395 Wellington Street OltawaON K I A O N 4 Canada

395. rue Wellington Ottawa ON K1A ON4 Canada

Your hie VOrnrmtaraocS

Our nie Norre felmtmw

The author has granted a nonexclusive licence allowing the National Library of Canada to reproduce, loan, distribute or seil copies of this thesis in microfom, paper or electronic formats.

L'auteur a accordé une licence non exclusive permettant à la Bibliothèque nationale du Canada de reproduire, prêter, distribuer ou vendre des copies de cette thèse sous la forme de microfiche/nlm, de reproduction sur papier ou sur format électronique. L'auteur conserve la propriété du droit d'auteur qui protège cette thèse. Ni la thèse ni des extraits substantiels de celle-ci ne doivent être imprimés ou autrement reproduits sans son autorisation.

The author retains ownership of the copyright in this thesis. Neither the thesis nor substantial extracts fiom it may be printed or othewise reproduced without the author's permission.

To m mum and dad, my cheerful skters and brother, y
and my loving wife, Liziren

This study focuses on several fùndamental and practical aspects of peracetic acid (Pa) brightening of softwood kraft pulps.
A PaEop bnghtening sequence was developed and optimised for a conventiond

Hemlock kraft pulp bleached by a solvent-assisted ozone treatment and subsequent oxidative extraction (ZnEo pulp). At a final brightness of about 88% ISO the strength properties and brightness stability of this TCF fully bleached pulp are similar to or better than those of a conventionally chiorine bleached pulp. The stability of an aqueous solution of peracetic acid was studied. It was found that peracetic acid is consumed by three reactions: i) spontaneous decomposition, ii) hydrolysis and iii) transition metal catalysed reactions. The spontaneous decomposition rate is maximal at pH 8.2 while both the hydrolysis and metal ion catalysed reactions increase with increasing

pH. At pH 10.5 or higher, the hydrolysis becomes dominant when the metal ion catalysed
reactions are minimized by metal chelation. The kinetics of the spontaneous decomposition and aIkaIine hydrolysis of peracetic acid were developed. The transition metal ion induced peracetic acid decomposition and the effect of the addition of chehtdadditives on the decomposition were studied under typical peracetic acid pulp bleaching conditions. The results show that a significant amount of peracetic acid may be wasted when metal ions are present, resulting in less efficient bleaching. A chelation pretreatment stage for pulp with high metal ion contents, especially rnanganese, leads to irnproved subsequent peracetic acid bleaching. However, for pulps with a low rnetal ion

per two moles of oxidant (peracetic a d and hydrogen peroxide) consumed. . It is found that aithough carbon dioxide is fonned under certain conditions. The model consists of three parallel and one consecutive reaction. and is based on reaction pathways reported for Iignin model compounds with peracetic acid. This suggests that the oqgen formation can be used for control of an industrial peracetic acid treatment. Therefore. One mole of oxygen is forme.such as DTPA or DTMPA. Finally. the amount of peracetic acid consumed in oxidation reactions can be determined as the dxerence between the total arnount of peracetic acid consumed and that consumed in wastetùl reactions as determined by oxygen formation. a kinetic mode1 of peracetic acid briçhtening of a soivent-assisted ozone delignified pulp was developed. The peracetic acid consumption in wasteful reactions was quantified by detemining the gaseous products evolved. The addition of sodium pyrophosphate eflectively deactivates the metal ions and consequently improves the bleaching performance. oxygen is the dominant product of the wasteful reactions. It was shown for an oxygen delignified softwood kraft pulp that there is a unique relationship between pulp brightness gain and peracetic acid consumption due to pulp oxidations irrespective of the brightening conditions. to the peracetic acid solution minimizes the Cu(I1) and Fe(II1) i n d u d decomposition of peracetic acid but increases the Mn(I1) induced decornposition. An optirnization search algorithm was used to find the kinetic parameters of the model. The kinetic model provides an adequate description of the disappearance rate of the chromophores in pulp at constant pH and peracetic acid concentration.

Russell Girard. for al1 their help. understanding and encouragement have bolstered me through this endeavour. Teik Ooi and Drs.Li and Ghosh for al1 the valuable discussions. . Lizhen. Limerick Pulp & Paper Research and Education Centre for their assistance and suggestions during the course of this work. Financial support fiom NSERC in the fonn of a Strategic Grant is greatly appreciated. RW. whose love. Hildebrand. M. encouragement and invaluable guidance throughout the course of this study. Thring. Mr. van Heiningen. Without them this work would not have been possible! 1 wish to thank Mr. XiaoZhu Zhang. Peters for their moral support dunng my study in Canada.ACKNOWLEDGEMENT 1 would like to express my deepest appreciation to my thesis s u p e ~ s o r sDrs. Mr. Special thanks to Le Zeng. Kang . My greatest thanks must go to my dear wife. It is a pleasure to extend gratitude toward a11 the members of the Dr. & Mrs. M. Ni and . I also wish to thank Dr. d'Entremont for his help with some of the experiments. support.

.

................................................. 49 Brightness Stability of the TCF Fully Bleached Pulp KINETICS OF PERACETIC ACID DECOMPOSITION PART 1 SPONTANEOUS DECOMPOSITION AT : TYPICAL PULP BLEACHING CONDITIONS . 54 ................................... 56 Experimental ........................ 37 Introduction .................................................................................. 34 Experimental ................ 59 Approcach ...........................*.................................................... 47 References ................... 33 ............... 36 Results and Discussion ....................................................................... 62 Abstract vii ............................... 46 Conclusions .............................BFUGHTENING OF A SOFTWOOD KRAFT PULP DELIGNIFIED BY METHANOLASSISTED OZONATION ........................... 46 Chernical Cost Evaluation of the ZnEoPaEop Sequence ........................... ... 55 Introduction ........... 37 Peracetic Acid Brightening (Pa) of ZnEo Delignified Pulp ................................................... 60 Results and Discussion ....................................... 46 Further Brightening of ZnEoPa Treated Pulp in an Eop Stage .. 32 Abstract ....................... 40 Further Brightening of ZnEoPaEop Treated Pulp by a Final Pa Treatment ...

.....90 92 .......... CHAPTER 6 THE ROLE OF TRANSITION METAL IONS DURING PEFWCETIC ACID BLEACHING OF CHEMICAL PULPS .............................. 7 7 Experimental ...................................................... 79 Establishment of Conditions for Determination of Hydrolysis Kinetics ............................................................................................ 106 Experimental .............................. 78 Results and Discussion ......................................................... 88 ........................................................................ 84 Predictions Obtained with the Hydrolysis and Decomposition Kinetics ................. 102 Introduction .................. 76 Introduction ...... 87 Effect of MgSO................ 68 CHAPTER 5 Abstract KINETICS OF PERACETIC ACID DECOMPOSITION PART II: ALKALINE HYDROLYSIS .References .... 103 ................................................................................ 79 Kinetics of the Alakline Hydrolysis of Peracetic Acid .. 104 Results and Discussion ............. 101 Abstracf ....................................................... 75 .. on the Consumption of Peracetic Acid Condusions References .......................................................

........... ......131 Results and Discussion ............ ....... ....e..... 117 119 CHAPTER 7 THE FORMATION OF GASEOUS PRODUCTS AND ITS RELATION TO PULP BLEACHING DURING TEE PERACETIC ACID TFtEATMENT ..1. .......... .............. ................ ....... .............. .................... ............ . ................... ........... 146 ............................ .. .... .. 135 The Effect of DTPA and DTMPA on Gas Formation and Peracetic Acid Decomposition . ............. 129 Abstract ..... .. 140 Conclusions References ...... . 135 The Formation of Gaseous Products during the Decomposition of Peracetic Acid ............ .... ...... .. ...... ....... Peracetic Acid ................. ...... .. 108 The Role of Transition Metal Ions during Peracetic Acid Bleaching of Chernical Pulps ..................... ....... .. ...... .... 138 The Formation of Gaseous Products and Its Relation to Peracetic Acid Bleaching ............ .... .. ............................. .. . .......... . .Effect of Additives on the Meta1 Catalysed Decomposition of ... ..................... . .. ....o..... ..... .. .. .... . 112 Conclusions References ......................... ............ 130 Introduction ...... ........... ............144 ....... . ........................ .....

.................................................................................. ..................... 191 192 196 Recommendations for Future Work THE COMPUTER OPTIMIZATION PROGRAM FOR THE KINETIC STUDY OF PERACETIC ACID BRIGHTENING ............................................. 179 Estimation of the Initial Values CHAPTER 9 CONCLUSIONS GeneralSummary ... 171 Modelling Results ..................................... 162 Experimental .............................................................................. 160 ...................................................... 197 ........................ 163 Results and Discussion ........................... 177 References .. 166 Abstract ................................................................................ 165 Development of the Kinetic Mode1 ....... .................BRIGHTENING OF AN OZONE DELIGNIFIED SOF'TWOOD KRAFT PULP ..................................................................... 174 Conclusions .. 161 Introduction ..........

90 C Meta1 Ion Contents of the Materials Used in This Study Table 5 ....................2 Rate Constant of the Spontaneous Decomposition as a Function of Temperature ................ 40 The Effect of NaOH Charge on the Eop Stage The Addition of DTPA to the Eop Stage Table 2 .2 . 3 .... The Fractional Factorial Design of b(39for Pa Brightening of ZnEo Delignified Pulp ... 63 Table 4......... 3 Table 3-7 .......... .......1. 87 Table 5.... to the Eop Stage Estimation of Bleaching Chernical Cost of the ZnEoPaEop Sequence .. 1 ....4 Table 3-5 ...........Table 3 ... Conditional Stability Constants of Metal Ion to DTPA Complexes a t pH 7.... 47 . .......... 38 The Effect of Reaction Time on Peracetic Acid Bleaching of ZnEo Delignified Pulp .. ... .. .....................2 ....................... 3 Table 3 ... The Required Time to Convert 95% of Residual Peracetic Acid to Hydrogen Peroxide ............ IO5 ...... 44 The Effect of Temperature and Reaction Time of the Eop Stage ........ 3 Table 6............................. ... Table 3........................... 66 Rate Constant of the Peracetic Acid Hydrolysis as a Function of Temperature ..... Table 6.. 43 ........................ 41 ..... ..... The Observed Second-order Rate Constant as a Function of pH a t 40°C .0 and 20°C ............. Table 4 4 .. 109 Peracetic Acid Bleaching of Oxygen Delignified Softwood Kraft Pulp (O Pulp) ...... Table 6 ............. 45 The Addition of MgSO............ 113 Table 6 ................. 88 The Composition of Magnesium Species in Aqueous Solution a t 40 O with Varying pH and MgSO......... Addition .......................

.........0..... Peracetic Acid Bleaching of Ozone Delignified Softwood Kraft Pulp .................................. xii .. ........... The Development of the Light Absorption Coeficient a t pH 6......... 50°C and Different Peracetic Acid Concentrations The Kinetic Parameters Obtained by the Book and Jeeves Search Algorithm at 50°C for the Brightening of ZE Pulp .............. 166 176 Table 8-2.Table 6-4.... ....... 117 The Formation of Gaseous Products and Its Relation to Bleaching during Peracetic Acid Treatment of an Oxygen Delignified Pulp Table 7-1....................... 141 Table 8-1...

.... 96 ..... ..5 and 40°C.. 71 Koubek's plot of Logk..... versus pH at 25"C...8 2 1 . ................... . ... 95 Effect of H'O... ......... 72 . ..... . pE. ............ ..... 74 ..... ............ 70 Figure 4 3 -..... ... ... . 100 ..... ... . ..... ............. on the consumption of peracetic acid at 40°C and pH of 95 ....... 69 ..... .... 40°C. ..... Figure 4 6 -..5 g/L DTMPA)..0 5 g / L DTMPA) .0 ....Figure 4-1. ... ... . with 103 m o n EDTA [8] .. 97 ...... 99 .. Comparison of determined and predicted peracetic acid and hydrogen peroxide concentrations (pH 9... Ranalysis of Koubek's data 181 with the kinetic mode1 developed in this study at 2s0C.......... ... Plot of k. .. .. 73 Figure 4-5. with IO3 m o n EDTA The Arrhenius plot of the spontaneous decomposition of peracetic acid ..... .. . Determination of the rate constants of the alkaline hydrolysis of peracetic acid (40-60°C..5. 05 g/L DTMPA) 051.. Addition of DTPA or DTMPA on the peracetic acid .... Figure 5-7. Effect of pH on the consumption of peracetic acid (40°C.. . Figure 5-2.... Figure 5 6 -.. Figure 4-2..... decomposition a t pH 82 and 40°C.... ........... Figure 5-5....... .... . 98 Figure 5-4......... . The effect of stabilizers on the decomposition of peracetic acid at 40°C...... .. .. ..... .....-20 .......1 . versus 2M/(l+M)' at 40°C..... ..5 ....0... pH = 5... Addition of DTPA or DTMPA on the peracetic acid decomposition a t pH 9.......2 0 pH. Effect of MgSO.. concentration on the disappearance rate of peracetic acid at pH 82 and 40°C .. ........ .. Figure 4 4 -. pH of 7.... ... .. Figure 5-3......... 94 Figure 5-1. 90 Comparison of the predicted and experimental relationship between & and pH a t 40°C .....

.0. Effect of additives on manganese catalysed peracetic acid decomposition (40°C.0. F(He)of 100mWmin Figure 7-4.5 g/L DTPA.0..P20... The formation of gaseous products and the consurnption of peracetic acid at 25OC...... 0..75 pprn Mn2'... 150 & Gas formation and the consumption of peracetic acid in the presence of 0. pH 7.......0.. pH 8..... 123 Figure 6-3......... DTMPA or MgSO.........2. 125 Figure 6-4..75 pprn Cu2'.... Effect of DTPA on the manganese catalysed decomposition of peracetic acid(40°C..0.......Stability of a peracetic acid soiution (40°C. Figure 6-5...... 0........... DTMPA or MgSO.75 ppm FeY....75 ppm Mn2'. 0-5 g/L DTPA) .... pH 7...0.... pH 6... 2 g/L Na. 0........ 151 .......75 pprn Mn(II) and a t 25"C.... pH 7.0. pH 7...... Figure 6-7.... 148 149 Figure 7-2... The stoichiometry of the peracetic acid consumption and the oxygen formation at 2S°C.....5 g DTMPA addition .. 124 .... pH 8. 2 g / L Na.....) Effect of additives on iron catalysed peracetic acid decomposition (40°C. 122 Effect of additives on copper catalysed peracetic acid decomposition (40°C........ Figure 7-3. DTMPA or MgSO... F(He) of 100 m u m i n and with 0 5 g/l DTMPA addition ... pH 5.. Effect of DTPA or DTMPA on the manganese catalysed decompositioo of peracetic acid (40°C. 0..5 g/L DTPA...... 0...... ... Effect of DTPA or DTMPA on the manganese catalysed decomposition of peracetic acid (40°C.........2.... 128 Figure 7-1.....5 g/L DTPA or DTMPA) The experimentai setup for the determination of gaseous products during peracetic acid decomposition ... 2 g/L Na......P20.........) ...5 g/L DTPA or DTMPA) .5 g / L DTPA....... pH 7.. .. ....)...... 126 127 Figure 6-6...75 pprn Mn2'.... .... pH 8.75 pprn Mn2'....0. F(He) of 100 mL/min and with 0.0.0..................P20.. 0.0.75 ppm metal ion concentration) Figure 6-2........0.0......2.................

....... 40-60°C.0...02 moVL DTPA added at 30 min...2... The stoichiometr-y of peracetic acid consumption and carbon dioxide formation in the presence of 0......... pH 5-7.. 155 Figure 7-9. The effect of DTPA addition on peracetic acid consumption and the oxygen formation at 25"C. 40-60°C.. F(He) of 100 m u m i n and with 0.... pH 5...... ..... The effect of pH on the Iight absorption coefficient development during Pa brightening of ozone delignified softwood kraft pulp (50°C and [CH3C03H]of 0. ............. 157 ......5-1.. 153 154 Figure 7-7..... 183 The proposed kinetic mode1 for peracetic acid brightening of ozone delignified softwood kraft pulp Estimation of C3.................... (50°C.0....... 158 The relationship between the pulp viscosity and the oxidant consumed in wasteful reactions (O or OQ pulp. 184 .. pH 8.11.... 1... and k..75 ppm Mn(U) and a t 25"C............. pH 5-7.. pH 7............5-1.. 30-120 min) Figure 7-12... 30-120 min) Figure 7.the presence of 0.......... 1...75 ppm Mn(1I) and at 2S°C...02 m o n DTMPA added at 30 min ...... 159 Figure 8-1.....5-1... The effect of DTMPA addition on peracetic acid consumption and oxygen formation in the presence of 0. Figure 7-8........5% pulp consistency....5-5% peracetic acid charge........75 ppm Mn@) at 2S°C.. 0.10.....1. pH 5.... ..........5% pulp consistency. F(He) of 100 m u m i n and with 0.... ... pH 5-7... 0.0493 moVL) ....... 0... The relationship between the wasted peracetic acid and hydrogen peroxide (O or OQ pulp.5% pulp consistency.5-5% peracetic acid charge... 185 Figure 8-3. F(He) of 70 m u m i n .. .. F(Be) of 100 milmin) Plausible mechanism of the carbon dioxide formation during peracetic acid decomposition ......... 30-120 min) .....5-5% peraceticacid charge...... [CH3C03H]of 0........0......... 40-60°C.. 156 Figure 7.... The relationship between the peracetic acid consumption due to the pulp oxidation and the pulp brightness (O or OQ pulp..2.. 152 Figure 7-6.0493 m o n ) Figure û-2.. pH 8...

p H 7...Figure 8-5.. pH 7..H] of 0..0.. C2.0........ Figure 8-7. Cornparison of mode1 predictions and experimental results (50°C. C3 and C (50°C.. [CH.. 188 Predictions of the development of Cl... [CH.. . pH 10..... pH 3..0493 moi&) ...H] of 0..and C (50°C....... ..... C... C. 187 Predictions of the development of Cl. C...C03H] of 0............ [CH3C0..C3and C (50°C.....0..... 190 xvi . 189 Figure 8-8.0493 moi&) .0...HJof 0...CO....0493 m o n ) Predictions of the development of C..0493 moüL) Figure 8-6.. [CH3C0..

NOMENCLATURE [cl [CH3C03H]. (mol/L) = diethylenetriaminepentaaceticacid = diethylenetriarninepentamethylenephosphonic acid = ethylenediarninetetraaceticacid DTMPA EDTA E = alkaline extraction stage = activation energy. Ea ECF Eo EOP (kcaVmol) = Elemental Chlorine Free = alkaline oxidative extraction = hydrogen peroxide reinforced oxidative extraction stage = hydrogen peroxide reinforced extraction stage = international = reaction = acid EP % ISO standard organization brightness k Ka rate constant ionization constant constant ko = pre-exponential k. DTPA = chromophore concentration = total titratable peracetic acid concentration. o = observed rate constant = ionization k M constant of water concentration to the dissociation constant stage = the ratio of proton P = hydrogen peroxide bleaching xvii .

Q TCF Zn = chelating stase = Totally Chlorine Free = solvent-assisted ozone bleaching stage .

CHAPTER 1 INTRODUCTION .

chlorine dioxide.g. (2) modifjmg the bleaching process by complete substitution of chlorine with chlorine dioxide. IO]. was . New regulations are forcing the pulp and paper industry to reduce the environmental impact of pulp bleaching. Totally Chlorine Free (TCF) bleaching processes are also emerging 16. and to reactivate the residual lignin for subsequent bleaching treatments. Several operational practices are rapidly being introduced into the pulp manufàcturing process such as: (1) lowering the lignin content of pulp pnor to entering the bleachery by extended delignification (e. such as chlorine. Among them. An aikaline stage is usudly included in the bleaching process to solubilize the oxidized lignin. Ozone. although known as an effective delignifier for nearly fifty years. bleaching of chemical pulps consists of two steps: (1) to remove the residual lignin.g. and (2) to brighten the pulp.BACKGROUND In pnnciple. are known as good delignification andfor brightening chemicals. oxygen. the so-called ECF (Elemental ChIorine-Free) process [5. oxygen. hypochlorite. such as in the Bleach Filtrate Recycle 78. process (BFRm) [9]. and the adoption of an alkali oxidative extraction stage (Eo) or a peroxide enhanced Eo stage (Eop) [ . e. The ECF bleaching process is now becoming the dominant bleaching technology for chemical puIps. hydrogen peroxide. hydrogen peroxide and peracids are possible substitutes for chlorine dioxide in the final brightening stages due to their high brightening capacity [ 6 ] . hydrogen peroxide and peracids are potential TCF bleaching chemicals. Oxidants.6]. MCC or RDH) 11-31 andor oxygen delignification [4]. Peracetic acid. ] (3) (partial) system closure of the bleach plant. peracids and ozone.

the kinetics of spontaneous decomposition were further investigated in the present work. or as an activation agent for oxygen or hydrogen peroxide stages [13. Also it is necessary to investigate the role of transition metal ions during peracetic acid bleaching. Others have found that some of the transition metal ions may catalyse the decomposition of peracetic acid under acidic conditions (27-3 11. enabling peracetic acid to become a promising candidate for pulp bleaching [l 1. peracetic acid decomposes at pulp bleaching conditions. one of the objectives of the present project was to develop the subsequent bnghtening sequence with peracetic acid and hydrogen peroxide. However. recent advances in peracetic acid production technology have significantly reduced the cost. Through earlier studies 122-261.181. It has been shown that peracetic acid can be used as a delignification agent [Il . high brightness TCF pulp. since Our preliminary experimental data showed that his kinetics did not accurately predict the decomposition of peracetic acid at the typical pulp bleaching conditions.3 11 that gaseous products. However. and CO. Koubek [27] shidied the peracetic acid decomposition in several buffer solutions. which is typically performed at a neutral pH. For a complete description of the disappearance rate of peracetic acid the kinetics of alkaline hydrolysis of peracetic acid must be known at a pH higher than 8. such as O.131. it was demonstrated that a solvent-assisted ozone process can be used to deligniQ chernical pulps to a low kappa number. In order to produce a high strength. or as a brightening agent in the final stages of an ECF or TCF process [l3. . It was also reported 12729. Sirnilar to hydrogen peroxide.19-21 J.19]. while maintaining good viscosity and strength properties. are formed dunng peracetic acid .considered too expensive for commercial application.2.

. More specifically the objectives d to develop and optimize a TCF brightening process including peracetic acid treatment of an ozone delignified hemlock kraft pulp to study the decomposition of peracetic acid under conditions typical to those of pulp brightening by peracetic acid to examine the role of transition metals during peracetic acid decomposition and their importance in peracetic acid bleaching to identa the relationship between the efficiency of pulp brightening and the gaseous products fonned as a result of peracetic acid decomposition to develop a kinetic model for peracetic acid brightening of an ozone deliçnified Hernlock kraft pulp OUTLINE OF THE THESIS This thesis focuses on the fundamental and practical aspects of peracetic acid brightening of softwood kraft pulps.decomposition. a kinetic model to describe the peracetic acid brightening is lackinç. the relationship between the gas formation and the efficiency of peracetic acid bleaching has not been established. OBJECTIVES The gened objective of the present project is to study the firndarnental and practical aspects of peracetic acid brightening of s o ~ o o kraft pu1ps. However. Finally.

Q. In Chapter 7. the inclusion of peracetic acid in a TCF bnghtening sequence for a Hemlock kraft pulp delignified by a methanol-assisted ozone process is described. In Chapter 8. The alkaline hydrolysis kinetics of peracetic acid are also reported. The fundamental phenornena associated with the presence of additives such as D m DTMPA. The role of transition metal ions during peracetic acid bleaching of chernical pulps is investigated in Chapter 6. In Chapter 5. In Chapter 3. peracetic acid bleaching and hydrogen peroxide bleaching is presented in Chapter 2. The kinetics of spontaneous decomposition of peracetic acid under conditions typical of pulp brightening by peracetic acid are described in Chapter 4. and MgSO.P. Chapter 9 summarizes the contributions to knowledge resulting fiom this study. the formation of gaseous products and its relation to pulp bleaching dunng the peracetic acid treatment is studied. the effect of pH on the disappearance of peracetic acid in an aqueous solution is discussed.The relevant literature review of peracetic acid decomposition. . a kinetic mode1 of peracetic acid brightening of an ozone delignified pulp is developed based on the reaction pathways reported in literature for peracetic acid treatment of lignin mode1 cornpounds. The optimum process conditions for the peracetic acid stage (Pa) and the hydrogen peroxide reinforced oxidative extraction stage (Eop) are also determined. on the peracetic acid decomposition and bleaching are examined.Na. The potential use of the quantitative determination of the amount of gaseous products formed by peracetic acid decomposition as an indicator of the efficiency of peracetic acid pulp bleaching is discussed.

1997.7.. 87(5): T 193 ( 1986) 2. CPPA.. and Improve Productivity and Puip Properties. Montreal. 42-47 Accepted for publication by Puip & Paper Canada.4. Decrease Emuent.. E. Kubes. J. 37-4 1 The Canadian Journal of Chernical Engineering. Feb. N. 1997. A New Technique for Pulping to Low Kappa Numbers in Batch Pulping: Results of Mill Trial.. March. K. 75. 3. and J.. K. 1997 Submitted t o Joumal of Wood Chemistry and Technology. 1997 Submitted t o Tappi Joumal. 1. Vol. Mjoberg and L. Sjodin.. 66(9):97 ( 1983) Volk J. 1997 REFERENCES 1. As far as possible. p. J. and G . 1996. p. Feb. G. N.. 75. Sect. and 8 have been written as self-contained papers suitable for publication with IittIe or no fürther modifications. Preprints the 82* CPPA Annual Meeting. March. Feb. B3 7 Andrews..an overview. Successfùl Lo-solidsn' Cooking at Hinton. Tech.5. The major content of these chapters is goinç to be or has been submitted or presented at respectively refereed journals and technical conferences. Teodorescu. Pulp Paper Can. Young.The work describeci in Chapters 3. Thus each chapter has its own abstract and references. RDH Kr& Pulping to Extend Deligiification. p. Oxygen in Bleaching Sequence . Vol. Liebergott. 4. J. 72(11):55 (1 989) van Lierop. Hartler.. uniform and standard syrnbols are used throughout the thesis.6. B. Tappi J. . Specifically: Chapter 3: Chapter 4: Chapter 5: Chapter 6: Chapter 7: Chapter 8: Submitted t o Papen ja Puu. April. 1997 The Canadian Joumal of Chernical Engineering. Sjoblom. Tappi J.

Substituting Chlorine Dioxide for Elemental Chlorine Makes the Bleach Plant Effluent Less Toxic. 1993 Non Chlorine Bleaching Conference. 11-3 Anderson. 1995. B. J. TAPPI 1992 Pulping Conference Proceedings. Laboratory Studies of Acetic Acid Bleaching. 1965. Section 4 4 Paper No. Proceedings. Fasten. FL. p. Tech. Peracetic Acid as a Selective Prebleaching Agent: an Effective Option for the Production of Fully Bleached TCF Kraft Pulps. TAPPl PRESS. Sect. Atlanta. Bleaching in Five Stages to Asymptotic Lirnit Using Only One Oxidant and Sodium Hydroxide. C. p. Anderson... CPPA. Alternatives for Achieving High Brightness TCF Pulps.sec. L.. SC. p. R T. Desprez and N. Tappi J. Atlanta. 123 Ferguson. Holtinger. and W.. R. H. Start and J. W. Lazorek. 1985 International Pulp Bleaching Conference Proceedings. 132 Rapson. HHI. h l p Paper Canada.. Preprints. Champion Moves Toward Closure with BFR Startup at Canton.. No Matter What You Call It. Amini and W. Troughton. Atlanta. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. Parker. p. TAPPI PRESS. R. K. A. C.. IW2. J. N. Tech. 1994 International Non-chlonne Bleaching Conference. Walsh. Peracetic Acid. 1985. 1219 Basta. G. TAPPI PRESS. 90(5):22 (1 992) Hill. J. J. B. Georgia. Hydrogen Peroxide Use in Chemical Pulp Bleaching.. Reeve. h l p & Paper. Proceedings.. H. CPPq Montreat. Quebec. On-site Generation and Use of Peroxy Acids in Chemical Pulp Bleaching. 1992 Tappi Bleach Plant Operations Short Course Notes. F. Amelia Island. Christiansen. W. P... Sponsored by Pulp & Paper and Emerging Technology Transfer Inc.. B59.3 Anderson. 1996. p. and R.Axesard. H. HoUie. and J. Wilkinson. W. Putp Bleaching-Principles and Practice. 4 13 Young. Montreal. 70(4):47 (1 996) Exclusive to Pulp and Paper Canada. B. 69(10):54 (1 986) Dence. TAPPI Annual Meeting. 81" CPPA Annual Meeting. Chlorine-fiee Bleaching 1s Here to Stay. B. Sect. CPPA Pacific and Western Branch AnnuaI Meeting Preprints. Preprint. C. F. J. P. P. p. and C. sec. 227 Devenyns. and D. Utilization of an Eop Stage During 100% CIOz Bleaching at Weldwood Hinton. 8-1 . Fredriksson. an Effective Alternative for Chlorine Compound Free Delignification of Kraft Pulp.. Lundgren.

Arnelia Island. 16(4):367-380 (1 996) Kan& G. 1993 Bailey. P.. 82"' CPPA Annual Meeting Tech. 49(1):9 (1966) Liebergott.. J. Devenyns. April. TAPPI PRESS. W.Gellerstedt. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. J. Improved Ozone Bleaching by Impreçnation of Chemical Pulps with An Acidified Mixture of 1. N. Montreai. van Heiningen. 1964 . Murphy. R P.D thesis. 1996. Peroxygen Prebleaching and Bleaching Technologies for Step-Wise Conversion fiom Conventional Chlorine Bleaching via ECF toTCF. Ozone Dioxane Bleaching of Chemical Pulps. Y. R. G.2 13 Koubek. van Heiningen. IO.and A R P. U. Wood Chem. Prepnnts. H. Desprez and N. R... D.The Kinetics and the Mechanism of the Decomposition of Aliphatic Peroxyacids in Aqueous Solutions. 70(3): 133 (1 996) Ni Y. A. 1996. Desprez and J.C. J. Magdzinsk and E. Washington. W.. Troughton. and Technology. Ozone Selectivity Improved with Use of Organic Solvent. Raleigh.B303 Ni. p. Proceedings of 1994 International Non-chlorine Bleaching Conference. E. Atlanta p. van Heiningen. Preprint. . Lora. K. p. 1994 Solinas M. FL.sec. March. Dence.S. Brown Univ. Y. and C. TAPPi PRESS. Ph. J. Y. F. and T.. L. Tappi J. 357 Devenyns. Pye.C. Peracids: The Pathway to High Brightness TCF Kraft Pulps. CPPA.. Peracid Delignification and Bleaching. Sect. C. N. TAPPI 1993 Pulping Conference Proceedings. Patent 5354423. 1994 TAPPI Pulping Conference Proceedings. Ni and A. Atlanta. 1996 International Pulp Bleaching Conference Proceedings. P. 341 Troughton..1 Ni. Peroxyacetic Acid Bleaching of Chemical Pulp. van Heiningen. Peracid Technology Review. and A. Pulp & Paper.4-Dioxane and Water. 1993 Workshop on Emerging Pulping and Chlorine-Free Bleaching Technology.. N.. A Novel Ozone Bleaching Technology for the AlcellmProcess.. p. F. Mechanism of Cellulose Protection in a Novel and Selective Ozone Pulp Bleaching Process.

J.363 (1 968) . M. p. p. p. Arhiv Za Kemiju. Advances in Chemistry Senes.. Vrbaski. 3 1. Garbuzyuk. Chem. Gavenko and 1. O... and G. The Intermediate Stages of Aldehyde Oxidation. Allen. A. M. D. Aguilo. Ya. 76. C. 26. 39. Kagan. Ukrainskii Khimicheskic Zhumaf. V. The Kinetics of Oxidation of Aldehydes to Acids and Acid Anhydrides. J. G. 55(6):584 (1 989) 30. Phys. and A. T. Influence o f Minera1 Salts ea on the D c y rate of Peroxyacetic Acid in Aqueous Solution.Lubarsky. Metal Ion Catalysed Oxidation of Acetaldehyde. Brihta. and 1.28.837 (1935) 29.267 (1 954) V a s p t p .

