process (Q-P1-Paa-P2), were tested experimentally, and performances were compared to ethylenediaminetetracetic acid (EDTA). PDA removed both Mn and Ca efficiently, leaving most Mg in the pulp after first chelation stage, while MGDA had a lower Ca removal, even using a higher pH and concentration. Residual hydrogen peroxide and kappa number after peroxide stages showed a similar bleaching efficiency between the studied compounds and EDTA.


Bleaching Chelating agents Methylglycinediacetic acid Paper pulp Pyridine-2,6-dicarboxylic acid (dipicolinic acid) 



This work was financially supported by FEDER funds through the Programa Operacional Factores de Competitividade—COMPETE and national funds by FCT—Fundação para a Ciência e Tecnologia within the Project PTDC-AAC-AMB-111206-2009.


  1. Abbot J, Brown DG (1990) Stabilization of iron-catalyzed hydrogen-peroxide decomposition by magnesium. Can J Chem 68:1537–1543CrossRefGoogle Scholar
  2. Area MC, Felissia FE (2005) Chelating agents management to obtain TCF bleached Eucalyptus grandis kraft pulps. Appita J 58:143–148Google Scholar
  3. Bajpai P (2012) Environmentally benign approaches for pulp bleaching, 2nd edn. Elsevier, AmsterdamGoogle Scholar
  4. BASF (2007) Technical information Ti/EVD 1418 e—Trilon® M typesGoogle Scholar
  5. Black G, Depp E, Corson BB (1949) Oxidation of certain methylpyridines to pyridine carboxylic acids. J Org Chem 14:14–21CrossRefGoogle Scholar
  6. Boskamp JV (1990) Detergent composition. Patent number EP358472Google Scholar
  7. Bucheli-Witschel M, Egli T (2001) Environmental fate and microbial degradation of aminopolycarboxylic acids. FEMS Microbiol Rev 25:69–106CrossRefGoogle Scholar
  8. Chandraghargi RS (2003) Interaction of manganese and copper with wood pulp fibers. Thesis for Master of Applied Science, Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, CanadaGoogle Scholar
  9. Colodette JL, Rothenberg S, Dence CW (1989) Factors affecting hydrogen-peroxide stability in the brightening of mechanical and chemimechanical pulps. II. Hydrogen-peroxide stability in the presence of sodium-silicate. J Pulp Pap Sci 15:3–10Google Scholar
  10. De Almeida JMH, Bachus H, Djodikromo ZP, Doerfler C, Hage R, Lienke J (2008) Bleaching of substrates. Patent number WO2008086937Google Scholar
  11. Dournel P (2009) Process for the bleaching of paper pulp. Patent number WO2009144190Google Scholar
  12. Elsander A, Ek M, Gellerstedt G (2000) Oxalic acid formation during ECF and TCF bleaching of kraft pulp. Tappi J 83:73–77Google Scholar
  13. Hong APK, Chen TC (1996) Chelating extraction and recovery of cadmium from soil using pyridine-2,6-dicarboxylic acid. Water Air Soil Pollut 86:335–346CrossRefGoogle Scholar
  14. Hyvonen H, Orama M, Arvelac R, Henriksson K, Saarinen H, Aksela R, Parene A, Jakara J, Renvall I (2006) Studies on three new environmentally friendly chelating ligands. Appita J 59:142–149Google Scholar
  15. Jefferis J, Zack K (2011) Detergent composition. Patent number WO2011100344Google Scholar
  16. Jones PW, Williams DR (2001) Speciation efficiency indices (SEI) and readily-biodegradable indices (RBI) for optimising ligand control of environmental and associated industrial processes. Int J Environ Anal Chem 81:73–88CrossRefGoogle Scholar
  17. Jones PW, Williams DR (2002) Chemical speciation simulation used to assess the efficiency of environment-friendly EDTA alternatives for use in the pulp and paper industry. Inorg Chim Acta 339:41–50CrossRefGoogle Scholar
  18. Knepper TP (2003) Synthetic chelating agents and compounds exhibiting complexing properties in the aquatic environment. Trac Trend Anal Chem 22:708–724CrossRefGoogle Scholar
  19. Kujala M, Sillanpaa M, Ramo J (2004) A method to leach manganese and some other metal cations from pulp matrix to aqueous phase for the subsequent ICP-AES analysis: a potential tool for controlling the metal profile in a pulp bleaching process. J Clean Prod 12:707–712CrossRefGoogle Scholar