CHAPTER 2 LITERATURE FkEVIEW .

pure peracetic acid can be obtained by a vacuum distillation technology in which excess acetic acid. the scale of consumption in a pulp bleaching application requires d e and economicai generation of peracetic acid at the mil1 site. but explodes violently when heated to 110°C [I Il. 1. an equiiibnum mixture of the reactants is normally available. acid-catalysed reaction of hydrogen peroxide with acetic acid. The manufacture of distilled peracetic acid requires the installation of a vacuum still. Peracetic acid is reported to be insensitive to impact.2 at 25°C [ O . Production and Properties of Peracetic Acid Peracetic acid is the mono-acetyi derivative of hydrogen peroxide. as shown in Equation (1): CH3CQH + H202 - CH3C03H + H20 Since the reaction is reversible. hydrogen peroxide and sulfùric acid catalyst are removed and recycled [l.1. PERACETIC ACID AS AN ALTERNATIVE CHEMICAL IN THE BLEACH PLANT New bleaching technologies which do not use chlorine-based chernicals continue to be developed in the pulp and paper industry worldwide in order to reduce the environmental impact of the bleach plants. The process hazards associated with the distillation of the acetic acid-peracetic acid solution are .9]. However. It has a single acidic proton with a pKa of 8. Peracetic acid is classified as a hazardous substance and its reçulations [ I transportation is restricted by Transporiation of Dangerous Goods (TDG) Il. Recent results have shown that peracetic acid is a low capital intensive. easily retrofitted and highly selective non-chlorine bleaching agent [l-91.The most important and widely used method I] of production of peracetic acid is the direct.1. Although peracetic acid is used for chernical syntheses.

which can cause severe bums to skin. and side-chain epoxidation of alkenes [20]. and must be considered in the design and operation of a distilled peracetic acid system [9]. Contacted areas must be washed immediately with large volumes of water to avoid tissue damage.2. It has a boiling point of 103°C and a vapour pressure of 20 rnrnHg at 25°C [Il]. rubber acid suit. eyes and body tissue. Generdly. Long-term exposure to peracetic acid can lead to liver damage.related to the detonabifity of concentrated mixtures. Baeyer-Villiger reaction This is a reaction whereby peracids oxidize ketones to esters [21]: . It is a weaker acid than acetic acid. Personal protective equipment should include a respirator in addition to splash proof goggles. Peracetic acid has a sharp. pungent odour.19j. aromatic ring oxidation initiated by ortho or para-hydroxylation [ 16.1. 1. and lung tumors [Il]. Exposure to the vapour causes lachrymation and possibly lung damage. three discrete pathways were identified: sidechain oxidation of a-carbonyl groups by the Baeyer-Villiger mechanism [ 12153. The oxidation potential of peracetic acid is about 1 . 1. Reactions of Peracetic Acid with Lignin Most of the present knowledge of the reactions of peracetic acid and lignin has been obtained tiom studies with lignin mode1 compounds.2. 0 6 with the hdf reaction shown in Equation (2): ~ CH3C03H + 2H + 2e+ CH3C02H+ H 2 0 (2) The principal hazard of peracetic acid is its corrosive nature. and rubber gloves. decreased white bIood count.

1.3.17]. as shown in Equation (5) [16.2.The reaction has been shown [22] to proceed by a mechanism involving nucleophilic attack of the peracetic acid on the carbonyl carbon. Products consistent with the Baeyer-Villiger mechanism were identified dunng peracetic acid treatment of lignin mode1 compounds with a-carbonyl groups at 60°C and pH 3 [ I 53. Epoxidation of alkenes Alkenes are converted to oxiranes by direct transfer of oxygen as in Equation (4) [20]. The resulting catechols fonned by the former reaction are first oxidized to ortho quinones.2. followed by migration of one of the ketone's alkyl or aryl groups. . and then to muconic acids. Hydroxylation The oxidation of phenols and their ethers by peracetic acid is commonly initiated by ortho and para-hydroxylation reactions [23]. while the etherification of a phenolic hydroxyl group or the presence of an extra methoxyl in the aromatic nucleus appears to have linle or no influence on the reaction rate 1. Hydroxylation at the para site gives hydroquinones which are subsequently converted to p-quinones and then to maleic and fùmaric acid derivatives [I7]. Aiso it was found that a ketone reacts somewhat slower than an aldehyde.2. The oxirane ring may be opened to give a glycol ester if strong acids are present.

Other studies confirmed that peracetic acid is higldy selective in removing lignin fiom wood [26. Furthmore. 1. Boeseken and Engieberts [17] showed that a direct ring cleavage could also ocarr without the formation of a quinone intermediate as show in Equation (6). Peracetic Acid Bleaching The use of peracetic acid as a delignifjhng agent was initially investigated by Poijak in 1948 as a method for preparing holocdulose fiom wood [25].McDonougb [18] found tbat the oxidation of creosol by peracetic acid in moderately alkaline solutions can be accounted for by a mechanism involving electrophilic attack of undissociated peracetic acid on the phenolate anion followed by demethyIation and subsequent nucleophllic attack by the peracetic anion on the resulting quinone intermediates. [24]. wbich was later confirmed by Kawamoto et al.27].3. The subject has .

5.28-321. Also it appears that a peracetic acid (or Pa) treatment at slightly acidic conditions of for exarnple. [3] showed that at a total hydrogen peroxide charge of 3% an oxygen . Pa charge expressed as H O can increase the delignification degree from 35% to 48. More recent work [1.9]. It was found that the maximum brightness gain during peracetic acid treatment of spruce kraft pulp occurred at neutrai pH. A similar peracetic acid treatment of an oxygen delignified pulp results in an increase in the deligiification degree of a following Eop stage fiom 20% to 40% [5]. For example.9% . during an Eop stage [5].3. ] For exarnple. a charge of 5% distilled peracetic acid decreased the kappa number by 62% and 41% after an alkaline extraction stage for hardwood and sofiwood kraft pulps respectively.6.321 supports the earlier findings that peracetic acid is a good delignification agent. pH of 2. Peracetic atid can d m be used as an activation agent before or after an oxygen as well as hydrogen peroxide stage to increase the delignification degree or pulp brightness gain [ .5 to 3.9] and as a briçhteninç agent in the final brighteninç stages of an ECF or TCF bleaching sequence [2. leads to a good delignification [29. peracetic acid pretreatment of an unbleached softwood kraft pulp at 1% 35. an activation asent for oxygen or hydrogen peroxide stages [5.9.30].5. while consistency (3 to 6%) and temperature (50 to 85°C) had little effect on the final pulp properties.recently been reviewed by Liebergott [ 5 ] . the reduction in kappa number obtained with peracetic acid was essentially similar to that of an equimolar quantity of chlorine. At pH of 7 to 9. Troughton et al. Bailey and Dence [28] published a research paper describing the use of peracetic acid for both delignification and brightening of chemical pulps.. It has been shown that peracetic acid can be used as a deIignification agent[ l.3 1.

A surprising fact was that the Pa bleached pulp showed normal reverted brightness (87. while a brightness of 82. Peracetic acid is aIso a good brightening chernical which can be used in the final stages of a bIeaching sequence [5. while the peroxide pulp brightness decreased to 76.90% ISO brightness with a peracetic acid charge of about 1%.9 and 89.5. Phillips et al. Thus he concluded that chlorine dioxide and peracetic acid bleaching may be combined in a single stage.4 can be bleached to a brightness of 74.07% peracetic acid charge. Brightening of a soflwood kraft pulp with CIO2 or peracetic acid produced a brightness of 83% at 0. Peracetic acid may also replace hydrogen peroxide in TCF bleachinç processes [4.8% ISO following a QPP sequence.1% ISO respectively. Liebergott [ 5 ] found that CE delignified sulphite pulps were bleached to 85 . The resulting pulps had a brightness of 85. pH 7.1% ISO is obtained by a QPPaP sequence.33 1.6% CIO. More recent work [5] showed that a Pa treatment of an OZEZ .45% Pa charge expressed as H202. which resulted in a higher brightness gain than either chlorine dioxide or peracetic acid bleaching alone.5% at 0.3%). 70°C and 8% pulp consistency. and 86.9% after 2 hr treatment at 10S0C. Rapson 1333 reported that a peracetic a d treatrnent of a well delignified kraft pulp with a brightness of 69% ISO leads to the production of hlly bleached pulp of 85% ISO brightness afier 4 hr at a 1.delignified softwood kraft pulp with an initial kappa number of 12.35.36]. [35]compared the effect of peracetic acid to hydrogen peroxide in the sequences of OZEZP and OZEZPa. The viscosity was unaffected. Rapson [34] reported that the optimum pH and temperature for chlorine dioxide and peracetic acid bleaching are similar and that the reactions between these two chernicals are negligible.

the drawback of peracetic acid bleaching was its high manufacturing cost.02increased the pulp bnghtness from 81.4% ISO. temperature.3 to 92.is given by: . Dupont. Studies of the spontaneous decomposition of various peracids have shown that the decomposition rate reaches its maximum when pH is equal to the pKa of the peracid [lO. Peracids decompose spontaneousiy in an aqueous solution to give the corresponding carboxylic acid and oxygen [ZO]. Until recently. peracetic acid may aIso be consumed by three wastefiil side reactions. 21 Spontaneous Decomposition . ROOH. 2 PERACETICACID DECOMPOSITION AND HYDROLYSIS A T TYPICAL PULP . Under typical peracetic acid bleaching conditions.1% ISO obtained with a peroxide stage at a charge of 1 %.37-4 11.8.bleached softwood kraft pulp at a charge of 1. BLEACHING CONDITIONS Peracids undergo decomposition and hydrolysis by a variety of reactions which depend on their structures. The rate of disappearance of the peracid. Eka Nobel and Degussa AG are arnong the companies who are marketing peroxy acids in the pulp and paper industry [1. ii) hydrolysis and iii) transition rnetal catdysed reactions.d[RooH1 dt = k [ROOH] [ROO-1 .111. pH and the presence of catalysts. which is superior to a brightness of 90.9].O% Pa as H. it is expected that in addition to the lignin oxidation reactions. notably transition metd ions. namely i) spontaneous decornposition. AIso it is not sufficiently stable to be shipped or stored for extended periods of time 19.

This leads to the conclusion that the electrophilic site is carbonyl carbon rather peroxidic oxygen.5 and then decreases proportionally when the pH is higher than 9. oxygen appeared predominately (83%) as OIW-O'Y [IO]. The reaction rate at 25°C reaches a maximum of 2. Koubek's data showed that the slopes of the two straight line sections deviated considerably fiom unity.9-10. Equations (9) and (1O) show that two straight-line portions with a dope of +1 and . which is also the pKa of peracetic acid.0.When peracetic acid containinç about 4% CH.7 x 105 Wrno1. He found the kinetics to be secondorder in total peracetic acid concentration. He explained this by the hypothesis that the systern . is plotted against pH.s at pH 8. However.2.COO1xOIXH was used. phosphate and borate buffers with H ethylenediaminetetraacetic acid (EDTA) as stabilizer.1 should be obtained if logk.0 as follows: The above kinetics do not include the pH range of 7.2 in carbonate. The rate constant inmeases proportionally with pH until it reaches 7.5 to 9. as shown in Equation (8) [ l O : ] -- The decomposition kinetics of peracetic acid were first studied by Koubek [l O] over the p range of 5.

Based on the experirnental results.0to 8.was complicated by the metal ion catalysed decomposition of peracetic acid [10]. Hydrotysis Hydrogen peroxide and acetic acid are formed upon hydrolysis of peracetic acid. This he explained with the hypothesis that phosphate may catdyse the hydrolysis of peracetic acid.H + H20 + CH. This is due to the fact that borate reacts rapidly with hydrogen peroxide to form peroxyborates so that peracetic acid hydrolysis is dominant.CO. and that a suitable chelating agent must be used to suppress the transition metal ion catalysed reactions when the spontaneous decomposition kinetics of peracetic acid are studied. he conduded that acid hydrolysis and the reaction of peracetic acid with hydrogen peroxide were responsible for the deviation.2. 2. Rucker and Cates [42] reported that the peracetic acid consumption in a borate buffer at a pH range of 7.9 is mainly due to hydrolysis.CO. Therefore. [43] and Koubek [ 1O].H + H.0.Oz (1 1) However. Acid hydrolysis of peracetic acid was studied by Bunton et al. especidly at a pH higher than 8. He also found that the rate constant is lower in an aqueous solution than that in a phosphate buffer. . hydrolysis represents a decrease in real bleaching power since hydrogen peroxide is not an effective bleaching agent under typicai peracetic acid bleaching conditions. and found that the metal catalysed reaction between peracetic acid and hydrogen peroxide is stilI considerable when DTPA is present. the above literature shows that hydrolysis should be considered. and not to spontaneous decomposition. Thus there is no loss of active oxysen in reaction (1 1): CH. Later McDonough [18] investigated the decomposition of peracetic acid in an aqueous solution in the presence of DTPA.

Fe (II).3 Transition Metal Catalysed Reactions 2.It was found [IO] that acid hydrolysis proceeds by nucleophilic attack of water on the protonated peracid molea. He also showed that the reaction order in cobaItous ion concentration varied fiom one at 10" mol/L to one-half at moVL. Koubek [IO] studied the metal ion catalysed decomposition of peracetic acid at pH 5. D'Ans and Mattner [44] reported that peracetic acid hydrolysis increases with increasing pH and MgSO. However. Both studies did not address the kinetics and mechanism of the decomposition of peracetic acid. He found that the kinetics were n first-order i the peracetic acid concentration.9 moVL NaOH solution at 12°C when the transition metal catalysed decomposition of peracetic acid and hydrogen peroxide is suppressed. and that the order of decreasing catalytic activity was Co(II). with its rate beinç first order in peracetic acid concentration as weil as acid concentration. but again the kinetics were not given. Mn(II). They found that manganese catalyses the decomposition of peracetic acid under formation of oxygen. Koubek [IO] observed that alkaline hydrolysis proceeds at a rapid rate which increases with increasing pH. the kinetics of the alkaline hydrolysis were not reported. and Cu(I1). carbon dioxide and c h o n monoxide.441. addition. Aikaline hydrolysis has been the subject of only cursory investigation [ 10. 2. Vrbaski and Brihta [46] reported the effect of cobalt on the decomposition of peracetic acid.4 in an ammonium acetate buffer.1 Transition metal catalysed decomposition of peracetic acid The first study conceming the catalytic decomposition of organic peracids in an aqueous solution was reported by Kagan and Lubarsky [45]. The .de.3. and becomes the dominant mechanism in a 0.

activation energy was found to be 21. The importance of transition metal catalysed decomposition of peracetic acid on the chemical pulp bleaching efficiency has not been examined. 232 Reaction of peracetic acid with hydrogen peroxide . McDonough [18] studied the reaction of peracetic acid and hydrogen peroxide in aqueous solutions at a pH range of 7 to 9. they confirrned that the kinetics are first order with respect to the peracetic acid concentration. On the contrag.4 1. + H20 + 0. Aiso it is worthwhie to investigate the effect of additives such as DTPq DTMPA Na. He proposed that the decornposition followed a radical mechanism.49. (1 2 ) Akiba and Simamura [49] carried out this reaction with ' labelled peroxybenzoate. Mn(I1) is the most harmful metal ion. The reaction between peracetic acid and hydrogen peroxide was first noted in 195 1 by D'Ans and Mattner [44] in their studies of the decomposition of peracetic acid in an alkaline solution.û. on peracetic acid decomposition and bleaching. and MgSO. followed by Co(I1) and Fe(m).. However. Ailen and Aguilo [48] reported second-order kinetics in peracetic acid concentration when they studied the manganese catalysed decomposition of peracetic acid in an acetic acid solution. Furthemore. the above authors didn't extend their study to a neutral pH range which is of interest for peracetic acid bnghtening. The reaction rate was found to increase with increasing .P.. + Hz02 + RCO.50] have reported that hydrogen peroxide reacts with peracids at a pH above 10 as: RCO. Vasyutyn et al. ' O and concluded that the evolved O2 came almost entirely fiom hydrogen peroxide. Later several workers [38.5. [47] reported that in an aqueous solution of peracetic acid without pH controt.6 kcal/mol.

Furthemore. He proposed that there are two reactions between peracetic acid and hydrogen peroxide. and that the cataiytic effect can be minimized by addition of phosphonc acid chelating agents. one of which is catalysed by traces of transition metals. + M"' + H1O Hz07 - RCO. A radical mechanism of the catatytic reaction between peracetic acid and hydrogen peroxide given by the overall reaction Equation ( 12) was proposed by Evans and Upton [50] as: RCO. E a s and Upton [SOI found that the reaction between peracetic acid and vn hydrogen peroxide is strongly catalysed by transition meta1 ions. They concluded that the mechanism of the uncatalysed reaction of peracetic acid and hydrogen peroxide is analogous to that of the spontaneous decomposition of peracetic acid given by Equation (8) as: However. Reaction mechanisms were proposed for these two reactions. O .-+ - RCOOH H. Evans and Upton [SOI examineci the reaction of peracetic acid and hydrogen peroxide at a pH of I O to I 1. this reaction is much more difficult than the nucleophilic attack of peracetic acid anion on peracetic acid since hydrogen peroxide is a much poorer electrophile than peracetic acid.37. Bal1 and Edwards [38] reported that the addition of EDTA stopped the catdytic reaction between Caro's acid (monoperoxysulphuric acid) and hydrogen peroxide at a pH range of 6 to 8. + + (MOH)"' + OH- RC0.pH.

HO2' (MOH)"' + H ' + O?'' ' 02-+ ( 16) Oz OH. Kagan and Lubarsky [45] studied the manganese caîalysed decomposition of peracetic acid in both acetic acid and water solutions. Carbon dioxide and oxygen were the main gaseous products formed in the acetic acid solution and water solution respectively. Contrary to this finding. Formation of Gaseous Products during Decomposition of Peracetic Acid Gaseous products are generated during the decomposition of peracetic acid and the reaction of peracetic acid with hydrogen peroxide [ 1O.46.4. Koubek [l O] also established that roughly 80% of the carbon dioxide formed arises from the acetate ion of the buffer.4 in an ammonium acetate buffer. Furthemore.45. The above authors did not extend their study to a neutral pH range. and claimed that the only gas formed is oxygen. Koukek [IO] later found that both oxygen and carbon dioxide are formed at a molar ratio of about one for cobalt catalysed decomposition of peracetic acid at pH 5. 3.+ Mn+ + ( 17) 2. the optimum pH for peracetic acid brightening [28. Later Allen and Aguilo [48] confirmed that carbon dioxide is the main gaseous product formed fiom the manganese catalysed decomposition of peracetic acid in an acetic acid soIution. They found that the composition of the gaseous products evolved during the peracetic acid decomposition was different for the two solutions. Vrbaski and Bnhta [46] investigated the cobalt catalysed decomposition of peracetic acid in an aqueous solution without pH control.48 3.33]. There has been a growing use . HYDROGEN PEROXIDE BLEACHING OF CHEMICAL PULPS The use of hydrogen peroxide as a pulp bleaching agent has been well documented since its introduction for mechanical pulp bleaching in 1940.

magnesium and calcium) compounds and sodium silicate appear to reduce the hydrogen peroxide decomposition when added to an alkaline peroxide stase 1581. which has been used in some ECF sequences to reach the final brightness target and decrease the chemical cost [5 1-52]. Hydrogen peroxide is also one of the p n m q chernicals used in TCF bleaching of chernical pulps. high temperature (r 100°C) and under pressure. 0 . 1 11. it is generally accepted that a high concentration of such radicais ieads to a poor selectivity and impaired bleaching Alkaline earth metal (e. . Recently. 1541 reported a modified version of hydrogen peroxide bleaching. Its commercial application showed an improved bleaching response at a Iower hydrogen peroxide consumption [55. Devenyns et al. Some transition metals catalyse the hydrogen peroxide decomposition and contribute 2[ to the formation of hydroxyl radicals. Although it has been reported that the presence of low concentrations of these radicai species may actualIy improve hydrogen peroxide bleaching 1571. Another typical appIication of peroxide is to reinfiorce an alkaline extraction stage (Ep) or an oxygen reinforcd extraction stage (Eop). A hydrogen peroxide treatment may be included in the final stages of a bleach plant to achieve higher brightness (292% ISO) and improved brightness stability for specialty puIps [l 11. the so called P(0) process.g. It has been shown that brightness and brightness stability are optimum when hydrogen peroxide is applied at the end of sequences such as OZP.and superoxide anion radicals.These compounds may form complexes with transition metais to lower their catalytic activities. which is operated at high consistency..of hydrogen peroxide in chemical pulp bleaching since the late 1980s due to the pressure to reduce the use of chlorine in the bleach pIant.56]. HO. OZEopP and O(QZ)Q(PO) [53].

are ofien used in the pulp and paper industry to minirnize the negative effect of metal ions. DiethyIene triamuiepentamethylenephosphonicacid (DTMPA) has also been s h o w to be an effective chelant [62]. which are polydentate ligand molecules. . A Mg/Mn ratio of over 30 is needed for effective hydrogen peroxide bleaching at a temperature range of 60 to 90°C.Proper management of metal ions is essential to achieve efficient hydrogen peroxide bleaching. and the MgMn ratio must be higher than 100 if the P(0) process is applied [6 11. Two methods have been shown to yield successfiil bleaching results: 1) chelation with DTPA at pH 4-7 followed by a washinç or pressing stage [59] and 2 ) an acid treatment at pH < 3 followed by washing and addition of magnesium salts to replenish the magnesium removed in the washing stage [60]. Chelants. Some typical chelants include ethylenediarninetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA).

FL. and R. F. p. Lundgren. L. Fredriksson. TAPPI PRESS. sec. Arnini and W. 5-4. Proceedings of 1996 International Non-chlorine Bleaching Conference. Atlanta. Amini. Sponsored by Pulp & Paper and Emerging Technofogy Transfer Inc. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. Troughton. N. Atlanta 93 p. U.. N.R. sec..REFERENCES Hill. and J. 357. Liebergott. Waish. Devenyns. N. Montreal.. and H. Peracid Delignification and Bleaching. Proceedings of 1994 International Nonchlorine Bleaching Conference. FL. Tech. Desprez and 1. Troughton. an Effective Alternative for Chlorine Compound Free Delignification of Kraft Pulp. J. Webster. Desprez and N. 13-2. On-site Peracids: Tools for Bleaching Strategies to Meet the Cluster Rule. Nimmerfioh. 1 1-3. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. B... Devenyns. Basta. TAPPI PRESS.. sec. p. F. 8 1" CPPA Annual Meeting. Wilkinson. 371. B.p. TAPPi 1 9 Pulping Conference Proceedings.. Anderson. 1994 TAPPI Pulping Conference Proceedings. A. and J. Alternatives for Achieving Hi& Brightness TCF Pulps. Holtinger. 10-1. Atlanta. B59. Fasten. Peracids: The Pathway to High Brightness TCF Kraft Pulps. Hyatt Orlando. TAPPI PRESS. On-site Generation and Use of Peroxy Acids in Chemical Pulp Bleaching Preprints. J.. Hyatt Orlando. FL. B. CPPA. Generation and Application of Peracids for Chemical Pulp Bleaching. P. and Considerations on How to Select Among Them. . Peroxygen Prebleaching and Bleaching Technologies for Step-Wise Conversion fiom Conventional Chlorine Bleaching via ECF toTCF. 1 1 . Amelia Island. Proceedings of 1996 International Non-chlorine Bleaching Conference. TAPPl PRESS. Peracetic Acid. p. FL. J. Hollie. Sect. Proceedings of 1994 International Non-chlorine Bleaching Conference. P. sec.. B.. H.A Cost Cornparison.. Swan. 341. Atlanta. Sustainable Development in STORA's Chemical PuIp Mills. 1994 TAPPI Pulping Conference Proceedings.. Suss. R T. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. TAPPI 1992 Pulping 2 9 Conference Proceedings. 1995. Arnelia Island.

34. 80(22):6393 (1958). Chern. E. Roger (ed. Origin of Succinjc Acid as An Oxidation Product of Lignin with Peracetic Acid.. A. 13. Oxidative Degradation of Guaiacylglycerol with Peracetic Acid. and R.. Technol.W. 68. Atlanta. Swem. and H. F. Engleberts. Chem. McCallum.73-106.W. 13(7):35 (1979). Reaction Products of Neutra1 Peracetic Acid Oxidation ofModel Lignin Phenols.Koubek.H. Relative Migatory Aptitudes...C. Boeseken. Japan. Ph. T. Soc. D..D Thesis. T. Am. Hawthorne.. Ph. Ind. Wood Res. Boyd.. T. Oxidation of Monomeric Lignin Model Compounds with Peracetic Acid. G. H.. p. J. 1964. Soc. 35 750(1932). p. Dence. Sci. Pulp Bleachinç-Pnnciples and Practice. . H. M. Peracetic Acid Decomposition and Oxidation of Lignin Model Phenols in Alkaline Solutions. Rapson. 1659 (1910). A Re-examination of the Peroxyacid Cleavage of Ketones. Japan. H.355-533. Kinoshita... University of Toronto (1972). Henderson. D.). Oki and H. 1292(1931). W. McDonough. 76(9): 7276(1975). J.. Migita. New York (1971). The Degradation by Peracetic Acid of Aromatic Cornpounds Structurally Related to Vanillyl Alcohol Elernents Present in Softwood Lignin.)... Ohkubo. Organic Peroxides. G. John Willey & Hassal1. Lignin.D thesis. H. J. Amsterdam. Nakano and N. Oki and K. Cellulose Chem. 1. 20. Brown Univ. and R. M. J. Y. J. 972 (1 965). Ishikawa.G. Proc. Nimz. Chem. Soc. 43S(1966). Ishikawa. Hatakeyarna. 1957. J. 79. The Kinetics and the Mechanism of the Decomposition of AIiphatic Peroxyacids in Aqueous Solutions.3 19 (1967). TAPPI PRESS. E. XLVII. C. and D. 97. Tappi. Soc. New York. J. Strumila. Organic Reactions. 1996. Pulp & Paper Canada. Japan. Chem. Reeve. S. J. Oxidation of Monohydric Phenols with Hydrogen Peroxide. John WiIey and Sons. Georgia. and K.11. p.Emmons. V. Oxidative Decomposition of Lignin. (ed. Sons Ltd. Sect. 9.and H. Schwind. Vol. Acad. Vol. ..

H. HHI. SC. The Bleaching of Pulp. B.C. Tappi J. Preparation of HoloceHulose Fibres fiom Loblolly Pinewood. H. 27. S.s 12. W. 4. Jean. N-G. N. H. K. Peracid Technology Review. A. P. Tappi J. F. . J. 167. Patent.. Metal Manasement in ECF Bleaching and the Effect on Peroxide Efficiency . and C. Feb.Sarkanen. N. Helsinki. Tappi J. Chang. 44(3):230 (196 1). W. Some Chemical and PhysicaI Properties of Pulps Prepared by MiId Oxidative Action. E. Proceedings of 1993 International Non-chlorine Bleaching Conference. T N P 1 Annual Meeting. Laboratory Studies of Acetic Acid Bleaching.. June. Rapson.March. S. 47(3): 157 (1964). Bergeron.. 1965. TAPPZ. Dence. A. C. Thompson. 1.. Preptint. W. and 0. Preprint. 1983.383 Poljak. Ludwig.C. Finland. Bailey. H.. Anderson. 227. Angew. Parker. 8. W. NY. 1985. 1963. Quebec. F.. p.. C. V. M. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. U. Troughton.. Rapson. Lignins. F. 49(1):9 (1966). R.. Jameel. p.S. Proceeding of the 8m International Symposium on Wood and Pulping Chemistry.Y. and C. Tappi J. Bleaching in Five Stages to Asymptotic Limit Using Only One Oxidant and Sodium hydroxide.. HolzafschluP mit Peressigaure. and W. Rapson... Johansson. 1993. and C. and H. 1993 Workshop on Emerging Pulping and Chlorine-Free Bleaching Technology. p458. W.. 8-1.. Proceedings of 1985 International Pulp Bleaching Conference. and P. Devenyns. 1995.. M. H. B. Geiierstedt. Raleigh. Johanson. Kaustinen. N.. The Role of pH in Bleaching.. B.. W. p. Philips. 39(5):284 (1 956). Kemp and R. ed.60A:45 (1948). p132. B. Peracetic Acid as a Selective Prebleaching Agent: an Effective Option for the Production of Fully Bleached TCF Kraft Pulps. sec. Wiley Interscience. Biggers. Peroxyacetic Acid Bleaching of Chemical Pulp. G. Eckert. Christiansen. 1971. H.372. Kawamoto. Reaction of Peroxyacids with Lignin and Lignin Model Compounds. Desprez and N. Leopold. Clark. A W. Chernid Composition and Physical Properties of Wood Fibres. B. Chem. Monograph No.

Vrbaski. Ya. Shang. Francis.. R. O. Tappi J.837 (1935). J. Koubek. Phys. 1226 (1956). Battaglia. "Kinetics and Mechanism of the Spontaneous Decomposition of Some Peroxoacids. J. 1 125-1 129 (1 956). D. J. Bunton. 2. A. J..L.267 (1 954). Cates. Ukrainskii Khimicheskic Zhumal. Durch Nebenreaktionen Geht Aktiver Sauerstoff Verloren. Edwards. 58(13):148 (1988). M. A. and J. 278 1-2875 (1 963). Robson. J. T. Edwards.140 ( 1 994). Chem. and D. Soc.C.R. 1994 TAPPI Pulping Conference Proceedings. 85. Soc. Tracer Studies in the Formation and Reaction of Organic Per-acids. Chem. 63. P. Atlanta. Arhiv Za Kemiju. 26. H. and 1.2' -bipyridine Catalysed Bleaching of Cotton Fibers with Peracetic Acid. J. J. The Intemediate Stages of Aldehyde Oxidation.. O. p. Vasyutyn. Baü. J. 55(6):584 (1989). Magnesiumhydroxyd und andere Stoffe Verhindem diesen Verlust. Chem. Jones. M. M. D Lubanky. T. Soc. Froass and 0. Angew.. M.M. Tarner. O... Goodman. E. p. A. F.. 77(6).368-370 (1 95 1). Decomposition of Inorganic Peroxyacids in Aqueous Alkali. M.. . K. M.J. Ball. " The Kinetics and Mechanism of the Decomposition and of Caro's Acid. 78. and P. Soc. Edwards. 89. L. J. D'Ans. X. O. V. C. L. Amer. J.. Mattner. 133. Llewellyn. J. Part 1. Garbuzyuk. Ibne-Rasa. Festes Magnesiumhydroxyd Beschleunigt die Hydrolyse. 2263-2268 (1963).. H a s e t t . J. and G. 39. R. Bnhta. 1345. Lewis and D. E. Pyun and J. C. 1". TAPPI PRESS. A Kinetic and Isotopic Study of the Decomposition of Monoperoxyphthalic Acid. Amer. Chem. Chem. J. 233 1-2333 (1967).. p. p. Aikali-and Metal-induced Decomposition of Peroxymonosulfate. Kagan. Hydrogen Peroxide and t-butyl Hydroperoxide". Y. Rucker. Influence of Mineral Salts on the Decay Rate of Peroxyacetic Acid in Aqueous Solution.. Chem. Gavenko and 1. Soc.W. Amer. Acetpersaure Erleidet in Verdümter Natronlauge Hydrolyse in Wasserstoffperoxyd und Acetat. Textile Res. Chem.in the EPO Stase. The Kinetics of Oxidation of Aldehydes to Acids and Acid Anhydrides. Haggett and P.

CPPA. W. Studies on Singlet Oxygen in Aqueous Solution. D. TAPPI 1993 Pulping Conference Proceedings. K. 53. F. J. Chem. Hermansson.. Devenyns. Optimum Use of Peroxide and Ozone in TCF Bleaching. Dence. and S. Diiiner... 1994. U. P P S . TAPPI PRESS. OZP Bleaching of Kraft Pulps to Full Brightness. Holtinger. p. CPPA. 1994. Tech. Sect.. p. Tetrahedron. Metal Ion Catalysed Oxidation of Acetaldehyde. J. International Pulp Bleaching Conference Papers Preprints. D. W. Geiierstedt. and 1. L. 1992 Tappi Bleach Plant Operations Short Course Notes.25 19-253 1 (1 970).. Tech. Pettersson. 26. C P P q Montreal. P. Bleaching at Weldwood Hinton. J. and M. G. p. Hydrogen Peroxide Use in Chemical Pulp Bleaching. B. Akiba. 15(2):J45 (1989). Start and J. TCF Bleaching . Montreal. Advances in Chemistry Series. Atlanta. Montreal. 1151. Aguilo... Applications to TCF Sequences.3.. 443. The Bleaching of Kraft PuIps. Anderson.363 ( 1968). S. Genngkd. Evans. International Pulp Bleaching Conference Papers Preprints. TAPPI PRESS. . Montreal. and P.799. Tibbling.29. 76. Sect. p. Atlanta. Tech. CPPA. W. Tech. Simamur* Decomposition of Sodium Peroxybenzoate in Sodium Hydroxide Solution. TAPPI PRESS. J. Soc. R. Troughton. Atlanta p. Desprez and N.C. and P. Norden. Tech. Dalton Trans. L. 1992. Rothenberg and C. 2(3):23 1 (1982) Colodette.. Basta. G. Lundgren. Wood Chem.3 19. CPPA Pacific and Western Branch Annual Meeting. G.. Prepnnts.1153 (1985). Part II. Lazorek. Sect. Factors AfFecting Hydrogen Peroxide Stability in the Brightening of Mechanical and Chemimechanical Pulps. J. Part 3. and N.. Part III. p. Sect. Chemical Aspects of Hydrogen Peroxide Bleaching. and A.Which Sequence to Choose?. 1993 TAPPI Pulping Conference Proceedings.Nguyen-Thi. Young.B. Internationd Pulp Bleaching Conference Papers Preprints. Utilization of an Eop Stage During 100% CIO. Section 4 4 Paper No. J. p. TCF/ECF BleachingPart 1-TCFBleaching. Lachenal. J. 123. 1994. Upton. P': One-stage Hydrogen Peroxide Bleaching of Previously Delignified Pulp. and 0.Allen.

Plumet. Appita. F. Peroxide Bleaching of Mechanicd PuIp fiom Pinus Radiata. Ek. Metals Control in TCF Bleaching . W.. . 1994 TAPPI Pulpinç Conference Proceedings. 61. Troughton. p. TAPPI PRESS. and L. 62. p. N. Desprez. P. M. 1 161.38 1. Devenyns. 1994 TAPPI Pulping Conference Proceedings. R. Axeçard.. E. 36(5):362 ( 1 983). Atlanta. The RoIe of Meta1 Ions in TCF Bleaching of Softwood Kraft Pulps. Bergnor. TAPPI PRESS. Atlanta.Implications for Kraft Bteaching Sequence Design.. J. Ekholm. Aifison.60. and U.

CHAPTER 3 PERACETIC ACID AND HYDROGEN PEROXIDE BRIGHTENING OF A SOlVWOOD KRAFT PULP DELIGNIFIED BY METHANOGASSISTED OZONA'IION .

ABSTRACT In earlier studies at the Limerick Pulp and Paper Centre. viscosity pulp. A fiactional factorial design with four parameters. However. it was demonstrated that conventional chernical pulps cm be delignified by a solvent-assisted ozone process to a low kappa number while still maintaining good viscosity and strength properties. hydrogen . Keywords: peracetic acid brightening. In this chapter. brightness. The effect of operating variables of the Eop stage. were also investigated. totally chlorine fiee bleaching. this brightness level is achieved by sequential application of a peracetic acid and an Eop stage. charge. each perforrned at three levels. ozone delignified s o b o o d kr& peroxide. a final brightening sequence was developed for this ozonated pulp with a peracetic acid treatment and an Eop stage. It was found that a single m peracetic acid stage c not produce a fùlly bleached pulp with a brightness above 88% ISO. Finally it was argued that a conventional softwood kraft pulp bleached to 88% ISO brightness by this TCF sequence of ZnEoPaEop has strength and bnghtness stability properties similar to or better than those of chlorine and chlorine dioxide bleached pulps. MgSO. such as the caustic charge. was used to optimize the process conditions of the peracetic acid stage. temperature and time.

8]. However.8 and a viscosity of 28. such as the tear index (at the same tensile index). are typically 10 .4 mPa. and generalIy in the range of 80 . which are capital intensive and generally less selective than the chlorine based processes. a well delignifed pulp with a kappa number of 5. For example. .s was subjected to a ZnEo sequence. it appears that the pulp strength properties. recent advances in the manufacture of peracetic acid have significantly reduced the cost.7. In most insiances. these TCF processes still have a number of weaknesses. although known as an effective delignification chemical for nearly fi@ years.4. Althougli a few papers [9-101 reported that TCF fùlly bleached pulps cm be produced with strength properties similar to those of conventionally bleached pulps.15% lower than those of pulps wt equd final bnghtness obtained by conventional chlorine-based ih bleaching [3.was until recently considered too expensive for commercial application [ 161. where Zn represents the solvent-assisted ozone bleaching stage. these TCF sequences require oxygen delignification ancilor other extended delignification techniques.INTRODUCTION Commercial production of TCF fblly bleached softwood kraft and sulfite pulps is now a reality [l-81. Furthemore. the final pulp brightness achieved in these bleaching processes is below 88% ISO.8]. However. Peracetic acid. Earlier studies at the Limerick Pulp and Paper Centre and at MacMillan Bloedel[l 1151 showed that a solvent-assisted ozone bleaching process can replace chlonnation as the delignification step while maintaining the same iignh-carbohydrate selectivity as that of chlorine bleaching.85% ISO [3-5.s can be obtained when an unbleached Hemlock kraft pulp with a kappa number of around 30 and a viscosity of about 33 rnPa.

.33] that a-carbonyl and quinone structures are effdvely removed.70°C and 8% pulp consistency.07% charge of peracetk acid. On the other hand.2 1-241. and limited results are available on the use of peracetic acid as a brightening chemical to produce fùlly bleached chemical pulps [19.25-281. The main objective of the present study was to develop a TCF brightening sequence . Most of the literature on peracetic acid in pulp bleaching deals with delignification [ 16. or peracetic acid produced a brightness of 83% ISO at a charge of 0.5% ISO at a peracetic acid charge of 0.18].making peraçetic acid a promisinç candidate for pulp bleaching [16. one might expect that a higher brightness could be achieved by a sequentiai treatment of chemical pulp with peracetic acid and hydrogen peroxide. pH 7. Rapson [28] reported the effect of pH on the briçhtness and viscosity development during peracetic acid treatrnent of a CEHCE delignified kraft pulp with a brightness of 69% ISO. Brightening of a softwood kraft pulp with C10. while a. It is known [32. and 86. Liebergott [19] found that CE delignified sulphite pulps could be bleached to 85 .90% ISO brightness with a peracetic acid charge of about 1%. The pulp brightness increased to 85% ISO after 4 hours at a 1. P-unsaturated double bonds are stable and continuously formed durinç conventional hydrogen peroxide bleaching. Therefore.17.29-3 11. A minimum viscosity loss was observed in the pH range of 8 to 9. Hydrogen peroxide is a good brightening chernical when the optimum conditions are used [8. as was confirrned by Liebergott (351 as well as Ni and Ooi [36].6% CIO. double bonds in residual liçnin are very reactive toward peracetic acid [34].45% expressed as equivalent weight of hydrogen peroxide [i 91. A hydrogen peroxide reinforced extraction stage (Eop) has been widely applied to achieve a higher final bnghtness at a reduced chemical cost [30-3 11.

1 hour. MgSO. The ozonated pulp was then subjected to an Eo stage at the following conditions: 2% NaOH charge. M e r Pa treatment. and DTPA obtained fiom Fisher Scientific (Nepean.24% peracetic acid charge equals to 1% H O on an equivalent oxidant basis. USA). 40% wlw acetic acid with the remainder being water.8 and viscosity of 28. . 205 kPa 0.7 ppm Mn and 1..8 ppm Fe. the pulp was washed thoroughIy with deionized water and the spent .5% ISO. high strength product comparable to conventionally bleached pulp. The methanol-assisted ozone bleaching (Zn) was camed out at a consistency of about 35% with a 70% methanol solution of pH 2 as impregnation liquor. The quantities of chernicals are expressed as a weight percentage of pure chernical on oven dried pulp. 2. of which over 90% was consumed during the course of the reaction. Reagent gade -O2. 7OoC. The ZnEo treated pulp has a transition metal ion content of 61. 10% pulp consistency. Ontario) were used without fùrther purification. kappa number of 5. The ZnEo pulp with a brightness of 56. pressure. EXPERIMENTAL Peracetic acid was purchased fiom Aldrich (Milwaukee.s respectively. 2. The peracetic acid brightening was camed out in a poIyethylene bag containing a suficient quantity of NaOH and water to provide the required initial pH and consistency. NaOH.4 mPa-s was obtained fiom MacMillan Bloedel Ltd. 5% wlw hydrogen peroxide.. Its composition is about 34% w/w peracetic acid.3 ppm Cu. The ozone charge was 2%. The kappa number and viscosity of the original unbleached Hemlock kraft pulp were about 30 and 33 mPa.usin3 peracetic acid and hydrogen peroxide for the ZnEo sofiwood kraft pulp to produce a fÙlI brightness.

is the average brightening result obtained at the first level (1%) of the first factor (peracetic acid charge) at different pHs. A hctiond fadorial design ofh(3') was used to optimize the process conditions. T230 om-89. . where Ij is the average brightness or viscosity when bleaching is performed at the first level of factorj and various levels of the other three factors. Pulp brightness. RIESULTS AND DISCUSSION 1. and each was investigated at three levels. For example. The Eop stage was performed under oxygen pressure in a specially designed stainless steel bomb with tefion liner to avoid direct contract between the puip sample and the metal surface. temperatures and pulp consistencies. Temperature.0) of the third factor (initial pH) at different peracetic acid charges. 1. II. viscosity and kappa number were determined in accordance with TAPPI methods T452 om-92. and T236 cm-85 or Tappi UM246. peracetic acid charge and pulp consistency were chosen as the four factors. Also included are the standard data analysis results. An oil bath was used to keep the bomb at the required temperature. Table 3-1 Iists the bleaching results &er 3 hr.liquor was titrated for its residual peracetic acid and hydrogen peroxide concentration following the iodometric method developed by Greenspan and Mackellar [37].. is the average brightening result obtained at the second level (pH 7. pH. respectively. spent liquor was analysai for residual H O . After the Eop stage. Peracetic Acid Brigbtening (Pa) of ZnEo Delignified Pulp The ZnEo semi-bleached pulp was subjected to a peracetic acid treatment (Pa). the pulp s l u q was washed thoroughly with deionized water and the . temperatures and pulp consistencies.

Visco. (OC) Brightness (% ISO) Viscosity (mPa. Diff.Table 3-1.7 22. The Fractional Factorial Design of b(3')for Pa Brighiening of ZnEo Delignified Pulp Run Pa Charge (Yo) F1 a Pulp Conc.6% I O was obtained between the pulps prepared at different S .5 24. a maximum brightness difference of 5. For example.s) 1 1. IIIi M The maximum differences listed indicates the maximum possible change in pulp properties which were caused by the variation in the Ievel of a specified factor.: Ii 25.8 U II.O IO Max. (%) Bleaching Results I Initial PH Temp.

20% pulp consistency. a fbrther increase in consistency to 30% l a d s to a slightly smaller brightness gain. Finally.5% peracetic acid charge.28]. 60°C and an initial pH of 7. The latter can be attributed to the h t that at higher temperature more peracetic acid is consumeci in wastefùl side reactions which generate harmful reactive species (see Chapter 6 for details). This may be explained by the difficulty of mixing pulp and chemicals at 30% consistency.initial pH levels of 5.5 to 2%. A cornparison of the maximum differences for both brightness and viscosity shows that pH is the most important operating parameter affecting the performance of a Pa treatment. an increase in puIp consistency from 10% to 20% improves the bleaching results by an additional 3.s. 7. An additional experiment performed at a temperature of 80°C shows that the brightness does not increase fùrther above that obtained at 60°C while the pulp viscosity is significantly fùrther c reduced to 14. it can be concluded that the optimum condition for peracetic acid bnghtening of ZnEo delignified pulp is 1. The ZnEoPa pulp produced at these optimum conditions has the following properties: 82.s viscosity and 1.7% brightness. Table 3-1 also indicates that a peracetic acid charge of 1.8 mPa. which is consistent with the findings of eariier studies [I9.1 shows that the pulp brightness increases with increasing temperature.0.24. Table 3. The optimum pH is in the neutral range. Therefore.6 mPa.0. 26. However.3% ISO brightness units. Based on the above analysis. while the pulp viscosity decreases slightly at the highest temperature.5% is appropriate since the fiirther increase in btightness is very small when the peracetic acid charge is raised fiom 1. . a temperature of about 60°C is optimum for peracetic acid brightening of the ZnEo delignified pulp.0 and 9.0.9 kappa number.

Therefore. It was found that an Eop stage gave the best brightening result.2 80.6 Residual Pa (% on charge) 28. the Eop stage was used for . initial pH of 7. confirming that peracetic acid is rather selective dunng final brightening [ 17. We fùrther studied the efFect of bleaching time at the above specified optimum conditions.5% Pa charge.For al1 the runs perfomed so far in this study a reaction time of 3 hours was chosen. it shows that the viscosity loss during peracetic acid bleaching is relatively smail when operated at the optimum conditions.2 26.7 82.4 27.9 21.5%.8 26.24. The results listed in Table 3-2 show that there is no need to extend the bleachins time beyond 3 hours. By fùrther increasing the charge of peracetic acid it can be shown that a brightness ceiling of about 84% ISO is obtained at a peracetic acid charse of 5%. Furtherrnore.28].7 82. Table 3-2.5 78.7 12. The pulp brightness afler either the Eo or Ep stage was about 2-3 units Iower than that after the Eop stage. it wras shown that the optimum peracetic acid charge is about 1. 20% pulp consistency.9 Viscosity (mPas) 28.6 1 2 3 15. Therefore.4 4 26. Further Bnghtening of ZnEoPa Treated Pulp in An Eop Stage In the previous section.0 2.The Effect of Reaction Time on Peracetic Acid Bleaching of ZnEo Delignified Pulp Bleaching Time (ho O Brightness (% ISO) 56.0 Other Conditions: 1. we fùrther treated the ZnEoPa pulp with either an Eo or an Ep or an Eop stage. 60°C.

0.5% to 1. pulp) 0. A fiirther increase in the HzOz 89.5% and charge fi-om 0. 0.20% consistency.1 H202 charge A fùlly bleached pulp of 88.2 NaOH charge It is known that the perhydroxyl ion. Therefore.0% brightness and 1 8.s viscosity can be obtained when subjecting the ZnEoPa pulp to an Eop stage with charges of 0. however the viscosity decreased to 15.5% H202charge. 2. Dressure. . The results in Table 3-3 suggest that a NaOH charge of 1-5% is the optimum level for the present conditions.9 mPa.1 Other conditions: 0. I05"C.0% raises the brightness to NaOH. conditions.1 Residual H.5% H O charge will be . the dominant form of H O under alkaline . (% on charge) 26.5 Brightness (% ISO) 85. used in the Eop stage.s. is the reactive species during peroxide brightening. The Effect of NaOH Charge on the Eop Stage NaOH Charge (% on 0. and the determination of the optimum conditions of this stage is described in the following sections. Table 3-3.0°/0. 2.1 rnPa..d.O.) .9 Viscosity (m Pas) 31.. 60 psi O.05% MgSO. Therefore optimization of the alkalinity is important for a maximum brightness gain.5% H202 1.further brightening of the ZnEoPa pulp. However. excessive caustic addition may cause aikali darkening. 60 min.

7 mPa.9 rnPa. Similar results were obsenred for hydrogen peroxide bleaching of an oxygen delignified kraft pulp [38].[41] found that DTPA addition to a hydrogen peroxide solution reduces the copper and manganese catalysed decomposition of hydrogen peroxide.s. This then .0% 1SO and viscosity of 18.43] that Fe3' chelated by EDTA or DTPA is still catalytically active towards hydrogen peroxide decomposition. In the experimental section. With a DTPA charge of 0. it is reasonable to assume that the effect of the addition of DTPA to the Eop stage depends on the metal ion profile in the original pulp. a TCF bleached pulp with a brightness of 88. it was reported that iron is by far the most dominant transition metal species in the ZnEo delignified pulp. a negative effect is expected if the iron content is relatively high in the pulp. It was also reported [42. The effect of DTPA addition to the Eop stage was investigated for the ZnEoPaEop sequence (Table 3-4). Colodette et a1. Therefore.40]. The latter was explained by the well known fact that DTPA in the bleaching liquor chelates and thus inactivates the metal ions released by the pulp [29].s was obtained without DTPA in the Eop stage. However. but enhances the iron catalysed decomposition.2%. the brightness did not change significantiy but the viscosity decreased to 16. A fûrther increase in the DTPA charge resulted in both a decrease in viscosity and brightness. However.2 3 DTPA addition . it is expected that a beneficial effect will be observed if the pulp sample contains more manganese and copper. As mentioned earlier. Also less residual hydrogen peroxide was present at the end of bleaching when more DTPA was charged to the Eop stage. this is contrary to other references which report that the inclusion of DTPA in the peroxide bleaching liquor results in a higher brightness gain as weU as a higher peroxide residual [39. Thus.

1.6 IO5OC 60 Dsi 0-m 88.pulp) Brightness (% ISO) Viscosity (mPas) 18.. The Addition of DTPA to the Eop Stage r DTPA charge (% on O-d. 0. is added to the Eop stage. 2. 2.6 Residual H202 (% on charge) O 0. This is in agreement with the çeneral consensus [46-491 that a suitable ratio of magnesium to transition metal ions should be maintained in hydrogen peroxide bleaching.4 MgSO. 1% MgSO.explains why in Our system the addition of DTPA has a detrimental effect on the performance of the Eop stage.3 84.05 to O.5% H. The results in Table 3-5 show that a brightness gain of about 3 to 4% 1SO and Mscosity increase of 6 to 7 mPa. Table 3-4. The addition of too much MgSO. reduces the brightness development.9 16.0 20. i e .2 0. 60 min ) . charge.4 0.0 88. .7 12. The cornpiete consumption of residual hydrogen peroxide in the absence of MgSO.1 O O Other conditions: 0.O.1 10.s are obtained when 0.45].5% NaOH. is an indicator of significant peroxide decomposition and thus less efficient use of hydrogen peroxide for brightening reactions. addition MgSO.3 84.05% MgS0.5 Temperature and reaction time The effect of temperature and reaction tirne on the Eop stage is shown in Table 3-6. 20% consistency.5 12. is known as a stabiiizer for hydrogen peroxide bleaching [44. however.

No DTPA is needed for this particular pulp since iron is the dominant transition rnetal ion present in the pulp.5% H 0 . Note also that more hydrogen peroxide remains at 95OC than at 10S°C. A hrther increase in the reaction time to 90 minutes at 105°C or to 120 minutes at 95°C deçreased the final Mscosity. The . 20. 105"C.O. 1.. 20% consistency.0 I1 pressure.d.0 88.5 27. charge. pulp) O Brightness (% ISO) 84.4 88. indicating that less hydrogen peroxide is decomposed during bleaching at 95°C.1 Viscosity (mPa.6 The optimum Eop condition B a d on the above reported results it is now possible to define the optimum operating . Therefore the optimum reaction time should be about 90 minutes at 95°C.3 0.2 87.A cornparison of pulps with similar brightness (Run 2 and 5) shows that a decrease in Table 3-5.1. 2. conditions of the Eop stage for the ZnEoPa treated pulp: 0. 60 psi oxygen pressure and 90 minutes.3 19.2 18..5% NaOH. 20% consistency. To compensate for the decrease in reaction rate at a lower temperature .1% MgSO.2 0.2 15.) Other conditions: 60 0.5 87. The Addition of MgSO.5% H. 60 psi Q temperature fiom 105°C to 9S°C improves the Mscosity by about 2 to 3 units.9 19. min.s) 12.02 (% on charge) O 0. 95OC. the reaction time of the Eop stage at 95°C was extended fiom 60 to 90 minutes.9 19.05 O1 .5 Residual H.4 17. charge (% on 0.5% NaOH and 0. to the Eop Stage MgSO.

5 27.final brightness and viscosity for these conditions are 88.O.5% NaOH. 60 psi 0.2 89.4 19.6 49.3 O 22. 1. Another characteristic of . Therefore.9 15.7 The optimized ZnEoPaEop pulp Forber [50]concluded that a fully bleached TCF pulp will exhibit strength properties comparable to those of conventionally bleached pulp if its viscosity is about 16 mPa. 0. due to insufficient sample.5% H.s) 19.s.1 86. (% on charge) 86. the strength properties of this TCF fully bleached pulp could not be determined.1 - Other conditions: 0.1% MgSO. charge. Table 3-6. It should be noted that this TCF sequence started with a conventional softwood kraft pulp of kappa number 30 without using any extended cooking or oxygen pre-delignification.1% 1SO and 2 1.8 mPa. 20% consistency. The Effect of Tempenture and Reaction Time of the Eop Stage Brightness (% ISO) Viscosity (mPa.s or higher.5 3 1. 2. it is reasonable to assume that the fùlly bleached Hemlock softwood krafi pulp obtained by the optimized ZnEoPaEop sequence will be as strong as chlorine and chlorine dioxide bleached pulps. pressure .3 88. Unfortunately.4 Residual H20.

The brightness reversion of both pulps was about 1. 4. However.$per tonne of pulp.1% 1SO and a viscosity of 21. the brightness can be further increased by a find Pa treatment at a charge of 0.s.5 rnPa.5% while the other conditions being the same as those of the first Pa stage. Brightness Stability of the TCF Fully Bleached Pulp TCF firlly bleached pulp samples of 88. the brightness of the ZnEoPaEop pulp was limited to about 89%.4% ISO brightness obtained by the ZnEoPaEop and ZnEoPaEopPa sequence respectively. The resulting bleached pulp has a brightness of 90. This is comparable to that of an ECF . which compares favourabiy with a reversion of 1.9% ISO for a conventionally chlorine and chlorine dioxide bleached pulp [ 1 O]. 5.1. 3. were subjected to rapid aging at 105OC for 1 hour.4% ISO and a viscosity of 20. Further Brightening of the ZnEoPaEop Treated Pulp by a Final Pa Treatment As s h o w in Section 2. Table 3-7 shows that the total cost of the bleaching chemicals used in the process is about 55 US.1 and 90.the present TCF sequence is that no chelants are used in the bleachinç sequence.1% ISO. Chernical Cost Evaluation of the ZnEoPaEop Sequence An economic evaluation was made of the chemical cost of the ZnEoPaEop sequence which produced a fùlly bleached Hernlock kraft pulp with a brightness of 88. Apparently the sequential treatment of pulp by peracetic acid and hydrogen peroxide leads to an increased brightness ceiling due to the complementary brightening chemistry of these two chemicals.s.8 mPa.

Cost (U-S.5 1. pulp) From reference [5 1] Other chernicai costs From reference 1 0 21 CONCLUSION A conventional sofiwood kraft pulp with kappa number of 30 has been bleached to 88% ISO brightness while maintaininç a viscosity of more than 20 mPa.S. The optimum conditiom for the peracetic acid and Eop stages have been .1.bleaching process [ 3 6 ] .53 0.S. This chapter focuses on the final brightening of ZnEo pulp by peracetic acid and hydrogen peroxide.5 H A MgSO4 O.$) 22.d. Table 3-7.0 Zn Eo 0 3 2.7 4.53 55-82 1 I Total chemical cost (U.0 1 .d.$/ton 0.18 03 . viscosity and brightness stability of this TCF filly bIeached kraft pulp are similar to or better t han those of chlotine-containing bleached pulp.9 O.0 2. Estimation of Bleaching Chernical Cost of the ZnEoPaEop Sequence Stage Chernicals Charge (% on 0.5% hydrogen peroxide charge.s by a ZnEoPaEop TCF sequence with 2% ozone.0 0. 1 O. 17.5 0.5% Pa and 0.5 1.06 6.3 0.5 4.puIp) Unit Price (U.%/kg) 1.6 Pa EOP Peracetic acid NaOH 1. The brightness.O NaOH 0 2 0. 1.

1% MgSO.5% and 0. 60 psi oxygen pressure.5% H2021. for supplying the ZnEo pulp. The unique . 90 min with 0. Those for the Pa stage are 20% pulp consistency .5% NaOH and 0. neutral pH and 3 hours. ACKNOWLEDGMENT The author thanks NSERC for financial support in the form of a Strategic Grant and MacMillan Bloedel Ltd. no chelation chernicals are required for this TCF bleaching sequence.60°C. 95"C. . charactenstic of this TCF sequence is that it can be applied to conventional sofiwood kraft pulp with a kappa number of about 30 .determined. Also. a The peracetic acid charge for the first and second Pa stage is 1..5% respectively. The optimum conditions for the reinforced Eop stage are 20% pulp consistency .

Fredriksson. FL. and L. H. and R. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. 1994 International Bleaching Conference. Sponsored by Pulp & Paper and Emerging Technolog Transfer Inc. J. and R. and J. sec. A. Vancouver.16. Proceedings of 1994 International Nonchlorine Bleaching Conference.1 Malinen. 1 1-4 Kubelka. Desprez and N. 13-2 Seccombe..sec. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. FL. TAPPI 1993 Pulping Conference Proceedings.Toikkanen. Wizani. FL. FL. Martens. B. 1 1-1 Basia. B. 341. Desprez.. June 13. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. Practical Mill Experience with the Use of Caro's Acid to Produce High Brightness TCF Pulps. Devenyns. Amelia Island. 10. Hyatt Orlando. Arnelia Island. Atlanta p. sec. 3-2 Troughton. Szopinski.Fasten. R. L. Pressurked Hydroçen Peroxide Bleachinç for Improved TCF Bleaching. R. R. Rantanen. G. N. p. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. R. sec. sec. Holtinger. FL. H. Ametia Island. Amelia Island. Peracids: The Pathway to High Brightness TCF Kraft Pulps. 1994. Hill. Troughton. Proceedings of 1994 International Non-chlorine Bleaching Conference. Lundgren. F. Proceedings of 1996 International Non-chlorine Bleaching Conference... TAPPI PRESS. 199. Proceedings of 1994 International Non-chlorine Bleaching Conference. and A. J. Alternatives for Achieving High Brightness TCF Pulps. Proceedings of 1994 International Non-chlorine Bleaching Conference. Haakana. June 1994 Devenyns.. P. V. Rautonen... TCF Bleaching to High Bnghtness: Bleaching Sequences and Pulp Properties. Kappel. Arnelia Island. 1994 International Pulp Bleaching Conf. Sustainable Development in STORA7sChemical Pulp Mills. 187 Stromberg. Proceedings of 1994 International Non-chlorine Bleaching Conference. J. p. Vancouver. FL. Enerbatch Extended Delignification for TCF Pulp. Neubauer. 1 1-3 Swan.REFERENCES Richard. T. Worldwide Survey: State-of-the-Art TCF Bleaching. . sec. and J... Peroxygen Prebleaching and Bleaching Technologies for Step-Wise Conversion from Conventional Chlorine Bleaching via ECF toTCF. W. F.

Germgard. U. and S. Nordén, OZP-Bleaching of Kraft Pulps to Full Bnçhtness, International Pulp Bleaching Conference Papers Prepnnts, Tech. Sect., CPPA, Montreal, 1994, p. 53 Ni, Y. and A. R. P. van Heiningen, Ozone Dioxiane Bleachinç of Chemical Pulps, U.S. Patent 5354423, 1994 Solinas M. and T. H. Murphy, Ozone Selectivity Improved with Use of Organic Solvent, PuIp & Paper, 7 ( ) 133 (1 996) 03: Ni, Y. and A. R. P. van Heiningen, J. Lora, L. Magdzinsk, and E.K. Pye, A Novel Ozone Bleaching Technology for the Alcell" Process, J. Wood Chem. And Techn., 16(4):367-380(1 996) Kang, G. J., Y. Ni and A. R. P. van Heiningen, Mechanism of Ceilulose Protection in a Novel and Seiective Ozone h l p Bleaching Process, Preprints. 82nd CPPA Annual Meeting Tech. Sect., C P P q Montreal, 1996, p. B303 Ni, Y. and A. R. P. van Heiningen, Improved Ozone Bleaching by Impregnation of Chemical Pulps with An Acified Mixture of 1,CDioxane and Water, Proceedings of 1996 International Bleaching Conf ,Washington, D. C., April, 1996, p.2 13

HiIl, R T., P. B. Walsh and J. A. HolIie, Peracetic Acid, an Effective Aitemative for
Chionne Compound Free Delignification of Kraft Pulp, TAPPI 1992 Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p. 1219 Devenyns, J., F. Desprez and N. Troughton, Peracetic Acid as a Selective Prebleaching Agent: an Effective Option for the Production of Fully Bleached TCF Kraft Pulps, Proceedings of 1993 International Non-chlorine Bleaching Conference, Sponsored by Pulp & Paper and Emerging Technology Transfer Inc., HHI, SC, sec.
8- 1

Amini, B. and J. Webster, On-site Peracids: Tools for Bleaching Strategies to Meet the Cluster Rule, and Considerations on How to Select Amonç Them, TAPPI 1994 Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p. 37 1. Liebergott, N.. Peracid Delignification and Bleaching of Chemical Pulp Pari II: Oxidation, Pulp & Paper Canada, 97(3):73 ( 1996) NimrnerfYoh, N. and H. U. Suss, Generation and Application of Peracids for Chemical Pulp Bleaching- A Cost Cornparison, Proceedings 1996 International Non-chlorine Bleaching Conference. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. Hyatt Orlando, FL, sec. 5-4

Gellerstedt, G., Peracid Technology Review 1993 Workshop on Emerging Pulping and Chlorine-Free Bleaching Technology, Preprint, Raleigh, N.C., March 3, 1993
Christiansen, C. B. and W. F. Parker, Laboratory Studies of Acetic Acid Bleaching, Preprint, T N P 1 Annual Meeting, 1965

Rapson, W. H. and C. B. Anderson,, Bleaching in Five Stages to Asymptotic Limit Using OnIy One Oxidant and Sodium hydroxide, Proceedings of 1985 International Pulp Bleaching Conference, Quebec, 1985, p. 227 Bailey, C. W. and C. W. Dence, Peroxyacetic Acid Bleaching of Chernical Pulp, Tappi 49(1):9 (1 966) Drefùs, C., Canadian Patent 433,069 (Feb 12, 1946) Haney, C. I., M. E. Martin and D. L. Sherk, U. S. Patent 2,442,332(June 1, 1948) Philips, R. B., A. W. Kemp and R. C. Eckert, U. S. Patent, 4,372,8 12, Feb. 8, 1983 Rapson, W. H., The Role of pH in Bleaching, Tappi, 39(5):284 (1956) Dence, C. W. and D. W. Reeve, Pulp Bleaching-Principles and Practice, TAPPI PRESS, Atlanta, Georgia, 1996, p. 41 1-442 Young, J., G. Start and J. Lazorek, Utilization of an Eop Stage During 100% CIO, Bleaching at WeIdwood Hinton, Preprints, CPPA Pacific and Western Branch Annual Meeting, Tech. Sect., CPPA, Montreal, 1992, Section 4 4 Paper No.3 Anderson, J. R., Hydrogen Peroxide Use in Chemical Pulp Bleaching, TAPPI 1992 Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p. 123 Bailey, C. W. and C. W. Dence, Reactions of AIkaline Hydrogen Peroxide with Softwood Lignin model Cornpounds, Spruce-milled Groundwood Lignin and Spruce Groundwood, Tappi J., 52(3):491(1969) Zhang, L. and G. Gelferstedt, The RoIe of Stilbene Structures in Photo-yellowing and ' the Mechanism of Photo-stabilization of High Yield Pulp by Thials, 7 ISWPC, Beijing, 1993, p. 759 Nimz, H. H., Analytical Methods in Wood, Pulping and Bleaching Chemistry, proceedings of the 8' International Symposium on Wood and Pulping Chemistry, TAPPI PRESS, Atlanta, 1995, Vol. 1, p. 1

Liebergott, N., The DI-PER Process, Time for Change, Peracid Delignification and BIeaching, Preprints, 8 Ia Annual Meeting, Tech. Sect. CPPA, Montreal, 1995, p. B157
Ni, Y. and T. Ooi, Laboratory Study on Bleaching Sofiwood Kraft Pulp by a TotalIy Chlorine Free Process Including the Novel Ozone Bleaching, Tappi J., 79(10): 167 ( 1996)

Greenspan, F. P. and D. G. Mackellar, Analysis of Aliphatic Peracids, Analy. Chem., 20(11): 1061 (1948) Xu, C. B., An Improved Peroxide Bleaching Process and its Use for ECF and TCF Sequences, Master Thesis, North-Carolina State University, 1994 van Lierop, B., N. Liebergott and M. G. Faubert, Using Oxygen and Peroxide to Bleach Kr& Pulps, Preprints. 79* Annual Meeting, Tech. Sect. CPPA, Montreal, 1993, p. B2 1

Mison, R. W., Peroxide Bleaching of Mechanical Pulp from Pinus Radiata, Appita, 36(S):3 62 ( 1983)
Colodette, J. L., S. Rothenberg and C. W. Dence, Factors Aftècting Hydrogen Peroxide Stability in the Brightening of Mechanicd and Chernimechanical Pulps. Part III: Hydrogen Peroxide Stability in the Presence of Magnesium and Combinations of Stabilizers, JPPS, 15(2):545 (1 989) Gellestedt, G. and R. Agnemo, The Reactions of Lignin with Alkaline Hydrogen Peroxide. Part III: The Oxidation of Conjugated Carbonyl Structures, Acta Chem. Scand., B34(4):275 (1 980)

Walling, C., M. Kun, and H. J. Schugar, The Iron(II1)-Ethylene Diamine Tetraacetic ()9 Acid-Peroxide System, lnorganic Chemistry, 9 4 : 3 1 (1 970)
Dick, R H. and D. H. Andrews,, The Bleaching of Groundwood Pulp with Peroxide, the Influence of Certain Metals on Bleach Response, Pulp and Paper Magazine of Canada, 66(3):T2O 1, 1965 Rapson, W. H., M. Wayman and C. B. Anderson, Hydrosulphite and Peroxide BIeaching of Nine Pure Species Groundwoods, Tappi J., 48(2): 1 13 (1 965) Devenyns, J., F. Desprez, N. Troughton and L. Plumet, Metals Control in TCF Bleaching - Implications for Kraft Bleaching Sequence Design, TAPPI 1994 Pulping

Conference Proceedings, TAPPI PRESS, Atlanta, p. 38 1
47.

Lapierre, L., J. Bouchard, R.M. Berry, and B. van Lierop, Chelation Prior to Hydrogen Peroxide Bleaching of Kat Pulps: An OveMew, Preprints, 8 1* CPPA rf Annual Meeting, Tech. Sect., CPPA, Montreal, 1995, B233 Basta, J., L. Holtinger, W. Hermansson, and P. Lundgren, TCF/ECF Bleaching: Part 1-TCF Bleaching, Proceedings of 1994 International P l Bleaching Conference, up Tech. Sect., C P P q Montreai, 1994, p.29

48.

49.

Ek, M., P. Axegird, E. Bergnor, and U. Ekholm, The Role of Metal Ions in TCFBleaching of Sofhvood Kat Pulps, 1994 TAPPI Pulping Conference Proceedings, rf TAPPI PRESS, Atlanta, p. 1 1 1 6
Forber, CL.,Chlorine and Chlorine Dioxide Replacements in K a t Pulp Bleaching, rf TAPPI 1992 Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p. 1209 Homer, G. H. and T.Govers, Ozone B a d ECF and TCF Bleaching, Mill Experience Laboratory Data and Cost Considerations, 1994 TAPPI Pulping Conference, TAPPI PRESS, Atlanta, p. 1051

50.

5 1.

CHAPTER 4 KINETICS OF PERACETIC A C I D DECOMPOSITION : PART 1 SPONTANEOUS DECOMPOSITION AT TYPICAL PULP BLEACHING CONDITIONS .

the kinetics of the spontaneous decomposition were developed. narnely i) spontaneous decomposition. which is the pKa of peracetic acid. ii) hydroiysis and iii) transition metal catalysed reactions. spontaneous decomposition. Keywords: kinetics. peracetic acid.2. the stability of peracetic acid was studied in an aqueous solution under conditions most likely encountered in industry. are potentially responsible for the consumption of peracetic acid. Furthemore.ABSTRACT Peracetic acid is one of the alternative non-chlorine bleaching chernicals for production of fiilly bleached chemical puips. In this paper. pulp bleaching . hydrolysis. It was found that three reactions. It was found that the reaction follows second-order kinetics with a maximum rate at pH 8. The developed kinetic equation provides a very good description of the experimental results obtained in this study.