  20. Lapierre L, Berry R, Bouchard J (2003) The effect of magnesium ions and chelants on peroxide bleaching. Holzforschung 57:627–633CrossRefGoogle Scholar
  21. List TC, Reinbold RS (2010) Compositions and methods for removing scale and inhibiting formation thereof. Patent number US2010000579Google Scholar
  22. Loureiro PEG, Evtuguin DV, Carvalho MGVS (2011) The final bleaching of eucalypt kraft pulps with hydrogen peroxide: relationship with industrial ECF bleaching history and cellulose degradation. J Chem Technol Biotechnol 86:381–390CrossRefGoogle Scholar
  23. Macauley E, Hong A (1995) Chelation extraction of lead from soil using pyridine-2,6-dicarboxylic acid. J Hazard Mater 40:257–270CrossRefGoogle Scholar
  24. Martell AE, Smith RM (2004) NIST standard reference database 46 version 8.0. NIST critically selected stability constants of metal complexes database. US Department of Commerce, National Institute of Standards and TechnologyGoogle Scholar
  25. Martins JG, Neto I, Pinto ISS, Soares EV, Barros MT, Soares HMVM (2014) Alternative chelating agents: evaluation of the ready-biodegradability and complexation properties. J Environ Sci Health A 49:1–11CrossRefGoogle Scholar
  26. Metsarinne S, Ronkainen E, Tuhkanen T, Aksela R, Sillanpaa M (2007) Biodegradation of novel amino acid derivatives suitable for complexing agents in pulp bleaching applications. Sci Total Environ 377:45–51CrossRefGoogle Scholar
  27. Ni Y, Liu Z (2000) Pulp bleaching. In: Kirk RE, Othmer DF (eds) Encyclopedia of chemical technology. Wiley, New YorkGoogle Scholar
  28. OECD (1992) Ready biodegradability 301. OECD guideline for testing of chemicals, vol 301Google Scholar
  29. Potucek F, Milichovsky M (2000) Kraft pulp bleaching with hydrogen peroxide and peracetic acid. Chem Pap 54:406–411Google Scholar
  30. Povoas TM, Angelico DAG, Egas APV, Loureiro PEG, Gando-Ferreira LM, Carvalho MGVS (2012) Prebleaching of eucalypt kraft pulp with OP stages: effect of an acid pretreatment or chelation step. Tappi J 11:31–38Google Scholar
  31. Rattinger GB, Cotter B, Fair MJ (1994) Liquid automatic dishwashing composition. Patent number WO9405763Google Scholar
  32. Renvall I, Askela R, Paren A (1997) Process for bleaching of a high yield pulp. Patent number WO9730209Google Scholar
  33. Rudie A (2000) Calcium in pulping and bleaching. Tappi J 83:36–37Google Scholar
  34. Schecher WD, McAvoy DC (2003) MINEQL+ a chemical equilibrium modeling system, version 4.5 for Windows. User’s Manual Hallowell, MaineGoogle Scholar
  35. Seccombe R (2008) Process for the bleaching of paper pulp. Patent number WO2008101952Google Scholar
  36. Seccombe R, Dournel P (2007) Process for the bleaching of mechanical paper pulp. Patent number WO2007085579Google Scholar
  37. Sillanpaa M, Raimo KB, Sihvonen ML (1995) Determination of Edta and Dtpa as their Fe(III) complexes in pulp and paper-mill process and waste-waters by liquid-chromatography. Anal Chim Acta 303:187–192CrossRefGoogle Scholar
  38. Singer AW, McElvain SM (1955) Organic synthesis. Collective 3:740Google Scholar
  39. Turner ET, Moore SB, Leuck JF (1997) Bleaching composition. Patent number US5616280Google Scholar
  40. Wuorimaa A, Jokela R, Aksela R (2006) Recent developments in the stabilization of hydrogen peroxide bleaching of pulps: an overview. Nord Pulp Pap Res J 21:435–443CrossRefGoogle Scholar
  41. Xiao HB, Tao XM, Wang YC, Qian SX, Shi GH, Li H (2008) Dipicolinate as acceptor in D–π–A chromophores: synthesis, characterization and fluorescence following single- and two-photon excitation. Tetrahedron Lett 49:6819–6822CrossRefGoogle Scholar

Copyright information

© Islamic Azad University (IAU) 2013

Authors and Affiliations

  • I. S. S. Pinto
    • 1
  • O. S. Ascenso
    • 2
  • M. T. Barros
    • 2
  • H. M. V. M. Soares
    • 1
  1. 1.REQUIMTE, Departamento de Engenharia Química, Faculdade de EngenhariaUniversidade do PortoPortoPortugal
  2. 2.REQUIMTE, CQFB, Departamento de Química, Faculdade de Ciência e TecnologiaUniversidade Nova de LisboaCaparicaPortugal

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