. the catalytic effect can Mrtuaily be eliminated by the addition of a suitable chelating agent [Z]. There are a few studies reporied in the literature on the decomposition kinetics of peroxyacids. a better understanding of the mechanism and kinetics of peracetic acid decomposition and its hydrolysis is of findamental importance for a commercial Pa stage. Peracetic acid decomposes spontaneously in an aqueous sohtion to give acetic acid and oxygen [3]. and has a single acidic proton with a pKa of 8. Therefore. It was found [4] that the decomposition kinetics of caro's acid in phosphate and carbonate buffers exhibit a second order dependence on the total caro's acid concentration.2 at 25°C [SI. Transition metal ions such as cobalt and manganese catalyze peracetic acid decomposition. peracetic acid cm be hydrolyzed to form hydrogen peroxide and acetic acid [33. Since the reaction is reversible.It is usually prepared by mixing acetic acid and hydrogen peroxide with sulfùric acid added as a catdyst [3]. an equilibrium mixture of reactants and products is normally available. Recent results have s h o w that peracetic acid is a less capital intensive. both the decomposition and the hydrolysis are undesirable.INTRODUCTION Environmenta1 concems and market pressure are forcing the pulp and paper industry to explore alternatives to conventionaI chlorine bleaching. easily retrofitted and highly selective Total Chlorine Free (TCF) bleaching agent when used under optimum conditions [ Il. However. In addition. Peracetic acid is the mono-acetyl derivative of hydrogen peroxide. Since hydrogen peroxide and oxygen are ineffective bleaching agents under typical peracetic acid bleaching (Pa) conditions. High purïty peracetic acid can be obtained by distillation.

A mechanism of peracetic acid decomposition was proposed which is compatible with the above kinetics. The rate constant increases proportionally with pH until it reaches 7.s at pH 8. The decomposition kinetics of peracetic acid were first studied by Koubek et al. He found that the dependence of the kinetics on the total peracetic acid concentration is second-order. 121 over the pH range of 5. Francis et al. However. phosphate and borate buffers with ethylenediaminetetraacetic acid (EDTA) as stabilizer. [ 5 ] found that for each pH unit increment the decomposition rate increased by a factor of 6 . This is different from the results obtained in phosphate and carbonate buffers by Bal1 and Edwards [4] who reported that an increase of one pH unit l a d s to an increase in the decomposition rate by a factor of 10. Francis et al.0.7 x 1V3 Umo1. It was postulated that the decomposition reaction involves a nucleophilic .2. The reaction rate at 2S°C reaches a maximum of 2.Recently. and then decreases proportionalIy with pH when the pH is higher than 9.9-10.5.2 in carbonate. which is the pKa of peracetic acid. and confirmed that the decomposition follows a second order dependence on the total caro's acid concentration. [ 5 ] reported a kinetic study of the decomposition of caro's acid under conditions more similar to those encountered during pulp bleaching.

The objective of this project is to investigate the stability of an aqueous solution of peracetic acid without the prescnce of buffers under typical conditions encountered during pulp bleaching. stabilizers and . similar to that observed by Francis et al.2. which leads to an increase in the ionic strength of the solution. we found that at a pH higher than 8. Koubek's kinetics did not include the pH range fiom 7.5 to 9.0. In addition. the kinetics of spontaneous decomposition of peracetic acid are reported in a pH range of 5. [SI when they studied the kinetics of caro's acid decomposition. Furthemore. the peracetic acid hydrolysis is not negligible.attack of a peracid anion on a peracid molecule as: However. They reported that the peracetic acid consumption in a borate buEer in the pH range of 7. In this chapter. This is due to the fact that borate reacts rapidly with hydrogen peroxide to form peroxyborates so that the hydrolysis of peracetic acid is favoured. the presence of buffer solutions may change the nature of how peracetic acid is consumed. Also. the effect of pH.The presence of buffers in his study. as was found by Rucker and Cates 163. in preiiminary experiments we found that Koubek's mode1 181 couid not accurately predict our experimental data obtained under typical conditions encountered during pulp bleaching. In the next chapter.0. and therefore a correction must be made to account for the peracetic acid consumption due to hydrolysis.9 is mainIy due to hydrolysis and not spontaneous decomposition.5 to 9.0to 8. might influence the decornposition rate of peracetic acid.

USA). The reaction was initiated by addition of the concentrated peracetic acid soIution to the reaction flask. USA) were used in the experirnents without fùriher purification . and DTPA fiorn Fisher Scientific (Nepean. The equilibrium peracetic acid consists of about 34% peracid. Ail the experiments were carried out in a 500 mL four-neck round-bottom flask immersed in a constant temperature bath. Reagent grade MgSO. 5% hydrogen peroxide.75 g/L (equivalent to 1.5% charse on oven dried pulp at 20% bleaching consistency). EXPERIMENTAL Equilibrium peracetic acid and ultra-pure grade NaOH were purchased fkom Aldrich (Milwaukee.hydrogen peroxide on the decomposition of peracetic acid as well as the kinetics of the peracetic acid hydrolysis will be discussed. The flask was cleaned by washing successively with glassware cleaner . reported values were the results of at least duplicate experiments. 40% acetic acid with the remainder being water (al1 in mass%). The pH was controlled at a constant value by an automatic titrator through addition of 10 N NaOH . . Ontario) and DTMPA from Buckman (Memphis. The initial peracetic acid concentration was always 3. Samples were withdrawn at predetermined time intervals and analysed in accordance with the iodometric method deveioped by Greenspan and Ail Mackellar [7]. The aqueous solution containing al1 required chernicals except peracetic acid was preheated to the desired temperature. 5% (w/w) sodium hydroxide solution and finally distilled and deionized water. deionized water.

Finally. 3.5 to 9. In Reaction (2). peracetic acid may be consumed in the following three reactions: 1. The experimental strategy of this project is to eliniinate the transition metal catalysed reactions by choosing an appropriate chelating agent. the presence of transition metals in a peracetic acid solution may induce fûrther decompositions as indicated by Reactions (3) and (4). . Spontaneous decomposition: 2 CH3C03H - 2 CH3C02H+ O. Since hydrogen peroxide at neutral pH is not reactive in terms of bleaching pulp.Transition metai catalyzed reactions: In the spontaneous decornposition (Reaction (l)).APPROACH In the pH mse of 5. thus representing a loss in oxidation power. This reaction becomes more important as the alkaiinity of the solution increases 181. In addition.. peracetic acid is decomposed to form acetic acid and O. it is possible to determine the peracetic acid consumed in both spontaneous decomposition and hydrolysis respectively.0. peracetic acid is hydrolyzed to form acetic acid and hydrogen peroxide. by measuring both the peracetic acid and hydroçen peroxide concentrationsduring the course of the reaction. Reaction (2) is also considered a wastefiil reaction.

5.5 g/L diethylenetriaminepentaacetic acid (DTPA) or diethylene triaminepentarnethylenephosphonicacid (DTMPA) is sufficient to give reproducible secondorder rates at pH of 5.0 is shown in Figure 4-1. Since hydrogen peroxide is very stable at the present conditions.5 to 9. The reduced consumption of peracetic acid with the chetant addition may be attributed to the transition metai catdyzed reactions.2 the hydrogen peroxide concentration after 2 hours at 40°C is about 9% higher than the initial hydrogen peroxide concentration.The effect of the addition of a chelating agent on the consumption rate of peracetic acid at pH 7. 5 g/L DTMPA was added to the peracetic acid solution to eliminate the transition metal catalyzed reactions. at a pH of 7. This accounts for about 4% of the total peracetic açid consumption in accordance with the stoichiometry of Reaction (2).5 t O 9. the increase in the hydrogen peroxide concentration can be used to quanti@ the extent of peracetic acid hydrolysis . we found t hat only DTMPA is an efficient stabilizer while DTPA is not. Therefore. For the blank system one can observe that afler an initial linear behaviour the integral form increases faster than the reaction tirne.the peracetic acid hydrolysis increases at a higher pH. The latter is a confirmation of the second order behaviour of the kinetics in total peracetic acid concentration. It was found that a concentration of 0.The fact that DTPA gives the same result as DTMPA indicates that at this pH range both DTPA and DTMPA are effective cheiating agents.0. Le. As report4 earlier [SI. It was found that at pH 8. as the pH inaeases further t O the range of 7. O. Reactions (3) and (4). Figure 4-1 also shows that the presence of chelating agents l a d s to a reduced rate of peracetic acid consurnption and a straight line behaviour of the data.0. However..5 to 7. where the intesral form of the kinetics for a secondorder reaction is plotted versus reaction time 191.

2. As s h o w in Table 4. ) for spontaneous decomposition in the pH range of 5. Table 4. with the hydrolysis kinetics developed in next chapter the disappearance of peracetic acid c m be corrected for the hydrolysis so that the spontaneous decomposition rate of peracetic acid can be determined over the pH range of 5. However. about 15% of the peracetic acid is consumed after 2 hours due to hydrolysis.5 to 9..1 shows that . : [CH.CO.k s peracetic acid hydrolysis.'] .e.versus time. As the pH increases beyond 8.2 since the hydrogen peroxide concentration remained almost constant.5 and 9.H].0 can be written as : where the total peracetic acid concentration is the sum of both undissociated and dissociated peracetic acid.0 in Table 4-1 is corrected for The second-order kinetics in total peracetic acid concentration ( [CH. A discussed above.H].0 and 40°C.2 1 3 This is in agreement with Koubek's results in 8. carbonate and phosphate buffers. k was obtained fiom the dope of straight line plots of the reciprocal of the total peracetic acid . of the peracetic acid of 8. k increases with pH up to the pK.H]. At pH 9.CO. = [CH3C03H]+ [CH. the obsewed second-order rate constant. at pHs of 8.5 to 8.1.CO. Thus it can be concluded that the peracetic acid hydrolysis is negligible in the 2) pH range of 5. k is decreased.(Reaction (). i.CO. RESULTS AND DISCUSSION Using the approach described above. concentration [CH. .5 to 9.0 under othenvise commercial peracetic acid bleaching condition.

The Observed Second-order &te Constant as a Function of pH at 40°C The dissociation of peracetic acid is controlled by the equilibrium: CH&O.COJ = C + & = M H] (8) where M is a constant at fixed pH and temperature.CO.H + CH.CO.COJ = [CH.CO.CO. + H' with K. By combining Equations (6) and (8) one obtains: [CH.HJ/[CH. Rearrangement of the equilibrium constant yieIds: [CH.CO.H](( 1 +M) and [CH.H] +M) J(I .Table 4-1.H]= M [CH.=[CH.CO.J w+]/[CH.CO.H].

i. The good agreement between the experimental and predicted values of 16. As a result.. As discussed earlier. It is important to note that Equation (14) produces a theoretical description of the effect of pH on the observed rate constant of spontaneous decomposition of peracetic acid. since the peracetic acid hydrolysis becomes important when the pH is higher than 8.2 have been corrected using the kinetics of the peracetic acid hydrolysis. . can be obtained from Equation (14) by plotting k versus 2M/(1 + M ) ~ . at the pKa of peracetic acid. k as: When the pH is 8. This plot is shown in Figure 4-2 for the data obtained at 40°C . k = 0. the rate equation is: Substitution of Equations (9) and (1 0) into Equation (1 2) yields: By comparing Equation (5) with Equation (13). the two data points at a pH of higher than 8. it is obvious that k . constant of spontaneous decomposition. .e. k . and Equation The rate constant of the spomaneous peracetic acid decomposition.2. (14) reduces to. reaches its maximum.5k . as a function . k. the ratio of the proton concentration to k the dissociation constant. is related to the rate . Therefore. M. the rate equation becomes: In tems of disappearance rate of total peracetic acid.2. is equal 1.Based on Koubek's mechanism [8] it can be assumed that the nucleophilic attack of a peracetic acid anion on a peracetic acid rnolecule is the rate-determining step.

at pH of 8.5 kcaVmol is found. 60°Cwere obtained. 35 and . Therefore the cataiytic reactions would be expected to form a larger proportion of the total reaction rate at pH less than 7 or larger than 9. A cornparison of k and k confirms that k.of pH in Figure 4-3 provides strong support for the reaction mechanism. Koubek's data and mathematicai model predictions are given in Figure 4-4.2. An activation energy of 22. the rate constant.one cm see that the presence of buffers in Koubek's study increases the spontaneous decomposition rate by a factor of about 2. However this value can only be considered as an estimate since his experimental data was influenced by the transition metal catalysed reactions.5. Koubek [SI attributed this deviation to the fact that the EDTA used in his experiments reduces the transition metal catalysed reactions (Reactions (3) and (4)). It is apparent fiom Figure 4-4 that Koubek's model prediction of his own data is rather poor at pH less than 7 and higher than 9. This compares with an activation energy of 30. = 0Sk which is predicted by . Using the data analysis technique descnbed above. Furthemore. k at 25. .s at 25°C and pH of 8.0 kcal/mol reported by Koubek [SI for the spontaneous decomposition of peracetic acid in carbonate and phosphate buffers. The activation energy of the spontaneous decornposition can be obtained fiom the Arrhenius plot s h o w in Figure 4-6.. but does not eliminate them entirely. compareci with a 16. They are Iisted in Table 4-2 together with the experimental data of k .7 x 1O-3 Umo1.5 where the rate of spontaneous decomposition is relatively low.2 obtained by Koubek [SI. Equation (14).of 2. Reanalysis of his data using Equation (14) also shows that there is a considerable deviation between the experimental data and that predicted by Equation (14).

can effectively eliminate the third reaction route.2 Therefore. The addition of chelating agents. CONCLUSION The stability of an aqueous solution of peracetic acid has been studied under typical puIp bleaching conditions. the rate of spontaneous decomposition of peracetic acid can be written as: where [CH3COjm is the total peracetic acid concentration. The consumption of peracetic acid without the presence of pulp occurs via three routes: i) spontaneous decornposition.Table 4-2. whiIe .5 to 8. Rate Constant of the Spontaneous Decomposition as a Function of Temperature Temperature ("C) l k h . at pH 8. iii) transition metal catalyzed reactions. T is the temperature in degrees Kelvin and M is the ratio of the proton concentration to the dissociation constant of peracetic acid. the hydrolysis is negligible and the peracetic acid consumption is mainly due to spontaneous decomposition. ii) hydrolysis. such as DTMPA. In the pH range of 5.2.

0.C03w). The activation energy is 22.5 kcahol . and that the maximum rate occurs at a pH of 8. we deveIoped a kinetic equation for the spontaneous decomposition of peracetic acid as : where M is the ratio of the proton concentration and the dissociation constant of peracetic acid.2.between pH of 8. ACKNOWLEDGMENT Financial support fiom NSERC in the fom of a Strategic Grant is greatly appreciated. It was found to be second-order with respect to the total peracetic acid concentration ([CH. The present kinetic equation gives a very good description of the experimental results obtained in this study. . the pKa of peracetic acid. Based on the earlier mechanism proposed by Koubek 181. the peracetic acid consumption is due to both spontaneous decomposition and hydrolysis. The kinetics of the spontaneous decomposition of peracetic acid were fùrther studied.2 to 9.

L. Soc. sec. M. Chem.. Devenyns. Tamer.C. March 6.. Chem. Aikali-and Metal-induced X. The Kinetics and the Mechanism of the Decomposition of Aliphatic peroxyacids in Aqueous Solutions. John Wiley and Sons. 78. 1972 .. 10. J. Haggett. Analysis of Aliphatic Per Acids. 20. John Wiley & Sons.362 Bali. R. FL. 1970. Amer. Sponsored by Puip & Paper and Engineering TechnologyTransfer Inc.D thesis. P.L.. Chem. O. Ibne-Rasa.. (1994).10. J. p. M. Battaglia.2263-2268 (1 963) Swem. F.. O. Pym. Brown University . Y. J. Amer.. Ph. W. Hydrogen Peroxide and r-butyl Hydroperoxide.1O63 (1948) Koubek. E. New York. Tappi J. G. J. O. H. D. J.2' -bipyridine Catalysed Bleaching of Cotton Fibers with Peracetic Acid Part 1. 2. and 0. MackeUar. J... Kinetics and Mechanism of the Spontaneous Decomposition of Some Peroxoacids. 77(6): 133 (1994) Rucker.. M. and D. and J. P. Decomposition of Peroxymonosulfate. F. The Kinetics and Mechanism of the Decomposition of and Caro's Acid.1 Koubeiq E. Cates. Edwards. ArneIia Island. A. D. and D. E. Edwards.1 129 (1 956) Francis. New York. 85. 1 125.. Proceedinçs of 1994 International Non-chlorine Bleaching Conf. Froass. (1 964) Levenspiel. 1. 58(13): 148 (1988) Greenspan.. Organic Peroxides. zndEd. VoL. Chernical Reaction Engineering. Analy. K. New York.REFERENCES Troughton. 1061. C. Desprez and J. Zhang. M. Textile Res.1. N. Soc. Peracids: The Pathway to High Brightness TCF Kraft Pulps.

pH of 7.0 .5 g/L DTPA Time (min) Figure 4-1.-= t -Blank d B l a n k + 0 5 g/L DTMPA . +Blank + 0. The effmt of stabilhers on the consumption of peracetic acid at 40°C.

0 6 . versus 2M/(l+M)' at 40°C.Figure 4-2.5 -9. Plot of 1. pH = 5.

.0 i Exnerimental ..5 I I W(l + M ) ~ t I f Figure 4-3. Cornparison of the predicted and experimental relationship between bbS pH at 40°C and ....--.....4 r e d i c t e d from k= M .4.2 4..Data ..-.

Figure 4-4. with IOa m o n EDTA [S] . Koubek's plot of hgkba versus pH at 2S°C.

Reandysis of Koubek's data [8] with the kinetic mode1 developed in this study at 25T.with 10J moVL EDTA .Figure 4-5.

Figure 4-6. Arrhenius plot of the sponbneous decomposition of peracetic acid .

CHAPTER 5 KINETICS OF PERACETIC ACID DECOMPOSITION PART LI: ALKALINE HYDROLYSIS .

peracetic acid. It is shown that three reactions are responsible for the disappearance of peracetic acid. The spontaneous decornposition reaches its maximum at pH 8. Keywords: kinetics.5 or higher. which reduces the rate of transition metal catalysed reactions. but enhances the rate of hydrotysis of peracetic acid. At pH 10.5 leads to the formation of a precipitate of Mg(OH). ii) hydrolysis and iii) transition metal catalysed reactions. Therefore the kinetics of peracetic acid hydrolysis were determined at the latter conditions. hydrogen peroxide. transition metal ions .2. namely i) spontaneous decomposition. Finally it was found that the addition of MgSO. the hydrolysis becomes dominant when the rnetal ion catalysed reactions is minimized by the addition of DTMPA. hydrolysis. decomposition.ABSTRACT The consumption of peracetic acid in an aqueous solution was studied. at pH 9. while both the hydrolysis and metal ion catalysed reactions increase as the pH increases. A theoretical kinetic equation is deveioped which gives an accurate description of the development of peracetic acid and hydrogen peroxide as a result of the hydrolysis reaction.

Both spontaneous and catalytic decomposition paths for Caro's acid were observed. we reported on the kinetics of the spontaneous decomposition. A number of technical papen have been published which deal with the application of peracetic acid. and becomes the dominant degradation route in a 0. Furthemore. Koubek [7J in his doctoral snidy. the stability of peracetic acid as a function of pH and the presence of chelants as well as its hydrolysis kinetics will be discussed. The e f i of pH on the stability of Caro's acid was studied by Bal1 and Edwards [8] and recently by Francis et al. fundamental knowledge of interest for the application of peracids.9 moUL NaOH solution at 12°C when the transition metal catalysed reaction of peracetic acid and hydrogen peroxide is suppressed. In chapter 4. the pKa value for the peroxidic proton of Caro's acid. or their mixture in the delignification stage and final brightness stages [I-41. such as peracetic acid and monoperoxysulfûric acid (Caro's acid). while the catalytic .INTRODUCTION Peracids. addition. he confirmed that the hydrolysis of peracetic acid is enhanced at a higher alkaii concentration. is still incomplete. the kinetics of the alkaline hydrolysis were included the effect of pH on the peracetic acid decomposition not established. However. such as the stability of peracetic acid under vanous bleaching conditions. However. [9].4. Caro's acid. are presently considered as alternatives for conventional chlorine containing chernicals in an effort to develop more environmental friendly bleaching processes. The spontaneous decomposition increases with increasing pH up t o 9. in this chapter. D'Ans and Mattner [6] reported that the hydrolysis of peracetic acid increases with increasing pH and MgSO.

Ragent grade H202. such as diethylenetriarnine pentaacetic acid (DTPA) and diethylenetnaminepentamethylenephosphonic acid (DTMPA).decomposition is more pronounced at a higher pH. The pH was controlled at a constant value by an automatic titrator through the addition of I O rnol/L NaOH. 5% hydrogen peroxide. its dependence on pH and the effect of the presence of chelants. USA). 40% acetic acid with the remainder being water (al1 in mass%). The equilibrium peracetic acid consists of about 34% peracid. Ontario). were studied. All the experiments were camed out in a 500 mL four-neck round-bottom flask immersed in a constant temperature bath. Furthemore. Ail reported values are the result of at . Samples were withdrawn at predetemined time intervals and analysed following the iodometric method developed by Greenspan and Mackellar [IO]. Therefore. DTPA and ethanot fiom Fisher Scientific (Nepean. and DTMPA from Buckman (Memphis. the objective was to develop the kinetics of peracetic acid hydrolysis. The reaction was initiated by addition of the concentrated peracetic acid sohtion to the reaction flask. An aqueous solution containing al1 required chernicals except peracetic acid was mixed and preheated to the desired temperature. EXPERIMENTAL Equilibrium peracetic acid and ultra-pure grade NaOH were purchased fiom Aldrich (Milwaukee. A review ofthe Iiterature showed that the kinetics of alkaline hydrolysis of peracetic acid are not yet established. USA) were used in the experiments without fiirther purification. the interaction between peracetic acid and hydrogen peroxide.

As a result. .8. the effect of the addition of metd chelants such as DTPA and DTMPA on the stability of peracetic acid waç first studied.H + H70.CO. with metal binding properties better than DTPA [14]. manganese. .CO. (2) Further evidence for this assurnption will be presented in the later part of this chapter. and an experiment perFormed in the presence of a large concentration of a radical scavenger.H .9. due to Reactions (1) and () respectively spontaneous decomposition and hydrolysis. RESULTS AND DISCUSSION Establishment of Conditions for Determination of Hydrolysis Kinetics Since it was reported [6.5 glI DTMPA results in a strong reduction in the rate of disappearance of peracetic acid. with or without the presence of ethanol. the increase in hydrogen peroxide concentration (by 27% after 3 hours) can only be explained by hydrolysis (Reaction (2)). Also. the presence of 0. It can be seen that the addition of DTPA.H + O. leads to a more rapid and extensive loss of peracetic acid than that obtained in the control experiment. However. (1) CH3C03H+ H20 . The results at 40°C and pH 9. catalyse the decomposition of peroxy acids. Also included is a control experiment without the addition of any chelants. copper and iron. while the hydrogen peroxide concentration now increases. in this case ethanol.1 13 that trace amounts of transition metal ions. .1. 2 CH3C0.5 are presented in Figure 5.least duplicate experiments. it is reasonable to assume that the disappearance of peracetic acid is only Z. such as cobalt. DTMPA is known to be a very good chelant.2 CH.CH.

2CH $0 3H Both peracetic acid and hydrogen peroxide are involved in the second reaction. The overall reaction is represented by Reaction (3).1 is higher with the addition of DTPA than that in the control experiment. it is known [15] that DTPA is oxidized by peracetic acid in a reaction with a stoichiometry of 3 moles of peracetic acid per mole of DTPA. Co@). Several workers have reported that the reactions between peracids and hydrogen peroxide are catalysed by transition metal ions [8.181. Most likely. the peracetic acid consumption rate in Figure 5. The overall reaction [ 181 could be written as: + " M 2CH 3 C 0 2 H + 0 2 (3) . As explanation it is proposed that the catalytic effect of transition metal ions can not entirely be eliminated by the presence of DTPA. F @ and Cu(II) catalysed decomposition of peracetic acid proceeds through n) e) a radical chah mechanism.T i reaction then may account for the fact that with the addition of hs 0. the M @ . Radical mechanisms have been proposed by McDonough [15] and later by Evans and Upton [18] to account for the disappearance of peracetic acid and hydrogen peroxide. in both the control experiment and the experiment with the presence of DTPA: In the fint reaction only peracetic acid is involved. there are two types of transition metal ion catalysed reactions which lead to the consumption of peracetic acid.15. In addition. A similar explanation was given by Koubek [7].5 g/L (equivalent to about 1 mmollL) DTPA the peracetic acid concentration is about 3 to 5 mmoVL lower than that in the control experiment. As proposed by Koubek [7].As noted above.

5 g/L DTPA present. Therefore. without transition metal ion catalysis) may take place as: RCO. It was fiirther tested the peracetic acid consumption due to Reaction (5) by increasing the initial hydrogen peroxide concentration from 0. wîll suppress these reactions. However.e. This was tested by following the peracetic acid and hydrogen peroxide concentrations in a 30% w/w ethano1 solution with 0. uncatalysed reaction between peroxy acids and hydrogen peroxide (i. it cm be concluded that Reaction (5) is negligible under these conditions. Reaction (5) is much more difficult than the nucleophilic attack of a peroxy acid anion on peroxy acid since hydrogen peroxide is a much poorer electrophile than peracetic acid. Reactions (3) and (4) may proceed through radical pathways.612 g/L.It was also reported [S. As discussed.5 it was found that the consumption rate of peracetic acid was not affected by this more than 4 fold increase in hydrogen peroxide concentration. + H20 + O2 (5) The mechanism proposed by Evans and Upton [18] is : This mechanism is very similar to that of the spontaneous decomposition of peracetic acid [7]. Frorn the results . Therefore. such as alcohol. one would expect that the presence of radical scavengers.2 and 9. 181 that a direct.612 g/Lto 2.In the presence of DTMPA at 40°C for both pH 8. + HzOz -+ RCO. and result in a lower disappearance rate of both peracetic acid and hydrogen peroxide.

The formation of less hydrogen peroxide in this case compared to that at pH 9. Comparison of the two control experiments in Figures 5. . The addition of DTPA and DTMPA on the consumption rate of peracetic acid was fùrther studied at a pH of 8. and the hydrogen peroxide concentration increases by 9% after 2 hours. as will be dernonstrated later.5 (27% increase) can be explained by the fact that the peracetic acid hydrolysis.5 g/L DTMPA present. The results are presented in Figure 5-2.37. The importance of this decomposition route becomes smail as the hydrogen peroxide concentration approaches zero.2. is more pronounced at a higher pH.5 the initial consumption rate of both hydrogen peroxide and peracetic acid are higher than those at pH 8.5 g/LDTPA addition.2 and 40°C.1 and 5-2 reveals that at pH 9. it can be observed that the presence of 30% w/w ethano! increases the stability of both peracetic acid and hydrogen peroxide. since hydrogen peroxide is the limiting reactant in Reaction (4). However. However.65 than that at 6. This again can be explained by the fact that Reaction (4) is favoured at a higher pH.2 than at pH 9.04-8.5 [ 151. both peracetic acid and hydrogen peroxide are more stable at pH 8. This fùrther confims that Reaction (4) is partialiy responsible for the consumption of both peracetic acid and hydrogen peroxide at the present conditions.shown in Figure 5-1.1 also shows that with 0. Comparison of Figure 5-2 with Figure 5.5. as is supported by the results of Bal1 and Edwards [8] that the metal ion catalysed reaction between Caro's acid and hydrogen peroxide is more pronounced at a pH of 9. the disappearance rate of peracetic acid is the slowest. with 0.2 is not as extensive as that at pH 9. Again. Reaction (2). This can be explained by a decrease in both Reactions (3) and (4) with decreasing pH. it is also possible that the oxidation of DTPA by peracetic acid at pH 8.26-1 1.

612 g/Lto 2.5 g / L DTMPA does not affect the reaction rate.2 than that at pH 9. It can also be seen that the increase in hydrogen peroxide concentration fiom 0.5 g/L DTMPA is a straight-line behaviour obtained.2 and 40°C are plotted in Figure 5-3 according to second-order reaction behaviour with respect to the peracetic acid concentration. Since the metal ion catalysed reactions (Reactions (3) and . The results obtained at pH 8. and that a higher hydrogen peroxide concentration favours Reaction (4).6 12 g/L in the presence of 0.612g/L to 2.6 12 g/L. The behaviour can be explained by insufficient suppression of the metal ion cataiysed reactions (Reactions (3) and (4)) by DTPA.6 12 g/L to 2. confirming that the disappearance rate of peracetic acid at pH 8.2 is dominated by spontaneous decomposition in Reaction (1) (see Chapter 4). The effect of pH on the consumption of peracetic acid at 40°C in the presence of DTMPA is s h o w in Figure 5-4.2 than that at pH 9. Once again Figure 5-3 codrms that the presence of ethanol results in a lower rate of disappearance of peracetic acid by suppressing Reactions (3) and (4).Therefore. However.7]. Only in the presence of 0.5 for the two control experiments rnust be due to the fact that the spontaneous decomposition is much faster at pH 8. This is consistent with the elirnination of the metal ion catalysed reactions (Reactions (3) and (4)) by the addition of DTMPq and the earlier conclusion that the uncatalysed reaction between peracid and hydrogen peroxide (Reaction (5)) is negligible. We examined Reaction (4) again by increasing the hydroçen peroxide concentration fiom 0.5 [5. the higher consumption rate of peracetic acid in the later phase of the reaction at pH 8. the increase in initial hydrogen peroxide concentration from 0.612 g/Lleads to a substantial increase in the disappearance rate of peracetic acid when DTMPA is replaced by DTPA.

[CH. since the results obtained at a DTMPA concentration of 2 g/L were identical to those at a DTMPA charge of 0.CO. the kinetics o f peracetic acid hydrolysis at pH 10. i. about 96% of peracetic acid is consumed via Reaction (1) after 2 h.H]. With the increase in hydroçen peroxide concentration resulting from Reaction (2). First it was confinned that the DTMPA concentration does not affect the reaction rate.5 to 12. at pH 9. At pH 8.5 g/L DTMPA were determined. d [CYCO3HI = .k ~CH. the peracetic acid consumption due to Reaction (1) is about 80% after 2 h. e.CO.. [CH. Reaction (1) is negligible.5 a. while the peracetic acid consumption is almost fully accounted for by the increase in hydrogen peroxide concentration.(4)) are minimized. At pH 10. peracetic acid is consumed either by spontaneous decomposition (Reaction (1)) or hydrolysis (Reaction (2)). Kinetics of the Aikaline Hydrolysis of Peracetic Acid After establishment of the appropriate reaction conditions described above. + H * .CO.0. = [CH3C03H]+ [CHJOJ The dissociation of peracetic acid is controlled by the equilibrium: CH3C0.5 and 12.5.H s CH3C0. It was found that the hydrolysis of peracetic acid is as: first-order in total peracetic acid concentration.Hl. the contribution of each of reactions (1) and (2) to the overall consumption of peracetic acid can be calculated.H]. dt where the total peracetic acid concentration is the sum of concentrations of both undissociated and dissociated peracetic acid. integral method was used to analyse the kinetic The data at constant pH and temperature.2.0 in the presence of 0.

[HC.] Rearrangement of the equilibrium constant yields: with M being a constant at a fixed pH and temperature.with K = C . one obtains : Since the mechanism o f the hydrolysis o f the peracetic acid and peracetic acid ion may be written as: the overall rate o f hydrolysis is given by: Substitution of Equations (1 1 ) and (12) into Equation (15) yields: . By combining Equation (IO) with (8). O ' [H+]/[CH3C03H] .

respectively.5 and 12. 0.9 and 1 1. and k. KJH']. It is evident that a straight line relationship exists .0. The results at pHs of 10. and are given in Table 5-1. This equation can be used to obtain the rate constants k. represent the rate constants k. The activation energies of the hydrolysis (Reactions (1 3) and (14)) obtained fi-omthe corresponding Arrhenius plots of the data shown in Table 5-1 are 14. respectively. k between & +w])/K. it is obvious that k . and The slope and the intercept of straight lines. while the dependence of & on temperaturewas taken into account. constants.50 and 60°C are shown in Figure 5-5. and [OH'] = Y.7 kcaVmol. followed by mathematicai rearrangement yields: .By comparing Equation (1 5) with Equation (7). is related to the rate . 1 1. versus KJ[H+]. and k as: Substitution of M = [H']/K. k. . It will be assumed that the effect of temperature on K. is negiigible over the narrow range of temperatures fi-om40 to 60°C.5. 11. and k by plotting k& +[H'])/K.0 and temperatures of 40. /[H+] into Equation (17).

5 50 Therefore. Therefore. or by hydrolysis. b t e Constant of Peracetic Acid Hydrolysis as a Function of Temperature Temperature ( O ) C 40 k. .s ) k2( Wmo1.s ) 0.5 g/L DTMPA are shown in Figure 5-6. the rate expressions used are: Figure 5-6 shows that these kinetic equations adequately describe the development of both peracetic acid and hydroçen peroxide during the course of the reaction.5.38 14.Table 5-1.00934 0. these conditions. The results At obtained at pH 9.40°C and 0.0206 7. peracetic acid is consumed either by spontaneous decomposition. the hydrolysis rate of peracetic acid can be expressed as: Prediction Obtained with the Hydrolysis and Decomposition Kinetics We fûrther tested the above kinetic expression by comparing the predicted and experimentally determined peracetic acid and hydrogen peroxide concentrations. whose kinetics were reported earlier [5]. ( L/mol.

It was proposed [2] that peracetic acid and hydroçen peroxide bleaching can be used in a sequence without washing . With Equation (19). up . the time required to convert 95% of the residual peraceiic acid to hydrogen peroxide in the (PaP) stage can be predicted.5 in the absence of chelants was investigated.4 23. it is expected that upon addition of caustic and hydrogen peroxide to continue the (PaP) sequence.2 The Effect of MgSO.O &er addition of caustic. Thus. the following conditions were taken: 1. the residual peracetic acid wilI be hydrolysed to hydrogen peroxide. 12% pulp consistency and 33% of residual peracetic acid. The Required Time to Convert 95% of Residual Peracetic Acid to Hydrogen feroxide Temperature ("C) Time to hydrolyse 95% of the residuai ~eracetic acid (min) 60 70 80 8. the so called (PaP) sequence. and an initial pH of 1 1.5% peracetic acid charge.0 to 9. Table 5-2. As an exarnple. Usually. It can be concluded that at 80-90°C the hydrolysis of peracetic acid to hydrogen peroxide is very fast. on the Consumption of Peracetic Acid Magiesium sulfate is usually added to peroxide bleachinç to minimize the transition metal catalysed decomposition of hydrogen peroxide [19].4 90 67. The results are show in Table 5-2. a significant amount of peracetic acid is present at the completion of the peracetic acid treatment. In the present study the effect of magnesium sulfate addition on the consumption of peracetic acid at 40°C and a pH of 5. It was found that the addition of MgSO.4 3.

. concentration increases.23].5. concentration of less than 0.2 or lower. on the peracetic acid consumption. addition as calculated from the sdubility product of Mg(OH). However. concentration is less than 94 g/L. both the hydrolysis and the transition metal catalysed reactions are important.5 and a MgSO. The same two mechanisms were considered in the present study to explain the effect of MgSO. (b) stabilization of superoxide anion radicals by Mg'.21]. However. thereby reducinç the propagation of the fiee radical chah decomposition reaction [22. the consumptions of both peracetic acid and hydrogen peroxide are mainly due to transition metal catalysed reactions. Table 5-3 lists the concentration of solid maçnesium hydroxide upon MgSO.0 p/L MgSO. which explains why at pH 8. at 2 g/L MgSO. It is proposed that at pH 9.25] at 40°C. It appears that at pH 8. [24. at pH 9.5 g/L has a negligible effect as s h o w in Figure 5-7. while at 6 g L MgSO. the dominant mechanism changes as the MgSO. as supported by the fact that the peracetic acid disappearance in the latter case is accompanied by the formation of an equivalent amount of hydrogen peroxide.to concentrations as high as 6 g/L has no effect on the peracetic acid consumption at pH 8. The following two mechanisms have been proposed to account for the observed stabilisation effect of MgSO. has no effect on the peracetic acid . the addition of MgSO. althouçh a MgSO. on an alkaline hydrogen peroxide solution: (a) transition metals are absorbed and deactivated by the magnesium hydroxide precipitate [20.5 g/L. concentration of Iess than 0. Thus.2 or lower. A further increase in the MgSO.2 or lower. no Mg(OH)? precipitate cm be formed if the MgSO. the hydrolysis is dominant. the peracetic acid consumption does change with the addition of more than 2. concentration to 9 g/Lenhances the hydrolysis of peracetic acid.

Table 5-3. The close correlation between the precipate formation of Mg(OH). is the absorption and deactivation of transition rnetals by a precipitate of Mg(O& . hydrolysis and metal ion catalysed reactions. However. Addition of chelants. The above results also explain that at practical bleaching conditions performed in the neutrd pH region the addition of MgSO. addition. namely spontaneous decomposition.2. such as DTMPA. will not improve peracetic acid bleaching. both peracetic acid and hydrogen peroxide are rapidly consumed in three reactions. DTPA. at pH 9. At pH 8. . and the peracetic acid consumption mechanism provides strong support that the stabilizing effect of MçSO.5 the arnount of precipitated Mg(OH)Zincreases rapidly with increasinç MçSO.consumption. The Composition of Magnesium Species in Aqueous Solution at 40°C Various pH and MgSO. Addition CONCLUSION The stability of equilibrium peracetic acid containing a significant amount of hydrogen peroxide was studied at different pH levels.

When the pH is higher than 8. . the spontaneous decomposition and metal ion catalysed reactions are negligible compared to hydrolysis. The rate expression is given by Equation (1 9)..2.suppressesthe metal ion catalysed reactions and thus improves the stability of both peracetic acid and hydrogen peroxide.CO.5. addition at pH 9.5 leads to formation of a precipitate of M g ( O m which reduces the rate of transition metal catalysed reactions but enhances that of the hydrolysis of peracetic acid. With 6 g/L MgSO. It was show that the kinetic equation deveioped in this study for the hydrolysis can very well predict the development of peracetic acid and hydrogen peroxide during the course of the reaction when the metal ion catalysed reactions are minimized and the kinetics of spontaneous decomposition are taken into account. The kinetics of peracetic acid hydrolysis were developed at the latter conditions. addition at pH 9.H]. the spontaneous decomposition decreases while both the hydrolysis and the metal ion catalysed reactions increase. With DTMPA present at pH 10.5 or higher. Finally it was found that the MgSO. ACKNOWLEDGMENT Financial support fiom NSERC in the fonn of a Strategïc Grant is greatly appreciated. the hydrolysis is mainly responsible for the consumption of peracetic acid. I t was found that the hydrolysis follows a first-order behaviour with respect to the total peracetic acid concentration [CH.

. Peracetic Acid. Walsh and J.. Amer. Edwards. McSweeny. G. Analysis of Aiiphatic per acids.368-370 (1% 1) Koubek.D thesis. Mackellar.75. L. 233 1-2333 ( 1967) . An Effective Alternative for Chlorine Compound Free Delignification of Kr& Pulp. Devenyns.. A. Proceedings of 1994 International Non-chlonne Bleaching Conf. 37-41. and J.170. New York. L. Edwards.. P. Canadian J. F. J. p.10. R.. J. 1O6 1. and D. Treatment of Softwood Kraft Pulps with Peroxymonosulfate Prior to Oxygen Delignification. B.. 63. F. and J.1O63 (1948) Ball. and P. Durch Nebenreaktionen geht aktiver Sauerstoff verloren. Eng. TAPPI PRESS.REFERENCES W. Desprez and J. Mattner. Tappi J. L. . Soc... 20. 1 125-1 139 (1956) Francis. and 0. Acetper-re erleidet in verdümter Natronlauge Hydrolyse in Wasserstoffperoxyd und Acetat.. Magnesiumhydroxyd und andere Stoffe verhindern diesen Verlust.. Chem. B 157. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. 133. P. Chem.. M. J.C. Analy. Froass. Jan. FL. 77(6). 1219 Liebergott. Zhang. of Chem. N. U.. J. Arnelia Island. Preprints. Ni and A. A Kinetic and Isotopic Study of the Decomposition of Monoperoxyphthalic Acid.140 (1994) Greenspan. Montreal. 194. Atlanta. Haggett.March 6. (1995) Springer. Alkali-and Metal-induced Decomposition of Peroxyrnonosulfate . P. R. O. Brown University. van Heiningen. Ph. Part 1: Spontaneous Decomposition at Typical Pulp Bnghtening Conditions. E. Chem. R T. Jones. X. Peracids: The Pathway to High Brightness TCF Kraft Pulps. P. E.199 (1 993) Troughton. (1994) Yuan. Tappi J. D. 1992 TAPPI Pulpinç Conference Proceedings. Tamer. Canada. R. 76(8). E. N. D. A. O. Hollie. (1 964) Bal]. Z. Angew. Y. The Kinetics and Mechanism of the Decomposition of Caro's Acid. 1. Di-per process: Time for a peracid delignification and bleaching.S. Technical section. The Kinetics and the Mechanism of the Decomposition of Aliphatic peroxyacids in Aqueous Solutions. Amer. Festes Magnesiumhydroxyd beschleunigt die Hydrolyse. J. Soc. Paper 10-1. Chem. 8 1st CPPA Annual meeting. 1997 D'Ans... Kinetics of Peracetic acid Decomposition. 89.. 78. and J..

. Tetrahedron. R. J. New York. and 0. Macmillian. The Intermediate Stages of Aldehyde Oxidation. W. Oxford Pergamon Press. Toronto. Studies on Singlet Oxygen in Aqueous Solution. Canada (1 972) Goodman. D. J. H.Lubarsky. p. M. O. Soc. USA. JPPS. Lindgren and 0. J. Dence.D Thesis. 2781-2875(1 963) Akiba. F.. Rothenberg. 4 ( ) 1 13 (1965) Sjostrom. Decomposition cf Inorganic Peroxyacids in Aqueous Alkali. 39. Part III: Hydrogen Peroxide Stability in the Presence of Magnesium and Combination of 52:4 Stabilizers.. 74:757 ( 197 1) IsBell.. Upton. Frush. B. J.2519-2531 ( 1 970) Evans. Anderson. 1 ( ) 5 5 ( 1989) anon. Dalton Trans. J. 837-847(1935) Vrbaski. Peracetic Acid Decomposition and Oxidation of Lignin Mode1 Phenols in Alkaline Solutions. E. Chem. T. 72 nd Edition. Peroxide Bleaching of Mechanical Pulp fiom Pinus Radiata. CRC Handbook of Chernistry and Physics. 26. T. and C. and G. M. and 1. W. Part 3. K. W. Ann Arbor. 362-370(1 983) McDonough.. Factors lnfluencing the Carbohydrate Degradation under Oxygen Aiakiine Bleaching. Chem. Carbohydr. Ph. Phys. and H.. L. D. Hydrosulphite and Peroxide 82: Bleaching of Nine Pure Species Groundwoods.. Simamura. Res. B. C RC Press Inc. Soc. Chem..p. Svensk Papperstidn. and M.Kagan M. Stephen. S.S. Robson. J. Solubilities of Inorganic and Orsanic Compounds. Theander. Valttila. J. 6(5). F. 1 15 1. Appita. Inhibition of Carbohydrate Degradation during Oxygen 41)65 Bleaching. The Kinetics of Oxidation of Aldehydes to Acids and Acid Anhydrides. W.583. and P. vol 26.. Decomposition of Sodium Peroxybenzoate in Sodium Hydroxide Solution.1963 . Factors Mecting Hydrogen Peroxide Stability in the Brightening of Mechanical and Chemimechanical Pulps. Papen ja Puu. H. Wayrnan and C. No. L. B.. Arhiv Za Kemiju.1 153 (1 985) Rapson.1954 Allison. Tappi J.. 5 ( 1 : 9 (1 972) Ericsson..267-284. and T.8-43 (1 992) Stephen. Brihta. and 0. 59:C25(1977) Colodette. H. University of Toronto.

O 20 40 60 80 100 120 140 Time (min) Figure 5-1. Addition of DTPA or DTMPA on the peracetic acid decomposition at pH 9.5 and 40°C .

2 and 40°C .. O S glL DTMPA *H.CO.A 2 O PCH.H. Addition of DTPA or DTMPA on the peracetic acid decomposition at pH 8.O.5 glL DTPA CH.00 1 I I I O 20 40 60 80 100 1 120 I Time (min) Figure 52. 0. Control ..5 g1L DTMPA 0.CO. -0.0.5 g/L DTPA 0. Control -0- 0. -0- H.H.H202.H.I CH.CO.

10%w/w EiOH . 30% wlw ELOH 3 t -U..612 giL H. 2. -v-O. acid at pH 8.5 glL DTMPA.~~~~~H. 2-612 giL H.2 and 40°C .5 g/L DTPA.O.0.612 g1L H..0. . 0.O.02 6 0.5 glL DTPA..1 -0. 1 -0-0.~. 2.5 giL DTPA.6t 2 gii H202.O.S~KDTMPA.612 g/L H.O. 9 50-O O 60- e 40- O 1O 20 30 40 50 60 Time (min) Figure 5 3 Effect of H O concentration on the disappearance rate of peracetic -.O w h 70 - . 0.5 glî DTPA.

.

Figure 5-5. Determination of the rate constants of the alkaline hydroIysis of peracetic acid (40-60°C. 10.5 g/L DTMPA) .5-12.0 pH. 0.

H] Deîermined [ .CO. 40°C.5 g/L DTMPA) .5.CO. HO] Determined [CH. .H] or [ .Cornpanson of determined and predicted peracetic acid and hydrogen peroxide concentrations (pH 9. 0. .- m o Predicted [CH. HO] 7 5 û ô O 7 0 8 û Time (min) Figure S.

Effect of MgSO. on the consumption of peracetic acid at 40°C and pH of 9.5 .O IO 20 30 40 50 70 Time (min) Figure 5-7.

CHAPTER 6 TRANSITION METAL ION CATALYSED DECOMPOSITION OF PERACETIC ACXD AND ITS EFFECT ON THE CHEMICAL PULP BLEACHING .

DTMPA. especially manganese. transition metal ions.ABSTRACT Peracetic acid (Pa) has emerged as a potential alternative for chlorine containing chemicals used for bleaching of chemical pulps. As expected. The fûndamental phenornena associated with the presence of additives such as DTPA. leads to an improved subsequent peracetic acid bleaching. However. Oxygen delignified and ozone delignified softwood kraft pulps were used.P. on peracetic acid decomposition and bleaching were also investigated. The reslilts indicated that the negative effect of some transition metal ions can be rninirnized by proper control of the process parameters.O. the addition of some chelants. we further exarnined the role of transition rnetal ions such as manganese. WhiIe transition metal ions have received much attention dunng alkaline peroxide bleaching. chelation . Keywords: peracetic acid bleaching.. Na. In this chapter. a close relationship between peracetic acid decomposition and pulp brightness development was observed and c o d m e d at constant bleaching conditions . A chelation pretreatment stage for pulp with high metal ion contents. decomposition. The addition of sodium pyrophosphate effectively deactivates the metal ions and consequently improves the bleaching performance. iron and copper during the course of peracetic acid bleaching. and MgSO. limited results are available with respect to their consequences in peracetic acid treatment. such as DTPA in the peracetic acid treatment may result in poor bleaching due to the fact that more peracetic acid is wasted in side reactions.

and iii) the . and found that it obeyed first-order kinetics in peracetic acid concentration. including peracetic atid decomposition reactions.INTRODUCTION Peroxy acids. ii) hydrolysis. Allen and Agulio [19] reported second-order kinetics in peracetic acid concentration when he studied the manganese catalysed decomposition of peracetic acid in an acetic acid solution.163 that these metal ions catalytically decompose peroxide. and confimed that the kinetics are first order with respect to the peracetic acid concentration.14. The impact of transition metai ions on alkaline peroxide bleaching has been addressed extensively [IJ O.163.Vasyutyn [18] reported that in an aqueous solution of peracetic acid without pH and control Mn2+is the most hamiful metal ion followed by Co2+ Fe)'. The above authors did not extend their study to neutral pH. It is believed 11 I.161. peracetic acid may be consumed in i) the spontaneous decomposition. the range which is of interest for peracetic acid bleachin~ pulps. studies on the influence of metai ions on peracetic acid decomposition are 1 rather scarce. have recently been identified as promising alternatives to chlorine containing chemicals for bleaching of chernical puIps [ 1-9 1. Koubek [ I 7 studied the metal ion catalysed decomposition of peracetic acid at pH 5. On the other hand. On the contrary. As discussed in Chapters 4 and 5. and the order of decreasing catalytic activity is Co'. while the radical species generated in the decomposition reactions result in more carbohydrate degradation. leadins to Iess effjcientbleaching. and Cu2+. Fe2+.4 in the absence of pulp fibres. such as peracetic acid (Pa) and rnonoperoxysulphuric acid (Px). Mn2+. of Our project is airning to gain fiindamental understanding of peracetic acid bleaching. Management of transition metals is therefore crucial in hydrogen peroxide bleaching [ 10.

The effects of additives such as D T P q DTMPA. DTPA from Fisher Scientific (Nepean. and MgSO. we investigated the metaf ion induced peracetic acid decomposition at a pH range of 5. Na.transition metal ion catalysed decomposition [17.. on the metal ion induced peracetic acid decornposition were studied by adding known arnounts of transition metal ions to the equilibrium peracetic acid.P.8 kappa . we reported the kinetics for the hydroiysis and the pH effect on the peracetic acid decomposition mictions. and the results were related to peracetic acid bleaching of both oxygen delignified and ozone delignified softwood kraft pulp. The underlying mechanisms were proposed. Distilled and deionized water was used in a11 experiments. The following sdts were used in the experiments: FeCI. In Chapter 4.. In this chapter.O. USA) were used in the experiments without fùrther purification.7% ISO brightness. CuS0.0. Ontario) and DTMPA fiom Buckman (Memphis. 5% W/W hydrogen peroxide and 40% wlw acetic acid with the remainder being water.MnSO. EXPERIMENTAL Equilibnum peracetic acid and ultra-pure grade NaOH were purchased fiom Aldrich (Milwaukee. The equiIibrium peracetic acid consists of about 34% w/w peracetic acid. In Chapter 5. USA). 13. Reagent grade chernicals. and CoSO.. An oxygen delignified softwood kraft pulp of 37. we established the rate expression for the spontaneous decomposition under the typical peracetic acid bleaching conditions. The mechanism and kinetics of the spontaneous decomposition were studied before [17].0 to 7. Its metal ion content was below the detection limits of the atomic absorption (AA) spectroscopic analysis method used in this study.20-211.

The metal ion contents of the pulps and chemicals determined by AAS analysis are shown in Table 6. round-bottom flask immersed in a constant temperature bath.The ozone charge was 1.01 Peracetic acid decomposition experiments were camed out in a 500 mL four-neck. pulp) of which 90% was consumeci.O.5 2.2.95 0. The reaction was initiated by addition of a concentrated peracetic acid .number and 23.1. Meta1 Ion Contents of the Materials Used in This Study ZnE Pulp ZnEQ Pulp - O Pulp OQ Pulp 40% DTPA - 80 g/L DTMPA 1 1 1 1 1 1 0. 10% pulp consistency for 45 minutes.8% (by weiçht on 0.5% pulp consistency for 30 min.8% ISO brighmess.4 mPa-s viscosity was used in this study. Chelation (Q) with 0. A subsequent alkali extraction stage (E) was perfonned at pH 11.80 0. Ozone bleaching (Zn) was camed out on a hemlock kraft pulp with 70% methanol-water of pH 2 as impregnation liquor following an earIier describeci procedure [22].1 kappa number and 22. The aqueous solution containing al1 the required chemicals except peracetic acid was preheated to the desired reaction temperature.d.77"C.5% DTPA was done at 50°C. 5. pH 5 .10 Equilibrium Peracetic Acid <0. The properties of the ZnE pulp were 53.40 61.0.8 mPa-s viscosity. Table 6-1.

viscosity and kappa number were determined in accordance with TAPPI methods T452 om-92. Pulp brightness.The Transition Meta1 Catalysed Decomposition of Peracetic Acid We first studied the systern in the absence of pulp fibres.75 ppm each of Cu".1. RESULTS AND DISCUSSION 1. are responsible for the so called metal ion induced .e. Obviousiy.5 % pulp consistency. the presence of these metal ions enhances the peracetic acid decomposition. M e r the Pa treatment. The effect of 0. the pulp was washed thoroughly with deionized water and the spent liquor was titrated to determine its residual peracetic acid and hydrogen peroxide concentration as well as final pH. Samples were withdrawn at predetermined times and analysed following the iodometric method developed by Greenspan and Mackellar [23] Peracetic acid bleaching was canied out in polyethylene baçs containing the required quantity of NaOH and water to provide the desired initial pH and consistency. Fe3+ Md' additions on the stability of a peracetic acid solution at pH 7.solution to the reaction flask. The pH was kept constant with an automatic titrator by addition of 10 moVL NaOH. and T236 cm-85. The bleaching expenments at constant peracetic acid concentration were conducted in a 500 mL four-neck. Preliminary bleaching runs were carried out to determine the rate of peracetic acid consumption. respectively. Cobalt was not included due to its negligible amount present in the chemical pulps as shown in Table 6. Subsequentiy. T230 om-89. the desired amount of peracetic acid was charged to the reaction mixture at regular time intervals to maintain a constant peracetic acid concentration. round-bottom flask at 1.0 is and presented in Figure 6-1. i. weii stirred.

This is supported by the observation that peracetic acid may oxidize Mn2+to MnO. The overall reaction shows that peracetic . Note that not only peracetic acid but also hydroçen peroxide consumption rates are much higher when metal ions are added. in tum.) was added.75 ppm Mn2+ (as MnSO./catalysed decomposition [ 171. A number of reactions may lead to the consumption of peracetic acid in the presence of metal ions: Only peracetic acid is involved. M O ' is produced fiorn the oxidation of ~ n " n. The overall reaction [24] is: CH3C03H+ H202-' CH3C02H+ H. This oxidation-reduction cycle explains why only a small amount of manganese is effective in enhancing the disappearance of both peracetic acid and hydrogen peroxide. and proposed that the reaction proceeds through a radical mechanism in which the perhydroxyl radicals are involved. reacts with hydrogen peroxide and is reduced to Mn2+ (Reaction (4)). by peracetic acid as described in Reaction (3). Permanganate.O + 0. The overall reaction can be writen in Equation (1): Both peracetic acid and hydrogen peroxide are involved. Fe2' and Cu2+ catalysed decomposition of peracetic acid proceeds through a radical chah mechanism. we found that permanganate is generated and then consumed during the course of the reaction when 0. [23. the Mn".l (2) Our data suggests that redox reactions also take place. CoZ+. McDonough [20) and Evans and Upton [24] studied the transition metal catalysed reaction of peracetic acid and hydrogen peroxide.25]. As proposed by Koubek [17]. For example.

) was also reporteci as a good stabiliser for alkaline peroxide solution [3 11 and peracetic acid [2 Il. DTMPA. instead of Mn2+to the equilibrium peracetic acid solution.75ppm each of copper.C03H + 40.H + 2 ~ n " 3H. iron and rnanganese respectively. and Na. 6-3 and 6-4 for the addition of 0.0and 40°C are presented in Figures 6-2. It should be pointed out that in the absence of trace amount of these metal ions. including DTPA.CO. Magnesium sulfate is usually added to oxygen delignification and peroxide bleaching to rninimize carbohydrate degradation andlor peroxide decomposition [30].C02H + H20 O2T + (2) We fùrther confirmed the above oxidation-reduction cycle by the addition of MnO. We fbrther confirmed that the rates of peracetic acid and . Therefore.P20. + 6H' + 5 H202 5 O11+ 2 ~ n ' + 8H20 + - CH. Reaction (2) is extremely slow under the condition studied.-' CH.P20. and found that the rates of the peracetic acid and hydrogen peroxide consumption are similar to those with the addition of ~ n " . 2. The Effect of Additives on the Metal Catalysed Decomposition of Peracetic Acid Chelants such as DTPA and DTMPA are known stabilisers that rninimize the metal ion catalysed peroxide decornposition dunng peroxide bleaching [26-291. in this study we investigated whether the presence of additives. We can observe in al1 three cases that the addition of tetrasodium pyrophosphate stabilises the peracetic acid solution. Tetrasodium pyrophosphate (Na. MgSO. can rninimize the metal ion induced peracetic acid decomposition.acid reacts with hydrogen peroxide to form oxygen: 5 CH.O + . The results at pH 7.2 MnOi + 6H' + 5 CH3CO2H (3) (4) 2 MnO.

O.hydrogen peroxide decompositions in the presence of Na. supporting that the metal ion induced decomposition is neçligible with the addition of Na. This accounts for the fact that the catalytic effect of both Cu2' and Fe3' on the peracetic acid decornposition is eliminated with the addition of either DTPA or DTMPA.0 and 20°C [32] Metal Ion 1 . which is in agreement with our finding in Chapter 5.PIO. the addition of magnesiurn sulfate does not affect the rate of oxidant consurnptions under this condition. 2.1 The effect of DTPA and DTMPA on FeY and Cu" catalysed decomposition of peracetic acid Figures 6-2 and 6-3 show that the addition of DTPA or DTMPA can almost eliminate the copper and femc induced peracetic acid decomposition as indicated by the similar profiles of the peracetic acid and hydrogen peroxide concentrations to those when Na. DTPA or DTMPA complexed copper 2 ] The or femc ion is largely unreactive towards metal ion induced decomposition reactions.. was present. Conditional Stability Constants of Metal Ion to DTPA Complexes at pH 7.P20. DTMPA is even stronger cheiant than DTPA [ 7 . As expected. We propose that both copper and femc ions can be strongly chelated by DTPA as indicated by the conditional stability constants of metal ion to DTPA complexes (Table 6-2).P. Table 6-2. can be adequately predicted with the kinetics of the spontaneous decomposition developed in Chapter 4.

Furthemore. It can also be noted that a sharp decrease in . McDonough found that the presence of DTPA in the bleaching stage drastically reduced the brightness gain. which was explained by the oxidation of DTPA by peracetic acid to its corresponding N-oxide. 0. so that a small amount of metal ions present in the reaction solution may be immediately chelated upon the addition of DTPA [20].0 containing 0.75 ppm Mn" has several consequences as can be seen in Figure 6-4. The peracetic acid decomposition is enhanced with the addition of either DTPA or DTMPA. rnight be explained by the assumption that chelation occurs much faster than oxidation. The effectiveness of DTPA in stabilizing peracetic acid solutions. although effect is much greater with the former.In an earlier study [20] on bleaching of groundwood pulp with peracetic acid. in Figures 6-2 and 6-3.5 g/L of DTPA (1 mmoVL) was present. The metal ion content in the solutions was not quantitatively deterrnined. it might be that the oxidized DTPA still exhibits some chelating properties and consequently elirninates the Cu2+ ~ e )induced peracetic acid or + decomposition.2 The effect of DTPA and DTMPA on Mn2+catalysed peracetic acid decomposition The addition of DTPA or DTMPA to an equilibrium peracetic acid solution of pH 7. DTPA can still stabilise a peracetic acid solution. If the sarne stoichiometry holds. the peracetic acid concentration decrease due to oxidation of the DTPA should be about 3 rnrnol/L. it was found [ZO] that in spite of its susceptibility to rapid oxidation. 2.10 and established that the stoichiornetry is 3 moles peracetic acid per mole of DTPA. He found that the oxidation occurs rapidly in a pH range of 6. This rnay explain the difference in peracetic acid concentration between the addition of DTPA and that of Na&û. In Figures 6-2 and 6-3. despite its susceptibility to oxidation. Altematively.

0and 7. is stabilised by the . Consequently. The addition of 0. The results in Figure 6-5 show that the disappearance profiles of both peracetic acid and hydrogen peroxide dunng the second cycle closely resembles those of the first cycle. Hydrogen peroxide.6-6 and 6-7 is also the effect of DTMPA on the manganese catalysed consumption of peracetic acid. Figures 6-6 and 6-7 show the addition of DTPA on the manganese catalysed decomposition of peracetic acid at pHs of 5. the experimental result that the addition of DTPA does not stabilise the Mn2+containing peracetic acid solution (Figure 6-4) could be explained by the hypothesis that the complex is capable to catalyse peracetic acid decornposition. indicating that ~n'+ is not as strongly chelated. weaker DTPA-h4n2+ The addition of DTPA on the manganese catalysed decomposition of peracetic acid was fûrther studied by adding peracetic acid and hydrogen peroxide to the reaction solution d e r 42 m n of reaction so that their concentrations were the same as those at the start of the i reaction.0 (Figure 6-6).peracetic acid occurs when the reaction time exceeds 20 minutes.0. but has a negligible effect at pH 5.0 and 6.5 @ DTMPA increases the rate of peracetic acid decomposition at pHs 6. Table 6-2 shows that the DTPA-MnZ'cornpiex is much less stable than the complexes of DTPA with either ~ e "or Cu". It shows that a lower pH leads to a higher decomposition rate of peracetic acid in the presence of DTPA and ~ n * ' . Included in Figures 6-4.0 (Figures 6-7 and 6-4). the addition of DTMPA stabilises hydrogen peroxide. On the other hand. Similarly. on the other hand. while the addition of DTPA lads to a much higher consumption rate of hydrogen peroxide relative to that of the control. it was reported that the addition of DTPA enhances the Fe3+cataIysed decomposition of hydrogen peroxide [33].

We therefore conclude that manganese present in the unchelated O pulp is mainly responsible for the enhanced peracetic acid decomposition. Therefore it is proposed that Mn" is oxidized to MnO. or Na. n.P. MgSO. The Role of Transition Metal Ions d u h g Peracetic Acid Bleaching of Chernical PuIps The following section describes the results of pulp bleaching with peracetic acid.addition of D W A in al1 three cases. can effectively deactivate the metal ions present in pulp fibres (Table 6-3). to the bleaching stage. instead of a pretreatment stage. By adding manganese (as MnSOJ at a charge corresponding t o the arnount of manganese removed in the chelation stage. The results in Table 6-3 show that a higher degree of delignification is achieved both in terrns of brightness gain and kappa number reduction when the oxygen delignified ih pulp is pretreated wt DTPA.O. by peracetic acid (Reaction (3)) at pHs 6 and 7 but not at pH 5. hydrogen peroxide may not be involved in the oxidation and reduction cycle since the oxidation of DTMPA by M O ' could be much faster than Reaction (4). 3. and thus causes the less efficient bleaching. DTMPA. Furthemore. Cornparison of these results with those obtained by peracetic acid bleaching of unchelated pulp indicates that the presence of either DTPA or DTMPA leads to a iower brightness gain and a smaller kappa number reduction. We also studied whether the addition of chelants / additives such as DTPA. we found that peracetic acid bleaching of the chelated pulp showed a delignification and brightness gain comparable to those obtained for peracetic acid bleaching of the unchelated pulp. First we performed peracetic acid bleaching of oxygen delignified pulp with and without DTPA pretreatment. while the presence of tetrasodium pyrophosphate improves the bleaching .

3 2.6 79.2 2.7 77.2 85.6 92.7 10. 0.4 35.2 73. 0. (%ISO) Viscosity (mPa-s) Residual Chernicals (% on charge) CH3C03H Unchelated O PU~P H20.8 83. Peracetic Acid Bleaching of Oxygen Delignified Softwood Kraft Pulp (O Pulp) Sarnple and condition Treatment time (min) Bright. pulp .8 23. 1.0 9.5% peracetic acid :hargeon 0. 60°C.Table 6-3.3% MgSO.5 5 1. 23.4 86.1 83.7 0.2 O.2 5.0.4 added 22.0 2.2 5. lnitial pH of 7.3% DTPA added -- 22.4 18.3 87.6 3.2 added Unchelated O pulp.7 4.4 20.9 21. 1.4 6.8 4.7 7.3% DTMPA added Unchelated O pulp.1 8.9 3 8.7 5.1 80.5 3.3 83.6 26.3 47.d.4 59.0 12. 0.8 3leaching Conditions: 10% consistency.0 9.9 2. 1 8. I 1.8% Na4P207 90.8 Chelated O PU~P 23.2 Unchelated O pulp.1 21.5 Unchelated O pulp.

performance. This is not unexpected since poor bleaching results are obtained when more peracetic acid is consumed in wastefui reactions. This is in agreement with the results obtained by McDonough [ZO]. It appears that both the deligiification degree and brightness gain are closely related to the residual peracetic acid afier bIeaching (Columns 3. Table 6-3 shows that the residual peracetic acid and hydrogen peroxide concentrations are lower with the addition of DTPA. This may be attributed to the loss in peracetic acid as a result of oxidation by DTPA. ancilor the enhanced oxidation-reduction cycle observed in the decomposition studies. 4 and 6). Therefore. leading to the wastefid consumption of peracetic acid without any bleaching effect.5 ppm manganese which corresponds to 6. As shown in Table 6-1. the oxygen delignified softwood kraft pulp contains 6 1.e.0. using both chelated . as was discussed in the previous section. the manganese induced decomposition of both peracetic acid and hydrogen peroxide must occur. while the residual hydrogen peroxide concentration was much higher. which then oxidizes DTMPA rather than hydrogen peroxide.679/ L at 40°C and pH 7.8 ppm Mn in the bleaching liquor. who observed that the addition of DTPA during peracetic acid bleachins of goundwood pulp resulted in a smaller b right ness gain. permanganate is fonned from the oxidation of Mn" by peracetic acid. These results are similar to those in Figures 6-4 and 6-7 where 0. although not to the level obtained with the chelated pulp. When DTMPA was added to the peracetic acid bleaching system. suggesting that the same mechanism prevails in the pulp bleaching systern: i. the residual peracetic acid concentration was lower than that of the control experirnent.75 ppm manganese was added to a peracetic acid solution. We fùrther tested this hypothesis by comparing the bleaching results obtained with a constant peracetic acid concentration of 1.

a Iower pulp viscosity is accompanied by a smaller amount of residual hydrogen peroxide. This suggests that the loss in pulp viscosity is mainly due to wastefùl reactions involving hydrogen peroxide whereby highly reactive radical species are generated. We found that the delignification degee and brightness gain were similar. much more peracetic acid was required to maintain the constant peracetic acid concentration for the unchelated pulp. We iùrther studied the effect of different additives on peracetic acid bleaching with a hemlock kraft pulp. i. This is consistent with the generat perception that peroxy acids are selective bleaching chemicals when used under optimum operating conditions. This is consistent with our earlier decomposition results which showed that presence of magnesium sulfate does not affect the stability of a peracetic acid solution. The decrease in pulp viscosity during peracetic acid bleaching is very small. These results are not inconsistent with the protective effect of MgSO. bleaching and CX_ delignification. Furîhermore. Comparison of Table 6-3 and 6-4 shows that the difference in bleaching results with or without DTPA pretreatment of the ZnE pulp is much smaller than that for the O pulp. It appears that the pulp viscosity a h r Pa treatment is related to the residual hydrogen peroxide present. which was first ozone-delignified (see experimental section for details) followed by an alkaline extraction stage. in &O. However. as shown in Table 6-3.and unchelated pulps at 1. The results are presented in Table 6-4. since the latter two are performed at a high pH while a neutrd pH is used for peracetic acid bleaching. This is attributed to .5% pulp consistency. The addition of magnesium suKate has a negiigible effect on the delignification degree and brightness gain.e. Table 6-3 shows thar the cellulose degradation is not af5ected by the addition of magnesium suIfàte.

the fact that the transition metal ion content. as evidenced by a lower brightness gain and a higher viscosity loss. Again. Thus it is possible that peracetic acid bieaching may be done without a preceding chelation stage for pulps with a low transition metal ion content. .5% peracetic acid was charged to the ZnE pulp. However. Again. as was s h o w in Table 6-1. especially manganese. the addition of MgSO. When only 0. especially manganese. The results in Table 6-4 were obtained with a peracetic acid charge of 2%. Table 6-4 shows that the addition of DTPA during peracetic acid bleaching of both the chelated and unchelated pulps is not beneficial. a chelation stage as a pretreatment is strongly recommended for peracetic acid bIeaching of puIp with a high transition metai ion content. during peracetic acid treatment has a negligible eFect on the bleaching response. in the ZnE pulp is much smaller than that in the O pulp. the difference with or without DTPA pretreatrnent was even smaller.

pulp CONCLUSIONS The transition metal ion induced decomposition of peracetic acid. is aiso present when rnanganese is ~ ' .0. Peracetic Acid Bleaching of Ozone Deiignified Softwood Kraft Pulp Sample and conditions Treat time (min) Bright. 2% peracetic acid charge on 0.3% MgSO.d. However.s ) I - Residual Chernicals (% on original) 1 Unchelated ZnE pulp Chelated ZnE pulp 1 Chelated Z n . The results show that a significant amoünt of peracetic acid may be wasted when metal ions are present. The metal ion induced decomposition may take place foliowing a radical mechanism.3% DTPA added in Pa Unchelated ZnE pulp 0. (%ISO) Viscosity (m ~ a . pulp 0.Table 6-4. and the effect of the addition of chelantdadditives on the decomposition were studied under typical peracetic acid pulp bleaching conditions. thus resultins in less efficient bleaching.3% DTPA added in Pa Unchelated ZnE pulp 0.Initial pH of 7. an oxidation-reduction cycle involvinç ~ present in the peracetic acid solution. added in Pa Bleaching Conditions: 10% consistency. 60°C. It was found that the presence of chelants such as DTPA or DTMPA minimizes the n and MnO.

Munro of E. Eddy Forest Products LTD for supplying the oxygen delignified softwood krafl puIp. such as DTPq in the peracetic acid bleaching may result in poor bleaching due to the fact that more peracetic acid is wasted in side reactions.Cu2' and Fe3+induced peracetic acid decomposition but increases the Mn" induced decomposition. while the less stable DTPA-Mn" complex can. However. B. the addition of some chelants. As expected. ACKNOWLXDGMENT The author thanks NSERC for financial support in the form of a Strategic Grant and F. l a d s to improved peracetic acid bleaching. especially manganese. and by the fact that only manganese participates in an oxidationreduction cycle. A chelation pretreatment stage for pulps with a high metai ion content. while Cu" and Fe3' do not. cheiation pnor to Pa treatrnent may not be necessary. The addition of sodium pyrophosphate effectively deactivates the metal ions and consequently improves the bleaching performance. This is explained by assuming that the more stable complexes of DTPA or DTMPA with Cu" and ~ e ) 'do not catalyse the decomposition reactions. . a close relationship between peracetic acid decomposition and pulp brightness development was observed and confirmed at constant bleaching conditions. For pulps with a 1ow metal ion content.

and L. Peracids: The Pathway to High Brightness TCF Kraft Pulps. 37 1. J. R T. N. B. Peracetic Acid as a Selective Prebleaching Agent: an Effective Option for the Production of Fully Bleached TCF Kraft Pulps.and D.W. D. p.. Hollie. MetaIs Control in TCF Bleaching . Devenyns. 97(3):73 (1996) Devenyns. Desprez and N.. Delignification of Aspen Wood using Hydrogen Peroxide and Peroxyrnonosulfate . and J. Peroxyacetic Acid Bleaching of Chemical Pulp. 49(1):9 (1966) Devenyns. Desprez and J. Atlanta. F. Proceedings of 1994 International Pulp Bleaching Conf . L. Atlanta. TAPPI 1992 Pulping Conference Proceedings. TAPPI PRESS. and C. Peracetic Acid. TAPPI PRESS. Lachenal.. A.. Peroxygen Prebleaching and Bleaching Technologies for Step-Wise Conversion corn Conventional Chlorine Bleaching via ECF toTCF. Peracid Delignification and BIeaching of Chemical Pulp Part II: Oxidation. 1994 TAPPI Pulping Conference Proceedings.3 8 1. Atlanta p. Walsh and J. Chlorine Compound Free Delignification of Kr& Pulp. Desprez and N. Plumet. Tappi J.Implications for Kraft Bleaching Sequence Design.RIEFERENCES Springer. an Effective Alternative for P. N. 341. Treatment of Sofiwood Kraft Pulps with Peroxymonosulfate Prior to Oxygen Delignification. and J. Dence. and Considerations on How to Select Among Them.Tappi J. 1994 TAPPI Pulping Conference Proceedings. TAPPI 1993 Pulping Conkence Proceedings. TAPPI PRESS. E. On-site Peracids: Tools for Bleaching Strategies to Meet the Cluster Rule. p. Pulp & Paper Canada... 1994 Amini. . B. Liebergott. Bailey. C. June.. 76(8): 194(1993) Springer. E. F. F.. Devenyns. Tappi J. Webster. p. N. Vancouver.. Troughton. Troughton. Atlanta. TAPPI PRESS. Desprez. C.W. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc.SC.. Proceedings of 1996 International Non-chlorine Bleaching Conference. Troughton. L. Benificid and Adverse Effect of Meta1 Ions in ZP Bleaching Sequences. F. McSweeny.. J. 1994 TAPPI Pulping Conference Proceedings. TAPPI PRESS. J. HHI. March. Chirat. 73( 1): 175 (1990) Hili. 1993 Troughton. 1219.

Abbot. Mackellar.. Montreal. On Wood and Pulping Chernistry. Practical Implications of Met& Management in Totdy Chlotine-Free (TCF)Pulp Production. DeGraw. Vol. Jan.. 1995. Berry. Ni and A. Bouchard. 8 1st CPPA annuai meeting.H. Chem.C. Proceedings of 1 994 International Pulp Bleaching Conf. and E. 66(3):T20 1. 1965 Jayarnant. 1996. Ed. G.. A. 1. and J. and the Influence of Certain Metals on Bleach Response. and T. The Bleaching of Groundwood Pulp with Peroxide. B. Brown Univ. p. K. F.. Melbourne.P. Preprints.Atlanta.93 (199 1) Hobbs. University of Toronto (1972) Swem. 1964 Vasyutyn.. Metal Ion Catalysed Oxidation of Acetaldehyde. Ph.P. K. Appita J. G.362 Gang. M. John Wiley and Sons. Y.Organic Peroxides. Yang. J. Ph. Symp. Vancouver. J. D. van Lierop. The Role of Radical Species in Peroxide Bleaching Process. Pulp and Paper Magazine of Canada. pl3233 Dick.. 1239 Lapierre. 82nd CPPA Annual Meeting. Mechanism of Cellulose Protection in a Novel and Selective Ozone Pulp Bleaching Process. Ukrainskii Khirnicheskic Zhumal. p.H. Analysis of Aliphatic Peracids.... Ya. On the Participitation of Hydroxyl Radicals in Oxygen and Hydrogen Peroxide Bleaching Process. Influence of Minera1 Salts on the Decay Rate of Peroxyacetic Acid in Aqueous Solution. Aguilo. M. E.Yoon. M. R. Andrews.363 (1 968) McDonough. The Kinetics and the Mechanisrn of the Decomposition of Aiiphatic Peroxyacids in Aqueous Solutions.. J. and B. van Heiningen. O. p. Australia. R. and D. Y. 76.D thesis. Gavenko and 1. Jansbo. 55(6):584 (1 989) Allen. Jan. Advances in Chemistry Series. 1970 . .1. Chelation Prior to Hydrogen Peroxide Bleaching of Kraft Pulps: an merview.R. p. Preprints.. Garbuzyuk. Montreal.. Procdmgs 6th Int.D Thesis. p. M. Vol. 20(11):1061 (1948) .and A. Analy.H. B303 Greenspan. Peracetic Acid Decomposition and Oxidation of Lignin Mode1 Phenols in Alkaline Solutions. 45(5):344 (1 992) Koubek. V. G. L. J.C. D. N. E. D. J. Reitberger.. T. June 1994 Gierer.

F. 77(3):59 (1 976) Anderson. Liebergott and M. Rothenberg and C. and M. Anderson.W. p. M. J. G. Factors Mecting Hydrogen Peroxide Stabiiity in the Brightening of Mechanical and Chernimechanical Pulps. J.. Chem. W. W. Michigan... D. 1993. p. 1 15 1 Kagan M. L. Montreal. p 4. Versene Chelating Agent. Chem. N. SS(1):l6l(l979) The Dow Chernical Company. R. Midland. Soc.Stenberg and B. Tappi J. D. B. Finlay Forest U e Flash Dryer as Reaction Tower for Bleaching Pulp... Lubarslq. J. Hydrosulphite and Peroxide Bleaching of Nine Pure Species Groundwoods. W. Part III: Hydrogen Peroxide Stability in the Presence of Magnesium and Combinations of Stabilizers. Optimised Hydrogen Peroxide Bleaching in Closed White-water Systems. The Intermediate Stages of Aldehyde Oxidation. Studies on Sin~let Oxygen in Aqueous Solution. Tappi J. 63(4): 1 1 l(1980) Rapson. Wayman and C. 1985. Brightening Response of Western Hemlock Refiner Groundwood to Hydrogen Peroxide.. H. 79th CPPA Annual Meeting.12 (1 993) Colodette. ss Pulp & Paper. J. M. I. Using Oxygen and Peroxide to Bleach Kr& Pulps. F. S. Dence. 48(2): 1 13 (1 965) Thiessn. Upton. Faubert. B. Sjogren. Pulp Paper Can..B2 1 Allison.Evans. 837-847 (1935) van Lierop. 15(2):545 ( 1989) . Appita. . R..... 39. 36(5):362 (1 983) Solines. Phys. Dalton Trans. E. and G. JPPS. Part 3. Peroxide Bleaching of Mechanical Pulp fiom Pinus Radiata. Preprints.

C ~ ( l l ) -A- 0 10 20 30 40 50 60 Time (min) Figure 6-1.5 solution (40°C. Effect of transition metal ions on the stability of a peracetic acid . 0.5S/L DTMPA C~(l1) -0- H. pH 7 0 0 7 ppm metal ion concentration) ....C03H.O. -A-CH.5 S/L DTMPA H20.H. 0.CO.07 z : -i-CH.0.

02 3 0. Effect of additives on copper catalysed peracetic acid decomposition (40°C.02. 4 H202. u -HH.01 O 0.CO.P. g L DTPA.CO.H. -OH.75 ppm Cuz+. -.O. Na4P20.H20.O.05 c . pH 7.. O O 0. -mUH.0.: w J -a-CH.H. DTMPA MgSO.CO..CO.O 0.00 O 1 0 20 30 40 50 60 Tirne (min) Figure 6-2.H.) 0.04 0 043 . 2 g/L Na.02. "O6 Control . Na4P20.MgSO. &H3C03H. I = .5 . Control d E c ... + e c O L 8 C 0. <H. DTPA DTPA OTMPA -n.H. H.0.H. DTMPA or MgSO.

0.07
5

î
s

E

0" .-

w

n

---

CH,CO,H, Control CH,C03H, Na4P20, - -CH3C03H,DTPA -i-CH3C03H,DTMPA CH,CO,H. MaSO.
-A

-

-A-

H202, Control

-o- H202,Na4P,0,

+

+

-OH202,DTPA -0-H,O,,DTMPA H-O-. MaSO-

O

10

Time (min)

(40°C, pH 7.0,0.75 p p m Fe*, 0.5

Figure 63. Effect of additives on iron catalysed peracetic acid decomposition 0 5 DTPA, DTMPA or MgSO,, 2 g/L Na,P,O,) .

A

I

-

-A4H,CO3H, -HH3C03H, --4H,C03H, -i-CH,C03H, , 3 0H HC3 ,

Control Na,P20, DTPA DTMPA MgSO,

H202. Control H202,Na4P207 + H,O,, DTPA -0H~O; DTMPA -OH20,, MgSO,
-A-

-XP-

O

10

30

40

Time (min)

Figure 6-4. Effect of additives on manganese catalysed peracetic acid decomposition (40°C, pH 7.0,0.75 ppm M2, 0.5 g / L DTPA, DTMPA or MgSO,, n' 2 g/L Na,PzO,)

O

10

20

30

40

50

60

70

80

90

Time (min)

Figure 6-5. Effkct of DTPA on the manganese catalysed decomposition of peracetic acid (40°C, pH 7 0 0 7 ppm Mn2+,0.5 g / L DTPA ) .,.5

-A-A-

-r-D-

-0-O-

CH,CO,H, Control H20,, Control CH,CO,H, DTMPA H20,, DTMPA CH,CO,H, DTPA H,02, DTPA

31O -

+* L
20

O
O

0

1-0

30

40

50

60

Time (min)

Figure 6-6.Effect of DTPA or DTMPA on the manganese catalysed decomposition of peracetic acid (40°C, pH 5.0, 0.75 ppm Mn", 0.5 g / L DTPA or DTMPA)

75 ppm ~ n " 0.Time (min) Figure 6-7. of peracetic acid (40°C. pH 6.Effect of DTPA or DTMPA on the manganese catalysed decomposition .5 g/L DTPA or DTMPA) .0.0.

CHAPTER 7 THE FORMATION OF GASEOUS PRODUCTS AND ITS RELATION TO PULP BLEACHING DURING THE PERACETIC ACID TREATMENT .

oxygen is the dominant product of the wastefül reactions. In this chapter. It is shown for an oxygen delignjfied sofiwood kraft pulp that there is a unique relationship between pulp brightness gain and peracetic acid consumption due to the pulp oxidation irrespective of the brightening conditions. The peracetic acid brightening results for an oxygen delignified s o ~ o o d kraft pulp are reported. Keywords: peracetic acid. This suggests that the oxygen formation can be used for control of an industrial peracetic acid treatment. peracetic acid is consumed by two cornpetitive pathways: oxidation of pulp and wasteful reactions such as decomposition and combination with peroxide. the peracetic acid consumed in wastefbl reactions is quantified by determining the gaseous products evolved. gas formation. the brightening efficiency during peracetic acid treatment can be determined by measuring the oxygen formation. It is found that a significant amount of peracetic acid is consumed by the wastehl reactions during the brightening. decomposition. It is found that aithough carbon dioxide is formed under certain conditions. The effect of process parameters on the peracetic acid brightening efficiency is determined. bn~htening.When used in pulp bleaching. Therefore. The oxygen formation is directly proportional to the consurnption of oxidants (as peracetic acid and hydrogen peroxide) in the wastefùl reactions with 2 moles of oxidant consumed per mole of oxygen formed. oxygen delignified softwood kraft pulp .

INTRODUCTION Peracids.131. Vrbaski and Bnhta [12] investiçated the cobalt catalysed decomposition of peracetic acid in an aqueous solution without pH control and claimed that oxygen was the oniy gas formed. Later. Therefore. It was also established [Io] that under typical hydrogen peroxide bleaching conditions the oxygen produced does not contribute to pulp bteaching. such as peracetic acid (Pa) and monoperoxysu1phuric acid (Px). have been identified as prornising alternatives to chlorine containing chemicals for bleaching of chemical pulps [l-81. It was found that oxygen is the only gas formed from hydrogen peroxide decomposition. Under typical peracetic acid bleaching conditions. and that two moles of hydrogen peroxide are decomposed per mole of oxygen formed. Martin [ I 51 and later Gonzalez-Siena [ 161 studied hydrogen peroxide decomposition by monitoring the gas formation dunng peroxide bleaching of groundwood pulps. it was found by Koubek [13] who studied the . in addition to the desirable Iignin oxidation reactions. Gaseous products are also formed during peracetic acid decomposition [ 1O. However. peracetic acid may be consumed by spontaneous and transition metal catalysed decomposition reactions [9. it is important to understand and monitor the peracetic acid decomposition in order to minimize these wastefùl side reactions during peracetic acid bleaching.141. Kagan and Lubarsky [IO] found that carbon dioxide and oxygen are the main gaseous products evolved during manganese catalysed decomposition of peracetic acid in acetic acid and water respectively. Allen and Aguilo Cl 11 confirmed that carbon dioxide is the main gaseous product generated fiom manganese cataIysed decomposition of peracetic acid in acetic acid solution.

5% wlw hydrogen peroxide and 4û% w/w acetic acid with the remainder being water. EXPERIMENTAL Peracetic acid and ultra-pure grade NaOH were purchased ftom Aldrich (Milwaukee. that both oxygen and carbon dioxide were formed in a ratio of about one to one. Furthemore.8. The peracetic acid consists of about 34% w/w peracetic acid. Ontario) and DTMPA from Buckman (Memphis.cobalt catalysed decomposition of peracetic acid at pH 5. a kappa number of 13. USA). Koubek [ 131 also established that roughly 80% of the carbon dioxide formed originated fiom the acetate ion of the buffer. the relationship between the gas formation and efficiency of peracetic acid brightening has never been exarnined. the relationship between gas formation and peracetic acid consumption is determined for typical peracetic acid brightening conditions.8 and a viscosity of 23. The above authors did not extend their studies to a neutd pH range.4 in an ammonium acetate buffer. Reagent grade chemicals. USA) were used in the experiments without hrther purification.9. Furthermore. DTPA fiom Fisher Scientific (Nepean.4 mPa-S. Its metal ion content was below the detection limits of the atomic absorption (AA) spectroscopic analysis method used in this study.17].The chelation .7% ISO brightness. Subsequently it is attempted to relate the gas formation to the brightening efficiency during peracetic acid treatment of an oxygen deIignified softwood kraft pulp. Distilled and deionized water was used in ail experiments. In this chapter. which is optimd for peracetic acid brightening [1. The oxygen delignified softwood kraft pulp used for peracetic acid bleaching had a 37.

Mixing was provided by a submersed 41 mm long magnetic stirrer bar driven by a magnetic drive placed undemeath the constant temperature bath. SampIes of peracetic acid solution were also withdrawn with a syringe. The flow rate of the helium transport gas was controlled by a mass flow controller (Edwards Model 825). The aqueous solution containing al1 the required chernicals except peracetic acid was preheated to the desired reaction temperature. The volume concentrations of oxygen and carbon dioxide in the helium gas Stream are related to the different gas flow rates as: . Any leaks of the system can be detected by the appearance of nitrogen in the gas sarnple. weighted and analysed following the iodometric method developed by Greenspan and Mackellar [ l 81. Ultra pure helium was bubbled through the solution to transport the gases generated by the reactions fiom the flask to a gas sampling loop of a gas chromatography (Fisher model 1200 Gas Partitioner ). The reaction was initiated by addition of a concentrated peracetic acid solution to the reaction flask. The experimental setup was s h o w in Figure 7-1. pH 5 . The pH was kept ih constant wt an automatic titrator by addition of 10 m o n NaOH. The first column is packed with 80-100 rnesh Columpakm PQ and the second with 60-80 mesh Molmlar Sieve 13X.5% pulp consistency and 30 minutes.5% DTPA was performed at S O T .stage (Q) with 0. dual-detector chrornatographic system to separate and measure the gaseous products. Experiments without pulp fibres were carried out in a well sealed 500 mL four-neck round-bottom flask immersed in a constant temperature bath. 2. The gas in the sampling loop was injected at predetermined time intervals into the gas partitioner for analysis. The gas partitioner employs a dualcolumn.

The molar quantities of peracetic acid and hydrogen peroxide consumed were calculated fiom the difference in the concentrations of peracetic acid and hydrogen peroxide at determined times t. Again ultra pure helium was bubbled through the suspension to cany the gaseous products out of the reaction. with mixing provided during the course of brightening by a mechanical stirrer.where F(O3 and F(C0J represent the volumetric flow rates of oxygen and carbon dioxide respectivefy generated by the reaction solution. the volume of 0.] 1O .and CO. evolved was then converted into moies using the ideal gas faw. fiom time t.[CO. and F(He) is the helium fiow rate.[O2] . and t. to t.5 and 1. and CO.. one can calculate F(O3 and F(C02) as: WJ = W e ) . The volume of 0. The helium gas flow rate was kept around 50 mL/min with the mass flow controller. [O. evolved during t i i e intemal of t. The total gas volume collected was measured by water displacement and the gas composition was determined by anaIysis with the gas .] 0 By integrating the flowrates of 0.5 % consistency. By solving Equations (1) and (2). now al1 the gas was collected in a I O L Tedlar gas sampiing bag. to t. However. can be determined. Peracetic acid brightening of pulp was conducted in a 1000 mL four-neck round bottom flask at 0. and CO.

0 and 6.0 under 5. respectively. It was established in Chapter 4 that the disappearance of peracetic acid under this condition is mainly due to the spontaneous decomposition.2 and 25°C with 0. The flow rate of helium was 100 mL/min and the mixing speed was 400 rpm. Pulp brightness.H + 0. as iliustrated in Equation (5): 2 CH3C0. . (5) Figure 7-2b shows that a negligible amount of CO. By plottins the peracetic acid consumption against the oxygen formation in Figure 73. is released and that O. is the only ças generated in the system at this condition.partitioner. T230 om-89. It was found that the oxygen formation is not af5ected by the helium gas flowrate or the mixing speed. and stimng speeds of 200 and 800 rpm.H -+ 2 CH.CO. and T236 cm-85. The experiments were repeated at helium flowrates of 70 and 300 &min. Samples of the spent liquor were withdrawn and titrated for the residual peracetic acid and hydrogen peroxide concentrations. After the peracetic acid treatment. This means that there are no significant transport limitations for the release of oxygen from the reaction system.5 g/L DTMPA present was presented in Figure 7-2. the pulp was thoroughiy washed with deionized water and made into handsheets. it c m be seen that the molar ratio of peracetic acid consumed and the O2 formed is quite close to 2 stipulated by Equation ( ) Similar experiments at pH of 7. viscosity and kappa number were determined in accordance with TAPPI methods T452 om-92. RESULTS AND DISCUSSION The Formation of Gaseous Products During the Decomposition of Peracetic Acid The result ofgas formation and decomposition of peracetic acid at pH 8.

released was still negligible (Figure 74b). such as cobalt. copper and iron catalyse the decomposition of peracetic acid. manganese.191 that trace amounts of transition metal ions.2 and 25°C (Figure 7-4).75 ppm Mn(I1) without the addition of DTMPA at pH 8. manganese is the main catalytic species responsible for enhanced peracetic acid decomposition during pulp bleaching as shown in Chapter 6. the 0 formation was also increased with the addition of Mn(Il). The overall reaction was . Kagan and Lubarsky [IO] and later Vrbaski and Brihta 1121 identified the stoichiometry of the manganese catalysed decomposition of peracetic acid in an aqueous solution as: McDonough [14] and later Evans and Upton (201 reporteci that the reactions of peracetic acid and hydrogen peroxide were catalysed by transition metal ions. It was further confirmed that the sum of the nurnber of moles of peracetic acid and hydrogen peroxide consumed was twice that of the number of moles of oxygen formed. As expected. but the amount of CO. for an aqueous solution of equilibrium peracetic acid the reIationship between the peracetic acid decomposition and the gas formation was examinec? in the presence of 0.13.otherwise the Same conditions confirmed the above conclusions that only oxyzen is generated and that the stoichiometry ofthe peracetic acid consumption to the oxygen formation is very close to 2. Therefore. Among these metals. Similady. It was found [ 10. the presence of Mn(I1) enhanced the disappearance rates of both peracetic acid and hydrogen peroxide (Figure 7-4a).

2. Further experiments showed that the formation of COzis increased by the addition of acetic acid in the presence of ~ n ' +This is . the molar ratio of the consumption of oxidants and the formation of oxygen is always 2 consistent with the experimental evidence. in agreement with the earIier result by Kagan and Lubarsky [ 103 as well as that of Allen and Agulio [l I l that carbon dioxide is the main gaseous product fiom the manganese catalysed decomposition of peracetic acid when it was carrieci out in an acetic acid solution.0. The effect of pH on the formation of gaseous products in the presence of 0.0 than at pH 8. The overall stoichiometry of the oxidationn reduction cycle is the same as Reaction (7).reported as [20]: Furthermore.2 to 5. the present experimental evidence as well as that reported in literature support that carbon dioxide is the fkrther oxidation product of acetic . (6) and ( ) 7. This is due to the fact that the reaction rates of Reactions (9. As will be shown below.0. it was reported [13] that both carbon dioxide and oxygen are the gaseous products when the cobalt catalysed decomposition of peracetic acid was performed in an ammonium acetate bufer of pH 5. As shown in Figure 7 3 % the disappearance rates of both peracetic acid and hydrogen peroxide are much slower at pH 5. it was established in Chapter 6 that there is also an oxidation-reduction cycle in the reaction system with the addition of M " . as discussed in Chapter 5 . As is evident fiom Reactions (5). Figure 7-5b shows that both oxygen and carbon dioxide are generated at pH 5.4.(6) and (7) are al1 decreased at a Iower pH. In addition.75 ppm Mn" was firther investigated by decreasing the pH eom 8.

the proposed mechanism satisfactorily accounts for the observed stoichiometry of the oxidant consumption and the carbon dioxide formation. (6) and (7) oxidizes acetic acid to produce a-peroxide compound O). generating d o n dioxide and fomaldehyde. The Effect of DTPA and DTMfA on Gas Formation and Peracetic Acid Decomposition The effect of DTPA and DTMPA addition on peracetic acid decomposition and oxygen formation at pH 8. it explains why a lower pH favours the formation of carbon dioxide. Thus. peracetic acid and hydrogen peroxide. The singlet oxygen. As can be seen in Figure 7-6. This is consistent with the suggestion of Kagan and Lubarsky [IO] that the stoichiometry of the oxidants consumed to carbon dioxide formed is 3 when manganese catalysed decomposition of peracetic acid is camed out in an acetic acid solution. which undergoes decarboxyiation under acidic conditions. the mechanism in Figure 7-7 is proposed to account for the formation of carbon dioxide. rather than a direct product fiom the decomposition of peracetic acid. In addition.acid. Subsequently. the amount of oxidant consumed was corrected for the oxygen formation according to the stoichiometry of Reactions (S). fomaldehyde is further oxidized by peracetic acid to formic acid as identified experimentally by Kagan and Lubarsky [IO]. Therefore for the experiments at pH 5. (6) and (7). the stoichiometry in terms of moles of corrected percetic acid and hydrogen peroxjde consumed per mole of carbon dioxide formed is approximately 3. are consumed per mole of oxysen generated. formed in Reactions (S).0 described above.2 was examined by adding either DTPA or DTMPA at the mid . Subsequently the molar carbon dioxide formation was plotted against this corrected rnolar amount of oxidant consumed. In the previous section it was shown that two moles of the oxidants. Therefore.

Furthemore. We confirmed this stoichiometry by comparing the initial quantity of DTPA added with the peracetic acid loss calculated as the difference between the total oxidant consumed and the oxidant decomposed as detennined by the formation of oxygen. The much slower rate in oxygen formation shown in Figure 7-9b is due to the fkct that DTMPA stabilizes both peracetic acid and hydrogen peroxide [9].point ofthe reaction (at 30 minutes). He found that DTPA was rapidIy oxidized by peracetic acid at ciifferent pH's varying fiom 6 to 10 in the absence of metal ions and obtained a stoichiometry of 3 moles peracetic acid per mole DTPA. It is also shown in Figures 7-8a and 7-8b that the addition of 0. As s h o w in Figures 7-8 and 7-9 respectively. Figure 7-9a shows that the oxidation of DTMPA by peracetic acid is negligible as evidenced by the absence of sharp decrease in the peracetic acid concentration after the DTMPA addition. . This is attributed to the fact that peracetic acid is being rapidIy consumed in a reaction with DTPA as was reported earlier by McDonough [14]. This couid be explained by the hypothesis that part of the DTPA still chelates with the metal ions but that any excess is rapidly consumed by peracetic acid [ 141.02 moVL DTPA at 30 minutes l a d s to the decrease in the disappearance rate of peracetic acid and hydrogen peroxide as well as the formation rate of oxygen.75 ppm Mn(I1) (Figure 7-8a).02 mol/L DTPA was added with or without the addition of 0. there is a sharp increase in peracetic acid consumption rate when 0. the stoichiometq of two moIes of oxidant consumed (both hydrogen peroxide and peracetic ahd) per mole of oxygen fomed in these experiments supports that the oxidation of DTMPA by peracetic acid and /or hydrogen peroxide can be neglected.

the amount of peracetic acid consumed in wastefùl reactions can be calculated fiom the gas fornation results and the amount of hydrogen peroxide consumed. These results are consistent with those obtained at the same conditions . Listed are the development of the residuaI amount of peracetic acid and hydrogen peroxide. pulp as well as of percentage of total arnount of peracetic acid consumed. The results in Table 7. does not contribute to pulp oxidation. However. The amount of peracetic acid and hydrogen peroxide consumed in wastefiil reactions is calculated fiom the formation of O2 and CO2using the appropriate stoichiometry. the amount of Ozand CO1formed. peracetic acid charge and reaction time on the gas formaion and its relation to pulp brightening during peracetic acid treatment were studied. Since it is reasonable to assume that at the present conditions hydrogen peroxide is ody consumed in wastehl reactions. The results of the peracetic acid treatment of an oxygen delignified pulp are presented in Table 7-1. and the bnghtness and viscosity of the bleached pulp. at pH 5 (Run 5) a small amount of carbon dioxide is formed. pH. SubsequentIy the amount of peracetic acid consumed in pulp oxidation reactions can be calculated as the difference between the total amount of peracetic acid consumed and that consumed in wastefùl reactions. i.e.d. It can also be seen that the total amount of peracetic acid consumed in wasteful reactions is much less at pH 5 than that at pH 7. Both the development of peracetic acid consumed in pulp oxidation reactions and that in wastefbl reactions are given in Table 7-1 expressecl in t e m s of percentage on 0.The Formation of Gaseous Products and Its Relation to Peracetic Acid Bleaching The effect of chelation.1 show that only oxygen is produced when peracetic acid brightening is performed at pH 7. pulp consistency.

d.d.02consurned in wastefid reactions (% on 0.6 2.Table 7-1. ~ ) I I I Pa consumed in pulp oxidation (% on 0. The formation of gaseous products and its relation to bleaching during peracetic acid treatment of an oxygen delignified pulp (Initial brightness of 37. pulp) Pa consumed in wastefùl reactions (% on 0.36 0.7 6ISO. pulp) O formation CO. pulp) I Temperature (OC) Bleaching tirne (min) Residual Pa 1 60 120 Il I 1 O-O9 Residual H202 (% on 0. initial I 1 Experimental Runs 1 Samples h l p consistency (%) Pa Charge (% on 0. / g Pa charged) Viscosity ( r n ~ a .d.d.d. pulp) H.43 81 Pa consumed by oxidation Total Pa consumed (%) l9 * pH was kept constant dunng the blëaching 1 . pu~p) Pa decomposed TotaI Pa consumed (%) 1 I I 1 20. formation (mmol CO.

1 shows that a higher consistency increases the pulp oxidation while the consurnption of peracetic acid in wastetùl reactions is slightly iower @uns 3 and 4).but without the presence of pulp fibres. obviously because the DTPA chelated pulp contains less residuai transition metals as shown in Chapter 6. that . Therefore a higher brightness gain and especially a higher brightening . An important result is that the data in Table 7. . However. The amount of peracetic acid wasted was plotted against the hydrogen peroxide wasted for al1 the experiments listed in Table 7-1. . A surpnsing result ofthe analysis in Table 7-1 is that the majority of the peracetic acid is consumed in wastehl reactions. presented in the previous sections. Figure 7-10 suggests that about half of the peracetic acid is wasted by Reaction (7) while spontaneous decomposition (Reaction (5)) and metal catalysed decomposition (Reaction (6)) are responsible for the other half of the peracetic acid wasted. Figure 7-10 shows that the molar ratio of peracetic acid wasted and hydrogen peroxide wasted is about 2. Cornparison of Run 1 with Run 2 confirrns that DTPA pretreatment leads to Iess peracetic acid decomposition and a higher brightness gain. The effect of pH on peracetic acid brightening is seen by comparing Run 5 and 2 at pH 5.171 peracetic acid brightening is more effective at a neutral pH than at a sliçhtly acidic condition. Since hydrogen peroxide is only wasted in Reaction (7) with a molar ratio of 1 between peracetic acid and hydrogen peroxide 1141. accounting for 59 to 87% of the total peracetic acid consumed. a higher pH also results in less efficient use of peracetic acid since 7 1% of the total peracetic acid consurned was lost by the wasteiùl reactions at pH 7 compared to 63% at pH 5.0 and 7.0 respectively. This is consistent with literature results [ 1 8 9 . The analysis shows that a higher pH leads to more oxidation of pulp and subsequently a higher brightness gain.

This could be explaùied by the fact that at a higher Pa charge the reactive lignin chromophores are rapidly consumed.1 1 is that the bnghtness gain and brightening efficiency can be predicted for a particular pulp independent of the process conditions. charçe minus residual) and the gas (O2 and CO2 ) generation. r As expected a h i ~ e brightness sain is obtained at higher peracetic acid charse under otherwise the same brightening conditions (see Runs 8. This may be . Figure 7-1 1 shows that there is a unique relationship between these two parameters. 2 and 3). This confirms that the peracetic acid consumption in wastefil reactions and by pulp oxidation are two completeiy independent phenornena. therefore. Frorn the peracetic acid consumption (Le. independent of the process conditions. an increase in peracetic acid charge results in a siçnificant lower briçhteninç efficiency. However. It is evident fiom Figure 7-12a that the viscosity of the resuIting pulp is closely related to the hydrogen peroxide consumption in wastefbl reactions. The brightness of the peracetic acid bleached pulps were plotted against the peracetic acid consumption due to the pulp oxidation reactions for al1 the experiments listed in Table 7-1.efficiency can be expected when peracetic acid brishtening is performed at hiçh consistency. a higher Ioss of hydrogen peroxide in wastefiil reactions is always accompanied by a lower pulp viscosity. The same argument explains why the peracetic acid brightening efficiency worsens when the peracetic acid treatment is extended fkom 30 to 120 minutes (Runs 7 and 8). while the peracetic acid concentration is still hi& so that the wastefûl reactions remain substantial. the practical importance of Figure 7. This constitutes a powefil tool for control and optimization of an industrial peracetic acid stage.

It is found that the pulp brightness gain is directly reiated to the peracetic acid . One mole of oxygen is generated per two moles of oxidants (peracetic acid and hydrogen peroxide) consumed. the latter information allows the detemination of the amount of peracetic acid used in pulp oxidation as the difference of the peracetic acid consumed (Le. such as singlet oxyçen and radicals. [21] that distilled peracetic acid (almost no hydrogen peroxide) is more selective than equifibnum peracetic acid in pulp delignification. At a relatively low pH (-5) CO. Thus. Since Figure 7. fiom the measurement of gas generation. Figure 7. pH 7 and 60°C. are generated in the wasteful reactions involved hydrogen peroxide.12b shows that this is indeed the case. CONCLUSIONS Oxygen is the main gaseous product produced fiom the decomposition of peracetic acid under typical brightening conditions. Furthemore.12b is that the pulp viscosity after peracetic acid treatment can also be predicted for a particular pulp independent of the process conditions. i. This is in agreement with the findig by Devenyns et ai. one can expect that the pulp viscosity l o s is also closely related to oxidant (peracetic acid and hydrogen peroxide) consumed in wasteful reactions. based on the stoichiometry of formation of O? and CO2 the amount of oxidant consumed in wasteful reactions can be calculated from the generation of these two gases.e. charge minus residual) and that what is wasted.10 shows that hydrogen peroxide and peracetic acid consumed in wastefùl reactions is closely related. The practical implication of Figure 7.explained by the hct that highly reactive oxyçen species. may also be formed fiom the wasteful reactions at a stoichiometry of 3 moles of oxidant consumed per mole of COSreleased.

independent of the process conditions. ACKNOWLEDGMENT The author thanks NSERC for financial support in the forrn of a Strategic Grant and F. Eddy Forest Products LTD for supplying the oxygen delignified softwood kraft pulp. .and CO. Munro of E.consumption in the oxidation of pulp. çeneration. the pulp viscosity loss is uniquely related to the loss in oxidant as measured by the O2and C O generation. Similady. B. These findings constitute a powerfùl tool for control and optirnization of an industriai peracetic acid stage. As a result the brightness gain of the pulp and brighteninç efficiency can be predicted fi-om the chemical consurnption (peracetic acid and hydrogen peroxide) and the 0.

R. 1993 TAPPI Pulping Conference Proceedings. Atlanta. Peracetic Acid.. D Lubarsky. Improved Oxygen Delignification With Interstage PeroxymonosulfÙnc Acid Treatment. Amini. 1994 TAPPI Pulping Conference Proceedings. Hollie. On-site Peracids: Tools for Bleaching Strategies to Meet the Cluster Rule. L.sec. and A. W. Advances in Chemistry Series. M. G. Treatment of Softwood Kr& Pulps with PeroxymonosuIfate Pnor to Oxygen Delignification. F. TAPPI 1992 Pulping Conference Proceedings. 76(8): 1 94 (1993) Geng. an Effective Alternative for Chlorine Compound Free Ddjgnjfication of Kr& Pulp. Boston. TAPPI PRESS. 357. Springer. Yuan. TAPPI PRESS. 10. T. 1994 TAPPI Pulping Conference Proceedings. Atlanta. Proceedings of 1994 International Non-chlorine rf Bleaching Conference. R. H. and Considerations on How to Select Among Them. A. p.. Jarneel. Peracid Delignification and Bleaching. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. G. Tappi J. Chem. Atlanta. B. p. FL. C. Allison.353. 78(10): 134 (1995) Liebergott. Tappi J.P. 49(1):9 (1966) Hill. Allen.. Dence. p. Devenyns.REFERENCES Bailey. Troughton. Y.van Heiningen. B. T. Vrbaski. H-m. Amelia Island. McSweeny. and J. p. McGrounther. Part 1 and Part II. Kinetics of Peracetic Acid Decomposition.. W. J. Peroxyacetic Acid Bleaching of Chemical Pulp. p. and G. Aguilo.. 371. B. Evans. 2. E. Webster.. and C. Mixed Peracids: Manufacture and Use as Non-Chlorine Delignification and Bleaching Agents. and K. TAPPI PRESS. 75. p.. Webster.37-47 (1997) Kagan. Peracids: The Pathway to High Brightness TCF Kat Pulps.. W.. N. Walsh and J. R. Metal ion catalyseci oxidation of acetaldehyde. C. 1219. Ni and A-RP. and J.1.J. Z. 76. N. Phys. Tappi J . The Intermediate Stages of Aldehyde Oxidation. 39.837 (1935). P. Chang. Amini.363 (1 968). B. and J. Canadian Journal of Chemical Engineering. TAPPI PRESS. Desprez and J. Brihta The Kinetics of Oxidation of Ndehydes to Acids and Acid . D. and 1.

. Troughton. p. D. Gavenko and 1. The Effect of Process Variables on the Decomposition of Hydrogen Peroxide in the Bleaching of Groundwood Pulp...Anhydrides.1 . The Bleaching of Eastern Spruce Groundwood with Alkaline Peroxide 1. 40(2):65 (1957) Gonzalez-Sierra.. W. Part 3. p. Ph. The RoIe of pH in Bleaching. sec. G. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. University of Toronto (1 972) Martin. 26. T. Soc. Chem. (1 977) Rapson. D. W... Chem. E. A. Brown Univ.and M.. Koubek. F. Mackellar.Y...D thesis.. Tappi J. 39(5):284 (1956).267 ( 1954).. . F. M. State Univ. Reaction Kinetics. J. Garbuzyuk. Of New York. H. Tappi J. MSc.. Peracetic Acid Decomposition and Oxidation of Lignin Model PhenoIs in Alkaline Solutions. Desprez and N.. N.D Thesis. Syracuse.F. SC. 6 Vasyutyn. Upton. Tappi J. Analy. Ukrainskii Khimicheskic Zhumal. M. O. College of Environmental Science & Forestry. The Bleachinç of Eastern Spruce Groundwood with Alkaline Peroxide 1. thesis. Arhiv Za Kemiju. 40(2):65 (1 957) McDonough. lnfluence of mineral salts on the decay rate of peroxyacetic acid in aqueous solution. J.. Greenspan. 1 151. Martin.. Reaction Kinetics. HHI. Ph. G. V. The Kinetics and the Mechanism of the Decornposition of Aliphatic Peroxyacids in Aqueous Solutions. 55(6):584 (1 989) Evans. J. Peracetic Acid as a Selective Prebleaching Agent: an Effective Option for the Production of Fully Bleached TCF Kraft hlps. and D.. Analysis of Aliphatic Peracids. Studies on Singlet Oxygen in Aqueous Solution. M. Dalton Trans. D. Proceedings of 1993 International Non-chlorine Bleaching Conference. 20(11): 1 O 1 (1 948). 1964. Ya. M. P. 1985 Devenyns. 8.

The experimentrl setup for the determiiiation of grseous products during peracetic rcid decomposition . 2 Calibration Gases Figure 7-1.f7' Mass Flowmeter Auto Reaction Titrator Vessel in Bath 2-way Swagelok u s O Whitey Valve 1.

.

5 g/L DTMPA addition .5 3O 15 O Formation (mmol) . Figure 7-3. pH 8.2. The stoichiometry of the peracetic acid consumption and the oxygen formation at 25*C. F(He) of 100 mL/min and with 0.

.

.

75 ppm Mn(ïï) and at 25OC. The stoichiometry of peracetic acid consumption and carbon dioxide formation in the presence of 0.2 4 6 CO.0. F(He) of 100 mllmin) . p H 5.Formation (mmol) Figure 7-6.

"T-\ H 1 II O-H oz* Figure 7-7.Plausible mechanism of the carbon dioxide formation during peracetic acid decomposition .

2. pH 8. F(He) of 100 mllmin and with 0. The effect of DTPA addition on peracetic acid consumption and the oxygen formation nt 25OC.O 20 40 60 80 Time (min) Time (min) (b) (a) Figure 7-8.02 niol/L DTPA added at 30 min .

.

. 0.5-596 peracetic acid charge. pH 5-7. 1.5-1.O 1 2 3 4 5 6 7 8 H. 40-60°C. 30-120 min) . The relationship between the wasted peracetic acid and hydrogen peroxide (O or OQ pulp.5% pulp consistency. O wasted (mmol) Figure 7-10.

5-1. The relationship between the peracetic acid consumption due to the pulp oxidation and the pulp brightness (O or OQ pulp.5% pulp consistency.d.CH.CO. pulp) Figure 7-11. 0. 30-120 min) .H consurnption in pulp oxidation (% on 0. 40-6O0C. 1. pH 57.55% peracetic acid charge.

02 wasted (% on 0. The relationship between the pulp viscosity and the oxidant coiisunied in wasteful reactions (O or OQ pulp.0.4 0.5% pulp consistency.2 0.8 1.1. pulp) (a) CH3C03Hand H.5-5% peracetic ricid charge.6 0.0 0.O O 2 4 6 H202 wasted (% on 0.d. 40-60°C.d. 0. pH 5-7.5-1. 30-120 min) . pulp) (b) Figure 7-12.

CHAPTER 8 A KINETIC MODEL FOR PERQCETIC ACID BRIGHTENING OF AN OZONE DELIGNIFIED SOFTWOOD KRAFT PULP .

ABSTRACT A kinetic model of peracetic acid brightening of a solvent-assisted ozone delignified puIp was developed. chromophore. Keywards: Peracetic acid brightening. The kinetic model provides an adequate description of the disappearance rate of the chromophores in pulp at constant pH and peracetic acid concentration. An optimization search aigorithm was used to find the kinetic parameters of the model. and is based on reaction pathways reported for lignin model compounds with peracetic acid. kinetic model. light absorption coefficient. ozone deIignified softwood kraft pulp . The model consists of three paralle1 and one consecutive reaction.

or 0.1 7 that peracetic 1 acid is a good delignifier when used in the prebleaching s t q e s . a kinetic model is developed for the peracetic acid bnghtening of a methanol-assisted ozone delignified and subsequently alkaline extracted (i-e. In addition.131.24]. The kinetic data was obtained by following the light absorption coefficient of the bleached pulp. The constant condition method of kinetic experimentation in which the bleaching chemicai concentrations. It has been shown [l -2. ZnE) pulp.s is bIeached by the Pa stage to a brightness of 82.8.1 O]. in which Zn represents a solvent-assisted ozone stage.66% as hydrogen peroxide.6 mPas with only about 1.13. For example.5% and viscosity of 28.INTRODUCTION Peracids have recently emersed as a potential alternative to chlorine containing chemicais for bleaching of chemid pulps [I . A similar experimental approach has been used to develop the kinetics of hydrogen peroxide bleaching of mechanical pulps [18-221 as well as that of chlorine dioxide bleaching of chernical pulps [23.5% peracetic acid by weight as peracetic acid.4 mPa.7% while maintaining a viscosity of 26. al1 representing reaction pathways identified in lignin mode1 cornpound . an optirnised Pa stage can effectively and selectively increase the bnghtness of a conventional soflwood kraft pulp as part of a ZnEoPaEop bleaching sequence. In the present chapter. peracetic acid (Pa) can also be applied in the Iater brightening stages as a substitute for chIorine dioxide [2. As shown in Chapter 3. it was reported in Chapter 3 that a ZnEo delignified Hedock kraft pulp with a bnghtness of 56. pH and temperature are held constant during the course of reaction was used in the present study. The kinetic model presented in this chapter consists of three parallel reactions and one consecutive reaction.

EXPERIMENTAL Equilibrium peracetic acid and ultra-pure grade NaOH were purchased fi-om Aldrich (Milwaukee. 5% W/W hydrogen peroxide and 40% wlw acetic acid with the rernainder being water.7 kappa number and 27. USA).241 for which the prime objective was to develop an empirical equation based on its ability to represent the experimental data rather than on fiindamental understanding of the detailed reaction mechanism. The Hooke and Jeeves search algorithm [25] was used to find the kinetic parameters of the model by minirnizing the sum of the squares of the differences between expenmental and model predicted values of the light absorption coefficient. The ozone . An ozonated and alkaline extracted softwood kraft pulp of 2. Ozone bleaching (Zn) was carried out on a Hernlock kraft pulp impregnated with 70% methanol-water of pH 2. This approach is different fiom that of other studies [IS-20.studies with peracetic acid. First order reaction behaviour with respect to the chromophore and peracetic acid (or peracetate anion) concentrations were assumed. following an earlier descnbed procedure 1261.5% ISO brightness. 47. The initial values were estimated fiom the data at conditions when only one or two reactions dominated the brightening development.1 mPa-s viscosity was used in this study. Its metal ion content was below the detection limits of the atomic absorption (AA) spectroscopic anaIysis method used in this study. Distilled and deionized water was used in al1 experiments. 23.8 1 m'/kg absorption coefficient. The equiiibnum peracetic acid consists of about 34% wlw peracetic acid. 6.

The pulp s l u q was preheated to the desired temperature.O. well stirred. The maximum change in peracetic acid concentration was les than 10%. and two hand sheets were made according to Tappi standard method T272 orn-92. round-bottom flask immersed in a constant temperature bath. The peracetic acid and hydrosen peroxide concentrations were determined foltowing the iodometric method developed by Greenspan and Mackellar [27].d. 77"C. IO% pulp consistency for 45 minutes.60/0@y weight on 0. Subsequently. 3 g r a m o. The viscosity and kappa number were deterrnined in accordance with T330 om-89 and T236 cm-85 respectively. Preliminary bleaching nins were conducted to determine the rate of peracetic acid consumption. pulp) of which 90% was consumed. pulp was used in each experiment and the pulp consistency was 0. The pulp bnghtness was determined following TAPPI method T452 0111-92.ci. The bleaching reaction was quenched by injecting an excess amount of KI dissolved in dilute sulfiiric acid.3%. The pulp was immediately washed with deionized water. A suitabie amount of NaOH was then added to adjust pH to the desired level. The pH was kept constant with an automatic titrator by addition of 10 m o n NaOH. The absorption coefficient was determined at 557 nm wavelength with Technjbrite Micro TB. .charse was 1. A subsequent alkali extraction stage (E) was perforrned at pH 1 1. the desired amount of peracetic acid w s charged to the reaction mixture at regular time intervals a to maintain a constant peracetic acid concentration.1C. Subsequently. The peracetic acid bleaching experiments at constant peracetic acid concentration were canied out in a 1000 mL four-neck. the required amount of peracetic acid solution was added to initiate the bleaching.

14. the initial chromophore disappearance rate is unchanged while the final degree of chromophore rernoval is reduced. The results listed in Table 8-1 as well as those in Figure 8. It is evident that the light absorption coefficient decreases rapidly at the beginning. the kinetics of peracetic acid brightening are described in tenns of the rate change in the light absorption coefficient. A similar behaviour has been observed for chlorine dioxide bleaching of chemical pulps and hydrogen peroxide bleaching of mechanical pulps [18-241. as the pH increases hrther fiom 7 to 10.0493 mol/L and temperature of 50°C .RESULTS AND DISCUSSION Since the light absorption coefficient of pulp is directly proportional to its chromophore concentration. The results are listed in Table 8-1. It shows that the chromophore disappearance rate and the final degree of chromophore removal are increased at a higher peracetic acid concentration. this pattern could be explaineci by large differences in reactivity of the different chromophore structures. These results are consistent with the general knowledge that the optimum pH of a peracetic acid brightening stage is in the neutral range [8. It is noted that pH has a significant eEect on both the chromophore disappearance rate and the final degree of chromophore removal. The development of the light absorption coefficient at pH 6.0329 to 0. .0 and different peracetic acid concentrations varying fiom 0. Figure 8-1 shows the results obtained at different pHs but a constant peracetic acid concentration of 0. However.28]. When the pH increases fiom 1 to 7.1 forrn the data base for the determination of the kinetic parameters during peracetic acid brightening of the ZnE pulp. but that the decrease becomes increasingly slower as the reaction continues. both of the above two parameters increase.0658 moi/L was also determined. As in these two other cases.

50°C and Different Peracetic Acid Concentrations ! Tirne (min) O 1 C.(m'kg) at different peracetic acid concentrations [fa]: 0. resulting in the formation of hydroquinones [30-341.0. which represent another chromophoric structure [3 1-34]. The oxidation of lignin-like material by peracetic atid has b e n studied.0329 moVL 2.81 [Pa]: 0.Table 8-1. mostly with model cornpounds [29-381.5. The overall reaction pathways which occur during peracetic acid bleaching of wood pulps can be sumrnarized by the following three general categories: 1.3 11 or be further oxidized to conjugated quinones.81 1. Development of the Kinetic Mode1 Typid chromophoric structures in pulps include conjugated lignin macromolecules. The Development of the Light Absorption Coefficient at pH 6. a d o n y l aromaîic moieties and quinones [29-301. Kawamoto et al. The hydroquinones can either be destroyed to colourIess water soluble products via electrophilic ring opening [30. They found that highly conjugated quinones were formed and that tiirther destruction .0658 moVL 2. Hydroxylation of the aromatic rings of lignin by electrophilic substitution. [3 11 studied the oxidation of biphenyl lignin model compounds with peracetic acid at pH 5.0493 mol/L 2.81 [Pa]: 0.

As a result. It has been found [35]that esters and their hydrolysis products were formed during the peracetic acid oxidation of a-carbonyl containing lignin mode1 compounds. and formed fiom Route 1 above can be fûrther oxidized to usually colourless and water soluble carboxylic acids via the BaeyerVillger reaction 1 1-331.35. peracetic acid .3. 3 3. It is important to point out that depending on the process conditions both nucleophilic and electrophilic rnechanisrns may contribute to the brightness increase during peracetic acid treatment.34. Therefore.H) is a strong electrophile [29. electrophilic attack is the main mechanism.30.of these conjugated quinones was a relatively slow process.2).rather than peracetate anion (CHJO. When the pH is substantially higher than 8.CO. These hishly conjugated quinones may be formed by condensation of quinonoid intermediates via a Diels-Alder mechanism f 391.') is the dominant species (the pKa of peracetic acid is 8. 2. Peracetic acid (CH. acetoguaiacone is signi£icantlyless reactive than vanillin due to the rnethyl substituent on the carbonyl carbon which stencally hinders the Baeyer-Villiger oxidation andor disfavours the nucleophilic attacking by peracetic acid.COJ [33. It was also found that a ketone is somewhat less reactive than an aldehyde. Conjugated quinones. The etherïfication of a phenolic hydroxyl group or the presence of an extra methoxyi in the aromatic nucleus appears to have little or no influence on the reaction rate [35].39]. Lignin structures containing an a-carbonyl group are oxidized via the Baeyer-Villiger reaction 135-381. It was established that .4042]is the dominant species. For example. both originally present. the strongly nucleophilic peracetate anion (CH. a nucleophilic attack is expected to be the main reaction mechanism at high pH. When the pH is in the range of 1 to 6.

is mainly responsible for the Baeyer-Villiger oxidation in the system we studied. This is supported by the results that the oxidation of benzophenone by peracetic acid in glacial acetic acid proceeds very slowly and that the addition of concentrated sulfùric acid greatly increases the reaction rate [44]. it was reported f43-461 that high concentrations of suIfùnc acid and perchloric acid catalyse the Baeyer-Villiger reaction. while the Baeyer-Villiger reaction takes place through a nucleophilic attack [35-381. the kinetic mode1 shown in Figure 8-2 . Ishikawa et al. and an extended reaction time. at a high peracetic acid concentration. [37] treated acetoguaiacone with 8% peracetic acid at 35°C and found that the oxidation of acetoguaiacone is quite slow. as was observed by Nirnz and Schwind 1351. However. high temperature. However. Because of these facts. experimentd results show that a high concentration of strong acid is required.hydroxylation of the aromatic rings proceeds via the electrophilic mechanism 130-341. we assume that peracetate anion. Similarly. For exarnple. In principle. Based on these identified reaction pathways. However. Based on these results. not peracetic acid. the Baeyer-VilIiger oxidation could take place at general acidic conditions. in the absence of a high concentration of strong acid. it is understandable that the best brightening is obtained at a neutral pH range where both peracetic acid and peracetate anion are present in significant quantities. the Baeyer-Villiger reaction may account for part of the substrate consumed. the Baeyer-Viiliger oxidation is expected to be slow under acidic conditions due to the low nucleophilicity of the undissociated peracid. Sarkanen and Suniki 1 7 found that the amount of side-chah oxidation via the 41 Baeyer-ViIliger oxidation remains smd at a low pH when they treated Douglas-fir meal with 10% peracetic acid in an aqueous solution.

.H] ... are destroyed via the Baeyer-Villiger mechanism by CH.\ C [CH$O. [CH. represented by the rate constant k.H via the hydroxylation route.$C. C. The conjugated quinones. . is consumed in two cornpetitive reactions. --dC3 = k4C. based on the model described in Figure 8-2. both the newly formed and those originally present. leading to the formation of either colourless products (Cp) or conjugated quinones (Ca.CO.. as discussed previously. Therefore.[C%CO. [CH&O.H] dC1 dt . and peracetate anion concentration.. FinalIy. C .+ kJ C.. rzte constants respectively.. ] dt Peracetic acid concentration. are oxidized to water soluble carboxylic acids via the Baeyer-Villiger reaction by peracetate anion CH.].H]. the following rate equations of peracetic acid brightening are obtained: . and k2 as their . The model in Figure 8-2 shows that the chromophoric Iignin macromoIecule C. with a rate constant of k. [CH.CO..is proposed for peracetic acid brightening of ozone delignified sofkwood kraft pulp.. C.] dC2 dt . the a- carbonyl containhg chromophores...CO. [ C H p . It is assumed that the reactions discussed in Figure 8-2 are first order with respect to hs the peracetic acid concentration and the chromophore concentration. Therefore..(k.CO. is eIectrophilicdly attacked by peracetic acid CH. with k. T i hypothesis is supporteci by the results of McDonough [33] that the kinetics of the oxidation of creosol by peracetic acid is fint order both in peracetic acid and creosol concentrations.CO.

with M beinç the ratio of the proton concentration to the dissociation constant of peracetic acid. [CH$%].H].C03H].C03H]. are constant at a fixed pH and temperature. 1 +M M Equations (6) to (8) can be solved analyticaily as: AIso the sum of a 1 the different chromophore concentrations at any time during the 1 . = k. and that of peracetate anion. Since the concentration of peracetic acid. [CH.are related to the total titrable peracetic acid concentration [CH3C0. Equations (1) to (3) can be simplified as: where k. i.e.[CH-. [H+]/K.. as in Equations (4) and (5).

1. which is known experimentally. in order to start the search algorithm. 2.1 shows that the initial rate of the chromophore disappearance is strongly dependent on the pH Since the concentration of peracetate anion increases dramatically while that of peracetic acid is relatively constant when the pH increases fi-om 1 to 7. easily with peracetate anion accordinç to the Baeyer-Villiger mechanism [35-381. C. With the knowledge of the disappearance rate of total chromophore concentration under different conditions. k. i. Figure 8.react . Equations (13) to (16) show that there are seven unknown variables: ki. it was assumed . 3 equations. (13). it is needed to provide initial values for six of the variables. (14) and (15) and 56 data points in the f o m of equation (16). The sarne technique was applied to determine the kinetics of chlorination.. C.[48..C .ki. and C. it is possible to determine the rate constants and the initial concentration of each of the three chromophores by an optimization technique which utilizes the Hooke and Jeeves search algorithm [25].while the oxidation of conjugated quinones proceed slowly in aqueous solutions [3 11. Estimation of the Initial Values 2.course of the peracetic acid treatment equals to the total chromophore concentration.e.. with the seventh being fixed by equation (16).49]. represented by C . Since it has ben s h o w that a-carbonyl compounds. the higher initial reaction rate in this pH region must be related to the higher peracetate anion concentration. Estimation of CSiandk.kj.

of 1.0 and 50°C. for the optimization procedure will be varied by two orders of magnitude around 2x10' Llmo1. However. for the optimization procedure it was assumed that 99% of the a-carbony1 chromophores initially present.8 1 m2/kgand the sum of C. In order to better quanti@ the initial reaction rate. the initial a-carbonyl group concentration..min is only a first order estimate. the initial value of k.81 to 1.that in the initial phase the Baeyer-Villiger oxidation of a-carbonyl chromophoric structures is the dominant reaction at a higher pH. the shortest time possible with our experimental set-up. Figure 8-3.85 m2kg estimated by extrapolating the initial four points in Figure 8-3 to zero time. by taking into consideration of the pKa. Furthemore.i and C.96 m'kg fiom the difference of the initial total chromophores. C. of 2. fùrther cxperiments were done to characterize the light absorption coefficient development during the first 4 minutes at pH 7. pH and the total peracetic acid concentration.i.. Ci . we . Following Equation (1 5). was estimated as 0. shows that the light absorption coefficient decreases rapidly fiom 2. i order to generate n a first order estimate of the initial value of k. . Only a vety rough estimate of the rate constant k can be obtained fiom the data in . of 2x10" L/mol.Therefore. disappeared in the first five . seconds.75 m2/kg. calculateci that k is approximately 2x 10' LImoLmin.min in order to evaluate the sensitivity of the procedure to this initiai guess of k. we estimated a k of 6x10 min-'. . Since it is realized that the calculated value of k. because the reaction of the cc-carbonylchromophores with peracetic anion appears to be essentially complete at the first data point of 5 seconds. C . The results in Figure 8-3 suggest that the Baeyer-Villiger oxidation is very fast since the first data point obtained at 5 seconds.

of 0. Therefore.2. Estimation of CZi and k . oxidation at pH 6. (7) and (8) reduce to: .57 m'kg and k is 0. Also because the actual concentration of peracetic acid is essentially the sarne when the pH is increased fiom 1. Cr and a-carbonyl containing chromophores. the estimate for C. As discussed earlier.min.. the Baeyer-Villiger oxidation of a-carbonyl containing chromophores is a fast reaction with k being about 2x10' L/mol. (shown in the previous section) and C . minutes.O. CH. Substitution of k to Equation (1 1) yields k of 4. Figure 8-1 shows that the chromophore removal is negligible after 50 minutes of reaction at pH 1. C by reaction with peracetate anion. which is achieved by peracetic acid and represented by reactions k. Since oxidation of both conjugated quinones.0. .0 to 6.0.96 m'/kg .is 0. C.00 145 min1. can be considered the ody reactian pathway tu remove chromophures at this pH. . the initial concentration of conjugated quinones. Equations (6).: i.i is calculated as .e. so that it takes less than one minute to complete this . at pH 1.so it is reasonable to assume that the hydroxylation reaction is completed within 50 minutes at this condition. From this plot shown in Figure 8-4 it follows that C.CO. it can thus be concluded that after 50 minutes at pH 6.7 L/mol.min.57 m'kg. and k2. the hydroxylation.0 the decrease in the light absorption coefficient is mainly due to the .0 is insignificant due to the very low peracetate anion concentration. it is assumed that the hydroxylation reaction at pH 6.. With C of 0. destruction of conjugated quinones.0 is also completed within 50 minutes. C. and the rate constant k can be estimated by plotting 1nC against time t at pH 6.0 for the data points obtained beyond 50 .2. Based on the above analysis.

CO. of 0. Equation (1 6) can be simplified .23 Estimation of k.0062 min-'. Taking into consideration the pH and the total concentration of peracetic acid in Equations (9) and (IO). An application of the exponential decay data fitting technique yields Equation (19) to mode1 the data points at pH 1.i. possible to determine the optimal value of these kinetic parameters using the data base shown in Figure 8-1 and Table 8-1 following the Hooke and Jeeves search algorithm [25].602 + 1. k. 3. and k.205 e'0-'06' (19) From a cornparison of Equations (18) and (1 9).O. and k. it follows that: and (1 -) - k. Therefore. respectively. shown in Figure 8-1. and k2 were estimated using the results obtained at pH 1.205 k.As a result. . and k2 are estimated as 2. both k and k wili be set equal to zero at pH 1 . in Figure 8.126 L/mol. By solving Equations (20) and (21). C. k. it is now .+ k .. Since the peracetate anion concentration. .both of the Baeyer-Villiger pathways c m be neglected. of 0. k. is extremely low at pH 1 . one obtains a k..O.. as discussed earlier.i. The .100 min-' and a k.O. Modelling Results With the estimation of the initial values of C. The values of k.1 as: O C = 1. k.].03 and 0. [CH.min. CZi. CIi = 1.

[3 11 who showed that fùrther oxidation of the conjugated quinones fomed via the hydroxylation pathway to colourIess products is quite slow at pH 5. The optimized results are Listed in Table 8-2. An example of a companson between calculated and measured light absorption coefficients at pH 7. other rate constants. The procedure was considered converged when. expected that the oxidation of conjugated quinones. k.H and C .CO. was varied by two orders of magnitude around the estimated value. CL proceeds slowly due to the lower concentration of CH.5 [3 Il.CO. acetoguaiacone reacts much faster than apocynol and vanillyl alcohol during peracetic acid treatment at a pH of 6 to 9. so their . for each data set at a fixed pH and peracetic acid concentration. It shows that k is much higher than the . It is apparent that the proposed kinetic model gives a good description of the development of the Iight absorption coefficient dunng . O . Thus it is HC. reaction rates largely depend on the concentrations of CH.0 is given in Figure 8-5.approach is to minimize the sum of squares of the difference between the experimental values of the total chromophore concentration and that of the model predictions. confhing that the oxidation of a-carbonyl containing chromophores. the surn of squares changed by less than O. 1% between iterations. is a fast reaction. This is in agreement with the findings by McDonough [333 that . C .at a pH lower than 7. while the other rate constants were varied by a factor of two. To ensure that the optirnised set of parameters indeed represented the unique solution of the kinetic modei for the present data.. It was found that the d u e s of the optimised pararneters were essentially the same as initial estimates of the kinetic parameters. the most uncertain parameter..0. as was supported by Kawamoto et al. Table 8-2 also shows that k is comparable to k .

.peracetic acid brightening of the ozone detignified pulp used in this study. At pH 3 in Figure 8-6 the destruction of chromophores C ..03 kz 0.0 in Figure 8-7.28 C3 Ci 3 kt 2.57 0.96 1-01 4. The degradation of conjugated quinones.chromophores is in agreement with the results by Nimz and Schwind [35] that about 42% acetoguaiacone is oxidized via the Baeyer-Villiger reaction at pH 3 and 60°C over a period of 60 minutes. C. A higher pH favours the degradation of conjugated quinones relative to at pH 3 which is in agreement with the finding by Nimz and Schwind [35]. C. min) CIi Estimated Optimized 1.7. G.7 20000 17700 1. are destroyed at 90 minutes. It can also be noticed that . the concentration of the conjugated quinones. increases slightly over the course of the reaction. The results are plotted in Figures 8-6 to 8-8 respectively. is accomplished within a f w seconds. the oxidation of the a d o n y l containing chromophores. the concentration-tirne profiles of the three different chromophores.. The behaviour of the C. is still incomplete at 90 minutes at pH 7.33 With the optirnized kinetic parameters. however.26 3. and the total chromophore concentration C was predicted at a pH of 3. At a higher pH of I O in Figure 8-8. However.O and 10. G. C. is completed d e r about 50 minutes while around 40% of the a-carbonyl containing chromophores. while e the CI chromophores are also removed within one hour.O. C b is complete in almost 20 minutes. C.126 0.54 0.17 k3 k4 0. it c m be seen that now the oxidation of conjugated quinones. Table 8-2.0. At pH 7. The Kinetic Parameters Obtained by the Hook and Jeeves Search Algorithm at 50°C for the Brightening of ZnE Pulp Initial chromophore concentration (m" /kg) Rate constants (L/mol.

The kinetic equations can adequately describe the developrnent of the light absorption coefficient of pulp under conditions of constant pH and peracetic acid concentration. are efficiently removed at pH 10. The model includes three parailel reactions.0 because the initial concentration of C.. A fitrther increase in pH to 10. The reaction rate of each of the three reactions is dependent on the pH during the peracetic acid treatment. oxidation of conjugated quinones. the overalI degree of chromophore removal is much less than that at pH 7.0. . CONCLUSIONS Based on reaction pathways identified in literature.chromophores. which are responsible for the overall removal of chromophores. a kinetic model for peracetic acid brightening of a solvent-assisted ozone delignified pulp has been developed. At pH 7. At pH 3 only hydroxylation is significant. while oniy the conjugated quinones are rernaining when the treatment is extended beyond 50 minutes at 50°C. Thus. chromophores is larger than that ofthe C. and oxidation of carbonyl containing iignin stmctures.0 significantly retards the hydroxylation rate. C. which explains the smalter removal of chromophores at this pH as compared to that at pH 7. is significantly reduced due to a much lower concentration of peracetic acid. both the hydroxylation and oxidation of carbonyl containing lignin structures is complete. This explains the experimental fact that optimum brightness gain can be obtained at a neutral pH ranse. namely hydroxylation. although both quinones. and thus for the decrease in the light absorption coefficient of the bleached pulp.at pH 1 0 the destruction rate of chromophores C. a-carbonyl containing chromophores. C2.

s .ACKNOWLEDGMENT NSERC's financial support in the form of a Strategic Grant i greatly appreciated.

sec. Webster.REFERENCES HiII. Peroxygen PrebIeaching and Bleaching Technologies for Step-Wise Conversion fiom Conventional Chlorine Bleaching via ECF toTCF. Proceedings... Montreal. TAPPI PRESS. Hollie. J. J. . BI57 rf Song. Treatment of Softwood Kraft Pulps with Peroxymonosulfate Prior to Oxygen Delignification. 1994 International Non-chlorine Bleaching Conference. 1992 Springer. Lundgren. H. Holtinger. Pulp & Paper Canada. 8. 37 1 Liebergott. N. Atlanta. L... Di-per process: Time for a peracid delignification and bleaching. p. A. TAPPI 1992 Pulping Conference Proceedings. p. Sponsored by Pulp & Paper and Emerging Technolog Transfer Inc. and J. Preprints. FL. and Considerations on How to Select Among Them. 12 19 Anderson. Desprez and N. Devenyns.1.. Tappi J. J. D. 1995. On-site Generation and Use of Peroxy Acids in Chemical Pulp Bleaching. P. Peracid Delignification and Bleaching of Chemical Pulp Part II: Oxidation. 10. Fasten. Prepnnts. Amelia Island. sec. R. Wilkinson. F. North Caroline State University. TAPPI PRESS. Peracids: The Pathway to High Brightness TCF Kraft Pulps. Atlanta. Desprez and J. McSweeny. TAPPI 1993 Pulping Conference Proceedings. T.. J. Devenyns. CPPq Montreal. Peroxyacid Bleaching of Conventional. B. p. Fredriksson. Atlanta. Sect. CPPA. Sponsored by Pulp & Paper wid Emerging Technology Transfer Inc. 1 1-3 Amini. and R. E. USA. Tech. TAPPI PRESS. MCC and RDH Kat Pulps. On-site Peracids: Tools for Bleaching Strategies to Meet the Cluster Rule. Tech. FL. F. Proceedings. p. Proceedings. Alternatives for Achieving f i g h Brightness TCF Pulps. p. the 8 1'' CPPA Annual Meeting. 1994 International Non-chlorine Bleaching Conference. B59.B. Ph. TAPPI 1994 Pulping Conference Proceedings.. Basta. N.D thesis. SI* CPPA Annual Meeting. Amini and W. L.. N. 1995. P. 97(3):73 (1996) Troughton. an Effective Alternative for Chlorine Compound Free Delignification of Kraft Pulp... Peracetic Acid. Amelia Island. Sect. 341. Walsh and J. 7 ( ) 194 (1 993) 68: Liebergott. R.. Troughton. and J.

P. C. Troughton. Graham. Peroxyacetic Acid Bleaching of Chernical Pulp.W. Sponsored by Pulp & Paper and Emerging T e c h n o l o ~ Transfer Inc. Raleigh. Preprint. Proceedings. C... Quebec.B. N. R. P. and C. JPPS 1 5(4):. March 3. Swan.and K.C. B.. Desprez and N. H. 1993 Workshop on Emerging Pulping and Chlorine-Free Bleaching Technology. 49(1):9 (1966). 1985. Sus. sec.Jl45(1989) Wright. sec. 1965. Sjogren. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. Abbot. Peroxide Bleaching of Mechanical Pulp Fractions fiom Radiata pine.. BIeaching in Five Stages to Asymptotic Limit Using Only One Oxidant and Sodium hydroxide. M. IS(1):1 1 l(1992) . and W.and C. Kinetics Models for Hydrogen Peroxide Bleaching of Mechanical Pulps. Sustainable Development in STORA's Chemical Pulp Mills.. and J. Ginting and J. HHI.. W. Kinetics of Hydrogen Peroxide Bleaching of Mechanid Pulp. 8-1 Bailey. 1996 International Non-chlorine Bleaching Conference.. 2(4):447(1982) Allison. Peracid Technology Review. Peracetic Acid as a Selective Prebleaching Agent: an Effective Option for the Production of Fully Bleached TCF Kraft Pulps. Abbot. Proceedings. L. 227 GeUerstedt.. Tech. p. Generation and Application of Peracids for Chemical Pulp Bleaching. Dence. F. and H. FL. 1996 International Non-chlorine BIeaching Conference. Laboratory Studies of Acetic Acid Bleaching. TAPPI Annual Meeting.Il. W. 13-2. Sponsored by Pulp & Paper and Emerging Technology Transfer Inc. Hyatt Orlando. B. Lundqvist.W.. 5-4. S. J. and B. Tappi J. Kinetic Models for Peroxide Bleaching under alkaline Conditions. SC. 1985 International Pulp Bleaching . FL. Devenyns. Nirnrnerfi-oh. Part 2: Equilibrium Models. 1 l(3): 349(1991) Wright. Tech. Wood Chem. Wood Chem. 82(1):16(1979) Moldenius. J. 1993 International Non-chlorine Bleaching Conference. Conference. Wood Chem. J. Y. Preprint. Part 1 : One and Two Chromophore Models. sec. p 132. Hyatt Orlando. Parker. U. Svensk Papperstidn. Rapson. F.A Cost Cornparison. N. G. J. Chnstiansen. Tech. 1993.. Kinetic Models for Peroxide Bleaching under Alkaline Conditions.Anderson.

the 8& International Symposium on Wood and Pulping Chemistry. and A. 3. Analy. 972(1965) .H. H.. G. Proceeding. Ph. Trans. B303 Greenspan. Y. van Heiningen. the 82nd Annual Meeting Preprints. Comp. XLVII. J. Reaction Products of Neutra1 Peracetic Acid Oxidation of Model Lignin Phenols. J. Chem. Japan. 8(2):212(196 1 ) Kang.. Migita. N. 1292(1931). Trans. CPPq 6. Lignins. 1971. Origin of Succinic Acid as An Oxidation Product of Lignin with Peracetic Acid. M. 13. Nakano. Andysis of Aliphatic Peracids. and D. Tappi J. Finland.. Oxidation of Monohydric Phenols with Hydroçen Peroxide. U. Engleberts. A.. Helsinki. 1996. University of Toronto. and N. Mechanism of Cellulose Protection CPPA in a Novel and Selective Ozone Pulp Bleaching Process. Oxidation of Monomeric Lignin Model Compounds with Peracetic Acid. l659(l9 10) Nimz. Canada (1972) Henderson. K. Peracetic Acid Decomposition and Oxidation of Lignin Mode1 Phenols in Aikaline Solutions. 34. H. Teder. p.. G. T.. CelluIose Chem. F. and H. Tech. Mackellar. J. p. Chem. The Role of pH in Bfeaching.. Amsterdam.. and R. 2 ( 1): 1061 (1948) 0I Rapson. Acad. Tormund. Soc. Chem..459 Boeseken. Tech. 1995. J. Direct Search Solutions of Numerical and Statistical Problems. Ind. Boyd. Ni and A. CPPq Montreal. Wiley Interscience. Soc. Sect.. Schwind. G. Strumila.383.Teder. Lignin. 97. H. and T. W.D Thesis.41(1977) Germgird. Jeeves. G..and H.G. Sarkanen. Proc. H. H. Mech. V-and C.. and D. Assoc. Pulp & Paper Canada. Reaction of Peroxyacids with Lignin and Li& Model Compounds. R. Tech. H. Kinetics of Chlorine Dioxide Bleaching. Chang and H. P. Rapson. Y. 35 750(1932) Kawamoto. J. 35 (1 979) Hatakeyarna. 3. R. Technof .. 76(9):72(1975) McDonough. P.A. 68. Kinetics of Chlorine Dioxide Prebleaching. p. TR3 1( 1980) Hooke. June. CPPA.. 39(5):284 (1956). Chem. Sci. Sect. and R. J.. Ludwig. Jameel. Sect. Preprints. Sect.

. Chlorination Kinetics of Kraft Pulp. Soc. P.. Chem. A.. 1957. Roger (ed. Organic Reactions. 21(1):J30 (1995) . The Peracetic Acid Cleavage of Unsymmetrical Ketones. R. John Willey & Sons Ltd. Soc. Institute of Paper Chemistry. van Heiningen. 1969 Jencks. Am. Y.. Oki and H. 1992. Crooks. Soc. J. C.. p. 62(2): 525 ( 1940) Sarkanen. Organic Peroxides.. Oxidation Products of Sarsapogenin Pregnanetriol-3. Chem. and J.. W. M. J. S.73. Ph. Wisconsin. McGill Univ. E. Y. J. Ishikawa. Dynamic Simulation of the First Two Stages of a Kraft Softwood Bleach Process.). W. and J. Am. Oxidative Decomposition of Lignin.. Ohkubo. Chem.. 435(1966) Kinoshita.. Oki and K. Wood Res. 20. J. Soc. p. S.. H. M. E. Vol. V. 3 19 (1967) Farrand. J. W. L. and D.T. Tappi J. Whittle. J.. Chem. Chem. Canada.D.). New York. Camuolo. Rohmann. Kubes and A. New York. Oxidative Degradation of Guaiacylglycerol with Peracetic Acid.C. P. 16. John Willey & Sons Ltd. H. Appleton. Delignification by Peracetic Acid. K. Jones. J. von E.20. 72(12):% 15 (1950) Friess. E. T. Eng. J. Suzuki. Soc. Am. 48(8):459 (1 965) Mackinnon. Japan. Speers. Am. V. E. 82.. E. 1989 Ni. 7I (7):257l (1949) Marker. Studies on Oxidative Delignification Mechanisms..J. The Degradation by Peracetic Acid of Aromatic Compounds Stmcturally Related to Vanillyl Alcohol Elements Present in Sofbood Lignin. Lefiler. L. Thesis. Reactivity of Nucleophilic Reagents toward Esters. Reaction of Per Acids II: The Reaction of Perbenzoic Acid with Simple Cyclic Ketones. 9.Ishikawa. J. JPPS.. and L. Yasuhiko. 1785 (1951) Doering.. G. USA. Peroxyacetic Acid Oxidation of 4-Methylphenols and Their Methyl Ethers.16. L. Hydroperoxide Oxidation of a-dicarbonyl Compounds. 13. Thesis. Org.. H. R.437. (ed. Japan Tappi. M. Ando. Turner. 1778 (1960) HassalI. J..

The e f f i of pH on the light absorption coefficient development during Pa brightening of ozone delignified softwood kraft pulp (50°C and [CH.Hl of 0.CO.Figure 8-1.0493 m o n ) .

Figure 8-2. The proposed kinetic mode1of peracetic acid brightening .

H] of 0.0 1 3.CO. 1.0493 m o n ) .0 ~ 4.5 l ' ~ Time (min) Figure 8-3. 0 .5 ~ l 4. and k.30 . [CB. (50°C.0. 0!0 0 0-5 ~ 1. p H 7.0 .5 I 20 [ i 25 = 3. Estimation of C. .

0.0493 moVL) . Estimation of CIiand k. pH 6.CO. (50°C.H] of 0. [CH.O 100 150 200 250 300 350 Time (min) Figure 8-4.

. .3.0493 m o a ) . Cornparison of mode1 predictions and experimental results (SOT.CO.0 1 O 10 M 30 40 50 ô0 70 80 90 100 Time (min) Figure 8-5. pH 7 0 [CH.HJ of 0.

. C. and C (5OUC. Predictions of the development of C. C.0493 moVL) ..pH 3.0. [CH3C03H]of 0.O 20 40 60 80 100 Time (min) Figure 8-6.

C.0493 moVL) .CO.H]of 0. and C ( 0 C pH 70 .. C. . 5°. Predictions of the development of C.O 20 40 60 80 1 Time (min) Figure 8-7. [CH..

pH 10. and C (SOT. C.Time (min) Figure 8-8..0493 m o n ) . C.0.. [CH3C03H] of 0. Predictions of the development of C.

CHAPTER 9 CONCLUSIONS .

1% MgSO. viscosity and brightness stability of this TCF fully bleached kraft pulp are similar to or better than those bleached 4 t h chlorine-containing chemicals.2 the hydrolysis is negligible and the peracetic acid consumption is mainly due to ..5% NaOH and 0. 60°C. peracetic acid t is consumed by three wasteful side reactions in addition to the desired oxidation reactions with pulp. No chelation chemicals are required for this TCF bleaching sequence.5 to 8. 1. a neutral pH and 3 hours. A final TCF brightening sequence of PaEop has been developed for a solvent assisted ozone delignifieci and oxidative extracted (ZnEo) Hemlock kraft pulp. 20% pulp consistency. With the ZnlEoPaEop bleaching process a conventional softwood kraft pulp with a kappa number of 30 could be bleached to 88% ISO brightness while rnaintaining a viscosity of more than 20 mPa. The addition of the chelating agent DTMPA to a dilute peracetic acid solution effectively suppresses the metal catalysed reactions of peracetic acid.5%. The optimum conditions for the peracetic acid and Eop stages have been detemined. ln a pH range of 5. T has been shown that under typical peracetic acid bleaching conditions. with 0. Those for the Pa stage are: a peracetic acid charge of 1.95"C. These unwanted reactions are: i) spontaneous decomposition.s with charges of 2% ozone. The brightness. The optimum conditions for the reinforced Eop stage are: 20% pulp consistency .GENERAL SUMMARY This thesis focuses on fundamental and practicai aspects of peracetic acid brightening of softwood kraft pulps. 90 min .5% H202 1.5% Pa and 0. 60 psi oxygen pressure.5% hydrogen peroxide. ii) hydrolysis and iii) transition meta1 catalysed reactions.

CO. pH is one of the important factors which determine how peracetic acid is consumed.0 the peracetic acid consumption is due to spontaneous decomposition and alkaline hydrolysis. the consumption of peracetic acid and hydrogen peroxide by decomposition reactions can be accurately predicted. It was found that the spontaneous decomposition reaches its maximum rate at pH 8.spontaneous decomposition. at pH 9. the hydrolysis is rnainly responsible for the consumption of peracetic acid. while between pH of 8.5 leads to formation of a precipitate of Mg(OH). The kinetics of the alkaline hydrolysis of peracetic acid were also developed.5 or higher the hydrolysis becomes dominant when the metal ion catalysed reactions are minimized by the addition of DTMPA. It was found that the spontaneous decomposition is second-order with respect to the total peracetic acid concentration ([CH.2 to 9. At pH 10. It was also found that the addition of MgSO. The kinetics of the spontaneous decomposition of peracetic acid were developed. When these kinetics are combined with those of the spontaneous decomposition developed earlier. The results show that a significant amount of peracetic acid c m be w s e when metal ions are present. The transition metal ion induced peracetic acid decomposition and the effect of the addition of cheiants/additiveson the decomposition were studied under the typical peracetic acid pulp bleaching conditions. which reduces the rate of transition metal catalysed reactions but enhances that of the hydrolysis of peracetic acid. The metal ion atd .2.5. With the addition of 6 g/L MgSO.H]J. The present experimental resuIts are well described by the developed kinetic equation. resulting in Iess efficient bleaching. at pH 9. while both the hydrolysis and metal ion catalysed reactions increase as the pH increases.

However. Le. pH 7 and 60°C.induced decomposition may proceed via a radical mechanism. Oqgen is the main gaseous product produced fiom the decomposition of peracetic acid under typical brightening conditions. This is explained by assuminç that the more stable complexes of DTPA or DTMPA with Cu2+and ~ e ) 'do not catalyse the decomposition reactions. to the peracetic acid bleach liquor may r m l t in poor bleaching due to the fact that peracetic acid is consumed by wastefùl reactions with DTPA. while Cu2+and ~ e do not.. In-situ addition of chelants such as DTPA or DTMPA to the peracetic acid solution minirnizes the Cu(II) and Fe(II1) induced peracetic acid decomposition but increases the M n 0 induced decomposition. while the less stable DTPA-M~I~' complex does.prevails when manganese is present in the peracetic acid solution at a pH of around 6. and by the fact that only rnanganese participates ~ ' in an oxidation-reduction cycle. the oxidation and reduction cycle involving Mn(I1) and MnO. such as DTPA. however. One mole of oxygen is generated per two moles of oxidants (peracetic acid and hydrogen peroxide) consumed. The addition of sodium pyrophosphate effdvely deactivates the metal ions and consequently improves the bleaching performance. A chelation pretreatment stage for pulps with a high metal ion content. A close inverse relationship between peracetic acid decomposition and pulp brightness development was observed and confinned at constant pH and peracetic acid condition. l a d s to improved subsequent peracetic acid bleaching. the addition of some chelants. while for pulps with a low content of metal ions chelation prior to Pa treatment may not be necessary. At a relatively low pH (-5) CO2 rnay also be formed fiom the wastefùl reactions at a . especially manganese.

based on the stoichiometry of formation of OZ and COZthe arnount of oxidant consumed in wastehl reactions can be calculated fiom the generation of these two gases. At pH 7. and thus for the decrease in the light absorption coefficient. generation. At pH 3 only hydroxylation is significant. the pulp viscosity loss is uniquely related to the loss in oxidant as measured by the 0. independent of the process conditions. As a result the brightness gain of the pulp and brightening efficiency can be predicted fiom the chernical consumption (peracetic acid and hydrogen peroxide) and the O3 and CO2 generation. Simiiarly. Thus. Furthermore.stoichiometry of 3 moles of oxidant consumed per mole of CO2released. oxidation ofconjugated quinones. The kinetic equations adequately describe the development of the light absorption coefficient of pulp at conditions of constant pH and peracetic acid concentration.e. It is found that the pulp bnghtness gain is directly related to the peracetic acid consumption in the oxidation of pulp. These findings contribute a powerfbl tool for control and optimization of an industrial peracetic acid stage. Finaliy. both the hydroxylation . and CO. and oxidation of carbonyl containing lignin structures. namely hydroxylation. which together are considered to be responsible for the overall removal of chromophores. The reaction rate of each of the three reactions is dependent on the pH during the peracetic acid treatment. a kinetic model for peracetic acid brightening of an ozone delignified pulp was developed based on the reaction pathways identified in the literature. charge minus residual) and that what is wasted. The model is based on three parallel reactions. the latter information allows the determination of the amount of peracetic acid used in pulp oxidation as the difference of the peracetic acid consumed (i.

RECOMMENDATIONS FOR FUTUlRE WORK to study the kinetics of manganese catalysed decomposition of peracetic acid to test the feasibitity of monitoring peracetic acid bleaching in a commercial bleach plant by detemining the generation rate of gaseous products from peracetic acid decomposition to identifi alternative stabilisers for peracetic acid bleaching other than sodium pyrophosphate to investigate the stability and consumption of an aqueous solution of distilled peracetic acid under typical peracetic acid bleaching conditions to determine the activation energies of the reactions which are responsible for the chromophore consurnption and generation during peracetic acid bleaching to determine the kinetics of peracetic acid brightening for different pulp types to develop a complete kinetic mode1 capable of describing industrial peracetic acid brightening .0 sigiificantly retards the hydroxylation rate.reactions and oxidation of carbonyl containing lignin structures go to completion. A fiirther increase in pH to 10. while the conjugated quinones are the only residual chromophores when the treatment is extended beyond 50 minutes at 50°C. resulting in a reduced removal level of chromophores compared to that at pH 7.0.

APPENDIX THE COMPUTER OPTIMIZATION PROGRAM FOR THE KINETIC STUDY OF PERACETIC ACID BIUGHTENING .

NUMBER OF PARAMETERS TO BE FIT PARVAL.PARSTP(I 2).NUMBER OF DATA POINTS NUMPAR-.ARRAY OF CK ACCOUNTED BY QUINONE STRUCTURE NUMSET-.FTAG.REFERENCE SUM OR THE LOWEST SUM OF SQUARES OF DIFFERENCE IN LIGNIN CONTENT NEWSUM-.ARRAY OF EXPERTMENTAL ABSORPTION COEFFICIENTS # CKC -.ARRAY OF SET NUMBERS OF SIZE NUMSET SEPTS-.l O).PARCNT MTEGER FLAG(lZ).PAROLD INTEGER STUMP.PAO( 12).NUMPT. TAG.PRn\ST OUT TEMPORARY AND FINAL PARAMETER VALUES * * .l O).l O). SETPTS( 12).PHV(I 2).LSTONE.NUMBER OF DATA SETS SETNUM-.SET C C C C C C C C C C C C C C C C c # # # # # # # # # # # # # # # # # # # # # # # # # CKE -.SETNUM( 12).EXECUTE HOOKE AND JEEVES SEARCH ALGORITHM * * .ARRAY OF CALCULATED ABSORPTION COEFFICIENTS # TIM ARRAY OF THE SAMPLING TLME # PA0 ARRAY OF TOTAL PERACETIC ACID CONCENTRATION # PHV .l O). CKC0( 12.ARRAY OF CURRENT PARAMETER VALUES PARSTP.ARRAY OF TEMPERATURE # VARIABLE DICTIONARY -- -- C C C C C C C C C CKI .C C c ******************************************************************* * MAIN PROGRAM FOR THE MODELLING OF BLEACHING PROCESS * ******************************************************************* C C C C c C C C C ******************************************************************** * THE ROLES OF THE MAIN PROGRAM ARE : * * .CURSUM.SUM OF SQUARES CALCULATED USING NEW # # # # # # # # # # # # # # # .ARRAY OF CURRENT STEP SIZES STPSZL.TEMP(12) REAL CK 1( 12.NUMSET.ARRAY OF STEP SIZES USED TO KEEP TRACK OF PROPER SEARCH METHOD CURSUM-.TIM( 12.NLTMPAR.1 O).ARRAY OF p H # TEMP -.READ I AND MANIPLLATE DATA N * * . C D ( 12.STPSZL(12) REAL NEWStTM.ARRAY OF CK ACCOUNTED BY HYDROXYLATION CKCO -.ARRAY OF NT-JMBER OF POINTS I EACH DATA SET N NUMPT -.l O ) REAL PARVAL(1Z).P W OUT FINAL COMPARISONS * ******************************************************************** MAL CKE(12.ARRAY OF CK ACCOUNTED BY CARBONYL STRUCTURE CK2 -.CKC(12.

C C C C C C C
C

# PARAMETER C # VALUES, TO BE COMPARED WITH CURSUM # FLAG -- ARRAY OF TAGS IDENTIFYING WHICH PARAMETERS # HAVE CHANGED VALUE IN THE ITERATION # P, STUMP,LSTONE,PARCNT,TAG,FTAG # COUNTERS OR TAGS

-

# # # # # #

C
TAG TO BYPASS ITERATION SCHEME TAG=O

C
C C C C

SET NLRLiZBER OF ITERATIONS

WRITE(*,12) 12 FORMAT(1 X,'NtTMBER OF ITERATIONS :') READ(*, *) SET C C READ EXPERIMENTAL DATA FROM INPUT DATA FILE C OPEN(2,FILE='CKSO. DAT', STATUS='OLD1) READ(2, *) NUMSET,NUMPT READ(2, *) ((TIM(I,J),CKE(I,J), J= 1,NUMPT), I= 1,NUMSET) READ(2,*) (PAO(I),PHV(I),TEMP(I), I= 1,NUIUSET)
C C C

READ INITIAL PARAMETER VALUE GUESSES AND STEP S E E S AND PRINT

READ(2,*) NLTMPAR DO 30 I= 1,NUMPAR READ(2, *) PARVAL(I), PARSTP(1) FLAG(I)=O WRITE(*,50 1) I,PARVAL(I) 50 1 FORMAT(2X,'INITIAL GUESS OF PARAMETER',IZ,'=',ZX,F 18.5) WRITE(*, 503) PARSTP(1) 503 FORMAT(2XtINITIAL STEP SUE=', 12X,F 1 5.7) 30 CONTINUE CLOSE(2) C C WRITE INITIAL PARAMETERS INTO OUTPUT FILE C OPEN(3,FILE='OUTSO.DAT',STATUS='NEW1) DO 777 I=l,NUMPAR WRITE(3.723) I,PARVAL(I),PARSTP(I)

723 FORMAT(1 X,'INITIAL GUESS FOR PAR4METERS',I3,3X'=',F l5.4,2X,F 15.4) 777 c o m m WRITE(3,121) LSTONE= 1 PARCNT= 1

C C C
C C
C

SET SUMTOO
CURSUM=O.O

C
C

CALL SUBROUTINE TO CALCULATE CK AND DETERMINE SUM OF SQUARES FOR THE INITIAL BASE CASE

+
C C
C

CALL SUMCwSET,NUMPT,TMCKE,PAO,PW,TEMP,PARVAL, PARSTP, CKC,CURSUM) GO TO THE END OF PROGRAM IF TAG = 1

IF (TAG .EQ. GOTO 999 1) 570 CONTINUE PARCNT= 1 C C START SEARCH PATTERN C DO 5 15 I= 1,NUMPAR PARCNT=I

C
C C

INCREASE THE PARAMETER VALUE BY CORRESPONDING STEP S E E
PAROLD=PARVAL(PARCNT) PARVAL(PARCNT)= PAROLD+PARSTP(PARCNT)

CALCULATE THE NEW SUM OF SQUARES C 57 1 CALL SUMCAL(NUMSET,NUMPT,TIM,CKE,PAO,PHV,TEMP,PMVAL, PARSTP, + CKC,NEWSUM) C C CHECK IF NEW MINUMUNI H M BEEN FOUND C IF (NEWSUM .GT. CURSUM ) GOTO 550 CuRSUM=NEWSUM FLAG(I)= 1

C C

PAROLD=PARVAL(l) STPSZL(I)=PARSTP(I)
C C C

DECREASE THE PARAMETER VALUE BY STEP SIZE

PARVAL(I)=PAROLD-STPSZL(1)-PARSTP(1) 531 C0NTNL.E C F C CHECK I NEW PARAMETER VALUE IS GREATER THAN O
C

I (PARVAL(1).GT. GûTO 532 F 0.0) STPSZL(I)=STPSZL(I)/8 PARVAL(I)=PAROLDSTPSZL(1)-P ARSTP(1) GOTO 53 1 532 CONTINUE GOTO 55 1 550 CONTINUE STPSZL(I)=P ARSTP(1) C C DECREASE PARAMETER VALUE BY STEP SIZE
C

PARVAL(PARCNT)=PAROLD-PARSTP(PARCNT)
533 CON-

C C C

CHECK I NEW PARAMETER VALUE IS GREATER THAN O F

I (PARVAL(1).GT. GOTO 534 F 0.0) STPSZL(I)=STPSZL(I)/8 PARVAL(I)=P AROLD-STPSZL(1) GOTO 533 534 C O N T r n 551 CONTINUE C C CALCULATE NEW SUM OF SQUARES
C

+
C
C C

CALL SUMCAL(NUMSET,NUMPT,TIM,CKE,PAO,PHV,TEMPARVAL,PARSTP, CKC,NEWSUM)

CHECK I NEW MTNlMUM HAS BEEN FOUND F
I (NEWSUM .LT. F CURSUM ) GOTO 180 PARVAL(I)=PAROLD GOTO 560

180 CONTTNUE

PARSTP(I)=STPSZL(I) CURSUM=NEWSUM FLAG(I)= 1 560 CONTINUE C C EXAMINE NEXT PARAMETER IF NPT ALL HAS BEEN EXAMINED
C 515 CONTINUE

C C INCREASE ITERATION COUNTER AND CHECK IF LIMlT OF ITERATION H M C BEEN MET C LSTONE=LSTONE+ 1 IF (LSTONE .GT. SET) GOTO 100 C C CHECK IF MINIMUM IS ENCLOSED

C
DO 575 I=l,NUMPAR IF (FLAG(1) .EQ.1) GOTO 574

PARSTP(I)=PARSTP(I)*0.90
CONTINUE FLAG(I)=O 575 CONTrNuE
574

C

C
C

PRINT MTERMEDIATE PARAMETER VALUES AND SUM OF SQUARES

STUMP=LSTONE-1 WRITE(*,801) STUMP 80 1 FORMAT(ZX,' ITERATION NUMBER = ',2X,I4) DO 802 I=1 , M A R WRITE(*, 803) I,PARVAL(I),PARSTP(1) , 803 FORMAT(IX,' BEST VALUE OF PARAMETER ',12,'= ' 1X,F18.5,3X,F10.4) 802 CONTINUE WRITE(*,804) CURS UM 804 FORMAT(2X,'SUM OF SQUARES AT THIS STAGE = ',2X,F15.7) GOTO 570 331 CONTINUE 100 CONTINUE C C PRINT FINAL PARAMETER VALUES AND SUM OF SQUARES C WRITE(*, 120)

C
C DETERMTNE MINIMUM S U M OF SQUARES AND FWAL PARAMETER VALUES
C

CALL SCIMCmSET,NllMPT,TIM,CKE,PAO,PHV,TEMP,PARVAL,PARSTP, CKC,NEWSUM) M'RITE(*, 122) NEWSUM 122 FORMAT(2X,'SUM OF SQUARES OF BEST FIT EQUALS ',FI 5.9) M'RITE(*, 120) WRITE(*, 121) WRITE(*, 120) DO 977 I=I,NUMPAR WRITE(*, 123) I,PARVAL(I),PARSTP(I) 123 FORMAT(lX,'BESTFITFORPARAMETER',I3,3X'=',F18.5,2X,F15.4) 977 CONTINUE 999 CONTINUE PAUSE C C PRINT COMPARISON OF EXPERLMENTAL AND PREDICTED VALUES C 124 WRITE(*,1 20) WRITE(*, 121) WRITE(*, 120) W T E ( * , 125) 125 FORMAT(IX,' TIME(MTN) CKC CKE') WRITE(*, 128) 128 FORMAT(1 X,' -------------------------') WRITE(*, 120) DO 130 I=I,NUMSET DO 132 J=l,NUMPT WRITE(*, 131) TIM(I,J),CKC(I,J),CKE(I,J) 131 FORMAT(4X,F8.2, I3X,F7.4,11 YF7.4) 132 CONTINUE 130 CONTINUE

+

C

c

WRITE OUTPUT DATA INTO FILE

C
WRITE(3,122)NEWSUM
WR..ITE(3,120)

WRITE(3,121) WRITE(3,120) DO 987 I=l ,NUMPAR WRITE(3,123) 1, PARVAL(I), PARSTP(1) 987 CONTINUE C C P W T COMPAFUSON OF EXPERIMENTAL AND PREDICTED VALUES

C
WRITE(3,120) WRITE(3,121) WFUTE(3,120) WRITE(3,125) WRITE(3, I 28) WRITE(3,120) DO 133 I=l,NUMSET DO 134 J=l,NUMPT WRITE(3,13 1) TIM(I,J),CKC(I,J),CKE(I,J) 134 CONTINUE 133 CONTTNUE WRITE(3,lZO) WRITE(3,121) WRITE(3,120) WRJTE(3,165) WTE(3,168) WRITE(3,lZO) 165 FORMAT(1X,' TIME(MIN) CK 1 CK2 CKX') 1 68 FORMAT(1X,' ---------- ---------- ---------- ---------'1 DO 163 I=l,NUMSET DO 164 J= 1,NUMPT WRITE(3,169) TIM(I,J),CK 1(I,J),CKZ(I,J),CKCO(I,J) 169 FORMAT(3X,F5 .Z,SXF7.4,S?C,F7.4,8X,F7.4) 164 CONTTNUE 163 CONTINUE CLOSE(3) STOP END C C

c ********************************************************************
C C C C

* SUBROUTINE SUMCAL TO CALCULATE THE SUM OF SQUARES OF * * THE DIFFERENCE OF EXPERIMENTAL AND MODEL PREDICTED DATA * **************************************************#*****************

SUBROUTINE S U M C A L O \ I U M S E T , N U M P T , T I M , C K E , P A O , P H V , T E M , +PARSTP,CKC,SUM) REAL CKE(12,l O),CKC( 12,I O),TIM(12,1O),PAO( I2),PHV( 12),TEMP( 1 2) 10,C20,C 1,C2,C3,C4 REAL PARVAL(I2),PARSTP(12),CURSUM,CKO,C REAL M,K 1,K2,K3,K4,R,CKALPHA,CK 1 CK2 RVTEGER NUMSET,NUMPT
C C C

SETSUMSTOO SUMl=O.O SUM=O.O

C C C

SET KNOWN PARAMETERS CKO=2.8 1 R=8.3 14 CKALPHA=PARVAL(6) 8 CK1C K 2 ~ 2 .1-CKALPHA

C C C

CALCULATE CKC FOR ALL DATA SETS

DO 840 I= 1,NUMSET PA=PAO(I) CKC(I,1)=2.8 1 M= 1O *(8.2-PHV(1)) * DO 850 J=2,NUMPT C 1O=PARVAL( 1) C20=CK 1CK2-C 1O K 1=PARVAL(2)*M*PN(I +M) K2=PARVAL(3)*M*PAI(l+M) K3=PARVAL(4)*PA/( 1+M) K4=PARVAL(S)*PA/( 1+M) C l=C 1O*EXP(-(KI +K2)*TIM(I,J)) C2=C 10iK2*EXP(-(K 1+K2)*TIM(I,J))/(K3-K 1-K2) C3=(C2O+C 1O*K2/(K 1+K2-K3))*EXP(-K3 *TIM(I,J)) C4=CKALPHA*EXP(-K4*TIM(I, J)) CKC(I,J)=C 1+C2+C3+C4 C C C
850

SUM THE SQUARES OF DIFFERENCES OF CKC AND CKE
SUM I=SUM 1+(CKC(I,J)-CKE(I,J))**3 SUM=StTMl

cowm

840 CONTINUE RETURN END .

NY 14609 USA Phone: 7161482-0300 Fax: 7161268-5989 O 1993.All Righis Resewed .East -. Applied Image. Inc. ---.APFLIED =IMAGE.---1653 Main Street Rochester. lnc ..

Sign up to vote on this title
UsefulNot useful